Diaqua­bis[4-(dimethyl­amino)­benzoato]-κ2O,O′;κO-(isonicotinamide-κN1)cobalt(II)

Hökelek, T.; Dal, H.; Tercan, B.; Aybirdi, Ö.; Necefoğlu, H.

doi:10.1107/S1600536809016602

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Pages m627-m628

doi:10.1107/S1600536809016602

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Diaquabis[4-(dimethylamino)benzoato]-κ²O,O′;κO-(isonicotinamide-κN¹)cobalt(II)

Tuncer Hökelek,^a Hakan Dal,^b Barış Tercan,^c Özgür Aybirdi ^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 30 April 2009; accepted 4 May 2009; online 14 May 2009)

The title Co^II complex, [Co(C₉H₁₀NO₂)₂(C₆H₆N₂O)(H₂O)₂], contains two 4-dimethylaminobenzoate (DMAB) anions, one isonicotinamide (INA) ligand and two coordinated water molecules. One of the DMAB anions acts as a bidentate ligand, while the other is monodentate. The four O atoms in the equatorial plane around the Co atom form a highly distorted square-planar arrangement, while the distorted octahedral coordination geometry is completed by the N atom of the INA ligand and the O atom of the second water molecule in the axial positions. An intramolecular O—H⋯O hydrogen bond between the monodentate-coordinated carboxyl group and a coordinated water molecule results in a six-membered ring with an envelope conformation. The dihedral angles between the carboxyl groups and the adjacent benzene rings are 4.29 (10)° for the monodentate ligand and 2.31 (13)° for the bidentate ligand, while the two benzene rings are oriented at a dihedral angle of 65.02 (5)°. The dihedral angles between the pyridine and benzene rings are 11.21 (5)° for the monodentate ligand and 74.60 (5)° for the bidentate ligand. In the crystal structure, intermolecular O—H⋯O, O—H⋯N and N—H⋯O hydrogen bonds link the molecules into a supramolecular structure.

Related literature

For general background, see: Adiwidjaja et al. (1978 ); Amiraslanov et al. (1979 ); Antolini et al. (1982 ); Antsyshkina et al. (1980 ); Bigoli et al. (1972 ); Catterick et al. (1974 ); Chen & Chen (2002 ); Hauptmann et al. (2000 ); Krishnamachari (1974 ); Shnulin et al. (1981 ). For related structures, see: Hökelek et al. (1995 , 1997 , 2007 , 2008 ); Hökelek & Necefoğlu (1996 , 1997 , 2007 ).

Experimental

Crystal data

[Co(C₉H₁₀NO₂)₂(C₆H₆N₂O)(H₂O)₂]
M_r = 545.45
Triclinic, $[P \overline 1]$
a = 6.85550 (10) Å
b = 8.1028 (2) Å
c = 22.4642 (3) Å
α = 90.9180 (10)°
β = 92.965 (2)°
γ = 93.230 (2)°
V = 1243.98 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.74 mm⁻¹
T = 100 K
0.50 × 0.30 × 0.16 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.764, T_max = 0.884
21784 measured reflections
6167 independent reflections
5279 reflections with I > 2σ(I)
R_int = 0.046

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.074
S = 1.04
6167 reflections
353 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Table 1
Selected bond lengths (Å)

Co1—O1	2.0397 (10)
Co1—O3	2.1845 (11)
Co1—O4	2.1445 (11)
Co1—O6	2.0410 (11)
Co1—O7	2.1490 (10)
Co1—N3	2.1314 (12)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H41⋯O3ⁱ	0.857 (18)	2.189 (19)	3.0426 (17)	173.8 (17)
N4—H42⋯O4ⁱⁱ	0.88 (2)	1.96 (2)	2.8101 (17)	161.9 (16)
O6—H61⋯N1ⁱⁱⁱ	0.918 (17)	1.956 (18)	2.8494 (17)	163.9 (17)
O6—H62⋯O2^iv	0.90 (2)	1.77 (2)	2.6640 (15)	172 (2)
O7—H71⋯O2	0.914 (15)	1.774 (16)	2.6532 (15)	160.5 (15)
O7—H72⋯O5^v	0.879 (18)	1.875 (18)	2.7478 (15)	171.6 (17)
Symmetry codes: (i) x-1, y+1, z; (ii) x, y+1, z; (iii) x-1, y-1, z; (iv) x-1, y, z; (v) x+1, y-1, 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: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809016602/xu2520sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809016602/xu2520Isup2.hkl

checkCIF report

Comment top

Nicotinamide (NA) is one form of niacin. A deficiency of this vitamin leads to loss of copper from the body, known as pellagra disease. Victims of pellagra show unusually high serum and urinary copper levels (Krishnamachari, 1974). The nicotinic acid derivative N,N-diethylnicotinamide (DENA) is an important respiratory stimulant (Bigoli et al., 1972). Transition metal complexes with biochemical molecules show interesting physical and/or chemical properties, through which they may find applications in biological systems (Antolini et al., 1982). Some benzoic acid derivatives, such as 4-aminobenzoic acid, have been extensively reported in coordination chemistry, as bifunctional organic ligands, due to the varieties of their coordination modes (Chen & Chen, 2002; Amiraslanov et al., 1979; Hauptmann et al., 2000).

The structure–function–coordination relationships of the arylcarboxylate ion in Co^II complexes of benzoic acid derivatives may also change depending on the nature and position of the substituted groups on the benzene ring, the nature of the additional ligand molecule or solvent, and the pH and temperature of synthesis, as in Zn^II complexes (Shnulin et al., 1981; Antsyshkina et al., 1980; Adiwidjaja et al., 1978). When pyridine and its derivatives are used instead of water molecules, the structure is completely different (Catterick et al., 1974).

The structure determination of the title compound, (I), a cobalt complex with two 4-dimethylaminobenzoate (DMAB) and one isonicotinamide (INA) ligands and two water molecules, was undertaken in order to determine the properties of the ligands and also to compare the results obtained with those reported previously.

In the monomeric title complex, (I), the Co atom is surrounded by two DMAB and INA ligands and two water molecules. One of the DMAB ions acts as a bidentate ligand, while the other and INA are monodentate ligands (Fig. 1). The four O atoms (O1, O3, O4 and O6 atoms) in the equatorial plane around the Co atom form a highly distorted square-planar arrangement, while the distorted octahedral coordination is completed by the N atom of the INA ligand (N1) and the O atom of the water molecule (O7) in the axial positions (Table 1 and Fig. 1).

The near equality of the C1—O1 [1.2682 (17) Å], C1—O2 [1.2628 (17) Å], C10—O3 [1.2743 (18) Å] and C10—O4 [1.2716 (18) Å] bonds in the carboxylate group indicates a delocalized bonding arrangement, rather than localized single and double bonds, and may be compared with the corresponding distances: 1.256 (6) and 1.245 (6) Å in [Mn(DENA)₂(C₇H₄ClO₂)₂(H₂O)₂], (II) (Hökelek et al., 2008), 1.265 (6) and 1.275 (6) Å in [Mn(C₉H₁₀NO₂)₂(H₂O)₄]. 2(H₂O), (III) (Hökelek & Necefoğlu, 2007), 1.260 (4) and 1.252 (4) Å in [Zn(DENA)₂(C₇H₄FO₂)₂(H₂O)₂], (IV) (Hökelek et al., 2007), 1.259 (9) and 1.273 (9) Å in Cu₂(DENA)₂(C₆H₅COO)₄, (V) (Hökelek et al., 1995), 1.279 (4) and 1.246 (4) Å in [Zn₂(DENA)₂(C₇H₅O₃)₄]. 2H₂O, (VI) (Hökelek & Necefoğlu, 1996), 1.251 (6) and 1.254 (7) Å in [Co(DENA)₂(C₇H₅O₃)₂(H₂O)₂], (VII) (Hökelek & Necefoğlu, 1997) and 1.278 (3) and 1.246 (3) Å in [Cu(DENA)₂(C₇H₄NO₄)₂(H₂O)₂], (VIII) (Hökelek et al., 1997). In (I), the average Co—O bond length is 2.1117 (11) Å and the Co atom is displaced out of the least-squares planes of the carboxylate groups (O1/C1/O2) and (O3/O4/C10) by -0.536 (1) Å and -0.012 (1) Å, respectively. The dihedral angle between the planar carboxylate groups and the adjacent benzene rings A (C2–C7) and B (C11–C16) are 4.29 (10)° and 2.31 (13)°, respectively, while those between rings A, B and C (N3/C19–C23) are A/B = 65.02 (5), A/C = 11.21 (5) and B/C = 74.60 (5)°. Intramolecular C—H···O hydrogen bond (Table 2) results in the formation of a six-membered ring D (Co1/O1/O2/O7/C1/H71) adopting envelope conformation, with atom Co1 displaced by 0.635 (1) Å from the plane of the other ring atoms.

In the crystal structure, strong intermolecular O—H···O, O—H···N 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 general background, see: Adiwidjaja et al. (1978); Amiraslanov et al. (1979); Antolini et al. (1982); Antsyshkina et al. (1980); Bigoli et al. (1972); Catterick et al. (1974); Chen & Chen (2002); Hauptmann et al. (2000); Krishnamachari (1974); Shnulin et al. (1981). For related structures, see: Hökelek et al. (1995, 1997, 2007, 2008); Hökelek & Necefoğlu (1996, 1997, 2007).

Experimental top

The title compound was prepared by the reaction of CoSO₄.H₂O (1.40 g, 5 mmol) in H₂O (30 ml) and INA (1.22 g, 10 mmol) in H₂O (20 ml) with sodium 4-dimethylaminobenzoate (1.65 g, 10 mmol) in H₂O (50 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).

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. Hydrogen bond is shown as dashed line.

Diaquabis[4-(dimethylamino)benzoato]-κ²O,O';κO- (isonicotinamide-κN¹)cobalt(II) top

Crystal data top

[Co(C₉H₁₀NO₂)₂(C₆H₆N₂O)(H₂O)₂]	Z = 2
M_r = 545.45	F(000) = 570
Triclinic, P1	D_x = 1.456 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.8555 (1) Å	Cell parameters from 9963 reflections
b = 8.1028 (2) Å	θ = 2.5–28.3°
c = 22.4642 (3) Å	µ = 0.74 mm⁻¹
α = 90.918 (1)°	T = 100 K
β = 92.965 (2)°	Block, brown
γ = 93.230 (2)°	0.50 × 0.30 × 0.16 mm
V = 1243.98 (4) Å³

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	6167 independent reflections
Radiation source: fine-focus sealed tube	5279 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.046
ϕ and ω scans	θ_max = 28.4°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −9→6
T_min = 0.764, T_max = 0.884	k = −10→10
21784 measured reflections	l = −27→29

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.074	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.033P)² + 0.378P] where P = (F_o² + 2F_c²)/3
6167 reflections	(Δ/σ)_max = 0.001
353 parameters	Δρ_max = 0.43 e Å⁻³
6 restraints	Δρ_min = −0.38 e Å⁻³

Crystal data top

[Co(C₉H₁₀NO₂)₂(C₆H₆N₂O)(H₂O)₂]	γ = 93.230 (2)°
M_r = 545.45	V = 1243.98 (4) Å³
Triclinic, P1	Z = 2
a = 6.8555 (1) Å	Mo Kα radiation
b = 8.1028 (2) Å	µ = 0.74 mm⁻¹
c = 22.4642 (3) Å	T = 100 K
α = 90.918 (1)°	0.50 × 0.30 × 0.16 mm
β = 92.965 (2)°

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	6167 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	5279 reflections with I > 2σ(I)
T_min = 0.764, T_max = 0.884	R_int = 0.046
21784 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	6 restraints
wR(F²) = 0.074	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.43 e Å⁻³
6167 reflections	Δρ_min = −0.38 e Å⁻³
353 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	0.43320 (3)	0.02268 (2)	0.277708 (9)	0.00947 (6)
O1	0.60678 (15)	0.17803 (12)	0.33279 (5)	0.0131 (2)
O2	0.86084 (15)	0.02285 (12)	0.35203 (5)	0.0149 (2)
O3	0.61788 (15)	0.00803 (12)	0.20163 (5)	0.0130 (2)
O4	0.31810 (15)	−0.10110 (12)	0.19727 (5)	0.0131 (2)
O5	−0.30534 (15)	0.58077 (12)	0.23291 (5)	0.0147 (2)
O6	0.21656 (16)	−0.06931 (13)	0.32895 (5)	0.0148 (2)
H61	0.240 (3)	−0.141 (2)	0.3594 (8)	0.039 (6)*
H62	0.100 (3)	−0.028 (3)	0.3359 (10)	0.048 (7)*
O7	0.57303 (16)	−0.18934 (13)	0.31208 (5)	0.0134 (2)
H71	0.688 (2)	−0.137 (2)	0.3264 (9)	0.036 (6)*
H72	0.605 (3)	−0.258 (2)	0.2840 (8)	0.041 (6)*
N1	1.23506 (18)	0.74180 (15)	0.43479 (6)	0.0133 (3)
N2	0.5720 (3)	−0.30713 (19)	−0.06317 (7)	0.0288 (4)
N3	0.25998 (18)	0.22383 (15)	0.25346 (5)	0.0107 (2)
N4	−0.0640 (2)	0.76078 (16)	0.20689 (6)	0.0151 (3)
H41	−0.147 (3)	0.836 (2)	0.2044 (8)	0.018 (5)*
H42	0.060 (3)	0.784 (2)	0.1996 (9)	0.024 (5)*
C1	0.7817 (2)	0.15986 (18)	0.35163 (6)	0.0112 (3)
C2	0.8986 (2)	0.31004 (17)	0.37515 (6)	0.0109 (3)
C3	0.8160 (2)	0.46310 (18)	0.37877 (7)	0.0134 (3)
H3	0.6851	0.4713	0.3667	0.016*
C4	0.9243 (2)	0.60278 (18)	0.39981 (7)	0.0145 (3)
H4	0.8646	0.7027	0.4025	0.017*
C5	1.1227 (2)	0.59587 (17)	0.41723 (6)	0.0113 (3)
C6	1.2061 (2)	0.44248 (18)	0.41310 (7)	0.0136 (3)
H6	1.3376	0.4342	0.4243	0.016*
C7	1.0954 (2)	0.30329 (18)	0.39263 (7)	0.0129 (3)
H7	1.1540	0.2027	0.3905	0.015*
C8	1.1348 (2)	0.86392 (19)	0.46908 (7)	0.0171 (3)
H8A	1.2225	0.9587	0.4781	0.026*
H8B	1.0942	0.8159	0.5055	0.026*
H8C	1.0223	0.8971	0.4461	0.026*
C9	1.4336 (2)	0.7219 (2)	0.45897 (9)	0.0234 (4)
H9A	1.4987	0.8288	0.4665	0.035*
H9B	1.5039	0.6615	0.4308	0.035*
H9C	1.4289	0.6624	0.4955	0.035*
C10	0.4778 (2)	−0.07098 (17)	0.17208 (7)	0.0115 (3)
C11	0.5002 (2)	−0.12862 (18)	0.11039 (7)	0.0142 (3)
C12	0.3496 (2)	−0.21833 (19)	0.07857 (7)	0.0180 (3)
H12	0.2317	−0.2404	0.0964	0.022*
C13	0.3706 (3)	−0.2755 (2)	0.02120 (8)	0.0226 (4)
H13	0.2663	−0.3337	0.0008	0.027*
C14	0.5478 (3)	−0.2470 (2)	−0.00686 (7)	0.0212 (4)
C15	0.7001 (3)	−0.1550 (2)	0.02534 (8)	0.0221 (4)
H15	0.8189	−0.1333	0.0080	0.027*
C16	0.6747 (2)	−0.09685 (19)	0.08242 (7)	0.0175 (3)
H16	0.7766	−0.0350	0.1026	0.021*
C17	0.7573 (3)	−0.2808 (3)	−0.09026 (9)	0.0377 (5)
H17A	0.7532	−0.3397	−0.1278	0.057*
H17B	0.8596	−0.3202	−0.0644	0.057*
H17C	0.7824	−0.1648	−0.0967	0.057*
C18	0.4093 (3)	−0.3871 (2)	−0.09781 (8)	0.0355 (5)
H18A	0.4509	−0.4176	−0.1364	0.053*
H18B	0.3058	−0.3125	−0.1022	0.053*
H18C	0.3631	−0.4844	−0.0778	0.053*
C19	0.3251 (2)	0.38257 (18)	0.25972 (7)	0.0127 (3)
H19	0.4555	0.4059	0.2721	0.015*
C20	0.2078 (2)	0.51366 (18)	0.24869 (7)	0.0130 (3)
H20	0.2596	0.6221	0.2525	0.016*
C21	0.0118 (2)	0.48028 (17)	0.23182 (6)	0.0103 (3)
C22	−0.0572 (2)	0.31584 (17)	0.22533 (7)	0.0114 (3)
H22	−0.1879	0.2891	0.2143	0.014*
C23	0.0708 (2)	0.19348 (17)	0.23553 (7)	0.0118 (3)
H23	0.0243	0.0841	0.2297	0.014*
C24	−0.1314 (2)	0.61288 (17)	0.22363 (7)	0.0117 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.00738 (11)	0.00874 (10)	0.01243 (11)	0.00157 (7)	0.00073 (7)	−0.00010 (7)
O1	0.0090 (5)	0.0130 (5)	0.0173 (6)	0.0029 (4)	−0.0020 (4)	−0.0014 (4)
O2	0.0098 (5)	0.0111 (5)	0.0239 (6)	0.0029 (4)	−0.0005 (4)	0.0000 (4)
O3	0.0104 (5)	0.0124 (5)	0.0160 (6)	0.0000 (4)	0.0006 (4)	−0.0011 (4)
O4	0.0103 (5)	0.0139 (5)	0.0152 (6)	0.0006 (4)	0.0024 (4)	−0.0006 (4)
O5	0.0076 (5)	0.0121 (5)	0.0246 (6)	0.0011 (4)	0.0016 (4)	−0.0013 (4)
O6	0.0102 (6)	0.0172 (5)	0.0182 (6)	0.0052 (4)	0.0041 (5)	0.0056 (4)
O7	0.0101 (6)	0.0119 (5)	0.0185 (6)	0.0029 (4)	0.0006 (5)	−0.0002 (4)
N1	0.0110 (6)	0.0120 (6)	0.0166 (7)	0.0018 (5)	−0.0017 (5)	−0.0023 (5)
N2	0.0426 (10)	0.0311 (8)	0.0138 (7)	0.0097 (7)	0.0043 (7)	−0.0034 (6)
N3	0.0099 (6)	0.0116 (6)	0.0106 (6)	0.0007 (5)	0.0014 (5)	0.0004 (5)
N4	0.0078 (7)	0.0108 (6)	0.0270 (8)	0.0029 (5)	0.0003 (6)	0.0032 (5)
C1	0.0111 (7)	0.0132 (7)	0.0095 (7)	0.0016 (6)	0.0014 (6)	0.0006 (5)
C2	0.0106 (7)	0.0130 (7)	0.0094 (7)	0.0010 (5)	0.0013 (6)	0.0011 (5)
C3	0.0092 (7)	0.0160 (7)	0.0151 (8)	0.0033 (6)	−0.0014 (6)	−0.0006 (6)
C4	0.0138 (8)	0.0121 (7)	0.0179 (8)	0.0041 (6)	0.0006 (6)	−0.0008 (6)
C5	0.0126 (7)	0.0122 (7)	0.0092 (7)	0.0004 (6)	0.0020 (6)	0.0012 (5)
C6	0.0100 (7)	0.0155 (7)	0.0154 (8)	0.0026 (6)	−0.0018 (6)	0.0015 (6)
C7	0.0119 (7)	0.0122 (7)	0.0148 (8)	0.0043 (6)	−0.0003 (6)	0.0008 (6)
C8	0.0209 (9)	0.0145 (7)	0.0159 (8)	0.0026 (6)	0.0009 (7)	−0.0032 (6)
C9	0.0155 (8)	0.0168 (8)	0.0368 (11)	0.0015 (6)	−0.0093 (8)	−0.0055 (7)
C10	0.0118 (7)	0.0080 (6)	0.0150 (8)	0.0027 (5)	0.0007 (6)	0.0019 (5)
C11	0.0161 (8)	0.0127 (7)	0.0141 (8)	0.0031 (6)	0.0013 (6)	0.0010 (6)
C12	0.0164 (8)	0.0199 (8)	0.0177 (8)	0.0020 (6)	0.0016 (7)	−0.0001 (6)
C13	0.0263 (10)	0.0228 (8)	0.0182 (9)	0.0021 (7)	−0.0046 (7)	−0.0023 (7)
C14	0.0322 (10)	0.0190 (8)	0.0133 (8)	0.0090 (7)	0.0016 (7)	0.0016 (6)
C15	0.0234 (9)	0.0249 (9)	0.0194 (9)	0.0053 (7)	0.0087 (7)	0.0028 (7)
C16	0.0187 (8)	0.0171 (7)	0.0171 (8)	0.0016 (6)	0.0025 (7)	0.0015 (6)
C17	0.0527 (14)	0.0452 (12)	0.0177 (10)	0.0161 (10)	0.0122 (9)	−0.0011 (8)
C18	0.0521 (14)	0.0385 (11)	0.0167 (9)	0.0174 (10)	−0.0056 (9)	−0.0080 (8)
C19	0.0090 (7)	0.0134 (7)	0.0155 (8)	−0.0002 (6)	−0.0003 (6)	0.0027 (6)
C20	0.0116 (7)	0.0098 (7)	0.0175 (8)	−0.0018 (5)	0.0002 (6)	0.0012 (6)
C21	0.0093 (7)	0.0120 (7)	0.0101 (7)	0.0022 (5)	0.0024 (6)	0.0011 (5)
C22	0.0089 (7)	0.0128 (7)	0.0123 (7)	−0.0002 (5)	0.0005 (6)	−0.0001 (5)
C23	0.0120 (7)	0.0099 (7)	0.0133 (7)	−0.0003 (5)	0.0007 (6)	−0.0008 (5)
C24	0.0116 (7)	0.0103 (7)	0.0132 (7)	0.0015 (5)	−0.0010 (6)	−0.0019 (5)

Geometric parameters (Å, º) top

Co1—O1	2.0397 (10)	C7—C2	1.390 (2)
Co1—O3	2.1845 (11)	C7—C6	1.382 (2)
Co1—O4	2.1445 (11)	C7—H7	0.9300
Co1—O6	2.0410 (11)	C8—H8A	0.9600
Co1—O7	2.1490 (10)	C8—H8B	0.9600
Co1—N3	2.1314 (12)	C8—H8C	0.9600
Co1—C10	2.5187 (15)	C9—H9A	0.9600
O1—C1	1.2682 (17)	C9—H9B	0.9600
O2—C1	1.2628 (17)	C9—H9C	0.9600
O3—C10	1.2743 (18)	C10—C11	1.473 (2)
O4—C10	1.2716 (18)	C11—C12	1.388 (2)
O5—C24	1.2353 (18)	C11—C16	1.393 (2)
O6—H61	0.919 (14)	C12—C13	1.380 (2)
O6—H62	0.903 (16)	C12—H12	0.9300
O7—H71	0.910 (14)	C13—C14	1.407 (2)
O7—H72	0.881 (15)	C13—H13	0.9300
N1—C5	1.4135 (18)	C15—C14	1.409 (3)
N1—C8	1.4668 (19)	C15—H15	0.9300
N1—C9	1.457 (2)	C16—C15	1.382 (2)
N2—C14	1.370 (2)	C16—H16	0.9300
N2—C17	1.444 (3)	C17—H17A	0.9600
N2—C18	1.443 (3)	C17—H17B	0.9600
N3—C19	1.3405 (19)	C17—H17C	0.9600
N3—C23	1.3456 (19)	C18—H18A	0.9600
N4—C24	1.3269 (19)	C18—H18B	0.9600
N4—H41	0.857 (19)	C18—H18C	0.9600
N4—H42	0.89 (2)	C19—H19	0.9300
C1—C2	1.492 (2)	C20—C19	1.386 (2)
C2—C3	1.395 (2)	C20—C21	1.387 (2)
C3—H3	0.9300	C20—H20	0.9300
C4—C3	1.381 (2)	C22—C21	1.392 (2)
C4—C5	1.401 (2)	C22—C23	1.375 (2)
C4—H4	0.9300	C22—H22	0.9300
C6—C5	1.401 (2)	C23—H23	0.9300
C6—H6	0.9300	C24—C21	1.503 (2)

O1—Co1—O3	100.06 (4)	C5—C4—H4	119.6
O1—Co1—O4	159.45 (4)	O5—C24—N4	122.77 (14)
O1—Co1—O6	105.47 (5)	O5—C24—C21	119.20 (13)
O1—Co1—O7	91.43 (4)	N4—C24—C21	118.02 (13)
O1—Co1—N3	89.64 (4)	C4—C3—C2	121.51 (14)
O1—Co1—C10	130.10 (5)	C4—C3—H3	119.2
O3—Co1—C10	30.39 (4)	C2—C3—H3	119.2
O4—Co1—O7	94.57 (4)	N1—C8—H8A	109.5
O4—Co1—O3	60.70 (4)	N1—C8—H8B	109.5
O4—Co1—C10	30.31 (4)	H8A—C8—H8B	109.5
O6—Co1—O3	152.10 (4)	N1—C8—H8C	109.5
O6—Co1—O4	94.88 (4)	H8A—C8—H8C	109.5
O6—Co1—O7	81.01 (4)	H8B—C8—H8C	109.5
O6—Co1—N3	90.00 (4)	C19—C20—C21	118.85 (13)
O6—Co1—C10	124.14 (5)	C19—C20—H20	120.6
O7—Co1—O3	87.37 (4)	C21—C20—H20	120.6
O7—Co1—C10	91.22 (4)	C15—C16—C11	121.55 (16)
N3—Co1—O3	101.34 (4)	C15—C16—H16	119.2
N3—Co1—O4	87.53 (4)	C11—C16—H16	119.2
N3—Co1—O7	170.90 (4)	C23—C22—C21	118.95 (14)
N3—Co1—C10	95.00 (5)	C23—C22—H22	120.5
C1—O1—Co1	127.70 (9)	C21—C22—H22	120.5
C10—O3—Co1	89.46 (9)	N3—C19—C20	123.23 (14)
C10—O4—Co1	91.35 (9)	N3—C19—H19	118.4
Co1—O7—H71	98.5 (13)	C20—C19—H19	118.4
Co1—O7—H72	113.3 (14)	C12—C13—C14	120.86 (16)
H71—O7—H72	105.6 (18)	C12—C13—H13	119.6
Co1—O6—H61	122.1 (13)	C14—C13—H13	119.6
Co1—O6—H62	129.3 (14)	N3—C23—C22	123.42 (13)
H61—O6—H62	105.6 (18)	N3—C23—H23	118.3
C19—N3—C23	117.19 (12)	C22—C23—H23	118.3
C19—N3—Co1	123.17 (10)	C20—C21—C22	118.31 (13)
C23—N3—Co1	119.40 (9)	C20—C21—C24	123.09 (13)
C5—N1—C9	116.82 (12)	C22—C21—C24	118.51 (13)
C5—N1—C8	116.04 (12)	C4—C5—C6	117.65 (13)
C9—N1—C8	111.97 (13)	C4—C5—N1	120.25 (13)
C24—N4—H42	123.3 (12)	C6—C5—N1	121.99 (14)
C24—N4—H41	116.2 (12)	C14—N2—C18	120.59 (16)
H42—N4—H41	120.5 (17)	C14—N2—C17	120.27 (17)
O4—C10—O3	118.49 (14)	C18—N2—C17	119.00 (15)
O4—C10—C11	120.43 (13)	C16—C15—C14	120.68 (16)
O3—C10—C11	121.07 (13)	C16—C15—H15	119.7
O4—C10—Co1	58.34 (8)	C14—C15—H15	119.7
O3—C10—Co1	60.14 (8)	N2—C14—C13	121.32 (17)
C11—C10—Co1	178.69 (11)	N2—C14—C15	121.24 (17)
O2—C1—O1	123.86 (13)	C13—C14—C15	117.43 (15)
O2—C1—C2	118.69 (13)	N1—C9—H9A	109.5
O1—C1—C2	117.45 (12)	N1—C9—H9B	109.5
C6—C7—C2	121.54 (14)	H9A—C9—H9B	109.5
C6—C7—H7	119.2	N1—C9—H9C	109.5
C2—C7—H7	119.2	H9A—C9—H9C	109.5
C12—C11—C16	117.82 (15)	H9B—C9—H9C	109.5
C12—C11—C10	121.25 (14)	N2—C17—H17A	109.5
C16—C11—C10	120.92 (14)	N2—C17—H17B	109.5
C7—C2—C3	117.57 (13)	H17A—C17—H17B	109.5
C7—C2—C1	121.09 (13)	N2—C17—H17C	109.5
C3—C2—C1	121.31 (13)	H17A—C17—H17C	109.5
C7—C6—C5	120.88 (14)	H17B—C17—H17C	109.5
C7—C6—H6	119.6	N2—C18—H18A	109.5
C5—C6—H6	119.6	N2—C18—H18B	109.5
C13—C12—C11	121.64 (16)	H18A—C18—H18B	109.5
C13—C12—H12	119.2	N2—C18—H18C	109.5
C11—C12—H12	119.2	H18A—C18—H18C	109.5
C3—C4—C5	120.84 (14)	H18B—C18—H18C	109.5
C3—C4—H4	119.6

O1—Co1—O3—C10	−172.09 (8)	C6—C7—C2—C3	0.2 (2)
O6—Co1—O3—C10	31.83 (13)	C6—C7—C2—C1	178.40 (14)
N3—Co1—O3—C10	−80.42 (8)	O2—C1—C2—C7	5.3 (2)
O4—Co1—O3—C10	0.19 (8)	O1—C1—C2—C7	−175.29 (14)
O7—Co1—O3—C10	96.92 (8)	O2—C1—C2—C3	−176.59 (14)
O1—Co1—O4—C10	21.94 (16)	O1—C1—C2—C3	2.8 (2)
O6—Co1—O4—C10	−165.93 (8)	C2—C7—C6—C5	0.3 (2)
N3—Co1—O4—C10	104.28 (8)	C16—C11—C12—C13	0.3 (2)
O7—Co1—O4—C10	−84.59 (8)	C10—C11—C12—C13	−178.73 (14)
O3—Co1—O4—C10	−0.19 (8)	C5—C4—C3—C2	1.3 (2)
O6—Co1—O1—C1	112.48 (12)	C7—C2—C3—C4	−1.0 (2)
N3—Co1—O1—C1	−157.62 (12)	C1—C2—C3—C4	−179.19 (14)
O4—Co1—O1—C1	−75.66 (17)	C12—C11—C16—C15	−1.3 (2)
O7—Co1—O1—C1	31.42 (12)	C10—C11—C16—C15	177.74 (14)
O3—Co1—O1—C1	−56.16 (12)	C23—N3—C19—C20	0.0 (2)
C10—Co1—O1—C1	−61.38 (13)	Co1—N3—C19—C20	−174.44 (11)
O1—Co1—N3—C19	21.32 (12)	C21—C20—C19—N3	1.8 (2)
O6—Co1—N3—C19	126.79 (12)	C11—C12—C13—C14	1.1 (2)
O4—Co1—N3—C19	−138.32 (12)	C19—N3—C23—C22	−2.0 (2)
O3—Co1—N3—C19	−78.86 (12)	Co1—N3—C23—C22	172.64 (11)
C10—Co1—N3—C19	−108.92 (12)	C21—C22—C23—N3	2.2 (2)
O1—Co1—N3—C23	−152.97 (11)	C19—C20—C21—C22	−1.5 (2)
O6—Co1—N3—C23	−47.50 (11)	C19—C20—C21—C24	174.91 (14)
O4—Co1—N3—C23	47.38 (11)	C23—C22—C21—C20	−0.3 (2)
O3—Co1—N3—C23	106.84 (11)	C23—C22—C21—C24	−176.92 (13)
C10—Co1—N3—C23	76.79 (11)	O5—C24—C21—C20	−150.39 (15)
Co1—O4—C10—O3	0.33 (13)	N4—C24—C21—C20	29.2 (2)
Co1—O4—C10—C11	179.46 (12)	O5—C24—C21—C22	26.1 (2)
Co1—O3—C10—O4	−0.32 (13)	N4—C24—C21—C22	−154.32 (14)
Co1—O3—C10—C11	−179.45 (12)	C3—C4—C5—C6	−0.6 (2)
O1—Co1—C10—O4	−170.13 (7)	C3—C4—C5—N1	175.64 (14)
O6—Co1—C10—O4	17.01 (10)	C7—C6—C5—C4	−0.1 (2)
N3—Co1—C10—O4	−76.38 (8)	C7—C6—C5—N1	−176.35 (14)
O7—Co1—C10—O4	96.97 (8)	C9—N1—C5—C4	172.91 (14)
O3—Co1—C10—O4	179.67 (13)	C8—N1—C5—C4	37.38 (19)
O1—Co1—C10—O3	10.20 (10)	C9—N1—C5—C6	−11.0 (2)
O6—Co1—C10—O3	−162.65 (7)	C8—N1—C5—C6	−146.50 (14)
N3—Co1—C10—O3	103.95 (8)	C11—C16—C15—C14	0.9 (2)
O4—Co1—C10—O3	−179.67 (13)	C18—N2—C14—C13	6.5 (2)
O7—Co1—C10—O3	−82.70 (8)	C17—N2—C14—C13	−177.97 (16)
Co1—O1—C1—O2	−19.4 (2)	C18—N2—C14—C15	−173.96 (16)
Co1—O1—C1—C2	161.23 (10)	C17—N2—C14—C15	1.6 (2)
O4—C10—C11—C12	−0.8 (2)	C12—C13—C14—N2	178.18 (15)
O3—C10—C11—C12	178.35 (13)	C12—C13—C14—C15	−1.4 (2)
O4—C10—C11—C16	−179.76 (13)	C16—C15—C14—N2	−179.16 (15)
O3—C10—C11—C16	−0.6 (2)	C16—C15—C14—C13	0.4 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H41···O3ⁱ	0.857 (18)	2.189 (19)	3.0426 (17)	173.8 (17)
N4—H42···O4ⁱⁱ	0.88 (2)	1.96 (2)	2.8101 (17)	161.9 (16)
O6—H61···N1ⁱⁱⁱ	0.92 (2)	1.96 (2)	2.8494 (17)	164 (2)
O6—H62···O2^iv	0.90 (2)	1.77 (2)	2.6640 (15)	172 (2)
O7—H71···O2	0.91 (2)	1.77 (2)	2.6532 (15)	161 (2)
O7—H72···O5^v	0.88 (2)	1.88 (2)	2.7478 (15)	172 (2)

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

Experimental details

Crystal data
Chemical formula	[Co(C₉H₁₀NO₂)₂(C₆H₆N₂O)(H₂O)₂]
M_r	545.45
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	6.8555 (1), 8.1028 (2), 22.4642 (3)
α, β, γ (°)	90.918 (1), 92.965 (2), 93.230 (2)
V (Å³)	1243.98 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.74
Crystal size (mm)	0.50 × 0.30 × 0.16

Data collection
Diffractometer	Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.764, 0.884
No. of measured, independent and observed [I > 2σ(I)] reflections	21784, 6167, 5279
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.074, 1.04
No. of reflections	6167
No. of parameters	353
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.38

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected bond lengths (Å) top

Co1—O1	2.0397 (10)	Co1—O6	2.0410 (11)
Co1—O3	2.1845 (11)	Co1—O7	2.1490 (10)
Co1—O4	2.1445 (11)	Co1—N3	2.1314 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H41···O3ⁱ	0.857 (18)	2.189 (19)	3.0426 (17)	173.8 (17)
N4—H42···O4ⁱⁱ	0.88 (2)	1.96 (2)	2.8101 (17)	161.9 (16)
O6—H61···N1ⁱⁱⁱ	0.918 (17)	1.956 (18)	2.8494 (17)	163.9 (17)
O6—H62···O2^iv	0.90 (2)	1.77 (2)	2.6640 (15)	172 (2)
O7—H71···O2	0.914 (15)	1.774 (16)	2.6532 (15)	160.5 (15)
O7—H72···O5^v	0.879 (18)	1.875 (18)	2.7478 (15)	171.6 (17)

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

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

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