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1.
Benzodithiazolium Chlorooxomolybdate(V): Preparation and Crystal Structure of (C6H4NS2)[MoOCl4] and (C6H4NS2)[MoOCl4·H2O] Red benzo‐1,3,2‐dithiazolium‐chlorooxomolybdate(V) (C6H4NS2)[MoOCl4] ( 1 ) was obtained by the reaction of benzo‐1,3,2‐dithiazoliumchloride and molybdenum(V)chloride oxide in dichlormethane under solvothermal conditions at 70 °C. In the presence of small amounts of concentrated hydrochloric acid the yellow compound (C6H4NS2)[MoOCl4·H2O] ( 2 ) is formed under analogue conditions. Both crystal structures ( 1 : monoclinic, C2/c, a = 799.2(1), b = 2091.5(2), c = 791.5(1) pm, β = 102.2(1)°, Z = 4; 2 : monoclinic, Cc, a = 953.7(1), b = 2468.9(3), c = 608.1(1) pm, β = 112.5(1)°, Z = 4) contain the planar benzo‐1,3,2‐dithiazolium ion. Within the structure of 1 the molybdenum atoms in the [MoOCl4]? ions are coordinated in a square pyramidal fashion with an oxygen atom in apical position and the basal plane formed by chlorine atoms. The nitrogen atom of the cation, which bears a partial negativ charge, expands the coordination to a distorted octahedron. The structure therefore is made up of ionic pairs {(C6H4NS2)+ [MoOCl4]?} with a Mo–N distance of 266 pm. 1 is paramagnetic with a magnetic moment of 1.7 B.M. corresponding to one unpaired electron per formula unit. In the structure of 2 the coordination of the [MoOCl4]? ion is expanded by the oxygen atom of a coordinating water molecule. The structure is dominated by hydrogen bonds between the oxygen atoms of the [MoOCl4·H2O]? ions which cause the concatenation of the anions to infinite chains. 相似文献
2.
On Thallium(I)-oxochloromolybdates: Synthesis and Crystal Structures of Tl[MoOCl4(NCCH3)], Tl[Mo2O2Cl7], and Tl2[Mo4O4Cl14] and the Structure of Tl2[MoCl6] Black crystals of Tl2[MoCl6] are formed in the reaction of TlCl with MoOCl3 in a sealed evacuated glass ampoule at 350 °C. The crystal structure analysis shows that Tl2[MoCl6] (cubic, Fm 3¯m, a = 986.35(7) pm) adopts the K2[PtCl6] structure with a Mo–Cl bond length of 236.6 pm. Tl[MoOCl4(NCCH3)] was obtained by the reaction of TlCl with MoOCl3 in acetonitrile in form of yellow, moisture sensitive crystals. The structure (orthorhombic, Cmcm, a = 746.0(1), b = 1463.8(3), c = 857.3(2) pm) is built of Tl+ cations and octahedral [MoOCl4(NCCH3)]– anions in which the acetonitrile ligand is bound in trans position to the oxygen. The reaction of TlCl and MoOCl3 in dichloromethane yields Tl[Mo2O2Cl7] and Tl2[Mo4O4Cl14] as green moisture sensitive crystals. The structure of Tl[Mo2O2Cl7] (orthorhombic, Pmmn, a = 694.3(1), b = 951.9(2), c = 904.7(1) pm) consists of Tl+ cations and dinuclear [Mo2O2Cl7]– anions, with two equidistant chlorine bridges of 248.2 and one longer chlorine bridge of 265.7 pm. The oxygen atoms are located in the trans positions of the longer chloro bridge. The structure of Tl2[Mo4O4Cl14] (triclinic, P1¯, a = 692.8(1), b = 919.6(1), c = 998.9(1) pm, α = 104.94(1)°, β = 90.31(1)°, γ = 108.14(1)°) is build of Tl+ cations and [Mo4O4Cl14]2– anions which form tetramers of distorted octahedral, edgesharing (MoOCl5) units with chlorine atoms in the bridging positions. The oxygen atoms are located in the trans positions of the longest chlorine bridges. 相似文献
3.
Polycationic Hg–As Frameworks with Trapped Anions. II Synthesis, Crystal Structure, and Magnetism of (Hg6As4)[MoCl6]Cl, (Hg6As4)[TiCl6]Cl, and (Hg6As4)[TiBr6]Br (Hg6As4)[MoCl6]Cl is obtained by reaction of Hg2Cl2, Hg, As, and MoCl4 in closed, evacuated glass ampoules in a temperature gradient 450 → 400 °C in form of dark red cubelike crystals. (Hg6As4)[TiCl6]Cl and (Hg6As4)[TiBr6]Br are also formed in closed, evacuated ampoules from Hg2X2 (X = Cl, Br), Hg, As, and Ti metal at 275 °C and 245 °C in form of dark green and black crystals, respectively. All three compounds are air and light sensitive. They crystallize isotypically (cubic, Pa 3, a = 1207.8(4) pm for (Hg6As4)[MoCl6]Cl, a = 1209.4(3) pm for (Hg6As4)[TiCl6]Cl, a = 1230.9(3) pm for (Hg6As4)[TiBr6]Br, Z = 4). The structures consist of a three‐dimensionally connected Hg–As framework which is made up of As2 groups (As–As distance averaged 242 pm) each connected via six Hg atoms to six neighbouring As2 groups. There are two cavities of different size in the polycationic framework. The bigger cavity is filled with [MoCl6]3–, [TiCl6]3–, and [TiBr6]3– ions of nearly ideal octahedral shape, the smaller cavity with discrete halide ions. The magnetic properties of the two Ti containing compounds are in accordance with a d1 paramagnetism. The temperature dependence and the magnitude of the magnetic moment can be interpreted with consideration of the spin‐orbit coupling. The so far known representatives of this structure type can be characterised by the ionic formula (Hg6Y4)4+[MX6]3–X– (Y = As, Sb; M = Sb3+, Bi3+, Mo3+, Ti3+; X = Cl, Br). 相似文献
4.
Synthesis and Structure of Mo2NCl7 The reaction of VN with MoCl5 at 175 °C in a sealed glass ampoule yields the molybdenum(V) nitride chloride Mo2NCl7 in form of air sensitive black crystals with the triclinic space group P1¯ and a = 905.7(8); b = 975.4((6); c = 1283.4(8) pm, α = 103.13(4)°; β = 109.83(5)° und γ = 98.58(5)°. The crystal structure is built up from dinuclear units [Mo2N2Cl7]3— and [Mo2Cl7]3+, which are connected by asymmetric nitrido bridges to form endless chains. Within both dinuclear units the Mo atoms are bridged by three Cl atoms resulting in a Mo‐Mo distance of 349.2(3) pm in the unit [Mo2N2Cl7]3—. In case of [Mo2Cl7]3+, however, a shorter Mo‐Mo distance of 289.4(3) pm is observed, which can be interpreted by a single bond. Correspondingly a reduced magnetic moment of 0.95 B.M. per Mo atom is observed. 相似文献
5.
Preparation and Crystal Structure of β-[SeCl3][MoOCl4] The reaction of Se4[MoOCl4] and Te4[MoOCl4] with SOCl2 as solvent at 150 °C and 80 °C yields [SeCl3][MoOCl4] and [TeCl3][MoOCl4] respectively within 3 to 6 days as yellow-brown, moisture-sensitive crystals. [TeCl3][MoOCl4] was obtained in the already known monoclinic form, while β-[SeCl3][MoOCl4] crystallizes in a new polymorphic triclinic form (P1¯, Z = 2, a = 752.7(2), b = 812.8(2), c = 956.9(3) pm, α = 92.55(3)°, β = 111.63(2)°, γ = 107.39(3)°). The structure contains centrosymmetric tetranuclear units ([SeCl3]2[Mo2O2Cl8]) which are analogous to the entities found in the structure of [SCl3][MoOCl4]. The packing of the molecules in β-[SeCl3][MoOCl4] and [SCl3][MoOCl4] is distinctely different. 相似文献
6.
Molybdenum(II) Halide Clusters with two Alcoholate Ligands: Syntheses and Crystal Structures of (C18H36N2O6Na)2[Mo6Cl12(OCH3)2] and (C18H36N2O6Na)2[Mo6Cl12(OC15H11)2] · 2C4H6O3 . Reaction of Mo6Cl12 with two equivalents of sodium methoxide in the presence of 2,2,2-crypt yields (C18H36N2O6Na)2[Mo6Cl12(OCH3)2] ( 1 ), which can be converted to (C18H36N2O6Na)2[Mo6Cl12(OC15H11)2] · 2C4H6O3 ( 2 ) by metathesis with 9-Anthracenemethanole in propylene carbonate. As confirmed by X-ray single crystal structure determination ( 1 : C2/m, a=25.513(8) Å, b=13.001(3) Å, c=10.128(3) Å, β=100.204(12)°; : C2/c, a=15.580(5) Å, b=22.337(5) Å, c=27.143(8) Å, β=98.756(10)°) the compounds contain anionic cluster units [Mo6ClCl(ORa)2]2? with two alcoholate ligands in terminal trans positions ( 1 : d(Mo—Mo) 2.597(2) Å to 2.610(2) Å, d(Mo—Cli) 2.471(3) Å to 2.493(4) Å, d(Mo—Cla) 2.417(8) Å and 2.427(8) Å, d(Mo—O) 2.006(13) Å; 2 : d(Mo—Mo) 2.599(3) Å to 2.628(3), d(Mo—Cli) 2.468(8) Å to 2.506(7) Å, d(Mo—Cla) 2.444(8) Å and 2.445(7) Å, d(Mo—O) 2.012(19) Å). 相似文献
7.
Synthesis and Crystal Structure of Mo2<>NCl8 and Mo3N2Cl11 The reaction of MoCl5 with Cl3VNCl at 140 °C in a sealed glass ampoule yields air sensitive black crystals of the mixed valent molybdenum(V, VI) nitride chloride, Mo2NCl8. It crystallizes in the monoclinic space group P2/c with a = 996.1(1), b = 629.4(1), c = 1780.8(3) pm, β = 101.82(2)°, and Z = 4. The crystal structure consists of dinuclear C2‐symmetrical units [Cl2(N≡)Mo(μ2‐Cl)3Mo(≡N)Cl2]— and [Cl4Mo(μ2‐Cl)MoCl4]+, connected in an alternating sequence by asymmetric nitrido bridges Mo≡N‐Mo to form chains. The reaction of Cl3VNCl with MoCl3 at 140 °C affords Mo3N2Cl11, but for the prolonged reaction period, MoNCl3 is observed in addition. Mo3N2Cl11 can also be obtained from MoNCl3 and MoCl5 (2:1) at 140 °C. It forms orthorhombic, black crystals with the space group Pca21 and a = 1256.1(1), b = 1001.9(1), c = 1330.10(5) pm, and Z = 4. The structure contains the same dinuclear units [Cl2(N≡)Mo(μ2‐Cl)3Mo(≡N)Cl2]— as in Mo2NCl8, which in this case are connected with MoCl4+ moieties by asymmetric nitrido bridges Mo≡N‐Mo forming chains. In Mo2NCl8 the Mo‐N distances in the nearly linear nitrido bridges are 167.6(2), and 214.8(2) pm, whereas in case of Mo3N2Cl11 two sets of Mo‐N distances of 166, 8(4) and 214, 0(4) pm as well as 166, 9(4) and 211, 9(4) pm are observed. 相似文献
8.
The compound (BiCl)[W6Cl14] was previously characterized as a product of the reduction of tungsten hexachloride with elemental bismuth. Another modification of BiW6Cl15 is now presented as (BiCl2)[W6Cl13], based on the results of an X‐ray single crystal structure determination (space group P21/c, a = 1354.3(2) pm, b = 1234.4(2) pm, c = 1538.9(2) pm, and β = 118.76(1) °). The structure of (BiCl2)[W6Cl13] contains chains of [(W6Cl8i)Cl4aCl2/2a–a]– clusters bridged by chlorine atoms. The (BiCl2)+ counterion exhibits two short Bi–Cl distances of 244.1(4) and 245.9(3) pm, respectively. 相似文献
9.
A. V. Virovets M. Laege B. Krebs O. A. Geras'ko V. E. Fedorov O. V. Shishkin Yu. T. Struchkov 《Journal of Structural Chemistry》1996,37(4):666-673
Crystal structures of (Et4N)2[Mo3S7Br6] (I) and (Et4N)(H9O4)[Mo3S7Cl6] (II) clusters belonging to the class of Mo3S 7 4+ were determined by X-ray diffraction analysis. Crystals I are orthorhombic a=19.106(3), b=12.930(2), c=29.887(5) Å, V=7383(2) Å3, space group Pbca, Z=8, dcalc=2.253 g/cm3, R(F)=0.0402, wR(F2)=0.0587 for 2493 Fhkl>4σ. Crystals II are monoclinic, a=17.106(3), b=18.882(4), c=11.006(2), Å, β=126.13(3)°, V=2871.2(9) Å3, space group Cc, Z=4, dcalc=2.147 g/cm3, R(F)=0.0181, wR(F2)=0.0445 for 2307 Fhkl>4σ. Structure I has an anion dimer with 3Sax…Cl=3.258(4)–3.404(4) Å; the dimer is similar to that observed in the structures of A2[M3X7Hal6], A=Ph4P+, Ph3EtP+, and PPN+. In structure II, infinite chains of anions bonded by 3Sax…Cl contacts of 3.183(3)–3.394(3) Å were found. A similar phenomenon was established earlier for the structure of (Et4N)(H9O4)[Mo3S7Br6] (III), which is not isostructural to II. Compounds II and III also differ in the structure of the H9O4 + cation: infinite helix in II and pyramid in III. 相似文献
10.
Polymeric, Band Shaped Tellurium Cations in the Structures of the Chloroberyllate Te7[Be2Cl6] and the Chlorobismutate (Te4)(Te10)[Bi4Cl16] Te7[Be2Cl6] is obtained at 250 °C in an eutectic Na2[BeCl4] / BeCl2 melt from Te, TeCl4 und BeCl2 in form of black crystals, which are sensitive towards hydrolysis in moist air. (Te4) (Te10)[Bi4Cl16] is prepared from Te, TeCl4 und BiCl3 by chemical vapour transport in sealed evacuated glass ampoules in a temperature gradient 150 ° → 90 °Cin form of needle shaped crystals with a silver lustre. The structures of both compounds were determined based on single crystal X‐ray diffraction data (Te7[Be2Cl6]: orthorhombic, Pnnm, Z = 2, a = 541.60(3), b = 974.79(6), c = 1664.4(1) pm; (Te4)(Te10)[Bi4Cl16]: triclinic, P1¯, Z = 2, a = 547.2(3), b = 1321.1(7), c = 1490(1) pm, α = 102.09(5)°, β = 95.05(5)°, γ = 96.69(4)°). The structure of Te7[Be2Cl6] consists of one‐dimensional polymeric cations (Te72+)n which form folded bands and of discrete [Be2Cl6]2— anions which form double tetrahedraconnected by a common edge. By a different way of folding compared with the cations present in the structures of Te7[MOX4]X (M = Nb, W; X = Cl, Br) the (Te72+)n cation in Te7[Be2Cl6]represents a new, isomeric form. The structure of (Te4)(Te10)[Bi4Cl16] contains two different polymeric cations. (Te102+)n consists of planar Te10 groups in the form of three corner‐sharing Te4 rings connected to folded bands. (Te42+)n forms in contrast to the so far notoriously observed discrete, square‐planar E42+ ions a chain of rectangular planar Te4 rings (Te—Te 274 and 281 pm) connected by Te‐Te bonds of 297 pm. [Bi4Cl16]4— has a complex one‐dimensional structure of edge‐ and corner‐sharing BiCl7 units. 相似文献
11.
Pr4S3[Si2O7] and Pr3Cl3[Si2O7]: Derivatives of Praseodymium Disilicate Modified by Soft Foreign Anions For synthesizing both the disilicate derivatives Pr4S3[Si2O7] and Pr3Cl3[Si2O7], Pr, Pr6O11 and SiO2 are brought to reaction with S and PrCl3, respectively, in suitable molar ratios (850 °C, 7 d) in evacuated silica tubes. By using NaCl as a flux, Pr4S3[Si2O7] crystallizes as pale green, transparent single crystals (tetragonal, I41/amd, a = 1201.6(1), c = 1412.0(2) pm, Z = 8) with the appearance of slightly compressed octahedra. On the other hand, Pr3Cl3[Si2O7] emerges as pale green, transparent platelets and crystallizes monoclinically (space group: P21, a = 530.96(6), b = 1200.2(1), c = 783.11(8) pm, β = 109.07(1)°, Z = 2). In both crystal structures ecliptically conformed [Si2O7]6– units of two corner‐linked [SiO4] tetrahedra with Si–O–Si bridging angles of 131° in the sulfide and 148° in the chloride disilicate are present. In Pr4S3[Si2O7] both crystallographically independent Pr3+ cations show coordination numbers of 8 + 1 (5 S2– and 3 + 1 O2–) and 9 (3 S2– and 6 O2–). For Pr1, Pr2 and Pr3 in Pr3Cl3[Si2O7] coordination numbers of 10 (5 Cl– and 5 O2–) and 9 (2 ×; 4 Cl– and 5 O2– or 3 Cl– and 6 O2–, respectively) occur. 相似文献
12.
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
13.
Crystal Structures, Vibrational Spectra, and Normal Coordinate Analysis of cis -(Et4N)[OsF2Cl4] and trans -(Ph4P)[OsF2Cl4] By oxidation of the pure fluorochloroosmates(IV) with KBrF4 or PbO2/trifluoracetic acid in dichloromethane the mixed pentavalent complex anions cis-[OsF2Cl4]– and trans-[OsF2Cl4]– are formed. X-ray structure determinations on single crystals have been performed of cis-(Et4N) · [OsF2Cl4] ( 1 ) (monoclinic, space group P21/n, a = 7.519(2), b = 17.648(2), c = 11.942(4) Å, β = 105.98(2)°, Z = 4) and trans-(Ph4P)[OsF2Cl4] ( 2 ) (tetragonal, space group P4/n, a = 12.677(2), c = 7.743(1) Å, Z = 2). Based on the molecular parameters of the X-ray determinations and assuming C2v point symmetry for the anion of 1 and D4h point symmetry for the anion of 2 the IR and Raman spectra have been assigned by normal coordinate analysis. Due to the stronger trans influence of chlorine as compared with fluorine for F · –Os–Cl′ axes significally different valence force constants are observed in comparison with symmetrically coordinated axes: fd(OsF · ) = 3.35, fd(OsF) = 3.73, fd(OsCl′) = 2.05 and fd(OsCl) with 1.98 and 2.00 mdyn/Å. 相似文献
14.
Molybdenum(II) Halide Clusters with six Alcoholate Ligands: (C18H36N2O6Na)2[Mo6Cl8(OCH3)6] · 6CH3OH and (C18H36N2O6Na)2[Mo6Cl8(OC6H5)6] . The reaction of Na2[Mo6Cl8(OCH3)6] and 2,2,2-crypt yields (C18H36N2O6Na)2[Mo6Cl8(OCH3)6] · 6 CH3OH ( 1 ), which is converted to (C18H36N2O6Na)2[Mo6Cl8(OC6H5)6] ( 2 ) by metathesis with phenol. According to single crystal structure determinations ( 1 : P3 1c, a=14.613(3) Å, c=21.036(8) Å; 2 : P3 1c, a=15.624(1) Å, c=19.671(2) Å) the compounds contain anionic clusters [Mo6Cl8i(ORa)6]2? ( 1 : d(Mo—Mo) 2.608(1) Å to 2.611(1) Å, d(Mo—Cl) 2.489(1) Å to 2.503(1) Å, d(Mo—O) 2.046(4) Å; 2 : d(Mo—Mo) 2.602(3) Å to 2.608(3) Å, d(Mo—Cl) 2.471(5) Å to 2.4992(5) Å, d(Mo—O) 2.091(14) Å). Electronic interactions of the halide cluster and the phenolate ligands in [Mo6Cl8(OC6H5)6]2? is investigated by means of UV/VIS spectroscopy and EHMO calculations. 相似文献
15.
The reaction of Se4[Mo2O2Cl8] with Se4[MCl6] (M = Zr, Hf) or of Se, SeCl4, MoOCl4, and MCl4 (M = Zr, Hf) at 120 °C in sealed evacuated glass ampoules gives (Se4)2[Mo2O2Cl8][MCl6] (M = Zr, Hf) in the form of dark‐green, air sensitive crystals in quantitative yield. The crystal structure analyses of both isotypic compounds (monoclinic, P21/c, Z = 2, a = 1336(2), b = 716(1), c = 1518(4) pm, β = 106.0(2)° for M = Zr; a = 1334.1(8), b = 715.03(9), c = 1518.2(3) pm, β = 106.00(2)° for M = Hf) show the presence of square‐planar Se42+, of dinuclear [Mo2O2Cl8]2—, and of almost regular octahedral [MCl6]2— ions. X‐ray crystallographic investigations on (Se4)2[Mo2O2Cl8][ZrCl6] give no hint for solid state phase transitions between —160 and 200 °C. This is in contrast to the related compounds Se4[Mo2O2Cl8] and Se4[ZrCl6] which both undergo phase transitions accompanied by reorientation of the cations and anions. (Se4)2[Mo2O2Cl8][ZrCl6] is paramagnetic and obeys the Curie‐Weiss law with a Weiss constant of —4(7) K indicating only weak interaction between the paramagnetic centres. The magnetic moment of 1.7(1) μB is consistent with the presence of MoV (d1 configuration) and supports the ionic formula. 相似文献
16.
Polymeric Iodoplumbates – Synthesis and Crystal Structures of (Pr3N–C2H4–NPr3)[Pb6I14(dmf)2] · 4 DMF, (Pr3N–C2H4–NPr3)[Pb(dmf)6][Pb5I14] · DMF, and (Me3N–C2H4–NMe3)2[Pb2I7]I (Pr3N–C2H4–NPr3)[Pb6I14(dmf)2] · 4 DMF ( 1 ) and (Pr3N–C2H4–NPr3)[Pb(dmf)6][Pb5I14] · DMF ( 2 ) have almost the same composition, but completely different structures. Both compounds are formed selectively depending on the reaction and crystallization conditions. In 2 the PbII atoms are coordinated either by six bridging I– ligands in the two-dimensional [Pb5I14]4– network or by six DMF ligands in the [Pb(dmf)6]2+ cations. In contrast, (Me3N–C2H4–NMe3)2[Pb2I7]I ( 3 ) contains non-coordinating I– anions between the iodoplumbate layers. The iodoplumbate anions in 2 and 3 consist of face and corner sharing PbI6 octahedra, whereas in 1 PbI6 and PbI5(dmf) octahedra share common edges to form a one-dimensional polymeric section of the PbI2 structure. (Pr3N–C2H4–NPr3)[Pb6I14(dmf)2] · 4 DMF ( 1 ): Space group P1, a = 920.1(3), b = 1597.2(5), c = 1613.9(4) pm, α = 66.02(2), β = 84.53(2), γ = 85.99(2)°, V = 2156(1) · 106 pm3; (Pr3N–C2H4–NPr3)[Pb(dmf)6][Pb5I14]·DMF ( 2 ): Space group P21, a = 1201.21(9), b = 3031.1(2), c = 1294.96(9) pm, β = 108.935(7)°, V = 4459.8(5) · 106 pm3; (Me3N–C2H4–NMe3)2[Pb2I7]I ( 3 ): Space group Pnma, a = 2349.9(2), b = 1623.83(9), c = 980.75(7) pm, V = 3742.4(5) · 106 pm3. 相似文献
17.
On Reactions of Hexachlorodiberyllate with Trimethylsilyl‐N‐dimethylamide. Crystal Structures of (Ph4P)3[Be2Cl5(OSiMe3)][BeCl3(Me2NSiMe3)], (Ph4P)[BeCl3(HNMe2)], and (Ph4P)(H2NMe2)[BeCl4] Reactions of bis‐tetraphenylphosphonium hexachlorodiberyllate, (Ph4P)2[Be2Cl6], with trimethylsilyl‐N‐dimethylamide under different conditions lead to the novel chloroberyllate derivatives (Ph4P)3[Be2Cl5(OSiMe3)][BeCl3(Me2NSiMe3)] ( 1 ), (Ph4P)[BeCl3(HNMe2)] ( 2 ), and (Ph4P)(H2NMe2)[BeCl4] ( 3 ). 1 ‐ 3 were characterized by IR spectroscopy and crystal structure determinations. 1· 4CH2Cl2: Space group P1¯, Z = 2, lattice dimensions at 193 K: a = 1115.6(1), b = 2110.7(2), c = 2145.0(3) pm, α = 71.38(1)°, β = 85.66(1)°, γ = 85.24(1)°, R1 = 0.0732. The [Be2Cl5(OSiMe3)]2— ion in the structure of 1 is derived from the [Be2Cl6]2— ion by substitution of a μ‐Cl ligand by the oxygen atom of the (OSiMe3)— group. The second anion, [BeCl3(Me2NSiMe3)]—, can be described as donor acceptor complex with a short Be—N bond of 179(1) pm. 2 : Space group P1¯, Z = 2, lattice dimensions at 193 K: a = 1063.1(1), b = 1072.0(1), c = 1238.3(1) pm, α = 87.55(1)°, β = 74.86(1)°, γ = 69.73(1)°, R1 = 0.0299. The anion of 2 forms a centrosymmetric dimer [BeCl3(HNMe2)]22— via N—H···Cl bridges of the two donor acceptor complex units with Be—N separations of 175.2(2) pm. 3 : Space group Pbca, Z = 8, lattice dimensions at 193 K: a = 926.9(1), b = 2164.7(1), c = 2732.7(1) pm, R1 = 0.0495. The structure of 3 contains centrosymmetric ion quadrupoles [(Me2NH2)(BeCl4)]22— forming by N—H···Cl bridges between (Me2NH2)+ and [BeCl4]2— ions. 相似文献
18.
Ulrich Müller Elke Conradi Ute Patt-Siebel Meinolf Kersting Inge Schmidt Abderraouf Khabou Kurt Dehnicke 《无机化学与普通化学杂志》1988,560(1):93-104
Spectroscopic and Crystallographic Characterization of [Cl3PNPCl3][MoOCl4] and Crystal Structure of [Cl3PNPCl3][MoCl6] [Cl3PNPCl3][MoCl6] was obtained by reaction of MoCl5 with [Cl3PNPCl3]Cl or [Cl3PNPCl3][PCl6]. Its crystal was determined by X-ray diffraction (R = 0.072 for 889 observed reflexions). Lattice parameters: a = 811.9, b = 2086, c = 1016 pm, β = 101.7°, space group P21/c, Z = 4. The [Cl3PNPCl3]+ ions have a similar structure as in Cl3PNPCl3 [PCl6] with PNP angles of 139°, but the crystal structures of the two compounds are not isotypic. Partial hydrolysis of [Cl3PNPCl3][MoCl6] yields [Cl3PNPCl3][MoOCl4] which forms green, very moisture sensitive crystals. X-ray diffraction patterns of [Cl3PNPCl3][MoOCl4] single crystals exhibit planes of diffuse scattered radiation perpendicular to c*, which show the presence of a two-dimensional disorder. Additional sharp reflexions correspond to an averaged structure with the lattice parameters a = 1598.4, b = 1141.2 and c = 415.1 pm, Z = 2, space group Pba2. Refinement of the averaged 相似文献
19.
Synthesis and Structure of [Re(NH)Cl2(PMe2Ph)3][TaCl6] and [(Me2PhP)3Cl2Re≡N]2VOCl2 The products of the reaction of ReNCl2(PMe2Ph)3 with TaCl5 are dependent on the solvent. In CH2Cl2 the solvent protonates the nitrido ligand to yield [Re(NH)Cl2(PMe2Ph)3][TaCl6] as air-stable, reddish brown needles with the space group P21/n and a = 1213.8(3), b = 1358.0(2), c = 2165.9(4) pm, β = 92.88(1)°, Z = 4. The Re atom of the cation exhibits an octahedral coordination with the phosphine ligands in meridional arrangement. The imido ligand is in trans-position to a Cl atom with a distance Re–N = 170.4(4) pm. When the reaction is carried out in toluene the dinuclear nitrido complex [Re(NTaCl5)Cl2(PMe2Ph)3] is obtained instead. The reaction of ReNCl2(PMe2Ph)3 with VCl3(THF)3 in toluene affords the threenuclear complex [Re2N2Cl4(PMe2Ph)5]VCl3, which upon crystallization at air gives air-stable, reddish-brown crystals of [(Me2PhP)3Cl2ReN]2VOCl2. They crystallize in the monoclinic space group P21 with a = 1519.2(5), b = 1257.1(1), c = 1564.3(6) pm, β = 102.86(2)°, and Z = 2. The threenuclear complex shows an almost linear arrangement Re≡N–V–N≡Re with distances Re–N 171(2) pm and V–N of 209(2) pm. 相似文献
20.
Phosphanimine and Phosphoraneiminato Complexes of Beryllium. Crystal Structures of [BeCl2(HNPPh3)2], [BeCl(HNPPh3)2(Py)]Cl, and [Be3Cl2(NPPh3)4] Tetraphenylphosphonium hexachlorodiberyllate, (Ph4P)2[Be2Cl6], reacts with lithium phosphoraneiminate, [LiNPPh3]6, in dichloromethane to give the three‐nuclear beryllium phosphoraneiminate [Be3Cl2(NPPh3)4] ( 3 ). As a by‐product the phosphaneimine complex [BeCl2(HNPPh3)2] ( 1 ) can be isolated, which reacts with pyridine to give the ionic complex [BeCl(HNPPh3)2(Py)]Cl ( 2 ). On the other hand, the silylated phosphanimine Me3SiNP(p‐tolyl)3 ( 5 ) does not react with BeCl2 or (Ph4P)2[Be2Cl6] forming the expected phosphoraneiminates. From CH2Cl2 solutions only the amino‐phosphonium salt [(C7H7)3PNH2]Cl ( 4 ) can be obtained. The compounds 1 ‐ 5 are characterized by single X‐ray analyses and by IR spectroscopy. 1 ·C7H8: Space group C2/c, Z = 4, lattice dimensions at 193 K: a = 1408.9(2), b = 1750.9(2), c = 1633.2(2) pm, β = 106.50(1)°; R1 = 0.0385. 1 forms a molecular structure with short Be—N distances of 169.8(3) pm. 2 ·Py: Space group P1¯, Z = 4, lattice dimensions at 193 K: a = 969.5(1), b = 2077.1(2), c = 2266.4(2) pm, α = 72.24(1)°, β = 87.16(1)°, γ = 77.42(2)°, R1 = 0.0776. 2 forms ion pairs in which the NH atoms of the phosphaneimine ligands act as hydrogen bridges with the chloride ion. The HNPPh3 ligand realizes short Be—N bonds of 169.0(6) pm, the Be—N distance of the pyridine molecule is 182.5(6) pm. 3 ·3CH2Cl2: Space group P1¯, Z = 2, lattice dimensions at 193 K: a = 1333.2(2), b = 1370.2(2), c = 2151.8(3) pm, α = 107.14(1)°, β = 91.39(1)°, γ = 105.15(1)°, R1 = 0.0917. The structure of the three‐nuclear molecule 3 corresponds with a Be2+ ion which is tetrahedrally coordinated by the nitrogen atoms of two {ClBe(NPPh3)2}— chelates. 4 ·CH2Cl2: Space group P21/c, Z = 4, lattice dimensions at 193 K: a = 1206.6(2), b = 1798.0(2), c = 1096.2(1) pm, β = 97.65(1)°, R1 = 0.0535. 4 forms dimeric units in which the NH2 groups of the [(C7H7)3PNH2]+ cations act as hydrogen bridges with the chloride ions to give centrosymmetric eight‐membered rings. 5 : Space group P21/n, Z = 4, lattice dimensions at 193 K: a = 1074.3(2), b = 2132.2(3), c = 1075.5(2) pm, β = 110.68(1)°, R1 = 0.0664. 5 forms molecules with distances PN of 154.6(3), SiN of 168.8(3) pm, and bond angle SiNP of 134.4(2)°. 相似文献