A bifunctional 2,2′:6′,2″-terpyridine-based ligand for ratiometric Cu(II) sensing

Synthesis and characterization of the bifunctional sensor receptor ligand N-([2,2′:6′,2″-terpyridine]-4′-yl)methyl)-N-propylacrylamide (1) and the model ligand N-([2,2′:6′,2″-terpyridine]-4′-yl)methyl)-N-propylisobutyramide (2) are described. Ligand 1 is a receptor for Cu(II) that is copolymerizable with N-isopropylacrylamide giving a ratiometric sensor of weakly bound Cu(II) in environmental waters. Ligand 2 is a model for copolymerized 1 whereby the reactive acrylamide group is replaced by isobutyramide. Solution speciation of complexes of Cu(II) and Zn(II) with 2 were investigated spectroscopically and their solid-state structures were studied through single-crystal X-ray diffraction. Solution UV–vis and fluorescence studies show a preference of 2 toward Cu(II) over Na(I), Zn(II), Cu(II), Co(II), Mn(II), Ni(II), Cd(II), and Pb(II) in accord with the Irving–Williams series and other coordination principles. Solution speciation determined in a weakly coordinating aqueous-organic (60?:?40 DMF/H₂O) medium indicates 1?:?1 Cu(II):2 binding as desired in that formation of [Cu(2)₂]²⁺ would crosslink the polymer sensor. The crystal structures of [Cu(2)(NO₃)₂] and [Zn(2)(NO₃)₂]·MeOH·1/2Et₂O display distorted octahedral geometries where 2 coordinates meridionally and two nitrate groups occupy the remaining sites around the metal center.     

Heteronuclear complexes of oxorhenium(V) with Fe(III), Co(II), Ni(II), Cu(II), Cd(II) and UO2(VI) and their biological activities

Heteronuclear complexes containing oxorhenium(V), with Fe(III), Co(II), Ni(II), Cu(II), Cd(II) and UO₂(VI) ions were prepared by the reaction of the complex ligands [ReO(HL¹)(PPh₃)(OH₂)Cl]Cl (a) and/or [ReO(H₂L²)(PPh₃)(OH₂)Cl]Cl (b), where H₂L¹?=?1-(2-hydroxyphenyl)butane-1,3-dione-3-(5,6-diphenyl-1,2,4-triazine-3-ylhydrazone) and H₃L²?=?1-(2-hydroxyphenyl)butane-1,3-dione-3-(1H-benzimidazol-2-ylhydrazone), with transition and actinide salts. Heterodinuclear complexes of ReO(V) with Fe(III), Co(II), Ni(II), Cu(II) and Cd(II) were obtained using a 1?:?1 mole ratio of the complex ligand and the metal salt. Heterotrinuclear complexes were obtained containing ReO(V) with UO₂(VI) and Cu(II) using 2?:?1 mole ratios of the complex ligand and the metal salts. The complex ligands a and b coordinate with the heterometal ion via a nitrogen of the heterocyclic ring and the nitrogen atom of the C=N⁷ group. All transition metal cations in the heteronuclear complexes have octahedral configurations, while UO₂(VI)?complexes have distorted dodecahedral geometry. The structures of the complexes were elucidated by IR, ESR, electronic and ¹H NMR spectra, magnetic moments, conductance and TG-DSC measurements. The antifungal activities of the complex ligands and their heteronuclear complexes towards Alternaria alternata and Aspergillus niger showed comparable behavior with some well-known antibiotics.     

Synthesis and biological evaluation of Cu(II), Zn(II), and Ni(II) 3-(4-nitrophenyl)acrylic acid complexes with diamines as potential urease inhibitors

Five new Cu(II), Zn(II), and Ni(II) 3-(4-nitrophenyl)acrylic acid complexes were synthesized and evaluated for inhibitory activity on jack bean urease. All five complexes were structurally determined by single crystal X-ray analysis. Compared with the positive reference acetohydroxamic acid (IC₅₀?=?13.25?μM), Cu(II) complexes 3 and 4 showed the strongest inhibitory activity against jack bean urease (IC₅₀?=?1.23 and 1.17?μM). Ni(II) and Zn(II) complexes also exhibited inhibitory activities (IC₅₀?=?10.09–13.10?μM).     

NNS tridentate thiosemicarbazide and 1,3,4-thiadiazole-2-amine complexes of some transition metal ions: syntheses,structure and fluorescence properties

The reactions of Zn(II), Mn(II), and Ni(II) acetates with 1-picolinoyl-4-phenyl-3-thiosemicarbazide (Hppts) yielded [Zn(ppts)₂]·CHCl₃ (3), [Mn(ppts)₂]·THF (4), and [Ni(ppts)₂]·THF (5), respectively, but HgCl₂ gave a cyclized product N-phenyl-5-(pyridin-2-yl)-1,3,4-oxadiazole-2-yl-amine (2). The treatment of Hppts with conc. H₂SO₄ formed N-phenyl-5-(pyridin-2-yl)-1,3,4-thiadiazole-2-yl-amine (1). Hppts is a nonfluorescent material, but 3, 4 and the cyclized products 1,3,4-oxadiazole/1,3,4-thiadiazole are fluorescent. The cyclized ligand N-phenyl-5-(pyridin-2-yl)-1,3,4-thiadiazole-2-amine (1) formed [Zn(2-Hppt)₂(OAc)₂] (6) and [Cd₂(2-Hppt)₂(OAc)₂(μ-OAc)₂] (7) in which Cd(II) has a binuclear acetate-bridged seven coordinate pentagonal bipyramidal geometry. Complex 7 is also a fluorescent material with maximum emission at 425 nm at an excitation wavelength of 254 nm.     

Organoselenium/Tellurium-Bearing Macroacyclic and Cyclic Ligand Systems and Their Complexation Reactions

Abstract

A series of phenol-substituted acyclic Schiff bases, 2,6-{RE(CH₂) _n N═C(CH₃)}₂-C₆H₂(4-CH₃)(OH), (E = Te: R = C₆H₅, n = 2(L _a), 3(L _b); R = C₆H₄-4-OCH₃, n = 2(L _c), 3(L _d); E = Se: R = C₆H₅, n = 2(L _e), 3(L _f)), of the type E₂N₂O have been synthesized by condensation of 2,6-diacetyl-4-methylphenol with arylchalcogenoalkylamines. This ligand framework is useful for designing molecular complexes with a variety of coordination modes depending upon the nature of the central metal atom. The reactivity of the tellurium-bearing macroacyclics ligands towards Zn(II), Cd(II), and Hg(II) has been examined. The ligands L _a?L _d with Zn(II) and Cd(II), and only L _a and L _b with Hg(II) form complexes of composition M₂X₄L, (X = Cl or Br), whereas L _c and L _d with Hg(II) give products of composition HgBr₂L. The modes of ligand interaction with Zn(II) and Cd(II) are different than that with Hg(II).

Following a multistep reaction involving abstraction of bridged Br atoms and subsequent addition of more ligand, the mercury complex, Hg₂Br₄L has been used for developing metallocyclic system of the type [Hg₂Br₂L₂]²⁺. The latter has been found to encapsulate Zn(II) and Cd(II) to give multimetallic systems.     

Four metal–organic architectures from a triphenyl-tricarboxylic acid: synthesis,crystal structures,and catalytic features

Semi-flexible aromatic polycarboxylic acids are gaining impetus in crystal engineering of functional coordination polymers. This work opens up the use of a triphenyl-tricarboxylic acid, 3,5-(4'-carboxylphenyl) benozoic acid (H₃cba), as a versatile and still unexplored linker for the synthesis of four new Mn(II), Ni(II), Zn(II), and Cd(II) coordination polymers, formulated as [Mn(μ₃-Hcba)(bpy)]_n?nH₂O (1), [Ni(μ-Hcba)(py)(H₂O)]_n (2), [Zn(μ-Hcba)(phen)(H₂O)]_n?nH₂O (3), and [Cd(μ₃-Hcba)(bpy)]_n?nH₂O (4). These compounds were prepared via a facile hydrothermal procedure using metal(II) chlorides, H₃cba, and supporting N-donor ligands (2,2?-pyridine, bpy; pyridine, py; 1,10-phenanthroline, phen) acting as crystallization mediators. Compounds 1–4 were fully characterized and their X-ray crystal structures were established, disclosing the metal–organic architectures that range from 1D double chains (1, 4) to 1D chains (2, 3). Thermal and catalytic properties of 1–4 were also investigated. In particular, catalytic potential of the obtained coordination polymers in the Knoevenagel condensation of benzaldehydes with propanedinitrile was evaluated, disclosing an excellent performance of several heterogeneous catalysts with up to 100% product yield.

Graphical abstract

Four new Mn(II), Ni(II), Zn(II), and Cd(II) 1D coordination polymers have been constructed and the structures and catalytic properties of the polymers were investigated.

     

Electrochemical Study of the Mixed Ligand Complexes of Co(II) and Ni(II) with Acetylsalicylic Acid and Nicotinamide

The interaction of acetylsalicylic acid (aspirin, aspH) and nicotinamide (NA) with Co(II) and Ni(II) ions was investigated using square-wave and cyclic voltammetry techniques. In the presence of Ni(II)/Co(II),nicotinamide gave new peaks at -0.85V and soh.12 V, corresponding to the reduction of Ni(II)-nicotinamide(log β_1:2 =5.97) and Co(II)-nicotinamide (log β_1:2 =5.19) complexes, respectively. In the presence of Ni(II)/Co(II), acetylsalicylic acid gave new peaks at -0.91V and -1.19 V, respectively, corresponding to the reductionof Ni(II)-salicylate (log β_1:2 =8.48) and Co(II)-salicylate (log β_1:2 =8.14) complexes. In the presence of nicotinamide, Ni(II)-salicylate and Co(II)-salicylate form mixed ligand complexes, reducing at -0.78V (log β_1:2:2 =9.68) and -1.14V (log β_1:2:2 =8.64), respectively.     

Green and efficient oxidation of benzylic alcohols with hydrogen peroxide catalyzed by an inorganic–organic hybrid catalyst

Inorganic–organic hybrid catalysts 1-POM(M) were prepared by electrostatic interaction between transition metal-substituted polyoxometalates, {[PW₁₁MO₃₉]^4? [M?=?Cr(III), Fe(III)], [PW₁₁MO₃₉]^5?, [M?=?Mn(II), Co(II), Ni(II), Cu(II), Zn(II)], [PW₁₁VO₄₀]^4?}, and branched organic polyammonium, (tris[2-(dimethylammonium)ethyl]-1,3,5-benzenetricarboxylate), and characterized by elemental analyses, UV–vis and FT IR spectroscopic techniques, XRD, SEM, and Thermogravimetric-Differential thermogravimetric analyses. The hybrid material 1-POM(Zn) was an efficient and selective heterogeneous catalyst in the oxidation of benzylic alcohols to their corresponding carbonyl compounds with hydrogen peroxide. The catalyst was reused several times without significant loss of catalytic activity.     

Synthesis and X-ray crystal structures of three new terpyridine-based Pb(II) complexes,cytotoxicity studies of {[Pb(ttpy)(μ-AcO)]2}(SCN)2

Synthesis and X-ray crystal structures of three new terpyridine-based Pb(II) complexes, {[Pb(ttpy)(μ-AcO)]₂}(SCN)₂ (1) (ttpy?=?4′-tolyl-2,2′:6′,2″-terpyridine), [Pb(Clphtpy)(AcO)(ClO₄)] (2), and [Pb(Clphtpy)(SCN)₂] (3) (Clphtpy?=?4′-(4-chlorophenyl)-2,2′:6′,2″-terpyridine), are described. The synthesized materials have been characterized, also, by CHN elemental analysis, ¹H NMR, and IR spectroscopy. The structural analyses showed that, in the solid state, the coordination number of Pb(II) in 1, 2, and 3 are six, seven, and five, respectively. In the complexes, the lone-pair electrons of Pb(II) are stereochemically active and the coordination geometry of Pb(II) is hemidirected. The structures of the three complexes were compared and the effect of counter ion is described. The antibacterial activity of 1 and previously reported {[Pb(ttpy)(μ-AcO)]₂}(PF₆)₂ (1A) and {[Pb(ttpy)(μ-AcO)I]₂} (1B) were tested by minimum inhibitory concentration method to investigate the effect of counter ions on biological activity of the compounds. Also, cytotoxicity test was assessed using 3-[4,5-dimethylthiazol-2-yl]-2,5 diphenyl tetrazolium bromide assay to determine the maximum non-toxic concentration of ttpy, Pb(II), and their complexes to HepG2 cells. Effective lead detoxification was observed for 1, 1A, and 1B.     

Synthesis, structural characterization and antimicrobial activity evaluation of metal complexes of sparfloxacin

The synthesis and characterization of binary Cu(II)- (1), Co(II)- (2), Ni(II)- (3), Mn(II)- (4), Cr(III)- (5), Fe(III)- (6), La(III)- (7), UO₂(VI)- (8) complexes with sparfloxacin (HL₁) and ternary Cu(II)- (9), Co(II)- (10), Ni(II)- (11), Mn(II)- (12), Cr(III)- (13), Fe(III)- (14), La(III)- (15), UO₂(VI)- (16) complexes with sparfloxacin (HL₁) and dl-alanine (H₂L₂) complexes are reported using elemental analysis, molar conductance, magnetic susceptibility, IR, UV–Vis, thermal analysis and ¹H-NMR spectral studies.The molar conductance measurements of all the complexes in DMF solution correspond to non-electrolytic nature.All complexes were of the high-spin type and found to have six-coordinate octahedral geometry except the Cu(II) complexes which were four coordinate, square planar and U- and La-atoms in the uranyl and lanthanide have a pentagonal bipyramidal coordination sphere. The antimicrobial activity of these complexes has been screened against two Gram-positive and two Gram-negative bacteria. Antifungal activity against two different fungi has been evaluated and compared with reference drug sparfloxacin. All the binary and ternary complexes showed remarkable potential antimicrobial activity higher than the recommended standard agents. Ni(II)- and Mn(II) complexes exhibited higher potency as compared to the parent drug against Gram-negative bacteria.     

Synthesis,structure and properties of three one-dimensional coordination polymers {[M(II)L(NCS)2](DMF)2} n (M(II)=cadmium(II), zinc(II), manganese(II); L=1,4-bis[2-(2-pyridyl)benzimidazolato]butane)

A tetradentate N-donor ligand 1,4-bis[2-(2-pyridyl)benzimidazolato]butane (L) was prepared for construction of a coordination framework. Three one-dimensional coordination polymers {[M(II)L(NCS)₂](DMF)₂} _n (M(II) = cadmium(II), 1, zinc(II), 2, manganese(II), 3) were obtained by reaction of metal ions and L in the presence of KSCN in DMF/water. The complexes are isostructural and consist of 1D zigzag [M(II)L(NCS)₂] _n chains and DMF molecules. Within the chains, the metal atoms are each octahedrally coordinated by four N atoms of L and two N atoms of the SCN^? anions. Complexes 1 and 2 in the solid state at room temperature exhibit intense photoluminescence at 453 and 433 nm, respectively.     

Reactions of divalent transition metal halides with 3,5-dimethyl-1-(hydroxymethyl)-pyrazole

Factors determining the complex formation reaction of copper(II), nickel(II) and cobalt(II) chloride and copper(II) bromide with 3,5-dimethyl-1-(hydroxymethyl)-pyrazole (HL) has been studied. Depending on experimental conditions, complexes with different composition were obtained: [CuCl₂(dmp)]₂ (I), [CuCl₂(dmp)₂]₂ (II), [CoCl₂(dmp)₂] (III) (dmp=3,5-dimethylpyrazole), [CuBr(L)]₂ (IV), [CoCl(L)(EtOH)]₄ (V) and [NiCl(L)(EtOH)]₄ (VI). The compounds were characterized by FTIR spectroscopy, solution conductivity and magnetic measurements. The crystal structure of [CoCl(L)(EtOH)]₄ has been determined by single crystal X-ray diffraction. The thermal decomposition of the compounds was studied and found to be continuous for all of the compounds. The desolvation mechanism of [MCl(L)(EtOH)]₄ (M=Co(II), Ni(II)) is explained on the basis of the route of complex formation of CoCl₂ with HL.     

Synthesis and characterization of manganese(II), nickel(II), copper(II) and zinc(II) Schiff-base complexes derived from 1,10-phenanthroline-2,9-dicarboxaldehyde and 2-mercaptoethylamine

The synthesis of a new Schiff base containing 1,10-phenanthroline-2,9-dicarboxaldehyde and 2-mercaptoethylamine is described. The reaction of 1,10-phenanthroline-2,9-dicarboxaldehyde with 2-mercaptoethylamine leads to 2,9-bis(2-ethanthiazolinyl)-1,10-phenanthroline (I) which undergoes rearrangement when reacted with manganese, nickel, copper or zinc ions to produce complexes of the tautomeric Schiff base 2,9-bis[2-(2-mercaptoethyl)-2-azaethene]-1,10-phenanthroline (L). The [M(L)Cl₂] complexes [where M = Mn(II), Ni(II), Cu(II) and Zn(II) ions] were characterized by physical and spectroscopic measurements which indicated that the ligand is a tetradentate N₄ chelating agent.     

Synthesis,Characterization and Antifungal Activity of Metal Complexes of 2-(5-((2-Chlorophenyl)Diazenyl)-2-Hydroxybenzylidene) Hydrazinecarbothioamide

Abstract

New metal complexes of Co(II), Cu(II), Ni(II), Zn(II), Mn(II), Fe(III), Ru(III), UO₂(II), and VO(II) with the Schiff base, 2-(5-((2-chlorophenyl)diazenyl)-2-hydroxy- benzylidene) hydrazine-carbothioamide (H₂L) have been prepared and characterized by elemental and thermal analyses, FT-IR, UV–Vis, mass spectra, ¹H-NMR, and ESR as well as conductivity and magnetic moments measurements. The IR spectra showed that the ligand acts as neutral tridentate, neutral bidentate or monobasic tridentate ligand. The geometries of metal complexes were either octahedral or square pyramidal. The ESR spectra of the solid copper(II) complexes indicated an axial symmetry type of a d_(x2-y2) ground state with considerably ionic or covalent environment. The effect of the presence of an azo group on the biological activity of the ligand was investigated. The ligand and its complexes are biologically inactive due to the presence of azo group.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the related elements to view the free supplemental file.     

Two copper complexes based on nitronyl nitroxide with different halides: structures and magnetic properties

Complexes based on different halogen-substituted nitronyl nitroxide radicals and Cu(II), Cu₃(hfac)₆(NIT-Ph-F)₂ (1) and Cu₃(hfac)₆(NIT-Ph-Cl)₂ (2) (hfac = hexafluoroacetylacetonate; NIT-Ph-F = 2-(4′-fluorophenyl)-4,4,5,5-tetramethyl-imidazoline-1-oxyl-3-oxide; NIT-Ph-Cl = 2-(4′-chlorphenyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide), were synthesized and characterized structurally and magnetically. X-ray crystal structure analyses show that 1 and 2 have similar centrosymmetric five-spin structures consisting of three Cu(II) ions bridged by two nitroxide ligands. The Cu(II) is coordinated by six oxygens to form an octahedron, while the five coordination of the terminal Cu(II) ion is square pyramidal. Magnetic measurements reveal strong antiferromagnetic interactions between Cu(II) ions and radicals in 1 (J = ?38.9 cm^?1) and weak antiferromagnetic interactions between Cu(II) ions and radicals in 2 (J = ?1.23 cm^?1), which may be explained by the bond length of the Cu–O_rad (2.468(2) Å) in 1, which is shorter than that (2.514(2) Å) in 2, and the dihedral angle (73.17(1)°) of the plane O7–O8–Cu(2)–O7A–O8A with the moiety O5–N1–C11–N2–O6 in 1 is smaller than (77.82(1)°) in 2.     

Studies on mononuclear transition metal chelates derived from a novel ( E,E )-dioxime: synthesis,characterization and biological activity

A novel vic-dioxime ligand with a thiourea moiety, (4E,5E)-1,3-bis{4-[(4-bromophenylamino)methylene]phenyl}-2-thiooxaimidazoline-4,5-dione dioxime (4) (bmdH₂) has been synthesized from N,N′-bis{4-[(4-bromophenylamino)methylene]phenyl}thiourea and (E,E)-dichloroglyoxime. The bmdH₂ ligand (4) forms transition metal complexes [M(bmdH)₂] with a metal?:?ligand ratio of 1?:?2 with M?=?Ni(II), Co(II), and Cu(II). The mononuclear Ni(II), Co(II) and Cu(II) complexes, [Ni(bmdH)₂] (5), [Co(bmdH)₂] (6) and [Cu(bmdH)₂] (7) have the metal ions coordinated through the two N,N atoms, as do most vic-dioximes. Elemental analyses, molar conductivity, magnetic susceptibility, IR, ¹H NMR spectra, and UV-Visible spectroscopy were used to elucidate the structures of the ligand and its complexes. Conductivity measurements have shown that the mononuclear complexes are non-electrolytes. In addition, the ligands and metal complexes were screened for antibacterial and antifungal activities by agar well diffusion techniques using DMF as solvent.     

Synthesis,characterization and crystal structures of copper(II), zinc(II) and vanadium(V) complexes,derived from 3-methyl-N′-(1-(pyridin-2-yl)ethylidene)benzohydrazide,with antibacterial activity

Three copper(II), zinc(II), and vanadium(V) complexes, [CuL(HL)]ClO₄ (1), [ZnL₂] (2) and [VO₂L] (3), where L is the anionic form of 3-methyl-N′-(1-(pyridin-2-yl)ethylidene)benzohydrazide (HL), were prepared and characterized by IR, UV–vis and single-crystal X-ray determination. X-ray analysis indicates that the complexes are mononuclear species, with the Cu and Zn ions in 1 and 2 in octahedral coordination, and with the V ion in 3 in trigonal bipyramidal coordination. The hydrazone compound and the three complexes were evaluated for antibacterial activities. The copper complex has effective activities.     

Complexation of the N,N′,O-donor ligand N-trans-(2′-hydroxycyclohexyl)-2-aminomethylpyridine

The potentially tridentate N,N′,O-donor N-trans-(2′-hydroxycyclohexyl)-2-aminomethylpyridine (1) forms ML₂ complexes with M(II)?=?Cu, Ni, and Zn. X-ray crystal structures of the isostructural Ni(II) and Zn(II) complexes confirm bis-tridentate coordination in significantly distorted octahedral geometries as the all-cis facial isomer. Structural comparisons with the previously reported all-trans facial Cu(II) and cis,cis,trans(N_py) facial Co(III) complexes are presented. Protonation constants for 1 and stability constants with Cu(II), Ni(II), and Zn(II) are reported, with both ML and ML₂ species defined. The trend for ML (log K ₁ values for Cu, Ni, and Zn of 8.3, 6.9, and 5.3, respectively) is conventional. Protonation and stability constants with Cu(II) for N,N-bis(2-pyridylmethyl)amine (2) were also defined. The log K ₁ value measured for 2 of 7.4 is very similar to that found for 1 of 8.3, despite the marked difference in the third donor group; it appears that the third donor of the tridentate ligand generally binds only poorly to Jahn–Teller elongated Cu(II) in solution.     

Organophosphorus Ligands in Studies of Metal Complexes. Investigations of Ligand Exchange and Multielement Trace Analysis using Dithiophosphinic Ligands

Abstract

On mixing organic solutions of [Et₂PS₂]M/n and [Prop₂PS₂]M/n [M=Pd(II), Pt(II), Rh(III), lr(III), Cr(III)] an equilibrium is obtained containing statistical amounts of the corresponding mixed ligand complexes as can be shown by 31P{¹H}-NMR, HPLC and FD-MS. With Pt(II)- and Pd(II)-chelates the kinetics of ligand exchange was determined by HPLC. Mixed complexes ML₂L′ and MLL′₂ were isolated from the equilibrium solutions in case of the more inert Cr(III)-, Rh(III)- and lr(III)-chelates by preparative HPLC. Pd(II), Pt(II) and Rh(III) can be determined quickly and simultaneously in aqueous solutions at nanogramm level by complexation with Et₂PS₂? in a modified sample loop followed by reversed phase HPLC.     

Syntheses and structural characterization of six ionic salts based on bis(benzimidazole)/bis(imidazole) and perchlorometallates of Zn and Cu

Six salts, ([(H₂L1)(ZnCl₄)] (1) (L1 = 1,1′-bis(benzimidazolyl)methane), [(H₂L1)(CuCl₄)]·H₂O (2), [(H₂L2)(ZnCl₄)] (3) (L2 = 1-(3-(1H-benzimidazol-1-yl)propyl)-1H-benzimidazole), [( H₂L2)(CuCl₄)] (4), [(H₂L3)(CuCl₄)]·H₂O (5) (L3 = 1- (4-(1H-benzimidazol-1-yl)butyl)-1H-benzimidazole), and [(H₂L4)(ZnCl₄)]·H₂O (6) (L4 = 3,6-bis(imidazol-1-yl)pyridazine)), derived from bis(benzimidazole)/bis(imidazole) and metal(II) chloride dihydrate (zinc(II) chloride and copper(II) chloride dihydrate) were prepared and characterized by IR, X-ray structure analysis, elemental analysis, and TG analysis. The aromatic rings of the cations in all of the compounds are planar. X-ray diffraction analysis revealed that all the complexes have 3-D layer network structures built from hydrogen bonds between the cations and chlorometallate anions. Water molecules also play an important role in structure extension in 2, 5, and 6. The arrangements of the anions and cations in their solid state are dominated not only by size and symmetry of the cations, but also by the non-covalent interactions existing in the crystal structures.