


Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989015019295/tk5394sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S2056989015019295/tk5394Isup2.hkl |
![]() | Chemical Markup Language (CML) file https://doi.org/10.1107/S2056989015019295/tk5394Isup3.cml |
CCDC reference: 1430755
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean
(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
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).
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).
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).
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).
C16H13NOS | Dx = 1.329 Mg m−3 |
Mr = 267.33 | Melting point: 342 K |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 9.1497 (3) Å | Cell parameters from 4082 reflections |
b = 14.7052 (5) Å | θ = 2.2–30.5° |
c = 10.0037 (3) Å | µ = 0.23 mm−1 |
β = 97.051 (1)° | T = 296 K |
V = 1335.80 (7) Å3 | Prism, brown |
Z = 4 | 0.36 × 0.31 × 0.26 mm |
F(000) = 560 |
Bruker X8 APEX diffractometer | 4082 independent reflections |
Radiation source: fine-focus sealed tube | 3071 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
φ and ω scans | θmax = 30.5°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | h = −7→13 |
Tmin = 0.670, Tmax = 0.746 | k = −20→21 |
25334 measured reflections | l = −14→14 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.048 | H-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 reflections | Δρmax = 0.37 e Å−3 |
172 parameters | Δρmin = −0.21 e Å−3 |
C16H13NOS | V = 1335.80 (7) Å3 |
Mr = 267.33 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.1497 (3) Å | µ = 0.23 mm−1 |
b = 14.7052 (5) Å | T = 296 K |
c = 10.0037 (3) Å | 0.36 × 0.31 × 0.26 mm |
β = 97.051 (1)° |
Bruker X8 APEX diffractometer | 4082 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | 3071 reflections with I > 2σ(I) |
Tmin = 0.670, Tmax = 0.746 | Rint = 0.031 |
25334 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.153 | H-atom parameters constrained |
S = 1.12 | Δρmax = 0.37 e Å−3 |
4082 reflections | Δρmin = −0.21 e Å−3 |
172 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.73318 (17) | 0.52736 (10) | 0.43834 (14) | 0.0426 (3) | |
C2 | 0.6952 (2) | 0.48778 (12) | 0.55605 (16) | 0.0513 (4) | |
H2 | 0.6186 | 0.4459 | 0.5516 | 0.062* | |
C3 | 0.7715 (2) | 0.51089 (13) | 0.67964 (16) | 0.0579 (5) | |
H3 | 0.7445 | 0.4862 | 0.7586 | 0.070* | |
C4 | 0.8872 (2) | 0.57054 (13) | 0.68451 (17) | 0.0596 (4) | |
H4 | 0.9383 | 0.5863 | 0.7675 | 0.071* | |
C5 | 0.9292 (2) | 0.60761 (12) | 0.56848 (17) | 0.0549 (4) | |
H5 | 1.0100 | 0.6464 | 0.5737 | 0.066* | |
C6 | 0.85101 (17) | 0.58725 (10) | 0.44272 (14) | 0.0425 (3) | |
C7 | 0.86549 (16) | 0.58789 (10) | 0.19776 (14) | 0.0435 (3) | |
C8 | 0.75763 (16) | 0.51143 (10) | 0.17601 (14) | 0.0408 (3) | |
C9 | 0.9905 (3) | 0.70539 (13) | 0.3367 (2) | 0.0689 (5) | |
H9A | 1.0003 | 0.7272 | 0.4278 | 0.103* | |
H9B | 1.0853 | 0.6874 | 0.3142 | 0.103* | |
H9C | 0.9512 | 0.7528 | 0.2768 | 0.103* | |
C10 | 0.75953 (16) | 0.45936 (11) | 0.06583 (14) | 0.0430 (3) | |
H10 | 0.8336 | 0.4735 | 0.0133 | 0.052* | |
C11 | 0.66396 (17) | 0.38420 (10) | 0.01526 (14) | 0.0432 (3) | |
C12 | 0.7201 (2) | 0.32215 (12) | −0.07117 (18) | 0.0563 (4) | |
H12 | 0.8150 | 0.3299 | −0.0935 | 0.068* | |
C13 | 0.6368 (3) | 0.24967 (15) | −0.1236 (3) | 0.0770 (6) | |
H13 | 0.6763 | 0.2088 | −0.1804 | 0.092* | |
C14 | 0.4954 (3) | 0.23710 (15) | −0.0928 (2) | 0.0744 (6) | |
H14 | 0.4397 | 0.1879 | −0.1283 | 0.089* | |
C15 | 0.4378 (2) | 0.29778 (15) | −0.0094 (2) | 0.0663 (5) | |
H15 | 0.3427 | 0.2893 | 0.0121 | 0.080* | |
C16 | 0.51940 (18) | 0.37157 (13) | 0.04339 (17) | 0.0550 (4) | |
H16 | 0.4778 | 0.4130 | 0.0979 | 0.066* | |
N1 | 0.89082 (15) | 0.62709 (9) | 0.32356 (13) | 0.0466 (3) | |
O1 | 0.92759 (14) | 0.61644 (9) | 0.10488 (12) | 0.0591 (3) | |
S1 | 0.62428 (4) | 0.50183 (3) | 0.28662 (4) | 0.05206 (15) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0506 (8) | 0.0451 (7) | 0.0335 (6) | 0.0048 (6) | 0.0115 (6) | 0.0010 (5) |
C2 | 0.0614 (10) | 0.0554 (9) | 0.0395 (7) | 0.0038 (7) | 0.0162 (7) | 0.0053 (6) |
C3 | 0.0759 (12) | 0.0629 (10) | 0.0359 (8) | 0.0138 (8) | 0.0103 (8) | 0.0093 (7) |
C4 | 0.0735 (11) | 0.0637 (10) | 0.0390 (7) | 0.0134 (9) | −0.0027 (7) | −0.0030 (7) |
C5 | 0.0626 (10) | 0.0528 (9) | 0.0479 (8) | 0.0018 (7) | 0.0014 (7) | −0.0070 (7) |
C6 | 0.0537 (8) | 0.0380 (7) | 0.0367 (7) | 0.0064 (6) | 0.0090 (6) | −0.0005 (5) |
C7 | 0.0451 (7) | 0.0476 (8) | 0.0390 (7) | −0.0009 (6) | 0.0101 (6) | 0.0039 (6) |
C8 | 0.0405 (7) | 0.0504 (8) | 0.0322 (6) | −0.0003 (6) | 0.0079 (5) | 0.0045 (5) |
C9 | 0.0953 (15) | 0.0483 (9) | 0.0663 (11) | −0.0214 (9) | 0.0228 (10) | −0.0069 (8) |
C10 | 0.0425 (7) | 0.0545 (8) | 0.0327 (6) | −0.0003 (6) | 0.0077 (5) | 0.0038 (6) |
C11 | 0.0459 (7) | 0.0500 (8) | 0.0328 (6) | −0.0006 (6) | 0.0019 (5) | 0.0059 (5) |
C12 | 0.0566 (9) | 0.0543 (9) | 0.0589 (10) | −0.0009 (7) | 0.0107 (8) | −0.0052 (7) |
C13 | 0.0818 (14) | 0.0585 (11) | 0.0914 (16) | −0.0055 (10) | 0.0138 (12) | −0.0195 (10) |
C14 | 0.0754 (13) | 0.0584 (11) | 0.0862 (14) | −0.0158 (10) | −0.0033 (11) | −0.0036 (10) |
C15 | 0.0503 (9) | 0.0789 (13) | 0.0677 (11) | −0.0139 (9) | −0.0012 (8) | 0.0097 (10) |
C16 | 0.0465 (8) | 0.0704 (11) | 0.0474 (8) | −0.0025 (7) | 0.0033 (6) | −0.0006 (8) |
N1 | 0.0583 (8) | 0.0404 (6) | 0.0429 (6) | −0.0045 (5) | 0.0130 (5) | 0.0001 (5) |
O1 | 0.0633 (7) | 0.0710 (8) | 0.0461 (6) | −0.0177 (6) | 0.0191 (5) | 0.0037 (5) |
S1 | 0.0473 (2) | 0.0749 (3) | 0.0361 (2) | −0.01066 (18) | 0.01376 (16) | −0.00324 (16) |
C1—C6 | 1.389 (2) | C9—N1 | 1.465 (2) |
C1—C2 | 1.395 (2) | C9—H9A | 0.9600 |
C1—S1 | 1.7510 (15) | C9—H9B | 0.9600 |
C2—C3 | 1.386 (3) | C9—H9C | 0.9600 |
C2—H2 | 0.9300 | C10—C11 | 1.461 (2) |
C3—C4 | 1.371 (3) | C10—H10 | 0.9300 |
C3—H3 | 0.9300 | C11—C12 | 1.398 (2) |
C4—C5 | 1.379 (3) | C11—C16 | 1.398 (2) |
C4—H4 | 0.9300 | C12—C13 | 1.376 (3) |
C5—C6 | 1.401 (2) | C12—H12 | 0.9300 |
C5—H5 | 0.9300 | C13—C14 | 1.379 (3) |
C6—N1 | 1.4154 (19) | C13—H13 | 0.9300 |
C7—O1 | 1.2215 (18) | C14—C15 | 1.371 (3) |
C7—N1 | 1.3777 (19) | C14—H14 | 0.9300 |
C7—C8 | 1.494 (2) | C15—C16 | 1.385 (3) |
C8—C10 | 1.344 (2) | C15—H15 | 0.9300 |
C8—S1 | 1.7505 (15) | C16—H16 | 0.9300 |
C6—C1—C2 | 120.73 (14) | H9A—C9—H9C | 109.5 |
C6—C1—S1 | 121.35 (11) | H9B—C9—H9C | 109.5 |
C2—C1—S1 | 117.89 (13) | C8—C10—C11 | 130.37 (14) |
C3—C2—C1 | 120.00 (17) | C8—C10—H10 | 114.8 |
C3—C2—H2 | 120.0 | C11—C10—H10 | 114.8 |
C1—C2—H2 | 120.0 | C12—C11—C16 | 117.82 (15) |
C4—C3—C2 | 119.42 (16) | C12—C11—C10 | 117.27 (14) |
C4—C3—H3 | 120.3 | C16—C11—C10 | 124.87 (15) |
C2—C3—H3 | 120.3 | C13—C12—C11 | 120.86 (18) |
C3—C4—C5 | 121.10 (16) | C13—C12—H12 | 119.6 |
C3—C4—H4 | 119.5 | C11—C12—H12 | 119.6 |
C5—C4—H4 | 119.5 | C12—C13—C14 | 120.6 (2) |
C4—C5—C6 | 120.48 (17) | C12—C13—H13 | 119.7 |
C4—C5—H5 | 119.8 | C14—C13—H13 | 119.7 |
C6—C5—H5 | 119.8 | C15—C14—C13 | 119.39 (19) |
C1—C6—C5 | 118.21 (14) | C15—C14—H14 | 120.3 |
C1—C6—N1 | 121.00 (13) | C13—C14—H14 | 120.3 |
C5—C6—N1 | 120.79 (15) | C14—C15—C16 | 120.82 (19) |
O1—C7—N1 | 120.60 (14) | C14—C15—H15 | 119.6 |
O1—C7—C8 | 120.56 (14) | C16—C15—H15 | 119.6 |
N1—C7—C8 | 118.81 (12) | C15—C16—C11 | 120.45 (18) |
C10—C8—C7 | 118.25 (13) | C15—C16—H16 | 119.8 |
C10—C8—S1 | 123.55 (12) | C11—C16—H16 | 119.8 |
C7—C8—S1 | 117.89 (11) | C7—N1—C6 | 124.35 (12) |
N1—C9—H9A | 109.5 | C7—N1—C9 | 116.37 (13) |
N1—C9—H9B | 109.5 | C6—N1—C9 | 118.12 (13) |
H9A—C9—H9B | 109.5 | C8—S1—C1 | 99.44 (7) |
N1—C9—H9C | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
C12—H12···O1i | 0.93 | 2.50 | 3.404 (2) | 164 |
Symmetry code: (i) −x+2, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C12—H12···O1i | 0.93 | 2.50 | 3.404 (2) | 164 |
Symmetry code: (i) −x+2, −y+1, −z. |
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.