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Acta Crystallogr Sect E Struct Rep Online. 2009 November 1; 65(Pt 11): m1423.
Published online 2009 October 23. doi:  10.1107/S1600536809043177
PMCID: PMC2971142

Tetra­aqua­bis­(1H-benzimidazole-5,6-di­carboxyl­ato-κN 3)cobalt(II) dimethyl­formamide disolvate dihydrate

Abstract

In the mononuclear title compound, [Co(C9H4N2O4)2(H2O)4]·2C3H7NO·2H2O, the CoII atom, which lies on a center of inversion, is coordinated by four water mol­ecules and two N atoms from two two symmetry-related 1H-benzimidazole-5,6-dicarboxyl­ate ligands in a distorted octa­hedral geometry. The packing is governed by inter­molecular O—H(...)O and N—H(...)O hydrogen-bonding inter­actions.

Related literature

For 1H-benzimidazole-5,6-dicarboxyl­ate complexes, see: Song et al. (2009a [triangle],b [triangle],c [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-m1423-scheme1.jpg

Experimental

Crystal data

  • [Co(C9H5N2O4)2(H2O)4]·2C3H7NO·2H2O
  • M r = 723.52
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-m1423-efi1.jpg
  • a = 8.5612 (17) Å
  • b = 9.1475 (18) Å
  • c = 11.642 (2) Å
  • α = 100.82 (3)°
  • β = 102.98 (3)°
  • γ = 114.11 (3)°
  • V = 769.9 (3) Å3
  • Z = 1
  • Mo Kα radiation
  • μ = 0.64 mm−1
  • T = 293 K
  • 0.30 × 0.24 × 0.21 mm

Data collection

  • Rigaku/MSC Mercury CCD diffractometer
  • Absorption correction: multi-scan (REQAB; Jacobson, 1998 [triangle]) T min = 0.831, T max = 0.877
  • 6161 measured reflections
  • 2751 independent reflections
  • 2594 reflections with I > 2σ(I)
  • R int = 0.020

Refinement

  • R[F 2 > 2σ(F 2)] = 0.038
  • wR(F 2) = 0.127
  • S = 0.96
  • 2751 reflections
  • 219 parameters
  • 10 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.58 e Å−3
  • Δρmin = −0.44 e Å−3

Data collection: RAPID-AUTO (Rigaku, 1998 [triangle]); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEPII (Johnson, 1976 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809043177/ng2669sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809043177/ng2669Isup2.hkl

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

Acknowledgments

The authors acknowledge Guang Dong Ocean University for supporting this work.

supplementary crystallographic information

Comment

From the structuralpoint of view, 1H-benzimidazole-5,6-dicarboxylic acid possesses two nitrogen atoms of imidazole ring and four oxygen atoms of carboxylate groups, and might be used as versatile linker in constructing coordination polymers with abundant hydrogen bonds. And based on this idea a series of coordination polymers fomed by this ligand have been reported by us: Pentaaqua(1H-benzimidazole-5,6- dicarboxylato-kN3)cobalt(II)pentahydrate (Song et al., 2009b), Pentaaqua(1H-benzimidazole-5,6-dicarboxylato-κN3)nickel(II)pentahydrate (Song et al., 2009c), catena-Poly[[diaqua(1,10-phenanthroline-k2N,N') nickel(II)]-µ-1H-benzimidazole-5,6-dicarboxylato-k2N3:O6] (Song et al., 2009a).In the present paper, we synthesized a novel coordination complex [Co(C9H4N2O4)2(H2O)4].2H2O.2C3H7NO.

As shown in Figure 1, the CoII atom exhibits an octahedral coordination sphere, defined by two N atoms from two different 1H-benzimidazole-5,6-dicarboxylate ligands, and four water molecules. The equatorial plane is defined by O1w, O2w, O1wi and O2wi atoms, while N1 and N1i occupy the axial position (symmetry codes: i = -x, 1 - y, 1 - z). The solvent (water and dimethylformamide) molecules are also present in the asymmetic unit. Inter/intramolecular O—H···O and N—H···O hydrogen bonds form a three-dimensional supramolecular network making the structure more stable(Fig 2).The hydrogen bonds are in the normal range(Table 1).

Experimental

A C3H7NO solution (20 mL)containing Co(NO3)2(0.1 mmol)and 1H-benzimidazole-5,6-dicarboxylic acid(0.2 mmol) was stirred for a few minutes in air,and left to stand at room temperature for about a few weeks, then the red crystals were obtained.

Refinement

Carbon and nitrogen bound H atoms were placed at calculated positions and were treated as riding on the parent C or N atoms with C—H = 0.93 Å, N—H = 0.86 Å, and with Uiso(H) = 1.2 Ueq(C, N). The water H-atoms were located in a difference map, and were refined with a distance restraint of O—H = 0.84 Å; their Uiso values were refined.

Figures

Fig. 1.
The structure of the title compound, showing the atomic numbering scheme with 30% probability displacement ellipsoids. [Symmetry codes: (i) -x, 1 - y, 1 - z.]
Fig. 2.
A view of the three-dimensional network constructed by O—H···O and N—H···O hydrogen bonding interactions.

Crystal data

[Co(C9H5N2O4)2(H2O)4]·2C3H7NO·2H2OZ = 1
Mr = 723.52F(000) = 377
Triclinic, P1Dx = 1.561 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.5612 (17) ÅCell parameters from 3420 reflections
b = 9.1475 (18) Åθ = 3.3–27.4°
c = 11.642 (2) ŵ = 0.64 mm1
α = 100.82 (3)°T = 293 K
β = 102.98 (3)°Block, red
γ = 114.11 (3)°0.30 × 0.24 × 0.21 mm
V = 769.9 (3) Å3

Data collection

Rigaku/MSC Mercury CCD diffractometer2751 independent reflections
Radiation source: fine-focus sealed tube2594 reflections with I > 2σ(I)
graphiteRint = 0.020
ω scansθmax = 25.2°, θmin = 3.3°
Absorption correction: multi-scan (REQAB; Jacobson, 1998)h = −10→10
Tmin = 0.831, Tmax = 0.877k = −10→10
6161 measured reflectionsl = −13→13

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.127H atoms treated by a mixture of independent and constrained refinement
S = 0.96w = 1/[σ2(Fo2) + (0.0795P)2 + 1.194P] where P = (Fo2 + 2Fc2)/3
2751 reflections(Δ/σ)max < 0.001
219 parametersΔρmax = 0.58 e Å3
10 restraintsΔρmin = −0.44 e Å3

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.
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 > σ(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)

xyzUiso*/Ueq
C10.1417 (4)0.8422 (3)0.1200 (2)0.0279 (6)
C20.2484 (3)0.8904 (3)0.2467 (2)0.0247 (5)
C30.1906 (3)0.7887 (3)0.3191 (2)0.0269 (5)
H30.25950.82010.40200.032*
C40.0277 (3)0.6389 (3)0.2654 (2)0.0248 (5)
C5−0.0742 (3)0.5940 (3)0.1405 (2)0.0272 (6)
C6−0.0194 (4)0.6932 (4)0.0667 (2)0.0309 (6)
H6−0.08880.6606−0.01630.037*
C70.1921 (4)0.9449 (4)0.0363 (3)0.0324 (6)
C80.4297 (3)1.0478 (3)0.3103 (2)0.0263 (5)
C9−0.2117 (4)0.4034 (3)0.2225 (3)0.0310 (6)
H9−0.29840.30640.22990.037*
C100.6732 (4)0.7964 (4)0.1713 (3)0.0344 (6)
H100.78010.89720.19550.041*
N30.6382 (3)0.7242 (3)0.2550 (2)0.0340 (5)
Co10.00000.50000.50000.02238 (18)
N1−0.2262 (3)0.4426 (3)0.1168 (2)0.0315 (5)
H1−0.31370.38460.04730.038*
N2−0.0630 (3)0.5150 (3)0.3148 (2)0.0282 (5)
C120.4674 (5)0.5710 (5)0.2251 (4)0.0552 (9)
H3A0.37420.60080.23300.083*
H3B0.48290.50940.28120.083*
H3C0.43300.50210.14140.083*
C110.7568 (6)0.8059 (5)0.3848 (3)0.0547 (9)
H4A0.86400.90360.39110.082*
H4B0.79070.72830.41450.082*
H4C0.69370.83930.43400.082*
O10.1079 (3)0.8972 (3)−0.0726 (2)0.0582 (7)
O20.3337 (4)1.0933 (3)0.0904 (2)0.0635 (8)
O30.4308 (3)1.1767 (3)0.3708 (2)0.0458 (6)
O40.5660 (3)1.0359 (3)0.3035 (3)0.0524 (6)
O50.5725 (3)0.7391 (3)0.06005 (19)0.0457 (6)
O1W0.0884 (2)0.7574 (2)0.57397 (17)0.0300 (4)
H2W0.02960.77840.61760.045*
H1W0.20070.81330.61260.045*
O2W0.2619 (3)0.5455 (2)0.50191 (19)0.0360 (5)
H4W0.25760.48810.43470.054*
H3W0.36300.63210.53810.054*
O3W0.1590 (3)0.2539 (3)0.3083 (2)0.0498 (6)
H5W0.24520.23120.32750.075*
H6W0.09050.20040.23430.075*
H20.367 (6)1.146 (5)0.041 (3)0.075*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0271 (13)0.0262 (13)0.0258 (13)0.0076 (11)0.0094 (10)0.0090 (10)
C20.0231 (12)0.0223 (12)0.0259 (13)0.0076 (10)0.0088 (10)0.0076 (10)
C30.0258 (13)0.0260 (13)0.0217 (12)0.0073 (11)0.0052 (10)0.0071 (10)
C40.0247 (12)0.0238 (12)0.0245 (12)0.0089 (10)0.0098 (10)0.0089 (10)
C50.0248 (13)0.0230 (13)0.0260 (13)0.0052 (11)0.0080 (10)0.0062 (10)
C60.0303 (14)0.0302 (14)0.0224 (13)0.0067 (12)0.0060 (11)0.0082 (11)
C70.0322 (14)0.0304 (14)0.0262 (14)0.0071 (12)0.0081 (11)0.0111 (11)
C80.0232 (13)0.0248 (13)0.0257 (13)0.0066 (11)0.0064 (10)0.0101 (11)
C90.0277 (14)0.0244 (13)0.0306 (14)0.0026 (11)0.0088 (11)0.0103 (11)
C100.0334 (15)0.0294 (14)0.0290 (14)0.0074 (12)0.0047 (12)0.0088 (11)
N30.0404 (13)0.0350 (13)0.0270 (12)0.0174 (11)0.0105 (10)0.0122 (10)
Co10.0203 (3)0.0186 (3)0.0219 (3)0.0040 (2)0.00591 (19)0.00645 (19)
N10.0243 (11)0.0260 (12)0.0229 (11)−0.0027 (9)0.0002 (9)0.0055 (9)
N20.0271 (11)0.0238 (11)0.0262 (11)0.0046 (9)0.0083 (9)0.0097 (9)
C120.052 (2)0.057 (2)0.060 (2)0.0169 (18)0.0275 (18)0.0332 (18)
C110.085 (3)0.055 (2)0.0270 (16)0.041 (2)0.0084 (16)0.0138 (15)
O10.0560 (15)0.0498 (14)0.0286 (11)−0.0072 (11)−0.0002 (10)0.0191 (10)
O20.0580 (15)0.0463 (14)0.0325 (12)−0.0183 (12)−0.0036 (11)0.0210 (11)
O30.0293 (11)0.0302 (11)0.0569 (14)0.0051 (9)0.0109 (10)−0.0062 (10)
O40.0218 (10)0.0340 (12)0.0823 (18)0.0077 (9)0.0093 (11)−0.0002 (11)
O50.0399 (12)0.0433 (12)0.0270 (11)−0.0014 (10)0.0014 (9)0.0144 (9)
O1W0.0238 (9)0.0245 (9)0.0318 (10)0.0058 (8)0.0057 (8)0.0051 (8)
O2W0.0250 (10)0.0296 (10)0.0399 (11)0.0049 (8)0.0114 (8)0.0004 (8)
O3W0.0428 (13)0.0590 (15)0.0395 (12)0.0271 (12)0.0088 (10)−0.0033 (11)

Geometric parameters (Å, °)

C1—C61.381 (4)N3—C121.462 (4)
C1—C21.424 (4)N3—C111.463 (4)
C1—C71.489 (4)Co1—O1W2.086 (2)
C2—C31.387 (4)Co1—O1Wi2.086 (2)
C2—C81.513 (4)Co1—O2Wi2.1007 (19)
C3—C41.393 (4)Co1—O2W2.1007 (19)
C3—H30.9300Co1—N22.146 (2)
C4—N21.395 (3)Co1—N2i2.146 (2)
C4—C51.398 (4)N1—H10.8600
C5—C61.382 (4)C12—H3A0.9600
C5—N11.382 (3)C12—H3B0.9600
C6—H60.9300C12—H3C0.9600
C7—O11.201 (4)C11—H4A0.9600
C7—O21.304 (4)C11—H4B0.9600
C8—O41.234 (3)C11—H4C0.9600
C8—O31.250 (3)O2—H20.839 (10)
C9—N21.315 (4)O1W—H2W0.8400
C9—N11.338 (4)O1W—H1W0.8400
C9—H90.9300O2W—H4W0.8399
C10—O51.253 (3)O2W—H3W0.8399
C10—N31.299 (4)O3W—H5W0.8400
C10—H100.9300O3W—H6W0.8399
C6—C1—C2120.8 (2)O1Wi—Co1—O2W88.64 (8)
C6—C1—C7115.4 (2)O2Wi—Co1—O2W180.0
C2—C1—C7123.8 (2)O1W—Co1—N290.82 (9)
C3—C2—C1120.3 (2)O1Wi—Co1—N289.18 (9)
C3—C2—C8115.8 (2)O2Wi—Co1—N290.29 (9)
C1—C2—C8123.9 (2)O2W—Co1—N289.71 (9)
C2—C3—C4118.9 (2)O1W—Co1—N2i89.18 (9)
C2—C3—H3120.6O1Wi—Co1—N2i90.82 (9)
C4—C3—H3120.6O2Wi—Co1—N2i89.71 (9)
C3—C4—N2131.3 (2)O2W—Co1—N2i90.29 (9)
C3—C4—C5119.7 (2)N2—Co1—N2i179.999 (1)
N2—C4—C5108.9 (2)C9—N1—C5107.1 (2)
C6—C5—N1132.1 (2)C9—N1—H1126.5
C6—C5—C4122.4 (2)C5—N1—H1126.5
N1—C5—C4105.5 (2)C9—N2—C4104.9 (2)
C1—C6—C5117.9 (2)C9—N2—Co1124.00 (18)
C1—C6—H6121.0C4—N2—Co1130.98 (18)
C5—C6—H6121.0N3—C12—H3A109.5
O1—C7—O2121.9 (3)N3—C12—H3B109.5
O1—C7—C1123.1 (3)H3A—C12—H3B109.5
O2—C7—C1115.0 (2)N3—C12—H3C109.5
O4—C8—O3125.2 (3)H3A—C12—H3C109.5
O4—C8—C2117.0 (2)H3B—C12—H3C109.5
O3—C8—C2117.7 (2)N3—C11—H4A109.5
N2—C9—N1113.6 (2)N3—C11—H4B109.5
N2—C9—H9123.2H4A—C11—H4B109.5
N1—C9—H9123.2N3—C11—H4C109.5
O5—C10—N3124.3 (3)H4A—C11—H4C109.5
O5—C10—H10117.8H4B—C11—H4C109.5
N3—C10—H10117.8C7—O2—H2114 (3)
C10—N3—C12120.6 (3)Co1—O1W—H2W113.1
C10—N3—C11120.7 (3)Co1—O1W—H1W113.3
C12—N3—C11118.2 (3)H2W—O1W—H1W110.9
O1W—Co1—O1Wi180.0Co1—O2W—H4W110.8
O1W—Co1—O2Wi88.64 (8)Co1—O2W—H3W130.9
O1Wi—Co1—O2Wi91.36 (8)H4W—O2W—H3W112.2
O1W—Co1—O2W91.36 (8)H5W—O3W—H6W112.2

Symmetry codes: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O2—H2···O5ii0.84 (1)1.75 (1)2.588 (3)177 (5)
O3W—H6W···O1iii0.841.982.800 (3)165
O3W—H5W···O3iv0.841.852.686 (3)179
O2W—H3W···O3v0.841.802.636 (3)174
O2W—H4W···O3W0.842.062.811 (3)148
O1W—H1W···O4v0.841.792.624 (3)170
O1W—H2W···O3Wi0.841.942.749 (3)161
N1—H1···O5iii0.861.982.782 (3)154
N1—H1···O5iii0.861.982.782 (3)154

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NG2669).

References

  • Jacobson, R. (1998). REQAB MSC, The Woodlands, Texas, USA.
  • Johnson, C. K. (1976). ORTEPII Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA.
  • Rigaku (1998). RAPID-AUTO Rigaku Corporation, Tokyo, Japan.
  • Rigaku/MSC (2002). CrystalStructure Rigaku/MSC, The Woodlands, Texas, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Song, W.-D., Wang, H., Hu, S.-W., Qin, P.-W. & Li, S.-J. (2009a). Acta Cryst. E65, m701. [PMC free article] [PubMed]
  • Song, W.-D., Wang, H., Li, S.-J., Qin, P.-W. & Hu, S.-W. (2009b). Acta Cryst. E65, m702. [PMC free article] [PubMed]
  • Song, W.-D., Wang, H., Qin, P.-W., Li, S.-J. & Hu, S.-W. (2009c). Acta Cryst. E65, m672. [PMC free article] [PubMed]

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