Crystal structure of bis­(3,5-di­methyl­pyridine-κN)bis­(methanol-κO)bis­(thio­cyanato-κN)cobalt(II)

Suckert, S.; Jess, I.; Näther, C.

doi:10.1107/S2056989016018326

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Volume 72| Part 12| December 2016| Pages 1824-1826

https://doi.org/10.1107/S2056989016018326

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Crystal structure of bis(3,5-dimethylpyridine-κN)bis(methanol-κO)bis(thiocyanato-κN)cobalt(II)

Stefan Suckert,^a ^* Inke Jess ^a and Christian Näther ^a

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

Edited by M. Weil, Vienna University of Technology, Austria (Received 8 November 2016; accepted 15 November 2016; online 18 November 2016)

The asymmetric unit of the title complex, [Co(NCS)₂(C₇H₉N)₂(CH₃OH)₂], comprises of one Co^II cation located on a centre of inversion, one thiocyanate ligand, one methanol ligand and one 3,5-dimethylpyridine ligand. The Co^II cation is octahedrally coordinated by two terminal N-bonding thiocyanate anions, two methanol molecules and two 3,5-dimethylpyridine ligands into a discrete complex. The complex molecules are linked by intermolecular O—H⋯S hydrogen bonding into chains that elongate in the direction parallel to the b axis.

Keywords: crystal structure; cobalt(II) thiocyanate complex; 3,5-dimethylpyridine ligand; hydrogen bonding.

CCDC reference: 1517370

1. Chemical context

For a long time, the synthesis of new molecular magnetic materials with desired physical properties has been a topic of interest in coordination chemistry (Liu et al., 2015 ). To reach this goal, paramagnetic cations must be linked by small anionic ligands such as, for example, thiocyanate anions that can mediate magnetic exchange between the cations (Palion-Gazda et al., 2015 ; Massoud et al., 2013 ). In this context, our group has already reported several thiocyanato coordination polymers which – depending on the metal cation and the neutral co-ligand – show different magnetic phenomena including a slow relaxation of the magnetization (Werner et al., 2014 , 2015a ,b ,c ). In this regard, discrete complexes are also of interest because a transformation into the desired polymeric compounds can be achieved through thermal decomposition, as shown in one of our previous studies (Näther et al., 2013 ). During our systematic work, compounds based on 3,5-dimethylpyridine as co-ligand should be prepared, for which only one thiocyanato compound is known (Price & Stone, 1984 ; Nassimbeni et al., 1986 ). In the course of our investigations with Co^II as the transition metal, crystals of the title compound, [Co(NCS)₂(C₇H₉N)₂(CH₃OH)₂], were obtained and characterized by single crystal X-ray diffraction. Unfortunately, no single-phase crystalline powder could be synthesized, which prevented further investigations of physical properties.

2. Structural commentary

The asymmetric unit of the title compound comprises of one Co^II cation, one thiocyanato anion, one methanol molecule and one neutral 3,5-dimethylpyridine co-ligand. The Co^II cation is located on a center of inversion; the thiocyanate anion, the methanol molecule as well as the 3,5-dimethylpyridine ligand are each located on general positions. The Co^II cation is octahedrally coordinated by two terminal N-bonded thiocyanato ligands, two methanol molecules and two 3,5-dimethylpyridine ligands in an all-trans configuration (Fig. 1). The Co—N bond length to the thiocyanate anion is significantly shorter [2.0898 (19) Å] than to the pyridine N atom of the 3,5-dimethylpyridine ligand [2.1602 (17) Å], which is in agreement with values reported in the literature (Goodgame et al., 2003 ; Wöhlert et al., 2014 ).

Figure 1
View of a discrete complex of the title compound, showing the atom labelling and anisotropic displacement ellipsoids drawn at the 50% probability level. [Symmetry code: (i) −x, −y + 1, −z + 1.]

3. Supramolecular features

The discrete complexes in the crystal are linked by pairs of intermolecular O—H⋯S hydrogen bonds between the hydroxyl H atom of the methanol ligand and the thiocyanato S atom of an adjacent complex into chains propagating parallel to the b axis (Fig. 2, Table 1). These pairs are located around centres of inversion.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯S1ⁱ	0.84	2.45	3.2885 (17)	175
Symmetry code: (i) x, y-1, z.

Figure 2
The crystal structure of the title compound in a view along the a axis, showing the intermolecular hydrogen bonding as dashed lines.

4. Database survey

To the best of our knowledge, there is only one thiocyanato coordination compound with 3,5-dimethylpyridine as a co-ligand deposited in the Cambridge Structure Database (Version 5.37, last update 2015; Groom et al., 2016 ). The structure consists of an Ni^II cation octahedrally coordinated by four 3,5-dimethylpyridine ligands and two N-bonded thiocyanate anions (Price et al., 1984; Nassimbeni et al., 1986). A general search for coordination compounds with 3,5-dimethylpyridine resulted in 159 structures, including the aforementioned ones. Exemplary are two Co compounds: in the first, the cation is octahedrally coordinated by two 3,5-dimethylpyridine ligands as well as one μ-1,3-bridging and one μ-1,1-bridging azide anion, linking them into chains (Lu et al., 2012 ), whereas in the second compound, the Co^II atom is octahedrally coordinated by four 3,5-dimethylpyridine ligands and two chloride anions, forming a discrete complex (Martone et al., 2007 ).

5. Synthesis and crystallization

Co(NCS)₂ and 3,5-dimethylpyridine were purchased from Alfa Aesar. Crystals of the title compound suitable for single crystal X-ray diffraction were obtained by the reaction of 43.8 mg Co(NCS)₂ (0.25 mmol) with 28.5 µl 3,5-dimethylpyridine (0.6 mmol) in methanol (1.5 ml) after a few days.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The C—H hydrogen atoms were positioned with idealized geometry and were refined with fixed isotropic displacement parameters U_iso(H) = 1.2U_eq(C) using a riding model. The O—H hydrogen atom was located in a difference map. For refinement, the bond length was constrained to 0.84 Å, with U_iso(H) = 1.5U_eq(O), using a riding model.

Table 2
Experimental details

Crystal data
Chemical formula	[Co(NCS)₂(C₇H₉N)₂(CH₄O)₂]
M_r	453.48
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	170
a, b, c (Å)	7.7027 (5), 7.8688 (5), 9.1970 (5)
α, β, γ (°)	87.403 (5), 81.419 (5), 76.295 (5)
V (Å³)	535.48 (6)
Z	1
Radiation type	Mo Kα
μ (mm⁻¹)	1.02
Crystal size (mm)	0.15 × 0.09 × 0.04

Data collection
Diffractometer	Stoe IPDS2
Absorption correction	Numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008 )
T_min, T_max	0.885, 0.923
No. of measured, independent and observed [I > 2σ(I)] reflections	6258, 2431, 2052
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.094, 1.08
No. of reflections	2431
No. of parameters	127
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.37
Computer programs: X-AREA (Stoe & Cie, 2008), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), XP in SHELXTL (Sheldrick, 2008), DIAMOND (Brandenburg, 1999 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1517370

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989016018326/wm5338sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989016018326/wm5338Isup2.hkl

checkCIF report

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: SHELXL2014 (Sheldrick, 2015); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: publCIF (Westrip, 2010).

Bis(3,5-dimethylpyridine-κN)bis(methanol-κO)bis(thiocyanato-κn)cobalt(II) top

Crystal data top

[Co(NCS)₂(C₇H₉N)₂(CH₄O)₂]	Z = 1
M_r = 453.48	F(000) = 237
Triclinic, P1	D_x = 1.406 Mg m⁻³
a = 7.7027 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.8688 (5) Å	Cell parameters from 6258 reflections
c = 9.1970 (5) Å	θ = 2.2–27.4°
α = 87.403 (5)°	µ = 1.02 mm⁻¹
β = 81.419 (5)°	T = 170 K
γ = 76.295 (5)°	Block, blue
V = 535.48 (6) Å³	0.15 × 0.09 × 0.04 mm

Data collection top

Stoe IPDS-2 diffractometer	2052 reflections with I > 2σ(I)
ω scans	R_int = 0.024
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)	θ_max = 27.4°, θ_min = 2.2°
T_min = 0.885, T_max = 0.923	h = −9→9
6258 measured reflections	k = −10→10
2431 independent reflections	l = −11→11

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.034	H-atom parameters constrained
wR(F²) = 0.094	w = 1/[σ²(F_o²) + (0.0503P)² + 0.2412P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.001
2431 reflections	Δρ_max = 0.37 e Å⁻³
127 parameters	Δρ_min = −0.37 e Å⁻³

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Co1	0.0000	0.5000	0.5000	0.02492 (13)
N1	0.1343 (3)	0.6688 (3)	0.3719 (2)	0.0319 (4)
C1	0.2064 (3)	0.7782 (3)	0.3253 (2)	0.0282 (4)
S1	0.30808 (9)	0.93060 (7)	0.25699 (6)	0.03616 (16)
O1	0.2263 (2)	0.2834 (2)	0.45808 (19)	0.0347 (4)
H1	0.2416	0.1917	0.4098	0.042*
C2	0.4115 (3)	0.2961 (4)	0.4380 (3)	0.0406 (6)
H2A	0.4455	0.3340	0.3370	0.061*
H2B	0.4891	0.1816	0.4566	0.061*
H2C	0.4261	0.3815	0.5069	0.061*
N11	0.1118 (3)	0.5678 (2)	0.68521 (19)	0.0268 (4)
C11	0.1607 (3)	0.4492 (3)	0.7899 (2)	0.0281 (4)
H11	0.1514	0.3327	0.7775	0.034*
C12	0.2242 (3)	0.4871 (3)	0.9156 (2)	0.0282 (4)
C13	0.2358 (3)	0.6584 (3)	0.9313 (2)	0.0291 (4)
H13	0.2780	0.6900	1.0158	0.035*
C14	0.1865 (3)	0.7841 (3)	0.8251 (2)	0.0287 (4)
C15	0.1263 (3)	0.7319 (3)	0.7033 (2)	0.0272 (4)
H15	0.0937	0.8165	0.6291	0.033*
C16	0.2780 (3)	0.3476 (3)	1.0281 (2)	0.0343 (5)
H16A	0.3882	0.2640	0.9867	0.051*
H16B	0.1807	0.2864	1.0554	0.051*
H16C	0.3001	0.4014	1.1155	0.051*
C17	0.1983 (4)	0.9710 (3)	0.8375 (3)	0.0374 (5)
H17A	0.2179	1.0218	0.7388	0.056*
H17B	0.2991	0.9747	0.8899	0.056*
H17C	0.0855	1.0382	0.8917	0.056*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0324 (2)	0.0230 (2)	0.0224 (2)	−0.01104 (16)	−0.00600 (15)	−0.00096 (14)
N1	0.0419 (11)	0.0315 (9)	0.0264 (9)	−0.0160 (8)	−0.0056 (8)	0.0007 (7)
C1	0.0330 (11)	0.0299 (10)	0.0226 (9)	−0.0070 (9)	−0.0062 (8)	−0.0034 (8)
S1	0.0456 (4)	0.0304 (3)	0.0358 (3)	−0.0184 (3)	−0.0004 (3)	−0.0018 (2)
O1	0.0328 (9)	0.0303 (8)	0.0428 (9)	−0.0089 (7)	−0.0054 (7)	−0.0103 (7)
C2	0.0308 (12)	0.0427 (13)	0.0512 (14)	−0.0114 (10)	−0.0092 (10)	−0.0056 (11)
N11	0.0334 (10)	0.0255 (9)	0.0240 (8)	−0.0101 (7)	−0.0064 (7)	−0.0018 (7)
C11	0.0367 (12)	0.0226 (10)	0.0278 (10)	−0.0104 (9)	−0.0071 (8)	−0.0014 (8)
C12	0.0304 (11)	0.0300 (11)	0.0252 (10)	−0.0089 (9)	−0.0037 (8)	−0.0014 (8)
C13	0.0320 (11)	0.0314 (11)	0.0261 (10)	−0.0098 (9)	−0.0051 (8)	−0.0059 (8)
C14	0.0322 (11)	0.0260 (10)	0.0292 (10)	−0.0096 (9)	−0.0027 (8)	−0.0045 (8)
C15	0.0323 (11)	0.0249 (10)	0.0261 (10)	−0.0091 (8)	−0.0051 (8)	−0.0008 (8)
C16	0.0418 (13)	0.0339 (12)	0.0299 (11)	−0.0110 (10)	−0.0114 (9)	0.0027 (9)
C17	0.0480 (14)	0.0283 (11)	0.0410 (13)	−0.0161 (10)	−0.0097 (11)	−0.0050 (9)

Geometric parameters (Å, º) top

Co1—N1	2.0898 (19)	C11—C12	1.390 (3)
Co1—N1ⁱ	2.0898 (19)	C11—H11	0.9500
Co1—O1ⁱ	2.1311 (16)	C12—C13	1.388 (3)
Co1—O1	2.1311 (16)	C12—C16	1.502 (3)
Co1—N11ⁱ	2.1602 (17)	C13—C14	1.386 (3)
Co1—N11	2.1602 (17)	C13—H13	0.9500
N1—C1	1.164 (3)	C14—C15	1.388 (3)
C1—S1	1.636 (2)	C14—C17	1.505 (3)
O1—C2	1.438 (3)	C15—H15	0.9500
O1—H1	0.8399	C16—H16A	0.9800
C2—H2A	0.9800	C16—H16B	0.9800
C2—H2B	0.9800	C16—H16C	0.9800
C2—H2C	0.9800	C17—H17A	0.9800
N11—C11	1.342 (3)	C17—H17B	0.9800
N11—C15	1.342 (3)	C17—H17C	0.9800

N1—Co1—N1ⁱ	180.0	C15—N11—Co1	121.16 (14)
N1—Co1—O1ⁱ	87.76 (7)	N11—C11—C12	123.78 (19)
N1ⁱ—Co1—O1ⁱ	92.24 (7)	N11—C11—H11	118.1
N1—Co1—O1	92.24 (7)	C12—C11—H11	118.1
N1ⁱ—Co1—O1	87.76 (7)	C13—C12—C11	116.89 (19)
O1ⁱ—Co1—O1	180.0	C13—C12—C16	122.06 (19)
N1—Co1—N11ⁱ	92.30 (7)	C11—C12—C16	121.05 (19)
N1ⁱ—Co1—N11ⁱ	87.70 (7)	C14—C13—C12	120.79 (19)
O1ⁱ—Co1—N11ⁱ	89.25 (6)	C14—C13—H13	119.6
O1—Co1—N11ⁱ	90.75 (6)	C12—C13—H13	119.6
N1—Co1—N11	87.70 (7)	C13—C14—C15	117.59 (19)
N1ⁱ—Co1—N11	92.30 (7)	C13—C14—C17	122.42 (19)
O1ⁱ—Co1—N11	90.75 (6)	C15—C14—C17	120.0 (2)
O1—Co1—N11	89.25 (6)	N11—C15—C14	123.23 (19)
N11ⁱ—Co1—N11	180.0	N11—C15—H15	118.4
C1—N1—Co1	167.28 (17)	C14—C15—H15	118.4
N1—C1—S1	179.04 (19)	C12—C16—H16A	109.5
C2—O1—Co1	124.49 (14)	C12—C16—H16B	109.5
C2—O1—H1	97.4	H16A—C16—H16B	109.5
Co1—O1—H1	131.5	C12—C16—H16C	109.5
O1—C2—H2A	109.5	H16A—C16—H16C	109.5
O1—C2—H2B	109.5	H16B—C16—H16C	109.5
H2A—C2—H2B	109.5	C14—C17—H17A	109.5
O1—C2—H2C	109.5	C14—C17—H17B	109.5
H2A—C2—H2C	109.5	H17A—C17—H17B	109.5
H2B—C2—H2C	109.5	C14—C17—H17C	109.5
C11—N11—C15	117.71 (17)	H17A—C17—H17C	109.5
C11—N11—Co1	121.05 (13)	H17B—C17—H17C	109.5

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···S1ⁱⁱ	0.84	2.45	3.2885 (17)	175

Symmetry code: (ii) x, y−1, z.

Acknowledgements

This project was supported by the Deutsche Forschungsgemeinschaft (project No. NA 720/5–1) and the State of Schleswig-Holstein. We thank Professor Dr Wolfgang Bensch for access to his experimental facilities.

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