1-Benzoyl-3-[(2-benzylsulfanyl)phenyl]thiourea

Article abstract of DOI:10.1107/S0108270112045167

In the title compound, C21H18N2OS2, a strong intramolecular N-H?O hydrogen bond [N?O = 2.642(3)?] between the amide N atom and the benzoyl O atom forms an almost planar six-membered ring in the central part of the molecule. In the crystal, molecules are p

Full text of DOI:10.1107/S0108270112045167

organic compounds
spectrum of (I) shows absorption bands at 3328 cmꢁ1 for
ꢀ(N—H), at 1336 cmꢁ1 for ꢀ(C—N) and at 748 cmꢁ1 for
ꢀ(C S). The absorption band at 748 cmꢁ1 for ꢀ(C S)
confirms the formation of the thiourea compound (Bombicz et
al., 2004). The strong ꢀ(C O) absorption band for (I) is at
1671 cmꢁ1, apparently decreased in frequency compared with
a typical carbonyl absorption (1700 cmꢁ1). This is interpreted
as being a result of its conjugated resonance with the phenyl
ring and the possible formation of an intramolecular hydrogen
Acta Crystallographica Section C
Crystal Structure
Communications
ISSN 0108-2701
1-Benzoyl-3-[(2-benzylsulfanyl)-
phenyl]thiourea
Tirtha Bhattacharjee,a Prasanta Gogoi,a Vedavati G.
Puranik,b Rupesh L. Gawadeb and Pranjit Barmana*
aDepartment of Chemistry, National Institute of Technology, Silchar 788 010, Assam,
India, and bCenter for Materials Characterization, National Chemical Laboratory,
Pune 411 008, India
Correspondence e-mail: barmanpranjit@yahoo.co.in
Received 1 October 2012
Accepted 31 October 2012
Online 9 November 2012
In the title compound, C21H18N2OS2, a strong intramolecular
˚
N—Hꢀ ꢀ ꢀO hydrogen bond [Nꢀ ꢀ ꢀO = 2.642 (3) A] between the
amide N atom and the benzoyl O atom forms an almost planar
six-membered ring in the central part of the molecule. In the
crystal, molecules are packed through weak N—Hꢀ ꢀ ꢀS inter-
actions. Intra- and intermolecular hydrogen bonds and van der
Waals interactions are the stabilizing forces for the crystal
structure.
bond with an N—H group. In the electronic spectrum of (I),
absorption bands are observed at ꢁmax = 240 and 270 nm. The
broad absorption band observed in the region ꢁmax = 240–
320 nm is due to ꢂ–ꢂ conjugation of the phenyl rings (ꢂ–ꢂ*
Comment
transition) and orbital overlapping between C O and C
S
Thioureas have been mentioned in the syntheses of hetero-
cycles (Singh et al., 2006) and coordination complexes (Kemp
et al., 1997), and particularly in medicinal chemistry (Murtaza
et al., 2012). They have been shown to possess antitubercular,
antithroid, anthelmintic, antibacterial, insecticidal and
rodenticidal properties (Schroeder, 1955; Huebhr et al., 1953;
Madan & Taneja, 1991), and have also been found as inter-
esting organic inhibitors for corrosion activity (Koch &
Bourne, 1998). In recent years, the structures and intra- and
intermolecular hydrogen-bonding behaviour of some N-aryl-
N0-benzoylthioureas have been thoroughly investigated
(Zhang et al., 1996; Cao et al., 1996; Dago et al., 1989;
Kaminsky et al., 2002). Single-crystal X-ray diffraction studies
of these thioureas have revealed the existence of a six-
membered ring formed by an intramolecular hydrogen bond
between the carbonyl O atom and an NH group (Zhou et al.,
2003). These features prompted us to study the antibacterial
activity, structure and hydrogen-bonding interactions of an N-
aryl-N0-benzoylthiourea with benzylsulfanyl as a substituent
on the aryl ring. In this paper, the solid-state synthesis, char-
acterization, crystal structure and antibacterial activity of
1-benzoyl-3-[(2-benzylsulfanyl)phenyl]thiourea, (I), are pre-
sented.
groups. The 1NMR spectrum of (I) in CDCl3 (400 MHz
spectrometer) shows the N—H resonance considerably
downfield from other resonances in the spectrum. The
Figure 1
Compound (I) was synthesized by an environmentally
friendly solid-state pasting-and-grinding method without the
use of any hazardous organic solvent (Fig. 1). The FT–IR
The molecular struicture of the title compound, showing the atom-
labelling scheme. Displacement ellipsoids are drawn at the 50%
probability level.
Acta Cryst. (2012). C68, o485–o487
doi:10.1107/S0108270112045167
# 2012 International Union of Crystallography o485

organic compounds
intramolecular C14—H14ꢀ ꢀ ꢀS2 interaction, forming an S(6)
ring, stabilize the molecular geometry and crystal packing
along with two other intramolecular hydrogen bonds (N2—
H1N2ꢀ ꢀ ꢀS1 and C6—H6ꢀ ꢀ ꢀO1), forming a five-membered
ring, and van der Waals interactions.
The crystal structure of (I) is further stabilized by three
intermolecular hydrogen bonds (N1—H1N1ꢀ ꢀ ꢀS2i, C2—
H2Aꢀ ꢀ ꢀS2i and C15—H15Aꢀ ꢀ ꢀO1ii; Table 2). Atoms S2, C8,
N1 and H1N1 form an eight-membered hydrogen-bonded
ring, resulting in a dimer around an inversion centre, as shown
in Fig. 2. These five-, six- and eight-membered hydrogen-
bonded rings can be described by the graph-set motifs S(5),
S(6) and R22(8), respectively (Fig. 2).
From the MIC (minimum inhibitory concentration) study of
(I) (see Experimental), it can be seen that the compound has
some amount of inhibitory activity against Gram-positive and
Gram-negative bacteria. Bacillus subtilis, Klebsiella pneumo-
niae and Esherichia coli are seen to be inhibited at concen-
trations of 3.125, 6.25 and 12.50 g lꢁ1 of (I), respectively.
Experimental
2-(Benzylsulfanyl)aniline was synthesized according to the literature
procedure of Shi et al. (2006). All the chemicals used were of Merck
purity. In a typical procedure, benzoyl chloride (1.16 ml, 0.01 mol)
was added dropwise to a solution of ammonium thiocyanate (0.76 g,
0.01 mol) in water (10 ml) and stirred for 1 h. The solid which formed
was filtered off, dried between sheets of filter paper and mixed with
2-(benzylsulfanyl)aniline (2.15 g, 0.01 mol). The solid mixture was
then ground in an agate mortar for 30 min, extracted with acetone
and diluted with cold water. The solid thiourea which formed was
filtered off, dried and recrystallized from methanol–dichloromethane
(1:1 v/v) to obtain white crystals suitable for X-ray diffraction analysis
(yield 90%; m.p. 369 K). 1H NMR (TMS, CDCl3): ꢃ 12.73 (s, 1H), 9.07
(s, 1H), 8.32 (d, J = 8.28 Hz, 1H), 7.93 (d, J = 6.88 Hz, 2H), 7.66 (t, J =
8 Hz, 1H), 7.55 (t, J = 8.1 Hz, 2H), 7.41 (d, J = 8 Hz, 1H), 7.34 (t, J =
8 Hz, 1H), 7.12–7.21 (m, 6H), 4.02 (s, 2H). 13C NMR (TMS, CDCl3): ꢃ
178.45, 166.28, 133.69, 129.22, 128.99, 128.42, 127.62, 127.27, 127.08,
39.99. FT–IR (KBr) ꢀmax (cmꢁ1): (C O) 1671, (N—H) 3328, (C—N)
1336, (C S) 748. UV–Visible (ꢁmax, EtOH): 240, 206. Analysis
calculated for C21H18N2OS2: C 66.66, H 4.76, N 7.40%; found: C
66.39, H 4.70, N 7.21%.
Figure 2
Capped-sticks diagrams showing the formation of the dimer of (I) via
hydrogen bonding. [Symmetry codes: (i) ꢁx; ꢁy þ 1; ꢁz; (ii) x; y ꢁ 1; z.]
chemical shift for N—H was found as a singlet at ꢃ 12.73 for
the H atom in the hydrogen bond. Another singlet of N—H
was at about at ꢃ 9.07. Two benzyl H atoms appear as a singlet
at ꢃ 4.02. Aromatic H atoms appear around ꢃ 7.21–8.33. The
13C NMR spectrum in CDCl3 (100 MHz) shows peaks at ꢃ
178.45, 166.28 and 39.99 for C S, C O and the benzyl
methylene C atom, respectively. Peaks at ꢃ 127.08–133.69
correspond to the aromatic C atoms.
Single crystals of (I) suitable for X-ray analysis were grown
from methanol–dichloromethane (1:1 v/v). The analysis of (I)
shows that it crystallizes in the monoclinic space group P21/c
with four molecules in the unit cell. In the molecule, the
C7—O1 and C8—S2 bonds show typical double-bond char-
acter (Table 1). All the C—N bonds are indicative of partial
double-bond character. The C8—N1 bond, due to its proxi-
mity to the carbonyl group, is slightly shorter compared to the
C9—N2 bond (Zhang et al., 1996; Jin et al., 1997). These bond
lengths are in agreement with the corresponding distances
observed in other 1-benzoyl-3-phenylthiourea molecules
reported in the Cambridge Structural Database (Allen, 2002)
[refcodes AMEBOJ (Arslan et al., 2003), ERENUK (Zhou et
al., 2004), GUWFIN (Yamin & Yusof, 2003b), HOFHIT
(Shanmuga Sundara Raj et al., 1999), HURYAU (Yamin &
Yusof, 2003a), PUYWIP (Usman et al., 2002), UKOQUG
(Zhou et al., 2003), WIRSEV (Zhang et al., 1996) and
XEQDAY (Li et al., 2000)].
In the antibacterial study, the MIC value of the synthesized
compound was determined according to the literature method of
Rangasamy et al. (2007). Klebsiella pneumoniae and Escherichia Coli
as Gram negative and Bacillus subtilis as Gram positive strains of
bacteria was used for the study. These bacteria were cultured in Luria
broth (LB) media and cultures were grown until they obtained a
growth equivalent to 0.5 McFarland’s Standard. A stock solution of
25 g lꢁ1 in 100% dimethyl sulfoxide of the compound was prepared.
The MIC was determined using 96 well plates. 200 ml of the
compound from the stock solution was added to the first well. From
the second well to the eighth well, 100 ml of LB media was added.
Now from the first well 100 ml of the solution was taken and added to
the second well and subsequently serially diluted until the eighth well
had a concentration of 195 mg mlꢁ1. To all the wells, 100 ml of
bacterial inoculum were added. The plates were then incubated at
310 K overnight. After the incubation period, 40 ml of MTT [3-(4,5-
dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide] solution [at a
concentration of 0.2 g lꢁ1 of Phosphate Buffer Saline (pH 7.4)] was
Like other N-benzoyl-N0-phenylthioureas, (I) possesses
intra- and intermolecular hydrogen-bonding interactions, as
detailed in Table 2. The strong intramolecular hydrogen-bond-
like N2—H1N2ꢀ ꢀ ꢀO1 interaction between carbonyl atom O1
and an NH group, forming a six-membered ring, and a weak
ꢂ
o486 Bhattacharjee et al.
C21H18N2OS2
Acta Cryst. (2012). C68, o485–o487

organic compounds
added to each well. The plates were again incubated for 40 min at
310 K. After the incubation period, the plates were checked for any
change in color. A change of colour to blue indicated bacterial growth
signifying that the compounds do not have any inhibitory activity,
while no change of colour means a positive result indicating inhibi-
tory activity of the compounds.
Table 1
Selected bond lengths (A).
˚
S2—C8
O1—C7
N1—C7
1.674 (3)
1.230 (4)
1.381 (4)
N1—C8
N2—C8
1.401 (4)
1.353 (4)
Crystal data
Table 2
3
ꢃ
˚
Hydrogen-bond geometry (A, ).
˚
C21H18N2OS2
Mr = 378.49
V = 1841.5 (3) A
Z = 4
Monoclinic, P21=c
Mo Kꢅ radiation
ꢆ = 0.30 mmꢁ1
T = 100 K
0.49 ꢄ 0.04 ꢄ 0.04 mm
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
˚
a = 19.8574 (18) A
N1—H1N1ꢀ ꢀ ꢀS2i
N2—H1N2ꢀ ꢀ ꢀO1
N2—H1N2ꢀ ꢀ ꢀS1
C2—H2Aꢀ ꢀ ꢀS2i
C6—H6ꢀ ꢀ ꢀO1
0.88
0.88
0.88
0.95
0.95
0.95
0.99
2.90
1.91
2.49
2.77
2.43
2.50
2.39
3.688 (4)
2.642 (3)
2.997 (3)
3.556 (4)
2.760 (4)
3.184 (4)
3.366 (4)
150
140
117
141
100
129
168
˚
b = 4.9195 (5) A
˚
c = 19.6197 (18) A
ꢄ = 106.089 (2)ꢃ
Data collection
C14—H14ꢀ ꢀ ꢀS2
C15—H15Aꢀ ꢀ ꢀO1ii
Bruker SMART APEX CCD area-
detector diffractometer
Absorption correction: multi-scan
(SADABS; Bruker, 2007)
Tmin = 0.866, Tmax = 0.990
8509 measured reflections
3231 independent reflections
2488 reflections with I > 2ꢇ(I)
Rint = 0.063
Symmetry codes: (i) ꢁx; ꢁy þ 1; ꢁz; (ii) x; y ꢁ 1; z.
Bruker (2007). SMART, SAINT and SADABS. Bruker AXS Inc., Madison,
Wisconsin, USA.
Refinement
R[F2 > 2ꢇ(F2)] = 0.064
wR(F2) = 0.138
S = 1.11
235 parameters
H-atom parameteꢁrs3 constrained
Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak
Ridge National Laboratory, Tennessee, USA.
Cao, Y., Zhao, B., Zhang, Y.-Q. & Zhang, D.-C. (1996). Acta Cryst. C52, 1772–
1774.
´
Dago, A., Shepelev, Yu., Fajardo, F., Alvarez, F. & Pomes, R. (1989). Acta
Cryst. C45, 1192–1194.
˚
Áꢈmax = 0.33 e A
ꢁ3
˚
3231 reflections
Áꢈmin = ꢁ0.30 e A
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Troxell, H. A. & Scholz, C. R. (1953). J. Am. Chem. Soc. 75, 2274–2275.
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9–15.
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(2007). J. Ethnopharmacol. 109, 331–337.
H atoms were placed in calculated positions, with C—H = 0.95 and
˚
0.99 A for aromatic and benzyl H atoms, respectively, and N—H =
˚
0.88 A, and refined as riding atoms with Uiso(H) = 1.2Ueq(C,N).
Data collection: SMART (Bruker, 2007); cell refinement: SAINT
(Bruker, 2007); data reduction: SAINT; program(s) used to solve
structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine
structure: SHELXL97 (Sheldrick, 2008); molecular graphics:
SHELXTL (Sheldrick, 2008); software used to prepare material for
publication: SHELXTL and ORTEPIII (Burnett & Johnson, 1996).
The authors thank the Director of NIT, Silchar, for
laboratory facilities, Mr Ranjan Dutta Kalita, Tezpur
University, for antibacterial studies and the Council of
Scientific and Industrial Research, CSIR, New Delhi, for the
award of a senior research fellowship to TB.
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5399.
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: FN3118). Services for accessing these data are
described at the back of the journal.
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¨ ¨ ¨
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´
ꢂ
Acta Cryst. (2012). C68, o485–o487
Bhattacharjee et al. C21H18N2OS2 o487

supplementary materials
supplementary materials
Acta Cryst. (2012). C68, o485–o487 [doi:10.1107/S0108270112045167]
1-Benzoyl-3-[(2-benzylsulfanyl)phenyl]thiourea
Tirtha Bhattacharjee, Prasanta Gogoi, Vedavati G. Puranik, Rupesh L. Gawade and Pranjit
Barman
1-Benzoyl-3-[(2-benzylsulfanyl)phenyl]thiourea
Crystal data
C21H18N2OS2
Mr = 378.49
F(000) = 792
Dx = 1.365 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 1378 reflections
θ = 2.6–24.3°
Monoclinic, P21/c
a = 19.8574 (18) Å
b = 4.9195 (5) Å
c = 19.6197 (18) Å
β = 106.089 (2)°
V = 1841.5 (3) Å3
Z = 4
µ = 0.30 mm−1
T = 100 K
Needle, colourless
0.49 × 0.04 × 0.04 mm
Data collection
Bruker SMART APEX CCD area-detector
diffractometer
Radiation source: fine-focus sealed tube
Graphite monochromator
ω scans
8509 measured reflections
3231 independent reflections
2488 reflections with I > 2σ(I)
Rint = 0.063
θ
max = 25.0°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Bruker, 2007)
h = −21→23
k = −5→5
T
min = 0.866, Tmax = 0.990
l = −23→17
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.064
wR(F2) = 0.138
Secondary atom site location: difference Fourier
map
Hydrogen site location: inferred from
neighbouring sites
S = 1.11
3231 reflections
235 parameters
0 restraints
Primary atom site location: structure-invariant
direct methods
H-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0507P)2]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.33 e Å−3
Δρmin = −0.30 e Å−3
Acta Cryst. (2012). C68, o485–o487
sup-1

supplementary materials
Special details
Experimental. Melting points was determined in an open capillary and was uncorrected. The UV–Visible spectrum was
recorded on a Cary100 Bio UV Vis spectrophotometer. The IR spectrum was obtained on a Perkin–Elmer 73633 FT–IR
spectrometer as a KBr Pellet. 1H and 13C NMR spectra were recorded on a Varian (400 MHz and 100 MHz) FT NMR
spectrometer using TMS as an internal standard and CDCl3 as solvent. The elemental analysis was conducted using
CHNS Perkin Elmer Model. 240 analyzer. Single crystal X-ray was collected on Bruker SMART APEX CCD
diffractometer.
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full
covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and
torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry.
An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2,
conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used
only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2
are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
y
z
Uiso*/Ueq
S1
0.35151 (4)
0.07128 (5)
0.22284 (11)
0.12021 (13)
0.0780
0.24021 (17)
0.3494 (2)
0.6259 (5)
0.6122 (6)
0.6842
0.12672 (5)
−0.04484 (5)
0.16257 (12)
0.07484 (14)
0.0610
0.0249 (3)
0.0404 (3)
0.0280 (6)
0.0235 (7)
0.028*
S2
O1
N1
H1N1
N2
0.19849 (13)
0.2242
0.2955 (5)
0.3540
0.05228 (14)
0.0937
0.0203 (6)
0.024*
H1N2
C1
0.13422 (16)
0.06821 (16)
0.0382
0.9309 (6)
1.0536 (7)
1.0013
0.17494 (17)
0.14910 (19)
0.1043
0.0198 (7)
0.0248 (8)
0.030*
C2
H2A
C3
0.04672 (19)
0.0019
1.2520 (7)
1.3335
0.1891 (2)
0.1716
0.0336 (9)
0.040*
H3
C4
0.0898 (2)
0.0744
1.3311 (8)
1.4658
0.2536 (2)
0.2806
0.0342 (9)
0.041*
H4
C5
0.1556 (2)
0.1857
1.2153 (8)
1.2729
0.27958 (19)
0.3238
0.0367 (10)
0.044*
H5
C6
0.17737 (19)
0.2222
1.0158 (7)
0.9351
0.24078 (18)
0.2590
0.0311 (9)
0.037*
H6
C7
0.16287 (16)
0.13451 (16)
0.23139 (16)
0.30378 (17)
0.33841 (19)
0.3871
0.7121 (7)
0.4126 (7)
0.0943 (6)
0.0495 (7)
−0.1509 (7)
−0.1795
0.13786 (17)
0.02985 (17)
0.02050 (17)
0.05132 (17)
0.02339 (19)
0.0441
0.0201 (8)
0.0228 (8)
0.0196 (7)
0.0227 (8)
0.0300 (9)
0.036*
C8
C9
C10
C11
H11
C12
H12
C13
H13
C14
H14
C15
0.3032 (2)
0.3273
−0.3085 (7)
−0.4449
−0.03384 (19)
−0.0521
0.0328 (9)
0.039*
0.2322 (2)
0.2077
−0.2645 (7)
−0.3716
−0.06423 (18)
−0.1036
0.0330 (9)
0.040*
0.19625 (18)
0.1477
−0.0648 (7)
−0.0368
−0.03773 (17)
−0.0593
0.0276 (8)
0.033*
0.37545 (17)
−0.0348 (7)
0.19253 (18)
0.0270 (8)
Acta Cryst. (2012). C68, o485–o487
sup-2

supplementary materials
H15A
H15B
C16
C17
H17
C18
H18
C19
H19
C20
H20
C21
H21
0.3347
−0.1568
−0.1432
0.0774 (7)
−0.0285 (7)
−0.1624
0.0596 (8)
−0.0170
0.2601 (8)
0.3228
0.1876
0.032*
0.4141
0.1835
0.032*
0.39813 (16)
0.45717 (16)
0.4846
0.26693 (18)
0.31547 (18)
0.3006
0.0237 (8)
0.0275 (8)
0.033*
0.47652 (18)
0.5164
0.3856 (2)
0.4185
0.0336 (9)
0.040*
0.4375 (2)
0.4509
0.4075 (2)
0.4552
0.0377 (10)
0.045*
0.3791 (2)
0.3523
0.3667 (8)
0.5029
0.3589 (2)
0.3737
0.0381 (10)
0.046*
0.35907 (19)
0.3188
0.2792 (7)
0.3551
0.2896 (2)
0.2571
0.0318 (9)
0.038*
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
S1
0.0245 (5)
0.0206 (5)
0.0242 (13)
0.0163 (14)
0.0226 (15)
0.0251 (17)
0.0223 (17)
0.033 (2)
0.0128 (5)
0.0634 (8)
0.0256 (15)
0.0276 (18)
0.0174 (17)
0.0101 (18)
0.016 (2)
0.0372 (5)
−0.0009 (4)
−0.0005 (5)
0.0052 (11)
0.0025 (12)
−0.0015 (12)
−0.0026 (14)
−0.0054 (14)
0.0060 (17)
0.0081 (18)
0.0125 (19)
0.0105 (17)
−0.0047 (14)
−0.0064 (15)
−0.0048 (14)
−0.0028 (15)
0.0043 (16)
0.0048 (17)
−0.0058 (19)
−0.0024 (16)
−0.0006 (15)
−0.0054 (14)
−0.0008 (15)
−0.0063 (17)
−0.0111 (19)
0.0068 (19)
0.0041 (16)
0.0085 (4)
0.0043 (4)
0.0028 (11)
0.0069 (12)
0.0062 (12)
0.0126 (14)
0.0114 (15)
0.0208 (19)
0.028 (2)
−0.0012 (4)
−0.0209 (5)
−0.0045 (11)
−0.0029 (13)
−0.0032 (12)
0.0056 (14)
0.0007 (15)
0.0081 (18)
0.0046 (17)
−0.0005 (17)
0.0084 (17)
0.0061 (14)
−0.0021 (15)
0.0034 (13)
0.0029 (14)
0.0067 (17)
0.0003 (16)
−0.0014 (15)
−0.0001 (15)
0.0009 (15)
−0.0009 (15)
−0.0021 (17)
0.0024 (18)
−0.0035 (18)
−0.0007 (19)
0.0038 (17)
S2
0.0351 (6)
0.0312 (14)
0.0271 (16)
0.0212 (15)
0.0275 (19)
0.038 (2)
0.055 (3)
0.040 (2)
0.024 (2)
0.026 (2)
0.0223 (18)
0.0239 (19)
0.0214 (18)
0.028 (2)
0.041 (2)
0.035 (2)
0.023 (2)
0.025 (2)
0.039 (2)
0.036 (2)
0.039 (2)
0.040 (2)
0.038 (2)
0.040 (2)
0.042 (2)
O1
N1
N2
C1
C2
C3
0.018 (2)
C4
0.052 (2)
0.020 (2)
C5
0.060 (3)
0.027 (2)
0.0123 (19)
0.0088 (16)
0.0086 (14)
0.0129 (15)
0.0140 (15)
0.0153 (16)
0.0224 (18)
0.026 (2)
C6
0.038 (2)
0.029 (2)
C7
0.0242 (18)
0.0259 (18)
0.0313 (18)
0.0363 (19)
0.040 (2)
0.0152 (19)
0.022 (2)
C8
C9
0.0101 (18)
0.0081 (18)
0.016 (2)
C10
C11
C12
C13
C14
C15
C16
C17
C18
C19
C20
C21
0.056 (3)
0.015 (2)
0.066 (3)
0.015 (2)
0.0187 (18)
0.0100 (16)
0.0045 (16)
0.0105 (15)
0.0117 (16)
0.0077 (17)
0.019 (2)
0.037 (2)
0.022 (2)
0.0288 (18)
0.0248 (18)
0.0221 (18)
0.0279 (19)
0.048 (2)
0.0107 (19)
0.0116 (19)
0.024 (2)
0.031 (2)
0.031 (2)
0.051 (2)
0.030 (2)
0.024 (2)
0.034 (2)
0.022 (2)
0.0134 (17)
Geometric parameters (Å, º)
S1—C10
S1—C15
S2—C8
O1—C7
1.786 (3)
C9—C10
1.414 (4)
1.839 (3)
1.674 (3)
1.230 (4)
C10—C11
C11—C12
C11—H11
1.398 (5)
1.384 (5)
0.9500
Acta Cryst. (2012). C68, o485–o487
sup-3

supplementary materials
N1—C7
N1—C8
N1—H1N1
N2—C8
N2—C9
N2—H1N2
C1—C6
C1—C2
C1—C7
C2—C3
C2—H2A
C3—C4
C3—H3
C4—C5
C4—H4
C5—C6
C5—H5
C6—H6
C9—C14
1.381 (4)
1.401 (4)
0.8800
C12—C13
C12—H12
C13—C14
C13—H13
C14—H14
C15—C16
C15—H15A
C15—H15B
C16—C17
C16—C21
C17—C18
C17—H17
C18—C19
C18—H18
C19—C20
C19—H19
C20—C21
C20—H20
C21—H21
1.388 (5)
0.9500
1.396 (5)
0.9500
1.353 (4)
1.421 (4)
0.8800
0.9500
1.508 (5)
0.9900
1.401 (4)
1.404 (4)
1.497 (4)
1.392 (5)
0.9500
0.9900
1.391 (4)
1.406 (5)
1.391 (5)
0.9500
1.373 (5)
0.9500
1.394 (5)
0.9500
1.388 (5)
0.9500
1.385 (5)
0.9500
1.382 (5)
0.9500
1.376 (5)
0.9500
0.9500
1.401 (4)
0.9500
C10—S1—C15
C7—N1—C8
C7—N1—H1N1
C8—N1—H1N1
C8—N2—C9
C8—N2—H1N2
C9—N2—H1N2
C6—C1—C2
C6—C1—C7
C2—C1—C7
C3—C2—C1
C3—C2—H2A
C1—C2—H2A
C4—C3—C2
C4—C3—H3
C2—C3—H3
C3—C4—C5
C3—C4—H4
C5—C4—H4
C6—C5—C4
C6—C5—H5
C4—C5—H5
C5—C6—C1
C5—C6—H6
C1—C6—H6
O1—C7—N1
O1—C7—C1
N1—C7—C1
N2—C8—N1
99.77 (15)
129.2 (3)
115.4
C12—C11—C10
C12—C11—H11
C10—C11—H11
C11—C12—C13
C11—C12—H12
C13—C12—H12
C12—C13—C14
C12—C13—H13
C14—C13—H13
C13—C14—C9
C13—C14—H14
C9—C14—H14
C16—C15—S1
C16—C15—H15A
S1—C15—H15A
C16—C15—H15B
S1—C15—H15B
121.4 (3)
119.3
119.3
115.4
119.1 (3)
120.5
131.2 (3)
114.4
120.5
114.4
120.9 (3)
119.6
118.4 (3)
116.4 (3)
125.2 (3)
120.0 (3)
120.0
119.6
120.4 (3)
119.8
119.8
120.0
111.1 (2)
109.4
120.6 (3)
119.7
109.4
119.7
109.4
120.3 (4)
119.8
109.4
H15A—C15—H15B
C17—C16—C21
C17—C16—C15
C21—C16—C15
C18—C17—C16
C18—C17—H17
C16—C17—H17
C17—C18—C19
C17—C18—H18
C19—C18—H18
C20—C19—C18
C20—C19—H19
108.0
119.8
118.8 (3)
119.7 (3)
121.5 (3)
120.7 (3)
119.7
119.7 (4)
120.1
120.1
121.0 (3)
119.5
119.7
119.5
120.1 (3)
120.0
121.1 (3)
120.9 (3)
118.0 (3)
115.4 (3)
120.0
119.1 (4)
120.5
Acta Cryst. (2012). C68, o485–o487
sup-4

supplementary materials
N2—C8—S2
127.9 (3)
116.6 (2)
118.6 (3)
124.1 (3)
117.2 (3)
119.6 (3)
119.3 (3)
121.0 (3)
C18—C19—H19
C21—C20—C19
C21—C20—H20
C19—C20—H20
C20—C21—C16
C20—C21—H21
C16—C21—H21
120.5
N1—C8—S2
121.3 (4)
119.4
C14—C9—C10
C14—C9—N2
C10—C9—N2
C11—C10—C9
C11—C10—S1
C9—C10—S1
119.4
120.0 (3)
120.0
120.0
C6—C1—C2—C3
C7—C1—C2—C3
C1—C2—C3—C4
C2—C3—C4—C5
C3—C4—C5—C6
C4—C5—C6—C1
C2—C1—C6—C5
C7—C1—C6—C5
C8—N1—C7—O1
C8—N1—C7—C1
C6—C1—C7—O1
C2—C1—C7—O1
C6—C1—C7—N1
C2—C1—C7—N1
C9—N2—C8—N1
C9—N2—C8—S2
C7—N1—C8—N2
C7—N1—C8—S2
C8—N2—C9—C14
C8—N2—C9—C10
C14—C9—C10—C11
N2—C9—C10—C11
−0.8 (5)
178.8 (3)
0.5 (5)
C14—C9—C10—S1
N2—C9—C10—S1
−178.7 (2)
−0.3 (4)
−63.3 (3)
115.4 (3)
−0.4 (5)
178.3 (3)
0.5 (5)
C15—S1—C10—C11
C15—S1—C10—C9
C9—C10—C11—C12
S1—C10—C11—C12
C10—C11—C12—C13
C11—C12—C13—C14
C12—C13—C14—C9
C10—C9—C14—C13
N2—C9—C14—C13
C10—S1—C15—C16
S1—C15—C16—C17
S1—C15—C16—C21
C21—C16—C17—C18
C15—C16—C17—C18
C16—C17—C18—C19
C17—C18—C19—C20
C18—C19—C20—C21
C19—C20—C21—C16
C17—C16—C21—C20
C15—C16—C21—C20
0.5 (5)
−1.2 (6)
0.9 (6)
0.1 (5)
−179.5 (3)
−0.2 (5)
179.1 (3)
−4.3 (5)
176.1 (3)
176.3 (3)
−3.3 (5)
−178.3 (3)
1.2 (5)
−0.1 (5)
−0.3 (5)
0.4 (5)
−177.9 (3)
−163.3 (2)
−136.0 (3)
47.0 (4)
1.2 (5)
−175.9 (3)
−1.4 (5)
0.9 (5)
2.1 (5)
−177.5 (3)
−13.0 (5)
168.7 (3)
−0.1 (5)
178.3 (3)
−0.2 (6)
0.1 (6)
−0.6 (5)
176.5 (3)
Hydrogen-bond geometry (Å, º)
D—H···A
D—H
H···A
D···A
D—H···A
N1—H1N1···S2i
N2—H1N2···O1
N2—H1N2···S1
C2—H2A···S2i
C6—H6···O1
0.88
0.88
0.88
0.95
0.95
0.95
0.99
2.90
1.91
2.49
2.77
2.43
2.50
2.39
3.688 (4)
2.642 (3)
2.997 (3)
3.556 (4)
2.760 (4)
3.184 (4)
3.366 (4)
150
140
117
141
100
129
168
C14—H14···S2
C15—H15A···O1ii
Symmetry codes: (i) −x, −y+1, −z; (ii) x, y−1, z.
Acta Cryst. (2012). C68, o485–o487
sup-5