Diaqua­bis(2-bromo­benzoato-κO)bis­(N,N-diethyl­nicotinamide-κN1)nickel(II)

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

doi:10.1107/S1600536809021795

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 7| July 2009| Pages m766-m767

doi:10.1107/S1600536809021795

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Diaquabis(2-bromobenzoato-κO)bis(N,N-diethylnicotinamide-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 ^dDepartment of Chemistry, Kafkas University, 63100 Kars, Turkey
^*Correspondence e-mail: merzifon@hacettepe.edu.tr

(Received 8 June 2009; accepted 9 June 2009; online 13 June 2009)

In the monomeric centrosymmetric title Ni^II complex, [Ni(C₇H₄BrO₂)₂(C₁₀H₁₄N₂O)₂(H₂O)₂], the Ni^II ion is located on an inversion center. The asymmetric unit contains one 2-bromobenzoate ligand, one diethylnicotinamide (DENA) ligand and one coordinated water molecule. The four O atoms in the equatorial plane around the Ni^II ion form a slightly distorted square-planar arrangement, while the slightly distorted octahedral coordination is completed by two N atoms of two DENA ligands in the axial positions. The dihedral angle between the benzene ring and the attached carboxylate group is 87.73 (15)°, while the pyridine and benzene rings are oriented at a dihedral angle of 42.48 (7)°. In the crystal structure, O—H⋯O hydrogen bonds link the molecules into a two-dimensional network parallel to (10 $[\overline{1}]$ ). In addition, C—H⋯O hydrogen bonds are observed.

Related literature

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

Experimental

Crystal data

[Ni(C₇H₄BrO₂)₂(C₁₀H₁₄N₂O)₂(H₂O)₂]
M_r = 851.22
Monoclinic, P 2₁ /n
a = 12.8506 (3) Å
b = 10.3448 (2) Å
c = 14.9418 (4) Å
β = 114.004 (2)°
V = 1814.53 (8) Å³
Z = 2
Mo Kα radiation
μ = 2.79 mm⁻¹
T = 100 K
0.34 × 0.25 × 0.12 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.442, T_max = 0.710
16814 measured reflections
4528 independent reflections
3603 reflections with I > 2σ(I)
R_int = 0.044

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.078
S = 1.04
4528 reflections
233 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.78 e Å⁻³
Δρ_min = −0.78 e Å⁻³

Table 1
Selected bond lengths (Å)

Ni1—O1	2.0359 (14)
Ni1—O4	2.0818 (15)
Ni1—N1	2.1207 (17)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H41⋯O3ⁱ	0.80 (3)	1.97 (3)	2.770 (2)	176 (4)
O4—H42⋯O2ⁱⁱ	0.78 (4)	1.88 (4)	2.623 (3)	161 (3)
C4—H4⋯O2ⁱⁱⁱ	0.93	2.54	3.172 (3)	126
C8—H8⋯O3ⁱ	0.93	2.31	3.241 (3)	177
C10—H10⋯O1^iv	0.93	2.47	3.392 (3)	172
C14—H14A⋯O2^v	0.97	2.50	3.448 (3)	166
C14—H14B⋯O3^vi	0.97	2.55	3.483 (3)	161
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) -x+1, -y, -z; (iii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (v) $[x-{\script{1\over 2}}, -y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (vi) -x, -y, -z-1.

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/S1600536809021795/ci2824sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809021795/ci2824Isup2.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). 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 diethylnicotinamide (DENA) 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^II ion on a centre of symmetry (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 two N atoms of two DENA ligands (N1, N1') in axial positions (Table 1 and Fig. 1).

The near equality of C1—O1 [1.267 (3) Å] and C1—O2 [1.240 (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), 1.2611 (17) and 1.2396 (19) Å in [Mn(DENA)₂(C₇H₄BrO₂)₂(H₂O)₂], (IX) (Hökelek et al., 2009c) and 1.2616 (17) and 1.2435 (18) Å in [Ni(DENA)₂(C₇H₄ClO₂)₂(H₂O)₂], (X) (Hökelek et al., 2009d). In (I), the average Ni—O bond length is 2.0589 (15) Å and the Ni1 atom is displaced out of the least-squares plane of the carboxylate group (O1/C1/O2) by 0.291 (1) Å. The dihedral angle between the planar carboxylate group and the benzene ring A (C2-C7) is 87.73 (15)°, while that between rings A and B (N1/C8-C12) is 42.48 (7)°.

In the crystal structure, intermolecular O—H···O hydrogen bonds (Table 2) link the molecules into a two-dimensional network parallel to the (1 0 1). In addition, C—H···O hydrogen bonds are observed.

Related literature top

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

Experimental top

The title compound was prepared by the reaction of NiSO₄.6H₂O (1.31 g, 5 mmol) in H₂O (20 ml) and i>N,N-diethylnicotinamide (1.78 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 compound, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Primed atoms are generated by the symmetry operator (1 - x, -y, -z).

Diaquabis(2-bromobenzoato-κO)bis(N,N- diethylnicotinamide-κN¹)nickel(II) top

Crystal data top

[Ni(C₇H₄BrO₂)₂(C₁₀H₁₄N₂O)₂(H₂O)₂]	F(000) = 868
M_r = 851.22	D_x = 1.558 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5301 reflections
a = 12.8506 (3) Å	θ = 2.5–28.3°
b = 10.3448 (2) Å	µ = 2.79 mm⁻¹
c = 14.9418 (4) Å	T = 100 K
β = 114.004 (2)°	Block, blue
V = 1814.53 (8) Å³	0.34 × 0.25 × 0.12 mm
Z = 2

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	4528 independent reflections
Radiation source: fine-focus sealed tube	3603 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
ϕ and ω scans	θ_max = 28.4°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −17→17
T_min = 0.442, T_max = 0.710	k = −13→13
16814 measured reflections	l = −19→18

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.078	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0334P)² + 0.7499P] where P = (F_o² + 2F_c²)/3
4528 reflections	(Δ/σ)_max = 0.001
233 parameters	Δρ_max = 0.78 e Å⁻³
0 restraints	Δρ_min = −0.78 e Å⁻³

Crystal data top

[Ni(C₇H₄BrO₂)₂(C₁₀H₁₄N₂O)₂(H₂O)₂]	V = 1814.53 (8) Å³
M_r = 851.22	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 12.8506 (3) Å	µ = 2.79 mm⁻¹
b = 10.3448 (2) Å	T = 100 K
c = 14.9418 (4) Å	0.34 × 0.25 × 0.12 mm
β = 114.004 (2)°

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	4528 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	3603 reflections with I > 2σ(I)
T_min = 0.442, T_max = 0.710	R_int = 0.044
16814 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.078	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.78 e Å⁻³
4528 reflections	Δρ_min = −0.78 e Å⁻³
233 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	0.17947 (2)	0.14287 (2)	0.072440 (17)	0.02619 (8)
Ni1	0.5000	0.0000	0.0000	0.01120 (9)
O1	0.46945 (12)	0.05353 (14)	0.11821 (10)	0.0154 (3)
O2	0.37193 (16)	−0.11792 (15)	0.13480 (13)	0.0270 (4)
O3	0.07077 (13)	0.11718 (14)	−0.39530 (10)	0.0173 (3)
O4	0.61679 (13)	0.15121 (15)	0.03504 (12)	0.0146 (3)
H41	0.607 (3)	0.219 (3)	0.056 (2)	0.036 (9)*
H42	0.621 (3)	0.159 (3)	−0.015 (3)	0.040 (9)*
N1	0.36374 (15)	0.12018 (16)	−0.08963 (12)	0.0134 (4)
N2	0.01992 (15)	−0.00539 (17)	−0.29453 (12)	0.0167 (4)
C1	0.41035 (18)	−0.0066 (2)	0.15502 (15)	0.0156 (4)
C2	0.38690 (18)	0.0695 (2)	0.23103 (15)	0.0163 (4)
C3	0.29000 (19)	0.1455 (2)	0.20453 (16)	0.0196 (4)
C4	0.2709 (2)	0.2248 (2)	0.27162 (17)	0.0247 (5)
H4	0.2060	0.2761	0.2521	0.030*
C5	0.3501 (2)	0.2258 (2)	0.36754 (18)	0.0278 (5)
H5	0.3394	0.2799	0.4128	0.033*
C6	0.4451 (2)	0.1473 (2)	0.39693 (18)	0.0269 (5)
H6	0.4967	0.1462	0.4622	0.032*
C7	0.4636 (2)	0.0699 (2)	0.32851 (16)	0.0217 (5)
H7	0.5281	0.0178	0.3484	0.026*
C8	0.36086 (18)	0.2475 (2)	−0.07399 (15)	0.0158 (4)
H8	0.4205	0.2842	−0.0210	0.019*
C9	0.27291 (18)	0.3269 (2)	−0.13331 (16)	0.0173 (4)
H9	0.2747	0.4151	−0.1207	0.021*
C10	0.18249 (17)	0.2735 (2)	−0.21145 (15)	0.0161 (4)
H10	0.1233	0.3249	−0.2531	0.019*
C11	0.18272 (17)	0.1406 (2)	−0.22590 (14)	0.0142 (4)
C12	0.27482 (17)	0.0686 (2)	−0.16478 (14)	0.0142 (4)
H12	0.2753	−0.0197	−0.1762	0.017*
C13	0.08624 (17)	0.08196 (19)	−0.31130 (15)	0.0139 (4)
C14	−0.07886 (18)	−0.0564 (2)	−0.37834 (16)	0.0187 (4)
H14A	−0.0945	−0.1439	−0.3640	0.022*
H14B	−0.0611	−0.0595	−0.4355	0.022*
C15	−0.18402 (19)	0.0266 (2)	−0.40082 (18)	0.0251 (5)
H15A	−0.2463	−0.0081	−0.4566	0.038*
H15B	−0.1687	0.1133	−0.4148	0.038*
H15C	−0.2036	0.0270	−0.3453	0.038*
C16	0.0277 (2)	−0.0429 (2)	−0.19692 (16)	0.0259 (5)
H16A	−0.0472	−0.0364	−0.1961	0.031*
H16B	0.0776	0.0171	−0.1486	0.031*
C17	0.0725 (2)	−0.1794 (3)	−0.16850 (19)	0.0348 (6)
H17A	0.0684	−0.2022	−0.1077	0.052*
H17B	0.1502	−0.1836	−0.1611	0.052*
H17C	0.0271	−0.2385	−0.2187	0.052*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.02396 (13)	0.03283 (15)	0.02130 (13)	0.00577 (10)	0.00871 (9)	0.00345 (10)
Ni1	0.01157 (17)	0.01200 (18)	0.00955 (17)	−0.00007 (13)	0.00379 (13)	−0.00031 (13)
O1	0.0171 (7)	0.0169 (7)	0.0139 (7)	−0.0024 (6)	0.0080 (6)	−0.0022 (6)
O2	0.0446 (11)	0.0170 (8)	0.0312 (9)	−0.0089 (7)	0.0275 (8)	−0.0057 (7)
O3	0.0209 (8)	0.0158 (7)	0.0119 (7)	−0.0003 (6)	0.0032 (6)	0.0022 (6)
O4	0.0173 (7)	0.0128 (8)	0.0139 (8)	−0.0008 (6)	0.0065 (6)	−0.0006 (6)
N1	0.0146 (8)	0.0135 (8)	0.0118 (8)	0.0001 (7)	0.0052 (7)	0.0011 (6)
N2	0.0174 (9)	0.0198 (9)	0.0112 (8)	−0.0032 (7)	0.0041 (7)	−0.0005 (7)
C1	0.0171 (10)	0.0166 (10)	0.0142 (10)	0.0028 (8)	0.0077 (8)	0.0016 (8)
C2	0.0209 (10)	0.0153 (11)	0.0184 (10)	−0.0030 (8)	0.0137 (9)	−0.0019 (8)
C3	0.0225 (11)	0.0203 (11)	0.0185 (11)	−0.0006 (9)	0.0110 (9)	0.0011 (9)
C4	0.0306 (13)	0.0230 (12)	0.0286 (13)	0.0011 (10)	0.0203 (11)	−0.0026 (10)
C5	0.0391 (14)	0.0261 (13)	0.0279 (13)	−0.0078 (11)	0.0237 (11)	−0.0110 (10)
C6	0.0300 (13)	0.0343 (14)	0.0189 (11)	−0.0101 (11)	0.0126 (10)	−0.0063 (10)
C7	0.0194 (11)	0.0260 (12)	0.0215 (11)	−0.0024 (9)	0.0101 (9)	−0.0025 (9)
C8	0.0172 (10)	0.0155 (10)	0.0142 (10)	−0.0013 (8)	0.0058 (8)	−0.0013 (8)
C9	0.0199 (10)	0.0128 (10)	0.0180 (10)	−0.0001 (8)	0.0064 (8)	−0.0002 (8)
C10	0.0159 (10)	0.0175 (10)	0.0135 (10)	0.0029 (8)	0.0046 (8)	0.0027 (8)
C11	0.0153 (10)	0.0159 (10)	0.0111 (9)	−0.0013 (8)	0.0052 (8)	0.0006 (8)
C12	0.0154 (10)	0.0146 (10)	0.0127 (10)	−0.0003 (8)	0.0058 (8)	0.0002 (8)
C13	0.0137 (9)	0.0109 (9)	0.0144 (10)	0.0021 (8)	0.0029 (8)	0.0009 (8)
C14	0.0189 (10)	0.0185 (11)	0.0161 (10)	−0.0049 (9)	0.0043 (8)	−0.0026 (8)
C15	0.0193 (11)	0.0290 (13)	0.0235 (12)	0.0002 (9)	0.0052 (9)	0.0036 (10)
C16	0.0253 (12)	0.0369 (14)	0.0144 (10)	−0.0126 (10)	0.0069 (9)	0.0000 (10)
C17	0.0284 (13)	0.0422 (16)	0.0254 (13)	−0.0081 (12)	0.0022 (11)	0.0177 (11)

Geometric parameters (Å, º) top

Br1—C3	1.906 (2)	C7—H7	0.93
Ni1—O1	2.0359 (14)	C8—N1	1.341 (3)
Ni1—O1ⁱ	2.0359 (14)	C8—H8	0.93
Ni1—O4	2.0818 (15)	C9—C8	1.387 (3)
Ni1—O4ⁱ	2.0818 (15)	C9—H9	0.93
Ni1—N1	2.1207 (17)	C10—C9	1.384 (3)
Ni1—N1ⁱ	2.1207 (17)	C10—H10	0.93
O1—C1	1.267 (3)	C11—C10	1.392 (3)
O2—C1	1.240 (3)	C11—C12	1.382 (3)
O3—C13	1.243 (2)	C11—C13	1.499 (3)
O4—H41	0.80 (3)	C12—N1	1.344 (3)
O4—H42	0.78 (3)	C12—H12	0.93
N2—C13	1.334 (3)	C14—C15	1.519 (3)
N2—C14	1.471 (3)	C14—H14A	0.97
N2—C16	1.473 (3)	C14—H14B	0.97
C2—C1	1.510 (3)	C15—H15A	0.96
C2—C7	1.387 (3)	C15—H15B	0.96
C3—C2	1.387 (3)	C15—H15C	0.96
C3—C4	1.392 (3)	C16—C17	1.518 (4)
C4—C5	1.379 (3)	C16—H16A	0.97
C4—H4	0.93	C16—H16B	0.97
C5—H5	0.93	C17—H17A	0.96
C6—C5	1.381 (4)	C17—H17B	0.96
C6—C7	1.393 (3)	C17—H17C	0.96
C6—H6	0.93

O1—Ni1—O1ⁱ	180.00 (7)	C2—C7—H7	119.6
O1—Ni1—O4	87.20 (6)	C6—C7—H7	119.6
O1ⁱ—Ni1—O4	92.80 (6)	N1—C8—C9	122.93 (19)
O1—Ni1—O4ⁱ	92.80 (6)	N1—C8—H8	118.5
O1ⁱ—Ni1—O4ⁱ	87.20 (6)	C9—C8—H8	118.5
O1—Ni1—N1	89.27 (6)	C8—C9—H9	120.4
O1ⁱ—Ni1—N1	90.73 (6)	C10—C9—C8	119.3 (2)
O1—Ni1—N1ⁱ	90.73 (6)	C10—C9—H9	120.4
O1ⁱ—Ni1—N1ⁱ	89.27 (6)	C9—C10—C11	118.11 (19)
O4ⁱ—Ni1—O4	180.00 (9)	C9—C10—H10	120.9
O4—Ni1—N1	92.52 (6)	C11—C10—H10	120.9
O4ⁱ—Ni1—N1	87.48 (6)	C10—C11—C13	118.60 (18)
O4—Ni1—N1ⁱ	87.48 (6)	C12—C11—C10	119.01 (19)
O4ⁱ—Ni1—N1ⁱ	92.52 (6)	C12—C11—C13	122.28 (18)
N1ⁱ—Ni1—N1	180.00 (16)	N1—C12—C11	123.15 (19)
C1—O1—Ni1	127.15 (13)	N1—C12—H12	118.4
Ni1—O4—H41	123 (2)	C11—C12—H12	118.4
Ni1—O4—H42	99 (2)	O3—C13—N2	122.44 (18)
H41—O4—H42	112 (3)	O3—C13—C11	118.57 (18)
C8—N1—Ni1	122.69 (14)	N2—C13—C11	118.99 (18)
C8—N1—C12	117.44 (18)	N2—C14—C15	111.57 (18)
C12—N1—Ni1	119.87 (14)	N2—C14—H14A	109.3
C13—N2—C14	118.61 (17)	N2—C14—H14B	109.3
C13—N2—C16	124.98 (18)	C15—C14—H14A	109.3
C14—N2—C16	115.85 (18)	C15—C14—H14B	109.3
O1—C1—C2	114.11 (18)	H14A—C14—H14B	108.0
O2—C1—O1	126.8 (2)	C14—C15—H15A	109.5
O2—C1—C2	119.06 (19)	C14—C15—H15B	109.5
C3—C2—C1	120.77 (19)	C14—C15—H15C	109.5
C7—C2—C1	121.2 (2)	H15A—C15—H15B	109.5
C7—C2—C3	118.0 (2)	H15A—C15—H15C	109.5
C2—C3—Br1	119.46 (17)	H15B—C15—H15C	109.5
C2—C3—C4	121.9 (2)	N2—C16—C17	112.8 (2)
C4—C3—Br1	118.60 (18)	N2—C16—H16A	109.0
C3—C4—H4	120.6	N2—C16—H16B	109.0
C5—C4—C3	118.8 (2)	C17—C16—H16A	109.0
C5—C4—H4	120.6	C17—C16—H16B	109.0
C5—C6—C7	119.8 (2)	H16A—C16—H16B	107.8
C5—C6—H6	120.1	C16—C17—H17A	109.5
C7—C6—H6	120.1	C16—C17—H17B	109.5
C4—C5—C6	120.6 (2)	C16—C17—H17C	109.5
C4—C5—H5	119.7	H17A—C17—H17B	109.5
C6—C5—H5	119.7	H17A—C17—H17C	109.5
C2—C7—C6	120.8 (2)	H17B—C17—H17C	109.5

O4ⁱ—Ni1—O1—C1	8.54 (17)	C1—C2—C7—C6	175.5 (2)
O4—Ni1—O1—C1	−171.46 (17)	C3—C2—C7—C6	−1.8 (3)
N1ⁱ—Ni1—O1—C1	−84.02 (17)	Br1—C3—C2—C1	5.0 (3)
N1—Ni1—O1—C1	95.98 (17)	Br1—C3—C2—C7	−177.63 (16)
O1—Ni1—N1—C8	58.46 (17)	C4—C3—C2—C1	−174.6 (2)
O1ⁱ—Ni1—N1—C8	−121.54 (17)	C4—C3—C2—C7	2.7 (3)
O1—Ni1—N1—C12	−120.53 (16)	Br1—C3—C4—C5	179.28 (18)
O1ⁱ—Ni1—N1—C12	59.47 (16)	C2—C3—C4—C5	−1.1 (4)
O4ⁱ—Ni1—N1—C8	151.29 (17)	C3—C4—C5—C6	−1.5 (4)
O4—Ni1—N1—C8	−28.71 (17)	C5—C6—C7—C2	−0.7 (4)
O4ⁱ—Ni1—N1—C12	−27.70 (16)	C7—C6—C5—C4	2.4 (4)
O4—Ni1—N1—C12	152.30 (16)	C9—C8—N1—C12	−2.1 (3)
Ni1—O1—C1—O2	10.3 (3)	C9—C8—N1—Ni1	178.91 (16)
Ni1—O1—C1—C2	−169.71 (13)	C10—C9—C8—N1	1.1 (3)
C14—N2—C13—O3	−3.5 (3)	C11—C10—C9—C8	1.4 (3)
C14—N2—C13—C11	176.21 (18)	C12—C11—C10—C9	−2.8 (3)
C16—N2—C13—O3	−174.5 (2)	C13—C11—C10—C9	−179.0 (2)
C16—N2—C13—C11	5.1 (3)	C10—C11—C12—N1	1.9 (3)
C13—N2—C14—C15	−88.5 (2)	C13—C11—C12—N1	177.95 (19)
C16—N2—C14—C15	83.4 (2)	C10—C11—C13—O3	61.2 (3)
C13—N2—C16—C17	−110.3 (2)	C10—C11—C13—N2	−118.5 (2)
C14—N2—C16—C17	78.4 (2)	C12—C11—C13—O3	−114.9 (2)
C3—C2—C1—O2	−88.9 (3)	C12—C11—C13—N2	65.5 (3)
C7—C2—C1—O2	93.8 (3)	C11—C12—N1—C8	0.5 (3)
C3—C2—C1—O1	91.1 (2)	C11—C12—N1—Ni1	179.58 (16)
C7—C2—C1—O1	−86.2 (2)

Symmetry code: (i) −x+1, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H41···O3ⁱⁱ	0.80 (3)	1.97 (3)	2.770 (2)	176 (4)
O4—H42···O2ⁱ	0.78 (4)	1.88 (4)	2.623 (3)	161 (3)
C4—H4···O2ⁱⁱⁱ	0.93	2.54	3.172 (3)	126
C8—H8···O3ⁱⁱ	0.93	2.31	3.241 (3)	177
C10—H10···O1^iv	0.93	2.47	3.392 (3)	172
C14—H14A···O2^v	0.97	2.50	3.448 (3)	166
C14—H14B···O3^vi	0.97	2.55	3.483 (3)	161

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

Experimental details

Crystal data
Chemical formula	[Ni(C₇H₄BrO₂)₂(C₁₀H₁₄N₂O)₂(H₂O)₂]
M_r	851.22
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	12.8506 (3), 10.3448 (2), 14.9418 (4)
β (°)	114.004 (2)
V (Å³)	1814.53 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.79
Crystal size (mm)	0.34 × 0.25 × 0.12

Data collection
Diffractometer	Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.442, 0.710
No. of measured, independent and observed [I > 2σ(I)] reflections	16814, 4528, 3603
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.670

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.078, 1.04
No. of reflections	4528
No. of parameters	233
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.78, −0.78

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	2.0359 (14)	Ni1—N1	2.1207 (17)
Ni1—O4	2.0818 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H41···O3ⁱ	0.80 (3)	1.97 (3)	2.770 (2)	176 (4)
O4—H42···O2ⁱⁱ	0.78 (4)	1.88 (4)	2.623 (3)	161 (3)
C4—H4···O2ⁱⁱⁱ	0.93	2.54	3.172 (3)	126
C8—H8···O3ⁱ	0.93	2.31	3.241 (3)	177
C10—H10···O1^iv	0.93	2.47	3.392 (3)	172
C14—H14A···O2^v	0.97	2.50	3.448 (3)	166
C14—H14B···O3^vi	0.97	2.55	3.483 (3)	161

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