A comparative study of the crystal structures of Ba(ClO₃)₂, Ba(BrO₃)₂ II, Pb(ClO₃)₂, and Sr(ClO₃)₂

Abstract

The crystal structures of the isotypic orthorhombic alkaline earth and lead halates Ba(C10 3 ) 2 , Ba(Br0 3 ) 2 II, and Pb(C10 3 ) 2 [Sr(C10 3 ) 2 -type, oFll, Fddl, Ζ = 8] were determined by single crystal X-ray diffraction data.The final R values (number of observed unique reflections) are 0.033(854), 0.067(853), and 0.051(720). The data obtained are compared with those of Sr(C10 3 ) 2 and discussed in terms of metal oxygen coordination and distortion of the halate ions, respectively. A stereochemical effect of the lone-pair of the lead ion is not observed. Brought to you by | University of California Authenticated Download Date | 6/9/15 1:32 PM P-00 © © η <N O © Ö © © I SrBcS m C* ·<-

Discovery of excellent ultraviolet nonlinear optical materials in chlorates and bromates with highly stereochemically active lone pairs

“…2c). 49 The stereochemical activity of the Pb 2+ -6s 2 lone pairs is not obvious because the eight Pb–O bond lengths are relatively close, but this remains to be verified by electron localization function analysis. BiO(BrO 3 ) crystallizes in the polar space group Pca 2 1 (No.…”

“…Rigorous screening yields 15 cases of simple noncentrosymmetric chlorates and bromates, including AClO 3 (A = NH 4 , K, Rb, Cs, Tl), M(ClO 3 ) 2 (M = Sr, Ba, Pb), ABrO 3 (A = K, Rb, Cs, Tl), M(BrO 3 ) 2 (M = Sr, Ba) and BiO(BrO 3 ). 24,25,[45][46][47][48][49][50] We have performed the structural optimization on them, and the structural rationality is proved by the suitable bond valence sum of 4.8-5.2 for Cl 5+ /Br 5+ in ClO 3 /BrO 3 groups. They are all in the polar crystal symmetries and most of them with similar chemical formula are isostructural and the crystal structures resemble one another.…”

“…43). 48,49 They are all characterized by distorted triangular pyramidal ClO 3 /BrO 3 and ionically bonded dodecahedral MO 8 .…”