Crystal structure of a CoII coordination polymer: catena-poly[[μ-aqua-bis­(μ-2-methyl­propano­ato)-κ2O:O′;κ2O:O-cobalt(II)] monohydrate]

Fischer, A.I.; Gurzhiy, V.V.; Aleksandrova, J.V.; Pakina, M.I.

doi:10.1107/S2056989017001360

research communications

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ISSN: 2056-9890

Volume 73| Part 3| March 2017| Pages 318-321

https://doi.org/10.1107/S2056989017001360

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Crystal structure of a Co^II coordination polymer: catena-poly[[μ-aqua-bis(μ-2-methylpropanoato)-κ²O:O′;κ²O:O-cobalt(II)] monohydrate]

Andrei I. Fischer,^a ^* Vladislav V. Gurzhiy,^b ^* Julia V. Aleksandrova ^a and Maria I. Pakina ^a

^aSt Petersburg State Institute of Technology, Moskovsky pr. 26, 190013, St Petersburg, Russian Federation, and ^bInstitute of Earth Sciences, St Petersburg State University, University Emb. 7/9, 199034, St Petersburg, Russian Federation
^*Correspondence e-mail: andreasfischer@mail.ru, vladgeo17@mail.ru

Edited by G. Smith, Queensland University of Technology, Australia (Received 6 December 2016; accepted 26 January 2017; online 3 February 2017)

In the title cobalt(II) coordination polymer with isobutyrate ligands, {[Co{CH(CH₃)₂CO₂}₂(H₂O)]·H₂O}_n, the Co²⁺ ion is hexacoordinated in a slightly distorted octahedral coordination environment defined by two O atoms from two bridging water molecules and four O atoms from four bridging carboxylate ligands. The carboxylates adopt two different coordination modes, μ-(κ²O:O′) and μ-(κ²O:O), forming a one-dimensional polymeric chain extending along [010]. The intra-chain cobalt⋯cobalt separation is 3.2029 (2) Å. The polymeric chains are linked by hydrogen bonds involving the water molecules of solvation, giving a two-dimensional network structure lying parallel to (100).

Keywords: crystal structure; polynuclear complexes; coordination polymer; cobalt carboxylates; cobalt(II) isobutyrate dihydrate.

CCDC reference: 1529830

1. Chemical context

Carboxylate anions still remain a popular choice as bridging ligands because of their ability to form diverse oligo- and polynuclear structures. Oligo- and polynuclear cobalt carboxylates in turn have attracted great attention because of their utilization in homogeneous oxidation catalysis (Gates, 1992 ; Parshall & Ittel, 1992 ; Partenheimer, 1995 ; Ward et al., 2013a ), and their interesting magnetic properties (Ward et al., 2013b ; Eremenko et al., 2009 ). Recently, we have reported on the crystal structures of the hydrated polymeric cobalt(II) propionate (Fischer et al., 2010 ) and butyrate (Fischer et al., 2011 ), which were prepared by the reaction of cobalt(II) carbonate hydrate with the corresponding aqueous carboxylic acid. The aim of these studies was to investigate the influence of the steric features of the carboxylate anion on the structure of the resulting compounds. Cobalt(II) carboxylates are of interest for our group as starting materials for the synthesis of mixed-valence cobalt carboxylates (Fischer, Kuznetsov & Belyaev, 2012 ; Fischer, Kuznetsov, Shchukarev & Belyaev, 2012 ). In addition, we intend to examine the catalytic activity of the cobalt(II) carboxylates obtained, which will be used for introduction into the sodalite cages of synthetic NaY zeolites, modified by decationation and dealuminizing methods.

As a part of our ongoing studies on these compounds, we describe here synthesis and crystal structure of the title compound, {[Co{CH(CH₃)₂CO₂}₂(H₂O)]·H₂O}_n, (I).

2. Structural commentary

The structure of (I) contains one independent Co²⁺ cation coordinated by four O atoms from four bridging isobutyrate ligands and two O atoms from two bridging water molecules (O1W) in a distorted octahedral coordination. A water molecule of solvation (O2W) is also present (Fig. 1). The Co—O bond lengths are in the range 2.0142 (6)–2.1777 (6) Å (Table 1) and the cis-angles about the Co²⁺ atom vary in the range 78.99 (3)–110.31 (2)°. This data correlates with the angles and the distances in cobalt(II) acetate dihydrate which has a similar structure (Jiao et al., 2000 ), as well as with the closely related cobalt(II) propionate dihydrate (Fischer et al., 2010) and cobalt(II) butyrate 1.7-hydrate (Fischer et al., 2011).

Table 1
Selected geometric parameters (Å, °)

Co1—O1A	2.0449 (6)	Co1—O1Bⁱ	2.1198 (6)
Co1—O2Aⁱ	2.0142 (6)	Co1—O1W	2.1768 (6)
Co1—O1B	2.1100 (6)	Co1—O1Wⁱ	2.1777 (6)

O1A—Co1—O1B	88.13 (3)	O2Aⁱ—Co1—O1Wⁱ	88.33 (3)
O1A—Co1—O1Bⁱ	89.41 (3)	O1B—Co1—O1Bⁱ	170.29 (2)
O1A—Co1—O1W	92.18 (3)	O1B—Co1—O1W	79.22 (2)
O1A—Co1—O1Wⁱ	88.29 (3)	O1Bⁱ—Co1—O1W	91.49 (2)
O2Aⁱ—Co1—O1A	175.30 (3)	O1B—Co1—O1Wⁱ	110.31 (2)
O2Aⁱ—Co1—O1B	89.99 (3)	O1Bⁱ—Co1—O1Wⁱ	78.99 (2)
O2Aⁱ—Co1—O1Bⁱ	93.14 (3)	O1W—Co1—O1Wⁱ	170.46 (2)
O2Aⁱ—Co1—O1W	91.70 (3)
Symmetry code: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 1
The coordination mode and atom-numbering scheme for (I)

. Displacement ellipsoids of the non H-atoms are drawn at the 50% probability level, with H atoms shown as spheres of arbitrary radius. [Symmetry codes: (i) −x + 1, y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (ii) −x + 1, y − $[{1\over 2}]$ , −z + $[{1\over 2}]$ .

The structure of (I) is based on infinite chains with _∞[Co(H₂O)((CH₃)₂CHCOO)₂] composition, extending along [010] (Fig. 2). The Co⋯Co distance within the chain is 3.2029 (2) Å. The formation of polymeric chains may be a plausible reason for the crystal growth being predominantly along the b axis. The bridging carboxylate groups adopt two coordination modes, μ-(κ²O:O′) and μ-(κ²O:O). The C—O bond lengths of the first group (involving O1A and O2A) have close values [1.2755 (10) and 1.2533 (10) Å], whereas those of the second group (involving O1B and O2B) have a more striking difference [1.2878 (9) and 1.2510 (11) Å]. The carboxylate O2B atom of the second group forms an inter-unit hydrogen bond with the bridging water molecule [O1W—H⋯O2Bⁱ = 2.6206 (9) Å] (Fig. 2, Table 2).

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W1⋯O2W	0.79 (2)	1.91 (2)	2.6638 (10)	161 (2)
O1W—H1W2⋯O2Bⁱ	0.88 (2)	1.79 (2)	2.6206 (9)	158 (2)
O2W—H2W1⋯O1Aⁱⁱ	0.86 (1)	2.01 (1)	2.7967 (9)	151 (1)
O2W—H2W2⋯O2Bⁱⁱⁱ	0.88 (1)	1.95 (1)	2.8087 (9)	163 (1)
C2B—H2B⋯O2Aⁱ	0.98	2.47	3.3094 (11)	144
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Figure 2
The one-dimensional polymeric structure of (I)

extending along [010], with the intramolecular hydrogen bond shown as a dashed line. The carbon-bound H atoms and the water molecule of solvation have been omitted.

3. Supramolecular features

Metal–organic chain polymers are linked together through the water molecule of solvation (O2W) by a system of hydrogen bonds, forming a sheet structure arranged parallel to (100) (Table 2, Fig. 3). Only weak van der Waals interactions link neighboring sheets in the crystal structure.

Figure 3
The packing diagram of (I)

, showing the interactions between the coordination polymer chains. Hydrogen bonds are shown as dashed lines. The carbon-bound H atoms are omitted for clarity.

4. Database survey

A survey of the Cambridge Structural Database (Groom et al., 2016 ) reveals only the following related one-dimensional polymeric structures of cobalt(II) carboxylates with composition _∞[Co(RCOO)₂(H₂O)]: acetate (Jiao et al., 2000), propionate (Fischer et al., 2010) and butyrate (Fischer et al., 2011).

5. Synthesis and crystallization

The title compound was synthesized using a similar procedure as for the synthesis of the analogous carboxylates cobalt(II) propionate dihydrate (Fischer et al., 2010) and cobalt(II) butyrate 1.7-hydrate (Fischer et al., 2011). To a mixture of isobutyric acid (8.8 g, 100 mmol) and water (100 ml), an excess of fresh cobalt(II) carbonate hexahydrate, CoCO₃·6H₂O, (13.6 g, 60 mmol) was added. The reaction mixture was periodically stirred in an ultrasonic bath at room temperature until the liberation of carbon dioxide ceased. The unreacted CoCO₃·6H₂O was removed by filtration, and the filtrate was allowed to stand at room temperature for slow evaporation. Red single crystals of (I) suitable for X-ray diffraction were obtained after several days. The yield was 81%.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. The hydrogen atoms of the water molecules were located from differenc maps and refined in an isotropic approximation with U_iso(H) set to 1.5U_eq(O). Other hydrogen atoms were placed in calculated positions and refined using a riding model with d(C—H) = 0.98 Å, U_iso(H) = 1.2U_eq(C) for the tertiary carbon atoms and d(C—H) = 0.96 Å, U_iso(H) = 1.5U_eq(C) for the methyl groups.

Table 3
Experimental details

Crystal data
Chemical formula	[Co(C₄H₇O₂)₂(H₂O)]·H₂O
M_r	269.15
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	11.9999 (4), 6.3815 (2), 16.1374 (6)
β (°)	109.540 (2)
V (Å³)	1164.59 (7)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	1.48
Crystal size (mm)	0.35 × 0.15 × 0.1

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.304, 0.417
No. of measured, independent and observed [I > 2σ(I)] reflections	25308, 5082, 4459
R_int	0.070
(sin θ/λ)_max (Å⁻¹)	0.807

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.068, 1.03
No. of reflections	5082
No. of parameters	152
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.25, −0.51
Computer programs: APEX2 and SAINT (Bruker, 2014), SHELXS97 (Sheldrick, 2008 ), SHELXL2012 (Sheldrick, 2015 ), DIAMOND (Brandenburg, 2012 ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 1529830

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2056989017001360/zs2371sup1.cif

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2012); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

catena-Poly[[µ-aqua-bis(µ-2-methylpropanoato)-κ²O:O';κ²O:O-cobalt(II)] monohydrate] top

Crystal data top

[Co(C₄H₇O₂)₂(H₂O)]·H₂O	F(000) = 564
M_r = 269.15	D_x = 1.535 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.9999 (4) Å	Cell parameters from 9959 reflections
b = 6.3815 (2) Å	θ = 3.5–49.6°
c = 16.1374 (6) Å	µ = 1.48 mm⁻¹
β = 109.540 (2)°	T = 100 K
V = 1164.59 (7) Å³	Prism, red
Z = 4	0.35 × 0.15 × 0.1 mm

Data collection top

Bruker APEXII CCD diffractometer	5082 independent reflections
Radiation source: fine-focus sealed tube	4459 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.070
φ and ω scans	θ_max = 35.0°, θ_min = 3.5°
Absorption correction: multi-scan (SADABS; Bruker, 2014)	h = −17→19
T_min = 0.304, T_max = 0.417	k = −10→4
25308 measured reflections	l = −26→26

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.026	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.068	w = 1/[σ²(F_o²) + (0.0362P)²] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
5082 reflections	Δρ_max = 1.25 e Å⁻³
152 parameters	Δρ_min = −0.51 e Å⁻³
4 restraints

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Co1	0.49462 (2)	0.68360 (2)	0.24090 (2)	0.00839 (4)
O1A	0.66165 (5)	0.60756 (10)	0.24434 (4)	0.01230 (11)
O2A	0.67317 (6)	0.26293 (11)	0.27311 (4)	0.01275 (11)
O1B	0.43294 (5)	0.41595 (10)	0.16212 (4)	0.01065 (11)
O2B	0.34759 (6)	0.20179 (10)	0.05000 (4)	0.01437 (12)
O1W	0.49903 (6)	0.45171 (10)	0.34088 (4)	0.01116 (11)
H1W1	0.4417 (17)	0.463 (3)	0.3540 (16)	0.017*
H1W2	0.5573 (18)	0.505 (3)	0.3843 (15)	0.017*
O2W	0.29615 (6)	0.39794 (11)	0.37156 (4)	0.01612 (12)
H2W1	0.2869 (13)	0.290 (2)	0.3380 (10)	0.024*
H2W2	0.3027 (13)	0.344 (2)	0.4235 (8)	0.024*
C1A	0.71817 (7)	0.43527 (13)	0.26448 (5)	0.01045 (14)
C2A	0.85034 (8)	0.44468 (14)	0.28101 (6)	0.01530 (15)
H2A	0.8621	0.5188	0.2314	0.018*
C3A	0.90702 (9)	0.2299 (2)	0.28691 (9)	0.0292 (2)
H3A1	0.9021	0.1576	0.3377	0.044*
H3A2	0.9885	0.2457	0.2917	0.044*
H3A3	0.8663	0.1508	0.2350	0.044*
C4A	0.90875 (11)	0.5731 (2)	0.36327 (11)	0.0409 (4)
H4A1	0.8738	0.7102	0.3563	0.061*
H4A2	0.9918	0.5855	0.3726	0.061*
H4A3	0.8976	0.5050	0.4130	0.061*
C1B	0.36124 (7)	0.38036 (14)	0.08390 (5)	0.01115 (14)
C2B	0.29432 (9)	0.56464 (14)	0.03069 (6)	0.01593 (16)
H2B	0.2944	0.6787	0.0714	0.019*
C3B	0.16552 (9)	0.50628 (19)	−0.02026 (7)	0.0238 (2)
H3B1	0.1637	0.3970	−0.0616	0.036*
H3B2	0.1245	0.6271	−0.0512	0.036*
H3B3	0.1278	0.4583	0.0201	0.036*
C4B	0.35856 (10)	0.64054 (17)	−0.03141 (6)	0.02213 (19)
H4B1	0.4358	0.6907	0.0025	0.033*
H4B2	0.3142	0.7519	−0.0676	0.033*
H4B3	0.3660	0.5265	−0.0680	0.033*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.00921 (6)	0.00625 (7)	0.00890 (5)	0.00009 (3)	0.00197 (4)	−0.00013 (3)
O1A	0.0120 (3)	0.0092 (3)	0.0155 (3)	0.0012 (2)	0.0043 (2)	0.0020 (2)
O2A	0.0116 (3)	0.0097 (3)	0.0164 (3)	0.0002 (2)	0.0040 (2)	0.0016 (2)
O1B	0.0120 (3)	0.0083 (3)	0.0091 (2)	0.00017 (19)	0.00020 (19)	−0.00006 (17)
O2B	0.0182 (3)	0.0100 (3)	0.0114 (3)	0.0011 (2)	0.0003 (2)	−0.00154 (19)
O1W	0.0129 (3)	0.0097 (3)	0.0104 (2)	−0.0009 (2)	0.0032 (2)	−0.00094 (18)
O2W	0.0229 (3)	0.0121 (3)	0.0144 (3)	−0.0006 (2)	0.0076 (2)	−0.0006 (2)
C1A	0.0106 (3)	0.0103 (4)	0.0103 (3)	0.0002 (2)	0.0032 (2)	0.0001 (2)
C2A	0.0105 (3)	0.0139 (4)	0.0217 (4)	−0.0002 (3)	0.0057 (3)	0.0017 (3)
C3A	0.0138 (4)	0.0223 (6)	0.0489 (7)	0.0050 (4)	0.0071 (4)	−0.0045 (5)
C4A	0.0179 (5)	0.0483 (9)	0.0492 (8)	−0.0048 (5)	0.0013 (5)	−0.0285 (6)
C1B	0.0123 (3)	0.0107 (4)	0.0093 (3)	0.0010 (3)	0.0022 (2)	0.0000 (2)
C2B	0.0209 (4)	0.0117 (4)	0.0114 (3)	0.0047 (3)	0.0004 (3)	0.0006 (3)
C3B	0.0187 (4)	0.0263 (6)	0.0210 (4)	0.0078 (4)	−0.0005 (3)	0.0026 (3)
C4B	0.0326 (5)	0.0146 (4)	0.0179 (4)	−0.0008 (4)	0.0067 (4)	0.0039 (3)

Geometric parameters (Å, º) top

Co1—O1A	2.0449 (6)	C2A—C4A	1.5176 (16)
Co1—O2Aⁱ	2.0142 (6)	C3A—H3A1	0.9600
Co1—O1B	2.1100 (6)	C3A—H3A2	0.9600
Co1—O1Bⁱ	2.1198 (6)	C3A—H3A3	0.9600
Co1—O1W	2.1768 (6)	C4A—H4A1	0.9600
Co1—O1Wⁱ	2.1777 (6)	C4A—H4A2	0.9600
O1A—C1A	1.2755 (10)	C4A—H4A3	0.9600
O2A—C1A	1.2533 (10)	C1B—C2B	1.5179 (12)
O1B—C1B	1.2878 (9)	C2B—H2B	0.9800
O2B—C1B	1.2510 (11)	C2B—C3B	1.5340 (14)
O1W—H1W1	0.79 (2)	C2B—C4B	1.5329 (14)
O1W—H1W2	0.88 (2)	C3B—H3B1	0.9600
O2W—H2W1	0.861 (12)	C3B—H3B2	0.9600
O2W—H2W2	0.884 (11)	C3B—H3B3	0.9600
C1A—C2A	1.5191 (12)	C4B—H4B1	0.9600
C2A—H2A	0.9800	C4B—H4B2	0.9600
C2A—C3A	1.5187 (15)	C4B—H4B3	0.9600

O1A—Co1—O1B	88.13 (3)	C4A—C2A—C3A	111.50 (9)
O1A—Co1—O1Bⁱ	89.41 (3)	C2A—C3A—H3A1	109.5
O1A—Co1—O1W	92.18 (3)	C2A—C3A—H3A2	109.5
O1A—Co1—O1Wⁱ	88.29 (3)	C2A—C3A—H3A3	109.5
O2Aⁱ—Co1—O1A	175.30 (3)	H3A1—C3A—H3A2	109.5
O2Aⁱ—Co1—O1B	89.99 (3)	H3A1—C3A—H3A3	109.5
O2Aⁱ—Co1—O1Bⁱ	93.14 (3)	H3A2—C3A—H3A3	109.5
O2Aⁱ—Co1—O1W	91.70 (3)	C2A—C4A—H4A1	109.5
O2Aⁱ—Co1—O1Wⁱ	88.33 (3)	C2A—C4A—H4A2	109.5
O1B—Co1—O1Bⁱ	170.29 (2)	C2A—C4A—H4A3	109.5
O1B—Co1—O1W	79.22 (2)	H4A1—C4A—H4A2	109.5
O1Bⁱ—Co1—O1W	91.49 (2)	H4A1—C4A—H4A3	109.5
O1B—Co1—O1Wⁱ	110.31 (2)	H4A2—C4A—H4A3	109.5
O1Bⁱ—Co1—O1Wⁱ	78.99 (2)	O1B—C1B—C2B	118.13 (8)
O1W—Co1—O1Wⁱ	170.46 (2)	O2B—C1B—O1B	122.42 (8)
C1A—O1A—Co1	130.11 (6)	O2B—C1B—C2B	119.42 (7)
C1A—O2A—Co1ⁱⁱ	131.28 (6)	C1B—C2B—H2B	108.3
Co1—O1B—Co1ⁱⁱ	98.44 (2)	C1B—C2B—C3B	111.27 (8)
C1B—O1B—Co1	135.89 (6)	C1B—C2B—C4B	109.15 (8)
C1B—O1B—Co1ⁱⁱ	125.09 (6)	C3B—C2B—H2B	108.3
Co1—O1W—Co1ⁱⁱ	94.70 (2)	C4B—C2B—H2B	108.3
Co1—O1W—H1W1	109.1 (16)	C4B—C2B—C3B	111.30 (8)
Co1ⁱⁱ—O1W—H1W1	116.6 (14)	C2B—C3B—H3B1	109.5
Co1—O1W—H1W2	98.2 (15)	C2B—C3B—H3B2	109.5
Co1ⁱⁱ—O1W—H1W2	127.6 (14)	C2B—C3B—H3B3	109.5
H1W1—O1W—H1W2	106 (2)	H3B1—C3B—H3B2	109.5
H2W1—O2W—H2W2	103.8 (14)	H3B1—C3B—H3B3	109.5
O2A—C1A—O1A	124.94 (8)	H3B2—C3B—H3B3	109.5
O2A—C1A—C2A	118.59 (7)	C2B—C4B—H4B1	109.5
O1A—C1A—C2A	116.46 (7)	C2B—C4B—H4B2	109.5
C1A—C2A—H2A	107.6	C2B—C4B—H4B3	109.5
C3A—C2A—C1A	113.25 (8)	H4B1—C4B—H4B2	109.5
C3A—C2A—H2A	107.6	H4B1—C4B—H4B3	109.5
C4A—C2A—C1A	108.94 (8)	H4B2—C4B—H4B3	109.5
C4A—C2A—H2A	107.6

Co1—O1A—C1A—C2A	−166.13 (6)	Co1ⁱⁱ—O1B—C1B—O2B	−16.84 (12)
Co1—O1A—C1A—O2A	12.38 (12)	Co1—O1B—C1B—C2B	−4.15 (12)
O1A—C1A—C2A—C3A	−168.74 (8)	Co1ⁱⁱ—O1B—C1B—C2B	165.09 (6)
O1A—C1A—C2A—C4A	66.57 (12)	O1B—C1B—C2B—C3B	−138.98 (8)
O2A—C1A—C2A—C3A	12.65 (12)	O1B—C1B—C2B—C4B	97.80 (9)
O2A—C1A—C2A—C4A	−112.03 (11)	O2B—C1B—C2B—C3B	42.89 (11)
Co1—O1B—C1B—O2B	173.93 (6)	O2B—C1B—C2B—C4B	−80.33 (10)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···O2W	0.79 (2)	1.91 (2)	2.6638 (10)	161 (2)
O1W—H1W2···O2Bⁱ	0.88 (2)	1.79 (2)	2.6206 (9)	158 (2)
O2W—H2W1···O1Aⁱⁱ	0.86 (1)	2.01 (1)	2.7967 (9)	151 (1)
O2W—H2W2···O2Bⁱⁱⁱ	0.88 (1)	1.95 (1)	2.8087 (9)	163 (1)
C2B—H2B···O2Aⁱ	0.98	2.47	3.3094 (11)	144

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

Acknowledgements

The authors thank the Research Center of X-ray Diffraction Studies at St Petersburg State University for the data collection. The work was supported financially within the state contract No. 14.Z50.31.0013 of March 19, 2014.

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