Di-μ-hydroxido-bis­[dimeth­yl(thio­cyanato-κN)tin(IV)]

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

doi:10.1107/S1600536812043462

metal-organic compounds

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Volume 68| Part 12| December 2012| Page m1436

doi:10.1107/S1600536812043462

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Di-μ-hydroxido-bis[dimethyl(thiocyanato-κN)tin(IV)]

Yaya Sow,^a ^* Libasse Diop,^a Kieran C. Molloy ^b and Gabriele Kociok-Köhn ^b

^aLaboratoire de Chimie Minerale et Analytique (LACHIMIA), Departement de Chimie, Faculte des Sciences et Techniques, Universite Cheikh Anta Diop, Dakar, Senegal, and ^bDepartment of Chemistry, University of Bath, Bath BA2 7AY, England
^*Correspondence e-mail: yayasow81@yahoo.fr

(Received 5 October 2012; accepted 19 October 2012; online 3 November 2012)

The Sn^IV 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.

Related literature

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

Crystal data

[Sn₂(CH₃)₄(NCS)₂(OH)₂]
M_r = 447.69
Orthorhombic, P c a b
a = 8.3440 (2) Å
b = 12.5214 (3) Å
c = 13.3871 (2) Å
V = 1398.67 (5) Å³
Z = 4
Mo Kα radiation
μ = 3.85 mm⁻¹
T = 150 K
0.15 × 0.15 × 0.10 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SORTAV; Blessing, 1995 ) T_min = 0.596, T_max = 0.699
20098 measured reflections
1603 independent reflections
1333 reflections with I > 2σ(I)
R_int = 0.055

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.056
S = 1.11
1603 reflections
71 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.06 e Å⁻³
Δρ_min = −0.64 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O—H10⋯Sⁱ	0.84 (2)	2.38 (2)	3.207 (3)	168 (4)
C2—H2C⋯Sⁱⁱ	0.98	2.79	3.746 (4)	164
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z]$ ; (ii) $[x-{\script{1\over 2}}, -y+1, -z+{\script{3\over 2}}]$ .

Data collection: COLLECT (Nonius, 1999 ); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: DENZO and SCALEPACK; 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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812043462/wm2689sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812043462/wm2689Isup2.hkl

checkCIF report

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 (96_wt%) 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.

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

	Fig. 1. The dinuclear complex of compound (I). Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (') -x,-y + 1, -z + 1.]
	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
M_r = 447.69	D_x = 2.116 Mg m⁻³
Orthorhombic, Pcab	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2bc 2ac	Cell parameters from 30989 reflections
a = 8.3440 (2) Å	θ = 2.9–27.5°
b = 12.5214 (3) Å	µ = 3.85 mm⁻¹
c = 13.3871 (2) Å	T = 150 K
V = 1398.67 (5) Å³	Block, colourless
Z = 4	0.15 × 0.15 × 0.10 mm

Data collection top

Nonius KappaCCD diffractometer	1603 independent reflections
Radiation source: fine-focus sealed tube	1333 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.055
584 1.0 degree images with ϕ and ω scans	θ_max = 27.5°, θ_min = 4.1°
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	h = −10→10
T_min = 0.596, T_max = 0.699	k = −16→16
20098 measured reflections	l = −17→17

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)] = 0.026	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.056	w = 1/[σ²(F_o²) + (0.0224P)² + 1.8745P] where P = (F_o² + 2F_c²)/3
S = 1.11	(Δ/σ)_max < 0.001
1603 reflections	Δρ_max = 1.06 e Å⁻³
71 parameters	Δρ_min = −0.64 e Å⁻³
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0026 (2)

Crystal data top

[Sn₂(CH₃)₄(NCS)₂(OH)₂]	V = 1398.67 (5) Å³
M_r = 447.69	Z = 4
Orthorhombic, Pcab	Mo Kα radiation
a = 8.3440 (2) Å	µ = 3.85 mm⁻¹
b = 12.5214 (3) Å	T = 150 K
c = 13.3871 (2) Å	0.15 × 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)
T_min = 0.596, T_max = 0.699	R_int = 0.055
20098 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	1 restraint
wR(F²) = 0.056	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	Δρ_max = 1.06 e Å⁻³
1603 reflections	Δρ_min = −0.64 e Å⁻³
71 parameters

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

	x	y	z	U_iso*/U_eq
Sn	0.20586 (3)	0.512859 (18)	0.486833 (17)	0.02446 (10)
S	0.55735 (12)	0.27972 (7)	0.69604 (7)	0.0356 (2)
O	0.0319 (3)	0.4300 (2)	0.5594 (2)	0.0365 (6)
N	0.3739 (3)	0.4101 (2)	0.5723 (2)	0.0301 (6)
C1	0.2597 (4)	0.4461 (3)	0.3467 (3)	0.0337 (8)
H1A	0.1938	0.3823	0.3361	0.051*
H1B	0.3733	0.4264	0.3445	0.051*
H1C	0.2371	0.4985	0.2942	0.051*
C2	0.2640 (4)	0.6541 (3)	0.5634 (3)	0.0326 (8)
H2A	0.2317	0.7159	0.5233	0.049*
H2B	0.3799	0.6566	0.5751	0.049*
H2C	0.2076	0.6556	0.6276	0.049*
C3	0.4481 (4)	0.3549 (3)	0.6243 (2)	0.0247 (7)
H10	0.054 (4)	0.377 (2)	0.596 (2)	0.033 (10)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sn	0.01938 (14)	0.02506 (15)	0.02894 (15)	0.00034 (9)	−0.00069 (9)	0.00358 (8)
S	0.0431 (5)	0.0317 (5)	0.0319 (5)	0.0115 (4)	−0.0139 (4)	−0.0056 (3)
O	0.0234 (13)	0.0358 (15)	0.0501 (16)	0.0009 (11)	−0.0028 (12)	0.0229 (12)
N	0.0249 (15)	0.0311 (16)	0.0342 (16)	0.0036 (13)	−0.0038 (13)	0.0023 (12)
C1	0.032 (2)	0.034 (2)	0.036 (2)	−0.0050 (16)	−0.0056 (15)	−0.0037 (15)
C2	0.034 (2)	0.033 (2)	0.0311 (19)	0.0002 (15)	0.0040 (15)	−0.0044 (15)
C3	0.0200 (17)	0.0275 (18)	0.0266 (16)	−0.0032 (14)	0.0030 (14)	−0.0071 (13)

Geometric parameters (Å, º) top

Sn—O	2.032 (2)	N—C3	1.160 (4)
Sn—C2	2.101 (4)	C1—H1A	0.9800
Sn—C1	2.102 (4)	C1—H1B	0.9800
Sn—Oⁱ	2.198 (2)	C1—H1C	0.9800
Sn—N	2.220 (3)	C2—H2A	0.9800
S—C3	1.625 (4)	C2—H2B	0.9800
O—Snⁱ	2.198 (2)	C2—H2C	0.9800
O—H10	0.842 (18)

O—Sn—C2	111.20 (13)	Sn—C1—H1A	109.5
O—Sn—C1	112.11 (13)	Sn—C1—H1B	109.5
C2—Sn—C1	136.11 (15)	H1A—C1—H1B	109.5
O—Sn—Oⁱ	69.90 (10)	Sn—C1—H1C	109.5
C2—Sn—Oⁱ	94.13 (12)	H1A—C1—H1C	109.5
C1—Sn—Oⁱ	94.06 (13)	H1B—C1—H1C	109.5
O—Sn—N	84.76 (10)	Sn—C2—H2A	109.5
C2—Sn—N	95.18 (12)	Sn—C2—H2B	109.5
C1—Sn—N	95.43 (13)	H2A—C2—H2B	109.5
Oⁱ—Sn—N	154.66 (10)	Sn—C2—H2C	109.5
Sn—O—Snⁱ	110.10 (10)	H2A—C2—H2C	109.5
Sn—O—H10	122 (3)	H2B—C2—H2C	109.5
Snⁱ—O—H10	128 (3)	N—C3—S	178.1 (3)
C3—N—Sn	172.5 (3)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O—H10···Sⁱⁱ	0.84 (2)	2.38 (2)	3.207 (3)	168 (4)
C2—H2C···Sⁱⁱⁱ	0.98	2.79	3.746 (4)	164

Symmetry codes: (ii) x−1/2, −y+1/2, z; (iii) x−1/2, −y+1, −z+3/2.

Experimental details

Crystal data
Chemical formula	[Sn₂(CH₃)₄(NCS)₂(OH)₂]
M_r	447.69
Crystal system, space group	Orthorhombic, Pcab
Temperature (K)	150
a, b, c (Å)	8.3440 (2), 12.5214 (3), 13.3871 (2)
V (Å³)	1398.67 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.85
Crystal size (mm)	0.15 × 0.15 × 0.10

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (SORTAV; Blessing, 1995)
T_min, T_max	0.596, 0.699
No. of measured, independent and observed [I > 2σ(I)] reflections	20098, 1603, 1333
R_int	0.055
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.056, 1.11
No. of reflections	1603
No. of parameters	71
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.06, −0.64

Computer programs: COLLECT (Nonius, 1999), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O—H10···Sⁱ	0.842 (18)	2.38 (2)	3.207 (3)	168 (4)
C2—H2C···Sⁱⁱ	0.98	2.79	3.746 (4)	164.2

Symmetry codes: (i) x−1/2, −y+1/2, z; (ii) x−1/2, −y+1, −z+3/2.

References

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 12| December 2012| Page m1436

doi:10.1107/S1600536812043462

Open

access