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1.
Conformation and Cross Linking of (CuCN)6‐Rings in Polymeric Cyanocuprates(I) equation/tex2gif-stack-8.gif [Cu2(CN)3] (n = 2, 3) The alkaline‐tricyano‐dicuprates(I) Rbequation/tex2gif-stack-9.gif[Cu2(CN)3] · H2O ( 1 ) and Csequation/tex2gif-stack-10.gif[Cu2(CN)3] · H2O ( 2 ) were synthesized by hydrothermal reaction of CuCN and RbCN or CsCN. The dialkylammonium‐tricyano‐dicuprates(I) [NH2(Me)2]equation/tex2gif-stack-11.gif[Cu2(CN)3] ( 3 ), [NH2(iPr)2]equation/tex2gif-stack-12.gif[Cu2(CN)3] ( 4 ), [NH2(Pr)2]equation/tex2gif-stack-13.gif[Cu2(CN)3] ( 5 ) and [NH2(secBu)2]equation/tex2gif-stack-14.gif[Cu2(CN)3] ( 6 ) were obtained by the reaction of dimethylamine, diisopropylamine, dipropylamine or di‐sec‐butylamine with CuCN and NaCN in the presence of formic acid. The crystal structures of these compounds are built up by (CuCN)6‐rings with varying conformations, which are connected to layers ( 1 ) or three‐dimensional zeolite type cyanocuprate(I) frameworks, depending on the size and shape of the cations ( 2 to 6 ). Crystal structure data: 1 , monoclinic, P21/c, a = 12.021(3)Å, b = 8.396(2)Å, c = 7.483(2)Å, β = 95.853(5)°, V = 751.4(3)Å3, Z = 4, dc = 2.728 gcm—1, R1 = 0.036; 2 , orthorhombic, Pbca, a = 8.760(2)Å, b = 6.781(2)Å, c = 27.113(5)Å, V = 1610.5(5)Å3, Z = 8, dc = 2.937 gcm—1, R1 = 0.028; 3 , orthorhombic, Pna21, a = 13.504(3)Å, b = 7.445(2)Å, c = 8.206(2)Å, V = 825.0(3)Å3, Z = 4, dc = 2.023 gcm—1, R1 = 0.022; 4 , orthorhombic, Pbca, a = 12.848(6)Å, b = 13.370(7)Å, c = 13.967(7)Å, V = 2399(2)Å3, Z = 8, dc = 1.702 gcm—1, R1 = 0.022; 5 , monoclinic, P21/n, a = 8.079(3)Å, b = 14.550(5)Å, c = 11.012(4)Å, β = 99.282(8)°, V = 1277.6(8)Å3, Z = 4, dc = 1.598 gcm—1, R1 = 0.039; 6 , monoclinic, P21/c, a = 16.215(4)Å, b = 13.977(4)Å, c = 14.176(4)Å, β = 114.555(5)°, V = 2922(2)Å3, Z = 8, dc = 1.525 gcm—1, R1 = 0.070.  相似文献   

2.
Synthesis and Crystal Structure of [Cr(NH3)6][Cr(NH3)2F4][BF4]2 The action of ammonium fluoride on a mixture of boron and chromium in a sealed Monel ampoule at 300 °C yields single crystals of [Cr(NH3)6][Cr(NH3)2F4][BF4]2. The crystal structure (tetragonal, P4/mbm, Z = 2, a = 1056.0(1), c = 781.7(1) pm; R1 = 0.0414; wR2 = 0.1087 for 411 reflections with I0 > 2σ(I)) contains [Cr(NH3)6]3+ and [Cr(NH3)2F4] octahedra and twice as many [BF4] tetrahedra that are arranged in a quadrupled super‐structure of the CsCl‐type of structure.  相似文献   

3.
Synthesis and Crystal Structure of the Tetrameric Nitrido Complex [Cu(CH3CN)4]2[W4N4Cl14(CH3CN)2] . The title compound has been prepared by the reaction of CuCl with WNCl3 in acetonitrile solution, forming red, moisture sensitive crystals. They were characterized by IR spectroscopy and by an X-ray structure determination. Space group I2/a, Z = 4, 2 027 observed unique reflections, R = 0.049. Lattice dimensions at -80°C: a = 2 527.0, b = 971.9, c = 2 137.5 pm, β = 106.01°. The compound consists of [Cu(CH3CN)4]+ ions, which are arranged to form strands, and of anions [W4N4Cl14(CH3CN)2]2?, in which the tungsten atoms were located at the vertices of a square and are linked with one another via linear W?N? W bridges. Two of the four tungsten atoms have four chlorine atoms as terminal ligands, the other two tungsten atoms have three chlorine atoms and an acetonitrile molecule as terminal ligands.  相似文献   

4.
Hydrogen Diazide – Synthesis and Crystal Structure of PPh4[N3HN3] PPh4[N3HN3] has been prepared from PPh4N3 and Me3SiN3 by the reaction with water or ethanol forming colourless nonexplosive crystal needles, which were characterized by IR spectroscopy and by a crystal structure determination. Space group C2/c, Z = 12, lattice dimensions at –70 °C: a = 3782.4(3), b = 727.8(2), c = 2512.4(2) pm, β = 110.13(1)°, R = 0.0841. The [N3HN3] ion is characterized by an asymmetric N–H…N hydrogen bridge with a NN distance of 272(1) pm.  相似文献   

5.
Synthesis and Crystal Structure of [(n‐Bu)4N][W6Cl18] Single‐crystals of [(n‐Bu)4N][W6Cl18] were obtained as thin needles by adding methanol to a solution of W6Cl18 and [(n‐Bu)4N]Cl in tetrahydrofuran. The structure was determined by single‐crystal X‐ray diffraction at 210 K. [(n‐Bu)4N][W6Cl18] crystallizes in the monoclinic space group C 2/c with Z = 8 and the lattice parameters a = 2175.6(1) pm, b = 1738.0(1) pm, c = 2160.36(9) pm, and β = 91.680(5) °. The crystal structure contains isolated [(W6Cl12i)Cl6a] clusters and [(n‐Bu)4N]+ ions.  相似文献   

6.
Inhaltsübersicht. Die Titelverbindung entsteht neben CuN3 · PPh3 bei der Einwirkung von Natriumazid auf CuCl2 und Triphenylphosphan in siedendem Acetonitril bei Anwesenheit von 15-Krone-5 als Lösungsvermittler für NaN3. (Ph3PNPPh3)2[Cu(N3)4] bildet schwarze Kristalle, die wir durch das IR-Spektrum und durch eine röntgenographische Strukturanalyse charakterisiert haben. Raumgruppe Pbca, Z = 4, (4245 beobachtete unabhängige Reflexe, R = 7,2%), Gitter-abmessungen (20°C):a = 1980, 1;b = 1618,8; c = 2014,3 pm. Die Verbindung besteht aus Kationen [Ph3PNPPh3]+ und Anionen [Cu(N3)4]2– der Symmetrie Ci, in denen das Cu-Atom planar von den α-N-Atomen der Azidgruppen mit Cu–N-Abständen von 197,2(4) und 189,5(4) pm umgeben ist. Synthesis and Crystal Structure of (Ph3PNPPh3)2[Cu(N3)4] The title compound is prepared besides CuN3 · PPh3 by the reaction of sodium azide with CuCl2 and PPh3 in boiling acetonitrile in the presence of 15-crown-5. (Ph3PNPPh3)2[Cu(N3)4] forms black crystals, which have been characterized by their IR spectrum as well as by an X-ray structure determination. Space group Pbca, Z = 4 (4245 observed independent reflexions, R = 0.072), lattice dimensions (20°C): A = 1980.1; b = 1618.8; c = 2014.3 pm. The compound consists of Ph3PNPPh3+ cations and anions [Cu(N3)4]2– with symmetry C1, in which the copper atom is planarly surrounded by the four nitrogen atoms of the azide groups with bond lengths Cu–N of 197.2(4) and 189.5(4) pm, respectively.  相似文献   

7.
Halomercurates: Syntheses and Crystal Structures of [Cu(en)2][Hg2Cl6], [Cu(en)2][Hg2Br6], and [Cu(en)2][HgBr4] Crystals of [Cu(en)2][Hg2Cl6] ( 1 ) have been obtained by layering a solution of Hg(NO3)2 and NaCl with a solution of [Cu(en)2]SO4. An analogous procedure, using NaBr instead of NaCl, gave crystals of [Cu(en)2][HgBr4] ( 3 ). Crystals of [Cu(en)2][Hg2Br6] ( 2 ) were obtained by gel crystallization using the same starting materials as for 3 . The complexes show very low solubility. The dinuclear anions of 1 consist of two nearly planar HgCl3 units related by a center of symmetry. In 2 infinite anionic chains are present, made up of parallel HgBr3 units. These units are packed in such a way as to produce a trigonal bipyramidal configuration around the Hg atoms. 3 contains mononuclear deformed tetrahedral [HgBr4]2– anions. In all three complexes the packing of the ions is such that halogen atoms of halomercurate anions complete a tetragonal bipyramidal coordination at Cu. The resulting Cu–Halogen distances are 2.924 Å for 1 , 3.036 Å for 2 and 3.085 and 3.119 Å for 3 . 1 : Space group P 1, Z = 1, lattice constants at 20 °C: a = 7.000(2), b = 7.526(2), c = 8.239(2) Å; α = 88.39(2), β = 86.06(2), γ = 86.10(3)°; R1 = 0.040. 2 : Space group P21/c, Z = 2, lattice constants at –50 °C: a = 7.185(1), b = 16.338(2), c = 7.814(1) Å; β = 94.88(2)°; R1 = 0.033. 3 : Space group P21/n, Z = 4, lattice constants at 20 °C: a = 8.055(3), b = 13.101(3), c = 13.814(3) Å; β = 91.24(3)°; R1 = 0.092.  相似文献   

8.
Action of Ammonium Fluoride on Scandium: Synthesis and Crystal Structures of (NH4)3[ScF6] and [Cu(NH3)4]3[ScF6]2 The action of (NH4)F on scandium in copper ampoules yields either (NH4)3[ScF6] or ScF3 and a small quantity of [Cu(NH3)4]3[ScF6]2, respectively, depending upon the molar ratio of the educts (NH4)F : Sc (6 : 1 and 4 : 1, respectively) and temperature. (NH4)3[ScF6] crystallizes with the cryolite type of structure: monoclinic, P21/n, Z = 2; a = 650.0(2); b = 651.4(2); c = 949.0(2) pm; β = 90.40(2)°, [Cu(NH3)4]3[ScF6]2 is triclinic, P‐1, Z = 1; a = 821.1(2); b = 821.2(2); c = 822.7(2) pm; α = 90.04(3); β = 90.00(3); γ = 90.16(3)°. In its chemical behaviour against (NH4)F, scandium parallels aluminium rather than gallium.  相似文献   

9.
Synthesis and Crystal Structure of K2Mn3S4 Single crystals of K2Mn3S4 have been prepared by a fusion reaction of potassium carbonate with manganese in a stream of hydrogen sulfide at 900 °C. K2Mn3S4 crystallizes in a new monoclinic layered structure type (P2/c, a = 7.244(2) Å, b = 5.822(1) Å, c = 11.018(5) Å, β = 112.33(3)°, Z = 2) which can be described as a stacking variant of the orthorhombic Cs2Mn3S4 structure type. Measurements of the magnetic susceptibilities show antiferro‐magnetic interactions.  相似文献   

10.
Synthesis and Crystal Structure of [Fe(MeCN)6][Fe2OCl6] [Fe(MeCN)6][Fe2OCl6] ( 2 ) is obtained by passing dry air through a solution of FeCl2 in acetonitrile in almost quantitative yield. 2 crystallises in the trigonal space group R 3 [a = b = 12.121(1), c = 29.875(6) Å, Z = 6]. The oxygen atom in the Fe2OCl6 anion occupies the 3 position and causes therefore an Fe–O–Fe angle of 180°. The refinement in the triclinic space group P1 leads to a slightly bent arrangement of the Fe–O–Fe fragment.  相似文献   

11.
Synthesis and Spectroscopic Characterization of [Rh(SeCN)6]3– and trans ‐[Rh(CN)2(SeCN)4]3–, Crystal Structure of (Me4N)3[Rh(SeCN)6] Treatment of RhCl3 with KSeCN in acetone yields a mixture of selenocyanato‐rhodates(III), from which [Rh(SeCN)6]3– and trans‐[Rh(CN)2(SeCN)4]3– have been isolated by ion exchange chromatography on diethylaminoethyl cellulose. The X‐ray structure determination on a single crystal of (Me4N)3[Rh(SeCN)6] (trigonal, space group R3, a = 14.997(2), c = 24.437(3) Å, Z = 6) reveals, that the compound crystallizes isotypically to (Me4N)3[Ir(SCN)6]. The exclusively via Se coordinated selenocyanato ligands are bonded with the average Rh–Se distance of 2.490 Å and the Rh–Se–C angle of 104.6°. In the low temperature IR and Raman spectra the metal ligand stretching modes ν(RhSe) of (n‐Bu4N)3[Rh(SeCN)6] ( 1 ) and trans‐(n‐Bu4N)3[Rh(CN)2(SeCN)4] ( 2 ) are in the range of 170–250 cm–1. In 2 νas(CRhC) is observed at 479 cm–1. The vibrational spectra are assigned by normal coordinate analysis based on the molecular parameters of the X‐ray determination. The valence force constants are fd(RhSe) = 1.08 ( 1 ), 1.10 ( 2 ) and fd(RhC) = 3.14 mdyn/Å ( 2 ). fd(RhS) = 1.32 mdyn/Å is determined for [Rh(SCN)6]3–, which has not been calculated so far. The 103Rh NMR resonances are 2287 ( 1 ), 1680 ppm ( 2 ) and the 77Se NMR resonances are –32.7 ( 1 ) and –110.7 ppm ( 2 ). The Rh–C bonding of the cyano ligand in 2 is confirmed by a dublett in the 13C NMR spectrum at 136.3 ppm.  相似文献   

12.
Synthesis and Coordination of 2-Acetylimino-1,3-dimethylimidazoline. The Crystal Structure of [Cu4I4(C7H11N3O)2] 2-Acetylimino–1,3-dimethylimidazoline ( 2 , ImNAc) obtained from 1,3-dimethyl-2-iminoimidazoline ( 1 ) and acetyl chloride forms with CuI the stepped cubane type complex [Cu4I4(ImNAc)2] ( 3 ); the X-ray structure of 3 is reported.  相似文献   

13.
Preparation, Crystal Structure, and Magnetism of [(CH3)2NH2][NdCl4(H2O)2] The complex water containing chloride [(CH3)2NH2][NdCl4(H2O)2] was prepared for the first time and the crystal structure was determined by X‐ray methods from single crystals. The compound crystallizes in the orthorhombic space group Cmca (Z = 8) with a = 1793.5(2) pm, b = 936.6(2) pm and c = 1232.8(2) pm. The anionic part of the structure is built up by chains of edge connected [NdCl4/2Cl2(H2O)2] trigondodecahedra. In order to study the interactions between the neodymium cation and the ligands magnetic measurements were carried out. The magnetic data were interpreted by ligand field calculations applying the angular overlap model.  相似文献   

14.
Synthesis and Crystal Structure of [Ba(18-Crown-6)(DMF)4][Cd(Se4)2] The title compound has been prepared by the reaction of a DMF-solution of lithium polyselenide with BaSe2 and cadmium acetate in the presence of 18-crown-6, forming black crystals. The compound was characterized by IR spectroscopy and by an X-ray structure determination. Space group P2/a, Z = 4, 5392 observed unique reflections, R = 0.048. Lattice dimensions at ?90°C: a = 2021.9(12); b = 1019.8(6); c= 2270.8(14)pm, ß = 106.98(4)°. The structure consists of [Ba(18-crown-6)(DMF)4]2+ ions, in which the barium ions are coordinated by the six oxygen atoms of the crown ether molecule and by four oxygen atoms of the DMF molecules, and of [Cd(Se4)2]2? ions. The cadmium atoms are coordinated by two tetraselenide ions in a chelating fashion.  相似文献   

15.
Synthesis and Structure Investigations of Iodocuprates(I). XV Iodocuprate(I) with Solvated Cations: [Li(CH3CN)4] [Cu2I3] and [Mg{(CH3)2CO}6][Cu2I4] [Li(CH3CN)4][Cu2I3] 1 and [Mg((CH3)2CO)6][Cu2I4] 2 were prepared by reactions of CuI with LiI in acetonitrile and of CuI with MgI2 in acetone. 1 crystallizes orthorhombic, Pnma, a = 552.7(2), b = 1258.8(8), c = 2516(1) pm, z = 4. [Li(CH3CN)4]+ cations are located between rod packings of CuI4 tetrahedra double chains [(CuI2/2I2/4)2]? parallel to the axis. Short intermolecular anion/cation contacts were observed. The crystal structure of 2 (monoclinic, P21/n, a = 1840(2), b = 1059.2(2), c = 1879(2)pm, β = 112.94(4)°, z = 4) is built up by [Mg((CH3)2CO)6]2+ cations forming a simple hexagonal sphere packing. The binuclear anions [Cu2I4]2? occupy holes in the trigonal prismatic channels formed by the cations.  相似文献   

16.
Preparation and Crystal Structure of Diammin Magnesium Diazide Mg(NH3)2(N3)2 Diammin magnesium diazide was synthesized from Mg3N2 and NH4N3 in liquid ammonia and crystallized at 150 °C under autogenous atmosphere of HN3 and NH3 using sealed ampoules. Mg(NH3)2(N3)2 is a colorless, microcrystalline powder which can detonate above 180 °C. Caution, preparation and manipulation of Mg(NH3)2(N3)2 is very dangerous! The crystal structure was solved from powder data using the Patterson method and a Rietveld refinement was performed (Mg(NH3)2(N3)2, I 4/m, no. 87; a = 6.3519(1), c = 7.9176(2) Å; Z = 2, R(F2)= 0.1162). The crystal structure of Mg(NH3)2(N3)2 is related to that of SnF4. It consists of planes built up from corner sharing Mg(NH3)2(N3)4 octahedra connected equatorially over their four azide bridges with the ammonia ligands being in trans position. IR data were collected and interpreted in accordance with the structural data.  相似文献   

17.
Preparation, Crystal Structure, and Magnetism of [(CH3)2NH2][PrCl4(H2O)2] The complex water containing chloride [(CH3)2NH2][PrCl4(H2O)2] has been prepared for the first time and the crystal structure has been determined from single crystal X‐ray diffraction data. The compound crystallizes orthorhombically in the space group Cmca (Z = 8) with a = 1796.6(2) pm, b = 940.7(1) pm, and c = 1238.4(2) pm. The anionic part of the structure is built up by chains of edge‐connected trigondodecahedra [PrCl6(H2O)2]3– according to [PrCl4/2Cl2(H2O)2], which are held together by dimethylammonium cations ([(CH3)2NH2]+). In order to study the interactions between the praseodymium cation (Pr3+) and the ligands magnetic measurements were carried out. The magnetic data were interpreted by ligand field calculations applying the angular overlap model.  相似文献   

18.
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   

19.
Synthesis and Crystal Structure of (PPh4)3[Re2NCl10] The rhenium(V) nitrido complex (PPh4)3[Re2NCl10] ( 1 ) is obtained from the reaction of (PPh4)[ReNCl4] with 1, 3‐dioxan‐(2‐ylmethyl)diphenyl phosphine in CH2Cl2/CH3CN in form of orange red crystals with the composition 1 ·2CH2Cl2 crystallizing in the triclinic space group P1¯ with a = 1210.7(2), b = 1232.5(1), c = 2756.3(5) pm, α = 99.68(1)°, β = 100.24(1)°, γ = 98.59(1)° and Z = 2. The crystal structure contains two symmetry independent, centrosymmetrical complex anions [Re2NCl10]3‐ with a symmetrical nitrido bridge Re=N=Re and distances Re(1) ‐ N(1) = 181.34(5) and Re(2) ‐ N(2) = 181.51(4) pm.  相似文献   

20.
Synthesis and Crystal Structure of Cs3AuO2 Bright orange single crystals of Cs3AuO2, sensitive to moisture and atmosphere, are obtained by reacting CsAu with a 1 : 1 molar mixture of Cs2O and CsO2 (CsAu : Cs2O : CsO2 = 3 : 2 : 2) in sealed silver crucibles under argon atmosphere at 380 °C for a period of 6 days. The crystal structure (Pearsoncode mP72, P21/n, a = 1019.6(3), b = 1984.3(7), c = 1028.5(4) pm, β = 93.96(1)°, Z = 12, 2562 reflections mit Io > 2σ(I), R1 = 0.0662, wR2 = 0.1660) is characterized by the presence of dumb‐bell‐shaped [O–Au–O]‐moieties (d(Au–O) = 200,8(2) pm), a common feature of oxoaurates(I).  相似文献   

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