New members of the A2M′M2″ structure family (A =Ca, Sr, Yb, La; M′=In,Sn,PbM′=In,Sn,Pb; M″=Si,GeM″=Si,Ge)

•Mixed metallides A2(In/Sn/Pb)(Si/Ge)2 were prepared for A=Ca, Sr, Yb, La.•The structures exhibit planar Si/Ge zig-zag chain segments of variable lengths.•In, Sn and Pb atoms are connecting the Si/Ge anions to planar nets.•Atomic size effects are investigated by the synthesis of mixed Ca/Sr germanides.•Bandstructure calculations indicate Si/Ge–Si/Ge π bonding contributions.

The new mixed tetrelides Sr2PbGe2Sr2PbGe2 and Yb2SnGe2Yb2SnGe2, several mixed Ca/Sr (AII) germanides A2II(Sn,Pb)Ge2 and two polymorphs of La2InSi2La2InSi2 represent new members of the general structure family of ternary alkaline-earth/lanthanoid main group silicides/germanides A2M′M2″(M′=In,Sn,Pb;M″=Si,Ge). All compounds were synthesized from melts of the elements and their crystal structures have been determined by means of single crystal X-ray diffraction. Sr2PbGe2Sr2PbGe2 (Cmmm, a=402.36(11), b=1542.3(4), c  =463.27(10) pm) crystallizes with the Mn2AlB2-typeMn2AlB2-type structure. In exhibiting infinite planar Ge zig-zag chains, it represents one border of the compound series. The other borderline case, where only [Ge2][Ge2] dumbbells are left as Ge building units, is represented by the Ca/Yb tin germanides Ca2SnGe2Ca2SnGe2 and Yb2SnGe2Yb2SnGe2 (Mo2FeB2-typeMo2FeB2-type; P4/mbm, a=748.58(13)/740.27(7), c=445.59(8)/435.26(5) pm). In between these two border structures compounds with variable Si/Ge chain lengths could be obtained by varying the averaged size of the AII cations: Ca0.45Sr1.55PbGe2Ca0.45Sr1.55PbGe2 (new structure type; Pbam, a=791.64(5), b=2311.2(2), c  =458.53(3) pm) contains planar six-membered chain segments [Ge6][Ge6]. Tetrameric pieces [Ge4][Ge4] are the conspicuous structure elements in Ca1.16Sr0.84SnGe2Ca1.16Sr0.84SnGe2 and La2InSi2La2InSi2 (La2InNi2-typeLa2InNi2-type; Pbam, a=781.01(2)/762.01(13), b=1477.95(3)/1494.38(6), c  =457.004(9)/442.1(3) pm). The tetragonal form of ’La2InSi2′ (exact composition: La2In1.07Si1.93La2In1.07Si1.93, P4/mbm, a=1309.11(12), c  =443.32(4) pm) also crystallizes in a new structure type, containing only [Si3][Si3] trimers as cutouts of the planar chains. In all structures the Si/Ge zig-zag chains/chain segments are connected by In/Sn/Pb atoms to form planar M layers, which are separated by pure A   layers. Band structure calculations within the FP-LAPW DFT approach together with the Zintl formalism, extended by the presence of hypervalent bonding of the heavier M′M′ elements, give insight into the chemical bonding of this series of p  -block metallides. An analysis of the band structure for the border phases Sr2PbGe2Sr2PbGe2 and Ca2SnGe2Ca2SnGe2 shows the considerable π bonding contributions within the Ge building units, which also become apparent from the short Ge–Ge bond lengths.

Graphical abstractExample of one of the mixed metallides A2(In/Sn/Pb)(Si/Ge)2 with planar Si/Ge zig-zag chain segments of variable lengths.Figure optionsDownload full-size imageDownload as PowerPoint slide