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Acta Crystallogr Sect E Struct Rep Online. 2009 January 1; 65(Pt 1): m37.
Published online 2008 December 10. doi:  10.1107/S1600536808040968
PMCID: PMC2967883

Di-μ-chlorido-bis­[(2,2′-bibenzimidazole)chloridocadmium(II)]

Abstract

The title binuclear complex, [Cd2Cl4(C14H10N4)2], was synthesized by the hydro­thermal reaction of CdCl2 and the ligand 2,2′-bibenzimidazole. The mol­ecule lies on an inversion center and the metal center displays a strongly distorted trigonal-bipyramidal geometry. The CdII ions are coordinated by two N atoms from the organic ligand, and by one terminal and two bridging chloride anions. The crystal structure involves inter­molecular N—H(...)Cl hydrogen bonds, resulting in a one-dimensional supra­molecular structure.

Related literature

For the synthesis of 2,2′-bibenzimidazole, see: Fieselmann et al. (1978 [triangle]). For general properties of CdII-based complex polymers, see: Meng et al. (2004 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-00m37-scheme1.jpg

Experimental

Crystal data

  • [Cd2Cl4(C14H10N4)2]
  • M r = 835.12
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-00m37-efi1.jpg
  • a = 11.824 (2) Å
  • b = 10.784 (2) Å
  • c = 22.828 (5) Å
  • β = 91.10 (3)°
  • V = 2910.1 (10) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 1.86 mm−1
  • T = 293 (2) K
  • 0.17 × 0.16 × 0.12 mm

Data collection

  • Rigaku R-AXIS RAPID-S diffractometer
  • Absorption correction: none
  • 14677 measured reflections
  • 3337 independent reflections
  • 2840 reflections with I > 2σ(I)
  • R int = 0.035

Refinement

  • R[F 2 > 2σ(F 2)] = 0.033
  • wR(F 2) = 0.060
  • S = 1.14
  • 3337 reflections
  • 190 parameters
  • H-atom parameters constrained
  • Δρmax = 0.29 e Å−3
  • Δρmin = −0.34 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: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

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

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808040968/bh2211sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808040968/bh2211Isup2.hkl

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

Acknowledgments

The author thanks Chifeng University for supporting this work.

supplementary crystallographic information

Comment

Bibenzimidazole has the potential to function as a bis-bidentate nitrogen ligand by coordinating to metal ions as a chelate. On the other hand, CdII-containing coordination polymers have attracted much attention as they are able to bond to different donors ligands simultaneously, because of the CdII large radius. Various coordination modes and potential applications in catalysis, fluorescent materials, NLO materials and so on (Meng et al. 2004) have been described. Here we report the crystal structure of the title complex prepared from CdCl2 and bibenzimidazole ligand (see experimental).

As show in Fig. 1, the complex lies on an inversion center, and Cd atoms have strongly distorted trigonal-bipyramidal geometry, being coordinated by two N atoms from the organic ligand, and by one terminal and two bridging Cl- anions. The two Cd centers are bridged by two chloride ions to give a dinuclear cadmium complex. Intermolecular N—H···Cl hydrogen bonds extend the dinuclear complex to a one dimensional chain in the crystal structure (Fig. 2).

Experimental

A mixture of CdCl2 (0.073 g, 0.40 mmol), bibenzimidazole (0.070 g, 0.30 mmol) and H2O (10 ml) was placed in a Teflon reactor, then heated to 433 K at 10.8 K/h; after maintaining the reaction at 433 K for three days, it was cooled to 303 K at 10.8 K/h. Crystals suitable for X-ray analysis were obtained.

Refinement

Raw diffraction data were used for refinement, since semi-empirical correction failed to properly correct absorption effects. All H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with N—H = 0.86 Å, C—H = 0.93 Å, and with Uiso(H) = 1.2Ueq(carrier atom).

Figures

Fig. 1.
The structure of the title compound with displacement ellipsoids at the 30% probability level.
Fig. 2.
One dimensional chain formed by hydrogen bonds (dashed lines) in the crystal structure of the title compound.

Crystal data

[Cd2Cl4(C14H10N4)2]F(000) = 1632
Mr = 835.12Dx = 1.906 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 13595 reflections
a = 11.824 (2) Åθ = 3.1–27.5°
b = 10.784 (2) ŵ = 1.86 mm1
c = 22.828 (5) ÅT = 293 K
β = 91.10 (3)°Prism, yellow
V = 2910.1 (10) Å30.17 × 0.16 × 0.12 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID-S diffractometer2840 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.035
graphiteθmax = 27.5°, θmin = 3.1°
ω scansh = −15→15
14677 measured reflectionsk = −14→14
3337 independent reflectionsl = −29→29

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)] = 0.033Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.060H-atom parameters constrained
S = 1.14w = 1/[σ2(Fo2) + (0.0213P)2 + 2.9529P] where P = (Fo2 + 2Fc2)/3
3337 reflections(Δ/σ)max = 0.002
190 parametersΔρmax = 0.29 e Å3
0 restraintsΔρmin = −0.34 e Å3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
C10.7642 (2)0.8420 (3)0.65287 (12)0.0352 (6)
C20.8455 (3)0.8628 (3)0.69666 (14)0.0488 (8)
H20.90960.91020.68960.059*
C30.8279 (3)0.8110 (3)0.75062 (15)0.0567 (9)
H30.88040.82520.78070.068*
C40.7338 (3)0.7380 (3)0.76151 (14)0.0569 (9)
H40.72520.70370.79850.068*
C50.6533 (3)0.7156 (3)0.71877 (13)0.0523 (9)
H50.59090.66580.72590.063*
C60.6688 (2)0.7699 (3)0.66449 (12)0.0370 (6)
C70.6614 (2)0.8380 (2)0.57409 (11)0.0314 (6)
C80.6263 (2)0.8657 (2)0.51432 (11)0.0314 (6)
C90.5301 (2)0.8803 (2)0.43105 (11)0.0319 (6)
C100.4514 (2)0.8770 (3)0.38526 (13)0.0409 (7)
H100.38170.83810.38890.049*
C110.4822 (3)0.9342 (3)0.33429 (13)0.0450 (7)
H110.43180.93430.30250.054*
C120.5875 (3)0.9926 (3)0.32871 (13)0.0441 (7)
H120.60501.03020.29340.053*
C130.6652 (2)0.9957 (2)0.37397 (12)0.0378 (6)
H130.73491.03430.37000.045*
C140.6356 (2)0.9386 (2)0.42626 (11)0.0306 (6)
Cd10.851704 (16)1.006362 (18)0.527622 (9)0.03487 (7)
Cl11.04814 (6)0.95042 (8)0.57022 (3)0.04315 (18)
Cl20.84050 (6)1.21444 (7)0.57132 (3)0.04270 (18)
N10.75762 (18)0.8824 (2)0.59515 (10)0.0343 (5)
N20.60522 (19)0.7697 (2)0.61309 (9)0.0386 (6)
H150.54160.73270.60720.046*
N30.52742 (18)0.8349 (2)0.48775 (9)0.0347 (5)
H160.47280.79460.50320.042*
N40.69432 (18)0.9280 (2)0.47931 (9)0.0324 (5)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0327 (15)0.0355 (15)0.0373 (15)0.0013 (11)0.0013 (12)0.0007 (12)
C20.0377 (17)0.058 (2)0.0510 (19)−0.0033 (15)−0.0065 (15)0.0030 (16)
C30.051 (2)0.071 (2)0.047 (2)0.0076 (18)−0.0105 (16)−0.0022 (18)
C40.058 (2)0.077 (3)0.0352 (18)0.0122 (19)0.0038 (16)0.0087 (17)
C50.0448 (19)0.067 (2)0.0455 (19)−0.0043 (16)0.0112 (15)0.0063 (16)
C60.0329 (15)0.0432 (17)0.0353 (15)0.0006 (12)0.0052 (12)−0.0024 (13)
C70.0283 (14)0.0314 (14)0.0348 (14)−0.0073 (11)0.0049 (11)−0.0026 (11)
C80.0276 (14)0.0320 (14)0.0348 (14)−0.0081 (11)0.0037 (11)−0.0045 (11)
C90.0307 (14)0.0312 (14)0.0338 (14)−0.0053 (11)0.0019 (11)−0.0052 (11)
C100.0329 (15)0.0450 (17)0.0446 (17)−0.0079 (13)−0.0029 (13)−0.0052 (14)
C110.0461 (18)0.0484 (18)0.0400 (17)−0.0064 (14)−0.0103 (14)−0.0030 (14)
C120.0552 (19)0.0410 (17)0.0363 (15)−0.0103 (14)0.0022 (14)0.0006 (13)
C130.0383 (15)0.0364 (15)0.0389 (15)−0.0119 (12)0.0071 (12)−0.0028 (13)
C140.0302 (14)0.0282 (13)0.0337 (14)−0.0057 (11)0.0044 (11)−0.0067 (11)
Cd10.02621 (11)0.03603 (12)0.04251 (12)−0.01089 (8)0.00477 (8)−0.00660 (10)
Cl10.0287 (3)0.0578 (4)0.0431 (4)−0.0050 (3)0.0039 (3)0.0038 (3)
Cl20.0364 (4)0.0389 (4)0.0533 (4)−0.0110 (3)0.0141 (3)−0.0121 (3)
N10.0256 (11)0.0377 (13)0.0396 (13)−0.0070 (9)0.0014 (10)0.0005 (10)
N20.0336 (13)0.0449 (14)0.0375 (13)−0.0157 (11)0.0039 (10)0.0001 (11)
N30.0265 (12)0.0396 (13)0.0380 (13)−0.0141 (10)0.0039 (10)−0.0025 (10)
N40.0288 (12)0.0355 (13)0.0330 (12)−0.0111 (10)0.0039 (9)−0.0015 (10)

Geometric parameters (Å, °)

C1—N11.389 (3)C9—C141.403 (3)
C1—C21.393 (4)C10—C111.373 (4)
C1—C61.399 (4)C10—H100.9300
C2—C31.372 (4)C11—C121.403 (4)
C2—H20.9300C11—H110.9300
C3—C41.389 (5)C12—C131.370 (4)
C3—H30.9300C12—H120.9300
C4—C51.371 (4)C13—C141.393 (4)
C4—H40.9300C13—H130.9300
C5—C61.386 (4)C14—N41.389 (3)
C5—H50.9300Cd1—N42.305 (2)
C6—N21.381 (3)Cd1—N12.338 (2)
C7—N11.317 (3)Cd1—Cl22.4602 (8)
C7—N21.341 (3)Cd1—Cl12.5725 (10)
C7—C81.450 (4)Cd1—Cl1i2.5903 (10)
C8—N41.327 (3)Cl1—Cd1i2.5903 (10)
C8—N31.348 (3)N2—H150.8600
C9—N31.385 (3)N3—H160.8600
C9—C101.387 (4)
N1—C1—C2131.0 (3)C13—C12—C11121.7 (3)
N1—C1—C6108.9 (2)C13—C12—H12119.1
C2—C1—C6120.1 (3)C11—C12—H12119.1
C3—C2—C1117.6 (3)C12—C13—C14117.4 (3)
C3—C2—H2121.2C12—C13—H13121.3
C1—C2—H2121.2C14—C13—H13121.3
C2—C3—C4121.8 (3)N4—C14—C13130.9 (2)
C2—C3—H3119.1N4—C14—C9109.0 (2)
C4—C3—H3119.1C13—C14—C9120.2 (3)
C5—C4—C3121.3 (3)N4—Cd1—N173.49 (8)
C5—C4—H4119.3N4—Cd1—Cl2118.63 (6)
C3—C4—H4119.3N1—Cd1—Cl2102.95 (6)
C4—C5—C6117.4 (3)N4—Cd1—Cl1144.04 (6)
C4—C5—H5121.3N1—Cd1—Cl193.11 (6)
C6—C5—H5121.3Cl2—Cd1—Cl196.65 (3)
N2—C6—C5132.8 (3)N4—Cd1—Cl1i91.81 (6)
N2—C6—C1105.5 (2)N1—Cd1—Cl1i154.49 (6)
C5—C6—C1121.7 (3)Cl2—Cd1—Cl1i102.39 (3)
N1—C7—N2113.1 (2)Cl1—Cd1—Cl1i86.78 (3)
N1—C7—C8119.9 (2)Cd1—Cl1—Cd1i93.22 (3)
N2—C7—C8127.0 (2)C7—N1—C1105.3 (2)
N4—C8—N3112.6 (2)C7—N1—Cd1112.71 (17)
N4—C8—C7120.4 (2)C1—N1—Cd1141.87 (18)
N3—C8—C7127.1 (2)C7—N2—C6107.1 (2)
N3—C9—C10131.9 (2)C7—N2—H15126.4
N3—C9—C14105.5 (2)C6—N2—H15126.4
C10—C9—C14122.5 (3)C8—N3—C9107.4 (2)
C11—C10—C9116.2 (3)C8—N3—H16126.3
C11—C10—H10121.9C9—N3—H16126.3
C9—C10—H10121.9C8—N4—C14105.6 (2)
C10—C11—C12122.0 (3)C8—N4—Cd1112.97 (16)
C10—C11—H11119.0C14—N4—Cd1140.52 (16)
C12—C11—H11119.0
N1—C1—C2—C3179.2 (3)C6—C1—N1—C71.1 (3)
C6—C1—C2—C3−0.3 (5)C2—C1—N1—Cd1−2.8 (5)
C1—C2—C3—C41.3 (5)C6—C1—N1—Cd1176.7 (2)
C2—C3—C4—C5−0.8 (5)N4—Cd1—N1—C7−4.14 (18)
C3—C4—C5—C6−0.8 (5)Cl2—Cd1—N1—C7112.26 (18)
C4—C5—C6—N2−178.4 (3)Cl1—Cd1—N1—C7−150.18 (18)
C4—C5—C6—C11.9 (5)Cl1i—Cd1—N1—C7−61.1 (2)
N1—C1—C6—N2−0.7 (3)N4—Cd1—N1—C1−179.5 (3)
C2—C1—C6—N2178.8 (3)Cl2—Cd1—N1—C1−63.1 (3)
N1—C1—C6—C5179.1 (3)Cl1—Cd1—N1—C134.5 (3)
C2—C1—C6—C5−1.3 (4)Cl1i—Cd1—N1—C1123.5 (3)
N1—C7—C8—N45.0 (4)N1—C7—N2—C60.7 (3)
N2—C7—C8—N4−175.5 (3)C8—C7—N2—C6−178.9 (3)
N1—C7—C8—N3−175.0 (3)C5—C6—N2—C7−179.7 (3)
N2—C7—C8—N34.6 (5)C1—C6—N2—C70.0 (3)
N3—C9—C10—C11178.9 (3)N4—C8—N3—C9−0.1 (3)
C14—C9—C10—C110.0 (4)C7—C8—N3—C9179.8 (3)
C9—C10—C11—C120.1 (5)C10—C9—N3—C8−178.9 (3)
C10—C11—C12—C13−0.1 (5)C14—C9—N3—C80.1 (3)
C11—C12—C13—C14−0.2 (4)N3—C8—N4—C140.1 (3)
C12—C13—C14—N4−178.9 (3)C7—C8—N4—C14−179.9 (2)
C12—C13—C14—C90.4 (4)N3—C8—N4—Cd1171.44 (17)
N3—C9—C14—N40.0 (3)C7—C8—N4—Cd1−8.5 (3)
C10—C9—C14—N4179.1 (2)C13—C14—N4—C8179.3 (3)
N3—C9—C14—C13−179.5 (2)C9—C14—N4—C80.0 (3)
C10—C9—C14—C13−0.3 (4)C13—C14—N4—Cd111.9 (5)
N4—Cd1—Cl1—Cd1i88.65 (9)C9—C14—N4—Cd1−167.4 (2)
N1—Cd1—Cl1—Cd1i154.46 (6)N1—Cd1—N4—C86.56 (18)
Cl2—Cd1—Cl1—Cd1i−102.11 (3)Cl2—Cd1—N4—C8−89.44 (19)
Cl1i—Cd1—Cl1—Cd1i0.0Cl1—Cd1—N4—C878.4 (2)
N2—C7—N1—C1−1.1 (3)Cl1i—Cd1—N4—C8165.38 (18)
C8—C7—N1—C1178.5 (2)N1—Cd1—N4—C14173.4 (3)
N2—C7—N1—Cd1−178.16 (18)Cl2—Cd1—N4—C1477.4 (3)
C8—C7—N1—Cd11.4 (3)Cl1—Cd1—N4—C14−114.8 (3)
C2—C1—N1—C7−178.4 (3)Cl1i—Cd1—N4—C14−27.8 (3)

Symmetry codes: (i) −x+2, −y+2, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N3—H16···Cl2ii0.862.393.221 (2)163

Symmetry codes: (ii) x−1/2, y−1/2, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BH2211).

References

  • Fieselmann, B. F., Hendrickson, D. N. & Stucky, G. D. (1978). Inorg. Chem.17, 2074–2077.
  • Meng, X. R., Song, Y. L., Hou, H. W., Han, H. Y., Xiao, B., Fan, Y. T. & Zhu, Y. (2004). Inorg. Chem.43, 3528–3536. [PubMed]
  • Rigaku (1998). RAPID-AUTO Rigaku Corporation, Tokyo, Japan.
  • Rigaku/MSC (2002). CrystalStructure Rigaku/MSC Inc., The Woodlands, Texas, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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