Tetra-aqua-bis(nicotinamide-κN)nickel(II) bis-(2-fluoro-benzoate).

The asymmetric unit of the title complex, [Ni(C(6)H(6)N(2)O)(2)(H(2)O)(4)](C(7)H(4)FO(2))(2), contains one-half of the complex cation with the Ni(II) atom located on an inversion center, and a 2-fluoro-benzoate (FB) counter-anion. The four O atoms in the equatorial plane around the Ni atom form a slightly distorted square-planar arrangement with an average Ni-O bond length of 2.079 Å, and the slightly distorted octa-hedral coordination is completed by the two N atoms of the nicotinamide (NA) ligands in the axial positions. The dihedral angle between the carboxyl group and the attached benzene ring is 28.28 (11)°, while the pyridine and benzene rings are oriented at a dihedral angle of 8.31 (4)°. In the crystal structure, 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 Contacts between the pyridine and benzene rings [centroid-centroid distance = 3.626 (1) Å] may further stabilize the crystal structure. The 2-fluoro-benzoate anion is disordered over two orientations, with an occupancy ratio of 0.85:0.15.

Related literature

For niacin, see: Krishnamachari (1974 ▶) and for the nicotinic acid derivative N,N-diethyl­nicotinamide, see: Bigoli et al. (1972 ▶). For related structures, see: Hökelek et al. (2009 ▶); Sertçelik et al. (2009 ▶).

Experimental

Crystal data

[Ni(C6H6N2O)2(H2O)4](C7H4FO2)2

M = 653.23

Triclinic,

a = 7.2529 (1) Å

b = 7.3315 (1) Å

c = 14.3831 (3) Å

α = 82.115 (2)°

β = 77.332 (2)°

γ = 63.664 (1)°

V = 668.05 (2) Å3

Z = 1

Mo Kα radiation

μ = 0.81 mm−1

T = 100 K

0.33 × 0.28 × 0.18 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.768, T max = 0.868

12196 measured reflections

3339 independent reflections

3241 reflections with I > 2σ(I)

R int = 0.020

Refinement

R[F 2 > 2σ(F 2)] = 0.026

wR(F 2) = 0.071

S = 1.04

3339 reflections

221 parameters

7 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.55 e Å−3

Δρmin = −0.70 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 datablocks I, global. DOI: 10.1107/S1600536809040392/xu2610sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809040392/xu2610Isup2.hkl

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

[Ni(C6H6N2O)2(H2O)4](C7H4FO2)2	Z = 1
Mr = 653.23	F(000) = 338
Triclinic, P1	Dx = 1.624 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.2529 (1) Å	Cell parameters from 9281 reflections
b = 7.3315 (1) Å	θ = 2.9–28.5°
c = 14.3831 (3) Å	µ = 0.81 mm−1
α = 82.115 (2)°	T = 100 K
β = 77.332 (2)°	Block, blue
γ = 63.664 (1)°	0.33 × 0.28 × 0.18 mm
V = 668.05 (2) Å3

Bruker Kappa APEXII CCD area-detector diffractometer	3339 independent reflections
Radiation source: fine-focus sealed tube	3241 reflections with I > 2σ(I)
graphite	Rint = 0.020
φ and ω scans	θmax = 28.5°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −9→9
Tmin = 0.768, Tmax = 0.868	k = −9→9
12196 measured reflections	l = −19→18

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.071	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0351P)2 + 0.4742P] where P = (Fo2 + 2Fc2)/3
3339 reflections	(Δ/σ)max < 0.001
221 parameters	Δρmax = 0.55 e Å−3
7 restraints	Δρmin = −0.70 e Å−3

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ni1	0.5000	0.5000	0.5000	0.00977 (8)
F1	0.68826 (15)	0.96457 (16)	0.86081 (7)	0.0165 (2)	0.85
F1'	0.3316 (12)	0.9351 (12)	0.6229 (2)	0.0341 (16)	0.15
O1	0.27958 (17)	0.42766 (17)	0.97115 (7)	0.0185 (2)
O2	0.90572 (16)	0.80284 (16)	0.68605 (7)	0.0151 (2)
O3	0.70091 (16)	0.95073 (15)	0.57688 (7)	0.0139 (2)
O4	0.36327 (16)	0.29566 (15)	0.53691 (7)	0.01338 (19)
H4A	0.317 (4)	0.256 (4)	0.4950 (15)	0.040 (6)*
H4B	0.457 (3)	0.184 (3)	0.5609 (16)	0.035 (6)*
O5	0.21175 (16)	0.74407 (16)	0.53176 (7)	0.0165 (2)
H5A	0.109 (3)	0.771 (4)	0.5817 (14)	0.038 (6)*
H5B	0.205 (4)	0.863 (3)	0.5056 (15)	0.032 (6)*
N1	0.54874 (18)	0.45933 (17)	0.64030 (8)	0.0115 (2)
N2	0.04456 (19)	0.57587 (19)	0.87183 (8)	0.0159 (2)
H2A	−0.0596	0.5881	0.9169	0.019*
H2B	0.0239	0.6181	0.8146	0.019*
C1	0.3928 (2)	0.4781 (2)	0.71424 (9)	0.0119 (2)
H1	0.2651	0.4963	0.7017	0.014*
C2	0.4136 (2)	0.4717 (2)	0.80876 (9)	0.0120 (2)
C3	0.6051 (2)	0.4424 (2)	0.82775 (10)	0.0138 (3)
H3	0.6241	0.4368	0.8901	0.017*
C4	0.7670 (2)	0.4217 (2)	0.75166 (10)	0.0141 (3)
H4	0.8966	0.4022	0.7623	0.017*
C5	0.7335 (2)	0.4306 (2)	0.65972 (10)	0.0132 (3)
H5	0.8432	0.4160	0.6092	0.016*
C6	0.2383 (2)	0.4915 (2)	0.89077 (10)	0.0134 (3)
C7	0.5243 (2)	0.9628 (2)	0.83226 (10)	0.0148 (3)
H9'	0.6417	0.9567	0.8511	0.018*	0.15
C8	0.5354 (2)	0.9368 (2)	0.73699 (9)	0.0116 (2)
C9	0.3553 (2)	0.9481 (2)	0.71176 (10)	0.0135 (3)
H9	0.3565	0.9329	0.6485	0.016*	0.85
C10	0.1751 (2)	0.9811 (2)	0.77808 (11)	0.0173 (3)
H10	0.0579	0.9859	0.7596	0.021*
C11	0.1708 (2)	1.0070 (2)	0.87229 (11)	0.0204 (3)
H11	0.0495	1.0310	0.9170	0.025*
C12	0.3461 (2)	0.9975 (2)	0.90026 (11)	0.0200 (3)
H12	0.3440	1.0141	0.9635	0.024*
C13	0.7298 (2)	0.8941 (2)	0.66226 (9)	0.0114 (2)

	U11	U22	U33	U12	U13	U23
Ni1	0.00894 (12)	0.01136 (12)	0.00765 (12)	−0.00371 (9)	−0.00012 (8)	−0.00058 (8)
F1	0.0127 (5)	0.0252 (5)	0.0127 (4)	−0.0076 (4)	−0.0042 (4)	−0.0034 (4)
F1'	0.030 (4)	0.037 (4)	0.036 (4)	−0.016 (3)	−0.006 (3)	0.001 (3)
O1	0.0174 (5)	0.0283 (6)	0.0095 (4)	−0.0104 (4)	−0.0026 (4)	0.0024 (4)
O2	0.0109 (5)	0.0206 (5)	0.0122 (4)	−0.0058 (4)	−0.0025 (4)	0.0013 (4)
O3	0.0137 (5)	0.0168 (5)	0.0107 (4)	−0.0064 (4)	−0.0025 (4)	0.0014 (4)
O4	0.0142 (5)	0.0141 (5)	0.0121 (4)	−0.0062 (4)	−0.0033 (4)	0.0006 (4)
O5	0.0129 (5)	0.0147 (5)	0.0149 (5)	−0.0026 (4)	0.0035 (4)	0.0007 (4)
N1	0.0115 (5)	0.0120 (5)	0.0100 (5)	−0.0044 (4)	−0.0012 (4)	−0.0008 (4)
N2	0.0130 (6)	0.0232 (6)	0.0097 (5)	−0.0075 (5)	−0.0005 (4)	0.0017 (4)
C1	0.0112 (6)	0.0132 (6)	0.0108 (6)	−0.0052 (5)	−0.0015 (5)	−0.0001 (5)
C2	0.0131 (6)	0.0120 (6)	0.0100 (6)	−0.0051 (5)	−0.0012 (5)	0.0002 (5)
C3	0.0157 (6)	0.0149 (6)	0.0111 (6)	−0.0063 (5)	−0.0043 (5)	0.0006 (5)
C4	0.0120 (6)	0.0147 (6)	0.0160 (6)	−0.0054 (5)	−0.0046 (5)	0.0004 (5)
C5	0.0109 (6)	0.0137 (6)	0.0136 (6)	−0.0047 (5)	−0.0006 (5)	−0.0003 (5)
C6	0.0147 (6)	0.0156 (6)	0.0104 (6)	−0.0076 (5)	−0.0006 (5)	−0.0013 (5)
C7	0.0141 (6)	0.0165 (6)	0.0142 (6)	−0.0066 (5)	−0.0034 (5)	−0.0004 (5)
C8	0.0104 (6)	0.0108 (6)	0.0119 (6)	−0.0039 (5)	−0.0008 (5)	0.0003 (4)
C9	0.0136 (6)	0.0130 (6)	0.0145 (6)	−0.0059 (5)	−0.0038 (5)	0.0011 (5)
C10	0.0117 (6)	0.0162 (6)	0.0233 (7)	−0.0061 (5)	−0.0027 (5)	0.0010 (5)
C11	0.0147 (7)	0.0224 (7)	0.0194 (7)	−0.0068 (6)	0.0043 (5)	−0.0015 (6)
C12	0.0205 (7)	0.0244 (7)	0.0127 (6)	−0.0086 (6)	0.0010 (5)	−0.0037 (5)
C13	0.0121 (6)	0.0113 (6)	0.0115 (6)	−0.0060 (5)	−0.0010 (5)	−0.0012 (5)

Ni1—O4	2.0925 (10)	C2—C3	1.3913 (19)
Ni1—O4i	2.0925 (10)	C2—C6	1.5012 (18)
Ni1—O5	2.0658 (10)	C3—C4	1.3871 (19)
Ni1—O5i	2.0658 (10)	C3—H3	0.9300
Ni1—N1	2.0834 (11)	C4—C5	1.3841 (19)
Ni1—N1i	2.0834 (11)	C4—H4	0.9300
O1—C6	1.2346 (17)	C5—H5	0.9300
O2—C13	1.2507 (17)	C7—C12	1.383 (2)
O3—C13	1.2728 (16)	C7—C8	1.3894 (19)
O4—H4A	0.887 (16)	C7—H9'	0.9300
O4—H4B	0.887 (16)	C8—C9	1.3963 (19)
O5—H5B	0.887 (16)	C8—C13	1.5088 (18)
O5—H5A	0.887 (15)	C9—C10	1.383 (2)
N1—C1	1.3427 (17)	C9—H9	0.9300
N1—C5	1.3474 (18)	C10—C11	1.386 (2)
N2—C6	1.3350 (18)	C10—H10	0.9300
N2—H2A	0.8600	C11—C12	1.387 (2)
N2—H2B	0.8600	C11—H11	0.9300
C1—C2	1.3924 (18)	C12—H12	0.9300
C1—H1	0.9300
O4—Ni1—O4i	180.0	C4—C3—C2	118.59 (12)
O5—Ni1—O4	90.92 (4)	C4—C3—H3	120.7
O5i—Ni1—O4	89.08 (4)	C2—C3—H3	120.7
O5—Ni1—O4i	89.08 (4)	C5—C4—C3	119.22 (13)
O5i—Ni1—O4i	90.92 (4)	C5—C4—H4	120.4
O5i—Ni1—O5	180.0	C3—C4—H4	120.4
O5i—Ni1—N1	87.25 (4)	N1—C5—C4	122.81 (13)
O5—Ni1—N1	92.75 (4)	N1—C5—H5	118.6
O5i—Ni1—N1i	92.75 (4)	C4—C5—H5	118.6
O5—Ni1—N1i	87.25 (4)	O1—C6—N2	123.50 (13)
N1—Ni1—O4	86.98 (4)	O1—C6—C2	119.09 (13)
N1i—Ni1—O4	93.02 (4)	N2—C6—C2	117.41 (12)
N1—Ni1—O4i	93.02 (4)	C12—C7—C8	122.85 (13)
N1i—Ni1—O4i	86.98 (4)	C12—C7—H9'	118.6
N1—Ni1—N1i	180.000 (1)	C8—C7—H9'	118.6
C1—N1—C5	117.73 (12)	C7—C8—C9	116.63 (12)
C1—N1—Ni1	121.30 (9)	C7—C8—C13	123.60 (12)
C5—N1—Ni1	120.73 (9)	C9—C8—C13	119.76 (12)
C6—N2—H2A	120.0	C10—C9—C8	121.97 (13)
C6—N2—H2B	120.0	C10—C9—H9	119.0
H2A—N2—H2B	120.0	C8—C9—H9	119.0
Ni1—O4—H4A	122.6 (16)	C9—C10—C11	119.44 (14)
Ni1—O4—H4B	106.3 (15)	C9—C10—H10	120.3
H4A—O4—H4B	106 (2)	C11—C10—H10	120.3
Ni1—O5—H5B	115.1 (15)	C10—C11—C12	120.41 (14)
Ni1—O5—H5A	133.2 (15)	C10—C11—H11	119.8
H5B—O5—H5A	106 (2)	C12—C11—H11	119.8
N1—C1—C2	123.02 (12)	C7—C12—C11	118.69 (14)
N1—C1—H1	118.5	C7—C12—H12	120.7
C2—C1—H1	118.5	C11—C12—H12	120.7
C3—C2—C1	118.63 (12)	O2—C13—O3	124.22 (12)
C3—C2—C6	118.92 (12)	O2—C13—C8	119.65 (12)
C1—C2—C6	122.44 (12)	O3—C13—C8	116.10 (12)
O5i—Ni1—N1—C1	−139.82 (11)	C3—C4—C5—N1	0.2 (2)
O5—Ni1—N1—C1	40.18 (11)	C3—C2—C6—O1	−19.6 (2)
O4—Ni1—N1—C1	−50.59 (10)	C1—C2—C6—O1	159.27 (13)
O4i—Ni1—N1—C1	129.41 (10)	C3—C2—C6—N2	161.24 (13)
O5i—Ni1—N1—C5	45.93 (11)	C1—C2—C6—N2	−19.8 (2)
O5—Ni1—N1—C5	−134.07 (11)	C12—C7—C8—C9	0.3 (2)
O4—Ni1—N1—C5	135.16 (11)	C12—C7—C8—C13	−178.58 (13)
O4i—Ni1—N1—C5	−44.84 (11)	C7—C8—C9—C10	−0.7 (2)
C5—N1—C1—C2	0.8 (2)	C13—C8—C9—C10	178.17 (12)
Ni1—N1—C1—C2	−173.61 (10)	C8—C9—C10—C11	1.0 (2)
N1—C1—C2—C3	−0.7 (2)	C9—C10—C11—C12	−0.8 (2)
N1—C1—C2—C6	−179.57 (12)	C8—C7—C12—C11	−0.1 (2)
C1—C2—C3—C4	0.3 (2)	C10—C11—C12—C7	0.4 (2)
C6—C2—C3—C4	179.22 (12)	C7—C8—C13—O2	28.4 (2)
C2—C3—C4—C5	−0.1 (2)	C9—C8—C13—O2	−150.41 (13)
C1—N1—C5—C4	−0.6 (2)	C7—C8—C13—O3	−153.53 (13)
Ni1—N1—C5—C4	173.85 (10)	C9—C8—C13—O3	27.64 (18)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1ii	0.86	2.03	2.8875 (17)	171
N2—H2B···O2iii	0.86	2.23	3.0654 (16)	164
O4—H4A···O3i	0.89 (2)	2.01 (3)	2.8372 (15)	155 (2)
O4—H4B···O3iv	0.89 (2)	1.87 (2)	2.7288 (15)	163 (2)
O5—H5A···O2iii	0.89 (2)	1.82 (2)	2.7001 (15)	175 (3)
O5—H5B···O3v	0.89 (2)	1.94 (2)	2.7774 (15)	157 (2)
C10—H10···O2iii	0.93	2.52	3.339 (2)	147
C12—H12···F1vi	0.93	2.51	3.4314 (19)	173

Table 1

Selected bond lengths (Å)

Ni1—O4	2.0925 (10)
Ni1—O5	2.0658 (10)
Ni1—N1	2.0834 (11)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O1i	0.86	2.03	2.8875 (17)	171
N2—H2B⋯O2ii	0.86	2.23	3.0654 (16)	164
O4—H4A⋯O3iii	0.887 (16)	2.01 (3)	2.8372 (15)	155 (2)
O4—H4B⋯O3iv	0.887 (16)	1.87 (2)	2.7288 (15)	163 (2)
O5—H5A⋯O2ii	0.887 (16)	1.82 (2)	2.7001 (15)	175 (3)
O5—H5B⋯O3v	0.887 (15)	1.94 (2)	2.7774 (15)	157 (2)
C10—H10⋯O2ii	0.93	2.52	3.339 (2)	147
C12—H12⋯F1vi	0.93	2.51	3.4314 (19)	173

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