Direct Synthesis and Characterization of New Copper(II) and Zinc(II) 5‐R‐Tetrazolato Complexes [R = Me, Ph, 4‐Py] with Ethylenediamine and DMSO as Coligands

Abstract

AbstractThree novel 5‐R‐tetrazolato complexes (R = Me, Ph, 4‐Py), namely [Zn2(MeCN4)4(DMSO)2] (1), [Cu2(PhCN4)4(en)2]·2DMSO (2), and [Cu(4‐PyCN4)2(DMSO)2]·4DMSO (3), were isolated as unexpected products under attempts to prepare heterometallic tetrazolates using a direct synthesis strategy in the Cu0‐ZnO‐en‐RCN4H‐DMSO system (en = ethylenediamine). The prepared compounds were characterized by elemental, single‐crystal X‐ray, and thermal analyses, and IR spectroscopy. Variation of the 5‐substituent of the tetrazole ring causes different composition of complexes 1–3 and diverse coordination modes of 5‐R‐tetrazolato ligands. Complex 1 is a 3D coordination polymer due to N1, N4‐bridging of 5‐methyltetrazolato anions. Complex 2, with en as a coligand, has a dinuclear structure with two copper atoms linked together by two 5‐phenyltetrazolato ligands by tetrazole N2, N3 bridges. Complex 3 represents a 2D coordination polymer, formed due to 5‐(4‐pyridyl)tetrazolato bridges between adjacent copper atoms (with the tetrazole and pyridine rings nitrogen atoms as coordination centers). DMSO molecules, included in all the compounds, are solvate and/or coordinated ones.