Diaqua­bis(4-methyl­amino­benzoato-κO)bis­(nicotinamide-κN1)cobalt(II)

Necefoğlu, H.; Aybirdi, Ö.; Tercan, B.; Ermiş, E.; Hökelek, T.

doi:10.1107/S1600536810010706

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 4| April 2010| Pages m448-m449

doi:10.1107/S1600536810010706

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Diaquabis(4-methylaminobenzoato-κO)bis(nicotinamide-κN¹)cobalt(II)

Hacali Necefoğlu,^a Özgür Aybirdi,^a Barış Tercan,^b Emel Ermiş ^c and Tuncer Hökelek ^d ^*

^aDepartment of Chemistry, Kafkas University, 36100 Kars, Turkey, ^bDepartment of Physics, Karabük University, 78050 Karabük, Turkey, ^cDepartment of Chemistry, Faculty of Science, Anadolu University, 26470 Yenibağlar, Eskişehir, Turkey, and ^dDepartment of Physics, Hacettepe University, 06800 Beytepe, Ankara, Turkey
^*Correspondence e-mail: merzifon@hacettepe.edu.tr

(Received 12 March 2010; accepted 22 March 2010; online 27 March 2010)

The asymmetric unit of the title Co^II complex, [Co(C₈H₈NO₂)₂(C₆H₆N₂O)₂(H₂O)₂], contains two half complex molecules with similar structures. The Co^II atoms are each located on an inversion center and each is coordinated by two 4-methylaminobenzoate (PMAB), two nicotinamide (NA) ligands and two water molecules in a distorted octahedral coordination. The dihedral angles between the carboxylate groups and the adjacent benzene rings are 3.0 (3) and 2.54 (19)°, while the pyridine and benzene rings are oriented at dihedral angles of 67.40 (8) and 66.25 (8)°. In the crystal structure, intermolecular O—H⋯O and N—H⋯O hydrogen bonds link the molecules into a supramolecular structure.

Related literature

For niacin, see: Krishnamachari (1974 ) and for the nicotinic acid derivative N,N-diethylnicotinamide, see: Bigoli et al. (1972 ). For related structures, see: Hökelek et al. (1996 ); Hökelek & Necefoğlu (1998 ); Hökelek et al. (2009a ,b ,c ).

Experimental

Crystal data

[Co(C₈H₈NO₂)₂(C₆H₆N₂O)₂(H₂O)₂]
M_r = 639.53
Triclinic, $[P \overline 1]$
a = 9.9014 (7) Å
b = 11.2891 (8) Å
c = 14.1824 (9) Å
α = 107.554 (5)°
β = 92.975 (4)°
γ = 92.836 (4)°
V = 1505.89 (18) Å³
Z = 2
Mo Kα radiation
μ = 0.63 mm⁻¹
T = 294 K
0.31 × 0.14 × 0.11 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.889, T_max = 0.934
25128 measured reflections
7337 independent reflections
3927 reflections with I > 2σ(I)
R_int = 0.050

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.120
S = 0.99
7337 reflections
433 parameters
11 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.64 e Å⁻³

Table 1
Selected bond lengths (Å)

Co1—O1	2.0553 (17)
Co1—O4	2.088 (2)
Co1—N2	2.153 (2)
Co2—O5	2.0696 (18)
Co2—O8	2.129 (2)
Co2—N5	2.159 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H41⋯O7ⁱ	0.88 (2)	1.75 (2)	2.618 (4)	173 (4)
O4—H42⋯O2ⁱⁱ	0.89 (4)	1.86 (4)	2.644 (3)	146 (4)
O8—H81⋯O3ⁱⁱⁱ	0.91 (2)	1.84 (2)	2.742 (3)	173 (3)
O8—H82⋯O6^iv	0.94 (3)	1.76 (3)	2.648 (3)	156 (3)
N3—H32⋯O2^v	0.91 (3)	2.04 (3)	2.939 (4)	168 (3)
N4—H4A⋯O4^v	0.88 (4)	2.53 (4)	3.288 (4)	145 (3)
N6—H61⋯O6^vi	0.90 (3)	2.08 (3)	2.973 (4)	169 (3)
N6—H62⋯O3ⁱ	0.88 (3)	2.36 (3)	3.124 (4)	146 (3)
Symmetry codes: (i) -x+1, -y+1, -z; (ii) -x+1, -y+1, -z+1; (iii) x, y+1, z; (iv) -x+2, -y+2, -z; (v) -x+2, -y+1, -z+1; (vi) 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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810010706/xu2735sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810010706/xu2735Isup2.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 asymmetric unit of the title complex, (I), contains two half molecules with Co atoms on inversion centers. Each molecule contains two 4-methylaminobenzoate (PMAB) and two nicotinamide (NA) ligands and two coordinated water molecules, all ligands being monodentate. The crystal structures of similar complexes of Cu^II, Co^II, Ni^II, Mn^II and Zn^II ions, [Cu(C₇H₅O₂)₂(C₁₀H₁₄N₂O)₂], (II) (Hökelek et al., 1996), [Co(C₆H₆N₂O)₂(C₇H₄NO₄)₂(H₂O)₂], (III) (Hökelek & Necefoğlu, 1998), [Ni(C₇H₄ClO₂)₂(C₆H₆N₂O)₂(H₂O)₂], (IV) (Hökelek et al., 2009a), [Mn(C₇H₄ClO₂)₂(C₁₀H₁₄N₂O)₂(H₂O)₂], (V) (Hökelek et al., 2009b) and [Zn(C₇H₄BrO₂)₂(C₆H₆N₂O)₂(H₂O)₂], (VI) (Hökelek et al., 2009c) have also been reported. In (II), the two benzoate ions are coordinated to the Cu atom as bidentate ligands, while in the other structures all ligands being monodentate.

Each of the two molecules in the asymmetric unit of the title complex, [Co(PMAB)₂(NA)₂(H₂O)₂], has a centre of symmetry and Co^II ion is surrounded by two PMAB and two NA ligands and two water molecules (Fig. 1). All ligands are monodentate. In each molecule, the four O atoms (O1, O4, O1', O4' and O5, O8, O5'', o8'') 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 N atoms of the NA ligands (N2, N2' and N5, N5'') in the axial positions (Fig. 1).

The near equality of the C1—O1 [1.274 (3) Å], C1—O2 [1.255 (3) Å] and C15—O5 [1.276 (3) Å], C15—O6 [1.262 (3) Å] bonds in the carboxylate groups indicate delocalized bonding arrangements, rather than localized single and double bonds. The average Co—O bond lengths are 2.0717 (19) and 2.0993 (19) Å (Table 1) and the Co atoms are displaced out of the least-squares planes of the carboxylate groups [(O1/C1/O2) and (O5/C15/O6)] by -0.4948 (1) and -0.3495 (1) Å, respectively. The dihedral angles between the planar carboxylate groups and the benzene rings A (C2—C7) and C (C16—C21) are 2.96 (27)° and 2.54 (19)°, respectively, while that between rings A and B (N2/C9—C13) and C and D (N5/C23—C27) are 67.40 (8) and 66.25 (8)°, respectively.

In the crystal structure, intermolecular O—H···O and N—H···O hydrogen bonds (Table 2) link the molecules into a supramolecular structure, in which they may be effective in the stabilization of the structure.

Related literature top

For niacin, see: Krishnamachari (1974) and for the nicotinic acid derivative N,N-diethylnicotinamide, see: Bigoli et al. (1972). For related structures, see: Hökelek et al. (1996); Hökelek & Necefoğlu (1998); Hökelek et al. (2009a,b,c).

Experimental top

The title compound was prepared by the reaction of CoSO₄.7(H₂O) (1.41 g, 5 mmol) in H₂O (30 ml) and NA (1.22 g, 10 mmol) in H₂O (20 ml) with sodium 4-methylaminobenzoate (1.74 g, 10 mmol) in H₂O (50 ml). The mixture was filtered and set aside to crystallize at ambient temperature for one week, 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).

Figures top

Fig. 1. The molecular 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 operators:(') 1 - x, 1 - y, 1 - z; ('') 2 - x, 2 - y, -z.

Diaquabis(4-methylaminobenzoato-κO)bis(nicotinamide- κN¹)cobalt(II) top

Crystal data top

[Co(C₈H₈NO₂)₂(C₆H₆N₂O)₂(H₂O)₂]	Z = 2
M_r = 639.53	F(000) = 666
Triclinic, P1	D_x = 1.410 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.9014 (7) Å	Cell parameters from 4808 reflections
b = 11.2891 (8) Å	θ = 2.5–22.9°
c = 14.1824 (9) Å	µ = 0.63 mm⁻¹
α = 107.554 (5)°	T = 294 K
β = 92.975 (4)°	Block, orange
γ = 92.836 (4)°	0.31 × 0.14 × 0.11 mm
V = 1505.89 (18) Å³

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	7337 independent reflections
Radiation source: fine-focus sealed tube	3927 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.050
ϕ and ω scans	θ_max = 28.3°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −10→13
T_min = 0.889, T_max = 0.934	k = −14→15
25128 measured reflections	l = −18→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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.120	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	w = 1/[σ²(F_o²) + (0.0507P)²] where P = (F_o² + 2F_c²)/3
7337 reflections	(Δ/σ)_max < 0.001
433 parameters	Δρ_max = 0.44 e Å⁻³
11 restraints	Δρ_min = −0.64 e Å⁻³

Crystal data top

[Co(C₈H₈NO₂)₂(C₆H₆N₂O)₂(H₂O)₂]	γ = 92.836 (4)°
M_r = 639.53	V = 1505.89 (18) Å³
Triclinic, P1	Z = 2
a = 9.9014 (7) Å	Mo Kα radiation
b = 11.2891 (8) Å	µ = 0.63 mm⁻¹
c = 14.1824 (9) Å	T = 294 K
α = 107.554 (5)°	0.31 × 0.14 × 0.11 mm
β = 92.975 (4)°

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	7337 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	3927 reflections with I > 2σ(I)
T_min = 0.889, T_max = 0.934	R_int = 0.050
25128 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	11 restraints
wR(F²) = 0.120	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	Δρ_max = 0.44 e Å⁻³
7337 reflections	Δρ_min = −0.64 e Å⁻³
433 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	0.5000	0.5000	0.03935 (17)
Co2	1.0000	1.0000	0.0000	0.03728 (17)
O1	0.56594 (18)	0.56020 (18)	0.38612 (14)	0.0449 (5)
O2	0.71996 (19)	0.7140 (2)	0.46562 (16)	0.0532 (6)
O3	0.8902 (2)	0.2578 (2)	0.27847 (16)	0.0663 (7)
O4	0.4510 (3)	0.3195 (2)	0.40609 (19)	0.0673 (7)
H41	0.447 (4)	0.285 (3)	0.3417 (13)	0.095 (14)*
H42	0.383 (3)	0.283 (4)	0.428 (3)	0.135 (18)*
O5	1.07631 (18)	0.95050 (19)	0.12042 (14)	0.0472 (5)
O6	1.1978 (2)	0.7922 (2)	0.04475 (15)	0.0528 (6)
O7	0.5387 (3)	0.7866 (4)	−0.21529 (18)	0.1282 (14)
O8	0.98305 (19)	1.1857 (2)	0.09213 (16)	0.0472 (5)
H81	0.958 (3)	1.207 (3)	0.1553 (12)	0.083 (12)*
H82	0.918 (3)	1.215 (3)	0.056 (2)	0.104 (15)*
N1	0.8652 (4)	0.6271 (3)	0.0185 (3)	0.0932 (13)
H1	0.931 (4)	0.680 (4)	0.027 (3)	0.101 (16)*
N2	0.7005 (2)	0.4443 (2)	0.52402 (18)	0.0444 (6)
N3	1.0849 (3)	0.2554 (3)	0.3640 (2)	0.0585 (8)
H31	1.122 (3)	0.222 (3)	0.3086 (17)	0.072 (12)*
H32	1.135 (3)	0.264 (3)	0.4217 (18)	0.075 (12)*
N4	1.3862 (4)	0.8673 (3)	0.4966 (2)	0.0738 (9)
H4A	1.441 (4)	0.808 (3)	0.495 (3)	0.125 (19)*
N5	0.7987 (2)	0.9412 (2)	0.02697 (17)	0.0395 (6)
N6	0.3613 (3)	0.7723 (3)	−0.1287 (2)	0.0589 (8)
H61	0.322 (3)	0.782 (4)	−0.0709 (19)	0.097 (15)*
H62	0.313 (3)	0.739 (3)	−0.1852 (18)	0.094 (14)*
C1	0.6647 (3)	0.6378 (3)	0.3879 (2)	0.0394 (7)
C2	0.7153 (3)	0.6358 (3)	0.2905 (2)	0.0407 (7)
C3	0.8201 (3)	0.7192 (3)	0.2835 (2)	0.0469 (8)
H3	0.8571	0.7793	0.3407	0.056*
C4	0.8694 (3)	0.7144 (3)	0.1946 (3)	0.0557 (9)
H4	0.9404	0.7704	0.1925	0.067*
C5	0.8157 (4)	0.6279 (3)	0.1075 (3)	0.0608 (9)
C6	0.7106 (4)	0.5444 (3)	0.1136 (2)	0.0702 (11)
H6	0.6731	0.4847	0.0564	0.084*
C7	0.6619 (3)	0.5501 (3)	0.2042 (2)	0.0581 (9)
H7	0.5910	0.4943	0.2068	0.070*
C8	0.8172 (6)	0.5427 (5)	−0.0756 (3)	0.130 (2)
H8A	0.8674	0.5600	−0.1266	0.194*
H8B	0.7227	0.5524	−0.0880	0.194*
H8C	0.8290	0.4588	−0.0756	0.194*
C9	0.7586 (3)	0.4567 (3)	0.6138 (2)	0.0510 (8)
H9	0.7126	0.4949	0.6694	0.061*
C10	0.8847 (3)	0.4149 (3)	0.6270 (2)	0.0586 (9)
H10	0.9228	0.4254	0.6905	0.070*
C11	0.9534 (3)	0.3580 (3)	0.5463 (2)	0.0504 (8)
H11	1.0387	0.3300	0.5544	0.060*
C12	0.8947 (3)	0.3427 (3)	0.4525 (2)	0.0372 (7)
C13	0.7679 (3)	0.3875 (3)	0.4461 (2)	0.0427 (7)
H13	0.7273	0.3771	0.3833	0.051*
C14	0.9565 (3)	0.2822 (3)	0.3585 (2)	0.0434 (7)
C15	1.1621 (3)	0.8704 (3)	0.1220 (2)	0.0412 (7)
C16	1.2203 (3)	0.8699 (3)	0.2201 (2)	0.0392 (7)
C17	1.3176 (3)	0.7886 (3)	0.2286 (2)	0.0444 (7)
H17	1.3464	0.7329	0.1716	0.053*
C18	1.3718 (3)	0.7889 (3)	0.3193 (2)	0.0506 (8)
H18	1.4372	0.7338	0.3227	0.061*
C19	1.3313 (3)	0.8698 (3)	0.4065 (2)	0.0512 (8)
C20	1.2335 (3)	0.9511 (3)	0.3987 (2)	0.0610 (9)
H20	1.2043	1.0065	0.4556	0.073*
C21	1.1798 (3)	0.9499 (3)	0.3069 (2)	0.0542 (8)
H21	1.1141	1.0046	0.3033	0.065*
C22	1.3480 (4)	0.9441 (4)	0.5901 (3)	0.0900 (13)
H22A	1.3968	0.9234	0.6426	0.135*
H22B	1.2524	0.9305	0.5946	0.135*
H22C	1.3693	1.0300	0.5959	0.135*
C23	0.7582 (3)	0.9468 (3)	0.1165 (2)	0.0473 (8)
H23	0.8186	0.9812	0.1716	0.057*
C24	0.6309 (3)	0.9038 (3)	0.1305 (2)	0.0555 (9)
H24	0.6069	0.9080	0.1939	0.067*
C25	0.5397 (3)	0.8547 (3)	0.0506 (2)	0.0500 (8)
H25	0.4525	0.8269	0.0590	0.060*
C26	0.5796 (3)	0.8473 (3)	−0.0430 (2)	0.0413 (7)
C27	0.7095 (3)	0.8909 (3)	−0.0501 (2)	0.0423 (7)
H27	0.7370	0.8850	−0.1130	0.051*
C28	0.4910 (3)	0.7982 (3)	−0.1358 (2)	0.0597 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0366 (3)	0.0502 (4)	0.0358 (3)	0.0086 (3)	0.0118 (2)	0.0174 (3)
Co2	0.0287 (3)	0.0528 (4)	0.0361 (3)	0.0039 (2)	0.0022 (2)	0.0220 (3)
O1	0.0377 (11)	0.0619 (13)	0.0409 (12)	−0.0003 (10)	0.0061 (9)	0.0244 (11)
O2	0.0475 (13)	0.0688 (15)	0.0435 (13)	−0.0024 (11)	0.0024 (10)	0.0185 (12)
O3	0.0491 (13)	0.1049 (19)	0.0384 (13)	0.0182 (13)	−0.0002 (11)	0.0104 (13)
O4	0.0795 (18)	0.0634 (16)	0.0509 (17)	−0.0046 (13)	0.0278 (14)	0.0030 (14)
O5	0.0372 (11)	0.0688 (14)	0.0457 (13)	0.0121 (10)	0.0036 (9)	0.0312 (11)
O6	0.0536 (13)	0.0680 (15)	0.0419 (13)	0.0137 (11)	0.0028 (11)	0.0229 (12)
O7	0.091 (2)	0.226 (4)	0.0340 (15)	−0.069 (2)	0.0089 (14)	0.001 (2)
O8	0.0396 (12)	0.0611 (14)	0.0403 (13)	0.0042 (10)	0.0031 (10)	0.0140 (12)
N1	0.137 (3)	0.079 (3)	0.060 (2)	−0.028 (2)	0.047 (2)	0.015 (2)
N2	0.0420 (14)	0.0562 (16)	0.0387 (15)	0.0089 (12)	0.0067 (12)	0.0188 (13)
N3	0.0435 (17)	0.078 (2)	0.048 (2)	0.0220 (15)	0.0064 (16)	0.0084 (17)
N4	0.107 (3)	0.070 (2)	0.0462 (19)	0.017 (2)	−0.0184 (18)	0.0227 (17)
N5	0.0330 (13)	0.0517 (15)	0.0356 (14)	0.0027 (11)	0.0041 (11)	0.0158 (12)
N6	0.0455 (18)	0.073 (2)	0.049 (2)	−0.0099 (15)	−0.0066 (16)	0.0087 (17)
C1	0.0327 (16)	0.0487 (19)	0.0444 (19)	0.0144 (14)	0.0059 (14)	0.0233 (16)
C2	0.0422 (17)	0.0439 (18)	0.0419 (18)	0.0071 (14)	0.0093 (14)	0.0204 (15)
C3	0.0459 (18)	0.0496 (19)	0.0495 (19)	−0.0011 (14)	0.0016 (15)	0.0224 (16)
C4	0.054 (2)	0.061 (2)	0.060 (2)	−0.0080 (16)	0.0127 (17)	0.0312 (19)
C5	0.084 (3)	0.052 (2)	0.052 (2)	−0.0005 (18)	0.0278 (19)	0.0217 (18)
C6	0.105 (3)	0.055 (2)	0.045 (2)	−0.020 (2)	0.022 (2)	0.0087 (18)
C7	0.068 (2)	0.055 (2)	0.050 (2)	−0.0122 (17)	0.0185 (17)	0.0154 (18)
C8	0.215 (6)	0.108 (4)	0.057 (3)	−0.038 (4)	0.054 (3)	0.012 (3)
C9	0.052 (2)	0.066 (2)	0.0403 (19)	0.0103 (16)	0.0120 (16)	0.0213 (17)
C10	0.054 (2)	0.083 (3)	0.041 (2)	0.0130 (18)	−0.0018 (16)	0.0220 (19)
C11	0.0420 (18)	0.065 (2)	0.047 (2)	0.0130 (15)	−0.0002 (15)	0.0199 (17)
C12	0.0331 (15)	0.0448 (17)	0.0357 (17)	0.0051 (13)	0.0026 (13)	0.0149 (14)
C13	0.0405 (17)	0.057 (2)	0.0330 (17)	0.0088 (14)	0.0019 (14)	0.0163 (15)
C14	0.0361 (17)	0.0513 (19)	0.0422 (19)	0.0084 (14)	0.0035 (15)	0.0123 (16)
C15	0.0321 (16)	0.053 (2)	0.0464 (19)	−0.0002 (14)	0.0020 (14)	0.0266 (17)
C16	0.0391 (16)	0.0417 (17)	0.0414 (18)	0.0016 (13)	−0.0041 (14)	0.0208 (15)
C17	0.0459 (17)	0.0493 (19)	0.0418 (18)	0.0056 (14)	0.0030 (14)	0.0193 (15)
C18	0.0485 (19)	0.053 (2)	0.056 (2)	0.0137 (15)	−0.0057 (16)	0.0263 (18)
C19	0.062 (2)	0.050 (2)	0.044 (2)	0.0020 (16)	−0.0131 (17)	0.0217 (17)
C20	0.084 (3)	0.057 (2)	0.041 (2)	0.0205 (19)	−0.0042 (18)	0.0108 (17)
C21	0.064 (2)	0.051 (2)	0.049 (2)	0.0187 (16)	−0.0065 (17)	0.0167 (17)
C22	0.134 (4)	0.087 (3)	0.046 (2)	0.007 (3)	−0.020 (2)	0.021 (2)
C23	0.0425 (18)	0.065 (2)	0.0356 (17)	−0.0014 (15)	−0.0003 (14)	0.0192 (16)
C24	0.0474 (19)	0.088 (3)	0.0362 (18)	−0.0034 (18)	0.0104 (15)	0.0261 (18)
C25	0.0361 (17)	0.068 (2)	0.0447 (19)	−0.0073 (15)	0.0085 (15)	0.0170 (17)
C26	0.0357 (16)	0.0489 (18)	0.0381 (17)	−0.0016 (13)	0.0039 (13)	0.0120 (15)
C27	0.0402 (17)	0.0529 (19)	0.0339 (17)	0.0028 (14)	0.0089 (14)	0.0125 (15)
C28	0.055 (2)	0.071 (2)	0.043 (2)	−0.0177 (18)	0.0018 (17)	0.0048 (18)

Geometric parameters (Å, º) top

Co1—O1	2.0553 (17)	C3—H3	0.9300
Co1—O1ⁱ	2.0553 (17)	C4—C5	1.384 (4)
Co1—O4	2.088 (2)	C4—H4	0.9300
Co1—O4ⁱ	2.088 (2)	C5—C6	1.392 (4)
Co1—N2	2.153 (2)	C6—C7	1.381 (4)
Co1—N2ⁱ	2.153 (2)	C6—H6	0.9300
Co2—O5	2.0696 (18)	C7—H7	0.9300
Co2—O5ⁱⁱ	2.0696 (18)	C8—H8A	0.9600
Co2—O8	2.129 (2)	C8—H8B	0.9600
Co2—O8ⁱⁱ	2.129 (2)	C8—H8C	0.9600
Co2—N5	2.159 (2)	C9—H9	0.9300
Co2—N5ⁱⁱ	2.159 (2)	C10—C9	1.380 (4)
O1—C1	1.274 (3)	C10—H10	0.9300
O2—C1	1.255 (3)	C11—C10	1.366 (4)
O3—C14	1.229 (3)	C11—H11	0.9300
O4—H41	0.876 (17)	C12—C11	1.381 (4)
O4—H42	0.89 (4)	C12—C14	1.481 (4)
O5—C15	1.276 (3)	C13—C12	1.385 (4)
O6—C15	1.262 (3)	C13—H13	0.9300
O7—C28	1.218 (4)	C15—C16	1.479 (4)
O8—H81	0.907 (14)	C16—C17	1.389 (4)
O8—H82	0.932 (18)	C16—C21	1.382 (4)
N1—C5	1.376 (4)	C17—C18	1.365 (4)
N1—C8	1.428 (5)	C17—H17	0.9300
N1—H1	0.84 (4)	C18—C19	1.389 (4)
N2—C9	1.335 (3)	C18—H18	0.9300
N2—C13	1.330 (3)	C19—C20	1.389 (4)
N3—C14	1.325 (4)	C20—C21	1.375 (4)
N3—H31	0.870 (19)	C20—H20	0.9300
N3—H32	0.909 (19)	C21—H21	0.9300
N4—C19	1.371 (4)	C22—H22A	0.9600
N4—C22	1.430 (5)	C22—H22B	0.9600
N4—H4A	0.87 (2)	C22—H22C	0.9600
N5—C23	1.336 (3)	C23—H23	0.9300
N5—C27	1.331 (3)	C24—C23	1.373 (4)
N6—C28	1.319 (4)	C24—H24	0.9300
N6—H61	0.904 (19)	C25—C24	1.369 (4)
N6—H62	0.878 (19)	C25—H25	0.9300
C1—C2	1.488 (4)	C26—C25	1.383 (4)
C2—C3	1.393 (4)	C26—C28	1.484 (4)
C2—C7	1.371 (4)	C27—C26	1.374 (4)
C3—C4	1.362 (4)	C27—H27	0.9300

O1ⁱ—Co1—O1	180.000 (1)	C7—C6—H6	119.9
O1—Co1—O4	92.44 (9)	C2—C7—C6	121.8 (3)
O1ⁱ—Co1—O4	87.56 (9)	C2—C7—H7	119.1
O1—Co1—O4ⁱ	87.56 (9)	C6—C7—H7	119.1
O1ⁱ—Co1—O4ⁱ	92.44 (9)	N1—C8—H8A	109.5
O1—Co1—N2	89.34 (8)	N1—C8—H8B	109.5
O1ⁱ—Co1—N2	90.66 (8)	N1—C8—H8C	109.5
O1—Co1—N2ⁱ	90.66 (8)	H8A—C8—H8B	109.5
O1ⁱ—Co1—N2ⁱ	89.34 (8)	H8A—C8—H8C	109.5
O4ⁱ—Co1—O4	180.00 (9)	H8B—C8—H8C	109.5
O4—Co1—N2	88.05 (10)	N2—C9—C10	122.1 (3)
O4ⁱ—Co1—N2	91.95 (10)	N2—C9—H9	118.9
O4—Co1—N2ⁱ	91.95 (10)	C10—C9—H9	118.9
O4ⁱ—Co1—N2ⁱ	88.05 (10)	C9—C10—H10	120.1
N2ⁱ—Co1—N2	180.0	C11—C10—C9	119.8 (3)
O5ⁱⁱ—Co2—O5	180.00 (10)	C11—C10—H10	120.1
O5—Co2—O8	90.59 (8)	C10—C11—C12	119.2 (3)
O5ⁱⁱ—Co2—O8	89.41 (8)	C10—C11—H11	120.4
O5—Co2—O8ⁱⁱ	89.41 (8)	C12—C11—H11	120.4
O5ⁱⁱ—Co2—O8ⁱⁱ	90.59 (8)	C11—C12—C13	117.2 (3)
O5—Co2—N5	89.28 (8)	C11—C12—C14	125.2 (3)
O5ⁱⁱ—Co2—N5	90.72 (8)	C13—C12—C14	117.6 (2)
O5—Co2—N5ⁱⁱ	90.72 (8)	N2—C13—C12	124.2 (3)
O5ⁱⁱ—Co2—N5ⁱⁱ	89.28 (8)	N2—C13—H13	117.9
O8ⁱⁱ—Co2—O8	180.00 (12)	C12—C13—H13	117.9
O8—Co2—N5	92.47 (8)	O3—C14—N3	121.5 (3)
O8ⁱⁱ—Co2—N5	87.53 (8)	O3—C14—C12	120.8 (3)
O8—Co2—N5ⁱⁱ	87.53 (8)	N3—C14—C12	117.7 (3)
O8ⁱⁱ—Co2—N5ⁱⁱ	92.47 (8)	O5—C15—C16	117.4 (3)
N5—Co2—N5ⁱⁱ	180.0	O6—C15—O5	123.2 (3)
C1—O1—Co1	128.64 (18)	O6—C15—C16	119.4 (3)
Co1—O4—H41	134 (2)	C17—C16—C15	121.3 (3)
Co1—O4—H42	111 (3)	C21—C16—C17	117.2 (3)
H42—O4—H41	106 (3)	C21—C16—C15	121.5 (3)
C15—O5—Co2	128.33 (19)	C16—C17—H17	119.4
Co2—O8—H81	125 (2)	C18—C17—C16	121.1 (3)
Co2—O8—H82	103 (2)	C18—C17—H17	119.4
H81—O8—H82	106 (2)	C17—C18—C19	121.5 (3)
C5—N1—C8	124.7 (3)	C17—C18—H18	119.2
C5—N1—H1	111 (3)	C19—C18—H18	119.2
C8—N1—H1	124 (3)	N4—C19—C20	121.9 (3)
C9—N2—Co1	123.3 (2)	N4—C19—C18	120.3 (3)
C13—N2—Co1	119.12 (19)	C20—C19—C18	117.7 (3)
C13—N2—C9	117.5 (2)	C19—C20—H20	119.9
C14—N3—H31	118 (2)	C21—C20—C19	120.2 (3)
C14—N3—H32	124 (2)	C21—C20—H20	119.9
H31—N3—H32	118 (3)	C16—C21—H21	118.9
C19—N4—C22	124.4 (3)	C20—C21—C16	122.2 (3)
C19—N4—H4A	116 (3)	C20—C21—H21	118.9
C22—N4—H4A	119 (3)	N4—C22—H22A	109.5
C23—N5—Co2	124.23 (19)	N4—C22—H22B	109.5
C27—N5—Co2	118.79 (18)	N4—C22—H22C	109.5
C27—N5—C23	116.9 (2)	H22A—C22—H22B	109.5
C28—N6—H61	124 (2)	H22A—C22—H22C	109.5
C28—N6—H62	116 (2)	H22B—C22—H22C	109.5
H62—N6—H61	120 (3)	N5—C23—C24	122.7 (3)
O1—C1—C2	116.6 (3)	N5—C23—H23	118.7
O2—C1—O1	124.1 (3)	C24—C23—H23	118.7
O2—C1—C2	119.3 (3)	C23—C24—H24	120.2
C3—C2—C1	121.4 (3)	C25—C24—C23	119.6 (3)
C7—C2—C1	121.1 (3)	C25—C24—H24	120.2
C7—C2—C3	117.5 (3)	C24—C25—C26	118.8 (3)
C2—C3—H3	119.3	C24—C25—H25	120.6
C4—C3—C2	121.3 (3)	C26—C25—H25	120.6
C4—C3—H3	119.3	C25—C26—C28	124.6 (3)
C3—C4—C5	121.2 (3)	C27—C26—C25	117.7 (3)
C3—C4—H4	119.4	C27—C26—C28	117.8 (3)
C5—C4—H4	119.4	N5—C27—C26	124.4 (3)
N1—C5—C4	120.0 (3)	N5—C27—H27	117.8
N1—C5—C6	122.1 (4)	C26—C27—H27	117.8
C4—C5—C6	117.9 (3)	O7—C28—N6	122.2 (3)
C5—C6—H6	119.9	O7—C28—C26	119.5 (3)
C7—C6—C5	120.2 (3)	N6—C28—C26	118.3 (3)

O4ⁱ—Co1—O1—C1	36.6 (2)	C1—C2—C3—C4	177.7 (3)
O4—Co1—O1—C1	−143.4 (2)	C7—C2—C3—C4	−1.1 (4)
N2ⁱ—Co1—O1—C1	124.6 (2)	C1—C2—C7—C6	−177.9 (3)
N2—Co1—O1—C1	−55.4 (2)	C3—C2—C7—C6	1.0 (5)
O8ⁱⁱ—Co2—O5—C15	32.2 (2)	C2—C3—C4—C5	1.1 (5)
O8—Co2—O5—C15	−147.8 (2)	C3—C4—C5—N1	178.4 (3)
N5—Co2—O5—C15	119.8 (2)	C3—C4—C5—C6	−0.8 (5)
N5ⁱⁱ—Co2—O5—C15	−60.2 (2)	N1—C5—C6—C7	−178.6 (4)
O1ⁱ—Co1—N2—C13	138.0 (2)	C4—C5—C6—C7	0.6 (5)
O1—Co1—N2—C13	−42.0 (2)	C5—C6—C7—C2	−0.7 (5)
O4ⁱ—Co1—N2—C13	−129.5 (2)	C11—C10—C9—N2	−0.4 (5)
O4—Co1—N2—C13	50.5 (2)	C12—C11—C10—C9	−0.4 (5)
O1ⁱ—Co1—N2—C9	−37.7 (2)	C13—C12—C11—C10	0.4 (4)
O1—Co1—N2—C9	142.3 (2)	C14—C12—C11—C10	−179.5 (3)
O4ⁱ—Co1—N2—C9	54.8 (2)	C11—C12—C14—O3	170.4 (3)
O4—Co1—N2—C9	−125.2 (2)	C11—C12—C14—N3	−9.6 (4)
O5ⁱⁱ—Co2—N5—C27	33.7 (2)	C13—C12—C14—O3	−9.5 (4)
O5—Co2—N5—C27	−146.3 (2)	C13—C12—C14—N3	170.5 (3)
O8ⁱⁱ—Co2—N5—C27	−56.8 (2)	N2—C13—C12—C11	0.4 (4)
O8—Co2—N5—C27	123.2 (2)	N2—C13—C12—C14	−179.7 (3)
O5ⁱⁱ—Co2—N5—C23	−149.3 (2)	O5—C15—C16—C17	−177.9 (2)
O5—Co2—N5—C23	30.7 (2)	O5—C15—C16—C21	2.4 (4)
O8ⁱⁱ—Co2—N5—C23	120.2 (2)	O6—C15—C16—C17	2.7 (4)
O8—Co2—N5—C23	−59.8 (2)	O6—C15—C16—C21	−177.0 (3)
Co1—O1—C1—O2	−18.0 (4)	C15—C16—C17—C18	179.6 (3)
Co1—O1—C1—C2	162.07 (17)	C21—C16—C17—C18	−0.7 (4)
Co2—O5—C15—O6	−12.4 (4)	C15—C16—C21—C20	−179.6 (3)
Co2—O5—C15—C16	168.20 (17)	C17—C16—C21—C20	0.7 (5)
C8—N1—C5—C4	−179.7 (4)	C16—C17—C18—C19	0.5 (5)
C8—N1—C5—C6	−0.5 (7)	C17—C18—C19—N4	179.3 (3)
Co1—N2—C9—C10	176.9 (2)	C17—C18—C19—C20	−0.1 (5)
C13—N2—C9—C10	1.1 (4)	N4—C19—C20—C21	−179.3 (3)
Co1—N2—C13—C12	−177.1 (2)	C18—C19—C20—C21	0.1 (5)
C9—N2—C13—C12	−1.1 (4)	C19—C20—C21—C16	−0.4 (5)
C22—N4—C19—C18	−178.1 (3)	C25—C24—C23—N5	−1.1 (5)
C22—N4—C19—C20	1.3 (6)	C26—C25—C24—C23	1.4 (5)
Co2—N5—C23—C24	−177.3 (2)	C27—C26—C25—C24	−0.5 (5)
C27—N5—C23—C24	−0.2 (4)	C28—C26—C25—C24	−179.0 (3)
Co2—N5—C27—C26	178.4 (2)	C25—C26—C28—O7	−174.4 (4)
C23—N5—C27—C26	1.2 (4)	C25—C26—C28—N6	7.8 (5)
O1—C1—C2—C3	178.0 (2)	C27—C26—C28—O7	7.1 (5)
O1—C1—C2—C7	−3.1 (4)	C27—C26—C28—N6	−170.7 (3)
O2—C1—C2—C3	−1.9 (4)	N5—C27—C26—C25	−0.9 (5)
O2—C1—C2—C7	176.9 (3)	N5—C27—C26—C28	177.7 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H41···O7ⁱⁱⁱ	0.88 (2)	1.75 (2)	2.618 (4)	173 (4)
O4—H42···O2ⁱ	0.89 (4)	1.86 (4)	2.644 (3)	146 (4)
O8—H81···O3^iv	0.91 (2)	1.84 (2)	2.742 (3)	173 (3)
O8—H82···O6ⁱⁱ	0.94 (3)	1.76 (3)	2.648 (3)	156 (3)
N3—H32···O2^v	0.91 (3)	2.04 (3)	2.939 (4)	168 (3)
N4—H4A···O4^v	0.88 (4)	2.53 (4)	3.288 (4)	145 (3)
N6—H61···O6^vi	0.90 (3)	2.08 (3)	2.973 (4)	169 (3)
N6—H62···O3ⁱⁱⁱ	0.88 (3)	2.36 (3)	3.124 (4)	146 (3)

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

Experimental details

Crystal data
Chemical formula	[Co(C₈H₈NO₂)₂(C₆H₆N₂O)₂(H₂O)₂]
M_r	639.53
Crystal system, space group	Triclinic, P1
Temperature (K)	294
a, b, c (Å)	9.9014 (7), 11.2891 (8), 14.1824 (9)
α, β, γ (°)	107.554 (5), 92.975 (4), 92.836 (4)
V (Å³)	1505.89 (18)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.63
Crystal size (mm)	0.31 × 0.14 × 0.11

Data collection
Diffractometer	Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.889, 0.934
No. of measured, independent and observed [I > 2σ(I)] reflections	25128, 7337, 3927
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.120, 0.99
No. of reflections	7337
No. of parameters	433
No. of restraints	11
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.64

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

Selected bond lengths (Å) top

Co1—O1	2.0553 (17)	Co2—O5	2.0696 (18)
Co1—O4	2.088 (2)	Co2—O8	2.129 (2)
Co1—N2	2.153 (2)	Co2—N5	2.159 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H41···O7ⁱ	0.876 (18)	1.747 (19)	2.618 (4)	173 (4)
O4—H42···O2ⁱⁱ	0.89 (4)	1.86 (4)	2.644 (3)	146 (4)
O8—H81···O3ⁱⁱⁱ	0.906 (19)	1.840 (19)	2.742 (3)	173 (3)
O8—H82···O6^iv	0.94 (3)	1.76 (3)	2.648 (3)	156 (3)
N3—H32···O2^v	0.91 (3)	2.04 (3)	2.939 (4)	168 (3)
N4—H4A···O4^v	0.88 (4)	2.53 (4)	3.288 (4)	145 (3)
N6—H61···O6^vi	0.90 (3)	2.08 (3)	2.973 (4)	169 (3)
N6—H62···O3ⁱ	0.88 (3)	2.36 (3)	3.124 (4)	146 (3)

Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+1, −y+1, −z+1; (iii) x, y+1, z; (iv) −x+2, −y+2, −z; (v) −x+2, −y+1, −z+1; (vi) 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 X-ray diffractometer. This work was financially supported by the Scientific and Technological Research Council of Turkey (grant No. 108 T657).

References

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
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