Crystal structure of trans-di­aqua­bis­(4-cyano­benzoato-κO)bis­(nicotinamide-κN1)cobalt(II)

Aşkın, G. Ş.; Necefoğlu, H.; Yılmaz Nayir, G.; Çatak Çelik, R.; Hökelek, T.

doi:10.1107/S2056989015008270

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ISSN: 2056-9890

Volume 71| Part 5| May 2015| Pages 561-563

https://doi.org/10.1107/S2056989015008270

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Crystal structure of trans-diaquabis(4-cyanobenzoato-κO)bis(nicotinamide-κN¹)cobalt(II)

Gülçin Şefiye Aşkın,^a Hacali Necefoğlu,^b,^c Gamze Yılmaz Nayir,^b Raziye Çatak Çelik ^d and Tuncer Hökelek ^a ^*

^aDepartment of Physics, Hacettepe University, 06800 Beytepe, Ankara, Turkey, ^bDepartment of Chemistry, Kafkas University, 36100 Kars, Turkey, ^cInternational Scientific Research Centre, Baku State University, 1148 Baku, Azerbaijan, and ^dScientific and Technological Application and Research Center, Aksaray University, 68100 Aksaray, Turkey
^*Correspondence e-mail: merzifon@hacettepe.edu.tr

Edited by M. Weil, Vienna University of Technology, Austria (Received 22 April 2015; accepted 27 April 2015; online 30 April 2015)

In the title complex, [Co(C₈H₄NO₂)₂(C₆H₆N₂O)₂(H₂O)₂], the Co^II atom is located on an inversion centre and is coordinated by two 4-cyanobenzoate (CNB) 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 sphere 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 22.11 (15)°, while the pyridine and benzene rings are oriented at a dihedral angle of 89.98 (5)°. In the crystal, intermolecular N—H⋯O and O—H⋯O hydrogen bonds link the molecules, enclosing R₂²(8) and R₄⁴(8) ring motifs, forming layers parallel to (100). The layers are linked via C—H⋯O and C—H⋯N hydrogen bonds, resulting in a three-dimensional network. A weak C—H⋯π interaction is also observed.

Keywords: crystal structure; cobalt(II); transition metal complexes of benzoic acid and nicotinamide derivatives.

CCDC reference: 1061935

1. Chemical context

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-relevant 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 Zn^II complexes of benzoic acid derivatives 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 (Shnulin et al., 1981 ; Nadzhafov 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 ). In this context, we synthesized the Co^II-containing title compound, trans-diaquabis(4-cyanobenzoato-κO)bis(nicotinamide-κN¹)cobalt(II), [Co(C₈H₄O₂N)₂(C₆H₆N₂O)₂(H₂O)₂], and report herein its crystal structure.

2. Structural commentary

In the mononuclear title complex, the Co^II atom is located on an inversion centre and is coordinated by two 4-cyanobenzoate (CNB) anions, two nicotinamide (NA) ligands and two water molecules, with all ligands coordinating in a monodentate manner (Fig. 1).

Figure 1
The molecular structure of the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Symmetry-related atoms are defined by symmetry code −x + 1, −y + 1, −z + 1.

The two symmetry-related carboxylate O atoms (O2 and O2ⁱ) and the two symmetry-related water O atoms (O4 and O4ⁱ) form a slightly distorted square-planar arrangement, while the slightly distorted octahedral coordination sphere is completed by the two symmetry-related N atoms (N2 and N2ⁱ) of the two NA ligands in the axial positions [symmetry code: (i) −x + 1, −y + 1, −z + 1] (Fig. 1).

The very similar C1—O1 [1.254 (2) Å] and C1—O2 [1.256 (2) Å], bond lengths of the carboxylate group indicate delocalized bonding arrangements, rather than localized single and double bonds. The Co—O bond lengths are 2.0835 (12) Å (for benzoate oxygen atoms) and 2.1350 (13) Å (for water oxygen atoms), and the Co—N bond length is 2.1390 (15) Å, close to standard values. The Co1 atom lies 0.3921 (1) Å above the planar (O1/O2/C1) carboxylate group. The O—Co—O and O—Co—N bond angles deviate only slightly from ideal values, with average values of 90 (3)° and 90 (2)°, respectively.

The dihedral angle between the planar carboxylate group (O1/O2/C1) and the adjacent benzene ring [A (C2–C7)] is 22.11 (15)°, while the benzene and pyridine [B (N2/C9–C13)] rings are oriented at a dihedral angle of 89.98 (5)°.

3. Supramolecular features

In the crystal, N—H⋯O_c (c = carboxylate), N—H⋯O_n (n = nicotinamide), O—H_w⋯O_c (w = water) and O—H_w⋯O_n hydrogen bonds (Table 1) link the molecules, enclosing R₂²(8) and R₄⁴(8) ring motifs (Bernstein et al., 1995 ), forming layers parallel to (100) (Fig. 2). The layers are linked via C—H_cnb⋯O_c (cnb = cyanobenzoate) and C—H_n⋯N_cnb hydrogen bonds (Table 1), resulting in a three-dimensional network. A weak C—H⋯π interaction is also observed.

Table 1
Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the C9–C13,N2 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H31⋯O3ⁱ	0.84 (3)	2.09 (3)	2.914 (3)	166 (3)
N3—H32⋯O1ⁱⁱ	0.87 (3)	2.13 (3)	2.910 (3)	148 (3)
O4—H41⋯O1ⁱⁱⁱ	0.85 (3)	1.82 (3)	2.658 (2)	166 (3)
O4—H42⋯O3^iv	0.80 (3)	2.11 (3)	2.877 (2)	161 (2)
C4—H4⋯O1^v	0.93	2.38	3.302 (3)	173
C9—H9⋯N1^vi	0.93	2.54	3.305 (5)	140
C6—H6⋯Cg2^vii	0.93	2.76	3.691 (2)	176
Symmetry codes: (i) -x, -y, -z+1; (ii) -x+1, -y, -z+1; (iii) -x+1, -y+1, -z+1; (iv) -x, -y+1, -z+1; (v) x-1, y, z; (vi) x+1, y, z+1; (vii) x, y, z-1.

Figure 2
Part of the crystal structure viewed down [100], where the b axis is horizontal and the c axis is vertical. Intermolecular N—H⋯O and O—H⋯O hydrogen bonds are shown as dashed lines. Non-bonding H atoms have been omitted for clarity.

4. Synthesis and crystallization

The title compound was prepared by the reaction of CoSO₄·7H₂O (1.41 g, 5 mmol) in H₂O (50 ml) and nicotinamide (1.22 g, 50 mmol) in H₂O (50 ml) with sodium 4-cyanobenzoate (1.69 g, 10 mmol) in H₂O (100 ml). The mixture was filtered and set aside to crystallize at ambient temperature for several days, giving pink-coloured single crystals.

5. Refinement

The experimental details including the crystal data, data collection and refinement are summarized in Table 2. Atoms H31 and H32 (for NH₂) and H41 and H42 (for H₂O) were located in a difference Fourier map and were refined freely. The aromatic C-bound H atoms were positioned geometrically with C—H = 0.93 Å, and constrained to ride on their parent atoms, with U_iso(H) = 1.2U_eq(C). The highest electron density and the deepest hole were found 0.80 Å and 0.83 Å, respectively, from Co1.

Table 2
Experimental details

Crystal data
Chemical formula	[Co(C₈H₄NO₂)₂(C₆H₆N₂O)₂(H₂O)₂]
M_r	631.46
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	296
a, b, c (Å)	7.6474 (3), 9.9266 (4), 10.2782 (4)
α, β, γ (°)	78.680 (2), 84.200 (3), 71.556 (2)
V (Å³)	725.13 (5)
Z	1
Radiation type	Mo Kα
μ (mm⁻¹)	0.65
Crystal size (mm)	0.43 × 0.29 × 0.16

Data collection
Diffractometer	Bruker SMART BREEZE CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2012 )
T_min, T_max	0.797, 0.901
No. of measured, independent and observed [I > 2σ(I)] reflections	16533, 3639, 3419
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.672

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.119, 1.07
No. of reflections	3639
No. of parameters	212
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.94, −0.49
Computer programs: APEX2 and SAINT (Bruker, 2012), SHELXS97 and SHELXL97 (Sheldrick, 2008 ), ORTEP-3 for Windows (Farrugia, 2012 ) and WinGX (Farrugia, 2012) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1061935

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989015008270/wm5151sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015008270/wm5151Isup2.hkl

checkCIF report

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).

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

Crystal data top

[Co(C₈H₄NO₂)₂(C₆H₆N₂O)₂(H₂O)₂]	Z = 1
M_r = 631.46	F(000) = 325
Triclinic, P1	D_x = 1.446 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.6474 (3) Å	Cell parameters from 9898 reflections
b = 9.9266 (4) Å	θ = 2.2–28.6°
c = 10.2782 (4) Å	µ = 0.65 mm⁻¹
α = 78.680 (2)°	T = 296 K
β = 84.200 (3)°	Prism, translucent light pink
γ = 71.556 (2)°	0.43 × 0.29 × 0.16 mm
V = 725.13 (5) Å³

Data collection top

Bruker SMART BREEZE CCD diffractometer	3639 independent reflections
Radiation source: fine-focus sealed tube	3419 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
φ and ω scans	θ_max = 28.6°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −10→10
T_min = 0.797, T_max = 0.901	k = −12→13
16533 measured reflections	l = −13→13

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.119	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0721P)² + 0.2871P] where P = (F_o² + 2F_c²)/3
3639 reflections	(Δ/σ)_max < 0.001
212 parameters	Δρ_max = 0.94 e Å⁻³
0 restraints	Δρ_min = −0.49 e Å⁻³

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 > 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	0.5000	0.5000	0.5000	0.02573 (12)
O1	0.6366 (2)	0.34341 (18)	0.23257 (16)	0.0459 (4)
O2	0.38784 (18)	0.47948 (14)	0.33110 (13)	0.0347 (3)
O3	0.0668 (2)	0.16139 (15)	0.50697 (18)	0.0476 (4)
O4	0.22430 (19)	0.57799 (15)	0.57811 (16)	0.0362 (3)
H41	0.250 (4)	0.608 (3)	0.644 (3)	0.064 (9)*
H42	0.147 (4)	0.643 (3)	0.538 (2)	0.038 (6)*
N1	−0.0584 (5)	0.1958 (4)	−0.1318 (4)	0.1083 (13)
N2	0.4952 (2)	0.28815 (16)	0.59167 (15)	0.0303 (3)
N3	0.1614 (3)	−0.0568 (2)	0.6345 (2)	0.0473 (5)
H31	0.080 (4)	−0.079 (3)	0.602 (3)	0.063 (9)*
H32	0.238 (4)	−0.121 (3)	0.690 (3)	0.054 (8)*
C1	0.4662 (2)	0.40272 (19)	0.24567 (17)	0.0300 (3)
C2	0.3451 (2)	0.37166 (19)	0.15590 (17)	0.0298 (3)
C3	0.1622 (3)	0.3852 (2)	0.19215 (19)	0.0382 (4)
H3	0.1098	0.4240	0.2675	0.046*
C4	0.0562 (3)	0.3414 (3)	0.1171 (2)	0.0457 (5)
H4	−0.0661	0.3486	0.1430	0.055*
C5	0.1336 (3)	0.2869 (3)	0.0037 (2)	0.0458 (5)
C6	0.3143 (4)	0.2788 (3)	−0.0368 (2)	0.0570 (7)
H6	0.3641	0.2460	−0.1152	0.068*
C7	0.4203 (3)	0.3198 (3)	0.0398 (2)	0.0470 (5)
H7	0.5424	0.3126	0.0137	0.056*
C8	0.0255 (4)	0.2372 (4)	−0.0727 (3)	0.0680 (8)
C9	0.6293 (2)	0.1956 (2)	0.66831 (19)	0.0339 (4)
H9	0.7280	0.2252	0.6841	0.041*
C10	0.6261 (3)	0.0585 (2)	0.7244 (2)	0.0428 (5)
H10	0.7210	−0.0033	0.7772	0.051*
C11	0.4798 (3)	0.0138 (2)	0.7013 (2)	0.0419 (4)
H11	0.4756	−0.0786	0.7379	0.050*
C12	0.3394 (2)	0.10851 (18)	0.62286 (18)	0.0307 (4)
C13	0.3539 (2)	0.24444 (18)	0.57084 (18)	0.0304 (3)
H13	0.2601	0.3088	0.5185	0.037*
C14	0.1776 (3)	0.07268 (19)	0.5848 (2)	0.0352 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.02515 (17)	0.02306 (18)	0.03406 (19)	−0.01019 (12)	−0.00572 (12)	−0.00978 (12)
O1	0.0315 (7)	0.0592 (9)	0.0516 (8)	−0.0103 (6)	−0.0066 (6)	−0.0234 (7)
O2	0.0355 (6)	0.0333 (6)	0.0400 (7)	−0.0084 (5)	−0.0111 (5)	−0.0157 (5)
O3	0.0445 (8)	0.0303 (7)	0.0743 (11)	−0.0156 (6)	−0.0241 (7)	−0.0061 (7)
O4	0.0290 (6)	0.0348 (7)	0.0464 (8)	−0.0075 (5)	−0.0060 (6)	−0.0120 (6)
N1	0.104 (2)	0.126 (3)	0.121 (3)	−0.030 (2)	−0.052 (2)	−0.065 (2)
N2	0.0304 (7)	0.0275 (7)	0.0370 (7)	−0.0115 (6)	−0.0065 (6)	−0.0082 (6)
N3	0.0515 (11)	0.0305 (8)	0.0691 (13)	−0.0229 (8)	−0.0187 (9)	−0.0046 (8)
C1	0.0332 (8)	0.0290 (8)	0.0312 (8)	−0.0130 (7)	−0.0068 (6)	−0.0040 (6)
C2	0.0342 (8)	0.0291 (8)	0.0288 (8)	−0.0102 (7)	−0.0060 (6)	−0.0078 (6)
C3	0.0361 (9)	0.0491 (11)	0.0349 (9)	−0.0137 (8)	−0.0023 (7)	−0.0184 (8)
C4	0.0368 (10)	0.0620 (14)	0.0475 (11)	−0.0207 (9)	−0.0054 (8)	−0.0196 (10)
C5	0.0500 (11)	0.0505 (12)	0.0437 (11)	−0.0140 (9)	−0.0159 (9)	−0.0190 (9)
C7	0.0396 (10)	0.0679 (15)	0.0403 (10)	−0.0181 (10)	0.0037 (8)	−0.0253 (10)
C6	0.0523 (13)	0.0836 (18)	0.0428 (11)	−0.0148 (12)	−0.0034 (9)	−0.0377 (12)
C8	0.0649 (16)	0.0794 (19)	0.0706 (17)	−0.0168 (14)	−0.0256 (13)	−0.0357 (15)
C9	0.0295 (8)	0.0345 (9)	0.0404 (9)	−0.0108 (7)	−0.0076 (7)	−0.0083 (7)
C10	0.0382 (10)	0.0349 (10)	0.0529 (12)	−0.0071 (8)	−0.0171 (8)	−0.0012 (8)
C11	0.0456 (11)	0.0248 (8)	0.0561 (12)	−0.0123 (8)	−0.0133 (9)	−0.0006 (8)
C12	0.0331 (8)	0.0241 (8)	0.0395 (9)	−0.0111 (6)	−0.0046 (7)	−0.0106 (7)
C13	0.0311 (8)	0.0240 (7)	0.0399 (9)	−0.0104 (6)	−0.0091 (7)	−0.0069 (7)
C14	0.0361 (9)	0.0270 (8)	0.0490 (10)	−0.0139 (7)	−0.0043 (7)	−0.0133 (7)

Geometric parameters (Å, º) top

Co1—O2	2.0835 (12)	C2—C7	1.391 (3)
Co1—O2ⁱ	2.0835 (12)	C3—C4	1.387 (3)
Co1—O4	2.1350 (13)	C3—H3	0.9300
Co1—O4ⁱ	2.1350 (13)	C4—C5	1.381 (3)
Co1—N2	2.1390 (15)	C4—H4	0.9300
Co1—N2ⁱ	2.1390 (15)	C5—C6	1.384 (4)
O1—C1	1.254 (2)	C5—C8	1.444 (3)
O2—C1	1.256 (2)	C6—H6	0.9300
O3—C14	1.234 (2)	C7—C6	1.380 (3)
O4—H41	0.85 (3)	C7—H7	0.9300
O4—H42	0.80 (3)	C9—C10	1.378 (3)
N1—C8	1.136 (4)	C9—H9	0.9300
N2—C9	1.341 (2)	C10—H10	0.9300
N2—C13	1.335 (2)	C11—C10	1.383 (3)
N3—C14	1.326 (3)	C11—H11	0.9300
N3—H31	0.84 (3)	C12—C11	1.388 (3)
N3—H32	0.87 (3)	C12—C13	1.385 (2)
C1—C2	1.506 (2)	C12—C14	1.497 (2)
C2—C3	1.381 (3)	C13—H13	0.9300

O2—Co1—O2ⁱ	180.0	C4—C3—H3	119.7
O2—Co1—O4	87.59 (6)	C3—C4—H4	120.3
O2ⁱ—Co1—O4	92.41 (6)	C5—C4—C3	119.5 (2)
O2—Co1—O4ⁱ	92.41 (6)	C5—C4—H4	120.3
O2ⁱ—Co1—O4ⁱ	87.59 (6)	C4—C5—C6	120.46 (19)
O4—Co1—O4ⁱ	180.000 (1)	C4—C5—C8	119.7 (2)
O2—Co1—N2	89.99 (6)	C6—C5—C8	119.8 (2)
O2ⁱ—Co1—N2	90.01 (5)	C5—C6—H6	120.1
O2—Co1—N2ⁱ	90.01 (5)	C7—C6—C5	119.8 (2)
O2ⁱ—Co1—N2ⁱ	89.99 (6)	C7—C6—H6	120.1
O4—Co1—N2	87.40 (6)	C2—C7—H7	119.9
O4ⁱ—Co1—N2	92.60 (6)	C6—C7—C2	120.3 (2)
O4—Co1—N2ⁱ	92.60 (6)	C6—C7—H7	119.9
O4ⁱ—Co1—N2ⁱ	87.40 (6)	N1—C8—C5	178.9 (4)
N2ⁱ—Co1—N2	180.00 (4)	N2—C9—C10	122.33 (17)
C1—O2—Co1	127.68 (11)	N2—C9—H9	118.8
Co1—O4—H41	97 (2)	C10—C9—H9	118.8
Co1—O4—H42	122.7 (18)	C9—C10—C11	119.16 (17)
H42—O4—H41	107 (3)	C9—C10—H10	120.4
C9—N2—Co1	123.03 (12)	C11—C10—H10	120.4
C13—N2—Co1	118.91 (12)	C10—C11—C12	119.24 (18)
C13—N2—C9	118.05 (16)	C10—C11—H11	120.4
C14—N3—H31	116 (2)	C12—C11—H11	120.4
C14—N3—H32	123.3 (19)	C11—C12—C14	124.94 (17)
H32—N3—H31	120 (3)	C13—C12—C11	117.65 (16)
O1—C1—O2	125.70 (17)	C13—C12—C14	117.35 (16)
O1—C1—C2	116.72 (16)	N2—C13—C12	123.58 (16)
O2—C1—C2	117.48 (15)	N2—C13—H13	118.2
C3—C2—C1	120.48 (16)	C12—C13—H13	118.2
C3—C2—C7	119.43 (17)	O3—C14—N3	122.08 (18)
C7—C2—C1	119.95 (17)	O3—C14—C12	119.90 (17)
C2—C3—C4	120.52 (18)	N3—C14—C12	118.00 (18)
C2—C3—H3	119.7

O4—Co1—O2—C1	−159.74 (16)	O2—C1—C2—C7	163.80 (19)
O4ⁱ—Co1—O2—C1	20.26 (16)	C1—C2—C3—C4	−172.77 (19)
N2—Co1—O2—C1	−72.35 (16)	C7—C2—C3—C4	2.9 (3)
N2ⁱ—Co1—O2—C1	107.65 (16)	C1—C2—C7—C6	174.2 (2)
O2—Co1—N2—C9	141.91 (15)	C3—C2—C7—C6	−1.6 (4)
O2ⁱ—Co1—N2—C9	−38.09 (15)	C2—C3—C4—C5	−1.5 (4)
O2—Co1—N2—C13	−37.22 (14)	C3—C4—C5—C6	−1.4 (4)
O2ⁱ—Co1—N2—C13	142.78 (14)	C3—C4—C5—C8	178.2 (2)
O4—Co1—N2—C9	−130.50 (15)	C4—C5—C6—C7	2.8 (4)
O4ⁱ—Co1—N2—C9	49.50 (15)	C8—C5—C6—C7	−176.8 (3)
O4—Co1—N2—C13	50.36 (14)	C2—C7—C6—C5	−1.3 (4)
O4ⁱ—Co1—N2—C13	−129.64 (14)	N2—C9—C10—C11	0.0 (3)
Co1—O2—C1—O1	−13.7 (3)	C12—C11—C10—C9	−0.4 (3)
Co1—O2—C1—C2	162.49 (12)	C13—C12—C11—C10	0.2 (3)
Co1—N2—C9—C10	−178.63 (15)	C14—C12—C11—C10	177.2 (2)
C13—N2—C9—C10	0.5 (3)	C11—C12—C13—N2	0.3 (3)
Co1—N2—C13—C12	178.47 (14)	C14—C12—C13—N2	−176.86 (17)
C9—N2—C13—C12	−0.7 (3)	C11—C12—C14—O3	−174.9 (2)
O1—C1—C2—C3	156.08 (19)	C11—C12—C14—N3	3.4 (3)
O1—C1—C2—C7	−19.6 (3)	C13—C12—C14—O3	2.1 (3)
O2—C1—C2—C3	−20.5 (3)	C13—C12—C14—N3	−179.63 (19)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

Cg2 is the centroid of the C9–C13,N2 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N3—H31···O3ⁱⁱ	0.84 (3)	2.09 (3)	2.914 (3)	166 (3)
N3—H32···O1ⁱⁱⁱ	0.87 (3)	2.13 (3)	2.910 (3)	148 (3)
O4—H41···O1ⁱ	0.85 (3)	1.82 (3)	2.658 (2)	166 (3)
O4—H42···O3^iv	0.80 (3)	2.11 (3)	2.877 (2)	161 (2)
C4—H4···O1^v	0.93	2.38	3.302 (3)	173
C9—H9···N1^vi	0.93	2.54	3.305 (5)	140
C6—H6···Cg2^vii	0.93	2.76	3.691 (2)	176

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

Acknowledgements

The authors acknowledge the Aksaray University, Science and Technology Application and Research Center, Aksaray, Turkey, for the use of the Bruker SMART BREEZE CCD diffractometer (purchased under grant No. 2010K120480 of the State Planning Organization).

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