Molecular and Low‐dimensional Coordination Compounds of Copper(II) and 3, 5‐Dimethylpyrazole — Synthesis,Crystal Structure,and Properties

Three 3, 5‐dimethylpyrazole (pz*) copper(II) complexes, [Cu(pz*)₄(H₂O)](ClO₄)₂ ( 1 ), [Cu(pz*)₂(NCS)₂]·H₂O ( 2 ), and [Cu(pz*)₂(OOCCH=CHCOO)(H₂O)]·1.5H₂O ( 3 ), have been synthesized and characterized with single crystal X‐ray structure analysis. 1 crystallizes in the tetragonal space group, 14/m, with a = 14.027 (3) Å, c = 16.301 (5) Å, and Z = 4. 2 crystallizes in the monoclinic space group, P2₁/c, with a = 8.008 (3) Å, b = 27.139 (9) Å, c = 8.934 (3) Å, β = 106.345 (6)°, and Z = 4. 3 crystallizes in the triclinic space group, P1¯, with a = 7.291 (9) Å, b = 10.891 (13) Å, c = 11.822 (14) Å, α = 80.90 (2)°, β = 79.73(2)°, γ = 70.60(2)°, and Z = 2. In 1 , one water molecule and four pz* ligands are coordinated to Cu^II. Two [Cu(pz*)₄(H₂O)]²⁺ units are connected to ClO₄^— via hydrogen bonds. One lattice water molecule is found in the unit cell of 2 , which forms an one‐dimensional chain via intermolecular hydrogen bonds with the N‐H atom of pz*. In 3 , the oxygen atom of the coordinated water molecule is connected with two C=O groups of two neighbouring maleic acid molecules to form a linear parallelogram structure. Another C=O group of maleic acid forms a hydrogen bond with the N‐H atom of pz* to create a two‐dimensional structure. The spectroscopic and bond properties are also discussed.     

Structural and NMR Studies of the Hexameric Copper(I) Complex with N‐n‐butyl‐N′‐ethoxycarbonyl‐thioureate

The copper sulfide mineral flotation collector, N‐n‐butyl‐N′‐ethoxycarbonyl‐thiourea (H₂bectu), and the 1:1 hexameric copper(I) thioureate complex, [Cu(Hbectu)]₆, have been characterized by single crystal X‐ray diffraction. H₂bectu crystallizes in the triclinic space group with a = 5.2754(4), b = 9.0042(7), c = 12.6030(9) Å, α = 80.528(6), β = 90.173(6), γ = 76.472(7)°. An intramolecular N‐H···O hydrogen bond between the thioamide proton and carbonyl oxygen forms a planar six‐membered ring in the central core of the molecule with C=O, C=S and C‐N bond lengths in accord with those reported for other N‐alkyl/aryl‐N′‐acyl‐thiourea compounds. [Cu(Hbectu)]₆ crystallizes in the monoclinic space group C2/c with a = 23.269(5), b = 13.243(4), c = 23.037(7) Å, β = 91.81(2)° as discrete hexameric clusters disposed about a crystallographic centre of symmetry with a Cu₆S₆ core consisting of two Cu₃S₃ chair‐shaped rings linked by coordination of the deprotonated amide nitrogen atom to a copper atom in the adjacent ring. The six ligands assemble as a paddlewheel structure with the ethoxy and n‐butyl substituents packing in an alternating head to tail arrangement. Temperature dependent solution ¹H NMR spectroscopic studies show that the hexameric structure of the complex is maintained in solution.     

Molecular Structure and a Density Functional Theoretical Study on 2‐Nitroimino‐5‐Nitro‐Hexahydro‐1,3,5‐Triazine (NNHT)

2‐Nitroimino‐5‐nitro‐hexahydro‐1,3,5‐triazine (NNHT), was synthesized and its structure was determined by single‐crystal X‐ray diffraction. The crystal is monoclinic, space group P2₁/c with crystal parameters of a = 9.4031(13) Å, b = 8.5891(12) Å, c = 9.0200(13) Å, β = 91.213(2)°, V = 728.33(18) ų, Z = 4, F(000) = 392, D_c = 1.734 g/cm³. The experimental geometry of NNHT was input to Gaussian‐03W program and optimized using DFT‐B3LYP/6‐311++G** method. The IR frequencies and NMR chemical shift were carried out and compared well with those of the experimental. The atomic net charges and the population analysis are discussed. The heat of formation (HOF) for NNHT was evaluated by designing an isodesmic reaction. The detonation velocity (D) and detonation pressure (P) were estimated by using the well known Kamlet‐Jacobs equation, based on the theoretical HOF.     

Green synthesis and crystal structure of 4,7‐diaryl‐2‐oxo(thio)‐1,2,3,4,5,6,7,8‐octahydroquinazoline‐5‐one derivatives

A green and convenient approach to the synthesis of novel 4,7‐diaryl‐2‐oxo(thio)‐1,2,3,4,5,6,7,8‐octahydroquinazoline‐5‐one derivatives from appropriate aromatic aldehydes and 5‐aryl‐1,3‐cyclohexanedione with urea or thiourea in the presence of dilute HCl as catalyst in water is described. This method provides several advantages such as environmental friendliness, low cost, high yields, and simple workup procedure. The structures of all compounds were characterized by elemental analysis, IR, MS, and ¹H NMR. The crystal and molecular structure of 4‐(4′‐chlorophenyl)‐7‐(4′‐methoxyphenyl)‐1,2,3,4,5,6,7,8‐octahydroquinazoline‐2,5‐dione 5m have been determined by single crystal X‐ray diffraction analysis. The crystal of compound 5m belongs to monoclinic with space group P‐2₁/c, a = 1.4353 (4) nm, b = 1.4011 (4) nm, c = 0.9248 (3) nm, α = 90.00°, β = 101.242 (6)°, γ = 90.00°, Z = 4, V = 1.8241 (9) nm³, R₁ = 0.0448, and wR₂ = 0.1022. J. Heterocyclic Chem., (2011).     

Synthesis,Crystal Structure,Photophysical and Electrochemical Properties of rac‐6,13‐Dihydro‐6,13‐methanopentacene

The title compound, rac‐6,13‐dihydro‐6,13‐methanopentacene ( 1 ), has been synthesized and characterized by elemental analysis, FT‐IR, ¹H NMR, UV‐Vis, HRMS spectra, cyclic voltammetry and single‐crystal X‐ray diffraction. The crystal belongs to orthorhombic, space group P2₁2₁2₁, with Z = 4 and cell dimensions a = 6.0185(4), b = 8.1914(6), c = 31.4080(19) Å. In the crystal structure, two types of intermolecular C–H···π hydrogen bonds are observed, and further stabilize the crystal structure. Its photophysical and electrochemical properties and complementary density functional theory (DFT) calculations are reported.     

One Dimensional Coordination Polymer Constructed by1,2—Bis（4—pyridinecarboxamido）ethane and Copper（Ⅱ）

The ligand [1,2‐bis(4‐pyridinecarboxamido)ethane] (L) and the coordination polymer |[Cu(L)₂(H₂O)]‐(NO₃)₂·6H₂O|·(1) haw been synthesized and characterized by ER and ¹H NMR spectra. Their molecular structures and the packing of 1 have been determined by single‐crystal X‐ray diffraction analysis. The Cu(n) in 1 is bridged by two ligands forming an infinite one‐dimensional chain like structure and L in 1 adopts a different conformation from its free state. 1 belongs to monoclinic, space group P2₁/n, a = 1.2896(3) nm, b = 1.2552(8) nm, c = 2.2903(19) nm, β = 93.04(5)°, Z = 4, V = 3.702(4) nm³. The TG and DTG experiments showed that the uncoordinated H₂O can be removed at low temperature by heating, and it does not decompose until 250 °C.     

Hydrothermal Synthesis and Characterization of a One—Dimen—sional Copper（Ⅰ） Halide Cluster with 1,10—Phenanthroline

The title compound Cu₂Cl₂phen (phen = 1,10‐phenanthroline, C₁₂H₈N₂) 1 was synthesized from CuCl₂·2H₂O, CuCl and phen by hydrothermal method and its structure was determined by single crystal X‐ray analysis. With phen, CuG forms one‐dimensional chains, which comprise two zigzag chains based on fused Cu‐X units and connected via covalent bonds. The compound contains two crystallographically unique monovalent copper ions, Cu(1) and Cu(2). The Cu(1) atom in the tetrahedral site, is coordinated to two bridging Cl^? and two N atoms in phen. The Cu(2) atom with a slightly distorted triangular planar geometry, is coordinated to three Cl^?. The compound 1 was crystallized in monoclinic, space group P2₁/n with a = 0.37338(4), b = 1.9510(2), c = 1.68008(19) nm, β = 95.605 (3)°, R = 0.0458, and was characterized by elemental analysis, IR spectrum and TGA analysis.     

Hydrogen‐Bonding in Cyclic 2‐(3‐Oxo‐3‐phenylpropyl)‐Substituted 1,3‐Diketones: 17O‐NMR Spectra and X‐Ray Structure Determination

Structures of cyclic 2‐(3‐oxo‐3‐phenylpropyl)‐substituted 1,3‐diketones 4a – c were determined by ¹⁷O‐NMR spectroscopy and X‐ray crystallography. In CDCl₃ solution, compounds 4a – c form an eight‐membered‐ring with intramolecular H‐bonding between the enolic OH and the carbonyl O(11)‐atom of the phenylpropyl group, as demonstrated by increased shielding of specifically labeled 4a – c in the ¹⁷O‐NMR spectra (Δδ(¹⁷O(11))=36 ppm). In solid state, intermolecular H‐bonding was observed instead of intramolecular H‐bonding, as evidenced by the X‐ray crystal‐structure analysis of compound 4b . Crystals of compound 4b at 293 K are monoclinic with a=11.7927 (12) Å, b=13.6230 (14) Å, c=9.8900 (10) Å, β=107.192 (2)°, and the space group is P2₁/c with Z=4 (refinement to R=0.0557 on 2154 independent reflections).     

Assembly and Crystal Structure of a Novel 1—D Coordination Polymer of Copper（Ⅱ）with Thiocyanate and 4—Cyanopyridine

A novel one‐dimensional coordination polymer, Catena‐poly [bis(4‐cyano‐pyridyl) copper(II)‐di‐thiocyanate], ¹_∞ [Cu^II‐(cypy)₂(μ_N.S‐SCN)₂] (cypy = 4‐cyano‐pyridyl), was synthesized in a solution reaction of Cu(NO₃)₂·3H₂O, 4‐cyano‐pyridine and KSCN in mole ratio of 1:2:2 at room temperature. Its crystal structure was determined by single‐crystal X‐ray diffraction. The crystal belongs to monoclinic crystal system, space group P2₁/c with cell parameters a = 1.0719(2), b = 1.8441(4), c =0.9144(2) nm, β = 110.49(3)° and Z = 4. A full‐matrix least‐squares refinement gave R₁ = 0. 0393 and wR₂= 0.0916 for 1554 reflections having 1 >2σ(I). The crystal is thermally stable up to approximately 170 °C.     

[1‐Allylpyridinium][Cu2Cl3]: Synthesis,X‐ray Structure and the Regularity of Crystal Architecture of 1‐Allyl/(amino)‐pyridinium Copper(I) Chloride π‐Complexes

By alternating‐current electrochemical technique crystals of copper(I) π‐complex with 1‐allylpyridinium chloride of [C₅H₅N(C₃H₅)][Cu₂Cl₃] ( 1 ) composition have been obtained and structurally investigated. Compound 1 crystallizes in monoclinic system, space group C2/c a = 24.035(1) Å, b = 11.4870(9) Å, c = 7.8170(5) Å, β = 95.010(5)°, V = 2150.0(2) ų (at 100 K), Z = 8, R = 0.028, for 4836 independent reflections. In the structure 1 trigonal‐pyramidal environment of π‐coordinated copper(I) atom is formed by a lengthened to 1.376(2) Å C=C bond of allyl group and by three chlorine atoms. Other two copper atoms are tetrahedrally surrounded by chlorine atoms only. The coordination polyhedra are combined into an original infinite (Cu₄Cl₆^2—)_n fragment. Structural comparison of 1 and the recently studied copper(I) chloride π‐complexes with 3‐amino‐, 2‐amino‐, 4‐amino‐1‐allylpyridinium chlorides of respective [LCu₂Cl₃] ( 2 ), [L₂Cu₂Cl₄] ( 3 ), and [LCuCl₂] ( 4 ) compositions allowed us to reveal the trend of the inorganic fragment complication which depends on pKa (base) value of the corresponding initial heterocycle.     

新颖双核钐硫酚化合物[(THF)3I2Sm(m-SAr)]2 (Ar = Ph, 4-Me2NC6H4)的合成与化合物[(THF)3I2Sm(m-S-4-Me2NC6H4)]2的晶体结构

Reactions of SmI2 in THF with ArSSAr produced two binuclear samarium thiolate complexes [（THF）3I2- Sm（μ-SAr）]2 [Ar=Ph （1）, 4-Me2NC6H4 （2）] in high yields. The structure of 2 was characterized by single crystal X-ray crystallography. The crystal of 2 belongs to the triclinic system with space group P 1 and a=0.95705（13） nm, b= 1.22287（14） nm, c= 1.26450（14） nm, a=64.194（11）°, B=78.491（13）°, y=76.176（12）°, V= 1.2860（3） nm^3, Z= 1,μ=4.783 mm^-1, Dc= 1.964 Mg/m^3, M= 1521.19, S= 1.046, R1=0.0358, wR2=0.0910. X-ray analysis revealed that 2 is a thiolate-bridged dimer in which each Sm atom adopts a distorted pentagonal bipyramidal coordi- nation geometry.     

Synthesis and Structural Study of Copper(I) or Silver(I) Complexes of 2,11‐Dithia‐4,5,6,7,8,9‐Hexahydro[3.3]paracyclophanes

The complexes of 2,11‐dithia‐4,5,6,7,8,9‐hexahydro[3.3]paracyclophane (dthhpcp) with Cu(I), i.e. [Cu₂I₂(dthhpcp)₂]·2H₂O 1 , or with Ag(I), i.e. [Ag(dthhpcp)(NO₃)]thf 2 and [Ag(dthpcp)(CF₃COO)] 3 , were prepared for structural study by single‐crystal X‐ray diffraction analysis. For these three complexes, dthhpcp serves as a bridging group in the polymeric structure through bridging sulfur atoms via metal, while the bonding of anion with the second metal atom forms the multi‐diminished structures. Complex 1 is a novel two‐dimensional coordination polymer composed of Cu₆ motifs, in which Cu₂I₂ formed a square planar unit to link the dthhpcp molecule. The two oxygen atoms of the nitrate anion as a bridge for two Ag atoms in complex 2 provides a three‐dimensional channel framework of silver(I) with a tetrahydrofuran molecule as a guest inside the open cavities. In contrast, the analogous reaction with silver triflouroacetate gave a complex 3 , which is composed of infinite linear chains of‐Ag‐dthhpcp‐Ag‐dthhpcp‐ along the a axis. Unit cell data: complex 1 , orthorhombic system, space group P2(1)2(1)2(1), a = 19.2982(11) Å b = 16.5661(10) Å, c = 25.3006(15) Å, β = 90°, Z = 8; complex 2 , orthorhombic system, space group Pna2(1), a = 8.8595(6) Å, b = 12.6901(9) Å, c = 19.8449(14) Å, β = 90°, Z = 4; complex 3 , monoclinic system, space group P2(1)/n, a = 8.845(3) Å, b = 20.841(6) Å, c = 11.061(3) Å, β = 107.832(6)°, Z = 4.     

Synthesis and Characterization of New Copper(I) Complexes Containing Thione Derivatives of 1, 2, 4‐Triazine. Crystal Structure of [Cu(PPh3)2(ATTO)]NO3 (ATTO = 4‐amino‐1, 2, 4‐triazin‐3(2H)‐thione‐5‐one)

The reaction of 4‐amino‐1, 2, 4‐triazin‐3(2H)‐thione‐5‐one (ATTO, 1 ) with [Cu(PPh₃)₂]NO₃ in ethanol led to the complex [Cu(PPh₃)₂(ATTO)]NO₃ ( 2 ). 2 was characterized by elemental analyses, IR, ¹H NMR and Raman spectroscopy. A single‐crystal X‐ray diffraction of compound 2 revealed that ATTO acts as a bidentate ligand via its nitrogen and sulfur atoms. Crystal data for 2 at 20 °C: space group P2₁/n with a = 975.7(1), b = 1533.5(2), c = 2504.2(3) pm, β = 92.25(1)°, Z = 4, R₁ = 0.0632.     

Palladium(II) Complexes with the Mixed‐Donor Ligand CH3S‐(CH2)3‐PPh2 Crystal Structures of [PdCl2{CH3S‐(CH2)3‐PPh2}n](n = 1, 2)

The phosphorus‐sulfur ligand 1‐(methylthio)‐3‐(diphenylphosphino)‐propane (S‐P3) has been synthesized and characterized by ¹H NMR and ¹³C NMR. Reactions of S‐P3 with [PdCl₂(PhCN)₂] afforded the complexes [PdCl₂(S‐P3)] ( I ) and [PdCl₂(S‐P3)₂] ( II ), in which S‐P3 acts as a bidentate and monodentate ligand, respectively. Compound I crystallizes in monoclinic space group P2₁/n (No. 14) with cell dimensions: a = 8.589(3), b = 15.051(3), c = 17.100(3)Å, β = 102.91(2)°, V = 2154.7(9)ų, Z = 4. Likewise, compound II crystallizes in monoclinic space group P2₁/n (No. 14) with a = 9.993(5), b = 8.613(4), c = 18.721(5)Å, β = 90.18(3)°, V = 1611.3(12)ų, Z = 2. Compound II has a trans square planar configuration with only the P‐site of the ligand bonded to the palladium atom.     

Syntheses and Crystal Structures of Copper(II) and Copper(I) dpp Complexes, [Cu(dpp)Br2] and [Cu(dpp)2][CuBr2] (dpp = 2,9‐diphenyl‐1,10‐phenanthroline)

The complexes [Cu(dpp)Br₂] ( 1 ) and [Cu(dpp)₂][CuBr₂] ( 2 ) (dpp = 2,9‐diphenyl‐1,10‐phenanthroline) were synthesized and characterized by single‐crystal X‐ray diffraction methods. Reaction of copper(II) bromide with the dpp ligand in dichloromethane at room temperature afforded 1 , which is a rare example of non‐square planar four‐coordinate copper(II) complexes. Complex 1 crystallizes in the monoclinic space group C2/c with a = 15.352(3), b = 13.192(3), c = 11.358(2) Å, β = 120.61(3)°, V = 1979.6(7) ų, Z = 4, D_calc = 1.865 g cm^?3. The coordination geometry about the copper center is distorted about halfway between square planar and tetrahedral. The Cu‐N distance is 2.032(2) Å and the Cu‐Br distance 2.3521(5) Å. Heating a CH₂Cl₂ or acetone solution of 1 resulted in complex 2 , which consists of a slightly distorted tetrahedral [Cu(dpp)₂]⁺ cation and a linear two‐coordinate [CuBr₂]^? anion. 2 crystallizes in the triclinic space group with a = 10.445(2), b = 11.009(2), c = 18.458(4) Å, α = 104.72(3), β = 94.71(3), γ = 103.50(3)°, V = 1973.3(7) ų, Z = 2, D_calc = 1.602 g cm^?3. The four Cu(1)‐N distances are between 2.042(3) and 2.067(3) Å, the distance of Cu(2)‐Br(1) 2.2268(8) Å, and the disordered Cu(3)‐Br(2) distances are 2.139(7) and 2.237(4) Å, respectively. Complex 2 could also be prepared by directly reacting CuBr with dpp in CH₂Cl₂.     

Synthesis and Crystal Structure of Two One—dimensional Chain Copper Complexes [Cu（TTA）2（4,4‘’—azpy）] and [Cu（TTA）2（3,3‘’—azpy）

Two copper complexes [Cu(TTA)₂(4,4′‐azpy)] (1) and [Cu‐(TTA)₂(3,3′‐azpy)] (2) (HTTA = 1,1,1‐trifluoro‐3‐(2‐thenoyl)‐acetone, 4,4′‐azpy = 4,4′‐azobispyridine, 3,3′‐azpy = 3,3′‐azobispyridine) were synthesized and characterized. The crystal structures were determined by X‐ray diffraction analysis. The crystal 1 belongs to triclinic with space group P1 , a = 0.8515(2) nm, b = 0.9259(2) nm, c = 0.9468(2) nm, a = 66.126(9)°, β = 79.667(9)°, γ = 90.13(1)°, Z = 1, V = 0.6692(2) nm³, D_c = 3.425 g/cm³, γ = 2.113 mm^?1, F(000) = 694, R₁ = 0.0594, wR₂ = 0.1499. The crystal 2 belongs to monoclinic with space group P2₁/c, a = 1.0661(2) nm, b = 1.4296(3) ran, c = 1.0041(3) nm, β = 114.50(3)°, V = 1.3926(5) nm³, Z = 2, D_c = 1.646 g/ cm³, μ = 1.015 mm^?1, F(000) = 694, R₁, = 0.0535, wR₂ = 0.1113. In the crystals of complexes 1 and 2, the copper atoms have distorted octahedral symmetry. The two compounds possess very similar one‐dimensional linear chains linked through the rodlike 4,4′‐azpy ligands or 3,3′‐azpy ligands.     

Synthesis and Crystal Structure of Bis[（2,6—pyridinedicar—boxylato）（methanol）dibenzyltion（Ⅳ）]

A novel seven‐coordinate dimer bis[(2,6‐pyridinedicarboxylato)(methanol)dibenzyltin(IV)] was synthesized by the reaction of (PhCH₂)₃SnCl with 2,6‐pyridine dicarboxylic acid in 1:1 molar ratio in methanol solution. The structure was characterized by elemental analysis, IR and ¹H NMR spectra, and the crystal structure was determined by X‐ray single crystal diffraction analysis. The crystal belongs to monoclinic space group P2₁/n, a =0.96250(19) nm, b = 1.0947(2) nm, c = 1.9965(4) nm, β = 92.31(3)°, Z = 2, V = 2.1019(7) nm³, D_c = 1.574 g/cm³, μ = 1.248 mm^?1, F(000)=1000, R₁ = 0.0675, wR₂ = 0.0836. In the crystals of the complex, each tin atom is seven‐coordinated in a distorted bipyramidal structure.     

Synthesis, Structure and Biological Activities of S-[α-（ 4-Methoxyphenylcarbonyl ）-2-（1,2,4-triazole-l-yl） ethyl-N, N-dime-thyldithiocarbamate

The title compound was prepared by reaction of N, N‐dimethyldithiocarbamate sodium with l‐bromo‐l‐(4‐methoxyphenylcarbonyl)‐2‐(1, 2, 4‐triazole‐l‐yl) ethane. Its crystal structure has been determined by X‐ray diffraction analysis. The crystal belongs to triclinic with space group Pī, a = 0.7339(2) nm, b = 1.1032(2) nm, c = 1.1203(2) nm, a = 90.27(3)°, β = 102.03(3)°, γ = 104.91(3)°, Z=2, V = 0.8556(3) nm³, D_c = 1.360 g/cm³, μ =0.325 mm^?1, F(000)=368, final R₁ =0.0475. The planes of 4‐methoxybenzyl group and triazole ring are nearly perpendicular to each other. The dihedral angle is 83.97°. There is an obvious π‐π stacking interaction between the molecules in the crystal lattice. The results of biological test show that the title compound has fungicidal and plant growth regulating activities.     

Bis(2,4,7‐tri­methyl­indenyl)­cobalt(II) and rac‐2,2′,4,4′,7,7′‐hexamethyl‐1,1′‐biindene

The crystal and molecular structures of bis(η⁵‐2,4,7‐tri­methyl­indenyl)­cobalt(II), [Co(C₁₂H₁₃)₂], (I), and rac‐2,2′,4,4′,7,7′‐hexamethyl‐1,1′‐biindene, C₂₄H₂₆, (II), are reported. In the crystal structure of (I), the Co atom lies on an inversion centre and the structure represents the first example of a bis(indenyl)cobalt complex exhibiting an eclipsed indenyl conformation. The (1R,1′R) and (1S,1′S) enantiomers of the three possible stereoisomers of (II), which form as by‐products in the synthesis of (I), cocrystallize in the monoclinic space group P2₁/c. In the unit cell of (II), alternating (1R,1′R) and (1S,1′S) enantiomers pack in non‐bonded rows along the a axis, with the planes of the indenyl groups parallel to each other and separated by 3.62 and 3.69 Å.     

Synthesis,Crystal Structure,and Characterization of Two Novel Five‐coordinate Zinc(II) Complexes with the Tripod Ligand Tris(N‐methylbenzimidazol‐2‐yl‐methyl)amine and α,β‐unsaturated Carboxylates

Two novel five‐coordinate zinc(II) complexes with the tripod ligand tris(N‐methylbenzimidazol‐2‐ylmethyl)amine (Mentb) and two different α,β‐unsaturated carboxylates, with the composition [Zn(Mentb)(acrylate)] (ClO₄)·DMF·1.5CH₃OH ( 1 ) and [Zn(Mentb)(cinnamate)](ClO₄)·2DMF·0.5CH₃OH ( 2 ), were synthesized and characterized by means of elemental analyses, electrical conductivity measurements, IR, UV, and ¹H NMR spectra. The crystal structure of two complexes have been determined by a single‐crystal X‐ray diffraction method, and show that the Zn^II atom is bonded to a Mentb ligand and a α,β‐unsaturated carboxylate molecule through four N atoms and one O atom, resulting in a distorted trigonal‐bipyramidal coordination [τ( 1 ) = 0.853, τ( 2 ) = 0.855], with approximate C₃ symmetry.