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1.
Solvothermal reactions of Cu2(OH)2CO3 with 1,3‐bis(pyridin‐4‐yl)propane (bpp) in the presence of aqueous ammonia in 4‐iodotoluene/CH3CN or 1,4‐diiodobenzene/CH3CN afforded two [Cu2I2]‐based coordination polymers, namely catena‐poly[[[di‐μ‐iodido‐dicopper(I)]‐bis[μ‐1,3‐bis(pyridin‐4‐yl)propane‐κ2N:N′]] p‐toluidine tetrasolvate], {[Cu2I2(C13H14N2)2]·4C7H9N}n, (I), and the analogous 1,4‐diiodobenzene monosolvate, {[Cu2I2(C13H14N2)2]·C6H4I2}n, (II). The [Cu2I2] unit of (I) lies on a centre of symmetry at the mid‐point of the two I atoms, while that of (II) has a twofold axis running through the I...I line. In (I) and (II), each Cu centre is tetrahedrally coordinated by two μ‐I and two N atoms from two different bpp ligands. Each rhomboid [Cu2I2] unit can be considered as a four‐connecting node linked to the symmetry‐related [Cu2I2] units via two pairs of bpp ligands to form a one‐dimensional double chain along the c axis. The dimensions of the [Cu2I2(bpp)2]2 rings in (I) and (II) are different, which may be due to the presence of different guest solvent molecules in the structures. In (I), one p‐toluidine molecule, derived from an Ullmann coupling reaction of 4‐iodotoluene with ammonia, interacts with the [Cu2I2] cluster fragment through N—H...I hydrogen bonds, while the two p‐toluidine molecules interact via N—H...N hydrogen bonds. In (II), two I atoms of each 1,4‐diiodobenzene molecule are linked to the I atoms of the [Cu2I2] fragments from a neighbouring chain via I...I secondary interactions.  相似文献   

2.
Synthesis and Crystal Structure of [Li(thf)4]2[Bi4I14(thf)2], [Li(thf)4]4[Bi5I19], and (Ph4P)4[Bi6I22] Solutions of BiI3 in THF or methanol react with MI (M = Li, Na) to form polynuclear iodo complexes of bismuth. The syntheses and results of X-ray structure analyses of compounds [Li(thf)4]2[Bi4I14(thf)2], [Li(thf)4]4[Bi5I19], [Na(thf)6]4[Bi6I22] and (Ph4P)4[Bi6I22] are described. The anions of these compounds consist of edge-sharing BiI6 and BiI5(thf) octahedra. The Bi atoms lie in a plane and are coordinated by bridging and terminal I atoms and by THF ligands in a distorted octahedral fashion. [Li(thf)4]2[Bi4I14(thf)2]: Space group P1 (No. 2), a = 1 159.9(6), b = 1 364.6(7), c = 1 426.5(7) pm, α = 114.05(3), β = 90.01(3), γ = 100.62(3)°. [Li(thf)4]4[Bi5I19]: Space group P21/n (No. 14), a = 1 653.0(9), b = 4 350(4), c = 1 836.3(13) pm, β = 114.70(4)°. [Na(thf)6]4[Bi6I22]: Space group P21/n (No. 14), a = 1 636.4(3), b = 2 926.7(7), c = 1 845.8(4) pm, β = 111.42(2)°. (Ph4P)4[Bi6I22]: Space group P1 (No. 2), a = 1 368.6(7), b = 1 508.1(9), c = 1 684.9(8) pm, α = 98.28(4), β = 95.13(4), γ = 109.48(4)°.  相似文献   

3.
Structurally Chemical Investigation of Monoammin Copper (I) Complexes : [CuNH3]2[Pt(CN)6], [CuNH3]2[Pt(CN)4] and Cu3[Co(CN)6] · 2NH3 The preparation and the properties of [CuNH3]2[Pt(CN)6], [CuNH3]2[Pt(CN)4] and Cu3[Co(CN)6] · 2NH3 are described. I.R. and Raman spectra have been recorded and assigned. According to X-ray powder diagrams, [CuNH3]2[Pt(CN)6] crystallizes in the trigonal space group D–P3 ml, a = 7.771, c = 5.988 Å, Z = 1. According to the spectroscopic and crystallographic data, it is concluded that the CuI ion is coordinated with one NH3 group and with the N atoms of the cyanometallate anions. The coordination number of the Cu+ is 4 in [CuNH3]2[Pt(CN)6] and 3 in [CuNH3]2[Pt(CN)4]. In the Cu3[Co(CN)6] · 2 NH3 complex two Cu atoms have the coordination number 2, the third Cu atom 4.  相似文献   

4.
Single crystals of two new modifications of [P(C6H5)4]2[Cu2I4] were obtained by reaction of granulated copper with iodine and [P(C6H5)4]I in dry acetone under nitrogen atmosphere. They crystallise monoclinically, space group P21/n (No. 14), a = 11.550(6), b = 7.236(2), c = 27.232(13) Å, β = 98.13(3)°, V = 2253(2) Å3, and Z = 2 ([P(C6H5)4]2[Cu2I4]-C), and space group Cc (No. 9), a = 17.133(5), b = 15.941(5), c = 18.762 (6) Å, β = 114.02(1)°, V = 4681(3) Å3, and Z = 4 ([P(C6H5)4]2[Cu2I4]-D), respectively. In these compounds the [CuI2]? anions form dimers di-μ-iodo-diiodocuprate(I), which are either planar ( C ) or folded ( D ).  相似文献   

5.
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   

6.
Syntheses and Crystal Structures of [Cu4(As4Ph4)2(PRR′2)4], [Cu14(AsPh)6(SCN)2(PEt2Ph)8], [Cu14(AsPh)6Cl2(PRR′2)8], [Cu12(AsPh)6(PPh3)6], [Cu10(AsPh)4Cl2(PMe3)8], [Cu12(AsSiMe3)6(PRR′2)6], and [Cu8(AsSiMe3)4(PtBu3)4] (R, R′ = Organic Groups) Through the reaction of CuSCN with AsPh(SiMe3)2 in the presence of tertiary phosphines the compounds [Cu4(As4Ph4)2(PRR′2)4] ( 1 – 3 ) ( 1 : R = R′ = nPr, 2 : R = R′ = Et; 3 : R = Me, R′ = nPr) and [Cu14(AsPh)6(SCN)2(PEt2Ph)8] ( 4 ) can be synthesised. Using CuCl instead of CuSCN results to the cluster complexes [Cu14(AsPh)6Cl2(PRR′2)8] ( 5–6 ) ( 5 : R = R′ = Et; 6 : R = Me, R′ = nPr), [Cu12(AsPh)6(PPh3)6] ( 7 ) and [Cu10(AsPh)4Cl2(PMe3)8] ( 8 ). Through reactions of CuOAc with As(SiMe3)3 in the presence of tertiary phosphines the compounds [Cu12(AsSiMe3)6(PRR′2)6] ( 9 – 11 ) ( 9 : R = R′ = Et; 10 : R = Ph, R′ = Et; 11 : R = Et, R′ = Ph) and [Cu8(AsSiMe3)4(PtBu3)4] ( 12 ) can be obtained. In each case the products were characterised by single‐crystal‐X‐ray‐structure‐analyses. As the main structure element 1 – 3 each have two As4Ph42–‐chains as ligands. In contrast 4 – 12 contain discrete AsR2–ligands.  相似文献   

7.
《Mendeleev Communications》2021,31(6):804-806
The reaction of CuI and 3,6-bis(diphenylphosphino)pyridazine (dppz) in MeCN leads to the wheel-shaped complex [Cu8I8(dppz)6], assembled from four [Cu2I2] units and six dppz ligands. This complex exhibits thermochromic luminescence with emission colors ranging from red (300 K) to deep red (77 K). When carried out in the presence of PPh3, the reaction of CuI with dppz gives a non-emissive cage-like complex [Cu2I2(dppz)3], in which two CuI units are P,P′-bridged by three dppz ligands.  相似文献   

8.
Syntheses and Crystal Structures of new Selenido‐ and Selenolato‐bridged Copper Clusters: [Cu38Se13(SePh)12(dppb)6] (1), [Cu(dppp)2][Cu25Se4(SePh)18(dppp)2] (2), [Cu36Se5(SePh)26(dppa)4] (3), [Cu58Se16(SePh)24(dppa)6] (4), and [Cu3(SeMes)3(dppm)] (5) The reactions of copper(I) chloride or copper(I) acetate with monodentate phosphine ligands (PR3; R = organic group) and Se(SiMe3)2 have already lead to the formation of CuSe clusters with up to 146 copper and 73 selenium atoms. If the starting materials and the bidentate phosphine ligands (Ph2P–(CH2)n–PPh2, n = 1: dppm, n = 3: dppp, n = 4: dppb; Ph2P–C≡C–PPh2: dppa) and silylated chalcogen derivates are changed (RSeSiMe3; R = Ph, Mes) a series of new CuSe clusters can be synthesized. From single crystal X‐ray structure analysis one can characterise [Cu38Se13(SePh)12(dppb)6] ( 1 ), [Cu(dppp)2] · [Cu25Se4(SePh)18(dppp)2] ( 2 ), [Cu36Se5(SePh)26(dppa)4] ( 3 ), [Cu58Se16(SePh)24(dppa)6] ( 4 ) and [Cu3(SeMes)3(dppm)] ( 5 ). In this new class of CuSe clusters, compounds 1 and 4 possess a spherical cluster skeleton, wheras 2 and 3 have a layered cluster core.  相似文献   

9.
The title compound, {[Cu(NH3)4][Cu(CN)3]2}n, features a CuI–CuII mixed‐valence CuCN framework based on {[Cu2(CN)3]}n anionic layers and [Cu(NH3)4]2+ cations. The asymmetric unit contains two different CuI ions and one CuII ion which lies on a centre of inversion. Each CuI ion is coordinated to three cyanide ligands with a distorted trigonal–planar geometry, while the CuII ion is ligated by four ammine ligands, with a distorted square‐planar coordination geometry. The interlinkage between CuI ions and cyanide bridges produces a honeycomb‐like {[Cu2(CN)3]}n anionic layer containing 18‐membered planar [Cu(CN)]6 metallocycles. A [Cu(NH3)4]2+ cation fills each metallocyclic cavity within pairs of exactly superimposed {[Cu2(CN)3]}n anionic layers, but there are no cations between the layers of adjacent pairs, which are offset. Pairs of N—H...N hydrogen‐bonding interactions link the N—H groups of the ammine ligands to the N atoms of cyanide ligands.  相似文献   

10.
The complexes [Cu2Br4]2?, [Cu2I4]2?, [Cu2I2Br2]2?, [Cu2I3Cl]2?, [Ag2Cl4]2? have been characterized as their isomorphous bis(triphenylphosphoranylidene)ammonium ([Ph3PNPPh3]+ = PNP+) salts by single crystal structural determinations. All anions show the centrosymmetric doubly halogen‐bridged forms [XM(μ‐X)2MX]2? with three‐coordinate metal atoms that have been observed in [M2X4]2? complexes with other large organic cations. In [Cu2I2Br2]2? the iodide ligands occupy the bridging positions and the bromide the terminal positions, while in [Cu2I3Cl]2?, obtained in an attempt to prepare [Cu2I2Cl2]2?, two of the iodide ligands occupy the bridging positions with the third iodide and the chloride ligand occupying two statistically disordered terminal positions. In [Ag2Cl4]2? the distortion from ideal trigonal coordination of the metal atom is greater than in the copper complexes, but less than in other previously reported [Ag2Cl4]2? complexes with organic cations. The ν(MX) bands have been assigned in the far‐IR spectra, and confirm previous observations regarding the unexpectedly simple IR spectra of [Cu2X4]2? complexes.  相似文献   

11.
Novel [2n]thiacalixarenepyrazine and [2n]thiacalixarenetriazine systems were synthesised by one-pot SNAr reactions. A screening of the metal-complexing ability of [26]hexathiacalix[3]arene[3]pyrazine revealed its affinity for CuI, CuII and AgI metal salts.  相似文献   

12.
前驱团簇[Et4N]4[MS4Cu4I6](M=Mo (1a); W (1b))与双齿桥连配体1, 2-双(4-吡啶基)乙烷(bpe)在苯胺溶液中反应, 生成2个结构相似的一维[MS4Cu4]团簇基配位聚合物{[MS4Cu4(bpe)2(ani)2I2]·3.5ani}n (M=Mo (2), W (3); ani=苯胺)。通过元素分析、红外光谱和X-射线单晶衍射对23进行了表征。晶体结构分析表明前驱团簇1a1b中五核马鞍形[MS4Cu4]簇核分别在23中得以保留, 2个桥连配体bpe连接相邻的簇核, 在[111]方向延伸形成一维“Z”字形链结构。  相似文献   

13.
Crystal Structures of trans ‐[NiBr2(pyridine)4] and [Ni(HNPEt3)4]I2 Turquoise single crystals of trans‐[NiBr2(pyridine)4] have been obtained by the reaction of excess pyridine with nickel(II) bromide/diacetonealcohol. According to the crystal structure determination the nickel atom is octahedrally coordinated by the two bromine atoms in trans‐position and by the nitrogen atoms of the pyridine molecules. Space group Pna21, Z = 4, lattice dimensions at 20 °C: a = 1592.9(2), b = 943.8(1), c = 1413.0(2) pm, R1 = 0.0492. Dark blue single crystals of the phosphoraneimine complex [Ni(HNPEt3)4]I2 have been obtained from NiI2/H2O with excess Me3SiNPEt3 and subsequent recrystallization from acetonitrile. According to the crystal structure determination the nickel atom is tetrahedrally coordinated by the nitrogen atoms of the HNPEt3 molecules. The iodide ions are connected via N–H…I contacts with the cation to form an ion triple. Space group P21/c, Z = 4, lattice dimensions at –80 °C: a = 1934.9(2), b = 1078.3(1), c = 1966.3(2) pm, β = 111.040(8)°; R1 = 0.043.  相似文献   

14.
Synthesis and Crystal Structure of [N(Hex)4] [Cu2(CN)3] [N(Hex)4][Cu2(CN)3] has been prepared by solvothermal reaction of CuCN with Tetra‐n‐hexylammoniumiodide in acetone. The crystal structure is built up by condensed (CuCN)6 and (CuCN)7 rings, forming a zeolith type cyanocuprate(I) framework [Cu2(CN)3]. Space group R3; α = 44.482(6), c = 21.283(4) Å, V = 36471(9) Å3; Z = 9.  相似文献   

15.
Single crystals of [Zn(NH3)4]3[Mo4Te4(CN)12] (I) and [Cd(NH3)4]3[W4Te4(CN)12] (II) were obtained by applying solutions of K7[Mo4Te4(CN)12] · 11H2O and K6[W4Te4(CN)12] · 5H2O in aqueous ammonia over solutions of ZnCl2 and Cd(NO3)2 in glycerol and were characterized by X-ray diffraction analysis. The IR spectra and thermal properties of compounds I and II were examined.  相似文献   

16.
前驱团簇[Et4N]4[MS4Cu4I6](M=Mo(1a);W(1b))与双齿桥连配体1,2-双(4-吡啶基)乙烷(bpe)在苯胺溶液中反应,生成2个结构相似的一维[MS4Cu4]团簇基配位聚合物{[MS4Cu4(bpe)2(ani)2I2]·3.5ani}n(M=Mo(2),W(3);ani=苯胺)。通过元素分析、红外光谱和X-射线单晶衍射对23进行了表征。晶体结构分析表明前驱团簇1a1b中五核马鞍形[MS4Cu4]簇核分别在23中得以保留,2个桥连配体bpe连接相邻的簇核,在[111]方向延伸形成一维"Z"字形链结构。  相似文献   

17.
On the Constitution of Cs2[FeO4] For the first time black, spherical single crystals of Cs2[FeO4] were prepared by an “oxydative exchange reaction” of NaFeO2 with CsO1,8 (molar ratio Fe:Cs = 1.00:2.10, Au-tube, 250°C 3d, 480°C 24d, 360°C 5d): Spacegroup Pnma with a = 842.86(12) pm, b = 628.12(10) pm, c = 1105.33(17) pm. Cs2[FeO4] is isotypic to β-K2SO4. The structure was determined by four circle diffractometer data [MoKα , 1384 of 1387 Io(hkl), R = 3.36%, Rw = 3.08%]; parameters as given in the text. The Madelung Part of Lattice Energy, MAPLE, Effective Coordination Numbers, ECoN, these via Mean Fictive Ionic Radii, MEFIR, and the Charge-distribution will be calculated and discussed.  相似文献   

18.
Iodoplumbates with Polymeric Anions – Synthesis and Crystal Structures of [Na3(OCMe2)12][Pb4I11(OCMe2)], (Ph4P)2[Pb5I12], and (Ph4P)4[Pb15I34(dmf)6] Reactions of PbI2 with NaI in polar organic solvents followed by crystallization with large cations yield iodoplumbate complexes with various compositions and structures. [Na3(OCMe2)12][Pb4I11(OCMe2)] 3 , (Ph4P)2[Pb5I12] 4 and (Ph4P)4[Pb15I34(dmf)6] 7 contain one-dimensional infinite anionic chains of face- or edge-sharing PbI6 or PbI5L (L = acetone, DMF) octahedra. [Na3(OCMe2)12][Pb4I11(OCMe2)] 3 : Space group P1 (No. 1), a = 1120.3(5), b = 1265.3(6), c = 1608.3(8) pm, α = 74.64(4), β = 70.40(4), γ = 85.24(4)°, V = 2071(2) · 106 pm3; (Ph4P)2[Pb5I12] 4 : Space group C2/c (No. 15), a = 787.00(10), b = 2812.0(5), c = 3115.9(5) pm, β = 96.240(13)°, V = 6885(2) · 106 pm3; (Ph4P)4[Pb15I34(dmf)6] 7 : Space group P21/n (No. 14), a = 2278.8(4), b = 1782.6(3), c = 2616.8(4) pm, β = 114.432(13)°, V = 9678(3) · 106 pm3.  相似文献   

19.
Syntheses and Structures of [Cu20Ga10Cl4Se23(PEt2Ph)12] and [Cu14In6Se7(iPrSe)18] CuCl and GaCl3 react with Se(SiMe3)2 in thf solution to yield in the presence of PEt2Ph [Cu20Ga10Cl4Se23(PEt2Ph)12] ( 1 ). Reaction of CuCl, InCl3 and TMEDA with iPrSeSiMe3 in DME results in the crystallisation of [Cu14In6Se7(iPrSe)18] ( 2 ). The structures of 1 and 2 were determined by X‐ray single crystal structure analysis and display two new types of molecular clusters formed by the elements of group 11, 13, and 16. However, both cluster structures show no analogy to the structures of the related bulk phases.  相似文献   

20.
The reaction of CuCl, LiAs(SiMe3)2 and dppb (Bis(diphenylphosphino)butane) leads to the formation of ionic cluster complexes. Depending on the reaction conditions one can isolate [Cu8As3(AsSiMe3)2(dppb)4]+[Cu{As2(SiMe3)2}{As4(SiMe3)4}] ( 1 ) and [Cu8As3(AsSiMe3)2(dppb)4]+[Cu{As(SiMe3)2}2] ( 2 ). The same reaction of CuCl, dppm (Bis(diphenylphosphino)methane) and LiSb(SiMe3)2 leads to the neutral cluster complex [Cu10(Sb3)2(SbSiMe3)2(dppm)6] ( 3 ). The structures of 1‐3 have been solved by X‐ray single crystal analyses.  相似文献   

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