Hydrogen-bonding patterns in 3-alkyl-3-hydroxy-indolin-2-ones

Article abstract of DOI:10.1107/S0108270110001058

The mol-ecules of racemic 3-benzoyl-methyl-3-hydroxy-indolin-2-one, C ₁₆H₁₃NO₃, (I), are linked by a combination of N-H...O and O-H...O hydrogen bonds into a chain of centrosymmetric edge-fused R 2 ²(10) and R 4

Full text of DOI:10.1107/S0108270110001058

organic compounds
Acta Crystallographica Section C
Crystal Structure
(VII) have been prepared as precursors for the formation of
chalcones by acid-catalysed dehydration reactions.
Communications
ISSN 0108-2701
Hydrogen-bonding patterns in 3-alkyl-
3-hydroxyindolin-2-ones
Diana Becerra,a Braulio Insuasty,a Justo Cobob and
Christopher Glidewellc*
a
´
Departamento de Quımica, Universidad de Valle, AA 25360 Cali, Colombia,
b
´
´
´
´
Departamento de Quımica Inorganica y Organica, Universidad de Jaen, 23071
Jaen, Spain, and cSchool of Chemistry, University of St Andrews, Fife KY16 9ST,
´
Scotland
Correspondence e-mail: cg@st-andrews.ac.uk
Received 17 December 2009
Accepted 8 January 2010
Online 22 January 2010
Compounds (I)–(VII) were prepared by reactions of isatin
with methyl ketones using basic catalysis (see scheme), as
were the analogues (VIII)–(XII). The compounds all contain a
stereogenic centre, at atom C3 in (I)–(VII) (Fig. 1), and if an
achiral base is employed as the catalytic agent, as here, the
products are obtained as racemic mixtures. However, if an
enantiomerically pure form of a chiral base is used, then the
products are found with a significant excess of one enantiomer
over the other, as in the syntheses of (IX) (Luppi et al., 2005),
(XI) (Luppi et al., 2006) and (XII) (Xing et al., 2007).
The molecules of racemic 3-benzoylmethyl-3-hydroxyindolin-
2-one, C16H13NO3, (I), are linked by a combination of N—
HÁ Á ÁO and O—HÁ Á ÁO hydrogen bonds into a chain of
centrosymmetric edge-fused R22(10) and R44(12) rings. Five
monosubstituted analogues of (I), namely racemic 3-hydroxy-
3-[(4-methylbenzoyl)methyl]indolin-2-one, C17H15NO3, (II),
racemic 3-[(4-fluorobenzoyl)methyl]-3-hydroxyindolin-2-one,
C16H12FNO3, (III), racemic 3-[(4-chlorobenzoyl)methyl]-3-
hydroxyindolin-2-one, C16H12ClNO3, (IV), racemic 3-[(4-
bromobenzoyl)methyl]-3-hydroxyindolin-2-one, C16H12BrN-
O3, (V), and racemic 3-hydroxy-3-[(4-nitrobenzoyl)methyl]-
indolin-2-one, C16H12N2O5, (VI), are isomorphous in space
group P1. In each of compounds (II)–(VI), a combination of
N—HÁ Á ÁO and O—HÁ Á ÁO hydrogen bonds generates a chain
of centrosymmetric edge-fused R22(8) and R22(10) rings, and
these chains are linked into sheets by an aromatic ꢀ–ꢀ
stacking interaction. No two of the structures of (II)–(VI)
exhibit the same combination of weak hydrogen bonds of C—
HÁ Á ÁO and C—HÁ Á Áꢀ(arene) types. The molecules of racemic
3-hydroxy-3-(2-thienylcarbonylmethyl)indolin-2-one, C14H11-
NO3S, (VII), form hydrogen-bonded chains very similar to
those in (II)–(VI), but here the sheet formation depends upon
a weak ꢀ–ꢀ stacking interaction between thienyl rings.
Comparisons are drawn between the crystal structures of
compounds (I)–(VII) and those of some recently reported
analogues having no aromatic group in the side chain.
As expected from the method of synthesis, (I)–(VII) all
crystallize as racemic mixtures and all crystallize in centro-
symmetric space groups. However, while compound (I), which
contains an unsubstituted phenyl ring in the side chain
(Fig. 1a), crystallizes in the space group P21/c, compounds
(II)–(VI), which all contain a single substituent at the
4-position of this ring (Fig. 1b–1f), are all isomorphous in the
space group P1. Compound (VII), which contains a 2-thienyl
unit rather than an aryl ring in the side chain (Fig. 1g), also
crystallizes in the space group P1 and the unit-cell repeat
Comment
We report here the structures of seven racemic 3-hydroxy-3-
(2-aryl-2-oxoethyl)indolin-2-ones, viz. compounds (I)–(VII)
(Fig. 1), which we compare with the structures of a number of
analogues, (VIII)–(XII), in the recent literature (Luppi et al.,
2005, 2006; Xing et al., 2007; Chen et al., 2009). Chalcones are
versatile bis-electrophilic reagents widely employed in the
synthesis of fused heterocyclic systems, and compounds (I)–
Acta Cryst. (2010). C66, o79–o86
doi:10.1107/S0108270110001058
# 2010 International Union of Crystallography o79

organic compounds
Figure 1
The molecular structures and atom-labelling schemes for (a) (I), (b) (II), (c) (III), (d) (IV), (e) (V), (f) (VI) and (g) (VII). Displacement ellipsoids are
drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
distances a, b and c are similar to those in compounds (II)–
(VI). The unit-cell angles have approximately complementary
values to those in (II)–(VI) and the atom coordinates in (VII)
are approximately related to those of the corresponding atoms
in (II)–(VI) by the transformation (1 À x, y, 1 À z). However,
comparison of the reduced-cell parameters shows that, despite
these similarities, compound (VII) is not isomorphous with the
series (II)–(VI).
the [010] direction. Antiparallel pairs of such chains are linked
by an O—HÁ Á ÁO hydrogen bond to generate a chain of
centrosymmetric edge-fused rings, in which R22(10) rings
centred at (12, n + 21, 21), where n represents an integer, alternate
with R44(12) rings centred at (21, n, 12), where n again represents
an integer (Fig. 2). Two chains of this type pass through each
unit cell but there are no direction-specific interactions of
structural significance between adjacent chains.
In the crystal structure of (I), molecules related by trans-
lation are linked by an N—HÁ Á ÁO hydrogen bond (Table 1) to
form a C(5) (Bernstein et al., 1995) chain running parallel to
Although compounds (II)–(VI) are isomorphous, they are
not strictly isostructural (Acosta et al., 2009), as the pattern of
the weaker hydrogen bonds of C—HÁ Á ÁO and C—HÁ Á Á
ꢀ
o80 Becerra et al.
C16H13NO3 and six analogues
Acta Cryst. (2010). C66, o79–o86

organic compounds
Figure 2
A stereoview of part of the crystal structure of (I), showing the formation
of a hydrogen-bonded chain of alternating R22(10) and R44(12) rings along
[100]. Hydrogen bonds are shown as dashed lines. For the sake of clarity,
H atoms bonded to C atoms have been omitted.
Figure 4
A stereoview of part of the crystal structure of (VII), showing the
formation of a hydrogen-bonded chain of alternating R22(8) and R22(10)
rings along [100]. Hydrogen bonds are shown as dashed lines. For the sake
of clarity, H atoms bonded to C atoms have been omitted. Note the
orientations of the unit cell and the chain relative to those in Fig. 3.
propagated solely by inversion, while a combination of
translation and inversion propagates the chain in (I).
However, one feature in common between these two chains is
that in neither type does ketonic atom O32 in the side chain
participate in the N—HÁ Á ÁO or O—HÁ Á ÁO hydrogen bonds.
The hydrogen-bonded chains in (II) are linked by a single
aromatic ꢀ–ꢀ stacking interaction involving the C321–C326
phenyl rings in the molecules at (x, y, z) and (2 À x, 1 À y,
2 À z) (Table 2). These two molecules form parts of the
Figure 3
A stereoview of part of the crystal structure of (II), showing the
formation of a hydrogen-bonded chain of alternating R22(8) and R22(10)
rings along [100]. Hydrogen bonds are shown as dashed lines. For the sake
of clarity, H atoms bonded to C atoms have been omitted.
1
2
1
2
1 3
2 2
hydrogen-bonded chains along (x, , ) and (x, , ), respec-
tively, so that propagation of this ꢀ–ꢀ stacking interaction
links the hydrogen-bonded chains into a sheet parallel to
(010).
ꢀ(arene) types differs between the members of the series, such
that no two of (II)–(VI) show an identical array of such
interactions. Indeed, no interactions of these types occur in the
structure of (II), while some of them are present in the
structures of each of (III)–(VI). It is thus convenient to
describe first the actions of the N—HÁ Á ÁO and O—HÁ Á ÁO
hydrogen bonds and the aromatic ꢀ–ꢀ stacking interactions in
compound (II), which are in fact the same in each of (II)–(VI),
and then briefly to note the actions of the weaker hydrogen
bonds in each of (III)–(VI).
The formation of hydrogen-bonded [100] chains containing
alternating R22(8) and R22(10) rings and linked by a ꢀ–ꢀ
stacking interaction into sheets parallel to (010) is common to
each of (II)–(VI) (Tables 1 and 2), and the sheet formation
provides another point of difference between the crystal
structures of (II)–(VI) on the one hand and that of (I) on the
other. However, the structures of each of (III)–(VI) exhibit
further weak interactions, different in each case, and thus
different from the structure of (II). In each of (IV), (V) and
(VI), although not in (II) or (III), there are C—HÁ Á ÁO
hydrogen bonds which reinforce, albeit weakly, the chains
along [100], and in each of (III) and (IV), but not in (II), (V)
or (VI), there is a C—HÁ Á Áꢀ(arene) hydrogen bond which
reinforces the linkage of the [100] chains into sheets. Although
the structures of both (V) and (VI) contain C—HÁ Á ÁO
hydrogen bonds, the number of these interactions differs in
the two structures (Table 1). In addition, it may be noted that
ketonic atom O32 is involved only in C—HÁ Á ÁO interactions in
compounds (IV), (V) and (VI), rather than in N—HÁ Á ÁO or
O—HÁ Á ÁO hydrogen bonds. Similarly, the only interaction
involving a nitro group O atom in (VI) is of C—HÁ Á ÁO type.
In compound (VII), a chain of edge-fused R22(8) and R22(10)
rings along [100] is formed (Fig. 4), similar to those in (II)–
In compound (II), symmetry-related pairs of O—HÁ Á ÁO
hydrogen bonds (Table 1) link the molecules at (x, y, z) and
(1 À x, 1 À y, 1 À z) to form an R22(10) motif, while similar
pairs of N—HÁ Á ÁO hydrogen bonds link the molecules at
(x, y, z) and (Àx, 1 À y, 1 À z) to form an R22(8) motif.
Propagation by inversion of these two motifs then generates a
chain of edge-fused rings running parallel to the [100] direc-
tion, in which the R22(10) rings are centred at (n + 12, 21, 12) and the
1
1
R22(8) rings are centred at (n, , ), where in both cases n
2
2
represents an integer (Fig. 3). This chain of rings differs from
that formed by (I) in two important respects. Firstly, both
hydrogen bonds in (II) utilize amidic atom O2 as the acceptor,
whereas in (I) the N—HÁ Á ÁO hydrogen bond utilizes hydroxy
atom O3 as the acceptor. Secondly, the chain in (II) is
ꢀ
Acta Cryst. (2010). C66, o79–o86
Becerra et al.
C16H13NO3 and six analogues o81

organic compounds
Figure 6
A stereoview of part of the crystal structure of (X) (CSD refcode
TAWFAZ; Luppi et al., 2005), showing the formation by the organic
components of a hydrogen-bonded sheet parallel to (100) and containing
R22(10) and R66(22) rings. Hydrogen bonds are shown as dashed lines. For
the sake of clarity, H atoms bonded to C atoms have been omitted.
Figure 5
A stereoview of part of the crystal structure of (IX) (CSD refcode
TAWDUR; Luppi et al., 2005), showing the formation of a hydrogen-
bonded chain of edge-fused R33(11) rings along [010]. Hydrogen bonds are
shown as dashed lines. For the sake of clarity, H atoms bonded to C atoms
have been omitted.
Compounds (IX) (CSD refcode TAWDUR; Luppi et al.,
2005) and (X) (CSD refcode TAWFAZ; Luppi et al., 2005)
were crystallized from the same solution following reaction of
5-bromoisatin with acetone catalysed by an enantiomerically
pure d-prolyl dipeptide. Compound (XI) is the pure R
enantiomer crystallizing in the space group P21, while (X) is a
hemihydrate of the racemic mixture, which crystallizes in the
space group C2/c. For (IX), the original report (Luppi et al.,
2005) indicated the formation of a hydrogen-bonded chain of
rings, although without providing any details, but the structure
of (X) was not mentioned at all. Re-examination of the
structure of (IX) using the deposited atomic coordinates
shows that molecules related by a 21 screw axis along (12, y, 0)
are linked by N—HÁ Á ÁO and O—HÁ Á ÁO hydrogen bonds to
form a chain of edge-fused R33(11) rings (Fig. 5), with no
direction-specific interactions between the chains.
(VI), but the orientation of the hydrogen-bonded structure
relative to the unit cell is different in (VII) from those in (II)–
(VI) (Figs. 3 and 4). As with (IV)–(VI), the structure of (VII)
contains two C—HÁ Á ÁO contacts within the hydrogen-bonded
chains; these have rather long HÁ Á ÁO distances and only one of
them involves hydroxy atom O3. However, the chains along
[100] are again linked into sheets, this time rather weakly, by a
ꢀ–ꢀ stacking interaction involving the thienyl rings of the
molecules at (x, y, z) and (1 À x, 1 À y, Àz). These rings are
˚
strictly parallel, with an interplanar spacing of 3.368 (2) A; the
˚
ring-centroid separation is 3.746 (2) A, corresponding to a
˚
ring-centroid offset of 1.640 (2) A. These two molecules are
components of the hydrogen-bonded chains along (x, 12, 21) and
1
1
(x, , À ), respectively, so that this ꢀ–ꢀ stacking interaction
2
2
links the hydrogen-bonded chains into a sheet parallel to
(010), similar to those in (II)–(VI).
Analysis of the structure of (X) using the deposited atomic
coordinates shows that the hydrogen bonding links the mol-
ecular components into a three-dimensional framework
structure, the formation of which is readily analysed in terms
of the actions of the three hydrogen bonds in turn. Enantio-
meric pairs of the organic component are linked by pairs of
symmetry-related O—HÁ Á ÁO hydrogen bonds, forming
centrosymmetric R22(10) dimers, analogous to those observed
in (II)–(VIII). These dimers are linked by the N—HÁ Á ÁO
hydrogen bond to form a sheet parallel to (100), containing
both R22(10) and R66(22) rings and lying in the domain (0 < x < 12)
(Fig. 6). The water molecule lies on a twofold rotation axis
It is of interest to compare the structures of (I)–(VII) with
those of some recently reported analogues, viz. (VIII)–(XII),
several of which have been reported only briefly, usually on a
simple proof-of-constitution or proof-of-configuration basis.
Compounds (VIII)–(XII) differ from (I)–(VII) in several
respects. Firstly, they have no aryl or heteroaryl group in the
side chain, thus reducing the scope for the formation of C—
HÁ Á ÁO and C—HÁ Á Áꢀ(arene) hydrogen bonds and of aromatic
ꢀ–ꢀ stacking interactions. Secondly, compounds (IX), (XI)
and (XII) crystallize in Sohncke space groups so that only a
single enantiomer is present in a given crystal (provided that
twinning is shown to be absent). Finally, compound (X) is a
hemihydrate, while solvent molecules are not found in any
other member of this series.
1
along (12, y, ) and forms pairs of O—HÁ Á ÁO hydrogen bonds
4
which link adjacent (100) sheets, so linking all of the molecules
into a single three-dimensional structure.
Compound (VIII) [Cambridge Structural Database (CSD;
Allen, 2002) refcode MUBMAY; Chen et al., 2009] crystallizes
as a racemic mixture in the space group P21/c, and a combi-
nation of N—HÁ Á ÁO and O—HÁ Á ÁO hydrogen bonds gener-
ates a chain of alternating R22(10) and R44(12) rings propagated
by translation and inversion along the [010] direction, entirely
analogous to the chain in (I).
The structure of the R enantiomer of (XI) (CSD refcode
TEQVUH; Luppi et al., 2006) was reported as a proof of
constitution and configuration, as shown by the value,
À0.006 (8), of the Flack x parameter (Flack, 1983), but no
description or discussion of the crystal structure was given.
This single enantiomer crystallizes in the space group P212121
and examination of the crystal structure using the deposited
ꢀ
o82 Becerra et al.
C16H13NO3 and six analogues
Acta Cryst. (2010). C66, o79–o86

organic compounds
Figure 7
Figure 8
A stereoview of part of the crystal structure of (XI) (CSD refcode
TEQVUH; Luppi et al., 2006), showing the formation of a hydrogen-
bonded chain of edge-fused R22(9) rings along [100]. Hydrogen bonds are
shown as dashed lines. For the sake of clarity, H atoms bonded to C atoms
have been omitted.
A stereoview of part of the crystal structure of (XII) (CSD refcode
YIFZIX; Xing et al., 2007), showing the formation of a hydrogen-bonded
chain of edge-fused R22(9) rings along [100]. Hydrogen bonds are shown as
dashed lines. For the sake of clarity, H atoms bonded to C atoms have
been omitted.
atomic coordinates shows the formation of a chain of edge-
fused R22(9) rings built from molecules related by the 21 screw
(XII), while in the racemic hemihydrate (X), where the
organic component is the same as in (IX), the N—HÁ Á ÁO and
O—HÁ Á ÁO hydrogen bonds between the organic molecules
form a sheet structure unlike any other compound in this
series.
For compounds (I)–(VII), the OÁ Á ÁO distances in the
O—HÁ Á ÁO hydrogen bonds are all very similar (Table 1), as
are the NÁ Á ÁO distances in the N—HÁ Á ÁO hydrogen bonds in
(II)–(VII). However, wide variations occur across this series in
the DÁ Á ÁA distances of the weaker interactions, suggesting that
many of these may be adventitious contacts rather than
significant structure builders.
3
axis along (x, , 1) and linked by N—HÁ Á ÁO and O—HÁ Á ÁO
4
hydrogen bonds (Fig. 7).
Compound (XII) (CSD refcode YIFZIX; Xing et al., 2007)
also crystallizes in the space group P212121 and the Flack x
parameter of 0.03 (8) indicates that only a single enantiomer is
present in the crystal selected for data collection. However,
the identity of this enantiomer is nowhere specified in the
original report, although the deposited coordinates corre-
spond to the S enantiomer, consistent with the reported use of
an l-prolyl amide as the catalytic base. The crystal structure
was described as consisting of a chain of centrosymmetric
R22(9) rings, but this description must be incorrect on two
grounds, firstly because centrosymmetric motifs cannot
contain an odd number of atoms, and secondly because
centrosymmetric motifs cannot be formed in the noncentro-
symmetric space group P212121. The packing diagram
provided by the authors does not show a chain. In fact, re-
examination of this structure shows that it contains a chain of
R22(9) rings entirely analogous to the chain in compound (XI),
but built from molecules related by the 21 screw axis along
Experimental
Samples of compounds (I)–(VII) were prepared following a reported
general procedure using piperidine as the catalytic base (Kusanur et
al., 2004). Yellow–brown crystals suitable for single-crystal X-ray
diffraction were grown by slow evaporation, at ambient temperature
and in air, of solutions in a mixture of ethanol and dimethyl-
formamide (1:1 v/v).
Analyses: for (I), yield 40%, m.p. 423–425 K (decomposition)
(literature value 442–445 K; Lindwall & Maclennan, 1932); MS (EI)
m/z (% abundance): 249 (6), 222 (100), 119 (41), 105 (86). For (II),
yield 43%, m.p. 458 K (decomposition) (literature value 458–460 K;
Lindwall & Maclennan, 1932); MS (EI) m/z (% abundance): 281 [M+]
(1), 263 (3), 236 (34), 119 (100). For (III), yield 46%, m.p. 489–491 K
(decomposition); MS (EI) m/z (% abundance): 285 [M+] (2), 267 (3),
240 (40), 123 (100), 119 (41). For (IV), yield 60%, m.p. 465–467 K
(decomposition) (literature value 470–472 K; Popp & Donigan,
1979); MS (EI) m/z (% abundance): 303 [M + 2] (0.6), 301 [M+] (1.4),
285 (1.2), 283 (2.5), 258 (15), 256 (40), 141 (32), 139 (100), 119 (57).
For (V), yield 55%, m.p. 462–464 K (decomposition) (literature value
448–453 K; Lindwall & Maclennan, 1932); MS (EI) m/z (% abun-
dance): 347 [M + 2] (1.1), 345 [M+] (1.0), 230 (1), 228 (1), 302 (31),
300 (32), 185 (100), 183 (98), 119 (95). For (VI), yield 45%, m.p. 449–
451 K (decomposition) (literature value 458–460 K; Popp & Donigan,
1
4
1
2
(x, , ) (Fig. 8).
In conclusion, compounds (I)–(XIII) discussed here exhibit
several distinct patterns formed by conventional strong
hydrogen bonds of N—HÁ Á ÁO and O—HÁ Á ÁO types. Thus, (I)
and (VIII) form entirely similar hydrogen-bonded chains,
despite the differences between the steric requirements of the
terminal groups in their side chains, viz. phenyl in (I) and
isopropyl in (VIII). A second pattern of chain formation is
found in the isomorphous compounds (II)–(VI), as well as in
(VII). A third type of chain formation is shared by the
enantiomerically pure compounds (XI) and (XII). By
contrast, the single enantiomer of compound (IX) forms a
chain type unlike those in any of racemic compounds (I)–
(VIII), or in the enantiomerically pure compounds (XI) and
ꢀ
Acta Cryst. (2010). C66, o79–o86
Becerra et al.
C16H13NO3 and six analogues o83

organic compounds
1979); MS (EI) m/z (% abundance): 312 [M+] (1.0), 294 (5.6), 267
(6.0), 150 (100), 119 (54). For (VII), yield 39%, m.p. 476–478 K
(decomposition); MS (EI) m/z (% abundance): 273 [M+] (1), 255 (4),
228 (34), 119 (51).
Data collection
Bruker–Nonius KappaCCD area-
detector diffractometer
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
Tmin = 0.939, Tmax = 0.978
15674 measured reflections
2528 independent reflections
1664 reflections with I > 2ꢄ(I)
Rint = 0.054
Compound (I)
Refinement
R[F2 > 2ꢄ(F2)] = 0.053
wR(F2) = 0.151
S = 1.11
190 parameters
H-atom parameteÀrs3 constrained
Crystal data
3
˚
C16H13NO3
Mr = 267.27
Monoclinic, P21=c
a = 13.876 (3) A
b = 5.7725 (8) A
V = 1241.6 (4) A
Z = 4
˚
Áꢅmax = 0.29 e A
À3
˚
2528 reflections
Áꢅmin = À0.33 e A
Mo Kꢂ radiation
ꢃ = 0.10 mmÀ1
T = 120 K
0.26 Â 0.23 Â 0.18 mm
˚
˚
˚
Compound (IV)
c = 16.280 (3) A
ꢁ = 107.799 (16)ꢁ
Crystal data
C16H12ClNO3
Mr = 301.72
Triclinic, P1
ꢆ = 96.33 (3)ꢁ
V = 662.4 (5) A
Z = 2
Mo Kꢂ radiation
ꢃ = 0.30 mmÀ1
T = 120 K
Data collection
3
˚
Bruker–Nonius KappaCCD area-
detector diffractometer
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
Tmin = 0.975, Tmax = 0.982
15921 measured reflections
2427 independent reflections
1903 reflections with I > 2ꢄ(I)
Rint = 0.050
˚
a = 6.987 (2) A
˚
b = 7.689 (4) A
˚
c = 12.907 (4) A
ꢂ = 99.30 (3)ꢁ
ꢁ = 101.82 (4)ꢁ
0.34 Â 0.22 Â 0.10 mm
Refinement
Data collection
R[F2 > 2ꢄ(F2)] = 0.057
wR(F2) = 0.144
S = 1.20
181 parameters
H-atom parameteÀrs3 constrained
Bruker–Nonius KappaCCD area-
detector diffractometer
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
Tmin = 0.920, Tmax = 0.971
2604 measured reflections
2604 independent reflections
2051 reflections with I > 2ꢄ(I)
˚
Áꢅmax = 0.25 e A
À3
˚
2427 reflections
Áꢅmin = À0.29 e A
Refinement
Compound (II)
R[F2 > 2ꢄ(F2)] = 0.043
wR(F2) = 0.114
S = 1.07
191 parameters
H-atom parameteÀrs3 constrained
Crystal data
˚
Áꢅmax = 0.25 e A
C17H15NO3
Mr = 281.30
Triclinic, P1
a = 6.873 (2) A
b = 7.6700 (17) A
˚
c = 13.394 (5) A
ꢂ = 99.48 (2)ꢁ
ꢁ = 101.68 (3)ꢁ
ꢆ = 96.33 (2)ꢁ
V = 674.4 (4) A
Z = 2
Mo Kꢂ radiation
ꢃ = 0.10 mmÀ1
T = 120 K
À3
˚
2604 reflections
Áꢅmin = À0.40 e A
3
˚
˚
Table 1
Hydrogen bonds and short intermolecular contacts (A, ) for compounds
(I)–(VII).
˚
ꢁ
˚
0.34 Â 0.21 Â 0.09 mm
Cg1 represents the centroid of the C3a/C4–C7/C7a ring.
Data collection
Compound D—HÁ Á ÁA
D—H HÁ Á ÁA DÁ Á ÁA
D—HÁ Á ÁA
Bruker–Nonius KappaCCD area-
detector diffractometer
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
Tmin = 0.968, Tmax = 0.992
15497 measured reflections
2520 independent reflections
1783 reflections with I > 2ꢄ(I)
Rint = 0.088
(I)
N1—H1Á Á ÁO3i
0.88
0.82
0.88
0.84
0.88
0.82
0.95
0.88
0.87
0.99
0.95
0.95
0.88
0.86
0.99
0.95
0.88
0.86
0.99
0.95
2.15
1.97
1.99
1.90
1.99
1.93
2.69
2.00
1.88
2.50
2.51
2.97
2.01
1.90
2.49
2.49
1.99
1.90
2.55
2.52
2.49
2.00
1.96
2.58
2.59
2.918 (3) 146
O3—H3Á Á ÁO2ii
2.762 (3) 163
2.838 (3) 162
2.729 (3) 169
2.842 (2) 163
2.746 (2) 172
3.614 (3) 164
2.843 (3) 160
2.752 (3) 174
3.276 (3) 135
3.281 (4) 138
3.890 (3) 164
2.851 (4) 160
2.746 (3) 167
3.257 (4) 134
3.271 (4) 140
2.848 (3) 164
2.756 (3) 175
3.330 (4) 135
3.308 (4) 140
3.304 (4) 143
2.843 (3) 160
2.736 (2) 158
3.443 (3) 151
3.382 (3) 137
(II)
(III)
N1—H1Á Á ÁO2iii
O3—H3Á Á ÁO2ii
N1—H1Á Á ÁO2iii
O3—H3Á Á ÁO2ii
Refinement
C325—H325Á Á ÁCg1iv
(IV)
N1—H1Á Á ÁO2iii
R[F2 > 2ꢄ(F2)] = 0.062
wR(F2) = 0.159
S = 1.05
191 parameters
H-atom parameteÀrs3 constrained
O3—H3Á Á ÁO2ii
C31—H31BÁ Á ÁO2ii
C323—H323Á Á ÁO32v
C325—H325Á Á ÁCg1iv
N1—H1Á Á ÁO2iii
˚
Áꢅmax = 0.33 e A
Áꢅmin = À0.28 e A
À3
˚
2520 reflections
(V)
O3—H3Á Á ÁO2ii
C31—H31BÁ Á ÁO2ii
C323—H323Á Á ÁO32v
N1—H1Á Á ÁO2iii
Compound (III)
(VI)
O3—H3Á Á ÁO2ii
Crystal data
C31—H31BÁ Á ÁO2ii
C323—H323Á Á ÁO32v
C16H12FNO3
Mr = 285.27
Triclinic, P1
ꢆ = 96.034 (9)ꢁ
V = 641.43 (10) A
Z = 2
C326—H326Á Á ÁO33vi 0.95
3
˚
(VII)
N1—H1Á Á ÁO2vii
O3—H3Á Á ÁO2ii
C7—H7Á Á ÁO3v
C31—H31BÁ Á ÁO2ii
0.88
0.82
0.95
0.99
˚
a = 6.8858 (7) A
Mo Kꢂ radiation
ꢃ = 0.11 mmÀ1
T = 120 K
0.57 Â 0.32 Â 0.20 mm
˚
b = 7.7074 (8) A
˚
c = 12.7010 (9) A
ꢂ = 98.229 (7)ꢁ
ꢁ = 103.667 (7)ꢁ
Symmetry codes: (i) x, À1 + y, z; (ii) 1 À x, 1 À y, 1 À z; (iii) Àx, 1 À y, 1 À z; (iv) 1 À x,
1 À y, 2 À z; (v) 1 + x, y, z; (vi) À1 + x, y, z; (vii) 2 À x, 1 À y, 1 À z.
ꢀ
o84 Becerra et al.
C16H13NO3 and six analogues
Acta Cryst. (2010). C66, o79–o86

organic compounds
Table 2
Compound (VII)
˚
Parameters (A) for interactions between the substituted aryl rings (C321–
C326) in the molecules at (x, y, z) and (2 À x, 1 À y, 1 À z) in compounds
(II)–(VI).
Crystal data
C14H11NO3S
Mr = 273.30
Triclinic, P1
ꢆ = 84.559 (15)ꢁ
3
˚
V = 601.8 (2) A
Z = 2
D1 is the interplanar spacing, D2 the ring-centroid separation and D3 the ring-
centroid offset (slippage).
˚
a = 6.5958 (7) A
b = 7.9577 (14) A
Mo Kꢂ radiation
ꢃ = 0.27 mmÀ1
T = 120 K
0.41 Â 0.23 Â 0.14 mm
˚
Compound
D1
D2
D3
˚
c = 12.045 (3) A
ꢂ = 78.51 (2)ꢁ
(II)
3.553 (2)
3.421 (2)
3.435 (2)
3.490 (3)
3.408 (2)
3.820 (2)
3.704 (2)
3.708 (2)
3.739 (3)
3.691 (2)
1.403 (2)
1.420 (2)
1.396 (2)
1.342 (3)
1.417 (2)
ꢁ = 76.555 (13)ꢁ
(III)
(IV)
(V)
(VI)
Data collection
Bruker–Nonius KappaCCD area-
detector diffractometer
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
Tmin = 0.885, Tmax = 0.963
14010 measured reflections
2355 independent reflections
1798 reflections with I > 2ꢄ(I)
Rint = 0.058
Compound (V)
Crystal data
C16H12BrNO3
Mr = 346.18
Triclinic, P1
a = 7.016 (3) A
b = 7.7349 (12) A
˚
c = 13.052 (6) A
ꢂ = 99.69 (3)ꢁ
ꢁ = 101.51 (4)ꢁ
ꢆ = 96.70 (3)ꢁ
V = 675.8 (4) A
Z = 2
Mo Kꢂ radiation
ꢃ = 3.05 mmÀ1
T = 120 K
0.46 Â 0.25 Â 0.22 mm
Refinement
3
˚
R[F2 > 2ꢄ(F2)] = 0.045
wR(F2) = 0.113
S = 1.04
2355 reflections
172 parameters
H-atom parameteÀrs3 constrained
˚
˚
Áꢅmax = 0.31 e A
À3
˚
˚
Áꢅmin = À0.31 e A
All H atoms were located in difference maps. H atoms bonded to C
or N atoms were then treated as riding atoms in geometrically
idealized positions, with C—H = 0.95 (aromatic and thienyl), 0.98
Data collection
Bruker–Nonius KappaCCD area-
detector diffractometer
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
Tmin = 0.385, Tmax = 0.553
18834 measured reflections
2800 independent reflections
2215 reflections with I > 2ꢄ(I)
Rint = 0.075
˚
˚
(CH3) or 0.99 A (CH2), and N—H = 0.88 A, and with Uiso(H) =
kUeq(C,N), where k = 1.5 for the methyl group in compound (II),
which was permitted to rotate but not to tilt, and 1.2 for all other H
atoms bonded to C or N atoms. H atoms bonded to O atoms were
permitted to ride at the positions deduced from difference maps, with
Refinement
R[F2 > 2ꢄ(F2)] = 0.040
wR(F2) = 0.087
S = 1.09
190 parameters
H-atom parameteÀrs3 constrained
Uiso(H) = 1.5Ueq(O), giving O—H distances in the range 0.82–0.87 A
˚
(Table 1). Compound (IV) was treated as a nonmerohedral twin. A
modified reflection data file was prepared using the TwinRotMat
option in PLATON (Spek, 2009) and used with the HKLF5 option in
SHELXL (Sheldrick, 2008), giving twin fractions of 0.269 (2) and
0.731 (2).
˚
Áꢅmax = 0.57 e A
À3
˚
2800 reflections
Áꢅmin = À0.73 e A
Compound (VI)
For all compounds, data collection: COLLECT (Nonius, 1999); cell
refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction:
EVALCCD (Duisenberg et al., 2003); program(s) used to solve
structure: SIR2004 (Burla et al., 2005); program(s) used to refine
structure: SHELXL97 (Sheldrick, 2008); molecular graphics:
PLATON (Spek, 2009); software used to prepare material for
publication: SHELXL97 and PLATON.
Crystal data
C16H12N2O5
Mr = 312.28
Triclinic, P1
ꢆ = 96.46 (2)ꢁ
V = 682.7 (3) A
Z = 2
3
˚
˚
a = 7.026 (1) A
Mo Kꢂ radiation
ꢃ = 0.12 mmÀ1
T = 120 K
0.27 Â 0.17 Â 0.12 mm
˚
b = 7.598 (3) A
˚
c = 13.365 (4) A
ꢂ = 97.54 (3)ꢁ
ꢁ = 102.67 (2)ꢁ
´
´
The authors thank the Servicios Tecnicos de Investigacion
of the Universidad de Jaen and the staff for the data collec-
´
Data collection
tion. DB and BI thank COLCIENCIAS and Universidad del
Bruker–Nonius KappaCCD area-
detector diffractometer
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
Tmin = 0.970, Tmax = 0.986
19392 measured reflections
2683 independent reflections
1528 reflections with I > 2ꢄ(I)
Rint = 0.096
´
Valle for financial support. JC thanks the Consejerıa de
Innovacion, Ciencia y Empresa (Junta de Andalucıa, Spain),
´
´
´
the Universidad de Jaen (project reference UJA_07_16_33)
and Ministerio de Ciencia e Innovacion (project reference
´
SAF2008-04685-C02-02) for financial support.
Refinement
R[F2 > 2ꢄ(F2)] = 0.057
wR(F2) = 0.158
S = 1.07
208 parameters
H-atom parameteÀrs3 constrained
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: SQ3233). Services for accessing these data are
described at the back of the journal.
˚
Áꢅmax = 0.29 e A
À3
˚
2683 reflections
Áꢅmin = À0.33 e A
ꢀ
Acta Cryst. (2010). C66, o79–o86
Becerra et al.
C16H13NO3 and six analogues o85

organic compounds
Kusanur, R. A., Ghate, M. & Kulkarni, M. V. (2004). J. Chem. Sci. 116, 265–
270.
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C16H13NO3 and six analogues
Acta Cryst. (2010). C66, o79–o86