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1.
Preparation of trans-[Mo6Cl8]Cl4Br22? Starting from Crystalline [Mo6Cl8]Cl4(H2O)2 and Crystal Structure of [(C6H5)4As]2[Mo6Cl8]Cl4Br2 The synthesis of the title compound is successful if the crystallized [(Mo6Cl8)Cl4(H2O)2] containing the H2O molecules in trans-position reacts with HBr + [(C6H5)4As]Br in ethanol in a heterogeneous reaction. The X-ray structure investigation confirms the existence of discrete trans-Br-substituted cluster anions of composition [(Mo6Cl8)Cl4Br2]2? in the crystal. The reaction in homogeneous solutions proceeds to Br-enriched compounds. [(C6H5)4As]2[(Mo6Cl8)Cl4Br2] crystallizes in the triclinic space group P¯1 with a = 11.071(2), b = 11.418(2), c = 12.813(2) Å, α = 116.10(2), β = 95.27(2) and γ = 94.41(2)° (?133°C). The crystal structure at ?133°C was determined from single crystal X-ray diffraction data (R1 = 0.026). The [(Mo6Cl8)Cl4Br2]2?-anions are not completely ordered but distributed statistically among the three positions which are possible within the limits of the ordered [Mo6Cl8]-cores (ratio 11:5:4). The frameworks of the anions consist of Mo6 cluster units with (slightly distorted) octahedral arrangement of the metal atoms (d(Mo? Mo): 2.600(1) up to 2.614(1) Å), which are coordinated by the halogeno ligands in a square-pyramidal manner. The details of the structure will be discussed and compared with similar [(Mo6X8)Y4] cluster units (X, Y ? Cl, Br). 相似文献
2.
Annette Kelley Subhash Akkina Goutham K. Devarapally Soujanya Nalla Divya Pasam Shravani Madhabushi Marcus R. Bond 《Acta Crystallographica. Section C, Structural Chemistry》2011,67(1):m22-m34
The structures of seven A2Cu4X10 compounds containing quasi‐planar oligomers are reported: bis(1,2,4‐trimethylpyridinium) hexa‐μ‐chlorido‐tetrachloridotetracuprate(II), (C8H12N)2[Cu4Cl10], (I), and the hexa‐μ‐bromido‐tetrabromidotetracuprate(II) salts of 1,2,4‐trimethylpyridinium, (C8H12N)2[Cu4Br10], (II), 3,4‐dimethylpyridinium, (C7H10N)2[Cu4Br10], (III), 2,3‐dimethylpyridinium, (C7H10N)2[Cu4Br10], (IV), 1‐methylpyridinium, (C6H8N)2[Cu4Br10], (V), trimethylphenylammonium, (C9H14N)2[Cu4Br10], (VI), and 2,4‐dimethylpyridinium, (C7H10N)2[Cu4Br10], (VII). The first four are isomorphous and contain stacks of tetracopper oligomers aggregated through semicoordinate Cu...X bond formation in a 4(,) stacking pattern. The 1‐methylpyridinium salt also contains oligomers stacked in a 4(,) pattern, but is isomorphous with the known chloride analog instead. The trimethylphenylammonium salt contains stacks of oligomers arranged in a 4(,) stacking pattern similar to the tetramethylphosphonium analog. These six structures feature inversion‐related organic cation pairs and hybrid oligomer/organic cation layers derived from the parent CuX2 structure. The 2,4‐dimethylpyridinium salt is isomorphous with the known (2‐amino‐4‐methylpyridinium)2Cu4Cl10 structure, in which isolated stacks of organic cations and of oligomers in a 4(,) pattern are found. In bis(3‐chloro‐1‐methylpyridinium) octa‐μ‐bromido‐tetrabromidopentacuprate(II), (C6H7ClN)[Cu5Br12], (VIII), containing the first reported fully halogenated quasi‐planar pentacopper oligomer, the oligomers stack in a 5(,) stacking pattern as the highest nuclearity [CunX2n+2]2− oligomer compound known with isolated stacking. Bis(2‐chloro‐1‐methylpyridinium) dodeca‐μ‐bromido‐tetrabromidoheptacuprate(II), (C6H7ClN)2[Cu7Br16], (IX), contains the second heptacopper oligomer reported and consists of layers of interleaved oligomer stacks with a 7[(,)][(−,−)] pattern isomorphous with that of the known 1,2‐dimethylpyridinium analog. All the oligomers reported here are inversion symmetric. 相似文献
3.
This work is part of our studies on the reactivity and crystal engineering of (1-diaminomethylene)thiourea (HATU). Structure and other properties of the selected products of the interaction of HATU with transition metal halides, also in the presence of 3% hydrogen peroxide as an oxidizing agent, have been investigated ((1) di-μ-((1-diaminomethylene)thiouron-1-ium)-κ4S:S-bis[chlorido((1-diaminomethylene)-thiouron-1-ium-κS)copper(I)] tetrachloride [(C2H7N4S)4CuI2Cl2]Cl4, (2) catena(bis(3,5-diamino-1,2,4-thiadiazol-2-ium)-bis(μ2-chlorido)-chloridocuprate(II)) [(C2H6N4S)2(Cu2Cl6)]∞, (3) 3,5-diamino-1,2,4-thiadiazol-2-ium pentachloridoferrate(III) (C2H6N4S)2[FeCl5], (4) 3,5-diamino-1,2,4-thiadiazol-2-ium chloride) (C2H6N4S)Cl, (5) 3,5-diamino-1,2,4-thiadiazol-2-ium tetrachloridozincate(II) (C2H7N4S)2[ZnCl4]. For (2) also magnetic properties have been characterized. Compound (3) contains unusual pentachloridoferrate(III) anions. 相似文献
4.
Bikshandarkoil R. Srinivasan Sunder N. Dhuri Ashish R. Naik 《Tetrahedron letters》2004,45(10):2247-2249
The recently reported sulfur transfer reagent benzyltriethylammonium tetracosathioheptamolybdate [(PhCH2)N(C2H5)3]6[Mo7S24] [Tetrahedron Lett. 2003, 44, 887] is correctly formulated as benzyltriethylammonium tetrathiomolybdate [(PhCH2)N(C2H5)3]2[MoS4]. The correct formulation explains the unusual sulfur transfer properties of [(PhCH2)N(C2H5)3]6[Mo7S24] observed in the earlier work. 相似文献
5.
The Ag(I) and Cu(I) complexes of 4-amino-3,5-dipentyl-4H-1,2,4-triazole (4-NH2-3,5-(C5H11)2tz) and 3,5-dipentyl-1H-1,2,4-triazole (3,5-(C5H11)2tzH) have been synthesized and characterized. X-Ray analysis shows that {Ag4[4-NH2-3,5-(C5H11)2tz]6}(BF4)4 is a tetranuclear complex featuring an Ag4tz6 cluster; {Ag[3,5-(C5H11)2tz]}n exhibits a 3D structure of lvt-a topology; and {Cu2[3,5-(C5H11)2tz]Br}n is a Cu4Br4-cluster based 3D complex with the dia topology. 相似文献
6.
Marija Vojnovi Draan Jozi Gerald Giester Berislav Peri Pavica Planini Nevenka Brni
evi 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(4):m219-m220
The novel title compound, [(CH3)4N]2[Ta6Br12(H2O)6]Br4·2H2O, with a [Ta6Br12]2+ cluster unit, has been prepared and structurally characterized. The compound crystallizes in space group C2/c, with a twofold axis passing through the cluster and the centre of symmetry located between the clusters. The nearest neighbouring cluster units are aligned along the crystallographic c axis, forming a one‐dimensional chain pattern. 相似文献
7.
《Journal of Coordination Chemistry》2012,65(3-4):299-306
Abstract The title compounds [MoOS3Cu3(Py)5Br] (3) and [MoOS3Cu3(Py)5I] (4) were obtained through the nest-shaped cluster [(n-Bu)4N]2[MoOS3Cu3BrCl2] (1) and twin-nest-shaped cluster [Et4N]4[Mo2Cu6S6O2Br2I4](2) by reacting with pyridine. They show nest-shaped skeletons, and are characterized structurally by single-crystal X-ray analysis. These are the first neutral nest-shaped Mo(W)-Cu(Ag)-S clusters. 相似文献
8.
《Polyhedron》1999,18(6):915-921
Unsaturated molecules such as nitriles are activated upon coordination to a dirhenium core. Acetonitrile is hydrolyzed in the presence of water to produce coordinated bridging acetamidate ligands as demonstrated by the reaction of [N(C4H9)4]2[Re2Cl8] with CH3CN and water in ethanol to form the acetamidate complexes, [N(C4H9)4][Re2Cl5(μ-CH3C(O)NH)(μ-CH3C(OH)N)]·3CH2Cl2 [I] and Re2Cl4(μ-CH3C(O)NH)(μ-dppm)2·4 CH2Cl2/0.833 EtOH [II]. Compound II is formed when I is reduced upon coordination of bis(diphenylphosphino)methane (dppm). Compounds I and II were characterized using X-ray crystallography and a variety of other spectroscopic methods. 相似文献
9.
Evgeny Goreshnik Dieter Schollmeier Marian Mys'kiv 《Acta Crystallographica. Section C, Structural Chemistry》2003,59(11):m478-m481
By using alternating‐current electrochemical synthesis, crystals of the CuIπ‐complexes bis(1‐allyl‐2‐aminopyridinium) di‐μ‐chloro‐bis[chlorocopper(I)], (C8H11N2)2[Cu2Cl4] or [H2NC5H4NC3H5][CuCl2], and bis(1‐allyl‐2‐aminopyridinium) di‐μ‐(chloro/bromo)‐bis[(chloro/bromo)copper(I)], (C8H11N2)2[Cu2Br2.2Cl1.8] or [H2NC5H4NC3H5][CuBr1.10Cl0.90], have been obtained and structurally investigated. In each of the isostructural (isomorphous) compounds, the distorted tetrahedral Cu environment involves three halide atoms and the C=C bond of the ligand. Both compounds reside on inversion centres, and the dimeric [Cu2X4·2H2NC5H4NC3H5] units are bonded into a three‐dimensional structure by N—H⋯X hydrogen bonds. The Br content in the terminal X1 position is much higher than that in the bridged X2 site. 相似文献
10.
A. Müller W. Eltzner S. Sarkar H. Bgge P. J. Aymonino N. Mohan U. Seyer P. Subramanian 《无机化学与普通化学杂志》1983,503(8):22-36
Preparation, Redox Properties, and Structures of Mononuclear ?Simple”? Mono-, and Dinitrosyl Complexes of Molybdenum with Hydroxylamido(?1), Oximato, Halogeno, and Pseudohalogeno Ligands The compounds [(C6H5)4P]2[Mo(NO)(H2NO)(NCS)4] 1 , [(C6H5)4P]2 [Mo(NO)((C2H5)2-CNO)(NCS)4] 2 , [(C6H5)4P]2[Mo(NO)2(NCS)4] · CH3OH, 3 [(C6H5)4P]3[Mo(NO)(CN)5] · 2H2O 4 , Cs2[Mo(NO)Cl4(H2O)] 5 and Cs2[Mo(NO)Cl5] 6 were prepared and characterized by complete X-ray structure analysis. All complexes have a nearly linear MoNO moiety, whereas in the anions of 1 and 2 a pentagonal-bipyramidal, in 3 — 6 an octahedral coordination sphere of Mo is present. Complexes with {MoNO}n configuration (n = 4, 5, 6) can be converted into each other by remarkable redox-reactions. Some novel reactions of the hydroxylamido(?1)-ligand (formation of 2 and 3 ) are discussed very shortly. 相似文献
11.
Lunyu Qu Ronghua Ma Yaguang Chen Yu Chen Chuntao Liu 《Journal of Thermal Analysis and Calorimetry》1995,45(1-2):275-287
The thermal properties of four heteropoly complexes α-K3H3[SiW11Ni(H2O)O39]·11.5H2O (I), α-K3H2[SiW11Fe(H2O)O39]·9H2O (II), α-[(C4H9)4N]3.5H1.5[SiW11Fe(H2O)O39]·4.5H2O (III) and α-[(C4H9)4N]3.5H2.5[SiW11Cu(H2O)O39]·6H2O (IV) were studied by means of TG, DTA and DSC. The activation energy and reaction order of the thermal decomposition reaction
of these complexes have been calculated.
Zusammenfassung Mittels TG, DTA und DSC wurden die thermischen Eigenschaften der vier heteropolaren Komplexe α-K3H3[SiW11Ni(H2O)O39]·11.5H2O (I), α-K3H2[SiW11Fe(H2O)O39]·9H2O (II), α-[(C4H9)4N]3.5H1,5[SiW11Fe(H2O)O39]·4.5H2O (III) und α-[(C4H9)4N]3.5H2,5 [SiW11Cu(H2O)O39]·6H2O (IV) untersucht. Die Aktivierungsenergie und Reaktionsordnung der thermischen Zersetzungsreaktion dieser Komplexe wurde berechnet.相似文献
12.
The synthesis, crystal and molecular structure of the first representatives of polynuclear technetium clusters are described. The composition of these clusters is: [Tc8Br4μ? Br8]Br. 2H2O; [H(H2O)2][Tc8Br4μ? Br8]Br; [H(H2O)2]2[Tc8Br4μ? Br8]Br2; [H3O(H2O)3]2[Tc6Br6μ3? Br5]; [(C4H9)4N]2[Tc6Br6μ3? Br5]; [H3O3]2[Tc6Br6μ3? Br5]. 4 H2O. It is shown that these clusters strongly differ in their structure from the known clusters of other d-elements. The crystal and molecular structure of hexabromotechetium acid (H3O)2TcBr6 is studied too. 相似文献
13.
Marija Vojnovi Draan Jozi Ivan Baic Sanda Ron
evi Pavica Planini 《Acta Crystallographica. Section C, Structural Chemistry》2004,60(1):m33-m34
The title compound, (C4H12N)4[Ta6Cl18]Cl, crystallizes in the cubic space group . The crystal structure contains two different types of coordination polyhedra, i.e. four tetrahedral [(CH3)4N]+ cations and one octahedral [(Ta6Cl12)Cl6]3− cluster anion, and one Cl− ion. The presence of three different kinds of Cl atoms [bridging (μ2), terminal and counter‐anion] in one molecule makes this substance unique in the chemistry of hexanuclear halide clusters of niobium and tantalum. The Ta6 octahedron has an ideal Oh symmetry, with a Ta—Ta interatomic distance of 2.9215 (7) Å. 相似文献
14.
《Electrochemistry communications》2003,5(5):378-382
The electrochemical behaviour of the copper-substituted Keggin-type and sandwich-type polyoxotungstate anions of the compounds α-[(C4H9)4N]4H[PW11CuIIO39] and α-B-[(C4H9)4N]7H3[CuII4(H2O)2(PW9O34)2] was studied by cyclic voltammetry in acetonitrile. In both cases two copper 1-electron reduction waves were detected in the cathodic scan. The first one was due to the reduction of one CuII to CuI in the polyoxoanion and the second one to the consecutive reduction of the preformed CuI to Cu0, with the consequent deposition/adsorption of the ejected metal atom at the glassy carbon electrode surface. In the anodic scan, Cu0 was re-oxidised with regeneration of the initial copper(II) complexes, via a CuI intermediate. The observed two-step reduction of copper(II) to copper(0) and the formation of intermediate species containing copper(I) is here reported for the first time for copper substituted polyoxotungstates. The co-ordination of the acetonitrile molecules to the copper ions must play a role in the formation of the copper(I) species, which are not detected in aqueous solution. 相似文献
15.
The compounds [C4H8ON(C3H5)2]+[Cu4Cl5]– (I), [C4H8ONH(C3H5)]+[CuBr2]– (II), and [C4H8ONH(C3H5)]+[CuBr1.41Cl0.59]– (III) were prepared for the first time by ac electrochemical synthesis from mono- and di-N-allyl derivatives of morpholinium and copper(I) halides in ethanol solution and structurally characterized. In the structure of I π-complex, the centrosymmetric Cu8Cl10 fragments are associated into layers perpendicular to the b axis. The N,N"-diallylmorpholinium cation functions as a bridge, which coordinates two copper atom of the adjacent inorganic fragments by both allyl groups. The trigonal-pyramidal surrounding of the Cu(I) atom, as well as the distorted tetrahedral coordination sphere of Cu(2), involves three chlorine atoms and the C=C bond, whereas the planar trigonal surrounding of the Cu(3) atom and trigonal-pyramidal surrounding of the Cu(4) atom involve only chlorine atoms. In the isostructural II and III σ-complexes, the edge-shared CuX4 tetrahedra form the infinite copper-halide chains running along the a axis. The inorganic fragments and organic N-allylmorpholinium cations are united into the three-dimensional crystal structures by N–H···X and C–H···X (X = Cl, Br) hydrogen bonds. 相似文献
16.
H. Binder R. Kellner K. Vaas M. Hein F. Baumann M. Wanner R. Winter W. Kaim W. Hnle Y. Grin U. Wedig M. Schultheiss R. K. Kremer H. G. von Schnering O. Groeger G. Engelhardt 《无机化学与普通化学杂志》1999,625(7):1059-1072
Halogenation of nido-B10H14 with C2H2Cl4, C2Cl6, Br2, or I2, produces by cluster degradation the (2 n)-closo-clusters B9X9 (X = Cl, Br, I). The synthesis of salts of the perhalogenated radical anions of the type (2 n + 1)-closo-[B9X9]· – and of the corresponding dianions (2 n + 2)-closo-[B9X9]2– from neutral B9X9 is described [n is the number of cluster atoms; (2 n), (2 n + 1), and (2 n + 2) is the number of cluster electrons]. Molecular and crystal structures of B9Cl9, B9Br9, [(C6H5)4P][B9Br9] · CH2Cl2, and [(C4H9)4N]2[B9Br9] · CH2Cl2 have been determined via X-ray diffraction. All three oxidation states of the cluster retain the tricapped trigonal prism. The reduction of the clusters B9X9 was shown by cyclic voltammetry in CH2Cl2 to proceed via two successive one-electron reversible steps, separated by at least 0.4 V. The paramagnetic radical anions [B9X9]· – (X = Cl, Br) were further characterized by magnetic susceptibility measurements of [Cp2Fe][B9X9] and [Cp2Co][B9X9], respectively. The EPR spectra of [B9X9]· – (X = Cl, Br, I) in glassy frozen CH2Cl2 solutions showed increasing g anisotropy for the heavier halogen derivatives, illustrating significant halogen participation at the singly occupied MO. The 11B NMR spectra of CD2Cl2 solutions of the neutral clusters B9X9 exhibit only one sharp resonance, indicating that the boron atoms are highly fluxional in solution. In contrast, two different boron resonances as expected for a rigid tricapped trigonal prism are clearly observed for the [B9X9]2– dianions in solutions and for solid B9Br9 in the 11B MAS NMR spectra. Temperature dependent 11B MAS NMR experiments on B9Br9 and [B9Br9]2– in the solid state show a reversible coalescence of the two resonances at higher temperature. 11B MAS NMR spectra and DTA measurements of [B9Br9]2– showed a phase transition. 相似文献
17.
A. V. Pavlyuk V. V. Kinzhibalo T. Lis M. G. Mys’kiv 《Russian Journal of Coordination Chemistry》2007,33(7):501-508
Crystals of the copper bromide complexes with N-allylisoquinolinium halides of the composition [C9H7N(C3H5)]2CuIICl2.86Br1.14 (I), [C9H7N(C3H5)]CuIBr2 · H2O (II), and [C9H7N(C3H5)]CuIBr2 (III) are prepared by ac electrochemical synthesis, and their structures are studied by X-ray diffraction analysis (DARCh-1 (for I) and KUMA/CCD (for II and III) diffractometers). The crystals of compound I are monoclinic: space group P21/n, a = 15.053(5) Å, b = 10.486(4) Å, c = 17.179(10) Å, γ = 109.77(3)°, V = 2552(4) Å3, Z = 4. The crystals of complex II are triclinic: space group P $\overline 1 $ , a = 7.040(1) Å, b = 7.610(2) Å, c = 12.460(2) Å, α = 79.54(3)°, β = 86.73(3)°, γ = 89.51(1)°, V = 655.4(2) Å3, Z = 2. The crystals of complex III are monoclinic: space group P21/n, a = 12.799(1) Å, b = 7.692(1) Å, c = 13.491(1) Å, β = 111.08(1)°, V = 1239.3(2) Å3, Z = 4. The structure of compound I is built of the CuIIX 4 2? tetrahedra and N-allylisoquinolinium cations united by the C-H···X contacts into corrugated layers. The crystal structure of π-complex II is formed of dimers of the composition [C9H7(C3H5)]2 Cu 2 I Br4 forming layers in the direction of the z axis due to the C-H···X contacts. An important role in structure formation belongs to water molecules that cross-link the organometallic layers through the O-H···X contacts into a three-dimensional framework. When kept in the mother liquor for 6 months, the crystals of compound II transformed into crystals of compound III, whose structure consists of {[C9H7(C3H5)]2Cu 2 I Br4} n columns united through the C-H···Br contacts (H···Br 2.84(3)?2.92(4) Å) into a three-dimensional framework. 相似文献
18.
A new dimorphic copper selenite bromide, Cu5(SeO3)4Br2 was obtained via chemical transport reactions. α-Cu5(SeO3)4Br2, monoclinic (1m) and β-Cu5(SeO3)4Br2, triclinic (1a) polymorphs were produced simultaneously upon reaction of amorphous, partially dehydrated copper selenite and copper bromide. 1m is similar to Cu5(SeO3)4Cl2, whereas 1a is distantly related to Ni5(SeO3)4Br2 and Co5(SeO3)4Br2. Attempts to reproduce synthesis of 1a via exchange reaction between Na2SeO3 and CuBr2 resulted in a new Na2[Cu7O2](SeO3)4Br4 (2). Current study demonstrates for the first time, that both chemical vapor and exchange reactions can be employed in preparation of new selenite halides. 相似文献
19.
Two benzene centered tri- and tetracyclopentadienyl ligands C6H3(CH2C5H5)3-1,3,5 (1) and C6H2(CH2C5H5)4-1,2,4,5 (2) and their titanium complexes C6H3[CH2C5H4Ti(C5H5)Cl2]3-1,3,5 (3), C6H3[CH2C5H4Ti(C5H4CH3)Cl2]3-1,3,5 (4), as well as C6H2[CH2C5H4Ti(C5H5)Cl2]4-1,2,4,5 (5) were synthesized and characterized by mass and 1H NMR spectra. In the presence of methylaluminoxane (MAO), 3, 4 and 5 are efficient catalysts for ethylene polymerization in toluene. The influence of the polymerization conditions such as catalyst concentration, MAO/Ti molar ratio, polymerization time and temperature were investigated in detail. 3, 4 and 5 produce linear polyethylene (PE) with broad molecular weight distributions (MWD) and a little lower molecular weight. 相似文献
20.
Wen-Hua Zhang Ke Li Qi Li Thomas C. W. Mak 《Journal of inclusion phenomena and macrocyclic chemistry》2012,74(1-4):353-359
In the crystal structure of [(n-C4H9)4N]+·[NH2(C2N2S)NHCOO?]·NH2CSNC(NH2)2 (1), guanylthiourea molecules and 1,3,5-thiadiazole-5-amido-2-carbamate ions are joined together by intermolecular N–H…O, N–H…N, and weak N–H…S hydrogen bonds to generate stacked host layers corresponding to the (110) family of planes, between which the tetra-n-butylammonium guest cations are orderly arranged in a sandwich-like manner. In the crystal structure of [(n-C3H7)4N]+·[NH2(C2N2S)NHCOO?]·NH2CSNC(NH2)2·H2O (2), the tetrapropyl ammonium cations are stacked within channels each composed of hydrogen bonded ribbons of guanylthiourea molecules, 1,3,5-thiadiazole-5-amido-2-carbamate ions and water molecules. 相似文献