trans-Tetra­aqua­bis­(isonicotinamide-κN 1)nickel(II) bis­(3-hy­droxy­benzoate) tetra­hydrate

Ibrahim Göker Zaman; Nagihan Çaylak Delibaş; Hacali Necefoğlu; Tuncer Hökelek

doi:10.1107/S1600536812002218

. 2012 Jan 21;68(Pt 2):m200–m201. doi: 10.1107/S1600536812002218

trans-Tetraaquabis(isonicotinamide-κN ¹)nickel(II) bis(3-hydroxybenzoate) tetrahydrate

Ibrahim Göker Zaman ^a, Nagihan Çaylak Delibaş ^b, Hacali Necefoğlu ^a, Tuncer Hökelek ^c,^*

PMCID: PMC3274920 PMID: 22346867

Abstract

The asymmetric unit of the title compound, [Ni(C₆H₆N₂O)₂(H₂O)₄](C₇H₅O₃)₂·4H₂O, contains one-half of the complex cation with the Ni^II ion located on an inversion center, a 3-hydroxybenzoate counter-anion and two uncoordinated water molecules. Four water O atoms in the equatorial plane around the Ni^II ion [Ni—O = 2.052 (2) and 2.079 (2) Å] form a slightly distorted square-planar arrangement, which is completed up to a distorted octahedron by the two N atoms [Ni—N = 2.075 (3) Å] from two isonicotinamide ligands. In the anion, the carboxylate group is twisted from the attached benzene ring by 8.8 (3)°. In the crystal, a three-dimensional hydrogen-bonding network, formed by classical O—H⋯O and N—H⋯O hydrogen bonds, consolidates the crystal packing, which also exhibits π–π interactions between the benzene and pyridine rings, with centroid–centroid distances of 3.455 (2) and 3.621 (2) Å, respectively.

Related literature

For general background, see: Bigoli et al. (1972 ▶); Krishnamachari (1974 ▶). For related structures, see: Hökelek et al. (2009a ▶,b ▶,c ▶,d ▶,e ▶); Sertçelik et al. (2009a ▶,b ▶).

Experimental

Crystal data

[Ni(C₆H₆N₂O)₂(H₂O)₄](C₇H₅O₃)₂·4H₂O
M _r = 721.29
Monoclinic,
a = 6.6884 (3) Å
b = 16.9271 (5) Å
c = 13.5543 (4) Å
β = 100.186 (3)°
V = 1510.37 (9) Å³
Z = 2
Mo Kα radiation
μ = 0.73 mm⁻¹
T = 100 K
0.46 × 0.33 × 0.18 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.750, T _max = 0.877
13495 measured reflections
3723 independent reflections
3365 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.051
wR(F ²) = 0.157
S = 1.26
3723 reflections
256 parameters
12 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.86 e Å⁻³
Δρ_min = −0.69 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: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812002218/cv5237sup1.cif

e-68-0m200-sup1.cif^{(19.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812002218/cv5237Isup2.hkl

e-68-0m200-Isup2.hkl^{(178.8KB, 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
N2—H21⋯O1ⁱ	0.83 (5)	2.20 (5)	3.018 (4)	169 (4)
N2—H22⋯O8ⁱⁱ	0.84 (5)	2.21 (5)	3.012 (4)	159 (5)
O3—H31⋯O7	0.79 (5)	1.91 (5)	2.696 (4)	175 (5)
O5—H51⋯O3ⁱⁱ	0.85 (4)	1.87 (4)	2.716 (3)	177 (5)
O5—H52⋯O1ⁱⁱⁱ	0.84 (5)	1.99 (6)	2.795 (4)	160 (6)
O6—H61⋯O4ⁱⁱ	0.85 (3)	1.86 (3)	2.693 (3)	169 (4)
O6—H62⋯O1^iv	0.85 (5)	1.87 (5)	2.685 (4)	159 (5)
O7—H71⋯O7^v	0.78 (4)	2.03 (3)	2.795 (4)	167 (6)
O7—H72⋯O2^vi	0.85 (5)	1.88 (5)	2.731 (4)	177 (5)
O8—H81⋯O7^vii	0.77 (4)	2.10 (4)	2.802 (4)	152 (6)
O8—H82⋯O2	0.83 (4)	1.93 (5)	2.752 (4)	171 (4)

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .

Acknowledgments

The authors are indebted to Anadolu University and the Medicinal Plants and Medicine Research Centre of Anadolu University, Eskişehir, Turkey, for the use of X-ray diffractometer.

supplementary crystallographic information

Comment

As a part of our ongoing investigation on transition metal complexes of nicotinamide (NA), one form of niacin (Krishnamachari, 1974), and/or the nicotinic acid derivative N,N-diethylnicotinamide (DENA), an important respiratory stimulant (Bigoli et al., 1972), the title compound (I) was synthesized and its crystal structure is reported herein.

The asymmetric unit of (I) (Fig. 1) contains one Ni^II ion on a centre of symmetry, one isonicotinamide (INA) ligand, one 3-hydroxybenzoate (HB) molecule, two coordinated and two uncoordinated water molecules, respectively. The structures of some DENA and/or NA complexes of Ni^II and Co(II) ions, [Ni(C₈H₅O₃)₂(C₁₀H₁₄N₂O)₂(H₂O)₂] (Sertçelik et al., 2009a), [Ni(C₆H₆N₂O)₂(H₂O)₄](C₇H₄FO₂)₂ (Hökelek et al., 2009a), [Ni(C₆H₆N₂O)₂(H₂O)₄](C₈H₅O₃)₂.2(H₂O) (Hökelek et al., 2009b), [Ni(C₇H₄BrO₂)₂(C₆H₆N₂O)₂(H₂O)₂] (Hökelek et al., 2009c), [Co(C₆H₆N₂O)₂(H₂O)₄](C₈H₅O₃)₂.2(H₂O) (Hökelek et al., 2009d), [Co(C₆H₆N₂O)(C₉H₁₀NO₂)₂(H₂O)₂] (Hökelek et al., 2009e) and [Co(C₈H₅O₃)₂(C₁₀H₁₄N₂O)₂(H₂O)₂] (Sertçelik et al., 2009b) have also been determined. In (I), INA ligands are monodentate. The four O atoms (O5, O6, and the symmetry-related atoms, O5', O6') in the equatorial plane around the Ni atom form a slightly distorted square-planar arrangement, while the slightly distorted octahedral coordination is completed by the two pyridine N atoms (N1, N1') of the INA ligands at 2.075 (3) Å from the Ni atom in the axial positions (Fig. 1). The average Ni—O bond length is 2.066 (2) Å. The intramolecular O—H···O hydrogen bonds (Table 1) link the uncoordinated water molecules to the HB anion. The dihedral angle between the planar carboxylate group (O1/O2/C1) and the benzene ring A (C2—C7) is 8.77 (27)°, while that between rings A and B (N1/C8—C12) is 1.53 (11)°.

In the crystal structure, intermolecular O—H···O and N—H···O hydrogen bonds (Table 1) link the molecules into a three-dimensional network, in which they may be effective in the stabilization of the structure. π–π Contacts between the benzene and phenyl rings, Cg1···Cg2 and Cg1···Cg2ⁱ, [symmetry code: (i) -1 + x, y, z, where Cg1 and Cg2 are centroids of the rings A (C2–C7) and B (N1/C8–C12), respectively] may further stabilize the structure, with centroid-centroid distances of 3.621 (2) and 3.455 (2) Å, respectively.

Experimental

The title compound was prepared by the reaction of NiSO₄.6H₂O (1.314 g, 5 mmol) in H₂O (100 ml) and INA (1.220 g, 10 mmol) in H₂O (50 ml) with sodium 3-hydroxybenzoate (1.601 g, 10 mmol) in H₂O (100 ml). The mixture was filtered and set aside to crystallize at ambient temperature for four weeks, giving blue single crystals.