Methyl 2-[(methyl­sulfon­yl)(prop­yl)amino]benzoate

Muhammad Shafiq; M Nawaz Tahir; Islam Ullah Khan; Muhammad Nadeem Arshad; Zeeshan Haider

doi:10.1107/S1600536809054920

. 2009 Dec 24;66(Pt 1):o248. doi: 10.1107/S1600536809054920

Methyl 2-[(methylsulfonyl)(propyl)amino]benzoate

Muhammad Shafiq ^a, M Nawaz Tahir ^b,^*, Islam Ullah Khan ^a, Muhammad Nadeem Arshad ^a, Zeeshan Haider ^a

PMCID: PMC2980136 PMID: 21580129

Abstract

The asymmetric unit of the title compound, C₁₂H₁₇NO₄S, contains two molecules, both of which show disorder of the two terminal C atoms of the propyl chain over two sets of sites with an occupancy ratio of 0.581 (6):0.419 (6). Intramolecular C—H⋯O interactions help to establish the molecular conformations: in one molecule, the dihedral angle between the methyl ester group and the benzene ring is 41.0 (2)°, whereas in the other molecule it is 36.12 (17)°. In the crystal, molecules are linked by intermolecular C—H⋯O and C—H⋯π interactions.

Related literature

For related structures, see: Shafiq et al. (2008 ▶, 2009a ▶,b ▶).

Experimental

Crystal data

C₁₂H₁₇NO₄S
M _r = 271.33
Monoclinic,
a = 10.1762 (4) Å
b = 15.0178 (6) Å
c = 18.0900 (8) Å
β = 92.787 (2)°
V = 2761.3 (2) Å³
Z = 8
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 296 K
0.25 × 0.12 × 0.10 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.955, T _max = 0.968
25991 measured reflections
5409 independent reflections
2607 reflections with I > 2σ(I)
R _int = 0.078

Refinement

R[F ² > 2σ(F ²)] = 0.062
wR(F ²) = 0.193
S = 1.01
5409 reflections
328 parameters
7 restraints
H-atom parameters constrained
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: 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 PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809054920/hb5288sup1.cif

e-66-0o248-sup1.cif^{(27.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809054920/hb5288Isup2.hkl

e-66-0o248-Isup2.hkl^{(259.5KB, hkl)}

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

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

Cg1 and Cg2 are the centroids of the C2–C7 and C14–C19 benzene rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯O8ⁱ	0.93	2.59	3.483 (6)	161
C11A—H11C⋯O1	0.96	2.57	3.486 (15)	159
C16—H16⋯O4	0.93	2.51	3.429 (5)	168
C20—H20C⋯O3ⁱⁱ	0.96	2.57	3.172 (6)	121
C21—H21A⋯O1	0.97	2.55	3.192 (6)	124
C12—H12A⋯Cg2ⁱⁱⁱ	0.96	2.84	3.660 (5)	144
C18—H18⋯Cg1^iv	0.93	2.87	3.588 (5)	135

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

Acknowledgments

MS gratefully acknowledges the Higher Education Commission, Islamabad, Pakistan, for providing a Scholarship under the Indigenous PhD Program (PIN 042–120567-PS2–276).

supplementary crystallographic information

Comment

In continuation to our work on the synthesis of benzothiazine derivatives, we have reported various molecules of this series (Shafiq et al., 2008, 2009a, 2009b). The title compound (I, Fig. 1, Fig. 2) is being reported here in this context.

The asymmtric unit of title compound consists of two molecules. In both molecules the two terminal C-atoms of propyl moiety are disordered over two set of sites with occupancy ratio of 0.581 (6):0.419 (6). The two molecules of asymmetric units differ from each other as the dihedral angle between methyl ester A (O2/C1/O1/C8) with benzene ring B (C2–C7) is 40.96 (21)°, whereas in the other molecule it is 36.12 (17)° between C (O6/C13/O5/C20) and D (C13–C19). The molecules are stabilized due to intra as well as intermolecular and C–H···π interactions (Table 1, Fig. 2).

Experimental

For the preparation of the title compound, the suspension of hexane-washed sodium hydride (50% in mineral oil) was prepared in dry dimethylformamide (3 ml). A solution of methyl N-methylsulfonylanthranilate (70 mg, 0.306 mmol) in dry dimethylformamide (5 ml) was added to the suspension and stirred for 45 min at room temperature. Then, a solution of propyl iodide (156.40 mg, 0.92 mmol) was added to it. The resulting white suspension was stirred for 2.5–3 h, added to ice and pH adjusted at 4–4.5 and kept in freezer. Solid product obtained was filtered and dried to obtain white prisms of title compound.