Crystal structure of di­aqua­bis­(N,N-di­ethyl­nicotinamide-κN1)bis­(2,4,6-tri­methyl­benzoato-κO1)cobalt(II)

Aşkın, G. Ş.; Necefoğlu, H.; Özkaya, S.; Çatak Çelik, R.; Hökelek, T.

doi:10.1107/S2056989016004059

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ISSN: 2056-9890

Volume 72| Part 4| April 2016| Pages 498-501

https://doi.org/10.1107/S2056989016004059

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Crystal structure of diaquabis(N,N-diethylnicotinamide-κN¹)bis(2,4,6-trimethylbenzoato-κO¹)cobalt(II)

Gülçin Şefiye Aşkın,^a Hacali Necefoğlu,^b Safiye Özkaya,^c 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, International Scientific Research Centre, Baku State University, 1148 Baku, Azerbaijan, ^cDepartment of Chemistry, Kafkas University, 36100 Kars, Turkey, 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 9 February 2016; accepted 10 March 2016; online 15 March 2016)

The centrosymmetric molecule in the monomeric title cobalt complex, [Co(C₁₀H₁₁O₂)₂(C₁₀H₁₄N₂O)₂(H₂O)₂], contains two water molecules, two 2,4,6-trimethylbenzoate (TMB) ligands and two diethylnicotinamide (DENA) ligands. All ligands coordinate to the Co^II atom in a monodentate fashion. The four O atoms around the Co^II atom form a slightly distorted square-planar arrangement, with the distorted octahedral coordination sphere completed by two pyridine N atoms of the DENA ligands. The dihedral angle between the planar carboxylate group and the adjacent benzene ring is 84.2 (4)°, while the benzene and pyridine rings are oriented at a dihedral angle of 38.87 (10)°. The water molecules exhibit both intramolecular (to the non-coordinating carboxylate O atom) and intermolecular (to the amide carbonyl O atom) O—H⋯O hydrogen bonds. The latter lead to the formation of layers parallel to (100), enclosing R₄⁴(32) ring motifs. These layers are further linked via weak C—H⋯O hydrogen bonds, resulting in a three-dimensional network. One of the two ethyl groups of the DENA ligand is disordered over two sets of sites with an occupancy ratio of 0.490 (13):0.510 (13).

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

CCDC reference: 1462884

1. Chemical context

N,N-Diethylnicotinamide (DENA), a nicotinic acid derivative, is an important respiratory stimulant (Bigoli et al., 1972 ). The crystal structure of the complex [Co(CH₃CO₂)₂(DENA)₂(H₂O)₂] [(II); Mikelashvili, 1982 ] is isostructural with the analogous Ni, Mn, Zn and Cd complexes (Sergienko et al., 1980 ). The structures of some complexes obtained from the reactions of transition metal(II) ions with DENA as ligand, e.g. [Cu₂(DENA)₂(C₆H₅COO)₄] [(III); Hökelek et al., 1995 ], [Zn₂(C₇H₅O₃)₄(DENA)₂]·2H₂O [(IV); Hökelek & Necefoğlu, 1996 ], [Mn(DENA)₂(NCS)₂] [(V); Bigoli et al., 1973a ], [Zn(DENA)₂(NCS)₂(H₂O)₂] [(VI); Bigoli et al., 1973b ] and [Cd(DENA)(SCN)₂] [(VII); Bigoli et al., 1972], have been determined previously. In complex (V), DENA is a bidentate ligand, while in complexes (III), (IV), (VI) and (VII), DENA is a monodentate ligand. In complex (III), the benzoate ion acts as a bidentate ligand, whereas in complex (IV), two of the benzoate ions act as monodentate ligands, while the other two are bidentate, bridging the two Zn^II atoms.

The structure–function–coordination relationships of arylcarboxylate ions in Co^II complexes of benzoic acid derivatives may 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 conditions and temperature of synthesis (Shnulin et al., 1981 ; Nadzhafov et al., 1981 ; Antsyshkina et al., 1980 ; Adiwidjaja et al., 1978 ). When pyridine or its derivatives are used instead of water molecules, the resulting structure is completely different (Catterick et al., 1974 ). In this context, we synthesized a Co^II-containing compound with 2,4,6-trimethylbenzoate (TMB) and DENA ligands, namely diaquabis(N,N-diethylnicotinamide-κN¹)bis(2,4,6-trimethylbenzoato-κO¹)cobalt(II), [Co(DENA)₂(TMB)₂(H₂O)₂], and report herein its crystal structure.

2. Structural commentary

The asymmetric unit of the mononuclear title complex contains one Co^II atom located on an inversion centre, one TMB ligand, one DENA ligand and one water molecule, with all ligands coordinating to the metal ion in a monodentate fashion (Fig. 1).

Figure 1
The molecular structure of the title complex with the atom-numbering scheme for the asymmetric unit. Unlabelled atoms are generated by symmetry code (1 − x, 1 − y, −z). Displacement ellipsoids are drawn at the 40% probability level. Intramolecular O—H⋯O hydrogen bonds are shown as dashed lines.

The two carboxylate O atoms (O2 and O2ⁱ) of the two symmetry-related TMB anions and the two symmetry-related water O atoms (O4 and O4ⁱ) form a slightly distorted square-planar arrangement around the Co1 atom. The slightly distorted octahedral coordination sphere is completed by the two pyridine N atoms (N1 and N1ⁱ) of the two symmetry-related DENA ligands in axial positions [symmetry code: (i) 1 − x, 1 − y, −z] (Fig. 1). The Co—O bond lengths for water oxygens atoms are by ca 0.1 Å longer than those involving the benzoate oxygen atoms. The Co—N bond length is the longest in the CoO₄N₂ octahedron (Table 1). The deviation of the O—Co—O and O—Co—N bond angles from ideal values is minute [range 87.66 (7) to 92.34 (7)° for cis angles; all trans angles are 180° due to symmetry]. The near equalities of the C1—O1 [1.245 (4) Å] and C1—O2 [1.254 (4) Å] bonds in the carboxylate group indicate delocalized bonding arrangements, rather than localized single and double bonds. The dihedral angle between the planar carboxylate group (O1/O2/C1) and the adjacent benzene ring A (C2–C7) is 84.2 (4)°, while the benzene (A) and pyridine rings (B) (N1/C11–C15) are inclined by a dihedral angle of 38.87 (10)°.

Table 1
Selected bond lengths (Å)

Co1—O2	2.0336 (18)	Co1—N1	2.1913 (19)
Co1—O4	2.1561 (18)

3. Supramolecular features

Intramolecular O—H_w⋯O_c (w = water, c = non-coordinating carboxylate O atom) hydrogen bonds (Table 2) link the water ligands to the TMB anions (Fig. 1). The other water H atom is involved in intermolecular O—H_w⋯O_DENA (O_DENA = carbonyl O atom of N,N-diethylnicotinamide) hydrogen bonds (Table 2), leading to the formation of layers parallel to (100) enclosing R₄⁴(32) ring motifs (Fig. 2). The layers are further linked into a three-dimensional network structure via weak C—H_TMB⋯O_c (TMB = 2,4,6-trimethylbenzoate) and C—H_DENA ⋯ O_DENA hydrogen bonds (Table 2), enclosing R₂²(7) ring motifs (Fig. 3).

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H1W⋯O1ⁱ	0.80 (6)	1.87 (6)	2.634 (3)	160 (7)
O4—H2W⋯O3ⁱⁱ	0.76 (7)	2.10 (7)	2.850 (3)	170 (7)
C10—H10A⋯O1ⁱⁱⁱ	0.96	2.43	3.365 (6)	165
C15—H15⋯O3^iv	0.93	2.50	3.420 (4)	172
Symmetry codes: (i) -x+1, -y+1, -z; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Figure 2
Part of the crystal structure viewed approximately down [100]. Intra- and intermolecular O—H⋯O hydrogen bonds, shown as dashed lines, enclose R₄⁴(32) ring motifs. Only one part of the disordered group and only H atoms involved in hydrogen bonding have been included for clarity.

Figure 3
A partial view of the crystal packing of the title compound. The O—H_w⋯O_c, O—H_w⋯O_DENA, C—H_TMB⋯O_c and C—H_DENA⋯O_DENA (w = water, c = carboxylate, DENA = N,N-diethylnicotinamide and TMB = 2,4,6-trimethylbenzoate) hydrogen bonds, enclosing R₂²(7) and R₄⁴(32) ring motifs, are shown as dashed lines (see Table 2

). Only one part of the disordered group and only H atoms involved in hydrogen bonding have been included for clarity.

4. Synthesis and crystallization

The title compound was prepared by the reaction of CoSO₄·7H₂O (1.41 g, 5 mmol) in H₂O (100 ml) and N,N-diethylnicotinamide (1.78 g, 10 mmol) in H₂O (10 ml) with sodium 2,4,6-trimethylbenzoate (1.86 g, 10 mmol) in H₂O (150 ml). The mixture was filtered and set aside to crystallize at ambient temperature for three weeks, giving pink single crystals.

5. Refinement

Experimental details including crystal data, data collection and refinement are summarized in Table 3. Atoms H1W and H2W (of the water molecule) were located in a difference Fourier map. Their coordinates were refined freely, with U_iso(H) = 1.5U_eq(O). C-bound H atoms were positioned geometrically, with C—H = 0.93, 0.96 and 0.97 Å for aromatic, methyl and methylene H atoms, respectively, and constrained to ride on their parent atoms, with U_iso(H) = k × U_eq(C), where k = 1.5 for methyl H atoms and k = 1.2 for other H atoms. The disordered ethyl group (C19, C20) was refined over two sets of sites with distance restraints and SIMU and DELU restraints (Sheldrick, 2008 ). The refined occupancy ratio of the two orientations is 0.490 (13):0.510 (13).

Table 3
Experimental details

Crystal data
Chemical formula	[Co(C₁₀H₁₁O₂)₂(C₁₀H₁₄N₂O)₂(H₂O)₂]
M_r	777.80
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	12.9646 (4), 10.8636 (3), 15.6297 (5)
β (°)	111.596 (3)
V (Å³)	2046.79 (12)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.47
Crystal size (mm)	0.45 × 0.40 × 0.33

Data collection
Diffractometer	Bruker SMART BREEZE CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2012 )
T_min, T_max	0.754, 0.861
No. of measured, independent and observed [I > 2σ(I)] reflections	42492, 5124, 3701
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.670

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.063, 0.155, 1.07
No. of reflections	5124
No. of parameters	270
No. of restraints	42
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.63, −0.39
Computer programs: APEX2 and SAINT (Bruker, 2012), SHELXS97 and SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012 ), WinGX (Farrugia, 2012) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1462884

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989016004059/wm5273sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989016004059/wm5273Isup2.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).

Diaquabis(N,N-diethylnicotinamide-κN¹)bis(2,4,6-trimethylbenzoato-κO¹)cobalt(II) top

Crystal data top

[Co(C₁₀H₁₁O₂)₂(C₁₀H₁₄N₂O)₂(H₂O)₂]	F(000) = 826
M_r = 777.80	D_x = 1.262 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9990 reflections
a = 12.9646 (4) Å	θ = 2.3–28.4°
b = 10.8636 (3) Å	µ = 0.47 mm⁻¹
c = 15.6297 (5) Å	T = 100 K
β = 111.596 (3)°	Block, translucent light pink
V = 2046.79 (12) Å³	0.45 × 0.40 × 0.33 mm
Z = 2

Data collection top

Bruker SMART BREEZE CCD diffractometer	5124 independent reflections
Radiation source: fine-focus sealed tube	3701 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
φ and ω scans	θ_max = 28.5°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −17→16
T_min = 0.754, T_max = 0.861	k = −14→14
42492 measured reflections	l = −20→20

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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.155	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0662P)² + 1.2728P] where P = (F_o² + 2F_c²)/3
5124 reflections	(Δ/σ)_max < 0.001
270 parameters	Δρ_max = 0.63 e Å⁻³
42 restraints	Δρ_min = −0.39 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	Occ. (<1)
Co1	0.5000	0.5000	0.0000	0.03723 (16)
O1	0.7500 (2)	0.6149 (3)	0.1133 (2)	0.1140 (12)
O2	0.64234 (15)	0.45260 (17)	0.10503 (11)	0.0476 (4)
O3	0.47496 (19)	0.62630 (18)	0.39053 (11)	0.0613 (5)
O4	0.41728 (17)	0.35512 (17)	0.04417 (13)	0.0495 (5)
H1W	0.358 (6)	0.358 (7)	0.004 (5)	0.201*
H2W	0.440 (6)	0.290 (6)	0.057 (5)	0.201*
N1	0.45672 (18)	0.62382 (18)	0.09231 (13)	0.0434 (5)
N2	0.3331 (3)	0.5092 (3)	0.30486 (19)	0.0929 (12)
C1	0.7318 (3)	0.5109 (3)	0.1382 (2)	0.0589 (8)
C2	0.8208 (2)	0.4486 (3)	0.21743 (19)	0.0546 (7)
C3	0.8883 (3)	0.3599 (3)	0.2011 (2)	0.0684 (9)
C4	0.9635 (3)	0.2965 (4)	0.2757 (3)	0.0784 (10)
H4	1.0091	0.2369	0.2654	0.094*
C5	0.9713 (3)	0.3208 (4)	0.3649 (2)	0.0761 (10)
C6	0.9055 (3)	0.4105 (4)	0.3785 (2)	0.0713 (9)
H6	0.9109	0.4279	0.4383	0.086*
C7	0.8310 (3)	0.4766 (3)	0.3068 (2)	0.0621 (8)
C8	0.7606 (4)	0.5758 (4)	0.3247 (3)	0.0895 (12)
H8A	0.7634	0.5690	0.3867	0.134*
H8B	0.6853	0.5668	0.2827	0.134*
H8C	0.7882	0.6550	0.3161	0.134*
C9	0.8814 (4)	0.3334 (5)	0.1040 (3)	0.1066 (15)
H9A	0.9321	0.2684	0.1052	0.160*
H9B	0.9005	0.4062	0.0783	0.160*
H9C	0.8072	0.3087	0.0670	0.160*
C10	1.0488 (4)	0.2448 (5)	0.4441 (3)	0.1131 (16)
H10A	1.1133	0.2225	0.4313	0.170*
H10B	1.0112	0.1717	0.4513	0.170*
H10C	1.0709	0.2923	0.4998	0.170*
C11	0.4479 (2)	0.5794 (2)	0.16908 (15)	0.0457 (6)
H11	0.4627	0.4964	0.1823	0.055*
C12	0.4181 (2)	0.6499 (2)	0.22983 (15)	0.0425 (6)
C13	0.4001 (3)	0.7736 (3)	0.21270 (19)	0.0602 (8)
H13	0.3822	0.8244	0.2531	0.072*
C14	0.4095 (3)	0.8204 (3)	0.1337 (2)	0.0735 (10)
H14	0.3980	0.9038	0.1201	0.088*
C15	0.4357 (3)	0.7430 (3)	0.07530 (18)	0.0574 (7)
H15	0.4390	0.7755	0.0213	0.069*
C16	0.4100 (3)	0.5942 (2)	0.31519 (16)	0.0501 (7)
C17	0.3272 (4)	0.4478 (4)	0.3879 (3)	0.1070 (16)
H17A	0.3127	0.3608	0.3753	0.128*
H17B	0.3983	0.4558	0.4381	0.128*
C18	0.2407 (5)	0.5002 (6)	0.4159 (4)	0.154 (3)
H18A	0.2431	0.4618	0.4719	0.231*
H18B	0.1695	0.4862	0.3685	0.231*
H18C	0.2528	0.5871	0.4258	0.231*
C19A	0.2227 (8)	0.5259 (10)	0.2181 (7)	0.080 (3)	0.490 (13)
H19A	0.1601	0.5419	0.2364	0.096*	0.490 (13)
H19B	0.2294	0.5928	0.1794	0.096*	0.490 (13)
C19B	0.2696 (8)	0.4402 (8)	0.2180 (5)	0.077 (3)	0.510 (13)
H19C	0.2477	0.3595	0.2318	0.093*	0.510 (13)
H19D	0.3135	0.4307	0.1798	0.093*	0.510 (13)
C20A	0.2102 (12)	0.4038 (11)	0.1694 (9)	0.128 (5)	0.490 (13)
H20A	0.1443	0.4049	0.1148	0.192*	0.490 (13)
H20B	0.2047	0.3392	0.2094	0.192*	0.490 (13)
H20C	0.2736	0.3896	0.1529	0.192*	0.490 (13)
C20B	0.1696 (11)	0.5203 (13)	0.1714 (9)	0.134 (5)	0.510 (13)
H20D	0.1236	0.4828	0.1146	0.201*	0.510 (13)
H20E	0.1933	0.5999	0.1592	0.201*	0.510 (13)
H20F	0.1281	0.5292	0.2109	0.201*	0.510 (13)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0546 (3)	0.0354 (2)	0.0260 (2)	−0.0004 (2)	0.0197 (2)	0.00073 (17)
O1	0.0881 (19)	0.100 (2)	0.115 (2)	−0.0333 (16)	−0.0081 (16)	0.0591 (18)
O2	0.0552 (11)	0.0477 (10)	0.0375 (9)	−0.0020 (9)	0.0143 (8)	0.0047 (8)
O3	0.1013 (16)	0.0519 (11)	0.0305 (9)	−0.0127 (11)	0.0240 (10)	−0.0057 (8)
O4	0.0709 (13)	0.0412 (10)	0.0428 (10)	−0.0004 (9)	0.0287 (9)	0.0037 (8)
N1	0.0644 (14)	0.0388 (11)	0.0315 (10)	0.0001 (10)	0.0231 (10)	0.0017 (8)
N2	0.121 (3)	0.122 (3)	0.0444 (14)	−0.066 (2)	0.0413 (17)	−0.0121 (15)
C1	0.0588 (18)	0.0664 (19)	0.0506 (16)	−0.0066 (15)	0.0188 (14)	0.0134 (14)
C2	0.0478 (16)	0.0628 (17)	0.0507 (15)	−0.0064 (14)	0.0154 (13)	0.0107 (13)
C3	0.0615 (19)	0.085 (2)	0.0600 (18)	−0.0051 (18)	0.0241 (16)	0.0060 (17)
C4	0.059 (2)	0.093 (3)	0.086 (2)	0.0135 (19)	0.0313 (19)	0.016 (2)
C5	0.0547 (19)	0.100 (3)	0.067 (2)	0.0009 (18)	0.0144 (16)	0.0269 (19)
C6	0.063 (2)	0.095 (3)	0.0503 (17)	−0.0042 (19)	0.0149 (15)	0.0123 (17)
C7	0.0588 (18)	0.072 (2)	0.0528 (17)	−0.0072 (15)	0.0173 (14)	0.0084 (14)
C8	0.108 (3)	0.088 (3)	0.074 (2)	0.013 (2)	0.036 (2)	0.002 (2)
C9	0.112 (3)	0.142 (4)	0.076 (3)	0.014 (3)	0.046 (3)	−0.005 (3)
C10	0.087 (3)	0.147 (4)	0.095 (3)	0.028 (3)	0.021 (2)	0.054 (3)
C11	0.0712 (18)	0.0384 (13)	0.0309 (11)	−0.0009 (12)	0.0229 (12)	0.0006 (9)
C12	0.0573 (15)	0.0439 (13)	0.0293 (11)	−0.0054 (11)	0.0193 (11)	−0.0032 (9)
C13	0.095 (2)	0.0503 (16)	0.0467 (14)	0.0119 (15)	0.0400 (16)	−0.0028 (12)
C14	0.136 (3)	0.0410 (15)	0.0594 (17)	0.0231 (17)	0.054 (2)	0.0102 (13)
C15	0.095 (2)	0.0469 (15)	0.0424 (13)	0.0085 (15)	0.0403 (15)	0.0102 (12)
C16	0.0799 (19)	0.0448 (14)	0.0334 (12)	−0.0066 (14)	0.0300 (13)	−0.0068 (10)
C17	0.167 (5)	0.104 (3)	0.069 (2)	−0.057 (3)	0.065 (3)	−0.003 (2)
C18	0.151 (5)	0.246 (8)	0.095 (4)	−0.066 (5)	0.080 (4)	−0.016 (4)
C19A	0.077 (7)	0.100 (7)	0.077 (6)	−0.026 (6)	0.043 (5)	−0.015 (5)
C19B	0.110 (6)	0.068 (5)	0.064 (5)	−0.040 (5)	0.043 (4)	−0.023 (4)
C20A	0.129 (10)	0.123 (9)	0.129 (9)	−0.050 (8)	0.045 (8)	−0.064 (8)
C20B	0.110 (9)	0.165 (13)	0.097 (9)	−0.019 (7)	0.004 (7)	−0.011 (8)

Geometric parameters (Å, º) top

Co1—O2	2.0336 (18)	C9—H9C	0.9600
Co1—O2ⁱ	2.0336 (18)	C10—H10A	0.9600
Co1—O4	2.1561 (18)	C10—H10B	0.9600
Co1—O4ⁱ	2.1561 (19)	C10—H10C	0.9600
Co1—N1	2.1913 (19)	C11—H11	0.9300
Co1—N1ⁱ	2.1913 (19)	C12—C11	1.381 (3)
O2—C1	1.254 (4)	C12—C16	1.503 (3)
O4—H1W	0.80 (7)	C13—C12	1.374 (4)
O4—H2W	0.76 (7)	C13—C14	1.382 (4)
N1—C11	1.336 (3)	C13—H13	0.9300
N1—C15	1.330 (3)	C14—C15	1.372 (4)
N2—C17	1.486 (4)	C14—H14	0.9300
N2—C19A	1.579 (11)	C15—H15	0.9300
N2—C19B	1.503 (8)	C16—N2	1.325 (4)
C1—O1	1.245 (4)	C17—H17A	0.9700
C1—C2	1.508 (4)	C17—H17B	0.9700
C2—C7	1.387 (4)	C18—C17	1.462 (7)
C3—C2	1.387 (5)	C18—H18A	0.9600
C3—C4	1.396 (5)	C18—H18B	0.9600
C3—C9	1.514 (5)	C18—H18C	0.9600
C4—H4	0.9300	C19A—C20A	1.508 (13)
C5—C4	1.385 (5)	C19A—H19A	0.9700
C5—C10	1.519 (5)	C19A—H19B	0.9700
C6—C5	1.363 (5)	C19B—C20B	1.508 (14)
C6—H6	0.9300	C19B—H19C	0.9700
C7—C6	1.381 (4)	C19B—H19D	0.9700
C7—C8	1.504 (5)	C20A—H20A	0.9600
C8—H8A	0.9600	C20A—H20B	0.9600
C8—H8B	0.9600	C20A—H20C	0.9600
C8—H8C	0.9600	C20B—H20D	0.9600
C9—H9A	0.9600	C20B—H20E	0.9600
C9—H9B	0.9600	C20B—H20F	0.9600

O2ⁱ—Co1—O2	180.00 (13)	C5—C10—H10A	109.5
O2—Co1—O4	88.12 (7)	C5—C10—H10B	109.5
O2ⁱ—Co1—O4	91.88 (7)	C5—C10—H10C	109.5
O2—Co1—O4ⁱ	91.88 (7)	H10A—C10—H10B	109.5
O2ⁱ—Co1—O4ⁱ	88.12 (7)	H10A—C10—H10C	109.5
O2—Co1—N1	90.01 (8)	H10B—C10—H10C	109.5
O2ⁱ—Co1—N1	89.99 (8)	N1—C11—C12	123.7 (2)
O2—Co1—N1ⁱ	89.99 (8)	N1—C11—H11	118.1
O2ⁱ—Co1—N1ⁱ	90.01 (8)	C12—C11—H11	118.1
O4—Co1—O4ⁱ	180.00 (9)	C11—C12—C16	121.1 (2)
O4—Co1—N1	87.66 (7)	C13—C12—C11	118.6 (2)
O4ⁱ—Co1—N1	92.34 (7)	C13—C12—C16	120.3 (2)
O4—Co1—N1ⁱ	92.34 (7)	C12—C13—C14	118.0 (2)
O4ⁱ—Co1—N1ⁱ	87.66 (7)	C12—C13—H13	121.0
N1—Co1—N1ⁱ	180.00 (7)	C13—C14—H14	120.2
C1—O2—Co1	129.21 (18)	C14—C13—H13	121.0
Co1—O4—H1W	99 (5)	C15—C14—C13	119.6 (3)
Co1—O4—H2W	125 (5)	C15—C14—H14	120.2
H1W—O4—H2W	115 (6)	N1—C15—C14	123.1 (2)
C11—N1—Co1	119.79 (16)	N1—C15—H15	118.5
C15—N1—Co1	123.32 (16)	C14—C15—H15	118.5
C15—N1—C11	116.9 (2)	O3—C16—N2	122.6 (2)
C16—N2—C17	119.0 (3)	O3—C16—C12	119.6 (2)
C16—N2—C19A	115.4 (4)	N2—C16—C12	117.9 (2)
C16—N2—C19B	126.5 (3)	N2—C17—H17A	109.1
C17—N2—C19A	118.7 (4)	N2—C17—H17B	109.1
C17—N2—C19B	112.2 (4)	C18—C17—N2	112.3 (5)
O1—C1—O2	125.6 (3)	C18—C17—H17A	109.1
O1—C1—C2	119.2 (3)	C18—C17—H17B	109.1
O2—C1—C2	115.1 (2)	H17A—C17—H17B	107.9
C3—C2—C1	120.3 (3)	C17—C18—H18A	109.5
C3—C2—C7	120.4 (3)	C17—C18—H18B	109.5
C7—C2—C1	119.3 (3)	C17—C18—H18C	109.5
C2—C3—C4	118.8 (3)	H18A—C18—H18B	109.5
C2—C3—C9	120.6 (3)	H18A—C18—H18C	109.5
C4—C3—C9	120.6 (4)	H18B—C18—H18C	109.5
C3—C4—H4	119.4	N2—C19A—H19A	111.1
C5—C4—C3	121.1 (3)	N2—C19A—H19B	111.1
C5—C4—H4	119.4	C20A—C19A—N2	103.1 (10)
C4—C5—C10	119.9 (4)	C20A—C19A—H19A	111.1
C6—C5—C4	118.4 (3)	C20A—C19A—H19B	111.1
C6—C5—C10	121.7 (4)	H19A—C19A—H19B	109.1
C5—C6—C7	122.4 (3)	N2—C19B—C20B	103.7 (9)
C5—C6—H6	118.8	N2—C19B—H19C	111.0
C7—C6—H6	118.8	N2—C19B—H19D	111.0
C2—C7—C8	120.4 (3)	C20B—C19B—H19C	111.0
C6—C7—C2	118.8 (3)	C20B—C19B—H19D	111.0
C6—C7—C8	120.8 (3)	H19C—C19B—H19D	109.0
C7—C8—H8A	109.5	C19A—C20A—H20A	109.5
C7—C8—H8B	109.5	C19A—C20A—H20B	109.5
C7—C8—H8C	109.5	C19A—C20A—H20C	109.5
H8A—C8—H8B	109.5	H20A—C20A—H20B	109.5
H8A—C8—H8C	109.5	H20A—C20A—H20C	109.5
H8B—C8—H8C	109.5	H20B—C20A—H20C	109.5
C3—C9—H9A	109.5	C19B—C20B—H20D	109.5
C3—C9—H9B	109.5	C19B—C20B—H20E	109.5
C3—C9—H9C	109.5	C19B—C20B—H20F	109.5
H9A—C9—H9B	109.5	H20D—C20B—H20E	109.5
H9A—C9—H9C	109.5	H20D—C20B—H20F	109.5
H9B—C9—H9C	109.5	H20E—C20B—H20F	109.5

O4—Co1—O2—C1	−165.8 (2)	C1—C2—C7—C8	−5.2 (5)
O4ⁱ—Co1—O2—C1	14.2 (2)	C3—C2—C7—C6	−3.2 (5)
N1—Co1—O2—C1	−78.1 (2)	C3—C2—C7—C8	177.8 (3)
N1ⁱ—Co1—O2—C1	101.9 (2)	C4—C3—C2—C1	−174.6 (3)
O2—Co1—N1—C11	−57.7 (2)	C4—C3—C2—C7	2.4 (5)
O2ⁱ—Co1—N1—C11	122.3 (2)	C9—C3—C2—C1	6.1 (5)
O2—Co1—N1—C15	123.9 (2)	C9—C3—C2—C7	−177.0 (3)
O2ⁱ—Co1—N1—C15	−56.1 (2)	C2—C3—C4—C5	0.0 (5)
O4—Co1—N1—C11	30.5 (2)	C9—C3—C4—C5	179.4 (4)
O4ⁱ—Co1—N1—C11	−149.5 (2)	C6—C5—C4—C3	−1.5 (6)
O4—Co1—N1—C15	−148.0 (2)	C10—C5—C4—C3	176.2 (4)
O4ⁱ—Co1—N1—C15	32.0 (2)	C7—C6—C5—C4	0.7 (5)
Co1—O2—C1—O1	2.1 (5)	C7—C6—C5—C10	−177.0 (4)
Co1—O2—C1—C2	179.24 (18)	C2—C7—C6—C5	1.6 (5)
Co1—N1—C11—C12	−178.2 (2)	C8—C7—C6—C5	−179.4 (3)
C15—N1—C11—C12	0.4 (4)	C13—C12—C11—N1	−2.4 (4)
Co1—N1—C15—C14	−179.5 (3)	C16—C12—C11—N1	−179.8 (3)
C11—N1—C15—C14	2.0 (5)	C11—C12—C16—O3	113.7 (3)
C16—N2—C17—C18	99.5 (5)	C11—C12—C16—N2	−64.8 (4)
C19A—N2—C17—C18	−49.9 (7)	C13—C12—C16—O3	−63.7 (4)
C19B—N2—C17—C18	−96.4 (6)	C13—C12—C16—N2	117.9 (4)
C16—N2—C19A—C20A	125.7 (6)	C14—C13—C12—C11	2.0 (5)
C17—N2—C19A—C20A	−83.8 (7)	C14—C13—C12—C16	179.5 (3)
C19B—N2—C19A—C20A	8.4 (7)	C12—C13—C14—C15	0.2 (5)
C16—N2—C19B—C20B	−89.3 (8)	C13—C14—C15—N1	−2.3 (6)
C17—N2—C19B—C20B	108.1 (8)	O3—C16—N2—C17	−1.6 (6)
C19A—N2—C19B—C20B	−0.6 (9)	O3—C16—N2—C19A	148.8 (5)
O1—C1—C2—C3	−99.3 (4)	O3—C16—N2—C19B	−163.2 (6)
O1—C1—C2—C7	83.8 (4)	C12—C16—N2—C17	176.8 (3)
O2—C1—C2—C3	83.4 (4)	C12—C16—N2—C19A	−32.8 (5)
O2—C1—C2—C7	−93.6 (4)	C12—C16—N2—C19B	15.2 (7)
C1—C2—C7—C6	173.8 (3)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H1W···O1ⁱ	0.80 (6)	1.87 (6)	2.634 (3)	160 (7)
O4—H2W···O3ⁱⁱ	0.76 (7)	2.10 (7)	2.850 (3)	170 (7)
C10—H10A···O1ⁱⁱⁱ	0.96	2.43	3.365 (6)	165
C15—H15···O3^iv	0.93	2.50	3.420 (4)	172

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

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 of Planning Organization).

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