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The title compound, C7H8N2O4S, exhibits a markedly polarized molecular-electronic structure. The mol­ecules are linked into a chain of edge-fused R{_3^3}(12) rings by two N-H...O=S hydrogen bonds [H...O = 2.10 and 2.21 Å, N...O = 2.900 (2) and 2.878 (2) Å, and N-H...O = 152 and 133°].

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103027641/sk1687sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270103027641/sk1687Isup2.hkl
Contains datablock I

CCDC reference: 231087

Comment top

The supramolecular structure of 4-nitroaniline (Tonogaki et al., 1993) consists of a hydrogen-bonded (4,4) sheet (Batten & Robson, 1998) built from a single type of R44(22) ring (Bernstein et al., 1995). This essentially straightforward mode of aggregation can be modified in a variety of ways by the introduction of simple C-substituents. These can be simple space-filling substituents which do not themselves participate in the supramolecular aggregation, but which nonetheless affect the hydrogen-bonding possibilities. Thus, a 2-methyl substituent generates a three-dimensional hydrogen-bonded framework structure (Ferguson et al., 2001), while 2- or 3-trifluoromethyl substituents generate, respectively, molecular ladders or sheets containing alternating R44(12) and R44(32) rings (Glidewell et al., 2002a). Alternatively, the additional substituents can themselves participate in the hydrogen bonding, as with a 3-amino substituent, where (4,4) nets of R44(24) rings are formed (Glidewell et al., 2001), or with a 6-cyano substituent, where the sheets contain alternating R22(12) and R66(36) rings (Glidewell et al., 2002b). Finally, if iodo substituents are present, there is the possibility of iodo···nitro interactions, as in the triclinic and orthorhombic polymorphs of 2-iodo-4-nitroaniline (McWilliam et al., 2001).

Continuing this study, we have now investigated the molecular and supramolecular structure of the title compound, (I). The supramolecular structure is again dominated by two N—H···O hydrogen bonds, but in both of these the acceptor is one of the sulfone O atoms. The nitro group does not participate at all in the intermolecular hydrogen bonding. \sch

Within the molecule of (I), the nitro group is nearly coplanar with the aryl ring, as shown by the torsion angles (Table 1), and the C—NH2 and C—NO2 bonds (Table 1) are both short for their types. The corresponding mean and lower-quartile reference values (Allen et al., 1987) are, respectively, 1.355 and 1.340 Å for C—NH2, and 1.468 and 1.460 Å for C—NO2. At the same time, the N—O bonds are both longer than the upper-quartile value of 1.215 Å for aromatic nitro groups, suggesting a significant contribution from the p-quinonoid form, (Ia). However, the C3—C4 and C5—C6 ring bonds are somewhat shorter than the analogous C4—C5 and C2—C3 bonds, respectively (Table 1), indicating a contribution also from the o-quinonoid form, (Ib), although the S—C and S—O distances, at their lower- and upper-quartile reference values, respectively, do not offer significant support for this.

The shorter of the two N—H···OS hydrogen bonds (Table 1) links the molecules of (I) into chains generated by translation. The amino atom N1 in the molecule at (x, y, z) acts as hydrogen-bond donor, via atom H1A, to sulfone atom O21 in the molecule at (x, y − 1, z), so forming a C(6) chain running parallel to the [010] direction. Eight of these chains pass through each unit cell and they are linked in pairs by the second, weaker, N—H···OS hydrogen bond. In this, atom N1 at (x, y, z) acts as hydrogen-bond donor, via atom H1B, to atom O22 in the molecule at (1/2 − x, y − 1/2, −z), so producing a second C(6) chain motif parallel to [010], this time generated by the 21 screw axis along (1/4, y, 0). The combination of the two independent C(6) motifs generates a chain of edge-fused R33(12) rings. There are four chains of rings passing through each unit cell, but there are no direction-specific interactions between adjacent chains. It is perhaps surprising that both aromatic ππ stacking interactions and dipolar nitro···nitro interactions are absent; indeed, the nitro O atoms play no role whatsoever in the supramolecular aggregation of (I).

The one-dimensional supramolecular structure of (I) may be contrasted with the two-dimensional structure of the analogous 2-cyano-4-nitroaniline, (II), where the cyano N and one of the nitro O atoms act as hydrogen-bond acceptors (Glidewell et al., 2004).

Experimental top

A sample of (I) was obtained many years ago from ICI Dyestuffs Division. Crystals suitable for single-crystal X-ray diffraction were grown from a solution in 2-ethoxyethanol.

Refinement top

The systematic absences permitted C2/c and Cc as possible space groups. C2/c was selected, and confirmed by the successful structure analysis. Because the unit cell in C2/c has a β value of 123.4295 (12)°, the cell was transformed to the non-standard setting I2/c in order to reduce the value of β. All H atoms were located in difference maps and were then treated as riding atoms, with C—H distances of 0.95 (aromatic) or 0.98 Å (methyl), and N—H distances of 0.88 Å.

Computing details top

Data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures top
[Figure 1] Fig. 1. The molecule of compound (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. Part of the crystal structure of (I), showing formation of a chain of edge-fused R33(12) rings along [010]. For the sake of clarity, H atoms bonded to C atoms have been omitted. The atoms marked with an asterisk (*), a hash (#), a dollar sign (), an ampersand () or an at sign () are at the symmetry positions (x, 1 + y, z), (1/2 − x, 1/2 + y, −z), (1/2 − x, y − 1/2, −z), (x, y − 1, z) and (1/2 − x, 3/2 + y, −z), respectively.
2-Methanesulfonyl-4-nitroaniline top
Crystal data top
C7H8N2O4SF(000) = 896
Mr = 216.21Dx = 1.624 Mg m3
Monoclinic, I2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -I 2ycCell parameters from 2026 reflections
a = 15.8657 (5) Åθ = 3.1–27.5°
b = 7.2366 (1) ŵ = 0.36 mm1
c = 16.4224 (5) ÅT = 120 K
β = 110.304 (1)°Block, orange
V = 1768.36 (8) Å30.40 × 0.35 × 0.30 mm
Z = 8
Data collection top
Nonius KappaCCD area-detector
diffractometer
2026 independent reflections
Radiation source: Rotating Anode1781 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.005
ϕ scans, and ω scans with κ offsetsθmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan
(DENZO-SMN; Otwinowski & Minor, 1997)
h = 1720
Tmin = 0.871, Tmax = 0.901k = 99
11417 measured reflectionsl = 2121
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.086H-atom parameters constrained
S = 1.10 w = 1/[σ2(Fo2) + (0.0425P)2 + 1.6784P]
where P = (Fo2 + 2Fc2)/3
2026 reflections(Δ/σ)max < 0.001
128 parametersΔρmax = 0.30 e Å3
0 restraintsΔρmin = 0.54 e Å3
Crystal data top
C7H8N2O4SV = 1768.36 (8) Å3
Mr = 216.21Z = 8
Monoclinic, I2/cMo Kα radiation
a = 15.8657 (5) ŵ = 0.36 mm1
b = 7.2366 (1) ÅT = 120 K
c = 16.4224 (5) Å0.40 × 0.35 × 0.30 mm
β = 110.304 (1)°
Data collection top
Nonius KappaCCD area-detector
diffractometer
2026 independent reflections
Absorption correction: multi-scan
(DENZO-SMN; Otwinowski & Minor, 1997)
1781 reflections with I > 2σ(I)
Tmin = 0.871, Tmax = 0.901Rint = 0.005
11417 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0340 restraints
wR(F2) = 0.086H-atom parameters constrained
S = 1.10Δρmax = 0.30 e Å3
2026 reflectionsΔρmin = 0.54 e Å3
128 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.16472 (9)0.01648 (19)0.15027 (9)0.0129 (3)
C20.14987 (9)0.17737 (19)0.14878 (9)0.0125 (3)
C30.12714 (9)0.2637 (2)0.21322 (9)0.0145 (3)
C40.11699 (10)0.1605 (2)0.27969 (9)0.0158 (3)
C50.12723 (10)0.0314 (2)0.28184 (10)0.0179 (3)
C60.15004 (10)0.1176 (2)0.21828 (10)0.0167 (3)
N10.19060 (9)0.10458 (17)0.09107 (8)0.0176 (3)
S20.15031 (2)0.31417 (5)0.06037 (2)0.01342 (12)
O210.14908 (8)0.50435 (14)0.08577 (7)0.0217 (3)
O220.22226 (7)0.25417 (16)0.03171 (7)0.0195 (3)
C210.04740 (10)0.2650 (2)0.02187 (10)0.0175 (3)
N40.09164 (9)0.2524 (2)0.34578 (8)0.0201 (3)
O410.08705 (9)0.42239 (17)0.34441 (8)0.0302 (3)
O420.07460 (8)0.15751 (19)0.40023 (7)0.0268 (3)
H30.11850.39380.21170.017*
H50.11840.10160.32710.021*
H60.15620.24820.21970.020*
H1A0.19850.22510.09430.021*
H1B0.19970.04190.04890.021*
H21A0.04520.13370.03710.026*
H21B0.04160.34010.07320.026*
H21C0.00210.29380.00120.026*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0103 (6)0.0142 (7)0.0141 (6)0.0001 (5)0.0043 (5)0.0015 (5)
C20.0117 (6)0.0128 (7)0.0135 (7)0.0010 (5)0.0050 (5)0.0001 (5)
C30.0120 (7)0.0146 (7)0.0158 (7)0.0001 (5)0.0034 (5)0.0026 (5)
C40.0125 (7)0.0233 (8)0.0126 (7)0.0021 (5)0.0056 (5)0.0027 (5)
C50.0174 (7)0.0225 (8)0.0151 (7)0.0008 (6)0.0073 (6)0.0051 (6)
C60.0191 (7)0.0138 (7)0.0183 (7)0.0013 (5)0.0079 (6)0.0036 (6)
N10.0264 (7)0.0120 (6)0.0184 (6)0.0013 (5)0.0129 (5)0.0006 (5)
S20.0148 (2)0.0117 (2)0.0158 (2)0.00057 (12)0.00792 (14)0.00188 (12)
O210.0296 (6)0.0104 (5)0.0268 (6)0.0020 (4)0.0118 (5)0.0009 (4)
O220.0170 (5)0.0233 (6)0.0234 (6)0.0013 (4)0.0135 (4)0.0047 (4)
C210.0174 (7)0.0205 (7)0.0155 (7)0.0006 (6)0.0066 (6)0.0039 (6)
N40.0154 (6)0.0315 (8)0.0135 (6)0.0045 (5)0.0052 (5)0.0026 (5)
O410.0377 (7)0.0305 (7)0.0250 (6)0.0094 (5)0.0143 (5)0.0073 (5)
O420.0217 (6)0.0464 (8)0.0156 (6)0.0017 (5)0.0108 (5)0.0007 (5)
Geometric parameters (Å, º) top
C1—C21.421 (2)S2—O211.4402 (11)
C2—C31.380 (2)S2—O221.4443 (11)
C3—C41.377 (2)S2—C211.7568 (15)
C4—C51.397 (2)C3—H30.95
C5—C61.368 (2)C5—H50.95
C6—C11.420 (2)C6—H60.95
C1—N11.341 (2)N1—H1A0.88
C4—N41.444 (2)N1—H1B0.88
N4—O411.232 (2)C21—H21A0.98
N4—O421.230 (2)C21—H21B0.98
C2—S21.7592 (14)C21—H21C0.98
N1—C1—C6120.02 (13)C1—N1—H1A120.0
N1—C1—C2123.20 (13)C1—N1—H1B120.0
C6—C1—C2116.77 (13)H1A—N1—H1B120.0
C3—C2—C1121.30 (13)O21—S2—O22118.25 (7)
C3—C2—S2117.06 (11)O21—S2—C21108.28 (7)
C1—C2—S2121.43 (11)O22—S2—C21108.51 (7)
C4—C3—C2119.71 (13)O21—S2—C2107.12 (7)
C4—C3—H3120.1O22—S2—C2109.25 (7)
C2—C3—H3120.1C21—S2—C2104.58 (7)
C3—C4—C5120.95 (14)S2—C21—H21A109.5
C3—C4—N4119.06 (14)S2—C21—H21B109.5
C5—C4—N4119.93 (14)H21A—C21—H21B109.5
C6—C5—C4119.54 (14)S2—C21—H21C109.5
C6—C5—H5120.2H21A—C21—H21C109.5
C4—C5—H5120.2H21B—C21—H21C109.5
C5—C6—C1121.62 (14)O42—N4—O41122.97 (14)
C5—C6—H6119.2O42—N4—C4118.58 (14)
C1—C6—H6119.2O41—N4—C4118.44 (13)
C1—C2—S2—C2175.0 (2)C3—C4—N4—O42173.3 (2)
C1—C2—S2—O21170.2 (2)C5—C4—N4—O41176.9 (2)
C1—C2—S2—O2240.9 (2)C5—C4—N4—O424.1 (2)
C3—C4—N4—O415.7 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O21i0.882.102.900 (2)152
N1—H1B···O220.882.212.878 (2)133
Symmetry code: (i) x, y1, z.

Experimental details

Crystal data
Chemical formulaC7H8N2O4S
Mr216.21
Crystal system, space groupMonoclinic, I2/c
Temperature (K)120
a, b, c (Å)15.8657 (5), 7.2366 (1), 16.4224 (5)
β (°) 110.304 (1)
V3)1768.36 (8)
Z8
Radiation typeMo Kα
µ (mm1)0.36
Crystal size (mm)0.40 × 0.35 × 0.30
Data collection
DiffractometerNonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-scan
(DENZO-SMN; Otwinowski & Minor, 1997)
Tmin, Tmax0.871, 0.901
No. of measured, independent and
observed [I > 2σ(I)] reflections
11417, 2026, 1781
Rint0.005
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.034, 0.086, 1.10
No. of reflections2026
No. of parameters128
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.30, 0.54

Computer programs: KappaCCD Server Software (Nonius, 1997), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97 and PRPKAPPA (Ferguson, 1999).

Selected geometric parameters (Å, º) top
C1—C21.421 (2)C4—N41.444 (2)
C2—C31.380 (2)N4—O411.232 (2)
C3—C41.377 (2)N4—O421.230 (2)
C4—C51.397 (2)C2—S21.7592 (14)
C5—C61.368 (2)S2—O211.4402 (11)
C6—C11.420 (2)S2—O221.4443 (11)
C1—N11.341 (2)S2—C211.7568 (15)
C1—C2—S2—C2175.0 (2)C3—C4—N4—O415.7 (2)
C1—C2—S2—O21170.2 (2)C5—C4—N4—O424.1 (2)
C1—C2—S2—O2240.9 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O21i0.882.102.900 (2)152
N1—H1B···O220.882.212.878 (2)133
Symmetry code: (i) x, y1, z.
 

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