Polarized molecular-electronic structures and supramolecular aggregation in 1-(6-amino-1,3-benzodioxol-5-yl)-3-arylprop-2-en-1-ones

Article abstract of DOI:10.1107/S0108270104020414

The molecular-electronic structure and supramolecular aggregation in 1-(6-amino-1,3-benzodioxol-5-yl)-3-arylprop-2-en-1-ones was investigated. The molecules of (I) were linked into simple sheets generated by translation, by means of one N-H...O and one C-H...π(arene) hydrogen bond. Compounds (I) and (II) crystallized with Z^' values of 1 and 2 while compound (II) formed two polymorphs which were monoclinic and triclinic denoted as (IIa) and (IIb). It was observed that the monoclinic polymorph had a higher density than the triclinic polymorph and was thermodynamically more stable form.

Full text of DOI:10.1107/S0108270104020414

organic compounds
0
Acta Crystallographica Section C
Crystal Structure
Communications
Compounds (I) and (III) crystallize with Z values of 1 and
, respectively, while compound (II) forms two polymorphs,
2
viz. monoclinic and triclinic, denoted (IIa) and (IIb), respec-
ISSN 0108-2701
tively, which crystallize concomitantly from dimethylform-
0
amide, with Z values of 1 and 2, respectively (Figs. 1±4). Of
the two polymorphs of (II), the monoclinic polymorph has a
signi®cantly higher density than the triclinic polymorph and
hence is probably the thermodynamically more stable form
Polarized molecular±electronic
structures and supramolecular
(Burger & Ramberger, 1979).
aggregation in 1-(6-amino-1,3-benzo-
dioxol-5-yl)-3-arylprop-2-en-1-ones
a
b
b
John N. Low, Justo Cobo, Manuel Nogueras, Paola
c
c
d
Cuervo, Rodrigo Abonia and Christopher Glidewell *
a
Department of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen
b
AB24 3UE, Scotland, Departamento de Qu Âõ mica Inorg a nica y Org a nica,
c
Universidad de Ja e n, 23071 Ja e n, Spain, Grupo de Investigaci o n de Compuestos
Heteroc Âõ clicos, Departamento de Qu Âõ mica, Universidad de Valle, AA 25360 Cali,
d
Colombia, and School of Chemistry, University of St Andrews, Fife KY16 9ST,
Scotland
Correspondence e-mail: cg@st-andrews.ac.uk
Received 12 August 2004
Accepted 16 August 2004
Online 18 September 2004
Molecules of 1-(6-amino-1,3-benzodioxol-5-yl)-3-(4-methyl-
phenyl)prop-2-en-1-one, C H NO , (I), 1-(6-amino-1,3-
benzodioxol-5-yl)-3-(4-methoxyphenyl)prop-2-en-1-one, C -
1
7
15
3
There is signi®cant bond ®xation within the amino-substi-
1
7
tuted aryl rings of (I)±(III) (Table 1). In particular, the C3aÐ
C4 and C7ÐC7a bonds are both short, while the C5ÐC6 and
C6ÐC7 bonds are long. In addition, the C6ÐC8 bond is short
H NO , (II), and 1-(6-amino-1,3-benzodioxol-5-yl)-3-[4-(tri-
5
1
4
¯
uoromethyl)phenyl]prop-2-en-1-one, C H F NO , (III), all
1
7
12
3
3
contain an intramolecular NÐHÁ Á ÁO hydrogen bond and all
exhibit polarized molecular±electronic structures. The mol-
ecules of (I) are linked into simple sheets, generated by
translation, by means of one NÐHÁ Á ÁO and one CÐ
for its type (mean value 1.488 AÊ ; Allen et al., 1987), while C8Ð
O8 is long (mean value 1.231 AÊ ). These values point to the
charge-separated form, (A) (see scheme below), as an
important contributor to the overall molecular±electronic
structure, alongside the delocalized form, (B). An entirely
similar pattern of distances (Table 1) is observed in the
analogous compounds (IV) and (V), the structures of which
have recently been reported (Low et al., 2002), although this
was not discussed or noted in the original report, which
focused exclusively on the supramolecular aggregation of (IV)
and (V).
HÁ Á Áꢀ(arene) hydrogen bond. Compound (II) crystallizes as
0
two concomitant polymorphs, viz. (IIa), with Z = 1 in P2 /c,
1
0
and (IIb), with Z = 2 in P1. In (IIa), intra- and intermolecular
NÐHÁ Á ÁO hydrogen bonds generate a helical chain of rings,
and these chains are linked into sheets by simple helical chains
built from a CÐHÁ Á Áꢀ(arene) hydrogen bond, while in (IIb),
the molecules are linked into simple chains by a CÐHÁ Á ÁO
0
hydrogen bond. In (III), where Z = 2, each type of molecule
forms a simple NÐHÁ Á ÁO hydrogen-bonded chain generated
by translation and the two types of chain are linked by a single
ꢀ±ꢀ stacking interaction.
Comment
A range of 2-aminochalcone derivatives have been prepared
for use as intermediates in the synthesis of new 6,7-methyl-
enedioxytetrahydroquinolin-4-ones, compounds with inter-
esting biological and pharmacological properties (Donnelly &
Farell, 1990; Prager & Thredgold, 1968; Kurasawa et al., 2002).
We report here the molecular and supramolecular structures
of three such compounds, (I)±(III), and compare them with
two further examples, (IV) and (V) (Low et al., 2002).
In all cases, the molecular skeletons are fairly close to being
planar but, as shown by the key torsion angles (Table 2), there
are some signi®cant deviations in most of the independent
examples. The sole exception is the type 1 molecule
(containing atom O11, etc.; Fig. 3a) of compound (III). The
®ve-membered rings show some ¯exibility of conformational
behaviour. Thus, this ring is planar in (IIa) [although not in
(IIb)] and in the type 2 molecule of compound (III), but it
o744 # 2004 International Union of Crystallography
DOI: 10.1107/S0108270104020414
Acta Cryst. (2004). C60, o744±o750

organic compounds
adopts an envelope conformation, with a folding across the
OÁ Á ÁO line, in (I), in both molecules of (IIb) and in the type 1
molecule of (III). For these rings, the ring-puckering para-
tions at the methoxy substituent (Table 2), and this alone is
suf®cient to preclude the possibility of any additional
symmetry
meter ' (Cremer & Pople, 1975) takes the values 31.1 (15)
All of the molecules contain an intramolecular NÐHÁ Á ÁO
hydrogen bond (Tables 3±6), in each case generating an S(6)
motif (Bernstein et al., 1995), and these may have some
in¯uence on the overall molecular conformations. The
supramolecular structures of (I) and (IIa) both depend upon a
combination of NÐHÁ Á ÁO and CÐHÁ Á Áꢀ(arene) hydrogen
bonds to generate sheets, but the structures differ consider-
ably in detail. In compound (I), the amine atom N5 in the
molecule at (x, y, z) acts as hydrogen-bond donor, via atom
H5B, to ring atom O1 in the molecule at (x, y � 1, z), so
generating by translation a C(7) chain running parallel to the
2
ꢀ
and 30.5 (9) in (I) and (III), respectively, and 30.9 (5) and
ꢀ
213.7 (5) in the two independent molecules of (IIb). The two
independent molecules in (IIb) exhibit different conforma-
Figure 1
The molecule of (I), showing the atom-labelling scheme. Displacement
ellipsoids are drawn at the 30% probability level and H atoms are shown
as small spheres of arbitrary radii.
Figure 2
The molecule of (IIa), showing the atom-labelling scheme. Displacement
ellipsoids are drawn at the 30% probability level and H atoms are shown
as small spheres of arbitrary radii.
Figure 4
The two independent molecules of (III), showing the atom-labelling
scheme for (a) the type 1 molecule and (b) the type 2 molecule.
Displacement ellipsoids are drawn at the 30% probability level and H
atoms are shown as small spheres of arbitrary radii.
Figure 3
Figure 5
The two independent molecules of (IIb), showing the atom-labelling
scheme for (a) the type 1 molecule and (b) the type 2 molecule.
Displacement ellipsoids are drawn at the 30% probability level and H
atoms are shown as small spheres of arbitrary radii.
Part of the crystal structure of (I), showing the formation of a chain
parallel to [010]. For the sake of clarity, H atoms bonded to C atoms have
been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the
symmetry positions (x, y � 1, z) and (x, 1 + y, z), respectively.
ꢁ
Acta Cryst. (2004). C60, o744±o750
John N. Low et al.
17
C H
3
15NO , two polymorphs of C17H15NO
4
, and C17
H F
12 3
NO
3
o745

organic compounds
[
(
010] direction (Fig. 5). In addition, atom C2 in the molecule at
x, y, z) acts as hydrogen-bond donor, via atom H2A, to the
translation a chain running parallel to the [100] direction
(Fig. 6). The combination of the [100] and [010] chains
1
3
C11±C16 ring in the molecule at (x � 1, y, z), so generating by
generates a sheet parallel to (001), lying in the domain < z <
2 4
(Fig. 7). Four sheets of this type pass through each unit cell,
but there are no direction-speci®c interactions between adja-
cent sheets.
The monoclinic polymorph (IIa) of compound (II) exhibits
two CÐHÁ Á Áꢀ(arene) hydrogen bonds in addition to the two
NÐHÁ Á ÁO interactions (Table 4). Amine atom N5 in the
molecule at (x, y, z) acts as donor, again via atom H5B, but this
1
time to carbonyl atom O8 in the molecule at (2 � x, y � ,
2
1
2
1
�
z), so producing a helical C (4)C(6)[S(6)] chain of rings
2
running parallel to the [010] direction and generated by the 2
1
1
screw axis along (1, y, ) (Fig. 8). This chain of rings may be
4
contrasted with the very simple chain formed by the NÐ
HÁ Á ÁO hydrogen bonds in compound (I) (Fig. 5). Of the two
CÐHÁ Á Áꢀ(arene) hydrogen bonds, that having atom C2 as the
donor simply reinforces the foregoing [010] chain. However,
that involving atom C13 in the molecule at (x, y, z) as donor to
Figure 6
Part of the crystal structure of (I), showing the formation of a chain
parallel to [100]. For the sake of clarity, H atoms bonded to C atoms not
involved in the motif shown have been omitted. Atoms marked with an
asterisk (*) or a hash (#) are at the symmetry positions (x � 1, y, z) and
(1 + x, y, z), respectively.
Figure 9
A stereoview of part of the crystal structure of polymorph (IIa), showing
the formation of an [010] chain generated by CÐHÁ Á Áꢀ(arene) hydrogen
bonds. For the sake of clarity, H atoms not involved in the motif shown
have been omitted.
Figure 7
A stereoview of part of the crystal structure of (I), showing the formation
of a sheet parallel to (001). For the sake of clarity, H atoms bonded to C
atoms not involved in the motif shown have been omitted.
Figure 8
Part of the crystal structure of polymorph (IIa), showing the formation of
Figure 10
a chain of rings parallel to [010]. For the sake of clarity, H atoms bonded
to C atoms have been omitted. Atoms marked with an asterisk (*), a hash
A stereoview of part of the crystal structure of polymorph (IIa), showing
the formation of a sheet parallel to (001). For the sake of clarity, the
intramolecular hydrogen bond and H atoms bonded to C atoms and not
involved in the motif shown have been omitted.
1
(
1
2
#) or an ampersand (&) are at the symmetry positions (2 � x, y � ,
2
1
1
�
z), (x, y � 1, z) and (2 � x, 2 + y, 2 � z), respectively.
ꢁ
o746 John N. Low et al.
17
C H15NO
3
, two polymorphs of C17
H
4 12
15NO , and C17H F
3
NO
3
Acta Cryst. (2004). C60, o744±o750

organic compounds
1
2
1
2
the C11±C16 ring in the molecule at (1 � x, y � , � z) not
atoms O11 and O21 in the molecules at (x � 1, y, z), so
generating C(7) chains by translation (Table 5 and Fig. 12).
These two chains are linked by an aromatic ꢀ±ꢀ stacking
interaction between the C111±C116 and C211±C216 rings
within the asymmetric unit. The dihedral angle between the
planes of these two rings is only 4.5 (2) , the interplanar
Ê
spacing is ca 3.5 A and the centroid±centroid separation is
Ê
3.618 (2) A. Propagation of this interaction then links the two
independent translational chains (Fig. 12)
only generates a second chain running parallel to [010], this
1
1
time generated by the 2 axis along ( , y, ) (Fig. 9), but also
1
2
4
serves to link all of the chain of rings into an (001) sheet
(
(
Fig. 10). In the triclinic polymorph (IIb), the type 1 molecules
Fig. 3a) are linked by means of a single CÐHÁ Á ÁO hydrogen
ꢀ
bond into chains generated by translation, while the type 2
molecules (Fig. 3b) are pendent from these chains and linked
to them by NÐHÁ Á ÁO hydrogen bonds (Fig. 11)
Each of the two independent molecules in compound (III)
forms a simple C(7) chain. The amine atoms N15 and N25 in
the molecules at (x, y, z) act as donors to, respectively, the ring
The simple and complex sheets in (I) and (IIa), the single
chains in (IIb) and the paired chains in (III) may be brie¯y
compared with the supramolecular structures of the analogues
0
(
IV) and (V) (Low et al., 2002). In (IV), where Z = 1, the sole
signi®cant intermolecular interactions are a CÐHÁ Á ÁO
hydrogen bond with a ring O atom as acceptor, which gener-
ates zigzag C(10) chains, and a ꢀ±ꢀ stacking interaction
0
linking these chains into sheets. In (V), where Z = 2, two NÐ
4
HÁ Á ÁO hydrogen bonds generate centrosymmetric R (16)
8
tetramers, which are weakly linked into chains by two rather
long CÐHÁ Á ÁO hydrogen bonds. Hence, for the ®ve
compounds (I)±(V), while their intramolecular properties are
all very similar, their supramolecular aggregation patterns are
all different. For no single example in this series could the
supramolecular structure be predicted from a knowledge of
the supramolecular structures of all the others.
Experimental
For the synthesis of (I), a solution of 6-amino-3,4-methylenedioxy-
acetophenone (0.5 g, 2.79 mmol), 4-tolualdehyde (0.33 g, 2.75 mmol),
ethanol (10 ml) and aqueous NaOH (0.5 ml, 20%) was heated under
re¯ux for 20 min. After cooling the mixture, the resulting precipitate
was ®ltered off and washed with ethanol, yielding (I) as a yellow solid
Figure 11
A stereoview of part of the crystal structure of polymorph (IIb), showing
the formation of a C(8) chain along [100]. For the sake of clarity, the
intramolecular hydrogen bond and H atoms bonded to C atoms and not
involved in the motif shown have been omitted.
(
yield 91%, m.p. 401 K). Spectroscopic analysis, IR (KBr disc, ꢁ,
�
1
cm ): 3454, 3278 (NH
2
), 1646 (C O), 1606 (C C), 1224 (OCH
, ꢂ): 2.33 (3H, s, CH ), 5.96 (2H, s, OCH O), 6.35
1H, s), 7.23 (2H, d, J = 8.0 Hz), 7.53 (1H, d, J = 15.4 Hz), 7.65 (1H, s),
.67 (2H, br s, NH ), 7.73 (2H, d, J = 8.0 Hz), 7.81 (1H, d, J = 15.4 Hz);
C NMR (DMSO-d , ꢂ): 21.0 (CH ), 95.8, 101.1 (OCH O), 108.0,
09.9, 122.7, 128.5, 129.4, 132.5, 137.7, 139.6, 141.0, 151.7, 152.7, 187.7
2
O);
1
H NMR (DMSO-d
6
3
2
(
7
2
13
6
3
2
1
+
(
C
7 7
O). MS (70 eV): m/e (%) 281 (41, [M ]), 190 (100, [M±C H ]).
Crystals of (I) suitable for single-crystal X-ray diffraction were grown
from a solution in ethanol. For the synthesis of (II), a solution
of 6-amino-3,4-methylenedioxyacetophenone (0.5 g, 2.79 mmol),
4-methoxybenzaldehyde (0.38 g, 2.79 mmol), ethanol (10 ml) and
aqueous NaOH (0.5 ml, 20%) was heated under re¯ux for 30 min.
After cooling the mixture, the resulting precipitate was ®ltered off
and crystallized from ethanol, giving (II) as an orange solid (yield
�
1
5
0%, m.p. 405 K). Spectroscopic analysis, IR (KBr disc, ꢁ, cm ):
461, 3303 (NH ), 1644 (C O), 1603 (C C), 1223 (OCH O);
, ꢂ): 3.89 (3H, s, OCH ), 5.93 (2H, s, OCH O), 6.19
1H, s), 6.57 (2H, br s, NH ), 6.91 (2H, d, J = 8.0 Hz), 7.26 (1H, s), 7.35
1H, d, J = 15.4 Hz), 7.47 (2H, d, J = 8.0 Hz), 7.71 (1H, d, J = 15.4 Hz);
3
2
2
1
H NMR (CDCl
3
3
2
(
(
2
13
3 3 2
C NMR (CDCl , ꢂ): 55.2 (OCH ), 96.8, l01.5 (OCH O), 108.2, 112.0,
14.5, 121.2, 128.3, 130.0, 138.9, 142.1, 150.0, 153.5, 161.2, 189.0
Figure 12
1
Part of the crystal structure of (III), showing the formation of a ꢀ-stacked
pair of chains parallel to [100]. For the sake of clarity, H atoms bonded to
C atoms have been omitted. Atoms marked with an asterisk (*) or a hash
+
(C
7 7
O). MS (70 eV): m/e (%) 297 (27, [M ]), 190 (100, [M±C H O]).
Crystallization from dimethylformamide gave a mixture of the
monoclinic polymorph (IIa) as red crystals (m.p. 382 K) and the
triclinic polymorph (IIb) as yellow crystals (m.p. 389 K). For the
(#) are at the symmetry positions (x � 1, y, z) and (1 + x, y, z),
respectively.
ꢁ
Acta Cryst. (2004). C60, o744±o750
John N. Low et al.
17
C H
3
15NO , two polymorphs of C17H15NO
4
, and C17
H F
12 3
NO
3
o747

organic compounds
Table 1
Selected bond distances (A) for compounds (I)±(V).
Ê
Bond
(I)
nil
(IIa)
(IIb)
Mol 1
1
(IIb)
Mol 2
2
(III)
Mol 1
1
(III)
Mol 2
2
(IV)
nil
(V)
Mol 1
1
(V)
Mol 2
2
x
nil
Cx3aÐCx4
Cx4ÐCx5
Cx5ÐCx6
Cx6ÐCx7
Cx7ÐCx7a
1.368 (3) 1.357 (2) 1.357 (2) 1.359 (2) 1.358 (3) 1.355 (3) 1.361 (2) 1.358 (2) 1.351 (2)
1.402 (3) 1.416 (2) 1.418 (2) 1.418 (2) 1.415 (3) 1.417 (3) 1.417 (2) 1.419 (2) 1.418 (2)
1.424 (3) 1.430 (2) 1.423 (2) 1.422 (2) 1.429 (3) 1.419 (3) 1.426 (2) 1.426 (2) 1.431 (2)
1.428 (3) 1.430 (2) 1.420 (2) 1.435 (2) 1.428 (3) 1.421 (3) 1.428 (2) 1.426 (2) 1.423 (2)
1.339 (3) 1.354 (2) 1.353 (2) 1.350 (2) 1.350 (3) 1.355 (3) 1.355 (2) 1.354 (2) 1.353 (2)
Cx7aÐCx3a 1.386 (3) 1.394 (2) 1.387 (2) 1.391 (2) 1.390 (3) 1.390 (3) 1.394 (2) 1.390 (2) 1.393 (2)
Cx5ÐNx5
Cx6ÐCx8
Cx8-Ox8
1.364 (3) 1.353 (2) 1.364 (2) 1.361 (2) 1.368 (2) 1.369 (3) 1.359 (2) 1.370 (2) 1.360 (2)
1.459 (3) 1.461 (2) 1.470 (2) 1.462 (2) 1.468 (2) 1.468 (3) 1.470 (2) 1.473 (2) 1.463 (2)
1.249 (3) 1.246 (2) 1.240 (2) 1.244 (2) 1.244 (4) 1.237 (2) 1.243 (2) 1.253 (2) 1.250 (2)
Table 2
Selected torsion angles ( ) for compounds (I)±(III).
ꢀ
Parameter
(I)
(IIa)
(IIb)
Mol 1
1
(IIb)
Mol 2
2
(III)
Mol 1
1
(III)
Mol 2
2
x
nil
nil
Cx5ÐCx6ÐCx8ÐCx9
� 177.8 (2)
179.63 (13) � 168.15 (13) � 175.23 (13) � 171.93 (18) � 156.36 (19)
153.13 (14) 171.9 (2) 176.7 (2)
Cx6ÐCx8ÐCx9ÐCx10
Cx8ÐCx9ÐCx10ÐCx11
Cx9ÐCx10ÐCx11ÐCx12
Cx13ÐCx14ÐOx14ÐCx41
� 159.1 (2) � 175.03 (14) � 170.48 (13)
178.4 (2)
� 9.0 (2)
179.77 (14) � 178.12 (13) � 176.05 (13) � 177.59 (19) � 177.65 (19)
5.1 (2) � 11.3 (2) 0.7 (3)
� 16.8 (2)
� 8.6 (3)
� 175.91 (13)
1.4 (2)
� 176.09 (14)
synthesis of (III), a solution of 6-amino-3,4-methylenedioxyaceto-
phenone (0.5 g, 2.79 mmol), 4-(tri¯uoromethyl)benzaldehyde (0.49 g,
Re®nement
Re®nement on F
2
2
2
o
2
w = 1/[ꢈ (F
) + (0.0198P)
2
2
2.79 mmol), ethanol (10 ml) and aqueous NaOH (0.5 ml, 20%) was
R[F > 2ꢈ(F )] = 0.061
wR(F ) = 0.135
S = 1.11
+ 1.4934P]
where P = (F
(Á/ꢈ)max < 0.001
Áꢉmax = 0.24 e A
Áꢉmin = � 0.21 e AÊ
2
2
o
2
c
+ 2F
)/3
heated under re¯ux for 25 min. After cooling the mixture, the
resulting precipitate was ®ltered off and washed with ethanol,
yielding (III) as an orange solid (yield 75%, m.p. 417 K). Spectro-
Ê
� 3
3
1
062 re¯ections
91 parameters
� 3
�
1
1
scopic analysis, IR (KBr disc, ꢁ, cm ): 3468, 3305 (NH
2
), 1646
, ꢂ): 5.94
O), 6.38 (1H, s, H6), 7.6 (1H, d, H8, J =
2
), 7.76 (2H, d, J = 8.0 Hz), 8.02 (1H, d, J =
H-atom parameters constrained
(C
O), 1606 (C C), 1228 (OCH
2 6
O); H NMR (DMSO-d
Table 3
Hydrogen-bonding geometry (A, ) for (I).
(
1H, s, H2), 5.98 (2H, s, OCH
2
Ê
ꢀ
1
5.0 Hz), 7.69 (2H, br s, NH
5.4 Hz), 8.15 (2H, d, J = 8.0 Hz); C NMR (DMSO-d
O), 108.0, 108.9, 113.5 (CF ), 125.5, 126.7, 129.3, 138.0, 139.1,
39.4, 152.2, 153.2, 187.1 (C O). MS (70 eV): m/e (%) 335 (100,
13
1
6
, ꢂ): 95.8, 101.2
Cg1 is the centroid of the C11±C16 ring.
(OCH
2
3
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
1
+
[M ]). Crystals of (III) suitable for single-crystal X-ray diffraction
were grown from a solution in ethanol.
N5ÐH5AÁ Á ÁO8
0.96
0.96
0.99
1.88
2.07
2.86
2.612 (3)
3.032 (3)
3.644 (4)
131
178
137
i
N5ÐH5BÁ Á ÁO1
ii
C2ÐH2AÁ Á ÁCg1
Compound (I)
Symmetry codes: (i) x; y � 1; z; (ii) x � 1; y; z.
Polymorph (IIa)
Crystal data
�
3
C
17
H
15NO
3
D
x
= 1.374 Mg m
Crystal data
r
M = 281.30
Mo Kꢄ radiation
�
3
Monoclinic, P2 =n
Cell parameters from 3062
re¯ections
C
M
17
H
15NO
4
D
x
= 1.427 Mg m
1
Ê
a = 10.530 (5) A
r
= 297.30
Mo Kꢄ radiation
Cell parameters from 3170
re¯ections
Ê
b = 7.362 (5) A
Ê
c = 17.546 (5) A
ꢀ
ꢅ = 5.3±27.5
ꢆ = 0.10 mm
T = 120 (2) K
Monoclinic, P2 =c
1
� 1
Ê
a = 17.5560 (4) A
ꢀ
Ê
b = 5.0914 (2) A
ꢀ
ꢃ = 91.719 (5)
V = 1359.6 (12) A
Z = 4
ꢅ = 2.9±27.5
ꢆ = 0.10 mm
T = 120 (2) K
Ê
3
Ê
ꢀ
Ê
�
1
Block, yellow
0.40 Â 0.30 Â 0.20 mm
c = 15.4869 (4) A
ꢃ = 91.9240 (16)
V = 1383.51 (7) A
Z = 4
3
Block, red
0.04 Â 0.02 Â 0.02 mm
Data collection
Nonius KappaCCD area-detector
diffractometer
2024 re¯ections with I > 2ꢈ(I)
Data collection
R
int = 0.065
ꢀ
'
scans, and ! scans with ꢇ offsets
Absorption correction: multi-scan
EvalCCD; Duisenberg et al.,
003)
min = 0.958, Tmax = 0.981
ꢅ
max = 27.5
Nonius KappaCCD area-detector
diffractometer
' and ! scans
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
T
14 325 measured re¯ections
3170 independent re¯ections
2271 re¯ections with I > 2ꢈ(I)
h = � 13 ! 12
(
2
T
k = � 9 ! 9
Rint = 0.038
ꢅmax = 27.5
ꢀ
l = � 22 ! 22
h = � 21 ! 22
k = � 6 ! 6
1
3
7 073 measured re¯ections
062 independent re¯ections
min = 0.959, Tmax = 0.998
l = � 20 ! 19
ꢁ
o748 John N. Low et al.
17
C H15NO
3
, two polymorphs of C17
H
4 12
15NO , and C17H F
3
NO
3
Acta Cryst. (2004). C60, o744±o750

organic compounds
Re®nement
Compound (III)
2
2
2
2
Re®nement on F
2
o
w = 1/[ꢈ (F ) + (0.0701P)
2
Crystal data
R[F > 2ꢈ(F )] = 0.045
wR(F ) = 0.128
S = 1.04
+ 0.2374P]
where P = (F
(Á/ꢈ)max = 0.002
2
2
2
c
o
+ 2F
)/3
C
M
17
H
12
F
3
NO
= 335.28
Triclinic, P1
a = 7.3420 (2) A
3
Z = 4
�
3
r
D
x
= 1.544 Mg m
Ê
� 3
3
2
169 re¯ections
01 parameters
Áꢉmax = 0.26 e A
Mo Kꢄ radiation
Cell parameters from 6611
re¯ections
ꢅ = 3.0±27.6
ꢆ = 0.13 mm
T = 120 (2) K
Block, red
0.60 Â 0.60 Â 0.50 mm
Ê
� 3
Ê
Áꢉmin = � 0.21 e A
Extinction correction: SHELXL97
Sheldrick, 1997)
Extinction coef®cient: 0.007 (2)
Ê
H-atom parameters constrained
b = 10.9241 (3) A
c = 18.7176 (5) A
ꢄ = 85.0180 (11)
ꢃ = 83.2280 (14)
ꢊ = 75.8180 (14)
V = 1442.71 (7) A
Ê
ꢀ
(
ꢀ
ꢀ
ꢀ
Ê
� 1
3
Table 4
Hydrogen-bonding geometry (A, ) for polymorph (IIa).
Ê
ꢀ
Data collection
Cg1 is the centroid of the C11±C16 ring and Cg2 is the centroid of the C3a/C4±
C7/C7a ring.
Nonius KappaCCD area-detector
diffractometer
6611 independent re¯ections
4510 re¯ections with I > 2ꢈ(I)
'
and ! scans
Absorption correction: multi-scan
SADABS; Sheldrick, 2003)
min = 0.920, Tmax = 0.937
Rint = 0.038
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
ꢀ
ꢅ
max = 27.6
(
T
h = � 9 ! 6
N5ÐH5AÁ Á ÁO8
0.96
0.96
0.99
0.95
1.95
2.49
2.84
2.81
2.6301 (15)
3.1232 (15)
3.640 (2)
126
123
138
130
i
k = � 14 ! 13
l = � 24 ! 24
N5ÐH5BÁ Á ÁO8
C2ÐH2BÁ Á ÁCg2
ii
iii
20 172 measured re¯ections
C13ÐH13Á Á ÁCg1
3.488 (2)
Re®nement
1
2
1
2
1 1
Symmetry codes: (i) 2 � x; y �
;
� z; (ii) x; y � 1; z; (iii) 1 � x; y �
;
2 2
� z.
2
2
2
2
Re®nement on F
2
R[F > 2ꢈ(F )] = 0.052
wR(F ) = 0.157
S = 1.04
o
w = 1/[ꢈ (F ) + (0.0874P)
2
+ 0.3568P]
where P = (F
(Á/ꢈ)max < 0.001
Áꢉmax = 0.77 e A
Áꢉmin = � 0.52 e AÊ
2
2
o
2
c
+ 2F
)/3
Polymorph (IIb)
Ê
� 3
6
4
611 re¯ections
33 parameters
� 3
Crystal data
H-atom parameters constrained
C
17
H15NO
4
Mo Kꢄ radiation
M
r
= 297.30
Triclinic, P1
a = 9.5352 (2) A
Cell parameters from 6517
re¯ections
Table 6
Hydrogen-bonding geometry (A, ) for (III).
Ê
ꢀ
Ê
ꢀ
ꢅ = 3.1±27.5
ꢆ = 0.10 mm
T = 120 (2) K
Ê
� 1
b = 10.6193 (3) A
c = 14.7611 (4) A
ꢄ = 89.1400 (14)
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
Ê
ꢀ
ꢀ
ꢀ
Ê
Block, yellow
0.45 Â 0.30 Â 0.20 mm
N15ÐH15AÁ Á ÁO18
0.96
0.96
0.96
0.96
1.91
2.26
1.91
2.09
2.637 (2)
3.161 (2)
2.662 (2)
3.024 (2)
131
156
134
165
ꢃ = 81.0970 (17)
i
N15ÐH15BÁ Á ÁO11
N25ÐH25AÁ Á ÁO28
ꢊ = 75.7540 (14)
V = 1430.83 (6) A
Z = 4
3
i
N25ÐH25BÁ Á ÁO21
�
3
Symmetry code: (i) x � 1; y; z.
D
x
= 1.380 Mg m
Data collection
1 1
For (I) and (IIa), the space groups P2 /n and P2 /c, respectively,
Nonius KappaCCD area-detector
diffractometer
4940 re¯ections with I > 2ꢈ(I)
were uniquely determined from the systematic absences. Crystals of
(IIb) and (III) are triclinic, and the space group P1 was selected and
then con®rmed by the structure analysis. All H atoms were located
from difference maps and subsequently treated as riding atoms, with
R
int = 0.035
ꢀ
'
and ! scans
Absorption correction: multi-scan
SADABS; Sheldrick, 2003)
min = 0.951, Tmax = 0.981
ꢅmax = 27.5
h = � 12 ! 12
k = � 13 ! 13
l = � 19 ! 19
(
T
Ê Ê
CÐH = 0.95 (CH), 0.98 (CH
and with Uiso(H) = 1.2Ueq(C,N), or 1.5Ueq(C) for the methyl groups.
3 2
) or 0.99 A (CH ) and NÐH = 0.96 A,
2
6
3 999 measured re¯ections
517 independent re¯ections
Ê
� 3
Ê
In compound (III), the highest residual peak (0.77 e A ) is 1.26 A
Ê
�
3
Ê
Re®nement
from F141 and the deepest hole (� 0.52 e A ) is 0.97 A from F141.
2
2
2
o
2
Re®nement on F
2
w = 1/[ꢈ (F
) + (0.0778P)
Careful inspection of electron-density maps indicated some libration
2
R[F > 2ꢈ(F )] = 0.049
wR(F ) = 0.137
S = 1.10
+ 0.1431P]
where P = (F
3
of the CF groups about the adjacent CÐC bonds, but gave no
2
2
2
c
o
+ 2F
)/3
grounds for modelling these groups with more than three F-atom sites
per group.
(Á/ꢈ)max = 0.001
Ê
� 3
� 3
6
3
512 re¯ections
99 parameters
Áꢉmax = 0.30 e A
Áꢉmin = � 0.37 e AÊ
For all four compounds, data collection: COLLECT (Nonius,
998). For compound (I), cell re®nement: DIRAX/LSQ (Duisenberg
H-atom parameters constrained
1
et al., 2000); data reduction: EvalCCD (Duisenberg et al., 2003);
program(s) used to solve structure: SIR97 (Altomare et al., 1999);
program(s) used to re®ne structure: OSCAIL (McArdle, 2003) and
SHELXL97 (Sheldrick, 1997). For compounds (IIa) and (III), cell
re®nement: DENZO (Otwinowski & Minor, 1997) and COLLECT;
data reduction: DENZO and COLLECT; program(s) used to solve
structure: SHELXS97 (Sheldrick, 1997); program(s) used to re®ne
structure: SHELXL97. For compound (IIb), cell re®nement:
DENZO and COLLECT; data reduction: DENZO and COLLECT;
program(s) used to solve structure: OSCAIL and SHELXS97;
Table 5
Hydrogen-bonding geometry (A, ) for polymorph (IIb).
Ê
ꢀ
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
N15ÐH15BÁ Á ÁO18
N25ÐH25AÁ Á ÁO28
N25ÐH25BÁ Á ÁO13
0.88
0.88
0.88
0.99
1.99
1.95
2.19
2.27
2.6451 (17)
2.6069 (19)
3.0586 (17)
3.221 (2)
130
131
170
161
i
C12ÐH12AÁ Á ÁO18
Symmetry code: (i) x � 1; y; z.
Acta Cryst. (2004). C60, o744±o750
ꢁ
John N. Low et al.
C
17
H
3
15NO , two polymorphs of C17H15NO
4
, and C17
H F
12 3
NO
3
o749

organic compounds
program(s) used to re®ne structure: OSCAIL and SHELXL97. For
all four compounds, molecular graphics: PLATON (Spek, 2003);
software used to prepare material for publication: SHELXL97 and
PRPKAPPA (Ferguson, 1999).
Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C.,
Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J.
Appl. Cryst. 32, 115±119.
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem.
Int. Ed. Engl. 34, 1555±1573.
Burger, A. & Ramberger, R. (1979). Mikrochim. Acta, 2, 259±271.
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354±1358.
Donnelly, J. A. & Farell, D. F. (1990). Tetrahedron, 46, 885±894.
Duisenberg, A. J. M., Hooft, R. W. W., Schreurs, A. M. M. & Kroon, J. (2000).
J. Appl. Cryst. 33, 893±898.
Duisenberg, A. J. M., Kroon-Batenburg, L. M. J. & Schreurs, A. M. M. (2003).
J. Appl. Cryst. 36, 220±229.
Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada.
Kurasawa, Y., Tsuruoka, A., Rikiishi, N., Fujiwara, N., Okamoto, Y. & Kim,
H. S. (2002). J. Heterocycl. Chem. 37, 791±798.
The X-ray data for compounds (II) and (III) were collected
at the EPSRC X-ray Crystallographic Service, University of
Southampton, England; the authors thank the staff for all their
help and advice. JNL thanks NCR Self-Service, Dundee, for
grants which have provided computing facilities for this work.
RA thanks `Fundaci o n para la Promoci o n de la Investigaci o n
y la Tecnolog Âõ a (Banco de la Rep u blica)' and Universidad del
Valle for ®nancial support. PC thanks COLCIENCIAS for a
doctoral fellowship. JC and MN thank Consejer Âõ a de Educa-
ci o n (Junta de Andaluc õ a, Spain) for ®nancial support.
Low, J. N., Cobo, J., Nogueras, M., S a nchez, A., Albornoz, A. & Abonia, R.
(
2002). Acta Cryst. C58, o42±o45.
McArdle, P. (2003). OSCAIL for Windows. Version 10. Crystallography
Centre, Chemistry Department, NUI Galway, Ireland.
Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands.
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276,
Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M.
Sweet, pp. 307±326. New York: Academic Press.
Prager, R. & Thredgold, M. (1968). Aust. J. Chem. 21, 229±241.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of
G oÈ ttingen, Germany.
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: SK1762). Services for accessing these data are
described at the back of the journal.
References
Sheldrick, G. M. (2003). SADABS. Version 2.10. University of G oÈ ttingen,
Germany.
Spek, A. L. (2003). J. Appl. Cryst. 36, 3±17.
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor,
R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1±19.
ꢁ
o750 John N. Low et al.
17
C H15NO
3
, two polymorphs of C17
H
4 12
15NO , and C17H F
3
NO
3
Acta Cryst. (2004). C60, o744±o750