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The title compound, [Sn(CH
3)
2(C
5H
10NO
2S
2)
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].
Supporting information
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.
The hydroxyl H atoms were located and refined.
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)
top
Crystal data top
[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) Å3 | Irregular block, colorless |
Z = 4 | 0.70 × 0.56 × 0.48 mm |
F(000) = 1032 | |
Data collection top
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 top
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)] = 0.027 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.073 | w = 1/[σ2(Fo2) + (0.036P)2] where P = (Fo2 + 2Fc2)/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+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0134 (5) |
Crystal data top
[Sn(CH3)2(C5H10NO2S2)2] | V = 2009.3 (4) Å3 |
Mr = 509.28 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 7.251 (1) Å | µ = 1.70 mm−1 |
b = 28.761 (3) Å | T = 298 K |
c = 9.635 (1) Å | 0.70 × 0.56 × 0.48 mm |
Data collection top
Siemens P4 diffractometer | 2457 reflections with I > 2σ(I) |
Absorption correction: empirical ψ scan (North et al., 1968) | Rint = 0.038 |
Tmin = 0.580, Tmax = 0.606 | 3 standard reflections every 97 reflections |
3859 measured reflections | intensity decay: none |
2964 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.027 | 0 restraints |
wR(F2) = 0.073 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.43 e Å−3 |
2964 reflections | Δρmin = −0.61 e Å−3 |
118 parameters | |
Special details top
Refinement. H atoms: riding, U(H) = 1.5Ueq(C). The hydroxyl H atoms were located
and refined. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
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—S1i | 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—S1i | 102.9 (1) | H2a—C2—H2c | 109.5 |
C2—Sn1—S1 | 107.5 (1) | H2b—C2—H2c | 109.5 |
C2—Sn1—S1i | 107.5 (1) | N1—C4—H4a | 108.6 |
S1—Sn1—S1i | 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) top
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···O1ii | 0.76 (4) | 1.90 (3) | 2.646 (3) | 170 (3) |
Symmetry code: (ii) x−1/2, y, −z+3/2. |
Experimental details
Crystal data |
Chemical formula | [Sn(CH3)2(C5H10NO2S2)2] |
Mr | 509.28 |
Crystal system, space group | Orthorhombic, Pnma |
Temperature (K) | 298 |
a, b, c (Å) | 7.251 (1), 28.761 (3), 9.635 (1) |
V (Å3) | 2009.3 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.70 |
Crystal size (mm) | 0.70 × 0.56 × 0.48 |
|
Data collection |
Diffractometer | Siemens P4 diffractometer |
Absorption correction | Empirical ψ scan (North et al., 1968) |
Tmin, Tmax | 0.580, 0.606 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3859, 2964, 2457 |
Rint | 0.038 |
(sin θ/λ)max (Å−1) | 0.703 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.027, 0.073, 1.05 |
No. of reflections | 2964 |
No. of parameters | 118 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.43, −0.61 |
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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.