Crystal structure of (Z)-ethyl 2-{5-[(2-benzyl­idene-3-oxo-2,3-di­hydro­benzo[b][1,4]thia­zin-4-yl)meth­yl]-1H-1,2,3-triazol-1-yl}acetate

M Ellouz; N K Sebbar; E M Essassi; Y Ouzidan; J T Mague

doi:10.1107/S2056989015022987

. 2015 Dec 6;71(Pt 12):o1022–o1023. doi: 10.1107/S2056989015022987

Crystal structure of (Z)-ethyl 2-{5-[(2-benzylidene-3-oxo-2,3-dihydrobenzo[b][1,4]thiazin-4-yl)methyl]-1H-1,2,3-triazol-1-yl}acetate

M Ellouz ^a, N K Sebbar ^a, E M Essassi ^a, Y Ouzidan ^b,^‡, J T Mague ^c,^*

PMCID: PMC4719958 PMID: 26870477

Abstract

The title compound, C₂₂H₂₀N₄O₃S, features two fused six-membered rings linked to a 1,2,3-triazole ring which is attached to an ethyl acetate group. The heterocycle in the benzothiazine residue has an envelope conformation with the S atom being the flap. The conformation of the ethyl acetate side chain, which is directed to the same side of the molecule as the C₆ ring of the fused-ring system, may be partially established by a pair of weak intramolecular C—H⋯O(carbonyl) interactions. The three-dimensional packing is aided by intermolecular C—H⋯O and C—H⋯N interactions.

Keywords: crystal structure, benzothiazine, triazole, conformation

Related literature

For the biological activity of 1,4-benzothiazine derivatives, see: Goyal et al. (2013 ▸); Gupta et al. (2011 ▸); Gautam et al. (2013 ▸); Deshmukh & Mulik (2004 ▸); Kumar et al. (2010 ▸); Hans et al. (2008 ▸); Gao et al. (2005 ▸); Bakavoli et al. (2007 ▸). For applications of 1,4-benzothiazine derivatives, see: Podsiadły et al. (2009 ▸); Hong et al. (2008 ▸). For structures of 1,4-benzothiazine derivatives, see: Sebbar et al. (2014 ▸). graphic file with name e-71-o1022-scheme1.jpg

Experimental

Crystal data

C₂₂H₂₀N₄O₃S
M _r = 420.48
Monoclinic,
a = 9.9767 (6) Å
b = 8.7342 (5) Å
c = 23.1027 (14) Å
β = 94.508 (1)°
V = 2006.9 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.19 mm⁻¹
T = 150 K
0.32 × 0.28 × 0.25 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2015 ▸) T _min = 0.86, T _max = 0.95
37542 measured reflections
5341 independent reflections
4380 reflections with I > 2σ(I)
R _int = 0.039

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.117
S = 1.04
5341 reflections
272 parameters
H-atom parameters constrained
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Data collection: APEX2 (Bruker, 2015 ▸); cell refinement: SAINT (Bruker, 2015 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXT (Sheldrick, 2015a ▸); program(s) used to refine structure: SHELXL (Sheldrick, 2015b ▸); molecular graphics: DIAMOND (Brandenburg & Putz, 2012 ▸); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▸).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015022987/tk5410sup1.cif

e-71-o1022-sup1.cif^{(1.1MB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015022987/tk5410Isup2.hkl

e-71-o1022-Isup2.hkl^{(425KB, hkl)}

Click here for additional data file.^{(8KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015022987/tk5410Isup3.cml

Click here for additional data file.^{(1.2MB, tif)}

. DOI: 10.1107/S2056989015022987/tk5410fig1.tif

The title molecule showing the labeling scheme and 50% probability ellipsoids. Intramolecular C—H⋯O interactions are shown by dotted lines.

Click here for additional data file.^{(1.2MB, tif)}

b . DOI: 10.1107/S2056989015022987/tk5410fig2.tif

Packing viewed down the b axis. Intermolecular C—H⋯O interactions are shown by dotted lines.

CCDC reference: 1439697

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
C2—H2⋯O2	0.95	2.55	3.4726 (18)	163
C16—H16B⋯O2	0.99	2.58	3.2981 (19)	129
C19—H19B⋯O1ⁱ	0.99	2.39	3.2547 (18)	146
C21—H21A⋯N4ⁱⁱ	0.99	2.57	3.526 (2)	162
C22—H22B⋯O2ⁱⁱⁱ	0.98	2.59	3.521 (2)	159

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

Acknowledgments

JTM thanks Tulane University for support of the Tulane Crystallography Laboratory.

supplementary crystallographic information

S1. Comment

4H-1,4-Benzothiazines possess a wide spectrum of biological and pharmacological activities due to the presence of a fold along the nitrogen···sulfur axis which is considered to be one of the structural features responsible for their activities (Gupta et al., 2011). During the past two decades, we have found a growing interest in 1,4-benzothiazines. In fact, the 1,4-benzothiazines are the best known to possess biologically diverse activities (Goyal et al., 2013) such as antimicrobial, (Gautam et al., 2013) antifungal (Hans et al., 2008), antioxidant agents (Kumar et al., 2010), inhibitors of beta-ribosidases (Gao et al., 2005), potential vasodilators (Deshmukh et al., 2004) and as potent lipoxygenase inhibitors (Bakavoli et al., 2007). 1,4- Benzothiazines are the basis for novel dyes (Podsiadły et al., 2009) and behave as semiconductors (Hong et al., 2008).

As a continuation of our research devoted to the development of substituted 1,4-benzothiazine derivatives (Sebbar et al., 2014), we report the synthesis of a new 1,4-benzothiazine derivative which is built from two fused six-membered rings linked to a 1,2,3-triazole ring which is attached to an ethylacetate group.

The conformation of the side chain may be partially established by the weak, intramolecular C16—H16B···O2 and C2—H2···O2 interactions (Fig. 1 and Table 1). The six-membered heterocyclic ring has puckering parameters Q = 0.5154 (11) Å, θ = 108.31 (14)° and φ = 162.81 (17)°. The pendant phenyl ring (C10–C15) makes a dihedral angle of 53.26 (5)° with the ring C1–C6 while the dihedral angle between the ring C1–C6 and the triazolyl ring is 76.31 (5)°. The packing is aided by intermolecular C—H···O and C—H···N interactions (Figs 2 and Table 1).

S2. Experimental

To a solution of 2-benzylidene-4-(prop-2-yn-1-yl)-2H-1,4-benzothiazin-3-one (0.2 g, 0.68 mmol) in ethanol (15 ml) was added ethyl azido-acetate (0.13 g, 1.03 mmol). The mixture was stirred under reflux for 24 h. After completion of the reaction (monitored by TLC), the solution was concentrated and the residue was purified by column chromatography on silica gel by using a mixture (hexane/ethyl acetate 9/1). Crystals were obtained when the solvent was allowed to evaporate. The solid product was purified by recrystallization from ethanol to afford yellow crystals in 14% yield.