trans-Tetra­aqua­bis­(isonicotinamide-κN1)cobalt(II) bis­(3-hy­droxy­benzoate) tetra­hydrate

Zaman, İ.G.; Çaylak Delibaş, N.; Necefoğlu, H.; Hökelek, T.

doi:10.1107/S1600536812003911

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Pages m249-m250

doi:10.1107/S1600536812003911

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trans-Tetraaquabis(isonicotinamide-κN¹)cobalt(II) bis(3-hydroxybenzoate) tetrahydrate

İIbrahim Göker Zaman,^a Nagihan Çaylak Delibaş,^b Hacali Necefoğlu ^a and Tuncer Hökelek ^c ^*

^aDepartment of Chemistry, Kafkas University, 36100 Kars, Turkey, ^bDepartment of Physics, Sakarya University, 54187 Esentepe, Sakarya, Turkey, and ^cDepartment of Physics, Hacettepe University, 06800 Beytepe, Ankara, Turkey
^*Correspondence e-mail: merzifon@hacettepe.edu.tr

(Received 24 January 2012; accepted 30 January 2012; online 4 February 2012)

The asymmetric unit of the title compound, [Co(C₆H₆N₂O)₂(H₂O)₄](C₇H₅O₃)₂·4H₂O, contains one-half of the complex cation with the Co^II ion located on an inversion center, a 3-hydroxybenzoate counter-anion and two uncoordinated water molecules. Four water O atoms in the equatorial plane around the Co^II ion [Co—O = 2.0593 (16) and 2.1118 (16) Å] form a slightly distorted square-planar arrangement, and the distorted octahedral geometry is completed by the two N atoms [Co—N = 2.1306 (18) Å] from two isonicotinamide ligands. In the anion, the carboxylate group is twisted from the attached benzene ring at 8.84 (17)°. In the crystal, a three-dimensional hydrogen-bonding network, formed by classical O—H⋯O and N—H⋯O hydrogen bonds, consolidates the crystal packing, which exhibits π–π interactions between the benzene and pyridine rings, with centroid–centroid distances of 3.458 (1) and 3.606 (1) Å, respectively.

Related literature

For related structures, see: Hökelek, Dal, Tercan, Özbek et al. (2009 ); Hökelek, Dal, Tercan, Aybirdi et al. (2009 ); Hökelek, Yılmaz, Tercan, Gürgen et al. (2009 ); Hökelek, Yılmaz, Tercan, Özbek et al. (2009 ); Hökelek, Yılmaz, Tercan, Sertçelik et al. (2009 ); Sertçelik et al. (2009a ,b ); Zaman et al. (2012 ).

Experimental

Crystal data

[Co(C₆H₆N₂O)₂(H₂O)₄](C₇H₅O₃)₂·4H₂O
M_r = 721.53
Monoclinic, P 2₁ /n
a = 6.7032 (2) Å
b = 17.0523 (4) Å
c = 13.5406 (3) Å
β = 100.194 (3)°
V = 1523.32 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.65 mm⁻¹
T = 100 K
0.29 × 0.28 × 0.14 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.840, T_max = 0.916
14243 measured reflections
3779 independent reflections
3590 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.086
S = 1.23
3779 reflections
258 parameters
16 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H21⋯O2ⁱ	0.86 (3)	2.18 (3)	3.031 (3)	170 (3)
N2—H22⋯O8ⁱⁱ	0.85 (4)	2.20 (4)	3.007 (3)	158 (3)
O3—H31⋯O7	0.91 (4)	1.81 (4)	2.711 (2)	170 (4)
O5—H51⋯O3ⁱⁱ	0.96 (3)	1.76 (3)	2.715 (2)	171 (3)
O5—H52⋯O2ⁱⁱⁱ	0.86 (3)	1.95 (4)	2.782 (2)	163 (4)
O6—H61⋯O4^iv	0.95 (3)	1.73 (3)	2.685 (2)	178 (4)
O6—H62⋯O2^v	0.82 (3)	1.89 (4)	2.683 (2)	161 (3)
O7—H71⋯O1ⁱ	0.98 (3)	1.76 (4)	2.740 (3)	179 (3)
O8—H81⋯O1	0.96 (4)	1.81 (4)	2.760 (3)	174 (3)
O8—H82⋯O7^vi	0.83 (5)	2.06 (4)	2.807 (3)	149 (5)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) -x+1, -y, -z+1; (iv) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (v) -x, -y, -z+1; (vi) $[-x-{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

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/S1600536812003911/cv5239sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812003911/cv5239Isup2.hkl

checkCIF report

Comment top

As a part of our ongoing investigation on transition metal complexes of nicotinamide (NA) and/or the nicotinic acid derivative N,N-diethylnicotinamide (DENA) (Hökelek, Dal, Tercan, Özbek et al., 2009; Hökelek, Dal, Tercan, Aybirdi et al., 2009; Hökelek, Yılmaz, Tercan, Gürgen et al., 2009; Hökelek, Yılmaz, Tercan, Özbek et al., 2009; Hökelek, Yılmaz, Tercan, Sertçelik et al., 2009; Sertçelik et al., 2009a,b), the title compound was synthesized and its crystal structure is reported herein.

The title compound (I) is isostructural with the related Ni complex (Zaman et al., 2012). In (I) (Fig. 1), 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 2.1306 (18) Å from the Co atom in the axial positions (Fig. 1). The average Co—O bond length is 2.0856 (16) Å. The intramolecular O—H···O hydrogen bonds (Table 1) link the uncoordinated water molecules to the HB anion. The dihedral angle between the planar carboxylate group (O1/O2/C1) and the benzene ring A (C2—C7) is 8.84 (17)°, while that between rings A and B (N1/C8—C12) is 1.24 (7)°.

In the crystal structure, intermolecular O—H···O and N—H···O hydrogen bonds (Table 1) link the molecules into a three-dimensional network, in which they may be effective in the stabilization of the structure. π–π Contacts between the benzene and pyridine rings, Cg1—Cg2 and Cg1—Cg2ⁱ, [symmetry code: (i) -1 + x, y, z, 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 distances of 3.606 (1) and 3.458 (1) Å, respectively.

Related literature top

For related structures, see: Hökelek, Dal, Tercan, Özbek et al. (2009); Hökelek, Dal, Tercan, Aybirdi et al. (2009); Hökelek, Yılmaz, Tercan, Gürgen et al. (2009); Hökelek, Yılmaz, Tercan, Özbek et al. (2009); Hökelek, Yılmaz, Tercan, Sertçelik et al. (2009); Sertçelik et al. (2009a,b); Zaman et al. (2012).

Experimental top

The title compound was prepared by the reaction of CoSO₄.7H₂O (1.406 g, 5 mmol) in H₂O (100 ml) and INA (1.220 g, 10 mmol) in H₂O (50 ml) with sodium 3-hydroxybenzoate (1.601 g, 10 mmol) in H₂O (100 ml). The mixture was filtered and set aside to crystallize at ambient temperature for three weeks, 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 molecular structure of (I) with the atom-numbering scheme [symmetry code: (') -x, -y, -z]. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bonds are shown as dashed lines.

trans-Tetraaquabis(isonicotinamide-κN¹)cobalt(II) bis(3-hydroxybenzoate) tetrahydrate top

Crystal data top

[Co(C₆H₆N₂O)₂(H₂O)₄](C₇H₅O₃)₂·4H₂O	F(000) = 754
M_r = 721.53	D_x = 1.573 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 9057 reflections
a = 6.7032 (2) Å	θ = 2.4–28.4°
b = 17.0523 (4) Å	µ = 0.65 mm⁻¹
c = 13.5406 (3) Å	T = 100 K
β = 100.194 (3)°	Block, orange
V = 1523.32 (7) Å³	0.29 × 0.28 × 0.14 mm
Z = 2

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	3779 independent reflections
Radiation source: fine-focus sealed tube	3590 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
ϕ and ω scans	θ_max = 28.4°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −8→8
T_min = 0.840, T_max = 0.916	k = −22→21
14243 measured reflections	l = −15→18

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) = 0.086	H atoms treated by a mixture of independent and constrained refinement
S = 1.23	w = 1/[σ²(F_o²) + (0.0269P)² + 1.4849P] where P = (F_o² + 2F_c²)/3
3779 reflections	(Δ/σ)_max < 0.001
258 parameters	Δρ_max = 0.47 e Å⁻³
16 restraints	Δρ_min = −0.42 e Å⁻³

Crystal data top

[Co(C₆H₆N₂O)₂(H₂O)₄](C₇H₅O₃)₂·4H₂O	V = 1523.32 (7) Å³
M_r = 721.53	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.7032 (2) Å	µ = 0.65 mm⁻¹
b = 17.0523 (4) Å	T = 100 K
c = 13.5406 (3) Å	0.29 × 0.28 × 0.14 mm
β = 100.194 (3)°

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	3779 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	3590 reflections with I > 2σ(I)
T_min = 0.840, T_max = 0.916	R_int = 0.019
14243 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	16 restraints
wR(F²) = 0.086	H atoms treated by a mixture of independent and constrained refinement
S = 1.23	Δρ_max = 0.47 e Å⁻³
3779 reflections	Δρ_min = −0.42 e Å⁻³
258 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	0.5000	0.0000	0.5000	0.00895 (12)
O1	0.1791 (2)	0.11648 (9)	0.83771 (12)	0.0148 (3)
O2	0.0778 (2)	0.04189 (9)	0.70323 (12)	0.0136 (3)
O3	0.0160 (3)	0.39111 (10)	0.72117 (13)	0.0160 (3)
H31	0.005 (6)	0.430 (2)	0.675 (3)	0.045 (11)*
O4	0.6007 (3)	0.33160 (9)	0.81945 (12)	0.0166 (3)
O5	0.6814 (2)	0.04700 (10)	0.40186 (12)	0.0141 (3)
H51	0.627 (6)	0.074 (2)	0.341 (2)	0.057 (12)*
H52	0.759 (5)	0.0138 (18)	0.380 (3)	0.039 (10)*
O6	0.2333 (2)	0.03327 (10)	0.40967 (13)	0.0157 (3)
H61	0.190 (5)	0.0815 (12)	0.378 (3)	0.039 (10)*
H62	0.151 (5)	0.0013 (15)	0.381 (3)	0.039 (10)*
O7	−0.0014 (3)	0.51872 (10)	0.60055 (13)	0.0168 (3)
H71	0.113 (5)	0.554 (2)	0.623 (3)	0.056 (12)*
H72	−0.006 (10)	0.516 (4)	0.541 (2)	0.13 (3)*
O8	−0.0938 (3)	0.06685 (11)	0.95512 (13)	0.0195 (4)
H81	−0.006 (5)	0.086 (2)	0.912 (3)	0.049 (11)*
H82	−0.200 (6)	0.054 (4)	0.917 (4)	0.16 (3)*
N1	0.5124 (3)	0.11063 (11)	0.57398 (14)	0.0107 (3)
N2	0.4839 (3)	0.39703 (12)	0.67598 (15)	0.0144 (4)
H21	0.473 (5)	0.441 (2)	0.705 (2)	0.023 (8)*
H22	0.440 (5)	0.396 (2)	0.613 (3)	0.030 (9)*
C1	0.1091 (3)	0.10798 (13)	0.74547 (16)	0.0112 (4)
C2	0.0580 (3)	0.18067 (12)	0.68279 (16)	0.0106 (4)
C3	0.0646 (3)	0.25369 (13)	0.72979 (16)	0.0118 (4)
H3	0.1019	0.2575	0.7991	0.014*
C4	0.0151 (3)	0.32060 (13)	0.67240 (17)	0.0122 (4)
C5	−0.0363 (3)	0.31556 (13)	0.56836 (17)	0.0141 (4)
H5	−0.0678	0.3607	0.5302	0.017*
C6	−0.0403 (3)	0.24293 (14)	0.52186 (17)	0.0141 (4)
H6	−0.0735	0.2395	0.4523	0.017*
C7	0.0052 (3)	0.17518 (13)	0.57864 (17)	0.0126 (4)
H7	0.0004	0.1265	0.5473	0.015*
C8	0.5612 (3)	0.11620 (13)	0.67453 (16)	0.0117 (4)
H8	0.5880	0.0703	0.7117	0.014*
C9	0.5732 (3)	0.18675 (13)	0.72507 (17)	0.0124 (4)
H9	0.6091	0.1881	0.7946	0.015*
C10	0.5308 (3)	0.25590 (12)	0.67073 (16)	0.0108 (4)
C11	0.4790 (3)	0.25056 (13)	0.56688 (17)	0.0122 (4)
H11	0.4491	0.2955	0.5281	0.015*
C12	0.4724 (3)	0.17733 (13)	0.52206 (16)	0.0119 (4)
H12	0.4386	0.1744	0.4525	0.014*
C13	0.5415 (3)	0.33216 (13)	0.72758 (17)	0.0118 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.01097 (19)	0.0073 (2)	0.00830 (19)	0.00020 (14)	0.00093 (14)	−0.00006 (14)
O1	0.0186 (8)	0.0140 (8)	0.0116 (7)	0.0004 (6)	0.0015 (6)	0.0008 (6)
O2	0.0155 (7)	0.0089 (7)	0.0159 (8)	−0.0015 (6)	0.0015 (6)	−0.0008 (6)
O3	0.0239 (8)	0.0094 (7)	0.0144 (8)	−0.0002 (6)	0.0022 (6)	−0.0015 (6)
O4	0.0260 (9)	0.0117 (8)	0.0113 (8)	−0.0024 (6)	0.0011 (6)	−0.0020 (6)
O5	0.0170 (8)	0.0133 (8)	0.0132 (7)	0.0007 (6)	0.0060 (6)	0.0012 (6)
O6	0.0159 (8)	0.0094 (7)	0.0188 (8)	0.0001 (6)	−0.0048 (6)	0.0009 (6)
O7	0.0196 (8)	0.0134 (8)	0.0164 (8)	−0.0028 (6)	0.0006 (7)	0.0005 (6)
O8	0.0235 (9)	0.0188 (9)	0.0177 (8)	−0.0023 (7)	0.0076 (7)	−0.0004 (7)
N1	0.0102 (8)	0.0107 (8)	0.0113 (8)	−0.0007 (6)	0.0020 (6)	−0.0010 (7)
N2	0.0211 (9)	0.0097 (9)	0.0117 (9)	0.0005 (7)	0.0014 (8)	−0.0025 (7)
C1	0.0091 (9)	0.0118 (10)	0.0134 (10)	−0.0006 (7)	0.0035 (7)	0.0011 (8)
C2	0.0094 (9)	0.0104 (10)	0.0125 (10)	−0.0010 (7)	0.0027 (7)	0.0016 (7)
C3	0.0119 (9)	0.0127 (10)	0.0108 (9)	−0.0021 (7)	0.0016 (8)	−0.0003 (8)
C4	0.0110 (9)	0.0098 (10)	0.0159 (10)	−0.0008 (7)	0.0023 (8)	−0.0016 (8)
C5	0.0145 (10)	0.0121 (10)	0.0153 (10)	−0.0012 (8)	0.0018 (8)	0.0033 (8)
C6	0.0145 (10)	0.0163 (11)	0.0110 (10)	−0.0013 (8)	0.0009 (8)	0.0001 (8)
C7	0.0125 (9)	0.0116 (10)	0.0139 (10)	−0.0021 (7)	0.0028 (8)	−0.0017 (8)
C8	0.0132 (9)	0.0095 (9)	0.0122 (10)	0.0000 (7)	0.0023 (8)	0.0012 (8)
C9	0.0127 (9)	0.0128 (10)	0.0116 (10)	−0.0006 (8)	0.0014 (8)	−0.0003 (8)
C10	0.0094 (9)	0.0092 (9)	0.0138 (10)	−0.0011 (7)	0.0025 (7)	−0.0013 (8)
C11	0.0136 (9)	0.0094 (10)	0.0132 (10)	−0.0008 (7)	0.0019 (8)	0.0008 (8)
C12	0.0129 (9)	0.0115 (10)	0.0114 (10)	−0.0012 (7)	0.0022 (8)	−0.0007 (8)
C13	0.0120 (9)	0.0108 (10)	0.0132 (10)	−0.0026 (7)	0.0039 (8)	−0.0019 (8)

Geometric parameters (Å, º) top

Co1—O5	2.1118 (16)	N2—H21	0.85 (3)
Co1—O5ⁱ	2.1118 (16)	N2—H22	0.85 (4)
Co1—O6	2.0593 (16)	C2—C1	1.507 (3)
Co1—O6ⁱ	2.0593 (16)	C2—C3	1.396 (3)
Co1—N1	2.1306 (18)	C2—C7	1.395 (3)
Co1—N1ⁱ	2.1306 (18)	C3—H3	0.9300
O1—C1	1.262 (3)	C4—C3	1.387 (3)
O2—C1	1.264 (3)	C5—C4	1.392 (3)
O3—C4	1.371 (3)	C5—C6	1.388 (3)
O3—H31	0.91 (4)	C5—H5	0.9300
O4—C13	1.237 (3)	C6—H6	0.9300
O5—H51	0.963 (18)	C7—C6	1.391 (3)
O5—H52	0.85 (2)	C7—H7	0.9300
O6—H61	0.948 (17)	C8—C9	1.379 (3)
O6—H62	0.82 (2)	C8—H8	0.9300
O7—H71	0.978 (18)	C9—C10	1.392 (3)
O7—H72	0.81 (2)	C9—H9	0.9300
O8—H81	0.960 (18)	C11—C10	1.390 (3)
O8—H82	0.83 (3)	C11—C12	1.386 (3)
N1—C8	1.346 (3)	C11—H11	0.9300
N1—C12	1.339 (3)	C12—H12	0.9300
N2—C13	1.328 (3)	C13—C10	1.506 (3)

O5ⁱ—Co1—O5	180.0	C7—C2—C3	120.2 (2)
O5—Co1—N1	88.91 (7)	C2—C3—H3	120.2
O5—Co1—N1ⁱ	91.09 (7)	C4—C3—C2	119.6 (2)
O5ⁱ—Co1—N1	91.09 (7)	C4—C3—H3	120.2
O5ⁱ—Co1—N1ⁱ	88.91 (7)	O3—C4—C3	118.1 (2)
O6—Co1—O5	93.32 (7)	O3—C4—C5	121.4 (2)
O6—Co1—O5ⁱ	86.68 (7)	C3—C4—C5	120.5 (2)
O6ⁱ—Co1—O5ⁱ	93.32 (7)	C4—C5—H5	120.1
O6ⁱ—Co1—O5	86.68 (7)	C6—C5—C4	119.7 (2)
O6—Co1—O6ⁱ	180.0	C6—C5—H5	120.1
O6—Co1—N1	89.59 (7)	C5—C6—C7	120.4 (2)
O6ⁱ—Co1—N1	90.41 (7)	C5—C6—H6	119.8
O6—Co1—N1ⁱ	90.41 (7)	C7—C6—H6	119.8
O6ⁱ—Co1—N1ⁱ	89.59 (7)	C2—C7—H7	120.2
N1ⁱ—Co1—N1	180.0	C6—C7—C2	119.6 (2)
C4—O3—H31	108 (2)	C6—C7—H7	120.2
Co1—O5—H51	123 (2)	N1—C8—C9	123.1 (2)
Co1—O5—H52	115 (2)	N1—C8—H8	118.5
H52—O5—H51	101 (3)	C9—C8—H8	118.5
Co1—O6—H61	132 (2)	C8—C9—C10	119.2 (2)
Co1—O6—H62	123 (2)	C8—C9—H9	120.4
H62—O6—H61	104 (2)	C10—C9—H9	120.4
H71—O7—H72	104 (3)	C9—C10—C13	118.31 (19)
H81—O8—H82	105 (3)	C11—C10—C9	118.0 (2)
C8—N1—Co1	121.36 (14)	C11—C10—C13	123.65 (19)
C12—N1—Co1	121.18 (14)	C10—C11—H11	120.5
C12—N1—C8	117.46 (19)	C12—C11—C10	119.0 (2)
C13—N2—H21	122 (2)	C12—C11—H11	120.5
C13—N2—H22	121 (2)	N1—C12—C11	123.2 (2)
H21—N2—H22	116 (3)	N1—C12—H12	118.4
O1—C1—O2	123.5 (2)	C11—C12—H12	118.4
O1—C1—C2	118.07 (19)	O4—C13—N2	123.2 (2)
O2—C1—C2	118.38 (19)	O4—C13—C10	119.00 (19)
C3—C2—C1	119.43 (19)	N2—C13—C10	117.83 (19)
C7—C2—C1	120.39 (19)

O5—Co1—N1—C8	−130.62 (16)	C1—C2—C7—C6	−179.56 (19)
O5ⁱ—Co1—N1—C8	49.38 (16)	C3—C2—C7—C6	0.2 (3)
O5—Co1—N1—C12	49.21 (16)	O3—C4—C3—C2	177.66 (19)
O5ⁱ—Co1—N1—C12	−130.79 (16)	C5—C4—C3—C2	−1.5 (3)
O6—Co1—N1—C8	136.06 (16)	C6—C5—C4—O3	−178.4 (2)
O6ⁱ—Co1—N1—C8	−43.94 (16)	C6—C5—C4—C3	0.7 (3)
O6—Co1—N1—C12	−44.12 (16)	C4—C5—C6—C7	0.5 (3)
O6ⁱ—Co1—N1—C12	135.88 (16)	C2—C7—C6—C5	−1.0 (3)
Co1—N1—C8—C9	179.20 (16)	N1—C8—C9—C10	0.8 (3)
C12—N1—C8—C9	−0.6 (3)	C8—C9—C10—C11	−0.4 (3)
Co1—N1—C12—C11	−179.88 (16)	C8—C9—C10—C13	178.98 (19)
C8—N1—C12—C11	0.0 (3)	C12—C11—C10—C9	−0.3 (3)
C3—C2—C1—O1	−8.0 (3)	C12—C11—C10—C13	−179.57 (19)
C3—C2—C1—O2	171.26 (19)	C10—C11—C12—N1	0.5 (3)
C7—C2—C1—O1	171.73 (19)	O4—C13—C10—C9	5.0 (3)
C7—C2—C1—O2	−9.0 (3)	O4—C13—C10—C11	−175.7 (2)
C1—C2—C3—C4	−179.20 (19)	N2—C13—C10—C9	−174.3 (2)
C7—C2—C3—C4	1.1 (3)	N2—C13—C10—C11	5.0 (3)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···O2ⁱⁱ	0.86 (3)	2.18 (3)	3.031 (3)	170 (3)
N2—H22···O8ⁱⁱⁱ	0.85 (4)	2.20 (4)	3.007 (3)	158 (3)
O3—H31···O7	0.91 (4)	1.81 (4)	2.711 (2)	170 (4)
O5—H51···O3ⁱⁱⁱ	0.96 (3)	1.76 (3)	2.715 (2)	171 (3)
O5—H52···O2ⁱ	0.86 (3)	1.95 (4)	2.782 (2)	163 (4)
O6—H61···O4^iv	0.95 (3)	1.73 (3)	2.685 (2)	178 (4)
O6—H62···O2^v	0.82 (3)	1.89 (4)	2.683 (2)	161 (3)
O7—H71···O1ⁱⁱ	0.98 (3)	1.76 (4)	2.740 (3)	179 (3)
O8—H81···O1	0.96 (4)	1.81 (4)	2.760 (3)	174 (3)
O8—H82···O7^vi	0.83 (5)	2.06 (4)	2.807 (3)	149 (5)

Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1/2, y+1/2, −z+3/2; (iii) x+1/2, −y+1/2, z−1/2; (iv) x−1/2, −y+1/2, z−1/2; (v) −x, −y, −z+1; (vi) −x−1/2, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	[Co(C₆H₆N₂O)₂(H₂O)₄](C₇H₅O₃)₂·4H₂O
M_r	721.53
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	6.7032 (2), 17.0523 (4), 13.5406 (3)
β (°)	100.194 (3)
V (Å³)	1523.32 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.65
Crystal size (mm)	0.29 × 0.28 × 0.14

Data collection
Diffractometer	Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.840, 0.916
No. of measured, independent and observed [I > 2σ(I)] reflections	14243, 3779, 3590
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.670

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.086, 1.23
No. of reflections	3779
No. of parameters	258
No. of restraints	16
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.42

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).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···O2ⁱ	0.86 (3)	2.18 (3)	3.031 (3)	170 (3)
N2—H22···O8ⁱⁱ	0.85 (4)	2.20 (4)	3.007 (3)	158 (3)
O3—H31···O7	0.91 (4)	1.81 (4)	2.711 (2)	170 (4)
O5—H51···O3ⁱⁱ	0.96 (3)	1.76 (3)	2.715 (2)	171 (3)
O5—H52···O2ⁱⁱⁱ	0.86 (3)	1.95 (4)	2.782 (2)	163 (4)
O6—H61···O4^iv	0.95 (3)	1.73 (3)	2.685 (2)	178 (4)
O6—H62···O2^v	0.82 (3)	1.89 (4)	2.683 (2)	161 (3)
O7—H71···O1ⁱ	0.98 (3)	1.76 (4)	2.740 (3)	179 (3)
O8—H81···O1	0.96 (4)	1.81 (4)	2.760 (3)	174 (3)
O8—H82···O7^vi	0.83 (5)	2.06 (4)	2.807 (3)	149 (5)

Symmetry codes: (i) −x+1/2, y+1/2, −z+3/2; (ii) x+1/2, −y+1/2, z−1/2; (iii) −x+1, −y, −z+1; (iv) x−1/2, −y+1/2, z−1/2; (v) −x, −y, −z+1; (vi) −x−1/2, y−1/2, −z+3/2.

Acknowledgements

The authors are indebted to Anadolu University and to the Medicinal Plants and Medicine Research Centre of Anadolu University, Eskişehir, Turkey, for the use of the X-ray diffractometer.

References

Bruker (2005). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Hökelek, T., Dal, H., Tercan, B., Aybirdi, Ö. & Necefoğlu, H. (2009). Acta Cryst. E65, m627–m628. Web of Science CSD CrossRef IUCr Journals Google Scholar
Hökelek, T., Dal, H., Tercan, B., Özbek, F. E. & Necefoğlu, H. (2009). Acta Cryst. E65, m1330–m1331. Web of Science CSD CrossRef IUCr Journals Google Scholar
Hökelek, T., Yılmaz, F., Tercan, B., Gürgen, F. & Necefoğlu, H. (2009). Acta Cryst. E65, m1101–m1102. Web of Science CSD CrossRef IUCr Journals Google Scholar
Hökelek, T., Yılmaz, F., Tercan, B., Özbek, F. E. & Necefoğlu, H. (2009). Acta Cryst. E65, m768–m769. Web of Science CSD CrossRef IUCr Journals Google Scholar
Hökelek, T., Yılmaz, F., Tercan, B., Sertçelik, M. & Necefoğlu, H. (2009). Acta Cryst. E65, m1130–m1131. Web of Science CSD CrossRef IUCr Journals Google Scholar
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sertçelik, M., Tercan, B., Şahin, E., Necefoğlu, H. & Hökelek, T. (2009a). Acta Cryst. E65, m326–m327. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sertçelik, M., Tercan, B., Şahin, E., Necefoğlu, H. & Hökelek, T. (2009b). Acta Cryst. E65, m389–m390. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zaman, İ. G., Çaylak Delibaş, N., Necefoğlu, H. & Hökelek, T. (2012). Acta Cryst. E68, m200–m201. Web of Science CSD CrossRef IUCr Journals Google Scholar

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