catena-Poly[[bis­(methanol-κO)bis­(thio­cyanato-κN)cobalt(II)]-μ-1,3-bis­(pyridin-4-yl)propane-κ2N,N′]

Wöhlert, S.; Näther, C.

doi:10.1107/S1600536812000499

metal-organic compounds

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Volume 68| Part 2| February 2012| Page m138

doi:10.1107/S1600536812000499

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catena-Poly[[bis(methanol-κO)bis(thiocyanato-κN)cobalt(II)]-μ-1,3-bis(pyridin-4-yl)propane-κ²N,N′]

Susanne Wöhlert ^a ^* and Christian Näther ^a

^aInstitut für Anorganische Chemie, Christian-Albrechts-Universität Kiel, Max-Eyth Strasse 2, D-24118 Kiel, Germany
^*Correspondence e-mail: swoehlert@ac.uni-kiel.de

(Received 3 January 2012; accepted 5 January 2012; online 11 January 2012)

The asymmetric unit of the title compound, [Co(NCS)₂(C₁₃H₁₄N₂)(CH₃OH)₂], consists of one cobalt(II) cation located on a center of inversion, one half of a 1,3-bis(pyridin-4-yl)propane ligand located on a twofold rotation axis, as well as one thiocyanate anion and one methanol molecule in general positions. The cobalt(II) cation is coordinated by two terminal N-bonded thiocyanate anions and two N-bonded 1,3-bis(pyridin-4-yl)propane ligands, as well as two O atoms of methanol molecules in a slightly distorted octahedral coordination mode. Adjacent cations are connected into chains parallel to [10 $[\overline{1}]$ ] by the bridging 1,3-bis(pyridin-4-yl)propane ligands. These chains are connected through intermolecular O—H⋯S hydrogen bonds between the methanol hydroxy group and the terminal S atom of the thiocyanate anion.

Related literature

For related structures, see: Merz et al. (2004 ). For background literature for this work, see: Boeckmann & Näther (2010 ); Wöhlert et al. (2011 ); Wriedt et al. (2009 ). For a description of the Cambridge Structural Database, see: Allen (2002 ).

Experimental

Crystal data

[Co(NCS)₂(C₁₃H₁₄N₂)(CH₄O)₂]
M_r = 437.44
Monoclinic, C 2/c
a = 20.5440 (12) Å
b = 7.5708 (3) Å
c = 13.4274 (7) Å
β = 95.176 (5)°
V = 2079.91 (18) Å³
Z = 4
Mo Kα radiation
μ = 1.04 mm⁻¹
T = 293 K
0.12 × 0.02 × 0.02 mm

Data collection

Stoe IPDS-2 diffractometer
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008 ) T_min = 0.971, T_max = 0.983
7860 measured reflections
2463 independent reflections
2105 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.081
S = 1.05
2463 reflections
125 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Selected bond lengths (Å)

Co1—N1	2.0887 (17)
Co1—O1	2.1372 (15)
Co1—N10	2.1624 (15)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O1⋯S1ⁱ	0.74 (4)	2.54 (4)	3.2539 (19)	165 (4)
Symmetry code: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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: 10.1107/S1600536812000499/wm2581sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812000499/wm2581Isup2.hkl

checkCIF report

Comment top

In the last few years we have demonstrated that thermal decomposition reactions are an elegante route for the selective synthesis of new ligand-deficient coordination polymers with cooperative magnetic properties (Boeckmann & Näther, 2010; Wöhlert et al., 2011). In this procedure ligand-rich precursor compounds based on paramagnetic transition metal thiocyanates and neutral monodentate or bidentate N-donor ligands are heated, leading to a stepwise loss of the neutral ligands, which yields ligand-deficient coordination compounds (Wriedt et al., 2009). For the preparation of new precursor compounds we have reacted cobalt(II) thiocyanate and 1,3-bis(pyridin-4-yl)-propane in methanol. In this reaction light-green single crystals of the title compound, [Co(NCS)₂(C₁₃H₁₄N₂)(CH₃OH)₂], were obtained, which were characterized by single-crystal X-ray diffraction.

In the crystal structure of the title compound the cobalt(II) cations are coordinated by two terminal N-bonded thiocyanate anions, two O-bonded methanol molecules and two N-bonded 1,3-bis(pyridin-4-yl)-propane ligands (Fig. 1). The octahedral coordination sphere of the cobalt(II) cation is slightly distorted with distances in the range of 2.0887 (17) Å to 2.1624 (15) Å. The angles around the cobalt(II) cations range from 88.43 (6) ° to 180 °. The Co(II) cations are bridged by the neutral 1,3-bis(pyridin-4-yl)-propane ligand into chains parallel to [101] (Fig. 2). These chains are further connected through intermolecular O—H···S hydrogen between the methanol molecules and terminal S atoms of the anions (Fig. 2, Table 2). It should be noted that according to a search in the CCDC database (CONQUEST; version 13.2011; Allen, 2002) one structure based on cobalt(II) thiocyanate and 1,3-bis(pyridin-4-yl)-propane has already been reported (Merz et al., 2004). In this structure the cobalt(II) cations are octahedrally coordinated by four 1,3-bis(pyridin-4-yl)-propane ligands and two terminal N-bonded thiocyanato anions. The cobalt(II) cations are linked by the 1,3-bis(pyridin-4-yl)-propane ligands into chains oriented along the crystallographic a-axis that are further connected by the neutral co-ligands into layers.

Related literature top

For related structures, see: Merz et al. (2004). For background literature for this work, see: Boeckmann & Näther (2010); Wöhlert et al. (2011); Wriedt et al. (2009). For a description of the Cambridge Structural Database, see: Allen (2002).

Experimental top

Cobalt(II) thiocyanate, 1,3-bis(pyridin-4-yl)-propane and methanol were obtained from Alfa Aesar and were used without further purification. 0.6 mmol (104.4 mg) cobalt(II) thiocyanate, 0.15 mmol (34.4 mg) 1,3-bis(pyridin-4-yl)-propane and 1 mL methanol were reacted in a closed snap-vial without stirring. After the mixture has been standing for several days at room temperature, light-green single crystals suitable for X-ray diffraction were obtained.

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. : Crystal structure of the title compound with labelling and displacement ellipsoids drawn at the 50% probability level. [Symmetry codes: i) -x+1/2; -y+1/2; -z+1 and ii) -x; y; -z+1/2.]
	Fig. 2. : Crystal structure of the title compound in a view along the b axis. O—H···S hydrogen bonds are depicted with dotted lines.

catena-Poly[[bis(methanol-κO)bis(thiocyanato- κN)cobalt(II)]-µ-1,3-bis(pyridin-4-yl)propane- κ²N,N'] top

Crystal data top

[Co(NCS)₂(C₁₃H₁₄N₂)(CH₄O)₂]	F(000) = 908
M_r = 437.44	D_x = 1.397 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 7860 reflections
a = 20.5440 (12) Å	θ = 2.9–28.0°
b = 7.5708 (3) Å	µ = 1.04 mm⁻¹
c = 13.4274 (7) Å	T = 293 K
β = 95.176 (5)°	Block, light-green
V = 2079.91 (18) Å³	0.12 × 0.02 × 0.02 mm
Z = 4

Data collection top

Stoe IPDS-2 diffractometer	2463 independent reflections
Radiation source: fine-focus sealed tube	2105 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ω scans	θ_max = 28.0°, θ_min = 2.9°
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)	h = −26→26
T_min = 0.971, T_max = 0.983	k = −9→9
7860 measured reflections	l = −17→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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.081	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0342P)² + 1.3966P] where P = (F_o² + 2F_c²)/3
2463 reflections	(Δ/σ)_max < 0.001
125 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

[Co(NCS)₂(C₁₃H₁₄N₂)(CH₄O)₂]	V = 2079.91 (18) Å³
M_r = 437.44	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 20.5440 (12) Å	µ = 1.04 mm⁻¹
b = 7.5708 (3) Å	T = 293 K
c = 13.4274 (7) Å	0.12 × 0.02 × 0.02 mm
β = 95.176 (5)°

Data collection top

Stoe IPDS-2 diffractometer	2463 independent reflections
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)	2105 reflections with I > 2σ(I)
T_min = 0.971, T_max = 0.983	R_int = 0.021
7860 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.081	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.25 e Å⁻³
2463 reflections	Δρ_min = −0.25 e Å⁻³
125 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.2500	0.2500	0.5000	0.04506 (12)
N1	0.30569 (8)	0.4522 (2)	0.44450 (13)	0.0576 (4)
C1	0.33565 (9)	0.5317 (3)	0.39083 (14)	0.0489 (4)
S1	0.37746 (3)	0.64359 (9)	0.31502 (4)	0.06640 (17)
N10	0.16009 (7)	0.3899 (2)	0.45687 (11)	0.0487 (4)
C10	0.10533 (9)	0.3059 (3)	0.42263 (15)	0.0539 (4)
H10	0.1051	0.1831	0.4236	0.065*
C11	0.04904 (9)	0.3927 (3)	0.38589 (15)	0.0574 (5)
H11	0.0123	0.3283	0.3625	0.069*
C12	0.04733 (9)	0.5744 (3)	0.38384 (14)	0.0525 (5)
C13	0.10384 (10)	0.6616 (3)	0.42123 (17)	0.0607 (5)
H13	0.1050	0.7844	0.4224	0.073*
C14	0.15805 (10)	0.5664 (3)	0.45640 (16)	0.0568 (5)
H14	0.1952	0.6279	0.4812	0.068*
C15	−0.01223 (10)	0.6752 (4)	0.34160 (16)	0.0639 (6)
H15A	−0.0263	0.7532	0.3928	0.077*
H15B	−0.0474	0.5923	0.3238	0.077*
C16	0.0000	0.7841 (4)	0.2500	0.0652 (8)
H16A	0.0375	0.8597	0.2666	0.078*	0.50
H16B	−0.0375	0.8597	0.2334	0.078*	0.50
O1	0.24410 (8)	0.1222 (3)	0.35756 (11)	0.0623 (4)
H1O1	0.2117 (13)	0.118 (4)	0.328 (2)	0.076 (9)*
C2	0.29545 (11)	0.1156 (4)	0.29272 (18)	0.0723 (7)
H2A	0.2931	0.2178	0.2502	0.108*
H2B	0.2909	0.0109	0.2524	0.108*
H2C	0.3369	0.1138	0.3319	0.108*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.03980 (18)	0.0573 (2)	0.03795 (17)	−0.00119 (15)	0.00289 (12)	0.00289 (15)
N1	0.0515 (9)	0.0658 (11)	0.0553 (9)	−0.0043 (8)	0.0043 (7)	0.0111 (8)
C1	0.0442 (9)	0.0541 (10)	0.0472 (9)	0.0013 (8)	−0.0023 (7)	0.0005 (8)
S1	0.0598 (3)	0.0797 (4)	0.0602 (3)	−0.0151 (3)	0.0084 (2)	0.0112 (3)
N10	0.0408 (7)	0.0627 (10)	0.0423 (8)	0.0013 (7)	0.0013 (6)	0.0001 (7)
C10	0.0463 (10)	0.0645 (12)	0.0506 (10)	−0.0046 (8)	0.0018 (8)	0.0022 (9)
C11	0.0423 (9)	0.0770 (14)	0.0522 (10)	−0.0071 (9)	0.0002 (8)	0.0007 (10)
C12	0.0426 (9)	0.0757 (13)	0.0391 (9)	0.0062 (9)	0.0037 (7)	−0.0040 (9)
C13	0.0564 (11)	0.0602 (13)	0.0633 (12)	0.0075 (10)	−0.0061 (9)	−0.0088 (10)
C14	0.0473 (10)	0.0624 (12)	0.0585 (11)	−0.0006 (9)	−0.0072 (8)	−0.0075 (10)
C15	0.0471 (10)	0.0889 (16)	0.0552 (11)	0.0141 (10)	0.0010 (9)	−0.0059 (11)
C16	0.0563 (16)	0.066 (2)	0.0705 (19)	0.000	−0.0128 (14)	0.000
O1	0.0474 (8)	0.0938 (12)	0.0454 (7)	0.0011 (8)	0.0029 (6)	−0.0106 (8)
C2	0.0583 (12)	0.1018 (19)	0.0582 (12)	0.0048 (12)	0.0135 (10)	−0.0160 (13)

Geometric parameters (Å, º) top

Co1—N1	2.0887 (17)	C12—C15	1.509 (3)
Co1—N1ⁱ	2.0887 (17)	C13—C14	1.374 (3)
Co1—O1	2.1372 (15)	C13—H13	0.9300
Co1—O1ⁱ	2.1372 (15)	C14—H14	0.9300
Co1—N10	2.1624 (15)	C15—C16	1.520 (3)
Co1—N10ⁱ	2.1624 (15)	C15—H15A	0.9700
N1—C1	1.158 (2)	C15—H15B	0.9700
C1—S1	1.628 (2)	C16—C15ⁱⁱ	1.520 (3)
N10—C14	1.337 (3)	C16—H16A	0.9700
N10—C10	1.337 (2)	C16—H16B	0.9700
C10—C11	1.382 (3)	O1—C2	1.428 (2)
C10—H10	0.9300	O1—H1O1	0.74 (3)
C11—C12	1.376 (3)	C2—H2A	0.9600
C11—H11	0.9300	C2—H2B	0.9600
C12—C13	1.390 (3)	C2—H2C	0.9600

N1—Co1—N1ⁱ	180.00 (10)	C13—C12—C15	121.2 (2)
N1—Co1—O1	90.07 (7)	C14—C13—C12	120.0 (2)
N1ⁱ—Co1—O1	89.93 (7)	C14—C13—H13	120.0
N1—Co1—O1ⁱ	89.93 (7)	C12—C13—H13	120.0
N1ⁱ—Co1—O1ⁱ	90.07 (7)	N10—C14—C13	123.36 (19)
O1—Co1—O1ⁱ	180.0	N10—C14—H14	118.3
N1—Co1—N10	91.57 (6)	C13—C14—H14	118.3
N1ⁱ—Co1—N10	88.43 (6)	C12—C15—C16	113.01 (16)
O1—Co1—N10	90.23 (6)	C12—C15—H15A	109.0
O1ⁱ—Co1—N10	89.77 (6)	C16—C15—H15A	109.0
N1—Co1—N10ⁱ	88.43 (6)	C12—C15—H15B	109.0
N1ⁱ—Co1—N10ⁱ	91.57 (6)	C16—C15—H15B	109.0
O1—Co1—N10ⁱ	89.77 (6)	H15A—C15—H15B	107.8
O1ⁱ—Co1—N10ⁱ	90.23 (6)	C15—C16—C15ⁱⁱ	114.3 (3)
N10—Co1—N10ⁱ	180.00 (8)	C15—C16—H16A	108.7
C1—N1—Co1	160.42 (17)	C15ⁱⁱ—C16—H16A	108.7
N1—C1—S1	179.7 (2)	C15—C16—H16B	108.7
C14—N10—C10	116.65 (17)	C15ⁱⁱ—C16—H16B	108.7
C14—N10—Co1	121.10 (13)	H16A—C16—H16B	107.6
C10—N10—Co1	122.08 (14)	C2—O1—Co1	125.17 (14)
N10—C10—C11	123.2 (2)	C2—O1—H1O1	110 (2)
N10—C10—H10	118.4	Co1—O1—H1O1	118 (2)
C11—C10—H10	118.4	O1—C2—H2A	109.5
C12—C11—C10	120.10 (19)	O1—C2—H2B	109.5
C12—C11—H11	120.0	H2A—C2—H2B	109.5
C10—C11—H11	120.0	O1—C2—H2C	109.5
C11—C12—C13	116.67 (18)	H2A—C2—H2C	109.5
C11—C12—C15	122.1 (2)	H2B—C2—H2C	109.5

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···S1ⁱⁱⁱ	0.74 (4)	2.54 (4)	3.2539 (19)	165 (4)

Symmetry code: (iii) −x+1/2, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Co(NCS)₂(C₁₃H₁₄N₂)(CH₄O)₂]
M_r	437.44
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	20.5440 (12), 7.5708 (3), 13.4274 (7)
β (°)	95.176 (5)
V (Å³)	2079.91 (18)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.04
Crystal size (mm)	0.12 × 0.02 × 0.02

Data collection
Diffractometer	Stoe IPDS2 diffractometer
Absorption correction	Numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)
T_min, T_max	0.971, 0.983
No. of measured, independent and observed [I > 2σ(I)] reflections	7860, 2463, 2105
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.660

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.081, 1.05
No. of reflections	2463
No. of parameters	125
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.25

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).

Selected bond lengths (Å) top

Co1—N1	2.0887 (17)	Co1—N10	2.1624 (15)
Co1—O1	2.1372 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···S1ⁱ	0.74 (4)	2.54 (4)	3.2539 (19)	165 (4)

Symmetry code: (i) −x+1/2, y−1/2, −z+1/2.

Acknowledgements

We gratefully acknowledge financial support from the DFG (project No. NA 720/3–1) and the State of Schleswig–Holstein. We thank Professor Dr Wolfgang Bensch for access to his experimental facilities. Special thanks go to Inke Jess for her support of the single-crystal measurements.

References

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