New members in the Nin+1(QO3)nX2 family:: Unusual 3D network based on Ni4ClO3 cubane-like clusters in Ni7(TeO3)6Cl2

Three new members in the family of nickel(II) tellurium(IV)/selenium(IV) oxyhalides generally formulated as Nin+1-(QO(3))(n)X-2 (Q = Te, X = Cl, n = 6, 10; Q = Se, X = Br, n = 4) have been synthesized by solid-state reactions of NiX2, QO(2), and NiO (or Ni2O3) at high temperature. The structure of Ni-7(TeO3)(6)Cl-2 features a novel 3D network based on Ni4ClO3 cubane-like clusters with Te atoms located at the cavities of the network. Ni4ClO3 clusters are interconnected into a hexagonal layer through additional O center dot center dot center dot O edges. The neighboring two layers are further interconnected, via sharing of common Ni(II) atoms, into a novel 3D network. The 3D open framework of Ni-5(SeO3)(4)-Br-2 is built from 2D nickel(II) oxybromide layers bridged by Se and additional Ni atoms. The structure of Ni-11(TeO3)(10)-Cl-2 features a condensed 3D network based on NiO5Cl, NiO6, and NiO5 polyhedra interconnected via corner and edge sharing, as well as O-Te-O bridges. The results of magnetic property measurements indicate that all three compounds display antiferromagnetic interactions between nickel(II) centers.