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Acta Cryst. (2007). E63, m2927    [ doi:10.1107/S1600536807054888 ]

Tris(2,2'-bi-1H-imidazole)cadmium(II) carbonate

M. Cao, B. Hu, F. Luo, C. Cheng and Z. Hu

Abstract top

The title compound, [Cd(C6H6N4)3]CO3, is composed of discrete cations and anions, which are each located on a twofold rotation axis. The central CdII ion exhibits a distorted octahedral geometry and is coordinated by six N atoms from three 2,2'-biimidazole molecules. The crystal packing is stabilized by N-H...O hydrogen bonds.

Comment top

There has been increasing interest in the recent years for the coordinating ability of 2,2'-biimidazole (H2biim) (Xia et al., 2006; Kamar et al., 2004). It is a bidentate chelating ligand with multiple proton-donor sites which can coordinate to a transition metal in its neutral (H2biim), singly-deprotonated (Hbiim−) and doubly-deprotonated (biim2−) forms. Furthermore, the uncoordinated N atoms, which may be protonated or not, can participate in various patterns of hydrogen bonds with other components of the structure, leading to a broad variety of crystalline structures.

Here, we report the synthesis and crystal structure of the title compound, consisting of [Cd(H2biim)3]2+ complex cations with CO32− acting as counter anions. The central CdII ion of the title compound exhibits a distorted octahedral geometry. It is coordinated to six N atoms from three 2,2'-biimidazole ligands.

The crystal packing is stabilized by N—H···O hydrogen bonds.

Related literature top

For related literature, see: Kamar et al. (2004); Xia et al. (2006); Xiao & Shreeve (2005).

Experimental top

2,2'-biimidazole was synthesized according to the literature procedure (Xiao & Shreeve, 2005). A mixture of Cd(CO3)2, 2,2'-biimidazole in 1:1 molar ratio with 10 ml water was sealed into a Teflon-lined pressure vessel and heated at 433 K for 72 h. After the mixture cooled to room temperature, yellow crystals were formed, coolected by filtration, washed in deionized water, and finally dried in air.

Refinement top

After having located them in a difference map, all H-atoms were fixed geometrically at ideal positions. They were allowed to ride on their parent atoms with C–H=0.93 Å and N–H=0.86 Å with Uiso(H)=1.2Ueq(C,N).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SMART (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL (Bruker, 2001).

Figures top
[Figure 1] Fig. 1. View of the molecular structure of the title compound, showing 50% probability displacement ellipsoids for the non-hydrogen atoms. [Symmetry codes:(a) 1 − x, 1 − y, z;(b) 1 − x, 1 − y, z]
[Figure 2] Fig. 2. Packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.
Tris(2,2'-bi-1H-imidazole)cadmium(II) carbonate top
Crystal data top
[Cd(C6H6N4)3]CO3Z = 4
Mr = 574.85F000 = 1152
Tetragonal, I41Dx = 1.699 Mg m−3
Hall symbol: I 4bwMo Kα radiation
λ = 0.71073 Å
a = 12.3477 (8) ÅCell parameters from 3277 reflections
b = 12.3477 (8) Åθ = 3.3–26.2º
c = 14.7379 (10) ŵ = 1.02 mm−1
α = 90ºT = 300 (2) K
β = 90ºBlock, yellow
γ = 90º0.30 × 0.20 × 0.20 mm
V = 2247.0 (3) Å3
Data collection top
Bruker SMART CCD area-detector
diffractometer		1936 independent reflections
Radiation source: fine-focus sealed tube1761 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.071
T = 300(2) Kθmax = 27.0º
phi and ω scansθmin = 2.2º
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		h = −15→15
Tmin = 0.749, Tmax = 0.822k = −15→15
6885 measured reflectionsl = −18→12
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.043  w = 1/[σ2(Fo2) + (0.0486P)2 + 13.566P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.132(Δ/σ)max < 0.001
S = 1.17Δρmax = 0.47 e Å−3
1936 reflectionsΔρmin = −0.45 e Å−3
160 parametersExtinction correction: none
1 restraintAbsolute structure: Flack (1983), 654 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: −0.15 (6)
Secondary atom site location: difference Fourier map
Crystal data top
[Cd(C6H6N4)3]CO3γ = 90º
Mr = 574.85V = 2247.0 (3) Å3
Tetragonal, I41Z = 4
a = 12.3477 (8) ÅMo Kα
b = 12.3477 (8) ŵ = 1.02 mm−1
c = 14.7379 (10) ÅT = 300 (2) K
α = 90º0.30 × 0.20 × 0.20 mm
β = 90º
Data collection top
Bruker SMART CCD area-detector
diffractometer		1936 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		1761 reflections with I > 2σ(I)
Tmin = 0.749, Tmax = 0.822Rint = 0.071
6885 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.043H-atom parameters constrained
wR(F2) = 0.132  w = 1/[σ2(Fo2) + (0.0486P)2 + 13.566P]
where P = (Fo2 + 2Fc2)/3
S = 1.17Δρmax = 0.47 e Å−3
1936 reflectionsΔρmin = −0.45 e Å−3
160 parametersAbsolute structure: Flack (1983), 654 Friedel pairs
1 restraintFlack parameter: −0.15 (6)
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.

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 > 2sigma(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) top
xyzUiso*/Ueq
Cd10.50000.50000.62805 (5)0.0349 (2)
C10.2725 (6)0.5529 (6)0.7110 (6)0.0338 (16)
C20.1821 (8)0.6941 (7)0.6645 (7)0.048 (2)
H20.12730.74450.65480.058*
C30.2828 (6)0.6956 (7)0.6299 (8)0.051 (2)
H30.30990.74960.59230.061*
C40.3048 (5)0.4522 (6)0.7546 (5)0.0307 (15)
C50.3097 (8)0.3090 (8)0.8389 (8)0.050 (2)
H50.29360.25680.88240.060*
C60.3972 (8)0.3106 (7)0.7806 (7)0.045 (2)
H60.45080.25780.77790.054*
C70.5318 (8)0.7177 (7)0.4728 (7)0.052 (2)
H70.54190.77520.51260.062*
C80.5272 (7)0.7257 (6)0.3827 (8)0.047 (2)
H80.53310.78910.34910.057*
C90.5070 (6)0.5591 (6)0.4221 (6)0.0349 (17)
N10.1769 (5)0.6027 (5)0.7172 (5)0.0363 (15)
H10.12210.58140.74850.044*
N20.3394 (5)0.6073 (5)0.6574 (5)0.0402 (16)
N30.2529 (5)0.3988 (5)0.8194 (5)0.0376 (15)
H3A0.19320.41820.84460.045*
N40.3932 (5)0.4014 (5)0.7273 (5)0.0378 (15)
N50.5194 (6)0.6120 (6)0.4973 (5)0.0393 (16)
N60.5124 (6)0.6240 (6)0.3486 (5)0.0420 (16)
H6A0.50760.60540.29250.050*
C110.50000.50000.1353 (17)0.030 (3)
O10.4868 (5)0.4101 (4)0.1714 (4)0.0392 (12)
O20.50000.50000.0415 (6)0.047 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd10.0302 (5)0.0455 (6)0.0290 (4)−0.0016 (5)0.0000.000
C10.027 (4)0.044 (4)0.030 (4)−0.001 (3)−0.001 (3)−0.001 (3)
C20.055 (5)0.045 (5)0.045 (5)0.007 (4)−0.008 (4)0.013 (4)
C30.041 (4)0.058 (5)0.054 (6)0.007 (4)−0.004 (5)0.028 (5)
C40.025 (3)0.037 (4)0.030 (4)−0.004 (3)0.002 (3)0.001 (3)
C50.050 (5)0.049 (5)0.051 (6)0.001 (4)0.000 (4)0.019 (4)
C60.048 (5)0.039 (4)0.048 (6)0.011 (4)−0.005 (4)0.009 (4)
C70.067 (6)0.041 (5)0.048 (6)−0.012 (4)−0.006 (5)−0.011 (4)
C80.065 (5)0.026 (3)0.051 (6)−0.004 (3)0.016 (5)0.004 (4)
C90.034 (4)0.036 (4)0.035 (4)−0.003 (3)−0.005 (3)0.004 (3)
N10.030 (3)0.046 (4)0.033 (4)0.004 (3)0.008 (3)0.005 (3)
N20.043 (4)0.038 (3)0.040 (4)0.001 (3)0.008 (3)0.011 (3)
N30.033 (3)0.040 (4)0.040 (4)0.004 (3)0.001 (3)0.011 (3)
N40.026 (3)0.045 (4)0.043 (4)0.003 (3)−0.004 (3)0.006 (3)
N50.048 (4)0.042 (4)0.028 (4)−0.007 (3)0.011 (3)−0.005 (3)
N60.053 (4)0.041 (4)0.031 (4)−0.004 (3)−0.002 (3)0.004 (3)
C110.036 (6)0.038 (7)0.016 (8)−0.002 (6)0.0000.000
O10.052 (3)0.033 (3)0.033 (3)−0.002 (2)−0.002 (3)0.005 (2)
O20.071 (6)0.032 (4)0.037 (5)0.009 (4)0.0000.000
Geometric parameters (Å, °) top
Cd1—N42.315 (7)C5—H50.9300
Cd1—N4i2.315 (7)C6—N41.370 (11)
Cd1—N5i2.383 (7)C6—H60.9300
Cd1—N52.383 (7)C7—C81.333 (14)
Cd1—N22.424 (7)C7—N51.364 (11)
Cd1—N2i2.424 (7)C7—H70.9300
C1—N21.326 (10)C8—N61.364 (11)
C1—N11.334 (10)C8—H80.9300
C1—C41.455 (11)C9—N51.296 (11)
C2—C31.344 (13)C9—N61.349 (11)
C2—N11.372 (11)C9—C9i1.469 (16)
C2—H20.9300N1—H10.8600
C3—N21.357 (10)N3—H3A0.8600
C3—H30.9300N6—H6A0.8600
C4—N41.323 (10)C11—O1i1.242 (12)
C4—N31.326 (10)C11—O11.242 (12)
C5—N31.343 (11)C11—O21.38 (3)
C5—C61.380 (14)
N4—Cd1—N4i101.6 (4)C5—C6—H6125.0
N4—Cd1—N5i98.5 (2)C8—C7—N5109.3 (8)
N4i—Cd1—N5i150.8 (2)C8—C7—H7125.4
N4—Cd1—N5150.8 (2)N5—C7—H7125.4
N4i—Cd1—N598.5 (2)C7—C8—N6107.7 (8)
N5i—Cd1—N572.1 (3)C7—C8—H8126.1
N4—Cd1—N273.1 (2)N6—C8—H8126.1
N4i—Cd1—N293.8 (2)N5—C9—N6112.5 (7)
N5i—Cd1—N2112.3 (2)N5—C9—C9i120.9 (5)
N5—Cd1—N284.8 (2)N6—C9—C9i126.6 (5)
N4—Cd1—N2i93.8 (2)C1—N1—C2107.4 (7)
N4i—Cd1—N2i73.1 (2)C1—N1—H1126.3
N5i—Cd1—N2i84.8 (2)C2—N1—H1126.3
N5—Cd1—N2i112.3 (2)C1—N2—C3105.3 (7)
N2—Cd1—N2i159.5 (4)C1—N2—Cd1109.8 (5)
N2—C1—N1111.0 (7)C3—N2—Cd1143.8 (6)
N2—C1—C4121.7 (7)C4—N3—C5108.2 (7)
N1—C1—C4127.3 (7)C4—N3—H3A125.9
C3—C2—N1105.6 (8)C5—N3—H3A125.9
C3—C2—H2127.2C4—N4—C6104.1 (7)
N1—C2—H2127.2C4—N4—Cd1114.4 (5)
C2—C3—N2110.6 (8)C6—N4—Cd1140.6 (6)
C2—C3—H3124.7C9—N5—C7105.6 (7)
N2—C3—H3124.7C9—N5—Cd1112.8 (5)
N4—C4—N3112.4 (7)C7—N5—Cd1141.4 (6)
N4—C4—C1119.9 (7)C9—N6—C8104.9 (8)
N3—C4—C1127.6 (7)C9—N6—H6A127.5
N3—C5—C6105.3 (8)C8—N6—H6A127.5
N3—C5—H5127.3O1i—C11—O1129 (2)
C6—C5—H5127.3O1i—C11—O2115.4 (11)
N4—C6—C5109.9 (8)O1—C11—O2115.4 (11)
N4—C6—H6125.0
N1—C2—C3—N21.4 (12)C1—C4—N4—Cd110.2 (9)
N2—C1—C4—N4−13.9 (12)C5—C6—N4—C40.3 (10)
N1—C1—C4—N4165.8 (8)C5—C6—N4—Cd1167.6 (8)
N2—C1—C4—N3169.1 (8)N4i—Cd1—N4—C486.5 (6)
N1—C1—C4—N3−11.2 (14)N5i—Cd1—N4—C4−114.8 (6)
N3—C5—C6—N40.6 (12)N5—Cd1—N4—C4−46.3 (9)
N5—C7—C8—N6−0.4 (11)N2—Cd1—N4—C4−4.0 (6)
N2—C1—N1—C20.3 (10)N2i—Cd1—N4—C4159.9 (6)
C4—C1—N1—C2−179.5 (8)N4i—Cd1—N4—C6−80.0 (10)
C3—C2—N1—C1−1.0 (11)N5i—Cd1—N4—C678.7 (10)
N1—C1—N2—C30.6 (10)N5—Cd1—N4—C6147.2 (9)
C4—C1—N2—C3−179.7 (8)N2—Cd1—N4—C6−170.4 (10)
N1—C1—N2—Cd1−170.7 (5)N2i—Cd1—N4—C6−6.5 (10)
C4—C1—N2—Cd19.1 (9)N6—C9—N5—C71.0 (10)
C2—C3—N2—C1−1.3 (11)C9i—C9—N5—C7179.0 (9)
C2—C3—N2—Cd1164.7 (8)N6—C9—N5—Cd1176.7 (5)
N4—Cd1—N2—C1−2.7 (5)C9i—C9—N5—Cd1−5.3 (11)
N4i—Cd1—N2—C1−103.7 (6)C8—C7—N5—C9−0.4 (11)
N5i—Cd1—N2—C189.8 (6)C8—C7—N5—Cd1−174.0 (7)
N5—Cd1—N2—C1158.0 (6)N4—Cd1—N5—C9−73.2 (7)
N2i—Cd1—N2—C1−54.7 (5)N4i—Cd1—N5—C9153.4 (5)
N4—Cd1—N2—C3−168.3 (11)N5i—Cd1—N5—C91.9 (4)
N4i—Cd1—N2—C390.6 (11)N2—Cd1—N5—C9−113.6 (6)
N5i—Cd1—N2—C3−75.9 (11)N2i—Cd1—N5—C978.3 (6)
N5—Cd1—N2—C3−7.6 (11)N4—Cd1—N5—C7100.1 (10)
N2i—Cd1—N2—C3139.7 (11)N4i—Cd1—N5—C7−33.2 (10)
N4—C4—N3—C51.6 (10)N5i—Cd1—N5—C7175.2 (11)
C1—C4—N3—C5178.8 (8)N2—Cd1—N5—C759.8 (10)
C6—C5—N3—C4−1.3 (11)N2i—Cd1—N5—C7−108.4 (10)
N3—C4—N4—C6−1.2 (9)N5—C9—N6—C8−1.3 (9)
C1—C4—N4—C6−178.6 (7)C9i—C9—N6—C8−179.1 (9)
N3—C4—N4—Cd1−172.4 (5)C7—C8—N6—C91.0 (10)
Symmetry codes: (i) −x+1, −y+1, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3A···O1ii0.861.902.737 (9)163
N1—H1···O2iii0.861.922.753 (8)163
N6—H6A···O1i0.861.802.644 (9)169
Symmetry codes: (ii) −y+1/2, x, z+3/4; (iii) y−1/2, −x+1, z+3/4; (i) −x+1, −y+1, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3A···O1i0.861.902.737 (9)163
N1—H1···O2ii0.861.922.753 (8)163
N6—H6A···O1iii0.861.802.644 (9)169
Symmetry codes: (i) −y+1/2, x, z+3/4; (ii) y−1/2, −x+1, z+3/4; (iii) −x+1, −y+1, z.
Acknowledgements top

We thank Xianggao Meng for assistance with testing and refining the structure of the compound.

references
References top

Bruker (2001). SMART, SAINT, SADABS and SHELXTL. Bruker AXS, Inc., Madison, Wisconsin, USA.

Flack, H. D. (1983). Acta Cryst. A39, 876–881.

Kamar, K. K., Falvello, L. R., Fanwick, P. E., Kim, J. & Goswami, S. (2004). Dalton Trans. pp. 1827–1831.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Xia, C.-K., Lu, C.-Z., Yuan, D.-Q., Zhang, Q.-Z., Wu, X.-Y., Xiang, S.-C., Zhang, J.-J. & Wu, D.-M. (2006). CrystEngComm, 8, 281–291.

Xiao, J.-C. & Shreeve, J. M. (2005). J. Org. Chem. 70, 3072–3078.