Darstellung,Kristallstruktur und IR-spektroskopische Untersuchung von Phosphor(V)-nitrid-imid,HPN2

Preparation, Crystal Structure, and IR-spectroscopic Investigation of Phosphorus Nitride Imide, HPN₂ Pure and fine crystalline phosphorus nitride imide (HPN₂) is obtained by heterogeneous ammonolysis of P₃N₅ with gaseous NH₃ (T = 580°C, p = 30 bar, 6 d). X-ray powder diffraction data has been used to refine the crystal structure of HPN₂ by the Rietveld full-profile technique (I4 2d; a = 461.82(2) pm, c = 702.04(3) pm; Z = 4; 41 reflections observed, 17° < 2Θ < 125°, CuKα₁, germanium monochromator; R(wp) = 0.072, R(I,hkl) = 0.048). In the solid HPN₂ contains a three-dimensional framework of corner-sharing PN₄-tetrahedra (P N: 159.9(4) pm; P N P: 130.1(4)°. The hydrogen atoms are covalently bonded to half of the nitrogen atoms. The IR spectrum exhibits six vibrational modes v(N H): 3224; v_as(PNP): 1330, 1223; v_as(PNHP): 971, 901: δ(PNP): 531 cm⁻¹).     

Darstellung und Kristallstruktur von NaBi2AuO5

Synthesis and Crystal Structure of NaBi₂AuO₅ NaBi₂AuO₅ was obtained by hydrothermal reaction of ‘Bi₂O₅’, Au₂O₃ · 2H₂O and saturated aqueous NaOH solution at temperatures from 300 to 600°C and oxygen pressure from 3 × 10⁸ to 6 × 10⁸ Pa for the first time. The crystal structure (P4 b2; a = 1 220.02(6) pm; b = 386.68(3) pm; Z = 4; R_w = 0.022) consists of bisphenoidic distorted AuO₄ groups, which are stacked in c-direction. They are connected by square pyramidal BiO₅ units. Sodium is occupying holes within the Au/Bi/O framework thus formed.     

Tetramethylammonium-calcium-triazid. Darstellung und Kristallstruktur

[N(CH₃)₄]Ca(N₃)₃,M=240.29, was prepared from aqueous solutions of tetramethylammoniumazide with calciumazide at 298 K. The crystals are tetragonala=936.6(7) pm,c=694.7(5)pm, space group P4/nmm,Z=2, (x)=1.31Mgm^–3. The crystal structure was determined by single crystal x-ray diffraction (234 Mo-K-reflections, =0.469 mm^–1,R=0.064). Calcium is octahedrally coordinated to six azide groups. The octahedra are connected via azide groups to a threedimensional array with the complex ammonium ions between. The terminal nitrogen atoms of the azide groups and the methyl groups are considerably disordered.

     

Darstellung und Kristallstruktur von Tetrakis(pentafluorphenylamino)silan

Synthesis and Crystal Structure of Tetrakis(pentafluorophenylamino)silane Colourless single-crystals of Tetrakis(pentafluorophenylamino) silane were obtained from the reaction of SiCl₄ with monolithiated pentafluoroaniline at low temperatures. The aminosilane has been characterized by various spectroscopic methods and its crystal structure has been determined by x-ray diffraction (for details see “Inhaltsübersicht”). Thermal condensation has not been achieved. However, reaction of silicon(IV)-chloride with pentafluoroaniline in the presence of triethylamine yielded the respective tricyclosilazane.     

Darstellung,Kristallstruktur und Eigenschaften von Kaliumhydrogencyanamid

Preparation, Crystal Structure, and Properties of Potassium Hydrogen Cyanamide For the preparation of KHCN₂ melamine has been reacted with potassium amide in liquid ammonia. After evaporation of the solvent the resulting solid has been transformed at 210°C. KHCN₂ (P2₁2₁2₁, a = 708.7(2), b = 909.0(2), c = 901.4(2) pm, Z = 8, R = 0.039, wR = 0.016) is yielded as a coarse crystalline product. In the solid K⁺ and HCN ions occur. As expected two significantly differing bond-distances C? N (117.3(5) pm) and HN? C (128.7(5) pm) have been found in the anion. According to IR-spectroscopy a non linear group N? C? N (174.4(4)°) is observed.     

Darstellung und Kristallstruktur von CsBO2

Preparation and Crystal Structure of CsBO₂ Colourless single crystals of CsBO₂ have been prepared from intimate mixtures of CsO_0.57 and B₂O₃ (Cs:B = 3.2:1.0; 600°C, 38 d). The structure determination from fourcircle diffractometer data (MoK, 443 I_o (h k l), R = 3.1%, R_w = 2.0%) confirms the isotypy with NaBO₂ and KBO₂: space group R 3 c; a = 1 363.7(2) pm, c = 836.5(2) pm; Z = 18. A characteristic structure unit is the planar cyclic anion [B₃O₆]^3?. Effective Coordination Numbers (ECoN), Mean Fictive Ionic Radii (MEFIR), the Madelung Part of Lattice Energy (MAPLE) and the Charge Distribution (CHARDI) are calculated and discussed.     

Darstellung,Kristallstruktur und Eigenschaften von KLi2As

Preparation, Crystal Structure, and Properties of KLi₂As The novel arsenide KLi₂As has been synthesized either from the elements or from mixtures of the binary components Li₃As and K₃As in sealed Nb ampoules at 823 K and 623 K, respectively. It crystallizes in the space group Pmmn (no. 59) with a = 445.8(9); b = 671.5(11); c = 627.0(12) pm and Z = 2 formula units. The metallic reflecting silvercoloured platelets hydrolize rapidly under wet air. The compound (Pearson code oP8) is isopuntal with BaLi₂Si and an intermediate between the Li₃N and the Na₃As type of structure. Potassium is distorted tetrahedrally coordinated by four As atoms (d(K? As) = 355 and 367 pm), arsenic by four potassium and six lithium atoms (d(As? K) = 355–367 pm; d(As? Li) = 260–265 pm) in form of a sphenocorona. Lithium is threefold coordinated (distorted trigonal planar) by arsenic and this unit is enveloped by a monocapped trigonal prism build by three lithium and four potassium atoms.     

Darstellung und Kristallstruktur von HfOS

Synthesis and Crystal Structure of HfOS On attempts to prepare binary and ternary hafnium sulfides a small quantity of single crystals was obtained which could be identified as HfOS. The new compound is cubic, space group P2₁3 with a = 5.6824(6) Å. It is isostructural with the cubic form o ZrOS. In order to refine the structure parameters intensity measurements were carried out by means of a four-circle single crystal diffractometer.     

Na5Br(OH)4: Darstellung und Kristallstruktur einer Verbindung im System NaOH/NaBr

Na₅Br(OH)₄: Synthesis and Structure of a Compound in the System NaOH/NaBr The pseudobinary system NaOH/NaBr is investigated by X-ray methods. The structure of the compound Na₅Br(OH)₄ was solved by single crystal data: Na₅Br(OH)₄: Pnma, Z = 8, a = 11.846(2) Å, b = 18.782(4) Å, c = 6.431(1) Å, Z(F_o) = 1 202 with (F_o)² ≥ 3σ(F_o)², Z(parameter) = 100, R/R_w = 0.030/0.035 The compound crystallizes in a new type of structure. Pairs of octahedra around O by 5 Na and 1 H to [Na₅(OH)]₂ are orientated in such a way to one another that two ions OH^? form a parallelogram hinting to unusual bent hydrogen bridge bonding.     

Darstellung und Kristallstruktur von Lithiumhydrogensulfid,LiHS

Preparation and Crystal Structure of Lithiumhydrogensulfide, LiHS Lithiumhydrogensulfide, LiHS, is prepared from lithiumamide, LiNH₂, by reaction with liquid hydrogensulfide. At 150°C the solubility of LiHS in H₂S is sufficient for the growth of single crystals in a temperature gradient within the autoclaves used. The X-ray structure determination at 295 K is characterized by the following data: Lithium occupies tetrahedral sites in a distorted cubic close-packed arrangement of S; in PtS sulfur occupies tetrahedral sites in a similar way in a distorted close packing of Pt. Hydrogen atoms of the HS^??ions are dynamically disordered in a split position linearly bound to S. At 228 K a thermal effect occurs in DSC-measurements indicating that below this temperature the HS^??ion has fixed positions.     

Zur Chemie und Strukturchemie von Phosphiden und Polyphosphiden. 581) Tetrabariumtriphosphid,Ba4P3: Darstellung und Kristallstruktur

Chemistry and Structural Chemistry of Phosphides and Polyphosphides. 58. Tetrabariumtriphosphide, Ba₄P₃: Preparation and Crystal Structure Ba₄P₃ is obtained from the elements in the molar ratio 4:3 or by reaction of Ba₃P₂ and Ba₅P₄ in the molar ratio 1:1 (steel ampoules with inner corundum crucibles; 1 490 K). The greyish black, easily hydrolysing compound crystallizes in a new structure type oP56. The structure shows two crystallographically independent dumbbells P₂^4? (d(P? P) = 225 and 232 pm) and isolated ions P^3? corresponding to (Ba²⁺)₈(P₂^4?)₄(P^3?)₄. The partial structure of the Ba atoms forms a complex network of trigonal prisms with tetrahedral and square pyramidal holes, as well as polyhedra with 14 faces (CN 10) which are icosahedron derivatives. The P^3? anions center trigonal prisms and the 14 face polyhedron. The P-atoms of the P₂^4? dumbbells center neighboring trigonal prisms with common square faces. (Pbam (no. 55); a = 1 325.4(2) pm, b = 1 256.2(2) pm, c = 1 127.3 pm; Z = 8).     

Darstellung und Kristallstruktur von Tl2PdCl4

Synthesis and Crystal Structure of Tl₂PdCl₄ Single crystals of Tl₂PdCl₄ can be obtained by hydrothermal synthesis [1, 2]. They show tetragonal symmetry with space group P4/mmm (No. 123). The lattice parameters are a = 7.163(1) Å and c = 4.282 (1) Å. The atomic arrangement of Tl₂PdCl₄ is explored by X‐ray crystal structure analysis. Tl₂PdCl₄ is isotypic with K₂PtCl₄.     

Einkristallzüchtung und Strukturverfeinerung von RbAu und CsAu

Single-Crystal Growth and Structure Refinement of RbAu and CsAu Single-crystals of RbAu and CsAu were obtained by the reaction of the alkalimetal azides with gold-powder at 400°C. The structures were determined from X-ray single-crystal diffraktometer data: space group Pm3m, Z = 1; RbAu, a = 4.098(1) Å, R/R_w(w = 1) = 0.011/0.011, N(F_o²) ≥ 3σ(F_o²) = 41 and N(var.) = 4; CsAu, a = 4.258(1) Å, R/R_w(w = 1) = 0.009/0.010, N(F_o²) ≥ 3σ(F_o²) = 34 and N(var.) = 4. Both compounds crystallize in the completely ordered CsCl-type with neglible deviations from the ideal 1:1-composition.     

Darstellung und Kristallstruktur von CsTe4

Preparation and Crystal Structure of CsTe₄ CsTe₄ results from a melting reaction at 570°C in sealed quartztubes. The starting materials Cs and Te in the molar ratio 1:4 are produced in a first step by controlled decomposition of the CsN₃ from mixtures of CsN₃ and Te (1:4) at 350°C. CsTe₄ is monoclinic, space group P2₁/c, with a = 7.857(1) Å, b = 7.286(1) Å, c = 14.155(2) Å, β = 93.83(1)°, and Z = 4. The tellurium atoms form a two-dimensional puckered layer built of from pseudo-trigonal-bipyramidal, T-shaped units Te₄^?. The central tellurium atom of this unit may be considered as a pseudo iodine. The compound is compared with other tellurides MTe_n having some like that unexpected principles of connection.     

Darstellung und Kristallstruktur von KSbS2

Preparation and Crystal Structure of KSbS₂ Red KSbS₂ was prepared in a aqueous solution of KHS and Sb₂S₃ under mild hydrothermal conditions. For crystallographic data see ?Inhaltsübersicht”?. There are SbS-chains, built up by ψ-trigonal bipyramids, which are connected by sharing edges. The K⁺-Ions between these chains have a nearly octaedric coordination.     

Synthese und Kristallstruktur von CaBiVO5

Synthesis and Crystal Structure of CaBiVO₅ Single crystals of the hitherto unknown compound CaBiVO₅ were prepared and investigated by X-ray work. It crystallizes with orthorhombic symmetry, space group D? Pbca, a = 11.2022, b = 5.4283, c = 15.5605 Å, Z = 8. The crystal structure is characterized by layers of the edge-linked CaO₇ polyhedra, isolated VO₄ tetrahedra and an asymmetric surrounding of Bi³⁺ by oxygen.     

Darstellung und Kristallstruktur von Cs8P8O24 · 8H2O

Synthesis and Crystal Structure of Cs₈P₈O₂₄ · 8H₂O Cs₈P₈O₂₄ · 8H₂O was obtained from Na₈P₈O₂₄ · 6H₂O by cation exchange. Crystal growth was achieved by applying gel techniques (agar agar). The crystal structure (P1 ; a = 766.6(8); b = 1 156.9(9); c = 1 163.4(9) pm; α = 100,2(1)°; β = 106.5(2)°; γ = 92.2(1)°; Z = 1; 4 099 unique diffractometer data; R = 0.051; R(w) = 0.037) contains cyclo-octaphosphate anions with point symmetry C_2h. The cesium atoms are coordinated irregularily by eight and ten oxygen atoms, respectively. The threedimensional linkage of the P₈O₂₄^8?-rings is established via bonds to cesium atoms and hydrogen bonds Provided by H₂O molecules.     

Darstellung und Kristallstruktur von Rb2Ni3Se4

Preparation and Crystal Structure of Rb₂Ni₃Se₄ The compound Rb₂Ni₃Se₄ was synthesized by heating a mixture of rubidium carbonate, nickel and selenium at 850°C in an atmosphere of hydrogen. The compound has a golden lustre and crystallizes with the K₂Pd₃S₄-type structure; a = 10.555(3) Å, b = 27.588(6) Å, c = 6.031(6) Å, Z = 8, Fddd (No. 70). The structure can be described as a stacking of layers of the composition Rb₂Ni₃Se₄ with a stacking sequence abcd. The electrostatic part of lattice energy (MAPLE) will be discussed for compounds of the compositions A₂M₃X₄ (A K, Rb, Cs; M Ni, Pd, Pt and X S, Se).     

Darstellung und Kristallstruktur von LnAl3Br12 (Ln = La,Ce, Pr,Nd, Sm,Gd) und thermischer Abbau zu LnBr3

Preparation and Crystal Structure of LnAl₃Br₁₂ (Ln = La, Ce, Pr, Nd, Sm, Gd) and Thermal Decomposition to LnBr₃ LnAl₃Br₁₂ (Ln = La, Ce, Pr, Nd, Sm, Gd) was prepared in crystalline form for the first time. The crystal structures of LaAl₃Br₁₂, PrAl₃Br₁₂, and NdAl₃Br₁₂ were determined on single crystals by X-ray methods. The isotypic compounds crystallize with trigonal symmetry, space group P 3₁12, Z = 3. A structural comparison to lanthanoide chloroaluminates of equal composition is given and thermal decomposition of LnAl₃Br₁₂ (Ln = Nd) to the corresponding lanthanoide tribromide is described.