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1.
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
2.
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
3.
Crystal Structures of (Ph4P)2[HfCl6]·2CH2Cl2 and (Ph4P)2[Hf2Cl10]·CH2Cl2 Colourless single crystals of (Ph4P)2[HfCl6]·2CH2Cl2 ( 1 ) and (Ph4P)2[Hf2Cl10]·CH2Cl2 ( 2 ) were obtained from hafniumtetrachloride and tetraphenylphosphonium chloride in dichloromethane solution, using the corresponding stoichiometry of the educts. Both compounds were characterized by X‐ray structure determinations. 1 : Space group P1¯, Z = 1, lattice dimensions at 193 K: a = 1018.3(1), b = 1121.0(1), c = 1240.1(1) pm, α = 70.55(1)°, β = 81.38(1)°, γ = 80.02(1)°, R1 = 0.0374. 2 : Space group P1¯, Z = 1, lattice dimensions at 193 K: a = 1124.4(1), b = 1141.9(1), c = 1281.4(1) pm, α = 63.80(1)°, β = 68.15(1)°, γ = 86.33(1)°, R1 = 0.0208. 相似文献
4.
Cyclothiazeno Complexes of Molybdenum(V), Molybdenum(VI), and Tungsten(VI). Crystal Structure of (PPh4)2[MoCl3(N3S2)]2 · 2 CH2Cl2 . From excess trithiazylchloride and molybdenum or tungsten hexacarbonyl, respectively, the cyclothiazeno complexes [MCl3(N3S2)]2(S2N2) are obtained. They possess metal atoms linked via a planar S2N2 ring. The corresponding bromo compounds [MBr3(N3S2)]2(S2N2) can be obtained in liquid bromine from S4N4 and MoBr4 or WBr6, respectively, or from S4N4 with the corresponding metal hexacarbonyls in the presence of bromine. Thermolysis of [WBr3(N3S2)]2(S2N2) yields [WBr3(N3S2)]2 which is dimerized via nitrogen bridges. When [MoCl3(N3S2)]2(S2N2) reacts with tetraphenylphosphonium chloride in dichloromethane, the S2N2 acts as reducing agent, and the paramagnetic molybdenum(V) complex (PPh4)2[MoCl3(N3S2)]2 · 2 CH2Cl2 is obtained (μeff = 1.2 B.M.). The i.r. spectra are reported. The crystal structure of (PPh4)2[MoCl3(N3S2)]2 · 2 CH2Cl2 was determined by X-ray diffraction (2524 independent reflexions, R = 0.052). It crystallizes in the space group P1 with the lattice con- stants a = 943.9, b = 1209.6, c = 1469.2 pm, α = 69.27, β = 72.20 and γ = 82.08°, Z = 1. There are tetraphenylphosphonium cations and centrosymmetric, dimeric anions [MoCl3(N3S2)]22?. The molybdenum atoms are part of six-membered cyclothiazeno rings MoN3S2 with MoN bond lengths of 177 and 197 pm; the N atom with the longer MoN bond is linked to the second Mo atom, so that a planar Mo2N2 ring results; this ring is nearly coplanar with the two MoN3S2 rings. Furthermore, each molybdenum atom is linked with three chlorine atoms with MoCl bond lengths of 240–242 pm, so that the Mo atoms possms a distorted octahedral coordination. 相似文献
5.
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
6.
Diiodoacetylene Complexes of Tungsten(IV). Crystal Structure of PPh4[WCl5(C2I2)] · 0.5 CH2Cl2 Tungsten hexachloride and diiodoacetylene react in CCl4 solution forming [WCl4(I? C?C? I)]2 which has a dimer structure with chloro bridges. In CH2Cl2, it reacts with PPh4Cl yielding PPh4[WCl5(I? C?C? I)] · 0.5 CH2Cl2. In both compounds the C2I2 ligands attain a marked increase in thermal stability by their side-one coordination to the tungsten atoms. The crystal structure of the PPh4⊕ salt was determined with X-ray diffraction data (3879 observed reflexions, R = 0.050). PPh4[WCl5(C2I2)] · 0.5 CH2Cl2 crystallizes in the space group P21/n with 8 formula units per unit cell. The lattice constants are a = 1723.0, b = 1681.2, c = 2214.6 pm and β = 94.38°. There are two crystallographically independent [WCl5(C2I2)]? ions which differ only slightly from one another. The C2I2 ligand has a staggered arrangement relative to the W? Cl groups, with C? C bond lengths of 127 pm. The infrared spectra are discussed. 相似文献
7.
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
8.
Crystal Structures of [Ph3PMe]Cl·CH2Cl2, [Ph4P]NO3·CH2Cl2, and [Ph4P]2[SiF6]·CH2Cl2 The crystal structures of the title compounds are determined by X‐ray diffraction. In all cases, the included dichloromethane molecules as well as the phosphonium cations are involved to form hydrogen bridges with the anions. [Ph3PMe]Cl·CH2Cl2 ( 1 ): Space group , Z = 2, lattice dimensions at 100 K: a = 890.3(1), b = 988.0(1), c = 1162.5(1) pm, α = 106.57(1)°, β = 91.79(1)°, γ = 92.60(1)°, R1 = 0.0253. [Ph4P]NO3·CH2Cl2 ( 2 ): Space group P21/n, Z = 4, lattice dimensions at 193 K: a = 1057.0(1), b = 1666.0(1), c = 1358.9(1) pm, β = 100.10(1)°, R1 = 0.0359. [Ph4P]2[SiF6]·CH2Cl2 ( 3 ): Space group , Z = 2, lattice dimensions at 193 K: a = 1063.9(1), b = 1233.1(1), c = 1782.5(2) pm, α = 76.88(1)°, β = 83.46(1)°, γ = 72.29(1)°, R1 = 0.0332. 相似文献
9.
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
10.
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
11.
Nitrosyl Complexes of Molybdenum (+II). Crystal Structures of [Mo(NO)Cl3 · POCl3]2 and [AsPh4]2[Mo(NO)Cl5] · 2 CH2Cl2 Solutions of MoCl5 in POCl3 react with NOCl forming the nitrosyl compound Mo(NO)Cl3 · 2POCl3 ( I ), which in CH2Cl2 cleaves off one solvate molecule, yielding the dimeric complex [Mo(NO)Cl3 · POCl3]2 ( II ). Reaction with AsPh4Cl in dichloro methane leads to the nitrosyl complexes AsPh4[Mo(NO)Cl4] · CH2Cl2 ( III ) and [AsPh4]2[Mo(NO)Cl5] · 2CH2Cl2 ( IV ), respectively. The i.r. spectra are recorded and assigned. [Mo(NO)Cl3 · POCl3]2 crystallizes monoclinic in the space group P21/c with two dimeric units per unit cell. The crystal structure was determined by X-ray diffraction methods (R = 0.040; 1391 observed, independent reflexions). Complex II is linked by chlorine bridges, forming a dimeric, centrosymmetric molecule of symmetry Ci. The N? O bond of the nitrosyl ligand is extremely short (108 pm), the Mo? N bond (181 pm) corresponds to a double bond. In trans position to the NO ligand, which is coordinated in linear array, there is the O atom of the solvate molecule POCl3. [AsPh4]2[Mo(NO)Cl5] · 2 CH2Cl2 crystallizes triclinic in the space group P1 with two units per unit cell (R = 0.039; 1967 observed, independent reflexions). The molybdenum atom is coordinated octahedrally by five Cl ligands and a nitrosyl group, as well coordinated in linear array (Mo? N? O 174°). The nitrosyl ligand exerts a significant trans-effect (r Mo? Cl(trans) = 247 pm, r MoCl4(eq)(average) = 239 pm). 相似文献
12.
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
13.
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
14.
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
15.
(PPh4)2[V2Cl9][VCl5] · CH2Cl2. Synthesis, I.R. Spectrum, and Crystal Structure The title compound was obtained by addition of CCl4 to a solution of PPh4Cl and excess VCl4 in CH2Cl2. It forms black crystals which are light and moisture sensitive. The i.r. spectrum is reported. The crystal structure was determined by X-ray diffraction (3044 independent reflexions, R = 0.063). Crystal data: triclinic, space group P1 , Z = 2, a = 1186, b 1325, c = 1995 pm, α 97.5, β 105.6°, γ 93.4°. The structure consists of PPh4+ cations, V2Cl9? and VCl5? anions and CH2Cl2 molecules. The V2Cl9? ions consist of face-sharing octahedra with a long V…?V distance of 333 pm; the VCl5? ions form nearly ideal trigonal bipyramids with V? Cl bonds of 228 pm (axial) and 218 pm (equatorial). Both anions deviate only marginally from D3h symmetry. Half of the cations is arranged to (PPh4+)2 pairs about inversion centers. 相似文献
16.
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
17.
Reaction of Trichloronitro Methane with Iron Carbonyls. Crystal Structure of (PPh4)2[Fe2OCl6] · 2 CH2Cl2 Trichloronitro methane reacts with Fe2(CO)9 or Fe3(CO)12 forming NO[FeOCl2] which is composed of Nitrosyl ions and polymeric [FeOCl2]?. The reaction of NO[FeOCl2] with POCl3 affords Fe(O2PCl2)3; with tetraphenyl phosphoniumchloride it forms the complex (PPh4)2[Fe2OCl6] which is soluble in CH2Cl2. The oxochloro ferrates are characterized by the aid of 57Fe-Mössbauer spectra and by i.r. spectra. A single crystal of (PPh4)2[Fe2OCl6] · 2 CH2Cl2 was used to carry out a structural investigation by means of X-ray diffraction data (space group P1 , Z = 1, a = 1157.2(2), b = 1363.8(3), c = 1140.3(2) pm, α = 109.22(1)°, β = 95.23(1)°, γ = 67.24(2)°, R = 0.052 for 3814 reflexions with F0 > 3σ). The [Cl3Fe? O? FeCl3]2?-anion is found to have a centre of symmetry and thus, in accordance with the i.r. spectra, contains a linear bridge. High thermal parameters of the bridging oxygen atom and the chlorine ligands, however, allow interpretations as orientation disorder of slightly bent anions. 相似文献
18.
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
19.
Preparation and Vibrational Spectra of Dichloro and Dibromodithiophosphate. Crystal Structures of [PPh3Me][PS2Cl2] and [PPh4][PS2Br2] Dichloro and dibromodithiophosphates [Cat+][PS2X2?] with a large organic cation can be obtained from P4S10, CatX and HX in CH2Cl2 (Cat+ = PPh4+, PPh3Me+; X = Cl, Br). The vibrational spectra (i.r. and Raman) of the [PS2X2]? ions are reported and discussed; force constants were calculated. The crystal structures of [PPh3Me][PS2Cl2] and [PPh4][PS2Br2] were determined and refined with X-ray diffraction data. In both cases, simple anions [PS2X2]? are present. [PPh3Me][PS2Cl2]: orthorhombic, space group P212121, a = 1089, b = 1334, c = 1476 pm, Z = 4, refinement to a residual index R = 0.046 for 1116 reflexions; the structure is isotopic with [PPh3Me][VO2Cl2]. [PPh4][PS2Br2]: tetragonal space group I4 , a = 1301, c = 721 pm, Z = 2, refinement to R = 0.065 for 357 reflexions; the structure is isotypic with [AsPh4][FeCl4] with [PS2Br2]? ions occupying positions of 4 -symmetry with statistical orientation (statistical superposition of Br and S positions). 相似文献
20.
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