794 C18HI6045

Data collection Dewick, P. M. (1988). In The Flavonoids -Advances in Research

Enraf-Nonius CAD-4 0max = 24.97 ° since 1980, edited by J. B. Harborne. New York: Chapman and
Hall.
diffractometer h = 0 ----, 11
Enraf-Nonius (1989). CAD-4 Software. Version 5.0. Enraf-Nonius,
w-20 scans k=0~ 16 Delft, The Netherlands.
Absorption correction: none 1 = - 14 ~ 13 Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge
2765 measured reflections 2 standard reflections National Laboratory, Tennessee, USA.
2606 independent reflections every 100 reflections Santhosh, K. C. (1994). PhD thesis. Indian Institute of Technology,
2267 reflections with frequency: 60 min Madras, India.
I > 3o'(/) intensity decay: 2% Sheldrick, G. M. (1990). Acta Cryst. A46, 467--473.
Rint = 0.0179 Sheldrick, G. M. (1993). SHELXL93. Program for the Refinement of
Crystal Structures. University of G6ttingen, Germany.
Refinement
Refinement on F 2 (A/o.)max < 0.001
RtF 2 > 2o'(F2)1 = 0.0502 Apmax = 0.656 e ,~-3
wR(F 2) = 0.1337 Apmin = --0.188 e ,~-3
S - 1.088 Extinction correction: none
2606 reflections Scattering factors from
272 parameters International Tables for
H atoms refined isotropically Crystallography (Vol. C)
w = 1/[o'2(F2) + (0.0642P) 2 Acta Cryst. (1997). C53, 7 9 4 - 7 9 7
+ 1.1547P]
where P = (Foz + 2F2)/3 Two Monoclinic Forms of Diclofenac Acid
Table 1. Selected geometric parameters (A, °)
CARLO CASTELLARIa AND STEFANO OTI'ANI b
s----ClO 1.763 (3) c2---c1 1.519 (4)
s----c2 1.839 (3) c2--c3 1.518 (4) ~Dipartimento di Chimica 'G. Ciamician', Universith di
01--c9 1.381 (3) c9--c8 1.373 (4)
Ol--Cl 1.408 (4) c8---c3 1.495 (4) Bologna, Via Selmi 2, 40126 Bologna, Italy, and bCentro
02--c3 1.189 (4) c17---c18 1.282 (6) Studi Fisica Macromolecole, c/o Dipartimento di Chimica
ClO---s--c2 108.93 (12) 01--c9--c7 115.1 (3) 'G. Ciamician', Universith di Bologna, Via Selmi 2, 40126
c9--01---c1 114.0 (2) 02---c3--c8 122.7 (3) Bologna, Italy. E-mail: stefano@frodo.ciam.unibo.it
c1---c2---c3 110.7 (2) 02--c3---c2 122.3 (3)
Ol--C 1--c2 113.7 (2) c8--c3---c2 115.0 (2) (Received 21 November 1996: accepted 3 February 1997)
c8--~9--0 l 124.1 (3)
c10--s---c2--c16 170.2 (2) 01--c9---c8--c3 -2.9 (4)
c9---01---c1--c2 50.9 (3) c9--c8---c3---c2 - 1.4 (4)
c3--422--c1--01 -53.5 (4) s--c2--c3--02 83.4 (3) Abstract
c16---c2----ci---01 -177.5 (3) c1--c2----c3--c8 27.7 (3) D i c l o f e n a c acid, [ 2 - ( 2 , 6 - d i c h l o r o p h e n y l a m i n o ) p h e n y l ] -
c1---4)1--c9--c8 -22.3 (4) c3---c2--c 16---c17 -63.0 (4)
acetic acid, ClaHI IC12NO2, crystallizes in t w o p o l y m o r -
Data collection: CAD-4 Software (Enraf-Nonius, 1989). Cell phic f o r m s in the m o n o c l i n i c system. In both forms,
refinement: CAD-4 Software. Data reduction: CAD-4 Software. m o l e c u l e s are l i n k e d to each other t h r o u g h the carboxyl
Program(s) used to solve structure: SHELXS86 (Sheldrick, groups g i v i n g rise to c e n t r o s y m m e t r i c dimers. N o inter-
1990). Program(s) used to refine structure: SHELXL93 action a m o n g different d i m e r s has b e e n found.
(Sheldrick, 1993). Molecular graphics: ORTEPII (Johnson,
1976).
Comment
T h e authors w i s h to t h a n k the R e g i o n a l S o p h i s t i c a t e d T h e crystal structure d e t e r m i n a t i o n o f d i c l o f e n a c acid
I n s t r u m e n t a t i o n Centre, Indian Institute o f T e c h n o l o g y , (HD) is part o f our structural studies on n o n - s t e r o i d a l
Madras, India, for data c o l l e c t i o n and Professor K. a n t i - i n f l a m m a t o r y agents (Castellari & Sabatino, 1994,
K. B a l a s u b r a m a n i a n , D e p a r t m e n t o f Chemistry, Indian 1996; Castellari & Ottani, 1995, 1996, 1997). In this
Institute o f T e c h n o l o g y , Madras, India, for helpful paper w e describe the X-ray crystal and m o l e c u l a r
discussions. structures o f t w o m o n o c l i n i c f o r m s o f d i c l o f e n a c acid,
namely, HD1 (space g r o u p P21/c) and H D 2 (space
Lists of atomic coordinates, displacement parameters, structure factors group C2/c). The crystal data o f H D 2 h a v e b e e n
and complete geometry have been deposited with the IUCr (Reference:

••,,
VJI050). Copies may be obtained through The Managing Editor,
International Union of Crystallography, 5 Abbey Square, Chester CH 1
2HU, England. H
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

© 1997 International Union of Crystallography Acta Crystallographica Section C

Printed in Great Britain - all rights reserved ISSN 0108-2701 ©1997
 CARLO CASTELLARI AND STEFANO OTTANI 795

published previously (Moser, Sallmann & Weisenberg,
1990; Kovala-Demertzi, Mentzafos & Terzis, 1993), but
no detailed structure analysis was reported.
In both forms, the molecules form centrosymmet-
ric dimers linked by hydrogen bonds between the car-
boxylic O atoms. The structure of the dimeric unit of
HD1 is reported in Fig. 1. The dimers are packed in
such a way that no strong interaction arises among them.
The N - - H group is located in a sterically hindered po-
sition and does not participate in intermolecular hydro-
gen bonds. On the contrary, as observed in diclofenac
salts (Castellari & Sabatino, 1994, 1996; Castellari &
Ottani, 1995, 1996, 1997), it originates a bifurcate intra-
molecular hydrogen bond interacting with the adjacent
acceptor atoms Cll and O1 (Tables 2 and 4). The two
forms are very closely related, differing significantly
only in the geometry of the carboxylic group, with the
largest differences occurring in the C----O bond lengths
and in the values of the C - - C - - - C - - O torsion angles. A
more effective 7r-electron delocalization is observed in
the carboxylic grout~ of HD1 [C14--O1 1.233 (3) and
C14--O2 1.289 (3)A] with respect to HD2 [C14--O1

~ ,,---,, CII ,--

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)

E~er~en~ Table 2. Hydrogen-bonding geometry (A, °)for HD1

D--H. • .A D--H H. • .A D. • .A D--H. • -A
Diclofenac sodium salt (Sigma, St. Louis, USA) was dissolved N 1--H 1. • .CI1 0.76 (2) 2.65 (2) 2.994 (2) 110 (2)
in water. The solution was acidified with HC1 (37%; Merck, N I - - H I . • .O1 0.76 (2) 2.37 (2) 3.033 (3) 146 (2)
Darmstad, Germany). The resulting powders were filtered, O2--HI I. • .O1 i 1.07 (3) 1.56 (4) 2.629 (3) 177 (3)
washed with water and dried in vacuo. Recrystallization of Symmetry code: (i) -x, -y, -z.
HD1 was from methanol by slow evaporation. Crystals of
HD2 were obtained by slow diffusion of an acetone solution Compound I-ID2
in n-hexane. Crystal data
CIaHllC12NO2 M o / C a radiation
Compound I-ID1
Mr = 296.14 A = 0.71069 ,~,
Crystal data Monoclinic Cell parameters from 25
CI4HllC12NO2 Mo Ka radiation C2/c reflections
Mr = 2 9 6 . 1 4 A = 0.71069 .~ a = 20.226 (4) ,~ 0 = 7-17 °
Monoclinic Cell parameters from 25 b = 6.971 (3) a, /z = 0.483 mm-1
P21/c reflections c = 20.061 (4) T = 293 (2) K
a = 8.384 (2) ,~ 0 = 7-12 ° 3V = 109.64 (2) ° Prismatic
b = 10.898 (2) ,~, # = 0.476 m m - i 2664 (1) ,~3 0.40 × 0.23 × 0.15 mm
c -- 14.822 (5) ,4, T = 293 (2) K Z=8 Colourless
/3 = 92.76 (2) ° Plate Dx = 1.477 Mg m -3
V = 1352.7 (6)/~3 0.40 × 0.15 × 0.10 mm D,, = 1.48 Mg m -3
Z=4 Colourless D,, measured by flotation
Dx = 1.454 Mg m -3 in a 1-bromo-3-chloro-
D m = 1.45 Mg m -3 propane/p-xylene mixture
Dm measured by flotation
in a 1-bromo-3-chloro- Data collection
propane/p-xylene mixture Enraf-Nonius CAD-4 Rim = 0.024
diffractometer 0max = 31.54 °
Data collection Profile data from o: scans h = - 2 9 ---+ 28
Enraf-Nonius CAD--4 Rim = 0.0374 Absorption correction: none k= -9--0 9
diffractometer 0ma~ = 29.98 ° 4383 measured reflections l = - 1 4 ---0 23
Profile data from w scans h=-ll --+ 11 2589 independent reflections 3 standard reflections
Absorption correction: none k = 0 ---+ 15 1743 reflections with frequency: 160 min
4079 measured reflections l = 0--+ 20 I > 20-(/) intensity decay: none
3940 independent reflections 3 standard reflections
1597 reflections with frequency: 160 min Refinement
I > 20-(/) intensity decay: none Refinement on F 2 Apmax = 0.247 e ,~-3
R[F2 > 20.(F2)] = 0.0374 Apmin = - 0 . 2 4 9 e ,~-3
Refinement wR(F2) = 0.1126 Extinction correction:
Refinement on F 2 (A/0-)max = --0.203 S = 1.057 SHELXL93 (Sheldrick,
R[F2 > 20-(F2)] = 0.0397 (for H l l ) 2582 reflections 1993)
wR(F2) = 0.1206 Apmax = 0.249 e ,a,-3 217 parameters Extinction coefficient:
S = 1.005 mflmin -- - 0 . 2 1 0 e ,~-3 All H atoms refined 0.0063 (6)
 C A R L O C A S T E L L A R I A N D STEFANO O T r A N I 797

w = 1/[o'2(Fo2) + (0.0635P) 2 Scattering factors f r o m Acta Cryst. (1997). C53, 797-799

+ 0.3396P] International Tables f o r
w h e r e P = (Fo2 + 2F~)/3
(A/o')max = 0.018
Crystallography (Vol. C) N-(2,3,5,6-Tetrachloropyrid-4-yl)cinnamide
o
Table 3. Selected geometric parameters (A, o) for HD2 WILLIAM CLEGG, MARK R. J. ELSEGOOD, RICHARD F. W .
CI!---C8 1.736 (2) C2--C13 1.507 (4) JACKSON, JOANNE L. FRASER AND LEE J. EMSDEN
CI2--CI2 1.724 (2) C14--O1 1.216 (2)
N 1---C7 !.399 (2) C14---O2 1.304 (2) Department o f Chemistry, University o f Newcastle upon
NI---CI 1.415 (3) O2--HI 1 0.87 (3)
Tyne, Newcastle upon Tyne NE1 7RU, England. E-mail:
C7--NI---CI 123.1 (2) O1---C!4--C13 122.4 (2) w. clegg @ ncl. ac. uk
C7--NI--HI 110.6(17) O2--C!4---C 13 !14.2(2)
CI--NI--H! 117.8(18) C 14---O2--H 11 109(2)
O 1------C14---O2 123.3 (2) (Received 24 February 1997; accepted 14 March 1997)
C2---Ci 3--Ci4---O1 -68.3 (3) C2--C13--C14--O2 109.4 (2)
o Abstract
Table 4. Hydrogen-bonding geometry (A, °)for HD2
D--H. • .A D--H H. • .A D. • .A D--H. • .A The title compound, C14H8ClnN20, is an unexpected
N i--H 1. • .CI I 0.75 (2) 2.59 (2) 2.987 (2) i 15 (2) side product of a reaction to convert an acid chloride
NI--HI. • .O1 0.75 (2) 2.31 (2) 2.946 (3) 143 (2) into a nitrile, the nature of which indicates the prob-
O2--HI 1- • .O1 i 0.87 (3) 1.77 (3) 2.646 (2) 178 (3)
able mechanism of the major reaction. In the crystal
Symmetry code: (i) ½ - x, - ½ - y, - z .
structure, a conjugated and approximately planar cinn-
For both polymorphs, no absorption correction was applied. amide framework is attached to an almost perpendicular
All the H atoms were experimentally located and their tetrachloro-substituted pyridyl ring, severe steric inter-
coordinates and displacement coefficients were isotropically actions overcoming the enhanced delocalization which
refined. would occur with coplanarity.
For both c o m p o u n d s , data collection: CAD-4 Software
( E n r a f - N o n i u s , 1989); cell refinement: CAD-4 Software; data
reduction: MoIEN (Fair, 1990); program(s) used to solve Comment
structures: SHELXS86 (Sheldrick, 1990); program(s) used to
During an investigation into the scope of the reaction
refine structures: SHELXL93 (Sheldrick, 1993); m o l e c u l a r
for the direct conversion of a carboxylic acid into a
graphics: ORTEPII (Johnson, 1976); software used to prepare
material for publication: SHELXL93.
nitrile under mild conditions (Tucker & Thomas, 1996),
cinnamoyl chloride, (2), was treated with 4-sulfon-
The authors thank Servizio Italiano di Diffusione amido-2,3,5,6-tetrachloropyridine, (3) (Iddon, Mack,
Dati Cristallografici del CNR (Parma) for access to the Suschitzky, Taylor & Wakefield, 1980) in the presence
Cambridge Data Files. of triethylamine and a catalytic amount of 4-dimethyl-
aminopyridine. Two products were isolated, the desired
3-phenylpropenenitrile, (4) (in 58% yield), and an
Lists of atomic coordinates, displacement parameters, structure factors
and complete geometry have been deposited with the IUCr (Reference:
unknown crystalline substance to which we initially
SK1077). Copies may be obtained through The Managing Editor, assigned the structure (5). However, X-ray structure
International Union of Crystallography, 5 Abbey Square, Chester CHI analysis established that the compound was in fact the
2HU, England. simple amide (1) (in 20% yield), in which loss of
SO2 from the presumed intermediate (5) had occurred
(Fig. 1).
References
Castellari, C. & Ottani, S. (1995). Acta Cryst. C51, 2612-2615. CI
Castellari, C. & Ottani, S. (1996). Acta Cryst. C52, 2619-2622. O CI~ " ~ N
Castellari, C. & Ottani, S. (1997). Acta Cryst. C53, 482-486.
Castellari, C. & Sabatino, P. (1994). Acta Cryst. C50, 1723-1726.
Castellari, C. & Sabatino, P. (1996). Acta Cryst. C52, 1708-1712.
H2NS°2 I cl
Enraf-Nonius (1989). CAD-4 Software. Version 5.0. Enraf-Nonius, (2) (3) Cl CI CI
Delft, The Netherlands. o O"-~"-N o C"-..~N
Fair, C. K. (1990). MolEN. An Interactive Intelligent System for Ph " ~ ' C N + either 'l I I1 °r p h / ~ H N ~ C ,
Crystal Structure Analysis. Enraf-Nonius, Delft, The Netherlands. (4) Ph~NSO2~"AXCI
Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge Cl Cl
National Laboratory, Tennessee, USA. 58-68% (5) 6--23% (1)
Kovala-Demertzi, D., Mentzafos, D. & Terzis, A. (1993). Polyhedron, Cl
12, 1361-1370. Cl ~/~...xvH
Moser, P., Sallmann, A. & Wiesenberg, I. (1990). J. Med. Chem. 33,
2358-2367. N- CI
Sheldrick, G. M. (1990). Acta Cryst. A46, 467-473. CI
Sheldrick, G. M. (1993). SHELXL93. Program for the Refinement of
Crystal Structures. University of G6ttingen, Germany. (6)

© 1997 Intemational Union of Crystallography Acta Crystallographica Section C

Printed in Great Britain - all rights reserved ISSN 0108-2701 © 1997