Tetragonal modification of 1,1,3,3,5,5-hexa­methyl­cyclo-1,3,5-tristanna­thia­ne

The space group of the title compound, [Sn₃S₃(CH₃)₆], reported as P4₁, is corrected to P4₂2₁2.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](Sn-C) = 0.008 Å
• R factor = 0.037
• wR factor = 0.080
• Data-to-parameter ratio = 33.8

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           28.21
         From the CIF: _reflns_number_total               1995
         Count of symmetry unique reflns         1233
         Completeness (_total/calc)            161.80%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured       762
         Fraction of Friedel pairs measured     0.618
         Are heavy atom types Z>Si present          yes
          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.

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S1. Comment

Tris(dimethyltin sulfide), 1,1,3,3,5,5-hexamethylcyclo-1,3,5-tristannatiane, (I), was the unexpected product in our attempt at synthesizing dimethyltin bis(dipropyldithiocarbamate) from dimethyltin dichloride, carbon disulfide and n-propylamine (see Experimental). The literature reports that the compound crystallizes in monoclinic (P2₁/c; Jacobsen & Krebs, 1977) and tetragonal (Menzebach & Bleckmann, 1975) modifications. The tetragonal modification was refined in the P4₁ space group; however, the checking program PLATON (Spek, 1990) finds missing symmetry elements, and the P4₂2₁2 space group is suggested. This space group is now authenticated in the present study. The two independent Sn atoms in the tetragonal modification exist in tetrahedral geometries; adjacent molecules are linked by an Sn···S interaction of 3.902 (2) Å into a linear chain.

S2. Experimental

A solution of carbon disulfide (5 mmol) in methanol (5 ml) was added to a methanolic solution (20 ml) of a mixture of dimethyltin(IV) chloride (2.5 mmol) and n-propylamine (5 mmol). The reagent solutions were cooled to 273 K, and the carbon disulfide solution was then added at a rate so that the temperature of the mixture did not rise above 278 K. The mixture was stirred at 275 K for 2 h. A cream-colored solid was formed that was collected by filtration and washed with cold methanol (2 × 5 ml). The product was recrystallized from a methanol/chloroform (3:2 v/v) mixture to afford colorless crystals.

S3. Refinement

Of the 1995 reflections, 1995 were unique and 779 were Friedel pairs.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. ORTEPII (Johnson, 1976) plot of tris(dimethyltin sulfide) at the 50% probability level. H atoms are shown as circles of arbitrary radii.

Tris(dimethyltin sulfide)

Crystal data

[Sn3S3(CH3)6]	Dx = 2.191 Mg m^−3
Mr = 542.45	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P41212	Cell parameters from 5984 reflections
a = 9.7249 (1) Å	θ = 2.4–28.2°
c = 17.3867 (3) Å	µ = 4.87 mm^−1
V = 1644.32 (4) Å^3	T = 298 K
Z = 4	Block, colorless
F(000) = 1008	0.22 × 0.14 × 0.08 mm

Data collection

Siemens CCD area-detector diffractometer	1995 independent reflections
Radiation source: fine-focus sealed tube	1545 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.088
Detector resolution: 8.33 pixels mm^-1	θmax = 28.2°, θmin = 2.4°
ω scan	h = −9→12
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	k = −12→12
Tmin = 0.414, Tmax = 0.697	l = −22→22
11469 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.037	H-atom parameters constrained
wR(F^2) = 0.080	w = 1/[σ^2(Fo^2) + (0.0368P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.94	(Δ/σ)max = 0.001
1995 reflections	Δρmax = 0.50 e Å^−3
59 parameters	Δρmin = −0.86 e Å^−3
0 restraints	Absolute structure: Flack & Schwarzenbach (1988)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.08 (7)

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

	x	y	z	Uiso*/Ueq
Sn1	0.07775 (5)	0.07775 (5)	0.0000	0.0479 (2)
Sn2	−0.23579 (5)	−0.08594 (5)	0.09172 (2)	0.0465 (2)
S1	−0.1643 (2)	0.1157 (2)	0.0190 (1)	0.0525 (5)
S2	−0.2704 (2)	−0.2704 (2)	0.0000	0.0526 (6)
C1	0.194 (1)	0.130 (1)	0.0992 (5)	0.094 (3)
C2	−0.4379 (9)	−0.0404 (9)	0.1321 (5)	0.080 (3)
C3	−0.0790 (8)	−0.1326 (7)	0.1729 (4)	0.058 (2)
H1a	0.2178	0.2257	0.0975	0.142*
H1b	0.2766	0.0758	0.1005	0.142*
H1c	0.1406	0.1119	0.1445	0.142*
H2a	−0.4531	−0.0859	0.1803	0.120*
H2b	−0.5043	−0.0719	0.0952	0.120*
H2c	−0.4473	0.0571	0.1389	0.120*
H3a	−0.0424	−0.0487	0.1936	0.088*
H3b	−0.0069	−0.1831	0.1480	0.088*
H3c	−0.1170	−0.1869	0.2138	0.088*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Sn1	0.0418 (2)	0.0418 (2)	0.0600 (4)	−0.0042 (3)	0.0024 (2)	−0.0024 (2)
Sn2	0.0384 (3)	0.0486 (3)	0.0525 (2)	−0.0019 (2)	0.0036 (2)	−0.0034 (2)
S1	0.048 (1)	0.041 (1)	0.068 (1)	0.0082 (8)	0.0048 (9)	0.0047 (8)
S2	0.0483 (9)	0.0483 (9)	0.061 (1)	−0.014 (1)	0.0057 (9)	−0.0057 (9)
C1	0.077 (7)	0.093 (8)	0.113 (7)	−0.010 (5)	−0.025 (6)	−0.025 (6)
C2	0.065 (6)	0.075 (6)	0.099 (6)	0.011 (4)	0.040 (5)	−0.004 (5)
C3	0.063 (5)	0.057 (4)	0.055 (4)	−0.013 (4)	−0.007 (4)	0.007 (3)

Geometric parameters (Å, º)

Sn1—C1	2.125 (8)	C1—H1a	0.9600
Sn1—C1^i	2.125 (8)	C1—H1b	0.9600
Sn2—C2	2.134 (7)	C1—H1c	0.9600
Sn2—C3	2.126 (7)	C2—H2a	0.9600
Sn1—S1	2.406 (2)	C2—H2b	0.9600
Sn1—S1^i	2.406 (2)	C2—H2c	0.9600
Sn2—S1	2.435 (2)	C3—H3a	0.9600
Sn2—S2	2.424 (2)	C3—H3b	0.9600
Sn2—S1^ii	3.902 (2)	C3—H3c	0.9600
C1—Sn1—C1^i	113.9 (5)	H1a—C1—H1b	109.5
C1—Sn1—S1	111.9 (3)	Sn1—C1—H1c	109.5
C1—Sn1—S1^i	105.3 (3)	H1a—C1—H1c	109.5
C1^i—Sn1—S1	105.3 (3)	H1b—C1—H1c	109.5
C1^i—Sn1—S1^i	111.9 (3)	Sn2—C2—H2a	109.5
S1—Sn1—S1^i	108.6 (1)	Sn2—C2—H2b	109.5
C2—Sn2—C3	119.1 (3)	H2a—C2—H2b	109.5
C2—Sn2—S1	105.5 (2)	Sn2—C2—H2c	109.5
C2—Sn2—S2	104.0 (3)	H2a—C2—H2c	109.5
C3—Sn2—S1	108.2 (2)	H2b—C2—H2c	109.5
C3—Sn2—S2	112.2 (2)	Sn2—C3—H3a	109.5
S1—Sn2—S2	107.1 (1)	Sn2—C3—H3b	109.5
Sn1—S1—Sn2	103.1 (1)	H3a—C3—H3b	109.5
Sn2—S2—Sn2^i	103.1 (1)	Sn2—C3—H3c	109.5
Sn1—C1—H1a	109.5	H3a—C3—H3c	109.5
Sn1—C1—H1b	109.5	H3b—C3—H3c	109.5
C1—Sn1—S1—Sn2	−79.7 (3)	S2—Sn2—S1—Sn1	−81.7 (1)
C1^i—Sn1—S1—Sn2	156.1 (3)	C3—Sn2—S2—Sn2^i	−80.4 (2)
S1^i—Sn1—S1—Sn2	36.1 (1)	C2—Sn2—S2—Sn2^i	149.5 (2)
C3—Sn2—S1—Sn1	39.5 (2)	S1—Sn2—S2—Sn2^i	38.2 (1)
C2—Sn2—S1—Sn1	168.0 (3)	S1^ii—Sn2—S2—Sn2^i	−140.2 (1)

Symmetry codes: (i) y, x, −z; (ii) −x−1/2, y−1/2, −z+1/4.