trans-Diaqua-bis-(4-fluoro-benzoato-κO)bis-(nicotinamide-κN)nickel(II).

In the mononuclear Ni(II) title complex, [Ni(C(7)H(4)FO(2))(2)(C(6)H(6)N(2)O)(2)(H(2)O)(2)], the Ni(II) atom, located on an inversion center, is coordinated by two nicotinamide and two 4-fluoro-benzoate ligands and two water mol-ecules in a distorted N(2)O(4) octa-hedral geometry. The dihedral angle between the carboxyl-ate 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 mol-ecule links the adjacent carboxyl-ate O atom via an intra-molecular 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 mol-ecules 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 = 617.18

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.030

wR(F 2) = 0.077

S = 1.04

3220 reflections

203 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.46 e Å−3

Δρmin = −0.57 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 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811044771/xu5359sup1.cif

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Ni(C7H4FO2)2(C6H6N2O)2(H2O)2]	F(000) = 636
Mr = 617.18	Dx = 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

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

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(Fo2) + (0.038P)2 + 0.689P] where P = (Fo2 + 2Fc2)/3
3220 reflections	(Δ/σ)max < 0.001
203 parameters	Δρmax = 0.46 e Å−3
0 restraints	Δρmin = −0.57 e Å−3

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.

	x	y	z	Uiso*/Ueq
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)

	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)

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)

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···O3iv	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···O4v	0.93	2.52	3.402 (3)	159
C8—H8···F1vi	0.93	2.53	3.1358 (18)	123
C9—H9···F1vi	0.93	2.55	3.129 (2)	121
C10—H10···O2vii	0.93	2.57	3.4060 (19)	150

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⋯O4iv	0.93	2.52	3.402 (3)	159
C8—H8⋯F1v	0.93	2.53	3.1358 (18)	123
C9—H9⋯F1v	0.93	2.55	3.129 (2)	121
C10—H10⋯O2vi	0.93	2.57	3.4060 (19)	150

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