Di­aqua­bis­(3-chloro­benzoato-κO)bis­(nicotinamide-κN1)cobalt(II)

Bozkurt, N.; Dilek, N.; Çaylak Delibaş, N.; Necefoğlu, H.; Hökelek, T.

doi:10.1107/S160053681301458X

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 6| June 2013| Pages m349-m350

doi:10.1107/S160053681301458X

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Diaquabis(3-chlorobenzoato-κO)bis(nicotinamide-κN¹)cobalt(II)

Nihat Bozkurt,^a Nefise Dilek,^b Nagihan Çaylak Delibaş,^c Hacali Necefoğlu ^a and Tuncer Hökelek ^d ^*

^aDepartment of Chemistry, Kafkas University, 36100 Kars, Turkey, ^bAksaray University, Department of Physics, 68100, Aksaray, Turkey, ^cDepartment of Physics, Sakarya University, 54187 Esentepe, Sakarya, Turkey, and ^dDepartment of Physics, Hacettepe University, 06800 Beytepe, Ankara, Turkey
^*Correspondence e-mail: merzifon@hacettepe.edu.tr

(Received 22 May 2013; accepted 27 May 2013; online 31 May 2013)

In the title complex, [Co(C₇H₄ClO₂)₂(C₆H₆N₂O)₂(H₂O)₂], the Co^II atom is located on an inversion center and is coordinated by two 3-chlorobenzoate (CB) anions, two nicotinamide (NA) ligands and two water molecules. The four O atoms in the equatorial plane form a slightly distorted square-planar arrangement, while the slightly distorted octahedral coordination is completed by the two N atoms of the NA ligands in the axial positions. The dihedral angle between the carboxylate group and the adjacent benzene ring is 9.14 (9)°, while the pyridine and benzene rings are oriented at a dihedral angle of 82.18 (8)°. In the crystal, N—H⋯O and O—H⋯O hydrogen bonds link the molecules into a two-dimensional network lying parallel to (101). π–π stacking between parallel pyridine rings of adjacent molecules [centroid–centroid distance = 3.7765 (8) Å] further stabilizes the crystal structure.

Related literature

For literature on niacin, see: Krishnamachari (1974 ). For information on the nicotinic acid derivative N,N-diethylnicotinamide, see: Bigoli et al. (1972 ). For related structures, see: Aydın et al. (2012 ); Hökelek et al. (1996 , 2009a ,b ); Hökelek & Necefoğlu (1998 , 2007 ); Necefoğlu et al. (2011a ,b ); Sertçelik et al. (2012a ,b ,c ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

[Co(C₇H₄ClO₂)₂(C₆H₆N₂O)₂(H₂O)₂]
M_r = 650.32
Monoclinic, P 2₁ /n
a = 11.5181 (3) Å
b = 8.8191 (2) Å
c = 13.5089 (3) Å
β = 90.546 (2)°
V = 1372.16 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.88 mm⁻¹
T = 294 K
0.35 × 0.22 × 0.18 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2012 ) T_min = 0.793, T_max = 0.854
18960 measured reflections
2797 independent reflections
2667 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.074
S = 1.11
2797 reflections
204 parameters
52 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H21⋯O3ⁱ	0.84 (3)	2.24 (3)	2.876 (2)	133 (2)
N2—H22⋯O4ⁱⁱ	0.87 (2)	2.27 (2)	3.012 (2)	143 (2)
O4—H41⋯O1ⁱⁱⁱ	0.92 (2)	1.68 (2)	2.5822 (16)	164 (2)
O4—H42⋯O3^iv	0.83 (3)	1.98 (3)	2.7892 (15)	166 (2)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) -x, -y+2, -z+2; (iv) x, y+1, z.

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); 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, 2012 ); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681301458X/su2606sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681301458X/su2606Isup2.hkl

checkCIF report

Comment top

As a part of our ongoing investigations of 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.

In the title mononuclear complex, Co^II atom is located on an inversion center and is coordinated by two 3-chlorobenzoate (CB) anions, two nicotinamide (NA) ligands and two water molecules, all ligands coordinating in a monodentate manner (Fig. 1). The crystal structures of similar complexes of Cu^II, Co^II, Ni^II, Mn^II and Zn^II ions, [Cu(C₇H₅O₂)₂(C₁₀H₁₄N₂O)₂] (Hökelek et al., 1996), [Cu(C₇H₄BrO₂)₂(C₆H₆N₂O)₂(H₂O)₂] (Necefoğlu et al., 2011a), [Co(C₆H₆N₂O)₂(C₇H₄NO₄)₂(H₂O)₂] (Hökelek & Necefoğlu, 1998), [Co(C₉H₉O₂)₂(C₁₀H₁₄N₂O)₂(H₂O)₂] (Necefoğlu et al., 2011b), [Co(C₇H₄IO₂)₂(C₆H₆N₂O)₂(H₂O)₂] (Aydın et al., 2012), [Co(C₈H₅O₃)₂(C₆H₆N₂O)₂(H₂O)₂] (Sertçelik et al., 2012a), [Ni(C₇H₄ClO₂)₂(C₆H₆N₂O)₂(H₂O)₂] (Hökelek et al., 2009a), [Ni(C₅H₅O₃)₂(C₆H₆N₂O)₂(H₂O)₂] (Sertçelik et al., 2012b), [Mn(C₉H₁₀NO₂)₂(H₂O)₄].2H₂O (Hökelek & Necefoğlu, 2007), [Zn(C₇H₄BrO₂)₂(C₆H₆N₂O)₂(H₂O)₂] (Hökelek et al., 2009b) and [Zn(C₈H₅O₃)₂(C₁₀H₁₄N₂O)₂(H₂O)₂] (Sertçelik et al., 2012c) have been reported. In the copper(II) complex mentioned above the two benzoate ions coordinate to the Cu^II atom as bidentate ligands, while in the other structures all the ligands coordinate in a monodentate manner.

In the title complex, Fig. 1, the four symmetry related O atoms (O2, O2a, O4 and O4a) [symmetry code: (a) - x, - y, - z] in the equatorial plane around the Co^II ion form a slightly distorted square-planar arrangement, while the slightly distorted octahedral coordination is completed by the two symmetry related N atoms of the NA ligands (N1 and N1a) in the axial positions. The near equalities of the C1—O1 [1.2435 (19) Å] and C1—O2 [1.2677 (18) Å] bonds in the carboxylate group indicate delocalized bonding arrangement, rather than localized single and double bonds. The Co—O bond lengths are 2.0592 (10) Å (for benzoate oxygens) and 2.1385 (10) Å (for water oxygens), and the Co—N bond length is 2.1641 (11) Å, close to standard values (Allen et al., 1987). The Co atom is displaced out of the mean-plane of the carboxylate group (O1/C1/O2) by -0.5077 (1) Å. The dihedral angle between the planar carboxylate group and the adjacent benzene ring (C2—C7) is 9.14 (9)°. The benzene (C2—C7) and the pyridine (N1/C8—C12) rings are oriented at a dihedral angle of 82.18 (8)°.

In the crystal, N—H···O and O—H···O hydrogen bonds (Table 1) link the molecules into a two-dimensional network lying parallel to (101). π···π stacking between the pyridine rings, Cg···Cgⁱ [symmetry code: (i) -x, -y+1, -z+2, where Cg is the centroid of ring N1/C8—C12] further stabilizes the crystal structure, with a centroid-centroid distance of 3.7765 (8) Å.

Related literature top

For literature on niacin, see: Krishnamachari (1974). For information on the nicotinic acid derivative N,N-diethylnicotinamide, see: Bigoli et al. (1972). For related structures, see: Aydın et al. (2012); Hökelek et al. (1996, 2009a,b); Hökelek & Necefoğlu (1998, 2007); Necefoğlu et al. (2011a,b); Sertçelik et al. (2012a,b,c). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound was prepared by the reaction of CoSO₄.H₂O (0.865 g, 5 mmol) in H₂O (25 ml) and nicotinamide (1.22 g, 50 mmol) in H₂O (100 ml) with sodium 3-chlorobenzoate (1.79 g, 10 mmol) in H₂O (100 ml) at room temperature. The mixture was filtered and set aside to crystallize at ambient temperature for several days, giving pink single crystals.

Computing details top

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); 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, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009).

Figures top

Fig. 1. The molecular structure of the title molecule, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level [symmetry code: (a) - x, - y, - z].

Diaquabis(3-chlorobenzoato-κO)bis(nicotinamide-κN¹)cobalt(II) top

Crystal data top

[Co(C₇H₄ClO₂)₂(C₆H₆N₂O)₂(H₂O)₂]	F(000) = 666
M_r = 650.32	D_x = 1.574 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4857 reflections
a = 11.5181 (3) Å	θ = 2.3–24.4°
b = 8.8191 (2) Å	µ = 0.88 mm⁻¹
c = 13.5089 (3) Å	T = 294 K
β = 90.546 (2)°	Block, pink
V = 1372.16 (6) Å³	0.35 × 0.22 × 0.18 mm
Z = 2

Data collection top

Bruker APEXII CCD area-detector diffractometer	2797 independent reflections
Radiation source: fine-focus sealed tube	2667 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ϕ and ω scans	θ_max = 26.4°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −14→14
T_min = 0.793, T_max = 0.854	k = −11→10
18960 measured reflections	l = −16→16

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.027	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.074	w = 1/[σ²(F_o²) + (0.0393P)² + 0.5258P] where P = (F_o² + 2F_c²)/3
S = 1.11	(Δ/σ)_max = 0.001
2797 reflections	Δρ_max = 0.32 e Å⁻³
204 parameters	Δρ_min = −0.33 e Å⁻³
52 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0334 (17)

Crystal data top

[Co(C₇H₄ClO₂)₂(C₆H₆N₂O)₂(H₂O)₂]	V = 1372.16 (6) Å³
M_r = 650.32	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 11.5181 (3) Å	µ = 0.88 mm⁻¹
b = 8.8191 (2) Å	T = 294 K
c = 13.5089 (3) Å	0.35 × 0.22 × 0.18 mm
β = 90.546 (2)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	2797 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2012)	2667 reflections with I > 2σ(I)
T_min = 0.793, T_max = 0.854	R_int = 0.027
18960 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	52 restraints
wR(F²) = 0.074	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	Δρ_max = 0.32 e Å⁻³
2797 reflections	Δρ_min = −0.33 e Å⁻³
204 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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 > 2sigma(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	0.00000	1.00000	1.00000	0.0221 (1)
Cl1	0.57400 (4)	0.77742 (8)	0.87425 (3)	0.0604 (2)
O1	0.17264 (10)	0.87980 (18)	1.18080 (9)	0.0518 (4)
O2	0.17291 (8)	0.94984 (12)	1.02212 (8)	0.0299 (3)
O3	0.16810 (10)	0.34420 (12)	0.81282 (10)	0.0415 (4)
O4	0.04558 (10)	1.07995 (12)	0.85606 (8)	0.0298 (3)
N1	−0.02319 (10)	0.77771 (13)	0.93492 (9)	0.0258 (3)
N2	0.23334 (16)	0.56716 (18)	0.76095 (16)	0.0592 (6)
C1	0.21833 (12)	0.88839 (17)	1.09796 (11)	0.0293 (4)
C2	0.33518 (12)	0.81535 (17)	1.08465 (11)	0.0286 (4)
C3	0.39495 (13)	0.83285 (18)	0.99657 (11)	0.0316 (4)
C4	0.49988 (13)	0.7599 (2)	0.98487 (12)	0.0368 (5)
C5	0.54679 (15)	0.6700 (2)	1.05879 (14)	0.0464 (6)
C6	0.48691 (17)	0.6533 (2)	1.14586 (14)	0.0496 (6)
C7	0.38168 (15)	0.7255 (2)	1.15907 (12)	0.0388 (5)
C8	0.06524 (12)	0.70512 (15)	0.89207 (11)	0.0268 (4)
C9	0.05526 (12)	0.56102 (15)	0.85229 (10)	0.0258 (4)
C10	−0.05151 (14)	0.48869 (16)	0.85705 (12)	0.0314 (4)
C11	−0.14353 (13)	0.56408 (18)	0.89921 (13)	0.0356 (5)
C12	−0.12591 (12)	0.70790 (16)	0.93721 (11)	0.0303 (4)
C13	0.15664 (14)	0.48213 (16)	0.80673 (12)	0.0304 (4)
H3	0.36460	0.89300	0.94610	0.0380*
H5	0.61770	0.62160	1.04990	0.0560*
H6	0.51750	0.59290	1.19620	0.0590*
H7	0.34200	0.71360	1.21820	0.0470*
H8	0.13670	0.75380	0.88890	0.0320*
H10	−0.06090	0.39100	0.83220	0.0380*
H11	−0.21640	0.51890	0.90200	0.0430*
H12	−0.18830	0.75810	0.96560	0.0360*
H21	0.221 (2)	0.659 (3)	0.7492 (19)	0.066 (7)*
H22	0.293 (2)	0.526 (3)	0.7323 (19)	0.063 (7)*
H41	−0.028 (2)	1.098 (3)	0.8311 (18)	0.069 (7)*
H42	0.079 (2)	1.163 (3)	0.8530 (17)	0.055 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0201 (2)	0.0183 (2)	0.0280 (2)	0.0011 (1)	0.0066 (1)	−0.0026 (1)
Cl1	0.0389 (2)	0.1013 (4)	0.0412 (3)	0.0171 (2)	0.0140 (2)	0.0029 (2)
O1	0.0339 (6)	0.0875 (10)	0.0342 (6)	0.0108 (6)	0.0090 (5)	0.0038 (6)
O2	0.0230 (5)	0.0306 (5)	0.0362 (5)	0.0039 (4)	0.0044 (4)	0.0007 (4)
O3	0.0403 (6)	0.0194 (5)	0.0651 (8)	0.0024 (4)	0.0211 (5)	−0.0007 (5)
O4	0.0297 (5)	0.0267 (6)	0.0332 (5)	−0.0023 (4)	0.0098 (4)	−0.0001 (4)
N1	0.0256 (6)	0.0205 (5)	0.0313 (6)	0.0005 (4)	0.0049 (5)	−0.0027 (4)
N2	0.0569 (10)	0.0231 (7)	0.0985 (14)	0.0036 (7)	0.0507 (10)	0.0049 (8)
C1	0.0247 (7)	0.0308 (7)	0.0324 (7)	−0.0020 (5)	0.0034 (5)	−0.0042 (6)
C2	0.0261 (7)	0.0297 (7)	0.0301 (7)	0.0001 (6)	−0.0001 (5)	−0.0025 (6)
C3	0.0273 (7)	0.0369 (8)	0.0307 (7)	0.0051 (6)	0.0000 (6)	0.0031 (6)
C4	0.0286 (7)	0.0489 (10)	0.0331 (8)	0.0054 (6)	0.0038 (6)	−0.0028 (7)
C5	0.0344 (8)	0.0564 (11)	0.0482 (10)	0.0200 (8)	−0.0027 (7)	0.0004 (8)
C6	0.0479 (10)	0.0572 (11)	0.0435 (10)	0.0165 (9)	−0.0075 (8)	0.0127 (8)
C7	0.0401 (9)	0.0459 (9)	0.0303 (8)	0.0038 (7)	0.0005 (6)	0.0045 (7)
C8	0.0251 (6)	0.0214 (6)	0.0339 (7)	−0.0006 (5)	0.0068 (5)	−0.0010 (5)
C9	0.0292 (7)	0.0197 (6)	0.0287 (7)	0.0017 (5)	0.0063 (5)	0.0004 (5)
C10	0.0336 (8)	0.0220 (7)	0.0388 (8)	−0.0030 (5)	0.0051 (6)	−0.0062 (5)
C11	0.0270 (7)	0.0312 (8)	0.0486 (9)	−0.0058 (6)	0.0062 (6)	−0.0072 (7)
C12	0.0249 (7)	0.0276 (7)	0.0384 (8)	0.0010 (5)	0.0073 (6)	−0.0032 (6)
C13	0.0320 (8)	0.0211 (7)	0.0382 (8)	0.0000 (5)	0.0112 (6)	−0.0025 (6)

Geometric parameters (Å, º) top

Co1—O2	2.0592 (9)	C2—C3	1.389 (2)
Co1—O4	2.1385 (11)	C3—C4	1.380 (2)
Co1—N1	2.1640 (12)	C4—C5	1.381 (2)
Co1—O2ⁱ	2.0592 (9)	C5—C6	1.377 (3)
Co1—O4ⁱ	2.1385 (11)	C6—C7	1.382 (3)
Co1—N1ⁱ	2.1640 (12)	C8—C9	1.3841 (19)
Cl1—C4	1.7350 (16)	C9—C13	1.497 (2)
O1—C1	1.2435 (19)	C9—C10	1.387 (2)
O2—C1	1.2676 (18)	C10—C11	1.379 (2)
O3—C13	1.2262 (18)	C11—C12	1.383 (2)
O4—H41	0.92 (2)	C3—H3	0.9300
O4—H42	0.83 (3)	C5—H5	0.9300
N1—C12	1.3344 (18)	C6—H6	0.9300
N1—C8	1.3392 (18)	C7—H7	0.9300
N2—C13	1.317 (2)	C8—H8	0.9300
N2—H21	0.84 (3)	C10—H10	0.9300
N2—H22	0.87 (2)	C11—H11	0.9300
C1—C2	1.504 (2)	C12—H12	0.9300
C2—C7	1.384 (2)

O2—Co1—O4	87.55 (4)	Cl1—C4—C3	119.73 (12)
O2—Co1—N1	88.84 (4)	C3—C4—C5	121.47 (15)
O2—Co1—O2ⁱ	180.00	Cl1—C4—C5	118.79 (13)
O2—Co1—O4ⁱ	92.45 (4)	C4—C5—C6	118.90 (16)
O2—Co1—N1ⁱ	91.16 (4)	C5—C6—C7	120.53 (17)
O4—Co1—N1	87.69 (4)	C2—C7—C6	120.25 (15)
O2ⁱ—Co1—O4	92.45 (4)	N1—C8—C9	123.09 (13)
O4—Co1—O4ⁱ	180.00	C8—C9—C13	121.62 (13)
O4—Co1—N1ⁱ	92.31 (4)	C8—C9—C10	118.33 (13)
O2ⁱ—Co1—N1	91.16 (4)	C10—C9—C13	120.05 (12)
O4ⁱ—Co1—N1	92.31 (4)	C9—C10—C11	118.86 (13)
N1—Co1—N1ⁱ	180.00	C10—C11—C12	119.01 (14)
O2ⁱ—Co1—O4ⁱ	87.55 (4)	N1—C12—C11	122.80 (13)
O2ⁱ—Co1—N1ⁱ	88.84 (4)	N2—C13—C9	117.24 (13)
O4ⁱ—Co1—N1ⁱ	87.69 (4)	O3—C13—N2	121.59 (16)
Co1—O2—C1	126.89 (9)	O3—C13—C9	121.16 (14)
H41—O4—H42	105 (2)	C2—C3—H3	120.00
Co1—O4—H41	99.0 (15)	C4—C3—H3	120.00
Co1—O4—H42	117.1 (16)	C4—C5—H5	121.00
Co1—N1—C8	121.14 (9)	C6—C5—H5	121.00
Co1—N1—C12	120.97 (9)	C5—C6—H6	120.00
C8—N1—C12	117.88 (12)	C7—C6—H6	120.00
H21—N2—H22	117 (2)	C2—C7—H7	120.00
C13—N2—H21	121.8 (16)	C6—C7—H7	120.00
C13—N2—H22	120.5 (17)	N1—C8—H8	118.00
O1—C1—O2	125.34 (14)	C9—C8—H8	118.00
O1—C1—C2	117.92 (13)	C9—C10—H10	121.00
O2—C1—C2	116.70 (13)	C11—C10—H10	121.00
C1—C2—C3	120.41 (13)	C10—C11—H11	121.00
C1—C2—C7	119.92 (13)	C12—C11—H11	120.00
C3—C2—C7	119.63 (14)	N1—C12—H12	119.00
C2—C3—C4	119.23 (14)	C11—C12—H12	119.00

O4—Co1—O2—C1	−177.85 (12)	O2—C1—C2—C7	−169.65 (14)
N1—Co1—O2—C1	−90.11 (12)	C1—C2—C3—C4	−177.53 (14)
O4ⁱ—Co1—O2—C1	2.15 (12)	C7—C2—C3—C4	0.1 (2)
N1ⁱ—Co1—O2—C1	89.89 (12)	C1—C2—C7—C6	177.50 (15)
O2—Co1—N1—C8	−26.16 (11)	C3—C2—C7—C6	−0.1 (2)
O2—Co1—N1—C12	153.10 (11)	C2—C3—C4—Cl1	178.62 (12)
O4—Co1—N1—C8	61.44 (11)	C2—C3—C4—C5	0.0 (2)
O4—Co1—N1—C12	−119.31 (11)	Cl1—C4—C5—C6	−178.62 (14)
O2ⁱ—Co1—N1—C8	153.84 (11)	C3—C4—C5—C6	0.1 (3)
O2ⁱ—Co1—N1—C12	−26.90 (11)	C4—C5—C6—C7	−0.1 (3)
O4ⁱ—Co1—N1—C8	−118.56 (11)	C5—C6—C7—C2	0.1 (3)
O4ⁱ—Co1—N1—C12	60.69 (11)	N1—C8—C9—C10	0.1 (2)
Co1—O2—C1—O1	−18.0 (2)	N1—C8—C9—C13	−178.77 (13)
Co1—O2—C1—C2	159.69 (10)	C8—C9—C10—C11	1.3 (2)
Co1—N1—C8—C9	177.93 (11)	C13—C9—C10—C11	−179.86 (14)
C12—N1—C8—C9	−1.4 (2)	C8—C9—C13—O3	146.12 (16)
Co1—N1—C12—C11	−177.98 (12)	C8—C9—C13—N2	−33.2 (2)
C8—N1—C12—C11	1.3 (2)	C10—C9—C13—O3	−32.7 (2)
O1—C1—C2—C3	−174.24 (15)	C10—C9—C13—N2	148.03 (17)
O1—C1—C2—C7	8.2 (2)	C9—C10—C11—C12	−1.3 (2)
O2—C1—C2—C3	7.9 (2)	C10—C11—C12—N1	0.0 (2)

Symmetry code: (i) −x, −y+2, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···O3ⁱⁱ	0.84 (3)	2.24 (3)	2.876 (2)	133 (2)
N2—H22···O4ⁱⁱⁱ	0.87 (2)	2.27 (2)	3.012 (2)	143 (2)
O4—H41···O1ⁱ	0.92 (2)	1.68 (2)	2.5822 (16)	164 (2)
O4—H42···O3^iv	0.83 (3)	1.98 (3)	2.7892 (15)	166 (2)

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

Experimental details

Crystal data
Chemical formula	[Co(C₇H₄ClO₂)₂(C₆H₆N₂O)₂(H₂O)₂]
M_r	650.32
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	294
a, b, c (Å)	11.5181 (3), 8.8191 (2), 13.5089 (3)
β (°)	90.546 (2)
V (Å³)	1372.16 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.88
Crystal size (mm)	0.35 × 0.22 × 0.18

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2012)
T_min, T_max	0.793, 0.854
No. of measured, independent and observed [I > 2σ(I)] reflections	18960, 2797, 2667
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.074, 1.11
No. of reflections	2797
No. of parameters	204
No. of restraints	52
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.33

Computer programs: APEX2 (Bruker, 2012), SAINT (Bruker, 2012), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), WinGX (Farrugia, 2012) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···O3ⁱ	0.84 (3)	2.24 (3)	2.876 (2)	133 (2)
N2—H22···O4ⁱⁱ	0.87 (2)	2.27 (2)	3.012 (2)	143 (2)
O4—H41···O1ⁱⁱⁱ	0.92 (2)	1.68 (2)	2.5822 (16)	164 (2)
O4—H42···O3^iv	0.83 (3)	1.98 (3)	2.7892 (15)	166 (2)

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

Acknowledgements

The authors are indebted to Aksaray University and Science and Technology Application and Research Center of Aksaray University, Aksaray, Turkey, for the use of the X-ray diffractometer.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Aydın, Ö., Çaylak Delibaş, N., Necefoğlu, H. & Hökelek, T. (2012). Acta Cryst. E68, m521–m522. CSD CrossRef IUCr Journals Google Scholar
Bigoli, F., Braibanti, A., Pellinghelli, M. A. & Tiripicchio, A. (1972). Acta Cryst. B28, 962–966. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Bruker (2012). APEX2, SAINT and SADABS. Bruker AXS Inc. Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Hökelek, T., Dal, H., Tercan, B., Özbek, F. E. & Necefoğlu, H. (2009a). Acta Cryst. E65, m466–m467. Web of Science CSD CrossRef IUCr Journals Google Scholar
Hökelek, T., Dal, H., Tercan, B., Özbek, F. E. & Necefoğlu, H. (2009b). Acta Cryst. E65, m607–m608. Web of Science CSD CrossRef IUCr Journals Google Scholar
Hökelek, T., Gündüz, H. & Necefoğlu, H. (1996). Acta Cryst. C52, 2470–2473. CSD CrossRef Web of Science IUCr Journals Google Scholar
Hökelek, T. & Necefoğlu, H. (1998). Acta Cryst. C54, 1242–1244. Web of Science CSD CrossRef IUCr Journals Google Scholar
Hökelek, T. & Necefoğlu, H. (2007). Acta Cryst. E63, m821–m823. Web of Science CSD CrossRef IUCr Journals Google Scholar
Krishnamachari, K. A. V. R. (1974). Am. J. Clin. Nutr. 27, 108–111. CAS PubMed Web of Science Google Scholar
Necefoğlu, H., Maracı, A., Özbek, F. E., Tercan, B. & Hökelek, T. (2011b). Acta Cryst. E67, m619–m620. Web of Science CSD CrossRef IUCr Journals Google Scholar
Necefoğlu, H., Özbek, F. E., Öztürk, V., Tercan, B. & Hökelek, T. (2011a). Acta Cryst. E67, m900–m901. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sertçelik, M., Çaylak Delibaş, N., Necefoğlu, H. & Hökelek, T. (2012a). Acta Cryst. E68, m1091–m1092. CSD CrossRef IUCr Journals Google Scholar
Sertçelik, M., Çaylak Delibaş, N., Necefoğlu, H. & Hökelek, T. (2012b). Acta Cryst. E68, m946–m947. CSD CrossRef IUCr Journals Google Scholar
Sertçelik, M., Çaylak Delibaş, N., Necefoğlu, H. & Hökelek, T. (2012c). Acta Cryst. E68, m1067–m1068. 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