Bis­[N,N-bis(2-hydroxy­ethyl)­di­thio­carbamato]­di­methyl­tin(IV)

The title compound, [Sn(CH₃)₂(C₅H₁₀NO₂S₂)₂], has crystallographic mirror symmetry (C-Sn-C on mirror plane) and the coordination polyhedron around the Sn atom is a tetrahedron [C-Sn-C 139.3 (2)° and S-Sn-S 82.3 (1)°] distorted towards a skew-trapezoidal bipyramid owing to an intramolecular Sn...S contact [3.0427 (6) Å]. The mol­ecules are linked into a linear chain by intermolecular O-H...O hydrogen bonds [O...O 2.646 (3) Å].

S1. Comment

The structures of a number of diorganotin(IV) bis(N,N-dithiocarbamates) have been reported. Among the dimethyltin derivatives, the dimethyldithiocarbamate (Kimura et al., 1972), the three modifications of the diethyldithiocarbamate (Lockhart et al., 1986; Morris & Schlemper, 1979) and the tetramethylenedithiocarbamate (Lockhart et al., 1985) have a dimethyltin skeleton is opened up to about 135°, so that the geometry is not a strict tetrahedron. The geometries of these and other bis(chelated) diorganotin compounds having such a bent skeleton have been described in terms of a skew-trapezoidal bipyramid (Ng et al., 1987). The dithiocarbamates display an intramolecular tin–sulfur interaction of about 3 Å, which is only about 0.5 Å longer than the covalent tin–sulfur distances. On the other hand, for the trimethyltin derivatives, as the interaction is much longer, the dithiocarbamate group is essentially monodentate (Lokaj et al., 1986).

The introduction of two hydroxy substituents in the diethyldithiocarbamato ligand results in the title compound whose molecules are stacked as a linear chain along the a axis. The component molecules are held together by strong hydrogen bonds; the intermolecular hydrogen bond [O···O 2.646 (3) Å and O—H···O 170 (3)°] is shorter than the intramolecular hydrogen bond [O···O 2.683 (3) Å and O—H···O 172 (4)°]. In the tellurium(II) and diiodotellurium(IV) deratives, the two hydroxy groups of each dithiocarbamato ligand are not linked; instead, the four hydroxy groups of one molecule are linked to the the hydroxy groups of adjacent molecules, but the hydrogen bonds are much weaker (Appa Rao et al., 1983; Rout et al.., 1983). Similarly, only intermolecular molecular hydrogen bonds are found in the nickel [O···O 2.707 (5) and 2.711 (5) Å] (Ramalingam et al., 1984) and copper [O···O 2.412 (2) Å] (Radha et al., 1985) derivatives.

S2. Experimental

A solution of carbon disulfide (1.5 ml) in methanol (5 ml) was added to a methanol solution (100 ml) of a mixture of dimethyltin dichloride (1.1 g, 5 mmol) and ethanolamine (3 ml, 31 mmol) in methanol (100 ml). Both solutions were initially cooled to 273 K and the carbon disulfide solution was added at a rate such that the temperature of the reaction mixture did not rise above 273 K. The yellow product that separated from the stirred mixture after several hours of stirring was collected and recrystallized from methanol to afford yellow crystals of the dimethyltin complex. The crystal used in the study was the only one suitable for the diffraction measurements. Because of the relatively large size, it was likely that the crystal would not be bathed in the X-ray radiation during a part of the measurements. However, the error was deemed to be minor as the structure was well behaved in the refinements.

S3. Refinement

The hydroxyl H atoms were located and refined.

Computing details

Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97.

Bis[(bis-2-hydroxyethyl)dithiocarbamato]dimethyltin(IV)

Crystal data

[Sn(CH3)2(C5H10NO2S2)2]	Dx = 1.683 Mg m^−3
Mr = 509.28	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pnma	Cell parameters from 46 reflections
a = 7.251 (1) Å	θ = 5.4–12.5°
b = 28.761 (3) Å	µ = 1.70 mm^−1
c = 9.635 (1) Å	T = 298 K
V = 2009.3 (4) Å^3	Irregular block, colorless
Z = 4	0.70 × 0.56 × 0.48 mm
F(000) = 1032

Data collection

Siemens P4 diffractometer	2457 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.038
Graphite monochromator	θmax = 30.0°, θmin = 2.2°
ω–2θ scans	h = −1→10
Absorption correction: empirical ψ scan (North et al., 1968)	k = −40→1
Tmin = 0.580, Tmax = 0.606	l = −1→13
3859 measured reflections	3 standard reflections every 97 reflections
2964 independent reflections	intensity decay: none

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)] = 0.027	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.073	w = 1/[σ^2(Fo^2) + (0.036P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
2964 reflections	Δρmax = 0.43 e Å^−3
118 parameters	Δρmin = −0.61 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0134 (5)

Special details

Refinement. H atoms: riding, U(H) = 1.5U_eq(C). The hydroxyl H atoms were located and refined.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Sn1	0.16118 (3)	0.7500	0.45628 (2)	0.0362 (1)
S1	0.39219 (9)	0.69254 (2)	0.54773 (6)	0.0478 (2)
S2	0.08077 (8)	0.64808 (2)	0.39708 (7)	0.0509 (2)
O1	0.5856 (3)	0.5521 (1)	0.6934 (2)	0.0626 (5)
O2	0.2683 (3)	0.5186 (1)	0.5909 (2)	0.0465 (4)
N1	0.3998 (2)	0.6060 (1)	0.4565 (2)	0.0340 (3)
C1	0.2148 (5)	0.7500	0.2393 (3)	0.0486 (7)
C2	−0.0670 (6)	0.7500	0.5942 (4)	0.0583 (9)
C3	0.2958 (3)	0.64440 (7)	0.4648 (2)	0.0358 (4)
C4	0.5955 (3)	0.60631 (8)	0.4991 (3)	0.0438 (5)
C5	0.6261 (3)	0.59845 (9)	0.6520 (3)	0.0499 (5)
C6	0.3297 (3)	0.56431 (7)	0.3850 (2)	0.0407 (4)
C7	0.1901 (3)	0.53671 (8)	0.4666 (2)	0.0440 (5)
H1	0.478 (5)	0.5439 (13)	0.658 (3)	0.08 (1)*
H2	0.206 (4)	0.5282 (12)	0.647 (3)	0.06 (1)*
H1a	0.3456	0.7500	0.2238	0.073*
H1b	0.1615	0.7772	0.1981	0.073*	0.50
H1c	0.1615	0.7227	0.1981	0.073*	0.50
H2a	−0.0234	0.7500	0.6883	0.087*
H2b	−0.1405	0.7227	0.5783	0.087*	0.50
H2c	−0.1405	0.7772	0.5783	0.087*	0.50
H4a	0.6489	0.6361	0.4737	0.066*
H4b	0.6606	0.5824	0.4476	0.066*
H5a	0.7538	0.6053	0.6742	0.075*
H5b	0.5493	0.6198	0.7042	0.075*
H6a	0.4331	0.5442	0.3632	0.061*
H6b	0.2741	0.5738	0.2979	0.061*
H7a	0.0865	0.5566	0.4897	0.066*
H7b	0.1446	0.5113	0.4101	0.066*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Sn1	0.0382 (1)	0.0365 (1)	0.0339 (1)	0.000	−0.0029 (1)	0.000
S1	0.0556 (3)	0.0313 (2)	0.0565 (3)	−0.0003 (2)	−0.0234 (3)	−0.0020 (2)
S2	0.0430 (3)	0.0411 (3)	0.0685 (4)	0.0005 (2)	−0.0179 (3)	−0.0022 (2)
O1	0.072 (1)	0.057 (1)	0.059 (1)	0.000 (1)	−0.025 (1)	0.013 (1)
O2	0.056 (1)	0.041 (1)	0.043 (1)	0.003 (1)	0.009 (1)	0.002 (1)
N1	0.036 (1)	0.033 (1)	0.033 (1)	−0.001 (1)	0.001 (1)	0.002 (1)
C1	0.042 (2)	0.068 (2)	0.036 (1)	0.000	0.000 (1)	0.000
C2	0.062 (2)	0.067 (2)	0.046 (2)	0.000	0.011 (2)	0.000
C3	0.042 (1)	0.031 (1)	0.035 (1)	−0.003 (1)	−0.003 (1)	0.002 (1)
C4	0.034 (1)	0.048 (1)	0.049 (1)	0.002 (1)	0.002 (1)	0.004 (1)
C5	0.049 (1)	0.049 (1)	0.052 (1)	0.003 (1)	−0.015 (1)	0.000 (1)
C6	0.054 (1)	0.034 (1)	0.035 (1)	−0.002 (1)	0.003 (1)	−0.005 (1)
C7	0.050 (1)	0.036 (1)	0.046 (1)	−0.005 (1)	0.000 (1)	−0.001 (1)

Geometric parameters (Å, º)

Sn1—C1	2.126 (3)	C1—H1a	0.9600
Sn1—C2	2.122 (4)	C1—H1b	0.9599
Sn1—S1	2.5127 (6)	C1—H1c	0.9599
Sn1—S1^i	2.5127 (6)	C2—H2a	0.9600
Sn1—S2	3.0427 (6)	C2—H2b	0.9599
S1—C3	1.744 (2)	C2—H2c	0.9599
S2—C3	1.694 (2)	C4—H4a	0.9701
O1—C5	1.423 (3)	C4—H4b	0.9700
O2—C7	1.423 (3)	C5—H5a	0.9701
N1—C3	1.341 (3)	C5—H5b	0.9700
N1—C4	1.477 (3)	C6—H6a	0.9699
N1—C6	1.472 (3)	C6—H6b	0.9700
C4—C5	1.507 (3)	C7—H7a	0.9699
C6—C7	1.507 (3)	C7—H7b	0.9701
O1—H1	0.88 (4)
C1—Sn1—C2	139.3 (2)	H2a—C2—H2b	109.5
C1—Sn1—S1	102.9 (1)	Sn1—C2—H2c	109.5
C1—Sn1—S1^i	102.9 (1)	H2a—C2—H2c	109.5
C2—Sn1—S1	107.5 (1)	H2b—C2—H2c	109.5
C2—Sn1—S1^i	107.5 (1)	N1—C4—H4a	108.6
S1—Sn1—S1^i	82.3 (1)	C5—C4—H4a	108.7
C3—S1—Sn1	95.4 (1)	N1—C4—H4b	108.7
C3—N1—C6	120.3 (2)	C5—C4—H4b	108.7
C3—N1—C4	121.2 (2)	H4a—C4—H4b	107.6
C6—N1—C4	117.9 (2)	O1—C5—H5a	108.9
N1—C3—S2	123.1 (2)	C4—C5—H5a	109.0
N1—C3—S1	117.2 (2)	O1—C5—H5b	109.2
S2—C3—S1	119.7 (1)	C4—C5—H5b	109.1
N1—C4—C5	114.3 (2)	H5a—C5—H5b	107.8
O1—C5—C4	112.6 (2)	N1—C6—H6a	108.6
N1—C6—C7	114.6 (2)	C7—C6—H6a	108.5
O2—C7—C6	111.4 (2)	N1—C6—H6b	108.6
Sn1—C1—H1a	109.5	C7—C6—H6b	108.7
Sn1—C1—H1b	109.5	H6a—C6—H6b	107.6
H1a—C1—H1b	109.5	O2—C7—H7a	109.3
Sn1—C1—H1c	109.5	C6—C7—H7a	109.3
H1a—C1—H1c	109.5	O2—C7—H7b	109.4
H1b—C1—H1c	109.5	C6—C7—H7b	109.4
Sn1—C2—H2a	109.5	H7a—C7—H7b	108.0
Sn1—C2—H2b	109.5

Symmetry code: (i) x, −y+3/2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.88 (4)	1.81 (4)	2.683 (3)	172 (4)
O2—H2···O1^ii	0.76 (4)	1.90 (3)	2.646 (3)	170 (3)

Symmetry code: (ii) x−1/2, y, −z+3/2.