O-(2-tert-Butyl-6-di­methyl­thio­carbamoyl-4-methylphenyl) N,N-di­methyl­thiocarbamate di­chloro­methane solvate

In the title compound, C₁₇H₂₆N₂OS₂·CH₂Cl₂, the C=S distances are 1.650 (4) and 1.679 (3) Å, and the torsion angle between the planes of the thio­carbamate and carbono­thio­yl fragments is 54.4 (2)°. The steric and electronic effects that these substituents exert on one another determine the observed anti configuration with respect to the phenyl C atoms to which they are attached.

S1. Comment

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.

S2. Experimental

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%).

S3. Refinement

The positional parameters of the H atoms were calculated geometrically and refined as riding, with a fixed U_iso value (1.2U_eq 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.

Computing details

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.

Figures

	Fig. 1. The molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are shown at the 40% probability level. The CH2Cl2 molecule is disorderd (see text).
	Fig. 2. A view of the pseudochannels along the [100] direction containing the CH2Cl2 molecules.

O-(2-tert-butyl-6-dimethylcarbonothioyl-4-methyl-phenyl) dimethylthiocarbamoate dichloromethane solvate.

Crystal data

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) Å^3	Prism, colorless
Z = 4	0.30 × 0.22 × 0.16 mm

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.167	H-atom parameters constrained
S = 0.99	w = 1/[σ^2(Fo^2) + (0.096P)^2] where P = (Fo^2 + 2Fc^2)/3
3851 reflections	(Δ/σ)max = 0.002
230 parameters	Δρmax = 0.50 e Å^−3
0 restraints	Δρmin = −0.43 e Å^−3

Special details

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 (Ų)

	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

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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