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

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

doi:10.1107/S1600536811017090

organic compounds

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ISSN: 2056-9890

Volume 67| Part 6| June 2011| Page o1383

doi:10.1107/S1600536811017090

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

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

^aTianjin Key Lab of Molecular Design and Drug Discovery, Tianjin Institute of Pharmaceutical Research, Tianjin 300193, People's Republic of China, and ^bSchool of Chinese Materia Medica, Tianjin University of Traditional Chinese Medicine, Tianjin 300193, People's Republic of China
^*Correspondence e-mail: czq0601@gmail.com

(Received 29 March 2011; accepted 6 May 2011; online 11 May 2011)

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, P 2₁ /c
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[F² > 2σ(F²)] = 0.030
wR(F²) = 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

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)
Symmetry code: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

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 ).

Supporting information

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

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

checkCIF report

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.

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

	Fig. 1. The structure of C₉H₁₄N₂O₆S with all non-H atom-labelling scheme and ellipsoids drawn at the 50% probability level.
	Fig. 2. Packing diagram of the title compound with hydrogen bonds.

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

Crystal data top

C₇H₈N₂O₅S·C₂H₆O	F(000) = 584
M_r = 278.28	D_x = 1.551 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4097 reflections
a = 11.709 (3) Å	θ = 1.8–27.9°
b = 8.8521 (18) Å	µ = 0.30 mm⁻¹
c = 12.439 (3) Å	T = 113 K
β = 112.459 (7)°	Prism, colourless
V = 1191.5 (5) Å³	0.20 × 0.18 × 0.16 mm
Z = 4

Data collection top

Rigaku Saturn CCD area detector diffractometer	2840 independent reflections
Radiation source: rotating anode	2091 reflections with I > 2σ(I)
Multilayer monochromator	R_int = 0.045
Detector resolution: 14.63 pixels mm^-1	θ_max = 27.9°, θ_min = 1.9°
ω and ϕ scans	h = −15→15
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −9→11
T_min = 0.943, T_max = 0.954	l = −16→16
12473 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.079	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	w = 1/[σ²(F_o²) + (0.0421P)²] where P = (F_o² + 2F_c²)/3
2840 reflections	(Δ/σ)_max = 0.001
177 parameters	Δρ_max = 0.33 e Å⁻³
1 restraint	Δρ_min = −0.36 e Å⁻³

Crystal data top

C₇H₈N₂O₅S·C₂H₆O	V = 1191.5 (5) Å³
M_r = 278.28	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.709 (3) Å	µ = 0.30 mm⁻¹
b = 8.8521 (18) Å	T = 113 K
c = 12.439 (3) Å	0.20 × 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)
T_min = 0.943, T_max = 0.954	R_int = 0.045
12473 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	1 restraint
wR(F²) = 0.079	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	Δρ_max = 0.33 e Å⁻³
2840 reflections	Δρ_min = −0.36 e Å⁻³
177 parameters

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

	x	y	z	U_iso*/U_eq
S1	0.23077 (3)	0.44845 (4)	0.61896 (3)	0.01396 (10)
O1	0.14081 (9)	0.51062 (11)	0.65857 (8)	0.0200 (2)
O2	0.34570 (9)	0.52619 (10)	0.64474 (8)	0.0187 (2)
O3	0.37065 (9)	0.01532 (12)	0.74369 (9)	0.0186 (2)
H3	0.4002 (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)
N1	0.27051 (11)	0.28099 (13)	0.67419 (10)	0.0160 (3)
N2	−0.13955 (11)	0.05910 (14)	0.59166 (10)	0.0185 (3)
C1	0.16076 (13)	0.42769 (17)	0.46762 (11)	0.0207 (3)
H1A	0.1501	0.5273	0.4306	0.031*
H1B	0.0799	0.3794	0.4472	0.031*
H1C	0.2132	0.3648	0.4404	0.031*
C2	0.19037 (12)	0.16067 (15)	0.67166 (11)	0.0138 (3)
C3	0.06316 (12)	0.17416 (16)	0.63523 (11)	0.0151 (3)
H3A	0.0237	0.2689	0.6104	0.018*
C4	−0.00540 (13)	0.04612 (16)	0.63584 (11)	0.0153 (3)
C5	0.04822 (13)	−0.09282 (16)	0.67288 (11)	0.0169 (3)
H5	−0.0010	−0.1780	0.6732	0.020*
C6	0.17558 (13)	−0.10593 (16)	0.70973 (11)	0.0165 (3)
H6	0.2141	−0.2009	0.7354	0.020*
C7	0.24676 (12)	0.01876 (16)	0.70925 (11)	0.0143 (3)
H1	0.3450 (15)	0.2597 (17)	0.6838 (12)	0.022 (4)*
O6	0.52899 (9)	0.24326 (11)	0.69398 (9)	0.0171 (2)
H6A	0.5557 (16)	0.1858 (19)	0.7445 (13)	0.033 (5)*
C8	0.52156 (14)	0.16205 (16)	0.58969 (12)	0.0210 (3)
H8A	0.4508	0.0912	0.5656	0.025*
H8B	0.5981	0.1029	0.6057	0.025*
C9	0.50525 (15)	0.27419 (19)	0.49432 (12)	0.0307 (4)
H9A	0.4315	0.3355	0.4814	0.046*
H9B	0.4957	0.2203	0.4226	0.046*
H9C	0.5780	0.3400	0.5168	0.046*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.01380 (18)	0.01101 (19)	0.01618 (18)	−0.00055 (13)	0.00473 (13)	−0.00005 (13)
O1	0.0206 (5)	0.0166 (5)	0.0246 (6)	0.0028 (4)	0.0106 (4)	−0.0020 (4)
O2	0.0151 (5)	0.0144 (5)	0.0242 (5)	−0.0039 (4)	0.0049 (4)	−0.0002 (4)
O3	0.0137 (5)	0.0142 (6)	0.0261 (6)	0.0028 (4)	0.0056 (4)	0.0053 (4)
O4	0.0184 (6)	0.0224 (6)	0.0383 (6)	0.0036 (5)	0.0111 (5)	0.0001 (5)
O5	0.0188 (6)	0.0236 (6)	0.0297 (6)	−0.0097 (5)	0.0095 (5)	−0.0065 (4)
N1	0.0103 (6)	0.0133 (6)	0.0232 (6)	0.0006 (5)	0.0051 (5)	0.0034 (5)
N2	0.0178 (6)	0.0221 (7)	0.0176 (6)	−0.0025 (5)	0.0092 (5)	−0.0037 (5)
C1	0.0209 (8)	0.0227 (8)	0.0164 (7)	−0.0004 (6)	0.0047 (6)	0.0010 (6)
C2	0.0156 (7)	0.0134 (7)	0.0134 (6)	−0.0015 (5)	0.0065 (5)	−0.0006 (5)
C3	0.0168 (7)	0.0138 (7)	0.0150 (6)	0.0011 (6)	0.0064 (5)	−0.0001 (5)
C4	0.0136 (7)	0.0201 (8)	0.0136 (7)	−0.0023 (6)	0.0068 (5)	−0.0034 (5)
C5	0.0210 (8)	0.0150 (7)	0.0163 (7)	−0.0066 (6)	0.0089 (6)	−0.0023 (5)
C6	0.0191 (7)	0.0133 (7)	0.0170 (7)	0.0011 (6)	0.0070 (6)	0.0019 (6)
C7	0.0145 (7)	0.0161 (8)	0.0127 (7)	0.0005 (6)	0.0055 (5)	−0.0007 (5)
O6	0.0188 (5)	0.0137 (6)	0.0184 (5)	0.0008 (4)	0.0069 (4)	0.0012 (4)
C8	0.0245 (8)	0.0192 (8)	0.0207 (7)	−0.0015 (6)	0.0102 (6)	−0.0032 (6)
C9	0.0349 (10)	0.0359 (10)	0.0249 (8)	0.0045 (8)	0.0155 (7)	0.0059 (7)

Geometric parameters (Å, º) top

S1—O1	1.4323 (10)	C3—C4	1.3906 (19)
S1—O2	1.4344 (10)	C3—H3A	0.9500
S1—N1	1.6254 (12)	C4—C5	1.378 (2)
S1—C1	1.7523 (14)	C5—C6	1.3875 (19)
O3—C7	1.3468 (17)	C5—H5	0.9500
O3—H3	0.830 (18)	C6—C7	1.3845 (19)
O4—N2	1.2345 (15)	C6—H6	0.9500
O5—N2	1.2302 (15)	O6—C8	1.4564 (16)
N1—C2	1.4119 (17)	O6—H6A	0.776 (15)
N1—H1	0.855 (16)	C8—C9	1.502 (2)
N2—C4	1.4571 (18)	C8—H8A	0.9900
C1—H1A	0.9800	C8—H8B	0.9900
C1—H1B	0.9800	C9—H9A	0.9800
C1—H1C	0.9800	C9—H9B	0.9800
C2—C3	1.3865 (19)	C9—H9C	0.9800
C2—C7	1.4130 (19)

O1—S1—O2	119.28 (6)	C5—C4—C3	122.62 (13)
O1—S1—N1	109.54 (6)	C5—C4—N2	118.98 (12)
O2—S1—N1	104.50 (6)	C3—C4—N2	118.37 (12)
O1—S1—C1	107.83 (7)	C4—C5—C6	118.70 (13)
O2—S1—C1	107.72 (7)	C4—C5—H5	120.7
N1—S1—C1	107.42 (7)	C6—C5—H5	120.7
C7—O3—H3	112.7 (12)	C7—C6—C5	120.31 (13)
C2—N1—S1	126.73 (10)	C7—C6—H6	119.8
C2—N1—H1	118.1 (10)	C5—C6—H6	119.8
S1—N1—H1	111.8 (10)	O3—C7—C6	123.89 (13)
O5—N2—O4	123.04 (12)	O3—C7—C2	115.83 (12)
O5—N2—C4	118.62 (12)	C6—C7—C2	120.28 (13)
O4—N2—C4	118.34 (12)	C8—O6—H6A	105.5 (13)
S1—C1—H1A	109.5	O6—C8—C9	108.88 (12)
S1—C1—H1B	109.5	O6—C8—H8A	109.9
H1A—C1—H1B	109.5	C9—C8—H8A	109.9
S1—C1—H1C	109.5	O6—C8—H8B	109.9
H1A—C1—H1C	109.5	C9—C8—H8B	109.9
H1B—C1—H1C	109.5	H8A—C8—H8B	108.3
C3—C2—N1	124.34 (12)	C8—C9—H9A	109.5
C3—C2—C7	119.51 (12)	C8—C9—H9B	109.5
N1—C2—C7	116.14 (12)	H9A—C9—H9B	109.5
C2—C3—C4	118.57 (13)	C8—C9—H9C	109.5
C2—C3—H3A	120.7	H9A—C9—H9C	109.5
C4—C3—H3A	120.7	H9B—C9—H9C	109.5

O1—S1—N1—C2	51.29 (13)	O5—N2—C4—C3	170.54 (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—C6	177.01 (11)
S1—N1—C2—C7	170.35 (10)	C4—C5—C6—C7	0.13 (19)
N1—C2—C3—C4	179.32 (12)	C5—C6—C7—O3	179.95 (12)
C7—C2—C3—C4	−0.63 (19)	C5—C6—C7—C2	0.25 (19)
C2—C3—C4—C5	1.0 (2)	C3—C2—C7—O3	−179.72 (11)
C2—C3—C4—N2	−176.78 (11)	N1—C2—C7—O3	0.33 (17)
O5—N2—C4—C5	−7.36 (18)	C3—C2—C7—C6	0.0 (2)
O4—N2—C4—C5	173.06 (12)	N1—C2—C7—C6	−179.95 (12)

Hydrogen-bond geometry (Å, º) top

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)

Symmetry code: (i) −x+1, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₇H₈N₂O₅S·C₂H₆O
M_r	278.28
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	113
a, b, c (Å)	11.709 (3), 8.8521 (18), 12.439 (3)
β (°)	112.459 (7)
V (Å³)	1191.5 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.30
Crystal size (mm)	0.20 × 0.18 × 0.16

Data collection
Diffractometer	Rigaku Saturn CCD area detector diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.943, 0.954
No. of measured, independent and observed [I > 2σ(I)] reflections	12473, 2840, 2091
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.079, 0.98
No. of reflections	2840
No. of parameters	177
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.36

Computer programs: RAPID-AUTO (Rigaku,1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), CrystalStructure (Rigaku/MSC, 2005).

Hydrogen-bond geometry (Å, º) top

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	0.776 (15)	2.003 (16)	2.7605 (14)	165.5 (18)

Symmetry code: (i) −x+1, y−1/2, −z+3/2.

Acknowledgements

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

References

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