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

Aman, F.; Siddiqui, W.A.; Ashraf, A.; Tahir, M.N.

doi:10.1107/S1600536812013827

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 5| May 2012| Page o1306

doi:10.1107/S1600536812013827

Open

access

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

Farhana Aman,^a Waseeq Ahmad Siddiqui,^a Adnan Ashraf ^a and M. Nawaz Tahir ^b ^*

^aUniversity of Sargodha, Department of Chemistry, Sargodha, Pakistan, and ^bUniversity of Sargodha, Department of Physics, Sargodha, Pakistan
^*Correspondence e-mail: dmntahir_uos@yahoo.com

(Received 27 March 2012; accepted 30 March 2012; online 4 April 2012)

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 R₂²(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, P 2₁ /c
a = 8.4950 (4) Å
b = 13.7560 (5) Å
c = 7.6677 (3) Å
β = 113.214 (1)°
V = 823.48 (6) Å³
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[F² > 2σ(F²)] = 0.036
wR(F²) = 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

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) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) -x, -y, -z; (iii) -x+1, -y, -z.

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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812013827/hb6713sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812013827/hb6713Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812013827/hb6713Isup3.cml

checkCIF report

Comment top

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)°.

Related literature top

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 top

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).

Computing details top

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

Figures top

	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.

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

Crystal data top

C₈H₇NO₃S	F(000) = 408
M_r = 197.21	D_x = 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 top

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

Refinement top

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(F_o²) + (0.0455P)² + 0.3408P] where P = (F_o² + 2F_c²)/3
2017 reflections	(Δ/σ)_max < 0.001
121 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.37 e Å⁻³

Crystal data top

C₈H₇NO₃S	V = 823.48 (6) Å³
M_r = 197.21	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.4950 (4) Å	µ = 0.36 mm⁻¹
b = 13.7560 (5) Å	T = 296 K
c = 7.6677 (3) Å	0.35 × 0.15 × 0.12 mm
β = 113.214 (1)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	2017 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1692 reflections with I > 2σ(I)
T_min = 0.915, T_max = 0.938	R_int = 0.022
7644 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.098	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.33 e Å⁻³
2017 reflections	Δρ_min = −0.37 e Å⁻³
121 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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) top

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) top

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.

Experimental details

Crystal data
Chemical formula	C₈H₇NO₃S
M_r	197.21
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	8.4950 (4), 13.7560 (5), 7.6677 (3)
β (°)	113.214 (1)
V (Å³)	823.48 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.36
Crystal size (mm)	0.35 × 0.15 × 0.12

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.915, 0.938
No. of measured, independent and observed [I > 2σ(I)] reflections	7644, 2017, 1692
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.098, 1.04
No. of reflections	2017
No. of parameters	121
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.37

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

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.

Acknowledgements

The authors acknowledge the provision of funds for the purchase of the diffractometer and encouragement by Dr Muhammad Akram Chaudhary, Vice Chancellor, University of Sargodha, Pakistan. The authors also acknowledge the technical support provided by Syed Muhammad Hussain Rizvi of Bana International, Karachi, Pakistan.

References

Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2005). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siddiqui, W. A., Ahmad, S., Siddiqui, H. L., Bukhari, M. H. & Parvez, M. (2008). Acta Cryst. E64, o1922. Web of Science CSD CrossRef IUCr Journals Google Scholar
Siddiqui, W. A., Ahmad, S., Siddiqui, H. L., Tariq, M. I. & Parvez, M. (2007). Acta Cryst. E63, o4585. Web of Science CSD CrossRef IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar