Octa­methyldi-μ3-oxido-bis­(μ2-thio­phene-3-acetato-κ2 O:O′)(thio­phene-3-acetato-κO)tetra­tin(IV)

Muhammad Danish; M Nawaz Tahir; Nazir Ahmad; Abdul Rauf Raza; Muhammad Ibrahim

doi:10.1107/S1600536809015475

. 2009 Apr 30;65(Pt 5):m609–m610. doi: 10.1107/S1600536809015475

Octamethyldi-μ₃-oxido-bis(μ₂-thiophene-3-acetato-κ² O:O′)(thiophene-3-acetato-κO)tetratin(IV)

Muhammad Danish ^a, M Nawaz Tahir ^b,^*, Nazir Ahmad ^a, Abdul Rauf Raza ^a, Muhammad Ibrahim ^a

PMCID: PMC2977640 PMID: 21583826

Abstract

In the centrosymmetric title compound, [Sn₄(CH₃)₈(C₆H₅O₂S)₄O₂], the central four-membered planar ring (Sn₂O₂) makes dihedral angles of 66.28 (12) and 77.43 (11)° with the heterocyclic rings of the bridging and monodentate ligands, respectively. One Sn^IV atom adopts a distorted SnO₃C₂ trigonal-bipyramidal geometry, with both C atoms in equatorial sites and the other a grossly distorted SnO₄C₂ octahedral or irregular arrangement. In the crystal, the molecules are connected into pillar-like polymeric units making R ₂ ²(12) ring motifs due to intermolecular C—H⋯O interactions. C–H⋯π interactions are also present. The O atoms of the chelating ligands and the S atom of the monodentate ligand are disordered over two sets of sites in a 0.65 (6):0.35 (6) ratio

Related literature

For related structures, see: Danish et al. (1995 ▶, 1996 ▶); Ng et al. (2001 ▶); Tahir et al. (1997a ▶,b ▶). For graph-set theory, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

[Sn₄(CH₃)₈(C₆H₅O₂S)₄O₂]
M _r = 1191.79
Triclinic,
a = 9.7330 (5) Å
b = 9.7403 (5) Å
c = 12.0432 (6) Å
α = 85.407 (2)°
β = 85.259 (1)°
γ = 71.256 (2)°
V = 1075.74 (10) Å³
Z = 1
Mo Kα radiation
μ = 2.54 mm⁻¹
T = 296 K
0.20 × 0.15 × 0.13 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.637, T _max = 0.719
19310 measured reflections
4012 independent reflections
3441 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.024
wR(F ²) = 0.059
S = 1.04
4012 reflections
250 parameters
H-atom parameters constrained
Δρ_max = 0.84 e Å⁻³
Δρ_min = −0.65 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809015475/hb2953sup1.cif

e-65-0m609-sup1.cif^{(26.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809015475/hb2953Isup2.hkl

e-65-0m609-Isup2.hkl^{(192.6KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Sn1—O1A	2.23 (2)
Sn1—O3	2.031 (2)
Sn1—O4	2.207 (3)
Sn1—C7	2.088 (5)
Sn1—C8	2.091 (4)
Sn2—O2A	2.312 (17)
Sn2—O3	2.0366 (19)
Sn2—C9	2.106 (5)
Sn2—C10	2.109 (4)
Sn2—O3ⁱ	2.127 (2)
Sn2—O4ⁱ	2.670 (3)

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Symmetry code: (i) Inline graphic .

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8C⋯O5ⁱⁱ	0.96	2.58	3.103 (6)	115
C5—H5⋯CgCⁱⁱⁱ	0.93	2.83	3.513 (5)	131
C10—H10C⋯CgCⁱ	0.96	2.80	3.697 (5)	156

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) . CgC is the centriod of the heterocyclic ring (C13–C16/S2A or C13–C16/S2B).

Acknowledgments

The authors acknowledge the Higher Education Commission, Islamabad, Pakistan, and Bana International, Karachi, Pakistan, for funding the purchase of the diffractometer and for technical support, respectively.

supplementary crystallographic information

Comment

In continuation to our interest with the tin chemistry in various forms (Danish et al., 1995, 1996), (Tahir et al., 1997a, 1997b), we report here the title compound (I), (Fig. 1).

The crystal structure of bis(dicyclohexylammonium 3-thienylacetate) (Ng et al., 2001) has been reported which shows disorder in the 3-thienylacetate unit. In our present complex the ligand is also in disorder. The O-atoms of chelating carboxylate are disordered over two sites with occupancy ratio of 0.65:0.35, whereas in other ligands the disorder is present at the S-atoms. In the title molecule symmetry related central four membered ring A (Sn2/O3/Sn2ⁱ/O3ⁱ; i = -x + 1, -y, -z + 1) is of course planar. The five membered rings B (C3—C5/S1/C6) and C (C13—C15/S2A/C16) are also planar. The dihedral angles between A/B, A/C and B/C are 66.28 (12)°, 77.43 (11)° and 71.23 (18)°, respectively. Due to intermolecular H-bonding, the stannoxanes are connected in pillar like polymeric form making R₂²(12) ring motifs (Bernstein et al., 1995), (Fig. 2). The molecules are also stabilized due to C–H···π interactions (Table 1).

Experimental

The complex was synthesized by refluxing (CH₃)₂SnO (1.66 g, 0.01 mol) and 3-thiopheneacetic acid (1.42 g, 0.01 mol) under argon, in toluene for 4–6 h. Water formed during the reaction was continuously removed by the use of Dean-Stark apparatus. The reaction mixture was brought to room temperature and then boiled with anhydrous activated charcoal and filtered through alumina column. Toluene was removed completely from the filtrate under vacuum. The solid mass thus obtained was purified by repeated crystallization from chloroform-ethanol (8:2) mixture, to obtain colourless prisms of (I).