A New Modification of Tellurite Phosphate: β-Te_3O_3(PO_4)_2

A new modification of tellurite phosphate, β-Te_3O_3(PO_4)_2, has been synthesized under hydrothermal conditions and its crystal structure was determined by single-crystal X-ray diffraction. It crystallizes in the monoclinic space group P2_1/n(No. 14), with a = 11.115(5), b = 4.7033(19), c = 17.287(7) ?, β = 106.086(5)°, V = 868.3(6) ?~3, Z = 4, P_2 Te_3 O_(11), M_r = 620.74, D_c = 4.748 g/cm~3, μ(Mo Kα) = 10.438 mm~(–1) and F(000) = 1096. The final full-matrix least-squares refinement converged to R = 0.0227, wR = 0.0534 for 1984 observed reflections with I 2σ(I), and R = 0.0240, w R = 0.0540 for all data(2070) and S = 1.117. β-Te_3O_3(PO_4)_2 is polymorphic with the known α-Te_3O_3(PO_4)_2(Weil H. M. et al. Z. Anorg. Allg. Chem. 2003, 629, 1068-1072). The crystal structure of β-Te_3O_3(PO_4)_2 features a three-dimensional(3D) network composed of Te_6 O_(22)~(20)-hexanuclear clusters interconnected by PO_4 groups. Te_6 O_(22) hexanuclear cluster is built from three Te_2 O_8 dimers(edge-sharing TeO_5 square pyramids) linked to each via sharing O-corners. The structure difference between α-and β-forms of Te_3O_3(PO_4)_2 lies in the polymerization of tellurite oxides Te_nO_m. 1D infinite ~1_∞{Te_3 O_(11)]~(10-)} single chains are presented in α-Te_3O_3(PO_4)_2, while 0D discrete Te_6 O_(22) hexanuclear clusters are observed for β-Te_3O_3(PO_4)_2. Moreover, thermal analyses, infrared spectra and UV-Vis-NIR diffuse reflectance are also presented.