N,N-Bis(2-hy­droxy­eth­yl)-4-methyl­benzene­sulfonamide

Nafeesa Mushtaq; Islam Ullah Khan; Muhammad Yar; Sadia Afzal; Jim Simpson

doi:10.1107/S1600536812041682

. 2012 Oct 20;68(Pt 11):o3142. doi: 10.1107/S1600536812041682

N,N-Bis(2-hydroxyethyl)-4-methylbenzenesulfonamide

Nafeesa Mushtaq ^a, Islam Ullah Khan ^a,^*, Muhammad Yar ^a, Sadia Afzal ^a, Jim Simpson ^b

PMCID: PMC3515243 PMID: 23284463

Abstract

In the title compound C₁₁H₁₇NO₄S, an intramolecular O—H⋯O hydrogen bond forms an S(8) ring and determines the conformation of the bis(2-hydroxyethyl) segment of the molecule, holding the two CH₂CH₂OH groups close to coplanar (r.m.s. deviation = 0.185 Å). In the crystal, O—H⋯O hydrogen bonds link the molecules into zigzag chains along the b axis. Weaker additional C—H⋯O and C—H⋯π contacts generate a three dimensional network, with molecules stacked along the b-axis direction.

Related literature

For pharmaceutical background to sulfonamides, see: Casini et al. (2002 ▶); Chambers & Jawetz (1998 ▶). For an alternative synthesis, see: Hori et al. (2011 ▶). For a related structure, see: Yoon et al. (2001 ▶). For standard bond lengths, see: Allen et al. (1987 ▶) and for hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₁H₁₇NO₄S
M _r = 259.32
Orthorhombic,
a = 17.9308 (5) Å
b = 7.1881 (2) Å
c = 19.8333 (6) Å
V = 2556.28 (13) Å³
Z = 8
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 296 K
0.16 × 0.12 × 0.10 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
3124 measured reflections
3124 independent reflections
2343 reflections with I > 2σ(I)

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.161
S = 0.99
3124 reflections
161 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: APEX2 and SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97, ORTEP-3 (Farrugia, 1997 ▶), enCIFer (Allen et al., 2004 ▶), PLATON (Spek, 2009 ▶) and publCIF (Westrip 2010 ▶).

Supplementary Material

Click here for additional data file.^{(22.1KB, cif)}

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536812041682/nk2181sup1.cif

e-68-o3142-sup1.cif^{(22.1KB, cif)}

Click here for additional data file.^{(153.4KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812041682/nk2181Isup2.hkl

e-68-o3142-Isup2.hkl^{(153.4KB, hkl)}

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

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

Cg1 is the centroid of the C1–C6 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4O⋯O3	0.76 (7)	1.89 (7)	2.634 (3)	166 (7)
O3—H3O⋯O4ⁱ	0.75 (4)	1.92 (4)	2.661 (3)	172 (4)
C10—H10A⋯O1ⁱⁱ	0.97	2.61	3.361 (3)	135
C3—H3⋯Cg1ⁱⁱⁱ	0.93	2.78	3.522 (2)	138

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

Acknowledgments

The authors acknowledge Mr Ejaz for his kind assistance with the X-ray data collection.

supplementary crystallographic information

Comment

Sulfonamides are an important class of drugs with antibacterial, diuretic, hypoglycemic, antithyroid and antitumor action (Casini et al., 2002). Certain sulfonamides are used in combination with other drugs as antimicrobial agents and this paved the way for an antibiotic revolution in medicine. Sulfonamides also act as anti-metabolites and compete for the enzyme involved in the production of folic acid (Chambers & Jawetz, 1998). Most sulfonamides behave as weak acids and binding to basic amino acids can occur. The crystal structure of a tritosylate of diethanolamine has been reported in which the three tosyl groups are separated from one another as much as possible, to minimize steric repulsion (Yoon et al., 2001). The promising pharmaceutical potential of sulfonamides has prompted us to synthesize and characterize diethanolamine derived sulfonamides. Diethanolamine (DEA) itself has skin irritant characteristics; however, when DEA is transformed into new materials, the resulting compounds may become pharmaceutically useful. We therefore synthesized N,N-bis(2-hydroxyethyl)-4-methylbenzenesulfonamide (N-tosyl diethanolamine) (1) and report its molecular and crystal structure here.

The molecular structure of (1) is shown in Fig. 1. The tolyl ring (C1···C6) is inclined at dihedral angles of 27.29 (0.16) ° and 37.78 (0.17) ° with respect to the N1/C8/C9 and N1/C10/C11 planes respectively. Bond distances (Allen et al., 1987) and angles within the molecule are normal and similar to those reported for N,N-bis(tosyloxyethyl)-p-toluenesulfonamide (Yoon et al., 2001). The nitrogen atom of the diethanolamine substituent is approximately sp³ hybridized with the geometry around the N1 atom close to pyramidal [C8—N1—S1 = 117.49 (14)°, C10—N1—S1 = 116.76 (14)° and C8—N1—C10 = 117.98 (18)°]. The two ethanol substituents are unsymmetrically oriented around the nitrogen atom with their conformations ultimately determined by an intramolecular O4—H4···O3 hydrogen bond that forms an S(8) ring (Bernstein et al., 1995).

In the crystal structure intermolecular O3—H3···O4 hydrogen bonds, Table 1, link molecules into zigzag chains along the b axis, Fig 2. C3—H3···π contacts, together with additional C10—H10A···O1 hydrogen bonds, further connect the chains to form a three-dimensional network structure, with molecules stacked along b, Fig 3.

Experimental

Tosyl chloride (0.836 g, 4.4 mmol) was added to a flask containing diethanolamine (0.42 g, 4 mmol) dissolved in CH₂Cl₂. Pyridine was added as a base (0.35 g, 4.4 mmol) and the solution refluxed for 4 hrs. On completion of the reaction, the pyridine was removed in vacuo and the product purified by crystallization. White crystals were obtained with an overall yield of 77%; Rf 0.13 (1:1 hexane and ethyl acetate). M.P: 95–98 0 C; 1H NMR 500 MHz, CDCl₃: 7.70 (d, 2H), 7.33 (d, 2H), 3.87 (t, –CH₂OH, 4H), 3.23 (t, –CH₂N–, 4H), 2.43 (s, –CH₃, 3H). The synthesis of (1) has also been reported using triethylamine rather than pyridine (Hori et al., 2011).