trans-Tetra­aqua­bis­(isonicotinamide-κN1)nickel(II) bis­(3-hy­droxy­benzoate) tetra­hydrate

Zaman, I.G.; Çaylak Delibaş, N.; Necefoğlu, H.; Hökelek, T.

doi:10.1107/S1600536812002218

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 2| February 2012| Pages m200-m201

doi:10.1107/S1600536812002218

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trans-Tetraaquabis(isonicotinamide-κN¹)nickel(II) bis(3-hydroxybenzoate) tetrahydrate

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

^aDepartment of Chemistry, Kafkas University, 36100 Kars, Turkey, ^bDepartment of Physics, Sakarya University, 54187 Esentepe, Sakarya, Turkey, and ^cDepartment of Physics, Hacettepe University, 06800 Beytepe, Ankara, Turkey
^*Correspondence e-mail: merzifon@hacettepe.edu.tr

(Received 16 January 2012; accepted 18 January 2012; online 21 January 2012)

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, P 2₁ /n
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[F² > 2σ(F²)] = 0.051
wR(F²) = 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

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)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) -x, -y, -z+1; (iv) -x+1, -y, -z+1; (v) -x, -y+1, -z+1; (vi) $[-x-{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (vii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812002218/cv5237sup1.cif

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

checkCIF report

Comment top

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.

Related literature top

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 top

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.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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).

Figures top

Fig. 1. The molecular structure of (I) with the atom-numbering scheme [symmetry code: (') - x, - y, -z]. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bonds are shown as dashed lines.

trans-Tetraaquabis(isonicotinamide-κN¹)nickel(II) bis(3-hydroxybenzoate) tetrahydrate top

Crystal data top

[Ni(C₆H₆N₂O)₂(H₂O)₄](C₇H₅O₃)₂·4H₂O	F(000) = 756
M_r = 721.29	D_x = 1.586 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 7580 reflections
a = 6.6884 (3) Å	θ = 2.4–28.4°
b = 16.9271 (5) Å	µ = 0.73 mm⁻¹
c = 13.5543 (4) Å	T = 100 K
β = 100.186 (3)°	Rod-shaped, blue
V = 1510.37 (9) Å³	0.46 × 0.33 × 0.18 mm
Z = 2

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	3723 independent reflections
Radiation source: fine-focus sealed tube	3365 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ϕ and ω scans	θ_max = 28.6°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −8→8
T_min = 0.750, T_max = 0.877	k = −22→21
13495 measured reflections	l = −17→15

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.157	H atoms treated by a mixture of independent and constrained refinement
S = 1.26	w = 1/[σ²(F_o²) + (0.0492P)² + 5.1781P] where P = (F_o² + 2F_c²)/3
3723 reflections	(Δ/σ)_max < 0.001
256 parameters	Δρ_max = 0.86 e Å⁻³
12 restraints	Δρ_min = −0.69 e Å⁻³

Crystal data top

[Ni(C₆H₆N₂O)₂(H₂O)₄](C₇H₅O₃)₂·4H₂O	V = 1510.37 (9) Å³
M_r = 721.29	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.6884 (3) Å	µ = 0.73 mm⁻¹
b = 16.9271 (5) Å	T = 100 K
c = 13.5543 (4) Å	0.46 × 0.33 × 0.18 mm
β = 100.186 (3)°

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	3723 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	3365 reflections with I > 2σ(I)
T_min = 0.750, T_max = 0.877	R_int = 0.029
13495 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	12 restraints
wR(F²) = 0.157	H atoms treated by a mixture of independent and constrained refinement
S = 1.26	Δρ_max = 0.86 e Å⁻³
3723 reflections	Δρ_min = −0.69 e Å⁻³
256 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Ni1	0.5000	0.0000	0.5000	0.00840 (16)
O1	−0.0786 (4)	0.04089 (13)	0.29703 (18)	0.0135 (5)
O2	−0.1778 (4)	0.11616 (14)	0.16276 (17)	0.0145 (5)
O3	−0.0150 (4)	0.39248 (14)	0.27901 (19)	0.0151 (5)
H31	−0.011 (8)	0.428 (3)	0.317 (4)	0.027 (13)*
O4	0.3941 (4)	0.32984 (14)	0.18014 (18)	0.0160 (5)
O5	0.3225 (4)	0.04752 (14)	0.59662 (18)	0.0128 (5)
H51	0.372 (9)	0.068 (3)	0.653 (3)	0.051 (17)*
H52	0.245 (8)	0.014 (3)	0.616 (5)	0.054 (18)*
O6	0.7696 (4)	0.03386 (14)	0.58654 (19)	0.0148 (5)
H61	0.803 (7)	0.0796 (16)	0.609 (3)	0.026 (12)*
H62	0.851 (7)	0.000 (3)	0.618 (4)	0.041 (16)*
O7	0.0025 (4)	0.51961 (15)	0.40009 (19)	0.0168 (5)
H71	−0.018 (9)	0.508 (4)	0.453 (2)	0.050*
H72	−0.101 (6)	0.548 (3)	0.380 (4)	0.047 (17)*
O8	0.0926 (4)	0.06780 (16)	0.04380 (19)	0.0192 (5)
H81	0.196 (5)	0.060 (4)	0.077 (4)	0.050*
H82	0.021 (7)	0.082 (3)	0.085 (3)	0.047 (17)*
N1	0.4858 (4)	0.10763 (15)	0.4259 (2)	0.0098 (5)
N2	0.5148 (5)	0.39569 (17)	0.3228 (2)	0.0140 (6)
H21	0.525 (7)	0.439 (3)	0.296 (3)	0.017 (11)*
H22	0.559 (8)	0.396 (3)	0.385 (4)	0.030 (13)*
C1	−0.1092 (5)	0.10742 (18)	0.2549 (2)	0.0112 (6)
C2	−0.0587 (5)	0.18065 (18)	0.3173 (2)	0.0106 (6)
C3	−0.0642 (5)	0.25416 (18)	0.2706 (2)	0.0110 (6)
H3	−0.1005	0.2580	0.2013	0.013*
C4	−0.0156 (5)	0.32139 (18)	0.3277 (3)	0.0120 (6)
C5	0.0358 (5)	0.31639 (19)	0.4314 (3)	0.0130 (6)
H5	0.0684	0.3619	0.4694	0.016*
C6	0.0386 (5)	0.2433 (2)	0.4783 (3)	0.0137 (6)
H6	0.0707	0.2399	0.5478	0.016*
C7	−0.0068 (5)	0.17514 (19)	0.4214 (2)	0.0121 (6)
H7	−0.0026	0.1261	0.4526	0.015*
C8	0.4370 (5)	0.11290 (18)	0.3253 (2)	0.0113 (6)
H8	0.4102	0.0666	0.2884	0.014*
C9	0.4250 (5)	0.18391 (18)	0.2748 (2)	0.0119 (6)
H9	0.3897	0.1851	0.2053	0.014*
C10	0.4660 (5)	0.25372 (18)	0.3287 (2)	0.0106 (6)
C11	0.5176 (5)	0.24858 (18)	0.4322 (2)	0.0124 (6)
H11	0.5467	0.2940	0.4706	0.015*
C12	0.5253 (5)	0.17508 (19)	0.4776 (2)	0.0118 (6)
H12	0.5594	0.1724	0.5471	0.014*
C13	0.4552 (5)	0.33050 (18)	0.2717 (2)	0.0115 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0102 (3)	0.0075 (3)	0.0072 (3)	−0.00025 (19)	0.00071 (19)	0.00018 (19)
O1	0.0146 (11)	0.0103 (10)	0.0151 (12)	0.0006 (8)	0.0015 (9)	0.0001 (8)
O2	0.0171 (12)	0.0151 (11)	0.0105 (11)	−0.0004 (9)	0.0007 (9)	−0.0006 (9)
O3	0.0218 (13)	0.0101 (11)	0.0132 (12)	0.0002 (9)	0.0022 (10)	0.0006 (9)
O4	0.0246 (13)	0.0122 (11)	0.0107 (11)	0.0019 (9)	0.0016 (10)	0.0017 (8)
O5	0.0145 (12)	0.0136 (11)	0.0113 (11)	−0.0003 (8)	0.0049 (9)	−0.0006 (9)
O6	0.0155 (12)	0.0098 (11)	0.0162 (12)	0.0000 (9)	−0.0052 (9)	−0.0013 (9)
O7	0.0199 (13)	0.0139 (11)	0.0155 (12)	0.0031 (9)	0.0004 (10)	0.0000 (9)
O8	0.0202 (13)	0.0214 (13)	0.0173 (13)	0.0031 (10)	0.0064 (10)	0.0001 (10)
N1	0.0084 (12)	0.0117 (12)	0.0096 (12)	0.0005 (9)	0.0025 (10)	0.0005 (9)
N2	0.0199 (15)	0.0109 (13)	0.0105 (14)	−0.0009 (10)	0.0007 (11)	0.0027 (10)
C1	0.0072 (13)	0.0127 (14)	0.0142 (15)	0.0003 (10)	0.0030 (11)	−0.0011 (11)
C2	0.0079 (14)	0.0115 (14)	0.0126 (15)	0.0008 (10)	0.0022 (11)	−0.0012 (11)
C3	0.0095 (14)	0.0147 (14)	0.0088 (14)	0.0014 (11)	0.0015 (11)	0.0008 (11)
C4	0.0094 (14)	0.0108 (14)	0.0160 (16)	0.0009 (11)	0.0027 (12)	0.0020 (12)
C5	0.0117 (14)	0.0129 (14)	0.0141 (16)	0.0003 (11)	0.0019 (12)	−0.0030 (11)
C6	0.0133 (15)	0.0172 (15)	0.0101 (15)	0.0010 (11)	0.0010 (12)	0.0001 (12)
C7	0.0129 (15)	0.0116 (14)	0.0124 (15)	0.0017 (11)	0.0034 (12)	0.0020 (11)
C8	0.0107 (14)	0.0113 (14)	0.0118 (15)	−0.0002 (11)	0.0019 (11)	−0.0009 (11)
C9	0.0120 (14)	0.0132 (14)	0.0105 (15)	0.0002 (11)	0.0016 (12)	0.0006 (11)
C10	0.0092 (14)	0.0102 (13)	0.0125 (15)	0.0011 (10)	0.0024 (11)	0.0018 (11)
C11	0.0143 (15)	0.0100 (14)	0.0129 (15)	0.0003 (11)	0.0026 (12)	−0.0011 (11)
C12	0.0107 (14)	0.0135 (14)	0.0115 (15)	0.0007 (11)	0.0028 (11)	−0.0003 (11)
C13	0.0100 (14)	0.0119 (14)	0.0133 (15)	0.0022 (11)	0.0038 (12)	0.0020 (11)

Geometric parameters (Å, º) top

Ni1—O5	2.079 (2)	N2—H21	0.83 (5)
Ni1—O5ⁱ	2.079 (2)	N2—H22	0.84 (5)
Ni1—O6	2.052 (2)	C2—C1	1.505 (4)
Ni1—O6ⁱ	2.052 (2)	C2—C3	1.394 (4)
Ni1—N1	2.075 (3)	C2—C7	1.395 (4)
Ni1—N1ⁱ	2.075 (3)	C3—H3	0.9300
O1—C1	1.263 (4)	C4—C3	1.383 (4)
O2—C1	1.260 (4)	C5—C4	1.389 (5)
O3—C4	1.373 (4)	C5—C6	1.390 (5)
O3—H31	0.79 (5)	C5—H5	0.9300
O4—C13	1.236 (4)	C6—H6	0.9300
O5—H51	0.85 (2)	C7—C6	1.391 (5)
O5—H52	0.85 (2)	C7—H7	0.9300
O6—H61	0.85 (2)	C8—H8	0.9300
O6—H62	0.85 (2)	C9—C8	1.378 (4)
O7—H71	0.784 (18)	C9—C10	1.391 (4)
O7—H72	0.85 (2)	C9—H9	0.9300
O8—H81	0.769 (18)	C10—C11	1.386 (5)
O8—H82	0.83 (2)	C10—C13	1.507 (4)
N1—C8	1.347 (4)	C11—H11	0.9300
N1—C12	1.341 (4)	C12—C11	1.385 (4)
N2—C13	1.326 (4)	C12—H12	0.9300

O5—Ni1—O5ⁱ	180.00 (9)	C7—C2—C1	120.3 (3)
O6—Ni1—O5	94.23 (10)	C2—C3—H3	120.1
O6ⁱ—Ni1—O5	85.77 (10)	C4—C3—C2	119.7 (3)
O6—Ni1—O5ⁱ	85.77 (10)	C4—C3—H3	120.1
O6ⁱ—Ni1—O5ⁱ	94.23 (10)	O3—C4—C3	118.2 (3)
O6ⁱ—Ni1—O6	180.0	O3—C4—C5	121.2 (3)
O6—Ni1—N1	89.53 (10)	C3—C4—C5	120.5 (3)
O6ⁱ—Ni1—N1	90.47 (10)	C4—C5—C6	119.9 (3)
O6—Ni1—N1ⁱ	90.47 (10)	C4—C5—H5	120.1
O6ⁱ—Ni1—N1ⁱ	89.53 (10)	C6—C5—H5	120.1
N1—Ni1—O5	89.02 (10)	C5—C6—C7	120.1 (3)
N1ⁱ—Ni1—O5	90.98 (10)	C5—C6—H6	120.0
N1—Ni1—O5ⁱ	90.98 (10)	C7—C6—H6	120.0
N1ⁱ—Ni1—O5ⁱ	89.02 (10)	C2—C7—H7	120.1
N1ⁱ—Ni1—N1	180.0	C6—C7—C2	119.8 (3)
C4—O3—H31	111 (4)	C6—C7—H7	120.1
Ni1—O5—H51	123 (4)	N1—C8—C9	122.8 (3)
Ni1—O5—H52	113 (4)	N1—C8—H8	118.6
H52—O5—H51	99 (6)	C9—C8—H8	118.6
Ni1—O6—H61	128 (3)	C8—C9—C10	119.4 (3)
Ni1—O6—H62	121 (4)	C8—C9—H9	120.3
H61—O6—H62	110 (5)	C10—C9—H9	120.3
H72—O7—H71	100 (4)	C9—C10—C13	118.5 (3)
H81—O8—H82	103 (4)	C11—C10—C9	117.9 (3)
C8—N1—Ni1	122.0 (2)	C11—C10—C13	123.6 (3)
C12—N1—Ni1	120.4 (2)	C10—C11—H11	120.4
C12—N1—C8	117.6 (3)	C12—C11—C10	119.3 (3)
C13—N2—H21	123 (3)	C12—C11—H11	120.4
C13—N2—H22	123 (3)	N1—C12—C11	122.9 (3)
H21—N2—H22	113 (4)	N1—C12—H12	118.5
O1—C1—C2	118.5 (3)	C11—C12—H12	118.5
O2—C1—O1	123.7 (3)	O4—C13—N2	123.2 (3)
O2—C1—C2	117.8 (3)	O4—C13—C10	119.0 (3)
C3—C2—C1	119.6 (3)	N2—C13—C10	117.9 (3)
C3—C2—C7	120.1 (3)

O5—Ni1—N1—C8	−131.1 (3)	C1—C2—C7—C6	−179.7 (3)
O5ⁱ—Ni1—N1—C8	48.9 (3)	C3—C2—C7—C6	0.2 (5)
O5—Ni1—N1—C12	48.7 (2)	O3—C4—C3—C2	177.5 (3)
O5ⁱ—Ni1—N1—C12	−131.3 (2)	C5—C4—C3—C2	−0.9 (5)
O6—Ni1—N1—C8	134.6 (3)	C6—C5—C4—O3	−178.4 (3)
O6ⁱ—Ni1—N1—C8	−45.4 (3)	C6—C5—C4—C3	0.0 (5)
O6—Ni1—N1—C12	−45.5 (2)	C4—C5—C6—C7	1.1 (5)
O6ⁱ—Ni1—N1—C12	134.5 (2)	C2—C7—C6—C5	−1.2 (5)
Ni1—N1—C8—C9	179.4 (2)	C10—C9—C8—N1	0.5 (5)
C12—N1—C8—C9	−0.5 (5)	C8—C9—C10—C11	−0.1 (5)
Ni1—N1—C12—C11	−179.8 (2)	C8—C9—C10—C13	179.0 (3)
C8—N1—C12—C11	0.1 (5)	C9—C10—C11—C12	−0.3 (5)
C3—C2—C1—O1	171.2 (3)	C13—C10—C11—C12	−179.4 (3)
C3—C2—C1—O2	−8.0 (4)	C9—C10—C13—O4	6.0 (5)
C7—C2—C1—O1	−8.9 (5)	C9—C10—C13—N2	−173.2 (3)
C7—C2—C1—O2	171.9 (3)	C11—C10—C13—O4	−175.0 (3)
C1—C2—C3—C4	−179.3 (3)	C11—C10—C13—N2	5.8 (5)
C7—C2—C3—C4	0.8 (5)	N1—C12—C11—C10	0.3 (5)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···O1ⁱⁱ	0.83 (5)	2.20 (5)	3.018 (4)	169 (4)
N2—H22···O8ⁱⁱⁱ	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···O3ⁱⁱⁱ	0.85 (4)	1.87 (4)	2.716 (3)	177 (5)
O5—H52···O1^iv	0.84 (5)	1.99 (6)	2.795 (4)	160 (6)
O6—H61···O4ⁱⁱⁱ	0.85 (3)	1.86 (3)	2.693 (3)	169 (4)
O6—H62···O1ⁱ	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)

Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1/2, y+1/2, −z+1/2; (iii) x+1/2, −y+1/2, z+1/2; (iv) −x, −y, −z+1; (v) −x, −y+1, −z+1; (vi) −x−1/2, y+1/2, −z+1/2; (vii) −x+1/2, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Ni(C₆H₆N₂O)₂(H₂O)₄](C₇H₅O₃)₂·4H₂O
M_r	721.29
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	6.6884 (3), 16.9271 (5), 13.5543 (4)
β (°)	100.186 (3)
V (Å³)	1510.37 (9)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.73
Crystal size (mm)	0.46 × 0.33 × 0.18

Data collection
Diffractometer	Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.750, 0.877
No. of measured, independent and observed [I > 2σ(I)] reflections	13495, 3723, 3365
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.673

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.157, 1.26
No. of reflections	3723
No. of parameters	256
No. of restraints	12
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.86, −0.69

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

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)

Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) x+1/2, −y+1/2, z+1/2; (iii) −x, −y, −z+1; (iv) −x+1, −y, −z+1; (v) −x, −y+1, −z+1; (vi) −x−1/2, y+1/2, −z+1/2; (vii) −x+1/2, y−1/2, −z+1/2.

Acknowledgements

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.

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