metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

catena-Poly[[(5,5′-di­methyl- 2,2′-bi­pyridine-κ2N,N′)cadmium(II)]-di-μ-chlorido]

aIslamic Azad University, Shahr-e-Rey Branch, Tehran, Iran, and bDepartment of Chemistry, Shahid Beheshti University, Tehran 1983963113, Iran
*Correspondence e-mail: v_amani2002@yahoo.com

(Received 26 August 2008; accepted 28 August 2008; online 6 September 2008)

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 ππ contact between the pyridine rings [centroid–centroid distance = 3.9807 (9) Å].

Related literature

For related literature, see: Chen et al. (2003[Chen, H.-B., Zhou, Z.-H., Wan, H.-L. & Ng, S. W. (2003). Acta Cryst. E59, m845-m846.]); Flook et al. (1973[Flook, R. J., Freeman, H. C., Huq, F. & Rosalky, J. M. (1973). Acta Cryst. B29, 903-906.]); Hu & Englert (2002[Hu, C. & Englert, U. (2002). CrystEngComm, 4, 20-25.]); Janiak et al. (1999[Janiak, C., Deblon, S., Wu, H. P., Kolm, M. J., Klufers, P., Piotrowski, H. & Mayer, P. (1999). Eur. J. Inorg. Chem. pp. 1507-1521.]); Satoh et al. (2001[Satoh, K., Suzuki, T. & Sawada, K. (2001). Monatsh. Chem. 132, 1145-1155.]); Zhou et al. (2003[Zhou, Y.-F., Xu, Y., Yuan, D.-Q. & Hong, M.-C. (2003). Acta Cryst. E59, m821-m823.]); Khalighi et al. (2008[Khalighi, A., Ahmadi, R., Amani, V. & Khavasi, H. R. (2008). Acta Cryst. E64, m1211-m1212.]).

[Scheme 1]

Experimental

Crystal data
  • [CdCl2(C12H12N2)]

  • Mr = 367.55

  • Monoclinic, C 2/c

  • 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[Sheldrick, G. M. (1998). SADABS. Bruker AXS, Madison, Wisconsin, USA.]) Tmin = 0.666, Tmax = 0.740

  • 4283 measured reflections

  • 1724 independent reflections

  • 1585 reflections with I > 2σ(I)

  • Rint = 0.052

Refinement
  • R[F2 > 2σ(F2)] = 0.032

  • wR(F2) = 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

Table 1
Selected geometric parameters (Å, °)

Cd1—Cl1i 2.7668 (10)
Cl1—Cd1 2.5457 (9)
N1—Cd1 2.355 (2)
Cl1—Cd1—Cl1i 85.18 (2)
Cl1—Cd1—Cl1ii 96.22 (3)
Cl1i—Cd1—Cl1ii 177.73 (2)
Cl1iii—Cd1—Cl1 104.77 (4)
N1—Cd1—Cl1iii 159.71 (6)
N1—Cd1—Cl1 93.57 (6)
N1iii—Cd1—Cl1 159.71 (6)
N1—Cd1—Cl1i 93.89 (5)
N1—Cd1—Cl1ii 84.24 (5)
N1—Cd1—N1iii 69.98 (10)
Symmetry codes: (i) -x, -y+1, -z+2; (ii) [x, -y+1, z-{\script{1\over 2}}]; (iii) [-x, y, -z+{\script{3\over 2}}].

Data collection: SMART (Bruker, 1998[Bruker (1998). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 1998[Bruker (1998). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXTL; molecular graphics: ORTEP-3 for Windows (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]); software used to prepare material for publication: WinGX (Farrugia, 1999[Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837-838.]).

Supporting information


Comment top

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 ππ 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.

Related literature top

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

Experimental top

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 top

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).

Computing details top

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

Figures top
[Figure 1] 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].
[Figure 2] Fig. 2. A packing diagram of the title compound.
catena-Poly[[(5,5'-dimethyl-2,2'-bipyridine- κ2N,N')cadmium(II)]-di-µ-chlorido] top
Crystal data top
[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 top
Bruker SMART CCD area-detector
diffractometer
1724 independent reflections
Radiation source: fine-focus sealed tube1585 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.052
ϕ and ω scansθmax = 29.2°, θmin = 4.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1998)
h = 2718
Tmin = 0.666, Tmax = 0.740k = 1211
4283 measured reflectionsl = 99
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)] = 0.032Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.089H-atom parameters constrained
S = 1.08 w = 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
Crystal data top
[CdCl2(C12H12N2)]V = 1307.9 (5) Å3
Mr = 367.55Z = 4
Monoclinic, C2/cMo Kα radiation
a = 20.365 (4) ŵ = 2.06 mm1
b = 9.3135 (19) ÅT = 298 K
c = 7.2313 (14) Å0.20 × 0.17 × 0.15 mm
β = 107.53 (3)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
1724 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1998)
1585 reflections with I > 2σ(I)
Tmin = 0.666, Tmax = 0.740Rint = 0.052
4283 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0320 restraints
wR(F2) = 0.089H-atom parameters constrained
S = 1.08Δρmax = 0.68 e Å3
1724 reflectionsΔρmin = 0.76 e Å3
78 parameters
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 > 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) top
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) top
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, º) top
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—N1i176.1 (3)
N1—C1—C2—C3178.6 (3)C6—N1—Cd1—Cl1i36.2 (3)
C1—C2—C4—C51.9 (4)C1—N1—Cd1—Cl1i138.71 (19)
C3—C2—C4—C5179.1 (3)C6—N1—Cd1—Cl1168.97 (17)
C2—C4—C5—C60.5 (4)C1—N1—Cd1—Cl116.1 (2)
C4—C5—C6—N12.8 (4)C6—N1—Cd1—Cl1ii83.57 (18)
C4—C5—C6—C6i177.9 (3)C1—N1—Cd1—Cl1ii101.5 (2)
C5—C6—N1—C12.5 (4)C6—N1—Cd1—Cl1iii95.14 (18)
C6i—C6—N1—C1178.2 (3)C1—N1—Cd1—Cl1iii79.8 (2)
C5—C6—N1—Cd1177.59 (18)Cd1ii—Cl1—Cd1—N193.61 (5)
C6i—C6—N1—Cd13.0 (3)Cd1ii—Cl1—Cd1—N1i58.77 (15)
C2—C1—N1—C60.1 (4)Cd1ii—Cl1—Cd1—Cl1i95.17 (2)
C2—C1—N1—Cd1174.8 (2)Cd1ii—Cl1—Cd1—Cl1ii0.0
C6—N1—Cd1—N1i1.14 (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, z1/2.

Experimental details

Crystal data
Chemical formula[CdCl2(C12H12N2)]
Mr367.55
Crystal system, space groupMonoclinic, C2/c
Temperature (K)298
a, b, c (Å)20.365 (4), 9.3135 (19), 7.2313 (14)
β (°) 107.53 (3)
V3)1307.9 (5)
Z4
Radiation typeMo Kα
µ (mm1)2.06
Crystal size (mm)0.20 × 0.17 × 0.15
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1998)
Tmin, Tmax0.666, 0.740
No. of measured, independent and
observed [I > 2σ(I)] reflections
4283, 1724, 1585
Rint0.052
(sin θ/λ)max1)0.686
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.032, 0.089, 1.08
No. of reflections1724
No. of parameters78
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.68, 0.76

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXTL (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top
Cd1—Cl1i2.7668 (10)N1—Cd12.355 (2)
Cl1—Cd12.5457 (9)
Cl1—Cd1—Cl1i85.18 (2)N1—Cd1—Cl193.57 (6)
Cl1—Cd1—Cl1ii96.22 (3)N1iii—Cd1—Cl1159.71 (6)
Cl1i—Cd1—Cl1ii177.73 (2)N1—Cd1—Cl1i93.89 (5)
Cl1iii—Cd1—Cl1104.77 (4)N1—Cd1—Cl1ii84.24 (5)
N1—Cd1—Cl1iii159.71 (6)N1—Cd1—N1iii69.98 (10)
Symmetry codes: (i) x, y+1, z+2; (ii) x, y+1, z1/2; (iii) x, y, z+3/2.
 

Acknowledgements

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

References

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