Darstellung und Kristallstruktur von Na2Mn3O7

Synthesis and Crystal-Structure of Na₂Mn₃O₇ Single crystals of Na₂Mn₃O₇ have been grown hydrothermally applying high oxygen pressure (p = 2 kbar). The new compound cystallizes triclinic; space group P1 ; a = 6.636(6) Å, b = 6.854(6) Å, c = 7.548(6) Å, α = 105.76(6)°, β = 106.86(6)°, γ = 111.60(6)°; Z = 2. The crystal structure has been solved and refined to R = 7.9% and R_w = 6.2% (diffractometer data, 1044 independent reflexions). The crystal structure consists of Mn₃O₇^2? anions with manganese coordinated octahedrally by oxygen. These layered anions are hold together by Na⁺ ions (coordination numbers 5 and 6).     

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).     

Darstellung und Kristallstruktur von trans-(Ph4As)2[OsCl2(NCS)(SCN)], Schwingungsspektren und Normalkoordinatenanalyse

Preparation and Crystal Structure of trans-(Ph₄As)₂[OsCl₂(NCS) (SCN) ], Vibrational Spectra and Normal Coordinate Analysis By treatment of trans-[OsCl₂I₄]^2? with (SCN)₂ in dichloromethane a mixture of different linkage isomers is formed, from which trans-[OsCl₂(NCS)(SCN)]^2? has been isolated by ion exchange chromatography on diethylaminoethyl cellulose. The X-Ray structure determination on a single crystal of trans-(Ph₄As)₂[OsCl₂(NCS)(SCN)] (triclinic, space group P 1 , a = 12.505(5), b = 12.056(5), c = 19.833(5) Å, α = 108.047(5)°, β = 91.964(5)°, γ = 117.048(5)°, Z = 2) reveals that two cis-positioned Thiocyanate(N) groups are coordinated with Os? N? C angles of 172.1° and 173.0° and two cis-positioned Thiocyanate(S) groups are coordinated with Os? S? C angles of 106.9° and 108.7°. Using the molecular parameters of the X-Ray determination the low temperature (10 K) IR and Raman spectra of the (n-Bu₄N) salt of the linkage isomer are assigned by a normal coordinate analysis based on a modified valence force field. The valence force constants are f_d(OsN) = 1.63 and f_d(OsS) = 1.30 mdyn/Å. Taking into account the trans influence a good agreement between observed and calculated frequencies is achieved.     

The crystal structure of tris (ethylenediamine), cobalt(III) hexacyanoferrate(III)dihydrate,Co(C2H8N2)3[Fe(CN)6] · 2H2O

The crystal structure of the title compound has been determined from three dimensional x-ray data obtained by the multiple film method. The space group is P2_l/n and the cell dimensions are: a = 14.90, b = 16.84, c = 8.38 Å; β = 93.5° Z = 4. The structure is formed by discrete Co (en) and Fe(CN) ions, both of which have an octahedral configuration. The Fe(CN) ions are approximately octahedrally surrounded by the Co (en) ions while arrangement of Fe (CN) ions around the Co(en) ions completely differs from an octahedron. The mean Fe? C and Co? C dustances are 1.91 and 2.01 Å, respectively. The water molecules do not play an important role in the structure and all distances between oxygen and other atoms indicate the presence of very weak hydrogen bonds. The salts M (en)₃ Q(CN)₆ · H₂O, where M = Co and Cr and Q = Cr, Mn, Fe and Co, are all isomorphous.     

Untersuchungen an SrYb2O4, CaYb2O4 und CaLu2O4; ein Beitrag zur Kristallstruktur des Calciumferrat(III)-Typs

Single crystals investigations at SrYb₂O₄, CaYb₂O, and CaLu₂O₄, and investigations at the systems CaO? Yb₂O₃ and CaO? Gd₂O₃ show, that the condition R > R must be fullfilled for the formation of compounds of the CaFe₂O₄-type. The anionic frame [MeO₄]^2? is inflexible. Any changing in volume of Me²⁺ is transmitted up to the limitation of the unit cell.     

Lithiumtriamidostannat(II), Li[Sn(NH2)3] – Synthese und Kristallstruktur

Lithium Triamidostannate(II), Li[Sn(NH₂)₃] – Synthesis and Crystal Structure Rusty-red glistening, transparent crystals of Li[Sn(NH₂)₃] were obtained by reaction of metallic lithium with tetraphenyl tin in liquid ammonia at 110 °C. The structure was determined from X-ray single-crystal diffractometer data: Space group P 2₁/n, Z = 4, a = 8.0419(9) Å, b = 7.1718(8) Å, c = 8.5085(7) Å, β = 90.763(8)°, R₁ (F _o ≥ 4σ(F _o)) = 2.8%, wR₂ (F ≥ 2σ(F )) = 5.3%, N(F ≥ 2σ(F )) = 1932, N(Var.) = 65. The crystal structure contains trigonal pyramidal complex anions [Sn(NH₂)₃]^– with tin at the apex, which are connected to layers of sequence A B A B … by lithium in tetrahedra-double units [Li(NH₂)_2/2(NH₂)₂]₂.     

Tetraammin-Lithium-Kationen zur Stabilisierung phenylsubstituierter Zintl-Anionen: Die Verbindung [Li(NH3)4]2[Sn2Ph4]

Tetraammine Lithium Cations Stabilizing Phenylsubstituted Zintl-Anions: The Compound [Li(NH₃)₄]₂[Sn₂Ph₄] Ruby-red, brittle single crystals of [Li(NH₃)₄]₂[Sn₂Ph₄] were synthesized by the reaction of diphenyltin dichloride and metallic lithium in liquid ammonia at ?35°C. The structure was determined from X-ray singlecrystal diffractometer data: Space group, P1 , Z = 1, a = 9.462(2) Å, b = 9.727(2) Å, c = 11.232(2) Å, α = 66.22(3)°, β = 85.78(3)°, γ = 61.83(3)°, R₁ (F ? 4σF) = 5.13%, wR₂ (F₀² ? 4σF) = 10.5%, N(F ? 4σF) = 779, N(Var.) = 163. The compound contains to Sb₂Ph₄ isosteric centres [Sn₂Ph₄]^2? as anions which are connected to rods by lithium cations in distorted tetrahedral coordination by ammonia. These rods are arranged parallel to one another in the b,c-plane, but stacked along [100].     

Darstellung,Kristallstruktur und Schwingungsspektren von (n-Bu4N)2[(Mo6I)(NCS)]

Synthesis, Crystal Structure, and Vibrational Spectra of (n-Bu₄N)₂[(Mo₆I)(NCS)] By treatment of [(Mo₆I)I]^2– with (SCN)₂ in dichloromethane at –20 °C the hexaisothiocyanato cluster anion [(Mo₆I)(NCS)]^2– is formed. The X-ray structure determination of (n-Bu₄N)₂[(Mo₆I)(NCS)] · 2 Me₂CO (monoclinic, space group P2₁/c, a = 13.168(5), b = 11.964(5), c = 24.636(5) Å, β = 104.960(5)°, Z = 2) shows, that the thiocyanate groups are coordinated exclusively via N atoms with Mo–N bond lengths of 2.141–2.150 Å, Mo–N–C angles of 166–178° and N–C–S-angles of 174–180°. The vibrational spectra exhibit characteristic innerligand vibrations at 2073–2054 (ν_CN), 846–844 (ν_CS) and 480–462 cm^–1 (δ_NCS).     

Die Kristallstruktur von Li2SnO3

Li₂SnO₃ crystallises monoclinic, C, with a = 5.295, b = 9.184, c = 10.032 Å and β = 100.13°; Z = 8. The positions of Sn were obtained from PATTERSON maps and the positions of O and Li by FOURIER difference method. Parameters were refined by least squares-method [1462 reflexes (h 01)–(h 71); R = 10.5%]. The average distances of Li? O are 2.07 Å, and 2.20 Å for Sn? O. The Li₂SnO₃ structure can be derived from the NaCl type: in a cubic closest packing of oxygen 2/3 of the octahedral holes are occupied by lithium and 1/3 by tin.     

Die Kristall- und MolekülStruktur von (S4N3)2SbCI5

The structure of (S₄N₃)₂SbCI₅ has been determined by X-ray methods using least-squares′ refinement. The compound crystallises monoclinic; C–P2₁/c, a = 9.24 Å, b = 17.77 Å, c = 11.29 Å, β = 110.06°, Z = 4. The antimony atom has a fivefold coordination the geometry being derived from a deformed octahedron, the S₄N-rings retained their planar shape.     

Synthese und Kristallstruktur von Sr2Zn(OH)6 und Ba2Zn(OH)6

Synthesis and Crystal Structure of Sr₂Zn(OH)₆ and Ba₂Zn(OH)₆ Crystallization from supersaturated sodium hydroxozincate solutions by adding solutions of alkali earth metal hydroxides yields crystals of Sr₂Zn(OH)₆ and Ba₂Zn(OH)₆. The X-ray structure determination on these crystals was successful including all hydrogen positions: Sr₂Zn(OH)₆: P2₁/n, Z = 2, a = 5.794(1) Å, b = 6.160(1) Å, c = 8.141(1) Å, b = 91.23(1)°, N(F ³° 2σ F) = 1127, N(Var.) = 53, R₁/wR₂ = 0.047/0.081Ba₂Zn(OH)₆: P2₁/n, Z = 2, a = 6.043(1) Å, b = 6.336(1) Å, c = 8.451(2) Å, b = 91.23(2)°, N(F ° 2σ F) = 1669, N(Var.) = 54, R₁/wR₂ = 0.029/0.067. Sr₂Zn(OH)₆ and Ba₂Zn(OH)₆ crystallize isotypic in a distorted Li₂O structure type. Sr²⁺ resp. Ba²⁺ form a cubic primitive arrangement. Distorted octahedra of OH^– around Zn²⁺ fill therein alternating cubic gaps in an ordered way.     

Zur Kristallchemie der Kupfer-Lanthanoid-Oxowolframate: (I) triklin-α-CuTbW2O8, (II) monoklin-CuInW2O8 und (III) monoklin-CuYW2O8

The Crystal Chemistry of Copper Rare-Earth Oxotungstates: (I): triclinic-α-CuTbW₂O₈, (II): monoclinic-CuInW₂O₈ and (III): monoclinic-CuYW₂O₈ Single crystals of (I), (II) and (III) were prepared by recrystallisation in closed systems and examined by X-ray technique. (I): space group C? P1 , a = 7.3080, b = 7.8945, c = 7.1476 Å, α = 115.23, β = 116.21, γ = 56.98°, Z = 2; (II): space group C? C2/c, a = 9.6576, b = 11.6496, c = 4.9863 Å, β = 91.17°, Z = 4; (III): space group C? P2/n, a = 10.0504, b = 5.8214, c = 5.0224 Å, β = 94.23°, Z = 2. The crystal structures are discussed with respect to calculations of the coulombterms of lattice energy and possible valence states of Cu²⁺ and Mo⁵⁺.     

Synthese und Struktur des ersten ternären Blei(II)-Oxocuprats(I): PbCu2O2

Synthesis and Structure of the First Ternary Lead(II) Copper(I) Oxide: PbCu₂O₂ PbCu₂O₂ can be prepared by solid state reaction or by precipitation from a basic aqueous solution. Single crystals of the new compound were prepared by recrystallisation from a molten mixture (PbO? Cu₂O) and investigated by X-ray diffractometer technique. PbCu₂O₂ crystallizes isotypically with the homologue silver compound PbAg₂O₂ (monoclinic with a = 8.22₃ Å, b = 8.28₉ Å, c = 6.01₅ Å, β = 132.6₂°, Z = 4, space group C? C 1 2/c 1). The crystallographic data from the X-ray investigation are reported. The structure is built by endless [PbO_4/4]- and [CuO_2/4]-chains. Pb²⁺ has a one-sided asymmetric coordination with four next oxygen neighbours and Cu⁺ forms a stretched dumbbell with two oxygen atoms.     

Synthese und Kristallstruktur von [N(Hex)4][Cu2(CN)3]

Synthesis and Crystal Structure of [N(Hex)₄] [Cu₂(CN)₃] [N(Hex)₄][Cu₂(CN)₃] has been prepared by solvothermal reaction of CuCN with Tetra‐n‐hexylammoniumiodide in acetone. The crystal structure is built up by condensed (CuCN)₆ and (CuCN)₇ rings, forming a zeolith type cyanocuprate(I) framework [Cu₂(CN)₃^—]. Space group R3; α = 44.482(6), c = 21.283(4) Å, V = 36471(9) ų; Z = 9.     

Korrelation Tolmanscher Kegelwinkel mit 1J-Werten von Phosphoniumfluorsulfonaten

The Correlation of Tolman's Cone Angles with ¹J of Phosphonium Fluorosulfonates A ¹H-n.m.r. study of three series of phosphonium salts [HPR_3?nH_n]X, and [HPPh₂R_1?nH_n]X and (R = aliphatic substituent and H, X = SO₃ F) gives a good relationship between increasing values of ¹J versus decreasing size of substituted phosphines. A method to obtain Tolman's cone angle is described.     

Zur Kristallstruktur von Ba2ZnO3

On the Crystal Structure of Ba₂ZnO₃ Single crystals of Ba₂ZnO₃ were prepared by solid state reaction. It crystallizes monoclinic: space group C ? C12/c1; a = 5.833; b = 11.376; c = 12.585 Å; β = 93.63°; Z = 8. The crystal structure is characterised by [ZnO₃] chains along [100]. They are connected by Ba²⁺ in seven fold oxygen coordination.     

Darstellung,Schwingungsspektren und Kristallstrukturen von [(Ph3P)2N]2[(W6Cl)I] · 2 Et2O · 2 CH2Cl2 und [(Ph3P)2N]2[(W6Cl)(NCS)] · 2 CH2Cl2

Synthesis, Crystal Structures, and Vibrational Spectra of [(Ph₃P)₂N]₂[(W₆Cl )I ] · 2 Et₂O · 2 CH₂Cl₂ and [(Ph₃P)₂N]₂[(W₆Cl )(NCS) ] · 2 CH₂Cl₂ By treatment of [(W₆Cl)I]^2– with (SCN)₂ in dichloromethane at –20 °C the hexaisothiocyanato cluster anion [(W₆Cl)(NCS)]^2– is formed. X‐ray structure determinations have been performed on single crystals of [(Ph₃P)₂N]₂[(W₆Cl)I] · 2 CH₂Cl₂ · 2 Et₂O ( 1 ) (triclinic, space group P1, a = 10.324(5), b = 14.908(3), c = 17.734(8) Å, α = 112.78(2)°, β = 99.13(3)°, γ = 92.02(3)°, Z = 1) and [(Ph₃P)₂N]₂[(W₆Cl)(NCS)] · 2 CH₂Cl₂ ( 2 ) (triclinic, space group P1, a = 11.115(2), b = 14.839(2), c = 17.036(3) Å, α = 104.46(1)°, β = 105.75(2)°, γ = 110.59(1)°, Z = 1). The thiocyanate ligands of 2 are bound exclusively via N atoms with W–N bond lengths of 2.091–2.107 Å, W–N–C angles of 173.1–176.9° and N–C–S angles of 178.1–179.3°. The vibrational spectra exhibit characteristic innerligand vibrations at 2067–2045 (ν_CN), 879–867 (ν_CS) and 490–482 (δ_NCS). Based on the molekular parameters of the X‐ray determination of 1 the vibrational spectra of the corresponding (n‐Bu₄N) salt of 1 are assigned by normal coordinate analysis. The valence force constants are f_d(WW) = 1.61, f_d(WI) = 1.23 and f_d(WCl) = 1.10 mdyn/Å.     

Die Kristallstruktur von NaBiO2

The crystal structure of NaBiO₂ NaBiO₂ crystallizes monoclinic in C with a = 7.39₄, b = 7.26₂, c = 5.88₆ Å, β = 127.7°; Z = 4. Parameters were refined by least-squares (555 hkl with |h?l| = 0 to 4; R = 10.9%). Angular groups [BiO₂] are twisted by 180°, forming chains [BiO_2/2O_2/2] along [001]. The MADELUNG part of lattice energy (MAPLE) is calculated and discussed.     

Zur Struktur der LiMIIMIIIF6-Verbindungen. Neue Verbindungen mit MIII=In und Ti

On the Structure of LiM^IIM^IIIF₆ Compounds. New Compounds with M^III=IN and Ti LiMn^IIInF₆ compounds with M^II = Mg, Mn, Co, Ni, Zn, Cd and Ca crystallize in the Na₂SiF₆ structure. The Ti(III) compound LiMgTiF₆ has trirutile structure, LiMnTiF₆ has Na₂SiF₆ and trirutile structure (H.-T. modification), LiCaTiF₆ and LiCdTiF₆ have Li₂ZrF₆ superstructure. With M^II = Co, Ni and Zn solid solutions trirutile — MF₂(rutile) could be only prepared. The lattice constants of all compounds are reported. For LiMnVF₆ and LiFeGaF₆ too dimorphism Na₂SiF₆ trirutile was observed. In the system LiNiCrF₆ (trirutile) — LiMnCrF₆ (Na₂SiF₆ structure) phase limits of both structures are determined in dependence on the ratio of ionic radii r/r. Magnetic data of the In compounds with M^II = Co and Ni and of the Ti(III) compounds with M^II = Mg, Zn, Mn, just as of α- and β-LiMnVF₆ are also given. The three structures only exist if r reaches from 0.6 to 1.2 Å and r from 0.5 to 0.8 Å. The stability-fields are determined by the ratio of ionic radii r/r_Li, r/r_Li and r/r: trirutile 0.9–1.2, Na₂SiF₆ type 1.2–～1.4 and Li₂ZrF₆ superstructure >1.4. The dependence of rate of ionic radii is explained by the different sharing of MF₆ octahedra.     

EPR-Einkristalluntersuchungen System Fe(NO)(Et2dsc)2/In(Et2dsc)3 (Et2dsc = Diethyldiselenocarbamat). Kristall- und Molekülstruktur von Tris(diethyldiselenocarbamato)indium(III), In(Et2dsc)3

Single Crystal Electron Paramagnetic Resonance Study on the System Fe(NO)(Et₂dsc)₂/In(Et₂dsc)₃ (Et₂dsc = diethyldiselenocarbamate). Crystal and Molecular Structure of Tris(diethyldiselenocarbamato)indium(III), In^III(Et₂dsc)₃ A single-crystal EPR study (T = 295 K) of Bis(diethyldiselenocarbamato)nitrosyliron(I) incorporated in Tris(diethyldiselenocarbamato)indium(III) is reported. The tensors g an A^N have rhombic symmetry with g₁ = 2.048, g₂ = 2.058, g₃ = 2.062 and A = 9.2 · 10^?4 cm^?1, A = 10.0 · 10^?4 cm^?1, A = 11.3 · 10^?4 cm^?1. The A values are discussed in terms of spin density distribution. The x-ray crystallographic data of In^III(Et₂dsc)₃ (space group P2₁/c, a = 6.731(3) Å, b = 18.05(9) Å, c = 20.914(10) Å, α = 90.02(2)°, β = 93.74(2)° and γ = 90.01(2)°) are given.