Structural relationships between new carbide La14Sn(MnC6)3 and fully ordered La11(MnC6)3

Crystals of the ternary La{sub 11}(MnC{sub 6}){sub 3} and new quaternary carbide La{sub 14}Sn(MnC{sub 6}){sub 3} phases were grown from La/Ni eutectic flux and their structures were determined by means of X-ray single crystal diffraction. La{sub 11}(MnC{sub 6}){sub 3} is a new superstructure variant of La{sub 3.67}MnC{sub 6} (previously reported disordered subcell: P6{sub 3}/m; a{sub 0}=8.806 A; c{sub 0}=5.329 A, Z=2). The superstructure (R3-bar ; a={radical}3a{sub 0}=15.2649(9) A; c=3c{sub 0}=16.013(1) A, Z=6; R{sub 1}=0.022) is realized by complete ordering of the La chains within the columns of face-sharing carbon octahedra, with alternating La-La distances leading to R-centering and enlargement of the unit cell. The structure of the quaternary carbide La{sub 14}Sn(MnC{sub 6}){sub 3} (P6-bar ; a=8.756(1) A; c=10.483(2) A, Z=1; R{sub 1}=0.026) is closely related to that of La{sub 11}(MnC{sub 6}){sub 3} with part of the MnC{sub 6} units replaced by Sn atoms. The structure and precise composition of La{sub 14}Sn(MnC{sub 6}){sub 3} can be derived from that of La{sub 11}(MnC{sub 6}){sub 3} by taking into account the extent of this substitution and variation in lanthanum siting in the chain of carbon octahedra. Band structure calculations indicate both phases are metallic; the La{sub 11}(MnC{sub 6}){sub 3} phase is stabilized bymore » the ordering of La atoms which induces a pseudogap at E{sub F}. -- La{sub 11}(MnC{sub 6}){sub 3} with fully ordered superstructure and a new carbide La{sub 14}Sn(MnC{sub 6}){sub 3} were obtained from La/Ni eutectic flux. Display Omitted« less