Piperidinium 4-hydr­oxy-3-methoxy­carbon­yl-1,2-benzothia­zin-2-ide 1,1-dioxide

Muhammad Nadeem Arshad; Muhammad Zia-ur-Rehman; Naveed Ahmed; Islam Ullah Khan

doi:10.1107/S1600536809036204

. 2009 Sep 12;65(Pt 10):o2451. doi: 10.1107/S1600536809036204

Piperidinium 4-hydroxy-3-methoxycarbonyl-1,2-benzothiazin-2-ide 1,1-dioxide

Muhammad Nadeem Arshad ^a, Muhammad Zia-ur-Rehman ^b, Naveed Ahmed ^c, Islam Ullah Khan ^a,^*

PMCID: PMC2970237 PMID: 21577906

Abstract

In the anion of the title compound, C₅H₁₂N⁺·C₁₀H₈NO₅S⁻, the thiazine ring adopts a distorted half-chair conformation and the enolic H atom is involved in an intramolecular O—H⋯O hydrogen bond, forming a six-membered ring. The anions and cations are connected via N—H⋯N and N—H⋯O interactions.

Related literature

For the synthesis of related molecules, see: Zia-ur-Rehman et al. (2005 ▶, 2006 ▶); Braun (1923 ▶). For the biological activity of 1,2-benzothiazine1,1-dioxides, see: Bihovsky et al. (2004 ▶); Turck et al. (1996 ▶); Zia-ur-Rehman et al. (2009 ▶). For related structures, see: Golič & Leban (1987 ▶).

Experimental

Crystal data

C₅H₁₂N⁺·C₁₀H₈NO₅S⁻
M _r = 340.39
Monoclinic,
a = 12.0423 (5) Å
b = 9.1791 (3) Å
c = 14.5193 (5) Å
β = 90.556 (2)°
V = 1604.85 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 296 K
0.39 × 0.33 × 0.29 mm

Data collection

Bruker KAPPA APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker 2007 ▶) T _min = 0.921, T _max = 0.940
16000 measured reflections
3690 independent reflections
2896 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.103
S = 1.03
3690 reflections
216 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.34 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: PLATON (Spek, 2009 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON.

Supplementary Material

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536809036204/bt5055sup1.cif

e-65-o2451-sup1.cif^{(20KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809036204/bt5055Isup2.hkl

e-65-o2451-Isup2.hkl^{(180.9KB, 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⋯O4	0.82	1.86	2.577 (2)	145
N1—H1N⋯N2ⁱ	0.932 (19)	1.951 (19)	2.881 (2)	175.4 (18)
N1—H2N⋯O2ⁱⁱ	0.87 (2)	1.91 (2)	2.7739 (18)	172.4 (18)

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

Acknowledgments

The authors are grateful to PCSIR Laboratories Complex, Lahore, for the provision of necessary facilities to complete this work.

supplementary crystallographic information

Comment

Owing to their application as non-steroidal anti-inflammatory agents (Turck et al., 1996), considerable attention has been given to synthetic and structural investigations of 1,2-benzothiazine1,1-dioxides and their precursor intermediates (Golič & Leban, 1987). These are known to possess a versatile range of biological activities and have been synthesized continuously since the very first synthesis (Braun, 1923). Among these, Piroxicam (Zia-ur-Rehman et al., 2005), and Meloxicam (Turck et al., 1996) are familiar for their analgesic action and are being used world wide as non-steroidal anti-inflammatory drugs (NSAIDs). Besides, these have also been found to be used for the treatment of rheumatoid arthritis, ankylosing spondylitis, osteoarthrosis and other inflammatory rheumatic and non- rheumatic processes, including onsets and traumatologic lesions. Some of the 3,4-dihydro-1,2-benzothiazine-3-carboxylate 1,1-dioxide α-ketomide and P(2)—P(3) peptide mimetic aldehyde compounds act as potent calpain I inhibitors (Bihovsky et al., 2004) while 1,2-benzothiazin-3-yl-quinazolin-4(3H)-ones possess anti-bacterial properties (Zia-ur-Rehman et al., 2006). As part of a research program synthesizing various bioactive benzothiazines (Zia-ur-Rehman et al., 2005, 2006, 2009), we, herein report the crystal structure of the title compound (Scheme and figure 1). The asymmetric unit contains one piperidinum cation and one 4-hydroxy-3-(methoxycarbonyl)-1,2-benzothiazin-2-ide 1,1-dioxide anion. The piperidinium cation displays a typical chair conformation. The thiazine ring of the anion, involving two double bonds, exhibits a distorted half-chair conformation and the enolic hydrogen on O1 is involved in intramolecular hydrogen bonding giving rise to a six membered hydrogen bond ring (Table 1). Both the ions are linked together through N—H···N and N—H···O interactions. Adjacent asymmetric units are linked through intermolecular N—H···O hydrogen bonds, resulting in zigzag chains lying along the b axis (Figure 2).

Experimental

A mixture of methyl 4-hydroxy-2H-1,2-benzothiazine-3-carboxylate-1,1-dioxide (2.693 g; 10.0 mmoles), piperidine (1.02 g, 12.0 mmoles) and toluene (25.0 ml) was heated to reflux for an hour. Solvent and excess piperdine were removed under vacuum and the resulting solids were dried and crystallized from ethanol. Yield: 78%.