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1.
Studies on Polyhalides. 30 On Decamethylferriciniumpolyiodides [(Me5C5)2Fe]Ix with x = 3, 5, 6.5: Preparation and Crystal Structures of a Triiodide (DMFc)I3, a Pentaiodide (DMFc)I5 and a Hexacosaiodide (DMFc)4I26 Decamethylferrocene (DMFc) may be oxidized by iodine analogous to ferrocene (Fc) to the decamethylferrocenium ion (DMFc)+ and precipitated as the crystalline solids decamethylferrocenium triiodide (DMFc)I3, decamethylferrocenium pentaiodide (DMFc)I5 and tetracisdecamethylferrocenium hexacosaiodide (DMFc)4I26. The two compounds with higher iodine content are new. These are characterized by X-ray diffraction methods on single crystals. The structures are built up from complex cations of expected geometry and isolated or remarkably connected polyiodide ions. Decamethylferrocenium triiodide C20H30FeI3 crystallizes monoclinically in C2/m with a = 1489.9(4) pm, b = 1133.0(2) pm, c = 765.9(3) pm, β = 111.76(3)° and Z = 2. The crystal structure follows the CsCl-type and contains isolated triiodide ions of the linear symmetric form. Decamethylferrocenium pentaiodide C20H30FeI5 crystallizes monoclinically in P21/c with a = 1130.0(2) pm, b = 1442.6(1) pm, c = 1716.6(2) pm, β = 96.62(1)° and Z = 4. The crystal structure may be deduced from the primitiv quadratic bundle of alternating cationic and anionic rods. It contains exceptionally isolated somewhat opened out pentaiodide ions. Tetrakisdecamethylferrocenium hexacosaiodide (C20H30Fe)4I26 crystallises monoclinically in P21/n with a = 1331.3(8) pm, b = 1319.4(4) pm, c = 3564(2) pm, β = 90.84(5)° and Z = 2. The crystal structure of this compound with unusual composition may be described as an inclusion compound with channels for the cations. The outstanding anionic grating may be derived from the primitive cubic lattice of iodide ions with iodine bridges on all edges by removing systematically 1/12 of the iodine molecules. 相似文献
2.
Synthesis, Crystal Structures, and Vibrational Spectra of [(Ph3P)2N]2[(W6Cl )I ] · 2 Et2O · 2 CH2Cl2 and [(Ph3P)2N]2[(W6Cl )(NCS) ] · 2 CH2Cl2 By treatment of [(W6Cl)I]2– with (SCN)2 in dichloromethane at –20 °C the hexaisothiocyanato cluster anion [(W6Cl)(NCS)]2– is formed. X‐ray structure determinations have been performed on single crystals of [(Ph3P)2N]2[(W6Cl)I] · 2 CH2Cl2 · 2 Et2O ( 1 ) (triclinic, space group P1, a = 10.324(5), b = 14.908(3), c = 17.734(8) Å, α = 112.78(2)°, β = 99.13(3)°, γ = 92.02(3)°, Z = 1) and [(Ph3P)2N]2[(W6Cl)(NCS)] · 2 CH2Cl2 ( 2 ) (triclinic, space group P1, a = 11.115(2), b = 14.839(2), c = 17.036(3) Å, α = 104.46(1)°, β = 105.75(2)°, γ = 110.59(1)°, Z = 1). The thiocyanate ligands of 2 are bound exclusively via N atoms with W–N bond lengths of 2.091–2.107 Å, W–N–C angles of 173.1–176.9° and N–C–S angles of 178.1–179.3°. The vibrational spectra exhibit characteristic innerligand vibrations at 2067–2045 (νCN), 879–867 (νCS) and 490–482 (δNCS). Based on the molekular parameters of the X‐ray determination of 1 the vibrational spectra of the corresponding (n‐Bu4N) salt of 1 are assigned by normal coordinate analysis. The valence force constants are fd(WW) = 1.61, fd(WI) = 1.23 and fd(WCl) = 1.10 mdyn/Å. 相似文献
3.
Studies on Polyhalides. 40. Ethyltrimethylammonium Pentaiodide (EtMe3N)I5 (EtMe3N)I5 has been prepared by the reaction of stoichiometric amounts of ethyltrimethylammonium iodide and iodine in methanol. It crystallizes in the orthorhombic space group Pna21 with a = 1011.3(1) pm, b = 1255.3(2) pm, c = 1237.7(2) pm and Z = 4. The anionic iodine partial structure is composed of puckered layers which may be derived by deforming a quadratic net with iodide ions in the knots and iodine molecules on the edges of the meshes. 相似文献
4.
Synthesis, Crystal Structures, and Vibrational Spectra of [(Mo6X)Y]2–; Xi = Cl, Br; Ya = NO3, NO2 By treatment of [(Mo6X)Y]2–; Xi = Ya = Cl, Br with AgNO3 or AgNO2 by strictly exclusion of oxygene in acetone the hexanitrato and hexanitrito cluster anions [(Mo6X)Y]2–, Ya = NO2, NO3 are formed. X-ray structure determinations of (Ph4As)2[(Mo6Cl)(NO3)] · 2 Me2CO ( 1 ) (monoclinic, space group P21/n, a = 12.696(3), b = 21.526(1), c = 14.275(5) Å, β = 115.02(2)°, Z = 2), (n-Bu4N)2[(Mo6Br)(NO3)] · 2 CH2Cl2 ( 2 ) (monoclinic, space group P21/n, a = 14.390(5), b = 11.216(5), c = 21.179(5)Å, β = 96.475(5)°, Z = 2) and (Ph4P)2[(Mo6Cl)(NO2)] (3) (monoclinic, space group P21/n, a = 11.823(5), b = 13.415(5), c = 19.286(5) Å, β = 105.090(5)°, Z = 2) reveal the coordination of the ligands via O atoms with (Mo–O) bond lengths of 2.11–2.13 Å, and (MoON) angles of 122–131°. The vibrational spectra of the nitrato compounds show the typical innerligand vibrations νas(NO2) (∼ 1500), νs(NO2) (∼ 1270) and ν(NO) (∼ 980 cm–1). The stretching vibrations ν(N=O) at 1460–1490 cm–1 and ν(N–O) in the range of 950–1000 cm–1 are characteristic for nitrito ligands coordinated via O atoms. 相似文献
5.
Synthesis, Crystal Structure, and Vibrational Spectra of (n-Bu4N)2[(Mo6I)(NCS)] By treatment of [(Mo6I)I]2– with (SCN)2 in dichloromethane at –20 °C the hexaisothiocyanato cluster anion [(Mo6I)(NCS)]2– is formed. The X-ray structure determination of (n-Bu4N)2[(Mo6I)(NCS)] · 2 Me2CO (monoclinic, space group P21/c, a = 13.168(5), b = 11.964(5), c = 24.636(5) Å, β = 104.960(5)°, Z = 2) shows, that the thiocyanate groups are coordinated exclusively via N atoms with Mo–N bond lengths of 2.141–2.150 Å, Mo–N–C angles of 166–178° and N–C–S-angles of 174–180°. The vibrational spectra exhibit characteristic innerligand vibrations at 2073–2054 (νCN), 846–844 (νCS) and 480–462 cm–1 (δNCS). 相似文献
6.
Studies on Polyhalides. 26. On N-Propylurotropinium Polyiodides UrPrIx with x = 5 and 7: Crystal Structures of a Pentaiodide and a Heptaiodide The salts UrPrIx with x = 5 and 7 are formed by the reaction of N-propylurotropinium iodide UrPrI with excess iodine I2 at room temperature from aqueous solution. N-propylurotropinium pentaiodide C9H19N4I5 crystallizes monoclinically in P21/n with a = 1007.6(3) pm, b = 1362.5(3) pm, c = 2899.0(9) pm, β = 91.49(3)º and Z = 8. The crystal structure is built up from parallel chains of cations UrPr+ and pairs of V-shaped pentaiodide anions I5? along [0 1 0]. N-propylurotropinium heptaiodide C9H19N4I7 crystallizes triclinically in P1 with a = 970.4(1) pm, b = 971.1(1) pm, c = 1357.8(2) pm, α = 106.83(1)º, β = 92.28(1)º, γ = 105.17(1)º and Z = 2. The crystal structure is stacked by alternating cationic and anionic double layers along [0 0 1]. The heptaiodide layer shows a two-dimensional network. 相似文献
7.
Studies on Polyhalides. 16. Preparation and Crystal Structures of Bipyridiniumpolyiodides Bipy · HIn with n = 3, 5, and 7 With simply protonated α,α′-Bipyridyl Bipy · H+ a triiodide Bipy · HI3, a pentaiodide Bipy · HI5 and a heptaiodide Bipy · HI7 may be prepared in the presence of iodide ions I? and dependent of the iodine I2 content. Bipyridiniumtriiodide C10H9N2I3 crystallizes at room temperature monoclinically in P21/n with a = 1 122.8(1) pm, b = 1 072.7(1) pm, c = 1 200.2(3) pm, β = 98.02(2)° and Z = 4. The crystal structure is built up from mixed cationic and anionic layers. Bipyridiniumpentaiodide C10H9N2I5 crystallizes at room temperature monoclinically in P21/c with a = 887.3(5) pm, b = 2 527.9(12) pm, c = 830.7(3) pm, β = 106.78(5)° and Z = 4. The crystal structure contains triiodide ions I3? till now uniquely connected by iodine molecules I2 in a trigonal planar way. Bipyridiniumheptaiodide C10H9N2I7 crystallizes at room temperature triclinically in P&1macr; with a = 713.1(3) pm, b = 1 007.9(3) pm, c = 1 464,8(4) pm, α = 81.07(3)°, β = 89.92(3)°, γ = 82.77(3)° and Z = 2. The crystal structure contains a V-shaped pentaiodide ion I5? completed by an iodine molecule I2 to a trigonal pyramidally shaped heptaiodide ion I7? and at the same time connected to a zigzag chain. 相似文献
8.
Synthesis of Copper and Silver Complexes with Pentadentate N,S and Hexadentate N,O Chelate Ligands – Characterization and Crystal Structures of {Cu2[C6H4(SO2)NC(O)]2(C5H5N)4}, {Cu2[C5H3N(CHNC6H4SCH3)2]2}(PF6)2, and {Ag[C5H3N(CHNC6H4SCH3)2]}PO2F2 In the course of the reaction of copper(II)-acetate monohydrate with 2,2′-bisbenzo[d][1,3]thiazolidyl in methanol the organic component is transformed to N,N′-bis-(2-thiophenyl)ethanediimine and subsequently oxidized to the N,N′-bis-(2-benzenesulfonyl)ethanediaciddiamide H4BBSED, which coordinates in its deprotonated form two Cu2+ ions. Crystallisation from pyridine/n-hexane yields [Cu2(BBSED)(py)4] · MeOH. It forms triclinic crystals with the space group P1 and a = 995.5(2) pm, b = 1076.1(3) pm, c = 1120.7(2) pm, α = 104.17(1)°, β = 105.28(1)°, γ = 113.10(1)° and Z = 1. In the centrosymmetrical dinuclear complex the copper ions are coordinated in a square-pyramidal arrangement by three nitrogen and two oxygen atoms. The Jahn-Teller effect causes an elongation of the axial bond by approximately 30 pm. The reactions of the pentadentate ligand 2,6-Bis-[(2- methylthiophenyl)-2-azaethenyl]pyridine BMTEP with salts of copper(I), copper(II) and silver(I) yield the complexes [CU2(BMTEP)2](PF6)2, [Cu(BMTEP)]X2 (X = BF, C1O) and [Ag(BMTEP)]X (X = PO2F, ClO). [Cu2(BMTEP)2](PF6)2 crystallizes from acetone/diisopropyl- ether in form of monoclinic crystals with the space group C2/c, and a = 1833.2(3) pm, b = 2267.30(14) pm, c = 1323.5(2) pm, β= 118.286(5)°, and 2 = 4. In the dinuclear complex cation with the symmetry C2 the copper ions are tetrahedrally coordinated by two bridging BMTEP ligands. The Cu? Cu distance of 278.3pm can be interpreted with weak Cu? Cu interactions which also manifest itself in a temperature independent paramagnetism of 0.45 B.M. The monomeric silver complex [Ag(BMTEP)]PO2F2 crystallizes from acetone/thf in the triclinic space group P1 with a = 768.7(3) pm, b = 1074.0(5) pm, c = 1356.8(5) pm, α = 99.52(2)°, β = 96.83(2)°, γ = 99.83(2)° and Z = 2. The central silver ion is coordinated by one sulfur and three nitrogen atoms of the ligand in a planar, semicircular arrangement. The bond lengths Ag? N = 240.4–261.7 and Ag? S = 257.2 pm are significantly elongated in comparison with single bonds. 相似文献
9.
Preparation and Crystal Structures of Silver(I) Mixed Ligand Complexes with Bibenzimidazole and Triphenylphosphane: [Ag(PPh3)2(bbimH2)](COOCH3) · 2 CH2Cl2 and [{Ag(PPh3)2}2(μ-bbim)] · 4 CH2Cl2 The title compounds are obtained from silver acetate, 2,2′-bibenzimidazole and PPh3. They are characterized by their IR, 1H-NMR, 31P-NMR spectra and crystal structure determinations. [Ag(PPh3)2(bbimH2)](COOCH3) · 2 CH2Cl2: Reaction in CH2Cl2. Space group C2/c, Z = 4, 3129 observed unique reflections, R = 0.033. Lattice parameters at 203 K: a = 1450.8; b = 1556.2; c = 2316.4 pm; β = 99.69°. The crystal structure is built up by monomeric molecules with distorted tetrahedral coordination of the silver atom (AgP2N2) and bibenzimidazole as a bidentate ligand. The acetate ion is linked to the NH-groups of the bibenzimidazole by hydrogen bonds. [{Ag(PPh3)2}2(μ-bbim)] · 4 CH2Cl2: Reaction in fused PPh3 at 180 °C. Space group P 1, Z = 1. 9227 observed unique reflections, R = 0.051. Lattice parameters at 203 K: a = 1276.5; b = 1352.1; c = 1408.1 pm; α = 96.97; β = 115.87; γ = 96.84°. The crystal structure is built up by centrosymmetric molecules with distorted tetrahedral coordination of the silver atoms (AgN2P2) and bibenzimidazolate(2–) as tetradentate bridging ligand. 相似文献
10.
Nina Herzmann Ingo Pantenburg Ingrid Müller Wieland Tyrra Gerd Meyer 《无机化学与普通化学杂志》2006,632(14):2209-2216
New Polyiodides of Cesium containing Double and Triple Decker Cations, [Cs(benzo‐18‐crown‐6)2]Ix and [Cs2(benzo‐18‐crown‐6)3](Ix)2 (x = 3, 5) [Cs(b18c6)2]Ix (x = 3 (1) , 5 (3) ) and [Cs2(b18c6)3](Ix)2 (x = 3 (2) , 5 (4) ) (b18c6 = benzo‐18‐crown‐6) have been synthesized by the reaction of benzo‐18‐crown‐6 (C16H24O6), cesium iodide (CsI) and iodine (I2) in acetonitrile ( 1 ), ethanol/dichloromethane ( 2 , 4 ) and 2‐methoxyethanol ( 3 ). Their crystal structures were determined on the basis of single crystal X‐ray data {( 1 ): monoclinic, C2/c, Z = 4, a = 2048.8(5), b = 1329.5(5), c = 1588.7(5) pm, β = 110.23(1)°; ( 2 ): monoclinic, C2/c, Z = 4, a = 2296.0(1), b = 2092.7(1), c = 1373.6(1) pm, β = 100.21(1)°; ( 3 ): monoclinic, P21/n, Z = 4, a = 1586.3(1), b = 1745.5(1), c = 1608.6(1) pm, β = 92.37(1)°; ( 4 ): triclinic, , Z = 2, a = 1241.7(1), b = 1539.8(2), c = 1938.4(2) pm, α = 91.15(1), β = 100.53(1), γ = 95.26(1)°}. As expected, double decker cations centered by Cs atoms, [Cs(b18c6)2]+, are found in the structures of ( 1 ) and ( 3 ). In contrast, the triple decker cation found in ( 2 ) and ( 4 ) is less common. The triiodide anions of ( 1 ) and ( 2 ) can be regarded as normal and the chain‐type pentaiodide anions of ( 3 ) and ( 4 ) fall into the known systematic sequence of these anions. The differences in the connectivity of the crystallographically independent I5? anions in ( 4 ) are surprising with respect to the fact that, so far, independent pentaiodide anions do not show variations in their scheme of connectivity within one crystal structure. 相似文献
11.
Studies of Polyhalides. 27. On Tetra(n-propyl)ammonium Polyiodides (n-Pr4N)In with n = 3, 5, 7: Preparation and Crystal Structures of a Triiodide (n-Pr4N)I3, a Pentaiodide (n-Pr4N)I5, and a Heptaiodide (n-Pr4N)I7 [(n-C3H7)4N]I3, [(n-C3H7)4N]I5 and [(n-C3H7)4N]I7 have been prepared by the reaction of tetra(n-propyl)ammoniumiodide [(n-C3H7)4N]I with iodine I2 in ethanol. Their crystal structures have been determined by single crystal X-ray diffraction methods. The triiodide is built up from layers of the quarternary ammonium ions n-Pr4N+ and from two independent differently packed centrosymmetric triiodide ions I3? which alternate with each other along [100]. The pentaiodide ion forms slightly puckered almost squared nets perpendicular [001] of iodide ions which are connected with four iodine molecules by secondary bonds. The meshes from twelve iodine atoms include the cations. The centrosymmetric Z-shaped heptaiodide ion is built up from a linear symmetric triiodide ion and two iodine molecules forming twisted rope ladders along [001] which are separated by stacks of cations. 相似文献
12.
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
13.
Karl-Friedrich Tebbe Taraneh Farida Harald Stegemann Harry Füllbier 《无机化学与普通化学杂志》1996,622(3):525-533
Studies on Polyhalides. 23. Crystal Structures of N-Alkylurotropinium Triiodides UrRI3 with R = Methyl, Ethyl, n-Propyl, and n-Butyl The salts UrRI3 may be prepared by the reaction of N-alkylurotropinium iodides UrRI with iodine I2 at room temperature from aqueous solution. N-methylurotropinium triiodide C7H15N4I3 crystallizes monoclinically in P21/c with a = 1300.8(2) pm, b = 1276.0(3) pm, c = 859.3(2) pm, β = 94.75(2)° and Z = 4. The crystal structure is built up from layers of cations UrMe+ and of linear symmetric triiodide ions I3? alternating along [100]. N-ethylurotropinium triiodide C8H17N4I3 crystallizes orthorhombically in Pnma with a = 1397.3(5) pm, b = 1221.3(2) pm, c = 886.2(2) pm and Z = 4. The cationic (UrEt+) and anionic (I3?) layers alternate along [0 10]. N-propylurotropinium triiodide C9H19N4I3 crystallizes monoclinically in P21/c with a = 1885.7(5) pm, b = 1657.1(5) pm, c = 1700.5(4) pm, β = 112.39(2)° and Z = 12. The three independent cations and anions are slightly, but differently distorted. N-butylurotropinium triiodide C10H21N4I3 crystallizes monoclinically in P21/m with a = 991.8(3) pm, b = 757.8(2) pm, c = 1128.2(2) pm, β = 90.73(2)° and Z = 2. The crystal structure is stacked by alternating cationic and anionic layers along [001]. The triiodide ion is asymmetric and linear. 相似文献
14.
Wolfgang Einholz Knut Vaas Christoph Wieloch Bernd Speiser Tina Wizemann Markus Strbele Hans‐Jürgen Meyer 《无机化学与普通化学杂志》2002,628(1):258-268
Chemical and Cyclovoltammetric Investigation of the Redoxreactions of the Decahalodecaborates closo ‐[B10X10]2– and hypercloso ‐[B10X10]· – (X = Cl, Br)1). Crystal Structure Analysis of Cs2[B10Br10] · 2 H2O The oxidation of the decachloro‐closo‐decaborates(2–) Cs2[B10Cl10] or [Me4N]2[B10Cl10] with Tl(CF3COO)3 leads to the corresponding radical monoanion hypercloso‐[B10Cl10] · –, which was characterized by ESR and UV/Vis spectroscopy. [B10Cl10] · – does not dimerize like [B10H10] · – but it is reduced by acetonitrile to the dianion [B10Cl10]2–. Cs2[B10Cl10] reacts with stronger oxidation agents like CoF3 (in dichloromethane) or XeF2 (in perfluorhexane), respectively, to yield B9Cl9 and, in traces, B8Cl8. In opposite to this, the decabromoderivative Cs2[B10Br10] does not show any reaction with Tl(CF3COO)3 in acetonitrile or with CoF3 in CH2Cl2. The oxidation of the dianions [B10X10]2– (X = Cl, Br) was studied by electroanalytical methods (cyclic voltammetry, chronoamperometry, chronocoulometry). Formal potentials were determined for the two steps of the reaction, which do not seem to be affected by structural rearrangements. The crystal structure of Cs2[B10Br10] · 2 H2O was analyzed by single‐crystal X‐ray diffraction. Cs2[B10Br10] · 2 H2O crystallizes monoclinic (space group I2/a, (no. 15), Z = 8, a = 1361.54(9) pm, b = 1215.89(5) pm, c = 3108.4(2) pm, α = 90°, β = 97.916(8)°, γ = 90°). The closo‐cluster B10Br102– has a bicapped square antiprismatic structure with idealized D4d symmetry. 相似文献
15.
Crystal Structures of Dipyridiniomethane Monohalogenohydro-closo-Decaborates(2–), [(C5H5N)2CH2][2-XB10H9]; X = Cl, Br, I [B10H10]2? reacts with chlorine, bromine and iodine or with N-halogenosuccinimide, yielding the monohalogenodecaborates [2-XB10H9]2? (X = Cl, Br, I), which are separated by ion exchange chromatography on diethylaminoethyl(DEAE) cellulose from the starting compound and higher halogenated products. The X-ray structure determinations of the isotypic chloro and bromo compounds [(C5H5N)2CH2][2-XB10H9] (monoclinic, space group C2/c, Z = 8; for X ? Cl: a = 33.174(5), b = 7.2809(4), c = 16.2232(7) Å, β = 113.307(7)°; for X = Br: a = 33.525(11), b = 7.281(2), c = 16.297(4) Å, β = 113.62(2)°) and of the iodo compound [(C5H5N)2CH2][2-IB10H9] (monoclinic, space group P21, Z = 2, a = 7.143(3), b = 13.568(4), c = 9.479(7) Å, β = 97.57(5)°) show columns of substituted boron clusters [2-XB10H9]2?, X = Cl, Br, I and bent dications [(C5H5N)2CH2]2+ along the shortest axis wich are assembled to alternating layers in the crystal lattice. 相似文献
16.
Harald Krautscheid 《无机化学与普通化学杂志》1995,621(12):2049-2054
Synthesis and Crystal Structures of (Ph4P)4[Bi8I28], (nBu4N)[Bi2I7], and (Et3PhN)2[Bi3I11] – Bismuth Iodo Complexes with Isolated and Polymeric Anions Solutions of BiI3 in methanol react with NaI and (nBu4N)(PF6) or (Et3NPh)(PF6) to form anionic bismuth iodo complexes (nBu4N)[Bi2I7] 1 and (Et3PhN)2[Bi3I11] 2 . In 1 Bi4I16 units, and in 2 Bi6I24 units are linked by common I-atoms to onedimensional infinite chains. Reaction of BiI3 with (Ph4P)(PF6) in methanol yields (Ph4P)4[Bi8I28] 3 . The anions of 1–3 consist of edge-sharing BiI6 octahedra. (nBu4N)[Bi2I7] 1 : Space group I2/m (No. 13), a = 1 082.3(5), b = 2 597.1(13), c = 1 206.1(6) pm, β = 93.17(2)°, V = 3 385(3) · 106 pm3; (Et3PhN)2[Bi3I11] 2 : Space group P1 (No. 2), a = 1 283.5(6), b = 1 345.9(7), c = 1 546.3(8) pm, α = 83.87(2), β = 74.24(2), γ = 68.26(2)°, V = 2 388(2) · 106 pm3; (Ph4P)4[Bi8I28] 3 : Space group P1 (No. 2), a = 1 329.3(4), b = 1 337.0(4), c = 2 193.1(5) pm, α = 104.20(2), β = 99.73(2), γ = 100.44(2)°, V = 3 622(2) · 106 pm3. 相似文献
17.
Phosphoraneiminato Complexes of Iodine. Syntheses and Crystal Structures of Ph3PNIO2 and Ph3PNSiMe3 · I2 Ph3PNIO2 has been prepared as yellow crystals by the reaction of Ph3PNSiMe3 with I2O5 in boiling acetonitrile, whereas the molecular complex Ph3PNSiMe3 · I2 is formed as brown crystals by the reaction of Ph3PNSiMe3 with iodine in acetonitrile solution. Both complexes were characterized by crystal structure determinations. Ph3PNIO2: Space group P21/n, Z = 4, 2 858 observed unique reflections, R = 0.039. Lattice dimensions at 19°C: a = 972.8(2), b = 1 743.4(3), c = 1 073.7(2) pm, β = 115.46(3)°. The compound forms monomeric molecules with pyramidal geometry at the iodine atom. The bond angle PNI (126.9°) is unusually small; the PN bond length of 159.2 pm corresponds with a double bond. Ph3PNSiMe3 · I2: Space group P1 , Z = 2, 3 560 observed unique reflections, R = 0.033. Lattice dimensions at 19°C: a = 941.2(2), b = 1 041.7(2), c = 1 287.4(3) pm, α = 78.34(1)°, β = 72.00(2)°, γ = 86.08(2)°. The compound forms monomeric molecules, in which the I2 molecule and the nitrogen atom of the phosphoraneimine molecule realize a linear N? I? I axis with a bond length N? I of 243.2 pm. 相似文献
18.
Synthesis and Structure of [(Me2PhP)3Cl2ReN]2NbCl4 and [Re3N3Cl5(PMe2Ph)6][NbCl6] The reaction of ReNCl2(PMe2Ph)3 with NbCl5 in toluene yields the trinuclear complexes [(Me2PhP)3Cl2ReN]2‐ NbCl4 (1) and [Re3N3Cl5(PMe2Ph)6][NbCl6] ( 2 ). 1 forms triclinic crystals with the composition 1 · 2 C7H8 (P 1, a = 1074.5(1), b = 1289.1(2), c = 1299.3(2) pm, α = 85.25(2)°, β = 81.04(2)°, γ = 86.02(1)°, Z = 1). In the centrosymmetric compound 1 two complexes ReNCl2(PMe2Ph)3 coordinate with their nitrido ligands a square planar, central unit NbCl4 to form an almost linear arrangement Re≡N–Nb–N≡Re. The length of the Re–N triple bonds is 172,2 pm, and the Nb–N distances of 216.0 pm correspond to coordinative single bonds. 2 forms orthorhombic crystals with the space group P212121 and a = 1286.0(1), b = 2109.2(4), c = 2436.2(3) pm, Z = 4. The three Re atoms are located at the corners of a triangle. They are connected by two asymmetric nitrido bridges and two asymmetric chloro bridges. The weakly bent nitrido bridges (Re–N–Re = 152° and 157°) are characterized by Re–N distances of 169 und 207 pm as well as 171 and 207 pm. Re1, in addition, binds a terminal nitrido ligand with Re1–N1 = 166 pm. 相似文献
19.
Tellurium Cations stabilized by Niobium Oxytrihalides: Synthesis and Crystal Structure of Te7NbOBr5 and Te7NbOCl5 The reaction of Te2Br with NbOBr3 in a sealed evacuated glass ampoule at 225°C yields Te7NbOBr5 in form of bright black needles. Te7NbOCl5 is obtained from tellurium, TeCl4 and NbOCl3 at 220°C. Both compounds crystallize orthorhombic in the space group Pcca (Te7NbOBr5: a = 2 651,9(4) pm, b = 836.6(1) pm, c = 794.6(1) pm; Te7NbOCl5: a = 2 597.7(5) pm, b = 805.1(1) pm, c = 791.2(1) pm). The crystal structure determinations show that Te7NbOBr5 and Te7NbOCl5 are built of one-dimensional polymeric tellurium cations, one-dimensional associated pyramidal NbOX4 groups (X = Cl, Br) and isolated halide anions. Magnetic properties of Te7NbOX5 were determined and confirm the expected diamagnetism. Te7NbOX5 can thus be formulated as [Te72+] [NbOX4?] (X?). The charge distribution in the structure type Te7MOX5 (M = W, Nb; X = Cl, Br) became clear by synthesis and characterisation of the two niobium containing compounds. 相似文献
20.
Bis(tetramethylammonium) dodecahydrododecaborate, [(CH3)4N]2[B12H12], and bis(tetramethylammonium) dodecahydrododecaborate acetonitrile, [(CH3)4N]2[B12H12] · CH3CN, were synthesized and characterized via Infrared, 1H and 11B NMR spectroscopy. [(CH3)4N]2[B12H12] crystallizes isopunctual to the alkali metal dodecaborates. The crystal structure of [(CH3)4N]2[B12H12] · CH3CN was determined from single crystal data and refined in the orthorhombic crystal system (Pcmn, no. 62, a = 898.68(8), b = 1312.85(9) c = 1994.5(1) pm, R(|F| , 4σ) = 5.9%, wR(F2) = 18.3%). Here, the geometry of the dodecaborate anion is that of an almost ideal icosahedron, less distorted than most other dodecaborates known. By low‐temperature Guinier‐Simon diffractometry phase transitions were detected for [(CH3)4N]2[B12H12] and [(CH3)4N]2[B12H12] · CH3CN at –70 and –15 °C, respectively. 相似文献