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Acta Crystallogr Sect E Struct Rep Online. 2008 October 1; 64(Pt 10): m1233.
Published online 2008 September 6. doi:  10.1107/S1600536808027657
PMCID: PMC2959444

catena-Poly[[(5,5′-dimethyl- 2,2′-bipyridine-κ2 N,N′)cadmium(II)]-di-μ-chlorido]

Abstract

The asymmetric unit of the title compound, [CdCl2(C12H12N2)]n, contains one half-mol­ecule; a twofold rotation axis passes through the Cd atom. The CdII atom is six-coordinated in a distorted octa­hedral configuration by two N atoms from 2,2′-bipyridine-5,5′-dimethyl and four bridging Cl atoms. The bridging function of the chloro atoms leads to a one-dimensional chain structure. There is a π–π contact between the pyridine rings [centroid–centroid distance = 3.9807 (9) Å].

Related literature

For related literature, see: Chen et al. (2003 [triangle]); Flook et al. (1973 [triangle]); Hu & Englert (2002 [triangle]); Janiak et al. (1999 [triangle]); Satoh et al. (2001 [triangle]); Zhou et al. (2003 [triangle]); Khalighi et al. (2008 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-m1233-scheme1.jpg

Experimental

Crystal data

  • [CdCl2(C12H12N2)]
  • M r = 367.55
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-m1233-efi2.jpg
  • a = 20.365 (4) Å
  • b = 9.3135 (19) Å
  • c = 7.2313 (14) Å
  • β = 107.53 (3)°
  • V = 1307.9 (5) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 2.06 mm−1
  • T = 298 (2) K
  • 0.20 × 0.17 × 0.15 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1998 [triangle]) T min = 0.666, T max = 0.740
  • 4283 measured reflections
  • 1724 independent reflections
  • 1585 reflections with I > 2σ(I)
  • R int = 0.052

Refinement

  • R[F 2 > 2σ(F 2)] = 0.032
  • wR(F 2) = 0.089
  • S = 1.08
  • 1724 reflections
  • 78 parameters
  • H-atom parameters constrained
  • Δρmax = 0.68 e Å−3
  • Δρmin = −0.76 e Å−3

Data collection: SMART (Bruker, 1998 [triangle]); cell refinement: SAINT (Bruker, 1998 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]).

Table 1
Selected geometric parameters (Å, °)

Supplementary Material

Crystal structure: contains datablocks I. DOI: 10.1107/S1600536808027657/hk2520sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808027657/hk2520Isup2.hkl

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

Acknowledgments

We are grateful to the Islamic Azad University, Shahr-e-Rey Branch, for financial support.

supplementary crystallographic information

Comment

In a recent paper, we reported the synthesis and crystal structure of [Zn(5,5'-dmbpy)Cl2], (Khalighi et al., 2008) [where 5,5'-dmbpy is 5,5'-dimethyl-2,2'-bipyridine]. Several CdII polymer complexes, with formula, [Cd(N—N)(µ-Cl)2]n, such as [Cd(phen)(µ-Cl)2]n, (II) (Chen et al., 2003), {[Cd(5,5'-dabpy)(µ-Cl)2].2H2O}n, (III) (Janiak et al., 1999) and [Cd(bipy)(µ-Cl)2]n, (IV) (Zhou et al., 2003) [where bipy is 2,2'-bipyridine, 5,5'-dabpy is 5,5'-diamino -2,2'-bipyridine and phen is 1,10-phenanthroline] have been synthesized and characterized by single-crystal X-ray diffraction methods. There are also several CdII polymer complexes, with formula, [Cd(µ-Cl)2L2]n, such as [Cd(µ-Cl)2(3,5-Me2py)2]n, (V), [Cd(µ-Cl)2(3,5-Br2py)2]n, (VI) and [Cd(µ-Cl)2(3,5-Cl2py)2]n, (VII) (Hu & Englert, 2002), [Cd(µ-Cl)2(3-Mepy)2]n, (VIII) (Satoh, et al., 2001) and [Cd(µ-Cl)2(im)2]n, (IX) (Flook et al., 1973) [where py is pyridine and im is imidazole] have been synthesized and characterized by single-crystal X-ray diffraction methods. We report herein the synthesis and crystal structure of the title compound (I).

The asymmetric unit of the title compound, (I), contains one half-molecule (Fig. 1). The CdII atom is six-coordinated in a distorted octahedral configuration by two N atoms from 2,2'-bipyridine-5,5'-dimethyl and four bridging Cl atoms. The bridging function of chloro atoms leads to a one-dimensional chain structure. The Cd—Cl and Cd—N bond lengths and angles (Table 1) are within normal ranges, as in (II), (III) and (IV).

In the crystal structure, the π—π contact (Fig. 2) between the pyridine rings, Cg4···Cg4i [symmetry code: (i) x, 1/2- y, z, where Cg4 is centroid of the ring (N1/C1/C2/C4-C6)] may stabilize the structure, with centroid-centroid distance of 3.9807 (9) Å.

Experimental

For the preparation of the title compound, a solution of 5,5'-dimethyl-2,2' -bipyridine (0.25 g, 1.33 mmol) in methanol (10 ml) was added to a solution of CdCl2.H2O (0.27 g, 1.33 mmol) in methanol (10 ml) at room temperature. The suitable crystals for X-ray analysis were obtained by methanol diffusion to a colorless solution in DMSO. Suitable crystals were isolated after one week (yield; 0.35 g, 71.6%, m.p. < 573 K).

Refinement

H atoms were positioned geometrically, with C-H = 0.93 and 0.96 Å for aromatic and methyl H, respectively, and constrained to ride on their parent atoms with Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level [symmetry code: (a) -x, y, 3/2 - z].
Fig. 2.
A packing diagram of the title compound.

Crystal data

[CdCl2(C12H12N2)]F(000) = 720
Mr = 367.55Dx = 1.867 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1004 reflections
a = 20.365 (4) Åθ = 4.1–29.2°
b = 9.3135 (19) ŵ = 2.06 mm1
c = 7.2313 (14) ÅT = 298 K
β = 107.53 (3)°Block, colorless
V = 1307.9 (5) Å30.20 × 0.17 × 0.15 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer1724 independent reflections
Radiation source: fine-focus sealed tube1585 reflections with I > 2σ(I)
graphiteRint = 0.052
[var phi] and ω scansθmax = 29.2°, θmin = 4.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)h = −27→18
Tmin = 0.666, Tmax = 0.740k = −12→11
4283 measured reflectionsl = −9→9

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)] = 0.032Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.089H-atom parameters constrained
S = 1.08w = 1/[σ2(Fo2) + (0.0543P)2 + 0.9451P] where P = (Fo2 + 2Fc2)/3
1724 reflections(Δ/σ)max = 0.011
78 parametersΔρmax = 0.68 e Å3
0 restraintsΔρmin = −0.76 e Å3

Special details

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 > σ(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)

xyzUiso*/Ueq
Cd10.00000.58047 (2)0.75000.03912 (12)
Cl10.07886 (4)0.41364 (6)0.99832 (11)0.04502 (17)
N10.06292 (10)0.7876 (2)0.8828 (3)0.0383 (4)
C10.12723 (13)0.7815 (3)1.0067 (4)0.0460 (5)
H10.14580.69181.04880.055*
C20.16716 (14)0.9023 (3)1.0746 (5)0.0480 (6)
C30.23917 (17)0.8878 (5)1.2093 (6)0.0674 (9)
H3A0.26650.83391.14660.081*
H3B0.23810.83891.32510.081*
H3C0.25890.98151.24220.081*
C40.13695 (15)1.0347 (3)1.0145 (4)0.0484 (6)
H40.16121.11871.05940.058*
C50.07094 (15)1.0418 (3)0.8883 (4)0.0435 (5)
H50.05041.13030.84860.052*
C60.03548 (12)0.9157 (2)0.8213 (4)0.0344 (4)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cd10.04181 (17)0.02643 (15)0.04102 (17)0.0000.00027 (11)0.000
Cl10.0458 (3)0.0370 (3)0.0479 (3)0.0092 (2)0.0074 (3)0.0073 (2)
N10.0373 (9)0.0313 (9)0.0426 (10)0.0009 (8)0.0064 (8)−0.0023 (8)
C10.0381 (11)0.0426 (13)0.0501 (13)0.0045 (10)0.0024 (10)−0.0068 (11)
C20.0364 (12)0.0536 (16)0.0507 (14)−0.0035 (10)0.0080 (11)−0.0133 (11)
C30.0394 (14)0.082 (2)0.070 (2)−0.0029 (15)−0.0003 (14)−0.0177 (18)
C40.0448 (13)0.0457 (14)0.0529 (15)−0.0112 (11)0.0117 (11)−0.0135 (12)
C50.0487 (13)0.0303 (10)0.0533 (14)−0.0046 (10)0.0179 (12)−0.0062 (10)
C60.0339 (10)0.0296 (11)0.0406 (11)0.0012 (7)0.0129 (9)−0.0020 (8)

Geometric parameters (Å, °)

Cd1—Cl1i2.5457 (9)C2—C31.502 (4)
Cd1—Cl1ii2.7668 (10)C3—H3A0.9600
Cd1—Cl1iii2.7668 (10)C3—H3B0.9600
Cl1—Cd12.5457 (9)C3—H3C0.9600
Cl1—Cd1ii2.7668 (10)C4—C51.380 (4)
Cd1—N1i2.355 (2)C4—H40.9300
N1—Cd12.355 (2)C5—C61.387 (3)
C1—N11.347 (3)C5—H50.9300
C1—C21.389 (4)C6—N11.336 (3)
C1—H10.9300C6—C6i1.501 (5)
C2—C41.388 (4)
Cd1—Cl1—Cd1ii94.82 (2)N1—C1—H1118.3
Cl1i—Cd1—Cl1ii96.22 (3)C2—C1—H1118.3
Cl1—Cd1—Cl1ii85.18 (2)C4—C2—C1116.9 (3)
Cl1i—Cd1—Cl1iii85.18 (2)C4—C2—C3122.5 (3)
Cl1—Cd1—Cl1iii96.22 (3)C1—C2—C3120.6 (3)
Cl1ii—Cd1—Cl1iii177.73 (2)C2—C3—H3A109.5
Cl1i—Cd1—Cl1104.77 (4)C2—C3—H3B109.5
N1—Cd1—Cl1i159.71 (6)H3A—C3—H3B109.5
N1i—Cd1—Cl1i93.57 (6)C2—C3—H3C109.5
N1—Cd1—Cl193.57 (6)H3A—C3—H3C109.5
N1i—Cd1—Cl1159.71 (6)H3B—C3—H3C109.5
N1—Cd1—Cl1ii93.89 (5)C5—C4—C2120.1 (3)
N1i—Cd1—Cl1ii84.24 (5)C5—C4—H4120.0
N1—Cd1—Cl1iii84.24 (5)C2—C4—H4120.0
N1i—Cd1—Cl1iii93.89 (5)C4—C5—C6119.4 (3)
N1—Cd1—N1i69.98 (10)C4—C5—H5120.3
C6—N1—C1119.0 (2)C6—C5—H5120.3
C6—N1—Cd1118.31 (15)N1—C6—C5121.2 (2)
C1—N1—Cd1122.49 (18)N1—C6—C6i116.64 (13)
N1—C1—C2123.3 (3)C5—C6—C6i122.15 (16)
N1—C1—C2—C42.3 (5)C1—N1—Cd1—N1i−176.1 (3)
N1—C1—C2—C3−178.6 (3)C6—N1—Cd1—Cl1i36.2 (3)
C1—C2—C4—C5−1.9 (4)C1—N1—Cd1—Cl1i−138.71 (19)
C3—C2—C4—C5179.1 (3)C6—N1—Cd1—Cl1−168.97 (17)
C2—C4—C5—C6−0.5 (4)C1—N1—Cd1—Cl116.1 (2)
C4—C5—C6—N12.8 (4)C6—N1—Cd1—Cl1ii−83.57 (18)
C4—C5—C6—C6i−177.9 (3)C1—N1—Cd1—Cl1ii101.5 (2)
C5—C6—N1—C1−2.5 (4)C6—N1—Cd1—Cl1iii95.14 (18)
C6i—C6—N1—C1178.2 (3)C1—N1—Cd1—Cl1iii−79.8 (2)
C5—C6—N1—Cd1−177.59 (18)Cd1ii—Cl1—Cd1—N193.61 (5)
C6i—C6—N1—Cd13.0 (3)Cd1ii—Cl1—Cd1—N1i58.77 (15)
C2—C1—N1—C6−0.1 (4)Cd1ii—Cl1—Cd1—Cl1i−95.17 (2)
C2—C1—N1—Cd1174.8 (2)Cd1ii—Cl1—Cd1—Cl1ii0.0
C6—N1—Cd1—N1i−1.14 (13)Cd1ii—Cl1—Cd1—Cl1iii178.20 (2)

Symmetry codes: (i) −x, y, −z+3/2; (ii) −x, −y+1, −z+2; (iii) x, −y+1, z−1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HK2520).

References

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