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C2v Symmetry (c2v + symmetry)
Selected AbstractsConfiguration of Octahedral Metal Compounds , Equilibrium, Crystal and Molecular Structure of Nickel(II) Complexes of Linear N2O4, N4S2 or N6 Donors Set Atoms LigandsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 6 2004Aminou Mohamadou Abstract Two new nickel(II) complexes of symmetric hexadentate mixed-ligand N,O [1,12-bis(2-pyridyl)-5,8-dioxa-2,11-diazadodecane (pydado)] and N,S [1,12-bis(2-pyridyl)-5,8-dithia-2,11-diazadodecane (pydadt)] donor atoms have been synthesised as perchlorate salts and characterised by X-ray crystallography and ligand-field spectroscopy. In both complexes the Ni2+ ion is hexacoordinate. The cation [Ni(pydado)]2+ is pseudo-octahedral with the two pyridyl groups in trans position; all Ni,N and Ni,O bond lengths are practically equivalent. In [Ni(pydadt)]2+ complex, however, the size of the thioether sulfur atoms imposes a C2v symmetry; the pyridyl groups and the sulfur atoms are in trans positions and all Ni,N bond lengths are equivalent. The comparison of these structures with those of octahedral cobalt, copper and zinc complexes with the same ligands shows that their configurations depend not only on the nature of the two central donor atoms of the ligand, but also on the nature of the metallic ion. In aqueous solution, the stability constants of the NiII chelates with these two ligands, determined by potentiometry, show the formation of [Ni(LH)]3+ and [NiL]2+ species in all cases. The chelating power of the pydadt ligand is slightly greater than that of pydado. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] Gas-Phase Electron-Diffraction Investigation and Quantum-Chemical Calculations of the Structure of 1,5-Dimethylsemibullvalene-2,4,6,8-tetracarboxylic DianhydrideHELVETICA CHIMICA ACTA, Issue 5 2003Svein Samdal The bridged homotropilidines have been of interest for decades because their molecules offer the potential for homoaromaticity. Although many of these have been shown not to be homoaromatic, the energy differences of the delocalized (homoaromatic) forms and the localized (nonhomoaromatic) ones, and the barriers to the interconversion of the localized forms via a Cope rearrangement, have been found to vary greatly. The title compound is a strong candidate for homoaromaticity, and, since the structures of the possible localized and delocalized forms could differ significantly, we have carried out an electron-diffraction investigation of it augmented by quantum-mechanical calculations with different basis sets at several levels of theory. Three models were explored: one representing a localized form of Cs symmetry, one a delocalized form of C2v symmetry, and one a 2,:,1 mixture of the localized/delocalized forms. Although none of the models could be ruled out, the experimental evidence slightly favors the Cs form. These results are consistent with those from the DFT B3PW91 calculations with basis sets ranging from 6-31G(d) to cc-pVTZ, which, surprisingly, predict essentially equal thermally corrected free energies for each. The results are discussed. [source] Trends of the bonding effect on the performance of DFT methods in electric properties calculations: A pattern recognition and metric space approach on some XY2 (X = O, S and Y = H, O, F, S, Cl) moleculesJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 2 2010Christos Christodouleas Abstract A test set of 10 molecules (open and ring forms of ozone and sulfur dioxide as well as water and hydrogen sulfide and their respective fluoro- and chloro-substituted analogs) of specific atmospheric interest has been formed as to assess the performance of various density functional theory methods in (hyper)polarizability calculations against well-established ab initio methods. The choice of these molecules was further based on (i) the profound change in the physics between isomeric systems, e.g., open (C2v) and ring (D3h) forms of ozone, (ii) the relation between isomeric forms, e.g., open and ring form of sulfur dioxide (both of C2v symmetry), and (iii) the effect of the substitution, e.g., in fluoro- and chloro-substituted water analogs. The analysis is aided by arguments chosen from the information theory, graph theory, and pattern recognition fields of Mathematics: In brief, a multidimensional space is formed by the methods which are playing the role of vectors with the independent components of the electric properties to act as the coordinates of these vectors, hence the relation between different vectors (e.g., methods) can be quantified by a proximity measure. Results are in agreement with previous studies revealing the acceptable and consistent behavior of the mPW1PW91, B3P86, and PBE0 methods. It is worth noting the remarkable good performance of the double hybrid functionals (namely: B2PLYP and mPW2PLYP) which are for the first time used in calculations of electric response properties. © 2009 Wiley Periodicals, Inc. J Comput Chem 2010 [source] Computational study of the cooperative effects of nitrogen and silicon atoms on the singlet,triplet energy spacing in 1,3-diradicals and the reactivity of their singlet statesJOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 4 2010Takeshi Nakamura Abstract Quantum chemical calculations were performed to investigate the cooperative effect of the nitrogen and silicon atoms on the singlet,triplet energy spacing and the reactivity of the singlet state in 1,2-diazacyclopentane-3,5-diyls and 1,2-diaza-4-silacyclopentane-3,5-diyls. The largest singlet,triplet energy gap (,=,,36.1,kcal/mol) found so far in localized 1,3-diradicals was in the C2v symmetry of 4,4-difluoro-1,2-diaza-4-silacyclopentane-3,5-diyl at the UB3LYP/6-31G(d) level of theory. The cooperative effect was also found in the energy differences of singlet diradicals with the corresponding ring-closing compounds, bicyclo[2.1.0]pentane derivatives. The singlet state of the 1,2-diaza-4-silacyclopentane-3,5-diyls was calculated to be energetically more stable than the ring-closing compound. The notable finding on the stability of the singlet diradicals may be attributed to the resonance structures that specifically stabilize the singlet state of diradicals. The computational studies predict that the singlet 1,2-diaza-4-silacyclopentane-3,5-diyl is a persistent molecule under conditions without intermolecular-trapping reagents. Copyright © 2010 John Wiley & Sons, Ltd. [source] Evidence from ESR studies for [Co(,-C2H4)3] produced at 77 K in a rotating cryostat,MAGNETIC RESONANCE IN CHEMISTRY, Issue 10 2006Lynda J. Hayton Abstract Co atoms were reacted with ethene at 77 K and the paramagnetic products studied by electron spin resonance (ESR) at X- and K-bands. The ESR spectra of the major product at both frequencies showed eight cobalt multiplets (ICo = 7/2) indicating a mono-cobalt complex. The spectra have orthorhombic g and cobalt hyperfine tensors and were simulated by the parameters; g1 = 2.284, g2 = 2.0027, g3 = 2.1527; A1 < , 25 MHz, A2 = , 109 MHz, A3 = , 198 MHz. Proton and 13C (1% natural abundance) hyperfine couplings were lower than the line widths (<2 MHz) indicating less than 0.5 spin transfer to the ethene ligands. We assigned the spectrum to a Jahn,Teller-distorted planar trigonal mono-cobalt tris-ethene [Co(,-C2H4)3] complex in C2v symmetry. The SOMO is either a 3dx2,y2 (2a1) orbital in a T-geometry or a 3dxy (b1) orbital in a Y-geometry but there is only a spin density, a2, of 0.30 in these d orbitals. The spin deficiency of 0.70 is attributed to two factors; spin transfer from the Co to ethene ,/,* orbitals and a 4p orbital contribution, b2, to the SOMO. Calculations of a2 and b2 have been made at three levels of spin transfer, ,. At , = 0.00a2 is 0.23 and b2 is 0.78, at , = 0.25a2 is 0.25 and b2 is 0.52 and at , = 0.50a2 is 0.28 and b2 is 0.23. The other possible assignment to a mono-cobalt bis-ethene complex [Co(,-C2H4)2] cannot be discounted from the ESR data alone but is considered unlikely on other grounds. The complex is stable up to ,220 K indicating a barrier to decomposition of ,50 kJ Mol,1 Copyright © 2006 John Wiley & Sons, Ltd. [source] A capped trigonal prismatic cadmium complex with tetra- and tridentate ligands: bis(triethanolamine)-,3N,O,O,;,4N,O,O,,O,,-cadmium(II) squarate monohydrateACTA CRYSTALLOGRAPHICA SECTION C, Issue 8 2004brahim Uçar In the crystal structure of the title compound, [Cd(C6H15NO3)2](C4O4)·H2O, a supramolecular structure is observed. The asymmetric unit consists of one unit of the cationic Cd complex, one water molecule and two half-squarate anions, each sitting on a crystallographic inversion center. The different coordinations of the two triethanolamine (TEA) ligands results in an unusual example of coordination number seven for the CdII ion. Both TEA ligands coordinate to the CdII ion, forming a distorted monocapped trigonal prismatic geometry with approximate C2v symmetry. One of the TEA ligands acts as an N,O,O,-tridentate ligand, whereas the other behaves as an N,O,O,,O,,-tetradentate donor. The anions and cations are linked to one another by hydrogen bonds between hydroxy H atoms of the TEA ligands and squarate O atoms. The crystal structure is stabilized by O,H,O hydrogen bonds between the unligated water molecule and a squarate O atom, together with a weak ,,ring interaction between the ethylene group of a TEA ligand and a squarate anion. [source] Evaluation of Electron Population Terms for ,rSe,3,4p, ,rS,3,3p, and ,rO,3,2p: How Do HOMO and LUMO Shrink or Expand Depending on Nuclear Charges?CHEMISTRY - A EUROPEAN JOURNAL, Issue 24 2008Waro Nakanishi Prof. Abstract Electron population terms ,, are evaluated for N=Se, S, and O. Calculations are performed on HOMO and LUMO constructed by pure atomic 4p(Se), 3p(S), and 2p(O) orbitals, employing the 6-311+G(3d) and/or 6-311++G(3df,3pd) basis sets at the HF, MP2, and DFT (B3,LYP) levels. Se4+, Se2+, Se0, and Se2, with the Oh symmetry are called G(A: Se) and HSe+, H2Se, and HSe, with the C,h or C2v symmetry are named G(B: Se), here [G(A+B: Se) in all]. HOMO and LUMO in G(A+B: N) (N=Se, S, and O) satisfy the conditions of the calculations for ,,. The ,,4p, ,,3p, and ,,2p values correlate well with the corresponding MO energies (,N) for all calculation levels employed. Plots of ,,HOMO and ,,LUMO versus Q(N) (N=Se, S, and O) at the HF and MP2 levels are analyzed as two correlations. However, the plots at the DFT level can be analyzed as single correlation. A regression curve is assumed for the analysis. Behaviors of ,, clarify how valence orbitals shrink or expand depending on Q(N). The applicability of ,, is examined to establish a new method that enables us to analyze chemical shifts with the charge effect separately from others. A utility program derived from the Gaussian 03 (NMRANAL-NH03G) is applied to evaluate ,, and examine the applicability to the NMR analysis. [source] Methylazacalixpyridines: Remarkable Bridging Nitrogen-Tuned Conformations and Cavities with Unique Recognition PropertiesCHEMISTRY - A EUROPEAN JOURNAL, Issue 36 2006Han-Yuan Gong Abstract Methylazacalix[n]pyridines (n = 4, 8) and methylazacalix[m]arene[n]pyridines (m = n = 2, 4) have been synthesized by a convenient fragment coupling approach starting from 2,6-dibromopyridine, 2,6-diaminopyridine, and benzene-1,3-diamine. Thanks to the intrinsic electronic nature of nitrogen, which can adopt mainly sp2 hybridization, allowing it variously to conjugate, partially conjugate, or not conjugate with the adjacent one or two pyridine rings, the resulting nitrogen-bridged calixpyridine derivatives act as a unique class of macrocyclic host molecules with intriguing conformational structures offering fine-tunable cavities and versatile recognition properties. Whilst in solution it is fluxional, in the solid state methylazacalix[4]pyridine adopts a 1,3-alternate conformation with a C2v symmetry in which every two bridging nitrogen atoms conjugate with one pyridine ring. After protonation, the methylazacalix[4]pyridinium species has a different conjugation system of its four bridging nitrogen atoms, yielding the similar twisted 1,3-alternate conformations with an approximate S4 symmetry. The cavity of each protonated methylazacalix[4]pyridine, however, varies finely to accommodate guest species of different size and geometry, such as planar DMF or HO2CCO2, ion, a twisted HO2CCO2, ion, and a tetrahedral ClO4, ion. As giant macrocyclic hosts, both methylazacalix[8]pyridine and methylazacalix[4]arene[4]pyridine interact efficiently with fullerenes C60 and C70 through van der Waals forces. Their ease of preparation, versatile conformational structures, and recognition properties make these multinitrogen-containing calixarenes or cyclophanes unique and powerful macrocyclic hosts in supramolecular chemistry. [source] Density Functional Theory (DFT) studies on the ground state of NO3(2A,2) radical and the first triplet state of NO3+cationCHINESE JOURNAL OF CHEMISTRY, Issue 3 2000Cao Xiao-Yan Abstract Density Functional Theory (DFT) studies on the ground states (2A,2) of NO3 radical and on die ground state (1A,;1) and the first triplet state (3E,) of NO3+ cation provide an unambiguous prediction about their geometrical structure: the ground states of both NO3 radical and NO3+ cation have D3h symmetry and the geometrical configuration of me first triplet state 3E, of NO3+ cation has C2v symmetry. It is shown that as for as the ionization energy calculations on NO3 radical are concerned, the results are only slightly different, no mater that gradient corrections of the exchange-correlation energy are included during self-consistent iterations or they are included as perturbations after the self-consistent iterations. [source] | ||||||||||||||||||||||