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Acta Crystallogr Sect E Struct Rep Online. 2008 June 1; 64(Pt 6): m845–m846.
Published online 2008 May 30. doi:  10.1107/S1600536808015596
PMCID: PMC2961362

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

Abstract

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 CoII 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 [triangle]); Hagen et al. (1993 [triangle]); Orpen et al. (1989 [triangle]); Turpeinen et al. (1987 [triangle]); Ye et al. (1997 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-0m845-scheme1.jpg

Experimental

Crystal data

  • [Co2(C2H3O2)4(C7H6N2)4(H2O)]
  • M r = 844.6
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-0m845-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.035
  • wR(F 2) = 0.077
  • S = 0.89
  • 5048 reflections
  • 252 parameters
  • 1 restraint
  • H-atom parameters constrained
  • Δρmax = 0.36 e Å−3
  • Δρmin = −0.57 e Å−3
  • Absolute structure: Flack (1983 [triangle]), with 2433 Friedel pairs
  • Flack parameter: 0.006 (12)

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

Table 1
Selected geometric parameters (Å, °)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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

supplementary crystallographic information

Comment

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).

Experimental

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).

Refinement

All hydrogen atoms were fixed in calculated positions and refined in riding mode with Uiso(H) = 1.2 Ueq. O—H, N—H and C—H bond lengths were fixed to 0.97, 0.86 and 0.96 Å, respectively. The number of Friedel pairs was 2433.

Figures

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 ...
Fig. 2.
View of the hydrogen bonding network (dashed green bonds) and crystal packing, looking down the c-axis.

Crystal data

[Co2(C2H3O2)4(C7H6N2)4(H2O)]Dx = 1.501 Mg m3
Mr = 844.6Melting point: N/A K
Orthorhombic, Aba2Mo Kα radiation λ = 0.71073 Å
Hall symbol: A 2 -2acCell parameters from 15135 reflections
a = 18.663 (4) Åθ = 1.8–29.5º
b = 8.8101 (18) ŵ = 0.95 mm1
c = 22.727 (5) ÅT = 150 (2) K
V = 3736.7 (13) Å3Block, red
Z = 40.1 × 0.09 × 0.08 mm
F000 = 1744

Data collection

Stoe IPDS diffractometerRint = 0.069
[var phi] oscillation scansθmax = 29.3º
Absorption correction: multi-scan(MULscanABS in PLATON03; Spek, 2003)θmin = 1.8º
Tmin = 0.914, Tmax = 0.956h = −25→25
24157 measured reflectionsk = −12→11
5048 independent reflectionsl = −31→31
3698 reflections with I > 2σ(I)

Refinement

Refinement on F2  w = 1/[σ2(Fo2) + (0.0441P)2] where P = (Fo2 + 2Fc2)/3
Least-squares matrix: full(Δ/σ)max < 0.001
R[F2 > 2σ(F2)] = 0.035Δρmax = 0.36 e Å3
wR(F2) = 0.078Δρmin = −0.57 e Å3
S = 0.89Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
5048 reflectionsExtinction coefficient: 0.00058 (8)
252 parametersAbsolute structure: Flack (1983), 2433 Friedel pairs
1 restraintFlack parameter: 0.006 (12)
H-atom parameters constrained

Special details

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)

xyzUiso*/Ueq
Co10.081808 (12)0.11188 (3)0.166836 (17)0.02569 (8)
O1W000.21585 (12)0.0248 (5)
H1W0.0227−0.07450.24120.03*
O20.10002 (8)−0.1571 (2)0.26630 (9)0.0362 (4)
O10.16471 (8)0.0148 (2)0.21784 (9)0.0305 (4)
O4−0.09188 (8)0.0772 (2)0.11088 (9)0.0314 (4)
O30.00530 (9)0.2253 (2)0.11937 (9)0.0365 (4)
N10.16209 (10)0.2216 (2)0.11482 (10)0.0300 (5)
N40.08897 (11)0.5364 (3)0.25660 (14)0.0434 (6)
H220.09240.63350.25370.052*
N30.07962 (10)0.2950 (2)0.22915 (11)0.0318 (5)
N20.26092 (9)0.3580 (3)0.10253 (11)0.0346 (5)
H120.30150.39960.11040.042*
C270.08124 (12)0.3017 (3)0.29057 (13)0.0331 (6)
C260.07634 (14)0.1894 (3)0.33343 (13)0.0389 (6)
H260.07170.08770.32320.047*
C170.16144 (11)0.2838 (3)0.05885 (12)0.0268 (5)
C220.08784 (13)0.4537 (3)0.30791 (15)0.0386 (7)
C120.22350 (12)0.3704 (3)0.05085 (12)0.0298 (5)
C210.08369 (13)0.4376 (3)0.21186 (15)0.0390 (6)
H210.0830.46690.17250.047*
C110.22226 (12)0.2688 (3)0.13860 (12)0.0329 (6)
H110.23670.24310.17650.04*
C3−0.05615 (12)0.1965 (3)0.10030 (12)0.0286 (5)
C130.23834 (15)0.4491 (3)−0.00066 (13)0.0409 (7)
H130.27970.5071−0.00490.049*
C160.11186 (14)0.2719 (3)0.01321 (13)0.0350 (6)
H160.07060.21360.01730.042*
C20.22415 (14)−0.1402 (4)0.28792 (14)0.0439 (7)
H2A0.2663−0.11470.26580.066*
H2B0.2225−0.24790.2940.066*
H2C0.2255−0.08950.32530.066*
C10.15851 (12)−0.0905 (3)0.25437 (12)0.0286 (5)
C4−0.09095 (15)0.3150 (4)0.06247 (15)0.0434 (7)
H4A−0.11430.2670.02970.065*
H4B−0.05520.38410.04820.065*
H4C−0.12570.36980.08530.065*
C250.07865 (17)0.2341 (4)0.39177 (15)0.0514 (8)
H250.07480.16070.4210.062*
C230.09133 (15)0.4981 (4)0.36623 (17)0.0508 (8)
H230.09670.59960.37660.061*
C150.12589 (16)0.3494 (4)−0.03822 (14)0.0448 (7)
H150.09320.3439−0.0690.054*
C240.08657 (17)0.3864 (4)0.40805 (17)0.0573 (9)
H240.08860.41220.44770.069*
C140.18851 (16)0.4367 (4)−0.04522 (14)0.0455 (7)
H140.19640.4871−0.08060.055*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Co10.01518 (10)0.02082 (13)0.04106 (16)−0.00018 (11)−0.00008 (19)0.00135 (18)
O1W0.0190 (10)0.0170 (12)0.0385 (14)0.0002 (9)00
O20.0257 (7)0.0211 (9)0.0618 (14)0.0010 (7)−0.0038 (8)0.0044 (9)
O10.0208 (7)0.0293 (10)0.0413 (11)0.0016 (7)−0.0033 (7)0.0022 (8)
O40.0185 (7)0.0307 (10)0.0450 (11)−0.0010 (6)−0.0023 (7)0.0060 (8)
O30.0191 (7)0.0347 (11)0.0558 (12)−0.0030 (7)−0.0059 (8)0.0147 (9)
N10.0189 (9)0.0282 (12)0.0429 (13)−0.0043 (8)−0.0002 (9)0.0011 (9)
N40.0312 (11)0.0187 (11)0.0802 (19)−0.0033 (9)0.0069 (12)−0.0051 (12)
N30.0253 (9)0.0194 (10)0.0506 (13)0.0005 (9)0.0034 (10)−0.0016 (9)
N20.0161 (8)0.0391 (13)0.0486 (14)−0.0069 (8)0.0019 (9)0.0006 (11)
C270.0199 (9)0.0234 (13)0.0562 (17)0.0021 (10)−0.0002 (11)−0.0076 (11)
C260.0376 (13)0.0283 (14)0.0508 (17)0.0062 (11)−0.0028 (12)−0.0050 (12)
C170.0214 (10)0.0212 (12)0.0377 (14)0.0021 (9)0.0032 (10)−0.0046 (10)
C220.0231 (11)0.0221 (13)0.071 (2)0.0000 (10)0.0002 (12)−0.0106 (13)
C120.0214 (10)0.0302 (15)0.0380 (14)−0.0002 (9)0.0044 (9)−0.0027 (11)
C210.0317 (12)0.0214 (12)0.0640 (19)−0.0009 (11)0.0095 (13)0.0013 (13)
C110.0202 (10)0.0376 (14)0.0410 (15)−0.0032 (10)−0.0018 (10)0.0031 (12)
C30.0197 (10)0.0299 (14)0.0364 (14)0.0046 (9)0.0000 (10)−0.0001 (11)
C130.0354 (13)0.0378 (16)0.0496 (18)−0.0009 (12)0.0130 (12)0.0006 (13)
C160.0276 (11)0.0312 (15)0.0462 (17)0.0012 (11)−0.0038 (11)−0.0101 (13)
C20.0308 (13)0.055 (2)0.0460 (18)0.0090 (12)−0.0084 (12)0.0021 (15)
C10.0240 (10)0.0215 (13)0.0404 (14)0.0048 (9)−0.0031 (10)−0.0063 (11)
C40.0350 (14)0.0406 (17)0.0545 (19)−0.0001 (12)−0.0108 (14)0.0165 (15)
C250.0548 (18)0.0489 (19)0.0504 (18)0.0122 (15)−0.0070 (16)−0.0068 (15)
C230.0376 (14)0.0388 (17)0.076 (2)0.0034 (13)−0.0068 (15)−0.0244 (18)
C150.0474 (15)0.0504 (19)0.0367 (16)0.0072 (14)−0.0048 (12)−0.0087 (14)
C240.0567 (18)0.055 (2)0.060 (2)0.0147 (16)−0.0184 (18)−0.0205 (19)
C140.0523 (16)0.0474 (18)0.0367 (16)0.0046 (14)0.0084 (13)0.0004 (14)

Geometric parameters (Å, °)

Co1—O32.0495 (18)C17—C161.394 (3)
Co1—O4i2.1044 (19)C17—C121.399 (3)
Co1—O12.1141 (17)C22—C231.383 (5)
Co1—O1W2.1315 (15)C12—C131.389 (4)
Co1—N12.139 (2)C21—H210.93
Co1—N32.147 (2)C11—H110.93
O1W—Co1i2.1315 (15)C3—C41.501 (4)
O1W—H1W0.97C13—C141.379 (4)
O2—C11.269 (3)C13—H130.93
O1—C11.250 (3)C16—C151.379 (4)
O4—C31.267 (3)C16—H160.93
O4—Co1i2.1044 (19)C2—C11.508 (3)
O3—C31.252 (3)C2—H2A0.96
N1—C111.314 (3)C2—H2B0.96
N1—C171.385 (3)C2—H2C0.96
N4—C211.342 (4)C4—H4A0.96
N4—C221.375 (4)C4—H4B0.96
N4—H220.86C4—H4C0.96
N3—C211.319 (4)C25—C241.400 (5)
N3—C271.397 (4)C25—H250.93
N2—C111.346 (3)C23—C241.371 (5)
N2—C121.371 (4)C23—H230.93
N2—H120.86C15—C141.408 (4)
C27—C261.391 (4)C15—H150.93
C27—C221.402 (4)C24—H240.93
C26—C251.384 (4)C14—H140.93
C26—H260.93
O3—Co1—O4i97.48 (8)C13—C12—C17123.2 (3)
O3—Co1—O1174.69 (7)N3—C21—N4113.3 (3)
O4i—Co1—O186.88 (7)N3—C21—H21123.3
O3—Co1—O1W90.09 (6)N4—C21—H21123.3
O4i—Co1—O1W90.78 (7)N1—C11—N2113.1 (2)
O1—Co1—O1W92.89 (6)N1—C11—H11123.4
O3—Co1—N188.66 (8)N2—C11—H11123.4
O4i—Co1—N187.79 (8)O3—C3—O4125.8 (2)
O1—Co1—N188.48 (7)O3—C3—C4117.0 (2)
O1W—Co1—N1177.97 (9)O4—C3—C4117.2 (2)
O3—Co1—N388.14 (8)C14—C13—C12116.4 (3)
O4i—Co1—N3174.38 (8)C14—C13—H13121.8
O1—Co1—N387.50 (8)C12—C13—H13121.8
O1W—Co1—N389.38 (8)C15—C16—C17117.9 (3)
N1—Co1—N392.19 (8)C15—C16—H16121.1
Co1i—O1W—Co1116.98 (13)C17—C16—H16121.1
Co1i—O1W—H1W108.1C1—C2—H2A109.5
Co1—O1W—H1W108.1C1—C2—H2B109.5
C1—O1—Co1126.63 (14)H2A—C2—H2B109.5
C3—O4—Co1i136.38 (16)C1—C2—H2C109.5
C3—O3—Co1136.17 (18)H2A—C2—H2C109.5
C11—N1—C17105.1 (2)H2B—C2—H2C109.5
C11—N1—Co1120.94 (18)O1—C1—O2124.4 (2)
C17—N1—Co1132.86 (15)O1—C1—C2118.4 (2)
C21—N4—C22107.3 (2)O2—C1—C2117.2 (2)
C21—N4—H22126.3C3—C4—H4A109.5
C22—N4—H22126.3C3—C4—H4B109.5
C21—N3—C27104.9 (2)H4A—C4—H4B109.5
C21—N3—Co1121.2 (2)C3—C4—H4C109.5
C27—N3—Co1133.63 (17)H4A—C4—H4C109.5
C11—N2—C12107.17 (19)H4B—C4—H4C109.5
C11—N2—H12126.4C26—C25—C24121.9 (4)
C12—N2—H12126.4C26—C25—H25119
C26—C27—N3131.9 (2)C24—C25—H25119
C26—C27—C22119.2 (3)C24—C23—C22117.3 (3)
N3—C27—C22108.8 (3)C24—C23—H23121.4
C25—C26—C27117.8 (3)C22—C23—H23121.4
C25—C26—H26121.1C16—C15—C14121.6 (3)
C27—C26—H26121.1C16—C15—H15119.2
N1—C17—C16131.3 (2)C14—C15—H15119.2
N1—C17—C12109.1 (2)C23—C24—C25120.8 (3)
C16—C17—C12119.6 (3)C23—C24—H24119.6
N4—C22—C23131.5 (3)C25—C24—H24119.6
N4—C22—C27105.6 (3)C13—C14—C15121.3 (3)
C23—C22—C27122.9 (3)C13—C14—H14119.3
N2—C12—C13131.3 (2)C15—C14—H14119.3
N2—C12—C17105.5 (2)

Symmetry codes: (i) −x, −y, z.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1W—H1W···O20.971.712.591 (2)149
N4—H22···O2ii0.861.872.717 (3)167
N2—H12···O4iii0.862.002.812 (2)157

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SI2092).

References

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