trans-Diaqua­bis­(4-fluoro­benzoato-κO)bis­(nicotinamide-κN1)nickel(II)

Necefoğlu, H.; Öztürk, V.; Özbek, F.E.; Adıgüzel, V.; Hökelek, T.

doi:10.1107/S1600536811044771

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Pages m1638-m1639

doi:10.1107/S1600536811044771

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trans-Diaquabis(4-fluorobenzoato-κO)bis(nicotinamide-κN¹)nickel(II)

Hacali Necefoğlu,^a Vijdan Öztürk,^a Füreya Elif Özbek,^a Vedat Adıgüzel ^a and Tuncer Hökelek ^b ^*

^aKafkas University, Department of Chemistry, 36100 Kars, Turkey, and ^bHacettepe University, Department of Physics, 06800 Beytepe, Ankara, Turkey
^*Correspondence e-mail: merzifon@hacettepe.edu.tr

(Received 21 October 2011; accepted 26 October 2011; online 29 October 2011)

In the mononuclear Ni^II title complex, [Ni(C₇H₄FO₂)₂(C₆H₆N₂O)₂(H₂O)₂], the Ni^II atom, located on an inversion center, is coordinated by two nicotinamide and two 4-fluorobenzoate ligands and two water molecules in a distorted N₂O₄ octahedral geometry. The dihedral angle between the carboxylate group and the adjacent benzene ring is 8.95 (8)°, while the pyridine ring and the benzene ring are oriented at a dihedral angle of 75.01 (7)°. The water molecule links the adjacent carboxylate O atom via an intramolecular O—H⋯O hydrogen bond. In the crystal, O—H⋯O, N—H⋯O, C—H⋯O and C—H⋯F hydrogen bonds link the molecules into a three-dimensional network. π–π stacking between parallel pyridine rings [centroid–centroid distance = 3.7287 (11) Å] is also observed.

Related literature

For literature on niacin, see: Krishnamachari (1974 ). For information on the nicotinic acid derivative N,N-diethylnicotinamide, see: Bigoli et al. (1972 ). For related structures, see: Hökelek et al. (1996 , 2009a ,b ); Hökelek & Necefoğlu (1998 , 2007); Necefoğlu et al. (2011 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

[Ni(C₇H₄FO₂)₂(C₆H₆N₂O)₂(H₂O)₂]
M_r = 617.18
Monoclinic, P 2₁ /c
a = 12.2001 (5) Å
b = 8.8473 (4) Å
c = 17.1341 (5) Å
β = 136.080 (2)°
V = 1282.86 (10) Å³
Z = 2
Mo Kα radiation
μ = 0.83 mm⁻¹
T = 100 K
0.29 × 0.22 × 0.18 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.803, T_max = 0.861
11926 measured reflections
3220 independent reflections
2874 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.077
S = 1.04
3220 reflections
203 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.57 e Å⁻³

Table 1
Selected bond lengths (Å)

Ni1—O1	2.0500 (9)
Ni1—O4	2.0872 (10)
Ni1—N1	2.1033 (13)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H21⋯O3ⁱ	0.84 (3)	2.15 (3)	2.8363 (19)	139 (2)
N2—H22⋯O4ⁱⁱ	0.86 (3)	2.28 (3)	2.955 (2)	135 (2)
O4—H41⋯O3ⁱⁱⁱ	0.841 (18)	1.94 (2)	2.7654 (16)	166 (3)
O4—H42⋯O2	0.88 (3)	1.70 (2)	2.5663 (14)	168 (4)
C6—H6⋯O4^iv	0.93	2.52	3.402 (3)	159
C8—H8⋯F1^v	0.93	2.53	3.1358 (18)	123
C9—H9⋯F1^v	0.93	2.55	3.129 (2)	121
C10—H10⋯O2^vi	0.93	2.57	3.4060 (19)	150
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) x, y-1, z; (iv) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (v) -x+1, -y+1, -z+2; (vi) x, y+1, z.

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/S1600536811044771/xu5359sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811044771/xu5359Isup2.hkl

checkCIF report

Comment top

As a part of our ongoing investigations of 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 was synthesized and its crystal structure is reported herein.

The asymmetric unit of the title mononuclear Ni^II complex, (Fig. 1), contains one-half molecule, the Ni^II atom being located on an inversion center. It consists of two nicotinamide (NA), two 4-fluorobenzoate (PFB) ligands and two coordinated water molecules, all ligands coordinating in a monodentate manner. The crystal structures of similar omplexes of Cu^II, Co^II, Ni^II, Mn^II and Zn^II ions, [Cu(C₇H₅O₂)₂(C₁₀H₁₄N₂O)₂] (Hökelek et al., 1996), [Co(C₆H₆N₂O)₂(C₇H₄NO₄)₂(H₂O)₂] (Hökelek & Necefouglu, 1998), [Co(C₉H₉O₂)₂(C₁₀H₁₄N₂O)₂(H₂O)₂] (Necefoğlu et al., 2011), [Ni(C₇H₄ClO₂)₂(C₆H₆N₂O)₂(H₂O)₂] (Hökelek et al., 2009a), [Mn(C₉H₁₀NO₂)₂(H₂O)₄].2H₂O (Hökelek & Necefoğlu, 2007) and [Zn(C₇H₄BrO₂)₂(C₆H₆N₂O)₂(H₂O)₂] (Hökelek et al., 2009b) have also been reported. In the copper(II) complex mentioned above the two benzoate ions coordinate to the Cu^II atom as bidentate ligands, while in the other structures all the ligands coordinate in a monodentate manner.

In the title complex, the four symmetry related O atoms (O1, O1', O4 and O4') 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 the two N atoms of the NA ligands (N1 and N1') in the axial positions. The near equalities of the C1—O1 [1.2695 (18) Å] and C1—O2 [1.2560 (16) Å] bonds in the carboxylate groups indicate delocalized bonding arrangements, rather than localized single and double bonds. The Ni—O bond lengths are 2.0500 (9) Å (for benzoate oxygen) and 2.0872 (10) Å (for water oxygen), and the Ni—N bond length is 2.1033 (13) Å, close to standard values (Allen et al., 1987). The intramolecular O—H···O hydrogen bonds (Table 1) link the water molecules to the carboxylate groups. The Ni atom is displaced out of the mean-plane of the carboxylate group (O1/C1/O2) by 0.5609 (1) Å. The dihedral angle between the planar carboxylate group and the adjacent benzene ring A (C2—C7) is 8.95 (8)°. The benzene A (C2—C7) and the pyridine B (N1/C8—C12) rings are oriented at a dihedral angle of A/B = 75.01 (7)°.

In the crystal, intermolecular O—H···O, N—H···O, C—H···O and C—H···F hydrogen bonds (Table 1) link the molecules into a three-dimensional network. There also exists a π–π contact between the pyridine rings, Cg2—Cg2ⁱ, may further stabilize the structure [centroid-centroid distance = 3.729 (1) Å; symmetry code: (i) 2 - x, -y, 1 - z; Cg2 is the centroid of the ring B (N1/C8—C12)].

Related literature top

For literature on niacin, see: Krishnamachari (1974). For information on the nicotinic acid derivative N,N-diethylnicotinamide, see: Bigoli et al. (1972). For related structures, see: Hökelek et al. (1996, 2009a,b); Hökelek & Necefouğlu (1998, 2007); Necefoğlu et al. (2011). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound was prepared by the reaction of NiSO₄.6H₂O (1.31 g, 5 mmol) in H₂O (25 ml) and NA (1.22 g, 10 mmol) in H₂O (25 ml) with sodium 4-fluorobenzoate (1.62 g, 10 mmol) in H₂O (100 ml) at room temperature. The mixture was filtered and set aside to crystallize at ambient temperature for two 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 the title molecule with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level [symmetry code ('): -x, 1-y, 1-z].

trans-Diaquabis(4-fluorobenzoato-κO)bis(nicotinamide- κN¹)nickel(II) top

Crystal data top

[Ni(C₇H₄FO₂)₂(C₆H₆N₂O)₂(H₂O)₂]	F(000) = 636
M_r = 617.18	D_x = 1.598 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6642 reflections
a = 12.2001 (5) Å	θ = 2.4–28.5°
b = 8.8473 (4) Å	µ = 0.83 mm⁻¹
c = 17.1341 (5) Å	T = 100 K
β = 136.080 (2)°	Block, blue
V = 1282.86 (10) Å³	0.29 × 0.22 × 0.18 mm
Z = 2

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	3220 independent reflections
Radiation source: fine-focus sealed tube	2874 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ϕ and ω scans	θ_max = 28.5°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −16→16
T_min = 0.803, T_max = 0.861	k = −11→11
11926 measured reflections	l = −22→23

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.077	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.038P)² + 0.689P] where P = (F_o² + 2F_c²)/3
3220 reflections	(Δ/σ)_max < 0.001
203 parameters	Δρ_max = 0.46 e Å⁻³
0 restraints	Δρ_min = −0.57 e Å⁻³

Crystal data top

[Ni(C₇H₄FO₂)₂(C₆H₆N₂O)₂(H₂O)₂]	V = 1282.86 (10) Å³
M_r = 617.18	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.2001 (5) Å	µ = 0.83 mm⁻¹
b = 8.8473 (4) Å	T = 100 K
c = 17.1341 (5) Å	0.29 × 0.22 × 0.18 mm
β = 136.080 (2)°

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	3220 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	2874 reflections with I > 2σ(I)
T_min = 0.803, T_max = 0.861	R_int = 0.028
11926 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.077	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.46 e Å⁻³
3220 reflections	Δρ_min = −0.57 e Å⁻³
203 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.0000	0.5000	0.5000	0.00935 (8)
O1	0.18950 (11)	0.45525 (13)	0.66805 (8)	0.0129 (2)
O2	0.35932 (12)	0.35155 (14)	0.66999 (8)	0.0182 (2)
O3	0.04376 (12)	1.15787 (12)	0.34180 (8)	0.0152 (2)
O4	0.11757 (12)	0.41708 (13)	0.46215 (8)	0.0127 (2)
H41	0.088 (2)	0.333 (2)	0.4293 (16)	0.020 (5)*
H42	0.209 (3)	0.398 (3)	0.532 (2)	0.049 (7)*
N1	0.08897 (13)	0.71649 (14)	0.52032 (9)	0.0114 (2)
N2	−0.00057 (17)	0.93579 (17)	0.26006 (11)	0.0180 (3)
H21	0.003 (2)	0.841 (3)	0.2615 (17)	0.030 (6)*
H22	−0.033 (3)	0.984 (3)	0.203 (2)	0.037 (6)*
F1	0.65268 (11)	0.13200 (13)	1.13785 (7)	0.0274 (2)
C1	0.31188 (15)	0.37925 (17)	0.71362 (11)	0.0124 (3)
C2	0.40420 (15)	0.31422 (18)	0.82813 (11)	0.0132 (3)
C3	0.36738 (18)	0.3548 (2)	0.88572 (12)	0.0192 (3)
H3	0.2866	0.4236	0.8538	0.023*
C4	0.45092 (19)	0.2929 (2)	0.99065 (12)	0.0229 (4)
H4	0.4270	0.3190	1.0296	0.027*
C5	0.56940 (17)	0.1923 (2)	1.03506 (11)	0.0185 (3)
C6	0.60852 (17)	0.14784 (19)	0.98051 (12)	0.0176 (3)
H6	0.6885	0.0779	1.0127	0.021*
C7	0.52424 (16)	0.21111 (18)	0.87575 (11)	0.0152 (3)
H7	0.5487	0.1840	0.8372	0.018*
C8	0.18734 (16)	0.78640 (18)	0.62049 (11)	0.0130 (3)
H8	0.2178	0.7358	0.6813	0.016*
C9	0.24541 (16)	0.93048 (18)	0.63733 (11)	0.0141 (3)
H9	0.3144	0.9750	0.7082	0.017*
C10	0.19927 (17)	1.00725 (17)	0.54715 (12)	0.0130 (3)
H10	0.2353	1.1048	0.5560	0.016*
C11	0.09784 (15)	0.93567 (17)	0.44284 (11)	0.0107 (3)
C12	0.04647 (15)	0.79094 (17)	0.43349 (11)	0.0112 (3)
H12	−0.0205	0.7430	0.3639	0.013*
C13	0.04432 (16)	1.01818 (17)	0.34384 (11)	0.0121 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.01259 (13)	0.00808 (15)	0.00725 (12)	−0.00057 (10)	0.00710 (10)	0.00028 (9)
O1	0.0143 (4)	0.0119 (5)	0.0089 (4)	0.0004 (4)	0.0072 (4)	0.0005 (4)
O2	0.0158 (5)	0.0271 (7)	0.0124 (4)	0.0011 (5)	0.0104 (4)	0.0016 (5)
O3	0.0245 (5)	0.0088 (5)	0.0148 (4)	−0.0002 (4)	0.0149 (4)	0.0003 (4)
O4	0.0166 (5)	0.0115 (6)	0.0104 (4)	−0.0011 (4)	0.0098 (4)	−0.0014 (4)
N1	0.0136 (5)	0.0107 (6)	0.0113 (5)	−0.0001 (5)	0.0094 (4)	0.0003 (5)
N2	0.0330 (7)	0.0096 (7)	0.0146 (6)	−0.0006 (6)	0.0183 (6)	0.0000 (5)
F1	0.0278 (5)	0.0348 (6)	0.0115 (4)	0.0072 (5)	0.0114 (4)	0.0094 (4)
C1	0.0127 (6)	0.0111 (7)	0.0097 (5)	−0.0039 (6)	0.0068 (5)	−0.0015 (5)
C2	0.0127 (6)	0.0146 (8)	0.0098 (5)	−0.0017 (6)	0.0073 (5)	−0.0007 (5)
C3	0.0187 (7)	0.0240 (9)	0.0143 (6)	0.0063 (7)	0.0117 (6)	0.0035 (6)
C4	0.0254 (7)	0.0318 (10)	0.0152 (6)	0.0062 (8)	0.0159 (6)	0.0027 (7)
C5	0.0176 (6)	0.0214 (9)	0.0092 (6)	0.0001 (7)	0.0072 (5)	0.0030 (6)
C6	0.0143 (6)	0.0181 (8)	0.0147 (6)	0.0036 (6)	0.0086 (5)	0.0032 (6)
C7	0.0146 (6)	0.0169 (8)	0.0135 (6)	−0.0008 (6)	0.0100 (5)	−0.0004 (6)
C8	0.0154 (6)	0.0130 (8)	0.0103 (5)	0.0009 (6)	0.0091 (5)	0.0007 (5)
C9	0.0164 (6)	0.0140 (8)	0.0103 (5)	−0.0015 (6)	0.0091 (5)	−0.0018 (6)
C10	0.0163 (6)	0.0097 (7)	0.0139 (6)	−0.0016 (6)	0.0112 (6)	−0.0011 (5)
C11	0.0130 (6)	0.0110 (7)	0.0105 (5)	0.0021 (6)	0.0092 (5)	0.0023 (5)
C12	0.0132 (6)	0.0112 (7)	0.0097 (5)	0.0001 (6)	0.0085 (5)	−0.0004 (5)
C13	0.0146 (6)	0.0122 (7)	0.0114 (6)	0.0001 (6)	0.0100 (5)	0.0005 (5)

Geometric parameters (Å, º) top

Ni1—O1	2.0500 (9)	C2—C7	1.386 (2)
Ni1—O1ⁱ	2.0500 (9)	C3—C4	1.390 (2)
Ni1—O4	2.0872 (10)	C3—H3	0.9300
Ni1—O4ⁱ	2.0872 (10)	C4—H4	0.9300
Ni1—N1	2.1033 (13)	C5—C4	1.369 (2)
Ni1—N1ⁱ	2.1033 (13)	C6—C5	1.378 (2)
O1—C1	1.2695 (18)	C6—C7	1.3906 (19)
O2—C1	1.2560 (16)	C6—H6	0.9300
O3—C13	1.2363 (18)	C7—H7	0.9300
O4—H41	0.84 (2)	C8—C9	1.384 (2)
O4—H42	0.88 (3)	C8—H8	0.9300
N1—C8	1.3421 (17)	C9—C10	1.3830 (19)
N1—C12	1.3435 (17)	C9—H9	0.9300
N2—C13	1.3264 (19)	C10—C11	1.3930 (19)
N2—H21	0.84 (2)	C10—H10	0.9300
N2—H22	0.86 (2)	C12—C11	1.383 (2)
F1—C5	1.3570 (16)	C12—H12	0.9300
C1—C2	1.5051 (18)	C13—C11	1.4970 (18)
C2—C3	1.3939 (19)

O1ⁱ—Ni1—O1	180.0	C4—C3—C2	120.28 (14)
O1—Ni1—O4	92.09 (4)	C4—C3—H3	119.9
O1ⁱ—Ni1—O4	87.91 (4)	C3—C4—H4	120.9
O1—Ni1—O4ⁱ	87.91 (4)	C5—C4—C3	118.16 (13)
O1ⁱ—Ni1—O4ⁱ	92.09 (4)	C5—C4—H4	120.9
O1—Ni1—N1	91.03 (4)	F1—C5—C4	118.72 (13)
O1ⁱ—Ni1—N1	88.97 (4)	F1—C5—C6	117.82 (14)
O1—Ni1—N1ⁱ	88.97 (4)	C4—C5—C6	123.46 (13)
O1ⁱ—Ni1—N1ⁱ	91.03 (4)	C5—C6—C7	117.73 (14)
O4—Ni1—O4ⁱ	180.00 (5)	C5—C6—H6	121.1
O4—Ni1—N1	89.05 (4)	C7—C6—H6	121.1
O4ⁱ—Ni1—N1	90.95 (4)	C2—C7—C6	120.67 (13)
O4—Ni1—N1ⁱ	90.95 (4)	C2—C7—H7	119.7
O4ⁱ—Ni1—N1ⁱ	89.05 (4)	C6—C7—H7	119.7
N1ⁱ—Ni1—N1	180.00 (8)	N1—C8—C9	122.88 (13)
C1—O1—Ni1	127.09 (9)	N1—C8—H8	118.6
Ni1—O4—H41	117.0 (13)	C9—C8—H8	118.6
Ni1—O4—H42	97.2 (15)	C8—C9—H9	120.5
H41—O4—H42	105 (2)	C10—C9—C8	118.96 (13)
C8—N1—Ni1	120.72 (9)	C10—C9—H9	120.5
C8—N1—C12	117.81 (13)	C9—C10—C11	118.73 (14)
C12—N1—Ni1	121.44 (9)	C9—C10—H10	120.6
C13—N2—H21	123.2 (14)	C11—C10—H10	120.6
C13—N2—H22	116.9 (15)	C10—C11—C13	119.43 (13)
H21—N2—H22	120 (2)	C12—C11—C10	118.63 (12)
O1—C1—C2	116.65 (12)	C12—C11—C13	121.92 (12)
O2—C1—O1	125.40 (12)	N1—C12—C11	122.98 (12)
O2—C1—C2	117.93 (13)	N1—C12—H12	118.5
C3—C2—C1	120.28 (13)	C11—C12—H12	118.5
C7—C2—C1	120.01 (12)	O3—C13—N2	121.96 (13)
C7—C2—C3	119.70 (13)	O3—C13—C11	120.56 (12)
C2—C3—H3	119.9	N2—C13—C11	117.48 (14)

O4—Ni1—O1—C1	−10.42 (12)	O2—C1—C2—C7	−8.4 (2)
O4ⁱ—Ni1—O1—C1	169.58 (12)	C1—C2—C3—C4	178.94 (15)
N1—Ni1—O1—C1	−99.50 (12)	C7—C2—C3—C4	0.3 (2)
N1ⁱ—Ni1—O1—C1	80.50 (12)	C1—C2—C7—C6	−178.74 (14)
O1—Ni1—N1—C8	−24.63 (11)	C3—C2—C7—C6	−0.1 (2)
O1ⁱ—Ni1—N1—C8	155.37 (11)	C2—C3—C4—C5	0.2 (3)
O1—Ni1—N1—C12	157.13 (10)	F1—C5—C4—C3	179.47 (15)
O1ⁱ—Ni1—N1—C12	−22.87 (10)	C6—C5—C4—C3	−1.0 (3)
O4—Ni1—N1—C8	−116.70 (11)	C7—C6—C5—F1	−179.28 (14)
O4ⁱ—Ni1—N1—C8	63.30 (11)	C7—C6—C5—C4	1.2 (3)
O4—Ni1—N1—C12	65.06 (10)	C5—C6—C7—C2	−0.6 (2)
O4ⁱ—Ni1—N1—C12	−114.94 (10)	N1—C8—C9—C10	0.7 (2)
Ni1—O1—C1—O2	20.1 (2)	C8—C9—C10—C11	−1.0 (2)
Ni1—O1—C1—C2	−158.24 (10)	C9—C10—C11—C12	0.4 (2)
Ni1—N1—C8—C9	−178.10 (10)	C9—C10—C11—C13	178.87 (13)
C12—N1—C8—C9	0.2 (2)	N1—C12—C11—C10	0.5 (2)
Ni1—N1—C12—C11	177.43 (10)	N1—C12—C11—C13	−177.86 (12)
C8—N1—C12—C11	−0.86 (19)	O3—C13—C11—C10	−23.7 (2)
O1—C1—C2—C3	−8.6 (2)	O3—C13—C11—C12	154.64 (13)
O1—C1—C2—C7	170.00 (14)	N2—C13—C11—C10	155.73 (14)
O2—C1—C2—C3	172.92 (14)	N2—C13—C11—C12	−25.9 (2)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···O3ⁱⁱ	0.84 (3)	2.15 (3)	2.8363 (19)	139 (2)
N2—H22···O4ⁱⁱⁱ	0.86 (3)	2.28 (3)	2.955 (2)	135 (2)
O4—H41···O3^iv	0.841 (18)	1.94 (2)	2.7654 (16)	166 (3)
O4—H42···O2	0.88 (3)	1.70 (2)	2.5663 (14)	168 (4)
C6—H6···O4^v	0.93	2.52	3.402 (3)	159
C8—H8···F1^vi	0.93	2.53	3.1358 (18)	123
C9—H9···F1^vi	0.93	2.55	3.129 (2)	121
C10—H10···O2^vii	0.93	2.57	3.4060 (19)	150

Symmetry codes: (ii) −x, y−1/2, −z+1/2; (iii) −x, y+1/2, −z+1/2; (iv) x, y−1, z; (v) −x+1, y−1/2, −z+3/2; (vi) −x+1, −y+1, −z+2; (vii) x, y+1, z.

Experimental details

Crystal data
Chemical formula	[Ni(C₇H₄FO₂)₂(C₆H₆N₂O)₂(H₂O)₂]
M_r	617.18
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	12.2001 (5), 8.8473 (4), 17.1341 (5)
β (°)	136.080 (2)
V (Å³)	1282.86 (10)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.83
Crystal size (mm)	0.29 × 0.22 × 0.18

Data collection
Diffractometer	Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.803, 0.861
No. of measured, independent and observed [I > 2σ(I)] reflections	11926, 3220, 2874
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.672

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.077, 1.04
No. of reflections	3220
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)	0.46, −0.57

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).

Selected bond lengths (Å) top

Ni1—O1	2.0500 (9)	Ni1—N1	2.1033 (13)
Ni1—O4	2.0872 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···O3ⁱ	0.84 (3)	2.15 (3)	2.8363 (19)	139 (2)
N2—H22···O4ⁱⁱ	0.86 (3)	2.28 (3)	2.955 (2)	135 (2)
O4—H41···O3ⁱⁱⁱ	0.841 (18)	1.94 (2)	2.7654 (16)	166 (3)
O4—H42···O2	0.88 (3)	1.70 (2)	2.5663 (14)	168 (4)
C6—H6···O4^iv	0.93	2.52	3.402 (3)	159
C8—H8···F1^v	0.93	2.53	3.1358 (18)	123
C9—H9···F1^v	0.93	2.55	3.129 (2)	121
C10—H10···O2^vi	0.93	2.57	3.4060 (19)	150

Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) −x, y+1/2, −z+1/2; (iii) x, y−1, z; (iv) −x+1, y−1/2, −z+3/2; (v) −x+1, −y+1, −z+2; (vi) x, y+1, z.

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 the X-ray diffractometer. This work was supported financially by the Scientific and Technological Research Council of Turkey (grant No. 106 T472).

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