Bis[2-(3-chloro­benzyl­idene)propanoato-κ2 O,O′]diethyl­tin(IV)

Niaz Muhammad; M Nawaz Tahir; Saqib Ali; Zia-ur-Rehman

doi:10.1107/S1600536808018321

. 2008 Jun 21;64(Pt 7):m946–m947. doi: 10.1107/S1600536808018321

Bis[2-(3-chlorobenzylidene)propanoato-κ² O,O′]diethyltin(IV)

Niaz Muhammad ^a,^*, M Nawaz Tahir ^b, Saqib Ali ^a, Zia-ur-Rehman ^a

PMCID: PMC2961729 PMID: 21202798

Abstract

In the molecule of the title compound, [Sn(C₂H₅)₂(C₁₀H₈ClO₂)₂], the Sn atom is six-coordinated in a distorted tetragonal–bipyramidal configuration by four O atoms in the equatorial plane and two C atoms in the axial positions. Intramolecular C—H⋯O hydrogen bonds result in the formation of two planar and two non-planar five-membered rings; the latter adopt envelope conformations. There are weak π–π interactions between aromatic rings, with centroid-to-centroid distances of 3.796 (2) and 4.171 (2) Å. There is also a single C—Cl⋯π interaction [C—Cl = 1.740 (4), Cl⋯π = 3.795 (2) C⋯π = 3.697 (4) Åand C—Cl⋯\p =73.45 (11)°].

Related literature

For general background, see: Xie et al. (1996 ▶); Nath et al. (2001 ▶); Crowe (1989 ▶); Gielen et al. (2000 ▶). For related literature, see: Hanif et al. (2007 ▶); Parvez et al. (1997 ▶).

Experimental

Crystal data

[Sn(C₂H₅)₂(C₁₀H₈ClO₂)₂]
M _r = 568.04
Triclinic,
a = 7.5171 (3) Å
b = 12.8388 (5) Å
c = 12.8712 (5) Å
α = 98.724 (2)°
β = 92.250 (2)°
γ = 100.148 (2)°
V = 1205.84 (8) Å³
Z = 2
Mo Kα radiation
μ = 1.31 mm⁻¹
T = 296 (2) K
0.25 × 0.18 × 0.15 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.756, T _max = 0.819
20475 measured reflections
4718 independent reflections
4364 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.027
wR(F ²) = 0.090
S = 1.23
4718 reflections
281 parameters
H-atom parameters constrained
Δρ_max = 1.19 e Å⁻³
Δρ_min = −0.70 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: APEX2; data reduction: SAINT (Bruker, 2007 ▶); 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 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808018321/hk2473sup1.cif

e-64-0m946-sup1.cif^{(23.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808018321/hk2473Isup2.hkl

e-64-0m946-Isup2.hkl^{(140.7KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

Sn—C1	2.110 (3)
Sn—C3	2.113 (4)
Sn—O3	2.1342 (19)
Sn—O1	2.137 (2)
Sn—O2	2.477 (2)
Sn—O4	2.556 (2)

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C1—Sn—C3	154.28 (15)
C1—Sn—O3	98.88 (12)
C3—Sn—O3	101.22 (13)
C1—Sn—O1	98.94 (11)
C3—Sn—O1	99.02 (12)
O3—Sn—O1	83.85 (8)
C1—Sn—O2	86.19 (12)
C3—Sn—O2	88.69 (13)
O3—Sn—O2	139.87 (8)
O1—Sn—O2	56.10 (7)
C1—Sn—O4	89.58 (11)
C3—Sn—O4	89.11 (12)
O3—Sn—O4	54.58 (7)
O1—Sn—O4	138.42 (7)
O2—Sn—O4	165.46 (7)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7A⋯O2	0.96	2.31	2.780 (5)	109
C8—H8⋯O1	0.93	2.30	2.736 (3)	108
C17—H17A⋯O3	0.96	2.31	2.749 (4)	107
C18—H18⋯O4	0.93	2.37	2.785 (3)	107

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Acknowledgments

The authors acknowledge the Higher Education Commision, Islamabad, Pakistan, for funding the purchase of the diffractometer and for financial support to NM for a PhD under the Indigenous Scholarship Scheme.

supplementary crystallographic information

Comment

Organotin compounds have attracted much interest owing to their potential use in industry and agriculture (Xie et al., 1996; Nath et al., 2001). In the pharmaceutical industry, a number of dialkyltin carboxylate derivatives are being used as efficient antitumor and anticancer agents (Crowe, 1989; Gielen et al., 2000). In continuation of our studies on the structural aspects of organotin(IV) carboxylates, we report herein the crystal structure of the title compound, (I).

In the molecule of (I) (Fig. 1), the Sn atom is six-coordinated in distorted tetragonal bipyramidal configuration (Table 1) by four O atoms in the equatorial plane and two C atoms in the apical positions. The bond lengths and angles are within normal ranges, which are comparable with the corresponding values in bis(3,4-methylenedioxybenzoyl)diethyltin(IV), (II) (Hanif et al., 2007) and diethylbis[3-(2-thienyl)-2-propenoato-O,O']tin(IV), (III) (Parvez et al., 1997). The Sn—C1 [2.110 (3) Å] and Sn—C3 [2.113 (4) Å] bonds in (I) are reported as 2.137 (6) and 2.138 (7) Å in (II) and 2.155 (2) Å in (III). On the other hand, the Sn—O bonds are in the range of [2.1342 (19)–2.556 (2) Å] in (I). They are reported as in the ranges of [2.142 (4)–2.544 (4) Å] in (II) and [2.105 (5) and 2.538 (6) Å] in (III).

Rings A (Sn/O1/O2/C5), B (Sn/O3/O4/C15), C (C9–C14) and D (C19–C24) are, of course, planar, and the dihedral angles between them are A/B = 3.05 (11)°, A/C = 2.10 (12)°, A/D = 1.58 (10)°, B/C = 1.73 (12)°, B/D = 4.41 (11)° and C/D = 3.68 (13)°. So, they are nearly coplanar. The intramolecular C—H···O hydrogen bonds (Table 2) result in the formation of two planar and two non-planar five-membered rings: E (O1/C5/C6/C8/H8), F (O4/C15/C16/C18/H18), G (O2/C5–C7/H7A) and H (O3/C15–C17/H17A), respectively. Rings G and H adopt envelope conformations, with H7A and H17A atoms displaced by 0.184 and 0.356 Å from the planes of the other ring atoms, respectively.

In the crystal structure, the molecules are elongated along the c axis and stacked along the a axis (Fig. 2). The weak π–π interactions between aromatic rings CgC···CgDⁱ and CgC···CgDⁱⁱ [symmetry codes: (i) x, y, z - 1 and (ii) x + 1, y, z - 1] may be effective in the stabilization of the structure, with centroid–centroid distances of 3.796 (2) and 4.171 (2) Å, respectively. There is also a single C—Cl···π interaction, C21—Cl2···CgCⁱⁱⁱ [symmetry code: (iii) x - 1, y, z + 1], at a distance of 3.797 (2) Å.

Experimental

The title compound (I), was prepared by the reaction of stoichiometric amounts of the sodium 3-(3-chlorophenyl)-2-methylacrylate (0.5 g, 2.29 mmol) and diethyltin(IV) dichloride (0.28 g, 1.14 mmol) in dry toluene (100 ml). The reaction mixture was refluxed for 7–8 h, and then allowed to stand overnight. The residual sodium salt was removed by filtration and the solvent was evaporated under reduced pressure leaving a solid residue. Crystals suitable for X-ray analysis were obtained by the recrystallization of the obtained solid residue from a mixture of chloroform/n-hexane (4:1) (yield 77%).