{4-Bromo-2-[(5-chloro-2-oxidophen­yl)imino­methyl]­phenolato-κ3 O,N,O′}(methanol-κO)(methano­lato-κO)­oxidovanadium(V)

Gholam Hossein Shahverdizadeh; Seik Weng Ng; Edward R T Tiekink; Babak Mirtamizdoust

doi:10.1107/S160053681200311X

. 2012 Jan 31;68(Pt 2):m221–m222. doi: 10.1107/S160053681200311X

{4-Bromo-2-[(5-chloro-2-oxidophenyl)iminomethyl]phenolato-κ³ O,N,O′}(methanol-κO)(methanolato-κO)oxidovanadium(V)

Gholam Hossein Shahverdizadeh ^a,^‡, Seik Weng Ng ^b,^c, Edward R T Tiekink ^b,^*, Babak Mirtamizdoust ^d

PMCID: PMC3274936 PMID: 22346883

Abstract

The title Schiff base complex, [V(C₁₃H₇BrClNO₂)(CH₃O)O(CH₃OH)], features a vanadyl group, a tridentate Schiff base ligand, and coordinated methanol and methanolate ligands. The NO₅ donor set is based on a distorted octahedron. Helical supramolecular chains along [010] are found in the crystal structure mediated by O—H⋯O hydrogen bonds formed between the coordinating methanol molecule and the phenolate O atom of the chlorobenzene residue.

Related literature

For the structures of (E)-2-(2-hydroxybenzylideneamino)phenolates containing halide atoms on the aromatic ring(s), see: Yenişehirli et al. (2010 ▶). For related Schiff base vanadyl complexes containing alcohol and alkoxide ligands, see: Hartung et al. (2007 ▶); Clague et al. (1993 ▶). For the crystallization procedure, see: Harrowfield et al. (1996 ▶).

Experimental

Crystal data

[V(C₁₃H₇BrClNO₂)(CH₃O)O(CH₄O)]
M _r = 454.57
Monoclinic,
a = 9.9585 (2) Å
b = 9.8949 (2) Å
c = 17.3612 (3) Å
β = 100.746 (2)°
V = 1680.74 (6) Å³
Z = 4
Cu Kα radiation
μ = 9.42 mm⁻¹
T = 100 K
0.20 × 0.20 × 0.02 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ▶) T _min = 0.255, T _max = 0.834
6974 measured reflections
3453 independent reflections
3125 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.131
S = 1.04
3453 reflections
221 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.37 e Å⁻³
Δρ_min = −0.93 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681200311X/hg5167sup1.cif

e-68-0m221-sup1.cif^{(19.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681200311X/hg5167Isup2.hkl

e-68-0m221-Isup2.hkl^{(169.4KB, hkl)}

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

Table 1. Selected bond lengths (Å).

V—O1	1.872 (2)
V—O2	1.937 (2)
V—O3	2.266 (2)
V—O4	1.766 (2)
V—O5	1.596 (2)
V—N1	2.170 (3)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O2ⁱ	0.84 (1)	1.89 (2)	2.702 (3)	163 (5)

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Symmetry code: (i) Inline graphic .

Acknowledgments

We gratefully acknowledge support of this study by Tabriz Azad University, and thank the Ministry of Higher Education (Malaysia) for funding structural studies through the High-Impact Research scheme (UM.C/HIR/MOHE/SC/12).

supplementary crystallographic information

Comment

Structural studies of complexes with (E)-2-(2-hydroxybenzylideneamino)phenolates containing halide atoms on the aromatic ring(s) are comparatively rare (Yenişehirli et al., 2010) and those of complexes containing the (E)-4-bromo-2-((5-chloro-2-hydroxyphenylimino)methyl)phenolate ligand have not been reported. Herein we report the oxo-vanadium(V) complex of this ligand, (I).

The V atom in (I) is coordinated by the O,N,O-tridentate Schiff base ligand, an oxido-O atom, an O atom of the methoxido ligand and an O atom of the methanol ligand. The resulting NO₅ donor set is based on an octahedron. The methanol ligand is trans to the oxido group and the V—O(methanol) bond length is significantly longer than the V—O(methanolate) bond, Table 1. The coordination geometry resembles those found in related V═O Schiff base compounds containing neutral and anionic forms of alcohols (Clague et al., 1993; Hartung et al., 2007).

The most prominent feature of the crystal packing is the formation of helical supramolecular chains along [010], Fig. 1 and Table 2. The connections between molecules are of the type O—H···O and involve the coordinated methanol molecule as the donor and the phenoxide-O atom of the chloro-substituted benzene ring as the acceptor.

Experimental

A solution of 4-chlorosalicylaldehyde (10 mmol) in EtOH (25 ml) was added drop-wise to a solution of 2-(aminomethyl)-4-bromophenol (10 mmol) in EtOH (15 ml). The mixture was refluxed for 5 h. The yellow precipitate was removed by filtration and recrystallized from MeOH solution. Then the ligand (0.8 mmol) was placed in one arm of a branched tube (Harrowfield et al., 1996) and oxovanadium(IV) bis(acetylacetonate) (0.8 mmol) placed in the other. Methanol was then added to fill both arms. The tube was sealed and the ligand-containing arm immersed in a bath at 333 K, while the other was left at ambient temperature. After two weeks, crystals were deposited in the arm held at ambient temperature. They were filtered off, washed with acetone and ether, and air-dried. Yield: 61%. M.pt.: 517 K.