Tetra-aqua-bis(isonicotinamide-κN)cobalt(II) bis-(4-formyl-benzoate) dihydrate.

The asymmetric unit of the crystal structure of the title complex, [Co(C(6)H(6)N(2)O)(2)(H(2)O)(4)](C(8)H(5)O(3))(2)·2H(2)O, contains one-half of the complex cation with the Co(II) ion located on an inversion center, a 4-formyl-benzoate (FB) counter-anion and an uncoordinated water mol-ecule. The four O atoms in the equatorial plane around the Co(II) ion form a slightly distorted square-planar arrangement with an average Co-O bond length of 2.086 Å; the slightly distorted octa-hedral coordination is completed by the two N atoms of the isonicotinamide (INA) ligands at a slightly longer distance [2.1603 (14) Å] in the axial positions. The dihedral angle between the carboxyl-ate group and the attached benzene ring is 5.93 (13)°, while the pyridine and benzene rings are oriented at a dihedral angle of 3.09 (6)°. In the crystal structure, O-H⋯O, N-H⋯O and C-H⋯O hydrogen bonds link the mol-ecules into a three-dimensional network. π-π Contacts between the benzene and pyridine rings [centroid-centroid distance = 3.758 (1) Å] may further stabilize the crystal structure.

Related literature

For general background to transition metal complexes of nicotinamide and/or the nicotinic acid derivative N,N-diethyl­nicotinamide, see: Bigoli et al. (1972 ▶); Krishnamachari (1974 ▶). For related structures, see: Hökelek et al. (2009 ▶); Sertçelik et al. (2009 ▶).

Experimental

Crystal data

[Co(C6H6N2O)2(H2O)4](C8H5O3)2·2H2O

M = 709.53

Triclinic,

a = 6.4490 (2) Å

b = 6.8836 (3) Å

c = 18.1792 (5) Å

α = 81.967 (3)°

β = 84.681 (3)°

γ = 72.564 (2)°

V = 761.28 (5) Å3

Z = 1

Mo Kα radiation

μ = 0.64 mm−1

T = 100 K

0.17 × 0.08 × 0.04 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.943, T max = 0.978

13740 measured reflections

3780 independent reflections

2884 reflections with I > 2σ(I)

R int = 0.054

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.074

S = 0.98

3780 reflections

236 parameters

9 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.36 e Å−3

Δρmin = −0.41 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: Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809033200/xu2594sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809033200/xu2594Isup2.hkl

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

[Co(C6H6N2O)2(H2O)4](C8H5O3)2·2H2O	Z = 1
Mr = 709.53	F(000) = 369
Triclinic, P1	Dx = 1.548 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.4490 (2) Å	Cell parameters from 4050 reflections
b = 6.8836 (3) Å	θ = 1.1–28.4°
c = 18.1792 (5) Å	µ = 0.64 mm−1
α = 81.967 (3)°	T = 100 K
β = 84.681 (3)°	Rod-shaped, orange
γ = 72.564 (2)°	0.17 × 0.08 × 0.04 mm
V = 761.28 (5) Å3

Bruker Kappa APEXII CCD area-detector diffractometer	3780 independent reflections
Radiation source: fine-focus sealed tube	2884 reflections with I > 2σ(I)
graphite	Rint = 0.054
φ and ω scans	θmax = 28.4°, θmin = 1.1°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −8→8
Tmin = 0.943, Tmax = 0.978	k = −9→8
13740 measured reflections	l = −24→24

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.074	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	w = 1/[σ2(Fo2) + (0.0308P)2] where P = (Fo2 + 2Fc2)/3
3780 reflections	(Δ/σ)max < 0.001
236 parameters	Δρmax = 0.36 e Å−3
9 restraints	Δρmin = −0.41 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	0.0000	0.0000	0.0000	0.01071 (11)
O1	−0.3206 (2)	0.68183 (19)	−0.08763 (7)	0.0168 (3)
O2	0.0316 (2)	0.55083 (19)	−0.12091 (7)	0.0154 (3)
O3	0.6316 (2)	−0.2347 (2)	0.31750 (7)	0.0191 (3)
O4	−0.5540 (2)	0.7430 (2)	−0.46372 (7)	0.0249 (3)
O5	0.1816 (2)	0.2025 (2)	−0.02613 (7)	0.0129 (3)
H51	0.226 (3)	0.251 (3)	0.0122 (9)	0.015*
H52	0.122 (3)	0.309 (2)	−0.0568 (9)	0.015*
O6	0.2398 (2)	−0.2399 (2)	−0.04719 (7)	0.0154 (3)
H61	0.382 (2)	−0.268 (3)	−0.0613 (10)	0.015*
H62	0.189 (3)	−0.321 (3)	−0.0685 (10)	0.015*
O7	0.1474 (2)	0.1218 (2)	0.58230 (7)	0.0212 (3)
H71	0.222 (3)	0.165 (3)	0.6122 (9)	0.015*
H72	0.239 (3)	−0.002 (2)	0.5679 (10)	0.015*
N1	0.1381 (2)	−0.0933 (2)	0.10768 (8)	0.0118 (3)
N2	0.3064 (2)	−0.1744 (2)	0.38109 (8)	0.0159 (4)
H2A	0.3647	−0.1901	0.4230	0.019*
H2B	0.1675	−0.1461	0.3796	0.019*
C1	−0.1665 (3)	0.6195 (3)	−0.13455 (10)	0.0133 (4)
C2	−0.2240 (3)	0.6309 (3)	−0.21448 (10)	0.0119 (4)
C3	−0.0588 (3)	0.5837 (3)	−0.26939 (10)	0.0149 (4)
H3	0.0859	0.5438	−0.2570	0.018*
C4	−0.1087 (3)	0.5957 (3)	−0.34277 (10)	0.0164 (4)
H4	0.0023	0.5630	−0.3795	0.020*
C5	−0.3246 (3)	0.6567 (3)	−0.36142 (10)	0.0150 (4)
C6	−0.4913 (3)	0.7031 (3)	−0.30633 (10)	0.0146 (4)
H6	−0.6359	0.7427	−0.3187	0.018*
C7	−0.4407 (3)	0.6900 (3)	−0.23320 (10)	0.0140 (4)
H7	−0.5517	0.7206	−0.1964	0.017*
C8	0.0137 (3)	−0.0686 (3)	0.17118 (10)	0.0130 (4)
H8	−0.1367	−0.0279	0.1683	0.016*
C9	0.0981 (3)	−0.1008 (3)	0.24058 (10)	0.0128 (4)
H9	0.0057	−0.0807	0.2830	0.015*
C10	0.3216 (3)	−0.1633 (3)	0.24610 (10)	0.0114 (4)
C11	0.4511 (3)	−0.1974 (3)	0.18124 (10)	0.0137 (4)
H11	0.6018	−0.2448	0.1830	0.016*
C12	0.3547 (3)	−0.1602 (3)	0.11403 (10)	0.0146 (4)
H12	0.4440	−0.1827	0.0710	0.018*
C13	0.4314 (3)	−0.1941 (3)	0.31843 (10)	0.0132 (4)
C14	−0.3744 (3)	0.6684 (3)	−0.43957 (11)	0.0203 (5)
H14	−0.251 (3)	0.611 (3)	−0.4732 (11)	0.025 (6)*

	U11	U22	U33	U12	U13	U23
Co1	0.0088 (2)	0.0147 (2)	0.00937 (19)	−0.00406 (16)	−0.00113 (14)	−0.00213 (14)
O1	0.0131 (7)	0.0241 (8)	0.0145 (7)	−0.0058 (6)	−0.0016 (5)	−0.0053 (6)
O2	0.0110 (7)	0.0181 (7)	0.0175 (7)	−0.0034 (6)	−0.0053 (5)	−0.0027 (6)
O3	0.0116 (7)	0.0274 (8)	0.0181 (7)	−0.0028 (6)	−0.0042 (6)	−0.0068 (6)
O4	0.0248 (8)	0.0311 (9)	0.0159 (7)	−0.0013 (7)	−0.0082 (6)	−0.0036 (6)
O5	0.0124 (7)	0.0173 (7)	0.0101 (7)	−0.0054 (6)	−0.0040 (5)	−0.0007 (5)
O6	0.0100 (7)	0.0195 (8)	0.0186 (7)	−0.0049 (6)	0.0001 (6)	−0.0078 (6)
O7	0.0157 (8)	0.0304 (9)	0.0191 (7)	−0.0062 (7)	−0.0028 (6)	−0.0079 (6)
N1	0.0107 (8)	0.0134 (8)	0.0123 (8)	−0.0047 (7)	−0.0004 (6)	−0.0021 (6)
N2	0.0137 (8)	0.0243 (9)	0.0106 (8)	−0.0048 (7)	−0.0051 (6)	−0.0033 (7)
C1	0.0166 (10)	0.0101 (10)	0.0147 (9)	−0.0058 (8)	−0.0034 (8)	−0.0011 (7)
C2	0.0132 (10)	0.0095 (9)	0.0138 (9)	−0.0041 (8)	−0.0028 (7)	−0.0006 (7)
C3	0.0114 (10)	0.0148 (10)	0.0185 (10)	−0.0031 (8)	−0.0032 (8)	−0.0024 (8)
C4	0.0154 (10)	0.0163 (10)	0.0155 (10)	−0.0024 (8)	0.0017 (8)	−0.0020 (8)
C5	0.0193 (10)	0.0133 (10)	0.0126 (9)	−0.0045 (8)	−0.0025 (8)	−0.0012 (8)
C6	0.0114 (10)	0.0160 (10)	0.0166 (10)	−0.0033 (8)	−0.0042 (8)	−0.0018 (8)
C7	0.0138 (10)	0.0132 (10)	0.0146 (9)	−0.0029 (8)	−0.0001 (8)	−0.0028 (8)
C8	0.0091 (9)	0.0152 (10)	0.0140 (9)	−0.0023 (8)	−0.0018 (7)	−0.0015 (8)
C9	0.0122 (10)	0.0160 (10)	0.0104 (9)	−0.0048 (8)	0.0010 (7)	−0.0022 (7)
C10	0.0141 (10)	0.0085 (9)	0.0127 (9)	−0.0038 (8)	−0.0039 (7)	−0.0014 (7)
C11	0.0089 (9)	0.0168 (10)	0.0161 (10)	−0.0040 (8)	−0.0032 (7)	−0.0021 (8)
C12	0.0108 (10)	0.0190 (10)	0.0136 (9)	−0.0036 (8)	0.0005 (7)	−0.0028 (8)
C13	0.0147 (10)	0.0112 (10)	0.0143 (9)	−0.0031 (8)	−0.0035 (8)	−0.0027 (7)
C14	0.0236 (12)	0.0214 (11)	0.0143 (10)	−0.0039 (10)	0.0002 (9)	−0.0033 (9)

Co1—O5	2.0570 (13)	C2—C3	1.387 (2)
Co1—O5i	2.0570 (13)	C3—C4	1.387 (2)
Co1—O6	2.1151 (12)	C3—H3	0.9300
Co1—O6i	2.1151 (12)	C4—H4	0.9300
Co1—N1	2.1603 (14)	C5—C4	1.388 (3)
Co1—N1i	2.1603 (14)	C5—C14	1.471 (3)
O1—C1	1.261 (2)	C6—C5	1.394 (2)
O2—C1	1.257 (2)	C6—C7	1.382 (2)
O3—C13	1.236 (2)	C6—H6	0.9300
O4—C14	1.214 (2)	C7—C2	1.394 (2)
O5—H51	0.916 (13)	C7—H7	0.9300
O5—H52	0.865 (14)	C8—H8	0.9300
O6—H61	0.899 (13)	C9—C8	1.383 (2)
O6—H62	0.871 (14)	C9—C10	1.384 (2)
O7—H71	0.892 (14)	C9—H9	0.9300
O7—H72	0.935 (13)	C10—C11	1.386 (2)
N1—C8	1.344 (2)	C10—C13	1.510 (2)
N1—C12	1.344 (2)	C11—C12	1.380 (2)
N2—C13	1.331 (2)	C11—H11	0.9300
N2—H2A	0.8600	C12—H12	0.9300
N2—H2B	0.8600	C14—H14	0.976 (19)
C2—C1	1.518 (2)
O5—Co1—O5i	180.00 (4)	C4—C3—C2	120.16 (17)
O5—Co1—O6	93.11 (5)	C4—C3—H3	119.9
O5i—Co1—O6	86.89 (5)	C3—C4—C5	119.95 (17)
O5—Co1—O6i	86.89 (5)	C3—C4—H4	120.0
O5i—Co1—O6i	93.11 (5)	C5—C4—H4	120.0
O5—Co1—N1	90.50 (5)	C4—C5—C6	120.09 (16)
O5i—Co1—N1	89.50 (5)	C4—C5—C14	119.15 (17)
O5—Co1—N1i	89.50 (5)	C6—C5—C14	120.75 (17)
O5i—Co1—N1i	90.50 (5)	C5—C6—H6	120.1
O6—Co1—O6i	180.00 (9)	C7—C6—C5	119.78 (17)
O6—Co1—N1	91.81 (5)	C7—C6—H6	120.1
O6i—Co1—N1	88.19 (5)	C2—C7—H7	119.9
O6—Co1—N1i	88.19 (5)	C6—C7—C2	120.21 (17)
O6i—Co1—N1i	91.81 (5)	C6—C7—H7	119.9
N1i—Co1—N1	180.00 (3)	N1—C8—C9	123.34 (16)
Co1—O5—H51	118.1 (12)	N1—C8—H8	118.3
Co1—O5—H52	114.2 (12)	C9—C8—H8	118.3
H51—O5—H52	106.5 (16)	C8—C9—C10	119.24 (16)
Co1—O6—H61	136.9 (12)	C8—C9—H9	120.4
Co1—O6—H62	114.8 (12)	C10—C9—H9	120.4
H62—O6—H61	106.4 (16)	C9—C10—C11	117.81 (16)
H71—O7—H72	106.5 (15)	C9—C10—C13	123.74 (16)
C8—N1—Co1	121.76 (12)	C11—C10—C13	118.44 (16)
C12—N1—Co1	121.13 (12)	C10—C11—H11	120.3
C12—N1—C8	116.80 (15)	C12—C11—C10	119.46 (17)
C13—N2—H2A	120.0	C12—C11—H11	120.3
C13—N2—H2B	120.0	N1—C12—C11	123.26 (16)
H2A—N2—H2B	120.0	N1—C12—H12	118.4
O2—C1—O1	125.45 (16)	C11—C12—H12	118.4
O2—C1—C2	117.12 (16)	O3—C13—N2	122.54 (16)
O1—C1—C2	117.42 (16)	O3—C13—C10	119.36 (16)
C3—C2—C1	119.50 (16)	N2—C13—C10	118.09 (16)
C3—C2—C7	119.82 (16)	O4—C14—C5	124.77 (19)
C7—C2—C1	120.68 (16)	O4—C14—H14	119.5 (11)
C2—C3—H3	119.9	C5—C14—H14	115.7 (11)
O5—Co1—N1—C8	119.00 (13)	C6—C5—C4—C3	−0.9 (3)
O5i—Co1—N1—C8	−61.00 (13)	C14—C5—C4—C3	−179.95 (17)
O5—Co1—N1—C12	−54.41 (14)	C4—C5—C14—O4	−170.50 (19)
O5i—Co1—N1—C12	125.59 (14)	C6—C5—C14—O4	10.4 (3)
O6—Co1—N1—C8	−147.87 (13)	C7—C6—C5—C4	0.6 (3)
O6i—Co1—N1—C8	32.13 (13)	C7—C6—C5—C14	179.65 (17)
O6—Co1—N1—C12	38.72 (14)	C5—C6—C7—C2	0.1 (3)
O6i—Co1—N1—C12	−141.28 (14)	C6—C7—C2—C1	178.94 (16)
Co1—N1—C8—C9	−171.09 (13)	C6—C7—C2—C3	−0.5 (3)
C12—N1—C8—C9	2.6 (3)	C10—C9—C8—N1	−0.6 (3)
Co1—N1—C12—C11	171.72 (14)	C8—C9—C10—C11	−2.1 (3)
C8—N1—C12—C11	−2.0 (3)	C8—C9—C10—C13	177.26 (16)
C3—C2—C1—O1	173.53 (16)	C9—C10—C11—C12	2.6 (3)
C3—C2—C1—O2	−5.6 (2)	C13—C10—C11—C12	−176.75 (16)
C7—C2—C1—O1	−5.9 (3)	C9—C10—C13—O3	−174.44 (17)
C7—C2—C1—O2	174.98 (16)	C9—C10—C13—N2	5.0 (3)
C1—C2—C3—C4	−179.23 (16)	C11—C10—C13—O3	4.9 (3)
C7—C2—C3—C4	0.2 (3)	C11—C10—C13—N2	−175.59 (16)
C2—C3—C4—C5	0.5 (3)	C10—C11—C12—N1	−0.6 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O4ii	0.86	2.13	2.9680 (19)	166
N2—H2B···O7iii	0.86	2.05	2.8659 (19)	158
O5—H51···O1iv	0.92 (2)	1.72 (2)	2.6355 (18)	175 (2)
O5—H52···O2	0.87 (2)	1.86 (2)	2.7236 (18)	171 (2)
O6—H61···O1v	0.90 (2)	1.87 (2)	2.7707 (19)	177 (1)
O6—H62···O2vi	0.87 (2)	1.92 (2)	2.7760 (19)	168 (2)
O7—H71···O3vii	0.89 (2)	1.85 (2)	2.7371 (19)	174 (2)
O7—H72···O4ii	0.94 (2)	1.98 (2)	2.9168 (19)	177 (2)
C9—H9···O7iii	0.93	2.56	3.458 (2)	161
C12—H12···O5viii	0.93	2.45	3.210 (2)	139

Table 1

Selected bond lengths (Å)

Co1—O5	2.0570 (13)
Co1—O6	2.1151 (12)
Co1—N1	2.1603 (14)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O4i	0.86	2.13	2.9680 (19)	166
N2—H2B⋯O7ii	0.86	2.05	2.8659 (19)	158
O5—H51⋯O1iii	0.916 (18)	1.723 (18)	2.6355 (18)	174.5 (18)
O5—H52⋯O2	0.868 (15)	1.863 (15)	2.7236 (18)	171.1 (18)
O6—H61⋯O1iv	0.899 (15)	1.872 (15)	2.7707 (19)	177.3 (11)
O6—H62⋯O2v	0.87 (2)	1.92 (2)	2.7760 (19)	168 (2)
O7—H71⋯O3vi	0.891 (19)	1.850 (18)	2.7371 (19)	173.7 (18)
O7—H72⋯O4i	0.936 (15)	1.982 (15)	2.9168 (19)	176.8 (17)
C9—H9⋯O7ii	0.93	2.56	3.458 (2)	161
C12—H12⋯O5vii	0.93	2.45	3.210 (2)	139

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