Synthesis and crystal structure of an organic semiconductor (ET)4[Hg2I6]

A new cation-radical salt (ET)₄[Hg₂I₆] (1), where ET is bis(ethylenedithio)tetrathiafulvalene, has been synthesized in the system ET-HgI₃ ^–-PhCl. An X-ray study of 1 (a=41.02(5),b=23.01(1),c=8.233(2) Å,V=7772(3) ų, space groupPc2₁ b,Z=4,d _calc=2.308 g cm^–3) has established its composition, chemical formula, and the main structural features. The ET cation-radicals are packed in the conducting layer, the type of packing is ; the [Hg₂I₆]^2– anion has a dimeric structure. The temperature dependence of the conductivity of the (ET)₄[Hg₂I₆] crystals (₃₀₀=6 Ohm^–1 cm^–1) has a semiconducting character.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1240–1244, July, 1994.We thank M. G. Kaplunov for his participation in the discussion of the obtained results.This work was financially supported by the Scientific Council on the Problems of High-Temperature Superconductivity (Grant No. 90346 Metallorg) and the Russian Foundation for Basic Research (Project No. 93-02-2384).     

Crystal structure of the organic metal (ET)2[Hg(SCN)2Cl] withT M-D=50 K

The composition and structure of the radical-ion salt (ET) ₂ [Hg(SCN) ₂ Cl], a new organic metal withT _M-D=50 K, were established in an x-ray structure investigation. Principal crystallographic data:a=36.69(1),b=8.302(8),c=11.732(8) Å, =90.02(6)°, space groupCc, Z=4,d _calc=2.08 g/cm ³ ,R=0.067. The crystal structure of the salt consists of an alternation of organic (cationic) and inorganic (anionic) layers along the axisa. The anionic layer consists of the polymeric chains in which the [Hg(SCN) ₂ Cl]^– ions are linked together along the axisc through secondary Hg···N bonds with lengths of 2.75(3) and 2.98(8) Å. On account of these interactions the trigonal configuration of the bonds of the Hg atom is built up to trigonal-bipyramidal. In the organic layer with a structure of the type the ET cations form dimers with an interplanar distance of 3.53 Å. ET cations belonging to neighboring dimers are linked together through shortened intermolecular S...S contacts with lengths of 3.40–3.50(2) Å.Institute of Chemical Physics, Russian Academy of Sciences, Chernogolovka 142432. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 4, pp. 903–909, April, 1992.     

Crystal structures of the organic metals (ET)2[Hg(SCN)Cl2] and (ET)2[Hg(SCN)2Br]

The compositions and structures of two new organic metals based on ET [where ET = bis(ethylenedithio)tetrathiafulvalene], viz., (ET)₂[Hg(SCN)Cl₂], with a metal-dielectric transition temperature (T_m-d) of 35°K, and (ET)₂[Hg(SCN)₂Br], with T_m-d = 140°K, were established by x-ray diffraction analysis. The crystal structures of the investigated compounds are similar to the structure of the previously studied organic metal (ET)₂[Hg(SCN)₂Cl] with T_m-d = 50°K. The principal crystallographic data for (ET)₂[Hg(SCN)Cl₂] are as follows: a = 36.64(1), b = 8.300(4), c = 11.798(1) Å, = 89.91(3)°, V = 3588.1(9) ų, space group Cc, Z = 4, d_calc = 2.05 g/cm³. The principal crystallographic data for (ET)₂[Hg(SCN)₂Br] are as follows: a = 37.088(14), b = 8.338(3), c = 11.738(5) Å, = 89.71(3)°, V = 3629.6(8) ų, space group C2/c, Z = 8, d_calc = 2.15 g/cm³. A characteristic feature of the crystal structure of the investigated compounds is alternation of the anion and cation layers along the a axis of the crystal. In the cation layer of the k type the ET are interconnected by shortened S...S intermolecular contacts (3.39–3.58 Å). The [Hg(SCN)_3–nX_n]^– anions (X = Cl, Br; n = 1, 2) form polymeric chains with one or two bridged SCN groups. A tendency for a decrease in the metal-dielectric transition temperature with a decrease in the volume of the anion is detected in the (ET)₂[Hg(SCN)_3–nX_n] salts, where X = Cl and Br, and n = 1 and 2.Institute of Chemical Physics, Russian Academy of Sciences, 142432 Chernogolovka. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 10, pp. 2323–2331, October, 1992.     

Crystal and molecular structure of organic semiconductor (ET)8[Hg4Cl12] · 2C6H6

A new organic semiconductor, (ET)₈[Hg₄C1₁₂] · 2C6H6, obtained in the ET⁺-HgCl ₃ ^– -PhF system has been studied by X-ray structural analysis. Radical cations of bis(ethylenedithio)tctrathiafulvalene (ET) in the organic layer of the structure are packed in stacks ofa-type. The average angle between the planes of ET cations from adjacent stacks is 50.1°. The anionic layer is formed by four-charge centrosymmetric [Hg₄Cl₁₂]^4– complexes and benzene solvate molecules. A comparative crystal-chemical study of the salts obtained by the reaction in the ET⁺-HgX ₃ ^– -PhY system (where X = Cl, Br, and I; Y = F, Cl, and Br) made it possible to reveal a substantial effect of the sizes of the X and Y atoms on the composition of the salts and on the structural characteristics of the layers, which are responsible for the various conductivities of these salts.Translated from Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 386–391, February, 1996     

New packing type of the conducting layer in the structure of the organic semiconductor (ET)6[Pb3Br9PhClMe2CO], the first ET-based lead-containing salt

A new organic semiconductor, (ET)₆[Pb₃Br₉PhClMe₂CO], which is the first radical cation salt based on bis(ethylenedithio)tetrathiafulvalene (ET) with a lead-containing anion, has been synthesized. The composition and crystal and molecular structure of this compound have been established by X-ray structural analysis. The crystal structure can be described as a layer structure. A new type of packing of ET radical cations has been found in the conducting layer. The anionic layer consists of [Pb₃Br₉ ^3–] _n polymeric anions and chlorobenzene and acetone solvate molecules bonded to polymeric anions through Br...H-C hydrogen bonds.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 910–916, May, 1995.This work was financially supported by the International Science Foundation (Grant RE1 000), the Scientific Council on the Problems of High-Temperature Superconductivity (Project No. 93030), and the Russian Foundation for Basic Research (Project No. 94-03-09950).     

双2-乙酰基二茂铁合汞的合成及其晶体结构

标题化合物(C24H22Fe2HgO2)3是由2 氯汞基 1 乙酰基二茂铁与乙二胺反应得到的,其结构通过单晶X 射线衍射法确定。其晶体属三斜晶系,P 1空间群,Mr=1964 12,a=10 193(2),b=11 504(2),c=14 413(3) ,α=92 21(3),β=104 12(3),γ=102 67(3)°,V=1591 55(5) 3,Z=1,Dc=2 049mg/cm3,μ=8 583mm-1,F(000)=942,最终偏离因子为R=0 0859,wR=0 2617。该晶体中同时含有meso型及dl型分子,各分子中Hg原子的配位情况不一样。meso分子中的两个二茂铁是相互平行的,而另两分子dl型的二茂铁是相互垂直的。Hg原子以桥联形式连接两个二茂铁部分。meso型与dl型分子通过Hg O弱配位作用相连。     

Heterobimetallic thiocyanato-bridged coordination polymers based on [Hg(SCN)4]: Synthesis, crystal structure, magnetic properties and ESR studies

Three new M/Hg bimetallic thiocyanato-bridged coordination polymers; [Hg(SCN)₄Ni(Im)₃]_∞1, [Hg(SCN)₄Mn(Im)₂]_∞2, and [Hg(SCN)₄Cu(Me-Im)₂ Hg(SCN)₄Cu(Me-Im)₄]_∞3, (Im=imidazole, Me-Im=N-methyl-imidazole), have been synthesized and characterized by means of elemental analysis, ESR, and single-crystal X-ray. X-ray diffraction analysis reveals that these three complexes all form 3D network structure, and their structures all contain a thiocyanato-bridged Hg?M?Hg chain (M=Mn, Ni, Cu) in which the metal and mercury centers exhibit different coordination environments. In complex 1, the [Hg(SCN)₄]²⁻ anion connects three [Ni(Im)₃]²⁺ using three SCN ligands giving rise to a 3D structure, and in complex 2, four SCN ligands bridge [Hg(SCN)₄]²⁻ and [Mn(Im)₂]²⁺ to form a 3D structure. The structure of 3 contains two copper atoms with distinct coordination environment; one is coordinated by four N-methyl-imidazole ligands and two axially elongated SCN groups, and another by four SCN groups (two elongated) and two N-methyl-imidazole ligands. The magnetic property of complex 1 has been investigated. The spin state structure in hetermetallic NiHgNi systems of complex 1 is irregular. The ESR spectra results of complex 3 demonstrate Cu²⁺ ion lie on octahedral environment.     

Synthesis and crystal structure of the octahedral cluster complex [Th(DMSO)8Cl][Re6Se7Cl7]

A cluster complex of the composition [Th(DMSO)₈Cl][Re₆Se₇Cl₇] has been obtained by interaction of ThCl₄ solution in DMSO with a water solution of K₃[Re₆Se₇Cl₇] and KCl. The compound crystallizes in the rhombic space group Pbcm with unit cell parameters a = 12.262(2) Å, b = 19.653(6) Å, c = 23.603(6) Å, V = 5688(2) ų, Z = 4, d _calc = 3.282 g/cm³. The structure is built from centrosymmetric cluster anions [Re₆Se₇Cl₇]^3? and complex cations [Th(DMSO)₈Cl]³⁺ possessing mirror-plane symmetry, half of the DMSO ligands being doubly disordered.     

BEDT-TTF-based radical cation salt with the cyanurate anion: synthesis,structure, conductivity,and polarized reflection spectra

The new conducting radical cation salt, bis(ethylenedithio)tetrathiafulvalene cyanurate, was synthesized. This salt is an organic metal down to 4 K. The crystal structure, conductivity, and optical properties of the salt were studied. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 96–101, January, 2008.     

Synthese,Eigenschaften und Struktur von oktamerem Titanimidchlorid [Ti(NSiMe3)Cl2]8

Synthesis, Properties, and Structure of Octameric Titanium Imide Chloride [Ti(NSiMe₃)Cl₂]₈ The reaction of TiCl₄ with N(SiMe₃)₃ in sealed glas-tubes yields the titanium imide chloride [Ti(NSiMe₃)Cl₂]₈ ( 1 ). It crystallizes in the space group C2/c with a = 2 704.5(4), b = 1 303.9(1), c = 2 205.4(2) pm, β = 112.78(1)°, Z = 4. In 1 six Ti atoms are linked together by chloro and trimethylsilylimido bridges to form a ring structure. Two TiCl₂-groups are bound in addition to the ring by two imido bridges. Upon annealing at 250°C 1 transformes to the isomeric polymer [Ti(NSiMe₃)Cl₂]_n. Above 250°C 1 decomposes under separation of Me₃SiCl affording TiNCl.     

Synthesis and Crystal Structure of [Cu (C_8H_4O_2F_3S) (2, 2' -bipy) ]

1INTRODUCTIONCoppercomplexesarewidelyusedascatalystsinthedecompositionofdisubsti-tutedperoxides"'-Theelectronicstructureandbondingatthecatalystscanbeprof-itablypursuedbystudyingmodelcomplexes.Generally,theCu(I)complexesareob-tainedbyreactionofCu(l)saltswithligands.Wereporthereamethodofpreparingcopper(I)complexbythereactionofCupowderwith2-thenoyltrifluoroacetone,2,2'-bipyinmethanol.2EXPERIMENTALReactionwascarriedoutundernitrogenatmosphere.2,2-bipy(1mmol)wasaddedtoamixtureof2-thenoyl…     

Structures and conductivities of isostructural synthetic metals (DOET)4[Hg2Cl6] and (DOET)4[Hg2Br6]

The structures of organic metals (DOET)₄[Hg₂Cl₆] (1) and (DOET)₄[Hg₂Br₆] (2), where DOET is (1,4-dioxanediyl-2,3-dithio)ethylenedithiotetrathiafulvalene, were established by X-ray diffraction analysis. Compounds 1 and 2 are isostructural, and their crystals have layered structures. The conducting layers formed by the stacked DOET^1/2+ cations alternate with the layers of the [Hg₂X₆]^2– anions (X = Cl, Br). The temperature dependence of the conductivity of salt 1 shows a metallic character in the range of 300—4 K. Compound 2 undergoes the metal—semiconductor phase transition (T_M—I) at 100 K.     

配合物[1-(4′-bromo-2′-fluorobenzyl)pyridinium]2[Ni(mnt)2]和[1-(4′-bromo-2′-fluorobenzyl)pyrazinium]2[Ni(mnt)2](mnt2-=maleonitriledithiolate dianion)的合成及晶体结构

本文报道两个含双(马来二氰基二硫烯)镍(Ⅱ)配合物阴离子的离子对化合物。对阳离子为1-(4′-溴-2′-氟苄基)吡啶 盐时,生成配合物1。晶体数据:三斜晶系,空间P1群,a=0.7086(2)nm,b=1.0968(3)nm,c=1.1775(3)nm,α=69.914(5)°,β=89.495(5)°,γ=74.765(5)°,V=0.8259(4)nm³,Z=1。对阳离子为1-(4′-溴-2′-氟苄基)吡嗪鎓盐时,生成配合物2。晶体数据:单斜晶系,空间群P2₁/n,a=0.71554(17)nm,b=1.4262(3)nm,c=1.6725(4)nm,β=100.396(4)°,V=1.6788(7)nm³,Z=4。两个配合物中,阴离子为拟平面结构,镍原子均位于对称中心。变换对阳离子上的芳环种类对晶体的堆积结构产生影响。     

New fulvalenium salts of bis(dicarbollide) cobalt and iron: Synthesis, crystal structure and electrical conductivity

New radical cation salts (BEDT-TTF)₂[3,3′-Co(1,2-C₂B₉H₁₁)₂] (1), (BEDT-TTF)₂[8-I-3,3′-Co(1,2-C₂B₉H₁₀)(1′,2′-C₂B₉H₁₁)] (2), (BMDT-TTF)[3,3′-Co(1,2-C₂B₉H₁₁)₂] (3) and (TMTSF)₂[3,3′-Fe(1,2-C₂B₉H₁₁)₂] (4) were synthesized and their crystal structures and electrical conductivities were determined. Compound 4 is isostructural to the earlier reported Co analogue. All the radical cation salts synthesized are semiconductors.     

Crystal structure of bis(l-arginine)copper(II) hexachlorodimercurate, [Cu(l-Arg)2]Hg2Cl6

By means of X-ray diffraction the chain structure of [Cu(l-Arg)₂]Hg₂Cl₆ (monoclinic, a = 10.2348(9) Å, b = 9.1386(7) Å, c = 14.8521(14) Å, β = 97.455(11)°, space group P2₁) is established. The chains are formed by square-planar [Cu(l-Arg)₂]²⁺ cations of the type trans-[Cu(N)₂(O)₂] (l-Arg is the zwitter-ion of arginine; Cu-N 1.992 Å and 1.938(6) Å, Cu-O 1.953 Å and 1.967(4) Å) that are bonded to two adjacent binuclear [Cl₂Hg(μ-Cl)₂HgCl₂]^2? ions through its clorine atoms Cl (Hg-Cl bonds are within 2.34–2.78 Å). With these two additional Cu…Cl contacts Cu adopts the geometry of an elongated octahedron with two apical Cl (Cu-Cl 2.961 Å and 3.064(3) Å).     

Synthesis,crystal structures,and redox behavior of bis(2-phenylindenyl) nickel and bis(2-phenylindenyl)zirconium dichloride

Redox reactions of the sandwich jn⁵-(Ph)Ind]₂Ni complex (1) (where (Ph)Ind is the 2-plrenylindenyl anion) in CH₂CI₂ and of the bent-sandwich (⁵-(Plr)Ind]₂ZrCl₂ complex (2) in THF have been studied by low-temperature cyclic voltammetry. Complex ( undergoes quasi-reversible two-step oxidation to cation i+ and dication 12+, which are stable at room temperature within the cyclic voltammetry time scale. Two-electron reduction of complex 1 is irreversible up to -50 °C, and this process is accompanied by destruction of the sandwich structure of the complex. Redaction of complex 2 is described by the conventional scheme for bent-sandwich complexes. According to this scheme, further one-electron reduction of radical anion 2- generates dianion 2^2–, which eliminates two CI^– ions to afford bisindcnyl sandwich complex (⁵-(Ph)lnd]₂Zr (3). This complex is stable at T < -45 °C within the cyclic voltammetry time scale and is capable of undergoing one-electron reduction to the corresponding radical anion 3-. Synthesis and crystal structures of complexes 1 and 2 are reported.Translated fromIzvestiya Akademii Nauk. Seriya Kidmicheskaya, No. 6, pp. 1529–1536, June, 1996.     

一价铜配合物〔Cu（C_8H_4F_3O_2S）（PPh_3）_2〕的合成和晶体

室温下，铜粉和２－噻吩甲酰三氟丙酮、三苯基膦在甲醇和四氢呋喃混合溶剂中反应，生成一价铜的配合物［Ｃｕ（Ｃ_８Ｈ_４Ｆ_３Ｏ_２Ｓ）（ＰＰｈ_３）_２］，测定了该配合物的晶体结构，结果表明，晶体属单斜晶系，Ｐ２_１／ｎ空间群，晶胞参数：ａ＝１０．５８４（１），ｂ＝１６．７３８（１），ｃ＝２２．７２８（９）Ａ；β＝９４．２２（２）°，Ｖ＝４０１５．２Ａ３，Ｍｒ＝７８５．２９，Ｚ＝４，Ｄｃ＝１０２９９ｇ／ｃｍ３，μ＝９．８６ｃｍ－１。晶体结构由直接法解出，使用块对角矩阵和全矩阵最小二乘法对原子参数进行修正，最后偏离因子Ｒ＝０．０４８，Ｒｗ＝０．０５４，其中４３９１个Ｉ＞３σ（Ｉ）的可观察衍射点参加了结构修正，结果表明，Ｃｕ原子由２个Ｏ原子和２个Ｐ原子配位，形成畸变四面体构型。     

Preparation and structure of (calix[8]arene methyl ether) · 2CDCl3

The methyl ether of calix[8]arene crystallizes from CDCl₃ with two molecules of the solvent per molecule of host. An X-ray structural investigation has shown that the CDCl₃ guests exist within the calixarene framework. The complex resides on a crystallographic center of inversion, and the cavity is roughly circular in projection as measured by the distance between centroids of aromatic rings related by the center: 14.5, 13.9, 10.1, and 11.2 Å. Six of the oxygen atoms are found on the inside and two on the outside. Crystals belong to the triclinic space group witha=11.741(9),b=11.810(9),c=12.484(8) Å, =94.74(8), =104.41(8), =111.30(9)°, andD _c =1.31 g cm^–3 forZ=1. Refinement led to a finalR value of 0.086 for 949 observed reflections. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82038 (10 pages).     

Synthesis and crystal structure of monoclinic Fe2(SeO4)3

Summary Crystals of monoclinic Fe₂(SeO₄)₃ were synthesized under hydrothermal conditions. The structure was determined by single crystal X-ray methods and refined in space group P2₁/n with 2 646 independent reflections (sin /<0.7 Å^–1) toR=0.033,R _w=0.037:a=8.530 (2) Å,b=8.888 (2) Å,c=11.952 (2) Å, =91.13 (1)°,V=906.0 ų,Z=4. The crystal structure is isotypic with the monoclinic modification of Fe₂(SO₄)₃, containing two different Fe(III) and three Se(VI) atomic positions. The FeO₆ and SeO₄ polyhedra are only slightly distorted, the mean Fe-O bond lengths are 1.986 Å and 2.004 Å, the average distances within the SeO₄ tetrahedra are each 1.628 Å. The isolated FeO₆ octahedra only share corners with SeO₄ tetrahedra to build a framework structure.

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Synthese und Kristallstruktur von monoklinem Fe₂(SeO₄)₃

Zusammenfassung Kristalle von monoklinem Fe₂(SeO₄)₃ wurden unter Hydrothermalbedingungen gezüchtet. Die Struktur wurde mit Einkristall-Röntgenmethoden bestimmt und in der Raumgruppe P2₁/n mit 2 646 unabhängigen Reflexen (sin /<0.7Å^–1) aufR=0.033,R _w=0.037 verfeinert:a=8.530(2) Å,b=8.888(2) Å,c=11.952(2) Å, =91.13(1)°,V=906.0 ų,Z=4. Die Kristallstruktur ist isotyp mit der monoklinen Modifikation von Fe₂(SO₄)₃, sie enthält zwei unterschiedliche Fe(III) und drei Se(VI) Atompositionen. Die FeO₆-Polyeder sind nur gering verzerrt, die mittleren Fe-O Bindungslängen sind 1.986 Å und 2.004 Å, die mittleren Abstände in den SeO₄-Tetraedern sind jeweils 1.628 Å. Die isolierten FeO₆-Oktaeder sind nur über gemeinsame Ecken mit SeO₄-Tetraedern verbunden, wobei eine Gerüststruktur entsteht.