(N-Cyclo­hexyl-N-methyl­di­thio­carbamato)­tri­phenyl­tin(IV)

The title compound, Ph₃Sn[S₂CN(Me)C₆H₁₁], has an iso­bidentate ligand, with the tin coordination geometry intermediate between tetrahedral and distorted trigonal bipyra­midal, owing to the presence of a long intramolecular Sn...S interaction of 3.0134 (8) Å.

Key indicators

• Single-crystal X-ray study
• T = 273 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.025
• wR factor = 0.070
• Data-to-parameter ratio = 20.9

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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S1. Comment

(Dithiocarbamato)diorganotin complexes such as bis(dimethyldithiocarbamato) dimethyltin (Kimura, et al., 1972) and bis(diethyldithiocarbamato)diphenyltin (Lindley & Carr, 1974) are known to show an expansion and distortion in their geometries due to weak intramolecular Sn···S interaction. The nature of the ligands and the substituents at the tin atom also have an influence on the coordination environment of the complex. The title compound, (I), a triorganotin system with an unsymmetrical ligand is isostructural to (N-butyl-N-methyldithiocarbamato)triphenyltin(IV), Ph₃Sn[S₂CN(CH₃C₄ H₉], (Kana et al., 2001) and (diethyldithiocarbamato)triphenyltin(IV) (Lindley & Carr, 1974). The isobidentate nature of the chelation, with Sn1—S1 = 2.4558 (6) Å and a weak intramolecular Sn1···S2 interaction of 3.0134 (8) Å [2.4631 (9) and 3.084 (1) Å respectively in Ph₃Sn(S₂CN(CH₃)C₄H₉)] caused a coordination between tetrahedral and distorted trigonal bipyramidal. The angles C6—Sn1—S1, C6—Sn1—C18 and C18—Sn1—S1 [116.14 (5), 116.63 (8) and 116,28 (6) Å, respectively] are close to 120°, as expected at equatorial positions, and the Cl2—Sn1—S2 angle at the non-linear axial position is 158.43 (6)°. Other bond parameters of the ligand are normal and similar to those in bis(N-cyclohexyl-N-methyldithiocarbamato)dimethyltin(IV), which has a severely distorted octahedral geometry (Awang et al., 2003.)

S2. Experimental

The title compound was synthesized by the addition of carbon disulfide, CS₂ (1.8 ml, 0.03 mol) to an ethanolic solution of N-methylcyclohaxylamine (4 ml, 0.03 mol) with stirring for one hour at 269 K. Triphenyltin(IV) chloride (11.6 g, 0.03 mol) solution was then added and the solution mixture was stirred for another hour. The resulting white precipitate was filtered, washed with cold ethanol and dried in vacuo. Some good quality crystals suitable for X-ray analysis were obained by recrystallization from a 1:1 mixture of ethanol and chloroform.

S3. Refinement

After their location in the difference Fourier map, all H-atoms were included in the refinement in geometrically calculated positions, and allowed to ride on the parent C atoms, with C—H = 0.93–0.98. respectively.

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; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).

Figures

Fig. 1. : Molecular structure of (I), with displacement ellipsoids drawn at the 50% probability level.

triphenyl(methylcyclohexyl)dithiocarbamato tin(IV)

Crystal data

[Sn(C8H14NS2)(C6H5)3]	Z = 2
Mr = 538.31	F(000) = 548
Triclinic, P1	Dx = 1.438 Mg m^−3
a = 9.7951 (17) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.342 (2) Å	Cell parameters from 6115 reflections
c = 11.952 (2) Å	θ = 1.8–27.6°
α = 75.037 (3)°	µ = 1.21 mm^−1
β = 75.962 (3)°	T = 273 K
γ = 89.058 (3)°	Block, white
V = 1242.9 (4) Å^3	0.53 × 0.42 × 0.26 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer	5658 independent reflections
Radiation source: fine-focus sealed tube	5341 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
Detector resolution: 83.66 pixels mm^-1	θmax = 27.6°, θmin = 1.8°
ω scan	h = −12→12
Absorption correction: multi-scan SADABS (Sheldrick, 1996)	k = −14→14
Tmin = 0.566, Tmax = 0.744	l = −15→15
15537 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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.070	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0401P)^2 + 0.3014P] where P = (Fo^2 + 2Fc^2)/3
5658 reflections	(Δ/σ)max < 0.001
271 parameters	Δρmax = 0.53 e Å^−3
0 restraints	Δρmin = −0.41 e Å^−3

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

	x	y	z	Uiso*/Ueq
Sn1	0.110896 (13)	0.304553 (11)	0.197516 (11)	0.04381 (6)
S1	0.27879 (6)	0.43476 (5)	0.02397 (5)	0.05226 (12)
S2	0.32599 (6)	0.17194 (5)	0.05500 (5)	0.05533 (13)
N1	0.46193 (19)	0.34731 (16)	−0.13134 (16)	0.0518 (4)
C1	−0.0336 (2)	0.0920 (2)	0.1389 (2)	0.0546 (5)
H1A	0.0510	0.0539	0.1405	0.066*
C2	−0.1422 (3)	0.0329 (2)	0.1163 (2)	0.0646 (6)
H2A	−0.1308	−0.0448	0.1042	0.077*
C3	−0.2672 (3)	0.0889 (3)	0.1115 (3)	0.0697 (7)
H3A	−0.3401	0.0499	0.0952	0.084*
C4	−0.2829 (3)	0.2016 (3)	0.1306 (3)	0.0765 (8)
H4A	−0.3668	0.2401	0.1270	0.092*
C5	−0.1760 (2)	0.2597 (2)	0.1554 (2)	0.0627 (6)
H5A	−0.1895	0.3363	0.1699	0.075*
C6	−0.0487 (2)	0.20625 (18)	0.15932 (17)	0.0446 (4)
C7	−0.0211 (3)	0.5583 (2)	0.1646 (2)	0.0617 (6)
H7A	0.0164	0.5637	0.0841	0.074*
C8	−0.0971 (3)	0.6525 (3)	0.1965 (3)	0.0786 (8)
H8A	−0.1096	0.7209	0.1379	0.094*
C9	−0.1541 (3)	0.6455 (3)	0.3138 (4)	0.0881 (10)
H9A	−0.2076	0.7083	0.3355	0.106*
C10	−0.1329 (4)	0.5472 (4)	0.3990 (3)	0.1023 (12)
H10A	−0.1705	0.5429	0.4794	0.123*
C11	−0.0552 (4)	0.4532 (3)	0.3664 (3)	0.0844 (9)
H11A	−0.0409	0.3862	0.4256	0.101*
C12	0.0012 (2)	0.45617 (19)	0.2486 (2)	0.0501 (4)
C13	0.1034 (3)	0.1495 (2)	0.4481 (2)	0.0579 (5)
H13A	0.0071	0.1472	0.4535	0.069*
C14	0.1527 (3)	0.0894 (3)	0.5451 (2)	0.0707 (7)
H14A	0.0897	0.0468	0.6151	0.085*
C15	0.2923 (3)	0.0918 (3)	0.5393 (2)	0.0720 (7)
H15A	0.3252	0.0510	0.6050	0.086*
C16	0.3852 (3)	0.1548 (3)	0.4359 (3)	0.0755 (7)
H16A	0.4812	0.1570	0.4318	0.091*
C17	0.3369 (2)	0.2146 (2)	0.3385 (2)	0.0603 (5)
H17A	0.4006	0.2566	0.2686	0.072*
C18	0.1943 (2)	0.21295 (18)	0.34347 (17)	0.0450 (4)
C19	0.3668 (2)	0.31636 (18)	−0.02848 (18)	0.0447 (4)
C20	0.4814 (3)	0.4727 (2)	−0.2059 (2)	0.0724 (7)
H20A	0.4174	0.5233	−0.1672	0.109*
H20B	0.4632	0.4750	−0.2818	0.109*
H20C	0.5765	0.5022	−0.2178	0.109*
C21	0.5516 (2)	0.2543 (2)	−0.1756 (2)	0.0507 (5)
H21A	0.5365	0.1809	−0.1085	0.061*
C22	0.5066 (3)	0.2184 (3)	−0.2729 (3)	0.0761 (8)
H22A	0.5188	0.2882	−0.3420	0.091*
H22B	0.4076	0.1923	−0.2464	0.091*
C23	0.5935 (3)	0.1149 (3)	−0.3071 (3)	0.0870 (9)
H23A	0.5726	0.0423	−0.2406	0.104*
H23B	0.5678	0.0963	−0.3744	0.104*
C24	0.7493 (3)	0.1487 (3)	−0.3401 (3)	0.0890 (10)
H24A	0.8024	0.0800	−0.3577	0.107*
H24B	0.7720	0.2167	−0.4112	0.107*
C25	0.7899 (3)	0.1833 (4)	−0.2400 (4)	0.1024 (13)
H25A	0.8896	0.2066	−0.2632	0.123*
H25C	0.7734	0.1132	−0.1708	0.123*
C26	0.7058 (3)	0.2893 (3)	−0.2067 (4)	0.0888 (10)
H26C	0.7307	0.3074	−0.1389	0.107*
H26A	0.7276	0.3617	−0.2733	0.107*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Sn1	0.04635 (9)	0.04229 (8)	0.04407 (9)	0.00936 (5)	−0.01259 (6)	−0.01267 (6)
S1	0.0553 (3)	0.0446 (3)	0.0552 (3)	0.0075 (2)	−0.0056 (2)	−0.0180 (2)
S2	0.0554 (3)	0.0465 (3)	0.0541 (3)	0.0077 (2)	0.0016 (2)	−0.0101 (2)
N1	0.0519 (9)	0.0471 (9)	0.0499 (9)	0.0021 (7)	0.0000 (7)	−0.0132 (7)
C1	0.0553 (11)	0.0490 (11)	0.0583 (12)	0.0068 (9)	−0.0107 (9)	−0.0153 (9)
C2	0.0720 (15)	0.0549 (13)	0.0659 (14)	−0.0072 (11)	−0.0068 (12)	−0.0232 (11)
C3	0.0576 (13)	0.0791 (17)	0.0716 (16)	−0.0144 (12)	−0.0108 (12)	−0.0225 (13)
C4	0.0470 (12)	0.0844 (19)	0.103 (2)	0.0066 (12)	−0.0217 (13)	−0.0308 (16)
C5	0.0507 (11)	0.0568 (13)	0.0840 (17)	0.0103 (10)	−0.0153 (11)	−0.0264 (12)
C6	0.0454 (9)	0.0449 (10)	0.0403 (9)	0.0043 (7)	−0.0070 (7)	−0.0089 (8)
C7	0.0706 (14)	0.0539 (12)	0.0713 (15)	0.0183 (11)	−0.0298 (12)	−0.0244 (11)
C8	0.0884 (19)	0.0575 (14)	0.114 (2)	0.0301 (13)	−0.0532 (18)	−0.0403 (15)
C9	0.0798 (18)	0.083 (2)	0.133 (3)	0.0376 (16)	−0.0431 (19)	−0.069 (2)
C10	0.116 (3)	0.112 (3)	0.086 (2)	0.039 (2)	−0.007 (2)	−0.057 (2)
C11	0.109 (2)	0.0761 (18)	0.0599 (15)	0.0291 (17)	−0.0041 (15)	−0.0215 (13)
C12	0.0508 (10)	0.0487 (11)	0.0554 (11)	0.0097 (8)	−0.0147 (9)	−0.0206 (9)
C13	0.0542 (12)	0.0675 (14)	0.0487 (11)	0.0061 (10)	−0.0092 (9)	−0.0130 (10)
C14	0.0920 (19)	0.0711 (16)	0.0444 (12)	0.0066 (14)	−0.0149 (12)	−0.0089 (11)
C15	0.101 (2)	0.0690 (16)	0.0564 (14)	0.0252 (14)	−0.0373 (14)	−0.0188 (12)
C16	0.0646 (15)	0.0904 (19)	0.0843 (19)	0.0186 (14)	−0.0387 (14)	−0.0273 (16)
C17	0.0524 (12)	0.0659 (14)	0.0605 (13)	0.0054 (10)	−0.0152 (10)	−0.0121 (11)
C18	0.0492 (10)	0.0441 (9)	0.0437 (9)	0.0096 (8)	−0.0134 (8)	−0.0136 (8)
C19	0.0405 (9)	0.0480 (10)	0.0472 (10)	0.0054 (7)	−0.0095 (7)	−0.0169 (8)
C20	0.0857 (18)	0.0516 (13)	0.0630 (15)	0.0025 (12)	0.0038 (13)	−0.0063 (11)
C21	0.0449 (10)	0.0514 (11)	0.0519 (11)	0.0036 (8)	−0.0008 (8)	−0.0170 (9)
C22	0.0710 (16)	0.0894 (19)	0.0893 (19)	0.0277 (14)	−0.0353 (14)	−0.0479 (16)
C23	0.0779 (18)	0.104 (2)	0.107 (2)	0.0306 (17)	−0.0327 (17)	−0.069 (2)
C24	0.0739 (18)	0.089 (2)	0.088 (2)	0.0141 (15)	0.0211 (15)	−0.0327 (17)
C25	0.0450 (13)	0.110 (3)	0.171 (4)	0.0178 (15)	−0.0224 (18)	−0.074 (3)
C26	0.0534 (14)	0.093 (2)	0.139 (3)	0.0060 (13)	−0.0232 (16)	−0.063 (2)

Geometric parameters (Å, º)

Sn1—S1	2.4558 (6)	C13—C18	1.375 (3)
Sn1—S2	3.0134 (8)	C13—C14	1.377 (4)
Sn1—C6	2.136 (2)	C13—H13A	0.9300
Sn1—C12	2.155 (2)	C14—C15	1.352 (4)
Sn1—C18	2.125 (2)	C14—H14A	0.9300
S1—C19	1.753 (2)	C15—C16	1.373 (4)
S2—C19	1.680 (2)	C15—H15A	0.9300
N1—C19	1.317 (3)	C16—C17	1.375 (4)
N1—C20	1.457 (3)	C16—H16A	0.9300
N1—C21	1.482 (3)	C17—C18	1.384 (3)
C1—C6	1.379 (3)	C17—H17A	0.9300
C1—C2	1.382 (3)	C20—H20A	0.9600
C1—H1A	0.9300	C20—H20B	0.9600
C2—C3	1.377 (4)	C20—H20C	0.9600
C2—H2A	0.9300	C21—C22	1.486 (3)
C3—C4	1.355 (4)	C21—C26	1.499 (3)
C3—H3A	0.9300	C21—H21A	0.9800
C4—C5	1.376 (4)	C22—C23	1.522 (4)
C4—H4A	0.9300	C22—H22A	0.9700
C5—C6	1.383 (3)	C22—H22B	0.9700
C5—H5A	0.9300	C23—C24	1.511 (4)
C7—C8	1.373 (3)	C23—H23A	0.9700
C7—C12	1.376 (3)	C23—H23B	0.9700
C7—H7A	0.9300	C24—C25	1.490 (5)
C8—C9	1.360 (5)	C24—H24A	0.9700
C8—H8A	0.9300	C24—H24B	0.9700
C9—C10	1.354 (5)	C25—C26	1.529 (4)
C9—H9A	0.9300	C25—H25A	0.9700
C10—C11	1.383 (4)	C25—H25C	0.9700
C10—H10A	0.9300	C26—H26C	0.9700
C11—C12	1.374 (4)	C26—H26A	0.9700
C11—H11A	0.9300
C6—Sn1—S1	116.14 (5)	C16—C15—H15A	120.2
C18—Sn1—C6	116.63 (8)	C15—C16—C17	120.3 (3)
C18—Sn1—S1	116.28 (6)	C15—C16—H16A	119.9
C12—Sn1—S2	158.43 (6)	C17—C16—H16A	119.9
C18—Sn1—C12	106.24 (8)	C16—C17—C18	120.6 (2)
C6—Sn1—C12	102.95 (8)	C16—C17—H17A	119.7
C12—Sn1—S1	94.08 (6)	C18—C17—H17A	119.7
C19—S1—Sn1	96.88 (7)	C13—C18—C17	118.0 (2)
C19—N1—C20	121.57 (19)	C13—C18—Sn1	119.07 (16)
C19—N1—C21	120.57 (17)	C17—C18—Sn1	122.89 (16)
C20—N1—C21	117.85 (18)	N1—C19—S2	124.29 (15)
C6—C1—C2	121.1 (2)	N1—C19—S1	117.26 (16)
C6—C1—H1A	119.5	S2—C19—S1	118.46 (11)
C2—C1—H1A	119.5	N1—C20—H20A	109.5
C3—C2—C1	120.2 (2)	N1—C20—H20B	109.5
C3—C2—H2A	119.9	H20A—C20—H20B	109.5
C1—C2—H2A	119.9	N1—C20—H20C	109.5
C4—C3—C2	119.2 (2)	H20A—C20—H20C	109.5
C4—C3—H3A	120.4	H20B—C20—H20C	109.5
C2—C3—H3A	120.4	N1—C21—C22	112.43 (19)
C3—C4—C5	120.8 (3)	N1—C21—C26	112.7 (2)
C3—C4—H4A	119.6	C22—C21—C26	113.1 (2)
C5—C4—H4A	119.6	N1—C21—H21A	106.0
C4—C5—C6	121.2 (2)	C22—C21—H21A	106.0
C4—C5—H5A	119.4	C26—C21—H21A	106.0
C6—C5—H5A	119.4	C21—C22—C23	110.2 (2)
C1—C6—C5	117.5 (2)	C21—C22—H22A	109.6
C1—C6—Sn1	124.21 (16)	C23—C22—H22A	109.6
C5—C6—Sn1	118.26 (16)	C21—C22—H22B	109.6
C8—C7—C12	121.9 (3)	C23—C22—H22B	109.6
C8—C7—H7A	119.1	H22A—C22—H22B	108.1
C12—C7—H7A	119.1	C24—C23—C22	111.2 (3)
C9—C8—C7	119.9 (3)	C24—C23—H23A	109.4
C9—C8—H8A	120.1	C22—C23—H23A	109.4
C7—C8—H8A	120.1	C24—C23—H23B	109.4
C10—C9—C8	119.9 (3)	C22—C23—H23B	109.4
C10—C9—H9A	120.0	H23A—C23—H23B	108.0
C8—C9—H9A	120.0	C25—C24—C23	110.3 (2)
C9—C10—C11	119.9 (3)	C25—C24—H24A	109.6
C9—C10—H10A	120.1	C23—C24—H24A	109.6
C11—C10—H10A	120.1	C25—C24—H24B	109.6
C12—C11—C10	121.7 (3)	C23—C24—H24B	109.6
C12—C11—H11A	119.2	H24A—C24—H24B	108.1
C10—C11—H11A	119.2	C24—C25—C26	111.5 (3)
C11—C12—C7	116.8 (2)	C24—C25—H25A	109.3
C11—C12—Sn1	121.58 (19)	C26—C25—H25A	109.3
C7—C12—Sn1	121.61 (17)	C24—C25—H25C	109.3
C18—C13—C14	121.0 (2)	C26—C25—H25C	109.3
C18—C13—H13A	119.5	H25A—C25—H25C	108.0
C14—C13—H13A	119.5	C21—C26—C25	109.0 (2)
C15—C14—C13	120.4 (2)	C21—C26—H26C	109.9
C15—C14—H14A	119.8	C25—C26—H26C	109.9
C13—C14—H14A	119.8	C21—C26—H26A	109.9
C14—C15—C16	119.7 (2)	C25—C26—H26A	109.9
C14—C15—H15A	120.2	H26C—C26—H26A	108.3
C18—Sn1—S1—C19	72.91 (9)	C13—C14—C15—C16	0.0 (4)
C6—Sn1—S1—C19	−70.15 (9)	C14—C15—C16—C17	−0.3 (4)
C12—Sn1—S1—C19	−176.73 (9)	C15—C16—C17—C18	0.4 (4)
C6—C1—C2—C3	1.2 (4)	C14—C13—C18—C17	−0.1 (4)
C1—C2—C3—C4	−0.8 (4)	C14—C13—C18—Sn1	−179.7 (2)
C2—C3—C4—C5	−0.4 (5)	C16—C17—C18—C13	−0.2 (4)
C3—C4—C5—C6	1.3 (5)	C16—C17—C18—Sn1	179.4 (2)
C2—C1—C6—C5	−0.4 (3)	C6—Sn1—C18—C13	−44.2 (2)
C2—C1—C6—Sn1	179.14 (17)	C12—Sn1—C18—C13	69.84 (19)
C4—C5—C6—C1	−0.8 (4)	S1—Sn1—C18—C13	172.93 (16)
C4—C5—C6—Sn1	179.6 (2)	C6—Sn1—C18—C17	136.21 (18)
C18—Sn1—C6—C1	−54.5 (2)	C12—Sn1—C18—C17	−109.76 (19)
C12—Sn1—C6—C1	−170.41 (18)	S1—Sn1—C18—C17	−6.7 (2)
S1—Sn1—C6—C1	88.39 (18)	C20—N1—C19—S2	173.0 (2)
C18—Sn1—C6—C5	124.98 (18)	C21—N1—C19—S2	−6.1 (3)
C12—Sn1—C6—C5	9.11 (19)	C20—N1—C19—S1	−7.4 (3)
S1—Sn1—C6—C5	−92.09 (18)	C21—N1—C19—S1	173.45 (15)
C12—C7—C8—C9	−0.8 (4)	Sn1—S1—C19—N1	174.03 (16)
C7—C8—C9—C10	1.6 (5)	Sn1—S1—C19—S2	−6.39 (12)
C8—C9—C10—C11	−1.1 (6)	C19—N1—C21—C22	104.1 (3)
C9—C10—C11—C12	−0.3 (6)	C20—N1—C21—C22	−75.0 (3)
C10—C11—C12—C7	1.1 (5)	C19—N1—C21—C26	−126.6 (3)
C10—C11—C12—Sn1	−176.0 (3)	C20—N1—C21—C26	54.2 (3)
C8—C7—C12—C11	−0.6 (4)	N1—C21—C22—C23	−174.9 (2)
C8—C7—C12—Sn1	176.6 (2)	C26—C21—C22—C23	56.0 (4)
C18—Sn1—C12—C11	−27.0 (3)	C21—C22—C23—C24	−55.0 (4)
C6—Sn1—C12—C11	96.1 (2)	C22—C23—C24—C25	56.5 (4)
S1—Sn1—C12—C11	−145.9 (2)	C23—C24—C25—C26	−57.7 (4)
C18—Sn1—C12—C7	155.96 (19)	N1—C21—C26—C25	174.7 (3)
C6—Sn1—C12—C7	−80.9 (2)	C22—C21—C26—C25	−56.4 (4)
S1—Sn1—C12—C7	37.07 (19)	C24—C25—C26—C21	56.8 (4)
C18—C13—C14—C15	0.2 (4)