Phase formation in the Ag2MoO4-CoMoO4-Al2(MoO4)3 system

The subsolidus region of the Ag₂MoO₄-CoMoO₄-Al₂(MoO₄)₃ ternary salt system was studied by X-ray powder diffraction analysis. New compounds Ag_1?x Co_1?x Al_{1 + x} (MoO₄)₃ (0 ≤ x ≤ 0.4) and AgCo₃Al(MoO₄)₅ were detected to form. The variable-composition phase Ag_1?x Co_1?x Al_{1 + x} (MoO₄)₃ is of the NASICON structure type (space group \(R\bar 3c\) ). AgCo₃Al(MoO₄)₅ crystallizes in the triclinic symmetry (space group \(P\bar 1\) Z = 2) with the unit cell parameters a = 6.9101(6), b = 17.519(1), c = 6.8241(6) Å, α = 87.356(7)°, β = 101.078(7)°, and γ = 91.985(9)°. The compounds are thermally stable until 770–780 and 760°C, respectively.     

Phase equilibria in the Tl2MoO4-Nd2(MoO4)3-Hf(MoO4)2 system and the crystal structure of double molybdate TlNd(MoO4)2

The Tl₂MoO₄-Nd₂(MoO₄)₃-Hf(MoO₄)₂ system was studied in the subsolidus region using X-ray powder diffraction. New triple molybdates were found to exist in this system: Tl₅NdHf(MoO₄)₆ (5: 1: 2), TlNdHf_0.5(MoO₄)₃ (1: 1: 1), and Tl₂NdHf₂(MoO₄)_6.5 (2: 1: 4). The first TlNd(MoO₄)₂ single crystals were grown from melt solutions with spontaneous nucleation. Their crystal structure was refined from X-ray diffraction data (Bruker X8 Apex automated diffractometer, MoK _α radiation, 386 F(hkl), R = 0.0136). The tetragonal unit cell parameters are as follows: a = 6.3000(2) Å, c = 9.5188(5) Å, V = 377.80(3) ų, Z = 2, ρ_calcd = 5.876 g/cm³, space group P4/nnc. The structure is a framework built of NdO₈ and TlO₈ tetragonal antiprisms linked via shared lateral edges and alternating in the checkerboard order. Layers share oxygen vertices with MoO₄ interlayer tetrahedra and are linked into the framework.     

Phase equilibria in the systems Rb2MoO4-R2(MoO4)3-Hf(MoO4)2 (R = Al, In, Sc, Fe(III)) and the crystal structure of double molybdate RbFe(MoO4)2

The systems Rb₂MoO₄-R₂(MoO₄)₃-Hf(MoO₄)₂ have been investigated in the subsolidus region by X-ray powder diffraction, DTA, and IR spectroscopy. Triple molybdates of the composition 5: 1: 2 are formed in the systems with R = Al, In, Sc, and Fe. Molybdates of composition 5: 1: 3 and 1: 1: 1 are found in the iron(III)-containing system in addition to the 5: 1: 2 molybdate. Single crystals of the double molybdate RbFe(MoO₄)₂, which is formed in the Rb₂MoO₄-Fe₂(MoO₄)₃ system, have been grown. The structure of this double molybdate has been refined using X-ray diffraction data (X8 APEX automated diffractometer, MoK _α radiation, 373 F(hkl), R = 0.0287). The trigonal unit cell parameters are the following: a = b = 5.6655(2) Å, c = 7.5061(4) Å, V = 208.65(1) ų, Z = 1, ρ_calc = 3.670 g/cm³, space group R3m1. The structure is formed by layers of FeO₆ octahedra sharing corners with MoO₄ tetrahedra and RbO₁₂ icosahedra.     

Double molybdate Tl2Mg4(MoO4)3: Synthesis, structure, and properties

Single crystals of molybdate Tl₂Mg₂(MoO₄)₃ are grown, and its crystal structure is refined in an X-ray diffraction experiment (an automated diffractometer, MoK _α radiation, 914 F(hkl) reflections, R = 0.0459). The crystal are cubic with a = b = c = 10.700(1) Å, V = 1225.0(2) ų, Z = 4, space group P2₁3. The mixed 3D framework of the structure is built of MoO₄ tetrahedra and two types of corner-sharing MgO₆ octahedra. Two types of thallium atoms occupy large interstices.     

New complex ytterbium molybdophosphates M 2 I Yb(PO4)(MoO4) (MI = K, Na): Synthesis and structure solution

Complex rare-earth molybdophosphates of sodium and potassium (Na₂Yb(PO₄)(MoO₄) (I) and K₂Yb(PO₄)(MoO₄) (II) are synthesized by solid-phase reactions at 600°C (for I) and 750°C (for II). The molybdophosphates are characterized using powder X-ray diffraction, laser second harmonic generation (SHG), IR spectroscopy, and differential thermal analysis. Their structures are refined using the Rietveld technique. The compounds are isostructural and crystallize in an orthorhombic system (space group Ibca, Z = 8). The unit cell parameters are a = 18.0086(1) Å, b = 12.0266(1) Å, c = 6.7742(1) Å for compound I and a = 19.6646(1) Å, b = 12.0570(1) Å, c = 6.8029(1) Å for compound II. The structures are built of YbO₈ chains extended along axis c and linked into layers through PO₄ tetrahedra. The Na⁺ cations (CN = 6) and the K⁺ cations (CN = 8) reside in the interlayer spaces.     

Phase formation in the Rb2MoO4-Er2(MoO4)3-Hf(MoO4)2 system and the crystal structure of new triple molybdate Rb5ErHf(MoO4)6

The subsolidus region of the Rb₂MoO₄-Er₂(MoO₄)₃-Hf(MoO₄)₂ ternary salt system is studied using X-ray powder diffraction. A novel 5: 1: 2 triple molybdate, Rb₅ErHf(MoO₄)₆, is found to form in the system. Crystals of Rb₅ErHf(MoO₄)₆ are flux-grown under spontaneous nucleation conditions. The composition and crystal structure of Rb₅ErHf(MoO₄)₆ are refined in a single-crystal X-ray diffraction experiment (X8 APEX diffractometer, MoK _α radiation, 1753 reflections, R = 0.0183). The crystals are trigonal; a = 10.7511(1) Å, c = 38.6543(7) Å, V = 3869.31(9) ų, d _calc = 4.462 g/cm³, Z = 6, space group $R\bar 3c$ . The mixed three-dimensional framework of the structure is formed of MoO₄ tetrahedra, each sharing corners with two ErO₆ and HfO₆ octahedra. Two types of Rb atoms occupy large cavities of the framework. The distribution of the Er³⁺ and Hf⁴⁺ cation over two positions is refined in the course of structure solution.     

Crystal growth,structure, and properties of manganese orthovanadate Mn3(VO4)2

Manganese orthovanadate Mn₃(VO₄)₂ single crystals were grown for the first time from a flux of MnO/V₂O₅/MoO₃. The flux and oxygen partial pressure used are the key factors for the crystal growth and prevention of the oxidation of Mn²⁺ and the reduction of V⁵⁺ during the crystallization process. The reduction and oxidation chemistry of Mn₃(VO₄)₂ was studied. Mn₃(VO₄)₂ is isostructural with magnesium orthovanadate Mg₃(VO₄)₂, orthorhombic, space group Cmca, a=6.247(1) Å, b=11.728(2) Å, c=8.491(2) Å and Z=4, as determined by single crystal X-ray diffraction. Because it is a Mn²⁺ deficient spinel structure there are two-dimensional sheets of Mn²⁺O₆ octahedra within the structure which show unusual ferrimagnetic properties.     

Phase formation in the Ag<Subscript>2</Subscript>MoO<Subscript>4</Subscript>-MgMoO<Subscript>4</Subscript>-Al<Subscript>2</Subscript>(MoO<Subscript>4</Subscript>)<Subscript>3</Subscript> system

The subsolidus region of the Ag₂MoO₄-MgMoO₄-Al₂(MoO₄)₃ ternary salt system has been studied by X-ray phase analysis. The formation of new compounds Ag_{1 ? x} Mg_{1 ? x} Al_{1 + x} (MoO₄)₃ (0 ≤ x ≤ 0.4) and AgMg₃Al(MoO₄)₅ has been determined. The Ag_{1 ? x} Mg_{1 ? x} Al_{1 + x} (MoO₄)₃ variable-composition phase is related to the NASICON type structure (space group R \(\bar 3\) c). AgMg₃Al(MoO₄)₅ is isostructural to sodium magnesium indium molybdate of the same formula unit and crystallizes in triclinic system (space group P \(\bar 1\), Z = 2) with the following unit cell parameters: a = 9.295(7) Å, b = 17.619(2) Å, c = 6.8570(7) Å, α = 87.420(9)°, β = 101.109(9)°, γ = 91.847(9)°. The compounds Ag_{1 ? x} Mg_{1 ? x} Al_{1 + x} (MoO₄)₃ and AgMg₃Al(MoO₄)₅ are thermally stable up to 790 and 820°C, respectively.     

Beiträge zum thermischen Verhalten und zur Kristallchemie von wasserfreien Phosphaten XXXII [1] Neue Orthophosphate des zweiwertigen Chroms — Mg3Cr3(PO4)4, Mg3, 75Cr2, 25(PO4)4, Ca3Cr3(PO4)4 und Ca2, 00Cr4, 00(PO4)4

Contributions on Crystal Chemistry and Thermal Behaviour of Anhydrous Phosphates. XXXII. New Orthophosphates of Divalent Chromium — Mg₃Cr₃(PO₄)₄, Mg_{3, 75}Cr_{2, 25}(PO₄)₄, Ca₃Cr₃(PO₄)₄ and Ca_{2, 00}Cr_{4, 00}(PO₄)₄ Solid state reactions via the gas phase led in the systems A₃(PO₄)₂ / Cr₃(PO₄)₂ (A = Mg, Ca) to the four new compounds Mg₃Cr₃(PO₄)₄ ( A ), Mg_3.75Cr_2.25(PO₄)₄ ( B ), Ca₃Cr₃(PO₄)₄ ( C ), and Ca_2.00Cr_4.00(PO₄)₄ ( D ). These were characterized by single crystal structure investigations [( A ): P2₁/n, Z = 1, a = 4.863(2) Å, b = 9.507(4) Å, c = 6.439(2) Å, β = 91.13(6)°, 1855 independend reflections, 63 parameters, R1 = 0.035, wR2 = 0.083; ( B ): P2₁/a, Z = 2, a = 6.427(2) Å, b = 9.363(2) Å, c = 10.051(3) Å, β = 106.16(3)°, 1687 indep. refl., 121 param., R1 = 0.032, wR2 = 0.085; ( C ): P‐1, Z = 2, a = 8.961(1) Å, b = 8.994(1) Å, c = 9.881(1) Å, α = 104.96(2)°, β = 106.03(2)°, γ = 110.19(2)°, 2908 indep. refl., 235 param., R1 = 0.036, wR2 = 0.111; ( D ): C2/c, Z = 4, a = 17.511(2) Å, b = 4.9933(6) Å, c = 16.825(2) Å, β = 117.95(1)°, 1506 indep. refl., 121 param., R1 = 0.034, wR2 = 0.098]. The crystal structures contain divalent chromium on various crystallographic sites, each showing a (4+n)‐coordination (n = 1, 2, 3). For the magnesium compounds and Ca_2.00Cr_4.00(PO₄)₄ a disorder of the divalent cations Mg²⁺/Cr²⁺ or Ca²⁺/Cr²⁺ is observed. Mg_3.75Cr_2.25(PO₄)₄ adopts a new structure type, while Mg₃Cr₃(PO₄)₄ is isotypic to Mg₃(PO₄)₂. Ca₃Cr₃(PO₄)₄ and Ca_2.00Cr_4.00(PO₄) ₄ are structurally very closely related and belong to the Ca₃Cu₃(PO₄)₄‐structure family. The orthophosphate Ca₉Cr(PO₄)₇, containing trivalent chromium, has been obtained besides C and D .     

Systems Tl2MoO4-E(MoO4)2, where E = Zr or Hf, and the crystal structure of Tl8Hf(MoO4)6

Systems Tl₂MoO₄-E(MoO₄)₂ (E = Zr, Hf) are studied using X-ray powder diffraction, DTA, and IR spectroscopy. Compounds Tl₈E(MoO₄)₆ and Tl₂E(MoO₄)₂ are found in these systems. T-x diagrams for the Tl₂MoO₄-Zr(MoO₄)₂ system are designed. Single crystals are grown and structure is solved for Tl₈Hf(MoO₄)₆. The compound crystallizes in a monoclinic structure with the unit cell parameters a = 9.9688(6) Å, b = 18.830(1) Å, c = 7.8488(5) Å, β = 108.538(1)°, Z = 2, space group C2/m. The main structural fragment is a [HfMo₆O₂₄]^8? isle group. Three crystallographically independent types of Tl polyhedra uniformly fill spaces between [HfMo₆O₂₄]^8? fragments to form a three-dimensional framework.     

Formation laws for scheelite-like triple molybdates LiMLn2(MoO4)4

The size factor is shown to be decisive in the structure formation of triple molybdates LiMLn₂(MoO₄)₄. The LiMLn₂(MoO₄)₄ compounds (where M is a large alkali metal) are formed when 0.48 Å ≤ r _M ⁺ ? r _Ln ³⁺ ≤ 0.60 Å.     

Phase formation in the system involving silver, magnesium, and indium molybdates

The subsolidus region of the Ag₂MoO₄-MgMoO₄-In₂(MoO₄)₃ ternary salt system has been studied by X-ray powder diffraction. The formation of new compounds Ag_{1 ? x} Mg_{1 ? x} In_{1 + x} (MoO₄)₃ (0 ≤ x ≤ 0.6) and AgMg₃In(MoO₄)₅ has been established. The unit cell parameters of solid-solution samples have been determined. The Ag_{1 ? x} Mg_{1 ? x} In_{1 + x} (MoO₄)₃ phase of variable composition has a NASICON-type structure (space group R $ \bar 3 $ c) AgMg₃In(MoO₄)₅ is isostructural to sodium magnesium indium molybdate of the same formula unit and crystallizes in triclinic system (space group P $ \bar 1 $ , Z = 2) with the following unit cell parameters: a = 7.0374(5) Å, b = 17.932(1) Å, c = 6.9822(4) Å, α = 87.309(6)°, β = 100.832(6)°, γ = 92.358(6)°. The compounds Ag_{1 ? x} Mg_{1 ? x} In_{1 + x} (MoO₄)₃ and AgMg3In(MoO₄)₅ are thermally stable up to 960 and 1030°C, respectively.     

Na4SeO5, ein neues Pentaoxoselenat(VI) – Synthese,Charakterisierung und Vergleich mit isotypem Na4MoO5

Na₄SeO₅, a Novel Pentaoxoselenate(VI) – Synthesis, Charakterisation, and Comparison with Na₄MoO₅ Na₄SeO₅ was prepared by high pressure solid state reaction at 500 °C and at a hydrostatic pressure of 2.5 Gpa from a mixture of Na₂O and Na₂SeO₄ in silver crucibles and Na₄MoO₅ by solid state reaction at 450 °C from a mixture of Na₂O and MoO₃. The crystal structures of both new compounds were solved and refined using X‐ray powder methods (Profilematching Na₄SeO₅: P1, a = 988.3(1), b = 988.4(1), c = 558.6(1) pm, α = 96.25(1)°, β = 96.24(1)°, γ = 113.41(1)°, R_p = 0.0783, R_wp = 0.1037. Profilematching Na₄MoO₅: P1, a = 999.5(1), b = 1002.0(1), c = 565.1(1) pm, α = 96.54(1)°, β = 96.29(1)°, γ = 113.35(1)°, R_p = 0.0623, R_wp = 0.0867). Both compounds contain novel XO₅^4– anions of approximately tetragonal pyramidal shape. The crystal structures are consistent with spectroscopic data (IR, Raman).     

Binary molybdates K4M2+(MoO4)3 (M2+=Mg, Mn, Co) and crystal structure of K4Mn(MoO4)3

Binary molybdates K₄M²⁺ (MoO₄)₃ (M²⁺=Mg, Mn, Co) isostructural to triclinic \ga-K₄Zn(WO₄)₃ were synthesized, and optimal conditions for their spontaneous crystallization were found. It was established by XRPA and DTA that at 530°C the structure of the compound with cobalt undergoes a transition to the orthorhombic structure of K₄Zn(MoO₄)₃. The structure of K₄Mn(MoO₄)₃ was determined from single crystal diffraction data (a=7.613, b=9.955, c=10.156 Å,α=92.28,β=106.66,γ=105.58°, Z=2, space group $P\bar 1$ , R=0.030). In this compound, Mn has a higher coordination number (CN=5+1) than that of Zn inα-K₄Zn(WO₄)₃ (CN=4+1). The main structural feature is pairs of MnO₆ octahedra linked by the bridging MoO₄ tetrahedra into ribbons stretching along the a axis. The structure is compared with related structures of binary molybdates and other members of the alluaudite family.     

Synthese und Struktur neuer Natriumhydrogensulfate Na(H3O)(HSO4)2; Na2(HSO4)2(H2SO4) und Na(HSO4)(H2SO4)2

Synthesis and Structure of New Sodium Hydrogen Sulfates Na(H₃O)(HSO₄)₂, Na₂(HSO₄)₂(H₂SO₄), and Na(HSO₄)(H₂SO₄)₂ Three acidic sodium sulfates have been synthesized from the system sodium sulfate/sulfuric acid and have been crystallographically characterized. Na(H₃O)(HSO₄)₂ ( A ) crystallizes in the space group P2₁/c with the unit cell parameters a = 6.974(2), b = 13.086(2), c = 8.080(3) Å, α = 105.90(4)°, V = 709.1 Å3, Z = 4. Na₂(HSO₄)₂(H₂SO₄) ( B ) is orthorhombic (space group Pna2₁) with the unit cell parameters a = 9.970(2), b = 6.951(1), c = 13.949(3) Å, V = 966.7 ų and Z = 4. Na(HSO₄)(H₂SO₄)₂ ( C ) crystallizes in the triclinic space group P1 with the unit cell parameters a = 5.084(1), b = 8.746(1), c = 11.765(3) Å, α = 68.86(2)°, β = 88.44(2)°, γ = 88.97(2)°, V = 487.8 Å3 and Z = 2. All three compounds contain SO₄ tetrahedra as HSO₄^? anions and additionally in B and C in form of H₂SO₄ molecules. The ratio H:SO₄ determines the connectivity degree in the hydrogen bond system. In A , there are zigzag chains and dimers additionally connected via oxonium ions. Complex chains consisting of cyclic trimers (two HSO₄^? and one H₂SO₄) are present in B . In structure C , several parallel chains are connected to columns due to the greater content of H₂SO₄. Sodium cations show a distorted octahedral coordination by oxygen in all three structures, the NaO₆ octahedra being “isolated” (connected via SO₄ tetrahedra only) in A . Pairs of octahedra with common edge form Na₂O₁₀ dimeric units in C . Such double octahedra are connected via common corners forming zigzag chains in B .     

Investigation par analyse thermique differentielle du systeme Gd2(MoO4)3-Bi2(MoO4)3

The phase diagram of the system Gd₂(MoO₄)₃-Bi(MoO₄)₃ has been studied by differential thermal analysis (DTA). Sealed platinum tubes were used as sample holders, in order to prevent the loss of Bi₂O₃ and MoO₃ through volatilization at high temperature. Various solid solutions and new phases are reported: α-Gd_2-x-Bi_x(MoO₄)₃, β -Gd_2-x-Bi_x(MoO₄)₃, α-Bi_2-xGd_x(MoO₄)₃, 3Gd₂(MoO₄)₃·2Bi₂(MoO₄)₃, etc.     

Phase equilibrium in the Cs2MoO4-Bi2(MoO4)3-Zn(MoO4)2 system and the crystal structure of new triple molybdate Cs5BiZr(MoO4)6

The subsolidus region of the Cs₂MoO₄-Bi₂(MoO₄)₃-Zr(MoO₄) system was studied by X-ray powder diffraction. Quasi-binary sections were elucidated, and triangulation performed. Triple molybdates with the component ratios 5: 1: 2 (S ₁) and 2: 1: 4 (S ₂) were prepared for the first time. Crystals of cesium bismuth zirconium molybdate of the 5: 1: 2 stoichiometry (Cs₅BiZr(MoO₄)₆) were grown from fluxed melts with spontaneous nucleation. The composition and crystal structure of this triple molybdate were refined using X-ray diffraction data (collected on X8 APEX automated diffractometer, MoK _α radiation, 2348 F(hkl), R = 0.0226). The trigonal unit cell parameters were as follows: a = b = 10.9569(2), c = 39.804(4) Å, V = 4138.4(4) ų, Z = 6, space group R $ \bar 3 The subsolidus region of the Cs₂MoO₄-Bi₂(MoO₄)₃-Zr(MoO₄) system was studied by X-ray powder diffraction. Quasi-binary sections were elucidated, and triangulation performed. Triple molybdates with the component ratios 5: 1: 2 (S ₁) and 2: 1: 4 (S ₂) were prepared for the first time. Crystals of cesium bismuth zirconium molybdate of the 5: 1: 2 stoichiometry (Cs₅BiZr(MoO₄)₆) were grown from fluxed melts with spontaneous nucleation. The composition and crystal structure of this triple molybdate were refined using X-ray diffraction data (collected on X8 APEX automated diffractometer, MoK _α radiation, 2348 F(hkl), R = 0.0226). The trigonal unit cell parameters were as follows: a = b = 10.9569(2), c = 39.804(4) ?, V = 4138.4(4) ?³, Z = 6, space group R c. The mixed-metal three-dimensional framework in this structure is built of Mo tetrahedra and two sorts of (Bi,Zr)O₆ octahedra. Large interstices accommodate two sorts of cesium atoms. The Bi³⁺ and Zr⁴⁺ cation distributions over two positions were refined during structure solution. Original Russian Text ? B.G. Bazarov, T.V. Namsaraeva, R.F. Klevtsova, A.G. Anshits, T.A. Vereshchagina, R.V. Kurbatov, L.A. Glinskaya, K.N. Fedorov, Zh.G. Bazarova, 2008, published in Zhurnal Neorganicheskoi Khimii, 2008, Vol. 53, No. 9, pp. 1585–1589.     

Synthesis,Crystal Structure,and Properties of the Sodium Molybdate Fluoride Na3MoO4F

The compound Na₃MoO₄F was synthesized by high temperature solution methods. Single‐crystal X‐ray diffraction analysis reveals that Na₃MoO₄F crystallizes in the orthorhombic space group Pnma (No. 62) with lattice constants a = 5.588(2) Å, b = 7.515(3) Å, c = 12.876(5) Å, and Z = 4. The crystal structure consists of isolated MoO₄ groups and [FNa₃]_∞ chains, which are connected by Na–O bonds to form a three‐dimensional framework. A detailed structure comparison between Na₃MoO₄F and NaMoO₃F was carried out. IR spectroscopy and bond valence sum analysis of Na₃MoO₄F indicate that the structure is reasonable. In addition, the electronic structure was investigated by the first‐principles method.     

Phase equilibria in the V2O5-NaVO3-Ca(VO3)2-Mn2V2O7 system and interactions of phases with H2SO4 and NaOH solutions

Phase composition of the V₂O₅-NaVO₃-Ca(VO₃)₂-Mn₂V₂O₇ system was studied, and a subsolidus phase diagram constructed. The tetrahedration of the diagram is determined by the fact that the end-member of Ca_1–x Mn _x (VO₃)₂ solid solution is in equilibrium with all compounds of the system (V₂O₅, NaVO₃, Ca(VO₃)₂), vanadium β-bronzes Na _x V₂O₅ (0.22 ≤ x ≤ 0.40) and κ-bronzes (0.25 ≤ x ≤ 0.45, 0 ≤ y ≤ 0.16), Mn₂V₂O₇, and Na₂Mn₃(V₂O₇)₂ and with the end-members of reciprocal solid solutions based on calcium and sodium metavanadates. At 20°C, the degree of vanadium dissolution α for Na₂Ca(VO₃)₄ is 100% for 0.5 ≤ pH ≤ 10; for the other phases of the system, vanadium dissolution ranges from 100 to 10% for pH below 3.5; in the alkaline pH range, ≤ 10%. Sodium for calcium substitution in Ca(VO₃)₂ increases α in aqueous NaOH to 20%. For Na₂Mn₃(V₂O₇)₂, α decreases from 92 to 80% as pH changes from 0.5 to 2.5; at pH above 4, α = 30%.     

Synthesis and crystal structure of new sodium oxothiocyanofluoroantimonate(III) Na2Sb5F9O3(NCS)2

Na₂Sb₅F₉O₃(NCS)₂, a new complex, has been synthesized from NaSCN and SbF₃ aqueous solutions and studied by chemical, X-ray diffraction, and thermal analyses and IR, ^121,123Sb NQR, and ¹⁹F NMR spectroscopy. Its layered structure (triclinic symmetry system, a = 6.9998(1) Å, b = 9.4180(1) Å, c = 13.1094(2) Å, α = 74.815(1)°, β = 78.188(1)°, γ = 82.779(1)°, Z = 2, space group P $\bar 1$ ) is built of Na⁺ cations and [Sb₁₀F₁₈O₆(NCS)₄]^4? decanuclear complex anions that consist of two [Sb₅F₉O₃(NCS)₂]^2? pentanuclear complex anions linked by two weak Sb-F ionic bonds (2.529(2) Å). Decanuclear complex anions are linked into layers by secondary Sb…F bonds and Na-F bonds. Van der Waals interactions link these layers into a framework. The complex is stable up to 200°C.