Red and Blue-Black Tin Monoxide, SnO: Pitfalls, Challenges, and Helpful Tools in Crystal Structure Determination of Low-Intensity Datasets from Microcrystals

Abstract

The crystal structures of red and blue-black tin(II) oxide, SnO, have been determined for the first time by single-crystal X-ray diffraction. Blue-black SnO crystallizes in the tetragonal space group P4/nmm, representing a layer structure consisting of the square-pyramidally coordinated tin and slightly distorted tetrahedrally coordinated oxygen atoms, in accordance with previous results. In contrast, red SnO crystallizes in the orthorhombic centrosymmetric space group Pbca rather than in the non-centrosymmetric space group Cmc2(1), as assumed for a long time. Its layer structure consists of very regular, trigonal-pyramidally coordinated tin atoms as well as trigonal-planar coordinated oxygen atoms. Special care was taken on space group determination, including lattice centering. C-centering could be excluded because of systematic absence violations detected when collecting and processing a primitive triclinic dataset and by generating precession images. In the absence of meaningful extinction conditions resulting from the very small crystal under examination, the structure was initially solved and refined in the triclinic space group P1. Subsequently, the observed atom coordinates were used to reconstruct the actual symmetry skeleton. The various possibilities to identify the correct space group starting from the triclinic solution are demonstrated, and the unique structural features of the crystal structure are visualized.