Bis(μ-2-{[oxido(phenyl)methylidene]hydrazinylidene}propanoato)bis[dibenzyl(ethanol)tin(IV)]

Shaojun Sun; Jie Yang

doi:10.1107/S1600536811011937

. 2011 Apr 7;67(Pt 5):m544. doi: 10.1107/S1600536811011937

Bis(μ-2-{[oxido(phenyl)methylidene]hydrazinylidene}propanoato)bis[dibenzyl(ethanol)tin(IV)]

Shaojun Sun ^a,^*, Jie Yang ^b

PMCID: PMC3089280 PMID: 21754282

Abstract

In the title complex, [Sn₂(C₇H₇)₄(C₁₀H₈N₂O₃)₂(C₂H₅OH)₂], the Sn(IV) atom is seven-coordinated in a distorted pentagonal–bipyramidal geometry by three O atoms and one N atom from the pyruvate benzoyl hydrazone ligand, one ethanol O atom and two axial C atoms from trans-benzyl groups, thus forming a dimeric molecule ( Inline graphic symmetry) via weak Sn—O interactions. The C atoms of one phenyl ring and the ethanol molecule are disordered over two sets of sites with site-occupancy factors of 0.57 (5):0.43 (5) and 0.79 (2):0.21 (2), respectively. Intermolecular O—H⋯O hydrogen bonds stabilize the crystal structure.

Related literature

For related structures, see: Sun & Hu (2007 ▶); Gielen et al. (2002 ▶).

Experimental

Crystal data

[Sn₂(C₇H₇)₄(C₁₀H₈N₂O₃)₂(C₂H₆O)₂]
M _r = 1102.42
Triclinic,
a = 8.7187 (18) Å
b = 11.385 (2) Å
c = 13.198 (3) Å
α = 96.170 (3)°
β = 93.728 (2)°
γ = 105.861 (3)°
V = 1246.8 (4) Å³
Z = 1
Mo Kα radiation
μ = 1.06 mm⁻¹
T = 298 K
0.45 × 0.37 × 0.23 mm

Data collection

Siemens SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.647, T _max = 0.793
6566 measured reflections
4356 independent reflections
3598 reflections with I > 2σ(I)
R _int = 0.017

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.116
S = 1.08
4356 reflections
298 parameters
H-atom parameters constrained
Δρ_max = 1.04 e Å⁻³
Δρ_min = −0.58 e Å⁻³

Data collection: SMART (Siemens, 1996 ▶); cell refinement: SAINT (Siemens, 1996 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811011937/lr2004sup1.cif

e-67-0m544-sup1.cif^{(22.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811011937/lr2004Isup2.hkl

e-67-0m544-Isup2.hkl^{(213.4KB, hkl)}

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

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

Sn1—C11	2.135 (6)
Sn1—O3	2.148 (3)
Sn1—C18	2.154 (6)
Sn1—N1	2.237 (4)
Sn1—O1	2.341 (3)
Sn1—O4	2.382 (4)
Sn1—O1ⁱ	2.772 (3)

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C11—Sn1—O3	97.42 (19)
C11—Sn1—C18	163.3 (2)
O3—Sn1—C18	94.77 (18)
C11—Sn1—N1	97.9 (2)
O3—Sn1—N1	70.83 (13)
C18—Sn1—N1	96.85 (18)
C11—Sn1—O1	88.59 (19)
O3—Sn1—O1	140.42 (12)
C18—Sn1—O1	89.30 (18)
N1—Sn1—O1	69.60 (12)
C11—Sn1—O4	84.9 (2)
O3—Sn1—O4	78.79 (13)
C18—Sn1—O4	86.28 (19)
N1—Sn1—O4	149.60 (14)
O1—Sn1—O4	140.79 (12)
C11—Sn1—O1ⁱ	80.32 (18)
O3—Sn1—O1ⁱ	154.13 (12)
C18—Sn1—O1ⁱ	83.72 (16)
N1—Sn1—O1ⁱ	135.04 (12)
O1—Sn1—O1ⁱ	65.45 (12)
O4—Sn1—O1ⁱ	75.34 (11)

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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
O4—H4⋯O2ⁱ	0.82	1.82	2.624 (6)	165

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Symmetry code: (i) Inline graphic .

Acknowledgments

We acknowledge financial support by the Clinical Laboratory of Liaocheng Hospital.

supplementary crystallographic information

Comment

Organotin derivatives of carboxylic acid ligands have been extensively studied due to their biological activities (Gielen et al., 2002). In our ongoing studies with Schiff base organotin(IV) compounds, the title compound has been synthesized and we report herein its crystal structure. The molecular structure of the compound is shown in Fig.1. The atoms O1, O3, N1 and O4 are coplanar within 0.0120 Å, which form the equatorial plane. Furthermore, the angle of the axial C11—Sn1—C18 is 163.3 (3)°, which deviates from the linear angle of 180°. These data indicate that the tin atom of this complex is in a distorted octahedral configuration. The O1 atom of the carboxylate residue also binds the other tin atom, Snⁱ, generating a Sn₂O₂ four-membered ring [symmetry code: 2 - x, 2 - y, -z]. The distances of Sn1–O1ⁱ 2.772 (4)Å are relatively longer than those of Sn1—O1 2.339 (4)Å (Table 1), but are comparable with those found in related seven-coordinate diorganotin systems (Sun et al., 2007). With weak interactions of Sn–O bonding, the structure of the title complex can be described as a dimer with crystallographically imposed 1 symmetry. and the coordination geometry of tin can be also described as a trans-C₂SnO₄N pentagonal bipyramid with the two benzyl groups occupying trans positions. The forming of the dimer leads to the shorter interaction between O and Oⁱ, because the interaction of two monomers surpass the repelling effect of two O atoms. Otherwise, there exhibit the disorder at the C12 to C17 aromatic ring moiety and the C25, C26 atoms of the coordinated ethonal solvate molecule.

Each Sn atom is also coordinated by an ethanol molecule, the Sn1—O4 bond distance being 2.424 (3) Å, which is comparable with those in the analogous (Sun et al., 2007), due to the formation of intradimeric hydrogen bonds, O2–O4ⁱ (or O2ⁱ–O4) 2.624 (6)Å (Table 2). These hydrogen bonds contribute to the stability and compactness of the crystal structure (Fig. 2).

Experimental

Pyruvic acid benzoyldrazone (1 mmol) and sodium ethoxide (1 mmol) was added to the solution of dry benzene (20 ml) in a Schlenk flask and stirred for 0.5 h. Dibenzyltin dichloride (1 mmol) was then added and the reaction mixture was stirred for 12 h at 313 K and then filtered. The solvent was gradually removed by evaporation under vacuum until a solid product was obtained. The solid was then recrystallized from ethanol and colorless crystals suitable for X-ray diffraction were obtained. Elemental analysis, calculated for C₂₆H₂₈N₂O₄Sn: C 56.66, H 5.12, N 5.08; found: C 56.51, H 5.34, N 5.01%.