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Acta Cryst. (2009). E65, m1664    [ doi:10.1107/S1600536809049034 ]

Bis(2,2'-bipyridine-[kappa]2N,N')chloridocobalt(II) perchlorate

Z. Gao and F. Li

Abstract top

In the cation of the title compound, [CoCl(C10H8N2)2]ClO4, the CoII atom displays a distorted trigonal-bipyramidal coordination geometry. The two pyridine rings in each 2,2'-bipyridine ligand form dihedral angles of 10.75 (12) and 4.28 (13)°. The crystal packing is stabilized by interionic C-H...O hydrogen bonds, C-H...[pi] interactions and aromatic [pi]-[pi] stacking interactions, with centroid-centroid distances of 3.616 (7) Å.

Comment top

Hydrogen bonding has been intensively investigated in organic crystalline solids, but is relatively unexplored in coordination complexes. In order to search the new functional hydrogen-bonded metal coordination network structures, chelating ligands such as 2,2'-bipyridine (Ruiz-Perez et al., 2002) were selected for study because they can simultaneously coordinate with the metal ions and provide potential intermolecular interaction sites.

In title compound (Fig. 1), the cobalt(II) atom has a distorted trigonal bipyramidal coordination geometry provided by one chloride anion and four nitrogen atoms from the two chelating 2, 2'-bipyridine molecules. The equatorial plane is defined by the N2, N4 and Cl1 atoms, and the sum of the N—Co—N and N—Co—Cl angles is 360.0 (3)°. The apical positions are occupied by the N1 and N3 atoms [N1—Co1—N3 = 174.58 (14)°]. The Co—N bond lenghts (Table 1) lie in the range 1.992 (3)-2.138 (3) Å. The N1/C1–C5, N2/C6–C10 and N3/C11–C15, N4/C16–C20 pyridine rings form dihedral angles of 10.75 (12) and 4.28 (13)°, respectively. The structure is similar to that reported previously for the corresponding copper(II) compound (Harrison et al., 1981). In the crystal structure, cations and anions interact through C—H···O hydrogen bonds (Table 2) to form a three-dimensional network. The structure is further stabilized by a C—H···π interaction (C11—H11···Cg1, 2.85 Å; C11—H11—Cg1, 155°; Cg1 is the centroid of the N2/C6–C10 pyridine ring) and by aromatic π–π stacking interactions involving centrosymmetrically related N3/C11–C15 pyridine rings, with a centroid-to-centroid distance of 3.616 (7) Å.

Related literature top

For the use of 2,2'-bipyridine in coordination chemistry, see: Ruiz-Perez et al. (2002). For the structure of the corresponding copper(II) compound, see: Harrison et al. (1981). Cg1 is the centroid of the N2/C6–C10 pyridine ring.

Experimental top

To a solution of Co(ClO4)2.6H2O and CoCl2.6H2O (1:1 molar ratio) in ethanol (10 mL) was added a solution of 2,2'-bipyridine (0.1562 g, 1 mmol) in ethanol (20 mL) and the resulting green solution was stirred for 8h at 333 K. The mixture was then filtered and the filtrate was allowed to stand at room temperature for one week to give well shaped green crystals suitable for X-ray analysis (yield 61%). Analysis calculated for C20H16Cl2N4O4Co: C 47.45, H, 3.19; N 11.07%; found: C 47.49, H 3.26, N, 11.12%.

Refinement top

All H atoms were positioned geometrically and constrained to ride on their parent atoms, with C—H = 0.93 Å and with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with 30% displacement ellipsoids.
Bis(2,2'-bipyridine-κ2N,N')chloridocobalt(II) perchlorate top
Crystal data top
[CoCl(C10H8N2)2]ClO4F(000) = 1028
Mr = 506.20Dx = 1.615 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2895 reflections
a = 10.7725 (12) Åθ = 2.6–25.8°
b = 12.2696 (14) ŵ = 1.12 mm−1
c = 16.333 (2) ÅT = 298 K
β = 105.361 (2)°Block, green
V = 2081.7 (4) Å30.40 × 0.21 × 0.19 mm
Z = 4
Data collection top
Bruker SMART CCD
diffractometer		3661 independent reflections
Radiation source: fine-focus sealed tube2458 reflections with I > 2σ(I)
graphiteRint = 0.029
φ and ω scansθmax = 25.0°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −12→12
Tmin = 0.664, Tmax = 0.816k = −14→14
10284 measured reflectionsl = −12→19
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.124H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0432P)2 + 2.7771P]
where P = (Fo2 + 2Fc2)/3
3661 reflections(Δ/σ)max = 0.001
280 parametersΔρmax = 0.50 e Å−3
1 restraintΔρmin = −0.39 e Å−3
Crystal data top
[CoCl(C10H8N2)2]ClO4V = 2081.7 (4) Å3
Mr = 506.20Z = 4
Monoclinic, P21/nMo Kα radiation
a = 10.7725 (12) ŵ = 1.12 mm−1
b = 12.2696 (14) ÅT = 298 K
c = 16.333 (2) Å0.40 × 0.21 × 0.19 mm
β = 105.361 (2)°
Data collection top
Bruker SMART CCD
diffractometer		3661 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2458 reflections with I > 2σ(I)
Tmin = 0.664, Tmax = 0.816Rint = 0.029
10284 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.043H-atom parameters constrained
wR(F2) = 0.124Δρmax = 0.50 e Å−3
S = 1.06Δρmin = −0.39 e Å−3
3661 reflectionsAbsolute structure: ?
280 parametersFlack parameter: ?
1 restraintRogers parameter: ?
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
xyzUiso*/Ueq
Co10.73259 (5)0.95539 (4)0.86267 (3)0.04181 (18)
N10.7739 (3)0.9517 (3)0.7508 (2)0.0531 (9)
Cl10.72296 (14)1.13977 (10)0.86111 (8)0.0720 (4)
Cl20.27386 (13)0.89418 (10)0.63357 (7)0.0653 (3)
N20.9032 (3)0.8579 (3)0.8932 (2)0.0504 (9)
N30.6929 (3)0.9438 (3)0.9747 (2)0.0514 (9)
N40.6035 (3)0.8263 (3)0.8383 (2)0.0527 (9)
O10.1665 (5)0.9455 (4)0.5784 (3)0.140 (2)
O20.2326 (4)0.8325 (4)0.6957 (2)0.1056 (14)
O30.3357 (5)0.8273 (4)0.5887 (3)0.143 (2)
O40.3567 (6)0.9733 (4)0.6800 (4)0.163 (2)
C10.7066 (5)1.0065 (4)0.6821 (3)0.0656 (13)
H10.63291.04400.68510.079*
C20.7427 (5)1.0089 (4)0.6077 (3)0.0682 (14)
H20.69391.04680.56090.082*
C30.8520 (5)0.9544 (4)0.6034 (3)0.0691 (14)
H30.87900.95620.55380.083*
C40.9217 (5)0.8970 (4)0.6730 (3)0.0617 (12)
H40.99550.85930.67080.074*
C50.8802 (4)0.8963 (3)0.7466 (3)0.0485 (10)
C60.9463 (4)0.8365 (3)0.8244 (3)0.0472 (10)
C71.0428 (5)0.7611 (4)0.8278 (3)0.0658 (13)
H71.07270.74730.78040.079*
C81.0942 (5)0.7065 (4)0.9037 (4)0.0742 (14)
H81.15890.65520.90720.089*
C91.0505 (5)0.7275 (4)0.9728 (3)0.0674 (13)
H91.08400.69091.02370.081*
C100.9553 (4)0.8044 (4)0.9653 (3)0.0624 (12)
H100.92590.81981.01270.075*
C110.7445 (5)1.0087 (4)1.0417 (3)0.0623 (12)
H110.80731.05881.03760.075*
C120.7073 (5)1.0034 (5)1.1160 (3)0.0689 (13)
H120.74471.04871.16150.083*
C130.6132 (5)0.9294 (4)1.1214 (3)0.0711 (15)
H130.58580.92451.17070.085*
C140.5602 (5)0.8629 (4)1.0530 (3)0.0679 (14)
H140.49590.81351.05570.082*
C150.6028 (4)0.8700 (4)0.9804 (3)0.0526 (11)
C160.5549 (4)0.8017 (3)0.9042 (3)0.0526 (11)
C170.4680 (5)0.7166 (4)0.8981 (4)0.0720 (14)
H170.43440.69990.94350.086*
C180.4323 (5)0.6573 (4)0.8242 (4)0.0835 (17)
H180.37340.60060.81930.100*
C190.4824 (5)0.6808 (4)0.7588 (4)0.0751 (15)
H190.45960.64040.70890.090*
C200.5678 (5)0.7659 (4)0.7675 (3)0.0632 (12)
H200.60220.78230.72240.076*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.0476 (3)0.0455 (3)0.0378 (3)−0.0002 (3)0.0210 (2)0.0038 (2)
N10.056 (2)0.058 (2)0.049 (2)0.0005 (19)0.0199 (17)0.0079 (18)
Cl10.1044 (10)0.0515 (6)0.0683 (8)−0.0031 (7)0.0372 (7)0.0040 (6)
Cl20.0797 (8)0.0674 (8)0.0556 (7)0.0164 (7)0.0302 (6)0.0039 (6)
N20.050 (2)0.057 (2)0.048 (2)−0.0015 (17)0.0184 (17)0.0080 (17)
N30.054 (2)0.053 (2)0.052 (2)0.0006 (18)0.0244 (17)0.0030 (17)
N40.050 (2)0.055 (2)0.056 (2)0.0011 (17)0.0181 (17)0.0032 (18)
O10.138 (4)0.217 (6)0.072 (3)0.099 (4)0.039 (3)0.055 (3)
O20.107 (3)0.131 (4)0.093 (3)0.021 (3)0.051 (2)0.047 (3)
O30.178 (5)0.176 (5)0.095 (3)0.094 (4)0.071 (3)−0.006 (3)
O40.191 (6)0.107 (4)0.184 (6)−0.048 (4)0.034 (5)−0.021 (4)
C10.073 (3)0.072 (3)0.052 (3)0.011 (3)0.018 (2)0.010 (2)
C20.086 (4)0.071 (3)0.045 (3)−0.004 (3)0.013 (3)0.007 (2)
C30.094 (4)0.073 (3)0.047 (3)−0.013 (3)0.031 (3)−0.001 (3)
C40.073 (3)0.066 (3)0.055 (3)−0.006 (3)0.032 (2)−0.009 (2)
C50.053 (3)0.046 (2)0.051 (2)−0.012 (2)0.022 (2)−0.005 (2)
C60.049 (2)0.045 (2)0.051 (2)−0.007 (2)0.020 (2)−0.0030 (19)
C70.070 (3)0.061 (3)0.071 (3)0.006 (3)0.026 (3)−0.008 (3)
C80.068 (3)0.061 (3)0.090 (4)0.015 (3)0.014 (3)−0.001 (3)
C90.067 (3)0.064 (3)0.070 (3)0.007 (3)0.016 (3)0.011 (3)
C100.063 (3)0.071 (3)0.055 (3)0.001 (3)0.020 (2)0.012 (2)
C110.069 (3)0.065 (3)0.057 (3)0.000 (2)0.023 (2)−0.001 (2)
C120.085 (4)0.075 (3)0.051 (3)0.014 (3)0.026 (3)0.004 (2)
C130.091 (4)0.080 (4)0.055 (3)0.019 (3)0.042 (3)0.016 (3)
C140.072 (3)0.073 (3)0.071 (3)0.008 (3)0.040 (3)0.020 (3)
C150.053 (3)0.053 (3)0.058 (3)0.012 (2)0.025 (2)0.016 (2)
C160.048 (3)0.047 (2)0.067 (3)0.008 (2)0.022 (2)0.015 (2)
C170.073 (3)0.060 (3)0.090 (4)−0.004 (3)0.034 (3)0.016 (3)
C180.077 (4)0.059 (3)0.109 (5)−0.019 (3)0.016 (3)0.007 (3)
C190.079 (4)0.055 (3)0.084 (4)−0.006 (3)0.007 (3)−0.001 (3)
C200.065 (3)0.063 (3)0.060 (3)−0.002 (2)0.015 (2)−0.001 (2)
Geometric parameters (Å, °) top
Co1—N31.992 (3)C6—C71.381 (6)
Co1—N11.992 (3)C7—C81.388 (7)
Co1—N42.075 (4)C7—H70.9300
Co1—N22.138 (3)C8—C91.358 (7)
Co1—Cl12.2645 (13)C8—H80.9300
N1—C11.344 (6)C9—C101.375 (6)
N1—C51.349 (5)C9—H90.9300
Cl2—O31.383 (4)C10—H100.9300
Cl2—O41.399 (5)C11—C121.375 (6)
Cl2—O11.412 (4)C11—H110.9300
Cl2—O21.428 (4)C12—C131.381 (7)
N2—C101.335 (5)C12—H120.9300
N2—C61.351 (5)C13—C141.379 (7)
N3—C151.348 (5)C13—H130.9300
N3—C111.349 (6)C14—C151.382 (6)
N4—C201.342 (5)C14—H140.9300
N4—C161.350 (5)C15—C161.475 (6)
C1—C21.370 (6)C16—C171.388 (6)
C1—H10.9300C17—C181.374 (7)
C2—C31.372 (7)C17—H170.9300
C2—H20.9300C18—C191.351 (7)
C3—C41.379 (7)C18—H180.9300
C3—H30.9300C19—C201.373 (6)
C4—C51.388 (6)C19—H190.9300
C4—H40.9300C20—H200.9300
C5—C61.476 (6)
N3—Co1—N1174.58 (14)N2—C6—C5115.2 (4)
N3—Co1—N479.94 (14)C7—C6—C5123.6 (4)
N1—Co1—N496.21 (14)C6—C7—C8118.5 (5)
N3—Co1—N297.25 (13)C6—C7—H7120.8
N1—Co1—N279.29 (13)C8—C7—H7120.8
N4—Co1—N296.25 (14)C9—C8—C7120.5 (5)
N3—Co1—Cl193.53 (10)C9—C8—H8119.8
N1—Co1—Cl191.89 (11)C7—C8—H8119.8
N4—Co1—Cl1137.20 (10)C8—C9—C10118.0 (5)
N2—Co1—Cl1126.54 (10)C8—C9—H9121.0
C1—N1—C5119.2 (4)C10—C9—H9121.0
C1—N1—Co1123.5 (3)N2—C10—C9123.1 (4)
C5—N1—Co1117.2 (3)N2—C10—H10118.5
O3—Cl2—O4111.8 (4)C9—C10—H10118.5
O3—Cl2—O1110.8 (3)N3—C11—C12122.2 (5)
O4—Cl2—O1109.5 (4)N3—C11—H11118.9
O3—Cl2—O2110.3 (3)C12—C11—H11118.9
O4—Cl2—O2104.9 (3)C11—C12—C13118.6 (5)
O1—Cl2—O2109.4 (3)C11—C12—H12120.7
C10—N2—C6118.8 (4)C13—C12—H12120.7
C10—N2—Co1128.0 (3)C14—C13—C12119.4 (4)
C6—N2—Co1112.2 (3)C14—C13—H13120.3
C15—N3—C11119.4 (4)C12—C13—H13120.3
C15—N3—Co1116.4 (3)C13—C14—C15119.8 (5)
C11—N3—Co1124.1 (3)C13—C14—H14120.1
C20—N4—C16118.7 (4)C15—C14—H14120.1
C20—N4—Co1127.7 (3)N3—C15—C14120.6 (4)
C16—N4—Co1113.5 (3)N3—C15—C16114.8 (4)
N1—C1—C2122.2 (5)C14—C15—C16124.5 (4)
N1—C1—H1118.9N4—C16—C17120.5 (5)
C2—C1—H1118.9N4—C16—C15115.0 (4)
C1—C2—C3119.0 (5)C17—C16—C15124.5 (4)
C1—C2—H2120.5C18—C17—C16119.3 (5)
C3—C2—H2120.5C18—C17—H17120.4
C2—C3—C4119.5 (4)C16—C17—H17120.4
C2—C3—H3120.3C19—C18—C17120.2 (5)
C4—C3—H3120.3C19—C18—H18119.9
C3—C4—C5119.2 (5)C17—C18—H18119.9
C3—C4—H4120.4C18—C19—C20118.5 (5)
C5—C4—H4120.4C18—C19—H19120.7
N1—C5—C4120.8 (4)C20—C19—H19120.7
N1—C5—C6115.4 (3)N4—C20—C19122.7 (5)
C4—C5—C6123.8 (4)N4—C20—H20118.6
N2—C6—C7121.2 (4)C19—C20—H20118.6
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C3—H3···O1i0.932.413.170 (6)139
C4—H4···O2ii0.932.503.365 (6)155
C10—H10···O3iii0.932.533.116 (6)122
C11—H11···Cg1iv0.932.853.709 (6)155
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x+1, y, z; (iii) x+1/2, −y+3/2, z+1/2; (iv) −x+2, −y+2, −z+2.
Table 1
Selected geometric parameters (Å) top
Co1—N31.992 (3)Co1—N22.138 (3)
Co1—N11.992 (3)Co1—Cl12.2645 (13)
Co1—N42.075 (4)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C3—H3···O1i0.932.413.170 (6)139
C4—H4···O2ii0.932.503.365 (6)155
C10—H10···O3iii0.932.533.116 (6)122
C11—H11···Cg1iv0.932.853.709 (6)155
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x+1, y, z; (iii) x+1/2, −y+3/2, z+1/2; (iv) −x+2, −y+2, −z+2.
Acknowledgements top

We acknowledge the financial support of the Science Foundation of Shandong.

references
References top

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Harrison, W. D., Kennedy, D. M., Ray, N. J., Sheahan, R. & Hathaway, B. J. (1981). J. Chem. Soc. Dalton Trans. pp. 1556–1554.

Ruiz-Perez, C., Luis, P. A. L., Lloret, F. & Julve, M. (2002). Inorg. Chim. Acta, 336, 131–136.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Spek, A. L. (2009). Acta Cryst. D65, 148–155.