In the chiral title compound, C
33H
42N
4O
2S
2, the dihedral angle between the imidazole ring planes is 79.47 (17)°. The packing is consolidated by van der Waals forces and weak C—H
S interactions.
Supporting information
CCDC reference: 672783
Key indicators
- Single-crystal synchrotron study
- T = 120 K
- Mean (C-C) = 0.005 Å
- R factor = 0.055
- wR factor = 0.128
- Data-to-parameter ratio = 20.2
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT601_ALERT_2_C Structure Contains Solvent Accessible VOIDS of . 49.00 A 3
Alert level G
ABSMU_01 Radiation type not identified. Calculation of
_exptl_absorpt_correction_mu not performed.
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
correct. If it is not, please give the correct count in the
_publ_section_exptl_refinement section of the submitted CIF.
From the CIF: _diffrn_reflns_theta_max 27.50
From the CIF: _reflns_number_total 7522
Count of symmetry unique reflns 4378
Completeness (_total/calc) 171.81%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 3144
Fraction of Friedel pairs measured 0.718
Are heavy atom types Z>Si present yes
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C9 = . S
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C13 = . S
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 1
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
1 ALERT level C = Check and explain
4 ALERT level G = General alerts; check
2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
1 ALERT type 2 Indicator that the structure model may be wrong or deficient
1 ALERT type 3 Indicator that the structure quality may be low
1 ALERT type 4 Improvement, methodology, query or suggestion
0 ALERT type 5 Informative message, check
A mixture of (4S,5S)-4,5-bis(1-cyclohexylimidazolium-3-methyl)-2,2-
dimethyl-1,3-dioxolane dibromide (1.29 g, 1.9 mmol), sulfur (0.18 g, 5.6 mmol), methanol (20 ml), pyridine (1.8 ml) and
1,8-diazabicyclo[5.4.0]undec-7-ene (1.26 g, 8.3 mmol) was heated at 338 K for
18 h. Once cooled to room temperature the mixture was opened to water (50 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 (0.92 g, 83%)
as a colourless foam that was recrystallized from methanol to give colourless
needles of (I); mp 470 K (from MeOH).
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: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); 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).
(4
S,5S)-4,5-Bis(3-cyclohexyl-2-thioxobenzimidazol-1-ylmethyl)-2,2-dimethyl-1,3-dioxolane
top
Crystal data top
C33H42N4O2S2 | F(000) = 1264 |
Mr = 590.83 | Dx = 1.198 Mg m−3 |
Monoclinic, C2 | Synchrotron radiation, λ = 0.68710 Å |
Hall symbol: C 2y | Cell parameters from 3328 reflections |
a = 21.876 (6) Å | θ = 2.2–27.8° |
b = 10.652 (3) Å | µ = 0.20 mm−1 |
c = 14.120 (4) Å | T = 120 K |
β = 95.398 (6)° | Block, colourless |
V = 3275.5 (16) Å3 | 0.05 × 0.04 × 0.03 mm |
Z = 4 | |
Data collection top
Bruker SMART CCD diffractometer | 5903 reflections with I > 2σ(I) |
Radiation source: Daresbury synchrotron | Rint = 0.036 |
Silicon monochromator | θmax = 27.5°, θmin = 1.8° |
ω scans | h = −29→23 |
11222 measured reflections | k = −14→14 |
7522 independent reflections | l = −15→18 |
Refinement top
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)] = 0.055 | H-atom parameters constrained |
wR(F2) = 0.128 | w = 1/[σ2(Fo2) + (0.0671P)2 + 0.1687P] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max = 0.001 |
7522 reflections | Δρmax = 0.36 e Å−3 |
372 parameters | Δρmin = −0.40 e Å−3 |
1 restraint | Absolute structure: Flack (1983), 3144 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.07 (7) |
Crystal data top
C33H42N4O2S2 | V = 3275.5 (16) Å3 |
Mr = 590.83 | Z = 4 |
Monoclinic, C2 | Synchrotron radiation, λ = 0.68710 Å |
a = 21.876 (6) Å | µ = 0.20 mm−1 |
b = 10.652 (3) Å | T = 120 K |
c = 14.120 (4) Å | 0.05 × 0.04 × 0.03 mm |
β = 95.398 (6)° | |
Data collection top
Bruker SMART CCD diffractometer | 5903 reflections with I > 2σ(I) |
11222 measured reflections | Rint = 0.036 |
7522 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.055 | H-atom parameters constrained |
wR(F2) = 0.128 | Δρmax = 0.36 e Å−3 |
S = 1.00 | Δρmin = −0.40 e Å−3 |
7522 reflections | Absolute structure: Flack (1983), 3144 Friedel pairs |
372 parameters | Absolute structure parameter: 0.07 (7) |
1 restraint | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | 0.73086 (4) | 0.02150 (7) | 0.70554 (5) | 0.02164 (17) | |
S2 | 0.84007 (4) | 0.22570 (7) | 0.94868 (5) | 0.02080 (16) | |
O1 | 0.89848 (10) | −0.2189 (2) | 0.86999 (15) | 0.0234 (5) | |
O2 | 0.81855 (10) | −0.24757 (18) | 0.96132 (14) | 0.0217 (5) | |
N1 | 0.77308 (12) | −0.1591 (2) | 0.58975 (18) | 0.0201 (5) | |
N2 | 0.84145 (11) | −0.0936 (2) | 0.70315 (16) | 0.0164 (5) | |
N3 | 0.81917 (11) | 0.0130 (2) | 1.04818 (16) | 0.0174 (5) | |
N4 | 0.88379 (11) | 0.1442 (2) | 1.12569 (17) | 0.0187 (5) | |
C1 | 0.78195 (14) | −0.0793 (3) | 0.6658 (2) | 0.0164 (6) | |
C2 | 0.82764 (15) | −0.2231 (3) | 0.5778 (2) | 0.0205 (6) | |
C3 | 0.84320 (15) | −0.3128 (3) | 0.5124 (2) | 0.0219 (6) | |
H3 | 0.8139 | −0.3437 | 0.4641 | 0.026* | |
C4 | 0.90343 (16) | −0.3548 (3) | 0.5210 (2) | 0.0262 (7) | |
H4 | 0.9154 | −0.4165 | 0.4779 | 0.031* | |
C5 | 0.94693 (16) | −0.3094 (3) | 0.5909 (2) | 0.0278 (7) | |
H5 | 0.9880 | −0.3389 | 0.5930 | 0.033* | |
C6 | 0.93160 (14) | −0.2220 (3) | 0.6575 (2) | 0.0239 (7) | |
H6 | 0.9610 | −0.1918 | 0.7059 | 0.029* | |
C7 | 0.87146 (14) | −0.1811 (3) | 0.6498 (2) | 0.0191 (6) | |
C8 | 0.86992 (14) | −0.0265 (3) | 0.7861 (2) | 0.0189 (6) | |
H8A | 0.8482 | 0.0541 | 0.7923 | 0.023* | |
H8B | 0.9130 | −0.0071 | 0.7757 | 0.023* | |
C9 | 0.86904 (13) | −0.0998 (3) | 0.8785 (2) | 0.0176 (6) | |
H9 | 0.8922 | −0.0512 | 0.9308 | 0.021* | |
C10 | 0.86347 (16) | −0.3145 (3) | 0.9129 (2) | 0.0255 (7) | |
C11 | 0.83314 (18) | −0.3989 (3) | 0.8362 (3) | 0.0346 (8) | |
H11A | 0.8645 | −0.4352 | 0.7993 | 0.052* | |
H11B | 0.8041 | −0.3498 | 0.7940 | 0.052* | |
H11C | 0.8111 | −0.4664 | 0.8657 | 0.052* | |
C12 | 0.90456 (19) | −0.3837 (4) | 0.9875 (3) | 0.0381 (9) | |
H12A | 0.9374 | −0.4260 | 0.9573 | 0.057* | |
H12B | 0.8804 | −0.4462 | 1.0187 | 0.057* | |
H12C | 0.9225 | −0.3239 | 1.0349 | 0.057* | |
C13 | 0.80586 (14) | −0.1337 (3) | 0.9095 (2) | 0.0170 (6) | |
H13 | 0.7769 | −0.1515 | 0.8520 | 0.020* | |
C14 | 0.77648 (14) | −0.0399 (3) | 0.9730 (2) | 0.0188 (6) | |
H14A | 0.7583 | 0.0294 | 0.9330 | 0.023* | |
H14B | 0.7427 | −0.0821 | 1.0024 | 0.023* | |
C15 | 0.84741 (14) | 0.1273 (3) | 1.0423 (2) | 0.0183 (6) | |
C16 | 0.83756 (14) | −0.0426 (3) | 1.1360 (2) | 0.0191 (6) | |
C17 | 0.82177 (15) | −0.1563 (3) | 1.1748 (2) | 0.0233 (7) | |
H17 | 0.7937 | −0.2123 | 1.1413 | 0.028* | |
C18 | 0.84907 (16) | −0.1842 (3) | 1.2649 (2) | 0.0287 (8) | |
H18 | 0.8390 | −0.2608 | 1.2941 | 0.034* | |
C19 | 0.89093 (17) | −0.1029 (3) | 1.3140 (2) | 0.0302 (8) | |
H19 | 0.9093 | −0.1262 | 1.3752 | 0.036* | |
C20 | 0.90623 (15) | 0.0113 (3) | 1.2752 (2) | 0.0251 (7) | |
H20 | 0.9344 | 0.0671 | 1.3089 | 0.030* | |
C21 | 0.87863 (14) | 0.0410 (3) | 1.1848 (2) | 0.0200 (6) | |
C22 | 0.71324 (14) | −0.1752 (3) | 0.5341 (2) | 0.0218 (6) | |
H22 | 0.6845 | −0.1130 | 0.5590 | 0.026* | |
C23 | 0.68706 (15) | −0.3058 (3) | 0.5503 (2) | 0.0258 (7) | |
H23A | 0.6841 | −0.3191 | 0.6191 | 0.031* | |
H23B | 0.7147 | −0.3706 | 0.5279 | 0.031* | |
C24 | 0.62329 (16) | −0.3178 (4) | 0.4961 (3) | 0.0334 (8) | |
H24A | 0.5946 | −0.2588 | 0.5233 | 0.040* | |
H24B | 0.6076 | −0.4041 | 0.5035 | 0.040* | |
C25 | 0.62588 (16) | −0.2890 (3) | 0.3902 (2) | 0.0303 (8) | |
H25A | 0.6512 | −0.3533 | 0.3619 | 0.036* | |
H25B | 0.5839 | −0.2934 | 0.3574 | 0.036* | |
C26 | 0.65257 (16) | −0.1606 (3) | 0.3747 (3) | 0.0322 (8) | |
H26A | 0.6247 | −0.0956 | 0.3963 | 0.039* | |
H26B | 0.6558 | −0.1478 | 0.3059 | 0.039* | |
C27 | 0.71624 (16) | −0.1458 (3) | 0.4289 (2) | 0.0266 (7) | |
H27A | 0.7456 | −0.2034 | 0.4019 | 0.032* | |
H27B | 0.7310 | −0.0587 | 0.4218 | 0.032* | |
C28 | 0.92048 (14) | 0.2584 (3) | 1.1462 (2) | 0.0193 (6) | |
H28 | 0.9126 | 0.3145 | 1.0896 | 0.023* | |
C29 | 0.98903 (14) | 0.2306 (3) | 1.1566 (2) | 0.0268 (7) | |
H29A | 1.0007 | 0.1868 | 1.0991 | 0.032* | |
H29B | 0.9993 | 0.1753 | 1.2122 | 0.032* | |
C30 | 1.02441 (17) | 0.3547 (3) | 1.1699 (3) | 0.0340 (8) | |
H30A | 1.0689 | 0.3366 | 1.1810 | 0.041* | |
H30B | 1.0175 | 0.4051 | 1.1109 | 0.041* | |
C31 | 1.00441 (16) | 0.4309 (3) | 1.2535 (3) | 0.0329 (8) | |
H31A | 1.0163 | 0.3854 | 1.3136 | 0.040* | |
H31B | 1.0260 | 0.5127 | 1.2565 | 0.040* | |
C32 | 0.93546 (15) | 0.4532 (3) | 1.2439 (2) | 0.0261 (7) | |
H32A | 0.9244 | 0.5087 | 1.1887 | 0.031* | |
H32B | 0.9237 | 0.4961 | 1.3016 | 0.031* | |
C33 | 0.89993 (16) | 0.3299 (3) | 1.2304 (2) | 0.0268 (7) | |
H33A | 0.9071 | 0.2781 | 1.2886 | 0.032* | |
H33B | 0.8554 | 0.3477 | 1.2196 | 0.032* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0258 (4) | 0.0213 (4) | 0.0178 (4) | 0.0050 (3) | 0.0019 (3) | 0.0001 (3) |
S2 | 0.0281 (4) | 0.0170 (3) | 0.0171 (4) | 0.0009 (3) | 0.0014 (3) | 0.0027 (3) |
O1 | 0.0274 (12) | 0.0237 (11) | 0.0200 (11) | 0.0070 (9) | 0.0066 (9) | 0.0056 (9) |
O2 | 0.0342 (13) | 0.0171 (11) | 0.0148 (10) | 0.0016 (9) | 0.0082 (9) | 0.0032 (8) |
N1 | 0.0248 (14) | 0.0191 (12) | 0.0160 (13) | −0.0019 (10) | −0.0007 (10) | 0.0004 (10) |
N2 | 0.0195 (13) | 0.0182 (11) | 0.0116 (12) | −0.0025 (10) | 0.0025 (10) | 0.0003 (10) |
N3 | 0.0219 (12) | 0.0180 (11) | 0.0126 (11) | −0.0025 (11) | 0.0033 (9) | 0.0008 (10) |
N4 | 0.0255 (14) | 0.0158 (11) | 0.0149 (12) | −0.0022 (10) | 0.0025 (10) | 0.0005 (10) |
C1 | 0.0224 (15) | 0.0143 (13) | 0.0122 (14) | −0.0013 (11) | 0.0004 (11) | 0.0035 (11) |
C2 | 0.0289 (16) | 0.0178 (13) | 0.0151 (15) | −0.0030 (13) | 0.0032 (12) | 0.0031 (12) |
C3 | 0.0326 (17) | 0.0199 (14) | 0.0136 (14) | −0.0034 (13) | 0.0038 (12) | 0.0002 (12) |
C4 | 0.042 (2) | 0.0213 (15) | 0.0175 (16) | 0.0037 (14) | 0.0125 (14) | −0.0002 (13) |
C5 | 0.0313 (18) | 0.0289 (16) | 0.0252 (17) | 0.0111 (14) | 0.0127 (14) | 0.0073 (14) |
C6 | 0.0236 (16) | 0.0340 (16) | 0.0145 (15) | 0.0007 (13) | 0.0036 (12) | 0.0015 (13) |
C7 | 0.0269 (16) | 0.0191 (14) | 0.0117 (14) | −0.0003 (12) | 0.0039 (12) | 0.0025 (11) |
C8 | 0.0190 (15) | 0.0217 (14) | 0.0154 (14) | −0.0024 (12) | −0.0015 (11) | −0.0010 (12) |
C9 | 0.0202 (15) | 0.0202 (14) | 0.0122 (13) | 0.0002 (12) | 0.0005 (11) | 0.0002 (11) |
C10 | 0.0372 (19) | 0.0206 (14) | 0.0197 (16) | 0.0054 (13) | 0.0069 (14) | 0.0013 (13) |
C11 | 0.050 (2) | 0.0259 (17) | 0.0290 (19) | −0.0014 (16) | 0.0083 (17) | −0.0079 (15) |
C12 | 0.054 (2) | 0.0331 (19) | 0.0275 (19) | 0.0147 (18) | 0.0066 (17) | 0.0080 (16) |
C13 | 0.0241 (16) | 0.0171 (13) | 0.0094 (13) | −0.0017 (11) | −0.0012 (11) | 0.0017 (11) |
C14 | 0.0198 (15) | 0.0196 (14) | 0.0171 (14) | −0.0009 (12) | 0.0029 (11) | −0.0010 (12) |
C15 | 0.0204 (15) | 0.0181 (14) | 0.0170 (14) | 0.0020 (12) | 0.0054 (11) | −0.0021 (12) |
C16 | 0.0234 (16) | 0.0199 (14) | 0.0143 (14) | −0.0019 (12) | 0.0037 (11) | −0.0004 (11) |
C17 | 0.0308 (18) | 0.0232 (15) | 0.0167 (15) | −0.0066 (13) | 0.0059 (13) | −0.0015 (13) |
C18 | 0.044 (2) | 0.0247 (16) | 0.0182 (16) | −0.0057 (15) | 0.0040 (14) | 0.0038 (13) |
C19 | 0.045 (2) | 0.0281 (16) | 0.0172 (16) | −0.0042 (15) | 0.0001 (14) | 0.0040 (14) |
C20 | 0.0354 (18) | 0.0248 (15) | 0.0148 (14) | −0.0046 (14) | 0.0003 (12) | 0.0019 (13) |
C21 | 0.0264 (15) | 0.0175 (14) | 0.0165 (14) | −0.0040 (12) | 0.0041 (11) | −0.0018 (12) |
C22 | 0.0253 (16) | 0.0219 (15) | 0.0172 (15) | 0.0017 (12) | −0.0024 (12) | −0.0040 (12) |
C23 | 0.0271 (17) | 0.0295 (17) | 0.0201 (16) | −0.0028 (13) | −0.0015 (13) | 0.0039 (13) |
C24 | 0.0300 (19) | 0.0405 (19) | 0.0289 (19) | −0.0083 (15) | −0.0010 (15) | −0.0035 (16) |
C25 | 0.0331 (18) | 0.0292 (18) | 0.0265 (17) | 0.0027 (15) | −0.0081 (14) | −0.0047 (15) |
C26 | 0.038 (2) | 0.0299 (17) | 0.0252 (18) | 0.0029 (15) | −0.0129 (15) | −0.0015 (15) |
C27 | 0.0336 (19) | 0.0256 (16) | 0.0188 (15) | −0.0077 (14) | −0.0079 (13) | 0.0045 (13) |
C28 | 0.0226 (15) | 0.0168 (14) | 0.0184 (14) | −0.0042 (11) | 0.0016 (11) | 0.0004 (11) |
C29 | 0.0256 (16) | 0.0272 (15) | 0.0287 (17) | −0.0027 (15) | 0.0080 (12) | −0.0100 (15) |
C30 | 0.0288 (18) | 0.0373 (19) | 0.037 (2) | −0.0118 (16) | 0.0098 (15) | −0.0145 (17) |
C31 | 0.0301 (19) | 0.0334 (18) | 0.034 (2) | −0.0080 (15) | −0.0030 (15) | −0.0124 (16) |
C32 | 0.0312 (18) | 0.0215 (15) | 0.0251 (17) | −0.0009 (14) | −0.0008 (14) | −0.0075 (14) |
C33 | 0.0271 (17) | 0.0235 (15) | 0.0297 (18) | 0.0001 (13) | 0.0029 (14) | −0.0040 (14) |
Geometric parameters (Å, º) top
S1—C1 | 1.684 (3) | C16—C17 | 1.387 (4) |
S2—C15 | 1.683 (3) | C16—C21 | 1.399 (4) |
O1—C9 | 1.433 (4) | C17—C18 | 1.386 (4) |
O1—C10 | 1.441 (4) | C17—H17 | 0.9500 |
O2—C13 | 1.430 (3) | C18—C19 | 1.396 (5) |
O2—C10 | 1.438 (4) | C18—H18 | 0.9500 |
N1—C1 | 1.369 (4) | C19—C20 | 1.388 (5) |
N1—C2 | 1.399 (4) | C19—H19 | 0.9500 |
N1—C22 | 1.472 (4) | C20—C21 | 1.396 (4) |
N2—C1 | 1.366 (4) | C20—H20 | 0.9500 |
N2—C7 | 1.400 (4) | C22—C27 | 1.525 (4) |
N2—C8 | 1.460 (4) | C22—C23 | 1.530 (4) |
N3—C15 | 1.372 (4) | C22—H22 | 1.0000 |
N3—C16 | 1.399 (4) | C23—C24 | 1.532 (5) |
N3—C14 | 1.459 (4) | C23—H23A | 0.9900 |
N4—C15 | 1.369 (4) | C23—H23B | 0.9900 |
N4—C21 | 1.391 (4) | C24—C25 | 1.533 (5) |
N4—C28 | 1.471 (4) | C24—H24A | 0.9900 |
C2—C3 | 1.393 (4) | C24—H24B | 0.9900 |
C2—C7 | 1.404 (4) | C25—C26 | 1.510 (5) |
C3—C4 | 1.386 (5) | C25—H25A | 0.9900 |
C3—H3 | 0.9500 | C25—H25B | 0.9900 |
C4—C5 | 1.391 (5) | C26—C27 | 1.533 (5) |
C4—H4 | 0.9500 | C26—H26A | 0.9900 |
C5—C6 | 1.386 (5) | C26—H26B | 0.9900 |
C5—H5 | 0.9500 | C27—H27A | 0.9900 |
C6—C7 | 1.381 (4) | C27—H27B | 0.9900 |
C6—H6 | 0.9500 | C28—C33 | 1.515 (4) |
C8—C9 | 1.523 (4) | C28—C29 | 1.522 (4) |
C8—H8A | 0.9900 | C28—H28 | 1.0000 |
C8—H8B | 0.9900 | C29—C30 | 1.534 (5) |
C9—C13 | 1.532 (4) | C29—H29A | 0.9900 |
C9—H9 | 1.0000 | C29—H29B | 0.9900 |
C10—C12 | 1.512 (5) | C30—C31 | 1.530 (5) |
C10—C11 | 1.512 (5) | C30—H30A | 0.9900 |
C11—H11A | 0.9800 | C30—H30B | 0.9900 |
C11—H11B | 0.9800 | C31—C32 | 1.520 (5) |
C11—H11C | 0.9800 | C31—H31A | 0.9900 |
C12—H12A | 0.9800 | C31—H31B | 0.9900 |
C12—H12B | 0.9800 | C32—C33 | 1.529 (5) |
C12—H12C | 0.9800 | C32—H32A | 0.9900 |
C13—C14 | 1.524 (4) | C32—H32B | 0.9900 |
C13—H13 | 1.0000 | C33—H33A | 0.9900 |
C14—H14A | 0.9900 | C33—H33B | 0.9900 |
C14—H14B | 0.9900 | | |
| | | |
C9—O1—C10 | 109.2 (2) | C16—C17—H17 | 121.7 |
C13—O2—C10 | 106.6 (2) | C17—C18—C19 | 122.0 (3) |
C1—N1—C2 | 109.8 (2) | C17—C18—H18 | 119.0 |
C1—N1—C22 | 123.0 (3) | C19—C18—H18 | 119.0 |
C2—N1—C22 | 127.2 (3) | C20—C19—C18 | 121.2 (3) |
C1—N2—C7 | 110.2 (2) | C20—C19—H19 | 119.4 |
C1—N2—C8 | 125.0 (2) | C18—C19—H19 | 119.4 |
C7—N2—C8 | 124.8 (2) | C19—C20—C21 | 117.4 (3) |
C15—N3—C16 | 109.6 (2) | C19—C20—H20 | 121.3 |
C15—N3—C14 | 124.0 (2) | C21—C20—H20 | 121.3 |
C16—N3—C14 | 126.4 (2) | N4—C21—C20 | 132.5 (3) |
C15—N4—C21 | 109.8 (2) | N4—C21—C16 | 107.0 (2) |
C15—N4—C28 | 122.7 (2) | C20—C21—C16 | 120.5 (3) |
C21—N4—C28 | 127.5 (2) | N1—C22—C27 | 112.2 (3) |
N2—C1—N1 | 107.1 (2) | N1—C22—C23 | 110.7 (2) |
N2—C1—S1 | 125.5 (2) | C27—C22—C23 | 112.6 (3) |
N1—C1—S1 | 127.4 (2) | N1—C22—H22 | 107.0 |
C3—C2—N1 | 132.8 (3) | C27—C22—H22 | 107.0 |
C3—C2—C7 | 120.4 (3) | C23—C22—H22 | 107.0 |
N1—C2—C7 | 106.8 (3) | C22—C23—C24 | 109.7 (3) |
C4—C3—C2 | 116.9 (3) | C22—C23—H23A | 109.7 |
C4—C3—H3 | 121.5 | C24—C23—H23A | 109.7 |
C2—C3—H3 | 121.5 | C22—C23—H23B | 109.7 |
C3—C4—C5 | 122.1 (3) | C24—C23—H23B | 109.7 |
C3—C4—H4 | 119.0 | H23A—C23—H23B | 108.2 |
C5—C4—H4 | 119.0 | C23—C24—C25 | 110.8 (3) |
C6—C5—C4 | 121.4 (3) | C23—C24—H24A | 109.5 |
C6—C5—H5 | 119.3 | C25—C24—H24A | 109.5 |
C4—C5—H5 | 119.3 | C23—C24—H24B | 109.5 |
C7—C6—C5 | 116.7 (3) | C25—C24—H24B | 109.5 |
C7—C6—H6 | 121.7 | H24A—C24—H24B | 108.1 |
C5—C6—H6 | 121.7 | C26—C25—C24 | 111.9 (3) |
C6—C7—N2 | 131.3 (3) | C26—C25—H25A | 109.2 |
C6—C7—C2 | 122.4 (3) | C24—C25—H25A | 109.2 |
N2—C7—C2 | 106.2 (3) | C26—C25—H25B | 109.2 |
N2—C8—C9 | 113.4 (2) | C24—C25—H25B | 109.2 |
N2—C8—H8A | 108.9 | H25A—C25—H25B | 107.9 |
C9—C8—H8A | 108.9 | C25—C26—C27 | 111.5 (3) |
N2—C8—H8B | 108.9 | C25—C26—H26A | 109.3 |
C9—C8—H8B | 108.9 | C27—C26—H26A | 109.3 |
H8A—C8—H8B | 107.7 | C25—C26—H26B | 109.3 |
O1—C9—C8 | 109.9 (2) | C27—C26—H26B | 109.3 |
O1—C9—C13 | 103.9 (2) | H26A—C26—H26B | 108.0 |
C8—C9—C13 | 116.8 (2) | C22—C27—C26 | 110.1 (3) |
O1—C9—H9 | 108.7 | C22—C27—H27A | 109.6 |
C8—C9—H9 | 108.7 | C26—C27—H27A | 109.6 |
C13—C9—H9 | 108.7 | C22—C27—H27B | 109.6 |
O2—C10—O1 | 105.3 (2) | C26—C27—H27B | 109.6 |
O2—C10—C12 | 107.4 (3) | H27A—C27—H27B | 108.1 |
O1—C10—C12 | 109.4 (3) | N4—C28—C33 | 111.9 (2) |
O2—C10—C11 | 111.2 (3) | N4—C28—C29 | 111.8 (2) |
O1—C10—C11 | 109.5 (3) | C33—C28—C29 | 112.7 (3) |
C12—C10—C11 | 113.6 (3) | N4—C28—H28 | 106.7 |
C10—C11—H11A | 109.5 | C33—C28—H28 | 106.7 |
C10—C11—H11B | 109.5 | C29—C28—H28 | 106.7 |
H11A—C11—H11B | 109.5 | C28—C29—C30 | 108.9 (3) |
C10—C11—H11C | 109.5 | C28—C29—H29A | 109.9 |
H11A—C11—H11C | 109.5 | C30—C29—H29A | 109.9 |
H11B—C11—H11C | 109.5 | C28—C29—H29B | 109.9 |
C10—C12—H12A | 109.5 | C30—C29—H29B | 109.9 |
C10—C12—H12B | 109.5 | H29A—C29—H29B | 108.3 |
H12A—C12—H12B | 109.5 | C31—C30—C29 | 112.0 (3) |
C10—C12—H12C | 109.5 | C31—C30—H30A | 109.2 |
H12A—C12—H12C | 109.5 | C29—C30—H30A | 109.2 |
H12B—C12—H12C | 109.5 | C31—C30—H30B | 109.2 |
O2—C13—C14 | 109.1 (2) | C29—C30—H30B | 109.2 |
O2—C13—C9 | 102.1 (2) | H30A—C30—H30B | 107.9 |
C14—C13—C9 | 117.1 (2) | C32—C31—C30 | 111.6 (3) |
O2—C13—H13 | 109.4 | C32—C31—H31A | 109.3 |
C14—C13—H13 | 109.4 | C30—C31—H31A | 109.3 |
C9—C13—H13 | 109.4 | C32—C31—H31B | 109.3 |
N3—C14—C13 | 113.8 (2) | C30—C31—H31B | 109.3 |
N3—C14—H14A | 108.8 | H31A—C31—H31B | 108.0 |
C13—C14—H14A | 108.8 | C31—C32—C33 | 111.4 (3) |
N3—C14—H14B | 108.8 | C31—C32—H32A | 109.3 |
C13—C14—H14B | 108.8 | C33—C32—H32A | 109.3 |
H14A—C14—H14B | 107.7 | C31—C32—H32B | 109.3 |
N4—C15—N3 | 107.1 (2) | C33—C32—H32B | 109.3 |
N4—C15—S2 | 126.8 (2) | H32A—C32—H32B | 108.0 |
N3—C15—S2 | 126.1 (2) | C28—C33—C32 | 110.1 (3) |
C17—C16—N3 | 131.2 (3) | C28—C33—H33A | 109.6 |
C17—C16—C21 | 122.3 (3) | C32—C33—H33A | 109.6 |
N3—C16—C21 | 106.6 (2) | C28—C33—H33B | 109.6 |
C18—C17—C16 | 116.6 (3) | C32—C33—H33B | 109.6 |
C18—C17—H17 | 121.7 | H33A—C33—H33B | 108.2 |
| | | |
C7—N2—C1—N1 | 1.2 (3) | C28—N4—C15—N3 | −178.7 (2) |
C8—N2—C1—N1 | −179.4 (2) | C21—N4—C15—S2 | −178.5 (2) |
C7—N2—C1—S1 | −177.2 (2) | C28—N4—C15—S2 | 3.0 (4) |
C8—N2—C1—S1 | 2.3 (4) | C16—N3—C15—N4 | 0.3 (3) |
C2—N1—C1—N2 | −0.9 (3) | C14—N3—C15—N4 | −179.9 (2) |
C22—N1—C1—N2 | 176.6 (3) | C16—N3—C15—S2 | 178.6 (2) |
C2—N1—C1—S1 | 177.4 (2) | C14—N3—C15—S2 | −1.6 (4) |
C22—N1—C1—S1 | −5.1 (4) | C15—N3—C16—C17 | 179.8 (3) |
C1—N1—C2—C3 | −179.9 (3) | C14—N3—C16—C17 | 0.1 (5) |
C22—N1—C2—C3 | 2.7 (5) | C15—N3—C16—C21 | −0.3 (3) |
C1—N1—C2—C7 | 0.3 (3) | C14—N3—C16—C21 | 179.9 (3) |
C22—N1—C2—C7 | −177.1 (3) | N3—C16—C17—C18 | 179.5 (3) |
N1—C2—C3—C4 | 178.7 (3) | C21—C16—C17—C18 | −0.4 (5) |
C7—C2—C3—C4 | −1.5 (4) | C16—C17—C18—C19 | −0.7 (5) |
C2—C3—C4—C5 | −0.6 (5) | C17—C18—C19—C20 | 1.3 (6) |
C3—C4—C5—C6 | 1.9 (5) | C18—C19—C20—C21 | −0.7 (5) |
C4—C5—C6—C7 | −1.0 (5) | C15—N4—C21—C20 | 179.0 (3) |
C5—C6—C7—N2 | −178.7 (3) | C28—N4—C21—C20 | −2.6 (5) |
C5—C6—C7—C2 | −1.1 (5) | C15—N4—C21—C16 | 0.0 (3) |
C1—N2—C7—C6 | 176.9 (3) | C28—N4—C21—C16 | 178.4 (3) |
C8—N2—C7—C6 | −2.5 (5) | C19—C20—C21—N4 | −179.2 (3) |
C1—N2—C7—C2 | −1.0 (3) | C19—C20—C21—C16 | −0.4 (5) |
C8—N2—C7—C2 | 179.6 (2) | C17—C16—C21—N4 | −180.0 (3) |
C3—C2—C7—C6 | 2.4 (5) | N3—C16—C21—N4 | 0.2 (3) |
N1—C2—C7—C6 | −177.7 (3) | C17—C16—C21—C20 | 0.9 (5) |
C3—C2—C7—N2 | −179.4 (3) | N3—C16—C21—C20 | −178.9 (3) |
N1—C2—C7—N2 | 0.4 (3) | C1—N1—C22—C27 | 122.3 (3) |
C1—N2—C8—C9 | 95.4 (3) | C2—N1—C22—C27 | −60.7 (4) |
C7—N2—C8—C9 | −85.2 (3) | C1—N1—C22—C23 | −111.1 (3) |
C10—O1—C9—C8 | −138.1 (2) | C2—N1—C22—C23 | 66.0 (4) |
C10—O1—C9—C13 | −12.4 (3) | N1—C22—C23—C24 | 176.9 (3) |
N2—C8—C9—O1 | 56.6 (3) | C27—C22—C23—C24 | −56.6 (4) |
N2—C8—C9—C13 | −61.3 (3) | C22—C23—C24—C25 | 55.6 (4) |
C13—O2—C10—O1 | 29.6 (3) | C23—C24—C25—C26 | −56.2 (4) |
C13—O2—C10—C12 | 146.1 (3) | C24—C25—C26—C27 | 55.6 (4) |
C13—O2—C10—C11 | −89.0 (3) | N1—C22—C27—C26 | −178.5 (3) |
C9—O1—C10—O2 | −9.5 (3) | C23—C22—C27—C26 | 55.9 (4) |
C9—O1—C10—C12 | −124.6 (3) | C25—C26—C27—C22 | −54.6 (4) |
C9—O1—C10—C11 | 110.2 (3) | C15—N4—C28—C33 | 116.4 (3) |
C10—O2—C13—C14 | −160.9 (2) | C21—N4—C28—C33 | −61.8 (4) |
C10—O2—C13—C9 | −36.4 (3) | C15—N4—C28—C29 | −116.1 (3) |
O1—C9—C13—O2 | 29.6 (3) | C21—N4—C28—C29 | 65.7 (4) |
C8—C9—C13—O2 | 150.7 (2) | N4—C28—C29—C30 | 175.5 (3) |
O1—C9—C13—C14 | 148.7 (2) | C33—C28—C29—C30 | −57.4 (4) |
C8—C9—C13—C14 | −90.2 (3) | C28—C29—C30—C31 | 55.1 (4) |
C15—N3—C14—C13 | 97.8 (3) | C29—C30—C31—C32 | −54.7 (4) |
C16—N3—C14—C13 | −82.4 (3) | C30—C31—C32—C33 | 54.2 (4) |
O2—C13—C14—N3 | 72.7 (3) | N4—C28—C33—C32 | −175.1 (2) |
C9—C13—C14—N3 | −42.5 (3) | C29—C28—C33—C32 | 57.8 (4) |
C21—N4—C15—N3 | −0.2 (3) | C31—C32—C33—C28 | −55.2 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C14—H14B···S2i | 0.99 | 2.86 | 3.806 (3) | 160 |
C18—H18···S1i | 0.95 | 2.78 | 3.633 (4) | 150 |
Symmetry code: (i) −x+3/2, y−1/2, −z+2. |
Experimental details
Crystal data |
Chemical formula | C33H42N4O2S2 |
Mr | 590.83 |
Crystal system, space group | Monoclinic, C2 |
Temperature (K) | 120 |
a, b, c (Å) | 21.876 (6), 10.652 (3), 14.120 (4) |
β (°) | 95.398 (6) |
V (Å3) | 3275.5 (16) |
Z | 4 |
Radiation type | Synchrotron, λ = 0.68710 Å |
µ (mm−1) | 0.20 |
Crystal size (mm) | 0.05 × 0.04 × 0.03 |
|
Data collection |
Diffractometer | Bruker SMART CCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11222, 7522, 5903 |
Rint | 0.036 |
(sin θ/λ)max (Å−1) | 0.672 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.128, 1.00 |
No. of reflections | 7522 |
No. of parameters | 372 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.36, −0.40 |
Absolute structure | Flack (1983), 3144 Friedel pairs |
Absolute structure parameter | 0.07 (7) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C14—H14B···S2i | 0.99 | 2.86 | 3.806 (3) | 160 |
C18—H18···S1i | 0.95 | 2.78 | 3.633 (4) | 150 |
Symmetry code: (i) −x+3/2, y−1/2, −z+2. |
As part of our ongoing investigations of chiral, C2-symmetric catalysts (Marshall & Harrison, 2007), the title compound, (I), an intermediate in the synthesis of such materials, has been synthesized and structurally characterized. There is a single molecule in the asymmetric unit of (I) (Fig. 1), with C9 and C13 showing the expected atomic chirality (both have S configuration). The dihedral angle between the imidazole rings (N1/N2/C1/C2/C7 and N3/N4/C15/C16/C21) is 79.47 (17)°.
Both the thio-imidazole ring systems display typical geometrical parameters, with the C—S bond lengths significantly longer than that of an isolated C=S double bond (~1.60 Å), which can be correlated with the contribution of resonance structures involving the lone pair electrons of the adjacent N atoms (Williamson et al., 2006). The terminal cyclohexane rings are normal chairs. Otherwise, the geometry of the molecule may be regarded as normal (Allen et al., 1995).
The crystal packing for (I) is consolidated by van der Walls forces and weak C—H···S interactions. (Table 2).