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

Hong-Ming Li; Zhi-Qiang Cai; Yi-Liang Li; Shi-Yu Zhang

doi:10.1107/S1600536811017090

. 2011 May 11;67(Pt 6):o1383. doi: 10.1107/S1600536811017090

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

Hong-Ming Li ^a,^b, Zhi-Qiang Cai ^a, Yi-Liang Li ^a, Shi-Yu Zhang ^b,^*

PMCID: PMC3120320 PMID: 21754773

Abstract

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.

Related literature

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

Crystal data

C₇H₈N₂O₅S·C₂H₆O
M _r = 278.28
Monoclinic,
a = 11.709 (3) Å
b = 8.8521 (18) Å
c = 12.439 (3) Å
β = 112.459 (7)°
V = 1191.5 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 113 K
0.20 × 0.18 × 0.16 mm

Data collection

Rigaku Saturn CCD area detector diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.943, T _max = 0.954
12473 measured reflections
2840 independent reflections
2091 reflections with I > 2σ(I)
R _int = 0.045

Refinement

R[F ² > 2σ(F ²)] = 0.030
wR(F ²) = 0.079
S = 0.98
2840 reflections
177 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Data collection: RAPID-AUTO (Rigaku, 1998 ▶); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; 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 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811017090/fl2343sup1.cif

e-67-o1383-sup1.cif^{(17.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811017090/fl2343Isup2.hkl

e-67-o1383-Isup2.hkl^{(139.4KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O6ⁱ	0.830 (18)	1.835 (19)	2.6619 (15)	173.6 (17)
N1—H1⋯O6	0.855 (16)	2.114 (16)	2.9601 (17)	170.2 (14)
O6—H6A⋯O2ⁱ	0.78 (2)	2.00 (2)	2.7605 (14)	166 (2)

Open in a new tab

Symmetry code: (i) Inline graphic .

Acknowledgments

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

supplementary crystallographic information

Comment

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).

Experimental

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.