Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2004 Chem. Eur. J. 2004

Supporting Information

for

A General and Versatile Approach to Thermally Generated

N-Heterocyclic Carbenes

Gregory Nyce, Szilard Csihony, Robert M. Waymouth,* and James L. Hedrick*

Center for Polymeric Interfaces and Macromolecular Assemblies

[*] G. W. Nyce, J. L. Hedrick

IBM Almaden Research Center 650 Harry Rd. San Jose, CA 95120 (USA)

Fax (+1) 408-927-1632 E-mail: Hedrick@almaden.ibm.com

S. Csihony, R. M. Waymouth

Stanford University Stauffer 1, Room 205, Stanford, CA 94305 (USA)

Fax (+1) 650-736-2262 E-mail: waymouth@stanford.edu

Table S1. Results of NHC adduct precatalysts for L-lactide polymerization. All experiments used benzyl alcohol as the initiator with a target DP of 100.

Entry Precatalyst Polymerization

Conditions %

Conv.

6 N NH CF3

THF, 65oC, 3h 0

7 N NH CF3

PhCH3, 110

oC, 12h 0

8

N N

H L

o-xylene, 144 oC, 48h 0

9 N N

H L

THF, 65 oC, 3h 0

10 N N

H L

PhCH3, 110 oC, 12h

0

NO2F3C CF3

F

FF

L =

Table S2. Rate Constants and activation parameters for decomposition of carbene adducts.

Ea / kJ mol-1 96.1 (±15.4)

SImMesHC6F5 ([CS2]=0.360 mol dm-3)

T / oC 39.5 54.1 59.0 63.7 68.5

kobs / sec -1 1.85(±0.83)

x10-5 1.01(±0.10)

x10-4 1.81(±0.10)

x10-4 3.06(±0.13)

x10-4 4.60(±0.60)

x10-4

∆H / kJ mol-1 100.7 (±7.4)

∆S / J mol-1 K-1 -12.5 (±22.4)

Ea / kJ mol-1 103.5 (±7.4)

SImMesHCCl3 ([CS2]=0.280 mol dm-3)

T / oC 34.6 39.3 44.3 49.1 53.9

kobs / sec -1 5.00(±1.50)

x10-5 8.39(±2.74)

x10-5 1.63(±0.44)

x10-4 2.64(±0.62)

x10-4 4.57(±1.20)

x10-4

∆H / kJ mol-1 93.4 (±15.4)

∆S / J mol-1 K-1 -22.0 (±48.6)

SImMesHC6F5 Conc. / mol dm-3 0.036 0.036 0.016 0.036

CS2 Conc. / mol dm-3 0.360 0.720 0.720 1.080

kobs / sec-1 at 68.5oC 4.60(±0.60)

x10-4 3.95(±0.67)

x10-4 3.93(±0.65)

x10-4 3.27(±0.65)

x10-4

Kinetic plots for thermolysis of adducts in the presence of CS2.

Figure S1. Thermolysis of the SImMesHCCl3 adduct at 49.1 oC.

Figure S2. First order plot of the decomposition of SImMesHCCl3 at 49.1 oC.

Figure S3. Second order plot of SImMesHCCl3 at 49.1 oC.

Figure S4. Activation energy for thermolysis of SImMesHCCl3.

Figure S5. Dependence of kobs for thermolysis of SImMesHC6F5 on [CS2], temperature and [SImMesHC6F5]0 (= 0.036 M, 0.016M).

Figure S6. Activation energy for thermolysis of SImMesHC6F5.

X-ray Crystal Structure of 4.

X-ray quality crystals of 4 were grown by cooling a saturated solution hexamethyldisiloxane:CH2Cl2 (90:10). A colorless crystal of approximate dimensions 0.10 x 0.28 x 0.36 mm was mounted on a glass fiber and transferred to a Bruker CCD platform diffractometer. The SMART1 program package was used to determine the unit-cell parameters and for data collection (25 sec/frame scan time for a sphere of diffraction data). The raw frame data was processed using SAINT2 and SADABS3 to yield the reflection data file. Subsequent calculations were carried out using the SHELXTL4 program. There were no systematic absences nor any diffraction symmetry other than the Friedel cond ition. The centrosymmetric triclinic space group P1 was assigned and later determined to be correct.

The structure was solved by direct methods and refined on F2 by full-matrix least-squares techniques. The analytical scattering factors5 for neutral atoms were used throughout the analysis. Hydrogen atoms were included using a riding model. There were four molecules of the formula unit present. Least-squares refinement yielded wR2 = 0.3077 and Goof = 1.036 for 1226 variables refined against 18670 data (0.80 Å resolution). As a comparison for refinement on F, R1 = 0.1000 for those 10306 data with I > 2.0σ(I). The higher than expected discrepancy indices are probably due to the large number of weak diffraction data.

Table S3. Crystal data and structure refinement for 4. Empirical formula C27 H27 F5 N2

Formula weight 474.51 Temperature 163(2) K Wavelength 0.71073 Å Crystal system Triclinic

Space group P1 Unit cell dimensions a = 16.0099(15) Å α= 90.114(2)°. b = 16.8809(16) Å β= 109.575(2)°. c = 18.9764(17) Å γ = 106.893(2)°.

Volume 4595.5(7) Å3 Z 8 Density (calculated) 1.372 Mg/m3 Absorption coefficient 0.109 mm-1

F(000) 1984 Crystal size 0.36 x 0.28 x 0.10 mm3 Theta range for data collection 1.15 to 26.37°. Index ranges -20 ≤ h ≤ 20, -21 ≤ k ≤ 20, -23 ≤ l ≤ 23

Reflections collected 44690 Independent reflections 18670 [R(int) = 0.0724] Completeness to theta = 26.37° 99.3 % Absorption correction None

Max. and min. transmission 0.9892 and 0.9619 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 18670 / 0 / 1226 Goodness-of-fit on F2 1.036

Final R indices [I>2sigma(I)] R1 = 0.1000, wR2 = 0.2575 R indices (all data) R1 = 0.1752, wR2 = 0.3077 Extinction coefficient 0.0016(4) Largest diff. peak and hole 0.643 and -0.587 e.Å-3

Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2 x 103)

for 4. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. ________________________________________________________________________________ x y z U(eq)

________________________________________________________________________________ N(1) 2948(3) 2377(3) 507(3) 25(1) N(2) 2378(3) 1221(3) 1025(3) 26(1)

C(1) 2367(4) 2081(3) 963(3) 21(1) C(2) 3032(4) 1662(3) 116(3) 30(1) C(3) 2505(7) 919(4) 373(5) 61(2) C(4) 2838(4) 3073(3) 88(3) 22(1)

C(5) 3607(4) 3797(3) 273(3) 24(1) C(6) 3556(4) 4455(3) -172(3) 30(1) C(7) 2775(4) 4409(4) -790(3) 31(1) C(8) 2013(4) 3686(3) -960(3) 27(1)

C(9) 2025(4) 3013(3) -533(3) 23(1) C(10) 4489(4) 3863(4) 921(4) 35(1) C(11) 2738(5) 5089(4) -1305(4) 37(2) C(12) 1173(4) 2258(4) -764(3) 32(1)

C(13) 1847(4) 666(3) 1399(3) 24(1) C(14) 871(4) 499(3) 1199(3) 25(1) C(15) 405(4) -54(3) 1582(3) 29(1) C(16) 858(4) -469(3) 2156(3) 28(1)

C(17) 1812(4) -309(3) 2326(3) 26(1) C(18) 2310(4) 253(3) 1964(3) 24(1) C(20) 328(5) -1062(4) 2559(3) 36(1) C(21) 3351(4) 405(4) 2198(4) 34(1)

C(22) 2757(4) 2595(3) 1729(3) 22(1) C(19) 302(4) 876(3) 565(3) 30(1) C(23) 2203(4) 2955(3) 1970(3) 25(1) C(24) 2529(4) 3466(3) 2629(3) 30(1)

C(25) 3439(4) 3614(3) 3094(3) 31(1) C(26) 4003(4) 3240(4) 2896(3) 30(1)

C(27) 3659(4) 2746(3) 2220(3) 27(1) F(1) 1298(2) 2810(2) 1541(2) 31(1)

F(2) 1975(3) 3813(2) 2825(2) 38(1) F(3) 3787(3) 4123(2) 3745(2) 44(1) F(4) 4882(2) 3365(2) 3366(2) 42(1) F(5) 4251(2) 2411(2) 2054(2) 32(1)

N(3) 2306(3) 6157(3) 2541(3) 26(1) N(4) 2858(3) 7320(3) 3378(3) 26(1) C(28) 2258(4) 7011(3) 2602(3) 24(1) C(29) 2581(8) 5892(5) 3264(4) 89(4)

C(30) 2972(5) 6623(4) 3823(3) 32(1) C(31) 1748(4) 5574(3) 1886(3) 25(1) C(32) 2205(4) 5176(3) 1553(3) 27(1) C(33) 1676(4) 4568(4) 941(3) 32(1)

C(34) 716(5) 4340(3) 653(3) 31(1) C(35) 274(4) 4733(4) 983(3) 30(1) C(36) 763(4) 5343(3) 1600(3) 25(1) C(37) 3245(4) 5381(4) 1837(4) 38(2)

C(38) 151(5) 3651(4) 15(3) 39(2) C(39) 221(4) 5705(4) 1945(3) 33(1) C(40) 2758(4) 8023(3) 3743(3) 25(1) C(41) 1950(4) 7972(3) 3912(3) 26(1)

C(42) 1945(4) 8651(4) 4330(3) 30(1) C(43) 2700(5) 9372(4) 4583(3) 32(1) C(44) 3480(5) 9408(4) 4402(3) 32(1) C(45) 3530(4) 8743(4) 3989(3) 30(1)

C(46) 1096(4) 7221(4) 3669(3) 33(1) C(47) 2676(5) 10064(4) 5074(4) 45(2) C(48) 4413(4) 8809(4) 3845(4) 37(2) C(49) 2603(4) 7543(3) 2044(3) 24(1)

C(50) 2028(4) 7908(3) 1524(3) 27(1) C(51) 2318(4) 8432(4) 1043(3) 30(1) C(52) 3230(5) 8612(4) 1067(3) 34(1) C(53) 3821(4) 8243(4) 1563(3) 30(1)

C(54) 3505(4) 7725(3) 2040(3) 25(1) F(6) 1140(2) 7761(2) 1487(2) 32(1)

F(7) 1741(3) 8776(2) 556(2) 42(1) F(8) 3538(3) 9134(2) 614(2) 45(1)

F(9) 4697(3) 8403(2) 1577(2) 44(1) F(10) 4119(2) 7397(2) 2516(2) 33(1) N(5) 6906(3) 5776(3) 4363(3) 26(1) N(6) 7445(3) 4905(3) 3830(3) 25(1)

C(55) 7515(4) 5785(3) 3935(3) 23(1) C(56) 6625(5) 4952(4) 4625(4) 35(2) C(57) 7230(5) 4497(4) 4452(4) 35(1) C(58) 7044(4) 6495(3) 4838(3) 26(1)

C(59) 6307(4) 6833(4) 4681(3) 32(1) C(60) 6386(5) 7506(4) 5164(4) 40(2) C(61) 7179(5) 7853(4) 5797(4) 42(2) C(62) 7904(5) 7513(3) 5934(3) 33(1)

C(63) 7851(4) 6843(3) 5473(3) 28(1) C(64) 5423(4) 6473(4) 4019(4) 45(2) C(65) 7243(6) 8550(4) 6327(4) 54(2) C(66) 8646(5) 6483(4) 5698(4) 39(2)

C(67) 8021(4) 4627(3) 3510(3) 23(1) C(68) 9001(4) 4967(3) 3767(3) 26(1) C(69) 9485(4) 4640(4) 3418(3) 28(1) C(70) 9058(4) 3986(4) 2847(3) 27(1)

C(71) 8093(4) 3652(3) 2617(3) 27(1) C(72) 7572(4) 3964(3) 2938(3) 27(1) C(73) 9546(4) 5649(3) 4408(3) 30(1) C(74) 9601(4) 3647(4) 2478(3) 35(1)

C(75) 6523(4) 3563(4) 2653(3) 30(1) C(76) 7183(4) 6124(3) 3179(3) 22(1) C(77) 7763(4) 6779(3) 2968(3) 23(1) C(78) 7483(4) 7151(3) 2326(3) 28(1)

C(79) 6577(4) 6850(4) 1842(3) 28(1) C(80) 5970(4) 6176(4) 2008(3) 27(1) C(81) 6264(4) 5820(3) 2663(3) 26(1) F(11) 8678(2) 7096(2) 3420(2) 29(1)

F(12) 8083(2) 7800(2) 2163(2) 34(1) F(13) 6280(2) 7202(2) 1209(2) 35(1)

F(14) 5087(2) 5879(2) 1529(2) 39(1) F(15) 5637(2) 5174(2) 2802(2) 32(1)

N(7) 7492(3) -115(3) 2493(2) 28(1) N(8) 6964(4) 756(3) 1658(3) 30(1) C(82) 7594(4) 773(3) 2423(3) 25(1) C(83) 7233(5) -533(4) 1743(3) 37(2)

C(84) 6628(5) -78(4) 1246(3) 41(2) C(85) 8067(4) -409(3) 3125(3) 26(1) C(86) 7608(4) -1072(3) 3447(3) 28(1) C(87) 8136(4) -1403(3) 4040(3) 29(1)

C(88) 9101(4) -1108(4) 4328(3) 29(1) C(89) 9531(4) -449(3) 4001(3) 27(1) C(90) 9053(4) -94(3) 3407(3) 28(1) C(91) 6558(4) -1429(4) 3159(4) 35(1)

C(92) 9653(4) -1506(4) 4950(3) 34(1) C(93) 9602(4) 570(4) 3065(3) 32(1) C(94) 7074(4) 1475(3) 1257(3) 28(1) C(95) 7864(4) 1841(4) 1071(3) 30(1)

C(96) 7888(5) 2515(4) 636(3) 35(1) C(97) 7133(5) 2815(4) 364(3) 40(2) C(98) 6353(5) 2440(4) 551(4) 43(2) C(99) 6303(5) 1774(4) 996(3) 37(2)

C(100) 8686(5) 1521(4) 1294(4) 41(2) C(101) 7165(6) 3514(4) -139(4) 53(2) C(102) 5429(5) 1386(5) 1159(5) 56(2) C(103) 7309(4) 1143(3) 3003(3) 26(1)

C(104) 6421(4) 859(3) 3046(3) 28(1) C(105) 6158(4) 1245(4) 3547(3) 32(1) C(106) 6791(5) 1926(4) 4029(3) 32(1) C(107) 7668(5) 2225(3) 4010(3) 32(1)

C(108) 7918(4) 1826(3) 3515(3) 27(1) F(16) 5767(2) 201(2) 2582(2) 38(1) F(17) 5298(3) 950(2) 3578(2) 45(1) F(18) 6520(3) 2305(2) 4504(2) 41(1)

F(19) 8301(3) 2887(2) 4490(2) 42(1) F(20) 8807(2) 2141(2) 3527(2) 34(1)

________________________________________________________________________________

Table 3. Bond lengths [Å] and angles [°] for gnibm1. _____________________________________________________

N(1)-C(4) 1.440(7) N(1)-C(1) 1.460(6) N(1)-C(2) 1.477(7) N(2)-C(13) 1.433(7)

N(2)-C(3) 1.435(8) N(2)-C(1) 1.460(7) C(1)-C(22) 1.526(7) C(2)-C(3) 1.479(8)

C(4)-C(5) 1.403(8) C(4)-C(9) 1.410(8) C(5)-C(6) 1.402(8) C(5)-C(10) 1.504(8)

C(6)-C(7) 1.380(9) C(7)-C(8) 1.396(8) C(7)-C(11) 1.512(8) C(8)-C(9) 1.398(7)

C(9)-C(12) 1.504(8) C(13)-C(18) 1.397(8) C(13)-C(14) 1.418(8) C(14)-C(15) 1.384(8)

C(14)-C(19) 1.512(8) C(15)-C(16) 1.404(8) C(16)-C(17) 1.392(8) C(16)-C(20) 1.502(8)

C(17)-C(18) 1.393(8) C(18)-C(21) 1.516(8) C(22)-C(27) 1.379(8) C(22)-C(23) 1.396(8)

C(23)-F(1) 1.351(6) C(23)-C(24) 1.370(8) C(24)-F(2) 1.339(7) C(24)-C(25) 1.374(9)

C(25)-F(3) 1.353(6) C(25)-C(26) 1.383(9)

C(26)-F(4) 1.343(7) C(26)-C(27) 1.379(8)

C(27)-F(5) 1.352(6) N(3)-C(29) 1.411(9) N(3)-C(31) 1.433(7) N(3)-C(28) 1.471(7)

N(4)-C(40) 1.447(7) N(4)-C(28) 1.457(7) N(4)-C(30) 1.469(7) C(28)-C(49) 1.530(7)

C(29)-C(30) 1.462(9) C(31)-C(32) 1.407(8) C(31)-C(36) 1.414(8) C(32)-C(33) 1.396(8)

C(32)-C(37) 1.498(8) C(33)-C(34) 1.379(9) C(34)-C(35) 1.378(8) C(34)-C(38) 1.512(8)

C(35)-C(36) 1.400(8) C(36)-C(39) 1.498(8) C(40)-C(45) 1.401(8) C(40)-C(41) 1.412(8)

C(41)-C(42) 1.397(8) C(41)-C(46) 1.503(8) C(42)-C(43) 1.388(9) C(43)-C(44) 1.388(9)

C(43)-C(47) 1.510(8) C(44)-C(45) 1.405(8) C(45)-C(48) 1.501(9) C(49)-C(50) 1.387(8)

C(49)-C(54) 1.389(8) C(50)-F(6) 1.348(7) C(50)-C(51) 1.371(8) C(51)-F(7) 1.336(6)

C(51)-C(52) 1.388(9) C(52)-F(8) 1.339(6)

C(52)-C(53) 1.384(9) C(53)-F(9) 1.341(7)

C(53)-C(54) 1.376(8) C(54)-F(10) 1.346(6) N(5)-C(58) 1.428(7) N(5)-C(55) 1.460(7)

N(5)-C(56) 1.474(7) N(6)-C(67) 1.438(7) N(6)-C(57) 1.458(7) N(6)-C(55) 1.465(7)

C(55)-C(76) 1.528(7) C(56)-C(57) 1.511(8) C(58)-C(59) 1.402(8) C(58)-C(63) 1.408(8)

C(59)-C(60) 1.407(9) C(59)-C(64) 1.502(9) C(60)-C(61) 1.393(10) C(61)-C(62) 1.390(9)

C(61)-C(65) 1.504(9) C(62)-C(63) 1.393(8) C(63)-C(66) 1.503(9) C(67)-C(72) 1.397(8)

C(67)-C(68) 1.411(8) C(68)-C(69) 1.392(8) C(68)-C(73) 1.505(8) C(69)-C(70) 1.386(8)

C(70)-C(71) 1.392(8) C(70)-C(74) 1.506(8) C(71)-C(72) 1.392(8) C(72)-C(75) 1.517(8)

C(76)-C(77) 1.379(7) C(76)-C(81) 1.407(8) C(77)-F(11) 1.367(6) C(77)-C(78) 1.371(8)

C(78)-F(12) 1.345(6) C(78)-C(79) 1.372(8)

C(79)-F(13) 1.344(6) C(79)-C(80) 1.379(8)

C(80)-F(14) 1.343(6) C(80)-C(81) 1.380(8) C(81)-F(15) 1.344(6) N(7)-C(85) 1.435(7)

N(7)-C(83) 1.458(7) N(7)-C(82) 1.470(7) N(8)-C(94) 1.433(7) N(8)-C(82) 1.458(7)

N(8)-C(84) 1.469(8) C(82)-C(103) 1.520(8) C(83)-C(84) 1.498(9) C(85)-C(86) 1.412(8)

C(85)-C(90) 1.416(8) C(86)-C(87) 1.391(8) C(86)-C(91) 1.511(8) C(87)-C(88) 1.386(8)

C(88)-C(89) 1.393(8) C(88)-C(92) 1.509(8) C(89)-C(90) 1.381(8) C(90)-C(93) 1.503(8)

C(94)-C(95) 1.397(9) C(94)-C(99) 1.406(8) C(95)-C(96) 1.407(8) C(95)-C(100) 1.497(9)

C(96)-C(97) 1.387(9) C(97)-C(98) 1.388(10) C(97)-C(101) 1.519(9) C(98)-C(99) 1.408(9)

C(99)-C(102) 1.497(10) C(103)-C(108) 1.390(8) C(103)-C(104) 1.393(8) C(104)-F(16) 1.344(6)

C(104)-C(105) 1.389(8) C(105)-F(17) 1.343(7)

C(105)-C(106) 1.374(9) C(106)-F(18) 1.352(6)

C(106)-C(107) 1.361(9) C(107)-F(19) 1.351(7) C(107)-C(108) 1.379(8) C(108)-F(20) 1.360(7)

C(4)-N(1)-C(1) 119.0(4) C(4)-N(1)-C(2) 117.0(4) C(1)-N(1)-C(2) 110.1(4)

C(13)-N(2)-C(3) 120.6(5) C(13)-N(2)-C(1) 121.9(4) C(3)-N(2)-C(1) 109.0(4) N(2)-C(1)-N(1) 102.3(4)

N(2)-C(1)-C(22) 112.4(4) N(1)-C(1)-C(22) 112.2(4) N(1)-C(2)-C(3) 104.8(5) N(2)-C(3)-C(2) 105.6(5)

C(5)-C(4)-C(9) 120.3(5) C(5)-C(4)-N(1) 117.5(5) C(9)-C(4)-N(1) 121.9(5) C(6)-C(5)-C(4) 119.0(5)

C(6)-C(5)-C(10) 119.9(5) C(4)-C(5)-C(10) 121.1(5) C(7)-C(6)-C(5) 121.9(5) C(6)-C(7)-C(8) 118.3(5)

C(6)-C(7)-C(11) 122.3(6) C(8)-C(7)-C(11) 119.3(6) C(7)-C(8)-C(9) 122.2(5) C(8)-C(9)-C(4) 118.4(5)

C(8)-C(9)-C(12) 118.3(5) C(4)-C(9)-C(12) 123.3(5) C(18)-C(13)-C(14) 119.3(5) C(18)-C(13)-N(2) 118.2(5)

C(14)-C(13)-N(2) 122.5(5) C(15)-C(14)-C(13) 119.0(5)

C(15)-C(14)-C(19) 117.9(5) C(13)-C(14)-C(19) 123.1(5)

C(14)-C(15)-C(16) 122.6(6) C(17)-C(16)-C(15) 117.1(5) C(17)-C(16)-C(20) 121.9(5) C(15)-C(16)-C(20) 121.0(6)

C(16)-C(17)-C(18) 122.1(5) C(17)-C(18)-C(13) 119.9(5) C(17)-C(18)-C(21) 118.6(5) C(13)-C(18)-C(21) 121.5(5)

C(27)-C(22)-C(23) 115.7(5) C(27)-C(22)-C(1) 123.6(5) C(23)-C(22)-C(1) 120.6(5) F(1)-C(23)-C(24) 116.9(5)

F(1)-C(23)-C(22) 119.8(5) C(24)-C(23)-C(22) 123.3(5) F(2)-C(24)-C(23) 121.0(6) F(2)-C(24)-C(25) 120.1(5)

C(23)-C(24)-C(25) 118.9(5) F(3)-C(25)-C(24) 120.4(5) F(3)-C(25)-C(26) 119.7(6) C(24)-C(25)-C(26) 119.9(5)

F(4)-C(26)-C(27) 120.9(5) F(4)-C(26)-C(25) 119.5(5) C(27)-C(26)-C(25) 119.7(6) F(5)-C(27)-C(22) 120.9(5)

F(5)-C(27)-C(26) 116.8(5) C(22)-C(27)-C(26) 122.4(5) C(29)-N(3)-C(31) 121.5(5) C(29)-N(3)-C(28) 109.7(5)

C(31)-N(3)-C(28) 122.6(4) C(40)-N(4)-C(28) 119.3(4) C(40)-N(4)-C(30) 116.8(4) C(28)-N(4)-C(30) 110.4(4)

N(4)-C(28)-N(3) 102.3(4) N(4)-C(28)-C(49) 111.9(4)

N(3)-C(28)-C(49) 112.8(4) N(3)-C(29)-C(30) 108.6(6)

C(29)-C(30)-N(4) 104.4(5) C(32)-C(31)-C(36) 119.4(5) C(32)-C(31)-N(3) 117.8(5) C(36)-C(31)-N(3) 122.5(5)

C(33)-C(32)-C(31) 119.1(5) C(33)-C(32)-C(37) 118.9(5) C(31)-C(32)-C(37) 122.0(5) C(34)-C(33)-C(32) 122.1(5)

C(35)-C(34)-C(33) 118.3(6) C(35)-C(34)-C(38) 120.3(6) C(33)-C(34)-C(38) 121.4(6) C(34)-C(35)-C(36) 122.4(6)

C(35)-C(36)-C(31) 118.6(5) C(35)-C(36)-C(39) 118.5(5) C(31)-C(36)-C(39) 122.8(5) C(45)-C(40)-C(41) 120.3(5)

C(45)-C(40)-N(4) 117.3(5) C(41)-C(40)-N(4) 122.1(5) C(42)-C(41)-C(40) 118.5(5) C(42)-C(41)-C(46) 118.1(5)

C(40)-C(41)-C(46) 123.4(5) C(43)-C(42)-C(41) 122.5(6) C(44)-C(43)-C(42) 117.7(5) C(44)-C(43)-C(47) 122.1(6)

C(42)-C(43)-C(47) 120.1(6) C(43)-C(44)-C(45) 122.4(6) C(40)-C(45)-C(44) 118.5(6) C(40)-C(45)-C(48) 121.9(5)

C(44)-C(45)-C(48) 119.6(5) C(50)-C(49)-C(54) 115.6(5) C(50)-C(49)-C(28) 121.0(5) C(54)-C(49)-C(28) 123.4(5)

F(6)-C(50)-C(51) 117.0(5) F(6)-C(50)-C(49) 119.5(5)

C(51)-C(50)-C(49) 123.5(6) F(7)-C(51)-C(50) 121.3(6)

F(7)-C(51)-C(52) 119.6(5) C(50)-C(51)-C(52) 119.1(5) F(8)-C(52)-C(53) 120.2(6) F(8)-C(52)-C(51) 120.5(6)

C(53)-C(52)-C(51) 119.3(5) F(9)-C(53)-C(54) 120.9(5) F(9)-C(53)-C(52) 119.4(5) C(54)-C(53)-C(52) 119.7(5)

F(10)-C(54)-C(53) 116.6(5) F(10)-C(54)-C(49) 120.7(5) C(53)-C(54)-C(49) 122.7(5) C(58)-N(5)-C(55) 121.0(4)

C(58)-N(5)-C(56) 118.1(4) C(55)-N(5)-C(56) 110.6(4) C(67)-N(6)-C(57) 118.7(4) C(67)-N(6)-C(55) 122.6(4)

C(57)-N(6)-C(55) 108.6(4) N(5)-C(55)-N(6) 103.0(4) N(5)-C(55)-C(76) 111.5(4) N(6)-C(55)-C(76) 111.1(4)

N(5)-C(56)-C(57) 104.3(4) N(6)-C(57)-C(56) 102.9(5) C(59)-C(58)-C(63) 119.0(5) C(59)-C(58)-N(5) 117.4(5)

C(63)-C(58)-N(5) 123.5(5) C(58)-C(59)-C(60) 119.4(6) C(58)-C(59)-C(64) 121.1(5) C(60)-C(59)-C(64) 119.5(6)

C(61)-C(60)-C(59) 122.1(6) C(62)-C(61)-C(60) 117.2(6) C(62)-C(61)-C(65) 121.0(7) C(60)-C(61)-C(65) 121.7(7)

C(61)-C(62)-C(63) 122.5(6) C(62)-C(63)-C(58) 119.7(6)

C(62)-C(63)-C(66) 118.4(6) C(58)-C(63)-C(66) 121.8(5)

C(72)-C(67)-C(68) 119.8(5) C(72)-C(67)-N(6) 116.9(5) C(68)-C(67)-N(6) 123.2(5) C(69)-C(68)-C(67) 118.0(5)

C(69)-C(68)-C(73) 118.6(5) C(67)-C(68)-C(73) 123.4(5) C(70)-C(69)-C(68) 123.5(6) C(69)-C(70)-C(71) 117.1(5)

C(69)-C(70)-C(74) 122.2(5) C(71)-C(70)-C(74) 120.6(5) C(70)-C(71)-C(72) 121.8(5) C(71)-C(72)-C(67) 119.7(5)

C(71)-C(72)-C(75) 118.3(5) C(67)-C(72)-C(75) 121.9(5) C(77)-C(76)-C(81) 115.0(5) C(77)-C(76)-C(55) 121.7(5)

C(81)-C(76)-C(55) 123.2(5) F(11)-C(77)-C(78) 116.5(5) F(11)-C(77)-C(76) 119.3(5) C(78)-C(77)-C(76) 124.2(5)

F(12)-C(78)-C(77) 121.0(5) F(12)-C(78)-C(79) 119.7(5) C(77)-C(78)-C(79) 119.3(5) F(13)-C(79)-C(78) 120.8(5)

F(13)-C(79)-C(80) 119.9(5) C(78)-C(79)-C(80) 119.3(5) F(14)-C(80)-C(79) 119.1(5) F(14)-C(80)-C(81) 120.5(5)

C(79)-C(80)-C(81) 120.4(5) F(15)-C(81)-C(80) 117.7(5) F(15)-C(81)-C(76) 120.5(5) C(80)-C(81)-C(76) 121.7(5)

C(85)-N(7)-C(83) 118.6(5) C(85)-N(7)-C(82) 123.3(4)

C(83)-N(7)-C(82) 108.0(4) C(94)-N(8)-C(82) 121.2(5)

C(94)-N(8)-C(84) 119.5(5) C(82)-N(8)-C(84) 111.1(4) N(8)-C(82)-N(7) 102.5(4) N(8)-C(82)-C(103) 111.8(5)

N(7)-C(82)-C(103) 111.0(4) N(7)-C(83)-C(84) 103.3(5) N(8)-C(84)-C(83) 103.8(5) C(86)-C(85)-C(90) 119.8(5)

C(86)-C(85)-N(7) 116.8(5) C(90)-C(85)-N(7) 123.3(5) C(87)-C(86)-C(85) 119.1(5) C(87)-C(86)-C(91) 119.5(5)

C(85)-C(86)-C(91) 121.4(5) C(88)-C(87)-C(86) 122.4(5) C(87)-C(88)-C(89) 116.9(5) C(87)-C(88)-C(92) 121.0(5)

C(89)-C(88)-C(92) 122.1(5) C(90)-C(89)-C(88) 123.9(6) C(89)-C(90)-C(85) 117.9(5) C(89)-C(90)-C(93) 118.6(5)

C(85)-C(90)-C(93) 123.4(5) C(95)-C(94)-C(99) 119.7(5) C(95)-C(94)-N(8) 123.7(5) C(99)-C(94)-N(8) 116.4(5)

C(94)-C(95)-C(96) 119.7(6) C(94)-C(95)-C(100) 122.3(5) C(96)-C(95)-C(100) 117.9(6) C(97)-C(96)-C(95) 121.7(6)

C(96)-C(97)-C(98) 117.7(6) C(96)-C(97)-C(101) 120.2(7) C(98)-C(97)-C(101) 122.1(7) C(97)-C(98)-C(99) 122.6(6)

C(94)-C(99)-C(98) 118.5(6) C(94)-C(99)-C(102) 121.8(6)

C(98)-C(99)-C(102) 119.6(6) C(108)-C(103)-C(104) 114.8(5)

C(108)-C(103)-C(82) 121.5(5) C(104)-C(103)-C(82) 123.6(5) F(16)-C(104)-C(105) 116.9(5) F(16)-C(104)-C(103) 120.6(5)

C(105)-C(104)-C(103) 122.5(5) F(17)-C(105)-C(106) 119.3(5) F(17)-C(105)-C(104) 121.0(5) C(106)-C(105)-C(104) 119.7(6)

F(18)-C(106)-C(107) 121.0(6) F(18)-C(106)-C(105) 119.0(6) C(107)-C(106)-C(105) 119.9(5) F(19)-C(107)-C(106) 120.5(5)

F(19)-C(107)-C(108) 120.1(6) C(106)-C(107)-C(108) 119.4(5) F(20)-C(108)-C(107) 117.0(5) F(20)-C(108)-C(103) 119.3(5)

C(107)-C(108)-C(103) 123.6(6) _____________________________________________________________

Table 4. Anisotropic displacement parameters (Å2x 103) for gnibm1. The anisotropic displacement factor exponent takes the form: -2π 2[ h2 a*2U11 + ... + 2 h k a* b* U12 ]

______________________________________________________________________________ U11 U22 U33 U23 U13 U12 ______________________________________________________________________________ N(1) 33(3) 21(2) 29(2) 8(2) 16(2) 13(2)

N(2) 33(3) 18(2) 31(3) 6(2) 16(2) 10(2) C(1) 21(3) 20(3) 22(3) 3(2) 11(2) 4(2) C(2) 38(3) 24(3) 35(3) 5(2) 21(3) 13(3) C(3) 106(7) 22(3) 91(6) 12(4) 79(6) 24(4)

C(4) 26(3) 23(3) 23(3) 3(2) 13(2) 8(2) C(5) 25(3) 23(3) 26(3) 2(2) 11(2) 9(2) C(6) 39(3) 18(3) 36(3) 6(2) 19(3) 7(3) C(7) 43(4) 25(3) 37(3) 9(3) 24(3) 17(3)

C(8) 34(3) 25(3) 25(3) 8(2) 13(3) 13(3) C(9) 28(3) 23(3) 24(3) 4(2) 14(2) 10(2) C(10) 31(3) 28(3) 42(4) 9(3) 13(3) 1(3) C(11) 56(4) 30(3) 37(3) 17(3) 25(3) 21(3)

C(12) 30(3) 30(3) 33(3) 5(3) 8(3) 9(3) C(13) 37(3) 15(3) 25(3) 2(2) 17(3) 8(2) C(14) 36(3) 18(3) 21(3) 0(2) 9(2) 8(2) C(15) 32(3) 18(3) 29(3) 0(2) 8(3) 1(2)

C(16) 40(3) 20(3) 21(3) 1(2) 9(3) 6(3) C(17) 33(3) 16(3) 25(3) -1(2) 4(2) 7(2) C(18) 30(3) 18(3) 24(3) -2(2) 8(2) 6(2) C(20) 40(4) 34(3) 32(3) 8(3) 14(3) 9(3)

C(21) 33(3) 32(3) 38(3) 9(3) 6(3) 17(3) C(22) 27(3) 18(3) 23(3) 5(2) 12(2) 6(2) C(19) 30(3) 21(3) 37(3) 6(2) 11(3) 8(2) C(23) 32(3) 14(3) 31(3) 6(2) 14(3) 8(2)

C(24) 44(4) 18(3) 33(3) 2(2) 25(3) 6(3) C(25) 44(4) 19(3) 25(3) -5(2) 17(3) -3(3) C(26) 30(3) 28(3) 26(3) -1(2) 8(3) 3(3) C(27) 35(3) 27(3) 28(3) 10(2) 21(3) 12(3)

F(1) 33(2) 28(2) 37(2) 3(2) 13(2) 15(2) F(2) 53(2) 31(2) 43(2) 3(2) 28(2) 19(2)

F(3) 57(2) 36(2) 31(2) -8(2) 17(2) 0(2) F(4) 32(2) 54(2) 32(2) -3(2) 8(2) 4(2)

F(5) 28(2) 36(2) 34(2) 2(2) 12(2) 11(2) N(3) 36(3) 18(2) 24(2) 4(2) 10(2) 9(2) N(4) 27(3) 24(2) 27(2) 1(2) 7(2) 10(2) C(28) 27(3) 21(3) 23(3) 3(2) 9(2) 5(2)

C(29) 152(10) 35(4) 36(4) -7(3) -33(5) 40(5) C(30) 42(4) 26(3) 26(3) 7(2) 8(3) 12(3) C(31) 33(3) 19(3) 23(3) 2(2) 9(2) 9(2) C(32) 38(3) 17(3) 32(3) 9(2) 18(3) 10(2)

C(33) 44(4) 22(3) 38(3) 7(3) 24(3) 12(3) C(34) 50(4) 20(3) 25(3) 8(2) 16(3) 11(3) C(35) 34(3) 28(3) 28(3) 6(2) 9(3) 11(3) C(36) 35(3) 18(3) 22(3) 3(2) 12(2) 7(2)

C(37) 38(4) 26(3) 58(4) 4(3) 24(3) 13(3) C(38) 55(4) 30(3) 27(3) -2(3) 11(3) 11(3) C(39) 31(3) 31(3) 34(3) -4(3) 9(3) 10(3) C(40) 35(3) 23(3) 19(3) 6(2) 9(2) 13(2)

C(41) 35(3) 24(3) 24(3) 9(2) 14(3) 12(3) C(42) 45(4) 28(3) 26(3) 5(2) 16(3) 18(3) C(43) 47(4) 28(3) 21(3) 5(2) 9(3) 15(3) C(44) 43(4) 22(3) 26(3) 2(2) 7(3) 10(3)

C(45) 37(3) 27(3) 22(3) 2(2) 4(3) 13(3) C(46) 39(4) 27(3) 36(3) 0(3) 20(3) 8(3) C(47) 71(5) 35(4) 32(3) 1(3) 15(3) 28(4) C(48) 30(3) 33(3) 39(4) -4(3) 8(3) 2(3)

C(49) 35(3) 14(3) 21(3) -1(2) 6(2) 8(2) C(50) 33(3) 19(3) 24(3) -1(2) 6(2) 7(2) C(51) 48(4) 26(3) 21(3) 6(2) 11(3) 20(3) C(52) 54(4) 22(3) 26(3) 5(2) 19(3) 7(3)

C(53) 30(3) 30(3) 27(3) 0(2) 11(3) 4(3) C(54) 27(3) 23(3) 22(3) 1(2) 5(2) 8(2) F(6) 30(2) 32(2) 34(2) 3(2) 8(2) 13(2) F(7) 63(3) 36(2) 28(2) 12(2) 10(2) 25(2)

F(8) 71(3) 32(2) 35(2) 12(2) 27(2) 8(2) F(9) 36(2) 47(2) 47(2) 5(2) 20(2) 4(2)

F(10) 32(2) 35(2) 36(2) 10(2) 11(2) 14(2) N(5) 34(3) 18(2) 28(2) 1(2) 14(2) 7(2)

N(6) 34(3) 18(2) 32(3) 7(2) 18(2) 12(2) C(55) 26(3) 22(3) 22(3) 2(2) 10(2) 7(2) C(56) 47(4) 23(3) 43(4) 6(3) 31(3) 4(3) C(57) 52(4) 20(3) 37(3) 7(3) 25(3) 8(3)

C(58) 39(3) 22(3) 28(3) 7(2) 21(3) 12(3) C(59) 40(4) 21(3) 38(3) 6(3) 16(3) 12(3) C(60) 53(4) 32(3) 54(4) 13(3) 35(4) 20(3) C(61) 75(5) 23(3) 39(4) 6(3) 34(4) 16(3)

C(62) 50(4) 21(3) 29(3) 4(2) 20(3) 6(3) C(63) 42(3) 21(3) 24(3) 3(2) 17(3) 9(3) C(64) 30(4) 44(4) 61(5) 3(3) 11(3) 19(3) C(65) 91(6) 34(4) 54(4) 8(3) 41(4) 27(4)

C(66) 41(4) 43(4) 31(3) 5(3) 11(3) 14(3) C(67) 34(3) 17(3) 22(3) 7(2) 13(2) 10(2) C(68) 36(3) 20(3) 23(3) 5(2) 12(3) 8(2) C(69) 30(3) 28(3) 27(3) 8(2) 10(3) 11(3)

C(70) 35(3) 27(3) 24(3) 10(2) 12(3) 16(3) C(71) 36(3) 20(3) 22(3) 5(2) 8(3) 10(2) C(72) 33(3) 25(3) 22(3) 8(2) 8(2) 11(3) C(73) 33(3) 23(3) 33(3) 2(2) 10(3) 10(3)

C(74) 41(4) 39(4) 33(3) 4(3) 17(3) 17(3) C(75) 29(3) 25(3) 33(3) 4(3) 11(3) 6(3) C(76) 26(3) 17(3) 24(3) 1(2) 10(2) 8(2) C(77) 26(3) 21(3) 25(3) -1(2) 12(2) 8(2)

C(78) 36(3) 20(3) 36(3) 1(2) 22(3) 8(2) C(79) 37(3) 28(3) 25(3) 7(2) 13(3) 16(3) C(80) 24(3) 27(3) 30(3) 1(2) 7(2) 9(2) C(81) 34(3) 21(3) 29(3) 5(2) 18(3) 8(2)

F(11) 26(2) 24(2) 33(2) 3(1) 8(1) 3(1) F(12) 40(2) 24(2) 40(2) 9(2) 23(2) 4(2) F(13) 44(2) 36(2) 28(2) 11(2) 11(2) 18(2) F(14) 31(2) 43(2) 36(2) 5(2) 5(2) 9(2)

F(15) 27(2) 28(2) 37(2) 5(2) 12(2) 1(1) N(7) 37(3) 20(2) 19(2) 1(2) 2(2) 8(2)

N(8) 43(3) 21(2) 22(2) 2(2) 6(2) 10(2) C(82) 31(3) 23(3) 22(3) 5(2) 8(2) 10(2)

C(83) 55(4) 27(3) 24(3) 0(3) 7(3) 15(3) C(84) 54(4) 36(4) 25(3) 3(3) 5(3) 13(3) C(85) 39(3) 21(3) 20(3) -1(2) 10(2) 13(3) C(86) 38(3) 17(3) 28(3) -1(2) 11(3) 6(2)

C(87) 40(4) 20(3) 30(3) 0(2) 16(3) 7(3) C(88) 39(4) 26(3) 25(3) 0(2) 12(3) 16(3) C(89) 33(3) 22(3) 22(3) -1(2) 8(2) 6(2) C(90) 41(3) 20(3) 25(3) -1(2) 12(3) 11(3)

C(91) 40(4) 28(3) 36(3) 4(3) 15(3) 8(3) C(92) 42(4) 32(3) 29(3) 8(3) 10(3) 15(3) C(93) 34(3) 30(3) 35(3) 7(3) 13(3) 12(3) C(94) 40(3) 25(3) 17(3) 4(2) 4(2) 14(3)

C(95) 47(4) 29(3) 20(3) 5(2) 11(3) 20(3) C(96) 56(4) 23(3) 31(3) 4(3) 17(3) 17(3) C(97) 68(5) 24(3) 28(3) -1(3) 13(3) 21(3) C(98) 58(5) 39(4) 32(3) 6(3) 7(3) 28(3)

C(99) 45(4) 34(3) 31(3) -1(3) 7(3) 18(3) C(100) 51(4) 45(4) 39(4) 9(3) 24(3) 23(3) C(101) 96(6) 36(4) 35(4) 18(3) 21(4) 34(4) C(102) 51(5) 58(5) 61(5) 17(4) 13(4) 28(4)

C(103) 36(3) 18(3) 22(3) 5(2) 6(2) 9(2) C(104) 35(3) 21(3) 24(3) 2(2) 5(3) 8(3) C(105) 30(3) 32(3) 33(3) 8(3) 10(3) 12(3) C(106) 50(4) 30(3) 28(3) 8(3) 20(3) 22(3)

C(107) 48(4) 15(3) 27(3) 0(2) 7(3) 9(3) C(108) 36(3) 19(3) 26(3) 8(2) 7(3) 12(3) F(16) 35(2) 32(2) 36(2) -3(2) 7(2) 3(2) F(17) 40(2) 49(2) 50(2) 6(2) 21(2) 15(2)

F(18) 57(2) 35(2) 36(2) 4(2) 18(2) 23(2) F(19) 55(2) 26(2) 34(2) -6(2) 11(2) 5(2) F(20) 31(2) 30(2) 33(2) 1(2) 8(2) 3(2) ______________________________________________________________________________

Table 5. Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2 x 10 3) for gnib m1.

________________________________________________________________________________ x y z U(eq) ______________________________________________________________________________

__ H(1A) 1718 2090 688 25 H(2A) 3694 1687 255 35

H(2B) 2762 1656 -436 35 H(3A) 1895 644 -25 73 H(3B) 2859 515 502 73 H(6A) 4075 4948 -45 35

H(8A) 1469 3651 -1380 32 H(10A) 4408 3353 1170 53 H(10B) 4629 4341 1281 53 H(10C) 5005 3938 733 53

H(11A) 3322 5550 -1111 56 H(11B) 2215 5291 -1329 56 H(11C) 2654 4867 -1811 56 H(12A) 694 2352 -1207 47

H(12B) 933 2156 -350 47 H(12C) 1338 1772 -886 47 H(15A) -247 -157 1451 35 H(17A) 2134 -593 2703 32

H(20A) 756 -1291 2938 54 H(20B) -158 -1517 2197 54 H(20C) 41 -766 2807 54 H(21A) 3545 59 2597 52

H(21B) 3681 994 2385 52 H(21C) 3501 261 1764 52 H(19A) -354 676 524 44 H(19B) 357 710 92 44

H(19C) 533 1484 669 44 H(28A) 1605 6995 2528 29

H(29A) 3054 5606 3313 107 H(29B) 2037 5496 3345 107

H(30A) 3639 6705 4112 39 H(30B) 2630 6564 4178 39 H(33A) 1987 4303 716 38 H(35A) -387 4584 784 36

H(37A) 3518 5813 2267 57 H(37B) 3481 5585 1436 57 H(37C) 3416 4880 1995 57 H(38A) 574 3438 -147 58

H(38B) -233 3869 -408 58 H(38C) -251 3199 187 58 H(39A) -447 5464 1659 49 H(39B) 405 6311 1934 49

H(39C) 350 5579 2467 49 H(42A) 1403 8618 4446 36 H(44A) 3999 9901 4562 39 H(46A) 1197 6793 3387 49

H(46B) 561 7379 3349 49 H(46C) 973 7001 4115 49 H(47A) 2066 9920 5134 67 H(47B) 2781 10583 4839 67

H(47C) 3165 10139 5569 67 H(48A) 4334 8298 3549 56 H(48B) 4927 8884 4325 56 H(48C) 4556 9287 3565 56

H(55A) 8171 6121 4235 27 H(56A) 5957 4656 4353 43 H(56B) 6740 5007 5172 43 H(57A) 7805 4561 4891 41

H(57B) 6889 3896 4301 41 H(60A) 5883 7731 5054 48 H(62A) 8457 7746 6357 39 H(64A) 5478 6014 3740 67

H(64B) 5314 6906 3688 67 H(64C) 4899 6265 4197 67

H(65A) 7848 8704 6737 81 H(65B) 6743 8367 6535 81

H(65C) 7178 9034 6054 81 H(66A) 8513 6017 5327 58 H(66B) 8724 6284 6194 58 H(66C) 9221 6913 5720 58

H(69A) 10144 4877 3581 33 H(71A) 7781 3199 2231 32 H(73A) 9115 5817 4595 44 H(73B) 9906 6129 4231 44

H(73C) 9971 5446 4814 44 H(74A) 10266 3955 2709 53 H(74B) 9389 3709 1940 53 H(74C) 9503 3056 2547 53

H(75A) 6345 3110 2256 45 H(75B) 6218 3981 2450 45 H(75C) 6328 3340 3069 45 H(82A) 8250 1088 2476 30

H(83A) 6886 -1131 1710 44 H(83B) 7791 -483 1607 44 H(84A) 6702 -49 748 49 H(84B) 5963 -353 1173 49

H(87A) 7823 -1847 4256 35 H(89A) 10191 -230 4198 32 H(91A) 6371 -1884 3448 52 H(91B) 6335 -1642 2626 52

H(91C) 6286 -992 3215 52 H(92A) 9225 -1956 5101 52 H(92B) 10040 -1087 5383 52 H(92C) 10054 -1732 4771 52

H(93A) 10269 689 3348 48 H(93B) 9427 1077 3084 48 H(93C) 9468 375 2540 48 H(96A) 8436 2772 526 42

H(98A) 5831 2641 371 51 H(10D) 8578 1054 1593 61

H(10E) 9246 1967 1593 61 H(10F) 8770 1332 841 61

H(10G) 7771 3689 -206 80 H(10H) 7077 3988 95 80 H(10I) 6668 3317 -630 80 H(10J) 5507 934 1473 84

H(10K) 4907 1162 685 84 H(10L) 5300 1808 1426 84 ________________________________________________________________________________

Table 6. Torsion angles [°] for gnibm1. ________________________________________________________________

C(13)-N(2)-C(1)-N(1) -176.5(5) C(3)-N(2)-C(1)-N(1) -28.4(6) C(13)-N(2)-C(1)-C(22) 62.9(6) C(3)-N(2)-C(1)-C(22) -148.9(6)

C(4)-N(1)-C(1)-N(2) 157.0(5) C(2)-N(1)-C(1)-N(2) 17.9(6) C(4)-N(1)-C(1)-C(22) -82.3(6) C(2)-N(1)-C(1)-C(22) 138.6(5)

C(4)-N(1)-C(2)-C(3) -141.7(6) C(1)-N(1)-C(2)-C(3) -1.8(7) C(13)-N(2)-C(3)-C(2) 176.8(5) C(1)-N(2)-C(3)-C(2) 28.1(8)

N(1)-C(2)-C(3)-N(2) -15.6(8) C(1)-N(1)-C(4)-C(5) 117.6(5) C(2)-N(1)-C(4)-C(5) -106.1(6) C(1)-N(1)-C(4)-C(9) -68.5(7)

C(2)-N(1)-C(4)-C(9) 67.8(7) C(9)-C(4)-C(5)-C(6) -0.3(8) N(1)-C(4)-C(5)-C(6) 173.7(5) C(9)-C(4)-C(5)-C(10) -178.4(5)

N(1)-C(4)-C(5)-C(10) -4.4(8) C(4)-C(5)-C(6)-C(7) -0.6(8) C(10)-C(5)-C(6)-C(7) 177.5(5) C(5)-C(6)-C(7)-C(8) 1.2(8)

C(5)-C(6)-C(7)-C(11) -175.5(5) C(6)-C(7)-C(8)-C(9) -0.8(8) C(11)-C(7)-C(8)-C(9) 176.0(5) C(7)-C(8)-C(9)-C(4) -0.1(8)

C(7)-C(8)-C(9)-C(12) -179.5(5) C(5)-C(4)-C(9)-C(8) 0.7(8) N(1)-C(4)-C(9)-C(8) -173.0(5) C(5)-C(4)-C(9)-C(12) 180.0(5)

N(1)-C(4)-C(9)-C(12) 6.3(8) C(3)-N(2)-C(13)-C(18) 88.2(7)

C(1)-N(2)-C(13)-C(18) -127.2(5) C(3)-N(2)-C(13)-C(14) -89.4(7)

C(1)-N(2)-C(13)-C(14) 55.2(7) C(18)-C(13)-C(14)-C(15) 1.6(8) N(2)-C(13)-C(14)-C(15) 179.2(5) C(18)-C(13)-C(14)-C(19) -176.2(5)

N(2)-C(13)-C(14)-C(19) 1.3(8) C(13)-C(14)-C(15)-C(16) -1.0(8) C(19)-C(14)-C(15)-C(16) 177.0(5) C(14)-C(15)-C(16)-C(17) -0.7(8)

C(14)-C(15)-C(16)-C(20) 179.8(5) C(15)-C(16)-C(17)-C(18) 1.7(8) C(20)-C(16)-C(17)-C(18) -178.7(5) C(16)-C(17)-C(18)-C(13) -1.1(8)

C(16)-C(17)-C(18)-C(21) 178.5(5) C(14)-C(13)-C(18)-C(17) -0.6(8) N(2)-C(13)-C(18)-C(17) -178.3(5) C(14)-C(13)-C(18)-C(21) 179.8(5)

N(2)-C(13)-C(18)-C(21) 2.1(8) N(2)-C(1)-C(22)-C(27) 61.7(6) N(1)-C(1)-C(22)-C(27) -53.0(7) N(2)-C(1)-C(22)-C(23) -119.2(5)

N(1)-C(1)-C(22)-C(23) 126.1(5) C(27)-C(22)-C(23)-F(1) -177.1(5) C(1)-C(22)-C(23)-F(1) 3.7(7) C(27)-C(22)-C(23)-C(24) 3.5(8)

C(1)-C(22)-C(23)-C(24) -175.7(5) F(1)-C(23)-C(24)-F(2) -1.2(7) C(22)-C(23)-C(24)-F(2) 178.2(5) F(1)-C(23)-C(24)-C(25) 178.3(5)

C(22)-C(23)-C(24)-C(25) -2.3(8) F(2)-C(24)-C(25)-F(3) -1.3(8) C(23)-C(24)-C(25)-F(3) 179.2(5) F(2)-C(24)-C(25)-C(26) 178.7(5)

C(23)-C(24)-C(25)-C(26) -0.8(8) F(3)-C(25)-C(26)-F(4) 2.3(8)

C(24)-C(25)-C(26)-F(4) -177.7(5) F(3)-C(25)-C(26)-C(27) -177.6(5)

C(24)-C(25)-C(26)-C(27) 2.4(9) C(23)-C(22)-C(27)-F(5) 178.2(5) C(1)-C(22)-C(27)-F(5) -2.6(8) C(23)-C(22)-C(27)-C(26) -1.8(8)

C(1)-C(22)-C(27)-C(26) 177.4(5) F(4)-C(26)-C(27)-F(5) -1.0(8) C(25)-C(26)-C(27)-F(5) 178.9(5) F(4)-C(26)-C(27)-C(22) 179.0(5)

C(25)-C(26)-C(27)-C(22) -1.1(9) C(40)-N(4)-C(28)-N(3) -159.1(4) C(30)-N(4)-C(28)-N(3) -19.7(6) C(40)-N(4)-C(28)-C(49) 79.9(6)

C(30)-N(4)-C(28)-C(49) -140.7(5) C(29)-N(3)-C(28)-N(4) 21.6(8) C(31)-N(3)-C(28)-N(4) 174.1(5) C(29)-N(3)-C(28)-C(49) 141.9(7)

C(31)-N(3)-C(28)-C(49) -65.6(6) C(31)-N(3)-C(29)-C(30) -168.7(6) C(28)-N(3)-C(29)-C(30) -15.8(10) N(3)-C(29)-C(30)-N(4) 3.0(10)

C(40)-N(4)-C(30)-C(29) 151.5(7) C(28)-N(4)-C(30)-C(29) 11.0(8) C(29)-N(3)-C(31)-C(32) -83.1(9) C(28)-N(3)-C(31)-C(32) 127.5(5)

C(29)-N(3)-C(31)-C(36) 92.1(9) C(28)-N(3)-C(31)-C(36) -57.2(7) C(36)-C(31)-C(32)-C(33) 0.8(8) N(3)-C(31)-C(32)-C(33) 176.2(5)

C(36)-C(31)-C(32)-C(37) -178.9(5) N(3)-C(31)-C(32)-C(37) -3.5(8) C(31)-C(32)-C(33)-C(34) -0.3(8) C(37)-C(32)-C(33)-C(34) 179.3(5)

C(32)-C(33)-C(34)-C(35) 0.3(8) C(32)-C(33)-C(34)-C(38) -176.9(5)

C(33)-C(34)-C(35)-C(36) -0.8(8) C(38)-C(34)-C(35)-C(36) 176.5(5)

C(34)-C(35)-C(36)-C(31) 1.2(8) C(34)-C(35)-C(36)-C(39) -177.0(5) C(32)-C(31)-C(36)-C(35) -1.2(8) N(3)-C(31)-C(36)-C(35) -176.4(5)

C(32)-C(31)-C(36)-C(39) 177.0(5) N(3)-C(31)-C(36)-C(39) 1.8(8) C(28)-N(4)-C(40)-C(45) -118.7(6) C(30)-N(4)-C(40)-C(45) 104.4(6)

C(28)-N(4)-C(40)-C(41) 67.0(7) C(30)-N(4)-C(40)-C(41) -69.9(7) C(45)-C(40)-C(41)-C(42) -0.4(8) N(4)-C(40)-C(41)-C(42) 173.7(5)

C(45)-C(40)-C(41)-C(46) -179.8(5) N(4)-C(40)-C(41)-C(46) -5.7(8) C(40)-C(41)-C(42)-C(43) 0.3(8) C(46)-C(41)-C(42)-C(43) 179.7(5)

C(41)-C(42)-C(43)-C(44) 0.5(8) C(41)-C(42)-C(43)-C(47) -176.2(5) C(42)-C(43)-C(44)-C(45) -1.2(9) C(47)-C(43)-C(44)-C(45) 175.5(5)

C(41)-C(40)-C(45)-C(44) -0.2(8) N(4)-C(40)-C(45)-C(44) -174.6(5) C(41)-C(40)-C(45)-C(48) 177.8(5) N(4)-C(40)-C(45)-C(48) 3.4(8)

C(43)-C(44)-C(45)-C(40) 1.0(8) C(43)-C(44)-C(45)-C(48) -177.0(5) N(4)-C(28)-C(49)-C(50) -123.6(5) N(3)-C(28)-C(49)-C(50) 121.7(5)

N(4)-C(28)-C(49)-C(54) 53.5(7) N(3)-C(28)-C(49)-C(54) -61.2(7) C(54)-C(49)-C(50)-F(6) 179.7(5) C(28)-C(49)-C(50)-F(6) -3.0(8)

C(54)-C(49)-C(50)-C(51) -1.6(8) C(28)-C(49)-C(50)-C(51) 175.7(5)

F(6)-C(50)-C(51)-F(7) -0.6(8) C(49)-C(50)-C(51)-F(7) -179.3(5)

F(6)-C(50)-C(51)-C(52) 179.1(5) C(49)-C(50)-C(51)-C(52) 0.3(9) F(7)-C(51)-C(52)-F(8) 0.9(8) C(50)-C(51)-C(52)-F(8) -178.8(5)

F(7)-C(51)-C(52)-C(53) -178.9(5) C(50)-C(51)-C(52)-C(53) 1.5(9) F(8)-C(52)-C(53)-F(9) -1.1(8) C(51)-C(52)-C(53)-F(9) 178.7(5)

F(8)-C(52)-C(53)-C(54) 178.3(5) C(51)-C(52)-C(53)-C(54) -2.0(9) F(9)-C(53)-C(54)-F(10) 0.4(8) C(52)-C(53)-C(54)-F(10) -179.0(5)

F(9)-C(53)-C(54)-C(49) -180.0(5) C(52)-C(53)-C(54)-C(49) 0.7(9) C(50)-C(49)-C(54)-F(10) -179.3(5) C(28)-C(49)-C(54)-F(10) 3.5(8)

C(50)-C(49)-C(54)-C(53) 1.0(8) C(28)-C(49)-C(54)-C(53) -176.1(5) C(58)-N(5)-C(55)-N(6) 154.6(5) C(56)-N(5)-C(55)-N(6) 10.3(6)

C(58)-N(5)-C(55)-C(76) -86.1(6) C(56)-N(5)-C(55)-C(76) 129.6(5) C(67)-N(6)-C(55)-N(5) -172.4(5) C(57)-N(6)-C(55)-N(5) -27.7(6)

C(67)-N(6)-C(55)-C(76) 68.1(6) C(57)-N(6)-C(55)-C(76) -147.2(5) C(58)-N(5)-C(56)-C(57) -135.8(5) C(55)-N(5)-C(56)-C(57) 9.6(7)

C(67)-N(6)-C(57)-C(56) -180.0(5) C(55)-N(6)-C(57)-C(56) 33.7(6) N(5)-C(56)-C(57)-N(6) -25.6(6) C(55)-N(5)-C(58)-C(59) 120.7(6)

C(56)-N(5)-C(58)-C(59) -97.6(6) C(55)-N(5)-C(58)-C(63) -63.4(7)

C(56)-N(5)-C(58)-C(63) 78.4(7) C(63)-C(58)-C(59)-C(60) -0.5(8)

N(5)-C(58)-C(59)-C(60) 175.7(5) C(63)-C(58)-C(59)-C(64) -178.7(6) N(5)-C(58)-C(59)-C(64) -2.6(8) C(58)-C(59)-C(60)-C(61) 0.1(9)

C(64)-C(59)-C(60)-C(61) 178.4(6) C(59)-C(60)-C(61)-C(62) 0.7(9) C(59)-C(60)-C(61)-C(65) -177.5(6) C(60)-C(61)-C(62)-C(63) -1.2(9)

C(65)-C(61)-C(62)-C(63) 177.1(6) C(61)-C(62)-C(63)-C(58) 0.8(9) C(61)-C(62)-C(63)-C(66) -175.9(5) C(59)-C(58)-C(63)-C(62) 0.0(8)

N(5)-C(58)-C(63)-C(62) -175.9(5) C(59)-C(58)-C(63)-C(66) 176.7(5) N(5)-C(58)-C(63)-C(66) 0.8(8) C(57)-N(6)-C(67)-C(72) 86.9(6)

C(55)-N(6)-C(67)-C(72) -131.7(5) C(57)-N(6)-C(67)-C(68) -90.3(6) C(55)-N(6)-C(67)-C(68) 51.0(7) C(72)-C(67)-C(68)-C(69) 2.1(7)

N(6)-C(67)-C(68)-C(69) 179.3(5) C(72)-C(67)-C(68)-C(73) -176.5(5) N(6)-C(67)-C(68)-C(73) 0.7(8) C(67)-C(68)-C(69)-C(70) -1.7(8)

C(73)-C(68)-C(69)-C(70) 177.0(5) C(68)-C(69)-C(70)-C(71) 0.2(8) C(68)-C(69)-C(70)-C(74) 179.8(5) C(69)-C(70)-C(71)-C(72) 0.8(8)

C(74)-C(70)-C(71)-C(72) -178.8(5) C(70)-C(71)-C(72)-C(67) -0.3(8) C(70)-C(71)-C(72)-C(75) 179.9(5) C(68)-C(67)-C(72)-C(71) -1.2(8)

N(6)-C(67)-C(72)-C(71) -178.5(5) C(68)-C(67)-C(72)-C(75) 178.6(5)

N(6)-C(67)-C(72)-C(75) 1.3(7) N(5)-C(55)-C(76)-C(77) 125.6(5)

N(6)-C(55)-C(76)-C(77) -120.1(5) N(5)-C(55)-C(76)-C(81) -51.7(7) N(6)-C(55)-C(76)-C(81) 62.6(6) C(81)-C(76)-C(77)-F(11) -177.5(4)

C(55)-C(76)-C(77)-F(11) 4.9(7) C(81)-C(76)-C(77)-C(78) 2.9(8) C(55)-C(76)-C(77)-C(78) -174.7(5) F(11)-C(77)-C(78)-F(12) -1.0(7)

C(76)-C(77)-C(78)-F(12) 178.5(5) F(11)-C(77)-C(78)-C(79) 178.7(5) C(76)-C(77)-C(78)-C(79) -1.7(8) F(12)-C(78)-C(79)-F(13) -0.5(8)

C(77)-C(78)-C(79)-F(13) 179.8(5) F(12)-C(78)-C(79)-C(80) 179.0(5) C(77)-C(78)-C(79)-C(80) -0.7(8) F(13)-C(79)-C(80)-F(14) 0.2(8)

C(78)-C(79)-C(80)-F(14) -179.3(5) F(13)-C(79)-C(80)-C(81) -178.8(5) C(78)-C(79)-C(80)-C(81) 1.7(8) F(14)-C(80)-C(81)-F(15) -0.2(8)

C(79)-C(80)-C(81)-F(15) 178.8(5) F(14)-C(80)-C(81)-C(76) -179.3(5) C(79)-C(80)-C(81)-C(76) -0.4(8) C(77)-C(76)-C(81)-F(15) 179.0(5)

C(55)-C(76)-C(81)-F(15) -3.4(8) C(77)-C(76)-C(81)-C(80) -1.8(8) C(55)-C(76)-C(81)-C(80) 175.7(5) C(94)-N(8)-C(82)-N(7) -157.8(5)

C(84)-N(8)-C(82)-N(7) -9.5(6) C(94)-N(8)-C(82)-C(103) 83.2(6) C(84)-N(8)-C(82)-C(103) -128.5(5) C(85)-N(7)-C(82)-N(8) 172.2(5)

C(83)-N(7)-C(82)-N(8) 27.6(6) C(85)-N(7)-C(82)-C(103) -68.3(7)

C(83)-N(7)-C(82)-C(103) 147.2(5) C(85)-N(7)-C(83)-C(84) 178.6(5)

C(82)-N(7)-C(83)-C(84) -35.0(6) C(94)-N(8)-C(84)-C(83) 137.7(6) C(82)-N(8)-C(84)-C(83) -11.2(7) N(7)-C(83)-C(84)-N(8) 27.4(7)

C(83)-N(7)-C(85)-C(86) -85.8(6) C(82)-N(7)-C(85)-C(86) 133.1(5) C(83)-N(7)-C(85)-C(90) 91.2(7) C(82)-N(7)-C(85)-C(90) -49.8(8)

C(90)-C(85)-C(86)-C(87) 0.2(8) N(7)-C(85)-C(86)-C(87) 177.3(5) C(90)-C(85)-C(86)-C(91) -179.6(5) N(7)-C(85)-C(86)-C(91) -2.5(8)

C(85)-C(86)-C(87)-C(88) -0.3(8) C(91)-C(86)-C(87)-C(88) 179.5(5) C(86)-C(87)-C(88)-C(89) 0.8(8) C(86)-C(87)-C(88)-C(92) -177.4(5)

C(87)-C(88)-C(89)-C(90) -1.4(8) C(92)-C(88)-C(89)-C(90) 176.8(5) C(88)-C(89)-C(90)-C(85) 1.3(8) C(88)-C(89)-C(90)-C(93) -175.2(5)

C(86)-C(85)-C(90)-C(89) -0.7(8) N(7)-C(85)-C(90)-C(89) -177.6(5) C(86)-C(85)-C(90)-C(93) 175.7(5) N(7)-C(85)-C(90)-C(93) -1.3(8)

C(82)-N(8)-C(94)-C(95) 62.2(7) C(84)-N(8)-C(94)-C(95) -83.5(7) C(82)-N(8)-C(94)-C(99) -122.7(6) C(84)-N(8)-C(94)-C(99) 91.6(7)

C(99)-C(94)-C(95)-C(96) 1.2(8) N(8)-C(94)-C(95)-C(96) 176.1(5) C(99)-C(94)-C(95)-C(100) -176.4(6) N(8)-C(94)-C(95)-C(100) -1.5(9)

C(94)-C(95)-C(96)-C(97) -2.0(9) C(100)-C(95)-C(96)-C(97) 175.7(6)

C(95)-C(96)-C(97)-C(98) 1.5(9) C(95)-C(96)-C(97)-C(101) -176.7(6)

C(96)-C(97)-C(98)-C(99) -0.3(10) C(101)-C(97)-C(98)-C(99) 177.9(6) C(95)-C(94)-C(99)-C(98) 0.0(9) N(8)-C(94)-C(99)-C(98) -175.3(5)

C(95)-C(94)-C(99)-C(102) 178.0(6) N(8)-C(94)-C(99)-C(102) 2.7(9) C(97)-C(98)-C(99)-C(94) -0.4(9) C(97)-C(98)-C(99)-C(102) -178.5(6)

N(8)-C(82)-C(103)-C(108) -123.2(5) N(7)-C(82)-C(103)-C(108) 123.0(5) N(8)-C(82)-C(103)-C(104) 53.7(7) N(7)-C(82)-C(103)-C(104) -60.1(7)

C(108)-C(103)-C(104)-F(16) 180.0(5) C(82)-C(103)-C(104)-F(16) 2.9(8) C(108)-C(103)-C(104)-C(105) 1.8(8) C(82)-C(103)-C(104)-C(105) -175.3(5)

F(16)-C(104)-C(105)-F(17) 2.3(8) C(103)-C(104)-C(105)-F(17) -179.4(5) F(16)-C(104)-C(105)-C(106) -179.2(5) C(103)-C(104)-C(105)-C(106) -0.9(9)

F(17)-C(105)-C(106)-F(18) -2.7(8) C(104)-C(105)-C(106)-F(18) 178.8(5) F(17)-C(105)-C(106)-C(107) 179.2(5) C(104)-C(105)-C(106)-C(107) 0.7(9)

F(18)-C(106)-C(107)-F(19) 3.0(8) C(105)-C(106)-C(107)-F(19) -178.9(5) F(18)-C(106)-C(107)-C(108) -179.6(5) C(105)-C(106)-C(107)-C(108) -1.5(9)

F(19)-C(107)-C(108)-F(20) -1.4(8) C(106)-C(107)-C(108)-F(20) -178.9(5) F(19)-C(107)-C(108)-C(103) -179.9(5) C(106)-C(107)-C(108)-C(103) 2.6(9)

C(104)-C(103)-C(108)-F(20) 178.8(5) C(82)-C(103)-C(108)-F(20) -4.0(8)

C(104)-C(103)-C(108)-C(107) -2.7(8) C(82)-C(103)-C(108)-C(107) 174.5(5) 3