Divalent metal 1,3-phenylenediacetate coordination polymers with rigid or flexible dipyridyl tethers: Chains, layers, and interpenetrated networks

Abstract

Hydrothermal synthesis has afforded four divalent metal 1,3-phenylenediacetate (1,3-phda) coordination polymers containing different dipyridyl-type ligands. {[Cu(1,3-phda)(dpa)(H 2O)]·H 2O} n ( 1, dpa = 4,4′-dipyridylamine) exhibits a simple 2-D (4,4) rhomboid grid structure. {[Co(1,3-phda)(bpy)]·1.5H 2O} n ( 2, bpy = 4,4′-bipyridine) also possesses a (4,4) layer structure, but with syn– syn bridged {Co 2(OCO) 2} dimeric kernels serving as 4-connected nodes. {[Co(H 2O) 4(3-bpmpH 2)](1,3-phda) 2·8H 2O} n ( 3, 3-bpmp = bis(3-pyridylmethyl)piperazine) manifests cationic 1-D [Co(H 2O) 4(3-bpmpH 2)] n 4 n + chains linked into higher dimensionality by unligated 1,3-phda anions and curled tetrameric water molecule units. {[Ni(1,3-phda)(4-bpmp)(H 2O) 2]·2H 2O} n ( 4, 4-bpmp = bis(4-pyridylmethyl)piperazine) has an underlying twofold interpenetrated 6 58 ( cds) 3-D network topology. Variable temperature magnetic susceptibility studies revealed the presence of weak antiferromagnetic coupling and zero-field splitting ( J = −1.65(4) cm −1 and D = 30.9(7) cm −1 with g = 2.20(1)) within the {Co 2(OCO) 2} dimers in 2.