(E)-1-[(5-Chloro-3-methyl-1-phenyl-1H-pyrazol-4-yl)methylidene] -2-phenylhydrazine: Sheets built from π-stacked hydrogen-bonded chains

Article abstract of DOI:10.1107/S2053229614000680

The reaction between 5-chloro-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde and phenylhydrazine proceeds via condensation to provide the title compound, C₁₇H₁₅ClN₄, (I), rather than via the alternative routes of simple nucleophilic substitution or cyclocondensation. With the exception of the phenyl group bonded directly to the pyrazole ring, the non-H atoms of (I) are nearly coplanar, with an r.m.s. deviation of 0.058?. The molecules are linked into C(7) chains by a single N - H?N hydrogen bond, and the chains are linked by π-π stacking interactions to form sheets.

Full text of DOI:10.1107/S2053229614000680

organic compounds
Acta Crystallographica Section C
nucleophilic substitution to form a hydrazinopyrazole, (II)
see Scheme). No evidence was found for a cyclocondensation
Structural Chemistry
(
ISSN 2053-2296
reaction, involving both condensation and substitution, which
would lead to the formation of a pyrazolo[3,4-b]pyrazole
derivative, (III) (see Scheme). This observation is consistent
with our previous observation (D ı´ az et al., 2010) of conden-
sation rather than substitution in the reaction between
(
E)-1-[(5-Chloro-3-methyl-1-phenyl-
6-chloro-4-(4-chlorophenyl)-3-methyl-1-phenyl-1H-pyrazolo-
3,4-b]pyridine-5-carbaldehyde and benzene-1,2-diamine,
1H-pyrazol-4-yl)methylidene]-
[
2
-phenylhydrazine: sheets built from
whereas reactions between amines and chloropyrimidine-
carbaldehydes reliably lead to substitution rather than
condensation (Cobo et al., 2008; Trilleras et al., 2009).
p-stacked hydrogen-bonded chains
a
a
b
Jorge Trilleras, Michael Utria, Justo Cobo and
c
Christopher Glidewell *
a
Grupo de Investigaci o´ n en Compuestos Heteroc ´ı clicos, Programa de Qu ´ı mica,
Facultad de Ciencias B a´ sicas, Universidad del Atl a´ ntico, Km 7 Antigua v ´ı a Puerto
b
Colombia, Barranquilla, Colombia, Departamento de Qu ´ı mica Inorg a´ nica y
c
Org a´ nica, Universidad de Ja e´ n, 23071 Ja e´ n, Spain, and School of Chemistry,
University of St Andrews, Fife KY16 9ST, Scotland
Correspondence e-mail: cg@st-andrews.ac.uk
Received 3 December 2013
Accepted 11 January 2014
The reaction between 5-chloro-3-methyl-1-phenyl-1H-pyra-
zole-4-carbaldehyde and phenylhydrazine proceeds via con-
densation to provide the title compound, C H ClN , (I),
17
15
4
rather than via the alternative routes of simple nucleophilic
substitution or cyclocondensation. With the exception of the
phenyl group bonded directly to the pyrazole ring, the non-H
atoms of (I) are nearly coplanar, with an r.m.s. deviation of
˚
0.058 A. The molecules are linked into C(7) chains by a single
N—Hꢀ ꢀ ꢀN hydrogen bond, and the chains are linked by ꢀ–ꢀ
stacking interactions to form sheets.
Keywords: crystal structure; p-stacked hydrogen-bonded chains;
condensation reaction; phenylhydrazine derivative.
1
. Introduction
Pyrazole rings are present in numerous natural products, as
well as in synthetic pharmacophores with biological activity,
and the structural diversity and biological importance of
pyrazole derivatives have made them attractive targets for
synthesis. Substituted 4-formylpyrazoles can be used as
precursors in the synthesis of fused pyrazole systems, and it
has been reported that nucleophilic displacement of chloro
substituents by nucleophiles based on heteroatoms such as N,
O or S can lead either to simple substitution or to intra-
molecular cyclization (Kaushik et al., 2010; Maluleka &
Mphahlele, 2013).
2
. Experimental
2.1. Synthesis and crystallization
We report here the structure of (E)-1-[(5-chloro-3-methyl-
A catalytic quantity of acetic acid was added to a solution
1
(
3
-phenyl-1H-pyrazol-4-yl)methylidene]-2-phenylhydrazine, (I)
Fig. 1), which was prepared by the reaction between 5-chloro-
-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde and phenyl-
of 5-chloro-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde
(221 mg, 1 mmol) and phenylhydrazine (108 mg, 1 mmol) in
ethanol (5ml), and this mixture was then heated under reflux
for 2 h. The solution was allowed to cool to ambient temper-
ature and the resulting solid product, (I), was collected by
hydrazine, where the reaction turns out to involve straight-
forward condensation to form compound (I), rather than
2
16 # 2014 International Union of Crystallography
doi:10.1107/S2053229614000680
Acta Cryst. (2014). C70, 216–219

organic compounds
Table 1
Experimental details.
Table 2
Selected geometric parameters ( A˚ , ).
ꢁ
Crystal data
Chemical formula
N1—N2
N2—C3
C3—C4
1.373 (3)
1.328 (3)
1.424 (3)
C4—C5
C5—N1
C41—N41
1.379 (3)
1.363 (3)
1.289 (3)
C
310.78
17
H
15ClN
4
M
r
Crystal system, space group
Temperature (K)
1
Monoclinic, P2 /n
120
11.773 (2), 9.9525 (18), 13.760 (3)
114.519 (10)
1466.9 (5)
4
Mo Kꢂ
0.26
N2—N1—C11—C12
C5—C4—C41—N41
C4—C41—N41—N42
ꢃ131.2 (2)
176.9 (2)
ꢃ175.5 (2)
C41—N41—N42—C421
N41—N42—C421—C422
ꢃ176.2 (2)
ꢃ10.3 (3)
˚
a, b, c (A)
ꢁ
ꢁ
V (A )
( )
˚
3
Z
Radiation type
ꢃ1
ꢃ (mm
Crystal size (mm)
)
development of a significant degree of aromatic delocalization
within the pyrazole ring.
0.36 ꢄ 0.33 ꢄ 0.21
Data collection
Diffractometer
Apart from the pendent phenyl ring (atoms C11–C16), the
non-H atoms in the molecule of (I) do not deviate markedly
from coplanarity; the maximum deviation from the mean
plane of these atoms is exhibited by atom N42, whose devia-
Bruker–Nonius KappaCCD diffrac-
tometer
Multi-scan (SADABS; Sheldrick,
Absorption correction
2003)
Tmin, Tmax
0.901, 0.946
23842, 3355, 2305
˚
˚
No. of measured, independent and
observed [I > 2ꢄ(I)] reflections
tion is 0.127 (2) A, and the r.m.s. deviation is 0.058 A. In
addition, the dihedral angle between the planes of the pyra-
zole and terminal phenyl ring (atoms C421–C426) is only
R
int
0.087
0.650
˚
ꢃ1
)
(sin ꢅ/ꢆ)max (A
ꢁ
1
.9 (2) , whereas that between the pyrazole and C11–C16
Refinement
2
ꢁ
2
2
phenyl rings is 48.5 (2) . The coplanarity, apart from the C11–
C16 phenyl ring, is most plausibly associated with the ꢀ–ꢀ
stacking interactions between inversion-related pairs of mol-
ecules, as discussed below, while the twist of the C11–C16 ring
out of the plane of the rest of the molecule may be influenced
by the contact between atoms C151 and H12, where the
R[F > 2ꢄ(F )], wR(F ), S
No. of reflections
No. of parameters
0.053, 0.139, 1.04
3355
200
H-atom parameters constrained
H-atom treatment
˚
ꢃ3
)
Áꢇmax, Áꢇmin (e A
0.36, ꢃ0.49
Computer programs: COLLECT (Hooft, 1998), DIRAX/LSQ (Duisenberg et al., 2000),
EVALCCD (Duisenberg et al., 2003), SIR2004 (Burla et al., 2005), SHELXL97
(Sheldrick, 2008) and PLATON (Spek, 2009).
˚
observed nonbonded distance in (I) of 2.94 A is almost iden-
˚
tical to the sum of the van der Waals radii (2.95 A; Bondi,
1
964; Rowland & Taylor, 1996). The molecules of (I) thus
filtration and washed with cold hexane (yield 63%, m.p. 452–
4
+
55 K). MS (70 eV), m/z: 310 (M ), 275, 193, 132, 91, 77, 69, 51,
exhibit no internal symmetry, and hence they are conforma-
tionally chiral; however, the centrosymmetric space group
confirms that equal numbers of the two conformational
enantiomers are present in the crystal.
41. Yellow crystals suitable for single-crystal X-ray diffraction
were grown by slow evaporation, at ambient temperature and
in the presence of air, of a solution in dimethylformamide–
ethanol (3:7 v/v).
2.2. Refinement
Crystal data, data collection and structure refinement
details are summarized in Table 1. All H atoms were located in
difference maps and then treated as riding atoms. H atoms
bonded to C atoms were permitted to ride in geometrically
idealized positions, with C—H = 0.95 (aromatic and alkenic)
˚
or 0.98 A (methyl) and U (H) = kU (C), where k = 1.5 for
iso
eq
the methyl group, which was permitted to rotate but not to tilt,
and 1.2 for the phenyl and alkenic groups. The H atom bonded
to atom N42 was similarly permitted to ride, with an N—H
˚
distance of 0.88 A and U (H) = 1.2U (N).
iso eq
3
. Results and discussion
Within the pyrazole ring of compound (I), the N2—C3 and
˚
N1—C5 bond lengths differ by less than 0.04 A (Table 2),
despite the fact that these two bonds are formally double and
single bonds, respectively; both these bonds are very signifi-
cantly longer than the isolated N41 C41 double bond.
Similarly, the C3—C4 and C4—C5 distances differ by less than
˚
Figure 1
The molecular structure of compound (I), showing the atom-labelling
scheme. Displacement ellipsoids are drawn at the 30% probability level.
0.06 A, although these two bonds are formally single and
double bonds, respectively. These observations point to the
ꢂ
Acta Cryst. (2014). C70, 216–219
Trilleras et al.
C
17
H
15ClN
4
217

organic compounds
Table 3
Hydrogen-bond geometry (A, ).
˚
ꢁ
Cg1 and Cg2 represent the centroids of the C421–C426 and C11–C16 rings,
respectively.
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
i
N42—H42ꢀ ꢀ ꢀN2
0.88
0.95
0.98
2.26
2.73
2.92
3.100 (3)
3.392 (2)
3.373 (2)
159
127
109
ii
C13—H13ꢀ ꢀ ꢀCg1
iii
C31—H31Aꢀ ꢀ ꢀCg2
1
2
1
2
1
2
1
2
Symmetry codes: (i) x þ ; ꢃy þ ; z þ ; (ii) ꢃx þ 1; ꢃy; ꢃz þ 1; (iii) ꢃx þ ,
1
1
y þ ; ꢃz þ .
2
2
It is of interest to consider what factors might be respon-
sible for the adoption of the observed conformation for (I), as
opposed to the other possible conformations, viz. (A)–(C) (see
Scheme), which all have nearly planar skeletons, apart from
the C11–C16 phenyl ring. The alternative orientation of the
C
N unit relative to the C—Cl bond in forms (I) and (A) is
reminiscent of the two alternative orientations (D) and (E) of
the formyl group observed in an extended series of chloro-
pyrimidine carbaldehydes (Cobo et al., 2008). A number of
factors were considered (Cobo et al., 2008) as plausible
contributors to the observation of these alternative confor-
mations, and two of these factors, namely electrostatics and
intermolecular hydrogen-bond formation, are relevant to the
present example. It may be assumed that the C5—Cl51 bond is
polarized, with the Cl atom carrying a partial negative charge;
since in the imino unit atom N41 also carries a partial negative
charge, the mutual repulsion of these charges favours forms (I)
Figure 3
Part of the crystal structure of compound (I), showing the ꢀ–ꢀ stacking
interactions between a pair of inversion-related molecules. For the sake
of clarity, the unit-cell outline and all H atoms have been omitted. The
atom marked with an asterisk (*) is at the symmetry position (ꢃx + 1,
ꢃy + 1, ꢃz + 1).
and (B) over forms (A) and (C). So far as hydrogen bonding is
concerned, the formation of an intermolecular N—Hꢀ ꢀ ꢀN
hydrogen bond, as discussed below, is most likely to be the
principal factor favouring the observed conformation (Fig. 1)
over the alternative conformation, i.e. (B).
The supramolecular assembly of (I) is determined by a
combination of an N—Hꢀ ꢀ ꢀN hydrogen bond (Table 3) and a
ꢀ
–ꢀ stacking interaction. The N—Hꢀ ꢀ ꢀN hydrogen bond links
molecules related by the n-glide plane at y = 0.25 into a C(7)
Bernstein et al., 1995) chain running parallel to the [101]
(
direction, in which the two conformational enantiomorphs
alternate (Fig. 2). Chains of this type are linked by ꢀ–ꢀ
stacking interactions. In the pair of inversion-related mol-
ecules at (x, y, z) and (ꢃx + 1, ꢃy + 1, ꢃz + 1), the pyrazole
ring of one molecule and the C421–C426 phenyl ring of the
other are nearly parallel, with a dihedral angle between their
ꢁ
planes of 1.9 (2) . The distance between the centroids of these
˚
two rings is 3.470 (2) A and the shortest perpendicular
distance from the centroid of one ring to the plane of the other
˚
˚
is 3.385 (2) A, giving a ring-centroid offset of ca 1.13 A.
Hence, the molecules in each such pair are linked by two ꢀ–ꢀ
stacking interactions (Fig. 3). The two molecules in the
reference ꢀ-stacked pair at (x, y, z) and (ꢃx + 1, ꢃy + 1, ꢃz + 1)
form parts, respectively, of the hydrogen-bonded chains across
1
3
Figure 2
the n-glide planes at y = and y = . Similarly, the molecule at
4 4
1
2
1
2
1
4
1
2
Part of the crystal structure of compound (I), showing the formation of a
hydrogen-bonded C(7) chain along [101]. For the sake of clarity, H atoms
bonded to C atoms have been omitted. Atoms marked with an asterisk
(
x + , ꢃy + , z + ), which lies in the chain across the n-glide
plane at y = , forms ꢀ–ꢀ stacking interactions with the mol-
3
1
3
1
2
1
2
1
2
ecule at (ꢃx + , y ꢃ , ꢃz + ), which itself forms part of the
(
*) or a hash (#) are at the symmetry positions (x + , ꢃy + , z + ) and
2
2
2
1
2
1
2
1
2
1
(x ꢃ , ꢃy + , z ꢃ ), respectively.
hydrogen-bonded chain across the n-glide plane at y = ꢃ . In
4
ꢂ
2
18 Trilleras et al.
C
17
H
15ClN
4
Acta Cryst. (2014). C70, 216–219

organic compounds
sum of the van der Waals radii, and to the associated atom C12
˚
at (ꢃx + 1, ꢃy, z + 1), with a Cꢀ ꢀ ꢀN distance of 3.419 (3) A,
ꢁ
corresponding to a C—Hꢀ ꢀ ꢀN angle of only 121 . The long
Hꢀ ꢀ ꢀN distance and the very small C—Hꢀ ꢀ ꢀN angle mean that
this contact is not structurally significant (Wood et al., 2009).
There are no short intermolecular contacts involving the Cl
atom.
The authors thank ‘Centro de Instrumentaci o´ n Cient ı´ fico-
T e´ cnica of Universidad de Ja e´ n’ and the staff for data collec-
tion. JT and MU thank UNIATLANTICO (Universidad del
Atl a´ ntico, Colombia) for financial support. JC thanks the
Consejer ı´ a de Innovaci o´ n, Ciencia y Empresa (Junta de
Andaluc ı´ a, Spain) and the Universidad de Ja e´ n for financial
support.
Figure 4
A stereoview of part of the crystal structure of compound (I), showing the
formation of a ꢀ-stacked sheet of hydrogen-bonded chains. For the sake
of clarity, H atoms bonded to C atoms have been omitted.
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: SF3218). Services for accessing these data are
described at the back of the journal.
this way, the hydrogen-bonded chains parallel to [101] are
linked into a ꢀ-stacked sheet lying parallel to (101) (Fig. 4).
There are two further direction-specific intermolecular
contacts, both of the C—Hꢀ ꢀ ꢀꢀ(arene) type (Table 3), which
require comment. Both of these contacts have C—Hꢀ ꢀ ꢀ(ring-
References
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Int. Ed. Engl. 34, 1555–1573.
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ꢁ
centroid) angles which are less than 130 and, on this basis,
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Caro, L., Giacovazzo, C., Polidori, G. & Spagna, R. (2005). J. Appl. Cryst. 38,
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2
009). In addition, the contact having the smaller D—Hꢀ ꢀ ꢀA
381–388.
angles also has a rather long Hꢀ ꢀ ꢀA distance and it involves
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Glidewell, C. (2008). Acta Cryst. B64, 596–609.
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one of the C—H bonds of the methyl group. When a methyl
group, having local C symmetry, is bonded to a planar ring,
3
having approximate local C symmetry, the resulting sixfold
2
Duisenberg, A. J. M., Hooft, R. W. W., Schreurs, A. M. M. & Kroon, J. (2000).
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rotational barrier is extremely low, i.e. of the order of only a
ꢃ1
few J mol (Tannenbaum et al., 1956; Naylor & Wilson, 1957),
so that such a methyl group is likely to be undergoing very
rapid rotation about the bond connecting the two entities in
question, here the C3—C31 bond, even in the solid state at low
temperatures (Riddell & Rogerson, 1996, 1997). Hence, we
conclude that neither of the C—Hꢀ ꢀ ꢀꢀ(arene) contacts is
structurally significant. Thus, although the C11–C16 phenyl
rings lie at the ends of the ꢀ-stacked dimers (Fig. 3), they play
no structural role, other than defining a lower bound for the
axial approach of such dimers to one another (cf. Fig. 4).
Perhaps surprisingly, imine-type atom N41 plays no role in the
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ꢂ
Acta Cryst. (2014). C70, 216–219
Trilleras et al.
C
17
H
15ClN
4
219

supplementary materials
supplementary materials
Acta Cryst. (2014). C70, 216-219 [doi:10.1107/S2053229614000680]
(
E)-1-[(5-Chloro-3-methyl-1-phenyl-1H-pyrazol-4-yl)methylidene]-2-phenyl-
hydrazine: sheets built from π-stacked hydrogen-bonded chains
Jorge Trilleras, Michael Utria, Justo Cobo and Christopher Glidewell
Computing details
Data collection: COLLECT (Hooft, 1998); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction:
EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to
refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare
material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
(E)-1-[(5-Chloro-3-methyl-1-phenyl-1H-pyrazol-4-yl)methylidene]-2-phenylhydrazine
Crystal data
C
M
17
H
15ClN
4
F(000) = 648
= 1.407 Mg m
−3
r
= 310.78
D
x
Monoclinic, P2
1
/n
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 3355 reflections
θ = 2.6–27.5°
µ = 0.26 mm
T = 120 K
Hall symbol: -P 2yn
a = 11.773 (2) Å
b = 9.9525 (18) Å
c = 13.760 (3) Å
β = 114.519 (10)°
−1
Block, yellow
0.36 × 0.33 × 0.21 mm
3
V = 1466.9 (5) Å
Z = 4
Data collection
Bruker–Nonius KappaCCD
diffractometer
Radiation source: Bruker–Nonius FR591
rotating anode
Tmin = 0.901, Tmax = 0.946
23842 measured reflections
3355 independent reflections
2305 reflections with I > 2σ(I)
Graphite monochromator
Detector resolution: 9.091 pixels mm
φ & ω scans
R
int = 0.087
-1
θmax = 27.5°, θmin = 2.6°
h = −15→15
k = −12→12
l = −17→17
Absorption correction: multi-scan
(
SADABS; Sheldrick, 2003)
Refinement
2
Refinement on F
Primary atom site location: structure-invariant
direct methods
Secondary atom site location: difference Fourier
map
Least-squares matrix: full
R[F > 2σ(F )] = 0.053
2
2
2
wR(F ) = 0.139
S = 1.04
Hydrogen site location: inferred from
neighbouring sites
H-atom parameters constrained
3
2
0
355 reflections
00 parameters
restraints
Acta Cryst. (2014). C70, 216-219
sup-1

supplementary materials
2
2
2
−3
w = 1/[σ (F
where P = (F
Δ/σ)max = 0.001
o
) + (0.0621P) + 1.0139P]
Δρmax = 0.36 e Å
2
2
−3
o
+ 2F
c
)/3
Δρmin = −0.49 e Å
(
2
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å )
x
y
z
Uiso*/Ueq
N1
0.48333 (18)
0.36968 (18)
0.3935 (2)
0.5236 (2)
0.5762 (2)
0.4900 (2)
0.5563 (2)
0.5999
0.02131 (19)
0.0719 (2)
0.1558 (2)
0.1625 (2)
0.0749 (2)
−0.0694 (2)
−0.1895 (2)
−0.2106
0.30004 (15)
0.28775 (16)
0.36891 (19)
0.43589 (18)
0.38850 (18)
0.22207 (18)
0.25351 (19)
0.3272
0.0219 (4)
0.0240 (5)
0.0235 (5)
0.0220 (5)
0.0225 (5)
0.0226 (5)
0.0241 (5)
0.029*
N2
C3
C4
C5
C11
C12
H12
C13
0.5580 (2)
0.6041
−0.2777 (2)
−0.3590
0.1764 (2)
0.1972
0.0265 (5)
0.032*
H13
C14
0.4930 (2)
0.4937
−0.2481 (2)
−0.3097
0.06943 (19)
0.0169
0.0266 (6)
0.032*
H14
C15
0.4265 (2)
0.3820
−0.1286 (3)
−0.1083
0.03817 (19)
−0.0355
0.0269 (6)
0.032*
H15
C16
0.4255 (2)
0.3804
−0.0393 (2)
0.0426
0.11489 (19)
0.0939
0.0253 (5)
0.030*
H16
C31
H31A
H31B
H31C
C41
0.2907 (2)
0.2107
0.2303 (3)
0.2050
0.3812 (2)
0.3234
0.0276 (6)
0.041*
0.3039
0.3271
0.3781
0.041*
0.2897
0.2078
0.4502
0.041*
0.5880 (2)
0.6765
0.2501 (2)
0.2484
0.52585 (18)
0.5613
0.0235 (5)
0.028*
H41
N41
N42
H42
C421
C422
H422
C423
H423
C424
H424
C425
H425
C426
H426
Cl51
0.52473 (19)
0.58770 (19)
0.6696
0.33070 (19)
0.4184 (2)
0.4234
0.55775 (15)
0.63754 (15)
0.6639
0.0231 (5)
0.0247 (5)
0.030*
0.5209 (2)
0.3908 (2)
0.3456
0.5003 (2)
0.5105 (2)
0.4617
0.67712 (18)
0.62639 (18)
0.5626
0.0226 (5)
0.0243 (5)
0.029*
0.3279 (2)
0.2395
0.5922 (3)
0.5983
0.6696 (2)
0.6351
0.0281 (6)
0.034*
0.3921 (2)
0.3485
0.6649 (2)
0.7203
0.7624 (2)
0.7917
0.0282 (6)
0.034*
0.5219 (2)
0.5671
0.6551 (2)
0.7049
0.8117 (2)
0.8750
0.0278 (6)
0.033*
0.5857 (2)
0.6741
0.5736 (2)
0.5679
0.76949 (19)
0.8040
0.0248 (5)
0.030*
0.73009 (5)
0.04036 (6)
0.42363 (5)
0.02856 (19)
2
Atomic displacement parameters (Å )
11
22
33
12
13
23
U
U
U
U
U
U
N1
N2
0.0167 (10)
0.0159 (10)
0.0229 (11)
0.0279 (11)
0.0274 (10)
0.0300 (11)
0.0005 (8)
0.0021 (8)
0.0105 (8)
0.0111 (9)
−0.0022 (8)
−0.0013 (9)
Acta Cryst. (2014). C70, 216-219
sup-2

supplementary materials
C3
0.0202 (12)
0.0205 (12)
0.0184 (12)
0.0191 (12)
0.0199 (12)
0.0237 (13)
0.0272 (14)
0.0236 (13)
0.0227 (12)
0.0204 (13)
0.0180 (12)
0.0230 (11)
0.0184 (10)
0.0231 (12)
0.0226 (12)
0.0223 (13)
0.0280 (14)
0.0290 (14)
0.0228 (13)
0.0179 (3)
0.0233 (13)
0.0223 (12)
0.0240 (12)
0.0234 (12)
0.0271 (13)
0.0245 (13)
0.0294 (14)
0.0334 (14)
0.0241 (13)
0.0312 (14)
0.0277 (13)
0.0244 (11)
0.0301 (11)
0.0226 (12)
0.0255 (12)
0.0295 (14)
0.0267 (13)
0.0272 (13)
0.0270 (13)
0.0327 (4)
0.0289 (13)
0.0243 (12)
0.0255 (12)
0.0287 (13)
0.0260 (13)
0.0359 (14)
0.0280 (13)
0.0248 (12)
0.0307 (13)
0.0324 (13)
0.0247 (12)
0.0218 (10)
0.0253 (10)
0.0239 (12)
0.0233 (12)
0.0328 (14)
0.0349 (14)
0.0288 (13)
0.0249 (12)
0.0342 (3)
−0.0008 (10)
−0.0010 (10)
−0.0011 (10)
−0.0050 (10)
−0.0017 (10)
−0.0017 (10)
−0.0046 (11)
−0.0043 (11)
0.0004 (10)
0.0014 (11)
0.0005 (10)
−0.0007 (9)
0.0004 (9)
0.0122 (10)
0.0105 (10)
0.0093 (10)
0.0133 (10)
0.0104 (10)
0.0168 (11)
0.0161 (11)
0.0111 (11)
0.0127 (11)
0.0122 (11)
0.0089 (10)
0.0092 (9)
0.0089 (9)
0.0116 (10)
0.0082 (10)
0.0118 (11)
0.0182 (12)
0.0136 (11)
0.0101 (10)
0.0099 (3)
0.0001 (10)
0.0006 (9)
C4
C5
0.0009 (10)
−0.0040 (10)
0.0001 (10)
−0.0018 (11)
−0.0062 (10)
−0.0002 (10)
0.0017 (10)
−0.0062 (11)
0.0019 (10)
−0.0003 (8)
−0.0054 (8)
0.0021 (9)
C11
C12
C13
C14
C15
C16
C31
C41
N41
N42
C421
C422
C423
C424
C425
C426
Cl51
0.0007 (10)
0.0006 (10)
0.0042 (11)
0.0041 (11)
−0.0035 (11)
−0.0003 (10)
0.0014 (3)
−0.0017 (10)
0.0040 (11)
−0.0013 (11)
−0.0031 (10)
−0.0002 (10)
−0.0041 (3)
Geometric parameters (Å, º)
N1—N2
1.373 (3)
C31—H31A
0.9800
N1—C11
N2—C3
1.429 (3)
1.328 (3)
1.424 (3)
1.488 (3)
1.379 (3)
1.363 (3)
1.445 (3)
1.705 (2)
1.383 (3)
1.395 (3)
1.384 (3)
0.9500
C31—H31B
C31—H31C
C41—N41
0.9800
0.9800
C3—C4
1.289 (3)
0.9500
C3—C31
C4—C5
C41—H41
N41—N42
1.357 (3)
1.391 (3)
0.8800
C5—N1
N42—C421
N42—H42
C4—C41
C5—Cl51
C11—C16
C11—C12
C12—C13
C12—H12
C13—C14
C13—H13
C14—C15
C14—H14
C15—C16
C15—H15
C16—H16
C421—C426
C421—C422
C422—C423
C422—H422
C423—C424
C423—H423
C424—C425
C424—H424
C425—C426
C425—H425
C426—H426
1.387 (3)
1.399 (3)
1.388 (3)
0.9500
1.387 (4)
0.9500
1.379 (4)
0.9500
1.394 (4)
0.9500
1.391 (4)
0.9500
1.386 (3)
0.9500
1.384 (3)
0.9500
0.9500
0.9500
C5—N1—N2
C5—N1—C11
N2—N1—C11
C3—N2—N1
N2—C3—C4
N2—C3—C31
110.27 (18)
130.1 (2)
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
109.5
109.5
119.58 (18)
105.78 (18)
111.6 (2)
120.7 (2)
Acta Cryst. (2014). C70, 216-219
sup-3

supplementary materials
C4—C3—C31
127.6 (2)
103.8 (2)
127.4 (2)
128.5 (2)
108.6 (2)
122.60 (18)
128.74 (19)
120.3 (2)
119.2 (2)
120.4 (2)
119.3 (2)
120.3
N41—C41—C4
119.7 (2)
120.1
C5—C4—C3
N41—C41—H41
C4—C41—H41
C5—C4—C41
120.1
C3—C4—C41
C41—N41—N42
N41—N42—C421
N41—N42—H42
C421—N42—H42
C426—C421—N42
118.5 (2)
119.1 (2)
120.5
N1—C5—C4
N1—C5—Cl51
C4—C5—Cl51
C16—C11—C12
C16—C11—N1
C12—C11—N1
C13—C12—C11
C13—C12—H12
C11—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
C11—C16—C15
C11—C16—H16
C15—C16—H16
120.5
118.8 (2)
C426—C421—C422
N42—C421—C422
C423—C422—C421
C423—C422—H422
C421—C422—H422
C424—C423—C422
C424—C423—H423
C422—C423—H423
C423—C424—C425
C423—C424—H424
C425—C424—H424
C426—C425—C424
C426—C425—H425
C424—C425—H425
C425—C426—C421
C425—C426—H426
C421—C426—H426
119.4 (2)
121.8 (2)
119.8 (2)
120.1
120.3
120.1
120.3 (2)
119.8
121.1 (2)
119.5
119.8
119.5
120.3 (2)
119.9
118.7 (2)
120.6
119.9
120.6
119.7 (2)
120.2
120.8 (2)
119.6
120.2
119.6
120.0 (2)
120.0
120.3 (2)
119.9
120.0
119.9
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—C4
C11—N1—C5—C4
N2—N1—C5—Cl51
C11—N1—C5—Cl51
C3—C4—C5—N1
C41—C4—C5—N1
C3—C4—C5—Cl51
C41—C4—C5—Cl51
C5—N1—C11—C16
N2—N1—C11—C16
C5—N1—C11—C12
N2—N1—C11—C12
C16—C11—C12—C13
−0.2 (3)
−177.6 (2)
0.3 (3)
N1—C11—C12—C13
177.9 (2)
−1.1 (4)
0.8 (4)
C11—C12—C13—C14
C12—C13—C14—C15
C13—C14—C15—C16
C12—C11—C16—C15
N1—C11—C16—C15
179.8 (2)
−0.3 (3)
−179.8 (2)
173.9 (2)
−5.6 (4)
0.0 (3)
−0.2 (4)
0.0 (4)
−177.3 (2)
−0.2 (4)
176.9 (2)
4.1 (4)
C14—C15—C16—C11
C5—C4—C41—N41
C3—C4—C41—N41
177.1 (2)
−176.57 (16)
0.5 (4)
C4—C41—N41—N42
−175.5 (2)
−176.2 (2)
169.6 (2)
−10.3 (3)
−0.8 (4)
179.1 (2)
0.4 (4)
C41—N41—N42—C421
N41—N42—C421—C426
N41—N42—C421—C422
C426—C421—C422—C423
N42—C421—C422—C423
C421—C422—C423—C424
C422—C423—C424—C425
C423—C424—C425—C426
C424—C425—C426—C421
N42—C421—C426—C425
C422—C421—C426—C425
0.1 (3)
−174.1 (2)
176.48 (19)
2.2 (4)
−130.8 (3)
46.0 (3)
0.3 (4)
−0.5 (4)
0.0 (4)
52.0 (3)
−131.2 (2)
0.7 (4)
−179.3 (2)
0.7 (4)
Acta Cryst. (2014). C70, 216-219
sup-4

supplementary materials
Hydrogen-bond geometry (Å, º)
Cg1 and Cg2 represent the centroids of the C421–C426 and C11–C16 rings, respectively.
D—H···A
D—H
H···A
D···A
D—H···A
i
N42—H42···N2
0.88
0.95
0.98
2.26
2.73
2.92
3.100 (3)
3.392 (2)
3.373 (2)
159
127
109
ii
C13—H13···Cg1
C31—H31A···Cg2
iii
Symmetry codes: (i) x+1/2, −y+1/2, z+1/2; (ii) −x+1, −y, −z+1; (iii) −x+1/2, y+1/2, −z+1/2.
Acta Cryst. (2014). C70, 216-219
sup-5

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