The reaction of 2-(2H-tetrazol-5-yl)pyridine (L1) with 1,6-dibromohexane results in formation of the isomers 2-(6′′-bromohexyl-(1-tetrazol-5-yl)pyridine (L2) and 2-(6′′-bromohexyl-(2-tetrazol-5-yl)pyridine (L3 compounds. X-ray crystal structures were obtained for complexes 1-5. In each complex, ligands L2 and L3 coordinate to the metal centre through the pyridyl N atom and the 1-N site of the tetrazole ring, and the pyridyl-tetrazole ligand remains planar in all cases except 3. Complexes 1 and 2 comprise a central Cu 2 Cl 2 dimeric core with Cu(II) in an essentially square-pyramidal coordination environment. Complexes 3 and 4 contain Co(II) in a distorted octahedral coordination environment.In 3, the pyridyl and tetrazole rings of L2 are twisted with respect to each other and the complex adopts a puckered conformation in its equatorial plane. Complex 5 contains water molecules coordinated to Fe(II) in the axial sites, which form hydrogen bonds to the perchlorate counter anions.3

This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. AbstractThe coordination of pyridyl-tetrazole derivatives containing ester substituents, at either the N-1 or N-2 position of the tetrazole ring, with copper(II) chloride results in the formation of either 1:1 or 1:2 copper to ligand complexes, depending on the ligand. However, when the ester functionality is changed to a carboxylate group, the resulting complexation reactions yield metal-organic frameworks. The resulting structures vary dramatically in pore size, depending on both reaction solvents and position of carboxylate group on the tetrazole ring.Despite the presence of sodium cations in the reaction mixtures, no sodium incorporation was ever observed in any of the complexes. This report represents the first attempts at producing copper(II) complexes of the N-1 and N-2 carboxylate derivative of this ligand.

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a b s t r a c tThe reaction of 2-(2H-tetrazol-5-yl)pyridine (L1) with 1,n-dibromoalkane (n = 3, 4, 6 or 8) results in the formation of the isomers 2-(n 00 -bromoalkyl-(1-tetrazol-5-yl)pyridine (L2A-D) and 2-(n 00 -bromoalkyl-(2-tetrazol-5-yl)pyridine (L3A-D). The reaction of L1 with 1-bromoalkanes also resulted in the formation of isomeric materials, namely 2-(n 00 -alkyl-(1-tetrazol-5-yl)pyridine (L4A-C) and 2-(n 00 -alkyl-(2-tetrazol-5-yl)pyridine (L5A-C). Complexation reactions of these ligands with the transition metal salts CuCl 2 Á2H 2-O, Co(NCS) 2 , NiCl 2 Á2H 2 O and ZnCl 2 were carried out in methanol and resulted in complexes containing a 1:1 metal:ligand stoichiometry except in the cases of the cobalt complexes where a 1:2 metal:ligand stoichiometry was obtained. The 1 H NMR spectra of the zinc complexes showed that the ligands containing the pendant arm in the 2-N position of the tetrazole ring bind the zinc ion more strongly than those containing the pendant arm in the 1-N position. The X-ray structures of two cobalt salts, Co(L5A) 2 (NCS) 2 and Co(L5C) 2 (NCS) 2 , are also discussed.