Molecular dynamics of cis‐1‐(2‐hydroxy‐5‐ methylphenyl)ethanone oxime and N‐(2‐hydroxy‐4‐methylphenyl)acetamide in solution studied by NMR spectroscopy

The formation of hydrogen bonds and molecular dynamics for the molecules cis‐1‐(2‐hydroxy‐5‐methylphenyl)ethanone oxime ( I ) and N‐(2‐hydroxy‐4‐methylphenyl)acetamide ( II ) have been investigated in solution using NMR. The results confirm the formation of O? H···O, O? H···N and O···H? N type inter‐ and intramolecular hydrogen bonds. Spin‐lattice relaxation times (T₁), activation energy of molecular dynamics and energy of intramolecular hydrogen bonds have been determined. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis,structure and in vitro antiproliferative activities of oxamido‐bridged dicopper(II) complexes: A comparative study of experimental evidence and molecular docking of DNA/protein binding

Two μ‐oxamido‐bridged dicopper(II) complexes, namely [Cu₂(hmpoxd)(H₂O)(phen)](ClO₄) ( 1 ) and [Cu₂(papo)(H₂O)(phen)](ClO₄)·2H₂O ( 2 ), where H₃hmpoxd and H₃papo represent N‐(2‐hydroxy‐5‐methylphenyl)‐N′‐[3‐(dimethylamino)propyl]oxamide and N‐(2‐hydroxylphenyl)‐N′‐(3‐aminopropyl)oxamide, respectively, and phen represents 1,10‐phenanthroline, were synthesized. Single‐crystal X‐ray crystallography and other methods revealed that the two copper(II) ions in complex 1 are bridged by the cis‐hmpoxd^3? with Cu···Cu separation of 5.1896(7) Å, in which the inner (Cu1) and outer (Cu2) copper(II) atoms are located in square‐planar and square‐pyramidal geometries, respectively. To evaluate the effects of bridging ligand hydrophobicity on DNA/protein binding and potential anticancer activities, comparative studies of the reactivity towards herring sperm DNA and protein bovine serum albumin (BSA) as well as cytotoxicity of complex 1 with our previously reported complex 2 were conducted theoretically and experimentally. The results indicate that the two complexes can interact interactively with DNA, and bind to BSA via the binding sites Trp213 for 1 and Trp134 for 2 . Interestingly, the in vitro anticancer activities and DNA/protein binding affinities consistently follow the order of 1 > 2 .     

Impact of Reaction Conditions on the Structures of Nickel(II) Complexes Based on 3‐(4‐Carboxyphenyl)propionic Acid

Two new nickel(II) complexes, [Ni(4, 4′‐bpy)(H₂O)₄]_n · n(cpp) · 0.5nH₂O ( 1 ) and [Ni(cpp)(4, 4′‐bpy)(H₂O)₂]_n ( 2 ) [4, 4′‐bpy = 4, 4′‐bipyridine, H₂cpp = 3‐(4‐carboxyphenyl)propionic acid] were synthesized and characterized by single‐crystal X‐ray diffraction, elemental analysis, IR spectroscopy, and thermal analysis. In complex 1 , Ni^II ions are bridged by 4, 4′‐bpy into 1D chains, and cpp ligands are not involved in the coordination, whereas in complex 2 , cpp ligands adopt a bis(monodentate) mode and link Ni^II ions into 2D (4, 4) grids with the help of 4, 4′‐bpy ligands. Triple interpenetration occurs, which results in the formation of a complicated 3D network. The difference in the structures of the two complexes can be attributed to the different reaction temperatures and bases.     

A One‐dimensional Lead(II) Coordination Polymer with Bridging Saccharinate and 2‐Aminomethylpyridine Ligands: Synthesis,IR Spectra,and Crystal Structure of [Pb(ampy)(μ‐sac)2]n

A complex with eight‐coordinate lead(II ) atom and saccharinate (sac) and 2‐aminomethylpyridine ligands was characterized by IR, elemental analysis and X‐ray crystallography. The lead(II ) complex crystallizes in the monoclinic crystal system with space group P2₁/c. The single crystal X‐ray analysis shows that the complex is a coordination polymer, [Pb(ampy)(μ‐sac)₂]_n, in which the lead(II ) ions have a highly distorted bicapped trigonal antiprism coordination. Lead(II ) ions are bridged by carboxyl groups of sac forming one‐dimensional linear chains, running parallel to the a axis. The intrachain Pb···Pb distances are 4.4490(3) and 4.4679(3)Å. The individual chains are connected by N—H···O_sulfonyl and C_ampy—H···O_sulfonyl type hydrogen bonds, resulting in a three‐dimensional network. The sac ligand acts as bidentate and bridging ligand, while ampy behaves as an N, N′ donor. The IR spectra of the lead(II ) complex are discussed in detail.     

Synthesis,X‐ray powder structure analysis and biological properties of a mononuclear Cu(II) complex of N‐2‐hydroxyhippuric acid

A mononuclear copper (II) complex of N‐2‐hydroxyhippuric acid (2HHA), [Cu(HA)(H₂O)₂], has been synthesized and characterized by spectroscopic and X‐ray powder diffraction studies. Crystal structure of [Cu(HA)(H₂O)₂] reveals a distorted square‐pyramidal geometry around the metal center. The crystal packing in the complex exhibits a three‐dimensional framework formed by intermolecular O? ; H···O and C? H···O hydrogen bonds. Toxicity and antitumor properties of the complex have been studied in vivo. The complex, capable of depleting glutathione (GSH) at nontoxic doses, may be utilized to sensitize drug‐resistant cells where resistance is due to an elevated level of GSH. Copyright © 2009 John Wiley & Sons, Ltd.     

Modular Construction,Structures, and Magnetic Properties of Two Manganese Coordination Polymers Based on 3,5‐Bis(2–carboxylphenoxy)benzoic Acid

Two manganese(II) coordination polymers, namely, [Mn_1.5(BCB)(bpy)_1.5(H₂O)]_n ( 1 ), and [Mn(HBCB)(bibp)₂(H₂O)] ( 2 ), were assembled from the mixed ligands of the flexible tripodal ligand of 3,5‐bis(2‐carboxylphenoxy)benzoic acid (H₃BCB) and two rigid N‐donors [bpy = 4,4′‐bipyridine, and bibp = 4,4′‐bis(imidazolyl)biphenyl]. Their structures were determined by single‐crystal X‐ray diffraction analyses and further characterized by elemental analyses (EA), IR spectra, powder X‐ray diffraction (PXRD), and thermogravimetric (TG) analyses. Structural analysis reveals that complex 1 is a 3D (3,4,6)‐connected {5 · 6²}₂{5⁶ · 6⁴ · 7 · 8² · 9²}{6⁴ · 8 · 9} net based on two kinds of inorganic nodes of dinuclear {Mn₂(COO)₂} SBUs and Mn(2) ions. Complex 2 is a hydrogen bonds based 3D supramolecule with 6‐connected {4¹² · 6³}‐ pcu net. Besides, the variable‐temperature susceptibilities of 1 and 2 were investigated.     

Syntheses,Crystal Structures,and Photocatalytic Activities of Three Copper Coordination Polymers Based on Bis(1H‐imidazol‐4‐yl)benzene/3‐(2‐Pyridyl)pyrazole

Three copper(II) coordination polymers (CuCPs), namely, [Cu_0.5(1,4‐bib)(SO₄)_0.5]_n ( 1 ), {[Cu(1,3‐bib)₂(H₂O)] · SO₄ · H₂O}_n ( 2 ), and [Cu(bpz)(SO₄)_0.5]_n ( 3 ), were assembled from the reaction of three N‐donors [1,4‐bib = 1,4‐bis(1H‐imidazol‐4‐yl)benzene, 1,3‐bib = 1,3‐bis(1H‐imidazol‐4‐yl)benzene, and Hbpz = 3‐(2‐pyridyl)pyrazole] with copper sulfate under hydrothermal conditions. Their structures were determined by single‐crystal X‐ray diffraction analyses and further characterized by elemental analyses (EA), IR spectroscopy, powder X‐ray diffraction (PXRD), and thermogravimetric analyses (TGA). Structure analyses reveal that complex 1 is a 3D 6‐connected {4¹² · 6³}‐ pcu net, complex 2 is a fourfold 3D 4‐connected 6⁶‐ dia net, whereas complex 3 is a 1D snake‐like chain, which further expanded into 3D supramolecular architectures with the help of C–H ··· O hydrogen bonds. Moreover, the photocatalytic tests demonstrate that the obtained CuCPs are photocatalysts in the degradation of MB with the efficiency is 86.4 % for 1 , 75.3 % for 2 , and 91.3 % for 3 after 2 h, respectively.     

A Structural Study of the Iminodiacetate Moiety Conformation in N‐(1‐adamantyl)‐iminodiacetate(2‐) Copper(II) Complexes

N,N‐bis(carboxymethyl)‐1‐adamantylamine acid (H₂BCAA) or N‐(1‐adamantyl)‐iminodiacetic acid forms zwitterions that are intra‐stabilized by a ‘bifurcated’ N⁺‐H···O(carboxyl)₂ interaction. In the crystal, both half‐protonated carboxyl groups of H₂BCAA^± are involved in linear O‐H···O inter‐molecular bridges of 2.46Å. In the studied BCAA‐Cu^II derivatives, the iminodiacetate‐moiety of the BCAA chelating ligand exhibits a mer‐NO₂ conformation in [Cu(BCAA)(H₂O)₂] ( 1 ) and [Cu(BCAA)(Him)]₂ ( 2 ), but a fac‐O₂+N(apical) conformation in [Cu(BCAA)(bpy)(H₂O)]·3.5H₂O ( 3 ) [Him = imidazole, bpy =2,2′‐bipyridine]. In clear contrast, dipyridylamine (dpya), as auxiliary ligand, seems to be unable to promote the fac‐O₂+N(apical) conformation in BCAA, as reveal the structures of two new salts with the trinuclear cation [(dpya)₂Cu‐μ₂‐Cu(BCAA)₂‐Cu(dpya)₂]²⁺ and the anions [Cu(BCAA)₂]^2? ( 4 ) or NO₃^? ( 5 ), respectively.     

齐聚噻吩衍生物电致变色性质

合成了四种齐聚噻吩衍生物：5,5"-二氰基-2,2’:5’,2"-三噻吩 (DCN3T), 5,5"’-二氰基-2,2’:5’,2":5",2"’-四噻吩 (DCN4T), 5,5"’-甲氧基-2,2’:5’,2":5",2"’-四噻吩(DMO4T) 和 4,4"-二羧基-5,5"-二丙基-2,2’:5’,2"-三噻吩 (BP3T-DCOOH),研究了它们的电致变色性质,研究结果发现,这四种齐聚噻吩衍生物膜在电场作用下,可以发生可逆的颜色变化。     

Synthesis,Crystal Structures,and Thermal Analyses of ­Copper(II) and Manganese(II) Mixed‐Ligand Coordination Polymers Constructed from Benzimidazole‐5, 6‐dicarboxylic Acid and N‐Donor Ligands

The coordination polymers, {[Cu(Hbidc)(2, 2′‐bpy)(H₂O)] · 2H₂O}_n ( 1 ) and {[Mn(Hbidc)(2, 2′‐bpy) (H₂O)₂] · 2H₂O}_n ( 2 ) (H₃bidc = benzimidazole‐5, 6‐dicarboxylic acid, 2, 2′‐bpy = 2, 2′‐bipyridine), were synthesized in solution and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis (TGA), and single‐crystal X‐ray diffraction. Complexes 1 and 2 consist of different 1D chain structures. In both compounds, 2, 2′‐bpy is chelating in a bidentate manner, whereas the Hbidc ligands in complexes 1 and 2 display chelating‐bridging tridentate and bridging bidentate coordination modes. The two complexes are further extended into 3D supramolecular structures through O–H ··· O and N–H ··· O hydrogen bonds. The thermal stabilities of complexes 1 and 2 were studied by thermogravimetric analyses (TGA).     

Synthesis,Crystal Structures,and Photoluminescence of Lanthanide Coordination Polymers with 4‐Acetamidobenzoate

The reactions of Ln(NO₃)₃ · 6H₂O and 4‐acetamidobenzoic acid (Haba) with 4,4′‐bipyridine (4,4′‐bpy) in ethanol solution resulted in three new lanthanide coordination polymers, namely {[Ln(aba)₃(H₂O)₂] · 0.5(4,4′‐bpy) · 2H₂O}_∞ [Ln = Sm ( 1 ), Gd ( 2 ), and Er ( 3 ), aba = 4‐acetamidobenzoate]. Compounds 1 – 3 are isomorphous and have one‐dimensional chains bridged by four aba anions. 4,4′‐Bipyridine molecules don’t take part in the coordination with Ln^III ions and occur in the lattice as guest molecules. Moreover, the adjacent 1D chains in the complex are further linked through numerous N–H ··· O and O–H ··· O hydrogen bonds to form a 3D supramolecular network. In addition, complex 1 in the solid state shows characteristic emission in the visible region at room temperature.     

An Aqua‐Bridged Helical‐Chain Copper(II)‐Saccharinato Polymer Linked into a Two‐Dimensional Supramolecular Framework

A new assembly [Cu₂(sac)₂(μ‐dmea)₂(μ‐H₂O)]_n (sac = saccharinate and Hdmea = 2‐dimethylaminoethanol) has been synthesized and characterized by elemental analysis, IR spectroscopy, thermal analysis and single crystal X‐ray diffraction. The complex crystallizes in the monoclinic space group C2/c and consists of dinuclear modules of [Cu₂(sac)₂(dmea)₂]. The sac ligand is N‐coordinated, while the dmea ligand is in the deprotanated form by losing the ethanol hydrogen atom and acts as a bidentate donor through the alkoxo group and N atom. The alkoxo group also serves as a bridge between two copper(II) ions, leading to an intra‐dimer Cu···Cu separation of 3.0229(7) Å. The dimeric units are bridged by aqua ligands to generate a one‐dimensional water‐bridged helical chain, in which the copper(II) ions exhibit a distorted square‐pyramidal CuN₂O₃ coordination. The Cu–Cu distance in the chain separated by the bridging aqua ligands is 5.297Å. The polymeric chains are further linked by π(sac)···π(sac) and C–H···π(sac) interactions into a two‐dimensional supramolecular network.     

Synthesis,crystal structure,and DNA binding of a new oxalato-bridged binuclear zinc(II) complex

A new binuclear zinc(II) complex bridged by μ-oxalate, and end-capped with 2,2′-bipyridine (bpy), [Zn₂(ox)(bpy)₄](ClO₄)₂ · H₂O, has been synthesized and characterized by elemental analyses, molar conductance, IR, and electronic spectra and single-crystal X-ray diffraction. The single-crystal X-ray analysis reveals that the [Zn₂(ox)(bpy)₄]²⁺ cation has two zinc(II) centers bridged by a planar bis(bidentate) oxalate group with Zn···Zn distance of 5.482(3) Å; each zinc(II) is in a distorted octahedral environment. The crystal structure is stabilized by non-classical C–H···O hydrogen bonds and π–π stacking interactions to form a 3-D supramolecular structure. The interaction of the complex with calf-thymus DNA (CT-DNA) was explored by using electronic and fluorescence spectra and viscosity measurements. The results reveal that the complex intercalates with CT-DNA with intrinsic binding constant of 4.1 × 10⁴ M^?1.     

Mononuclear Co(III), Ni(II) and Cu(II) complexes of 2‐(2,4‐dichlorobenzamido)‐N'‐(3,5‐di‐tert‐butyl‐2‐hydroxybenzylidene)benzohydrazide: Structural insight and biological assay

A series of mononuclear metal complexes of Co(III), Ni(II) and Cu(II) with 2‐(2,4‐dichlorobenzamido)‐N′‐(3,5‐di‐tert‐butyl‐2‐hydroxybenzylidene)benzohydrazide ( LH ₃ ) have been synthesized and characterized using various physico‐chemical, spectroscopic and single crystal X‐ray diffraction techniques. Structural studies of [Co( LH )( LH ₂ )]·H₂O ( 4 ) revealed the presence of both amido and imidol tautomeric forms of LH ₃ , resulting in a distorted octahedral geometry around the Co(III) ion. [Ni( LH )(H₂O)]·H₂O ( 5 ) and [Cu( LH )(H₂O)]·H₂O ( 6 ) are isomorphous structures and crystallize in the monoclinic P2₁/c space group. The crystal structures of 4 , 5 and 6 are stabilized by hydrogen bonds formed by the enclathrated water molecules, C‐H···π and π···π interactions. Complexes along with the ligand ( LH ₃ ) were screened for their in vivo anti‐inflammatory activity (carrageenan‐induced rat paw edema method) and in vitro antioxidant activity (DPPH free radical scavenging assay). Metal complexes have shown significant anti‐inflammatory and antioxidant potential.     

Synthesis and Crystal Structures of Manganese(II) and ­Cobalt(II) Complexes with 2, 6‐Dimethoxybenzoic Acid and Additional N‐Donor Ligands

Three coordination compounds [Mn₃(dmb)₆(H₂O)₄(4, 4′‐bpy)₃(EtOH)]_n ( 1 ) and [M(dmb)₂(pyz)₂ (H₂O)₂] [M^II = Co ( 2 ), Mn ( 3 )] (Hdmb = 2, 6‐dimethoxybenzoic acid, 4, 4′‐bpy = 4, 4′‐bipyridine, pyz = pyrazine) were synthesized and characterized by single‐crystal X‐ray diffraction analysis. Compound 1 consists of infinite 1D polymeric chains, in which the metal entities are bridged by 4, 4′‐bpy ligands. There are four crystallographically independent Mn^II atoms in the linear chain with different coordination modes, which is only scarcely reported for linear polymers. The isostructural crystals of 2 and 3 are composed of neutral mononuclear complexes. In crystal the complexes are combined into chains by intermolecular O–H ··· N hydrogen bonds and π–π interactions between antiparallel pyrazine molecules.     

Tetrakis(1‐adamantylcarboxylato)dikupfer(II) Cu2(1‐Ad)4 – Synthese,Struktur und X‐/Q‐Band‐EPR‐Untersuchungen

Tetrakis(1‐adamantylcarboxylato)dicopper(II) Cu₂(1‐Ad)₄ – Synthesis, Structure and X‐/Q‐band EPR Investigations The synthesis and the crystal structure of tetrakis(1‐adamantylcarboxylato)dicopper(II) are reported. [Cu₂(1‐Ad)₄·2DMF] ( 1 , 1‐Ad = adamantylcarboxylate) crystallizes in the space group (Z = 2) with two crystallographically distinguishable complexes in the unit cell. The averaged Cu‐Cu distance of 260.5 pm is smaller than that found for Cu₂(ac)₄·2H₂O. The combination of temperature‐dependent X‐ and Q‐band powder EPR investigations in the temperature range 6 ≤ T ≤ 295 K show the presence of an antiferromagnetically coupled Cu‐Cu dimer and allow a precise determination of the spin‐Hamiltonian parameter. A comparison of those with that derived for Cu₂(ac)₄·2H₂O indicate a higher symmetry within the Cu₂O₈ central unit of [Cu₂(1‐Ad)₄·2DMF].     

Desulfuration and Cyclization of (Z)‐2‐[Amino(pyridine‐2‐yl)methylene]‐ hydrazonecarbothioamide in the Presence of Manganese(II)

The reaction of (Z)‐2‐[amino(pyridine‐2‐yl)methylene]hydrazonecarbothioamide (HAm4DH) with Mn(ClO₄)₂·6H₂O afforded different mononuclear or polynuclear manganese(II) complexes, the nature of which apparently depended on the solvent used. For example, in ethanol a compound of formula [Mn(HAm4DH)₂](ClO₄)₂ ( 1 ) was obtained, where HAm4DH coordinates as a common tridentate NNS donor, but the [Mn(bpy)₂(NCS)₂] complex ( 2 ) (bpy = 2,2'‐bipyridine) has also been obtained – probably due to C–N bond cleavage of the thiosemicarbazone. Nevertheless, in a basic aqueous medium [Mn(bpy)₃](ClO₄)₂·0.5bpy ( 3 ) is formed and there is structural evidence for chemical transformations of the thiosemicarbazone promoted by Mn^II. Thus, the sulfate in {[Mn(py)₄Mn(py)₂(H₂O)₂(μ‐SO₄)₂]·4H₂O}_n ( 4 ) or sulfate and cyclooctasulfur in [Mn(pta)₂(pdo)]₄(SO₄)₂·4H₂O·S₈] ( 5 ), where pta is 3‐(pyridin‐2‐yl)‐1,2,4‐triazol‐5‐amine and pdo is (2R,4R/2S,4S)‐pentane‐2,4‐diolato, arise from the desulfuration and oxidation of the thiosemicarbazone ligand. The structures of complexes 2 to 5 were established by single‐crystal X‐ray diffraction. The formation of pta is the result of the oxidative cyclization of HAm4DH. In the polynuclear complex 4 , the sulfate acts as an (O,O') bridge between alternating Mn(py)₂(H₂O)₂ and Mn(py)₄ centers. In the tetranuclear complex 5 , pta acts as a bischelating ligand through the N‐pyridine and N‐triazole, and pdo act as a bridge between two manganese atoms. It is also noteworthy that in complexes 4 and 5 hydrogen bonds give rise to different self‐assembly behaviour that leads to complicated supramolecular structures.     

A new one‐dimensional nickel metal–organic framework: catena‐poly[[[diaquabis(4‐{[(1‐phenyl‐1H‐tetrazol‐5‐yl)sulfanyl]methyl}benzoato‐κO)nickel(II)]‐μ‐4,4′‐bipyridine‐κ2N:N′] monohydrate]

The title complex, {[Ni(C₁₅H₁₁N₄O₂S)₂(C₁₀H₈N₂)(H₂O)₂]·H₂O}_n, was synthesized by the reaction of nickel chloride, 4‐{[(1‐phenyl‐1H‐tetrazol‐5‐yl)sulfanyl]methyl}benzoic acid (HL) and 4,4′‐bipyridine (bpy) under hydrothermal conditions. The asymmetric unit contains two half Ni^II ions, each located on an inversion centre, two L⁻ ligands, one bpy ligand, two coordinated water molecules and one unligated water molecule. Each Ni^II centre is six‐coordinated by two monodentate carboxylate O atoms from two different L⁻ ligands, two pyridine N atoms from two different bpy ligands and two terminal water molecules, displaying a nearly ideal octahedral geometry. The Ni^II ions are bridged by 4,4′‐bipyridine ligands to afford a linear array, with an Ni...Ni separation of 11.361 (1) Å, which is further decorated by two monodentate L⁻ ligands trans to each other, resulting in a one‐dimensional fishbone‐like chain structure. These one‐dimensional fishbone‐like chains are further linked by O—H...O, O—H...N and C—H...O hydrogen bonds and π–π stacking interactions to form a three‐dimensional supramolecular architecture. The thermal stability of the title complex was investigated via thermogravimetric analysis.     

Cadmium(II) Complexes with Mixed cis‐Epoxysuccinate and 2,2′‐Bipyridyl‐Like Ligands: Syntheses,Crystal Structures,and Luminescent Properties

Two new Cd^II complexes, [Cd( ces )(phen)]_∞ ( 1 ) and {[Cd( ces )(bpy)(H₂O)](H₂O)}₂ ( 2 ), were prepared by slow solvent evaporation methods from mixtures of cis‐epoxysuccinic acid and Cd(ClO₄)₂ · 6H₂O in the presence of phen or bpy co‐ligand ( ces = cis‐epoxysuccinate, phen = 1,10‐phenanthroline, and bpy = 2,2′‐bipyridine). Single‐crystal X‐ray diffraction analyses show that complex 1 has a one‐dimensional (1D) helical chain that is further assembled into a two‐dimensional (2D) sheet, and then an overall three‐dimensional (3D) network by the interchain C–H ··· O hydrogen bonds. Complex 2 features a dinuclear structure, which is further interlinked into a 3D supramolecular network by the co‐effects of intermolecular C–H ··· O and C–H ··· π hydrogen bonds as well as π ··· π stacking interactions. The structural differences between 1 and 2 are attributable to the intervention of different 2,2′‐bipyridyl‐like co‐ligands. Moreover, 1 and 2 exhibit intense solid‐state luminescence at room temperature, which mainly originates from the intraligand π→π* transitions of aromatic co‐ligands.     

Five Coordinated Zinc(II) and Tris‐Chelate Cadmium(II) Complexes with 2,2′‐Diamino‐5,5′‐dimethyl‐4,4′‐bithiazole – Syntheses,Spectroscopic Characterization,and Crystal Structure

The new synthesized ligand (DADMBTZ = 2,2′‐diamino‐5,5′‐dimethyl‐4,4′‐bithiazole), which is mentioned in this text, is used for preparing the two new complexes [Zn(DADMBTZ)₃](ClO₄)₂. 0.8MeOH.0.2H₂O ( 1 ) and [Cd(DADMBTZ)₃](ClO₄)₂ ( 2 ). The characterization was done by IR, ¹H, ¹³C NMR spectroscopy, elemental analysis and single crystal X‐ray determination. In reaction with DADMBTZ, zinc(II) and cadmium(II) show different characterization. In 2 , to form a tris‐chelate complex with nearly C₃ symmetry for coordination polyhedron, DADMBTZ acts as a bidentate ligand. In 1 , this difference maybe relevant to small radii of Zn²⁺ which make one of the DADMBTZ ligands act as a monodentate ligand to form the five coordinated Zn²⁺ complex. In both 1 and 2 complexes the anions are symmetrically different. 1 and 2 complexes form 2‐D and 3‐D networks via N‐H···O and N‐H···N hydrogen bonds, respectively.