Bis[2-(hy­droxy­imino­meth­yl)phenolato]nickel(II): a second monoclinic polymorph

Julia A Rusanova; Elena A Buvaylo; Eduard B Rusanov

doi:10.1107/S1600536811001383

. 2011 Jan 15;67(Pt 2):m222–m223. doi: 10.1107/S1600536811001383

Bis[2-(hydroxyiminomethyl)phenolato]nickel(II): a second monoclinic polymorph

Julia A Rusanova ^a,^*, Elena A Buvaylo ^a, Eduard B Rusanov ^b

PMCID: PMC3051639 PMID: 21522882

Abstract

The title compound, [Ni(C₇H₆NO₂)₂], (I), is a second monoclinic polymorph of the compound, (II), reported by Srivastava et al. [Acta Cryst. (1967), 22, 922] and Mereiter [Private communication (2002) CCDC refcode NISALO01]. The bond lengths and angles are similar in both structures. The molecule in both structures lies on a crystallographic inversion center and both have an internal hydrogen bond. The title compound crystallizes in the space group P2₁/c (Z = 2), whereas compound (II) is in the space group P2₁/n (Z = 2) with a similar cell volume but different cell parameters. In both polymorphs, molecules are arranged in the layers but in contrast to the previously published compound (II) where the dihedral angle between the layers is 86.3°, in the title polymorph the same dihedral angle is 29.4°. The structure of (I) is stabilized by strong intramolecular O—H⋯O hydrogen bonding between the O—H group and the phenolate O atom.

Related literature

For the original monoclinic polymorph, see: Srivastava et al. (1967 ▶); Mereiter (2002 ▶). For background to direct synthesis, see: Nesterov et al. (2004 ▶, 2006 ▶); Kovbasyuk et al. (1998 ▶); Vassilyeva et al. (1997 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

[Ni(C₇H₆NO₂)₂]
M _r = 330.97
Monoclinic,
a = 4.9912 (2) Å
b = 7.4717 (3) Å
c = 17.4152 (7) Å
β = 90.653 (3)°
V = 649.42 (5) Å³
Z = 2
Mo Kα radiation
μ = 1.51 mm⁻¹
T = 296 K
0.53 × 0.36 × 0.11 mm

Data collection

Bruker SMART APEXII diffractometer
Absorption correction: numerical (SADABS; Sheldrick, 2002 ▶) T _min = 0.501, T _max = 0.851
4678 measured reflections
1342 independent reflections
1096 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.030
wR(F ²) = 0.072
S = 1.06
1342 reflections
121 parameters
All H-atom parameters refined
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); 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/S1600536811001383/br2156sup1.cif

e-67-0m222-sup1.cif^{(13.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811001383/br2156Isup2.hkl

e-67-0m222-Isup2.hkl^{(66.3KB, hkl)}

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

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

N1—Ni1	1.8661 (19)
Ni1—O1	1.8292 (16)

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O1—Ni1—N1

93.08 (8)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O1ⁱ	0.80 (3)	1.80 (3)	2.511 (2)	146 (4)

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors gratefully acknowledge the Ukrainian State Fund for Fundamental Researchers (SFFR) for financial support of the Research Program (Chemistry).

supplementary crystallographic information

Comment

The cell dimensions of the title modification after transformation from P2₁/c to P2₁/n setting, are: a=18.062, b=7.472, c=4.991, β =105.39, whereas the cell dimensions of the reported compound (II) monoclinic P2₁/n modification are: a = 13. 830, b = 4.880, c = 10.200 Å; β = 110.43° ( Srivastava et al., 1967). The asymmetric unit of the title compound contains half molecule (Fig. 1), lying across a crystallographic inversion centre. The bond lengths and angles are within normal ranges (Allen et al., 1987) and are comparable with the structure of the compound (II).

Experimental

The title compound was prepared by direct synthesis: manganese powder (0.06 g, 1 mmol), Ni(OAc)₂ (0.25 g, 1 mmol), salicylic aldehyde (0.21 ml, 2 mmol), NH₂OH^.HCl (0.14 g, 2 mmol), dimethylformamide (20 ml) were heated to 323–333 K and stirred magnetically for 40 min, until total dissolution of the manganese powder was observed. The transparent brown solution was allowed to stand at room temperature and brown-green crystals of the title compound suitable for X-ray analysis precipitated within few days. They were collected by filter-suction, washed with dry PrⁱOH and finally dried in vacuo at room temperature (yield; 0.12 g)