Ternäre Halogenide vom Typ A3MX6. III [1, 2]. Synthese,Strukturen und Ionenleitfähigkeit der Halogenide Na3MX6 (X = Cl,Br)

Ternary Halides of the A₃MX₆ Type. III [1, 2]. Synthesis, Structures, and Ionic Conductivity of the Halides Na₃MX₆ (X = Cl, Br) The bromides Na₃MBr₆ crystallize with the stuffed LiSbF₆-type structure (type I; M = Sm? Gd) or with the structure of the mineral cryolite (type II; M = Gd? Lu). The structure types were refined from single crystal X-ray data (Na₃SmBr₆: trigonal, space group R3 , a = 740.8(2) pm, c = 1 998.9(8) pm, Z = 3; Na₃YBr₆: monoclinic, space group P2₁/n, a = 721.3(4) pm, b = 769.9(2) pm, c = 1 074.8(4) pm, β = 90.60(4)°, Z = 2). Reversible phase transitions from one structure to the other occur. The phase transition temperatures were determined for the bromides as well as for the chlorides Na₃MCl₆ (M = Eu? Lu). The refinement of both structures for one compound was possible for Na₃GdBr₆ (I: trigonal, space group R3 , a = 737.1(5) pm, c = 1 887(2) pm, Z = 3; II: monoclinic, space group P2₁/n, a = 725.2(1) pm, b = 774.1(3) pm, c = 1 080.1(3) pm, β = 90.76(3)°, Z = 2). All compounds exhibit ionic conductivity of the sodium ions which decreases with the change from type I to type II. The conductivity of the bromides is always higher when compared with the respective chlorides.     

Die Kristallstrukturen von ErSeI und NaErSe2

The Crystal Structures of ErSeI and NaErSe₂ It is reported about attempts to synthesize lanthanoide selenidehalides of the formula LnSeX (X ? Cl, Br, I) exemplary for Ln ? Er. The relative stabilities of these compounds are discussed. X-ray crystal structure analysis revealed for the compounds ErSeBr and ErSeI the FeOCl-structure type (space group Pmmn, Z = 2, a = 406.3(5) pm, b = 559.2(6) pm, and c = 795(1) pm, and a = 418.26(6) pm, b = 558.4(1) pm, and c = 889.0(2) pm, respectively). A corresponding chloride was not found within the scope of this investigation. From the educts Er₂Se₃ and ErCl₃ in the presence of NaCl as flux in Nb-ampoules the compound NaErSe₂ was formed instead which crystallizes in an α-NaFeO₂-type structure (space group R3 m, Z = 3, a = 408.41(2) pm and c = 2067.4(2) pm).     

Einkristallstrukturbestimmungen der kubischen Hochdruckelpasolithe Rb2LiFeF6 und Cs2NaFeF6: Druck-Abstands-Paradoxon ohne Änderung der Koordinationszahl

Single Crystal Structure Determinations of the Cubic High Pressure Elpasolites Rb₂LiFeF₆ and Cs₂NaFeF₆: Pressure-Distance Paradox without Change of Coordination Number At single crystals of metastable high pressure phases of Rb₂LiFeF₆ (a = 824.4 pm) and Cs₂NaFeF₆ (a = 873,9 pm) the parameters of the cubic elpasolite structure (Fm3 m, Z = 4) were determined by X-ray methods. Compared to the 12L-structures of the normal pressure phases (R3 m, hex. Z = 6) only the distances within the 12-coordination, Rb? F = 291.7 resp. Cs? F = 309.9 pm, are compressed by 2–3%. However, the octahedral distances Fe? F = 194.6 pm and Li? F = 217.6 pm resp. Fe? F = 194.9 pm and Na? F = 242.0 pm, are enlarged by 1–4%, though there was no increase in coordination number. This paradoxical behaviour is discussed. Difference Fourier syntheses reveal disorder only for the lithium positions in Rb₂LiFeF₆, which are 30 pm off-center, corresponding to a splitting of distances Li? F into 188, 247 and 4 × 220 pm.     

LiSr2[ReN4] und LiBa2[ReN4] – isotype Nitridorhenate(VII)

LiSr₂[ReN₄] and LiBa₂[ReN₄] – isotypic Nitridorhenates(VII) The quaternary nitridorhenates(VII) LiAE₂[ReN₄] (AE = Sr, Ba) were synthesized by reaction of the metals with molecular nitrogen at 850–900 °C. The plate‐like, nearly colourless crystals were investigated by X‐ray single crystal methods and were identified as isotypic phases: LiSr₂[ReN₄] (LiBa₂[ReN₄]); monoclinic, P2₁/m; a = 614.64(8) pm (651.04(12) pm), b = 585.97(6) pm (b = 598.86(9) pm), c = 689.70(17) pm (737.43(5) pm), β = 106.375(4)° (108.535(2)°); Z = 2. Crystals of the strontium compound were systematically twinned along [001]. In the crystal structures of the quaternary compounds the alkaline earth‐ and nitride‐ ions are arranged in the motif of the InNi₂‐type structure. Strontium and barium are in a trigonal prismatic coordination by nitrogen (Sr–N: 261.0(7)–284.3(4) pm; Ba–N: 278.0(7)–303.0(6) pm). One half of the tetrahedral voids within the partial structure formed by stacking of trigonal prismatic rod layers is occupied by rhenium (formation of [Re^VIIN₄]^5–‐tetrahedra; Re–N: 181.0(6)–184.5(8) pm), lithium takes the positions of the remaining tetrahedral sites (Li–N: 2 × 198(1) pm, 224(2) pm and 228(2) pm for the strontium phase). In the barium compound the lithium positions show a larger shift from the tetrahedral centres towards a tetrahedral plane (Li–N: 2 × 195(1) pm, 213(2) pm and 304(2) pm).     

Sr5[NbN4]N ‐ A Nitridoniobate(V) Nitride Containing Isolated [NbN4]7‐ Tetrahedra and Octahedral Chains 1(Sr4Sr2/2N7+)

Sr₅[NbN₄]N (transparent, red single crystals) was synthesized by reaction of Sr2N with Nb under nitrogen at ambient pressure and 1223 K. The crystal structure was solved and refined in the space group Pbcm (no. 57), Z = 4, with lattice constants a = 646.6(3) pm, b = 1792.5(9) pm, c = 729.8(4) pm, and R = 0.019, wR² = 0.034. The crystal structure contains both isolated tetrahedra [NbN₄]^7‐ as well as chains of corner sharing octahedra 1(Sr₄Sr_2/2N⁷⁺). Strontium is irregularly coordinated by nitrogen (CN = 4 ‐ 6, Sr‐N: 252.3(4) ‐ 340.8(3) pm); nitrogen is located in a distorted octahedral environment by strontium and niobium (Nb‐N: 194.5(4) ‐ 199.2(2) pm). By formal reduction of the structural building units to their centers a close structural relationship to both the NiAs and the CaSi type structure is evident.     

Das Kupfer–Iridiumborid Cu2Ir4B3 mit einer vom ZnIr4B3‐Typ abgeleiteten Schichtstruktur

The Copper Iridium Boride Cu₂Ir₄B₃ with a Layer Structure Derived from the ZnIr₄B₃ Type The new compound Cu₂Ir₄B₃ (orthorhombic, Cmcm, a = 283.21(2) pm, b = 2540.6(1) pm, c = 281.06(2) pm, Z = 2, 209 reflexions, 18 parameters, R = 0.043) was prepared by reaction of the elements. The structure is related to the ZnIr₄B₃ type. It contains slabs composed of Ir₆B‐ und Ir₆‐prisms which alternate with copper double layers.     

BiGaIn2S6 – Synthese,Struktur und Eigenschaften

BiGaIn₂S₆ – Synthesis, Structure, and Properties The novel compound BiGaIn₂S₆ was obtained in the quaternary system Bi–Ga–In–S. BiGaIn₂S₆ forms red transparent platelets and exhibits a range of homogeneity between BiGa₁In₂S₆ and BiGa_0.8In_2.2S₆. The compound is a semiconductor with E_g(opt.) = 1.9 eV. – BiGaIn₂S₆ crystallizes monoclinically forming a new structure type (a = 1112.0 pm, b = 380.6 pm, c = 1228.0 pm, β = 116.30°, Z = 2, space group P2₁/m, no. 11). The S atoms form strongly corrugated 2 D fragments of the (hc)₂ sphere packing type. The In atoms occupy octahedral holes (d(In–S) = 262 pm) and the Ga atoms tetrahedral holes (d(Ga–S) = 234 pm) inside the 2 D-layers. The Bi atoms on the top of trigonal BiS₃ pyramids (d(Bi–S) = 265 pm) are at the periphery of the layers and have four additional S ligands from the neigbouring layer at much larger distances (d(Bi–S) = 319 pm). – The bonding of a Bi^III sulfide is analyzed for the first time by the Electron Localization Function (ELF).     

Die Reaktion von SeCl4 mit Übergangsmetalltetrachloriden. Synthese und Kristallstrukturen von (SeCl3)2MCl6 mit M = Zr,Hf, Mo,Re

The Reaction of SeCl₄ with Transition Metal Tetrachlorides. Synthesis and Crystal Structures of (SeCl₃)₂MCl₆ with M = Zr, Hf, Mo, Re The transition metal tetrachlorides ZrCl₄, HfCl₄ and MoCl₄ react with SeCl₄ in closed ampoules at temperatures of 140°C to (SeCl₃)₂MCl₆ (M = Zr, Hf, Mo) which are all isotypic and crystallize in the (SeCl₃)₂ReCl₆ structure type (orthorhombic, Fdd2, Z = 8, lattice constants for M = Zr: a = 1165.7(1)pm, b = 1287.2(2)pm, c = 2180.2(2)pm; for M = Hf: a = 1162.9(2)pm, b = 1285.0(2)pm, c = 2178.2(3)pm; for M = Mo: a = 1153.8(1)pm, b = 1267.7(1)pm, c = 2147.4(2)pm). The Cl^? ions form a hexagonal closest packing with one fourth of the octahedral holes filled by Se⁴⁺ and M⁴⁺ in an ordered way. The MCl₆ octahedra are regular, the SeCl₆ octahedra are distorted with 3 short and 3 long Se? Cl bonds (mean 215 pm and 287 pm). The structures can thus be regarded as built of SeCl₃⁺ and MCl₆^2? ions. Magnetic susceptibility measurements show for M = Zr the expected diamagnetic behavior, for M = Mo and Re paramagnetic behavior according to the Curie-Weiss law with magnetic moments of 2.5 B. M. for M = Mo and 3.7 B. M. for M = Re corresponding to 2 and 3 unpaired electrons respectivly.     

Quaternäre Chloride des zweiwertigen Europiums mit dreiwertigen Übergangsmetallen: Synthese und Kristallstruktur von Na6Eu3M4Cl24 (M = Ti,V, Cr)

Quaternary Chlorides of Divalent Europium and Trivalent Transition Metal Ions: Synthesis and Crystal Structure of Na₆Eu₃M₄Cl₂₄ (M = Ti, V, Cr) The reaction of EuCl₂, NaCl and MCl₃ (M = Ti, V, Cr) yields the chlorides Na₆Eu₃M₄Cl₂₄. According to X‐ray single crystal investigations, their crystal structure is a variant of the monoclinic cryolite‐type structure. One crystallographic site is occupied by Na1 and Eu simultaneously. For charge compensation the Na2 site is not fully occupied. In Na₆Eu₃Ti₄Cl₂₄ (P2₁/n, Z = 1/2, a = 663.8(1) pm, b = 718.3(1) pm, c = 953.3(2) pm, β = 91.55(2)°, R_all = 0.0314), Na₆Eu₃V₄Cl₂₄ (P2₁/n, Z = 1/2, a = 660.4(1) pm, b = 715.8(1) pm, c = 946.5(2) pm, β = 91.41(2)°, R_all = 0.0313) and Na₆Eu₃Cr₄Cl₂₄ (P2₁/n, Z = 1/2, a = 654.8(1) pm, b = 706.5(1) pm, c = 945.4(2) pm, β = 91.07(2)°, R_all = 0.0368) the ratio of Na1 : Eu amounts to 5 : 3. The colours of the compounds, orange yellow for M = Ti, orange red for M = V and dark red for M = Cr, indicate electronic interactions between Eu²⁺ and M³⁺.     

Preparation and Crystal Structures of some Binary Pnictides of Scandium,Zirconium, and Hafnium: Sc5Bi3, ZrBi, α‐HfSb,HfBi, HfBi2, and the Compound Zr5Bi3X1–x,Possibly Stabilized by an Impurity (X)

The title compounds were prepared by reaction of the elemental components. Of these Sc₅Bi₃ is a new compound. Its orthorhombic β‐Yb₅Sb₃ type crystal structure was determined from single‐crystal X‐ray data: Pnma, a = 1124.4(1) pm, b = 888.6(1) pm, c = 777.2(1) pm, R = 0.024 for 1140 structure factors and 44 variable parameters. For the other compounds we have established the crystal structures. ZrBi has ZrSb type structure with a noticeable homogeneity range. This structure type was also found for the low temperature (α) form of HfSb and for HfBi. For α‐HfSb this structure was refined from single‐crystal X‐ray data: Cmcm, a = 377.07(4) pm, b = 1034.7(1) pm, c = 1388.7(1) pm, R = 0.043 for 432 F values and 22 variables. HfBi₂ has TiAs₂ type structure: Pnnm, a = 1014.2(2) pm, b = 1563.9(3) pm, c = 396.7(1) pm. The structure was refined from single‐crystal data to a residual of R = 0.074 for 1038 F values and 40 variables. In addition, a zirconium bismuthide, possibly stabilized by light impurity elements X and crystallizing with the hexagonal Mo₅Si₃C_1–x type structure, was observed: Zr₅Bi₃X_1–x, a = 873.51(6) pm, c = 599.08(5) pm. The positions of the heavy atoms of this structure were refined from X‐ray powder film data. Various aspects of impurity stabilization of intermetallics are discussed.     

Zur Kenntnis der Phasen A2−2xSn5+xCl12 (A = K,In)

On the A_2?2xSn_5+xCl₁₂ (A = K, In) Phases The refinement of the structure of A_2-2xSn_5+xCl₁₂ compounds (A = K⁺, In⁺) with single crystal data is reported. They crystallize with the Th₇S₁₂ type arrangement (a = 1192(2) pm, c = 428.9(8) pm (K-compound); a = 1189.8(6) pm, c = 431.2(3) pm (In-compound)) for which we propose the space group P6 . The possibility of meroedric twinning is discussed. Due to the composition of these compounds the structure is necessarily disordered and this leads to a wide range of homogeneity which can be influenced by the size and the polarity of the A type cation.     

Kristallstruktur von Tl4Fe(CN)6

Crystal Structure of Tl₄Fe(CN)₆ Single crystals of Tl₄Fe(CN)₆ have been prepared for the first time and its crystal structure was determined. The pale yellow compound crystallizes in the triclinic space group P1 (No. 2) with the lattice parameters a = 726.6(1) pm, b = 797.4(8) pm, c = 1 336.0(1) pm, α = 104.7(9)°, β = 90.0(8)°, γ = 97.6(7)°, Z = 2 in a new structure type.     

Die Kristallstruktur von Ph3PNBr · Br2

Crystal Structure of Ph₃PNBr · Br₂ Ph₃PNBr · Br₂ ( 1 ) has been prepared besides of other products from the reaction of Ph₃PNH with bromine, forming orange‐yellow single crystals which are characterized by IR‐spectroscopy and by a crystal structure determination. Space group P2₁/n, Z = 4, lattice dimensions at 20 °C: a = 916.76(10), b = 1351.42(8), c = 1494.9(2) pm, β = 96.191(5)°, R₁ = 0.0538. 1 has a molecular structure in which the Br₂ molecule is coordinated at the nitrogen atom of the N‐bromine‐phosphoraneimine Ph₃PNBr in a linear arrangement N–Br–Br with bond lengths N–Br of 224.5(6) pm and Br–Br of 248.4(1) pm. The nitrogen atom of 1 is ψ‐tetrahedrally coordinated in addition by the phosphorus atom with a P–N distance of 165.3(6) pm and by the covalently bonded bromine atom with a bond length of 188.9(6) pm.     

Die Zinn-Rhodiumboride SnRh3B1−x,Sn4Rh6B und Sn5Rh6B2

The Tin Rhodium Borides SnRh₃B_1–x, Sn₄Rh₆B, and Sn₅Rh₆B₂ The new compounds SnRh₃B_1–x (x ～ 0.2, tetragonal, P4/mbm, a = 570.31(2) pm, c = 835.99(8) pm, Z = 4, 514 reflexions, 26 parameters, R = 0.026), Sn₄Rh₆B (hexagonal, P6₃/mmc, a = 560.01(3) pm, c = 1367.5(1) pm, Z = 2, 746 reflexions, 17 parameters, R = 0.035), and Sn₅Rh₆B₂ (hexagonal, P6 2m, a = 654.80(7) pm, c = 557.32(9) pm, Z = 1, 361 reflexions, 16 parameters, R = 0.039) were prepared by reaction of the elements. SnRh₃B_1–x crystallizes with the filled U₃Si type of structure, a distortion variant of the cubic perovskite; the structure of Sn₄Rh₆B may be derived from the hexagonal perovskite BaNiO₃. Both compounds contain nearly regular Rh₆B-octahedra. Sn₅Rh₆B₂ with the Sn₅Ir₆B₂ type of structure contains isolated colums composed of trigonal Rh₆B-prisms.     

Chloroantimonate(III): Die Kristallstruktur des 4,4′-Dipyridylium-pentachloroantimonats, (C10H8N2H2)SbCl5

Chloroantimonates(III): Crystal Structure of 4,4′-Dipyridylium Pentachloroantimonate, (C₁₀H₈N₂H₂)SbCl₅ (C₁₀H₈N₂H₂)SbCl₅ crystallizes in the triclinic space group P1 with a= 843.1(5), b = 958.6(8), c = 1098.0(10) pm, α = 112.45(6), β = 101.95(6), γ = 97.78(6)° and Z = 2. The structure is built up of 4,4 °-dipyridylium cations and pentachloroantimonate anions. The Sb atoms are distorted octahedrally coordinated. Mean distances are Sb? Cl = 242 pm (1×), Sb? Cl = 255 pm (2×), Sb ? Cl = 275 pm (2×) and Sb…?Cl.= 319 pm (1× ). The anions build up dimers.     

Über die Kristallstrukturen der Cyanokomplexe [Co(NH3)6][Fe(CN)6], [Co(NH3)6]2[Ni(CN)4]3 · 2 H2O und [Cu(en)2][Ni(CN)4]

On the Crystal Structures of the Cyano Complexes [Co(NH₃)₆][Fe(CN)₆], [Co(NH₃)₆]₂[Ni(CN)₄]₃ · 2 H₂O, and [Cu(en)₂][Ni(CN)₄] Of the three title compounds X‐ray structure determinations were performed with single crystals. [Co(NH₃)₆][Fe(CN)₆] (a = 1098.6(6), c = 1084.6(6) pm, R3, Z = 3) crystallizes with the CsCl‐like [Co(NH₃)₆][Co(CN)₆] type structure. [Co(NH₃)₆]₂[Ni(CN)₄]₃ · 2 H₂O (a = 805.7(5), b = 855.7(5), c = 1205.3(7) pm, α = 86.32(3), β = 100.13(3), γ = 90.54(3)°, P1, Z = 1) exhibits a related cation lattice, the one cavity of which is occupied by one anion and 2 H₂O, whereas the other contains two anions parallel to each other with distance Ni…Ni: 423,3 pm. For [Cu(en)₂][Ni(CN)₄] (a = 650.5(3), b = 729.0(3), c = 796.5(4) pm, α = 106.67(2), β = 91.46(3), γ = 106.96(2)°, P1, Z = 1) the results of a structure determination published earlier have been confirmed. The compound is weakly paramagnetic and obeys the Curie‐Weiss law in the range T < 100 K. The distances within the complex ions of the compounds investigated (Co–N: 195.7 and 196.4 pm, Ni–C: 186.4 and 186.9 pm, resp.) and their hydrogen bridge relations are discussed.     

Synthesis and Structure of the Ordered Modification of Ba6EuF12Cl2

Crystals of ordered Ba₆EuF₁₂Cl₂ were found to form during high temperature flux growth. The structure was refined in the hexagonal space group P 6 to R^F(R ) = 0.024(0.024) for 326 reflections and 46 parameters. Lattice parameters are a = b = 1059.27(8) pm and c = 416.36(2) pm; Z = 1. The structure is isotypic to Ba₇F₁₂Cl₂. No solid solution of Ba/Eu was observed, the Eu²⁺ ions are located in the channels formed by 3 + 6 fluorine ions, occupying only one of the three metal sites of the Ba₇F₁₂Cl₂ structure.     

Subcell and Superstructure of a High‐Temperature (β‐) Modification of the Mercury(I) Dimolybdate(VI) Hg2Mo2O7

A new (β‐)modification of the mercury molybdate Hg₂Mo₂O₇, thermodynamically stable at temperatures above 390 ± 10 °C, was prepared by solid state reaction of HgO with MoO₂ in sealed silica tubes. Its crystal structure, determined from single‐crystal X‐ray data, has a very pronounced subcell: space group P2/c, a = 600.9(1) pm, b = 388.7(1) pm, c = 1428.4(2) pm, β = 105.88(1)°, Z = 2, R = 0.052 for 797 structure factors and 52 variable parameters. In the superstructure of this high‐temperature β‐modification the a and the b axes of the subcell are doubled: C2/c, a = 1201.9(2) pm, b = 777.3(1) pm, c = 1428.4(2) pm, β = 105.88(1)°, Z = 8, R = 0.040 for 1490 F values and 110 variables. Like the previously reported low‐temperature α‐modification, the β‐modification consists of two‐dimensionally infinite sheets of edge‐ and corner‐sharing MoO₆ octahedra. These sheets are linked by Hg₂ pairs. Thus, the structures of the two modifications (α and β) differ essentially only in the orientation of the Hg₂ pairs, which are located between the sheets of the MoO₆ octahedra. The superstructure of the β‐modification differs from the subcell‐structure by the puckering of the sheets of MoO₆ octahedra. A hypothetical displacive phase transition between the subcell‐structure (corresponding to the potential high‐temperature structure) and the superstructure of β‐Hg₂Mo₂O₇ is discussed.     

Die Kristallstruktur des Dodekamethyl-hexasila-tetraphospha-adamantans (Sime2)6P4

Crystal Structure of Dodecamethyl-hexasila-tetraphospha-adamantane (Sime₂)₆P₄ Dodecamethyl-hexasila-tetraphospha-adamantane (Sime₂)₆P₄ crystallizes in the cubic space group I 4 3m with a = 1081.7 pm and Z = 2 formula units. The bond lengths are P? Si = 224.9 pm, C? Si = 186.4 pm and C? H = 87 pm. The bond angles at the P-atoms are 104.4° and at the Si-atoms 118.8°. – The structure of the isotypic compound (Geme₂)₆P₄ was refined.     

La6(BN3)O6, ein Nitridoborat‐Oxid des Lanthans

La₆(BN₃)O₆, a Nitridoborate Oxide of Lanthanum Single‐crystals of La₆(BN₃)O₆ were formed in reactions of Li₃BN₂, Li₃N, and LaOCl at 950 °C. The structure was solved by single‐crystal X‐ray diffraction. La₆(BN₃)O₆crystallizes with the space group Cmcm (no. 63) containing Z = 4 formula units in the unit cell, with lattice parameters of a = 366.88(3) pm, b = 2509.2(3) pm, and c = 1101.1(1) pm (R1 = 0.054, wR2 = 0.065 for all collected symmetry independant reflections). The crystal structure reflects typical patterns obtained in structures of nitridoborates. Tri‐nitridoborate ions are coordinated by La³⁺ ions in a tricapped trigonal prismatic arrangement, being stacked via shared trigonal faces to form columns. The arrangement of the columns in the structure provides space for O^2— ions with CN = 4, 5, and 6.