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Acta Cryst. (2008). E64, m582    [ doi:10.1107/S1600536808007617 ]

cis-Bis(2,2'-bipyridyl)dicyanatocobalt(II)

L. I. Jia, L.-Q. Kong and D.-C. Li

Abstract top

In the title complex, [Co(NCO)2(C10H8N2)2], the Co atom is coordinated by four N atoms from two 2,2'-bipyridyl ligands and two N atoms from two cyanate anions in a distorted octahedral geometry. The Co atom lies on a twofold rotation axis. The average Co-N bond length is 2.126 (7) Å. Weak intermolecular C-H...O interactions lead to the formation of a three-dimensional network.

Comment top

Organometallic Co derivatives are applied as catalysts in polymerization reactions of polar olefins and for the elucidation of the hypothetical mechanism of these polymerization reactions (Milani et al., 2003). In recent years the synthesis of the without bridge bonding mononucleate complexs was used to find out the information to design the multidimensional structure complexes, so the homologic ligands complex [Co(2,2'-bipy)2(N3)2].Cl.2H2O was reported(Tang et al., 2004). In this paper, Co(C10H8N2)2(NCO)2 was synthesized by the reaction of CoCl2.6H2O, 2,2'-bipyridyl and NaOCN at room temperature and the structure of the resulting complex is presented here (Fig. 1).

The Co atom lies on a special position (Wyckoff position 4c, site symmetry 2). It is formed by coordination of two 2,2'-bipyridyls ligands and two cyanate anions. The coordination gemotry of the central Co atom is distorted octahedral with four N atoms from two 2,2'-bipyridyls and two N atoms from two cyanate anions. The equatorial plane consists of N1, N2, N3 and N3iwith an average bond length of 2.135 (3) Å. The apical positions are occupied by a cyanate anion and a N atom from a 2,2'-bipyridyl with the bond length 2.027 (3) Å 2.162 (3) Å, respectively. The distances Co—N(2,2'-bipyridyl) in the title complex are significantly longer (2.176 (3) Å and 2.162 (3) Å) than those in the comparable bond length (1.950 (3) Å and 1.954 (3) Å, Tang et al.(2004)). The complexes arrange into a three-dimensional network via weak intermolecular C—H···O interactions (H···O distances: 2.499 (3) Å and 2.481 (4) Å; C···O distances: 3.417 (5) Å and 3.084 (7) Å)..

Related literature top

For the crystal structures of cobalt complexes with homologic ligands, see: Veidis et al. (1981); Tang et al. (2004). For related literature, see: Milani et al. (2003).

Experimental top

CoCl2.6H2O(0.0476 g 0.2 mmol) was dissolved in 10 ml MeOH, the solution was then added to an aqueous solution of 2,2'-bipyridyl(0.0316 g 0.2 mmol). The reaction mixture was stirred for 10 minutes until the solution color became red. NaOCN(0.0130 g 0.2 mmol) was added to the reaction mixture. The mixture was filtered and red single crystals were obtained by slow evaporation of the mother liquid for three weeks at room temperature. Elemental analysis for C22H16Co N6S2 calculated: C 58.03, H 3.54, N 18.45%; found: C 58.23, H 3.23, N 18.30%.

Refinement top

All H atoms were placed geometrically and treated as riding on their parent atoms with C—H 0.93 Å (2,2'-bipyridyl) [Uiso(H) = 1.2Ueq(C)].

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SMART (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The crystal structure of the title compound showing the atomic numbering and 30% probability displacement ellipsoids. H atoms have been omitted for clarity. The second ligand is generated by i: –x+1, y, –z+3/2.
(I) top
Crystal data top
[Co(NCO)2(C10H8N2)2]F000 = 932
Mr = 455.34Dx = 1.434 Mg m−3
Orthorhombic, PbcnMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P2n2abCell parameters from 1484 reflections
a = 14.148 (12) Åθ = 2.5–20.8º
b = 9.774 (8) ŵ = 0.85 mm−1
c = 15.253 (13) ÅT = 298 (2) K
V = 2109 (3) Å3Plate, red
Z = 40.30 × 0.25 × 0.06 mm
Data collection top
Bruker Smart 1000
diffractometer		1870 independent reflections
Radiation source: fine-focus sealed tube1009 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.078
T = 298(2) Kθmax = 25.0º
φ & ω scansθmin = 2.5º
Absorption correction: multi-scan
[SADABS; Sheldrick, 1996)		h = −16→14
Tmin = 0.786, Tmax = 0.951k = −11→9
10457 measured reflectionsl = −18→17
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.039H-atom parameters constrained
wR(F2) = 0.078  w = 1/[σ2(Fo2) + (0.0386P)2 + 2.2714P]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max = 0.001
1870 reflectionsΔρmax = 0.25 e Å−3
141 parametersΔρmin = −0.30 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Co(NCO)2(C10H8N2)2]V = 2109 (3) Å3
Mr = 455.34Z = 4
Orthorhombic, PbcnMo Kα
a = 14.148 (12) ŵ = 0.85 mm−1
b = 9.774 (8) ÅT = 298 (2) K
c = 15.253 (13) Å0.30 × 0.25 × 0.06 mm
Data collection top
Bruker Smart 1000
diffractometer		1870 independent reflections
Absorption correction: multi-scan
[SADABS; Sheldrick, 1996)		1009 reflections with I > 2σ(I)
Tmin = 0.786, Tmax = 0.951Rint = 0.078
10457 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.039141 parameters
wR(F2) = 0.078H-atom parameters constrained
S = 1.00Δρmax = 0.25 e Å−3
1870 reflectionsΔρmin = −0.30 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
xyzUiso*/Ueq
Co10.50001.02936 (6)0.75000.0514 (2)
N10.45099 (19)1.1668 (3)0.6615 (2)0.0780 (10)
N20.42837 (17)0.8651 (2)0.68223 (17)0.0525 (7)
N30.36432 (16)1.0105 (3)0.81603 (17)0.0538 (7)
O10.4129 (2)1.3351 (3)0.5593 (2)0.1331 (13)
C10.4337 (2)1.2469 (5)0.6118 (3)0.0737 (12)
C20.3390 (2)0.8363 (3)0.7088 (2)0.0501 (8)
C30.2898 (2)0.7277 (4)0.6735 (2)0.0655 (10)
H30.22890.70810.69270.079*
C40.3309 (3)0.6491 (4)0.6103 (3)0.0802 (12)
H40.29830.57540.58630.096*
C50.4205 (3)0.6794 (4)0.5821 (2)0.0738 (11)
H50.44960.62750.53880.089*
C60.4657 (2)0.7879 (4)0.6196 (2)0.0669 (10)
H60.52630.80900.60020.080*
C70.3019 (2)0.9245 (3)0.7788 (2)0.0511 (9)
C80.2077 (2)0.9216 (3)0.8059 (3)0.0676 (10)
H80.16450.86420.77840.081*
C90.1797 (3)1.0036 (4)0.8731 (3)0.0808 (13)
H90.11721.00200.89210.097*
C100.2434 (3)1.0881 (4)0.9122 (2)0.0804 (12)
H100.22561.14440.95850.096*
C110.3354 (2)1.0883 (3)0.8814 (2)0.0685 (10)
H110.37901.14600.90820.082*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.0391 (3)0.0536 (4)0.0615 (4)0.0000.0011 (3)0.000
N10.064 (2)0.078 (2)0.092 (3)0.0116 (17)0.0007 (18)0.0301 (19)
N20.0402 (15)0.0601 (19)0.0573 (19)0.0020 (13)0.0000 (14)−0.0038 (14)
N30.0457 (15)0.0555 (19)0.0603 (19)0.0050 (14)0.0027 (14)−0.0032 (14)
O10.115 (2)0.152 (3)0.133 (3)0.055 (2)0.025 (2)0.070 (2)
C10.052 (2)0.090 (4)0.079 (3)0.020 (2)0.018 (2)0.012 (2)
C20.0385 (19)0.056 (2)0.056 (2)−0.0010 (17)−0.0047 (17)0.0121 (17)
C30.051 (2)0.070 (3)0.076 (3)−0.011 (2)−0.0061 (19)0.004 (2)
C40.087 (3)0.077 (3)0.077 (3)−0.020 (2)−0.011 (2)−0.012 (2)
C50.074 (3)0.074 (3)0.072 (3)0.001 (2)0.001 (2)−0.019 (2)
C60.053 (2)0.079 (3)0.069 (3)−0.0057 (19)−0.0008 (19)−0.009 (2)
C70.0420 (19)0.047 (2)0.064 (3)0.0030 (16)0.0052 (16)0.0113 (16)
C80.046 (2)0.071 (3)0.086 (3)−0.0028 (18)0.009 (2)0.010 (2)
C90.053 (2)0.092 (4)0.097 (3)0.012 (2)0.028 (2)0.016 (3)
C100.079 (3)0.077 (3)0.086 (3)0.014 (2)0.033 (3)0.002 (2)
C110.062 (2)0.066 (3)0.078 (3)0.0021 (19)0.013 (2)−0.009 (2)
Geometric parameters (Å, °) top
Co1—N1i2.027 (3)C3—H30.9300
Co1—N12.027 (3)C4—C51.371 (4)
Co1—N22.162 (3)C4—H40.9300
Co1—N2i2.162 (3)C5—C61.364 (4)
Co1—N32.176 (3)C5—H50.9300
Co1—N3i2.176 (3)C6—H60.9300
N1—C11.117 (4)C7—C81.396 (4)
N2—C61.327 (4)C8—C91.360 (4)
N2—C21.358 (3)C8—H80.9300
N3—C111.319 (4)C9—C101.361 (5)
N3—C71.345 (3)C9—H90.9300
O1—C11.213 (4)C10—C111.384 (4)
C2—C31.378 (4)C10—H100.9300
C2—C71.469 (4)C11—H110.9300
C3—C41.363 (4)
N1i—Co1—N197.0 (2)C4—C3—H3120.2
N1i—Co1—N2166.18 (11)C2—C3—H3120.2
N1—Co1—N290.76 (12)C3—C4—C5119.6 (4)
N1i—Co1—N2i90.76 (12)C3—C4—H4120.2
N1—Co1—N2i166.18 (11)C5—C4—H4120.2
N2—Co1—N2i84.07 (14)C6—C5—C4118.1 (4)
N1i—Co1—N392.83 (12)C6—C5—H5121.0
N1—Co1—N393.59 (11)C4—C5—H5121.0
N2—Co1—N375.22 (11)N2—C6—C5123.8 (3)
N2i—Co1—N397.44 (10)N2—C6—H6118.1
N1i—Co1—N3i93.59 (11)C5—C6—H6118.1
N1—Co1—N3i92.83 (12)N3—C7—C8121.0 (3)
N2—Co1—N3i97.44 (10)N3—C7—C2116.1 (3)
N2i—Co1—N3i75.22 (11)C8—C7—C2123.0 (3)
N3—Co1—N3i170.29 (13)C9—C8—C7119.3 (3)
C1—N1—Co1172.6 (3)C9—C8—H8120.3
C6—N2—C2117.9 (3)C7—C8—H8120.3
C6—N2—Co1125.4 (2)C8—C9—C10119.7 (3)
C2—N2—Co1116.6 (2)C8—C9—H9120.2
C11—N3—C7118.4 (3)C10—C9—H9120.2
C11—N3—Co1125.1 (2)C9—C10—C11118.4 (4)
C7—N3—Co1115.9 (2)C9—C10—H10120.8
N1—C1—O1178.3 (5)C11—C10—H10120.8
N2—C2—C3120.9 (3)N3—C11—C10123.2 (3)
N2—C2—C7115.3 (3)N3—C11—H11118.4
C3—C2—C7123.7 (3)C10—C11—H11118.4
C4—C3—C2119.6 (3)
Symmetry codes: (i) −x+1, y, −z+3/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C10—H10···O1ii0.932.503.236 (5)137
C5—H5···O1iii0.932.483.198 (5)134
Symmetry codes: (ii) −x+1/2, −y+5/2, z+1/2; (iii) −x+1, −y+2, −z+1.
Table 1
Selected geometric parameters (Å, °) top
Co1—N1i2.027 (3)Co1—N2i2.162 (3)
Co1—N12.027 (3)Co1—N32.176 (3)
Co1—N22.162 (3)Co1—N3i2.176 (3)
N1i—Co1—N197.0 (2)N2—Co1—N375.22 (11)
N1i—Co1—N2166.18 (11)N2i—Co1—N397.44 (10)
N1—Co1—N290.76 (12)N1i—Co1—N3i93.59 (11)
N1i—Co1—N2i90.76 (12)N1—Co1—N3i92.83 (12)
N1—Co1—N2i166.18 (11)N2—Co1—N3i97.44 (10)
N2—Co1—N2i84.07 (14)N2i—Co1—N3i75.22 (11)
N1i—Co1—N392.83 (12)N3—Co1—N3i170.29 (13)
N1—Co1—N393.59 (11)
Symmetry codes: (i) −x+1, y, −z+3/2.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C10—H10···O1ii0.932.503.236 (5)137
C5—H5···O1iii0.932.483.198 (5)134
Symmetry codes: (ii) −x+1/2, −y+5/2, z+1/2; (iii) −x+1, −y+2, −z+1.
Acknowledgements top

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references
References top

Milani, B., Stabon, E., Zangrando, E., Mestroni, G., Sommazzi, A. & Zannoni, C. (2003). Inorg. Chim. Acta, 349, 209–216.

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

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

Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Tang, X. F., Ma, Y. S., Liang, F. P., Hu, R. X. & Yu, K. B. (2004). Hua Xue Ying Yong Yu Yanjiu, 16, 459-462.

Veidis, M. V., Dockum, B., Charron, F. F. & Reiff, W. M. (1981). Inorg. Chim. Acta, 53, L197–L199.