New intermetallic indium compounds EuAuIn2, EuPdIn4, GdRhIn2, YbRhln4, and YbPdIn4 were obtained by reaction of the elements. GdRhIn2 was synthesized in an arc-melting furnace, while EuAuIn2, EuPdln4, YbRhIn4, and YbPdIn4 were prepared in sealed tantalum tubes in a high-frequency furnace. The five compounds were investigated by X-ray diffraction both on powders and single crystals. EuAuIn2 and GdRhIn2 adopt the MgCuAl2 type structure with space group Cmcm. Single crystal X-ray data yielded a = 468.1(2), b = 1105.5(4), c = 753.5(4) pm, wR2 = 0.096, 343 F2 values for EuAuIn2 and a = 435.0(1), b = 1013.3(3), c = 783.6(2) pm, wR2 = 0.042, 608 F2 values for GdRhIn2 with 16 variables for each refinement. The two structures may be described as gold or rhodium filled versions of the host lattices Euln2 and GdIn2 . The three-dimensional indium networks of EuAuIn2 and GdRhIn2 resemble the lonsdaleite structure. Both structures are built up from three-dimensional [Auln2] and [Rhln2] poly anions in which the europium and gadolinium atoms occupy distorted hexagonal tubes. The modulations of the In-In distances within the indium networks are compared with other MgCuAl2 type indides. EuPdIn4 and YbPdIn4 crystallize with the YNiAl4 type, space group Cmcm: a = 454.8(2), b = 1703.2(8), c = 738.0(3) pm, wR2 = 0.044, 501 F2 values for EuPdIn4 and a = 445.8(2), b = 1666.0(4), c = 747.3(2) pm, wR2 = 0.050, 711 F2 values for YbPdIn4 with 24 variables for each refinement. In contrast, YbRhln4 adopts the LaCoAl4 type, space group Pmma: a = 863.7(2), b = 422.5(1), c = 743.1(1) pm, wR2 = 0.051, 467 F2 values and 24 variables. EuPdIn4, YbPdlIn4, and YbRhIn4 too consist of three-dimensional [Pdln4] and [Rhln4] polyanions in which the europium and ytterbium atoms are located in distorted hexagonal and pentagonal channels. Common structural motifs of these indides are distorted bcc-like indium cubes which are compared with the structures of Y2CoIn8, YCoIn5, EuRh2ln8, and elemental indium. Chemical bonding in these indides is briefly discussed
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Hoffmann et al. (2000) studied this question.
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