Structural chemistry of mercury chalcohalides. III. Crystal structure of Hg<Subscript>3</Subscript>S<Subscript>2</Subscript>Cl<Subscript>1.5</Subscript>Br<Subscript>0.5</Subscript> polymorphs

Single crystals of two new mercury thiohalides of the composition Hg₃S₂Cl_{2? x}Br_x(x = 0.5) have been grown from gas phase and studied by X-ray crystallography. Structure refinement for monoclinic (I) and cubic (II) phases (I: a = 16.841(2) Å, b = 9.128(2) Å, c = 9.435(4) Å; β = 90.080(10)°, V = 1450.3(7) ų, space group _C2/_{m, Z} = 8, _R = 0.0528; II: a = 18.006(2) Å, V = 5837.8(11) ų, space group \(Pm\bar 3n\), Z = 32, R = 0.0503) clearly shows that they are polymorphs of the same composition Hg₃S₂Cl_1.5Br_0.5. The monoclinic modification I is similar to the synthetic phases γ-Hg₃S₂Cl₂, β-Hg₃S₂Br₂, Hg₃Se₂Br₂ and to the analogue of radtkeite mineral, Hg₃S₂ClI. The modification II is isostructural to the synthetic β-Hg₃S₂Cl₂. In both structures, each S atom coordinates three Hg atoms with the formation of pyramidal SHg₃ units (Hg-S 2.37–2.48 Å; HgSHg 93.1–97.5 ). The SHg₃ units are linked through Hg vertices into corrugated layers [Hg₁₂S₈]_∞∞ (I) and isolated cubic groups [Hg₁₂S₈] (II). Similarly to other mercury chalcohalides, the crystal structures are basically determined by the halogen atoms which form a cubic sublattice incorporating the Hg-S moieties.     

Crystal structure of the synthetic analog of grechishchevite and Hg-X (X = S,Se, Te) bond topology in mercury chalcogen halides

This paper analyzes the structural data available for the synthetic analog of the mineral grechishchevite Hg₃S₂Br_1.00Cl_0.50I_0.50. The crystal structure of the synthetic mineral is refined. For chalcogen halides Hg₃X₂Hal₂ (X = S, Se, Te; Hal = Cl, Br, I), the paper presents an inventory of infinite and isolated ribbons, layers, and frameworks of covalently bonded Hg-X radicals growing into the pseudocubic matrix of halogen atoms.Original Russian Text Copyright © 2004 by N. V. Pervukhina, S. V. Borisov, S. A. Magarill, D. Yu. Naumov, V. I. Vasiliev, and B. G. NenashevTranslated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 3, pp. 462–470, May–June, 2004.     

Crystalline and molecular structures of two halogenated propionamides CF2XCF2CONH2 (X = H, Cl)

Using the XRD method, the crystalline and molecular structures of two halogenated propionamides, CF₂XCF₂CONH₂, X = H (I) and Cl (II), have been studied. Crystals I and II are monoclinic: space group P2₁/c, Z = 4; (I) a = 10.967 Å, b = 5.406 Å, c = 10.063 Å, β = 107.86°; (II) a = 11.979 Å, b = 5.608 Å, c = 10.042 Å, β = 99.31°. Structures I and II were solved by the direct method and refined by the full-matrix least-square method to R = 0.112 (I) and 0.139 (II) over all 1299 (I) and 1175 (II) independent measured reflections (a CAD-4 autodiffractometer, λMoK _α).     

Crystal structure of the synthetic analog of radtkeite Hg<Subscript>3</Subscript>S<Subscript>2</Subscript>Cl<Subscript>1.00</Subscript>I<Subscript>1.00</Subscript>

The results of structural studies of the synthetic analog of the radtkeite mineral Hg₃S₂Cl_1.00I_1.00 are analyzed. The crystal structure of the compound has been refined; the unit cell parameters are a _m = 16.827(4) , b _m = 9.117(1) , c _m = 13.165(5) , = 130.17(2)°, V = 1543.3(8) ³, space group C2/m, Z = 8, R = 0.0527. A possible transition a ₀ = a _m; b ₀ = a _m + 2c _m; c ₀ = –b _m to the pseudo-orthorhombic F cell previously determined for radtkeite, where one of the angles ( ₀ ) is slightly different from 90° (89.55°), has been found. Each sulfur atom in the structure is bonded to three mercury atoms, forming SHg₃ umbrellas with distances 2.240(6) –2.474(8) and angles HgSHg 94.7(2)°–102.9(2)°. The SHg₃ fragments are linked through Hg vertices to form corrugated [Hg₁₂S₈] layers. The halogen atoms lie inside and between the [Hg₁₂S₈] layers; the distances are Hg-Cl and Hg-I 2.783(7) , 2.961(7) , and 3.083(4) –3.311(3) , respectively.Original Russian Text Copyright © 2004 by N. V. Pervukhina, S. V. Borisov, S. A. Magarill, D. Yu. Naumov, V. I. Vasiliev, and B. G. NenashevTranslated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 4, pp. 755–758, July–August, 2004.This revised version was published online in April 2005 with a corrected cover date.     

Crystal and molecular structures of new fullerides, (Ph4P)2C60Hal (Hal=Br or I) and (Ph4As)2C60Cl

New air-stable fullerides, (Ph₄P)₂C₆₀Hal (Hal=Br or I) and (Ph₄As)₂C₆₀Cl, were synthesized, and their crystal structure were determined. A comparative crystal-chemical analysis of the fullerides under study demonstrated that they are isostructural, described by the general formula (Ph₄X)₂C₆₀Hal (X=P or As, and Hal=Cl, Br, or I), and crystallize in the triclinic system. The C₆₀ ⁻ and Hal⁻ anions occupy special centrosymmetric positions. The (Ph₄P)⁺ and (Ph₄As)⁺ cations occupy general positions. The principal parameters of the molecular structures are reported. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1982–1986, November, 1997.     

Crystalline host-guest complexes involving carboxylic acid hosts and a dimethyl sulphoxide guest. X-ray crystal structures of two inclusion species

The host compounds 2,2-binaphthyl-3,3-dicarboxylic acid (1) and 1,13–1-terphenyl-2,4,4-tricarboxylic acid (2) have been synthesized, and crystal structures of their inclusion compounds with DMSO {1a [1·DMSO(11)];2a [2·DMSO (12)]} have been determined from single crystal X-ray diffraction data. The crystals show monoclinic symmetry withZ=4 (P2₁/n for1a andP2₁/c for2a), with the unit cell dimensionsa=11.567(1),b=10.206(1),c=17.579(1) Å,=100.50(1)° for1a, anda=14.910(1),b=6.732(1),c=26.084(1) Å,=100.41(1)° for2a. The structural models were refined toR=0.032 with 3127 reflections for1a, andR=0.035 with 3175 observations for2a, collected atT=173(1) K. Both structures comprise a characteristic molecular recognition pattern for DMSO via strong (CO)O–HO(=S) hydrogen bonds and possible C–HO contacts, the latter ones from the guest methyl groups to the carbonyl oxygen of the host carboxyl groups. In the crystals H-bonded endless chains of alternating host and guest molecules are formed, which are held together by ordinary van der Waals' forces. Additionally, host2 binds a second DMSO molecule by a single (CO)O–HO(=S) bond.Supplementary Data relating to this article have been deposited with the British Library at Boston Spa, Wetherby, West Yorkshire, U.K., as Supplementary Publication No. SUP 82186 (9 pages)     

Synthesis and crystal structure of the deuterated organic conductor, (d8-ET)4[Hg2(SCN)4Cl2]

On the basis of completely deuterated bis(ethylenedithio)tetrathiafulvalene (d₈-ET), new organic conductors, (d₈-ET)₄[Hg₂(SCN)₄Cl₂] and (d₈-ET)₂[Hg(SCN)₂Br] have been synthesized and studied by X-ray structural analysis. Unlike nondeuterated organic metalsk-(ET)₂[Hg(SCN)_3–n X _n ] (X = Cl or Br;n=1 and 2), the crystal structure of (d₈-ET)₄[Hg₂(SCN)₄Cl₄] exhibits -type packing of the d₈-ET radical cations in the conducting layer and a polymeric structure of anions, in which both the SCN groups and the Cl atoms are involved in the bridging bonds. The crystals of (d₈-ET)₂[Hg(SCN)₂Br] and the nondeuterated form (ET)₂[Hg(SCN)₂Br] are isostructural.Translated fromIzvestiya Akademii Nauk. Seriya Khlmicheskaya, No. 5, pp. 905–909, 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).     

Synthesis,structure, and magnetic properties of bis (3-amino-2-chloropyridinium)tetrahalocuprate(II) [halide = Cl or Br]

The reaction of CuX₂ (X = Cl or Br) with 3-amino-2-chloropyridine in aqueous acids (HX; X = Cl or Br) yields bis(3-amino-2-chloropyridinium)tetrachlorocuprate(II) and bis(3-amino-2-chloropyridinium)tetrabromocuprate(II). Both compounds have been characterized by IR, powder X-ray diffraction, single-crystal X-ray diffraction and temperature dependent magnetic susceptibility. The compounds are isomorphous and exhibit weak antiferromagnetic interactions.     

Complexation of (N, N-diethylthiocarbamoylmethyl) diphenylphosphine sulfide with silver nitrate. The structure of the [Ag{Ph2P(S)CH2C(S)NEt2}2]NO3 complex

(N, N-Diethylthiocarbamoylmethyl)diphenylphosphine sulfide, Ph₂P(S)CH₂C(S)NEt₂, forms a distorted tetragonal bisligand complex [AgL₂]NO₃ with Ag⁺. The stability constant of the complex in acetonitrile was estimated by spectrophotometry (logK=3.7). Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 846–852, April, 1997.     

Synthesis and crystal structure of Fe[(Te1.5Se0.5)O5]Cl,the first iron compound with selenate(IV) and tellurate(IV) groups

During the search for selenium analogues of FeTe₂O₅Cl, the new iron (III) tellurate(IV) selenate(IV) chloride with the composition Fe[(Te_1.5Se_0.5)O₅]Cl was synthesized by chemical vapor transport (CVT) reaction and characterized by TGA-, EDX-,SCXRD-analysis, as well as IR and Raman spectroscopy. It was found that Fe[(Te_1.5Se_0.5)O₅]Cl crystallizes in the monoclinic space group P2₁/c with unitcell parameters a = 5.183(3) Å, b = 15.521(9) Å, c = 7.128(5) Å and β = 107.16(1)°. The crystal structure of Fe[(Te_1.5Se_0.5)O₅]Cl represents a new structure type and contains electroneutral heteropolyhedral layers formed by dimers of the [FeO₅Cl]^8– octahedra, linked via common O-O edges, and mixed [Te₃SeO₁₀]^4- tetramers. Adjacent layers are stacked along the b axis and linked by weak residual bonds. The new compound is stable up to 420 °C. DFT calculations predict Fe[(Te_1.5Se_0.5)O₅]Cl to be a wide-gap semiconductor with the band gap of ca. 2.7 eV.     

Electronic structure and one-electron properties of the MoO2Cl2 molecule. Electronic spectra of the MoO2Cl2, MoO2Br2 and WO2Br2 molecules

The SCF-X -SW method in an overlapping atomic spheres approximation has been used to calculate the electronic structure, ionization potentials, energies and oscillator strengths of the allowed optical transitions and also some of the one-electron properties of the MoO₂Cl₂ molecule. The electronic absorption spectra of vapours over molybdenum and tungsten dioxodibromides have been measured. Interpretation of the experimental electronic absorption spectra of the MoO₂Cl₂, MoO₂Br₂ and WO₂Br₂ molecules is discussed.     

Molecular and crystal structure of Bis(η5-cyclopentadienyl)titanium(IV) Dibromide,Ti(η5-C5H5)2Br2

The crystal and molecular structure of Bis(η⁵-cyclopentadienyl)titanium(IV) dibromide, Ti(η⁵?C₅H₅)₂Br₂, has been investigated by an X-ray structure determination. Crystal data: triclinic, a = 7.872(5), b = 11.807(5), c = 12.310(3) Å, α = 107.62(3), β = 100.83(4), γ = 90.69(4)°, V = 1 068(14) ų, T = 293, space group P1 , Z = 4 (there are two crystallographically independent molecules in the asymmetric unit cell and their conformations are similar). Final R and R_w values are 0.068 and 0.073, respectively. The structural results are compared to those for similar type molecules.     

4-hydroxy-2-quinolones. 94. Improved synthesis and structure of 1-hydroxy-3-oxo-5,6-dihydro-3h-pyrrolo[3,2,1-i,j]-quinoline-2-carboxylic acid ethyl ester

A modified method is proposed for preparation and purification, and the special features of the spatial structure have been studied for the ethyl ester of 1-hydroxy-3-oxo-5,6-dihydro-3H-pyrrolo[3,2,1-i,j]-quinoline-2-carboxylic acid. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 718–723, May, 2006.     

CH3SS与XO (X＝F,Cl, Br)反应过程的电子密度拓扑研究

利用MP2/6-311＋＋G(d,p)//B3LYP/6-311＋＋G(d,p)对CH3SS与XO (X＝F, Cl, Br)的反应机理进行了研究. 着重从电子密度拓扑分析角度讨论了化学键的生成和断裂. 计算结果表明单线态反应为主要反应通道, 且由于该通道的反应能垒低、放热明显, 说明CH3SS与XO在大气中比较容易进行. 电子密度拓扑分析表明, 在单线态抽氢反应通道中存在着四元环状过渡结构, 随着反应进行, 此四元环状过渡结构通过一个T-型结构变为三元环状过渡结构, 最后环状结构消失得到产物.     

Crystalline inclusion compounds of tetrabenzo-18-crown-6 with uncharged organic molecules. Solid-state structure of the nitroethane complex

Tetrabenzo-18-crown-6 (1) shows distinct solid-state inclusion properties towards a number of OH-acidic, CH-acidic and low-polar uncharged organic molecules. The single crystal X-ray analysis of the inclusion complex between1 and EtNO₂ (11) is reported. Crystals are monoclinic,P2₁/c, witha=12.887(1),b=19.365(2),c=10.776(1) Å, =96.33(2)^o,D _c=1.321g cm^–1,Z=4. The host macroring has a conformation similar to a dentist's-chair. The complex is stabilized mainly by C–H...O type interactions involving the methyl group of the EtNO₂ guest molecule which is highly disordered. The nitroethane guests are trapped in channels formed by the host macrocycles. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82150 (11 pages)     

Coordinated and clathrated guests in the 3infinity[Hg6As4]4+ bicompartmental framework: synthesis,crystal and electronic structure,and properties of the novel supramolecular complexes [Hg6As4](CrBr6)Br and [Hg6As4](FeBr6)Hg0.6

Two new supramolecular complexes [Hg(6)As(4)](CrBr(6))Br (1) and [Hg(6)As(4)](FeBr(6))Hg(0.6) (2) have been prepared by the standard ampoule technique and their crystal structures determined. Both crystallize in the cubic space group Pa$\bar 3$ with the unit cell parameter a=12.275(1) (1) and 12.332(1) A (2), and Z=4. Their structures consist of bicompartmental, three-dimensional [Hg(6)As(4)](4+) frameworks with cavities of two different sizes occupied by guest anions of different type. The bigger cavities are filled with the octahedral MBr(6) (n-) ions (M=Cr or Fe; n=3 or 4), whereas the smaller cavities trap either Br- ions (1) or Hg(0) (2). The analysis of the host-guest contacts has allowed a classification of the octahedral guests as coordinated and the monatomic guests as clathrated. Magnetic measurements and ESR spectroscopy data have given information about the interaction between the host and guests. Band structure calculations (HF and hybrid DFT level) indicate that both 1 and 2 are non-metallic, with a band gap of approximately 1.5 eV (B3LYP), and that the interaction between the host and guests is of predominantly electrostatic character. It is shown that though the electrostatic host-guest interaction is weak it plays an important role in assembling the perfectly ordered supramolecular architectures.     

Re-determination of the crystal structure and investigation of thermal decomposition of the Chugaev’s salt, [Pt(NH3)5Cl]Cl3·H2O

The crystal structure of the salt [Pt(NH₃)₅Cl]Cl₃·H₂O has been re-determined by single crystal X-ray diffraction and the salt has been studied by the thermal analysis. It is shown that one molecule of crystallization water enters into the salt composition. Intermediate products of thermal decomposition of the salt have been isolated and explored by IR spectroscopy and powder X-ray diffraction.     

Synthesis and the crystal structure of a supramolecular adduct of the [Mo3O4(H2O)6Cl3]+ cluster complex with macrocyclic cavitand cucurbituril

The crystalline supramolecular compound of composition {(C₃₆H₃₆N₂₄O₁₂)[Mo₃O₄(H₂O)₆Cl₃]₂}Cl₂·14H₂O was obtained by slow concentration of a hydrochloric solution of the cluster aqua complex [Mo₃O₄(H₂O)₉]⁴⁺ and macrocyclic cavitand cucurbituril (C₃₆H₃₆N₂₄O₁₂). The molecular and crystal structure of the supramolecular adduct was established by X-ray diffraction analysis.     

The first X-ray crystal structure of a mercury(II) complex with an SP(N)3-based ligand: Synthesis and crystal structure of SP(NC5H10)3 and [Hg{SP(NC5H10)3}Cl2]2

The synthesis, spectral characteristics (IR and NMR), elemental analysis and X-ray crystal structure of phosphorothioic triamide SP(NC₅H₁₀)₃ (1) and its dinuclear mercury(II) complex [Hg₂(μ-Cl)₂(Cl)₂{SP(NC₅H₁₀)₃}₂] (2) were investigated. A survey using the Cambridge Structural Database (CSD, version 5.38, May 2017) shows structures of coordination compounds of Au, Ag, Cd, Cu, Li, Mo, Ni, Pd, Te, Ti, Zn, and Zr with sulfur-donor SP(N)₃-based ligands; the complex 2 is the first example of a mercury complex with the SP(N)₃-based ligand studied by X-ray crystallography. Valence bond calculation was performed for the Hg–S bond in 2 and compared with the Hg–O bond in the only structure with a Cl₂Hg–OP(N)₃ structural motive in the CSD. The calculation confirms a more covalent nature of the Hg–S bond with respect to the Hg–O bond made by the EP(N)₃-based ligands (E?=?S, O). The supramolecular structures based on C–H···S?=?P contacts in 1 and C–H···S═P and C–H···Cl–Hg assemblies in 2 are discussed.