pH Controlled Pathway and Systematic Hydrothermal Phase Diagram for Elaboration of Synthetic Lead Nickel Selenites

The PbO–NiO–SeO2 ternary system was fully
studied using constant hydrothermal conditions at 473 K. It yields
the establishment of the corresponding phase diagram using a systematic
assignment of reaction products by both powder and single-crystal
X-ray diffraction. It leads to the preparation of three novel lead
nickel selenites, α-PbNi­(SeO3)2 (I), β-PbNi­(SeO3)2 (II), and PbNi2(SeO2OH)2(SeO3)2 (III), and one novel lead cobalt selenite,
α-PbCo­(SeO3)2 (IV), which
have been structurally characterized. The crystal structures of the
α-forms I, IV, and III are based on a 3D complex nickel selenite frameworks, whereas the
β-PbNi­(SeO3)2 modification (II) consists of nickel selenite sheets stacked in a noncentrosymmetric
structure, second-harmonic generation active. The pH value of the
starting solution was shown to play an essential role in the reactive
processes. Magnetic measurements of I, III, and IV are discussed.