Diaqua­(isonicotinamide-κN1)(4-meth­oxy­benzoato-κ2O,O′)(4-meth­oxy­benzoato-κO)cobalt(II)

Hökelek, T.; Süzen, Y.; Tercan, B.; Tenlik, E.; Necefoğlu, H.

doi:10.1107/S160053681002194X

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Pages m784-m785

doi:10.1107/S160053681002194X

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Diaqua(isonicotinamide-κN¹)(4-methoxybenzoato-κ²O,O′)(4-methoxybenzoato-κO)cobalt(II)

Tuncer Hökelek,^a ^* Yasemin Süzen,^b Barış Tercan,^c Erdinç Tenlik ^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 3 June 2010; accepted 8 June 2010; online 16 June 2010)

In the title complex, [Co(C₈H₇O₃)₂(C₆H₆N₂O)(H₂O)₂], the Co^II atom is coordinated by three O atoms from two 4-methoxybenzoate ligands, which act in different modes, viz. monodentate and bidentate, two water molecules and one N atom of the isonicotinamide ligand in a distorted octahedral geometry. The monodentate-coordinated carboxylate group is involved in an intramolecular O—H⋯O hydrogen bond with the coordinated water molecule. In the crystal structure, intermolecular O—H⋯O and N—H⋯O hydrogen bonds link the molecules into layers parallel to the ab plane. The crystal packing is further stabilized by weak C—H⋯O hydrogen bonds and π–π interactions indicated by the short distance of 3.6181 (8) Å between the centroids of the benzene and pyridine rings of neighbouring molecules.

Related literature

For general background to niacin and the nicotinic acid derivative N,N-diethylnicotinamide, see: Krishnamachari (1974 ) and Bigoli et al. (1972 ), respectively. For related structures, see: Greenaway et al. (1984 ); Hökelek et al. (2009a ,b ,c ,d ); Necefoğlu et al. (2010 ).

Experimental

Crystal data

[Co(C₈H₇O₃)₂(C₆H₆N₂O)(H₂O)₂]
M_r = 519.36
Monoclinic, P 2₁
a = 8.2666 (2) Å
b = 6.8055 (2) Å
c = 20.5415 (4) Å
β = 99.808 (2)°
V = 1138.74 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.81 mm⁻¹
T = 100 K
0.39 × 0.32 × 0.28 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.739, T_max = 0.791
11263 measured reflections
4838 independent reflections
4597 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.022
wR(F²) = 0.050
S = 1.01
4838 reflections
333 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.24 e Å⁻³
Absolute structure: Flack (1983 ), 1761 Friedel pairs
Flack parameter: 0.015 (7)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O2ⁱ	0.79 (3)	2.11 (3)	2.877 (2)	164.0 (17)
N2—H2B⋯O1ⁱⁱ	0.91 (3)	2.16 (3)	3.050 (2)	167 (2)
O8—H81⋯O4	0.83 (3)	1.84 (3)	2.6577 (17)	167 (3)
O8—H82⋯O7ⁱⁱⁱ	0.89 (2)	1.86 (3)	2.7427 (16)	172 (2)
O9—H91⋯O6^iv	0.786 (19)	2.078 (19)	2.8384 (16)	163 (2)
O9—H92⋯O4^v	0.91 (3)	1.72 (3)	2.6307 (18)	174.1 (15)
C8—H8A⋯O7^vi	0.96	2.53	3.466 (2)	166
C16—H16B⋯O4^vii	0.96	2.52	3.4752 (18)	171
Symmetry codes: (i) x+1, y, z; (ii) x+1, y+1, z; (iii) x-1, y-1, z; (iv) x-1, y+1, z; (v) x, y+1, z; (vi) $[-x+2, y-{\script{3\over 2}}, -z+2]$ ; (vii) $[-x+2, y-{\script{1\over 2}}, -z+1]$ .

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: ORTEP-3 for Windows (Farrugia, 1997 ); 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/S160053681002194X/cv2727sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681002194X/cv2727Isup2.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 has been synthesized. Herein we report its crystal structure.

The title compound, (I), is a monomeric complex, where the Co^II ion is surrounded by two methoxybenzoate (MB) anions, one isonicotinamide (INA) ligand and two coordinated water molecules. One of the MB anions acts as a bidentate ligand, while the other is monodentate. The structures of similar complexes , [Mn(C₉H₁₀NO₂)₂(C₆H₆N₂O)(H₂O)₂] (II) (Hökelek et al., 2009a), [Co(C₉H₁₀NO₂)₂(C₆H₆N₂O)(H₂O)₂] (III) (Hökelek et al., 2009b), [Cd(C₈H₇O₂)₂(C₆H₆N₂O)₂(H₂O)].H₂O (IV) (Necefoğlu et al., 2010), [Zn(C₉H₁₀NO₂)₂(C₆H₆N₂O)(H₂O)₂] (V) (Hökelek et al., 2009c) and [Zn(C₈H₈NO₂)₂(C₆H₆N₂O)₂].H₂O (VI) (Hökelek et al., 2009d) have also been determined.

In (I) (Fig. 1), the four O atoms (O1, O2, O5 and O9) in the equatorial plane around the Co1 form a highly distorted square-planar arrangement, while the distorted octahedral coordination geometry is completed by the N atom (N1) of INA ligand and the O atom (O8) of the second water molecule in the axial positions. The average Co—O bond length is 2.1171 (12) Å and the Co atom is displaced out of the least-squares planes of the carboxylate groups (O1/C1/O2) and (O4/C9/O5) by -0.0061 (2) Å and -0.5367 (2) Å, respectively. The dihedral angle between the planar carboxylate groups and the adjacent benzene rings A (C2—C7) and B (C9—C14) are 12.12 (12)° and 9.26 (13)°, respectively, while those between rings A, B and C (N1/C17—C21) are A/B = 78.18 (4), A/C = 74.20 (5) and B/C = 6.23 (5) °. The intramolecular O—H···O hydrogen bond (Table 1) between the monodentate-coordinated carboxyl group and a coordinated water molecule results in a six-membered ring D (Co1/O4/O5/O8/C9/H81) adopting envelope conformation, with atom Co1 displaced by -0.5481 (2) Å from the plane of the other ring atoms. In (I), the O1—Co1—O2 angle is 60.32 (4)°. The corresponding O—M—O (where M is a metal) angles are 54.71 (4)° in (IV), 60.03 (6)° in (V), 59.02 (8)° in (VI) and 55.2 (1)° in [Cu(Asp)₂(py)₂] (where Asp is acetylsalicylate and py is pyridine) [(VII); Greenaway et al., 1984].

In the crystal structure, intermolecular O—H···O and N—H···O hydrogen bonds (Table 1) link the molecules into layers parallel to ab plane. The crystal packing is further stabilized by the weak C—H···O hydrogen bonds (Table 1). The π–π contact between the benzene and pyridine rings, Cg2—Cg3ⁱ [symmetry code: (i) x, y + 1, z, where Cg2 and Cg3 are the centroids of the rings B (C9—C14) and C (N1/C17—C21), respectively] may also stabilize the structure, with centroid-centroid distance of 3.6181 (8) Å.

Related literature top

For general background to niacin and the nicotinic acid derivative N,N-diethylnicotinamide, see: Krishnamachari (1974) and Bigoli et al. (1972), respectively. For related structures, see: Greenaway et al. (1984); Hökelek et al. (2009a,b,c,d); Necefoğlu et al. (2010).

Experimental top

The title compound was prepared by the reaction of CoSO₄.7H₂O (2.81 g, 10 mmol) in H₂O (50 ml) and INA (2.44 g, 20 mmol) in H₂O (50 ml) with sodium 4-methoxybenzoate (3.48 g, 20 mmol) in H₂O (100 ml). The mixture was filtered and set aside to crystallize at ambient temperature for one week, giving brown 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: ORTEP-3 for Windows (Farrugia, 1997); 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. Displacement ellipsoids are drawn at the 50% probability level. Dashed line indicates the hydrogen-bonding.

Diaqua(isonicotinamide-κN¹)(4-methoxybenzoato- κ²O,O')(4-methoxybenzoato-κO)cobalt(II) top

Crystal data top

[Co(C₈H₇O₃)₂(C₆H₆N₂O)(H₂O)₂]	F(000) = 538
M_r = 519.36	D_x = 1.515 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 6882 reflections
a = 8.2666 (2) Å	θ = 2.5–28.4°
b = 6.8055 (2) Å	µ = 0.81 mm⁻¹
c = 20.5415 (4) Å	T = 100 K
β = 99.808 (2)°	Block, brown
V = 1138.74 (5) Å³	0.39 × 0.32 × 0.28 mm
Z = 2

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	4838 independent reflections
Radiation source: fine-focus sealed tube	4597 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
ϕ and ω scans	θ_max = 28.4°, θ_min = 1.0°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −11→9
T_min = 0.739, T_max = 0.791	k = −8→9
11263 measured reflections	l = −27→27

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.022	w = 1/[σ²(F_o²) + (0.0215P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.050	(Δ/σ)_max = 0.003
S = 1.01	Δρ_max = 0.29 e Å⁻³
4838 reflections	Δρ_min = −0.24 e Å⁻³
333 parameters	Absolute structure: Flack (1983), 1761 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.015 (7)
Secondary atom site location: difference Fourier map

Crystal data top

[Co(C₈H₇O₃)₂(C₆H₆N₂O)(H₂O)₂]	V = 1138.74 (5) Å³
M_r = 519.36	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 8.2666 (2) Å	µ = 0.81 mm⁻¹
b = 6.8055 (2) Å	T = 100 K
c = 20.5415 (4) Å	0.39 × 0.32 × 0.28 mm
β = 99.808 (2)°

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	4838 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	4597 reflections with I > 2σ(I)
T_min = 0.739, T_max = 0.791	R_int = 0.020
11263 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.022	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.050	Δρ_max = 0.29 e Å⁻³
S = 1.01	Δρ_min = −0.24 e Å⁻³
4838 reflections	Absolute structure: Flack (1983), 1761 Friedel pairs
333 parameters	Absolute structure parameter: 0.015 (7)

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	0.83963 (2)	0.92738 (3)	0.717117 (8)	0.01106 (5)
O1	0.87439 (13)	0.72789 (18)	0.79844 (5)	0.0132 (2)
O2	0.75818 (13)	1.01182 (18)	0.81134 (5)	0.0145 (2)
O3	0.68768 (15)	0.5746 (2)	1.08004 (5)	0.0212 (3)
O4	0.78237 (13)	0.51498 (18)	0.63163 (5)	0.0156 (2)
O5	0.95880 (13)	0.76378 (18)	0.65605 (5)	0.0146 (2)
O6	1.43741 (13)	0.13627 (18)	0.56391 (5)	0.0160 (2)
O7	1.44482 (14)	1.65456 (18)	0.77779 (5)	0.0160 (2)
O8	0.60930 (14)	0.78883 (19)	0.68139 (6)	0.0147 (2)
H81	0.652 (3)	0.692 (4)	0.6668 (10)	0.024 (6)*
H82	0.564 (3)	0.750 (4)	0.7153 (12)	0.052 (7)*
O9	0.72143 (15)	1.1511 (2)	0.66328 (6)	0.0177 (3)
H91	0.639 (2)	1.126 (4)	0.6396 (10)	0.024 (6)*
H92	0.749 (2)	1.277 (4)	0.6543 (9)	0.021 (5)*
N1	1.05301 (16)	1.0966 (2)	0.74674 (6)	0.0127 (3)
N2	1.62169 (17)	1.4016 (3)	0.79899 (7)	0.0175 (3)
H2A	1.643 (2)	1.290 (4)	0.8055 (9)	0.015 (5)*
H2B	1.708 (3)	1.486 (4)	0.8026 (10)	0.033 (6)*
C1	0.80942 (19)	0.8473 (3)	0.83434 (7)	0.0130 (3)
C2	0.79173 (19)	0.7843 (3)	0.90221 (7)	0.0140 (3)
C3	0.86387 (19)	0.6109 (3)	0.92813 (7)	0.0172 (3)
H3	0.9323	0.5420	0.9046	0.021*
C4	0.8362 (2)	0.5378 (3)	0.98853 (7)	0.0190 (4)
H4	0.8862	0.4220	1.0056	0.023*
C5	0.7328 (2)	0.6403 (3)	1.02288 (7)	0.0172 (4)
C6	0.6650 (2)	0.8189 (3)	0.99909 (8)	0.0200 (4)
H6	0.6001	0.8901	1.0235	0.024*
C7	0.69427 (19)	0.8905 (3)	0.93914 (7)	0.0172 (4)
H7	0.6489	1.0099	0.9233	0.021*
C8	0.7330 (2)	0.3780 (3)	1.10016 (8)	0.0238 (4)
H8A	0.6763	0.3397	1.1352	0.036*
H8B	0.8493	0.3718	1.1154	0.036*
H8C	0.7038	0.2906	1.0633	0.036*
C9	0.92278 (19)	0.5941 (2)	0.63394 (7)	0.0125 (3)
C10	1.05374 (18)	0.4757 (2)	0.60954 (7)	0.0122 (4)
C11	1.0197 (2)	0.2936 (3)	0.57978 (7)	0.0160 (3)
H11	0.9117	0.2493	0.5716	0.019*
C12	1.14209 (19)	0.1759 (3)	0.56200 (7)	0.0160 (3)
H12	1.1168	0.0551	0.5416	0.019*
C13	1.30388 (19)	0.2427 (3)	0.57528 (7)	0.0135 (3)
C14	1.33919 (17)	0.4281 (3)	0.60267 (6)	0.0160 (3)
H14	1.4464	0.4749	0.6093	0.019*
C15	1.2158 (2)	0.5421 (3)	0.61986 (7)	0.0148 (3)
H15	1.2406	0.6651	0.6386	0.018*
C16	1.4086 (2)	−0.0503 (3)	0.53119 (7)	0.0191 (4)
H16A	1.5118	−0.1095	0.5271	0.029*
H16B	1.3448	−0.0312	0.4880	0.029*
H16C	1.3501	−0.1347	0.5566	0.029*
C17	1.20276 (19)	1.0299 (3)	0.74076 (7)	0.0156 (3)
H17	1.2125	0.9018	0.7261	0.019*
C18	1.34326 (19)	1.1433 (3)	0.75550 (7)	0.0143 (3)
H18	1.4452	1.0910	0.7518	0.017*
C19	1.32986 (18)	1.3358 (2)	0.77577 (7)	0.0119 (3)
C20	1.17472 (17)	1.4047 (3)	0.78314 (6)	0.0132 (3)
H20	1.1614	1.5323	0.7975	0.016*
C21	1.04258 (19)	1.2809 (3)	0.76878 (7)	0.0145 (3)
H21	0.9402	1.3273	0.7746	0.017*
C22	1.47067 (19)	1.4762 (2)	0.78517 (7)	0.0135 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.00979 (9)	0.00942 (10)	0.01397 (8)	−0.00058 (10)	0.00201 (6)	−0.00009 (9)
O1	0.0127 (5)	0.0116 (6)	0.0158 (5)	0.0014 (5)	0.0036 (4)	−0.0003 (4)
O2	0.0120 (6)	0.0131 (6)	0.0190 (5)	0.0013 (5)	0.0042 (4)	0.0016 (5)
O3	0.0236 (7)	0.0243 (8)	0.0170 (5)	0.0001 (6)	0.0068 (5)	0.0039 (5)
O4	0.0115 (5)	0.0136 (6)	0.0223 (5)	−0.0021 (5)	0.0046 (4)	−0.0018 (5)
O5	0.0133 (5)	0.0123 (6)	0.0191 (5)	−0.0025 (5)	0.0051 (4)	−0.0027 (5)
O6	0.0133 (5)	0.0146 (7)	0.0201 (5)	0.0021 (5)	0.0033 (4)	−0.0031 (5)
O7	0.0144 (6)	0.0106 (6)	0.0237 (5)	0.0000 (5)	0.0057 (4)	−0.0008 (5)
O8	0.0124 (6)	0.0125 (7)	0.0192 (5)	−0.0017 (5)	0.0029 (4)	−0.0006 (5)
O9	0.0139 (6)	0.0125 (7)	0.0246 (6)	−0.0031 (5)	−0.0029 (5)	0.0033 (5)
N1	0.0124 (6)	0.0120 (7)	0.0137 (5)	−0.0005 (6)	0.0024 (5)	0.0007 (5)
N2	0.0111 (6)	0.0087 (9)	0.0324 (7)	−0.0007 (6)	0.0029 (5)	−0.0019 (7)
C1	0.0066 (7)	0.0138 (8)	0.0178 (7)	−0.0038 (6)	0.0000 (6)	−0.0006 (6)
C2	0.0121 (7)	0.0141 (9)	0.0153 (6)	−0.0031 (7)	0.0010 (5)	0.0003 (6)
C3	0.0148 (8)	0.0194 (10)	0.0174 (7)	0.0026 (7)	0.0031 (6)	−0.0007 (7)
C4	0.0178 (8)	0.0183 (10)	0.0202 (7)	0.0026 (7)	0.0015 (6)	0.0033 (7)
C5	0.0148 (8)	0.0226 (10)	0.0139 (6)	−0.0037 (7)	0.0019 (6)	0.0004 (6)
C6	0.0211 (9)	0.0204 (10)	0.0201 (7)	0.0019 (7)	0.0076 (6)	−0.0029 (7)
C7	0.0174 (7)	0.0140 (11)	0.0206 (7)	−0.0004 (7)	0.0042 (6)	−0.0006 (6)
C8	0.0236 (9)	0.0289 (13)	0.0188 (7)	−0.0002 (8)	0.0030 (6)	0.0080 (7)
C9	0.0140 (8)	0.0123 (9)	0.0112 (6)	0.0002 (6)	0.0017 (6)	0.0016 (6)
C10	0.0117 (7)	0.0137 (10)	0.0115 (6)	0.0007 (6)	0.0025 (5)	0.0023 (5)
C11	0.0116 (8)	0.0175 (9)	0.0189 (7)	−0.0026 (7)	0.0025 (6)	−0.0010 (7)
C12	0.0167 (8)	0.0138 (9)	0.0174 (7)	−0.0025 (7)	0.0029 (6)	−0.0037 (6)
C13	0.0150 (8)	0.0143 (9)	0.0116 (6)	0.0008 (7)	0.0031 (5)	0.0004 (6)
C14	0.0126 (6)	0.0170 (8)	0.0187 (6)	−0.0038 (9)	0.0034 (5)	−0.0018 (8)
C15	0.0175 (8)	0.0120 (9)	0.0151 (6)	−0.0023 (7)	0.0031 (6)	−0.0033 (6)
C16	0.0222 (8)	0.0158 (10)	0.0191 (6)	0.0021 (8)	0.0035 (6)	−0.0044 (7)
C17	0.0151 (8)	0.0119 (9)	0.0198 (7)	0.0013 (7)	0.0030 (6)	−0.0024 (6)
C18	0.0101 (7)	0.0135 (9)	0.0200 (7)	0.0021 (7)	0.0047 (6)	−0.0011 (6)
C19	0.0121 (7)	0.0126 (8)	0.0116 (6)	−0.0016 (6)	0.0031 (5)	0.0008 (6)
C20	0.0139 (7)	0.0089 (10)	0.0175 (6)	0.0032 (7)	0.0048 (5)	−0.0019 (6)
C21	0.0122 (8)	0.0142 (9)	0.0178 (7)	0.0008 (7)	0.0047 (6)	−0.0010 (6)
C22	0.0136 (7)	0.0136 (10)	0.0145 (6)	−0.0018 (6)	0.0052 (5)	−0.0022 (5)

Geometric parameters (Å, º) top

Co1—O1	2.1338 (11)	C6—C5	1.392 (3)
Co1—O2	2.2301 (11)	C6—H6	0.9300
Co1—O5	2.0506 (11)	C7—C6	1.383 (2)
Co1—O8	2.1394 (12)	C7—H7	0.9300
Co1—O9	2.0317 (13)	C8—H8A	0.9600
Co1—N1	2.1077 (13)	C8—H8B	0.9600
O1—C1	1.276 (2)	C8—H8C	0.9600
O2—C1	1.260 (2)	C10—C9	1.502 (2)
O3—C5	1.3662 (19)	C10—C11	1.389 (2)
O3—C8	1.431 (2)	C10—C15	1.395 (2)
O4—C9	1.2729 (19)	C11—H11	0.9300
O5—C9	1.258 (2)	C12—C11	1.387 (2)
O6—C13	1.3730 (19)	C12—C13	1.395 (2)
O6—C16	1.437 (2)	C12—H12	0.9300
O7—C22	1.237 (2)	C14—C13	1.392 (3)
O8—H81	0.83 (2)	C14—C15	1.375 (2)
O8—H82	0.89 (3)	C14—H14	0.9300
O9—H91	0.79 (2)	C15—H15	0.9300
O9—H92	0.91 (2)	C16—H16A	0.9600
N1—C17	1.344 (2)	C16—H16B	0.9600
N1—C21	1.342 (2)	C16—H16C	0.9600
N2—C22	1.333 (2)	C17—C18	1.385 (2)
N2—H2A	0.79 (2)	C17—H17	0.9300
N2—H2B	0.91 (2)	C18—H18	0.9300
C2—C1	1.489 (2)	C19—C18	1.385 (2)
C2—C3	1.387 (2)	C19—C20	1.398 (2)
C2—C7	1.398 (2)	C20—H20	0.9300
C3—C4	1.392 (2)	C21—C20	1.371 (2)
C3—H3	0.9300	C21—H21	0.9300
C4—H4	0.9300	C22—C19	1.493 (2)
C5—C4	1.386 (2)

O1—Co1—O2	60.32 (4)	C6—C7—H7	119.8
O1—Co1—O8	88.94 (4)	O3—C8—H8A	109.5
O5—Co1—O1	96.83 (4)	O3—C8—H8B	109.5
O5—Co1—O2	156.69 (4)	O3—C8—H8C	109.5
O5—Co1—O8	92.47 (5)	H8A—C8—H8B	109.5
O5—Co1—N1	90.44 (5)	H8A—C8—H8C	109.5
O8—Co1—O2	91.64 (5)	H8B—C8—H8C	109.5
O9—Co1—O1	153.01 (5)	O4—C9—C10	117.72 (14)
O9—Co1—O2	95.22 (5)	O5—C9—O4	124.05 (14)
O9—Co1—O5	108.09 (5)	O5—C9—C10	118.23 (13)
O9—Co1—O8	79.99 (5)	C11—C10—C9	121.43 (14)
O9—Co1—N1	92.80 (5)	C11—C10—C15	118.24 (15)
N1—Co1—O1	97.30 (5)	C15—C10—C9	120.23 (14)
N1—Co1—O2	88.29 (5)	C10—C11—H11	119.1
N1—Co1—O8	172.76 (5)	C12—C11—C10	121.90 (15)
C1—O1—Co1	91.92 (10)	C12—C11—H11	119.1
C1—O2—Co1	87.97 (10)	C11—C12—C13	118.61 (16)
C5—O3—C8	117.25 (14)	C11—C12—H12	120.7
C9—O5—Co1	127.62 (10)	C13—C12—H12	120.7
C13—O6—C16	118.14 (12)	O6—C13—C14	115.31 (13)
Co1—O8—H81	93.8 (15)	O6—C13—C12	124.54 (15)
Co1—O8—H82	109.5 (15)	C14—C13—C12	120.15 (15)
H81—O8—H82	108 (2)	C13—C14—H14	119.9
Co1—O9—H91	117.3 (17)	C15—C14—C13	120.10 (14)
Co1—O9—H92	134.2 (12)	C15—C14—H14	119.9
H91—O9—H92	108 (2)	C10—C15—H15	119.6
C17—N1—Co1	121.84 (11)	C14—C15—C10	120.90 (16)
C21—N1—Co1	120.64 (11)	C14—C15—H15	119.6
C21—N1—C17	117.40 (14)	O6—C16—H16A	109.5
C22—N2—H2A	125.4 (14)	O6—C16—H16B	109.5
C22—N2—H2B	118.0 (14)	O6—C16—H16C	109.5
H2A—N2—H2B	117 (2)	H16A—C16—H16B	109.5
O1—C1—C2	118.41 (15)	H16A—C16—H16C	109.5
O2—C1—O1	119.79 (14)	H16B—C16—H16C	109.5
O2—C1—C2	121.77 (15)	N1—C17—C18	122.89 (16)
C3—C2—C7	118.77 (14)	N1—C17—H17	118.6
C3—C2—C1	120.01 (15)	C18—C17—H17	118.6
C7—C2—C1	121.09 (15)	C17—C18—H18	120.5
C2—C3—C4	121.42 (16)	C19—C18—C17	119.09 (15)
C2—C3—H3	119.3	C19—C18—H18	120.5
C4—C3—H3	119.3	C18—C19—C20	118.15 (15)
C3—C4—H4	120.6	C18—C19—C22	122.94 (15)
C5—C4—C3	118.90 (17)	C20—C19—C22	118.75 (15)
C5—C4—H4	120.6	C19—C20—H20	120.6
O3—C5—C4	123.71 (17)	C21—C20—C19	118.87 (17)
O3—C5—C6	115.79 (15)	C21—C20—H20	120.6
C4—C5—C6	120.49 (15)	N1—C21—C20	123.53 (15)
C7—C6—C5	119.92 (16)	N1—C21—H21	118.2
C7—C6—H6	120.0	C20—C21—H21	118.2
C5—C6—H6	120.0	O7—C22—N2	122.40 (15)
C2—C7—H7	119.8	O7—C22—C19	119.83 (14)
C6—C7—C2	120.36 (16)	N2—C22—C19	117.72 (15)

O2—Co1—O1—C1	0.09 (8)	C7—C2—C1—O2	10.6 (2)
O5—Co1—O1—C1	175.24 (9)	C3—C2—C1—O1	8.3 (2)
O8—Co1—O1—C1	−92.40 (9)	C7—C2—C1—O1	−167.51 (14)
O9—Co1—O1—C1	−27.20 (15)	C1—C2—C3—C4	−173.46 (15)
N1—Co1—O1—C1	83.91 (9)	C7—C2—C3—C4	2.4 (2)
O1—Co1—O2—C1	−0.10 (8)	C1—C2—C7—C6	173.09 (15)
O5—Co1—O2—C1	−12.36 (15)	C3—C2—C7—C6	−2.8 (2)
O8—Co1—O2—C1	87.75 (9)	C2—C3—C4—C5	0.7 (3)
O9—Co1—O2—C1	167.84 (9)	O3—C5—C4—C3	175.05 (15)
N1—Co1—O2—C1	−99.50 (9)	C6—C5—C4—C3	−3.5 (2)
O1—Co1—O5—C9	60.93 (12)	C7—C6—C5—O3	−175.47 (15)
O2—Co1—O5—C9	71.64 (17)	C7—C6—C5—C4	3.2 (2)
O8—Co1—O5—C9	−28.29 (12)	C2—C7—C6—C5	0.0 (2)
O9—Co1—O5—C9	−108.57 (12)	C11—C10—C9—O4	5.9 (2)
N1—Co1—O5—C9	158.34 (12)	C11—C10—C9—O5	−174.93 (13)
O1—Co1—N1—C17	75.29 (12)	C15—C10—C9—O4	−170.39 (13)
O1—Co1—N1—C21	−108.72 (11)	C15—C10—C9—O5	8.8 (2)
O2—Co1—N1—C17	135.07 (12)	C9—C10—C11—C12	−174.61 (14)
O2—Co1—N1—C21	−48.93 (11)	C15—C10—C11—C12	1.7 (2)
O5—Co1—N1—C17	−21.65 (12)	C9—C10—C15—C14	174.66 (14)
O5—Co1—N1—C21	154.35 (11)	C11—C10—C15—C14	−1.7 (2)
O9—Co1—N1—C17	−129.79 (12)	C13—C12—C11—C10	0.8 (2)
O9—Co1—N1—C21	46.21 (12)	C11—C12—C13—O6	175.92 (14)
Co1—O1—C1—O2	−0.17 (14)	C11—C12—C13—C14	−3.3 (2)
Co1—O1—C1—C2	177.95 (12)	C15—C14—C13—O6	−175.95 (13)
Co1—O2—C1—O1	0.16 (14)	C15—C14—C13—C12	3.3 (2)
Co1—O2—C1—C2	−177.89 (13)	C13—C14—C15—C10	−0.8 (2)
C8—O3—C5—C4	−8.5 (2)	N1—C17—C18—C19	−1.6 (2)
C8—O3—C5—C6	170.10 (14)	C20—C19—C18—C17	2.6 (2)
Co1—O5—C9—O4	19.3 (2)	C22—C19—C18—C17	−172.69 (13)
Co1—O5—C9—C10	−159.84 (9)	C18—C19—C20—C21	−1.3 (2)
C16—O6—C13—C12	5.3 (2)	C22—C19—C20—C21	174.22 (13)
C16—O6—C13—C14	−175.44 (13)	N1—C21—C20—C19	−1.2 (2)
Co1—N1—C17—C18	175.31 (11)	O7—C22—C19—C18	151.80 (15)
C21—N1—C17—C18	−0.8 (2)	N2—C22—C19—C18	−25.7 (2)
Co1—N1—C21—C20	−173.91 (11)	O7—C22—C19—C20	−23.5 (2)
C17—N1—C21—C20	2.3 (2)	N2—C22—C19—C20	158.99 (13)
C3—C2—C1—O2	−173.63 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O2ⁱ	0.79 (3)	2.11 (3)	2.877 (2)	164.0 (17)
N2—H2B···O1ⁱⁱ	0.91 (3)	2.16 (3)	3.050 (2)	167 (2)
O8—H81···O4	0.83 (3)	1.84 (3)	2.6577 (17)	167 (3)
O8—H82···O7ⁱⁱⁱ	0.89 (2)	1.86 (3)	2.7427 (16)	172 (2)
O9—H91···O6^iv	0.786 (19)	2.078 (19)	2.8384 (16)	163 (2)
O9—H92···O4^v	0.91 (3)	1.72 (3)	2.6307 (18)	174.1 (15)
C8—H8A···O7^vi	0.96	2.53	3.466 (2)	166
C16—H16B···O4^vii	0.96	2.52	3.4752 (18)	171

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

Experimental details

Crystal data
Chemical formula	[Co(C₈H₇O₃)₂(C₆H₆N₂O)(H₂O)₂]
M_r	519.36
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	100
a, b, c (Å)	8.2666 (2), 6.8055 (2), 20.5415 (4)
β (°)	99.808 (2)
V (Å³)	1138.74 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.81
Crystal size (mm)	0.39 × 0.32 × 0.28

Data collection
Diffractometer	Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.739, 0.791
No. of measured, independent and observed [I > 2σ(I)] reflections	11263, 4838, 4597
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.669

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.022, 0.050, 1.01
No. of reflections	4838
No. of parameters	333
No. of restraints	?
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.24
Absolute structure	Flack (1983), 1761 Friedel pairs
Absolute structure parameter	0.015 (7)

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), 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—H2A···O2ⁱ	0.79 (3)	2.11 (3)	2.877 (2)	164.0 (17)
N2—H2B···O1ⁱⁱ	0.91 (3)	2.16 (3)	3.050 (2)	167 (2)
O8—H81···O4	0.83 (3)	1.84 (3)	2.6577 (17)	167 (3)
O8—H82···O7ⁱⁱⁱ	0.89 (2)	1.86 (3)	2.7427 (16)	172 (2)
O9—H91···O6^iv	0.786 (19)	2.078 (19)	2.8384 (16)	163 (2)
O9—H92···O4^v	0.91 (3)	1.72 (3)	2.6307 (18)	174.1 (15)
C8—H8A···O7^vi	0.96	2.5300	3.466 (2)	166
C16—H16B···O4^vii	0.96	2.5200	3.4752 (18)	171

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

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 diffractometer. This work was supported financially by Kafkas University Research Fund (grant No. 2009-FEF-03).

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