Two isomeric reaction products: Hydrogen-bonded sheets in methyl 4-(5-amino-3-phenyl-1H-pyrazol-1-yl)-3-nitro-benzoate and hydrogen-bonded chains of edge-fused rings in methyl 3-nitro-4-[(5-phenyl-1H-pyrazol-3-yl)amino] benzoate

Article abstract of DOI:10.1107/S010827010703346X

In methyl 4-(5-amino-3-phenyl-1H-pyrazol-1-yl)-3-nitro-benzo-ate, C17H14N4O4, the molecules are linked into complex sheets by a combination of N - H...N, N - H...O and C - H...O hydrogen bonds. In the isomeric methyl 3-nitro-4-[(5-phenyl-1H-pyrazol-3-yl)a

Full text of DOI:10.1107/S010827010703346X

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
pyrazole generated only compound (III), the direct analogue
of compound (II) (Portilla et al., 2007). Compound (I) and its
analogues should prove to be useful for the synthesis of
pyrazolobenzotriazepines, which have applications as drug,
agrochemical and dye intermediates (Tachibana & Kaneko,
1989).
ISSN 0108-2701
Two isomeric reaction products:
hydrogen-bonded sheets in methyl
4-(5-amino-3-phenyl-1H-pyrazol-
1-yl)-3-nitrobenzoate and hydrogen-
bonded chains of edge-fused rings
in methyl 3-nitro-4-[(5-phenyl-1H-
pyrazol-3-yl)amino]benzoate
Jaime Portilla,a Ernesto G. Mata,b Justo Cobo,c John N.
Lowd and Christopher Glidewelle*
a
Â
Departamento de Quõmica, Universidad de Valle, AA 25360 Cali, Colombia,
b
Â
Â
CONICET ± Facultad de Ciencias Bioquõmicas y Farmaceuticas, Universidad
Nacional de Rosario, Suipacha 531, S2002LRK, Argentina, cDepartamento de
Â
Â
Â
Â
Â
Quõmica Inorganica y Organica, Universidad de Jaen, 23071 Jaen, Spain,
dDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen
AB24 3UE, Scotland, and eSchool of Chemistry, University of St Andrews,
Fife KY16 9ST, Scotland
Correspondence e-mail: cg@st-andrews.ac.uk
Received 9 July 2007
Accepted 10 July 2007
Online 9 August 2007
In methyl 4-(5-amino-3-phenyl-1H-pyrazol-1-yl)-3-nitrobenzo-
ate, C17H14N4O4, the molecules are linked into complex
sheets by a combination of NÐHÁ Á ÁN, NÐHÁ Á ÁO and CÐ
HÁ Á ÁO hydrogen bonds. In the isomeric methyl 3-nitro-4-[(5-
phenyl-1H-pyrazol-3-yl)amino]benzoate, molecules exhibit a
polarized molecular±electronic structure and are linked into
chains of edge-fused rings by a combination of NÐHÁ Á ÁO and
CÐHÁ Á ÁO hydrogen bonds.
In (I), the CÐC bond distances within the aryl ring fall in
Ê
the range 1.381 (3)±1.400 (3) A, consistent with essentially
unperturbed aromatic delocalization, while the remaining
bond distances are all typical of their types (Allen et al., 1987).
By contrast, in (II), the C53ÐC54 and C55ÐC56 bond
distances are both signi®cantly shorter than the remaining
bonds in this ring (Table 2), while the C52ÐN52 bond is short
for its type. In addition, the N52ÐO521 bond, which partici-
pates in an intramolecular hydrogen bond (Table 3), is long for
its type. These observations, taken together, provide evidence
for the polarized forms (IIa) and (IIb) as important contri-
butors of the overall molecular±electronic structure of
compound (II). A similar conclusion was drawn from the
intramolecular geometry of compound (III) (Portilla et al.,
2007).
Comment
We report here the molecular and supramolecular structures
of the title compounds, (I) and (II) (Figs. 1 and 2), which are
the products from the two alternative pathways for the reac-
tion of methyl 4-¯uoro-3-nitrobenzoate with 5-amino-3-
phenylpyrazole. The reaction in which atom N1 of the pyra-
zole ring acts as the nucleophile generates compound (I),
while compound (II) is formed in the reaction in which the
amino N atom of the pyrazole ring acts as the nucleophile (see
reaction scheme below). The product mixture appears to be
very sensitive to the polarity of the solvent employed; in a
1:7 v/v mixture of dimethyl sulfoxide and methanol as the
solvent, compounds (I) and (II) are formed in equimolar
quantities, but compound (II) was the sole product isolated
from the corresponding reaction in neat dimethyl sulfoxide.
An analogous reaction in neat dimethyl sulfoxide using
5-amino-3-methylpyrazole in place of 5-amino-3-phenyl-
The molecules of (I) are linked into sheets by a combination
of NÐHÁ Á ÁN, NÐHÁ Á ÁO and CÐHÁ Á ÁO hydrogen bonds
(Table 1), and the formation of the sheet is readily analyzed in
terms of two simple one-dimensional substructures. Atoms N5
and C16 in the molecule at (x, y, z) act as hydrogen-bond
donors to pyrazole atom N2 and nitro atom O121, respec-
tively, both in the molecule at (32 x, 21 + y, 21 z), so forming a
C(5)C(6)[R22(13)] chain of rings (Bernstein et al., 1995)
running parallel to the [010] direction and generated by the 21
1
screw axis along (34, y, ) (Fig. 3). In the second substructure,
4
o510 # 2007 International Union of Crystallography
DOI: 10.1107/S010827010703346X
Acta Cryst. (2007). C63, o510±o513

organic compounds
atom N5 at (x, y, z) acts as a hydrogen-bond donor to ketonic
1
generating by inversion a cyclic dimer containing concentric
R22(22) and R22(26) rings, embedding two symmetry-related
R12(7) rings (Fig. 5). In addition, atom C53 in the molecule at
3
1
atom O141 in the molecule at (
+ x,
y,
+ z), so
2
2
2
forming a simple C(10) chain running parallel to the [101]
direction and generated by the n-glide plane at y = 34 (Fig. 4).
The combination of the chains parallel to [010] and [101]
generates a sheet parallel to (101), but there are no signi®cant
direction-speci®c interactions between adjacent sheets.
In addition to the intramolecular NÐHÁ Á ÁO hydrogen
bond, the structure of (II) contains three signi®cant inter-
molecular hydrogen bonds (Table 3), which combine to
generate a one-dimensional hydrogen-bonded structure of
considerable elegance. Atoms N2 and C36 in the molecule at
(x, y, z) both act as hydrogen-bond donors to carbonyl atom
O541 in the molecule at (1
x, 2
y, 1
z), thereby
Figure 2
A molecule of (II), showing the atom-labelling scheme. Displacement
ellipsoids are drawn at the 30% probability level.
Figure 3
A stereoview of part of the crystal structure of (I), showing the formation
of a hydrogen-bonded chain of rings along [010]. For the sake of clarity, H
atoms bonded to C atoms not involved in the motif shown have been
omitted.
Figure 1
A molecule of (I), showing the atom-labelling scheme. Displacement
ellipsoids are drawn at the 30% probability level.
ꢀ
Acta Cryst. (2007). C63, o510±o513
Portilla et al. C17H14N4O4 o511

organic compounds
(x, y, z) acts as a hydrogen-bond donor to nitro atom O522 in
1
the molecule at (1 x, y,
z), so forming a further cyclic
2
motif, this time an R22(10) ring generated by the twofold
rotation axis along (12, y, 41 ). Propagation of these two motifs by
successive inversion and rotation then generates a complex
chain of edge-fused rings running parallel to the [001] direc-
tion (Fig. 6). Two chains of this type, related to one another by
the C-centring operation, pass through each unit cell, but
Figure 6
A stereoview of part of the crystal structure of (II), showing the
formation of a hydrogen-bonded chain of edge-fused rings along [001].
For the sake of clarity, H atoms not involved in the motifs shown have
been omitted.
there are no signi®cant direction-speci®c interactions between
adjacent chains.
In contrast with the complexity of the chain of rings formed
by (II), the methyl analogue (III) forms a simpler chain of
edge-fused rings containing alternating R22(16) and R22(22)
rings, both generated by inversion using CÐHÁ Á ÁO and NÐ
HÁ Á ÁO hydrogen bonds, respectively (Portilla et al., 2007).
Figure 4
A stereoview of part of the crystal structure of (I), showing the formation
of a hydrogen-bonded C(10) chain along [101]. For the sake of clarity, H
atoms bonded to C atoms have been omitted.
Experimental
A solution of 5-amino-3-phenyl-1H-pyrazole (2 mmol) and methyl
4-¯uoro-3-nitrobenzoate (2 mmol) in dimethyl sulfoxide±methanol
(8 ml of a 1:7 v/v mixture) was heated under re¯ux with magnetic
stirring for 10 min. The mixture was cooled to ambient temperature
and the resulting solid was collected by ®ltration and washed with
methanol (3 Â 6 ml). Recrystallization of the crude reaction product
from dimethyl sulfoxide gave compound (II). The resulting ®ltrate
was evaporated under reduced pressure, and the resulting solid was
crystallized successively from methanol and dimethyl sulfoxide to
give compound (I). Compound (I) was obtained in 46% yield
according to the above procedure as yellow crystals suitable for
single-crystal X-ray diffraction (m.p. 476±477 K). Analysis found: C
59.2, H 4.3, N 16.2%; C17H14N4O4 requires: C 60.3, H 4.2, N 16.6%.
Compound (II) was obtained in 48% yield according to the above
procedure as orange crystals suitable for single-crystal X-ray
diffraction (m.p. 530±531 K), and as the sole product when a similar
reaction was carried out in neat dimethyl sulfoxide (2 ml) at 298 K for
2 h (yield 90%). Analysis found: C 60.2, H 4.7, N 16.4%; C17H14N4O4
requires: C 60.3, H 4.2, N 16.6%.
Compound (I)
Crystal data
3
Ê
C17H14N4O4
Mr = 338.32
V = 1565.90 (18) A
Z = 4
Figure 5
Part of the crystal structure of (II), showing the formation of a
centrosymmetric hydrogen-bonded dimer. For the sake of clarity, H
atoms not involved in the motif shown have been omitted. Atoms
marked with an asterisk (*) are at the symmetry position (1 x, 2 y,
Monoclinic, P21=n
Mo Kꢁ radiation
ꢂ = 0.11 mm
T = 120 (2) K
0.55 Â 0.35 Â 0.19 mm
1
Ê
a = 12.3516 (8) A
Ê
b = 7.5202 (4) A
Ê
c = 17.1564 (13) A
ꢀ = 100.699 (5)ꢁ
1
z).
ꢀ
o512 Portilla et al. C17H14N4O4
Acta Cryst. (2007). C63, o510±o513

organic compounds
Data collection
For (I), the space group P21/n was uniquely assigned from the
systematic absences. For (II), the systematic absences permitted Cc
and C2/c as possible space groups; C2/c was selected and con®rmed
by the subsequent structure analysis. All H atoms were located in
difference maps and then treated as riding atoms. H atoms bonded to
C atoms were allowed to ride in geometrically idealized positions,
Bruker±Nonius KappaCCD
diffractometer
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
Tmin = 0.951, Tmax = 0.980
37526 measured re¯ections
3597 independent re¯ections
2266 re¯ections with I > 2ꢃ(I)
Rint = 0.057
Ê
with CÐH distances of 0.95 (aromatic and pyrazole) or 0.98 A
Re®nement
R[F2 > 2ꢃ(F2)] = 0.056
wR(F2) = 0.178
S = 1.08
227 parameters
H-atom parameters constrained
(methyl), and with Uiso(H) = kUeq(C), where k = 1.5 for the methyl
groups and 1.2 for all other H atoms bonded to C atoms. H atoms
bonded to N atoms were permitted to ride at the positions deduced
Ê
from difference maps, all giving NÐH distances of 0.87 A, with
Uiso(H) = 1.2Ueq(N).
3
Ê
Áꢄmax = 0.33 e A
3
Ê
0.39 e A
3597 re¯ections
Áꢄmin
=
Table 1
Hydrogen-bond geometry (A, ) for (I).
ꢁ
Ê
For both compounds, data collection: COLLECT (Hooft, 1999);
cell re®nement: DIRAX/LSQ (Duisenberg et al., 2000); data reduc-
tion: EVALCCD (Duisenberg et al., 2003); program(s) used to solve
structure: SIR2004 (Burla et al., 2005) and WinGX (Farrugia, 1999);
program(s) used to re®ne structure: OSCAIL (McArdle, 2003) and
SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek,
2003); software used to prepare material for publication: SHELXL97
and PRPKAPPA (Ferguson, 1999).
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
N5ÐH5AÁ Á ÁN2i
0.87
0.87
0.95
2.33
2.18
2.39
3.131 (3)
3.024 (3)
3.304 (3)
154
163
161
N5ÐH5BÁ Á ÁO141ii
C16ÐH16Á Á ÁO121i
Symmetry codes: (i) x ‡ 32; y ‡ 21; z ‡ 21; (ii) x
;
y ‡ 32; z
.
1
2
1
2
Compound (II)
Â
The authors thank `Servicios Tecnicos de Investigacion' of
the Universidad de Jaen and the staff for data collection. JC
Â
Â
Crystal data
3
Ê
Â
Â
thanks the Consejerõa de Innovacion, Ciencia y Empresa
C17H14N4O4
Mr = 338.32
Monoclinic, C2=c
V = 2988.1 (7) A
Z = 8
Â
Â
(Junta de Andalucõa, Spain) and the Universidad de Jaen
for ®nancial support. JP thanks COLCIENCIAS and
UNIVALLE (Universidad del Valle, Colombia) for ®nancial
support that has also supported a short stay at Instituto de
Quõmica Organica de Sõntesis, Universidad Nacional de
Rosario, Argentina. EGM thanks CONICETand Universidad
Nacional de Rosario for ®nancial support.
Mo Kꢁ radiation
1
Ê
a = 31.0506 (4) A
ꢂ = 0.11 mm
T = 120 (2) K
Ê
b = 5.4210 (11) A
Ê
c = 20.7251 (12) A
0.50 Â 0.29 Â 0.28 mm
ꢀ = 121.071 (6)ꢁ
Â
Â
Â
Data collection
Bruker±Nonius KappaCCD
diffractometer
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
Tmin = 0.947, Tmax = 0.967
33526 measured re¯ections
3420 independent re¯ections
2488 re¯ections with I > 2ꢃ(I)
Rint = 0.044
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: SK3149). Services for accessing these data are
described at the back of the journal.
Re®nement
R[F2 > 2ꢃ(F2)] = 0.048
wR(F2) = 0.134
S = 1.11
227 parameters
H-atom parameters constrained
References
3
Ê
Áꢄmax = 0.28 e A
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.
3
Ê
0.36 e A
3420 re¯ections
Áꢄmin
=
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem.
Int. Ed. Engl. 34, 1555±1573.
Burla, M. C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G. L., De
Caro, L., Giacovazzo, C., Polidori, G. & Spagna, R. (2005). J. Appl. Cryst. 38,
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Duisenberg, A. J. M., Hooft, R. W. W., Schreurs, A. M. M. & Kroon, J. (2000).
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J. Appl. Cryst. 36, 220±229.
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837±838.
Table 2
Selected bond lengths (A) for (II).
Ê
C51ÐN5
C51ÐC52
C52ÐC53
C53ÐC54
C54ÐC55
1.364 (2)
1.425 (2)
1.391 (2)
1.378 (3)
1.404 (2)
C55ÐC56
C56ÐC51
C52ÐN52
N52ÐO521
N52ÐO522
1.370 (3)
1.419 (3)
1.448 (2)
1.2522 (19)
1.2262 (19)
Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada.
Hooft, R. W. W. (1999). COLLECT. Nonius BV, Delft, The Netherlands.
McArdle, P. (2003). OSCAIL for Windows. Version 10. Crystallography
Centre, Chemistry Department, NUI Galway, Ireland.
Portilla, J., Mata, E. G., Nogueras, M., Cobo, J., Low, J. N. & Glidewell, C.
(2007). Acta Cryst. C63, o38±o41.
Table 3
Hydrogen-bond geometry (A, ) for (II).
ꢁ
Ê
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
È
Sheldrick, G. M. (1997). SHELXL97. University of Gottingen, Germany.
Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Gottingen,
N5ÐH5Á Á ÁO521
N2ÐH2Á Á ÁO541i
C36ÐH36Á Á ÁO541i
C53ÐH53Á Á ÁO522ii
0.87
0.87
0.95
0.95
1.89
1.96
2.36
2.54
2.600 (2)
2.828 (2)
3.266 (3)
3.487 (2)
137
171
159
173
È
Germany.
Spek, A. L. (2003). J. Appl. Cryst. 36, 7±13.
Tachibana, K. & Kaneko, Y. (1989). Japanese Kokai Tokkyo Koho, Japanese
Patent 01003187A2. Japanese Patent Application 87-159281 (1987).
Symmetry codes: (i) x ‡ 1; y ‡ 2; z ‡ 1; (ii) x ‡ 1; y; z ‡ 12.
ꢀ
Acta Cryst. (2007). C63, o510±o513
Portilla et al. C17H14N4O4 o513