2-Ammonio-5-chloro-4-methyl-benzene-sulfonate, its 1-methyl-2-pyrrolidone and dimethyl sulfoxide monosolvates and a corrected structure of 2,2′-(1,4-phenyl-ene)di(4,5-di-hydro-imidazolium) bis-(4-aminobenzene- sulfonate) dihydrate

Article abstract of DOI:10.1107/S0108270111054205

2-Ammonio-5-chloro-4-methyl-benzene-sulfonate, C₇H ₈ClNO₃S, (Ia), is an inter-mediate in the synthesis of lake red azo pigments. The present structure determination from single-crystal data confirms the results of a previous powder diffraction determination [Bekoe, Thoms, Bruening, Alig, van de Streek, Lakatos, Glaubitz & Schmidt (2010). Z. Kristallogr. 225, 382-387]. The zwitterionic tautomeric form is confirmed. During a polymorph screening, two additional pseudopolymorphs were obtained, viz. 2-ammonio-5-chloro-4-methyl-ben-zene-sulfonate 1-methyl-2-pyrrolidone monosolvate, C₇H₈ClNO ₃S·C₅H₉NO, (Ib), and 2-ammonio-5-chloro-4-methyl-benzene-sulfonate dimethyl sulfoxide monosolvate, C₇H₈ClNO₃S·C₂H₆OS, (Ic). The mol-ecules of (Ib) have crystallo-graphic m symmetry. The 1-methyl-2-pyrrolidone solvent mol-ecule has an envelope conformation and is disordered around the mirror plane. The structure shows hydrogen-bonded ladders of mol-ecules [graph-set notation C₂²(6)R₂ ²(12)] in the [010] direction. The benzene groups of adjacent ladders are also stacked in this direction. A different type of hydrogen-bonded ladder [graph-set notation C(6)R₂²(4)R₄ ⁴(12)] occurs in (Ic). In (Ia), (Ib) and (Ic), the mol-ecules correspond to the zwitterionic tautomer. The structure of the cocrystal of 4-amino-benzene-sulfonic acid with 1,4-bis-(4,5-dihydro-imidazol-2-yl)benzene [Shang, Ren, Wang, Lu & Yang (2009). Acta Cryst. E65, o2221-o2222] is corrected; it actually contains 4-amino-benzene-sulfonate anions and 2,2′-(1,4-phenyl-ene)di(dihydroimidazolium) dications, i.e. 2,2′-(1,4-phenyl-ene)di(4,5-dihydro-imidazolium) bis-(4-amino-benzene- sulfonate) dihydrate, C₁₂H₁₆N₄ ²⁺·2C₆H₆NO₃S ^-·2H₂O. Hence, all known structures of amino-benzene-sulfonic acid complexes contain ionic or zwitterionic mol-ecules; there is no known structure with a neutral amino-benzene-sulfonic acid mol-ecule.

Full text of DOI:10.1107/S0108270111054205

organic compounds
Acta Crystallographica Section C
Crystal Structure
contain ionic or zwitterionic molecules; there is no known
structure with a neutral aminobenzenesulfonic acid molecule.
Communications
ISSN 0108-2701
Comment
2-Ammonio-5-chloro-4-methylbenzenesulfonate, (Ia), also
called CLT acid (from chloro-amino-toluenesulfonic acid), is
industrially produced on the scale of several tens of thousands
of tonnes per year. It is used as an intermediate in the
synthesis of lake red azo pigments (e.g. Pigment Red 52:1,
52:2, 53, 53:1, 53:2, 53:3) for newspapers and journals. It can
exist in two possible tautomers, viz. as a non-zwitterion
(2-amino-5-chloro-4-methylbenzenesulfonic acid), having an
–NH2 and an –SO3H group, and as a zwitterion (2-ammonio-5-
2-Ammonio-5-chloro-4-methyl-
benzenesulfonate, its 1-methyl-
2-pyrrolidone and dimethyl sulfoxide
monosolvates and a corrected
structure of 2,20-(1,4-phenylene)-
di(4,5-dihydroimidazolium) bis(4-
aminobenzenesulfonate) dihydrate
+
ꢁ
chloro-4-methylbenzenesulfonate), with –NH3 and –SO3
groups. A crystal structure of the compound was determined
a
b
a
¨
by Beko et al. (2010) from powder diffraction data, as no
´
Sandor L. Beko, Jan W. Bats and Martin U. Schmidt *
¨
suitable single crystals were available at that time. The powder
data clearly showed that the compound exists as the zwitter-
ionic tautomer.
aInstitute of Inorganic and Analytical Chemistry, University of Frankfurt, Max-von-
Laue-Strasse 7, D-60438-Frankfurt am Main, Germany, and bInstitute of Organic
Chemistry and Chemical Biology, University of Frankfurt, Max-von-Laue-Strasse 7,
D-60438-Frankfurt am Main, Germany
Polymorph screening of (Ia) was performed by crystallizing
the compound from a variety of solvents and using various
methods of crystallization. The polymorph screening resulted
in single crystals suitable for X-ray diffraction of the solvent-
free compound (Ia), its 1-methyl-2-pyrrolidone (NMP)
monosolvate, (Ib), and its dimethyl sulfoxide (DMSO)
monosolvate, (Ic). Other polymorphs, pseudopolymorphs or
hydrates could not be found.
Correspondence e-mail: m.schmidt@chemie.uni-frankfurt.de
Received 13 December 2011
Accepted 16 December 2011
Online 6 January 2012
2-Ammonio-5-chloro-4-methylbenzenesulfonate, C7H8ClN-
O3S, (Ia), is an intermediate in the synthesis of lake red azo
pigments. The present structure determination from single-
crystal data confirms the results of a previous powder
¨
¨
diffraction determination [Beko, Thoms, Bruning, Alig, van
de Streek, Lakatos, Glaubitz & Schmidt (2010). Z. Kristallogr.
225, 382–387]. The zwitterionic tautomeric form is confirmed.
During a polymorph screening, two additional pseudopoly-
morphs were obtained, viz. 2-ammonio-5-chloro-4-methyl-
benzenesulfonate 1-methyl-2-pyrrolidone monosolvate, C7H8-
ClNO3SꢀC5H9NO, (Ib), and 2-ammonio-5-chloro-4-methyl-
benzenesulfonate dimethyl sulfoxide monosolvate, C7H8Cl-
NO3SꢀC2H6OS, (Ic). The molecules of (Ib) have crystallo-
graphic m symmetry. The 1-methyl-2-pyrrolidone solvent
molecule has an envelope conformation and is disordered
around the mirror plane. The structure shows hydrogen-
bonded ladders of molecules [graph-set notation C22(6)R22(12)]
in the [010] direction. The benzene groups of adjacent ladders
are also stacked in this direction. A different type of
hydrogen-bonded ladder [graph-set notation C(6)R22(4)-
R44(12)] occurs in (Ic). In (Ia), (Ib) and (Ic), the molecules
correspond to the zwitterionic tautomer. The structure of the
cocrystal of 4-aminobenzenesulfonic acid with 1,4-bis(4,5-
dihydroimidazol-2-yl)benzene [Shang, Ren, Wang, Lu & Yang
(2009). Acta Cryst. E65, o2221–o2222] is corrected; it actually
contains 4-aminobenzenesulfonate anions and 2,20-(1,4-
phenylene)di(dihydroimidazolium) dications, i.e. 2,20-(1,4-
phenylene)di(4,5-dihydroimidazolium) bis(4-aminobenzene-
The molecular structure of (Ia) is shown in Fig. 1. The result
¨
of the previous powder diffraction determination (Beko et al.,
2010) and the tautomeric form are confirmed, but the
hydrogen-bonding system (Table 1) is more accurately derived
from the present single-crystal determination. The molecules
are connected by N—Hꢀ ꢀ ꢀO hydrogen bonds to form double
layers parallel to (010). A weak intermolecular C—Hꢀ ꢀ ꢀO
contact also adds to the stabilization within the layer. Adja-
cent double layers are connected by a very weak inter-
molecular Cmethyl—Hꢀ ꢀ ꢀCl contact with an Hꢀ ꢀ ꢀCl distance of
2+
sulfonate) dihydrate, C12H16N4 ꢀ2C6H6NO3Sꢁꢀ2H2O. Hence,
¨
˚
3.02 A. For a further description of the structure, see Beko et
al. (2010).
all known structures of aminobenzenesulfonic acid complexes
Acta Cryst. (2012). C68, o45–o50
doi:10.1107/S0108270111054205
# 2012 International Union of Crystallography o45

organic compounds
Figure 1
The molecular structure of (Ia), showing the atom-labelling scheme.
Displacement ellipsoids are drawn at the 50% probability level.
Figure 3
Compound (Ib) crystallizes in the monoclinic space group
P21/m with the 2-ammonio-5-chloro-4-methylbenzenesulfon-
ate molecule positioned on a crystallographic mirror plane.
The NMP solvent molecule is disordered about the crystal-
lographic mirror plane and has a C10-envelope conformation.
The molecular structure and numbering scheme are shown in
Fig. 2 and the crystal packing is shown in Fig. 3. The 2-amino-
5-chloro-4-methyl-benzenesulfonate molecules are connected
by two intermolecular N—Hꢀ ꢀ ꢀO hydrogen bonds between
The crystal packing of (Ib), viewed down [010]. Hydrogen bonds are
shown as dashed lines and C-bound H atoms have been omitted for
clarity. Displacement ellipsoids are drawn at the 50% probability level.
running in the b-axis direction, are locked together with
neighbouring ladders along the a-axis direction, resulting in a
two-dimensional framework parallel to the (001) plane.
The DMSO solvate, (Ic), crystallizes in the triclinic space
group P1. The asymmetric unit contains one 2-ammonio-5-
chloro-4-methylbenzenesulfonate molecule and one DMSO
molecule. The molecular structure and numbering scheme are
shown in Fig. 5 and the crystal packing is shown in Fig. 6. The
+
ꢁ
the –NH3 and –SO3 groups (Table 2) to form a ladder
structure in the [010] direction (Fig. 4). In graph-set notation
(Etter et al., 1990; Bernstein et al., 1995), the hydrogen-bond
pattern of the ladder structure is C22(6)R22(12). The third H
atom of the –NH3+ group forms an N—Hꢀ ꢀ ꢀO hydrogen bond
with the NMP molecule. The benzene groups of adjacent
ladders form stacks along [010]. The interplanar distance in
˚
the stack is b/2 = 3.473 (3) A, which is a suitable distance for
ꢀ–ꢀ contacts between the benzene groups. Hence the ladders,
Figure 4
Figure 2
A section of the structure of (Ib), showing the hydrogen-bonded ladders
and the stacking of the benzene groups; the view direction is [001].
Hydrogen bonds are shown as dashed lines and C-bound H atoms have
been omitted for clarity. Displacement ellipsoids are drawn at the 50%
probability level. [Symmetry codes: (i) ꢁx + 1, ꢁy, ꢁz + 1; (ii) x, ꢁy + 12,
z.]
The molecular structure of (Ib), showing the atom-labelling scheme.
Displacement ellipsoids are drawn at the 50% probability level. The
second possible position of the disordered 1-methyl-2-pyrrolidone
molecule has been omitted. Dotted lines indicate hydrogen bonds.
[Symmetry code: (A) x, ꢁy + , z.]
1
2
ꢂ
o46 Beko et al. C7H8ClNO3S and related compounds
Acta Cryst. (2012). C68, o45–o50
¨

organic compounds
Figure 7
A view of the ladder structure of (Ic). Hydrogen bonds are shown as
dashed lines and C-bound H atoms have been omitted for clarity.
Displacement ellipsoids are drawn at the 50% probability level.
[Symmetry codes: (i) ꢁx + 1, ꢁy + 1, ꢁz + 1; (ii) x + 1, y, z; (iv) ꢁx + 2,
ꢁy + 1, ꢁz + 1; (v) x ꢁ 1, y, z.]
Figure 5
The molecular structure of (Ic), showing the atom-labelling scheme.
Displacement ellipsoids are drawn at the 50% probability level. Dotted
lines indicate hydrogen bonds.
interaction (Table 3). Adjacent ladders are connected by a
weak intermolecular DMSO–DMSO C—Hꢀ ꢀ ꢀO interaction.
The ladders form a hexagonal rod packing.
molecules are arranged by hydrogen bonding (Table 3) to
form a ladder structure parallel to the a-axis direction. A
detailed view of the ladder structure is shown in Fig. 7. Each 2-
ammonio-5-chloro-4-methylbenzenesulfonate molecule is
connected by four N—Hꢀ ꢀ ꢀO hydrogen bonds to three
neighbouring molecules. The N1—H1B bond is bifurcated and
has longer Hꢀ ꢀ ꢀO contact distances than the remaining
hydrogen bonds. In terms of graph-set analysis, the hydrogen-
bond pattern of the ladder structure is C(6)R44(12). Here, C(6)
represents the repetition of the structure along the a-axis
direction by the N1—H1Cꢀ ꢀ ꢀO1ii hydrogen bond [symmetry
code: (ii) x + 1, y, z], while the ring structure results from the
combination of N1—H1Cꢀ ꢀ ꢀO1ii and N1—H1Bꢀ ꢀ ꢀO2i hydro-
gen bonds and an inversion centre [symmetry code: (i) ꢁx + 1,
ꢁy + 1, ꢁz + 1]. The bifurcated N1—H1B bond, which is
involved in both an intra- and an intermolecular hydrogen
bond, results in an additional four-membered ring [graph-set
notation R22(4)]. The DMSO solvent molecule is attached to
the ladder by an additional N—Hꢀ ꢀ ꢀO hydrogen bond and by
a very weak intermolecular DMSO–sulfonate C—Hꢀ ꢀ ꢀO
In all three structures, the main molecule exists as a
2-ammoniobenzenesulfonate zwitterion rather than as
2-aminobenzenesulfonic acid. A search of the Cambridge
Structural Database (Version 5.32, with August 2011 update;
Allen, 2002) for compounds containing 2-, 3- and 4-amino-
benzenesulfonic acid revealed 29 entries with a zwitterionic
molecule. Only the structure of Shang et al. (2009) is reported
to contain a neutral molecule. Surprisingly, the three S—O
bond distances in that determination are almost equal, which
is rather suspicious for a sulfonic acid. Therefore, we decided
to redetermine that structure from the published reflection
data. The results are presented here as structure (II). As
expected, the assignment of the sulfonic acid H atom turned
out to be incorrect. Also, one of the H-atom positions on the
water molecule had to be modified. The revised structure
contains 4-aminobenzenesulfonate anions and 1,4-bis(4,5-
dihydroimidazol-2-yl)benzene dications, rather than neutral
molecules. Thus, all reported crystal structures of amino-
benzenesulfonic acids contain zwitterionic molecules or ions.
There is no known structure with a neutral aminobenzene-
sulfonic acid molecule. The corrected hydrogen bonds of
structure (II) are given in Table 4. A view of the structure is
shown in Fig. 8. For a discussion of the structure, see Shang et
al. (2009).
In the structures reported here, all H atoms of the ammonio
groups are donors of N—Hꢀ ꢀ ꢀO hydrogen bonds. In (Ia),
which does not contain solvent molecules, all three H atoms
are connected to sulfonate O atoms of neighbouring mol-
ecules, resulting in a two-dimensional framework. In both (Ib)
and (Ic), one N—H bond donates a hydrogen bond to a
solvent O atom. Thus, only two H atoms are left for hydrogen-
bond formation with sulfonate O atoms. In both cases, this
results in ladder-type structures, but they are rather different:
in (Ib), each molecule in the ladder is connected to only two
neighbouring molecules, resulting in R22(12) rings, while in (Ic),
each molecule is connected to three neighbouring molecules,
resulting in R22(4) and R44(12) rings.
Figure 6
The crystal packing of (Ic), viewed down [100]. Hydrogen bonds are
shown as dashed lines and C-bound H atoms have been omitted for
clarity. Displacement ellipsoids are drawn at the 50% probability level.
ꢂ
Acta Cryst. (2012). C68, o45–o50
Beko et al.
C7H8ClNO3S and related compounds o47
¨

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
¨

organic compounds
Table 1
Hydrogen-bond geometry (A, ) for (Ia).
Table 3
Hydrogen-bond geometry (A, ) for (Ic).
ꢃ
ꢃ
˚
˚
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
N1—H1Aꢀ ꢀ ꢀO3i
N1—H1Bꢀ ꢀ ꢀO1ii
N1—H1Cꢀ ꢀ ꢀO2iii
C3—H3Aꢀ ꢀ ꢀO1ii
C7—H7Cꢀ ꢀ ꢀCl1iv
0.91 (4)
0.84 (4)
0.93 (4)
0.95
1.88 (4)
2.05 (4)
1.95 (4)
2.37
2.772 (4)
2.831 (4)
2.809 (3)
3.148 (3)
3.925 (3)
166 (4)
156 (3)
155 (3)
138
N1—H1Aꢀ ꢀ ꢀO4
N1—H1Bꢀ ꢀ ꢀO2
N1—H1Bꢀ ꢀ ꢀO2i
N1—H1Cꢀ ꢀ ꢀO1ii
C9—H9Bꢀ ꢀ ꢀO4iii
C9—H9Cꢀ ꢀ ꢀO3iv
0.96 (3)
0.93 (2)
0.93 (2)
0.82 (3)
0.98
1.74 (3)
2.31 (2)
2.10 (2)
2.02 (3)
2.40
2.695 (2)
3.013 (2)
2.883 (2)
2.818 (2)
3.356 (3)
3.231 (3)
173 (2)
132 (2)
141 (2)
162 (3)
166
0.98
3.02
154
0.98
2.50
131
3
2
1
2
1
2
Symmetry codes: (i) x ꢁ 1; y; z; (ii) x ꢁ 1; y; z ꢁ 1; (iii) x; ꢁy þ ; z ꢁ ; (iv) x ꢁ ,
ꢁy þ 1; z.
Symmetry codes: (i) ꢁx þ 1; ꢁy þ 1; ꢁz þ 1; (ii) x þ 1; y; z; (iii) ꢁx þ 2; ꢁy þ 2,
ꢁz þ 1; (iv) ꢁx þ 2; ꢁy þ 1; ꢁz þ 1.
Table 2
Hydrogen-bond geometry (A, ) for (Ib).
ꢃ
˚
Table 4
Hydrogen-bond geometry (A, ) for (II).
ꢃ
˚
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
N1—H1Aꢀ ꢀ ꢀO2i
N1—H1Bꢀ ꢀ ꢀO3
C3—H3Aꢀ ꢀ ꢀO3
0.86 (2)
0.86 (3)
0.95
1.98 (2)
1.90 (3)
2.33
2.785 (2)
2.750 (2)
3.112 (3)
156 (2)
169 (3)
139
N1—H1Aꢀ ꢀ ꢀO3i
N1—H1Bꢀ ꢀ ꢀO1ii
N1—H1Bꢀ ꢀ ꢀO2ii
N2—H2Bꢀ ꢀ ꢀO4iii
N3—H3Bꢀ ꢀ ꢀO2iv
O4—H4Aꢀ ꢀ ꢀO2
O4—H4Bꢀ ꢀ ꢀO1v
1.00 (3)
0.87 (3)
0.87 (3)
0.78 (3)
0.79 (2)
0.81 (2)
0.80 (3)
1.97 (3)
2.40 (3)
2.48 (3)
2.04 (3)
2.12 (2)
2.04 (2)
2.02 (3)
2.949 (3)
3.174 (3)
3.214 (3)
2.756 (3)
2.894 (3)
2.822 (3)
2.816 (3)
167 (2)
149 (2)
143 (2)
152 (2)
169 (2)
161 (2)
172 (3)
Symmetry code: (i) ꢁx þ 1; ꢁy; ꢁz þ 1.
Compound (Ib)
1
1
2
1
2
1
2
1
2
1
2
Symmetry codes: (i) x; ꢁy þ ; z ꢁ ; (ii) ꢁx þ ; ꢁy; z ꢁ ; (iii) x ꢁ ; ꢁy þ ; ꢁz þ 1;
2
1
2
3
2
1
3
2
(iv) x ꢁ ; y; ꢁz þ ; (v) x þ ; y; ꢁz þ .
2
Crystal data
3
˚
C7H8ClNO3SꢀC5H9NO
V = 727.44 (19) A
Z = 2
Mr = 320.79
Monoclinic, P21=m
Mo Kꢁ radiation
ꢆ = 0.42 mmꢁ1
T = 165 K
˚
a = 9.1917 (17) A
Refinement
˚
b = 6.9457 (11) A
R[F2 > 2ꢇ(F2)] = 0.036
wR(F2) = 0.081
S = 0.98
3481 reflections
169 parameters
H atoms treated by a mixture of
independent and constrained
refinement
˚
c = 11.8265 (13) A
0.40 ꢄ 0.36 ꢄ 0.10 mm
ꢅ = 105.538 (7)ꢃ
ꢁ3
˚
Áꢈmax = 0.42 e A
Data collection
ꢁ3
˚
Áꢈmin = ꢁ0.38 e A
Siemens SMART 1K CCD area-
detector diffractometer
Absorption correction: multi-scan
(SADABS; Sheldrick, 2000)
Tmin = 0.889, Tmax = 0.959
12236 measured reflections
2552 independent reflections
2131 reflections with I > 2ꢇ(I)
Rint = 0.028
Compound (II)
Crystal data and Data collection
See Shang et al. (2009)
Refinement
R[F2 > 2ꢇ(F2)] = 0.037
wR(F2) = 0.101
S = 1.01
2552 reflections
139 parameters
H atoms treated by a mixture of
independent and constrained
refinement
Refinement
R[F2 > 2ꢇ(F2)] = 0.030
wR(F2) = 0.065
S = 0.87
H atoms treated by a mixture of
independent and constrained
refinement
ꢁ3
˚
Áꢈmax = 0.56 e A
ꢁ3
˚
Áꢈmin = ꢁ0.57 e A
ꢁ3
˚
Áꢈmax = 0.20 e A
Áꢈmin = ꢁ0.22 e A
2346 reflections
205 parameters
ꢁ3
˚
Compound (Ic)
Crystal data
C7H8ClNO3SꢀC2H6OS
ꢉ = 81.207 (17)ꢃ
V = 628.83 (18) A
Z = 2
Mo Kꢁ radiation
ꢆ = 0.64 mmꢁ1
T = 167 K
Compound (Ia) was refined in the nonstandard space group Ia,
rather than in Cc, in order to avoid a very large monoclinic angle of
ꢅ = 129.887 (1)ꢃ. N- and O-bound H atoms were taken from differ-
ence Fourier syntheses and refined. C-bound H atoms were posi-
tioned geometrically and treated as riding, with aromatic C—H =
3
˚
Mr = 299.78
Triclinic, P1
a = 6.0394 (12) A
˚
˚
b = 9.4441 (14) A
˚
c = 11.8044 (16) A
ꢁ = 71.078 (11)ꢃ
ꢅ = 89.466 (16)ꢃ
0.40 ꢄ 0.30 ꢄ 0.20 mm
˚
0.95 A, methyl C—H = 0.98 A and methylene C—H = 0.99 A, and
˚
˚
Uiso(H) = 1.2Ueq(non-methyl C) or 1.5Ueq(methyl C) for (Ia), (Ib)
˚
and (Ic), and with aromatic C—H = 0.93 A and methylene
˚
C—H = 0.97 A, and Uiso(H) = 1.2Ueq(C) for (II). The H atoms on
Data collection
Siemens SMART 1K CCD area-
detector diffractometer
Absorption correction: multi-scan
(SADABS; Sheldrick, 2000)
Tmin = 0.779, Tmax = 0.880
10341 measured reflections
3481 independent reflections
2398 reflections with I > 2ꢇ(I)
Rint = 0.057
atoms C7 and C12 of (Ib) were taken from a difference synthesis and
refined. The pyrrolidone ring atoms C9, C10 and C11 of (Ib) were
found to be displaced from the mirror plane and so they are disor-
dered and were refined with site-occupation factors of 0.5.
ꢂ
Acta Cryst. (2012). C68, o45–o50
Beko et al.
C7H8ClNO3S and related compounds o49
¨

organic compounds
Data collection: SMART (Siemens, 1995) for (Ia), (Ib) and (Ic);
SMART (Bruker, 1998) for (II). Cell refinement: SAINT (Siemens,
1995) for (Ia); SMART (Siemens, 1995) for (Ib) and (Ic); SAINT
(Bruker, 1998) for (II). Data reduction: SAINT (Siemens, 1995) for
(Ia), (Ib) and (Ic); SAINT (Bruker, 1998) for (II). For all compounds,
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: SHELXL97.
References
Allen, F. H. (2002). Acta Cryst. B58, 380–388.
¨
¨
Beko, S. L., Thoms, S. D., Bruning, J., Alig, E., van de Streek, J., Lakatos, A.,
Glaubitz, C. & Schmidt, M. U. (2010). Z. Kristallogr. 225, 382–387.
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem.
Int. Ed. 34, 1555–1573.
Bruker (1998). SMART, SAINT and SADABS. Bruker AXS Inc., Madison,
Wisconsin, USA.
Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262.
Flack, H. D. (1983). Acta Cryst. A39, 876–881.
Shang, S.-M., Ren, C.-X., Wang, X., Lu, L.-D. & Yang, X.-J. (2009). Acta Cryst.
E65, o2221–o2222.
¨
Sheldrick, G. M. (2000). SADABS. University of Gottingen, Germany.
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: SK3426). Services for accessing these data are
described at the back of the journal.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Siemens (1995). SAINT and SMART. Siemens Analytical X-ray Instruments
Inc., Madison, Wisconsin, USA.
ꢂ
o50 Beko et al. C7H8ClNO3S and related compounds
Acta Cryst. (2012). C68, o45–o50
¨