2-(4-Chloro­phen­yl)-3,5-dimethyl-1λ6,2-thia­zine-1,1-dione

Braim, R.R.; Aziz Ketuly, K.; Hadi, A.H.A.; Khaledi, H.

doi:10.1107/S1600536811038852

organic compounds

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ISSN: 2056-9890

Volume 67| Part 10| October 2011| Page o2775

https://doi.org/10.1107/S1600536811038852

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2-(4-Chlorophenyl)-3,5-dimethyl-1λ⁶,2-thiazine-1,1-dione

Rostam R. Braim,^a Kamal Aziz Ketuly,^b A. Hamid A. Hadi ^b and Hamid Khaledi ^b ^*

^aDepartment of Chemistry,University of Salahaddin-Erbil, KurdistanIraq, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: khaledi@siswa.um.edu.my

(Received 16 September 2011; accepted 21 September 2011; online 30 September 2011)

In the title compound, C₁₂H₁₂ClNO₂S, the S atom is displaced by 0.708 (2) Å out of the plane through the remaining atoms of the thiazine ring (r.m.s. deviation = 0.0823 Å). This plane makes a dihedral angle of 89.33 (7)° with the phenyl ring. In the crystal, adjacent molecules are connected through C—H⋯O hydrogen bonds into layers parallel to the bc plane.

Related literature

For the structure of the 4-methoxyphenyl analogue, see: Fanghanel et al. (1998 ). For some reactions of sultones and sultams, see: Imam Ismail (1990 ).

Experimental

Crystal data

C₁₂H₁₂ClNO₂S
M_r = 269.74
Monoclinic, P 2₁ /c
a = 11.2237 (1) Å
b = 15.1606 (2) Å
c = 7.8752 (1) Å
β = 108.4503 (8)°
V = 1271.15 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.45 mm⁻¹
T = 100 K
0.28 × 0.24 × 0.19 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.884, T_max = 0.919
11365 measured reflections
2768 independent reflections
2447 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.080
S = 1.04
2768 reflections
156 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.43 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯O1ⁱ	0.95	2.57	3.3384 (18)	138
C9—H9⋯O2ⁱⁱ	0.95	2.44	3.3339 (19)	156
Symmetry codes: (i) -x+1, -y+1, -z+2; (ii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536811038852/vm2124sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811038852/vm2124Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811038852/vm2124Isup3.cml

checkCIF report

Comment top

Sultones are cyclic sulfonate esters of hydroxy sulfonic acids and may be saturated or unsaturated. It is well known that the reaction of unsaturated sultones with primary amines forms the corresponding sultams, a cyclic sulfonamide in which the S—N bond is part of the ring (Imam Ismail, 1990). The title sultam compound was obtained through the reaction of the sultone, 4,6-dimethyl-2,2-dioxo-1,2-oxathiine, with p-chloroaniline. Similar to what was observed in the structure of the 4-methoxyphenyl analogue (Fanghanel et al., 1998), the thiazine ring adopts a half-chair conformation with the S atom displaced by 0.708 (2) Å from the plane passing through the remaining five atoms of the ring, C2,C3,C4,C6 and N1. This plane and the phenyl ring make a dihedral angle of 89.33 (7)°. In the crystal, intermolecular C—H···O hydrogen bonds connect the molecules to form a two-dimensional network parallel to the bc plane (Table 1).

Related literature top

For the structure of the 4-methoxyphenyl analogue, see: Fanghanel et al. (1998). For some reactions of sultones and sultams, see: Imam Ismail (1990).

Experimental top

A mixture of 4,6-dimethyl-2,2-dioxo-1,2-oxathiine (1.6 g, 0.01 mol) and p-chloroaniline (1.28 g, 0.01 mol) in a conical flask was heated at 150°C for an hour. The content was cooled to room temperature and then washed with an aqueous solution (10 ml) of HCl (0.1 N). The white solid was collected, washed with water and dried over silica-gel. The X-ray quality crystals were obtained from a methanol solution at room temperature.

Structure description top

For the structure of the 4-methoxyphenyl analogue, see: Fanghanel et al. (1998). For some reactions of sultones and sultams, see: Imam Ismail (1990).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Figures top

Fig. 1. Molecular structure of the title compound with thermal ellipsoids at the 50% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius.

2-(4-Chlorophenyl)-3,5-dimethyl-1λ⁶,2-thiazine-1,1-dione top

Crystal data top

C₁₂H₁₂ClNO₂S	F(000) = 560
M_r = 269.74	D_x = 1.409 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4756 reflections
a = 11.2237 (1) Å	θ = 2.7–30.5°
b = 15.1606 (2) Å	µ = 0.45 mm⁻¹
c = 7.8752 (1) Å	T = 100 K
β = 108.4503 (8)°	Block, colorless
V = 1271.15 (3) Å³	0.28 × 0.24 × 0.19 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	2768 independent reflections
Radiation source: fine-focus sealed tube	2447 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
φ and ω scans	θ_max = 27.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→14
T_min = 0.884, T_max = 0.919	k = −19→19
11365 measured reflections	l = −10→10

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.080	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0375P)² + 0.7004P] where P = (F_o² + 2F_c²)/3
2768 reflections	(Δ/σ)_max = 0.001
156 parameters	Δρ_max = 0.38 e Å⁻³
0 restraints	Δρ_min = −0.43 e Å⁻³

Crystal data top

C₁₂H₁₂ClNO₂S	V = 1271.15 (3) Å³
M_r = 269.74	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.2237 (1) Å	µ = 0.45 mm⁻¹
b = 15.1606 (2) Å	T = 100 K
c = 7.8752 (1) Å	0.28 × 0.24 × 0.19 mm
β = 108.4503 (8)°

Data collection top

Bruker APEXII CCD diffractometer	2768 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2447 reflections with I > 2σ(I)
T_min = 0.884, T_max = 0.919	R_int = 0.027
11365 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.080	H-atom parameters constrained
S = 1.04	Δρ_max = 0.38 e Å⁻³
2768 reflections	Δρ_min = −0.43 e Å⁻³
156 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.

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
Cl1	1.15452 (4)	0.78261 (3)	0.78766 (6)	0.03679 (13)
S1	0.67185 (3)	0.54702 (2)	0.90462 (5)	0.01583 (10)
O1	0.57169 (10)	0.60996 (7)	0.84129 (15)	0.0224 (2)
O2	0.76889 (10)	0.56910 (7)	1.06785 (14)	0.0236 (2)
N1	0.73994 (11)	0.53279 (8)	0.74623 (16)	0.0169 (3)
C1	0.72390 (16)	0.49244 (12)	0.4367 (2)	0.0266 (4)
H1A	0.6744	0.4541	0.3397	0.040*
H1B	0.8133	0.4784	0.4645	0.040*
H1C	0.7095	0.5542	0.3992	0.040*
C2	0.68489 (13)	0.47796 (10)	0.59948 (19)	0.0180 (3)
C3	0.60397 (14)	0.41358 (10)	0.6087 (2)	0.0195 (3)
H3	0.5626	0.3814	0.5029	0.023*
C4	0.57720 (13)	0.39124 (9)	0.7697 (2)	0.0181 (3)
C5	0.51384 (16)	0.30477 (10)	0.7770 (2)	0.0264 (3)
H5A	0.4946	0.3006	0.8898	0.040*
H5B	0.5697	0.2563	0.7697	0.040*
H5C	0.4358	0.3010	0.6763	0.040*
C6	0.61295 (13)	0.44386 (9)	0.9154 (2)	0.0171 (3)
H6	0.6053	0.4233	1.0254	0.021*
C7	0.84013 (13)	0.59335 (10)	0.75099 (19)	0.0173 (3)
C8	0.81380 (15)	0.68225 (10)	0.7151 (2)	0.0233 (3)
H8	0.7297	0.7028	0.6841	0.028*
C9	0.91055 (15)	0.74081 (11)	0.7247 (2)	0.0270 (4)
H9	0.8936	0.8017	0.7006	0.032*
C10	1.03192 (15)	0.70909 (11)	0.7698 (2)	0.0243 (3)
C11	1.05906 (14)	0.62056 (11)	0.8042 (2)	0.0237 (3)
H11	1.1431	0.6000	0.8337	0.028*
C12	0.96219 (14)	0.56223 (10)	0.7952 (2)	0.0202 (3)
H12	0.9794	0.5013	0.8191	0.024*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0280 (2)	0.0363 (2)	0.0456 (3)	−0.01448 (18)	0.01096 (19)	0.00453 (19)
S1	0.01745 (18)	0.01486 (18)	0.01607 (18)	−0.00151 (13)	0.00658 (14)	−0.00116 (13)
O1	0.0240 (6)	0.0180 (5)	0.0280 (6)	0.0041 (4)	0.0121 (5)	0.0018 (4)
O2	0.0258 (6)	0.0265 (6)	0.0175 (5)	−0.0090 (5)	0.0051 (5)	−0.0038 (4)
N1	0.0166 (6)	0.0177 (6)	0.0175 (6)	−0.0017 (5)	0.0071 (5)	−0.0011 (5)
C1	0.0287 (8)	0.0336 (9)	0.0188 (8)	−0.0013 (7)	0.0094 (7)	−0.0017 (6)
C2	0.0170 (7)	0.0204 (7)	0.0157 (7)	0.0049 (6)	0.0038 (6)	0.0001 (6)
C3	0.0188 (7)	0.0191 (7)	0.0184 (7)	0.0016 (6)	0.0028 (6)	−0.0035 (6)
C4	0.0151 (7)	0.0156 (7)	0.0224 (7)	0.0017 (5)	0.0045 (6)	0.0007 (6)
C5	0.0303 (8)	0.0179 (7)	0.0306 (8)	−0.0065 (7)	0.0093 (7)	−0.0030 (6)
C6	0.0172 (7)	0.0154 (7)	0.0196 (7)	−0.0010 (5)	0.0070 (6)	0.0022 (5)
C7	0.0164 (7)	0.0201 (7)	0.0163 (7)	−0.0009 (6)	0.0062 (5)	0.0019 (5)
C8	0.0181 (7)	0.0217 (8)	0.0298 (8)	0.0025 (6)	0.0070 (6)	0.0053 (6)
C9	0.0271 (8)	0.0193 (8)	0.0349 (9)	0.0000 (7)	0.0103 (7)	0.0063 (7)
C10	0.0204 (8)	0.0278 (8)	0.0249 (8)	−0.0079 (6)	0.0077 (6)	0.0028 (6)
C11	0.0164 (7)	0.0296 (8)	0.0252 (8)	0.0021 (6)	0.0069 (6)	0.0048 (6)
C12	0.0206 (7)	0.0206 (7)	0.0199 (7)	0.0019 (6)	0.0072 (6)	0.0034 (6)

Geometric parameters (Å, º) top

Cl1—C10	1.7416 (16)	C4—C5	1.501 (2)
S1—O2	1.4369 (11)	C5—H5A	0.9800
S1—O1	1.4382 (11)	C5—H5B	0.9800
S1—N1	1.6703 (12)	C5—H5C	0.9800
S1—C6	1.7104 (14)	C6—H6	0.9500
N1—C2	1.3987 (19)	C7—C12	1.385 (2)
N1—C7	1.4430 (18)	C7—C8	1.390 (2)
C1—C2	1.496 (2)	C8—C9	1.386 (2)
C1—H1A	0.9800	C8—H8	0.9500
C1—H1B	0.9800	C9—C10	1.381 (2)
C1—H1C	0.9800	C9—H9	0.9500
C2—C3	1.351 (2)	C10—C11	1.384 (2)
C3—C4	1.433 (2)	C11—C12	1.386 (2)
C3—H3	0.9500	C11—H11	0.9500
C4—C6	1.350 (2)	C12—H12	0.9500

O2—S1—O1	116.33 (7)	H5A—C5—H5B	109.5
O2—S1—N1	107.56 (6)	C4—C5—H5C	109.5
O1—S1—N1	108.60 (6)	H5A—C5—H5C	109.5
O2—S1—C6	111.35 (7)	H5B—C5—H5C	109.5
O1—S1—C6	110.61 (7)	C4—C6—S1	120.91 (12)
N1—S1—C6	101.21 (7)	C4—C6—H6	119.5
C2—N1—C7	122.44 (12)	S1—C6—H6	119.5
C2—N1—S1	120.46 (10)	C12—C7—C8	120.75 (14)
C7—N1—S1	115.81 (10)	C12—C7—N1	119.36 (13)
C2—C1—H1A	109.5	C8—C7—N1	119.87 (13)
C2—C1—H1B	109.5	C9—C8—C7	119.85 (14)
H1A—C1—H1B	109.5	C9—C8—H8	120.1
C2—C1—H1C	109.5	C7—C8—H8	120.1
H1A—C1—H1C	109.5	C10—C9—C8	118.88 (15)
H1B—C1—H1C	109.5	C10—C9—H9	120.6
C3—C2—N1	120.91 (13)	C8—C9—H9	120.6
C3—C2—C1	122.43 (14)	C9—C10—C11	121.75 (15)
N1—C2—C1	116.63 (13)	C9—C10—Cl1	119.19 (13)
C2—C3—C4	123.45 (14)	C11—C10—Cl1	119.05 (12)
C2—C3—H3	118.3	C10—C11—C12	119.23 (14)
C4—C3—H3	118.3	C10—C11—H11	120.4
C6—C4—C3	121.54 (13)	C12—C11—H11	120.4
C6—C4—C5	120.04 (14)	C7—C12—C11	119.54 (14)
C3—C4—C5	118.34 (13)	C7—C12—H12	120.2
C4—C5—H5A	109.5	C11—C12—H12	120.2
C4—C5—H5B	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O1ⁱ	0.95	2.57	3.3384 (18)	138
C9—H9···O2ⁱⁱ	0.95	2.44	3.3339 (19)	156

Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) x, −y+3/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₂ClNO₂S
M_r	269.74
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	11.2237 (1), 15.1606 (2), 7.8752 (1)
β (°)	108.4503 (8)
V (Å³)	1271.15 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.45
Crystal size (mm)	0.28 × 0.24 × 0.19

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.884, 0.919
No. of measured, independent and observed [I > 2σ(I)] reflections	11365, 2768, 2447
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.080, 1.04
No. of reflections	2768
No. of parameters	156
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.43

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O1ⁱ	0.95	2.57	3.3384 (18)	137.8
C9—H9···O2ⁱⁱ	0.95	2.44	3.3339 (19)	156.4

Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) x, −y+3/2, z−1/2.

Acknowledgements

Financial support form the University of Malaya is highly appreciated (PPP grant No. PS359/2009 C).

References

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