Synthesis,Crystal Structure and Lithium Motion of Li8SeN2 and Li8TeN2

The compounds Li₈EN₂ with E = Se, Te were obtained in form of orange microcrystalline powders from reactions of Li₂E with Li₃N. Single crystal growth of Li₈SeN₂ additionally succeeded from excess lithium. The crystal structures were refined using single‐crystal X‐ray diffraction as well as X‐ray and neutron powder diffraction data (I4₁md, No. 109, Z = 4, Se: a = 7.048(1) Å, c = 9.995(1) Å, Te: a = 7.217(1) Å, c = 10.284(1) Å). Both compounds crystallize as isotypes with an anionic substructure motif known from cubic Laves phases and lithium distributed over four crystallographic sites in the void space of the anionic framework. Neutron powder diffraction pattern recorded in the temperature range from 3 K to 300 K and X‐ray diffraction patterns using synchrotron radiation taken from 300 K to 1000 K reveal the structural stability of both compounds in the studied temperature range until decomposition. Motional processes of lithium atoms in the title compounds were revealed by temperature dependent NMR spectroscopic investigations. Those are indicated by significant changes of the ⁷Li NMR signals. Lithium motion starts for Li₈SeN₂ above 150 K whereas it is already present in Li₈TeN₂ at this temperature. Quantum mechanical calculations of NMR spectroscopic parameters reveal clearly different environments of the lithium atoms determined by the electric field gradient, which are sensitive to the anisotropy of charge distribution at the nuclear sites. With respect to an increasing coordination number according to 2 + 1, 3, 3 + 1, and 4 for Li(3), Li(4), Li(2), and Li(1), respectively, the values of the electric field gradients decrease. Different environments of lithium predicted by quantum mechanical calculations are confirmed by ⁷Li NMR frequency sweep experiments at low temperatures.     

Silver Vanadyl(IV) ortho‐Pyrophosphate: Synthesis,Crystal Structure,and Characterization of the (V≡O)2+ Group

Ag₆(V^IVO)₂(PO₄)₂(P₂O₇) was obtained by reaction of Ag₃PO₄ and (VO)₂P₂O₇ (sealed ampoule, 550 °C, 3 d). The crystal structure of the new mixed ortho‐pyrophosphate was determined from X‐ray single‐crystal data [Pnma, Z = 4, a = 12.759(3) Å, b = 17.340(4) Å, c = 6.418(1) Å, R₁ = 0.071, wR₂ = 0.184 for 3174 unique reflections with F_o > 4σ(F_o), 141 variables]. Ag⁺ ions are located in between layers [(V^IVO)₂(PO₄)₂(P₂O₇)]^6–. Equilibrium relations of the new phosphate to neighboring phases were determined. The electronic structure of the (V^IV≡O)²⁺ group was investigated by polarized electronic absorption spectroscopy (ν̃_1a = 9450 cm^–1, ν̃_1b = 9950 cm^–1, ν̃₂ = 14750 cm^–1), EPR spectroscopy [X‐ and Q‐band, powder and single crystal, orthorhombic crystal g‐tensor with g₁ = 1.9445(3), g₂ = 1.9521(3), g₃ = 1.9695(3)], and magnetic measurements (powder, μ_exp/μ_B = 1.71, Θ_p = –1.7 K).     

The New Homoleptic Tetracyanamidoaluminate LiBa2[Al(CN2)4]

The new tetracyanamidoaluminate LiBa₂[Al(CN₂)₄] was prepared by solid state metathesis reaction in a fused copper ampoule from a mixture of BaF₂, AlF₃, and Li₂(CN₂) at 550 °C. The crystal structure was solved and refined based on single‐crystal X‐ray diffraction data [P2₁2₁2₁, Z = 4, a = 6.843(1) Å, b = 11.828(2) Å, c = 11.857(2) Å]. The compound belongs to the known formula type LiM₂[Al(CN₂)₄] (M = Sr, Eu) containing the homoleptic [Al(CN₂)₄]^5– ion. However, LiBa₂[Al(CN₂)₄] forms a distinct crystal structure, containing a two‐dimensional [(NCN)_2/2Li(NCN)₂Al(NCN)_2/2] network with four‐coordinate Li⁺ and Al³⁺ ions. Two crystallographically independent Ba²⁺ ions are situated in eightfold environment of terminal nitrogen atoms of cyanamide ions.     

Synthesis and Structure of Lithium Cadmium Selenite Hydroxide,LiCd2(SeO3)2(OH)

The new compound LiCd₂(SeO₃)₂(OH) has been hydrothermally synthesized and characterized by single‐crystal X‐ray diffraction and IR spectroscopy. It is built up from a network of edge‐ and vertex‐sharing pyramidal [SeO₃]^2— groups, distorted CdO₆ octahedra, and CdO₇ monocapped trigonal prisms. The cadmium‐centred groups form infinite columns, onto which Se atoms (as [SeO₃]^2— groups) are grafted. Cross‐linking between the columns results in a three‐dimensional framework which encapsulates [100] channels occupied by the tetrahedrally‐coordinated lithium cations. The H atom of the hydroxyl group appears to participate in a weak, bifurcated, hydrogen bond. Crystal data: LiCd₂(SeO₃)₂(OH), M_r = 502.67, monoclinic, P2₁/c (No. 14), a = 5.8184 (3)Å, b = 10.2790 (5)Å, c = 11.5021 (5)Å, β = 90.446(1)°, V = 687.89 (9)ų, Z = 4, R(F) = 0.021, wR(F²) = 0.046.     

Two Modifications of (TeO)(HAsO4) and its Dehydration Product (Te3O3)(AsO4)2 – Three more Examples of Tellurium(IV) with a Fivefold Oxygen Coordination

Two modifications of (TeO)(HAsO₄) were obtained by reacting tellurium dioxide with arsenic acid under boiling conditions (modification I, acid concentration 80 wt‐%) or under hydrothermal conditions (modification II, acid concentration 50 wt‐%). The crystal structures of the two modifications were determined from single‐crystal X‐ray data [modification I: P2₁/c, Z = 4, a = 7.4076(10), b = 5.9596(7), c = 9.5523(11) Å, β = 102.589(8)°, 2893 structure factors, 68 parameters, R[F² > 2σ(F²)] = 0.0247, wR₂(F² all) = 0.0530; modification II: P2₁/c, Z = 4, a = 6.2962(4), b = 4.7041(3), c = 13.9446(8) Å, β = 94.528(3)°, 2549 structure factors, 69 parameters, R[F² > 2σ(F²)] = 0.0207, wR₂(F² all) = 0.0462)]. Dehydration of (TeO)(HAsO₄)‐II at temperatures above 260 °C results in the formation of polycrystalline (Te₃O₃)(AsO₄)₂. Single crystals of the anhydrous product were grown either by heating stoichiometric amounts of the binary oxides TeO₂ and As₂O₅ in closed silica glass ampoules or with higher concentrated arsenic acid (80 wt‐%) under hydrothermal conditions at 220 °C. The common features in the crystal structures of (Te₃O₃)(AsO₄)₂ [P$\bar{1}$ , Z = 4, a = 6.5548(4), b = 7.6281(6), c = 15.0464(15) Å, α = 140.212(6), β = 102.418(9)°, γ = 77.346(5)°, 5718 structure factors, 146 parameters, R[F² > 2σ(F²)] = 0.0351, wR₂(F² all) = 0. 1093] and in that of the two modifications of acidic (TeO)(HAsO₄) are [TeO₅] square‐pyramids and [AsO₄] tetrahedra. In anhydrous (Te₃O₃)(AsO₄)₂ and in (TeO)(HAsO₄)‐II, a layered arrangement of the building units is found, whereas in the (TeO)(HAsO₄)‐I structure strands are formed. Different hydrogen bonding interactions are present in the two modifications of (TeO)(HAsO₄).     

Synthesis,Crystal Structure and Properties of Li2Cu5(PO4)4

Li₂Cu^II₅(PO₄)₄ has been obtained by various reactions starting from copper or Cu₂O. Crystallization was achieved using I₂ as oxidant and mineralizer. The new orthophosphate crystallizes in space group P$\bar{1}$ , Z = 2, with a = 6.0502(3) Å, b = 9.2359(4) Å, c = 11.4317(5) Å, α = 75.584(2)°, β = 80.260(2)°, γ = 74.178(2)°, at 293 K. Its structure has been determined from X‐ray single‐crystal data and refined to R₁ = 0.022{wR₂ = 0.058 for 4633 unique reflections with F_o > 4σ (F_o)}. From magnetic measurements μ_eff = 1.51 μ_B/Cu and θ_P = –37.4 K have been determined. The Vis/NIR spectrum of aqua‐green Li₂Cu₅(PO₄)₄ shows a single broad band centered around $\bar{1}$ = 12000 cm^–1. Magnetic behavior and spectrum are discussed within the angular overlap model.     

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.     

Influence of the Counterions on the Structures of Ternary Zn/Sn/Se Anions: Synthesis and Properties of [Rb10(H2O)14.5][Zn4(μ4‐Se)2(SnSe4)4] and [Ba5(H2O)32][Zn5Sn(μ3‐Se)4(SnSe4)4]

Reactions of rubidium or barium salts of the ortho‐selenostannate anion, [Rb₄(H₂O)₄][SnSe₄] ( 1 ) or [Ba₂(H₂O)₅][SnSe₄] ( 2 ) with Zn(OAc)₂ or ZnCl₂ in aqueous solution yielded two novel compounds with different ternary Zn/Sn/Se anions, [Rb₁₀(H₂O)_14.5][Zn₄(μ₄‐Se)₂(SnSe₄)₄] ( 3 ) and [Ba₅(H₂O)₃₂][Zn₅Sn(μ₃‐Se)₄(SnSe₄)₄] ( 4 ). 1 – 4 have been determined by means of single crystal X‐ray diffraction: 1 : triclinic space group lattice dimensions at 203 K: a = 8.2582(17) Å, b = 10.634(2) Å, c = 10.922(2) Å, α = 110.16(3)°, β = 91.74(3)°, γ = 97.86(3)°, V = 888.8(3) ų; R₁ [I > 2σ(I)] = 0.0669; wR₂ = 0.1619; 2 : orthorhombic space group Pnma; lattice dimensions at 203 K: a = 17.828(4) Å, b = 11.101(2) Å, c = 6.7784(14) Å, V = 1341.5(5) ų; R₁ [I > 2σ(I)] = 0.0561; wR₂ = 0.1523; 3 : triclinic space group ; lattice dimension at 203 K: a = 17.431(4) Å, b = 17.459(4) Å, c = 22.730(5) Å, α = 105.82(3)°, β = 99.17(3)°, γ = 90.06(3)°, V = 6563.1(2) ų; R₁ [I > 2σ(I)] = 0.0822; wR₂ = 0.1782; 4 : monoclinic space group P2₁/c; lattice dimensions at 203 K: a = 25.231(5) Å, b = 24.776(5) Å, c = 25.396(5) Å, β = 106.59(3)°, V = 15215.0(5) ų; R₁ [I > 2σ(I)] = 0.0767; wR₂ = 0.1734. The results serve to underline the crucial role of the counterion for the type of ternary anion to be observed in the crystal. Whereas Rb⁺(aq) stabilizes a P1‐type Zn/Sn/Se supertetrahedron in 3 like K⁺, the Ba²⁺(aq) ions better fit to an anionic T3‐type Zn/Sn/Se cluster arrangement as do Na⁺ ions. It is possible to estimate a radius:charge ratio for the stabilization of the two structural motifs.     

Synthesis,Characterization and Crystal Structure of Novel Mixed Bridged Trinuclear Oxo‐Centered Iron(III), Chromium(III) Complexes Containing Terminal Unsaturated Carboxylato and Acrylic Acid Dimer Anion Ligands

Three new oxo‐centered trinuclear mixed‐bridged carboxylate complexes with terminal unsaturated ligands ([M₂M′(μ₃‐O)(μ‐O₂C₃H₃)₅(μ‐O₄C₆H₇)(O₂C₃H₃) (H₂O)₂]·2H₂O [M = Fe, M′ = Fe ( 1 ); M = Fe, M′ = Cr ( 2 ); M = Cr, M′ = Fe ( 3 )]) have been synthesized and characterized by means of elemental analyses, IR spectra and crystal structure analyses. The compounds crystallize isotypically in the orthorhombic space group type Pbcn with a = 24.622(3) Å, b = 16.304(2) Å, c = 17.491(2) Å, V = 7021.5(15) ų ( 1 ), a = 24.708(5) Å, b = 16.290(2) Å, c = 17.394(2) Å, V = 7001.0(18) ų ( 2 ), a = 24.611(4) Å, b = 16.300(3) Å, c = 17.359(3) Å, V = 6964(2) ų ( 3 ), and Z = 8. The infrared spectra show resolved bands arising from ν_asym(OCO) and ν_sym(OCO) vibrations of monodentate and bridging carboxylate ligands along with those of ν_asym(M₂M′O) vibrations in the complexes.     

Three Ternary Rare Earth(III) Complexes Based on 3‐[(4,6‐Dimethyl‐2‐pyrimidinyl)thio]‐propanoic Acid and 1,10‐Phenanthroline: Synthesis,Crystal Structure and Antioxidant Activity

Three ternary rare earth [Nd^III ( 1 ), Sm^III ( 2 ) and Y^III ( 3 )] complexes based on 3‐[(4,6‐dimethyl‐2‐pyrimidinyl)thio]‐propanoic acid (HL) and 1,10‐phenanthroline (Phen) were synthesized and characterized by IR and UV/Vis spectroscopy, TGA, and single‐crystal X‐ray diffraction. The crystal structures showed that complexes 1 – 3 contain dinuclear rare earth units bridged by four propionate groups and are of general formula [REL₃(Phen)]₂ · nH₂O (for 1 and 2 : n = 2; for 3 : n = 0). All rare earth ions are nine‐coordinate with distorted mono‐capped square antiprismatic coordination polyhedra. Complex 1 crystallizes in the monoclinic system, space group P2₁/c with a = 16.241(7) Å, b = 16.095(7) Å, c = 19.169(6) Å, β = 121.48(2)°. Complex 2 crystallizes in the monoclinic system, space group P2₁/c with a = 16.187(5) Å, b = 16.045(4) Å, c = 19.001(4) Å, β = 120.956(18)°. Complex 3 crystallizes in the triclinic system, space group P1 with a = 11.390(6) Å, b = 13.636(6) Å, c = 15.958(7) Å, α = 72.310(17)°, β = 77.548(15)°, γ = 78.288(16)°. The antioxidant activity test shows that all complexes own higher antioxidant activity than free ligands.     

Neue Thiophosphate: Die Verbindungen Li6Ln3(PS4)5 (Ln: Y,Gd, Dy,Yb, Lu) und Ag3Y(PS4)2

New Thiophosphates: The Compounds Li₆Ln₃(PS₄)₅ (Ln: Y, Gd, Dy, Yb, Lu) and Ag₃Y(PS₄)₂ The new thiophosphates Li₆Ln₃(PS₄)₅ (Ln: Y, Gd, Dy, Yb, Lu) were synthesized by heating mixtures of Ln, P, S, and Li₂S₄ at 900 °C (100 h) and they were investigated by single crystal X‐ray methods. The compounds with Ln = Y (a = 28.390(2), b = 10.068(1), c = 33.715(2) Å, β = 113.85(1)°), Gd (a = 28.327(2), b = 10.074(1), c = 33.822(2) Å, β = 114.297(7)°), Dy (a = 28.124(6), b = 10.003(2), c = 33.486(7) Å, β = 113.89(3)°), Yb (a = 28.178(3), b = 9.977(1), c = 33.392(4) Å, β = 113.65(1)°), and Lu (a = 28.169(6), b = 10.002(2), c = 33.432(7) Å, β = 113.54(3)°) are isotypic and crystallize in a new structure type (C2/c; Z = 12). Main feature are PS₄ tetrahedra isolated from each other surrounding the Ln and Li atoms via their S atoms. The coordination number of the five crystallographically independent Ln atoms is eight, but the polyhedra are quite different and they are interlinked to larger units extending in [010]. The environment of the Li atoms is irregular and formed by five to six S atoms. The crystal structure is compared with that of Li₉Ln₂(PS₄)₅ (Ln: Nd, Gd). For the synthesis of Ag₃Y(PS₄)₂ (a = 16.874(3), b = 9.190(2), c = 9.312(2) Å, β = 123.17(3)°) a mixture of Y, P, S, and Ag₂S was heated to 700 °C (50 h). The thiophosphate crystallizes in a new structure type (C2/c; Z = 4) composed of isolated PS₄ tetrahedra. The two crystallographically independent Ag atoms are surrounded by four S atoms in the shape of distorted tetrahedra. The Ag(1)S₄ polyhedra are cornershared to strands running along [001], which are linked together via Ag(2)S₄ tetrahedra. The environment of the Y atoms is composed of eight S atoms each building distorted square antiprisms. These polyhedra are connected with each other via common edges to a strand running along [001].     

Sr3(BS3)2 und Sr3(B3S6)2: Zwei neue nicht‐oxidische Chalkogenoborate mit trigonal‐planar koordiniertem Bor

Sr₃(BS₃)₂ and Sr₃(B₃S₆)₂: Two Novel Non‐oxidic Chalcogenoborates with Boron in a Trigonal‐Planar Coordination The thioborates Sr₃(BS₃)₂ and Sr₃(B₃S₆)₂ were prepared from strontium sulfide, amorphous boron and sulfur in solid state reactions at a temperature of 1123 K. In a systematic study on the structural cation influence on this type of ternary compounds, the crystal structures were determined by single crystal X‐ray diffraction. Sr₃(BS₃)₂ crystallizes in the monoclinic spacegroup C2/c (No. 15) with a = 10.187(4) Å, b = 6.610(2) Å, c = 15.411(7) Å, β = 102.24(3)° and Z = 4. The crystal structure of Sr₃(B₃S₆)₂ is trigonal, spacegroup R3¯ (Nr. 148), with a = 8.605(1) Å, c = 21.542(4) Å and Z = 3. Sr₃(BS₃)₂ contains isolated [BS₃]^3— anions with boron in a trigonal‐planar coordination. The strontium cations are found between the layers of orthothioborate anions. Sr₃(B₃S₆)₂ consists of cyclic [B₃S₆]^3— anions and strontium cations, respectively.     

Synthesis,Structure and Thermodynamic Property of a New Lithium Borate: Li4[B8O13(OH)2]·3H2O

A new hydrated lithium borate, Li₄[B₈O₁₃(OH)₂]·3H₂O, has been hydrothermally synthesized and characterized by single crystal X‐ray diffraction, FT‐IR spectroscopy, simultaneous TGA‐DTA and chemical analysis. It crystallizes in the triclinic, space group , a=8.4578(5) Å, b=8.7877(5) Å, c=10.8058(7) Å, α=87.740(3)°, β=71.819(3)°, γ=61.569(3)°, Z=2, V=665.26(7) ų, D_c=2.043 g/cm³. Its crystal structure features polyborate anionic layers with the larger odd 13‐membered boron rings constructed by [B₈O₁₃(OH)₂]^4? FBBs. Through designing the thermochemical cycle, the standard molar enthalpy of formation of this borate was determined to be ?(7953.8±6.6) kJ·mol^?1 by using a heat conduction microcalorimeter.     

Alkoxo‐Verbindungen des dreiwertigen Eisen: Synthese und Charakterisierung von [Fe2(OtBu)6], [Fe2Cl2(OtBu)4], [Fe2Cl4(OtBu)2] und [N(nBu)4]2[Fe6OCl6(OMe)12]

Alkoxo Compounds of Iron(III): Syntheses and Characterization of [Fe₂(OtBu)₆], [Fe₂Cl₂(OtBu)₄], [Fe₂Cl₄(OtBu)₂] and [N(nBu)₄]₂[Fe₆OCl₆(OMe)₁₂] The reaction of iron(III)chloride in diethylether with sodium tert‐butylat yielded the homoleptic dimeric tert‐‐butoxide Fe₂(OtBu)₆ ( 1 ). The chloro‐derivatives [Fe₂Cl₂(OtBu)₄] ( 2 ), and [Fe₂Cl₄(OtBu)₂] ( 3 ) could be synthesized by ligand exchange between 1 and iron(III)chloride. Each of the molecules 1 , 2 , and 3 consists of two edge‐sharing tetrahedrons, with two tert‐butoxo‐groups as μ₂‐bridging ligands. For the synthesis of the alkoxides 1 , 2 , and 3 diethylether plays an important role. In the first step the dietherate of iron(III)chloride FeCl₃(OEt₂)₂ ( 4 ) is formed. The reaction of iron(III)chloride with tetrabutylammonium methoxide in methanol results in the formation of a tetrabutylammonium methoxo‐chloro‐oxo‐hexairon cluster [N(nBu)₄]₂[Fe₆OCl₆(OMe)₁₂] ( 5 ). Crystal structure data: 1 , triclinic, P1¯, a = 9.882(2) Å, b = 10.523(2) Å, c = 15.972(3) Å, α = 73.986(4)°, β = 88.713(4)°, γ = 87.145(4)°, V = 1594.4(5) ų, Z = 2, d_c = 1.146 gcm^—1, R₁ = 0.044; 2 , monoclinic, P2₁/n, a = 11.134(2) Å, b = 10.141(2) Å, c = 12.152(2) Å und β = 114.157(3)°, V = 1251.8(4) ų, Z = 2, d_c = 1.377 gcm^—1, R₁ = 0.0581; 3 , monoclinic, P2₁/n, a = 6.527(2) Å, b = 11.744(2) Å, c = 10.623(2), β = 96.644(3)°, V = 808.8(2) ų, Z = 2, d_c = 1.641 gcm^—1, R₁ = 0.0174; 4 , orthorhombic, Iba2, a = 23.266(5) Å, b = 9.541(2) Å, c = 12.867(3) Å, V = 2856(2) ų, Z = 8, d_c = 1.444 gcm^—1, R₁ = 0.0208; 5 , trigonal, P3₁, a = 13.945(2) Å, c = 30.011(6) Å, V = 5054(2) ų, Z = 6, d_c = 1.401 gcm^—1; R_c = 0.0494.     

Alkoholyse von [Fe2(OtBu)6] als einfacher Weg zu neuen Eisen(III)‐Alkoxo‐Verbindungen: Synthesen und Kristallstrukturen von [Fe2(OtAmyl)6], [Fe5OCl(OiPr)12], [Fe5O(OiPr)13], [Fe5O(OiBu)13], [Fe5O(OCH2CF3)13], [Fe5O(OnPr)13] und [Fe9O3(OnPr)21] · iPrOH

Alcoholysis of [Fe₂(O^tBu)₆] as a Simple Route to New Iron(III)‐Alkoxo Compounds: Synthesis and Crystal Structures of [Fe₂(O^tAmyl)₆], [Fe₅OCl(OⁱPr)₁₂], [Fe₅O(OⁱPr)₁₃], [Fe₅O(OⁱBu)₁₃], [Fe₅O(OCH₂CF₃)₁₃], [Fe₅O(OⁿPr)₁₃], and [Fe₉O₃(OⁿPr)₂₁] · ⁿPrOH New alkoxo‐iron compounds can be synthesized easily by alcoholysis of [Fe₂(O^tBu)₆] ( 1 ). Due to different bulkyness of the alcohols used, three different structure types are formed: [Fe₂(OR)₆], [Fe₅O(OR)₁₃] and [Fe₉O₃(OR)₂₁] · ROH. We report synthesis and crystal structures of the compounds [Fe₅OCl(OⁱPr)₁₂] ( 2 ), [Fe₂(O^tAmyl)₆] ( 3 ), [Fe₅O(OⁱPr)₁₃] ( 4 ), [Fe₅O(OⁱBu)₁₃] ( 5 ), [Fe₅O(OCH₂CF₃)₁₃] ( 6 ), [Fe₉O₃(OⁿPr)₂₁] · ⁿPrOH ( 7 ) and [Fe₅O(OⁿPr)₁₃] ( 8 ). Crystallographic Data: 2 , tetragonal, P 4/n, a = 16.070(5) Å, c = 9.831(5) Å, V = 2539(2) ų, Z = 2, d_c = 1.360 gcm^?3, R₁ = 0.0636; 3 , monoclinic, P 2₁/c, a = 10.591(5) Å, b = 10.654(4) Å, c = 16.740(7) Å, β = 104.87(2)°, V = 1826(2) ų, Z = 2, d_c = 1.154 gcm^?3, R₁ = 0.0756; 4 , triclinic, , a = 20.640(3) Å, b = 21.383(3) Å, c = 21.537(3) Å, α = 82.37(1)°, β = 73.15(1)°, γ = 61.75(1)°, V = 8013(2) ų, Z = 6, d_c = 1.322 gcm^?3, R₁ = 0.0412; 5 , tetragonal, P 4cc, a = 13.612(5) Å, c = 36.853(5) Å, V = 6828(4) ų, Z = 4, d_c = 1.079 gcm^?3, R₁ = 0.0609; 6 , triclinic, , a = 12.039(2) Å, b = 12.673(3) Å, c = 19.600(4) Å, α = 93.60(1)°, β = 97.02(1)°, γ = 117.83(1)°, V = 2600(2) ų, Z = 2, d_c = 2.022 gcm^?3, R₁ = 0.0585; 7 , triclinic, , a = 12.989(3) Å, b = 16.750(4) Å, c = 21.644(5) Å, α = 84.69(1)°, β = 86.20(1)°, γ = 77.68(1)°, V = 4576(2) ų, Z = 2, d_c = 1.344 gcm^?3, R₁ = 0.0778; 8 , triclinic, , a = 12.597(5) Å, b = 12.764(5) Å, c = 16.727(7) Å, α = 91.94(1)°, β = 95.61(1)°, γ = 93.24(2)°, V = 2670(2) ų, Z = 2, d_c = 1.323 gcm^?3, R₁ = 0.0594.     

Crystal Structures,Dimorphism and Lithium Mobility of Li7MO6 (M = Bi,Ru, Os)

Li₇MO₆ (M = Bi, Ru, Os) have been synthesized by solid state reaction of Li₂O with Bi₂O₃, or MO₂ (M = Ru, Os) and characterized using powder X‐ray diffraction, differential scanning calorimetry, magnetic susceptibility (for M = Ru, Os), ionic conductivity and ⁶Li solid state NMR (for M = Bi) measurements. All three compounds exhibit a temperature induced triclinic – rhombohedral phase transition. Structures of the new low temperature triclinic phases have been refined by the Rietveld method from powder X‐ray data using atomic parameters of Li₇TaO₆ as a starting model ( Li₇BiO₆ : triclinic, , a = 5.5071(1), b = 6.0425(1), c = 5.5231(1) Å, α = 116.912(1), β = 120.867(1), γ = 62.234(1)°, V = 133.96(1) ų, Z = 1, T = 230 K; Li₇RuO₆ : triclinic, , a = 5.3654(1), b = 5.8584(1), c = 5.3496(1) Å, α = 117.182(1), β = 119.117(1), γ = 62.632(1)°, V = 124.43(1) ų, Z = 1, T = 295 K; Li₇OsO₆ : triclinic, , a = 5.3786(1), b = 5.8725(1), c = 5.3591(1) Å, α = 117.193(1), β = 119.277(1), γ = 62.700(1)°, V = 125.15(1) ų, Z = 1, T = 295 K). Upon cooling, Li₇RuO₆ and Li₇OsO₆ undergo a magnetic transition at 12 and 13 K, respectively, from the paramagnetic to the antiferromagnetic state. The higher ionic conductivity of Li₇BiO₆ at T < 300 °C, as compared to Li₇RuO₆ and Li₇OsO₆, can be ascribed to the undergoing of the triclinic – rhombohedral transition at a much lower temperature. At T > 300 °C, the ionic conductivity of all three compounds increases sharply due to the melting of the lithium sublattice; for Li₇RuO₆ and Li₇OsO₆ the latter effect is superimposed by the phase transitions to the rhombohedral modifications.     

Syntheses and Structures of Two Selenite Chloride Hydrates: Co(HSeO3)Cl · 3 H2O and Cu(HSeO3)Cl · 2 H2O

The first selenite chloride hydrates, Co(HSeO₃)Cl · 3 H₂O and Cu(HSeO₃)Cl · 2 H₂O, have been prepared from solution and characterised by single‐crystal X‐ray diffraction. The cobalt phase adopts an unusual “one‐dimensional” structure built up from vertex‐sharing pyramidal [HSeO₃]^2–, and octahedral [CoO₂(H₂O)₄]^2– and [CoO₂(H₂O)₂Cl₂]^4– units. Inter‐chain bonding is by way of hydrogen bonds or van der Waals' interactions. The atomic arrangement of the copper phase involves [HSeO₃]^2– pyramids and Jahn‐Teller distorted [CuCl₂(H₂O)₄] and [CuO₄Cl₂]^8– octahedra, sharing vertices by way of Cu–O–Se and Cu–Cl–Cu bonds. Crystal data: Co(HSeO₃)Cl · 3 H₂O, M_r = 276.40, triclinic, space group P 1 (No. 2), a = 7.1657(5) Å, b = 7.3714(5) Å, c = 7.7064(5) Å, α = 64.934(1)°, β = 68.894(1)°, γ = 71.795(1)°, V = 337.78(7) ų, Z = 2, R(F) = 0.036, wR(F) = 0.049. Cu(HSeO₃)Cl · 2 H₂O, M_r = 263.00, orthorhombic, space group Pnma (No. 62), a = 9.1488(3) Å, b = 17.8351(7) Å, c = 7.2293(3) Å, V = 1179.6(2) ų, Z = 8, R(F) = 0.021, wR(F) = 0.024.     

Konformation und Vernetzung von (CuCN)6‐Ringen in polymeren Cyanocupraten(I) [Cu2(CN)3—] (n = 2, 3)

Conformation and Cross Linking of (CuCN)₆‐Rings in Polymeric Cyanocuprates(I) equation/tex2gif-stack-8.gif [Cu₂(CN)₃^—] (n = 2, 3) The alkaline‐tricyano‐dicuprates(I) Rbequation/tex2gif-stack-9.gif[Cu₂(CN)₃] · H₂O ( 1 ) and Csequation/tex2gif-stack-10.gif[Cu₂(CN)₃] · H₂O ( 2 ) were synthesized by hydrothermal reaction of CuCN and RbCN or CsCN. The dialkylammonium‐tricyano‐dicuprates(I) [NH₂(Me)₂]equation/tex2gif-stack-11.gif[Cu₂(CN)₃] ( 3 ), [NH₂(iPr)₂]equation/tex2gif-stack-12.gif[Cu₂(CN)₃] ( 4 ), [NH₂(Pr)₂]equation/tex2gif-stack-13.gif[Cu₂(CN)₃] ( 5 ) and [NH₂(secBu)₂]equation/tex2gif-stack-14.gif[Cu₂(CN)₃] ( 6 ) were obtained by the reaction of dimethylamine, diisopropylamine, dipropylamine or di‐sec‐butylamine with CuCN and NaCN in the presence of formic acid. The crystal structures of these compounds are built up by (CuCN)₆‐rings with varying conformations, which are connected to layers ( 1 ) or three‐dimensional zeolite type cyanocuprate(I) frameworks, depending on the size and shape of the cations ( 2 to 6 ). Crystal structure data: 1 , monoclinic, P2₁/c, a = 12.021(3)Å, b = 8.396(2)Å, c = 7.483(2)Å, β = 95.853(5)°, V = 751.4(3)ų, Z = 4, d_c = 2.728 gcm^—1, R₁ = 0.036; 2 , orthorhombic, Pbca, a = 8.760(2)Å, b = 6.781(2)Å, c = 27.113(5)Å, V = 1610.5(5)ų, Z = 8, d_c = 2.937 gcm^—1, R₁ = 0.028; 3 , orthorhombic, Pna2₁, a = 13.504(3)Å, b = 7.445(2)Å, c = 8.206(2)Å, V = 825.0(3)ų, Z = 4, d_c = 2.023 gcm^—1, R₁ = 0.022; 4 , orthorhombic, Pbca, a = 12.848(6)Å, b = 13.370(7)Å, c = 13.967(7)Å, V = 2399(2)ų, Z = 8, d_c = 1.702 gcm^—1, R₁ = 0.022; 5 , monoclinic, P2₁/n, a = 8.079(3)Å, b = 14.550(5)Å, c = 11.012(4)Å, β = 99.282(8)°, V = 1277.6(8)ų, Z = 4, d_c = 1.598 gcm^—1, R₁ = 0.039; 6 , monoclinic, P2₁/c, a = 16.215(4)Å, b = 13.977(4)Å, c = 14.176(4)Å, β = 114.555(5)°, V = 2922(2)ų, Z = 8, d_c = 1.525 gcm^—1, R₁ = 0.070.     

Synthesis,Crystal Structure,and Magnetic Properties of (2,2′‐dipyridylamine)(X−) Copper(II) Complexes (X−: Cyanate,Dicyanamide, Acetate,Thiocyanato)

The synthesis, structure, and magnetic properties of four 2,2′‐dipyridylamine ligand (abbreviated as Hdpa) containing copper(II) complexes. There is one binuclear compound, which is [Cu₂(μ_1,1‐NCO)₂(NCO)₂(Hdpa)₂] ( 1 ), and three mononuclear compounds, which are [Cu{N(CN)₂}₂(Hdpa)₂] ( 2 ), [Cu(CH₃CO₂)(Hdpa)₂·N(CN)₂] ( 3 ), and [Cu(NCS)(Acac)] ( 4 ). Compounds 1 and 4 crystallize in the monoclinic system, space group P2(1)/c and Z = 4, with a = 8.2465(6) Å, b = 9.3059(7) Å, c = 16.0817(12) Å, β = 91.090(1)°, and V = 1233.90(16) ų for 1 and a = 7.6766(6) Å, b = 21.888(3) Å, c = 10.4678(12) Å, β = 90.301(2)°, and V= 1758.8(4) ų for 4 . Compounds 2 and 3 crystallize in the triclinic system, space group P‐1 and Z = 1, with a = 8.1140(3) Å, b = 8.2470(3) Å, c = 9.3120(4) Å, β = 102.2370(10)°, and V = 592.63(4) ų for 2 and a = 7.4780(2) Å, b = 12.5700(3) Å, c = 13.0450(3) Å, β = 96.351(2)°, and V = 1211.17(5) ų for 3 . Complex ( 1 ), the magnetic data was fitted by the Bleaney‐Bowers equation (1). A very good fit was derived with J = 23.96, Θ = ?1.5 (g = 1.97). Complex ( 1 ) shows the ferromagnetism. Complexes ( 2 ), ( 3 ) and ( 4 ) of have the it is the typical paramagnetic behavior of unpaired electrons. Under a low temperature around 25 K, complexes ( 2 ) and ( 3 ) show weak ferromagnetic behavior. They are the cause of hydrogen bonds.     

Das Lanthaniodidethanid o‐La5I9(C2) – Die orthorhombische Hochtemperaturmodifikation

The Lanthanumiodideethanide o‐La₅I₉(C₂) – The Orthorhombic High Temperature Modification o‐La₅I₉(C₂) is synthesized by reaction of LaI₃, La metal and graphite powder in sealed Ta containers at 850 °C < T < 900 °C. It crystallizes in the orthorhombic space group Pbca with a = 8.0247(16) Å, b = 16.887(3) Å, c = 35.886(7) Å. o‐Ce₅I₉(C₂) is isotypic with the lattice parameters a = 7.9284(4) Å, b = 16.714(1) Å, c = 35.530(3) Å. o‐La₅I₉(C₂) transforms at 800 °C to the triclinic low temperature modification t‐La₅I₉(C₂). The transformation is reversible. The La atoms form trigonal bipyramids centered by C₂ groups. These units are connected by iodine atoms above the faces (f), edges (e) and corners according to La₅(C₂)I(f)ⁱI(e)^i?i_2/2I(e)^i?a_7/2I(e)^a?i_7/2. The C‐C distance in the C₂ unit is 1.45(2) Å. The crystals with greenish luster are moisture sensitive.