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1.
Thio-chloro Compounds of Pentavalent Niobium and Tungsten: WSCl3, [WSCl4]22?, [WSCl5]2?, [NbSCl4]?. Crystal Structure of PPh4[NbSCl4] Black WSCl3 was obtained by reduction of (WSCl4)2 with C2Cl4. With PPh4Cl in CH2Cl2 it yields (PPh4)2[WSCl4]2 which has a dimeric structure with chloro bridges according to its i. r. spectrum. Iodide reduces PPh3Me[WSCl5] in CH2Cl2 to (PPh3Me)2[WSCl5], from which (PPh3Me)2[WSBr5 · BBr3] is obtained by reaction with BBr3. From PPh4Cl in CH2Cl2 and raw NbSCl3 (obtained by solid state reaction of NbCl5 with B2S3) PPh4[NbSCl4] is formed. The crystal structure of PPh4-[NbSCl4] was determined and refined with X-ray diffraction data (residual index R = 0.066 for 1017 reflexions). It crystallizes in the AsPh4[RuNCl4] structure type (space group P4/n) with the lattice constants a = 1303 and c = 760 pm. The quadratic-pyramidal [NbSCl4]? ion has a Nb?S bond length of 209 pm. The i. r. spectra of all compounds are discussed. 相似文献
2.
Thiochlorowolframates with Tungsten(V) and (VI). Crystal Structures of PPh4[WSCl4] and (PPh4)2[WS2Cl4] · 2 CH2Cl2 Diamagnetic (NEt4)2[WSCl4]2, having tungsten atoms linked via sulfur atoms, is obtained by the reaction of WCl5 with NEt4SH as well as by the reduction of WSCl4 with NEt4I in dichloromethane. If the reduction is performed with PPh4I, PPh4[WSCl4] with monomer anions is formed. Reaction of WCl6 with H2S in dichloromethane yields brown, insoluble WS2Cl2 which has terminal W?S groups and bridging W? S? W groups according to its IR spectrum. WS2Cl2 and PPh4Cl react to afford PPh4[WS2Cl3] · 2 CH2Cl2 and (PPh4)2[WS2Cl4] · 2 CH2Cl2. IR spectra are reported. The crystal structures of PPh4[WSCl4] and (PPh4)2[WS2Cl4] · 2 CH2Cl2 were determined by X-ray diffraction. PPh4[WSCl4]: tetragonal, space group P4/n, Z = 2, a = 1292.3 pm, c = 763.2 pm; R = 0.054 for 898 observed reflexions. The [WSCl4]? ion has the structure of a square pyramid with a rather short W?S bond of 206 pm length. (PPh4)2[WS2Cl4] · 2 CH2Cl2: triclinic, space group P1 , a = 1017.7, b = 1114.5, c = 1243.4 pm, α = 70.61, β = 79.73, γ = 80.80°; R = 0.076 for 1804 reflexions. The [WS2Cl4]2? has cis configuration; as it is situated on an inversion center it shows positional disorder. 相似文献
3.
Preparation and vibrational spectra of the complexes [MBr6]?, [Br5MN3]? and [Br5MNPPh3]? of niobium and tantalum. Cyrstal structure of PPh4[NbBr6] The compounds PPh4[MBr6] and PPh4[MBr5N3] are obtained by reaction of MBr5 with PPh4Br or PPh4N3, respectively, in CH2Cl2 solution (M ? Nb, Ta). The azido complexes PPh4[MBr5N3] can also be obtained by reactions of the hexabromo complexes with iodine azide. According to its i.r. spectrum the symmetry of the [MBr6]? ion is lower than Oh in the solide state. This is corfirmed for PPh4[NbBr6] by a crystal structure analysis; it crystallizes in the monoclinic space group B2/b with four formula units in the unit cell and with the lattice constants a = 2301, b = 1777, c = 686 pm and γ = 96,6°. The structure was determined with X-ray diffraction data and was refined to a residual index of R = 0.055. The [NbBr6]? ion has the symmetry Ci, the deviations from Oh being small. In the azido complexes [MBr5N3]? the azido groups are covalently linked with the metal. From [NbBr5N3]? and PPh3 the complex [Br5Nb?N?PPh3]?, is obtained; for the analogous formation of the corresponding Ta complex photochemical activation is necessary. In this way the complex [Cl5Nb?N?AsPh3]? can also be obtained. I.r. spectra of all the compounds are reported and assigned. 相似文献
4.
Reactions of Uranium Pentabromide. Crystal Structures of PPh4[UBr6], PPh4[UBr6] · 2CCl4, (PPh4)2[UBr6] · 4CH3CN, and (PPh4)2[UO2Br4] · 2CH2Cl2 PPh4[UBr6] and PPh4[UBr6] · 2CCl4 were obtained from UBr5 · CH3CN and tetraphenylphosphonium bromide in dichloromethane, the latter being precipitated by CCl4. Their crystal structures were determined by X-ray diffraction. PPh4[UBr6]: 2101 observed reflexions, R = 0.090, space group C2/c, Z = 4, a = 2315.5, b = 695.0, c = 1805.2 pm, β = 96.38°. PPh4[UBr6] · 2CCl4: 2973 reflexions, R = 0.074, space group P21/c, Z = 4, a = 1111.5, b = 2114.2, c = 1718.7 pm, β = 95.42°. Hydrogen sulfide reduces uranium pentabromide to uranium tetrabromide. Upon evaporation, bromide is evolved from solutions of UBr5 with 1 or more then 3 mol equivalents of acetonitrile in dichlormethane yielding UBr4 · CH3CN and UBr4 · 3CH3CN, respectively. These react with PPh4Br in acetonitrile affording (PPh4)2[UBr6] · 4CH3CN, the crystal structure of which was determined: 2663 reflexions, R = 0.050, space group P21/c, Z = 2, a = 981.8, b = 2010.1, c = 1549.3 pm, β = 98.79°. By reduction of uranium pentabromide with tetraethylammonium hydrogen sulfide in dichloromethane (NEt4)2[U2Br10] was obtained; (PPh4)2[U2Br10] formed from UBr4 and PPh4Br in CH2Cl2. Both compounds are extremely sensitive towards moisture and oxygen. The crystal structure of the oxydation product of the latter compound, (PPh4)2[U02Br4]· 2 CH2Cl2, was determined: 2163 reflexions, R = 0.083, space group C2/c, Z = 4, a = 2006.3, b = 1320.6, c = 2042,5 pm, β = 98.78°. Mean values for the UBr bond lengths in the octahedral anions are 266.2 pm for UBr6-, 276.7 pm for UBr62? and 282.5 pm for UO2Br42? 相似文献
5.
Adducts of Oxotetrachloro-niobate (V). Formation, Vibrational Spectra, and Crystal Structures of PPh4[NbOCl4(OH2)] and (PPh4)2[NbOCl4(O2PCl2)] · 2 CH2Cl2 Crystalline (PPh4)2[NbOCl4(O2PCl2)] · 2 CH2Cl2 was obtained by hydrolysis of PPh4[NbSCl4] in the presence of POCl3 in CH2Cl2. Experiments to obtain the same compound from PPh4Cl, POCl3, NbCl5, and H2O yielded PPh4[NbOCl4(OH2)]. I.R. spectra of both compounds are discussed. The crystal structure determinations with X-ray diffraction data in both cases show quadratic-pyramidal NbOCl4? ions to which a molecule of either H2O or a PO2Cl2? ion is attached in trans-position to the O atom. PPh4[NbOCl4(OH2)]: tetragonal, space group P4/n, a = 1 308, c = 734 pm, Z = 2, packing as in the AsPh4[RuNCl4] type; refinement down to R = 0.046 for 681 reflexions. (PPh4)2[NbOCl4(O2PCl2)] · 2 CH2Cl2: triclinic, space group P1 , a = 1172, b = 1187, c = 2105 pm, α = 88.40, β = 83.20, γ = 71.28°, Z = 2, packing similar as in (AsPh4)2[NbOCl5] · 2 CH2Cl2; refinement to R = 0.059 for 2 502 reflexions. 相似文献
6.
Novel Routes to the Synthesis of Thiohalogeno- and Cyclothioarsenates(III). Crystal Structures of PPh4[As2SBr6] · CH3CN and PPh4[SAsS5] By reactions of (PPh4)2[As2Cl8] and (PPh4)2[As2Br8] with Na2S4 in acetonitrile (PPh4)2[As2SCl6] · CH3CN and (PPh4)2[As2SBr6] · CH3CN were obtained, respectively. Using K2S5, PPh4[As2SCl5] and PPh4[SAsS5] were the products. The latter can also be obtained from PPh4[As2SCl5] and Na2S4, while PPh4[As3S3Br4] is formed from PPh4[As2SBr5] with K2S5. Two X-ray crystal structure determinations were performed. PPh4[As2SBr6] · CH3CN: triclinic, P1 , Z = 2, a = 1200.4(7), b = 1507.3(6), c = 1594.4(8) pm, α = 81.59(2), β = 78.22(3), γ = 80.58(2)°, R = 0.096 for 2298 observed reflexions. The structure contains [As2SBr6]2? -ions in which the two Sb atoms are joined via one S and two Br atoms. PPh4[SAsS5]: triclinic, P1 , Z = 2, a = 1133.9(4), b = 1142.5(4), c = 1186.9(5) pm, α = 102.77(4), β = 107.74(3), γ = 106.65(3)°, R = 0.043 für 2677 reflexions. In the [SAsS5]? -ion an AsS5 ring in the chair conformation is present. 相似文献
7.
The Chlorooxoarsenates(III) (PPh4)2[As4O2Cl10] · 2 CH3CN and (PPh4)2[As2OCl6] · 3 CH3CN (PPh4)2[As2Cl8] can be prepared from As2O3, SOCl2 and PPh4Cl in acetonitrile. Its oxidation with chlorine yields PPh4[AsCl6]. This was also obtained directly from arsenic, chlorine and PPh4Cl, (PPh4)2[As4O2Cl10] · 2 CH3CN being a side product; the latter was obtained with high yield from AsCl3, As2O3 and PPh4Cl in acetonitrile. By addition of PPh4Cl it was converted to (PPh4)2[As2OCl6] · 3 CH3CN. According to their X-ray crystal structure analyses, both crystallize in the triclinic space group P 1. The [As4O2Cl10]2– ion can be regarded as a centrosymmetric association product of two Cl2AsOAsCl2 molecules and two Cl– ions, each Cl– ion being coordinated with all four As atoms. In the [As2OCl6]2– ion the As atoms are linked via the O atom and two Cl atoms. 相似文献
8.
Reaction of Tin Chlorides with Polysulfides. Crystal Structures of (PPh4)2[SnCl2(S6)2], (PPh4)2[Sn4Cl4S5(S3)O], and (PPh4)2[SnCl6] · S8 · 2CH3CN . The reaction of PPh4[SnCl3] with Na2S4 in acetonitrile in the presence of small amounts of water yields (PPh4)2[Sn4Cl4S5(S3)O] and minor amounts of (PPh4)2[SnCl2(S6)2], PPh4Cl · 2S8 and (PPh4)2[SnCl6]. SnCl4 is partially reduced by (PPh4)2Sx, PPh4[SnCl3] and (PPh4)2[SnCl6] · S8 · 2CH3CN being produced. According to the X-ray crystal structure determination the [Sn4Cl4S5(S3)O]2?-ion consists of an O atom that is coordinated by four Sn atoms which in turn are liked with one another by five single S atoms and one S3 group. In the [SnCl2(S6)2]2?-ion the Sn atom is octahedrally coordinated by two Cl atoms in trans arrangement and by two chelating S6 groups. Octahedral [SnCl6]2? ions and S8 molecules in the crown conformation are present in (PPh4)4[SnCl6] · S8 · 2CH3CN. 相似文献
9.
The Oxochlorotantalates (PPh4)2[Ta2OCl9]2 · 2 CH2Cl2, (PPh4)2[Ta2OCl10] · 2 CH3CN, and (K-18-crown-6)4[Ta4O6Cl12] · 12 CH2Cl2 (K-18-crown-6)4[Ta4O6Cl12] · 12 CH2Cl2 was obtained from a reaction of tantalum pentachloride, K2S5 and 18-crwon-6 in dichlormethane. According to its crystal structure analysis it is tetragonal (space group I 4 2d) and contains [Ta4O6Cl12]4– ions that have an adamantane-like Ta4O6 skeleton. Each K+ ion is coordinated by the oxygen atoms of the crown ether molecule from one side and with three Cl atoms of one [Ta4O6Cl12]4– ion from the opposite side. (PPh4)2[Ta2OCl10] · 2 CH3CN was a product from PPh4Cl and TaCl5 in acetonitrile in the presence of Na2S4. Its crystals are monoclinic (space group P21/c) and contain centrosymmetric [Ta2OCl10]2– ions having a linear Ta–O–Ta grouping with short bonds (Ta–O 189 pm). TaCl5 and H2S formed a solid substance (TaSCl3) from which a small amount of (PPh4)2[Ta2OCl9]2 · 2 CH2Cl2 was obtained by the reaction with PPh4Cl in CH2Cl2. The anions in the monoclinic crystals (space group P21/n) consist of two Ta2OCl9– units which are joined by chloro bridges; each Ta2OCl9– unit has a nearly linear Ta–O–Ta group with differing bond lengths (179 and 202 pm). The oxygen in the compounds probably was introduced by traces of water in the crown ether, acetonitrile or H2S, respectively. 相似文献
10.
Thiobromo Complexes of Arsenic and Antimony. Preparation and Crystal Structures of (PPh4)2[As2SBr6] · CH2Br2 and (PPh4)2[Sb2SBr6] · CH2Br2 (PPh4)2[As2SBr6] · CH2Br2 is formed by the reaction of As2S3, PPh4I and HI in dibromomethane. It can also be obtained, as well as (PPh4)2[Sb2SBr6] · CH2Br2, from (PPh4)2[As2Br8] and (PPh4)3[Sb2Br9], respectively, with bistrimethylsilylsulfide. The crystal structures of the title compounds were determined by X-ray diffraction. They are isotypic with (PPh4)2[As2SCl6] · C2H4Cl2. In the anions [M2SBr6]2? the M atoms (As or Sb) have a distorted octahedral coordination, the two octahedra share acommon face with one bridging S and two Br atoms; the lone electron pairs occupy the trans positions to the S atom. Crystal data: triclinic, space group P1 , Z = 2; (PPh4)2[As2SBr6] · CH2Br2, a = 119.1, b = 1203.6, c = 2067.5 pm α= 94.89, β = 97.78, γ = 112.20°, 3046 independent observed reflexions, R = 0.083; (PPh4)2[Sb2SBr6] · CH2Br2, a = 1198.9, b = 1224.3, c = 2085.5pm, α = 95.04, β = 98.48, γ = 112.13°C, 2380 reflexions, R = 0.079. 相似文献
11.
(PPh4)2[WO2Cl3]2 · 2 CH2Cl2. Synthesis, Vibrational Spectrum, and Crystal Structure Depending on the stoichiometry and the solvent, dichloromethane or 1.2-dichloroethane, WO2Cl2 reacts with tetraphenylphosphonium chloride affording (PPh4)2[WO2Cl4] or (PPh4)2[WO2Cl3]2, respectively. Both compounds are easily soluble in dichloromethane, from which they can be crystallized under incorporation of two molecules CH2Cl2 per formula unit. The crystalline compounds have been characterized by their IR and Raman spectra. According to the X-ray crystal structure analysis, (PPh4)2[WO2Cl3]2 · 2 CH2Cl2 crystallizes in the triclinic space group P1 with one formula unit per unit cell (986 independent observed reflexions, R = 0.061). Lattice constants: a = 1100.2, b = 1116.9, c = 1238.4 pm, = 69.40, = 80.46 and = 85.62°. The crystals consist of PPh4⊕ ions, centrosymmetric [WO2Cl3]22? anions and CH2Cl2 molecules. In the anions, the tungsten atoms are linked via two oxo bridges with WO distances of 184 and 252 pm. The distorted octahedral coordination around each tungsten atom is completed by three terminal chloro and one terminal oxo ligand (WO bond length 166 pm), the latter being in trans position to the longer WO bridging bond. (PPh4)2[WO2Cl4] · 2 CH2Cl2 also forms triclinic crystals that are isotypic with (PPh4)2[WOCl5] · 2 CH2Cl2 and in which the anions must have orientational disorder. 相似文献
12.
Synthesis and Crystal Structure of (PPh4)3[Re2NCl10] The rhenium(V) nitrido complex (PPh4)3[Re2NCl10] ( 1 ) is obtained from the reaction of (PPh4)[ReNCl4] with 1, 3‐dioxan‐(2‐ylmethyl)diphenyl phosphine in CH2Cl2/CH3CN in form of orange red crystals with the composition 1 ·2CH2Cl2 crystallizing in the triclinic space group P1¯ with a = 1210.7(2), b = 1232.5(1), c = 2756.3(5) pm, α = 99.68(1)°, β = 100.24(1)°, γ = 98.59(1)° and Z = 2. The crystal structure contains two symmetry independent, centrosymmetrical complex anions [Re2NCl10]3‐ with a symmetrical nitrido bridge Re=N=Re and distances Re(1) ‐ N(1) = 181.34(5) and Re(2) ‐ N(2) = 181.51(4) pm. 相似文献
13.
Bromo Complexes of Molybdenum(IV) [MoBr6]2? and [Mo2Br10]2?. Crystal Structure of (PPh3Me)2[MoBr6] · 2 CH2Br2 The bromomolybdates(IV) (PPh3Me)2[MoBr6] · 2 CH2Br2 and (PPh4)2[Mo2Br10] are obtained by reactions of molybdenum tetrabromide with PPh3MeBr and PPh4Br, respectively. They form black-brown, hydrolysis sensitive crystal powders. The crystal structure of (PPh3Me)2[MoBr6] · 2 CH2Br2 was determined by X-ray diffraction (2376 independent observed reflexions, R = 0.082). Crystal data: a = 1024, b = 1131, c = 1179 pm, α = 108.2°, β = 106.8°, γ = 99.0°, space group P1 , Z = 1. The compound consists of PPh3Me+ ions, CH2Br2 molecules and nearly octahedral [MoBr6]2? ions with MoBr bond lengths between 252.7 and 254.0 pm. 相似文献
14.
Thiochloroarsenates (III): Preparation, Vibrational Spectra, and Crystal Structures of PPh4[As2SCl5] and (PPh4)2[As2SCl6] · C2H4Cl2 PPh4[As2SCl5] can be obtained from As2S3 + PPh4Cl with HCl in CH2Cl2 or 1,2-C2H4Cl2. It reacts with a second mole of PPh4Cl to yield (PPh4)2[As2SCl6]. The latter also is formed by the reaction of As2S5 + 2 PPh4Cl with HCl, a second product being (PPh4)2[As2Cl8]. The i.r. and Raman spectra of the title compounds are reported. Their crystal structures were determined by X-ray diffraction. Crystal data: PPh4[As2SCl5], monoclinic, space group P21/n, a = 1175.8, b = 1508.0, c = 1593.4 pm, β = 96.22°, Z = 4; (PPh4)2[As2SCl6] · C2H4Cl2, triclinic, P1, a = 1166.3, b = 1188.2, c = 2044.6 pm, α = 95.47, β = 97.53, γ = 111.05°, Z = 2. Including the lone electron pairs, the coordination of the As atoms in the [As2SCl5]− ion is distorted trigonal-bipyramidal with the S, one Cl atom, and an electron pair in equatorial positions; the two bipyramids around the two As atoms share a common edge. The As atoms in the [As2SCl6]2− ion have a distorted octahedral coordination, the two octahedra share a common face; the lone electron pairs are in the trans positions to the S atom. 相似文献
15.
Thiochloro Anions of Molybdenum (IV). Crystal Structure of (NEt4)3[Mo3(μ3-S)(μ-S2)3Cl6]Cl μ CH2Cl2. Crystal Structure, Magnetic Properties, and EPR-Spectrum of (NEt4)2 [Mo2(μ-S2)(μ-Cl)2Cl6] From molybdenum pentachloride and tetraethylammonium hydrogensulfide in CH2Cl2 an insoluble product of composition (NEt4)2[Mo2S3Cl9] was obtained along with a brown solution, from which (NEt4)2[Mo2(S2)Cl8] was crystallized. The insoluble product and NEt4Cl react in CH2Cl2 to yield, among others, (NEt4)3[Mo3(S)(S2)3Cl6]Cl · CH2Cl2. The latter crystallizes in the orthorhombic space group Pnma, a = 2495.8, b = 1501.2, c = 1295.6 pm, Z = 4. According to the crystal structure determination (3070 observed reflexions, R = 0.049) the [Mo3(S)(S2)3Cl6]2? ion consists of an Mo3 triangle with Mo? Mo bonds, each side of the triangle is bridged by disulfido groups and one sulfur atom is capped over the Mo3 triangle; the single chloride ion is looseley associated to three S atoms. (NEt4)2[Mo2(S2)Cl8] also crystallizes in the space group Pnma, a = 1425.6, b = 1129.9, c = 2004.7 pm, Z = 4; structure determination with 1703 observed reflexions, R = 0.061. In the [Mo2(S2)Cl8]2? ion the Mo atoms are bridged via one disulfido group and two chlorine atoms. There is a Mo? Mo bond, but according to the magnetic properties and the EPR spectrum each Mo atom still possesses one unpaired electron. 相似文献
16.
Dieter Fenske Bernhard Czeska Christina Schumacher Roland E. Schmidt Kurt Dehnicke 《无机化学与普通化学杂志》1985,520(1):7-17
Disulfido-Bridged Halo Complexes of Molybdenum (V). Crystal Sructures of (PPh3Me)2 [Cl4Mo (μ-S2)2MoCl4]. 2 CH2Cl2 and (PPh4)2[Br4Mo(μ-S2)2MoBr4]. 3CH2Br2 . Mo(S2)Cl3 is prepared by an improved method; the i.r. spectrum is reported. In dichloro methane solution it reacts with (PPh3Me)Cl forming the complex (PPh3Me)2[Cl4Mo(μ-S2)2MoCl4] · 2 CH2Cl2. The bromo complex (PPh4)2[Br4Mo(μ-S2)2MoBr4] · 3 CH2Br2 is obtained by reaction of MoBr4 with S7NH and subsequent treatment of the reaction mixture with PPh4Br in CH2Br2 solution. Both complexes are characterized by i.r. spectra and structural analyses by X-ray methods. (PPh3Me)2[Cl4Mo(μ-S2)2MoCl4] · 2 CH2Cl2 crystallizes monoclinic in the space group P21/c with two formula units per unit cell (5268 observed independent reflexions, R = 4.0%). The lattice dimensions are: a = 1097 pm, b = 1510 pm, c = 1591 pm, β = 104.4°. (PPh4)2[Br4Mo(μ-S2)2MoBr4] · 3 CH2Br2 crystallizes triclinic in the space group P&1macr; with two formula units per unit cell and the lattice constants a = 1328 pm, b = 1573 pm, c = 1719 pm, α = 95.8°, β = 96.3°, γ = 74.1°. Both compounds are of ionical structure with PPh3Me⊕ and PPh4⊕ cations, respectively, and anions [X4MO(μ-S2)2MoX4]2? very similar to each other. The molybdenum atoms are bridged by two disulfido ligands and are bonded directly with a bond length of 286 pm. The terminal halogen atoms add up to coordination number nine at the molybdenum. 相似文献
17.
Syntheses and Crystal Structures of the Thiochloroantimonates(III) PPh4[Sb2SCl5] and (PPh4)2[Sb2SCl6]. CH3CN (PPh4)2Sb3Cl11, obtained from Sb2S3, PPh4Cl and HCl, reacts with Na2S4 in acetonitrile forming PPh4[Sb2SCl5]. From this and Na2S4 or from (PPh4)2[Sb2Cl8] and Na2S4 or K2S5 in acetonitrile (PPh4)2[Sb2SCl6] · CH3CN is obtained. Data obtained from the X-ray crystal structure determinations are: PPh4[Sb2SCl5], monoclinic, space group P21/c, a = 1002.9(3), b = 1705.6(5), c = 1653.7(5) pm, β = 99.12(2)°, Z = 4, R = 0.068 for 1283 reflextions; (PPh4)2[Sb2SCl6] · CH3CN, triclinic, space group P1 , a = 1287.8(7), b = 1343.6(9), c = 1696.5(9) pm, α = 69.82(5), β = 85.08(4), γ = 71.54(6)°, Z = 2, R = 0.059 for 6409 reflexions. In every anion two Sb atoms are linked via one sulfur and one ore two chloro atoms, respectively. Paris of [SbSCl5]? ions are associated via Sb …? S and Sb …? Cl contacts forming dimer units. In both compounds every Sb atom has a distorted octahedral coordination when the lone electron pair is included in the counting. 相似文献
18.
C. Lau A. Dietrich M. Plate P. Dierkes B. Neumüller S. Wocadlo W. Massa K. Harms K. Dehnicke 《无机化学与普通化学杂志》2003,629(3):473-478
Crystal Structures of the Hexachlorometalates NH4[SbCl6], NH4[WCl6], [K(18‐crown‐6)(CH2Cl2)]2[WCl6]·6CH2Cl2 and (PPh4)2[WCl6]·4CH3CN The crystal structures of the title compounds were determined by single crystal X‐ray methods. NH4[SbCl6] and NH4[WCl6] crystallize isotypically in the space group C2/c with four formula units per unit cell. The NH4+ ions occupy a twofold crystallographic axis, whereas the metal atoms of the [MCl6]— ions occupy a centre of inversion. There exist weak interionic hydrogen bridges. [K(18‐crown‐6)(CH2Cl2)]2[WCl6]·6CH2Cl2 crystallizes in the orthorhombic space group R3¯/m with Z = 3. The compound forms centrosymmetric ion triples, in which the potassium ions are coordinated with a WCl3 face each. In trans‐position to it the chlorine atom of a CH2Cl2 molecule is coordinated so that, together with the oxygen atoms of the crown ether, coordination number 10 is achieved. (PPh4)2[WCl6]·4CH3CN crystallizes in the monoclinic space group P21/c with Z = 4. This compound, too, forms centrosymmetric ion triples, in which in addition the acetonitrile molecules are connected with the [WCl6]2— ion via weak C—H···Cl contacts. 相似文献
19.
A. Müller A. Hildebrand E. Krickemeyer D. Slter H. Bgge A. Armatage 《无机化学与普通化学杂志》1992,614(8):115-120
(PPh4)[(ReO2S2)CuI] and (NEt4)2[ReOS3)Cu3Cl4]: Fixation of the up to now not Isolated Ions [ReO2S2]? and [ReOS3]? Utilizing the Stability of the CuS2(Re) and Cu3S3(Re) Fragments (PPh4)[(ReO2S2)CuI] ( 1 ) and (NEt4)2[ReOS3)Cu3Cl4] ( 2 ) containing the up to now not isolated oxothioperrhenate ions [ReO2S2]? and [ReOS3]? as ligands, have been prepared by the reaction of (NEt4)[ReS4] with PPh3 and CuI in acetone in the presence of (PPh4)I (( 1 )) or with CuCl in CH2Cl2 in the presence of (NEt4)Cl (( 2 )), respectively. 1 and 2 have been characterized by X-ray structure analysis, elemental analysis and spectroscopic studies (IR, UV/Vis). The electronic spectra show bands which can approximately be assigned to interesting low-energy charge-transfer-transitions of the type d(Cu) → d(Re). For crystal data see Inhaltsübersicht. 相似文献
20.
Claus Friebel Klaus-Dieter Scherfise Wolfgang Willing Ulrich Müller Kurt Dehnicke 《无机化学与普通化学杂志》1987,546(3):21-32
E.P.R. and Ligand Field Spectra of Chlorovanadates(IV). The Crystal Structure of PPh4[VxTi2–xCl9] (x = 0.15) Black, moisture-sensitive crystals of PPh4[VxTi2–xCl9] (x = 0.15) are formed by the reaction of titanium tetrachloride and PPh4[VCl5] in dichloromethane. Its EPR and ligand field spectra as well as those of PPh4[VCl5] and (PPh4)2[V2Cl9][VCl5] · CH2Cl2 were recorded. In the mixed crystals of PPh4[V0.15Ti1.85Cl9], the existence of [VTiCl9]? ions consisting of trigonally distorted, face sharing octahedra can be proven by the spectra. The spectra of the compounds with [VCl5]? ions can only be explained when a significant Jahn-Teller distortion of the trigonal bipyramids is assumed; this distortion was not detected in the crystal structure determination of (PPh4)2[V2Cl9][VCl5] · CH2Cl2. The crystal structure of PPh4[V0.15Ti1.85Cl9] was determined by X-ray diffraction (2588 independent observed reflexions, R = 0.044). Crystal data: triclinic, space group P1 , a = 1090.4, b = 1217.4, c = 1287.7 pm, α = 73.19°, β = 69.87°, γ = 82.15°, Z = 2. The compound consists of PPh4⊕ and [V0.15Ti1.85Cl9]? ions. In the anions, Ti and V atoms are distributed statistically in the two face sharing octahedra. 相似文献