N-Acetyl-4-[(2-hydroxybenzylidene)-amino]benzenesulfonamide monohydrate and N-acetyl-4-[(5-bromo-2-hydroxybenzylidene)amino]benzenesulfonamide monohydrate

Article abstract of DOI:10.1107/S0108270105017853

Molecules of the title compounds, C₁₅H₁₄N ₂O₄S·H₂O and C₁₅H ₁₃BrN₂O₄S·H₂O, adopt an E configuration about the azomethine C=N double bond. In both molecules, the two benzene rings and the azomethine group are practically coplanar, as a result of intramolecular hydrogen bonds involving the hydroxy O atom and azomethine N atom. The angular disposition of the bonds about the S atom deviates significantly from that of a regular tetrahedron. In the crystal structures, both compounds form two-dimensional layers parallel to the (100) plane.

Full text of DOI:10.1107/S0108270105017853

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
inhibitory interaction. We report here the crystal struc-
tures of N-acetyl-4-[(2-hydroxybenzylidene)amino]benzene-
sulfonamide monohydrate, (I), and N-acetyl-4-[(5-bromo-
2-hydroxybenzylidene)amino]benzenesulfonamide monohy-
drate, (II), as part of this study.
ISSN 0108-2701
N-Acetyl-4-[(2-hydroxybenzylidene)-
amino]benzenesulfonamide mono-
hydrate and N-acetyl-4-[(5-bromo-
2-hydroxybenzylidene)amino]-
The atom-numbering schemes and views of the molecules of
(I) and (II) are shown in Figs. 1 and 2, respectively. Both (I)
benzenesulfonamide monohydrate
and (II) adopt an E con®guration about the azomethine C
N
Yurii M. Chumakov,a* Victor I. Tsapkov,b Gabriele
Bocellic and Boris Ya. Antosyaka
double bond, with torsion angles of 180.0 (3) and 179.1 (2)ꢀ,
respectively. The differences in the bond lengths and angles in
(I) and (II) are within three times the combined values of their
aInstitute of Applied Physics, Academy of Sciences of Moldova, Academy Street 5,
MD2028 Chisinau, Moldova, bDepartment of Chemistry, State University of
Moldova, Mateevici Street 60, MD2009 Chisinau, Moldova, and cIMEM±CNR,
Parma, Italy
Ê
s.u. values. The S1ÐC11 distance of 1.760 (3) A in (I) and (II)
is a normal single-bond value and matches well with those
observed in other sulfonamides (Singh et al., 1984; Abra-
menko & Sergienko, 2002). The SÐN bond distances in (I)
and (II) have a considerable amount of double-bond char-
acter. The SÐO distances are similar to those found in
analogous structures. These distances do not vary signi®cantly
in the sulfonamide structures, despite the differing inter-
molecular interaction patterns observed. The bond lengths
and angles in the benzene rings have characteristic values. The
angular disposition of the bonds about atom S1 deviates
signi®cantly from that of a regular tetrahedron, with the
Correspondence e-mail: chumakov.xray@phys.asm.md
Received 14 March 2005
Accepted 6 June 2005
Online 22 June 2005
Molecules of the title compounds, C15H14N2O4SÁH2O and
C15H13BrN2O4SÁH2O, adopt an E con®guration about the
azomethine C N double bond. In both molecules, the two
benzene rings and the azomethine group are practically
coplanar, as a result of intramolecular hydrogen bonds
involving the hydroxy O atom and azomethine N atom. The
angular disposition of the bonds about the S atom deviates
signi®cantly from that of a regular tetrahedron. In the crystal
structures, both compounds form two-dimensional layers
parallel to the (100) plane.
Comment
Sulfonamides constitute an important class of antimicrobial
agents which exert antibacterial action by inhibiting the
enzyme dihydropteroate synthase competitively towards the
substrate p-aminobenzoate (PAB). This enzyme catalyses the
formation of dihydropteroate from PAB and hydroxymethyl-
dihydropteridine pyrophosphate (Brown, 1971), so its inhibi-
tion leads to bacteriostasis. It is known that N-acetyl-4-
aminobenzenesulfonamide belongs to the class of sulfonamide
drugs with short-term action and it is widely applied in medical
practice for the treatment of diseases caused by various coccal
infections. The presence of the amino group in this compound
leads to condensation with aldehydes and ketones, thus
enlarging the number of functional groups and changing its
chemical and medicobiological properties. A detailed study of
the structural features of inhibitors in relation to their bio-
logical activity is an important step towards the deduction of
the interaction mechanisms of enzyme inhibition and provides
useful knowledge for the design of the most suitable mol-
ecules according to the stereo-electronic requirements of the
Figure 1
A view of (I), including the water molecule, showing the atomic labelling
scheme. Displacement ellipsoids are drawn at the 50% probability level
and H atoms are shown as small circles of arbitrary radii.
Figure 2
A view of (II), including the water molecule, showing the atomic labelling
scheme. Displacement ellipsoids are drawn at the 50% probability level
and H atoms are shown as small circles of arbitrary radii.
o460 # 2005 International Union of Crystallography
DOI: 10.1107/S0108270105017853
Acta Cryst. (2005). C61, o460±o463

organic compounds
largest angle being O2ÐS1ÐO3 [120.0 (1)ꢀ in (I) and (II)]
and the smallest being O3ÐS1ÐN2 [104.4 (1) and 104.3 (1)ꢀ
in (I) and (II), respectively]. These distortions of bond angles
may be caused by S1ÐO2Á Á ÁCg (ꢀ-ring) interactions (Spek,
2003), where Cg is the centroid of the C8±C13 aromatic ring at
symmetry position (x, y 1, z) in (I) and (x, y + 1, z) in (II).
The O2Á Á ÁCg and S2Á Á ÁCg separations for (I) are 3.142 and
superimposition of the molecules of (I) and (II), with a
Ê
weighted r.m.s. deviation of 0.066 A for atoms N1/C1±C13,
illustrating the isostructural nature of these compounds.
In (I) and (II), in molecules related by a b cell translation,
Ê
short intermolecular contacts of 2.99 and 2.95 A, respectively,
exist between carbonyl atom C14 and sulfonyl atom O2. These
molecules are linked by O1WÐH1WÁ Á ÁO4, O1WÐ
H2WÁ Á ÁO4 and O1WÐH2WÁ Á ÁO2 hydrogen bonds (Tables 2
and 4), which leads to the close approach of atoms O2 and C14
due to rotation of the sulfonamide and acetyl moieties about
the S1ÐN2 and N2ÐC14 bonds. In the related structures of
2-[4-(acetylaminosulfonyl)phenylcarbamoyl]benzoic acid (ph-
thalylsulfacetamide), (III) (Singh et al., 1984), and p-amino-
benzenesulfonacetamide, (IV) (Basak & Mazumdar, 1982),
where the water molecule is absent in the crystal packing, the
O2ÐS1ÐN2ÐC14 and S1ÐN2ÐC14ÐO4 torsion angles are
53.2 and 61.5ꢀ, and 6.8 and 7.2ꢀ, respectively, whereas in (I)
and (II), these angles are 46.0 (3) and 45.8 (2)ꢀ, and 4.3 (4)
and 3.8 (4)ꢀ, respectively. In (III) and (IV), the above-
mentioned intermolecular contacts between the carbonyl C
Ê
Ê
3.137 A, respectively, and for (II) are 3.802 and 3.804 A,
respectively, and the angles between the O2ÐCg vectors and
the normals to the C8±C13 benzene rings are 8.3 and 9.06ꢀ,
respectively, for (I) and (II).
The sulfonamide and acetyl moieties are capable of a
variety of conformational states by means of rotations about
the S1ÐN2 and N2ÐC14 bonds. The dihedral angles
describing these conformations are 70.5 (3) and 176.6 (2)ꢀ in
(I), and 70.9 (2) and 177.1 (1)ꢀ in (II). Fig. 3 shows a
Ê
and sulfonyl O atoms are 4.69 and 4.39 A, respectively. A
check of the Cambridge Structural Database [Version 5.25
(Allen, 2002) and ConQuest (Bruno et al., 2002)] for close
contacts between such atoms has been carried out (R factor
less than 0.075) for compounds containing the benzoyl-
sulfacetamide fragment and in which the given contact ranges
Ê
from 2.9 to 3.22 A. Only two such compounds were found,
Figure 3
A superimposition of the structures of (I) (dashed lines) and (II).
Figure 4
Figure 5
Part of the crystal structure of (I), viewed along the b axis, showing the
formation of the two-dimensional network. H atoms not involved in
hydrogen bonding have been omitted for clarity.
A packing diagram for (II), viewed along the b axis, showing the
formation of the two-dimensional network. H atoms not involved in
hydrogen bonding have been omitted for clarity.
ꢁ
Acta Cryst. (2005). C61, o460±o463
Chumakov et al.
C15H14N2O4SÁH2O and C15H13BrN2O4SÁH2O o461

organic compounds
Data collection
namely 2,8-dimethoxy-5,11-di-p-tosyl-5,6,11,12-tetrahydrodi-
benzo[b,f]diazocine-6,12-dione (Filipenko et al. 1988) and the
silver salt of N-(p-aminophenylsulfonyl)acetamide (Ghosh et
Bruker SMART CCD area-detector
diffractometer
! scans
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
Tmin = 0.951, Tmax = 0.974
11981 measured re¯ections
2696 independent re¯ections
1966 re¯ections with I > 2ꢅ(I)
Rint = 0.057
ꢃmax = 25.0ꢀ
Ê
al., 1990), for which the OÁ Á ÁC separations are 3.13 and 3.05 A,
h = 30 ! 30
respectively.
k = 5 ! 5
l = 14 ! 14
In the molecules of (I) and (II), the two benzene rings and
the azomethine group are practically coplanar, due to intra-
molecular O1ÐHÁ Á ÁN1 hydrogen bonds. The deviations of
atoms N1/C1±C13 from the best-®t plane through them are
Re®nement
Re®nement on F2
R[F2 > 2ꢅ(F2)] = 0.054
wR(F2) = 0.113
w = 1/[ꢅ2(Fo2) + (0.0529P)2
+ 0.2401P]
Ê
between 0.043 and 0.042 A in (I), and between 0.098 and
Ê
0.096 A in (II). In the structure of (III), where the above-
2
where P = (Fo + 2Fc2)/3
S = 1.06
2696 re¯ections
221 parameters
H atoms treated by a mixture of
independent and constrained
re®nement
(Á/ꢅ)max = 0.008
mentioned intramolecular hydrogen bond is absent, the two
benzene rings are rotated by 62.1ꢀ with respect to one another.
The molecular packings of (I) and (II) are shown in Figs. 4
and 5, viewed down the b axis in both cases. Both compounds
are arranged in the form of in®nite two-dimensional layers
parallel to the (100) plane, as a result of NÐHÁ Á ÁO, CÐHÁ Á ÁO
and OÐHÁ Á ÁO hydrogen bonds (Tables 2 and 4). Between
these layers, there are intermolecular van der Waals inter-
actions. The two structures are essentially isomorphous; the
slight lengthening of the a cell dimension in bromo compound
(II) compared with that in (I) is attributable to the increased
size of Br compared with H.
3
Ê
Áꢆmax = 0.22 e A
3
Ê
0.30 e A
Áꢆmin
=
Table 2
Hydrogen-bond geometry (A, ) for (I).
ꢀ
Ê
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
O1ÐH1OÁ Á ÁN1
0.83 (5)
0.84 (4)
0.84 (4)
0.86
0.84 (3)
0.93
1.86 (5)
2.51 (4)
2.11 (4)
1.91
2.16 (4)
2.49
2.626 (4)
3.054 (3)
2.897 (4)
2.740 (4)
2.960 (4)
3.188 (3)
152 (4)
124 (3)
155 (5)
161
157 (4)
132
O1WÐH1WÁ Á ÁO2i
O1WÐH1WÁ Á ÁO4i
N2ÐH2BÁ Á ÁO1W
O1WÐH2WÁ Á ÁO4ii
C10ÐH10AÁ Á ÁO3iii
Experimental
1
2
1
2
1
Symmetry codes: (i) x;
y; z ‡ 12; (ii) x; 21 y; z ‡ 12; (iii) x;
y; z
.
2
Schiff bases (I) and (II) were prepared by condensation of salicylic
acid (1.05 g, 10 mmol) and 5-bromosalicylaldehyde (2.01 g, 10 mmol)
with N-acetyl-4-aminobenzenesulfonamide (2.14 g, 10 mmol) in
boiling ethanol. The products precipitated from the reaction mixtures
in yields of 61 and 65%, respectively. Both compounds were recrys-
tallized from alcohol solution.
Compound (II)
Crystal data
Compound (I)
C15H13BrN2O4SÁH2O
Mo Kꢂ radiation
Cell parameters from 8514
re¯ections
Mr = 415.26
Monoclinic, P21=c
Crystal data
3
Ê
a = 26.858 (3) A
ꢃ = 5.6±28.1
ꢄ = 2.64 mm
T = 298 K
C15H14N2O4SÁH2O
Dx = 1.440 Mg m
Mo Kꢂ radiation
Cell parameters from 4944
re¯ections
1
Ê
b = 4.855 (2) A
Mr = 336.37
Monoclinic, P21=c
Ê
c = 12.708 (3) A
ꢁ = 91.428 (12)ꢀ
Ê
V = 1656.6 (8) A
Prism, yellow
0.24 Â 0.23 Â 0.11 mm
Ê
a = 25.486 (3) A
3
Ê
b = 4.8964 (13) A
ꢃ = 3.3±28.3
ꢄ = 0.24 mm
T = 298 K
1
Ê
c = 12.605 (3) A
Z = 4
Dx = 1.665 Mg m
3
ꢁ = 99.44 (3)ꢀ
V = 1551.7 (6) A
Z = 4
3
Ê
Prism, yellow
0.26 Â 0.13 Â 0.11 mm
Table 3
Selected geometric parameters (A, ) for (II).
ꢀ
Ê
Table 1
Selected geometric parameters (A, ) for (I).
ꢀ
Ê
Br1ÐC4
S1ÐO2
S1ÐO3
S1ÐN2
S1ÐC11
1.901 (3)
1.429 (2)
1.432 (2)
1.649 (2)
1.760 (3)
O1ÐC1
O4ÐC14
N1ÐC7
N1ÐC8
N2ÐC14
1.344 (4)
1.211 (3)
1.277 (4)
1.421 (3)
1.385 (3)
S1ÐO2
S1ÐO3
S1ÐN2
S1ÐC11
O1ÐC1
1.424 (2)
1.431 (2)
1.651 (3)
1.760 (3)
1.354 (5)
O4ÐC14
N1ÐC8
N1ÐC7
N2ÐC14
1.223 (3)
1.423 (4)
1.277 (4)
1.376 (3)
O2ÐS1ÐO3
O2ÐS1ÐN2
O2ÐS1ÐC11
O3ÐS1ÐN2
O3ÐS1ÐC11
N2ÐS1ÐC11
C7ÐN1ÐC8
S1ÐN2ÐC14
O1ÐC1ÐC6
O1ÐC1ÐC2
119.95 (12)
108.50 (11)
109.03 (12)
104.31 (11)
108.79 (12)
105.25 (11)
121.9 (2)
124.28 (18)
121.9 (3)
119.2 (2)
Br1ÐC4ÐC5
Br1ÐC4ÐC3
N1ÐC7ÐC6
N1ÐC8ÐC13
N1ÐC8ÐC9
S1ÐC11ÐC12
S1ÐC11ÐC10
O4ÐC14ÐC15
N2ÐC14ÐC15
O4ÐC14ÐN2
119.90 (19)
119.9 (2)
122.5 (2)
124.6 (2)
116.8 (2)
119.2 (2)
120.0 (2)
123.2 (3)
114.6 (2)
122.2 (3)
O2ÐS1ÐO3
O2ÐS1ÐN2
O2ÐS1ÐC11
O3ÐS1ÐN2
O3ÐS1ÐC11
N2ÐS1ÐC11
C7ÐN1ÐC8
S1ÐN2ÐC14
O1ÐC1ÐC2
120.03 (12)
108.32 (13)
109.11 (13)
104.44 (12)
108.81 (13)
105.08 (13)
122.0 (2)
O1ÐC1ÐC6
N1ÐC7ÐC6
N1ÐC8ÐC13
N1ÐC8ÐC9
S1ÐC11ÐC10
S1ÐC11ÐC12
O4ÐC14ÐC15
N2ÐC14ÐC15
O4ÐC14ÐN2
121.6 (3)
123.1 (2)
124.6 (2)
116.8 (2)
120.1 (2)
119.2 (2)
123.2 (3)
115.1 (2)
121.7 (3)
124.81 (19)
118.9 (3)
ꢁ
o462 Chumakov et al. C15H14N2O4SÁH2O and C15H13BrN2O4SÁH2O
Acta Cryst. (2005). C61, o460±o463

organic compounds
Ê
subject to an OÐH restraint of 0.84 (4) A. All other H atoms were
Data collection
Ê
placed in idealized positions, with aromatic CÐH = 0.93 A,
Bruker SMART CCD area-detector
diffractometer
! scans
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
Tmin = 0.549, Tmax = 0.748
13900 measured re¯ections
2893 independent re¯ections
2446 re¯ections with I > 2ꢅ(I)
Rint = 0.029
Ê
Ê
methyl CÐH = 0.96 A and NÐH = 0.86 A, and included in the
re®nement in the riding-model approximation, with Uiso(H) =
1.2Ueq(C,N).
ꢃmax = 25.0ꢀ
h = 31 ! 31
For both compounds, data collection: SMART (Bruker, 2003); cell
re®nement: SAINT (Bruker, 2003); data reduction: SAINT; structure
solution: SHELXS97 (Sheldrick, 1997); structure re®nement:
SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek,
2003); publication software: PLATON.
k = 5 ! 5
l = 15 ! 15
Re®nement
Re®nement on F2
R[F2 > 2ꢅ(F2)] = 0.033
wR(F2) = 0.085
S = 1.03
2892 re¯ections
230 parameters
H atoms treated by a mixture of
independent and constrained
re®nement
w = 1/[ꢅ2(Fo2) + (0.0482P)2
+ 0.6173P]
where P = (Fo2 + 2Fc2)/3
(Á/ꢅ)max = 0.043
3
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: HJ1053). Services for accessing these data are
described at the back of the journal.
Ê
Áꢆmax = 0.57 e A
3
Ê
0.42 e A
Áꢆmin
=
References
Table 4
Hydrogen-bond geometry (A, ) for (II).
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DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
O1ÐH1Á Á ÁN1
0.83 (4)
0.85 (4)
0.85 (4)
0.86
0.84 (4)
0.93
0.93
1.88 (4)
2.46 (4)
2.13 (5)
1.92
2.31 (4)
2.54
2.58
2.627 (4)
3.085 (3)
2.889 (4)
2.749 (3)
2.991 (4)
3.211 (3)
2.945 (4)
149 (3)
130 (4)
148 (5)
161
138 (4)
129
104
O1WÐH1WÁ Á ÁO2i
O1WÐH1WÁ Á ÁO4i
N2ÐH2BÁ Á ÁO1W
O1WÐH2WÁ Á ÁO4ii
C10ÐH10AÁ Á ÁO3iii
C12ÐH12AÁ Á ÁO3
Symmetry codes: (i) x;
y; z ‡ 12; (ii) x; 21 y; z ‡ 12; (iii) x;
y; z
.
2
1
2
1
2
1
È
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È
Gottingen, Germany.
Hydroxy H atoms and all water H atoms were found in difference
maps at an intermediate stage of the re®nement and were re®ned
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ꢁ
Acta Cryst. (2005). C61, o460±o463
Chumakov et al.
C15H14N2O4SÁH2O and C15H13BrN2O4SÁH2O o463