A new modification of CuTi(2)S(4) was prepared from the elements at 425 degrees C. It crystallizes in the rhombohedral space group Rm, with lattice parameters of a = 7.0242(4) A, c = 34.834(4) A, and V = 1488.4(2) A(3) (Z = 12). Two topologically different interlayer regions exist between the close-packed S layers that alternate along the c axis: one comprises both Cu (in tetrahedral voids) and Ti atoms (in octahedral voids), and the second exclusively Ti atoms (again in octahedral voids). In contrast to the known modification, the spinel, Cu-Ti interactions of 2.88 A occur that have bonding character according to the electronic structure calculations. Both CuTi(2)S(4) modifications are metallic Pauli paramagnets due to Ti d contributions. The Pauli susceptibility of the Rm form is larger than that of the thiospinel in quantitative agreement with the LMTO-ASA band structure calculations. The irreversible transformation to the spinel takes place at temperatures above 450 degrees C.
A ternary sulfide exists on the quasi-binary section La 2 S 3 -Sb 2 S 3 , La 7+δ Sb 9-δ S 24 . This material exhibits a small but significant phase range with at least -0.296(4) e δ e 0.134(6). La 7+δ Sb 9-δ S 24 forms a new structure type, space group P2 1 /c, with a ) 8.7115(9) Å, b ) 14.3450(15) Å, c ) 15.2657(16) Å, β ) 90.105(2)°(Z ) 2) for δ ) 0.13. This structure contains chains of severely distorted SbS 5 square antiprisms, interconnected by eight-and nine-coordination La atoms. One position is mixed-occupied by La and Sb, with the La content ranging at least from 57% to 35%. La 7 Sb 9 S 24 is a blackish material with a computed gap >1.5 eV.
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