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Two New μ‐(1,3‐Azido)‐Bridged Polymers: Alternating Single and Double Bridges in a 1D Nickel( II ) Complex and Uniform Bridge in a 2D Copper( II ) Complex: Syntheses, Single‐Crystal Structures and Magnetic Studies
Author(s) -
Manna Subal Chandra,
Konar Sanjit,
Zangrando Ennio,
Drew Michael G. B.,
Ribas Joan,
Ray Chaudhuri Nirmalendu
Publication year - 2005
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200400930
Subject(s) - chemistry , triclinic crystal system , crystallography , orthorhombic crystal system , nickel , perchlorate , crystal structure , stereochemistry , copper , magnetic susceptibility , ion , organic chemistry
Two polymeric azido bridged complexes [Ni 2 L 2 (N 3 ) 3 ] n (ClO 4 ) n ( 1 ) and [Cu(bpds) 2 (N 3 )] n (ClO 4 ) n (H 2 O) 2.5 n ( 2 ) [L = Schiff base, obtained from the condensation of pyridine‐2‐aldehyde with N , N ,2,2‐tetramethyl‐1,3‐propanediamine; bpds = 4,4'‐bipyridyl disulfide] have been synthesized and their crystal structures have been determined. Complex 1 , C 26 H 42 ClN 15 Ni 2 O 4 , crystallizes in a triclinic system, space group P $\tilde {1}$ with a = 8.089(13), b = 9.392(14), c = 12.267(18) Å, α = 107.28(1), β = 95.95(1), γ = 96.92(1)° and Z = 2; complex 2 , C 20 H 21 ClCuN 7 O 6.5 S 4 , crystallizes in an orthorhombic system, space group Pnna with a = 10.839(14), b = 13.208(17), c = 19.75(2) Å and Z = 4. The crystal structure of 1 consists of 1D polymers of nickel(L) units, alternatively connected by single and double bridging μ‐(1,3‐N 3 ) ligand with isolated perchlorate anions. Variable temperature magnetic susceptibility data of the complex have been measured and the fitting of magnetic data was carried out applying the Borrás‐Almenar formula for such types of alternating one‐dimensional S = 1 systems, based on the Hamiltonian H = – J Σ( S 2 i S 2 i –1 + α S 2 i S 2 i +1 ). The best‐fit parameters obtained are J =–106.7 ± 2 cm –1 ; α = 0.82 ± 0.02; g = 2.21 ± 0.02. Complex 2 is a 2D network of 4,4 topology with the nodes occupied by the Cu II ions, and the edges formed by single azide and double bpds connectors. The perchlorate anions are located between pairs of bpds. The magnetic data have been fitted considering the complex as a pseudo‐one‐dimensional system, with all copper( II ) atoms linked by μ(1,3‐azido) bridging ligands at axial positions (long Cu ··· N 3 distances) since the coupling through long bpds is almost nil. The best‐fit parameters obtained with this model are J = –1.21 ± 0.2 cm –1 , g = 2.14 ± 0.02. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)