New Quaternary Compounds R3Ni0.5SiS7 (R – Y, Sm, La) with the La3Mn0.5SiS7 Structure

  • Oleksandr Smitiukh Lesya Ukrainka Volyn National University, Lutsk, Ukraine
  • Oleg Marchuk Lesya Ukrainka Volyn National University, Lutsk, Ukraine
Keywords: quaternary sulfides, rare-earth metal, crystal structure, X-ray powder method


The new sulfides Y3Ni0.5SiS7, Sm3Ni0.5SiS7, and La3Ni0.5SiS7 exist in the quasi-ternary systems Y2S3 – NiS – SiS2, Sm2S3 – NiS – SiS2, and La2S3 – NiS – SiS2, respectively, for which the isothermal sections at 770 K were investigated. The crystal structure of the sulfides was determined by the X-ray powder method. It belongs to the La3Mn0.5SiS7 structure type (S.G. Р63; Pearson symbol hP23), with the lattice parameters а = 0.97643(4) nm; с = 0.56377(4) nm (Y3Ni0.5SiS7), а = 0.99599(8) nm; с = 0.56583(5) nm (Sm3Ni0.5SiS7), and а = 1.02830(6) nm; с = 0.57412(4) nm (La3Ni0.5SiS7). The structure of obtained sulfides is as follows: Y, Sm, and La atoms are located in the 6с site and center trigonal prisms with two additional S atoms. Ni atoms occupy the 2а site (0.5 occupancy) and have octahedral surrounding of S atoms. The coordination number of Si atoms (the 2b site) is 4. The Ni-centered octahedra form infinite chains [Ni 6S]n.


Fu Huiying, Environmentally friendly and earth-abundant colloidal chalcogenide nanocrystals for photovoltaic applications, J. Mater. Chem. C. 6(3), 414 (2018).

F.F. Jaldurgam, Z. Ahmad, F. Touati. Low-Toxic, Earth-Abundant Nanostructured Materials for Thermoelectric Applications, Nanomaterials 11(4), 895 (2021);

M.R. Huch, L.D. Gulay, I.D. Olekseyuk, Crystal structures of the R3Mg0.5GeS7 (R = Y, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho and Er) compounds, J. Alloys Compd. 424, 114 (2006);

L.D. Gulay, M. Daszkiewicz, M.R. Huch, A. Pietraszko, Ce3Mg0.5GeS7 from single-crystal data Acta Cryst., Sect. E. 63, i187 (2007);

O.M. Strok, M. Daszkiewicz, L.D. Gulay, Crystal structure of R3Mg0.5DSe7 (R = Ce, Pr; D = Si, Ge), Chem. Met. Alloys. 8, 16 (2015).

J. He, Z. Wang, X. Zhang, Y. Cheng, Y. Gong, X. Lai, C. Zheng, J. Lin, F. Huang, Synthesis, structure, magnetic and photoelectric properties of Ln3M0.5M′Se7 (Ln = La, Ce, Sm; M = Fe, Mn; M′ = Si, Ge) and La3MnGaSe7, RSC Adv. 5, 52629 (2015);

Y. Pei, X. Shi, A. LaLonde, H. Wang, L. Chen, G.J. Snyder, Convergence of electronic bands for high performance bulk thermoelectric, Nature 473, 66 (2011);

F.Q. Huang, P. Brazis, C.R. Kannewurf, J.A. Ibers, Syntheses, Structures, and Physical Properties of the New Quaternary Rare-Earth Chalcogenides RbNd2CuS4, RbSm2CuS4, CsLa2CuSe4, CsSm2CuSe4, RbEr2Cu3S5, CsGd2Ag3Se5, CsTb2Ag3Se5, and Rb2Gd4Cu4S9, Am. Chem. Soc. 122, 80 (2000);

L.D. Gulay, D. Kaczorowski, A. Szajek, A. Pietraszko, Crystal and electronic structure and magnetic properties of CeRhPb, J. Phys. Chem. Solids 69 (8), 1934 (2009);

L. Akselrud, Yu. Grin, WinCSD: software package for crystallographic calculations (Version 4), J. Appl. Cryst. 47(2), 803 (2014);

K. Momma, F. Izumi, VESTA 3 for three-dimensional visualization of crystal, J. Appl. Crystallogr. 44, 1272 (2011);

A. Michelet, J. Flahaut, Chimie minerale. Sur de nouvelles familles de composes forms par les sulfures des terres rares avec le sulfure de germanium ou le sulfure de silicium, C.R. Acad. Sci. 268, 326 (1969).

G. Perez, M. Duale, Chimie minerale. Sur une nouvelle famille de combinaisons sulfurees des terres rares de formule generale Ln4Si3S12 (Ln = Ce-Gd), С.R. Acad. Sci. 269, 984 (1969).

A. Michelet, G. Perez, J. Etienne, M. Darriet-Duale, Sur Une Nouvelle Famille de Combinaisons Des Terres Rares de Formules Ln2SiS5 (Ln = La à Nd) et Ln2GeS5 (Ln = La), C.R. Acad. Sci. 271, 513 (1970).

M. Daszkiewicz, L.D. Gulay, I.R. Ruda, O.V. Marchuk, A. Pietraszko, La2SiS5, Acta Cryst. Sect. E. 63(12), i197 (2007).

O.M. Aliev, G.G. Khasaev, T.Kh. Kurbanov, Synthesis and physicochemical study of the Me2+Ln4S7(Se7) type compounds, Bull. Soc. Chim. Fr. 1, 26 (1986).

G. Collin, P. Laruelle, Structure cristalline de. La6MnSi2S14, C.R. Seances l'Acad. Sci. 270, 410 (1970).

O. Marchuk, O. Smitiukh, Crystal structure of sulfides R3Co(Ni)0,5SiS7 (R – Ce, Pr), Proceedings of the Taras Shevchenko Scientific Society. Chemical sciences. LXVI, 134 (2021) (In Ukrainian).

Kh.O. Melnychuk, M. M. Poznanska, O.V. Marchuk, L.D. Hulai, Modern Chemical Problems: a collection of report abstracts of II International scientific conference of students, postgraduates, and young scientists, 19–21 March 2019, Vinnytsia city / Vasyl Stus Donetsk National University: (edited by O.M. Shendryk) Vinnytsia, 2019, 248 s (In Ukrainian).

Kh.O. Melnychuk, O.V. Marchuk, L.D. Hulai, The crystal structure of Tb3Ga1.67S7, Scientific bulletin of Chernivtsi University, Chemistry series, 781, 80 (2016) (In Ukrainian).

Kh.O. Melnychuk, O.V. Marchuk, L.D. Hulai, The crystal structure of Ho3Ni0.5SiS7 Scientific bulletin of Uzhhorod National University, Chemistry series 2(36), 10 (2016) (In Ukrainian).

Kh.O. Melnychuk, O.V. Marchuk, I.D. Olekseyuk, L.D. Hulai, The NiS – Er2S3 – SiS2 system at 770 K Collection of scientific papers. 2(33), 14 (2014) (In Russian).

J. Peters, B. Krebs, Silicon disulphide and silicon diselenide: a reinvestigation, Acta Cryst., Sect. B, 38, 1270 (1982);

A.J. Campbell, D.L. Heinz, High pressure acoustic wave velocities and equations of state of the alkali chlorides, J. Phys. Chem. Solids 54, 157 (1993).

T. Schleid, ChemInform Abstract: Crystal Structures of D-Y2S3 and Y2OS2, Eur. J. Solid State Inorg. Chem. 29 (6), 1015-1028 (1992);

A. Atsushi, Ts. Sachiko, Crystal Structure of Samarium Sesquisulfide, α-Sm2S3, N. Izumi, Anal. Sci. 12(1), 151 (1996);

A.A. Eliseev, G.M. Kuz'micheva, Sulfide and fluorosulfides IK-meterials, phase diagrams, structure and properties of sulfides of Gallium, Indium, rare-eart elements, Report of the Academy of Sciences SSSR 246, 1162 (1979) (In Russian).

How to Cite
SmitiukhO., & MarchukO. (2022). New Quaternary Compounds R3Ni0.5SiS7 (R – Y, Sm, La) with the La3Mn0.5SiS7 Structure. Physics and Chemistry of Solid State, 23(4), 640-646.
Scientific articles (Chemistry)