Zur Chemie und Strukturchemie der Phosphide und Polyphosphide. 26. Dibariumheptaphosphidchlorid Ba2P7Cl,eine Verbindung mit dem polycyclischen Anion P

Chemistry and Structural Chemistry of Phosphides and Polyphosphides. 26. Dibariumheptaphosphidechloride Ba₂P₇Cl, a Compound with the Polycyclic Anion P Ba₂P₇Cl is formed by the synthesis of Ba₃P₁₄ from the elements in a melt of BaCl₂ (dehydrated) at 1170 K. The compound forms light rubyred platelets which decompose in protic systems immediately to phosphanes. Ba₂P₇Cl crystallizes in the space group P2₁/m with Z = 2 formular units (a = 1172.6(2) pm; b = 682.9(1) pm; c = 633.7(1) pm; β = 95.27(2)°). The structure (964 reflexions hkl, R = 0.035) is related to the NaCl type, in which the half of the anionic positions is occupied by the gravi-centers of the polycyclic anions P. The bond lengths d(P? P) show the typical topological dependence for the anionic heptaphosphanortricyclene system: (d : 226.4 pm in the three-membered ring; 214.5 pm ring to bridge; 217.2 pm bridge to bridge head). The Ba atoms are surrounded by 9 and 10 non metallic atoms, respectively. Cl^? is coordinated tetrahedrally by Ba.     

Dibrommethylsulfoniumsalze – Darstellung und Kristallstruktur [1]

Dibromomethylsulfoniumsalts — Preparation and Crystal Structure The salts CH₃SBrA^? (A^? = SbCl, AsF) were prepared by various routes and characterized by their Ramanspectra. CH₃SBrAsF crystallized in the monoclinic space group P2₁/c with a = 770,5(4) pm, b = 942,4(12) pm, c = 1329,3(14) pm, β = 100,28(6)°, Z = 4. Distances and bond angles in the cation are as expected.     

Synthese und Struktur von AlTaO4

Synthesis and Structure of AlTaO₄ Single crystals of AlTaO₄ were prepared between 1310–1360°C and investigated by X-ray single crystal methods. It crystallizes with tetragonal symmetry (a = 460.6₅; c = 298.5 pm; space group D–P4₂/mnm). AlTaO₄ has got a statistical metal distribution with rutil structure. It shows metastable character in respect to lower temperatures.     

Darstellung und Kristallstruktur von Barium-Cadmium-Thiostannat (iv) BaCdSnS4

Preparation and Crystal Structure of Barium-Cadmium-Thiostannate (IV) BaCdSnS₄ BaCdSnS₄ was prepared for the first time and the crystal structure determined by single crystal X-ray investigations. Lattice constants: a = 2186 ± 2; b = 2169 ± 1; c = 1318 ± 0.5 pm. Space group: C–Fdd2. There are pairs of edge-sharing tetrahedrons linked together characteristically to form twodimensional endless nets. The crystal structure is described and discussed.     

Zur Kristallstruktur von MnF3 und MnPtF6

On the Crystal Structure of MnF₃ and MnPtF₆ Single crystal investigations of MnF₃ (rubyred) confirmed the crystal structure based on powder data [2]: monoclinic, space group C 2/c?C (No. 15) with a = 892.02 pm, b = 504.72 pm, c = 1 347.48 pm, β = 92.64° with Z = 12. The corresponding determination of the crystal structure of MnPtF₆, yellow, confirmed the unit cell [3] with a = 510.47 pm, c = 1 421.0 pm and γ = 120°, Z = 3 space group R 3 -C (No. 148). For both compounds detailed parameters respectively interatomic distances have been obtained.     

Zur Kenntnis komplexer Fluoride mit Cu2+ und Pd2+: MPtF6 (M  Pd,Cu) und RbCuPdF5

On Complex Fluorides with Cu²⁺ and Pd²⁺: MPtF₆ (M ? Pd, Cu) and RbCuPdF₅ For the first time single crystals of PdPtF₆ (green), trigonal-rhomboedric, a = 503.8, c = 1431.6 pm, spcgr. R3 ? C (No. 148), Z = 3, CuPtF₆ (orange), triclinic, a = 495.2, b = 498.5, c = 962.4 pm, α = 89.98, β = 104.23, γ = 120.35°, spcgr. P1 ? C (No. 2), Z = 2 and RbCuPdF₅ (orange brown, in connection with investigations on M^IPd₂F₅ [1]), orthorhombic, a = 626.9, b = 719.9, c = 1076.3 pm, spcgr. Pnma? D (No. 62), Z = 4, four circle diffractometer data, have been obtained.     

Synthese und Kristallstruktur von PbMo5O8; ein reduziertes Oxomolybdat mit Mo10O28-Oktaederdoppeln

Synthesis and Crystal Structure of PbMo₅O₈; a reduced Oxomolybdate with Mo₁₀O₂₈ Double Octahedra The crystal structure of the new phase PbMo₅O₈ contains oligometric Mo clusters which consist of two edge-sharing Mo₆ octahedra connected according to Mo₁₀OOO. The compound is isotypic with LaMo₅O₈. Isolated, divalent Pb atoms are located in the “channels” of the monoclinic structure (a = 999.3(2) pm, b = 924.7(1) pm, c = 753.6(2) pm, β = 109.39(2)°, P2₁/a. Compared to the compound In ₁₁Mo₄₀O₆₂ the Mo? O distances (average 206 pm) and the Mo? Mo distances within the octahedral units (average 275 pm) are slightly decreased by 1 and 4 pm, respectively. The very short Mo? Mo distances (278 pm) between the cluster units which are not observed in In₁₁Mo₄₀O₆₂ (320 pm) are due to excess electrons in these inter-cluster bonds which would otherwise occupy antibonding cluster states.     

Kristallstruktur und Eigenschaften von Calcium- und Strontiumhexathiodiphosphat(IV), Ca2P2S6 und Sr2P2S6, mit einem Beitrag zu Ca5P8 und Pb2P2S6

Crystal Structure and Properties of Calcium and Strontium Hexathiodiphosphate(IV), Ca₂P₂S₆ and Sr₂P₂S₆, with a Contribution on Ca₅P₈ and Pb₂P₂S₆ Ca₂P₂S₆ and Sr₂P₂S₆ were prepared from metal and a mixture of red phosphorus and sulfur (molar ratio M:P:S = 1:1:3) in 2 corundum crucibles inserted in quartz ampullae under vacuum (20 d 900°C). The compounds were obtained as colourless, crystalline powders containing single crystals. They crystallize in the Sn₂P₂S₆ (high temperature form) type structure (P2₁/c, Z = 2): Ca₂P₂S₆ a = 653.2(2)pm, b = 728.1(2)pm, c = 1110.1(4)pm, β = 124.00(4)°, d = 2.50(2); Sr₂P₂S₆ a = 664.3(2)pm, b = 755.7(3)pm, c = 1139.7(3)pm, β = 124.07(2)°, d = 2.97(2). The anions P₂S have staggered confirmation and are arranged with the motif of a cubic close-packing. Sr²⁺ is coordinated by 8S which form a twofold face-capped trigonal prism and belong to 4P₂S. Structure calculations clearly show that Pb₂P₂S₆ also crystallizes in P2₁/c and not in Pc [1]. Also, Raman- and IR-spectra of Ca₅P₈ were recorded at 20°C. The stretching vibrations of P were assigned in analogy to those of P₂S in alkaline earth hexathiodiphosphates(IV). The range of their frequencies (480 to 340 cm^?1) is essentially smaller and shifted to smaller values compared with P₂S in Ca₂P₂S₆ and Sr₂P₂S₆ (620 to 390 cm^?1). The symmetry of P is not D_3d but C_2h as in the case of P₂S.     

Thermisches Verhalten und Kristallstruktur von YAl3Cl12

Thermal Behaviour and Crystal Structure of YAl₃Cl₁₂ We determined the thermodynamic data of YAl₃Cl₁₂ ΔH = ?739.9 ± 3 kcal/mol and S = 136.1 ± 4 cal/K · mol by total pressure measurements and ΔH = ?739.1 ± 1.6 kcal/mol by solution calorimetry. Using DTA-investigations we established the phase diagram in the system AlCl₃–YCl₃. The crystal structure was refined on the basis of single crystal data (P3₁ 12; Z = 3; a = 1 046.8(2); c = 1 562.3(3) pm).     

Zur Synthese und Kristallstruktur von LiPdAlF6 und PdZrF6

Synthesis and Crystal Structure of LiPdAlF₆ and PdZrF₆ . For the first time single crystals of the new compounds LiPdAlF₆ and PdZrF₆ have been obtained. LiPdAlF₆ (blue) crystallizes trigonal, space group P3 1c—D (No. 163; LiCaAlF₆-type [2]), in an ordered structure variant of the Li₂[ZrF₆]-structure [3], with a=497.21(9) pm, c=914.0(9) pm and Z=2. PdZrF₆ (also blue) is isotypic with LiSbF₆ [4] and crystallizes trigonal-rhomboedric with a=552,3(1) pm, c=1 447,5(4) pm, space group R 3 —C (No. 148) and Z=3.     

Zur Insertion in die Lanthanoid–Kohlenstoffbindung Synthese und Struktur von [CpSm(C6H5CH2NNO)]2 und [K(18-Krone-6)CpYb(NCS)2]∞

On the Insertion into the Lanthanide–Carbon Bond. Synthesis and Structure of [Cp Sm(C₆H₅CH₂NNO)]₂ and [K(18-crown-6)Cp Yb(NCS)₂]_∞ The compound [CpSm(CH₂C₆H₅)(thf)] was investigated, regarding its reactions with small molecules. The main subject was to detect an insertion into the Ln–C bond. With N₂O an insertion reaction is observed, yielding the dimer [CpSm(C₆H₅CH₂NNO)]₂ ( 1 ). The structural data of 1 was collected by a single crystal X-Ray diffraction analysis. (Space group P 1, Z = 1, a = 982.8(2) pm, b = 1052.2(2) pm, c = 1383.8(3) pm, α = 89.29(3)°, β = 73.64(3)°, γ = 66.41(3)°). In the dimer, the two Samarium ions are linked via an (η¹ : η²) bridge by two benzyl diazotato ligands. A nearly planar six-membered central Sm₂N₂O₂-ring is formend. Two pentamethylcyclopentadienyl ligands complete the coordination sphere of each Samarium ion, which are thus surrounded by four ligands each and have a distorted tetrahedral coordination geometry. An insertion of a SCN^– fragment in the Ln–C bond could not be observed. The substitution of the benzyl ligand leads to a polymeric chain structure. The new compound [K(18-crown-6)CpYb(NCS)₂]_∞ 2 contains a tetrahedrally coordinated Yb(III)-ion. (Space group P2₁/n}, Z = 4, a = 1640.6(3) pm, b = 1482.2(3) pm, c = 1674.5(3) pm, β = 102.82(1)°).     

Einkristalluntersuchungen an Fluoroperowskiten MPdF3 (M = Rb,K) und PdF2

Single Crystal Investigations on Fluoroperovskites MPdF₃ (M = Rb, K) and PdF₂ Single crystal investigations on PdF₂ (violet) confirm the tetragonale rutile structure [1, 2] with a = 495.44(3) pm, c = 338.48(3) pm, Z = 2, space group P4₂/mnm-D (No. 136) (x_F = 0.3058(8)). RbPdF₃ and KPdF₃ have been obtained. RbPdF₃ and KPdF₃ both ruby-red single crystals crystallize cubic (perovskite-structure), space group Pm3m-O (No. 221) with a = 429.41(8) pm (RbPdF₃) respectively a = 424.30(4) pm (KPdF₃).     

Zur Kristallstruktur von La[AuF4]3, dem Anfangsglied der Reihe M[AuF4]3−xFx (x = 0, 0,5 und 1)

On the Crystal Structure of La[AuF₄]₃, the Final Link in the Series M[AuF₄]_3?xF_x (x = 0, 0.5 and 1) Yellow La(AuF₄)₃ was prepared for the first time in form of single crystals and investigated by X-ray methods. It crystallizes in space group R3 c-D (Nr. 167) with a = 1056.2(2) pm, c = 1633.7(8) pm, Z = 6.     

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,Kristallstrukturen und Schwingungsspektren von [OsBr(acac)(PPh3)] und [OsBr(acac)(AsPh3)]

Synthesis, Crystal Structures, and Vibrational Spectra of [OsBr(acac)(PPh₃)] and [OsBr(acac)(AsPh₃)] By reaction of tetrabromoacetylacetonatoosmate(IV) with PPh₃ or AsPh₃ in ethanol the complexes [OsBr(acac)(PPh₃)] ( 1 ) and [OsBr(acac)(AsPh₃)] ( 2 ) are formed, which are purified by chromatography on silica gel. X-ray structure determinations of single crystals of ( 1 ) (monoclinic, space group P 2₁/n, a = 13.035(2), b = 18.2640(14), c = 16.636(3) Å, β = 112.776(14)°, Z = 4) and ( 2 ) (monoclinic, space group P 2₁/c, a = 13.23(5), b = 18.35(2), c = 16.65(2) Å, β = 112.9(5)°, Z = 4) result in mean bond distances Os–P = 2.413, Os–As = 2.483, Os–Br = 2.488 and Os–O = 2.037 Å. The vibrational spectra (10 K) exhibit the inner ligand vibrations of the acac, PPh₃ and AsPh₃ groups with nearly constant frequencies and the stretching vibrations of OsP at 499–522, of OsAs at 330–339, of OsBr at 213–214 and of OsO in the range 460–694 cm^–1.     

Hydroxoverbindungen. 12. Kristallstruktur und Konstitution von Natrium-trihydroxozinkat Na[Zn(OH)3] bei 190 K

Hydroxo Compounds. 12. Crystal Structure and Constitution of Sodium Trihydroxozincate Na[Zn(OH)₃] 1 The crystal structure of the very sensitive sodium trihydroxozincate Na[Zn(OH)₃] 1 has been determined at 190 K. Contrary to the observations of trigonal planar [Zn(OH)₃]^? anions at 298 K, the structure of 1 at lower temperatures is characterized by 1-dimensional chains [Zn(OH)₂(OH)_2/2]^? with the much more plausible (distorted) tetrahedral coordination of the Zn atoms (P4₂bc? C_4v ⁶; Nr. 106; a = 1083.9 pm; c = 530.8 pm; Z = 8; Zn? O = 194.3–200.5 pm). The H positions were determined unambigeously from the X-ray data in complete agreement with calculations of potential profiles. There are pronounced hydrogen bond distances present. The Na atoms are coordinated by (5+1) oxygen atoms (Na? O = 234.8–248.8 pm and 282.7 pm). The noncentric coordination of the atoms as well as the strong anisotropic and anharmonic temperature tensors indicate a second order phase transition between 190 K and 298 K.     

Zur Kristallstruktur von SmZrF7 mit einem Anhang über EuSnF7 und YSnF7

On the Crystal Structure of SmZrF₇ with an Appendix on EuSnF₇ and YSnF₇ SmZrF₇ again was obtained as colourless single crystals and investigated by X-ray methods: It crystallizes in space group P 2₁/c-C (Nr. 14; P 2₁/n) with a = 1 140.9(2) pm, b = 574.6(1) pm, c = 914,4(2) pm, β = 107.32(2)°, Z = 4 but not in space group P 2₁-C (Nr. 4) [1]. In addition EuSnF₇ and YSnF₇ are isotypic with the following lattice constants: EuSnF₇: a = 1 121.8(2) pm, b = 563.7(1) pm, c = 901.7(1) pm, β = 107.35(2)° with Z = 4; YSnF₇: a = 1 106.7(2) pm, b = 556.4(1) pm, c = 884.7(1) pm, β = 107.51(1)° and Z = 4 (Powder data).     

Chemie und Strukturchemie von Phosphiden und Polyphosphiden. 53. Darstellung,Eigenschaften und Schwingungsspektren der Käfiganionen P113− und As113−

Chemistry and Structural Chemistry of Phosphides and Polyphosphides. 53. Preparation, Properties, and Vibrational Spectra of the Cage Anions P₁₁^3? and As₁₁^3? The Zintl-phases M₃X₁₁ (M = Na, K, Rb, Cs; X = P, As) are prepared from the elements or from M₃X₇ and X. The compounds undergo a first-order phase transition from the crystalline to the plastically crystalline state. Unit cell and space group of both modifications and the transition temperature T_c are determined. The vibrational spectra of the crystalline compounds and the Raman spectrum of the P₁₁^3? anion in en-solution as well are measured. The assignment of the frequencies is given, based on the 32-D₃ symmetry of the X₁₁^3? cage anion. Normal coordinate analysis is carried out in terms of Cartesian coordinates to avoid the problem of redundancies in using internal coordinates. The force constants [mdyn Å^?1] obtained for the characteristic bonds r, s, and t are: f = 1.34, f = 1.20, f = 1.08; f = 1.1, f = 0.91. Normal vibrations and the potential energy distribution (PED) are discussed.     

Bis[N-(trimethylsilyl)iminobenzoyl]phosphanide des Lithiums und Zinks – Synthese sowie NMR-spektroskopische,strukturelle und quantenchemische Untersuchungen

Acyl- and Alkylidenephosphanes. XXXV. Bis[ N -(trimethylsilyl)iminobenzoyl]phosphanides of Lithium and Zinc – Syntheses as well as NMR Spectroscopic, Structural, and Quantumchemical Studies From the reaction of bis(tetrahydrofuran)lithium bis(trimethylsilyl)phosphanide with two equivalents of benzonitrile in 1,2-dimethoxyethane, the yellow dme complex ( 2 a ) of lithium bis[N-(trimethylsilyl)iminobenzoyl]phosphanide ( 2 ) was obtained in 69% yield. However, the intermediate {1-[N-lithium-N-(trimethylsilyl)amido]benzylidene}trimethylsilylphosphane ( 1 ), formed by an analogous 1 : 1 addition in diethyl ether, turned out to be unstable and as a consequence could be characterized by nmr spectroscopic methods only; attempts to isolate the compound failed, but small amounts of the neutral complex 2 b , with the ligands benzonitrile and tetrahydrofuran coordinated to lithium, precipitated. The reaction of compound 2 with zinc(II) chloride in diethyl ether gives the orange-red spiro-complex zinc bis{bis[N-(trimethylsilyl)iminobenzoyl]phosphanide} ( 3 ); this complex is also formed from bis[N-(trimethylsilyl)iminobenzoyl]phosphane ( 4 ), easily amenable by a lithium hydrogen exchange of 2 a with trifluoroacetic acid [18], and zinc bis[bis(trimethylsilyl)amide]. As derived from nmr spectroscopic studies and x-ray structure determinations, compounds 2 a {δ³¹P +63.3 ppm; P2₁/n; Z = 4; R₁ = 0.067}, 2 b {δ³¹P +63.3 ppm; P2₁/c; Z = 4; R₁ = 0.063}, 3 {δ³¹P +58.2 ppm; C2/c; Z = 4; R₁ = 0.037} and 4 {δ³¹P +58.1 ppm [18]} exist as cyclic 3-imino-2λ³σ²-phosphapropenylamides and -propenylamine, respectively, in solution as well as in the solid state. Unlike hydrogen derivative 4 the bis[N-(trimethylsilyl)iminobenzoyl]phosphanide fragments N,N′-coordinating either a lithium or a zinc cation are characterized by almost completely equalized bond lengths; typical mean distances and angles are: PC 180.3 and 178.7; CN 130.5 and 131.8; N–Si 175.3 and 179.3; N–Li 202.3; N–Zn 203.5 pm; CPC 108.8° and 110.5°; PCN 130.9° and 132.9°; CN–Li 113.0°, CN–Zn 117.4°; N–Li–N 104.6°; N–Zn–N 108.8°. Alterations in the shape of the six membered chelate rings, caused by an exchange of the 3-imino-2λ³σ²-phosphapropenylamide or related 2λ³σ²-phospha-1,3-dionate units for the corresponding phosphorus free ligands, are discussed in detail. The results of quantumchemical DFT-B3LYP calculations coincide very well with the experimentally obtained findings.     

Tellur-Polykationen stabilisiert durch Nioboxidhalogenide: Synthese und Kristallstrukturen von Te7NbOBr5 und Te7NbOCl5

Tellurium Cations stabilized by Niobium Oxytrihalides: Synthesis and Crystal Structure of Te₇NbOBr₅ and Te₇NbOCl₅ The reaction of Te₂Br with NbOBr₃ in a sealed evacuated glass ampoule at 225°C yields Te₇NbOBr₅ in form of bright black needles. Te₇NbOCl₅ is obtained from tellurium, TeCl₄ and NbOCl₃ at 220°C. Both compounds crystallize orthorhombic in the space group Pcca (Te₇NbOBr₅: a = 2 651,9(4) pm, b = 836.6(1) pm, c = 794.6(1) pm; Te₇NbOCl₅: a = 2 597.7(5) pm, b = 805.1(1) pm, c = 791.2(1) pm). The crystal structure determinations show that Te₇NbOBr₅ and Te₇NbOCl₅ are built of one-dimensional polymeric tellurium cations, one-dimensional associated pyramidal NbOX₄ groups (X = Cl, Br) and isolated halide anions. Magnetic properties of Te₇NbOX₅ were determined and confirm the expected diamagnetism. Te₇NbOX₅ can thus be formulated as [Te₇²⁺] [NbOX₄^?] (X^?). The charge distribution in the structure type Te₇MOX₅ (M = W, Nb; X = Cl, Br) became clear by synthesis and characterisation of the two niobium containing compounds.