A simple hydrogen-bonded chain in (3Z)-3-{1-[(5-phenyl-1H-pyrazol-3-yl) amino]ethyl-idene}-4,5-dihydro-furan-2(3H)-one, and a hydrogen-bonded ribbon of centrosymmetric rings in the self-assembled adduct (3Z)-3-{1-[(5-methyl-1H- pyrazol-3-yl)amino]ethyl-idene}-4,5-dihydro-furan-2(3H)-one-6-(2-hydroxy-ethyl) -2,5-dimethyl-pyrazolo[1,5-a]pyrimidin-7(4H)-one (1/1)

Article abstract of DOI:10.1107/S0108270109052846

(3Z)-3-{1-[(5-Phenyl-1H-pyrazol-3-yl)amino]ethyl-idene}-4, 5-dihydro-furan-2(3H)-one, C₁₅H₁₅N₃O ₂, (I), and the stoichiometric adduct (3Z)-3-{1-[(5-methyl-1H- pyrazol-3-yl)-amino]ethyl-idene}-4,5-dihydro-furan-2(3H)-one-6-(2-hydroxy-ethyl) -2,5-dimethyl-pyrazolo[1,5-a]pyrimidin-7(4H)-one (1/1), C₁₀H ₁₃N₃O₂·C₁₀H ₁₃N₃O₂, (II), in which the two components have the same composition but different constitutions, are formed in the reactions of 2-acetyl-4-butyrolactone with 5-amino-3-phenyl-1H-pyrazole and 5-amino-3-methyl-1H-pyra-zole, respectively. In each compound, the furan-one component contains an intra-molecular N - H...O hydrogen bond. The mol-ecules of (I) are linked into a chain by a single inter-molecular N - H...O hydrogen bond, while in (II), a combination of one O - H...N hydrogen bond, within the selected asymmetric unit, and two N - H...O hydrogen bonds link the mol-ecular components into a ribbon containing alternating centrosymmetric R₄⁴(20) and R₆ ⁶(22) rings.

Full text of DOI:10.1107/S0108270109052846

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
very versatile route for the synthesis of new fused heterocyclic
compounds with precisely defined regiochemistry (Portilla et
al., 2008), and fused pyrazole derivatives are potentially
valuable for drug and pesticide applications (Elguero,
1984,1996). Here, we report the structures of the two title
compounds, (I) and (II) (Figs. 1 and 2), which result from the
condensation reactions between 2-acetyl-4-butyrolactone and
two 5-amino-1H-pyrazoles carrying different hydrocarbyl
substituents at position 3 (see reaction scheme).
ISSN 0108-2701
A simple hydrogen-bonded chain in
(3Z)-3-{1-[(5-phenyl-1H-pyrazol-3-yl)-
amino]ethylidene}-4,5-dihydrofuran-
2(3H)-one, and a hydrogen-bonded
ribbon of centrosymmetric rings in the
self-assembled adduct (3Z)-3-{1-[(5-
methyl-1H-pyrazol-3-yl)amino]ethyl-
idene}-4,5-dihydrofuran-2(3H)-one–
6-(2-hydroxyethyl)-2,5-dimethyl-
pyrazolo[1,5-a]pyrimidin-7(4H)-one
(1/1)
Jairo Quiroga,a Jaime Portilla,b Justo Coboc and
Christopher Glidewelld*
a
´
Departamento de Quımica, Universidad de Valle, AA 25360 Cali, Colombia,
b
´
Departamento de Quımica, Universidad de los Andes, Cra. 1E No. 18A-10, Edificio
c
´
´
´
H, AA 4976 Bogota, DC, Colombia, Departamento de Quımica Inorganica y
Organica, Universidad de Jaen, 23071 Jaen, Spain, and dSchool of Chemistry,
University of St Andrews, St Andrews, Fife KY16 9ST, Scotland
Correspondence e-mail: cg@st-andrews.ac.uk
´
´
´
Received 3 December 2009
Accepted 8 December 2009
Online 12 December 2009
(3Z)-3-{1-[(5-Phenyl-1H-pyrazol-3-yl)amino]ethylidene}-4,5-
dihydrofuran-2(3H)-one, C15H15N3O2, (I), and the stoichio-
metric adduct (3Z)-3-{1-[(5-methyl-1H-pyrazol-3-yl)amino]-
ethylidene}-4,5-dihydrofuran-2(3H)-one–6-(2-hydroxyethyl)-
2,5-dimethylpyrazolo[1,5-a]pyrimidin-7(4H)-one (1/1), C10-
H13N3O2ꢀC10H13N3O2, (II), in which the two components
have the same composition but different constitutions, are
formed in the reactions of 2-acetyl-4-butyrolactone with
5-amino-3-phenyl-1H-pyrazole and 5-amino-3-methyl-1H-
pyrazole, respectively. In each compound, the furanone
component contains an intramolecular N—Hꢀ ꢀ ꢀO hydrogen
bond. The molecules of (I) are linked into a chain by a single
intermolecular N—Hꢀ ꢀ ꢀO hydrogen bond, while in (II), a
combination of one O—Hꢀ ꢀ ꢀN hydrogen bond, within the
selected asymmetric unit, and two N—Hꢀ ꢀ ꢀO hydrogen bonds
link the molecular components into a ribbon containing
alternating centrosymmetric R44(20) and R66(22) rings.
The reaction between equimolar quantities of the lactone
and 5-amino-3-phenyl-1H-pyrazole provides (3Z)-3-{1-[(5-
phenyl-1H-pyrazol-3-yl)amino]ethylidene}-4,5-dihydrofuran-
2(3H)-one, (I), which apparently results from a simple
condensation involving only the 2-acetyl substituent in the
lactone reagent, to form a product in which the lactone ring
survives intact (see reaction scheme). By contrast, the corre-
sponding reaction between the same lactone reagent and
5-amino-3-methyl-1H-pyrazole proceeds along two different
reaction pathways. One of these pathways is entirely analog-
ous to that which forms compound (I), leading to the product
denoted (A) in the reaction scheme. The second pathway
involves both carbonyl functions in the lactone component,
which itself undergoes ring opening, so that this pathway is
indeed a cyclocondensation reaction giving a fused hetero-
cyclic system in the product denoted (B) in the reaction
Comment
The condensation reactions between substituted amino-
pyrazoles and dicarbonyl compounds provide a potentially
Acta Cryst. (2010). C66, o25–o28
doi:10.1107/S0108270109052846
# 2010 International Union of Crystallography o25

organic compounds
(B) of (II), the C12—C13 and C13—C13A bonds in (II) differ
˚
in length by almost 0.04 A, while the corresponding differ-
ences in (I) and in component (A) of (II) are no more than
half of this value. In addition, the C13A—N17A bond in (II) is
rather longer than the corresponding bonds in the unfused
pyrazole rings of both (I) and (II), indicating stronger bond
fixation in the fused pyrazole ring than in either of the unfused
pyrazole rings.
Figure 1
The molecular structure of compound (I), showing the atom-labelling
scheme and the intramolecular hydrogen bond (dashed line). Displace-
ment ellipsoids are drawn at the 30% probability level and H atoms are
shown as small spheres of arbitrary radii.
The molecules of (I) contain an intramolecular N—Hꢀ ꢀ ꢀO
hydrogen bond (Table 2, Fig. 1) forming an S(6) motif
(Bernstein et al., 1995), and molecules related by the 21 screw
axis along (12, y, 34) are linked into chains by a second N—Hꢀ ꢀ ꢀO
hydrogen bond to form an S(6)C(9)C21(7) chain of rings
running parallel to the [010] direction (Fig. 3). Two chains of
Figure 2
The independent molecular components of compound (II), showing the
atom-labelling scheme and the hydrogen bonds within the asymmetric
unit (dashed line). Displacement ellipsoids are drawn at the 30%
probability level and H atoms are shown as small spheres of arbitrary
radii.
scheme. Product (II), which crystallizes from the reaction
between 5-amino-3-methyl-1H-pyrazole and the lactone, is a
1:1 hydrogen-bonded adduct formed by the primary products
(A) and (B), which are, in fact, isomeric with one another
despite their very different constitutions.
Within the molecule of compound (I), the C2—O2 and
C3—C6 bonds (Table 1) are both long for their types [mean
˚
values (Allen et al., 1987) = 1.201 and 1.340 A, respectively,
˚
upper quartile values = 1.206 and 1.348 A, respectively] and
˚
the C2—C3 bond is short for its type (mean value = 1.464 A,
˚
lower quartile value = 1.453 A), while the N7—C6 bond is
significantly shorter than the N7—C13 bond. These values
provide evidence for electronic polarization in the vinylogous
amide fragment of (I), indicating that the form (Ia) is a
significant contributor to the overall electronic structure. A
similar pattern of distances is found in component (A) of
compound (II) (Table 3), but the deviations from the expected
values are all somewhat smaller in (II), indicative of a lesser
degree of electronic polarization in this component. A similar
pattern is found also in the vinylogous amide fragment in
component (B) of (II), indicating a contribution from the form
(IIa). Consistent with this observation concerning component
Figure 3
Part of the crystal structure of compound (I), showing the formation of a
hydrogen-bonded chain of rings running parallel to [010]. For the sake of
clarity, H atoms bonded to C atoms have been omitted. Dashed lines
indicate hydrogen bonds. Atoms marked with an asterisk (*), a dollar sign
1
2
($) or an ampersand (&) are at the symmetry positions (1 ꢂ x, ꢂ + y,
3
2
ꢂ z), (1 ꢂ x, 12 + y, 32 ꢂ z) and (x, ꢂ1 + y, z), respectively.
ꢁ
o26 Quiroga et al.
C15H15N3O2 and C10H13N3O2ꢀC10H13N3O2
Acta Cryst. (2010). C66, o25–o28

organic compounds
Table 1
Selected bond lengths (A) for (I).
˚
C2—O2
C2—C3
C3—C6
C6—N7
N7—C13
1.232 (3)
1.413 (3)
1.369 (3)
1.338 (3)
1.380 (3)
N11—N12
N12—C13
C13—C14
C14—C15
C15—N11
1.341 (2)
1.324 (3)
1.394 (3)
1.371 (3)
1.340 (2)
Table 2
Hydrogen-bond geometry (A, ) for (I).
ꢃ
˚
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
N7—H7ꢀ ꢀ ꢀO2
0.88
0.88
1.97
1.97
2.709 (2)
2.784 (2)
141
154
N11—H11ꢀ ꢀ ꢀO2i
1
2
3
2
Symmetry code: (i) ꢂx þ 1; y ꢂ ; ꢂz þ .
Figure 4
A stereoview of part of the crystal structure of (II), showing the
formation of a hydrogen-bonded ribbon parallel to [100]. For the sake of
clarity, H atoms bonded to C atoms have been omitted. Dashed lines
indicate hydrogen bonds.
Compound (I)
Crystal data
3
˚
C15H15N3O2
Mr = 269.30
V = 1291.6 (3) A
Z = 4
Monoclinic, P21=c
Mo Kꢂ radiation
ꢃ = 0.10 mmꢂ1
T = 120 K
0.39 ꢄ 0.25 ꢄ 0.14 mm
˚
a = 10.4969 (17) A
this type, related to one another by inversion, pass through
each unit cell, but there are no direction-specific interactions
between adjacent chains. In particular, there are neither
C—Hꢀ ꢀ ꢀꢀ(arene) hydrogen bonds nor aromatic ꢀ–ꢀ stacking
interactions in the structure of (I).
˚
b = 9.8550 (9) A
˚
c = 12.6739 (16) A
ꢁ = 99.883 (9)ꢃ
Data collection
Bruker–Nonius KappaCCD area-
detector diffractometer
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
Tmin = 0.964, Tmax = 0.987
19109 measured reflections
2536 independent reflections
1704 reflections with I > 2ꢄ(I)
Rint = 0.056
Within the selected asymmetric unit of (II) (Fig. 2), the two
components are linked by a fairly short and almost linear
O—Hꢀ ꢀ ꢀN hydrogen bond (Table 4), and there is also an
intramolecular N—Hꢀ ꢀ ꢀO hydrogen bond, analogous to that
in (I). Two further N—Hꢀ ꢀ ꢀO hydrogen bonds then link the
bimolecular aggregates into a ribbon containing two types of
centrosymmetric ring and running parallel to the [100] direc-
Refinement
R[F2 > 2ꢄ(F2)] = 0.048
wR(F2) = 0.128
S = 1.07
182 parameters
H-atom parameteꢂrs3 constrained
1
1 1
tion. Within the ribbon, R44(20) rings centred at (n + , , ),
˚
Áꢅmax = 0.22 e A
Áꢅmin = ꢂ0.26 e A
2
2 2
ꢂ3
where n represents an integer, alternate with R66(22) rings
˚
2536 reflections
1
1
centred at (n, , ), where n again represents an integer
(Fig. 4).
2
2
Compound (II)
Crystal data
Experimental
C10H13N3O2ꢀC10H13N3O2
ꢆ = 99.172 (15)ꢃ
For the synthesis of compound (I), a mixture of 2-acetyl-4-butyro-
lactone (1 mmol), 5-amino-3-phenyl-1H-pyrazole (1 mmol) and
4-toluenesulfonic acid (0.01 mmol) in ethanol (15 ml) was heated
under reflux with magnetic stirring for 18 h. The mixture was cooled
to ambient temperature and the solvent was removed under reduced
pressure. The resulting solid product was recrystallized from
dimethylformamide to yield (I) as colourless crystals (yield 63%, m.p.
595–596 K). MS (70 eV) m/z (%): 269 (5, M+), 251 (35), 104 (25),
18 (100).
3
˚
V = 982.7 (3) A
Z = 2
Mr = 414.46
Triclinic, P1
a = 8.0402 (11) A
˚
Mo Kꢂ radiation
ꢃ = 0.10 mmꢂ1
T = 120 K
0.38 ꢄ 0.23 ꢄ 0.16 mm
˚
b = 8.2025 (17) A
˚
c = 15.348 (3) A
ꢂ = 91.999 (14)ꢃ
ꢁ = 99.785 (12)ꢃ
Data collection
Bruker–Nonius KappaCCD area-
detector diffractometer
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
Tmin = 0.963, Tmax = 0.984
21688 measured reflections
3857 independent reflections
2739 reflections with I > 2ꢄ(I)
Rint = 0.044
For the synthesis of compound (II), a mixture of 2-acetyl-4-
butyrolactone (1 mmol), 5-amino-3-methyl-1H-pyrazole (1 mmol)
and 4-toluenesulfonic acid (0.01 mmol) in ethanol (15 ml) was heated
under reflux with magnetic stirring for 23 h. The reaction mixture was
cooled to ambient temperature and the solvent was removed under
reduced pressure. The resulting solid product was recrystallized from
dimethylformamide to yield (II) as colourless crystals (yield 48%,
m.p. 493–494 K). MS (70 eV) m/z (%): 207 (6, M+), 189 (23), 152 (8),
86 (41), 43 (100).
Refinement
R[F2 > 2ꢄ(F2)] = 0.046
wR(F2) = 0.123
S = 1.07
275 parameters
H-atom parameteꢂrs3 constrained
˚
Áꢅmax = 0.23 e A
ꢂ3
˚
3857 reflections
Áꢅmin = ꢂ0.33 e A
ꢁ
Acta Cryst. (2010). C66, o25–o28
Quiroga et al.
C15H15N3O2 and C10H13N3O2ꢀC10H13N3O2 o27

organic compounds
Table 3
Selected bond lengths (A) for (II).
PLATON (Spek, 2009); software used to prepare material for
publication: SHELXL97 and PLATON.
˚
N11—C12
C12—C13
C13—C13A
C13A—N14
N14—C15
C15—C16
1.325 (2)
1.399 (3)
1.361 (3)
1.351 (2)
1.351 (2)
1.362 (3)
1.422 (3)
1.389 (2)
1.364 (2)
1.365 (2)
1.229 (2)
C22—O22
C22—C23
C23—C26
C26—N27
N27—C33
N31—N32
N32—C33
C33—C34
C34—C35
C35—N31
1.221 (2)
1.429 (3)
1.356 (3)
1.357 (2)
1.386 (2)
1.351 (2)
1.329 (3)
1.389 (3)
1.374 (3)
1.331 (3)
JQ and JP thank COLCIENCIAS, Universidad del Valle
and Universidad de los Andes for financial support. JC thanks
´
the Consejerıa de Innovacion, Ciencia y Empresa (Junta de
Andalucıa, Spain), the Universidad de Jaen (project reference
´
´
´
C16—C17
´
UJA_07_16_33), and Ministerio de Ciencia e Innovacion
C17—N17A
N17A—N11
C13A—N17A
C17—O17
(project reference SAF2008-04685-C02-02) for financial
support.
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: FA3210). Services for accessing these data are
described at the back of the journal.
Table 4
Hydrogen-bond geometry (A, ) for (II).
ꢃ
˚
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
References
O16—H16ꢀ ꢀ ꢀN32
N27—H27ꢀ ꢀ ꢀO22
N14—H14ꢀ ꢀ ꢀO16i
N31—H31ꢀ ꢀ ꢀO17ii
0.86
0.88
0.88
0.88
1.93
1.99
1.86
1.93
2.784 (2)
2.712 (2)
2.736 (2)
2.740 (2)
175
139
172
153
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.
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,
381–388.
Symmetry codes: (i) x þ 1; y; z; (ii) ꢂx þ 1; ꢂy þ 1; ꢂz þ 1.
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.
Elguero, J. (1984). Pyrazoles and their Benzo Derivatives, edited by A. R.
Katritzky & C. W. Rees, Comprehensive Heterocyclic Chemistry, Vol. 5, pp.
167–303. Oxford: Pergamon.
Elguero, J. (1996). Pyrazoles, edited by A. R. Katritzky, C. W. Rees & E. F.
Scriven, Comprehensive Heterocyclic Chemistry, Vol. 2, pp. 1–75. Oxford:
Pergamon.
Nonius (1999). COLLECT. Nonius BV, Delft, The Netherlands.
Portilla, J., Quiroga, J., Nogueras, M., de la Torre, J. M., Cobo, J., Low, J. N. &
Glidewell, C. (2008). Acta Cryst. B64, 72–83.
¨
Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Gottingen,
Germany.
All H atoms were located in difference maps. H atoms bonded to C
or N atoms were then treated as riding in geometrically idealized
positions, with C—H = 0.95 (aromatic or pyrazole), 0.98 (CH3) or
˚
˚
0.99 A (CH2) and N—H = 0.88 A, and with Uiso(H) = kUeq(carrier),
where k = 1.5 for the methyl groups, which were permitted to rotate
but not to tilt, and 1.2 for all other H atoms bonded to C or N atoms.
The H atom bonded to an O atom in compound (II) was permitted to
ride at the position deduced from the difference maps, with Uiso(H) =
˚
1.5Ueq(O), giving an O—H distance of 0.86 A.
For both compounds, data collection: COLLECT (Nonius, 1999);
cell refinement: 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); program(s) used to refine
structure: SHELXL97 (Sheldrick, 2008); molecular graphics:
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Spek, A. L. (2009). Acta Cryst. D65, 148–155.
ꢁ
o28 Quiroga et al.
C15H15N3O2 and C10H13N3O2ꢀC10H13N3O2
Acta Cryst. (2010). C66, o25–o28