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o °H
C I ~ C I
References
Alex, G., Srinivasan, S., Krishnasamy, V., Suresh, R. V., Iyer, R. &
Iyer, P. R. (1993). Acta Cryst. C49, 70-73. HD1/HD2
published previously (Moser, Sallmann & Weisenberg, salts (Castellari & Sabatino, 1994, 1996; Castellari &
1990; Kovala-Demertzi, Mentzafos & Terzis, 1993), but Ottani, 1995, 1996, 1997), it originates a bifurcate intra-
no detailed structure analysis was reported. molecular hydrogen bond interacting with the adjacent
In both forms, the molecules form centrosymmet- acceptor atoms Cll and O1 (Tables 2 and 4). The two
ric dimers linked by hydrogen bonds between the car- forms are very closely related, differing significantly
boxylic O atoms. The structure of the dimeric unit of only in the geometry of the carboxylic group, with the
HD1 is reported in Fig. 1. The dimers are packed in largest differences occurring in the C----O bond lengths
such a way that no strong interaction arises among them. and in the values of the C - - C - - - C - - O torsion angles. A
The N - - H group is located in a sterically hindered po- more effective 7r-electron delocalization is observed in
sition and does not participate in intermolecular hydro- the carboxylic grout~ of HD1 [C14--O1 1.233 (3) and
gen bonds. On the contrary, as observed in diclofenac C14--O2 1.289 (3)A] with respect to HD2 [C14--O1
C12
,-, 0~.--,c4
Fig. I. ORTEPII (Johnson, 1976) diagram of the HD1 dimer showing the atom labelling. Intramolecular hydrogen bonds are indicated by light
lines, whereas dashed light lines have been used for intermolecular hydrogen bonds. Atoms are represented by displacement ellipsoids of
50% probability. [Symmetry code for the unlabelled molecule: -x, -y, -z.]
02 Cll
C4 2
Fig. 2. ORTEPII (Johnson, 1976) diagram of the HD2 dimer showing the atom labelling. Intramolecular hydrogen bonds are indicated by light
lines, whereas dashed light lines have been used for intermolecular hydrogen bonds. Atoms are represented by displacement ellipsoids of
50% probability. [Symmetry code for the unlabelled molecule: ~1 - x , - y - ~,
I --Z.]
796 T W O I S O M E R S O F C14HllC12NO2
1.216 (2), C 1 4 - - - O 2 1.304 ( 2 ) A ] a n d the torsion a n g l e 3937 reflections Extinction correction: none
C 2 - - C 1 3 - - - C 1 4 - - - O 2 is 96.3 (3) in H D 1 and 109.4 (2) ° 216 parameters Scattering factors from
in H D 2 . Also, the O - - - H and O . . . O d i s t a n c e s [1.07 (4) All H atoms refined International Tables for
w = 1/[0-2(Fo2) + (0.0407P) 2 Crystallography (Vol. C)
a n d 1 . 5 6 ( 4 ) in H D 1 , a n d 0 . 8 7 ( 4 ) and 1 . 7 7 ( 3 ) A in
+ 0.322P]
H D 2 ] reflect m o r e d e l o c a l i z e d O C O 7r-electrons in H D 1. where P = (Fo2 + 2F,2)/3
T h e a n g l e s b e t w e e n the least-squares planes o f the t w o
a r o m a t i c rings are 7 0 . 0 0 (9) and 69.28 (8) ° for H D 1 and
Table 1. Selected geometric parameters (,4, °)for HD1
H D 2 , respectively. In both f o r m s , the a m i n e m o i e t y (N 1,
CI1---C~ 1.738(3) C13--C14 1.500(3)
C1, C7, H I ) is p y r a m i d a l , w i t h the N a t o m out o f the C12--~12 1.733 (2) CI4----O1 1.233 (3)
C1, C7, H1 p l a n e by 0.195 (2) in H D 1 and 0.187 (2),~, N I ---C7 1.390 (3) C 14---4)2 1.289 (3)
N I---C 1 1.411 (3) O2--H11 1.07(4)
in H D 2 . I n s p e c t i o n o f d e n s i t y v a l u e s s h o w s that H D 2
C2---C 13 1.502 (4)
g i v e s a m o r e efficient crystal p a c k i n g (Dx 1.477 against
C7--NI---CI 122.1 (2) OI---4714---4)2 123.7 (2)
1 . 4 5 4 M g m -3 in H D 1 ) , w h i c h c o r r e s p o n d s also to a C7--NI--HI 115.0(18) OI---CI4----C13 121.1 (2)
m o r e a s y m m e t r i c h y d r o g e n bridge. CI--NI--H1 113.8(19) O2---C 14----C13 115.2(2)
C1--N 1--477--4212 - 6 2 . 6 (3) C2---C13----CI4---O2 96.3 (3)
C2--C 1 3 ~ C 14-4)1 - 8 2 . 0 (3)