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

Shirvan, S.A.; Haydari Dezfuli, S.

doi:10.1107/S1600536812023860

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page m846

doi:10.1107/S1600536812023860

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

Sadif A. Shirvan ^a ^* and Sara Haydari Dezfuli ^a

^aDepartment of Chemistry, Islamic Azad University, Omidieh Branch, Omidieh, Iran
^*Correspondence e-mail: sadif_shirvan1@yahoo.com

(Received 21 May 2012; accepted 25 May 2012; online 31 May 2012)

In the crystal of the title polymeric compound, [CdBr₂(C₁₂H₁₂N₂)]_n, the Cd^II cation is located on a twofold rotation axis. The Cd^II cation is six-coordinated in a distorted octahedral geometry formed by two N atoms from the 5,5′-dimethyl-2,2′-bipyridine ligand and four bridging Br⁻ anions. The bridging function of the Br⁻ anions leads to a polymeric chain running along the c axis.

Related literature

For related structures, see: Ahmadi et al. (2008 , 2010 ); Albada et al. (2004 ); Amani et al. (2007 , 2009 ); Han et al. (2006 ); Kalateh et al. (2010 ); Karaca et al. (2009 ); Khalighi et al. (2008 ); Maheshwari et al. (2007 ); Tadayon Pour et al. (2008 ); Zhang (2007 ).

Experimental

Crystal data

[CdBr₂(C₁₂H₁₂N₂)]
M_r = 456.45
Monoclinic, C 2/c
a = 19.637 (5) Å
b = 9.6563 (15) Å
c = 7.485 (2) Å
β = 104.76 (2)°
V = 1372.4 (6) Å³
Z = 4
Mo Kα radiation
μ = 7.39 mm⁻¹
T = 298 K
0.12 × 0.11 × 0.09 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.435, T_max = 0.548
5378 measured reflections
1346 independent reflections
1015 reflections with I > 2σ(I)
R_int = 0.110

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.091
S = 1.03
1346 reflections
78 parameters
H-atom parameters constrained
Δρ_max = 0.85 e Å⁻³
Δρ_min = −0.70 e Å⁻³

Table 1
Selected bond lengths (Å)

Cd1—N1	2.352 (4)
Cd1—Br1	2.6676 (8)
Cd1—Br1ⁱ	2.9351 (10)
Symmetry code: (i) $[x, -y, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812023860/xu5547sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812023860/xu5547Isup2.hkl

checkCIF report

Comment top

5,5'-Dimethyl-2,2'-bipyridine (5,5'-dmbipy), is a good bidentate ligand, and numerous complexes with 5,5'-dmbipy have been prepared, such as that of zinc (Khalighi et al., 2008), indium (Kalateh et al., 2010), iron (Amani et al., 2007), platin (Amani et al., 2009; Maheshwari et al., 2007), copper (Albada et al., 2004), gold (Karaca et al., 2009), cadmium (Ahmadi et al., 2008,2010) and mercury (Tadayon Pour et al., 2008). Here, we report the synthesis and structure of the title compound.

The asymmetric unit of the title compound, (Fig. 1), 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 5,5'-dimethyl-2,2'-bipyridine and four bridging Br atoms. The bridging function of the bromide atoms leads to a one-dimensional chain structure. The Cd—Br and Cd—N bond lengths and angles (Table 1) are within normal range [Cd(phen)(µ-Br)₂]_n, (Zhang, 2007) and [Cd(bipy)(µ-Br)₂]_n, (Han et al., 2006) [where phen is 1,10-phenanthroline and bipy is 2,2'-bipyridine].

Related literature top

For related structures, see: Ahmadi et al. (2008, 2010); Albada et al. (2004); Amani et al. (2007, 2009); Han et al. (2006); Kalateh et al. (2010); Karaca et al. (2009); Khalighi et al. (2008); Maheshwari et al. (2007); Tadayon Pour et al. (2008); Zhang (2007).

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 CdBr₂.4H₂O (0.46 g, 1.33 mmol) in methanol (10 ml) at room temperature. The suitable crystals for X-ray diffraction experiment were obtained by methanol diffusion to a colorless solution in DMSO. Suitable crystals were isolated after one week (yield; 0.45 g, 74.1%).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level [Symmetry codes: (a) 1 - x,y,1/2 - z].

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

Crystal data top

[CdBr₂(C₁₂H₁₂N₂)]	F(000) = 864
M_r = 456.45	D_x = 2.209 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 19.637 (5) Å	Cell parameters from 5378 reflections
b = 9.6563 (15) Å	θ = 2.2–26.0°
c = 7.485 (2) Å	µ = 7.39 mm⁻¹
β = 104.76 (2)°	T = 298 K
V = 1372.4 (6) Å³	Prism, colorless
Z = 4	0.12 × 0.11 × 0.09 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	1346 independent reflections
Radiation source: fine-focus sealed tube	1015 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.110
ω scans	θ_max = 26.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −22→24
T_min = 0.435, T_max = 0.548	k = −10→11
5378 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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.091	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0403P)²] where P = (F_o² + 2F_c²)/3
1346 reflections	(Δ/σ)_max = 0.004
78 parameters	Δρ_max = 0.85 e Å⁻³
0 restraints	Δρ_min = −0.70 e Å⁻³

Crystal data top

[CdBr₂(C₁₂H₁₂N₂)]	V = 1372.4 (6) Å³
M_r = 456.45	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 19.637 (5) Å	µ = 7.39 mm⁻¹
b = 9.6563 (15) Å	T = 298 K
c = 7.485 (2) Å	0.12 × 0.11 × 0.09 mm
β = 104.76 (2)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	1346 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1015 reflections with I > 2σ(I)
T_min = 0.435, T_max = 0.548	R_int = 0.110
5378 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.091	H-atom parameters constrained
S = 1.03	Δρ_max = 0.85 e Å⁻³
1346 reflections	Δρ_min = −0.70 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
C1	0.3751 (3)	0.2708 (6)	−0.0036 (8)	0.0498 (15)
H1	0.3565	0.1843	−0.0435	0.060*
C2	0.3367 (3)	0.3894 (7)	−0.0747 (9)	0.0549 (16)
C3	0.2663 (4)	0.3740 (9)	−0.2097 (11)	0.085 (3)
H3A	0.2355	0.3221	−0.1537	0.102*
H3B	0.2718	0.3261	−0.3175	0.102*
H3C	0.2465	0.4639	−0.2444	0.102*
C4	0.3660 (3)	0.5147 (7)	−0.0143 (9)	0.0600 (18)
H4	0.3423	0.5960	−0.0591	0.072*
C5	0.4299 (3)	0.5211 (6)	0.1118 (8)	0.0506 (15)
H5	0.4494	0.6067	0.1527	0.061*
C6	0.4659 (3)	0.4006 (5)	0.1792 (8)	0.0421 (13)
N1	0.4378 (2)	0.2774 (5)	0.1198 (6)	0.0412 (11)
Cd1	0.5000	0.07821 (6)	0.2500	0.0476 (2)
Br1	0.41572 (3)	−0.09792 (6)	0.02140 (9)	0.0507 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.041 (3)	0.047 (3)	0.054 (4)	−0.004 (3)	−0.001 (3)	0.008 (3)
C2	0.041 (3)	0.066 (4)	0.055 (4)	0.003 (3)	0.008 (3)	0.020 (3)
C3	0.048 (4)	0.109 (6)	0.086 (6)	0.006 (4)	−0.005 (4)	0.034 (5)
C4	0.055 (4)	0.061 (4)	0.069 (4)	0.026 (3)	0.026 (3)	0.029 (4)
C5	0.062 (4)	0.040 (3)	0.056 (4)	0.012 (3)	0.027 (3)	0.007 (3)
C6	0.044 (3)	0.036 (3)	0.049 (3)	0.003 (2)	0.017 (3)	0.007 (2)
N1	0.033 (2)	0.038 (2)	0.049 (3)	0.0021 (18)	0.003 (2)	0.006 (2)
Cd1	0.0456 (4)	0.0318 (3)	0.0530 (4)	0.000	−0.0102 (3)	0.000
Br1	0.0474 (4)	0.0423 (3)	0.0550 (4)	−0.0094 (2)	−0.0006 (3)	−0.0064 (2)

Geometric parameters (Å, º) top

C1—N1	1.339 (6)	C5—C6	1.388 (8)
C1—C2	1.400 (8)	C5—H5	0.9300
C1—H1	0.9300	C6—N1	1.339 (7)
C2—C4	1.366 (10)	C6—C6ⁱ	1.481 (11)
C2—C3	1.497 (9)	Cd1—N1	2.352 (4)
C3—H3A	0.9600	Cd1—N1ⁱ	2.352 (4)
C3—H3B	0.9600	Cd1—Br1	2.6676 (8)
C3—H3C	0.9600	Cd1—Br1ⁱ	2.6676 (8)
C4—C5	1.366 (9)	Cd1—Br1ⁱⁱ	2.9351 (10)
C4—H4	0.9300	Cd1—Br1ⁱⁱⁱ	2.9352 (10)

N1—C1—C2	122.3 (6)	C5—C6—C6ⁱ	123.0 (4)
N1—C1—H1	118.8	C6—N1—C1	120.0 (5)
C2—C1—H1	118.8	C6—N1—Cd1	117.6 (3)
C4—C2—C1	117.3 (5)	C1—N1—Cd1	122.4 (4)
C4—C2—C3	123.3 (6)	N1—Cd1—N1ⁱ	70.3 (2)
C1—C2—C3	119.4 (6)	N1—Cd1—Br1	94.81 (10)
C2—C3—H3A	109.5	N1ⁱ—Cd1—Br1	163.48 (11)
C2—C3—H3B	109.5	N1—Cd1—Br1ⁱ	163.48 (11)
H3A—C3—H3B	109.5	N1ⁱ—Cd1—Br1ⁱ	94.81 (10)
C2—C3—H3C	109.5	Br1—Cd1—Br1ⁱ	100.78 (4)
H3A—C3—H3C	109.5	N1—Cd1—Br1ⁱⁱ	84.78 (12)
H3B—C3—H3C	109.5	N1ⁱ—Cd1—Br1ⁱⁱ	89.13 (12)
C5—C4—C2	120.2 (6)	Br1—Cd1—Br1ⁱⁱ	96.79 (3)
C5—C4—H4	119.9	Br1ⁱ—Cd1—Br1ⁱⁱ	87.96 (3)
C2—C4—H4	119.9	N1—Cd1—Br1ⁱⁱⁱ	89.13 (12)
C4—C5—C6	120.4 (6)	N1ⁱ—Cd1—Br1ⁱⁱⁱ	84.78 (12)
C4—C5—H5	119.8	Br1—Cd1—Br1ⁱⁱⁱ	87.96 (2)
C6—C5—H5	119.8	Br1ⁱ—Cd1—Br1ⁱⁱⁱ	96.79 (3)
N1—C6—C5	119.7 (5)	Br1ⁱⁱ—Cd1—Br1ⁱⁱⁱ	172.56 (3)
N1—C6—C6ⁱ	117.3 (3)	Cd1—Br1—Cd1ⁱⁱⁱ	92.04 (3)

N1—C1—C2—C4	0.5 (10)	C1—N1—Cd1—N1ⁱ	−177.4 (6)
N1—C1—C2—C3	−178.9 (6)	C6—N1—Cd1—Br1	−172.9 (4)
C1—C2—C4—C5	−0.6 (10)	C1—N1—Cd1—Br1	10.0 (5)
C3—C2—C4—C5	178.8 (6)	C6—N1—Cd1—Br1ⁱ	26.4 (8)
C2—C4—C5—C6	0.2 (10)	C1—N1—Cd1—Br1ⁱ	−150.8 (4)
C4—C5—C6—N1	0.2 (10)	C6—N1—Cd1—Br1ⁱⁱ	90.7 (4)
C4—C5—C6—C6ⁱ	−177.8 (7)	C1—N1—Cd1—Br1ⁱⁱ	−86.4 (4)
C5—C6—N1—C1	−0.3 (9)	C6—N1—Cd1—Br1ⁱⁱⁱ	−85.0 (4)
C6ⁱ—C6—N1—C1	177.8 (6)	C1—N1—Cd1—Br1ⁱⁱⁱ	97.8 (4)
C5—C6—N1—Cd1	−177.5 (4)	N1—Cd1—Br1—Cd1ⁱⁱⁱ	88.96 (12)
C6ⁱ—C6—N1—Cd1	0.5 (9)	N1ⁱ—Cd1—Br1—Cd1ⁱⁱⁱ	63.9 (4)
C2—C1—N1—C6	−0.1 (9)	Br1ⁱ—Cd1—Br1—Cd1ⁱⁱⁱ	−96.53 (2)
C2—C1—N1—Cd1	177.0 (5)	Br1ⁱⁱ—Cd1—Br1—Cd1ⁱⁱⁱ	174.26 (2)
C6—N1—Cd1—N1ⁱ	−0.2 (3)	Br1ⁱⁱⁱ—Cd1—Br1—Cd1ⁱⁱⁱ	0.0

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

Experimental details

Crystal data
Chemical formula	[CdBr₂(C₁₂H₁₂N₂)]
M_r	456.45
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	19.637 (5), 9.6563 (15), 7.485 (2)
β (°)	104.76 (2)
V (Å³)	1372.4 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	7.39
Crystal size (mm)	0.12 × 0.11 × 0.09

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.435, 0.548
No. of measured, independent and observed [I > 2σ(I)] reflections	5378, 1346, 1015
R_int	0.110
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.091, 1.03
No. of reflections	1346
No. of parameters	78
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.85, −0.70

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Cd1—N1	2.352 (4)	Cd1—Br1ⁱ	2.9351 (10)
Cd1—Br1	2.6676 (8)

Symmetry code: (i) x, −y, z+1/2.

Acknowledgements

We are grateful to the Islamic Azad University, Omidieh Branch, for financial support.

References

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