Variation of 2 D Hydrogen Bond Topology in Diaqua-tetrafluoromanganates(III): 2-picoH[MnF4(H2O)2], TMEDAH2[MnF4(H2O)2]2, and TMBDAH2[MnF4(H2O)2]2

The crystal structures of three new diaqua-tetrafluoro-manganate(III) compounds with different organic N-cations have been determined: 2-picoH[MnF₄(H₂O)₂] 1 (2-pico = 2-methyl-pyridine), space group P2₁/c, a = 9.439, b = 13.662, c = 7.641 Å, β = 91.31°; R = 0.059; TMEDAH₂[MnF₄(H₂O)₂]₂ 2 (TMEDA = N,N,N′,N′-tetramethyl ethane diamine), space group P2₁/c, a = 5.421, b = 15.970, c = 9.677 Å, β = 96.37°, R = 0.031, and TMBDAH₂[MnF₄(H₂O)₂]₂ 3 (TMBDA = N,N,N′,N′-tetramethyl-1,4-butane-diamine), space group P2₁/n, a = 12.631, b = 5.577, c = 12.976 Å, β = 98.10°, R = 0.040. All three compounds show 2 D H-bonding networks of [MnF₄(H₂O)₂]^– anions separated by the organic cations. However, the topology of the anionic H-bonding nets is different for each compound. The anions are strongly elongated by the Jahn-Teller effect and are arranged in a ferrodistortive way in compounds 1 and 2 , whereas in compound 3 the arrangement is described as in a herringbone-like antiferrodistortive variant.     

Ein Fluoridphosphat von Mangan(III) mit ungewöhnlicher Schichtstruktur: Na7[Mn5F13(PO4)3(H2O)3]

A Fluoride Phosphate of Manganese(III) with Unusual Layer Structure: Na₇[Mn₅F₁₃(PO₄)₃(H₂O)₃] The title compound was crystallized from a solution of MnF₃ · 3 H₂O in aqueous HF by addition of NaH₂PO₄ · H₂O in 2 M phosphoric acid. The crystal structure has been determined at 295 and 150 K on a trigonal crystal twinned by merohedry: Space group P3c1, Z = 4, a = 1055,0(1), c = 2314,0(1) pm (a = 1052,5(1), c = 2304,2(1) pm at 150 K), wR₂ = 0.0651 (0.0651). The structure contains anionic layers formed by triangular moieties of three [MnF₃O₂(H₂O)] octahedra sharing one common μ₃-F atom and bridged by three phosphate groups. Three of those groups, respectively, are interconnected by two [MnF₃O₃] octahedra over six phosphate O-atoms to form a trigonal layer in the a,b plane. Stacking of these layers gives channels along the c axis in which most of the Na⁺ ions are located. The [MnF₃O₂(H₂O)] octahedra show strong elongation along the μ₃-F–Mn–OH₂ axis mainly due to the Jahn-Teller effect whereas in the [MnF₃O₃] octahedra with C₃ symmetry weak signs only of a dynamical Jahn-Teller-effect can be observed. The magnetic properties (μ_eff = 4.61 μ_B, 3-D ordering point T_N = 3.3 K) were determined on powders and possible magnetic exchange pathways are discussed.     

The First Aqua Pentafluoro Manganates(III) – Syntheses and Structures

For the first time aqua pentafluoro manganate(III) compounds with different organic N-cations have been prepared and their crystal structures have been determined: N,N′-DMenH₂[MnF₅(H₂O)] · H₂O 1 (N,N′-DMen = N,N′-Dimethylethylenediamine), space group P2₁/c, a = 916.0, b = 1004.8, c = 1247.9 pm, β = 106.03°, R = 0.035; NMpipzH₂ · [MnF₅(H₂O)] · H₂O 2 (NMpipz = N-Methylpiperazine), space group P2₁/n, a = 757.7, b = 1261.9, c = 1197.1 pm, β = 105.09°, R = 0.027; N,N′-DMpipzH₂[MnF₅(H₂O)] · 2 HF 3 (N,N′-DMpipz = N,N′-Dimethylpiperazine), space group P1, a = 677.1, b = 863.9, c = 1187.7 pm, α = 79.18°, β = 81.63° γ = 67.62°, R = 0.026; and N,N-DMenH₂[MnF₅(H₂O)] · 1/2 HF 4 (N,N-DMen = N,N-Dimethylethylenediamine), space group P1, a = 859.3, b = 1086.5, c = 1092.0 pm, α = 86.96°, β = 78.52° γ = 89.01°, R = 0.035. In all compounds the [MnF₅(H₂O)]^2– octahedra are connected via H-bonds forming 3 D and 2 D network arrangements. The anions are strongly elongated by the Jahn-Teller effect. The FTIR spectra are presented.     

Doppelkettenstruktur von (pipzH2)[MnF2(HPO4)(H2O)](H2PO4)

By adding piperazine to a hydrofluoric and phosphoric acid solution of Manganese(III) fluoride, the fluoride phosphate (pipzH₂)[MnF₂(HPO₄)(H₂O)](H₂PO₄) can be crystallized. Its structure is built by piperazinium(2+) cations, (H₂PO₄)^? anions, and an anionic double‐chain of [HPO₄] tetrahedra and [MnO₃F₂(H₂O)] octahedra. The structure is triclinic, space group P , Z = 2, a = 622.97(4), b = 923.46(6), c = 1183.62(7) pm, α = 98.343(6)°, β = 100.747(7)°, γ = 107.642(5)°, R = 0.0289. It is worth noting that a ferrodistortive Jahn‐Teller order is observed with [MnO₃F₂(H₂O)] octahedra strongly elongated along the F–Mn–OH₂ axes perpendicular to the chain plane. The structure is stabilized by very strong hydrogen bonds.     

Kristallstrukturen von Verbindungen A2[MnF3(SO4)] (A = Rb,NH4, Cs): Jahn‐Teller‐Ordnung in Mangan(III)‐fluoridsulfaten. I.

Jahn‐Teller Ordering in Manganese(III) Fluoride Sulphates. I. Crystal Structures of A₂[MnF₃(SO₄)] (A = Rb, NH4, Cs) The three isostructural fluorosulphatomanganates(III) A₂[MnF₃(SO₄)] (A = Rb, NH₄, Cs) crystallize in space group P2₁/c, Z = 4. Rb₂[MnF₃(SO₄)]: a = 7.271, b = 11.091, c = 8.776Å, β = 92.26°, R = 0.033; (NH₄)₂[MnF₃(SO₄)]: a = 7.299, b = 10.157, c = 8.813Å, β = 91.51°, R = 0.025; Cs₂[MnF₃(SO₄)]: a = 7.365, b = 11.611, c = 9.211, β = 92.30°, R = 0.029. In the chain anions [MnF₃(SO₄)]^2— manganese(III) is coordinated by two trans‐terminal and two trans‐bridging fluorine ligands, and by the O‐atoms of two briding sulphate ligands in trans position. The Jahn‐Teller effect induces a variety of antiferrodistortive ordering resulting in distorted [MnF₄O₂] octahedra with alternating elongation of F—Mn—F — and O—Mn—O — axes, respectively. Thus, only asymmetrical bridges are formed.     

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.     

Jahn‐Teller‐Ordnung in Mangan(III)‐fluoridsulfaten. II. Phasenübergang und Verzwillingung bei K2[MnF3(SO4)] und 1D Magnetismus in Verbindungen A2[MnF3(SO4)] (A = K,NH4, Rb,Cs)

Jahn‐Teller Ordering in Manganese(III) Fluoride Sulfates. II. Phase Transition and Twinning of K₂[MnF₃(SO₄)] and 1D Magnetism in Compounds A₂[MnF₃(SO₄)] (A = K, NH₄, Rb, Cs) According to single‐crystal X‐ray investigations, K₂[MnF₃(SO₄)] crystallizes at low temperature, like the isostructural Rb, NH₄, and Cs analogues in space group P2₁/c, Z = 4, e.g. at 100 K with a = 7.197, b = 10.704, c = 8.427Å, β = 91.84°. Below about 300 K, the crystals are found to be [001] axis twins. Using a new integration method for area detector records, nearly complete intensity data could be gained allowing for structure refinements of similar quality as for untwinned crystals (e.g. at 100 K: wR₂ = 0.050, R = 0.020 for all reflections). With rising temperature, the monoclinic angle approaches continuously 90°. For an ordering parameter Δβ = β?90° a 2^nd‐order phase transition is observed with an exponent λ = 0.17. At the transition temperature of 280 K resulting from the fit, the monoclinic structure changes – with delay – to orthorhombic with the minimum super‐group Pnca, a = 7.243, b = 10.763, c = 8.457Å, R = 0.024, as found in an early structure determination at room temperature by Edwards 1971. In the chain‐like [MnF₃(SO₄)]^2? anions, manganese(III) is octahedrally coordinated by two trans‐terminal and two trans‐bridging fluorine ligands as well as by the O atoms of two trans‐bridging sulfate ligands. At low temperature, the octahedral elongation by the Jahn‐Teller effect alternates between a F–Mn–F and an O–Mn–O axis (antiferrodistortive ordering). All bridges are asymmetric. From about 320 K on they become symmetric. Due to 2D dynamical Jahn‐Teller effect all octahedra appear compressed. All compounds A₂[MnF₃(SO₄)] show 1D antiferromagnetism. The antiferrodistortive Jahn‐Teller order at low temperatures and the small bridge angles explain the much lower magnetic exchange energies and their inverse relation to the bridge angles as compared with other fluoromanganate(III) chain compounds with the usual ferrodistortive ordering.     

Darstellung,Kristallstruktur, Schwingungsspektren und Normalkoordinatenanalyse von K2[OsCl5(CO)] · H2O

Synthesis, Crystal Structure, Vibrational Spectra, and Normal Coordinate Analysis of K₂[OsCl₅(CO)] · H₂O The X-ray structure determination of K₂[OsCl₅(CO)] · H₂O (monoclinic, space group P2₁/c a = 13.600(2), b = 7.122(1), c = 22.186(11) Å, β = 98.66(3)°, Z = 8) revealed two crystallographic independent bat very similar complex anions [OsCl₅(CO)]^2? with rough C_4v point symmetry. Due to the stronger trans influence of the carbonyl group the bond lengths in the Cl? Os? CO axis Os? Cl = 2.449(2), 2.430(2) Å are langer as compared with the octahedron basis Os? Cl = 2.340-2.370 Å. The water of crystallization is coordinated to potassium (K? OH₂ = 2.625-2.815 Å). Using the molecular parameters the IR and Raman spectra are assigned by normal coordinate analysis. The valence force constants are f_d(CO) = 15.30, f_d(OsC) = 3.88, f_d(OsCl) = 1.81, f_d(OsCl) = 1.36, f_d(OH) = 7.65, 7.82, 7.79 mdyn/Å. The strengthening of the Os? C bond by stronger back donation of the Os^III(d⁵) complex in comparison with the isostructural Os^IV (d⁴) compound is discussed.     

Darstellung und Kristallstruktur von Tetraphenylphosphonium-Hexathiocyanatorhodat(III), [P(C6H5)4]3[Rh(SCN)6]

Preparation and Crystal Structure of Tetraphenylphosphonium Hexathiocyanatorhodate(III), [P(C₆H₅)₄]₃[Rh(SCN)₆] By treatment of RhCl₃ · n H₂O with KSCN in water a mixture of the linkage isomers [Rh(NCS)_n(SCN)_6–n]^3?, n = 0–2 is formed which is separated by ion exchange chromatography on diethylaminoethyl cellulose. The X-ray structure determination on a single crystal of [P(C₆H₅)₄]₃[Rh(SCN)₆] (monoclinic, space group C1c1, a = 13.620(5), b = 22.929(13), c = 22.899(9) Å, β = 98.55(3)°, Z = 4) confirms the coordination of all ligands via S with the middle Rh? S distance of 2.372 Å and Rh? S? C angles of 109°. The SCN groups are nearly linear with 175° and averaged bondlengths S? C 1.63 and C? N 1.14 Å. The crystal lattice is build up by layers of complex anions and voluminous cations with no specific interactions but which are closely connected by thiocyanate ligands and phenyl rings.     

A Novel Coordination Polymer Based on Decavanadate Units Linked by Copper(II) Ethylenediamine Complexes

Summary: A novel coordination polymer[{Cu(en)₂}(V₁₀O₂₈)]_n · 2n[Cu(en)₂(H₂O)] · 2n(H₃BO₃) · 2n(H₂O) was obtained by hydrothermal reaction. The compound crystallizes in the monoclinic crystal system, in the C2/c space group, with a = 26.490 (3) Å; b = 11.6558 (11) Å; c = 19.8426 (19) Å; β = 124.011 (1)°; V = 5078.6(8) ų. The solid structure is formed by polymeric chains, [Cu(en)₂(H₂O)]²⁺ cations, and boric acid and water solvate molecules, stabilized through a multiple hydrogen bond network.     

Zur Koordinationschemie von cis-Trioxowolfram(VI)-Komplexen. Die Kristallstrukturen von LWO3 · 3 H2O, [L′WO2(OH)]Br, [LWO2Br]Br, [L2W2O5](S2O6) · 4 H2O und [LWO2(μ-O)WO(O2)2(OH2)] (L = 1,4,7-Triazacyclononan; L′ = 1,4,7-Trimethyl-1,4,7-triazacyclononan)

Coordination-chemistry of cis-Trioxotungsten(VI) Complexes. Crystal Structures of LWO₃ · 3 H₂O, [L′WO₂(OH)]Br, [LWO₂Br]Br, [L₂W₂O₅](S₂O₆) · 4 H₂O and [LWO₂(μ-O)WO(O₂)₂(OH₂)] (L = 1,4,7-Triazacyclonane; L′ = 1,4,7-Trimethyl-1,4,7-triazacyclononane) The cyclic triamines 1,4,7-triazacyclononane (L; C₆H₁₅N₃) and 1,4,7-trimethyl-1,4,7-triazacyclononane (L′; C₉H₂₁N₃) react in aqueous solution with WO₃ affording LWO₃ · 3 H₂O, 1 , and L′WO₃ · 3 H₂O, respectively, which yield [L′WO₂(OH)]Br, 2 , and [LWO₂Br]Br, 3 , in concentrated HBr solutions. In aqueous CH₃SO₃H solution 1 dimerizes. The iodide and dithionate 4 salts of [L₂W₂O₅]²⁺ have been isolated. In 35% H₂O₂ complex 1 yields the neutral species [LWO₂(μ-O)WO(O₂)₂(H₂O)] 5 . The crystal structures of 1 – 5 have been determined by X-ray analysis. Crystal data: 1 : P2₁/c; a = 7.729(2), b = 14.887(3), c = 10.774(2) Å, β = 90.77(2)°, Z = 4; 2 : Cc; 8.910(3), b = 12.220(6), c = 13.279(6) Å, β = 101.31(3)°, Z = 4; 3 : Cmc2₁, a = 8.857(5), b = 12.062(7), c = 11.218(7) Å, Z = 4; 4 : Cc, a = 17.601(7), b = 12.906(7), c = 14.107(8) Å, β = 124.08(4)°, Z = 4; 5 : P2₁2₁2₁; a = 8.452(4), b = 11.301(6), c = 13.750(6) Å, Z = 4.     

Syntheses and structures of nine-coordinate K3[DyIII(nta)2(H2O)]·5H2O and eight-coordinate (NH4)3[DyIII(nta)2] complexes

K₃[Dy^III(nta)₂(H₂O)]·5H₂O and (NH₄)₃[Dy^III(nta)₂] have been synthesized in aqueous solution and characterized by IR, elemental analysis and single-crystal X-ray diffraction techniques. In K₃[Dy^III(nta)₂(H₂O)]·5H₂O the Dy^III ion is nine coordinated yielding a tricapped trigonal prismatic conformation, and its crystal belongs to monoclinic system and C2/c space group. The crystal data are as follows: a = 15.373(5) Å, b = 12.896(4) Å, c = 26.202(9) Å; β = 96.122(5)°, V = 5165(3) ų, Z = 8, D _c = 1.965 g·cm^?3, μ = 3.458 mm^?1, F(000) = 3016, R ₁ = 0.0452 and wR ₂ = 0.1025 for 4550 observed reflections with I ≥ 2σ(I). In (NH₄)₃[Dy^III(nta)₂] the Dy^III ion is eight coordinated yielding a usual dicapped trigonal anti-prismatic conformation, and its crystal belongs to monoclinic system and C2/c space group. The crystal data are as follows: a = 13.736(3) Å, b = 7.9389(16) Å, c = 18.781(4) Å; β = 104.099(3)°, V = 1986.3(7) ų, Z = 2, D _c = 1.983 g·cm^?3, μ = 3.834 mm^?1, F(000) = 1172, R ₁ = 0.0208 and wR ₂ = 0.0500 for 2022 observed reflections with I ≥ 2σ(I). The results indicate that the difference in counter ion also influences coordination numbers and structures of rare earth metal complexes with aminopolycarboxylic acid ligands.     

Synthese,Charakterisierung und Kristallstrukturen von Tetraiodoferraten(III)

Preparation, Characterization, and Crystal Structures of Tetraiodoferrates(III) The extremely air and moisture sensitive tetraiodoferrates MFeI₄ with M = K, Rb and Cs have been synthesized by reaction of Fe, MI and I₂ at 300°C in closed quartz ampoules. The essentially more stable alkylammonium tetraiodoferrates NR₄FeI₄ with R = H, C₂H₅, n-C₃H₇, n-C₄H₉ and n-C₅H₁₁ can be obtained by reaction of Fe, NR₄I and I₂ in nitromethane. The Raman and UV/Vis-spectra of the black compounds show the existence of tetrahedral [FeI₄]^? ions in the structures. The crystal structure of the monoclinic CsFeI₄ (CsTlI₄ type, spgr P2₁/c; a = 7.281(1) Å; b = 17.960(3) Å; c = 8.248(2) Å; β = 107.35(15)°) is built up by tetrahedral [FeI₄]^? ions and CsI₁₁ polyhedra. The crystal structure of the orthorhombic (n-C₅H₁₁)₄NFeI₄ (spgr Pnna; a = 20.143(4) Å; b = 12.683(3) Å; c = 12.577(3) Å) contains tetrahedral [(n-C₅H₁₁)₄N]⁺ ions and [FeI₄]^? ions, respectively.     

Isopropylammonium Layered Uranyl Chromates: Syntheses and Crystal Structures of [(CH3)2CHNH3]3[(UO2)3(CrO4)2O(OH)3] and[(CH3)2CHNH3]2[(UO2)2(CrO4)3(H2O)]

Two novel isopropylamine‐templated uranyl chromates, [(CH₃)₂CHNH₃]₃[(UO₂)₃(CrO₄)₂O(OH)₃] ( 1 ) and [(CH₃)₂CHNH₃]₂[(UO₂)₂(CrO₄)₃(H₂O)] ( 2 ) were prepared by hydrothermal method at 100 °C. The compounds were characterized by electron microprobe analysis and X‐ray diffraction crystal structure analysis [ 1 : trigonal, P31m, a = 9.646(4), c = 8.469(4) Å, V = 682.4(5) ų; 2 : monoclinic, P2₁/c, a = 11.309(3), b = 11.465(3), c = 17.055(5) Å, β = 99.150(6)°, V = 2183.2(11) ų]. The structure of 1 is based upon trimers of uranyl bipyramids interlinked by CrO₄ tetrahedra to form [(UO₂)₃(CrO₄)₂O(OH)₃]^3– layers, whereas, in the structure of 2 , UO₇ and UO₆(H₂O) pentagonal bipyramids are linked through CrO₄ tetrahedra into the [(UO₂)₂(CrO₄)₃(H₂O)]^2– layers. The structures show many similarities to related uranyl selenate compounds, thus providing additional data on similarities and differences between uranyl sulfates, chromates, selenates, and molybdates.     

Jahn‐Teller‐Ordnung in pipzH2[Mn2F8], einem Fluoromanganat(III) mit neuer Schichtstruktur

Jahn‐Teller Ordering in pipzH₂[Mn₂F₈], a Fluoromanganate(III) with a New Layer Structure From a solution of (pipzH₂)[MnF₂(HPO₄)(H₂O)]·(H₂PO₄) in concentrated hydrofluoric acid the title compound could be crystallized and was characterized by X‐ray crystallography: monoclinic, space group P2₁/n, Z = 8, a = 13.275(1), 10.400(1), c = 14.928(1) Å, β = 112.337(8), R = 0.0265. The structure shows a new type of anionic layers [Mn₂F₈] built of dimers of edge‐sharing [MnF₆] octahedra linked via common vertices, alternating with layers of piperazinium(2+) cations. A dense network of hydrogen bonds N–H···F achieves a strong 3D interconnection. Strong elongation of the [MnF₆] octahedra is observed due to the Jahn‐Teller effect.The long axes show parallel (ferrodistortive) orientation within the dimers, but the ordering between the dimers is antiferrodistorive. A possible mechanism of formation is discussed on the basis of precursor structures.     

Nine-coordinate rare earth metal complexes with aminopolycarboxylic acids: Mononuclear (NH4)3[TbIII(ttha)]·5H2O and binuclear (NH4)4[Tb 2 III (dtpa)2]·9H2O

The two title coordination compounds, (NH₄)₃[Tb^III(ttha)]·5H₂O (ttha = triethylenetetramine-N,N,N′,N″,N‴,N‴-hexaacetic acid) and (NH₄)₄[Tb ₂ ^III (ttha)]·9H₂O (dtpa = diethylenetriamine-N,N,N′,N″,N″-pentaacetic acid), have been prepared and characterized by FT-IR, elemental analyses, TG-DTA and single crystal X-ray diffraction techniques. The (NH₄)₃[Tb^III(ttha)]·5H₂O compound is monoclinic, P2₁/c; a = 10.398(1) Å, b = 12.791(1) Å, c = 23.199(2) Å; β = 90.914(2)°; V = 3084.9(5) ų; Z = 4; D _calc = 1.704 g/cm³; μ(MoK _α ) = 2.376 mm^™; R = 0.023 and wR ² = 0.049 for 5429 observed reflections with I ≥ 2σ(I). The [Tb^III(ttha)]³⁻ complex anion in the crystal has a nine-coordinate mononuclear molecular structure with pseudo-monocapped square-antiprismatic configuration. The (NH₄)₄[Tb ₂ ^III (dtpa)₂]·9H₂O compound is triclinic, P-1; a = 9.739(1) Å, b = 10.010(1) Å, c = 12.968(2) Å; α= 85.890(2)°, β = 77.338(2)°, γ = 77.587(2)°; V = 1204.2(2) ų; Z = 1; D _calc = 1.832 g/cm³; μ(MoK _α ) = 3.015 mm^™; R = 0.024 and wR ² = 0.060 for 4750 observed reflections with I ≥ 2σ(I). The [Tb ₂ ^III (dtpa)₂]₄₋ complex anion has a binuclear structure in the crystal; the two Tb^III centers are equivalent and have a nine-coordinate environment with the same pseudo-tricapped trigonal-prismatic configuration. The thermal analysis revealed that the coordination cores of the (NH₄)₃[Tb^III(ttha)]·5H₂O and (NH₄)₄[Tb ₂ ^III (dtpa)₂]·9H₂O compounds are stable up to 221°C and 252°C, respectively. Original Russian Text Copyright ? 2008 by J. Wang, X. Zh. Liu, X. F. Wang, G. R. Gao, Zh. Q. Xing, X. D. Zhang, and R. Xu The text was submitted by the authors in English. Zhurnal Strukturnoi Khimii, Vol. 49, No. 1, pp. 81–89, January–February, 2008.     

Synthese und Kristallstruktur von K2(HSO4)(H2PO4), K4(HSO4)3(H2PO4) und Na(HSO4)(H3PO4)

Synthesis and Crystal Structure of K₂(HSO₄)(H₂PO₄), K₄(HSO₄)₃(H₂PO₄), and Na(HSO₄)(H₃PO₄) Mixed hydrogen sulfate phosphates K₂(HSO₄)(H₂PO₄), K₄(HSO₄)₃(H₂PO₄) and Na(HSO₄)(H₃PO₄) were synthesized and characterized by X‐ray single crystal analysis. In case of K₂(HSO₄)(H₂PO₄) neutron powder diffraction was used additionally. For this compound an unknown supercell was found. According to X‐ray crystal structure analysis, the compounds have the following crystal data: K₂(HSO₄)(H₂PO₄) (T = 298 K), monoclinic, space group P 2₁/c, a = 11.150(4) Å, b = 7.371(2) Å, c = 9.436(3) Å, β = 92.29(3)°, V = 774.9(4) ų, Z = 4, R₁ = 0.039; K₄(HSO₄)₃(H₂PO₄) (T = 298 K), triclinic, space group P 1, a = 7.217(8) Å, b = 7.521(9) Å, c = 7.574(8) Å, α = 71.52(1)°, β = 88.28(1)°, γ = 86.20(1)°, V = 389.1(8)ų, Z = 1, R₁ = 0.031; Na(HSO₄)(H₃PO₄) (T = 298 K), monoclinic, space group P 2₁, a = 5.449(1) Å, b = 6.832(1) Å, c = 8.718(2) Å, β = 95.88(3)°, V = 322.8(1) ų, Z = 2, R₁ = 0,032. The metal atoms are coordinated by 8 or 9 oxygen atoms. The structure of K₂(HSO₄)(H₂PO₄) is characterized by hydrogen bonded chains of mixed H_nS/PO₄^– tetrahedra. In the structure of K₄(HSO₄)₃(H₂PO₄), there are dimers of H_nS/PO₄^– tetrahedra, which are further connected to chains. Additional HSO₄^– tetrahedra are linked to these chains. In the structure of Na(HSO₄)(H₃PO₄) the HSO₄^– tetrahedra and H₃PO₄ molecules form layers by hydrogen bonds.     

Synthese und spektroskopische Charakterisierung von Fluorocarbonylosmaten sowie Normalkoordinatenanalyse und Kristallstruktur von fac-[OsF3Br2(CO)]2–

Synthesis and Spectroscopic Characterization of Fluorocarbonylosmates, Normal Coordinate Analysis and Crystal Structure of fac -[OsF₃Br₂(CO)]^2– By treatment of (n-Bu₄N)₂[OsBr₅(CO)] with TlF in C₆H₅CF₃ fac-(n-Bu₄N)₂[OsF₃Br₂(CO)] is formed, from which salts with the cations (Et₄N)⁺, (py₂CH₂)²⁺, Tl⁺ and Cs⁺ are obtainable. Oxidation of the by-product [OsF₅(CO)]^2– with Cl₂ yields [OsF₅(CO)]^– which ¹⁹F NMR spectrum reveals a quintet (δ_F = 89.9) and a dublet (43.5 ppm) in the ratio 1 : 4 with coupling constants ²J_FF = 94.9 Hz. Simultaneously produced mer-[OsF₃Cl₂(CO)]^– exhibits in the high field region a triplet (δ_F = –70.4) and a dublet (–66.2 ppm) in the ratio 1 : 2 and ²J_FF = 9.5 Hz. The X-ray structure determinations of fac-Tl₂[OsF₃Br₂(CO)] ( 1 ) (monoclinic P2₁/n, a = 11.143(12), b = 11.654(4), c = 13.751(10) Å, β = 91.50(6)°, Z = 8) and fac-(py₂CH₂)[OsF₃Br₂(CO)] · 1/2(CH₃)₂CO ( 2 ) (triclinic, P 1, a = 8.432(1), b = 9.009(1), c = 12.402(2) Å, α = 80.30(1), β = 79.68(2), γ = 68.14(1)°, Z = 2) result in nearly C_s symmetry of the complex anion with bond lengths in the ranges Os–F = 1.98–2.08, Os–Br = 2.45–2.46, Os–C = 1.83–1.84, C–O = 1.10 – 1.17 Å. Using the molecular parameters of the X-ray determinations the IR spectra have been assigned by normal coordinate analysis. The valence force constants are f_d(CO) = 15.4–15.7, f_d(OsC) = 4.4–4.7, f_d(OsF) = 2.4–2.7, f_d(OsF˙) = 1.6–2.0, f_d(OsBr) = 1.7–2.1 mdyn/Å.     

Die Kristallstruktur der hydratisierten Cyanokomplexe NMe4MnII[(Mn, Cr)III(CN)6] · 3 H2O und NMe4Cd[MIII(CN)6] · 3 H2O (MIII = Fe,Co): Verwandte des Berliner Blaus

The Crystal Structure of the Hydrated Cyano Complexes NMe₄Mn^II[(Mn, Cr)^III(CN)₆] · 3 H₂O and NMe₄Cd[M^III(CN)₆] · 3 H₂O (M^III = Fe, Co): Compounds Related to Prussian Blue The crystal structures of the isotypic tetragonal compounds (space group I4, Z = 10) NMe₄Mn^II · [(Mn, Cr)^III(CN)₆] · 3 H₂O (a = 1653.2(4), c = 1728.8(6) pm), NMe₄Cd[Fe(CN)₆] · 3 H₂O (a = 1642.7(1), c = 1733.1(1) pm) and NMe₄Cd[Co(CN)₆] · 3 H₂O (a = 1632.1(2), c = 1722.4(3) pm) were determined by X‐rays. They exhibit ⊥ c cyanobridged layers of octahedra [M^III(CN)₆] and [M^IIN₄(OH₂)₂], which punctually are interconnected also || c to yield altogether a spaceous framework. The M^II atoms at the positions linking into the third dimension are only five‐coordinated and form square pyramids [M^IIN₅] with angles N–M^II–N near 104° and distances of Mn–N: 1 × 214, 4 × 219 pm; Cd–N: 1 × 220 resp. 222, 4 × 226 resp. 228 pm. Further details and structural relations within the family of Prussian Blue are reported and discussed.     

Influence of the Organic Species and Oxoanion in the Synthesis of two Uranyl Sulfate Hydrates, (H3O)2[(UO2)2(SO4)3­(H2O)]·7H2O and (H3O)2[(UO2)2(SO4)3(H2O)]·4H2O,and a Uranyl Selenate‐Selenite [C5H6N][(UO2)(SeO4)(HSeO3)]

Two uranyl sulfate hydrates, (H₃O)₂[(UO₂)₂(SO₄)₃(H₂O)] · 7H₂O (NDUS) and (H₃O)₂[(UO₂)₂(SO₄)₃(H₂O)] · 4H₂O (NDUS1), and one uranyl selenate‐selenite [C₅H₆N][(UO₂)(SeO₄)(HSeO₃)] (NDUSe), were obtained and their crystal structures solved. NDUS and NDUSe result from reactions in highly acidic media in the presence of L ‐cystine at 373 K. NDUS crystallized in a closed vial at 278 K after 5 days and NDUSe in an open beaker at 278 K after 2 weeks. NDUS1 was synthesized from aqueous solution at room temperature over the course of a month. NDUS, NDUS1, and NDUSe crystallize in the monoclinic space group P2₁/n, a = 15.0249(4) Å,b = 9.9320(2) Å, c = 15.6518(4) Å, β = 112.778(1)°, V = 2153.52(9) ų,Z = 4, the tetragonal space group P4₃2₁2, a = 10.6111(2) Å,c = 31.644(1) Å, V = 3563.0(2) ų, Z = 8, and in the monoclinic space group P2₁/n, a = 8.993(3) Å, b = 13.399(5) Å, c = 10.640(4) Å,β = 108.230(4)°, V = 1217.7(8) ų, Z = 4, respectively.The structural units of NDUS and NDUS1 are two‐dimensional uranyl sulfate sheets with a U/S ratio of 2/3. The structural unit of NDUSe is a two‐dimensional uranyl selenate‐selenite sheets with a U/Se ratio of 1/2. In‐situ reaction of the L ‐cystine ligands gives two distinct products for the different acids used here. Where sulfuric acid is used, only H₃O⁺ cations are located in the interlayer space, where they balance the charge of the sheets, whereas where selenic acid is used, interlayer C₅H₆N⁺ cations result from the cyclization of the carboxyl groups of L ‐cystine, balancing the charge of the sheets.