Trichlorido{2-dimeth­oxy­methyl-4-methyl-6-[(quinolin-8-yl)imino­meth­yl]phenolato-κ3 N,N′,O 1}tin(IV)

Keisuke Kawamoto; Takashi Shibahara

doi:10.1107/S1600536812002528

. 2012 Jan 31;68(Pt 2):m208. doi: 10.1107/S1600536812002528

Trichlorido{2-dimethoxymethyl-4-methyl-6-[(quinolin-8-yl)iminomethyl]phenolato-κ³ N,N′,O ¹}tin(IV)

Keisuke Kawamoto ^a, Takashi Shibahara ^a,^*

PMCID: PMC3274925 PMID: 22346872

Abstract

In the title compound, [Sn(C₂₀H₁₉N₂O₃)Cl₃], the Sn^IV ion is surrounded by a tridentate monoanionic Schiff base and by three meridional chloride ions in a six-coordinated distorted octahedral geometry. The Sn—Cl bond [2.366 (2) Å] trans to nitrogen is shorter than the others [2.438 (2) and 2.414 (2) Å]. The N—Sn—N angle [76.19 (11)°] is smaller than the O—Sn—N angle [87.89 (10)°] in the Schiff base ligand. No classical intermolecular hydrogen-bonding interactions are observed. The crystal packing exhibits π–π stacking interactions, with a distance of 3.595 (2) Å between the centroids of the phenolate ring and the benzene ring of the quinoline group of inversion-related molecules.

Related literature

For a related structure, see: Takano & Shibahara (2008 ▶).

Experimental

Crystal data

[Sn(C₂₀H₁₉N₂O₃)Cl₃]
M _r = 560.43
Triclinic,
a = 7.213 (5) Å
b = 11.786 (8) Å
c = 13.197 (8) Å
α = 72.300 (13)°
β = 79.10 (3)°
γ = 89.89 (3)°
V = 1047.5 (13) Å³
Z = 2
Mo Kα radiation
μ = 1.63 mm⁻¹
T = 93 K
0.23 × 0.22 × 0.11 mm

Data collection

Rigaku Mercury70 diffractometer
Absorption correction: multi-scan (REQAB; Rigaku, 1998 ▶) T _min = 0.779, T _max = 0.836
15965 measured reflections
5989 independent reflections
5512 reflections with F ² > 2σ(F ²)
R _int = 0.020

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.101
S = 1.04
5989 reflections
292 parameters
H-atom parameters constrained
Δρ_max = 1.51 e Å⁻³
Δρ_min = −1.24 e Å⁻³

Data collection: CrystalClear (Rigaku, 2007) ▶; cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SIR2004 (Burla et al., 2005 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: CrystalStructure (Rigaku, 2010 ▶); software used to prepare material for publication: CrystalStructure .

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812002528/pk2385sup1.cif

e-68-0m208-sup1.cif^{(32.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812002528/pk2385Isup2.hkl

e-68-0m208-Isup2.hkl^{(293.2KB, hkl)}

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

Acknowledgments

The authors thank Ms Kanako Ichikawa for the preparation of the title compound and the Japan Private School Promotion Foundation for financial support.

supplementary crystallographic information

Comment

The title compound is a tin(IV) complex with a Schiff base ligand, which was obtained by the condensation reaction of 8-aminoquinoline with 2-hydroxy-5-methylisophthalaldehyde. The synthetic method of the complex was reported, and the ¹H NMR spectrum in DMSO-d₆ revealed that the formyl group of the aldehyde changed to the acetal group on coordination to tin(IV) (Takano & Shibahara, 2008).

In this paper, we report the X-ray analysis of the title compound using a different synthetic method from the previous one: 1) acetylacetone tin(IV) dichloride salt, Sn^IVCl₂(C₅H₇O₂)₂, was used in place of SnCl₄.5H₂O. 2) the new method does not require heating. 3) tetrabutyl ammonium chloride was added to supply chloride ion. The new method gives orange block crystals of the title compound by slow ligand exchange reaction from acetylacetonate to Schiff base, while the previous method gives yellow powder by heating at 60°C for 2~3 h. The ¹H NMR spectrum of the crystals is identical to that of the yellow powder.

In the X-ray structure, the tin(IV) complex has a six-coordinated distorted octahedral geometry coordinated by a tridentate monoanionic Schiff base and by three meridional chloride ions (Fig. 1). The difference in trans influence between imino N and Cl induces different Sn1—Cl distances [Sn1—Cl1, 2.438 (2) Å; Sn1—Cl2, 2.414 (2) Å; Sn1—Cl3, 2.366 (2) Å]. The N1—Sn1—N2 angle [76.20 (11)°] is smaller than the O1—Sn—N1 angle [87.89 (10)°] in the Schiff base ligand. Although no intermolecular interaction via hydrogen bonding was observed in the crystal packing, the crystal packing exhibits π-π stacking interactions with a distance of 3.595 (2) Å between the centroids of aromatic rings (Fig. 2).

Experimental

To a solution of acetylacetone tin(IV) dichloride salt, Sn^IVCl₂(C₅H₇O₂)₂ (50.24 mg, 0.13 mmol) in methanol (60 ml) was added tetrabutyl ammonium chloride (36.72 mg, 0.13 mmol). To the methanol solution was added 8-aminoquinoline (19.09 mg, 0.13 mmol) and 2-hydroxy-5-methylisophthalaldehyde (21.58 mg, 0.13 mmol). Orange block single crystals of title compound suitable for X-ray analysis were obtained after leaving the solution to stand for three weeks at room temperature in the dark.