2,3-Dihydro-1λ⁶,2-benzothia­zine-1,1,4-trione

Abstract

In the title compound, C₈H₇NO₃S, the benzene ring is oriented at a dihedral angle of 69.25 (7)° to the S and O atoms of the sulfonyl group. The heterocyclic ring approximates to an envelope, with the N atom in the flap position. In the crystal, mol­ecules are linked by N—H⋯O_c (c = carbon­yl) hydrogen bonds, forming C(5) chains along [001]. Two R ₂ ²(10) loops arise from pairs of C—H⋯O hydrogen bonds and a weak aromatic π–π stacking inter­action [centroid–centorid separation = 3.8404 (11) Å] also occurs.

Related literature  

For chemical background and related structures, see: Siddiqui et al. (2007 ▶, 2008 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental  

Crystal data  

• C₈H₇NO₃S

• M _r = 197.21

• Monoclinic,

• a = 8.4950 (4) Å

• b = 13.7560 (5) Å

• c = 7.6677 (3) Å

• β = 113.214 (1)°

• V = 823.48 (6) ų

• Z = 4

• Mo Kα radiation

• μ = 0.36 mm⁻¹

• T = 296 K

• 0.35 × 0.15 × 0.12 mm

Data collection  

• Bruker Kappa APEXII CCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.915, T _max = 0.938

• 7644 measured reflections

• 2017 independent reflections

• 1692 reflections with I > 2σ(I)

• R _int = 0.022

Refinement  

• R[F ² > 2σ(F ²)] = 0.036

• wR(F ²) = 0.098

• S = 1.04

• 2017 reflections

• 121 parameters

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.33 e Å⁻³

• Δρ_min = −0.37 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; 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, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812013827/hb6713Isup3.cml

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
N1—H1⋯O3i	0.80 (2)	2.34 (2)	3.028 (2)	144 (2)
C2—H2⋯O2ii	0.93	2.58	3.443 (2)	154
C8—H8A⋯O2iii	0.97	2.48	3.273 (2)	139

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

supplementary crystallographic information

Comment

The title compound (I), (Fig. 1) has been synthesized as a pre-cursor. The crystal structures of 2-methyl-2H-1,2-benzothiazin-4(3H)-one 1,1-dioxide (Siddiqui et al., 2007) has been published which is related to (I).

The dihedral angle between the benzene ring and S1/O1/O2 is 69.25 (7)°. The heterocyclic ring C (C1/C6—C8/N1/S1) is twisted with puckering parameters (Cremer & Pople, 1975) Q = 0.5149 (15) Å, θ = 62.25 (19)° and π = 43.7 (2)°. The molecules are linked in the form of C(5) chains (Bernstein et al., 1995) along the c-axis due to H-bondings between amide and carbonyl O-atoms (Table 1, Fig. 2). The neighbouring polyneric chains are interlinked due to C—H···O bonds with two R₂²(10) ring motifs (Table 1, Fig. 2), where CH are of benzene and methylene groups and the same O-atom is of sulfonyl group. There exist π–π interaction between the centroids of the benzene rings at a distance of 3.8404 (11)°.

Experimental

A mixture of (0.5 g, 1.96 mmol) 4-hydroxy-3-carbomethoxy-2H-1,2- benzothiazine 1,1-dioxide (Siddiqui et al., 2008) and anhydrous lithium iodide (1.3 g, 9.79 mmol) was subjected to reflux in dimethyl sulphoxide (15 ml) for five h. The dark brown reaction mixture was then poured into crushed ice (100 g). The formed dark yellow precipitates were filtered, washed with cold water (3×25 ml) and dried to get (0.36 g, 1.8 mmol, 92%) of the crude product. Recrystallization of the crude product in ethyl acetate yielded light yellow needles of (I) (m.p. 415–417 K).

IR (KBr) (v_max, cm^-1): 3269 (NH), 3078 (Ar. CH), 1683 (C=O), 1577 (NH, def.), 1419 (CH, def.) 1330, 1176 (SO₂).

Refinement

The coordinates of H-atom of amide were refined. The H-atoms of aryl and methylene groups were positioned geometrically at C—H = 0.93 and C—H = 0.97 Å, respectively and included in the refinement as riding with U_iso(H) = xU_eq(C, N), where x = 1.2 for all H atoms.

Figures

Fig. 1.

View of the title compound with displacement ellipsoids drawn at the 50% probability level.

Fig. 2.

Partial packing diagram for (I) showing C(5) chains extending along [001]. The chains are interlinked with R22(10) rings due to C—H···O bondings. The H-atoms not involved in H-bondings are omitted for clarity.

Crystal data

C8H7NO3S	F(000) = 408
Mr = 197.21	Dx = 1.591 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1692 reflections
a = 8.4950 (4) Å	θ = 2.6–28.3°
b = 13.7560 (5) Å	µ = 0.36 mm−1
c = 7.6677 (3) Å	T = 296 K
β = 113.214 (1)°	Needle, light yellow
V = 823.48 (6) Å3	0.35 × 0.15 × 0.12 mm
Z = 4

Data collection

Bruker Kappa APEXII CCD diffractometer	2017 independent reflections
Radiation source: fine-focus sealed tube	1692 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
Detector resolution: 7.50 pixels mm-1	θmax = 28.3°, θmin = 2.6°
ω scans	h = −11→8
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −16→18
Tmin = 0.915, Tmax = 0.938	l = −10→10
7644 measured reflections

Refinement

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.098	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0455P)2 + 0.3408P] where P = (Fo2 + 2Fc2)/3
2017 reflections	(Δ/σ)max < 0.001
121 parameters	Δρmax = 0.33 e Å−3
0 restraints	Δρmin = −0.37 e Å−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	0.28018 (5)	0.04479 (3)	0.18815 (6)	0.0352 (2)
O1	0.21934 (19)	−0.00868 (10)	0.3084 (2)	0.0539 (5)
O2	0.25497 (18)	0.00747 (10)	0.00536 (19)	0.0499 (5)
O3	0.55335 (18)	0.29145 (11)	0.1183 (2)	0.0532 (5)
N1	0.4843 (2)	0.06118 (11)	0.3034 (2)	0.0405 (5)
C1	0.1985 (2)	0.16427 (11)	0.1625 (2)	0.0297 (4)
C2	0.0353 (2)	0.18011 (14)	0.1537 (3)	0.0392 (5)
C3	−0.0234 (2)	0.27484 (15)	0.1446 (3)	0.0447 (6)
C4	0.0788 (2)	0.35176 (14)	0.1427 (3)	0.0430 (6)
C5	0.2406 (2)	0.33587 (13)	0.1476 (3)	0.0363 (5)
C6	0.30357 (19)	0.24184 (11)	0.1576 (2)	0.0285 (4)
C7	0.4782 (2)	0.22672 (12)	0.1609 (2)	0.0331 (5)
C8	0.5621 (2)	0.12808 (13)	0.2121 (3)	0.0429 (6)
H1	0.502 (3)	0.0766 (17)	0.410 (3)	0.0486*
H2	−0.03448	0.12804	0.15398	0.0471*
H3	−0.13293	0.28633	0.13970	0.0537*
H4	0.03854	0.41499	0.13799	0.0516*
H5	0.30824	0.38842	0.14422	0.0436*
H8A	0.56037	0.09765	0.09725	0.0514*
H8B	0.68115	0.13745	0.29619	0.0514*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
S1	0.0387 (3)	0.0236 (2)	0.0436 (3)	−0.0023 (2)	0.0165 (2)	−0.0012 (2)
O1	0.0633 (10)	0.0355 (7)	0.0697 (10)	−0.0056 (6)	0.0335 (8)	0.0110 (6)
O2	0.0576 (9)	0.0383 (7)	0.0513 (8)	−0.0023 (6)	0.0188 (7)	−0.0148 (6)
O3	0.0408 (8)	0.0479 (8)	0.0783 (10)	−0.0039 (6)	0.0314 (7)	0.0131 (7)
N1	0.0384 (8)	0.0292 (8)	0.0486 (8)	0.0044 (6)	0.0116 (7)	0.0025 (6)
C1	0.0308 (8)	0.0278 (8)	0.0307 (7)	0.0003 (6)	0.0123 (6)	−0.0008 (6)
C2	0.0305 (9)	0.0446 (10)	0.0442 (9)	−0.0037 (7)	0.0164 (7)	0.0001 (8)
C3	0.0320 (9)	0.0579 (12)	0.0475 (10)	0.0120 (8)	0.0192 (8)	0.0034 (9)
C4	0.0462 (11)	0.0384 (10)	0.0452 (10)	0.0154 (8)	0.0189 (8)	0.0017 (8)
C5	0.0425 (10)	0.0273 (8)	0.0409 (9)	0.0022 (7)	0.0184 (7)	0.0013 (7)
C6	0.0295 (8)	0.0273 (8)	0.0299 (7)	0.0012 (6)	0.0129 (6)	0.0006 (6)
C7	0.0309 (8)	0.0327 (9)	0.0372 (8)	−0.0018 (7)	0.0152 (7)	−0.0016 (7)
C8	0.0321 (9)	0.0371 (10)	0.0625 (12)	0.0031 (7)	0.0219 (8)	−0.0036 (8)

Geometric parameters (Å, º)

S1—O1	1.4262 (16)	C4—C5	1.378 (3)
S1—O2	1.4273 (14)	C5—C6	1.390 (2)
S1—N1	1.6219 (18)	C6—C7	1.488 (2)
S1—C1	1.7646 (16)	C7—C8	1.511 (2)
O3—C7	1.213 (2)	C2—H2	0.9300
N1—C8	1.462 (3)	C3—H3	0.9300
N1—H1	0.80 (2)	C4—H4	0.9300
C1—C2	1.379 (3)	C5—H5	0.9300
C1—C6	1.401 (2)	C8—H8A	0.9700
C2—C3	1.387 (3)	C8—H8B	0.9700
C3—C4	1.372 (3)
O1—S1—O2	119.80 (9)	C1—C6—C7	122.30 (14)
O1—S1—N1	107.55 (9)	O3—C7—C6	121.31 (16)
O1—S1—C1	109.00 (9)	O3—C7—C8	119.00 (17)
O2—S1—N1	107.42 (9)	C6—C7—C8	119.66 (15)
O2—S1—C1	108.99 (8)	N1—C8—C7	115.70 (16)
N1—S1—C1	102.72 (8)	C1—C2—H2	121.00
S1—N1—C8	114.49 (12)	C3—C2—H2	120.00
C8—N1—H1	112.6 (18)	C2—C3—H3	120.00
S1—N1—H1	108.9 (19)	C4—C3—H3	120.00
C2—C1—C6	121.15 (15)	C3—C4—H4	120.00
S1—C1—C6	119.06 (13)	C5—C4—H4	120.00
S1—C1—C2	119.76 (13)	C4—C5—H5	120.00
C1—C2—C3	119.05 (17)	C6—C5—H5	120.00
C2—C3—C4	120.56 (18)	N1—C8—H8A	108.00
C3—C4—C5	120.39 (18)	N1—C8—H8B	108.00
C4—C5—C6	120.48 (17)	C7—C8—H8A	108.00
C5—C6—C7	119.36 (15)	C7—C8—H8B	108.00
C1—C6—C5	118.34 (16)	H8A—C8—H8B	107.00
O1—S1—N1—C8	−170.75 (13)	C2—C1—C6—C7	−178.08 (15)
O2—S1—N1—C8	59.04 (14)	S1—C1—C6—C5	−176.60 (13)
C1—S1—N1—C8	−55.82 (14)	C1—C2—C3—C4	0.6 (3)
O1—S1—C1—C2	−36.22 (16)	C2—C3—C4—C5	0.8 (3)
O2—S1—C1—C2	96.19 (16)	C3—C4—C5—C6	−1.0 (3)
N1—S1—C1—C2	−150.09 (14)	C4—C5—C6—C1	0.0 (3)
O1—S1—C1—C6	141.74 (12)	C4—C5—C6—C7	179.44 (17)
O2—S1—C1—C6	−85.85 (14)	C1—C6—C7—C8	−13.2 (2)
N1—S1—C1—C6	27.87 (14)	C5—C6—C7—O3	−14.6 (2)
S1—N1—C8—C7	53.31 (19)	C1—C6—C7—O3	164.83 (15)
S1—C1—C2—C3	176.30 (15)	C5—C6—C7—C8	167.41 (16)
C6—C1—C2—C3	−1.6 (3)	O3—C7—C8—N1	166.31 (15)
S1—C1—C6—C7	3.99 (19)	C6—C7—C8—N1	−15.6 (2)
C2—C1—C6—C5	1.3 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3i	0.80 (2)	2.34 (2)	3.028 (2)	144 (2)
C2—H2···O2ii	0.93	2.58	3.443 (2)	154
C8—H8A···O2iii	0.97	2.48	3.273 (2)	139

Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x, −y, −z; (iii) −x+1, −y, −z.