Thiocyanate Ligands Research Articles

SYNTHESIS AND STRUCTURE OF POTASSIUM TETRAETHYLAMMONIUM HEXATHIOCYANATOPLATINATE(IV)

Potassium tetraethylammonium hexathiocyanatoplatinate(IV) (Et4N)(K)[Pt(SCN)6] (I) was synthesized by the reaction of potassium hexathiocyanatoplatinate(IV) with tetraethylammonium chloride in acetonitrile aqueous solution. Slow evaporation of the solvent led to the formation of large red-brown crystals. The product structure was determined by XRDA. The X-ray diffraction pattern of crystal I was carried out on a Bruker D8 QUEST diffractometer (MoKα radiation, λ = 0.71073 Å, graphite monochromator). [С14H20N7KPtS6, M = 712.92, Crystal system monoclinic, space group C 2/c, a = 10.432(8), b = 14.767(13), c = 16.300(13) Å, V = 2510(4) Å3, Z = 4, µ = 6.272 mm-1, F(000) = 1384, crystal size 0.86×0.66×0.50 mm]. The tetrahedral configuration of the tetraethylammonium cation is slightly distorted (CNC angles are 105.5(5)º-111.8(4)º, bond lengths N-С are 1.503(5)-1.519(5) Å). Platinum ions in anions have octahedral coordination (trans-angles SPtS are 180º, cis-angles SPtS are (88.47(4)º-91.53(4)º). The bond lengths Pt-S are equal to 2.373 (2)-2.37(2) Å. Potassium cations are coordinated by six nitrogen atoms of thiocyanate groups (distances N K (2.828(4)-2.896 (4) Å). Trans-angles NKN (128.44 (15)º-146.9 (2)º) are far from ideal values for the octahedron. Bridged thiocyanate ligands are bonded cations of the platinum and potassium. Ambidentate thiocyanate ligands are simultaneously coordinated to the K+ cation by nitrogen atoms. By means of the bridged thiocyanate ligands a three-dimensional coordination polymer is formed. The resulting structure is a three-dimensional grid, in the cells of which the cations of tetraethylammonium (Et4N)+ are located.

Iron(II) Spin Crossover (SCO) Materials Based on Dipyridyl-N-Alkylamine

We present here a new series of spin crossover (SCO) Fe(II) complexes based on dipyridyl-N-alkylamine and thiocyanate ligands, with the chemical formulae [Fe(dpea)2(NCS)2] (1) (dpea = 2,2’-dipyridyl-N-ethylamine), I-[Fe(dppa)2(NCS)2], (2) II-[Fe(dppa)2(NCS)2], and (2’) (dppa = 2,2’-dipyridyl-N-propylamine). The three complexes displayed nearly identical discrete molecular structures, where two chelating ligands (dpea (1) and dppa (2 and 2’)) stand in the cis-positions, and two thiocyanato-κN ligands complete the coordination sphere in the two remaining cis-positions. Magnetic studies as a function of temperature revealed the presence of a complete high-spin (HS) to low-spin (LS) transition at T1/2 = 229 K for 1, while the two polymorphs I-[Fe(dppa)2(NCS)2] (2) and II-[Fe(dppa)2(NCS)2] (2’) displayed similar magnetic behaviors with lower transition temperatures (T1/2 = 211 K for 2; 212 K for 2’). Intermolecular contacts in the three complexes indicated the absence of any significant interaction, in agreement with the gradual SCO behaviors revealed by the magnetic data. The higher transition temperature observed for complex 1 agrees well with the more pronounced linearity of the Fe–N–C angles recently evidenced by experimental and theoretical magnetostructural studies.

Solvent assisted synthesis, structural characterization and biological evaluation of cobalt(II) and nickel(II) complexes of Schiff bases generated from benzyl carbazate and cyclic ketones

A series of mononuclear cobalt and nickel complexes of the types [M(NCS)2(L1)2], M = Co 1 or Ni 2, [M(NCS)2(L2)2]·nH2O, M = Co (n = 0) 3 or Ni (n = 2) 4 and [M(NCS)2(L3)2], M = Co 5 or Ni 6, where L1 = benzyl 2-(cyclobutanylidene)hydrazinecarboxylate, L2 = benzyl 2-(cyclopentanylidene)hydrazinecarboxylate and L3 = benzyl 2-(cyclohexanylidene)hydrazinecarboxylate, were synthesized by template reactions of the metal nitrates, ammonium thiocyanate and benzyl carbazate (bc) with cyclobutanone (cb), cyclopentanone (cp) or cyclohexanone (ch). These compounds have been characterized by elemental analysis, infrared, electronic absorption and 1H NMR spectroscopies, together with single crystal X-ray diffraction. Crystal structures of the complexes 1, 3–6 showed that the Schiff base ligands coordinate to the metal ions via the azomethine nitrogen and carbonyl oxygen atoms. In each case the two thiocyanate ligands coordinate through their nitrogen atoms resulting in complexes with a six coordinate octahedral geometry. The thermal stability of the complexes was investigated by TG-DTA and all of the compounds (1–6) undergo endothermic followed by exothermic decomposition processes to form the respective metal oxides. The antibacterial activity of the cobalt(II) and nickel(II) complexes was examined against Gram positive and Gram negative bacteria at concentrations between 40 and 80 μg mL−1. The binding interaction of human serum albumin (HSA) with compounds 1–6 was explored by multi-spectroscopic techniques and docking studies revealed the complexes bind to HSA through hydrophobic interactions. The cytotoxic activity of all of the compounds was evaluated against the K-562 (leukemia cell line) by MTT assays and, remarkably, all of the complexes were found to show good activity towards this cancer cell line. DAPI (4′,6-diamidino-2-phenylindole) staining assay further confirmed that complexes induced leukemia cancer cell death by an apoptosis mechanism.

On the Magnetic Coupling and Spin Crossover Behavior in Complexes Containing the Head-to-Tail [FeII2(μ-SCN)2] Bridging Unit: A Magnetostructural Experimental and Theoretical Study.

A new dinuclear complex [{Fe(tpc-OBn)(NCS)(μ-NCS)}2] (1) based on the tripodal tpc-OBn ligand (tpc-OBn = tris(2-pyridyl)benzyloxymethane), containing bridging μ-κN:κS-SCN and terminal κN-SCN thiocyanate ligands, has been prepared and characterized by single crystal X-ray diffraction, magnetic studies, and DFT theoretical calculations. This complex represents the first example of dinuclear FeII complex with double μ-κN:κS-SCN bridges in a head-to-tail configuration that exhibits ferromagnetic coupling between metal ions (JFeFe = +1.08 cm-1). Experimental and theoretical magnetostructural studies on this kind of infrequent FeII dinuclear complex containing a centrosymmetrically [Fe2(μ-SCN)2] bridging fragment show that the magnitude and sign of the magnetic coupling parameter, JFeFe, depend to a large extent on the Fe-N-C (α) angle, so that JFeFe decreases linearly when α decreases. The calculated crossover point below which the magnetic interactions change from ferromagnetic to antiferromagnetic is found at 162.3°. In addition, experimental results obtained in this work and those reported in the literature suggest that large Ntripodal-FeII distances and bent N-bound terminal κN-SCN ligands favor the high spin state of the FeII ions, while short Ntripodal-FeII distances and almost linear Fe-N-C angles favor a stronger ligand field, which enables the FeII ions to show spin crossover (SCO) behavior.

Performance improvement of Ru II complexes pyridinyl backbone on dye-sensitized solar cells (DSSC)

Two new series of RuII complexes (6–10 bearing an imine bond and 16–20 bearing a sulfonamidate fragment) based 8-aminoquinoline backbone were prepared and characterized by NMR, FT-IR, elemental analysis, UV–vis, CV etc. and tested as a photoactive dye for dye-sensitized solar cells (DSSC). The performance of the RuII-arene containing imine bond complex types (6–10) as a dye on DSSCs produced cells with power conversion efficiencies (PCEs) of around 0.03–0.10%. The [(N-Quinoline-8-yl-benzenesulfonamido)(p-cymene)chlororuthenium(II)] (SD-E1311) complex, which we previously produced was tested instead of the complexes bearing the imine bond (6–10) and its PCE for SD-E1311 was found as 0.12%. Herein, the increase of the Voc is quite interesting and, for this reason, the sulfonamidate based complexes were selected for the backbone structure. To enhance immobilization to the titanium oxide layer and solubility and electron injection of the corresponding excited dye on the DSSC process, 2,2′-bipyridine-4,4′-dicarboxylic acid as the anchor group and thiocyanate ligands were selected instead of p-cymene and chloro ligands over the sulfonamidate complex. Then, the photoactive dye properties of the new RuII complexes (16–20) were investigated and the results showed that the 16–20 dyes bearing sulfonamidate, carboxylic anchoring and thiocyanate fragments benefited the short-circuit current and the open-circuit voltage, and had PCEs of 1.26%, 1.08%, 1.58%, 0.90% and 1.36% under AM1.5G irradiation, respectively. The working devices, results also show that the 16–20 dyes demonstrated average performances with a PCEmax. of 1.58% which was occurred with 18 complex.

The structure of coordination precursors as an effective tool for governing of size and morphology of ZnS and ZnO nanoparticles

The zinc sulphide and zinc oxide micro- and nanoparticles of different shapes were synthesized from the five zinc coordination precursors, via controlled thermal decomposition process. The precursors were synthesized from zinc thiocyanate and N-donor ligands (2-aminopyrimidine, 1H-1,2,4-triazole and hexamethylenetetraamine), and they possessed different molecular and crystal structures (confirmed by X-ray crystallographic and spectroscopic studies). The proper set of parameters of precursors conversion process allows producing of ZnS in cubic (sphalerite) and hexagonal (wurtzite) form, as well as ZnO in hexagonal form. The relationship between the particles geometry (size and morphology) and the precursor structure, as well as the parameters of thermal conversion process was investigated.

Crystal structures of bis-[4-(di-methyl-amino)-pyridinium] tetra-kis-(thio-cyanato-κN)manganate(II) and tris-[4-(di-methyl-amino)-pyridinium] penta-kis(thio-cyanato-κN)manganate(II).

The crystal structures of the title salts, (C7H11N2)2[Mn(NCS)4] (1) and (C7H11N2)3[Mn(NCS)5] (2), consist of manganese(II) cations that are tetra-hedrally (1) or trigonal-bipyramidally (2) coordinated to four or five terminal N-bonded thio-cyanate ligands, respectively, into discrete anionic complexes. The negative charge is compensated by two (1) or three (2) 4-(di-methyl-amino)-pyridinium cations, which are protonated at the pyridine N atom. The asymmetric unit of compound 1 consists of one anionic complex and two 4-(di-methyl-amino)-pyridinium cations, whereas that of compound 2 consists of two anionic complexes and six 4-(di-methyl-amino)-pyridinium cations, all of them located in general positions. These complexes are linked by N-H⋯S, C-H⋯S and C-H⋯N hydrogen-bonding inter-actions between the 4-(di-methyl-amino)-pyridinium cations and the thio-cyanate ligands into three-dimensional network structures.

A mercury(II) mixed-ligand coordination polymer constructed from 4,7-diphenyl-1,10-phenanthroline and thiocyanate ligands: Crystal structure studies, spectroscopic characterization, and thermal analyses

A mercury(II) mixed-ligand coordination polymer constructed from 4,7-diphenyl-1,10-phenanthroline and thiocyanate ligands: Crystal structure studies, spectroscopic characterization, and thermal analyses

Anion coordination directed synthesis patterns for [Ni4] aggregates: structural changes for thiocyanate coordination and ligand arm hydrolysis

Competitive bridging modes of HO− and NCS− were explored for four NiII-based coordination aggregates in cubane and dicubane topology.

Oxoiron(IV) complexes as synthons for the assembly of heterobimetallic centers such as the Fe/Mn active site of Class Ic ribonucleotide reductases.

Nonheme oxoiron(IV) complexes can serve as synthons for generating heterobimetallic oxo-bridged dimetal complexes by reaction with divalent metal complexes. The formation of FeIII-O-CrIII and FeIII-O-MnIII complexes is described herein. The latter complexes may serve as models for the FeIII-X-MnIII active sites of an emerging class of Fe/Mn enzymes represented by the Class 1c ribonucleotide reductase from Chlamydia trachomatis and the R2-like ligand-binding oxidase (R2lox) found in Mycobacterium tuberculosis. These synthetic complexes have been characterized by UV-Vis, resonance Raman, and X-ray absorption spectroscopy, as well as electrospray mass spectrometry. The FeIII-O-CrIII complexes exhibit a three-band UV-Vis pattern that differs from the simpler features associated with FeIII-O-FeIII complexes. The positions of these features are modulated by the nature of the supporting polydentate ligand on the iron center, and their bands intensify dramatically in two examples upon the binding of an axial cyanate or thiocyanate ligand trans to the oxo bridge. In contrast, the FeIII-O-MnIII complexes resemble FeIII-O-FeIII complexes more closely. Resonance Raman characterization of the FeIII-O-MIII complexes reveals an 18O-sensitive vibration in the range of 760-890cm-1. This feature has been assigned to the asymmetric FeIII-O-MIII stretching mode and correlates reasonably with the Fe-O bond distance determined by EXAFS analysis. The likely binding of an acetate as a bridging ligand to the FeIII-O-MnIII complex 12 lays the foundation for further efforts to model the heterobimetallic active sites of Fe/Mn enzymes.

2,2′-Bipyridine – A new electrolyte additive in dye-sensitized solar cells

In this work 2,2′-bipyridine (bipy) is introduced as a new nitrogen containing electrolyte additive in Dye-sensitized solar cells (DSCs) as an alternative to the commonly used 4-tert-butylpyridine (TBP). Bipy was shown to substitute the thiocyanate ligands in the N719 ruthenium dye ~4 times slower than TBP at elevated temperatures 80–85°C and therefore reduce the thermal degradation of N719 relative to TBP. The thermal stability experiments were performed in sealed glass ampules filled with a colloidal solution of N719 dyed TiO2 nano-particles in an ionic liquid electrolyte with either TBP or bipy as N-additive. The glass ampules were opened after various time intervals between 0 and 2000h of heating at either 80 or 85°C and the N719 and its degradation products were extracted from the TiO2 nano particles and analyzed by LC-UV/Vis-MS. After 1000h at 85°C in dark, 85% of N719 was intact in an electrolyte containing 0.2M bipy whereas the same number was 67% for TBP. DSCs prepared with bipy in the electrolyte was shown to perform equally well as DSCs with TBP containing electrolytes with light to electricity performance of 4.5% for both N-additives. 2,2′-bipyridine may therefore be used as an alternative to TBP as N-additive in DSCs.

An investigation of the leaching of Pt and Pd from cooperite, sperrylite and column bioleached concentrates in thiocyanate-cyanide systems

This study investigates the effectiveness of a combined thiocyanate-cyanide leach system in Pt and Pd containing minerals with a view to simplifying the traditional smelt-matte-refine process for PGE recovery by providing a route that is potentially more economical and environmentally more sustainable. Initial studies performed on the key Pt minerals, cooperite (PtS2) and sperrylite (PtAs2) in batch stirred tank reactors explored the effect of lixiviant concentration, temperature, pH, oxidants and the influence of a mixed lixiviant system on Pt extraction and compared this to individual systems. Overall, cooperite demonstrated improved Pt extraction in the mixed (SCN−/CN−/[Fe(CN)6]3−) and SCN−/CN− systems, obtaining 54% and 56% Pt extraction, respectively. Sperrylite did not leach well but showed enhanced Pt extractions in the CN−/[Fe(CN)6]3− and the mixed (SCN−/CN−/[Fe(CN)6]3−) system achieving, 5.9% and 8.1% extraction, respectively.Subsequent column leach tests conducted on a low grade Merensky concentrate, revealed that a mixed lixiviant system comprising of SCN−, CN− and [Fe(CN)6]3− again displayed enhanced extraction relative to a system consisting of either SCN−/CN− or CN−/[Fe(CN)6]3−; achieving 47% Pt extraction over a 55day period and close to 100% Pd extraction over 30days. It is concluded that ferricyanide acts as an oxidant promoting the dissolution of Pt and Pd, whereas the formation of heterogeneous (mixed) ligand complexes containing both thiocyanate and cyanide ligands, is postulated to ensure enhanced stability of the Pt and Pd in the leach solution.

(Thiocyanato-κS)tris(triphenylphosphane-κP)silver(I)

In the mononuclear title complex, [Ag(SCN)(C18H15P)3], the AgIcenter is in a slightly distorted tetrahedral coordination geometry formed by one S atom from a terminal thiocyanate ligand and three P atoms from three triphenylphosphane ligands. In the crystal, weak C—H...N hydrogen bonds connect molecules into a two-dimensional network parallel to (10\overline{1}). One of the phenyl rings is disordered over two positions which were refined with an occupancy ratio of 0.715 (16):0.285 (16).

Halogen bond preferences of thiocyanate ligand coordinated to Ru(II) via sulphur atom

Halogen bonding between [Ru(bpy)(CO)2(S-SCN)2] (bpy = 2,2’-bipyridine), I2 was studied by co-crystallising the metal compound and diiodine from dichloromethane. The only observed crystalline product was found to be [Ru(bpy)(CO)2(S-SCN)2]⋅I2 with only one NCS⋅⋅⋅I2 halogen bond between I2 and the metal coordinated S atom of one of the thiocyanate ligand. The dangling nitrogen atoms were not involved in halogen bonding. However, computational analysis suggests that there are no major energetic differences between the NCS⋅⋅⋅I2 and SCN⋅⋅⋅I2 bonding modes. The reason for the observed NCS⋅⋅⋅I2 mode lies most probably in the more favourable packing effects rather than energetic preferences between NCS⋅⋅⋅I2 and SCN⋅⋅⋅I2 contacts.

New Supramolecular Coordination Polymers Based on Cd(II) and Co(II) with Ethyl Nicotinate and Thiocyanate Ligands as Effective Catalysts for Removal of Organic Dyes

Two new 3D- supramolecular coordination polymers (SCP) were synthesized by the reactions of ethyl nicotinate (EN) ligand and SCN ion with Cd(II) and Co(II) ions. Two different structures, {[Cd(SCN)2(EN)2]}, SCP 1 and {[Co2(NCS)4(EN)8]}, SCP 2, were characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy, and thermal analysis. The structure of the SCP 1 consists of cyclic (CdSCN)n building blocks exhibiting chair conformation creating 1D-chain decorated by the coordinated EN on both sides while Cd atom exhibits octahedral geometry. The structure of 2 consists of two chemically identical and crystallographically different coordination complexes containing two distinct cobalt atoms, Co1 and Co2 each exhibits octahedral geometry. The structures of 1 and 2 extend to 3D-network via H-bonds and π–π stacking. The catalytic behavior of the SCP 1 and 2 for the degradation of acid blue 92 dye (AB-92) was also studied. The reaction is first order with respect to AB-92 dye. The irradiation of the reaction with UV-light enhanced the rate of AB-92 mineralization. Mineralization of AB-92 was investigated by FT-IR spectra. Disodium salt of terephthalic acid photoluminescence probing technology was carried out to identify the reactive oxygen species. The efficiency of recycled the catalysts 1 and 2 and mechanism of degradation of AB-92 dye were also investigated. The kinetic data indicated that 1 and 2 are effective catalysts for degradation of AB-92.

Interactions Between Thiocyanate-Free Bis-Tridentate Ru Complexes and Iodide in Dye-Sensitized Solar Cells

Abstract The intermolecular interactions of thiocyanate-free Ru terpyridyl complexes containing a 2,6-disubstituted pyridine as a tridentate donor ligand (BTP, FT19, and TUS-29 dyes) with iodide ions are investigated using density functional theory. Similar to N749 dye with three thiocyanate ligands, the oxidized thiocyanate-free complexes mainly interact with I − and I 2 − ions via the donor ligands. Oxidized BTP with a pyridine-2,6-ditetrazolyl ligand can be regenerated by three different mechanisms: (A) by one I − through a one-step mechanism, (B) by two I − ions via a two-step mechanism, or (C) by I 2 − via a one-step mechanism. Oxidized FT19 with a pyridine-2,6-dicarboxylate ligand can be regenerated via mechanism B or C. Although oxidized TUS-29 with a pyridine-2,6-dicarboxyamidato ligand can be reduced through mechanism C, the regeneration reaction is rather incomplete. The much lower dye-sensitized solar cell performance using TUS-29 dye than N749 is attributed to its inferior regeneration ability.

Mononuclear mercury(II) complexes containing bipyridine derivatives and thiocyanate ligands: Synthesis, characterization, crystal structure determination, and luminescent properties

A series of mercury(II) complexes, [Hg(NN)(SCN)2] (NN is 4,4′-dimethyl-2,2′-bipyridine in 1, 5,5′-dimethyl-2,2′-bipyridine in 2, 6,6′-dimethyl-2,2′-bipyridine in 3 and 6-methyl-2,2′-bipyridine in 4), were prepared from the reactions of Hg(SCN)2 with mentioned ligands in methanol. Suitable crystals of these complexes were obtained for X-ray diffraction measurement by methanol diffusion into a DMSO solution. The four complexes were thoroughly characterized by spectral methods (IR, UV–Vis, 13C{1H}NMR, 1H NMR and luminescence), elemental analysis (CHNS) and single crystal X-ray diffraction. The X-ray structural analysis indicated that in the structures of these complexes, the mercury(II) cation is four-coordinated in a distorted tetrahedral configuration by two S atoms from two thiocyanate anions and two N atoms from one chelating 2,2′-bipyridine derivative ligand. Also, in these complexes intermolecular interactions, for example CH⋯N hydrogen bonds (in 1–4), CH⋯S hydrogen bonds (in 1, 2 and 4), π … π interactions (in 2–4), Hg⋯N interactions (in 2) and S⋯S interactions (in 4), are effective in the stabilization of the crystal structures and the formation of the 3D supramolecular complexes. Furthermore, the luminescence spectra of the title complexes show that the intensity of their emission bands are stronger than the emission bands for the free bipyridine derivative ligands.

Catena-Poly[[μ2-4,4′-bis(pyridin-3-ylethynyl)-1,1′-biphenyl-κ2 N:N′]bis(μ2-thiocyanato-κ2 N:S)bis(thiocyanato-κS)dimercury(II)

In the title polymer, [Hg2(SCN)4(C26H16N2)] n , the two equivalent HgII atoms are coordinated by one N atom of a bridging 4,4′-bis(pyridin-3-ylethynyl)-1,1′-biphenyl ligand, two S atoms of two thiocyanates and one N atom of a thiocyanate, giving rise to a distored tetrahedral coordination environment. Two thiocyanate ligands bridge symmetry-related metal atoms to form a polymeric chain extending parallel to [001], and another bridging mode is accomplished by the organic ligand that is located about an inversion centre. The dihedral angle between the coordinating pyridine ring and the benzene ring is 11.4 (2)°, and the two coordinating pyridine rings in the organic ligand are parallel by symmetry. The point group of the ligand in the compound is thus close to C 2h . The result of the mode of the organic ligands is the formation of zigzag sheets connected via bridging thiocyanate ligands.

Structural comparison of copper(II) thiocyanate pyridine complexes

Copper(II) thiocyanate forms a series of closely related complexes when reacted with substituted pyridines (XPy) in methanol. Although these compounds are nominally square planar trans-[Cu(NCS)2(XPy)2], most show N,S-thiocyanate bridging via long Cu–S bonds of ⩾2.7Å. The resulting Jahn-Teller (J-T) distorted octahedra form edge-sharing chains. However, these units can also form sheets or small oligomers. For some 2- or 3-substituted pyridines, isolated square planar trans-[Cu(NCS)2(XPy)2], J-T distorted octahedral trans-[Cu(NCS)2(XPy)2(MeOH)2], or square pyramid trans-[Cu(NCS)2(XPy)2(MeOH)] were isolated. Polymorphism and/or solvento isomers appear to be common, being identified for five of 21 ligands studied. Use of 2-NH2Py produces methoxy-bridged dimers [Cu2(NCS)2(2-NH2Py)2(μ-OMe)2] that are further linked via bridging thiocyanate to form a sheet structure. Unusual aryl bromide metal chelation is noted in the mixed ligand complex trans-[Cu(NCS)2(2-BrPy)(3-BrPy)]. When LL=4,4′-bipyridyl (Bpy) or pyrazine (Pyz) is used, bridging by both the organic and thiocyanate ligands produces sheet networks, trans-[Cu(NCS)2(LL)].

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.