A new polymorph of N-(6-methylpyridin-2-yl)mesitylenesulfonamide

Article abstract of DOI:10.1107/S0108270113025936

A new polymorph is reported of the pharmaceutically active sulfapyridine derivative, N-(6-methylpyridin-2-yl)mesitylenesulfonamide, in the zwitterionic form 2-methyl-6-{[(2,4,6-trimethylbenzene)sulfonyl]azanidyl}pyridin-1-ium, C₁₅H₁₈N₂O₂S. The observed dimorphism is solvent dependent. The phase described previously [Beloso, Castro, Garcia-Vazquez, Perez-Lourido, Romero and Sousa (2003). Z. Anorg. Allg. Chem. 629, 275-284] crystallizes from ethanol and several other organic solvents, whereas the new form described here is obtained as a phase-pure product from methanol. The molecules in both dimorphic phases are very similar and adopt the conformation which is also predicted for an individual molecule by force field calculations. However, the two forms differ in their packing and hydrogen bonding. Results from solvent-assisted grinding indicate that the new form is less stable than the previously published phase.

Full text of DOI:10.1107/S0108270113025936

pharmaceuticals and natural products
Acta Crystallographica Section C
Crystal Structure
which can be reproducibly obtained from methanol as a phase-
pure solid (Fig. 1).
Communications
ISSN 0108-2701
A new polymorph of N-(6-methyl-
pyridin-2-yl)mesitylenesulfonamide
Fangfang Pan and Ulli Englert*
Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, 52074
Aachen, Germany
2. Experimental
Correspondence e-mail: ullrich.englert@ac.rwth-aachen.de
2.1. Synthesis and crystallization
Received 10 May 2013
The title compound was prepared according to the method
of Beloso et al. (2003). 2-Amino-6-methylpyridine (2.000 g,
18.49 mmol) and 2,4,6-methylphenylsulfonyl chloride (4.045 g,
18.49 mmol) were dissolved in dichloromethane (20 ml).
Sodium carbonate (2.003 g, 18.49 mmol) in water (20 ml) was
added dropwise. The reaction mixture was stirred overnight
and water (100 ml) was added. The organic layer was sepa-
rated and dried with anhydrous magnesium sulfate. The
solvent was evaporated and the resulting oil was suspended in
ethanol, and polymorph I was obtained as a white solid.
Colourless block-shaped crystals of polymorph II were grown
by slow evaporation of a solution of polymorph I in methanol
at room temperature.
Accepted 19 September 2013
A new polymorph is reported of the pharmaceutically active
sulfapyridine derivative, N-(6-methylpyridin-2-yl)mesitylene-
sulfonamide, in the zwitterionic form 2-methyl-6-{[(2,4,6-tri-
methylbenzene)sulfonyl]azanidyl}pyridin-1-ium, C15H18N2O2S.
The observed dimorphism is solvent dependent. The phase
described previously [Beloso, Castro, Garcıa-Vazquez, Perez-
Lourido, Romero & Sousa (2003). Z. Anorg. Allg. Chem. 629,
275–284] crystallizes from ethanol and several other organic
solvents, whereas the new form described here is obtained as a
phase-pure product from methanol. The molecules in both
dimorphic phases are very similar and adopt the conformation
which is also predicted for an individual molecule by force
field calculations. However, the two forms differ in their
packing and hydrogen bonding. Results from solvent-assisted
grinding indicate that the new form is less stable than the
previously published phase.
´
´
´
2.2. Refinement
Crystal data, data collection and structure refinement
details are summarized in Table 1. H atoms were treated as
˚
˚
riding, with C—H = 0.95 A for aryl or 0.98 A for methyl
groups, and with Uiso(H) = 1.2Ueq(C) for aryl and Uiso(H) =
1.5Ueq(C) for methyl groups. The N-bound H atom was
Keywords: crystal structure; pharmaceutically active
compounds; sulfapyridine derivatives; zwitterions;
polymorphism; packing polymorphs.
1. Introduction
Polymorphism is a common phenomenon in many classes of
compounds (McCrone, 1965), among them many nitrogen-
containing drugs. As far as the pharmaceutically active
sulfonamides are concerned, polymorphism is well docu-
mented for 4-amino-N-pyridinylbenzenesulfonamide (Bern-
stein, 1984; Burger et al., 1980; Gouda et al., 1977; Kuhnert-
¨
Brandstatter & Wunsch, 1969; Mesley & Houghton, 1967;
Pratt et al., 2011; Yang & Guillory, 1972). The title compound,
N-(6-methylpyridin-2-yl)mesitylenesulfonamide, (1), is a sul-
fapyridine derivative; Beloso et al. (2003) described a form to
which we will refer as phase I. The original authors crystallized
phase I from ethanol, but our experiments revealed that the
same phase is found from a variety of other organic solvents,
such as dichloromethane, acetone, tetrahydrofuran and pro-
pan-2-ol. We report here a new polymorph of N-(6-methyl-
pyridin-2-yl)mesitylenesulfonamide, denoted polymorph II,
Figure 1
Experimental powder pattern of the new polymorph, II (top profile,
black), and calculated pattern based on the single-crystal diffraction
result (bottom profile, red in the electronic version of the journal).
Acta Cryst. (2013). C69, 1217–1220
doi:10.1107/S0108270113025936
# 2013 International Union of Crystallography 1217

pharmaceuticals and natural products
Table 1
Experimental details.
Table 2
Selected geometric parameters (A, ).
ꢂ
˚
Crystal data
Chemical formula
Mr
S1—O1
S1—O2
S1—N2
S1—C7
1.4504 (15)
1.4434 (14)
1.5940 (17)
1.793 (2)
N1—C2
N1—C1
N2—C1
1.365 (3)
1.370 (3)
1.336 (3)
C15H18N2O2S
290.37
Triclinic, P1
100
7.9753 (11), 8.1446 (11), 11.7776 (16)
86.829 (3), 81.600 (3), 67.124 (3)
697.29 (16)
2
Mo Kꢀ
0.24
0.19 ꢄ 0.10 ꢄ 0.09
Crystal system, space group
Temperature (K)
˚
a, b, c (A)
O1—S1—O2
O1—S1—N2
O2—S1—N2
O1—S1—C7
O2—S1—C7
N2—S1—C7
C2—N1—C1
115.15 (9)
105.04 (9)
113.34 (9)
106.20 (9)
109.16 (9)
107.44 (9)
124.98 (18)
C1—N2—S1
N2—C1—N1
N2—C1—C5
N1—C1—C5
C3—C2—N1
N1—C2—C6
122.42 (14)
113.68 (17)
130.48 (19)
115.83 (18)
118.79 (19)
116.93 (18)
ꢀ, ꢁ, ꢂ (ꢂ)
3
˚
V (A )
Z
Radiation type
ꢃ (mmꢃ1
Crystal size (mm)
)
Data collection
Diffractometer
Bruker D8 diffractometer with an
APEX CCD detector
similar conformation as a head-to-tail dimer linked by pico-
line–imide N—Hꢀ ꢀ ꢀN hydrogen bonds, with graph-set nota-
Absorption correction
Tmin, Tmax
Multi-scan (SADABS; Bruker, 1998)
0.957, 0.979
9103, 3195, 2527
No. of measured, independent and
observed [I > 2ꢄ(I)] reflections
Rint
0.043
0.657
ꢃ1
˚
(sin ꢅ/ꢆ)max (A
)
Refinement
R[F2 > 2ꢄ(F2)], wR(F2), S
No. of reflections
No. of parameters
0.046, 0.115, 1.03
3195
189
H-atom treatment
H atoms treated by a mixture of
independent and constrained
refinement
ꢃ3
˚
Áꢇmax, Áꢇmin (e A
)
0.45, ꢃ0.39
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2009), SHELXS97
(Sheldrick, 2008), SHELXL2012 (Sheldrick, 2008) and PLATON (Spek, 2009).
located in a difference Fourier map, and both the coordinates
and the atomic displacement parameter were freely refined.
˚
The final N1—H1N bond length is 0.86 (2) A, with
2
Uiso(H1N) = 0.020 (6) A .
˚
3. Results and discussion
Fig. 2 shows a displacement ellipsoid plot of the molecule of II,
and selected interatomic distances and angles have been
compiled in Table 2. In order to discuss the structural rela-
tionship between the two polymorphs, it is necessary to
describe briefly the previously reported phase I (Beloso et al.,
2003). Its asymmetric unit contains two molecules of very
Figure 3
The hydrogen-bonded (dashed lines) dimer in (a) phase I and (b) phase
II. H atoms bonded to C atoms have been omitted for clarity. (c) An
overlay of the molecules of phases I and II underlines their conforma-
tional similarity. The molecule associated with atom S1 in phase I is
shown with dashed bonds and the molecule of II with solid bonds.
Figure 2
The molecular structure of polymorph II, with displacement ellipsoids
drawn at the 50% probability level.
ꢁ
1218 Pan and Englert C15H18N2O2S
Acta Cryst. (2013). C69, 1217–1220

pharmaceuticals and natural products
Table 3
Hydrogen-bond geometry (A, ).
Table 4
ꢂ
˚
Comparison of the experimentally observed molecular conformation in
form I (Beloso et al., 2003; average over two independent molecules), in
form II (this work) and for the minimum-energy conformation (force
field calculations).
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
N1—H1Nꢀ ꢀ ꢀO1i
0.86 (2)
2.05 (2)
2.879 (2)
161.9
Torsion angle (ꢂ)
X-ray,
polymorph I
X-ray,
polymorph II
Force field minimum
Symmetry code: (i) ꢃx þ 2; ꢃy þ 1; ꢃz þ 1.
N1—C1—N2—S1
C1—N2—S1—C7
N2—S1—C7—C8
ꢃ177.3
ꢃ176.39 (13)
63.45 (17)
58.08 (17)
ꢃ177.5
62.1
54.9
61.1
41.8
deprotonated imide N atom features strong delocalization of
the electrons. Consequently, for both polymorphs, the imide–
˚
picoline N—C bonds are short [1.336 (3) A in polymorph II,
˚
and 1.347 (3) and 1.342 (2) A in the two residues of poly-
morph I] and the Npicoline—Cpicoline—Nimide—S torsion angles
are small [ꢃ176.39 (13)ꢂ in polymorph II, and ꢃ175.96 (14)
and ꢃ178.70 (13)ꢂ in the two residues of polymorph I].
Figure 4
Despite the clear differences in the intermolecular
hydrogen bonds, the conformations of the individual mol-
ecules of polymorphs I and II are very similar, as shown in
Fig. 3(c) and Table 4. Table 4 also describes the minimum
energy conformation of a molecule in the gas phase according
to simple force field calculations; an augmented MM2 force
field was used (Fujitsu, 2003). The resulting minimum energy
conformation is shown in Fig. 4. Fig. 5 underlines that the
arrangement of the hydrogen-bonded pairs is different in both
forms: I and II are genuine packing polymorphs. Form II is
associated with an overall packing coefficient (Spek, 2009) of
70.0%, lower than that for polymorph I (71.6%). This slightly
inferior space filling of the new polymorph, its lower melting
point (433.8–435.1 versus 437.9–439.4 K for polymorph I) and
its lower density indicate that the new phase might be ther-
modynamically less stable than polymorph I. More conclusive
evidence stems from solvent-assisted grinding: we recall that
the title compound, (1), is soluble in many common organic
solvents but scarcely soluble in water. The new phase, II, is
partially transformed into phase I when ground for 3 min with
Minimum energy conformation of an isolated zwitterionic molecule of N-
(6-methylpyridin-2-yl)mesitylenesulfonamide according to force field
calculations.
tion R22(8) (Etter et al., 1990) (Fig. 3a). The two aminopicoline
rings involved in this hydrogen-bonded pair subtend an angle
of 46.86 (8)ꢂ, presumably a compromise of steric repulsion
between the trimethylphenyl groups and attraction due to
weak intermolecular C—Hꢀ ꢀ ꢀO contacts. In the new phase, II,
the asymmetric unit consists of a single molecule, and a
different arrangement between hydrogen-bonded neighbours
is found: an O atom of the sulfone group rather than the amide
N atom acts as hydrogen-bond acceptor (Table 3), generating
a 12-membered ring with graph-set notation R22(12) (Fig. 3b);
for reasons of symmetry, the aminopicoline rings are coplanar.
Chemical intuition suggests, and structural parameters of
reported sulfapyridine derivatives (Koo & Lee, 1979; Basak et
al., 1984; Bernstein, 1988; Bar & Bernstein, 1985; Gelbrich et
al., 2007; Pratt et al., 2011; Coles et al., 1999, 2000; Threlfall et
al., 1998; Ghorab et al., 2012) confirm, that the tautomer with a
Figure 5
Comparison of the packing in (left) polymorph I and (right) polymorph II as projections on the bc plane.
ꢁ
Acta Cryst. (2013). C69, 1217–1220
Pan and Englert C15H18N2O2S 1219

pharmaceuticals and natural products
Financial support from the China Scholarship Council for
FP is gratefully acknowledged.
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: FM3002). Services for accessing these data are
described at the back of the journal.
References
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Basak, A. K., Chaudhuri, S. & Mazumdar, S. K. (1984). Acta Cryst. C40, 1848–
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Beloso, I., Castro, J., Garcıa-Vazquez, J. A., Perez-Lourido, P., Romero, J. &
´
´
´
Sousa, A. (2003). Z. Anorg. Allg. Chem. 629, 275–284.
Bernstein, I. B. A. J. (1984). J. Pharm. Sci. 74, 255–263.
Bernstein, J. (1987). Conformational Polymorphism. Organic Solid State
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Bernstein, J. (1988). Acta Cryst. C44, 900–902.
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Bruker (2002). SMART. Bruker AXS Inc., Madison, Wisconsin, USA.
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Burger, A., Schulte, K. & Ramberger, R. (1980). J. Therm. Anal. 19, 475–484.
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Structure Report Archive. University of Southampton, England. Access via
http://ecrystals.chem.soton.ac.uk/XXX/, XXX = 177, 178, 179, 180, 183, 185,
193, 197.
Figure 6
Experimental powder patterns of polymorph I (bottom profile, blue in
the electronic version of the journal), polymorph II (middle profile,
magenta) and polymorph II after solvent-assisted grinding (top profile,
black); the arrows drawn downwards from the last (marked in green)
indicate partial conversion of form II into form I.
Coles, S. J., Ward, S. C., Hursthouse, M. B. & Threlfall, T. L. (1999). Crystal
Structure Report Archive. University of Southampton, England. Access via
http://ecrystals.chem.soton.ac.uk/163/.
Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262.
Fujitsu (2003). CAChe Program. Fujitsu Co. Ltd, Tokyo, Japan.
Gelbrich, T., Threlfall, T. L., Bingham, A. L. & Hursthouse, M. B. (2007). Acta
Cryst. C63, o323–o326.
Ghorab, M. M., Al-Said, M. S., Ghabbour, H. A., Chantrapromma, S. & Fun,
H.-K. (2012). Acta Cryst. E68, o1030.
a drop of water; the corresponding powder results are
compiled in Fig. 6. No conversion between the polymorphs is
observed upon grinding without any solvent.
Gouda, M. W., Ebian, A. R., Moustafa, M. A. & Khalil, S. A. (1977). Drug Dev.
Ind. Pharm. 3, 273–290.
Koo, C. H. & Lee, Y. J. (1979). Arch. Pharm. Res. 2, 99–110.
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Kuhnert-Brandstatter, M. & Wunsch, S. (1969). Microchim. Acta, 57, 1308–
1321.
McCrone, W. C. (1965). Physics and Chemistry of the Organic Solid State,
edited by D. Fox, M. M. Labes & A. Weissberger, Vol. 2, pp. 725–767. New
York: Interscience.
Mesley, R. J. & Houghton, E. E. (1967). J. Pharm. Pharmacol. 19, 295–304.
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http://ecrystals.chem.soton.ac.uk/160/.
4. Conclusion
The individual molecules in both forms do not differ signifi-
cantly but rather adopt a conformation similar to that
predicted for an isolated zwitterionic molecule. Global
packing arguments, such as space filling or density, favour
form I. If we follow the general expectation (Bernstein, 1987)
and assume that the alternative polymorphs of the title
compound are associated with comparable lattice energies, we
may conclude that a contribution stabilizing the new form II is
required. We may speculate that more efficient hydrogen
bonds can be responsible for its existence.
Yang, S. S. & Guillory, J. K. (1972). J. Pharm. Sci. 61, 26–40.
ꢁ
1220 Pan and Englert C15H18N2O2S
Acta Cryst. (2013). C69, 1217–1220

supplementary materials
supplementary materials
Acta Cryst. (2013). C69, 1217-1220 [doi:10.1107/S0108270113025936]
A new polymorph of N-(6-methylpyridin-2-yl)mesitylenesulfonamide
Fangfang Pan and Ulli Englert
Computing details
Data collection: SMART (Bruker, 2001); cell refinement: SMART (Bruker, 2001); data reduction: SAINT (Bruker, 1999);
program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2012
(Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication:
SHELXL2012 (Sheldrick, 2008).
2-Methyl-6-{[(2,4,6-trimethylbenzene)sulfonyl]azanidyl}pyridin-1-ium
Crystal data
C15H18N2O2S
Z = 2
Mr = 290.37
Triclinic, P1
F(000) = 308
Dx = 1.383 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 1269 reflections
θ = 2.7–25.4°
a = 7.9753 (11) Å
b = 8.1446 (11) Å
c = 11.7776 (16) Å
α = 86.829 (3)°
β = 81.600 (3)°
γ = 67.124 (3)°
V = 697.29 (16) Å3
µ = 0.24 mm−1
T = 100 K
Block, colourless
0.19 × 0.10 × 0.09 mm
Data collection
Bruker D8
9103 measured reflections
3195 independent reflections
2527 reflections with I > 2σ(I)
Rint = 0.043
diffractometer with APEX CCD detector
Radiation source: Incoatec microsource
Multilayer optics monochromator
ω scans
θ
max = 27.8°, θmin = 2.7°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
h = −10→10
k = −10→10
l = −15→14
T
min = 0.957, Tmax = 0.979
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.046
wR(F2) = 0.115
Secondary atom site location: difference Fourier
map
Hydrogen site location: inferred from
neighbouring sites
S = 1.03
3195 reflections
189 parameters
0 restraints
H atoms treated by a mixture of independent
and constrained refinement
w = 1/[σ2(Fo2) + (0.0461P)2 + 0.4133P]
where P = (Fo2 + 2Fc2)/3
Primary atom site location: structure-invariant
direct methods
(Δ/σ)max < 0.001
Δρmax = 0.45 e Å−3
Δρmin = −0.39 e Å−3
Acta Cryst. (2013). C69, 1217-1220
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.
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
0.82705 (7)
0.92771 (19)
0.63729 (18)
0.8318 (2)
0.902 (3)
0.8525 (2)
0.7867 (3)
0.7785 (3)
0.6797 (3)
0.6436
0.55137 (6)
0.36086 (18)
0.60458 (19)
0.8557 (2)
0.772 (3)
0.6346 (2)
0.8102 (3)
1.0257 (3)
1.1637 (3)
1.2834
0.30180 (4)
0.31141 (12)
0.28521 (12)
0.53085 (14)
0.570 (2)
0.01535 (14)
0.0192 (3)
0.0205 (3)
0.0159 (4)
0.020 (6)*
0.0168 (4)
0.0159 (4)
0.0173 (4)
0.0192 (4)
0.023*
O1
O2
N1
H1N
N2
0.41429 (14)
0.43271 (16)
0.56965 (17)
0.50479 (17)
0.5287
C1
C2
C3
H3
C4
0.6325 (3)
0.5645
1.1258 (3)
1.2213
0.40230 (18)
0.3564
0.0200 (4)
0.024*
H4
C5
0.6820 (3)
0.6462
0.9540 (3)
0.9314
0.36666 (17)
0.2976
0.0186 (4)
0.022*
H5
C6
0.8320 (3)
0.7837
1.0474 (3)
1.1742
0.68275 (18)
0.7024
0.0235 (5)
0.035*
H6A
H6B
H6C
C7
0.9662
0.9980
0.6778
0.035*
0.7811
0.9840
0.7422
0.035*
0.9465 (3)
1.1358 (3)
1.2314 (3)
1.3583
0.6237 (3)
0.5800 (3)
0.6356 (3)
0.6089
0.18139 (16)
0.18110 (17)
0.08962 (17)
0.0904
0.0147 (4)
0.0164 (4)
0.0171 (4)
0.021*
C8
C9
H9
C10
C11
H11
C12
C13
H13A
H13B
H13C
C14
H14A
H14B
H14C
C15
H15A
H15B
1.1491 (3)
0.9640 (3)
0.9062
0.7289 (3)
0.7663 (3)
0.8285
−0.00333 (17)
−0.00193 (17)
−0.0652
0.0179 (4)
0.0188 (4)
0.023*
0.8585 (3)
1.2450 (3)
1.3601
0.7172 (3)
0.4724 (3)
0.4910
0.08756 (17)
0.27382 (18)
0.2691
0.0170 (4)
0.0198 (4)
0.030*
1.2725
0.3456
0.2630
0.030*
1.1731
0.5110
0.3493
0.030*
1.2579 (3)
1.1801
0.7826 (3)
0.8970
−0.10316 (18)
−0.1336
0.0236 (5)
0.035*
1.3002
0.6915
−0.1633
0.035*
1.3643
0.7943
−0.0775
0.035*
0.6587 (3)
0.6326
0.7662 (3)
0.8291
0.07493 (18)
0.0022
0.0213 (5)
0.032*
0.5807
0.8435
0.1388
0.032*
Acta Cryst. (2013). C69, 1217-1220
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supplementary materials
H15C
0.6334
0.6576
0.0756
0.032*
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
S1
0.0155 (3)
0.0232 (8)
0.0148 (7)
0.0155 (8)
0.0199 (9)
0.0132 (9)
0.0142 (9)
0.0187 (10)
0.0170 (10)
0.0164 (10)
0.0269 (12)
0.0171 (10)
0.0183 (10)
0.0137 (9)
0.0231 (11)
0.0227 (11)
0.0177 (10)
0.0168 (10)
0.0267 (11)
0.0206 (11)
0.0159 (3)
0.0151 (7)
0.0257 (8)
0.0153 (9)
0.0156 (9)
0.0208 (10)
0.0183 (10)
0.0166 (10)
0.0180 (11)
0.0217 (11)
0.0210 (11)
0.0134 (10)
0.0128 (10)
0.0188 (10)
0.0156 (10)
0.0171 (10)
0.0154 (10)
0.0198 (11)
0.0254 (12)
0.0251 (12)
0.0150 (2)
0.0206 (8)
0.0215 (8)
0.0164 (9)
0.0142 (8)
0.0136 (9)
0.0182 (10)
0.0201 (10)
0.0207 (11)
0.0155 (10)
0.0228 (11)
0.0139 (9)
0.0179 (10)
0.0195 (10)
0.0157 (10)
0.0153 (10)
0.0173 (10)
0.0220 (11)
0.0207 (11)
0.0178 (10)
−0.0066 (2)
−0.0089 (6)
−0.0088 (6)
−0.0057 (7)
−0.0060 (7)
−0.0077 (8)
−0.0059 (8)
−0.0053 (8)
−0.0032 (8)
−0.0056 (8)
−0.0084 (9)
−0.0065 (8)
−0.0054 (8)
−0.0069 (8)
−0.0087 (8)
−0.0056 (9)
−0.0052 (8)
−0.0060 (9)
−0.0139 (10)
−0.0074 (9)
−0.00188 (18)
−0.0042 (6)
−0.0014 (6)
−0.0022 (7)
−0.0031 (7)
0.0013 (7)
0.00050 (18)
0.0029 (6)
−0.0003 (6)
0.0026 (7)
0.0005 (7)
0.0004 (8)
−0.0020 (8)
−0.0011 (8)
0.0049 (8)
0.0013 (8)
−0.0016 (9)
−0.0008 (7)
−0.0026 (8)
−0.0028 (8)
−0.0021 (8)
0.0015 (8)
−0.0018 (8)
0.0037 (8)
0.0004 (9)
0.0022 (9)
O1
O2
N1
N2
C1
C2
0.0014 (8)
C3
0.0009 (8)
C4
−0.0012 (8)
−0.0016 (8)
−0.0054 (9)
−0.0010 (8)
−0.0022 (8)
−0.0008 (8)
−0.0004 (8)
−0.0051 (8)
−0.0036 (8)
−0.0047 (8)
0.0013 (9)
C5
C6
C7
C8
C9
C10
C11
C12
C13
C14
C15
−0.0064 (8)
Geometric parameters (Å, º)
S1—O1
S1—O2
S1—N2
S1—C7
N1—C2
N1—C1
N1—H1N
N2—C1
C1—C5
C2—C3
C2—C6
C3—C4
C3—H3
C4—C5
C4—H4
C5—H5
C6—H6A
C6—H6B
C6—H6C
C7—C8
1.4504 (15)
C7—C12
1.418 (3)
1.4434 (14)
1.5940 (17)
1.793 (2)
1.365 (3)
1.370 (3)
0.86 (2)
1.336 (3)
1.415 (3)
1.364 (3)
1.496 (3)
1.400 (3)
0.9500
C8—C9
1.386 (3)
1.516 (3)
1.392 (3)
0.9500
C8—C13
C9—C10
C9—H9
C10—C11
C10—C14
C11—C12
C11—H11
C12—C15
C13—H13A
C13—H13B
C13—H13C
C14—H14A
C14—H14B
C14—H14C
C15—H15A
C15—H15B
C15—H15C
1.384 (3)
1.506 (3)
1.391 (3)
0.9500
1.513 (3)
0.9800
0.9800
0.9800
1.370 (3)
0.9500
0.9800
0.9800
0.9500
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
1.410 (3)
O1—S1—O2
115.15 (9)
C9—C8—C7
118.65 (18)
Acta Cryst. (2013). C69, 1217-1220
sup-3

supplementary materials
O1—S1—N2
O2—S1—N2
O1—S1—C7
O2—S1—C7
N2—S1—C7
C2—N1—C1
C2—N1—H1N
C1—N1—H1N
C1—N2—S1
N2—C1—N1
N2—C1—C5
N1—C1—C5
C3—C2—N1
C3—C2—C6
N1—C2—C6
C2—C3—C4
C2—C3—H3
C4—C3—H3
C5—C4—C3
C5—C4—H4
C3—C4—H4
C4—C5—C1
C4—C5—H5
C1—C5—H5
C2—C6—H6A
C2—C6—H6B
H6A—C6—H6B
C2—C6—H6C
H6A—C6—H6C
H6B—C6—H6C
C8—C7—C12
C8—C7—S1
C12—C7—S1
105.04 (9)
113.34 (9)
106.20 (9)
109.16 (9)
107.44 (9)
124.98 (18)
117.0 (15)
118.0 (15)
122.42 (14)
113.68 (17)
130.48 (19)
115.83 (18)
118.79 (19)
124.28 (19)
116.93 (18)
118.86 (19)
120.6
C9—C8—C13
C7—C8—C13
C8—C9—C10
C8—C9—H9
116.94 (17)
124.40 (18)
122.68 (18)
118.7
C10—C9—H9
C11—C10—C9
C11—C10—C14
C9—C10—C14
C10—C11—C12
C10—C11—H11
C12—C11—H11
C11—C12—C7
C11—C12—C15
C7—C12—C15
C8—C13—H13A
C8—C13—H13B
118.7
117.36 (18)
121.18 (18)
121.43 (18)
123.24 (19)
118.4
118.4
117.89 (18)
116.56 (18)
125.54 (18)
109.5
109.5
H13A—C13—H13B
C8—C13—H13C
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
120.6
121.48 (19)
119.3
H13A—C13—H13C
H13B—C13—H13C
C10—C14—H14A
C10—C14—H14B
H14A—C14—H14B
C10—C14—H14C
H14A—C14—H14C
H14B—C14—H14C
C12—C15—H15A
C12—C15—H15B
H15A—C15—H15B
C12—C15—H15C
H15A—C15—H15C
H15B—C15—H15C
119.3
119.99 (19)
120.0
120.0
109.5
109.5
109.5
109.5
109.5
109.5
120.14 (18)
117.37 (14)
122.46 (15)
O1—S1—N2—C1
O2—S1—N2—C1
C7—S1—N2—C1
S1—N2—C1—N1
S1—N2—C1—C5
C2—N1—C1—N2
C2—N1—C1—C5
C1—N1—C2—C3
C1—N1—C2—C6
N1—C2—C3—C4
C6—C2—C3—C4
C2—C3—C4—C5
C3—C4—C5—C1
N2—C1—C5—C4
N1—C1—C5—C4
176.23 (15)
−57.23 (18)
63.45 (17)
−176.39 (13)
2.4 (3)
O1—S1—C7—C12
N2—S1—C7—C12
C12—C7—C8—C9
S1—C7—C8—C9
124.46 (16)
−123.54 (17)
2.2 (3)
−179.41 (14)
−176.71 (18)
1.7 (3)
C12—C7—C8—C13
S1—C7—C8—C13
C7—C8—C9—C10
C13—C8—C9—C10
C8—C9—C10—C11
C8—C9—C10—C14
C9—C10—C11—C12
C14—C10—C11—C12
C10—C11—C12—C7
C10—C11—C12—C15
C8—C7—C12—C11
−178.80 (17)
2.2 (3)
−1.7 (3)
−3.1 (3)
177.32 (18)
0.2 (3)
176.22 (18)
1.6 (3)
−178.12 (18)
0.8 (3)
−177.67 (19)
0.5 (3)
179.10 (19)
−0.3 (3)
−1.3 (3)
−178.71 (19)
0.0 (3)
−179.20 (19)
−1.3 (3)
Acta Cryst. (2013). C69, 1217-1220
sup-4

supplementary materials
O1—S1—C7—C8
O2—S1—C7—C8
N2—S1—C7—C8
O2—S1—C7—C12
−53.92 (17)
−178.64 (14)
58.08 (17)
S1—C7—C12—C11
−179.59 (14)
177.58 (18)
−0.8 (3)
C8—C7—C12—C15
S1—C7—C12—C15
−0.26 (19)
Hydrogen-bond geometry (Å, º)
D—H···A
N1—H1N···O1i
D—H
0.86 (2)
H···A
D···A
D—H···A
161.9
2.05 (2)
2.879 (2)
Symmetry code: (i) −x+2, −y+1, −z+1.
Comparison of the experimentally observed molecular conformation in form (I) (Beloso et al., 2003; average over two
independent molecules), in form (II) (this work) and for the minimum-energy conformation (force field calculations).
Torsion angle (°)
N1—C1—N2—S1
C1—N2—S1—C7
N2—S1—C7—C8
X-ray (I)
-177.3
62.1
X-ray (II)
Force field minimum
-176.39 (13)
63.45 (17)
58.08 (17)
-177.5
61.1
54.9
41.8
Acta Cryst. (2013). C69, 1217-1220
sup-5