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

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

doi:10.1107/S1600536808007617

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 4| April 2008| Page m582

doi:10.1107/S1600536808007617

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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, and ^cDongchang College of Liaocheng University, Liaocheng, Shandong 252000, People's Republic of China
^*Correspondence e-mail: lidacheng62@lcu.edu.cn

(Received 31 January 2008; accepted 20 March 2008; online 29 March 2008)

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 ).

Experimental

Crystal data

[Co(NCO)₂(C₁₀H₈N₂)₂]
M_r = 455.34
Orthorhombic, P b c n
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[F² > 2σ(F²)] = 0.039
wR(F²) = 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

Table 1
Selected geometric parameters (Å, °)

Co1—N1	2.027 (3)
Co1—N2	2.162 (3)
Co1—N3	2.176 (3)

N1ⁱ—Co1—N1	97.0 (2)
N1ⁱ—Co1—N2	166.18 (11)
N1—Co1—N2	90.76 (12)
N2—Co1—N2ⁱ	84.07 (14)
N1ⁱ—Co1—N3	92.83 (12)
N1—Co1—N3	93.59 (11)
N2—Co1—N3	75.22 (11)
N2ⁱ—Co1—N3	97.44 (10)
N3—Co1—N3ⁱ	170.29 (13)
Symmetry code: (i) $[-x+1, y, -z+{\script{3\over 2}}]$ .

Table 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) $[-x+{\script{1\over 2}}, -y+{\script{5\over 2}}, z+{\script{1\over 2}}]$ ; (iii) -x+1, -y+2, -z+1.

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.

Supporting information

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

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

checkCIF report

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%.

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

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]	F(000) = 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 = 2.5–20.8°
b = 9.774 (8) Å	µ = 0.85 mm⁻¹
c = 15.253 (13) Å	T = 298 K
V = 2109 (3) Å³	Plate, red
Z = 4	0.30 × 0.25 × 0.06 mm

Data collection top

Bruker Smart 1000 diffractometer	1870 independent reflections
Radiation source: fine-focus sealed tube	1009 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.078
ϕ & ω scans	θ_max = 25.0°, θ_min = 2.5°
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 top

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.078	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0386P)² + 2.2714P] where P = (F_o² + 2F_c²)/3
1870 reflections	(Δ/σ)_max = 0.001
141 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

[Co(NCO)₂(C₁₀H₈N₂)₂]	V = 2109 (3) Å³
M_r = 455.34	Z = 4
Orthorhombic, Pbcn	Mo Kα radiation
a = 14.148 (12) Å	µ = 0.85 mm⁻¹
b = 9.774 (8) Å	T = 298 K
c = 15.253 (13) Å	0.30 × 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)
T_min = 0.786, T_max = 0.951	R_int = 0.078
10457 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.078	H-atom parameters constrained
S = 1.00	Δρ_max = 0.25 e Å⁻³
1870 reflections	Δρ_min = −0.30 e Å⁻³
141 parameters

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

	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) top

	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, º) top

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 code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

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.

Experimental details

Crystal data
Chemical formula	[Co(NCO)₂(C₁₀H₈N₂)₂]
M_r	455.34
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	298
a, b, c (Å)	14.148 (12), 9.774 (8), 15.253 (13)
V (Å³)	2109 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.85
Crystal size (mm)	0.30 × 0.25 × 0.06

Data collection
Diffractometer	Bruker Smart 1000 diffractometer
Absorption correction	Multi-scan [SADABS; Sheldrick, 1996)
T_min, T_max	0.786, 0.951
No. of measured, independent and observed [I > 2σ(I)] reflections	10457, 1870, 1009
R_int	0.078
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.078, 1.00
No. of reflections	1870
No. of parameters	141
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.30

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Co1—N1ⁱ	2.027 (3)	Co1—N2ⁱ	2.162 (3)
Co1—N1	2.027 (3)	Co1—N3	2.176 (3)
Co1—N2	2.162 (3)	Co1—N3ⁱ	2.176 (3)

N1ⁱ—Co1—N1	97.0 (2)	N2—Co1—N3	75.22 (11)
N1ⁱ—Co1—N2	166.18 (11)	N2ⁱ—Co1—N3	97.44 (10)
N1—Co1—N2	90.76 (12)	N1ⁱ—Co1—N3ⁱ	93.59 (11)
N1ⁱ—Co1—N2ⁱ	90.76 (12)	N1—Co1—N3ⁱ	92.83 (12)
N1—Co1—N2ⁱ	166.18 (11)	N2—Co1—N3ⁱ	97.44 (10)
N2—Co1—N2ⁱ	84.07 (14)	N2ⁱ—Co1—N3ⁱ	75.22 (11)
N1ⁱ—Co1—N3	92.83 (12)	N3—Co1—N3ⁱ	170.29 (13)
N1—Co1—N3	93.59 (11)

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···O1ⁱⁱ	0.93	2.50	3.236 (5)	136.7
C5—H5···O1ⁱⁱⁱ	0.93	2.48	3.198 (5)	134.1

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

Acknowledgements

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

References

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