Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010301905X/gd1269sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010301905X/gd1269Isup2.hkl |
CCDC reference: 224665
To a stirred solution of 2-tert-butyl-4-methylphenol (2.00 g, 12.17 mmol) in anhydrous tetrahydrofuran (75 ml) was added solid NaH (0.30 g, 12.17 mmol) in small portions. After the mixture had been stirred for 1 h, dimethylthiocarbamoyl chloride (3.01 g, 24.35 mmol) was added. The mixture was again stirred for 1 h at room temperature and was then heated to reflux for 12 h, after which the mixture was cooled to room temperature and quenched with water (30 ml). The organic phase was diluted with diethyl ether (75 ml) and washed successively with water (30 ml) and a saturated Na2CO3 solution (30 ml). The organic layer was then dried with Na2SO4, filtered and concentrated with a rotary evaporator. The yellow solid obtained was disolved in dichloromethane (25 ml), and slow evaporation of the solvent afforded yellow crystals of (I) (yield 0.66 g, 16.1%; m.p. 360–363 K). IR (CHCl3, cm−1): 3022, 2970, 2875, 1596, 1523, 1482, 1433, 1397, 1365, 1289, 1137, 1060, 930, 865, 824; 1H NMR (300 MHz, CDCl3, TMS internal reference): δ 7.18 (1H, d, ArH), 6.73 (1H, d, ArH), 3.47 (3H, s, NMe), 3.42 (3H, s, NMe), 3.39 (3H, s, NMe), 3.34 (3H, s, NMe), 2.3 (3H, s, ArMe), 1.36 (9H, s, tBu); EI mass spectrum: m/z 338 (M+, 70%).
The positional parameters of the H atoms were calculated geometrically and refined as riding, with a fixed Uiso value (1.2Ueq of the parent atom) and C—H distances in the range 0.93–0.97 Å. Dichloromethane solvent molecules were refined isotropically at two positions, each with an occupancy of 0.5.
Data collection: SMART (Bruker, Date); cell refinement: SMART; data reduction: SAINT (Bruker, Date); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, Date); software used to prepare material for publication: SHELXTL.
C17H26N2OS2·CH2Cl2 | F(000) = 896 |
Mr = 423.44 | Dx = 1.282 Mg m−3 |
Monoclinic, P21/c | Melting point = 360–363 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 9.5032 (5) Å | Cell parameters from 5414 reflections |
b = 21.4599 (10) Å | θ = 2.5–31.0° |
c = 11.7601 (7) Å | µ = 0.50 mm−1 |
β = 113.791 (1)° | T = 291 K |
V = 2194.5 (2) Å3 | Prism, colorless |
Z = 4 | 0.30 × 0.22 × 0.16 mm |
Bruker Smart Apex CCD area-detector diffractometer | 2621 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.051 |
Graphite monochromator | θmax = 25.0°, θmin = 1.9° |
ω scans | h = −11→11 |
17814 measured reflections | k = −25→25 |
3851 independent reflections | l = −13→13 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.061 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.167 | H-atom parameters constrained |
S = 0.99 | w = 1/[σ2(Fo2) + (0.096P)2] where P = (Fo2 + 2Fc2)/3 |
3851 reflections | (Δ/σ)max = 0.002 |
230 parameters | Δρmax = 0.50 e Å−3 |
0 restraints | Δρmin = −0.43 e Å−3 |
C17H26N2OS2·CH2Cl2 | V = 2194.5 (2) Å3 |
Mr = 423.44 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.5032 (5) Å | µ = 0.50 mm−1 |
b = 21.4599 (10) Å | T = 291 K |
c = 11.7601 (7) Å | 0.30 × 0.22 × 0.16 mm |
β = 113.791 (1)° |
Bruker Smart Apex CCD area-detector diffractometer | 2621 reflections with I > 2σ(I) |
17814 measured reflections | Rint = 0.051 |
3851 independent reflections |
R[F2 > 2σ(F2)] = 0.061 | 0 restraints |
wR(F2) = 0.167 | H-atom parameters constrained |
S = 0.99 | Δρmax = 0.50 e Å−3 |
3851 reflections | Δρmin = −0.43 e Å−3 |
230 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
S1 | 0.89931 (13) | 0.07964 (5) | 0.65310 (9) | 0.0657 (3) | |
S2 | 0.55062 (10) | 0.15940 (4) | 0.31664 (9) | 0.0550 (3) | |
O1 | 0.8930 (2) | 0.18298 (9) | 0.52637 (18) | 0.0420 (5) | |
N1 | 0.7945 (3) | 0.19348 (14) | 0.6647 (2) | 0.0501 (7) | |
N2 | 0.6323 (3) | 0.04116 (13) | 0.3565 (3) | 0.0492 (7) | |
C1 | 0.8323 (3) | 0.11071 (14) | 0.3568 (3) | 0.0372 (7) | |
C2 | 0.9362 (3) | 0.15065 (14) | 0.4426 (3) | 0.0381 (7) | |
C3 | 1.0783 (3) | 0.16520 (14) | 0.4404 (3) | 0.0395 (7) | |
C4 | 1.1099 (3) | 0.13730 (15) | 0.3466 (3) | 0.0439 (8) | |
H4 | 1.2038 | 0.1458 | 0.3427 | 0.053* | |
C5 | 1.0098 (4) | 0.09775 (15) | 0.2592 (3) | 0.0422 (8) | |
C6 | 0.8728 (4) | 0.08444 (14) | 0.2665 (3) | 0.0424 (8) | |
H6 | 0.8049 | 0.0570 | 0.2094 | 0.051* | |
C7 | 0.6732 (3) | 0.09908 (15) | 0.3490 (3) | 0.0410 (8) | |
C8 | 1.0484 (4) | 0.06931 (17) | 0.1575 (3) | 0.0577 (10) | |
H8A | 1.0699 | 0.0257 | 0.1739 | 0.069* | |
H8B | 1.1370 | 0.0898 | 0.1551 | 0.069* | |
H8C | 0.9627 | 0.0744 | 0.0789 | 0.069* | |
C9 | 1.1924 (3) | 0.21119 (15) | 0.5329 (3) | 0.0455 (8) | |
C10 | 1.2319 (5) | 0.19289 (19) | 0.6668 (3) | 0.0706 (11) | |
H10A | 1.1418 | 0.1964 | 0.6843 | 0.085* | |
H10B | 1.3107 | 0.2200 | 0.7211 | 0.085* | |
H10C | 1.2681 | 0.1506 | 0.6799 | 0.085* | |
C11 | 1.1235 (4) | 0.27691 (17) | 0.5096 (4) | 0.0692 (11) | |
H11A | 1.0312 | 0.2774 | 0.5243 | 0.083* | |
H11B | 1.0997 | 0.2887 | 0.4251 | 0.083* | |
H11C | 1.1963 | 0.3058 | 0.5648 | 0.083* | |
C12 | 1.3437 (4) | 0.2144 (2) | 0.5160 (4) | 0.0738 (12) | |
H12A | 1.4113 | 0.2438 | 0.5739 | 0.089* | |
H12B | 1.3234 | 0.2274 | 0.4328 | 0.089* | |
H12C | 1.3912 | 0.1741 | 0.5308 | 0.089* | |
C13 | 0.8588 (4) | 0.15340 (16) | 0.6141 (3) | 0.0441 (8) | |
C14 | 0.7630 (4) | 0.25728 (18) | 0.6230 (4) | 0.0643 (11) | |
H14A | 0.8582 | 0.2793 | 0.6443 | 0.077* | |
H14B | 0.7037 | 0.2769 | 0.6625 | 0.077* | |
H14C | 0.7061 | 0.2581 | 0.5345 | 0.077* | |
C15 | 0.7482 (5) | 0.1729 (2) | 0.7623 (3) | 0.0735 (12) | |
H15A | 0.6579 | 0.1474 | 0.7269 | 0.088* | |
H15B | 0.7263 | 0.2086 | 0.8017 | 0.088* | |
H15C | 0.8299 | 0.1492 | 0.8227 | 0.088* | |
C16 | 0.4738 (4) | 0.02652 (19) | 0.3360 (4) | 0.0707 (11) | |
H16A | 0.4505 | 0.0449 | 0.4008 | 0.085* | |
H16B | 0.4614 | −0.0179 | 0.3368 | 0.085* | |
H16C | 0.4052 | 0.0429 | 0.2571 | 0.085* | |
C17 | 0.7395 (5) | −0.01144 (17) | 0.3949 (4) | 0.0630 (10) | |
H17A | 0.7174 | −0.0394 | 0.3260 | 0.076* | |
H17B | 0.7284 | −0.0331 | 0.4622 | 0.076* | |
H17C | 0.8429 | 0.0037 | 0.4215 | 0.076* | |
Cl1 | 0.5741 (4) | 0.08778 (18) | 0.9278 (3) | 0.1034 (12)* | 0.50 |
Cl2 | 0.2629 (3) | 0.07516 (13) | 0.9204 (3) | 0.0771 (7)* | 0.50 |
C18 | 0.4239 (13) | 0.1172 (5) | 0.9771 (10) | 0.101 (2)* | 0.50 |
H18A | 0.4639 | 0.1168 | 1.0672 | 0.121* | 0.50 |
H18B | 0.4000 | 0.1600 | 0.9498 | 0.121* | 0.50 |
Cl1A | 0.5570 (5) | 0.11043 (19) | 0.9325 (4) | 0.1097 (13)* | 0.50 |
Cl2A | 0.2987 (5) | 0.0560 (2) | 0.9671 (4) | 0.1473 (16)* | 0.50 |
C18A | 0.4598 (13) | 0.0871 (5) | 1.0129 (10) | 0.101 (2)* | 0.50 |
H18C | 0.5282 | 0.0586 | 1.0744 | 0.121* | 0.50 |
H18D | 0.4523 | 0.1236 | 1.0588 | 0.121* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0849 (7) | 0.0581 (6) | 0.0589 (6) | 0.0082 (5) | 0.0341 (6) | 0.0148 (5) |
S2 | 0.0457 (5) | 0.0594 (6) | 0.0636 (6) | 0.0125 (4) | 0.0260 (4) | 0.0039 (4) |
O1 | 0.0481 (12) | 0.0405 (12) | 0.0446 (12) | −0.0015 (10) | 0.0263 (11) | −0.0047 (10) |
N1 | 0.0510 (17) | 0.0614 (19) | 0.0465 (16) | −0.0083 (14) | 0.0287 (14) | −0.0132 (14) |
N2 | 0.0468 (16) | 0.0470 (17) | 0.0558 (18) | −0.0024 (13) | 0.0228 (14) | 0.0020 (13) |
C1 | 0.0368 (17) | 0.0365 (17) | 0.0403 (17) | 0.0043 (13) | 0.0177 (15) | 0.0035 (14) |
C2 | 0.0431 (17) | 0.0378 (17) | 0.0364 (17) | 0.0055 (14) | 0.0191 (15) | 0.0003 (13) |
C3 | 0.0384 (17) | 0.0388 (17) | 0.0405 (17) | 0.0040 (14) | 0.0148 (14) | 0.0041 (14) |
C4 | 0.0380 (17) | 0.050 (2) | 0.0489 (19) | 0.0051 (15) | 0.0231 (16) | 0.0035 (16) |
C5 | 0.0456 (18) | 0.0416 (18) | 0.0425 (18) | 0.0087 (15) | 0.0209 (16) | 0.0022 (15) |
C6 | 0.0435 (18) | 0.0425 (18) | 0.0405 (18) | 0.0017 (15) | 0.0163 (15) | −0.0042 (14) |
C7 | 0.0416 (18) | 0.049 (2) | 0.0341 (17) | 0.0013 (15) | 0.0171 (15) | −0.0026 (14) |
C8 | 0.062 (2) | 0.066 (2) | 0.054 (2) | 0.0032 (18) | 0.0325 (19) | −0.0062 (18) |
C9 | 0.0402 (18) | 0.048 (2) | 0.048 (2) | −0.0042 (15) | 0.0172 (16) | −0.0043 (15) |
C10 | 0.074 (3) | 0.074 (3) | 0.052 (2) | −0.019 (2) | 0.013 (2) | −0.007 (2) |
C11 | 0.063 (2) | 0.050 (2) | 0.092 (3) | −0.0103 (19) | 0.030 (2) | −0.001 (2) |
C12 | 0.045 (2) | 0.095 (3) | 0.081 (3) | −0.014 (2) | 0.025 (2) | −0.025 (2) |
C13 | 0.0407 (17) | 0.057 (2) | 0.0343 (17) | −0.0093 (15) | 0.0148 (15) | −0.0044 (15) |
C14 | 0.064 (2) | 0.058 (2) | 0.085 (3) | −0.0012 (19) | 0.045 (2) | −0.019 (2) |
C15 | 0.075 (3) | 0.105 (3) | 0.054 (2) | −0.012 (2) | 0.040 (2) | −0.016 (2) |
C16 | 0.056 (2) | 0.076 (3) | 0.084 (3) | −0.015 (2) | 0.032 (2) | 0.003 (2) |
C17 | 0.071 (3) | 0.043 (2) | 0.078 (3) | −0.0023 (18) | 0.033 (2) | 0.0017 (18) |
S1—C13 | 1.650 (4) | C10—H10B | 0.9600 |
S2—C7 | 1.679 (3) | C10—H10C | 0.9600 |
O1—C13 | 1.358 (3) | C11—H11A | 0.9600 |
O1—C2 | 1.395 (3) | C11—H11B | 0.9600 |
N1—C13 | 1.327 (4) | C11—H11C | 0.9600 |
N1—C14 | 1.444 (5) | C12—H12A | 0.9600 |
N1—C15 | 1.453 (4) | C12—H12B | 0.9600 |
N2—C7 | 1.316 (4) | C12—H12C | 0.9600 |
N2—C16 | 1.461 (4) | C14—H14A | 0.9600 |
N2—C17 | 1.464 (4) | C14—H14B | 0.9600 |
C1—C6 | 1.386 (4) | C14—H14C | 0.9600 |
C1—C2 | 1.387 (4) | C15—H15A | 0.9600 |
C1—C7 | 1.499 (4) | C15—H15B | 0.9600 |
C2—C3 | 1.396 (4) | C15—H15C | 0.9600 |
C3—C4 | 1.391 (4) | C16—H16A | 0.9600 |
C3—C9 | 1.543 (4) | C16—H16B | 0.9600 |
C4—C5 | 1.376 (4) | C16—H16C | 0.9600 |
C4—H4 | 0.9300 | C17—H17A | 0.9600 |
C5—C6 | 1.370 (4) | C17—H17B | 0.9600 |
C5—C8 | 1.513 (4) | C17—H17C | 0.9600 |
C6—H6 | 0.9300 | Cl1—C18 | 1.854 (12) |
C8—H8A | 0.9600 | Cl2—C18 | 1.666 (11) |
C8—H8B | 0.9600 | C18—H18A | 0.9700 |
C8—H8C | 0.9600 | C18—H18B | 0.9700 |
C9—C10 | 1.516 (5) | Cl1A—C18A | 1.645 (12) |
C9—C12 | 1.530 (4) | Cl2A—C18A | 1.554 (12) |
C9—C11 | 1.532 (5) | C18A—H18C | 0.9700 |
C10—H10A | 0.9600 | C18A—H18D | 0.9700 |
C13—O1—C2 | 122.2 (2) | C9—C11—H11C | 109.5 |
C13—N1—C14 | 122.1 (3) | H11A—C11—H11C | 109.5 |
C13—N1—C15 | 119.9 (3) | H11B—C11—H11C | 109.5 |
C14—N1—C15 | 117.9 (3) | C9—C12—H12A | 109.5 |
C7—N2—C16 | 120.3 (3) | C9—C12—H12B | 109.5 |
C7—N2—C17 | 124.1 (3) | H12A—C12—H12B | 109.5 |
C16—N2—C17 | 115.4 (3) | C9—C12—H12C | 109.5 |
C6—C1—C2 | 118.2 (3) | H12A—C12—H12C | 109.5 |
C6—C1—C7 | 118.1 (3) | H12B—C12—H12C | 109.5 |
C2—C1—C7 | 123.5 (3) | N1—C13—O1 | 109.4 (3) |
C1—C2—O1 | 119.7 (3) | N1—C13—S1 | 126.5 (2) |
C1—C2—C3 | 122.3 (3) | O1—C13—S1 | 124.0 (2) |
O1—C2—C3 | 117.7 (3) | N1—C14—H14A | 109.5 |
C4—C3—C2 | 116.0 (3) | N1—C14—H14B | 109.5 |
C4—C3—C9 | 121.3 (3) | H14A—C14—H14B | 109.5 |
C2—C3—C9 | 122.7 (3) | N1—C14—H14C | 109.5 |
C5—C4—C3 | 123.5 (3) | H14A—C14—H14C | 109.5 |
C5—C4—H4 | 118.2 | H14B—C14—H14C | 109.5 |
C3—C4—H4 | 118.2 | N1—C15—H15A | 109.5 |
C6—C5—C4 | 118.1 (3) | N1—C15—H15B | 109.5 |
C6—C5—C8 | 120.3 (3) | H15A—C15—H15B | 109.5 |
C4—C5—C8 | 121.6 (3) | N1—C15—H15C | 109.5 |
C5—C6—C1 | 121.9 (3) | H15A—C15—H15C | 109.5 |
C5—C6—H6 | 119.1 | H15B—C15—H15C | 109.5 |
C1—C6—H6 | 119.1 | N2—C16—H16A | 109.5 |
N2—C7—C1 | 118.1 (3) | N2—C16—H16B | 109.5 |
N2—C7—S2 | 123.1 (2) | H16A—C16—H16B | 109.5 |
C1—C7—S2 | 118.4 (2) | N2—C16—H16C | 109.5 |
C5—C8—H8A | 109.5 | H16A—C16—H16C | 109.5 |
C5—C8—H8B | 109.5 | H16B—C16—H16C | 109.5 |
H8A—C8—H8B | 109.5 | N2—C17—H17A | 109.5 |
C5—C8—H8C | 109.5 | N2—C17—H17B | 109.5 |
H8A—C8—H8C | 109.5 | H17A—C17—H17B | 109.5 |
H8B—C8—H8C | 109.5 | N2—C17—H17C | 109.5 |
C10—C9—C12 | 107.2 (3) | H17A—C17—H17C | 109.5 |
C10—C9—C11 | 109.4 (3) | H17B—C17—H17C | 109.5 |
C12—C9—C11 | 106.9 (3) | Cl2—C18—Cl1 | 112.9 (6) |
C10—C9—C3 | 112.0 (3) | Cl2—C18—H18A | 109.0 |
C12—C9—C3 | 111.6 (3) | Cl1—C18—H18A | 109.0 |
C11—C9—C3 | 109.5 (3) | Cl2—C18—H18B | 109.0 |
C9—C10—H10A | 109.5 | Cl1—C18—H18B | 109.0 |
C9—C10—H10B | 109.5 | H18A—C18—H18B | 107.8 |
H10A—C10—H10B | 109.5 | Cl2A—C18A—Cl1A | 129.4 (8) |
C9—C10—H10C | 109.5 | Cl2A—C18A—H18C | 104.9 |
H10A—C10—H10C | 109.5 | Cl1A—C18A—H18C | 104.9 |
H10B—C10—H10C | 109.5 | Cl2A—C18A—H18D | 104.9 |
C9—C11—H11A | 109.5 | Cl1A—C18A—H18D | 104.9 |
C9—C11—H11B | 109.5 | H18C—C18A—H18D | 105.8 |
H11A—C11—H11B | 109.5 |
Experimental details
Crystal data | |
Chemical formula | C17H26N2OS2·CH2Cl2 |
Mr | 423.44 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 291 |
a, b, c (Å) | 9.5032 (5), 21.4599 (10), 11.7601 (7) |
β (°) | 113.791 (1) |
V (Å3) | 2194.5 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.50 |
Crystal size (mm) | 0.30 × 0.22 × 0.16 |
Data collection | |
Diffractometer | Bruker Smart Apex CCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17814, 3851, 2621 |
Rint | 0.051 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.061, 0.167, 0.99 |
No. of reflections | 3851 |
No. of parameters | 230 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.50, −0.43 |
Computer programs: SMART (Bruker, Date), SMART, SAINT (Bruker, Date), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, Date), SHELXTL.
S1—C13 | 1.650 (4) | N1—C13 | 1.327 (4) |
S2—C7 | 1.679 (3) | N2—C7 | 1.316 (4) |
O1—C13 | 1.358 (3) | C1—C7 | 1.499 (4) |
O1—C2 | 1.395 (3) | ||
C13—O1—C2 | 122.2 (2) | N1—C13—O1 | 109.4 (3) |
N2—C7—C1 | 118.1 (3) | N1—C13—S1 | 126.5 (2) |
N2—C7—S2 | 123.1 (2) | O1—C13—S1 | 124.0 (2) |
C1—C7—S2 | 118.4 (2) |
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The synthesis of substituted thiophenols from the corresponding phenols requires the initial preparation and purification of substituted O-phenylthiocarbamoates. The latter compounds are necessary for the Newman–Kwart thermal rearrangement, which is the key step in the transformation of O-phenylthiocarbamoates to the corresponding S-phenylthiocarbamoates (Newman & Karnes, 1966). In order to prepare a series of substituted thiophenols, we decided to undertake the synthesis and structural characterization of substituted O-thiocarbamoates. We report here the preparation of the title O-thiocarbamoate, (I).
Compound (I) crystallizes with a disordered molecule of dichloromethane in the monoclinic space group P21/c by slow evaporation of a concentrated dichloromethane solution. A search of the Cambridge Crystallographic Database (CONQUEST, Version 1.4; Cambridge Structural Database, 2002) revealed that there are no solid-state structure reports of aromatic compounds possessing both thiocarbamoate and carbonothioyl moieties. Thus, (I) is the first of its kind to be crystallographically characterized.
The crystal structure features distinctly short C═S bond distances for C13═S1 and C7═S2 (Table 1). The shorter C13═S1 bond distance, which corresponds to the thiocarbamoate group, is associated with the marginally longer C13═N1 bond, while the longer C7═S2 bond, which corresponds to the carbonothioyl group, is associated with the marginally shorter C7═N2 bond.
The bond lengths and angles of the thiocarbamoate group of (I) are comparable to those of the related compounds N,N-diethylthiocarbamic acid 2-[(diethylamino)carbonyl]-3-formylphenyl ester (Stanetty et al., 2002) and the sterically demanding O-{2-[bis(pyrazol-1'-yl)methyl]-6-tert-butyl-4- methylphenyl}-N,N-dimethylthiocarbamoate (Higgs & Carrano, 2002). Thus, the bond angles around the sp2-hybridized C atoms of the thiocarbamoate moities of all three compounds are very similar, with values of 109.4 (3), 110.1 (2), and 110.1 (2)° for the N—C—O angle, 126.5 (2), 126.9 (2) and 126.5 (2)° for the N—C—S angle, and 124.0 (2), 123.0 (2) and 123.4 (2)° for the O—C—S angle, respectively. Although the corresponding bond lengths are comparable for the three compounds, the C═S bond length of (I) is the shortest of all at 1.647 (4) Å, including those of other related thiocarbamoates (Bandarage et al., 1994; Rao et al., 2000). The geometric parameters of the carbonothioyl fragment, on the other hand, are comparable to those of the related compounds N,N-dimethylthiobenzamide (Walter et al., 1976) and 2-hydroxy-N,N-dimethylthiobenzamide (Pertlik, 1990). The dihedral angle between the thiocarbamoate plane, defined by atoms S1, O1, N1 and C13–C15, and the aromatic C1–C6 ring is 70.2 (1)°, which reflects the steric congestion due to the presence of the bulky tert-butyl and the sulfur-containing groups. This is further reflected in the dihedral angle between the carbonothioyl moiety and the aromatic ring [62.8 (2)°]. The corresponding dihedral angle between the thiocarbamoate and carbonothioyl moieties is 54.4 (2)°.
Interestingly, the dichloromethane molecules pack along pseudochannels, which can be viewed along the [100] axis in Fig. 2. Examination of the structure with PLATON (Spek, 2003) shows that there are intermolecular interactions between atoms Cl1 and Cl1A on dichloromethane and atom H15A on the dimethylamino group of the thiocarbamoate functionality, as well as between atom Cl2 and atom H17A on atom C17 of the carbonothioyl fragment. Another interaction is observed between atom Cl2A and atom H6 on atom C6 of the aromatic ring. These interactions, together with the weak S2···H18A hydrogen bond (2.86 Å), are probably responsible for stabilizing the dichloromethane molecule in the observed position. There are also short intramolecular contacts that need comment. Thus, there are three C—H···O1 interactions, to atoms H10A, H11A and H14C (2.36, 2.42 and 2.43 Å). The first two appear to be determined by the proximity of the tert-butyl group to atom O1, whereas that to H14C appears to be determined by the planarity of the thiocarbamoate fragment, which brings the C14 methyl group close to atom O1. The latter geometric feature is also responsible for the short contact between atoms H15C (on C15) and S1, with an H···S distance of 2.78 Å, some 0.16 Å shorter than the sum of the van der Waals radii (Bondi, 1964). An analogous intramolecular contact between atoms H16C and S2 (2.81 Å) arises as a result of the planarity of the carbonothioyl moiety.