Design, synthesis and crystallographic study of novel indole-based cyano derivatives as key building blocks for heteropolycyclic compounds of major complexity

Article abstract of DOI:10.1107/S2053229617015789

A four-stage reaction sequence has been designed and developed for the synthesis of highly functionalized enolate esters as key building blocks for the synthesis of novel heteropolycyclic compounds of potential pharmaceutical value. The sequence starts with simple commercially available indoles and proceeds via 3-(indol-3-yl)-3-oxopropanenitriles, which react with 2-bromobenzaldehyde to form the corresponding chalcones; these are readily reduced to dihydrochalcones, which are in turn acylated to form the enolate esters. The compounds in this sequence have been characterized by IR and ¹H and ¹³C NMR spectroscopy, by mass spectrometry and by elemental analysis. The molecular and supramolecular structures are reported for representative examples, namely (E)-3-(2-bromophenyl)-2-(1-methyl-1H-indole-3-carbonyl)acrylonitrile, C₁₉H₁₃BrN₂O, (Ib), (2RS)-2-(2-bromobenzyl)-3-(1-methyl-1H-indol-3-yl)-3-oxopropanenitrile, C₁₉H₁₅BrN₂O, (IIb), and (2RS)-3-(1-benzyl-1H-indol-3-yl)-2-(2-bromobenzyl)-3-oxopropanenitrile, C₂₅H₁₉BrN₂O, (IIc), the latter two of which crystallize with Z′ = 2, and (E)-1-(1-acetyl-1H-indol-3-yl)-3-(2-bromophenyl)-2-cyanoprop-1-en-1-yl acetate, C₂₂H₁₇BrN₂O, (III), and (E)-1-(1-benzyl-1H-indol-3-yl)-3-(2-bromophenyl)-2-cyanoprop-1-en-1-yl benzoate, C₃₂H₂₃BrN₂O, (IV). The structure of the related chalcone (E)-2-benzoyl-3-(2-bromophenyl)prop-2-enenitrile, (V), has been redetermined at 100 K, where it is monoclinic, as opposed to the triclinic form reported at ambient temperature.Crystal structures have been determined for representative compounds along a four-stage synthetic sequence newly developed for the production from simple indoles of highly functionalized enolate esters as key building blocks for the synthesis of novel heteropolycyclic compounds.

Full text of DOI:10.1107/S2053229617015789

research papers
Design, synthesis and crystallographic study of
novel indole-based cyano derivatives as key
building blocks for heteropolycyclic compounds
of major complexity
ISSN 2053-2296
a
a
a
b
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Andres C. Garcıa, Rodrigo Abonıa, Luz M. Jaramillo-Gomez, Justo Cobo and
Christopher Glidewellc*
Received 3 October 2017
Accepted 30 October 2017
b
aDepartment of Chemistry, Universidad del Valle, AA 25360 Cali, Colombia, Departamento de Quımica Inorganica y
´
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Organica, Universidad de Jaen, 23071 Jaen, Spain, and cSchool of Chemistry, University of St Andrews, Fife KY16 9ST,
Edited by D. S. Yufit, University of Durham,
England
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Scotland. *Correspondence e-mail: cg@st-andrews.ac.uk
Keywords: synthetic design; synthesis; hetero-
cyclic compounds; chalcones; dihydro-
chalcones; enolate esters; crystal structure;
molecular conformation; hydrogen bonding;
supramolecular assembly; privileged substruc-
tures.
A four-stage reaction sequence has been designed and developed for the
synthesis of highly functionalized enolate esters as key building blocks for the
synthesis of novel heteropolycyclic compounds of potential pharmaceutical
value. The sequence starts with simple commercially available indoles and
proceeds via 3-(indol-3-yl)-3-oxopropanenitriles, which react with 2-bromo-
benzaldehyde to form the corresponding chalcones; these are readily reduced to
dihydrochalcones, which are in turn acylated to form the enolate esters. The
CCDC references: 1582887; 1582886;
1582885; 1582884; 1582883; 1582882
1
compounds in this sequence have been characterized by IR and H and 13C
NMR spectroscopy, by mass spectrometry and by elemental analysis. The
molecular and supramolecular structures are reported for representative
examples, namely (E)-3-(2-bromophenyl)-2-(1-methyl-1H-indole-3-carbonyl)-
acrylonitrile, C19H13BrN2O, (Ib), (2RS)-2-(2-bromobenzyl)-3-(1-methyl-1H-in-
dol-3-yl)-3-oxopropanenitrile, C19H15BrN2O, (IIb), and (2RS)-3-(1-benzyl-1H-
indol-3-yl)-2-(2-bromobenzyl)-3-oxopropanenitrile, C25H19BrN2O, (IIc), the
latter two of which crystallize with Z0 = 2, and (E)-1-(1-acetyl-1H-indol-3-yl)-
3-(2-bromophenyl)-2-cyanoprop-1-en-1-yl acetate, C22H17BrN2O, (III), and (E)-
1-(1-benzyl-1H-indol-3-yl)-3-(2-bromophenyl)-2-cyanoprop-1-en-1-yl benzoate,
C32H23BrN2O, (IV). The structure of the related chalcone (E)-2-benzoyl-3-(2-
bromophenyl)prop-2-enenitrile, (V), has been redetermined at 100 K, where
it is monoclinic, as opposed to the triclinic form reported at ambient
temperature.
Supporting information: this article has
supporting information at journals.iucr.org/c
1. Introduction
The indole core is present in a wide range of naturally
occurring and synthetic compounds and it is regarded as one
of the most important ‘privileged substructures’ because of the
wide spectrum of biological activities displayed by many of its
derivatives (Biswal et al., 2012), particularly indole-based
heteropolycyclic compounds, such as the anticancer agent
´
ellipticine (Stiborova et al., 2011), the antihypertensive drug
reserpine (Baumeister et al., 2003) and the anti-obesity agent
evodiamine (Wang et al., 2008). As part of our current
program on the development of novel routes for the synthesis
´
of new heterocyclic derivatives of biological interest (Abonıa,
´
´
2014; Abonıa et al., 2016; Insuasty et al., 2017; Ramırez-Prada
et al., 2017), we now report the design, synthesis and structural
study of novel cyano derivatives, containing the indole core in
their structures, as valuable key intermediates for the
construction of novel indole-based heteropolycyclic com-
pounds of major structural complexity.
# 2017 International Union of Crystallography
1040 https://doi.org/10.1107/S2053229617015789
Acta Cryst. (2017). C73, 1040–1049

research papers
Thus, we describe here a newly designed and developed
four-step sequence for the preparation of the esters (E)-1-(1-
acetyl-1H-indol-3-yl)-3-(2-bromophenyl)-2-cyanoprop-1-en-1-yl
acetate and (E)-1-(1-benzyl-1H-indol-3-yl)-3-(2-bromophen-
yl)-2-cyanoprop-1-en-1-yl benzoate as important synthetic
intermediates starting with the cyanoacetylation of the 1H-
indole [(A), where R = H, Me or PhCH2] (see Scheme 1) by
reaction with cyanoacetic acid in acetic anhydride to provide
the corresponding indolyl(oxo)propanenitriles (B). The inter-
mediates (B) undergo a condensation reaction with 2-bromo-
benzaldehyde under basic conditions to give the corres-
ponding cyanoheterochalcones (I), in yields of 92–95%, and
we report here the structure of the derivative containing an
N-methyl substituent, namely (E)-3-(2-bromophenyl)-2-(1-
methyl-1H-indole-3-carbonyl)acrylonitrile, (Ib).
Acetylation, using acetic anhydride, of the dihydrochalcone
containing an N—H group, compound (IIa), gives the diacetyl
product (E)-1-(1-acetyl-1H-indol-3-yl)-3-(2-bromophenyl)-2-
cyanoprop-1-en-1-yl acetate, (III), while benzoylation using
benzoyl chloride of the N-benzyl analogue (IIc) yielded (E)-1-
(1-benzyl-1H-indol-3-yl)-3-(2-bromophenyl)-2-cyanoprop-1-en-
1-yl benzoate, (IV) (see Scheme 2), and we report here the
structures of both (III) and (IV), which have been designed as
synthetic precursors in order to generate complex hetero-
pentacyclic derivatives.
We also report here a redetermination of the structure of
the chalcone 2-benzoyl-3-(2-bromophenyl)acrylonitrile, (V),
which is related to chalcone (I), but with a simple phenyl
group in place of the substituted indolyl unit. The structure of
this chalcone has been reported recently at ambient
temperature, in the space group P1, with Z0 = 2 (Dhiman et al.,
2016), but the structure was refined only to R1 = 0.157 and
wR2 = 0.341, with S = 1.410. As we had occasion to prepare
this compound at an early stage in the present study, we have
taken the opportunity to collect a new data set at 100 K, where
the compound is monoclinic, space group P21/n with Z0 = 1,
suggesting the possibility of temperature-dependent poly-
morphism.
Reduction of the cyanoheterochalcones using sodium
borohydride forms the dihydro analogues (II) and we report
the structures of two of these, containing either an N-methyl
substituent, i.e. (2RS)-2-(2-bromobenzyl)-3-(1-methyl-1H-in-
dol-3-yl)-3-oxopropanenitrile, (IIb), or an N-benzyl substi-
tuent, i.e. (2RS)-3-(1-benzyl-1H-indol-3-yl)-2-(2-bromobenzyl)-
3-oxopropanenitrile, (IIc). This reduction of the C C double
bond in chalcones (I) is highly specific, with yields in the range
82–93%, and with no evidence for any reduction of either the
carbonyl or the cyano groups.
2. Experimental
2.1. Synthesis and crystallization
The initial indoles (A) (see Scheme 1), where R = H, Me or
PhCH2, are all commercially available. For the synthesis of the
indolyl(oxo)propanenitrile precursors (B), a mixture of the
appropriate indole (1.0 mmol), cyanoacetic acid (1.2 mmol)
and acetic anhydride (2–3 ml) was held at 380 K for 1.5 h, with
stirring throughout, and the progress of the reactions was
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Acta Cryst. (2017). C73, 1040–1049
Garcıa et al.
Novel indole-based cyano derivatives 1041

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monitored using thin-layer chromatography (TLC). When the
indole component had been completely consumed, the solu-
tions were held at 273 K overnight, and the resulting solid
products (B) were collected by filtration and washed with cold
methanol (2 ꢁ 1.0 ml).
Analysis found: C 62.1, H 3.6, N 8.0%; C19H13BrN2O requires:
C 62.5, H 3.6, N 7.7%.
(E)-2-(1-Benzyl-1H-indole-3-carbonyl)-3-(2-bromophenyl)-
acrylonitrile, (Ic): yield 92%, m.p. 453 K; IR (ATR): 3068
1
(C—H), 2225 (CN), 1616 (C O), 1517 (C C); H NMR
3-(1H-Indol-3-yl)-3-oxopropanenitrile: yield 79%, m.p. 516 K;
IR (KBr): 3225 (N—H), 2253 (CN), 1643 (C O), 1581
(C C) cmꢂ1; 1H NMR (DMSO-d6): ꢀ 4.47 (s, CH2), 7.19–7.27
(m, 2H), 7.47–7.52 (m, 1H), 8.10–8.16 (m, 1H), 8.36 (s, 1H),
12.14 (s, 1H, NH); MS (70 eV) m/z (%): 184 (23, M+)
144 (100), 116 (27), 89 (26).
(CDCl3): ꢀ 5.44 (s, 2H), 7.19–7.29 (m, 2H), 7.33–7.45 (m, 7H),
7.50 (td, J = 7.7, 1.2 Hz, 1H), 7.73 (dd, J = 8.0, 1.1 Hz, 1H), 8.19
(dd, J = 7.8, 1.6 Hz, 1H), 8.36 (s, 1H), 8.46–8.63 (m, 2H); 13C
NMR (CDCl3): ꢀ 51.2 (CH2Ph), 110.5, 114.2 (Cq), 114.5 (Cq),
117,4 (CN), 123.1, 123.6, 124.4, 126.1 (Cq), 127.3, 127.6 (Cq),
128.0, 128.5, 129.2, 130.0, 132.7 (Cq), 132.9, 133.4, 135.1 (Cq),
136.6, 137.0 (Cq), 151.9, 178.3 (C O); MS (70 eV) m/z (%):
442/440 (8/8, M+), 361 (12), 234 (5), 91 (100). Analysis found:
C 67.9, H 4.0, N 6.5%; C26H17BrN2O requires: C 68.0, H 3.9, N
6.4%.
For the reduction of chalcones (I) to dihydrochalcones (II),
the appropriate chalcone (I) (1.0 mmol) was dissolved in a
mixture of 1,4-dioxane and methanol (1:4 v/v, 5 ml) and the
solution were stirred vigorously at 343 K as sodium borohy-
dride (1.0 equivalent) was added portionwise. When the
starting chalcone had been consumed, as indicated by TLC,
the solutions were cooled to ambient temperature and the
resulting precipitates were collected by filtration and washed
with cold methanol (2 ꢁ 1.0 ml). No further purification was
necessary.
3-(1-Methyl-1H-indol-3-yl)-3-oxopropanenitrile: yield 73%,
m.p. 426 K; IR (KBr): 3110 (C—H), 2250 (CN), 1643 (C O),
1581 (C C) cmꢂ1; 1H NMR (CDCl3): ꢀ 3.88 (s, 2H, CH2), 3.90
(s, 3H, CH3), 7.31–7.48 (m, 3H), 7.81 (s, 1H), 8.27–8.37 (m,
1H); 13C NMR (CDCl3): ꢀ 29.6 (CH2), 33.9 (CH3), 110.1, 114.2
(Cq), 114.9 (CN), 122.3, 123.5, 124.2, 126.1 (Cq), 136.2, 137.5
(Cq), 180.5 (C O).
3-(1-Benzyl-1H-indol-3-yl)-3-oxopropanenitrtile: yield 72%,
m.p. 397 K; IR (KBr): 3105 (C—H), 2252 (CN), 1662 (C O),
1602 (C C) cmꢂ1; 1H NMR (CDCl3): ꢀ 3.90 (s, 2H, CH2CN),
5.41 (s, 2H, CH2Ph), 7.21 (dd, J = 7.5, 2.1 Hz, 2H), 7.30–7.40
(m, 6H), 7.85 (s, 1H), 8.37 (dd, J = 8.4, 1.7 Hz, 1H), 13C NMR
(CDCl3): ꢀ 29.8 (CH2), 51.1 (CH2Ph), 110.6, 114.7 (Cq), 114.8
(CN), 122.5, 123.6, 124.4, 126.3 (Cq), 127.2, 128.5, 129.2, 135.1
(Cq), 135.2, 137.1 (Cq), 180.6 (C O). Analysis found: C 78.9,
H 5.4, N 9.9%; C18H14N2O requires: C 78.8, H 5.1, N 10.2%.
For the synthesis of chalcones (I), a mixture of the corre-
sponding oxopropanenitrile (B) (1.0 mmol), 2-bromobenz-
aldehyde (1.2 mmol) and triethylamine (1.2 ml) in ethanol
(4 ml) was heated under reflux for 2 h. Once precursor (B) had
been consumed, as shown by TLC, the mixtures were cooled
to ambient temperature and the resulting solid products (I)
were collected by filtration and washed with cold methanol
(2 ꢁ 1.0 ml); no further purification was required.
2-(2-Bromobenzyl)-3-(1H-indol-3-yl)-3-oxopropanenitrile,
(IIa): yield 82%, m.p. 519 K; IR (ATR): 3259 (N—H), 2247
1
(CN), 1616 (C O), 1579 (C C) cmꢂ1; H NMR (DMSO-
d6): ꢀ 3.34–3.37 (m, 2H), 5.06 (t, J = 9.6 Hz, 1H), 7.21–7.29 (m,
3H), 7.38 (t, J = 8.3 Hz, 1H), 7.52 (bt, 2H), 7.64 (d, J = 8.3 Hz,
1H), 8.18 (d, J = 8.4 Hz, 1H), 8.61 (s, 1H), 12.27 (s, 1H, NH).
13C (DMSO-d6): ꢀ 35.4, 39.9, 112.5, 113.7 (Cq), 118.4 (CN),
121.5, 122.5, 123.6, 124.2 (Cq), 125.4 (Cq), 127.8, 128.4, 129.3
(Cq), 131.6, 132.7, 136.0 (Cq), 136.8, 184.3 (C O); MS
(70 eV) m/z (%): 354/352 (2.9/2.5, M+) 144 (100), 273 (43),
116 (23), 89 (13). Analysis found: C 61.1, H 3.9, N 7.8%;
C18H13BrN2O requires: C 61.2, H 3.7, N 7.9%.
(E)-3-(2-Bromophenyl)-2-(1H-indole-3-carbonyl)acrylonitrile,
(Ia): yield 95%, m.p. 522 K; IR (ATR): 3174 (N—H), 2218
(CN), 1631 (C O), 1579 (C C) cmꢂ1; 1H NMR (DMSO-d6):
ꢀ 7.26–7.35 (m, 2H), 7.53 (t, J = 8.1 Hz, 1H), 7.58 (d, J = 8.0 Hz,
1H), 7.64 (t, J = 8.0 Hz, 1H), 7.86 (d, J = 7.9 Hz, 1H), 8.13 (d, J=
7.9 Hz, 1H), 8.22 (d, J = 8.0 Hz, 1H), 8.28 (s, 1H), 8.52 (s, 1H),
12.39 (s, 1H, NH); 13C NMR (DMSO-d6): ꢀ 113.1 (Cq), 113.9,
115.9 (CN), 117.0, 121.8, 122.8 (Cq), 123.1 (Cq), 125.0, 126.5,
128.7 (Cq), 130.6, 131.4, 133.2 (Cq), 133.7, 136.8 (Cq), 137.2,
151.0, 180.9 (C O); MS (70 eV) m/z (%): 352/350 (22/22, M+)
144 (100), 271 (41), 116 (37), 89 (62). Analysis found: C 61.4,
H 3.0, N 8.1%; C18H11BrN2O requires: C 61.6, H 3.2, N 8.0%.
(E)-3-(2-Bromophenyl)-2-(1-methyl-1H-indole-3-carbonyl)-
acrylonitrile, (Ib): yield 92%, m.p. 436 K; IR (ATR): 3018 (C—
2-(2-Bromobenzyl)-3-(1-methyl-1H-indol-3-yl)-3-oxopropane-
nitrile, (IIb): yield 93%, m.p. 419 K; IR (ATR): 3059 (C—H),
;
2249 (CN), 1641 (C O), 1577 (C C) cmꢂ1 1H NMR
(CDCl3): ꢀ 3.38 (dd, J = 13.8, 9.5 Hz, 1H), 3.61 (dd, J = 13.8,
6.1 Hz, 1H), 3.89 (s, 3H, CH3), 4.53 (dd, J = 9.5, 6.1 Hz, 1H),
7.19 (td, J = 7.7, 1.7 Hz, 1H), 7.28–7.50 (m, 5H), 7.61 (dd, J =
8.0, 1.3 Hz, 1H), 7.89 (s, 1H), 8.43 (ddd, J = 6.8, 3.0, 1.5 Hz,
1H); 13C NMR (CDCl3): ꢀ 33.9 (NCH3), 36.5 (CH2), 40.4 (CH),
110, 114.1 (Cq), 117.9 (CN), 122.7, 123.5, 124.2 (Cq), 124.3,
126.5 (Cq), 128.1, 129.4, 132.4, 132.9, 135.8 (Cq), 136.2, 137.6
(Cq), 183.1 (C O); MS (70 eV) m/z (%): 368/366 (2/2, M+),
287 (9), 158 (100), 130 (17), 83 (61). Analysis found: C 62.3, H
4.1, N 8.0%; C19H15BrN2O requires: C 62.1, H 4.1, N 7.6%.
3-(1-Benzyl-1H-indol-3-yl)-2-(2-bromobenzyl)-3-oxopropane-
nitrile, (IIc): yield 91%, m.p. 419 K; IR (ATR): 3059 (C—H),
1
H), 2212 (CN), 1635 (C O), 1581 (C C) cmꢂ1; H NMR
(CDCl3): ꢀ 3.95 (s, 3H, CH3), 7.35–7.57 (m, 5H), 7.75 (dd, J =
8.0, 1.3 Hz, 1H), 8.20 (dd, J = 7.8, 1.7 Hz, 1H), 8.35 (s, 1H),
8.44–8.54 (m, 1H), 8.58 (s, 1H); 13C NMR (CDCl3): 34.0 (CH3),
110.0, 113.9 (Cq), 114.1 (Cq), 117.8 (CN), 123.1, 123.5, 124.3,
126.1 (Cq), 127.4 (Cq), 128.0, 130.0, 132.8 (Cq), 132.9, 133.5,
137.2, 137.4 (Cq), 152.2, 178.6 (C O); MS (70 eV) m/z (%):
366/364 (38/40, M+), 285 (100), 236 (19), 158 (66), 152 (35).
2250 (CN), 1641 (C O), 1568 (C C) cmꢂ1 1H NMR
;
(CDCl3): ꢀ 3.34 (dd, J = 13.7, 9.8 Hz, 1H), 3.55 (dd, J = 13.6,
6.0 Hz, 1H), 4.50 (dd, J = 9.8, 6.0 Hz, 1H), 5.29–5.45 (m, 2H),
7.12–7.32 (m, 4H), 7.33–7.47 (m, 7H), 7.56 (dd, J = 8.0, 1.2 Hz,
1H), 7.89 (s, 1H), 8.42–8.50 (m, 1H); 13C (CDCl3): ꢀ 37.1
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1042 Garcıa et al. Novel indole-based cyano derivatives
Acta Cryst. (2017). C73, 1040–1049

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(CH2), 40.7 (CH), 51.1 (CH2Ph), 110.4, 114.5 (Cq), 117.6 (CN),
122.8, 123.7, 124.2 (Cq), 124.4, 126.7 (Cq), 127.6, 128.1, 128.7,
129.3, 129.4, 132.4, 132.9, 134.7 (Cq), 135.3, 135.6 (Cq), 137.3
(Cq), 183.6 (C O); MS (70 eV) m/z (%): 444/442 (8/8, M+),
234 (15), 149 (8), 91 (100). Analysis found: C 66.8, H 4.3, N
6.9%; C25H19BrN2O requires: C 67.7, H 4.3, N 6.3%.
(CDCl3): ꢀ 7.43 (t, J = 7.7 Hz, 1H), 7.48–7.63 (m, 3H), 7.65–7.79
(m, 2H), 7.88–8.03 (m, 2H), 8.27 (d, J = 7.9 Hz, 1H), 8.38 (s,
1H); 13C NMR (CDCl3): ꢀ 113.7 (Cq), 115.8 (CN), 126.5 (Cq),
128.2, 128.9, 129.6, 130.2, 132.2 (Cq), 133.6, 133.7, 133.8, 135.5
(Cq), 154.1, 188.7 (C O).
Crystals of compounds (Ib), (IIb), (IIc) and (V) suitable for
single-crystal X-ray diffraction were grown by slow evapora-
tion, at ambient temperature and in the presence of air, of
solutions in chloroform; crystals of (III) and (IV) were grown,
under similar conditions from solutions in acetic acid/acetic
anhydride and dichloromethane/hexane (1:1 v/v), respectively.
For the synthesis of (E)-1-(1-acetyl-1H-indol-3-yl)-3-(2-
bromophenyl)-2-cyanoprop-1-en-1-yl acetate, (III), a mixture
of dihydrochalcone (IIa) (1.4 mmol) and acetic anhydride
(5 ml) was stirred at 373 K. When the dihydrochalcone had all
been consumed, as indicated by TLC, the residual acetyl
compounds were removed under reduced pressure and the
resulting solid was purified by flash chromatography on silica
gel using hexane/diethyl ether (60/40, then 50/50, then 60/40
v/v) as eluent to give (III): yield 56%, m.p. 424 K; IR (ATR):
3007 (C—H), 2242 (CN), 1721 (C O), 1680 (C O), 1533
(C C) cmꢂ1; 1H NMR (CDCl3): ꢀ 2.30 (s, 3H, CH3), 2.73 (s,
3H, CH3), 3.89 (s, 2H, CH2), 7.22 (td, J = 7.7, 1.8 Hz, 1H), 7.32–
7.50 (m, 4H), 7.57–7.78 (m, 2H), 8.18 (s, 1H), 8.46–8.60 (m,
1H), 13C NMR (CDCl3): ꢀ 20.7 (CH3), 23.9 (CH3), 34.6 (CH2),
101.9 (Cq), 114.5 (Cq), 117.2, 118.1 (CN), 119.7, 124.5 (Cq),
124.6, 126.2, 127.3 (Cq), 127.8, 127.9, 129.2, 130.7, 133.2, 135.5
(Cq), 135.6 (Cq), 154.9 (Cq), 167.0 (OC O), 168.6 (NC O);
MS (70 eV) m/z (%): 438/436 (12/12, M+), 396/394 (60/59),
273 (100), 186 (14). Analysis found: C60.7, H 4.1, N 6.2%;
C22H17BrN2O3 requires: C 60.4, H 3.9, N 6.4%.
2.2. Refinement
Crystal data, data collection and structure refinement
details are summarized in Table 1. For all the compounds
described here, the atom labelling is based on the systematic
chemical names. Several low-angle reflections which had been
attenuated by the beam stop were omitted from the refine-
ments; thus, for (III), 120 and 122, and for (V), 110. All H
atoms were located in difference maps and then treated as
riding atoms in geometrically idealized positions, with C—H =
˚
0.95 (aromatic), 0.98 (CH3), 0.99 (CH2) or 1.00 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. In the final analysis of variance for (IIc),
2
there was a large value, i.e. 3.292, of K = mean(Fo )/mean(Fc2)
For the synthesis of (E)-1-(1-benzyl-1H-indol-3-yl)-3-(2-
bromophenyl)-2-cyanoprop-1-en-1-yl benzoate, (IV), a mix-
ture of dihydrochalcone (IIc) (1.0 mmol), chloroform (7.0 ml)
and triethylamine (5.0 mmol) was stirred for 20 min at
ambient temperature. Benzoyl chloride (4.0 mmol) was then
added dropwise and stirring was continued until TLC showed
that the dihydrochalcone had all been consumed. The mixture
was then extracted with a saturated aqueous solution of
sodium hydrogen carbonate (2 ꢁ 3 ml) and the organic phase
was dried over anhydrous magnesium sulfate. The solvent was
removed under reduced pressure and the crude product (IV)
was purified by flash chromatography using dichloromethane/
hexane (45/55, then 50/50, then 55/45 and finally 60/40 v/v) to
give an 87/13 mixture of the E and Z isomers. Yield 88%, m.p.
394–395 K; IR (ATR): 3067 (C—H), 2210 (CN), 1737 (C O),
1560 (C C), 1238 (C—O—C) cmꢂ1; 1H NMR (CDCl3): ꢀ 3.90
(s, 2H, CH2Ar), 5.39 (s, 2H, CH2Ph), 6.89–7.19 (m, 16H), 8.05–
8.32 (m, 3H); 13C NMR (CDCl3): ꢀ 34.7 (CH2Ar), 50.9
(CH2Ph), 96.8 (Cq), 108.3 (Cq), 110.8, 119.3 (CN), 120.5, 121.6,
123.0, 124.7 (Cq), 126.1 (Cq), 127.0, 127.8, 128.1, 128.2 (Cq),
128.8, 128.9 (ꢁ2 C, CH and Cq), 129.0, 130.4, 130.8, 131.9,
133.0, 134.2, 135.9 (Cq), 136.3 (Cq), 157.2 (Cq), 163.1
(OC O); MS (70 eV) m/z (%): 547/545 (32/30, M+), 234 (40),
105 (90), 90 (100). Analysis found: C 70.0, H 4.5, N 5.0%;
C32H21BrN2O requires: C 70.2, H 4.2, N 5.1%.
for the group of 1060 very weak reflections having Fc/Fc(max)
in the range 0.000 < Fc/Fc(max) < 0.010; the corresponding
value for (III) was 1.727 for 440 reflections having Fc/Fc(max)
in the range 0.000 < Fc/Fc(max) < 0.008, and for (IV) was 1.612
for 728 reflections having Fc/Fc(max) in the range 0.000 <
Fc/Fc(max) < 0.014.
3. Results and discussion
Chalcone (Ib) and esters (III) and (IV) all crystallize with Z0 =
1, but dihydrochalcones (IIb) and (IIc) both crystallize with
Z0 = 2, albeit in different space groups, viz. P21/n and P1,
respectively. For each of (IIb) and (IIc), examination of the
atomic coordinates using PLATON (Spek, 2009) revealed no
additional symmetry, although the two molecules in the
selected asymmetric unit of (IIc) are approximately, but not
exactly, related by a noncrystallographic inversion centre at
3
4
3
4
(14, , ).
In each of the molecules in the structures reported here,
there is a series of substituents, i.e. benzyl or benzylidene,
carbonyl or carboxylate, cyano, and indolyl or phenyl,
disposed about a central C—C bond, and the relative orien-
tations of these substituents, as indicated by the relevant
torsion angles (Table 2), show some interesting variations.
Thus, for example, the carbonyl and cyano substituents in
compounds (Ib) and (V) adopt mutually trans and cis
arrangements, respectively; likewise, in both (III) and (IV),
these two substituents are trans to one another, whereas these
substituents exhibit synclinal arrangements in all of the inde-
pendent molecules of (IIb) and (IIc). In general, the bromo
(E)-2-Benzoyl-3-(2-bromophenyl)acrylonitrile, (V), was ob-
tained as an orange solid in a manner similar to that used for
the the preparation of chalcones (I), but using benzoylaceto-
nitrile and 2-bromobenzaldehyde. Yield 52%, m.p. 399–400 K
(399–401 K; Dhiman et al., 2016); IR (ATR): 3088 (C—H),
2225 (CN), 1651 (C O), 1577 (C C) cmꢂ1. 1H NMR
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Table 1
Experimental details.
(Ib)
(IIb)
(IIc)
Crystal data
Chemical formula
Mr
C19H13BrN2O
365.22
C19H15BrN2O
367.24
C25H19BrN2O
443.32
Crystal system, space group
Temperature (K)
a, b, c (A)
ꢁ, ꢂ, ꢃ (ꢃ)
Triclinic, P1
100
9.188 (5), 9.308 (5), 10.887 (5)
113.56 (2), 90.782 (18),
116.173 (16)
745.3 (7)
2
Mo Kꢁ
2.76
Monoclinic, P21/n
100
13.728 (6), 14.901 (6), 15.507 (6)
90, 92.165 (19), 90
Triclinic, P1
100
10.912 (4), 12.544 (8), 15.583 (7)
89.23 (4), 79.49 (3), 73.20 (3)
˚
3
˚
V (A )
3170 (2)
8
Mo Kꢁ
2.60
2006.0 (18)
4
Mo Kꢁ
2.07
Z
Radiation type
ꢄ (mmꢂ1
Crystal size (mm)
)
0.33 ꢁ 0.21 ꢁ 0.19
0.40 ꢁ 0.30 ꢁ 0.10
0.22 ꢁ 0.21 ꢁ 0.10
Data collection
Diffractometer
Absorption correction
Bruker D8 Venture
Multi-scan (SADABS; Bruker,
2016)
Bruker D8 Venture
Multi-scan (SADABS; Bruker,
2016)
Bruker D8 Venture
Multi-scan (SADABS; Bruker,
2016)
Tmin, Tmax
0.446, 0.591
46632, 3467, 3296
0.489, 0.771
79963, 7297, 5456
0.737, 0.813
96931, 9244, 6872
No. of measured, independent and
observed [I > 2ꢅ(I)] reflections
Rint
0.040
0.653
0.090
0.651
0.112
0.651
ꢂ1
˚
(sin ꢆ/ꢇ)max (A
)
Refinement
R[F2 > 2ꢅ(F2)], wR(F2), S
No. of reflections
No. of parameters
0.020, 0.049, 1.07
3467
209
0.034, 0.072, 1.05
7297
417
0.042, 0.084, 1.02
9244
523
H-atom treatment
H-atom parameters constrained
w = 1/[ꢅ2(Fo2) + (0.0202P)2
+ 0.6373P]
H-atom parameters constrained
w = 1/[ꢅ2(Fo2) + (0.0217P)2
+ 3.7392P]
H-atom parameters constrained
w = 1/[ꢅ2(Fo2) + (0.025P)2
+ 2.2423P]
2
2
2
where P = (Fo + 2Fc2)/3
where P = (Fo + 2Fc2)/3
where P = (Fo + 2Fc2)/3
ꢂ3
˚
Áꢈmax, Áꢈmin (e A
)
0.40, ꢂ0.39
0.54, ꢂ0.76
0.40, ꢂ0.57
(III)
(IV)
(V)
Crystal data
Chemical formula
Mr
C22H17BrN2O3
437.28
C32H23BrN2O2
547.42
C16H10BrNO
312.15
Crystal system, space group
Temperature (K)
Monoclinic, C2/c
100
19.406 (9), 8.773 (4), 23.028 (9)
90, 103.318 (15), 90
3815 (3)
8
Mo Kꢁ
2.18
Monoclinic, P21/c
100
14.886 (4), 8.129 (3), 21.432 (6)
90, 104.638 (12), 90
2509.3 (14)
4
Mo Kꢁ
1.67
Monoclinic, P21/n
100
10.986 (4), 8.977 (4), 13.209 (5)
90, 97.140 (17), 90
1292.6 (9)
4
Mo Kꢁ
3.17
˚
a, b, c (A)
ꢁ, ꢂ, ꢃ (ꢃ)
3
˚
V (A )
Z
Radiation type
ꢄ (mmꢂ1
Crystal size (mm)
)
0.42 ꢁ 0.32 ꢁ 0.24
0.21 ꢁ 0.12 ꢁ 0.12
0.27 ꢁ 0.26 ꢁ 0.23
Data collection
Diffractometer
Absorption correction
Bruker D8 Venture
Multi-scan (SADABS; Bruker,
2016)
Bruker D8 Venture
Multi-scan (SADABS; Bruker,
2016)
Bruker D8 Venture
Multi-scan (SADABS; Bruker,
2016)
Tmin, Tmax
0.420, 0.594
49228, 4379, 3435
0.676, 0.818
87392, 6999, 5828
0.366, 0.482
30048, 2985, 2754
No. of measured, independent and
observed [I > 2ꢅ(I)] reflections
Rint
0.057
0.650
0.074
0.693
0.036
0.652
ꢂ1
˚
(sin ꢆ/ꢇ)max (A
)
Refinement
R[F2 > 2ꢅ(F2)], wR(F2), S
No. of reflections
No. of parameters
0.056, 0.136, 1.08
4379
255
0.036, 0.086, 1.05
6999
334
0.022, 0.053, 1.11
2985
172
H-atom treatment
H-atom parameters constrained
w = 1/[ꢅ2(Fo2) + (0.0427P)2
+ 18.903P]
H-atom parameters constrained
w = 1/[ꢅ2(Fo2) + (0.0363P)2
+ 2.1078P]
H-atom parameters constrained
w = 1/[ꢅ2(Fo2) + (0.023P)2
+ 0.9733P]
2
2
2
where P = (Fo + 2Fc2)/3
where P = (Fo + 2Fc2)/3
where P = (Fo + 2Fc2)/3
ꢂ3
˚
Áꢈmax, Áꢈmin (e A
)
0.80, ꢂ1.90
Computer programs: APEX3 (Bruker, 2016), SAINT (Bruker, 2016), SIR92 (Altomare et al., 1994), SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).
0.46, ꢂ0.94
0.34, ꢂ0.52
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˚
plane of the central spacer by 0.581 (2) and 0.507 (2) A,
respectively. The molecule of compound (Ib) thus exhibits no
internal symmetry and so it is conformationally chiral; the
centrosymmetric space group (Table 1) indicates that equal
numbers of the two conformational enantiomers are present.
The bond lengths present no unusual features (cf. Allen et al.,
1987); in particular, they provide no evidence for any delo-
calization of charge from indole atom N21 onto carbonyl atom
O28.
The molecules of dihydrochalcones (IIb) and (IIc) (Figs. 2
and 3) both contain a stereogenic centre. For each of these
compounds, the asymmetric units were selected such that the
type 1 molecule, containing atom Br12, has an R configuration
at atom C12, while the type 2 molecule, containing atom Br22,
has an S configuration at atom C22. This ensures that the two
independent molecules in the selected asymmetric units are
linked within the asymmetric units by hydrogen bonds having
an aromatic C—H unit as the donor (Table 3), and having an
O- or N-atom acceptor, respectively. The centrosymmetric
space groups for (IIb) and (IIc) (Table 1) confirm that each of
Figure 1
The molecular structure of compound (Ib), showing the atom-labelling
scheme. Displacement ellipsoids are drawn at the 50% probability level.
substituents occupy locations remote from the cyano substi-
tuents (cf. Figs. 1–6).
In chalcone (Ib) (Fig. 1), the central spacer unit comprising
atoms N1/C1–C3/C28/C31 is planar, as expected, but the two
cyclic substituents are both twisted out of this plane. Thus, the
dihedral angle between the planes of the spacer unit and the
phenyl ring is 39.45 (6)ꢃ, while the dihedral angle between the
spacer and the indolyl unit is 36.23 (5)ꢃ, with a dihedral angle
between the indolyl and phenyl ring systems of 75.25 (4)ꢃ;
hence, atoms C23 and O28 are displaced on either side the
Figure 2
Figure 3
The structures of the two independent molecules in the structure of
compound (IIb), showing the atom-labelling scheme for (a) a type 1
molecule having the (2R)-configuration and (b) a type 2 molecule having
the (2S)-configuration. Displacement ellipsoids are drawn at the 50%
probability level.
The structures of the two independent molecules in the structure of
compound (IIc), showing the atom-labelling scheme for (a) a type 1
molecule having the (2R)-configuration and (b) a type 2 moleucle having
the (2S)-configuration. Displacement ellipsoids are drawn at the 50%
probability level.
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Table 2
Selected torsion angles (ꢃ).
(Indolyl)C—C—
C—C(N)a
O—C—
C—C(N)b
(NC)C—C—
C—C(Br)c
(Ib)
ꢂ29.8 (2)
141.1 (2)
ꢂ139.9 (2)
151.1 (2)
ꢂ150.1 (2)
6.6 (5)
1.0 (2)
ꢂ153.71 (14)
152.77 (14)
ꢂ39.4 (3)
41.5 (3)
147.66 (16)
ꢂ77.7 (3)
50.5 (3)
(IIb), x = 1
(IIb), x = 2
(IIc), x = 1
(IIc), x = 2
(III)
ꢂ31.9 (3)
ꢂ93.1 (3)
34.5 (3)
97.4 (3)
ꢂ167.3 (3)
174.10 (13)
27.4 (2)
171.0 (3)
ꢂ98.04 (10)
134.3 (16)
(IV)
(V)
Notes: (a) In (Ib), C23—C28—C2—C1; in (IIb) and (IIc), Cx33 Cx34—Cx2—Cx1 (x = 1
or 2); in (III) and (IV), C13—C1—C2—C21; in (V), C21—C27—C2—C1. (b) In (Ib),
O28—C28—C2—C1; in (IIb) and (IIc), Ox23—Cx3—Cx2—Cx1 (x = 1 or 2); in (III) and
(IV), O11—C1—C2—C21; in (V), O27—C27—C2—C1. (b) In (Ib) and (V), C2—C3—
C31—C32; in (IIb) and (IIc), Cx2—Cx27—Cx21—Cx22 (x = 1 or 2); in (III) and (IV),
C2—C3—C31—C32.
Table 3
Hydrogen bonds and short intra- and intermolecular contacts (A, ).
ꢃ
˚
Figure 4
The molecular structure of compound (III), showing the atom-labelling
scheme. Displacement ellipsoids are drawn at the 30% probability level.
Cg1, Cg2 and Cg3 represent the centroids of the C31–C36, C13A/C14–C17/
C17A and C181–C196 rings, respectively.
Compound D—Hꢄ ꢄ ꢄA
D—H Hꢄ ꢄ ꢄA Dꢄ ꢄ ꢄA
D—Hꢄ ꢄ ꢄA
these compounds has crystallized as a racemic mixture, as
expected, since the synthetic pathway (see Scheme 1) involves
no reagents capable of promoting enantioselectivity. In each
of the independent molecules of compound (IIb), the atoms of
the benzyl unit are effectively coplanar, as are those of the
indolyl-C( O)—C unit; the maximum deviation of any of the
(Ib)
(IIb)
(IIc)
C24—H24ꢄ ꢄ ꢄCg1i
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
2.77
2.57
2.62
2.57
2.45
2.76
2.92
2.97
2.55
2.59
2.73
2.69
3.544 (3) 139
C125—H125ꢄ ꢄ ꢄO23
C225—H225ꢄ ꢄ ꢄN11
C231—H23Aꢄ ꢄ ꢄO23ii
C17—H17ꢄ ꢄ ꢄO18iii
C35—H35ꢄ ꢄ ꢄCg2iv
C36—H36ꢄ ꢄ ꢄCg3v
C183—H183ꢄ ꢄ ꢄCg1vi
C33—H33ꢄ ꢄ ꢄN1i
3.446 (3) 153
3.304 (4) 129
3.415 (4) 143
3.133 (5) 129
3.582 (5) 146
3.739 (2) 146
2.807 (2) 148
3.425 (3) 154
3.459 (2) 153
3.431 (2) 131
3.506 (2) 144
(III)
(IV)
(V)
˚
component atoms from this latter plane is 0.0447 (19) A for
˚
atom C12, with an r.m.s. deviation of 0.026 A in the type 1
˚
molecule and of 0.024 (2) A for atom C22 with an r.m.s.
˚
deviation of 0.012 A in the type 2 molecule. Moreover, these
C36—H36ꢄ ꢄ ꢄO27vii
C3—H3ꢄ ꢄ ꢄCg1vi
C23—H23ꢄ ꢄ ꢄCg1viii
Symmetry codes: (i) x, y + 1, z; (ii) ꢂx ꢂ 1, ꢂy + 2, ꢂz + 2; (iii) ꢂx + 1, ꢂy + 1, ꢂz; (iv)
ꢂx + 32, y + 12, ꢂz + 12; (v) ꢂx + 1, ꢂy + 2, ꢂz + 1; (vi) ꢂx + 1, ꢂy + 1, ꢂz + 1; (vii) ꢂx + 1,
1
2
ꢂy, ꢂz + 1; (viii) x + 12, ꢂy + 21, z ꢂ
.
two units are almost parallel in each molecule, with dihedral
angles between them of only 5.78 (5) and 6.10 (5)ꢃ in the
molecules of types 1 and 2, respectively (Fig. 2). Entirely
similar comments apply to the molecules of compound (IIc)
(Fig. 3), where the dihedral angles between the planes of the
benzyl and indolylcarbonyl units are 11.91 (6) and 13.09 (7)ꢃ
in the molecules of types 1 and 2, respectively; the dihedral
Figure 5
The molecular structure of compound (IV), showing the atom-labelling
scheme. Displacement ellipsoids are drawn at the 50% probability level.
Figure 6
The molecular structure of compound (V), showing the atom-labelling
scheme. Displacement ellipsoids are drawn at the 50% probability level.
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dihedral angles between the indolyl and bromobenzyl units in
(III) and (IV) are 36.91 (9) and 79.27 (4)ꢃ, respectively.
As noted above, the structure of compound (V) has recently
been reported at ambient temperature and refined in the
space group P1 with Z0 = 2 (Dhiman et al., 2016). Comparison
of the atomic coordinates for corresponding pairs of atoms in
this structure showed that the two molecules in the selected
asymmetric unit are very precisely related by a noncrystallo-
graphic 21 screw axis along (x, 34, 34), and a detailed examination
of this structure for additional symmetry elements (PLATON;
Spek, 2009) found a 100% fit to space group P21/n with Z0 = 1,
˚
˚
in a unit cell with dimensions a = 10.896 A, b = 8.952 A, c =
ꢃ
˚
13.292 A and ꢂ = 96.15 , very similar to the monoclinic unit
cell found here at 100 K. Although a request to the authors of
the original report for a copy of their .hkl file proved fruitless,
we are nonetheless reasonably confident that compound (V)
does not, in fact, exhibit temperature-dependent poly-
morphism, but that the ambient-temperature structure was
refined in the wrong space group. The high values of the R
factors and the goodness-of-fit parameter resulting from the
ambient temperature refinement are probably, in large part, a
consequence of the rather indifferent quality of the data set
used, where Rint = 0.386. At 100 K, the conformation of
compound (V) resembles that of (Ib), with dihedral angles
between the central spacer unit on the one hand and the
substituted and unsubstituted phenyl rings on the other of
48.63 (6) and 51.91 (7)ꢃ, respectively.
The supramolecular assembly in compounds (Ib), (IIb) and
(IIc) is very simple. In the structure of (Ib), a single C—
Hꢄ ꢄ ꢄꢉ(arene) hydrogen bond (Table 3) links molecules
related by translation into simple chains running parallel to
the [010] direction, while in (IIb), the two molecules in the
selected asymmetric unit are linked by a C—Hꢄ ꢄ ꢄO hydrogen
bond, but there are no direction-specific interactions between
adjacent bimolecular units. The two independent molecules in
compound (IIc) are linked within the selected asymmetric unit
by a C—Hꢄ ꢄ ꢄN hydrogen bond and pairs of type 2 molecules
are linked by paired C—Hꢄ ꢄ ꢄO hydrogen bonds to form a
cyclic centrosymmetric R22(14) ring, so forming a four-mol-
ecule aggregate in which the type 1 molecules are simply
pendent from the central ring (Fig. 7).
Figure 7
Part of the crystal structure of compound (IIc), showing the formation of
a centrosymmetric four-molecule aggregate. For the sake of clarity, the
unit-cell outline and H atoms bonded to those C atoms not involved in the
motif shown have all been omitted. The Br atoms marked with an asterisk
(*) are at the symmetry position (ꢂx ꢂ 1, ꢂy + 2, ꢂz + 2).
angles between the planes of the indolyl units and the C atoms
of the N-benzyl units are 82.52 (7) and 82.07 (7)ꢃ, respectively.
Atoms C1, C2, C3, C21 and N21 in the central spacer unit of
compound (III) are coplanar, but substituent atoms O11 and
C13 are displaced on either side of this plane by 0.283 (4) and
0.087 (6) A, respectively, indicating a slight twist around the
C1 C2 double bond. In contrast, in compound (IV), both of
these atoms are displaced to the same side of the C1–C3/C21/
˚
˚
N21 plane by 0.114 (2) and 0.038 (3) A, respectively. The
In contrast to the rather simple assembly in compounds
(Ib), (IIb) and (IIc), that in compound (III) is more complex,
and a combination of C—Hꢄ ꢄ ꢄO and C—Hꢄ ꢄ ꢄꢉ(arene)
hydrogen bonds links the molecules into sheets. Inversion
related pairs of molecules are linked by symmetry-related C—
Hꢄ ꢄ ꢄO hydrogen bonds to form a cyclic centrosymmetric
dimer, characterized by an R22(12) motif (Etter, 1990; Etter et
1
al., 1990; Bernstein et al., 1995) and centred at (12, , 0). This
2
dimeric unit is directly linked by the C—Hꢄ ꢄ ꢄꢉ hydrogen bond
1
to four other dimers centred respectively at (0, 0, ꢂ ), (0, 1,
2
1
2
1
2
1
2
ꢂ ), (1, 0, ) and (1, 1, ), so forming a sheet lying parallel to
(101) (Fig. 8). Two sheets of this type, related to one another
by the C-centring operation pass through each unit cell, but
there are no direction-specific interactions between adjacent
sheets. Two independent C—Hꢄ ꢄ ꢄꢉ(arene) hydrogen bonds
link the molecules of compound (IV) into a chain of centro-
Figure 8
A stereoview of part of the crystal structure of compound (III), showing
the formation of a hydrogen-bonded sheet lying parallel to (101). For the
sake of clarity, H atoms not involved in the motifs shown have been
omitted.
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Figure 11
A stereoview of part of the crystal structure of compound (V), showing
the formation of a hydrogen-bonded chain running parallel to the [101]
direction. Hydrogen bonds are shown as dashed lines and, for the sake of
clarity, H atoms not involved in the motifs shown have been omitted.
Figure 9
Part of the crystal structure of compound (IV), showing a hydrogen-
bonded chain of rings running parallel to [010]. For the sake of clarity, H
atoms not involved in the motifs shown have been omitted.
The supramolecular assembly of compound (V) was not
mentioned in the original report (Dhiman et al., 2016) and we
therefore discuss it here. Four hydrogen bonds are present
(Table 3) and these together link the molecules into very
complex sheets, whose formation can, however, be readily
analysed in terms of two simpler one-dimensional substruc-
tures (Ferguson et al., 1998a,b; Gregson et al., 2000). The C—
Hꢄ ꢄ ꢄN and C—Hꢄ ꢄ ꢄO hydrogen bonds combine to form a
ribbon running parallel to the [010] direction, in which R22(14)
rings centred at (12, n, 21) alternate with R44(22) rings centred at
(12, n + 12, 12), where n represents an integer in each case (Fig. 10).
There are also two C—Hꢄ ꢄ ꢄꢉ(arene) hydrogen bonds present
in the structure, both involving the same aryl ring as the
acceptor with the two donor group approaching opposite faces
of the ring, such that the H3iꢄ ꢄ ꢄCg2ꢄ ꢄ ꢄH23ii angle is 174ꢃ
symmetric rings running parallel to the [010] direction, in
which two types ring alternate, involving the C-benzyl and N-
benzyl rings, respectively (Table 3 and Fig. 9).
Figure 10
Part of the crystal structure of compound (V), showing the formation of a
ribbon containing alternating R22(14) and R44(22) rings, running parallel to
the [010] direction. Hydrogen bonds are shown as dashed lines and, for
the sake of clarity, H atoms not involved in the motifs shown have been
omitted. The Br atoms marked with an asterisk (*), a hash (#) or a dollar
sign ($) are at the symmetry positions (x, y + 1, z), (ꢂx + 1, ꢂy + 1, ꢂz + 1)
and (ꢂx + 1, ꢂy, ꢂz + 1), respectively.
Figure 12
Part of the crystal structure of compound (V), showing the formation of a
hydrogen-bonded sheet lying parallel to (101). Hydrogen bonds are
shown as dashed lines and, for the sake of clarity, H atoms not involved in
the motifs shown have been omitted.
ꢀ
´
1048 Garcıa et al. Novel indole-based cyano derivatives
Acta Cryst. (2017). C73, 1040–1049

research papers
1
2
[symmetry codes: (i) ꢂx + 1, ꢂy + 1, ꢂz + 1; (ii) x ꢂ , ꢂy + 12,
Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A.,
Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst.
27, 435.
1
2
z + ]. One of these, that involving atom H3, lies within the
ribbon generated by the C—Hꢄ ꢄ ꢄN and C—Hꢄ ꢄ ꢄO hydrogen
bonds, while the second, involving atom H23, links R22(14)
dimers generated by paired C—Hꢄ ꢄ ꢄO hydrogen bonds into a
chain running parallel to the [101] direction (Fig. 11). The
combination of the ribbon along [010] and the chain along
[101] generates a complex sheet structure lying parallel to
(101) (Fig. 12).
Baumeister, A. A., Hawkins, M. F. & Uzelac, S. M. (2003). J. Hist.
Neurosci. 12, 207–220.
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew.
Chem. Int. Ed. Engl. 34, 1555–1573.
Biswal, S., Sahoo, U., Sethy, S., Kumar, H. K. S. & Banerjee, M. (2012).
Asian J. Pharm. Clin. Res. 5, 1–6.
Bruker (2016). APEX3, SAINT and SADABS. Bruker AXS Inc.,
Madison, Wisconsin, USA.
Dhiman, S., Saini, H. K., Nandwana, N. K., Kumar, D. & Kumar, A.
(2016). RSC Adv. 6, 23987–23994.
Etter, M. C. (1990). Acc. Chem. Res. 23, 120–126.
Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46,
256–262.
Acknowledgements
´
The authors thank the Centro de Instrumentacion Cientıfico-
Tecnica of the Universidad de Jaen and the staff for the data
´
´
´
Ferguson, G., Glidewell, C., Gregson, R. M. & Meehan, P. R. (1998a).
Acta Cryst. B54, 129–138.
collection.
Ferguson, G., Glidewell, C., Gregson, R. M. & Meehan, P. R. (1998b).
Acta Cryst. B54, 139–150.
Funding information
Gregson, R. M., Glidewell, C., Ferguson, G. & Lough, A. J. (2000).
Acta Cryst. B56, 39–57.
Funding for this research was provided by: COLCIENCIAS
´
and Universidad del Valle, Consejerıa de Economıa, Innova-
cion, Ciencia y Empleo (Junta de Andalucıa, Spain) and the
´
´
Insuasty, D., Abonıa, R., Insuasty, B., Quiroga, J., Laali, K. K.,
Nogueras, M. & Cobo, J. (2017). ACS Comb. Sci. 19, 555–563.
´
´
´
Universidad de Jaen.
´ ´
Ramırez-Prada, J., Robledo, S. M., Velez, I. D., Crespo, M. P.,
´
Quiroga, J., Abonıa, R., Montoya, A., Svetaz, L., Zacchino, S. &
Insuasty, B. (2017). Eur. J. Med. Chem. 131, 237–254.
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8.
Spek, A. L. (2009). Acta Cryst. D65, 148–155.
References
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Abonıa, R. (2014). Curr. Org. Synth. 11, 773–786.
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Abonıa, R., Castillo, J., Insuasty, B., Quiroga, J., Sortino, M.,
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Eckschlager, T., Kizek, R. & Frei, E. (2011). Interdiscip. Toxicol. 4,
98–105.
Nogueras, M. & Cobo, J. (2016). Arab. J. Chem. doi:org/10.1016/
j.arabjc.2016.11.016.
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& Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–S19.
Wang, T., Wang, Y., Kontani, Y., Kobayashi, Y., Sato, Y., Mori, N. &
Yamashita, H. (2008). Endocrinology, 149, 358–366.
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Acta Cryst. (2017). C73, 1040–1049
Garcıa et al.
Novel indole-based cyano derivatives 1049

supporting information
supporting information
Acta Cryst. (2017). C73, 1040-1049 [https://doi.org/10.1107/S2053229617015789]
Design, synthesis and crystallographic study of novel indole-based cyano
derivatives as key building blocks for heteropolycyclic compounds of major
complexity
Andrés C. García, Rodrigo Abonía, Luz M. Jaramillo-Gómez, Justo Cobo and Christopher
Glidewell
Computing details
For all structures, data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT
(Bruker, 2016); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure:
SHELXL2014 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for
publication: SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).
(E)-3-(2-Bromophenyl)-2-(1-methyl-1H-indole-3-carbonyl)acrylonitrile (Ib)
Crystal data
C19H13BrN2O
Z = 2
Mr = 365.22
Triclinic, P1
F(000) = 368
Dx = 1.628 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 3467 reflections
θ = 2.5–27.7°
a = 9.188 (5) Å
b = 9.308 (5) Å
c = 10.887 (5) Å
α = 113.56 (2)°
β = 90.782 (18)°
γ = 116.173 (16)°
V = 745.3 (7) Å3
µ = 2.76 mm−1
T = 100 K
Block, yellow
0.33 × 0.21 × 0.19 mm
Data collection
Bruker D8 Venture
diffractometer
Radiation source: INCOATEC high brilliance
microfocus sealed tube
46632 measured reflections
3467 independent reflections
3296 reflections with I > 2σ(I)
Rint = 0.040
Multilayer mirror monochromator
φ and ω scans
Absorption correction: multi-scan
(SADABS; Bruker, 2016)
θmax = 27.7°, θmin = 2.5°
h = −11→11
k = −12→12
l = −14→14
T
min = 0.446, Tmax = 0.591
Refinement
Refinement on F2
S = 1.07
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.020
wR(F2) = 0.049
3467 reflections
209 parameters
0 restraints
Acta Cryst. (2017). C73, 1040-1049
sup-1

supporting information
Hydrogen site location: inferred from
neighbouring sites
H-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0202P)2 + 0.6373P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.001
Δρmax = 0.40 e Å−3
Δρmin = −0.39 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
C1
C2
C3
0.29057 (17)
0.41876 (18)
0.57679 (18)
0.72260 (18)
0.8179
0.14946 (19)
0.2564 (2)
0.39150 (19)
0.40212 (19)
0.4924
0.81720 (15)
0.82078 (15)
0.82260 (14)
0.86046 (14)
0.8513
0.0189 (3)
0.0119 (3)
0.0100 (3)
0.0098 (3)
0.012*
H3
C28
O28
N21
C22
H22
C23
C23A
C24
H24
C25
H25
C26
H26
C27
H27
C27A
C211
H21A
H21B
H21C
C31
C32
Br32
C33
H33
C34
H34
C35
H35
0.58375 (18)
0.71080 (13)
0.21687 (15)
0.31281 (17)
0.2916
0.44624 (17)
0.43162 (17)
0.52727 (18)
0.6262
0.47404 (19)
0.5386
0.32693 (19)
0.2934
0.52896 (19)
0.67527 (14)
0.33281 (16)
0.31821 (19)
0.2088
0.48493 (18)
0.61089 (19)
0.79570 (19)
0.8660
0.87307 (19)
0.9982
0.7718 (2)
0.8302
0.77826 (14)
0.82765 (11)
0.50736 (12)
0.59208 (14)
0.5923
0.67852 (14)
0.64119 (14)
0.68562 (14)
0.7565
0.62369 (15)
0.6519
0.51994 (15)
0.4807
0.0098 (3)
0.0150 (2)
0.0101 (2)
0.0100 (3)
0.012*
0.0087 (3)
0.0090 (3)
0.0105 (3)
0.013*
0.0126 (3)
0.015*
0.0131 (3)
0.016*
0.22994 (18)
0.1303
0.28581 (17)
0.07277 (18)
0.0497
0.5887 (2)
0.5194
0.51137 (19)
0.1855 (2)
0.0716
0.47382 (15)
0.4037
0.53536 (14)
0.39592 (16)
0.3949
0.0120 (3)
0.014*
0.0094 (3)
0.0150 (3)
0.022*
0.0963
−0.0244
0.1829
0.2029
0.3077
0.4103
0.022*
0.022*
0.75642 (17)
0.88829 (17)
1.00583 (2)
0.93663 (18)
1.0270
0.85086 (18)
0.8831
0.71789 (19)
0.6585
0.29564 (18)
0.25981 (18)
0.32293 (2)
0.17583 (19)
0.1542
0.1236 (2)
0.0669
0.1542 (2)
0.1167
0.91350 (14)
0.88333 (14)
0.75519 (2)
0.94167 (15)
0.9195
1.03316 (15)
1.0751
1.06365 (15)
1.1255
0.0091 (3)
0.0092 (3)
0.01222 (5)
0.0114 (3)
0.014*
0.0127 (3)
0.015*
0.0130 (3)
0.016*
Acta Cryst. (2017). C73, 1040-1049
sup-2

supporting information
C36
H36
0.67111 (18)
0.5797
0.2388 (2)
0.2586
1.00457 (15)
1.0263
0.0116 (3)
0.014*
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
N1
C1
C2
C3
0.0142 (6)
0.0131 (7)
0.0114 (7)
0.0109 (6)
0.0111 (6)
0.0135 (5)
0.0087 (5)
0.0115 (6)
0.0092 (6)
0.0097 (6)
0.0107 (6)
0.0154 (7)
0.0175 (7)
0.0116 (7)
0.0105 (6)
0.0111 (7)
0.0082 (6)
0.0078 (6)
0.01107 (7)
0.0092 (6)
0.0134 (7)
0.0137 (7)
0.0099 (6)
0.0248 (7)
0.0160 (7)
0.0103 (6)
0.0092 (6)
0.0108 (6)
0.0108 (5)
0.0106 (6)
0.0121 (7)
0.0099 (6)
0.0120 (7)
0.0105 (7)
0.0097 (6)
0.0170 (7)
0.0153 (7)
0.0110 (6)
0.0123 (7)
0.0079 (6)
0.0090 (6)
0.01656 (8)
0.0110 (7)
0.0117 (7)
0.0140 (7)
0.0140 (7)
0.0258 (7)
0.0128 (7)
0.0092 (6)
0.0086 (6)
0.0096 (6)
0.0181 (5)
0.0105 (6)
0.0105 (6)
0.0097 (6)
0.0086 (6)
0.0088 (6)
0.0125 (7)
0.0133 (7)
0.0108 (7)
0.0093 (6)
0.0134 (7)
0.0086 (6)
0.0082 (6)
0.01307 (8)
0.0129 (7)
0.0134 (7)
0.0123 (7)
0.0115 (7)
0.0094 (6)
0.0096 (6)
0.0055 (6)
0.0044 (5)
0.0068 (5)
0.0036 (4)
0.0039 (5)
0.0073 (6)
0.0059 (5)
0.0068 (5)
0.0050 (6)
0.0066 (6)
0.0125 (6)
0.0075 (6)
0.0063 (5)
0.0015 (6)
0.0027 (5)
0.0019 (5)
0.00725 (6)
0.0048 (5)
0.0050 (6)
0.0055 (6)
0.0062 (6)
0.0057 (5)
0.0042 (5)
0.0033 (5)
0.0021 (5)
0.0041 (5)
−0.0017 (4)
0.0019 (5)
0.0051 (5)
0.0045 (5)
0.0046 (5)
0.0026 (5)
0.0050 (6)
0.0061 (6)
0.0025 (5)
0.0051 (5)
−0.0020 (6)
−0.0002 (5)
0.0010 (5)
0.00570 (5)
0.0012 (5)
0.0003 (5)
0.0038 (5)
0.0027 (5)
0.0187 (6)
0.0092 (6)
0.0050 (5)
0.0039 (5)
0.0048 (5)
0.0067 (4)
0.0053 (5)
0.0070 (6)
0.0055 (5)
0.0058 (5)
0.0031 (5)
0.0043 (6)
0.0098 (6)
0.0064 (6)
0.0056 (5)
0.0035 (6)
0.0030 (5)
0.0039 (5)
0.00963 (6)
0.0047 (6)
0.0074 (6)
0.0082 (6)
0.0059 (6)
C28
O28
N21
C22
C23
C23A
C24
C25
C26
C27
C27A
C211
C31
C32
Br32
C33
C34
C35
C36
Geometric parameters (Å, º)
N1—C1
1.146 (2)
C25—H25
0.9500
C1—C2
C2—C3
C2—C28
C3—C31
1.435 (2)
1.345 (2)
1.516 (2)
1.462 (2)
0.9500
1.2253 (19)
1.447 (2)
1.3528 (19)
1.385 (2)
1.459 (2)
1.385 (2)
0.9500
C26—C27
C26—H26
C27—C27A
C27—H27
C211—H21A
C211—H21B
C211—H21C
C31—C36
C31—C32
C32—C33
C32—Br32
C33—C34
C33—H33
C34—C35
C34—H34
1.384 (2)
0.9500
1.390 (2)
0.9500
0.9800
0.9800
C3—H3
C28—O28
C28—C23
N21—C22
N21—C27A
N21—C211
C22—C23
C22—H22
C23—C23A
C23A—C24
C23A—C27A
0.9800
1.397 (2)
1.402 (2)
1.381 (2)
1.8959 (15)
1.385 (2)
0.9500
1.441 (2)
1.398 (2)
1.411 (2)
1.388 (2)
0.9500
Acta Cryst. (2017). C73, 1040-1049
sup-3

supporting information
C24—C25
C24—H24
C25—C26
1.379 (2)
0.9500
1.405 (2)
C35—C36
C35—H35
C36—H36
1.384 (2)
0.9500
0.9500
N1—C1—C2
C3—C2—C1
C3—C2—C28
C1—C2—C28
C2—C3—C31
C2—C3—H3
C31—C3—H3
178.21 (16)
123.11 (14)
117.10 (13)
119.78 (13)
129.71 (13)
115.1
C26—C27—C27A
C26—C27—H27
C27A—C27—H27
N21—C27A—C27
N21—C27A—C23A
C27—C27A—C23A
N21—C211—H21A
N21—C211—H21B
H21A—C211—H21B
N21—C211—H21C
H21A—C211—H21C
H21B—C211—H21C
C36—C31—C32
C36—C31—C3
116.53 (14)
121.7
121.7
128.84 (14)
108.03 (12)
123.12 (14)
109.5
109.5
109.5
109.5
109.5
115.1
O28—C28—C23
O28—C28—C2
C23—C28—C2
C22—N21—C27A
C22—N21—C211
C27A—N21—C211
N21—C22—C23
N21—C22—H22
C23—C22—H22
C22—C23—C23A
C22—C23—C28
C23A—C23—C28
C24—C23A—C27A
C24—C23A—C23
C27A—C23A—C23
C25—C24—C23A
C25—C24—H24
C23A—C24—H24
C24—C25—C26
C24—C25—H25
C26—C25—H25
C27—C26—C25
C27—C26—H26
C25—C26—H26
122.07 (13)
117.42 (13)
120.49 (13)
108.76 (12)
126.51 (13)
124.52 (12)
110.62 (13)
124.7
109.5
116.99 (13)
122.58 (13)
120.20 (13)
122.72 (13)
117.14 (11)
120.13 (11)
118.77 (14)
120.6
120.6
120.09 (13)
120.0
120.0
120.46 (14)
119.8
C32—C31—C3
124.7
C33—C32—C31
C33—C32—Br32
C31—C32—Br32
C32—C33—C34
C32—C33—H33
C34—C33—H33
C33—C34—C35
C33—C34—H34
C35—C34—H34
C36—C35—C34
C36—C35—H35
C34—C35—H35
C35—C36—C31
C35—C36—H36
C31—C36—H36
105.98 (13)
128.88 (13)
124.91 (13)
119.08 (13)
134.34 (14)
106.58 (13)
118.17 (14)
120.9
120.9
121.77 (14)
119.1
119.1
121.31 (14)
119.3
119.8
120.95 (14)
119.5
119.5
119.3
C1—C2—C3—C31
−4.1 (2)
C22—N21—C27A—C27
C211—N21—C27A—C27
C22—N21—C27A—C23A
C211—N21—C27A—C23A
C26—C27—C27A—N21
C26—C27—C27A—C23A
C24—C23A—C27A—N21
C23—C23A—C27A—N21
C24—C23A—C27A—C27
C23—C23A—C27A—C27
C2—C3—C31—C36
179.90 (14)
4.9 (2)
0.57 (15)
−174.47 (13)
−178.17 (14)
1.1 (2)
178.21 (12)
−1.26 (15)
−1.2 (2)
C28—C2—C3—C31
C3—C2—C28—O28
C1—C2—C28—O28
C3—C2—C28—C23
C1—C2—C28—C23
C27A—N21—C22—C23
C211—N21—C22—C23
N21—C22—C23—C23A
N21—C22—C23—C28
O28—C28—C23—C22
C2—C28—C23—C22
176.84 (13)
−28.16 (19)
152.77 (14)
150.23 (14)
−28.8 (2)
0.38 (16)
175.30 (13)
−1.15 (16)
−175.81 (13)
164.56 (14)
−13.7 (2)
179.37 (13)
−38.0 (2)
147.66 (16)
C2—C3—C31—C32
Acta Cryst. (2017). C73, 1040-1049
sup-4

supporting information
O28—C28—C23—C23A
C2—C28—C23—C23A
C22—C23—C23A—C24
C28—C23—C23A—C24
C22—C23—C23A—C27A
C28—C23—C23A—C27A
C27A—C23A—C24—C25
C23—C23A—C24—C25
C23A—C24—C25—C26
C24—C25—C26—C27
C25—C26—C27—C27A
−9.2 (2)
C36—C31—C32—C33
−1.3 (2)
172.51 (13)
−177.89 (15)
−3.0 (2)
1.45 (15)
176.39 (13)
0.2 (2)
179.45 (15)
0.9 (2)
−1.0 (2)
C3—C31—C32—C33
C36—C31—C32—Br32
C3—C31—C32—Br32
C31—C32—C33—C34
Br32—C32—C33—C34
C32—C33—C34—C35
C33—C34—C35—C36
C34—C35—C36—C31
C32—C31—C36—C35
C3—C31—C36—C35
173.30 (13)
177.45 (10)
−7.92 (18)
0.4 (2)
−178.40 (11)
0.7 (2)
−0.8 (2)
−0.1 (2)
1.2 (2)
−173.32 (14)
0.0 (2)
Hydrogen-bond geometry (Å, º)
D—H···A
C24—H24···Cg1i
D—H
0.95
H···A
D···A
3.544 (3)
D—H···A
139
2.77
Symmetry code: (i) x, y+1, z.
(2RS)-2-(2-Bromobenzyl)-3-(1-methyl-1H-indol-3-yl)-\ 3-oxopropanenitrile (IIb)
Crystal data
C19H15BrN2O
Mr = 367.24
F(000) = 1488
Dx = 1.539 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 7297 reflections
θ = 2.4–27.6°
Monoclinic, P21/n
a = 13.728 (6) Å
b = 14.901 (6) Å
c = 15.507 (6) Å
β = 92.165 (19)°
V = 3170 (2) Å3
Z = 8
µ = 2.60 mm−1
T = 100 K
Plate, yellow-brown
0.40 × 0.30 × 0.10 mm
Data collection
Bruker D8 Venture
diffractometer
Radiation source: INCOATEC high brilliance
microfocus sealed tube
79963 measured reflections
7297 independent reflections
5456 reflections with I > 2σ(I)
Rint = 0.090
Multilayer mirror monochromator
φ and ω scans
Absorption correction: multi-scan
(SADABS; Bruker, 2016)
θmax = 27.6°, θmin = 2.4°
h = −17→17
k = −18→19
l = −20→20
T
min = 0.489, Tmax = 0.771
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.034
wR(F2) = 0.072
S = 1.05
7297 reflections
417 parameters
0 restraints
Hydrogen site location: inferred from
neighbouring sites
H-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0217P)2 + 3.7392P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.002
Δρmax = 0.54 e Å−3
Δρmin = −0.76 e Å−3
Acta Cryst. (2017). C73, 1040-1049
sup-5

supporting information
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
N11
C11
C12
H12
0.18232 (18)
0.2371 (2)
0.30553 (18)
0.2725
0.42519 (15)
0.47754 (16)
0.54607 (16)
0.6059
0.29826 (14)
0.27615 (16)
0.24554 (15)
0.2438
0.0248 (5)
0.0168 (5)
0.0133 (5)
0.016*
C13
O13
0.33425 (18)
0.34791 (14)
0.39870 (19)
0.4337
0.51972 (15)
0.44049 (11)
0.55156 (16)
0.4936
0.15332 (15)
0.13777 (11)
0.30549 (15)
0.3035
0.0133 (5)
0.0198 (4)
0.0146 (5)
0.018*
C127
H12A
H12B
C121
C122
Br12
C123
H123
C124
H124
C125
H125
C126
H126
N131
C132
H132
C133
C13A
C134
H134
C135
H135
C136
H136
C137
H137
C17A
C131
H13A
H13B
H13C
N21
0.4423
0.5985
0.2834
0.018*
0.37709 (18)
0.35456 (18)
0.34405 (2)
0.33681 (19)
0.3223
0.34047 (19)
0.3284
0.3616 (2)
0.3636
0.37979 (19)
0.3945
0.33943 (15)
0.32742 (18)
0.3100
0.34426 (18)
0.36750 (18)
0.38778 (18)
0.3906
0.40367 (19)
0.4165
0.40119 (19)
0.4134
0.38127 (19)
0.3798
0.36354 (18)
0.3262 (2)
0.3095
0.2734
0.3867
0.22989 (19)
0.57268 (16)
0.65859 (16)
0.75572 (2)
0.67677 (17)
0.7361
0.60709 (17)
0.6188
0.52069 (17)
0.4730
0.50432 (17)
0.4449
0.72482 (13)
0.68181 (16)
0.7100
0.59041 (16)
0.57742 (16)
0.50255 (17)
0.4442
0.51530 (18)
0.4649
0.60133 (18)
0.6081
0.67663 (17)
0.7350
0.66288 (16)
0.82032 (16)
0.8504
0.8291
0.8457
0.33176 (16)
0.39815 (16)
0.42667 (16)
0.34672 (2)
0.51225 (16)
0.5300
0.57167 (16)
0.6305
0.54579 (17)
0.5865
0.45965 (16)
0.4422
0.02457 (13)
0.10035 (15)
0.1525
0.09058 (15)
0.00110 (15)
−0.04959 (15)
−0.0250
−0.13629 (17)
−0.1716
−0.17306 (16)
−0.2326
−0.12446 (16)
−0.1492
−0.03762 (15)
0.00842 (17)
0.0621
−0.0351
−0.0126
0.79585 (15)
0.0134 (5)
0.0131 (5)
0.01692 (7)
0.0153 (5)
0.018*
0.0186 (6)
0.022*
0.0194 (6)
0.023*
0.0181 (5)
0.022*
0.0130 (4)
0.0129 (5)
0.016*
0.0132 (5)
0.0126 (5)
0.0156 (5)
0.019*
0.0196 (6)
0.024*
0.0196 (6)
0.023*
0.0163 (5)
0.020*
0.0132 (5)
0.0190 (6)
0.029*
0.029*
0.029*
0.0273 (6)
Acta Cryst. (2017). C73, 1040-1049
sup-6

supporting information
C21
C22
H22
0.2823 (2)
0.34802 (18)
0.3133
0.27789 (16)
0.20737 (16)
0.1484
0.77344 (16)
0.74254 (15)
0.7423
0.0164 (5)
0.0126 (5)
0.015*
C23
O23
0.37571 (18)
0.39429 (14)
0.44284 (18)
0.4848
0.23082 (15)
0.30937 (11)
0.20000 (16)
0.1527
0.64954 (15)
0.63232 (11)
0.79972 (15)
0.7760
0.0137 (5)
0.0198 (4)
0.0140 (5)
0.017*
C227
H22A
H22B
C221
C222
Br22
C223
H223
C224
H224
C225
H225
C226
H226
N231
C232
H232
C233
C23A
C234
H234
C235
H235
C236
H236
C237
H237
C27A
C231
H23A
H23B
H23C
0.4787
0.2575
0.7973
0.017*
0.42413 (18)
0.40507 (18)
0.39344 (2)
0.39041 (19)
0.3797
0.39156 (19)
0.3811
0.40795 (19)
0.4074
0.42517 (18)
0.4380
0.36915 (16)
0.35817 (18)
0.3381
0.38029 (18)
0.40570 (18)
0.43411 (19)
0.4402
0.4530 (2)
0.4708
0.17826 (16)
0.09155 (16)
−0.00513 (2)
0.07332 (17)
0.0135
0.14326 (17)
0.1313
0.23065 (17)
0.2787
0.24722 (16)
0.3069
0.02132 (13)
0.06868 (16)
0.0442
0.15829 (15)
0.16573 (16)
0.23648 (17)
0.2958
0.21792 (19)
0.2655
0.89260 (15)
0.92183 (15)
0.84159 (2)
1.00809 (16)
1.0266
1.06685 (16)
1.1260
1.04010 (16)
1.0804
0.95389 (16)
0.9360
0.52880 (13)
0.60173 (15)
0.6548
0.58849 (15)
0.49902 (15)
0.44611 (16)
0.4682
0.36101 (17)
0.3240
0.0130 (5)
0.0138 (5)
0.01913 (7)
0.0166 (5)
0.020*
0.0177 (5)
0.021*
0.0177 (5)
0.021*
0.0159 (5)
0.019*
0.0140 (4)
0.0136 (5)
0.016*
0.0126 (5)
0.0133 (5)
0.0180 (5)
0.022*
0.0231 (6)
0.028*
0.4466 (2)
0.4615
0.41896 (19)
0.4144
0.39814 (18)
0.3488 (2)
0.3322
0.13043 (19)
0.1198
0.05918 (18)
−0.0002
0.07874 (16)
−0.07415 (16)
−0.1007
0.32817 (17)
0.2697
0.37893 (16)
0.3568
0.46411 (15)
0.51695 (17)
0.5723
0.0237 (6)
0.028*
0.0190 (6)
0.023*
0.0143 (5)
0.0177 (5)
0.027*
0.4065
0.2939
−0.1041
−0.0817
0.4953
0.4753
0.027*
0.027*
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
N11
C11
0.0269 (14)
0.0179 (15)
0.0141 (14)
0.0116 (13)
0.0268 (11)
0.0138 (14)
0.0084 (13)
0.0297 (12)
0.0211 (13)
0.0124 (11)
0.0140 (12)
0.0137 (9)
0.0134 (11)
0.0160 (12)
0.0177 (12)
0.0111 (12)
0.0133 (12)
0.0142 (12)
0.0189 (9)
−0.0120 (11)
−0.0018 (11)
−0.0004 (9)
−0.0020 (9)
−0.0008 (8)
0.0003 (10)
−0.0027 (10)
−0.0031 (10)
−0.0050 (10)
−0.0005 (10)
−0.0007 (10)
0.0017 (8)
0.0050 (10)
0.0003 (10)
0.0006 (9)
−0.0007 (9)
−0.0017 (7)
−0.0030 (9)
−0.0021 (9)
C12
C13
O13
C127
C121
0.0166 (12)
0.0157 (12)
−0.0009 (10)
−0.0020 (10)
Acta Cryst. (2017). C73, 1040-1049
sup-7

supporting information
C122
Br12
C123
C124
C125
C126
N131
C132
C133
C13A
C134
C135
C136
C137
C17A
C131
N21
0.0092 (13)
0.02524 (15)
0.0123 (14)
0.0149 (14)
0.0158 (14)
0.0164 (14)
0.0130 (11)
0.0106 (13)
0.0116 (13)
0.0085 (13)
0.0123 (13)
0.0133 (14)
0.0143 (14)
0.0116 (14)
0.0074 (13)
0.0241 (16)
0.0259 (15)
0.0172 (14)
0.0133 (13)
0.0118 (13)
0.0284 (12)
0.0127 (14)
0.0081 (13)
0.0126 (13)
0.03058 (16)
0.0155 (14)
0.0140 (14)
0.0135 (14)
0.0130 (13)
0.0160 (12)
0.0138 (14)
0.0094 (13)
0.0091 (13)
0.0157 (14)
0.0196 (15)
0.0188 (16)
0.0122 (14)
0.0094 (13)
0.0190 (15)
0.0160 (12)
0.01184 (11)
0.0182 (12)
0.0287 (14)
0.0234 (13)
0.0149 (12)
0.0134 (10)
0.0164 (12)
0.0150 (12)
0.0163 (12)
0.0176 (12)
0.0265 (14)
0.0343 (15)
0.0231 (13)
0.0164 (12)
0.0135 (12)
0.0317 (13)
0.0205 (12)
0.0122 (11)
0.0157 (12)
0.0114 (8)
0.0147 (11)
0.0168 (12)
0.0155 (12)
0.01197 (12)
0.0176 (12)
0.0280 (13)
0.0226 (13)
0.0155 (11)
0.0124 (10)
0.0157 (11)
0.0158 (11)
0.0183 (12)
0.0196 (13)
0.0330 (15)
0.0404 (16)
0.0295 (14)
0.0200 (12)
0.0135 (12)
0.0139 (12)
0.01379 (12)
0.0152 (13)
0.0119 (12)
0.0186 (13)
0.0225 (13)
0.0125 (10)
0.0116 (12)
0.0127 (12)
0.0128 (12)
0.0170 (12)
0.0191 (13)
0.0099 (12)
0.0138 (12)
0.0155 (12)
0.0191 (13)
0.0243 (13)
0.0111 (12)
0.0122 (12)
0.0133 (12)
0.0197 (10)
0.0145 (12)
0.0140 (12)
0.0130 (12)
0.01466 (12)
0.0165 (13)
0.0110 (12)
0.0168 (13)
0.0189 (12)
0.0135 (10)
0.0111 (12)
0.0124 (12)
0.0123 (12)
0.0188 (13)
0.0169 (13)
0.0117 (13)
0.0149 (13)
0.0132 (12)
0.0205 (13)
−0.0031 (9)
−0.00209 (10)
−0.0036 (10)
−0.0048 (11)
−0.0012 (11)
0.0012 (10)
−0.0015 (8)
−0.0013 (9)
−0.0009 (9)
−0.0021 (9)
0.0009 (10)
0.0007 (11)
−0.0018 (11)
−0.0025 (10)
−0.0020 (9)
0.0009 (11)
0.0088 (11)
0.0001 (11)
0.0009 (9)
0.0026 (10)
0.0007 (7)
0.0006 (10)
0.0021 (9)
0.0032 (10)
0.00296 (11)
0.0019 (10)
0.0004 (11)
0.0003 (10)
−0.0002 (10)
0.0012 (8)
−0.0021 (10)
0.00211 (10)
−0.0026 (10)
−0.0021 (10)
−0.0044 (11)
−0.0049 (10)
−0.0028 (8)
−0.0032 (10)
−0.0010 (10)
−0.0022 (10)
0.0004 (10)
0.0019 (11)
−0.0011 (10)
−0.0032 (10)
−0.0042 (10)
−0.0026 (11)
0.0008 (11)
−0.0023 (10)
0.0000 (10)
−0.0029 (10)
0.0013 (8)
−0.0017 (10)
−0.0009 (10)
−0.0037 (10)
−0.00141 (10)
−0.0025 (10)
−0.0033 (10)
−0.0040 (10)
−0.0028 (10)
−0.0028 (9)
−0.0028 (10)
−0.0028 (10)
−0.0022 (10)
0.0009 (10)
0.0021 (11)
0.0011 (9)
−0.00004 (9)
−0.0023 (10)
0.0005 (10)
0.0083 (10)
0.0013 (10)
−0.0008 (8)
−0.0013 (9)
−0.0001 (9)
−0.0002 (9)
−0.0021 (10)
−0.0081 (11)
−0.0010 (10)
0.0032 (10)
−0.0014 (9)
0.0026 (10)
−0.0055 (10)
−0.0016 (10)
−0.0005 (9)
0.0006 (9)
C21
C22
C23
O23
0.0009 (7)
0.0005 (9)
0.0008 (9)
C227
C221
C222
Br22
C223
C224
C225
C226
N231
C232
C233
C23A
C234
C235
C236
C237
C27A
C231
−0.0019 (9)
−0.00100 (9)
0.0039 (10)
0.0019 (10)
−0.0066 (10)
0.0002 (10)
−0.0027 (8)
0.0005 (9)
0.0050 (10)
0.0033 (9)
0.0009 (9)
0.0039 (10)
0.0020 (10)
0.0001 (12)
0.0026 (12)
0.0022 (11)
0.0025 (10)
−0.0011 (10)
−0.0002 (9)
0.0042 (10)
0.0058 (11)
−0.0025 (11)
−0.0086 (11)
−0.0007 (9)
−0.0034 (10)
−0.0005 (11)
−0.0044 (11)
−0.0044 (10)
−0.0032 (11)
Geometric parameters (Å, º)
N11—C11
C11—C12
C12—C13
C12—C127
C12—H12
C13—O13
1.145 (3)
N21—C21
1.141 (3)
1.478 (3)
1.548 (3)
1.555 (3)
1.0000
C21—C22
C22—C23
C22—C227
C22—H22
C23—O23
1.476 (3)
1.545 (3)
1.551 (3)
1.0000
1.221 (3)
1.229 (3)
Acta Cryst. (2017). C73, 1040-1049
sup-8

supporting information
C13—C133
1.444 (3)
1.511 (3)
0.9900
C23—C233
1.440 (3)
1.508 (3)
0.9900
C127—C121
C127—H12A
C127—H12B
C121—C122
C121—C126
C122—C123
C122—Br12
C123—C124
C123—H123
C124—C125
C124—H124
C125—C126
C125—H125
C126—H126
N131—C132
N131—C17A
N131—C131
C132—C133
C132—H132
C133—C13A
C13A—C134
C13A—C17A
C134—C135
C134—H134
C135—C136
C135—H135
C136—C137
C136—H136
C137—C17A
C137—H137
C131—H13A
C131—H13B
C131—H13C
C227—C221
C227—H22A
C227—H22B
C221—C222
C221—C226
C222—C223
C222—Br22
C223—C224
C223—H223
C224—C225
C224—H224
C225—C226
C225—H225
C226—H226
N231—C232
N231—C27A
N231—C231
C232—C233
C232—H232
C233—C23A
C23A—C234
C23A—C27A
C234—C235
C234—H234
C235—C236
C235—H235
C236—C237
C236—H236
C237—C27A
C237—H237
C231—H23A
C231—H23B
C231—H23C
0.9900
0.9900
1.393 (3)
1.395 (3)
1.385 (3)
1.908 (2)
1.388 (3)
0.9500
1.383 (4)
0.9500
1.390 (4)
0.9500
1.397 (3)
1.399 (3)
1.387 (3)
1.906 (2)
1.384 (4)
0.9500
1.388 (4)
0.9500
1.389 (3)
0.9500
0.9500
0.9500
1.354 (3)
1.384 (3)
1.455 (3)
1.391 (3)
0.9500
1.449 (3)
1.399 (3)
1.408 (3)
1.383 (4)
0.9500
1.403 (4)
0.9500
1.385 (4)
0.9500
1.393 (3)
0.9500
0.9800
1.346 (3)
1.388 (3)
1.460 (3)
1.386 (3)
0.9500
1.448 (3)
1.400 (3)
1.407 (3)
1.382 (4)
0.9500
1.401 (4)
0.9500
1.383 (4)
0.9500
1.393 (3)
0.9500
0.9800
0.9800
0.9800
0.9800
0.9800
N11—C11—C12
C11—C12—C13
C11—C12—C127
C13—C12—C127
C11—C12—H12
C13—C12—H12
C127—C12—H12
O13—C13—C133
O13—C13—C12
C133—C13—C12
C121—C127—C12
C121—C127—H12A
C12—C127—H12A
178.2 (3)
107.97 (19)
111.3 (2)
109.5 (2)
109.4
N21—C21—C22
C21—C22—C23
C21—C22—C227
C23—C22—C227
C21—C22—H22
C23—C22—H22
C227—C22—H22
O23—C23—C233
O23—C23—C22
C233—C23—C22
C221—C227—C22
C221—C227—H22A
C22—C227—H22A
178.4 (3)
108.47 (19)
112.0 (2)
108.6 (2)
109.2
109.4
109.4
109.2
109.2
123.6 (2)
118.3 (2)
118.1 (2)
113.1 (2)
109.0
123.9 (2)
118.6 (2)
117.5 (2)
113.1 (2)
109.0
109.0
109.0
Acta Cryst. (2017). C73, 1040-1049
sup-9

supporting information
C121—C127—H12B
C12—C127—H12B
H12A—C127—H12B
C122—C121—C126
C122—C121—C127
C126—C121—C127
C123—C122—C121
C123—C122—Br12
C121—C122—Br12
C122—C123—C124
C122—C123—H123
C124—C123—H123
C125—C124—C123
C125—C124—H124
C123—C124—H124
C124—C125—C126
C124—C125—H125
C126—C125—H125
C125—C126—C121
C125—C126—H126
C121—C126—H126
C132—N131—C17A
C132—N131—C131
C17A—N131—C131
N131—C132—C133
N131—C132—H132
C133—C132—H132
C132—C133—C13
C132—C133—C13A
C13—C133—C13A
C134—C13A—C17A
C134—C13A—C133
C17A—C13A—C133
C135—C134—C13A
C135—C134—H134
C13A—C134—H134
C134—C135—C136
C134—C135—H135
C136—C135—H135
C137—C136—C135
C137—C136—H136
C135—C136—H136
C136—C137—C17A
C136—C137—H137
C17A—C137—H137
N131—C17A—C137
N131—C17A—C13A
C137—C17A—C13A
109.0
109.0
107.8
C221—C227—H22B
C22—C227—H22B
H22A—C227—H22B
C222—C221—C226
C222—C221—C227
C226—C221—C227
C223—C222—C221
C223—C222—Br22
C221—C222—Br22
C224—C223—C222
C224—C223—H223
C222—C223—H223
C223—C224—C225
C223—C224—H224
C225—C224—H224
C224—C225—C226
C224—C225—H225
C226—C225—H225
C225—C226—C221
C225—C226—H226
C221—C226—H226
C232—N231—C27A
C232—N231—C231
C27A—N231—C231
N231—C232—C233
N231—C232—H232
C233—C232—H232
C232—C233—C23
C232—C233—C23A
C23—C233—C23A
C234—C23A—C27A
C234—C23A—C233
C27A—C23A—C233
C235—C234—C23A
C235—C234—H234
C23A—C234—H234
C234—C235—C236
C234—C235—H235
C236—C235—H235
C237—C236—C235
C237—C236—H236
C235—C236—H236
C236—C237—C27A
C236—C237—H237
C27A—C237—H237
N231—C27A—C237
N231—C27A—C23A
C237—C27A—C23A
109.0
109.0
107.8
117.0 (2)
123.2 (2)
119.8 (2)
122.2 (2)
117.56 (18)
120.21 (18)
119.1 (2)
120.4
120.4
120.4 (2)
119.8
119.8
119.3 (2)
120.3
117.1 (2)
123.3 (2)
119.6 (2)
122.0 (2)
118.02 (18)
119.95 (18)
119.3 (2)
120.4
120.4
120.5 (2)
119.7
119.7
119.4 (2)
120.3
120.3
121.9 (2)
119.1
120.3
121.7 (2)
119.1
119.1
119.1
109.22 (19)
126.4 (2)
124.3 (2)
110.0 (2)
125.0
109.2 (2)
126.1 (2)
124.6 (2)
110.4 (2)
124.8
125.0
124.8
128.4 (2)
106.2 (2)
125.3 (2)
119.1 (2)
134.5 (2)
106.3 (2)
118.6 (2)
120.7
120.7
121.2 (2)
119.4
119.4
121.4 (2)
119.3
127.6 (2)
106.1 (2)
126.2 (2)
119.1 (2)
134.6 (2)
106.3 (2)
118.4 (2)
120.8
120.8
121.4 (3)
119.3
119.3
121.5 (2)
119.3
119.3
116.9 (2)
121.5
119.3
116.7 (2)
121.6
121.5
121.6
129.1 (2)
108.2 (2)
122.7 (2)
129.1 (2)
108.0 (2)
122.9 (2)
Acta Cryst. (2017). C73, 1040-1049
sup-10

supporting information
N131—C131—H13A
N131—C131—H13B
H13A—C131—H13B
N131—C131—H13C
H13A—C131—H13C
H13B—C131—H13C
109.5
109.5
109.5
109.5
109.5
109.5
N231—C231—H23A
N231—C231—H23B
H23A—C231—H23B
N231—C231—H23C
H23A—C231—H23C
H23B—C231—H23C
109.5
109.5
109.5
109.5
109.5
109.5
C11—C12—C13—O13
C127—C12—C13—O13
C11—C12—C13—C133
−39.4 (3)
81.8 (3)
C21—C22—C23—O23
C227—C22—C23—O23
C21—C22—C23—C233
41.5 (3)
−80.5 (3)
−139.9 (2)
98.1 (3)
59.6 (3)
179.33 (19)
80.5 (3)
−99.3 (3)
−1.8 (4)
178.4 (2)
175.73 (18)
−4.1 (3)
2.1 (4)
−175.5 (2)
−0.5 (4)
−1.3 (4)
1.6 (4)
−0.1 (4)
179.7 (2)
−0.6 (3)
−177.4 (2)
178.6 (2)
0.8 (3)
−178.1 (3)
3.3 (4)
−0.7 (4)
−179.3 (2)
179.7 (3)
1.9 (5)
−0.6 (3)
−178.5 (2)
0.5 (4)
−180.0 (3)
−1.6 (4)
1.4 (4)
141.1 (2)
−97.6 (3)
−58.0 (3)
−177.27 (19)
−77.7 (3)
102.7 (3)
0.9 (4)
−178.7 (2)
−177.55 (19)
2.8 (3)
C127—C12—C13—C133
C11—C12—C127—C121
C13—C12—C127—C121
C12—C127—C121—C122
C12—C127—C121—C126
C126—C121—C122—C123
C127—C121—C122—C123
C126—C121—C122—Br12
C127—C121—C122—Br12
C121—C122—C123—C124
Br12—C122—C123—C124
C122—C123—C124—C125
C123—C124—C125—C126
C124—C125—C126—C121
C122—C121—C126—C125
C127—C121—C126—C125
C17A—N131—C132—C133
C131—N131—C132—C133
N131—C132—C133—C13
N131—C132—C133—C13A
O13—C13—C133—C132
C12—C13—C133—C132
O13—C13—C133—C13A
C12—C13—C133—C13A
C132—C133—C13A—C134
C13—C133—C13A—C134
C132—C133—C13A—C17A
C13—C133—C13A—C17A
C17A—C13A—C134—C135
C133—C13A—C134—C135
C13A—C134—C135—C136
C134—C135—C136—C137
C135—C136—C137—C17A
C132—N131—C17A—C137
C131—N131—C17A—C137
C132—N131—C17A—C13A
C131—N131—C17A—C13A
C136—C137—C17A—N131
C227—C22—C23—C233
C21—C22—C227—C221
C23—C22—C227—C221
C22—C227—C221—C222
C22—C227—C221—C226
C226—C221—C222—C223
C227—C221—C222—C223
C226—C221—C222—Br22
C227—C221—C222—Br22
C221—C222—C223—C224
Br22—C222—C223—C224
C222—C223—C224—C225
C223—C224—C225—C226
C224—C225—C226—C221
C222—C221—C226—C225
C227—C221—C226—C225
C27A—N231—C232—C233
C231—N231—C232—C233
N231—C232—C233—C23
N231—C232—C233—C23A
O23—C23—C233—C232
C22—C23—C233—C232
O23—C23—C233—C23A
C22—C23—C233—C23A
C232—C233—C23A—C234
C23—C233—C23A—C234
C232—C233—C23A—C27A
C23—C233—C23A—C27A
C27A—C23A—C234—C235
C233—C23A—C234—C235
C23A—C234—C235—C236
C234—C235—C236—C237
C235—C236—C237—C27A
C232—N231—C27A—C237
C231—N231—C27A—C237
C232—N231—C27A—C23A
C231—N231—C27A—C23A
C236—C237—C27A—N231
−0.7 (4)
177.78 (19)
0.0 (4)
0.4 (4)
−0.2 (4)
−0.4 (4)
179.2 (2)
0.6 (3)
178.6 (2)
−176.3 (2)
−0.5 (3)
177.6 (3)
−2.9 (4)
2.6 (4)
−177.9 (2)
−177.3 (3)
−1.4 (5)
0.3 (3)
176.2 (2)
0.3 (4)
177.5 (3)
1.0 (4)
−1.0 (4)
−0.2 (4)
179.1 (3)
1.1 (4)
−0.4 (3)
−178.5 (2)
−178.0 (2)
−0.1 (4)
179.3 (3)
−4.0 (4)
0.2 (3)
177.0 (2)
−180.0 (3)
Acta Cryst. (2017). C73, 1040-1049
sup-11

supporting information
C136—C137—C17A—C13A
C134—C13A—C17A—N131
C133—C13A—C17A—N131
C134—C13A—C17A—C137
C133—C13A—C17A—C137
1.5 (4)
178.1 (2)
0.1 (3)
−1.5 (4)
−179.5 (2)
C236—C237—C27A—C23A
−1.0 (4)
180.0 (2)
0.3 (3)
0.9 (4)
−178.8 (2)
C234—C23A—C27A—N231
C233—C23A—C27A—N231
C234—C23A—C27A—C237
C233—C23A—C27A—C237
Hydrogen-bond geometry (Å, º)
D—H···A
D—H
H···A
D···A
D—H···A
153
C125—H125···O23
0.95
2.57
3.446 (3)
(2RS)-3-(1-benzyl-1H-indol-3-yl)-\ 2-(2-bromobenzyl)-3-oxopropanenitrile (IIc)
Crystal data
C25H19BrN2O
Z = 4
Mr = 443.32
Triclinic, P1
F(000) = 904
Dx = 1.468 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 9244 reflections
θ = 2.2–27.6°
a = 10.912 (4) Å
b = 12.544 (8) Å
c = 15.583 (7) Å
α = 89.23 (4)°
β = 79.49 (3)°
γ = 73.20 (3)°
V = 2006.0 (18) Å3
µ = 2.07 mm−1
T = 100 K
Plate, colourless
0.22 × 0.21 × 0.10 mm
Data collection
Bruker D8 Venture
diffractometer
Radiation source: INCOATEC high brilliance
microfocus sealed tube
96931 measured reflections
9244 independent reflections
6872 reflections with I > 2σ(I)
Rint = 0.112
Multilayer mirror monochromator
φ and ω scans
Absorption correction: multi-scan
(SADABS; Bruker, 2016)
θmax = 27.6°, θmin = 2.2°
h = −14→14
k = −16→16
l = −20→20
T
min = 0.737, Tmax = 0.813
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.042
wR(F2) = 0.084
S = 1.02
9244 reflections
523 parameters
0 restraints
Hydrogen site location: inferred from
neighbouring sites
H-atom parameters constrained
w = 1/[σ2(Fo2) + (0.025P)2 + 2.2423P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.002
Δρmax = 0.40 e Å−3
Δρmin = −0.57 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.
Acta Cryst. (2017). C73, 1040-1049
sup-12

supporting information
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
y
z
Uiso*/Ueq
N11
C11
C12
H12
0.5097 (2)
0.5794 (2)
0.6656 (2)
0.7183
0.73044 (17)
0.64664 (19)
0.53736 (18)
0.5464
0.58025 (14)
0.59130 (15)
0.60712 (15)
0.6512
0.0195 (5)
0.0131 (5)
0.0120 (5)
0.014*
C13
O13
0.7577 (2)
0.71866 (16)
0.5832 (2)
0.5311
0.48592 (19)
0.50668 (14)
0.45808 (19)
0.4499
0.52103 (15)
0.45193 (11)
0.64171 (15)
0.5978
0.0135 (5)
0.0195 (4)
0.0143 (5)
0.017*
C127
H12A
H12B
C121
C122
Br12
C123
H123
C124
H124
C125
H125
C126
H126
N131
C132
H132
C133
C13A
C134
H134
C135
H135
C136
H136
C137
H137
C17A
C131
H13A
H13B
C141
C142
H142
C143
H143
C144
H144
C145
0.6427
0.3836
0.6488
0.017*
0.4926 (2)
0.5251 (2)
0.69435 (3)
0.4382 (3)
0.4620
0.3165 (3)
0.2569
0.2820 (2)
0.1989
0.3682 (2)
0.3421
1.05957 (19)
0.9391 (2)
0.8986
0.8832 (2)
0.9782 (2)
0.9828 (2)
0.9101
1.0950 (2)
1.0997
0.49869 (19)
0.4672 (2)
0.37370 (2)
0.5025 (2)
0.4766
0.5757 (2)
0.6020
0.6105 (2)
0.6614
0.5712 (2)
0.5943
0.31755 (16)
0.39054 (19)
0.4230
0.41133 (19)
0.34516 (19)
0.3297 (2)
0.3658
0.2608 (2)
0.2509
0.72782 (15)
0.80876 (16)
0.81581 (2)
0.88675 (17)
0.9407
0.88513 (18)
0.9382
0.80614 (17)
0.8049
0.72888 (16)
0.6750
0.58068 (13)
0.60079 (15)
0.6574
0.52668 (15)
0.45581 (15)
0.36647 (16)
0.3405
0.31686 (17)
0.2559
0.0142 (5)
0.0183 (5)
0.02901 (8)
0.0260 (6)
0.031*
0.0265 (6)
0.032*
0.0222 (6)
0.027*
0.0157 (5)
0.019*
0.0148 (4)
0.0154 (5)
0.019*
0.0133 (5)
0.0133 (5)
0.0170 (5)
0.020*
0.0217 (6)
0.026*
1.2021 (2)
1.2780
1.1995 (2)
1.2712
1.0870 (2)
1.1538 (2)
1.2325
0.2051 (2)
0.1586
0.2166 (2)
0.1775
0.28790 (19)
0.2766 (2)
0.3007
0.35422 (17)
0.3181
0.44269 (16)
0.4686
0.49215 (15)
0.63886 (16)
0.6178
0.0224 (6)
0.027*
0.0174 (5)
0.021*
0.0129 (5)
0.0218 (6)
0.026*
1.1805
0.1941
0.6367
0.026*
1.0984 (2)
1.1034 (2)
1.1446
1.0485 (2)
1.0501
0.9916 (2)
0.9546
0.9885 (2)
0.3190 (2)
0.4222 (2)
0.4651
0.4633 (2)
0.5349
0.3996 (2)
0.4273
0.2956 (2)
0.73197 (16)
0.75954 (17)
0.7199
0.84465 (17)
0.8626
0.90330 (16)
0.9616
0.87698 (16)
0.0149 (5)
0.0202 (5)
0.024*
0.0214 (6)
0.026*
0.0179 (5)
0.022*
0.0184 (5)
Acta Cryst. (2017). C73, 1040-1049
sup-13

supporting information
H145
C146
H146
N21
C21
C22
0.9507
1.0409 (2)
1.0373
−0.0140 (2)
−0.0827 (2)
−0.1675 (2)
−0.2217
0.2514
0.2560 (2)
0.1851
0.75831 (17)
0.84265 (19)
0.95153 (18)
0.9411
0.9174
0.79148 (17)
0.7734
0.92059 (14)
0.90939 (15)
0.89134 (15)
0.8486
0.022*
0.0182 (5)
0.022*
0.0192 (5)
0.0127 (5)
0.0119 (5)
0.014*
H22
C23
O23
−0.2577 (2)
−0.21598 (16)
−0.0836 (2)
−0.1419
1.00946 (18)
0.99589 (14)
1.02767 (19)
1.1008
0.97633 (15)
1.04483 (11)
0.85264 (15)
0.8409
0.0121 (5)
0.0193 (4)
0.0140 (5)
0.017*
C227
H22A
H22B
C221
C222
Br22
C223
H223
C224
H224
C225
H225
C226
H226
N231
C232
H232
C233
C23A
C234
H234
C235
H235
C236
H236
C237
H237
C27A
C231
H23B
H23A
C241
C242
H242
C243
H243
C244
H244
C245
−0.0334
1.0405
0.8964
0.017*
0.0100 (2)
−0.0218 (2)
−0.19115 (3)
0.0658 (3)
0.0407
0.1898 (3)
0.2508
0.2247 (2)
0.3099
0.1361 (2)
0.1617
−0.55993 (18)
−0.4425 (2)
−0.4059
−0.3829 (2)
−0.4724 (2)
−0.4707 (2)
−0.3978
−0.5773 (2)
−0.5775
0.97895 (19)
0.9938 (2)
1.08181 (2)
0.9457 (2)
0.9565
0.8817 (2)
0.8489
0.8658 (2)
0.8217
0.9140 (2)
0.9025
1.17202 (16)
1.09431 (19)
1.0531
1.08334 (19)
1.16068 (18)
1.1906 (2)
1.1566
1.2708 (2)
1.2910
0.76913 (15)
0.68648 (16)
0.67357 (2)
0.61163 (17)
0.5562
0.61815 (17)
0.5671
0.69909 (16)
0.7038
0.77368 (16)
0.8290
0.91369 (13)
0.89647 (15)
0.8426
0.96888 (15)
1.03560 (15)
1.12156 (15)
1.1479
1.16723 (16)
1.2258
0.0134 (5)
0.0192 (5)
0.03007 (8)
0.0278 (6)
0.033*
0.0234 (6)
0.028*
0.0180 (5)
0.022*
0.0151 (5)
0.018*
0.0137 (4)
0.0137 (5)
0.016*
0.0124 (5)
0.0111 (4)
0.0159 (5)
0.019*
0.0191 (5)
0.023*
−0.6849 (2)
−0.7565
−0.6888 (2)
−0.7613
−0.5817 (2)
−0.6569 (2)
−0.6932
1.3230 (2)
1.3779
1.2960 (2)
1.3316
1.21439 (19)
1.2033 (2)
1.2854
1.12889 (16)
1.1619
1.04415 (16)
1.0178
0.99891 (15)
0.85626 (16)
0.8583
0.0198 (5)
0.024*
0.0166 (5)
0.020*
0.0123 (5)
0.0191 (5)
0.023*
−0.7294
1.1714
0.8779
0.023*
−0.5981 (2)
−0.5973 (2)
−0.6364
−0.5399 (2)
−0.5384
−0.4846 (2)
−0.4451
−0.4871 (2)
1.16213 (19)
1.0580 (2)
1.0129
1.0189 (2)
0.9468
1.0852 (2)
1.0586
1.1902 (2)
0.76315 (15)
0.73402 (17)
0.7727
0.64900 (17)
0.6300
0.59180 (16)
0.5336
0.61982 (16)
0.0145 (5)
0.0194 (5)
0.023*
0.0204 (5)
0.025*
0.0178 (5)
0.021*
0.0187 (5)
Acta Cryst. (2017). C73, 1040-1049
sup-14

supporting information
H245
C246
H246
−0.4506
−0.5431 (2)
−0.5437
1.2363
1.22815 (19)
1.2999
0.5805
0.70545 (16)
0.7246
0.022*
0.0156 (5)
0.019*
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
N11
C11
C12
C13
0.0183 (11)
0.0118 (11)
0.0126 (11)
0.0137 (11)
0.0193 (9)
0.0179 (11)
0.0158 (12)
0.0112 (11)
0.0124 (12)
0.0243 (10)
0.0106 (11)
0.0143 (12)
0.0197 (13)
0.03083 (16)
0.0390 (17)
0.0372 (16)
0.0234 (14)
0.0183 (13)
0.0157 (10)
0.0165 (12)
0.0140 (12)
0.0120 (11)
0.0171 (12)
0.0268 (14)
0.0242 (14)
0.0172 (13)
0.0107 (11)
0.0283 (15)
0.0170 (12)
0.0200 (13)
0.0154 (13)
0.0206 (13)
0.0219 (13)
0.0141 (12)
0.0189 (11)
0.0154 (12)
0.0125 (11)
0.0117 (11)
0.0236 (10)
0.0115 (11)
0.0119 (11)
0.0184 (13)
0.03471 (17)
0.0362 (16)
0.0263 (14)
0.0198 (13)
0.0181 (11)
−0.0017 (9)
−0.0041 (9)
−0.0006 (9)
−0.0041 (9)
0.0016 (7)
−0.0036 (9)
−0.0093 (9)
−0.0092 (10)
−0.00258 (12)
−0.0199 (13)
−0.0165 (12)
−0.0077 (10)
−0.0096 (10)
0.0001 (8)
−0.0011 (9)
−0.0034 (9)
−0.0040 (9)
−0.0046 (10)
−0.0052 (11)
−0.0023 (10)
−0.0015 (9)
−0.0043 (9)
0.0042 (10)
0.0007 (9)
−0.0076 (10)
−0.0064 (10)
−0.0043 (10)
−0.0104 (10)
−0.0059 (10)
−0.0018 (9)
−0.0040 (9)
−0.0007 (9)
−0.0040 (9)
0.0013 (7)
0.0017 (9)
0.0015 (9)
0.0006 (9)
0.0105 (11)
0.0105 (11)
0.0145 (12)
0.0112 (9)
−0.0027 (9)
−0.0011 (9)
−0.0017 (9)
−0.0024 (7)
−0.0017 (9)
−0.0003 (9)
0.0017 (10)
0.00779 (12)
0.0026 (12)
−0.0091 (12)
−0.0029 (11)
0.0013 (10)
−0.0008 (8)
−0.0021 (9)
−0.0011 (9)
−0.0009 (9)
0.0000 (10)
−0.0071 (10)
−0.0080 (11)
−0.0019 (10)
−0.0011 (9)
0.0003 (11)
0.0015 (9)
0.0099 (11)
−0.0007 (10)
−0.0014 (10)
0.0060 (10)
0.0011 (10)
0.0026 (9)
−0.0024 (9)
−0.0003 (9)
−0.0002 (9)
−0.0025 (7)
−0.0005 (9)
0.0010 (9)
−0.0023 (9)
−0.0025 (9)
−0.0062 (7)
−0.0021 (9)
−0.0020 (9)
−0.0053 (10)
−0.01353 (12)
−0.0049 (11)
0.0068 (11)
0.0024 (11)
−0.0030 (10)
−0.0045 (8)
−0.0015 (9)
−0.0035 (9)
−0.0014 (9)
−0.0046 (10)
−0.0007 (10)
0.0035 (10)
−0.0004 (10)
−0.0016 (9)
−0.0056 (10)
−0.0063 (9)
−0.0075 (11)
−0.0074 (11)
−0.0056 (10)
−0.0067 (10)
−0.0106 (10)
−0.0010 (9)
−0.0001 (9)
−0.0033 (9)
−0.0028 (9)
−0.0062 (7)
−0.0029 (9)
−0.0010 (9)
−0.0044 (10)
−0.00826 (11)
−0.0029 (11)
0.0048 (10)
−0.0008 (10)
O13
C127
C121
C122
Br12
C123
C124
C125
C126
N131
C132
C133
C13A
C134
C135
C136
C137
C17A
C131
C141
C142
C143
C144
C145
C146
N21
C21
C22
C23
O23
C227
C221
C222
Br22
C223
C224
C225
0.0161 (12)
0.0170 (12)
0.0203 (13)
0.02806 (16)
0.0300 (15)
0.0236 (14)
0.0154 (12)
0.0152 (12)
0.0139 (10)
0.0157 (12)
0.0139 (11)
0.0141 (11)
0.0183 (12)
0.0236 (13)
0.0175 (13)
0.0125 (12)
0.0144 (11)
0.0140 (12)
0.0114 (11)
0.0191 (13)
0.0244 (14)
0.0182 (12)
0.0215 (13)
0.0212 (13)
0.0190 (11)
0.0127 (11)
0.0125 (11)
0.0152 (11)
0.0185 (9)
0.0156 (12)
0.0141 (12)
0.0178 (13)
0.02740 (16)
0.0155 (13)
0.0196 (14)
0.0268 (15)
0.0167 (12)
0.0128 (10)
0.0116 (12)
0.0121 (12)
0.0136 (12)
0.0157 (12)
0.0124 (12)
0.0207 (14)
0.0197 (13)
0.0136 (12)
0.0174 (13)
0.0147 (12)
0.0237 (14)
0.0259 (15)
0.0152 (13)
0.0154 (13)
0.0223 (14)
0.0163 (11)
0.0094 (11)
0.0094 (11)
0.0096 (11)
0.0123 (9)
0.0144 (11)
0.0145 (11)
0.0164 (12)
0.02352 (15)
0.0295 (15)
0.0208 (13)
0.0122 (11)
0.0148 (12)
0.0146 (12)
0.0192 (13)
0.02276 (16)
0.0118 (13)
0.0171 (13)
0.0209 (13)
−0.0017 (9)
−0.0064 (9)
0.0010 (10)
0.00809 (11)
−0.0010 (12)
−0.0025 (11)
−0.0043 (9)
0.0031 (10)
0.00540 (12)
0.0038 (11)
−0.0002 (11)
0.0015 (10)
Acta Cryst. (2017). C73, 1040-1049
sup-15

supporting information
C226
N231
C232
C233
C23A
C234
C235
C236
C237
C27A
C231
C241
C242
C243
C244
C245
C246
0.0147 (12)
0.0111 (9)
0.0179 (12)
0.0161 (10)
0.0141 (12)
0.0112 (11)
0.0100 (11)
0.0175 (12)
0.0222 (13)
0.0191 (13)
0.0162 (12)
0.0124 (11)
0.0252 (14)
0.0164 (12)
0.0186 (13)
0.0148 (12)
0.0197 (13)
0.0194 (13)
0.0109 (11)
0.0149 (12)
0.0120 (10)
0.0117 (12)
0.0107 (11)
0.0101 (11)
0.0147 (12)
0.0115 (12)
0.0187 (13)
0.0200 (13)
0.0108 (11)
0.0145 (13)
0.0133 (12)
0.0195 (13)
0.0247 (14)
0.0150 (12)
0.0174 (13)
0.0166 (13)
−0.0078 (9)
−0.0002 (8)
−0.0006 (9)
−0.0027 (9)
−0.0037 (9)
−0.0042 (9)
−0.0079 (10)
−0.0027 (10)
−0.0032 (9)
−0.0050 (9)
0.0000 (10)
−0.0011 (9)
−0.0067 (10)
−0.0073 (10)
−0.0042 (10)
−0.0096 (10)
−0.0043 (9)
−0.0034 (9)
−0.0030 (8)
−0.0026 (9)
−0.0023 (9)
−0.0007 (9)
−0.0038 (9)
−0.0002 (10)
0.0023 (10)
−0.0015 (10)
0.0000 (9)
−0.0073 (10)
−0.0070 (9)
−0.0085 (11)
−0.0107 (11)
−0.0058 (10)
−0.0066 (10)
−0.0091 (10)
0.0019 (9)
−0.0018 (8)
−0.0015 (9)
−0.0008 (9)
0.0000 (9)
0.0001 (10)
−0.0059 (10)
−0.0043 (10)
0.0007 (10)
0.0008 (9)
0.0132 (11)
0.0146 (11)
0.0128 (11)
0.0155 (12)
0.0233 (13)
0.0178 (12)
0.0123 (11)
0.0136 (11)
0.0156 (12)
0.0135 (12)
0.0223 (13)
0.0253 (14)
0.0188 (12)
0.0225 (13)
0.0213 (12)
0.0006 (10)
0.0022 (9)
0.0076 (10)
−0.0007 (10)
−0.0023 (10)
0.0028 (10)
−0.0008 (9)
Geometric parameters (Å, º)
N11—C11
1.137 (3)
N21—C21
1.139 (3)
C11—C12
C12—C13
C12—C127
C12—H12
1.468 (3)
1.544 (3)
1.554 (3)
1.0000
C21—C22
C22—C23
C22—C227
C22—H22
1.468 (3)
1.545 (3)
1.551 (3)
1.0000
C13—O13
1.227 (3)
1.435 (3)
1.510 (3)
0.9900
C23—O23
1.226 (3)
1.436 (3)
1.511 (3)
0.9900
C13—C133
C127—C121
C127—H12A
C127—H12B
C121—C122
C121—C126
C122—C123
C122—Br12
C123—C124
C123—H123
C124—C125
C124—H124
C125—C126
C125—H125
C126—H126
N131—C132
N131—C17A
N131—C131
C132—C133
C132—H132
C133—C13A
C13A—C134
C23—C233
C227—C221
C227—H22A
C227—H22B
C221—C222
C221—C226
C222—C223
C222—Br22
C223—C224
C223—H223
C224—C225
C224—H224
C225—C226
C225—H225
C226—H226
N231—C232
N231—C27A
N231—C231
C232—C233
C232—H232
C233—C23A
C23A—C234
0.9900
0.9900
1.393 (3)
1.396 (3)
1.387 (4)
1.902 (3)
1.384 (4)
0.9500
1.381 (4)
0.9500
1.383 (3)
0.9500
1.391 (3)
1.396 (3)
1.385 (4)
1.903 (2)
1.381 (4)
0.9500
1.378 (4)
0.9500
1.387 (3)
0.9500
0.9500
0.9500
1.351 (3)
1.389 (3)
1.472 (3)
1.390 (3)
0.9500
1.351 (3)
1.390 (3)
1.473 (3)
1.388 (3)
0.9500
1.447 (3)
1.398 (3)
1.444 (3)
1.401 (3)
Acta Cryst. (2017). C73, 1040-1049
sup-16

supporting information
C13A—C17A
C134—C135
C134—H134
C135—C136
C135—H135
C136—C137
C136—H136
C137—C17A
C137—H137
C131—C141
C131—H13A
C131—H13B
C141—C142
C141—C146
C142—C143
C142—H142
C143—C144
C143—H143
C144—C145
C144—H144
C145—C146
C145—H145
C146—H146
1.409 (3)
1.381 (3)
0.9500
1.398 (4)
0.9500
1.382 (4)
0.9500
1.393 (3)
0.9500
1.506 (3)
0.9900
0.9900
1.389 (4)
1.390 (4)
1.391 (4)
0.9500
1.385 (4)
0.9500
C23A—C27A
C234—C235
C234—H234
C235—C236
C235—H235
C236—C237
C236—H236
C237—C27A
C237—H237
C231—C241
C231—H23B
C231—H23A
C241—C242
C241—C246
C242—C243
C242—H242
C243—C244
C243—H243
C244—C245
C244—H244
C245—C246
C245—H245
C246—H246
1.406 (3)
1.382 (3)
0.9500
1.402 (4)
0.9500
1.379 (3)
0.9500
1.392 (3)
0.9500
1.507 (3)
0.9900
0.9900
1.385 (3)
1.388 (3)
1.388 (4)
0.9500
1.387 (4)
0.9500
1.384 (4)
0.9500
1.387 (4)
0.9500
1.384 (3)
0.9500
1.390 (3)
0.9500
0.9500
0.9500
N11—C11—C12
C11—C12—C13
C11—C12—C127
C13—C12—C127
C11—C12—H12
178.1 (3)
109.69 (19)
109.87 (19)
108.84 (18)
109.5
N21—C21—C22
C21—C22—C23
C21—C22—C227
C23—C22—C227
C21—C22—H22
177.5 (3)
110.56 (19)
109.81 (19)
108.10 (19)
109.4
C13—C12—H12
109.5
C23—C22—H22
109.4
C127—C12—H12
O13—C13—C133
O13—C13—C12
109.5
C227—C22—H22
O23—C23—C233
O23—C23—C22
109.4
123.3 (2)
118.9 (2)
117.8 (2)
113.25 (19)
108.9
108.9
108.9
108.9
107.7
116.5 (2)
123.7 (2)
119.8 (2)
122.5 (2)
117.2 (2)
120.30 (19)
119.3 (3)
120.4
123.7 (2)
118.8 (2)
117.35 (19)
112.96 (19)
109.0
109.0
109.0
109.0
107.8
116.9 (2)
124.0 (2)
119.1 (2)
122.2 (2)
117.78 (19)
120.00 (18)
119.6 (2)
120.2
C133—C13—C12
C121—C127—C12
C121—C127—H12A
C12—C127—H12A
C121—C127—H12B
C12—C127—H12B
H12A—C127—H12B
C122—C121—C126
C122—C121—C127
C126—C121—C127
C123—C122—C121
C123—C122—Br12
C121—C122—Br12
C124—C123—C122
C124—C123—H123
C233—C23—C22
C221—C227—C22
C221—C227—H22A
C22—C227—H22A
C221—C227—H22B
C22—C227—H22B
H22A—C227—H22B
C222—C221—C226
C222—C221—C227
C226—C221—C227
C223—C222—C221
C223—C222—Br22
C221—C222—Br22
C224—C223—C222
C224—C223—H223
Acta Cryst. (2017). C73, 1040-1049
sup-17

supporting information
C122—C123—H123
C125—C124—C123
C125—C124—H124
C123—C124—H124
C124—C125—C126
C124—C125—H125
C126—C125—H125
C125—C126—C121
C125—C126—H126
C121—C126—H126
C132—N131—C17A
C132—N131—C131
C17A—N131—C131
N131—C132—C133
N131—C132—H132
C133—C132—H132
C132—C133—C13
C132—C133—C13A
C13—C133—C13A
C134—C13A—C17A
C134—C13A—C133
C17A—C13A—C133
C135—C134—C13A
C135—C134—H134
C13A—C134—H134
C134—C135—C136
C134—C135—H135
C136—C135—H135
C137—C136—C135
C137—C136—H136
C135—C136—H136
C136—C137—C17A
C136—C137—H137
C17A—C137—H137
N131—C17A—C137
N131—C17A—C13A
C137—C17A—C13A
N131—C131—C141
N131—C131—H13A
C141—C131—H13A
N131—C131—H13B
C141—C131—H13B
H13A—C131—H13B
C142—C141—C146
C142—C141—C131
C146—C141—C131
C141—C142—C143
C141—C142—H142
120.4
119.8 (2)
120.1
120.1
120.1 (2)
119.9
119.9
121.8 (2)
119.1
C222—C223—H223
C225—C224—C223
C225—C224—H224
C223—C224—H224
C224—C225—C226
C224—C225—H225
C226—C225—H225
C225—C226—C221
C225—C226—H226
C221—C226—H226
C232—N231—C27A
C232—N231—C231
C27A—N231—C231
N231—C232—C233
N231—C232—H232
C233—C232—H232
C232—C233—C23
C232—C233—C23A
C23—C233—C23A
C234—C23A—C27A
C234—C23A—C233
C27A—C23A—C233
C235—C234—C23A
C235—C234—H234
C23A—C234—H234
C234—C235—C236
C234—C235—H235
C236—C235—H235
C237—C236—C235
C237—C236—H236
C235—C236—H236
C236—C237—C27A
C236—C237—H237
C27A—C237—H237
N231—C27A—C237
N231—C27A—C23A
C237—C27A—C23A
N231—C231—C241
N231—C231—H23B
C241—C231—H23B
N231—C231—H23A
C241—C231—H23A
H23B—C231—H23A
C242—C241—C246
C242—C241—C231
C246—C241—C231
C241—C242—C243
C241—C242—H242
120.2
119.7 (2)
120.2
120.2
120.3 (2)
119.8
119.8
121.3 (2)
119.3
119.1
119.3
109.16 (19)
127.8 (2)
122.94 (19)
110.2 (2)
124.9
109.04 (19)
127.2 (2)
123.64 (19)
110.2 (2)
124.9
124.9
124.9
126.9 (2)
106.3 (2)
126.8 (2)
118.9 (2)
134.8 (2)
106.4 (2)
118.6 (2)
120.7
120.7
121.6 (2)
119.2
119.2
121.2 (2)
119.4
127.0 (2)
106.3 (2)
126.8 (2)
118.7 (2)
134.8 (2)
106.5 (2)
118.7 (2)
120.7
120.7
121.4 (2)
119.3
119.3
121.3 (2)
119.4
119.4
116.9 (2)
121.5
119.4
117.0 (2)
121.5
121.5
121.5
129.2 (2)
108.0 (2)
122.8 (2)
112.18 (19)
109.2
109.2
109.2
109.2
107.9
118.9 (2)
120.3 (2)
120.7 (2)
120.5 (2)
119.7
129.0 (2)
107.97 (19)
123.0 (2)
111.72 (19)
109.3
109.3
109.3
109.3
107.9
119.0 (2)
120.8 (2)
120.2 (2)
120.7 (2)
119.6
Acta Cryst. (2017). C73, 1040-1049
sup-18

supporting information
C143—C142—H142
C144—C143—C142
C144—C143—H143
C142—C143—H143
C145—C144—C143
C145—C144—H144
C143—C144—H144
C144—C145—C146
C144—C145—H145
C146—C145—H145
C145—C146—C141
C145—C146—H146
C141—C146—H146
119.7
119.9 (2)
120.1
120.1
120.0 (2)
120.0
120.0
119.9 (2)
120.1
120.1
120.7 (2)
119.6
C243—C242—H242
C244—C243—C242
C244—C243—H243
C242—C243—H243
C245—C244—C243
C245—C244—H244
C243—C244—H244
C244—C245—C246
C244—C245—H245
C246—C245—H245
C241—C246—C245
C241—C246—H246
C245—C246—H246
119.6
119.9 (2)
120.1
120.1
119.8 (2)
120.1
120.1
120.0 (2)
120.0
120.0
120.5 (2)
119.7
119.6
119.7
C11—C12—C13—O13
C127—C12—C13—O13
C11—C12—C13—C133
−31.9 (3)
88.3 (3)
151.1 (2)
−88.6 (2)
−61.9 (3)
177.96 (19)
−93.1 (3)
87.4 (3)
2.0 (4)
−177.5 (2)
−177.34 (17)
3.1 (3)
−3.0 (4)
176.3 (2)
1.6 (4)
0.7 (4)
−1.8 (4)
0.4 (3)
179.9 (2)
0.1 (3)
177.4 (2)
−178.4 (2)
−0.1 (3)
174.1 (2)
−9.1 (4)
−3.9 (4)
172.9 (2)
−179.2 (3)
−0.9 (4)
0.0 (3)
C21—C22—C23—O23
C227—C22—C23—O23
C21—C22—C23—C233
34.5 (3)
−85.7 (3)
−150.1 (2)
89.7 (2)
58.8 (3)
179.53 (18)
87.4 (3)
−92.0 (3)
0.9 (4)
−178.5 (2)
−179.65 (18)
0.9 (3)
−0.9 (4)
179.7 (2)
0.5 (4)
C127—C12—C13—C133
C11—C12—C127—C121
C13—C12—C127—C121
C12—C127—C121—C122
C12—C127—C121—C126
C126—C121—C122—C123
C127—C121—C122—C123
C126—C121—C122—Br12
C127—C121—C122—Br12
C121—C122—C123—C124
Br12—C122—C123—C124
C122—C123—C124—C125
C123—C124—C125—C126
C124—C125—C126—C121
C122—C121—C126—C125
C127—C121—C126—C125
C17A—N131—C132—C133
C131—N131—C132—C133
N131—C132—C133—C13
N131—C132—C133—C13A
O13—C13—C133—C132
C12—C13—C133—C132
O13—C13—C133—C13A
C12—C13—C133—C13A
C132—C133—C13A—C134
C13—C133—C13A—C134
C132—C133—C13A—C17A
C13—C133—C13A—C17A
C17A—C13A—C134—C135
C133—C13A—C134—C135
C13A—C134—C135—C136
C227—C22—C23—C233
C21—C22—C227—C221
C23—C22—C227—C221
C22—C227—C221—C222
C22—C227—C221—C226
C226—C221—C222—C223
C227—C221—C222—C223
C226—C221—C222—Br22
C227—C221—C222—Br22
C221—C222—C223—C224
Br22—C222—C223—C224
C222—C223—C224—C225
C223—C224—C225—C226
C224—C225—C226—C221
C222—C221—C226—C225
C227—C221—C226—C225
C27A—N231—C232—C233
C231—N231—C232—C233
N231—C232—C233—C23
N231—C232—C233—C23A
O23—C23—C233—C232
C22—C23—C233—C232
O23—C23—C233—C23A
C22—C23—C233—C23A
C232—C233—C23A—C234
C23—C233—C23A—C234
C232—C233—C23A—C27A
C23—C233—C23A—C27A
C27A—C23A—C234—C235
C233—C23A—C234—C235
C23A—C234—C235—C236
−0.2 (4)
0.2 (4)
−0.6 (3)
178.9 (2)
−0.4 (3)
−175.8 (2)
180.0 (2)
0.3 (3)
−172.6 (2)
12.3 (4)
7.0 (4)
−168.1 (2)
−179.3 (3)
1.1 (4)
−0.1 (3)
−179.8 (2)
0.8 (3)
178.4 (2)
−1.5 (4)
177.7 (3)
1.3 (4)
179.9 (3)
−0.8 (4)
Acta Cryst. (2017). C73, 1040-1049
sup-19

supporting information
C134—C135—C136—C137
C135—C136—C137—C17A
C132—N131—C17A—C137
C131—N131—C17A—C137
C132—N131—C17A—C13A
C131—N131—C17A—C13A
C136—C137—C17A—N131
C136—C137—C17A—C13A
C134—C13A—C17A—N131
C133—C13A—C17A—N131
C134—C13A—C17A—C137
C133—C13A—C17A—C137
C132—N131—C131—C141
C17A—N131—C131—C141
N131—C131—C141—C142
N131—C131—C141—C146
C146—C141—C142—C143
C131—C141—C142—C143
C141—C142—C143—C144
C142—C143—C144—C145
C143—C144—C145—C146
C144—C145—C146—C141
C142—C141—C146—C145
C131—C141—C146—C145
0.3 (4)
C234—C235—C236—C237
0.2 (4)
0.5 (4)
179.6 (2)
−4.8 (4)
0.3 (3)
−1.5 (4)
179.0 (2)
1.5 (4)
−0.1 (3)
−177.6 (2)
−177.7 (2)
1.2 (4)
179.4 (2)
0.1 (3)
0.3 (4)
C235—C236—C237—C27A
C232—N231—C27A—C237
C231—N231—C27A—C237
C232—N231—C27A—C23A
C231—N231—C27A—C23A
C236—C237—C27A—N231
C236—C237—C27A—C23A
C234—C23A—C27A—N231
C233—C23A—C27A—N231
C234—C23A—C27A—C237
C233—C23A—C27A—C237
C232—N231—C231—C241
C27A—N231—C231—C241
N231—C231—C241—C242
N231—C231—C241—C246
C246—C241—C242—C243
C231—C241—C242—C243
C241—C242—C243—C244
C242—C243—C244—C245
C243—C244—C245—C246
C242—C241—C246—C245
C231—C241—C246—C245
C244—C245—C246—C241
176.0 (2)
−179.7 (2)
−0.5 (4)
179.2 (2)
−0.1 (3)
−0.1 (4)
−179.4 (2)
−16.2 (3)
169.0 (2)
89.9 (3)
−89.6 (3)
1.4 (3)
−178.2 (2)
−1.1 (4)
−0.1 (4)
1.0 (4)
−0.4 (3)
179.1 (2)
−0.8 (4)
−179.1 (2)
4.5 (4)
−178.5 (2)
−85.5 (3)
94.2 (3)
−1.8 (3)
177.9 (2)
1.8 (4)
−0.4 (4)
−1.0 (4)
1.0 (4)
0.4 (3)
−179.3 (2)
Hydrogen-bond geometry (Å, º)
D—H···A
D—H
H···A
D···A
D—H···A
C225—H225···N11
C231—H23A···O23i
0.95
0.99
2.62
2.57
3.304 (4)
3.415 (4)
129
143
Symmetry code: (i) −x−1, −y+2, −z+2.
(E)-1-(1-Acetyl-1H-indol-3-yl)-3-(2-bromophenyl)-2-cyanoprop-1-en-1-yl acetate (III)
Crystal data
C22H17BrN2O3
Mr = 437.28
F(000) = 1776
Dx = 1.523 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 4412 reflections
θ = 2.5–27.6°
Monoclinic, C2/c
a = 19.406 (9) Å
b = 8.773 (4) Å
c = 23.028 (9) Å
β = 103.318 (15)°
V = 3815 (3) Å3
Z = 8
µ = 2.18 mm−1
T = 173 K
Block, colourless
0.42 × 0.32 × 0.24 mm
Acta Cryst. (2017). C73, 1040-1049
sup-20