Kristallstruktur von (NH4)3SnF7: Ein Doppelsalz gemäß (NH4)3[SnF6]F und kein (NH4)4SnF8

Crystal Structure of (NH₄)₃SnF₇: A Double Salt According to (NH₄)₃[SnF₆]F and not (NH₄)₄SnF₈ (NH₄)₃SnF₇ is obtained as colourless single crystals from the reaction of NH₄HF₂ with tin powder at 300°C. The crystal structure (cubic, Pm3m, Z = 1, a = 602.5(1) pm at 293 K; a = 598.0(1) pm at 100 K) contains [SnF₆]^2? octahedra and lonesome F^? ions surrounded by NH₄⁺ cations only; it may be considered as a derivative of the Cu₃Au-type of structure according to Cu₃[Au]□ ?(NH₄)₃[SnF₆]F. The F^? ions of the [SnF₆]^2? octahedra with their Sn⁴⁺ centre in the origin of the unit cell at m3m are disordered in different ways at 293 and 100 K, respectively.     

Synthese,Kristallstruktur und thermischer Abbau von Fluoroaluminaten der Zusammensetzung (NH4)[M(H2O)6][AlF6] (M = Zn,Ni), [Zn(H2O)6][AlF5(H2O)] und (PyH)4[Al2F10] · 4 H2O

Synthesis, Crystal Structure and Thermal Behaviour of Fluoroaluminates of the Composition (NH₄)[M(H₂O)₆](AlF₆) (M = Zn, Ni), [Zn(H₂O)₆][AlF₅(H₂O)], and (PyH)₄[Al₂F₁₀] · 4 H₂O Four new fluoroaluminates were obtained from fluoroacidic solutions of respective metal salts. The compounds of zinc ( I a : P2₁/c, a = 12.688(3), b = 6.554(1), c = 12.697(3) Å, β = 95.21(3)°, V = 1051.5(4) ų, Z = 4) and nickel ( I b : P2₁/c, a = 12.685(3), b = 6.517(1), c = 12.664(2)Å, β = 94.55(2)°, V = 1043.6(4) ų, Z = 4) are isotypic and represent a new structure type consisting of two different cations, NH₄⁺ and [M(H₂O)₆]²⁺ and [AlF₆]^3–‐anions. [Zn(H₂O)₆][AlF₅(H₂O)] ( II : C2/m, a = 10.769(2), b = 13.747(3), c = 6.487(1)Å, β = 100.02(3)°, V = 945.7(3) ų, Z = 4) is characterized by a H₂O/F‐disorder in the [AlF₅(H₂O)]‐octahedra in two trans positions. In (PyH)₄[Al₂F₁₀] · 4 H₂O ( III : Cmc2₁, a = 15.035(3), b = 20.098(4), c = 12.750(4) Å, V = 5364(2) ų, Z = 8), bioctahedral [Al₂F₁₀]^4– anions have been found for the first time. The structures are described and discussed in comparison. The new compounds were used as precursors in order to obtain new AlF₃‐phases. However, the thermal decomposition did not result in the formation of any new metastable AlF₃‐phase. Instead, phase mixtures of either α‐AlF₃ and β‐AlF₃ or AlF₃ and MF₂ were obtained.     

Die Einwirkung von Ammoniumfluorid auf Scandium: Synthese und Kristallstrukturen von (NH4)3[ScF6] und [Cu(NH3)4]3[ScF6]2

Action of Ammonium Fluoride on Scandium: Synthesis and Crystal Structures of (NH₄)₃[ScF₆] and [Cu(NH₃)₄]₃[ScF₆]₂ The action of (NH₄)F on scandium in copper ampoules yields either (NH₄)₃[ScF₆] or ScF₃ and a small quantity of [Cu(NH₃)₄]₃[ScF₆]₂, respectively, depending upon the molar ratio of the educts (NH₄)F : Sc (6 : 1 and 4 : 1, respectively) and temperature. (NH₄)₃[ScF₆] crystallizes with the cryolite type of structure: monoclinic, P2₁/n, Z = 2; a = 650.0(2); b = 651.4(2); c = 949.0(2) pm; β = 90.40(2)°, [Cu(NH₃)₄]₃[ScF₆]₂ is triclinic, P‐1, Z = 1; a = 821.1(2); b = 821.2(2); c = 822.7(2) pm; α = 90.04(3); β = 90.00(3); γ = 90.16(3)°. In its chemical behaviour against (NH₄)F, scandium parallels aluminium rather than gallium.     

Metallampullen als Mini‐Autoklaven: Synthese und Kristallstrukturen der Ammoniakate [Al(NH3)4Cl2][Al(NH3)2Cl4] und (NH4)2[Al(NH3)4Cl2][Al(NH3)2Cl4]Cl2

Metal Ampoules as Mini‐Autoclaves: Syntheses and Crystal Structures of [Al(NH₃)₄Cl₂][Al(NH₃)₂Cl₄] and (NH₄)₂[Al(NH₃)₄Cl₂][Al(NH₃)₂Cl₄]Cl₂ The salts [Al(NH₃)₄Cl₂]⁺[Al(NH₃)₂Cl₄]^–≡AlCl₃ · 3 NH₃ ( 1 ) and (NH₄⁺)²[Al(NH₃)₄Cl₂]⁺[Al(NH₃)₂Cl₄]^–(Cl^–)₂≡ AlCl₃ · 3 NH₃ · (NH₄)Cl ( 2 ) have been obtained as single crystals during the reactions of aluminum and aluminum trichloride, respectively, with ammonium chloride in sealed Monel metal containers. The crystal structure of 1 was determined again [triclinic, P‐1; a = 574.16(10); b = 655.67(12); c = 954.80(16) pm; α = 86.41(2); β = 87.16(2); γ = 84.89(2)°], that of 2 for the first time [monoclinic, I2/m; a = 657.74(12); b = 1103.01(14); c = 1358.1(3) pm; β = 103.24(2)°].     

Reaktionen am metallischen Substrat: Einkristalle von Ni(NH3)2V2F8

Reactions at the Metallic Substrate: Single Crystals of Ni(NH₃)₂V₂F₈ Except for the main product (NH₄)₂[TaF₇] and some [Ni(NH₃)₆][TaF₆]₂, the new light green Ni(NH₃)₂V₂F₈ is obtained by the reaction of (NH₄)F with tantalum and vanadium (molar ratio of (NH₄)F : Ta : V = 36 : 6 : 1) at 400 °C in a sealed Monel ampoule (Cu32Ni68). The crystal structure (orthorhombic, Fmmm, Z = 4, a = 752.9(1), b = 762.9(1), c = 1307.6(2) pm) is related to that of (NH₄)[VF₄]. According to {Ni(NH₃)₂}_0,5[VF₄], corrugated layers of vertex-connected octahedra [VF_4/2F_2/1] are stacked in the [001] direction. Between these layers trans-{Ni(NH₃)₂} units are inserted so that Ni²⁺ enhances its coordination number to 6 by two times two F^– from the layers above and below.     

Kristallstrukturen,Schwingungsspektren und Normalkoordinatenanalyse von fac‐(Et4N)[OsF3Cl3] und fac‐(Et4N)[IrF3Cl3]

Crystal Structures, Vibrational Spectra and Normal Coordinate Analysis of fac ‐(Et₄N)[OsF₃Cl₃] and fac ‐(Et₄N)[IrF₃Cl₃] By careful oxidation of the pure fluorochloroosmates(IV) or ‐iridates(IV) with BrF₃ or KBrF₄ in dichloromethane the mixed pentavalent complex anions fac‐[OsF₃Cl₃]^– and fac‐[IrF₃Cl₃]^– are formed. X‐ray structure determinations on single crystals have been performed of cis‐(Et₄N)[OsF₃Cl₃] ( 1 ) (orthorhombic, space group Pbca, a = 11.225(5), b = 12.020(5), c = 21.873(5) Å, Z = 8) and fac‐(Et₄N)[IrF₃Cl₃] ( 2 ) (orthorhombic, space group Pbca, a = 11.269(10) b = 12.049(1), c = 21.801(3) Å, Z = 8). Based on the molecular parameters of the X‐ray determinations the IR and Raman spectra for the anion of 1 and 2 have been assigned by normal coordinate analysis. The Osmium compound exhibits slightly higher valence force constants as compared with the Iridium complex: f_d(OsF) = 3.25, f_d(IrF) = 3.25, f_d(OsCl) = 2.35 and f_d(IrCl) = 2.25 mdyn/Å.     

Synthese und Kristallstruktur von [Cr(NH3)6][Cr(NH3)2F4][BF4]2

Synthesis and Crystal Structure of [Cr(NH₃)₆][Cr(NH₃)₂F₄][BF₄]₂ The action of ammonium fluoride on a mixture of boron and chromium in a sealed Monel ampoule at 300 °C yields single crystals of [Cr(NH₃)₆][Cr(NH₃)₂F₄][BF₄]₂. The crystal structure (tetragonal, P4/mbm, Z = 2, a = 1056.0(1), c = 781.7(1) pm; R₁ = 0.0414; wR₂ = 0.1087 for 411 reflections with I₀ > 2σ(I)) contains [Cr(NH₃)₆]³⁺ and [Cr(NH₃)₂F₄]^– octahedra and twice as many [BF₄]^– tetrahedra that are arranged in a quadrupled super‐structure of the CsCl‐type of structure.     

Darstellung,Kristallstruktur, thermischer Abbau und Schwingungsspektren von [Co(NH3)6]2[Be4O(CO3)6] · 10 H2O

Preparation, Crystal Structure, Thermal Decomposition, and Vibrational Spectra of [Co(NH₃)₆]₂[Be₄O(CO₃)₆] · 10 H₂O [Co(NH₃)₆]₂[Be₄O(CO₃)₆] · 10 H₂O is a suitable compound for the quantitative determination of beryllium. It can be obtained by reaction of aqueous solutions of carbonatoberyllate with [Co(NH₃)₆]Cl₃. The crystal structure (trigonal‐rhombohedral, R3c (Nr. 161), a = 1071,6(1) pm, c = 5549,4(9) pm, V_EZ = 5519(1) · 10⁶ pm³, Z = 6, R1(I ≥ 2σ(I)) = 0,037, wR2(I ≥ 2σ(I)) = 0,094) contains [Co(NH₃)₆]³⁺‐ and [Be₄O(CO₃)₆]^6–‐ions, which are directly hydrogen bonded as well as with water molecules. The complex cations and anions occupy the positions of a distorted anti‐CaF₂‐type. The thermal decomposition, IR and Raman spectra are presented and discussed.     

Benzodithiazolium‐Chlorooxomolybdate(V): Darstellung und Kristallstruktur von (C6H4NS2)[MoOCl4] und (C6H4NS2)[MoOCl4·H2O]

Benzodithiazolium Chlorooxomolybdate(V): Preparation and Crystal Structure of (C₆H₄NS₂)[MoOCl₄] and (C₆H₄NS₂)[MoOCl₄·H₂O] Red benzo‐1,3,2‐dithiazolium‐chlorooxomolybdate(V) (C₆H₄NS₂)[MoOCl₄] ( 1 ) was obtained by the reaction of benzo‐1,3,2‐dithiazoliumchloride and molybdenum(V)chloride oxide in dichlormethane under solvothermal conditions at 70 °C. In the presence of small amounts of concentrated hydrochloric acid the yellow compound (C₆H₄NS₂)[MoOCl₄·H₂O] ( 2 ) is formed under analogue conditions. Both crystal structures ( 1 : monoclinic, C2/c, a = 799.2(1), b = 2091.5(2), c = 791.5(1) pm, β = 102.2(1)°, Z = 4; 2 : monoclinic, Cc, a = 953.7(1), b = 2468.9(3), c = 608.1(1) pm, β = 112.5(1)°, Z = 4) contain the planar benzo‐1,3,2‐dithiazolium ion. Within the structure of 1 the molybdenum atoms in the [MoOCl₄]^? ions are coordinated in a square pyramidal fashion with an oxygen atom in apical position and the basal plane formed by chlorine atoms. The nitrogen atom of the cation, which bears a partial negativ charge, expands the coordination to a distorted octahedron. The structure therefore is made up of ionic pairs {(C₆H₄NS₂)⁺ [MoOCl₄]^?} with a Mo–N distance of 266 pm. 1 is paramagnetic with a magnetic moment of 1.7 B.M. corresponding to one unpaired electron per formula unit. In the structure of 2 the coordination of the [MoOCl₄]^? ion is expanded by the oxygen atom of a coordinating water molecule. The structure is dominated by hydrogen bonds between the oxygen atoms of the [MoOCl₄·H₂O]^? ions which cause the concatenation of the anions to infinite chains.     

From Isolated Polyanions to 1‐D Structure: Synthesis and Crystal Structure of Hybrid Fluorides {[(C2H4NH3)3NH]4+}2 · (H3O)+ · [Al7F30]9– and {[(C2H4NH3)3NH]4+}2 · [Al7F29]8– · (H2O)2

Two new hybrid fluorides, {[(C₂H₄NH₃)₃NH]⁴⁺}₂ · (H₃O)⁺ · [Al₇F₃₀]^9– ( I ) and {[(C₂H₄NH₃)₃NH]⁴⁺}₂ · [Al₇F₂₉]^8– · (H₂O)₂ ( II ), are synthesized by solvothermal method. The structure determinations are performed by single crystal technique. The symmetry of both crystals is triclinic, sp. gr. P 1, I : a = 9.1111(6) Å, b = 10.2652(8) Å, c = 11.3302(8) Å, α = 110.746(7)°, β = 102.02(1)°, γ = 103.035(4)°, V = 915.9(3) ų, Z = 1, R = 0.0489, R_w = 0.0654 for 2659 reflections, II : a = 8.438(2) Å, b = 10.125(2) Å, c = 10.853(4) Å, α = 106.56(2)°, β = 96.48(4)°, γ = 94.02(2)°, V = 877.9(9) ų, Z = 1, R = 0.0327, R_w = 0.0411 for 3185 reflections. In I , seven corner‐sharing AlF₆ octahedra form a [Al₇F₃₀]^9– anion with pseudo 3 symmetry; such units are found in the pyrochlore structure. The aluminum atoms lie at the corners of two tetrahedra, linked by a common vertex. In II , similar heptamers are linked in order to build infinite (Al₇F₂₉)_n^8– chains oriented along a axis. In both compounds, organic moieties are tetra protonated and establish a system of hydrogen bonds N–H…F with four Al₇F₃₀^9– heptamers in I and with three inorganic chains in II .     

Structural Investigations and Thermal Behavior of (NH4)[Cr(C2O4)2]·2H2O

Single crystals of ammonium chromium(III) dioxalate dihydrate (or ammonium diaquo bis(μ‐oxalato)chromate(III)) have been obtained from aqueous solution of oxalic acid and ammonium dichromate. A pale violet crystal of good optical quality was used for the structure determination at ?100(2) and 25(2) °C, respectively. The basic crystallographic data for the low temperature data set are as follows: monoclinic, space group C2/m, a = 6.597(2) Å, b = 7.301(2) Å, c = 9.983(3) Å, β = 92.32(2)°, V = 480.5(2) ų. The structure was solved by direct methods and refined (using anisotropic displacement parameters for all non‐hydrogen atoms) to a final residual of R1 = 0.032 for 503 independent observed reflections (I>2σ(I)). The compound is isotypic with the corresponding rubidium salt. The structure is built up from alternating layers parallel to (001) containing (NH₄)⁺ ions or Cr(C₂O₄)₂(H₂O)₂ octahedra, respectively. The corners of the octahedra consist of four O atoms from two oxalate groups and two additional water molecules. The ammonium cations (occupying Wyckoff‐site 2a) are disordered among two possible orientations. They provide linkage between different octahedral layers by hydrogen bridging. The water molecules in turn form hydrogen bridges with adjacent octahedra within the same layer. Further structural characterization included infrared spectroscopy. According to DTA/TG experiments the present compound shows several thermal processes in the range between room temperature and 900 °C.     

Synthesis,Crystal Structure of a New Structure Type,and Thermal Analysis of the Ammonium Borophosphate (NH4)2[B2P3O11(OH)]

(NH₄)₂[B₂P₃O₁₁(OH)] was synthesized as a crystalline colorless powder by reaction of (NH₄)₂HPO₄, H₃BO₃, and H₃PO₄ under hydrothermal conditions at 180 °C. According to X‐ray single‐crystal investigations (NH₄)₂[B₂P₃O₁₁(OH)] crystallizes in a new structure type in the orthorhombic space group P2₁2₁2₁ (no. 19) [Z = 4, a = 4.509(3), b = 14.490(11), c = 16.401(12) Å, R₁ = 0.046, wR₂ = 0.093, 1682 data, 200 parameters]. The crystal structure comprises infinite layers of corner‐sharing borate, phosphate and hydroxo‐phosphate tetrahedra with ammonium ions in‐between. The loop‐Branched (lB) zweier‐single layer reveals an open‐Branched (oB) vierer‐single ring as fundamental building unit (FBU), which was observed in (NH₄)₂Mn^II[B₂P₃O₁₁(OH)₂]Cl^[1] for the first time. Besides the spectroscopic properties the thermal behavior is presented as well.     

Darstellung und Strukturaufklärung von Ammonium‐tetraamminlithium‐amidotrithiophosphat‐Ammoniak(1/1) (NH4) [Li(NH3)4] [P(NH2)S3] · NH3

Synthesis and Crystal Structure of Ammonium Tetraamminelithium Amidotrithiophosphate‐Ammonia(1/1)(NH₄)[Li(NH₃)₄][P(NH₂)S₃]·NH₃ Colourless crystals of (NH₄)[Li(NH₃)₄][P(NH₂)S₃]·NH₃ were prepared by the reduction of P₄S₁₀ with a solution of lithium in liquid ammonia. The X‐ray structure determination shows them to contain the pseudo‐tetrahedral amidotrithiophosphate anion [P(NH₂)S₃]²⁻ (point group C_S), which is the hitherto unknown final member of a series of previously characterized amidothiophosphates. The ammonium ion and the ammonia molecule of solvation form an diamminehydrogen(1+)‐ion N₂H₇⁺ with a short, nearly linear hydrogen bond of 2.864(3) Å.     

Die Kristallstruktur von cis‐ und trans‐N‐iso‐Propylamidodimethylindium, [(CH3)2In‐N(H)iC3H7]2

The Crystal Structure of cis‐ and trans‐N‐iso‐Propylamidodimethyl Indium, [(CH₃)₂In‐N(H)ⁱC₃H₇]₂ According to the X‐ray structure determination [(CH₃)₂In‐N(H)ⁱC₃H₇]₂ (prepared from InMe₃ (Me = CH₃) and H₂NⁱPr (ⁱPr = CH(CH₃)₂) crystallizes in the monoclinic space group P2₁/n with 3 dimeric trans as well as 3 dimeric cis isomers per unit cell. The centrosymmetric form has a planar In₂N₂ core with In—N bonds of 222.1(4) and 222.9(5) pm, respectively, the skeleton of the cis isomer with In—N bonds of 221.4(4) pm is slightly folded (13.7°). Some ¹H, ¹³C NMR, IR, and Raman data are reported.     

[2+4] and [2+2] Cycloaddition Reactions of N‐Sulfinyl Carboxylic Acid Amides with (CF3)2BNMe2. Crystal Structure of cyclo‐(CF3)2B‐NMe2‐S(=O)‐N=C(p‐CH3C6H4)‐O

N‐sulfinylacylamides R‐C(=O)‐N=S=O react with (CF₃)₂BNMe₂ ( 1 ) to form, by [2+4] cycloaddition, six‐membered rings cyclo‐(CF₃)₂B‐NMe₂‐S(=O)‐N=C(R)‐O for R = Me ( 2 ), t‐Bu ( 3 ), C₆H₅ ( 4 ), and p‐CH₃C₆H₄ ( 5 ) while N‐sulfinylcarbamic acid esters R‐O‐C(=O)‐N=S=O react with 1 to yield mixtures of six‐membered (cyclo‐(CF₃)₂B‐NMe₂‐S(=O)‐N=C(OR)‐O) and four‐membered rings (cyclo‐(CF₃)₂B‐NMe₂‐S(=O)‐N(C=O)OR) for R = Me ( 6 and 9 ), Et ( 7 and 10 ), and C₆H₅ ( 8 and 11 ). The structure of 5 has been determined by X‐ray diffraction.     

Synthese und Struktur von RbHfF5, Rb2Zr3F12O und Rb2Hf3F12O — zwei Oxidfluoride mit zentraler trigonal‐planarer [M3O]‐Gruppe

Synthesis and Structure of RbHfF₅, Rb₂Zr₃F₁₂O and Rb₂Hf₃F₁₂O — two Oxydefluorides with Central Trigonal‐plane [M₃O] Group Colorless RbHfF₅ crystallizes isotypic with (NH₄)ZrF₅ and TlHfF₅ monoclinic, space group P2₁/c ‐ C_2h (No. 14) with a = 776.6, b = 789.6, c = 789.8 pm, and β = 120.52°. Also colorless Rb₂Zr₃F₁₂O crystallizes trigonal, space group R3¯m — D₃d (No. 166), with a = 771.9 and c = 2963.0 pm, isotypic is Rb₂Hf₃F₁₂O with a = 769.2 pm and c = 2986.1 pm. Both compounds are isotypic with Tl₂Zr₃F₁₂O.     

Struktur und 1D‐magnetische Eigenschaften von (pipzH2)[MnF4(H2PO4)]

Structure and 1D‐magnetic properties of (pipzH₂)[MnF₄(H₂PO₄)] From hydrofluoric and phosphoric acid solution of Manganese(III), using piperazinium(2+) counter cations (pipzH₂²⁺) the chain‐anion [MnF₄(H₂PO₄)]^2— can be stabilized providing an interesting model system for studying the magnetic exchange interaction via phosphate bridges. Depending on the HF/H₃PO₄ excess (pipzH₂)[MnF₄(H₂PO₄)] crystallizes in two polymorphs I und II , differing mainly in the orientation of the cations. Form I is monoclinic, space group P2₁/c, Z = 4, a = 6.749(1), b = 12.039(1), c = 12.501(1) Å, β = 94.420(4)°, R = 0.023, Form II crystallizes in the same space group type P2₁/c, Z = 4, a = 6.651(1), b = 12.799(1), c = 12.825(1) Å, β = 110.312(5)°, R = 0.037. The Mn³⁺ ions are octahedrally surrounded by four terminal fluoride ligands and axially by bidentate bridging dihydrogenphosphate groups. The shape of the chain anions is very close in both modifications and characteristic for ferrodistortive Jahn‐Teller ordering.The Mn—O‐bonds along the chain direction are strongly elongated (distances 2.16 to 2.21 Å) whereas all Mn—F bond (1.81—1.88Å) are ruther short. On a large single crystal of form I 1D‐antiferromagnetic properties were found. By fitting an appropriate model based on the temperature dependence of the correlation lengths using an anisotropy constant D/k = —2.9 K a remarkably high exchange energy of J/k = —1.6(1) K along the chains could be determined.     

Zwei Galliumfluorid-Ammoniakate: Ga(NH3)F3 und Ga(NH3)2F3

Two Gallium Fluoride Ammine Complexes: Ga(NH₃)F₃ and Ga(NH₃)₂F₃ Two gallium trifluoride ammines, Ga(NH₃)F₃ and Ga(NH₃)₂F₃, are obtained as single crystals through oxidation of gallium metal with NH₄HF₂ (Ga : NH₄HF₂ = 1 : 1.5) and NH₄F (Ga : NH₄F = 1 : 3.5), respectively, at 450 °C and 400 °C. Ga(NH₃)F₃ crystallizes with the non-centrosymmetric space group Abm2 (a = b = 544.6(2) pm, c = 986.6(4) pm) forming two-dimensional layers of [Ga(NH₃)F₅] octahedra. The addition of another NH₃ molecule in Ga(NH₃)₂F₃ (orthorhombic, Immm, a = 700.0(3) pm, b = 724.7(2) pm, c = 393.1(1) pm) leads to one-dimensional rods of [Ga(NH₃)₂F₄] octahedra running parallel [001] which are stacked in the [010] direction. Infrared spectra suggest hydrogen bonding (N–H…F) in Ga(NH₃)F₃, for Ga(NH₃)₂F₃ an unequivocal statement is not possible.