Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536800020134/na6025sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536800020134/na6025Isup2.hkl |
CCDC reference: 155907
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.
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.
Fig. 1. ORTEPII (Johnson, 1976) plot of tris(dimethyltin sulfide) at the 50% probability level. H atoms are shown as circles of arbitrary radii. |
[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) Å3 | T = 298 K |
Z = 4 | Block, colorless |
F(000) = 1008 | 0.22 × 0.14 × 0.08 mm |
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 on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.037 | H-atom parameters constrained |
wR(F2) = 0.080 | w = 1/[σ2(Fo2) + (0.0368P)2] where P = (Fo2 + 2Fc2)/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) |
[Sn3S3(CH3)6] | Z = 4 |
Mr = 542.45 | Mo Kα radiation |
Tetragonal, P41212 | µ = 4.87 mm−1 |
a = 9.7249 (1) Å | T = 298 K |
c = 17.3867 (3) Å | 0.22 × 0.14 × 0.08 mm |
V = 1644.32 (4) Å3 |
Siemens CCD area-detector diffractometer | 1995 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 1545 reflections with I > 2σ(I) |
Tmin = 0.414, Tmax = 0.697 | Rint = 0.088 |
11469 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | H-atom parameters constrained |
wR(F2) = 0.080 | Δρmax = 0.50 e Å−3 |
S = 0.94 | Δρmin = −0.86 e Å−3 |
1995 reflections | Absolute structure: Flack & Schwarzenbach (1988) |
59 parameters | Absolute structure parameter: 0.08 (7) |
0 restraints |
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* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
Sn1—C1 | 2.125 (8) | C1—H1a | 0.9600 |
Sn1—C1i | 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—S1i | 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—S1ii | 3.902 (2) | C3—H3c | 0.9600 |
C1—Sn1—C1i | 113.9 (5) | H1a—C1—H1b | 109.5 |
C1—Sn1—S1 | 111.9 (3) | Sn1—C1—H1c | 109.5 |
C1—Sn1—S1i | 105.3 (3) | H1a—C1—H1c | 109.5 |
C1i—Sn1—S1 | 105.3 (3) | H1b—C1—H1c | 109.5 |
C1i—Sn1—S1i | 111.9 (3) | Sn2—C2—H2a | 109.5 |
S1—Sn1—S1i | 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—Sn2i | 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) |
C1i—Sn1—S1—Sn2 | 156.1 (3) | C3—Sn2—S2—Sn2i | −80.4 (2) |
S1i—Sn1—S1—Sn2 | 36.1 (1) | C2—Sn2—S2—Sn2i | 149.5 (2) |
C3—Sn2—S1—Sn1 | 39.5 (2) | S1—Sn2—S2—Sn2i | 38.2 (1) |
C2—Sn2—S1—Sn1 | 168.0 (3) | S1ii—Sn2—S2—Sn2i | −140.2 (1) |
Symmetry codes: (i) y, x, −z; (ii) −x−1/2, y−1/2, −z+1/4. |
Experimental details
Crystal data | |
Chemical formula | [Sn3S3(CH3)6] |
Mr | 542.45 |
Crystal system, space group | Tetragonal, P41212 |
Temperature (K) | 298 |
a, c (Å) | 9.7249 (1), 17.3867 (3) |
V (Å3) | 1644.32 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 4.87 |
Crystal size (mm) | 0.22 × 0.14 × 0.08 |
Data collection | |
Diffractometer | Siemens CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.414, 0.697 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11469, 1995, 1545 |
Rint | 0.088 |
(sin θ/λ)max (Å−1) | 0.665 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.080, 0.94 |
No. of reflections | 1995 |
No. of parameters | 59 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.50, −0.86 |
Absolute structure | Flack & Schwarzenbach (1988) |
Absolute structure parameter | 0.08 (7) |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97.
Sn1—C1 | 2.125 (8) | Sn1—S1 | 2.406 (2) |
Sn2—C2 | 2.134 (7) | Sn2—S1 | 2.435 (2) |
Sn2—C3 | 2.126 (7) | Sn2—S2 | 2.424 (2) |
C1—Sn1—C1i | 113.9 (5) | C2—Sn2—S2 | 104.0 (3) |
C1—Sn1—S1 | 111.9 (3) | C3—Sn2—S1 | 108.2 (2) |
C1—Sn1—S1i | 105.3 (3) | C3—Sn2—S2 | 112.2 (2) |
S1—Sn1—S1i | 108.6 (1) | S1—Sn2—S2 | 107.1 (1) |
C2—Sn2—C3 | 119.1 (3) | Sn1—S1—Sn2 | 103.1 (1) |
C2—Sn2—S1 | 105.5 (2) | Sn2—S2—Sn2i | 103.1 (1) |
Symmetry code: (i) y, x, −z. |
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.