Accurate X‐ray diffraction data required for proper evaluation of bond valence sums and global instability indexes: redetermination of the crystal structures of diamond‐like Cu2CdSiS4 and Cu2HgSnS4 as a case study

• Published in: Acta crystallographica. Section C, Crystal structure communications Crystal structure communications, 2023-09, Vol.79 (9), p.353-364
• Main Authors: Treece, Megan M, Kelly, Jordan C, Rosello, Kate E, Craig, Andrew J, Aitken, Jennifer A
• Format: Article
• Language: English
• Subjects: Cadmium; Crystal structure; Crystallography; Diamonds; Instrumentation; Inversion; Ions; Mathematical analysis; Mercury; Stability analysis; Tin; X-ray diffraction
• ISSN: 0108-2701; 1600-5759; 2053-2296
• DOI: 10.1107/S2053229623006848

Our calculations of the global instability index (G) values for some diamond‐like materials with the general formula I2–II–IV–VI4 have indicated that the structures may be unstable or incorrectly determined. To compute the G value of a given compound, the bond valence sums (BVSs) must first be calculated using a crystal structure. Two examples of compounds with high G values, based on data from the literature, are the wurtz–stannite‐type dicopper cadmium silicon tetrasulfide (Cu2CdSiS4) and the stannite‐type dicopper mercury tin tetrasulfide (Cu2HgSnS4), which were first reported in 1967 and 1965, respectively. In the present study, Cu2CdSiS4 and Cu2HgSnS4 were prepared by solid‐state synthesis at 1000 and 900 °C, respectively. The phase purity was assessed by powder X‐ray diffraction. Optical diffuse reflectance UV/Vis/NIR spectroscopy was used to estimate the optical bandgaps of 2.52 and 0.83 eV for Cu2CdSiS4 and Cu2HgSnS4, respectively. The structures were solved and refined using single‐crystal X‐ray diffraction data. The structure type of Cu2CdSiS4 was confirmed, where Cd2+, Si4+ and two of the three crystallographically unique S2− ions lie on a mirror plane. The structure type of Cu2HgSnS4 was also verified, where all ions lie on special positions. The S2− ion resides on a mirror plane, the Cu+ ion is situated on a fourfold rotary inversion axis and both the Hg2+ and the Sn4+ ions are located on the intersection of a fourfold rotary inversion axis, a mirror plane and a twofold rotation axis. Using the crystal structures solved and refined here, the G values were reassessed and found to be in the range that indicates reasonable strain for a stable crystal structure. This work, together with some examples gathered from the literature, shows that accurate data collected on modern instrumentation should be used to reliably calculate BVSs and G values.