


Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680706148X/sj2406sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S160053680706148X/sj2406Isup2.hkl |
CCDC reference: 673067
A mixture of (4R,5R)-4,5-bis(1-methylimidazolium-3-ethyl)-2,2-dimethly-1,3-dioxolane dibromide (0.46 g, 0.96 mmol), methanol (10 ml), pyridine (0.5 ml), sulfur (0.09 g, 2.89 mmol), and 1,8-diazabicyclo[5.4.0]undec-7-ene (0.64 g, 4.23 mmol) was heated at 338 K for 18 h. Once cooled to room temperature the mixture was opened to water (40 ml) and extracted with chloroform (3 × 20 ml). The combined extracts were dried over magnesium sulfate, filtered and concentrated under reduced pressure to leave a brown residue. The crude product was purified by column chromatography (SiO2, ethyl acetate: petroleum ether v/v 1:1, loaded as a dichloromethane solution) to give the title compound (0.34 g, 93%) as a colourless solid which was recrystallized from diethyl ether, acetone (v/v 1:1) to give colourless blades of (I); mp 390 K.
The small crystal used for data collection was a weak scatterer, which may correlate with the rather high residuals.
The H atoms were placed in calculated positions (C—H = 0.95–1.00 Å) and refined as riding with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C). The methyl groups were allowed to rotate, but not to tip, to best fit the electron density.
Data collection: COLLECT (Nonius, 1998); cell refinement: HKL SCALEPACK (Otwinowski & Minor 1997); data reduction: HKL DENZO (Otwinowski & Minor 1997), HKL SCALEPACK (Otwinowski & Minor 1997) and SORTAV (Blessing 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
C17H26N4O2S2 | F(000) = 816 |
Mr = 382.54 | Dx = 1.278 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 10746 reflections |
a = 6.827 (5) Å | θ = 2.9–27.5° |
b = 20.732 (9) Å | µ = 0.29 mm−1 |
c = 14.071 (8) Å | T = 120 K |
β = 93.68 (2)° | Blade, colourless |
V = 1988 (4) Å3 | 0.15 × 0.07 × 0.03 mm |
Z = 4 |
Nonius KappaCCD diffractometer | 4275 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.131 |
Graphite monochromator | θmax = 27.7°, θmin = 3.0° |
ω and ϕ scans | h = −8→8 |
21365 measured reflections | k = −26→26 |
8499 independent reflections | l = −18→18 |
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)] = 0.097 | H-atom parameters constrained |
wR(F2) = 0.241 | w = 1/[σ2(Fo2) + (0.1095P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max < 0.001 |
8499 reflections | Δρmax = 1.19 e Å−3 |
458 parameters | Δρmin = −0.38 e Å−3 |
1 restraint | Absolute structure: Flack (1983), with 3717 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.03 (14) |
C17H26N4O2S2 | V = 1988 (4) Å3 |
Mr = 382.54 | Z = 4 |
Monoclinic, P21 | Mo Kα radiation |
a = 6.827 (5) Å | µ = 0.29 mm−1 |
b = 20.732 (9) Å | T = 120 K |
c = 14.071 (8) Å | 0.15 × 0.07 × 0.03 mm |
β = 93.68 (2)° |
Nonius KappaCCD diffractometer | 4275 reflections with I > 2σ(I) |
21365 measured reflections | Rint = 0.131 |
8499 independent reflections |
R[F2 > 2σ(F2)] = 0.097 | H-atom parameters constrained |
wR(F2) = 0.241 | Δρmax = 1.19 e Å−3 |
S = 1.01 | Δρmin = −0.38 e Å−3 |
8499 reflections | Absolute structure: Flack (1983), with 3717 Friedel pairs |
458 parameters | Absolute structure parameter: 0.03 (14) |
1 restraint |
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 | ||
S1 | 1.0766 (3) | −0.09444 (11) | 0.37993 (15) | 0.0358 (6) | |
S2 | 1.1011 (3) | 0.25588 (10) | 0.38446 (15) | 0.0379 (6) | |
O1 | 0.9082 (7) | 0.0267 (2) | 0.7294 (3) | 0.0281 (13) | |
O2 | 0.9200 (8) | 0.1377 (2) | 0.7253 (4) | 0.0319 (14) | |
N1 | 0.6913 (9) | −0.0893 (3) | 0.4156 (4) | 0.0287 (15) | |
N2 | 0.8869 (8) | −0.0746 (3) | 0.5447 (4) | 0.0225 (15) | |
N3 | 1.3291 (10) | 0.2429 (3) | 0.5522 (4) | 0.0322 (16) | |
N4 | 1.4920 (9) | 0.2678 (3) | 0.4321 (4) | 0.0313 (16) | |
C1 | 0.8820 (11) | −0.0868 (4) | 0.4470 (6) | 0.0286 (19) | |
C2 | 0.5784 (11) | −0.0793 (4) | 0.4942 (6) | 0.0283 (19) | |
H2 | 0.4391 | −0.0788 | 0.4916 | 0.034* | |
C3 | 0.6915 (12) | −0.0707 (4) | 0.5710 (6) | 0.034 (2) | |
H3 | 0.6502 | −0.0633 | 0.6333 | 0.041* | |
C4 | 1.0701 (12) | −0.0718 (4) | 0.6069 (6) | 0.033 (2) | |
H4A | 1.1718 | −0.0987 | 0.5790 | 0.039* | |
H4B | 1.0455 | −0.0898 | 0.6702 | 0.039* | |
C5 | 1.1441 (12) | −0.0030 (4) | 0.6182 (6) | 0.034 (2) | |
H5A | 1.2525 | −0.0024 | 0.6684 | 0.041* | |
H5B | 1.1993 | 0.0104 | 0.5579 | 0.041* | |
C6 | 0.9947 (13) | 0.0455 (4) | 0.6431 (5) | 0.034 (2) | |
H6 | 0.8902 | 0.0486 | 0.5901 | 0.041* | |
C7 | 1.0671 (13) | 0.1117 (4) | 0.6699 (6) | 0.035 (2) | |
H7 | 1.1940 | 0.1086 | 0.7093 | 0.042* | |
C8 | 1.0929 (14) | 0.1560 (4) | 0.5824 (6) | 0.039 (2) | |
H8A | 1.1866 | 0.1354 | 0.5410 | 0.046* | |
H8B | 0.9652 | 0.1597 | 0.5454 | 0.046* | |
C9 | 1.1676 (12) | 0.2245 (4) | 0.6086 (6) | 0.033 (2) | |
H9A | 1.0589 | 0.2558 | 0.5977 | 0.039* | |
H9B | 1.2114 | 0.2259 | 0.6770 | 0.039* | |
C10 | 1.5189 (14) | 0.2460 (4) | 0.5853 (6) | 0.039 (2) | |
H10 | 1.5697 | 0.2378 | 0.6486 | 0.046* | |
C11 | 1.6230 (11) | 0.2632 (4) | 0.5099 (6) | 0.037 (2) | |
H11 | 1.7604 | 0.2707 | 0.5110 | 0.044* | |
C12 | 1.3064 (11) | 0.2562 (4) | 0.4560 (6) | 0.0285 (19) | |
C13 | 0.8483 (12) | 0.0842 (4) | 0.7781 (5) | 0.034 (2) | |
C14 | 0.9443 (16) | 0.0811 (5) | 0.8777 (6) | 0.056 (3) | |
H14A | 0.9187 | 0.1213 | 0.9114 | 0.084* | |
H14B | 1.0862 | 0.0754 | 0.8745 | 0.084* | |
H14C | 0.8903 | 0.0447 | 0.9119 | 0.084* | |
C15 | 0.6255 (13) | 0.0889 (4) | 0.7705 (7) | 0.050 (3) | |
H15A | 0.5843 | 0.1265 | 0.8064 | 0.076* | |
H15B | 0.5694 | 0.0497 | 0.7966 | 0.076* | |
H15C | 0.5792 | 0.0935 | 0.7034 | 0.076* | |
C16 | 0.6178 (12) | −0.1033 (4) | 0.3189 (6) | 0.039 (2) | |
H16A | 0.4858 | −0.1218 | 0.3195 | 0.058* | |
H16B | 0.7054 | −0.1341 | 0.2903 | 0.058* | |
H16C | 0.6126 | −0.0633 | 0.2815 | 0.058* | |
C17 | 1.5424 (12) | 0.2842 (4) | 0.3361 (6) | 0.039 (2) | |
H17A | 1.6842 | 0.2913 | 0.3356 | 0.058* | |
H17B | 1.4727 | 0.3235 | 0.3152 | 0.058* | |
H17C | 1.5042 | 0.2487 | 0.2927 | 0.058* | |
S3 | 0.3242 (3) | −0.08682 (10) | −0.11152 (15) | 0.0346 (5) | |
S4 | 0.4476 (3) | 0.27361 (10) | −0.13945 (14) | 0.0315 (5) | |
O3 | 0.6325 (8) | 0.0390 (2) | 0.2112 (4) | 0.0354 (14) | |
O4 | 0.6722 (7) | 0.1490 (2) | 0.2102 (4) | 0.0318 (14) | |
N5 | −0.0519 (9) | −0.0961 (3) | −0.0621 (4) | 0.0286 (16) | |
N6 | 0.1467 (9) | −0.0640 (3) | 0.0544 (5) | 0.0290 (16) | |
N7 | 0.6796 (9) | 0.2483 (3) | 0.0229 (4) | 0.0239 (15) | |
N8 | 0.8460 (9) | 0.2680 (3) | −0.1002 (4) | 0.0284 (15) | |
C18 | 0.1379 (11) | −0.0834 (4) | −0.0398 (5) | 0.0272 (18) | |
C19 | −0.1644 (12) | −0.0857 (4) | 0.0162 (6) | 0.037 (2) | |
H19 | −0.3020 | −0.0916 | 0.0184 | 0.044* | |
C20 | −0.0388 (11) | −0.0657 (4) | 0.0878 (6) | 0.030 (2) | |
H20 | −0.0720 | −0.0547 | 0.1504 | 0.036* | |
C21 | 0.3238 (12) | −0.0426 (4) | 0.1091 (6) | 0.034 (2) | |
H21A | 0.4264 | −0.0762 | 0.1054 | 0.041* | |
H21B | 0.2945 | −0.0381 | 0.1768 | 0.041* | |
C22 | 0.4043 (12) | 0.0216 (4) | 0.0743 (6) | 0.034 (2) | |
H22A | 0.5163 | 0.0129 | 0.0349 | 0.041* | |
H22B | 0.3009 | 0.0434 | 0.0334 | 0.041* | |
C23 | 0.4715 (11) | 0.0666 (4) | 0.1552 (5) | 0.0289 (19) | |
H23 | 0.3603 | 0.0758 | 0.1961 | 0.035* | |
C24 | 0.5638 (12) | 0.1292 (3) | 0.1247 (5) | 0.0260 (19) | |
H24 | 0.6549 | 0.1209 | 0.0732 | 0.031* | |
C25 | 0.4178 (11) | 0.1814 (4) | 0.0942 (5) | 0.0258 (18) | |
H25A | 0.3175 | 0.1847 | 0.1418 | 0.031* | |
H25B | 0.3501 | 0.1692 | 0.0325 | 0.031* | |
C26 | 0.5161 (11) | 0.2471 (4) | 0.0840 (6) | 0.0288 (19) | |
H26A | 0.4158 | 0.2782 | 0.0587 | 0.035* | |
H26B | 0.5635 | 0.2622 | 0.1482 | 0.035* | |
C27 | 0.8729 (13) | 0.2427 (4) | 0.0525 (6) | 0.036 (2) | |
H27 | 0.9249 | 0.2326 | 0.1150 | 0.044* | |
C28 | 0.9747 (11) | 0.2542 (4) | −0.0237 (6) | 0.0288 (19) | |
H28 | 1.1136 | 0.2530 | −0.0248 | 0.035* | |
C29 | 0.6561 (11) | 0.2632 (4) | −0.0717 (5) | 0.0283 (19) | |
C30 | 0.7339 (12) | 0.0893 (4) | 0.2601 (6) | 0.037 (2) | |
C31 | 0.9550 (12) | 0.0815 (5) | 0.2540 (7) | 0.055 (3) | |
H31A | 1.0230 | 0.1175 | 0.2872 | 0.082* | |
H31B | 0.9866 | 0.0814 | 0.1871 | 0.082* | |
H31C | 0.9974 | 0.0408 | 0.2840 | 0.082* | |
C32 | 0.6749 (17) | 0.0963 (5) | 0.3611 (6) | 0.060 (3) | |
H32A | 0.7504 | 0.1312 | 0.3927 | 0.090* | |
H32B | 0.7014 | 0.0558 | 0.3957 | 0.090* | |
H32C | 0.5345 | 0.1062 | 0.3606 | 0.090* | |
C33 | −0.1337 (12) | −0.1177 (4) | −0.1555 (6) | 0.039 (2) | |
H33A | −0.2612 | −0.1382 | −0.1485 | 0.058* | |
H33B | −0.0440 | −0.1487 | −0.1823 | 0.058* | |
H33C | −0.1507 | −0.0805 | −0.1982 | 0.058* | |
C34 | 0.8937 (12) | 0.2850 (4) | −0.1942 (6) | 0.035 (2) | |
H34A | 1.0232 | 0.3055 | −0.1917 | 0.053* | |
H34B | 0.7950 | 0.3151 | −0.2219 | 0.053* | |
H34C | 0.8956 | 0.2461 | −0.2336 | 0.053* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0335 (13) | 0.0382 (13) | 0.0357 (12) | −0.0003 (11) | 0.0030 (10) | −0.0042 (10) |
S2 | 0.0347 (13) | 0.0385 (14) | 0.0395 (13) | −0.0065 (10) | −0.0047 (10) | 0.0006 (10) |
O1 | 0.034 (3) | 0.018 (3) | 0.033 (3) | −0.004 (2) | 0.010 (3) | 0.000 (2) |
O2 | 0.032 (3) | 0.024 (3) | 0.042 (3) | −0.002 (2) | 0.014 (3) | 0.007 (3) |
N1 | 0.040 (4) | 0.010 (3) | 0.035 (4) | 0.007 (3) | −0.004 (3) | 0.005 (3) |
N2 | 0.018 (3) | 0.023 (4) | 0.027 (3) | −0.009 (3) | 0.006 (3) | −0.001 (3) |
N3 | 0.039 (4) | 0.023 (4) | 0.034 (4) | 0.000 (3) | 0.005 (4) | −0.004 (3) |
N4 | 0.030 (4) | 0.033 (4) | 0.033 (4) | 0.001 (3) | 0.013 (3) | −0.001 (3) |
C1 | 0.023 (4) | 0.010 (4) | 0.051 (5) | −0.003 (3) | −0.012 (4) | 0.007 (4) |
C2 | 0.017 (4) | 0.027 (5) | 0.041 (5) | 0.000 (4) | 0.002 (4) | −0.002 (4) |
C3 | 0.038 (5) | 0.029 (5) | 0.037 (5) | −0.002 (4) | 0.021 (4) | −0.004 (4) |
C4 | 0.038 (5) | 0.024 (5) | 0.035 (5) | 0.010 (4) | −0.007 (4) | −0.004 (4) |
C5 | 0.039 (5) | 0.035 (5) | 0.029 (5) | 0.002 (4) | 0.001 (4) | −0.009 (4) |
C6 | 0.052 (6) | 0.030 (5) | 0.021 (4) | 0.008 (4) | 0.000 (4) | −0.007 (4) |
C7 | 0.052 (6) | 0.023 (5) | 0.031 (5) | 0.005 (4) | 0.006 (4) | −0.002 (4) |
C8 | 0.048 (6) | 0.036 (5) | 0.031 (5) | −0.015 (4) | 0.003 (4) | 0.009 (4) |
C9 | 0.036 (5) | 0.032 (5) | 0.031 (5) | −0.005 (4) | 0.004 (4) | −0.007 (4) |
C10 | 0.064 (7) | 0.022 (5) | 0.028 (5) | 0.012 (4) | −0.011 (5) | 0.000 (4) |
C11 | 0.018 (4) | 0.040 (6) | 0.052 (6) | −0.010 (4) | 0.003 (4) | −0.005 (5) |
C12 | 0.025 (4) | 0.020 (4) | 0.043 (5) | −0.001 (4) | 0.019 (4) | 0.003 (4) |
C13 | 0.046 (5) | 0.023 (5) | 0.036 (5) | −0.003 (4) | 0.016 (4) | 0.000 (4) |
C14 | 0.096 (8) | 0.039 (6) | 0.035 (5) | −0.009 (6) | 0.018 (5) | 0.000 (5) |
C15 | 0.042 (6) | 0.021 (5) | 0.090 (7) | −0.001 (4) | 0.023 (5) | 0.002 (5) |
C16 | 0.029 (5) | 0.044 (6) | 0.044 (5) | −0.008 (4) | 0.007 (4) | −0.011 (4) |
C17 | 0.031 (5) | 0.040 (6) | 0.046 (5) | −0.012 (4) | 0.008 (4) | −0.010 (4) |
S3 | 0.0304 (12) | 0.0326 (12) | 0.0412 (12) | −0.0007 (10) | 0.0048 (9) | −0.0001 (10) |
S4 | 0.0220 (11) | 0.0397 (13) | 0.0323 (11) | 0.0040 (10) | −0.0029 (9) | 0.0048 (10) |
O3 | 0.042 (3) | 0.014 (3) | 0.048 (4) | −0.001 (2) | −0.015 (3) | −0.001 (3) |
O4 | 0.029 (3) | 0.026 (3) | 0.038 (3) | 0.003 (2) | −0.015 (3) | 0.001 (2) |
N5 | 0.034 (4) | 0.017 (4) | 0.033 (4) | 0.002 (3) | −0.006 (3) | −0.003 (3) |
N6 | 0.029 (4) | 0.023 (4) | 0.034 (4) | 0.001 (3) | −0.006 (3) | 0.006 (3) |
N7 | 0.021 (4) | 0.029 (4) | 0.021 (3) | 0.002 (3) | 0.002 (3) | −0.004 (3) |
N8 | 0.028 (4) | 0.019 (4) | 0.038 (4) | 0.005 (3) | 0.003 (3) | 0.003 (3) |
C18 | 0.038 (5) | 0.015 (4) | 0.028 (4) | −0.009 (4) | 0.002 (4) | 0.006 (4) |
C19 | 0.033 (5) | 0.028 (5) | 0.049 (5) | −0.007 (4) | −0.001 (4) | −0.005 (4) |
C20 | 0.021 (5) | 0.030 (5) | 0.040 (5) | −0.004 (4) | 0.009 (4) | −0.003 (4) |
C21 | 0.038 (5) | 0.025 (5) | 0.037 (5) | −0.002 (4) | −0.005 (4) | 0.007 (4) |
C22 | 0.037 (5) | 0.023 (5) | 0.042 (5) | −0.012 (4) | 0.002 (4) | 0.001 (4) |
C23 | 0.026 (5) | 0.025 (5) | 0.035 (5) | 0.003 (3) | −0.005 (4) | −0.002 (4) |
C24 | 0.034 (5) | 0.024 (5) | 0.021 (4) | 0.010 (4) | 0.007 (4) | −0.005 (3) |
C25 | 0.026 (4) | 0.026 (5) | 0.024 (4) | 0.000 (3) | −0.010 (3) | −0.003 (3) |
C26 | 0.028 (5) | 0.020 (4) | 0.039 (5) | 0.000 (3) | 0.005 (4) | 0.002 (4) |
C27 | 0.057 (6) | 0.019 (5) | 0.031 (5) | −0.011 (4) | −0.013 (4) | 0.004 (4) |
C28 | 0.020 (4) | 0.022 (4) | 0.045 (5) | 0.004 (4) | 0.001 (4) | 0.008 (4) |
C29 | 0.029 (5) | 0.017 (4) | 0.041 (5) | −0.016 (4) | 0.017 (4) | −0.015 (4) |
C30 | 0.041 (5) | 0.027 (5) | 0.039 (5) | 0.001 (4) | −0.023 (4) | 0.007 (4) |
C31 | 0.045 (6) | 0.029 (5) | 0.086 (7) | −0.016 (5) | −0.025 (5) | 0.000 (6) |
C32 | 0.102 (9) | 0.035 (6) | 0.041 (6) | −0.014 (5) | −0.012 (6) | 0.007 (4) |
C33 | 0.035 (5) | 0.030 (5) | 0.050 (6) | −0.011 (4) | −0.002 (4) | 0.005 (4) |
C34 | 0.041 (5) | 0.027 (5) | 0.040 (5) | 0.013 (4) | 0.018 (4) | −0.004 (4) |
S1—C1 | 1.685 (9) | S3—C18 | 1.675 (8) |
S2—C12 | 1.672 (9) | S4—C29 | 1.675 (9) |
O1—C6 | 1.437 (9) | O3—C30 | 1.406 (9) |
O1—C13 | 1.447 (9) | O3—C23 | 1.430 (9) |
O2—C7 | 1.417 (10) | O4—C24 | 1.431 (9) |
O2—C13 | 1.439 (9) | O4—C30 | 1.471 (9) |
N1—C1 | 1.349 (9) | N5—C18 | 1.339 (9) |
N1—C2 | 1.403 (10) | N5—C19 | 1.400 (10) |
N1—C16 | 1.449 (10) | N5—C33 | 1.465 (10) |
N2—C1 | 1.397 (9) | N6—C20 | 1.379 (10) |
N2—C3 | 1.409 (10) | N6—C18 | 1.383 (9) |
N2—C4 | 1.480 (9) | N6—C21 | 1.460 (9) |
N3—C10 | 1.350 (11) | N7—C27 | 1.363 (10) |
N3—C12 | 1.381 (9) | N7—C29 | 1.366 (9) |
N3—C9 | 1.450 (10) | N7—C26 | 1.452 (9) |
N4—C12 | 1.353 (9) | N8—C28 | 1.375 (9) |
N4—C11 | 1.372 (10) | N8—C29 | 1.386 (9) |
N4—C17 | 1.456 (10) | N8—C34 | 1.426 (10) |
C2—C3 | 1.299 (10) | C19—C20 | 1.346 (10) |
C2—H2 | 0.9500 | C19—H19 | 0.9500 |
C3—H3 | 0.9500 | C20—H20 | 0.9500 |
C4—C5 | 1.518 (11) | C21—C22 | 1.533 (10) |
C4—H4A | 0.9900 | C21—H21A | 0.9900 |
C4—H4B | 0.9900 | C21—H21B | 0.9900 |
C5—C6 | 1.490 (11) | C22—C23 | 1.520 (10) |
C5—H5A | 0.9900 | C22—H22A | 0.9900 |
C5—H5B | 0.9900 | C22—H22B | 0.9900 |
C6—C7 | 1.500 (11) | C23—C24 | 1.517 (11) |
C6—H6 | 1.0000 | C23—H23 | 1.0000 |
C7—C8 | 1.554 (11) | C24—C25 | 1.515 (10) |
C7—H7 | 1.0000 | C24—H24 | 1.0000 |
C8—C9 | 1.546 (11) | C25—C26 | 1.529 (11) |
C8—H8A | 0.9900 | C25—H25A | 0.9900 |
C8—H8B | 0.9900 | C25—H25B | 0.9900 |
C9—H9A | 0.9900 | C26—H26A | 0.9900 |
C9—H9B | 0.9900 | C26—H26B | 0.9900 |
C10—C11 | 1.362 (11) | C27—C28 | 1.336 (11) |
C10—H10 | 0.9500 | C27—H27 | 0.9500 |
C11—H11 | 0.9500 | C28—H28 | 0.9500 |
C13—C14 | 1.511 (11) | C30—C32 | 1.510 (12) |
C13—C15 | 1.521 (11) | C30—C31 | 1.526 (12) |
C14—H14A | 0.9800 | C31—H31A | 0.9800 |
C14—H14B | 0.9800 | C31—H31B | 0.9800 |
C14—H14C | 0.9800 | C31—H31C | 0.9800 |
C15—H15A | 0.9800 | C32—H32A | 0.9800 |
C15—H15B | 0.9800 | C32—H32B | 0.9800 |
C15—H15C | 0.9800 | C32—H32C | 0.9800 |
C16—H16A | 0.9800 | C33—H33A | 0.9800 |
C16—H16B | 0.9800 | C33—H33B | 0.9800 |
C16—H16C | 0.9800 | C33—H33C | 0.9800 |
C17—H17A | 0.9800 | C34—H34A | 0.9800 |
C17—H17B | 0.9800 | C34—H34B | 0.9800 |
C17—H17C | 0.9800 | C34—H34C | 0.9800 |
C6—O1—C13 | 108.7 (5) | C30—O3—C23 | 108.0 (5) |
C7—O2—C13 | 105.5 (6) | C24—O4—C30 | 106.1 (5) |
C1—N1—C2 | 107.7 (6) | C18—N5—C19 | 110.9 (6) |
C1—N1—C16 | 125.7 (7) | C18—N5—C33 | 125.3 (7) |
C2—N1—C16 | 126.5 (6) | C19—N5—C33 | 123.8 (7) |
C1—N2—C3 | 107.8 (6) | C20—N6—C18 | 109.6 (6) |
C1—N2—C4 | 123.7 (6) | C20—N6—C21 | 125.1 (7) |
C3—N2—C4 | 128.4 (6) | C18—N6—C21 | 125.3 (7) |
C10—N3—C12 | 111.9 (7) | C27—N7—C29 | 111.6 (6) |
C10—N3—C9 | 124.8 (7) | C27—N7—C26 | 125.7 (6) |
C12—N3—C9 | 123.2 (7) | C29—N7—C26 | 122.3 (6) |
C12—N4—C11 | 111.3 (6) | C28—N8—C29 | 108.7 (6) |
C12—N4—C17 | 123.5 (7) | C28—N8—C34 | 127.2 (6) |
C11—N4—C17 | 125.2 (6) | C29—N8—C34 | 124.1 (6) |
N1—C1—N2 | 106.9 (7) | N5—C18—N6 | 105.3 (6) |
N1—C1—S1 | 126.3 (6) | N5—C18—S3 | 127.7 (6) |
N2—C1—S1 | 126.8 (5) | N6—C18—S3 | 127.0 (6) |
C3—C2—N1 | 110.4 (7) | C20—C19—N5 | 106.3 (7) |
C3—C2—H2 | 124.8 | C20—C19—H19 | 126.8 |
N1—C2—H2 | 124.8 | N5—C19—H19 | 126.8 |
C2—C3—N2 | 107.2 (7) | C19—C20—N6 | 107.9 (7) |
C2—C3—H3 | 126.4 | C19—C20—H20 | 126.1 |
N2—C3—H3 | 126.4 | N6—C20—H20 | 126.1 |
N2—C4—C5 | 111.2 (6) | N6—C21—C22 | 113.3 (6) |
N2—C4—H4A | 109.4 | N6—C21—H21A | 108.9 |
C5—C4—H4A | 109.4 | C22—C21—H21A | 108.9 |
N2—C4—H4B | 109.4 | N6—C21—H21B | 108.9 |
C5—C4—H4B | 109.4 | C22—C21—H21B | 108.9 |
H4A—C4—H4B | 108.0 | H21A—C21—H21B | 107.7 |
C6—C5—C4 | 115.5 (7) | C23—C22—C21 | 113.0 (7) |
C6—C5—H5A | 108.4 | C23—C22—H22A | 109.0 |
C4—C5—H5A | 108.4 | C21—C22—H22A | 109.0 |
C6—C5—H5B | 108.4 | C23—C22—H22B | 109.0 |
C4—C5—H5B | 108.4 | C21—C22—H22B | 109.0 |
H5A—C5—H5B | 107.5 | H22A—C22—H22B | 107.8 |
O1—C6—C5 | 109.8 (7) | O3—C23—C24 | 100.4 (6) |
O1—C6—C7 | 100.6 (6) | O3—C23—C22 | 110.6 (6) |
C5—C6—C7 | 117.2 (7) | C24—C23—C22 | 115.1 (7) |
O1—C6—H6 | 109.6 | O3—C23—H23 | 110.1 |
C5—C6—H6 | 109.6 | C24—C23—H23 | 110.1 |
C7—C6—H6 | 109.6 | C22—C23—H23 | 110.1 |
O2—C7—C6 | 104.6 (7) | O4—C24—C25 | 109.2 (6) |
O2—C7—C8 | 109.4 (7) | O4—C24—C23 | 102.1 (6) |
C6—C7—C8 | 113.2 (7) | C25—C24—C23 | 114.5 (7) |
O2—C7—H7 | 109.8 | O4—C24—H24 | 110.3 |
C6—C7—H7 | 109.8 | C25—C24—H24 | 110.3 |
C8—C7—H7 | 109.8 | C23—C24—H24 | 110.3 |
C9—C8—C7 | 114.0 (7) | C24—C25—C26 | 112.2 (6) |
C9—C8—H8A | 108.8 | C24—C25—H25A | 109.2 |
C7—C8—H8A | 108.8 | C26—C25—H25A | 109.2 |
C9—C8—H8B | 108.8 | C24—C25—H25B | 109.2 |
C7—C8—H8B | 108.8 | C26—C25—H25B | 109.2 |
H8A—C8—H8B | 107.6 | H25A—C25—H25B | 107.9 |
N3—C9—C8 | 111.2 (6) | N7—C26—C25 | 115.4 (6) |
N3—C9—H9A | 109.4 | N7—C26—H26A | 108.4 |
C8—C9—H9A | 109.4 | C25—C26—H26A | 108.4 |
N3—C9—H9B | 109.4 | N7—C26—H26B | 108.4 |
C8—C9—H9B | 109.4 | C25—C26—H26B | 108.4 |
H9A—C9—H9B | 108.0 | H26A—C26—H26B | 107.5 |
N3—C10—C11 | 106.3 (7) | C28—C27—N7 | 106.4 (7) |
N3—C10—H10 | 126.8 | C28—C27—H27 | 126.8 |
C11—C10—H10 | 126.8 | N7—C27—H27 | 126.8 |
C10—C11—N4 | 107.1 (7) | C27—C28—N8 | 109.1 (7) |
C10—C11—H11 | 126.5 | C27—C28—H28 | 125.5 |
N4—C11—H11 | 126.5 | N8—C28—H28 | 125.5 |
N4—C12—N3 | 103.3 (7) | N7—C29—N8 | 104.2 (6) |
N4—C12—S2 | 127.9 (6) | N7—C29—S4 | 128.8 (6) |
N3—C12—S2 | 128.8 (6) | N8—C29—S4 | 127.0 (6) |
O2—C13—O1 | 106.0 (6) | O3—C30—O4 | 105.9 (5) |
O2—C13—C14 | 111.7 (7) | O3—C30—C32 | 112.3 (7) |
O1—C13—C14 | 106.6 (7) | O4—C30—C32 | 106.5 (7) |
O2—C13—C15 | 106.6 (7) | O3—C30—C31 | 110.6 (7) |
O1—C13—C15 | 109.4 (6) | O4—C30—C31 | 108.4 (7) |
C14—C13—C15 | 116.1 (8) | C32—C30—C31 | 112.8 (7) |
C13—C14—H14A | 109.5 | C30—C31—H31A | 109.5 |
C13—C14—H14B | 109.5 | C30—C31—H31B | 109.5 |
H14A—C14—H14B | 109.5 | H31A—C31—H31B | 109.5 |
C13—C14—H14C | 109.5 | C30—C31—H31C | 109.5 |
H14A—C14—H14C | 109.5 | H31A—C31—H31C | 109.5 |
H14B—C14—H14C | 109.5 | H31B—C31—H31C | 109.5 |
C13—C15—H15A | 109.5 | C30—C32—H32A | 109.5 |
C13—C15—H15B | 109.5 | C30—C32—H32B | 109.5 |
H15A—C15—H15B | 109.5 | H32A—C32—H32B | 109.5 |
C13—C15—H15C | 109.5 | C30—C32—H32C | 109.5 |
H15A—C15—H15C | 109.5 | H32A—C32—H32C | 109.5 |
H15B—C15—H15C | 109.5 | H32B—C32—H32C | 109.5 |
N1—C16—H16A | 109.5 | N5—C33—H33A | 109.5 |
N1—C16—H16B | 109.5 | N5—C33—H33B | 109.5 |
H16A—C16—H16B | 109.5 | H33A—C33—H33B | 109.5 |
N1—C16—H16C | 109.5 | N5—C33—H33C | 109.5 |
H16A—C16—H16C | 109.5 | H33A—C33—H33C | 109.5 |
H16B—C16—H16C | 109.5 | H33B—C33—H33C | 109.5 |
N4—C17—H17A | 109.5 | N8—C34—H34A | 109.5 |
N4—C17—H17B | 109.5 | N8—C34—H34B | 109.5 |
H17A—C17—H17B | 109.5 | H34A—C34—H34B | 109.5 |
N4—C17—H17C | 109.5 | N8—C34—H34C | 109.5 |
H17A—C17—H17C | 109.5 | H34A—C34—H34C | 109.5 |
H17B—C17—H17C | 109.5 | H34B—C34—H34C | 109.5 |
C2—N1—C1—N2 | −0.6 (8) | C19—N5—C18—N6 | −0.5 (8) |
C16—N1—C1—N2 | −177.6 (7) | C33—N5—C18—N6 | 179.2 (7) |
C2—N1—C1—S1 | −178.7 (6) | C19—N5—C18—S3 | −178.0 (6) |
C16—N1—C1—S1 | 4.3 (11) | C33—N5—C18—S3 | 1.7 (11) |
C3—N2—C1—N1 | 0.8 (8) | C20—N6—C18—N5 | 0.4 (8) |
C4—N2—C1—N1 | 176.6 (6) | C21—N6—C18—N5 | −177.5 (6) |
C3—N2—C1—S1 | 178.9 (6) | C20—N6—C18—S3 | 177.9 (6) |
C4—N2—C1—S1 | −5.4 (10) | C21—N6—C18—S3 | 0.0 (11) |
C1—N1—C2—C3 | 0.2 (9) | C18—N5—C19—C20 | 0.4 (9) |
C16—N1—C2—C3 | 177.1 (7) | C33—N5—C19—C20 | −179.3 (7) |
N1—C2—C3—N2 | 0.3 (9) | N5—C19—C20—N6 | −0.1 (9) |
C1—N2—C3—C2 | −0.7 (8) | C18—N6—C20—C19 | −0.2 (9) |
C4—N2—C3—C2 | −176.2 (7) | C21—N6—C20—C19 | 177.8 (7) |
C1—N2—C4—C5 | 94.4 (8) | C20—N6—C21—C22 | −110.2 (8) |
C3—N2—C4—C5 | −90.7 (9) | C18—N6—C21—C22 | 67.4 (10) |
N2—C4—C5—C6 | 48.6 (9) | N6—C21—C22—C23 | 137.8 (7) |
C13—O1—C6—C5 | 150.7 (6) | C30—O3—C23—C24 | 36.5 (8) |
C13—O1—C6—C7 | 26.5 (7) | C30—O3—C23—C22 | 158.5 (7) |
C4—C5—C6—O1 | 56.9 (9) | C21—C22—C23—O3 | 63.6 (9) |
C4—C5—C6—C7 | 170.7 (7) | C21—C22—C23—C24 | 176.5 (7) |
C13—O2—C7—C6 | 35.2 (7) | C30—O4—C24—C25 | 153.0 (6) |
C13—O2—C7—C8 | 156.8 (6) | C30—O4—C24—C23 | 31.5 (7) |
O1—C6—C7—O2 | −37.8 (7) | O3—C23—C24—O4 | −41.2 (7) |
C5—C6—C7—O2 | −156.7 (7) | C22—C23—C24—O4 | −159.9 (6) |
O1—C6—C7—C8 | −156.8 (7) | O3—C23—C24—C25 | −159.1 (6) |
C5—C6—C7—C8 | 84.3 (9) | C22—C23—C24—C25 | 82.2 (9) |
O2—C7—C8—C9 | 63.8 (9) | O4—C24—C25—C26 | 54.5 (8) |
C6—C7—C8—C9 | −180.0 (7) | C23—C24—C25—C26 | 168.2 (6) |
C10—N3—C9—C8 | −106.2 (8) | C27—N7—C26—C25 | −95.3 (9) |
C12—N3—C9—C8 | 70.3 (9) | C29—N7—C26—C25 | 92.9 (8) |
C7—C8—C9—N3 | 132.0 (8) | C24—C25—C26—N7 | 53.4 (9) |
C12—N3—C10—C11 | 1.5 (9) | C29—N7—C27—C28 | 0.0 (9) |
C9—N3—C10—C11 | 178.4 (7) | C26—N7—C27—C28 | −172.5 (7) |
N3—C10—C11—N4 | −2.1 (9) | N7—C27—C28—N8 | 1.0 (9) |
C12—N4—C11—C10 | 2.1 (9) | C29—N8—C28—C27 | −1.7 (8) |
C17—N4—C11—C10 | −179.0 (8) | C34—N8—C28—C27 | 177.9 (7) |
C11—N4—C12—N3 | −1.1 (8) | C27—N7—C29—N8 | −1.1 (8) |
C17—N4—C12—N3 | 179.9 (7) | C26—N7—C29—N8 | 171.8 (6) |
C11—N4—C12—S2 | −179.4 (6) | C27—N7—C29—S4 | 178.9 (6) |
C17—N4—C12—S2 | 1.6 (11) | C26—N7—C29—S4 | −8.3 (11) |
C10—N3—C12—N4 | −0.3 (8) | C28—N8—C29—N7 | 1.7 (7) |
C9—N3—C12—N4 | −177.2 (7) | C34—N8—C29—N7 | −178.0 (7) |
C10—N3—C12—S2 | 178.0 (6) | C28—N8—C29—S4 | −178.3 (6) |
C9—N3—C12—S2 | 1.1 (11) | C34—N8—C29—S4 | 2.0 (11) |
C7—O2—C13—O1 | −18.3 (7) | C23—O3—C30—O4 | −17.9 (8) |
C7—O2—C13—C14 | 97.4 (8) | C23—O3—C30—C32 | 97.9 (8) |
C7—O2—C13—C15 | −134.8 (7) | C23—O3—C30—C31 | −135.1 (7) |
C6—O1—C13—O2 | −6.3 (7) | C24—O4—C30—O3 | −9.8 (8) |
C6—O1—C13—C14 | −125.4 (7) | C24—O4—C30—C32 | −129.5 (7) |
C6—O1—C13—C15 | 108.2 (7) | C24—O4—C30—C31 | 108.9 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···S1i | 0.95 | 2.86 | 3.703 (8) | 148 |
C16—H16C···O3 | 0.98 | 2.35 | 3.321 (10) | 171 |
C33—H33C···O1ii | 0.98 | 2.49 | 3.424 (10) | 160 |
C34—H34C···O2iii | 0.98 | 2.33 | 3.266 (10) | 160 |
Symmetry codes: (i) x−1, y, z; (ii) x−1, y, z−1; (iii) x, y, z−1. |
Experimental details
Crystal data | |
Chemical formula | C17H26N4O2S2 |
Mr | 382.54 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 120 |
a, b, c (Å) | 6.827 (5), 20.732 (9), 14.071 (8) |
β (°) | 93.68 (2) |
V (Å3) | 1988 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.29 |
Crystal size (mm) | 0.15 × 0.07 × 0.03 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 21365, 8499, 4275 |
Rint | 0.131 |
(sin θ/λ)max (Å−1) | 0.654 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.097, 0.241, 1.01 |
No. of reflections | 8499 |
No. of parameters | 458 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.19, −0.38 |
Absolute structure | Flack (1983), with 3717 Friedel pairs |
Absolute structure parameter | 0.03 (14) |
Computer programs: COLLECT (Nonius, 1998), HKL SCALEPACK (Otwinowski & Minor 1997), HKL DENZO (Otwinowski & Minor 1997), HKL SCALEPACK (Otwinowski & Minor 1997) and SORTAV (Blessing 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997).
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···S1i | 0.95 | 2.86 | 3.703 (8) | 148 |
C16—H16C···O3 | 0.98 | 2.35 | 3.321 (10) | 171 |
C33—H33C···O1ii | 0.98 | 2.49 | 3.424 (10) | 160 |
C34—H34C···O2iii | 0.98 | 2.33 | 3.266 (10) | 160 |
Symmetry codes: (i) x−1, y, z; (ii) x−1, y, z−1; (iii) x, y, z−1. |
As part of our ongoing investigations of chiral, C2-symmetric catalysts (Marshall & Harrison, 2007), the title compound, (I), which is an intermediate in such materials, has been synthesized and structurally characterized.
There are two molecules of (I) in the asymmetric unit (Fig. 1). All the chiral centres (C6, C7, C23, C24) possess their expected R configuarations. The dihedral angle between the N1/N2/C1/C2/C3 (IM1) and N3/N4/C10/C11/C12 (IM2) imidazole rings is 23.7 (5)°; that between the N5/N6/C18/C19/C20 (IM3) and N7/N8/C27/C28/C29 (IM4) planes is 31.4 (5)°. The thio-imidazole rings show their expected geometries (Marshall & Harrison, 2007; Williamson et al., 2006) and indeed all the geometrical parameters of the two molecules may be regarded as normal (Allen et al., 1987).
The crystal packing for (I) features short face-to-face contacts between the imidazole rings with a centroid-centroid separation of 3.675 (8) Å for IM1···IM2i (i = 2 - x, 1/2 + y, 1 - z) and 3.669 (8) Å for IM3···IM4ii (ii = 1 - x, -1/2 + y, -z). Such contacts are usually referred to as aromatic π–π stacking. However, the aromatic nature of the thio-imidazole ring is questionable (Williamson et al., 2006). If these really represent attractive intermolecular forces in the crystal, then [010] chains of molecules arise (Fig. 2). Some short C—H···S and C—H···O contacts (Table 1) also occur in the crystal.