organic compounds
with acetone and dried at room temperature. IR (KBr, ꢃ, cmꢁ1): 3091
(m), 3039 (m), 2854 (m), 2613 (m), 1757 (w), 1560 (s), 1477 (m), 1375
(m), 1230 (s), 1195 (s), 1116 (s), 1043 (s), 739 (m), 719 (m), 636 (s);
1H NMR (300 MHz, d6-DMSO): ꢄ 7.57 (s, 1H, Ar—H), 7.05 (s, 1H,
+
Ar—H), 6.9–6.0 [s (broad), 3H, Ar—NH3 ], 2.29 (s, 3H, Ar—CH3);
elemental analysis calculated for C7H8ClNO3S (%): C 37.93, H 3.64,
N 6.32, S 14.47; found: C 37.67, H 3.58, N 6.16, S 14.68.
Suitable single crystals of (Ib) were obtained by treatment of the
purified starting material (20 mg) with 1-methyl-2-pyrrolidone (3 ml)
in an ultrasonic bath at room temperature for 30 min. After 2 d,
colourless plate-shaped crystals of (Ib) were obtained. The precipi-
tate was isolated by filtration and dried for one day at room
temperature. IR (KBr, ꢃ, cmꢁ1): 3101 (m), 3040 (m), 3017 (m), 2961
(m), 2926 (m), 2855 (m), 2833 (m), 2613 (s), 1773 (m), 1757 (m), 1734
(m), 1684 (s), 1653 (s), 1633 (m), 1591 (m), 1576 (s), 1560 (s), 1541 (s),
1522 (s), 1508 (s), 1477 (s), 1437 (m), 1375 (s), 1288 (m), 1230 (s), 1196
(s), 1165 (s), 1117 (s), 1080 (m), 1043 (s), 739 (s), 719 (s), 636 (s), 567
Figure 8
The revised molecular structure of (II), showing the atom-labelling
scheme. Displacement ellipsoids are drawn at the 50% probability level.
Unlabelled atoms are related to labelled atoms by an inversion centre at
the mid-point of the central six-membered ring.
1
(s); H NMR (300 MHz, d6-DMSO): ꢄ 7.57 (s, 1H, Ar—H), 7.04 (s,
+
1H, Ar—H), 5.00–3.50 [s (broad), 3H, Ar—NH3 ], 3.32–3.27 [m, 2H,
CH2 (NMP)], 2.69 [s, 3H, CH3 (NMP)], 2.28 (s, 3H, Ar—CH3), 2.19–
2.15 [m, 2H, CH2 (NMP)], 1.95–1.84 [m, 2H, CH2 (NMP)]; elemental
analysis calculated for C7H8ClNO3SꢀC5H9NO (%): C 44.93, H 5.34, N
8.73, S 10.00; found: C 44.72, H 5.31, N 8.62, S 10.20.
Experimental
The polymorph screening of (Ia) was carried out using commercially
available 2-ammonio-5-chloro-4-methylbenzenesulfonate, obtained
from abcr GmbH and Co. KG, Germany (purity >98%). For purifi-
cation, the starting material was recrystallized twice from boiling
water. Compound (Ia) was found to be soluble at room temperature
in quinoline, morpholine, 2-picoline, N,N0-dimethylformamide, N,N0-
dimethylacetamide, 1-methyl-2-pyrrolidone (NMP) and dimethyl
sulfoxide (DMSO). Subsequently, different methods of crystallization
were employed, including: (i) slurry experiments by suspending (Ia)
in different solvents at room temperature; (ii) evaporation crystal-
lization at room temperature and at 353 K; (iii) slow or rapid anti-
solvent crystallization by overlaying a solution of (Ia) with an
antisolvent; (iv) heating under reflux with subsequent slow or fast
cooling; (v) treatment of a solution or a suspension of (Ia) in an
ultrasonic bath at room temperature; (vi) slow or rapid vapour
diffusion experiments by diffusion of an antisolvent into a solution of
(Ia) via the gas phase. A multitude of different organic solvents were
used as antisolvents, e.g. ketones, ethers, esters, alcohols, benzene,
benzene derivatives (e.g. toluene, picolines and chlorobenzenes) and
alkanes, and water. All solids thus obtained were analysed using
X-ray powder diffraction data recorded under ambient conditions in
transmission mode on a Stoe STADI-P diffractometer with a Ge(111)
monochromator and a linear position-sensitive detector using Cu Kꢁ1
Suitable single crystals of (Ic) were obtained by treatment of the
purified starting material (500 mg) with dimethyl sulfoxide (3 ml) in
an ultrasonic bath at room temperature for 30 min. After 3 d,
colourless block-shaped crystals of (Ic) were obtained. The precipi-
tate was isolated by filtration and dried for 1 d at room temperature.
IR (KBr, ꢃ, cmꢁ1): 3121 (m), 3086 (m), 3063 (m), 3007 (m), 2920 (m),
2853 (m), 2627 (m), 1593 (m), 1558 (s), 1549 (s), 1506 (s), 1373 (s),
1308 (m), 1290 (m), 1238 (s), 1204 (s), 1165 (s), 1117 (s), 1078 (s), 1038
(s), 1003 (s), 735(s), 721 (s), 710 (m), 637 (s), 563 (s); 1H NMR
(300 MHz, d6-DMSO): ꢄ 7.56 (s, 1H, Ar—H), 7.03 (s, 1H, Ar—H),
+
5.50–3.50 [s (broad), 3H, Ar—NH3 ], 2.54 (s, 6H, DMSO), 2.28 (s, 3H,
Ar—CH3); elemental analysis calculated for C7H8ClNO3SꢀC2H6OS (%):
C 36.06, H 4.71, N 4.67, S 21.39; found: C 35.90, H 4.72, N 4.52, S 21.56.
Compound (Ia)
Crystal data
3
˚
C7H8ClNO3S
Mr = 221.65
Monoclinic, Ia
V = 874.68 (10) A
Z = 4
Mo Kꢁ radiation
ꢆ = 0.65 mmꢁ1
T = 173 K
˚
˚
a = 4.9308 (3) A
b = 32.364 (2) A
˚
c = 5.4922 (4) A
0.40 ꢄ 0.20 ꢄ 0.06 mm
ꢅ = 93.654 (1)ꢃ
˚
radiation (ꢂ = 1.5406 A).
IR spectra were measured on an FT–IR-8300 device (Shimadzu).
The samples were prepared as KBr pellets, with 300 mg KBr to 2 mg
of sample. 1H NMR spectra were measured on a Bruker Avance 300
device at 300 MHz in tubes filled with d6-DMSO and about 5 mg of
substance. Elemental analyses (CHNS) were carried out on an
Elementar (vario MICRO cube) elemental analyser; about 1 to 4 mg
of each sample was placed in a tin vessel and measured at 1423 K
under a helium atmosphere with addition of oxygen during the
measurement.
Data collection
Siemens SMART 1K CCD area-
detector diffractometer
Absorption correction: multi-scan
(SADABS; Sheldrick, 2000)
Tmin = 0.693, Tmax = 0.962
5429 measured reflections
2101 independent reflections
1934 reflections with I > 2ꢇ(I)
Rint = 0.038
Refinement
R[F2 > 2ꢇ(F2)] = 0.040
wR(F2) = 0.093
S = 1.05
2101 reflections
131 parameters
2 restraints
H atoms treated by a mixture of
independent and constrained
refinement
Colourless single crystals of (Ia) were obtained by dissolving the
purified starting material (400 mg) in 1-methyl-2-pyrrolidone (30 ml)
under reflux and then filtering the hot solution. The solution was left
for evaporation crystallization at room temperature for 54 weeks.
Upon reduction of the supernatant to 5 ml, colourless single crystals
of (Ia) had formed. The precipitate was isolated by filtration, washed
ꢁ3
˚
Áꢈmax = 0.68 e A
ꢁ3
˚
Áꢈmin = ꢁ0.51 e A
Absolute structure: Flack (1983),
with 986 Friedel pairs
Flack parameter: 0.04 (8)
ꢂ
o48 Beko et al. C7H8ClNO3S and related compounds
Acta Cryst. (2012). C68, o45–o50
¨