線結晶構造解析

X

線結晶構造解析はすべて共同研究者の理化学研究所所属、橋爪大輔博士に依頼して測定をお願いした。得られた回折データは

RAXIS-CS Imaging Plate

回折計にて収集した。

構造解析は

SIR-97

を使用して直接法により行った²⁷⁾。

Table 5-2. Atomic coordinates and equivalent isotropic displacement parameters (Å2) for 4c.

U(is) is defined as one third of the trace of the orthogonalized Uij tensor.

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x y z U(is)

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N(1) 0.13588(13) -0.0034(2) -0.02577(12) 0.0195(5)

N(2) 0.22203(14) 0.1250(2) 0.05568(12) 0.0207(5)

N(3) 0.32413(14) 0.0309(2) -0.01854(13) 0.0229(6)

N(4) 0.21820(14) -0.0744(2) -0.08334(13) 0.0219(6)

N(5) 0.05680(14) 0.0711(2) 0.03977(13) 0.0209(5)

N(6) -0.02178(14) 0.1413(2) 0.10503(13) 0.0214(5)

C(1) 0.14861(17) -0.0764(3) -0.07834(15) 0.0208(6)

C(2) 0.20340(16) 0.0486(3) 0.00366(15) 0.0194(6)

C(3) 0.29374(16) 0.1544(3) 0.07017(14) 0.0199(6)

C(4) 0.34332(17) 0.1070(3) 0.03340(15) 0.0224(7)

C(5) 0.25248(16) 0.0026(3) -0.03278(14) 0.0196(6)

C(6) 0.06704(16) 0.0014(3) -0.01037(15) 0.0192(6)

C(7) -0.01114(16) 0.0709(3) 0.05196(15) 0.0207(6)

C(8) -0.08731(17) 0.1448(3) 0.11882(15) 0.0200(6)

C(9) 0.32236(16) 0.2361(3) 0.12855(16) 0.0228(7)

C(10) 0.37626(17) 0.3151(3) 0.12355(16) 0.0233(7)

C(11) 0.40602(16) 0.3893(3) 0.17929(16) 0.0232(7)

C(12) 0.38114(17) 0.3784(3) 0.24080(16) 0.0257(7)

C(20) 0.3713(2) 0.2651(4) 0.37865(18) 0.0427(10)

C(21) 0.2708(2) 0.4063(4) 0.33147(19) 0.0392(9)

C(22) 0.2455(2) 0.1988(4) 0.3145(2) 0.0483(11)

C(23) -0.09843(16) 0.2185(3) 0.17714(15) 0.0204(6)

C(24) -0.05516(17) 0.3162(3) 0.19525(15) 0.0217(6)

C(25) -0.06238(17) 0.3846(3) 0.25201(16) 0.0227(7)

C(26) -0.11244(17) 0.3501(3) 0.29037(15) 0.0238(7)

C(27) -0.15558(16) 0.2516(3) 0.27405(15) 0.0224(7)

C(28) -0.14866(16) 0.1872(3) 0.21604(15) 0.0204(6)

C(29) -0.01304(17) 0.4902(3) 0.27156(17) 0.0259(7)

C(30) -0.0224(2) 0.5688(3) 0.20695(18) 0.0339(8)

C(31) 0.06819(18) 0.4509(3) 0.2967(2) 0.0342(8)

C(32) -0.0320(2) 0.5604(3) 0.33191(19) 0.0334(8)

C(33) -0.20883(17) 0.2172(3) 0.31942(16) 0.0250(7)

C(34) -0.1633(2) 0.1974(3) 0.39661(17) 0.0321(8)

C(35) -0.26522(19) 0.3128(3) 0.31782(18) 0.0319(8)

C(36) -0.2509(2) 0.1074(3) 0.29329(18) 0.0342(8)

C(37A) 0.3671(2) 0.7703(4) -0.03721(18) 0.0406(9)

Cl(1A) 0.46423(7) 0.77871(11) 0.00050(6) 0.0550(3)

Cl(2A) 0.34752(7) 0.67171(14) -0.10671(7) 0.0717(4)

Cl(3A) 0.32215(7) 0.73707(12) 0.02826(6) 0.0654(4)

C(37B) 0.1204(2) 0.3478(4) 0.0434(2) 0.0455(10)

Cl(1B) 0.18169(11) 0.4128(2) 0.00022(11) 0.1194(8)

Cl(2B) 0.12264(9) 0.42217(13) 0.12183(8) 0.0787(5)

Cl(3B) 0.02981(10) 0.34982(15) -0.00961(10) 0.1094(7)

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Table 5-3. Bond lengths [Å] and angles [°] for 4c.

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N(1)-C(2) 1.390(4) N(1)-C(6) 1.394(4)

N(1)-C(1) 1.405(4) N(2)-C(2) 1.336(4)

N(2)-C(3) 1.343(4) N(3)-C(4) 1.334(4)

N(3)-C(5) 1.339(4) N(4)-C(1) 1.329(4)

N(4)-C(5) 1.375(4) N(5)-C(6) 1.328(4)

N(6)-C(8) 1.319(4) N(5)-C(7) 1.349(4)

N(6)-C(7) 1.381(4) C(1)-C(8)#1 1.460(4)

C(2)-C(5) 1.404(4) C(3)-C(4) 1.422(4)

C(3)-C(9) 1.485(4) C(4)-H(4) 0.9500

C(6)-C(7)#1 1.431(4) C(7)-C(6)#1 1.431(4)

C(8)-C(1)#1 1.460(4) C(8)-C(23) 1.488(4)

C(9)-C(10) 1.393(4) C(9)-C(14) 1.399(4)

C(10)-C(11) 1.398(4) C(10)-H(10) 0.9500

C(11)-C(12) 1.399(4) C(11)-C(15) 1.534(5)

C(12)-C(13) 1.395(5) C(12)-H(12) 0.9500

C(13)-C(19) 1.543(5) C(13)-C(14) 1.400(4) C(14)-H(14) 0.9500 C(15)-C(18) 1.536(5) C(15)-C(16) 1.541(5) C(15)-C(17) 1.547(5) C(16)-H(16A) 0.9800 C(16)-H(16B) 0.9800 C(16)-H(16C) 0.9800 C(17)-H(17A) 0.9800 C(17)-H(17B) 0.9800 C(17)-H(17C) 0.9800 C(18)-H(18A) 0.9800 C(18)-H(18B) 0.9800 C(18)-H(18C) 0.9800 C(19)-C(20) 1.522(5) C(19)-C(22) 1.541(5) C(19)-C(21) 1.543(5) C(20)-H(20A) 0.9800 C(20)-H(20B) 0.9800 C(20)-H(20C) 0.9800 C(21)-H(21A) 0.9800 C(21)-H(21B) 0.9800 C(21)-H(21C) 0.9800

C(29)-C(30) 1.540(5) C(29)-C(31) 1.544(4) C(29)-C(32) 1.553(5) C(30)-H(30A) 0.9800 C(30)-H(30B) 0.9800 C(30)-H(30C) 0.9800 C(31)-H(31A) 0.9800 C(31)-H(31B) 0.9800 C(31)-H(31C) 0.9800 C(32)-H(32A) 0.9800 C(32)-H(32B) 0.9800 C(32)-H(32C) 0.9800 C(33)-C(36) 1.533(5) C(33)-C(35) 1.537(5) C(33)-C(34) 1.552(4) C(34)-H(34A) 0.9800 C(34)-H(34B) 0.9800 C(34)-H(34C) 0.9800 C(35)-H(35A) 0.9800 C(35)-H(35B) 0.9800 C(35)-H(35C) 0.9800 C(36)-H(36A) 0.9800 C(36)-H(36B) 0.9800 C(36)-H(36C) 0.9800 C(37A)-Cl(3A) 1.742(4) C(37A)-Cl(2A) 1.754(4) C(37A)-Cl(1A) 1.782(4) C(37A)-H(37A) 1.0000 C(37B)-Cl(3B) 1.748(4) C(37B)-Cl(2B) 1.756(4) C(37B)-Cl(1B) 1.760(5) C(37B)-H(37B) 1.0000

C(2)-N(1)-C(6) 133.1(3) C(2)-N(1)-C(1) 105.6(2) C(6)-N(1)-C(1) 121.2(2) C(2)-N(2)-C(3) 112.9(3) C(4)-N(3)-C(5) 112.9(3) C(1)-N(4)-C(5) 104.3(3) C(6)-N(5)-C(7) 116.5(3) C(8)-N(6)-C(7) 119.3(3) N(4)-C(1)-N(1) 113.1(3) N(4)-C(1)-C(8)#1 128.3(3) N(1)-C(1)-C(8)#1 118.7(3) N(2)-C(2)-N(1) 130.3(3) N(2)-C(2)-C(5) 124.6(3) N(1)-C(2)-C(5) 105.1(2) N(2)-C(3)-C(4) 122.3(3) N(2)-C(3)-C(9) 118.5(3) C(4)-C(3)-C(9) 119.2(3) N(3)-C(4)-C(3) 124.3(3)

N(3)-C(4)-H(4) 117.8 C(3)-C(4)-H(4) 117.8

N(3)-C(5)-N(4) 125.0(3) N(3)-C(5)-C(2) 123.0(3) N(4)-C(5)-C(2) 111.9(3) N(5)-C(6)-N(1) 119.8(3) N(5)-C(6)-C(7)#1 124.5(3) N(1)-C(6)-C(7)#1 115.8(3) N(5)-C(7)-N(6) 116.8(3) N(5)-C(7)-C(6)#1 119.0(3) N(6)-C(7)-C(6)#1 124.1(3) N(6)-C(8)-C(1)#1 121.0(3) N(6)-C(8)-C(23) 119.4(3) C(1)#1-C(8)-C(23) 119.7(3) C(10)-C(9)-C(14) 120.3(3) C(10)-C(9)-C(3) 120.4(3)

C(10)-C(11)-C(12) 117.3(3) C(10)-C(11)-C(15) 121.9(3) C(12)-C(11)-C(15) 120.7(3) C(13)-C(12)-C(11) 123.1(3) C(13)-C(12)-H(12) 118.5 C(11)-C(12)-H(12) 118.5 C(12)-C(13)-C(14) 118.2(3) C(12)-C(13)-C(19) 119.8(3) C(14)-C(13)-C(19) 122.0(3) C(9)-C(14)-C(13) 120.1(3) C(9)-C(14)-H(14) 120.0 C(13)-C(14)-H(14) 120.0 C(11)-C(15)-C(18) 110.8(3) C(11)-C(15)-C(16) 112.0(3) C(18)-C(15)-C(16) 107.3(3) C(11)-C(15)-C(17) 107.7(3) C(18)-C(15)-C(17) 110.0(3) C(16)-C(15)-C(17) 109.1(3) C(15)-C(16)-H(16A) 109.5 C(15)-C(16)-H(16B) 109.5 H(16A)-C(16)-H(16B) 109.5 C(15)-C(16)-H(16C) 109.5 H(16A)-C(16)-H(16C) 109.5 H(16B)-C(16)-H(16C) 109.5 C(15)-C(17)-H(17A) 109.5 C(15)-C(17)-H(17B) 109.5 H(17A)-C(17)-H(17B) 109.5 C(15)-C(17)-H(17C) 109.5 H(17A)-C(17)-H(17C) 109.5 H(17B)-C(17)-H(17C) 109.5 C(15)-C(18)-H(18A) 109.5 C(15)-C(18)-H(18B) 109.5 H(18A)-C(18)-H(18B) 109.5 C(15)-C(18)-H(18C) 109.5 H(18A)-C(18)-H(18C) 109.5 H(18B)-C(18)-H(18C) 109.5 C(20)-C(19)-C(22) 109.2(3) C(20)-C(19)-C(13) 110.2(3) C(22)-C(19)-C(13) 111.3(3) C(20)-C(19)-C(21) 109.6(3) C(22)-C(19)-C(21) 108.1(3) C(13)-C(19)-C(21) 108.4(3) C(19)-C(20)-H(20A) 109.5 C(19)-C(20)-H(20B) 109.5 H(20A)-C(20)-H(20B) 109.5 C(19)-C(20)-H(20C) 109.5 H(20A)-C(20)-H(20C) 109.5 H(20B)-C(20)-H(20C) 109.5 C(19)-C(21)-H(21A) 109.5 C(19)-C(21)-H(21B) 109.5 H(21A)-C(21)-H(21B) 109.5 C(19)-C(21)-H(21C) 109.5 H(21A)-C(21)-H(21C) 109.5 H(21B)-C(21)-H(21C) 109.5 C(19)-C(22)-H(22A) 109.5 C(19)-C(22)-H(22B) 109.5 H(22A)-C(22)-H(22B) 109.5 C(19)-C(22)-H(22C) 109.5

C(28)-C(27)-C(26) 117.9(3) C(28)-C(27)-C(33) 121.9(3) C(26)-C(27)-C(33) 120.2(3) C(27)-C(28)-C(23) 120.7(3) C(27)-C(28)-H(28) 119.7 C(23)-C(28)-H(28) 119.7 C(25)-C(29)-C(30) 110.2(3) C(25)-C(29)-C(31) 108.4(3) C(30)-C(29)-C(31) 109.9(3) C(25)-C(29)-C(32) 112.5(3) C(30)-C(29)-C(32) 107.5(3) C(31)-C(29)-C(32) 108.2(3) C(29)-C(30)-H(30A) 109.5 C(29)-C(30)-H(30B) 109.5 H(30A)-C(30)-H(30B) 109.5 C(29)-C(30)-H(30C) 109.5 H(30A)-C(30)-H(30C) 109.5 H(30B)-C(30)-H(30C) 109.5 C(29)-C(31)-H(31A) 109.5 C(29)-C(31)-H(31B) 109.5 H(31A)-C(31)-H(31B) 109.5 C(29)-C(31)-H(31C) 109.5 H(31A)-C(31)-H(31C) 109.5 H(31B)-C(31)-H(31C) 109.5 C(29)-C(32)-H(32A) 109.5 C(29)-C(32)-H(32B) 109.5 H(32A)-C(32)-H(32B) 109.5 C(29)-C(32)-H(32C) 109.5 H(32A)-C(32)-H(32C) 109.5 H(32B)-C(32)-H(32C) 109.5 C(36)-C(33)-C(35) 108.7(3) C(36)-C(33)-C(27) 112.3(3) C(35)-C(33)-C(27) 109.5(3) C(36)-C(33)-C(34) 107.8(3) C(35)-C(33)-C(34) 109.6(3) C(27)-C(33)-C(34) 108.8(3) C(33)-C(34)-H(34A) 109.5 C(33)-C(34)-H(34B) 109.5 H(34A)-C(34)-H(34B) 109.5 C(33)-C(34)-H(34C) 109.5 H(34A)-C(34)-H(34C) 109.5 H(34B)-C(34)-H(34C) 109.5 C(33)-C(35)-H(35A) 109.5 C(33)-C(35)-H(35B) 109.5 H(35A)-C(35)-H(35B) 109.5 C(33)-C(35)-H(35C) 109.5 H(35A)-C(35)-H(35C) 109.5 H(35B)-C(35)-H(35C) 109.5 C(33)-C(36)-H(36A) 109.5 C(33)-C(36)-H(36B) 109.5 H(36A)-C(36)-H(36B) 109.5 H(36A)-C(36)-H(36C) 109.5 H(36B)-C(36)-H(36C) 109.5 Cl(3A)-C(37A)-Cl(2A) 112.0(3) Cl(3A)-C(37A)-Cl(1A) 109.76(19) Cl(2A)-C(37A)-Cl(1A) 110.4(2) Cl(3A)-C(37A)-H(37A) 108.2 Cl(2A)-C(37A)-H(37A) 108.2 Cl(1A)-C(37A)-H(37A) 108.2 Cl(3B)-C(37B)-Cl(2B) 108.5(2) Cl(3B)-C(37B)-Cl(1B) 111.1(2) Cl(2B)-C(37B)-Cl(1B) 109.0(3) Cl(3B)-C(37B)-H(37B) 109.4 Cl(2B)-C(37B)-H(37B) 109.4 Cl(1B)-C(37B)-H(37B) 109.4

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Table 5-4. Anisotropic displacement parameters (Å) for 4c.

The anisotropic displacement factor exponent takes the form: -2π2[ h2a*2U11 + ... + 2 h k a* b* U12 ] ______________________________________________________________________________

U11 U22 U33 U23 U13 U12

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N(1) 0.0192(12) 0.0211(14) 0.0201(11) -0.0035(10) 0.0083(10) -0.0002(10) N(2) 0.0198(13) 0.0238(14) 0.0198(11) -0.0014(10) 0.0076(10) -0.0013(11) N(3) 0.0195(13) 0.0287(15) 0.0220(12) -0.0015(11) 0.0081(10) -0.0007(11) N(4) 0.0190(12) 0.0269(15) 0.0216(11) -0.0029(11) 0.0087(10) -0.0007(11) N(5) 0.0202(13) 0.0211(14) 0.0239(12) -0.0014(10) 0.0103(10) -0.0021(11) N(6) 0.0200(13) 0.0238(14) 0.0227(12) -0.0035(11) 0.0096(10) -0.0023(11) C(1) 0.0230(15) 0.0197(16) 0.0225(13) 0.0004(12) 0.0110(12) 0.0011(13) C(2) 0.0177(14) 0.0214(16) 0.0209(13) 0.0026(12) 0.0080(11) -0.0017(12) C(3) 0.0208(15) 0.0217(16) 0.0174(12) 0.0003(12) 0.0052(11) -0.0014(12) C(4) 0.0172(14) 0.0272(17) 0.0231(14) 0.0015(12) 0.0052(11) -0.0021(13) C(5) 0.0208(15) 0.0210(16) 0.0176(12) -0.0032(11) 0.0062(11) -0.0013(12) C(6) 0.0170(14) 0.0220(16) 0.0198(13) 0.0008(12) 0.0070(11) -0.0003(12) C(7) 0.0218(15) 0.0208(16) 0.0219(13) -0.0009(12) 0.0100(11) 0.0004(12) C(8) 0.0233(15) 0.0183(16) 0.0197(13) 0.0002(12) 0.0081(11) 0.0018(12) C(9) 0.0177(14) 0.0249(17) 0.0247(14) -0.0030(13) 0.0036(12) 0.0011(13) C(10) 0.0230(15) 0.0256(17) 0.0238(14) -0.0019(13) 0.0105(12) -0.0006(13) C(11) 0.0169(14) 0.0233(17) 0.0287(15) -0.0022(13) 0.0044(12) -0.0007(13) C(12) 0.0188(15) 0.0285(18) 0.0289(15) -0.0083(14) 0.0042(12) 0.0002(13) C(13) 0.0223(16) 0.0253(17) 0.0280(15) -0.0038(13) 0.0082(12) -0.0006(13) C(14) 0.0208(15) 0.0241(17) 0.0299(15) -0.0022(13) 0.0109(12) -0.0018(13) C(15) 0.0259(17) 0.0254(18) 0.0380(17) -0.0039(15) 0.0119(14) -0.0047(14) C(16) 0.034(2) 0.034(2) 0.048(2) -0.0056(17) 0.0187(16) -0.0102(17) C(17) 0.0229(17) 0.030(2) 0.056(2) -0.0039(17) 0.0078(16) -0.0032(15) C(18) 0.0275(18) 0.0265(19) 0.0422(19) -0.0025(15) 0.0069(15) -0.0011(15)

C(26) 0.0235(15) C(27) 0.0186(14) C(28) 0.0175(14) C(29) 0.0250(16) C(30) 0.040(2) C(31) 0.0257(17) C(32) 0.0332(19) C(33) 0.0212(15) C(34) 0.0319(18) C(35) 0.0252(17) C(36) 0.0322(19) C(37A) 0.049(2) Cl(1A) 0.0532(7) Cl(2A) 0.0558(7) Cl(3A) 0.0691(8) C(37B) 0.055(3) Cl(1B) 0.1055(13) Cl(2B) 0.1108(12) Cl(3B) 0.0920(12) _________________ 0.0269(18) 0.0213(13) -0.0065(13) 0.0061(12) 0.0020(13) 0.0251(17) 0.0248(14) -0.0018(13) 0.0079(12) 0.0024(13) 0.0220(16) 0.0221(14) -0.0028(12) 0.0057(11) 0.0004(12) 0.0235(17) 0.0307(15) -0.0065(13) 0.0098(13) -0.0035(14) 0.0268(19) 0.0371(18) -0.0029(15) 0.0137(15) -0.0072(16) 0.033(2) 0.0450(19) -0.0119(16) 0.0101(15) -0.0051(15) 0.0287(19) 0.0396(18) -0.0123(15) 0.0117(15) -0.0051(15) 0.0300(18) 0.0264(15) -0.0035(13) 0.0110(12) -0.0001(14) 0.041(2) 0.0260(16) -0.0002(15) 0.0130(14) 0.0026(16) 0.042(2) 0.0325(17) -0.0011(16) 0.0145(14) 0.0036(16) 0.043(2) 0.0341(17) -0.0071(16) 0.0201(15) -0.0085(16) 0.045(2) 0.0307(17) 0.0056(17) 0.0164(16) 0.0173(19) 0.0540(7) 0.0587(6) -0.0006(5) 0.0156(5) 0.0029(5) 0.0925(11) 0.0633(7) -0.0333(7) 0.0085(6) 0.0192(7) 0.0836(10) 0.0561(6) 0.0330(6) 0.0392(6) 0.0275(7) 0.041(2) 0.042(2) 0.0014(18) 0.0154(19) 0.015(2) 0.1499(18) 0.1326(15) 0.0844(14) 0.0857(12) 0.0636(13) 0.0602(9) 0.0721(8) -0.0214(7) 0.0362(8) -0.0012(8) 0.0785(11) 0.1209(13) 0.0489(10) -0.0415(10) -0.0231(9) _____________________________________________________________

Table 5-5. Hydrogen coordinates and isotropic displacement parameters for 4c.

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x y z U(eq)

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H(4) 0.3934 0.1312 0.0467 0.027

H(10) 0.3931 0.3187 0.0816 0.028

H(12) 0.4016 0.4269 0.2796 0.031

H(14) 0.2600 0.1759 0.1930 0.029

H(16A) 0.4287 0.5064 0.0673 0.056

H(16B) 0.4945 0.4156 0.0853 0.056

H(16C) 0.5120 0.5479 0.0987 0.056

H(17A) 0.5524 0.3592 0.2089 0.055

H(17B) 0.5341 0.4273 0.2733 0.055

H(17C) 0.5793 0.4878 0.2240 0.055

H(18A) 0.4414 0.5897 0.2473 0.049

H(18B) 0.4006 0.6198 0.1671 0.049

H(18C) 0.4867 0.6472 0.1969 0.049

H(20A) 0.4073 0.3270 0.3836 0.064

H(20B) 0.3942 0.1941 0.3688 0.064

H(20C) 0.3556 0.2573 0.4226 0.064

H(21A) 0.2303 0.4260 0.2906 0.059

H(21B) 0.3089 0.4653 0.3387 0.059

H(21C) 0.2517 0.4005 0.3737 0.059

H(22A) 0.2669 0.1242 0.3096 0.072

H(22B) 0.2036 0.2127 0.2737 0.072

H(22C) 0.2283 0.2005 0.3579 0.072

H(24) -0.0207 0.3364 0.1690 0.026

H(26) -0.1175 0.3953 0.3291 0.029

H(32A) -0.0012 0.6289 0.3405 0.050

H(32B) -0.0224 0.5146 0.3751 0.050

H(32C) -0.0843 0.5822 0.3182 0.050

H(34A) -0.1337 0.2650 0.4137 0.048

H(34B) -0.1305 0.1320 0.3981 0.048

H(34C) -0.1970 0.1825 0.4268 0.048

H(35A) -0.2944 0.3245 0.2691 0.048

H(35B) -0.2390 0.3831 0.3357 0.048

H(35C) -0.2982 0.2919 0.3476 0.048

H(36A) -0.2155 0.0460 0.2933 0.051

H(36B) -0.2816 0.1186 0.2452 0.051

H(36C) -0.2824 0.0873 0.3247 0.051

H(37A) 0.3494 0.8465 -0.0569 0.049

H(37B) 0.1361 0.2674 0.0551 0.055

________________________________________________________________________________

Table 5-6. Torsion angles [°] for 4c.

___________________________________________________________________________________

C(5)-N(4)-C(1)-N(1) -0.2(3) C(5)-N(4)-C(1)-C(8)#1 -179.0(3) C(2)-N(1)-C(1)-N(4) 0.5(3) C(6)-N(1)-C(1)-N(4) -176.6(3) C(2)-N(1)-C(1)-C(8)#1 179.4(3) C(6)-N(1)-C(1)-C(8)#1 2.3(4)

C(3)-N(2)-C(2)-N(1) 179.1(3) C(3)-N(2)-C(2)-C(5) 0.1(4) C(6)-N(1)-C(2)-N(2) -3.1(6) C(1)-N(1)-C(2)-N(2) -179.7(3) C(6)-N(1)-C(2)-C(5) 176.1(3) C(1)-N(1)-C(2)-C(5) -0.5(3) C(2)-N(2)-C(3)-C(4) -0.5(4) C(2)-N(2)-C(3)-C(9) -178.1(3) C(5)-N(3)-C(4)-C(3) -0.2(4) N(2)-C(3)-C(4)-N(3) 0.6(5) C(9)-C(3)-C(4)-N(3) 178.2(3) C(4)-N(3)-C(5)-N(4) -179.5(3) C(4)-N(3)-C(5)-C(2) -0.2(4) C(1)-N(4)-C(5)-N(3) 179.3(3) C(1)-N(4)-C(5)-C(2) -0.1(4) N(2)-C(2)-C(5)-N(3) 0.3(5) N(1)-C(2)-C(5)-N(3) -179.0(3) N(2)-C(2)-C(5)-N(4) 179.7(3) N(1)-C(2)-C(5)-N(4) 0.4(3) C(7)-N(5)-C(6)-N(1) -179.8(3) C(7)-N(5)-C(6)-C(7)#1 1.0(5) C(2)-N(1)-C(6)-N(5) 3.6(5) C(1)-N(1)-C(6)-N(5) 179.8(3) C(2)-N(1)-C(6)-C(7)#1 -177.1(3) C(1)-N(1)-C(6)-C(7)#1 -0.9(4) C(6)-N(5)-C(7)-N(6) 178.7(3) C(6)-N(5)-C(7)-C(6)#1 -0.9(5) C(8)-N(6)-C(7)-N(5) 179.6(3) C(8)-N(6)-C(7)-C(6)#1 -0.8(5) C(7)-N(6)-C(8)-C(1)#1 -0.7(4) C(7)-N(6)-C(8)-C(23) 178.5(3) N(2)-C(3)-C(9)-C(10) -144.4(3) C(4)-C(3)-C(9)-C(10) 37.8(4) N(2)-C(3)-C(9)-C(14) 38.9(4) C(4)-C(3)-C(9)-C(14) -138.8(3) C(14)-C(9)-C(10)-C(11) -0.6(5) C(3)-C(9)-C(10)-C(11) -177.2(3) C(9)-C(10)-C(11)-C(12) 1.9(5) C(9)-C(10)-C(11)-C(15) 178.9(3) C(10)-C(11)-C(12)-C(13) -1.4(5) C(15)-C(11)-C(12)-C(13) -178.5(3) C(11)-C(12)-C(13)-C(14) -0.4(5) C(11)-C(12)-C(13)-C(19) 178.8(3) C(10)-C(9)-C(14)-C(13) -1.3(5) C(3)-C(9)-C(14)-C(13) 175.4(3) C(12)-C(13)-C(14)-C(9) 1.8(5) C(19)-C(13)-C(14)-C(9) -177.4(3) C(10)-C(11)-C(15)-C(18) 132.2(3)

C(1)#1-C(8)-C(23)-C(24) -152.6(3) C(28)-C(23)-C(24)-C(25) -0.8(4) C(8)-C(23)-C(24)-C(25) -177.3(3) C(23)-C(24)-C(25)-C(26) 1.6(4) C(23)-C(24)-C(25)-C(29) 178.9(3) C(24)-C(25)-C(26)-C(27) -0.6(5) C(29)-C(25)-C(26)-C(27) -177.7(3) C(25)-C(26)-C(27)-C(28) -1.3(5) C(25)-C(26)-C(27)-C(33) 178.9(3) C(26)-C(27)-C(28)-C(23) 2.1(4) C(33)-C(27)-C(28)-C(23) -178.1(3) C(24)-C(23)-C(28)-C(27) -1.1(4) C(8)-C(23)-C(28)-C(27) 175.4(3) C(26)-C(25)-C(29)-C(30) -126.9(3) C(24)-C(25)-C(29)-C(30) 56.0(4) C(26)-C(25)-C(29)-C(31) 112.7(3) C(24)-C(25)-C(29)-C(31) -64.4(4) C(26)-C(25)-C(29)-C(32) -6.9(4) C(24)-C(25)-C(29)-C(32) 176.0(3) C(28)-C(27)-C(33)-C(36) 0.2(4) C(26)-C(27)-C(33)-C(36) -179.9(3) C(28)-C(27)-C(33)-C(35) -120.6(3) C(26)-C(27)-C(33)-C(35) 59.2(4) C(28)-C(27)-C(33)-C(34) 119.6(3) C(26)-C(27)-C(33)-C(34) -60.6(4)

___________________________________________________________________________________

Symmetry transformations used to generate equivalent atoms:

#1 -x,-y,-z

Table 5-7. Atomic coordinates and equivalent isotropic displacement parameters (Å²) for 7b.

U(is) is defined as one third of the trace of the orthogonalized Uij tensor.

________________________________________________________________________________

x y z U(is)

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F(1) 0.05570(4) 0.32906(4) 0.23506(4) 0.02749(16)

F(2) 0.19135(4) 0.32176(4) 0.20979(4) 0.02641(15)

O(1) 0.14723(5) 0.34049(4) 0.34439(4) 0.02798(18)

N(1) 0.12800(5) 0.22447(5) 0.42341(5) 0.02118(17)

N(2) 0.12800(6) 0.04021(5) 0.30055(6) 0.0291(2)

N(3) 0.12771(4) 0.20783(5) 0.27734(5) 0.01796(16)

C(1) 0.12721(5) 0.17683(5) 0.35416(6) 0.01833(18)

C(2) 0.12738(6) 0.09117(6) 0.36333(7) 0.0247(2)

C(3) 0.12772(7) 0.07360(7) 0.22472(7) 0.0296(2)

C(4) 0.12761(6) 0.15635(6) 0.21218(6) 0.0247(2)

C(5) 0.13837(5) 0.30231(5) 0.41516(5) 0.01826(18)

C(6) 0.14072(6) 0.35741(6) 0.48985(6) 0.02105(19)

C(7) 0.14301(9) 0.30765(7) 0.56914(7) 0.0340(3)

C(8) 0.21589(7) 0.41279(8) 0.48398(8) 0.0360(3)

C(9) 0.06257(6) 0.40909(7) 0.48798(7) 0.0269(2)

B(1) 0.13024(6) 0.30350(6) 0.26471(6) 0.0194(2)

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Table 5-8. Bond lengths [Å] and angles [°] for 7b.

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F(1)-B(1) 1.3776(12) F(2)-B(1) 1.3736(12) O(1)-C(5) 1.3165(11) O(1)-B(1) 1.4557(13) N(1)-C(5) 1.2932(12) N(1)-C(1) 1.3690(12) N(2)-C(2) 1.3177(14) N(2)-C(3) 1.3475(15) N(3)-C(1) 1.3469(12) N(3)-C(4) 1.3530(12) N(3)-B(1) 1.5809(13) C(1)-C(2) 1.4110(13) C(2)-H(2) 0.958(13) C(3)-C(4) 1.3707(15) C(3)-H(3) 0.964(15) C(4)-H(4) 0.963(13) C(5)-C(6) 1.5125(13) C(6)-C(7) 1.5244(15) C(6)-C(8) 1.5323(15) C(6)-C(9) 1.5350(14) C(7)-H(7A) 0.980(15) C(7)-H(7B) 0.993(15) C(7)-H(7C) 0.995(16) C(8)-H(8A) 1.012(15) C(8)-H(8B) 1.019(17) C(8)-H(8C) 0.974(17) C(9)-H(9A) 0.983(14) C(9)-H(9B) 0.978(14) C(9)-H(9C) 0.958(15)

C(5)-O(1)-B(1) 123.87(8) C(5)-N(1)-C(1) 118.56(8) C(2)-N(2)-C(3) 116.75(9) C(1)-N(3)-C(4) 119.30(8) C(1)-N(3)-B(1) 119.60(7) C(4)-N(3)-B(1) 121.09(8) N(3)-C(1)-N(1) 123.09(8) N(3)-C(1)-C(2) 118.21(9) N(1)-C(1)-C(2) 118.69(9) N(2)-C(2)-C(1) 123.24(10) N(2)-C(2)-H(2) 119.6(8) C(1)-C(2)-H(2) 117.2(8) N(2)-C(3)-C(4) 122.48(10) N(2)-C(3)-H(3) 118.3(9) C(4)-C(3)-H(3) 119.2(9) N(3)-C(4)-C(3) 120.01(10) N(3)-C(4)-H(4) 117.2(8) C(3)-C(4)-H(4) 122.8(8) N(1)-C(5)-O(1) 124.98(8) N(1)-C(5)-C(6) 120.57(8) O(1)-C(5)-C(6) 114.45(8) C(5)-C(6)-C(7) 111.03(8) C(5)-C(6)-C(8) 108.89(8) C(7)-C(6)-C(8) 110.45(9) C(5)-C(6)-C(9) 106.98(8) C(7)-C(6)-C(9) 109.40(9) C(8)-C(6)-C(9) 110.03(9) C(6)-C(7)-H(7A) 109.9(9) C(6)-C(7)-H(7B) 109.0(9) H(7A)-C(7)-H(7B) 107.6(13) C(6)-C(7)-H(7C) 109.2(8) H(7A)-C(7)-H(7C) 108.9(13)

C(6)-C(8)-H(8C) 108.4(10) H(8A)-C(8)-H(8C) 107.9(12) H(8B)-C(8)-H(8C) 111.1(13) C(6)-C(9)-H(9A) 108.4(8) C(6)-C(9)-H(9B) 110.8(8) H(9A)-C(9)-H(9B) 108.6(11) C(6)-C(9)-H(9C) 110.4(9) H(9A)-C(9)-H(9C) 110.9(12) H(9B)-C(9)-H(9C) 107.6(12) F(2)-B(1)-F(1) 110.65(8) F(2)-B(1)-O(1) 110.32(8) F(1)-B(1)-O(1) 110.70(8) F(2)-B(1)-N(3) 108.61(8) F(1)-B(1)-N(3) 108.87(8) O(1)-B(1)-N(3) 107.59(7)

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Symmetry transformations used to generate equivalent atoms:

Table 5-9. Anisotropic displacement parameters (Å) for 7b.

The anisotropic displacement factor exponent takes the form: -2π²[ h²a*²U11 + ... + 2 h k a* b* U12 ] ______________________________________________________________________________

U11 U22 U33 U23 U13 U12

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F(1) 0.0203(3) 0.0249(3) 0.0373(3) 0.0067(2) -0.0036(2) 0.0035(2) F(2) 0.0224(3) 0.0290(3) 0.0278(3) 0.0062(2) 0.0030(2) -0.0018(2) O(1) 0.0460(5) 0.0172(3) 0.0208(3) 0.0022(3) -0.0026(3) -0.0045(3) N(1) 0.0246(4) 0.0178(4) 0.0212(4) 0.0011(3) 0.0012(3) 0.0010(3) N(2) 0.0270(4) 0.0190(4) 0.0412(5) -0.0037(4) -0.0064(4) 0.0007(3) N(3) 0.0140(3) 0.0187(4) 0.0212(4) -0.0010(3) -0.0021(3) 0.0007(3) C(1) 0.0137(4) 0.0177(4) 0.0236(4) 0.0012(3) -0.0002(3) 0.0001(3) C(2) 0.0240(5) 0.0177(4) 0.0324(5) 0.0025(4) -0.0003(4) -0.0005(3) C(3) 0.0297(5) 0.0250(5) 0.0343(5) -0.0098(4) -0.0088(4) 0.0044(4) C(4) 0.0237(5) 0.0259(5) 0.0243(5) -0.0052(4) -0.0052(4) 0.0028(4) C(5) 0.0165(4) 0.0182(4) 0.0201(4) 0.0019(3) -0.0014(3) 0.0017(3) C(6) 0.0213(4) 0.0203(4) 0.0216(4) -0.0023(3) -0.0031(3) 0.0026(3) C(7) 0.0504(7) 0.0317(6) 0.0199(5) -0.0016(4) -0.0040(5) 0.0132(5) C(8) 0.0259(5) 0.0424(7) 0.0396(6) -0.0159(5) -0.0002(5) -0.0085(5) C(9) 0.0250(5) 0.0248(5) 0.0309(5) -0.0031(4) -0.0018(4) 0.0060(4) B(1) 0.0203(5) 0.0175(4) 0.0204(4) 0.0025(3) -0.0014(4) 0.0003(3) ______________________________________________________________________________

Table 5-10. Hydrogen coordinates and isotropic displacement parameters for 7b.

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x y z U(eq)

________________________________________________________________________________

H(2) 0.1274(8) 0.0701(8) 0.4184(8) 0.027(3)

H(3) 0.1278(9) 0.0376(9) 0.1778(9) 0.041(4)

H(4) 0.1272(8) 0.1805(8) 0.1581(8) 0.030(3)

H(7A) 0.1450(9) 0.3443(9) 0.6168(9) 0.045(4)

H(7B) 0.1934(9) 0.2740(9) 0.5698(9) 0.042(4)

H(7C) 0.0928(9) 0.2736(9) 0.5727(9) 0.041(4)

H(8A) 0.2179(9) 0.4477(9) 0.5353(9) 0.041(4)

H(8B) 0.2135(10) 0.4491(10) 0.4331(10) 0.052(4)

H(8C) 0.2645(10) 0.3785(10) 0.4834(9) 0.050(4)

H(9A) 0.0619(9) 0.4443(9) 0.5370(9) 0.035(3)

H(9B) 0.0141(8) 0.3743(8) 0.4890(8) 0.030(3)

H(9C) 0.0604(9) 0.4410(9) 0.4386(10) 0.041(4)

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Table 5-11. Torsion angles [°] for 7b.

___________________________________________________________________________________

C(4)-N(3)-C(1)-N(1) 179.40(8) B(1)-N(3)-C(1)-N(1) 0.65(13) C(4)-N(3)-C(1)-C(2) 0.59(13) B(1)-N(3)-C(1)-C(2) -178.16(8) C(5)-N(1)-C(1)-N(3) -7.53(13) C(5)-N(1)-C(1)-C(2) 171.28(9) C(3)-N(2)-C(2)-C(1) -0.60(15) N(3)-C(1)-C(2)-N(2) 0.00(14) N(1)-C(1)-C(2)-N(2) -178.86(9) C(2)-N(2)-C(3)-C(4) 0.63(16) C(1)-N(3)-C(4)-C(3) -0.57(14) B(1)-N(3)-C(4)-C(3) 178.17(9) N(2)-C(3)-C(4)-N(3) -0.06(16) C(1)-N(1)-C(5)-O(1) 1.05(14) C(1)-N(1)-C(5)-C(6) -179.27(8) B(1)-O(1)-C(5)-N(1) 13.02(15) B(1)-O(1)-C(5)-C(6) -166.69(8) N(1)-C(5)-C(6)-C(7) 8.85(13) O(1)-C(5)-C(6)-C(7) -171.43(9) N(1)-C(5)-C(6)-C(8) 130.67(10) O(1)-C(5)-C(6)-C(8) -49.61(11) N(1)-C(5)-C(6)-C(9) -110.45(10) O(1)-C(5)-C(6)-C(9) 69.27(10) C(5)-O(1)-B(1)-F(2) -135.68(9) C(5)-O(1)-B(1)-F(1) 101.50(10) C(5)-O(1)-B(1)-N(3) -17.35(12) C(1)-N(3)-B(1)-F(2) 130.06(8) C(4)-N(3)-B(1)-F(2) -48.67(11) C(1)-N(3)-B(1)-F(1) -109.38(9) C(4)-N(3)-B(1)-F(1) 71.89(11) C(1)-N(3)-B(1)-O(1) 10.63(11) C(4)-N(3)-B(1)-O(1) -168.09(8)

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Symmetry transformations used to generate equivalent atoms:

Table 5-12. Atomic coordinates and equivalent isotropic displacement parameters (Å²) for 8a.

U(is) is defined as one third of the trace of the orthogonalized Uij tensor.

________________________________________________________________________________

x y z U(is)

________________________________________________________________________________

F(1) 0.08068(11) -0.03996(9) 0.43921(5) 0.0295(2)

F(2) 0.31070(13) -0.06731(9) 0.50760(4) 0.0308(2)

O(1A) 0.3625(6) -0.0758(4) 0.4054(2) 0.0147(4)

O(1B) 0.3290(7) -0.0718(4) 0.3947(2) 0.0147(4)

N(1) 0.28294(13) 0.15290(11) 0.45095(5) 0.0139(2)

N(2) 0.45811(13) 0.13721(11) 0.36343(5) 0.0154(2)

N(3) 0.33533(13) 0.44333(11) 0.45432(5) 0.0144(2)

N(4) -0.06919(17) 0.81670(14) 0.72229(6) 0.0286(3)

C(1) 0.38051(15) 0.21323(12) 0.40828(5) 0.0132(2)

C(2) 0.40132(15) 0.36339(12) 0.41141(5) 0.0148(2)

C(3) 0.24081(14) 0.37945(12) 0.49776(5) 0.0130(2)

C(4) 0.21268(15) 0.23372(13) 0.49516(5) 0.0147(2)

C(5) 0.17087(14) 0.47128(12) 0.54632(5) 0.0132(2)

C(6) 0.20018(15) 0.61869(13) 0.54461(5) 0.0152(2)

C(7) 0.13865(16) 0.70823(13) 0.58995(6) 0.0165(2)

C(8) 0.04703(15) 0.65000(13) 0.63812(5) 0.0158(2)

C(9) 0.01593(16) 0.50339(14) 0.64024(6) 0.0171(2)

C(10) 0.07655(16) 0.41526(13) 0.59442(6) 0.0164(2)

C(11) -0.01689(16) 0.74238(14) 0.68512(6) 0.0193(2)

C(12) 0.43774(15) -0.00060(13) 0.36201(6) 0.0159(2)

C(13) 0.51493(16) -0.09017(13) 0.31210(6) 0.0183(2)

C(14) 0.3733(2) -0.11184(18) 0.26051(7) 0.0323(3)

C(15) 0.5708(3) -0.23389(17) 0.33948(7) 0.0363(4)

C(16) 0.6641(2) -0.01337(19) 0.28402(10) 0.0438(5)

Table 5-13. Bond lengths [Å] and angles [°] for 8a.

___________________________________________________________________________________

F(1)-B(1) 1.3771(18) F(2)-B(1) 1.3773(18)

O(1A)-C(12) 1.332(3) O(1A)-B(1) 1.454(3)

O(1B)-C(12) 1.316(4) O(1B)-B(1) 1.472(4)

N(1)-C(1) 1.3497(15) N(1)-C(4) 1.3546(15)

N(1)-B(1) 1.5849(18) N(2)-C(12) 1.3032(16)

N(2)-C(1) 1.3669(15) N(3)-C(2) 1.3150(15)

N(3)-C(3) 1.3614(15) N(4)-C(11) 1.1511(18)

C(1)-C(2) 1.4197(16) C(2)-H(2) 0.982(18)

C(3)-C(4) 1.3858(17) C(3)-C(5) 1.4799(16)

C(4)-H(4) 0.958(18) C(5)-C(6) 1.4031(17)

C(5)-C(10) 1.4042(16) C(6)-C(7) 1.3910(16)

C(6)-H(6) 0.967(17) C(7)-C(8) 1.4014(17)

C(7)-H(7) 0.979(18) C(8)-C(9) 1.3984(18)

C(8)-C(11) 1.4399(17) C(9)-C(10) 1.3877(17)

C(9)-H(9) 0.955(18) C(10)-H(10) 0.972(19)

C(12)-C(13) 1.5128(16) C(13)-C(15) 1.526(2)

C(13)-C(16) 1.528(2) C(13)-C(14) 1.538(2)

C(14)-H(14A) 0.9800 C(14)-H(14B) 0.9800

C(14)-H(14C) 0.9800 C(15)-H(15A) 0.9800

C(15)-H(15B) 0.9800 C(15)-H(15C) 0.9800

C(16)-H(16A) 0.9800 C(16)-H(16B) 0.9800

C(16)-H(16C) 0.9800

C(12)-O(1A)-B(1) 123.8(3) C(12)-O(1B)-B(1) 123.6(3) C(1)-N(1)-C(4) 120.50(10) C(1)-N(1)-B(1) 120.18(10) C(4)-N(1)-B(1) 119.31(10) C(12)-N(2)-C(1) 118.38(10) C(2)-N(3)-C(3) 118.55(10) N(1)-C(1)-N(2) 123.33(11) N(1)-C(1)-C(2) 116.92(10) N(2)-C(1)-C(2) 119.76(10) N(3)-C(2)-C(1) 123.38(11) N(3)-C(2)-H(2) 119.9(11) C(1)-C(2)-H(2) 116.7(11) N(3)-C(3)-C(4) 119.93(11) N(3)-C(3)-C(5) 117.52(10) C(4)-C(3)-C(5) 122.55(11) N(1)-C(4)-C(3) 120.68(11) N(1)-C(4)-H(4) 115.2(11)

C(7)-C(6)-C(5) 120.87(11) C(7)-C(6)-H(6) 121.6(11) C(5)-C(6)-H(6) 117.5(11) C(6)-C(7)-C(8) 119.42(11) C(6)-C(7)-H(7) 118.5(10) C(8)-C(7)-H(7) 122.1(10) C(9)-C(8)-C(7) 120.36(11) C(9)-C(8)-C(11) 120.07(11) C(7)-C(8)-C(11) 119.57(12) C(10)-C(9)-C(8) 119.71(11) C(10)-C(9)-H(9) 122.9(11) C(8)-C(9)-H(9) 117.4(11) C(9)-C(10)-C(5) 120.78(11) C(9)-C(10)-H(10) 116.7(11) C(5)-C(10)-H(10) 122.5(11) N(4)-C(11)-C(8) 179.34(15) N(2)-C(12)-O(1B) 125.0(2) N(2)-C(12)-O(1A) 124.64(17) O(1B)-C(12)-O(1A) 14.84(19) N(2)-C(12)-C(13) 120.95(11) O(1B)-C(12)-C(13) 113.0(2) O(1A)-C(12)-C(13) 114.19(17) C(12)-C(13)-C(15) 109.75(11) C(12)-C(13)-C(16) 111.27(11) C(15)-C(13)-C(16) 110.93(14) C(12)-C(13)-C(14) 106.14(11) C(15)-C(13)-C(14) 109.94(13) C(16)-C(13)-C(14) 108.69(14) C(13)-C(14)-H(14A) 109.5 C(13)-C(14)-H(14B) 109.5 H(14A)-C(14)-H(14B) 109.5 C(13)-C(14)-H(14C) 109.5 H(14A)-C(14)-H(14C) 109.5 H(14B)-C(14)-H(14C) 109.5 C(13)-C(15)-H(15A) 109.5 C(13)-C(15)-H(15B) 109.5 H(15A)-C(15)-H(15B) 109.5 C(13)-C(15)-H(15C) 109.5 H(15A)-C(15)-H(15C) 109.5 H(15B)-C(15)-H(15C) 109.5 C(13)-C(16)-H(16A) 109.5 C(13)-C(16)-H(16B) 109.5 H(16A)-C(16)-H(16B) 109.5 C(13)-C(16)-H(16C) 109.5 H(16A)-C(16)-H(16C) 109.5 H(16B)-C(16)-H(16C) 109.5 F(1)-B(1)-F(2) 111.56(11) F(1)-B(1)-O(1A) 115.3(2) F(2)-B(1)-O(1A) 105.2(2) F(1)-B(1)-O(1B) 103.6(2) F(2)-B(1)-O(1B) 117.1(2) O(1A)-B(1)-O(1B) 13.42(17) F(1)-B(1)-N(1) 108.90(11) F(2)-B(1)-N(1) 108.02(11) O(1A)-B(1)-N(1) 107.55(16) O(1B)-B(1)-N(1) 107.41(18)

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Table 5-14. Anisotropic displacement parameters (Å) for 8a.

The anisotropic displacement factor exponent takes the form: -2π²[ h²a*²U11 + ... + 2 h k a* b* U12 ] ______________________________________________________________________________

U11 U22 U33 U23 U13 U12

______________________________________________________________________________

F(1) 0.0268(4) 0.0208(4) 0.0421(5) -0.0092(4) 0.0120(4) -0.0104(3) F(2) 0.0510(6) 0.0146(4) 0.0271(4) 0.0065(3) 0.0062(4) -0.0008(4) O(1A) 0.0158(7) 0.0125(4) 0.0159(7) -0.0007(5) 0.0010(6) -0.0003(5) O(1B) 0.0158(7) 0.0125(4) 0.0159(7) -0.0007(5) 0.0010(6) -0.0003(5) N(1) 0.0159(4) 0.0104(4) 0.0155(4) -0.0007(3) 0.0027(3) -0.0007(3) N(2) 0.0176(5) 0.0120(5) 0.0169(5) -0.0020(4) 0.0038(4) 0.0017(4) N(3) 0.0162(5) 0.0113(4) 0.0158(4) -0.0001(3) 0.0015(3) 0.0002(3) N(4) 0.0301(6) 0.0291(6) 0.0273(6) -0.0094(5) 0.0077(5) -0.0016(5) C(1) 0.0139(5) 0.0121(5) 0.0136(5) 0.0002(4) 0.0012(4) 0.0002(4) C(2) 0.0163(5) 0.0112(5) 0.0172(5) 0.0011(4) 0.0029(4) 0.0002(4) C(3) 0.0129(5) 0.0120(5) 0.0142(5) 0.0000(4) 0.0005(4) 0.0004(4) C(4) 0.0163(5) 0.0132(5) 0.0150(5) -0.0005(4) 0.0037(4) -0.0006(4) C(5) 0.0132(5) 0.0127(5) 0.0138(5) -0.0005(4) 0.0001(4) 0.0016(4) C(6) 0.0156(5) 0.0139(5) 0.0162(5) -0.0010(4) 0.0025(4) -0.0008(4) C(7) 0.0174(5) 0.0144(5) 0.0177(5) -0.0034(4) 0.0016(4) -0.0004(4) C(8) 0.0148(5) 0.0183(6) 0.0141(5) -0.0030(4) 0.0003(4) 0.0021(4) C(9) 0.0192(6) 0.0180(6) 0.0144(5) 0.0015(4) 0.0026(4) 0.0028(4) C(10) 0.0187(5) 0.0139(5) 0.0167(5) 0.0011(4) 0.0031(4) 0.0016(4) C(11) 0.0196(6) 0.0204(6) 0.0181(5) -0.0027(4) 0.0017(4) -0.0007(5) C(12) 0.0161(5) 0.0138(5) 0.0181(5) -0.0011(4) 0.0034(4) 0.0009(4) C(13) 0.0210(6) 0.0134(5) 0.0211(6) -0.0039(4) 0.0054(4) 0.0018(4) C(14) 0.0395(8) 0.0335(8) 0.0236(7) -0.0057(6) -0.0007(6) 0.0087(7) C(15) 0.0573(11) 0.0272(8) 0.0243(7) -0.0006(6) 0.0020(7) 0.0247(7) C(16) 0.0417(10) 0.0294(8) 0.0636(12) -0.0181(8) 0.0338(9) -0.0080(7) B(1) 0.0256(7) 0.0107(6) 0.0219(6) -0.0009(5) 0.0086(5) -0.0029(5) ______________________________________________________________________________

Table 5. Hydrogen coordinates and isotropic displacement parameters for 8a.

________________________________________________________________________________

x y z U(is)

________________________________________________________________________________

H(2) 0.467(2) 0.408(2) 0.3789(9) 0.024(4)

H(4) 0.143(2) 0.1830(19) 0.5231(8) 0.023(4)

H(6) 0.265(2) 0.6551(19) 0.5109(8) 0.020(4)

H(7) 0.162(2) 0.8105(19) 0.5872(8) 0.020(4)

H(9) -0.044(2) 0.4682(19) 0.6746(8) 0.023(4)

H(10) 0.050(2) 0.314(2) 0.5974(8) 0.026(4)

H(14A) 0.4163 -0.1709 0.2271 0.048

H(14B) 0.3374 -0.0191 0.2434 0.048

H(14C) 0.2758 -0.1593 0.2782 0.048

H(15A) 0.4712 -0.2853 0.3534 0.054

H(15B) 0.6523 -0.2187 0.3752 0.054

H(15C) 0.6250 -0.2900 0.3075 0.054

H(16A) 0.7104 -0.0732 0.2515 0.066

H(16B) 0.7530 0.0051 0.3169 0.066

H(16C) 0.6244 0.0772 0.2656 0.066

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Table 5-16. Torsion angles [°] for 8a.

___________________________________________________________________________________

C(4)-N(1)-C(1)-N(2) 178.45(11) B(1)-N(1)-C(1)-N(2) -0.51(17) C(4)-N(1)-C(1)-C(2) -1.47(16)B (1)-N(1)-C(1)-C(2) 179.57(11) C(12)-N(2)-C(1)-N(1) -0.42(17) C(12)-N(2)-C(1)-C(2) 179.49(11) C(3)-N(3)-C(2)-C(1) -0.61(17) N(1)-C(1)-C(2)-N(3) 2.13(17) N(2)-C(1)-C(2)-N(3) -177.79(11) C(2)-N(3)-C(3)-C(4) -1.53(17) C(2)-N(3)-C(3)-C(5) 178.78(10) C(1)-N(1)-C(4)-C(3) -0.57(17) B(1)-N(1)-C(4)-C(3) 178.40(11) N(3)-C(3)-C(4)-N(1) 2.16(17) C(5)-C(3)-C(4)-N(1) -178.17(10) N(3)-C(3)-C(5)-C(6) 1.80(16) C(4)-C(3)-C(5)-C(6) -177.88(11) N(3)-C(3)-C(5)-C(10) -177.85(10) C(4)-C(3)-C(5)-C(10) 2.46(17) C(10)-C(5)-C(6)-C(7) 0.61(17) C(3)-C(5)-C(6)-C(7) -179.05(11) C(5)-C(6)-C(7)-C(8) 0.35(18) C(6)-C(7)-C(8)-C(9) -0.73(18) C(6)-C(7)-C(8)-C(11) -179.98(11) C(7)-C(8)-C(9)-C(10) 0.13(18) C(11)-C(8)-C(9)-C(10) 179.37(11) C(8)-C(9)-C(10)-C(5) 0.86(18) C(6)-C(5)-C(10)-C(9) -1.23(17) C(3)-C(5)-C(10)-C(9) 178.43(11) C(9)-C(8)-C(11)-N(4) -105(14) C(7)-C(8)-C(11)-N(4) 74(14) C(1)-N(2)-C(12)-O(1B) 10.1(4) C(1)-N(2)-C(12)-O(1A) -8.0(3) C(1)-N(2)-C(12)-C(13) 177.76(11) B(1)-O(1B)-C(12)-N(2) -18.9(6) B(1)-O(1B)-C(12)-O(1A) 74.9(11) B(1)-O(1B)-C(12)-C(13) 172.6(4) B(1)-O(1A)-C(12)-N(2) 17.9(6) B(1)-O(1A)-C(12)-O(1B) -78.7(12) B(1)-O(1A)-C(12)-C(13) -167.5(3) N(2)-C(12)-C(13)-C(15) 145.10(14) O(1B)-C(12)-C(13)-C(15) -45.9(3) O(1A)-C(12)-C(13)-C(15) -29.7(3) N(2)-C(12)-C(13)-C(16) 21.93(18) O(1B)-C(12)-C(13)-C(16) -169.0(3) O(1A)-C(12)-C(13)-C(16) -152.9(3) N(2)-C(12)-C(13)-C(14) -96.15(14) O(1B)-C(12)-C(13)-C(14) 72.9(3) O(1A)-C(12)-C(13)-C(14) 89.0(3) C(12)-O(1A)-B(1)-F(1) 105.6(4) C(12)-O(1A)-B(1)-F(2) -131.1(4) C(12)-O(1A)-B(1)-O(1B) 75.4(12) C(12)-O(1A)-B(1)-N(1) -16.1(5) C(12)-O(1B)-B(1)-F(1) 130.4(4) C(12)-O(1B)-B(1)-F(2) -106.4(4) C(12)-O(1B)-B(1)-O(1A) -77.5(12) C(12)-O(1B)-B(1)-N(1) 15.3(6) C(1)-N(1)-B(1)-F(1) -117.69(12) C(4)-N(1)-B(1)-F(1) 63.34(15) C(1)-N(1)-B(1)-F(2) 120.99(12) C(4)-N(1)-B(1)-F(2) -57.98(15) C(1)-N(1)-B(1)-O(1A) 7.9(3) C(4)-N(1)-B(1)-O(1A) -171.0(2) C(1)-N(1)-B(1)-O(1B) -6.1(3)

Table 5-17. Atomic coordinates and equivalent isotropic displacement parameters (Å²) for 8c.

U(is) is defined as one third of the trace of the orthogonalized Uij tensor.

________________________________________________________________________________

x y z U(eq)

________________________________________________________________________________

F(1) 0.22459(4) 0.41707(10) 0.34470(4) 0.0272(2)

O(1) 0.28955(8) 0.2760(4) 0.22621(6) 0.0123(4)

N(1) 0.37866(7) 0.2500 0.36497(6) 0.0114(2)

N(2) 0.46020(8) 0.2500 0.22813(6) 0.0131(2)

N(3) 0.55972(8) 0.2500 0.44513(7) 0.0147(2)

C(1) 0.46078(9) 0.2500 0.31639(8) 0.0117(2)

C(2) 0.55215(9) 0.2500 0.36054(8) 0.0148(3)

C(3) 0.47581(9) 0.2500 0.49341(8) 0.0115(2)

C(4) 0.38517(9) 0.2500 0.45249(8) 0.0131(3)

C(5) 0.48715(9) 0.2500 0.58876(7) 0.0122(3)

C(6) 0.58164(10) 0.2500 0.62506(8) 0.0159(3)

C(7) 0.59380(10) 0.2500 0.71456(8) 0.0189(3)

C(8) 0.51252(11) 0.2500 0.76870(8) 0.0192(3)

C(9) 0.41826(11) 0.2500 0.73366(8) 0.0195(3)

C(10) 0.40581(10) 0.2500 0.64460(8) 0.0168(3)

C(11) 0.37629(9) 0.2500 0.18835(8) 0.0127(2)

C(12) 0.37318(9) 0.2500 0.09035(7) 0.0129(3)

C(13) 0.47723(10) 0.2500 0.05339(9) 0.0194(3)

C(14) 0.31705(7) 0.43462(15) 0.06021(6) 0.0192(2)

B(1) 0.27344(10) 0.2500 0.31983(9) 0.0155(3)

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Table 5-18. Bond lengths [Å] and angles [°] for 8c.

_______________________________________________________________________________

F(1)-B(1) 1.3693(10) O(1)-O(1)#1 0.353(5)

O(1)-C(11) 1.3282(15) O(1)-B(1) 1.4733(17)

N(1)-C(1) 1.3453(15) N(1)-C(4) 1.3548(15)

N(1)-B(1) 1.5914(17) N(2)-C(11) 1.2959(16)

N(2)-C(1) 1.3635(15) N(3)-C(2) 1.3106(16)

N(3)-C(3) 1.3630(15) C(1)-C(2) 1.4172(17)

C(2)-H(2) 1.008(17) C(3)-C(4) 1.3851(17)

C(3)-C(5) 1.4809(16) C(4)-H(4) 0.974(19)

C(5)-C(6) 1.4017(17) C(5)-C(10) 1.4026(17)

C(6)-C(7) 1.3923(18) C(6)-H(6) 0.963(17)

C(7)-C(8) 1.3858(19) C(7)-H(7) 1.019(19)

C(8)-C(9) 1.391(2) C(8)-H(8) 0.952(19)

C(9)-C(10) 1.3861(17) C(9)-H(9) 0.964(16)

C(10)-H(10) 0.984(17) C(11)-O(1)#1 1.3282(15) C(11)-C(12) 1.5144(16) C(12)-C(13) 1.5255(17) C(12)-C(14)#1 1.5394(12) C(12)-C(14) 1.5395(12) C(13)-H(13A) 0.983(17) C(13)-H(13B) 1.006(13) C(14)-H(14A) 1.003(13) C(14)-H(14B) 1.012(12) C(14)-H(14C) 0.937(13) B(1)-F(1)#1 1.3693(10) B(1)-O(1)#1 1.4732(17)

O(1)#1-O(1)-C(11) 82.36(11) O(1)#1-O(1)-B(1) 83.10(9) C(11)-O(1)-B(1) 123.25(11) C(1)-N(1)-C(4) 120.16(10) C(1)-N(1)-B(1) 120.11(10) C(4)-N(1)-B(1) 119.73(10) C(11)-N(2)-C(1) 118.64(10) C(2)-N(3)-C(3) 118.67(10) N(1)-C(1)-N(2) 123.58(11) N(1)-C(1)-C(2) 117.33(11) N(2)-C(1)-C(2) 119.10(10) N(3)-C(2)-C(1) 123.28(11)

N(3)-C(2)-H(2) 120.0(9) C(1)-C(2)-H(2) 116.8(9)

N(3)-C(3)-C(4) 119.67(11) N(3)-C(3)-C(5) 117.20(10) C(4)-C(3)-C(5) 123.13(11) N(1)-C(4)-C(3) 120.90(11) N(1)-C(4)-H(4) 114.2(10) C(3)-C(4)-H(4) 124.9(10) C(6)-C(5)-C(10) 118.46(11) C(6)-C(5)-C(3) 119.56(11)

C(8)-C(7)-C(6) 120.30(12) C(8)-C(7)-H(7) 119.9(10) C(6)-C(7)-H(7) 119.8(10) C(7)-C(8)-C(9) 119.99(12) C(7)-C(8)-H(8) 117.7(12) C(9)-C(8)-H(8) 122.3(12) C(10)-C(9)-C(8) 119.91(13) C(10)-C(9)-H(9) 118.4(9) C(8)-C(9)-H(9) 121.7(9) C(9)-C(10)-C(5) 120.95(12) C(9)-C(10)-H(10) 117.6(10) C(5)-C(10)-H(10) 121.5(10) N(2)-C(11)-O(1) 124.96(11) N(2)-C(11)-O(1)#1 124.95(11) O(1)-C(11)-O(1)#1 15.3(2) N(2)-C(11)-C(12) 119.91(10) O(1)-C(11)-C(12) 114.54(10) O(1)#1-C(11)-C(12) 114.55(10) C(11)-C(12)-C(13) 110.38(10) C(11)-C(12)-C(14)#1 108.43(7) C(13)-C(12)-C(14)#1 110.27(7) C(11)-C(12)-C(14) 108.43(7) C(13)-C(12)-C(14) 110.27(7) C(14)#1-C(12)-C(14) 109.01(10) C(12)-C(13)-H(13A) 109.9(10) C(12)-C(13)-H(13B) 111.0(7) H(13A)-C(13)-H(13B) 106.8(8) C(12)-C(14)-H(14A) 110.6(7) C(12)-C(14)-H(14B) 111.0(7) H(14A)-C(14)-H(14B) 108.6(9) C(12)-C(14)-H(14C) 112.5(8) H(14A)-C(14)-H(14C) 107.3(11) H(14B)-C(14)-H(14C) 106.7(10) F(1)-B(1)-F(1)#1 111.85(11) F(1)-B(1)-O(1)#1 116.54(11) F(1)#1-B(1)-O(1)#1 104.37(11) F(1)-B(1)-O(1) 104.37(11) F(1)#1-B(1)-O(1) 116.54(11) O(1)#1-B(1)-O(1) 13.78(19) F(1)-B(1)-N(1) 108.24(7) F(1)#1-B(1)-N(1) 108.24(7) O(1)#1-B(1)-N(1) 107.24(9) O(1)-B(1)-N(1) 107.25(9)

________________________________________________________________________________

Symmetry transformations used to generate equivalent atoms:

#1 x,-y+1/2,z

Table 5-19. Anisotropic displacement parameters (Å) for 8a.

The anisotropic displacement factor exponent takes the form: -2π²[ h²a*²U11 + ... + 2 h k a* b* U12 ] ______________________________________________________________________________

U11 U22 U33 U23 U13 U12

______________________________________________________________________________

F(1) 0.0186(3) 0.0379(4) 0.0252(3) -0.0067(2) -0.0043(2) 0.0121(2) O(1) 0.0113(4) 0.0150(11) 0.0106(4) -0.0002(5) 0.0005(3) 0.0015(5) N(1) 0.0109(5) 0.0143(5) 0.0091(5) 0.000 0.0005(4) 0.000 N(2) 0.0129(5) 0.0166(5) 0.0097(5) 0.000 0.0000(4) 0.000 N(3) 0.0122(5) 0.0193(5) 0.0125(5) 0.000 0.0005(4) 0.000 C(1) 0.0115(5) 0.0121(5) 0.0116(5) 0.000 0.0022(4) 0.000 C(2) 0.0118(6) 0.0186(6) 0.0138(6) 0.000 0.0006(4) 0.000 C(3) 0.0127(6) 0.0102(5) 0.0115(5) 0.000 0.0004(4) 0.000 C(4) 0.0131(6) 0.0164(6) 0.0098(5) 0.000 0.0009(4) 0.000 C(5) 0.0158(6) 0.0098(5) 0.0109(5) 0.000 -0.0015(4) 0.000 C(6) 0.0156(6) 0.0174(6) 0.0145(6) 0.000 -0.0011(5) 0.000 C(7) 0.0191(6) 0.0219(7) 0.0156(6) 0.000 -0.0048(5) 0.000 C(8) 0.0276(7) 0.0197(6) 0.0102(6) 0.000 -0.0016(5) 0.000 C(9) 0.0217(7) 0.0240(7) 0.0129(6) 0.000 0.0034(5) 0.000 C(10) 0.0166(6) 0.0215(6) 0.0124(6) 0.000 0.0001(5) 0.000 C(11) 0.0128(6) 0.0137(6) 0.0118(5) 0.000 0.0024(4) 0.000 C(12) 0.0136(6) 0.0172(6) 0.0078(5) 0.000 0.0001(4) 0.000 C(13) 0.0163(6) 0.0292(7) 0.0129(6) 0.000 0.0033(5) 0.000 C(14) 0.0194(5) 0.0223(5) 0.0158(4) 0.0036(4) 0.0004(3) 0.0027(4) B(1) 0.0096(6) 0.0267(8) 0.0102(6) 0.000 0.0004(5) 0.000 ______________________________________________________________________________

Table 5-20. Hydrogen coordinates and isotropic displacement parameters for 8c.

________________________________________________________________________________

x y z U(is)

________________________________________________________________________________

H(2) 0.6133(12) 0.2500 0.3236(11) 0.022(4)

H(4) 0.3219(14) 0.2500 0.4821(11) 0.029(5)

H(6) 0.6388(12) 0.2500 0.5883(10) 0.020(4)

H(7) 0.6628(14) 0.2500 0.7403(11) 0.028(4)

H(8) 0.5240(15) 0.2500 0.8295(13) 0.039(6)

H(9) 0.3605(12) 0.2500 0.7699(10) 0.024(4)

H(10) 0.3380(13) 0.2500 0.6222(11) 0.023(4)

H(13A) 0.4746(12) 0.2500 -0.0102(11) 0.024(4)

H(13B) 0.5139(9) 0.372(2) 0.0710(8) 0.027(3)

H(14A) 0.3142(10) 0.4401(17) -0.0046(8) 0.034(3)

H(14B) 0.3500(9) 0.5588(18) 0.0821(7) 0.022(3)

H(14C) 0.2521(10) 0.4374(18) 0.0806(8) 0.027(3)

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Table 5-21. Torsion angles [°] for 8c.

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C(4)-N(1)-C(1)-N(2) 180.0 B(1)-N(1)-C(1)-N(2) 0.0

C(4)-N(1)-C(1)-C(2) 0.0 B(1)-N(1)-C(1)-C(2) 180.0

C(11)-N(2)-C(1)-N(1) 0.0 C(11)-N(2)-C(1)-C(2) 180.0

C(3)-N(3)-C(2)-C(1) 0.0 N(1)-C(1)-C(2)-N(3) 0.0

N(2)-C(1)-C(2)-N(3) 180.0 C(2)-N(3)-C(3)-C(4) 0.0

C(2)-N(3)-C(3)-C(5) 180.0 C(1)-N(1)-C(4)-C(3) 0.0

B(1)-N(1)-C(4)-C(3) 180.0 N(3)-C(3)-C(4)-N(1) 0.0

C(5)-C(3)-C(4)-N(1) 180.0 N(3)-C(3)-C(5)-C(6) 0.0

C(4)-C(3)-C(5)-C(6) 180.0 N(3)-C(3)-C(5)-C(10) 180.0

C(4)-C(3)-C(5)-C(10) 0.0 C(10)-C(5)-C(6)-C(7) 0.0

C(3)-C(5)-C(6)-C(7) 180.0 C(5)-C(6)-C(7)-C(8) 0.0

C(6)-C(7)-C(8)-C(9) 0.0 C(7)-C(8)-C(9)-C(10) 0.0

C(8)-C(9)-C(10)-C(5) 0.0 C(6)-C(5)-C(10)-C(9) 0.0

C(3)-C(5)-C(10)-C(9) 180.0 C(1)-N(2)-C(11)-O(1) 9.34(13) C(1)-N(2)-C(11)-O(1)#1 -9.34(13) C(1)-N(2)-C(11)-C(12) 180.0 O(1)#1-O(1)-C(11)-N(2) -95.37(8) B(1)-O(1)-C(11)-N(2) -18.8(3) B(1)-O(1)-C(11)-O(1)#1 76.53(18) O(1)#1-O(1)-C(11)-C(12) 93.53(5) B(1)-O(1)-C(11)-C(12) 170.06(13) N(2)-C(11)-C(12)-C(13) 0.0

O(1)-C(11)-C(12)-C(13) 171.59(12) O(1)#1-C(11)-C(12)-C(13) -171.59(12) N(2)-C(11)-C(12)-C(14)#1 120.89(7) O(1)-C(11)-C(12)-C(14)#1 -67.52(13) O(1)#1-C(11)-C(12)-C(14)#1 -50.70(14) N(2)-C(11)-C(12)-C(14) -120.89(7) O(1)-C(11)-C(12)-C(14) 50.70(14) O(1)#1-C(11)-C(12)-C(14) 67.52(13) O(1)#1-O(1)-B(1)-F(1) -153.16(8) C(11)-O(1)-B(1)-F(1) 130.70(18) O(1)#1-O(1)-B(1)-F(1)#1 -29.28(8) C(11)-O(1)-B(1)-F(1)#1 -105.42(19) C(11)-O(1)-B(1)-O(1)#1 -76.14(18) O(1)#1-O(1)-B(1)-N(1) 92.15(3) C(11)-O(1)-B(1)-N(1) 16.0(2) C(1)-N(1)-B(1)-F(1) -119.29(7) C(4)-N(1)-B(1)-F(1) 60.71(7) C(1)-N(1)-B(1)-F(1)#1 119.29(7) C(4)-N(1)-B(1)-F(1)#1 -60.71(7) C(1)-N(1)-B(1)-O(1)#1 7.22(10) C(4)-N(1)-B(1)-O(1)#1 -172.78(10) C(1)-N(1)-B(1)-O(1) -7.21(10) C(4)-N(1)-B(1)-O(1) 172.79(10)

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Symmetry transformations used to generate equivalent atoms:

Table 5-22. Atomic coordinates and equivalent isotropic displacement parameters (Å²) for 8d.

U(is) is defined as one third of the trace of the orthogonalized Uij tensor.

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x y z U(is)

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F(1A) 0.39172(9) 0.51964(5) 0.05209(2) 0.01972(13)

F(2A) 0.68203(9) 0.53289(6) 0.03979(2) 0.02076(13)

O(1A) 0.57526(11) 0.61927(7) 0.09382(2) 0.02118(15)

O(2A) 0.46008(13) 0.85295(9) -0.18299(3) 0.02837(19)

N(1A) 0.49798(11) 0.70064(7) 0.03231(2) 0.01570(14)

N(2A) 0.41670(13) 0.78787(8) 0.09038(3) 0.01871(16)

N(3A) 0.37877(12) 0.89003(8) -0.00590(3) 0.01881(16)

C(1A) 0.42921(13) 0.78824(8) 0.05181(3) 0.01665(16)

C(2A) 0.36911(15) 0.88310(9) 0.03105(3) 0.01937(18)

C(3A) 0.45228(13) 0.80265(8) -0.02492(3) 0.01636(16)

C(4A) 0.51174(14) 0.70710(8) -0.00546(3) 0.01677(16)

C(5A) 0.46075(13) 0.81364(8) -0.06621(3) 0.01667(16)

C(6A) 0.53694(15) 0.73006(9) -0.08870(3) 0.01918(18)

C(7A) 0.54082(15) 0.74035(10) -0.12769(3) 0.02090(19)

C(8A) 0.46684(15) 0.83576(10) -0.14508(3) 0.02135(19)

C(9A) 0.39292(16) 0.92109(10) -0.12305(3) 0.0235(2)

C(10A) 0.39000(15) 0.91017(9) -0.08421(3) 0.02077(19)

C(11A) 0.51425(19) 0.76151(14) -0.20649(4) 0.0299(3)

C(12A) 0.49280(14) 0.70645(9) 0.10920(3) 0.01748(17)

C(13A) 0.49995(15) 0.70822(9) 0.15180(3) 0.01992(18)

C(14A) 0.37311(19) 0.79715(11) 0.16715(3) 0.0267(2)

C(15A) 0.68810(18) 0.73982(13) 0.16383(4) 0.0286(2)

C(16A) 0.45628(19) 0.58940(11) 0.16714(4) 0.0265(2)

B(1A) 0.54091(15) 0.58751(9) 0.05479(3) 0.01669(18)

C(1B) 0.06467(15) 0.10938(9) 0.13721(3) 0.01883(17)

C(2B) 0.11912(16) 0.04174(9) 0.10665(3) 0.0222(2)

C(3B) 0.04553(13) 0.18191(8) 0.06377(3) 0.01592(16)

C(4B) -0.00523(14) 0.25121(9) 0.09327(3) 0.01737(17)

C(5B) 0.03573(13) 0.21628(8) 0.02395(3) 0.01584(16)

C(6B) 0.09925(14) 0.14333(9) -0.00405(3) 0.01801(17)

C(7B) 0.09202(14) 0.17410(9) -0.04158(3) 0.01902(17)

C(8B) 0.02043(14) 0.27874(9) -0.05250(3) 0.01782(17)

C(9B) -0.04483(14) 0.35224(9) -0.02512(3) 0.01850(17)

C(10B) -0.03664(14) 0.32038(9) 0.01250(3) 0.01757(17)

C(11B) -0.02455(17) 0.41321(12) -0.10199(3) 0.0259(2)

C(12B) 0.00386(14) 0.12420(9) 0.20004(3) 0.01864(17)

C(13B) 0.16197(19) 0.01082(14) 0.24900(4) 0.0312(3)

C(14B) -0.1575(2) -0.02159(13) 0.23518(4) 0.0322(3)

C(15B) -0.0603(2) 0.15584(12) 0.26834(3) 0.0294(3)

C(16B) -0.01225(15) 0.06850(10) 0.23845(3) 0.02072(18)

B(1B) -0.03312(16) 0.29913(10) 0.16323(3) 0.01825(19)

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Table 3. Bond lengths [Å] and angles [°] for 8d.

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F(1A)-B(1A) 1.3932(14) F(2A)-B(1A) 1.3705(13) O(1A)-C(12A) 1.3255(12) O(1A)-B(1A) 1.4554(14) O(2A)-C(8A) 1.3618(14) O(2A)-C(11A) 1.4265(18) N(1A)-C(4A) 1.3498(13) N(1A)-C(1A) 1.3521(13) N(1A)-B(1A) 1.5825(14) N(2A)-C(12A) 1.2990(14) N(2A)-C(1A) 1.3753(14) N(3A)-C(2A) 1.3185(14) N(3A)-C(3A) 1.3561(13) C(1A)-C(2A) 1.4092(15) C(2A)-H(2A) 0.992(18) C(3A)-C(4A) 1.3908(14) C(3A)-C(5A) 1.4750(15) C(4A)-H(4A) 0.948(17) C(5A)-C(6A) 1.3992(14) C(5A)-C(10A) 1.4058(15) C(6A)-C(7A) 1.3913(15) C(6A)-H(6A) 0.971(18) C(7A)-C(8A) 1.3953(16) C(7A)-H(7A) 0.978(19) C(8A)-C(9A) 1.3972(17) C(9A)-C(10A) 1.3865(16) C(9A)-H(9A) 0.987(17) C(10A)-H(10A) 1.015(18) C(11A)-H(11A) 0.99(2) C(11A)-H(11B) 0.979(19) C(11A)-H(11C) 1.011(18) C(12A)-C(13A) 1.5134(15) C(13A)-C(14A) 1.5320(16) C(13A)-C(16A) 1.5376(17) C(13A)-C(15A) 1.5384(18) C(14A)-H(14A) 1.02(2) C(14A)-H(14B) 1.01(2) C(14A)-H(14C) 1.02(2) C(15A)-H(15A) 1.022(19) C(15A)-H(15B) 0.98(2) C(15A)-H(15C) 0.97(2) C(16A)-H(16A) 1.01(2) C(16A)-H(16B) 1.015(19) C(16A)-H(16C) 1.00(2) F(1B)-B(1B) 1.3682(14) F(2B)-B(1B) 1.3824(14) O(1B)-C(12B) 1.3146(13) O(1B)-B(1B) 1.4671(14) O(2B)-C(8B) 1.3615(13) O(2B)-C(11B) 1.4284(15) N(1B)-C(1B) 1.3492(13) N(1B)-C(4B) 1.3504(13) N(1B)-B(1B) 1.5889(14) N(2B)-C(12B) 1.2996(14)

C(8B)-C(9B) 1.3990(15) C(9B)-C(10B) 1.3882(15) C(9B)-H(9B) 1.001(19) C(10B)-H(10B) 0.996(18) C(11B)-H(11D) 1.00(2) C(11B)-H(11E) 0.99(2) C(11B)-H(11F) 1.00(2) C(12B)-C(16B) 1.5201(15) C(13B)-C(16B) 1.5347(18) C(13B)-H(13A) 1.00(2) C(13B)-H(13B) 1.02(2) C(13B)-H(13C) 0.98(2) C(14B)-C(16B) 1.5371(18) C(14B)-H(14D) 1.03(2) C(14B)-H(14E) 1.00(2) C(14B)-H(14F) 1.01(2) C(15B)-C(16B) 1.5263(17) C(15B)-H(15D) 1.01(2) C(15B)-H(15E) 0.98(2) C(15B)-H(15F) 0.95(2)

C(12A)-O(1A)-B(1A) 120.77(9) C(8A)-O(2A)-C(11A) 117.41(10) C(4A)-N(1A)-C(1A) 120.26(9) C(4A)-N(1A)-B(1A) 122.01(8) C(1A)-N(1A)-B(1A) 117.39(8) C(12A)-N(2A)-C(1A) 118.50(9) C(2A)-N(3A)-C(3A) 118.67(9) N(1A)-C(1A)-N(2A) 122.84(9) N(1A)-C(1A)-C(2A) 117.40(9) N(2A)-C(1A)-C(2A) 119.76(9) N(3A)-C(2A)-C(1A) 123.14(9) N(3A)-C(2A)-H(2A) 118.1(10) C(1A)-C(2A)-H(2A) 118.7(10) N(3A)-C(3A)-C(4A) 119.90(9) N(3A)-C(3A)-C(5A) 117.04(9) C(4A)-C(3A)-C(5A) 123.05(9) N(1A)-C(4A)-C(3A) 120.60(9) N(1A)-C(4A)-H(4A) 114.3(10) C(3A)-C(4A)-H(4A) 125.0(10) C(6A)-C(5A)-C(10A) 117.85(10) C(6A)-C(5A)-C(3A) 122.15(9) C(10A)-C(5A)-C(3A) 120.00(9) C(7A)-C(6A)-C(5A) 121.58(10) C(7A)-C(6A)-H(6A) 116.7(10) C(5A)-C(6A)-H(6A) 121.7(10) C(6A)-C(7A)-C(8A) 119.70(10) C(6A)-C(7A)-H(7A) 119.1(11) C(8A)-C(7A)-H(7A) 121.2(11) O(2A)-C(8A)-C(7A) 124.43(11) O(2A)-C(8A)-C(9A) 116.01(10) C(7A)-C(8A)-C(9A) 119.56(10) C(10A)-C(9A)-C(8A) 120.30(10) C(10A)-C(9A)-H(9A) 121.9(10) C(8A)-C(9A)-H(9A) 117.7(10) C(9A)-C(10A)-C(5A) 120.99(10) C(9A)-C(10A)-H(10A) 120.7(10) C(5A)-C(10A)-H(10A) 118.3(10) O(2A)-C(11A)-H(11A) 103.3(12) O(2A)-C(11A)-H(11B) 110.8(11) H(11A)-C(11A)-H(11B) 110.4(16) O(2A)-C(11A)-H(11C) 111.1(11) H(11A)-C(11A)-H(11C) 110.5(16) H(11B)-C(11A)-H(11C) 110.4(15) N(2A)-C(12A)-O(1A) 124.68(10) N(2A)-C(12A)-C(13A) 120.85(9) O(1A)-C(12A)-C(13A) 114.42(9)

C(14A)-C(13A)-C(15A) 109.29(10) C(16A)-C(13A)-C(15A) 109.15(10) C(13A)-C(14A)-H(14A) 109.1(11) C(13A)-C(14A)-H(14B) 110.8(11) H(14A)-C(14A)-H(14B) 108.4(16) C(13A)-C(14A)-H(14C) 112.5(11) H(14A)-C(14A)-H(14C) 108.8(16) H(14B)-C(14A)-H(14C) 107.2(15) C(13A)-C(15A)-H(15A) 107.7(11) C(13A)-C(15A)-H(15B) 111.9(13) H(15A)-C(15A)-H(15B) 111.2(17) C(13A)-C(15A)-H(15C) 111.0(12) H(15A)-C(15A)-H(15C) 108.1(16) H(15B)-C(15A)-H(15C) 107.0(17) C(13A)-C(16A)-H(16A) 111.3(13) C(13A)-C(16A)-H(16B) 111.5(11) H(16A)-C(16A)-H(16B) 107.4(16) C(13A)-C(16A)-H(16C) 110.9(12) H(16A)-C(16A)-H(16C) 106.5(17) H(16B)-C(16A)-H(16C) 109.1(16) F(2A)-B(1A)-F(1A) 110.69(9) F(2A)-B(1A)-O(1A) 111.11(9) F(1A)-B(1A)-O(1A) 110.28(9) F(2A)-B(1A)-N(1A) 110.79(8) F(1A)-B(1A)-N(1A) 106.49(8) O(1A)-B(1A)-N(1A) 107.33(8) C(12B)-O(1B)-B(1B) 123.40(9) C(8B)-O(2B)-C(11B) 117.44(9) C(1B)-N(1B)-C(4B) 120.12(9) C(1B)-N(1B)-B(1B) 118.76(9) C(4B)-N(1B)-B(1B) 120.97(8) C(12B)-N(2B)-C(1B) 118.76(10) C(2B)-N(3B)-C(3B) 119.08(9) N(1B)-C(1B)-N(2B) 123.18(9) N(1B)-C(1B)-C(2B) 117.34(9) N(2B)-C(1B)-C(2B) 119.47(10) N(3B)-C(2B)-C(1B) 123.00(10) N(3B)-C(2B)-H(2B) 118.6(11) C(1B)-C(2B)-H(2B) 118.5(11) N(3B)-C(3B)-C(4B) 119.20(9) N(3B)-C(3B)-C(5B) 117.12(8) C(4B)-C(3B)-C(5B) 123.67(9) N(1B)-C(4B)-C(3B) 121.18(9) N(1B)-C(4B)-H(4B) 115.7(11) C(3B)-C(4B)-H(4B) 123.1(11) C(10B)-C(5B)-C(6B) 117.82(9) C(10B)-C(5B)-C(3B) 122.16(9) C(6B)-C(5B)-C(3B) 120.02(9) C(7B)-C(6B)-C(5B) 120.97(9) C(7B)-C(6B)-H(6B) 120.3(11) C(5B)-C(6B)-H(6B) 118.7(11) C(6B)-C(7B)-C(8B) 120.46(9) C(6B)-C(7B)-H(7B) 122.5(11) C(8B)-C(7B)-H(7B) 117.0(11) O(2B)-C(8B)-C(7B) 115.67(9) O(2B)-C(8B)-C(9B) 124.81(10) C(7B)-C(8B)-C(9B) 119.52(9) C(10B)-C(9B)-C(8B) 119.47(10)

C(16B)-C(13B)-H(13A) 109.0(13) C(16B)-C(13B)-H(13B) 111.3(11) H(13A)-C(13B)-H(13B) 109.5(17) C(16B)-C(13B)-H(13C) 110.1(13) H(13A)-C(13B)-H(13C) 106.2(18) H(13B)-C(13B)-H(13C) 110.6(17) C(16B)-C(14B)-H(14D) 108.6(12) C(16B)-C(14B)-H(14E) 110.2(12) H(14D)-C(14B)-H(14E) 109.0(17) C(16B)-C(14B)-H(14F) 111.0(12) H(14D)-C(14B)-H(14F) 109.1(16) H(14E)-C(14B)-H(14F) 108.9(16) C(16B)-C(15B)-H(15D) 110.5(13) C(16B)-C(15B)-H(15E) 110.8(12) H(15D)-C(15B)-H(15E) 110.0(17) C(16B)-C(15B)-H(15F) 111.7(12) H(15D)-C(15B)-H(15F) 107.1(18) H(15E)-C(15B)-H(15F) 106.5(17) C(12B)-C(16B)-C(15B) 111.04(9) C(12B)-C(16B)-C(13B) 109.04(9) C(15B)-C(16B)-C(13B) 110.19(11) C(12B)-C(16B)-C(14B) 107.34(9) C(15B)-C(16B)-C(14B) 109.50(11) C(13B)-C(16B)-C(14B) 109.67(11) F(1B)-B(1B)-F(2B) 110.86(9) F(1B)-B(1B)-O(1B) 110.67(9) F(2B)-B(1B)-O(1B) 110.45(10) F(1B)-B(1B)-N(1B) 109.89(9) F(2B)-B(1B)-N(1B) 107.67(8) O(1B)-B(1B)-N(1B) 107.18(8) ________________________________________________________________________________

Symmetry transformations used to generate equivalent atoms:

Table 5-29. Anisotropic displacement parameters (Å) for 8d.

The anisotropic displacement factor exponent takes the form: -2π²[ h²a*²U11 + ... + 2 h k a* b* U12 ] ______________________________________________________________________________

U11 U22 U33 U23 U13 U12

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F(1A) 0.0205(3) 0.0140(3) 0.0247(3) 0.0009(2) 0.0016(2) -0.0001(2) F(2A) 0.0202(3) 0.0189(3) 0.0233(3) -0.0015(2) 0.0029(2) 0.0062(2) O(1A) 0.0257(4) 0.0187(3) 0.0190(3) -0.0028(3) -0.0016(3) 0.0072(3) O(2A) 0.0339(5) 0.0321(5) 0.0191(4) 0.0062(3) -0.0010(3) 0.0022(4) N(1A) 0.0163(3) 0.0127(3) 0.0181(3) -0.0012(3) 0.0010(3) 0.0005(3) N(2A) 0.0225(4) 0.0160(3) 0.0176(4) -0.0010(3) 0.0019(3) 0.0023(3) N(3A) 0.0215(4) 0.0141(3) 0.0209(4) -0.0011(3) 0.0020(3) 0.0018(3) C(1A) 0.0178(4) 0.0136(4) 0.0186(4) -0.0011(3) 0.0020(3) 0.0011(3) C(2A) 0.0233(5) 0.0139(4) 0.0209(4) -0.0018(3) 0.0021(3) 0.0040(3) C(3A) 0.0162(4) 0.0134(3) 0.0195(4) -0.0007(3) 0.0023(3) -0.0001(3) C(4A) 0.0177(4) 0.0138(4) 0.0188(4) -0.0010(3) 0.0020(3) 0.0011(3) C(5A) 0.0172(4) 0.0141(4) 0.0188(4) 0.0010(3) 0.0011(3) -0.0003(3) C(6A) 0.0223(4) 0.0166(4) 0.0186(4) 0.0017(3) 0.0019(3) 0.0028(3) C(7A) 0.0234(5) 0.0205(4) 0.0188(4) 0.0019(3) 0.0020(3) 0.0016(4) C(8A) 0.0208(4) 0.0239(5) 0.0193(4) 0.0040(4) -0.0005(3) -0.0015(4) C(9A) 0.0258(5) 0.0199(4) 0.0247(5) 0.0054(4) -0.0006(4) 0.0024(4) C(10A) 0.0227(5) 0.0162(4) 0.0234(5) 0.0022(3) 0.0000(4) 0.0024(3) C(11A) 0.0304(6) 0.0407(7) 0.0186(5) 0.0015(5) 0.0018(4) 0.0009(5) C(12A) 0.0186(4) 0.0152(4) 0.0187(4) -0.0023(3) 0.0011(3) -0.0002(3) C(13A) 0.0234(5) 0.0193(4) 0.0170(4) -0.0015(3) 0.0010(3) 0.0019(3) C(14A) 0.0347(6) 0.0249(5) 0.0205(5) -0.0001(4) 0.0063(4) 0.0066(4) C(15A) 0.0272(6) 0.0343(6) 0.0242(5) -0.0065(5) -0.0025(4) -0.0016(5) C(16A) 0.0354(6) 0.0217(5) 0.0223(5) 0.0025(4) 0.0012(4) 0.0002(4) B(1A) 0.0193(5) 0.0133(4) 0.0175(4) -0.0008(3) 0.0007(4) 0.0024(3)

C(1B) 0.0236(5) 0.0162(4) 0.0167(4) -0.0003(3) 0.0003(3) 0.0037(3) C(2B) 0.0325(6) 0.0167(4) 0.0176(4) -0.0011(3) 0.0016(4) 0.0076(4) C(3B) 0.0173(4) 0.0132(4) 0.0172(4) -0.0010(3) 0.0006(3) 0.0008(3) C(4B) 0.0209(4) 0.0141(4) 0.0172(4) -0.0003(3) 0.0017(3) 0.0023(3) C(5B) 0.0163(4) 0.0150(4) 0.0163(4) -0.0008(3) 0.0006(3) 0.0009(3) C(6B) 0.0206(4) 0.0152(4) 0.0182(4) -0.0015(3) 0.0014(3) 0.0023(3) C(7B) 0.0220(4) 0.0176(4) 0.0175(4) -0.0015(3) 0.0019(3) 0.0010(3) C(8B) 0.0174(4) 0.0197(4) 0.0164(4) 0.0005(3) 0.0004(3) -0.0010(3) C(9B) 0.0194(4) 0.0178(4) 0.0183(4) 0.0007(3) -0.0002(3) 0.0028(3) C(10B) 0.0192(4) 0.0160(4) 0.0175(4) -0.0007(3) 0.0008(3) 0.0025(3) C(11B) 0.0266(5) 0.0299(6) 0.0213(5) 0.0072(4) 0.0016(4) 0.0068(4) C(12B) 0.0221(4) 0.0167(4) 0.0171(4) -0.0004(3) -0.0007(3) 0.0006(3) C(13B) 0.0335(6) 0.0379(7) 0.0221(5) 0.0073(5) -0.0009(4) 0.0080(5) C(14B) 0.0404(7) 0.0295(6) 0.0264(6) 0.0075(5) -0.0048(5) -0.0123(5) C(15B) 0.0437(7) 0.0273(5) 0.0172(4) -0.0009(4) 0.0039(4) 0.0017(5) C(16B) 0.0262(5) 0.0204(4) 0.0155(4) 0.0010(3) 0.0006(3) -0.0005(4) B(1B) 0.0227(5) 0.0146(4) 0.0175(4) -0.0015(3) 0.0026(4) 0.0016(4) ______________________________________________________________________________

Table 5-30. Hydrogen coordinates and isotropic displacement parameters for 8d.

________________________________________________________________________________

x y z U(is)

________________________________________________________________________________

H(2A) 0.317(2) 0.9481(15) 0.0448(5) 0.027(4)

H(4A) 0.559(2) 0.6410(15) -0.0168(5) 0.023(4)

H(6A) 0.587(2) 0.6610(15) -0.0779(5) 0.025(4)

H(7A) 0.593(2) 0.6793(17) -0.1425(5) 0.032(5)

H(9A) 0.341(2) 0.9875(15) -0.1361(5) 0.024(4)

H(10A) 0.335(2) 0.9715(15) -0.0681(5) 0.026(4)

H(11A) 0.491(3) 0.7907(17) -0.2322(6) 0.038(5)

H(11B) 0.445(2) 0.6932(17) -0.2019(5) 0.032(5)

H(11C) 0.643(2) 0.7448(16) -0.2027(5) 0.030(4)

H(14A) 0.379(3) 0.7957(17) 0.1957(6) 0.039(5)

H(14B) 0.249(3) 0.7799(17) 0.1588(6) 0.036(5)

H(14C) 0.401(2) 0.8777(17) 0.1582(5) 0.035(5)

H(15A) 0.693(2) 0.7437(17) 0.1926(5) 0.035(5)

H(15B) 0.725(3) 0.812(2) 0.1526(6) 0.048(6)

H(15C) 0.770(3) 0.6823(18) 0.1559(6) 0.039(5)

H(16A) 0.336(3) 0.5641(19) 0.1586(6) 0.047(6)

H(16B) 0.459(2) 0.5881(16) 0.1957(5) 0.032(5)

H(16C) 0.540(3) 0.5313(19) 0.1576(6) 0.043(5)

H(2B) 0.166(2) -0.0341(16) 0.1119(5) 0.030(4)

H(4B) -0.048(2) 0.3267(15) 0.0897(5) 0.026(4)

H(6B) 0.147(2) 0.0692(16) 0.0035(5) 0.028(4)

H(7B) 0.138(2) 0.1226(16) -0.0625(5) 0.032(5)

H(9B) -0.095(2) 0.4283(16) -0.0321(5) 0.031(4)

H(10B) -0.085(2) 0.3740(15) 0.0314(5) 0.026(4)

H(14E) -0.125(3) -0.0809(18) 0.2164(6) 0.041(5)

H(14F) -0.272(3) 0.0140(18) 0.2272(6) 0.039(5)

H(15D) -0.065(3) 0.119(2) 0.2939(6) 0.047(6)

H(15E) -0.173(3) 0.1921(17) 0.2621(6) 0.038(5)

H(15F) 0.024(3) 0.2156(18) 0.2701(6) 0.039(5)

________________________________________________________________________________

Table 5-31. Torsion angles [°] for 8d.

___________________________________________________________________________________

C(4A)-N(1A)-C(1A)-N(2A) -178.01(9) B(1A)-N(1A)-C(1A)-N(2A) 8.52(15) C(4A)-N(1A)-C(1A)-C(2A) 1.82(15) B(1A)-N(1A)-C(1A)-C(2A) -171.64(9) C(12A)-N(2A)-C(1A)-N(1A) 8.50(16) C(12A)-N(2A)-C(1A)-C(2A) -171.34(10) C(3A)-N(3A)-C(2A)-C(1A) -1.01(17) N(1A)-C(1A)-C(2A)-N(3A) -0.67(16) N(2A)-C(1A)-C(2A)-N(3A) 179.17(10) C(2A)-N(3A)-C(3A)-C(4A) 1.54(15) C(2A)-N(3A)-C(3A)-C(5A) -179.96(10) C(1A)-N(1A)-C(4A)-C(3A) -1.33(15) B(1A)-N(1A)-C(4A)-C(3A) 171.83(9) N(3A)-C(3A)-C(4A)-N(1A) -0.40(15) C(5A)-C(3A)-C(4A)-N(1A) -178.81(9) N(3A)-C(3A)-C(5A)-C(6A) 178.64(10) C(4A)-C(3A)-C(5A)-C(6A) -2.91(16) N(3A)-C(3A)-C(5A)-C(10A) -1.72(15) C(4A)-C(3A)-C(5A)-C(10A) 176.73(10) C(10A)-C(5A)-C(6A)-C(7A) -1.02(16) C(3A)-C(5A)-C(6A)-C(7A) 178.63(10) C(5A)-C(6A)-C(7A)-C(8A) -0.22(17) C(11A)-O(2A)-C(8A)-C(7A) 7.46(17) C(11A)-O(2A)-C(8A)-C(9A) -172.35(11) C(6A)-C(7A)-C(8A)-O(2A) -178.45(11) C(6A)-C(7A)-C(8A)-C(9A) 1.35(17) O(2A)-C(8A)-C(9A)-C(10A) 178.59(11) C(7A)-C(8A)-C(9A)-C(10A) -1.23(18) C(8A)-C(9A)-C(10A)-C(5A) -0.03(18) C(6A)-C(5A)-C(10A)-C(9A) 1.14(16) C(3A)-C(5A)-C(10A)-C(9A) -178.52(10) C(1A)-N(2A)-C(12A)-O(1A) -3.64(16) C(1A)-N(2A)-C(12A)-C(13A) 173.48(9) B(1A)-O(1A)-C(12A)-N(2A) -19.89(16) B(1A)-O(1A)-C(12A)-C(13A) 162.81(9) N(2A)-C(12A)-C(13A)-C(14A) 13.64(15) O(1A)-C(12A)-C(13A)-C(14A) -168.96(10) N(2A)-C(12A)-C(13A)-C(16A) 135.90(11) O(1A)-C(12A)-C(13A)-C(16A) -46.70(13) N(2A)-C(12A)-C(13A)-C(15A) -105.58(12) O(1A)-C(12A)-C(13A)-C(15A) 71.83(12) C(12A)-O(1A)-B(1A)-F(2A) 154.04(9) C(12A)-O(1A)-B(1A)-F(1A) -82.84(12) C(12A)-O(1A)-B(1A)-N(1A) 32.77(13) C(4A)-N(1A)-B(1A)-F(2A) 38.16(13) C(1A)-N(1A)-B(1A)-F(2A) -148.50(9) C(4A)-N(1A)-B(1A)-F(1A) -82.27(11) C(1A)-N(1A)-B(1A)-F(1A) 91.07(10) C(4A)-N(1A)-B(1A)-O(1A) 159.63(9) C(1A)-N(1A)-B(1A)-O(1A) -27.02(12) C(4B)-N(1B)-C(1B)-N(2B) -175.45(11) B(1B)-N(1B)-C(1B)-N(2B) 8.86(16) C(4B)-N(1B)-C(1B)-C(2B) 3.15(16) B(1B)-N(1B)-C(1B)-C(2B) -172.54(10)

C(4B)-C(3B)-C(5B)-C(6B) 176.35(10) C(10B)-C(5B)-C(6B)-C(7B) 0.67(16) C(3B)-C(5B)-C(6B)-C(7B) -179.72(10) C(5B)-C(6B)-C(7B)-C(8B) -0.24(16) C(11B)-O(2B)-C(8B)-C(7B) -169.63(10) C(11B)-O(2B)-C(8B)-C(9B) 10.81(16) C(6B)-C(7B)-C(8B)-O(2B) -179.87(10) C(6B)-C(7B)-C(8B)-C(9B) -0.28(16) O(2B)-C(8B)-C(9B)-C(10B) 179.89(10) C(7B)-C(8B)-C(9B)-C(10B) 0.34(16) C(8B)-C(9B)-C(10B)-C(5B) 0.11(16) C(6B)-C(5B)-C(10B)-C(9B) -0.61(16) C(3B)-C(5B)-C(10B)-C(9B) 179.79(10) C(1B)-N(2B)-C(12B)-O(1B) -5.27(18) C(1B)-N(2B)-C(12B)-C(16B) 172.25(10) B(1B)-O(1B)-C(12B)-N(2B) -9.43(18) B(1B)-O(1B)-C(12B)-C(16B) 173.01(10) N(2B)-C(12B)-C(16B)-C(15B) 169.99(11) O(1B)-C(12B)-C(16B)-C(15B) -12.28(15) N(2B)-C(12B)-C(16B)-C(13B) 48.39(15) O(1B)-C(12B)-C(16B)-C(13B) -133.88(11) N(2B)-C(12B)-C(16B)-C(14B) -70.35(14) O(1B)-C(12B)-C(16B)-C(14B) 107.38(12) C(12B)-O(1B)-B(1B)-F(1B) 140.10(10) C(12B)-O(1B)-B(1B)-F(2B) -96.74(12) C(12B)-O(1B)-B(1B)-N(1B) 20.28(14) C(1B)-N(1B)-B(1B)-F(1B) -139.92(10) C(4B)-N(1B)-B(1B)-F(1B) 44.43(13) C(1B)-N(1B)-B(1B)-F(2B) 99.24(11) C(4B)-N(1B)-B(1B)-F(2B) -76.41(12) C(1B)-N(1B)-B(1B)-O(1B) -19.60(13) C(4B)-N(1B)-B(1B)-O(1B) 164.75(9) ___________________________________________________________________________________

Symmetry transformations used to generate equivalent atoms:

参考文献参考文献参考文献参考文献

1) (a) R. Tsien, Y. Fluorescent Chemosensors for Ion and Molecule Recognition; Czarnik, A. W.

Ed.; ACS: Washington, DC, 1993, p. 130.

(b) P. Bamfield, Chromic Phenomena–Technological Applications of Colour Chemistry; RS·C:

Cambridge, 2001.

(c) H. Zollinger, Color Chemistry: Syntheses, Properties, and Applications of Organic Dyes and Pigments, 3rd ed.; Wiley-VCH: Weinheim, 2003.

(d) K. Hunger Ed. Industrial Dyes: Chemistry, Properties, Applications; Wiley-VCH:

Weinheim, 2003.

2) 伊与田正彦：「材料有機化学」，朝倉書店，2002.

3) Joseph R. Lalpwocz Principles of Fluorescence Spectroscopy, 2nd ed.; KLUWER ACADEMIC / PLENUM PUBLISHERS: New York, 1999, p. 531.

4) (a) A. Loudet, K. Burgess, Chem. Rev., 2007, 107, 4891.

(b) Y. Urano, D. Asanuma, Y. Hama, Y. Koyama, T. Barrett, M. Kamiya, T. Nagano, T. Watanabe, A. Hasegawa, P. Choyke, H. Kobayashi, Nat. Med. 2009, 15, 104.

5) (a) G. Patonay, J. Salon, J. Sowell, L. Strekowski, Molecules 2004, 9, 40.

(b) C.-H. Tung, Biopolymers 2004, 76, 391.

6) (a) T. Goto, Pure Appl. Chem. 1968, 17, 421.

(b) T. Goto, S. Inoue, S. Sugiura, K. Nishikawa, M. Isobe, Y. Abe, Tetrahedron Lett. 1968, 4035.

7) (a) R. Saito, T. Hirano, H. Niwa; M. Ohashi, J. Chem. Soc., Perkin Trans. 2 1997, 1711.

(b) Y. Imai, T. Shibata, S. Maki, H. Niwa, M. Ohashi, T. Hirano, J. Photochem. Photobiol. A 2001, 146, 95.

(d) T. Hirano, Y. Takahashi, H. Kondo, D. Maki, S. Kojima, H. Ikeda, H. Niwa, Photochem.

Photobiol. Sci. 2008, 7, 197.

8) 今井一洋：「生物発光と化学発光」，広川書店，1989.

9) (a) S. Blanchard, I. Rodriguez, C. Kuehm-Caubère, P. Renard, B. Pfeiffer, G. Guillaumet, P.

12) (a) I. D. W. Samuel, G. A. Turnbull, Chem. Rev. 2007, 107, 1272.

(b) N. Tessler, Adv. Mater. 1999, 11, 363

13) (a) G. De With, S. Harkema, D. Feil, Acta Crystallogr., Sect. B 1976, 32, 3178.

(b) E. Theophil, The Chemistry of Heterocycles, Thieme, New York, 1995.

14) Joseph R. Lalpwocz Principles of Fluorescence Spectroscopy, 2nd ed.; KLUWER ACADEMIC / PLENUM PUBLISHERS: New York, 1999, p. 5.

15) R. J. P. Williams, Chem. Rev. 1956, 2, 299.

16) (a) V. I. Minkin, M. N. Glukhovtsev, B. Y. Simkin, Aromaticity and Antiaromaticity, Electronic and Structural Aspects; Wiley: New York, 1994, p. 217.

(b) F. Stöckner, R. Beckert, D. Gleich, E. Birckner, W. Günther, H. Görls, G. Vaughan, Eur. J.

Org. Chem. 2007, 1237.

17) C. Yang, C. Hsu, P. Chou, H. Cheng, Y. Su, M. Leung, J. Phys. Chem. B, 2010, 114, 756

18) J. D. Anderson, E. M. McDonald, P. A. Lee, M. L. Anderson, E. L. Ritchie, H. K. Hall, T.

Hopkins, E. A. Mash, J. Wang, A. Padias, S. Thayumanavan, S. Barlow, S. R. Marder, G. E.

Jabbour, S. Shaheen, B. Kippelen, N. Peyghambarian R. M. Wightman, and N. R. Armstrong, J.

Am. Chem. Soc. 1998, 120, 9646.

19) M. J. Frisch et al. Gaussian 03, Revision C.02, Gaussian, Inc.: Wallingford, CT, 2004.

20) A. D. Becke, J. Chem. Phys. 1993, 98, 5648.

21) C. Lee, W. Yang, R. G. Parr, Phys. Rev. B 1988, 37, 785.

22) P. J. Stephens, F. J. Devlin, C. F. Chabalowski, M. J. Frisch, J. Phys. Chem. 1994, 98, 11623.

23) (a) P. v. R. Schleyer, C. Maerker, A. Dransfeld, H. Jiao, N. J. R. v. E. Hommes, J. Am. Chem.

Soc. 1996, 118, 6317.

(b)Z. F. Chen, C. S. Wannere, C. Corminboeuf, R. Puchta, P. v. R. Schleyer, Chem. Rev. 2005, 105, 3842.

24) (a) Y. Li, Y. Liu, W. Bu, J. Gup, Y. Wang, Chem. Commun. 2000, 1551

(b) K. Ono, K. Yoshikawa, Y. Tsuji, H. Yamaguchi, R. Uozumi, M. Tomura, K. Taga, K. Saito, Tetrahedron, 2007, 63, 9354.

25) C. Reichardt, Solvents and Solvent Effects in Organic Chemistry, 3rd ed.; Wiley-VCH:

Weinheim, 2003.

26) (a) M. M. Sartin, F. Camerel, R. Ziessel, A. J. Bard, J. Phys. Chem. C, 2008, 112, 10833.

(b) Y. Zhou, Y. Xiao, D. Li, M. Fu, X. Qian, J. Org. Chem., 2008, 73, 1571.

27) Altomare, A.; Burla, M. C.; Camalli, M.; Cascarano, G. L.; Giacovazzo, C.; Guagliardi, A.;

Moliterni, A. G.; Polidori, G.; Spagna, R. J. Appl. Cryst. 1999, 32, 115

謝辞謝辞謝辞謝辞

本研究は、電気通信大学電気通信学研究科量子物質工学専攻平野研究室において平野誉助教授の指導のもと行われたものであり、

ここに心から厚く御礼申し上げます。

また、研究を遂行するに当たり絶えず御助言を頂いた丹羽治樹教授、牧昌次郎助手、大橋陽子博士に深く感謝いたします。

共同研究として、 X 線結晶構造解析を行って頂き、様々な御助言を頂いた橋爪大輔博士に深く感謝いたします。

大阪府立大学にて固体蛍光における御助言並びに固体蛍光分光光度計を貸していただきました水野一彦教授、池田浩准教授、測定を手伝っていただいた吉本祐一氏に深く感謝いたします。

長い間苦楽を共にした丹羽・平野研究室の皆様に深く感謝いたします。

最後に、大学院進学に理解を示し精神的、経済的援助を頂いた両親・家族に深く感謝いたします。

平成

22

年

3

月八谷聡二郎

関連論文の印刷公表の方法及び時期

（１）全著者名 Sojiro Hachiya, Daisuke Hashizume, Shojiro Maki, Haruki Niwa, Takashi Hirano.

論文題目「Synthesis and properties of bis(pyrazino[2’,3’:4,5]imidazole)-fused 1,2,5,6-tetrahydro-1,4,5,8,9,10-hexaazaanthracenes: a new fluorescent nitrogen—rich heterocycle」

平成２２年 Tetrahedron Lett. 2010, 51, 1401.（本文第二章の研究内容）

（２）全著者名 Sojiro Hachiya, Takayuki Inagaki, Daisuke Hashizume, Shojiro Maki, Haruki Niwa, Takashi Hirano.

論文題目「Synthesis and fluorescence properties of difluoro[amidopyrazinato-O,N] boron derivatives: a new boron-containing fluorophore」

平成２２年 Tetrahedron Lett.2010, 51, 1613.（本文第三章の研究内容）

Synthesis and properties of bis(pyrazino[2

⁰

,3

⁰

:4,5]imidazole)-fused 1,2,5,6-tetrahydro-1,4,5,8,9,10-hexaazaanthracenes: a new ﬂuorescent nitrogen-rich heterocycle

Sojiro Hachiya^a, Daisuke Hashizume^b, Shojiro Maki^a, Haruki Niwa^a, Takashi Hirano^a,^*

aDepartment of Applied Physics and Chemistry, The University of Electro-Communications, Chofu, Tokyo 182-8585, Japan

bAdvanced Technology Support Division, RIKEN, Wako, Saitama 351-0198, Japan

a r t i c l e i n f o

Article history:

Received 5 December 2009 Revised 4 January 2010 Accepted 7 January 2010 Available online 11 January 2010

a b s t r a c t

Nitrogen-rich heterocycles, bis(pyrazino[2⁰,3⁰:4,5]imidazole)-fused 1,2,5,6-tetrahydro-1,4,5,8,9,10-hexa-azaanthracenes (BPI-HAAs) were prepared by conventional Pd(OAc)2/BINAP-catalyzed C–N coupling reactions of 5-aryl-3-bromoaminopyrazines. The BPI-HAA core is a planar structure with aromaticity, and this heterocycle exhibits red ﬂuorescence and moderate electron-accepting characteristics.

Fluorescent compounds are widely used in applications such as ﬂuorescent sensors for live-cell imaging and light-emitting compo-nents for organic light-emitting devices.¹Many ﬁelds depend on ad-vances in new ﬂuorescent compounds.² Fluorescent compounds based on bioluminescence³are promising because of their high-per-formance for light generation. Aminopyrazine is the core structure of the bioluminescence-related compound ethioluciferamine, derived from the ostracodCypridina,⁴and AF-350, derived from the jellyﬁsh Aequorea.⁵Aminopyrazines are also useful precursors for preparing bioluminescent substrates and light-emitter compounds.^4b,6In this study we then have attempted to prepare a new ﬂuorescent com-pound by modiﬁcation of an aminopyrazine derivative. As one of our target compounds, we tried to prepare 9,10-dihydro-1,4,5,8,9,10-hexaazaanthracene by C–N cross-coupling reactions^7–

9with 3-bromoaminopyrazine (1) and serendipitously generated a ﬂuorescent nitrogen-rich heterocycle, bis(pyrazino[2⁰,3⁰ :4,5]imid-azole)-fused 1,2,5,6-tetrahydro-1,4,5,8,9,10-hexaazaanthracene (BPI-HAA,2) (Scheme 1).¹⁰We report herein the synthesis and fun-damental properties of the new heterocycle2.

3,5-dialkylphenyl group. The reactions mainly produced red compounds2band2cin 7% and 6% yields, respectively. Molecular weights of2indicate that four molecules of1make up2, and the

1H NMR spectra of 2 indicate their symmetric structures. X-ray crystal structure analysis of 2bconﬁrmed its BPI-HAA structure (Fig. 1A) (cf.Supplementary data). Crystals of2bcontain two chloro-form molecules per unit cell. The solid-state structure of2bhas a planar core seven-fused ring system, and 3,5-di-t-butylphenyl groups are twisted with dihedral angles of 27°(C3 and C11) and 43°(C7 and C15). The core seven-fused ring system shows a bond length alternation (Fig. 1B).

N NH₂

Br R

Pd(OAc)₂ BINAP Cs₂CO₃

N N N R

N N N

toluene 100 °C

8 9

10 11 12

13 14 15 Tetrahedron Letters 51 (2010) 1401–1403

Contents lists available atScienceDirect

Tetrahedron Letters

j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / t e t l e t

Generation of2suggests that the C–N coupling reactions of1 produce 9,10-dihydro-1,4,5,8,9,10-hexaazaanthracenes as inter-mediates, and further condensation reactions of dihydrohexaaza-anthracenes with 1 produce 2. The reaction processes that generate2include four Pd-catalyzed C–N couplings, two nucleo-philic C–N couplings, and three dehydrogenations. In an attempt to regulate the preparation of 2b, we increased the amount of Pd(OAc)2(55 mol %) and BINAP (50 mol %), resulting in the gener-ation of orange compound3b(22% yield) instead of2b. Compound 3bconsists of three molecules of1b.¹¹

t-Bu

N t-Bu

N N N

N N t-Bu

t-Bu

structures. The absorption maxima (kab) and ﬂuorescence emission maxima (kf) of2bshowed a slight blue shift compared to those of 2aand2c, indicating that the bulky 3,5-di-t-butylphenyl groups of 2bare twisted against the planar BPI-HAA skeleton more than the 4-t-butylphenyl and 3,5-dihexylphenyl groups of 2a and 2c, respectively. Thek_abandk_fvalues of2bin various solvents indicate a slight dependency on solvent polarity (cf.Supplementary data).

Because the core ring system of2is a nitrogen-rich heterocycle, 2is expected to have electron-accepting characteristics.¹²Square wave voltammograms (SWVs) of2showed two reduction peaks at1.0 and1.5 V versus Fc/Fc⁺in CH2Cl2. Cyclic voltammograms of2indicated that the ﬁrst reduction at1.0 V showed reversible waves, whereas the waves of the second reduction at1.5 V were semi-reversible (cf.Supplementary data). The values of the ﬁrst reduction potentials indicate that2has an electron-accepting abil-ity similar to that ofp-benzoquinone.¹³

To better understand the observed properties of2, DFT calcula-tions on the core BPI-HAA [2(H), R = H] and tetraphenyl-substi-tuted BPI-HAA [2(Ph), R = Ph] were conducted at the B3LYP/6-31G(d) level.^14–17Optimized structures of2(H) and2(Ph) have a planar core seven-fused ring, and bond length alternation of their core ring systems is similar to that observed by X-ray structure of2b. Calculated dihedral angles of the phenyl groups against the core ring system in2(Ph) are 16° (C3 and C11) and 3°(C7 and C15). These values are smaller than the corresponding values

ob-N N

N R

N N

1.325

1.4051.334 1.380 1.353 1.322 1.428 1.341 1.349 1.379

1.394 1.322

1.381 1.346

1.436

1.406

side view

top view

A

B

1.461

Figure 1.Molecular structure of2b(A) whose hydrogen atoms were omitted for clarity and selected bond distances in a partial structure of2b(B).

4.0

2.0

0.0

700 600 500 400 300

1.0

0.5

0.0 wavelength / nm

Abs Fl

ε x 10−4 intensity

Figure 2.UV–vis absorption (Abs) and ﬂuorescence (Fl) spectra of2a(blue),2b (black), and2c(red) in CHCl3at 25°C.

Table 1

UV–vis absorption, ﬂuorescence emission, and reduction potentials of2

Compounds kaba

(nm) [e/10⁴] kfa

(nm) [Uf] E^red(V)^b

2a 551 [3.9],

513 [4.2], 425 [4.1], 329 [4.2]

616, 571 [0.75]

1.00 1.35

2b 538 [3.6],

503 [3.8], 420 [3.6], 323 [3.7]

603, 563 [0.71]

0.97 1.50

2c 550 [3.6],

513 [3.8], 426 [4.0], 334 [3.9]

616, 570 [0.75]

1.00 1.51

aIn CHCl3.

b0.10 Mn-Bu4NClO4in CH2Cl2, Pt electrode, scanning rate 100 mV s¹,Vversus Fc/Fc⁺.

1402 S. Hachiya et al. / Tetrahedron Letters 51 (2010) 1401–1403

energy fromS0toS1for2(Ph) was calculated by TD-DFT [B3LYP/6-31G(d)] to be 2.30 eV (540 nm, oscillator strength = 0.60), which is well similar to those of the observed lowest energy absorption bands of2. Nucleus induced chemical shift (NICS) values¹⁸at the centers of the A–D rings in2(H) were calculated to range from 1.3 to13.5 at the GIAO-B3LYP/6-31+G(d)//B3LYP/6-31G(d) level (Fig. 3). The values for the A and D rings are similar to that of pyr-azine, and the value for the C ring is similar to that of imidazole.¹⁸ These negative NICS values for the A, C, and D rings predict that the BPI-HAA ring system has aromatic characteristics, while the B rings show a small negative value.

In conclusion, we successfully prepared a heterocyclic seven-fused ring system, BPI-HAA2by conventional Pd(OAc)₂ /BINAP-cat-alyzed C–N coupling reactions of1. The BPI-HAA core is a planar structure with aromatic characteristics. Because2has both ﬂuores-cent and electron-accepting characteristics, it will be useful as a new ﬂuorophore and as a new electron-carrier for biological and materials science. The nitrogen-rich structure of2will also be use-ful as a ligand for making metal ion-complexes, and an investiga-tion of metal ion-complex formainvestiga-tion with2is now in progress.

Acknowledgments

This work was supported by a grant from the Japan Science and Technology Agency for Research for Promoting Technological Seeds. We acknowledge technical assistance in computing the quantum chemical calculations from the Information Technology Center of UEC.

Supplementary data

Supplementary data (experimental details,¹H NMR spectra of1, 2, and3b, single crystal X-ray analysis, UV–vis absorption and ﬂuo-rescence spectra, and DFT calculation data) associated with this article can be found, in the online version, at doi:10.1016/

Harriman, A. New J. Chem.2007, 31, 496–501; (d) Ulrich, G.; Ziessel, R.;

Harriman, A.Angew. Chem., Int. Ed.2008,47, 1184–1201.

3. (a) Saito, R.; Hirano, T.; Niwa, H.; Ohashi, M.J. Chem. Soc., Perkin Trans. 21997, 1711–1716; (b) Kojima, S.; Ohkawa, H.; Hirano, T.; Niwa, H.; Ohashi, M.;

Inouye, S.; Tsuji, F. I.Tetrahedron Lett.1998, 39, 5239–5243; (c) Imai, Y.;

Shibata, T.; Maki, S.; Niwa, H.; Ohashi, M.; Hirano, T.J. Photochem. Photobiol. A 2001,146, 95–107; (d) Takamuki, Y.; Maki, S.; Niwa, H.; Ikeda, H.; Hirano, T.

Tetrahedron2005,61, 10073–10080.

4. (a) Kishi, Y.; Goto, T.; Hirata, Y.; Shimomura, O.; Johnson, F. H.Tetrahedron Lett.

1966, 3427–3436; (b) Kishi, Y.; Goto, T.; Inoue, S.; Sugiura, S.; Kishimoto, H.

Tetrahedron Lett.1966, 3445–3450.

5. (a) Shimomura, O.; Johnson, F. H.Biochemistry1972,11, 1602–1607; (b) Kishi, Y.; Tanino, H.; Goto, T.Tetrahedron Lett.1972, 2747–2748.

6. (a) Goto, T.; Inoue, S.; Sugiura, S.Tetrahedron Lett.1968, 3873–3876; (b) Inoue, S.; Sugiura, S.; Kakoi, H.; Goto, T.Tetrahedron Lett.1969, 1609–1610; (c) Inoue, S.; Sugiura, S.; Kakoi, H.; Hasizume, K.; Goto, T.; Iio, H.Tetrahedron Lett.1975, 141–144; (d) Nakamura, H.; Aizawa, M.; Takeuchi, D.; Murai, A.; Shimomura, O.

Tetrahedron Lett.2000,41, 2185–2188; (e) Wu, C.; Kawasaki, K.; Ohgiya, S.;

Ohmiya, Y.Tetrahedron Lett.2006,47, 753–756.

7. (a) Guram, A. S.; Rennels, R. A.; Buchwald, S. L.Angew. Chem., Int. Ed.1995,34, 1348–1350; (b) Louie, J.; Hartwig, J. F.Tetrahedron Lett.1995,36, 3609–3612.

8. Reviews: (a) Hartwig, J. F.Angew. Chem., Int. Ed.1998,37, 2046–2067; (b) Wolfe, J. P.; Wagaw, S.; Marcoux, J.-F.; Buchwald, S. L.Acc. Chem. Res.1998,31, 805–818; (c) Yang, B. H.; Buchwald, S. L.J. Organomet. Chem.1999,576, 125–

146; (d) Muci, A. R.; Buchwald, S. L.Top. Curr. Chem.2002,219, 131–209.

9. Pd(OAc)2/BINAP-catalyzed C–N coupling: (a) Wolfe, J. P.; Wagaw, S.; Buchwald, S. L.J. Am. Chem. Soc.1996,118, 7215–7217; (b) Wolfe, J. P.; Buchwald, S. L.

Tetrahedron Lett.1997,38, 6359–6362; (c) Wolfe, J. P.; Buchwald, S. L.J. Org.

Chem.2000,65, 1144–1157.

10. Palladium-catalyzed C–N coupling reactions were well applied for construction of heterocyclic fused ring systems: (a) Loones, K. T. J.; Maes, B. U. W.; Dommisse, R. A.; Lemiere, G. L. F.Chem. Commun.2004, 2466–2467; (b) Dajka-Halasz, B.;

Monsieurs, K.; Elias, O.; Karolyhazy, L.; Tapolcsanyi, P.; Maes, B. U. W.; Riedl, Z.;

Hajos, G.; Dommisse, R. A.; Lemiere, G. L. F.; Kosmrlj, J.; Matyus, P.Tetrahedron 2004,60, 2283–2291; (c) Loones, K. T. J.; Maes, B. U. W.; Meyers, C.; Deruytter, J.J.

Org. Chem.2006,71, 260–264; (d) Loones, K. T. J.; Maes, B. U. W.; Herrebout, W. A.;

Dommisse, R. A.; Lemiere, G. L. E.; Van der Veken, B. J.Tetrahedron2007,63, 3818–

3825; (e) Loones, K. T. J.; Maes, B. U. W.; Dommisse, R. A.Tetrahedron2007,63, 8954–8961; (f) Meyers, C.; Rornbouts, G.; Loones, K. T. J.; Coelho, A.; Maes, B. U.

W.Adv. Synth. Cat.2008,350, 465–470; (g) Franck, P.; Hostyn, S.; Dajka-Halasz, B.; Polonka-Balint, A.; Monsieurs, K.; Matyus, P.; Maes, B. U. W.Tetrahedron2008, 64, 6030–6037; (h) Hostyn, S.; Van Baelen, G.; Lemiere, G. L. F.; Maes, B. U. W.Adv.

Synth. Cat.2008,350, 2653–2660; (i) Van Baelen, G.; Meyers, C.; Lemiere, G. L. F.;

Hostyn, S.; Dommisse, R.; Maes, L.; Augustyns, K.; Haemers, A.; Pieters, L.; Maes, B. U. W. Tetrahedron 2008, 64, 11802–11809; (j) Boganyi, B.; Kaman, J.

J. Heterocycl. Chem.2009,46, 33–38.

11. While2were stable compounds under laboratory conditions,3bwas unstable and slowly decomposed during handling.

12. (a) Minkin, V. I.; Glukhovtsev, M. N.; Simkin, B. Y. Aromaticity and Antiaromaticity, Electronic and Structural Aspects; Wiley: New York, 1994. pp 217–229; (b) Stöckner, F.; Beckert, R.; Gleich, D.; Birckner, E.; Günther, W.;

Görls, H.; Vaughan, G.Eur. J. Org. Chem.2007, 1237–1243; (c) Bunz, U. H. F.

Chem. Eur. J.2009,15, 6780–6789.

13. Sawyer, D. T.; Sobkowiak, A.; Roberts, J. L., Jr.Electrochemistry for Chemists, 2nd ed.; Wiley: New York, 1995. pp 446–451.

14. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.;

Cheeseman, J. R.; Montgomery, J. A., Jr.; Vreven, T.; Kudin, K. N.; Burant, J. C.;

Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.;

Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.;

Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A.

J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G.

−7.6

−13.5

−1.3

−8.4 N

N N

N N N

N N

A B B

C C

Figure 3.NICS values of2(H).

S. Hachiya et al. / Tetrahedron Letters 51 (2010) 1401–1403 1403

Synthesis and ﬂuorescence properties of diﬂuoro[amidopyrazinato-O,N]boron derivatives: a new boron-containing ﬂuorophore

Sojiro Hachiya^a, Takayuki Inagaki^a, Daisuke Hashizume^b, Shojiro Maki^a, Haruki Niwa^a, Takashi Hirano^a,^*

aDepartment of Applied Physics and Chemistry, The University of Electro-Communications, Chofu, Tokyo 182-8585, Japan

bAdvanced Technology Support Division, RIKEN, Wako, Saitama 351-0198, Japan

a r t i c l e i n f o

Article history:

Received 22 December 2009 Revised 18 January 2010 Accepted 22 January 2010 Available online 28 January 2010

a b s t r a c t

New boron-containing ﬂuorophores, diﬂuoro[amidopyrazinato-O,N]boron (APB) derivatives, were pre-pared from amidopyrazines. The ﬂuorescence properties of APB were successfully modulated by an aryl substitution at the C8 position.

Cypridinaoxyluciferin (Scheme 1) and coelenteramide are the light-emitter compounds for bioluminescence of the ostracod Cyp-ridina¹and the jellyﬁshAequorea,²respectively. These light-emitter compounds have an amidopyrazine core structure. We investigated the ﬂuorescence properties of the derivatives ofCypridina oxyluci-ferin and coelenteramide and found that the excited singlet states of these compounds have an intramolecular charge transfer (ICT) character and show ﬂuorescence solvatochromism.³Because ﬂuo-rescent compounds are widely used in many applications, such as ﬂuorescent sensors for biological imaging and light-emitting com-ponents for organic light-emitting devices,⁴one of our goals is to design a new ﬂuorescent compound based onCypridina oxyluci-ferin and coelenteramide. We attempted to modify the chemical structure of amidopyrazine using the methodology for preparing boron dipyrromethene (BODIPY).⁵We then successfully prepared new boron-containing ﬂuorophores, diﬂuoro[amidopyrazinato-O,N]boron (APB) derivatives (2), by the reactions of amidopyrazines (1) with BF3(Scheme 1). In this Letter, we describe the synthesis and ﬂuorescence properties of these APB derivatives2.

Pivalamidopyrazine1awas treated with BF₃Et₂O in the pres-ence ofN,N-diisopropylethylamine (DIPEA) at room temperature to give 8-t-butyl APB (2a) in 83% yield.⁶Although acetamidopyr-azine1balso reacted with BF₃Et₂O in the presence of DIPEA, we could not isolate2bfrom the complex mixture of products. This re-sult suggests that deprotonation of the methyl group at C8 induces decomposition of2b. Therefore, it would be preferable to use an amidopyrazine having a tertiary or aryl group at C8 for preparing APB compounds. We were also able to convert benzamidopyrazine 1cand its derivatives1dand1eto the corresponding APBs2c–ein 40 60% yields. Crystal structure analysis of2aconﬁrmed its APB

of 2a shows a bond length alternation (Fig. 1B). Unfortunately, however, APBs (2) were slowly decomposed to give1by solvolysis in a protic solvent such as methanol.

UV–vis absorption and ﬂuorescence spectra of the APB deriva-tives (2) were measured in cyclohexane, chloroform, and acetoni-trile.^8,9 It was conﬁrmed that the excitation spectra of the ﬂuorescence agree with the corresponding absorption spectra.

The spectral data are summarized inTable 1.Figure 2shows repre-sentative spectra in chloroform. The lowest energy absorption bands of 2a and 2c in chloroform were observed at 331 and 353 nm, respectively, and ﬂuorescence emission maxima (kf) of 2aand2cwere observed at 384 and 402 nm with quantum yields

N N

NH O

NH NH₂ N NH

N N

O R

Cypridina oxyluciferin

N N

BO ^R

FF BF3·Et2O DIPEA, CH₂Cl₂

RT 1a: R = C(CH )

1 2 3 4 5

6 7

2a (83%) Tetrahedron Letters 51 (2010) 1613–1615

Contents lists available atScienceDirect

Tetrahedron Letters

j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / t e t l e t

(Uf) to be 0.12 and 0.15, respectively. This result indicates that the introduction of a phenyl group instead of atert-butyl group at C8 induces 20 nm red shifts of the lowest energy absorption and ﬂuo-rescence emission bands. Thus, the expansion of thep-electronic conjugation at C8 of the APB skeleton effectively modulates the spectroscopic characteristics. Another phenyl substitution effect appears to be an increase of the extinction coefﬁcient of the lowest energy absorption band compared to that of2a. The absorption maxima (kab) and thekfvalues of2a,2c, and2dindicate a slight dependency on solvent polarity,¹⁰ whereas theUfvalue of 2cin acetonitrile and that of2dwere less than 0.01. On the other hand, 4-methoxyphenyl derivative2eshowed ﬂuorescence solvatochro-mism (Fig. 3). Although the lowest energy absorption bands of2e showed a small solvent-dependent variation at around 370 nm, thekfvalue of2ewas red shifted with increased solvent polarity.¹⁰ This result indicates that the ICT character of the excited singlet state of2eis much greater than that of the ground state.

To better understand the observed structural and spectroscopic properties of the APB derivatives (2), DFT and time-dependent (TD) DFT calculations on2 and amidopyrazines1a and1cwere con-ducted at the B3LYP/6-31G(d) level (Table 2).^11–14Optimized struc-ture of2a was very similar to the X-ray crystal structure of2a, whose boron-containing ring is bent. The HOMO and LUMO levels of2aand2cwere lower than those of1aand1c, indicating that the electron-accepting character of the APB derivative is greater than that of the corresponding amidopyrazine. Although the excitation wavelengths (kex) calculated for2 were predicted to be shorter than theirkabvalues observed in cyclohexane, the relative differ-ences in thekexandk_abvalues among2aand2c–eagree well with each other. The ﬁnding that the oscillator strength (f) of2cis great-er than that of2aalso matches the difference in theevalues of the lowest energy absorption bands of2aand2c.Figure 4shows the electron distribution of the HOMOs and LUMOs of2cand2e. While the HOMO and LUMO densities of2care located on the APB skel-eton, the HOMO and LUMO densities of2eare mainly localized on the 4-methoxyphenyl moiety and the APB skeleton, respec-tively. This result supports the premise that the excited singlet side view

top view

N N

B O C(CH₃)₃ FF ^1.456

1.317 1.293

1.411 1.371

1.581

1.348 1.318 1.353

1.347

A

B

1.369

Figure 1.Molecular structure of2a(A) with the atomic displacements drawn at the 50% probability level and selected bond distances in a partial structure of2a(B).

3.0

2.0

1.0

0.0

1.0

0.5

0.0

a b c a

b c

ε x 10−4 normalized intensity

A B

Table 1

Electronic absorption and ﬂuorescence of2aand2c–ein various solvents at 25°C Compound Solvent kab/nm (e/10⁴)^a kf/nm (Uf)^b

2a C6H12 332 (0.86) 384 (0.078)

CHCl3 331 (1.1) 384 (0.12)

CH3CN 329 (0.88) 386 (0.10)

2c C6H12 351 (2.6), 274 (1.7) 398 (0.18)

CHCl3 353 (2.7), 274 (1.7) 402 (0.15) CH3CN 349 (2.7), 268 (1.7) 395 (0.008)

2d C6H12 351 (2.0), 271 (1.4) 404 (0.013)

CHCl3 354 (2.1), 271 (1.4) 408 (0.004) CH3CN 351 (2.0), 266 (1.4) n.d.^c 2e C6H12 382 (3.0), 365 (3.2), 298 (1.2), 281

(1.2)

411, 396 (0.29) CHCl3 373 (2.9), 286 (1.1) 429 (0.16) CH3CN 363 (2.9), 291 (1.1) 478 (0.062)

aAbsorption maximum (kab) and extinction coefﬁcient (ein dm³mol¹cm¹).

b Fluorescence emission maximum (kf) and quantum yield (Uf).

c Fluorescence was weak.

1614 S. Hachiya et al. / Tetrahedron Letters 51 (2010) 1613–1615

ドキュメント内新規蛍光色素の開発研究 (ページ 134-185)

X

RAXIS-CS Imaging Plate

SIR-97

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謝辞 謝辞 謝辞 謝辞

本研究は、電気通信大学 電気通信学研究科 量子物質工学専攻 平野 研究室に おいて平野 誉 助教授の指導のもと 行われたものであ り、

ここに心から厚く御礼申し上げます。

ま た 、 研 究 を 遂 行 す る に 当 た り 絶 え ず 御 助 言 を 頂 い た 丹 羽 治 樹 教授、牧 昌次郎 助手、大橋 陽子 博士に深く感謝いたします。

共同研究として、 X 線結晶構造解析を行って頂き、様々な御助言 を頂いた橋爪 大輔 博士に深く感謝いたします。

大 阪府立大学にて固 体蛍光における御 助言並びに固体蛍 光分光光 度計 を貸していただき ました水野一彦教 授、池田浩准教授 、測定を 手伝っていただいた吉本祐一氏に深く感謝いたします。

長 い間苦楽を共にし た丹羽・平野研究 室の皆様に深く感 謝いたし ます。

最 後に、大学院進学 に理解を示し精神 的、経済的援助を 頂いた両 親・家族に深く感謝いたします。

22

3

Synthesis and properties of bis(pyrazino[2

,3

:4,5]imidazole)-fused 1,2,5,6-tetrahydro-1,4,5,8,9,10-hexaazaanthracenes: a new ﬂuorescent nitrogen-rich heterocycle

Tetrahedron Letters

A

B

Synthesis and ﬂuorescence properties of diﬂuoro[amidopyrazinato-O,N]boron derivatives: a new boron-containing ﬂuorophore

Tetrahedron Letters

A

B

A B

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謝辞謝辞謝辞謝辞

本研究は、電気通信大学電気通信学研究科量子物質工学専攻平野研究室において平野誉助教授の指導のもと行われたものであり、

また、研究を遂行するに当たり絶えず御助言を頂いた丹羽治樹教授、牧昌次郎助手、大橋陽子博士に深く感謝いたします。

共同研究として、 X 線結晶構造解析を行って頂き、様々な御助言を頂いた橋爪大輔博士に深く感謝いたします。

大阪府立大学にて固体蛍光における御助言並びに固体蛍光分光光度計を貸していただきました水野一彦教授、池田浩准教授、測定を手伝っていただいた吉本祐一氏に深く感謝いたします。

長い間苦楽を共にした丹羽・平野研究室の皆様に深く感謝いたします。

最後に、大学院進学に理解を示し精神的、経済的援助を頂いた両親・家族に深く感謝いたします。