Methanol Ligands Research Articles

Pseudo-tetrahedral semi-sandwich cycloruthenated compounds: 1H NMR data and DFT-calculations about the racemisation process of the ruthenium atom

The partial substitution of the acetonitrile ligand of compound 1a 〚(η 6-C 6H 6)Ru(C 6H 4-2-CH 2NMe 2)(NCMe)〛 +PF 6 – by CD 3OD was observed while running the 1H NMR spectra of 1a in this solvent, this giving rise to the formation of 1b. In opposition to 1a, the 1H NMR spectrum of 1b is temperature-dependent, as at T > 40 °C the coalescence of the signals of the –CH 2NMe 2 protons was observed, this being an evidence for the fast racemisation of the Ru centre in 1b at the NMR timescale. DFT-calculations allowed us to envision a likely process for this racemisation. It should take place via the decoordination of the methanol ligand at an early step of the reaction, followed by the inversion of the configuration of the thus-obtained 16 e – species ( 2). The transition state ( 3) for this latter reaction was identified and the total free energy of the racemisation was thus calculated, affording a value close to the activation energy found experimentally by 1H NMR (∼13 kcal mol –1 vs ∼15.5 kcal mol –1, respectively).

Thermochemistry of adducts of tin(IV) bromide with ligands containing amide or thioamide groups

The compounds [SnBr 4(L) 2] (where L is formamide (fa), acetamide (a), N, N-dimethylacetamide (dma), benzamide (ba), thioacetamide (ta), N, N-dimethylthioformamide (dmtf), N, N-dimethylthioacetamide (dmta) or thiobenzamide (tba)) were synthesized and characterized by melting points, elemental analysis, thermal analysis and IR spectroscopy. The enthalpies of dissolution of the adducts, tin(IV) bromide and ligands in methanol were measured and by using thermochemical cycles the following thermochemical parameters for the adducts have been determined: the standard enthalpies for the Lewis acid/base reactions (Δ r H θ ), the standard enthalpies of formation (Δ f H θ ), the standard enthalpies of decomposition (Δ D H θ ), the lattice standard enthalpies (Δ M H θ ) and the standard enthalpies of the Lewis acid/base reactions in the gaseous phase (Δ r H θ (g). The mean bond dissociation enthalpies of the tin(IV)oxygen ( D ̄ ( Sn S) ) and tin(IV)sulphur bonds ( D ̄ ( Sn O) ) have been estimated.

Trans-bis(benzoato-O)tetrakis(methanol-O)iron(II): ligand bulk is not structure-determining.

The title compound, [Fe(C7H5O2)2(CH4O)4], is a centrosymmetric six-coordinate Fe(II) complex coordinated by two axial monodentate benzoate ligands and four methanol ligands in the equatorial plane [Fe-O(benzoate) 2.0935 (7) A, and Fe-O(methanol) 2.1310 (7) and 2.1290 (7) A]. The benzoate ligands adopt monodentate ligation, rather than a bridged polymeric structure, because of strong intra- and intermolecular hydrogen bonds to the methanol ligands. This structure is nearly identical to that obtained with a much bulkier carboxylate ligand [Chavez, Que & Tolman (2001). Chem. Commun. pp. 111-112].

(Methanol){α-5,10,15:β-20-tetrakis[2-(chloroacetamido)phenyl]porphyrin}zinc(II) chloroform solvate

The pentacoordinated Zn atom in the title compound, [Zn(C52H36Cl4N8O4)(CH4O)]·CHCl3, is displaced from the porphyrin N4 plane towards the axial methanol ligand by 0.269 (2) Å. The average Zn—N(porphyrin) distance is 2.063 (9) Å and the axial Zn—O(MeOH) distance is 2.147 (5) Å.

Thermochemistry of adducts of tin(IV) chloride with ligands containing amide or thioamide groups

The compounds [SnCl 4(L) 2] (where L is formamide (fa), acetamide (a), N, N-dimethylformamide (dmf), N, N-dimethylacetamide (dma), benzamide (ba), thioacetamide (ta), N, N-dimethylthioformamide (dmtf), N, N-dimethylthioacetamide (dmta) or thiobenzamide (tba), were synthesized and characterized by melting point, elemental analysis, thermal studies and IR spectroscopy. The enthalpies of dissolution of the adducts, tin(IV) chloride and ligands in methanol were measured and by using thermochemical cycles, the following thermochemical parameters for the adducts have been determined: the standard enthalpies for the Lewis acid/base reactions (Δ r H θ ), the standard enthalpies of formation (Δ f H θ ), the standard enthalpies of decomposition (Δ D H θ ), the lattice standard enthalpies (Δ M H θ ) and the standard enthalpies of the Lewis acid/base reactions in the gaseous phase (Δ r H θ (g)). The mean standard enthalpies of the tin(IV)–oxygen ( D ̄ ( Sn O) ) and tin(IV)–sulphur bonds ( D ̄ ( Sn O) ) have been estimated.

An imidazole-based P–N bridging ligand and its binuclear copper(I), silver(I) and palladium(I) complexes: synthesis, characterizations and X-ray structures

Reaction of 1-methylimidazole with n-BuLi in tetrahydrofuran at −78°C followed by addition of chlorodiphenylphosphine afforded a P–N bridging ligand, 2-(diphenylphosphino)-1-methylimidazole (dpim) in good yield. The structure of the ligand was determined by single crystal X-ray analysis. Reaction of a stoichiometric amount of the ligand with [Cu(MeCN) 4]ClO 4 in acetonitrile led to the binuclear complex [Cu 2(μ-dpim) 3(MeCN)](ClO 4) 2·2CH 3CN ( 1·2CH 3CN), whose structure was determined by single crystal X-ray analysis. The solid state structure shows that the two copper ions are held by three dpim ligands and the coordination geometry around each metal atom is different, one being three- and the other being four-coordinated. One of the copper ions forms a distorted tetrahedral array with two P and one N atoms from the dpim ligand and an additional N atom from an acetonitrile ligand, whereas the other copper ion is three coordinated with two N and one P atoms from the dpim ligand. The nitrate-bridged polymeric silver(I) complex, {[Ag 2(μ-dpim) 2(NO 3)](NO 3)} n ( 2) was prepared by the reaction of equimolar amounts of the ligand and silver nitrate in methanol and was characterized by IR, NMR and X-ray analysis. The dimeric unit, [Ag 2(μ-dpim) 2], possesses an eight-membered annular core structure with two ligands bridging the two metal ions in a head-to-tail configuration. Two types of nitrate ions are present in 2: one makes an infinite one-dimensional chain by joining the dimeric units through its two oxygen atoms in an anti– anti bridging mode whereas the other is disordered with a half occupancy and is located at the left and right sides of the chain. The dynamic behavior of 2 in acetone was also studied by variable temperature 31P NMR. The binuclear palladium(I) complex [Pd 2Cl 2(dpim) 2] ( 4) was prepared by a conproportionation reaction between complex [PdCl 2(dpim) 2] ( 3) and [Pd(dba) 2] (dba=dibenzylideneaceton). Only one geometric isomer, probably head-to-tail (HT), was formed in this reaction. Complex 3 was prepared by treating [PdCl 2(PhCN) 2] with two moles of ligand in dichloromethane solution. In this complex the ligand acts as a P-monodentate. In solution it exists as a mixture of cis and trans isomers.

Thermochemistry of adducts of tin(IV) bromide with amide and thioamide ligands

The compounds SnBr 4· nL (where L is urea (u), 1,1-dimethylurea (1,1-dmu), 1,3-dimethylurea (1,3-dmu), tetramethylurea (tmu), thiourea (tu), tetramethylthiourea (tmu) or 1-allyl-2-thiourea (atu) and n=2, 3 or 4) were synthesized and characterized by melting points, elemental analysis, thermal analysis and IR spectroscopy. The enthalpies of dissolution of the adducts, tin(IV) bromide and ligands in methanol were measured and by using thermochemical cycles the following thermochemical parameters for the adducts have been determined: the standard enthalpies for the Lewis acid/base reaction (Δ r H 0); the standard enthalpies of formation (Δ f H 0); the standard enthalpies of decomposition (Δ D H 0); the lattice standard enthalpies (Δ M H 0) and the standard enthalpies of the Lewis acid/base reaction in the gaseous phase (Δ r H 0(g)). The mean standard enthalpies of the tinoxygen ( D ̄ ( Sn O) ) and tinsulphur ( D ̄ ( Sn S) ) bonds have been estimated.

1-D coordination polymers containing benzenedicarboxylate

The preparation and crystal structures of [Cu(1,3-bdc)(py) 3].1 1 2 H 2O ( 1), [Cu(1,3-bdc)(py) 3].H 2O.CH 3OH ( 2), [Co(1,3-bdc)(py) 3(H 2O)] ( 3), [Co(1,3-bdc)(py) 3(CH 3OH)].H 2O ( 4), [Cu(1,3-bdc)(py) 2] ( 5), [Co(1,3-bdc)(CH 3OH) 4] ( 6) and [Ni(1,3-bdc)(CH 3OH) 4] ( 7) are described (1,3-bdc=1,3-benzenedicarboxylic acid; py=pyridine). 1– 4 form straight-chain 1-D coordination polymers with interdigitated pyridyl ligands that are engaged in C-H···π hydrogen bonds. 6 and 7 form similar 1-D polymeric chains, but the smaller methanol ligands allow the bdc groups to stack to form π···π interactions. 5 forms a rectangular 2-D grid structure with insufficient space for guest inclusion.

Anilino Radical Complexes of Cobalt(III) and Manganese(IV) and Comparison with Their Phenoxyl Analogues

The pendent arm macrocyclic aniline ligands 1-(2-amino-3,5-di-tert-butylbenzyl)-4,7-dimethyl-1,4,7-triazacyclononane, H[L1], and 1,4,7-tris(2-amino-3,5-di-tert-butylbenzyl)-1,4,7-triazacyclononane, H3[L2], have been synthesized. The reaction of these ligands in methanol (1:1) and/or ethanol with CoII(ClO4)2·6H2O and potassium di-tert-butylacetylacetonate (1:1) or MnII(acetate)2·4H2O in the presence of air produced the anilido complexes [CoIII(L1)(Bu2acac)](ClO4) (1) and [MnIV(L2)]X (X = ClO4 (2), BPh4 (2‘)), respectively. The reaction of H3[L2] and CuCl2·2H2O in ethanol produced upon addition of NaClO4 blue crystals of [CuII(H3L2)Cl](ClO4) (3) containing two coordinated and one uncoordinated aniline pendent arm. Complexes 1, 2, and 3 have been structurally characterized by X-ray crystallography. Electrochemically, 1 is reversibly oxidized with formation of the paramagnetic anilino radical species [CoIII(L1•)(Bu2acac)]2+ (S = 1/2) whereas the cyclic voltammogram of 2 displays three ligand-centered one-elec...

Trans-(Methanol)(methyldiphenylphosphine)bis(pentane-2,4-dionato)cobalt(III) hexafluorophosphate hydrate

The title compound [Co(C5H7O2)2(C13H13P)(CH4O)]PF6·H2O, (I), which was converted from trans-[Co(acac)2(PMePh2)(H2O)]PF6 (acac is pentane-2,4-dionato) by recrystallization from aqueous methanol, has been confirmed as have a coordinated methanol ligand. The molecular structure of the complex cation, trans-[Co(acac)2(PMePh2)(MeOH)]+, is similar to that of the above aqua complex found in the ClO4 salt [Kashiwabara et al. (1995). Bull. Chem. Soc. Jpn, 68, 883–888]. The Co—O bond length for the coordinated methanol is 2.059 (3) Å. There is an intermolecular hydrogen bond between the OH group of the coordinated methanol and one of the O atoms of the acac ligands in an adjacent complex cation [O5⋯O3′ = 2.914 (4) Å], giving a centrosymmetric dimeric dicationic complex.

Trans-(Methanol)(methyldiphenylphosphine)bis(pentane-2,4-dionato)cobalt(III) hexafluorophosphate hydrate.

The title compound [Co(C(5)H(7)O(2))(2)(C(13)H(13)P)(CH(4)O)]PF(6).H(2)O, (I), which was converted from trans-[Co(acac)(2)(PMePh(2))(H(2)O)]PF(6) (acac is pentane-2,4-dionato) by recrystallization from aqueous methanol, has been confirmed as have a coordinated methanol ligand. The molecular structure of the complex cation, trans-[Co(acac)(2)(PMePh(2))(MeOH)](+), is similar to that of the above aqua complex found in the ClO(4) salt [Kashiwabara et al. (1995). Bull. Chem. Soc. Jpn, 68, 883-888]. The Co-O bond length for the coordinated methanol is 2.059 (3) A. There is an intermolecular hydrogen bond between the OH group of the coordinated methanol and one of the O atoms of the acac ligands in an adjacent complex cation [O5.O3' = 2.914 (4) A], giving a centrosymmetric dimeric dicationic complex.

Molecular structure, characterization and magnetic properties of novel mixed-valence copper(I,II) α,β-unsaturated carboxylate complexes with triphenylphosphine and methanol ligands

Two new mixed-valence tetranuclear copper(I,II) α,β-unsaturated carboxylate complexes Cu 2 ICu 2 IIA 6(PPh 3) 4(CH 3OH) 2 ( 1, A=CH 2CH–COO −; 2, A=CH 2C(CH 3)–COO −) have been synthesized by partial reduction of Cu 2A 4(H 2O) 2 by triphenylphosphine in methanol solution, and characterized by elemental analyses, IR, ESR, electronic reflectance spectroscopies as well as magnetic susceptibility measurements. In complex 2 two copper(II) atoms in a molecule are linked by four carboxylate groups forming a dimeric unit Cu 2 IIA 4, and each copper(II) atom coordinates with a copper(I) moiety through a μ 2-O,O′ carboxylate group. The electronic reflectance spectra in the solid state suggest a square pyramidal coordination environment around the copper(II) atoms. Bond valence calculations further confirm the presence of the mixed-valence system and the oxidation state of the copper atoms. Room temperature X-band ESR spectra of powdered samples and variable-temperature magnetic susceptibility studies indicate the presence of strong antiferromagnetic exchange interactions between two copper(II) atoms, with 2 J=−310 cm −1 for complex 1 and 2 J=−288 cm −1 for complex 2. The formation mechanism of the title complexes and the structural interconversion among related mixed-valence copper(I,II) carboxylate complexes are also discussed.

Thermochemistry of adducts of tin(IV) chloride with amides and thioamides

The compounds [SnCl 4(L) 2] (where L is urea (u), 1,1-dimethylurea (1,1-dmu), 1,3-dimethylurea (1,3-dmu), tetramethylurea (tmu), thiourea (tu), tetramethylthiourea (tmtu) or 1-allyl-2-thiourea (atu)) were synthesized and characterized by melting points, elemental analysis, thermal studies and IR spectroscopy. The enthalpies of dissolution of the adducts, tin(IV) chloride and ligands in methanol were measured and by using thermochemical cycles the following thermochemical parameters for the adducts, have been determined: the standard enthalpies for the Lewis acid/base reactions (Δ r H θ ), the standard enthalpies of formation (Δ f H θ ), the standard enthalpies of decomposition (Δ D H θ ), the lattice standard enthalpies (Δ M H θ ) and the standard enthalpies of the Lewis acid/base reactions in the gaseous phase (Δ r H θ (g)). The mean standard enthalpies of the tin-oxygen (D̄(Sn–O)) and tin-sulphur (D̄(Sn–S)) bonds have been estimated.

Gibbs Transfer Energies of Macrocyclic Ligands in Methanol+N-methyl-2-pyrrolidinone Mixtures by Solubility and Partition Measurements

The standard Gibbs transfer energies of 18-crown-6,dibenzo-18-crown-6, cryptands 21, 22 and 222 frommethanol to methanol + N-methyl-2-pyrrolidinone(NMP) mixtures were determined from solubility andpartition measurements at 30 °C. While the Gibbs energy of transfer of 18-C-6 is positive,increases up to XNMP = 0.7 and thereafter decreases, the transfer energy ofdibenzo-18-C-6 is negative and decreases with the addition of NMP. However,the transfer energy of cryptand 21becomes increasingly negative with theaddition of NMP while that of cryptand 22 ispositive and increases under the sameconditions. For cryptand 222, the transferenergy is slightly negative up toXNMP = 0.5 butdecreases markedly at higher compositions of NMP. These results have been explainedin terms of the various types of interaction between the ligand molecules, solventcomponents and the effect of solvent–solvent interactions on them.

Comparative Study of the Luminescence Properties of the Europium(III) Complexes of the Squarate, Phenylsquarate, and (Diphenylamino)squarate Ligands.

Reaction of EuCl(3).6H(2)O with 3-phenyl-4-hydroxycyclobut-3-ene-1,2-dione (phenylsquarate) in methanol produces the polymeric complex {Eu(&mgr;-C(6)H(5)C(4)O(3))(2)(C(6)H(5)C(4)O(3))(2)(CH(3)OH)(2)(H(2)O)(2).(CH(3)OH)}(n)() (1) which crystallizes in the space group P2(1)/n with a = 13.4049(5) Å, b = 13.7043(7) Å, c = 18.5026(6) Å, beta = 106.351(4) degrees, and Z = 4. The Eu(III) ion is eight coordinate with two bridging and two pendant phenylsquarate ligands, the coordination polyhedron being completed by two aqua and two methanol ligands. The emission spectra of 1 and the already reported europium(III) squarate, [Eu(H(2)O)(4)](2)(C(4)O(4))(3) (2), and europium(III) (diphenylamino)squarate, {Eu[&mgr;-(C(6)H(5))(2)NC(4)O(3)](2)[(C(6)H(5))(2)NC(4)O(3)][NO(3)][H(2)O](4)}(2).4H(2)O (3) show emissions dominated by the Eu(3+)((5)D(0) --> (7)F(j)) transitions which are typical for Eu(3+) species in low-symmetry sites. For 1 the emission occurs at room temperature and is apparently sensitized by the phenyl substituents on the phenylsquarate ligand groups; for 2 and 3 the emission is only observed at low temperature (77 K). The broad band (370-575 nm) in the excitation spectrum of 3 at 77 K is consistent with excimer formation, which can be attributed to enhanced pi-pi interactions between the C(4)-cycles of neighboring phenylsquarate ligand groups whose centroid.centroid separation decreases from 3.630(7) Å at room temperature (293 K) to 3.565(7) Å at 96 K. The temperature dependence of the luminescence of all three complexes revealed strong Eu.Eu interactions which keep the energy transport process in the dynamic regime.

Photoredox Properties of Iron(III) Fluoro Complexes Containing Tetradentate Open‐Chain N2O2Ligands

AbstractTetradentate open‐chain Schiff base N2O2‐ligands of acacen, benacen or salen type and fluoride anions F− coordinate to the iron(III) central atom in methanol forming the complexes [Fe(N2O2)(CH3OH)F]. The complexes do not undergo spontaneous redox changes when kept in the dark. Their irradiation into intraligand or ligand‐to‐metal charge transfer bands causes the photoreduction of Fe(III) to Fe(II) associated with oxidation of metanol to its radical CH2OH. The final products of the primary photoredox and secondary dark redox processes, Fe(II) and CH2O, are formed in a 2:1 molar ratio. The efficiency of the axial methanol ligand photooxidation is strongly wavelength dependent and influenced by the peripheral groups R of the tetradentate ligands

Structural and Spectroscopic Comparisons between (μ-Oxo)- and (μ-Hydroxo)bis(μ-carboxylato)diiron(III) Complexes That Contain All-Oxygen-Donor Ligands

Treatment of the (μ-oxo)bis(μ-carboxylato)diiron(III) complex [Fe2(μ-O)(μ-XDK)(CH3OH)6]2+, where XDK2- = the dianion of m-xylylenediamine bis(Kemp's triacid imide), with 2 equiv of 1,1,1,5,5,5-hexafluoroacetylacetone (hfacH) and Et3N led to substitution of two methanol ligands by a bidentate hfac- anion at each metal center. The green bis(aqua) complex [Fe2(μ-O)(μ-XDK)(hfac)2(H2O)2] (3) was crystallographically characterized and presents water ligands bound trans to the bridging oxo group. Omission of Et3N from the above synthesis afforded an orange adduct, which is assigned as the (μ-hydroxo)(μ-XDK)bis(hfac)diiron(III) complex. Analytically pure samples of this [Fe2(μ-OH)(μ-XDK)(hfac)2(H2O)2]+ (4) cation were obtained as the salt of the noncoordinating anion tetrakis(3,5-bis(trifluoromethyl)phenyl)borate. Protonation of the oxo bridge in compound 3 leads to significant structural changes that are localized to the {Fe−O−Fe} core. The optical spectrum of 3 contains a broad ligand-field transition centered ...

Counterion Effect on CO/Styrene Copolymerization Catalyzed by Cationic Palladium(II) Organometallic Complexes: An Interionic Structural and Dynamic Investigation Based on NMR Spectroscopy

Complexes [Pd(η1,η2-C8H12OMe)bipy]+X- (2a−f) (where X = BPh4- (a), CF3SO3- (b), BF4- (c), PF6- (d), SbF6- (e), and B(3,5-(CF3)2C6H3)4- (f); bipy = 2,2‘-bipyridine; C8H12OMe = cyclooctenylmethoxy group) were synthesized by the reaction of the dimer [Pd(η1,η2-C8H12OMe)Cl]2 (1) with the bipy ligand in methanol containing Y+X- salts. They were characterized in solution by multinuclear and multidimensional NMR spectroscopy. The solid-state structure of complex 2d was obtained by X-ray single-crystal investigation. The catalytic activity of complexes 2 toward CO/styrene copolymerization in methylene chloride was tested and related to the type of counterion. The order of the catalytic activity of complexes 2a−f is the following: BPh4- ≪ CF3SO3- < BF4- < PF6- < SbF6- < B(3,5-(CF3)2C6H3)4-. If the copolymerization reactions are carried out in the presence of an excess of the bipy ligand, the anion effect is less important and the order is the following: BPh4- ≪ CF3SO3- < BF4- ≈ B(3,5-(CF3)2C6H3)4- ≈ PF6- ≈ SbF6-. The interionic structure of all complexes was investigated in CD2Cl2 at room and low temperature by 19F{1H} HOESY and 1H NOESY NMR spectroscopies. In solution, the counterions are located above or below the bipy ligand shifted toward the pyridine ring trans to the Pd−C σ bond, while in the crystal structure of 2d, they are settled sideways to the cationic moiety. The best anion in catalysis is the least strong coordinating one that shows the weakest interionic contacts in the 19F{1H} HOESY or 1H NOESY NMR spectra. The dynamic process that exchanges the two pyridyl rings was investigated by variable-temperature NMR spectroscopy in CD2Cl2. The activation parameters were determined. ΔG⧧298 values range from 54 to 58 kJ/mol. The negative values of ΔS⧧ (−58/−108 J K-1 mol-1), for all compounds, with the exception of 2f, suggest an associative mechanism.

Molybdenum−Pterin Chemistry. 2. Reinvestigation of Molybdenum(IV) Coordination by Flavin Gives Evidence for Partial Pteridine Reduction

The coordination of alloxazine and pterins to molybdenum(IV) is demonstrated in this study. The synthesis of MoOCl3(pteridineH), where pteridineH is the protonated form of 1,3,7,8-tetramethylalloxazine (tmaz), 2-pivaloyl-6,7-dimethylpterin (piv-dmp), and 6,7-dimethylpterin (dmp), proceeds readily starting from Mo(IV)Cl4(acetonitrile)2 and the pteridine ligand in chloroform or methanol. X-ray crystal structures of MoOCl3(tmazH) (1) and MoOCl3(piv-dmpH) (2) show that Mo chelates each pteridine at the carbonyl oxygen and pyrazine nitrogen and that the pteridine ligand is protonated at the other nitrogen in the pyrazine ring. A third X-ray structure for MoOCl3(H3dmp) (4) is included in this work since its determination permits the comparison of metrical parameters for the oxidized and reduced forms of a pterin in identical molybdenum coordination environments. The major difference observed in the structures of 2 as compared to 4 is the Mo−N5 bond length which is significantly shorter in compound 4 containing ...

Some complexes derived from zinc salicylate or 3,5-di-tert-butylsalicylate. The crystal structure of (2,2′-bipyridyl)(methanol)( O-salicylato)( O,O′-salicylato)zinc

The aqua ligands of diaquabis(salicylato)zinc and diaquabis(3,5-di-tert-butylsalicylato)zinc are easily displaced generating related bis-pyridine and 2,2′-bipyridyl complexes. Attempts to recrystallise the tert-butylsalicylate from ethanol resulted in replacement of the aqua ligands by ethanol ligands. The attempted recrystallisation of (2,2′-bipyridyl)bis(salicylato)zinc from methanol led to the isolation of octahedral [Zn(O 2CC 6H 4OH-2) 2(bipy)(MeOH)] in which one salicylato ligand is coordinated in a monodentate fashion and the other in a bidentate chelating manner, both coordination modes involving carboxylate rather than hydroxyl oxygen coordination. The methanol is strongly bonded trans to a nitrogen of the chelating 2,2′-bipyridyl and three further intramolecular six-membered hydrogen bonded rings are present, generated from interactions between the carboxyl and hydroxyl groups of the salicylate ligands and the hydroxyl group of the methanol ligand.