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991.
Marijana Gavranić Branko Kaitner Ernest Meštrović 《Journal of chemical crystallography》1996,26(1):23-28
The structures of N-(-naphthyl)-2-oxy-1-naphthaldimine1 and N-(-naphthyl)-2-oxy-1-naphthaldimine2 have been investigated by X-ray analysis and by spectroscopic methods. Crystals of1 are monoclinic, space groupPn, with cell dimensionsa=10.823(3),b=5.826(2),c=11.899 (3) Å, and =99.66(3)°. Compound2 crystallizes in the orthorhombic space groupPca21 witha=17.564(3),b=6.314(2), andc=13.663(4) Å. The IR spectra exhibited neither N–H nor O–H stretching frequencies. The existence of theintramolecular hydrogen bonding of N–H...O type was predicted by spectroscopic experiment but unequivocally established by diffraction experiment in both cases1 and2. The molecules1 and2 are significantly planar with considerable quinoid effect at the 2-oxy-naphthaldimine moiety. Although essentially planar, both molecules1 and2 show the delocalization of -electrons only in the central part of the molecules including C=N imino group with pendent ring carbon atoms.Intermolecular attractions in the crystals belong to weak van der Waals interactions-between discrete planar molecules spatially arranged into the expectedherringbone motif in the solid state. 相似文献
992.
Huafeng Shen Jian Cheng Wang Simon G. Bott Michael G. Richmond 《Journal of chemical crystallography》1994,27(11):649-656
Thermolysis of Ru3(CO)12 with 2,3-bis(diphenylphosphino)maleic anhydride (bma) in toluene solution gives the new compounds Ru3(CO)10(bma) (2), Ru2(CO)6(bma) (3), and
(4). All compounds have been isolated and characterized in solution by IR and31P NMR spectroscopy. The solid-state structures of2, as the monohydrate, and4 were established by X-ray crystallography. Ru3(CO)10(bma)·H2O crystallizes in the monoclinic space groupC2/c,a=12.741(2) ?,b=19.548(2) ?,c=32.973(4) ?, β=96.847(9)°,V=8154(2) ?3,Z=8,d
calc=1.740 g cm−3;R=0.046,R
w
=0.051 for 2541 observed reflections withl>3σ(l). The bma ligand in2 is bound to the triruthenium frame in a bridging fashion, with equatorially disposed PPh2 groups. The X-ray structure of2 reveals an extreme twisting of the maleic anhydride ring away from the plane defined by the plane of the three ruthenium
atoms, along with a significant lengthening of the maleic anhydride C=C π bond.
crystallizes in the monoclinic space groupP21/c,a=9.3113(5) ?,b=18.164(1) ?,c=20.097(1) ?, β-102.021(4)°,V=3324.5(3) ?3,Z=4,d
calc=1.671 g cm−3;R=0.024,R
w
=0.030 for 3499 observed reflections withl>3σ(l). The presence of the μ2 moiety and P−C (maleic anhydride) bond cleavage attendant in the formation of4 are confirmed by X-ray analysis. The relationship of the compounds3 and4 to the dimeric compounds Ru2(CO)6(bpcd) and
[where bpcd=4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione] is discussed. Independent studies dealing with Ru3(CO)10(bma) (bridging isomer) have shown that cluster2 is stable in toluene solution at elevated temperature and does not afford compounds3 and4, suggesting the intermediacy of the putative chelating isomer of Ru3(CO)10(bma) (1) as the source of3 and4. 相似文献
993.
Leonard R. MacGillivray Michael J. Zaworotko 《Journal of chemical crystallography》1994,24(10):703-705
The crystal and molecular structure of 2,6-dihydroxybenzoic acid has been determined by single crystal X-ray diffraction. The crystals are monoclinic witha=5.4084(5),b=5.2240(7),c=22.986(4) Å, =94.69(3)°, space group P21/c,Z=4,V=647.27(16) Å3,d
c
=1.58Mg m–3, The acid crystallizes as hydrogen bonded carboxylic dimers which pack to generate a herringbone motif of the type typically encountered in polycyclic aromatic compounds. 相似文献
994.
H. Ünver M. Yıldız D. Mehmet Zengin S. Özbey E. Kendi 《Journal of chemical crystallography》2001,31(4):211-216
N-(3-pyridil)-2-oxo-1-naphthylidenemethylamine (C16H12N2O) was studied by elemental analysis, IR, 1H NMR, and UV–visible techniques and X-ray diffraction methods. The UV–visible spectrum of the compound was investigated in solutions effect polarity. The polarity of the some solvents was modifierly the additional (CF3COOH) and [(C2H5)3N]. The compound is in tautomeric equilibrium (phenol-imine O–H···N and keto-amine O···H–N forms) in polar and nonpolar solvents. The keto-amine form is observed in basic solutions of DMSO, ethanol, chloroform, benzene, cyclohexane, and in acidic solutions of chloroform and benzene, but not in acidic solutions of DMSO and ethanol. The compound crystallizes in the monoclinic, space group P21/a with a = 7.010(5) Å, b = 13.669(4) Å, c = 12.764(4) Å, = 101.23(4)°, V = 1199.6(10) Å3, Z = 4, D
c = 1.375 g/cm3, (Mo K) = 0.088 mm–1, R = 0.045 for 1658 reflections [I > 2(I)]. The title compound is not planar two Schiff base moieties A [C1–C11, O1] and B [N1, C12, C13, N2, C14, C15, C16] are inclined at an angle of 27.4(1)° reflecting mainly the twist about C12–N1 [C11–C12–N1–C13, 29.7(2)°]. There is a strong intramolecular hydrogen bond (O–H···N) of 2.529(2) Å. 相似文献
995.
Wang R Li Q Wu R Wu G Yu Z 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2008,70(4):793-798
The molecular interactions of pyrazine (PZ) with n-propanol, chloroform, and tetrahydrofuran (THF) have been investigated by employing ultraviolet spectroscopy and quantum chemical calculation methods. A new quantity, excess absorption coefficient, was introduced to represent the strength of the interaction. It was found that the interaction decreased in the order: PZ-propanol>PZ-chloroform>PZ-THF. The Benesi-Hildebrand method indicated that the interaction stoichiometries of the PZ-chloroform and PZ-THF systems were both 1:1 and the equilibrium constants were determined to be 2.07 and 0.64M(-1), respectively. Using a nonlinear fitting method, we demonstrated that the PZ-propanol was a two-step 1:2 interaction pair and the equilibrium constants were determined to be 8.8 and 0.19M(-1). Quantum chemical calculations showed the existence of hydrogen-bonding interactions in all the three system: normal Ncdots, three dots, centeredH-O hydrogen bond in the PZ-propanol system, unconventional Ncdots, three dots, centeredH-C hydrogen bond in the PZ-chloroform, and weak N-C-Hcdots, three dots, centeredO hydrogen bond in the PZ-THF system. Methodologically, we pointed out that special care must be taken when the Benesi-Hildebrand method is used to evaluate 1:2 interactions. 相似文献
996.
Hinne Hettema 《Foundations of Chemistry》2008,10(2):135-142
Michael Weisberg’s recent 2007 paper on the chemical bond makes the claim that the chemical notion of the covalent bond is
in trouble. This note casts doubts on that claim.
相似文献
Hinne HettemaEmail: |
997.
Sachiko Yoshihashi-Suzuki Izuru Sato Kunio Awazu 《International journal of mass spectrometry》2008,270(3):134-138
Matrix-assisted laser desorption and ionization by infrared laser (IR-MALDI) is expected to be an effective methods for soft-ionization of high-molecular weight proteins and intracellular proteins. IR-MALDI is not widely used because its low sensitivity, complexity, high cost, and as it does not work well on commercial MALDI time-of-flight mass spectrometers (TOFMSs). We employed a tunable mid-infrared (MIR) laser as a light source for MALDI to investigate the IR-MALDI. The laser wavelength can be tuned within a range from 5.5 to 10.0 μm, and included several biomaterial group vibration modes. We evaluated the wavelength dependence of ionization in IR-MALDI for four matrices: succinic acid, urea, 3,5-dimethoxy-4-hydroxycinnamic acid (sinapic acid) and 2,5-dihydroxybenzoic acid (DHB). These matrices contained various groups of vibration modes, and absorbed an infrared (IR) energy at a specific wavelength. The mass spectra of angiotensin II was obtained at a specific wavelength corresponding to the CO stretching and benzene ring vibration mode. In IR-MALDI, we considered the strong molecular bond attracting an electron from a neighboring hydrogen atom, possibly protonating the hydrogen atom. 相似文献
998.
Mark D. Gould Christopher Taylor Stephen K. Wolff Graham S. Chandler Dylan Jayatilaka 《Theoretical chemistry accounts》2008,119(1-3):275-290
Formulae for hermitian operators representing covalent, ionic, and total bond indices are derived. The eigenstates of these
operators come in pairs, and can be considered as bonding, anti-bonding and lone-pair orbitals. The form of these operators
is derived by generalising the rule that the bond order be defined as the net number of bonding electron pairs. The percentage
of covalency and ionicity of a chemical bond may be obtained, and bond indices can also be defined between groups of atoms.
The calculation of the bond indices depends only on the electron density operator, and certain projection operators used to
represent each atom in the molecule. Bond indices are presented for a series of first and second row hydrides and fluorides,
hydrocarbons, a metal complex, a Diels–Alder reaction and a dissociative reaction. In general the agreement between the bond
indices is in accord with chemical intuition. The bond indices are shown to be stable to basis set expansion. 相似文献
999.
1000.
The geometry of Re2Cl82− has been optimized for the eclipsed (D
4h
) equilibrium conformation and for the staggered (D
4d
) conformation at BP86/TZ2P. The nature of the Re–Re bond which has a formal bond order four has been studied with an energy
decomposition analysis (EDA). The EDA investigation indicates that the contribution of the b
2 (δ
xy
) orbitals to the Re–Re bond in the ground state is negligibly small. The vertical excitation of one and two electrons from the bonding δ orbital into the antibonding δ* orbitals yielding the singly and doubly excited states and gives a destabilization of 17.5 and 36.1 kcal/mol, respectively, which is nearly the same as the total excitation energies.
The preference for the D
4h
geometry with eclipsing Re–Cl bonds is explained in terms of hyperconjugation rather than δ bonding. This is supported by the calculation of the triply bonded Re2Cl8 which also has an eclipsed energy minimum structure. The calculations also suggest that the Re–Re triple bond in Re2Cl8 is stronger than the Re–Re quadruple bond in Re2Cl82−. A negligible contribution of the δ orbital to the metal–metal bond strength is also calculated for Os2Cl8 which is isoelectronic with Re2Cl82−.
Contribution of the Mark S. Gordon 65th Birthday Festschrift Issue.
Theoretical Studies of Inorganic Compounds. 38. Part 37 (2006) Bessac F, Frenking G, Inorg Chem 45:6956. 相似文献