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

Ahmadi, R.; Khalighi, A.; Kalateh, K.; Amani, V.; Khavasi, H.R.

doi:10.1107/S1600536808027657

metal-organic compounds

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Volume 64| Part 10| October 2008| Page m1233

doi:10.1107/S1600536808027657

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

Roya Ahmadi,^a Aida Khalighi,^a Khadijeh Kalateh,^a Vahid Amani ^a ^* and Hamid Reza Khavasi ^b

^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 Cd^II 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 ); Flook et al. (1973 ); Hu & Englert (2002 ); Janiak et al. (1999 ); Satoh et al. (2001 ); Zhou et al. (2003 ); Khalighi et al. (2008 ).

Experimental

Crystal data

[CdCl₂(C₁₂H₁₂N₂)]
M_r = 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 ) 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[F² > 2σ(F²)] = 0.032
wR(F²) = 0.089
S = 1.08
1724 reflections
78 parameters
H-atom parameters constrained
Δρ_max = 0.68 e Å⁻³
Δρ_min = −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 ); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

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

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

checkCIF report

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 Cd^II 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 Cd^II 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 Cd^II 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.

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).

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

	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.

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

Crystal data top

[CdCl₂(C₁₂H₁₂N₂)]	F(000) = 720
M_r = 367.55	D_x = 1.867 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1004 reflections
a = 20.365 (4) Å	θ = 4.1–29.2°
b = 9.3135 (19) Å	µ = 2.06 mm⁻¹
c = 7.2313 (14) Å	T = 298 K
β = 107.53 (3)°	Block, colorless
V = 1307.9 (5) Å³	0.20 × 0.17 × 0.15 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	1724 independent reflections
Radiation source: fine-focus sealed tube	1585 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.052
ϕ and ω scans	θ_max = 29.2°, θ_min = 4.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)	h = −27→18
T_min = 0.666, T_max = 0.740	k = −12→11
4283 measured reflections	l = −9→9

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.089	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0543P)² + 0.9451P] where P = (F_o² + 2F_c²)/3
1724 reflections	(Δ/σ)_max = 0.011
78 parameters	Δρ_max = 0.68 e Å⁻³
0 restraints	Δρ_min = −0.76 e Å⁻³

Crystal data top

[CdCl₂(C₁₂H₁₂N₂)]	V = 1307.9 (5) Å³
M_r = 367.55	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 20.365 (4) Å	µ = 2.06 mm⁻¹
b = 9.3135 (19) Å	T = 298 K
c = 7.2313 (14) Å	0.20 × 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)
T_min = 0.666, T_max = 0.740	R_int = 0.052
4283 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.089	H-atom parameters constrained
S = 1.08	Δρ_max = 0.68 e Å⁻³
1724 reflections	Δρ_min = −0.76 e Å⁻³
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

	x	y	z	U_iso*/U_eq
Cd1	0.0000	0.58047 (2)	0.7500	0.03912 (12)
Cl1	0.07886 (4)	0.41364 (6)	0.99832 (11)	0.04502 (17)
N1	0.06292 (10)	0.7876 (2)	0.8828 (3)	0.0383 (4)
C1	0.12723 (13)	0.7815 (3)	1.0067 (4)	0.0460 (5)
H1	0.1458	0.6918	1.0488	0.055*
C2	0.16716 (14)	0.9023 (3)	1.0746 (5)	0.0480 (6)
C3	0.23917 (17)	0.8878 (5)	1.2093 (6)	0.0674 (9)
H3A	0.2665	0.8339	1.1466	0.081*
H3B	0.2381	0.8389	1.3251	0.081*
H3C	0.2589	0.9815	1.2422	0.081*
C4	0.13695 (15)	1.0347 (3)	1.0145 (4)	0.0484 (6)
H4	0.1612	1.1187	1.0594	0.058*
C5	0.07094 (15)	1.0418 (3)	0.8883 (4)	0.0435 (5)
H5	0.0504	1.1303	0.8486	0.052*
C6	0.03548 (12)	0.9157 (2)	0.8213 (4)	0.0344 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.04181 (17)	0.02643 (15)	0.04102 (17)	0.000	0.00027 (11)	0.000
Cl1	0.0458 (3)	0.0370 (3)	0.0479 (3)	0.0092 (2)	0.0074 (3)	0.0073 (2)
N1	0.0373 (9)	0.0313 (9)	0.0426 (10)	0.0009 (8)	0.0064 (8)	−0.0023 (8)
C1	0.0381 (11)	0.0426 (13)	0.0501 (13)	0.0045 (10)	0.0024 (10)	−0.0068 (11)
C2	0.0364 (12)	0.0536 (16)	0.0507 (14)	−0.0035 (10)	0.0080 (11)	−0.0133 (11)
C3	0.0394 (14)	0.082 (2)	0.070 (2)	−0.0029 (15)	−0.0003 (14)	−0.0177 (18)
C4	0.0448 (13)	0.0457 (14)	0.0529 (15)	−0.0112 (11)	0.0117 (11)	−0.0135 (12)
C5	0.0487 (13)	0.0303 (10)	0.0533 (14)	−0.0046 (10)	0.0179 (12)	−0.0062 (10)
C6	0.0339 (10)	0.0296 (11)	0.0406 (11)	0.0012 (7)	0.0129 (9)	−0.0020 (8)

Geometric parameters (Å, º) top

Cd1—Cl1ⁱ	2.5457 (9)	C2—C3	1.502 (4)
Cd1—Cl1ⁱⁱ	2.7668 (10)	C3—H3A	0.9600
Cd1—Cl1ⁱⁱⁱ	2.7668 (10)	C3—H3B	0.9600
Cl1—Cd1	2.5457 (9)	C3—H3C	0.9600
Cl1—Cd1ⁱⁱ	2.7668 (10)	C4—C5	1.380 (4)
Cd1—N1ⁱ	2.355 (2)	C4—H4	0.9300
N1—Cd1	2.355 (2)	C5—C6	1.387 (3)
C1—N1	1.347 (3)	C5—H5	0.9300
C1—C2	1.389 (4)	C6—N1	1.336 (3)
C1—H1	0.9300	C6—C6ⁱ	1.501 (5)
C2—C4	1.388 (4)

Cd1—Cl1—Cd1ⁱⁱ	94.82 (2)	N1—C1—H1	118.3
Cl1ⁱ—Cd1—Cl1ⁱⁱ	96.22 (3)	C2—C1—H1	118.3
Cl1—Cd1—Cl1ⁱⁱ	85.18 (2)	C4—C2—C1	116.9 (3)
Cl1ⁱ—Cd1—Cl1ⁱⁱⁱ	85.18 (2)	C4—C2—C3	122.5 (3)
Cl1—Cd1—Cl1ⁱⁱⁱ	96.22 (3)	C1—C2—C3	120.6 (3)
Cl1ⁱⁱ—Cd1—Cl1ⁱⁱⁱ	177.73 (2)	C2—C3—H3A	109.5
Cl1ⁱ—Cd1—Cl1	104.77 (4)	C2—C3—H3B	109.5
N1—Cd1—Cl1ⁱ	159.71 (6)	H3A—C3—H3B	109.5
N1ⁱ—Cd1—Cl1ⁱ	93.57 (6)	C2—C3—H3C	109.5
N1—Cd1—Cl1	93.57 (6)	H3A—C3—H3C	109.5
N1ⁱ—Cd1—Cl1	159.71 (6)	H3B—C3—H3C	109.5
N1—Cd1—Cl1ⁱⁱ	93.89 (5)	C5—C4—C2	120.1 (3)
N1ⁱ—Cd1—Cl1ⁱⁱ	84.24 (5)	C5—C4—H4	120.0
N1—Cd1—Cl1ⁱⁱⁱ	84.24 (5)	C2—C4—H4	120.0
N1ⁱ—Cd1—Cl1ⁱⁱⁱ	93.89 (5)	C4—C5—C6	119.4 (3)
N1—Cd1—N1ⁱ	69.98 (10)	C4—C5—H5	120.3
C6—N1—C1	119.0 (2)	C6—C5—H5	120.3
C6—N1—Cd1	118.31 (15)	N1—C6—C5	121.2 (2)
C1—N1—Cd1	122.49 (18)	N1—C6—C6ⁱ	116.64 (13)
N1—C1—C2	123.3 (3)	C5—C6—C6ⁱ	122.15 (16)

N1—C1—C2—C4	2.3 (5)	C1—N1—Cd1—N1ⁱ	−176.1 (3)
N1—C1—C2—C3	−178.6 (3)	C6—N1—Cd1—Cl1ⁱ	36.2 (3)
C1—C2—C4—C5	−1.9 (4)	C1—N1—Cd1—Cl1ⁱ	−138.71 (19)
C3—C2—C4—C5	179.1 (3)	C6—N1—Cd1—Cl1	−168.97 (17)
C2—C4—C5—C6	−0.5 (4)	C1—N1—Cd1—Cl1	16.1 (2)
C4—C5—C6—N1	2.8 (4)	C6—N1—Cd1—Cl1ⁱⁱ	−83.57 (18)
C4—C5—C6—C6ⁱ	−177.9 (3)	C1—N1—Cd1—Cl1ⁱⁱ	101.5 (2)
C5—C6—N1—C1	−2.5 (4)	C6—N1—Cd1—Cl1ⁱⁱⁱ	95.14 (18)
C6ⁱ—C6—N1—C1	178.2 (3)	C1—N1—Cd1—Cl1ⁱⁱⁱ	−79.8 (2)
C5—C6—N1—Cd1	−177.59 (18)	Cd1ⁱⁱ—Cl1—Cd1—N1	93.61 (5)
C6ⁱ—C6—N1—Cd1	3.0 (3)	Cd1ⁱⁱ—Cl1—Cd1—N1ⁱ	58.77 (15)
C2—C1—N1—C6	−0.1 (4)	Cd1ⁱⁱ—Cl1—Cd1—Cl1ⁱ	−95.17 (2)
C2—C1—N1—Cd1	174.8 (2)	Cd1ⁱⁱ—Cl1—Cd1—Cl1ⁱⁱ	0.0
C6—N1—Cd1—N1ⁱ	−1.14 (13)	Cd1ⁱⁱ—Cl1—Cd1—Cl1ⁱⁱⁱ	178.20 (2)

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

Experimental details

Crystal data
Chemical formula	[CdCl₂(C₁₂H₁₂N₂)]
M_r	367.55
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	20.365 (4), 9.3135 (19), 7.2313 (14)
β (°)	107.53 (3)
V (Å³)	1307.9 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.06
Crystal size (mm)	0.20 × 0.17 × 0.15

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1998)
T_min, T_max	0.666, 0.740
No. of measured, independent and observed [I > 2σ(I)] reflections	4283, 1724, 1585
R_int	0.052
(sin θ/λ)_max (Å⁻¹)	0.686

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.089, 1.08
No. of reflections	1724
No. of parameters	78
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	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—Cl1ⁱ	2.7668 (10)	N1—Cd1	2.355 (2)
Cl1—Cd1	2.5457 (9)

Cl1—Cd1—Cl1ⁱ	85.18 (2)	N1—Cd1—Cl1	93.57 (6)
Cl1—Cd1—Cl1ⁱⁱ	96.22 (3)	N1ⁱⁱⁱ—Cd1—Cl1	159.71 (6)
Cl1ⁱ—Cd1—Cl1ⁱⁱ	177.73 (2)	N1—Cd1—Cl1ⁱ	93.89 (5)
Cl1ⁱⁱⁱ—Cd1—Cl1	104.77 (4)	N1—Cd1—Cl1ⁱⁱ	84.24 (5)
N1—Cd1—Cl1ⁱⁱⁱ	159.71 (6)	N1—Cd1—N1ⁱⁱⁱ	69.98 (10)

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

Acknowledgements

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

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