Transition metal sulfur dioxide hexafluoroarsenates and hexafluoroantimonates (original) (raw)
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Inorganic Chemistry, 2002
The new compound trifluoroacetylsulfenyl trifluoroacetate, CF 3 C(O)SOC(O)CF 3 , which possesses two identical carbonyl substituents attached to the S−O bond, has been synthesized. The IR and UV spectra of the gas phase as well as the 13 C NMR spectrum of the solution in CDCl 3 were recorded and assigned. Quantum chemical calculations were performed with the ab initio methods HF and MP2 and the density functional approach B3LYP. The 6-31G* basis set was chosen in all calculations. The molecule possesses a skew structure, and according to all computational methods, the syn−syn structure (CdO bonds of both C(O)CF 3 groups synperiplanar to S−O bond) represents the most stable conformer. In agreement with the quantum chemical calculations, the presence of small amounts (e5%) of a second conformer (anti−syn) cannot be excluded on the basis of the IR spectrum. The calculated values for the torsional angle around the S−O bond (δ(C−S−O−C)) of the syn−syn form are smaller than 80°( 72−78°). Comparison with theoretical results for the corresponding disulfide CF 3 C(O)SSC(O)CF 3 and peroxide CF 3 C(O)OOC(O)CF 3 indicates that the structural properties of sulfenyl compounds are more similar to those of disulfides than to those of peroxides.
Vibrational Spectroscopy, 2007
The infrared spectra of [CH 3 (CH 2) 2 NH 3 ] 2 SiF 6 , [CH 3 (CH 2) 3 NH 3 ] 2 SiF 6 and [(C 2 H 5) 2 NH 2 ] 2 SiF 6 compounds, synthesized by us, were recorded at room temperature and discussed. For the butylammonium hexafluorosilicate which crystallized in orthorhombic system with P321 (Z = 1), and ethylammonium hexafluorosilicate crystallizes at room temperature in the monoclinic system with P2 1 as space group the discussions are made in relation to previously mentioned crystal structures. The vibrational spectra of the cations indicate that they are disordered and hydrogen bonded to the anions. Hydrogen bonding in these compounds is indicated by overtone and combination modes possessing appreciable intensities. The results are compared to density functional theory B3LYP and semi-empirical PM3 calculations. Full thermodynamic properties and geometries are also located and characterized.
Three hexafluoridoiridates(IV), Ca[IrF6].2H2O, Sr[IrF6].2H2O and Ba[IrF6]
Acta crystallographica. Section C, Crystal structure communications, 2007
The structures of the hexafluoridoiridates(IV) of calcium, Ca[IrF(6)].2H(2)O [calcium hexafluoridoiridate(IV) dihydrate], strontium, Sr[IrF(6)].2H(2)O [strontium hexafluoridoiridate(IV) dihydrate], and barium, Ba[IrF(6)] [barium hexafluoridoiridate(IV)], have been determined by single-crystal X-ray analysis. The first two compounds are isomorphous. Their metal cations are eight-coordinated in a distorted square-antiprismatic coordination environment, and their anions are represented by an almost ideal octahedron. These two structures can be described as frameworks in which all atoms occupy general positions. Sr[RhF(6)] and Ba[RhF(6)] have a different space group (R\overline{3}m, from powder diffraction data) but similar cell dimensions. The structures are very close to that of Ba[IrF(6)]. The cation is in a cuboctahedral coordination. The metal atoms are located on special positions of \overline{3} symmetry, while the F atoms are in general positions.
Organometallics, 1995
The chemistry of organically templated metal sulfates has attracted interest from the materials science community and the development of synthetic strategies for the preparation of organic-inorganic hybrid materials with novel structures and special properties is of current interest. Sulfur-oxygen-metal linkages provide the possibility of using sulfate tetrahedra as building units to form new solid-state materials. A series of novel organically templated metal sulfates of 2-aminopyridinium (2ap) with aluminium(III), cobalt(II), magnesium(II), nickel(II) and zinc(II) were obtained from the respective aqueous solutions and studied by single-crystal X-ray diffraction. The compounds crystallize in centrosymmetric triclinic unit cells in three structure types: type 1 for 2-aminopyridinium hexaaquaaluminium(III) bis(sulfate) tetrahydrate, (C 5 H 7 N 2)[Al(H 2 O) 6 ](SO 4) 2 Á4H 2 O, (I); type 2 for bis(2-aminopyridinium) tris-[hexaaquacobalt(II)] tetrakis(sulfate) dihydrate, (C 5 H 7 N 2) 2 [Co(H 2 O) 6 ] 3 (SO 4) 4 Á-2H 2 O, (II), and bis(2-aminopyridinium) tris[hexaaquamagnesium(II)] tetrakis-(sulfate) dihydrate, (C 5 H 7 N 2) 2 [Mg(H 2 O) 6 ] 3 (SO 4) 4 Á2H 2 O, (III); and type 3 for bis(2-aminopyridinium) hexaaquanickel(II) bis(sulfate), (C 5 H 7 N 2) 2 [Ni(H 2 O) 6 ]-(SO 4) 2 , (IV), and bis(2-aminopyridinium) hexaaquazinc(II) bis(sulfate), (C 5 H 7 N 2) 2 [Zn(H 2 O) 6 ](SO 4) 2 , (V). The templating role of the 2ap cation in all of the reported crystalline substances is governed by the formation of characteristic charge-assisted hydrogen-bonded pairs with sulfate anions and the presence ofinteractions between the cations. Additionally, both coordinated and uncoordinated water molecules are involved in hydrogen-bond formation. As a consequence, extensive three-dimensional hydrogen-bonding patterns are formed in the reported crystal structures. Data collection Diffractometer Rigaku Oxford Diffraction Xcalibur Atlas Rigaku Oxford Diffraction Xcalibur Atlas Absorption correction Analytical [CrysAlis PRO (Rigaku Oxford Diffraction, 2015), based on expressions derived by Clark & Reid (1995)] Analytical [CrysAlis PRO (Rigaku Oxford Diffraction, 2015), based on expressions derived by Clark & Reid (1995)] T min , T max 0.879, 0.909 0.694, 0.921 No. of measured, independent and observed [I > 2(I)] reflections 11780, 2662, 2341 7323, 2563, 2120 R int 0.026 0.032 (sin /) max (Å À1) 0.695 0.696 Refinement R[F 2 > 2(F 2)], wR(F 2), S 0.026, 0.060, 1.07 0.037, 0.078, 1.08 No. of reflections 2662 2563 No. of parameters 160 160 No. of restraints 6 6 Á max , Á min (e Å À3) 0.31, À0.44 0.38, À0.56
Cyclic sulfonium salts with S... O interactions 2. Molecular structures with six-membered rings
Structural …, 1991
chloride (4) and 1 -(8'carboxylatonaphtyl)-2-methyl-3-oxo-3H-1,2-naphto-(1,8-d,e)-thiazin-l-ium dipolar ion (5) cyclic sulfonium salts were prepared and their chemical properties investigated (spirosulfurane-formation, hydrolysis). The molecular structures obtained from x-ray diffraction can be described with a considerably distorted trigonal bipyramidal arrangement of the ligands about the sulfonium center, with O/N--S 9 9 9 0----apical angles of 173.9, 164.9, 156.6, and 159.0 ~ as well as with S--O/N apical bond lengths of 1.648, 1.671, 1.664, and 1.682 A. The structures exhibit relatively short S 9 9 9 0 close contacts with interatomic distances of 2.253, 2.448, 2.795, and 2.619 •.
Synthesis and characterization of alkyl-2,2,2-trifluoroethyl sulphites
Polyhedron, 1993
new asymmetric organic sulphites, R'CH20S(0)OCH2CF3 (R' = H, CH,, CH,Cl, C2H, or C3H7) were prepared and characterized by elemental analyses, IR, mass and multinuclear ('H, ' 3C, "F) NMR spectral studies. The quantitative increase of 'H NMR chemical shift difference of non-equivalent protons with bulk of the R' substituent is reported.