Conversion of substituted 5-aryloxypyrazole-carbaldehydes into reduced 3,4'-bipyrazoles: Synthesis and characterization, and the structures of four precursors and two products, and their supramolecular assembly in zero, one and two dimensions

Article abstract of DOI:10.1107/S2053229619006752

The reaction of 5-chloro-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde with phenols under basic conditions yields the corresponding 5-aryloxy derivatives; the subsequent reaction of these carbaldehydes with substituted acetophenones yields the correspondin

Full text of DOI:10.1107/S2053229619006752

research papers
Conversion of substituted 5-aryloxypyrazole-
carbaldehydes into reduced 3,40-bipyrazoles:
synthesis and characterization, and the structures
of four precursors and two products, and their
supramolecular assembly in zero, one and two
dimensions
ISSN 2053-2296
Received 1 May 2019
Accepted 11 May 2019
Haruvegowda Kiran Kumar,a Hemmige S. Yathirajan,a Nagaraj Manju,b Balakrishna
Kalluraya,b Ravindranath S. Rathorec and Christopher Glidewelld*
Edited by A. R. Kennedy, University of Strath-
clyde, Scotland
aDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysuru 570 006, India, bDepartment of
Studies in Chemistry, Mangalore University, Mangalagangotri, Mangalore 574 199, India, cDepartment of Bioinformatics,
School of Earth, Biological and Environmental Sciences, Central University of South Bihar, Gaya 824 236, India, and
dSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland. *Correspondence e-mail: cg@st-andrews.ac.uk
Keywords: synthesis; heterocyclic compounds;
bipyrazoles; crystal structure; disorder;
hydrogen bonding; supramolecular assembly.
CCDC references: 1915426; 1915425;
The reaction of 5-chloro-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde with
phenols under basic conditions yields the corresponding 5-aryloxy derivatives;
the subsequent reaction of these carbaldehydes with substituted acetophenones
yields the corresponding chalcones, which in turn undergo cyclocondensation
reactions with hydrazine in the presence of acetic acid to form N-acetylated
reduced bipyrazoles. Structures are reported for three 5-aryloxycarbaldehydes
and the 5-piperidino analogue, and for two reduced bipyrazole products. 5-(2-
Chlorophenoxy)-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde, C17H13ClN2O2,
(II), which crystallizes with Z0 = 2 in the space group P1, exhibits orientational
disorder of the carbaldehyde group in each of the two independent molecules.
Each of 3-methyl-5-(4-nitrophenoxy)-1-phenyl-1H-pyrazole-4-carbaldehyde,
C17H13N3O4, (IV), 3-methyl-5-(naphthalen-2-yloxy)-1-phenyl-1H-pyrazole-4-
carbaldehyde, C21H16N2O2, (V), and 3-methyl-1-phenyl-5-(piperidin-1-yl)-1H-
pyrazole-4-carbaldehyde, C16H19N3O, (VI), (3RS)-2-acetyl-5-(4-azidophenyl)-
50-(2-chlorophenoxy)-30-methyl-10-phenyl-3,4-dihydro-10H,2H-[3,40-bipyrazole]
C27H22ClN7O2, (IX) and (3RS)-2-acetyl-5-(4-azidophenyl)-30-methyl-50-(naph-
thalen-2-yloxy)-10-phenyl-3,4-dihydro-10H,2H-[3,40-bipyrazole] C31H25N7O2, (X),
has Z0 = 1, and each is fully ordered. The new compounds have all been fully
1915424; 1915423; 1915422; 1915421
Supporting information: this article has
supporting information at journals.iucr.org/c
1
characterized by analysis, namely IR spectroscopy, H and 13C NMR spectro-
scopy, and mass spectrometry. In each of (II), (V) and (IX), the molecules are
linked into ribbons, generated respectively by combinations of C—Hꢀ ꢀ ꢀN, C—
Hꢀ ꢀ ꢀꢀ and C—Clꢀ ꢀ ꢀꢀ interactions in (II), C—Hꢀ ꢀ ꢀO and C—Hꢀ ꢀ ꢀꢀ hydrogen
bonds in (V), and C—Hꢀ ꢀ ꢀN and C—Hꢀ ꢀ ꢀO hydrogen bonds in (IX). The
molecules of compounds (IV) and (IX) are both linked into sheets, by multiple
C—Hꢀ ꢀ ꢀO and C—Hꢀ ꢀ ꢀꢀ hydrogen bonds in (IV), and by two C—Hꢀ ꢀ ꢀꢀ
hydrogen bonds in (IX). A single C—Hꢀ ꢀ ꢀN hydrogen bond links the molecules
of (X) into centrosymmetric dimers. Comparisons are made with the structures
of some related compounds.
1. Introduction
Pyrazole derivatives exhibit a wide variety of biological
activity, including antibacterial and antifungal activity
(Satheesha Rai et al., 2008; Isloor et al., 2009; Vijesh et al.,
2013) and analgesic and anti-inflammatory activity (Girisha et
al., 2010; Isloor et al., 2010; Vijesh et al., 2013). In addition, the
N-phenylpyrazole fragment is present in a number of drugs
(Kramer, 2015; Alam et al., 2016). As part of our programme
# 2019 International Union of Crystallography
768 https://doi.org/10.1107/S2053229619006752
Acta Cryst. (2019). C75, 768–776

research papers
on the synthesis and structural characterization of pyrazole
derivatives with potential biological activity, we report here
the synthesis and structures of several 5-substituted 1-phenyl-
pyrazole-4-carbaldehydes which have been used as precursors
for the synthesis of reduced 3,40-bipyrazoles, approached via
the intermediate chalcones. Thus, we report the synthesis of
the precursors (II), (IV), (V) and (VI), the chalcone inter-
mediates (VII) and (VIII), and the bipyrazole products (IX)
and (X), together with the structures of compounds (II), (IV)–
(VI), (IX) and (X) (Scheme 1 and Figs. 1–6), which we com-
pare with the recently reported structures of the related
precursors (I) (Shahani et al., 2011), (III) (Vinutha et al., 2014;
Glidewell et al., 2019), (XI) (Sunitha et al., 2016) and (XII)
(Cuartas, et al., 2017), and with those of a related intermediate
2. Experimental
2.1. Synthesis and crystallization
For the synthesis of the aryloxy derivatives (II), (IV) and
(V), a mixture of 5-chloro-3-methyl-1-phenyl-1H-pyrazole-4-
carbaldehyde (1.0 g, 4.5 mmol), the appropriate phenol
(6.8 mmol) and solid potassium hydroxide (0.38 g, 6.8 mmol)
in dimethyl sulfoxide (10 ml) was heated at 333 K for 6 h. The
mixtures were then cooled to ambient temperature and
poured onto crushed ice, after which the resulting solids were
collected by filtration, washed with water and dried in air.
Crystals suitable for single-crystal X-ray diffraction were
obtained by slow evaporation, at ambient temperature and in
the presence of air, of solutions in ethanol. Compound (II):
yield 79%, m.p. 364–366 K. Compound (IV): yield 68%, m.p.
378–379 K. Compound (V): yield 80%, m.p. 408–410 K.
For the synthesis of compound (VI), potassium carbonate
(0.94 g, 6.8 mmol) was added to a well-stirred solution of
piperidine (0.58 g, 6.8 mmol) in ethanol (25 ml) and stirring
was continued for 30 min at ambient temperature. To this
suspension, 5-chloro-3-methyl-1-phenyl-1H-pyrazole-4-carbal-
dehyde (1.0 g, 4.5 mmol) was added and the mixture was
heated under reflux for 2 h. The mixture was cooled to ambient
temperature and the excess solvent was removed under
reduced pressure. The resulting solid was washed with cold
water and recrystallized from ethanol to give crystals suitable
for single-crystal X-ray diffraction (yield 68%, m.p. 385–387 K).
For the synthesis of the bipyrazoles (IX) and (X), the
appropriate precursor [(II) for (IX) or (V) for (X)] (6.2 mmol)
was added to a well-stirred solution of 4-azidoacetophenone
(1.0 g, 6.2 mmol) and potassium hydroxide (0.34 g, 6.2 mmol)
in ethanol (20 ml), and stirring was continued at ambient
temperature for 30 min. The resulting solids were collected by
filtration, washed with cold water and recrystallized from
ethanol–dimethylformamide (3:1 v/v) to give the interme-
diates 1-(4-azidophenyl)-3-[5-(2-chlorophenoxy)-3-methyl-1-
phenyl-1H-pyrazol-4-yl]prop-2-en-1-one, (VII), and 1-(4-
azidophenyl)-3-[5-(naphthalen-2-yloxy)-3-methyl-1-phenyl-1H-
pyrazol-4-yl]prop-2-en-1-one, (VIII), respectively. Despite
repeated attempts using a wide variety of solvents, we have
been unable to grow crystals of compounds (VII) and (VIII)
suitable for single-crystal X-ray diffraction. Compound (VII):
yield 77%, m.p. 435–438 K. Compound (VIII): yield 74%, m.p.
489–490 K.
A mixture containing one of these chalcones (10 mmol) and
hydrazine hydrate (15 mmol) in acetic acid (15 ml) was stirred
overnight at 353 K, poured onto crushed ice (50 g) and
allowed to warm to ambient temperature. The resulting solids
were collected by filtration, dried in air and crystallized from
ethanol–dimethylformamide (3:1 v/v) to give the products
(IX) and (X); crystals suitable for single-crystal X-ray
diffraction were selected directly from the prepared samples.
Compound (IX): yield 72%, m.p. 412–414 K. Compound (X):
yield, 68%, m.p. 452–453 K.
chalcone and two reduced bipyridyl products (Cuartas et al.,
2017). The compounds were prepared by nucleophilic substi-
tution of 5-chloro-3-methyl-1-phenyl-1H-pyrazole-4-carbal-
dehyde with an amine or a phenol under basic conditions to
yield the precursor carbaldehydes (I)–(VI); reaction of such a
precursor with an acetyl compound produces chalcone inter-
mediates (VII) and (VIII), cyclocondensation of which with
hydrazine produces the reduced bipyrazole products (IX) and
(X) (Scheme 1).
1
Full characterization data (analysis, IR, H and 13C NMR
and mass spectrometry) are provided in the supporting
information for compounds (II) and (IV)–(X).
Conversion of 5-aryloxypyrazolecarbaldehydes to 3,40-bipyrazoles 769
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Table 1
Experimental details.
Experiments were carried out at 296 K with Mo Kꢁ radiation using a Bruker APEXII CCD diffractometer. Absorption was corrected for by multi-scan methods
(SADABS; Bruker, 2015). H-atom parameters were constrained.
(II)
(IV)
(V)
Crystal data
Chemical formula
Mr
Crystal system, space group
C17H13ClN2O2
312.74
Triclinic, P1
10.3034 (4), 11.4856 (4),
14.4725 (5)
81.013 (2), 69.861 (2), 69.990 (2)
1509.47 (10)
C17H13N3O4
323.30
Monoclinic, P21/c
14.1163 (9), 11.7268 (7), 9.3982 (5)
C21H16N2O2
328.36
Monoclinic, P21/n
7.7302 (6), 17.2550 (16),
13.1989 (11)
90, 106.079 (2), 90
1691.7 (2)
˚
a, b, c (A)
ꢁ, ꢂ, ꢃ (ꢂ)
90, 94.259 (3), 90
1551.47 (16)
3
˚
V (A )
Z
4
0.26
4
0.10
4
0.08
ꢄ (mmꢃ1
Crystal size (mm)
)
0.19 ꢄ 0.16 ꢄ 0.13
0.20 ꢄ 0.15 ꢄ 0.15
0.20 ꢄ 0.16 ꢄ 0.14
Data collection
Tmin, Tmax
0.902, 0.967
35720, 6296, 4051
0.945, 0.985
28186, 3956, 2361
0.954, 0.988
34394, 4311, 2711
No. of measured, independent and
observed [I > 2ꢅ(I)] reflections
Rint
0.042
0.629
0.037
0.672
0.049
0.672
ꢃ1
˚
(sin ꢆ/ꢇ)max (A
)
Refinement
R[F2 > 2ꢅ(F2)], wR(F2), S
No. of reflections
0.042, 0.112, 1.03
6296
0.043, 0.121, 1.01
3956
0.047, 0.130, 1.03
4311
No. of parameters
No. of restraints
Áꢈmax, Áꢈmin (e A
425
2
0.20, ꢃ0.26
219
0
0.19, ꢃ0.15
227
0
0.17, ꢃ0.25
ꢃ3
˚
)
(VI)
(IX)
(X)
Crystal data
Chemical formula
Mr
C16H19N3O
269.34
C27H22ClN7O2
511.97
C31H25N7O2
527.58
Crystal system, space group
˚
a, b, c (A)
Monoclinic, P21/n
8.9432 (7), 16.0546 (14),
10.1155 (8)
90, 97.777 (2), 90
1439.0 (2)
Triclinic, P1
10.8804 (4), 11.3363 (4),
11.5737 (4)
97.294 (2), 90.050 (2), 117.840 (2)
1249.15 (8)
Triclinic, P1
10.4911 (11), 11.2048 (12),
13.5943 (17)
105.323 (3), 93.505 (3), 117.460 (3)
1335.9 (3)
ꢁ, ꢂ, ꢃ (ꢂ)
3
˚
V (A )
Z
4
0.08
2
0.19
2
0.09
ꢄ (mmꢃ1
Crystal size (mm)
)
0.20 ꢄ 0.15 ꢄ 0.10
0.19 ꢄ 0.17 ꢄ 0.14
0.15 ꢄ 0.13 ꢄ 0.12
Data collection
Tmin, Tmax
0.950, 0.992
27358, 3000, 1869
0.930, 0.973
31603, 5197, 3299
0.926, 0.990
16901, 5470, 2883
No. of measured, independent and
observed [I > 2ꢅ(I)] reflections
Rint
0.047
0.629
0.044
0.629
0.038
0.629
ꢃ1
˚
(sin ꢆ/ꢇ)max (A
)
Refinement
R[F2 > 2ꢅ(F2)], wR(F2), S
No. of reflections
0.047, 0.141, 1.05
3000
0.045, 0.126, 1.01
5197
0.055, 0.178, 1.01
5470
No. of parameters
No. of restraints
183
0
336
0
0.26, ꢃ0.26
363
0
0.25, ꢃ0.25
ꢃ3
˚
Áꢈmax, Áꢈmin (e A
)
0.29, ꢃ0.18
Computer programs: APEX2 (Bruker, 2015), SAINT (Bruker, 2015), SHELXT (Sheldrick, 2015a), SHELXL2014 (Sheldrick, 2015b) and PLATON (Spek, 2009).
2.2. Refinement
had been attenuated by the beam stop [reflection 100 in each
of (IV) and (IX), 010 in (II), 001 in (X) and 011 in (V)] were
omitted from the final refinements. It was apparent from an
early stage that in each of the two independent molecules of
compound (II) the formyl group was disordered over two sets
of atomic sites having unequal occupancies. For the minor-
disorder component of each molecule, the bonded distances
and the 1,3 nonbonded distances were restrained to be the
same as the corresponding distances in the major form, subject
Crystal data, data collection and structure refinement
details are summarized in Table 1. All H atoms were located in
difference maps and they were then treated as riding atoms in
geometrically idealized positions, with C—H = 0.93 (aromatic
˚
and formyl), 0.96 (CH3), 0.97 (CH2) or 0.98 A (aliphatic), and
with Uiso(H) = kUeq(C), 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. Small numbers of low-angle reflections which
Conversion of 5-aryloxypyrazolecarbaldehydes to 3,40-bipyrazoles
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Figure 1
The structures of the two independent molecules in compound (II),
showing the atom-labelling scheme and the disorder of the carbaldehyde
groups. The major disorder components are drawn using full lines and the
minor components are drawn using broken lines. Displacement ellipsoids
are drawn at the 30% probability level.
Figure 2
The molecular structure of compound (IV), showing the atom-labelling
scheme. Displacement ellipsoids are drawn at the 30% probability level.
˚
to s.u. values of 0.01 and 0.02 A, respectively. In addition, the
˚
0.094 (3) A in (X), with ring conformations intermediate
between the envelope and half-chair forms.
anisotropic displacement parameters for corresponding pairs
of partial-occupancy formyl C-atom sites (C141/C341 and
C241/C441) were constrained to be the same; subject to these
conditions, the occupancies of the two sets of atomic sites
refined to 0.682 (6) and 0.318 (6) in molecule 1, and to
0.536 (5) and 0.464 (5) in molecule 2.
The two independent molecules of compound (II) are
involved in entirely different types of hydrogen bonding
(Table 2). Inversion-related pairs of type 1 molecules are
linked by a pair of C—Hꢀ ꢀ ꢀN hydrogen bonds to form a cyclic
centrosymmetric dimer characterized by an R22(14) (Etter,
1990; Etter et al., 1990; Bernstein et al., 1995) motif and
centred at (12, 0, 1). The type 2 molecules form a second type of
centrosymmetric dimer containing inversion-related C—
3. Results and discussion
1
1
Compound (II) crystallizes with Z0 = 2 in the space group P1,
but a search for possible additional symmetry revealed none;
all of the other compounds discussed here crystallize with Z0 =
1. In addition, both molecules in compound (II) exhibit
orientation disorder of the carbaldehyde units, where the two
disorder components are related by a rotation of ca 180ꢂ about
the exocyclic C—C bonds (Fig. 1); in the crystal selected for
data collection, the occupancies of the disorder components
are 0.682 (6) and 0.318 (6) in the type 1 molecule containing
atom N11, and 0.536 (5) and 0.464 (5) in the type 2 molecule
containing atom N21. By contrast, the molecules in all of the
other compounds considered here are fully ordered.
Hꢀ ꢀ ꢀꢀ(arene) hydrogen bonds and centred at (12, , ). These
2
2
two hydrogen-bonded dimers are linked by a C—Clꢀ ꢀ ꢀꢀ(pyr-
None of the compounds exhibits any internal symmetry, so
that all of them are conformationally chiral, but the space
groups (Table 1) confirm that all have crystallized as racemic
mixtures. The reference molecules were selected such that all
have the same sign for the torsion angle Nx2—Nx1—Cx11—
Cx12, where x is 1 or 2 for compound (II), and nul otherwise.
In addition, compounds (IX) and (X) both contain a stereo-
genic centre at atom C43 (Figs. 5 and 6), and in the selected
reference molecules, this atom has the S configuration. In each
of the products (IX) and (X), the reduced pyrazole ring is very
slightly puckered out of planarity, with ring-puckering ampli-
Figure 3
The molecular structure of compound (V), showing the atom-labelling
scheme. Displacement ellipsoids are drawn at the 30% probability level.
˚
tudes (Cremer & Pople, 1975) of 0.120 (3) A in (IX) and
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Table 2
Hydrogen-bond parameters (A, ).
ꢂ
˚
Cg1 represents the centroid of the C211–C216 ring, Cg2 the centroid of the
C11–C16 ring and Cg3 the centroid of the N1/N2/C3–C5 ring.
Compound D—Hꢀ ꢀ ꢀA
D—H Hꢀ ꢀ ꢀA Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
(II)
C156—H156ꢀ ꢀ ꢀN12i 0.93
2.59
2.80
2.59
2.64
2.57
2.53
2.50
2.84
2.50
2.96
2.78
2.97
2.96
2.58
2.59
2.60
3.433 (3)
152
140
171
152
139
174
139
135
160
C255—H255ꢀ ꢀ ꢀCg1ii 0.93
3.635 (3)
3.509 (3)
3.483 (3)
3.330 (3)
3.456 (2)
3.259 (3)
3.564 (2)
3.386 (2)
(III)
(IV)
C52—H52ꢀ ꢀ ꢀO41iii
0.93
0.93
C56—H56ꢀ ꢀ ꢀCg2ii
C14—H14ꢀ ꢀ ꢀO412iv 0.93
C52—H52ꢀ ꢀ ꢀO41v
0.93
C55—H55ꢀ ꢀ ꢀO411vi 0.93
C53—H53ꢀ ꢀ ꢀCg2vii
0.93
(V)
C51—H51ꢀ ꢀ ꢀO41viii 0.93
C12—H12ꢀ ꢀ ꢀCg3ii
C53—H53ꢀ ꢀ ꢀCg2ii
C15—H15ꢀ ꢀ ꢀCg3ix
0.93
0.93
0.93
3.4804 (17) 117
3.6477 (19) 155
(VI)
(IX)
(X)
3.848 (3)
3.761 (3)
3.378 (5)
3.228 (4)
3.397 (4)
159
140
144
126
139
C52—H52Aꢀ ꢀ ꢀCg2x 0.97
C14—H14ꢀ ꢀ ꢀN451xi 0.93
C55—H55ꢀ ꢀ ꢀO421xii 0.93
C44—H44Aꢀ ꢀ ꢀN2ii
0.97
Symmetry codes: (i) ꢃx + 1, y, ꢃz + 2; (ii) ꢃx + 1, ꢃy + 1, ꢃz + 1; (iii) x, y ꢃ 1, z; (iv)
1
2
1
2
1
2
ꢃx + 1, y ꢃ , ꢃz + 12; (v) x, ꢃy + 21, z ꢃ ; (vi) ꢃx + 1, y ꢃ , ꢃz + 32; (vii) x, ꢃy + 21, z + 12;
(viii) x + 1, y, z; (ix) x + 21, ꢃy + 23, z + 21; (x) ꢃx + 21, y ꢃ , ꢃz + 32; (xi) ꢃx + 1, ꢃy + 1, ꢃz;
1
2
Figure 4
The molecular structure of compound (VI), showing the atom-labelling
scheme. Displacement ellipsoids are drawn at the 30% probability level.
(xii) ꢃx + 2, ꢃy + 2, ꢃz + 1.
parallel to the [010] direction, and that having atom C55 as the
donor links molecules related by the 21 screw axis along (12, y, 43)
into a C(5) chain, also running parallel to [010]. In combina-
tion, these two motifs give rise to a sheet of R44(34) rings lying
parallel to (100) and spanning the entire domain 0 < x < 1
(Fig. 8). A second sheet of this type, related to the first by
inversion also spans the domain 0 < x < 1, so that these two
sheets are interwoven. The two sheets are linked into a bilayer
structure by a chain-of-rings motif built from C—Hꢀ ꢀ ꢀO and
C—Hꢀ ꢀ ꢀꢀ(arene) hydrogen bonds and running parallel to the
[001] direction (Fig. 9); however, there are no direction-
specific interactions between adjacent bilayers, so that the
supramolecular assembly is strictly two-dimensional.
(pyrazole) interaction, where the Clꢀ ꢀ ꢀcentroid distance of
˚
3.4275 (11) A is somewhat shorter than the typical value of
˚
3.6 A (Imai et al., 2008) found for C—Clꢀ ꢀ ꢀꢀ(arene) inter-
actions. Propagation of these interactions by inversion and
translation then generates a complex chain of rings running
parallel to the [011] direction (Fig. 7).
The supramolecular assembly in compound (IV) takes the
form of a complex sheet built from three independent C—
Hꢀ ꢀ ꢀO hydrogen bonds, together with a C—Hꢀ ꢀ ꢀꢀ(arene)
hydrogen bond (Table 2), but the analysis of the assembly can
be simplified by the identification of simple substructures
(Ferguson et al., 1998a,b; Gregson et al., 2000). The hydrogen
bond having atom C14 as the donor links molecules related by
the 21 screw axis along (21, y, 14) to form a C(14) chain running
The molecules of compound (V) are linked into a ribbon in
the form of a chain of rings by a combination of C—Hꢀ ꢀ ꢀO and
Figure 5
The molecular structure of compound (IX), showing the atom-labelling
scheme. Displacement ellipsoids are drawn at the 30% probability level.
Figure 6
The molecular structure of compound (X), showing the atom-labelling
scheme. Displacement ellipsoids are drawn at the 30% probability level.
Conversion of 5-aryloxypyrazolecarbaldehydes to 3,40-bipyrazoles
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C—Hꢀ ꢀ ꢀꢀ(arene) hydrogen bonds (Table 2). Molecules
related by translation are linked into C(8) chains by the C—
Hꢀ ꢀ ꢀO hydrogen bonds, and inversion-related pairs of such
chains are linked by the C—Hꢀ ꢀ ꢀꢀ(arene) hydrogen bond to
form a chain of rings running parallel to the [100] direction
(Fig. 10).
Two C—Hꢀ ꢀ ꢀꢀ hydrogen bonds, one having the pyrazole
ring as the acceptor and the other having the N-phenyl ring as
the acceptor, link the molecules of compound (VI) into sheets
whose formation is readily analysed in terms of two one-
dimensional (1D) substructures. Molecules related by the
3
4
n-glide plane at y = are linked by the C—Hꢀ ꢀ ꢀꢀ(pyrazole)
hydrogen bond to form a chain running parallel to the [101]
direction, and molecules related by the 21 screw axis along
(14, y, 34) are linked by the C—Hꢀ ꢀ ꢀꢀ(arene) hydrogen bond to
form a second chain, this time running parallel to the [010]
direction. The combination of chains along [010] and [101]
generates a sheet lying parallel to (101) (Fig. 11).
The structures of the reduced bipyrazoles (IX) and (X)
contain no C—Hꢀ ꢀ ꢀꢀ hydrogen bonds. In compound (IX), a
combination of C—Hꢀ ꢀ ꢀN and C—Hꢀ ꢀ ꢀO hydrogen bonds
(Table 2) links the molecules into a chain of rings running
parallel to [111] in which R22(22) rings containing C—Hꢀ ꢀ ꢀO
1
hydrogen bonds and centred at (n, n, n ꢃ ) alternate with
2
R22(32) rings containing C—Hꢀ ꢀ ꢀN hydrogen bonds and
Figure 7
1
1
Part of the crystal structure of compound (II), showing the formation of a
chain running parallel to the [011] direction and built from C—Hꢀ ꢀ ꢀN and
C—Hꢀ ꢀ ꢀꢀ(arene) hydrogen bonds and C—Clꢀ ꢀ ꢀꢀ(pyrazole) interactions.
Hydrogen bonds are drawn as dashed lines and, for the sake of clarity, H
atoms not involved in the motifs shown have been omitted.
centred at (n + , n + , n), where n represents an integer in
each case (Fig. 12). By contrast, the very simple supra-
2
2
Figure 9
Figure 8
Part of the crystal structure of compound (IV), showing the formation of
a chain of rings running parallel to [001] and built from C—Hꢀ ꢀ ꢀO and
C—Hꢀ ꢀ ꢀꢀ(arene) hydrogen bonds. Hydrogen bonds are drawn as dashed
lines and, for the sake of clarity, H atoms not involved in the motifs shown
have been omitted.
Part of the crystal structure of compound (IV), showing the formation of
a sheet lying parallel to (100) and built from C—Hꢀ ꢀ ꢀO hydrogen bonds.
Hydrogen bonds are drawn as dashed lines and, for the sake of clarity, H
atoms not involved in the motifs shown have been omitted.
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molecular assembly in compound (X) is based on a single
hydrogen bond of C—Hꢀ ꢀ ꢀN type which links inversion-
related pairs of molecules into centrosymmetric R22(12) dimers
(Fig. 13).
Overall, therefore, the supramolecular assembly is finite, or
zero-dimensional (0D), in compound (X), 1D in each of
compounds (II), (V) and (IX), and two-dimensional (2D) in
compounds (IV) and (VI).
It is worthwhile briefly comparing the supramolecular
assembly in the compounds reported here with that in the
structures of some related compounds. In the starting material
5-chloro-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde, in-
version-related pairs of molecules are linked by paired C—
Hꢀ ꢀ ꢀO hydrogen bonds to form R22(16) dimers, which are
linked into sheets by a C—Hꢀ ꢀ ꢀꢀ(arene) hydrogen bond
(Trilleras et al., 2005). 3-Methyl-5-phenoxy-1-phenyl-1H-
pyrazole-4-carbaldehyde, (I) (see Scheme 1), can be regarded
as the unsubstituted parent compound for the substituted
compounds (II)–(V). Both C—Hꢀ ꢀ ꢀN and C—Hꢀ ꢀ ꢀO hydro-
gen bonds are absent from the structure, but inversion-related
pairs of molecules are linked into centrosymmetric dimers by
C—Hꢀ ꢀ ꢀꢀ(arene) hydrogen bonds (Shahani et al., 2011).
The structure of 5-(4-chlorophenoxy)-3-methyl-1-phenyl-
1H-pyrazole-4-carbaldehyde, (III), has been reported recently
(Vinutha et al., 2014), but the structure description given was
both sparse and incomplete. We have now taken the oppor-
tunity to redetermine this structure, using a rather larger data
Figure 10
Part of the crystal structure of compound (V), showing the formation of a
chain of rings running parallel to the [100] direction and built from C—
Hꢀ ꢀ ꢀO and C—Hꢀ ꢀ ꢀꢀ(arene) hydrogen bonds. Hydrogen bonds are
drawn as dashed lines and, for the sake of clarity, H atoms not involved in
the motifs shown have been omitted.
Figure 11
Figure 12
Part of the crystal structure of compound (VI), showing the formation of
a sheet lying parallel to (101) and built from C—Hꢀ ꢀ ꢀꢀ(pyrazole) and C—
Hꢀ ꢀ ꢀꢀ(arene) hydrogen bonds. Hydrogen bonds are drawn as dashed
lines and, for the sake of clarity, H atoms not involved in the motifs shown
have been omitted.
Part of the crystal structure of compound (IX), showing the formation of
a chain of rings running parallel to the [111] direction and built from C—
Hꢀ ꢀ ꢀO and C—Hꢀ ꢀ ꢀN hydrogen bonds. Hydrogen bonds are drawn as
dashed lines and, for the sake of clarity, H atoms not involved in the
motifs shown have been omitted.
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Figure 15
Figure 13
Part of the crystal structure of compound (III), showing the formation of
a chain parallel to the [100] direction and built from C—Clꢀ ꢀ ꢀꢀ(pyrazole)
interactions. The Clꢀ ꢀ ꢀ(ring centroid) contacts are drawn as tapered lines
and, for the sake of clarity, H atoms have all been omitted.
Part of the crystal structure of compound (X), showing the formation of a
cyclic dimer. Hydrogen bonds are drawn as dashed lines and, for the sake
of clarity, H atoms not involved in the motifs shown have been omitted.
Atoms marked with an asterisk (*) are at the symmetry position (ꢃx + 1,
ꢃy + 1, ꢃz + 1).
C—Hꢀ ꢀ ꢀꢀ(arene) and C—Hꢀ ꢀ ꢀO types and centred at (12, n, 21),
where n represents an integer in each case (Fig. 14). In addi-
tion, molecules related by translation along [100] are linked
into chains (Fig. 15) by a C—Clꢀ ꢀ ꢀꢀ(pyrazole) interaction,
set and it is this determination to which we now refer
(Glidewell et al., 2019). A combination of C—Hꢀ ꢀ ꢀO and C—
Hꢀ ꢀ ꢀꢀ(arene) hydrogen bonds links the molecules of (III) into
a chain of rings running parallel to the [010] direction, in which
centrosymmetric dimers built from C—Hꢀ ꢀ ꢀꢀ(arene) hydro-
i
˚
with geometric parameters Clꢀ ꢀ ꢀCg = 3.5143 (11) A and C—
Clꢀ ꢀ ꢀCgi = 112.54 (8)ꢂ [Cg represents the centroid of the
pyrazole ring; symmetry code: (i) x ꢃ 1, y, z]. The combination
of the chains along [100] and [010] generates a sheet lying
parallel to (001).
1
1
gen bonds and centred at (21, n + , ) alternate with centro-
2
2
symmetric rings containing four hydrogen bonds, two each of
The molecules of compound (XI) are linked by a single C—
Hꢀ ꢀ ꢀO hydrogen bond to form chains (Sunitha et al., 2016),
and those of compound (XII) are linked into a chain of rings
by a combination of C—Hꢀ ꢀ ꢀN and C—Hꢀ ꢀ ꢀꢀ(arene)
hydrogen bonds (Cuartas et al., 2017). Two reduced 3,40-bi-
pyrazoles derived from compound (XII) are linked, respec-
tively, into a chain of rings and a sheet (Cuartas et al., 2017).
In summary, C—Hꢀ ꢀ ꢀN hydrogen bonds are present in the
structures of compounds (I), (II), (IX), (X) and (XII), C—
Hꢀ ꢀ ꢀO hydrogen bonds are present in (III) (V), (IX) and (XI),
C—Hꢀ ꢀ ꢀꢀ hydrogen bonds are present in (I)–(VI) and (XII),
but C—Clꢀ ꢀ ꢀꢀ interactions are present only in (II). Thus, quite
modest changes in molecular constitution can give rise to
significant changes in the spectrum of direction-specific
intermolecular interactions and hence in the patterns of
supramolecular assembly.
Figure 14
Acknowledgements
Part of the crystal structure of compound (III), showing the formation of
a chain of rings running parallel to the [010] direction and built from C—
Hꢀ ꢀ ꢀO and C—Hꢀ ꢀ ꢀꢀ(arene) hydrogen bonds. Hydrogen bonds are
drawn as dashed lines and, for the sake of clarity, H atoms not involved in
the motifs shown have been omitted.
HKK is grateful to the University of Mysore for research
facilities. RSR thanks SAIF, IIT, Madras, for provision of the
X-ray facility. HKK is grateful to the UGC–BSR for a stipend.
Conversion of 5-aryloxypyrazolecarbaldehydes to 3,40-bipyrazoles 775
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Gregson, R. M., Glidewell, C., Ferguson, G. & Lough, A. J. (2000).
Acta Cryst. B56, 39–57.
Imai, Y. N., Inoue, Y., Nakanishi, I. & Kitaura, K. (2008). Protein Sci.
17, 1129–1137.
HSY is grateful to the UGC, New Delhi, for the award of a
BSR Faculty Fellowship for three years.
Isloor, A. M., Kalluraya, B. & Shetty, P. (2009). Eur. J. Med. Chem. 44,
3784–3787.
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Conversion of 5-aryloxypyrazolecarbaldehydes to 3,40-bipyrazoles
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supporting information
Acta Cryst. (2019). C75, 768-776 [https://doi.org/10.1107/S2053229619006752]
Conversion of substituted 5-aryloxypyrazolecarbaldehydes into reduced 3,4′-bi-
pyrazoles: synthesis and characterization, and the structures of four precursors
and two products, and their supramolecular assembly in zero, one and two
dimensions
Haruvegowda Kiran Kumar, Hemmige S. Yathirajan, Nagaraj Manju, Balakrishna Kalluraya,
Ravindranath S. Rathore and Christopher Glidewell
Computing details
For all structures, data collection: APEX2 (Bruker, 2015); cell refinement: SAINT (Bruker, 2015); data reduction: SAINT
(Bruker, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure:
SHELXL2014 (Sheldrick, 2015b); molecular graphics: PLATON (Spek, 2009); software used to prepare material for
publication: SHELXL2014 (Sheldrick, 2015b) and PLATON (Spek, 2009).
5-(2-Chlorophenoxy)-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde (II)
Crystal data
C17H13ClN2O2
Z = 4
Mr = 312.74
Triclinic, P1
F(000) = 648
Dx = 1.376 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 7620 reflections
θ = 1.5–28.5°
a = 10.3034 (4) Å
b = 11.4856 (4) Å
c = 14.4725 (5) Å
α = 81.013 (2)°
β = 69.861 (2)°
γ = 69.990 (2)°
V = 1509.47 (10) Å3
µ = 0.26 mm−1
T = 296 K
Block, colourless
0.19 × 0.16 × 0.13 mm
Data collection
Bruker APEXII CCD
diffractometer
35720 measured reflections
6296 independent reflections
4051 reflections with I > 2σ(I)
Rint = 0.042
Radiation source: fine focus sealed tube
Graphite monochromator
Detector resolution: 0.3333 pixels mm-1
φ and ω scans
Absorption correction: multi-scan
(SADABS; Bruker, 2015)
θ
max = 26.6°, θmin = 1.5°
h = −12→12
k = −14→14
l = −18→18
T
min = 0.902, Tmax = 0.967
Acta Cryst. (2019). C75, 768-776
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Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.042
wR(F2) = 0.112
S = 1.03
6296 reflections
425 parameters
2 restraints
Hydrogen site location: inferred from
neighbouring sites
H-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0353P)2 + 0.7109P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.20 e Å−3
Δρmin = −0.26 e Å−3
Special details
Experimental. Characterisation data for compounds (II) and (IV) - (X).
Compound (II). . IR (KBr, cm-1) 1717 (C=O), 1566 (C=N). NMR (CDCl3) δ(1H) 2.56 (s, 3H, CH3), 6.92 (dd, 1H, J=0.80
Hz, J= 6.44 Hz, H2 of 2-chlorophenyl), 7.09 (m, 1H, 2-chlorophenyl), 7.17 (m, 1H, 2-chlorophenyl), 7.34 (t, 1H, 2-
chlorophenyl), 7.43 (t, 3H, H3,H4,H5 of N-phenyl), 7.69 (d, 2H, J=6.40 Hz, H2, H6 of N-phenyl), 9.54 (s, 1H, aldehyde);
δ(13C) 14.60 (CH3), 108.77, 117.17, 122.87, 122.87, 123.58, 125.79, 128.12, 128.27, 129.28, 131.25, 136.80, 150.86,
151.88, 152.21, 182.73 (aldehyde). MS (m/z) 313/315 (M+ + 1). Analysis: found C 65.3, H 4.3, N 8.9%; C17H13ClN2O2
requires C 65.3, H 4.2, N 9.0%.
Compound (IV). IR (KBr, cm-1) 1667 (C=O), 1610 (C=N), 1545 (NO2), 1340 (NO2). NMR (CDCl3) δ(1H) 2.61 (s, 3H,
CH3), 7.12 (d, 2H, J= 4.44 Hz, H2,H6 of N-phenyl), 7.43-7.46 (m, 3H, H3,H4,H5 of N-phenyl), 7.59 (d, 2H, J=7.42 Hz)
and 8.23 (d, 2H, J= 7.42 Hz) (AB, 4-nitrophenyl), 9.78 (s, 1H, aldehyde); δ(13C) 13.96 (CH3), 109.36, 116.17, 122.85,
126.25, 128.62, 129.50, 136.34, 144.16, 149.16, 151.30, 160.70, 182.43 (aldehyde). MS (m/z) 324 (M+ + 1). Analysis:
found C 63.3, H 4.0, N 12.7%; C17H13N3O4 requires C 63.2, H 4.1, N 13.0%.
Compound (V). IR (KBr, cm-1) 1719 (C=O), 1555 (C=N). NMR (CDCl3) δ(1H) 2.31 (s, 3H, CH3), 7.28 (m, 3H, Ar-H),
7.40 (m, 4H, Ar-H), 7.68 (d, 2H, J=6.80 Hz, Ar-H), 7.71 (d, 1H, J=6.40 Hz, Ar-H), 7.83 (d, 1H, J=6.40 Hz, Ar-H), 7.85
(d, 1H, J=7.20 Hz, Ar-H), 9.65 (s, 1H, aldehyde); δ(13C) 14.62 (CH3), 109.09, 111.60, 116.87, 122.77, 125.57, 127.25,
127.32, 127.86, 128.07, 129.29, 130.61, 130.77, 133.90, 136.92, 150.93, 152.39, 154.88, 183.09 (aldehyde). MS (m/z)
329 (M+ + 1). Analysis: found C 76.8, H 5.0, N 8.6%; C21H16N2O2 requires C 76.8, H 4.9, N 8.5%.
Compound (VI). IR (KBr, cm-1) 1722 (C=O), 1534 (C=N). NMR (CDCl3) δ(1H) 2.32 (s, 3H, CH3), 2.98-3.67 (m, 10H,
piperidine), 6.97 (d, 2H, J= 7.87 Hz, H2,H6 of N-phenyl), 7.24 (m, 3H, H3,H4,H5 of N-phenyl), 9.70 (s, 1H, aldehyde);
δ(13C) 12.97 (CH3), 45.65 (CH2), 57.51(CH2), 125.76, 126.8,127.43, 128.69, 129.86, 136.43, 145.39, 148.21, 151.27,
183.43 (aldehyde). MS (m/z) 270 (M+ + 1). Analysis: found C 71.4, H 7.0, N 15.5%; C16H19N3O requires C 71.3, H 7.1, N
15.6%.
Compound (VII). IR (KBr, cm-1) 2359 (azide), 1650 (C=O), 1592 (C=N). NMR (CDCl3) δ(1H) 2.52 (s, 3H, CH3), 6.62 (d,
1H, Ar-H), 6.90 (d, 1H, J= 15.80 Hz, oalkenic H), 6.98 (d, 2H, J=8.64 Hz, H2, H6 of azidophenyl), 7.03 (m, 2H, Ar-H),
7.28 (d, 2H, J= 8.64 Hz, H3,H5 of azidophenyl), 7.36 (m, 2H, Ar-H), 7.55 (d, 1H, J=15.80 Hz, alkenic H), 7.60 (m, 4H,
Ar-H). MS (m/z) 456 (M+ + 1) for C25H1835ClN5O2. Analysis: found C 66.0, H 4.0, N 15.5%; C25H18ClN5O2 requires C
65.9, H 4.0, N 15.4%.
Compound (VIII). IR (KBr, cm-1) 2354 (azide), 1676 (C=O), 1565 (C=N). NMR (CDCl3) δ(1H) : 2.56 (s, 3H, CH3), 6.67
(m, 2H, Ar-H), 6.96 (d, 1H, J= 15.80 Hz, alkenic H), 7.06 (d, 2H, J=8.58 Hz, H2,H6 of azidophenyl), 7.10 (m, 3H, Ar-H),
7.26 (d, 2H, J= 8.64 Hz, H3,H5 of azidophenyl), 7.43 (m, 2H, Ar-H), 7.58 (d, 1H, J=15.80 Hz, alkenic H), 7.60 (m, 5H,
Ar-H). MS (m/z) 472 (M+ + 1). Analysis: found C 74.0, H 4.4, N 14.7%; C29H21N5O2 requires C 73.9, H 6.5, N 14.9%.
Compound (IX). IR (KBr, cm-1) 2359 (azide), 1650 (C=O), 1592 (C=N). NMR (CDCl3) δ(1H) 2.02 (s, 3H, acyl CH3),
2.42 (s,3H, CH3), 3.26 (dd, J=5.1 Hz & 17.4 Hz, 1H, -CH2), 3.57 (dd, J=12.3 Hz and 17.4 Hz, 1H, -CH2), 5.37 (dd, J=5.1
Acta Cryst. (2019). C75, 768-776
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Hz and 12.3 Hz, 1H, -CH), 6.62 (d, J=8.1 Hz, 1H, Ar-H), 7.18 (d, J= 7.8 Hz, 2H, H2 and H6 of azidophenyl), 7.32 (m,
4H, Ar-H), 7.38 (m, 4H, Ar-H), 7.44(d, J= 7.8 Hz, 2H, H3 and H5 of azidophenyl); δ(13C) 12.93 (CH3, acetyl), 22.46
(CH3, pyrazole), 52.18 (CH2, pyrazoline), 54.91 (-CH, pyrazoline), 109.09, 111.60, 116.87, 122.77, 125.57, 127.25,
127.32, 127.86, 128.07, 129.29, 130.61, 130.77, 131.28 133.90, 136.92, 138.54, 150.93, 152.39, 155.87, 158.92, 171.24
(C=O). MS (m/z) 512/514 (M+ + 1). Analysis: found C 63.4, H 4.3, N 19.2%; C27H22ClN7O2 requires C 63.3, H 4.4, N
19.2%.
Compound (X). IR (KBr, cm-1) 2365 (azide), 1698 (C=O),1587 (C=N). NMR (CDCl3) δ(1H) 2.12 (s, 3H, acyl CH3), 2.42
(s, 3H, CH3), 3.27 (dd, J=5.2 Hz and 17.1 Hz, 1H, -CH2), 3.53 (dd, J=12.4 Hz and 17.1 Hz, 1H, -CH2), 5.33 (dd, J=5.0 Hz
and 12.4 Hz, 1H, -CH), 6.62 (m, 3H, Ar-H), 7.13 (d, J=7.7 Hz, 2H, H2,H6 of azidophenyl), 7.28 (m, 4H, Ar-H), 7.39 (m,
5H, Ar-H), 7.40 (d, J=7.6 Hz, 2H, H3,H5 of azidophenyl); δ(13C) 12.28 (CH3 acetyl), 22.40 (CH3, pyrazole), 51.12 (CH2,
pyrazoline), 53.78 (-CH, pyrazoline), 108.13, 111.60, 117.85, 121.77, 127.56, 127.88, 128.42, 128.68, 128.97, 129.39,
130.68, 131.54, 132.23, 132.69, 133.77, 134.28 135.87, 136.72, 137.54, 149.93, 152.22, 155.86, 157.92, 172.30 (C=O).
MS (m/z) 528 (M+ + 1). Analysis: found C 70.4, H 4.6, N 18.8%; C31H25N7O2 requires C 70.6, H 4.8, N 18.6%.
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance
matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles;
correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate
(isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
y
z
Uiso*/Ueq
Occ. (<1)
N11
N12
C13
C14
0.46537 (19)
0.4865 (2)
0.6283 (3)
0.7027 (2)
0.5939 (2)
0.3208 (2)
0.2864 (3)
0.3575
0.1451 (3)
0.1222
0.0389 (3)
−0.0562
0.0738 (3)
0.0016
0.2138 (3)
0.2360
0.6907 (3)
0.6134
0.7447
0.20203 (16)
0.14789 (18)
0.1122 (2)
0.1431 (2)
0.1991 (2)
0.2481 (2)
0.3315 (3)
0.3598
0.3729 (4)
0.4283
0.3349 (3)
0.3641
0.2535 (3)
0.2271
0.2094 (2)
0.1534
0.0485 (3)
0.0426
0.0952
0.97485 (11)
1.06314 (12)
1.04671 (15)
0.94887 (15)
0.90689 (14)
0.96916 (14)
0.8960 (2)
0.8483
0.8937 (2)
0.8432
0.9633 (2)
0.9612
1.0363 (2)
1.0847
1.03989 (17)
1.0903
1.12701 (17)
1.1862
1.1386
0.0428 (4)
0.0481 (5)
0.0471 (5)
0.0478 (5)
0.0436 (5)
0.0427 (5)
0.0814 (9)
0.098*
0.1052 (13)
0.126*
0.0826 (9)
0.099*
0.0741 (8)
0.089*
0.0596 (7)
0.072*
0.0652 (7)
0.098*
0.098*
C15
C111
C112
H112
C113
H113
C114
H114
C115
H115
C116
H116
C131
H13A
H13B
H13C
O151
C151
C152
Cl12
0.7541
−0.0332
1.1079
0.098*
0.60317 (16)
0.6655 (2)
0.7316 (2)
0.74176 (7)
0.24826 (13)
0.1640 (2)
0.2059 (2)
0.35534 (6)
0.81410 (10)
0.73937 (14)
0.64638 (15)
0.62745 (5)
0.0502 (4)
0.0392 (5)
0.0437 (5)
0.0646 (2)
Acta Cryst. (2019). C75, 768-776
sup-3

supporting information
C153
H153
C154
H154
C155
H155
C156
H156
C141
H141
O141
C341
H341
O341
N21
0.7915 (3)
0.8371
0.7838 (3)
0.8236
0.7176 (3)
0.7133
0.6578 (2)
0.6123
0.8530 (8)
0.9112
0.9129 (3)
0.865 (2)
0.8920
0.9538 (8)
0.35991 (17)
0.25244 (19)
0.3205 (2)
0.4720 (2)
0.4906 (2)
0.3173 (2)
0.4180 (3)
0.5163
0.1277 (3)
0.1554
0.0093 (3)
−0.0431
−0.0324 (2)
−0.1132
0.0449 (2)
0.0169
0.1221 (15)
0.0811
0.1571 (3)
0.133 (4)
0.1666
0.0736 (8)
0.30621 (16)
0.36825 (17)
0.4062 (2)
0.3700 (2)
0.30728 (19)
0.25752 (19)
0.1774 (2)
0.1524
0.56909 (17)
0.5063
0.5845 (2)
0.5322
0.6772 (2)
0.6875
0.75491 (17)
0.8176
0.9098 (7)
0.9492
0.8223 (2)
0.886 (2)
0.8217
0.9322 (6)
0.36519 (12)
0.32225 (13)
0.23383 (16)
0.21647 (16)
0.30224 (16)
0.46428 (15)
0.50657 (19)
0.4705
0.0627 (7)
0.075*
0.0704 (8)
0.085*
0.0604 (7)
0.072*
0.0486 (5)
0.058*
0.056 (2)
0.067*
0.0759 (12)
0.056 (2)
0.067*
0.108 (3)
0.0399 (4)
0.0464 (4)
0.0466 (5)
0.0470 (5)
0.0412 (5)
0.0414 (5)
0.0653 (7)
0.078*
0.682 (6)
0.682 (6)
0.682 (6)
0.318 (6)
0.318 (6)
0.318 (6)
N22
C23
C24
C25
C211
C212
H212
C213
H213
C214
H214
C215
H215
C216
H216
C231
H23A
H23B
H23C
O251
C251
C252
Cl22
C253
H253
C254
H254
C255
H255
C256
H256
C241
H241
0.3710 (3)
0.4389
0.2275 (3)
0.1974
0.1287 (3)
0.0303
0.1720 (2)
0.1034
0.1348 (3)
0.0821
0.1683 (3)
0.1383
0.2464 (3)
0.2693
0.2920 (2)
0.3459
0.6031 (2)
0.6320
0.65666 (19)
0.7214
0.61408 (18)
0.6502
0.51849 (17)
0.4906
0.0796 (9)
0.096*
0.0686 (7)
0.082*
0.0627 (7)
0.075*
0.0525 (6)
0.063*
0.2365 (3)
0.2393
0.1374
0.4796 (3)
0.5633
0.4795
0.16684 (19)
0.1593
0.1944
0.0674 (7)
0.101*
0.101*
0.2787
0.4432
0.1037
0.101*
0.61405 (15)
0.6978 (2)
0.8440 (2)
0.91523 (7)
0.9323 (2)
1.0313
0.8744 (3)
0.9342
0.7287 (3)
0.6899
0.24538 (14)
0.3141 (2)
0.2532 (2)
0.10054 (6)
0.3149 (2)
0.2744
0.4354 (2)
0.4764
0.4961 (2)
0.5782
0.32537 (12)
0.33282 (15)
0.31538 (14)
0.28375 (5)
0.32515 (16)
0.3131
0.35251 (18)
0.3593
0.36995 (19)
0.3882
0.0525 (4)
0.0417 (5)
0.0414 (5)
0.06481 (19)
0.0532 (6)
0.064*
0.0579 (6)
0.070*
0.0615 (7)
0.074*
0.6397 (3)
0.5408
0.5717 (19)
0.5400
0.4354 (2)
0.4762
0.386 (3)
0.4223
0.36030 (18)
0.3723
0.1239 (9)
0.0703
0.0551 (6)
0.066*
0.056 (2)
0.067*
0.536 (5)
0.536 (5)
Acta Cryst. (2019). C75, 768-776
sup-4

supporting information
O241
C441
H441
O441
0.7078 (4)
0.599 (2)
0.6916
0.3480 (4)
0.392 (3)
0.3673
0.1156 (3)
0.1335 (10)
0.1403
0.0786 (15)
0.056 (2)
0.067*
0.536 (5)
0.464 (5)
0.464 (5)
0.464 (5)
0.5767 (6)
0.4465 (6)
0.0535 (4)
0.113 (2)
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
N11
N12
C13
C14
0.0443 (10)
0.0519 (12)
0.0515 (14)
0.0457 (13)
0.0487 (13)
0.0422 (12)
0.0538 (16)
0.064 (2)
0.0500 (16)
0.0460 (15)
0.0484 (14)
0.0687 (17)
0.0590 (10)
0.0341 (11)
0.0381 (12)
0.0620 (4)
0.0635 (16)
0.0738 (19)
0.0668 (17)
0.0488 (13)
0.048 (2)
0.0524 (11)
0.0614 (12)
0.0541 (14)
0.0535 (14)
0.0452 (13)
0.0479 (13)
0.103 (2)
0.143 (3)
0.113 (3)
0.102 (2)
0.0775 (18)
0.0828 (19)
0.0459 (9)
0.0475 (13)
0.0499 (13)
0.0567 (4)
0.080 (2)
0.0300 (9)
0.0318 (9)
0.0388 (12)
0.0423 (12)
0.0325 (11)
0.0356 (11)
0.0669 (18)
0.078 (2)
0.0722 (19)
0.0664 (17)
0.0460 (13)
0.0498 (14)
0.0311 (7)
0.0320 (10)
0.0367 (11)
0.0602 (4)
0.0361 (13)
0.0599 (17)
0.0746 (18)
0.0459 (12)
0.042 (6)
−0.0158 (9)
−0.0112 (8)
−0.0155 (8)
−0.0174 (10)
−0.0118 (10)
−0.0077 (10)
−0.0129 (9)
−0.0176 (14)
−0.0293 (17)
−0.0251 (15)
−0.0129 (13)
−0.0133 (11)
−0.0307 (13)
−0.0052 (7)
−0.0111 (9)
−0.0112 (9)
−0.0106 (3)
−0.0116 (11)
−0.0254 (14)
−0.0360 (14)
−0.0192 (11)
−0.009 (3)
0.0035 (8)
0.0057 (8)
−0.0015 (10)
−0.0034 (10)
−0.0011 (9)
−0.0005 (9)
0.0357 (16)
0.050 (2)
0.0127 (18)
0.0129 (16)
0.0129 (12)
0.0031 (13)
0.0018 (6)
0.0005 (9)
0.0032 (9)
0.0168 (3)
−0.0040 (12)
−0.0264 (15)
−0.0057 (13)
0.0044 (11)
0.008 (4)
−0.0195 (10)
−0.0170 (11)
−0.0145 (11)
−0.0145 (10)
−0.0110 (10)
−0.0174 (16)
−0.012 (2)
−0.0116 (16)
−0.0250 (15)
−0.0194 (13)
−0.0209 (15)
−0.0088 (7)
−0.0079 (9)
−0.0085 (10)
−0.0174 (3)
−0.0148 (14)
−0.0080 (15)
−0.0167 (13)
−0.0179 (11)
−0.021 (2)
C15
C111
C112
C113
C114
C115
C116
C131
O151
C151
C152
Cl12
C153
C154
C155
C156
C141
O141
C341
O341
N21
0.077 (2)
0.0510 (15)
0.0539 (14)
0.072 (4)
0.098 (2)
0.072 (4)
0.0554 (18)
0.048 (2)
0.059 (5)
0.059 (2)
0.042 (6)
0.128 (7)
−0.0294 (16)
−0.021 (2)
−0.015 (4)
0.0018 (14)
−0.009 (3)
−0.039 (4)
0.0044 (16)
0.008 (4)
0.133 (7)
−0.006 (5)
0.0005 (8)
0.0045 (9)
0.0000 (10)
−0.0010 (10)
−0.0062 (10)
−0.0004 (9)
0.0132 (13)
0.0285 (16)
0.0171 (13)
0.0060 (13)
0.0036 (11)
0.0128 (14)
0.0028 (8)
0.0049 (10)
0.0031 (9)
−0.0094 (3)
0.0334 (9)
0.0387 (10)
0.0479 (13)
0.0467 (13)
0.0333 (11)
0.0394 (12)
0.0447 (14)
0.0627 (18)
0.0727 (19)
0.0492 (15)
0.0411 (13)
0.0672 (17)
0.0354 (8)
0.0347 (11)
0.0334 (11)
0.0488 (4)
0.0457 (10)
0.0550 (12)
0.0491 (13)
0.0522 (14)
0.0424 (12)
0.0421 (12)
0.0747 (18)
0.089 (2)
0.0770 (19)
0.0786 (19)
0.0624 (15)
0.0818 (19)
0.0493 (9)
0.0538 (14)
0.0525 (13)
0.0603 (4)
0.0446 (10)
0.0527 (11)
0.0492 (13)
0.0446 (12)
0.0511 (12)
0.0467 (12)
0.0599 (15)
0.0703 (18)
0.0540 (15)
0.0573 (15)
0.0563 (14)
0.0606 (16)
0.0780 (11)
0.0396 (11)
0.0358 (11)
0.0825 (5)
−0.0131 (8)
−0.0157 (9)
−0.0172 (11)
−0.0192 (11)
−0.0118 (9)
−0.0150 (10)
−0.0051 (13)
−0.0095 (16)
−0.0289 (15)
−0.0269 (14)
−0.0176 (11)
−0.0228 (15)
−0.0147 (7)
−0.0187 (10)
−0.0128 (10)
−0.0051 (3)
−0.0175 (8)
−0.0249 (9)
−0.0216 (11)
−0.0142 (10)
−0.0153 (10)
−0.0168 (10)
−0.0168 (12)
−0.0279 (15)
−0.0204 (14)
−0.0099 (12)
−0.0192 (11)
−0.0361 (14)
−0.0248 (8)
−0.0134 (9)
−0.0105 (9)
−0.0261 (3)
N22
C23
C24
C25
C211
C212
C213
C214
C215
C216
C231
O251
C251
C252
Cl22
Acta Cryst. (2019). C75, 768-776
sup-5

supporting information
C253
C254
C255
C256
C241
O241
C441
O441
0.0371 (12)
0.0547 (15)
0.0649 (17)
0.0394 (13)
0.045 (6)
0.045 (2)
0.045 (6)
0.110 (4)
0.0729 (18)
0.0691 (18)
0.0568 (16)
0.0600 (16)
0.081 (3)
0.109 (3)
0.081 (3)
0.153 (5)
0.0538 (14)
0.0645 (16)
0.0699 (17)
0.0645 (15)
0.053 (3)
0.073 (2)
0.053 (3)
0.066 (3)
−0.0200 (12)
−0.0314 (14)
−0.0198 (13)
−0.0101 (11)
−0.031 (5)
−0.032 (2)
−0.031 (5)
−0.057 (4)
−0.0199 (11)
−0.0263 (13)
−0.0263 (13)
−0.0181 (11)
−0.022 (3)
−0.0038 (18)
−0.022 (3)
−0.020 (3)
0.0049 (12)
0.0019 (13)
−0.0094 (13)
−0.0068 (12)
0.004 (3)
0.003 (2)
0.004 (3)
0.044 (3)
Geometric parameters (Å, º)
N11—C15
1.344 (3)
N21—C25
1.344 (3)
N11—N12
N11—C111
N12—C13
C13—C14
C13—C131
C14—C15
1.385 (2)
1.428 (3)
1.319 (3)
1.414 (3)
1.492 (3)
1.375 (3)
1.400 (8)
1.58 (2)
1.357 (2)
1.368 (3)
1.370 (3)
1.378 (4)
0.9300
1.354 (4)
0.9300
1.357 (4)
0.9300
1.372 (3)
0.9300
0.9300
N21—N22
N21—C211
N22—C23
C23—C24
C23—C231
C24—C25
1.384 (2)
1.430 (3)
1.318 (3)
1.411 (3)
1.491 (3)
1.374 (3)
1.410 (11)
1.508 (13)
1.354 (2)
1.377 (3)
1.380 (3)
1.381 (3)
0.9300
1.360 (4)
0.9300
1.363 (3)
0.9300
1.377 (3)
0.9300
0.9300
C14—C141
C14—C341
C15—O151
C111—C112
C111—C116
C112—C113
C112—H112
C113—C114
C113—H113
C114—C115
C114—H114
C115—C116
C115—H115
C116—H116
C131—H13A
C131—H13B
C131—H13C
O151—C151
C151—C156
C151—C152
C152—C153
C152—Cl12
C153—C154
C153—H153
C154—C155
C154—H154
C155—C156
C155—H155
C156—H156
C141—O141
C24—C241
C24—C441
C25—O251
C211—C216
C211—C212
C212—C213
C212—H212
C213—C214
C213—H213
C214—C215
C214—H214
C215—C216
C215—H215
C216—H216
C231—H23A
C231—H23B
C231—H23C
O251—C251
C251—C252
C251—C256
C252—C253
C252—Cl22
C253—C254
C253—H253
C254—C255
C254—H254
C255—C256
C255—H255
C256—H256
C241—O241
0.9600
0.9600
0.9600
0.9600
0.9600
0.9600
1.394 (2)
1.376 (3)
1.378 (3)
1.378 (3)
1.728 (2)
1.369 (4)
0.9300
1.374 (4)
0.9300
1.376 (3)
0.9300
1.392 (2)
1.376 (3)
1.376 (3)
1.383 (3)
1.721 (2)
1.368 (3)
0.9300
1.372 (3)
0.9300
1.379 (3)
0.9300
0.9300
1.272 (10)
0.9300
1.286 (17)
Acta Cryst. (2019). C75, 768-776
sup-6

supporting information
C141—H141
C341—O341
C341—H341
0.9300
1.271 (13)
0.9300
C241—H241
C441—O441
C441—H441
0.9300
1.283 (17)
0.9300
C15—N11—N12
109.92 (17)
131.34 (17)
118.73 (16)
105.69 (16)
111.49 (19)
120.3 (2)
128.3 (2)
130.6 (4)
104.06 (19)
125.3 (4)
119.0 (8)
136.8 (8)
121.68 (19)
108.84 (18)
129.5 (2)
119.5 (2)
121.6 (2)
118.93 (18)
119.3 (3)
120.4
120.4
121.5 (3)
119.2
119.2
118.7 (3)
120.7
120.7
121.1 (3)
119.4
119.4
119.9 (2)
120.1
C25—N21—N22
109.99 (16)
131.70 (17)
118.27 (16)
105.52 (17)
111.66 (18)
120.1 (2)
128.2 (2)
132.2 (9)
104.14 (18)
123.1 (8)
120.9 (9)
134.9 (9)
120.89 (18)
108.69 (18)
130.25 (19)
119.5 (2)
118.85 (18)
121.68 (19)
119.2 (2)
120.4
120.4
121.4 (2)
119.3
119.3
119.0 (2)
120.5
120.5
121.1 (2)
119.5
119.5
119.8 (2)
120.1
C15—N11—C111
N12—N11—C111
C13—N12—N11
C25—N21—C211
N22—N21—C211
C23—N22—N21
N12—C13—C14
N22—C23—C24
N12—C13—C131
C14—C13—C131
C15—C14—C141
C15—C14—C13
C141—C14—C13
C15—C14—C341
C13—C14—C341
N11—C15—O151
N11—C15—C14
N22—C23—C231
C24—C23—C231
C25—C24—C241
C25—C24—C23
C241—C24—C23
C25—C24—C441
C23—C24—C441
N21—C25—O251
N21—C25—C24
O151—C15—C14
C112—C111—C116
C112—C111—N11
C116—C111—N11
C111—C112—C113
C111—C112—H112
C113—C112—H112
C114—C113—C112
C114—C113—H113
C112—C113—H113
C113—C114—C115
C113—C114—H114
C115—C114—H114
C114—C115—C116
C114—C115—H115
C116—C115—H115
C111—C116—C115
C111—C116—H116
C115—C116—H116
C13—C131—H13A
C13—C131—H13B
H13A—C131—H13B
C13—C131—H13C
H13A—C131—H13C
H13B—C131—H13C
C15—O151—C151
C156—C151—C152
C156—C151—O151
C152—C151—O151
C151—C152—C153
O251—C25—C24
C216—C211—C212
C216—C211—N21
C212—C211—N21
C211—C212—C213
C211—C212—H212
C213—C212—H212
C214—C213—C212
C214—C213—H213
C212—C213—H213
C213—C214—C215
C213—C214—H214
C215—C214—H214
C214—C215—C216
C214—C215—H215
C216—C215—H215
C215—C216—C211
C215—C216—H216
C211—C216—H216
C23—C231—H23A
C23—C231—H23B
H23A—C231—H23B
C23—C231—H23C
H23A—C231—H23C
H23B—C231—H23C
C25—O251—C251
C252—C251—C256
C252—C251—O251
C256—C251—O251
C251—C252—C253
120.1
109.5
109.5
109.5
109.5
109.5
109.5
116.19 (16)
120.2 (2)
122.55 (18)
117.18 (19)
119.7 (2)
120.1
109.5
109.5
109.5
109.5
109.5
109.5
117.88 (16)
120.3 (2)
116.61 (19)
123.02 (19)
119.5 (2)
Acta Cryst. (2019). C75, 768-776
sup-7

supporting information
C151—C152—Cl12
C153—C152—Cl12
C154—C153—C152
C154—C153—H153
C152—C153—H153
C153—C154—C155
C153—C154—H154
C155—C154—H154
C154—C155—C156
C154—C155—H155
C156—C155—H155
C151—C156—C155
C151—C156—H156
C155—C156—H156
O141—C141—C14
O141—C141—H141
C14—C141—H141
O341—C341—C14
O341—C341—H341
C14—C341—H341
119.99 (17)
120.30 (18)
120.1 (2)
120.0
120.0
120.2 (2)
119.9
119.9
120.2 (2)
119.9
119.9
119.6 (2)
120.2
120.2
122.4 (5)
118.8
118.8
112.0 (19)
124.0
C251—C252—Cl22
C253—C252—Cl22
C254—C253—C252
C254—C253—H253
C252—C253—H253
C253—C254—C255
C253—C254—H254
C255—C254—H254
C254—C255—C256
C254—C255—H255
C256—C255—H255
C251—C256—C255
C251—C256—H256
C255—C256—H256
O241—C241—C24
O241—C241—H241
C24—C241—H241
O441—C441—C24
O441—C441—H441
C24—C441—H441
120.09 (17)
120.40 (17)
120.1 (2)
119.9
119.9
120.3 (2)
119.8
119.8
119.9 (2)
120.0
120.0
119.8 (2)
120.1
120.1
118.2 (12)
120.9
120.9
118.2 (15)
120.9
124.0
120.9
C15—N11—N12—C13
C111—N11—N12—C13
N11—N12—C13—C14
N11—N12—C13—C131
N12—C13—C14—C15
C131—C13—C14—C15
N12—C13—C14—C141
C131—C13—C14—C141
N12—C13—C14—C341
C131—C13—C14—C341
N12—N11—C15—O151
C111—N11—C15—O151
N12—N11—C15—C14
C111—N11—C15—C14
C141—C14—C15—N11
C13—C14—C15—N11
C341—C14—C15—N11
C141—C14—C15—O151
C13—C14—C15—O151
C341—C14—C15—O151
C15—N11—C111—C112
N12—N11—C111—C112
C15—N11—C111—C116
N12—N11—C111—C116
C116—C111—C112—C113
N11—C111—C112—C113
C111—C112—C113—C114
−0.5 (2)
178.80 (18)
0.8 (3)
−179.6 (2)
−0.8 (3)
179.6 (2)
177.3 (9)
−2.3 (10)
176 (2)
C25—N21—N22—C23
C211—N21—N22—C23
N21—N22—C23—C24
N21—N22—C23—C231
N22—C23—C24—C25
C231—C23—C24—C25
N22—C23—C24—C241
C231—C23—C24—C241
N22—C23—C24—C441
C231—C23—C24—C441
N22—N21—C25—O251
C211—N21—C25—O251
N22—N21—C25—C24
C211—N21—C25—C24
C241—C24—C25—N21
C23—C24—C25—N21
C441—C24—C25—N21
C241—C24—C25—O251
C23—C24—C25—O251
C441—C24—C25—O251
C25—N21—C211—C216
N22—N21—C211—C216
C25—N21—C211—C212
N22—N21—C211—C212
C216—C211—C212—C213
N21—C211—C212—C213
C211—C212—C213—C214
−0.2 (2)
177.93 (18)
0.3 (2)
−178.8 (2)
−0.4 (3)
178.7 (2)
172.2 (13)
−8.8 (14)
−176.2 (17)
2.9 (17)
−175.75 (17)
6.5 (3)
0.0 (2)
−177.8 (2)
−171.4 (14)
0.2 (2)
176.8 (15)
3.8 (14)
175.4 (2)
−8.0 (15)
166.6 (2)
−11.1 (3)
−13.3 (3)
169.0 (2)
−0.9 (4)
−3 (2)
−178.96 (18)
1.9 (3)
0.0 (2)
−179.2 (2)
−177.5 (10)
0.5 (2)
−177.4 (18)
1.3 (11)
179.3 (2)
1.4 (19)
−19.3 (4)
161.6 (2)
161.9 (2)
−17.2 (3)
−1.4 (5)
179.9 (3)
1.3 (6)
178.9 (2)
1.3 (5)
Acta Cryst. (2019). C75, 768-776
sup-8

supporting information
C112—C113—C114—C115
C113—C114—C115—C116
C112—C111—C116—C115
N11—C111—C116—C115
C114—C115—C116—C111
N11—C15—O151—C151
C14—C15—O151—C151
C15—O151—C151—C156
C15—O151—C151—C152
C156—C151—C152—C153
O151—C151—C152—C153
C156—C151—C152—Cl12
O151—C151—C152—Cl12
C151—C152—C153—C154
Cl12—C152—C153—C154
C152—C153—C154—C155
C153—C154—C155—C156
C152—C151—C156—C155
O151—C151—C156—C155
C154—C155—C156—C151
C15—C14—C141—O141
C13—C14—C141—O141
C341—C14—C141—O141
C15—C14—C341—O341
C141—C14—C341—O341
C13—C14—C341—O341
−0.4 (6)
−0.3 (5)
0.6 (4)
179.4 (2)
0.2 (5)
−110.9 (2)
70.4 (3)
29.1 (3)
−153.42 (19)
−0.7 (3)
−178.17 (19)
−179.69 (16)
2.8 (3)
C212—C213—C214—C215
−0.6 (5)
−0.4 (4)
0.6 (4)
C213—C214—C215—C216
C214—C215—C216—C211
C212—C211—C216—C215
N21—C211—C216—C215
N21—C25—O251—C251
C24—C25—O251—C251
C25—O251—C251—C252
C25—O251—C251—C256
C256—C251—C252—C253
O251—C251—C252—C253
C256—C251—C252—Cl22
O251—C251—C252—Cl22
C251—C252—C253—C254
Cl22—C252—C253—C254
C252—C253—C254—C255
C253—C254—C255—C256
C252—C251—C256—C255
O251—C251—C256—C255
C254—C255—C256—C251
C25—C24—C241—O241
C23—C24—C241—O241
C441—C24—C241—O241
C25—C24—C441—O441
C241—C24—C441—O441
C23—C24—C441—O441
0.0 (4)
−179.9 (2)
−117.7 (2)
67.6 (3)
−153.77 (19)
29.0 (3)
−0.3 (3)
−177.63 (18)
178.53 (17)
1.3 (2)
0.6 (4)
0.4 (3)
179.7 (2)
−0.5 (4)
0.4 (4)
−178.51 (17)
−0.3 (4)
0.3 (4)
0.6 (3)
0.3 (3)
177.94 (19)
−0.5 (4)
1 (2)
−176.7 (9)
0 (10)
−176.6 (18)
3 (9)
6 (4)
177.4 (2)
−0.3 (4)
−9 (3)
−179.1 (12)
35 (8)
177.0 (16)
34 (8)
−8 (3)
Hydrogen-bond geometry (Å, º)
D—H···A
D—H
H···A
D···A
D—H···A
C156—H156···N12i
C255—H255···Cg3ii
0.93
0.93
2.59
2.80
3.433 (3)
3.635 (3)
152
140
Symmetry codes: (i) −x+1, −y, −z+2; (ii) −x+1, −y+1, −z+1.
3-Methyl-5-(4-nitrophenoxy)-1-phenyl-1H-pyrazole-4-carbaldehyde (IV)
Crystal data
C17H13N3O4
Mr = 323.30
F(000) = 672
Dx = 1.384 Mg m−3
Monoclinic, P21/c
a = 14.1163 (9) Å
b = 11.7268 (7) Å
c = 9.3982 (5) Å
β = 94.259 (3)°
V = 1551.47 (16) Å3
Z = 4
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 4821 reflections
θ = 1.4–30.8°
µ = 0.10 mm−1
T = 296 K
Block, colourless
0.20 × 0.15 × 0.15 mm
Acta Cryst. (2019). C75, 768-776
sup-9

supporting information
Data collection
Bruker APEXII CCD
28186 measured reflections
diffractometer
3956 independent reflections
2361 reflections with I > 2σ(I)
Rint = 0.037
Radiation source: fine focus sealed tube
Graphite monochromator
Detector resolution: 0.3333 pixels mm-1
φ and ω scans
Absorption correction: multi-scan
(SADABS; Bruker, 2015)
θ
max = 28.6°, θmin = 2.3°
h = −18→18
k = −15→15
l = −12→12
T
min = 0.945, Tmax = 0.985
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.043
wR(F2) = 0.121
Hydrogen site location: inferred from
neighbouring sites
H-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0385P)2 + 0.5804P]
where P = (Fo2 + 2Fc2)/3
S = 1.01
3956 reflections
219 parameters
0 restraints
(Δ/σ)max < 0.001
Δρmax = 0.19 e Å−3
Δρmin = −0.15 e Å−3
Primary atom site location: difference Fourier
map
Extinction correction: SHELXL2014
(Sheldrick, 2015b),
Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Extinction coefficient: 0.0064 (11)
Special details
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance
matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles;
correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate
(isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
y
z
Uiso*/Ueq
N1
N2
C3
C4
0.86994 (10)
0.96335 (10)
0.98509 (13)
0.90857 (13)
0.83639 (13)
0.82349 (12)
0.75167 (13)
0.7326
0.70832 (15)
0.6590
0.73745 (17)
0.7083
0.80937 (17)
0.8290
0.85318 (15)
0.9021
1.08136 (14)
1.1212
0.04307 (11)
0.07594 (12)
0.12942 (14)
0.13138 (14)
0.07652 (14)
−0.01374 (14)
−0.09122 (16)
−0.1081
−0.14363 (18)
−0.1950
−0.1204 (2)
−0.1564
−0.04447 (18)
−0.0291
0.00968 (16)
0.0614
0.18030 (18)
0.1570
0.28782 (14)
0.28157 (15)
0.40292 (19)
0.49144 (18)
0.41151 (18)
0.16813 (18)
0.1842 (2)
0.2745
0.0648 (2)
0.0747
−0.0681 (2)
−0.1479
−0.0831 (2)
−0.1735
0.03427 (19)
0.0235
0.4311 (2)
0.3580
0.0439 (3)
0.0467 (4)
0.0463 (4)
0.0471 (4)
0.0457 (4)
0.0442 (4)
0.0552 (5)
0.066*
0.0674 (6)
0.081*
0.0711 (6)
0.085*
0.0680 (6)
0.082*
0.0561 (5)
0.067*
0.0648 (5)
0.097*
C5
C11
C12
H12
C13
H13
C14
H14
C15
H15
C16
H16
C31
H31A
Acta Cryst. (2019). C75, 768-776
sup-10

supporting information
H31B
H31C
C41
H41
O41
O51
C51
C52
H52
C53
H53
C54
C55
H55
C56
H56
N54
O411
O412
1.1086
1.0763
0.91097 (17)
0.9677
0.1548
0.2619
0.17425 (17)
0.2070
0.5223
0.4314
0.6348 (2)
0.6710
0.097*
0.097*
0.0625 (5)
0.075*
0.84724 (12)
0.74717 (9)
0.68931 (12)
0.69553 (13)
0.7389
0.63630 (13)
0.6394
0.57244 (12)
0.56359 (13)
0.5183
0.62287 (13)
0.6182
0.51327 (12)
0.52206 (15)
0.45836 (11)
0.17227 (14)
0.04733 (10)
0.12862 (15)
0.24277 (15)
0.2687
0.31763 (15)
0.3954
0.27586 (16)
0.16141 (17)
0.1352
0.08639 (16)
0.0084
0.35609 (18)
0.45668 (17)
0.31846 (16)
0.71320 (15)
0.43900 (14)
0.49678 (18)
0.46518 (18)
0.4028
0.52768 (19)
0.5091
0.61811 (18)
0.6451 (2)
0.7042
0.5831 (2)
0.5991
0.69134 (19)
0.6681 (2)
0.77356 (18)
0.0781 (5)
0.0592 (4)
0.0463 (4)
0.0496 (4)
0.060*
0.0512 (4)
0.061*
0.0484 (4)
0.0544 (5)
0.065*
0.0536 (5)
0.064*
0.0662 (5)
0.1137 (7)
0.0883 (5)
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
N1
N2
C3
C4
0.0479 (8)
0.0457 (8)
0.0540 (10)
0.0629 (11)
0.0568 (11)
0.0487 (10)
0.0553 (11)
0.0568 (12)
0.0757 (15)
0.0945 (17)
0.0712 (13)
0.0585 (12)
0.0826 (15)
0.1000 (12)
0.0639 (8)
0.0511 (10)
0.0542 (10)
0.0523 (11)
0.0418 (9)
0.0486 (10)
0.0583 (11)
0.0526 (10)
0.1183 (16)
0.0690 (10)
0.0408 (7)
0.0458 (8)
0.0347 (8)
0.0341 (8)
0.0336 (8)
0.0370 (9)
0.0525 (11)
0.0620 (13)
0.0687 (14)
0.0621 (13)
0.0485 (10)
0.0596 (12)
0.0513 (11)
0.0851 (11)
0.0432 (7)
0.0438 (9)
0.0474 (10)
0.0437 (10)
0.0554 (11)
0.0624 (12)
0.0445 (10)
0.0765 (13)
0.0660 (12)
0.1129 (14)
0.0444 (8)
−0.0016 (6)
0.0006 (6)
0.0017 (7)
−0.0001 (8)
−0.0012 (7)
0.0063 (7)
−0.0019 (9)
−0.0055 (10)
0.0113 (12)
0.0078 (12)
−0.0004 (9)
−0.0064 (10)
−0.0012 (10)
−0.0015 (9)
−0.0105 (6)
−0.0049 (8)
−0.0046 (8)
−0.0008 (8)
0.0040 (8)
0.0128 (6)
0.0112 (7)
0.0051 (8)
0.0097 (8)
0.0182 (8)
0.0067 (8)
0.0108 (9)
0.0017 (11)
−0.0108 (11)
0.0066 (11)
0.0147 (9)
−0.0015 (10)
0.0087 (11)
0.0233 (8)
0.0349 (7)
0.0155 (8)
0.0188 (8)
0.0083 (9)
0.0074 (8)
0.0196 (9)
0.0202 (9)
0.0111 (9)
0.0609 (14)
0.0358 (9)
−0.0032 (6)
0.0000 (7)
0.0018 (8)
0.0497 (8)
0.0504 (10)
0.0452 (9)
0.0488 (10)
0.0474 (9)
0.0588 (11)
0.0828 (16)
0.0666 (14)
0.0476 (11)
0.0500 (11)
0.0754 (14)
0.0542 (12)
0.0520 (8)
0.0748 (9)
0.0458 (9)
0.0496 (10)
0.0582 (11)
0.0486 (10)
0.0547 (11)
0.0603 (11)
0.0705 (11)
0.1644 (19)
0.0875 (11)
−0.0014 (7)
−0.0013 (7)
−0.0055 (7)
−0.0076 (9)
−0.0178 (11)
−0.0214 (11)
−0.0088 (10)
−0.0047 (9)
−0.0040 (10)
−0.0119 (9)
−0.0131 (7)
−0.0144 (6)
−0.0075 (8)
0.0022 (8)
C5
C11
C12
C13
C14
C15
C16
C31
C41
O41
O51
C51
C52
C53
C54
C55
C56
N54
O411
O412
0.0008 (8)
−0.0060 (8)
0.0025 (9)
−0.0048 (9)
−0.0086 (8)
0.0135 (9)
0.0205 (11)
0.0230 (9)
0.0012 (9)
−0.0097 (10)
−0.0166 (12)
0.0012 (10)
Acta Cryst. (2019). C75, 768-776
sup-11

supporting information
Geometric parameters (Å, º)
N1—C5
N1—N2
N1—C11
N2—C3
C3—C4
1.346 (2)
1.3792 (19)
1.425 (2)
1.318 (2)
1.412 (2)
1.490 (3)
1.379 (2)
1.436 (3)
1.349 (2)
1.378 (2)
1.383 (2)
1.382 (3)
0.9300
1.371 (3)
0.9300
1.366 (3)
0.9300
1.379 (3)
0.9300
0.9300
C31—H31A
C31—H31B
C31—H31C
C41—O41
C41—H41
O51—C51
C51—C52
C51—C56
C52—C53
C52—H52
C53—C54
C53—H53
C54—C55
C54—N54
C55—C56
C55—H55
C56—H56
N54—O411
N54—O412
0.9600
0.9600
0.9600
1.205 (2)
0.9300
1.392 (2)
1.375 (2)
1.377 (2)
1.374 (2)
0.9300
1.374 (2)
0.9300
1.373 (3)
1.464 (2)
1.373 (2)
0.9300
C3—C31
C4—C5
C4—C41
C5—O51
C11—C12
C11—C16
C12—C13
C12—H12
C13—C14
C13—H13
C14—C15
C14—H14
C15—C16
C15—H15
C16—H16
0.9300
1.208 (2)
1.217 (2)
C5—N1—N2
110.74 (14)
130.35 (14)
118.85 (13)
104.96 (13)
112.24 (16)
119.70 (16)
128.05 (17)
103.77 (15)
129.73 (17)
126.36 (18)
119.02 (15)
108.26 (15)
132.58 (15)
120.40 (17)
121.39 (15)
118.21 (16)
119.28 (19)
120.4
C3—C31—H31A
C3—C31—H31B
H31A—C31—H31B
C3—C31—H31C
H31A—C31—H31C
H31B—C31—H31C
O41—C41—C4
O41—C41—H41
C4—C41—H41
C5—O51—C51
C52—C51—C56
C52—C51—O51
C56—C51—O51
C53—C52—C51
C53—C52—H52
C51—C52—H52
C52—C53—C54
C52—C53—H53
C54—C53—H53
C55—C54—C53
C55—C54—N54
C53—C54—N54
C54—C55—C56
C54—C55—H55
C56—C55—H55
109.5
109.5
109.5
109.5
109.5
109.5
126.9 (2)
116.5
116.5
118.98 (13)
122.32 (16)
122.25 (15)
115.38 (15)
118.61 (16)
120.7
120.7
118.99 (17)
120.5
C5—N1—C11
N2—N1—C11
C3—N2—N1
N2—C3—C4
N2—C3—C31
C4—C3—C31
C5—C4—C3
C5—C4—C41
C3—C4—C41
N1—C5—O51
N1—C5—C4
O51—C5—C4
C12—C11—C16
C12—C11—N1
C16—C11—N1
C11—C12—C13
C11—C12—H12
C13—C12—H12
C14—C13—C12
C14—C13—H13
C12—C13—H13
C15—C14—C13
C15—C14—H14
C13—C14—H14
120.4
120.5 (2)
119.8
119.8
120.0 (2)
120.0
120.5
122.36 (16)
118.60 (17)
119.02 (18)
118.77 (16)
120.6
120.0
120.6
Acta Cryst. (2019). C75, 768-776
sup-12

supporting information
C14—C15—C16
C14—C15—H15
C16—C15—H15
C15—C16—C11
C15—C16—H16
C11—C16—H16
120.7 (2)
119.7
119.7
119.23 (19)
120.4
120.4
C55—C56—C51
C55—C56—H56
C51—C56—H56
O411—N54—O412
O411—N54—C54
O412—N54—C54
118.85 (17)
120.6
120.6
123.20 (19)
118.24 (18)
118.56 (19)
C5—N1—N2—C3
C11—N1—N2—C3
N1—N2—C3—C4
N1—N2—C3—C31
N2—C3—C4—C5
C31—C3—C4—C5
N2—C3—C4—C41
C31—C3—C4—C41
N2—N1—C5—O51
C11—N1—C5—O51
N2—N1—C5—C4
C11—N1—C5—C4
C3—C4—C5—N1
C41—C4—C5—N1
C3—C4—C5—O51
C41—C4—C5—O51
C5—N1—C11—C12
N2—N1—C11—C12
C5—N1—C11—C16
N2—N1—C11—C16
C16—C11—C12—C13
N1—C11—C12—C13
C11—C12—C13—C14
C12—C13—C14—C15
−0.03 (18)
177.50 (14)
0.99 (19)
−178.18 (15)
−1.54 (19)
177.54 (18)
174.50 (17)
−6.4 (3)
−177.14 (14)
5.7 (3)
−0.94 (19)
−178.10 (16)
1.44 (18)
−174.41 (18)
176.93 (18)
1.1 (3)
−32.5 (3)
150.56 (16)
148.36 (18)
−28.6 (2)
−1.3 (3)
179.59 (17)
1.1 (3)
C13—C14—C15—C16
C14—C15—C16—C11
C12—C11—C16—C15
N1—C11—C16—C15
C5—C4—C41—O41
C3—C4—C41—O41
N1—C5—O51—C51
C4—C5—O51—C51
C5—O51—C51—C52
C5—O51—C51—C56
C56—C51—C52—C53
O51—C51—C52—C53
C51—C52—C53—C54
C52—C53—C54—C55
C52—C53—C54—N54
C53—C54—C55—C56
N54—C54—C55—C56
C54—C55—C56—C51
C52—C51—C56—C55
O51—C51—C56—C55
C55—C54—N54—O411
C53—C54—N54—O411
C55—C54—N54—O412
C53—C54—N54—O412
−0.2 (3)
0.0 (3)
0.7 (3)
179.87 (17)
−1.9 (3)
−176.9 (2)
−136.63 (16)
48.3 (3)
32.7 (3)
−149.82 (17)
3.2 (3)
−179.48 (16)
−0.7 (3)
−2.0 (3)
176.39 (16)
2.2 (3)
−176.22 (17)
0.3 (3)
−3.1 (3)
179.48 (17)
179.3 (2)
0.8 (3)
0.0 (3)
−178.45 (18)
−0.4 (3)
Hydrogen-bond geometry (Å, º)
D—H···A
D—H
H···A
D···A
D—H···A
C14—H14···O412i
C52—H52···O41ii
C55—H55···O411iii
C53—H53···Cg2iv
0.93
0.93
0.93
0.93
2.57
2.53
2.50
2.84
3.330 (3)
3.456 (2)
3.259 (3)
3.564 (2)
139
174
139
135
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x, −y+1/2, z−1/2; (iii) −x+1, y−1/2, −z+3/2; (iv) x, −y+1/2, z+1/2.
3-Methyl-5-(naphthalen-2-yloxy)-1-phenyl-1H-pyrazole-4-carbaldehyde (V)
Crystal data
C21H16N2O2
Mr = 328.36
Monoclinic, P21/n
a = 7.7302 (6) Å
b = 17.2550 (16) Å
c = 13.1989 (11) Å
β = 106.079 (2)°
V = 1691.7 (2) Å3
Acta Cryst. (2019). C75, 768-776
sup-13

supporting information
Z = 4
F(000) = 688
Dx = 1.289 Mg m−3
θ = 2.0–29.0°
µ = 0.08 mm−1
T = 296 K
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 4456 reflections
Block, brown
0.20 × 0.16 × 0.14 mm
Data collection
Bruker APEXII CCD
diffractometer
34394 measured reflections
4311 independent reflections
2711 reflections with I > 2σ(I)
Rint = 0.049
Radiation source: fine focus sealed tube
Graphite monochromator
Detector resolution: 0.3333 pixels mm-1
φ and ω scans
Absorption correction: multi-scan
(SADABS; Bruker, 2015)
θ
max = 28.6°, θmin = 2.4°
h = −9→10
k = −23→23
l = −17→17
T
min = 0.954, Tmax = 0.988
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.047
wR(F2) = 0.130
S = 1.03
4311 reflections
227 parameters
0 restraints
Hydrogen site location: inferred from
neighbouring sites
H-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0511P)2 + 0.449P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.17 e Å−3
Δρmin = −0.25 e Å−3
Special details
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance
matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles;
correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate
(isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
y
z
Uiso*/Ueq
N1
N2
C3
C4
0.49965 (16)
0.32134 (17)
0.2601 (2)
0.3964 (2)
0.5463 (2)
0.60936 (19)
0.7251 (2)
0.7348
0.8265 (2)
0.9065
0.8099 (3)
0.8775
0.38271 (8)
0.36741 (8)
0.32861 (10)
0.31630 (10)
0.35199 (9)
0.42022 (9)
0.47936 (9)
0.4949
0.51508 (11)
0.5544
0.49299 (12)
0.5176
0.43857 (10)
0.38728 (10)
0.45616 (13)
0.55195 (13)
0.53568 (12)
0.38274 (11)
0.42849 (13)
0.4973
0.37058 (16)
0.4010
0.26867 (17)
0.2298
0.0354 (3)
0.0415 (3)
0.0404 (4)
0.0393 (4)
0.0356 (3)
0.0328 (3)
0.0411 (4)
0.049*
0.0522 (5)
0.063*
0.0616 (6)
0.074*
C5
C11
C12
H12
C13
H13
C14
H14
C15
H15
C16
H16
0.6933 (3)
0.6820
0.5936 (2)
0.5160
0.43438 (12)
0.4197
0.39740 (10)
0.3573
0.22374 (15)
0.1544
0.28053 (13)
0.2503
0.0598 (5)
0.072*
0.0447 (4)
0.054*
Acta Cryst. (2019). C75, 768-776
sup-14

supporting information
C31
H31A
H31B
H31C
C41
H41
O41
O51
C51
H51
C52
C53
H53
C54
H54
C54A
C55
H55
C56
H56
C57
H57
C58
H58
C58A
0.0691 (2)
0.0073
0.0115
0.0654
0.3834 (3)
0.4890
0.2458 (2)
0.72116 (14)
0.9302 (2)
0.9925
0.7727 (2)
0.6730 (2)
0.5655
0.7369 (2)
0.6702
0.9017 (2)
0.9757 (3)
0.9116
0.30215 (13)
0.3213
0.3216
0.2465
0.27328 (11)
0.2654
0.24671 (9)
0.35620 (8)
0.33196 (9)
0.3013
0.36509 (9)
0.41139 (11)
0.4342
0.42215 (11)
0.4517
0.38972 (10)
0.40256 (12)
0.4319
0.42740 (16)
0.3586
0.4780
0.4270
0.64338 (15)
0.6969
0.65573 (13)
0.59018 (8)
0.75230 (12)
0.7163
0.69996 (12)
0.75088 (14)
0.7130
0.85672 (14)
0.8914
0.91541 (12)
1.02489 (14)
1.0614
0.0597 (5)
0.090*
0.090*
0.090*
0.0526 (5)
0.063*
0.0737 (5)
0.0467 (3)
0.0358 (3)
0.043*
0.0362 (4)
0.0492 (4)
0.059*
0.0522 (5)
0.063*
0.0401 (4)
0.0530 (5)
0.064*
1.1380 (3)
1.1842
1.2360 (3)
1.3483
1.1689 (2)
1.2346
1.0003 (2)
0.37294 (13)
0.3820
0.32887 (12)
0.3096
0.31377 (11)
0.2833
0.34402 (9)
1.07740 (14)
1.1493
1.02410 (15)
1.0605
0.91914 (14)
0.8849
0.86189 (12)
0.0588 (5)
0.071*
0.0577 (5)
0.069*
0.0486 (4)
0.058*
0.0357 (4)
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
N1
N2
C3
C4
0.0282 (7)
0.0287 (7)
0.0342 (8)
0.0386 (9)
0.0313 (8)
0.0296 (7)
0.0413 (9)
0.0493 (10)
0.0722 (14)
0.0767 (14)
0.0494 (10)
0.0395 (10)
0.0580 (11)
0.0737 (10)
0.0296 (6)
0.0315 (8)
0.0329 (8)
0.0374 (9)
0.0450 (10)
0.0455 (8)
0.0557 (9)
0.0449 (9)
0.0423 (9)
0.0443 (9)
0.0358 (8)
0.0420 (9)
0.0455 (10)
0.0593 (12)
0.0670 (13)
0.0473 (10)
0.0760 (14)
0.0540 (11)
0.0734 (10)
0.0782 (9)
0.0417 (9)
0.0453 (9)
0.0583 (11)
0.0606 (12)
0.0302 (7)
−0.0012 (5)
−0.0034 (6)
−0.0035 (7)
0.0018 (7)
0.0048 (7)
0.0015 (6)
0.0001 (7)
−0.0127 (8)
−0.0135 (10)
−0.0114 (11)
−0.0078 (8)
−0.0148 (9)
0.0038 (9)
−0.0013 (8)
0.0051 (5)
0.0025 (6)
0.0013 (7)
0.0154 (8)
0.0110 (8)
0.0041 (5)
0.0036 (6)
0.0120 (7)
0.0166 (7)
0.0082 (6)
0.0068 (6)
0.0084 (7)
0.0166 (9)
0.0393 (11)
0.0327 (10)
0.0131 (8)
0.0153 (9)
0.0284 (9)
0.0523 (9)
0.0039 (5)
0.0076 (6)
0.0061 (6)
0.0034 (8)
0.0139 (9)
0.0019 (6)
−0.0029 (6)
−0.0081 (7)
−0.0001 (7)
0.0022 (6)
0.0027 (6)
−0.0052 (7)
−0.0026 (9)
0.0030 (10)
−0.0055 (9)
−0.0056 (7)
−0.0146 (11)
0.0080 (9)
0.0165 (8)
0.0068 (5)
0.0016 (7)
0.0050 (7)
0.0015 (8)
−0.0113 (9)
0.0367 (7)
0.0429 (9)
0.0402 (9)
0.0309 (8)
0.0318 (8)
0.0383 (9)
0.0625 (12)
0.0655 (13)
0.0451 (10)
0.0380 (9)
0.0642 (13)
0.0537 (11)
0.0916 (12)
0.0297 (6)
0.0333 (8)
0.0291 (8)
0.0470 (10)
0.0514 (11)
C5
C11
C12
C13
C14
C15
C16
C31
C41
O41
O51
C51
C52
C53
C54
Acta Cryst. (2019). C75, 768-776
sup-15

supporting information
C54A
C55
C56
C57
C58
0.0398 (9)
0.0565 (12)
0.0611 (12)
0.0466 (11)
0.0409 (9)
0.0326 (8)
0.0454 (9)
0.0643 (12)
0.0744 (14)
0.0665 (13)
0.0554 (11)
0.0377 (8)
0.0348 (8)
0.0392 (10)
0.0329 (9)
0.0476 (11)
0.0432 (10)
0.0350 (8)
−0.0031 (7)
−0.0084 (9)
−0.0137 (10)
0.0001 (9)
0.0068 (8)
−0.0019 (6)
0.0098 (7)
0.0149 (9)
−0.0004 (9)
−0.0076 (9)
0.0009 (8)
0.0061 (7)
−0.0009 (7)
−0.0089 (9)
0.0020 (9)
0.0077 (9)
0.0033 (8)
0.0056 (6)
C58A
Geometric parameters (Å, º)
N1—C5
1.3408 (19)
C31—H31C
0.9600
N1—N2
N1—C11
N2—C3
C3—C4
C3—C31
C4—C5
1.3824 (17)
1.4240 (19)
1.318 (2)
1.420 (2)
1.491 (2)
1.381 (2)
1.444 (2)
1.3455 (18)
1.378 (2)
1.381 (2)
1.382 (2)
0.9300
1.370 (3)
0.9300
1.375 (3)
0.9300
1.373 (2)
0.9300
0.9300
C41—O41
C41—H41
O51—C52
C51—C52
C51—C58A
C51—H51
C52—C53
C53—C54
C53—H53
C54—C54A
C54—H54
C54A—C58A
C54A—C55
C55—C56
C55—H55
C56—C57
C56—H56
C57—C58
C57—H57
C58—C58A
C58—H58
1.210 (2)
0.9300
1.4008 (18)
1.350 (2)
1.412 (2)
0.9300
1.404 (2)
1.359 (2)
0.9300
1.411 (2)
0.9300
1.414 (2)
1.416 (2)
1.354 (3)
0.9300
1.394 (3)
0.9300
1.363 (2)
0.9300
1.413 (2)
0.9300
C4—C41
C5—O51
C11—C16
C11—C12
C12—C13
C12—H12
C13—C14
C13—H13
C14—C15
C14—H14
C15—C16
C15—H15
C16—H16
C31—H31A
C31—H31B
0.9600
0.9600
C5—N1—N2
C5—N1—C11
N2—N1—C11
C3—N2—N1
N2—C3—C4
N2—C3—C31
C4—C3—C31
C5—C4—C3
C5—C4—C41
C3—C4—C41
N1—C5—O51
N1—C5—C4
O51—C5—C4
C16—C11—C12
C16—C11—N1
C12—C11—N1
111.14 (12)
129.29 (12)
119.30 (12)
105.01 (13)
111.76 (14)
119.97 (16)
128.26 (16)
104.03 (14)
127.95 (16)
127.96 (16)
117.02 (13)
108.04 (13)
134.67 (14)
120.67 (14)
118.22 (14)
121.09 (13)
H31B—C31—H31C
O41—C41—C4
O41—C41—H41
C4—C41—H41
C5—O51—C52
C52—C51—C58A
C52—C51—H51
C58A—C51—H51
C51—C52—O51
C51—C52—C53
O51—C52—C53
C54—C53—C52
C54—C53—H53
C52—C53—H53
C53—C54—C54A
C53—C54—H54
109.5
125.07 (19)
117.5
117.5
120.97 (12)
119.83 (14)
120.1
120.1
116.15 (13)
122.23 (15)
121.41 (14)
118.57 (15)
120.7
120.7
121.75 (16)
119.1
Acta Cryst. (2019). C75, 768-776
sup-16

supporting information
C11—C12—C13
C11—C12—H12
C13—C12—H12
C14—C13—C12
C14—C13—H13
C12—C13—H13
C13—C14—C15
C13—C14—H14
C15—C14—H14
C16—C15—C14
C16—C15—H15
C14—C15—H15
C15—C16—C11
C15—C16—H16
C11—C16—H16
C3—C31—H31A
C3—C31—H31B
H31A—C31—H31B
C3—C31—H31C
H31A—C31—H31C
119.06 (15)
120.5
120.5
120.38 (17)
119.8
119.8
120.02 (17)
120.0
120.0
120.44 (17)
119.8
119.8
119.40 (16)
120.3
120.3
109.5
109.5
109.5
109.5
109.5
C54A—C54—H54
C54—C54A—C58A
C54—C54A—C55
C58A—C54A—C55
C56—C55—C54A
C56—C55—H55
C54A—C55—H55
C55—C56—C57
C55—C56—H56
C57—C56—H56
C58—C57—C56
C58—C57—H57
C56—C57—H57
C57—C58—C58A
C57—C58—H58
C58A—C58—H58
C51—C58A—C58
C51—C58A—C54A
C58—C58A—C54A
119.1
118.46 (14)
123.10 (16)
118.41 (15)
121.20 (17)
119.4
119.4
120.24 (17)
119.9
119.9
120.69 (18)
119.7
119.7
120.52 (17)
119.7
119.7
121.90 (15)
119.14 (14)
118.93 (15)
C5—N1—N2—C3
C11—N1—N2—C3
N1—N2—C3—C4
N1—N2—C3—C31
N2—C3—C4—C5
C31—C3—C4—C5
N2—C3—C4—C41
C31—C3—C4—C41
N2—N1—C5—O51
C11—N1—C5—O51
N2—N1—C5—C4
1.54 (17)
176.03 (13)
−1.31 (18)
179.93 (15)
0.64 (19)
179.27 (17)
−176.73 (16)
1.9 (3)
N1—C11—C16—C15
C5—C4—C41—O41
C3—C4—C41—O41
N1—C5—O51—C52
177.84 (16)
175.77 (19)
−7.5 (3)
146.36 (14)
−40.5 (3)
174.26 (13)
−0.5 (2)
148.23 (15)
−37.0 (2)
−0.9 (3)
−175.35 (16)
1.6 (3)
C4—C5—O51—C52
C58A—C51—C52—O51
C58A—C51—C52—C53
C5—O51—C52—C51
173.68 (13)
−0.1 (2)
C5—O51—C52—C53
C51—C52—C53—C54
O51—C52—C53—C54
C52—C53—C54—C54A
C53—C54—C54A—C58A
C53—C54—C54A—C55
C54—C54A—C55—C56
C58A—C54A—C55—C56
C54A—C55—C56—C57
C55—C56—C57—C58
C56—C57—C58—C58A
C52—C51—C58A—C58
C52—C51—C58A—C54A
C57—C58—C58A—C51
C57—C58—C58A—C54A
C54—C54A—C58A—C51
C55—C54A—C58A—C51
C54—C54A—C58A—C58
C55—C54A—C58A—C58
−1.17 (18)
−174.96 (14)
0.34 (17)
177.71 (16)
−173.21 (17)
4.2 (3)
131.39 (17)
−42.0 (2)
−50.3 (2)
136.31 (15)
−0.5 (2)
−178.77 (15)
1.1 (3)
−0.7 (3)
−0.3 (3)
0.9 (3)
C11—N1—C5—C4
C3—C4—C5—N1
−0.9 (3)
C41—C4—C5—N1
C3—C4—C5—O51
C41—C4—C5—O51
C5—N1—C11—C16
N2—N1—C11—C16
C5—N1—C11—C12
N2—N1—C11—C12
C16—C11—C12—C13
N1—C11—C12—C13
C11—C12—C13—C14
C12—C13—C14—C15
C13—C14—C15—C16
C14—C15—C16—C11
C12—C11—C16—C15
177.24 (18)
−177.22 (18)
0.9 (3)
0.0 (3)
−1.2 (3)
1.4 (3)
−176.80 (16)
1.1 (2)
177.50 (17)
−0.5 (3)
−0.5 (2)
−178.71 (15)
177.54 (16)
−0.7 (2)
−0.4 (3)
Acta Cryst. (2019). C75, 768-776
sup-17

supporting information
Hydrogen-bond geometry (Å, º)
D—H···A
D—H
H···A
D···A
D—H···A
C51—H51···O41i
C12—H12···Cg1ii
C53—H53···Cg2ii
0.93
0.93
0.93
2.50
2.96
2.78
3.386 (2)
3.4804 (17)
3.6477 (19)
160
117
155
Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y+1, −z+1.
3-Methyl-1-phenyl-5-(piperidin-1-yl)-1H-pyrazole-4-carbaldehyde (VI)
Crystal data
C16H19N3O
Mr = 269.34
F(000) = 576
Dx = 1.243 Mg m−3
Monoclinic, P21/n
a = 8.9432 (7) Å
b = 16.0546 (14) Å
c = 10.1155 (8) Å
β = 97.777 (2)°
V = 1439.0 (2) Å3
Z = 4
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 3504 reflections
θ = 2.4–28.1°
µ = 0.08 mm−1
T = 296 K
Block, colourless
0.20 × 0.15 × 0.10 mm
Data collection
Bruker APEXII CCD
diffractometer
27358 measured reflections
3000 independent reflections
1869 reflections with I > 2σ(I)
Rint = 0.047
Radiation source: fine focus sealed tube
Graphite monochromator
Detector resolution: 0.3333 pixels mm-1
φ and ω scans
Absorption correction: multi-scan
(SADABS; Bruker, 2015)
θ
max = 26.6°, θmin = 2.4°
h = −11→11
k = −20→20
l = −12→12
T
min = 0.950, Tmax = 0.992
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.047
wR(F2) = 0.141
S = 1.05
3000 reflections
H-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0563P)2 + 0.4589P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.29 e Å−3
Δρmin = −0.18 e Å−3
183 parameters
0 restraints
Hydrogen site location: inferred from
neighbouring sites
Extinction correction: SHELXL2014
(Sheldrick, 2015b),
Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Extinction coefficient: 0.011 (2)
Special details
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance
matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles;
correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate
(isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.
Acta Cryst. (2019). C75, 768-776
sup-18

supporting information
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
y
z
Uiso*/Ueq
N1
N2
C3
C4
C5
C11
C12
H12
C13
H13
C14
H14
C15
H15
C16
H16
C31
H31A
H31B
H31C
C41
H41
O41
N51
C52
H52A
H52B
C53
H53A
H53B
C54
0.35185 (18)
0.39911 (19)
0.3664 (2)
0.3031 (2)
0.2954 (2)
0.3634 (2)
0.2377 (2)
0.1447
0.2501 (3)
0.1656
0.3876 (3)
0.3962
0.5118 (3)
0.6040
0.5011 (2)
0.5860
0.3991 (3)
0.4450
0.3067
0.62845 (10)
0.66723 (12)
0.61450 (15)
0.53927 (13)
0.55100 (12)
0.67370 (12)
0.68566 (13)
0.6644
0.72930 (14)
0.7373
0.76093 (15)
0.7897
0.75014 (15)
0.7727
0.70600 (14)
0.6981
0.63675 (19)
0.6909
0.6373
0.5963
0.46445 (16)
0.4179
0.45590 (13)
0.50265 (10)
0.43642 (16)
0.3857
0.4524
0.42096 (16)
0.3745
0.4697
0.40178 (14)
0.3483
0.68452 (15)
0.57496 (17)
0.4763 (2)
0.51801 (18)
0.65407 (18)
0.80659 (19)
0.8697 (2)
0.8324
0.9883 (2)
1.0312
1.0431 (2)
1.1235
0.9793 (2)
1.0158
0.8610 (2)
0.8185
0.3393 (2)
0.3412
0.2787
0.3100
0.4411 (2)
0.4859
0.32399 (16)
0.74926 (15)
0.7089 (2)
0.6916
0.6272
0.8158 (2)
0.7900
0.8254
0.9484 (2)
0.9432
0.0453 (4)
0.0531 (5)
0.0522 (5)
0.0479 (5)
0.0427 (5)
0.0448 (5)
0.0520 (5)
0.062*
0.0618 (6)
0.074*
0.0674 (7)
0.081*
0.0685 (7)
0.082*
0.0574 (6)
0.069*
0.0774 (8)
0.116*
0.116*
0.116*
0.0646 (6)
0.078*
0.0913 (6)
0.0456 (4)
0.0616 (6)
0.074*
0.074*
0.0653 (6)
0.078*
0.078*
0.0596 (6)
0.071*
0.4666
0.2749 (3)
0.2456
0.2855 (2)
0.24068 (18)
0.1312 (3)
0.1842
0.0682
0.0347 (3)
−0.0323
−0.0269
0.1283 (3)
0.1778
0.0629
0.2464 (2)
0.1969
H54A
H54B
C55
H55A
H55B
C56
0.3982
0.46891 (15)
0.5204
0.4523
0.48331 (13)
0.5291
1.0173
0.9851 (2)
1.0045
1.0648
0.87430 (19)
0.8975
0.071*
0.0560 (6)
0.067*
0.067*
0.0489 (5)
0.059*
0.3124
0.3381 (2)
0.4074
H56A
H56B
0.3972
0.4339
0.8621
0.059*
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
N1
N2
0.0486 (9)
0.0523 (10)
0.0487 (10)
0.0596 (11)
0.0407 (9)
0.0498 (10)
−0.0008 (8)
0.0034 (8)
0.0135 (7)
0.0161 (8)
0.0070 (7)
0.0169 (9)
Acta Cryst. (2019). C75, 768-776
sup-19

supporting information
C3
C4
C5
0.0477 (12)
0.0496 (12)
0.0402 (10)
0.0491 (12)
0.0516 (12)
0.0809 (17)
0.102 (2)
0.0754 (17)
0.0505 (13)
0.0787 (17)
0.0819 (16)
0.1297 (16)
0.0496 (9)
0.0649 (14)
0.0580 (13)
0.0655 (14)
0.0619 (13)
0.0515 (11)
0.0675 (14)
0.0587 (13)
0.0497 (12)
0.0418 (11)
0.0548 (13)
0.0562 (14)
0.0501 (14)
0.0559 (14)
0.0552 (14)
0.108 (2)
0.0713 (16)
0.1042 (15)
0.0509 (10)
0.0685 (15)
0.0693 (16)
0.0564 (14)
0.0641 (14)
0.0534 (12)
0.0430 (11)
0.0356 (10)
0.0383 (10)
0.0434 (11)
0.0508 (12)
0.0508 (13)
0.0471 (13)
0.0676 (16)
0.0655 (14)
0.0483 (14)
0.0397 (12)
0.0387 (10)
0.0355 (8)
0.0110 (10)
0.0092 (10)
0.0035 (9)
0.0123 (9)
0.0067 (8)
0.0059 (8)
0.0055 (9)
0.0110 (10)
0.0180 (12)
−0.0025 (13)
−0.0150 (13)
0.0049 (10)
0.0186 (12)
0.0041 (11)
0.0068 (9)
0.0035 (7)
0.0039 (11)
0.0142 (11)
0.0247 (11)
0.0098 (10)
0.0044 (9)
0.0149 (11)
0.0054 (9)
0.0056 (8)
C11
C12
C13
C14
C15
C16
C31
C41
O41
N51
C52
C53
C54
C55
C56
−0.0002 (9)
−0.0007 (10)
0.0075 (12)
0.0009 (13)
−0.0100 (13)
−0.0028 (10)
0.0014 (15)
0.0097 (13)
0.0246 (12)
−0.0103 (8)
−0.0166 (12)
−0.0159 (12)
−0.0045 (11)
−0.0004 (11)
−0.0026 (10)
0.0065 (9)
0.0015 (10)
0.0024 (11)
0.0030 (10)
0.0043 (12)
0.0091 (11)
0.0238 (14)
−0.0009 (11)
−0.0075 (9)
0.0041 (7)
−0.0052 (11)
−0.0012 (12)
0.0074 (11)
0.0079 (10)
0.0101 (9)
0.0503 (13)
0.0700 (15)
0.0611 (14)
0.0427 (12)
0.0414 (11)
Geometric parameters (Å, º)
N1—C5
N1—N2
N1—C11
N2—C3
C3—C4
1.361 (3)
C31—H31B
C31—H31C
C41—O41
C41—H41
N51—C52
N51—C56
C52—C53
C52—H52A
C52—H52B
C53—C54
C53—H53A
C53—H53B
C54—C55
C54—H54A
C54—H54B
C55—C56
0.9600
0.9600
1.386 (2)
1.424 (2)
1.311 (3)
1.422 (3)
1.498 (3)
1.400 (3)
1.434 (3)
1.377 (2)
1.380 (3)
1.380 (3)
1.381 (3)
0.9300
1.375 (3)
0.9300
1.369 (4)
0.9300
1.383 (3)
0.9300
0.9300
1.209 (3)
0.9300
1.465 (3)
1.469 (2)
1.493 (3)
0.9700
0.9700
1.514 (3)
0.9700
0.9700
1.519 (3)
0.9700
0.9700
1.493 (3)
0.9700
C3—C31
C4—C5
C4—C41
C5—N51
C11—C12
C11—C16
C12—C13
C12—H12
C13—C14
C13—H13
C14—C15
C14—H14
C15—C16
C15—H15
C16—H16
C31—H31A
C55—H55A
C55—H55B
C56—H56A
C56—H56B
0.9700
0.9700
0.9700
0.9600
C5—N1—N2
C5—N1—C11
N2—N1—C11
C3—N2—N1
N2—C3—C4
111.91 (16)
130.03 (15)
118.02 (16)
104.94 (17)
112.29 (17)
O41—C41—C4
O41—C41—H41
C4—C41—H41
C5—N51—C52
C5—N51—C56
126.5 (2)
116.7
116.7
120.08 (16)
119.72 (15)
Acta Cryst. (2019). C75, 768-776
sup-20

supporting information
N2—C3—C31
C4—C3—C31
C5—C4—C3
C5—C4—C41
C3—C4—C41
N1—C5—N51
N1—C5—C4
N51—C5—C4
119.9 (2)
127.8 (2)
104.59 (18)
128.1 (2)
126.73 (19)
120.83 (16)
106.22 (16)
132.91 (19)
120.2 (2)
120.24 (18)
119.60 (18)
119.8 (2)
120.1
120.1
120.0 (2)
120.0
120.0
120.1 (2)
119.9
119.9
120.5 (2)
119.8
119.8
119.4 (2)
120.3
120.3
109.5
109.5
109.5
C52—N51—C56
N51—C52—C53
N51—C52—H52A
C53—C52—H52A
N51—C52—H52B
C53—C52—H52B
H52A—C52—H52B
C52—C53—C54
C52—C53—H53A
C54—C53—H53A
C52—C53—H53B
C54—C53—H53B
H53A—C53—H53B
C53—C54—C55
C53—C54—H54A
C55—C54—H54A
C53—C54—H54B
C55—C54—H54B
H54A—C54—H54B
C56—C55—C54
C56—C55—H55A
C54—C55—H55A
C56—C55—H55B
C54—C55—H55B
H55A—C55—H55B
N51—C56—C55
N51—C56—H56A
C55—C56—H56A
N51—C56—H56B
C55—C56—H56B
H56A—C56—H56B
112.51 (16)
110.39 (18)
109.6
109.6
109.6
109.6
108.1
111.81 (19)
109.3
109.3
109.3
109.3
107.9
110.77 (18)
109.5
109.5
109.5
109.5
108.1
111.16 (18)
109.4
109.4
109.4
109.4
108.0
110.90 (17)
109.5
109.5
109.5
C12—C11—C16
C12—C11—N1
C16—C11—N1
C11—C12—C13
C11—C12—H12
C13—C12—H12
C14—C13—C12
C14—C13—H13
C12—C13—H13
C15—C14—C13
C15—C14—H14
C13—C14—H14
C14—C15—C16
C14—C15—H15
C16—C15—H15
C11—C16—C15
C11—C16—H16
C15—C16—H16
C3—C31—H31A
C3—C31—H31B
H31A—C31—H31B
C3—C31—H31C
H31A—C31—H31C
H31B—C31—H31C
109.5
109.5
109.5
109.5
108.0
C5—N1—N2—C3
C11—N1—N2—C3
N1—N2—C3—C4
N1—N2—C3—C31
N2—C3—C4—C5
C31—C3—C4—C5
N2—C3—C4—C41
C31—C3—C4—C41
N2—N1—C5—N51
C11—N1—C5—N51
N2—N1—C5—C4
C11—N1—C5—C4
C3—C4—C5—N1
C41—C4—C5—N1
C3—C4—C5—N51
2.2 (2)
−175.79 (16)
−2.3 (2)
178.66 (18)
1.5 (2)
−179.5 (2)
−170.3 (2)
8.7 (3)
−179.19 (16)
−1.5 (3)
−1.3 (2)
176.41 (18)
−0.1 (2)
171.6 (2)
177.5 (2)
N1—C11—C12—C13
C11—C12—C13—C14
C12—C13—C14—C15
C13—C14—C15—C16
C12—C11—C16—C15
N1—C11—C16—C15
C14—C15—C16—C11
C5—C4—C41—O41
C3—C4—C41—O41
N1—C5—N51—C52
C4—C5—N51—C52
N1—C5—N51—C56
C4—C5—N51—C56
C5—N51—C52—C53
C56—N51—C52—C53
179.70 (19)
0.2 (3)
0.8 (3)
−1.3 (4)
0.2 (3)
179.78 (18)
0.8 (3)
−178.4 (2)
−8.4 (4)
156.64 (19)
−20.6 (3)
−56.2 (3)
126.5 (2)
−152.67 (19)
58.0 (3)
Acta Cryst. (2019). C75, 768-776
sup-21