Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104025636/bm1582sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104025636/bm1582Isup2.hkl |
CCDC reference: 259034
Compound (I) was prepared by the method of Rosenhauer et al. (1929), but is now commercially available from Aldrich. Crystals of (I) were grown by slow evaporation of ethanol solutions, although good single crystals were extremely rare.
H atoms of the NH groups were clearly identified in difference syntheses and refined freely, but with N—H distances restrained equal (command SADI). Other H atoms were included using a riding model, with C—H bond lengths fixed at 0.95 Å, and with Uiso(H) = 1.2Ueq(C). The Flack parameter was refined on the basis of 7657 Friedel pairs.
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXL97.
C9H7NS | F(000) = 2688 |
Mr = 161.22 | Dx = 1.374 Mg m−3 |
Monoclinic, Cc | Mo Kα radiation, λ = 0.71073 Å |
a = 19.9772 (14) Å | Cell parameters from 5773 reflections |
b = 19.9588 (14) Å | θ = 2.8–29.6° |
c = 15.6622 (11) Å | µ = 0.34 mm−1 |
β = 93.014 (4)° | T = 133 K |
V = 6236.2 (8) Å3 | Block, brown-yellow |
Z = 32 | 0.28 × 0.24 × 0.24 mm |
Bruker SMART1000 CCD area-detector diffractometer | 12944 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.034 |
Graphite monochromator | θmax = 28.7°, θmin = 1.4° |
Detector resolution: 8.192 pixels mm-1 | h = −26→26 |
ω and ϕ scans | k = −26→26 |
44742 measured reflections | l = −20→20 |
15776 independent reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.034 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.078 | w = 1/[σ2(Fo2) + (0.0429P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.96 | (Δ/σ)max = 0.001 |
15776 reflections | Δρmax = 0.33 e Å−3 |
825 parameters | Δρmin = −0.18 e Å−3 |
30 restraints | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.03 (3) |
C9H7NS | V = 6236.2 (8) Å3 |
Mr = 161.22 | Z = 32 |
Monoclinic, Cc | Mo Kα radiation |
a = 19.9772 (14) Å | µ = 0.34 mm−1 |
b = 19.9588 (14) Å | T = 133 K |
c = 15.6622 (11) Å | 0.28 × 0.24 × 0.24 mm |
β = 93.014 (4)° |
Bruker SMART1000 CCD area-detector diffractometer | 12944 reflections with I > 2σ(I) |
44742 measured reflections | Rint = 0.034 |
15776 independent reflections |
R[F2 > 2σ(F2)] = 0.034 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.078 | Δρmax = 0.33 e Å−3 |
S = 0.96 | Δρmin = −0.18 e Å−3 |
15776 reflections | Absolute structure: Flack (1983) |
825 parameters | Absolute structure parameter: 0.03 (3) |
30 restraints |
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. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) − 13.0388 (0.0074) x + 14.7780 (0.0055) y − 1.9734 (0.0064) z = 3.8161 (0.0073) * 0.0018 (0.0010) S7 * 0.0104 (0.0014) N7 * 0.0017 (0.0015) C71 * −0.0072 (0.0016) C72 * −0.0083 (0.0017) C73 * 0.0001 (0.0018) C74 * 0.0146 (0.0018) C75 * 0.0024 (0.0019) C76 * −0.0104 (0.0017) C77 * −0.0027 (0.0016) C78 * −0.0024 (0.0016) C79 Rms deviation of fitted atoms = 0.0072 15.3630 (0.0050) x − 12.1731 (0.0076) y + 2.3590 (0.0058) z = 3.3949 (0.0105) Angle to previous plane (with approximate e.s.d.) = 10.19 (0.06) * 0.0618 (0.0010) S6 * −0.0651 (0.0014) N6 * −0.0043 (0.0016) C61 * 0.0153 (0.0016) C62 * −0.0020 (0.0016) C63 * −0.0318 (0.0017) C64 * −0.0073 (0.0017) C65 * 0.0395 (0.0018) C66 * 0.0453 (0.0016) C67 * −0.0099 (0.0015) C68 * −0.0415 (0.0016) C69 Rms deviation of fitted atoms = 0.0367 13.9239 (0.0068) x − 13.8573 (0.0055) y + 2.2306 (0.0062) z = 4.4646 (0.0072) Angle to previous plane (with approximate e.s.d.) = 6.40 (0.06) * −0.0380 (0.0009) S3 * 0.0279 (0.0014) N3 * 0.0023 (0.0015) C31 * −0.0132 (0.0015) C32 * 0.0088 (0.0015) C33 * 0.0280 (0.0017) C34 * −0.0046 (0.0017) C35 * −0.0314 (0.0017) C36 * −0.0235 (0.0016) C37 * 0.0084 (0.0016) C38 * 0.0352 (0.0017) C39 Rms deviation of fitted atoms = 0.0236 14.9790 (0.0054) x − 12.6653 (0.0078) y + 2.3130 (0.0060) z = 9.5053 (0.0098) Angle to previous plane (with approximate e.s.d.) = 4.59 (0.06) * 0.0247 (0.0010) S2 * −0.0287 (0.0014) N2 * 0.0001 (0.0015) C21 * 0.0108 (0.0016) C22 * −0.0019 (0.0016) C23 * −0.0130 (0.0017) C24 * −0.0084 (0.0018) C25 * 0.0192 (0.0018) C26 * 0.0233 (0.0016) C27 * −0.0061 (0.0015) C28 * −0.0199 (0.0016) C29 Rms deviation of fitted atoms = 0.0169 14.1806 (0.0056) x − 13.7452 (0.0068) y + 1.7273 (0.0061) z = 1.5265 (0.0081) Angle to previous plane (with approximate e.s.d.) = 4.47 (0.06) * 0.0316 (0.0010) S5 * −0.0316 (0.0014) N5 * 0.0002 (0.0015) C51 * 0.0191 (0.0015) C52 * 0.0006 (0.0016) C53 * −0.0335 (0.0017) C54 * −0.0027 (0.0017) C55 * 0.0256 (0.0017) C56 * 0.0308 (0.0016) C57 * −0.0013 (0.0016) C58 * −0.0389 (0.0016) C59 Rms deviation of fitted atoms = 0.0245 12.2587 (0.0078) x − 15.3875 (0.0052) y + 2.1615 (0.0064) z = 1.8935 (0.0104) Angle to previous plane (with approximate e.s.d.) = 7.37 (0.06) * −0.0615 (0.0010) S4 * 0.0514 (0.0014) N4 * 0.0025 (0.0016) C41 * −0.0115 (0.0017) C42 * 0.0090 (0.0016) C43 * 0.0298 (0.0018) C44 * 0.0016 (0.0018) C45 * −0.0449 (0.0018) C46 * −0.0429 (0.0016) C47 * 0.0207 (0.0016) C48 * 0.0458 (0.0016) C49 Rms deviation of fitted atoms = 0.0355 14.7393 (0.0056) x − 13.1283 (0.0075) y + 1.7635 (0.0062) z = 8.9734 (0.0075) Angle to previous plane (with approximate e.s.d.) = 9.70 (0.06) * 0.0028 (0.0010) S1 * 0.0007 (0.0014) N1 * 0.0001 (0.0016) C11 * 0.0042 (0.0016) C12 * −0.0040 (0.0016) C13 * −0.0108 (0.0017) C14 * 0.0067 (0.0018) C15 * 0.0059 (0.0017) C16 * −0.0030 (0.0016) C17 * 0.0016 (0.0015) C18 * −0.0044 (0.0017) C19 Rms deviation of fitted atoms = 0.0050 − 12.7364 (0.0076) x + 15.0918 (0.0055) y − 1.7830 (0.0065) z = 4.3777 (0.0098) Angle to previous plane (with approximate e.s.d.) = 8.06 (0.06) * 0.0174 (0.0010) S8 * −0.0165 (0.0014) N8 * −0.0010 (0.0016) C81 * 0.0085 (0.0016) C82 * −0.0063 (0.0017) C83 * −0.0083 (0.0017) C84 * −0.0007 (0.0018) C85 * 0.0129 (0.0018) C86 * 0.0134 (0.0016) C87 * −0.0044 (0.0015) C88 * −0.0150 (0.0017) C89 Rms deviation of fitted atoms = 0.0111 ============================================================================= Hydrogen bond angles at sulfur: 111.49 (0.48) H01 - S2 - C21 109.96 (0.47) H02 - S1 - C11 110.55 (0.45) H03 - S4 - C41 109.69 (0.46) H04 - S3 - C31 110.22 (0.47) H05 - S6 - C61 110.47 (0.54) H06 - S5 - C51 111.40 (0.46) H07 - S8 - C81 111.38 (0.54) H08 - S7 - C71 |
x | y | z | Uiso*/Ueq | ||
S1 | 0.81085 (3) | 0.26931 (3) | 0.31781 (3) | 0.03204 (12) | |
N1 | 0.75907 (8) | 0.23079 (8) | 0.46264 (10) | 0.0231 (3) | |
H01 | 0.7824 (10) | 0.2618 (9) | 0.4885 (12) | 0.035 (6)* | |
C11 | 0.76132 (9) | 0.22192 (10) | 0.37739 (11) | 0.0240 (4) | |
C12 | 0.71963 (9) | 0.16987 (10) | 0.34070 (12) | 0.0270 (4) | |
H12 | 0.7199 | 0.1615 | 0.2810 | 0.032* | |
C13 | 0.67992 (10) | 0.13240 (10) | 0.38904 (12) | 0.0294 (4) | |
H13 | 0.6527 | 0.0984 | 0.3628 | 0.035* | |
C14 | 0.67824 (9) | 0.14319 (10) | 0.47954 (12) | 0.0264 (4) | |
C15 | 0.63920 (10) | 0.10531 (11) | 0.53378 (13) | 0.0337 (5) | |
H15 | 0.6116 | 0.0703 | 0.5107 | 0.040* | |
C16 | 0.64061 (10) | 0.11855 (11) | 0.62007 (13) | 0.0338 (5) | |
H16 | 0.6138 | 0.0929 | 0.6562 | 0.041* | |
C17 | 0.68125 (10) | 0.16948 (10) | 0.65451 (12) | 0.0308 (4) | |
H17 | 0.6816 | 0.1785 | 0.7141 | 0.037* | |
C18 | 0.72102 (9) | 0.20691 (10) | 0.60338 (12) | 0.0262 (4) | |
H18 | 0.7492 | 0.2412 | 0.6274 | 0.031* | |
C19 | 0.71938 (9) | 0.19374 (9) | 0.51567 (11) | 0.0233 (4) | |
S2 | 0.84232 (3) | 0.34881 (3) | 0.57529 (3) | 0.03542 (12) | |
N2 | 0.89341 (8) | 0.38688 (8) | 0.42980 (9) | 0.0228 (3) | |
H02 | 0.8702 (9) | 0.3537 (9) | 0.4088 (12) | 0.031 (6)* | |
C21 | 0.89075 (9) | 0.39699 (10) | 0.51483 (11) | 0.0241 (4) | |
C22 | 0.93113 (9) | 0.45038 (10) | 0.55032 (12) | 0.0275 (4) | |
H22 | 0.9308 | 0.4595 | 0.6098 | 0.033* | |
C23 | 0.96984 (9) | 0.48810 (11) | 0.50070 (13) | 0.0296 (4) | |
H23 | 0.9958 | 0.5235 | 0.5259 | 0.036* | |
C24 | 0.97233 (9) | 0.47553 (10) | 0.41094 (12) | 0.0261 (4) | |
C25 | 1.01215 (10) | 0.51221 (11) | 0.35582 (13) | 0.0336 (5) | |
H25 | 1.0385 | 0.5486 | 0.3777 | 0.040* | |
C26 | 1.01323 (10) | 0.49578 (12) | 0.27089 (14) | 0.0365 (5) | |
H26 | 1.0407 | 0.5203 | 0.2344 | 0.044* | |
C27 | 0.97375 (10) | 0.44276 (10) | 0.23793 (12) | 0.0303 (4) | |
H27 | 0.9750 | 0.4316 | 0.1791 | 0.036* | |
C28 | 0.93341 (9) | 0.40675 (10) | 0.28935 (11) | 0.0256 (4) | |
H28 | 0.9063 | 0.3713 | 0.2663 | 0.031* | |
C29 | 0.93272 (9) | 0.42295 (9) | 0.37648 (11) | 0.0227 (4) | |
S3 | 0.90866 (2) | 0.68809 (3) | 0.58709 (3) | 0.02978 (11) | |
N3 | 0.87004 (7) | 0.62185 (8) | 0.44621 (9) | 0.0232 (3) | |
H03 | 0.8979 (9) | 0.6489 (9) | 0.4222 (12) | 0.025 (5)* | |
C31 | 0.86325 (9) | 0.63043 (9) | 0.53037 (11) | 0.0222 (4) | |
C32 | 0.81453 (9) | 0.58886 (10) | 0.56935 (12) | 0.0253 (4) | |
H32 | 0.8077 | 0.5934 | 0.6286 | 0.030* | |
C33 | 0.77838 (9) | 0.54337 (10) | 0.52223 (12) | 0.0260 (4) | |
H33 | 0.7469 | 0.5160 | 0.5494 | 0.031* | |
C34 | 0.78643 (9) | 0.53560 (9) | 0.43234 (12) | 0.0248 (4) | |
C35 | 0.74858 (10) | 0.49143 (11) | 0.37956 (13) | 0.0318 (5) | |
H35 | 0.7163 | 0.4632 | 0.4038 | 0.038* | |
C36 | 0.75755 (10) | 0.48844 (11) | 0.29307 (13) | 0.0338 (5) | |
H36 | 0.7316 | 0.4584 | 0.2579 | 0.041* | |
C37 | 0.80522 (10) | 0.53001 (11) | 0.25725 (12) | 0.0311 (4) | |
H37 | 0.8114 | 0.5278 | 0.1976 | 0.037* | |
C38 | 0.84312 (9) | 0.57379 (10) | 0.30693 (12) | 0.0271 (4) | |
H38 | 0.8752 | 0.6018 | 0.2820 | 0.033* | |
C39 | 0.83393 (9) | 0.57676 (9) | 0.39479 (11) | 0.0219 (4) | |
S4 | 0.97719 (3) | 0.70611 (3) | 0.33231 (3) | 0.03334 (12) | |
N4 | 1.02633 (7) | 0.75843 (8) | 0.47826 (10) | 0.0232 (3) | |
H04 | 0.9934 (8) | 0.7362 (10) | 0.4982 (12) | 0.025 (5)* | |
C41 | 1.03125 (9) | 0.75353 (10) | 0.39287 (12) | 0.0254 (4) | |
C42 | 1.08412 (10) | 0.79153 (10) | 0.35709 (13) | 0.0299 (4) | |
H42 | 1.0901 | 0.7894 | 0.2974 | 0.036* | |
C43 | 1.12538 (10) | 0.83010 (10) | 0.40710 (13) | 0.0320 (5) | |
H43 | 1.1602 | 0.8542 | 0.3818 | 0.038* | |
C44 | 1.11820 (9) | 0.83569 (10) | 0.49729 (12) | 0.0275 (4) | |
C45 | 1.15751 (10) | 0.87664 (11) | 0.55275 (14) | 0.0353 (5) | |
H45 | 1.1935 | 0.9014 | 0.5310 | 0.042* | |
C46 | 1.14509 (11) | 0.88165 (11) | 0.63745 (14) | 0.0382 (5) | |
H46 | 1.1718 | 0.9102 | 0.6738 | 0.046* | |
C47 | 1.09273 (10) | 0.84451 (11) | 0.67087 (13) | 0.0333 (5) | |
H47 | 1.0839 | 0.8485 | 0.7297 | 0.040* | |
C48 | 1.05417 (9) | 0.80237 (10) | 0.61899 (12) | 0.0276 (4) | |
H48 | 1.0196 | 0.7764 | 0.6421 | 0.033* | |
C49 | 1.06625 (9) | 0.79813 (9) | 0.53189 (11) | 0.0236 (4) | |
S5 | 0.57183 (3) | 0.52639 (3) | 0.39626 (3) | 0.03448 (12) | |
N5 | 0.51569 (7) | 0.49100 (8) | 0.53906 (9) | 0.0228 (3) | |
H05 | 0.5417 (9) | 0.5211 (9) | 0.5629 (12) | 0.026 (5)* | |
C51 | 0.51897 (9) | 0.48144 (10) | 0.45433 (11) | 0.0235 (4) | |
C52 | 0.47582 (9) | 0.43085 (10) | 0.41698 (12) | 0.0273 (4) | |
H52 | 0.4765 | 0.4222 | 0.3574 | 0.033* | |
C53 | 0.43422 (9) | 0.39525 (10) | 0.46456 (12) | 0.0269 (4) | |
H53 | 0.4061 | 0.3621 | 0.4379 | 0.032* | |
C54 | 0.43171 (9) | 0.40644 (10) | 0.55450 (12) | 0.0254 (4) | |
C55 | 0.39140 (9) | 0.36942 (11) | 0.60863 (13) | 0.0309 (4) | |
H55 | 0.3620 | 0.3361 | 0.5849 | 0.037* | |
C56 | 0.39397 (10) | 0.38089 (11) | 0.69520 (14) | 0.0344 (5) | |
H56 | 0.3664 | 0.3558 | 0.7310 | 0.041* | |
C57 | 0.43750 (10) | 0.42987 (11) | 0.73055 (13) | 0.0328 (5) | |
H57 | 0.4394 | 0.4374 | 0.7905 | 0.039* | |
C58 | 0.47745 (9) | 0.46704 (10) | 0.67980 (12) | 0.0279 (4) | |
H58 | 0.5068 | 0.5001 | 0.7043 | 0.034* | |
C59 | 0.47437 (9) | 0.45552 (9) | 0.59156 (12) | 0.0233 (4) | |
S6 | 0.60393 (3) | 0.60492 (3) | 0.65385 (3) | 0.03778 (13) | |
N6 | 0.65100 (7) | 0.64641 (8) | 0.50756 (10) | 0.0236 (3) | |
H06 | 0.6290 (11) | 0.6126 (9) | 0.4857 (14) | 0.046 (7)* | |
C61 | 0.64934 (9) | 0.65580 (10) | 0.59262 (12) | 0.0266 (4) | |
C62 | 0.68848 (10) | 0.71035 (10) | 0.62751 (13) | 0.0300 (4) | |
H62 | 0.6881 | 0.7193 | 0.6870 | 0.036* | |
C63 | 0.72571 (10) | 0.74923 (11) | 0.57835 (13) | 0.0315 (4) | |
H63 | 0.7509 | 0.7852 | 0.6035 | 0.038* | |
C64 | 0.72779 (9) | 0.73684 (10) | 0.48816 (12) | 0.0256 (4) | |
C65 | 0.76722 (10) | 0.77391 (11) | 0.43312 (14) | 0.0332 (5) | |
H65 | 0.7924 | 0.8112 | 0.4548 | 0.040* | |
C66 | 0.76970 (11) | 0.75685 (11) | 0.34874 (13) | 0.0360 (5) | |
H66 | 0.7970 | 0.7819 | 0.3125 | 0.043* | |
C67 | 0.73214 (10) | 0.70255 (11) | 0.31564 (13) | 0.0318 (4) | |
H67 | 0.7345 | 0.6907 | 0.2571 | 0.038* | |
C68 | 0.69176 (9) | 0.66616 (10) | 0.36743 (12) | 0.0257 (4) | |
H68 | 0.6656 | 0.6300 | 0.3446 | 0.031* | |
C69 | 0.68985 (9) | 0.68310 (9) | 0.45388 (12) | 0.0240 (4) | |
S7 | 0.66694 (2) | 0.93520 (3) | 0.66205 (3) | 0.02775 (11) | |
N7 | 0.62177 (8) | 0.87677 (8) | 0.51856 (9) | 0.0228 (3) | |
H07 | 0.6499 (9) | 0.9015 (9) | 0.4944 (12) | 0.024 (5)* | |
C71 | 0.61644 (9) | 0.88288 (9) | 0.60385 (11) | 0.0222 (4) | |
C72 | 0.56614 (9) | 0.84280 (10) | 0.64061 (12) | 0.0274 (4) | |
H72 | 0.5605 | 0.8454 | 0.7004 | 0.033* | |
C73 | 0.52649 (10) | 0.80128 (10) | 0.59220 (12) | 0.0301 (4) | |
H73 | 0.4935 | 0.7753 | 0.6185 | 0.036* | |
C74 | 0.53331 (9) | 0.79582 (10) | 0.50207 (12) | 0.0275 (4) | |
C75 | 0.49344 (11) | 0.75431 (11) | 0.44726 (14) | 0.0358 (5) | |
H75 | 0.4589 | 0.7281 | 0.4701 | 0.043* | |
C76 | 0.50372 (11) | 0.75112 (12) | 0.36161 (14) | 0.0384 (5) | |
H76 | 0.4767 | 0.7225 | 0.3256 | 0.046* | |
C77 | 0.55386 (10) | 0.78990 (11) | 0.32725 (13) | 0.0336 (5) | |
H77 | 0.5609 | 0.7872 | 0.2678 | 0.040* | |
C78 | 0.59316 (9) | 0.83191 (10) | 0.37827 (12) | 0.0278 (4) | |
H78 | 0.6267 | 0.8587 | 0.3543 | 0.033* | |
C79 | 0.58307 (9) | 0.83475 (9) | 0.46602 (11) | 0.0234 (4) | |
S8 | 0.73176 (3) | 0.95669 (3) | 0.40555 (3) | 0.03450 (12) | |
N8 | 0.77999 (8) | 1.01220 (8) | 0.54994 (9) | 0.0235 (3) | |
H08 | 0.7496 (10) | 0.9872 (11) | 0.5746 (14) | 0.045 (7)* | |
C81 | 0.78417 (9) | 1.00670 (10) | 0.46482 (11) | 0.0242 (4) | |
C82 | 0.83538 (10) | 1.04614 (10) | 0.42755 (12) | 0.0289 (4) | |
H82 | 0.8402 | 1.0442 | 0.3676 | 0.035* | |
C83 | 0.87674 (10) | 1.08580 (10) | 0.47606 (13) | 0.0304 (4) | |
H83 | 0.9106 | 1.1106 | 0.4497 | 0.037* | |
C84 | 0.87061 (9) | 1.09114 (10) | 0.56624 (12) | 0.0267 (4) | |
C85 | 0.91119 (11) | 1.13227 (11) | 0.62019 (13) | 0.0339 (5) | |
H85 | 0.9456 | 1.1583 | 0.5969 | 0.041* | |
C86 | 0.90156 (11) | 1.13525 (11) | 0.70658 (13) | 0.0356 (5) | |
H86 | 0.9291 | 1.1634 | 0.7425 | 0.043* | |
C87 | 0.85107 (10) | 1.09678 (10) | 0.74129 (12) | 0.0303 (4) | |
H87 | 0.8446 | 1.0992 | 0.8009 | 0.036* | |
C88 | 0.81064 (9) | 1.05550 (10) | 0.69065 (11) | 0.0263 (4) | |
H88 | 0.7767 | 1.0294 | 0.7149 | 0.032* | |
C89 | 0.82024 (9) | 1.05250 (9) | 0.60269 (11) | 0.0230 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0369 (3) | 0.0363 (3) | 0.0234 (2) | −0.0121 (2) | 0.0056 (2) | −0.0032 (2) |
N1 | 0.0251 (8) | 0.0217 (9) | 0.0225 (8) | −0.0034 (7) | 0.0017 (6) | −0.0024 (6) |
C11 | 0.0231 (9) | 0.0242 (10) | 0.0247 (9) | 0.0023 (8) | 0.0014 (7) | −0.0019 (7) |
C12 | 0.0289 (10) | 0.0277 (11) | 0.0241 (9) | −0.0014 (8) | −0.0009 (8) | −0.0042 (8) |
C13 | 0.0275 (10) | 0.0284 (11) | 0.0318 (10) | −0.0041 (8) | −0.0027 (8) | −0.0054 (8) |
C14 | 0.0234 (9) | 0.0249 (10) | 0.0307 (10) | 0.0000 (8) | 0.0003 (8) | 0.0000 (8) |
C15 | 0.0304 (10) | 0.0334 (12) | 0.0374 (11) | −0.0086 (9) | 0.0028 (9) | 0.0007 (9) |
C16 | 0.0305 (11) | 0.0356 (12) | 0.0362 (11) | −0.0033 (9) | 0.0095 (9) | 0.0061 (9) |
C17 | 0.0330 (10) | 0.0339 (12) | 0.0261 (10) | 0.0010 (9) | 0.0061 (8) | 0.0007 (8) |
C18 | 0.0269 (10) | 0.0242 (10) | 0.0276 (10) | −0.0024 (8) | 0.0022 (8) | −0.0025 (8) |
C19 | 0.0211 (9) | 0.0230 (10) | 0.0260 (9) | 0.0012 (7) | 0.0027 (7) | 0.0008 (7) |
S2 | 0.0395 (3) | 0.0430 (3) | 0.0246 (2) | −0.0177 (2) | 0.0095 (2) | −0.0066 (2) |
N2 | 0.0242 (8) | 0.0221 (8) | 0.0222 (8) | −0.0034 (7) | 0.0024 (6) | −0.0029 (6) |
C21 | 0.0225 (9) | 0.0266 (11) | 0.0233 (9) | 0.0008 (8) | 0.0013 (7) | −0.0025 (7) |
C22 | 0.0277 (10) | 0.0307 (11) | 0.0242 (9) | −0.0017 (8) | 0.0013 (7) | −0.0056 (8) |
C23 | 0.0241 (9) | 0.0312 (11) | 0.0331 (10) | −0.0048 (8) | −0.0021 (8) | −0.0059 (8) |
C24 | 0.0230 (9) | 0.0253 (11) | 0.0298 (10) | 0.0005 (8) | 0.0000 (7) | 0.0026 (8) |
C25 | 0.0293 (10) | 0.0328 (12) | 0.0384 (11) | −0.0103 (9) | −0.0002 (9) | 0.0052 (9) |
C26 | 0.0330 (11) | 0.0387 (13) | 0.0384 (11) | −0.0045 (9) | 0.0073 (9) | 0.0123 (10) |
C27 | 0.0331 (11) | 0.0333 (11) | 0.0247 (9) | 0.0026 (9) | 0.0042 (8) | 0.0033 (8) |
C28 | 0.0264 (9) | 0.0241 (10) | 0.0261 (9) | 0.0011 (8) | 0.0006 (7) | 0.0017 (7) |
C29 | 0.0204 (9) | 0.0219 (10) | 0.0257 (9) | 0.0025 (7) | 0.0013 (7) | 0.0034 (7) |
S3 | 0.0349 (3) | 0.0326 (3) | 0.0222 (2) | −0.0104 (2) | 0.0045 (2) | −0.00193 (19) |
N3 | 0.0237 (8) | 0.0226 (9) | 0.0237 (8) | −0.0038 (6) | 0.0048 (6) | 0.0008 (6) |
C31 | 0.0223 (9) | 0.0210 (9) | 0.0236 (9) | 0.0012 (7) | 0.0030 (7) | 0.0027 (7) |
C32 | 0.0285 (10) | 0.0248 (10) | 0.0231 (9) | 0.0021 (8) | 0.0056 (7) | 0.0054 (7) |
C33 | 0.0272 (9) | 0.0224 (10) | 0.0289 (10) | −0.0026 (8) | 0.0053 (8) | 0.0072 (8) |
C34 | 0.0249 (9) | 0.0196 (9) | 0.0300 (10) | 0.0011 (7) | 0.0011 (7) | 0.0027 (7) |
C35 | 0.0316 (10) | 0.0259 (11) | 0.0377 (12) | −0.0059 (9) | 0.0006 (9) | 0.0028 (9) |
C36 | 0.0343 (11) | 0.0305 (12) | 0.0357 (11) | −0.0053 (9) | −0.0058 (9) | −0.0046 (9) |
C37 | 0.0341 (10) | 0.0333 (12) | 0.0258 (10) | 0.0025 (9) | 0.0009 (8) | −0.0051 (8) |
C38 | 0.0255 (9) | 0.0275 (11) | 0.0290 (10) | 0.0002 (8) | 0.0063 (8) | −0.0002 (8) |
C39 | 0.0229 (9) | 0.0195 (9) | 0.0233 (9) | 0.0011 (7) | 0.0007 (7) | 0.0002 (7) |
S4 | 0.0414 (3) | 0.0351 (3) | 0.0243 (2) | −0.0125 (2) | 0.0095 (2) | −0.0045 (2) |
N4 | 0.0230 (8) | 0.0227 (8) | 0.0244 (8) | −0.0012 (7) | 0.0059 (6) | 0.0017 (6) |
C41 | 0.0299 (10) | 0.0214 (10) | 0.0257 (10) | 0.0012 (8) | 0.0084 (8) | 0.0026 (7) |
C42 | 0.0339 (10) | 0.0257 (11) | 0.0317 (10) | −0.0021 (8) | 0.0153 (8) | 0.0017 (8) |
C43 | 0.0284 (10) | 0.0271 (11) | 0.0414 (12) | −0.0018 (8) | 0.0114 (9) | 0.0064 (9) |
C44 | 0.0247 (9) | 0.0226 (10) | 0.0350 (10) | 0.0008 (8) | −0.0009 (8) | 0.0072 (8) |
C45 | 0.0304 (11) | 0.0275 (12) | 0.0472 (13) | −0.0065 (9) | −0.0056 (9) | 0.0098 (9) |
C46 | 0.0410 (12) | 0.0311 (12) | 0.0404 (12) | −0.0053 (10) | −0.0174 (10) | 0.0033 (9) |
C47 | 0.0343 (11) | 0.0350 (12) | 0.0297 (10) | 0.0027 (9) | −0.0061 (9) | 0.0020 (9) |
C48 | 0.0229 (9) | 0.0305 (11) | 0.0288 (10) | 0.0014 (8) | −0.0041 (8) | 0.0047 (8) |
C49 | 0.0211 (9) | 0.0208 (10) | 0.0286 (9) | 0.0040 (7) | −0.0012 (7) | 0.0016 (7) |
S5 | 0.0383 (3) | 0.0408 (3) | 0.0246 (2) | −0.0157 (2) | 0.0043 (2) | −0.0019 (2) |
N5 | 0.0210 (8) | 0.0238 (9) | 0.0237 (8) | −0.0037 (6) | 0.0012 (6) | −0.0029 (6) |
C51 | 0.0218 (9) | 0.0245 (10) | 0.0240 (9) | 0.0011 (7) | −0.0003 (7) | −0.0002 (7) |
C52 | 0.0278 (9) | 0.0266 (11) | 0.0266 (9) | −0.0006 (8) | −0.0058 (8) | −0.0035 (8) |
C53 | 0.0239 (9) | 0.0238 (10) | 0.0321 (10) | −0.0035 (8) | −0.0067 (8) | −0.0015 (8) |
C54 | 0.0194 (8) | 0.0233 (10) | 0.0332 (10) | 0.0028 (7) | −0.0013 (7) | 0.0018 (8) |
C55 | 0.0240 (10) | 0.0279 (11) | 0.0407 (12) | −0.0055 (8) | 0.0014 (8) | 0.0034 (9) |
C56 | 0.0296 (10) | 0.0328 (12) | 0.0415 (12) | −0.0035 (9) | 0.0103 (9) | 0.0083 (9) |
C57 | 0.0339 (11) | 0.0372 (12) | 0.0282 (10) | 0.0013 (9) | 0.0086 (8) | 0.0011 (9) |
C58 | 0.0269 (9) | 0.0262 (11) | 0.0310 (10) | −0.0018 (8) | 0.0048 (8) | −0.0022 (8) |
C59 | 0.0205 (9) | 0.0220 (10) | 0.0276 (9) | 0.0030 (7) | 0.0021 (7) | 0.0025 (7) |
S6 | 0.0407 (3) | 0.0466 (3) | 0.0269 (3) | −0.0182 (3) | 0.0089 (2) | −0.0082 (2) |
N6 | 0.0219 (8) | 0.0225 (9) | 0.0260 (8) | −0.0040 (7) | −0.0011 (6) | −0.0017 (7) |
C61 | 0.0205 (9) | 0.0299 (11) | 0.0292 (10) | 0.0008 (8) | 0.0006 (7) | −0.0039 (8) |
C62 | 0.0262 (9) | 0.0322 (11) | 0.0316 (10) | −0.0017 (8) | 0.0014 (8) | −0.0097 (8) |
C63 | 0.0235 (9) | 0.0286 (11) | 0.0421 (11) | −0.0045 (8) | −0.0014 (8) | −0.0097 (9) |
C64 | 0.0206 (9) | 0.0230 (10) | 0.0328 (10) | 0.0011 (7) | −0.0030 (7) | 0.0012 (8) |
C65 | 0.0278 (10) | 0.0267 (11) | 0.0444 (12) | −0.0058 (8) | −0.0046 (9) | 0.0035 (9) |
C66 | 0.0330 (11) | 0.0364 (12) | 0.0383 (12) | −0.0074 (9) | 0.0004 (9) | 0.0155 (9) |
C67 | 0.0350 (11) | 0.0319 (12) | 0.0281 (10) | −0.0019 (9) | −0.0019 (8) | 0.0081 (8) |
C68 | 0.0273 (9) | 0.0228 (10) | 0.0265 (9) | −0.0011 (8) | −0.0033 (7) | 0.0034 (7) |
C69 | 0.0194 (9) | 0.0209 (9) | 0.0315 (10) | 0.0031 (7) | −0.0002 (7) | 0.0039 (7) |
S7 | 0.0325 (3) | 0.0303 (3) | 0.0207 (2) | −0.0059 (2) | 0.00357 (18) | 0.00005 (19) |
N7 | 0.0231 (8) | 0.0241 (9) | 0.0213 (8) | −0.0017 (7) | 0.0038 (6) | 0.0013 (6) |
C71 | 0.0234 (9) | 0.0198 (10) | 0.0236 (9) | 0.0051 (7) | 0.0040 (7) | 0.0017 (7) |
C72 | 0.0297 (10) | 0.0263 (10) | 0.0267 (9) | 0.0019 (8) | 0.0081 (8) | 0.0051 (8) |
C73 | 0.0313 (10) | 0.0253 (11) | 0.0341 (11) | −0.0039 (8) | 0.0067 (8) | 0.0056 (8) |
C74 | 0.0263 (10) | 0.0228 (10) | 0.0335 (10) | 0.0008 (8) | 0.0028 (8) | 0.0009 (8) |
C75 | 0.0365 (11) | 0.0286 (12) | 0.0423 (12) | −0.0082 (9) | 0.0014 (9) | −0.0024 (9) |
C76 | 0.0377 (12) | 0.0309 (12) | 0.0459 (13) | −0.0061 (10) | −0.0050 (10) | −0.0097 (10) |
C77 | 0.0353 (11) | 0.0364 (12) | 0.0290 (10) | 0.0012 (9) | 0.0008 (8) | −0.0060 (9) |
C78 | 0.0257 (9) | 0.0296 (11) | 0.0281 (10) | −0.0007 (8) | 0.0030 (8) | −0.0034 (8) |
C79 | 0.0223 (9) | 0.0221 (10) | 0.0257 (9) | 0.0024 (7) | 0.0003 (7) | 0.0003 (7) |
S8 | 0.0436 (3) | 0.0377 (3) | 0.0229 (2) | −0.0159 (2) | 0.0082 (2) | −0.0056 (2) |
N8 | 0.0239 (8) | 0.0239 (9) | 0.0230 (8) | −0.0025 (7) | 0.0042 (6) | 0.0002 (6) |
C81 | 0.0278 (9) | 0.0227 (10) | 0.0225 (9) | −0.0006 (8) | 0.0057 (7) | −0.0005 (7) |
C82 | 0.0324 (10) | 0.0292 (11) | 0.0259 (10) | −0.0032 (8) | 0.0094 (8) | 0.0016 (8) |
C83 | 0.0316 (10) | 0.0271 (11) | 0.0332 (11) | −0.0038 (8) | 0.0080 (8) | 0.0052 (8) |
C84 | 0.0267 (9) | 0.0230 (10) | 0.0305 (10) | 0.0017 (8) | 0.0013 (8) | 0.0027 (8) |
C85 | 0.0357 (11) | 0.0275 (11) | 0.0382 (11) | −0.0070 (9) | −0.0018 (9) | 0.0039 (9) |
C86 | 0.0408 (12) | 0.0288 (12) | 0.0359 (11) | −0.0018 (9) | −0.0108 (9) | −0.0022 (9) |
C87 | 0.0358 (10) | 0.0312 (11) | 0.0232 (9) | 0.0052 (9) | −0.0045 (8) | −0.0016 (8) |
C88 | 0.0253 (9) | 0.0268 (11) | 0.0267 (9) | 0.0032 (8) | 0.0009 (7) | 0.0010 (8) |
C89 | 0.0220 (9) | 0.0221 (10) | 0.0248 (9) | 0.0036 (7) | −0.0002 (7) | −0.0006 (7) |
S1—C11 | 1.6856 (19) | C72—C73 | 1.351 (3) |
N1—C11 | 1.350 (2) | C73—C74 | 1.429 (3) |
N1—C19 | 1.391 (2) | C74—C79 | 1.403 (3) |
C11—C12 | 1.433 (3) | C74—C75 | 1.409 (3) |
C12—C13 | 1.351 (3) | C75—C76 | 1.369 (3) |
C13—C14 | 1.436 (3) | C76—C77 | 1.396 (3) |
C14—C19 | 1.402 (3) | C77—C78 | 1.375 (3) |
C14—C15 | 1.404 (3) | C78—C79 | 1.401 (2) |
C15—C16 | 1.376 (3) | S8—C81 | 1.689 (2) |
C16—C17 | 1.392 (3) | N8—C81 | 1.345 (2) |
C17—C18 | 1.378 (3) | N8—C89 | 1.381 (2) |
C18—C19 | 1.397 (3) | C81—C82 | 1.439 (3) |
S2—C21 | 1.6892 (19) | C82—C83 | 1.349 (3) |
N2—C21 | 1.351 (2) | C83—C84 | 1.428 (3) |
N2—C29 | 1.379 (2) | C84—C85 | 1.405 (3) |
C21—C22 | 1.431 (3) | C84—C89 | 1.412 (3) |
C22—C23 | 1.353 (3) | C85—C86 | 1.378 (3) |
C23—C24 | 1.432 (3) | C86—C87 | 1.400 (3) |
C24—C29 | 1.405 (3) | C87—C88 | 1.376 (3) |
C24—C25 | 1.409 (3) | C88—C89 | 1.402 (3) |
C25—C26 | 1.371 (3) | N1—H01 | 0.863 (14) |
C26—C27 | 1.402 (3) | C12—H12 | 0.9500 |
C27—C28 | 1.372 (3) | C13—H13 | 0.9500 |
C28—C29 | 1.403 (2) | C15—H15 | 0.9500 |
S3—C31 | 1.6887 (19) | C16—H16 | 0.9500 |
N3—C31 | 1.343 (2) | C17—H17 | 0.9500 |
N3—C39 | 1.385 (2) | C18—H18 | 0.9500 |
C31—C32 | 1.439 (2) | N2—H02 | 0.864 (14) |
C32—C33 | 1.354 (3) | C22—H22 | 0.9500 |
C33—C34 | 1.434 (3) | C23—H23 | 0.9500 |
C34—C35 | 1.402 (3) | C25—H25 | 0.9500 |
C34—C39 | 1.407 (3) | C26—H26 | 0.9500 |
C35—C36 | 1.377 (3) | C27—H27 | 0.9500 |
C36—C37 | 1.402 (3) | C28—H28 | 0.9500 |
C37—C38 | 1.371 (3) | N3—H03 | 0.874 (13) |
C38—C39 | 1.399 (2) | C32—H32 | 0.9500 |
S4—C41 | 1.689 (2) | C33—H33 | 0.9500 |
N4—C41 | 1.350 (2) | C35—H35 | 0.9500 |
N4—C49 | 1.378 (2) | C36—H36 | 0.9500 |
C41—C42 | 1.438 (3) | C37—H37 | 0.9500 |
C42—C43 | 1.348 (3) | C38—H38 | 0.9500 |
C43—C44 | 1.432 (3) | N4—H04 | 0.866 (13) |
C44—C45 | 1.403 (3) | C42—H42 | 0.9500 |
C44—C49 | 1.411 (3) | C43—H43 | 0.9500 |
C45—C46 | 1.366 (3) | C45—H45 | 0.9500 |
C46—C47 | 1.405 (3) | C46—H46 | 0.9500 |
C47—C48 | 1.377 (3) | C47—H47 | 0.9500 |
C48—C49 | 1.400 (3) | C48—H48 | 0.9500 |
S5—C51 | 1.6876 (19) | N5—H05 | 0.865 (14) |
N5—C51 | 1.346 (2) | C52—H52 | 0.9500 |
N5—C59 | 1.389 (2) | C53—H53 | 0.9500 |
C51—C52 | 1.432 (3) | C55—H55 | 0.9500 |
C52—C53 | 1.348 (3) | C56—H56 | 0.9500 |
C53—C54 | 1.430 (3) | C57—H57 | 0.9500 |
C54—C59 | 1.404 (3) | C58—H58 | 0.9500 |
C54—C55 | 1.409 (3) | N6—H06 | 0.867 (14) |
C55—C56 | 1.373 (3) | C62—H62 | 0.9500 |
C56—C57 | 1.403 (3) | C63—H63 | 0.9500 |
C57—C58 | 1.373 (3) | C65—H65 | 0.9500 |
C58—C59 | 1.399 (3) | C66—H66 | 0.9500 |
S6—C61 | 1.693 (2) | C67—H67 | 0.9500 |
N6—C61 | 1.347 (2) | C68—H68 | 0.9500 |
N6—C69 | 1.384 (2) | N7—H07 | 0.851 (13) |
C61—C62 | 1.432 (3) | C72—H72 | 0.9500 |
C62—C63 | 1.345 (3) | C73—H73 | 0.9500 |
C63—C64 | 1.437 (3) | C75—H75 | 0.9500 |
C64—C69 | 1.404 (3) | C76—H76 | 0.9500 |
C64—C65 | 1.408 (3) | C77—H77 | 0.9500 |
C65—C66 | 1.368 (3) | C78—H78 | 0.9500 |
C66—C67 | 1.402 (3) | N8—H08 | 0.888 (14) |
C67—C68 | 1.380 (3) | C82—H82 | 0.9500 |
C68—C69 | 1.398 (3) | C83—H83 | 0.9500 |
S7—C71 | 1.6859 (19) | C85—H85 | 0.9500 |
N7—C71 | 1.351 (2) | C86—H86 | 0.9500 |
N7—C79 | 1.383 (2) | C87—H87 | 0.9500 |
C71—C72 | 1.429 (3) | C88—H88 | 0.9500 |
C11—N1—C19 | 124.79 (16) | C89—C84—C83 | 117.33 (17) |
N1—C11—C12 | 116.29 (17) | C86—C85—C84 | 120.7 (2) |
N1—C11—S1 | 121.67 (14) | C85—C86—C87 | 119.88 (19) |
C12—C11—S1 | 122.04 (14) | C88—C87—C86 | 121.18 (18) |
C13—C12—C11 | 121.51 (17) | C87—C88—C89 | 119.04 (18) |
C12—C13—C14 | 121.00 (18) | N8—C89—C88 | 120.48 (17) |
C19—C14—C15 | 118.41 (18) | N8—C89—C84 | 118.77 (16) |
C19—C14—C13 | 117.58 (17) | C88—C89—C84 | 120.74 (17) |
C15—C14—C13 | 123.99 (18) | C11—N1—H01 | 120.9 (14) |
C16—C15—C14 | 120.50 (19) | C19—N1—H01 | 114.3 (14) |
C15—C16—C17 | 120.16 (19) | C13—C12—H12 | 119.2 |
C18—C17—C16 | 120.88 (18) | C11—C12—H12 | 119.2 |
C17—C18—C19 | 119.01 (18) | C12—C13—H13 | 119.5 |
N1—C19—C18 | 120.16 (17) | C14—C13—H13 | 119.5 |
N1—C19—C14 | 118.82 (16) | C16—C15—H15 | 119.7 |
C18—C19—C14 | 121.02 (17) | C14—C15—H15 | 119.7 |
C21—N2—C29 | 124.91 (16) | C15—C16—H16 | 119.9 |
N2—C21—C22 | 116.33 (16) | C17—C16—H16 | 119.9 |
N2—C21—S2 | 121.40 (14) | C18—C17—H17 | 119.6 |
C22—C21—S2 | 122.27 (14) | C16—C17—H17 | 119.6 |
C23—C22—C21 | 121.23 (17) | C17—C18—H18 | 120.5 |
C22—C23—C24 | 121.12 (18) | C19—C18—H18 | 120.5 |
C29—C24—C25 | 118.52 (18) | C21—N2—H02 | 116.2 (14) |
C29—C24—C23 | 117.40 (17) | C29—N2—H02 | 118.8 (14) |
C25—C24—C23 | 124.08 (19) | C23—C22—H22 | 119.4 |
C26—C25—C24 | 120.5 (2) | C21—C22—H22 | 119.4 |
C25—C26—C27 | 120.02 (19) | C22—C23—H23 | 119.4 |
C28—C27—C26 | 121.05 (18) | C24—C23—H23 | 119.4 |
C27—C28—C29 | 119.09 (18) | C26—C25—H25 | 119.7 |
N2—C29—C28 | 120.25 (17) | C24—C25—H25 | 119.7 |
N2—C29—C24 | 118.98 (16) | C25—C26—H26 | 120.0 |
C28—C29—C24 | 120.77 (17) | C27—C26—H26 | 120.0 |
C31—N3—C39 | 125.25 (16) | C28—C27—H27 | 119.5 |
N3—C31—C32 | 116.63 (16) | C26—C27—H27 | 119.5 |
N3—C31—S3 | 121.60 (14) | C27—C28—H28 | 120.5 |
C32—C31—S3 | 121.76 (14) | C29—C28—H28 | 120.5 |
C33—C32—C31 | 120.56 (17) | C31—N3—H03 | 116.3 (13) |
C32—C33—C34 | 121.56 (17) | C39—N3—H03 | 118.4 (13) |
C35—C34—C39 | 118.38 (17) | C33—C32—H32 | 119.7 |
C35—C34—C33 | 124.19 (17) | C31—C32—H32 | 119.7 |
C39—C34—C33 | 117.40 (17) | C32—C33—H33 | 119.2 |
C36—C35—C34 | 120.87 (19) | C34—C33—H33 | 119.2 |
C35—C36—C37 | 119.62 (19) | C36—C35—H35 | 119.6 |
C38—C37—C36 | 121.09 (18) | C34—C35—H35 | 119.6 |
C37—C38—C39 | 119.21 (18) | C35—C36—H36 | 120.2 |
N3—C39—C38 | 120.55 (17) | C37—C36—H36 | 120.2 |
N3—C39—C34 | 118.58 (16) | C38—C37—H37 | 119.5 |
C38—C39—C34 | 120.84 (17) | C36—C37—H37 | 119.5 |
C41—N4—C49 | 125.14 (16) | C37—C38—H38 | 120.4 |
N4—C41—C42 | 116.19 (17) | C39—C38—H38 | 120.4 |
N4—C41—S4 | 121.27 (14) | C41—N4—H04 | 114.6 (13) |
C42—C41—S4 | 122.53 (14) | C49—N4—H04 | 120.1 (13) |
C43—C42—C41 | 120.94 (18) | C43—C42—H42 | 119.5 |
C42—C43—C44 | 121.85 (18) | C41—C42—H42 | 119.5 |
C45—C44—C49 | 118.08 (18) | C42—C43—H43 | 119.1 |
C45—C44—C43 | 125.07 (18) | C44—C43—H43 | 119.1 |
C49—C44—C43 | 116.82 (18) | C46—C45—H45 | 119.3 |
C46—C45—C44 | 121.3 (2) | C44—C45—H45 | 119.3 |
C45—C46—C47 | 120.0 (2) | C45—C46—H46 | 120.0 |
C48—C47—C46 | 120.45 (19) | C47—C46—H46 | 120.0 |
C47—C48—C49 | 119.49 (18) | C48—C47—H47 | 119.8 |
N4—C49—C48 | 120.31 (17) | C46—C47—H47 | 119.8 |
N4—C49—C44 | 119.02 (16) | C47—C48—H48 | 120.3 |
C48—C49—C44 | 120.65 (18) | C49—C48—H48 | 120.3 |
C51—N5—C59 | 124.93 (16) | C51—N5—H05 | 117.6 (14) |
N5—C51—C52 | 116.31 (17) | C59—N5—H05 | 117.4 (14) |
N5—C51—S5 | 121.36 (14) | C53—C52—H52 | 119.3 |
C52—C51—S5 | 122.33 (14) | C51—C52—H52 | 119.3 |
C53—C52—C51 | 121.41 (17) | C52—C53—H53 | 119.4 |
C52—C53—C54 | 121.14 (17) | C54—C53—H53 | 119.4 |
C59—C54—C55 | 118.09 (17) | C56—C55—H55 | 119.5 |
C59—C54—C53 | 117.67 (17) | C54—C55—H55 | 119.5 |
C55—C54—C53 | 124.18 (18) | C55—C56—H56 | 120.1 |
C56—C55—C54 | 120.92 (19) | C57—C56—H56 | 120.1 |
C55—C56—C57 | 119.74 (18) | C58—C57—H57 | 119.5 |
C58—C57—C56 | 121.00 (19) | C56—C57—H57 | 119.5 |
C57—C58—C59 | 119.10 (18) | C57—C58—H58 | 120.5 |
N5—C59—C58 | 120.28 (17) | C59—C58—H58 | 120.5 |
N5—C59—C54 | 118.53 (17) | C61—N6—H06 | 117.5 (16) |
C58—C59—C54 | 121.14 (17) | C69—N6—H06 | 117.5 (16) |
C61—N6—C69 | 124.82 (16) | C63—C62—H62 | 119.1 |
N6—C61—C62 | 116.21 (17) | C61—C62—H62 | 119.1 |
N6—C61—S6 | 121.23 (15) | C62—C63—H63 | 119.7 |
C62—C61—S6 | 122.55 (15) | C64—C63—H63 | 119.7 |
C63—C62—C61 | 121.84 (18) | C66—C65—H65 | 119.7 |
C62—C63—C64 | 120.60 (18) | C64—C65—H65 | 119.7 |
C69—C64—C65 | 118.40 (17) | C65—C66—H66 | 119.9 |
C69—C64—C63 | 117.68 (17) | C67—C66—H66 | 119.9 |
C65—C64—C63 | 123.89 (18) | C68—C67—H67 | 119.8 |
C66—C65—C64 | 120.70 (19) | C66—C67—H67 | 119.8 |
C65—C66—C67 | 120.24 (19) | C67—C68—H68 | 120.4 |
C68—C67—C66 | 120.49 (19) | C69—C68—H68 | 120.4 |
C67—C68—C69 | 119.24 (18) | C71—N7—H07 | 118.4 (14) |
N6—C69—C68 | 120.36 (17) | C79—N7—H07 | 116.6 (13) |
N6—C69—C64 | 118.74 (17) | C73—C72—H72 | 119.3 |
C68—C69—C64 | 120.90 (17) | C71—C72—H72 | 119.3 |
C71—N7—C79 | 124.93 (16) | C72—C73—H73 | 119.4 |
N7—C71—C72 | 116.20 (17) | C74—C73—H73 | 119.4 |
N7—C71—S7 | 120.96 (14) | C76—C75—H75 | 119.5 |
C72—C71—S7 | 122.84 (14) | C74—C75—H75 | 119.5 |
C73—C72—C71 | 121.41 (17) | C75—C76—H76 | 120.0 |
C72—C73—C74 | 121.16 (18) | C77—C76—H76 | 120.0 |
C79—C74—C75 | 118.03 (18) | C78—C77—H77 | 119.6 |
C79—C74—C73 | 117.48 (18) | C76—C77—H77 | 119.6 |
C75—C74—C73 | 124.49 (18) | C77—C78—H78 | 120.4 |
C76—C75—C74 | 121.0 (2) | C79—C78—H78 | 120.4 |
C75—C76—C77 | 120.0 (2) | C81—N8—H08 | 117.6 (15) |
C78—C77—C76 | 120.88 (19) | C89—N8—H08 | 117.2 (15) |
C77—C78—C79 | 119.18 (19) | C83—C82—H82 | 119.3 |
N7—C79—C78 | 120.25 (17) | C81—C82—H82 | 119.3 |
N7—C79—C74 | 118.82 (16) | C82—C83—H83 | 119.4 |
C78—C79—C74 | 120.92 (17) | C84—C83—H83 | 119.4 |
C81—N8—C89 | 125.18 (16) | C86—C85—H85 | 119.7 |
N8—C81—C82 | 116.12 (17) | C84—C85—H85 | 119.7 |
N8—C81—S8 | 121.62 (14) | C85—C86—H86 | 120.1 |
C82—C81—S8 | 122.27 (14) | C87—C86—H86 | 120.1 |
C83—C82—C81 | 121.33 (17) | C88—C87—H87 | 119.4 |
C82—C83—C84 | 121.26 (18) | C86—C87—H87 | 119.4 |
C85—C84—C89 | 118.49 (17) | C87—C88—H88 | 120.5 |
C85—C84—C83 | 124.18 (18) | C89—C88—H88 | 120.5 |
C19—N1—C11—C12 | −0.5 (3) | C59—N5—C51—C52 | 0.4 (3) |
C19—N1—C11—S1 | 179.85 (14) | C59—N5—C51—S5 | −179.00 (14) |
N1—C11—C12—C13 | 0.6 (3) | N5—C51—C52—C53 | 0.2 (3) |
S1—C11—C12—C13 | −179.70 (16) | S5—C51—C52—C53 | 179.64 (15) |
C11—C12—C13—C14 | −0.3 (3) | C51—C52—C53—C54 | −0.2 (3) |
C12—C13—C14—C19 | −0.2 (3) | C52—C53—C54—C59 | −0.4 (3) |
C12—C13—C14—C15 | −178.7 (2) | C52—C53—C54—C55 | −177.47 (19) |
C19—C14—C15—C16 | 1.1 (3) | C59—C54—C55—C56 | −0.2 (3) |
C13—C14—C15—C16 | 179.7 (2) | C53—C54—C55—C56 | 176.87 (19) |
C14—C15—C16—C17 | −0.4 (3) | C54—C55—C56—C57 | −0.3 (3) |
C15—C16—C17—C18 | −0.6 (3) | C55—C56—C57—C58 | 0.4 (3) |
C16—C17—C18—C19 | 0.9 (3) | C56—C57—C58—C59 | 0.0 (3) |
C11—N1—C19—C18 | 179.77 (18) | C51—N5—C59—C58 | 176.60 (18) |
C11—N1—C19—C14 | 0.0 (3) | C51—N5—C59—C54 | −1.0 (3) |
C17—C18—C19—N1 | −179.97 (17) | C57—C58—C59—N5 | −178.07 (17) |
C17—C18—C19—C14 | −0.2 (3) | C57—C58—C59—C54 | −0.5 (3) |
C15—C14—C19—N1 | 178.95 (17) | C55—C54—C59—N5 | 178.23 (16) |
C13—C14—C19—N1 | 0.3 (3) | C53—C54—C59—N5 | 1.0 (2) |
C15—C14—C19—C18 | −0.8 (3) | C55—C54—C59—C58 | 0.6 (3) |
C13—C14—C19—C18 | −179.43 (17) | C53—C54—C59—C58 | −176.64 (17) |
C29—N2—C21—C22 | 1.4 (3) | C69—N6—C61—C62 | 3.4 (3) |
C29—N2—C21—S2 | −178.47 (14) | C69—N6—C61—S6 | −175.96 (14) |
N2—C21—C22—C23 | −0.3 (3) | N6—C61—C62—C63 | −1.1 (3) |
S2—C21—C22—C23 | 179.63 (16) | S6—C61—C62—C63 | 178.20 (16) |
C21—C22—C23—C24 | −0.6 (3) | C61—C62—C63—C64 | −0.4 (3) |
C22—C23—C24—C29 | 0.5 (3) | C62—C63—C64—C69 | 0.0 (3) |
C22—C23—C24—C25 | −179.11 (19) | C62—C63—C64—C65 | −177.84 (19) |
C29—C24—C25—C26 | −1.5 (3) | C69—C64—C65—C66 | −1.6 (3) |
C23—C24—C25—C26 | 178.1 (2) | C63—C64—C65—C66 | 176.2 (2) |
C24—C25—C26—C27 | 0.9 (3) | C64—C65—C66—C67 | 0.9 (3) |
C25—C26—C27—C28 | 0.3 (3) | C65—C66—C67—C68 | 0.7 (3) |
C26—C27—C28—C29 | −1.0 (3) | C66—C67—C68—C69 | −1.4 (3) |
C21—N2—C29—C28 | 177.81 (17) | C61—N6—C69—C68 | 175.23 (17) |
C21—N2—C29—C24 | −1.6 (3) | C61—N6—C69—C64 | −3.9 (3) |
C27—C28—C29—N2 | −179.01 (17) | C67—C68—C69—N6 | −178.47 (17) |
C27—C28—C29—C24 | 0.4 (3) | C67—C68—C69—C64 | 0.7 (3) |
C25—C24—C29—N2 | −179.79 (17) | C65—C64—C69—N6 | 179.97 (17) |
C23—C24—C29—N2 | 0.6 (3) | C63—C64—C69—N6 | 2.0 (3) |
C25—C24—C29—C28 | 0.8 (3) | C65—C64—C69—C68 | 0.8 (3) |
C23—C24—C29—C28 | −178.82 (17) | C63—C64—C69—C68 | −177.12 (17) |
C39—N3—C31—C32 | 0.3 (3) | C79—N7—C71—C72 | −0.7 (3) |
C39—N3—C31—S3 | −178.66 (14) | C79—N7—C71—S7 | 179.32 (14) |
N3—C31—C32—C33 | 0.5 (3) | N7—C71—C72—C73 | 0.1 (3) |
S3—C31—C32—C33 | 179.45 (15) | S7—C71—C72—C73 | −179.94 (16) |
C31—C32—C33—C34 | −0.9 (3) | C71—C72—C73—C74 | 0.0 (3) |
C32—C33—C34—C35 | −177.25 (19) | C72—C73—C74—C79 | 0.5 (3) |
C32—C33—C34—C39 | 0.6 (3) | C72—C73—C74—C75 | −179.3 (2) |
C39—C34—C35—C36 | −0.1 (3) | C79—C74—C75—C76 | 1.2 (3) |
C33—C34—C35—C36 | 177.67 (19) | C73—C74—C75—C76 | −179.0 (2) |
C34—C35—C36—C37 | 0.1 (3) | C74—C75—C76—C77 | −0.7 (3) |
C35—C36—C37—C38 | −0.1 (3) | C75—C76—C77—C78 | −0.4 (3) |
C36—C37—C38—C39 | 0.1 (3) | C76—C77—C78—C79 | 1.0 (3) |
C31—N3—C39—C38 | 177.42 (18) | C71—N7—C79—C78 | −179.48 (17) |
C31—N3—C39—C34 | −0.6 (3) | C71—N7—C79—C74 | 1.2 (3) |
C37—C38—C39—N3 | −178.09 (17) | C77—C78—C79—N7 | −179.76 (18) |
C37—C38—C39—C34 | −0.1 (3) | C77—C78—C79—C74 | −0.5 (3) |
C35—C34—C39—N3 | 178.14 (17) | C75—C74—C79—N7 | 178.72 (17) |
C33—C34—C39—N3 | 0.2 (3) | C73—C74—C79—N7 | −1.1 (3) |
C35—C34—C39—C38 | 0.1 (3) | C75—C74—C79—C78 | −0.6 (3) |
C33—C34—C39—C38 | −177.84 (17) | C73—C74—C79—C78 | 179.62 (18) |
C49—N4—C41—C42 | 2.1 (3) | C89—N8—C81—C82 | 0.4 (3) |
C49—N4—C41—S4 | −176.98 (14) | C89—N8—C81—S8 | −179.13 (14) |
N4—C41—C42—C43 | −0.7 (3) | N8—C81—C82—C83 | 0.4 (3) |
S4—C41—C42—C43 | 178.42 (16) | S8—C81—C82—C83 | 179.99 (17) |
C41—C42—C43—C44 | −0.7 (3) | C81—C82—C83—C84 | −1.1 (3) |
C42—C43—C44—C45 | −177.5 (2) | C82—C83—C84—C85 | −178.9 (2) |
C42—C43—C44—C49 | 0.8 (3) | C82—C83—C84—C89 | 1.0 (3) |
C49—C44—C45—C46 | −1.7 (3) | C89—C84—C85—C86 | −0.6 (3) |
C43—C44—C45—C46 | 176.6 (2) | C83—C84—C85—C86 | 179.2 (2) |
C44—C45—C46—C47 | 1.1 (3) | C84—C85—C86—C87 | 0.3 (3) |
C45—C46—C47—C48 | 0.7 (3) | C85—C86—C87—C88 | 0.2 (3) |
C46—C47—C48—C49 | −1.8 (3) | C86—C87—C88—C89 | −0.4 (3) |
C41—N4—C49—C48 | 176.25 (18) | C81—N8—C89—C88 | 178.68 (17) |
C41—N4—C49—C44 | −2.1 (3) | C81—N8—C89—C84 | −0.6 (3) |
C47—C48—C49—N4 | −177.21 (17) | C87—C88—C89—N8 | −179.21 (17) |
C47—C48—C49—C44 | 1.1 (3) | C87—C88—C89—C84 | 0.0 (3) |
C45—C44—C49—N4 | 178.94 (17) | C85—C84—C89—N8 | 179.72 (17) |
C43—C44—C49—N4 | 0.5 (3) | C83—C84—C89—N8 | −0.1 (3) |
C45—C44—C49—C48 | 0.6 (3) | C85—C84—C89—C88 | 0.5 (3) |
C43—C44—C49—C48 | −177.82 (17) | C83—C84—C89—C88 | −179.39 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H01···S2 | 0.86 (1) | 2.48 (1) | 3.3345 (17) | 174 (2) |
N2—H02···S1 | 0.86 (1) | 2.47 (1) | 3.3166 (16) | 167 (2) |
N3—H03···S4 | 0.87 (1) | 2.46 (1) | 3.3156 (16) | 168 (2) |
N4—H04···S3 | 0.87 (1) | 2.44 (1) | 3.2898 (16) | 166 (2) |
N5—H05···S6 | 0.87 (1) | 2.49 (1) | 3.3431 (17) | 170 (2) |
N6—H06···S5 | 0.87 (1) | 2.46 (2) | 3.3149 (16) | 169 (2) |
N7—H07···S8 | 0.85 (1) | 2.46 (1) | 3.3037 (16) | 170 (2) |
N8—H08···S7 | 0.89 (1) | 2.43 (1) | 3.3109 (16) | 169 (2) |
C18—H18···S2 | 0.95 | 2.98 | 3.768 (2) | 141 |
C28—H28···S1 | 0.95 | 2.93 | 3.719 (2) | 141 |
C38—H38···S4 | 0.95 | 2.99 | 3.767 (2) | 140 |
C48—H48···S3 | 0.95 | 2.93 | 3.708 (2) | 140 |
C58—H58···S6 | 0.95 | 2.99 | 3.772 (2) | 141 |
C68—H68···S5 | 0.95 | 2.93 | 3.720 (2) | 141 |
C78—H78···S8 | 0.95 | 2.95 | 3.732 (2) | 141 |
C88—H88···S7 | 0.95 | 2.97 | 3.751 (2) | 140 |
C28—H28···S3i | 0.95 | 3.05 | 3.701 (2) | 127 |
C72—H72···S4ii | 0.95 | 2.91 | 3.6996 (19) | 142 |
C12—H12···S7i | 0.95 | 2.85 | 3.6091 (19) | 138 |
C26—H26···S7iii | 0.95 | 2.95 | 3.845 (2) | 157 |
Symmetry codes: (i) x, −y+1, z−1/2; (ii) x−1/2, −y+3/2, z+1/2; (iii) x+1/2, −y+3/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C9H7NS |
Mr | 161.22 |
Crystal system, space group | Monoclinic, Cc |
Temperature (K) | 133 |
a, b, c (Å) | 19.9772 (14), 19.9588 (14), 15.6622 (11) |
β (°) | 93.014 (4) |
V (Å3) | 6236.2 (8) |
Z | 32 |
Radiation type | Mo Kα |
µ (mm−1) | 0.34 |
Crystal size (mm) | 0.28 × 0.24 × 0.24 |
Data collection | |
Diffractometer | Bruker SMART1000 CCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 44742, 15776, 12944 |
Rint | 0.034 |
(sin θ/λ)max (Å−1) | 0.676 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.078, 0.96 |
No. of reflections | 15776 |
No. of parameters | 825 |
No. of restraints | 30 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.33, −0.18 |
Absolute structure | Flack (1983) |
Absolute structure parameter | 0.03 (3) |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP (Siemens, 1994), SHELXL97.
S1—C11 | 1.6856 (19) | S5—C51 | 1.6876 (19) |
N1—C11 | 1.350 (2) | N5—C51 | 1.346 (2) |
N1—C19 | 1.391 (2) | N5—C59 | 1.389 (2) |
C12—C13 | 1.351 (3) | C52—C53 | 1.348 (3) |
C13—C14 | 1.436 (3) | C53—C54 | 1.430 (3) |
S2—C21 | 1.6892 (19) | S6—C61 | 1.693 (2) |
N2—C21 | 1.351 (2) | N6—C61 | 1.347 (2) |
N2—C29 | 1.379 (2) | N6—C69 | 1.384 (2) |
C22—C23 | 1.353 (3) | C62—C63 | 1.345 (3) |
C23—C24 | 1.432 (3) | C63—C64 | 1.437 (3) |
S3—C31 | 1.6887 (19) | S7—C71 | 1.6859 (19) |
N3—C31 | 1.343 (2) | N7—C71 | 1.351 (2) |
N3—C39 | 1.385 (2) | N7—C79 | 1.383 (2) |
C32—C33 | 1.354 (3) | C72—C73 | 1.351 (3) |
C33—C34 | 1.434 (3) | C73—C74 | 1.429 (3) |
S4—C41 | 1.689 (2) | S8—C81 | 1.689 (2) |
N4—C41 | 1.350 (2) | N8—C81 | 1.345 (2) |
N4—C49 | 1.378 (2) | N8—C89 | 1.381 (2) |
C42—C43 | 1.348 (3) | C82—C83 | 1.349 (3) |
C43—C44 | 1.432 (3) | C83—C84 | 1.428 (3) |
C11—N1—C19 | 124.79 (16) | C51—N5—C59 | 124.93 (16) |
C21—N2—C29 | 124.91 (16) | C61—N6—C69 | 124.82 (16) |
C31—N3—C39 | 125.25 (16) | C71—N7—C79 | 124.93 (16) |
C41—N4—C49 | 125.14 (16) | C81—N8—C89 | 125.18 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H01···S2 | 0.863 (14) | 2.475 (14) | 3.3345 (17) | 174.2 (19) |
N2—H02···S1 | 0.864 (14) | 2.468 (14) | 3.3166 (16) | 167.2 (19) |
N3—H03···S4 | 0.874 (13) | 2.456 (14) | 3.3156 (16) | 168.0 (18) |
N4—H04···S3 | 0.866 (13) | 2.444 (14) | 3.2898 (16) | 165.8 (18) |
N5—H05···S6 | 0.865 (14) | 2.488 (14) | 3.3431 (17) | 169.7 (18) |
N6—H06···S5 | 0.867 (14) | 2.461 (15) | 3.3149 (16) | 169 (2) |
N7—H07···S8 | 0.851 (13) | 2.463 (14) | 3.3037 (16) | 169.7 (18) |
N8—H08···S7 | 0.888 (14) | 2.434 (14) | 3.3109 (16) | 169 (2) |
C18—H18···S2 | 0.95 | 2.98 | 3.768 (2) | 141 |
C28—H28···S3i | 0.95 | 3.05 | 3.701 (2) | 127 |
C72—H72···S4ii | 0.95 | 2.91 | 3.6996 (19) | 142 |
C12—H12···S7i | 0.95 | 2.85 | 3.6091 (19) | 138 |
C26—H26···S7iii | 0.95 | 2.95 | 3.845 (2) | 157 |
Symmetry codes: (i) x, −y+1, z−1/2; (ii) x−1/2, −y+3/2, z+1/2; (iii) x+1/2, −y+3/2, z−1/2. |
Bond | mol. 1 | mol. 2 | mol. 3 | mol. 4 | mol. 5 | mol. 6 | mol. 7 | mol. 8 |
S═C1 | 1.689 | 1.693 | 1.692 | 1.693 | 1.691 | 1.697 | 1.689 | 1.692 |
N—C1 | 1.352 | 1.353 | 1.345 | 1.352 | 1.348 | 1.350 | 1.353 | 1.347 |
C1—C2 | 1.437 | 1.436 | 1.443 | 1.441 | 1.437 | 1.436 | 1.433 | 1.443 |
C2—C3 | 1.354 | 1.357 | 1.357 | 1.351 | 1.350 | 1.348 | 1.354 | 1.352 |
C3—C4 | 1.438 | 1.434 | 1.436 | 1.434 | 1.433 | 1.440 | 1.432 | 1.430 |
C4—C5 | 1.407 | 1.412 | 1.405 | 1.405 | 1.412 | 1.411 | 1.412 | 1.407 |
C5—C6 | 1.378 | 1.374 | 1.379 | 1.369 | 1.376 | 1.371 | 1.372 | 1.380 |
C6—C7 | 1.396 | 1.406 | 1.406 | 1.409 | 1.407 | 1.406 | 1.400 | 1.404 |
C7—C8 | 1.380 | 1.375 | 1.374 | 1.379 | 1.376 | 1.383 | 1.378 | 1.379 |
N—C9 | 1.393 | 1.382 | 1.387 | 1.381 | 1.392 | 1.387 | 1.385 | 1.383 |
C4—C9 | 1.406 | 1.409 | 1.411 | 1.415 | 1.408 | 1.408 | 1.408 | 1.416 |
C8—C9 | 1.400 | 1.408 | 1.401 | 1.403 | 1.402 | 1.401 | 1.403 | 1.405 |
We are interested in the structures and optical properties of formal `mercaptans' of aromatic N-heterocycles, in which, however, the usual tautomer is the thione form, with a double bond to the S atom and a protonated N atom. We have published studies of 2-mercaptothiazoline (thiazoline-2-thione; Flakus Tyl & Jones, 2002) and 4-mercaptopyridine (pyridine-4-thione; Flakus Miros & Jones, 2002); the former consists of inversion-symmetric dimers, hydrogen-bonded by N—H···S═C systems, whereas the latter forms zigzag chains, also via N—H···S═C hydrogen bonds. Pyridine-2-thione (Reynolds et al., 1995) also forms inversion-symmetric dimers, and it has found use as a ligand in transition metal chemistry (Reynolds et al., 1995; Usón et al., 1990).
Here, we report the structure of quinoline-2(1H)-thione (I), an important reagent in analytical chemistry (Karagiannidis et al., 1990; Paneli & Voulgaropoulos, 1991; Steed & Tocher, 1992; Leeaphon et al., 1993; Kitagawa et al., 1993; Aslanidis et al., 1998). Solution IR spectra (Flakus, 1994) indicated the presence of inversion-symmetric hydrogen-bonded dimers. Both the thione and the mercaptan forms have been found in low-temperature matrices by IR spectroscopy (Prusinowska et al., 1995). \sch
The structure determination of (I) establishes the presence of the expected thione form of the molecule, but the most striking feature is the presence of eight independent molecules (Fig. 1). The Cambridge Structural Database (CSD, Version 7/04; Allen, 2002) contains only 61 hits with Z' ≥ 8, out of a total of 322421 entries. We can see no evidence that unrecognized twinning or structure modulation has led to an inappropriate cell, and a variety of programs have failed to indicate any overlooked symmetry. Together with the Flack parameter (Flack, 1983) of 0.03 (3), this is good evidence for the absence of a global inversion centre, despite the rather high mean (E2-1) value of 0.869.
All eight molecules of (I) are closely similar and essentially planar (all mean deviations of non-H atoms from planarity are less than 0.03 Å). The molecular dimensions may be regarded as normal, e.g. the short N—C1 and longer N—C9 bonds, the short C2—C3 and long C3—C4 bonds consistent with the thione tautomer, the C═S bond lengths, and the widened angle at N typical of protonated pyridinic systems (Table 1). Note that the numbering is chosen to allow an easy comparison of the independent molecules (the first digit of each atom label is the molecule number) and does not correspond to the IUPAC numbering. Rigid-body libration corrections (Schomaker & Trueblood, 1968) can be applied successfully because of the lack of torsional degrees of freedom, and lie in the range 0.002–0.005 Å (Table 3).
The molecules form the expected inversion-symmetric pairs via N—H···S hydrogen bonding (Fig. 1, Table 2), although the symmetry is only approximate rather than exact. Thus, the ring systems within each pair are not exactly parallel [interplanar angles: molecule 1/molecule 2 2.54 (6), 2/3 6.51 (6), 5/6 6.17 (6), 7/8 1.45 (6)°, with planes calculated through all non-H atoms]. The H···S═C angles are in the range 109.7 (5)–111.5 (5)°. Each H atom at C8 is forced into proximity with the S atom of the hydrogen-bonded partner, but these contacts (one of which is given as an example in Table 2) should not necessarily be regarded as hydrogen bonds. Similarly, the other C—H···S contacts given for completeness in Table 2 may not be of great structural significance.
The extended packing in the region z ≈ 0 involves chains of hydrogen-bonded pairs parallel to [110] (Fig. 2), or to [110] in the region z ≈ 1/2. Each chain consists of only one type of pair, e.g. only molecules 1 and 2. The chains lie in common layers in which only translational symmetry is involved. In Fig. 2, successive pairs in the chain are related by the C-centring operator (x − 1/2, 1/2 + y, z), while the operator (1/2 + x, 1/2 + y, z) transforms one chain into its counterpart four chains lower.
The current interest in crystal packing and `engineering' extends to structures with high Z' [see, for example, Steed (2003), and references therein]. Why should such effects arise? There seems, at first, to be little reason why compound (I) should have Z' = 8, when its smaller analogue pyridine-2-thione has Z' = 1 (Reynolds et al., 1995), although the lack of global symmetry in the hydrogen-bonded pairs could easily lead to Z' = 2. A rationalization may be sought in the stacking geometry within the layers of (I). As can be seen from Fig. 1, molecules 2, 3, 6 and 7 (with coordinates as chosen for the asymmetric unit) are stacked above each other. This is confirmed in Fig. 2, which shows two stacks, the second being composed of molecules 1, 4, 5 and 8 in that order. All the rings are approximately parallel (maximum interplanar angles 10°), but are offset, as is expected for stable packing (Hunter & Sanders, 1990). The offsetting is such that the central C4—C9 bond, common to both rings, lies above the centre of the pyridine ring of the neighbouring molecule in the stack. However, a closer inspection shows that the molecules thereby acquire different environments. If we denote the interaction of C4—C9 lying over the ring centre as →, then the four independent interactions in one stack are: molecule 7 → molecule 6 → molecule 3 → molecule 2 ← molecule 7' (generated by stack translation). This can be seen in Fig. 3. Thus the stacking is such that there are three interactions in one direction, but the fourth is in the opposite direction. This explains the factor 4 that changes Z' from 2 to 8. In the second independent stack, the interactions are analogous: molecule 1 → molecule 4 → molecule 5 → molecule 8 ← molecule 1'.
Thus one can, at least phenomenologically, explain the Z' value, although it would presumably be impossible, given the current state of knowledge, to predict the packing or explain the detailed causes. It would clearly be a worthwhile exercise to attempt to grow crystals of alternative polymorphs of (I), but in our hands the compound was most unwilling to crystallize adequately from any solvent.