SHUBHASISH MUKHERJEE et al.

1831

Compound (II) Supplementary data for this paper are available from the IUCr
Crystal data electronic archives (Reference: CF1330). Services for accessing these
data are described at the back of the journal.
Ct7HI6N205 Mo Ka radiation
Mr = 328.32 A = 0.71073 A,
Monoclinic Cell parameters from 2974
Cc reflections References
a = 17.9115 (13) ,~, 0 = 2.09-28.54 ° Allen, F. H. & Kennard, O. (1993). Chem. Des. Autom. News, 8,
b = 11.6279 (13) A, # = 0.102 m m -~ 31-37.
Bonnet-Delpon, D., Brgur, J.-P., Lequeux, T. & Ourevitch, M. (1996).
c = 7.7010 (7) A T = 180 (2) K
Tetrahedron, 52, 59-70.
/3 = 95.842 (3) ° Block
Bravo, P., Bruche, L., Farina, A., Fronza, G., Meiile, S. V. & Merli,
V = 1595.6 (3) ,~3 0.40 × 0.38 x 0.32 m m A. (1993). Tetrahedron Asymmetr)', 4, 2131-2134.
Z=4 Pale yellow Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354-1358.
D, = 1.367 Mg m -3 Cum, G., Aversa, M. C. & Uccella, N. (1968). Gazz. Chim. ltal. 98,
Dm not measured 782-794.
Flack, H. D. (1983). Acta Co'st. A39, 876-881.
Data collection Fletcher, D. A., McMeeking, R. F. & Parkin, D. (1996). J. Chem. Inf.
Siemens S M A R T area- 1714 reflections with Comput. Sci. 36, 746-749.
detector diffractometer I > 2o-(/) Hammer, J. & Macaluso, A. (1964). Chem. Rev. 64, 473-495.
scans R,nt = 0.055 Huisgen, R. (1968). Angew. Chem. Int. Ed. Engl. 7, 321-328.
Absorption correction: 0m,x = 28.54 ° Sheldrick, G. M. (1994). SHELXTL/PC Reference Manual Version
5.0. Siemens Analytical X-ray Instruments Inc., Madison, Wiscon-
multi-scan (SADABS; h = - 1 2 - - - , 23
sin, USA.
Sheldrick, 1996) k = - 1 5 ---, 15 Sheldrick, G. M. (1996). SADABS. Program for Empirical Absorp-
Train -- 0.96, Tm~ = 0.968 l = - 9 ~ 10 tion Correction of Area Detector Data. University of G6ttingen,
4693 measured reflections Intensity decay: none Germany.
2388 independent reflections Sheldrick, G. M. (1997). SHELXL97. Program for the Refinement of
Crystal Structures. University of G6ttingen, Germany.
Refinement Siemens (1994). SMART. Version 4.021. Data Collection Software.
Refinement on F 2 w = 1/[o.2(Fo2) + (0.0442P) 2] Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin,
R[F2 > 2o-(F2)] = 0.043 where P = (F,,2 + 2F,2)/3 USA.
wR(F2) = 0.098 (A/o.)max < 0.001 Siemens (1995). SAINT. Version 4.021. Data Integration Software.
Apm~x = 0 . 1 6 e A -3 Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin,
S = 0.912
Z21Pmin = - 0 . 1 9 e ,~-3 USA.
2388 reflections Spek, A. L. (1998). PLATONfor Windows. University of Utrecht, The
218 parameters Extinction correction: none
Netherlands.
H-atom parameters Scattering factors from
constrained International Tables for
Crystallography (Vol. C)
T a b l e 2. Selected geometric parameters (A, ° ) f o r (II)
01--c5 1.397 (3) N2~3 1.491 (3) Acta Cryst. ( 1 9 9 9 ) . C 5 5 , 1 8 3 1 - 1 8 3 3
OI--N2 1.453 (3) C3--C4 1.541 (4)
O4---N3 1.225 (4) C4--C5 1.506 (41
O5--N3 1.233 (4) A new polymorph of sulfathiazole
C5--O1--N2 104.9 (2) N2---C3--C4 103.3 (2)
O1--N2--C3 105.68 (19) C5---C4--C3 104.5 (2)
O~-N3---O5 124.2 (3) O 1--C5--C4 106.1 (2) DAVID S. HUGHES,'* MICHAEL B. HURSTHOUSE,° TERRY
C5--O 1--N2--C3 -39.5 (2) N2--O 1--C5--C4 38.0 (2) THRELFALLc AND STEWART TAVENER c
O 1--N2~C3---C4 24.2 (3) C3---C4---C5--O 1 -22.0 (3)
N2--C3--C4--C5 - 1.9 (3) ~Department of Chemistry, University of Wales Cardiff, PO
The crystal structure of (II) is non-centrosymmetric, but the Box 912, Park Place, Cardiff CF1 3TB, Wales, bDepartment
Flack parameter [1.9 (13); Hack, 1983] was indeterminate and of Chemistry, University of Southampton, Highfield,
hence the absolute structure could not be determined. Southampton S017 1BJ, England, and 'Department of
For both compounds, data collection: SMART (Siemens, Chemistry, University of York, Heslington, York YOIO 5DD,
1994); cell refinement: SAINT (Siemens, 1995); data re- England. E-mail: mbh @soton, ac. uk
duction: SAINT; program(s) used to solve structures:
SHELXTL/PC (Sheldrick, 1994); program(s) used to refine (Received 3 June 1999; accepted 26 July 1999)
structures: SHELXL97 (Sheldrick, 1997), molecular graphics:
SHELXTL/PC; software used to prepare material for publica-
tion: SHELXTL/PC. Abstract
Crystals of sulfathiazole, 4-amino-N-thiazol-2-ylidene-
W e w i s h to a c k n o w l e d g e t h e u s e o f t h e E P S R C ' s b e n z e n e s u l f o n a m i d e , C 9 H 9 N 3 0 2 S 2 , f o r m e d f r o m boil-
C h e m i c a l D a t a b a s e S e r v i c e at D a r e s b u r y L a b o r a t o r y i n g w a t e r are s h o w n to be a fifth p o l y m o r p h . T h e c r y s -
( F l e t c h e r et al., 1996) for a c c e s s to t h e C a m b r i d g e tal s t r u c t u r e c o n t a i n s t w o i n d e p e n d e n t m o l e c u l e s , w h i c h
S t r u c t u r a l D a t a b a s e ( A l l e n & K e n n a r d , 1993). associate through hydrogen bonds and van der Waals

© 1999 International Union of Crystallography Acta Crystallographica Section C

Printed in Great Britain - all rights reserved ISSN 0108-2701 © 1999
1832 C9H9N302S2

interactions to produce a two-dimensional sheet struc-

ture.

Comment
Sulfathiazole (4- amino- N- thiazol - 2 - ylidenebenzene-
sulfonamide), (I), first prepared in 1938, was one of the
earliest examples of the potent antimicrobial drugs de-
rived from sulfanilamide, commonly called the sulfon-
amides. The polymorphism of sulfathiazole has been
extensively investigated and Burger & Dialer (1983)
have described it as the 'classic' polymorphic com-
pound. Four polymorphs have previously been struc-
turally identified (Kruger & Gafner, 1971, 1972; Babilev
et al., 1987), and their hydrogen-bonding patterns dis-
cussed (Blagden et al., 1998). As part of our own ex-
tensive study of the polymorphism of this compound,
of its solvates and adducts, and of its potential use as
a supramolecular linker, we have shown that the form
from boiling water which has long been termed poly-
morph II in the pharmaceutical literature and which has Fig. 2. The unit-cell contents for sulfathiazole,polymorph V. viewed
been assumed to have one of the previously known along a.
structures, does in fact have a new structure which there-
fore identifies a fifth polymorph. A preliminary report of The detailed discussion of the structures of the four
this finding has been published (Hughes et al., 1997), previously crystallographically recognized polymorphs
and a structure determination based on powder XRD concentrated on the networks of molecules connected
analysis has appeared (Chan et al., 1999). We present via 'classical' hydrogen bonds, i.e. N - - H . . - N and N - -
here the single-crystal structure of this new polymorph. H . . . O . Not unnaturally, the final descriptions depend
H~N~H critically on the cut-off values for the N . . . N and
N - . . O contacts. Using the fairly large D . . . A value of
3.3 ,~, (Table 1), we find that, of the hydrogen-bonding
|1 14 interactions in the present structure, all but two are weak
O-~sI~O and occur only within the layers.
I s tt The sheets mentioned above are formed by juxta-
positioning of alternating rows of A and B mol-
H H ecules created by 21 screw-axis relationships. The
(I) two strongest hydrogen bonds, with D . . . A distances
The crystal structure contains two independent mol- of 2.794 (4) and 2.865 (4),~,, occur between thiazole
ecules which we term A and B. These associate into two N - - H groups and sulfonyl O atoms, between A and B
infinite (AB) sheets, parallel to the ab face of the unit rows. The next set, owith D--.A distances in the range
cell and centred approximately at z - ¼ and ~. 3 A view 3.010 (4)-3.061 (4) A, involve the NH2 H atoms and sul-
of the two independent molecules showing the atom fonyl O atoms, one within an A row, one within a B row
numbering is given in Fig. 1, and the packing diagram, and one between A B rows. The remaining contacts iden-
viewed along a, shows the layer structure (Fig. 2). tified involve two further oamine-sulfonyl-O interactions
of 3.116 (4) and 3.211 (4) A, and one amine-amine inter-
action of 3.267 (4) ~,. Two of the hydrogen bonds, how-
c-~NIl ~)~C15 ,. 011 022 ~ C 2 6 c~
ever, involve small D - - H . - . A angles of 132(3) and
141 (3) °, and are likely to be very weak. All other in-
'--' [Link] L) ~LN12 ~ N 2 1 7 4 ~ 2 termolecular contacts are greater than the van der Waals
~ 5 ~ S12 radii sums.
C17 ~7~

Experimental
Fig. 1. A general view of the molecular structures of the two inde-
pendent molecules of sulfathiazole, polymorph V. The ellipsoids Crystals of the new polymorph of sulfathiazole were obtained
are drawn at the 35% probability level and H atoms are shown as by evaporation to dryness of a boiling aqueous solution,
spheres of arbitrary radii. followed by drying above 373 K (Anwar et al., 1989).
 D. S. H U G H E S , M. B. H U R S T H O U S E , T. T H R E L F A L L A N D S. T A V E N E R 1833

Crystal data Supplementary data for this paper are available from the IUCr
C9HgN302S2 Mo Ko~ radiation electronic archives (Reference: FG1566)• Services for accessing these
Mr = 255.31 A = 0.71073 A, data are described at the back of the journal.
Monoclinic Cell parameters from 2749
P2,/n reflections
a = 10.399 (2) A, 0 = 3.05-25.00 ° References
b = 15.132(3) A, # = 0.462 m m - t Anwar, J., Tarling, S. E. & Barnes, P. (1989). J. Pharm. Sci. 78,
c = 14.280 (3) ,~, T = 150(2) K 337-342.
/3 = 91.21 (3) ° Block Babilev, F. V., Bei'skii, V. K., Simonov, A. & Arzamastsev, A. P.
V = 2246.6 (8) ]k3 0.15 × 0.10 × 0.08 m m (1987). Khim. Farm. Zh. 21, i 275-1280.
Z=8 Colourless Blagden, N., Davey, R. J., Lieberman, H. F., Williams, L., Payne,
D~ = 1.51 Mg m -3 R., Roberts, R., Rowe, R. & Docherty, R. (1998). J. Chem. Soc.
Faraday Trans. 94, 1035-1044.
Dm not measured Blessing, R. H. (1995). Acta Co'st. A51, 33-38.
Burger, A. & Dialer, D. (1983). Pharm. Acta Heir. 58, 72-78.
Data collection Chan, F. C., Anwar, J., Cernik, R., Barnes, P. & Wilson, R. M. (1999).
Nonius KappaCCD area- 3936 independent reflections J. Appl. Cryst. 32, 436-441.
detector diffractometer 2749 reflections with Chemical Crystallography Laboratory (1993). CAMERON. A Molecu-
~o + w scans to fill the I > 2o'(/) lar Graphics Package. Chemical Crystallography Laboratory, Uni-
versity of Oxford, England.
Ewald sphere Rint = 0.098
Hooft, R. (1998). COLLECT Software. Nonius BV, Delft, The
Absorption correction: 0max ---- 25 °
Netherlands.
multi-scan (SORTA V; h = - 1 2 - - , 12 Hughes, D. S., Hursthouse, M. B., Lancaster, R. W., Tavener, S.,
Blessing, 1995) k = - 1 7 --~ 17 Threlfall, T. L. & Turner, P. (1997)• J. Pharm. Pharmacol. 49, $4,
Tmin = 0 . 8 6 8 , Tmax = 0.990 l = - 1 6 - - , 16 20.
28 369 measured reflections Intensity decay: none Kruger, G. J. & Gafner, G. (1971). Acta Crvst. B27, 326--333.
Kruger, G. J. & Gafner, G. (1972). Acta Cryst. B28, 272-283•
Refinement Otwinowski, Z. & Minor, W. ( 1997)• Methods Enzymol. 276, 307-326.
Sheldrick. G. M. (1990)• Acta Co'st. A46, 467-473.
Refinement on F 2 (/~/O')max ---- - 0 . 0 3 8
Sheldrick, G. M. (1997)• SHELX97. Release 97-2. Program for the
R(F) = 0.046 Z~Pmax = 0.256 e A -3 Refinement of Crystal Structures. University of G6ttingen, Germany.
wR(F 2) = 0.079 Apmi, = --0.373 e A,-3
S = 0.858 Extinction correction: none
3936 reflections Scattering factors from
319 parameters International Tables for
H atoms: see below Crystallography (Vol. C) Acta Cryst. ( 1 9 9 9 ) . C 5 5 , 1 8 3 3 - 1 8 3 5
w = 1/[o-2(F,,2) + (0.1P) 2]
where P = (Foe + 2F,?)/3
N-(4-Chlorophenyl)-N-methylcyanamide
T a b l e 1. Hydrogen-bonding geometry (A, o)
O m H • ..A D--H H. • .A D. • .A D--H...A IAN D. CUNNINGHAM,a MARK E. LIGHT b AND MICHAEL B.
NII--HI0- -NIT 0.90(2) 2.14(2) 3.016(4) 165(3) HURSTHOUSEb
NII--HI0- •O11~ 0•90(2) 2.54(3) 3.211 (4) 132(3)
NII--Hll • .022" 0.93 (2) 2.10 (2) 3.010 (4) 167 (5) ~Department of Chemistry, School of Physical Sciences,
NI3--HI7. .O21"' 0.86 2.04 2.865 (4) 161
N2 I--H20. .O12" 0.90(2) 2.24(2) 3.061 (4) 152(3) University of Surrey, Guilford GU2 5XH, England, and
N21--H21 • .O21' 0.90(2) 2.37(3) 3.116(4) 141 (3) b University of Southampton, Department of Chemistry,
N21--H21 • .N22' 0.90 (2) 2.44 (2) 3.267 (4) 154 (3) Highfield, Southampton S017 1BJ, England. E-mail:
N23--H27. .O11" 0.86 1.94 2.794 (4) 173 light@ [Link]
Symmetry codes: (i) ½ - x, ~ + y , - - ½ - z; (ii) - x , 1 - y , - z ; (iii)
½ +x,~ -y,z- ½" (iv) - x , - > ' , - z ; (v) ½ - x , y - ½,½ - z;(vi) (Received 7 July 1999; accepted 28 July 1999)
I- - - y , ½+Z.
I +X ~ ~

The H atoms on Nl 1 and N21 were refined isotropically using

DFIX restraints (Sheldrick, 1997); all other H atoms were Abstract
treated as riding atoms. A n X - r a y s t r u c t u r a l a n a l y s i s o f t h e title c o m p o u n d ,
Data collection: DENZO (Otwinowski & Minor, 1997) and C8H7C1N2, s h o w s an e s s e n t i a l l y p l a n a r m o l e c u l e , b u t
COLLECT (Hooft, 1998). Cell refinement: DENZO and COL- w i t h an u n u s u a l l y l o n g a r y l - C to p l a n a r - N b o n d .
LECT. Data reduction: DENZO and COLLECT. Program(s)
used to solve structure: SHELXS97 (Sheldrick, 1990)• Pro-
gram(s) used to refine structure: SHELXL97 (Sheldrick, 1997). Comment
Molecular graphics: CAMERON (Chemical Crystallography
In t h e c o u r s e o f o n - g o i n g i n v e s t i g a t i o n s o f N - a r y l -
Laboratory, 1993). Software used to prepare material for pub-
lication: SHELXL97. c y a n o g u a n i d i n e s , t h e title c o m p o u n d , (1), w a s p r e p a r e d
a n d i s o l a t e d . In s i m p l e N - a r y l c y a n o g u a n i d i n e s s u c h as
W e t h a n k t h e E P S R C for s u p p o r t o f t h e c r y s t a l l o g r a - N - c y a n o - N ' - ( 4 - m e t h o x y p h e n y l ) g u a n i d i n e , (2), t h e aryl-
p h y facilities at S o u t h a m p t o n U n i v e r s i t y . bearing amino lone pair conjugates predominantly with

© 1999 International Union of Crystallography Acta Crystallographica Section C

Printed in Great Britain - all rights reserved ISSN 0108-2701 © 1999