Crystal structure of catena-poly[[[di­aqua­bis­(2,4,6-tri­methyl­benzoato-κO)cobalt(II)]-μ-aqua-κ2O:O] dihydrate]

Hökelek, T.; Akduran, N.; Özkaya, S.; Necefoğlu, H.

doi:10.1107/S2056989017005564

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 73| Part 5| May 2017| Pages 708-712

https://doi.org/10.1107/S2056989017005564

Open

access

Crystal structure of catena-poly[[[diaquabis(2,4,6-trimethylbenzoato-κO)cobalt(II)]-μ-aqua-κ²O:O] dihydrate]

Tuncer Hökelek,^a ^* Nurcan Akduran,^b Safiye Özkaya ^c and Hacali Necefoğlu ^c,^d

^aDepartment of Physics, Hacettepe University, 06800 Beytepe, Ankara, Turkey, ^bSANAEM, Saray Mahallesi, Atom Caddesi, No. 27, 06980 Saray-Kazan, Ankara, Turkey, ^cDepartment of Chemistry, Kafkas University, 36100 Kars, Turkey, and ^dInternational Scientific Research Centre, Baku State University, 1148 Baku, Azerbaijan
^*Correspondence e-mail: merzifon@hacettepe.edu.tr

Edited by T. J. Prior, University of Hull, England (Received 31 March 2017; accepted 12 April 2017; online 13 April 2017)

The asymmetric unit of the title one-dimensional polymeric compound, {[Co(C₁₀H₁₁O₂)₂(H₂O)₃]·2H₂O}_n, contains one Co^II cation situated on a centre of inversion, one-half of a coordinating water molecule, one 2,4,6-trimethylbenzoate (TMB) anion together with one coordinating and one non-coordinating water molecule; the TMB anion acts as a monodentate ligand. In the anion, the carboxylate group is twisted away from the attached benzene ring by 84.9 (2)°. The Co^II atom is coordinated by two TMB anions and two water molecules in the basal plane, while another water molecule bridges the Co^II atoms in the axial directions, forming polymeric chains running along [001]. The coordination environment for the Co^II cation is a slightly distorted octahedron. The coordinating and bridging water molecules link to the carboxylate groups via intra- and intermolecular O—H⋯O hydrogen bonds, enclosing S(6) ring motifs, while the coordinating, bridging and non-coordinating water molecules link to the carboxylate groups and the coordinating water molecules link to the non-coordinating water molecules via O—H⋯O hydrogen bonds, enclosing R₂²(8) and R₃³(8) ring motifs. Weak C—H⋯O and C—H⋯π interactions may further stabilize the crystal structure.

Keywords: crystal structure; cobalt(II); transition metal complex; benzoic acid derivative.

CCDC reference: 1543701

1. Chemical context

Transition metal complexes with ligands of biochemical interest, such as imidazole and some N-protected amino acids, 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 the 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 ).

The solid-state structures of anhydrous zinc(II) carboxylates include one-dimensional (Guseinov et al., 1984 ; Clegg et al., 1986a ), two-dimensional (Clegg et al., 1986b , 1987 ) and three-dimensional (Capilla & Aranda, 1979 ) polymeric motifs of different types, while discrete monomeric complexes with octahedral or tetrahedral coordination geometry are found if water or other donor molecules coordinate to the Zn^II cation (van Niekerk et al., 1953 ; Usubaliev et al., 1992 ).

The structures of some mononuclear polymeric complexes obtained from the reactions of transition metal(II) ions with nicotinamide (NA) and/or some benzoic acid derivatives as ligands have been determined, e.g. {Mn(C₁₁H₁₄NO₂)₂(H₂O)₃·2H₂O}_n [(II); Hökelek et al., 2009 )], [Mn(C₇H₄FO₂)₂(H₂O)]_n [(III); Necefoğlu et al., 2011 )], {[Pb(C₉H₉O₂)₂(C₆H₆N₂O)]·H₂O}_n [(IV); Hökelek et al., 2011 )], {[Pb(C₇H₅O₃)₂(C₆H₆N₂O)]H₂O}_n [(V); Zaman et al., 2012 )] and {[Zn(C₇H₄ClO₂)₂(H₂O)]}_n [(VI); Bozkurt et al., 2013 )], where the transition metal(II) cations are bridged by water molecules in (II), 4-fluorobenzoate anions in (III), nicotinamide ligands in (IV), 3-hydroxybenzoate anions in (V) and 3-chlorobenzoate anions in (VI). The synthesis and structure determination of the title compound, (I), a one-dimensional polymeric cobalt(II) complex with two 2,4,6-trimethylbenzoate (TMB) ligands and four coordinating and two non-coordinating water molecules, was undertaken in order to compare the results obtained with those reported previously. Its crystal structure is reported herein.

2. Structural commentary

The asymmetric unit of the title one-dimensional polymeric compound, (I), contains one Co^II cation situated on a centre of inversion, one-half of a coordinating water molecule, one 2,4,6-trimethylbenzoate (TMB) anion together with the one coordinating and one non-coordinating water molecules; the TMB anion acts as a monodentate ligand (Fig. 1).

Figure 1
The asymmetric unit of the title molecule with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

The Co^II atom is coordinated by two TMB anions and two water molecules in the basal plane while another water molecule bridges the Co^II atoms in the axial directions, resulting in a slightly distorted octahedral coordination sphere around each Co²⁺ cation, and forming polymeric chains (Fig. 2) running along [001] (Figs. 3 and 4). The cobalt cation is formally Co²⁺ within the structure, in line with the presence of bridging water molecules rather than bridging hydroxide groups. This is confirmed by softness-sensitive BVS calculations (Adams, 2001 ), which identify the BVS for the Co atom to be 2.05 (5).

Figure 2
Partial view of the polymeric chain of the title compound. H atoms of the 2,4,6-trimethylbenzoate (TMB) anions have been omitted for clarity.

Figure 3
A partial packing diagram of the title one-dimensional polymeric compound in a view approximately along the b axis, where the c axis is horizontal and the a axis is vertical. H atoms have been omitted for clarity.

Figure 4
View of the hydrogen bonding and packing of the title one-dimensional polymeric compound along the c axis. H atoms not involved in classical hydrogen bonds have been omitted for clarity.

The two carboxylate O atoms (O1 and O1ⁱ) of the two symmetry-related TMB anions and the two symmetry-related water O atoms (O3 and O3ⁱ) around the Co^II cation form a slightly distorted square-planar arrangement with an average Co1—O bond length of 2.058 (2) Å. The slightly distorted octahedral coordination is completed by the symmetry-related bridging O atoms (O4 and O4ⁱ) with a Co1—O4 bond length of 2.2060 (11) Å in the axial directions (Fig. 2) [symmetry code: (i) 1 − x, 1 − y, 1 − z]. The Co—O bond lengths are in the range of 2.041 (2)–2.2060 (11) Å. Among the Co—O coordinations the Co1—O3 bond [2.041 (2) Å] is the shortest and the Co1—O4 bond [2.2060 (11) Å] is the longest, probably as a result of the bidentate bridging coordination of O4 with a very wide Co1—O4—Co1ⁱⁱ bond angle of 132.95 (13)° [symmetry code: (ii) 1 − x, y, $[{1\over 2}]$ − z]. The Co1 atom lies 0.2077 (1) Å above the carboxylate (O1/O2/C1) group, which makes a dihedral angle of 84.9 (2)° with the adjacent benzene (C2–C7) ring.

Neighboring Co^II atoms are bridged by H₂O molecules (Fig. 2) and they are also coordinated by monodentate carboxylate groups. The non-coordinating oxygen atoms of the carboxylate groups interact with the bridging water molecules via short hydrogen bonds (Table 1 and Fig. 5), increasing the Lewis basicity of the bridging water molecules by attracting the protons of the water molecules to the oxygen atoms of the carboxylate groups. Intramolecular O—H_brdW⋯O_c and intermolecular O—H_coordW⋯O_c (brdW = bridging water, coordW = coordinating water and c = carboxylate) hydrogen bonds (Table 1) link the bridging and coordinating water molecules to the carboxylate oxygen atoms, enclosing S(6) ring motifs (Fig. 5).

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C2–C7 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H31⋯O1ⁱ	0.80 (2)	1.90 (2)	2.697 (3)	170 (5)
O3—H32⋯O5	0.82 (3)	1.91 (3)	2.724 (5)	174 (3)
O4—H41⋯O2ⁱⁱ	0.83 (3)	1.82 (3)	2.622 (3)	164 (4)
O5—H52⋯O2ⁱⁱⁱ	0.82 (3)	1.98 (4)	2.726 (4)	151 (6)
C10—H10C⋯O5^iv	0.96	2.59	3.466 (7)	152
C6—H6⋯Cg1^v	0.93	3.28	4.063 (4)	143
C9—H9A⋯Cg1^v	0.96	3.40	3.961 (7)	120
Symmetry codes: (i) $[-x+1, y, -z+{\script{1\over 2}}]$ ; (ii) $[x, -y+1, z-{\script{1\over 2}}]$ ; (iii) $[-x+1, y, -z+{\script{3\over 2}}]$ ; (iv) -x+1, -y+1, -z+1; (v) $[-x+{\script{1\over 2}}, y+{\script{3\over 2}}, -z-{\script{1\over 2}}]$ .

Figure 5
Part of the crystal structure. Intramolecular and intermolecular O—H⋯O hydrogen bonds, enclosing S(6), R₂²(8) and R₃³(8) ring motifs, are shown as dashed lines. H atoms not involved in classical hydrogen bonds have been omitted for clarity.

3. Supramolecular features

In the crystal, O—H_coordW ⋯ O_c and O—H_coordW⋯O_noncoordW, O—H_noncoordW⋯O_c, O—H_brdW⋯O_c (noncoordW = non-coordinating water) hydrogen bonds (Table 1) link the molecules, enclosing R₂²(8) and R₃³(8) ring motifs, respectively (Fig. 5). O—H⋯O hydrogen bonds (Table 1) also link the hydrogen-bonded polymeric chains running along [001] into networks parallel to (011) (Fig. 4). The crystal structure is further stabilized by weak C—H⋯O and C—H⋯π interactions (Table 1).

4. Comparison with related structures

In the crystal structure of a similar complex, catena-poly[[[diaquabis[4-(diethylamino)benzoato-κO¹]manganese(II)]-μ-aqua]dihydrate], {[Mn(C₁₁H₁₄NO₂)₂(H₂O)₃]·2(H₂O)}_n, (II), (Hökelek et al., 2009), the two independent Mn^II atoms are located on a centre of symmetry and are coordinated by two 4-(diethylamino)benzoate (DEAB) anions and two water molecules in the basal plane, while another water molecule bridges the Mn atoms in the axial directions, forming polymeric chains as in the title compound, (I). In (II), the Mn—O bond lengths are in the range 2.1071 (14)–2.2725 (13) Å. The Mn—O bond lengths [2.2725 (13) and 2.2594 (13) Å] for the bridging water molecule are the longest with an Mn—O—Mn bond angle of 128.35 (6)°.

In the crystal structure of catena-[bis(μ₂-aqua)tetraaquatetrakis(2,4,6-trimethylbenzoato-O)dinickel(II) tetrahydrate, {[Ni(C₁₀H₁₁O₂)₂(H₂O)₃]·2H₂O}_n, [(VII; Indrani et al., 2009 )], the two independent Ni^II atoms are located on a centre of symmetry and are coordinated by two 2,4,6-trimethylbenzoate (TMB) anions and two water molecules in the basal plane, while another water molecule bridges the Ni atoms in the axial directions, forming polymeric chains as in the title compound, (I). In (VII), the Ni—O bond lengths are in the range 2.0337 (15)–2.1316 (13) Å. The Ni—O bond lengths [2.1316 (13) and 2.1299 (13) Å] for the bridging water molecule are the longest with an Ni—O—Ni bond angle of 134.65 (7)°.

We also solved the crystal structure of catena-poly[[[diaquabis(2,4,6-trimethylbenzoato-κO¹)manganese(II)], {[Mn(C₁₀H₁₁O₂)₂(H₂O)₃]·2H₂O}_n, (VIII), which had previously been reported by Chen et al. (2007 ). In (VIII), the Mn^II atom and the bridging water O atom are located on a centre of symmetry and the Mn^II atom is coordinated by two 2,4,6-trimethylbenzoate (TMB) anions and two water molecules in the basal plane, while another water molecule bridges the Mn^II cations in the axial directions, forming polymeric chains as in the title compound, (I). The Mn—O bond lengths are in the range 2.1409 (15)–2.2734 (7) Å. The Mn—O bond length [2.2734 (7) Å] for the bridging water molecule is the longest with an Mn—O—Mn bond angle of 128.41 (8)°.

In the title compound, (I), the near equalities of the C1—O1 [1.259 (4) Å] and C1—O2 [1.246 (4) Å] bonds in the carboxylate groups indicate delocalized bonding arrangements, rather than localized single and double bonds. The O2—C1—O1 bond angle [124.5 (3)°] is increased slightly compared to the free acid [122.2°] due to the coordination of oxygen atom (O1) to the metal atom. The O2—C1—O1 bond angle may be compared with the corresponding values of 121.96 (18) and 122.35 (18)° in (II), 124.0 (2)° in (III), 120.6 (6) and 121.3 (7)° in (IV), 121.7 (2) and 121.9 (3)° in (V), 123.47 (14)° in (VI), 124.29 (18) and 124.33 (18)° in (VII) and 124.02 (16)° in (VIII). The benzoate ions coordinate to the metal atoms in a monodentate fashion in (II), (III), (VI), (VII) and (VIII), and they are bidentate in (IV) and (V).

The Co1⋯Co1ⁱⁱ distance [4.045 (15) Å] across the chain (Fig. 2) and the Co1—O4—Co1ⁱⁱ bond angle [132.95 (13)°] in (I) may be compared with the corresponding values of 4.079 (4) Å and 128.35 (6)° in (II), 4.951 (3) Å in (III), 9.795 (4) Å in (IV), 7.363 (4) Å in (V), 4.3798 (3) Å in (VI), 3.932 Å and 134.65 (7)° in (VII) and 4.049 (15) Å and 128.41 (8)° in (VIII). According to these results, when the transition metal(II) atoms are bridged by the water molecules the M—O_brdW—M (M = transition metal and brdW = bridging water) bond angles increase, while the M—O_brdW bond lengths decrease with increasing atomic number, Z, of the transition metal(II) atoms and the M⋯M distances across the polymeric chains are almost the same, independent of the type of anion coordinating to the metal(II) atoms.

5. Synthesis and crystallization

The title compound was prepared by the reaction of CoSO₄·7H₂O (0.70 g, 2.5 mmol) with sodium 2,4,6-trimethylbenzoate (0.93 g, 5 mmol) in H₂O (150 ml) at room temperature. The mixture was set aside to crystallize at ambient temperature for eight weeks, giving pink single crystals (yield: 0.96 g, 81%). FT–IR: 3630, 3405, 3209, 2286, 2069, 1612, 1535, 1446, 1400, 1181, 1114, 1031, 893, 857, 827, 758, 690, 615, 570, 490, 478, 401.

6. Refinement

The experimental details including the crystal data, data collection and refinement are summarized in Table 2. H atoms of water molecules were located in difference-Fourier maps and refined with distance and angle restraints (SIMU, DELU and ISOR restraints in SHELXL). Bond lengths and angles for water molecules are: O3—H31 = 0.806 (19), O3—H32 = 0.818 (18), O4—H41 = 0.827 (18), O5—H51 = 0.812 (10), O5—H52 = 0.820 (10) Å and H31—O3—H32 = 107 (4) and H51—O5—H52 = 107 (4)° The C-bound H atoms were positioned geometrically with C—H = 0.93 and 0.96 Å for aromatic and methyl 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 aromatic H atoms. The maximum and minimum electron densities were found 0.89 Å and 0.82 Å from Co1. The high residual electron density value of 2.178 e Å⁻¹ may be due to the poor quality of the crystal.

Table 2
Experimental details

Crystal data
Chemical formula	[Co(C₁₀H₁₁O₂)₂(H₂O)₃]·2H₂O
M_r	475.39
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	29.5261 (5), 10.1413 (2), 8.0906 (2)
β (°)	91.894 (4)
V (Å³)	2421.27 (9)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.75
Crystal size (mm)	0.35 × 0.29 × 0.20

Data collection
Diffractometer	Bruker SMART BREEZE CCD diffractometer
Absorption correction	Multi-scan SADABS; Bruker, 2012
T_min, T_max	0.779, 0.864
No. of measured, independent and observed [I > 2σ(I)] reflections	25445, 2957, 2448
R_int	0.058
(sin θ/λ)_max (Å⁻¹)	0.664

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.060, 0.166, 1.09
No. of reflections	2957
No. of parameters	161
No. of restraints	74
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	2.18, −0.52
Computer programs: APEX2 and SAINT (Bruker, 2012), SHELXS97 and SHELXL97 (Sheldrick, 2008 ), ORTEP-3 for Windows and WinGX (Farrugia, 2012 ) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1543701

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989017005564/pj2043sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017005564/pj2043Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); 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, 2012); software used to prepare material for publication: WinGX publication routines (Farrugia, 2012) and PLATON (Spek, 2009).

catena-Poly[[[diaquabis(2,4,6-trimethylbenzoato-κO)cobalt(II)]-µ-aqua-κ²O:O] dihydrate] top

Crystal data top

[Co(C₁₀H₁₁O₂)₂(H₂O)₃]·2H₂O	F(000) = 1004
M_r = 475.39	D_x = 1.304 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 9882 reflections
a = 29.5261 (5) Å	θ = 2.8–28.1°
b = 10.1413 (2) Å	µ = 0.75 mm⁻¹
c = 8.0906 (2) Å	T = 296 K
β = 91.894 (4)°	Block, translucent light pink
V = 2421.27 (9) Å³	0.35 × 0.29 × 0.20 mm
Z = 4

Data collection top

Bruker SMART BREEZE CCD diffractometer	2957 independent reflections
Radiation source: fine-focus sealed tube	2448 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.058
φ and ω scans	θ_max = 28.2°, θ_min = 1.4°
Absorption correction: multi-scan SADABS; Bruker, 2012	h = −38→39
T_min = 0.779, T_max = 0.864	k = −12→13
25445 measured reflections	l = −10→10

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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.166	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ²(F_o²) + (0.0725P)² + 9.9721P] where P = (F_o² + 2F_c²)/3
2957 reflections	(Δ/σ)_max < 0.001
161 parameters	Δρ_max = 2.18 e Å⁻³
74 restraints	Δρ_min = −0.52 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	0.02399 (18)
O1	0.55057 (8)	0.6264 (2)	0.4251 (3)	0.0409 (6)
O2	0.57111 (9)	0.7216 (3)	0.6626 (3)	0.0503 (7)
O3	0.45248 (10)	0.6292 (3)	0.4084 (3)	0.0492 (7)
H31	0.4484 (17)	0.625 (6)	0.310 (2)	0.086 (17)*
H32	0.4289 (10)	0.656 (4)	0.446 (5)	0.057 (13)*
O4	0.5000	0.4132 (3)	0.2500	0.0274 (6)
H41	0.5249 (8)	0.378 (4)	0.237 (5)	0.048 (10)*
O5	0.37711 (14)	0.7250 (4)	0.5521 (4)	0.0768 (10)
H51	0.3607 (18)	0.785 (4)	0.522 (7)	0.103 (15)*
H52	0.385 (2)	0.740 (6)	0.649 (3)	0.100 (15)*
C1	0.57564 (11)	0.7012 (3)	0.5121 (4)	0.0348 (6)
C2	0.61375 (11)	0.7694 (3)	0.4254 (4)	0.0366 (7)
C3	0.65665 (13)	0.7129 (4)	0.4284 (5)	0.0509 (9)
C4	0.69080 (15)	0.7756 (5)	0.3429 (6)	0.0625 (11)
H4	0.7196	0.7386	0.3439	0.075*
C5	0.68271 (16)	0.8917 (5)	0.2564 (5)	0.0647 (12)
C6	0.64030 (15)	0.9461 (4)	0.2567 (5)	0.0567 (11)
H6	0.6349	1.0245	0.1997	0.068*
C7	0.60467 (13)	0.8874 (4)	0.3403 (4)	0.0450 (8)
C8	0.55866 (16)	0.9483 (5)	0.3372 (7)	0.0689 (12)
H8A	0.5409	0.9133	0.2458	0.103*
H8B	0.5614	1.0421	0.3252	0.103*
H8C	0.5441	0.9286	0.4387	0.103*
C9	0.7209 (2)	0.9563 (8)	0.1634 (8)	0.109 (2)
H9A	0.7152	0.9467	0.0465	0.164*
H9B	0.7491	0.9145	0.1941	0.164*
H9C	0.7225	1.0482	0.1911	0.164*
C10	0.66644 (18)	0.5874 (5)	0.5233 (7)	0.0777 (15)
H10A	0.6629	0.6028	0.6391	0.117*
H10B	0.6970	0.5597	0.5049	0.117*
H10C	0.6457	0.5198	0.4860	0.117*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0380 (3)	0.0218 (3)	0.0124 (3)	−0.00099 (18)	0.00338 (18)	−0.00010 (16)
O1	0.0549 (14)	0.0470 (13)	0.0210 (9)	−0.0202 (10)	0.0055 (9)	−0.0019 (9)
O2	0.0670 (16)	0.0616 (16)	0.0227 (10)	−0.0243 (13)	0.0073 (10)	−0.0082 (10)
O3	0.0633 (16)	0.0626 (17)	0.0221 (11)	0.0257 (13)	0.0050 (10)	0.0023 (11)
O4	0.0375 (15)	0.0275 (13)	0.0175 (12)	0.000	0.0044 (10)	0.000
O5	0.087 (2)	0.094 (3)	0.0492 (18)	0.032 (2)	−0.0007 (16)	−0.0010 (18)
C1	0.0459 (16)	0.0352 (15)	0.0234 (13)	−0.0057 (12)	0.0017 (11)	0.0016 (11)
C2	0.0439 (16)	0.0405 (16)	0.0255 (13)	−0.0142 (13)	0.0024 (11)	−0.0034 (12)
C3	0.051 (2)	0.056 (2)	0.046 (2)	−0.0079 (17)	0.0059 (15)	0.0018 (17)
C4	0.048 (2)	0.084 (3)	0.056 (2)	−0.011 (2)	0.0104 (17)	0.005 (2)
C5	0.063 (3)	0.088 (3)	0.043 (2)	−0.033 (2)	0.0041 (18)	0.011 (2)
C6	0.072 (3)	0.057 (2)	0.0398 (19)	−0.027 (2)	−0.0063 (17)	0.0137 (17)
C7	0.055 (2)	0.0468 (19)	0.0326 (16)	−0.0138 (15)	−0.0030 (14)	0.0054 (14)
C8	0.071 (3)	0.060 (3)	0.075 (3)	0.002 (2)	−0.005 (2)	0.024 (2)
C9	0.081 (4)	0.163 (6)	0.083 (4)	−0.057 (4)	0.011 (3)	0.042 (4)
C10	0.070 (3)	0.068 (3)	0.095 (4)	0.015 (2)	0.015 (3)	0.025 (3)

Geometric parameters (Å, º) top

Co1—O1	2.074 (2)	C3—C10	1.509 (6)
Co1—O1ⁱ	2.074 (2)	C4—C5	1.387 (7)
Co1—O3	2.041 (2)	C4—H4	0.9300
Co1—O3ⁱ	2.041 (2)	C5—C9	1.524 (6)
Co1—O4	2.2060 (11)	C6—C5	1.368 (7)
Co1—O4ⁱ	2.2060 (11)	C6—H6	0.9300
O1—C1	1.259 (4)	C7—C6	1.402 (5)
O2—C1	1.246 (4)	C7—C8	1.492 (6)
O3—H31	0.806 (19)	C8—H8A	0.9600
O3—H32	0.818 (18)	C8—H8B	0.9600
O4—Co1ⁱⁱ	2.2060 (11)	C8—H8C	0.9600
O4—H41	0.827 (18)	C9—H9A	0.9600
O5—H51	0.812 (10)	C9—H9B	0.9600
O5—H52	0.820 (10)	C9—H9C	0.9600
C2—C1	1.513 (4)	C10—H10A	0.9600
C2—C3	1.390 (5)	C10—H10B	0.9600
C2—C7	1.401 (5)	C10—H10C	0.9600
C3—C4	1.395 (5)

O1—Co1—O1ⁱ	180.00 (9)	C4—C3—C10	120.5 (4)
O1—Co1—O4	87.53 (7)	C3—C4—H4	119.3
O1ⁱ—Co1—O4	92.47 (7)	C5—C4—C3	121.5 (4)
O1—Co1—O4ⁱ	92.47 (7)	C5—C4—H4	119.3
O1ⁱ—Co1—O4ⁱ	87.53 (7)	C4—C5—C9	119.7 (5)
O3—Co1—O1	89.44 (11)	C6—C5—C4	118.9 (4)
O3ⁱ—Co1—O1	90.56 (11)	C6—C5—C9	121.4 (5)
O3—Co1—O1ⁱ	90.56 (11)	C5—C6—C7	122.1 (4)
O3ⁱ—Co1—O1ⁱ	89.44 (11)	C5—C6—H6	119.0
O3ⁱ—Co1—O3	180.00 (12)	C7—C6—H6	119.0
O3—Co1—O4	86.80 (8)	C2—C7—C6	117.7 (4)
O3ⁱ—Co1—O4	93.20 (8)	C2—C7—C8	121.4 (3)
O3—Co1—O4ⁱ	93.20 (8)	C6—C7—C8	120.9 (4)
O3ⁱ—Co1—O4ⁱ	86.80 (8)	C7—C8—H8A	109.5
O4ⁱ—Co1—O4	180.0	C7—C8—H8B	109.5
C1—O1—Co1	128.67 (19)	C7—C8—H8C	109.5
Co1—O3—H32	131 (3)	H8A—C8—H8B	109.5
Co1—O3—H31	114 (4)	H8A—C8—H8C	109.5
H32—O3—H31	107 (4)	H8B—C8—H8C	109.5
Co1—O4—Co1ⁱⁱ	132.95 (13)	C5—C9—H9A	109.5
Co1—O4—H41	108 (3)	C5—C9—H9B	109.5
Co1ⁱⁱ—O4—H41	92 (3)	C5—C9—H9C	109.5
H51—O5—H52	107 (4)	H9A—C9—H9B	109.5
O1—C1—C2	116.7 (3)	H9A—C9—H9C	109.5
O2—C1—O1	124.5 (3)	H9B—C9—H9C	109.5
O2—C1—C2	118.9 (3)	C3—C10—H10A	109.5
C3—C2—C1	119.7 (3)	C3—C10—H10B	109.5
C3—C2—C7	121.3 (3)	C3—C10—H10C	109.5
C7—C2—C1	119.0 (3)	H10A—C10—H10B	109.5
C2—C3—C4	118.5 (4)	H10A—C10—H10C	109.5
C2—C3—C10	121.1 (4)	H10B—C10—H10C	109.5

O3—Co1—O1—C1	105.4 (3)	C1—C2—C3—C10	−2.7 (6)
O3ⁱ—Co1—O1—C1	−74.6 (3)	C7—C2—C3—C4	−0.7 (6)
O4—Co1—O1—C1	−167.8 (3)	C7—C2—C3—C10	178.7 (4)
O4ⁱ—Co1—O1—C1	12.2 (3)	C1—C2—C7—C6	−178.0 (3)
O1—Co1—O4—Co1ⁱⁱ	−46.09 (7)	C1—C2—C7—C8	1.5 (5)
O1ⁱ—Co1—O4—Co1ⁱⁱ	133.91 (7)	C3—C2—C7—C6	0.6 (5)
O3—Co1—O4—Co1ⁱⁱ	43.49 (9)	C3—C2—C7—C8	−179.9 (4)
O3ⁱ—Co1—O4—Co1ⁱⁱ	−136.51 (9)	C2—C3—C4—C5	0.1 (7)
Co1—O1—C1—O2	−7.3 (5)	C10—C3—C4—C5	−179.3 (5)
Co1—O1—C1—C2	172.4 (2)	C3—C4—C5—C6	0.6 (7)
C3—C2—C1—O1	−94.3 (4)	C3—C4—C5—C9	−179.5 (5)
C3—C2—C1—O2	85.4 (4)	C7—C6—C5—C4	−0.7 (7)
C7—C2—C1—O1	84.4 (4)	C7—C6—C5—C9	179.4 (5)
C7—C2—C1—O2	−95.9 (4)	C2—C7—C6—C5	0.1 (6)
C1—C2—C3—C4	177.9 (3)	C8—C7—C6—C5	−179.4 (4)

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

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C2–C7 ring.

D—H···A	D—H	H···A	D···A	D—H···A
O3—H31···O1ⁱⁱ	0.80 (2)	1.90 (2)	2.697 (3)	170 (5)
O3—H32···O5	0.82 (3)	1.91 (3)	2.724 (5)	174 (3)
O4—H41···O2ⁱⁱⁱ	0.83 (3)	1.82 (3)	2.622 (3)	164 (4)
O5—H52···O2^iv	0.82 (3)	1.98 (4)	2.726 (4)	151 (6)
C10—H10C···O5ⁱ	0.96	2.59	3.466 (7)	152
C6—H6···Cg1^v	0.93	3.28	4.063 (4)	143
C9—H9A···Cg1^v	0.96	3.40	3.961 (7)	120

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

Acknowledgements

The authors acknowledge the Scientific and Technological Research Application and Research Center, Sinop University, Turkey, for the use of the Bruker D8 QUEST diffractometer.

References

Adams, St. (2001). Acta Cryst. B57, 278–287. Web of Science CrossRef CAS IUCr Journals Google Scholar
Adiwidjaja, G., Rossmanith, E. & Küppers, H. (1978). Acta Cryst. B34, 3079–3083. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Amiraslanov, I. R., Mamedov, Kh. S., Movsumov, E. M., Musaev, F. N. & Nadzhafov, G. N. (1979). Zh. Strukt. Khim. 20, 1075–1080. CAS Google Scholar
Antolini, L., Battaglia, L. P., Bonamartini Corradi, A., Marcotrigiano, G., Menabue, L., Pellacani, G. C. & Saladini, M. (1982). Inorg. Chem. 21, 1391–1395. CSD CrossRef CAS Web of Science Google Scholar
Antsyshkina, A. S., Chiragov, F. M. & Poray-Koshits, M. A. (1980). Koord. Khim. 15, 1098–1103. Google Scholar
Bozkurt, N., Dilek, N., Çaylak Delibaş, N., Necefoğlu, H. & Hökelek, T. (2013). Acta Cryst. E69, m381–m382. CSD CrossRef IUCr Journals Google Scholar
Bruker (2012). APEX2, SAINT and SADABS. Bruker AXS Inc. Madison, Wisconsin, USA. Google Scholar
Capilla, A. V. & Aranda, R. A. (1979). Cryst. Struct. Commun. 8, 795–798. Google Scholar
Catterick (neé Drew), J., Hursthouse, M. B., New, D. B. & Thornton, P. (1974). J. Chem. Soc. Chem. Commun. pp. 843–844. Google Scholar
Chen, H. J. & Chen, X. M. (2002). Inorg. Chim. Acta, 329, 13–21. Web of Science CSD CrossRef CAS Google Scholar
Chen, M. S., Hu, J. R., deng, Y. F., Kuang, D. Z., Zhang, C. H., Feng, Y. L. & Peng, Y. L. (2007). Chin. J. Inorg. Chem. 23, 145–148. CAS Google Scholar
Clegg, W., Little, I. R. & Straughan, B. P. (1986a). Acta Cryst. C42, 919–920. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Clegg, W., Little, I. R. & Straughan, B. P. (1986b). Acta Cryst. C42, 1701–1703. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Clegg, W., Little, I. R. & Straughan, B. P. (1987). Acta Cryst. C43, 456–457. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Guseinov, G. A., Musaev, F. N., Usubaliev, B. T., Amiraslanov, I. R. & Mamedov, Kh. S. (1984). Koord. Khim. 10, 117–122. CAS Google Scholar
Hauptmann, R., Kondo, M. & Kitagawa, S. (2000). Z. Kristallogr. New Cryst. Struct. 215, 169–172. CAS Google Scholar
Hökelek, T., Dal, H., Tercan, B., Aybirdi, Ö. & Necefoğlu, H. (2009). Acta Cryst. E65, m747–m748. Web of Science CSD CrossRef IUCr Journals Google Scholar
Hökelek, T., Tercan, B., Şahin, E., Aktaş, V. & Necefoğlu, H. (2011). Acta Cryst. E67, m1057–m1058. Web of Science CSD CrossRef IUCr Journals Google Scholar
Indrani, M., Ramasubramanian, R., Fronczek, F. R., Vasanthacharya, N. Y. & Kumaresan, S. (2009). J. Mol. Struct. 931, 35–44. Web of Science CSD CrossRef CAS Google Scholar
Nadzhafov, G. N., Shnulin, A. N. & Mamedov, Kh. S. (1981). Zh. Strukt. Khim. 22, 124–128. CAS Google Scholar
Necefoğlu, H., Özbek, F. E., Öztürk, V., Tercan, B. & Hökelek, T. (2011). Acta Cryst. E67, m1003–m1004. Web of Science CSD CrossRef IUCr Journals Google Scholar
Niekerk, J. N. van, Schoening, F. R. L. & Talbot, J. H. (1953). Acta Cryst. 6, 720–723. CSD CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shnulin, A. N., Nadzhafov, G. N., Amiraslanov, I. R., Usubaliev, B. T. & Mamedov, Kh. S. (1981). Koord. Khim. 7, 1409–1416. CAS Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Usubaliev, B. T., Guliev, F. I., Musaev, F. N., Ganbarov, D. M., Ashurova, S. A. & Movsumov, E. M. (1992). Zh. Strukt. Khim. 33, m203–m207. Google Scholar
Zaman, İ. G., Çaylak Delibaş, N., Necefoğlu, H. & Hökelek, T. (2012). Acta Cryst. E68, m257–m258. CSD CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.