Synthesis and crystal structure of triytterbium chloroorthosilicate, Yb3(SiO4)2Cl

Abstract

Crystals of a new lanthanide orthosilicate, Yb3(Si04)2Cl, were prepared by vapor transport in a chlorine atmosphere. A complete single-crystal structural analysis showed that the crystal class is orthorhombic, a = 6.731 (2), b = 17.556 (8), c = 6.129 (2) A.With 4 formula units in space group Pnma the calculated density is 6.77 g cm'3. A full-matrix leastsquares structure factor refinement effected with the 460 observed reflections collected by the -scan procedure and anisotropic thermal parameters for the Yb atoms gave R = 3.0% and Rw = 2.2%. The ytterbium atoms are in two sites and are eight-coordinated as Yb06Cl2 square antiprisms and as Yb07Cl dodecahedra that can also be described as Yb-(Si04)5Cl octahedra. The presence of the chlorine atoms causes some long Yb-0 bonds. ri$-Tetracarbonyldiphosphinechromium(0) far side of the Yb(l)-(Si04)4 plane. The shortest 0(2)-Cl distance is 3.165 A. Only the 0(5) oxygen atoms are completely separated from the chlorines; one of these gives the shortest Yb-0 bond: Yb(l)-0(1)5,2.19 A.

Inorganic Lanthanide Compounds with Complex Anions

“…Halide ortho -silicates of the rare-earth elements are mainly known with Cl - as the halide component. Those with the composition M 3 Cl(SiO 4 ) 2 crystallize either in a monoclinic (A-type) or an orthorhombic (B-type) modification. − The A-type occurs with the larger M 3+ ions and the B-type with the smaller ones (cf. Table ).…”

Synthese und Kristallstrukturen von Bromid—Thiosilicaten Ln3Br[SiS4]2 der Lanthanide (Ln = La, Ce, Pr, Nd, Sm, Gd)

“…Sie gehören dem von Gravereau et al 1988 beschriebenen Strukturtyp der LanthanidϪHalogenidϪ Oxosilicate [3] (AϪTyp) an. Das (2) (7) 98 (8) 74 (7) Ϫ2 (6) 14 (6) Ϫ2(6) S1 133 (7) 85 (7) 137 (7) 34 (6) 38 (6) 29 (6) S2 99 (7) 116 (7) 85 (7) 11 (6) Ϫ5 (5) Ϫ16 (6) S3 85 (7) 111 (7) 155 (7) Ϫ25(6) 0(6) 10(6) S4 107 (7) 125 (7) 86 (7) Ϫ16 (6) 12 (5) 4 ϪTetraeder kaum Änderungen in den Bindungslängen und Ϫwinkeln. Die Pr1ϪSϪAbstände unterscheiden sich wenig, so beträgt die maximale Abweichung für die Abstände Pr1ϪS1 d und Pr1ϪS3 a 7 pm.…”

The non-isotypic pair CsCe[SiS4] and CsCe[SiSe4]: A structural comparison

“…In these cases, compounds such as M 3 Cl[SiO 4 ] 2 (two types) [2][3][4][5][6], M 3 Cl 3 [Si 2 O 7 ] [3,7], M 3 Cl 5 [SiO 4 ] (two types) [3,6,[8][9][10], and M 6 Cl 10 [Si 4 O 12 ] [6,[11][12][13] serve as prominent examples. The expansion of this class of compounds from the oxo-ligand to the heavier chalcogens (Ch = S, Se) provides additional changes.…”

“…Due to the commercial unavailability of SiSe 2 , the above-mentioned route to synthesize the selenosilicate CsCe[SiSe 4 ] is not possible. Instead, the reaction of cerium metal (Ce: 99.9%; ChemPur, Karlsruhe, Germany), elemental selenium (Se: 99.999%; ChemPur, Karlsruhe, Germany) and silicon (Si: 99.999%; Roth, Karlsruhe, Germany) with an excess of cesium chloride (CsCl: 99.9%; ChemPur, Karlsruhe, Germany) according to 4 Ce + 3 Si + 12 Se + 3 CsCl → 3 CsCe[SiSe 4 ] + CeCl 3 in evacuated silica ampoules for 7 days at 850 • C yields yellow, platelet-shaped single crystals of CsCe[SiSe 4 ]. Unlike the thiosilicate, the selenosilicate undergoes complete hydrolysis, so the bulk material was protected with paraffin in order to obtain suitable crystals for single crystal X-ray diffraction experiments (Tables 1-3).…”