Synthesis, Crystal Structure, Spectroscopic and Magnetic Properties of an Unprecedented Three-Dimensional CuII Coordination Compound of 1,2-Bis(1,2,4-triazol-4-yl)ethane

Abstract

A novel three‐dimensional copper(II) compound of the formula [Cu3(btre)5(H2O)2](ClO4)6·H2O (btre = 1,2‐bis(1,2,4‐triazol‐4‐yl)ethane) has been synthesized. The structure has been solved at 150 K by single‐crystal X‐ray analysis. The compound [C30H44Cu3N30O2·6(ClO4)·H2O] crystallizes in the triclinic space group P1bar with a = 12.488(1), b = 13.195(1), c = 19.756(2) Å, α = 78.959(8), β = 84.553(8), γ = 63.869(7)°, V = 2868.4(5) Å3, Z = 2 (trinuclear CuII units), 6484 reflections [I > 4σ(I)], RF = 0.0581, wR2 = 0.1214. The structure of this coordination polymer consists of a three‐dimensional network built up from linear trinuclear CuII cations of formula [Cu3(btre)5(H2O)2]6+. This crystallographically independent unit comprises a linear array of three CuII ions linked by triple N1,N2‐1,2,4‐triazole bridges, yielding Cu1–Cu2 = 3.893(1) Å and Cu2–Cu3 = 3.889(1) Å. These linear trinuclear CuII units are linked by various pathways involving tridentate and tetradentate bridging btre ligands, which yields an unprecedented three‐dimensional network. The CuII ions are weakly antiferromagnetically coupled with J = –1.01(2) cm–1 (based on the Hamiltonian: H = –J[SCu1·SCu2 + SCu2·SCu3] using the expression for the molar magnetic susceptibility S = 1/2 of a linear trinuclear system). The nature and the magnitude of the antiferromagnetic exchange have been discussed on the basis of the structural features.

Self-assembly from silver(І) salts and 3,5-dimethyl-4-amino-1,2,4-triazole: syntheses and crystal structures

“…The capability of the 1,2,4-triazole ligands to form a bridge between transition-metal ions by establishing the N1,N2 coordination mode makes them very useful for obtaining polynuclear coordination compounds [2]. Substituents have been attached to the N4 of the 1,2,4-triazole in order to prevent coordination at this position.…”

A new silver(I) coordination polymer containing 3-methylthio-(1H)-1,2,4-triazole as precursor for preparation of silver nanorods

“…These advantages make 1,2,4-triazoles very useful for the synthesis of various polynuclear coordination compounds [11]. As the metal center, Ag(I), is a favorable ion for the construction of coordination polymers due to its flexibility and positive coordination tendency with N and S donor atoms [12][13][14][15], the reaction of 1,2,4-triazole and its derivatives with Ag(I) salts have produced various coordination polymers with interesting properties [16][17][18][19][20][21][22][23][24][25].…”

A novel three-dimensional network silver coordination polymer with flexible bis(1,2,4-triazol-4-yl)ethane

“…Recently, we reported a series of transition metal coordination polymers with the flexible ligand 1,2-bis (1,2,4-triazol-1-yl)ethane (bte) [9]. The ligand 1,2-bis(1,2,4-triazol-4-yl)ethane (btre) is an isomer of 1,2-bis(1,2,4-triazol-1-yl)ethane (bte) but is not well studied [8] and no Ag-btre complex was synthesized up to now. In the present work, we report a new three-dimensional network silver coordination polymer {[Ag(btre)](ClO 4 )} n (1) with the self-assembly reaction of the flexible ligand 1,2-bis(1,2,4-triazol-4-yl) ethane (btre) and AgClO 4 .…”

“…On the other hand, a large number of mononuclear, oligonuclear, and polynuclear transition metal complexes of 1-and 4-substituted 1,2,4-triazole derivatives have been synthesized and characterized because of their unique properties and novel topologies [5][6][7][8]. Few silver coordination polymers with flexible 1-substituted 1,2,4-triazole ligands bis (1,2,4-triazol-1-yl)methane (btm) [6] and 1,2-bis(1,2,4-triazol-1-yl)ethane (bte) [7] were synthesized and structurally characterized.…”