Crystal structure of incommensurate η-Cu1.235Sn intermetallic

Abstract

The crystallographic parameters of the incommensurately ordered phase η of the composition Cu1.235Sn are reported. This phase belongs to the group of ordered Ni2In/NiAs-type phases, with a NiAs-type arrangement Cu(1)Sn and additional Cu(2) atoms partially occupying trigonal-bipyramidal interstices in an ordered fashion, leading to the formula Cu(1)Cu(2)0.235Sn = Cu1.235Sn. The structure model, afterward refined on the basis of powder X-ray diffraction data, has been derived on the basis of the slightly Cu-poorer commensurately ordered η′-Cu6Sn5 (=Cu1.2Sn) phase but also on previously reported commensurate structure models η8-Cu1.25Sn and η4+1-Cu1.243Sn derived from selected area electron diffraction data. In line with a recent work (Leineweber, Wieser & Hügel, Scr. Mater. 2020, 183, 66-70), the incommensurate η phase is regarded as a metastable phase formed upon partitionless ordering of the η high-temperature phase with absent long-range ordering of the Cu(2) atoms. The previously described η8 and η4+1 superstructure are actually of the same phase, and the corresponding superstructure models can be regarded as approximant structures of the η phase. The refined structure model is described in 3+1 dimensional superspace group symmetry C2/c(q 10-q 3)00 with a unit cell of the average structure with lattice parameters of a av = 4.21866(3) Å, b av = 7.31425(5) Å, c av = 5.11137(3) Å and b av = 90.2205(5)° and a unit cell volume V = 157.717(2) Å3. The modulation vector is with q 1 = 0.76390(4), q 3 = 1.51135(5), and governs the spatial modulation of the occupancy of the Cu(2) atoms described by a Crenel function. The occupational ordering is accompanied by displacive modulations of the atoms constituting the crystal structure, ensuring reasonable interatomic distances on a local level. In particular, the spatial requirements of pairs of edge-sharing Cu(2)Sn5 trigonal bipyramids (Cu(2)2Sn8) lead to a measurable splitting of some fundamental reflections in the powder diffraction data. This splitting is considerable smaller in η′-Cu1.20Sn, which lacks such pairs due to the lower Cu content.