Synthesis and Crystal Structure of the Nitridosilicates Ca5[Si2N6] and Ca7[NbSi2N9]

Ca₅[Si₂N₆] and Ca₇[NbSi₂N₉] were obtained by reaction of Ca₃N₂, Ca₂N and Si₃N₄ (with addition of niobium powder in case of Ca₇[NbSi₂N₉]) in closed tantalum ampoules at temperatures at 1060 °C and 1000 °C, respectively. Ca₅[Si₂N₆] is monoclinic C2/c with a = 983.6(2) pm, b = 605.2(1) pm, c = 1275.7(3), β = 100.20(3)° and Z = 4 crystallising homotypically to Ba₅[Si₂N₆]. The crystal structure contains pairs of edgesharing SiN₄ tetrahedra forming isolated nitridosilicate anions of [Si₂N₆]^10?. Ca₇[NbSi₂N₉] is monoclinic P2₁/m with a = 605.1(1), b = 994.6(2), c = 899.7(2), β = 92.10(1)°, Z = 2 and crystallises in an hitherto unknown structure type. Ca₇[NbSi₂N₉] contains isolated anions [NbSi₂N₉]^14? which are composed of two edgesharing SiN₄ tetrahedra and an edge‐sharing NbN₅ pyramid. So far, such a pseudotrisilicate unit has not been observed in the family of silicates.     

Solvothermal Synthesis and Crystal Structures of Two Thioantimonate(V) Compounds with the [SbS4]3— Anion Acting as a Monodentate Ligand: [Mn(C6H18N4)(C6H19N4)]SbS4 and [Mn(C6H14N2)3]2[Mn(C6H14N2)2(SbS4)2]·6H2O

The two novel thioantimonate(V) compounds [Mn(C₆H₁₈N₄)(C₆H₁₉N₄)]SbS₄ ( I ) and [Mn(C₆H₁₄N₂)₃][Mn(C₆H₁₄N₂)₂(SbS₄)₂]·6H₂O ( II ) were synthesized under solvothermal conditions by reacting elemental Mn, Sb and S in the stoichiometric ratio in 5 ml tris(2‐aminoethyl)amine (tren) at 140 °C or chxn (trans‐1, 2‐diaminocyclohexane, aqueous solution 50 %) at 130 °C. Compound I crystallises in the triclinic space group P1¯, a = 9.578(2), b = 11.541(2), c = 12.297(2)Å, α = 62.55(1), β = 85.75(1), γ = 89.44(1)°, V = 1202.6(4)ų, Z = 2, and II in the monoclinic space group C2/c, a = 32.611(2), b = 13.680(1), c = 19.997(1)Å, β = 117.237(5)°, V = 7931.7(8)ų, Z = 4. In I the Mn²⁺ cation is surrounded by one tetradentate tren molecule, one protonated tren acting as a monodentate ligand and a monodentate [SbS₄]^3— anion yielding a distorted octahedral environment. In II one unique Mn²⁺ ion is in an octahedral environment of three bidentate chxn molecules and the second independent Mn²⁺ ion is coordinated by two chxn ligands and two monodentate [SbS₄]^3— units leading to a distorted octahedral surrounding. The compounds were investigated and characterized with thermal and spectroscopic methods.     

Ca3[BN2]I3: The First Halide‐Rich Alkaline Earth Nitrido­borate with Isolated [BN2]3– Units

The title compound Ca₃[BN₂]I₃ was obtained from reactions of mixtures of the starting materials Ca₃[BN₂]₂ and CaI₂ in a 1:4 ratio in sealed Nb tubes at 1223 K. The crystal structure was solved from powder synchrotron diffraction data. Ca₃[BN₂]I₃ is the first example of a halide‐rich nitridoborate crystallizing in the rhombohedral space group R32 [no. 155, Pearson code: hR96; Z = 12; a = 16.70491(2) Å, c = 12.41024(2) Å]. The crystal structure is built up by two interpenetrating networks of condensed edge‐sharing [BN₂]@Ca₆ and [□]@I₆ trigonal antiprisms (□ = void). In Ca₃[BN₂]I₃ two crystallograhically distinct [BN₂]^3– anions are present with d(B1–N) = 1.393(2) Å and d(B2–N) = 1.369(9) Å. Their bond angles are practically linear, varying only slightly: N–B1–N = 179(1)° and N–B2–N = 180°. Vibrational spectra were interpreted based on the D_∞h symmetry of the discrete linear [N–B–N]^3– moieties, considering the site symmetry reduction and the presence of two distinct [BN₂]^3– groups.     

Control of Oxidation States of Transition Elements (Cr,Mn) in Nitridometalates and the Solid Solution Series Li6(Ca1‐xSrx)2[Mn2N6]

The formation of ternary nitridometalates from the elements in the case of the systems Li—Cr, V, Mn—N leads to compounds which contain the transition metals in the highest (V^V, Cr^VI) or a comparably high (Mn^V) oxidation state. In the corresponding calcium and strontium systems, the transition metals show a lower oxidation state (V^III, Cr^III, Mn^III). Transition metals with intermediate oxidation states (Cr^V, Mn^IV) are present in the quaternary (mixed cation) compounds Li₄Sr₂[CrN₆], Li₆Ca₂[MnN₆], and Li₆Sr₂[MnN₆] (R3¯(#148), a = 585.9(3) pm, c = 1908.6(4) pm, Z = 3), as well as in the solid solution series Li₆(Ca_1—xSr_x)₂[MnN₆].     

Ca2[BN2]H: The First Nitridoborate Hydride — Synthesis,Crystal Structure,and Vibrational Spectra

Ca₂[BN₂]H was synthesized from a mixture of the binary components Ca₃N₂, CaH₂ and BN (molar ratio 1 : 1 : 2) in a sealed steel ampoule encapsulated in an evacuated silica tube at 1273 K. Ca₂[BN₂]H crystallizes in the orthorhombic space group Pnma (no. 62) with a = 9.2015(8)Å, b = 3.6676(2)Å and c = 9.9874(12)Å (Z = 4; Pearson symbol oP24). The crystal structure is a filled variant of the Co₂P type and can be formulated as Co₂P(□^t)₃(□^py)₃ ≡ Ca₂[N—B—N]H(□^t)₂(□^py)₃ (□^t and □^py = tetrahedral and square‐pyramidal hole, respectively). The d(B—N) bond lengths and bond angle for the linear [N—B—N]^3— anion are: d(B—N1) = 1.324(3)Å, d(B—N2) = 1.350(2)Å and ∠N—B—N = 177.2(2)°. The vibrational spectra of Ca₂[BN₂]H confirm the presence of [N—B—N]^3— groups deviating only slightly from the ideal D_∞h symmetry. The vibrational frequencies and the ?(B—N) force constants are discussed and compared with those of the isotypic compound Ca₂[BN₂]F.     

Struktur und magnetische Eigenschaften von Bis{3‐amino‐1,2,4‐triazolium(1+)}pentafluoromanganat(III): (3‐atriazH)2[MnF5]

Structure and Magnetic Properties of Bis{3‐amino‐1,2,4‐triazolium(1+)}pentafluoromanganate(III): (3‐atriazH)₂[MnF₅] The crystal structure of (3‐atriazH)₂[MnF₅], space group P1, Z = 4, a = 8.007(1) Å, b = 11.390(1) Å, c = 12.788(1) Å, α = 85.19(1)°, β = 71.81(1)°, γ = 73.87(1)°, R = 0.034, is built by octahedral trans‐chain anions [MnF₅]^2–_∞ separated by the mono‐protonated organic amine cations. The [MnF₆] octahedra are strongly elongated along the chain axis (<Mn–F_ax> 2.135 Å, <Mn–F_eq> 1.842 Å), mainly due to the Jahn‐Teller effect, the chains are kinked with an average bridge angle Mn–F–Mn = 139.3°. Below 66 K the compound shows 1D‐antiferromagnetism with an exchange energy of J/k = –10.8 K. 3D ordering is observed at T_N = 9.0 K. In spite of the large inter‐chain separation of 8.2 Å a remarkable inter‐chain interaction with |J′/J| = 1.3 · 10^–5 is observed, mediated probably by H‐bonds. That as well as the less favourable D/J ratio of 0.25 excludes the existence of a Haldene phase possible for Mn³⁺ (S = 2).     

Inverse-Tunable Red Luminescence and Electronic Properties of Nitridoberylloaluminates Sr2−xBax[BeAl3N5]:Eu2+ (x=0–2)

The nitridoberylloaluminate Ba₂[BeAl₃N₅]:Eu²⁺ and solid solutions Sr_2−xBa_x[BeAl₃N₅]:Eu²⁺ (x=0.5, 1.0, 1.5) were synthesized in a hot isostatic press (HIP) under 50 MPa N₂ atmosphere at 1200 °C. Ba₂[BeAl₃N₅]:Eu²⁺ crystallizes in triclinic space group (no. 2) (Z=2, a=6.1869(10), b=7.1736(13), c=8.0391(14) Å, α=102.754(8), β=112.032(6), γ=104.765(7)°), which was determined from single-crystal X-ray diffraction data. The lattice parameters of the solid solution series have been obtained from Rietveld refinements and show a nearly linear dependence on the atomic ratio Sr : Ba. The electronic properties and the band gaps of M₂[BeAl₃N₅] (M=Sr, Ba) have been investigated by a combination of soft X-ray spectroscopy and density functional theory (DFT) calculations. Upon irradiation with blue light (440–450 nm), the nitridoberylloaluminates exhibit intense orange to red luminescence, which can be tuned between 610 and 656 nm (fwhm=1922–2025 cm⁻¹ (72–87 nm)). In contrast to the usual trend, the substitution of the smaller Sr²⁺ by larger Ba²⁺ leads to an inverse-tunable luminescence to higher wavelengths. Low-temperature luminescence measurements have been performed to exclude anomalous emission.     

The Sodium (Iso)Cyanurates Nax[H3–xC3N3O3]·yH2O (x = 1–3, y = 0, 1): A Key‐Series for Understanding the Crystal Chemistry of Metal (Iso)Cyanurates

The (iso)cyanurates Na[H₂C₃N₃O₃] · H₂O, Na₂[HC₃N₃O₃] · H₂O, Na₂[HC₃N₃O₃], and Na₃[C₃N₃O₃] were synthesized phase pure from Na₂CO₃ · 10H₂O, NaOH, and cyanuric acid, respectively, in aqueous solution by carefully adjusting the crystallization conditions. The crystal structures of all compounds were determined by single‐crystal X‐ray diffraction {Na₂[HC₃N₃O₃] · H₂O: P1 , a = 3.51660(10) Å, b = 7.8300(3) Å, c = 11.3966(4) Å, α = 86.4400(10)°, β = 85.5350(10)°, γ = 85.0720(10)°, Z = 2, R₁ = 0.030, wR₂ = 0.078; Na₂[HC₃N₃O₃]: Pnma, a = 6.3409(6) Å, b = 12.2382(13) Å, c = 6.5919(7) Å, Z = 4, R₁ = 0.045, wR₂ = 0.079; Na₃[C₃N₃O₃]: R3 c, a = 11.7459(3) Å, c = 6.5286(3) Å, Z = 3, R₁ = 0.039, wR₂ = 0.066}. The structures show ribbons (Na[H₂C₃N₃O₃] · H₂O), dimers (Na₂[HC₃N₃O₃] · H₂O), chains (Na₂[HC₃N₃O₃]), or columns (Na₃[C₃N₃O₃]) of hydrogen‐bonded and parallel stacked (iso)cyanurate anions. These motifs are shown to be characteristic for certain degrees of protonation and hydration, and all (iso)cyanurate crystal structures found so far were classified accordingly. X‐ray powder patterns, thermogravimetry curves, IR and UV/Vis spectra were measured for all compounds.     

Aquachloro[N,N′‐ethylenebis(salicylideneiminato)]manganese(III)

The title compound, aqua­chloro{2,2′‐[1,2‐ethanediyl­bis­(nitrilo­methyl­idyne)]­diphenolato‐κ⁴O,N,N′,O′}manganese(III),[MnCl(C₁₆H₁₄N₂O₂)(H₂O)], is a neutral manganese(III) complex with a pseudo‐octahedral metal centre. The equatorial plane comprises the four donor atoms of the tetradentate Schiff base ligand [Mn—O 1.886 (4) and 1.893 (4) Å, and Mn—N 1.978 (5) and 1.982 (5) Å], with a water mol­ecule [Mn—O 2.383 (4) Å] and a Cl^? ligand [Mn—Cl 2.4680 (16) Å] completing the coordination sphere. The distorted geometry is highlighted by the marked displacement of the Mn^III ion out of the least‐squares plane of the four Schiff base donor atoms by 0.165 (2) Å. These monomeric Mn^III centres are then linked into a polymeric array via hydrogen bonds between the coordinated water mol­ecule and the phenolic O‐atom donors of an adjacent Mn^III centre [O—H?O 2.789 (5) and 2.881 (5) Å].     

Li4Ca3Si2N6 and Li4Sr3Si2N6 – Quaternary Lithium Nitridosilicates with Isolated [Si2N6]10– Ions

The isotypic nitridosilicates Li₄Ca₃Si₂N₆ and Li₄Sr₃Si₂N₆ were synthesized by reaction of strontium or calcium with Si(NH)₂ and additional excess of Li₃N in weld shut tantalum ampoules. The crystal structure, which has been solved by single‐crystal X‐ray diffraction (Li₄Sr₃Si₂N₆: C2/m, Z = 2, a = 6.1268(12), b = 9.6866(19), c = 6.2200(12) Å, β = 90.24(3)°, wR₂ = 0.0903) is made up from isolated [Si₂N₆]^10– ions and is isotypic to Li₄Sr₃Ge₂N₆. The bonding angels and distances within the edge‐sharing [Si₂N₆]^10– double‐tetrahedra are strongly dependent on the lewis acidity of the counterions. This finding is discussed in relation to the compounds Ca₅Si₂N₆ and Ba₅Si₂N₆, which also exhibit isolated [Si₂N₆]^10– ions.     

NaSc3[HPO3]2[HPO2(OH)]6: Synthesis,Crystal Structure,and Thermal Decomposition

NaSc₃[HPO₃]₂[HPO₂(OH)]₆ was prepared by use of a phosphorus acid flux route. The crystal structure was determined from single‐crystal X‐ray diffraction data: triclinic, space group P$\bar{1}$ (No. 2), a = 7.4507(11) Å, b = 9.6253(17) Å, c = 9.6141(16) Å, α = 115.798(4)°, β = 101.395(4)°, γ = 101.136(3)°, V = 577.29(16) Å³ and Z = 1. The crystal structure of NaSc₃[HPO₃]₂[HPO₂(OH)]₆ contains two kinds of phosphate(III) groups: HPO₃^2– and HPO₂(OH)^–. Phosphate(III)‐tetrahedra, NaO₆ and ScO₆ octahedra together form a (3,6)‐connected net. During heating hydrogen and water are released and Sc[PO₃]₃ is formed as the main crystalline decomposition product.     

Ca3Mn2O7

The tricalcium dimanganese heptaoxide (Ca₃Mn₂O₇) member of the Ruddlesden–Popper series Ca_n+1Mn_nO_3n+1, i.e. with n = 2, was previously reported with an I‐centred tetragonal lattice [a_t = 3.68 and c_t = 19.57 Å] by Fawcett, Sunstrom, Greenblatt, Croft & Ramanujachary [Chem. Mater. (1998), 10 , 3643–3651]. It is now found to be orthorhombic, with an A‐­centred lattice [a = 5.2347 (6), b = 5.2421 (2) and c = 19.4177 (19) Å]. The structure has been refined in space group A2₁am using X‐ray single‐crystal diffraction data and assuming the existence of twin domains related by the (10) plane. A comparison with the basic perovskite structure CaMnO₃ (n = ∞) is proposed.     

K6[Mn2O6] und K6[Fe2 O6] - ein Vergleich

K₆[Mn₂O₆] and K₆[Fe₂O₆] - a Comparison K₆[Mn₂O₆] has been prepared (dark-red single crystals). The structure (a = 8.88₆, b = 6.76₀, c = 11.39₄ Å, γ = 132.1°, space group P2₁, Z = 2, 1151 symmetry independent reflections hk0–hk9, R = 0.051) shows Al₂Cl₆-like anions [Mn₂O₆]^6?. By unit-cell transformation to the monoclinic setting P2₁/a (a = 6.76₀, b = 11.39₄, c = 6.63₈ Å, β = 96,9°) the structural similarity to K₆[Fe₂O₆] becomes evident. The Madelung Part of Lattice Energy, MAPLE, is calculated.     

Das erste Oxomanganat(II): Na14Mn2O9 = Nal4[MnO14]2O

The First Oxomanganate(II): Na₁₄Mn₂O₉ = Na₁₄[MnO₄]₂O Na₁₄Mn₂O₉ crystallizes trigonal, space group P3 , a = b = 6.66₉, c = 9.35₃ Å. The crystal structure han been refined by diffractometer data (1124 undependent reflections) to R = 0.050. Mn²⁺ is surrounded tetrahedrally (Mn? O = 2.09 Å). Effective Coordination Numbers, ECoN, and the Madelung Part of Lattice Energy, MAPLE, are calculated. Na₁₄Mn₂O₉ represents the most kation-rich ternary oxid of the alkali metals.     

Synthesis and Thermal Behaviour of Compounds in the System [Ph4P]Cl/BiCl3 and the Crystal Structures of [Ph4P]3[Bi2Cl9] · 2 CH2Cl2 and [Ph4P]2[Bi2Cl8] · 2 CH3COCH3

Six polynuclear chlorobismuthates are formed in the reaction between BiCl₃ and Ph₄PCl by variation of the molar ratio of the educts, the solvents and the crystallisation methods: [Ph₄P]₃[Bi₂Cl₉] · 2 CH₂Cl₂, [Ph₄P]₃[Bi₂Cl₉] · CH₃COCH₃, [Ph₄P]₂[Bi₂Cl₈] · 2 CH₃COCH₃, [Ph₄P]₄[Bi₄Cl₁₆] · 3 CH₃CN, [Ph₄P]₄[Bi₆Cl₂₂], and [Ph₄P]₄[Bi₈Cl₂₈]. We report the crystal structure of [Ph₄P]₃[Bi₂Cl₉] · 2 CH₂Cl₂ which crystallises with triclinic symmetry in the S. G. P1 No. 2, with the lattice parameters a = 13.080(3) Å, b = 14.369(3) Å, c = 21.397(4) Å, α = 96.83(1)°, β = 95.96(1)°, γ = 95.94(2)°, V = 3943.9(1) ų, Z = 2. The anion is formed from two face‐sharing BiCl₆‐octahedra. [Ph₄P]₂[Bi₂Cl₈] · 2 CH₃COCH₃ crystallises with monoclinic symmetry in the S. G. P2₁/n, No. 14, with the lattice parameters a = 14.045(5) Å, b = 12.921(4) Å, c = 17.098(3) Å, β = 111.10(2)°, V = 2894.8(2) ų, Z = 2. The anion is a bi‐octahedron of two square‐pyramids, joined by a common edge. The octahedral coordination is achieved with two acetone ligands. [Ph₄P]₄[Bi₄Cl₁₆] · 3 CH₃CN crystallises in the triclinic S. G., P1, No. 2, with the lattice parameters a = 14.245(9) Å, b = 17.318(6) Å, c = 24.475(8) Å, α = 104.66(3)°, β = 95.93(3)°, γ = 106.90(4)°, V = 5486(4) ų, Z = 2. Two Bi₂Cl₈ dimers in syn‐position form the cubic anion. Lattice parameters of [Ph₄P]₃[Bi₂Cl₉] · CH₃COCH₃ are also given. The solvated compounds are desolvated at approximately 100 °C. [Ph₄P]₃[Bi₂Cl₉] · 2 CH₂Cl₂ and [Ph₄P]₃[Bi₂Cl₉] · CH₃COCH₃ show the same sequence of phase transitions after desolvation. All compounds melt into a liquid in which some order is observed and transform on cooling into the glassy state.     

The Phase Diagram of the System [Ph4P]Br/BiBr3. Synthesis,Crystal Structure,Thermal Behaviour,and Vibrational Spectra of [Ph4P]3[Bi2Br9] · CH3COCH3 and two Modifications of [Ph4P]4[Bi6Br22]

The phase diagram of the system [Ph₄P]Br/BiBr₃ was investigated with the aid of DSC, TG and temperature dependent X‐ray powder diffraction measurements. By varying the reaction conditions, stoichiometry and crystallisation conditions of the reaction between BiBr₃ and [Ph₄P]Br four polynuclear bromobismuthates are formed. We report here the crystal structure of the solvation product [Ph₄P]₃[Bi₂Br₉] · CH₃COCH₃, which crystallises with monoclinic symmetry in the S. G. P2₁/n No. 14, a = 12.341(1), b = 32.005(3), c = 19.929(3) Å, β = 99.75(2)°, V = 7758(7) ų, Z = 4 and the crystal structures of two modifications of the compound [Ph₄P]₄[Bi₆Br₂₂]. The α‐form, crystallises with triclinic symmetry in the S. G. P1 No. 2, a = 13.507(4) Å, b = 14.434(4) Å, c = 17.709(5) Å, α = 81.34(2)°, β = 72.42(2)°, γ = 72.53(2)°, V = 3132.7(1) ų, Z = 2. The high‐temperature β‐form, crystallises with triclinic symmetry in the S. G. P1 No. 2, a = 13.893(4) Å, b = 14.267(3) Å, c = 16.580(3), α = 100.13(2)°, β = 96.56(2)°, γ = 110.01(2)°, V = 2985.5(1) ų, Z = 2. Lattice parameters of [Ph₄P]₄[Bi₈Br₂₈] are also given. The thermal behaviour of the compounds and in addition the vibrational spectra of [Ph₄P]₃[Bi₂Br₉] · CH₃COCH₃ are presented and discussed.     

一个新颖的由Zn配合物修饰的Keggin型钴钨酸盐：[Zn(2,2’-bipy)3]3{[Zn(2,2’-bipy)2(H2O)]2 [HCoW12O40] 2 }.H2O

通过水热合成技术,一个新颖的基于Zn配合物修饰的Keggin型钴钨酸的有机-无机杂化化合物：[Zn(2,2’-bipy)3]3{[Zn(2,2’-bipy)2(H2O)]2 [HCoW12O40] 2 }.H2O已经被合成,化合物通过红外光谱、热重分析和单晶X-射线衍射进行了表征。单晶X-射线衍射的结果显示标题化合物是由一个单支撑的{[Zn(2,2’-bipy)2(H2O)]2 [HCoW12O40] 2}6-多阴离子,三个[Zn(2,2’-bipy)3]2+阳离子和一个水分子构成。有趣的是[Zn(1)(2,2’-bipy)3]2+阳离子通过氢键连接在一起形成螺旋链。另外标题化合物在空气中是稳定的,并且在室温下显示了强的荧光。     

A candidate for a single‐chain magnet: [Mn3(OAc)6(py)2(H2O)2]n (OAc is acetate and py is pyridine)

The title complex, catena‐poly[di‐μ₃‐acetato‐κ⁶O:O:O′‐tetra‐μ₂‐acetato‐κ⁴O:O;κ⁴O:O′‐diaquabis(pyridine‐κN)trimanganese(II)], [Mn₃(CH₃COO)₆(C₆H₅N)₂(H₂O)₂]_n, is a true one‐dimensional coordination polymer, in which the Mn^II centres form a zigzag chain along [010]. The asymmetric unit contains two metal centres, one of which (Mn1) lies on an inversion centre, while the other (Mn2) is placed close to an inversion centre on a general position. Since all the acetates behave as bridging ligands, although with different μ₂‐ and μ₃‐coordination modes, a one‐dimensional polymeric structure is formed, based on trinuclear repeat units (Mn1...Mn2...Mn2′), in which the Mn2 and Mn2′ sites are related by an inversion centre. Within this monomeric block, the metal–metal separations are Mn1...Mn2 = 3.36180 (18) Å and Mn2...Mn2′ = 4.4804 (3) Å. Cation Mn1, located on an inversion centre, displays an [MnO₆] coordination sphere, while Mn2, on a general position, has a slightly stronger [MnO₅N] ligand field, as the sixth coordination site is occupied by a pyridine molecule. Both centres approximate an octahedral ligand field. The chains are parallel in the crystal structure and interact via hydrogen bonds involving coordinated water molecules. However, the shortest metal–metal separation between two chains [5.3752 (3) Å] is large compared with the intrachain interactions. These structural features are compatible with a single‐chain magnet behaviour, as confirmed by preliminary magnetic studies.     

Reaction of Pertechnetate in Highly Alkaline Solution: Synthesis and Characterization of the Nitridotrioxotechnetate Ba[TcO3N]

The preparation of novel technetium oxides, their characterization and the general investigation of technetium chemistry are of significant importance, since fundamental research has so far mainly focused on the group homologues. Whereas the structure chemistry of technetium in strongly oxidizing media is dominated by the anion, our recent investigation yielded the new anion. Brown single crystals of Ba[TcO₃N] were obtained under hydrothermal conditions starting from Ba(OH)₂ ⋅ 8H₂O and NH₄[TcO₄] at 200 °C. crystallizes in the monoclinic crystal system with the space group P2₁/n (a=7.2159(4) Å, b=7.8536(5) Å, c=7.4931(4) Å and β=104.279(2)°). The crystal structure of consists of isolated tetrahedra, which are surrounded by Ba²⁺ cations. XANES measurements complement the oxidation state +VII for technetium and Raman spectroscopic experiments on Ba[TcO₃N] single crystals exhibit characteristic Tc−O and Tc−N vibrational modes.