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These isostructural compounds crystallize in the Cu<jats:sub>4<\/jats:sub>NiSi<jats:sub>2<\/jats:sub>S<jats:sub>7<\/jats:sub>structure type, which can be considered as a superstructure of cubic diamond or sphalerite. The monovalent (Cu<jats:sup>+<\/jats:sup>), divalent (Fe<jats:sup>2+<\/jats:sup>or Co<jats:sup>2+<\/jats:sup>) and tetravalent (Ge<jats:sup>4+<\/jats:sup>) cations adopt tetrahedral geometries, each being surrounded by four S<jats:sup>2\u2212<\/jats:sup>anions. The divalent cation and one of the sulfide ions lie on crystallographic twofold axes. These tetrahedra share corners to create a three-dimensional framework structure. All of the tetrahedra align along the same crystallographic direction, rendering the structure non-centrosymmetric and polar (space group<jats:italic>C<\/jats:italic>2). Analysis of X-ray powder diffraction data revealed that the structures are the major phase of the reaction products. Thermal analysis indicated relatively high melting temperatures, near 1273\u2005K.<\/jats:p>","DOI":"10.1107\/s2056989020007872","type":"journal-article","created":{"date-parts":[[2020,6,19]],"date-time":"2020-06-19T08:28:27Z","timestamp":1592555307000},"page":"1117-1121","update-policy":"https:\/\/doi.org\/10.1107\/cm_01","source":"Crossref","is-referenced-by-count":4,"title":["Syntheses and crystal structures of the quaternary thiogermanates Cu<sub>4<\/sub>FeGe<sub>2<\/sub>S<sub>7<\/sub>and Cu<sub>4<\/sub>CoGe<sub>2<\/sub>S<sub>7<\/sub>"],"prefix":"10.1107","volume":"76","author":[{"given":"Andrew J.","family":"Craig","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Stanislav S.","family":"Stoyko","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Allyson","family":"Bonnoni","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Jennifer A.","family":"Aitken","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"329","published-online":{"date-parts":[[2020,6,19]]},"reference":[{"key":"hb7920_bb1","doi-asserted-by":"crossref","first-page":"4714","DOI":"10.1021\/cm0105357","volume":"13","author":"Aitken","year":"2001","journal-title":"Chem. 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