Experimental determination of the deformation electron density in hydrogen peroxide by combination of x-ray and neutron diffraction measurements

Savariault, Jean‐Michel; Lehmann, M. S.

doi:10.1021/ja00524a012

Cited by 172 publications

(115 citation statements)

References 9 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Apparently, the overlap of spherical 0.67 (12) O (1) -0.32 (8) neutral atoms is sufficient to account for the density in the peroxide bond. A nearly identical electron density was found by Savariault & Lehmann (1980)for the ~ 6H20 (Elerman, Bats & Fuess, 1983). These maps were peroxide bond in H20 2.…”

Section: Bond Distances (A) and Bond Angles (O)supporting

confidence: 69%

“…Despite the crystallographic interactions (including hydrogen bonding of the peroxide hydrogen with the water oxygen), the S-O(2)-O(1)-H(1) torsion angle is very close to that [90.2(4) ° ] in solid hydrogen peroxide (Savariault & Lehmann, 1980). The O-O distance is also very close to their value [1-458 (4)A] for hydrogen peroxide.…”

Section: X =mentioning

confidence: 65%

“…a tendency for peroxide-bond breakage in HSO~-upon oxidation (Thompson, 1981)], we were interested not only in comparison of the O-O distance with that in $20 2-and in H20 2 but also a comparison of deformation density with that observed for H20 2 (Savariault & Lehmann, 1980), for SO 2- (Kirfel & Will, 1980, 1981, and for $2032- (Elerman, Bats & Fuess, 1983).…”

Section: X =mentioning

confidence: 99%

See 2 more Smart Citations

Structure, deformation density and atomic charges in potassium hydrogenperoxomonosulfate monohydrate, KHSO5.H2O

Schlemper¹,

Thompson²,

Fair³

et al. 1984

Acta Crystallogr C

View full text Add to dashboard Cite

Introduetlon. Although potassium hydrogenperoxomonosulfate is sold in an impure form commercially, pure salts of peroxomonosulfate have not been previously available. We have developed a procedure involving hydrolysis of K2S208 that affords highly pure KHSOs.H20. This product yielded crystals suitable for the first determination of the structure of the HSO~-ion. An earlier X-ray study (Kyrki & Lappalainen, 1965) reported an orthorhombic unit cell but did not include a structure determination.Because of the difference in chemistry of oxidation- -(Kirfel & Will, 1980, 1981, and for $2032-(Elerman, Bats & Fuess, 1983).0108-2701/84/I 11781-05501.50Experimental. Concentrated solution of sodium peroxodisulfate was converted to the acid by passage through a column of Dowex 50X8 cation-exchange resin in the hydrogen form. The solution was concentrated in a rotary evaporator and hydrolyzed by heating at 323 K until no peroxodisulfate was detected. The solution was then neutralized to pH 3.5 by addition of KHCO 3 in an ice bath, filtered and freeze-dried. The residue was redissolved in a small quantity of water at room temperature and filtered. The filtrate was chilled in an ice bath and the crystals that formed were filtered, washed with a small quantity of absolute ethanol and dried between sheets of filter paper. Iodometric analysis indicated a bulk composition approximating KHSOs.-H20. Plate-like crystal; ~0.07 x 0.23 x 0.27 mm; Enraf-Nonius CAD-4 diffractometer; T maintained by constant flow of N 2 gas; 24 reflections, 0 = 9-15 °, used for cell dimensions; empirical ~,-scan absorption (range of transmission = 0.

show abstract

Section: Bond Distances (A) and Bond Angles (O)supporting

confidence: 69%

Section: X =mentioning

confidence: 65%

Section: X =mentioning

confidence: 99%

See 1 more Smart Citation

Structure, deformation density and atomic charges in potassium hydrogenperoxomonosulfate monohydrate, KHSO5.H2O

Schlemper¹,

Thompson²,

Fair³

et al. 1984

Acta Crystallogr C

View full text Add to dashboard Cite

show abstract

“…l.ti, #,j, Oij, V E,, Stewart & Jensen (1967) Kvick & Popelier (1992); (e) Jeffrey, Ruble, McMullan & Pople (1987); (f) Coppens (1967); (g) Jeffrey, Ruble, McMullan, DeFrees, Binkley & Pople (1980); (h) Savariault & Lehmann (1980); (i) Swaminathan, Craven & McMullan (1984); (j) Boese, Maulitz & Stellberg (1994); (k) Nijveldt & Vos (1988); (/) Kampermann, Ruble & Craven (1994).…”

Section: Compute Molecular Propertiesmentioning

confidence: 99%

Molecular electric moments and electric field gradients from X-ray diffraction data: model studies

Spackman¹,

Byrom²

1996

Acta Crystallogr Sect B

View full text Add to dashboard Cite

Model X-ray data sets, with and without the inclusion of experimental thermal motion parameters, have been computed via Fourier transformation of ab initio molecular electron densities for 12 different molecular crystals. These datasets were then analysed with three different multipole models of varying sophistication and, from the multipole functions, molecular dipole and second moments, as well as electric field gradients (EFG's), at each nuclear site were computed and compared with results obtained from the original ab initio wavefunctions. The results provide valuable insight into the reliability of these properties, extracted in the same way from experimental X-ray data. Not all molecular systems display identical trends, but a general pattern is discernible. Specifically, dipole moments are typically underestimated by a small but significant amount (~ 10-15%), the trace of the second moment tensor is well determined but overestimated by a few per cent and electric field gradients at protons are confirmed to be well within reach of a careful charge density analysis of X-ray diffraction data.

show abstract

“…Since the space group of NDE is noncentrosymmetric the experimental Ap.o deformation densities suffer from the fact that only the amplitude and not the phase of the structure factor can be determined from the X-ray experiment. This has the effect of reducing the height and smearing out the features in the deformation density map (Savariault & Lehmann, 1980;Stevens, 1981).…”

Section: Electron Density Mapsmentioning

confidence: 99%

Experimental electron density distribution of (1R,2S,3R,4R)-3,4-epoxy-1,2,3,4-tetrahydro-1,2-naphthalenediol

Klein¹,

Stevens²

1988

Acta Crystallogr Sect B

View full text Add to dashboard Cite

Careful X-ray diffraction measurements at 100 K have been used to map the electron density distribution in a single crystal of trans-3,4-epoxy-1,2,3,4-tetrahydro-1,2-naphthalenediol, a small-molecule model for the ultimate carcinogenic metabolites of some polycyclic aromatic hydrocarbons. A least-squares-refinement procedure has been used in which additional multipole parameters are added to describe the distortions of the atomic electron distributions as a result of covalent bonding. The refinement also yields improved estimates of the X-ray phases, which have been used to plot maps of the electron distribution. In the epoxide ring, one C atom is found to be more positive than the other, suggesting that it would be the preferred site of attack by nucleophiles such as DNA bases, in agreement with 0108-7681/88/010050-06503.00 other experimental evidence. Covalent-bond peaks lie outside the lines joining the atom centers of the epoxide ring, and lone-pair density on the epoxide O atom corresponds to largely unhybridized s and p orbitals.

show abstract

Experimental determination of the deformation electron density in hydrogen peroxide by combination of x-ray and neutron diffraction measurements

Cited by 172 publications

References 9 publications

Structure, deformation density and atomic charges in potassium hydrogenperoxomonosulfate monohydrate, KHSO5.H2O

Structure, deformation density and atomic charges in potassium hydrogenperoxomonosulfate monohydrate, KHSO5.H2O

Molecular electric moments and electric field gradients from X-ray diffraction data: model studies

Experimental electron density distribution of (1R,2S,3R,4R)-3,4-epoxy-1,2,3,4-tetrahydro-1,2-naphthalenediol

Contact Info

Product

Resources

About

Experimental determination of the deformation electron density in hydrogen peroxide by combination of x-ray and neutron diffraction measurements

Cited by 172 publications

References 9 publications

Structure, deformation density and atomic charges in potassium hydrogenperoxomonosulfate monohydrate, KHSO5.H2O

Structure, deformation density and atomic charges in potassium hydrogenperoxomonosulfate monohydrate, KHSO5.H2O

Molecular electric moments and electric field gradients from X-ray diffraction data: model studies

Experimental electron density distribution of (1R*,2S*,3R*,4R*)-3,4-epoxy-1,2,3,4-tetrahydro-1,2-naphthalenediol

Contact Info

Product

Resources

About

Experimental electron density distribution of (1R,2S,3R,4R)-3,4-epoxy-1,2,3,4-tetrahydro-1,2-naphthalenediol