[3-(Dimethyl­amino)benzoato]triphenyl­tin(IV)

Yip Foo Win; Siang Guan Teoh; Sie Tiong Ha; Reza Kia; Hoong-Kun Fun

doi:10.1107/S1600536808036337

. 2008 Nov 13;64(Pt 12):m1530–m1531. doi: 10.1107/S1600536808036337

[3-(Dimethylamino)benzoato]triphenyltin(IV)

Yip Foo Win ^a,^‡, Siang Guan Teoh ^a, Sie Tiong Ha ^b, Reza Kia ^c, Hoong-Kun Fun ^c,^*

PMCID: PMC2959792 PMID: 21581146

Abstract

In the title compound, [Sn(C₆H₅)₃(C₉H₁₀NO₂)], the Sn atom is coordinated by three phenyl groups and a carboxylate anion in a distorted tetrahedral geometry. An intramolecular C—H⋯O interaction forms an S(7) ring motif. The dihedral angles between the benzoate group and the other three phenyl rings are 76.94 (8), 66.82 (8) and 42.34 (9)°. The crystal structure is further stabilized by intermolecular C—H⋯π interactions.

Related literature

For hydrogen-bond motifs, see Bernstein et al. (1995 ▶). For values of bond lengths, see Allen et al. (1987 ▶). For related literature on triorganotin(IV) complexes see, for example: Willem et al. (1997 ▶); Novelli et al. (1999 ▶); Gielen et al. (2000 ▶); Tian et al. (2005 ▶); Baul et al. (2001 ▶); Win et al. (2006 ▶, 2007a ▶,b ▶); Yeap & Teoh (2003 ▶).

Experimental

Crystal data

[Sn(C₆H₅)₃(C₉H₁₀NO₂)]
M _r = 514.17
Triclinic,
a = 9.1140 (2) Å
b = 10.0027 (2) Å
c = 14.5066 (4) Å
α = 100.925 (1)°
β = 103.106 (1)°
γ = 110.778 (1)°
V = 1150.13 (5) Å³
Z = 2
Mo Kα radiation
μ = 1.13 mm⁻¹
T = 100.0 (1) K
0.46 × 0.42 × 0.17 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.623, T _max = 0.830
18268 measured reflections
5259 independent reflections
5141 reflections with I > 2σ(I)
R _int = 0.017

Refinement

R[F ² > 2σ(F ²)] = 0.017
wR(F ²) = 0.049
S = 1.08
5259 reflections
282 parameters
H-atom parameters constrained
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.56 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005 ▶); program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808036337/kp2195sup1.cif

e-64-m1530-sup1.cif^{(23.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808036337/kp2195Isup2.hkl

e-64-m1530-Isup2.hkl^{(257.5KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Sn1—O1	2.0649 (11)
Sn1—C1	2.1239 (15)
Sn1—C13	2.1260 (14)
Sn1—C7	2.1290 (14)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8A⋯O2	0.93	2.43	3.126 (2)	132
C24—H24A⋯Cg1ⁱ	0.93	2.88	3.6772 (19)	144
C26—H26B⋯Cg2ⁱⁱ	0.96	2.74	3.672 (2)	164

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

Acknowledgments

The authors thank the Malaysian Government and Universiti Sains Malaysia for the RU research grant 101/PKIMIA/815002 and facilities. HKF and RK thanks the Malaysian Government and Universiti sains Malaysia for the Science Fund grant No. 305/PFIZIK/613312. RK thanks Universiti Sains Malaysia for a post-doctoral research fellowship.

supplementary crystallographic information

Comment

Triorganotin(IV) complexes are well known for their biological properties as well as industrial applications (Willem et al., 1997; Novelli et al., 1999; Gielen et al., 2000; Tian et al., 2005). Generally, triphenyltin(IV) carboxylate complexes are commonly found as monomeric structures with four-coordinated distorted tetrahedral or five-coordinated trigonal bipyramid geometries (Baul et al., 2001; Yeap & Teoh, 2003; Win et al., 2007b). In a recent study, the coordination geometry of (3,5-dinitrobenzoato)triphenyltin(IV) is found to be distorted tetrahedral due to the long range interaction of the carboxylate anion coordinated to the Sn moiety in an isobidentate fashion (Win et al., 2006). In addition, triphenyltin(IV) carboxylates are also able to form polymeric structures (Tian et al., 2005; Win et al., 2007a). In the polymeric system, the carboxylate anions act as bridging bidentate ligands in the bonding to the neighbouring tin(IV) resulting in a polymeric structure with the tin atom exhibiting trigonal bipyramid geometry as shown in the complex, catena-poly[[triphenyltin(IV)–2,4-dinitrobenzoato] (Win et al., 2007a). Based on the crystallographic structural study, the title complex [3-(dimethylamino)benzoato]triphenyltin(IV) has a monomeric four-coordinated distorted tetrahedral structure which is similar to that found for [4-(diethylamino)benzoato-κO]triphenyltin(IV) (Win et al., 2007b).

The bond lengths (Allen et al., 1987) and angles in the molecule (I, Fig. 1, Table 1) are within normal ranges. The Sn atom is coordinated by the three phenyl groups and a carboxylate anion in a distorted tetrahedral geometry. An intramolecular hydrogen bond C—H···O forms a seven-membered ring, characterized as S(7) motif (Bernstein et al., 1995). The dihedral angles between the phenyl-carboxylate group and the other three phenyl rings are 76.94 (8), 66.82 (8), and 42.34 (9)°, respectively. The crystal structure (Fig. 2), is further stabilized by intermolecular C—H···π (x 2) (Table 2) interactions.

Experimental

The complex [3-(dimethylamino)benzoato]triphenyltin(IV) was obtained by heating under reflux a 1:1 molar mixture of triphenyltin(IV) hydroxide (1.10 g, 3 mmol) and 3-(dimethylamino)benzoic acid (0.50 g, 3 mmol) in acetonitrile (50 ml) for an hour. The clear brown solution was isolated by filtration and kept in a bottle. After eight days, brown crystals (1.01 g, 65.7% yield) were collected. Melting point: 413.2–414.5 K. Analysis found for C₂₇H₂₅NO₂Sn: C, 63.05; H, 4.91; N, 2.67; Sn, 23.00%. Calculated found for C₂₇H₂₅NO₂Sn: C, 63.07; H, 4.90; N, 2.72; Sn, 23.08%. FTIR as KBr disc (cm_-1): υ (C—H) aromatic 3065, 3051, 3026; υ (C—H) saturated 2989, 2908, 2810; υ (COO)_as 1625, υ (COO)_s 1322, υ (C—N) 1227, υ (Sn—O) 445. ¹H-NMR: δ: phenyl protons 7.42–7.49 (9H, m); 7.79–7.81 (6H, m); benzene 6.86–6.88 (1H, dd); 7.24–7.28 (1H, t); 7.51–7.53 (2H, d); N-(CH3)2 2.95 (6H, s) p.p.m.. ¹³C-NMR: δ: phenyl carbons C_ipso 139.01 (648.9 Hz), C_ortho 137.36 (47.9 Hz), C_meta 129.31 (63.2 Hz), C_para 130.28; benzene 114.84, 117.18, 119.31, 129.57, 134.59, 150.85; N-(CH₃)₂ 41.04; COO 174.05 p.p.m.. ¹¹⁹Sn-NMR: υ: -114.19 p.p.m..