The crystal structure of girvasite, NaCa2Mg3(PO4)3(CO3)(H2O)6, a complex phosphate carbonate hydrate based upon electroneutral heteropolyhedral layers

• Published in: Russian Geology and Geophysics
• Main Authors: Krivovichev, S.V., Britvin, S.N., Chernyatieva, A.P., Yakovenchuk, V.N.
• Format: Article in Journal/Newspaper
• Language: English
• Published: Russian Geology and Geophysics 2015
• Subjects: crystal structure; phosphate-carbonate; complexation; structural complexity; Kola peninsula; Kola Peninsula; Sokolova; Yegorov; kola peninsula
• Online Access: https://doi.org/10.1016/j.rgg.2015.01.009; http://hdl.handle.net/11701/2271

Crystal chemical formula of girvasite. As it was mentioned above, the initial formula of girvasite proposed by Sokolova and Yegorov-Tismenko (1990) on the basis of crystal-structure determination is NaCa2Mg3(OH)2H2(PO4)3(CO3)(H2O)4. However, determination of all H sites in this work revealed no hydroxyl groups or protonated PO43- anions. Instead, all O atoms not bonded to P5+ or C4+ cations form two strong hydrogen bonds each, thus belonging to H2O groups. This observation allows us to revise the crystal chemical formula of girvasite as NaCa2Mg3(PO4)3(CO3)(H2O)6. This formula excludes simultaneous occurrence of the basic (OH)- and acid (PO3OH)2- anions originally postulated for girvasite by Sokolova and Yegorov-Tismenko (1990). The crystal structure of girvasite, NaCa2Mg3(PO4)3(CO3)(H2O)6, has been refined using X-ray diffraction data collected at 173 K, which allowed to revise its crystal chemical formula. The mineral is monoclinic, P21/c, a = 6.4784(2), b = 12.2313(3), с = 21.3494(6) Å, β = 89.624(2), V = 1691.67(8) Å3 (at 173 K), Z = 4, R1 = 0.037 for 6471 unique observed reflections. The crystal structure of girvasite contains three Mg, two Ca and one Na sites. The Mg atoms are octahedrally coordinated by O atoms and H2O molecules. The Ca sites are coordinated by eight anions each, whereas the Na site has a coordination number equal to seven. The crystal structure is based upon heteropolyhedral sheets formed by polymerization of Mg octahedra, PO4 tetrahedra and CO3 groups. The sheets consist of fundamental building units (FBBs) formed by two Mg octahedra that share edges to form dimers decorated by three PO4 tetrahedra and linked to a unit consisting of a MgO6 octahedron sharing an edge with a carbonate triangle. The FBBs polymerize to form chains running parallel to the a axis. The chains are further polymerized to compose heteropolyhedral sheets stuffed by the Ca2+ and Na+ cations, and H2O groups to form electroneutral layers parallel to (001). The adjacent layers connect to each other via a complex system of hydrogen bonds. The interesting feature of the structure is a bidentate coordination of Mg2 atom by a CO3 group. The O14-Mg2-O16 angle is shortened from 90o (expected for a regular octahedron) to 60.46o, whereas the O14-C-O16 angle is shortened from 120o to 115.92o. Girvasite is the most structurally complex mineral among natural phosphate carbonates known to date. Its high structural complexity reflects its chemical complexity and high hydration state, which are the result of the specific geochemical and thermodynamic conditions of its formation (low-temperature and low-pressure interactions of phosphate-bearing solutions with primary dolomite carbonatites). The Russian Foundation for Basic Research (grant # 14-05-00910) and internal grant of St. Petersburg State University (# 3.38.136.2014). X-ray diffraction measurements have been performed at the SPbSU X-ray Diffraction Resource Centre.