Bis(dicyclo­hexyl­ammonium) μ-oxalato-κ4 O 1,O 2:O 1′,O 2′-bis­[aqua­(oxalato-κ2 O 1,O 2)diphenyl­stannate(IV)]

Ndongo Gueye; Libasse Diop; K C Kieran Molloy; Gabrielle Kociok-Köhn

doi:10.1107/S1600536810046738

. 2010 Nov 24;66(Pt 12):m1645–m1646. doi: 10.1107/S1600536810046738

Bis(dicyclohexylammonium) μ-oxalato-κ⁴ O ¹,O ²:O ^1′,O ^2′-bis[aqua(oxalato-κ² O ¹,O ²)diphenylstannate(IV)]

Ndongo Gueye ^a, Libasse Diop ^a,^*, K C Kieran Molloy ^b, Gabrielle Kociok-Köhn ^b

PMCID: PMC3011489 PMID: 21589314

Abstract

The structure of the title compound, (C₁₂H₂₄N)₂[Sn₂(C₆H₅)₄(C₂O₄)₃(H₂O)₂], consists of a bischelating oxalate ion, located on an inversion center, which is linked to two SnPh₂ groups. The coordination sphere of the Sn(IV) ion is completed by a monochelating oxalate anion and a water molecule. The Sn(IV) atoms are thus seven-coordinated. The discrete binuclear units are further connected by hydrogen bonds, leading to a supramolecular crystal structure. The asymmetric unit contains one half dianion and one (Cy₂NH₂)⁺ cation.

Related literature

For background to organotin(IV) chemistry, see: Ballmann et al. (2009 ▶); Diallo et al. (2007 ▶); Diassé-Sarr et al. (1997 ▶); Ng et al. (1992 ▶); Singh et al. (2008 ▶); de Sousa et al. (2007 ▶); Wang et al. (2009 ▶); Xanthopoulou et al. (2007 ▶, 2008 ▶); Zia-ur-Rahman et al. (2007 ▶). For related Sn(IV) structures, see: Diop et al. (2002 ▶, 2003 ▶).

Experimental

Crystal data

(C₁₂H₂₄N)₂[Sn₂(C₆H₅)₄(C₂O₄)₃(H₂O)₂]
M _r = 1210.52
Monoclinic,
a = 13.1725 (4) Å
b = 14.6121 (4) Å
c = 14.1139 (4) Å
β = 100.869 (2)°
V = 2667.88 (13) Å³
Z = 2
Mo Kα radiation
μ = 1.00 mm⁻¹
T = 150 K
0.2 × 0.2 × 0.2 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SORTAV; Blessing, 1995 ▶) T _min = 0.825, T _max = 0.825
48411 measured reflections
6114 independent reflections
4069 reflections with I > 2σ(I)
R _int = 0.126

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.082
S = 1.01
6114 reflections
341 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.54 e Å⁻³
Δρ_min = −0.72 e Å⁻³

Data collection: COLLECT (Nonius, 2000 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO (Otwinowski & Minor, 1997 ▶) 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: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810046738/bh2310sup1.cif

e-66-m1645-sup1.cif^{(22.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810046738/bh2310Isup2.hkl

e-66-m1645-Isup2.hkl^{(293.2KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H7B⋯O4ⁱ	0.90 (4)	1.77 (4)	2.663 (3)	175 (4)
N—H1A⋯O3ⁱⁱ	0.84 (4)	2.12 (3)	2.910 (4)	155 (3)
N—H1A⋯O4ⁱⁱ	0.84 (4)	2.37 (4)	2.986 (4)	130 (3)
N—H1B⋯O6ⁱⁱⁱ	0.91 (4)	2.08 (4)	2.960 (4)	164 (4)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

supplementary crystallographic information

Comment

In the dynamic of our research work on organotin(IV) chemistry (Diallo et al., 2007; Diassé-Sarr et al., 1997) because of several applications found (Xanthopoulou et al., 2007, 2008; Zia-ur-Rahman et al., 2007; Singh et al., 2008; Wang et al., 2009; Ballmann et al., 2009; de Sousa et al., 2007) and our interest in the coordinating behaviour of oxyanions in this family of compounds, we had yet reported the crystal structures of C₂O₄(SnPh₃)₂ (Diop et al., 2003) and SO₄(SnPh₃)₂.H₂O (Diop et al., 2002) and have initiated here the study of the interactions between (Cy₂NH₂)₂C₂O₄.2H₂O and C₂O₄(SnPh₃)₂ which has yielded the studied compound.

The asymmetric unit consists of one half of the molecule, located about an inversion centre at the mid-point of the C3—C3ⁱ bond (symmetry code i: -x, 1 - y, -z). In its units structure two SnPh₂ residues are linked by a central bichelating oxalate ion [O₅O₆:O₅O₆] and every SnPh₂ residue is then linked to another monochelating anion [O1, O2]. A water molecule completes the tin centre coordination to seven, which can be described as a distorted trans-C₂SnO₅ pentagonal bipyramidal geometry [C—Sn—C angle: 168.75 (13)°]. Within the bridging carboxylate all the C—O bonds are equal within experimental error, implying complete delocalization of double-bond character within this residue. The bond lengths C1—O1 and C2—O2, [1.273 (4) Å], and C2—O3, C1—O4 [1.225 (4) and 1.247 (4) Å] indicate respectively a single and double bond character; the bond length C1—O4 results from involvement of O4 in two distinct hydrogen bonds. Among the Sn—O bonds, Sn1—O6 is notably longer, O6 being the only oxygen of this kind involved in hydrogen bonding.

Every moiety is then connected to its neighbour by three types of hydrogen bonds: one O—H···O type involving an H atom of the water molecule and one O atom of monochelating oxalate [O7—H7B···O4], one N—H···O contact involving one O atom of the bichelating oxalate anion and the cation [N—H1B···O6] and a third bifurcated one also involving the cation [N—H1A···O3 and N—H1A···O4], giving a supramolecular crystal structure.

A similar structure, bearing butyl groups in place of phenyl, was previously reported (Ng et al., 1992).

Experimental

Crystals of the title compound were obtained by allowing (Cy₂NH₂)₂C₂O₄.2H₂O (90 mmol in 15 ml e thanol) to react with C₂O₄(SnPh₃)₂ (45 mmol in 15 ml e thanol). The mixture was stirred during several hours and slow solvent evaporation afforded crystals suitable for X-rays studies.