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In a combined synthetic, X-ray single-crystal and bond-theoretical study the phase widths of SrIn 4  and the related Sr 3 In 11  upon a sucessive substitution of indium against the more electronpoor, more electronegative and only slightly smaller element mercury have been studied. Along the 1 : 4 section Sr(In 1-x Hg x ) 4  the monoclinic structure of SrIn 4  ( EuIn 4 -type structure) is stable up to x =0.14(1) ( SrIn 3.44 Hg 0.56 : monoclinic, C2/m, a = 1208.3(6), b = 502:5(2), c = 997.7(6) pm, b = 115.16(3)°, Z = 4, R1 = 0.0324). Further increased mercury content results in a distinct stability region of the very common BaAl 4  structure type (tetragonal, I4=mmm, Z = 2), which starts at x =0.241(7) ( SrIn 3.04 Hg 0.96 : a = 4694(2), c = 1246.4(7) pm, R1 = 0.0374) and reaches up to the fully ordered compound SrIn 2 Hg 2  (x =0.5: a = 456.4(3), c = 1273.5(11) pm, R1 = 0.0572). Unexpectedly, in the small composition range from x=0.68(1) to 0.758(6) ( SrIn 1.16 Hg 2.84 : a=1178.5(4), b = 495.20(12), c = 1016.8(4) pm, b = 119.67(2)°, R1 = 0.0542; SrIn 0.97 Hg 3.03 : a = 1167.30(4), b = 495.32(2), c = 1018.50(3) pm, b = 119.657(2)°, R1 = 0.0426) the EuIn 4  structure type exhibits a further small stability range. The structures of the two slightly different In- and Hg-rich variants of the EuIn 4  type are described and compared, indicating the similarities to the KHg 2  (layers of folded In=Hg ladders) and the BaAl 4  structure type (flat square pyramids) as well as to the structure of elemental mercury (rhombohedra). From samples of an intermediate In=Hg ratio (e. g. x =0.55), the new 1 : 3 compound SrIn 1.2 Hg 1.8  (monoclinic, C2=m, a = 1168.5(13), b = 497.0(4), c = 1471(2) pm, b = 92.07(10)°, Z = 8, R1 = 0.0818) is formed. It crystallizes in a new structure type, which - according to the compound’s composition - can be described as a stacking variant of the EuIn 4  and the KHg 2  structure type. In contrast to the wide stability ranges of the 1 : 4 compounds, only a very small substitution of In ranging up to only 6% of Hg is possible in the binary indide Sr 3 In 11  ( Sr 3 In 10.32 (8)Hg 0.68 (8): La 3 Al 11  structure type, orthorhombic, Immm, a = 487 : 6(2), b = 1140.2(5), c = 1421.1(7) pm, Z = 2, R1 = 0.0703). The formation, stability ranges and the In=Hg ‘coloring’ of the polyanions are discussed for all compounds taking into account geometric (radius ratios, molar volumes, Sr coordination polyhedra etc.) and electronic aspects, which have been evaluated using FP-LAPW band structure calculations.

Strontium-Metallide im Bereich des Schnitts SrIn 4 – SrHg 4 / Strontium Metallides along the Section SrIn 4 – SrHg 4