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Acta Cryst. (2012). E68, m1436    [ doi:10.1107/S1600536812043462 ]

Di-[mu]-hydroxido-bis[dimethyl(thiocyanato-[kappa]N)tin(IV)]

Y. Sow, L. Diop, K. C. Molloy and G. Kociok-Köhn

Abstract top

The SnIV atom in the centrosymmetric title complex, [Sn2(CH3)4(NCS)2(OH)2], adopts a distorted trigonal-bipyramidal coordination environment defined by two methyl C atoms and one bridging hydroxide group in the equatorial plane while the other bridging hydroxide group and the N atom of the thiocyanate anion are in the apical >positions. The dinuclear species are linked through O-H...S and C-H... S hydrogen-bonding interactions into a three-dimensional network.

Comment top

Organotin complexes may interact with biological systems in many different ways as bactericides, fungicides, acaricides and industrial biocides (Davies, 2004; Gielen et al., 1991; Gielen, 1996; Kamruddin et al., 1996; Khoo & Ng, 2001; Tsangaris & Williams, 1992). Many tin compounds containing the Sn(CH3)2 residue tiogether with a four-membered distannoxane [Sn(µ-OH)]2 ring have been reported (Chandrasekhar et al., 2007; Ng, 1998). In the context of new Sn(CH3)2-residue containing compounds we have initiated the structural study of the interactions between (NH4)SCN and Sn(CH3)2Cl2, which has yielded the title complex, [Sn(CH3)2(OH)(SCN)]2, (I).

The asymmetric unit of compound (I) is situated close to an inversion centre, which generates a dimer containing a central Sn2O2 ring; the tin(IV) atom is five-coordinated by two methyl groups, two bridging oxygen atoms and one nitrogen atom of the thiocyanate anion, forming a distorted trigonal bipyramid (Fig. 1). The sum of the angles at the tin atom, involving the carbon atoms and one O atom is 359.47 °; the nitrogen and the other oxygen atom Oi [(i) -x,-y + 1, -z + 1] are at the apical positions. The angles involving N and the atoms of the equatorial plane [N1—Sn1—C2 = 95.18 (12)°, N—Sn—C1 = 95.43 (13)°, N—Sn—O1 = 84.76 (10)°] show a significant deviation from the perfect trigonal-bipyramidal configuration. The bond lengths Sn—C [2.101 (4), 2.102 (4) Å] and Sn—N [2.220 (3) Å] are quite similar while the two Sn—O bond lengths [Sn—O1 = 2.032 (2), Sn—Oi = 2.198 (2) Å] are different but are in the range of typical Sn—O(bridging) distances (Ng, 1998; Chandrasekhar et al., 2007). The Sn—N and Sn—C bond length are likewise in the range of reported values (Cox & Wardell, 1996; Ng, 1998; Okio et al., 2003; Chandrasekhar et al., 2007). The SCN- anion is almost linear [N—C3—S = 178.1 (3)°], as in the structure of [(CH3)4N][Sn(C6H5)3(SCN)2] (Okio et al., 2003). The Sn—N—C angle deviates more from linearity [C3—N—Sn = 172.5 (3)°].

The dinuclear species are linked through O—H···S hydrogen bonds into layers parallel to (001) (Fig. 2); C—H···S hydrogen bonding interactions (Table 1) lead to the formation of a three-dimensional network.

Related literature top

For background to organotin(IV) chemistry, see: Davies (2004); Gielen et al. (1991); Gielen (1996); Kamruddin et al. (1996); Khoo & Ng (2001); Tsangaris & Williams (1992). For structures containing the four-membered distannoxane [Sn(µ-OH)]2 unit, see: Chandrasekhar et al. (2007); Ng (1998). For related structures, see: Cox & Wardell (1996); Okio et al. (2003).

Experimental top

All chemicals were purchased from Aldrich (Germany) and used without any further purification. The salt (NH4)SCN was obtained by mixing KSCN with NH4Cl in ethanol 96%. The title compound (I) was synthesized by reacting Sn(CH3)2Cl2 with (NH4)SCN in ethanol (96wt%) in a 1:1 ratio. After stirring for two hours a clear solution was obtained that was slowly evaporated, yielding colourless crystals with a melting point of 502 K.

Refinement top

Hydrogen atoms bonded to the O atom have been located in difference Fourier maps and have been freely refined. The other hydrogen atoms have been placed onto calculated position and refined using a riding model, with C—H distances of 0.98 Å and Uiso(H)= 1.5Ueq(C).

Computing details top

Data collection: COLLECT (Nonius, 1999); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The dinuclear complex of compound (I). Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (') -x,-y + 1, -z + 1.]
[Figure 2] Fig. 2. View of the hydrogen bonding system (dashed lines) between the sulfur atom of the SCN- anion and the H atom of the bridging OH group, as well as C—H···S interactions. O atoms are red, S atoms olive, N atoms blue, Sn atoms green, H atoms yellow and C atoms grey.
Di-µ-hydroxido-bis[dimethyl(thiocyanato-κN)tin(IV)] top
Crystal data top
[Sn2(CH3)4(NCS)2(OH)2]F(000) = 848
Mr = 447.69Dx = 2.116 Mg m3
Orthorhombic, PcabMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2bc 2acCell parameters from 30989 reflections
a = 8.3440 (2) Åθ = 2.9–27.5°
b = 12.5214 (3) ŵ = 3.85 mm1
c = 13.3871 (2) ÅT = 150 K
V = 1398.67 (5) Å3Block, colourless
Z = 40.15 × 0.15 × 0.10 mm
Data collection top
Nonius KappaCCD
diffractometer
1603 independent reflections
Radiation source: fine-focus sealed tube1333 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.055
584 1.0 degree images with φ and ω scansθmax = 27.5°, θmin = 4.1°
Absorption correction: multi-scan
(SORTAV; Blessing, 1995)
h = 1010
Tmin = 0.596, Tmax = 0.699k = 1616
20098 measured reflectionsl = 1717
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.026H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.056 w = 1/[σ2(Fo2) + (0.0224P)2 + 1.8745P]
where P = (Fo2 + 2Fc2)/3
S = 1.11(Δ/σ)max < 0.001
1603 reflectionsΔρmax = 1.06 e Å3
71 parametersΔρmin = 0.64 e Å3
1 restraintExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0026 (2)
Crystal data top
[Sn2(CH3)4(NCS)2(OH)2]V = 1398.67 (5) Å3
Mr = 447.69Z = 4
Orthorhombic, PcabMo Kα radiation
a = 8.3440 (2) ŵ = 3.85 mm1
b = 12.5214 (3) ÅT = 150 K
c = 13.3871 (2) Å0.15 × 0.15 × 0.10 mm
Data collection top
Nonius KappaCCD
diffractometer
1603 independent reflections
Absorption correction: multi-scan
(SORTAV; Blessing, 1995)
1333 reflections with I > 2σ(I)
Tmin = 0.596, Tmax = 0.699Rint = 0.055
20098 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.026H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.056Δρmax = 1.06 e Å3
S = 1.11Δρmin = 0.64 e Å3
1603 reflectionsAbsolute structure: ?
71 parametersFlack parameter: ?
1 restraintRogers parameter: ?
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Sn0.20586 (3)0.512859 (18)0.486833 (17)0.02446 (10)
S0.55735 (12)0.27972 (7)0.69604 (7)0.0356 (2)
O0.0319 (3)0.4300 (2)0.5594 (2)0.0365 (6)
N0.3739 (3)0.4101 (2)0.5723 (2)0.0301 (6)
C10.2597 (4)0.4461 (3)0.3467 (3)0.0337 (8)
H1A0.19380.38230.33610.051*
H1B0.37330.42640.34450.051*
H1C0.23710.49850.29420.051*
C20.2640 (4)0.6541 (3)0.5634 (3)0.0326 (8)
H2A0.23170.71590.52330.049*
H2B0.37990.65660.57510.049*
H2C0.20760.65560.62760.049*
C30.4481 (4)0.3549 (3)0.6243 (2)0.0247 (7)
H100.054 (4)0.377 (2)0.596 (2)0.033 (10)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sn0.01938 (14)0.02506 (15)0.02894 (15)0.00034 (9)0.00069 (9)0.00358 (8)
S0.0431 (5)0.0317 (5)0.0319 (5)0.0115 (4)0.0139 (4)0.0056 (3)
O0.0234 (13)0.0358 (15)0.0501 (16)0.0009 (11)0.0028 (12)0.0229 (12)
N0.0249 (15)0.0311 (16)0.0342 (16)0.0036 (13)0.0038 (13)0.0023 (12)
C10.032 (2)0.034 (2)0.036 (2)0.0050 (16)0.0056 (15)0.0037 (15)
C20.034 (2)0.033 (2)0.0311 (19)0.0002 (15)0.0040 (15)0.0044 (15)
C30.0200 (17)0.0275 (18)0.0266 (16)0.0032 (14)0.0030 (14)0.0071 (13)
Geometric parameters (Å, º) top
Sn—O2.032 (2)N—C31.160 (4)
Sn—C22.101 (4)C1—H1A0.9800
Sn—C12.102 (4)C1—H1B0.9800
Sn—Oi2.198 (2)C1—H1C0.9800
Sn—N2.220 (3)C2—H2A0.9800
S—C31.625 (4)C2—H2B0.9800
O—Sni2.198 (2)C2—H2C0.9800
O—H100.842 (18)
O—Sn—C2111.20 (13)Sn—C1—H1A109.5
O—Sn—C1112.11 (13)Sn—C1—H1B109.5
C2—Sn—C1136.11 (15)H1A—C1—H1B109.5
O—Sn—Oi69.90 (10)Sn—C1—H1C109.5
C2—Sn—Oi94.13 (12)H1A—C1—H1C109.5
C1—Sn—Oi94.06 (13)H1B—C1—H1C109.5
O—Sn—N84.76 (10)Sn—C2—H2A109.5
C2—Sn—N95.18 (12)Sn—C2—H2B109.5
C1—Sn—N95.43 (13)H2A—C2—H2B109.5
Oi—Sn—N154.66 (10)Sn—C2—H2C109.5
Sn—O—Sni110.10 (10)H2A—C2—H2C109.5
Sn—O—H10122 (3)H2B—C2—H2C109.5
Sni—O—H10128 (3)N—C3—S178.1 (3)
C3—N—Sn172.5 (3)
Symmetry code: (i) x, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O—H10···Sii0.84 (2)2.38 (2)3.207 (3)168 (4)
C2—H2C···Siii0.982.793.746 (4)164
Symmetry codes: (ii) x1/2, y+1/2, z; (iii) x1/2, y+1, z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O—H10···Si0.842 (18)2.38 (2)3.207 (3)168 (4)
C2—H2C···Sii0.982.793.746 (4)164.2
Symmetry codes: (i) x1/2, y+1/2, z; (ii) x1/2, y+1, z+3/2.
references
References top

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