Bis(N-cyclo­hexyl-N-methyl­di­thio­carbamato)­di­methyl­tin(IV)

The mol­ecule of the title compound, [Sn(CH₃)₂(C₈H₁₄NS₂)₂], occupies a special position on a crystallographic mirror plane which coincides with the plane of the di­methyl­tin group. The severely distorted coordination tetrahedron formed by the four strong bonds of the Sn atom [Sn—C = 2.101 (4) and 2.108 (5) Å, Sn—S = 2.5169 (7) Å, C—Sn—C = 137.0 (2)° and S—Sn—S = 84.46 (3)°] is expanded to a distorted octahedron due to weak intramolecular Sn...S interactions of 2.9785 (6) Å.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.032
• wR factor = 0.081
• Data-to-parameter ratio = 23.7

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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S1. Comment

The comparison of the geometry of numerous bis(dithiocarbamato)dimethyltin and bis(dithiocarbamato)diphenyltin complexes reveals interesting differences between dimethyltin and diphenyltin derivatives. It turns out that dimethyltin complexes show in most cases substantially larger C—Sn—C angles than their diphenyltin analogues [e.g. 136.0 (1)° in Me₂Sn(S₂CNMe₂)₂ (Kimura at al., 1972) and 101.4 (6)° in Ph₂Sn(S₂CNEt₂)₂ (Lindley & Carr, 1974)]. Furthermore, in diphenyltin complexes, one of the ligands usually chelates the Sn atom symmetrically, whereas the other ligand shows a considerable difference in the Sn—S bond distances. On the contrary, in dimethyltin complexes, both ligands display the same coordination pattern with one shorter Sn—S bond and one longer Sn···S `secondary' contact.

The geometry of the title compound, (I), is typical for the bis(dithiocarbamato)dimethyltin complexes and illustrates the features outlined above. As well as its analogue, bis[N,N-bis(2-hydroxyethyl)dithiocarbamato]dimethyltin(IV) (Farina et al., 2000), molecule (I) has a crystallographic mirror plane, coinciding with the C9/Sn1/C10 plane. The severely distorted coordination tetrahedron formed by the four strong bonds of the Sn atom [Sn1—C9 = 2.101 (4), Sn1—C10 = 2.108 (5) and Sn1—S1 = 2.5169 (7) Å; C9—Sn1—C10 = 137.0 (2)° and S1—Sn1—S1ⁱ = 84.46 (3)°; symmetry code: (i) x, 1.5 − y, z] is promoted to a distorted octahedron due to weak intramolecular Sn1···S2 interactions of 2.9785 (6) Å, the S2—Sn1—S2ⁱ angle being 146.35 (2)°

The Sn1 atom shows very small displacement from the plane of the coordinating atoms S1, S2, S1A and S2A [0.0048 (8) Å]; the four-membered chelate ring is almost planar and the torsion angle Sn1—S1—C8—S2 is −6.89 (15)°.

S2. Experimental

To a solution of N-methylcyclohexylamine (3.9 ml, 0.04 mol) in ethanol was added with stirring at 273 K, carbon disulfide (1.8 ml, 0.03 mol). After stirring for 2 h, 3.295 g (0.015 mol) of dimethyltin(IV) chloride (10.00 ml) was added dropwise to the mixture. The mixture was then stirred vigorously for 1 h. The white solid obtained was recrystallized from chloroform.

S3. Refinement

After their location in a difference map, all H atoms were fixed geometrically at ideal positions and allowed to ride on the parent atoms, with C—H = 0.93–0.97 Å. However, the H atoms at C9 and C10 were located and refined f reely and then fixed.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).

Figures

Fig. 1. The molecular structure of the title compound, (I), with 50% probability displacement ellipsoids

Bis(N-cyclohexyl-N-methyldithiocarbamato)dimethyltin(IV)

Crystal data

[Sn(CH3)2(C8H14NS2)2]	Dx = 1.480 Mg m^−3
Mr = 525.40	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pnma	Cell parameters from 4467 reflections
a = 13.2000 (9) Å	θ = 2.0–27.6°
b = 19.9650 (14) Å	µ = 1.44 mm^−1
c = 8.9503 (6) Å	T = 293 K
V = 2358.7 (3) Å^3	Block, light yellow
Z = 4	0.27 × 0.22 × 0.16 mm
F(000) = 1080

Data collection

Bruker SMART APEX CCD area-detector diffractometer	2795 independent reflections
Radiation source: fine-focus sealed tube	2441 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
Detector resolution: 83.66 pixels mm^-1	θmax = 27.6°, θmin = 2.0°
ω scans	h = −17→16
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −25→25
Tmin = 0.696, Tmax = 0.802	l = −11→11
15359 measured reflections

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.081	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0415P)^2 + 0.8626P] where P = (Fo^2 + 2Fc^2)/3
2795 reflections	(Δ/σ)max < 0.001
118 parameters	Δρmax = 0.74 e Å^−3
0 restraints	Δρmin = −0.33 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Sn1	0.356754 (18)	0.7500	0.16669 (3)	0.04299 (10)
S1	0.22144 (5)	0.66527 (3)	0.22612 (8)	0.04575 (17)
S2	0.41923 (5)	0.60720 (3)	0.13864 (11)	0.0616 (2)
C1	0.2710 (2)	0.41283 (13)	0.1818 (3)	0.0519 (7)
H1A	0.2389	0.4210	0.0860	0.062*
H1B	0.2185	0.4019	0.2537	0.062*
C2	0.3452 (3)	0.35471 (15)	0.1684 (3)	0.0633 (9)
H2A	0.3087	0.3145	0.1397	0.076*
H2B	0.3942	0.3645	0.0907	0.076*
C3	0.4003 (3)	0.34241 (14)	0.3147 (4)	0.0635 (8)
H3A	0.3520	0.3272	0.3891	0.076*
H3B	0.4500	0.3072	0.3005	0.076*
C4	0.4525 (2)	0.40427 (14)	0.3711 (4)	0.0648 (8)
H4A	0.5078	0.4156	0.3044	0.078*
H4B	0.4809	0.3954	0.4691	0.078*
C5	0.3799 (2)	0.46317 (13)	0.3812 (3)	0.0495 (6)
H5A	0.3293	0.4542	0.4572	0.059*
H5B	0.4170	0.5031	0.4102	0.059*
C6	0.32787 (19)	0.47514 (11)	0.2323 (3)	0.0398 (5)
H6A	0.3809	0.4839	0.1582	0.048*
C7	0.16135 (19)	0.52808 (14)	0.3003 (3)	0.0487 (6)
H7A	0.1274	0.5706	0.2990	0.073*
H7B	0.1652	0.5119	0.4011	0.073*
H7C	0.1243	0.4967	0.2403	0.073*
C8	0.30031 (18)	0.59560 (11)	0.2045 (3)	0.0383 (5)
C9	0.4502 (4)	0.7500	0.3566 (6)	0.0846 (17)
H9A	0.4313	0.7163	0.4030	0.102*
H9B	0.5074	0.7500	0.3311	0.102*
C10	0.3764 (4)	0.7500	−0.0670 (5)	0.0687 (12)
H10B	0.3581	0.7850	−0.1074	0.082*
H10A	0.4425	0.7500	−0.0650	0.082*
N1	0.26326 (14)	0.53576 (9)	0.2403 (2)	0.0384 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Sn1	0.03687 (15)	0.03148 (14)	0.06062 (18)	0.000	−0.00282 (10)	0.000
S1	0.0385 (3)	0.0294 (3)	0.0693 (4)	0.0033 (2)	0.0024 (3)	0.0010 (3)
S2	0.0381 (4)	0.0323 (3)	0.1143 (7)	0.0004 (3)	0.0151 (4)	0.0088 (3)
C1	0.0631 (18)	0.0335 (13)	0.0591 (16)	−0.0064 (12)	−0.0017 (13)	−0.0044 (11)
C2	0.090 (2)	0.0293 (13)	0.071 (2)	0.0016 (14)	0.0077 (16)	−0.0055 (12)
C3	0.079 (2)	0.0346 (14)	0.077 (2)	0.0067 (14)	0.0101 (16)	0.0076 (13)
C4	0.0639 (19)	0.0416 (15)	0.089 (2)	0.0090 (14)	−0.0074 (16)	0.0124 (14)
C5	0.0532 (15)	0.0344 (13)	0.0609 (16)	0.0030 (11)	−0.0069 (13)	0.0009 (11)
C6	0.0446 (13)	0.0260 (10)	0.0486 (13)	−0.0001 (10)	0.0052 (11)	0.0013 (10)
C7	0.0426 (14)	0.0405 (13)	0.0629 (17)	−0.0029 (11)	0.0100 (12)	0.0020 (12)
C8	0.0351 (12)	0.0291 (11)	0.0507 (13)	0.0005 (9)	−0.0034 (10)	0.0010 (9)
C9	0.081 (4)	0.059 (3)	0.114 (4)	0.000	−0.047 (3)	0.000
C10	0.084 (3)	0.051 (2)	0.071 (3)	0.000	0.018 (2)	0.000
N1	0.0350 (10)	0.0296 (9)	0.0508 (12)	−0.0006 (8)	0.0014 (8)	0.0010 (8)

Geometric parameters (Å, º)

Sn1—S1	2.5169 (7)	C4—C5	1.520 (4)
Sn1—S2	2.9785 (6)	C4—H4A	0.9700
Sn1—C9	2.101 (4)	C4—H4B	0.9700
Sn1—C10	2.108 (5)	C5—C6	1.518 (4)
Sn1—S1^i	2.5169 (6)	C5—H5A	0.9700
S1—C8	1.748 (2)	C5—H5B	0.9700
S2—C8	1.693 (3)	C6—N1	1.482 (3)
C1—C6	1.522 (3)	C6—H6A	0.9800
C1—C2	1.524 (4)	C7—N1	1.457 (3)
C1—H1A	0.9700	C7—H7A	0.9600
C1—H1B	0.9700	C7—H7B	0.9600
C2—C3	1.518 (4)	C7—H7C	0.9600
C2—H2A	0.9700	C8—N1	1.330 (3)
C2—H2B	0.9700	C9—H9A	0.8294
C3—C4	1.502 (4)	C9—H9B	0.7880
C3—H3A	0.9700	C10—H10B	0.8231
C3—H3B	0.9700	C10—H10A	0.8727
S1—Sn1—S1^i	84.46 (3)	H4A—C4—H4B	108.0
S2—Sn1—S2^i	146.35 (2)	C6—C5—C4	110.8 (2)
C9—Sn1—C10	137.0 (2)	C6—C5—H5A	109.5
C9—Sn1—S1	104.23 (13)	C4—C5—H5A	109.5
C10—Sn1—S1	107.28 (10)	C6—C5—H5B	109.5
C9—Sn1—S1^i	104.23 (13)	C4—C5—H5B	109.5
C10—Sn1—S1^i	107.28 (10)	H5A—C5—H5B	108.1
C8—S1—Sn1	95.09 (8)	N1—C6—C5	110.3 (2)
C6—C1—C2	109.2 (2)	N1—C6—C1	113.4 (2)
C6—C1—H1A	109.8	C5—C6—C1	110.8 (2)
C2—C1—H1A	109.8	N1—C6—H6A	107.3
C6—C1—H1B	109.8	C5—C6—H6A	107.3
C2—C1—H1B	109.8	C1—C6—H6A	107.3
H1A—C1—H1B	108.3	N1—C7—H7A	109.5
C3—C2—C1	111.3 (2)	N1—C7—H7B	109.5
C3—C2—H2A	109.4	H7A—C7—H7B	109.5
C1—C2—H2A	109.4	N1—C7—H7C	109.5
C3—C2—H2B	109.4	H7A—C7—H7C	109.5
C1—C2—H2B	109.4	H7B—C7—H7C	109.5
H2A—C2—H2B	108.0	N1—C8—S2	123.21 (18)
C4—C3—C2	112.1 (2)	N1—C8—S1	117.98 (18)
C4—C3—H3A	109.2	S2—C8—S1	118.81 (13)
C2—C3—H3A	109.2	Sn1—C9—H9A	103.2
C4—C3—H3B	109.2	Sn1—C9—H9B	109.1
C2—C3—H3B	109.2	H9A—C9—H9B	115.7
H3A—C3—H3B	107.9	Sn1—C10—H10B	113.6
C3—C4—C5	111.5 (3)	Sn1—C10—H10A	95.9
C3—C4—H4A	109.3	H10B—C10—H10A	107.6
C5—C4—H4A	109.3	C8—N1—C7	121.5 (2)
C3—C4—H4B	109.3	C8—N1—C6	120.68 (19)
C5—C4—H4B	109.3	C7—N1—C6	117.60 (19)
C9—Sn1—S1—C8	−73.01 (15)	Sn1—S1—C8—N1	173.42 (18)
C10—Sn1—S1—C8	77.28 (14)	Sn1—S1—C8—S2	−6.89 (15)
S1^i—Sn1—S1—C8	−176.32 (8)	S2—C8—N1—C7	178.4 (2)
C6—C1—C2—C3	57.0 (3)	S1—C8—N1—C7	−1.9 (3)
C1—C2—C3—C4	−55.1 (4)	S2—C8—N1—C6	3.6 (3)
C2—C3—C4—C5	53.4 (4)	S1—C8—N1—C6	−176.72 (17)
C3—C4—C5—C6	−54.6 (3)	C5—C6—N1—C8	90.7 (3)
C4—C5—C6—N1	−175.7 (2)	C1—C6—N1—C8	−144.4 (2)
C4—C5—C6—C1	57.8 (3)	C5—C6—N1—C7	−84.3 (3)
C2—C1—C6—N1	176.6 (2)	C1—C6—N1—C7	40.7 (3)
C2—C1—C6—C5	−58.7 (3)

Symmetry code: (i) x, −y+3/2, z.