2-[(3-Bromo­anilino)meth­yl]-1,2-benzo­thia­zol-3(2H)-one

Abstract

The title compound, C₁₄H₁₁BrN₂OS, was synthesized by the reaction of 1,2-benzothia­zol-3(2H)-one with formalin and 3-bromo­aniline in ethanol. The 1,2-benzothia­zolone ring system is approximately planar [maximum deviation = 0.0142 (s.u.?) Å] and forms a dihedral angle of 79.19 (5)° with the benzene ring. In the crystal, molecules are linked by N—H⋯O, C—H⋯O and C—H⋯Br interactions.

Related literature  

For background to the synthesis of benzoisothia­zolone deriv­atives, see: Davis (1972 ▶); Elgazwy & Abdel-Sattar (2003 ▶). For the biological activity of 1,2-benzoisothia­zolone derivatives, see: Taubert et al. (2002 ▶). For structural studies of related alkyl 3-oxo-2,3-dihydro-1,2-benzothia­zole-2-carboxyl­ate derivatives, see: Wang et al. (2011 ▶); Wang, Yang et al. (2011a ▶,b ▶)

Experimental  

Crystal data  

• C₁₄H₁₁BrN₂OS

• M _r = 335.22

• Monoclinic,

• a = 7.351 (2) Å

• b = 22.781 (7) Å

• c = 8.559 (3) Å

• β = 109.580 (4)°

• V = 1350.5 (7) ų

• Z = 4

• Mo Kα radiation

• μ = 3.19 mm⁻¹

• T = 153 K

• 0.38 × 0.37 × 0.31 mm

Data collection  

• Rigaku AFC10/Saturn724+ diffractometer

• Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.374, T _max = 0.436

• 11631 measured reflections

• 3587 independent reflections

• 2709 reflections with I > 2σ(I)

• R _int = 0.037

Refinement  

• R[F ² > 2σ(F ²)] = 0.032

• wR(F ²) = 0.069

• S = 1.00

• 3587 reflections

• 176 parameters

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

• Δρ_max = 0.44 e Å⁻³

• Δρ_min = −0.52 e Å⁻³

Data collection: CrystalClear (Rigaku, 2008 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and DIAMOND (Brandenburg, 1999 ▶); software used to prepare material for publication: SHELXTL and publCIF (Westrip, 2010 ▶).

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812012263/rz2723Isup3.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
N2—H2N⋯O1i	0.82 (2)	2.14 (2)	2.939 (2)	167 (2)
C3—H3⋯O1ii	0.95	2.59	3.484 (3)	157
C10—H10⋯Br1iii	0.95	2.93	3.545 (3)	124
C14—H14⋯O1i	0.95	2.46	3.207 (3)	135

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

supplementary crystallographic information

Comment

The work presented herein is part of our interest in synthesizing various benzisothiazolone derivatives and confirming their structures by X-ray analysis (Wang et al., 2011; Wang, Yang et al., 2011a,b). These compounds will be utilized for the study of comparative bioactivity.

The molecular structure of the title compound is shown in Fig. 1. In the molecule, the benzisothiazolone ring system is approximately planar with a maximum deviation from the mean plane of 0.0142 A ° for the atom C1, and the dihedral angle between the benzene ring and the benzisothiazolone ring is 79.169 (5)°. In the crystal structure, intermolecular N—H···O, C—H···O and C—H···Br hydrogen bonds (Table 1) link molecules into a three-dimensional network (Fig. 2).

Experimental

An ethanol solution (20 ml) containing 1,2-benzothiazol-3(2H)-one (1.51 g, 0.01 mol), formalin (1 mL) and 3-bromoaniline (1.72 g, 0.01 mol) was stirred at room temperature for 4.5 h to afford the title compound (1.97 g, yield 58.8%). Single crystals suitable for X-ray measurements were obtained by recrystallization of the title compound from trichloromethane/methanol (1:1 v/v) at room temperature.

Refinement

The amine H atom was located in a difference Fourier map and refined freely. All other H atoms were placed at calculated positions and refined in riding mode, with C—H = 0.95–0.99 Å. The U_iso(H) values were constrained to be 1.5U_eq(C) for the methyl H atoms or 1.2U_eq(C) for the remaining H atoms.

Figures

Fig. 1.

The molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level. H atoms are presented as small spheres of arbitrary radius.

Fig. 2.

A view of the C—H···O and C—H···Br interactions (dashed lines) in the crystal structure of the title compound.

Crystal data

C14H11BrN2OS	F(000) = 672
Mr = 335.22	Dx = 1.649 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4184 reflections
a = 7.351 (2) Å	θ = 2.7–29.1°
b = 22.781 (7) Å	µ = 3.19 mm−1
c = 8.559 (3) Å	T = 153 K
β = 109.580 (4)°	Block, colourless
V = 1350.5 (7) Å3	0.38 × 0.37 × 0.31 mm
Z = 4

Data collection

Rigaku AFC10/Saturn724+ diffractometer	3587 independent reflections
Radiation source: Rotating Anode	2709 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.037
Detector resolution: 28.5714 pixels mm-1	θmax = 29.1°, θmin = 2.7°
phi and ω scans	h = −10→9
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −31→30
Tmin = 0.374, Tmax = 0.436	l = −11→11
11631 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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.069	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ2(Fo2) + (0.0289P)2 + 0.160P] where P = (Fo2 + 2Fc2)/3
3587 reflections	(Δ/σ)max < 0.001
176 parameters	Δρmax = 0.44 e Å−3
0 restraints	Δρmin = −0.52 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Br1	0.37553 (3)	0.693276 (11)	0.83530 (3)	0.03101 (8)
O1	1.1959 (2)	0.47887 (6)	1.16801 (16)	0.0223 (3)
S1	1.30876 (8)	0.60263 (2)	1.48237 (6)	0.02068 (12)
N1	1.2660 (2)	0.56804 (7)	1.29651 (19)	0.0181 (4)
C13	0.6410 (3)	0.69583 (9)	0.9710 (3)	0.0220 (4)
C7	1.2302 (3)	0.50892 (9)	1.2939 (2)	0.0174 (4)
N2	1.0771 (2)	0.60956 (8)	1.0275 (2)	0.0184 (4)
C5	1.2107 (3)	0.43397 (10)	1.5099 (3)	0.0218 (4)
H5	1.1821	0.4025	1.4327	0.026*
C3	1.2648 (3)	0.47107 (10)	1.7852 (3)	0.0253 (5)
H3	1.2716	0.4638	1.8963	0.030*
C1	1.2822 (3)	0.53648 (9)	1.5741 (2)	0.0181 (4)
C9	0.9559 (3)	0.65290 (9)	1.0506 (2)	0.0172 (4)
C10	1.0203 (3)	0.69745 (9)	1.1676 (3)	0.0261 (5)
H10	1.1519	0.6985	1.2368	0.031*
C14	0.7614 (3)	0.65249 (9)	0.9498 (2)	0.0182 (4)
H14	0.7134	0.6229	0.8682	0.022*
C6	1.2401 (3)	0.49047 (9)	1.4604 (2)	0.0168 (4)
C8	1.2648 (3)	0.59860 (9)	1.1440 (2)	0.0184 (4)
H8A	1.3328	0.6366	1.1755	0.022*
H8B	1.3384	0.5747	1.0891	0.022*
C2	1.2955 (3)	0.52715 (10)	1.7396 (3)	0.0237 (5)
H2	1.3246	0.5584	1.8174	0.028*
C4	1.2239 (3)	0.42447 (10)	1.6723 (3)	0.0259 (5)
H4	1.2051	0.3861	1.7078	0.031*
C12	0.7015 (3)	0.74034 (11)	1.0860 (3)	0.0324 (5)
H12	0.6149	0.7697	1.0973	0.039*
C11	0.8935 (4)	0.74030 (11)	1.1840 (3)	0.0349 (6)
H11	0.9402	0.7703	1.2645	0.042*
H2N	1.017 (3)	0.5816 (10)	0.975 (3)	0.023 (6)*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Br1	0.02204 (12)	0.03134 (14)	0.03771 (15)	0.00613 (10)	0.00744 (9)	0.00158 (11)
O1	0.0263 (8)	0.0235 (8)	0.0165 (8)	−0.0016 (7)	0.0064 (6)	−0.0054 (6)
S1	0.0272 (3)	0.0200 (3)	0.0155 (3)	−0.0026 (2)	0.0080 (2)	−0.0035 (2)
N1	0.0253 (9)	0.0177 (9)	0.0124 (9)	−0.0007 (7)	0.0076 (7)	−0.0009 (7)
C13	0.0227 (10)	0.0203 (11)	0.0235 (12)	0.0014 (9)	0.0083 (9)	0.0035 (9)
C7	0.0150 (9)	0.0194 (11)	0.0166 (11)	0.0010 (8)	0.0038 (8)	−0.0013 (8)
N2	0.0189 (9)	0.0179 (9)	0.0162 (9)	0.0000 (7)	0.0029 (7)	−0.0024 (7)
C5	0.0182 (10)	0.0234 (11)	0.0229 (12)	0.0000 (9)	0.0059 (8)	0.0005 (9)
C3	0.0220 (11)	0.0365 (13)	0.0191 (12)	0.0016 (10)	0.0092 (9)	0.0068 (10)
C1	0.0137 (9)	0.0231 (11)	0.0178 (11)	−0.0009 (8)	0.0054 (8)	0.0001 (8)
C9	0.0207 (10)	0.0151 (10)	0.0164 (10)	0.0000 (8)	0.0071 (8)	0.0024 (8)
C10	0.0239 (11)	0.0211 (11)	0.0289 (13)	−0.0026 (10)	0.0032 (9)	−0.0066 (9)
C14	0.0228 (11)	0.0176 (10)	0.0150 (11)	−0.0001 (8)	0.0073 (8)	0.0006 (8)
C6	0.0128 (9)	0.0212 (10)	0.0155 (10)	0.0019 (8)	0.0038 (7)	0.0014 (8)
C8	0.0208 (10)	0.0215 (11)	0.0154 (10)	−0.0010 (9)	0.0095 (8)	0.0005 (8)
C2	0.0229 (11)	0.0314 (13)	0.0177 (11)	0.0002 (9)	0.0079 (9)	−0.0016 (9)
C4	0.0232 (11)	0.0277 (12)	0.0279 (13)	0.0004 (10)	0.0098 (9)	0.0081 (10)
C12	0.0337 (13)	0.0256 (12)	0.0389 (14)	0.0061 (11)	0.0134 (11)	−0.0091 (11)
C11	0.0392 (14)	0.0251 (13)	0.0382 (14)	−0.0003 (11)	0.0100 (11)	−0.0165 (11)

Geometric parameters (Å, º)

Br1—C13	1.908 (2)	C3—C4	1.398 (3)
O1—C7	1.229 (2)	C3—H3	0.9500
S1—N1	1.7074 (17)	C1—C6	1.393 (3)
S1—C1	1.740 (2)	C1—C2	1.403 (3)
N1—C7	1.371 (3)	C9—C10	1.393 (3)
N1—C8	1.476 (2)	C9—C14	1.401 (3)
C13—C14	1.378 (3)	C10—C11	1.389 (3)
C13—C12	1.379 (3)	C10—H10	0.9500
C7—C6	1.464 (3)	C14—H14	0.9500
N2—C9	1.388 (3)	C8—H8A	0.9900
N2—C8	1.427 (2)	C8—H8B	0.9900
N2—H2N	0.82 (2)	C2—H2	0.9500
C5—C4	1.378 (3)	C4—H4	0.9500
C5—C6	1.394 (3)	C12—C11	1.379 (3)
C5—H5	0.9500	C12—H12	0.9500
C3—C2	1.376 (3)	C11—H11	0.9500
N1—S1—C1	90.41 (9)	C11—C10—H10	119.8
C7—N1—C8	120.30 (16)	C9—C10—H10	119.8
C7—N1—S1	116.28 (13)	C13—C14—C9	118.83 (19)
C8—N1—S1	123.42 (13)	C13—C14—H14	120.6
C14—C13—C12	123.6 (2)	C9—C14—H14	120.6
C14—C13—Br1	117.97 (16)	C1—C6—C5	120.22 (18)
C12—C13—Br1	118.46 (17)	C1—C6—C7	113.01 (18)
O1—C7—N1	122.90 (18)	C5—C6—C7	126.76 (18)
O1—C7—C6	128.46 (19)	N2—C8—N1	114.72 (16)
N1—C7—C6	108.64 (17)	N2—C8—H8A	108.6
C9—N2—C8	122.78 (18)	N1—C8—H8A	108.6
C9—N2—H2N	112.0 (16)	N2—C8—H8B	108.6
C8—N2—H2N	117.8 (16)	N1—C8—H8B	108.6
C4—C5—C6	119.1 (2)	H8A—C8—H8B	107.6
C4—C5—H5	120.5	C3—C2—C1	117.7 (2)
C6—C5—H5	120.5	C3—C2—H2	121.2
C2—C3—C4	121.8 (2)	C1—C2—H2	121.2
C2—C3—H3	119.1	C5—C4—C3	120.3 (2)
C4—C3—H3	119.1	C5—C4—H4	119.9
C6—C1—C2	121.0 (2)	C3—C4—H4	119.9
C6—C1—S1	111.65 (15)	C13—C12—C11	116.9 (2)
C2—C1—S1	127.33 (17)	C13—C12—H12	121.5
N2—C9—C10	122.76 (19)	C11—C12—H12	121.5
N2—C9—C14	118.63 (19)	C12—C11—C10	121.6 (2)
C10—C9—C14	118.60 (19)	C12—C11—H11	119.2
C11—C10—C9	120.5 (2)	C10—C11—H11	119.2
C1—S1—N1—C7	0.55 (16)	S1—C1—C6—C7	0.5 (2)
C1—S1—N1—C8	−179.97 (16)	C4—C5—C6—C1	0.1 (3)
C8—N1—C7—O1	0.0 (3)	C4—C5—C6—C7	−179.39 (19)
S1—N1—C7—O1	179.45 (15)	O1—C7—C6—C1	−179.89 (19)
C8—N1—C7—C6	−179.87 (16)	N1—C7—C6—C1	−0.1 (2)
S1—N1—C7—C6	−0.4 (2)	O1—C7—C6—C5	−0.4 (3)
N1—S1—C1—C6	−0.57 (15)	N1—C7—C6—C5	179.41 (18)
N1—S1—C1—C2	−179.34 (19)	C9—N2—C8—N1	74.6 (2)
C8—N2—C9—C10	14.7 (3)	C7—N1—C8—N2	76.3 (2)
C8—N2—C9—C14	−166.54 (18)	S1—N1—C8—N2	−103.16 (19)
N2—C9—C10—C11	179.0 (2)	C4—C3—C2—C1	0.7 (3)
C14—C9—C10—C11	0.3 (3)	C6—C1—C2—C3	−0.2 (3)
C12—C13—C14—C9	0.5 (3)	S1—C1—C2—C3	178.47 (16)
Br1—C13—C14—C9	−178.70 (15)	C6—C5—C4—C3	0.4 (3)
N2—C9—C14—C13	−179.28 (18)	C2—C3—C4—C5	−0.9 (3)
C10—C9—C14—C13	−0.5 (3)	C14—C13—C12—C11	−0.3 (4)
C2—C1—C6—C5	−0.2 (3)	Br1—C13—C12—C11	178.94 (18)
S1—C1—C6—C5	−179.05 (15)	C13—C12—C11—C10	0.0 (4)
C2—C1—C6—C7	179.34 (18)	C9—C10—C11—C12	0.0 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···O1i	0.82 (2)	2.14 (2)	2.939 (2)	167 (2)
C3—H3···O1ii	0.95	2.59	3.484 (3)	157
C10—H10···Br1iii	0.95	2.93	3.545 (3)	124
C14—H14···O1i	0.95	2.46	3.207 (3)	135

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