Poly[bis-(cyanato-κN)bis-(μ-pyrazine-κN:N')cobalt(II)].

In the crystal structure of the title compound, [Co(NCO)(2)(C(4)H(4)N(2))(2)](n), the Co(II) cation is coordinated by four N-bonded pyrazine ligands and two N-bonded cyanate anions in a slightly distorted octa-hedral geometry. The crystal structure consists of μ-N:N' pyrazine-bridged cobalt cyanate chains; these are further linked by additional μ-N:N'-bridging pyrazine ligands into layers, which are stacked perpendicular to the crystallographic a axis. The C and O atoms in both crystallographic independent cyanate anions are disordered in two orientations and were refined using a split model with site occupation factor ratios of 0.75/0.25 and 0.7/0.3.

Related literature

For related pyrazine structures, see: Lloret et al. (1999 ▶); Real et al. (1991 ▶); Lu et al. (1997 ▶); Wriedt et al. (2009 ▶). For general background, see: Näther & Greve (2003 ▶); Näther et al. (2003 ▶); Wriedt et al. (2008 ▶, 2009 ▶); Näther et al. (2007 ▶); Näther & Jess (2004 ▶).

Experimental

Crystal data

[Co(NCO)2(C4H4N2)2]

M = 303.15

Monoclinic,

a = 25.5712 (17) Å

b = 10.1230 (8) Å

c = 10.1863 (7) Å

β = 104.763 (8)°

V = 2549.8 (3) Å3

Z = 8

Mo Kα radiation

μ = 1.35 mm−1

T = 170 K

0.24 × 0.14 × 0.07 mm

Data collection

Stoe IPDS-1 diffractometer

Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008 ▶) T min = 0.789, T max = 0.903

11369 measured reflections

2684 independent reflections

2058 reflections with I > 2σ(I)

R int = 0.039

Refinement

R[F 2 > 2σ(F 2)] = 0.051

wR(F 2) = 0.139

S = 1.04

2684 reflections

198 parameters

H-atom parameters constrained

Δρmax = 0.71 e Å−3

Δρmin = −1.17 e Å−3

Data collection: X-AREA (Stoe & Cie, 2008 ▶); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: XCIF in SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809005686/bt2872sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809005686/bt2872Isup2.hkl

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

[Co(NCO)2(C4H4N2)2]	F(000) = 1224
Mr = 303.15	Dx = 1.579 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 8000 reflections
a = 25.5712 (17) Å	θ = 14.1–25.9°
b = 10.1230 (8) Å	µ = 1.35 mm−1
c = 10.1863 (7) Å	T = 170 K
β = 104.763 (8)°	Block, yellow
V = 2549.8 (3) Å3	0.24 × 0.14 × 0.07 mm
Z = 8

Stoe IPDS-1 diffractometer	2684 independent reflections
Radiation source: fine-focus sealed tube	2058 reflections with I > 2σ(I)
graphite	Rint = 0.039
φ scans	θmax = 27.1°, θmin = 2.9°
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)	h = −32→32
Tmin = 0.789, Tmax = 0.903	k = −12→12
11369 measured reflections	l = −13→13

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.139	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0575P)2 + 18.631P] where P = (Fo2 + 2Fc2)/3
2684 reflections	(Δ/σ)max = 0.001
198 parameters	Δρmax = 0.71 e Å−3
0 restraints	Δρmin = −1.17 e Å−3

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	Occ. (<1)
Co1	0.629290 (19)	0.75059 (4)	0.63502 (4)	0.01326 (17)
N1	0.62838 (13)	0.5943 (3)	0.7846 (3)	0.0162 (6)
C1	0.66193 (17)	0.5983 (3)	0.9072 (4)	0.0224 (8)
H1	0.6868	0.6695	0.9297	0.027*
C2	0.66194 (17)	0.5014 (4)	1.0044 (3)	0.0224 (8)
H2	0.6864	0.5088	1.0916	0.027*
N2	0.62829 (13)	0.3981 (3)	0.9778 (3)	0.0171 (6)
C3	0.59444 (17)	0.3935 (4)	0.8537 (3)	0.0230 (8)
H3	0.5700	0.3215	0.8305	0.028*
C4	0.59412 (17)	0.4920 (4)	0.7578 (4)	0.0225 (8)
H4	0.5690	0.4864	0.6714	0.027*
N11	0.63140 (13)	0.9093 (3)	0.4902 (3)	0.0163 (6)
C11	0.67047 (17)	0.9151 (4)	0.4247 (4)	0.0228 (8)
H11	0.6992	0.8528	0.4461	0.027*
C12	0.67008 (17)	1.0102 (3)	0.3260 (4)	0.0222 (8)
H12	0.6984	1.0110	0.2810	0.027*
N12	0.63094 (13)	1.1005 (3)	0.2930 (3)	0.0167 (6)
C13	0.59214 (17)	1.0958 (4)	0.3588 (4)	0.0259 (9)
H13	0.5637	1.1590	0.3381	0.031*
C14	0.59239 (18)	1.0000 (4)	0.4575 (4)	0.0259 (9)
H14	0.5641	0.9993	0.5025	0.031*
N21	0.54684 (14)	0.7557 (3)	0.5817 (3)	0.0238 (7)
C21	0.5047 (3)	0.7083 (8)	0.5445 (8)	0.0347 (16)	0.75
O21	0.4602 (3)	0.6596 (9)	0.5110 (10)	0.109 (4)	0.75
O21'	0.4627 (6)	0.7506 (17)	0.4184 (18)	0.052 (4)	0.25
C21'	0.5054 (9)	0.7583 (16)	0.498 (2)	0.023 (4)	0.25
N31	0.71251 (14)	0.7443 (3)	0.6873 (3)	0.0218 (7)
C31	0.7539 (3)	0.7288 (7)	0.7698 (8)	0.0250 (15)	0.70
O31	0.7962 (3)	0.7135 (8)	0.8513 (7)	0.074 (3)	0.70
C31'	0.7530 (9)	0.7621 (19)	0.734 (2)	0.030 (6)*	0.30
O31'	0.8018 (11)	0.771 (2)	0.789 (3)	0.098 (8)*	0.30

	U11	U22	U33	U12	U13	U23
Co1	0.0272 (3)	0.0060 (2)	0.0076 (2)	−0.00033 (18)	0.00627 (18)	0.00004 (16)
N1	0.0307 (18)	0.0095 (13)	0.0085 (13)	−0.0035 (11)	0.0050 (13)	0.0015 (10)
C1	0.037 (2)	0.0124 (16)	0.0150 (16)	−0.0096 (15)	0.0022 (16)	0.0021 (13)
C2	0.037 (2)	0.0160 (17)	0.0103 (15)	−0.0053 (15)	−0.0003 (16)	0.0024 (13)
N2	0.0319 (18)	0.0090 (13)	0.0093 (13)	−0.0019 (11)	0.0033 (13)	0.0010 (10)
C3	0.039 (2)	0.0161 (17)	0.0119 (16)	−0.0099 (15)	0.0021 (16)	0.0006 (13)
C4	0.036 (2)	0.0161 (17)	0.0110 (15)	−0.0066 (15)	−0.0009 (16)	0.0028 (13)
N11	0.0312 (18)	0.0083 (13)	0.0119 (13)	0.0028 (11)	0.0100 (13)	0.0027 (10)
C11	0.036 (2)	0.0137 (17)	0.0241 (18)	0.0075 (15)	0.0172 (17)	0.0096 (14)
C12	0.036 (2)	0.0147 (16)	0.0220 (17)	0.0080 (15)	0.0182 (17)	0.0087 (14)
N12	0.0331 (18)	0.0079 (13)	0.0129 (14)	0.0033 (11)	0.0126 (14)	0.0015 (10)
C13	0.041 (2)	0.0177 (18)	0.0257 (19)	0.0137 (16)	0.0198 (19)	0.0117 (15)
C14	0.039 (2)	0.0179 (18)	0.0278 (19)	0.0093 (16)	0.0216 (18)	0.0111 (15)
N21	0.0311 (18)	0.0192 (16)	0.0204 (15)	−0.0023 (14)	0.0056 (16)	−0.0001 (12)
C21	0.034 (4)	0.032 (4)	0.040 (4)	0.000 (3)	0.014 (3)	−0.027 (3)
O21	0.041 (4)	0.137 (8)	0.152 (8)	−0.033 (4)	0.031 (5)	−0.114 (7)
O21'	0.027 (7)	0.061 (11)	0.055 (9)	0.012 (7)	−0.016 (8)	−0.038 (8)
C21'	0.040 (12)	0.004 (8)	0.023 (9)	0.001 (7)	0.003 (9)	0.004 (6)
N31	0.0318 (18)	0.0171 (16)	0.0183 (15)	0.0012 (13)	0.0099 (15)	−0.0002 (12)
C31	0.038 (4)	0.018 (3)	0.016 (3)	0.007 (3)	0.001 (3)	−0.010 (3)
O31	0.052 (4)	0.089 (5)	0.055 (4)	0.036 (4)	−0.031 (4)	−0.053 (4)

Co1—N21	2.039 (3)	N11—C11	1.337 (5)
Co1—N31	2.059 (3)	C11—C12	1.390 (5)
Co1—N11	2.191 (3)	C11—H11	0.9500
Co1—N2i	2.193 (3)	C12—N12	1.333 (5)
Co1—N12ii	2.197 (3)	C12—H12	0.9500
Co1—N1	2.200 (3)	N12—C13	1.332 (5)
N1—C1	1.324 (5)	N12—Co1iv	2.197 (3)
N1—C4	1.339 (5)	C13—C14	1.397 (5)
C1—C2	1.394 (5)	C13—H13	0.9500
C1—H1	0.9500	C14—H14	0.9500
C2—N2	1.337 (5)	N21—C21	1.151 (8)
C2—H2	0.9500	N21—C21'	1.18 (2)
N2—C3	1.338 (5)	C21—O21	1.206 (9)
N2—Co1iii	2.193 (3)	O21'—C21'	1.19 (3)
C3—C4	1.395 (5)	N31—C31'	1.04 (2)
C3—H3	0.9500	N31—C31	1.182 (8)
C4—H4	0.9500	C31—O31	1.195 (9)
N11—C14	1.334 (5)	C31'—O31'	1.24 (4)
N21—Co1—N31	179.45 (13)	N1—C4—H4	119.2
N21—Co1—N11	90.19 (12)	C3—C4—H4	119.2
N31—Co1—N11	89.76 (12)	C14—N11—C11	116.8 (3)
N21—Co1—N2i	90.23 (12)	C14—N11—Co1	121.8 (2)
N31—Co1—N2i	89.23 (12)	C11—N11—Co1	121.2 (2)
N11—Co1—N2i	90.53 (11)	N11—C11—C12	121.5 (3)
N21—Co1—N12ii	90.19 (12)	N11—C11—H11	119.2
N31—Co1—N12ii	90.35 (12)	C12—C11—H11	119.2
N11—Co1—N12ii	89.45 (10)	N12—C12—C11	121.6 (3)
N2i—Co1—N12ii	179.58 (12)	N12—C12—H12	119.2
N21—Co1—N1	90.57 (12)	C11—C12—H12	119.2
N31—Co1—N1	89.49 (12)	C13—N12—C12	117.1 (3)
N11—Co1—N1	178.55 (11)	C13—N12—Co1iv	121.0 (2)
N2i—Co1—N1	90.70 (10)	C12—N12—Co1iv	121.9 (2)
N12ii—Co1—N1	89.32 (10)	N12—C13—C14	121.3 (3)
C1—N1—C4	116.7 (3)	N12—C13—H13	119.3
C1—N1—Co1	120.9 (2)	C14—C13—H13	119.3
C4—N1—Co1	122.5 (2)	N11—C14—C13	121.6 (3)
N1—C1—C2	122.1 (3)	N11—C14—H14	119.2
N1—C1—H1	118.9	C13—C14—H14	119.2
C2—C1—H1	118.9	C21—N21—C21'	34.7 (8)
N2—C2—C1	121.5 (3)	C21—N21—Co1	153.4 (5)
N2—C2—H2	119.3	C21'—N21—Co1	150.6 (11)
C1—C2—H2	119.3	N21—C21—O21	177.2 (8)
C2—N2—C3	116.5 (3)	N21—C21'—O21'	174 (2)
C2—N2—Co1iii	120.1 (2)	C31'—N31—C31	24.8 (10)
C3—N2—Co1iii	123.4 (2)	C31'—N31—Co1	163.3 (12)
N2—C3—C4	121.6 (3)	C31—N31—Co1	150.1 (5)
N2—C3—H3	119.2	N31—C31—O31	178.7 (10)
C4—C3—H3	119.2	N31—C31'—O31'	174 (2)
N1—C4—C3	121.6 (3)

Table 1

Selected geometric parameters (Å, °)

Co1—N21	2.039 (3)
Co1—N31	2.059 (3)
Co1—N11	2.191 (3)
Co1—N2i	2.193 (3)
Co1—N12ii	2.197 (3)
Co1—N1	2.200 (3)

Symmetry codes: (i) ; (ii) .