metal-organic compounds
Dibromido(6-methyl-2,2′-bipyridine-κ2N,N′)cobalt(II)
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
In the molecule of the title compound, [CoBr2(C11H10N2)], the CoII atom is four-coordinated in a distorted tetrahedral geometry by two N atoms from a chelating 6-methyl-2,2′-bipyridine ligand and two terminal Br atoms. In the crystal, π–π stacking interactions between the pyridine rings along the a-axis direction [centroid–centroid distance = 3.761 (7) Å] and C—H⋯Br hydrogen bonds in the bc plane together generate the three-dimensional packing.
Related literature
For related structures, see: Ahmadi et al. (2008a,b, 2009); Amani et al. (2009); Kalateh et al. (2010); Newkome et al. (1982); Onggo et al. (2005); Shirvan et al. (2012); Shirvan & Haydari Dezfuli (2012).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2007); cell SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97.
Supporting information
10.1107/S1600536812045230/hy2600sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812045230/hy2600Isup2.hkl
For the preparation of the title compound, a solution of 6-mbipy (0.28 g, 0.26 ml, 1.65 mmol) in acetonitrile (10 ml) was added to a solution of CoBr2 (0.36 g, 1.65 mmol) in acetonitrile (10 ml) and the resulting blue solution was stirred for 20 min at 313 K. This solution was left to evaporate slowly at room temperature. After one week, blue needle crystals of the title compound were isolated (yield: 0.47 g, 73.2%).
All H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93 (CH) and 0.96 (CH3) Å and with Uiso(H) = 1.2Ueq(C). The highest residual electron density was found 0.96 Å from Br1 the deepest hole 0.79 Å from Br1.
Data collection: APEX2 (Bruker, 2007); cell
SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).[CoBr2(C11H10N2)] | F(000) = 748 |
Mr = 388.94 | Dx = 2.000 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 6393 reflections |
a = 7.5541 (7) Å | θ = 3.1–26.0° |
b = 9.7249 (7) Å | µ = 7.49 mm−1 |
c = 17.7352 (16) Å | T = 173 K |
β = 97.392 (7)° | Needle, blue |
V = 1292.05 (19) Å3 | 0.45 × 0.13 × 0.10 mm |
Z = 4 |
Bruker APEXII CCD diffractometer | 2519 independent reflections |
Radiation source: fine-focus sealed tube | 1546 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.099 |
ϕ and ω scans | θmax = 26.0°, θmin = 3.1° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −7→9 |
Tmin = 0.379, Tmax = 0.512 | k = −10→11 |
6393 measured reflections | l = −21→21 |
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)] = 0.085 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.164 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0569P)2 + 5.329P] where P = (Fo2 + 2Fc2)/3 |
2519 reflections | (Δ/σ)max = 0.002 |
145 parameters | Δρmax = 2.16 e Å−3 |
0 restraints | Δρmin = −1.13 e Å−3 |
[CoBr2(C11H10N2)] | V = 1292.05 (19) Å3 |
Mr = 388.94 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.5541 (7) Å | µ = 7.49 mm−1 |
b = 9.7249 (7) Å | T = 173 K |
c = 17.7352 (16) Å | 0.45 × 0.13 × 0.10 mm |
β = 97.392 (7)° |
Bruker APEXII CCD diffractometer | 2519 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 1546 reflections with I > 2σ(I) |
Tmin = 0.379, Tmax = 0.512 | Rint = 0.099 |
6393 measured reflections |
R[F2 > 2σ(F2)] = 0.085 | 0 restraints |
wR(F2) = 0.164 | H-atom parameters constrained |
S = 1.05 | Δρmax = 2.16 e Å−3 |
2519 reflections | Δρmin = −1.13 e Å−3 |
145 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 | ||
C3 | 0.1467 (17) | 0.3377 (14) | 0.1282 (7) | 0.046 (3) | |
H3 | 0.1126 | 0.2832 | 0.1669 | 0.056* | |
C4 | 0.1737 (16) | 0.2801 (14) | 0.0583 (7) | 0.046 (3) | |
H4 | 0.1588 | 0.1861 | 0.0501 | 0.055* | |
Br1 | 0.04264 (18) | 0.91295 (15) | 0.11995 (7) | 0.0501 (4) | |
N2 | 0.2940 (12) | 0.7342 (12) | −0.0213 (5) | 0.042 (3) | |
C6 | 0.2426 (15) | 0.5016 (13) | 0.0149 (6) | 0.034 (3) | |
C7 | 0.2897 (14) | 0.6000 (13) | −0.0435 (6) | 0.034 (3) | |
C8 | 0.3225 (16) | 0.5617 (15) | −0.1157 (6) | 0.045 (3) | |
H8 | 0.3190 | 0.4698 | −0.1303 | 0.054* | |
C9 | 0.3607 (16) | 0.6643 (16) | −0.1658 (6) | 0.045 (4) | |
H9 | 0.3865 | 0.6417 | −0.2142 | 0.055* | |
C10 | 0.3601 (18) | 0.7992 (16) | −0.1431 (6) | 0.049 (4) | |
H10 | 0.3798 | 0.8692 | −0.1768 | 0.059* | |
N1 | 0.2173 (12) | 0.5578 (10) | 0.0835 (5) | 0.031 (2) | |
C11 | 0.3303 (17) | 0.8297 (15) | −0.0711 (6) | 0.043 (3) | |
H11 | 0.3356 | 0.9212 | −0.0558 | 0.052* | |
Br2 | 0.54925 (17) | 0.79979 (15) | 0.16326 (7) | 0.0467 (4) | |
Co1 | 0.2680 (2) | 0.76329 (17) | 0.09004 (8) | 0.0345 (4) | |
C5 | 0.2222 (17) | 0.3629 (13) | 0.0021 (6) | 0.040 (3) | |
H5 | 0.2414 | 0.3255 | −0.0444 | 0.047* | |
C2 | 0.1726 (16) | 0.4806 (14) | 0.1384 (7) | 0.041 (3) | |
C1 | 0.144 (2) | 0.5546 (17) | 0.2094 (7) | 0.070 (5) | |
H1A | 0.2213 | 0.5171 | 0.2516 | 0.084* | |
H1B | 0.0218 | 0.5439 | 0.2183 | 0.084* | |
H1C | 0.1697 | 0.6505 | 0.2042 | 0.084* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C3 | 0.033 (7) | 0.049 (9) | 0.057 (7) | 0.002 (7) | 0.002 (6) | 0.001 (6) |
C4 | 0.036 (7) | 0.036 (8) | 0.061 (8) | 0.007 (6) | −0.010 (6) | −0.022 (6) |
Br1 | 0.0389 (8) | 0.0543 (10) | 0.0579 (8) | 0.0073 (7) | 0.0089 (6) | −0.0186 (6) |
N2 | 0.023 (5) | 0.072 (8) | 0.029 (5) | 0.002 (5) | 0.002 (4) | −0.013 (5) |
C6 | 0.020 (6) | 0.042 (7) | 0.038 (6) | 0.008 (6) | −0.002 (4) | −0.013 (5) |
C7 | 0.020 (6) | 0.047 (8) | 0.033 (6) | 0.007 (6) | 0.002 (4) | −0.009 (5) |
C8 | 0.034 (7) | 0.062 (9) | 0.037 (6) | 0.010 (7) | −0.002 (5) | −0.026 (6) |
C9 | 0.025 (6) | 0.077 (11) | 0.035 (6) | 0.010 (7) | 0.005 (5) | −0.005 (6) |
C10 | 0.053 (9) | 0.060 (10) | 0.035 (6) | 0.019 (8) | 0.005 (6) | −0.003 (6) |
N1 | 0.021 (5) | 0.034 (6) | 0.039 (5) | −0.002 (4) | 0.010 (4) | −0.007 (4) |
C11 | 0.046 (8) | 0.047 (9) | 0.038 (6) | −0.012 (7) | 0.011 (5) | −0.001 (6) |
Br2 | 0.0342 (7) | 0.0557 (9) | 0.0488 (7) | 0.0003 (7) | −0.0004 (5) | −0.0266 (6) |
Co1 | 0.0306 (9) | 0.0390 (11) | 0.0347 (8) | −0.0018 (8) | 0.0070 (6) | −0.0138 (7) |
C5 | 0.042 (8) | 0.034 (7) | 0.042 (6) | 0.001 (6) | 0.002 (5) | −0.006 (6) |
C2 | 0.026 (7) | 0.046 (8) | 0.049 (7) | −0.005 (6) | −0.001 (5) | −0.005 (6) |
C1 | 0.095 (13) | 0.077 (12) | 0.040 (7) | −0.029 (10) | 0.014 (7) | −0.001 (7) |
Co1—Br1 | 2.352 (2) | C7—C8 | 1.386 (14) |
Co1—Br2 | 2.3698 (19) | C8—C9 | 1.391 (19) |
Co1—N1 | 2.035 (10) | C8—H8 | 0.9300 |
Co1—N2 | 2.029 (8) | C9—C10 | 1.372 (19) |
C3—C4 | 1.399 (17) | C9—H9 | 0.9300 |
C3—C2 | 1.411 (18) | C10—C11 | 1.357 (16) |
C3—H3 | 0.9300 | C10—H10 | 0.9300 |
C4—C5 | 1.366 (18) | N1—C2 | 1.309 (15) |
C4—H4 | 0.9300 | C11—H11 | 0.9300 |
N2—C11 | 1.334 (16) | C5—H5 | 0.9300 |
N2—C7 | 1.362 (16) | C2—C1 | 1.491 (18) |
C6—N1 | 1.369 (13) | C1—H1A | 0.9600 |
C6—C5 | 1.373 (17) | C1—H1B | 0.9600 |
C6—C7 | 1.487 (17) | C1—H1C | 0.9600 |
C4—C3—C2 | 118.3 (13) | C2—N1—C6 | 120.7 (11) |
C4—C3—H3 | 120.8 | C2—N1—Co1 | 125.8 (8) |
C2—C3—H3 | 120.8 | C6—N1—Co1 | 113.3 (8) |
C5—C4—C3 | 119.5 (13) | N2—C11—C10 | 123.0 (13) |
C5—C4—H4 | 120.2 | N2—C11—H11 | 118.5 |
C3—C4—H4 | 120.2 | C10—C11—H11 | 118.5 |
C11—N2—C7 | 118.3 (10) | N2—Co1—N1 | 81.3 (4) |
C11—N2—Co1 | 127.0 (9) | N2—Co1—Br1 | 118.0 (3) |
C7—N2—Co1 | 114.4 (8) | N1—Co1—Br1 | 119.0 (3) |
N1—C6—C5 | 120.9 (11) | N2—Co1—Br2 | 111.2 (3) |
N1—C6—C7 | 115.8 (10) | N1—Co1—Br2 | 109.1 (3) |
C5—C6—C7 | 123.3 (10) | Br1—Co1—Br2 | 114.06 (7) |
N2—C7—C8 | 121.6 (12) | C4—C5—C6 | 119.6 (11) |
N2—C7—C6 | 114.5 (9) | C4—C5—H5 | 120.2 |
C8—C7—C6 | 123.9 (12) | C6—C5—H5 | 120.2 |
C7—C8—C9 | 118.3 (13) | N1—C2—C3 | 120.9 (11) |
C7—C8—H8 | 120.9 | N1—C2—C1 | 115.6 (12) |
C9—C8—H8 | 120.9 | C3—C2—C1 | 123.4 (12) |
C10—C9—C8 | 119.3 (11) | C2—C1—H1A | 109.5 |
C10—C9—H9 | 120.3 | C2—C1—H1B | 109.5 |
C8—C9—H9 | 120.3 | H1A—C1—H1B | 109.5 |
C11—C10—C9 | 119.5 (13) | C2—C1—H1C | 109.5 |
C11—C10—H10 | 120.3 | H1A—C1—H1C | 109.5 |
C9—C10—H10 | 120.3 | H1B—C1—H1C | 109.5 |
C2—C3—C4—C5 | −0.6 (18) | C7—N2—Co1—N1 | −7.8 (8) |
C11—N2—C7—C8 | 0.2 (16) | C11—N2—Co1—Br1 | 60.6 (11) |
Co1—N2—C7—C8 | −173.8 (8) | C7—N2—Co1—Br1 | −126.1 (7) |
C11—N2—C7—C6 | −178.2 (10) | C11—N2—Co1—Br2 | −74.0 (10) |
Co1—N2—C7—C6 | 7.8 (12) | C7—N2—Co1—Br2 | 99.4 (7) |
N1—C6—C7—N2 | −2.6 (14) | C2—N1—Co1—N2 | −176.7 (10) |
C5—C6—C7—N2 | 176.5 (11) | C6—N1—Co1—N2 | 6.3 (7) |
N1—C6—C7—C8 | 179.1 (10) | C2—N1—Co1—Br1 | −59.5 (10) |
C5—C6—C7—C8 | −1.8 (18) | C6—N1—Co1—Br1 | 123.5 (7) |
N2—C7—C8—C9 | 0.1 (17) | C2—N1—Co1—Br2 | 73.7 (9) |
C6—C7—C8—C9 | 178.3 (11) | C6—N1—Co1—Br2 | −103.3 (7) |
C7—C8—C9—C10 | −1.7 (18) | C3—C4—C5—C6 | −0.5 (18) |
C8—C9—C10—C11 | 3.1 (19) | N1—C6—C5—C4 | 0.9 (18) |
C5—C6—N1—C2 | −0.2 (16) | C7—C6—C5—C4 | −178.1 (10) |
C7—C6—N1—C2 | 178.9 (10) | C6—N1—C2—C3 | −0.9 (17) |
C5—C6—N1—Co1 | 177.0 (9) | Co1—N1—C2—C3 | −177.7 (9) |
C7—C6—N1—Co1 | −3.9 (11) | C6—N1—C2—C1 | −178.3 (11) |
C7—N2—C11—C10 | 1.2 (18) | Co1—N1—C2—C1 | 4.9 (15) |
Co1—N2—C11—C10 | 174.3 (10) | C4—C3—C2—N1 | 1.3 (18) |
C9—C10—C11—N2 | −3 (2) | C4—C3—C2—C1 | 178.5 (13) |
C11—N2—Co1—N1 | 178.8 (11) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1A···Br1i | 0.96 | 2.89 | 3.849 (14) | 178 |
C8—H8···Br2ii | 0.93 | 2.89 | 3.771 (14) | 158 |
Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) −x+1, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | [CoBr2(C11H10N2)] |
Mr | 388.94 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 173 |
a, b, c (Å) | 7.5541 (7), 9.7249 (7), 17.7352 (16) |
β (°) | 97.392 (7) |
V (Å3) | 1292.05 (19) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 7.49 |
Crystal size (mm) | 0.45 × 0.13 × 0.10 |
Data collection | |
Diffractometer | Bruker APEXII CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2001) |
Tmin, Tmax | 0.379, 0.512 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6393, 2519, 1546 |
Rint | 0.099 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.085, 0.164, 1.05 |
No. of reflections | 2519 |
No. of parameters | 145 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 2.16, −1.13 |
Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006).
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1A···Br1i | 0.96 | 2.89 | 3.849 (14) | 178 |
C8—H8···Br2ii | 0.93 | 2.89 | 3.771 (14) | 158 |
Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) −x+1, −y+1, −z. |
Acknowledgements
We are grateful to the Islamic Azad University, Omidieh Branch, for financial support.
References
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Recently, we reported the synthesis and crystal structure of [In(6-mbipy)Cl3(DMSO)], (II) (Shirvan et al., 2012) and [Cd(6-mbipy)Br2(DMSO)], (III) (Shirvan & Haydari Dezfuli, 2012) (6-mbipy = 6-methyl-2,2'-bipyridine, DMSO = dimethyl sulfoxide). 6-Methyl-2,2'-bipyridine is a good ligand and a few complexes with 6-mbipy have been prepared, such as that of [Hg(6-mbipy)Cl2], (IV) (Ahmadi et al., 2008a), [Pt(6-mbipy)Cl4], (V) (Amani et al., 2009), [Pb4(NO3)8(6-mbipy)4], (VI) (Ahmadi et al., 2009), [Zn(6-mbipy)Br2], (VII) (Kalateh et al., 2010), [Zn(6-mbipy)Cl2], (VIII) (Ahmadi et al., 2008b), [Pd(6-mbipy)Cl2], (IX) (Newkome et al., 1982) and [Ru(6-mbipy)3][BF4]2, (X) (Onggo et al., 2005). We report herein the synthesis and crystal structure of the title compound, (I).
In the title compound (Fig. 1), the CoII atom is four-coordinated in a distorted tetrahedral geometry by two N atoms from a chelating 6-mbipy ligand and two terminal Br atoms (Table 1). In the crystal, intermolecular C—H···Br hydrogen bonds and π–π contacts (Table 2, Fig. 2) between the pyridine rings, Cg2···Cg3i [symmetry code: (i) 1-x, 1-y, -z, Cg2 and Cg3 are the centroids of the rings N1/C2–C6 and N2/C7–C11, respectively], with a centroid–centroid distance of 3.761 (7) Å, stabilize the structure.