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Acta Cryst. (2010). E66, m209-m210    [ doi:10.1107/S1600536810003065 ]

Poly[[aqua([mu]4-1H-benzimidazole-5,6-dicarboxylato-[kappa]4N3:O5:O5':O6)(N,N-dimethylformamide-[kappa]O)cadmium(II)] dihydrate]

H. Wang, S.-J. Li, W.-D. Song, X.-F. Li and D.-L. Miao

Abstract top

In the title compound, {[Cd(C9H4N2O4)(C3H7NO)(H2O)]·2H2O}n, the CdII atom is coordinated by one N atom and three O atoms from four different 1H-benzimidazole-5,6-dicarboxylate (Hbidc) ligands, one O atom from one dimethylformamide ligand, and one O atom from a water molecule in a distorted octahedral geometry. The Hbidc ligands connect the Cd atoms into a two-dimensional network parallel to (001). N-H...O and O-H...O hydrogen bonds involving the water molecules are observed in the crystal structure.

Comment top

From the structural point of view, 1H-benzimidazole-5,6-dicarboxylic acid (H3bidc) possesses two N atoms of imidazole ring and four O atoms of carboxylate groups and might be used as versatile linker in constructing coordination polymers with abundant hydrogen bonds. Based on this idea, a series of coordination polymers fomed by this ligand have been reported by us: catena-poly[[diaqua(1,10-phenanthroline-κ2N,N')nickel(II)]- µ-Hbidc-κ2N3:O6] (Song, Wang, Hu et al., 2009), pentaaqua(Hbidc-κN3)cobalt(II) pentahydrate (Song, Wang, Li et al., 2009), pentaaqua(Hbidc-κN3)nickel(II) pentahydrate (Song, Wang, Qin et al., 2009), and tetraaquabis(Hbidc-κN3)cobalt(II) dimethylformamide disolvate dihydrate (Wang et al., 2009). In the present paper, we report the title complex.

As shown in Fig. 1, the CdII atom exhibits an octahedral coordination geometry, defined by three O atoms from three different Hbidc ligands, one N atom from another Hbidc ligand, one O atom from a dimethylformamide ligand and one O atom from a water molecule. The equatorial plane is defined by O1W, O10, N1i and O3iii atoms, while O1 and O4ii occupy the axial positions [symmetry codes: (i) -x, 1-y, 1-z; (ii) 1+x, y, z; (iii) -x, -y, 1-z]. Two solvent water molecules are present in the asymmetic unit. O—H···O and N—H···O hydrogen bonds are observed in the crystal structure with hydrogen-bond geometry in the normal range (Fig. 2 and Table 1).

Related literature top

For related structures of 1H-benzimidazole-5,6-dicarboxylate complexes, see: Song, Wang, Hu et al. (2009); Song, Wang, Li et al. (2009); Song, Wang, Qin et al. (2009); Wang et al. (2009).

Experimental top

A dimethylformamide solution (20 ml) containing CdCl2(0.1 mmol) and H3bidc (0.2 mmol) was stirred for a few minutes in air, and then left to stand at room temperature. Colorless crystals were obtained in a few weeks.

Refinement top

C- and N-bound H atoms were placed at calculated positions and treated as riding on the parent atoms, with C—H = 0.93 (CH), 0.96 (CH3), N—H = 0.86 Å and with Uiso(H) = 1.2(1.5 for methyl)Ueq(C, N). The water H-atoms were located in a difference Fourier map and refined as riding, with a distance restraint of O—H = 0.84 Å and with Uiso(H) = 1.5Ueq(O). The highest residual electron density was found 1.07 Å from Cd1 and the deepest hole 0.97 Å from Cd1.

Computing details top

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

Figures top
[Figure 1] Fig. 1. The asymmetric unit of the title compound, showing the 30% probability displacement ellipsoids. [Symmetry codes: (i) -x, 1-y, 1-z; (ii) 1+x, y, z; (iii) -x, -y,1-z.]
[Figure 2] Fig. 2. A view of the crystal packing. Hydrogen bonds are shown as dashed lines.
Poly[[aqua(µ4-1H-benzimidazole-5,6-dicarboxylato- κ4N3:O5:O5':O6)(N,N- dimethylformamide-κO)cadmium(II)] dihydrate] top
Crystal data top
[Cd(C9H4N2O4)(C3H7NO)(H2O)]·2H2OZ = 2
Mr = 443.69F(000) = 444
Triclinic, P1Dx = 1.881 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.7729 (16) ÅCell parameters from 3441 reflections
b = 9.1648 (18) Åθ = 3.3–27.4°
c = 11.458 (2) ŵ = 1.44 mm−1
α = 102.76 (3)°T = 293 K
β = 97.70 (3)°Block, colorless
γ = 94.96 (3)°0.29 × 0.25 × 0.21 mm
V = 783.2 (3) Å3
Data collection top
Rigaku/MSC Mercury CCD
diffractometer		2800 independent reflections
Radiation source: fine-focus sealed tube1539 reflections with I > 2σ(I)
graphiteRint = 0.121
ω scansθmax = 25.2°, θmin = 3.3°
Absorption correction: multi-scan
(REQAB; Jacobson, 1998)		h = −9→7
Tmin = 0.680, Tmax = 0.752k = −10→10
6197 measured reflectionsl = −13→13
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.086Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.223H-atom parameters constrained
S = 1.14 w = 1/[σ2(Fo2) + (0.0683P)2 + 2.7388P]
where P = (Fo2 + 2Fc2)/3
2800 reflections(Δ/σ)max < 0.001
219 parametersΔρmax = 2.12 e Å−3
9 restraintsΔρmin = −1.80 e Å−3
Crystal data top
[Cd(C9H4N2O4)(C3H7NO)(H2O)]·2H2Oγ = 94.96 (3)°
Mr = 443.69V = 783.2 (3) Å3
Triclinic, P1Z = 2
a = 7.7729 (16) ÅMo Kα radiation
b = 9.1648 (18) ŵ = 1.44 mm−1
c = 11.458 (2) ÅT = 293 K
α = 102.76 (3)°0.29 × 0.25 × 0.21 mm
β = 97.70 (3)°
Data collection top
Rigaku/MSC Mercury CCD
diffractometer		2800 independent reflections
Absorption correction: multi-scan
(REQAB; Jacobson, 1998)		1539 reflections with I > 2σ(I)
Tmin = 0.680, Tmax = 0.752Rint = 0.121
6197 measured reflectionsθmax = 25.2°
Refinement top
R[F2 > 2σ(F2)] = 0.086H-atom parameters constrained
wR(F2) = 0.223Δρmax = 2.12 e Å−3
S = 1.14Δρmin = −1.80 e Å−3
2800 reflectionsAbsolute structure: ?
219 parametersFlack parameter: ?
9 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cd10.32811 (14)0.19007 (13)0.58926 (9)0.0427 (4)
O10.1397 (12)0.1778 (11)0.7248 (7)0.043 (2)
O2−0.1244 (11)0.1608 (11)0.7803 (8)0.043 (2)
O1W0.5202 (9)0.0812 (8)0.7112 (7)0.045 (3)
O100.4501 (13)0.4197 (11)0.7028 (8)0.048 (3)
N1−0.1716 (14)0.7274 (13)0.5549 (9)0.037 (3)
N20.0418 (16)0.7573 (12)0.7100 (10)0.046 (3)
H20.12470.80190.76760.055*
N30.6296 (17)0.5826 (15)0.8605 (11)0.057 (4)
C1−0.0542 (18)0.8220 (17)0.6334 (13)0.044 (4)
H1−0.03820.92450.63620.053*
C2−0.1506 (16)0.5900 (15)0.5837 (12)0.035 (3)
C3−0.2450 (15)0.4482 (15)0.5278 (10)0.031 (3)
H3−0.33530.43700.46330.037*
C4−0.1988 (17)0.3261 (16)0.5722 (11)0.037 (3)
C5−0.0634 (17)0.3421 (14)0.6700 (11)0.033 (3)
C60.0295 (17)0.4860 (17)0.7241 (12)0.045 (4)
H60.12030.49990.78870.054*
C7−0.0192 (16)0.6032 (16)0.6778 (10)0.033 (3)
C8−0.0144 (18)0.2164 (15)0.7258 (12)0.039 (3)
C110.758 (3)0.606 (2)0.9664 (14)0.086 (6)
H11A0.76490.51230.99070.128*
H11B0.72500.67931.03060.128*
H11C0.86930.64070.94910.128*
C120.587 (2)0.713 (2)0.8183 (16)0.077 (6)
H12A0.56130.68680.73130.116*
H12B0.68350.79070.84450.116*
H12C0.48590.74770.85060.116*
C100.560 (2)0.4477 (19)0.7957 (13)0.054 (4)
H100.59750.36550.82260.065*
O3W0.7681 (13)0.2252 (9)1.0089 (11)0.127 (6)
H5W0.84650.21240.96500.190*
H6W0.69980.14460.98910.190*
O2W0.2935 (7)0.0032 (12)0.8739 (9)0.080 (4)
H3W0.39060.02070.85220.120*
H4W0.22730.05100.83640.120*
C9−0.2912 (17)0.1756 (17)0.5120 (11)0.036 (3)
O3−0.2155 (12)0.0562 (10)0.5048 (7)0.041 (2)
O4−0.4532 (9)0.1698 (8)0.4625 (7)0.043 (2)
H1W0.62790.10810.73150.065*
H2W0.4982−0.00840.67110.065*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd10.0451 (7)0.0367 (7)0.0457 (6)−0.0036 (5)0.0070 (4)0.0115 (5)
O10.040 (6)0.042 (6)0.043 (5)−0.015 (5)0.005 (4)0.013 (4)
O20.033 (5)0.041 (6)0.059 (6)−0.002 (5)0.007 (4)0.024 (5)
O1W0.040 (5)0.038 (6)0.049 (5)−0.017 (5)0.006 (4)0.004 (5)
O100.054 (6)0.044 (7)0.039 (5)−0.003 (5)−0.005 (5)0.006 (5)
N10.035 (6)0.030 (7)0.042 (6)0.000 (6)0.000 (5)0.006 (5)
N20.056 (8)0.023 (7)0.053 (7)−0.007 (6)0.011 (6)0.002 (6)
N30.062 (9)0.034 (8)0.064 (8)0.003 (7)−0.009 (7)0.004 (7)
C10.048 (9)0.035 (9)0.064 (9)0.014 (7)0.021 (8)0.031 (8)
C20.030 (7)0.029 (8)0.057 (8)0.011 (6)0.020 (6)0.020 (7)
C30.025 (6)0.043 (9)0.023 (6)−0.010 (6)0.001 (5)0.010 (6)
C40.035 (8)0.040 (9)0.034 (7)−0.009 (7)0.003 (6)0.009 (6)
C50.045 (8)0.022 (7)0.033 (7)0.002 (6)0.006 (6)0.008 (6)
C60.032 (8)0.055 (10)0.043 (8)−0.006 (7)−0.007 (6)0.016 (7)
C70.029 (7)0.047 (9)0.029 (7)0.016 (7)0.003 (5)0.016 (6)
C80.041 (9)0.027 (8)0.043 (8)−0.011 (7)0.010 (6)−0.002 (6)
C110.105 (16)0.080 (15)0.052 (10)0.008 (12)−0.028 (10)0.001 (10)
C120.083 (14)0.063 (14)0.078 (12)0.011 (11)0.036 (10)−0.013 (10)
C100.065 (11)0.049 (11)0.049 (9)0.012 (9)0.009 (8)0.009 (8)
O3W0.171 (17)0.126 (15)0.085 (10)−0.006 (12)0.049 (10)0.020 (10)
O2W0.075 (8)0.090 (10)0.088 (8)0.009 (7)0.027 (7)0.041 (8)
C90.037 (8)0.044 (9)0.030 (7)0.006 (7)0.008 (6)0.015 (6)
O30.056 (6)0.028 (6)0.039 (5)0.000 (5)0.011 (4)0.005 (4)
O40.044 (6)0.037 (6)0.041 (5)−0.009 (5)0.008 (4)−0.001 (4)
Geometric parameters (Å, °) top
Cd1—N1i2.226 (11)C3—C41.382 (19)
Cd1—O102.266 (9)C3—H30.9300
Cd1—O12.287 (8)C4—C51.404 (18)
Cd1—O3ii2.314 (9)C4—C91.472 (18)
Cd1—O1W2.344 (9)C5—C61.414 (18)
Cd1—O4iii2.373 (7)C5—C81.489 (19)
O1—C81.278 (16)C6—C71.359 (19)
O2—C81.261 (14)C6—H60.9300
O1W—H1W0.8380C11—H11A0.9600
O1W—H2W0.8382C11—H11B0.9600
O10—C101.236 (17)C11—H11C0.9600
N1—C11.301 (17)C12—H12A0.9600
N1—C21.388 (17)C12—H12B0.9600
N2—C11.346 (17)C12—H12C0.9600
N2—C71.400 (17)C10—H100.9300
N2—H20.8600O3W—H5W0.8411
N3—C101.320 (19)O3W—H6W0.8398
N3—C111.426 (19)O2W—H3W0.8389
N3—C121.43 (2)O2W—H4W0.8393
C1—H10.9300C9—O31.279 (16)
C2—C71.359 (18)C9—O41.302 (14)
C2—C31.407 (17)
N1i—Cd1—O1096.6 (4)C3—C4—C9118.6 (11)
N1i—Cd1—O1103.1 (4)C5—C4—C9119.8 (13)
O10—Cd1—O189.6 (3)C4—C5—C6119.5 (13)
N1i—Cd1—O3ii90.6 (4)C4—C5—C8123.9 (12)
O10—Cd1—O3ii172.6 (3)C6—C5—C8116.6 (12)
O1—Cd1—O3ii86.9 (3)C7—C6—C5117.3 (12)
N1i—Cd1—O1W169.1 (3)C7—C6—H6121.3
O10—Cd1—O1W88.5 (3)C5—C6—H6121.3
O1—Cd1—O1W86.5 (3)C6—C7—C2124.0 (13)
O3ii—Cd1—O1W84.8 (3)C6—C7—N2132.0 (12)
N1i—Cd1—O4iii85.9 (3)C2—C7—N2103.9 (12)
O10—Cd1—O4iii93.7 (3)O2—C8—O1123.0 (14)
O1—Cd1—O4iii170.0 (3)O2—C8—C5117.4 (13)
O3ii—Cd1—O4iii88.7 (3)O1—C8—C5119.3 (11)
O1W—Cd1—O4iii84.1 (3)N3—C11—H11A109.5
C8—O1—Cd1130.4 (8)N3—C11—H11B109.5
H1W—O1W—H2W112.2H11A—C11—H11B109.5
C10—O10—Cd1127.5 (11)N3—C11—H11C109.5
C1—N1—C2103.9 (12)H11A—C11—H11C109.5
C1—N1—Cd1i118.8 (10)H11B—C11—H11C109.5
C2—N1—Cd1i137.1 (9)N3—C12—H12A109.5
C1—N2—C7106.8 (11)N3—C12—H12B109.5
C1—N2—H2126.6H12A—C12—H12B109.5
C7—N2—H2126.6N3—C12—H12C109.5
C10—N3—C11123.2 (15)H12A—C12—H12C109.5
C10—N3—C12119.1 (14)H12B—C12—H12C109.5
C11—N3—C12117.5 (15)O10—C10—N3126.5 (16)
N1—C1—N2113.5 (13)O10—C10—H10116.7
N1—C1—H1123.2N3—C10—H10116.7
N2—C1—H1123.2H5W—O3W—H6W105.9
C7—C2—N1111.8 (12)H3W—O2W—H4W103.7
C7—C2—C3120.0 (13)O3—C9—O4121.1 (12)
N1—C2—C3128.2 (13)O3—C9—C4122.1 (12)
C4—C3—C2117.7 (11)O4—C9—C4116.8 (13)
C4—C3—H3121.2C9—O3—Cd1ii128.7 (8)
C2—C3—H3121.2C9—O4—Cd1iv118.5 (7)
C3—C4—C5121.6 (12)
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x, −y, −z+1; (iii) x+1, y, z; (iv) x−1, y, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W···O2iii0.841.922.757 (11)177
O1W—H2W···O4ii0.841.852.649 (12)159
O2W—H3W···O1W0.842.162.888 (9)145
O2W—H4W···O10.842.002.811 (11)162
O3W—H5W···O2iii0.842.112.810 (12)140
O3W—H6W···O2Wv0.842.292.766 (14)117
N2—H2···O2Wvi0.862.182.970 (16)152
Symmetry codes: (iii) x+1, y, z; (ii) −x, −y, −z+1; (v) −x+1, −y, −z+2; (vi) x, y+1, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W···O2i0.841.922.757 (11)177
O1W—H2W···O4ii0.841.852.649 (12)159
O2W—H3W···O1W0.842.162.888 (9)145
O2W—H4W···O10.842.002.811 (11)162
O3W—H5W···O2i0.842.112.810 (12)140
O3W—H6W···O2Wiii0.842.292.766 (14)117
N2—H2···O2Wiv0.862.182.970 (16)152
Symmetry codes: (i) x+1, y, z; (ii) −x, −y, −z+1; (iii) −x+1, −y, −z+2; (iv) x, y+1, z.
Acknowledgements top

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

references
References top

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