Di-μ3-oxido-bis­(μ2-quinaldato-κ2 O:O)­bis­(quinaldato-κ2 N,O)tetra­kis[di-n-butyl­tin(IV)]

Hongyun Wang; Handong Yin

doi:10.1107/S1600536807066378

. 2007 Dec 18;64(Pt 1):m197–m198. doi: 10.1107/S1600536807066378

Di-μ₃-oxido-bis(μ₂-quinaldato-κ² O:O)bis(quinaldato-κ² N,O)tetrakis[di-n-butyltin(IV)]

Hongyun Wang ^a, Handong Yin ^a,^*

PMCID: PMC2915128 PMID: 21200544

Abstract

The title tetranuclear Sn^IV complex, [Sn₄(C₄H₉)₈(C₁₀H₆NO₂)₄O₂], is a cluster built up by inversion symmetry around the central Sn₂O₂ ring. The coordination geometries of the Sn atoms involved can be classified into two types: the five-coordinate Sn atoms of the central Sn₂O₂ core have a trigonal–bipyramidal geometry, with axial positions occupied by a μ₃-O atom and a μ₂-O atom belonging to the nonchelating quinaldate ligand. The peripheral Sn atoms are six-coordinate, with a distorted octahedral geometry. The methyl group of an n-butyl ligand is disordered over two sites, with occupancies of 0.643 (12) and 0.357 (12).

Related literature

For related tin complexes, see: Ma et al. (2004 ▶); Tian et al. (2005 ▶).

Experimental

Crystal data

[Sn₄(C₄H₉)₈(C₁₀H₆NO₂)₄O₂]
M _r = 1652.29
Monoclinic,
a = 13.096 (5) Å
b = 12.551 (5) Å
c = 22.278 (9) Å
β = 93.971 (5)°
V = 3653 (3) Å³
Z = 2
Mo Kα radiation
μ = 1.41 mm⁻¹
T = 298 (2) K
0.52 × 0.31 × 0.24 mm

Data collection

Bruker SMART diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.517, T _max = 0.714
18614 measured reflections
6437 independent reflections
4499 reflections with I > 2σ(I)
R _int = 0.042

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.127
S = 1.00
6437 reflections
410 parameters
169 restraints
H-atom parameters constrained
Δρ_max = 0.92 e Å⁻³
Δρ_min = −0.49 e Å⁻³

Data collection: SMART (Siemens, 1996 ▶); cell refinement: SAINT (Siemens, 1996 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: SHELXTL (Siemens, 1996 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807066378/bh2155sup1.cif

e-64-0m197-sup1.cif^{(26.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807066378/bh2155Isup2.hkl

e-64-0m197-Isup2.hkl^{(315.1KB, hkl)}

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

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

Sn1—O5	2.042 (4)
Sn1—O5ⁱ	2.141 (4)
Sn1—O1	2.304 (4)
Sn1—N1	3.184 (5)
Sn2—O5	2.049 (4)
Sn2—O3	2.111 (4)
Sn2—O1	2.488 (4)
Sn2—N2	2.539 (5)

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O5—Sn1—C25	110.7 (2)
O5—Sn1—C21	113.6 (2)
C25—Sn1—C21	135.5 (3)
O5—Sn1—O5ⁱ	74.10 (15)
C25—Sn1—O5ⁱ	98.0 (2)
C21—Sn1—O5ⁱ	97.2 (2)
O5—Sn1—O1	72.85 (14)
C25—Sn1—O1	94.3 (2)
C21—Sn1—O1	95.2 (2)
O5ⁱ—Sn1—O1	146.94 (14)
O5—Sn1—N1	129.19 (14)
C25—Sn1—N1	70.85 (19)
C21—Sn1—N1	78.7 (2)
O5ⁱ—Sn1—N1	156.19 (13)
O1—Sn1—N1	56.67 (14)
O5—Sn2—O3	80.36 (15)
O5—Sn2—C29	105.4 (2)
O3—Sn2—C29	103.7 (2)
O5—Sn2—C33	102.6 (2)
O3—Sn2—C33	105.7 (2)
C29—Sn2—C33	142.1 (3)
O5—Sn2—O1	68.81 (14)
O3—Sn2—O1	149.11 (14)
C29—Sn2—O1	83.4 (2)
C33—Sn2—O1	83.5 (2)
O5—Sn2—N2	149.32 (15)
O3—Sn2—N2	69.24 (16)
C29—Sn2—N2	86.3 (2)
C33—Sn2—N2	82.4 (2)
O1—Sn2—N2	141.64 (14)

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Symmetry code: (i) Inline graphic .

Acknowledgments

We thank the National Natural Science Foundation of China (20771053) and the Natural Science Foundation of Shandong Province (2005ZX09) for financial support.

supplementary crystallographic information

Comment

The title compound, (I), is a cluster containing four Sn atoms (Fig. 1). The whole molecule lies on an inversion center, with a central Sn₂O₂ core. The structure is similar to that previously characterized with 3-hydroxypyridine-2-carboxylate as main ligand (Tian et al., 2005). The three-coordinated µ₃ atom O5 in the Sn₂O₂ ring is bonded to a Bu₂SnO₂N unit. Moreover, the C1 carboxylate group coordinates to each independent Sn atom in a bridging mode (Fig. 2). The geometry of the Sn1 atom in the Sn₂O₂ ring is distorted trigonal-bipyramidal with atoms O1 and O5ⁱ [symmetry code (i): -x + 1, -y + 2, -z] in axial positions, while two n-butyl groups and atom O5 form the equatorial plane. For the Sn2 atoms, six primary bonds are formed: three to the O atoms, two to the C atom of n-butyl groups, and one to the chelating quinoline N atom. Thus, the Sn2 centers display a distorted octahedral coordinated geometry. The Sn—O and Sn—N bond lengths (Table 1) are similar to those observed in related organotin carboxylates (Ma et al., 2004).

Experimental

The reaction was carried out under a nitrogen atmosphere. Quinaldic acid (1 mmol) and sodium ethoxide (1.2 mmol) were dissolved in ethanol (30 ml) in a Schlenk flask and stirred for 0.5 h. Dibutyltin dichloride (1 mmol) was then added and the reaction mixture was stirred for 12 h at 313 K. The resulting clear solution was evaporated under vacuum. The product was crystallized from a mixture of dichloromethane/methanol (1:1). Yield: 83%; m.p. 426 K. Analysis: calculated for C₇₂H₉₆N₄O₁₀Sn₄: C 52.33, H 5.86, N 3.39%. found: C 52.27, H 5.95, N 3.47%.