Rapid intermolecular acid–alcohol hydrogen-bonded proton exchange and geometrical disorder, well below the melting temperature, form the basis of the observed amorphous behavior of salicyl salicylate 1. Compound 1 was observed in a stable, undercooled amorphous phase by ¹H and ¹³C NMR spectroscopy, and its crystal structure was determined by single-crystal X-ray diffraction. The amorphous state of 1 was confirmed by small-angle X-ray scattering (SAXS) studies.

References

1 J. C. MacDonald, G. M. Whitesides, Chem. Rev. 1994, 94, 2383.
10.1021/cr00032a007
CAS Web of Science® Google Scholar
2 J. D. Dunitz, A. Gavezzotti, Acc. Chem. Res. 1999, 32, 677.
10.1021/ar980007+
CAS Web of Science® Google Scholar
3 V. R. Thalladi, R. Boese, H.-C. Weiss, Angew. Chem. 2000, 112, 942; Angew. Chem. Int. Ed. 2000, 39, 918.
10.1002/(SICI)1521-3757(20000303)112:5<942::AID-ANGE942>3.0.CO;2-D
Google Scholar
4 J. S. Moore, Curr. Opin. Coll. Interf. Sci. 1999, 4, 108.
10.1016/S1359-0294(99)00018-7
CAS Web of Science® Google Scholar
5 R. P. Sijbesma, F. H. Beijer, L. Brunsveld, B. J. B. Folmer, J. H. K. K. Hirschberg, R. F. M. Lange, J. K. L. Lowe, E. W. Meijer, Science 1997, 278, 1601.
10.1126/science.278.5343.1601
CAS PubMed Web of Science® Google Scholar
6 B. Greener, J. Rose, Chem. Commun. 1999, 23, 2361.
10.1039/a906756f
Web of Science® Google Scholar
7 M. Shibakami, A. Sekiya, Acta Crystallogr. Sect. C 1995, 51, 326.
10.1107/S0108270194003653
Web of Science® Google Scholar
8 J. H. Bilgram, U. Dürig, M. Wächter, J. Cryst. Growth 1982, 57, 1.
10.1016/0022-0248(82)90241-X
CAS Web of Science® Google Scholar
9 2D Gradient COSY and 2D Gradient HMQC NMR spectra were recorded for CDCl₃ solutions of 3.
Google Scholar
10 C. J. Pouchert, J. Behnke, The Aldrich Library of ¹³C and ¹H FT-NMR Spectra, Vol. 2, 1st ed., Aldrich Chemical, Milwaukee, WI, 1993: benzoic acid, o-anisic acid, methyl benzoate, salicylic acid, phenyl benzoate.
Google Scholar
11 S. N. Vinogradov, R. H. Linnell, Hydrogen Bonding, Van Nostrand Reinhold, New York, 1971.
Google Scholar
12 Spectra recorded at 100.6 MHz (293 K) using a 2.5 mm CPMAS probe (12 kHz rotation).
Google Scholar
13 3: ¹³C NMR (270 MHz, [D₆]acetone): δ=165.7 (C1), 169.5 (C2), 113.3 (C3), 162.5 (C4), 131.8 (C5), 137.3 (C6), 120.5 (C7), 118.3 (C8), 151.1 (C9), 132.9 (C10), 135.1 (C11), 127.5 (C12), 125.0 (C13), 124.7 (C14); 3: ¹³C NMR (270 MHz, CDCl₃): δ=168.8 (C1), 169.9 (C2), 111.9 (C3), 162.0 (C4), 130.8 (C5), 136.5 (C6), 119.6 (C7), 117.7 (C8), 150.5 (C9), 132.8 (C10), 135.0 (C11), 126.7 (C12), 124.1 (C13), 122.5 (C14).
Google Scholar
14 3: ¹H NMR (270 MHz, CDCl₃): δ=11.24 (s br.; OH), 10.26 (s sh; COOH), 8.11 (dd, J=7.8, 1.9 Hz; H10), 8.04 (dd, J=7.8, 1.6 Hz; H5), 7.65 (dt, J=8.1, 1.6 Hz; H11), 7.51 (ddd, J=9.0, 7.5, 1.9 Hz; H6), 7.38 (dd, J=7.8, 1.2 Hz; H12), 7.23 (dd, J=8.1, 2.6 Hz; H13), 7.01 (dd, J=8.4, 1.2 Hz; H8), 6.91 (ddd, J=8.1, 7.8, 0.9 Hz; H7).
Google Scholar
15 Crystal data for 3: C₁₄H₁₀O₅, M_r=258.22, monoclinic, space group Cc (no. 9), a=12.965(4), b=12.982(4), c=15.530(3) Å, β=114.039(15)°, V=2387.2(11) Å³, Z=4, ρ_calcd=1.431 g cm⁻³, μ(Mo_Kα)=0.7107 Å, F(000)=1064, T=150 K; colorless rhombs, 0.45×0.40×0.35 mm, Rigaku AFC6 four-circle diffractometer, Oxford Cryosystems N₂ cooler (150 K) 2105 independent reflections. The structure was solved by direct methods, all non-hydrogen atoms were refined anisotropically using full-matrix least-squares based on F ² to give R₁=0.0341, wR₂=0.0913 for 1644 independently observed reflections (|F_o|>2σ(|F_o|)) and 366 parameters. Crystallographic data (excluding structure factors) for the structure reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC-143946. Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax: (+44) 1223-336-033; e-mail: [email protected]).
Google Scholar
16 G. Bruno, L. Randaccio, Acta Crystallogr. Sect. B 1980, 36, 1711.
10.1107/S0567740880007030
Web of Science® Google Scholar
17 M. Sundaralingham, L. H. Jensen, Acta Crystallogr. 1965, 18, 1053;
10.1107/S0365110X65002517
PubMed Web of Science® Google Scholar
W. Cochran, Acta Crystallogr. 1953, 6, 260.
10.1107/S0365110X53000752
CAS Web of Science® Google Scholar
18 M. Haisa, S. Kashino, S-I. Hanada, K. Tanaka, S. Okazaki, M. Shibagaki, Acta Crystallogr. Sect. B 1982, 38, 1480.
10.1107/S0567740882006189
Web of Science® Google Scholar
19 SAXS: 0.7 mm diameter cylinder of 3. Rigaku RU200 rotating anode, graphite-monochromated (μ(Cu_Kα)=1.5418 cm⁻¹, 50 kV, 100 mA) and Marresearch Imaging Plate System, 300.0 mm sample to plate distance.
Google Scholar
20 C. K. Johnson, ORTEP, Report ORNL-5138, Oak Ridge National Laboratory, Oak Ridge, TN, 1976.
Google Scholar
21 G. R. Desiraju, Angew. Chem. 1995, 107, 2541; Angew. Chem. Int. Ed. Engl. 1995, 34, 2311.
10.1002/ange.19951072105
Google Scholar

Citing Literature

Volume39, Issue20

October 16, 2000

Pages 3601-3604

Hydrogen Bonding Interactions in Amorphous Salicyl Salicylate

Abstract

References

Citing Literature

References

Information

About Wiley Online Library

Help & Support

Opportunities

Connect with Wiley

Hydrogen Bonding Interactions in Amorphous Salicyl Salicylate

Abstract

References

Citing Literature

References

Related

Information