supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers buy article online

hy2099 scheme

Acta Cryst. (2007). E63, m2981    [ doi:10.1107/S1600536807056188 ]

Di-[mu]-chlorido-bis{chlorido[2-(2-pyridyl)-1H-benzimidazole]cadmium(II)}

C.-K. Xia, W. Wu, L.-Y. Huang and J.-M. Xie

Abstract top

The title compound, [Cd2Cl4(C12H9N3)2], was prepared under hydrothermal conditions. In the centrosymmetric dimeric molecule, two CdII atoms are bridged by two Cl atoms. One terminal Cl atom and two N atoms from a bidentate chelating 2-(2-pyridyl)benzimidazole ligand complete a distorted square-pyramidal geometry around each CdII atom. A three-dimensional network is constructed via intermolecular N-H...Cl and weak C-H...Cl hydrogen bonds, as well as [pi]-[pi] interactions between adjacent ligands with a centroid-to-centroid distance of 3.49 (1) Å between the benzimidazolyl and pyridyl groups and a centroid-to-centroid distance of 3.54 (1) Å between the imidazolyl rings.

Comment top

The 2-(2-pyridyl)benzimidazole ligand is often used to act as bidentate chelating ligand in metal complexes and those complexes can be mononuclear (Muller-Buschbaum & Quitmann, 2003), dinuclear (Dave & Czernuszewicz, 1994) or trinuclear (Tangoulis et al., 1996). The noncoordinating N—H group of the ligand acts as hydrogen bond donor for the formation of robust heteromeric hydrogen bonds, contributing to the crystal packing. Herein we report the synthesis and structure of the title compound with the 2-(2-pyridyl)benzimidazole ligand.

The title compound is a centrosymmetric dimeric complex. The CdII atom is five-coordinated in an N2Cl3 environment with a distorted square-pyramidal geometry (Fig. 1). Two CdII atoms are bridged by two Cl atoms, forming a coplanar Cd2Cl2 unit. The coordination geometry is completed by one terminal Cl atom and two N atoms from the chelating 2-(2-pyridyl)benzimidazole ligand (Table 1). Intermolecular N—H···Cl and C—H···Cl hydrogen bonds, as well as π–π interactions between the pyridyl and benzimidazole groups of two adjacent dinuclear units, with a centroid-to-centroid distance of 3.49 (1) Å, lead to a one-dimensional chain (Fig. 2). The individual chains are associated with each other through π–π interactions between the imidazole rings of the neighboring chains, with a centroid-to-centroid distance of 3.54 (1) Å, forming a two-dimensional layer structure. The layers are further connected into a three-dimensional network through weak C—H···Cl interactions [H2A···Cl2i = 2.92 Å, C2···Cl2i = 3.600 (2) Å, C2—H2A···Cl2i = 131°; symmetry code: (i) x, y − 1, z](Fig. 3).

Related literature top

For related literature, see: Alcade et al. (1992); Dave & Czernuszewicz (1994); Muller-Buschbaum & Quitmann (2003); Tangoulis et al. (1996).

Experimental top

A solution of CdCl2·2.5H2O (0.14 g, 0.61 mmol), 2-(2-pyridyl)benzimidazole (0.08 g, 0.41 mmol) (Alcade et al., 1992) and H2O (15 ml) was stirred under ambient condition, then sealed in a 25 ml Teflon-lined stainless steel vessel, heated at 383 K for 3 d and cooled to room temperature. The resulting product was collected by filtration, washed with distilled water and dried in air (yield 80%).

Refinement top

H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93 and N—H = 0.86Å and Uiso(H) = 1.2Ueq(C, N).

Computing details top

Data collection: CrystalClear (Rigaku, 2002); cell refinement: CrystalClear (Rigaku, 2002); data reduction: CrystalClear (Rigaku, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1994); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry code: (i) 1 − x, 1 − y, 1 − z.]
[Figure 2] Fig. 2. A view of the one-dimensional chain in the title compound. H atoms have been omitted for clarity. Hydrogen bonds are shown as dashed lines.
[Figure 3] Fig. 3. The crystal packing of the title compound. Hydrogen bonds are shown as dashed lines.
Di-µ-chlorido-bis[chlorido[2-(2-pyridyl)-1H-benzimidazole]cadmium(II)] top
Crystal data top
[Cd2Cl4(C12H9N3)2]Z = 1
Mr = 757.04F000 = 368
Triclinic, P1Dx = 2.032 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 7.852 (2) ÅCell parameters from 1784 reflections
b = 8.971 (2) Åθ = 3.2–27.5º
c = 9.466 (3) ŵ = 2.18 mm−1
α = 103.224 (1)ºT = 293 (2) K
β = 101.050 (2)ºPrism, colorless
γ = 100.665 (4)º0.40 × 0.25 × 0.15 mm
V = 618.5 (3) Å3
Data collection top
Rigaku Mercury CCD
diffractometer		2765 independent reflections
Radiation source: fine-focus sealed tube2646 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.015
T = 293(2) Kθmax = 27.5º
ω scanθmin = 3.2º
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2002)		h = −10→7
Tmin = 0.525, Tmax = 0.718k = −11→11
4683 measured reflectionsl = −12→11
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.023H-atom parameters constrained
wR(F2) = 0.062  w = 1/[σ2(Fo2) + (0.0411P)2 + 0.1317P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.002
2765 reflectionsΔρmax = 0.48 e Å−3
163 parametersΔρmin = −1.04 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Cd2Cl4(C12H9N3)2]γ = 100.665 (4)º
Mr = 757.04V = 618.5 (3) Å3
Triclinic, P1Z = 1
a = 7.852 (2) ÅMo Kα
b = 8.971 (2) ŵ = 2.18 mm−1
c = 9.466 (3) ÅT = 293 (2) K
α = 103.224 (1)º0.40 × 0.25 × 0.15 mm
β = 101.050 (2)º
Data collection top
Rigaku Mercury CCD
diffractometer		2765 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2002)		2646 reflections with I > 2σ(I)
Tmin = 0.525, Tmax = 0.718Rint = 0.015
4683 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.023163 parameters
wR(F2) = 0.062H-atom parameters constrained
S = 1.05Δρmax = 0.48 e Å−3
2765 reflectionsΔρmin = −1.04 e Å−3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cd10.702580 (19)0.513530 (16)0.653164 (14)0.02650 (7)
Cl10.46761 (8)0.67515 (7)0.60517 (6)0.03671 (13)
Cl20.99264 (7)0.68125 (6)0.66049 (6)0.03132 (12)
C10.8247 (3)0.1778 (3)0.6348 (2)0.0313 (4)
H1A0.81540.17610.53500.038*
C20.8710 (3)0.0522 (3)0.6827 (3)0.0343 (5)
H2A0.8920−0.03220.61610.041*
C30.8851 (3)0.0548 (3)0.8302 (3)0.0338 (5)
H3A0.9153−0.02830.86460.041*
C40.8540 (3)0.1826 (3)0.9277 (2)0.0305 (4)
H4A0.86350.18701.02810.037*
C50.8084 (3)0.3032 (2)0.8712 (2)0.0226 (4)
C60.7681 (3)0.4433 (2)0.9627 (2)0.0219 (4)
C70.7286 (3)0.6161 (2)1.1522 (2)0.0247 (4)
C80.7131 (3)0.7043 (3)1.2898 (2)0.0321 (4)
H8A0.73990.67261.37680.039*
C90.6561 (3)0.8398 (3)1.2894 (3)0.0367 (5)
H9A0.64230.90071.37830.044*
C100.6179 (3)0.8898 (3)1.1581 (3)0.0358 (5)
H10A0.58260.98391.16320.043*
C110.6318 (3)0.8019 (3)1.0226 (3)0.0311 (4)
H11A0.60530.83410.93600.037*
C120.6873 (3)0.6625 (2)1.0208 (2)0.0239 (4)
N10.7931 (2)0.3006 (2)0.72678 (19)0.0250 (3)
N20.7126 (2)0.55058 (19)0.90301 (18)0.0237 (3)
N30.7801 (2)0.4761 (2)1.11117 (19)0.0250 (3)
H3B0.81340.42051.16940.030*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd10.02836 (11)0.03118 (10)0.02066 (10)0.00903 (7)0.00083 (7)0.01128 (7)
Cl10.0397 (3)0.0401 (3)0.0265 (3)0.0207 (2)−0.0043 (2)0.0030 (2)
Cl20.0294 (3)0.0367 (3)0.0305 (3)0.0082 (2)0.0051 (2)0.0162 (2)
C10.0372 (12)0.0334 (10)0.0232 (10)0.0104 (9)0.0057 (9)0.0074 (8)
C20.0384 (12)0.0284 (10)0.0327 (11)0.0120 (9)0.0038 (9)0.0028 (9)
C30.0371 (12)0.0297 (10)0.0356 (12)0.0138 (9)0.0019 (9)0.0123 (9)
C40.0363 (11)0.0319 (10)0.0242 (10)0.0113 (9)0.0022 (8)0.0115 (8)
C50.0192 (9)0.0256 (9)0.0223 (9)0.0050 (7)0.0014 (7)0.0084 (7)
C60.0179 (8)0.0261 (9)0.0212 (9)0.0049 (7)0.0010 (7)0.0089 (7)
C70.0201 (9)0.0286 (9)0.0231 (9)0.0034 (7)0.0022 (7)0.0073 (8)
C80.0308 (11)0.0391 (11)0.0216 (10)0.0040 (9)0.0031 (8)0.0051 (8)
C90.0337 (12)0.0399 (12)0.0292 (11)0.0073 (10)0.0063 (9)−0.0022 (9)
C100.0332 (12)0.0334 (11)0.0384 (12)0.0143 (9)0.0048 (10)0.0034 (9)
C110.0294 (11)0.0333 (10)0.0329 (11)0.0124 (9)0.0045 (9)0.0121 (9)
C120.0204 (9)0.0274 (9)0.0221 (9)0.0045 (7)0.0028 (7)0.0062 (7)
N10.0270 (9)0.0257 (8)0.0219 (8)0.0059 (7)0.0032 (7)0.0081 (6)
N20.0241 (8)0.0286 (8)0.0203 (8)0.0091 (7)0.0038 (6)0.0096 (6)
N30.0267 (9)0.0279 (8)0.0205 (8)0.0068 (7)0.0013 (6)0.0101 (6)
Geometric parameters (Å, °) top
Cd1—N22.2956 (17)C6—N21.321 (2)
Cd1—N12.3581 (17)C6—N31.350 (3)
Cd1—Cl22.4657 (8)C7—N31.385 (3)
Cd1—Cl12.5852 (7)C7—C121.399 (3)
Cd1—Cl1i2.5782 (7)C7—C81.401 (3)
C1—N11.334 (3)C8—C91.371 (3)
C1—C21.389 (3)C8—H8A0.9300
C1—H1A0.9300C9—C101.413 (4)
C2—C31.374 (3)C9—H9A0.9300
C2—H2A0.9300C10—C111.379 (3)
C3—C41.390 (3)C10—H10A0.9300
C3—H3A0.9300C11—C121.396 (3)
C4—C51.385 (3)C11—H11A0.9300
C4—Cl2ii3.690 (2)C12—N21.392 (3)
C4—H4A0.9300N3—Cl2ii3.2708 (18)
C5—N11.344 (3)N3—H3B0.8600
C5—C61.477 (3)
N2—Cd1—N171.68 (6)N3—C6—C5125.53 (17)
N2—Cd1—Cl2101.94 (5)N3—C7—C12105.75 (17)
N1—Cd1—Cl2101.14 (5)N3—C7—C8132.14 (19)
N2—Cd1—Cl1i141.01 (5)C12—C7—C8122.10 (19)
N1—Cd1—Cl1i89.60 (5)C9—C8—C7116.4 (2)
Cl2—Cd1—Cl1i115.34 (2)C9—C8—H8A121.8
N2—Cd1—Cl195.34 (4)C7—C8—H8A121.8
N1—Cd1—Cl1151.59 (5)C8—C9—C10122.1 (2)
Cl2—Cd1—Cl1106.34 (3)C8—C9—H9A119.0
Cl1i—Cd1—Cl185.21 (2)C10—C9—H9A119.0
Cd1i—Cl1—Cd194.79 (2)C11—C10—C9121.3 (2)
N1—C1—C2122.4 (2)C11—C10—H10A119.3
N1—C1—H1A118.8C9—C10—H10A119.3
C2—C1—H1A118.8C10—C11—C12117.3 (2)
C3—C2—C1118.7 (2)C10—C11—H11A121.3
C3—C2—H2A120.6C12—C11—H11A121.3
C1—C2—H2A120.6N2—C12—C11130.41 (19)
C2—C3—C4119.5 (2)N2—C12—C7108.79 (17)
C2—C3—H3A120.2C11—C12—C7120.80 (19)
C4—C3—H3A120.2C1—N1—C5118.60 (17)
C5—C4—C3118.2 (2)C1—N1—Cd1124.66 (14)
C5—C4—Cl2ii110.35 (14)C5—N1—Cd1116.71 (13)
C3—C4—Cl2ii128.49 (14)C6—N2—C12105.63 (16)
C5—C4—H4A120.9C6—N2—Cd1115.58 (13)
C3—C4—H4A120.9C12—N2—Cd1138.63 (13)
N1—C5—C4122.49 (19)C6—N3—C7107.08 (16)
N1—C5—C6114.19 (16)C6—N3—Cl2ii124.62 (12)
C4—C5—C6123.30 (18)C7—N3—Cl2ii125.61 (12)
N2—C6—N3112.74 (17)C6—N3—H3B126.5
N2—C6—C5121.72 (17)C7—N3—H3B126.5
N2—Cd1—Cl1—Cd1i−140.85 (5)N2—Cd1—N1—C1177.38 (19)
N1—Cd1—Cl1—Cd1i−80.23 (9)Cl2—Cd1—N1—C1−83.59 (18)
Cl2—Cd1—Cl1—Cd1i115.02 (2)Cl1i—Cd1—N1—C132.19 (17)
Cl1i—Cd1—Cl1—Cd1i0.0Cl1—Cd1—N1—C1111.32 (17)
N1—C1—C2—C3−0.1 (4)N2—Cd1—N1—C5−0.68 (14)
C1—C2—C3—C4−0.4 (4)Cl2—Cd1—N1—C598.35 (14)
C2—C3—C4—C50.4 (4)Cl1i—Cd1—N1—C5−145.87 (14)
C2—C3—C4—Cl2ii−158.16 (17)Cl1—Cd1—N1—C5−66.74 (18)
C3—C4—C5—N10.1 (3)N3—C6—N2—C120.4 (2)
Cl2ii—C4—C5—N1162.33 (15)C5—C6—N2—C12179.52 (18)
C3—C4—C5—C6178.6 (2)N3—C6—N2—Cd1176.70 (13)
Cl2ii—C4—C5—C6−19.2 (2)C5—C6—N2—Cd1−4.2 (2)
N1—C5—C6—N23.5 (3)C11—C12—N2—C6179.2 (2)
C4—C5—C6—N2−175.0 (2)C7—C12—N2—C6−0.5 (2)
N1—C5—C6—N3−177.46 (19)C11—C12—N2—Cd14.2 (4)
C4—C5—C6—N34.0 (3)C7—C12—N2—Cd1−175.48 (15)
N3—C7—C8—C9−179.7 (2)N1—Cd1—N2—C62.49 (14)
C12—C7—C8—C9−0.4 (3)Cl2—Cd1—N2—C6−95.44 (14)
C7—C8—C9—C10−1.0 (4)Cl1i—Cd1—N2—C667.61 (16)
C8—C9—C10—C111.7 (4)Cl1—Cd1—N2—C6156.59 (14)
C9—C10—C11—C12−0.7 (4)N1—Cd1—N2—C12177.1 (2)
C10—C11—C12—N2179.6 (2)Cl2—Cd1—N2—C1279.2 (2)
C10—C11—C12—C7−0.7 (3)Cl1i—Cd1—N2—C12−117.76 (19)
N3—C7—C12—N20.5 (2)Cl1—Cd1—N2—C12−28.8 (2)
C8—C7—C12—N2−178.94 (19)N2—C6—N3—C7−0.1 (2)
N3—C7—C12—C11−179.27 (19)C5—C6—N3—C7−179.20 (18)
C8—C7—C12—C111.3 (3)N2—C6—N3—Cl2ii−162.33 (12)
C2—C1—N1—C50.6 (3)C5—C6—N3—Cl2ii18.6 (3)
C2—C1—N1—Cd1−177.40 (18)C12—C7—N3—C6−0.2 (2)
C4—C5—N1—C1−0.6 (3)C8—C7—N3—C6179.1 (2)
C6—C5—N1—C1−179.19 (19)C12—C7—N3—Cl2ii161.78 (12)
C4—C5—N1—Cd1177.57 (16)C8—C7—N3—Cl2ii−18.9 (3)
C6—C5—N1—Cd1−1.0 (2)
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y+1, −z+2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3B···Cl2ii0.862.453.2708 (18)160
C4—H4A···Cl2ii0.932.833.690 (2)155
Symmetry codes: (ii) −x+2, −y+1, −z+2.
Table 1
Selected geometric parameters (Å, °) top
Cd1—N22.2956 (17)Cd1—Cl12.5852 (7)
Cd1—N12.3581 (17)Cd1—Cl1i2.5782 (7)
Cd1—Cl22.4657 (8)
N2—Cd1—N171.68 (6)Cl2—Cd1—Cl1i115.34 (2)
N2—Cd1—Cl2101.94 (5)N2—Cd1—Cl195.34 (4)
N1—Cd1—Cl2101.14 (5)N1—Cd1—Cl1151.59 (5)
N2—Cd1—Cl1i141.01 (5)Cl2—Cd1—Cl1106.34 (3)
N1—Cd1—Cl1i89.60 (5)Cl1i—Cd1—Cl185.21 (2)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3B···Cl2ii0.862.453.2708 (18)160
C4—H4A···Cl2ii0.932.833.690 (2)155
Symmetry codes: (ii) −x+2, −y+1, −z+2.
Acknowledgements top

We thank the Social Development Foundation of Jiangsu Province, China (grant No. BS2006038) and the Social Development Foundation of Zhenjiang, Jiangsu Province, China (grant No. SH2006057) for financial support.

references
References top

Alcade, E., Dinares, I., Perez-Garia, L. & Roca, T. (1992). Synthesis, pp. 295–398.

Dave, B. C. & Czernuszewicz, R. S. (1994). Inorg. Chim. Acta, 227, 33–41.

Muller-Buschbaum, K. & Quitmann, C. C. (2003). Inorg. Chem. 42, 2742–2750.

Rigaku (2002). CrystalClear. Version 1.35. Rigaku Corporation, Tokyo, Japan.

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

Siemens (1994). SHELXTL. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Tangoulis, V., Malamatari, D. A., Soulti, K., Stergiou, V., Raptopoulou, C. P., Terzis, A., Kabanos, T. A. & Kessissoglou, D. P. (1996). Inorg. Chem. 35, 4974–4983.