Di-n-but­yl{1-[1-(2-hydroxy­phen­yl)ethyl­idene]-5-[1-(2-oxidophen­yl)ethyl­idene]thio­carbazonato-κ3 O 5,N 5,S}tin(IV)

Md Abu Affan; Dayang N A Chee Chee; Zaini Assim; Seik Weng Ng

doi:10.1107/S1600536810016016

. 2010 May 8;66(Pt 6):m618–m619. doi: 10.1107/S1600536810016016

Di-n-butyl{1-[1-(2-hydroxyphenyl)ethylidene]-5-[1-(2-oxidophenyl)ethylidene]thiocarbazonato-κ³ O ⁵,N ⁵,S}tin(IV)

Md Abu Affan ^a, Dayang N A Chee Chee ^a, Zaini Assim ^a, Seik Weng Ng ^b,^*

PMCID: PMC2979428 PMID: 21579277

Abstract

The ‘symmetrical’ 1,5-bis[1-(2-hydroxyphenyl)ethylidene]thiocarbazone Schiff base condenses with dibutyltin oxide to form the title complex, [Sn(C₄H₉)₂(C₁₇H₁₆N₄O₂S)], in which the deprotonated ligand O,N,S-chelates to the Sn atom of two crystallographically independent molecules. The ligand bears a formal negative charge on the S and one O atom; the other O atom retains its H atom. The Sn atoms are five-coordinated in a cis-C₂NOSSn trigonal-bipyramidal environment, and the apical sites are occupied by the O and S atoms. In both molecules, the hydroxy group is hydrogen bonded to a double-bonded N atom, generating a six-membered ring. The amino group is a donor to the coordinated O atom of an adjacent molecule, the hydrogen-bonding interaction giving rise to a helical chain running along the b axis. In one of the independent molecules, the atoms of one of the n-butyl groups are disordered over two sets of sites with equal occupancy. In the other independent molecule, the atoms of both n-butyl groups are disordered over two sets of sites with equal occupancy and, in addition, the Sn and S atoms were also refined as disordered over two sets of sites with equal occupancy.

Related literature

For the synthesis of 1,5-bis(2-hydroxybenzaldehyde) dithiocarbohydrazone, see: Ren et al. (1999 ▶).

Experimental

Crystal data

[Sn(C₄H₉)₂(C₁₇H₁₆N₄O₂S)]
M _r = 573.31
Monoclinic,
a = 24.8858 (17) Å
b = 9.4528 (7) Å
c = 23.6254 (17) Å
β = 112.756 (1)°
V = 5125.0 (6) Å³
Z = 8
Mo Kα radiation
μ = 1.11 mm⁻¹
T = 100 K
0.36 × 0.08 × 0.08 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan SADABS (Sheldrick, 1996 ▶) T _min = 0.691, T _max = 0.917
47957 measured reflections
11772 independent reflections
7256 reflections with I > 2σ(I)
R _int = 0.076

Refinement

R[F ² > 2σ(F ²)] = 0.058
wR(F ²) = 0.172
S = 1.12
11772 reflections
607 parameters
161 restraints
H-atom parameters constrained
Δρ_max = 1.77 e Å⁻³
Δρ_min = −1.75 e Å⁻³

Data collection: APEX2 software (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810016016/lh5030sup1.cif

e-66-0m618-sup1.cif^{(47.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810016016/lh5030Isup2.hkl

e-66-0m618-Isup2.hkl^{(575.6KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯O1ⁱ	0.86	2.24	3.054 (7)	159
N7—H7⋯O3ⁱⁱ	0.86	2.21	2.982 (7)	150
O2—H2⋯N4	0.84	1.79	2.503 (8)	141
O4—H4⋯N8	0.84	1.82	2.529 (8)	141

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

Acknowledgments

We thank MOSTI (grant No. 06-01-09-SF0046), Universiti Malaysia Sarawak and the University of Malaya for supporting this study.

supplementary crystallographic information

Comment

There are many crystallographic studies on metal derivatives of the Schiff bases derived by condensing salicyldehyde (and acetophenone) with semithiocarbazide (and thiocarbazide). 1,5-Bis(2-hydroxyacetophenone) thiocarbazone is a 'symmetrical' ligand; however, in the title di-n-butyltin derivative (Scheme I, Fig. 1), the doubly-deprotonated ligand chelates in a O,N,S-manner and only part of the molecule is used in coordination. There are two independent molecules. The tin atoms are five coordinate in a cis-C₂NOSSn trigonal bipyramidal environment, and the apical sites are occupied by the oxgen and sulfur atoms. The hydroxy group is hydrogen bonded to a double-bond nitrogen atom to generate a six-membered ring.

Experimental

1,5-Bis(2-hydroxyacetophenone) thiocarbazone was synthesized by using a literature method (Ren et al., 1999). The compound (0.66 g, 2 mmole) was dissolved in methanol (20 ml). Potassium hydroxide (0.23 g, 4 mmol) dissolved in methanol (5 ml) was added. The orange solution was then treated with di-n-butyltin dichloride (0.61 g, 2 mmol) in methanol (10 ml). The mixture was heated for an hour. The solution was filtered. The evaporation of the solvent gave a product that was recrystallized from ethanol in 60% yield; m.p. 401-403 K.