Tetra­aqua­bis(isonicotinamide-κN1)cobalt(II) bis­(4-formyl­benzoate) dihydrate

Hökelek, T.; Yılmaz, F.; Tercan, B.; Sertçelik, M.; Necefoğlu, H.

doi:10.1107/S1600536809033200

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 9| September 2009| Pages m1130-m1131

doi:10.1107/S1600536809033200

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Tetraaquabis(isonicotinamide-κN¹)cobalt(II) bis(4-formylbenzoate) dihydrate

Tuncer Hökelek,^a ^* Filiz Yılmaz,^b Barış Tercan,^c Mustafa Sertçelik ^d and Hacali Necefoğlu ^d

^aDepartment of Physics, Hacettepe University, 06800 Beytepe, Ankara, Turkey, ^bDepartment of Chemistry, Faculty of Science, Anadolu University, 26470 Yenibağlar, Eskişehir, Turkey, ^cDepartment of Physics, Karabük University, 78050 Karabük, Turkey, and ^dDepartment of Chemistry, Kafkas University, 63100 Kars, Turkey
^*Correspondence e-mail: merzifon@hacettepe.edu.tr

(Received 19 August 2009; accepted 20 August 2009; online 26 August 2009)

The asymmetric unit of the crystal structure of the title complex, [Co(C₆H₆N₂O)₂(H₂O)₄](C₈H₅O₃)₂·2H₂O, contains one-half of the complex cation with the Co^II ion located on an inversion center, a 4-formylbenzoate (FB) counter-anion and an uncoordinated water molecule. 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 octahedral 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 carboxylate 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 molecules 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_r = 709.53
Triclinic, $[P \overline 1]$
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[F² > 2σ(F²)] = 0.034
wR(F²) = 0.074
S = 0.98
3780 reflections
236 parameters
9 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.41 e Å⁻³

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⋯O1^iv	0.899 (15)	1.872 (15)	2.7707 (19)	177.3 (11)
O6—H62⋯O2^v	0.87 (2)	1.92 (2)	2.7760 (19)	168 (2)
O7—H71⋯O3^vi	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⋯O5^vii	0.93	2.45	3.210 (2)	139
Symmetry codes: (i) x+1, y-1, z+1; (ii) -x, -y, -z+1; (iii) -x, -y+1, -z; (iv) x+1, y-1, z; (v) x, y-1, z; (vi) -x+1, -y, -z+1; (vii) -x+1, -y, -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: Mercury (Macrae et al., 2006 ); 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/S1600536809033200/xu2594sup1.cif

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

checkCIF report

Comment top

As a part of our ongoing investigation on 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 title compound is a monomeric complex, with Co^II ion on a centre of symmetry, consisting of two INA ligands, four coordinated water molecules, two FB anions and two uncoordinated water molecules. The structures of some DENA and/or INA complexes of Co^II ion, [Co(C₈H₅O₃)₂(C₁₀H₁₄N₂O)₂(H₂O)₂] (Sertçelik et al., 2009) and [Co(C₆H₆N₂O)(C₉H₁₀NO₂)₂(H₂O)₂] (Hökelek et al., 2009) have also been determined.

In the title compound, INA ligands are monodentate. The four O atoms (O5, O6, and the symmetry-related atoms, O5', O6') in the equatorial plane around the Co atom form a slightly distorted square-planar arrangement, while the slightly distorted octahedral coordination is completed by the two pyridine N atoms (N1, N1') of the INA ligands at 2.1603 (14) Å from the Co atom in the axial positions (Table 1, Fig. 1). The average Co—O bond length is 2.0861 (13) Å. The O—H···O hydrogen bond (Table 2) links the coordinated water molecule to the FB anion. The dihedral angle between the planar carboxylate group (O1/O2/C1) and the benzene ring A (C2—C7) is 5.93 (13)°, while that between rings A and B (N1/C8—C12) is 3.09 (6)°.

In the crystal structure, O—H···O, N—H···O and C—H···O hydrogen bonds (Table 2) link the molecules into a three-dimensional network, in which they may be effective in the stabilization of the structure. The π–π contact between the benzene and pyridine rings, Cg1—Cg2, [where Cg1 and Cg2 are centroids of the rings A (C2—C7) and B (N1/C8—C12), respectively] may further stabilize the structure, with centroid-centroid distance of 3.758 (1) Å.

Related literature top

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 top

The title compound was prepared by the reaction of CoSO₄.7H₂O (1.41 g, 5 mmol) in H₂O (25 ml) and INA (1.22 g, 10 mmol) in H₂O (40 ml) with sodium 4-formylbenzoate (1.72 g, 10 mmol) in H₂O (50 ml). The mixture was filtered and set aside to crystallize at ambient temperature for several days, giving orange 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: Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

Fig. 1. The structure of the title molecule with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Primed atoms are generated by the symmetry operator:(') -x, -y, -z. Dashed line indicates the hydrogen-bonding.

Tetraaquabis(isonicotinamide-κN¹)cobalt(II) bis(4-formylbenzoate) dihydrate top

Crystal data top

[Co(C₆H₆N₂O)₂(H₂O)₄](C₈H₅O₃)₂·2H₂O	Z = 1
M_r = 709.53	F(000) = 369
Triclinic, P1	D_x = 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

Data collection top

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

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)] = 0.034	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(F_o²) + (0.0308P)²] where P = (F_o² + 2F_c²)/3
3780 reflections	(Δ/σ)_max < 0.001
236 parameters	Δρ_max = 0.36 e Å⁻³
9 restraints	Δρ_min = −0.41 e Å⁻³

Crystal data top

[Co(C₆H₆N₂O)₂(H₂O)₄](C₈H₅O₃)₂·2H₂O	γ = 72.564 (2)°
M_r = 709.53	V = 761.28 (5) Å³
Triclinic, P1	Z = 1
a = 6.4490 (2) Å	Mo Kα radiation
b = 6.8836 (3) Å	µ = 0.64 mm⁻¹
c = 18.1792 (5) Å	T = 100 K
α = 81.967 (3)°	0.17 × 0.08 × 0.04 mm
β = 84.681 (3)°

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	3780 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	2884 reflections with I > 2σ(I)
T_min = 0.943, T_max = 0.978	R_int = 0.054
13740 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	9 restraints
wR(F²) = 0.074	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	Δρ_max = 0.36 e Å⁻³
3780 reflections	Δρ_min = −0.41 e Å⁻³
236 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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)*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º) top

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···O1^iv	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···O1^v	0.90 (2)	1.87 (2)	2.7707 (19)	177 (1)
O6—H62···O2^vi	0.87 (2)	1.92 (2)	2.7760 (19)	168 (2)
O7—H71···O3^vii	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···O5^viii	0.93	2.45	3.210 (2)	139

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

Experimental details

Crystal data
Chemical formula	[Co(C₆H₆N₂O)₂(H₂O)₄](C₈H₅O₃)₂·2H₂O
M_r	709.53
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	6.4490 (2), 6.8836 (3), 18.1792 (5)
α, β, γ (°)	81.967 (3), 84.681 (3), 72.564 (2)
V (Å³)	761.28 (5)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.64
Crystal size (mm)	0.17 × 0.08 × 0.04

Data collection
Diffractometer	Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.943, 0.978
No. of measured, independent and observed [I > 2σ(I)] reflections	13740, 3780, 2884
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.669

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.074, 0.98
No. of reflections	3780
No. of parameters	236
No. of restraints	9
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.41

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Mercury (Macrae et al., 2006), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Selected bond lengths (Å) top

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

Hydrogen-bond geometry (Å, º) top

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···O1^iv	0.899 (15)	1.872 (15)	2.7707 (19)	177.3 (11)
O6—H62···O2^v	0.87 (2)	1.92 (2)	2.7760 (19)	168 (2)
O7—H71···O3^vi	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···O5^vii	0.93	2.45	3.210 (2)	139

Symmetry codes: (i) x+1, y−1, z+1; (ii) −x, −y, −z+1; (iii) −x, −y+1, −z; (iv) x+1, y−1, z; (v) x, y−1, z; (vi) −x+1, −y, −z+1; (vii) −x+1, −y, −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 Kafkas University Research Fund (grant No. 2009-FEF-03).

References

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