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1.
The Crystal Structures of PPh4[MCl5(NCMe)] · MeCN (M = Ti, Zr), two Modifications of PPh4[TiCl5(NCMe)] and of cis ‐TiCl4(NCMe)2 · MeCN The title compounds were obtained by reactions of TiCl4 or ZrCl4, respectively, with PPh4Cl and acetonitrile in the presence of S2Cl2. PPh4[TiCl5(NCMe)] · MeCN is unstable and emanates the incorporated acetonitrile. PPh4[TiCl5(NCMe)] forms the two modifications aP114 and mP228, the latter being more stable. The crystal structures were determined by X‐ray diffraction. Triclinic PPh4[TiCl5(NCMe)]‐(aP114) crystallizes in a distorted variety at the tetragonal AsPh4[RuNCl4] type, i. e. with PPh4+ ions that are piled to columns in the c direction; the [TiCl5(NCMe)]– ions are tilted vs. this direction and thus cause the symmetry reduction from P4/n to P1. PPh4[TiCl5(NCMe)] · MeCN and PPh4[ZrCl5(NCMe)] · MeCN also have the same packing principle as in AsPh4[RuNCl4] with a symmetry reduction from P4/n to P1121/n and a doubled c axis. Instead, PPh4[TiCl5(NCMe)]‐(mP228) has a packing with (PPh4+)2 pairs. Orthorhombic TiCl4(NCMe)2 · MeCN contains molecules having two acetonitrile ligands attached to the Ti atom in a cis configuration. 相似文献
2.
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
3.
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
4.
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
5.
Synthesis and Crystal Structure of (PPh4)2[Mo2(S2)2Cl8] · 2 CH3CN and its Topotactic Transformation to (PPh4)2[Mo2(S2)2Cl8] MoS2Cl3 was prepared from molybdenum and S2Cl2 at 200 °C. Its reaction with PPh4Cl in acetonitrile yielded (PPh4)2[Mo2(S2)2Cl8] · 2 CH3CN. In vacuum or upon warming, it loses the acetronitrile without degradation of the crystals. According to the X-ray crystal structure determinations both compounds, with and without acetonitrile, are triclinic. They contain the same [Cl4Mo(μ-S2)2MoCl4]2– ions, in which the Mo atoms are joined by two disulfido groups and an Mo–Mo bond. Details of the crystal packings and their topotactic transformation are given. 相似文献
6.
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
7.
The Orientation of the Re2Cl82– Ions in (PPh4)2[Re2Cl8] · 2 L (L = Acetonitrile, Dichloromethane) (PPh4)2[Re2Cl8] · 2 MeCN was obtained in small yields from PPh4Cl and ReCl5 in the presence of Na2S4 or K2S5 in acetontrile. Its crystal structure was determined by X‐ray diffraction. The crystals are nearly isotypic with those of (PPh4)2[Re2Cl8] · 2 CH2Cl2. The PPh4+ ions, the solvent molecules, and the chlorine atoms occupy nearly identical positions in both triclinic structures. Nevertheless, 98% of the Re≡Re groups are differently oriented within the slightly elongated Cl8 cubes surrounding them. The space requirement of the elongated cubes seems to be more important for the orientation than electrostatic forces. The PPh4+ ions form (PPh4+)2 pairs around inversion centers. 相似文献
8.
Cyclic Polyselenidoarsenates(III) and Polyselenidoantimonates(III): PPh4[Se5AsSe], PPh4[AsSe6–xS x ], (PPh4)2[As2Se6] · 2 CH3CN, and (PPh4)2[Se6SbSe]2 In acetonitrile, AsCl3 and sodiumphenolate formed Cl2AsOPh which then was reacted with PPh4Se5 and finally with Na2Se to yield PPh4[Se5AsSe]. With Na2S instead of Na2Se, PPh4[AsSe6–xSx] was obtained; the sulfur contents increased with increasing reaction temperature and time (x = 0.21 to 1.09). With PPh4Se2 instead of PPh4Se5, (PPh4)2[1,4-As2Se6] · 2 CH3CN and PPh4[Se5AsSe] were the products. With SbCl3 instead of AsCl3, (PPh4)2[Se6SbSe]2 formed. PPh4[Se5AsSe] can also be produced from As2Se3, PPh4Br, Na2Se and selenium in acetonitrile. The crystal structure of PPh4[SeAsSe5] is isotypic with PPh4[S5AsS] (X-ray structure analysis with 2414 observed reflexions, R = 0.038). The Se5AsSe– ion consists of a six-membered AsSe5 ring in chair conformation, and the As atom has an additional terminal Se atom. The compounds PPh4[AsSe6–xSx] have the same crystal structures, with sulfur atoms taking all selenium positions at random, but with a preference for the terminal position. The anion in (PPh4)2[As2Se6] · 2 CH3CN also has a six-membered ring structure in chair conformation, with two arsenic atoms in positions 1 and 4. The centrosymmetric anion in (PPh4)2[Se6SbSe]2 consists of a central Sb2Se2 ring, and a Se6 ligand is bonded in a chelating manner to each Sb atom (X-ray structure analysis with 2669 observed reflexions, R = 0.099). 77Se-NMR spectra are reported. 相似文献
9.
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
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.
Synthesis and Crystal Structures of (PPh4)2[In(S4)(S6)Cl] and (PPh4)2[In(S4)Cl3] InCl and PPh4Cl yield (PPh4)2[In2Cl6] in acetonitrile. This reacts with Na2S4 in presence of PPh4Cl, forming (PPh4)2[In(S4)(S6)Cl]. Its crystal structure was determined by X-ray diffraction (R = 0.075, 2 282 observed reflexions). It is isotypic with (PPh4)2[In(S4)(S6)Br] and contains anions with trigonal-bipyramidal coordination of In, Cl occupying an axial position, and the S4 and S6 groups being bonded in a chelate manner. The reaction of (PPh4)2[In2Cl6] and sulfur in acetonitrile yielded (PPh4)2[InCl5] and (PPh4)2[In(S4)Cl3]. The crystal structure analysis of the latter (R = 0.072, 4 080 reflexions) revealed an anion with distorted trigonal-bipyramidal coordination of In, the S4 group occupying one axial and one equatorial position; the S4 group shows positional disorder. 相似文献
12.
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
13.
Synthesis and Crystal Structures of (PPh4)2[TeS3] · 2 CH3CN and (PPh4)2[Te(S5)2] (PPh4)2[TeS3] · 2 CH3CN was obtained by the reaction of PPh4Cl, Na2S4 and Te in acetonitrile. With sulfur it reacts yielding (PPh4)2[Te(S5)2]. The crystal structures of both products were determined by X-ray diffraction. (PPh4)2[TeS3] · 2 CH3CN: triclinic, space group P1 , Z = 2, R = 0.041 for 4 629 reflexions; it contains trigonal-pyramidal [TeS3]2? ions with an average Te? S bond length of 233 pm. (PPh3)2[Te(S5)2]: monoclinic, P21/n, Z = 2, R = 0.037 for 2 341 reflexions. In the [Te(S5)2]2? ion the tellurium atom has a nearly square coordination by four S atoms. Along with the Te atoms each of the two S5 groups forms a ring with chair conformation. 相似文献
14.
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
15.
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
16.
Crystal Structures of [ReCl4(PhC?CPh)]2 · 2 CH2Cl2 and PPh4[ReOCl4] Single crystals of [ReCl4(PhC?CPh)]2 · 2 CH2Cl2 were obtained by chilling dilute solutions of the solvate [ReCl4(PhC?CPh)POCl3] in CH2Cl2. PPh4[ReOCl4] was formed by the reaction of the diphenyl acetylene complex [ReCl5(PhC?CPh)] with PPh4Cl · H2O in CH2Cl2 solution. [ReCl4(PhC?CPh)]2 · 2 CH2Cl2: space group P21/c, Z = 2, 2244 observed independent reflexions, R = 0.038. Lattice parameters (19°C): a = 987.2 pm; b = 1533.9 pm; c = 1193.8 pm; β = 90.17° The compound forms centrosymmetrical dimeric molecules with ReCl2Re bridges with Re? Cl distances of 241.2 and 267.6 pm. The longer Re? Cl bond is situated in trans-position to the equatorial, side-on coordinated diphenyl acetylene ligand with mean Re? C distances of 200 pm. PPh4[ReOCl4]: space group P4/n, Z = 2, 1487 observed, independent reflexions, R = 0.047. Lattice parameters (19°C): a = b = 1272.0 pm; c = 771.3 pm. The compound crystallizes in the AsPh4[RuNCl4] type; it consists of [ReOCl4]? anions and PPh4+ cations. The anions are tetragonal with C4v symmetry and bond lengths Re? O = 165.4 pm and Re? Cl = 232.6 pm; the bond angle OReCl is 106.7°. 相似文献
17.
Thiocomplexes of Molybdenum. Crystal Structure of a Mixed Single Crystal (PPh3Me)2[Mo2Br6(NO)4]/(PPh3Me)2[Mo2Br6S2(NO)2] The reactions of (PPh4)2MoS4 with MoBr4 and MoBr2(NO)2 resp. lead to the binuclear complexes (PPh4)2[S2MoS2MoBr3(SMe2)] and (PPh4)[S2MoS2MoBr2(NO)2], in which the molybdenum atoms are linked by sulfido bridges. The preparation of (PPh3Me)2S6 and (AsPh4)2S7 from Na2S4 and PPh3MeBr, and AsPh4Cl, respectively, in ethanol solution is described. Disulfido briges are a feature of (AsPh4)2[Mo2Br6(S2)2(SMe2)2], which is obtained from MoBr4(SMe2)2 and (AsPh4)2S7. Mixed single crystals containing 2/3 (PPh3Me)2[Mo2Br6(NO)4] and 1/3 (PPh3Me)2[Mo2Br6S2(NO)2] are formed in the reaction of MoBr2(NO)2 with (PPh3Me)2S6, as shown by X-ray single crystal structure determination. The compound crystallizes monoclinic in the space group C2/c (Internat. Tab. Nr. 15) with four formula units per unit cell (2351 independent observed reflexions, Rw = 0.037). The cell parameters are a = 1603 pm, b = 1549 pm, c = 1863 pm; β = 92.2°. The complexes consist of PPh3Me⊕ cations and the dimeric anions [Mo2Br6(NO)4]2? and [Mo2Br6S2(NO)2]2? which occur in the ratio 2:1. In these the molybdenum atoms are connected via MoBr2Mo bridges of slightly different lengths (Mo? Br 265 pm and 267 pm) forming a controsymmetric double octahedron. All molybdenum atoms have two terminal bromo ligands with Mo? Br bond lengths of 258 pm and 260 pm; in the [Mo2Br6(NO)4]2? ion each molybdenum has two covalently bonded nitrosyl groups on cis-position with Mo? N bond lengths of 183 pm. In the [Mo2Br6S2(NO)2]2? ion one of the two nitrosyl groups at each metal atom is substituted by a terminal sulfido ligand with a Mo? S bond length of 240 pm. The i.r. spectra are reported. 相似文献
18.
PPh4[As3S3Cl4] and PPh4[As3S3Br4] When As2S3 reacts with PPh4X and HX in 1,2-C2H4X2 (X = Cl, Br), the title compounds are obtained as minor products; the main products are PPh4[As2SX5]. Their crystal structures were determined by X-ray diffraction. PPh4[As3S3Cl4]: a = 1187.7, b = 1090.9, c = 1191.8 pm, α = 82.91, β = 88,93, γ = 88.52°; twins with twin plane (100); R = 0.109 for 1618 observed reflexions of one twin crystal. PPh4[As3S3Br4]: a = 1119.7, b = 1177.5, c = 1204.1 pm, α = 81.59, β = 85.88, γ = 88.25°; R = 0.061 for 2331 observed reflexions. Both compounds crystallize in the space group P1 , Z = 2, and can be considered to be isotypic. Nevertheless, PPh4[As3S3Br4] does not form twins as PPh4[As3S3Cl4]. The crystals consist of PPh4+ and [As3S3X4]? ions. In the anions, the three As atoms of an As3S3 ring in the chair conformation are commonly joined to an X atom and each As atom is bonded to one further terminal X atom. Cations and anions are packed in alternating layers. 相似文献
19.
Formation of PPh4[WOCl4 · THF] and PPh4Cl · 4As4S3 from W(CO)6 and PPh4[As2SCl5] and their Crystal Structures When W(CO)6 and PPh4[As2SCl5] are irradiated with UV light in tetrahydrofurane, PPh4[WOCl4 · THF], PPh4 Cl· 4As4S3 and PPh4[Cl2H] are obtained. X-ray crystal structure determinations were performed. PPh4[WOCl4 · THF], monoclinic, space group P21/c, Z = 4, a = 1207.5(2), b = 1003.7(2), c = 2642.0(5) pm, β = 114.71(1)°, R = 0.049% for 2824 reflexions; PPh4+ and [WOCl4. THF]? ions are present, the WOCl4 group having the shape of a tetragonal Pyramid with a short W ? O bond (169 pm) and the THF molecule being weakly associated (W? O 236 pm). PPh4Cl · 4AsS3, tetragonal, I41/a, Z = 4, a = 1742.3(3), c = 1664.5(4) pm, R = 0.066% for 1350 reflexions; it consists of separate PPh4+ and Cl? ions and As4S3 molecules. 相似文献
20.
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