2-[(E)-1,1-Dioxo-2-(2,4,5-tri­fluoro­benz­yl)-3,4-di­hydro-2H-1,2-benzo­thia­zin-4-yl­idene]acetic acid

Shaojuan Zhu; Shagufta Parveen; Changjin Zhu

doi:10.1107/S1600536814013245

. 2014 Jun 14;70(Pt 7):o775. doi: 10.1107/S1600536814013245

2-[(E)-1,1-Dioxo-2-(2,4,5-trifluorobenzyl)-3,4-dihydro-2H-1,2-benzothiazin-4-ylidene]acetic acid

Shaojuan Zhu ^a, Shagufta Parveen ^a, Changjin Zhu ^a,^*

PMCID: PMC4120568 PMID: 25161563

Abstract

In the asymmetric unit of the title compound, C₁₇H₁₂F₃NO₄S, there are two conformationally similar molecules in which the heterocyclic thiazine ring adopts a half-chair conformation, with the dihedral angle between the two benzene rings being 24.84 (8) and 37.42 (8)°. In the crystal, the molecules form dimers through cyclic carboxylic acid O—H⋯O hydrogen-bonding associations [graph set R ² ₂(8)] and are extended into chains along [101] through weak C—H⋯O_sulfinyl hydrogen bonds [graph set R ² ₂(14)]..

Related literature

For pharmaceutical and biological properties of 1,2-benzothiazines, see: Zia-ur-Rehman et al. (2005 ▶); Lombardino et al. (1971 ▶); Bihovsky et al. (2004 ▶); For synthetic details of the title compound, see: Parveen et al. (2014b ▶). For related structures, see: Yang et al. (2012 ▶); Parveen et al. (2014a ▶). For graph-set analysis, see: Etter et al. 1990 ▶). graphic file with name e-70-0o775-scheme1.jpg

Experimental

Crystal data

C₁₇H₁₂F₃NO₄S
M _r = 383.34
Triclinic,
a = 8.0028 (10) Å
b = 14.249 (2) Å
c = 15.076 (2) Å
α = 104.631 (8)°
β = 99.915 (6)°
γ = 104.237 (6)°
V = 1561.2 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.27 mm⁻¹
T = 153 K
0.31 × 0.26 × 0.18 mm

Data collection

Rigaku AFC10/Saturn724+ CCD-detector diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008 ▶) T _min = 0.932, T _max = 0.964
20894 measured reflections
8293 independent reflections
6954 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.114
S = 1.00
8293 reflections
477 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.43 e Å⁻³

Data collection: CrystalClear (Rigaku, 2008 ▶); cell refinement: CrystalClear (Rigaku, 2008 ▶); data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 1998 ▶); software used to prepare material for publication: CrystalStructure (Rigaku, 2008 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536814013245/zs2301sup1.cif

e-70-0o775-sup1.cif^{(38.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814013245/zs2301Isup2.hkl

e-70-0o775-Isup2.hkl^{(405.6KB, hkl)}

Click here for additional data file.^{(19.5KB, mol)}

Supporting information file. DOI: 10.1107/S1600536814013245/zs2301Isup3.mol

Click here for additional data file.^{(6.3KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814013245/zs2301Isup4.cml

CCDC reference: 1007103

Additional supporting information: 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—H3O⋯O8ⁱ	0.85 (3)	1.86 (3)	2.7063 (17)	172 (3)
O7—H7O⋯O4ⁱⁱ	0.92 (3)	1.73 (3)	2.6473 (17)	177 (2)
C15—H15⋯O6	0.95	2.34	3.267 (2)	165
C32—H32⋯O2	0.95	2.61	3.539 (2)	165

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

Acknowledgments

This work was supported by the National Natural Science Foundation of China (grant No. 21272025), the Research Fund for the Doctoral Program of Higher Education of China (grant No. 20111101110042) and the Science and Technology Commission of Beijing (China) (grant No. Z131100004013003).

supplementary crystallographic information

S1. Comment

1,2-Benzothiazine-1,1-dioxide derivatives are reported as having anti- inflammatory and anti-bacterial activities (Lombardino et al., 1971) while some of its derivatives have been found to be calpain 1 inhibitors (Bihovsky et al., 2004). More recently, its derivatives were reported as aldose reductase inhibitors (Parveen et al., 2014b). Herein, we report the structure of the title derivative, C₁₇H₁₂F₃NO₄S, which is the E isomer of the previously published isomer 2-[(Z)-1,1-dioxo-2-(2,4,5-trifluorobenzyl)-3,4- dihydro-2H-1,2-benzothiazin-4-ylidene]acetic acid (Parveen et al., 2014a).

In the title compound, there are two conformationally similar molecules (A and B) in the asymmetric unit (Fig. 1). The dihedral angles between mean plane of the two benzene rings [(C1—C6) and (C10—C15) in A and (C18–C23) and (C27–C32) in B] are 37.42 (8) and 24.84 (7)°, respectively. These values compare with 43.28 (9)° in the Z isomer (Parveen et al., 2014a). The heterocyclic thiazine ring adopts a half-chair conformation. The acetic acid substituent groups show only minor conformational differences: torsion angles C8—C7—C16—C17 and C7—C16—C17—O3 [169.7 (16) and 174.59 (17)°, respectively] in A campare with C25—C24— C33—C34 and C24—C33—C34—O7 [-179.25 (16) and -168.18 (17), respectively] in B.

In the crystal the molecules form centrosymmetric dimers through intermolecular cyclic carboxylic acid O—H···O hydrogen-bonding associations [graph set R²₂(8) (Etter et al., 1990)]. These dimers form one-dimensional chains which extend along [101] (Fig. 2), through weak duplex C—H···O_sulfinyl hydrogen-bonding associations (Table 1) [graph set R²₂(14)].

S2. Experimental

A mixture of E-2-[2-(2,4,5-Trifluorobenzyl)-1,1-dioxido-2H-1,2-benzothiazin- 4(3H)-ylidene]acetic acid methyl ester (0.5 mmol), 10 M hydrochloric acid (8 mL), and 1,4-dioxane (5 mL) was refluxed at 60°C for 2 h. The crude product obtained was washed with cold water (3 times, 10 mL) and purified by flash chromatography with CH₂Cl₂ and methanol (100:1) as eluent, which afforded a white solid product on concentration under vacuum. Recrystallization from ethanol gave crystals of the title compound suitable for the X-ray analysis (yield = 60%).