Crystal structure of bis-(3,5-di-methyl-pyridine-κN)bis-(methanol-κO)bis-(thio-cyanato-κN)cobalt(II).

The asymmetric unit of the title complex, [Co(NCS)2(C7H9N)2(CH3OH)2], comprises of one CoII cation located on a centre of inversion, one thio-cyanate ligand, one methanol ligand and one 3,5-di-methyl-pyridine ligand. The CoII cation is octa-hedrally coordinated by two terminal N-bonding thio-cyanate anions, two methanol mol-ecules and two 3,5-di-methyl-pyridine ligands into a discrete complex. The complex mol-ecules are linked by inter-molecular O-H⋯S hydrogen bonding into chains that elongate in the direction parallel to the b axis.

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 CoII 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.

Structural commentary

The asymmetric unit of the title compound comprises of one CoII cation, one thio­cyanato anion, one methanol mol­ecule and one neutral 3,5-di­methyl­pyridine co-ligand. The CoII 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 CoII 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.]

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.

Figure 2

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

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) .

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 NiII 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 CoII atom is octa­hedrally coordinated by four 3,5-di­methyl­pyridine ligands and two chloride anions, forming a discrete complex (Martone et al., 2007 ▸).

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.

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
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[F 2 > 2σ(F 2)], wR(F 2), S	0.034, 0.094, 1.08
No. of reflections	2431
No. of parameters	127
H-atom treatment	H-atom parameters constrained
Δρmax, Δρmin (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 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016018326/wm5338sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989016018326/wm5338Isup2.hkl

CCDC reference: 1517370

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Co(NCS)2(C7H9N)2(CH4O)2]	Z = 1
Mr = 453.48	F(000) = 237
Triclinic, P1	Dx = 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

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

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(Fo2) + (0.0503P)2 + 0.2412P] where P = (Fo2 + 2Fc2)/3
S = 1.08	(Δ/σ)max = 0.001
2431 reflections	Δρmax = 0.37 e Å−3
127 parameters	Δρmin = −0.37 e Å−3

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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

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