Synthesis and characterization of platinum – selenium derivatives: X-ray structure of <Emphasis Type="Italic">trans</Emphasis>-Pt(PEt<Subscript>3</Subscript>)<Subscript>2</Subscript>(SePh)<Subscript>2</Subscript>

The crystal structure of trans-[((bis)triethylphosphine)(bis(phenylselenato))platinum (II)] has been determined by single crystal X-ray diffraction. Crystallization occurs in the triclinic space group P-1 (No. 2) with a = 8.9964(2) ?, b = 11.5103(2) ?, c = 14.9335(3) ?; α = 85.8750(10)°, β = 72.5350(10)°, γ = 68.4450(10)°. Details of the structure and spectroscopic results are presented and discussed and comparisons are made with related square planar platinum (II) structures.     

Structural Features of <Emphasis Type="Italic">Ortho</Emphasis>-hydroxy Bis-phenols and Their Comparison with <Emphasis Type="Italic">Para</Emphasis>-hydroxy Bis-phenols

Abstract The crystal structures of four bis-phenols are reported to substantiate the fact that the weak interactions play a major role in the crystal packing of bis-phenols. The reaction of 2,4-dimethylphenol with aldehydes such as 2-naphthaldehyde, terephthaldehyde in the presence of trifluoracetic acid gave 2-[bis(2-hydroxy 3,5-dimethylphenyl)methyl]naphthalene (1) and 4-[bis(2-hydroxy 3,5-dimethylphenyl) methyl]benzaldehyde (2), respectively. The 2-[bis-(2-hydroxy 3,5-dimethylphenyl)-methyl]naphthalene (1) crystallizes in orthorhombic, Pbca, a = 11.905(3) ?, b = 18.788(5) ?, c = 18.894(5) ?, 4-[bis(2-hydroxy 3,5-dimethylphenyl)methyl] benzaldehyde (2) in monoclinic, Cc, a = 8.880(3) ?, b = 16.394(7) ?, c = 13.700(5) ?, γ = 104.542(2)°. The reaction of 2-nitrobenzaldehyde with 2,4-dimethylphenol gave 2-benzo[c] isoxazo-3-yl 4,6-dimethylphenol (3) and its crystal parameters are orthorhombic, P2₁2₁2₁, a = 7.737(6) ?, b = 11.885(9) ?, c = 13.336(8) ?. The reaction of 2,6-dimethylphenol with 4-nitrobenzaldehyde and 2-chlorobenzaldehyde gave bis(4-hydroxy 3,5-dimethylphenyl)(4-nitrophenyl)methane (4) and bis(4-hydroxy 3,5-dimethylphenyl)(2-chlorophenyl)methane (5), respectively. The bis(4-hydroxy 3,5dimethylphenyl)(4-nitrophenyl)methane (4) crystallizes in monoclinic, C2/c, a = 25.921(1) ?, b = 12.202(4) ?, c = 15.6084(7) ?, β = 122.172(4)°, and bis(4-hydroxy 3,5-dimethylphenyl) (2-chlorophenyl)methane crystallizes as acetonitrile solvate (5) in triclinic, P-1, a = 12.314(3) ?, b = 14.111(3) ?, c = 15.078(5) ?, α = 98.268(2)°, β = 111.268(2)°, γ = 114.304(1)˚. The unit cell of 5 contains two pairs of crystallographically unsymmetric molecules of bis-phenols. Index abstract The crystal structures of four bis-phenols are reported to substantiate the fact that the weak interactions plays a major role in crystal packing and can induce symmetry non-equivalence among bis-phenols in unit cell of bis-phenols.      

The X-ray crystal structures of three bis(cyclopentadienyl)titanium(IV) derivatives

The X-ray crystal structures of (aqua)bis(cyclopentadienyl)chlorotitanium(IV) trifluoromethanesulfonate, bis(aqua)bis(cyclopentadienyl)titanium(IV) bis(trifluoromethanesul-fonate) and bis(cyclopentadienyl)bis(trifluoromethanesulfonato)titanium(IV) show a pseudo-tetrahedral array of Cp ring centroids and oxygen or oxygen and chloride donors around titanium, and varied long-range packing motifs dependent on the availability of hydrogen bond acceptors within the lattice.     

Crystal Structures of 1,7-Bis(furyl)-4-(1,3-dithiolan-2-ylidene)-1,6-heptadiene-3,5-dione and 1,7-bis(thienyl)-4-(1,3-dithiolan-2-ylidene)-1,6-heptadiene-3,5-dione

Abstract  

The title compounds (bis(alkenoyl) ketene dithioacetals) were prepared starting from the cyclic acyl ketene dithioacetal and aromatic aldehydes. These compounds were characterized by IR, ¹H NMR, mass spectral studies and X-ray crystal structure analysis. The bis(furyl) ketene dithioacetal crystallized in the space group P[`\text1] P{\bar{\text{1}}} with unit cell dimensions a = 7.7626(12) ?, b = 9.0217(13) ?, c = 26.827(5) ?, α = 86.271(14)°, β = 87.643(14)°, γ = 66.286(11)° and the structure was refined to an R-factor of 0.0528 while bis(thienyl) ketene dithioacetal crystallized in the space group P2₁/c with unit cell dimensions a = 10.2433(9) ?, b = 10.4142(6) ?, c = 18.0973(18) ?, β = 106.0° and the structure was refined to an R-factor of 0.0446. The ketenedithioacetal functionality present between the carbonyl groups prevents the possibility of keto-enol tautomerization in these compounds. In both the crystal structures, the crystal packing is stabilized by C–H···O hydrogen bonds as well as van der Waals interactions.     

Crystal and Molecular Structures of Six Differently with Halogen Substituted Bis (benzylimido) perylene

The structures of bis (3,5‐dichlorobenzylimido) perylene, bis (3‐chlorobenzylimido) perylene, bis (3‐fluorobenzylimido) perylene, bis (3,5‐difluorobenzylimido) perylene, bis (4‐chlorobenzylimido) perylene, and bis (2,6‐difluorobenzylimido) perylene were solved by single crystal analysis. The compounds crystallize in four different space groups, that is, in sequence of the compounds listed P‐1, P‐1, P2₁/a, C2/c, Pbcn, P2₁/n, respectively, although their chemical constitutions are very similar. The packing in different arrangements causes the twist of the benzene ring to differ with respect to the perylene ring and amounts to 111.4°, 112.3°, 98.6°, 105.1°, 80.3°, 72.0° for the sequence of compounds listed, respectively. The first two compounds crystallizing in space group P‐1 are isomorphous in structure and exhibit the same dark blue color. The C‐F bond distances lie between 1.36 and 1.38 Å, the C‐Cl bond distances between 1.73 and 1.75 Å. For all six structures investigated the planes of two adjacent perylene skeleton planes are 3.43 to 3.50 Å apart and the tilt angles versus the shortest unit cell dimension lie between 20° and 45°.     

Hydrogen Bonding in the Crystal Structures of New Imidazolium Triflimide Protic Ionic Liquids

Abstract  The synthesis and crystal structures of 1,3-diamino-2-methylimidazolium bis(trifluoromethylsulfonyl)imide (1), 1,3-dihydroxy-2-methylimidazolium bis(trifluoromethylsulfonyl)imide (2) and 1-(2-(diethylammonio)ethyl)-3-methylimidazolium bis(bis(trifluoromethylsulfonyl)imide) (4) are reported. The salts 1, 2 and 4 have melting points below 100 °C, the intermediate 1-(2-(diethylamino)ethyl)-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (3) is liquid at room temperature. Compound 1 is monoclinic, space group P2₁/n with a = 8.4979(4) ?, b = 12.2803(6) ?, c = 13.9400(7) ?, β = 93.086(4)°, and Z = 4. Compound 2 is monoclinic, space group P2₁/c with a = 7.6165(2) ?, b = 20.5323(8) ?, c = 9.7654(3) ?, β = 111.046(2)°, and Z = 4. Compound 4 is triclinic, space group with a = 8.5313(4) ?, b = 9.2157(4) ?, c = 20.5812(8) ?, α = 84.668(2)°, β = 83.738(2)°, γ = 63.096(2)°, and Z = 2. The ions in 1 build a network of N–H···O hydrogen bonds, in 2 they are linked to chains by O–H···N and bifurcated O–H···O hydrogen bonds, whereas in 4 they form pairs by N–H···O contacts. The triflimide anions adopt transoid conformations. Index Abstract  Short interionic contacts, conformational flexibility, and disorder phenomena were identified in the crystal structures of three new, low-melting, protic imidazolium triflimides.      

Utilization and Modification of Perovskite-Type Layered Structures as Inorganic-Organic Hybrid Materials

Abstract

The aromatic ammonium-based layered halide compounds were obtained of bis(4-nitroanilinium)tetrachlorocadmate and bis(2-methyl-4-nitroanilinium) tetrachlorocadmate, aiming at a new type of inorganic-organic hybrid layered material. X-ray diffraction analyses of the single crystals revealed that both of the crystals take an alternate layered structure of the organic bilayer and the inorganic sheet. Cadmium ion and chloride anions form six-coordinated octahedra whose corner anions are shared with the neighboring octahedra for the crystal of bis(4-nitroanilinium)tetrachlorocadmate. In the case of bis(2-methyl-4-nitroanilinium) tetrachlorocadmate crystal the inorganic portion takes distorted four-coordinated tetrahedra. The structure of the inorganic portion for the latter crystal can be considered to be caused by the distortion of a perovskite-type octahedron due to the introduction of a bulky organic molecule.     

Rh(I) and Pd(II) complexes of methoxy functionalized heterocyclic carbene: Synthesis and characterization

A new methoxy functionalized 2‐(trichloromethyl)‐1,3‐diarylimidazolidin (6) was synthesized as the precursor for N‐heterocyclic carbene complexes of Pd(II) and Rh(I) by the condensation of N,N'‐bis(2,4‐dimethoxyphenyl)‐1,2‐diaminoethane with chloral. The structures of all compounds have been elucidated by a combination of multinuclear NMR spectroscopy, elemental analysis and in one instance, by single crystal X‐ray diffraction. Compound 8, C₂₇H₃₄N₂O₄ClRh, crystallizes in the triclinic space group P‐1 with cell dimensions a = 9.7642(12)Å, b = 11.1914(11)Å, c = 13.0102(14)Å, α = 104.034(9)°, β = 106.658(9)°, γ = 99.658(9)° with Z = 2. The molecular structure of 8 shows the geometry around the Rh metal to be a slightly distorted square planar. The crystal structure shows the formation of centrosymmetric dimers via intermolecular C‐H...Cl hydrogen bonds. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis and X‐ray structure of two conformational isomers of [Zn(medpt)(SCN)2], medpt = bis (3 – aminopropyl)methylamine

Two conformational isomers of [Zn (medpt)(NCS)₂], medpt=bis(3‐aminopropyl) methylamine, (1) and (2) have been synthesised and the crystal structures are determined using single crystal X‐ray diffraction. The structures of the complexes have been solved by Patterson method and refined by full‐matrix least‐ squares techniques to R1 = 0.0524 for (1) and R1 = 0.0506 for (2), respectively. The geometry around the Zn(II) centre in both isomers is distorted trigonal bipyramidal. The two pendent thiocyanate moieties in (1), with Zn–N–C angles 167.9(4)–173.9(4)º, coordinate the mental centre almost linearly while the corresponding coordinations in (2) are significantly bent [Zn–N–C angles 150.8(3)–153.1(2)°]. Intermolecular N–H…S hydrogen bonds stabilise the crystal packing in the complexes forming infinite chains parallel to the [100] direction. The combinations of molecular chains generate three/two dimensional supramolecular framework in complexes (1) and (2). (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal structure of the UO2SO4 · 2SO(CH3)2 compound: A new type of uranyl sulfate ribbons and the UO2SO4 · 2SO (CH3)2-UO2SO4 · 2CO(NH2)2 morphotropic transition

Single crystals of bis(dimethyl sulfoxide) uranyl sulfate are prepared, and their crystal structure is determined using X-ray diffraction analysis. The crystals are monoclinic, space group P2₁/c, a = 12.9189(8) ?, b = 7.9008(5) ?, c = 12.1405(7) ?, β = 95.677(1)°, R ₁ = 0.0216, wR ₂ = 0.0468 for 2761 unique reflections with F > 2σ(F). The crystal structure of the UO₂SO₄ · 2Dmso compound (where Dmso is dimethyl sulfoxide) is built up of infinite uncharged ribbons of the composition [UO₂SO₄ · 2Dmso]_∞, in which the SO₄ tetrahedron is tridentately coordinated to two uranyl groups. The differences between the structures of the uranyl sulfate compounds formed upon replacement of dimethyl sulfoxide by other molecules are considered. Original Russian Text ? E.V. Alekseev, E.V. Suleĭmanov, E.V. Chuprunov, G.K. Fukin, E.V. Baranov, 2007, published in Kristallografiya, 2007, Vol. 52, No. 2, pp. 283–286.     

Synthesis, spectral, and single crystal X-ray structural studies on (2,2′-bipyridyl)bis(dimethyldithiocarbamato) zinc(II) and (1,10-phenanthroline) bis(dimethyldithiocarbamato)zinc(II)

Synthesis, spectral, and single crystal X-ray structural studies on (2,2-bipyridyl)bis (dimethyldithiocarbamato)zinc(II) (1) and (l,10-phenanthroline)bis(dimethyldithiocarbamato)zinc(II) (2) complexes are reported in this paper. The complex (1) crystallizes in the orthorhombic lattice, space group Pcca, a = 18.456(3), b = 6.529(2), and c = 17.092(2) Å. The complex (2) crystallizes in the monoclinic space group C2/c, a = 13.372(2), b = 13.850(2), c = 24.680(3) Å, and = 102.71(4)°. IR spectra of the complexes (1) and (2) show the thioureide (C-N) bands at 1489 and 1510 cm^–1, respectively, which are lower than the value observed for the parent bisdithiocarbamate. Reduction in the thioureide stretching frequency is due to the increase in coordination around the zinc ion and the resultant increase in electron density. Thermal studies indicate that the 1,10-phenanthroline adduct is marginally more stable than the other complex. X-ray crystal structures of the two adducts show them to be octahedrally coordinated and monomeric in nature. The Zn-S distances are longer than those observed in the parent bisdithiocarbamate. The thioureide C-N bond distances in (1) and in (2) indicate the partial double bond character. The most important structural changes as a result of the adduct formation are observed in the Zn-S bond distances and S-Zn-S bond angles, in terms of very significant increases in Zn-S bond distances and reductions in S-Zn-S angles, compared to the parent bisdithiocarbamate. The observed changes are indicative of a strong steric force in operation in the adducts rather than electronic effects.     

Crystal structure ofcis-bis[1-(2-thienyl)-4, 4,4-trifluoro-1,3-butanedionato]-bis (4-methylpyridine)nickel(II)

The crystal structure of the 4-methylpyridine adduct of bis[1-(2-thienyl)-4, 4,4-trifluoro-1,3-butanedionatolnickel(II) was determined by a three-dimensional x-ray analysis using counter data. The crystals are monoclinic,C2/c, witha = 9.330,b = 18.278,c = 17.855 Å, and = 95.1°. The structure was refined by full-matrix least squares toR = 0.10. The molecule has a two-fold axis, and both enantiomers withcis configuration occur in the crystal. The solvation by 4-methylpyridine is shown to weaken the chelate bonds in the same way as doestrans hydration.     

Crystal structures of gold,silver, and sodium chalcogenides: Sphenoidal interpretation

The crystal structures of 13 chalcogenides of Na, Au(I), and Ag(I) in the Na_{2 − n} (Au,Ag) _n (S,Se,Te) series, where 0 ≤ n ≤ 2, are interpreted from unified positions based on the sphenoidal representation. Its essence is in the consideration of the entire crystal space (with packing X atoms in the framework of close-packing, body-centered, or hybrid schemes) as a set of elementary space units (sphenoids). Unified one-dimensional associates of sphenoids, the so-called basic rods, with sets of possible atomic positions in them are selected for all structures. The mutual effect of the dimensional and stoichiometric ratios of all components on the features of filling rod positions is analyzed. New possibilities in the crystallochemical and crystal-geometry analysis of inorganic compounds whose structures are characterized by a relatively uniform distribution of atoms are demonstrated by the example of chalcogenides.     

Synthesis,Characterization and Crystal Structure of Tetraphenylphosphonium Bis(2-thioxo-1,3-dithiole-4,5-dithiolato)-Nickelate Acetone Solvate Crystal

Abstract  

A new crystal of tetraphenylphosphonium bis(2-thioxo-1,3-dithiole-4,5-dithiolato)-nickelate acetone solvate (BPNI) has been prepared at room temperature and characterized by elemental analysis, UV–Vis–NIR absorption spectrum and X-ray single crystal determination. The complex crystallized in monoclinic space group P2/c with unit cell dimensions a = 24.5350 (6) ?, b = 7.3097 (2) ?, c = 23.1141 (6) ?, β = 115.585 (2)°, V = 3738.89 (17) ?³, Z = 4, D _x .= 1.5081 (1) g cm⁻³. The X-ray structure determination revealed that the crystal is centro-symmetrical and there are two halves of independent cations in the molecule.     

Synthesis and crystal structure of 1-vinyl-cis-2,3-diphenylaziridine

1-Vinyl-cis-2,3-diphenylaziridine, C₁₆H₁₅N, has been synthesized and characterized by spectroscopic methods and single crystal X-ray analysis. The structure was studied at room temperature (2a) (18°C) and at low temperature (2b) (–70°C). The title compound crystallizes in the space group Cm with Z=2 showing no phase transformation between the two temperatures. The cell parameters area=8.258(3),b=15.880(3),c=5.827(2)Å, =122.32(2)° for (2a) anda=8.188(2),b=15.762(3),c=5.724(1)Å, =121.57(2)° for (2b). Both the studies show nearly the same conformation. With the exception of the vinyl group, the molecule hasm symmetry, so, the asymmetric unit is half a molecule. The mirror plane of the space group cuts the aziridine ring through the N atom. The vinyl group is distributed on two symmetrical positions by means of the same mirror plane. In this way, the crystal is built with the two diastereoisomers of the title compound.     

A novel porous network with interpenetrating topology

A new Co^II coordination polymer with complicated topology, namely [Co(bpp)₂Cl₂]n (1) (bpp=1,3‐bis(4‐pyridyl)propane), has been designed and synthesized based on flexible ligand under basic condition. The complex was characterized by single‐crystal X‐ray analysis and infrared spectroscopy. The Co^II ions are linked into a 3D structure via bpp molecules. Four independent frameworks are related by translation along the c tetragonal axis in the usual interpenetration topology for diamondoid frames. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Refinement,comparisonal study and EPR measurements on the molecular structure of NN‐diethyldithiocarbamate of Zn(II) and Cd(II)

The accidental formation of Zn(II) bis(N,N‐diethyldithiocarbamate) (1) and Cd(II) bis(N,N diethyldithiocarbamate) (2) during the synthesis of the target heterobinuclear Mo‐Cd‐dithiocarbamate or Mo‐Zn‐dithiocarbamtes were crystallized and the molecular structures were determined. As the dispute over the presence of Mo with Zn‐dithiocarbamate existed, single crystal EPR measurement was performed. Interestingly the doublet EPR signals of ⁶³Cu and ⁶⁵Cu patterns were observed. Single crystals of Zn₂(Et₂dtc)₄ containing approximately 2% of Cu²⁺ in the host lattice showed the doublet spectral characteristic of the Cu²⁺ ions (S = 1/2, I = 3/2). Both the molecular structures 1 and 2 were identical dimers. The cell parameters of the crystals were refined with low residual factor compared to those of the reported structures. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Mercury complexes with thiacrowns: the crystal structure of bis(1,4,7-trithiacyclodecane) mercury(II) hexafluorophosphate

We report the synthesis, crystal structure, and NMR spectroscopy for the mercury(II) complex with the crown thioether 1,4,7-trithiacyclodecane (10S3) , bis(1,4,7-trithiacyclodecane) mercury(II) hexafluorophosphate (1). The 10S3 ligand coordinates in tridentate fashion and readily forms a distorted bis octahedral complex, an unusual coordination geometry for Hg(II). The crystal structure shows the two 10S3 ligands arranged in a trans or anti fashion around the mercury center, yielding the meso stereoisomer. Bond distances and angles are very comparable to those found in the structure of the perchlorate salt of the complex cation although the hexafluorophosphate salt shows slightly longer and more varied Hg–S distances (2.623(2) , 2.708(2), 2.784(2) Å) with a tetragonal elongation. The ¹⁹⁹Hg¹H NMR spectrum exhibits a single resonance with a chemical shift at –596 ppm consistent with a hexakis(thioether) coordination environment around the mercury center. Crystal data for 1: C2/c, a = 19.184(3) Å, b = 15.235(2) Å, c = 11.3791(15) Å, = 123.358(2)°, V = 2777.9(6) ų, Z = 4.     

Synthesis and crystal structure of bis(4-methylpiperidine-dithiocarbamato-S,S′)-palladium(II)

The complex bis(4-methylpiperidine-dithiocarbamato-S,S′)-palladium(II) was synthesized by the reaction of 4-methyl-1-piperidine dithiocarbamic acid with palladium(II) chloride. Its structure was determined by X-ray crystal diffraction analysis. It crystallizes in the monoclinic P2₁/c space group with the crystal cell parameters a=8.6491(8) ?, b=18.7305(16) ?, c=11.9933(10) ?, β=107.074(1)°, V=1857.3(3) ?³ and Z=4. The palladium (II) ion is bonded to four sulfur atoms, belonging to two dithiocarbamate ligands, in a distorted square planar geometry. The X-ray data suggest a pronounced electronic delocalization in the two NCS₂ moieties.