Crystal Chemistry of Dichalcogenides MX2

Crystal-chemical analysis of the structures of metal (other than REE) dichalcogenides of composition X:M = 2:1 has been carried out. It is shown that there are two types of structure depending on the formal degree of metal oxidation. The first group are compounds M(X₂) containing metals in the oxidation state 2+ and covalently bonded pairs of chalcogen elements; the main structural types here are cubic (pyrite) and orthorhombic (marcasite) FeS₂. The second group involves the compounds MX₂ with metals in the formal oxidation state 4+ and chalcogenide ions X ₂ ^- ; the main structural types in this group are CdI₂, CdCl₂, MoS₂. The bond lengths M–X, X–X, and X...X are analyzed; it is shown that the high polarizability of the chalcogenide ions is reflected in shortened X...X distances. In the covalently bonded pairs X–X, the bond lengths change within the following limits: 2.03-2.30, 2.35-2.55, and 2.70-2.83 for X...X ion contacts, the minimal values are 3.07, 3.10, and 3.20 (X = S, Se, and Te, respectively).     

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.     

Structure and properties of the ion pair charge-transfer complex of octacyanotungstate(IV) with the 2,2′-bipyridinium dication

The X-ray crystal structure of (bpyH2)2[W(CN)8]·4H2 O (bpyH2=2,2-bipyridinium) is described. The [W(CN)8]4– anion has an approximately square antiprismatic (D4d) conformation, seemingly imposed by strong anion–water–cation hydrogen-bonding interactions. Bond distances in the anion are: WC 2.150(5), 2.163(5); CN 1.128(6), 1.145(6)Å and the angles WCN are 177.6(5), 178.3(5)°. The dihydrate and the anhydrous salt are both intensely black solids, exhibiting ion-pair charge-transfer interaction between cation and anion. E.s.r. spectra indicate that 30% of the tungsten is present as WV in the solid state, but that in solution only the WIV complex is present. The electron withdrawing effect of the cation is discussed and compared with that in a series of salts with different bipyridinium cations.     

The crystal and molecular structure of acetonitrilechlorodicyclopentadienyltitanium tetrachloroferrate(III). Some Mössbauer and X-ray photoelectron spectroscopic data

Summary The title compound crystallizes in the orthorhombic space group P2₁2₁2₁ with Z=4 and lattice parametersa=1744.2(4),b=1360.7(4),c=751.3(5) pm. An x-ray analysis shows the compound to consist of discrete (h⁵-C₅H₅)₂-Ti(Cl)NCMe⁺ cations and FeCl ₄ ^– anions. The cation has a distorted tetrahedral structure (Ti-C: 231.9-237.6 pm; Ti-Z: 203 and 204pm; Ti-Cl: 230.4 pm; Ti-N: 213.5 pm; Z-Ti-Z: 133.2°; Cl-Ti-N: 91.7° (Z: centre of cyclopentadienyl ring). The relatively short Ti-Cl bond length indicates a modest Ti-Cl -bonding contribution. The tetrachloroferrate(III) anion possesses a nearly undistorted tetrahedral geometry (Fe-Cl: 216.0–218.5 pm; Cl-Fe-Cl: 109.0–111.1°). Mössbauer and x-ray photoelectron spectroscopic data confirm the crystallographically derived structural features.     

Structure of (BEDT-TTF)-Based Organic Metals with Photochromic Nitroprusside Anion (BEDT-TTF)4M[FeNO(CN)5]2, where M = Na+, K+, NH+4, Tl+, Rb+, and Cs+

The crystal and molecular structures of a family of three-component radical cation salts bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF), (BEDT-TTF)₄M[NP]₂, where M = Na⁺, K⁺, NH⁺ ₄, Tl⁺, Rb⁺, and Cs⁺and NP is the nitroprusside anion [FeNO(CN)₅]^2–, are studied by X-ray structure analysis. These salts are isostructural and behave as stable metals down to helium temperatures. Their structures are characterized by radical cation layers of the "-type alternating with layers of complex anions [M⁺(NP^2–)₂]^3–. The conducting radical cation system and photochromic nitroprusside anion in the crystals were shown to affect each other. On the one hand, this changes the geometric parameters of the nitroprusside anion as compared to those of the Na₂[NP] · 2H₂O crystals in the ground state and, on the other hand, makes the geometries of the two crystallographically independent BEDT-TTF molecules with a different number of shortened contacts with the anion different. Based on the data of crystallochemical analysis of the (BEDT-TTF)₄M[FeNO(CN)₅]₂structures, we suggest their possible routes of chemical modification with the purpose of changing their physical properties.     

Electron Density Calculations for Crystals with a NaCl Lattice

The ab initio local DFT method combined with the ab initio pseudopotential technique is used to calculate valence electron densities in series of crystal substances MA (M = Li, Na, K, Rb, Ag, Mg, Ca; A = F, Cl, Br, O, S) with a NaCl lattice. Systematic variations of valence electron density depending on the atomic number of anion and cation have been found. According to electron density distribution, the compounds are classified into three groups: a) oxides and fluorides; b) sulfides, chlorides, and bromides; c) noble metal halides. In oxides and fluorides, the maximum of valence electron density is in the middle of the M–M bond. In sulfides, chlorides, and bromides, the minimum density is in the middle of the M–M bond, with two symmetric maxima or two shoulders (depending on the atomic number of the cation) lying away from the center of the bond. In noble metal halides, the maximum of valence density is on the metal due to the presence of metal d-states, and the density map is rotated through 90° relative to the map of alkali and alkali earth metals, so that the Hal–Hal bond becomes an analog of the M–M bond.     

Ab Initio Study of the Acetylene–Allene Rearrangement in 2-Propargylpyrrole, 2-Propargylfuran, and 2-Propargylthiophene

Ab initio (MP4/6-31G*//RHF/6-31+G*) calculations have been performed to study the acetylene–allene rearrangement in X–CH₂–CCH propargyl systems, where X = ethenyl, E-1-butadienyl, 2-pyrrolyl, 2-furanyl, and 2-thienyl. The spatial and electronic structures, as well as the relative stability, of the initial and final acetylene structures and the corresponding allenes are examined. Migration of the triple bond from the terminal position into the chain, including the stage of allene structure formation, is shown to be thermodynamically favorable for the whole series of compounds. The propargyl substituents of heterocycles isomerize as readily as open diene systems. The differences in the isomerization energies in the series of allenyl- and 1-propynyl-substituted pyrrole, furan, and thiophene are mainly due to the differences in the nature of long-range interactions between heteroatoms and the tricarbon system.     

Rhenium(I) tricarbonyl complexes with bispyridine ligands attached to sulfur-rich core: Syntheses, structures and properties

Rhenium(I) tricarbonyl complexes with bispyridine ligands bearing sulfur-rich pendant, Re(CO)₃(Medpydt)X (Medpydt = dimethyl 2-(di(2-pyridyl)methylene)-1,3-dithiole-4,5-dicarboxylate; X = Cl, 1; X = Br, 2) and Re(CO)₃(MebpyTTF)X (MebpyTTF = 4,5-bis(methyloxycabonyl)-4′,5′-(4′-methyl-2,2′-dipyrid-4-ylethylenedithio)-tetrathiafulvalene; X = Cl, 5; X = Br, 6), were prepared from the reactions between Re(CO)₅X (X = Cl, Br) and Medpydt or MebpyTTF, respectively. Hydrolysis of the above complexes afforded the analogues with carboxylate derivatives, Re(CO)₃(H₂dpydt)X (X = Cl, 3; X = Br, 4) and Re(CO)₃(H₂bpyTTF)X (X = Cl, 7; X = Br, 8). The crystal structures for complexes 1 · 2H₂O, 5 and 6 were determined using X-ray single crystal diffraction. UV-Vis absorption spectra of the rhenium complexes show the intraligand and MLCT transitions. Electrochemical behaviors of all new compounds were studied with cyclic voltammetry. Upon irradiation, complexes 3-6 exhibit blue to red emissions in fluid solutions at the room temperature. The performance of complexes 3, 4, 7 and 8 as photosensitizers for anatase TiO₂ solar cells was preliminarily investigated as well.     

Crystallochemical Analysis of Rare-Earth Halogen-Containing π-Complexes

Ninety-six halogen-containing -complexes of rare-earth elements were studied to reveal how the volume of the area of action of the Ln atom in coordination polyhedra LnC _n X _m (X = F, Cl, Br) depends on its nature, coordination and oxidation numbers, and on the number of Ln–X bonds. A method was proposed for estimating the ligand sizes in the coordination sphere by making use of the molecular Voronoi–Dirichlet polyhedra. The effect of the ligand sizes on the stability of -complexes and formation of aghostic contacts in their structures was analyzed.     

Acid–Base Zeta-Metric Titration of Quartz Dispersions in Ethanol Solutions of Electrolytes

The conductivity of dilute quartz suspensions and electrophoretic mobility of quartz particles in solutions with the concentration C = 10^–5–10^–2 M XBr (X = H, Cs, Na, and Li) and NaOH, as well as in mixed solutions of 10^–4 M XBr (X = Cs, Na, and Li) + 10^–4–10^–2 M HBr and 10^–4 M XBr + 10^–4–10^–2 M XOH (X = Cs, Na, and Li) in ethanol containing 6 vol % of water were measured using conductometry and microelectrophoresis. The values of surface conductivity of quartz were calculated by the Wagner formula and used to calculate zeta potential by the Henry–Booth formula. The resultant dependences (logC) suggest that the value and sign of zeta potential are determined not only by the adsorption of potential-determining ions ⁺ and ^–, but also by the competitive specific adsorption of all ions of the aforementioned electrolytes, the adsorption values increasing in a cation series Li⁺ < Na⁺ < Cs⁺ < H⁺ and an anion series Br^– < OH^–. In particular, it is found that the titration of the above suspensions with XOH bases results in the reversal of zeta potential sign from negative to positive at a concentration depending on the adsorption capacity of alkali cation.     

B—Z bond dissociation energies of <Emphasis Type="Italic">para</Emphasis>-substituted phenylboranes: a problem for Nau's definition of polar ground-state effects

UB3LYP/6-311++g(2df,p) and RMP2/6-311++g(d,p) methods were used to calculate B—Z bond dissociation energies (BDE) of para-substituted phenylboranes (X—C₆H₄—BH—Z). It was found that the slopes () of regressions between B—Z BDEs and substituent _p constants increase in the order B—Cl (between –0.24 and 0.21 kcal/mol) < B—H (0.06-0.33 kcal/mol) < B—F (0.48-0.78 kcal/mol) < B—CH₃ (0.83–1.28 kcal/mol) < B—Li (2.62-3.73 kcal/mol). Since all the homolysis reactions give the same boron radical, the large variation of indicates that the substituent effects on energies of the ground-state molecules are important for the substituent effects on BDEs. However, the ground-state stabilization energies, calculated using either Nau's method or our method, do not show any correlation with the polarization of the B—Z bond as defined by the electronegativity difference between the group X—C₆H₄—BH and Z. Therefore, the theory that the remote substituent effects on Y—Z BDEs are dependent on the Y—Z polarity should be discarded.     

Incorporation of a tripodal ligand with a (N,O,O)-donor set into a new family of nickel and cobalt spin clusters

The reaction of Ni(OAc)₂, NiX₂ (X = Cl, Br) or CoCl₂ with the proligand 2-amino-2-methyl-1,3-propanediol (ampdH₂) affords a new family of tetranuclear complexes. The syntheses of [Ni₄(OAc)₄(ampdH)₄] (1) and [M₄X₄(ampdH)₄] (M = Ni, X = Cl, 2; M = Ni, X = Br, 3; M = Co, X = Cl, 4) are reported, together with the single crystal X-ray structures of 1, 2 and 4 and the magnetochemical characterization of 1, 3 and 4. Each member of this family of complexes displays a low symmetry structure that incorporates a {M₄O₄} core unit based on a distorted cubane. Magnetic measurements reveal ferromagnetic exchange interactions for 1, 3 and 4. These give rise to S = 4 ground state spins for the tetranuclear Ni complexes and an anisotropic effective S′ = 2 ground state for the Co complex.     

Specific nonbonded interactions in the structures of M3X7 4+ and M3X4 4+ (M=Mo,W; X=O,S, Se) clusters

Specific nonbonded interactions (SNI) involving the chalcogens in the structures of (₃–X)(₂–X₂)₃M₃ ⁴⁺ and (₃–X)(₂–X)₃M₃ ⁴⁺ (M = Mo, W; X = 0, S, Se) clusters are examined. Interionic contacts significantly shorter than the sum of the van der Waals or ionic radii are fomd between the X atom of the X₂ ligands that occupy the axial position relative to the M₃ plane and the N, chalcogen, or halide of the counterion or identical ion. Centrosymmetric dimers involving the (₂-X₂) ligands are observed in the stmctures of several M₃X₄ ⁴⁺ derivatives. The X...X distance in these is also much less than the sum of the van der Waals radii. These SNI open occur in spite of the Coulombic repulsion of similarly charged species. The SNZ are classified using existing data. They play a definite role in forming of the crystal structure.Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences. Translated from Zhurnal Strukturnoi Khimii, Vol. 34, No. 2, pp. 150–167, March–April, 1993.     

Crystal Structures and Packing of 2,4,6-tris(4-Fluorophenoxy)-1,3,5-triazine and 2,4,6-tris(3,4-Dimethylphenoxy)-1,3,5-triazine. New Materials for Octupolar Nonlinear Optics

The crystal structures and packing of 2,4,6-tris(4-fluorophenoxy)-1,3,5-triazine and 2,4,6-tris(3,4-dimethylphenoxy)-1,3,5-triazine are discussed. These structures have been determined as a continuation of a series of octupolar NLO materials we have been investigating. The crystal structures are characterized by C–H...F and C–H... hydrogen bonds, respectively. A characteristic of these triazine structures is the presence of dimeric Piedfort Units (PU) that are extended into more elaborate two-dimensional (2-D) networks. The structure of the fluoro derivative is compared with that of the corresponding unsubstituted and chloro/bromo-substituted derivatives. The structure of the dimethyl triazine is compared with that of the corresponding 4-methyl derivative. The noncentrosymmetric nature of the dimethyl derivative was confirmed by a powder SHG signal at 1.064 m of the order of 0.5 × KDP. Interestingly, the dimethyl derivative studied here is isostructural with the corresponding 4-methyl triazine. This H/Me isostructurality is shown to be an uncommon phenomenon by an analysis with the CSD.     

(N,N, N′, N′-tetramethylethylenediammonium)Cu2X6 (X=Cl,Br): crystal structure and magnetic interactions

Summary The crystal structures of (Me₄enH₂)Cu₂Cl₆ and (Me₄enH₂)Cu₂Br₆ have been determined. The triclinic crystals contain chains of symmetrically bibridged [Cu₂X₆]^2– dimers. Within the dimers the Cu–X distances average 2.299 Å (Cl) and 2.408 Å (Br) and the Cu–X–Cu angles are 96.4(1)^o (Cl) and 95.7(1)^o (Br). Longer Cu–X bonds, 2.679(1)Å (Cl) and 2.761(3)Å (Br), link dimers together into infinite chains via asymmetrical bridges. The bridging angles for the asymmetric bridge are 92.2(1)^o (Cl) and 89.4(1)^o (Br). Magnetic susceptibility data for both compounds are indicative of antiferromagnetic coupling. Analyses of the data yields J/k=–23(1)K (Cl) and –82(2)K (Br) for the interdimer coupling and J/k=–5(1)K (Cl) and –4(1)K (Br). The intradimer coupling for the chloride is in accord with magneto-structure relations deduced for similar salts. Similarly, the increased antiferromagnetic contribution upon substitution of Cl by Br follows trends previously observed.     

Optical Limiting Devices Based on C60 Derivatives in Sol-Gel Hybrid Organic-Inorganic Materials

A guest-host solid state device based on hybrid organic-inorganic materials and fullerene derivatives has been fabricated for optical limiting applications. Different 3-glycidoxypropyltrimethoxysilane derived hybrid matrices have been synthesized to increase the optical limiting performances. These matrices have shown high laser damage fluences, low light scattering, good transmittance in the visible range and allowed to deposit 10–100 m thick films per single layer. The C₆₀ derivatives have been functionalized with Si tri-alkoxide terminal groups and have reached a final concentration in the solid matrix up to 2 × 10^–2 M·l^–1. A multilayer system with a bottleneck structure has been developed to optimize a laser protection device.     

Molecular structure of 6-methyleneoxytetracycline hydrobromide

The structure of 4(dimethylamino)-1, 4, 4a, 5, 5a, 6, 11, 12a-octahydro-3, 5, 10, 12, 12a-pentahydroxy-6-methylene-1, 11-dioxo-2-naphthacenecarboxamide hydrobromide salt was determined by an X-ray analysis. One methacycline cation and one bromide anion were found in the asymmetric unit of an orthorhombic cell, space group P2₁2₁2₁,a 9.580(1),b 12.147(2),c 18.735(3) å,V2180.0(5) å³, Z4,D _c 1.59 g cm^–3, (MoK) 19.15 cm^–1. The structure was solved and refined toR(F) 0.062 andR _w(F) 0.064 by a full matrix least-squares procedure. The conformation of the methacycline cation is found to be similar to that reported for 6-demethyl-7-chlorotetracycline hydrochloride trihydrate.     

Quantum-Chemical Investigation of Intermediates in the Addition of Phenylsulfenium Cation to Substituted Acetylenes

The reaction paths for the transformations of substituted acetylenes (X—CC—Y; X, Y = H, Me, Ph, CN) in reaction with phenylsulfenium cation were studied by quantum-chemical methods. It was shown that the reactions take place with the formation of acyclic and cyclic cationic intermediates. The factor that determines the structure and characteristics of these cations is the induction and polarizing action of the substituents in the acetylenes and to a lesser degree their electron-donor characteristics. The resonance effect of the phenyl substituent has a predominantly levelling action on the distribution of charges.     

Coordination of Ce(III) and Nd(III) with pentaethylene glycol in the presence of picrate anion: Spectroscopic and X-ray structural studies

¹H NMR evidence for direct coordination between the Ln(III) ion and the oxygen atoms of the pentaethylene glycol (EO5) ligand and the picrate anion (Pic) in [Ln(Pic)₂(EO5)][Pic] {Ln = Ce and Nd} complexes are confirmed by single X-ray diffraction. No dissociation of Ln–O bonds in dimethyl sulfoxide-d solution was observed in NMR studies conducted at different temperatures ranging 25–100 °C. The Ln(III) ion was chelated to nine oxygen atoms from the EO5 ligand in a hexadentate manner and the two Pic anions in each bidentate and monodentate modes. Both compounds are isostructural and crystallized in monoclinic with space group P2₁/c. Coordination environment around the Ce1 and Nd1 atoms can be described as tricapped trigonal prismatic and monocapped square antiprismatic geometries, respectively. The crystal packing of the complexes have stabilized by one dimensional (1D) chains along the [0 0 1] direction to form intermolecular O–HO and C–HO hydrogen bonding. The molar conductance of the complexes in DMSO solution indicated that both compounds are ionic. The complexes had a good thermal stability. Under the UV-excitation, these complexes exhibited the red-shift emission.