Structural studies on single crystals of Chevrel phase selenides REMo6Se8 (RE = La, Ce, Pr, Nd, or Sm) at 298 K

We report on structural studies at room temperature of rare-earth based Che vrel phase selenides of the formula RExMo6Se8, where RE stands for a light rare-earth La (1), Ce (2), Pr (3), Nd (4), or Sm (5). The single crystals w ere grown at 1650 degrees C < T < 1690 degrees C from off-stoichiometric st arting compositions, with the exception of 3, which was grown at 1710 degre es C from a stoichiometric charge (congruently melting material). The cryst al structures were solved in space group R (3) over bar (No. 148; Z = 1) an d found to be isostructural with the well-known Chevrel phases having large cations (e.g., PbMo6S8, REMo6S8). The structures are based on Mo6Se8 metal lic clusters that are slightly rotated inside a pseudocubic rare-earth subl attice. Structural refinements revealed that the origin site, occupied by t he RE atoms, exhibits slight deficiencies, leading to a RExMo6Se8 compositi on, with x ranging between similar to 0.82 and similar to 0.92: 1 La0.88Mo6 Se8, a(rh) = 6.7577(9) Angstrom, alpha(rh) = 88.62(2)degrees; 2a Ce0.82Mo6S e8, a(rh) = 6.7407-(6) Angstrom, alpha(rh) = 88.83(2)degrees; 2b Ce0.92Mo6S e8, a(rh)= 6.7473(9) Angstrom, alpha(rh) = 88.69(2)degrees; 3 Pr0.86Mo6Se8, a(rh) = 6.7385(6) Angstrom, alpha(rh) = 88.81(2)degrees; 4 Nd0.85Mo6Se8, a (rh) = 6.7286(5) Angstrom, alpha rh = 88.85(1)degrees; and 5 Sm0.87Mo6Se8, a(rh) = 6.7182(2) Angstrom, alpha(rh) = 88.956(3)degrees. All of the struct ural data presented in this work (lattice constants, positional parameters and interatomic distances) concern an average RE content of x approximate t o 0.87. In this way, any influence due to electronic effects (VEC number) c an be discarded, and exact correlations between these parameters and the io nic radius of the rare-earth atoms can then be established.