True symmetry or pseudosymmetry: 5-amino-1-(4-methylphenylsulfonyl)-4- pyrazolin-3-one and a comparison with its 1-phenylsulfonyl analogue

Article abstract of DOI:10.1107/S0108270112049906

The title compound, C₁₀H11N₃O₃S, (I), crystallizes as the NH tautomer. The two rings subtend an interplanar angle of 72.54(4)°. An intramolecular hydrogen bond is formed from the NH₂ group to a sulfonyl O atom.

Full text of DOI:10.1107/S0108270112049906

organic compounds
0
Acta Crystallographica Section C
Crystal Structure
Communications
zole obtained by intramolecular cyclization of N -(2-cyano-
acetyl)-4-methylbenzenesulfonohydrazide. Some time ago, we
reported the structure of the corresponding 1-phenyl deriva-
tive, (II) (Elgemeie et al., 1998).
ISSN 0108-2701
True symmetry or pseudosymmetry:
5
4
-amino-1-(4-methylphenylsulfonyl)-
-pyrazolin-3-one and a comparison
with its 1-phenylsulfonyl analogue
Compound (I) can potentially exist in a different tautomeric
hydroxy) form. However, spectroscopic studies indicated the
(
1
3
a
a
presence of the NH tautomer in solution (e.g. the C NMR
signal at 172.65 p.p.m. indicates a carbonyl C atom rather than
a C—OH group). X-ray analysis (Fig. 1) establishes the
exclusive presence of the ketonic form in the solid state; all H
atoms could be located unambiguously, and bond lengths are
also consistent with the NH form. Molecular dimensions
Galal H. Elgemeie, Shahinaz H. Sayed and Peter G.
b
Jones *
a
Chemistry Department, Faculty of Science, Helwan University, Cairo, Egypt, and
b
Institut f u¨ r Anorganische und Analytische Chemie, Technische Universit a¨ t
Braunschweig, Postfach 3329, D-38023 Braunschweig, Germany
Correspondence e-mail: p.jones@tu-bs.de
(
Table 1) may be regarded as normal. Atoms N2 and N3 are
˚
pyramidally coordinated; they lie 0.31 (1) and 0.21 (1) A,
respectively, out of the plane of their three substituents. The
Received 30 November 2012
Accepted 5 December 2012
Online 15 December 2012
pyrazoline ring is reasonably planar (r.m.s. deviation =
˚
0
.04 A), although its largest absolute torsion angle is N1—
The title compound, C H N O S, (I), crystallizes as the NH
11
ꢀ
10
3
3
N2—C3—C4, ꢂ10.30 (11) . The two rings subtend an inter-
tautomer. The two rings subtend an interplanar angle of
ꢀ
ꢀ
planar angle of 72.54 (4) , and their orientation is further
described by the torsion angles C12—C11—S1—O2 =
72.54 (4) . An intramolecular hydrogen bond is formed from
the NH group to a sulfonyl O atom. The molecular packing
2
ꢀ
ꢀ
ꢂ0.31 (11) and N2—N1—S1—O3 = ꢂ179.59 (7) . In other
words, C12—C11 is synperiplanar to S1—O2, and N1—N2 is
antiperiplanar to S1—O3. An intramolecular N3—
H03Aꢁ ꢁ ꢁO3 hydrogen bond is observed, albeit with a narrow
involves layers of molecules parallel to the bc plane at x ’ 0, 1
etc., with two classical linear hydrogen bonds (amino–sulfonyl
and pyrazoline–carbonyl N—Hꢁ ꢁ ꢁO) and a further interaction
(
amino–sulfonyl N—Hꢁ ꢁ ꢁO) completing a three-centre system
ꢀ
angle of 116.6 (14) at the H atom; at N3, atoms H03A and
with the intramolecular contact. The analogous phenyl
derivative, (II) [Elgemeie, Hanfy, Hopf & Jones (1998). Acta
Cryst. C54, 136–138], crystallizes with essentially the same unit
cell and packing pattern, but with two independent molecules
that differ significantly in the orientation of the phenyl groups.
The space group is P2 /c for (I) but P2 for (II), which is thus a
H03B lie out of the plane (of the pyrazoline ring plus N3) by
˚
.28 (2) and 0.25 (2) A, respectively, both in the opposite
0
direction to atom O3.
The molecular packing of (I) involves thick layers of mol-
ecules parallel to the bc plane at x ’ 0, 1 etc. (Fig. 2); the tolyl
groups project into the space between the layers (Fig. 3). In
1
1
pseudosymmetric counterpart of (I).
the order shown in Table 2, hydrogen bond 1 forms eight-
2
membered rings of the common graph set R (8) (Bernstein et
2
al., 1995) over an inversion centre, hydrogen bonds 2 and 3
Comment
Recent reports from our laboratory have demonstrated the
effectiveness of a variety of N-sulfonylated heterocycles and
other antimetabolites as antiplastic agents in a number of
experimental murine tumour systems (Elgemeie & Sood,
2006; Elgemeie et al., 2009). These compounds have been
shown to cause inhibition of thymidine and uridine incor-
poration into DNA and RNA, and appear to constitute a new
class of antimetabolites (Elgemeie et al., 2007). It was of
interest to study their stereostructures and evaluate the effects
of various structural modifications on their biological activity.
Recently, some of our synthesized N-sulfonylated pyrazoles
proved to be inhibitors of the enzyme cathepsin B (Myers et
al., 2007). Members of this class, along with functional group
analogues, were synthesized in an effort to define the struc-
tural requirements for activity. We report here the synthesis
and structure of the title compound, (I), an N-sulfonated pyra-
Figure 1
The molecular structure of (I), showing the atom-numbering scheme.
Displacement ellipsoids are drawn at the 50% probability level. The
dashed line indicates the intramolecular N—Hꢁ ꢁ ꢁO hydrogen bond.
9
0
# 2013 International Union of Crystallography
doi:10.1107/S0108270112049906
Acta Cryst. (2013). C69, 90–92

organic compounds
Figure 4
Figure 2
A packing diagram for (II) (Elgemeie et al., 1998), viewed parallel to the a
axis. The first independent molecule is drawn with full bonds and the
second with open bonds. For clarity, phenyl rings are reduced to the
ipso-C atom, and all H atoms not involved in hydrogen bonding have also
been omitted. Hydrogen bonds are indicated by thick (two-centre) or thin
dashed lines (three-centre) and are numbered analogously to those of (I)
in Table 2, with an additional ‘a’ for those with the donor in molecule 1
and ‘b’ for those with the donor in molecule 2. The origin has been shifted
A packing diagram for (I), viewed parallel to the a axis. For clarity, the
tolyl rings are reduced to the ipso-C atom, and all H atoms not involved in
hydrogen bonding have also been omitted. Hydrogen bonds are indicated
by thick (two-centre) or thin dashed lines (three-centre) and are
numbered according to their order in Table 2.
form a three-centre system (2 is the intramolecular hydrogen
bond mentioned above), and hydrogen bond 4 connects the
along the b axis to be consistent with Fig. 2, but not along the c axis, where
1
it would be shifted by with respect to (I).
2
4
R (8) rings in the direction of the diagonals [011] and [011].
ii
2
1
2
We note that the H03Bꢁ ꢁ ꢁO2 [symmetry code: (ii) x, ꢂy + ,
1
2
˚
z + ] contact of 2.76 (2) A would complete a bifurcated
hydrogen-bond system with hydrogen bond 3, but we regard it
as too long.
Several years ago, we published the structure of the phenyl
analogue, (II), of (I) (Elgemeie et al., 1998). The unit cells are
˚
strikingly similar, except that the a axis of (II) is around 1.2 A
shorter [for (II): a = 10.7794 (19), b = 7.8301 (8) and c =
ꢀ
˚
1
1.8317 (12) A, and ꢀ = 97.505 (8) , at 173 K]. The space
group of (II) was originally thought to be P2 /c, but a more
1
detailed analysis showed that the true space group was P21.
The packing diagram of (II) is shown in Fig. 4. The two
Figure 5
A least-squares fit of the two molecules of (II). The r.m.s. deviation for all
˚
atoms except the non-ipso atoms of the phenyl ring is 0.06 A. Molecule 1
(unprimed atoms) was inverted and is shown with dashed bonds.
independent molecules in the asymmetric unit, which are
related to each other by a local inversion centre, differ
significantly in the orientation of the phenyl rings (Fig. 5), with
ꢀ
torsion angles N1—S1—C11—C12 = 109.5 (3) and ꢂ73.0 (3) .
The two independent molecules of (II) form an exactly
equivalent set of hydrogen bonds to each other and to (I), so
that the packing pattern is topologically the same in both
structures. Compound (II) is thus a pseudosymmetric coun-
terpart of (I). The absence of the methyl group leads to the
shorter a axis in (II).
Experimental
Compound (I) was obtained by refluxing an ethanolic solution (30 ml)
0
of N -(2-cyanoacetyl)-4-methylbenzenesulfonohydrazide (2.53 g,
0.01 mol) containing a few drops of piperidine for 1 h. After cooling,
the precipitate, (I), was filtered off and recrystallized from ethanol
Figure 3
A packing diagram for (I), viewed parallel to the b axis. Dashed lines
indicate hydrogen bonds.
ꢃ
Acta Cryst. (2013). C69, 90–92
Elgemeie et al.
C
10
11 3 3
H N O S
91

organic compounds
Table 1
Selected geometric parameters (A, ).
Table 2
Hydrogen-bond geometry (A, ).
˚
ꢀ
˚
ꢀ
O1—C3
N1—C5
N1—N2
N2—C3
1.2483 (13)
1.4184 (13)
1.4188 (12)
1.3891 (14)
N3—C5
C3—C4
C4—C5
1.3478 (13)
1.4284 (14)
1.3702 (14)
D—Hꢁ ꢁ ꢁA
D—H
Hꢁ ꢁ ꢁA
Dꢁ ꢁ ꢁA
D—Hꢁ ꢁ ꢁA
i
N2—H02ꢁ ꢁ ꢁO1
0.891 (17)
0.859 (18)
0.859 (18)
0.859 (18)
1.926 (18)
2.333 (17)
2.512 (17)
1.986 (18)
2.8153 (12)
2.8241 (13)
2.9359 (12)
2.8322 (12)
175.4 (16)
116.6 (14)
111.3 (13)
168.0 (16)
N3—H03Aꢁ ꢁ ꢁO3
N3—H03Aꢁ ꢁ ꢁO2
ii
iii
O3—S1—N1—N2
C5—N1—N2—C3
N1—N2—C3—C4
N2—C3—C4—C5
ꢂ179.59 (7)
8.76 (11)
C3—C4—C5—N1
N2—N1—C5—C4
O2—S1—C11—C12
ꢂ2.41 (12)
ꢂ3.86 (11)
ꢂ0.31 (11)
N3—H03Bꢁ ꢁ ꢁO1
1
2
1
2
3
2
1
2
ꢂ10.30 (11)
Symmetry codes: (i) ꢂx þ 2; ꢂy þ 1; ꢂz; (ii) x; ꢂy þ
; z þ
; (iii) x; ꢂy þ
; z þ
.
7.95 (12)
ꢀ
1
09.5 ; Uiso(H) = 1.5Ueq(C)] allowed to rotate but not tip; slow
ꢂ1
(
yield 87%; m.p. 500 K). IR (KBr, ꢁ, cm ): 3550, 3500, 3420 (NH
2
,
convergence of this group may indicate some degree of rotational
disorder. Other H atoms were included using a riding model starting
˚
from calculated positions [C—H = 0.95 A and Uiso(H) = 1.2Ueq(C)].
1
NH), 1630 (C O, s); H NMR (DMSO): ꢂ 2.34 (s, 3H, CH
3
), 4.48 (s,
); MS, m/z =
S: C 47.42, H 4.37,
1
H, CH), 6.88 (s, br, 2H, NH
2
), 7.41–7.92 (m, 4H, C
6
H
4
2
53. Elemental analysis calculated for C10
H
11
3
N O
3
Data collection: CrysAlis PRO (Oxford Diffraction, 2011); cell
refinement: CrysAlis PRO; data reduction: CrysAlis PRO;
program(s) used to solve structure: SHELXS97 (Sheldrick, 2008);
program(s) used to refine structure: SHELXL97 (Sheldrick, 2008);
molecular graphics: XP (Siemens, 1994); software used to prepare
material for publication: SHELXL97.
N 16.59, O 18.95, S 12.66%; found: C 47.66, H 4.47, N 16.62, O 19.18, S
2.71%.
1
Crystal data
˚
V = 1104.63 (4) A
3
C
10
11
H N
3 3
O S
M
r
= 253.28
Z = 4
Mo Kꢃ radiation
ꢄ = 0.29 mm
T = 100 K
Monoclinic, P2 =c
1
˚
a = 11.9857 (2) A
ꢂ1
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: FA3297). Services for accessing these data are
described at the back of the journal.
˚
b = 7.9094 (2) A
˚
c = 11.6777 (2) A
0.35 ꢄ 0.30 ꢄ 0.10 mm
ꢀ
ꢀ
= 93.778 (2)
Data collection
References
Oxford Xcalibur Eos diffractometer
Absorption correction: multi-scan
55463 measured reflections
3349 independent reflections
3081 reflections with I > 2ꢅ(I)
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem.
Int. Ed. Engl. 34, 1555–1573.
Elgemeie, G. H., Elghandour, A. H. & Abd Elaziz, G. W. (2007). Synth.
Commun. 37, 2827–2834.
Elgemeie, G. E. H., Hanfy, N., Hopf, H. & Jones, P. G. (1998). Acta Cryst. C54,
(
CrysAlis PRO; Oxford
Diffraction, 2011)
min = 0.962, Tmax = 1.000
R
int = 0.029
T
136–138.
Refinement
2
Elgemeie, G. H. & Sood, S. A. (2006). Synth. Commun. 36, 743–753.
Elgemeie, G. H., Zaghary, W. A., Amin, K. A. & Nasr, T. M. (2009). J.
Carbohydr. Chem. 28, 161–170.
Myers, M. C., Napper, A. D., Motlekar, N., Shah, P. P., Chiu, C.-H., Beavers,
M. P., Diamond, S. L., Huryn, D. M. & Smith, A. B. III (2007). Bioorg. Med.
Chem. Lett. 17, 4761–4766.
2
R[F > 2ꢅ(F )] = 0.031
wR(F ) = 0.083
S = 1.05
H atoms treated by a mixture of
independent and constrained
refinement
2
˚
ꢂ3
Áꢆmax = 0.44 e A
3
1
349 reflections
67 parameters
Áꢆmin = ꢂ0.44 e A˚
ꢂ3
Oxford Diffraction (2011). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton,
Oxfordshire, England.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Siemens (1994). XP. Siemens Analytical X-ray Instruments Inc., Madison,
Wisconsin, USA.
The N-bound H atoms were refined freely. The methyl group was
˚
refined as an idealized rigid group [C—H = 0.98 A and H—C—H =
ꢃ
9
2
Elgemeie et al.
10 11 3
C H N O
3
S
Acta Cryst. (2013). C69, 90–92

supplementary materials
supplementary materials
Acta Cryst. (2013). C69, 90-92 [doi:10.1107/S0108270112049906]
True symmetry or pseudosymmetry: 5-amino-1-(4-methylphenylsulfonyl)-4-
pyrazolin-3-one and a comparison with its 1-phenylsulfonyl analogue
Galal H. Elgemeie, Shahinaz H. Sayed and Peter G. Jones
5-Amino-1-(4-methylphenylsulfonyl)-4-pyrazolin-3-one
Crystal data
C
M
10
H
11
N
3
O
3
S
F(000) = 528
= 1.523 Mg m
−3
r
= 253.28
D
x
Monoclinic, P2
1
/c
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 20410 reflections
θ = 2.4–30.8°
µ = 0.29 mm
T = 100 K
a = 11.9857 (2) Å
b = 7.9094 (2) Å
c = 11.6777 (2) Å
β = 93.778 (2)°
V = 1104.63 (4) Å
Z = 4
−1
3
Tablet, colourless
0.35 × 0.30 × 0.10 mm
Data collection
Oxford Xcalibur Eos
diffractometer
Radiation source: Enhance (Mo) X-ray Source
Graphite monochromator
Detector resolution: 16.1419 pixels mm
ω scans
55463 measured reflections
3349 independent reflections
3081 reflections with I > 2σ(I)
R
int = 0.029
-1
θmax = 30.9°, θmin = 3.1°
h = −17→17
k = −11→11
l = −16→16
Absorption correction: multi-scan
(
CrysAlis PRO; Oxford Diffraction, 2011)
T
min = 0.962, Tmax = 1.000
Refinement
2
Refinement on F
Secondary atom site location: difference Fourier
map
Hydrogen site location: inferred from
neighbouring sites
Least-squares matrix: full
R[F > 2σ(F )] = 0.031
2
2
2
wR(F ) = 0.083
S = 1.05
H atoms treated by a mixture of independent
and constrained refinement
3
1
0
349 reflections
67 parameters
restraints
2
2
2
w = 1/[σ (F
o
) + (0.0375P) + 0.8152P]
2
2
where P = (F
o
+ 2F )/3
c
Primary atom site location: structure-invariant
direct methods
(Δ/σ)max = 0.008
Δρmax = 0.44 e Å
Δρmin = −0.44 e Å
−
3
−
3
Acta Cryst. (2013). C69, 90-92
sup-1

supplementary materials
Special details
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.
2
2
Refinement. Refinement of F against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F ,
2
2
2
conventional R-factors R are based on F, with F set to zero for negative F . The threshold expression of F > σ(F ) is used
only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F
2
are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.
2
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å )
x
y
z
Uiso*/Ueq
S1
0.82267 (2)
0.92704 (7)
0.86903 (7)
0.82447 (7)
0.89922 (7)
0.90457 (8)
0.9571 (15)
0.86198 (8)
0.8868 (14)
0.8723 (14)
0.90350 (8)
0.87726 (9)
0.8622
0.20196 (3)
0.70212 (10)
0.08937 (10)
0.15888 (11)
0.38073 (11)
0.44047 (12)
0.390 (2)
0.22306 (2)
0.02289 (7)
0.14307 (7)
0.34220 (7)
0.21784 (7)
0.10377 (8)
0.0653 (14)
0.39905 (8)
0.4299 (14)
0.4407 (14)
0.10757 (9)
0.22022 (9)
0.2446
0.00923 (7)
0.01415 (16)
0.01331 (16)
0.01446 (16)
0.00910 (16)
0.01045 (17)
0.021 (4)*
0.01302 (18)
0.020 (4)*
0.019 (4)*
0.01048 (19)
0.01122 (19)
0.013*
O1
O2
O3
N1
N2
H02
N3
0.50217 (13)
0.410 (2)
H03A
H03B
C3
0.591 (2)
0.61599 (14)
0.66602 (14)
0.7779
C4
H4
C5
0.87772 (8)
0.68587 (9)
0.64353 (10)
0.6889
0.52327 (13)
0.25427 (14)
0.18606 (16)
0.1166
0.28673 (9)
0.17167 (9)
0.06803 (10)
0.0237
0.00963 (18)
0.01096 (19)
0.0170 (2)
0.020*
C11
C12
H12
C13
H13
C14
C15
H15
C16
H16
C17
H17A
H17B
H17C
0.53346 (10)
0.5036
0.22144 (17)
0.1741
0.03042 (11)
−0.0398
0.0198 (2)
0.024*
0.46595 (9)
0.51177 (10)
0.4674
0.32476 (16)
0.39525 (17)
0.4684
0.09343 (10)
0.19568 (11)
0.2385
0.0162 (2)
0.0191 (2)
0.023*
0.62106 (10)
0.6512
0.36036 (16)
0.4080
0.23585 (10)
0.3059
0.0167 (2)
0.020*
0.34648 (10)
0.2962
0.35846 (19)
0.2995
0.05166 (12)
0.1011
0.0237 (3)
0.036*
0.3337
0.3176
−0.0273
0.036*
0.3318
0.4803
0.0540
0.036*
2
Atomic displacement parameters (Å )
11
22
33
12
13
23
U
U
U
U
U
U
S1
0.01033 (12)
0.0163 (4)
0.0140 (4)
0.0184 (4)
0.0113 (4)
0.00810 (12)
0.0134 (4)
0.0107 (4)
0.0140 (4)
0.0090 (4)
0.00918 (12)
0.0132 (4)
0.0152 (4)
0.0108 (3)
0.0071 (4)
−0.00069 (8)
0.0029 (3)
−0.00006 (8)
0.0043 (3)
0.0001 (3)
−0.0003 (3)
0.0013 (3)
0.00048 (8)
0.0053 (3)
−0.0032 (3)
0.0039 (3)
0.0004 (3)
O1
O2
O3
N1
0.0018 (3)
−0.0033 (3)
−0.0012 (3)
Acta Cryst. (2013). C69, 90-92
sup-2

supplementary materials
N2
0.0140 (4)
0.0189 (5)
0.0089 (4)
0.0123 (4)
0.0086 (4)
0.0098 (4)
0.0136 (5)
0.0146 (5)
0.0113 (5)
0.0141 (5)
0.0144 (5)
0.0119 (5)
0.0103 (4)
0.0118 (4)
0.0109 (4)
0.0096 (4)
0.0102 (4)
0.0117 (4)
0.0218 (6)
0.0271 (6)
0.0183 (5)
0.0235 (6)
0.0213 (6)
0.0298 (7)
0.0073 (4)
0.0084 (4)
0.0117 (4)
0.0119 (4)
0.0101 (4)
0.0113 (4)
0.0155 (5)
0.0172 (5)
0.0188 (5)
0.0199 (5)
0.0144 (5)
0.0288 (6)
0.0001 (3)
−0.0025 (3)
0.0012 (3)
0.0000 (3)
−0.0009 (3)
−0.0009 (4)
0.0030 (4)
0.0020 (4)
0.0002 (4)
0.0039 (4)
0.0012 (4)
0.0034 (5)
0.0028 (3)
0.0011 (3)
0.0007 (3)
0.0022 (4)
0.0003 (3)
0.0009 (3)
−0.0008 (4)
−0.0036 (4)
0.0003 (4)
0.0027 (4)
0.0006 (4)
−0.0024 (4)
0.0019 (3)
−0.0014 (3)
0.0015 (4)
0.0002 (4)
−0.0014 (3)
0.0000 (4)
−0.0068 (4)
−0.0074 (5)
0.0006 (4)
−0.0057 (5)
−0.0061 (4)
−0.0018 (5)
N3
C3
C4
C5
C11
C12
C13
C14
C15
C16
C17
Geometric parameters (Å, º)
S1—O2
1.4293 (8)
C14—C15
1.3970 (17)
S1—O3
1.4313 (8)
1.6889 (9)
1.7578 (11)
C14—C17
C15—C16
N2—H02
1.5057 (16)
1.3897 (16)
0.891 (17)
0.859 (18)
0.859 (18)
0.9500
S1—N1
S1—C11
O1—C3
N1—C5
N1—N2
N2—C3
N3—C5
C3—C4
C4—C5
C11—C12
C11—C16
C12—C13
C13—C14
1.2483 (13)
1.4184 (13)
1.4188 (12)
1.3891 (14)
1.3478 (13)
1.4284 (14)
1.3702 (14)
1.3901 (15)
1.3950 (15)
1.3911 (16)
1.3938 (17)
N3—H03A
N3—H03B
C4—H4
C12—H12
C13—H13
C15—H15
C16—H16
C17—H17A
C17—H17B
C17—H17C
0.9500
0.9500
0.9500
0.9500
0.9800
0.9800
0.9800
O2—S1—O3
O2—S1—N1
O3—S1—N1
O2—S1—C11
O3—S1—C11
N1—S1—C11
C5—N1—N2
C5—N1—S1
N2—N1—S1
C3—N2—N1
O1—C3—N2
O1—C3—C4
N2—C3—C4
C5—C4—C3
N3—C5—C4
N3—C5—N1
C4—C5—N1
C12—C11—C16
C12—C11—S1
120.36 (5)
105.22 (5)
105.12 (5)
108.52 (5)
109.99 (5)
106.70 (5)
106.79 (8)
121.71 (7)
111.77 (7)
107.56 (8)
121.13 (10)
130.79 (10)
108.02 (9)
107.51 (9)
131.15 (10)
119.73 (9)
109.12 (9)
121.13 (10)
118.99 (8)
C15—C14—C17
C16—C15—C14
C15—C16—C11
C3—N2—H02
121.21 (11)
121.20 (11)
118.95 (10)
118.2 (11)
113.6 (11)
116.5 (11)
115.2 (11)
115.2 (15)
126.2
N1—N2—H02
C5—N3—H03A
C5—N3—H03B
H03A—N3—H03B
C5—C4—H4
C3—C4—H4
126.2
C11—C12—H12
C13—C12—H12
C12—C13—H13
C14—C13—H13
C16—C15—H15
C14—C15—H15
C15—C16—H16
C11—C16—H16
C14—C17—H17A
120.6
120.6
119.2
119.2
119.4
119.4
120.5
120.5
109.5
Acta Cryst. (2013). C69, 90-92
sup-3

supplementary materials
C16—C11—S1
C11—C12—C13
C12—C13—C14
C13—C14—C15
C13—C14—C17
119.87 (8)
118.75 (11)
121.52 (11)
118.42 (11)
120.37 (11)
C14—C17—H17B
109.5
H17A—C17—H17B
C14—C17—H17C
H17A—C17—H17C
H17B—C17—H17C
109.5
109.5
109.5
109.5
O2—S1—N1—C5
O3—S1—N1—C5
C11—S1—N1—C5
O2—S1—N1—N2
O3—S1—N1—N2
C11—S1—N1—N2
C5—N1—N2—C3
S1—N1—N2—C3
N1—N2—C3—O1
N1—N2—C3—C4
O1—C3—C4—C5
N2—C3—C4—C5
C3—C4—C5—N3
C3—C4—C5—N1
N2—N1—C5—N3
S1—N1—C5—N3
N2—N1—C5—C4
−179.86 (8)
−51.83 (9)
64.97 (9)
S1—N1—C5—C4
−133.79 (8)
−0.31 (11)
−133.86 (10)
112.62 (10)
178.57 (9)
45.01 (11)
−68.50 (10)
−1.86 (18)
177.00 (10)
0.8 (2)
O2—S1—C11—C12
O3—S1—C11—C12
N1—S1—C11—C12
O2—S1—C11—C16
O3—S1—C11—C16
N1—S1—C11—C16
C16—C11—C12—C13
S1—C11—C12—C13
C11—C12—C13—C14
C12—C13—C14—C15
C12—C13—C14—C17
C13—C14—C15—C16
C17—C14—C15—C16
C14—C15—C16—C11
C12—C11—C16—C15
S1—C11—C16—C15
52.38 (8)
−179.59 (7)
−62.80 (8)
8.76 (11)
144.13 (7)
167.27 (9)
−10.30 (11)
−169.30 (11)
7.95 (12)
0.9 (2)
−178.94 (12)
−1.67 (19)
178.19 (12)
0.67 (19)
177.50 (11)
−2.41 (12)
176.21 (9)
46.28 (13)
−3.86 (11)
1.14 (18)
−177.71 (10)
Hydrogen-bond geometry (Å, º)
D—H···A
D—H
H···A
D···A
D—H···A
i
N2—H02···O1
0.891 (17)
0.859 (18)
0.859 (18)
0.859 (18)
1.926 (18)
2.333 (17)
2.512 (17)
1.986 (18)
2.8153 (12)
2.8241 (13)
2.9359 (12)
2.8322 (12)
175.4 (16)
116.6 (14)
111.3 (13)
168.0 (16)
N3—H03A···O3
N3—H03A···O2
N3—H03B···O1
ii
iii
Symmetry codes: (i) −x+2, −y+1, −z; (ii) x, −y+1/2, z+1/2; (iii) x, −y+3/2, z+1/2.
Acta Cryst. (2013). C69, 90-92
sup-4