Di-μ-acetato-μ-aqua-bis­[acetatobis(1H-benzimidazole)cobalt(II)]

Zimmermann, I.; Keene, T.D.; Neels, A.; Decurtins, S.

doi:10.1107/S1600536808015596

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 6| June 2008| Pages m845-m846

doi:10.1107/S1600536808015596

Open

access

Di-μ-acetato-μ-aqua-bis[acetatobis(1H-benzimidazole)cobalt(II)]

Iwan Zimmermann,^a Tony D. Keene,^a Antonia Neels ^b and Silvio Decurtins ^a ^*

^aDepartement für Chemie und Biochemie, Universität Bern, Freiestrasse 3, CH-3012 Bern, Switzerland, and ^bInstitut de Microtechnique, Jaquet Droz 1, CP 526, CH-2002 Neuchâtel, Switzerland
^*Correspondence e-mail: silvio.decurtins@iac.unibe.ch

(Received 14 May 2008; accepted 23 May 2008; online 30 May 2008)

In the title compound, [Co₂(C₂H₃O₂)₄(C₇H₆N₂)₄(H₂O)], the half-molecule in the asymmetric unit is completed by a crystallographic twofold rotation axis to give the full molecule. The Co^II ions are approximately octahedrally coordinated with a cis-N₂O₄ coordination sphere. The compound features intramolecular O—H⋯O hydrogen bonds between the non-bridging acetate groups and the bridging water molecule, and intermolecular N—H⋯O hydrogen bonds between the acetates and amine H atoms of the benzimidazoles which determine the molecular packing in the crystal structure.

Related literature

For related literature, see: Brown et al. (2004 ); Hagen et al. (1993 ); Orpen et al. (1989 ); Turpeinen et al. (1987 ); Ye et al. (1997 ).

Experimental

Crystal data

[Co₂(C₂H₃O₂)₄(C₇H₆N₂)₄(H₂O)]
M_r = 844.6
Orthorhombic, A b a 2
a = 18.663 (4) Å
b = 8.8101 (18) Å
c = 22.727 (5) Å
V = 3736.7 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.95 mm⁻¹
T = 150 (2) K
0.1 × 0.09 × 0.08 mm

Data collection

Stoe IPDS diffractometer
Absorption correction: multi-scan (MULscanABS in PLATON; Spek, 2003 ) T_min = 0.914, T_max = 0.956
24157 measured reflections
5048 independent reflections
3698 reflections with I > 2σ(I)
R_int = 0.069

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.077
S = 0.89
5048 reflections
252 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.57 e Å⁻³
Absolute structure: Flack (1983 ), with 2433 Friedel pairs
Flack parameter: 0.006 (12)

Table 1
Selected geometric parameters (Å, °)

Co1—O3	2.0495 (18)
Co1—O4ⁱ	2.1044 (19)
Co1—O1	2.1141 (17)
Co1—O1W	2.1315 (15)
Co1—N1	2.139 (2)
Co1—N3	2.147 (2)

O3—Co1—O4ⁱ	97.48 (8)
O3—Co1—O1	174.69 (7)
O4ⁱ—Co1—O1	86.88 (7)
O3—Co1—O1W	90.09 (6)
O4ⁱ—Co1—O1W	90.78 (7)
O1—Co1—O1W	92.89 (6)
O3—Co1—N1	88.66 (8)
O4ⁱ—Co1—N1	87.79 (8)
O1—Co1—N1	88.48 (7)
O1W—Co1—N1	177.97 (9)
O3—Co1—N3	88.14 (8)
O4ⁱ—Co1—N3	174.38 (8)
O1—Co1—N3	87.50 (8)
O1W—Co1—N3	89.38 (8)
N1—Co1—N3	92.19 (8)
Co1ⁱ—O1W—Co1	116.98 (13)
Symmetry code: (i) -x, -y, z.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W⋯O2	0.97	1.71	2.591 (2)	149
N4—H22⋯O2ⁱⁱ	0.86	1.87	2.717 (3)	167
N2—H12⋯O4ⁱⁱⁱ	0.86	2.00	2.812 (2)	157
Symmetry codes: (ii) x, y+1, z; (iii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z]$ .

Data collection: EXPOSE in IPDS Software (Stoe & Cie, 2000 ); cell refinement: CELL in IPDS Software; data reduction: INTEGRATE in IPDS Software; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: DIAMOND (Brandenberg, 1999 ); software used to prepare material for publication: SHELXL97 and WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808015596/si2092sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808015596/si2092Isup2.hkl

checkCIF report

Comment top

The title compound belongs to an extensive group of compounds which share the same (µ₂-acetato)-(µ₂-aquo)-di-M(II) core (see for example Turpeinen et al. 1987; Brown et al. 2004; Hagen et al. 1993), indicating that this motif is favourable under a variety of synthetic conditions and for many different metals. The compound crystallizes from a solution of benzimidazole, cobalt acetate tetrahydrate and oxalic acid dihydrate in methanol which was left to evaporate over five days at room temperature. The title complex, with its bridging water molecule lying on a twofold rotation axis, is isostructural with the previously reported Mn(II) congener (Ye et al., 1997) and the structure comprises two Co(II) ions bridged by two acetate anions and one water molecule with the remainder of each approximately octahedral Co(II) coordination sphere being completed by coordination by the imine N atoms from two benzimidazole molecules and one monodentate acetate group (Fig. 1). All bond lengths and angles are in accordance with literature values (Orpen et al., 1992). The water molecule hydrogen bonds to the uncoordinated oxygen atom of the monodentate acetate groups within the dimer with a short H···O distance of 1.714 (2) Å (Fig. 2, Table 2). The monodentate acetate groups show that there is a large degree of delocalization in the carboxylate group with C—O bonds of 1.250 (3) (C1—O1) and 1.269 (3) Å (C1—O2), (Table 1). The shorter C1—O1 distance implies that this bond has more of a carbonyl character than C1—O2, as seen in the Mn(II) congener, indicating that the hydrogen bond between O2 and H1w affects the delocalization. The amine hydrogen atoms all take part in hydrogen bonds to acetate anions in neighbouring dimer groups to create the crystal packing. All acetates are involved in intermolecular hydrogen bonding, which forms planes of dimers in the ab-plane (Fig. 2, Table 2).

Related literature top

For related literature, see: Brown et al. (2004); Hagen et al. (1993); Orpen et al. (1992); Turpeinen et al. (1987); Ye et al. (1997).

Experimental top

Single crystals of the title compound suitable for X-ray diffraction experiments were obtained by dissolving cobalt(II) acetate tetrahydrate (1 mmol, 249 mg) and oxalic acid dihydrate (1 mmol, 126 mg) in a saturated solution of benzimidazole in methanol (30 ml). The subsequent solution was left to evaporate at room temperature for five days before red crystals formed. IR (KBr disc, transmission, cm^-1): 3088 (m), 2982 (m), 2910 (m), 2836 (w), 1629 (s), 1606 (s), 1491 (m), 1420 (s), 1341 (w), 1304 (m), 1273 (m), 1251 (m), 1011 (w), 963 (w), 887 (w), 775 (w), 741 (s), 653 (m), 619 (w), 547 (w), 428 (w).

Computing details top

Data collection: EXPOSE in IPDS Software (Stoe & Cie, 2000); cell refinement: CELL in IPDS Software (Stoe & Cie, 2000); data reduction: INTEGRATE in IPDS Software (Stoe & Cie, 2000); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenberg, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and WinGX (Farrugia, 1999).

Figures top

	Fig. 1. Asymmetric unit and selected symmetry equivalents with thermal ellipsoids at the 50% probability level. Hydrogen atoms (except H1w) and atom labels for the symmetry equivalent atoms (symmetry code: -x, -y, z) omitted for clarity. Hydrogen bonds depicted by dashed lines.
	Fig. 2. View of the hydrogen bonding network (dashed green bonds) and crystal packing, looking down the c-axis.

Di-µ-acetato-µ-aqua-bis[acetatobis(1H-benzimidazole)cobalt(II)] top

Crystal data top

[Co₂(C₂H₃O₂)₄(C₇H₆N₂)₄(H₂O)]	D_x = 1.501 Mg m⁻³
M_r = 844.6	Melting point: N/A K
Orthorhombic, Aba2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: A 2 -2ac	Cell parameters from 15135 reflections
a = 18.663 (4) Å	θ = 1.8–29.5°
b = 8.8101 (18) Å	µ = 0.95 mm⁻¹
c = 22.727 (5) Å	T = 150 K
V = 3736.7 (13) Å³	Block, red
Z = 4	0.1 × 0.09 × 0.08 mm
F(000) = 1744

Data collection top

Stoe IPDS diffractometer	3698 reflections with I > 2σ(I)
ϕ oscillation scans	R_int = 0.069
Absorption correction: multi-scan (MULscanABS in PLATON03; Spek, 2003)	θ_max = 29.3°, θ_min = 1.8°
T_min = 0.914, T_max = 0.956	h = −25→25
24157 measured reflections	k = −12→11
5048 independent reflections	l = −31→31

Refinement top

Refinement on F²	w = 1/[σ²(F_o²) + (0.0441P)²] where P = (F_o² + 2F_c²)/3
Least-squares matrix: full	(Δ/σ)_max < 0.001
R[F² > 2σ(F²)] = 0.035	Δρ_max = 0.36 e Å⁻³
wR(F²) = 0.078	Δρ_min = −0.57 e Å⁻³
S = 0.89	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
5048 reflections	Extinction coefficient: 0.00058 (8)
252 parameters	Absolute structure: Flack (1983), 2433 Friedel pairs
1 restraint	Absolute structure parameter: 0.006 (12)
H-atom parameters constrained

Crystal data top

[Co₂(C₂H₃O₂)₄(C₇H₆N₂)₄(H₂O)]	V = 3736.7 (13) Å³
M_r = 844.6	Z = 4
Orthorhombic, Aba2	Mo Kα radiation
a = 18.663 (4) Å	µ = 0.95 mm⁻¹
b = 8.8101 (18) Å	T = 150 K
c = 22.727 (5) Å	0.1 × 0.09 × 0.08 mm

Data collection top

Stoe IPDS diffractometer	5048 independent reflections
Absorption correction: multi-scan (MULscanABS in PLATON03; Spek, 2003)	3698 reflections with I > 2σ(I)
T_min = 0.914, T_max = 0.956	R_int = 0.069
24157 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	H-atom parameters constrained
wR(F²) = 0.078	Δρ_max = 0.36 e Å⁻³
S = 0.89	Δρ_min = −0.57 e Å⁻³
5048 reflections	Absolute structure: Flack (1983), 2433 Friedel pairs
252 parameters	Absolute structure parameter: 0.006 (12)
1 restraint

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.

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

	x	y	z	U_iso*/U_eq
Co1	0.081808 (12)	0.11188 (3)	0.166836 (17)	0.02569 (8)
O1W	0	0	0.21585 (12)	0.0248 (5)
H1W	0.0227	−0.0745	0.2412	0.03*
O2	0.10002 (8)	−0.1571 (2)	0.26630 (9)	0.0362 (4)
O1	0.16471 (8)	0.0148 (2)	0.21784 (9)	0.0305 (4)
O4	−0.09188 (8)	0.0772 (2)	0.11088 (9)	0.0314 (4)
O3	0.00530 (9)	0.2253 (2)	0.11937 (9)	0.0365 (4)
N1	0.16209 (10)	0.2216 (2)	0.11482 (10)	0.0300 (5)
N4	0.08897 (11)	0.5364 (3)	0.25660 (14)	0.0434 (6)
H22	0.0924	0.6335	0.2537	0.052*
N3	0.07962 (10)	0.2950 (2)	0.22915 (11)	0.0318 (5)
N2	0.26092 (9)	0.3580 (3)	0.10253 (11)	0.0346 (5)
H12	0.3015	0.3996	0.1104	0.042*
C27	0.08124 (12)	0.3017 (3)	0.29057 (13)	0.0331 (6)
C26	0.07634 (14)	0.1894 (3)	0.33343 (13)	0.0389 (6)
H26	0.0717	0.0877	0.3232	0.047*
C17	0.16144 (11)	0.2838 (3)	0.05885 (12)	0.0268 (5)
C22	0.08784 (13)	0.4537 (3)	0.30791 (15)	0.0386 (7)
C12	0.22350 (12)	0.3704 (3)	0.05085 (12)	0.0298 (5)
C21	0.08369 (13)	0.4376 (3)	0.21186 (15)	0.0390 (6)
H21	0.083	0.4669	0.1725	0.047*
C11	0.22226 (12)	0.2688 (3)	0.13860 (12)	0.0329 (6)
H11	0.2367	0.2431	0.1765	0.04*
C3	−0.05615 (12)	0.1965 (3)	0.10030 (12)	0.0286 (5)
C13	0.23834 (15)	0.4491 (3)	−0.00066 (13)	0.0409 (7)
H13	0.2797	0.5071	−0.0049	0.049*
C16	0.11186 (14)	0.2719 (3)	0.01321 (13)	0.0350 (6)
H16	0.0706	0.2136	0.0173	0.042*
C2	0.22415 (14)	−0.1402 (4)	0.28792 (14)	0.0439 (7)
H2A	0.2663	−0.1147	0.2658	0.066*
H2B	0.2225	−0.2479	0.294	0.066*
H2C	0.2255	−0.0895	0.3253	0.066*
C1	0.15851 (12)	−0.0905 (3)	0.25437 (12)	0.0286 (5)
C4	−0.09095 (15)	0.3150 (4)	0.06247 (15)	0.0434 (7)
H4A	−0.1143	0.267	0.0297	0.065*
H4B	−0.0552	0.3841	0.0482	0.065*
H4C	−0.1257	0.3698	0.0853	0.065*
C25	0.07865 (17)	0.2341 (4)	0.39177 (15)	0.0514 (8)
H25	0.0748	0.1607	0.421	0.062*
C23	0.09133 (15)	0.4981 (4)	0.36623 (17)	0.0508 (8)
H23	0.0967	0.5996	0.3766	0.061*
C15	0.12589 (16)	0.3494 (4)	−0.03822 (14)	0.0448 (7)
H15	0.0932	0.3439	−0.069	0.054*
C24	0.08657 (17)	0.3864 (4)	0.40805 (17)	0.0573 (9)
H24	0.0886	0.4122	0.4477	0.069*
C14	0.18851 (16)	0.4367 (4)	−0.04522 (14)	0.0455 (7)
H14	0.1964	0.4871	−0.0806	0.055*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.01518 (10)	0.02082 (13)	0.04106 (16)	−0.00018 (11)	−0.00008 (19)	0.00135 (18)
O1W	0.0190 (10)	0.0170 (12)	0.0385 (14)	0.0002 (9)	0	0
O2	0.0257 (7)	0.0211 (9)	0.0618 (14)	0.0010 (7)	−0.0038 (8)	0.0044 (9)
O1	0.0208 (7)	0.0293 (10)	0.0413 (11)	0.0016 (7)	−0.0033 (7)	0.0022 (8)
O4	0.0185 (7)	0.0307 (10)	0.0450 (11)	−0.0010 (6)	−0.0023 (7)	0.0060 (8)
O3	0.0191 (7)	0.0347 (11)	0.0558 (12)	−0.0030 (7)	−0.0059 (8)	0.0147 (9)
N1	0.0189 (9)	0.0282 (12)	0.0429 (13)	−0.0043 (8)	−0.0002 (9)	0.0011 (9)
N4	0.0312 (11)	0.0187 (11)	0.0802 (19)	−0.0033 (9)	0.0069 (12)	−0.0051 (12)
N3	0.0253 (9)	0.0194 (10)	0.0506 (13)	0.0005 (9)	0.0034 (10)	−0.0016 (9)
N2	0.0161 (8)	0.0391 (13)	0.0486 (14)	−0.0069 (8)	0.0019 (9)	0.0006 (11)
C27	0.0199 (9)	0.0234 (13)	0.0562 (17)	0.0021 (10)	−0.0002 (11)	−0.0076 (11)
C26	0.0376 (13)	0.0283 (14)	0.0508 (17)	0.0062 (11)	−0.0028 (12)	−0.0050 (12)
C17	0.0214 (10)	0.0212 (12)	0.0377 (14)	0.0021 (9)	0.0032 (10)	−0.0046 (10)
C22	0.0231 (11)	0.0221 (13)	0.071 (2)	0.0000 (10)	0.0002 (12)	−0.0106 (13)
C12	0.0214 (10)	0.0302 (15)	0.0380 (14)	−0.0002 (9)	0.0044 (9)	−0.0027 (11)
C21	0.0317 (12)	0.0214 (12)	0.0640 (19)	−0.0009 (11)	0.0095 (13)	0.0013 (13)
C11	0.0202 (10)	0.0376 (14)	0.0410 (15)	−0.0032 (10)	−0.0018 (10)	0.0031 (12)
C3	0.0197 (10)	0.0299 (14)	0.0364 (14)	0.0046 (9)	0.0000 (10)	−0.0001 (11)
C13	0.0354 (13)	0.0378 (16)	0.0496 (18)	−0.0009 (12)	0.0130 (12)	0.0006 (13)
C16	0.0276 (11)	0.0312 (15)	0.0462 (17)	0.0012 (11)	−0.0038 (11)	−0.0101 (13)
C2	0.0308 (13)	0.055 (2)	0.0460 (18)	0.0090 (12)	−0.0084 (12)	0.0021 (15)
C1	0.0240 (10)	0.0215 (13)	0.0404 (14)	0.0048 (9)	−0.0031 (10)	−0.0063 (11)
C4	0.0350 (14)	0.0406 (17)	0.0545 (19)	−0.0001 (12)	−0.0108 (14)	0.0165 (15)
C25	0.0548 (18)	0.0489 (19)	0.0504 (18)	0.0122 (15)	−0.0070 (16)	−0.0068 (15)
C23	0.0376 (14)	0.0388 (17)	0.076 (2)	0.0034 (13)	−0.0068 (15)	−0.0244 (18)
C15	0.0474 (15)	0.0504 (19)	0.0367 (16)	0.0072 (14)	−0.0048 (12)	−0.0087 (14)
C24	0.0567 (18)	0.055 (2)	0.060 (2)	0.0147 (16)	−0.0184 (18)	−0.0205 (19)
C14	0.0523 (16)	0.0474 (18)	0.0367 (16)	0.0046 (14)	0.0084 (13)	0.0004 (14)

Geometric parameters (Å, º) top

Co1—O3	2.0495 (18)	C17—C16	1.394 (3)
Co1—O4ⁱ	2.1044 (19)	C17—C12	1.399 (3)
Co1—O1	2.1141 (17)	C22—C23	1.383 (5)
Co1—O1W	2.1315 (15)	C12—C13	1.389 (4)
Co1—N1	2.139 (2)	C21—H21	0.93
Co1—N3	2.147 (2)	C11—H11	0.93
O1W—Co1ⁱ	2.1315 (15)	C3—C4	1.501 (4)
O1W—H1W	0.97	C13—C14	1.379 (4)
O2—C1	1.269 (3)	C13—H13	0.93
O1—C1	1.250 (3)	C16—C15	1.379 (4)
O4—C3	1.267 (3)	C16—H16	0.93
O4—Co1ⁱ	2.1044 (19)	C2—C1	1.508 (3)
O3—C3	1.252 (3)	C2—H2A	0.96
N1—C11	1.314 (3)	C2—H2B	0.96
N1—C17	1.385 (3)	C2—H2C	0.96
N4—C21	1.342 (4)	C4—H4A	0.96
N4—C22	1.375 (4)	C4—H4B	0.96
N4—H22	0.86	C4—H4C	0.96
N3—C21	1.319 (4)	C25—C24	1.400 (5)
N3—C27	1.397 (4)	C25—H25	0.93
N2—C11	1.346 (3)	C23—C24	1.371 (5)
N2—C12	1.371 (4)	C23—H23	0.93
N2—H12	0.86	C15—C14	1.408 (4)
C27—C26	1.391 (4)	C15—H15	0.93
C27—C22	1.402 (4)	C24—H24	0.93
C26—C25	1.384 (4)	C14—H14	0.93
C26—H26	0.93

O3—Co1—O4ⁱ	97.48 (8)	C13—C12—C17	123.2 (3)
O3—Co1—O1	174.69 (7)	N3—C21—N4	113.3 (3)
O4ⁱ—Co1—O1	86.88 (7)	N3—C21—H21	123.3
O3—Co1—O1W	90.09 (6)	N4—C21—H21	123.3
O4ⁱ—Co1—O1W	90.78 (7)	N1—C11—N2	113.1 (2)
O1—Co1—O1W	92.89 (6)	N1—C11—H11	123.4
O3—Co1—N1	88.66 (8)	N2—C11—H11	123.4
O4ⁱ—Co1—N1	87.79 (8)	O3—C3—O4	125.8 (2)
O1—Co1—N1	88.48 (7)	O3—C3—C4	117.0 (2)
O1W—Co1—N1	177.97 (9)	O4—C3—C4	117.2 (2)
O3—Co1—N3	88.14 (8)	C14—C13—C12	116.4 (3)
O4ⁱ—Co1—N3	174.38 (8)	C14—C13—H13	121.8
O1—Co1—N3	87.50 (8)	C12—C13—H13	121.8
O1W—Co1—N3	89.38 (8)	C15—C16—C17	117.9 (3)
N1—Co1—N3	92.19 (8)	C15—C16—H16	121.1
Co1ⁱ—O1W—Co1	116.98 (13)	C17—C16—H16	121.1
Co1ⁱ—O1W—H1W	108.1	C1—C2—H2A	109.5
Co1—O1W—H1W	108.1	C1—C2—H2B	109.5
C1—O1—Co1	126.63 (14)	H2A—C2—H2B	109.5
C3—O4—Co1ⁱ	136.38 (16)	C1—C2—H2C	109.5
C3—O3—Co1	136.17 (18)	H2A—C2—H2C	109.5
C11—N1—C17	105.1 (2)	H2B—C2—H2C	109.5
C11—N1—Co1	120.94 (18)	O1—C1—O2	124.4 (2)
C17—N1—Co1	132.86 (15)	O1—C1—C2	118.4 (2)
C21—N4—C22	107.3 (2)	O2—C1—C2	117.2 (2)
C21—N4—H22	126.3	C3—C4—H4A	109.5
C22—N4—H22	126.3	C3—C4—H4B	109.5
C21—N3—C27	104.9 (2)	H4A—C4—H4B	109.5
C21—N3—Co1	121.2 (2)	C3—C4—H4C	109.5
C27—N3—Co1	133.63 (17)	H4A—C4—H4C	109.5
C11—N2—C12	107.17 (19)	H4B—C4—H4C	109.5
C11—N2—H12	126.4	C26—C25—C24	121.9 (4)
C12—N2—H12	126.4	C26—C25—H25	119
C26—C27—N3	131.9 (2)	C24—C25—H25	119
C26—C27—C22	119.2 (3)	C24—C23—C22	117.3 (3)
N3—C27—C22	108.8 (3)	C24—C23—H23	121.4
C25—C26—C27	117.8 (3)	C22—C23—H23	121.4
C25—C26—H26	121.1	C16—C15—C14	121.6 (3)
C27—C26—H26	121.1	C16—C15—H15	119.2
N1—C17—C16	131.3 (2)	C14—C15—H15	119.2
N1—C17—C12	109.1 (2)	C23—C24—C25	120.8 (3)
C16—C17—C12	119.6 (3)	C23—C24—H24	119.6
N4—C22—C23	131.5 (3)	C25—C24—H24	119.6
N4—C22—C27	105.6 (3)	C13—C14—C15	121.3 (3)
C23—C22—C27	122.9 (3)	C13—C14—H14	119.3
N2—C12—C13	131.3 (2)	C15—C14—H14	119.3
N2—C12—C17	105.5 (2)

Symmetry code: (i) −x, −y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···O2	0.97	1.71	2.591 (2)	149
N4—H22···O2ⁱⁱ	0.86	1.87	2.717 (3)	167
N2—H12···O4ⁱⁱⁱ	0.86	2.00	2.812 (2)	157

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

Experimental details

Crystal data
Chemical formula	[Co₂(C₂H₃O₂)₄(C₇H₆N₂)₄(H₂O)]
M_r	844.6
Crystal system, space group	Orthorhombic, Aba2
Temperature (K)	150
a, b, c (Å)	18.663 (4), 8.8101 (18), 22.727 (5)
V (Å³)	3736.7 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.95
Crystal size (mm)	0.1 × 0.09 × 0.08

Data collection
Diffractometer	Stoe IPDS diffractometer
Absorption correction	Multi-scan (MULscanABS in PLATON03; Spek, 2003)
T_min, T_max	0.914, 0.956
No. of measured, independent and observed [I > 2σ(I)] reflections	24157, 5048, 3698
R_int	0.069
(sin θ/λ)_max (Å⁻¹)	0.688

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.078, 0.89
No. of reflections	5048
No. of parameters	252
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.57
Absolute structure	Flack (1983), 2433 Friedel pairs
Absolute structure parameter	0.006 (12)

Computer programs: EXPOSE in IPDS Software (Stoe & Cie, 2000), CELL in IPDS Software (Stoe & Cie, 2000), INTEGRATE in IPDS Software (Stoe & Cie, 2000), SIR92 (Altomare et al., 1994), DIAMOND (Brandenberg, 1999), SHELXL97 (Sheldrick, 2008) and WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top

Co1—O3	2.0495 (18)	Co1—N3	2.147 (2)
Co1—O4ⁱ	2.1044 (19)	O2—C1	1.269 (3)
Co1—O1	2.1141 (17)	O1—C1	1.250 (3)
Co1—O1W	2.1315 (15)	O4—C3	1.267 (3)
Co1—N1	2.139 (2)	O3—C3	1.252 (3)

O3—Co1—O4ⁱ	97.48 (8)	O1—Co1—N1	88.48 (7)
O3—Co1—O1	174.69 (7)	O1W—Co1—N1	177.97 (9)
O4ⁱ—Co1—O1	86.88 (7)	O3—Co1—N3	88.14 (8)
O3—Co1—O1W	90.09 (6)	O4ⁱ—Co1—N3	174.38 (8)
O4ⁱ—Co1—O1W	90.78 (7)	O1—Co1—N3	87.50 (8)
O1—Co1—O1W	92.89 (6)	O1W—Co1—N3	89.38 (8)
O3—Co1—N1	88.66 (8)	N1—Co1—N3	92.19 (8)
O4ⁱ—Co1—N1	87.79 (8)	Co1ⁱ—O1W—Co1	116.98 (13)

Symmetry code: (i) −x, −y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···O2	0.97	1.714	2.591 (2)	148.5
N4—H22···O2ⁱⁱ	0.86	1.87	2.717 (3)	167
N2—H12···O4ⁱⁱⁱ	0.86	2.00	2.812 (2)	157

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

Acknowledgements

This work was supported by the Swiss National Science Foundation (grant No. 200020-116003).

References

Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435. CrossRef Web of Science IUCr Journals Google Scholar
Brandenberg, K. (1999). DIAMOND. Crystal Impact GbR, Germany. Google Scholar
Brown, D. A., Glass, W. K., Fitzpatrick, N. J., Kemp, T. J., Errington, W., Clarkson, G. J., Haase, W., Karsten, F. & Mahdy, A. H. (2004). Inorg. Chim. Acta, 357, 1411–1436. Web of Science CSD CrossRef CAS Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Hagen, K. S., Lachicotte, R., Kitaygorodskiy, A. & Elbouadili, A. (1993). Angew. Chem. Int. Ed. Engl. 32, 1321–1324. CSD CrossRef Web of Science Google Scholar
Orpen, A. G., Brammer, L., Allen, F. H., Kennard, O., Watson, D. G. & Taylor, R. (1989). J. Chem. Soc. Dalton Trans. pp. S1–83. CrossRef Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stoe & Cie (2000). IPDS Software. Stoe & Cie GmbH, Darmstadt, Germany. Google Scholar
Turpeinen, U., Hämäläinen, R. & Reedijk, J. (1987). Polyhedron, 6, 1603–1610. CSD CrossRef CAS Web of Science Google Scholar
Ye, B.-H., Mak, T., Williams, I. D. & Li, X.-Y. (1997). J. Chem. Soc. Chem. Commun. pp. 1813–1814. CrossRef Google Scholar