metal-organic compounds
Dibromido(6,6′-dimethyl-2,2′-bipyridine-κ2N,N′)cobalt(II)
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
In the title compound, [CoBr2(C12H12N2)], the CoII 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
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Refinement
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Data collection: APEX2 (Bruker, 2005); cell 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
10.1107/S1600536812041980/xu5630sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812041980/xu5630Isup2.hkl
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%).
H atoms were positioned geometrically with C—H = 0.93 and 0.96 Å and constrained to ride on their parent atoms, Uiso(H) = 1.2Ueq(C) for methyl H atoms and 1.2Ueq(C) for aromatic H atoms.
Data collection: APEX2 (Bruker, 2005); cell
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).[CoBr2(C12H12N2)] | F(000) = 780 |
Mr = 402.97 | Dx = 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 |
Bruker APEXII CCD area detector diffractometer | 2766 independent reflections |
Radiation source: fine-focus sealed tube | 1753 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.068 |
ω scans | θmax = 26.0°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −8→9 |
Tmin = 0.149, Tmax = 0.302 | k = −12→11 |
7259 measured reflections | l = −22→22 |
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(Fo2) + (0.0371P)2] where P = (Fo2 + 2Fc2)/3 |
2766 reflections | (Δ/σ)max = 0.005 |
154 parameters | Δρmax = 0.51 e Å−3 |
0 restraints | Δρmin = −0.56 e Å−3 |
[CoBr2(C12H12N2)] | V = 1406.5 (2) Å3 |
Mr = 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)° |
Bruker APEXII CCD area detector diffractometer | 2766 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 1753 reflections with I > 2σ(I) |
Tmin = 0.149, Tmax = 0.302 | Rint = 0.068 |
7259 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.089 | H-atom parameters constrained |
S = 0.95 | Δρmax = 0.51 e Å−3 |
2766 reflections | Δρmin = −0.56 e Å−3 |
154 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
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) |
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) |
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) |
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)] |
Mr | 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) |
Tmin, Tmax | 0.149, 0.302 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7259, 2766, 1753 |
Rint | 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 |
Δρmax, Δρmin (e Å−3) | 0.51, −0.56 |
Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008).
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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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 CoII 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.