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Acta Cryst. (2011). E67, o1383    [ doi:10.1107/S1600536811017090 ]

N-(2-Hydroxy-5-nitrophenyl)methanesulfonamide ethanol monosolvate

H.-M. Li, Z.-Q. Cai, Y.-L. Li and S.-Y. Zhang

Abstract top

In the title compound, C7H8N2O5S·C2H6O, the dihedral angle between the aromatic ring and the nitro group is 8.78 (9)° and the S atom is displaced by 0.226 (3) Å from the plane of the aromatic ring. In the crystal, the ethanol molecule is involved in hydrogen bonding to two separate sulfonamide molecules, as a donor in an O-H...O interaction and as an acceptor in an N-H...O interaction. Weak C-H...O hydrogen bonding is also present.

Comment top

Nimesulide is a COX-2 inhibitor that has a high affinity for aromatase. Clinical data for Nimesulide in the treatment of several breast cancer patients have recently been presented (Diaz-Cruz et al., 2005).

The title compound (Fig 1) is an important intermediate in the preparation of nimesulide derivatives. Some derivatives of nimesulide have been reported to have a high affinity for aromatase (Su et al., 2006, Wang et al., 2007). Herein, the synthesis and the crystal structure of the title compound are reported.

The dihedral angle between the plane of the aromatic ring and the plane formed by the three atoms of the nitro group is 8.78 (9)° and the deviation of the Sulfur atom from the plane of the aromatic ring is -0.2258 (27) Å. In the crystal packing, The ethanol molecule is involved in hydrogen bonding to two separate sulfonamide molecules (Table 1), as a donor in an O—H···O interaction and as an acceptor in an N—H···O interaction. Weak C—H···O hydrogen bonding is also present (Fig. 2).

Related literature top

The title compound is an intermediate in the preparation of derivatives of the aromatase inhibitor nimesulide [systematic name N-(4-nitro-2-phenoxyphenyl)methanesulfonamide]. For background to the bioactivity and applications of nimesulide, see: Diaz-Cruz et al. (2005). For the synthesis of other nimesulide derivatives, see: Su et al. (2006); Wang et al. (2007). For a related structure, see: Gowda et al., 2007).

Experimental top

NaH (60% powder, 18 g, 0.75 mol) was added to a solution of 2-amino-4-nitrophenol (19.3 g, 0.125 mol) in anhydrous DMF (200 mL) at room temperature. After being stirred at the same temperature for 30 min, methanesulfonyl chloride (57.3 g, 0.5 mol) was added to the mixture, and the stirring was continued overnight at room temperature. H2O (400 mL) was added to the mixture, and then it was neutralized with 5 N HCl until pH=1–2. The intermediate precipitate was collected by filtration and washed with H2O, which was used iinn the next reaction without further purification. The intermediate was added to a 3 N NaOH aq. solution and was stirred at 353 K overnight. After being cooled, it was neutralized with 5 N HCl until pH=1–2. The precipitated solid was collected and washed with H2O to provide the desired product, which was then recrystalized from ethano to give colourless single crystals suitable for X-ray diffraction.

Refinement top

All H atoms were geometrically positioned (C—H 0.95–0.99 Å) and treated as riding, with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: RAPID-AUTO (Rigaku,1998); cell refinement: RAPID-AUTO (Rigaku,1998); data reduction: RAPID-AUTO (Rigaku,1998); 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: CrystalStructure (Rigaku/MSC, 2005).

Figures top
[Figure 1] Fig. 1. The structure of C9H14N2O6S with all non-H atom-labelling scheme and ellipsoids drawn at the 50% probability level.
[Figure 2] Fig. 2. Packing diagram of the title compound with hydrogen bonds.
N-(2-Hydroxy-5-nitrophenyl)methanesulfonamide ethanol monosolvate top
Crystal data top
C7H8N2O5S·C2H6OF(000) = 584
Mr = 278.28Dx = 1.551 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4097 reflections
a = 11.709 (3) Åθ = 1.8–27.9°
b = 8.8521 (18) ŵ = 0.30 mm−1
c = 12.439 (3) ÅT = 113 K
β = 112.459 (7)°Prism, colourless
V = 1191.5 (5) Å30.20 × 0.18 × 0.16 mm
Z = 4
Data collection top
Rigaku Saturn CCD area detector
diffractometer		2840 independent reflections
Radiation source: rotating anode2091 reflections with I > 2σ(I)
multilayerRint = 0.045
Detector resolution: 14.63 pixels mm-1θmax = 27.9°, θmin = 1.9°
ω and φ scansh = −15→15
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		k = −9→11
Tmin = 0.943, Tmax = 0.954l = −16→16
12473 measured reflections
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)] = 0.030Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.079H atoms treated by a mixture of independent and constrained refinement
S = 0.98 w = 1/[σ2(Fo2) + (0.0421P)2]
where P = (Fo2 + 2Fc2)/3
2840 reflections(Δ/σ)max = 0.001
177 parametersΔρmax = 0.33 e Å−3
1 restraintΔρmin = −0.36 e Å−3
Crystal data top
C7H8N2O5S·C2H6OV = 1191.5 (5) Å3
Mr = 278.28Z = 4
Monoclinic, P21/cMo Kα radiation
a = 11.709 (3) ŵ = 0.30 mm−1
b = 8.8521 (18) ÅT = 113 K
c = 12.439 (3) Å0.20 × 0.18 × 0.16 mm
β = 112.459 (7)°
Data collection top
Rigaku Saturn CCD area detector
diffractometer		2840 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		2091 reflections with I > 2σ(I)
Tmin = 0.943, Tmax = 0.954Rint = 0.045
12473 measured reflectionsθmax = 27.9°
Refinement top
R[F2 > 2σ(F2)] = 0.030H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.079Δρmax = 0.33 e Å−3
S = 0.98Δρmin = −0.36 e Å−3
2840 reflectionsAbsolute structure: ?
177 parametersFlack parameter: ?
1 restraintRogers parameter: ?
Special details top

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) top
xyzUiso*/Ueq
S10.23077 (3)0.44845 (4)0.61896 (3)0.01396 (10)
O10.14081 (9)0.51062 (11)0.65857 (8)0.0200 (2)
O20.34570 (9)0.52619 (10)0.64474 (8)0.0187 (2)
O30.37065 (9)0.01532 (12)0.74369 (9)0.0186 (2)
H30.4002 (16)−0.069 (2)0.7674 (14)0.038 (6)*
O4−0.18590 (9)0.18630 (12)0.56941 (9)0.0263 (3)
O5−0.20141 (9)−0.05693 (11)0.57761 (9)0.0240 (3)
N10.27051 (11)0.28099 (13)0.67419 (10)0.0160 (3)
N2−0.13955 (11)0.05910 (14)0.59166 (10)0.0185 (3)
C10.16076 (13)0.42769 (17)0.46762 (11)0.0207 (3)
H1A0.15010.52730.43060.031*
H1B0.07990.37940.44720.031*
H1C0.21320.36480.44040.031*
C20.19037 (12)0.16067 (15)0.67166 (11)0.0138 (3)
C30.06316 (12)0.17416 (16)0.63523 (11)0.0151 (3)
H3A0.02370.26890.61040.018*
C4−0.00540 (13)0.04612 (16)0.63584 (11)0.0153 (3)
C50.04822 (13)−0.09282 (16)0.67288 (11)0.0169 (3)
H5−0.0010−0.17800.67320.020*
C60.17558 (13)−0.10593 (16)0.70973 (11)0.0165 (3)
H60.2141−0.20090.73540.020*
C70.24676 (12)0.01876 (16)0.70925 (11)0.0143 (3)
H10.3450 (15)0.2597 (17)0.6838 (12)0.022 (4)*
O60.52899 (9)0.24326 (11)0.69398 (9)0.0171 (2)
H6A0.5557 (16)0.1858 (19)0.7445 (13)0.033 (5)*
C80.52156 (14)0.16205 (16)0.58969 (12)0.0210 (3)
H8A0.45080.09120.56560.025*
H8B0.59810.10290.60570.025*
C90.50525 (15)0.27419 (19)0.49432 (12)0.0307 (4)
H9A0.43150.33550.48140.046*
H9B0.49570.22030.42260.046*
H9C0.57800.34000.51680.046*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.01380 (18)0.01101 (19)0.01618 (18)−0.00055 (13)0.00473 (13)−0.00005 (13)
O10.0206 (5)0.0166 (5)0.0246 (6)0.0028 (4)0.0106 (4)−0.0020 (4)
O20.0151 (5)0.0144 (5)0.0242 (5)−0.0039 (4)0.0049 (4)−0.0002 (4)
O30.0137 (5)0.0142 (6)0.0261 (6)0.0028 (4)0.0056 (4)0.0053 (4)
O40.0184 (6)0.0224 (6)0.0383 (6)0.0036 (5)0.0111 (5)0.0001 (5)
O50.0188 (6)0.0236 (6)0.0297 (6)−0.0097 (5)0.0095 (5)−0.0065 (4)
N10.0103 (6)0.0133 (6)0.0232 (6)0.0006 (5)0.0051 (5)0.0034 (5)
N20.0178 (6)0.0221 (7)0.0176 (6)−0.0025 (5)0.0092 (5)−0.0037 (5)
C10.0209 (8)0.0227 (8)0.0164 (7)−0.0004 (6)0.0047 (6)0.0010 (6)
C20.0156 (7)0.0134 (7)0.0134 (6)−0.0015 (5)0.0065 (5)−0.0006 (5)
C30.0168 (7)0.0138 (7)0.0150 (6)0.0011 (6)0.0064 (5)−0.0001 (5)
C40.0136 (7)0.0201 (8)0.0136 (7)−0.0023 (6)0.0068 (5)−0.0034 (5)
C50.0210 (8)0.0150 (7)0.0163 (7)−0.0066 (6)0.0089 (6)−0.0023 (5)
C60.0191 (7)0.0133 (7)0.0170 (7)0.0011 (6)0.0070 (6)0.0019 (6)
C70.0145 (7)0.0161 (8)0.0127 (7)0.0005 (6)0.0055 (5)−0.0007 (5)
O60.0188 (5)0.0137 (6)0.0184 (5)0.0008 (4)0.0069 (4)0.0012 (4)
C80.0245 (8)0.0192 (8)0.0207 (7)−0.0015 (6)0.0102 (6)−0.0032 (6)
C90.0349 (10)0.0359 (10)0.0249 (8)0.0045 (8)0.0155 (7)0.0059 (7)
Geometric parameters (Å, °) top
S1—O11.4323 (10)C3—C41.3906 (19)
S1—O21.4344 (10)C3—H3A0.9500
S1—N11.6254 (12)C4—C51.378 (2)
S1—C11.7523 (14)C5—C61.3875 (19)
O3—C71.3468 (17)C5—H50.9500
O3—H30.830 (18)C6—C71.3845 (19)
O4—N21.2345 (15)C6—H60.9500
O5—N21.2302 (15)O6—C81.4564 (16)
N1—C21.4119 (17)O6—H6A0.776 (15)
N1—H10.855 (16)C8—C91.502 (2)
N2—C41.4571 (18)C8—H8A0.9900
C1—H1A0.9800C8—H8B0.9900
C1—H1B0.9800C9—H9A0.9800
C1—H1C0.9800C9—H9B0.9800
C2—C31.3865 (19)C9—H9C0.9800
C2—C71.4130 (19)
O1—S1—O2119.28 (6)C5—C4—C3122.62 (13)
O1—S1—N1109.54 (6)C5—C4—N2118.98 (12)
O2—S1—N1104.50 (6)C3—C4—N2118.37 (12)
O1—S1—C1107.83 (7)C4—C5—C6118.70 (13)
O2—S1—C1107.72 (7)C4—C5—H5120.7
N1—S1—C1107.42 (7)C6—C5—H5120.7
C7—O3—H3112.7 (12)C7—C6—C5120.31 (13)
C2—N1—S1126.73 (10)C7—C6—H6119.8
C2—N1—H1118.1 (10)C5—C6—H6119.8
S1—N1—H1111.8 (10)O3—C7—C6123.89 (13)
O5—N2—O4123.04 (12)O3—C7—C2115.83 (12)
O5—N2—C4118.62 (12)C6—C7—C2120.28 (13)
O4—N2—C4118.34 (12)C8—O6—H6A105.5 (13)
S1—C1—H1A109.5O6—C8—C9108.88 (12)
S1—C1—H1B109.5O6—C8—H8A109.9
H1A—C1—H1B109.5C9—C8—H8A109.9
S1—C1—H1C109.5O6—C8—H8B109.9
H1A—C1—H1C109.5C9—C8—H8B109.9
H1B—C1—H1C109.5H8A—C8—H8B108.3
C3—C2—N1124.34 (12)C8—C9—H9A109.5
C3—C2—C7119.51 (12)C8—C9—H9B109.5
N1—C2—C7116.14 (12)H9A—C9—H9B109.5
C2—C3—C4118.57 (13)C8—C9—H9C109.5
C2—C3—H3A120.7H9A—C9—H9C109.5
C4—C3—H3A120.7H9B—C9—H9C109.5
O1—S1—N1—C251.29 (13)O5—N2—C4—C3170.54 (12)
O2—S1—N1—C2−179.82 (11)O4—N2—C4—C3−9.04 (18)
C1—S1—N1—C2−65.57 (13)C3—C4—C5—C6−0.8 (2)
S1—N1—C2—C3−9.6 (2)N2—C4—C5—C6177.01 (11)
S1—N1—C2—C7170.35 (10)C4—C5—C6—C70.13 (19)
N1—C2—C3—C4179.32 (12)C5—C6—C7—O3179.95 (12)
C7—C2—C3—C4−0.63 (19)C5—C6—C7—C20.25 (19)
C2—C3—C4—C51.0 (2)C3—C2—C7—O3−179.72 (11)
C2—C3—C4—N2−176.78 (11)N1—C2—C7—O30.33 (17)
O5—N2—C4—C5−7.36 (18)C3—C2—C7—C60.0 (2)
O4—N2—C4—C5173.06 (12)N1—C2—C7—C6−179.95 (12)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3—H3···O6i0.830 (18)1.835 (19)2.6619 (15)173.6 (17)
N1—H1···O60.855 (16)2.114 (16)2.9601 (17)170.2 (14)
O6—H6A···O2i0.78 (2)2.00 (2)2.7605 (14)166 (2)
Symmetry codes: (i) −x+1, y−1/2, −z+3/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3—H3···O6i0.830 (18)1.835 (19)2.6619 (15)173.6 (17)
N1—H1···O60.855 (16)2.114 (16)2.9601 (17)170.2 (14)
O6—H6A···O2i0.78 (2)2.00 (2)2.7605 (14)166 (2)
Symmetry codes: (i) −x+1, y−1/2, −z+3/2.
Acknowledgements top

The authors thank the State Key Laboratory of Elemento-organic Chemistry, Nankai University, for the data collection.

references
References top

Diaz-Cruz, E. S., Shapiro, C. L. & Brueggemeier, R. W. (2005). J. Clin. Endocrinol. Metab. 90, 2563–2570.

Gowda, B. T., Foro, S. & Fuess, H. (2007). Acta Cryst. E63, o2337.

Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.

Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.

Rigaku/MSC (2005). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Su, B., Diaz-Cruz, E. S., Landini, S. & Brueggemeier, R. W. (2006). J. Med. Chem. 49, 1413–1419.

Wang, M., Lacy, G., Gao, M., Miller, K. D., Sledge, G. W. & Zheng, Q.-H. (2007). Bioorg. Med. Chem. Lett. 17, 332–336.