Diaqua­bis(2-bromo­benzoato-κO)bis­(nicotinamide-κN1)nickel(II)

Hökelek, T.; Yılmaz, F.; Tercan, B.; Özbek, F.E.; Necefoğlu, H.

doi:10.1107/S1600536809021710

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 7| July 2009| Pages m768-m769

doi:10.1107/S1600536809021710

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Diaquabis(2-bromobenzoato-κO)bis(nicotinamide-κN¹)nickel(II)

Tuncer Hökelek,^a ^* Filiz Yılmaz,^b Barış Tercan,^c F. Elif Özbek ^d and Hacali Necefoğlu ^d

^aDepartment of Physics, Hacettepe University, 06800 Beytepe, Ankara, Turkey, ^bDepartment of Chemistry, Faculty of Science, Anadolu University, 26470 Yenibağlar, Eskişehir, Turkey, ^cDepartment of Physics, Karabük University, 78050 Karabük, Turkey, and ^dKafkas University, Department of Chemistry, 63100 Kars, Turkey
^*Correspondence e-mail: merzifon@hacettepe.edu.tr

(Received 8 June 2009; accepted 8 June 2009; online 13 June 2009)

The title Ni^II complex, [Ni(C₇H₄BrO₂)₂(C₆H₆N₂O)₂(H₂O)₂], is centrosymmetric. It contains two 2-bromobenzoate (BB) ligands, two nicotinamide (NA) ligands and two water molecules, all of them being monodentate. The four O atoms 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 N atoms of the NA ligands in the axial positions. The dihedral angle between the carboxylate group and the adjacent benzene ring is 30.81 (17)°, while the pyridine and benzene rings are oriented at a dihedral angle of 84.66 (6)°. In the crystal structure, O—H⋯O and N—H⋯O hydrogen bonds link the molecules into a supramolecular structure. A weak C—H⋯π interaction is also found.

Related literature

For general background, see: Antolini et al. (1982 ); Bigoli et al. (1972 ); Krishnamachari (1974 ); Nadzhafov et al. (1981 ); Shnulin et al. (1981 ). For related structures, see: Hökelek et al. (2009a ,b ,c ); Özbek et al. (2009 ); Sertçelik et al. (2009a ,b ,c ); Tercan et al. (2009 ).

Experimental

Crystal data

[Ni(C₇H₄BrO₂)₂(C₆H₆N₂O)₂(H₂O)₂]
M_r = 739.02
Monoclinic, P 2₁ /n
a = 7.8851 (2) Å
b = 18.2865 (4) Å
c = 9.7574 (3) Å
β = 106.609 (2)°
V = 1348.23 (6) Å³
Z = 2
Mo Kα radiation
μ = 3.74 mm⁻¹
T = 100 K
0.52 × 0.27 × 0.22 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.306, T_max = 0.436
12686 measured reflections
3368 independent reflections
2899 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.090
S = 1.06
3368 reflections
203 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.48 e Å⁻³
Δρ_min = −0.55 e Å⁻³

Table 1
Selected bond lengths (Å)

Ni1—O1	2.0806 (16)
Ni1—O4	2.1012 (17)
Ni1—N1	2.068 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H21⋯O2ⁱ	0.82 (4)	2.09 (4)	2.864 (3)	156 (4)
N2—H22⋯O3ⁱⁱ	0.79 (4)	2.22 (4)	2.951 (3)	153 (4)
O4—H41⋯O2ⁱⁱⁱ	0.86 (4)	1.77 (4)	2.612 (2)	165 (5)
O4—H42⋯O3^iv	0.83 (4)	2.09 (4)	2.886 (2)	162 (3)
C9—H9⋯Cg1^v	0.93	2.89	3.617 (3)	136
Symmetry codes: (i) -x+1, -y+1, -z; (ii) -x+2, -y+1, -z; (iii) -x+1, -y+1, -z+1; (iv) -x+2, -y+1, -z+1; (v) -x, -y, -z+1. Cg1 is the centroid of the C2–C7 ring.

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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809021710/xu2538sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809021710/xu2538Isup2.hkl

checkCIF report

Comment top

Transition metal complexes with biochemically active ligands frequently show interesting physical and/or chemical properties, as a result they may find applications in biological systems (Antolini et al., 1982). The structural functions and coordination relationships of the arylcarboxylate ion in transition metal complexes of benzoic acid derivatives change depending on the nature and position of the substituent groups on the benzene ring, the nature of the additional ligand molecule or solvent, and the medium of the synthesis (Nadzhafov et al., 1981; Shnulin et al., 1981). Nicotinamide (NA) is one form of niacin and a deficiency of this vitamin leads to loss of copper from the body, known as pellagra disease. Victims of pellagra show unusually high serum and urinary copper levels (Krishnamachari, 1974). On the other hand, the nicotinic acid derivative N,N-diethylnicotinamide (DENA) is an important respiratory stimulant (Bigoli et al., 1972).

The structure determination of the title compound, (I), a nickel complex with two 2-bromobenzoate (BB), two nicotinamide (NA) ligands and two water molecules, was undertaken in order to determine the properties of the ligands and also to compare the results obtained with those reported previously.

Compound (I) is a monomeric complex, with the Ni atom on a centre of symmetry. It contains two BB, two NA ligands and two water molecules (Fig. 1). All ligands are monodentate. The four O atoms (O1, O4, and the symmetry-related atoms, O1', O4') 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 N atoms of the NA ligands (N1, N1') in the axial positions (Table 1 and Fig. 1).

The near equality of the C1—O1 [1.260 (3) Å] and C1—O2 [1.258 (3) Å] bonds in the carboxylate group indicates a delocalized bonding arrangement, rather than localized single and double bonds, and may be compared with the corresponding distances: 1.262 (3) and 1.249 (3) Å in [Mn(DENA)₂(C₈H₅O₃)₂(H₂O)₂], (II) (Sertçelik et al., 2009a), 1.263 (4) and 1.249 (4) Å in [Ni(DENA)₂(C₈H₅O₃)₂(H₂O)₂], (III) (Sertçelik et al., 2009b), 1.262 (5) and 1.257 (5) Å in [Co(DENA)₂(C₈H₅O₃)₂(H₂O)₂], (IV) (Sertçelik et al., 2009c), 1.244 (4) and 1.270 (4) Å in [Co(NA)₂(H₂O)₄](C₇H₄FO₂)₂, (V) (Özbek et al., 2009), 1.284 (2), 1.248 (2) and 1.278 (2), 1.241 (2) Å in [Zn(NA)₂(C₈H₈NO₂)₂], (VI) (Tercan et al., 2009), 1.267 (3) and 1.258 (3) Å in [Ni(NA)₂(C₇H₄ClO₂)₂(H₂O)₂], (VII) (Hökelek et al., 2009a), 1.263 (2) and 1.240 (2) Å in [Zn(DENA)₂(C₇H₄BrO₂)₂(H₂O)₂], (VIII) (Hökelek et al., 2009b), and 1.2611 (17) and 1.2396 (19) Å in [Mn(DENA)₂(C₇H₄BrO₂)₂(H₂O)₂], (IX) (Hökelek et al., 2009c). In (I), the average Ni—O bond length is 2.0909 (17) Å and the Ni atom is displaced out of the least-squares plane of the carboxylate group (O1/C1/O2) by -0.595 (1) Å. The dihedral angle between the planar carboxylate group and the benzene ring A (C2—C7) is 30.81 (17)°, while that between rings A and B (N1/C8—C12) is 84.66 (6)°.

In the crystal structure, intermolecular O—H···O and N—H···O hydrogen bonds (Table 2) link the molecules into a supramolecular structure, in which they may be effective in the stabilization of the structure. A weak C—H···π interaction (Table 2) is also found.

Related literature top

For general background, see: Antolini et al. (1982); Bigoli et al. (1972); Krishnamachari (1974); Nadzhafov et al. (1981); Shnulin et al. (1981). For related structures, see: Hökelek et al. (2009a,b,c); Özbek et al. (2009); Sertçelik et al. (2009a,b,c); Tercan et al. (2009). Cg1 is centroid of the C2–C7 ring.

Experimental top

The title compound was prepared by the reaction of Ni(SO₄).6(H₂O) (1.31 g, 5 mmol) in H₂O (20 ml) and NA (1.22 g, 10 mmol) in H₂O (20 ml) with sodium 2-bromobenzoate (2.23 g, 10 mmol) in H₂O (50 ml). The mixture was filtered and set aside to crystallize at ambient temperature for 2 d, 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).

Figures top

Fig. 1. The molecular structure of the title molecule with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Primed atoms are generated by the symmetry operator (1 - x, 1-y, 1-z).

Diaquabis(2-bromobenzoato-κO)bis(nicotinamide-κN¹)nickel(II) top

Crystal data top

[Ni(C₇H₄BrO₂)₂(C₆H₆N₂O)₂(H₂O)₂]	F(000) = 740
M_r = 739.02	D_x = 1.820 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5380 reflections
a = 7.8851 (2) Å	θ = 2.5–28.4°
b = 18.2865 (4) Å	µ = 3.74 mm⁻¹
c = 9.7574 (3) Å	T = 100 K
β = 106.609 (2)°	Block, blue
V = 1348.23 (6) Å³	0.52 × 0.27 × 0.22 mm
Z = 2

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	3368 independent reflections
Radiation source: fine-focus sealed tube	2899 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ϕ and ω scans	θ_max = 28.4°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −10→10
T_min = 0.306, T_max = 0.436	k = −24→21
12686 measured reflections	l = −12→13

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.090	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0538P)² + 0.96P] where P = (F_o² + 2F_c²)/3
3368 reflections	(Δ/σ)_max < 0.001
203 parameters	Δρ_max = 1.48 e Å⁻³
0 restraints	Δρ_min = −0.55 e Å⁻³

Crystal data top

[Ni(C₇H₄BrO₂)₂(C₆H₆N₂O)₂(H₂O)₂]	V = 1348.23 (6) Å³
M_r = 739.02	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.8851 (2) Å	µ = 3.74 mm⁻¹
b = 18.2865 (4) Å	T = 100 K
c = 9.7574 (3) Å	0.52 × 0.27 × 0.22 mm
β = 106.609 (2)°

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	3368 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	2899 reflections with I > 2σ(I)
T_min = 0.306, T_max = 0.436	R_int = 0.029
12686 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.090	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 1.48 e Å⁻³
3368 reflections	Δρ_min = −0.55 e Å⁻³
203 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
Br1	0.40260 (3)	0.212024 (14)	0.17902 (3)	0.02187 (10)
Ni1	0.5000	0.5000	0.5000	0.01048 (11)
O1	0.6201 (2)	0.40537 (9)	0.45455 (18)	0.0137 (3)
O2	0.3946 (2)	0.36790 (10)	0.27275 (19)	0.0162 (4)
O3	0.9542 (2)	0.51033 (10)	0.17931 (19)	0.0184 (4)
O4	0.7554 (2)	0.54252 (10)	0.58888 (19)	0.0149 (4)
H41	0.724 (6)	0.574 (2)	0.643 (4)	0.045 (11)*
H42	0.838 (5)	0.5193 (19)	0.643 (4)	0.024 (8)*
N1	0.5076 (3)	0.54372 (11)	0.3063 (2)	0.0129 (4)
N2	0.8578 (3)	0.57987 (14)	−0.0186 (2)	0.0194 (5)
H21	0.776 (5)	0.6019 (19)	−0.074 (4)	0.034 (10)*
H22	0.935 (5)	0.5647 (18)	−0.048 (4)	0.023 (8)*
C1	0.5546 (3)	0.36682 (13)	0.3452 (2)	0.0126 (4)
C2	0.6793 (3)	0.31957 (13)	0.2910 (3)	0.0130 (4)
C3	0.6274 (3)	0.25649 (14)	0.2082 (3)	0.0138 (5)
C4	0.7416 (3)	0.22059 (13)	0.1454 (3)	0.0160 (5)
H4	0.7036	0.1793	0.0893	0.019*
C5	0.9119 (3)	0.24655 (15)	0.1666 (3)	0.0176 (5)
H5	0.9876	0.2235	0.1227	0.021*
C6	0.9699 (3)	0.30671 (14)	0.2531 (3)	0.0175 (5)
H6	1.0859	0.3230	0.2705	0.021*
C7	0.8537 (3)	0.34266 (13)	0.3137 (3)	0.0143 (5)
H7	0.8934	0.3833	0.3711	0.017*
C8	0.3703 (3)	0.58033 (13)	0.2194 (3)	0.0143 (5)
H8	0.2668	0.5848	0.2464	0.017*
C9	0.3762 (3)	0.61133 (14)	0.0923 (3)	0.0167 (5)
H9	0.2792	0.6367	0.0354	0.020*
C10	0.5299 (3)	0.60410 (14)	0.0504 (3)	0.0159 (5)
H10	0.5376	0.6246	−0.0348	0.019*
C11	0.6709 (3)	0.56580 (13)	0.1378 (3)	0.0131 (5)
C12	0.6545 (3)	0.53690 (13)	0.2651 (3)	0.0134 (5)
H12	0.7500	0.5117	0.3243	0.016*
C13	0.8401 (3)	0.55041 (14)	0.1008 (3)	0.0152 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.01372 (14)	0.01967 (16)	0.03198 (17)	−0.00559 (9)	0.00611 (11)	−0.00455 (10)
Ni1	0.00719 (19)	0.0141 (2)	0.0102 (2)	0.00053 (14)	0.00254 (15)	0.00033 (15)
O1	0.0115 (8)	0.0168 (9)	0.0122 (8)	0.0021 (6)	0.0022 (6)	−0.0009 (6)
O2	0.0082 (7)	0.0226 (10)	0.0164 (8)	0.0018 (6)	0.0015 (6)	−0.0023 (7)
O3	0.0133 (8)	0.0269 (10)	0.0156 (9)	0.0064 (7)	0.0049 (7)	0.0048 (7)
O4	0.0083 (8)	0.0191 (10)	0.0166 (9)	0.0012 (7)	0.0024 (7)	−0.0005 (7)
N1	0.0108 (9)	0.0138 (10)	0.0142 (10)	0.0004 (7)	0.0036 (8)	−0.0001 (8)
N2	0.0131 (10)	0.0324 (13)	0.0143 (10)	0.0074 (9)	0.0063 (9)	0.0062 (9)
C1	0.0105 (10)	0.0152 (12)	0.0126 (11)	0.0013 (8)	0.0043 (9)	0.0026 (9)
C2	0.0103 (10)	0.0143 (12)	0.0143 (11)	0.0018 (8)	0.0034 (9)	0.0015 (9)
C3	0.0102 (10)	0.0162 (12)	0.0137 (11)	−0.0005 (8)	0.0013 (9)	0.0018 (9)
C4	0.0166 (11)	0.0127 (12)	0.0172 (12)	0.0027 (9)	0.0025 (9)	−0.0012 (9)
C5	0.0165 (12)	0.0207 (14)	0.0166 (12)	0.0065 (9)	0.0064 (10)	0.0025 (10)
C6	0.0113 (11)	0.0205 (13)	0.0209 (12)	−0.0004 (9)	0.0051 (10)	0.0010 (10)
C7	0.0110 (10)	0.0149 (12)	0.0165 (11)	0.0010 (8)	0.0031 (9)	0.0005 (9)
C8	0.0095 (10)	0.0163 (12)	0.0167 (11)	0.0020 (8)	0.0029 (9)	0.0001 (9)
C9	0.0093 (10)	0.0211 (13)	0.0175 (12)	0.0051 (9)	0.0002 (9)	0.0043 (10)
C10	0.0132 (11)	0.0224 (13)	0.0130 (11)	0.0022 (9)	0.0052 (9)	0.0032 (9)
C11	0.0117 (11)	0.0146 (12)	0.0139 (11)	0.0007 (8)	0.0051 (9)	−0.0004 (9)
C12	0.0117 (10)	0.0135 (12)	0.0155 (11)	0.0011 (8)	0.0046 (9)	0.0000 (9)
C13	0.0113 (11)	0.0203 (13)	0.0145 (11)	0.0005 (9)	0.0044 (9)	−0.0019 (9)

Geometric parameters (Å, º) top

Br1—C3	1.896 (2)	C3—C4	1.390 (3)
Ni1—O1ⁱ	2.0806 (16)	C4—C5	1.383 (4)
Ni1—O1	2.0806 (16)	C4—H4	0.9300
Ni1—O4	2.1012 (17)	C5—C6	1.382 (4)
Ni1—O4ⁱ	2.1012 (17)	C5—H5	0.9300
Ni1—N1	2.068 (2)	C6—C7	1.390 (3)
Ni1—N1ⁱ	2.068 (2)	C6—H6	0.9300
O1—C1	1.260 (3)	C7—H7	0.9300
O2—C1	1.258 (3)	C8—H8	0.9300
O3—C13	1.241 (3)	C9—C8	1.377 (3)
O4—H41	0.86 (4)	C9—H9	0.9300
O4—H42	0.83 (4)	C10—C9	1.391 (3)
N1—C8	1.347 (3)	C10—H10	0.9300
N1—C12	1.337 (3)	C11—C10	1.383 (3)
N2—H21	0.82 (4)	C11—C12	1.390 (3)
N2—H22	0.79 (4)	C12—H12	0.9300
C1—C2	1.513 (3)	C13—N2	1.327 (3)
C2—C7	1.394 (3)	C13—C11	1.505 (3)
C3—C2	1.400 (4)

O1ⁱ—Ni1—O1	180.000 (1)	C4—C3—Br1	115.24 (18)
O1—Ni1—O4	87.40 (7)	C4—C3—C2	121.6 (2)
O1ⁱ—Ni1—O4	92.60 (7)	C3—C4—H4	120.2
O1ⁱ—Ni1—O4ⁱ	87.40 (7)	C5—C4—C3	119.7 (2)
O1—Ni1—O4ⁱ	92.60 (7)	C5—C4—H4	120.2
O4—Ni1—O4ⁱ	180.00 (10)	C4—C5—H5	119.9
N1—Ni1—O1	89.60 (7)	C6—C5—C4	120.2 (2)
N1ⁱ—Ni1—O1	90.40 (7)	C6—C5—H5	119.9
N1—Ni1—O1ⁱ	90.40 (7)	C5—C6—C7	119.5 (2)
N1ⁱ—Ni1—O1ⁱ	89.60 (7)	C5—C6—H6	120.3
N1—Ni1—O4	87.68 (7)	C7—C6—H6	120.3
N1ⁱ—Ni1—O4	92.32 (7)	C2—C7—H7	119.0
N1—Ni1—O4ⁱ	92.32 (7)	C6—C7—C2	122.0 (2)
N1ⁱ—Ni1—O4ⁱ	87.68 (7)	C6—C7—H7	119.0
N1—Ni1—N1ⁱ	180.00 (10)	N1—C8—C9	123.0 (2)
C1—O1—Ni1	122.99 (15)	N1—C8—H8	118.5
Ni1—O4—H41	95 (3)	C9—C8—H8	118.5
Ni1—O4—H42	124 (2)	C8—C9—C10	118.8 (2)
H42—O4—H41	105 (4)	C8—C9—H9	120.6
C8—N1—Ni1	122.66 (15)	C10—C9—H9	120.6
C12—N1—Ni1	119.53 (16)	C9—C10—H10	120.6
C12—N1—C8	117.8 (2)	C11—C10—C9	118.8 (2)
C13—N2—H21	121 (3)	C11—C10—H10	120.6
C13—N2—H22	118 (2)	C10—C11—C12	118.7 (2)
H21—N2—H22	118 (3)	C10—C11—C13	124.0 (2)
O1—C1—C2	117.8 (2)	C12—C11—C13	117.3 (2)
O2—C1—O1	124.7 (2)	N1—C12—C11	123.0 (2)
O2—C1—C2	117.4 (2)	N1—C12—H12	118.5
C3—C2—C1	124.1 (2)	C11—C12—H12	118.5
C7—C2—C1	118.8 (2)	O3—C13—N2	122.8 (2)
C7—C2—C3	117.0 (2)	O3—C13—C11	119.9 (2)
C2—C3—Br1	123.11 (17)	N2—C13—C11	117.2 (2)

O4—Ni1—O1—C1	−145.89 (18)	C1—C2—C7—C6	−172.5 (2)
O4ⁱ—Ni1—O1—C1	34.11 (18)	C3—C2—C7—C6	2.3 (4)
N1—Ni1—O1—C1	−58.20 (18)	Br1—C3—C2—C1	−10.9 (3)
N1ⁱ—Ni1—O1—C1	121.80 (18)	Br1—C3—C2—C7	174.53 (17)
O1—Ni1—N1—C8	137.00 (19)	C4—C3—C2—C1	171.3 (2)
O1ⁱ—Ni1—N1—C8	−43.00 (19)	C4—C3—C2—C7	−3.2 (4)
O1—Ni1—N1—C12	−44.08 (18)	Br1—C3—C4—C5	−176.67 (19)
O1ⁱ—Ni1—N1—C12	135.92 (18)	C2—C3—C4—C5	1.2 (4)
O4—Ni1—N1—C12	43.33 (18)	C3—C4—C5—C6	1.7 (4)
O4ⁱ—Ni1—N1—C12	−136.67 (18)	C4—C5—C6—C7	−2.6 (4)
O4—Ni1—N1—C8	−135.59 (19)	C5—C6—C7—C2	0.5 (4)
O4ⁱ—Ni1—N1—C8	44.41 (19)	C10—C9—C8—N1	0.7 (4)
Ni1—O1—C1—O2	−19.9 (3)	C11—C10—C9—C8	0.2 (4)
Ni1—O1—C1—C2	155.74 (16)	C12—C11—C10—C9	−0.9 (4)
Ni1—N1—C8—C9	178.11 (19)	C13—C11—C10—C9	176.4 (2)
C12—N1—C8—C9	−0.8 (4)	C10—C11—C12—N1	0.8 (4)
Ni1—N1—C12—C11	−178.89 (18)	C13—C11—C12—N1	−176.7 (2)
C8—N1—C12—C11	0.1 (4)	O3—C13—C11—C10	−173.8 (2)
O1—C1—C2—C3	156.0 (2)	O3—C13—C11—C12	3.5 (4)
O1—C1—C2—C7	−29.6 (3)	N2—C13—C11—C10	4.7 (4)
O2—C1—C2—C3	−28.0 (4)	N2—C13—C11—C12	−178.0 (2)
O2—C1—C2—C7	146.4 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···O2ⁱⁱ	0.82 (4)	2.09 (4)	2.864 (3)	156 (4)
N2—H22···O3ⁱⁱⁱ	0.79 (4)	2.22 (4)	2.951 (3)	153 (4)
O4—H41···O2ⁱ	0.86 (4)	1.77 (4)	2.612 (2)	165 (5)
O4—H42···O3^iv	0.83 (4)	2.09 (4)	2.886 (2)	162 (3)
C9—H9···Cg1^v	0.93	2.89	3.617 (3)	136

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

Experimental details

Crystal data
Chemical formula	[Ni(C₇H₄BrO₂)₂(C₆H₆N₂O)₂(H₂O)₂]
M_r	739.02
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	7.8851 (2), 18.2865 (4), 9.7574 (3)
β (°)	106.609 (2)
V (Å³)	1348.23 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.74
Crystal size (mm)	0.52 × 0.27 × 0.22

Data collection
Diffractometer	Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.306, 0.436
No. of measured, independent and observed [I > 2σ(I)] reflections	12686, 3368, 2899
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.670

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.090, 1.06
No. of reflections	3368
No. of parameters	203
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.48, −0.55

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

Selected bond lengths (Å) top

Ni1—O1	2.0806 (16)	Ni1—N1	2.068 (2)
Ni1—O4	2.1012 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···O2ⁱ	0.82 (4)	2.09 (4)	2.864 (3)	156 (4)
N2—H22···O3ⁱⁱ	0.79 (4)	2.22 (4)	2.951 (3)	153 (4)
O4—H41···O2ⁱⁱⁱ	0.86 (4)	1.77 (4)	2.612 (2)	165 (5)
O4—H42···O3^iv	0.83 (4)	2.09 (4)	2.886 (2)	162 (3)
C9—H9···Cg1^v	0.93	2.89	3.617 (3)	136

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

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.

References

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