Dibromido(6,6′-dimethyl-2,2′-bipyridine-κ2N,N′)cobalt(II)

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

doi:10.1107/S1600536812041980

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 11| November 2012| Page m1363

doi:10.1107/S1600536812041980

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Dibromido(6,6′-dimethyl-2,2′-bipyridine-κ²N,N′)cobalt(II)

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

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

(Received 6 October 2012; accepted 7 October 2012; online 13 October 2012)

In the title compound, [CoBr₂(C₁₂H₁₂N₂)], the Co^II atom is four-coordinated in a distorted tetrahedral geometry by two N atoms from a 6,6′-dimethyl-2,2′-bipyridine ligand and by two terminal Br atoms. Intermolecular C—H⋯Br hydrogen bonds and π–π stacking between the pyridine rings in the bc plane [centroid–centroid distance = 3.725 (3) Å] are present in the crystal structure.

Related literature

For related structures, see: Akbarzadeh Torbati et al. (2010 ); Alizadeh et al. (2011 , 2009 ); Itoh et al. (2005 ); Kou et al. (2008 ); Onggo et al. (2005 ); Shirvan & Haydari Dezfuli (2012 ).

Experimental

Crystal data

[CoBr₂(C₁₂H₁₂N₂)]
M_r = 402.97
Monoclinic, P 2₁ /c
a = 7.6550 (6) Å
b = 10.2577 (9) Å
c = 18.0030 (16) Å
β = 95.779 (7)°
V = 1406.5 (2) Å³
Z = 4
Mo Kα radiation
μ = 6.88 mm⁻¹
T = 298 K
0.30 × 0.24 × 0.18 mm

Data collection

Bruker APEXII CCD area detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.149, T_max = 0.302
7259 measured reflections
2766 independent reflections
1753 reflections with I > 2σ(I)
R_int = 0.068

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.089
S = 0.95
2766 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.56 e Å⁻³

Table 1
Selected bond lengths (Å)

Co1—N1	2.044 (4)
Co1—N2	2.037 (4)
Co1—Br1	2.3594 (10)
Co1—Br2	2.3588 (10)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8⋯Br1ⁱ	0.93	2.92	3.696 (5)	142
C12—H12C⋯Br1ⁱⁱ	0.96	2.89	3.847 (6)	172
Symmetry codes: (i) -x, -y+1, -z; (ii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT (Bruker, 2005); 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/S1600536812041980/xu5630sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812041980/xu5630Isup2.hkl

checkCIF report

Comment top

6,6'-Dimethyl-2,2'-bipyridine (6,6'-dmbipy), is a good bidentate ligand, and numerous complexes with 6,6'-dmbipy have been prepared, such as that of zinc (Alizadeh et al., 2009), copper (Itoh et al., 2005), cadmium (Shirvan & Haydari Dezfuli, 2012), cobalt (Akbarzadeh Torbati et al., 2010), nickel (Kou et al., 2008), ruthenium (Onggo et al., 2005) and mercury (Alizadeh et al., 2011). We report herein the synthesis and crystal structure of the title compound.

In the title compound, (Fig. 1), the Co^II atom is four-coordinated in a distorted tetrahedral geometry by two N atoms from a 6,6'-dimethyl-2,2'-bipyridine and two terminal Br atoms. The Co—Br and Co—N bond lengths and angles are collected in Table 1.

In the crystal structure, intermolecular C—H···Br hydrogen bonds (Table 2) and π-π contacts (Fig. 2) between the pyridine rings, Cg2—Cg3ⁱ [symmetry cods: (i) -x, 1 - y, -z, where Cg2 and Cg3 are centroids of the rings (N1/C2–C6) and (N2/C7–C11), respectively] may stabilize the structure, with centroid–centroid distance of 3.725 (3) Å.

Related literature top

For related structures, see: Akbarzadeh Torbati et al. (2010); Alizadeh et al. (2011, 2009); Itoh et al. (2005); Kou et al. (2008); Onggo et al. (2005); Shirvan & Haydari Dezfuli (2012).

Experimental top

For the preparation of the title compound, a solution of 6,6'-dimethyl-2,2'-bipyridine (0.25 g, 1.33 mmol) in methanol (10 ml) was added to a solution of CoBr₂ (0.29 g, 1.33 mmol) in acetonitrile (15 ml) and the resulting blue solution was stirred for 15 min at 313 K. This solution was left to evaporate slowly at room temperature. After one week, blue block crystals of the title compound were isolated (yield 0.41 g, 76.5%).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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.
	Fig. 2. Unit-cell packing diagram for title molecule. Hydrogen bonds are shown as dashed lines.

Dibromido(6,6'-dimethyl-2,2'-bipyridine-κ²N,N')cobalt(II) top

Crystal data top

[CoBr₂(C₁₂H₁₂N₂)]	F(000) = 780
M_r = 402.97	D_x = 1.903 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7259 reflections
a = 7.6550 (6) Å	θ = 2.3–26.0°
b = 10.2577 (9) Å	µ = 6.88 mm⁻¹
c = 18.0030 (16) Å	T = 298 K
β = 95.779 (7)°	Block, blue
V = 1406.5 (2) Å³	0.30 × 0.24 × 0.18 mm
Z = 4

Data collection top

Bruker APEXII CCD area detector diffractometer	2766 independent reflections
Radiation source: fine-focus sealed tube	1753 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.068
ω scans	θ_max = 26.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −8→9
T_min = 0.149, T_max = 0.302	k = −12→11
7259 measured reflections	l = −22→22

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.089	H-atom parameters constrained
S = 0.95	w = 1/[σ²(F_o²) + (0.0371P)²] where P = (F_o² + 2F_c²)/3
2766 reflections	(Δ/σ)_max = 0.005
154 parameters	Δρ_max = 0.51 e Å⁻³
0 restraints	Δρ_min = −0.56 e Å⁻³

Crystal data top

[CoBr₂(C₁₂H₁₂N₂)]	V = 1406.5 (2) Å³
M_r = 402.97	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.6550 (6) Å	µ = 6.88 mm⁻¹
b = 10.2577 (9) Å	T = 298 K
c = 18.0030 (16) Å	0.30 × 0.24 × 0.18 mm
β = 95.779 (7)°

Data collection top

Bruker APEXII CCD area detector diffractometer	2766 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1753 reflections with I > 2σ(I)
T_min = 0.149, T_max = 0.302	R_int = 0.068
7259 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.089	H-atom parameters constrained
S = 0.95	Δρ_max = 0.51 e Å⁻³
2766 reflections	Δρ_min = −0.56 e Å⁻³
154 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	0.3959 (11)	0.8727 (6)	−0.0503 (3)	0.074 (2)
H1A	0.4872	0.8803	−0.0098	0.089*
H1B	0.2921	0.9159	−0.0372	0.089*
H1C	0.4338	0.9122	−0.0942	0.089*
C2	0.3572 (8)	0.7343 (6)	−0.0648 (3)	0.0494 (14)
C3	0.3757 (8)	0.6766 (7)	−0.1338 (3)	0.0566 (16)
H3	0.4156	0.7252	−0.1723	0.068*
C4	0.3342 (9)	0.5468 (7)	−0.1441 (3)	0.0651 (18)
H4	0.3435	0.5077	−0.1901	0.078*
C5	0.2791 (8)	0.4753 (6)	−0.0865 (3)	0.0550 (15)
H5	0.2506	0.3876	−0.0930	0.066*
C6	0.2665 (7)	0.5352 (5)	−0.0188 (3)	0.0397 (12)
C7	0.2137 (7)	0.4644 (5)	0.0477 (3)	0.0421 (12)
C8	0.1766 (8)	0.3330 (5)	0.0476 (3)	0.0570 (16)
H8	0.1821	0.2838	0.0045	0.068*
C9	0.1312 (9)	0.2751 (6)	0.1121 (4)	0.0687 (19)
H9	0.1056	0.1865	0.1131	0.082*
C10	0.1245 (8)	0.3503 (6)	0.1744 (4)	0.0592 (16)
H10	0.0960	0.3120	0.2185	0.071*
C11	0.1592 (8)	0.4813 (6)	0.1731 (3)	0.0504 (14)
C12	0.1535 (10)	0.5666 (7)	0.2391 (3)	0.077 (2)
H12A	0.0704	0.6355	0.2275	0.092*
H12B	0.2677	0.6033	0.2525	0.092*
H12C	0.1187	0.5164	0.2801	0.092*
N1	0.3039 (6)	0.6627 (4)	−0.0087 (2)	0.0385 (10)
N2	0.2047 (6)	0.5381 (4)	0.1095 (2)	0.0387 (10)
Co1	0.26905 (10)	0.72871 (7)	0.09589 (3)	0.0414 (2)
Br1	0.03425 (10)	0.87570 (7)	0.10302 (4)	0.0703 (2)
Br2	0.52149 (9)	0.80174 (6)	0.17019 (3)	0.0598 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.109 (6)	0.062 (4)	0.054 (3)	−0.021 (4)	0.019 (4)	0.010 (3)
C2	0.053 (4)	0.056 (3)	0.039 (3)	0.008 (3)	0.002 (3)	0.006 (2)
C3	0.057 (4)	0.082 (5)	0.032 (3)	0.006 (3)	0.009 (3)	0.003 (3)
C4	0.067 (5)	0.085 (5)	0.043 (3)	0.013 (4)	0.007 (3)	−0.025 (3)
C5	0.056 (4)	0.058 (4)	0.051 (3)	0.002 (3)	0.005 (3)	−0.019 (3)
C6	0.034 (3)	0.043 (3)	0.040 (3)	0.003 (2)	−0.001 (2)	−0.011 (2)
C7	0.035 (3)	0.037 (3)	0.051 (3)	0.002 (2)	−0.007 (2)	−0.003 (2)
C8	0.056 (4)	0.041 (3)	0.070 (4)	−0.008 (3)	−0.012 (3)	−0.012 (3)
C9	0.066 (5)	0.038 (3)	0.099 (5)	−0.010 (3)	−0.010 (4)	0.012 (3)
C10	0.054 (4)	0.051 (4)	0.072 (4)	−0.013 (3)	0.001 (3)	0.018 (3)
C11	0.046 (4)	0.053 (4)	0.052 (3)	−0.005 (3)	0.006 (3)	0.011 (3)
C12	0.112 (6)	0.076 (5)	0.047 (3)	−0.018 (4)	0.027 (4)	0.006 (3)
N1	0.042 (3)	0.039 (2)	0.035 (2)	−0.002 (2)	0.0043 (19)	−0.0038 (17)
N2	0.038 (3)	0.034 (2)	0.043 (2)	−0.005 (2)	0.0007 (19)	−0.0013 (18)
Co1	0.0525 (5)	0.0357 (4)	0.0369 (3)	−0.0046 (3)	0.0083 (3)	−0.0058 (3)
Br1	0.0725 (5)	0.0601 (4)	0.0781 (4)	0.0177 (4)	0.0062 (3)	−0.0207 (3)
Br2	0.0619 (4)	0.0660 (4)	0.0508 (3)	−0.0135 (3)	0.0023 (3)	−0.0131 (3)

Geometric parameters (Å, º) top

C1—C2	1.468 (8)	C8—C9	1.379 (8)
C1—H1A	0.9600	C8—H8	0.9300
C1—H1B	0.9600	C9—C10	1.367 (9)
C1—H1C	0.9600	C9—H9	0.9300
C2—N1	1.345 (6)	C10—C11	1.370 (8)
C2—C3	1.396 (7)	C10—H10	0.9300
C3—C4	1.377 (9)	C11—N2	1.360 (6)
C3—H3	0.9300	C11—C12	1.481 (8)
C4—C5	1.371 (9)	C12—H12A	0.9600
C4—H4	0.9300	C12—H12B	0.9600
C5—C6	1.378 (7)	C12—H12C	0.9600
C5—H5	0.9300	Co1—N1	2.044 (4)
C6—N1	1.347 (6)	Co1—N2	2.037 (4)
C6—C7	1.490 (7)	Co1—Br1	2.3594 (10)
C7—N2	1.354 (6)	Co1—Br2	2.3588 (10)
C7—C8	1.377 (7)

C2—C1—H1A	109.5	C10—C9—C8	118.8 (6)
C2—C1—H1B	109.5	C10—C9—H9	120.6
H1A—C1—H1B	109.5	C8—C9—H9	120.6
C2—C1—H1C	109.5	C9—C10—C11	121.0 (6)
H1A—C1—H1C	109.5	C9—C10—H10	119.5
H1B—C1—H1C	109.5	C11—C10—H10	119.5
N1—C2—C3	120.1 (5)	N2—C11—C10	120.1 (5)
N1—C2—C1	117.7 (5)	N2—C11—C12	116.9 (5)
C3—C2—C1	122.1 (5)	C10—C11—C12	122.9 (5)
C4—C3—C2	119.2 (5)	C11—C12—H12A	109.5
C4—C3—H3	120.4	C11—C12—H12B	109.5
C2—C3—H3	120.4	H12A—C12—H12B	109.5
C5—C4—C3	120.0 (5)	C11—C12—H12C	109.5
C5—C4—H4	120.0	H12A—C12—H12C	109.5
C3—C4—H4	120.0	H12B—C12—H12C	109.5
C4—C5—C6	119.0 (6)	C2—N1—C6	120.4 (4)
C4—C5—H5	120.5	C2—N1—Co1	126.0 (3)
C6—C5—H5	120.5	C6—N1—Co1	113.5 (3)
N1—C6—C5	121.3 (5)	C7—N2—C11	119.4 (4)
N1—C6—C7	115.9 (4)	C7—N2—Co1	113.8 (3)
C5—C6—C7	122.8 (5)	C11—N2—Co1	126.8 (3)
N2—C7—C8	121.3 (5)	N2—Co1—N1	81.30 (15)
N2—C7—C6	115.4 (4)	N2—Co1—Br2	115.50 (12)
C8—C7—C6	123.3 (5)	N1—Co1—Br2	116.88 (13)
C7—C8—C9	119.4 (6)	N2—Co1—Br1	114.33 (13)
C7—C8—H8	120.3	N1—Co1—Br1	115.65 (12)
C9—C8—H8	120.3	Br2—Co1—Br1	110.57 (4)

N1—C2—C3—C4	1.8 (9)	C5—C6—N1—Co1	178.5 (4)
C1—C2—C3—C4	−178.9 (6)	C7—C6—N1—Co1	−2.2 (6)
C2—C3—C4—C5	−1.4 (10)	C8—C7—N2—C11	0.4 (8)
C3—C4—C5—C6	−0.1 (10)	C6—C7—N2—C11	−179.4 (5)
C4—C5—C6—N1	1.3 (9)	C8—C7—N2—Co1	179.1 (5)
C4—C5—C6—C7	−177.9 (5)	C6—C7—N2—Co1	−0.6 (6)
N1—C6—C7—N2	1.9 (7)	C10—C11—N2—C7	0.6 (8)
C5—C6—C7—N2	−178.8 (5)	C12—C11—N2—C7	179.4 (5)
N1—C6—C7—C8	−177.9 (5)	C10—C11—N2—Co1	−177.9 (4)
C5—C6—C7—C8	1.4 (9)	C12—C11—N2—Co1	0.8 (8)
N2—C7—C8—C9	−0.7 (9)	C7—N2—Co1—N1	−0.4 (4)
C6—C7—C8—C9	179.0 (5)	C11—N2—Co1—N1	178.2 (5)
C7—C8—C9—C10	0.0 (10)	C7—N2—Co1—Br2	−116.1 (3)
C8—C9—C10—C11	1.1 (10)	C11—N2—Co1—Br2	62.5 (5)
C9—C10—C11—N2	−1.4 (10)	C7—N2—Co1—Br1	113.9 (3)
C9—C10—C11—C12	180.0 (6)	C11—N2—Co1—Br1	−67.5 (5)
C3—C2—N1—C6	−0.6 (8)	C2—N1—Co1—N2	−179.1 (5)
C1—C2—N1—C6	−180.0 (6)	C6—N1—Co1—N2	1.5 (4)
C3—C2—N1—Co1	180.0 (4)	C2—N1—Co1—Br2	−64.8 (5)
C1—C2—N1—Co1	0.6 (8)	C6—N1—Co1—Br2	115.7 (3)
C5—C6—N1—C2	−0.9 (8)	C2—N1—Co1—Br1	68.0 (5)
C7—C6—N1—C2	178.3 (5)	C6—N1—Co1—Br1	−111.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···Br1ⁱ	0.93	2.92	3.696 (5)	142
C12—H12C···Br1ⁱⁱ	0.96	2.89	3.847 (6)	172

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

Experimental details

Crystal data
Chemical formula	[CoBr₂(C₁₂H₁₂N₂)]
M_r	402.97
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	7.6550 (6), 10.2577 (9), 18.0030 (16)
β (°)	95.779 (7)
V (Å³)	1406.5 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	6.88
Crystal size (mm)	0.30 × 0.24 × 0.18

Data collection
Diffractometer	Bruker APEXII CCD area detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.149, 0.302
No. of measured, independent and observed [I > 2σ(I)] reflections	7259, 2766, 1753
R_int	0.068
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.089, 0.95
No. of reflections	2766
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.51, −0.56

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Co1—N1	2.044 (4)	Co1—Br1	2.3594 (10)
Co1—N2	2.037 (4)	Co1—Br2	2.3588 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···Br1ⁱ	0.93	2.92	3.696 (5)	142
C12—H12C···Br1ⁱⁱ	0.96	2.89	3.847 (6)	172

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

Acknowledgements

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

References

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