Organically Templated Layered Uranyl Molybdate [C3H9NH+] 4

minerals Article Organically Templated Layered Uranyl Molybdate + [C3H9NH ]4[(UO2)3(MoO4)5] Structurally Based on Mineral-Related Modular Units Evgeny Nazarchuk 1,*, Dmitri Charkin 2, Oleg Siidra 1,3 and Stepan Kalmykov 2 1 Department of Crystallography, Saint-Petersburg State University, University emb. 7/9, 199034 St. Petersburg, Russia; [email protected] 2 Department of Chemistry, Moscow State University, GSP-1, 119991 Moscow, Russia; [email protected] (D.C.); [email protected] (S.K.) 3 Kola Science Center, Russian Academy of Sciences, 184200 Apatity, Russia * Correspondence: [email protected]; Tel.: +7-921-156-14-79 Received: 5 July 2020; Accepted: 24 July 2020; Published: 25 July 2020 + Abstract: A new organically templated uranyl molybdate [C3H9NH ]4[(UO2)3(MoO4)5] was prepared by a hydrothermal method at 220 ◦C. The compound is monoclinic, Cс, a = 16.768(6), b = 20.553(8), 3 c = 11.897(4) Å, β = 108.195(7), V = 3895(2) Å , R1 = 0.05. The crystal structure is based upon 4 [(UO2)3(MoO4)5] − uranyl molybdate layers. The isopropylammonium cations are located in the + interlayer. The layers in the structure of [C3H9NH ]4[(UO2)3(MoO4)5] are considered as modular VI architectures. Topological analysis of layers with UO2:TO4 ratio of 3:5 (T = S, Cr, Se, Mo) was performed. Modular description is employed to elucidate the relationships between different structural 4 topologies of [(UO2)3(TO4)5] − layers and inorganic uranyl-based nanotubules. The possible existence of uranyl molybdate nanotubules is discussed. Keywords: uranyl molybdates; uranyl sulfates; uranyl selenates; crystal structure; layered structures; minerals; nanotubules 1. Introduction Investigations of natural and synthetic compounds of hexavalent uranium are important both for materials science and mineralogy. Uranium minerals are important constituents of oxidation zones of uranium deposits [1,2]. The development of the nuclear industry also requires further investigations in the area of safe nuclear waste management [3]. The latter requires proper understanding of phase formation processes, relationships between chemical compositions, crystal structures, and properties of the compounds formed. Of particular interest are both the chemical nature of the possible secondary phases and their interactions with the geological environment [4]. In the last two decades, particular attention has been paid to the hexavalent uranium (uranyl) compounds containing organic moieties, which are important for lanthanide/actinide separation. Common among these are the hybrid materials wherein the organic molecules are directly coordinated to the uranyl cation as ligands [5,6]. The templated structures based on weakly bonded organic and inorganic parts are less numerous [7] but exhibit essentially larger structural diversity of inorganic motifs. The uranium compounds are formed during various steps of the nuclear cycle and present in the nuclear waste [3]. They accumulate various nuclides, thus preventing their migration into the environment [4]. The composition of nuclear waste is extremely complex and can contain both newly formed phases, as well as products of interaction between the fuel and container material, as well as with geological environment. The molybdenum isotopes (95Mo, 97Mo, 98Mo and 100Mo), formed Minerals 2020, 10, 659; doi:10.3390/min10080659 www.mdpi.com/journal/minerals Minerals 2020, 10, 659 2 of 12 Minerals 2020, 10, 659 2 of 12 95 97 98 100 duringwith geological the fission environment. process, are relativelyThe molybdenum stable and isotopes accumulate ( Mo, in Mo, the wasteMo and fuel. TopologicallyMo), formed during similar andthe even fission isostructural process, are compounds relatively stable are also and known accumulate in the in chemistry the waste of fuel. pentavalent Topologically neptunium similar [ 7and]. evenThough isostructural the natural compounds and synthetic are also known uranyl in compounds the chemistry are of generally pentavalent formed neptunium under [7]. essentially Though the natural and synthetic uranyl compounds are generally formed under essentially different conditions, their crystal structures demonstrate topological relationships [8]. Of more different conditions, their crystal structures demonstrate topological relationships [8]. Of more than than 300 primary and secondary uranium minerals known to date (http://rruff.info/ima), the latter 300 primary and secondary uranium minerals known to date (http://rruff.info/ima), the latter demonstrate the expected richer structural chemistry wherein uranium most commonly forms a demonstrate the expected richer structural chemistry wherein uranium most commonly forms a linear uranyl cation coordinated by four, five, or six ligands in the equatorial plane. The coordination linear uranyl cation coordinated by four, five, or six ligands in the equatorial plane. The coordination polyhedra can share only edges, only corners, or both edges and corners between each other or also polyhedra can share only edges, only corners, or both edges and corners between each other or also with tetrahedral polyhedra of oxyanions. The group of compounds structurally based on exclusively with tetrahedral polyhedra of oxyanions. The group ofVI compounds structurally based on exclusively corner sharing between UOn polyhedra and TO4 (T = S, Cr, Se, Mo) tetrahedra is represented in corner sharing between UOn polyhedra and TO4 (TVI = S, Cr, Se, Mo) tetrahedra is represented in the thesecondary secondary minerals. minerals. Their Their structures structures exhibit exhibit two types two typesof 0D, offour 0D 1,D four, and 1 fourD, and 2D fourcomplexes 2D complexes (Figure (Figure1). 1). Figure 1. Heteropolyhedral complexes with corner sharing only between UOn bipyramids and TO4 Figure 1. Heteropolyhedral complexes with corner sharing only between UOn bipyramids and TO4 tetrahedra in the mineral crystal structures: (a) belakovskiite, (b) bluelizardite, (c) bobcookite, (d) tetrahedra in the mineral crystal structures: (a) belakovskiite, (b) bluelizardite, (c) bobcookite, (d) meisserite, meisserite, (e) shumwayite, (f) walpurgite, (g) autunite, (h) straßmannite, (i) wetherillite and (j) (e) shumwayite, (f) walpurgite, (g) autunite, (h) straßmannite, (i) wetherillite and (j) beshtauite. beshtauite. The 0D complexes are observed in the sulfate minerals belakovskiite, Na7(UO2)(SO4)4(SO3OH) 3H2O[9] The 0D complexes are observed in the sulfate minerals belakovskiite,· and bluelizardite, Na7(UO2)(SO4)4Cl 2H2O[10], which are the secondary products of uraninite weathering; Na7(UO2)(SO4)4(SO3OH)∙3H2O [9]· and bluelizardite, Na7(UO2)(SO4)4Cl∙2H2O [10], which are the both species have been found in the Blue Lizard mine, San Juan, UT, USA. Though a large number of secondary products of uraninite weathering; both species have been found in the Blue Lizard mine, natural uranyl sulfates has been described [11], the complexes observed in belakovskiite (Figure1a) and San Juan, UT, USA. Though a large number of natural uranyl sulfates has been described [11], the bluelizardite (Figure1b) are yet unique. complexes observed in belakovskiite (Figure 1а) and bluelizardite (Figure 1b) are yet unique. The same locality also bears bobcookite, NaAl(UO2)2(SO4)4 18H2O[12], fermiite, Na4(UO2)(SO4)3 3H2O, The same locality also bears bobcookite, NaAl(UO· 2)2(SO4)4∙18H2O [12], fermiite,· 2 and oppenheimerite, Na2(UO2)(SO4)2 3H2O[13], whose structures are comprised of [(UO2)(SO4)2(H2O)] − Na4(UO2)(SO4)3∙3H2O, and oppenheimerite,· Na2(UO2)(SO4)2∙3H2O [13], whose structures are chains (Figure1 с). This topology is common for synthetic uranyl sulfates, selenates, comprised of [(UO2)(SO4)2(H2O)]2− chains (Figure 1с). This topology is common for synthetic uranyl and chromates [14]. They are also present in the structures of rietveldite, Fe(UO )(SO ) 5H O[15] sulfates, selenates, and chromates [14]. They are also present in the structures2 of4 rietveldite,2· 2 and svornostite, K Mg[(UO )(SO ) ] 8H O[16]. The chains observed in the structure of meisserite, Fe(UO2)(SO4)2∙5H22O [15] and2 svornostite,4 2 2 2 K2Mg[(UO2)(SO4)2]2∙8H2O [16]. The chains observed in the · 2 Na5(UO2)(SO4)3(SO3OH) H2O[17] can be derived from [(UO2)(SO4)2(H2O)] − chains [18] via the addition · Minerals 2020, 10, 659 3 of 12 of a protonated sulfate tetrahedron (Figure1d). The structure of shumwayite, ((UO )(SO )(H O) ) H O[19] 2 4 2 2 2· 2 is formed by association of [(UO2)(SO4)(H2O)2] chains (Figure1e) and water via hydrogen bonding. In the structures of deloryite, Cu (UO )(MoO ) (OH) [20], walpurgite, (BiO) (UO )(AsO ) 2H O[21], 4 2 4 2 6 4 2 4 2· 2 and orthowalpurgite, (BiO) (UO )(AsO ) 2H O[22], the [(UO )(TO ) ]2 chains are comprised of UO 4 2 4 2· 2 2 4 2 − 6 tetragonal bipyramids and TO4 tetrahedra sharing vertices (Figure1f). Their association leads to the formation of autunite-type layers (Figure1g) [23]. n+ A large number of uranium minerals with a common formula A [(UO2)(TO4)](H2O)mXk adopt the V structures based on autunite-related [(UO2)(T O4)]− layers. Therein, A may stand for a single, double, or even triple-charged cation while T is P or As, and X is generally F or OH. The layers observed in the structures of magnesioleydetite, Mg(UO )(SO ) 11H O, straßmannite, Al(UO )(SO ) F 16H O[24], 2 4 2· 2 2 4 2 · 2 geschieberite, K (UO )(SO ) 2H O[25], and leydetite, Fe(UO )(SO ) 11H O[26] are topologically 2 2 4 2· 2 2 4 2· 2 identical (Figure1h). Therein, four out of five equatorial vertices of uranium polyhedra are occupied by oxygen atoms of sulfate tetrahedra while the fifth is occupied by a water molecule; all such vertices are similarly oriented in the layer plane. The layers in the structure of wetherillite, Na Mg(UO ) (SO ) 18H O[12], differ in that the vertices occupied by water molecules exhibit two 2 2 2 4 4· 2 positions (Figure1i). Yet another layered arrangement is formed by vertex-sharing UO 6(H2O) and SO4 moieties (Figure1j) in the structure of beshtauite, (NH ) (UO )(SO ) 2H O[27].

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