Incorrect atom connectivity in X-ray structure solutions associated with a "partial polar ambiguity": A non-macrocyclic structure for the macrocyclic lead complex, [η4-Me8taa]Pb

New Journal of Chemistry

Volumn 22, Issue 5, 1998, Pages 523-530

  Kuchta, Matthew C ^a   Parkin, Gerard ^a  

^a Och Spine at New York Presbyterian Hospitals   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000559761     PISSN: 11440546     EISSN: None     Source Type: Journal    
DOI: 10.1039/a709201f     Document Type: Article

References (98)

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55. 8taa]Pb.
56. The most likely "chemical interpretation" of the structure as illustrated in Fig. 5 would be to incorporate hydrogen atoms on N1 and N1′.
57. The ability to locate atoms in incorrect positions is also related to the concept of homometric structures, i.e. different structures with the same Patterson map. See: Patterson and Pattersons, eds. J. P. Glusker, B. K. Patterson and M. Rossi, Oxford University Press, New York, 1987.
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67. It is well-known that, for polar space groups, two minima exist in a least-squares refinement procedure, corresponding to chemically identical structures that are related by a reflection perpendicular to the polar axis. However, the two structures will differ slightly in bond lengths as a consequence of the polar dispersion error, so that it is essential to establish that the correct polarity has been determined. See ref. 28.
68. It should be noted that the relationship between the z coordinates of the true and false locations z(C2X) = -z(C2X*) is only true because Pb is arbitrarily situated at z = 0. More generally, the relationship would be z(C2X) = z(Pb) - z(C2X*), if Pb were not to be located at z = 0.
69. (a) G. Bernardinelli and H. D. Flack, Acta Crystallogr., Sect. A, 1987, 43, 75;
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73. For the 530 lead structures listed in Version 5.12 of the Cambridge Structural Database, the R value ranges are distributed as follows: 0.00 < R ≤ 0.05 (56.09%), 0.05 < R ≤ 0.10 (39.43%), 0.10 < R ≤ 0.15 (3.21%), 0.15 < R ≤ 0.20 (1.13%), 0.20 < R ≤ 1.00 (0.14%).
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77. 3 are the three main axes components of the thermal ellipsoid.
78. 1 for C1, C11 and C32 are 15.58, 5.22 and 5.08, respectively.
79. 1 for C1 and C32 are 8.40 and 15.15, respectively.
80. The covalent radii of H and Pb are 0.30 and 1.54 Å, respectively; the van der Waals radius of H is 1.20 Å, while that of lead can be estimated as 0.8 Å greater than its covalent radius. See ref. 24.
81. For example, there are 47 occurrences of nonbonded Pb⋯H interactions in the range 2.0-2.7 Å listed in the Cambridge Structural Database (Version 5.12). References to interactions in the range 2.0-2.5 Å comprise: (a) N. S. Hosmane, K.-J. Lu, H. Zhu, U. Siriwardane, M. S. Shet and J. A. Maguire, Organometallics, 1990, 9, 808;
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89. This statement is concerned specifically with situations where there is a significant structural difference between the two solutions, and does not apply to situations in which small deviations from centrosymmetry may be insufficient to prevent a strictly non-centrosymmetric structure from being refined in a centrosymmetric space group.
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93. For another example of a structure that was initially refined in the centrosymmetric P1 but is better described as the non-centrosymmetric P1 see: J. C. Calabrese and K. H. Gardner, Acta Crystallogr., Sect. C, 1985, 41, 389.
94. (a) J. P. McNally, V. S. Leong, N. J. Cooper, ACS Symposium Series 357, American Chemical Society, Washington, DC, 1987, pp. 6-23;
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97. 2 can be seen to be related to the C-centered modification by an approximate doubling of the b axis. Despite this coincidence, axial photographs confirmed the cell lengths in each case, and examination of the molecular packing indicated distinct differences between the two structures. We thank Professor R. E. Marsh for his evaluation concerning the difference in packing between the C-centered and primitive modifications.
98. 1 (No. 36), Cmcm (No. 63) and C2cm (No. 40) are 3.71, 14.88 and 7.28, respectively.