Crystal structure of 1,2-diphenyl-5,7-di-tert-butylspiro[2.5]octa- 1,4,7-trien-6-one, a possible model for diphenylvinylidenephenonium ions

Journal of Organic Chemistry

Volumn 64, Issue 12, 1999, Pages 4370-4375

  Rappoport, Zvi ^a,b   Kobayashi, Shinjiro ^b   Stanger, Amnon ^b,c   Boese, Roland ^d  

^a HEBREW UNIVERSITY OF JERUSALEM   (Israel)

^b KYUSHU UNIVERSITY   (Japan)

^c TECHNION ISRAEL INSTITUTE OF TECHNOLOGY   (Israel)

^d UNIVERSITY OF DUISBURG ESSEN   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

1,2 DIPHENYL 5,7 DI TERT BUTYLSPIRO[2.5]OCTA 1,4,7 TRIEN 6 ONE; BIPHENYL DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL BOND; CONFORMATION; CRYSTAL STRUCTURE; STRUCTURE ANALYSIS; X RAY CRYSTALLOGRAPHY;

EID: 0033546215     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo982482r     Document Type: Article

References (35)

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14. The criteria for significance of X-ray structural data are difficult to classify, although attempts have been made by the Cambridge Crystallographic Data Centre (CCDC). For carbon atoms that are linked by double or triple bonds, we prefer to restrict ourselves to the inclusion of high-angle data (2Θ ≥ 60° for Mo radiation) because otherwise, in the standard refinement procedures, the distances tend to become too short. This is easily explained by the fact that the refinement procedure of (spherical) atoms tries to shift the atoms together so that the bonding electron density is "absorbed" and a minimum residual electron density results. Low-temperature experiments with a higher localization of electron densities and high-angle data with the higher contribution of core electrons will avoid such an artifact. However, it should be noted that the inclusion of the high-angle data, which are weaker and therefore measured with a lower accuracy, produce higher R-values. In contrast, low-temperature experiments (e.g., T < 150 K) tend to give longer intramolecular distances, which is a different artifact, but can be roughly corrected (see Dunitz, J. D. Angew. Chem. 1988, 100, 910; Angew. Chem., Int. Ed. Engl. 1988, 27, 880). This kind of correction gives a lengthening of 0.001-0.002 Å for 3.
15. The criteria for significance of X-ray structural data are difficult to classify, although attempts have been made by the Cambridge Crystallographic Data Centre (CCDC). For carbon atoms that are linked by double or triple bonds, we prefer to restrict ourselves to the inclusion of high-angle data (2Θ ≥ 60° for Mo radiation) because otherwise, in the standard refinement procedures, the distances tend to become too short. This is easily explained by the fact that the refinement procedure of (spherical) atoms tries to shift the atoms together so that the bonding electron density is "absorbed" and a minimum residual electron density results. Low-temperature experiments with a higher localization of electron densities and high-angle data with the higher contribution of core electrons will avoid such an artifact. However, it should be noted that the inclusion of the high- angle data, which are weaker and therefore measured with a lower accuracy, produce higher R-values. In contrast, low-temperature experiments (e.g., T < 150 K) tend to give longer intramolecular distances, which is a different artifact, but can be roughly corrected (see Dunitz, J. D. Angew. Chem. 1988, 100, 910; Angew. Chem., Int. Ed. Engl. 1988, 27, 880). This kind of correction gives a lengthening of 0.001-0.002 Å for 3.
16. 3 carbon atom of 50.71(1)° were claimed for 2-p-chlorophenyl-3,3-dimethyl-1-methoxycyclopropene (Søtofte, I.; Cross-land, I. Acta Chem. Scand. 1989, 43, 168), which fulfills nonspecified significance criteria, see: Chemie-Rekorde; Quadbeck-Seeger, H.-J., Ed.; Wiley-VCH: Weinheim, 1997; p 178.
17. 3 carbon atom of 50.71(1)° were claimed for 2-p-chlorophenyl-3,3-dimethyl-1-methoxycyclopropene (Søtofte, I.; Cross- land, I. Acta Chem. Scand. 1989, 43, 168), which fulfills nonspecified significance criteria, see: Chemie-Rekorde; Quadbeck-Seeger, H.-J., Ed.; Wiley-VCH: Weinheim, 1997; p 178.
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21. Here, one ethynyl group is synclinal and the other is antiperiplanar to the proximal bonds; see also ref 6.
22. Because of the symmetry of the molecule, the IUPAC and the CSD numbering schemes are different. Where there are differences, the IUPAC numbering is given in parentheses. The bond lengths and angles here are reported according to the IUPAC scheme.
23. In the 19 compounds found in the CSD with phenyl rings in the C(1), C(2) positions of a cyclopropene fragment, all of the rings are almost coplanar with the three-membered ring.
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25. The comparison between the two types of error calculations gives a measure of the type of reproducibility of the experimental results. Thus, the two extreme cases are (a) the average sum is zero and the average error is large, and (b) the two are equal. Case (a) suggests an alternating effect of reproducibility (i.e., some bonds are calculated to be shorter and some are calculated to be longer than they are). Case (b) suggests that all of the bond lengths are slightly different than the experimental values.
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30. This approach was successfully employed in strained aromatic systems. (a) Stanger, A. J. Am. Chem. Soc. 1991, 113, 8277. (b) Stanger, A. J. Am. Chem. Soc. 1998, 120, 12034.
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35. See, for example: Streitwieser, A.; Heathcock, C. H.; Kosower, E. M. Introduction to Organic Chemistry, 4th ed.; Macmillan Publishing Company: New York, 1992; pp 89-90.