Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104010479/av1182sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104010479/av1182Isup2.hkl |
CCDC reference: 243624
Crystals of (I) were obtained by recrystallization from morpholine through careful evaporation of the solvent, to yield colorless crystals suitable for X-ray diffraction determination. The compound was also recrystallized from other organic solvents. However, smaller twinned crystals were obtained by recrystallization from acetic acid. Powder diffraction patterns indicate that the recrystallized samples only contained one phase of (I).
The analyzed crystal was mounted in a sealed glass capillary. We analyzed at least two samples but were unable to find pure untwinned crystals. Many reflections showed a typical split. A twin analysis of all reflections with the TWINABS program (Sheldrick, 1999) revealed twinning with two crystal components for our sample, i.e. 28932 reflections for component 1, 28809 for component 2 and 3295 for both. Since numerous reflections of this non-merohedral twin resulted in relatively poor data quality due to partial overlapping, an HKLF-5 file was generated for structural refinement, including 12812 corrected reflections (10496 reflections from the main component and 2316 overlapping reflections from the twin component). 2742 of them were rejected as systematic absence violations. The ratio of minimum to maximum apparent transmission is 0.8562. A subset of the data from crystals of (I) displayed a twofold axial symmetry with an extinction (0k0, k = 2n) which is the characteristic of space groups P21 (No. 4) or P21/m (No. 11). The non-centrosymmetric space group was found to be correct during the structural analysis. However, the refinement was unsatisfactory unless all 10070 measured reflections, which suffered from a non-merohedral twinning effect treated by the HKLF-5 approach mentioned above, were taken into account. The ratio of the two twin components was refined to 0.0349 (22) using the BASF instruction. The introduction of twinning reduced the R value from 14.22% to 6.29%. The disordered atoms (C32A and C32B) were split over two sites, the occupancies of which were refined with anisotropic models to final occupancies of 0.644 (2) for atom C32B and 0.354 (2) for atom C32A. H atoms were placed in geometrically calculated positions, with aryl C—H distances of 0.95 Å and aliphatic C—H distances of 0.98 Å, and were isotropically refined using a riding model, with Uiso(H) = 1.2Ueq(C). Please check added text.
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 and local programs.
C38H32N2 | F(000) = 1096 |
Mr = 516.66 | Dx = 1.211 Mg m−3 |
Monoclinic, P21 | Melting point: 449 K |
Hall symbol: P 2yb | Mo Kα radiation, λ = 0.71073 Å |
a = 14.447 (2) Å | Cell parameters from 10068 reflections |
b = 11.0153 (16) Å | θ = 1.4–29.0° |
c = 17.803 (3) Å | µ = 0.07 mm−1 |
β = 90.602 (3)° | T = 90 K |
V = 2833.0 (7) Å3 | Parallepiped, colorless |
Z = 4 | 0.30 × 0.20 × 0.20 mm |
Plateform with APEX CCD detector diffractometer | 10070 independent reflections |
Radiation source: fine-focus sealed tube | 4919 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.000 |
Detector resolution: 512 pixels mm-1 | θmax = 29.0°, θmin = 1.4° |
ϕ and ω scans | h = −19→19 |
Absorption correction: multi-scan (TWINABS in SAINT-Plus; Sheldrick, 1999) | k = 0→15 |
Tmin = 0.971, Tmax = 0.995 | l = 0→24 |
10070 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.063 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.130 | H-atom parameters constrained |
S = 0.90 | w = 1/[σ2(Fo2) + (0.0466P)2] where P = (Fo2 + 2Fc2)/3 |
10070 reflections | (Δ/σ)max < 0.001 |
735 parameters | Δρmax = 0.52 e Å−3 |
1 restraint | Δρmin = −0.29 e Å−3 |
C38H32N2 | V = 2833.0 (7) Å3 |
Mr = 516.66 | Z = 4 |
Monoclinic, P21 | Mo Kα radiation |
a = 14.447 (2) Å | µ = 0.07 mm−1 |
b = 11.0153 (16) Å | T = 90 K |
c = 17.803 (3) Å | 0.30 × 0.20 × 0.20 mm |
β = 90.602 (3)° |
Plateform with APEX CCD detector diffractometer | 10070 independent reflections |
Absorption correction: multi-scan (TWINABS in SAINT-Plus; Sheldrick, 1999) | 4919 reflections with I > 2σ(I) |
Tmin = 0.971, Tmax = 0.995 | Rint = 0.000 |
10070 measured reflections |
R[F2 > 2σ(F2)] = 0.063 | 1 restraint |
wR(F2) = 0.130 | H-atom parameters constrained |
S = 0.90 | Δρmax = 0.52 e Å−3 |
10070 reflections | Δρmin = −0.29 e Å−3 |
735 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
N1 | 0.42973 (18) | 0.8901 (3) | −0.20375 (16) | 0.0386 (8) | |
N2 | 0.6406 (2) | 0.8633 (3) | 0.33192 (15) | 0.0357 (7) | |
C1 | 0.3332 (2) | 0.8752 (4) | −0.2171 (2) | 0.0405 (9) | |
C2 | 0.2713 (3) | 0.9461 (4) | −0.1798 (2) | 0.0520 (11) | |
H2 | 0.2926 | 1.0055 | −0.1450 | 0.062* | |
C3 | 0.1743 (3) | 0.9304 (5) | −0.1933 (2) | 0.0553 (13) | |
C4 | 0.1465 (3) | 0.8437 (4) | −0.2436 (2) | 0.0525 (12) | |
H4 | 0.0820 | 0.8316 | −0.2516 | 0.063* | |
C5 | 0.2058 (3) | 0.7752 (4) | −0.2822 (2) | 0.0510 (11) | |
H5 | 0.1838 | 0.7171 | −0.3175 | 0.061* | |
C6 | 0.2999 (3) | 0.7904 (4) | −0.2696 (2) | 0.0435 (10) | |
H6 | 0.3426 | 0.7426 | −0.2971 | 0.052* | |
C7 | 0.1114 (4) | 1.0133 (6) | −0.1548 (3) | 0.110 (2) | |
H7A | 0.0781 | 1.0628 | −0.1921 | 0.165* | |
H7B | 0.1470 | 1.0664 | −0.1212 | 0.165* | |
H7C | 0.0668 | 0.9663 | −0.1256 | 0.165* | |
C8 | 0.4927 (2) | 0.8880 (4) | −0.2644 (2) | 0.0399 (9) | |
C9 | 0.4722 (3) | 0.9534 (4) | −0.3288 (2) | 0.0430 (10) | |
H9 | 0.4152 | 0.9959 | −0.3333 | 0.052* | |
C10 | 0.5365 (3) | 0.9564 (4) | −0.3878 (2) | 0.0603 (13) | |
H10 | 0.5221 | 1.0007 | −0.4322 | 0.072* | |
C11 | 0.6186 (3) | 0.8970 (6) | −0.3821 (3) | 0.0798 (19) | |
H11 | 0.6623 | 0.9021 | −0.4215 | 0.096* | |
C12 | 0.6386 (3) | 0.8282 (6) | −0.3178 (3) | 0.0798 (19) | |
H12 | 0.6950 | 0.7842 | −0.3141 | 0.096* | |
C13 | 0.5749 (3) | 0.8245 (5) | −0.2587 (2) | 0.0596 (13) | |
H13 | 0.5884 | 0.7782 | −0.2149 | 0.072* | |
C14 | 0.4631 (2) | 0.8832 (4) | −0.12804 (19) | 0.0341 (8) | |
C15 | 0.5388 (2) | 0.9530 (4) | −0.1054 (2) | 0.0357 (9) | |
H15 | 0.5690 | 1.0037 | −0.1407 | 0.043* | |
C16 | 0.5706 (2) | 0.9487 (3) | −0.03098 (19) | 0.0334 (8) | |
H16 | 0.6221 | 0.9971 | −0.0163 | 0.040* | |
C17 | 0.5282 (2) | 0.8753 (3) | 0.02174 (18) | 0.0302 (8) | |
C18 | 0.4534 (2) | 0.8053 (3) | −0.00282 (19) | 0.0343 (8) | |
H18 | 0.4239 | 0.7528 | 0.0319 | 0.041* | |
C19 | 0.4207 (2) | 0.8097 (3) | −0.0757 (2) | 0.0340 (9) | |
H19 | 0.3687 | 0.7620 | −0.0901 | 0.041* | |
C20 | 0.5596 (2) | 0.8718 (3) | 0.10151 (18) | 0.0312 (8) | |
C21 | 0.5909 (2) | 0.9754 (3) | 0.1386 (2) | 0.0342 (9) | |
H21 | 0.5936 | 1.0499 | 0.1118 | 0.041* | |
C22 | 0.6181 (2) | 0.9731 (3) | 0.2130 (2) | 0.0351 (9) | |
H22 | 0.6392 | 1.0455 | 0.2365 | 0.042* | |
C23 | 0.6150 (2) | 0.8654 (3) | 0.25428 (19) | 0.0305 (8) | |
C24 | 0.5838 (2) | 0.7603 (3) | 0.21783 (19) | 0.0321 (8) | |
H24 | 0.5809 | 0.6858 | 0.2447 | 0.039* | |
C25 | 0.5572 (2) | 0.7640 (3) | 0.14323 (19) | 0.0311 (8) | |
H25 | 0.5366 | 0.6915 | 0.1195 | 0.037* | |
C26 | 0.6738 (2) | 0.7550 (3) | 0.3666 (2) | 0.0343 (9) | |
C27 | 0.6447 (3) | 0.7255 (4) | 0.4379 (2) | 0.0489 (11) | |
H27 | 0.6026 | 0.7778 | 0.4626 | 0.059* | |
C29 | 0.7357 (3) | 0.5480 (4) | 0.4382 (3) | 0.0556 (13) | |
H29 | 0.7567 | 0.4762 | 0.4625 | 0.067* | |
C30 | 0.7666 (3) | 0.5749 (4) | 0.3683 (3) | 0.0487 (11) | |
H30 | 0.8086 | 0.5214 | 0.3444 | 0.058* | |
C31 | 0.7369 (2) | 0.6812 (3) | 0.3307 (2) | 0.0373 (9) | |
H31 | 0.7597 | 0.7014 | 0.2824 | 0.045* | |
C33 | 0.6427 (3) | 0.9731 (3) | 0.3737 (2) | 0.0372 (9) | |
C34 | 0.5657 (3) | 1.0464 (4) | 0.3794 (2) | 0.0436 (10) | |
H34 | 0.5095 | 1.0237 | 0.3550 | 0.052* | |
C35 | 0.5700 (4) | 1.1519 (4) | 0.4200 (2) | 0.0565 (12) | |
H35 | 0.5168 | 1.2021 | 0.4237 | 0.068* | |
C36 | 0.6506 (4) | 1.1850 (4) | 0.4550 (2) | 0.0595 (13) | |
H36 | 0.6531 | 1.2593 | 0.4821 | 0.071* | |
C37 | 0.7290 (3) | 1.1124 (4) | 0.4520 (2) | 0.0547 (12) | |
H37 | 0.7845 | 1.1348 | 0.4776 | 0.066* | 0.356 (8) |
C32A | 0.6615 (8) | 0.5729 (12) | 0.5464 (6) | 0.058 (4) | 0.356 (8) |
H32A | 0.6598 | 0.6384 | 0.5836 | 0.087* | 0.356 (8) |
H32B | 0.7127 | 0.5176 | 0.5585 | 0.087* | 0.356 (8) |
H32C | 0.6029 | 0.5280 | 0.5471 | 0.087* | 0.356 (8) |
C28 | 0.6748 (3) | 0.6229 (4) | 0.4739 (2) | 0.0494 (11) | |
H28 | 0.6538 | 0.6040 | 0.5229 | 0.059* | 0.644 (8) |
C32B | 0.8177 (5) | 1.1514 (6) | 0.4846 (4) | 0.064 (3) | 0.644 (8) |
H32D | 0.8243 | 1.1186 | 0.5356 | 0.096* | 0.644 (8) |
H32E | 0.8198 | 1.2403 | 0.4866 | 0.096* | 0.644 (8) |
H32F | 0.8684 | 1.1215 | 0.4535 | 0.096* | 0.644 (8) |
C38 | 0.7235 (3) | 1.0057 (4) | 0.4104 (2) | 0.0449 (10) | |
H38 | 0.7762 | 0.9545 | 0.4071 | 0.054* | |
N3 | 0.1397 (2) | 0.3956 (3) | 0.17160 (15) | 0.0344 (7) | |
N4 | −0.06884 (18) | 0.3667 (3) | 0.70335 (15) | 0.0371 (7) | |
C39 | 0.1399 (2) | 0.2857 (3) | 0.12883 (19) | 0.0345 (9) | |
C40 | 0.2204 (3) | 0.2539 (3) | 0.0922 (2) | 0.0391 (9) | |
H40 | 0.2731 | 0.3053 | 0.0957 | 0.047* | |
C41 | 0.2252 (3) | 0.1465 (4) | 0.0499 (2) | 0.0461 (11) | |
C42 | 0.1468 (3) | 0.0746 (4) | 0.0464 (2) | 0.0510 (12) | |
H42 | 0.1483 | 0.0011 | 0.0186 | 0.061* | |
C43 | 0.0664 (3) | 0.1074 (4) | 0.0825 (2) | 0.0471 (11) | |
H43 | 0.0134 | 0.0566 | 0.0789 | 0.057* | |
C44 | 0.0625 (3) | 0.2135 (3) | 0.1237 (2) | 0.0413 (10) | |
H44 | 0.0070 | 0.2363 | 0.1482 | 0.050* | |
C45 | 0.3133 (4) | 0.1104 (5) | 0.0137 (3) | 0.0791 (16) | |
H45A | 0.3197 | 0.1538 | −0.0340 | 0.119* | |
H45B | 0.3128 | 0.0227 | 0.0042 | 0.119* | |
H45C | 0.3655 | 0.1307 | 0.0469 | 0.119* | |
C46 | 0.1719 (2) | 0.5035 (3) | 0.1359 (2) | 0.0327 (8) | |
C47 | 0.2364 (2) | 0.5780 (3) | 0.1702 (2) | 0.0349 (9) | |
H47 | 0.2604 | 0.5589 | 0.2186 | 0.042* | |
C48 | 0.2660 (3) | 0.6826 (4) | 0.1322 (2) | 0.0425 (10) | |
H48 | 0.3096 | 0.7353 | 0.1557 | 0.051* | |
C49 | 0.2328 (3) | 0.7097 (4) | 0.0620 (2) | 0.0451 (11) | |
H49 | 0.2535 | 0.7809 | 0.0373 | 0.054* | |
C50 | 0.1698 (3) | 0.6350 (4) | 0.0269 (2) | 0.0473 (11) | |
H50 | 0.1474 | 0.6530 | −0.0221 | 0.057* | |
C51 | 0.1399 (3) | 0.5328 (4) | 0.0646 (2) | 0.0438 (10) | |
H51 | 0.0959 | 0.4811 | 0.0408 | 0.053* | |
C52 | 0.1157 (2) | 0.3934 (3) | 0.24843 (19) | 0.0319 (8) | |
C53 | 0.0863 (2) | 0.4986 (3) | 0.28523 (19) | 0.0315 (8) | |
H53 | 0.0844 | 0.5735 | 0.2588 | 0.038* | |
C54 | 0.0602 (2) | 0.4949 (3) | 0.35928 (19) | 0.0303 (8) | |
H54 | 0.0403 | 0.5676 | 0.3828 | 0.036* | |
C55 | 0.0621 (2) | 0.3876 (3) | 0.40101 (19) | 0.0314 (8) | |
C56 | 0.0925 (2) | 0.2834 (3) | 0.36395 (19) | 0.0328 (8) | |
H56 | 0.0952 | 0.2086 | 0.3905 | 0.039* | |
C57 | 0.1187 (2) | 0.2868 (3) | 0.28959 (19) | 0.0329 (9) | |
H57 | 0.1393 | 0.2143 | 0.2662 | 0.039* | |
C58 | 0.0303 (2) | 0.3836 (3) | 0.48003 (18) | 0.0299 (8) | |
C59 | −0.0437 (2) | 0.4534 (3) | 0.50360 (19) | 0.0339 (8) | |
H59 | −0.0730 | 0.5062 | 0.4685 | 0.041* | |
C60 | −0.0763 (2) | 0.4493 (3) | 0.5761 (2) | 0.0351 (9) | |
H60 | −0.1272 | 0.4989 | 0.5899 | 0.042* | |
C61 | −0.0355 (2) | 0.3731 (3) | 0.62892 (19) | 0.0325 (8) | |
C62 | 0.0398 (2) | 0.3021 (4) | 0.60653 (19) | 0.0347 (9) | |
H62 | 0.0691 | 0.2497 | 0.6419 | 0.042* | |
C63 | 0.0721 (2) | 0.3072 (3) | 0.53369 (19) | 0.0331 (8) | |
H63 | 0.1234 | 0.2584 | 0.5198 | 0.040* | |
C64 | −0.1651 (2) | 0.3798 (4) | 0.7152 (2) | 0.0415 (10) | |
C65 | −0.2264 (3) | 0.3093 (5) | 0.6767 (2) | 0.0573 (12) | |
H65 | −0.2060 | 0.2500 | 0.6418 | 0.069* | |
C66 | −0.3252 (3) | 0.3279 (4) | 0.6907 (2) | 0.0603 (14) | |
C67 | −0.3508 (3) | 0.4156 (4) | 0.7413 (2) | 0.0547 (12) | |
H67 | −0.4150 | 0.4280 | 0.7495 | 0.066* | |
C68 | −0.2919 (3) | 0.4834 (5) | 0.7791 (3) | 0.0631 (13) | |
H68 | −0.3127 | 0.5426 | 0.8138 | 0.076* | |
C69 | −0.1980 (3) | 0.4657 (4) | 0.7667 (2) | 0.0482 (11) | |
H69 | −0.1545 | 0.5135 | 0.7941 | 0.058* | |
C70 | −0.3884 (4) | 0.2479 (6) | 0.6531 (3) | 0.117 (2) | |
H70A | −0.4278 | 0.2947 | 0.6186 | 0.175* | |
H70B | −0.4270 | 0.2069 | 0.6902 | 0.175* | |
H70C | −0.3536 | 0.1872 | 0.6247 | 0.175* | |
C71 | −0.0056 (2) | 0.3680 (4) | 0.7648 (2) | 0.0369 (9) | |
C72 | −0.0255 (3) | 0.3042 (4) | 0.8297 (2) | 0.0414 (9) | |
H72 | −0.0824 | 0.2616 | 0.8336 | 0.050* | |
C73 | 0.0387 (3) | 0.3022 (4) | 0.8900 (2) | 0.0579 (12) | |
H73 | 0.0251 | 0.2579 | 0.9343 | 0.070* | |
C74 | 0.1207 (3) | 0.3642 (5) | 0.8849 (3) | 0.0708 (16) | |
H74 | 0.1642 | 0.3611 | 0.9253 | 0.085* | |
C75 | 0.1407 (3) | 0.4310 (5) | 0.8213 (3) | 0.0702 (16) | |
H75 | 0.1970 | 0.4753 | 0.8184 | 0.084* | |
C76 | 0.0772 (3) | 0.4331 (4) | 0.7610 (2) | 0.0541 (12) | |
H76 | 0.0906 | 0.4790 | 0.7174 | 0.065* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0275 (16) | 0.051 (2) | 0.0367 (18) | 0.0062 (16) | −0.0049 (13) | 0.0032 (17) |
N2 | 0.0463 (18) | 0.0272 (18) | 0.0334 (18) | 0.0052 (16) | −0.0065 (13) | −0.0032 (15) |
C1 | 0.038 (2) | 0.046 (2) | 0.038 (2) | 0.014 (2) | 0.0031 (16) | 0.018 (2) |
C2 | 0.045 (2) | 0.068 (3) | 0.043 (2) | 0.019 (2) | −0.0047 (19) | 0.007 (2) |
C3 | 0.043 (2) | 0.079 (4) | 0.044 (3) | 0.030 (3) | 0.0146 (19) | 0.010 (2) |
C4 | 0.048 (3) | 0.064 (3) | 0.045 (3) | −0.008 (2) | −0.005 (2) | 0.003 (2) |
C5 | 0.053 (3) | 0.046 (3) | 0.054 (3) | 0.000 (2) | 0.004 (2) | 0.014 (2) |
C6 | 0.037 (2) | 0.040 (3) | 0.053 (3) | −0.002 (2) | −0.0055 (18) | 0.013 (2) |
C7 | 0.086 (4) | 0.148 (7) | 0.096 (5) | 0.038 (4) | −0.017 (3) | −0.041 (5) |
C8 | 0.028 (2) | 0.046 (3) | 0.045 (2) | 0.001 (2) | −0.0006 (16) | −0.004 (2) |
C9 | 0.047 (2) | 0.042 (2) | 0.040 (2) | −0.012 (2) | 0.0006 (18) | −0.001 (2) |
C10 | 0.063 (3) | 0.062 (3) | 0.056 (3) | −0.031 (3) | 0.014 (2) | −0.017 (2) |
C11 | 0.057 (3) | 0.118 (5) | 0.064 (3) | −0.046 (3) | 0.020 (3) | −0.053 (3) |
C12 | 0.036 (3) | 0.127 (6) | 0.076 (4) | 0.004 (3) | −0.008 (2) | −0.051 (4) |
C13 | 0.041 (2) | 0.087 (4) | 0.050 (3) | 0.010 (3) | −0.005 (2) | −0.016 (3) |
C14 | 0.031 (2) | 0.031 (2) | 0.040 (2) | 0.0077 (18) | −0.0011 (15) | 0.0041 (18) |
C15 | 0.035 (2) | 0.032 (2) | 0.039 (2) | 0.0010 (18) | 0.0026 (16) | 0.0047 (18) |
C16 | 0.0277 (19) | 0.031 (2) | 0.041 (2) | 0.0045 (17) | −0.0009 (15) | 0.0037 (18) |
C17 | 0.0259 (18) | 0.0250 (19) | 0.040 (2) | 0.0045 (17) | −0.0010 (14) | 0.0050 (17) |
C18 | 0.036 (2) | 0.027 (2) | 0.040 (2) | 0.0007 (18) | 0.0016 (16) | 0.0066 (17) |
C19 | 0.0277 (19) | 0.030 (2) | 0.044 (2) | 0.0016 (17) | −0.0053 (16) | 0.0029 (18) |
C20 | 0.0288 (19) | 0.029 (2) | 0.036 (2) | 0.0037 (17) | 0.0007 (14) | 0.0038 (18) |
C21 | 0.036 (2) | 0.028 (2) | 0.038 (2) | 0.0018 (18) | 0.0007 (16) | 0.0019 (17) |
C22 | 0.036 (2) | 0.026 (2) | 0.044 (2) | −0.0007 (17) | 0.0017 (16) | −0.0014 (18) |
C23 | 0.0262 (18) | 0.030 (2) | 0.036 (2) | 0.0064 (18) | 0.0028 (14) | −0.0038 (18) |
C24 | 0.0250 (19) | 0.032 (2) | 0.040 (2) | 0.0015 (17) | −0.0003 (15) | 0.0049 (17) |
C25 | 0.0258 (18) | 0.032 (2) | 0.035 (2) | 0.0002 (17) | −0.0006 (15) | 0.0002 (17) |
C26 | 0.038 (2) | 0.028 (2) | 0.037 (2) | 0.0032 (18) | −0.0099 (17) | −0.0028 (17) |
C27 | 0.060 (3) | 0.045 (3) | 0.042 (3) | −0.004 (2) | −0.004 (2) | −0.005 (2) |
C29 | 0.067 (3) | 0.031 (3) | 0.067 (3) | −0.010 (2) | −0.040 (3) | 0.011 (2) |
C30 | 0.049 (3) | 0.030 (2) | 0.066 (3) | 0.015 (2) | −0.025 (2) | −0.016 (2) |
C31 | 0.035 (2) | 0.033 (2) | 0.043 (2) | 0.0086 (18) | −0.0128 (17) | −0.0082 (18) |
C33 | 0.045 (2) | 0.028 (2) | 0.039 (2) | 0.0012 (19) | 0.0003 (17) | −0.0038 (17) |
C34 | 0.052 (3) | 0.034 (2) | 0.045 (2) | 0.010 (2) | 0.0035 (19) | −0.0052 (19) |
C35 | 0.078 (3) | 0.043 (3) | 0.049 (3) | 0.012 (3) | 0.010 (2) | −0.005 (2) |
C36 | 0.098 (4) | 0.030 (3) | 0.051 (3) | 0.004 (3) | 0.006 (3) | −0.006 (2) |
C37 | 0.078 (3) | 0.036 (3) | 0.050 (3) | −0.007 (2) | −0.014 (2) | −0.008 (2) |
C32A | 0.059 (8) | 0.062 (9) | 0.052 (9) | 0.009 (7) | 0.000 (6) | 0.018 (7) |
C28 | 0.068 (3) | 0.037 (3) | 0.042 (3) | −0.009 (2) | −0.015 (2) | 0.010 (2) |
C32B | 0.083 (6) | 0.043 (5) | 0.065 (5) | 0.000 (4) | −0.037 (4) | −0.001 (4) |
C38 | 0.055 (3) | 0.032 (2) | 0.049 (3) | −0.003 (2) | −0.004 (2) | −0.004 (2) |
N3 | 0.0457 (18) | 0.0244 (18) | 0.0331 (17) | −0.0051 (15) | 0.0031 (13) | −0.0044 (14) |
N4 | 0.0267 (16) | 0.047 (2) | 0.0381 (18) | −0.0038 (16) | 0.0039 (13) | 0.0054 (16) |
C39 | 0.043 (2) | 0.028 (2) | 0.032 (2) | −0.0039 (19) | 0.0003 (16) | −0.0014 (17) |
C40 | 0.046 (2) | 0.028 (2) | 0.043 (2) | −0.0052 (19) | 0.0048 (18) | −0.0034 (18) |
C41 | 0.066 (3) | 0.031 (2) | 0.042 (3) | 0.000 (2) | 0.011 (2) | −0.0011 (19) |
C42 | 0.090 (4) | 0.026 (2) | 0.037 (2) | −0.003 (2) | −0.001 (2) | −0.0040 (19) |
C43 | 0.067 (3) | 0.033 (2) | 0.041 (3) | −0.011 (2) | −0.006 (2) | −0.0030 (19) |
C44 | 0.047 (2) | 0.032 (2) | 0.045 (2) | −0.009 (2) | −0.0010 (18) | −0.0059 (18) |
C45 | 0.096 (4) | 0.059 (3) | 0.083 (4) | −0.003 (3) | 0.032 (3) | −0.013 (3) |
C46 | 0.037 (2) | 0.028 (2) | 0.033 (2) | −0.0031 (18) | 0.0095 (16) | −0.0029 (17) |
C47 | 0.033 (2) | 0.034 (2) | 0.038 (2) | −0.0072 (18) | 0.0106 (16) | −0.0093 (18) |
C48 | 0.038 (2) | 0.030 (2) | 0.059 (3) | −0.0129 (18) | 0.016 (2) | −0.019 (2) |
C49 | 0.052 (3) | 0.030 (2) | 0.054 (3) | 0.001 (2) | 0.022 (2) | 0.003 (2) |
C50 | 0.058 (3) | 0.042 (3) | 0.042 (3) | 0.005 (2) | 0.010 (2) | 0.006 (2) |
C51 | 0.053 (3) | 0.036 (2) | 0.043 (3) | −0.001 (2) | 0.0019 (19) | −0.0057 (19) |
C52 | 0.0274 (19) | 0.032 (2) | 0.036 (2) | −0.0063 (18) | −0.0007 (15) | −0.0017 (18) |
C53 | 0.0268 (19) | 0.028 (2) | 0.040 (2) | −0.0013 (16) | −0.0004 (15) | 0.0014 (17) |
C54 | 0.0248 (18) | 0.030 (2) | 0.036 (2) | 0.0002 (16) | −0.0002 (15) | −0.0006 (17) |
C55 | 0.0286 (19) | 0.028 (2) | 0.038 (2) | −0.0032 (17) | −0.0022 (15) | −0.0007 (18) |
C56 | 0.0318 (19) | 0.032 (2) | 0.035 (2) | −0.0012 (17) | −0.0039 (15) | 0.0021 (17) |
C57 | 0.035 (2) | 0.025 (2) | 0.039 (2) | −0.0004 (17) | −0.0019 (16) | −0.0041 (17) |
C58 | 0.0245 (18) | 0.0285 (19) | 0.037 (2) | −0.0046 (17) | −0.0008 (14) | 0.0025 (17) |
C59 | 0.031 (2) | 0.032 (2) | 0.039 (2) | −0.0005 (18) | −0.0023 (15) | 0.0082 (18) |
C60 | 0.0262 (19) | 0.034 (2) | 0.045 (2) | −0.0013 (17) | 0.0058 (16) | 0.0024 (19) |
C61 | 0.0257 (18) | 0.030 (2) | 0.042 (2) | −0.0072 (17) | −0.0017 (15) | 0.0037 (18) |
C62 | 0.0290 (19) | 0.036 (2) | 0.039 (2) | 0.0008 (18) | −0.0072 (15) | 0.0037 (18) |
C63 | 0.0253 (18) | 0.032 (2) | 0.042 (2) | −0.0041 (17) | −0.0017 (15) | 0.0007 (18) |
C64 | 0.033 (2) | 0.053 (3) | 0.038 (2) | −0.007 (2) | −0.0020 (16) | 0.019 (2) |
C65 | 0.048 (3) | 0.077 (3) | 0.047 (3) | −0.021 (3) | −0.004 (2) | 0.015 (2) |
C66 | 0.058 (3) | 0.071 (4) | 0.051 (3) | −0.035 (3) | −0.033 (2) | 0.023 (3) |
C67 | 0.066 (3) | 0.054 (3) | 0.044 (3) | 0.009 (3) | 0.007 (2) | 0.004 (2) |
C68 | 0.066 (3) | 0.056 (3) | 0.067 (3) | 0.002 (3) | −0.007 (2) | 0.024 (3) |
C69 | 0.036 (2) | 0.054 (3) | 0.055 (3) | 0.010 (2) | 0.0128 (18) | 0.022 (2) |
C70 | 0.116 (5) | 0.142 (7) | 0.092 (5) | −0.035 (5) | 0.023 (4) | −0.034 (5) |
C71 | 0.030 (2) | 0.041 (2) | 0.039 (2) | 0.003 (2) | −0.0007 (16) | −0.003 (2) |
C72 | 0.044 (2) | 0.037 (2) | 0.043 (2) | 0.009 (2) | −0.0027 (18) | −0.0002 (19) |
C73 | 0.064 (3) | 0.052 (3) | 0.057 (3) | 0.024 (3) | −0.012 (2) | −0.011 (2) |
C74 | 0.047 (3) | 0.101 (4) | 0.064 (3) | 0.029 (3) | −0.015 (2) | −0.041 (3) |
C75 | 0.037 (2) | 0.111 (5) | 0.063 (3) | −0.011 (3) | 0.005 (2) | −0.043 (3) |
C76 | 0.040 (2) | 0.081 (4) | 0.041 (2) | −0.014 (2) | 0.0056 (18) | −0.015 (2) |
N1—C8 | 1.419 (4) | C32B—H32F | 0.9800 |
N1—C1 | 1.422 (4) | C38—H38 | 0.9500 |
N1—C14 | 1.429 (4) | N3—C52 | 1.415 (4) |
N2—C33 | 1.420 (5) | N3—C46 | 1.428 (4) |
N2—C26 | 1.424 (4) | N3—C39 | 1.430 (4) |
N2—C23 | 1.428 (4) | N4—C64 | 1.416 (4) |
C1—C2 | 1.365 (5) | N4—C61 | 1.417 (4) |
C1—C6 | 1.403 (6) | N4—C71 | 1.418 (4) |
C2—C3 | 1.430 (6) | C39—C44 | 1.375 (5) |
C2—H2 | 0.9500 | C39—C40 | 1.385 (5) |
C3—C4 | 1.367 (6) | C40—C41 | 1.404 (5) |
C3—C7 | 1.464 (6) | C40—H40 | 0.9500 |
C4—C5 | 1.336 (6) | C41—C42 | 1.383 (6) |
C4—H4 | 0.9500 | C41—C45 | 1.488 (6) |
C5—C6 | 1.385 (5) | C42—C43 | 1.382 (6) |
C5—H5 | 0.9500 | C42—H42 | 0.9500 |
C6—H6 | 0.9500 | C43—C44 | 1.382 (5) |
C7—H7A | 0.9800 | C43—H43 | 0.9500 |
C7—H7B | 0.9800 | C44—H44 | 0.9500 |
C7—H7C | 0.9800 | C45—H45A | 0.9800 |
C8—C13 | 1.382 (5) | C45—H45B | 0.9800 |
C8—C9 | 1.384 (5) | C45—H45C | 0.9800 |
C9—C10 | 1.409 (5) | C46—C47 | 1.379 (5) |
C9—H9 | 0.9500 | C46—C51 | 1.385 (5) |
C10—C11 | 1.358 (7) | C47—C48 | 1.405 (5) |
C10—H10 | 0.9500 | C47—H47 | 0.9500 |
C11—C12 | 1.401 (7) | C48—C49 | 1.367 (5) |
C11—H11 | 0.9500 | C48—H48 | 0.9500 |
C12—C13 | 1.405 (6) | C49—C50 | 1.372 (6) |
C12—H12 | 0.9500 | C49—H49 | 0.9500 |
C13—H13 | 0.9500 | C50—C51 | 1.381 (5) |
C14—C19 | 1.383 (5) | C50—H50 | 0.9500 |
C14—C15 | 1.393 (5) | C51—H51 | 0.9500 |
C15—C16 | 1.398 (5) | C52—C57 | 1.385 (5) |
C15—H15 | 0.9500 | C52—C53 | 1.400 (5) |
C16—C17 | 1.386 (5) | C53—C54 | 1.376 (4) |
C16—H16 | 0.9500 | C53—H53 | 0.9500 |
C17—C18 | 1.395 (5) | C54—C55 | 1.396 (5) |
C17—C20 | 1.487 (4) | C54—H54 | 0.9500 |
C18—C19 | 1.377 (4) | C55—C56 | 1.397 (5) |
C18—H18 | 0.9500 | C55—C58 | 1.485 (4) |
C19—H19 | 0.9500 | C56—C57 | 1.381 (4) |
C20—C21 | 1.391 (5) | C56—H56 | 0.9500 |
C20—C25 | 1.401 (5) | C57—H57 | 0.9500 |
C21—C22 | 1.379 (5) | C58—C59 | 1.385 (5) |
C21—H21 | 0.9500 | C58—C63 | 1.405 (5) |
C22—C23 | 1.396 (5) | C59—C60 | 1.379 (4) |
C22—H22 | 0.9500 | C59—H59 | 0.9500 |
C23—C24 | 1.399 (5) | C60—C61 | 1.388 (5) |
C24—C25 | 1.379 (4) | C60—H60 | 0.9500 |
C24—H24 | 0.9500 | C61—C62 | 1.401 (5) |
C25—H25 | 0.9500 | C62—C63 | 1.384 (4) |
C26—C27 | 1.379 (5) | C62—H62 | 0.9500 |
C26—C31 | 1.384 (5) | C63—H63 | 0.9500 |
C27—C28 | 1.368 (6) | C64—C65 | 1.359 (5) |
C27—H27 | 0.9500 | C64—C69 | 1.404 (6) |
C29—C30 | 1.358 (6) | C65—C66 | 1.466 (6) |
C29—C28 | 1.367 (6) | C65—H65 | 0.9500 |
C29—H29 | 0.9500 | C66—C67 | 1.375 (6) |
C30—C31 | 1.413 (5) | C66—C70 | 1.429 (7) |
C30—H30 | 0.9500 | C67—C68 | 1.312 (6) |
C31—H31 | 0.9500 | C67—H67 | 0.9500 |
C33—C38 | 1.379 (5) | C68—C69 | 1.391 (6) |
C33—C34 | 1.379 (5) | C68—H68 | 0.9500 |
C34—C35 | 1.369 (5) | C69—H69 | 0.9500 |
C34—H34 | 0.9500 | C70—H70A | 0.9800 |
C35—C36 | 1.365 (6) | C70—H70B | 0.9800 |
C35—H35 | 0.9500 | C70—H70C | 0.9800 |
C36—C37 | 1.388 (6) | C71—C72 | 1.385 (5) |
C36—H36 | 0.9500 | C71—C76 | 1.396 (5) |
C37—C38 | 1.392 (5) | C72—C73 | 1.412 (5) |
C37—C32B | 1.467 (8) | C72—H72 | 0.9500 |
C37—H37 | 0.9500 | C73—C74 | 1.371 (6) |
C32A—C28 | 1.418 (11) | C73—H73 | 0.9500 |
C32A—H32A | 0.9800 | C74—C75 | 1.384 (7) |
C32A—H32B | 0.9800 | C74—H74 | 0.9500 |
C32A—H32C | 0.9800 | C75—C76 | 1.404 (6) |
C28—H28 | 0.9500 | C75—H75 | 0.9500 |
C32B—H32D | 0.9800 | C76—H76 | 0.9500 |
C32B—H32E | 0.9800 | ||
C8—N1—C1 | 120.4 (3) | H32D—C32B—H32F | 109.5 |
C8—N1—C14 | 120.3 (3) | H32E—C32B—H32F | 109.5 |
C1—N1—C14 | 118.2 (3) | C33—C38—C37 | 121.0 (4) |
C33—N2—C26 | 118.7 (3) | C33—C38—H38 | 119.5 |
C33—N2—C23 | 119.8 (3) | C37—C38—H38 | 119.5 |
C26—N2—C23 | 121.1 (3) | C52—N3—C46 | 122.0 (3) |
C2—C1—C6 | 118.9 (4) | C52—N3—C39 | 120.1 (3) |
C2—C1—N1 | 119.9 (4) | C46—N3—C39 | 117.7 (3) |
C6—C1—N1 | 121.2 (3) | C64—N4—C61 | 118.6 (3) |
C1—C2—C3 | 119.6 (4) | C64—N4—C71 | 120.6 (3) |
C1—C2—H2 | 120.2 | C61—N4—C71 | 119.9 (3) |
C3—C2—H2 | 120.2 | C44—C39—C40 | 120.6 (4) |
C4—C3—C2 | 118.4 (4) | C44—C39—N3 | 121.3 (3) |
C4—C3—C7 | 124.2 (4) | C40—C39—N3 | 118.1 (3) |
C2—C3—C7 | 117.3 (5) | C39—C40—C41 | 120.8 (4) |
C5—C4—C3 | 123.0 (4) | C39—C40—H40 | 119.6 |
C5—C4—H4 | 118.5 | C41—C40—H40 | 119.6 |
C3—C4—H4 | 118.5 | C42—C41—C40 | 117.5 (4) |
C4—C5—C6 | 118.9 (4) | C42—C41—C45 | 122.1 (4) |
C4—C5—H5 | 120.6 | C40—C41—C45 | 120.4 (4) |
C6—C5—H5 | 120.6 | C43—C42—C41 | 121.4 (4) |
C5—C6—C1 | 121.1 (4) | C43—C42—H42 | 119.3 |
C5—C6—H6 | 119.4 | C41—C42—H42 | 119.3 |
C1—C6—H6 | 119.4 | C44—C43—C42 | 120.4 (4) |
C3—C7—H7A | 109.5 | C44—C43—H43 | 119.8 |
C3—C7—H7B | 109.5 | C42—C43—H43 | 119.8 |
H7A—C7—H7B | 109.5 | C39—C44—C43 | 119.2 (4) |
C3—C7—H7C | 109.5 | C39—C44—H44 | 120.4 |
H7A—C7—H7C | 109.5 | C43—C44—H44 | 120.4 |
H7B—C7—H7C | 109.5 | C41—C45—H45A | 109.5 |
C13—C8—C9 | 120.1 (4) | C41—C45—H45B | 109.5 |
C13—C8—N1 | 120.6 (4) | H45A—C45—H45B | 109.5 |
C9—C8—N1 | 119.3 (3) | C41—C45—H45C | 109.5 |
C8—C9—C10 | 119.5 (4) | H45A—C45—H45C | 109.5 |
C8—C9—H9 | 120.3 | H45B—C45—H45C | 109.5 |
C10—C9—H9 | 120.3 | C47—C46—C51 | 119.0 (4) |
C11—C10—C9 | 121.1 (5) | C47—C46—N3 | 121.3 (3) |
C11—C10—H10 | 119.5 | C51—C46—N3 | 119.7 (3) |
C9—C10—H10 | 119.5 | C46—C47—C48 | 118.9 (4) |
C10—C11—C12 | 119.6 (4) | C46—C47—H47 | 120.6 |
C10—C11—H11 | 120.2 | C48—C47—H47 | 120.6 |
C12—C11—H11 | 120.2 | C49—C48—C47 | 120.9 (4) |
C11—C12—C13 | 119.8 (5) | C49—C48—H48 | 119.6 |
C11—C12—H12 | 120.1 | C47—C48—H48 | 119.6 |
C13—C12—H12 | 120.1 | C48—C49—C50 | 120.7 (4) |
C8—C13—C12 | 120.0 (5) | C48—C49—H49 | 119.7 |
C8—C13—H13 | 120.0 | C50—C49—H49 | 119.7 |
C12—C13—H13 | 120.0 | C49—C50—C51 | 118.5 (4) |
C19—C14—C15 | 118.7 (3) | C49—C50—H50 | 120.7 |
C19—C14—N1 | 121.3 (3) | C51—C50—H50 | 120.7 |
C15—C14—N1 | 120.0 (3) | C50—C51—C46 | 122.1 (4) |
C14—C15—C16 | 120.3 (3) | C50—C51—H51 | 119.0 |
C14—C15—H15 | 119.8 | C46—C51—H51 | 119.0 |
C16—C15—H15 | 119.8 | C57—C52—C53 | 117.6 (3) |
C17—C16—C15 | 121.2 (3) | C57—C52—N3 | 121.3 (3) |
C17—C16—H16 | 119.4 | C53—C52—N3 | 121.1 (3) |
C15—C16—H16 | 119.4 | C54—C53—C52 | 120.7 (3) |
C16—C17—C18 | 117.2 (3) | C54—C53—H53 | 119.6 |
C16—C17—C20 | 122.0 (3) | C52—C53—H53 | 119.6 |
C18—C17—C20 | 120.9 (3) | C53—C54—C55 | 122.1 (3) |
C19—C18—C17 | 122.2 (3) | C53—C54—H54 | 118.9 |
C19—C18—H18 | 118.9 | C55—C54—H54 | 118.9 |
C17—C18—H18 | 118.9 | C54—C55—C56 | 116.7 (3) |
C18—C19—C14 | 120.4 (3) | C54—C55—C58 | 121.6 (3) |
C18—C19—H19 | 119.8 | C56—C55—C58 | 121.7 (3) |
C14—C19—H19 | 119.8 | C57—C56—C55 | 121.4 (3) |
C21—C20—C25 | 117.0 (3) | C57—C56—H56 | 119.3 |
C21—C20—C17 | 121.7 (3) | C55—C56—H56 | 119.3 |
C25—C20—C17 | 121.3 (3) | C56—C57—C52 | 121.5 (3) |
C22—C21—C20 | 121.9 (3) | C56—C57—H57 | 119.3 |
C22—C21—H21 | 119.1 | C52—C57—H57 | 119.3 |
C20—C21—H21 | 119.1 | C59—C58—C63 | 117.0 (3) |
C21—C22—C23 | 120.7 (3) | C59—C58—C55 | 121.2 (3) |
C21—C22—H22 | 119.6 | C63—C58—C55 | 121.7 (3) |
C23—C22—H22 | 119.6 | C60—C59—C58 | 122.5 (3) |
C22—C23—C24 | 118.1 (3) | C60—C59—H59 | 118.7 |
C22—C23—N2 | 120.9 (3) | C58—C59—H59 | 118.7 |
C24—C23—N2 | 121.0 (3) | C59—C60—C61 | 120.4 (3) |
C25—C24—C23 | 120.5 (3) | C59—C60—H60 | 119.8 |
C25—C24—H24 | 119.8 | C61—C60—H60 | 119.8 |
C23—C24—H24 | 119.8 | C60—C61—C62 | 118.1 (3) |
C24—C25—C20 | 121.8 (3) | C60—C61—N4 | 121.2 (3) |
C24—C25—H25 | 119.1 | C62—C61—N4 | 120.7 (3) |
C20—C25—H25 | 119.1 | C63—C62—C61 | 121.0 (3) |
C27—C26—C31 | 119.7 (4) | C63—C62—H62 | 119.5 |
C27—C26—N2 | 119.5 (3) | C61—C62—H62 | 119.5 |
C31—C26—N2 | 120.8 (3) | C62—C63—C58 | 120.9 (3) |
C28—C27—C26 | 121.8 (4) | C62—C63—H63 | 119.5 |
C28—C27—H27 | 119.1 | C58—C63—H63 | 119.5 |
C26—C27—H27 | 119.1 | C65—C64—C69 | 119.5 (4) |
C30—C29—C28 | 120.9 (4) | C65—C64—N4 | 120.2 (4) |
C30—C29—H29 | 119.6 | C69—C64—N4 | 120.4 (4) |
C28—C29—H29 | 119.6 | C64—C65—C66 | 117.7 (4) |
C29—C30—C31 | 120.9 (4) | C64—C65—H65 | 121.1 |
C29—C30—H30 | 119.6 | C66—C65—H65 | 121.1 |
C31—C30—H30 | 119.6 | C67—C66—C70 | 124.4 (5) |
C26—C31—C30 | 117.8 (4) | C67—C66—C65 | 118.6 (4) |
C26—C31—H31 | 121.1 | C70—C66—C65 | 116.9 (5) |
C30—C31—H31 | 121.1 | C68—C67—C66 | 123.9 (5) |
C38—C33—C34 | 119.5 (4) | C68—C67—H67 | 118.0 |
C38—C33—N2 | 118.9 (3) | C66—C67—H67 | 118.0 |
C34—C33—N2 | 121.7 (3) | C67—C68—C69 | 117.9 (5) |
C35—C34—C33 | 120.3 (4) | C67—C68—H68 | 121.0 |
C35—C34—H34 | 119.9 | C69—C68—H68 | 121.0 |
C33—C34—H34 | 119.9 | C68—C69—C64 | 122.4 (4) |
C36—C35—C34 | 120.1 (4) | C68—C69—H69 | 118.8 |
C36—C35—H35 | 120.0 | C64—C69—H69 | 118.8 |
C34—C35—H35 | 120.0 | C66—C70—H70A | 109.5 |
C35—C36—C37 | 121.4 (4) | C66—C70—H70B | 109.5 |
C35—C36—H36 | 119.3 | H70A—C70—H70B | 109.5 |
C37—C36—H36 | 119.3 | C66—C70—H70C | 109.5 |
C36—C37—C38 | 117.7 (4) | H70A—C70—H70C | 109.5 |
C36—C37—C32B | 121.8 (5) | H70B—C70—H70C | 109.5 |
C38—C37—C32B | 120.2 (5) | C72—C71—C76 | 119.1 (3) |
C36—C37—H37 | 121.1 | C72—C71—N4 | 120.0 (3) |
C38—C37—H37 | 121.1 | C76—C71—N4 | 120.9 (3) |
C28—C32A—H32A | 109.5 | C71—C72—C73 | 120.1 (4) |
C28—C32A—H32B | 109.5 | C71—C72—H72 | 120.0 |
H32A—C32A—H32B | 109.5 | C73—C72—H72 | 120.0 |
C28—C32A—H32C | 109.5 | C74—C73—C72 | 120.2 (4) |
H32A—C32A—H32C | 109.5 | C74—C73—H73 | 119.9 |
H32B—C32A—H32C | 109.5 | C72—C73—H73 | 119.9 |
C29—C28—C27 | 118.9 (4) | C73—C74—C75 | 120.5 (4) |
C29—C28—C32A | 106.4 (6) | C73—C74—H74 | 119.8 |
C27—C28—C32A | 134.6 (7) | C75—C74—H74 | 119.8 |
C29—C28—H28 | 120.5 | C74—C75—C76 | 119.6 (4) |
C27—C28—H28 | 120.5 | C74—C75—H75 | 120.2 |
C37—C32B—H32D | 109.5 | C76—C75—H75 | 120.2 |
C37—C32B—H32E | 109.5 | C71—C76—C75 | 120.5 (4) |
H32D—C32B—H32E | 109.5 | C71—C76—H76 | 119.7 |
C37—C32B—H32F | 109.5 | C75—C76—H76 | 119.7 |
C8—N1—C1—C2 | −138.0 (4) | C32B—C37—C38—C33 | −174.2 (5) |
C14—N1—C1—C2 | 54.0 (5) | C52—N3—C39—C44 | 55.9 (5) |
C8—N1—C1—C6 | 40.5 (5) | C46—N3—C39—C44 | −129.3 (4) |
C14—N1—C1—C6 | −127.5 (4) | C52—N3—C39—C40 | −124.3 (4) |
C6—C1—C2—C3 | 1.7 (6) | C46—N3—C39—C40 | 50.5 (5) |
N1—C1—C2—C3 | −179.8 (3) | C44—C39—C40—C41 | −0.9 (6) |
C1—C2—C3—C4 | 0.1 (6) | N3—C39—C40—C41 | 179.4 (3) |
C1—C2—C3—C7 | −176.7 (4) | C39—C40—C41—C42 | 0.0 (6) |
C2—C3—C4—C5 | −1.8 (6) | C39—C40—C41—C45 | −177.2 (4) |
C7—C3—C4—C5 | 174.8 (5) | C40—C41—C42—C43 | 0.6 (6) |
C3—C4—C5—C6 | 1.4 (6) | C45—C41—C42—C43 | 177.8 (4) |
C4—C5—C6—C1 | 0.5 (6) | C41—C42—C43—C44 | −0.4 (6) |
C2—C1—C6—C5 | −2.0 (6) | C40—C39—C44—C43 | 1.1 (6) |
N1—C1—C6—C5 | 179.4 (3) | N3—C39—C44—C43 | −179.2 (3) |
C1—N1—C8—C13 | −136.4 (4) | C42—C43—C44—C39 | −0.5 (6) |
C14—N1—C8—C13 | 31.4 (6) | C52—N3—C46—C47 | 44.0 (5) |
C1—N1—C8—C9 | 45.5 (5) | C39—N3—C46—C47 | −130.6 (3) |
C14—N1—C8—C9 | −146.8 (4) | C52—N3—C46—C51 | −137.7 (3) |
C13—C8—C9—C10 | −1.2 (6) | C39—N3—C46—C51 | 47.6 (5) |
N1—C8—C9—C10 | 177.0 (4) | C51—C46—C47—C48 | 1.4 (5) |
C8—C9—C10—C11 | −0.5 (6) | N3—C46—C47—C48 | 179.6 (3) |
C9—C10—C11—C12 | 2.2 (7) | C46—C47—C48—C49 | −1.0 (5) |
C10—C11—C12—C13 | −2.1 (7) | C47—C48—C49—C50 | −0.1 (6) |
C9—C8—C13—C12 | 1.3 (7) | C48—C49—C50—C51 | 0.9 (6) |
N1—C8—C13—C12 | −176.9 (4) | C49—C50—C51—C46 | −0.5 (6) |
C11—C12—C13—C8 | 0.3 (7) | C47—C46—C51—C50 | −0.6 (6) |
C8—N1—C14—C19 | −136.3 (4) | N3—C46—C51—C50 | −178.9 (3) |
C1—N1—C14—C19 | 31.7 (5) | C46—N3—C52—C57 | −155.2 (3) |
C8—N1—C14—C15 | 44.8 (5) | C39—N3—C52—C57 | 19.4 (5) |
C1—N1—C14—C15 | −147.2 (4) | C46—N3—C52—C53 | 26.0 (5) |
C19—C14—C15—C16 | −0.3 (5) | C39—N3—C52—C53 | −159.4 (3) |
N1—C14—C15—C16 | 178.6 (3) | C57—C52—C53—C54 | −0.9 (5) |
C14—C15—C16—C17 | 0.3 (5) | N3—C52—C53—C54 | 177.9 (3) |
C15—C16—C17—C18 | 0.5 (5) | C52—C53—C54—C55 | 0.3 (5) |
C15—C16—C17—C20 | −178.5 (3) | C53—C54—C55—C56 | 0.4 (5) |
C16—C17—C18—C19 | −1.4 (5) | C53—C54—C55—C58 | −177.5 (3) |
C20—C17—C18—C19 | 177.7 (3) | C54—C55—C56—C57 | −0.4 (5) |
C17—C18—C19—C14 | 1.4 (5) | C58—C55—C56—C57 | 177.5 (3) |
C15—C14—C19—C18 | −0.5 (5) | C55—C56—C57—C52 | −0.3 (5) |
N1—C14—C19—C18 | −179.4 (3) | C53—C52—C57—C56 | 0.9 (5) |
C16—C17—C20—C21 | 36.5 (5) | N3—C52—C57—C56 | −177.9 (3) |
C18—C17—C20—C21 | −142.5 (4) | C54—C55—C58—C59 | 35.7 (5) |
C16—C17—C20—C25 | −144.8 (3) | C56—C55—C58—C59 | −142.1 (4) |
C18—C17—C20—C25 | 36.2 (5) | C54—C55—C58—C63 | −145.8 (3) |
C25—C20—C21—C22 | −0.2 (5) | C56—C55—C58—C63 | 36.4 (5) |
C17—C20—C21—C22 | 178.5 (3) | C63—C58—C59—C60 | −0.3 (5) |
C20—C21—C22—C23 | −0.1 (5) | C55—C58—C59—C60 | 178.3 (3) |
C21—C22—C23—C24 | 0.2 (5) | C58—C59—C60—C61 | −0.2 (5) |
C21—C22—C23—N2 | −178.3 (3) | C59—C60—C61—C62 | 0.5 (5) |
C33—N2—C23—C22 | 19.0 (5) | C59—C60—C61—N4 | −179.2 (3) |
C26—N2—C23—C22 | −154.3 (3) | C64—N4—C61—C60 | 34.4 (5) |
C33—N2—C23—C24 | −159.4 (3) | C71—N4—C61—C60 | −135.0 (4) |
C26—N2—C23—C24 | 27.3 (5) | C64—N4—C61—C62 | −145.4 (4) |
C22—C23—C24—C25 | 0.1 (5) | C71—N4—C61—C62 | 45.2 (5) |
N2—C23—C24—C25 | 178.5 (3) | C60—C61—C62—C63 | −0.4 (5) |
C23—C24—C25—C20 | −0.4 (5) | N4—C61—C62—C63 | 179.4 (3) |
C21—C20—C25—C24 | 0.5 (5) | C61—C62—C63—C58 | −0.1 (5) |
C17—C20—C25—C24 | −178.2 (3) | C59—C58—C63—C62 | 0.5 (5) |
C33—N2—C26—C27 | 47.7 (5) | C55—C58—C63—C62 | −178.1 (3) |
C23—N2—C26—C27 | −138.9 (3) | C61—N4—C64—C65 | 52.9 (5) |
C33—N2—C26—C31 | −130.2 (4) | C71—N4—C64—C65 | −137.8 (4) |
C23—N2—C26—C31 | 43.2 (5) | C61—N4—C64—C69 | −127.0 (4) |
C31—C26—C27—C28 | −1.7 (6) | C71—N4—C64—C69 | 42.3 (5) |
N2—C26—C27—C28 | −179.6 (3) | C69—C64—C65—C66 | 0.5 (6) |
C28—C29—C30—C31 | 0.3 (6) | N4—C64—C65—C66 | −179.3 (3) |
C27—C26—C31—C30 | 2.4 (5) | C64—C65—C66—C67 | 0.5 (6) |
N2—C26—C31—C30 | −179.7 (3) | C64—C65—C66—C70 | −176.3 (5) |
C29—C30—C31—C26 | −1.7 (5) | C70—C66—C67—C68 | 175.5 (5) |
C26—N2—C33—C38 | 49.6 (5) | C65—C66—C67—C68 | −1.0 (6) |
C23—N2—C33—C38 | −123.9 (4) | C66—C67—C68—C69 | 0.4 (7) |
C26—N2—C33—C34 | −129.5 (4) | C67—C68—C69—C64 | 0.7 (6) |
C23—N2—C33—C34 | 57.1 (5) | C65—C64—C69—C68 | −1.2 (6) |
C38—C33—C34—C35 | 1.1 (6) | N4—C64—C69—C68 | 178.7 (4) |
N2—C33—C34—C35 | −179.8 (4) | C64—N4—C71—C72 | 43.5 (5) |
C33—C34—C35—C36 | 0.0 (6) | C61—N4—C71—C72 | −147.3 (4) |
C34—C35—C36—C37 | −1.4 (7) | C64—N4—C71—C76 | −136.5 (4) |
C35—C36—C37—C38 | 1.6 (7) | C61—N4—C71—C76 | 32.6 (6) |
C35—C36—C37—C32B | 175.3 (5) | C76—C71—C72—C73 | −2.0 (6) |
C30—C29—C28—C27 | 0.5 (6) | N4—C71—C72—C73 | 178.0 (4) |
C30—C29—C28—C32A | −176.6 (7) | C71—C72—C73—C74 | 0.4 (6) |
C26—C27—C28—C29 | 0.2 (6) | C72—C73—C74—C75 | 1.3 (7) |
C26—C27—C28—C32A | 176.2 (8) | C73—C74—C75—C76 | −1.4 (7) |
C34—C33—C38—C37 | −1.0 (6) | C72—C71—C76—C75 | 1.8 (6) |
N2—C33—C38—C37 | 180.0 (4) | N4—C71—C76—C75 | −178.1 (4) |
C36—C37—C38—C33 | −0.4 (6) | C74—C75—C76—C71 | −0.1 (7) |
Experimental details
Crystal data | |
Chemical formula | C38H32N2 |
Mr | 516.66 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 90 |
a, b, c (Å) | 14.447 (2), 11.0153 (16), 17.803 (3) |
β (°) | 90.602 (3) |
V (Å3) | 2833.0 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.07 |
Crystal size (mm) | 0.30 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Plateform with APEX CCD detector diffractometer |
Absorption correction | Multi-scan (TWINABS in SAINT-Plus; Sheldrick, 1999) |
Tmin, Tmax | 0.971, 0.995 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10070, 10070, 4919 |
Rint | 0.000 |
(sin θ/λ)max (Å−1) | 0.682 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.063, 0.130, 0.90 |
No. of reflections | 10070 |
No. of parameters | 735 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.52, −0.29 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEPIII for Windows (Farrugia, 1997), SHELXL97 and local programs.
N1—C8 | 1.419 (4) | N3—C52 | 1.415 (4) |
N1—C1 | 1.422 (4) | N3—C46 | 1.428 (4) |
N1—C14 | 1.429 (4) | N3—C39 | 1.430 (4) |
N2—C33 | 1.420 (5) | N4—C64 | 1.416 (4) |
N2—C26 | 1.424 (4) | N4—C61 | 1.417 (4) |
N2—C23 | 1.428 (4) | N4—C71 | 1.418 (4) |
C17—C20 | 1.487 (4) | C55—C58 | 1.485 (4) |
C8—N1—C1 | 120.4 (3) | C52—N3—C46 | 122.0 (3) |
C8—N1—C14 | 120.3 (3) | C52—N3—C39 | 120.1 (3) |
C1—N1—C14 | 118.2 (3) | C46—N3—C39 | 117.7 (3) |
C33—N2—C26 | 118.7 (3) | C64—N4—C61 | 118.6 (3) |
C33—N2—C23 | 119.8 (3) | C64—N4—C71 | 120.6 (3) |
C26—N2—C23 | 121.1 (3) | C61—N4—C71 | 119.9 (3) |
C14—N1—C1—C2 | 54.0 (5) | C52—N3—C39—C44 | 55.9 (5) |
C8—N1—C1—C6 | 40.5 (5) | C46—N3—C39—C40 | 50.5 (5) |
C14—N1—C8—C13 | 31.4 (6) | C52—N3—C46—C47 | 44.0 (5) |
C1—N1—C8—C9 | 45.5 (5) | C39—N3—C46—C51 | 47.6 (5) |
C1—N1—C14—C19 | 31.7 (5) | C39—N3—C52—C57 | 19.4 (5) |
C8—N1—C14—C15 | 44.8 (5) | C46—N3—C52—C53 | 26.0 (5) |
C16—C17—C20—C21 | 36.5 (5) | C54—C55—C58—C59 | 35.7 (5) |
C18—C17—C20—C25 | 36.2 (5) | C56—C55—C58—C63 | 36.4 (5) |
C33—N2—C23—C22 | 19.0 (5) | C64—N4—C61—C60 | 34.4 (5) |
C26—N2—C23—C24 | 27.3 (5) | C71—N4—C61—C62 | 45.2 (5) |
C33—N2—C26—C27 | 47.7 (5) | C61—N4—C64—C65 | 52.9 (5) |
C23—N2—C26—C31 | 43.2 (5) | C71—N4—C64—C69 | 42.3 (5) |
C26—N2—C33—C38 | 49.6 (5) | C64—N4—C71—C72 | 43.5 (5) |
C23—N2—C33—C34 | 57.1 (5) | C61—N4—C71—C76 | 32.6 (6) |
The crystal structure of the title compound, TPD, (I), was first reported by a synchrotron single-crystal diffraction experiment with a microcrystal, on Station 9.8 of the Daresbury SRS, based on an orthorhombic structure of (I). The data were deposited in the Cambridge Structural Database, refcode 174279 (Kennedy et al., 2002), although the coordinates of several atoms were incorrect. The aim of the present work was to provide a complete structural analysis to correct this error in the existing literature mentioned above and to support the findings obtained from density-functional theory for predicting the reorganization energy (Malagoli & Brédas, 2000; Lin et al., 2003). \sch
Colorless crystals of (I) obtained in this study with more careful recrystallization experiments from morpholine revealed that the compound crystallizes in the monoclinic space group P21 [a = 14.447 (2), b = 11.0153 (16) and c = 17.803 (3) Å, β = 90.602 (3)° and Z = 4] with a pseudo-orthogonal lattice at 90 (2) K, rather than the orthorhombic space group P212121 (Kennedy et al., 2002). The β angle of monoclinic P21 is close to 90° and thus the crystals appear orthorhombic when twinned. The twinning phenomenon of (I) was frequently observed during our X-ray investigations. It is not possible to prevent twinning, even under idealized conditions such as low temperature, slow crystal growth or crystallization from different solvents. It is quite clear that the second polymorph of (I) proposed by Kennedy et al. does not exist, because the simulated profile of the monoclinic P21 structure has completely accounted for the peaks in the powder diffraction data. The additional peaks mentioned by Kennedy et al. arise from the reduction of symmetry from orthorhombic to monoclinic, with β = 90.602°, rather than from a form II of (I).
Selected geometric parameters for (I) are given in Table 1. In the structure of (I), the asymmetric unit consists of two independent molecules, A and B (Fig. 1), which are arranged along [100] to form vertical layers of alternately stacked A and B molecules (Fig. 2). Molecule A shows a great deal of rotational movement in the four terminal aryl rings, resulting in two disordered tolyl groups spilt over two sites, the occupancies of which refined to 64.4 (8)% for atom C32B and 35.6 (8)% for atom C32A. Molecule B exhibits a nearly cis configuration of the two terminal tolyls with respect to these ring planes.
Although the individual rings are essentially planar, the two central biphenyl groups are twisted as a consequence of the H atoms in the ortho positions, which introduce repulsive steric forces, resulting in non-planar π–π interactions across the C—C inter-ring bond. The magnitude of this twist is almost equivalent for the two independent molecules, such that the torsion angles are C16—C17—C20—C21 36.5 (5), C18—C17—C20—C25 36.2 (5), C56—C55—C58—C63 36.4 (5) and C54—C55—C58—C59 35.7 (5)°. The inter-ring distances are C17—C20 1.487 (4) and C55—C58 1.485 (4) Å, in close agreement with the values obtained in a recent theoretical study (Lin et al., 2003) and those of the neutron single-crystal diffraction data of an unsubstituted biphenyl (Cailleau & Baudour, 1979).
Four independent N atoms for both A and B molecules are nominally sp3 hybridized, but with some planarization of the molecule to take advantage of the resonance delocalization with the benzene rings, which leads to C—N—C bond angles close to 120°, displaying features of sp2 hybridization. The angle sums around these N atoms are ca 359° for atoms N1 and N4, and ca 360° for atoms N2 and N3 (Table 1). Molecular-orbital calculations also revealed that the highest occupied molecular orbital (HOMO) of (I) is strongly delocalized across all benzene rings of the molecule of (I), with significant contributions from the lone pair electrons of the N (Sugiyama et al., 1998). This geometric feature of molecules of (I) in the crystal lattice (similar to that of its radical cation state, i.e. sp2 hybridization and a planar conformation) provides favorable conditions for geometric reorganization during the charge-transfer process (Malagoli & Brédas, 2000). The N—C bond distances vary from 1.415 to 1.430 Å, and these results are in excellent agreement with the experimental crystal structure of triphenylamine (Sobolev et al., 1985).
The three rings connected to each N atom adopt a propeller-like orientation, with torsion angles (the plane of the rings with respect to the plane defined by the N atom and its three attached C atoms) varying from 31.4 (6)–54.0 (5)° for atom N1, 19.0 (5)–57.1 (5)° for N2, 19.4 (5)–55.9 (5)° for N3 and 32.6 (6)–52.9 (4)° for N4. The twisted conformation results from the steric effect of the H atoms in the ortho positions of the benzene rings. This twisted conformation can protect the N atoms from chemical attack, e.g. H-donors etc., to lose the hole-transport function, so that (I) has an excellent lifetime when used as a photoreceptor during the repetitive xerographic cycling process.