catena-Poly[[(4,4′-dimethyl-2,2′-bipyridine-κ2N,N′)cadmium]-di-μ-bromido]

Shirvan, S.A.; Haydari Dezfuli, S.; Khazali, F.; Borsalani, A.

doi:10.1107/S1600536812046636

metal-organic compounds

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Volume 68| Part 12| December 2012| Pages m1493-m1494

doi:10.1107/S1600536812046636

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catena-Poly[[(4,4′-dimethyl-2,2′-bipyridine-κ²N,N′)cadmium]-di-μ-bromido]

Sadif A. Shirvan,^a ^* Sara Haydari Dezfuli,^a Fereydoon Khazali ^a and Ali Borsalani ^b

^aDepartment of Chemistry, Omidieh Branch, Islamic Azad University, Omidieh, Iran, and ^bDepartment of Petroleum Engineering, Omidieh Branch, Islamic Azad University, Omidieh, Iran
^*Correspondence e-mail: sadifchemist@hotmail.com

(Received 11 November 2012; accepted 12 November 2012; online 17 November 2012)

In the crystal of the title polymeric compound, [CdBr₂(C₁₂H₁₂N₂)]_n, the Cd^II cation is located on a twofold rotation axis and is six-coordinated in a distorted octahedral geometry formed by two N atoms from the 4,4′-dimethyl-2,2′-bipyridine ligand and by four bridging Br⁻ anions. The bridging function of the Br⁻ anions leads to a polymeric chain running along the c axis. Weak C—H⋯π interactions observed between adjacent chains are effective in the stabilization of the three-dimensional packing.

Related literature

For related structures, see: Ahmadi et al. (2008 ); Alizadeh et al. (2010 ); Amani et al. (2009 ); Bellusci et al. (2008 ); Han et al. (2006 ); Hojjat Kashani et al. (2008 ); Kalateh et al. (2008 , 2010 ); Shirvan & Haydari Dezfuli (2012 ); Sofetis et al. (2006 ); Willett et al. (2001 ); Yousefi et al. (2008 ); Zhang (2007 ).

Experimental

Crystal data

[CdBr₂(C₁₂H₁₂N₂)]
M_r = 456.45
Monoclinic, C 2/c
a = 17.979 (4) Å
b = 10.5319 (18) Å
c = 7.4496 (16) Å
β = 108.403 (17)°
V = 1338.5 (5) Å³
Z = 4
Mo Kα radiation
μ = 7.58 mm⁻¹
T = 298 K
0.25 × 0.21 × 0.20 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.188, T_max = 0.246
3392 measured reflections
1313 independent reflections
909 reflections with I > 2σ(I)
R_int = 0.095

Refinement

R[F² > 2σ(F²)] = 0.079
wR(F²) = 0.155
S = 1.24
1313 reflections
78 parameters
H-atom parameters constrained
Δρ_max = 1.20 e Å⁻³
Δρ_min = −0.88 e Å⁻³

Table 1
Selected bond lengths (Å)

Cd1—N1	2.357 (10)
Cd1—Br1	2.6852 (17)
Cd1—Br1ⁱ	2.8789 (16)
Symmetry code: (i) $[x, -y+2, z-{\script{1\over 2}}]$ .

Table 2
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the N1-pyridine ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4B⋯Cgⁱⁱ	0.96	2.84	3.575 (16)	135
Symmetry code: (ii) $[x, -y+1, z-{\script{1\over 2}}]$ .

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/S1600536812046636/xu5649sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812046636/xu5649Isup2.hkl

checkCIF report

Comment top

Recently, we reported the synthes and crystal structure of [CdBr₂(4,4'-dmbpy)(DMSO)], (Shirvan & Haydari Dezfuli, 2012) [where 4,4'-dmbpy is 4,4'-dimethyl-2,2'-bipyridine and DMSO is dimethyl sulfoxide]. 4,4'-Dimethyl-2,2'-bipyridine is a good bidentate ligand, and numerous complexes with 4,4'-dmbipy have been prepared, such as that of mercury (Kalateh et al., 2008; Yousefi et al., 2008), indium (Ahmadi et al., 2008), iron (Amani et al., 2009), platin (Hojjat Kashani et al., 2008), silver (Bellusci et al., 2008), gallium (Sofetis et al., 2006), copper (Willett et al., 2001), cadmium (Kalateh et al., 2010) and zinc (Alizadeh et al., 2010). Here, we report the synthesis and structure of the title compound.

The asymmetric unit of the title compound, (Fig. 1), contains half-molecule; a twofold rotation axis passes through the Cd atom. The Cd^II cation is six-coordinated in a distorted octahedral geometry formed by two N atoms from the 4,4'-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 b axis. The Cd—N and Cd—Br 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); Alizadeh et al. (2010); Amani et al. (2009); Bellusci et al. (2008); Han et al. (2006); Hojjat Kashani et al. (2008); Kalateh et al. (2008, 2010); Shirvan & Haydari Dezfuli (2012); Sofetis et al. (2006); Willett et al. (2001); Yousefi et al. (2008); Zhang (2007).

Experimental top

For the preparation of the title compound, a solution of 4,4'-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 (5 ml) at room temperature. The suitable crystals for X-ray diffraction experiment were obtained by methanol diffusion to a colorless solution in dimethylformamide. 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 50% probability level.

catena-Poly[[(4,4'-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 = 2.265 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3392 reflections
a = 17.979 (4) Å	θ = 2.3–26.0°
b = 10.5319 (18) Å	µ = 7.58 mm⁻¹
c = 7.4496 (16) Å	T = 298 K
β = 108.403 (17)°	Prism, colorless
V = 1338.5 (5) Å³	0.25 × 0.21 × 0.20 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	1313 independent reflections
Radiation source: fine-focus sealed tube	909 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.095
ω scans	θ_max = 26.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −22→22
T_min = 0.188, T_max = 0.246	k = −12→12
3392 measured reflections	l = −7→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)] = 0.079	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.155	H-atom parameters constrained
S = 1.24	w = 1/[σ²(F_o²) + (0.0098P)² + 54.7076P] where P = (F_o² + 2F_c²)/3
1313 reflections	(Δ/σ)_max = 0.022
78 parameters	Δρ_max = 1.20 e Å⁻³
0 restraints	Δρ_min = −0.88 e Å⁻³

Crystal data top

[CdBr₂(C₁₂H₁₂N₂)]	V = 1338.5 (5) Å³
M_r = 456.45	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 17.979 (4) Å	µ = 7.58 mm⁻¹
b = 10.5319 (18) Å	T = 298 K
c = 7.4496 (16) Å	0.25 × 0.21 × 0.20 mm
β = 108.403 (17)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	1313 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	909 reflections with I > 2σ(I)
T_min = 0.188, T_max = 0.246	R_int = 0.095
3392 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.079	0 restraints
wR(F²) = 0.155	H-atom parameters constrained
S = 1.24	w = 1/[σ²(F_o²) + (0.0098P)² + 54.7076P] where P = (F_o² + 2F_c²)/3
1313 reflections	Δρ_max = 1.20 e Å⁻³
78 parameters	Δρ_min = −0.88 e Å⁻³

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	0.92501 (14)	0.2500	0.0312 (4)
Br1	0.09337 (9)	1.08683 (16)	0.4997 (2)	0.0439 (5)
N1	−0.0688 (6)	0.7414 (11)	0.1090 (15)	0.030 (3)
C6	−0.0397 (7)	0.6266 (12)	0.1779 (18)	0.023 (3)
C5	−0.0804 (7)	0.5157 (13)	0.111 (2)	0.030 (3)
H5	−0.0585	0.4376	0.1574	0.036*
C1	−0.1384 (8)	0.7427 (15)	−0.025 (2)	0.042 (4)
H1	−0.1579	0.8209	−0.0767	0.050*
C3	−0.1535 (8)	0.5209 (14)	−0.025 (2)	0.031 (3)
C4	−0.2002 (8)	0.4012 (14)	−0.094 (2)	0.040 (4)
H4A	−0.2098	0.3586	0.0101	0.048*
H4B	−0.1712	0.3462	−0.1505	0.048*
H4C	−0.2493	0.4229	−0.1869	0.048*
C2	−0.1825 (8)	0.6396 (14)	−0.091 (2)	0.036 (3)
H2	−0.2318	0.6478	−0.1806	0.043*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.0363 (8)	0.0203 (7)	0.0304 (9)	0.000	0.0011 (6)	0.000
Br1	0.0434 (10)	0.0394 (9)	0.0520 (12)	−0.0169 (7)	0.0195 (8)	−0.0153 (8)
N1	0.032 (6)	0.027 (5)	0.022 (6)	−0.009 (5)	−0.005 (4)	−0.006 (5)
C6	0.018 (6)	0.024 (6)	0.030 (7)	0.002 (5)	0.009 (5)	0.002 (6)
C5	0.019 (6)	0.031 (7)	0.045 (9)	0.002 (5)	0.015 (6)	−0.002 (6)
C1	0.034 (8)	0.030 (7)	0.046 (9)	0.003 (6)	−0.008 (7)	0.010 (7)
C3	0.027 (7)	0.042 (8)	0.023 (7)	0.001 (6)	0.005 (5)	−0.010 (6)
C4	0.037 (8)	0.044 (9)	0.035 (8)	−0.012 (7)	0.006 (6)	−0.003 (7)
C2	0.026 (7)	0.042 (8)	0.031 (8)	0.002 (6)	−0.005 (6)	0.004 (7)

Geometric parameters (Å, º) top

Cd1—N1ⁱ	2.357 (10)	C5—C3	1.383 (18)
Cd1—N1	2.357 (10)	C5—H5	0.9300
Cd1—Br1ⁱ	2.6852 (17)	C1—C2	1.34 (2)
Cd1—Br1	2.6852 (17)	C1—H1	0.9300
Cd1—Br1ⁱⁱ	2.8789 (16)	C3—C2	1.39 (2)
Cd1—Br1ⁱⁱⁱ	2.8790 (16)	C3—C4	1.513 (19)
Br1—Cd1ⁱⁱⁱ	2.8789 (16)	C4—H4A	0.9600
N1—C1	1.331 (16)	C4—H4B	0.9600
N1—C6	1.353 (17)	C4—H4C	0.9600
C6—C5	1.384 (18)	C2—H2	0.9300
C6—C6ⁱ	1.49 (2)

N1ⁱ—Cd1—N1	69.7 (5)	N1—C6—C6ⁱ	116.2 (7)
N1ⁱ—Cd1—Br1ⁱ	162.8 (3)	C5—C6—C6ⁱ	122.4 (7)
N1—Cd1—Br1ⁱ	95.0 (3)	C3—C5—C6	120.1 (13)
N1ⁱ—Cd1—Br1	95.0 (3)	C3—C5—H5	119.9
N1—Cd1—Br1	162.8 (3)	C6—C5—H5	119.9
Br1ⁱ—Cd1—Br1	101.21 (9)	N1—C1—C2	125.0 (14)
N1ⁱ—Cd1—Br1ⁱⁱ	85.5 (3)	N1—C1—H1	117.5
N1—Cd1—Br1ⁱⁱ	90.4 (3)	C2—C1—H1	117.5
Br1ⁱ—Cd1—Br1ⁱⁱ	86.77 (5)	C5—C3—C2	117.4 (13)
Br1—Cd1—Br1ⁱⁱ	96.39 (5)	C5—C3—C4	121.0 (13)
N1ⁱ—Cd1—Br1ⁱⁱⁱ	90.4 (3)	C2—C3—C4	121.6 (12)
N1—Cd1—Br1ⁱⁱⁱ	85.5 (3)	C3—C4—H4A	109.5
Br1ⁱ—Cd1—Br1ⁱⁱⁱ	96.39 (5)	C3—C4—H4B	109.5
Br1—Cd1—Br1ⁱⁱⁱ	86.77 (5)	H4A—C4—H4B	109.5
Br1ⁱⁱ—Cd1—Br1ⁱⁱⁱ	175.03 (9)	C3—C4—H4C	109.5
Cd1—Br1—Cd1ⁱⁱⁱ	93.23 (5)	H4A—C4—H4C	109.5
C1—N1—C6	116.9 (12)	H4B—C4—H4C	109.5
C1—N1—Cd1	124.3 (10)	C1—C2—C3	119.1 (12)
C6—N1—Cd1	118.6 (8)	C1—C2—H2	120.4
N1—C6—C5	121.3 (11)	C3—C2—H2	120.4

N1ⁱ—Cd1—Br1—Cd1ⁱⁱⁱ	−90.1 (3)	Br1ⁱⁱⁱ—Cd1—N1—C6	−89.3 (10)
N1—Cd1—Br1—Cd1ⁱⁱⁱ	−63.5 (10)	C1—N1—C6—C5	0 (2)
Br1ⁱ—Cd1—Br1—Cd1ⁱⁱⁱ	95.88 (5)	Cd1—N1—C6—C5	175.0 (10)
Br1ⁱⁱ—Cd1—Br1—Cd1ⁱⁱⁱ	−176.16 (7)	C1—N1—C6—C6ⁱ	177.6 (15)
Br1ⁱⁱⁱ—Cd1—Br1—Cd1ⁱⁱⁱ	0.0	Cd1—N1—C6—C6ⁱ	−7.7 (19)
N1ⁱ—Cd1—N1—C1	177.1 (15)	N1—C6—C5—C3	−2 (2)
Br1ⁱ—Cd1—N1—C1	−11.0 (12)	C6ⁱ—C6—C5—C3	−179.3 (14)
Br1—Cd1—N1—C1	148.7 (10)	C6—N1—C1—C2	2 (2)
Br1ⁱⁱ—Cd1—N1—C1	−97.8 (12)	Cd1—N1—C1—C2	−171.9 (13)
Br1ⁱⁱⁱ—Cd1—N1—C1	85.0 (12)	C6—C5—C3—C2	1 (2)
N1ⁱ—Cd1—N1—C6	2.9 (7)	C6—C5—C3—C4	−177.8 (13)
Br1ⁱ—Cd1—N1—C6	174.7 (9)	N1—C1—C2—C3	−3 (3)
Br1—Cd1—N1—C6	−25.6 (17)	C5—C3—C2—C1	1 (2)
Br1ⁱⁱ—Cd1—N1—C6	87.9 (10)	C4—C3—C2—C1	−179.7 (15)

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

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the N1-pyridine ring.

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4B···Cg^iv	0.96	2.84	3.575 (16)	135

Symmetry code: (iv) x, −y+1, z−1/2.

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)	17.979 (4), 10.5319 (18), 7.4496 (16)
β (°)	108.403 (17)
V (Å³)	1338.5 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	7.58
Crystal size (mm)	0.25 × 0.21 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.188, 0.246
No. of measured, independent and observed [I > 2σ(I)] reflections	3392, 1313, 909
R_int	0.095
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.079, 0.155, 1.24
No. of reflections	1313
No. of parameters	78
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.0098P)² + 54.7076P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	1.20, −0.88

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

Selected bond lengths (Å) top

Cd1—N1	2.357 (10)	Cd1—Br1ⁱ	2.8789 (16)
Cd1—Br1	2.6852 (17)

Symmetry code: (i) x, −y+2, z−1/2.

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the N1-pyridine ring.

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4B···Cgⁱⁱ	0.96	2.8348	3.575 (16)	135

Symmetry code: (ii) x, −y+1, z−1/2.

Acknowledgements

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

References

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Volume 68| Part 12| December 2012| Pages m1493-m1494

doi:10.1107/S1600536812046636

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