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

doi:10.1107/S1600536808007617

Acta Crystallogr Sect E Struct Rep Online. 2008 April 1; 64(Pt 4): m582.

Published online 2008 March 29. doi: 10.1107/S1600536808007617

PMCID: PMC2960999

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

LI Jia,^a^b Ling-Qian Kong,^c and Da-Cheng Li^a^*

^aSchool of Chemistry and Chemical Engineering, Liaocheng University, Shandong 252059, People’s Republic of China

^bLiaocheng Vocational and Technical College, Liaocheng, Shandong 252000, People’s Republic of China

^cDongchang College of Liaocheng University, Liaocheng, Shandong 252000, People’s Republic of China

Correspondence e-mail: lidacheng62/at/lcu.edu.cn

Received January 31, 2008; Accepted March 20, 2008.

This is an open-access article distributed under the terms of the Creative Commons Attribution Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Abstract

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.

Related literature

For the crystal structures of cobalt complexes with analogous ligands, see: Veidis et al. (1981

); Tang et al. (2004

). For related literature, see: Milani et al. (2003

An external file that holds a picture, illustration, etc.
Object name is e-64-0m582-scheme1.jpg Object name is e-64-0m582-scheme1.jpg

Experimental

Crystal data

[Co(NCO)₂(C₁₀H₈N₂)₂]
M _r = 455.34
Orthorhombic,
a = 14.148 (12) Å
b = 9.774 (8) Å
c = 15.253 (13) Å
V = 2109 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.84 mm⁻¹
T = 298 (2) K
0.30 × 0.25 × 0.06 mm

Data collection

Bruker SMART 1000 diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T _min = 0.786, T _max = 0.951
10457 measured reflections
1870 independent reflections
1009 reflections with I > 2σ(I)
R _int = 0.078

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.078
S = 1.00
1870 reflections
141 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: SMART (Siemens, 1996

); cell refinement: SAINT (Siemens, 1996

); data reduction: SAINT; 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.

Table 1

Selected geometric parameters (Å, °)

Table 2

Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808007617/fi2060sup1.cif

Click here to view.^{(15K, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808007617/fi2060Isup2.hkl

Click here to view.^{(92K, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

We acknowledge the Natural Science Foundation of Liaocheng University (X051002).

supplementary crystallographic information

Comment

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)..

Experimental

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%.

Figures

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.

Crystal data

[Co(NCO)₂(C₁₀H₈N₂)₂]	F₀₀₀ = 932
M_r = 455.34	D_x = 1.434 Mg m⁻³
Orthorhombic, Pbcn	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -P2n2ab	Cell parameters from 1484 reflections
a = 14.148 (12) Å	θ = 2.5–20.8º
b = 9.774 (8) Å	µ = 0.85 mm⁻¹
c = 15.253 (13) Å	T = 298 (2) K
V = 2109 (3) Å³	Plate, red
Z = 4	0.30 × 0.25 × 0.06 mm

Data collection

Bruker Smart 1000 diffractometer	1870 independent reflections
Radiation source: fine-focus sealed tube	1009 reflections with I > 2σ(I)
Monochromator: graphite	R_int = 0.078
T = 298(2) K	θ_max = 25.0º
& ω scans	θ_min = 2.5º
Absorption correction: multi-scan[SADABS; Sheldrick, 1996)	h = −16→14
T_min = 0.786, T_max = 0.951	k = −11→9
10457 measured reflections	l = −18→17

Refinement

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.039	H-atom parameters constrained
wR(F²) = 0.078	w = 1/[σ²(F_o²) + (0.0386P)² + 2.2714P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max = 0.001
1870 reflections	Δρ_max = 0.25 e Å⁻³
141 parameters	Δρ_min = −0.30 e Å⁻³
Primary atom site location: structure-invariant direct methods	Extinction correction: none

Special details

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)

	x	y	z	U_iso*/U_eq
Co1	0.5000	1.02936 (6)	0.7500	0.0514 (2)
N1	0.45099 (19)	1.1668 (3)	0.6615 (2)	0.0780 (10)
N2	0.42837 (17)	0.8651 (2)	0.68223 (17)	0.0525 (7)
N3	0.36432 (16)	1.0105 (3)	0.81603 (17)	0.0538 (7)
O1	0.4129 (2)	1.3351 (3)	0.5593 (2)	0.1331 (13)
C1	0.4337 (2)	1.2469 (5)	0.6118 (3)	0.0737 (12)
C2	0.3390 (2)	0.8363 (3)	0.7088 (2)	0.0501 (8)
C3	0.2898 (2)	0.7277 (4)	0.6735 (2)	0.0655 (10)
H3	0.2289	0.7081	0.6927	0.079*
C4	0.3309 (3)	0.6491 (4)	0.6103 (3)	0.0802 (12)
H4	0.2983	0.5754	0.5863	0.096*
C5	0.4205 (3)	0.6794 (4)	0.5821 (2)	0.0738 (11)
H5	0.4496	0.6275	0.5388	0.089*
C6	0.4657 (2)	0.7879 (4)	0.6196 (2)	0.0669 (10)
H6	0.5263	0.8090	0.6002	0.080*
C7	0.3019 (2)	0.9245 (3)	0.7788 (2)	0.0511 (9)
C8	0.2077 (2)	0.9216 (3)	0.8059 (3)	0.0676 (10)
H8	0.1645	0.8642	0.7784	0.081*
C9	0.1797 (3)	1.0036 (4)	0.8731 (3)	0.0808 (13)
H9	0.1172	1.0020	0.8921	0.097*
C10	0.2434 (3)	1.0881 (4)	0.9122 (2)	0.0804 (12)
H10	0.2256	1.1444	0.9585	0.096*
C11	0.3354 (2)	1.0883 (3)	0.8814 (2)	0.0685 (10)
H11	0.3790	1.1460	0.9082	0.082*

Atomic displacement parameters (Å²)

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0391 (3)	0.0536 (4)	0.0615 (4)	0.000	0.0011 (3)	0.000
N1	0.064 (2)	0.078 (2)	0.092 (3)	0.0116 (17)	0.0007 (18)	0.0301 (19)
N2	0.0402 (15)	0.0601 (19)	0.0573 (19)	0.0020 (13)	0.0000 (14)	−0.0038 (14)
N3	0.0457 (15)	0.0555 (19)	0.0603 (19)	0.0050 (14)	0.0027 (14)	−0.0032 (14)
O1	0.115 (2)	0.152 (3)	0.133 (3)	0.055 (2)	0.025 (2)	0.070 (2)
C1	0.052 (2)	0.090 (4)	0.079 (3)	0.020 (2)	0.018 (2)	0.012 (2)
C2	0.0385 (19)	0.056 (2)	0.056 (2)	−0.0010 (17)	−0.0047 (17)	0.0121 (17)
C3	0.051 (2)	0.070 (3)	0.076 (3)	−0.011 (2)	−0.0061 (19)	0.004 (2)
C4	0.087 (3)	0.077 (3)	0.077 (3)	−0.020 (2)	−0.011 (2)	−0.012 (2)
C5	0.074 (3)	0.074 (3)	0.072 (3)	0.001 (2)	0.001 (2)	−0.019 (2)
C6	0.053 (2)	0.079 (3)	0.069 (3)	−0.0057 (19)	−0.0008 (19)	−0.009 (2)
C7	0.0420 (19)	0.047 (2)	0.064 (3)	0.0030 (16)	0.0052 (16)	0.0113 (16)
C8	0.046 (2)	0.071 (3)	0.086 (3)	−0.0028 (18)	0.009 (2)	0.010 (2)
C9	0.053 (2)	0.092 (4)	0.097 (3)	0.012 (2)	0.028 (2)	0.016 (3)
C10	0.079 (3)	0.077 (3)	0.086 (3)	0.014 (2)	0.033 (3)	0.002 (2)
C11	0.062 (2)	0.066 (3)	0.078 (3)	0.0021 (19)	0.013 (2)	−0.009 (2)

Geometric parameters (Å, °)

Co1—N1ⁱ	2.027 (3)	C3—H3	0.9300
Co1—N1	2.027 (3)	C4—C5	1.371 (4)
Co1—N2	2.162 (3)	C4—H4	0.9300
Co1—N2ⁱ	2.162 (3)	C5—C6	1.364 (4)
Co1—N3	2.176 (3)	C5—H5	0.9300
Co1—N3ⁱ	2.176 (3)	C6—H6	0.9300
N1—C1	1.117 (4)	C7—C8	1.396 (4)
N2—C6	1.327 (4)	C8—C9	1.360 (4)
N2—C2	1.358 (3)	C8—H8	0.9300
N3—C11	1.319 (4)	C9—C10	1.361 (5)
N3—C7	1.345 (3)	C9—H9	0.9300
O1—C1	1.213 (4)	C10—C11	1.384 (4)
C2—C3	1.378 (4)	C10—H10	0.9300
C2—C7	1.469 (4)	C11—H11	0.9300
C3—C4	1.363 (4)

N1ⁱ—Co1—N1	97.0 (2)	C4—C3—H3	120.2
N1ⁱ—Co1—N2	166.18 (11)	C2—C3—H3	120.2
N1—Co1—N2	90.76 (12)	C3—C4—C5	119.6 (4)
N1ⁱ—Co1—N2ⁱ	90.76 (12)	C3—C4—H4	120.2
N1—Co1—N2ⁱ	166.18 (11)	C5—C4—H4	120.2
N2—Co1—N2ⁱ	84.07 (14)	C6—C5—C4	118.1 (4)
N1ⁱ—Co1—N3	92.83 (12)	C6—C5—H5	121.0
N1—Co1—N3	93.59 (11)	C4—C5—H5	121.0
N2—Co1—N3	75.22 (11)	N2—C6—C5	123.8 (3)
N2ⁱ—Co1—N3	97.44 (10)	N2—C6—H6	118.1
N1ⁱ—Co1—N3ⁱ	93.59 (11)	C5—C6—H6	118.1
N1—Co1—N3ⁱ	92.83 (12)	N3—C7—C8	121.0 (3)
N2—Co1—N3ⁱ	97.44 (10)	N3—C7—C2	116.1 (3)
N2ⁱ—Co1—N3ⁱ	75.22 (11)	C8—C7—C2	123.0 (3)
N3—Co1—N3ⁱ	170.29 (13)	C9—C8—C7	119.3 (3)
C1—N1—Co1	172.6 (3)	C9—C8—H8	120.3
C6—N2—C2	117.9 (3)	C7—C8—H8	120.3
C6—N2—Co1	125.4 (2)	C8—C9—C10	119.7 (3)
C2—N2—Co1	116.6 (2)	C8—C9—H9	120.2
C11—N3—C7	118.4 (3)	C10—C9—H9	120.2
C11—N3—Co1	125.1 (2)	C9—C10—C11	118.4 (4)
C7—N3—Co1	115.9 (2)	C9—C10—H10	120.8
N1—C1—O1	178.3 (5)	C11—C10—H10	120.8
N2—C2—C3	120.9 (3)	N3—C11—C10	123.2 (3)
N2—C2—C7	115.3 (3)	N3—C11—H11	118.4
C3—C2—C7	123.7 (3)	C10—C11—H11	118.4
C4—C3—C2	119.6 (3)

Symmetry codes: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···O1ⁱⁱ	0.93	2.50	3.236 (5)	137
C5—H5···O1ⁱⁱⁱ	0.93	2.48	3.198 (5)	134

Symmetry codes: (ii) −x+1/2, −y+5/2, z+1/2; (iii) −x+1, −y+2, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: FI2060).

References

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. [PubMed]
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.

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