Bis(μ-4-fluoro-2,6-diformyl­phenolato)bis­[diaqua­nickel(II)] dichloride

Yin Zheng; Shi-Rong Li; Hong Zhou; Zhi-Quan Pan; Yi-Zhi Li

doi:10.1107/S1600536810016284

. 2010 May 19;66(Pt 6):m668. doi: 10.1107/S1600536810016284

Bis(μ-4-fluoro-2,6-diformylphenolato)bis[diaquanickel(II)] dichloride

Yin Zheng ^a, Shi-Rong Li ^b, Hong Zhou ^a, Zhi-Quan Pan ^a,^*, Yi-Zhi Li ^c

PMCID: PMC2979620 PMID: 21579311

Abstract

In the title dinuclear nickel(II) complex, [Ni₂(C₈H₄FO₃)₂(H₂O)₄]Cl₂, synthesized by the reaction between 4-fluoro-2,6-diformylphenol and nickel(II) chloride in methanol, the coordination cation is located on an inversion center and the Ni^II atom adopts a slightly distorted octahedral coordination geometry. The two Ni atoms are bridged by two phenolate O atoms and the intramolecular Ni⋯Ni distance is 3.0751 (9) Å. The crystal structure is stabilized by O—H⋯Cl hydrogen bonds.

Related literature

For the synthesis of related compounds and their properties, see: Thompson et al. (1996 ▶); Zhou et al. (2005 ▶); Raimondi et al. (2004 ▶); Taniguchi (1984 ▶); Mohanta et al. (1998 ▶); Wang et al. (1997 ▶). For related structures, see: Adhikary et al. (1987 ▶); Zhou et al. (2007 ▶).

Experimental

Crystal data

[Ni₂(C₈H₄FO₃)₂(H₂O)₄]Cl₂
M _r = 594.61
Monoclinic,
a = 8.3299 (14) Å
b = 13.576 (2) Å
c = 9.9965 (17) Å
β = 114.623 (3)°
V = 1027.6 (3) Å³
Z = 2
Mo Kα radiation
μ = 2.16 mm⁻¹
T = 291 K
0.26 × 0.22 × 0.20 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.603, T _max = 0.672
5827 measured reflections
2018 independent reflections
1708 reflections with I > 2σ(I)
R _int = 0.041

Refinement

R[F ² > 2σ(F ²)] = 0.051
wR(F ²) = 0.119
S = 1.05
2018 reflections
157 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.94 e Å⁻³

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810016284/gk2267sup1.cif

e-66-0m668-sup1.cif^{(17.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810016284/gk2267Isup2.hkl

e-66-0m668-Isup2.hkl^{(99.3KB, 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
O4—H4A⋯Cl1	0.85 (5)	2.44 (3)	3.198 (4)	149 (6)
O4—H4B⋯Cl1ⁱ	0.85 (5)	2.45 (3)	3.241 (4)	154 (5)
O5—H5C⋯Cl1ⁱⁱ	0.85 (2)	2.61 (4)	3.313 (4)	141 (5)
O5—H5A⋯Cl1ⁱⁱⁱ	0.86 (6)	2.39 (4)	3.101 (4)	142 (5)

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

Acknowledgments

The authors would like to thank the National Science Foundation of China for financial support (No. 20871097).

supplementary crystallographic information

Comment

Phenoxide-bridged dinuclear complexes have been extensively studied for several decades, most of them were derived from the cyclocondensation of 2,6-diformyl-4-R-phenol and alkyldiamine in the presence of metal ions (Thompson et al.,1996; Zhou et al., 2005; Raimondi et al., 2004).With short distances between the two metal ions in the complexes, they show special electrical and magnetic properties (Mohanta et al., 1998; Wang et al., 1997). Adhikary et al. reported a phenoxide-bridged dinuclear nickel(II) complex, obtained directly from the mixture of 2,6-diformyl-4-methyl-phenol and nickel(II) perchlorate (Adhikary et al., 1987). Here we report the crystal structure of a new dinuclear Ni^II complex with fluorine substituent in the phenyl ring. The diference between the title complex and the one Adhikary reported is that they have different substituents in the phenyl ring and different counter-anions.

The coordination cation consists of two 2,6-diformyl-4-flurophenolate ligands, four water molecules, two Ni^II ions (Fig. 1). The chlorine ions do not participate in coordination to the Ni atoms. Each Ni atom has a slightly distorted octahedral coordination geometry and it deviates from the equatorial plane defined by four coordinating oxygen atoms of the organic ligand by 0.0266 (4) Å. The axial positions are occupied by two water molecules with Ni–O distances of 2.057 (4) Å and 2.067 (4) Å.The Ni—O distance in the basal plane is in the range of 1.995 (4) Å - 2.019 (3) Å. The presence of the two bridging phenolate O atoms gives rise to a short metal-metal contact of 3.0751 (9) Å that is slightly longer than those of binuclear nickel(II) complexes with macrocyclic phenoxo-bridging ligands (Zhou et al., 2007).

Experimental

2, 6-Diformyl-4-fluorophenol was prepared according to the literature method (Taniguchi, 1984). To a solution of 2,6-diformyl-4-fluorinphenol (1 mmol, 0.17 g) in absolute methanol (10 ml) was added a methanol solution (10 ml) containing NiCl₂2H₂O (1 mmol, 0.17 g). The solution was stirred vigorously for 24 h at room temperature and filtrated. The dark-green block-shaped crystals suitable for X-ray diffraction analysis were obtained by slow evaporation of solvent over a period of two weeks.