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In the title compound, C16H13NOS, the 1,4-thia­zine ring displays a screw-boat conformation. The conformation about the ethene bond [1.344 (2) Å] is Z. The plane of the fused benzene ring makes a dihedral angle of 58.95 (9)° with the pendent phenyl ring, indicating a twisted conformation in the mol­ecule. In the crystal, mol­ecules are linked by pairs of C—H...O hydrogen bonds, forming inversion dimers.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989015019295/tk5394sup1.cif
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2056989015019295/tk5394Isup2.hkl
Contains datablock I

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2056989015019295/tk5394Isup3.cml
Supplementary material

CCDC reference: 1430755

Key indicators

  • Single-crystal X-ray study
  • T = 296 K
  • Mean [sigma](C-C) = 0.002 Å
  • R factor = 0.048
  • wR factor = 0.153
  • Data-to-parameter ratio = 23.7

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT412_ALERT_2_C Short Intra XH3 .. XHn H5 .. H9A .. 1.88 Ang. PLAT905_ALERT_3_C Negative K value in the Analysis of Variance ... -0.937 Report
Alert level G PLAT380_ALERT_4_G Incorrectly? Oriented X(sp2)-Methyl Moiety ..... C9 Check PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L= 0.600 5 Note PLAT954_ALERT_1_G Reported (CIF) and Actual (FCF) Kmax Differ by . 1 Units
0 ALERT level A = Most likely a serious problem - resolve or explain 0 ALERT level B = A potentially serious problem, consider carefully 2 ALERT level C = Check. Ensure it is not caused by an omission or oversight 3 ALERT level G = General information/check it is not something unexpected 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

Over the years, 4H-1,4-benzothiazines have constituted an important class of heterocycles which, even when part of a complex molecule, possess a wide spectrum of biological activities (Schiaffella et al., 2006; Gupta et al., 2009; Armenise et al., 2000). Due to the presence of a fold along the nitrogen—sulfur axis, the biological activity of some 1,4-benzothiazines is similar to that of phenothiazines, featuring the same structural specificity (Bansode et al., 2009; Dixit et al., 2009; Dixit et al., 2008; Thomas et al., 2003). Generally, benzothiazine and derivatives have found widespread application as analgesic (Warren et al., 1987), antibacterial (Armenise et al., 2012; Sabatini et al., 2008), anticancer (Jacquot et al., 2001), anticonvulsant (Kalluraya et al., 2005) and anthelmintic (Munirajasekar et al., 2011) agents. As a continuation of our research work devoted to the development of N-substituted benzothiazine and evaluating their potential pharmacological activities, we have checked the action of iodomethane towards (E)-2-benzylidene-2H-benzo[b][1,4]thiazin-3(4H)-one under phase-transfer catalysis conditions using tetra n-butylammonium bromide (TBAB) as catalyst and potassium carbonate as base (Sebbar et al., 2014a, Sebbar et al., 2014b; Zerzouf et al., 2001). This led to the characterization of the title compound, Scheme 1.

The molecule of the title compound is build up from two fused six-membered rings linked as shown in Fig.1. The dihedral angle between the (C1 to C6) and (C11 to C16) benzene rings is 58.95 (9)°.

In the crystal, the molecules are linked together by a hydrogen bond (C12–H12···O1) in a way to build a dimer, as shown in Fig. 2 and Table 1.

Related literature top

For background to the pharmacological activity and potential applications of benzothiazines, see: Schiaffella et al. (2006); Gupta et al. (2009); Armenise et al. (2000); Bansode et al. (2009); Dixit et al. (2009); Dixit et al. (2008); Thomas et al. (2003). For medicinal applications; see: Warren et al. (1987); Armenise et al. (2012); Sabatini et al. (2008); Jacquot et al. (2001); Kalluraya et al. (2005); Munirajasekar et al. (2011). For similar compounds, see: Sebbar et al. (2014a,b); Zerzouf et al. (2001).

Experimental top

To a solution of 2-(benzylidene)-3,4-dihydro-2H-1,4-benzothiazin-3-one (0.5 g, 2 mmol), potassium carbonate (0.55 g, 4 mmol) and tetra n-butyl ammonium bromide (0.064 g, 0.2 mmol) in DMF (15 ml) was added iodomethane (0.25 ml, 4 mmol). Stirring was continued at room temperature for 12 h. The mixture was filtered and the solvent removed. The residue was extracted with water. The organic compound was chromatographed on a column of silica gel with ethyl acetate-hexane (9/1) as eluent. Brown crystals were isolated when the solvent was allowed to evaporate (yield: 53%; m.p. = 342 K).

Refinement top

The H atoms were located in a difference map and treated as riding with C—H = 0.93 Å (aromatic) and C—H = 0.96 Å (methyl), and with Uiso(H) = 1.2 Ueq (aromatic) and Uiso(H) = 1.5 Ueq (methyl).

Structure description top

Over the years, 4H-1,4-benzothiazines have constituted an important class of heterocycles which, even when part of a complex molecule, possess a wide spectrum of biological activities (Schiaffella et al., 2006; Gupta et al., 2009; Armenise et al., 2000). Due to the presence of a fold along the nitrogen—sulfur axis, the biological activity of some 1,4-benzothiazines is similar to that of phenothiazines, featuring the same structural specificity (Bansode et al., 2009; Dixit et al., 2009; Dixit et al., 2008; Thomas et al., 2003). Generally, benzothiazine and derivatives have found widespread application as analgesic (Warren et al., 1987), antibacterial (Armenise et al., 2012; Sabatini et al., 2008), anticancer (Jacquot et al., 2001), anticonvulsant (Kalluraya et al., 2005) and anthelmintic (Munirajasekar et al., 2011) agents. As a continuation of our research work devoted to the development of N-substituted benzothiazine and evaluating their potential pharmacological activities, we have checked the action of iodomethane towards (E)-2-benzylidene-2H-benzo[b][1,4]thiazin-3(4H)-one under phase-transfer catalysis conditions using tetra n-butylammonium bromide (TBAB) as catalyst and potassium carbonate as base (Sebbar et al., 2014a, Sebbar et al., 2014b; Zerzouf et al., 2001). This led to the characterization of the title compound, Scheme 1.

The molecule of the title compound is build up from two fused six-membered rings linked as shown in Fig.1. The dihedral angle between the (C1 to C6) and (C11 to C16) benzene rings is 58.95 (9)°.

In the crystal, the molecules are linked together by a hydrogen bond (C12–H12···O1) in a way to build a dimer, as shown in Fig. 2 and Table 1.

For background to the pharmacological activity and potential applications of benzothiazines, see: Schiaffella et al. (2006); Gupta et al. (2009); Armenise et al. (2000); Bansode et al. (2009); Dixit et al. (2009); Dixit et al. (2008); Thomas et al. (2003). For medicinal applications; see: Warren et al. (1987); Armenise et al. (2012); Sabatini et al. (2008); Jacquot et al. (2001); Kalluraya et al. (2005); Munirajasekar et al. (2011). For similar compounds, see: Sebbar et al. (2014a,b); Zerzouf et al. (2001).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT-Plus (Bruker, 2009); data reduction: SAINT-Plus (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound with the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as small circles.
[Figure 2] Fig. 2. Supramolecular association in the title compound, showing inversion dimers of molecules linked through C12—H12···O1 hydrogen bond (dashed lines).
(Z)-2-Benzylidene-4-methyl-2H-benzo[b][1,4]thiazin-3(4H)-one top
Crystal data top
C16H13NOSDx = 1.329 Mg m3
Mr = 267.33Melting point: 342 K
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 9.1497 (3) ÅCell parameters from 4082 reflections
b = 14.7052 (5) Åθ = 2.2–30.5°
c = 10.0037 (3) ŵ = 0.23 mm1
β = 97.051 (1)°T = 296 K
V = 1335.80 (7) Å3Prism, brown
Z = 40.36 × 0.31 × 0.26 mm
F(000) = 560
Data collection top
Bruker X8 APEX
diffractometer
4082 independent reflections
Radiation source: fine-focus sealed tube3071 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.031
φ and ω scansθmax = 30.5°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Bruker, 2009)
h = 713
Tmin = 0.670, Tmax = 0.746k = 2021
25334 measured reflectionsl = 1414
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.048H-atom parameters constrained
wR(F2) = 0.153 w = 1/[σ2(Fo2) + (0.0757P)2 + 0.2379P]
where P = (Fo2 + 2Fc2)/3
S = 1.12(Δ/σ)max < 0.001
4082 reflectionsΔρmax = 0.37 e Å3
172 parametersΔρmin = 0.21 e Å3
Crystal data top
C16H13NOSV = 1335.80 (7) Å3
Mr = 267.33Z = 4
Monoclinic, P21/cMo Kα radiation
a = 9.1497 (3) ŵ = 0.23 mm1
b = 14.7052 (5) ÅT = 296 K
c = 10.0037 (3) Å0.36 × 0.31 × 0.26 mm
β = 97.051 (1)°
Data collection top
Bruker X8 APEX
diffractometer
4082 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2009)
3071 reflections with I > 2σ(I)
Tmin = 0.670, Tmax = 0.746Rint = 0.031
25334 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0480 restraints
wR(F2) = 0.153H-atom parameters constrained
S = 1.12Δρmax = 0.37 e Å3
4082 reflectionsΔρmin = 0.21 e Å3
172 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.73318 (17)0.52736 (10)0.43834 (14)0.0426 (3)
C20.6952 (2)0.48778 (12)0.55605 (16)0.0513 (4)
H20.61860.44590.55160.062*
C30.7715 (2)0.51089 (13)0.67964 (16)0.0579 (5)
H30.74450.48620.75860.070*
C40.8872 (2)0.57054 (13)0.68451 (17)0.0596 (4)
H40.93830.58630.76750.071*
C50.9292 (2)0.60761 (12)0.56848 (17)0.0549 (4)
H51.01000.64640.57370.066*
C60.85101 (17)0.58725 (10)0.44272 (14)0.0425 (3)
C70.86549 (16)0.58789 (10)0.19776 (14)0.0435 (3)
C80.75763 (16)0.51143 (10)0.17601 (14)0.0408 (3)
C90.9905 (3)0.70539 (13)0.3367 (2)0.0689 (5)
H9A1.00030.72720.42780.103*
H9B1.08530.68740.31420.103*
H9C0.95120.75280.27680.103*
C100.75953 (16)0.45936 (11)0.06583 (14)0.0430 (3)
H100.83360.47350.01330.052*
C110.66396 (17)0.38420 (10)0.01526 (14)0.0432 (3)
C120.7201 (2)0.32215 (12)0.07117 (18)0.0563 (4)
H120.81500.32990.09350.068*
C130.6368 (3)0.24967 (15)0.1236 (3)0.0770 (6)
H130.67630.20880.18040.092*
C140.4954 (3)0.23710 (15)0.0928 (2)0.0744 (6)
H140.43970.18790.12830.089*
C150.4378 (2)0.29778 (15)0.0094 (2)0.0663 (5)
H150.34270.28930.01210.080*
C160.51940 (18)0.37157 (13)0.04339 (17)0.0550 (4)
H160.47780.41300.09790.066*
N10.89082 (15)0.62709 (9)0.32356 (13)0.0466 (3)
O10.92759 (14)0.61644 (9)0.10488 (12)0.0591 (3)
S10.62428 (4)0.50183 (3)0.28662 (4)0.05206 (15)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0506 (8)0.0451 (7)0.0335 (6)0.0048 (6)0.0115 (6)0.0010 (5)
C20.0614 (10)0.0554 (9)0.0395 (7)0.0038 (7)0.0162 (7)0.0053 (6)
C30.0759 (12)0.0629 (10)0.0359 (8)0.0138 (8)0.0103 (8)0.0093 (7)
C40.0735 (11)0.0637 (10)0.0390 (7)0.0134 (9)0.0027 (7)0.0030 (7)
C50.0626 (10)0.0528 (9)0.0479 (8)0.0018 (7)0.0014 (7)0.0070 (7)
C60.0537 (8)0.0380 (7)0.0367 (7)0.0064 (6)0.0090 (6)0.0005 (5)
C70.0451 (7)0.0476 (8)0.0390 (7)0.0009 (6)0.0101 (6)0.0039 (6)
C80.0405 (7)0.0504 (8)0.0322 (6)0.0003 (6)0.0079 (5)0.0045 (5)
C90.0953 (15)0.0483 (9)0.0663 (11)0.0214 (9)0.0228 (10)0.0069 (8)
C100.0425 (7)0.0545 (8)0.0327 (6)0.0003 (6)0.0077 (5)0.0038 (6)
C110.0459 (7)0.0500 (8)0.0328 (6)0.0006 (6)0.0019 (5)0.0059 (5)
C120.0566 (9)0.0543 (9)0.0589 (10)0.0009 (7)0.0107 (8)0.0052 (7)
C130.0818 (14)0.0585 (11)0.0914 (16)0.0055 (10)0.0138 (12)0.0195 (10)
C140.0754 (13)0.0584 (11)0.0862 (14)0.0158 (10)0.0033 (11)0.0036 (10)
C150.0503 (9)0.0789 (13)0.0677 (11)0.0139 (9)0.0012 (8)0.0097 (10)
C160.0465 (8)0.0704 (11)0.0474 (8)0.0025 (7)0.0033 (6)0.0006 (8)
N10.0583 (8)0.0404 (6)0.0429 (6)0.0045 (5)0.0130 (5)0.0001 (5)
O10.0633 (7)0.0710 (8)0.0461 (6)0.0177 (6)0.0191 (5)0.0037 (5)
S10.0473 (2)0.0749 (3)0.0361 (2)0.01066 (18)0.01376 (16)0.00324 (16)
Geometric parameters (Å, º) top
C1—C61.389 (2)C9—N11.465 (2)
C1—C21.395 (2)C9—H9A0.9600
C1—S11.7510 (15)C9—H9B0.9600
C2—C31.386 (3)C9—H9C0.9600
C2—H20.9300C10—C111.461 (2)
C3—C41.371 (3)C10—H100.9300
C3—H30.9300C11—C121.398 (2)
C4—C51.379 (3)C11—C161.398 (2)
C4—H40.9300C12—C131.376 (3)
C5—C61.401 (2)C12—H120.9300
C5—H50.9300C13—C141.379 (3)
C6—N11.4154 (19)C13—H130.9300
C7—O11.2215 (18)C14—C151.371 (3)
C7—N11.3777 (19)C14—H140.9300
C7—C81.494 (2)C15—C161.385 (3)
C8—C101.344 (2)C15—H150.9300
C8—S11.7505 (15)C16—H160.9300
C6—C1—C2120.73 (14)H9A—C9—H9C109.5
C6—C1—S1121.35 (11)H9B—C9—H9C109.5
C2—C1—S1117.89 (13)C8—C10—C11130.37 (14)
C3—C2—C1120.00 (17)C8—C10—H10114.8
C3—C2—H2120.0C11—C10—H10114.8
C1—C2—H2120.0C12—C11—C16117.82 (15)
C4—C3—C2119.42 (16)C12—C11—C10117.27 (14)
C4—C3—H3120.3C16—C11—C10124.87 (15)
C2—C3—H3120.3C13—C12—C11120.86 (18)
C3—C4—C5121.10 (16)C13—C12—H12119.6
C3—C4—H4119.5C11—C12—H12119.6
C5—C4—H4119.5C12—C13—C14120.6 (2)
C4—C5—C6120.48 (17)C12—C13—H13119.7
C4—C5—H5119.8C14—C13—H13119.7
C6—C5—H5119.8C15—C14—C13119.39 (19)
C1—C6—C5118.21 (14)C15—C14—H14120.3
C1—C6—N1121.00 (13)C13—C14—H14120.3
C5—C6—N1120.79 (15)C14—C15—C16120.82 (19)
O1—C7—N1120.60 (14)C14—C15—H15119.6
O1—C7—C8120.56 (14)C16—C15—H15119.6
N1—C7—C8118.81 (12)C15—C16—C11120.45 (18)
C10—C8—C7118.25 (13)C15—C16—H16119.8
C10—C8—S1123.55 (12)C11—C16—H16119.8
C7—C8—S1117.89 (11)C7—N1—C6124.35 (12)
N1—C9—H9A109.5C7—N1—C9116.37 (13)
N1—C9—H9B109.5C6—N1—C9118.12 (13)
H9A—C9—H9B109.5C8—S1—C199.44 (7)
N1—C9—H9C109.5
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C12—H12···O1i0.932.503.404 (2)164
Symmetry code: (i) x+2, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C12—H12···O1i0.932.503.404 (2)164
Symmetry code: (i) x+2, y+1, z.
 

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