Darstellung und Kristallstruktur von (n-Bu4N)3[Ir(NCS)(SCN)5]

Preparation and Crystal Structure of (n-Bu₄N)₃[Ir(NCS)(SCN)₅] The evaporated ethanolic extrakt of the reaction product of K₃[IrCl₆] and HNO₃, refluxed with an aqueous KSCN solution yields a mixture of the linkage isomers [Ir(NCS)_n(SCN)_6?-n]^3?, n = 0? 2, and small amounts of linkage isomeric chloropentarhodanoiridates(III), from which [Ir(NCS)(SCN)₅]^3? has been isolated by ion exchange chromatography on DEAE-cellulose. The X-Ray structure determination on a single crystal of (n-Bu₄N)₃[Ir(NCS)(SCN)₅] (monoclinic, space group P 2₁/a, a = 17.513(5), b = 32.607(5), c = 23.661(5) Å, β = 94.757(5)°, Z = 8) confirms the existance of a heteroleptic hexakis(thiocyanato(N)-thiocyanato(S))iridate(III) with an Ir? N distance of 2.03 Å and Ir? S bond lengths between 2.29 and 2.38 Å. The SCN groups with angles between 166 and 175° are nearly linear with Ir? S? C angles from 99.9 to 109.4°. The Ir? N? C angles of the two crystallographic independent anions are 166 and 174°.     

Spectroscopic studies and crystal structure of a dimeric Zn(II) complex with diethyl (pyridin-2-ylmethyl)phosphate

The crystal structure of [Zn₂(2-pmOpe)₂Cl₄] (2-pmOpe?=?diethyl (pyridin-2-ylmethyl)phosphate) was determined by X-ray-diffraction method. The compound was also characterized by IR, far-IR, 1H, and ³¹P NMR spectroscopy. In this compound, 2-pmOpe is a bidentate N,O-bridging ligand and Zn(II) are slightly distorted tetrahedral ZnNOCl₂. Zn(II) ions are doubly bridged by the 2-pmOpe ligands, resulting in a dinuclear species. The structure is stabilized by intermolecular C–H?···?O and C–H?···?Cl hydrogen bonds. The spectral properties are in agreement with the structural data.     

Synthesis,Characterization and Crystal Structures of new Palladium(II) Complexes and the first Platinum(III) Complex Containing ATT (ATT = 6‐Aza‐2‐thiothymine)

Treatment of the ligand 6‐aza‐2‐thiothymine (ATT, HL, 1 ) with palladium chloride in methanol forms the ionic complex [(HL)₄Pd]Cl₂·8MeOH ( 2 ), while its reaction with palladium iodide in same solvent produces the neutral complex trans‐[(HL)₂PdI₂]·2MeOH ( 3 ) in high yields. The reaction of 1 with Na₂[PdCl₄] in the presence of sodium acetate in a molar ratio of 2:1:2 and with platinum(II) chloride in presence of sodium acetate led to the dimer tetranuclear complexes [(L₄Pd₂)NaCl]₂·8MeOH ( 4 ) and [L₄Pt₂Cl₂]·6MeOH·H₂O ( 5 ). The latter is the first Pt^III complex of the ligand. All complexes were characterized by elemental analyses and IR spectroscopy and the crystal structures of 2 , 3 , 4 and 5 are determined by single‐crystal X‐ray diffraction. Crystal data for 2 at ?80 °C: triclinic space group , a = 1006.6(1), b = 1006.9(1), c = 1158.1(1) pm, α = 85.20(1)°, β = 83.84(1)°, γ = 88.91(1)°, Z = 1, R₁ = 0.0278; for 3 at ?80 °C: triclinic space group , a = 490.5(1), b = 977.2(2), c = 1116.8(2) pm, α = 90.26(1)°, β = 102.33(1)°, γ = 96.08(1)°, Z = 1, R₁ = 0.0394; for 4 at ?80 °C: orthorhombic space group Ccca, a = 1791.7(2), b = 1874.1(2), c = 2044.0(1) pm, Z = 4, R₁ = 0.0341 and for 5 at ?80 °C: monoclinic space group P2₁/c, a = 1464.3(1), b = 2003.7(1), c = 1368.5(1) pm, β = 95.66(1)°, Z = 4, R₁ = 0.0429.     

Darstellung,Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalyse der bindungsisomeren Chlororhodanoiridate(III) trans-[IrCl2(SCN)4]3− und trans-[IrCl2(NCS)(SCN)3]3−

Preparation, Crystal Structures, Vibrational Spectra, and Normal Coordinate Analysis of the Linkage Isomeric Chlororhodanoiridates(III) trans-[IrCl₂(SCN)₄]^3? and trans-[IrCl₂(NCS)(SCN)₃]^3? By treatment of Na₂[IrCl₆] with NaSCN in 2N HCl the linkage isomers trans-[IrCl₂(SCN)₄]^3? and trans-[IrCl₂(NCS)(SCN)₃]^3? are formed which have been separated by ion exchange chromatography on diethylaminoethyl cellulose. X-ray structure determinations on single crystals of trans-(n-Bu₄N)₃[IrCl₂(SCN)₄] ( 1 ) (monoclinic, space group P2₁/a, a = 18.009(4), b = 15.176(3), c = 23.451(4) Å, β = 93.97(2)°, Z = 4) and trans-(Me₄N)₃[IrCl₂(NCS)(SCN)₃] ( 2 ) (monoclinic, space group P2₁/a, a = 17.146(5), b = 9.583(5), c = 18.516(5) Å, β = 109.227(5)°, Z = 4) reveal the complete ordering of the complex anions. The via S or N coordinated thiocyanate groups are bonded with Ir? S? C angles of 105.7–109.7° and the Ir? N? C angle of 171.4°. The torsion angles Cl? Ir? S? C and N? Ir? S? C are 3.6–53.0°. The IR and Raman spectra of ( 1 ) are assigned by normal coordinate analysis using the molecular parameters of the X-ray determination. The valence force constants are f_d(IrS) = 1.52 and f_d(IrCl) = 1.72 mdyn/Å.     

Darstellung,Kristallstruktur und Normalkoordinatenanalyse der bindungsisomeren Pentachlororhodanoosmate(IV)

Preparation, Crystal Structure and Normal Coordinate Analysis of Linkage Isomeric Pentachlororhodanoosmates(IV) By treatment of [OsCl₅I]^2? with (SCN)₂ in dichloromethane the linkage isomers [OsCl₅(NCS)]^2? and [OsCl₅(SCN)]^2? are formed which have been separated by ion exchange chromatography on diethylaminoethyl cellulose. The X-ray structure determination on single crystals of (Ph₄As)₂[OsCl₅(NCS)] (monoclinic, space group P2₁/a, a = 18.872(2), b = 11.6024(2), c = 22.786(1), β = 109.057(1)°, Z = 4) and (Ph₄As)₂[OsCl₅(SCN)] (monoclinic, space group P2₁/a, a = 19.057(2), b = 11.306(2), c = 22.612(1), β = 106.64(2)°, Z = 4) reveals the complete ordering of the complex anions. The thiocyanate group is located above one of the Cl ligands of the equatorial plane with the Os? N? C angle of 166.1° for N bonding and the Os? S? C angle of 109.9° for S bonding. The IR and Raman spectra of both linkage isomers known from literature are assigned by normal coordinate analysis based on the general valence force field using the molecular parameters of the X-ray determination. The valence force constants are f_d(OsN) = 1,81 and f_d(OsS) = 1,32 mdyn/Å. Taking into account increments of the trans influence a good adjustment between observed and calculated frequencies is achieved.     

Synthese und Kristallstruktur des Zirkonocen-Alkinyl-Alkenyl-Komplexes (Z)?Cp2Zr(CCPh){C(Ph) = C(H)P(SiMe3)2}

Synthesis and Crystal Structure of the Zirkonocene Alkynyl Alkenyl Complex (Z)? Cp₂Zr(C?CPh){C(Ph) = C(H)P(SiMe₃)₂} The reaction of ( Z )? Cp₂Zr(C(Ph) = C(H)P(SiMe₃)₂}(Cl) with lithium phenylacetylide yields the zirconocene alkynyl alkenyl complex ( Z )? Cp₂Zr(C?CPh){C(Ph) = C(H)P(SiMe₃)₂} ( 1 ). 1 was characterised spectroscopically (IR, NMR, MS) and by X-ray structure determination. The complex crystallises triclinic in the space group P1 with a = 10.561(10), b = 11.226(12), c = 14.274(13) Å, α = 70.87(7), β = 77.70(7), γ = 77.85(7)°. In 1 , there are two different Zr? C bond distances (Zr? C(=C) 2.415(6), Zr? C(?C) 2.309(6) Å). A Zr? P interaction (Zr? P 2.774(3) Å) is observed in the solid state.     

The gas-phase structure of bis(fluorosulfonyl)difluoromethane, (SO2F)2CF2

New synthetic pathways and the infrared spectrum of bis(fluorosulfonyl)difluoromethane, (SO₂F)₂CF₂, are reported. The geometric structure and conformational properties of the title compound have been studied by gas electron diffraction. Depending on the rotational position of the two SO₂F groups, four conformers with different symmetries can occur in this compound: C_2v symmetry, if both S? F bonds stagger the CF₂ group. C₂ or C_s symmetry, if one S?O bond of each group staggers the CF₂ group. The experimental electron diffraction intensities can be fitted equally well with a C₁ conformer or with a mixture of C_2v, C₂ and C_s conformers, in a ratio of 3:2:5. The following geometric parameters (r_a distances, ∠_α angles with 3σ uncertainties) were derived: C? F = 1.340(6) Å, S?O = 1.412(2) Å, S? F = 1.550(3) Å, C? S = 1.848(4) Å, S? C? S = 113.6(7)°, F? C? F = 110.0(10)°, O?S?O = 124.6(18)°, C? S? F = 96.5(16)° and C? S?O = 108.4(14)°.     

Darstellung,Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalyse von vier bindungsisomeren Tetrachlorodirhodanoosmaten(IV)

Preparation, Crystal Structures, Vibrational Spectra, and Normal Coordinate Analysis of Four Linkage Isomeric Tetrachlorodirhodanoosmates(IV) By treatment of cis- or trans-[OsCl₄I₂]^2? with (SCN)₂ in dichloromethane the linkage isomers cis-[OsCl₄(NCS)₂]^2? ( 1 ), trans-[OsCl₄(NCS)(SCN)]^2? ( 2 ), cis-[OsCl₄(NCS)(SCN)]^2? ( 3 ) and trans-[OsCl₄(SCN)₂]^2? ( 4 ) are formed which have been separated by ion exchange chromatography on diethylaminoethyl cellulose. The X-Ray structure determinations on single crystals of cis-(Ph₄As)₂[OsCl₄(NCS)₂] (triclinic, space group P1 , a = 10.019(5), b = 11.702(5), c = 21.922(5) Å, α = 83.602(5)°, β = 85.718(5)°, γ = 73.300(5)°, Z = 2), trans-(Ph₄As)₂[OsCl₄ · (NCS)(SCN)] (monoclinic, space group P2₁/c, a = 18.025(5), b = 11.445(5), c = 23.437(5) Å, β = 94.208(5)°, Z = 4), cis-(Ph₄As)₂[OsCl₄(NCS)(SCN)] (triclinic, space group P1 , a = 10.579(5), b = 11.682(5), c = 22.557(5) Å, α = 81.073(5)°, β = 85.807(5)°, γ = 87.677(5)°, Z = 2) and trans-(Ph₄As)₂ · [OsCl₄(SCN)₂] (triclinic, space group P1 , a = 10.615(5), b = 11.691(5), c = 11.907(5) Å, α = 111.314(5)°, β = 96.718(5)°, γ = 91.446(5)°, Z = 1) reveal the complete ordering of the complex anions. The via N or S coordinated thiocyanate groups are located nearly direct above one of the cis-positioned Cl ligands with Os? N? C angles of 171.2° and 174.3° ( 1 ), 162.3° ( 2 ), 172° ( 3 ) and Os? S? C angles of 108.3° ( 2 ), 105.7° ( 3 ) and 105.5° ( 4 ). Using the molecular parameters of the X-Ray determinations the low temperature (10 K) IR and Raman spectra of the (n-Bu₄N) salts of all four linkage isomers are assigned by normal coordinate analyses based on a modified valence force field. The valence force constants are f_d(OsN) = 1.59 ( 1 ), 1.67 ( 2 ), 1.60 ( 3 ) and f_d(OsS) = 1.27 ( 2 ), 1.31 ( 3 ) and 1.32 mdyn Å^?1 ( 4 ). Taking into account increments of the trans influence a good agreement between observed and calculated frequencies is achieved.     

Kristall- und MolekülStruktur von Tetramethyl(dimethylthiophosphinato)-stiboran (CH3)4SbOP(S) (CH3)2

Crystal and Molecular Structure of Tetramethyl(dimethylthiophosphinato)stiborane (CH₃)₄SbOP (S) (CH₃)₂ (CH₃)₄SbOP(S)(CH₃)₂ crystallizes in the triclinic space-group P1 with a = 7.125, b = 9.297, c = 18.861 Å, α = 77.44°, ß = 83.86°, γ = 79.91° and four formula units per cell. Stibonium is distorted trigonal-bipyramidal and phosphorous distorted tetrahedral surrounded. The mean values of bondlengths are: Sb? C_eq = 2.108, Sb? C_ax = 2.147, Sb? O = 2.641, P? C = 1.819, P? O = 1.514, and P? S = 1.987 Å.     

Darstellung,Schwingungsspektren und Normalkoordinatenanalyse von mer-[OsCl3I(NCS)]2− sowie Kristallstrukturanalyse von zwei Modifikationen des mer-(Ph4As)2[OsCl3I(NCS)2c]

Preparation, Vibrational Spectra, and Normal Cooordinate Analysis of mer-[OsCl₃I(NCS)₂^c]^2? and Crystal Structures of two Modifications of mer-(Ph₄As)₂[OsCl₃I(NCS)₂^c] By treatment of cis-/trans-[OsCl₄I₂]^2? or fac-[OsCl₃I₃]^2? with (SCN)₂ in dichloromethane mixtures of different linkage isomers are formed, from which mer-[OsCl₃I(NCS)]^2? has been isolated by ion exchange chromatography on diethylaminoethyl cellulose. With tetraphenylarsonium ions mer-(Ph₄As)₂[OsCl₃I(NCS)₂^c] crystallizes in two different modifications. From acetone solution the high-temperature form α precipitates above ?10°C, the low-temperature form β below, ?65°C. The X-Ray structure determinations on single crystals of α-mer-(Ph₄As)₂[OsCl₃I(NCS)₂^c] (triclinic, space group P 1 , a = 10.245(5), b = 11.690(5), c = 22.027(5) Å, α = 83.650(5)°, β = 85.734(5)°, γ = 72.566(5)°, Z = 2) and β-mer-(Ph₄As)₂[OsCl₃I(NCS)₂^c] (triclinic, space group P 1 , a = 10.959(5), b = 11.122(5), c = 21.745(5) Å, α = 97.677(5)°, β = 92.339(5)°, γ = 104.712(5)°, Z = 2) reveal the ordering of the complex anions, which significantly differ in their geometry. The via N coordinated thiocyanate groups exhibit Os? N? C angles of 172.7° and 173.3° (α) and of 164.4° and 175.4° (β). Using the molecular parameters of the X-Ray determinations the low temperature (10 K) IR and Raman spectra of the (n-Bu₄N) salt of the complex anion are assigned by a normal coordinate analysis based on a modified valence force field. The valence force constants are f_d(OsN) = 1.66 and 1.64 mdyn/Å. Taking into account the trans influence a good agreement between observed and calculated frequencies is achieved.     

Synthesis and reactivity with M(II) (M=Co and Cu) chloride of 1-[(2-carboxyethyl)benzene]-3-[benzothiazole]triazene

Reaction of ethyl anthranilate, sodium nitrite, and 2-aminobenzothiazole produces a new triazenide compound, 1-[(2-carboxyethyl)benzene]-3-[benzothiazole]triazene (HL), which has been characterized by X-ray crystallography and NMR spectrum. In the presence of Et₃N, reaction of HL and CuCl₂?·?2H₂O or CoCl₂?·?6H₂O in THF/methanol affords a tetranuclear copper(II) complex [Cu₄L₄(µ-OMe)₄]?·?4THF (1) and a cobalt(III) complex [CoL′₃] (2) (L′ is 1-[benzothiazole] triazene ion), accompanied by C–N bond cleavage of HL. They are characterized by X-ray crystallography and magnetic susceptibility measurement. Magnetic studies indicate significant antiferromagnetic coupling between the copper(II) centers for 1. The value obtained for the coupling constant J is ?585?cm^?1.     

Sulfur‐assisted Chloride and Triphenylphosphine Dissociation of Palladium(II) Complex with Phenyloxythiocarbonyl,PhOC(S), Containing Ligand: X‐Ray Structure of [Pd(PPh3)2{η1‐C(S)OPh}(Cl)]

Treatment of Pd(PPh₃)₄ with phenylchlorothionoformate, PhOC(S)Cl, in dichloromethane at ?20 °C produces the phenyloxythiocarbonyl complex [Pd(PPh₃)₂{η¹‐C(S)OPh}(Cl)], 1 . The ³¹P{¹H} NMR spectrum of 1 shows the dissociation of either the chloride or the triphenylphosphine ligand to form complex [Pd(PPh₃)₂(η²‐SCOPh)][Cl], 2 or the dipalladium complex [Pd(PPh₃)Cl]₂(μ,η²‐SCOPh)₂, 3 . Continuous stirring of the dichloromethane solution of 1 at room temperature for 4 h forms the dipalladinum complex [Pd(PPh₃)Cl]₂(μ,η²‐SCOPh)₂, 3 as the final product. Respective reactions of 1 and Et₂NCS₂Na or dppa {bis(diphenylphosphino)amine} gives complex [Pd(PPh₃){η¹‐C(S)OPh}(η²‐S₂CNEt₂)], 4 or [Pd(PPh₃){η¹‐C(S)OPh}(η²‐dppa)][Cl], 5 . Complex 1 is determined by single‐crystal X‐ray diffraction and crystallized in the monoclinic space group P2₁ with Z = 4. The cell dimensions of 1 are as follows: a = 9.5613(1) Å, b = 33.6732(3) Å, c = 12.2979(1) Å.     

Darstellung,Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalyse von vier bindungsisomeren Trichlorotrirhodanoosmaten(IV)

Preparation, Crystal Structures, Vibrational Spectra, and Normal Coordinate Analysis of four Linkage Isomeric Trichlorotrirhodanoosmates(IV) By treatment of fac-[OsCl₃I₃]^2? with (SCN)₂ in dichloromethane the linkage isomers fac-[OsCl₃(NCS)₃]^2? ( 1 ), mer-[OsCl₃(NCS)₂^c(SCN)]^2? ( 2 ), mer-[OsCl₃(NCS)(SCN)₂^t]^2? ( 3 ), and mer-[OsCl₃(NCS)(SCN)₂^c]^2? ( 4 ) are formed which have been separated by ion exchange chromatography on diethylaminoethyl cellulose. X-Ray structure determinations have been performed on single crystals of fac-(Ph₄As)₂[OsCl₃(NCS)₃] (triclinic, space group P1 , a = 12.142(5), b = 13.233(5), c = 19.300(5) Å, α = 98.642(5)º, β = 100.509(5)º, γ = 112.514(5)º, Z = 2), mer-(Ph₄As)₂[OsCl₃(NCS)₂^c (SCN)] · acetone (triclinic, space group P1 , a = 11.707(5), b = 13.238(5), c = 19.048(5) Å, α = 75.960(5)º, β = 88.981(5)º, γ = 69.999(5)º, Z = 2), mer-(Ph₄As)₂[OsCl₃(NCS)(SCN)₂ ^t] (triclinic, space group P1, a = 10.6861(12), b = 11.6587(5), c = 12.5232(5) Å, α = 112.069(8)º, β = 95.052(8)º, γ = 92.559(7)º, Z = 1) and mer-(Ph₄As)₂[OsCl₃(NCS)(SCN)₂ ^c] · 2acetone (triclinic, space group P1 , a = 11.444(5), b = 14.661(5), c = 15.830(5) Å, α = 75.790(5)º, β = 80.273(5)º, γ = 75.205(5)º, Z = 2). The complex anions are completely ordered. The via N or S coordinated thiocyanate groups are located nearly direct above one of the cis-positioned Cl ligands with Os? N? C angles of 169.1º, 171.5º, 175.7º ( 1 ), 175.6º, 178.6º ( 2 ), 172º ( 3 ), and 173.1º ( 4 ) and Os? S? C angles of 106.2º ( 2 ), 106.1º, 106.6º ( 3 ), 105.1º, and 108.2º ( 4 ). Using the molecular parameters of the X-Ray determinations the low temperature (10 K) IR and Raman spectra of the (n-Bu₄N) salts of all four linkage isomers have been assigned by normal coordinate analyses based on a modified valence force field. The valence force constants are f_d(OsN) = 1.71 ( 1 ), 1.46 and 1.62 ( 2 ), 1.69 ( 3 ), and 1.61 ( 4 ), f_d(OsS) = 1.27 ( 2 ), 1.36 ( 3 ), 1.32, and 1.49 mdyn/Å ( 4 ). Taking into account increments of the trans influence a good agreement between observed and calculated frequencies is achieved.     

Synthesis,characterization and in vitro cytotoxicity screening of some triarylbismuth(V) di(N‐salicylidene)amino carboxylates and the crystal structure of (2‐HOC6H4CHNCH2CO2)2Bi(C6H5)3

Four novel triarylbismuth(V) di(N‐salicylidene)amino carboxylates were synthesized. Their structures were confirmed by IR, ¹H NMR, ¹³C NMR and elemental analysis. The crystal structure of (2‐HOC₆H₄CH?NCH₂CO₂)₂BiPh₃ was determined by X‐ray diffraction. The in vitro cytotoxicity of all compounds against three human cancer cells (HL‐60, BGC‐823 and MDA‐MB‐435) at 10 µM are reported. Copyright © 2005 John Wiley & Sons, Ltd.     

Oxo(trisyl)boran (Me3Si)3C?BO als Zwischenstufe

Oxo(trisyl)borane (Me₃Si)₃C? B?O as an Intermediate The acyclic trisylboranes R? B(OSiMe₃)? Cl ( 4 a ) and R? B(OH)? H ( 5 a ) and the cyclic boranes (? RB? O? CO? CO? O? ) ( 1 a ) and (? RB? O? RB? O? SO₂? O? ) ( 6 a ) [R = (Me₃Si)₃C, “Trisyl”] are thermolyzed in the gasphase to give well-defined products. The tris(trisyl)boroxine (? RB? O? )₃ ( 2 a ) is formed from 4 a and 5 a at 140 and 160°C, respectively, besides Me₃SiCl and H₂, respectively, whereas the six-membered ring [? BMe? CH(SiMe₃)? SiMe₂? O? SiMe₂? CH₂? ] ( 8 ) is the product from 1 a and 6 a at 600 and 700°C, respectively, besides CO/CO₂ and SO₃, respectively. The oxoborane R? B?O is presumably a common intermediate. It is stabilized at the lower temperature by cyclotrimerization to give 2 and at the higher temperature by a sequence of several intramolecular steps: a 1,3-silyl shift along the chain C? B? O, an exchange of Me and Me₃SiO along the chain Si? C? B, and a C? H addition to the B?C double bond; the steps can be rationalized by analogous known reactions. The gas-phase thermolysis at 600°C of the dioxaboracyclohexenes (? BR? O? CR′ = CH? CRR′? O? ) ( 7 b? d ; R = Me, iPr, tBu; R′ = Me) yields the boroxines (RBO)₃ and the enones Me? CO? CH?CHR? Me; the cyclohexene 7 e (R = Me; R′ = CF₃) is not decomposed at 600°C.     

Synthese und Kristallstrukturen der Wolfram(VI)-Alkin-Komplexe [W2(O)(OMe)6(Et?Se?CC?Se?Et)2] und Li[W(OMe)5(Et?Te?CC?Te?Et)]

Synthesis and Crystal Structures of the Tungsten(VI)-alkyne Complexes [W₂(O)(OMe)₆(Et? Se? C?C? Se? Et)₂] and Li[W(OMe)₅(Et? Te? C?C? Te? Et)] The title compounds have been prepared by reactions of lithium methanolate with [WCl₄(Et? Se? C?C? Se? Et)(THF)] and [WCl₄(Et? Te? C?C? Te? Et)(THF)], respectively, in diethylether suspensions. Both complexes were characterized by crystal structure determinations. [W₂(O)(OMe)₆(Et? Se? C?C? Se? Et)₂]: Space group P1 , Z = 2, structure determination with 4 320 observed unique reflections, R = 0.041. Lattice dimensions at ?70°C: a = 949.3, b = 1 225.3, c = 1 285.0 pm, α = 82.48°; γ = 82.44°; β = 81.44°. The tungsten atoms are bridged by three μ₂-O-atoms of the OMe groups; the alkyne ligands are coordinated side-on in a metallacyclopropene-like fashion. Li[W(OMe)₅(Et? Te? C?C? Te? Et)]: Space group P1 , Z = 2, structure determination with 9 381 observed unique reflections, R = 0.038. Lattice dimensions at ?70°C: a = 983.4, b = 1606.9, c = 1971.5 pm, α = 66.09°, β = 84.29°, γ = 79.83°. The lithium ions link the [W(OMe)₅(Et? Te? C?C? Te? Et)]^? anions to a trimeric ion ensemble via the O atoms of three OMe groups of each anion.     

Darstellung und Kristallstruktur von Tetraphenylphosphonium-Hexathiocyanatorhodat(III), [P(C6H5)4]3[Rh(SCN)6]

Preparation and Crystal Structure of Tetraphenylphosphonium Hexathiocyanatorhodate(III), [P(C₆H₅)₄]₃[Rh(SCN)₆] By treatment of RhCl₃ · n H₂O with KSCN in water a mixture of the linkage isomers [Rh(NCS)_n(SCN)_6–n]^3?, n = 0–2 is formed which is separated by ion exchange chromatography on diethylaminoethyl cellulose. The X-ray structure determination on a single crystal of [P(C₆H₅)₄]₃[Rh(SCN)₆] (monoclinic, space group C1c1, a = 13.620(5), b = 22.929(13), c = 22.899(9) Å, β = 98.55(3)°, Z = 4) confirms the coordination of all ligands via S with the middle Rh? S distance of 2.372 Å and Rh? S? C angles of 109°. The SCN groups are nearly linear with 175° and averaged bondlengths S? C 1.63 and C? N 1.14 Å. The crystal lattice is build up by layers of complex anions and voluminous cations with no specific interactions but which are closely connected by thiocyanate ligands and phenyl rings.     

Tetrakis(chloromethyl)phosphonium chloride monohydrate

Tetrakis­(chloro­methyl)­phospho­nium chloride monohydrate, C₄H₈Cl₄P⁺·Cl^?·H₂O or P(CH₂Cl)₄⁺·Cl^?·H₂O, is the first crystal structure determination of a tetrakis­(halogeno­methyl)­phospho­nium compound to date. The only comparable structures known so far are of phospho­nium ions containing just one halogeno­methyl group. The solvent water mol­ecule interacts with the Cl^? anion via hydrogen bonds, with O?Cl distances of 3.230 (2) and 3.309 (2) Å. The structure also contains several C—H?Cl^? and C—H?O contacts, though with longer D?A distances [D?A 3.286 (3)–3.662 (2) Å] or bent D—H?A angles. For these reasons, the C—H?Cl^? and C—H?O interactions should not be considered as strong hydrogen bonds.     

Contributions on thermal behaviour and crystal chemistry of anhydrous phosphates. XIX. Tri-chromium(II)-bis-phosphate Cr3(PO4)2 (≙ Cr6(PO4)4) – A transition metal(II)-orthophosphate with new structure type

Deep blue-violet single crystals of hitherto unknown chromous orthophosphate have been obtained reducing CrPO₄ by elemental Cr at temperatures above 1050°C in evacuated silica ampoules (NH₄I or I₂ as mineraliser). The complex structure of Cr₃(PO₄)₂ (P2₁2₁2₁, Z = 8, a = 8.4849(10) Å, b = 10.3317(10) Å, c = 14.206(2) Å) contains six crystallographically independent Cr²⁺ per unit cell. Five of them are coordinated by four oxygen atoms which form a distorted (roof shaped) square plane as first coordination sphere at interatomic distances 1.96 Å ? d(Cr? O) ? 2.15 Å. Their coordination is completed by additional oxygen atoms (2 or 3) at distances 2.32 Å ? d(Cr? O) ? 3.21 Å. The sixth Cr²⁺ shows six-fold octahedral coordination with strong radial distortion (d(Cr? O): 1.97, 2.04, 2.15, 2.28, 2.29, 2.53 Å). The four different [PO₄] groups exhibit only minor deviations from ideal tetrahedral geometry (1.51 Å ? d(P? O) ? 1.57 Å, 104.3° ? ∠(O? P? O) ? 114.4°). An unusually low magnetic moment μ_exp = 4.28(2) μ_B (θ_P = ?54.8(5) K) has been observed for Cr²⁺.