Extended networks, porous sheets, and chiral frameworks. Thorium materials containing mixed geometry anions: Structures and properties of Th(SeO3)(SeO4), Th(IO3)2(SeO4)(H2O)3·H2O, and Th(CrO4)(IO3)2

Three novel Th(IV) compounds containing heavy oxoanions, Th(SeO3)(SeO4) (1), Th(IO3)2(SeO4)(H2O)3·H2O (2), and Th(CrO4)(IO3)2 (3), have been synthesized under mild hydrothermal conditions. Each of these three distinct structures contain trigonal pyramidal and tetrahedral oxoanions. Compound 1 adopts a three-dimensional structure formed from ThO9 tricapped trigonal prisms, trigonal pyramidal selenite, SeO32–, anions containing Se(IV), and tetrahedral selenate, SeO42–, anions containing Se(VI). The structure of 2 contains two-dimensional porous sheets and occluded water molecules. The Th centers are found as isolated ThO9 tricapped trigonal prisms and are bound by four trigonal pyramidal iodate anions, two tetrahedral selenate anions, and three coordinating water molecules. In the structure of 3, the Th(IV) cations are found as ThO9 tricapped trigonal prisms. Each Th center is bound by six IO31– anions and three CrO42– anions forming a chiral three-dimensional structure. Second-harmonic generation of 532 nm light from 1064 nm radiation by a polycrystalline sample of 3 was observed. Crystallographic data (193 K, MoKα, image): 1; monoclinic, P21/c; image, image, image, image, image, image for 91 parameters with 1462 reflections with image; 2, monoclinic, P21/n, image, image, image, image, image, image for 158 parameters with 2934 reflections with image; 3, orthorhombic, P212121, image, image, image, image, image for 129 parameters with 2035 reflections with image.