S. V. Konovalikhin

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

The composition and structure of the radical-ion salt (ET)2[Hg(SCN)2Cl], a new organic metal withTM-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, β=90.02(6)°, space groupCc, Z=4,dcalc=2.08 g/cm3,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)2Cl]− 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 κ 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.

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 (Tm-d) of 35°K, and (ET)2[Hg(SCN)2Br], with Tm-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 Tm-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, β = 89.91(3)°, V = 3588.1(9) Å3, space group Cc, Z = 4, dcalc = 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, β = 89.71(3)°, V = 3629.6(8) Å3, space group C2/c, Z = 8, dcalc = 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−nXn]− 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−nXn] salts, where X = Cl and Br, and n = 1 and 2.

Crystal and molecular structure of (BEDT-TTF)4Cd2I6

The new radical-cation salt (BEDT-TTF)4Cd2I6 has been studied by x-ray diffraction (a=19.284(6), b=12.84(1), c=7.869 (2) Å; α=72.77(4), β=94.44(2), γ= 103.97(3)o, space group P1, Z=1, dcalc=2.32 g/cm3). The radical cation (BEDT-TTF)1/2+ and the Cd2I62− anions form organic and inorganic layers alternating along the a axis. In the organic layer, (BEDT-TTF)1/2+ are arranged in stacks and ribbons. The radical-cations in the ribbon are packed “side to side” and are joined to one another through shortened intermolecular contacts S...S 3.346(5)-3.657(4) Å. The Cd2I62− anion is dimeric. The Cd atom has a distorted tetrahedral bond configuration, with bond lengths Cd-I 2.722(l)-2.886(1) Å and valence angles I-Cd-I 93.8(1)-114.1(1)∘.

Bis(ethylenedithio)tetrathiafulvalene bromide-ethylkne glycol: (BEDT-TTF)2Br·C2H4(OH)2. A new organic metal

A synthesis is reported for a new radical-cation salt (BEDT- TTF)2Br·C2H4(OH)2 having metallic electric conductance up to − 200 K. X-ray diffraction structural analysis was used to establish the existence of weak hydrogen bonds connecting the bromide ions with ethylene glycol molecules into infinite chains.

A new ligand, BEDT-TTF: crystal and molecular structure of (BEDT-TTF)Cu3I4

X-ray structural examination of (BEDT-TTF)Cu3I4 crystals has shown for the first time that BEDT-TTF, previously known solely as a neutral molecule or cation-radical, acts as a bidentate ligand in binding Cu atoms.

Unusual transformations of arylhydrazonoyl chlorides of ethyl oxalate

X-ray diffraction structural analysis, IR,13C NMR, and PMR spectroscopy was used to establish that the products of the reactions of arylhydrazonoyl chlorides of ethyl oxalate and sodium ethylate are 1,4-diaryl-3,6-dicarboethoxy-1,4-dihydro-1,2,4,5-tetrazines and 1-aryl-3-carboethoxy-4-arylhydrazono-5-pyrazolones.

Geminal systems. 50. Solvolysis of 1-tosyloxy-Δ2-1,2,3-triazoline-5,5-dicarboxylate esters and the structure of the solvolysis product, O-tosyl-N-α,α-bis(ethoxycarbonyl)-β-methoxyethylhydroxylamine

Solvolysis of 1-tosyloxy-Δ2-1,2,3-triazoline-5,5-dicarboxylic acid esters (1) occurs via elimination of N2 and leads predominantly to N-β-hydroxylethyl-O-tosylhydroxylamines (II), whose structure was determined unequivocally by x-ray structural analysis. The mechanism of solvolysis of triazolines (I) is discussed, along with the structural characteristics and stabilization factors of the O-tosylhydroxylamine products (II).