supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportcited insimilar papers Open access

Acta Cryst. (2009). E65, m37    [ doi:10.1107/S1600536808040968 ]

Di-[mu]-chlorido-bis[(2,2'-bibenzimidazole)chloridocadmium(II)]

G. Liu

Abstract top

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.

Comment top

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).

Related literature top

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

Experimental top

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 top

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).

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); 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: SHELXTL (Sheldrick,2008); software used to prepare material for publication: SHELXTL (Sheldrick,2008).

Figures top
[Figure 1] Fig. 1. The structure of the title compound with displacement ellipsoids at the 30% probability level.
[Figure 2] Fig. 2. One dimensional chain formed by hydrogen bonds (dashed lines) in the crystal structure of the title compound.
Di-µ-chlorido-bis[(2,2'-bibenzimidazole)chloridocadmium(II)] top
Crystal data top
[Cd2Cl4(C14H10N4)2]F(000) = 1632
Mr = 835.12Dx = 1.906 Mg m−3
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 mm−1
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 top
Rigaku R-AXIS RAPID-S
diffractometer		2840 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 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)] = 0.033Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.060H-atom parameters constrained
S = 1.14 w = 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 Å−3
0 restraintsΔρmin = −0.34 e Å−3
Crystal data top
[Cd2Cl4(C14H10N4)2]V = 2910.1 (10) Å3
Mr = 835.12Z = 4
Monoclinic, C2/cMo Kα radiation
a = 11.824 (2) ŵ = 1.86 mm−1
b = 10.784 (2) ÅT = 293 K
c = 22.828 (5) Å0.17 × 0.16 × 0.12 mm
β = 91.10 (3)°
Data collection top
Rigaku R-AXIS RAPID-S
diffractometer		2840 reflections with I > 2σ(I)
14677 measured reflectionsRint = 0.035
3337 independent reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.033H-atom parameters constrained
wR(F2) = 0.060Δρmax = 0.29 e Å−3
S = 1.14Δρmin = −0.34 e Å−3
3337 reflectionsAbsolute structure: ?
190 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
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) top
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, °) top
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, °) top
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.
Table 1
Selected geometric parameters (Å, °) top
Cd1—N42.305 (2)Cd1—Cl12.5725 (10)
Cd1—N12.338 (2)Cd1—Cl1i2.5903 (10)
Cd1—Cl22.4602 (8)
N4—Cd1—Cl2118.63 (6)Cl2—Cd1—Cl196.65 (3)
N4—Cd1—Cl1144.04 (6)N1—Cd1—Cl1i154.49 (6)
Symmetry codes: (i) −x+2, −y+2, −z+1.
Table 2
Hydrogen-bond geometry (Å, °) top
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.
Acknowledgements top

The author thanks Chifeng University for supporting this work.

references
References top

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.

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.