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

The title complex, [Co(C(6)H(6)N(2)O)(2)(H(2)O)(4)](C(7)H(4)FO(2))(2), contains one Co(II) atom (site symmetry ), two monodentate nicotin-amide (NA) ligands, four coordinated water mol-ecules and two 2-fluoro-benzoate (FB) anions. The four O atoms in the equatorial plane around the Co atom form a slightly distorted square-planar arrangement, while the slightly distorted octa-hedral coordination is completed by the two N atoms of the NA ligands in the axial positions. The dihedral angle between the carboxyl group and the adjacent benzene ring is 29.8 (3)°, while the pyridine and benzene rings are oriented at a dihedral angle of 7.97 (12)°. In the crystal structure, mol-ecules are linked by O-H⋯O, N-H⋯O and N-H⋯F hydrogen bonds, forming an infinite three-dimensional network. π-π Contacts between the pyridine and benzene rings [centroid-centroid distance = 3.673 (3) Å] may further stabilize the crystal structure.

Related literature

For general background, see: Antolini et al. (1982 ▶); Krishnamachari (1974 ▶); Nadzhafov et al. (1981 ▶). For related structures, see: Hökelek & Necefoğlu (1996 ▶, 1998 ▶); Hökelek et al. (1997 ▶, 2007 ▶); Necefoğlu et al. (2002 ▶); Tercan et al. (2009 ▶).

Experimental

Crystal data

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

M = 653.45

Triclinic,

a = 7.2913 (2) Å

b = 7.4522 (4) Å

c = 14.4853 (5) Å

α = 82.160 (2)°

β = 77.275 (3)°

γ = 63.740 (3)°

V = 687.83 (5) Å3

Z = 1

Mo Kα radiation

μ = 0.70 mm−1

T = 294 K

0.35 × 0.25 × 0.20 mm

Data collection

Rigaku R-AXIS RAPID-S diffractometer

Absorption correction: multi-scan (Blessing, 1995 ▶) T min = 0.807, T max = 0.865

14875 measured reflections

2817 independent reflections

2679 reflections with I > 2σ(I)

R int = 0.044

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.122

S = 1.08

2817 reflections

220 parameters

10 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.37 e Å−3

Δρmin = −0.42 e Å−3

Data collection: CrystalClear (Rigaku/MSC, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809006771/xu2482sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809006771/xu2482Isup2.hkl

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

[Co(C6H6N2O)2(H2O)4](C7H4FO2)2	Z = 1
Mr = 653.45	F(000) = 337
Triclinic, P1	Dx = 1.578 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.2913 (2) Å	Cell parameters from 4045 reflections
b = 7.4522 (4) Å	θ = 2.9–26.4°
c = 14.4853 (5) Å	µ = 0.70 mm−1
α = 82.160 (2)°	T = 294 K
β = 77.275 (3)°	Prism, pink
γ = 63.740 (3)°	0.35 × 0.25 × 0.20 mm
V = 687.83 (5) Å3

Rigaku R-AXIS RAPID-S diffractometer	2817 independent reflections
Radiation source: fine-focus sealed tube	2679 reflections with I > 2σ(I)
graphite	Rint = 0.044
ω scans	θmax = 26.4°, θmin = 2.9°
Absorption correction: multi-scan (Blessing, 1995)	h = −9→9
Tmin = 0.807, Tmax = 0.865	k = −8→9
14875 measured reflections	l = −18→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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.122	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ2(Fo2) + (0.0649P)2 + 0.4285P] where P = (Fo2 + 2Fc2)/3
2817 reflections	(Δ/σ)max < 0.001
220 parameters	Δρmax = 1.37 e Å−3
10 restraints	Δρmin = −0.42 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
Co1	0.5000	0.5000	0.5000	0.0306 (2)
F1	0.6929 (4)	0.9615 (4)	0.85873 (18)	0.0632 (7)
O1	0.2777 (4)	0.4281 (5)	0.97121 (18)	0.0544 (7)
O2	0.9068 (4)	0.8007 (4)	0.68460 (17)	0.0433 (6)
O3	0.7033 (4)	0.9537 (4)	0.57755 (17)	0.0414 (6)
O4	0.6387 (4)	0.7065 (4)	0.46282 (17)	0.0398 (6)
H41	0.695 (6)	0.741 (6)	0.504 (3)	0.057 (13)*
H42	0.529 (7)	0.818 (6)	0.449 (4)	0.10 (2)*
O5	0.7856 (4)	0.2570 (4)	0.46679 (18)	0.0450 (6)
H51	0.896 (5)	0.227 (7)	0.419 (3)	0.070 (15)*
H52	0.799 (7)	0.140 (5)	0.499 (3)	0.053 (12)*
N1	0.5506 (4)	0.4540 (4)	0.64340 (18)	0.0334 (6)
N2	0.0471 (5)	0.5743 (5)	0.8720 (2)	0.0460 (8)
H21	−0.056 (5)	0.588 (6)	0.918 (2)	0.047 (11)*
H22	0.019 (6)	0.640 (5)	0.819 (2)	0.041 (10)*
C1	0.3949 (5)	0.4742 (5)	0.7168 (2)	0.0337 (7)
H1	0.2679	0.4926	0.7042	0.040*
C2	0.4139 (5)	0.4691 (5)	0.8104 (2)	0.0348 (7)
C3	0.6044 (6)	0.4392 (5)	0.8293 (2)	0.0393 (8)
H3	0.6229	0.4340	0.8913	0.047*
C4	0.7650 (5)	0.4175 (5)	0.7546 (3)	0.0408 (8)
H4	0.8937	0.3981	0.7654	0.049*
C5	0.7332 (5)	0.4248 (5)	0.6634 (2)	0.0380 (7)
H5	0.8434	0.4089	0.6135	0.046*
C6	0.2384 (6)	0.4906 (6)	0.8914 (2)	0.0393 (8)
C7	0.7326 (5)	0.8934 (5)	0.6617 (2)	0.0326 (7)
C8	0.5407 (5)	0.9340 (5)	0.7363 (2)	0.0330 (7)
C9	0.3610 (5)	0.9450 (5)	0.7114 (3)	0.0381 (7)
H9	0.3613	0.9304	0.6486	0.046*
C10	0.1833 (6)	0.9768 (6)	0.7779 (3)	0.0474 (9)
H10	0.0663	0.9813	0.7601	0.057*
C11	0.1798 (7)	1.0021 (7)	0.8708 (3)	0.0572 (11)
H11	0.0593	1.0261	0.9155	0.069*
C12	0.3539 (7)	0.9920 (7)	0.8980 (3)	0.0544 (10)
H12	0.3526	1.0070	0.9609	0.065*
C13	0.5296 (6)	0.9593 (6)	0.8305 (2)	0.0411 (8)

	U11	U22	U33	U12	U13	U23
Co1	0.0292 (3)	0.0361 (4)	0.0231 (3)	−0.0124 (3)	−0.0019 (2)	−0.0010 (2)
F1	0.0543 (14)	0.0868 (19)	0.0507 (14)	−0.0276 (14)	−0.0144 (11)	−0.0109 (13)
O1	0.0510 (16)	0.084 (2)	0.0263 (13)	−0.0306 (15)	−0.0069 (11)	0.0080 (13)
O2	0.0319 (12)	0.0595 (16)	0.0341 (13)	−0.0166 (11)	−0.0066 (10)	0.0025 (11)
O3	0.0418 (13)	0.0504 (14)	0.0300 (12)	−0.0196 (11)	−0.0077 (10)	0.0065 (10)
O4	0.0449 (14)	0.0440 (14)	0.0350 (13)	−0.0226 (12)	−0.0102 (11)	0.0017 (10)
O5	0.0385 (14)	0.0435 (14)	0.0371 (14)	−0.0100 (11)	0.0063 (11)	0.0005 (11)
N1	0.0340 (14)	0.0389 (15)	0.0252 (13)	−0.0145 (12)	−0.0041 (10)	−0.0003 (11)
N2	0.0397 (17)	0.063 (2)	0.0298 (16)	−0.0209 (15)	−0.0032 (13)	0.0059 (14)
C1	0.0331 (16)	0.0400 (17)	0.0272 (15)	−0.0151 (14)	−0.0060 (12)	−0.0001 (13)
C2	0.0388 (17)	0.0374 (17)	0.0269 (15)	−0.0161 (14)	−0.0057 (13)	0.0014 (13)
C3	0.0453 (19)	0.0452 (19)	0.0297 (16)	−0.0196 (16)	−0.0137 (14)	0.0028 (14)
C4	0.0348 (17)	0.047 (2)	0.0424 (19)	−0.0175 (15)	−0.0128 (14)	0.0020 (15)
C5	0.0325 (16)	0.0429 (18)	0.0353 (17)	−0.0147 (14)	−0.0032 (13)	−0.0005 (14)
C6	0.048 (2)	0.048 (2)	0.0246 (16)	−0.0241 (17)	−0.0045 (14)	0.0009 (14)
C7	0.0362 (17)	0.0342 (16)	0.0306 (16)	−0.0177 (14)	−0.0068 (13)	−0.0004 (12)
C8	0.0335 (16)	0.0317 (16)	0.0322 (16)	−0.0137 (13)	−0.0052 (13)	0.0012 (12)
C9	0.0386 (18)	0.0392 (18)	0.0396 (18)	−0.0188 (15)	−0.0092 (14)	0.0000 (14)
C10	0.0323 (18)	0.050 (2)	0.060 (2)	−0.0193 (16)	−0.0063 (16)	0.0021 (18)
C11	0.042 (2)	0.068 (3)	0.052 (2)	−0.022 (2)	0.0101 (18)	−0.008 (2)
C12	0.051 (2)	0.070 (3)	0.035 (2)	−0.022 (2)	0.0032 (17)	−0.0094 (18)
C13	0.0383 (18)	0.047 (2)	0.0354 (18)	−0.0158 (16)	−0.0067 (14)	−0.0024 (15)

Co1—O4i	2.143 (3)	C2—C1	1.387 (4)
Co1—O4	2.143 (3)	C2—C3	1.390 (5)
Co1—O5i	2.075 (3)	C3—H3	0.9300
Co1—O5	2.075 (3)	C4—C3	1.375 (5)
Co1—N1	2.145 (3)	C4—H4	0.9300
Co1—N1i	2.145 (3)	C5—C4	1.381 (5)
F1—C13	1.348 (4)	C5—H5	0.9300
O1—C6	1.232 (4)	C6—C2	1.499 (5)
O2—C7	1.244 (4)	C7—C8	1.505 (5)
O3—C7	1.270 (4)	C8—C9	1.399 (5)
O4—H41	0.91 (5)	C8—C13	1.384 (5)
O4—H42	0.90 (3)	C9—C10	1.379 (5)
O5—H51	0.90 (4)	C9—H9	0.9300
O5—H52	0.91 (2)	C10—H10	0.9300
N1—C1	1.342 (4)	C11—C10	1.377 (6)
N1—C5	1.342 (4)	C11—H11	0.9300
N2—C6	1.330 (5)	C12—C11	1.378 (6)
N2—H21	0.87 (2)	C12—C13	1.376 (5)
N2—H22	0.87 (2)	C12—H12	0.9300
C1—H1	0.9300
O4i—Co1—O4	180.0	C2—C3—H3	120.6
O4i—Co1—N1	86.31 (10)	C4—C3—C2	118.7 (3)
O4—Co1—N1	93.69 (10)	C4—C3—H3	120.6
O4i—Co1—N1i	93.69 (10)	C3—C4—C5	119.3 (3)
O4—Co1—N1i	86.31 (10)	C3—C4—H4	120.3
O5i—Co1—O4i	91.75 (12)	C5—C4—H4	120.3
O5—Co1—O4i	88.25 (12)	N1—C5—C4	123.0 (3)
O5i—Co1—O4	88.25 (12)	N1—C5—H5	118.5
O5—Co1—O4	91.75 (12)	C4—C5—H5	118.5
O5i—Co1—O5	180.0	O1—C6—N2	123.5 (3)
O5i—Co1—N1	92.59 (11)	O1—C6—C2	119.1 (3)
O5—Co1—N1	87.41 (11)	N2—C6—C2	117.3 (3)
O5i—Co1—N1i	87.41 (11)	O2—C7—O3	124.3 (3)
O5—Co1—N1i	92.59 (11)	O2—C7—C8	119.3 (3)
N1—Co1—N1i	180.000 (1)	O3—C7—C8	116.3 (3)
Co1—O4—H41	124 (3)	C9—C8—C7	119.6 (3)
Co1—O4—H42	101 (4)	C13—C8—C7	123.9 (3)
H41—O4—H42	106 (3)	C13—C8—C9	116.5 (3)
Co1—O5—H51	136 (3)	C8—C9—H9	119.2
Co1—O5—H52	116 (3)	C10—C9—C8	121.5 (3)
H51—O5—H52	107 (3)	C10—C9—H9	119.2
C1—N1—Co1	121.3 (2)	C9—C10—H10	120.1
C5—N1—C1	117.3 (3)	C11—C10—C9	119.7 (4)
C5—N1—Co1	121.1 (2)	C11—C10—H10	120.1
C6—N2—H21	118 (3)	C10—C11—C12	120.4 (4)
C6—N2—H22	122 (3)	C10—C11—H11	119.8
H21—N2—H22	118 (4)	C12—C11—H11	119.8
N1—C1—C2	123.3 (3)	C11—C12—H12	120.6
N1—C1—H1	118.3	C13—C12—C11	118.8 (4)
C2—C1—H1	118.3	C13—C12—H12	120.6
C1—C2—C3	118.4 (3)	F1—C13—C12	117.1 (3)
C1—C2—C6	122.5 (3)	F1—C13—C8	119.8 (3)
C3—C2—C6	119.1 (3)	C12—C13—C8	123.0 (4)
O4i—Co1—N1—C1	−51.9 (3)	O1—C6—C2—C3	−19.9 (5)
O4—Co1—N1—C1	128.1 (3)	N2—C6—C2—C1	−20.0 (5)
O4i—Co1—N1—C5	135.3 (3)	N2—C6—C2—C3	161.2 (3)
O4—Co1—N1—C5	−44.7 (3)	O2—C7—C8—C9	−149.0 (3)
O5i—Co1—N1—C1	39.7 (3)	O2—C7—C8—C13	30.0 (5)
O5—Co1—N1—C1	−140.3 (3)	O3—C7—C8—C9	29.2 (4)
O5i—Co1—N1—C5	−133.1 (3)	O3—C7—C8—C13	−151.7 (3)
O5—Co1—N1—C5	46.9 (3)	C7—C8—C9—C10	178.3 (3)
Co1—N1—C1—C2	−172.2 (3)	C13—C8—C9—C10	−0.8 (5)
C5—N1—C1—C2	0.9 (5)	C7—C8—C13—F1	4.5 (5)
Co1—N1—C5—C4	172.4 (3)	C7—C8—C13—C12	−178.5 (4)
C1—N1—C5—C4	−0.8 (5)	C9—C8—C13—F1	−176.4 (3)
C3—C2—C1—N1	−0.8 (5)	C9—C8—C13—C12	0.5 (6)
C6—C2—C1—N1	−179.5 (3)	C8—C9—C10—C11	1.1 (6)
C1—C2—C3—C4	0.5 (5)	C12—C11—C10—C9	−1.2 (7)
C6—C2—C3—C4	179.3 (3)	C11—C12—C13—F1	176.4 (4)
C5—C4—C3—C2	−0.4 (5)	C11—C12—C13—C8	−0.6 (7)
N1—C5—C4—C3	0.5 (6)	C13—C12—C11—C10	1.0 (7)
O1—C6—C2—C1	158.9 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···O1ii	0.87 (2)	2.04 (3)	2.902 (5)	171 (4)
N2—H22···F1iii	0.87 (2)	2.54 (4)	2.916 (5)	107 (2)
N2—H22···O2iii	0.87 (2)	2.26 (3)	3.116 (5)	172 (4)
O4—H41···O3	0.91 (5)	2.06 (4)	2.885 (4)	151 (4)
O4—H42···O3iv	0.90 (3)	1.86 (5)	2.761 (4)	178 (5)
O5—H51···O2v	0.90 (4)	1.80 (4)	2.695 (4)	172 (4)
O5—H52···O3vi	0.91 (2)	1.95 (4)	2.798 (4)	156 (4)

Co1—O4	2.143 (3)
Co1—O5	2.075 (3)
Co1—N1	2.145 (3)

O4—Co1—N1	93.69 (10)
O4—Co1—N1i	86.31 (10)
O5i—Co1—N1	92.59 (11)
O5—Co1—N1	87.41 (11)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H21⋯O1ii	0.87 (2)	2.04 (3)	2.902 (5)	171 (4)
N2—H22⋯F1iii	0.87 (2)	2.54 (4)	2.916 (5)	107 (2)
N2—H22⋯O2iii	0.87 (2)	2.26 (3)	3.116 (5)	172 (4)
O4—H41⋯O3	0.91 (5)	2.06 (4)	2.885 (4)	151 (4)
O4—H42⋯O3iv	0.90 (3)	1.86 (5)	2.761 (4)	178 (5)
O5—H51⋯O2v	0.90 (4)	1.80 (4)	2.695 (4)	172 (4)
O5—H52⋯O3vi	0.91 (2)	1.95 (4)	2.798 (4)	156 (4)

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