Tetra­kis(3-cyano­pyridine-κN1)bis­(thio­cyanato-κN)cobalt(II) 1,4-dioxane disolvate

Diehr, S.; Wöhlert, S.; Boeckmann, J.; Näther, C.

doi:10.1107/S1600536811051087

metal-organic compounds

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Volume 67| Part 12| December 2011| Page m1898

https://doi.org/10.1107/S1600536811051087

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Tetrakis(3-cyanopyridine-κN¹)bis(thiocyanato-κN)cobalt(II) 1,4-dioxane disolvate

Stephan Diehr,^a Susanne Wöhlert,^a ^* Jan Boeckmann ^a and Christian Näther ^a

^aInstitut für Anorganische Chemie, Christian-Albrechts-Universität Kiel, Max-Eyth-Strasse 2, 24098 Kiel, Germany
^*Correspondence e-mail: swoehlert@ac.uni-kiel.de

(Received 18 November 2011; accepted 28 November 2011; online 30 November 2011)

In the crystal structure of the title compound, {[Co(NCS)₂(C₆H₄N₂)₄]·2C₄H₈O₂}, the Co^II cations are octahedrally coordinated by two terminal N-bonded thiocyanate anions and four N-bonded 3-cyanopyridine ligands. The asymmetric unit consists of one Co^II cation, which is located on a special position with site symmetry 2/m, one thiocyanate anion and one dioxane molecule, located on a crystallographic mirror plane, as well as one 3-cyanopyridine ligand in a general position. The crystal structure consists of discrete complexes of [Co(NCS)₂(3-cyanopyridine)₄], as well as two non-coordinating 1,4-dioxane solvent molecules 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_r = 767.75
Monoclinic, C 2/m
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[F² > 2σ(F²)] = 0.044
wR(F²) = 0.098
S = 1.17
2271 reflections
143 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536811051087/wm2564sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811051087/wm2564Isup2.hkl

checkCIF report

Comment top

Recently, we became interested in new transition metal thiocyanato coordination polymers with terminal thiocyanate anions that can be used as precursors in thermal decomposition reactions in order to prepare new coordination compounds in which the metal cations are linked by the anionic ligands (Boeckmann & Näther, 2010, 2011; Wöhlert et al., 2011). In our ongoing investigation in this field we have reacted cobalt(II) thiocyanate and 3-cyanopyridine in dioxane. In this reaction light-red single crystals of the title compound were obtained, which were characterized by single-crystal X-ray diffraction.

In the crystal structure of the title compound, [Co(NCS)₂(C₆H₄N₂)₄]^.2(C₄H₈O₂), the cobalt(II) cations are coordinated by two terminal N-bonded thiocyanate anions and by four 3-cyanopyridine ligands into discrete complexes which are located on special positions with site symmetry 2/m (Fig. 1). The octahedral coordination sphere of the cobalt(II) cations is slightly distorted with distances in the range of 2.036 (2) Å to 2.2451 (16) Å. The angles around the cobalt(II) cations range from 89.67 (6)° to 180 °. The discrete complexes are stacked into columns that elongate in the direction of the c-axis (Fig. 2). From this arrangement channels are formed in which the disordered dioxane molecules are located. It should be noted that according to a search in the CCDC database (CONQUEST Ver. 1.13.2011; Allen, 2002) discrete complexes based on cobalt(II) thiocyanate and 3-cyanopyridine with solvate molecules (i.e. ethanol and dichloromethane) have already been reported (Kilkenny & Nassimbeni, 2001).

Related literature top

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 top

Cobalt(II) thiocyanate and 3-cyanopyridine were obtained from Alfa Aesar, and 1,4-dioxane from Sigma Aldrich. 0.25 mmol (44.0 mg) Co(NCS)₂^.xH₂O, 0.50 mmol (52.1 mg) 3-cyanopyridine and 1.5 ml 1,4-dioxane were reacted in a closed snap-vial without stirring. After the mixture has been standing for several days at room temperature light-red single crystals of the title compound were obtained on slow evaporation of the solvent.

Structure description top

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).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2008); cell refinement: X-AREA (Stoe & Cie, 2008); data reduction: X-AREA (Stoe & Cie, 2008); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. : The molecular moieties of the crystal structure of the title compound with atom labelling and displacement ellipsoids drawn at the 30% probability level. The disorder of the dioxane ligand is shown by full and open bonds. [Symmetry codes: i: -x + 1, -y + 1, -z + 1; ii: -x + 1, y, -z + 1; iii: x, -y + 1, z.]
	Fig. 2. : Crystal structure of the title compound with view along the crystallographic a-axis. The non-coordinated 1,4-dioxane were omitted for clarity.

Tetrakis(3-cyanopyridine-κN¹)bis(thiocyanato-κN)cobalt(II) 1,4-dioxane disolvate top

Crystal data top

[Co(NCS)₂(C₆H₄N₂)₄]·2C₄H₈O₂	F(000) = 794
M_r = 767.75	D_x = 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

Data collection top

Stoe IPDS-2 diffractometer	2271 independent reflections
Radiation source: fine-focus sealed tube	1997 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.061
ω scans	θ_max = 28.0°, θ_min = 2.1°
Absorption correction: numerical (X-RED32 and X-SHAPE; Stoe & Cie, 2008)	h = −20→20
T_min = 0.911, T_max = 0.941	k = −18→18
14354 measured reflections	l = −13→13

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.098	H-atom parameters constrained
S = 1.17	w = 1/[σ²(F_o²) + (0.0397P)² + 0.8865P] where P = (F_o² + 2F_c²)/3
2271 reflections	(Δ/σ)_max < 0.001
143 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

[Co(NCS)₂(C₆H₄N₂)₄]·2C₄H₈O₂	V = 1829.61 (14) Å³
M_r = 767.75	Z = 2
Monoclinic, C2/m	Mo Kα radiation
a = 15.5222 (6) Å	µ = 0.64 mm⁻¹
b = 14.1865 (7) Å	T = 293 K
c = 10.0762 (4) Å	0.12 × 0.10 × 0.08 mm
β = 124.454 (3)°

Data collection top

Stoe IPDS-2 diffractometer	2271 independent reflections
Absorption correction: numerical (X-RED32 and X-SHAPE; Stoe & Cie, 2008)	1997 reflections with I > 2σ(I)
T_min = 0.911, T_max = 0.941	R_int = 0.061
14354 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.098	H-atom parameters constrained
S = 1.17	Δρ_max = 0.26 e Å⁻³
2271 reflections	Δρ_min = −0.27 e Å⁻³
143 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	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

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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

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

Experimental details

Crystal data
Chemical formula	[Co(NCS)₂(C₆H₄N₂)₄]·2C₄H₈O₂
M_r	767.75
Crystal system, space group	Monoclinic, C2/m
Temperature (K)	293
a, b, c (Å)	15.5222 (6), 14.1865 (7), 10.0762 (4)
β (°)	124.454 (3)
V (Å³)	1829.61 (14)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.64
Crystal size (mm)	0.12 × 0.10 × 0.08

Data collection
Diffractometer	Stoe IPDS2
Absorption correction	Numerical (X-RED32 and X-SHAPE; Stoe & Cie, 2008)
T_min, T_max	0.911, 0.941
No. of measured, independent and observed [I > 2σ(I)] reflections	14354, 2271, 1997
R_int	0.061
(sin θ/λ)_max (Å⁻¹)	0.659

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.098, 1.17
No. of reflections	2271
No. of parameters	143
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.27

Computer programs: X-AREA (Stoe & Cie, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2010), XCIF in SHELXTL (Sheldrick, 2008).

Acknowledgements

We gratefully acknowledge financial support by the State of Schleswig-Holstein and the Deutsche Forschungsgemeinschaft (project No. NA 720/3–1). We thank Professor Dr Wolfgang Bensch for access to his experimental facility.

References

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