(E)-2-(1,3-Benzothiazol-2-yl)-3-(4-fluorophenyl)acrylonitrile: A chain of π-stacked hydrogen-bonded rings

Article abstract of DOI:10.1107/S0108270113013267

The title compound, C₁₆H₉FN₂S, crystallizes as a nonmerohedral twin with twin rotation about the reciprocal-lattice vector [101]*. The molecules are nearly planar and the dihedral angle between the planes of the two aryl r

Full text of DOI:10.1107/S0108270113013267

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
Compound (I) crystallizes as a nonmerohedral twin. The
molecule is nearly planar, as shown by the key torsion angles
(Table 1), while the dihedral angle between the mean planes of
the two aryl rings is only 4.4 (2)ꢀ. By contrast, in compounds
(II) (Cobo et al., 2005) and (III) (Cobo et al., 2006), which are
isomorphous and isostructural, the aryl ring is twisted out of
the plane of the rest of the molecule by ca 38ꢀ in each case. On
the other hand, in compound (IV) (Cobo et al., 2009), which
ISSN 0108-2701
(E)-2-(1,3-Benzothiazol-2-yl)-3-(4-
fluorophenyl)acrylonitrile: a chain
of p-stacked hydrogen-bonded rings
a
a
b
´
Jorge Trilleras, Kelly Velasquez, Justo Cobo and
Christopher Glidewellc*
a
´
´
´
Grupo de Investigacion en Compuestos Heterocıclicos, Programa de Quımica,
´
´
´
Facultad de Ciencias Basicas, Universidad del Atlantico, Km 7 Antigua vıa Puerto
b
´
´
Colombia, Barranquilla, Colombia, Departamento de Quımica Inorganica y
Organica, Universidad de Jaen, 23071 Jaen, Spain, and cSchool of Chemistry,
´
´
´
University of St Andrews, Fife KY16 9ST, Scotland
Correspondence e-mail: cg@st-andrews.ac.uk
Received 14 May 2013
Accepted 14 May 2013
The title compound, C16H9FN2S, crystallizes as a nonmerohe-
dral twin with twin rotation about the reciprocal-lattice vector
[101]*. The molecules are nearly planar and the dihedral angle
between the planes of the two aryl rings is only 4.4 (2)ꢀ. The
molecules are linked by pairs of C—Hꢁ ꢁ ꢁN hydrogen bonds to
form cyclic centrosymmetric R22(18) dimers, which are linked
into chains by an aromatic ꢀ–ꢀ stacking interaction. Com-
parisons are made with some related 3-aryl-2-thienylacrylo-
nitriles.
contains both fully ordered molecules and fourfold disordered
molecules resulting in a Z0 value of 0.75 in the space group
C2/m, the non-H atoms of the ordered molecules all lie on
mirror planes, while those of the disordered molecule are
coplanar within experimental uncertainty, although not
constrained to be so by symmetry. Similarly, the non-H atoms
of compound (V) (Cobo et al., 2006) are, apart from the
methyl C atom of the 4-methoxy substituent, very nearly
coplanar. No obvious simple explanation presents itself for
Comment
Acetonitrile derivatives are useful and versatile precursors for
the synthesis of heterocyclic molecules having potential
biological activity; in particular they provide a useful route to
acrylonitrile derivatives. Although such derivatives are, in
general, easy to synthesize, a wide diversity of methods is
available, utilizing both conventional thermal reactions and
those mediated by microwave irradiation (Quiroga et al., 2000,
2001; Dawood et al., 2010). While Knoevenagel-type products
can be obtained under conventional thermal conditions in the
presence of catalytic quantities of base, giving yields in the
good to very low range, the corresponding condensation
reactions conducted in solvent-free systems under microwave
irradiation generally give better yields in much reduced
reaction times (Lenarda˜o et al., 2007). We have now prepared
the title compound, (E)-2-(1,3-benzothiazol-2-yl)-3-(4-fluoro-
phenyl)acrylonitrile, (I), using the microwave induced con-
densation reaction between 2-(1,3-benzothiazol-2-yl)aceto-
nitrile and 4-fluorobenzaldehyde under solvent-free condi-
tions, which provided a satisfactory yield in a very short
reaction time under environmentally friendly conditions, and
we report here the molecular and supramolecular structure of
compound (I) (Fig. 1), which we compare with the analogues
(II)–(V) (Cobo et al., 2005, 2006, 2009) (see Scheme).
Figure 1
The molecular structure of compound (I), showing the atom-labelling
scheme. Displacement ellipsoids are drawn at the 30% probability level.
Acta Cryst. (2013). C69, 671–673
doi:10.1107/S0108270113013267
# 2013 International Union of Crystallography 671

organic compounds
the nonplanarity in compounds (II) and (III), as opposed to
the exact or near skeletal planarity in compounds (I), IV) and
(V). However, it may also be noted here that the 2-thienyl
units in the nonplanar molecules of compounds (II) and (III)
are disordered over two sets of sites, corresponding to two
different orientations about the exocyclic C—C bond and
differing by 180ꢀ, with site occupancies of 0.802 (3) and
0.198 (3) in (II), and 0.798 (3) and 0.202 (3) in (III), while no
such disorder is apparent in the planar molecules of
compounds (I), (IV) and (V).
In the molecule of compound (I), the nitrile unit exhibits a
long C—C bond and a short C—N bond (Table 1), in common
with the nitrile units of compounds (II)–(V). There is evidence
for some slight bond fixation in the fused aryl ring of
compound (I), with the C24—C25 and C26—C27 bonds
somewhat shorter than the remaining bonds in this ring. The
other bonded distances in (I) show no unusual features. As
expected, the geometry at atom C2 is strictly planar, but all of
the interbond angles at C2 differ from the ideal value of 120ꢀ;
the C—C—C angle at atom C3 is markedly larger than the
ideal value (Table 1).
The molecules of compound (I) are linked by inversion-
related pairs of C—Hꢁ ꢁ ꢁN hydrogen bonds (Table 2) to form a
cyclic centrosymmetric dimer (Fig. 2) characterized by an
R22(18) motif (Bernstein et al., 1995). Dimers of this type are
weakly linked into a chain by an aromatic ꢀ–ꢀ stacking
interaction. The fluorinated aryl ring of the molecule at (x, y,
z) and the fused aryl ring of the molecule at (x + 1, y, z) make a
dihedral angle of 4.4 (2)ꢀ; the shortest perpendicular distance
from the centroid of one ring to the plane of the other ring is
Figure 3
A stereoview of part of the crystal structure of compound (I), showing the
formation of a ꢀ-stacked chain of hydrogen-bonded dimers along [100].
For the sake of clarity, H atoms not involved in the motif shown have
been omitted.
˚
ca 3.41 A and the ring-centroid separation is 3.883 (2) A,
˚
corresponding to a ring-centroid offset of ca 1.86 A. The
hydrogen-bonded dimers are thus linked into a chain running
parallel to the [100] direction, in which the R22(18) dimers are
centred at (n, , ), where n represents an integer (Fig. 3).
˚
1
2
1
2
It is of interest briefly to compare the supramolecular
assembly in compound (I) with the corresponding behaviour
in compounds (II)–(V). There are C—Hꢁ ꢁ ꢁN hydrogen bonds
present in the crystal structures of isostructural compounds
(II) and (III); as in compound (I), the nitrile N atom in (II)
and (III) acts as the hydrogen-bond acceptor, but here the
donor is the C—H bond of the central spacer unit, as opposed
to a ring C atom in compound (I). In this way, molecules of (II)
and (III) which are related by an n-glide plane are linked into
C(5) chains running parallel to [101]. There are no direction-
specific intermolecular interactions in the structure of com-
pound (IV), but the ordered molecules are nonetheless
arranged such that they enclose continuous rectangular
channels along the twofold rotation axes in the space group
C2/m, within which the fourfold disordered molecules are
located across sites of 2/m symmetry. There are no direction-
specific intermolecular interactions in the structure of
compound (V), which simply consists of effectively isolated
molecules.
Experimental
An intimate mixture of 2-(1,3-benzothiazol-2-yl)acetonitrile and
4-fluorobenzaldehyde (1 mmol of each component) was subjected to
microwave irradiation (maximum power 150 W) for 10 min under
solvent-free conditions at a controlled temperature and pressure of
473 K and 250 psi (1 psi = 6894.76 Pa), respectively, using a focused
microwave reaction (CEM Discover). After cooling the reaction
mixture to ambient temperature, product (I) was isolated by crys-
Figure 2
Part of the crystal structure of compound (I), showing the formation of a
hydrogen-bonded R22(18) dimer. For the sake of clarity, the unit-cell
outline and H atoms not involved in the motif shown have been omitted.
Atoms marked with an asterisk (*) are at the symmetry position (ꢃx,
ꢃy + 1, ꢃz + 1).
ꢂ
672 Trilleras et al.
C16H9FN2S
Acta Cryst. (2013). C69, 671–673

organic compounds
Table 1
Selected geometric parameters (A, ).
Table 2
Hydrogen-bond geometry (A, ).
ꢀ
˚
ꢀ
˚
N1—C1
C1—C2
C23A—C24
C24—C25
1.152 (3)
1.441 (3)
1.403 (3)
1.377 (4)
C25—C26
C26—C27
C27—C27A
C27A—C23A
1.409 (4)
1.381 (3)
1.390 (3)
1.408 (3)
D—Hꢁ ꢁ ꢁA
C25—H25ꢁ ꢁ ꢁN1i
Symmetry code: (i) ꢃx; ꢃy þ 1; ꢃz þ 1.
D—H
Hꢁ ꢁ ꢁA
Dꢁ ꢁ ꢁA
D—Hꢁ ꢁ ꢁA
0.95
2.57
3.440 (4)
152
N1—C1—C2
C1—C2—C3
C1—C2—C22
179.3 (3)
122.7 (2)
115.0 (2)
C3—C2—C22
C2—C3—C31
122.3 (2)
132.8 (2)
bad outlier reflection 101, partially attenuated by the beamstop, was
omitted.
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); soft-
ware used to prepare material for publication: SHELXL97 and
PLATON.
C1—C2—C3—C31
C22—C2—C3—C31
C1—C2—C22—N23
C1—C2—C22—S21
0.6 (5)
ꢃ179.1 (2)
ꢃ3.5 (4)
C3—C2—C22—N23
C3—C2—C22—S21
C2—C3—C31—C32
C2—C3—C31—C36
176.3 (2)
ꢃ4.0 (3)
7.9 (5)
ꢃ174.4 (3)
176.24 (18)
tallization of the reaction mixture, at ambient temperature and in air,
from ethanol to give brown crystals suitable for single-crystal X-ray
diffraction (yield 50%; m.p. 423–425 K). MS (EI, 70 eV) m/z (%): 281
[(M + 1)+, 10], 280 (M+, 39), 279 (100), 254 (22).
´
The authors thank ‘Centro de Instrumentacion Cientıfico-
Tecnica of Universidad de Jaen’ and the staff for data collec-
´
´
´
´
tion. JT and KV thank Universidad del Atlantico and
COLCIENCIAS for financial support. JC thanks the Conse-
Crystal data
3
´
jerıa de Innovacion, Ciencia y Empresa (Junta de Andalucıa,
Spain) and the Universidad de Jaen for financial support.
´
´
˚
C16H9FN2S
Mr = 280.32
V = 1264.8 (4) A
Z = 4
´
Monoclinic, P21=n
Mo Kꢂ radiation
ꢃ = 0.26 mmꢃ1
T = 120 K
0.39 ꢄ 0.35 ꢄ 0.20 mm
˚
a = 8.2432 (12) A
˚
b = 13.327 (3) A
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: SK3489). Services for accessing these data are
described at the back of the journal.
˚
c = 11.6819 (19) A
ꢁ = 99.743 (11)ꢀ
Data collection
References
Bruker–Nonius KappaCCD
diffractometer
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
Tmin = 0.906, Tmax = 0.950
2899 measured reflections
2899 independent reflections
1997 reflections with I > 2ꢄ(I)
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem.
Int. Ed. Engl. 34, 1555–1573.
Burla, M. C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G. L., De
Caro, L., Giacovazzo, C., Polidori, G. & Spagna, R. (2005). J. Appl. Cryst. 38,
381–388.
Cobo, D., Quiroga, J., Cobo, J. & Glidewell, C. (2009). Acta Cryst. C65, o444–o446.
Cobo, D., Quiroga, J., Cobo, J., Low, J. N. & Glidewell, C. (2005). Acta Cryst.
E61, o3639–o3641.
Cobo, D., Quiroga, J., de la Torre, J. M., Cobo, J., Low, J. N. & Glidewell, C.
(2006). Acta Cryst. C62, o550–o553.
Refinement
R[F2 > 2ꢄ(F2)] = 0.049
wR(F2) = 0.130
S = 1.09
182 parameters
H-atom parameteꢃrs3 constrained
˚
Áꢅmax = 0.34 e A
ꢃ3
˚
2899 reflections
Áꢅmin = ꢃ0.37 e A
Dawood, K. M., Elwan, N. M., Farahat, A. A. & Abdel-Wahab, B. F. (2010).
J. Heterocycl. Chem. 47, 243–267.
Duisenberg, A. J. M., Hooft, R. W. W., Schreurs, A. M. M. & Kroon, J. (2000).
J. Appl. Cryst. 33, 893–898.
Duisenberg, A. J. M., Kroon-Batenburg, L. M. J. & Schreurs, A. M. M. (2003).
J. Appl. Cryst. 36, 220–229.
Hooft, R. W. W. (1998). COLLECT. Nonius BV, Delft, The Netherlands.
Lenarda˜o, E. J., Silva, M. S., Mendes, S. R., de Azambuja, F., Jacob, R. G., Silva
dos Santos, P. C. & Perin, G. (2007). J. Braz. Chem. Soc. 18, 943–950.
All H atoms were located in difference maps and were then treated
as riding atoms in geometrically idealized positions, with C—H =
˚
0.95 A and Uiso(H) = 1.2Ueq(C). Conventional refinement converged
to R = 0.069 and analysis of the observed and calculated structure
factor data at this stage indicated nonmerohedral twinning, with a
twinning matrix of (0.399, 0, ꢃ0.601/ 0, ꢃ1, 0/ ꢃ1.399, 0, ꢃ0.399). Using
the original input reflection file (16480 measured reflections, of which
2900 were unique with a merging index of 0.0696), a modified file was
prepared by use of the TwinRotMat option in PLATON (Spek,
2009); this was used in the subsequent refinement, giving twin frac-
tions of 0.819 (3) and 0.181 (3). In the final cycles of refinement, the
´
Quiroga, J., Cruz, S., Insuasty, B. & Abonıa, R. (2000). Heterocycl. Commun. 6,
275–282.
Quiroga, J., Cruz, S., Insuasty, B., Abonıa, R., Nogueras, M., Sanchez, A.,
´
Cobo, J. & Low, J. N. (2001). J. Heterocycl. Chem. 38, 53–60.
´
¨
Sheldrick, G. M. (2003). SADABS. University of Gottingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Spek, A. L. (2009). Acta Cryst. D65, 148–155.
ꢂ
Acta Cryst. (2013). C69, 671–673
Trilleras et al. C16H9FN2S 673

supplementary materials
supplementary materials
Acta Cryst. (2013). C69, 671-673 [doi:10.1107/S0108270113013267]
(E)-2-(1,3-Benzothiazol-2-yl)-3-(4-fluorophenyl)acrylonitrile: a chain of π-
stacked hydrogen-bonded rings
Jorge Trilleras, Kelly Velásquez, Justo Cobo and Christopher Glidewell
(E)-2-(1,3-Benzothiazol-2-yl)-3-(4-fluorophenyl)acrylonitrile
Crystal data
C16H9FN2S
Mr = 280.32
F(000) = 576
Dx = 1.472 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 2900 reflections
θ = 2.8–27.5°
Monoclinic, P21/n
Hall symbol: -P 2yn
a = 8.2432 (12) Å
b = 13.327 (3) Å
c = 11.6819 (19) Å
β = 99.743 (11)°
V = 1264.8 (4) Å3
Z = 4
µ = 0.26 mm−1
T = 120 K
Block, brown
0.39 × 0.35 × 0.20 mm
Data collection
Bruker–Nonius KappaCCD
diffractometer
Radiation source: Bruker–Nonius FR591
rotating anode
Graphite monochromator
Detector resolution: 9.091 pixels mm-1
φ & ω scans
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
Tmin = 0.906, Tmax = 0.950
2899 measured reflections
2899 independent reflections
1997 reflections with I > 2σ(I)
Rint = 0.0000
θ
max = 27.5°, θmin = 2.9°
h = −10→10
k = −17→17
l = −14→15
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.049
wR(F2) = 0.130
Secondary atom site location: difference Fourier
map
Hydrogen site location: inferred from
neighbouring sites
S = 1.09
2899 reflections
182 parameters
0 restraints
Primary atom site location: structure-invariant
direct methods
H-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0548P)2 + 0.6112P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.001
Δρmax = 0.34 e Å−3
Δρmin = −0.37 e Å−3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
y
z
Uiso*/Ueq
N1
0.4507 (3)
0.60285 (16)
0.3715 (2)
0.0338 (5)
Acta Cryst. (2013). C69, 671-673
sup-1

supplementary materials
C1
0.4517 (3)
0.4514 (3)
0.5690 (3)
0.5526
0.51738 (19)
0.41065 (18)
0.36372 (19)
0.2934
0.3567 (2)
0.3370 (2)
0.2885 (2)
0.2800
0.0261 (5)
0.0258 (5)
0.0267 (5)
0.032*
C2
C3
H3
S21
C22
N23
C23A
C24
H24
C25
H25
C26
H26
C27
H27
C27A
C31
C32
H32
C33
H33
C34
F34
C35
H35
C36
H36
0.29074 (8)
0.3145 (3)
0.2051 (2)
0.0915 (3)
−0.0429 (3)
−0.0640
0.22740 (5)
0.35624 (19)
0.39923 (15)
0.32781 (19)
0.3473 (2)
0.4133
0.34760 (6)
0.3737 (2)
0.42593 (18)
0.4504 (2)
0.5063 (2)
0.5308
0.0305 (2)
0.0261 (5)
0.0256 (5)
0.0256 (5)
0.0294 (6)
0.035*
−0.1438 (3)
−0.2348
0.2687 (2)
0.2810
0.5249 (2)
0.5632
0.0305 (6)
0.037*
−0.1151 (3)
−0.1866
0.1705 (2)
0.1178
0.4884 (2)
0.5025
0.0333 (6)
0.040*
0.0158 (3)
0.0357
0.1501 (2)
0.0840
0.4323 (2)
0.4074
0.0323 (6)
0.039*
0.1177 (3)
0.7152 (3)
0.7773 (3)
0.7220
0.22943 (18)
0.39951 (18)
0.49749 (19)
0.5459
0.4135 (2)
0.2470 (2)
0.2621 (2)
0.3012
0.0262 (5)
0.0254 (5)
0.0324 (6)
0.039*
0.9183 (3)
0.9602
0.52394 (19)
0.5904
0.2205 (2)
0.2303
0.0336 (6)
0.040*
0.9977 (3)
1.13733 (18)
0.9438 (3)
1.0017
0.4528 (2)
0.47945 (11)
0.35539 (19)
0.3074
0.1645 (2)
0.12503 (14)
0.1497 (2)
0.1119
0.0293 (6)
0.0392 (4)
0.0295 (6)
0.035*
0.8021 (3)
0.7628
0.32955 (19)
0.2625
0.1917 (2)
0.1827
0.0283 (6)
0.034*
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
N1
0.0341 (13)
0.0237 (12)
0.0262 (13)
0.0271 (13)
0.0311 (4)
0.0279 (13)
0.0273 (14)
0.0244 (13)
0.0239 (13)
0.0244 (3)
0.0414 (13)
0.0018 (10)
0.0018 (11)
0.0003 (10)
0.0001 (10)
−0.0015 (3)
0.0029 (10)
0.0005 (9)
0.0117 (10)
0.0074 (10)
0.0055 (10)
0.0058 (10)
0.0152 (3)
0.0058 (10)
0.0072 (9)
0.0039 (10)
0.0067 (11)
0.0100 (10)
0.0111 (12)
0.0128 (12)
0.0058 (10)
0.0077 (10)
0.0166 (12)
0.0168 (12)
0.0101 (11)
0.0237 (8)
0.0010 (10)
0.0020 (11)
0.0008 (10)
−0.0020 (10)
−0.0035 (3)
0.0032 (10)
0.0016 (9)
C1
0.0283 (13)
0.0273 (13)
0.0293 (13)
0.0390 (4)
C2
C3
S21
C22
N23
C23A
C24
C25
C26
C27
C27A
C31
C32
C33
C34
F34
0.0246 (12)
0.0257 (11)
0.0249 (12)
0.0290 (13)
0.0269 (13)
0.0330 (14)
0.0356 (14)
0.0248 (12)
0.0264 (12)
0.0315 (14)
0.0335 (14)
0.0251 (13)
0.0331 (8)
0.0258 (13)
0.0230 (11)
0.0285 (13)
0.0296 (14)
0.0371 (15)
0.0352 (15)
0.0288 (14)
0.0272 (13)
0.0235 (13)
0.0254 (13)
0.0233 (13)
0.0311 (14)
0.0364 (9)
0.0283 (13)
0.0290 (11)
0.0234 (12)
0.0302 (14)
0.0294 (13)
0.0337 (15)
0.0349 (15)
0.0271 (12)
0.0274 (12)
0.0438 (16)
0.0475 (17)
0.0334 (14)
0.0538 (10)
0.0013 (10)
0.0030 (11)
−0.0002 (12)
−0.0059 (12)
−0.0024 (12)
−0.0003 (11)
0.0023 (10)
0.0047 (11)
−0.0012 (11)
0.0014 (11)
−0.0020 (7)
0.0012 (10)
−0.0017 (11)
0.0006 (12)
0.0036 (12)
−0.0017 (12)
−0.0010 (11)
0.0004 (10)
−0.0007 (12)
0.0001 (12)
0.0040 (11)
0.0007 (8)
Acta Cryst. (2013). C69, 671-673
sup-2

supplementary materials
C35
C36
0.0282 (13)
0.0290 (13)
0.0312 (14)
0.0238 (13)
0.0302 (14)
0.0325 (14)
0.0042 (11)
0.0002 (11)
0.0085 (11)
0.0061 (11)
−0.0025 (11)
−0.0037 (11)
Geometric parameters (Å, º)
N1—C1
1.152 (3)
C26—H26
0.9500
C1—C2
1.441 (3)
1.355 (3)
1.465 (3)
1.453 (3)
0.9500
C27—C27A
C27—H27
C27A—C23A
C31—C36
C31—C32
C32—C33
C32—H32
C33—C34
C33—H33
C34—F34
C34—C35
C35—C36
C35—H35
C36—H36
1.390 (3)
0.9500
C2—C3
C2—C22
C3—C31
C3—H3
1.408 (3)
1.399 (3)
1.403 (3)
1.380 (3)
0.9500
S21—C27A
S21—C22
C22—N23
N23—C23A
C23A—C24
C24—C25
C24—H24
C25—C26
C25—H25
C26—C27
1.732 (2)
1.749 (3)
1.304 (3)
1.398 (3)
1.403 (3)
1.377 (4)
0.9500
1.378 (4)
0.9500
1.358 (3)
1.373 (4)
1.385 (3)
0.9500
1.409 (4)
0.9500
0.9500
1.381 (3)
N1—C1—C2
179.3 (3)
122.7 (2)
115.0 (2)
122.3 (2)
132.8 (2)
113.6
C26—C27—C27A
C26—C27—H27
C27A—C27—H27
C27—C27A—C23A
C27—C27A—S21
C23A—C27A—S21
C36—C31—C32
C36—C31—C3
117.7 (2)
121.1
C1—C2—C3
C1—C2—C22
121.1
C3—C2—C22
122.2 (2)
128.5 (2)
109.31 (18)
118.3 (2)
117.0 (2)
124.7 (2)
120.3 (2)
119.8
C2—C3—C31
C2—C3—H3
C31—C3—H3
113.6
C27A—S21—C22
N23—C22—C2
N23—C22—S21
C2—C22—S21
C22—N23—C23A
N23—C23A—C24
N23—C23A—C27A
C24—C23A—C27A
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
89.05 (11)
123.2 (2)
116.56 (18)
120.25 (18)
109.7 (2)
125.3 (2)
115.4 (2)
119.3 (2)
118.5 (2)
120.7
C32—C31—C3
C33—C32—C31
C33—C32—H32
C31—C32—H32
C34—C33—C32
C34—C33—H33
C32—C33—H33
F34—C34—C35
F34—C34—C33
C35—C34—C33
C34—C35—C36
C34—C35—H35
C36—C35—H35
C35—C36—C31
C35—C36—H36
C31—C36—H36
119.8
119.2 (2)
120.4
120.4
118.6 (2)
118.6 (2)
122.7 (2)
117.7 (2)
121.2
120.7
121.5 (2)
119.3
119.3
121.2
120.8 (2)
119.6
121.8 (2)
119.1
119.6
119.1
C1—C2—C3—C31
C22—C2—C3—C31
C1—C2—C22—N23
0.6 (5)
N23—C23A—C27A—C27
C24—C23A—C27A—C27
N23—C23A—C27A—S21
179.5 (2)
−1.1 (4)
0.5 (3)
−179.1 (2)
−3.5 (4)
Acta Cryst. (2013). C69, 671-673
sup-3

supplementary materials
C1—C2—C22—S21
176.24 (18)
176.3 (2)
−4.0 (3)
−0.4 (2)
179.9 (2)
−179.6 (2)
0.7 (3)
C24—C23A—C27A—S21
179.90 (18)
−179.1 (3)
−0.09 (19)
7.9 (5)
C3—C2—C22—N23
C22—S21—C27A—C27
C22—S21—C27A—C23A
C2—C3—C31—C32
C3—C2—C22—S21
C27A—S21—C22—N23
C27A—S21—C22—C2
C2—C22—N23—C23A
S21—C22—N23—C23A
C22—N23—C23A—C24
C22—N23—C23A—C27A
N23—C23A—C24—C25
C27A—C23A—C24—C25
C23A—C24—C25—C26
C24—C25—C26—C27
C25—C26—C27—C27A
C26—C27—C27A—C23A
C26—C27—C27A—S21
C2—C3—C31—C36
−174.4 (3)
1.6 (4)
C36—C31—C32—C33
C3—C31—C32—C33
C31—C32—C33—C34
C32—C33—C34—F34
C32—C33—C34—C35
F34—C34—C35—C36
C33—C34—C35—C36
C34—C35—C36—C31
C32—C31—C36—C35
C3—C31—C36—C35
179.3 (3)
−0.3 (4)
179.9 (2)
−0.8 (3)
−179.7 (2)
1.0 (4)
−179.3 (2)
−1.0 (4)
179.4 (2)
1.0 (4)
−0.4 (4)
−0.1 (4)
0.1 (4)
0.3 (4)
−1.6 (4)
0.5 (4)
−179.5 (2)
179.3 (2)
Hydrogen-bond geometry (Å, º)
D—H···A
C25—H25···N1i
D—H
H···A
D···A
3.440 (4)
D—H···A
152
0.95
2.57
Symmetry code: (i) −x, −y+1, −z+1.
Acta Cryst. (2013). C69, 671-673
sup-4