Synthesis of 2-D graphite-like and 3-D diamond-like silver(I) polymers with 1,3-imidazolidine-2-thione

Two metal–organic coordination polymers, [Ag₂(imdt)₃(OAc)₂] _n (1) (imdt = 1,3-imidazolidine-2-thione, OAc = CH₃COO^?) and [Ag(imdt)Cl] _n (2), were synthesized under similar conditions by using Et₃N (triethylamine) as buffering agent. X-ray diffraction shows that 1 crystallizes in the monoclinic system, C2 /c space group, a = 13.822(5) Å, b = 9.082(3) Å, c = 16.965(6) Å, V = 2114.2(14) ų, Z = 8, D _c = 2.012 g cm^?3. Compound 2 crystallizes in the orthorhombic system, P2₁2₁2₁ space group, a = 7.993(6) Å, b = 7.993(6) Å, c = 10.548(7) Å, V = 673.9(7) ų, Z = 4, D _c = 2.419 g cm^?3. Both 1 and 2 exhibit different architectures due to their different anions. Compound 1 shows a 2-D graphite-like network structure and 2 shows a 3-D diamond-like network structure.     

Versatility of heterocyclic thioamides in the construction of a trinuclear cluster [Cu3I3(dppe)3 (SC5H4NH)] and Cu(I) linear polymers {Cu6(SC5H4NH)6I6}n x 2nCH3CN and {Cu(I)6 (SC3H6N2)6X6}n (X = Br, I)

Reaction of copper(I) iodide with pyridine-2-thione (2-SC5H4NH) and 1,2-bis(diphenylphosphino)ethane (dppe) in a CH3CN-CHCl3 mixture yielded a triangular cluster, [Cu3I3(mu2-P,P-dppe)3 (eta1-SC5H4NH)], 1. Similar reaction with 2-SC5H4NH and a series of diphosphanes, Ph2P-X-Ph2P {X = -CH2- (dppm), -(CH2)3- (dppp), -(CH2)4- (dppb), -CH=CH- (dppen)}, gave a novel iodo-bridged hexanuclear Cu(I) linear polymer,{Cu6(mu3-SC5H4NH)4 (mu2-SC5H4NH)2 (I4)(mu-I)2-}n x 2nCH3CN, 2. Reactions of copper(I) iodide/copper(I) bromide with 1,3-imidazolidine-2-thione (SC3H6N2) in a CH3CN-CHCl3 mixture yielded hexanuclear Cu(I) linear chain polymers, [{Cu6(mu3-SC3H6N2)2 (mu2-SC3H6N2)4X2 (mu-X)4}n] (X = Br, 4; I, 5). In compound 1, two iodide atoms and one dppe form the dinuclear Cu(mu2-I)2 (mu2-dppe)Cu core, and two dppe ligands bridge this core with the third Cu(I) center coordinated to 2-SC5H4NH via the S atom. The chain polymer 2 has a centrosymmetric hexanuclear central core, Cu6S6I4 (mu-I)2--, formed by dimerization of six-membered trinuclear motifs, Cu3(mu2-SC3H6N2)3I3 via (mu3-S) bonding modes of the thione ligand, and has four terminal and two bridging iodine atoms in trans-orientations. Linear chains are separated by the nonbonded acetonitrile molecules. In 4 and 5, three copper(I) bromide or copper(I) iodide moieties and three SC3H6N2 ligands combined via bridging S donor atoms to form the six-membered trinuclear Cu3(mu2-SC3H6N2)3I3 cores which polymerized via S and X atoms in a side-on fashion to form linear chain polymers, [{Cu6(mu3-SC3H6N2)2 (mu2-SC3H6N2)4X2(mu-X)4}n]. The (mu3-S) modes of bonding of neutral heterocyclic thioamides are first examples, as are trinuclear cluster and linear polymers rare examples in copper chemistry.     

Construction of a novel copper(I) chain polymer of hexanuclear Cu6(2-SC5H4NH)6I6 cores with a new (mu 3-S) mode of bonding of pyridine-2-thione and of an unusual triangular Cu3I3(dppe)3(2-SC5H4NH) cluster

The reactions of copper(I) iodide with pyridine-2-thione (2-SC(5)H(4)NH) in the presence of a series of diphosphane ligands, Ph(2)P[bond]X[bond]Ph(2)P [X = [bond](CH(2))(m)[bond], m = 1(dppm), 2 (dppe), 3 (dppp), 4 (dppb); [bond]CH[double bond]CH[bond] (dppen)], yielded an iodo-bridged hexanuclear Cu(I) linear polymer, [Cu(6)(mu(3)-SC(5)H(4)NH)(4)(mu(2)-SC(5)H(4)NH)(2)(I(4))(mu-I)(2)-](n).2nCH(3)CN (1). A similar reaction with 1,2-bis(diphenylphosphino)ethane (dppe) and 2-SC(5)H(4)NH yielded a triangular cluster, Cu(3)I(3)(dppe)(3)(2-SC(5)H(4)NH), 2. In the chain polymer 1, three Cu(I) iodide and three 2-SC(5)H(4)NH ligands combined via bridging S donor atoms to form a boat-shaped trinuclear Cu(3)S(3)I(3) core, and two such cores combined in an inverse manner via four S-donor atoms (mu(3)-S) to form a centrosymmetric hexanuclear repeat unit, Cu(6)S(6)I(4)(mu-I)(2-), which finally formed the iodo-bridged infinite linear chain polymer 1. Linear chains are separated by the nonbonded acetonitrile molecules. Polymer 1 is the first such example of a linear chain formed by the hexanuclear Cu(6)S(6)I(6) core in copper chemistry as well as in metal-heterocyclic thioamide chemistry. In addition, it has the first mu(3)-S mode of neutral pyridine-2-thione ever reported. In the moiety Cu(3)I(3)(dppe)(3) of 2, two copper(I) centers are bridged by the iodide ligands forming a Cu(mu-I)(2)Cu core, while a third copper(I) center is terminally bonded to another iodide ligand. Polymer 2 is also rare, and the first triangular cluster of Cu(I) with an heterocyclic thioamide.     

From discrete [Y(DMF)8][Cu4(mu3-I)2(mu-I)3I2] ion pairs to extended [Y(DMF)6(H2O)2][Cu7(mu4-I)3(mu3-I)2(mu-I)4(I)]1infinity and [Y(DMF)6(H2O)3][Cu(I)7Cu(II)2(mu3-I)8(mu-I)6]2infinity arrays by H-bond templating in a confined solvent-free environment

An ionic heterometallic species [Y(DMF)(8)][Cu(4)(micro(3)-I)(2)(micro-I)(3)I(2)](1) was isolated from a solution of CuI, NH(4)I and YI(3)(Pr(i)OH)(4) in DMF-isopropoxyethanol, and was converted in a confined environment by progressive substitution of the DMF ligands with water molecules first into a 1D zig-zag structure [Y(DMF)(6)(H(2)O)(2)][Cu(7)(micro(4)-I)(3)(micro(3)-I)(2)(micro-I)(4)(I)](1infinity)(2) and finally into a 2D sheet [Y(DMF)(6)(H(2)O)(3)][Cu(I)(7)Cu(II)(2)(micro(3)-I)(8)(micro-I)(6)](2infinity)(3) by H-bond templating.     

Construction of new heteroselenometallic clusters: formation of crownlike [Et4N]4[(mu5-WSe4)(CuI)5(mu-I)2] and octahedral polymeric [(mu6-WSe4)Cu6I4(py)4]n from planar [Et4N]4[(mu4-WSe4)Cu4I6] with additional faces

The coplanar cluster compound [Et4N]4[(mu4-WSe4)Cu4I6] (1) was prepared from reaction of [Et4N]2[WSe4] with 4 equiv of CuI in N,N-dimethylformamide (DMF) solution in the presence of [Et(4)N]I. Treatment of 1 with pyridine (py) in dry MeCN gave the neutral cluster [(mu4-WSe4)Cu4(py)6I2] (2) in good yield. Recrystallization of 1 from py/i-PrOH resulted in the reorganization of the coplanar WSe4Cu4 core and the formation of a neutral polymeric cluster [(mu3-WOSe3)Cu3(py)3(mu-I)]n (3) containing a nest-shaped OWSe3Cu3 core and a terminal W=O bond. The interaction of cluster 1 with excess PPh3 in CH3Cl3 gave [(mu3-WSe4)Cu3(PPh3)3(mu3-I)] (4) which has a cubanelike SeWSe3Cu3I core. Treatment of 1 with 1 equiv of CuI in dimethyl sulfoxide (DMSO) yielded [Et4N]4[(mu5-WSe4)(CuI)5(mu-I)2] (5) which has a crown-like core structure. Treatment of 1 in DMF with 2 equiv of CuI in the presence of py resulted in the formation of a two-dimensional polymeric cluster, [(mu6-WSe4)Cu6I4(py)4]n (6), consisting of an octahedral WSe4Cu6 repeating unit. The solid-state structures of clusters 3, 5, and 6 have been further established by X-ray crystallography. The nonlinear optical properties of 6 have been also investigated. Cluster 6 was found to exhibit good photostability and a large optical limiting effect with the limiting threshold being ca. 0.3 J cm(-2).     

二维网状铜(Ⅱ)配位聚合物{Cu(μ2-C10H8N2O3)( μ2-C6H12N4)1/2}n的合成和晶体结构

The novel copper(Ⅱ) coordination polymer with 2-oxo-propionic acid benzoyl hydrazone and hexamethylenetetramine ligands, {Cu(μ₂-C₁₀H₈N₂O₃)( μ₂-C₆H₁₂N₄)_1/2}_n (C₁₀H₈N₂O₃^2- is the dinegative ion of 2-oxo-propionicacid benzoyl hydrazone), has been synthesized and characterized by elemental analysis and IR spectroscopy. The crystal structure was determined by single crystal X-ray diffraction analysis. The results show that the crystal of the title coordination polymer belongs to monoclinic space group C2/c, the cell parameters are as follows: a=1.787 5(2) nm, b=0.730 93(9) nm, c=2.038 2(2) nm, β=92.890(2)°, and V=2.659 6(5) nm³, Z=8, D_c=1.687 Mg·m^-3, μ(Mo Kα)=1.659 mm^-1, F(000)=1 384, R=0.031 1, wR=0.079 0 for 2 454 observed reflections (I>2σ(I)) out of 2887 unique reflections. In this copper(Ⅱ) coordination polymer, each copper(Ⅱ) ion is five-coordinated with a geometry of distorted square-pyramid. Two oxygen atoms of the carboxyl of each C₁₀H₈N₂O₃^2- acts as a bridge to bond two neighboring copper(Ⅱ) ions, leading to an infinite one-dimensional chainlike coordination polymer. Each chain is linked by coordinated hexamethylenetetramines with its neighbors to form an infinite two-dimensional network structure. CCDC: 255347.     

Chloro(N-ethyl-1,3-imidazolidine-2-thione)gold(I): Spectroscopic studies and x-ray structure

Summary Chloro(N-ethyl-1,3-imidazolidine-2-thione)gold(II) crystallizes in the triclinic space group P¯I with cell dimensions:a=7.213(2)Å,b=7.857(7)Å,c=9.056(3)Å, =108.54°, =100.06(3)°, =107.27(4)° and Z=2.,The structure was refined by a least squares method to a conventional R factor of 7.3%, using 2157 reflections. The metal atom is bonded through the sulfur atom of the ligand which is consistent with the¹³C n.m.r. spectra of the complexes in d₆-acetone. The structure of the complex and coordination around metal are compared with other linear gold(I) complexes.     

Bis(N-propyl-1,3-imidazolidine-2-thione)gold(I) chloride: Crystal and molecular structure

Summary The crystal and molecular structures of bis(N-propyl-1,3-imidazolidine-2-thione)gold(I) chloride, [(PrImt)₂Au]Cl, has been determined from three-dimensional x-ray intensity data collected on a CAD4 diffractometer. The compound crystallizes in the monoclinic space group P2₁/n witha=7.195(7),b=15.283(3),c=15.899(6) Å, =91.7(1) and Z = 4. Atomic parameters were refined by full-matrix least-squares methods to the R value of 6.2% for 2272 observed reflections. Gold(I) exhibits the usual linear coordination with S(1)-Au-S(10) angle of 177.7(1)°. The two [Prlmt] molecules are arranged intrans configuration which is attributed to the effects of intermolecular H-bonding between N-H and the halogen. The Au-S bond length is compared with the corresponding bond length in several known structures in order to evaluate thetrans influence of phosphorus, sulfur and chloride ligands on the Au-S bond.     

The crystal and molecular structure of chlorobis(N-ethyl-1 3-imidazolidine-2-thione)copper(I)

Summary The crystal structure of the title compound has been determined from x-ray diffractometer data by the heavy-atom method and refined anisotropically by least-squares calculations. Crystals are monoclinic, space groupP 2₁/c, with unit cell dimensions:a=7.321(1),b=14.622(2),c=14.827(2) Å,=92.95(2), Z=4. The finalR index is 4.6%. The copper coordination is trigonal, involving the sulphur atoms of twoN-ethyl-1,3-imidazolidine-2-thione molecules and one chlorine atom. The structure is held together by two intramolecular N-HCl hydrogen bonds and by normal van der Waals interactions.     

Synthesis of homoleptic tris(organo-chelate)iridium(III) complexes by spontaneous ortho-metallation of electronrich olefin-derived N,N′-diarylcarbene ligands and the X-ray structures of fac-[Ir{CN(C6H4Me-p) (CH2)2NC6H3Me-p}3] and mer-Ir{CN(C6H4Me-p)(CH2)2NC6H3Me-p}2 {CN(C6H4Me-p)(CH2)2NC6H4Me-p}Cl (a product of HCl cleavage)

Treatment of [{Ir(COD)(μ-Cl)}₂] with excess of the electron-rich olefin [$\text{CN(Ar)(CH}{}_2\text{)}{}_2\text{N}$Ar]₂ (abbreviated as (L^Ar)₂, Ar = C₆H₄Me-p or C₆H₄OMe-p) affords the ortho-metallated tricycle [$\text{Ir(L}{}^{\mathrm{A}}\text{r}$)₃], which for Ar = C₆H₄Me-p (Ia) with HCL yields [$\text{Ir(L}{}^{\mathrm{A}}\text{r}$)₂(L^Ar)]Cl (IV); X-ray data show that in IV there is an unexpectedly close Ir?C(o-aryl) contact (2;52(1) Å) involving the “free” L^Ar which compares with an IrC(o-aryl) distance of 2.09(3) Å in Ia or 2.07(3) Å in the ortho-metallated L^Ar ligand of complex IV.     

一个新的二维配位聚合物:{Cu_2[C_(10)H_8Cl_2NO_4]_2[C_(10)H_8N_2]_3}_n的合成及其晶体结构

采用铜(Ⅱ)盐和3,5-二氯水杨醛缩丝氨酸以及4,4′-联吡啶在乙醇水溶液中合成了具有二维层状的配位聚合物.通过元素分析、红外光谱对该配位聚合物进行了表征,并利用X射线单晶衍射仪对其结构进行了鉴定.晶体结构表明,该标题配合物属三斜方晶系,空间群C2/c,晶胞参数为a=2.711(3)nm,b=2.711(3)nm,c=4.977(5)nm;α=90.00°,β=90.00°,γ=120.00°,V=3.167 8 nm3,Z=18,Dc=1.173 g.cm-3,F(000)=11 448,μ=0.807 mm-1,R1=0.078 8,wR2=0.187 2.     

Synthesis of 3-cyano-3-ethoxycarbonyl-4-methyl-6-phenylpyridine-2(1H)-thione and its alkylation

The condensation of acetaldehyde with cyanothioacetamide and ethyl benzoylacetate in the presence of N-methylmorpholine leads to the formation of 3-cyano-5-ethoxycarbonyl-4-methyl-6-phenylpyridine-2(1H)-thione. Alkylation of the last afforded the corresponding substituted 2-alkythiopyridines.T. G. Shevchenko Lugansk State Pedagogical Institute, Lugansk 348011, Ukraine. N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences (RAN),Moscow 117913, Russia.Translated from Khimiya Geterotsklicheskh Soedinenii, No. 12, pp. 1645–1646, December, 1999.     

Synthesis and transformations of 6-amino-3,5-dicyano-4ethylpyridine-2(1H)-thione

The condensation of propionaldehyde with cyanothioacetamide gives 6-amino-3,5-dicyano-4-ethylpyridine-2(1H)-thione, which was used to obtain substituted 2-alkylthiopyridines, 2-ethylthio-6- ethylaminopyridine, and pyrazolo[3,4-b]pyridine.T. G. Shevchenko Lugansk State Pedagogical Institute, 348011 Lugansk. N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Science, 117913 Moscow. Translated from Khimiya Geterotsklicheskikh Soedinenii, No. 8, pp. 1094–1098, August, 1996. Original article submitted March 4, 1996; revision submitted July 1, 1996.     

Synthesis, Chemical Characterization, and Molecular Structure of Au8{Fe(CO)4}4(dppe)2 and Au6Cu2{Fe(CO)4}4(dppe)2

The new Au₈{Fe(CO)₄}₄(P^P)₂ and Au₆Cu₂{Fe(CO)₄}₄(P^P)₂ (P^P=dppm, dppe) neutral cluster compounds were isolated in good yields by condensation of the [Au₃{Fe(CO)₄}₂(P^P)]^- anions with Au(SEt₂)Cl and CuCl, respectively, and have been characterized by IR, NMR and microanalyses. The molecular structures of Au₈{Fe(CO)₄}₄(dppe)₂ and Au₆Cu₂{Fe(CO)₄}₄(dppe)₂ have been determined by X-ray diffraction studies. Both molecules adopt a stereogeometry of the heavy atoms consisting of a triangulated and corrugated ribbon twisted around the elongation direction. Contrary to the expectations the latter displays the two copper atoms in the sites of highest connectivity. This implies that site exchange between copper and gold occurs during the synthesis.     

Synthese von Kupfer- und Silberkomplexen mit fünfzähnigen N,S- und sechszähnigen N,O-Chelatliganden – Charakterisierung und Kristallstrukturen von {Cu2[C6H4(SO2)NC(O)]2(C5H5N)4}, {Cu2[C5H3N(CHNC6H4SCH3)2]2}(PF6)2 und {Ag[C5H3N(CHNC6H4SCH3)2]}PO2F2

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.     

Hydrothermal Synthesis and Crystal Structure of a Three-dimensional Compound {Mn（H2O）4（VO）2（PO4）2}n

1 INTRODUCTION Current research interest is focused on the designof structures built up from octahedral and tetrahedralbuilding blocks[1]. During the wide investigations intransition-metal phosphates for many years, a num-ber of new mixed transition-metal phosphates havebeen reported[2]. A great number of manganese phos-phates were largely discovered as minerals[1]. On theother hand, many vanadium phosphates have alsobeen prepared recently partly because of their poten-tial applications …