Tetra-kis(3-cyano-pyridine-κN)bis-(thio-cyanato-κN)cobalt(II) 1,4-dioxane disolvate.

In the crystal structure of the title compound, {[Co(NCS)(2)(C(6)H(4)N(2))(4)]·2C(4)H(8)O(2)}, the Co(II) cations are octa-hedrally coordinated by two terminal N-bonded thio-cyanate anions and four N-bonded 3-cyano-pyridine ligands. The asymmetric unit consists of one Co(II) cation, which is located on a special position with site symmetry 2/m, one thio-cyanate anion and one dioxane mol-ecule, located on a crystallographic mirror plane, as well as one 3-cyano-pyridine ligand in a general position. The crystal structure consists of discrete complexes of [Co(NCS)(2)(3-cyano-pyridine)(4)], as well as two non-coordinating 1,4-dioxane solvent mol-ecules which are disordered due to symmetry.

Related literature

For related structures, see: Kilkenny & Nassimbeni (2001 ▶). For background to this work, see: Boeckmann & Näther (2010 ▶, 2011 ▶); Wöhlert et al. (2011 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶).

Experimental

Crystal data

[Co(NCS)2(C6H4N2)4]·2C4H8O2

M = 767.75

Monoclinic,

a = 15.5222 (6) Å

b = 14.1865 (7) Å

c = 10.0762 (4) Å

β = 124.454 (3)°

V = 1829.61 (14) Å3

Z = 2

Mo Kα radiation

μ = 0.64 mm−1

T = 293 K

0.12 × 0.10 × 0.08 mm

Data collection

Stoe IPDS-2 diffractometer

Absorption correction: numerical (X-RED32 and X-SHAPE; Stoe & Cie, 2008) ▶ T min = 0.911, T max = 0.941

14354 measured reflections

2271 independent reflections

1997 reflections with I > 2σ(I)

R int = 0.061

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.098

S = 1.17

2271 reflections

143 parameters

H-atom parameters constrained

Δρmax = 0.26 e Å−3

Δρmin = −0.27 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 ▶) and DIAMOND (Brandenburg, 2010 ▶); software used to prepare material for publication: XCIF in SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811051087/wm2564sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811051087/wm2564Isup2.hkl

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

[Co(NCS)2(C6H4N2)4]·2C4H8O2	F(000) = 794
Mr = 767.75	Dx = 1.394 Mg m−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2y	Cell parameters from 14354 reflections
a = 15.5222 (6) Å	θ = 2.1–28.0°
b = 14.1865 (7) Å	µ = 0.64 mm−1
c = 10.0762 (4) Å	T = 293 K
β = 124.454 (3)°	Block, light-red
V = 1829.61 (14) Å3	0.12 × 0.10 × 0.08 mm
Z = 2

Stoe IPDS-2 diffractometer	2271 independent reflections
Radiation source: fine-focus sealed tube	1997 reflections with I > 2σ(I)
graphite	Rint = 0.061
ω scans	θmax = 28.0°, θmin = 2.1°
Absorption correction: numerical (X-RED32 and X-SHAPE; Stoe & Cie, 2008)	h = −20→20
Tmin = 0.911, Tmax = 0.941	k = −18→18
14354 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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.098	H-atom parameters constrained
S = 1.17	w = 1/[σ2(Fo2) + (0.0397P)2 + 0.8865P] where P = (Fo2 + 2Fc2)/3
2271 reflections	(Δ/σ)max < 0.001
143 parameters	Δρmax = 0.26 e Å−3
0 restraints	Δρmin = −0.27 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	0.5000	0.5000	0.5000	0.03493 (15)
S1	0.12527 (6)	0.5000	0.14723 (11)	0.0599 (2)
N1	0.34226 (17)	0.5000	0.3366 (3)	0.0451 (5)
N11	0.48617 (12)	0.61900 (11)	0.63377 (18)	0.0432 (4)
N12	0.7165 (2)	0.7574 (2)	1.1532 (3)	0.0901 (8)
C1	0.2515 (2)	0.5000	0.2576 (3)	0.0391 (5)
C11	0.56168 (16)	0.63928 (14)	0.7862 (2)	0.0470 (4)
H11	0.6154	0.5960	0.8449	0.056*
C12	0.56356 (18)	0.72207 (16)	0.8610 (3)	0.0531 (5)
C13	0.4847 (2)	0.78700 (17)	0.7760 (3)	0.0665 (6)
H13	0.4844	0.8432	0.8233	0.080*
C14	0.4063 (2)	0.76611 (18)	0.6192 (3)	0.0696 (7)
H14	0.3516	0.8082	0.5583	0.084*
C15	0.40956 (17)	0.68248 (16)	0.5528 (3)	0.0539 (5)
H15	0.3559	0.6695	0.4465	0.065*
C16	0.6490 (2)	0.74119 (19)	1.0243 (3)	0.0675 (7)
O31	0.6959 (2)	0.5000	0.1030 (3)	0.0958 (10)
C31	0.8027 (5)	0.5305 (4)	0.1665 (7)	0.084 (2)	0.50
H31A	0.8122	0.5958	0.1966	0.101*	0.50
H31B	0.8183	0.5213	0.0878	0.101*	0.50
C32	0.8720 (5)	0.4714 (5)	0.3113 (7)	0.087 (2)	0.50
H32A	0.9443	0.4792	0.3518	0.104*	0.50
H32B	0.8535	0.4063	0.2835	0.104*	0.50
O32	0.8526 (3)	0.5000	0.4305 (3)	0.0994 (11)
C33	0.7480 (5)	0.4743 (4)	0.3704 (6)	0.083 (2)	0.50
H33A	0.7341	0.4862	0.4504	0.100*	0.50
H33B	0.7372	0.4085	0.3439	0.100*	0.50
C34	0.6764 (5)	0.5311 (4)	0.2226 (7)	0.0811 (18)	0.50
H34A	0.6047	0.5214	0.1842	0.097*	0.50
H34B	0.6927	0.5968	0.2454	0.097*	0.50

	U11	U22	U33	U12	U13	U23
Co1	0.0262 (2)	0.0399 (3)	0.0286 (2)	0.000	0.00942 (18)	0.000
S1	0.0296 (4)	0.0637 (5)	0.0687 (5)	0.000	0.0173 (3)	0.000
N1	0.0295 (10)	0.0522 (13)	0.0391 (11)	0.000	0.0108 (9)	0.000
N11	0.0391 (8)	0.0451 (8)	0.0415 (8)	0.0013 (7)	0.0205 (7)	−0.0009 (6)
N12	0.0892 (17)	0.0930 (18)	0.0677 (14)	−0.0095 (14)	0.0321 (13)	−0.0358 (13)
C1	0.0380 (13)	0.0406 (13)	0.0349 (12)	0.000	0.0183 (10)	0.000
C11	0.0435 (10)	0.0493 (11)	0.0428 (9)	0.0018 (8)	0.0212 (8)	−0.0045 (8)
C12	0.0555 (12)	0.0534 (12)	0.0550 (11)	−0.0057 (10)	0.0340 (10)	−0.0120 (9)
C13	0.0743 (17)	0.0518 (12)	0.0812 (16)	0.0049 (11)	0.0487 (14)	−0.0127 (11)
C14	0.0649 (15)	0.0585 (14)	0.0782 (16)	0.0219 (12)	0.0362 (13)	0.0052 (12)
C15	0.0458 (11)	0.0549 (12)	0.0533 (11)	0.0096 (9)	0.0233 (9)	0.0027 (9)
C16	0.0716 (16)	0.0665 (15)	0.0647 (14)	−0.0050 (12)	0.0387 (13)	−0.0232 (12)
O31	0.0758 (19)	0.153 (3)	0.0465 (13)	0.000	0.0271 (14)	0.000
C31	0.093 (4)	0.110 (6)	0.067 (3)	0.005 (3)	0.056 (3)	0.003 (3)
C32	0.066 (3)	0.109 (7)	0.074 (3)	0.006 (3)	0.033 (3)	−0.004 (3)
O32	0.087 (2)	0.144 (3)	0.0476 (14)	0.000	0.0270 (14)	0.000
C33	0.109 (4)	0.090 (6)	0.065 (3)	−0.001 (3)	0.058 (3)	0.004 (3)
C34	0.083 (4)	0.089 (5)	0.082 (3)	0.011 (3)	0.053 (3)	0.015 (3)

Co1—N1i	2.036 (2)	C15—H15	0.9300
Co1—N1	2.036 (2)	O31—C31iii	1.464 (7)
Co1—N11i	2.2451 (16)	O31—C31	1.464 (7)
Co1—N11	2.2451 (16)	O31—C34	1.466 (6)
Co1—N11ii	2.2451 (16)	O31—C34iii	1.466 (6)
Co1—N11iii	2.2451 (16)	C31—C32	1.488 (8)
S1—C1	1.615 (3)	C31—H31A	0.9599
N1—C1	1.162 (3)	C31—H31B	0.9599
N11—C11	1.334 (2)	C32—O32	1.451 (6)
N11—C15	1.339 (3)	C32—H32A	0.9600
N12—C16	1.140 (3)	C32—H32B	0.9601
C11—C12	1.387 (3)	O32—C33	1.423 (7)
C11—H11	0.9300	O32—C33iii	1.423 (7)
C12—C13	1.376 (3)	O32—C32iii	1.451 (6)
C12—C16	1.439 (3)	C33—C34	1.493 (7)
C13—C14	1.375 (4)	C33—H33A	0.9600
C13—H13	0.9300	C33—H33B	0.9600
C14—C15	1.377 (3)	C34—H34A	0.9600
C14—H14	0.9300	C34—H34B	0.9599
N1i—Co1—N1	180.00 (10)	N11—C15—C14	123.2 (2)
N1i—Co1—N11i	90.33 (6)	N11—C15—H15	118.4
N1—Co1—N11i	89.67 (6)	C14—C15—H15	118.4
N1i—Co1—N11	89.67 (6)	N12—C16—C12	179.2 (3)
N1—Co1—N11	90.33 (6)	C31—O31—C34	105.1 (4)
N11i—Co1—N11	180.0	C31iii—O31—C34iii	105.1 (4)
N1i—Co1—N11ii	90.33 (6)	O31—C31—C32	105.9 (4)
N1—Co1—N11ii	89.67 (6)	O31—C31—H31A	110.9
N11i—Co1—N11ii	97.52 (8)	C32—C31—H31A	109.7
N11—Co1—N11ii	82.48 (8)	O31—C31—H31B	110.6
N1i—Co1—N11iii	89.67 (6)	C32—C31—H31B	110.7
N1—Co1—N11iii	90.33 (6)	H31A—C31—H31B	109.0
N11i—Co1—N11iii	82.48 (8)	O32—C32—C31	106.3 (4)
N11—Co1—N11iii	97.52 (8)	O32—C32—H32A	110.8
N11ii—Co1—N11iii	180.00 (5)	C31—C32—H32A	112.0
C1—N1—Co1	172.6 (2)	O32—C32—H32B	110.1
C11—N11—C15	117.11 (18)	C31—C32—H32B	109.0
C11—N11—Co1	122.24 (13)	H32A—C32—H32B	108.7
C15—N11—Co1	119.56 (13)	C33iii—O32—C32iii	107.3 (4)
N1—C1—S1	179.8 (2)	C33—O32—C32	107.3 (4)
N11—C11—C12	122.9 (2)	O32—C33—C34	108.2 (4)
N11—C11—H11	118.6	O32—C33—H33A	110.0
C12—C11—H11	118.6	C34—C33—H33A	110.5
C13—C12—C11	119.4 (2)	O32—C33—H33B	110.2
C13—C12—C16	120.3 (2)	C34—C33—H33B	109.4
C11—C12—C16	120.2 (2)	H33A—C33—H33B	108.5
C14—C13—C12	117.9 (2)	O31—C34—C33	106.0 (4)
C14—C13—H13	121.1	O31—C34—H34A	111.0
C12—C13—H13	121.1	C33—C34—H34A	111.3
C13—C14—C15	119.5 (2)	O31—C34—H34B	109.9
C13—C14—H14	120.2	C33—C34—H34B	109.8
C15—C14—H14	120.2	H34A—C34—H34B	108.8