New rare earth metal-rich indides RE14Ni3In3 (RE = Sc, Y, Gd-Tm, Lu) - synthesis and crystal chemistry

摘要

The rare earth-nickel-indides RE14Ni3In3 (RE = Sc, Y, Gd-Tm, Lu) were synthesized from the elements by arc-melting and subsequent annealing. The compounds were investigated on the basis of X-ray powder and single crystal data: Lu14CO2In3 type, P4(2)/ nmc, Z = 4, a = 888.1(1), c = 2134.7(4), wR2 = 0.0653, 1381 F-2 values, 63 variables for Sc13.89Ni3.66In2.45; a = 961.2(1), c = 2316.2(5), wR2 = 0.0633, 1741 F-2 values, 64 variables for Y13.84Ni3.19In2.97; a = 965.3(1), c = 2330.5(5), wR2 = 0.0620, 1765 F-2 values, 63 variables for Gd14Ni3.29In2.71; a = 956.8(1), c = 2298.4(5), wR2 = 0.0829, 1707 F-2 values, 64 variables for Tb13.82Ni3.36In2.82; a = 951.7(1), c = 2289.0(5), wR2 = 0.0838, 1794 F-2 values, 64 variables for Dy13.60Ni3.34In3.06; a = 948.53(7), c = 2270.6(1), wR2 = 0.1137, 1191 F-2 values, 64 variables for Ho13.35N6.17In3.48; a = 943.5(1), c = 2269.1(5), wR2 = 0.0552, 1646 F-2 values, 64 variables for Er13.53Ni3.14In3.33; a = 938.42(7), c = 2250.8(1), wR2 = 0. 1051, 1611 F-2 values, 64 variables for Tm13.47Ni3.28IIn3.25; a = 937.3(1), c = 2249.6(5), wR2 = 0.0692, 1604 F-2 values, 64 variables for Tm13.80Ni3.49In2.71; and a = 933.4(1), c = 2263.0(5), wR2 = 0.0709, 1603 F-2 values, 64 variables for Lu13.94Ni3.07In2.99. The RE14Ni3In3 indides show significant Ni/In mixing on the 4c In1 site. Except the gadolinium compound, the RE14Ni3In3 intermetallics also reveal RE/In mixing on the 4c REI site, leading to the refined compositions. Due to the high rare earth metal content, the seven crystallographically independent RE sites have between 9 and 10 nearest RE neighbors. The RE14Ni3In3 structures can be described as a complex intergrowth of rare earth-based polyhedra. Both nickel sites have a distorted trigonal-prismatic rare earth coordination. An interesting feature is the In2-In2 dumb-bell at an In2-In2 distance of 304 pm (for Gd14Ni3.29In2.71). The crystal chemical peculiarities of the RE14Ni3In3 indides are briefly discussed. (c) 2005 Elsevier Inc. All rights reserved.