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Received 19 June 2007; received in revised form 3 July 2007; accepted 5 July 2007
Available online 14 July 2007
Abstract
The crystallization of the title compound from the MeOH resulted in three crystalline forms depending on the concentration of the
solution, one of which contains N–H N hydrogen bonds between pyridine and amide moieties, while the second one is constituted by
amide-to-amide N–H O hydrogen bonds and the third one crystallizes in a different crystalline phase (threads) and the phase could not
be identified. These three phases have shown different behaviours in TGA and DSC studies.
Ó 2007 Elsevier B.V. All rights reserved.
0022-2860/$ - see front matter Ó 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2007.07.006
340 L. Rajput, K. Biradha / Journal of Molecular Structure 876 (2008) 339–343
Fig. 1. Photographs of the crystals illustrating the morphological differences in three forms (a) form A became opaque as it looses the solvent; (b) form B
remains perfectly crystalline at room temperature; (c) form C (thin fibers), remains crystalline at room temperature.
In A-form, the molecule maintains a 3-fold symmetry hydrogen bonded layer structure formed by T-shaped mol-
and hence it forms a honeycomb grid like structure via ecules. These layers are joined together by synthon-I and
N–H N hydrogen bonds. While in B-form the molecule O–H O hydrogen bonding with water molecules (N–
does not exhibit a 3-fold symmetry and exhibits a T-shape H O and O–H N). The IR spectra clearly shows the
geometry (Fig. 2). As a consequence they assemble via N– differences in carbonyl frequencies of the amide groups,
H O (between amides, synthon-I), and O–H N which confirms the fact that carbonyls are hydrogen
(between H2O and pyridine) hydrogen bonds. The inter- bonded in form B (1666 cm 1) but not in form A and C
planar angles between amide and central C6-rings are (1682 cm 1) [5].
about the same in both the forms (29.5° in A and 30°, The C-form has thin threads like morphology and char-
33.1°, 34.4 in B). However, the inter-planar angles of pyri- acterized by powder X-ray diffraction. The X-ray powder
dine with central C6 (9.6°, 8.4°, 27.5°) and with amide analysis confirms that the diffraction pattern for C-form
plane in B (21.5°, 25.7°, 61.6°) are different from those in is different from those of form A and B (Fig. 4). Moreover,
A (68°, 38.7°). B- and C-forms are crystalline at room temperature unlike
Two of the three amide groups involve in the formation form A, which losses the solvent and there by the crystal-
of amide-to-amide hydrogen bonds with neighbouring line nature.
molecules along c-axis such that it forms a linear chain The three compounds have shown different melting
(synthon-I, Fig. 3). We note here that the hydrogen bond- behaviours. The form A and C shows initial melting at
ing synthon-I observed in this structure does not contain an 186–190 °C and the remaining solid (more in case of A-
usual inversion centre but contains a glide plane (H O, form) sticks to the walls of the melting tube which finally
N O, N–H O: 2.23 Å, 3.066(2) Å, 165°; 1.96 Å, melts at 272–274 °C (A-form) and 278–280 °C (C-form).
2.787(2) Å, 162°). The third amide group of 1a forms N– However, B-form shows a single melting point at 272–
H O hydrogen bonds with water molecule (1.98 Å, 276 °C. To study this behaviour further we have investi-
2.770(3) Å, 152°). Two out of the three pyridine moieties gated TGA and DSC of these compounds (Fig. 5). In
involved in O–H N hydrogen bonds with water (2.04 Å, TGA, the temperatures at which they loose the solvent
2.873(4) Å, 175°; 2.11 Å; 2.852(4) Å, 165°) whereas the are different for all the three forms. A-form is loosing
third pyridine involved in C–H N hydrogen bonds absorbed water [6] at 126 °C, whereas B-form and C-form
(2.97 Å, 3.552(4) Å, 122°). In brief, the structure can be loose the included water completely at about 162 and
described as a C–H O (2.79 Å, 3.587(4) Å, 145°; 2.84 Å, 185 °C, respectively. Therefore, up to 250 °C the weight
3.477(4) Å, 126°) and C–H N (2.85 Å, 3.611(4) Å, 139°) loss is different for all there forms. However, from 250 °C
Fig. 2. Molecular structures of 1a: (a) in the crystal structures of form B; and (b) form A; notice the difference in geometries.
342 L. Rajput, K. Biradha / Journal of Molecular Structure 876 (2008) 339–343
Fig. 3. Illustrations for the crystal structure of 1a in form B: (a) 1D-chain formed via synthon-I along c-axis; (b) top view of 1D-chain; (c) 2D-layer formed
via C–H O and C–H N hydrogen bonds; (d) unit cell showing the joining of the layers via hydrogen bonds, notice that the water molecules exist
between the layers.
a 110 A-Form
B-Form b
100 C C-Form 60
A-Form
80 40
70 30
60 20
50
10 A A
40
B 0
30
-10
0 100 200 300 400 500 50 100 150 200 250 300
Temperature (0C) Temperature (0C)
Fig. 5. (a) TGA (b) DSC spectra for the three forms.
References
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Acknowledgements [5] The IR-spectra for all three compounds were given in Supplementary
information.
[6] This compound has been reported to take up atmospheric water after
We gratefully acknowledge financial support from the desorbtion of MeOH (Ref. [4b]). The elemental analysis after
Department of Science and Technology (DST) and DST- desorbtion of MeOH shows that it can take up to 5 molecules of
FIST for single crystal X-ray facility. L.R. thanks IIT water per one molecule of 1a: Found: C, 54.38%; H, 5.15%; N,
(Kharagpur) for research fellowship. 15.91%; Calcd: C, 54.54%; H, 5.30%; N, 15.90%.
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