Ein Natrium‐Oxocobaltat(II)‐Hydroxid: Na5[CoO3]OH ≡ Na10[CoO3]{[CoO3](OH)2}

A Sodium‐Oxocobaltate(II)‐Hydroxide: Na₅[CoO₃]OH ≡ Na₁₀[CoO₃]{[CoO₃](OH)₂} Na₁₀[CoO₃]{[CoO₃](OH)₂} has been obtained from a redox reaction between cobalt metal and CdO in the presence of NaOH and Na₂O at 600 °C (21 d) as red single crystals. The structure has been determined from single crystal data (IPDS‐data, Pnma, Z = 4, a = 988.5(1) pm, b = 1013.9(2) pm, c = 1186.3(2) pm, wR2 = 0.079). Furthermore IR data and aspects of the Madelung part of the lattice energy are presented.     

Ein Natrium‐Oxocobaltat(II)‐Sulfat: Na8[CoO3][SO4]2

A Sodium Oxocobaltate(II) Sulfate: Na₈[CoO₃][SO₄]₂ Na₈[CoO₃][SO₄]₂ has been obtained from a redox reaction between cobalt metal and CdO in the presence of Na₂SO₄ and Na₂O at 550 °C (15 d) as red single crystals. The structure has been determined from single crystal data (IPDS‐data, T = 170 K, Cmcm, Z = 4, a = 806.88(9) pm, b = 2232.1(3) pm, c = 705.97(9) pm, R_all = 0.047). Magnetic properties and spectroscopic investigations are reported and discussed within the Angular‐Overlap‐Model.     

Zur Synthese und Kristallstruktur von Na10[M3O6][MO3] (M = Fe,Mn) mit einer Bemerkung zu den magnetischen Eigenschaften

Synthesis and Crystal Structure of Na₁₀[M₃O₆][MO₃] (M = Fe, Mn) with a Remark on the Magnetic Properties Single crystals of Na₁₀[M₃O₆][MO₃] (M = Mn, Fe) may be obtained via a redox reaction of CdO with the respective transition metal in the presence of Na₂O and a flux as red single crystals, which are sensitive to moisture. The crystal structure (determined from IPDS data, , Z = 6) contains isolated trigonal aplanar [MO₃] units and layers of [MO₄] tetrahedra connected via corners to three‐membered rings, which share common edges resulting in the formation of twelve‐membered rings. The statistical occupancy of 21 out of 60 sodium atoms per unit cell is discussed and calculations of the Madelung Part of the Lattice Energy (MAPLE) are given. Furthermore, we report on the magnetic properties of Na₁₀[Mn₃O₆][MnO₃] in close relation to the structural entities.     

[HN(C2H5)3][B5O6(OH)4]的合成、结构和热稳定性

利用水热法合成了五硼酸三乙胺[HN(C2H5)3][B5O6(OH)4], 并利用单晶X射线衍射技术解析了其结构, 同时利用傅立叶红外分析、元素分析及热分析技术加以佐证. 该化合物属于单斜晶系, 其空间群为P21/c, 相应的晶胞参数为a=1.0036(2) nm, b=1.1353(2) nm, c=1.4843(3) nm和β=106.54(3)°. 它由孤立的五硼酸阴离子[B5O6(OH)4]-和三乙胺阳离子[HN(C2H5)3]+构成. 五硼酸阴离子[B5O6(OH)4]-通过氢键构成三维网状结构, [HN(C2H5)3]+位于其中的孔道中.     

Zur Kenntnis eines Alkali-Erdalkalimetall-Cadmium-Oxovanadats: KBaCd2(VO4)(V2O7)

On an Alkali Alkaline-Earth Cadmium Oxovanadate: KBaCd₂(VO₄)(V₂O₇) Single crystals of KBaCd₂(VO₄)(V₂O₇) have been prepared by crystallization from melts. X-ray investigations led to monoclinic symmetry, space group C? P2₁/n, a = 10.359(3), b = 6.986(2), c = 15.331(3) Å, β = 94.77(2), Z = 4. The hitherto unknown compound represents a new structure type and is one of those few examples containing VO₄ and V₂O₇ groups.     

Cadmium in tetragonal pyramidaler Koordination im Barium-Cadmium-Oxovanadat: Ba2Cd3(VO4)2(V2O7)

Cadmium in Square Pyramids of Oxygen in the Barium Cadmium Oxovanadate: Ba₂Cd₃(VO₄)₂(V₂O₇) Single crystals of Ba₂Cd₃(VO₄)₂(V₂O₇) have been prepared by crystallization of a melt of BaCO₃, CdO and V₂O₅. It shows orthorhombic symmetry, space group D? P2₁2₁2₁, a = 7.206(2), b = 9.978(1), c = 19.617(3) Å, Z = 4. The crystal structure is characterized by (VO₄)^3? and (V₂O₇)^4? groups, CdO₆ octahedra, BaO₁₂ and BaO₉ polyhedra and with respect to Cd containing oxides unusual square pyramids of O^2? around Cd²⁺. The observed [CdO₄] zickzack chains are connected by VO₄ tetrahedra, V₂O₇ double tetrahedra and CdO₅ pyramids, forming a tunnel structure along [100]. The tunnels are filled by barium.     

新型磷-钒-氧层状化合物[H2en]2[H3O]6[Co(H2O)2(VO)8(OH)4(PO4)8]的水热合成与晶体结构

金属磷酸盐材料在吸附、离子交换、离子传导和催化剂方面有潜在的应用前景[1～5]. 近年来, 通过水热反应合成了一些A-V-P-O化合物. 在这些化合物中, A一般为碱金属或有机阳离子, 如层状结构的[H2N(C4H8)2NH2][(VO)4(OH)4(PO4)2][6] 和[H2N(C2H4)3NH2][(VO)8(HPO4)3(PO4)4*(OH)2]*2H2O[6], 一维链状结构的 [H2NCH2CH2NH3(VO)(PO4)][7], 手性双螺旋结构的 [(CH3)2NH2]K4[(VO)10(H2O)2(OH)4(PO4)7]*H2O[8]以及具有三维骨架结构的化合物 [H3N(CH2)3NH3K(VO)3(PO4)3][9], [H3N(CH2)3NH3]2[V(H2O)2(VO)6(OH)2(HPO4)3(PO4)5]*3H2O[10]和[H3N(CH2)2NH3][(VO)3(H2O)2(PO4)2(HPO4)4][11].     

Methanol als Ligand in Natriumphenolat: Darstellung und Struktur von [Na(CH3OH)4][OC6H5]

Methanol as a Ligand in Sodium Phenoxide: The Synthesis and Crystal Structure of [Na(CH₃OH)₄][OC₆H₅] By the reaction of sodium and phenol in N-methyl-?-caprolactam (NMC) sodium phenoxide has been yielded, which forms a complex with the furthermore obtained methanol of [Na(CH₃OH)₄][OC₆H₅]. The single crystals crystallize triclinic, space group P1 , with the lattice constants a = 6.613(3) Å, b = 10.537(4) Å, c = 10.656(4) Å, α = 108.27(2)°, β = 98.21(2) and γ = 95.26(2)°. Sodium is coordinated by six oxygen atoms of methanol in the form of an octahedron. These coordination polyhedrons are connected by sharing edges forming chain, whereas, the oxygen of phenoxide is not involved in the coordination of sodium. Although it is attached to the chain by hydrogen bonding.     

Ein neues Oxoberyllat: K2Na4[O2BeOBeO2]

On K₂Na₄[O₂BeOBeO₂] For the first time colourless single crystals of K₂Na₄[Be₂O₅] which are isotypic with K₂Na₄[Co₂O₅] [2] and Rb₂Na₄[Co₂O₅] have been prepared by heating e.g. a well ground mixture of K₂O, Na₂O and BeO (K:Na:Be = 2.2:4.4:2; 750°C; 21 d; Ni-tube). The crystal structure was solved by four-circle diffractometer data [Siemens AED 2; 389 I_o(hkl); space group P4₂/mnm; Z = 2; a = 595.17(4) pm, c = 1 002.66(9) pm; R = 4.1%; R_w = 2.3%]. Mean Fictive Ionic Radii, MEFIR, Effective Coordination Numbers, ECoN, the Madelung Part of Lattice Energy, MAPLE, and the charge distribution are calculated.     

An Ortho‐silicate‐hydroxide: Rb5[SiO4][OH]

Rb₅[SiO₄][OH] crystallizes in the monoclinc space group C2/m with a = 737.3(1) pm, b = 1073.7(2) pm, c = 1207.2(2) pm, β = 106.07(2)° and Z = 4 (single crystal data; R1= 0.0681 all data). Layers of edge‐connected distorted trigonal prismatic [(OH)Rb₆] entities and isolated tetrahedral [SiO₄] units present the main structural features of this unprecedented structure type.     

Polyol-Metall-Komplexe. XIII [1]. Na2[Be(C4H6O3)2] · 5H2O und Na2[Pb(C4H6O3)2] · 3H2O – zwei homoleptische Bis-polyolato-metallate mit Beryllium und mit Blei

Polyol Metal Complexes. XIII. Na₂[Be(C₄H₆O₃)₂] · 5H₂O and Na₂[Pb(C₄H₆O₃)₂] · 3H₂O – Two Homoleptic Bis Polyolato Metallates with Beryllium and with Lead Na₂[Be(C₄H₆O₃)₂] · 5H₂O ( 1 ) and Na₂[Pb(C₄H₆O₃)₂] · 3H₂O ( 2 ) crystallize from concentrated, alkaline aqueous solutions. The polyol anhydroerythritol is deprotonated twice in the mononuclear, homoleptic complex anions. The preference of beryllium for the binding of cis-furanoid diols is shown. In 2 , a stereochemically active lone pair at the central atom is the reason for the construction of low dimensional aggregates from three plumbate and three sodium ions.     

Von kleinen Bausteinen zu neuen Poly‐alkoxo‐oxometallat‐Derivaten: Synthese und Strukturaufklärung von K4[VIV12O12(OCH3)16(C4O4)6], Cs10[VIV24O24(OCH3)32(C4O4)12][VIV8O8(OCH3)16(C2O4)] und M2[VIV8O8(OCH3)16(VIVOF4)] (M = [N(nBu)4] bzw. [NEt4])

>From Small Fragments to New Poly‐alkoxo‐oxo‐metalate Derivatives: Syntheses and Crystal Structures of K₄[V^IV₁₂O₁₂(OCH₃)₁₆(C₄O₄)₆], Cs₁₀[V^IV₂₄O₂₄(OCH₃)₃₂(C₄O₄)₁₂][V^IV₈O₈(OCH₃)₁₆(C₂O₄)], and M₂[V^IV₈O₈(OCH₃)₁₆(V^IVOF₄)] (M = [N(nBu)₄] or [NEt₄]) By solvothermal reaction of ortho‐vanadicacid ester [VO(OMe)₃] with squaric acid and potassium or caesium hydroxide the compounds K₄[V^IV₁₂O₁₂(OCH₃)₁₆(C₄O₄)₆] ( 2 ) and Cs₁₀[V^IV₂₄O₂₄(OCH₃)₃₂(C₄O₄)₁₂][V^IV₈O₈(OCH₃)₁₆(C₂O₄)] ( 3 ) could be syntesized. With tetra‐n‐butyl‐ or tetra‐n‐ethylammonium fluoride [N(nBu)₄]₂[V^IV₈O₈(OCH₃)₁₆(V^IVOF₄)] ( 4 ) and [N(Et)₄]₂[V^IV₈O₈(OCH₃)₁₆(V^IVOF₄)] ( 5 ) could be isolated. In 2 and 3 the corners of a tetrahedron or cube resp. are occupied by {(VO)₃(OMe)₄} groups and connected along the edges of the tetrahedron resp. cube by six or twelve resp. squarato‐groups. The octanuclear anions in the compounds 3 , 4 , and 5 are assumedly built up by fragments of the ortho‐vanadicacid ester [VO(OMe)₃]. Around the anions C₂O₄^2— or VOF₄^— these oligormeric chains are closed to a ring . Crystal data: 2 , tetragonal, P4₃, a = 18.166(3)Å, c = 29.165(7)Å, V = 9625(3)ų, Z = 4, d_c = 1.469 gcm^—3; 3 , orthorhombic, Pbca, a = 29.493(5)Å, b = 25.564(4)Å, c = 31.076Å, V = 23430(6)ų, Z = 4, d_c = 1.892 gcm^—3; 4 , monoclinic, P2₁/n, a = 9.528(1)Å, b = 23.021(2)Å, c = 19.303(2)Å, β = 92.570(2)°, V = 4229.8(5)ų, Z = 2, d_c = 1.391 gcm^—3; 5 , monoclinic, P2₁/n, a = 16.451(2)Å, b = 8.806(1)Å, c = 23.812(1)Å, β = 102.423(2)°, V = 3368.7(6)ų, Z = 2, d_c = 1.534 gcm^—3.     

Synthesis, Structure Characterization and Biological Activity of Layered Vanadium Oxides [ NH3 （ CH2 ）2 NH （ CH2 ）2 NH3 ] [ V6 O14 ]

Introduction Over the past decades, polyoxometalates(POMs)have been attracting extensive interestowing to the widerange of their topological properties and potential appli-cations in catalysis, photochemistry, electrochromism,and magnetism[1,2]. Meanwhile, owing to the potentialapplication of polyoxometalaes as anticancer and antivi-ral drugs, their complexes have attracted increasing in-terest of both inorganic chemists and biochemists[3]. Itis well known that polyoxometalates are excellent …     

A New Example of the Structure Type A2[{Z2R4}X9]: Synthesis and Crystal Structure of Na2[{(ON)Ce4}Cl9]

First single crystals of Na₂[{(ON)Ce₄}Cl₉] were obtained during synthesis attempts for the cerium nitride chloride Ce₂NCl₃(= {N₂Ce₄}Cl₆). With a molar ratio of 8:10:3 for Ce, CeCl₃ and NaN₃ along with an excess of the flux NaCl, the mixture obviously contained a small amount of CeOCl that led to the formation of quinary Na₂[{(ON)Ce₄}Cl₉]. It crystallizes in the monoclinic space group P2₁/m(no. 11) with two formula units in the unit cell with dimensions of a = 813.21(6) pm, b = 1146.13(9) pm, c = 942.86(7) pm and β = 107.504(5) °. As the dominating structural feature {ZCe₄}^9.5+ tetrahedra are fused through trans‐oriented edges to generate chains (Z = ¹/₂ O + ¹/₂ N) just as in the structurally isotypic compounds A₂[{Z₂R₄}X₉] (A = Na, K; R = Pr, Nd, Gd; X = Cl, Br; Z = O, O/N).     

Die Kristallstrukturen der Polytelluride [Ca(DMF)6]Te4, [Sr(15-Krone-5)2]Te4 · H2O, {[BaCl(18-Krone-6)(DMF)2]2[BaCl(18-Krone-6)(DMF) (H2O)]2(Te4)2} und [Ph3PNPPh3]2Te5 · 2 DMF

Crystal Structures of the Polytellurides [Ca(DMF)₆]Te₄, [Sr(15-Crown-5)₂]Te₄ · H₂O, {[BaCl(18-Crown-6)(DMF)₂]₂[BaCl(18-Crown-6)(DMF) (H₂O)]₂(Te₄)₂}, and [Ph₃PNPPh₃]₂Te₅ · 2 DMF The title compounds were formed by alkalimetal polytelluride solutions in dimethylformamide (DMF) in the presence of the corresponding counter ions as well as in the presence of 15-crown-5 or 18-crown-6. Single crystals were obtained upon using additional diethylether. [Ca(DMF)₆]Te₄: Space group C2/c, Z = 4, 1024 observed unique reflections, R = 0.055. Lattice dimensions at ?70°C: a = 1776.1; b = 813.0 c = 2545.9pm; β = 102.90°. The compound consists of centrosymmetric [Ca(DMF)⁶]²⁺ ions, in which the calcium ions are octahedrally coordinated by the six oxygen atoms of the DMF molecules, and chain-like Te [Sr)15-crown-5)₂]Te₄ · H₂O: Space group C2/c, Z = 4, 3322 observed unique reflections, R = 0.058. Lattice dimensions at ?70°C: a = 1450.5; b = 1407.3; c = 1660.9 pm; β = 110.22°. The compounds forms centrosymmetric cations [Sr(15-crown-5) ₂]²⁺, in which the Sr²⁺ ion is sandwich-like surrounded by the ten oxygen atoms of the crown ether molecules, and chain-like Te₄^2? ions, which are associated in the lattice forming polymeric chains. {[BaCl(18-crown-6)(DMF) ₂]₂[BaCl(18-crown-6)(DMF)· (H₂O)] ₂(Te₄)₂}: Space group P1 , Z = 1, 3189 observed unique reflections, R = 0.054. Lattice dimensions at 19°C: a = 986.1; b = 1052.8; c = 2696.4 pm; α = 89.34°; β = 88.68°; γ = 89.56°. The compound consists of chain-like Te ions without symmetry and of the two somewhat different cations [BaCl(18-crown-6)(DMF) ₂]₂²⁺, in which the Ba²⁺ ions dimerize via centroysmmetric rings. Along with the six oxygen atoms of the crown ether molecules and the oxygen atoms of the DMF molecules, the oxygen atoms of the DMF and water molecule, respectively, the Ba⁺ ions achieve coordination number ten. [Ph₃PNPPh₃]₂Te₅ · 2DMF: Space group Pc, Z = 2, 5971 observed unique reflections, R = 0.058. Lattice dimensions at 20°C: a = 20°C: a = 1085.2; b = 1287.0; c = 2715.9 pm; β = 90.19°. The compounds consists of [Ph₃PNPPh₃]₊ ions, chain-like Te₅^2? ions, and incorporate DME molecules without bonding interaction. The ₅^2? ions are associate via polymeric chains in which left- and right handed individuals are alternating.     

Synthese und Kristallstrukturen der Seltenerd-Komplexe [LaI2(THF)5]+I3−, [SmCl3(THF)4], [ErCl2(THF)5]+ [ErCl4(THF)2]−, [ErCl3(DME)2] und [Na(18-Krone-6)(THF)2]+ [YbBr4(THF)2]−

Syntheses and Crystal Structures of the Rare-Earth Complexes [LaI₂(THF)₅]⁺I₃^?, [SmCl₃(THF)₄], [ErCl₂(THF)₅]⁺ [ErCl₄(THF)₂]^?, [ErCl₃(DME)₂], and [Na(18-Crown-6)(THF)₂]⁺[YbBr₄(THF)₂]^? [LaI₂(THF)₅]⁺I₃^? ( 1 ) is obtained as red crystals from lanthanum powder and 1,2-diiodoethane in THF on exposure to light. Space group Pbcn, Z = 4, lattice dimensions at ?83°C: a = 1264.9, b = 2218.9, c = 1199.1 pm, R = 0.031. The lanthanum atom of the cation of 1 is coordinated with iodine atoms in the axial positions in a pentagonal-bipyramidal way. [SmCl₃(THF)₄] ( 2 ) originates as colourless crystals on heating SmCl₃ with excess THF in the presence of Me₃SiNPEt₃. Space group P2₁/c, Z = 8, lattice dimensions at ?50°C: a = 3092.7, b = 826.2, c = 1758.3 pm, β = 93.85°, R = 0.054. Just like the known sample that crystallizes within the space group F2dd, 2 forms monomeric molecules in which the samarium atom is coordinated with two chlorine atoms in the axial positions in a distorted pentagonal-bipyramidal way. [ErCl₂(THF)₅]⁺[ErCl₄(THF)₂]^? ( 3 ). Pale pink single crystals of 3 were prepared according to the described method by reaction of erbium powder with trimethylchlorosilane and methanol in THF. Space group C2/c, Z = 4, lattice dimensions at ?50°C: a = 1246.3, b = 1145.7, c = 2726.0 pm, β = 91.293°, R = 0.036. The erbium atom of the cation of 3 has a pentagonal-bipyramidal coordination with the chlorine atoms in the axial positions. Within the anion the THF molecules are in trans-arrangement of the octahedrally coordinated erbium atom. [ErC1₃(DME)₂] ( 4 ) originates as pink single crystals from ₃ with excess boiling 1,2-dimethoxyethane. Space group P2₁/c, Z = 4, lattice dimensions at ?50°C: a = 1137.2, b = 886.5, c = 1561.1 pm, β = 104.746°, R = 0.032. 4 forms monomeric molecules in which the erbium atom has a pentagonal-bipyramidal surrounding with two chlorine atoms in the axial positions. [Na(18-Krone-6)(THF)₂]⁺ [YbBr₄(THF)₂]^? ( 5 ) is formed as by-product by the reaction of YbBr₃ with NaN(SiMe₃)₂ in THF in the presence-of 18-crown-6 forming colourless crystals. Space group P1 , Z = 1, lattice dimensions at ?70°C: a = 934.6, b = 988.9, c = 1208.0 pm, α = 73.82°, β = 72.98°, γ = 76.89°, R = 0.029. 5 contains isolated [YbBr₄(THF)₂]^?ions, in which the THF molecules are arranged in trans-position.     

Synthesis and characterization of Na11[CuO4][SO4]3

Na₁₁[CuO₄][SO₄]₃ was obtained from a redox reaction of CuO with Na₂O₂ in the presence of Na₂O and Na₂SO₄ in sealed Ag containers under Ar atmosphere at 600°C. The crystal structure has been determined from X-ray single crystal data at 293 and 170 K (Pnma, Z=4). The lattice parameters have been refined from X-ray powder data at 293 K as well: a=1597.06(6) pm, b=703.26(3) pm, c=1481.95(6) pm. The structure contains isolated distorted square-planar [CuO₄]⁵⁻ anions and non-coordinating sulfate groups. Furthermore, we report calculations of the Madelung Part of the Lattice Energy (MAPLE) and some of the physical properties of Na₁₁[CuO₄][SO₄]₃.     

Three New Thioantimonates(V): Solvothermal Syntheses and Crystal Structures of [M(chxn)3]3(SbS4)2·4H2O (M = Ni,Co) and [Co(dien)2][Co(tren)SbS4]2·4H2O

The three new thioantimonates(V) [Ni(chxn)₃]₃(SbS₄)₂·4H₂O ( I ), [Co(chxn)₃]₃(SbS₄)₂·4H₂O ( II ) (chxn is trans‐1,2‐diaminocyclohexane) and [Co(dien)₂][Co(tren)SbS₄]₂·4H₂O ( III ) (dien is diethylenetriamine and tren is tris(2‐aminoethyl)amine) were synthesized under solvothermal conditions. Compounds I and II are isostructural crystallizing in space group C2/c. The structures are composed of isolated [M(chxn)₃]²⁺ complexes (M = Ni, Co), [SbS₄]^3? anions and crystal water molecules. Short S···N/S···O/O···O separations indicate hydrogen bonding interactions between the different constituents. Compound III crystallizes in space group and is composed of [Co(dien)₂]²⁺ and [Co(tren)SbS₄]^? anions and crystal water molecules. In the cationic complex the Co²⁺ ion is in an octahedral environment of two dien ligands whereas in [Co(tren)SbS₄]^? the Co²⁺ ion is in a trigonal bipyramidal coordination of four N atoms of tren and one S atom of the [SbS₄]^3? anion, i.e., two different coordination polyhedra around Co²⁺ coexist in this compound. Like in the former compounds an extended hydrogen bonding network connects the complexes and the water molecules into a three‐dimensional network.     

新型化合物[Ni(en)2V6O14]n的水热合成与晶体结构

金属 -氧簇合物在催化吸附、医药临床、能量存储和材料科学等方面的应用越来越受到关注 [1～ 3 ] .钒 -氧簇合物的结构新颖 ,在材料领域中具有广泛的应用前景 .采用水热合成技术 ,以简单的无机、有机起始原料在相对低温下制备金属 -氧簇合物晶体是近年来刚刚兴起的研究工作 [4 ] ,并且已经合成出一维链状化合物 Cu(prn) 2 V2 O6[5]、层状结构 Ni(C10 H8N2 ) 2 V3 O8.5[6]及三维网状结构 (H2 en Me)[Ni(en) 2 V12 O2 8][7] .我们采用水热技术合成了由 { V V 2 O7} n 单元层与桥配体 [Ni(en) 2 ]2 +构建的三维无机 -有机化合物 [Ni(en…     

Na3F[WO4]: A Sodium Fluoride Ortho‐Oxotungstate(VI) with Strands of Face‐Shared Fluoride‐Centred Sodium Octahedra According to $^{1}_{\infty}\rm \{[FNa_{6/2}]^{2+}\}$

During the reaction of Na₂[WO₄] with YF₃ purposed to yield fluoride‐derivatized yttrium oxotungstates(VI), colourless platelet‐shaped single crystals of Na₃F[WO₄] emerged as main product. The title compound crystallizes orthorhombically in the space group Pnma (a = 559.59(5), b = 751.02(7), c = 1285.98(9) pm) with four formula units per unit cell. Besides isolated ortho‐oxotungstate units [WO₄]^2? (d(W–O) = 176–178 pm) the crystal structure contains two crystallographically independent Na⁺ cations which are both octahedrally coordinated by four oxygen atoms and two fluoride anions. The F^? anions are surrounded by six sodium cations (d(F–Na) = 224–242 pm) also in an octahedral fashion. These octahedra built up chains along [100] by sharing trans‐oriented faces according to , which are stacked according to a hexagonal closest rod‐packing. The cationic strands are surrounded, interconnected and charge‐balanced by isolated [WO₄]^2? tetrahedra with almost ideal shape and every O^2? ligand is terminally coordinated by three Na⁺ cations.