2-(N-Phenyl­methane­sulfonamido)­ethyl 1H-pyrrole-2-carboxyl­ate

Salman Tariq Khan; Peng Yu; Aisha Nelofar; Zaheer Ahmed; Suchada Chantrapromma

doi:10.1107/S160053681101261X

. 2011 Apr 13;67(Pt 5):o1125–o1126. doi: 10.1107/S160053681101261X

2-(N-Phenylmethanesulfonamido)ethyl 1H-pyrrole-2-carboxylate

Salman Tariq Khan ^a,^*, Peng Yu ^b, Aisha Nelofar ^a, Zaheer Ahmed ^c, Suchada Chantrapromma ^d,^‡

PMCID: PMC3089296 PMID: 21754438

Abstract

In the title compound, C₁₄H₁₆N₂O₄S, the ethoxycarbonyl group is nearly planar, with an r.m.s. deviation of 0.0067 Å, and is almost coplanar with the pyrrole ring [dihedral angle = 5.81 (15)°], whereas it is inclined at a dihedral angle of 61.90 (13)° to the phenyl ring. The dihedral angle between the pyrrole and phenyl rings is 56.15 (13)°. In the crystal, centrosymmetrically related molecules are linked into dimers by pairs of N—H⋯O hydrogen bonds, forming rings of R ₂ ²(10) graph-set motif. The dimers are further connected by weak intermolecular C—H⋯O hydrogen bonds and C—H⋯π interactions, forming layers parallel to the bc plane.

Related literature

For the pharmacological and biological activity of pyrrole-2-carboxylate derivatives and sulfonamides, see: Brienne et al. (1987 ▶); Burnham et al. (1998 ▶); Fan et al. (2008 ▶); Fu et al. (2002 ▶); Gupton et al. (1999 ▶); Manzanaro et al. (2006 ▶); Mayer et al. (2009 ▶); Yoshikawa et al. (1993 ▶, 1998 ▶). For a related structure, see: Khan et al. (2010 ▶). For standard bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₁₄H₁₆N₂O₄S
M _r = 308.36
Monoclinic,
a = 12.186 (2) Å
b = 5.6516 (11) Å
c = 22.160 (4) Å
β = 104.47 (3)°
V = 1477.8 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 153 K
0.32 × 0.08 × 0.06 mm

Data collection

Rigaku Saturn CCD area-detector diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T _min = 0.928, T _max = 0.986
12044 measured reflections
3499 independent reflections
2726 reflections with I > 2σ(I)
R _int = 0.050

Refinement

R[F ² > 2σ(F ²)] = 0.059
wR(F ²) = 0.152
S = 1.06
3499 reflections
196 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.50 e Å⁻³

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681101261X/rz2576sup1.cif

e-67-o1125-sup1.cif^{(18.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053681101261X/rz2576Isup2.hkl

e-67-o1125-Isup2.hkl^{(171.6KB, hkl)}

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

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

Cg1 is the centroid of the C2–C5/N1 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.92 (4)	1.99 (4)	2.894 (3)	167 (3)
C6—H6B⋯O4ⁱⁱ	0.99	2.53	3.415 (3)	148
C7—H7A⋯O4ⁱⁱⁱ	0.99	2.55	3.406 (3)	145
C7—H7B⋯O1^iv	0.99	2.54	3.431 (3)	150
C6—H6A⋯Cg1^v	0.99	2.91	3.899 (3)	173

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) .

Acknowledgments

STK acknowledges funding from the Industrial Linkage Programme of the Pakistan Council of Scientific and Industrial Research (PCSIR) Laboratories. PY is grateful to Tianjin University of Science & Technology for a research grant (No. 2009 0431). SC thanks the Prince of Songkla University for generous support through the CMRU. STK also thanks Dr Song Haibin (State Key Laboratory of Elemento-Organic Chemistry, Nankai University) for the data collection.

supplementary crystallographic information

Comment

Pyrrole-2-carboxylate based heterocyclic compounds, either naturally occurring or synthetic, have shown various pharmacological and biological activities such as anticancer (Burnham et al., 1998; Gupton et al., 1999; Fan et al., 2008), antidiabetic, aldose reductase inhibition (Mayer et al., 2009; Manzanaro et al., 2006) anti-inflammatory and analgesic activities (Fu et al., 2002). Likewise, compounds containing the sulfonamide moiety have their own biological importance as antifilarial (Brienne et al., 1987) anti-inflammatory, antipyretic, analgesic and antiallergy agents (Yoshikawa et al., 1993; Yoshikawa et al., 1998) The title compound was synthesized as an intermediate which will be used in search of new potent anti-inflammatory and/or analgesic agents. Its crystal structure analysis was undertaken in order to establish the conformation of the various groups.

Fig. 1 shows the molecular structure of the title compound, in which the ethylcarboxylate unit (C1/C2/O1/O2/C6/C7) is planar with r.m.s. of 0.0067 (2) Å. This unit is almost co-planar with the pyrrole ring whereas is inclined to the benzene ring with dihedral angles of 5.81 (15) and 61.90 (13)°, respectively. The dihedral angle between the pyrrole and benzene rings is 56.15 (13)°. The orientation of the methylsulfonamide group (C14/S1/O3/O3/N2) with respect to the ethylcarboxylate unit can be indicated by the torsion angles S1–N2–C7–C6 = 121.87 (18)° and C14–S1–N2–C7 = 72.67 (18)°. The bond lengths are in normal ranges (Allen et al., 1987) and comparable to those reported for a related structure (Khan et al., 2010).

In the crystal structure (Fig. 2), N—H···O hydrogen interactions (Table 1) link centrosymmetrically related molecules into dimers forming rings of R²₂(10) graph-set motif. The dimers are further arranged into layers parallel to the bc plane by weak intermolecular C—H···O hydrogen bonds and C—H···π interactions (Table 1).

Experimental

The title compound was prepared by mixing 2-(phenylamino)ethyl-1H-pyrrole-2-carboxylate (1.0 g, 1.8 mmol), triethylamine (0.88 g, 8.8 mmol) and methanesulfonyl chloride (0.1 g, 8.8 mmol) in dichloromethane (6 ml) under nitrogen in sealed tube. The reaction mixture was stirred for 4 h at 273 K. The mixture was poured onto ice, and then sodium bicarbonate (10 ml, 10%) was added and the solution stirred for 10 minutes. The organic layer was separated and the aqueous layer was extracted with dichloromethane. The combined organic layers were dried over MgSO₄, filtered and concentrated, yielding the a white precipitate of the title compound. Colourless needle-shaped single crystals of the title compound suitable for X-ray structure determination were recrystalized from dichloromethane by the slow evaporation of the solvent at room temperature after several days.