Structural variation from trinuclears to 1D chains: Syntheses,structures and properties

Five complexes [Co₃(Hpmad)₆]·(4‐sb)₂·(CH₃COO)₂·(H₂O)₂ ( 1 ), [Co₃(Hpmad)₆]·(3‐sb)₂·(CH₃COO)₂·(H₂O)_0.5 ( 2 ), [Co(Hpmad)₂(4‐sb)]_n ( 3 ), [Co(Hpmad)₂(3‐sb)]_n ( 4 ) and {[Co(Hpmad)(SO₄)(H₂O)₂]·H₂O}_n ( 5 ) [Hpmad is 2‐pyrimidineamidoxime, H₂(4‐sb) is 4‐sulfobenzoic acid and H₂(3‐sb) is 3‐sulfobenzoic acid], were prepared at room temperature. Complexes 1 – 5 were characterized by elemental analyses, single crystal X‐ray diffractions, powder X‐ray diffractions, infrared spectra, thermogravimetric analyses, fluorescence spectra and magnetic susceptibility measurements. Complexes 1 and 2 possess the linear trinuclear Co²⁺ structures. Complexes 3 and 4 exhibit similar one‐dimensional (1D) chains. Complex 5 comprises the 1D helical chain. The change of anion in cobalt salt from CH₃COO^? to Cl^? to SO₄^2? leads to the structural evolution from the linear trinuclear Co²⁺ structure to the 1D chain to the 1D helical chain. Complexes 1 – 5 exhibit the Hpmad‐based emissions. The magnetic properties of 1–5 were also investigated.     

Three-dimensional hybrid networks based on aspartic acid

Three-dimensional achiral coordination polymers of the general formula M₂(D, l-NHCH (COO)CH₂COO)₂·C₄H₄N₂ where M = Ni and Co and pyrazine acts as the linker molecule have been prepared under hydrothermal conditions starting with [M(L-NHCH(COO)CH₂COO)·3H₂O] possessing a helical chain structure. A three-dimensional hybrid compound of the formula Pb_2.5[N{CH(COO) CH₂COO}₂2H₂O] has also been prepared hydrothermally starting with aspartic acid and Pb(NO₃)₂. In this lead compound, where a secondary amine formed by the dimerisation of aspartic acid acts as the ligand, there is two-dimensional inorganic connectivity and one-dimensional organic connectivity.     

Synthesis and Structural Characterization of Six Pentanuclear and Tetranuclear Mo/W‐Cu‐S Clusters with Bis(diphenylphosphanyl) Methane

Six heterothiometalic clusters, namely, [WS₄Cu₄(dppm)₄](ClO₄)₂ · 2DMF · MeCN ( 1 ), [MoS₄Cu₄(dppm)₄](NO₃)₂ · MeCN ( 2 ) [MoS₄Cu₃(dppm)₃](ClO₄) · 4H₂O ( 3 ), [WS₄Cu₃(dppm)₃](NO₃) · 4H₂O ( 4 ), [WS₄Cu₃(dppm)₃]SCN · CH₂Cl₂ ( 5 ), and [WS₄Cu₃(dppm)₃]I · CH₂Cl₂ ( 6 ) [dppm = bis (diphenylphosphanyl)methane] were synthesized. Compounds 1 – 4 were obtained by the reactions of (NH₄)₂MS₄ (M = Mo, W) with [Cu₂(μ₂‐dppm)₂(MeCN)₂(ClO₄)₂] {or [Cu(dppm)(NO₃)]₂} in the presence of 1,10‐phen in mixed solvent (CH₃CN/CH₂Cl₂/DMF for 1 and 2 , CH₂Cl₂/CH₃OH/DMF for 3 and 4 . Compounds 5 and 6 were obtained by one‐pot reactions of (NH₄)₂WS₄ with dppm and CuSCN (or CuI) in CH₂Cl₂/CH₃OH. These clusters were characterized by single‐crystal X‐ray diffraction as well as IR, ¹H NMR, and ³¹P NMR spectroscopy. Structure analysis showed that compounds 1 and 2 are “saddle‐shaped” pentanuclear cationic clusters, whereas compounds 3 – 6 are “flywheel‐shaped” tetranuclear cationic clusters. In 1 and 2 , the MS₄^2– unit (M = W, Mo) is coordinated by four copper atoms, which are further bridged by four dppm molecules. In compounds 3 – 6 , the MS₄^2– unit is coordinated by three copper atoms and each copper atom is bridged by three dppm ligands.     

Syntheses,Structures and Characterization of Four Metal‐Organic Frameworks constructed by 2,2′,6,6′‐Tetramethoxy‐4,4′‐biphenyldicarboxylic Acid

Four metal‐organic frameworks (MOFs), {[Mn_3.5L(OH)(HCOO)₄(DMF)] · H₂O} ( 1 ), {[In_2.5L₂O(OH)_1.5(H₂O)₂] · DMF · CH₃CN · 2H₂O} ( 2 ), {[Pb₄L₃O(DMA)] · CH₃CN} ( 3 ), and {[LaL(NO₃)(DMF)₂] · 2H₂O} ( 4 ) were synthesized by utilizing the ligand 2,2′,6,6′‐tetramethoxy‐4,4′‐biphenyldicarboxylic acid (H₂L) via solvothermal methods. All MOFs were characterized by single‐crystal X‐ray diffraction, powder X‐ray diffraction, thermogravimetric analysis, and infrared spectroscopy. In 1 , the Mn²⁺ ions are interconnected by formic groups in situ produced via DMF decomposition to form a rare 2D macrocyclic plane, which is further linked by L^2– to construct the final 3D network. In 2 , 1D zip‐like infinite chain is formed and then interconnected to build the 3D framework. In 3 , a [Pb₆(μ₄‐O)₂(O₂C)₁₀(DMA)₂] cluster with a centrosymmetric [Pb₆(μ₄‐O)₂]⁸⁺ octahedral core is formed in the 3D structure. In 4 , the La³⁺ ions are connected with each other through carboxylate groups of L^2– to generate 1D zigzag chain, which is further linked by L^2– to construct a 3D network with sra topology. Solid photoluminescence properties of 3 and 4 were also investigated.     

Syntheses,structures of Mn(II), Ni(II), Cu(II) and Zn(II) coordination complexes based on 3,4,5-trifluorobenzeneseleninic acid and N-donor ligands

Abstract

Five new coordination complexes [Mn^II (L₁)₂(4,4′-bpy)]_n (1), [Ni^II (L₁)₂(4,4′-bpy)]_n (2), [Zn^II (L₁)₂(4,4′-bpy)]_n (3), [Cu^II (L₁)₂(phen)₂]Cl₂ (4) and [Cu^II ₂(L₁)₂(2,2′-bpy)₂]Cl₂ (5) (HL₁?=?3,4,5-trifluorobenzeneseleninic acid, 4,4′-bpy = 4,4′-bipyridine, 2,2′-bpy = 2,2′-bipyridine and phen = 1,10-phenanthroline), have been synthesized and characterized by single-crystal X-ray diffraction, powder X-ray diffraction (PXRD), elemental analysis and IR spectroscopy. Complexes 1–3 display similar layers structures. In 1–3, the adjacent layers are further connected through π···π interactions to form three-dimensional supramolecular structures. Complexes 4 and 5 show a dimer containing an eight-membered ring. The dimer extends into three-dimensional supramolecular structures through π···π interactions, C–H···F and C–H···Cl interactions.     

Substituent and Temperature Effect on the Assemblies of Three Lead(II) Coordination Polymers based on Asymmetrical Biphenyl Tritopic Ligands

Three Pb‐based metal‐organic frameworks, [Pb₆(L1)₄] · H₂O ( 1 ), [Pb₂(L2)₂(H₂O)] · H₂O ( 2 ), and [Pb(L2)(H₂O)] · H₂O ( 3 ) were constructed based on two asymmetrical tritopic ligands, 3‐(2′,5′‐dicarboxylphenyl)benzoic acid (H₃L1) and 3‐(2′,5′‐dicarboxylphenyl)pyridine acid (H₂L2), under hydrothermal conditions. The substituents on the two ligands and the induced temperature had effects on the resulting structures. All of the complexes were structurally characterized by X‐ray diffraction analyses and further identified by infrared spectra, elemental analyses, powder X‐ray diffraction, and thermogravimetric analyses. Complexes 1 and 3 are 3D frameworks, which construct from 1D inorganic Pb–O–Pb rod‐shaped secondary building units (SBUs) and H₃L1/H₂L2 ligands as pillars. Complex 2 is a 3D framework based on discrete tetranuclear Pb₄(COO)₈ clusters SBUs and H₂L2 ligands. The effects of both the substituent groups on the aromatic rings and the reaction temperature are discussed in details. The fluorescence properties and thermal stabilities of complexes 1 – 3 were also measured.     

Reaktionen von Organometallverbindungen. VI1. Bildung von Trichloroplumbaten(II) beim Zerfall von Dimethylbleidichlorid in Pyridin und Homologen

Reactions of organometal compounds. VI. Formation of Trichloroplumbates(II) by decomposition of dimethyl lead dichloride in pyridine and its homologues (CH₃)₂PbCl₂ disproportionates in pyridine, 2-methylpyridine and quinoline solution to give (CH₃)₂PbCl and – as a result of the decomposition of the second disproportionation product CH₃PbCl₃ in the presence of the bases – the trichloroplumbates(II) of the N-methylated bases: [C₅H₅N · CH₃][PbCl₃], [C₆G₇N · CH₃][PbCl₃] and [C₉H₇N · CH₃] · [PbCl₃]. N-methylpyridinium-trichloroplumbate(II) crystallizes orthorhombic, space group Pna2₁ or Pnma.     

Zur Kenntnis des Aluminiumchlorids. Die Umsetzung von AlCl3 mit PCl5 und Methylamin

Aluminium trichloride forms the adducts AlCl₃ · NH₂CH₃, AlCl₃ · 2NH₂CH₃, AlCl₃ · 4NH₂CH₃; AlCl₃ · NH₃CH₃Cl, AlCl₃ · 2NH₃CH₃Cl. The interaction between AlCl₃, PCl₅ and NH₃CH₃Cl in the molar ratio 1:3:2 proceeds according to the reaction equation in “Inhaltsübersicht”. On applying other stoichiometric amounts, [Cl₂(NHCH₃)P? N(CH₃)? AlCl₃] · HCl and [Cl₃P? N(CH₃)? AlCl₃] · HCl are obtained; the latter reacts as [Cl₃P? NHCH₃][AlCl₄]. At the molar ratio AlCl₃:PCl₅:NH₃CH₃Cl = 1:2:4 a compound is formed being presumably the six-membered heterocycle formulated in “Inhaltsübersicht”. With [Cl₃P?N? PCl₃] and aluminium chloride [Cl₃P?N? PCl₃][AlCl₄] is formed.     

[Mo2(O2C–CH3)4 · 1/2 {(CH2)6N4} · 1/2 CH2Cl2] – ein Donor‐Akzeptor‐Komplex mit supramolekularer Struktur

[Mo₂(O₂C–CH₃)₄ · ¹/₂ {(CH₂)₆N₄} · ¹/₂ CH₂Cl₂] – a Donor‐Acceptor Complex with Supramolecular Structure Yellow single crystals of [Mo₂(O₂C–CH₃)₄ · ¹/₂ {(CH₂)₆N₄} · ¹/₂ CH₂Cl₂] ( 1 ) have been obtained by the reaction of the silylated phosphaneimine Me₃SiNPEt₃ with [Mo₂(O₂C–CH₃)₄] in dichloromethane solution. 1 forms a three‐dimensional network with linear N–Mo:Mo–N and tetrahedral (CH₂)₆N₄Mo₄ moieties, which is topologically related with the PtS type. Space group P4₂/nnm, Z = 4, lattice dimensions at –70 °C: a = b = 1121.7(1), c = 1395.0(3) pm, R₁ = 0.0413.     

Tetraphenylphosphonium-trichloroplumbat(II), PPh4PbCl3 · CH3CN

Tetraphenylphosphonium Trichloroplumbate(II), PPh₄PbCl₃ · CH₃CN PPh₄PbCl₃ · CH₃CN was obtained by reaction of PbCl₂ and PPh₄Cl in acetonitrile. It was also formed along with (PPh₄)₂Se₂Cl₆ when PbSe was treated with chlorine in the presence of PPh₄Cl. Its crystal structure was determined by X-ray diffraction (R = 0.029 for 4186 reflections). The triclinic crystals contain PbCl₃^– ions that are associated to polymer chains. Each Pb atom has distorted square pyramidal coordination; the pyramids share two opposite basal edges. The chloro bridges are rather asymmetrical.     

On Verdigris,Part III: Crystal Structure,Magnetic and Spectral Properties of Anhydrous Copper(II) Acetate,a Paddle Wheel Chain

Pure anhydrous Cu(CH₃COO)₂ was obtained both, by thermal dehydration of Cu(CH₃COO)₂ · H₂O and by drying a commercially purchased mixture of Cu(CH₃COO)₂ · H₂O and Cu(CH₃COO)₂ in a nitrogen atmosphere using P₂O₅ as drying agent. The crystal structure was solved ab initio from synchrotron X‐ray powder diffraction (XRPD) data at 150 °C and from laboratory XRPD data at ambient conditions and found to be isotypic to anhydrous chromium(II), molybdenum(II) and rhodium(II) acetate. Cu(CH₃COO)₂ crystallizes in space group P1 (no. 2) with lattice parameters of a = 5.1486(3) Å, b = 7.5856(6) Å, c = 8.2832(6) Å, α = 77.984(4)°, β = 75.911(8)°, γ = 84.256(6)° at ambient conditions. Cu₂(CH₃COO)₄ paddle wheels with short (2.6 Å) Cu–Cu distances form chains in a direction, which is the main motif in the crystal structure. Due to their identical structural main motif Cu(CH₃COO)₂ · H₂O and Cu(CH₃COO)₂ exhibit a similar bluish‐green color, almost identical UV/Vis spectra and comparable magnetic properties. The temperature dependent magnetic susceptibility also indicates only weak inter‐dimer spin exchange between neighbouring Cu₂(CH₃COO)₄ paddle wheels.     

Synthesis,Structures and Spectroscopic Properties of Platinum(II), Palladium(II) and Copper(I) Halide Complexes with Pyrimidine‐phosphine Ligand

The reactions of pyrimidine‐phosphine ligand N‐[(diphenylphosphino)methyl]‐2‐pyrimidinamine ( L ) with various metal salts of Pt^II, Pd^II and Cu^I provide three new halide metal complexes, Pt₂Cl₄(μ‐L)₂·2CH₂Cl₂ ( 1 ), Pd₂Cl₄(μ‐L)₂ ( 2 ), and [Cu₂(μ‐I)₂L₂]_n ( 3 ). Single crystal X‐ray diffraction studies show that complexes 1 and 2 display a similar bimetallic twelve‐membered ring structure, while complex 3 consists of one‐dimensional polymeric chains, which are further connected into a 2‐D supramolecular framework through hydrogen bonds. In the binuclear complexes 1 and 2 , the ligand L serves as a bridge with the N and P as coordination atoms, but in the polymeric complex 3 , both bridging and chelating modes are adopted by the ligand. The spectroscopic properties of complexes 1 ‐ 3 as well as L have been investigated, in which complex 3 exhibits intense photoluminescence originating from intraligand charge transfer (ILCT) π→π* and metal‐to‐ligand charge‐transfer (MLCT) excited states both in acetonitrile solution and solid state, respectively.     

Synthese und Kristallstruktur von Praseodympropionat-trihydrat,Pr(CH3CH2COO)3(H2O)3

Synthesis and Crystal Structure of Praseodymium Propionate Trihydrate, Pr(CH₃CH₂COO)₃(H₂O)₃ Single crystals of Pr(CH₃CH₂COO)₃(H₂O)₃ were obtained by dissolving freshly prepared praseodymium hydroxide in diluted propionic acid. The crystal structure (monoclinic, P2₁/c, Z = 4, a = 1034.2(2) pm, b = 1521.2(3) pm, c = 2086.3(7) pm, β = 102.87(2)°, R1 = 0.0864, wR2 = 0.1196) consists of one-dimensional infinite chains parallel [010]. Pr1 and Pr2 are coordinated by four tridentate-bridging propionate groups. Additionally, Pr1 is coordinated by three “coordination water” molecules, Pr2 by two bidentate propionate groups. There are, in addition, three “crystal water” molecules so that praseodymium propionate trihydrate should be formulated as [(H₂O)₃Pr1(CH₃CH₂COO)₄Pr2(CH₃CH₂COO)₂] (H₂O)₃.     

Synthesis,Crystal Structures and Properties of Two Novel Co（Ⅱ） and Cd（Ⅱ） Complexes of N-AcetyI-L-glutamic Acid and Imidazole Ligands

Two novel complexes {[Co（A-glu）（Im）2]·0.5H2O}n （1） and [Cd（A-glu）（Im）3]n （2） （H2A-glu=N-acetyl-L-glutamic acid, Im=imidazole） have been synthesized from the reaction of H2A-glu with Co（CH3COO）2·4H2O or Cd（CH3COO）2·2H2O in the presence of Im. Both of the complexes display different coordination environment and similar one-dimensional chain structure. The magnetic susceptibility measurements for 1 show a weak antiferromagnetic interaction between two cobalt（Ⅱ） ions bridged by A-glu ligand. The complex 2 exhibits an intense fluorescent emission in solid state at room temperature.     

Die Kristall- und Molekülstrukturen von In(CH3COO)3 · 2,2′-Dipyridin und In(CH3COO)3 · 1,10-Phenanthrolin – Verbindungen mit Indium der Koordinationszahl 8

Crystal and Molecular Structures of In(CH₃COO)₃ · 2,2′-Dipyridine and In (CH₃COO)₃ · 1,10-Phenanthroline – Compounds of Indium with Coordination Number 8 In(CH₃COO)₃ · 2,2′-dipyridine and In(CH₃COO)₃ · 1,10-phenanthrline crystallize in the monoclinic space group P2₁/c with a = 844.7(3), b = 1 408.8(5), c = 1 466.6(5) pm, β = 84.9(1)°, Z = 4 (dipyridine complex) and a = 811.9(3), b = 1 555.3(5), c = 1 447.3(5) pm, β = 90.6 (1)°, Z = 4 (phenanthroline complex). The structures were determined by the heavy atom method from 2202 and 2617 independent reflections and have been refined by full matrix least-squares methods to R = 3.49 and 4.35%, respectively. In both complexes the acetate ligands and the N-donor ligand are bidentate, In attaining the coordination number 8. The donor atoms are arranged in the form of a distorted dodecahedron. Some distances and angles: see ?Inhaltsübersicht”?.     

Effects of metal ions and ligands on transesterification: synthesis,structures, and catalytic activities of a series of cation–anionic complexes with dipyridylamine ligands

A series of cation–anion complexes derived by 2,2′-dipyridylamine (Hdpa) and carboxylate ligands with formulas [Ni(Hdpa)₂(CH₃COO)]Cl(CH₃OH) (1), [Co(Hdpa)₂(CH₃COO)]Cl(CH₃OH) (2), [Ni(Hdpa)₂(CH₃CH₂CH₂COO)]Cl (3), [Co(Hdpa)₂(CH₃CH₂CH₂COO)]Cl (4), [Ni(Hdpa)₂(C₆H₅COO)]Cl (5), and [Co(Hdpa)₂(C₆H₅COO)]Cl (6), were synthesized and characterized by IR, elemental analysis, MS(ESI), TG analysis, UV-Vis, and fluorescence spectra. X-ray single crystal structural analysis showed that the coordination geometries of metal ions in these complexes are similar and they are cation–anion species. The hydrogen-bonding structures are 1-D chains through the N–H···Cl bonds. There are weak stacking interactions between pyridine rings in 1–4, while there are no stacking interactions in 5 and 6. We have investigated the transesterification of phenyl acetate with methanol catalyzed by 1–6 under mild conditions; 1–4 are homogeneous catalysts while 5 and 6 are heterogeneous catalysts due to their poor solubility in methanol. Cobalt complexes exhibit higher catalytic activities than corresponding nickel complexes. Complex 4 is the best catalyst of these six complexes.     

Syntheses and crystal structures of two complexes based on 2-amino-4,6-bis(4-pyridyl)-1,3,5-triazine

Two compounds based on 2-amino-4,6-bis(4-pyridyl)-1,3,5-triazine (4-HABPT), [Co(4-HABPT)₂(H₂O)₄](CH₃COO)₂ (1), and Zn(4-HABPT)₂Cl₂ (2) were obtained at room temperature. Single-crystal X-ray diffraction analyses indicate that 1 crystallizes in the triclinic P 1 with cobalt(II) coordinated by two 4-HABPT and four waters, two acetates are counter ions. The complex cations and acetates are linked to a 3-D framework by hydrogen bonds. Compound 2 crystallizes in the orthorhombic Pnc2 with zinc(II) coordinated by two 4-HABPT and two chlorides in a tetrahedral geometry; the complex also forms a 3-D framework by hydrogen bonds and π?···?π interactions.     

Synthesis,crystal structure,and luminescence of a new zinc(II) coordination polymer based on 2-naphthol-5-carboxylate and 4,4′-bipyridine

To further explore the coordination possibilities of naphthalene-based carboxylic acids, a Zn^II coordination polymer, [Zn₃(L)₆(bipy)₂] _n (1), with bulky 2-naphthol-5-carboxylate (L) and bridging 4,4′-bipyridine (bipy), was synthesized and characterized. Structural analysis reveals that 1 is a 1-D polymeric chain with trinuclear units as nodes, which are further extended via interchain secondary interactions, such as O–H ··· O hydrogen-bonding and aromatic π ··· π stacking interactions, to form an overall 3-D framework. Complex 1 exhibits strong solid-state luminescence emission at room temperature, mainly originating from intraligand π→π* transition of L.     

Synthesis and characterization of polystyrene-anchored monobasic bidentate Schiff base and its complexes with bi-, tri-, tetra- and hexavalent metal ions

A new monobasic bidentate ON donor Schiff base PS–LH₂ (where PS–LH₂ = polystyrene-anchored Schiff base obtained by condensation of chloromethylated polystyrene (containing 1.17 mmol of chlorine per gram of resin cross-linked with 2% divinylbenzene), 2-hydroxy-1-naphaldehyde and 4-aminosalicylic acid has been synthesized. PS–LH₂ reacts with metal complexes to form polystyrene-anchored complexes: PS–LHM(CH₃Coo) · DMF (where M = Cu, Zn, Cd, UO₂), PS–LHZr(OH)₂(CH₃Coo) · 2DMF, PS–LHFeCl₂ · 2DMF, PS–LHM′(CH₃Coo) · 3DMF (where M′ = Mn and Ni) and PS–LHMoo₂(acac), where acacH = acetylacetone. The polystyrene-anchored complexes have been characterized by elemental analysis, IR, ESR and magnetic susceptibility measurements. The per cent reaction conversion of PS–LH₂ to polystyrene supported coordination compounds lies between 30–95. Shifts of the azomethine ν(C=N) and phenolic ν(C–O) stretches are indicative of ON donor behaviour of the polystyrene-anchored ligands. The complexes, PS–LHCu(CH₃Coo) · DMF, PS–LHFecl₂ · 2DMF, PS–LHMn(CH₃Coo) · 3DMF and PS–LHNi(CH₃Coo) · 3DMF are paramagnetic, while PS–LHZn(CH₃Coo) · DMF, PS–LHCd(CH₃COO) · DMF, PS–LHUo₂(CH₃Coo) · DMF, PS–LHZr(OH)₂(CH₃COO) · 2DMF and PS–LHMoO₂(acac) are diamagnetic. The copper(II) complex exhibits a square planar structure, zinc(II) and cadmium(II) complexes have tetrahedral structures, nickel(II), manganese(II), iron(III), dioxomolybdenum(VI) and dioxouranium(VI) complexes have octahedral structure and zirconium(IV) complex is pentagonal bipyramidal.     

Synthesis, Spectral and Thermal Analyses of Novel Bi- and Polyhomonuclear Complexes of Pyrimidine Bisazo-dianil Derivatives

Seven new bi‐ and polyhomonuclear transition metal complexes with three polyhydroxlated bisazodianil ligands were synthesized and characterized. The ligands were derived from condensation of 6‐(5‐formyl‐2‐hydroxyphenylazo)‐2,4‐dihydroxypyrimidine with aliphatic diamines (H₈L¹, H₈L² and H₆L³). The data of elemental and thermal analyses, molar conductance measurement, IR, electronic and ESR spectra as well as magnetic moment measurements support the formation of [L¹Co₇Cl₆(H₂O)₁₀]·22H₂O ( 1 ), [H₂L²Mn₆Cl₆(H₂O)₈]·3H₂O·2EtOH ( 3 ), [L²Co₈Cl₈(H₂O)₁₂]·24H₂O ( 4 ), [H₄L³Co₂Cl₂(H₂O)₂]·8H₂O·2EtOH ( 6 ) with a tetrahedral geometry and [H₂L¹Ni₅Cl₄(H₂O)₁₆]·19H₂O·EtOH ( 2 ), [L²Ni₈Cl₈(H₂O)₂₈]·8H₂O·EtOH ( 5 ) with an octahedral geometry while [H₆L³Cu₃(H₂O)₇]Cl₃·10H₂O ( 7 ) has a distorted tetrahedral arrangement. The mode of bonding between the metal ions and the ligand molecules is determined and the metal‐metal interaction was studied. The activation thermo‐kinetic parameters for the thermal decomposition steps of the complexes E*, ΔH*, ΔS*, and ΔG* were calculated.