N-(Benzothia­zol-2-yl)-3-chloro­benzamide

Khawar Rauf, M.; Bolte, M.; Badshah, A.

doi:10.1107/S1600536809016481

organic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page o1245

doi:10.1107/S1600536809016481

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N-(Benzothiazol-2-yl)-3-chlorobenzamide

M. Khawar Rauf,^a Michael Bolte ^b and Amin Badshah ^c ^*

^aDepartment of Chemistry, Quaid-i-Azam University, Islamabad 45320, Pakistan, ^bInstitut für Anorganische Chemie, J. W. Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt/Main, Germany, and ^cDepartment of Chemistry, Islamia University of Bahawalpur, Pakistan
^*Correspondence e-mail: aminbadshah@yahoo.com

(Received 29 April 2009; accepted 2 May 2009; online 14 May 2009)

The title molecule, C₁₄H₉ClN₂OS, exists in the solid state in its amide form with a typical C=O bond length, as well as shortened C—N bonds. The plane containing the HNCO atoms subtends dihedral angles of 12.3 (4) and 8.1 (3)° with the planes of the phenyl ring and benzothiazole group, respectively, whereas the dihedral angle between the planes of the phenyl ring and the benzothiazole group is 5.96 (6)°. In the crystal, molecules form intermolecular N—H⋯N hydrogen bonds, generating independent scissor-like R²₂(8) dimers.

Related literature

For geometric data, see: Allen et al. (1987 ); For related structures, see: Garden et al. (2005 ); Wardell et al. (2005 ).

Experimental

Crystal data

C₁₄H₉ClN₂OS
M_r = 288.74
Monoclinic, C 2/c
a = 26.6613 (19) Å
b = 7.5766 (5) Å
c = 12.6729 (10) Å
β = 99.729 (6)°
V = 2523.1 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.46 mm⁻¹
T = 173 K
0.39 × 0.38 × 0.35 mm

Data collection

Stoe IPDS II two-circle diffractometer
Absorption correction: multi-scan [MULABS (Spek, 2009 ); Blessing, 1995 )] T_min = 0.841, T_max = 0.856
9132 measured reflections
2352 independent reflections
2084 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.079
S = 1.03
2352 reflections
177 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N2ⁱ	0.94 (2)	2.02 (2)	2.9429 (18)	168.9 (17)
Symmetry code: (i) $[-x+1, y, -z+{\script{3\over 2}}]$ .

Data collection: X-AREA (Stoe & Cie, 2001 ); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009) and XP in SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809016481/hg2508sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809016481/hg2508Isup2.hkl

checkCIF report

Comment top

We report here the structure of the title compound, (I) (Fig. 1), which has been separated from an impure sample of thiourea by column chromatography as a by-product, a part of our ongoing studies related to N,N'-disubstituted thioureas and heterocyclic compounds. These include N—H···N hydrogen bonds, with possible oxygen-sulfur intramolecular interactions (Fig. 2). In this class of componds, N—H···O, C—H···O and N—H···N hydrogen bonds, and weak π–π stacking interactions are the only direction-specific intermolecular interactions (Garden et al., 2005; Wardell et al., 2005). The molecules of (I) are nearly planar, as shown by the leading torsion angles [C11—C1—N1—C2 174.90 (12) and C1—N1—C2—N2 -171.57 (13)°], and the amide group adopts the usual trans conformation; the bond lengths and inter-bond angles present no unusual values (Allen et al., 1987).

Related literature top

For geometric data, see: Allen et al. (1987); For related structures, see: Garden et al. (2005); Wardell et al. (2005).

Experimental top

Freshly prepared and steam-distilled 3-chlorobenzoyl isothiocyanate (1.98 g, 10 mmol) was stirred in acetone (30 ml) for 20 min. Neat 2-aminobenzothiazole (1.50 g, 10 mmol) was then added and the resulting mixture was stirred for 1 h. The reaction mixture was then poured into 300 ml (approx.) acidified (pH 4) water and stirred well. The solid product was separated and washed with deionized water. One of the fraction obtained as a by-product during the column chromatography of the target thiourea was recrystallized from methanol/1,1-dichloromethane (1:10 v/v) to give fine crystals of (I), with an overall fractional yield of 15%.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA (Stoe & Cie, 2001); data reduction: X-AREA (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009) and XP in SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of (I) showing atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Packing diagram of (I) with view onto the ac plane. Hydrogen bonds shown as dashed lines. H atoms are omitted for clarity.

N-(Benzothiazol-2-yl)-3-chlorobenzamide top

Crystal data top

C₁₄H₉ClN₂OS	F(000) = 1184
M_r = 288.74	D_x = 1.520 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 8429 reflections
a = 26.6613 (19) Å	θ = 3.6–25.9°
b = 7.5766 (5) Å	µ = 0.46 mm⁻¹
c = 12.6729 (10) Å	T = 173 K
β = 99.729 (6)°	Block, light yellow
V = 2523.1 (3) Å³	0.39 × 0.38 × 0.35 mm
Z = 8

Data collection top

Stoe IPDS II two-circle diffractometer	2352 independent reflections
Radiation source: fine-focus sealed tube	2084 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
ω scans	θ_max = 25.6°, θ_min = 3.6°
Absorption correction: multi-scan [MULABS (Spek, 2009); Blessing, 1995)]	h = −32→32
T_min = 0.841, T_max = 0.856	k = −8→9
9132 measured reflections	l = −15→15

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.028	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.079	w = 1/[σ²(F_o²) + (0.051P)² + 0.8598P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
2352 reflections	Δρ_max = 0.29 e Å⁻³
177 parameters	Δρ_min = −0.23 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0071 (6)

Crystal data top

C₁₄H₉ClN₂OS	V = 2523.1 (3) Å³
M_r = 288.74	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 26.6613 (19) Å	µ = 0.46 mm⁻¹
b = 7.5766 (5) Å	T = 173 K
c = 12.6729 (10) Å	0.39 × 0.38 × 0.35 mm
β = 99.729 (6)°

Data collection top

Stoe IPDS II two-circle diffractometer	2352 independent reflections
Absorption correction: multi-scan [MULABS (Spek, 2009); Blessing, 1995)]	2084 reflections with I > 2σ(I)
T_min = 0.841, T_max = 0.856	R_int = 0.038
9132 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	0 restraints
wR(F²) = 0.079	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.29 e Å⁻³
2352 reflections	Δρ_min = −0.23 e Å⁻³
177 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	0.762196 (14)	0.69837 (6)	0.65336 (3)	0.03053 (14)
S1	0.500738 (13)	0.23662 (5)	0.45176 (3)	0.01915 (13)
O1	0.58693 (4)	0.40431 (15)	0.51591 (8)	0.0241 (3)
N1	0.54529 (4)	0.34541 (16)	0.65241 (10)	0.0178 (3)
H1	0.5448 (7)	0.325 (2)	0.7252 (17)	0.032 (5)*
C1	0.58602 (5)	0.41061 (19)	0.61190 (11)	0.0179 (3)
N2	0.46256 (4)	0.23590 (16)	0.62817 (10)	0.0185 (3)
C2	0.50288 (5)	0.27653 (19)	0.58813 (11)	0.0167 (3)
C3	0.42583 (5)	0.16277 (19)	0.54925 (12)	0.0185 (3)
C4	0.44015 (5)	0.15038 (19)	0.44819 (12)	0.0191 (3)
C5	0.40794 (6)	0.0750 (2)	0.36146 (12)	0.0242 (3)
H5	0.4179	0.0661	0.2932	0.029*
C6	0.36121 (6)	0.0141 (2)	0.37817 (13)	0.0275 (4)
H6	0.3388	−0.0391	0.3207	0.033*
C7	0.34626 (6)	0.0292 (2)	0.47829 (13)	0.0273 (4)
H7	0.3136	−0.0118	0.4873	0.033*
C8	0.37807 (5)	0.1024 (2)	0.56412 (12)	0.0234 (3)
H8	0.3677	0.1117	0.6320	0.028*
C11	0.62782 (5)	0.49568 (19)	0.68791 (11)	0.0188 (3)
C12	0.67079 (5)	0.5438 (2)	0.64573 (12)	0.0200 (3)
H12	0.6734	0.5140	0.5740	0.024*
C13	0.70955 (5)	0.6348 (2)	0.70855 (12)	0.0213 (3)
C14	0.70650 (6)	0.6824 (2)	0.81238 (12)	0.0245 (3)
H14	0.7333	0.7463	0.8547	0.029*
C15	0.66341 (6)	0.6349 (2)	0.85358 (12)	0.0249 (3)
H15	0.6607	0.6672	0.9248	0.030*
C16	0.62434 (6)	0.5413 (2)	0.79260 (12)	0.0220 (3)
H16	0.5953	0.5083	0.8222	0.026*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0200 (2)	0.0423 (3)	0.0307 (2)	−0.00460 (15)	0.00835 (16)	0.00331 (17)
S1	0.0228 (2)	0.0232 (2)	0.0121 (2)	0.00280 (14)	0.00466 (14)	0.00001 (13)
O1	0.0263 (6)	0.0325 (6)	0.0148 (6)	−0.0019 (4)	0.0074 (4)	−0.0004 (4)
N1	0.0188 (6)	0.0221 (7)	0.0128 (6)	0.0014 (5)	0.0041 (5)	0.0011 (5)
C1	0.0199 (7)	0.0189 (7)	0.0161 (8)	0.0046 (5)	0.0061 (5)	0.0018 (5)
N2	0.0183 (6)	0.0227 (7)	0.0143 (6)	0.0024 (5)	0.0019 (5)	0.0000 (5)
C2	0.0207 (7)	0.0178 (7)	0.0121 (7)	0.0050 (5)	0.0040 (5)	0.0019 (5)
C3	0.0203 (7)	0.0188 (7)	0.0156 (7)	0.0042 (6)	0.0008 (5)	0.0014 (5)
C4	0.0220 (7)	0.0184 (7)	0.0167 (7)	0.0044 (6)	0.0024 (6)	0.0011 (6)
C5	0.0322 (8)	0.0214 (8)	0.0172 (8)	0.0050 (6)	−0.0009 (6)	−0.0020 (6)
C6	0.0301 (8)	0.0230 (8)	0.0256 (9)	0.0001 (6)	−0.0060 (6)	−0.0029 (6)
C7	0.0233 (8)	0.0253 (9)	0.0311 (9)	−0.0005 (6)	−0.0015 (6)	0.0036 (7)
C8	0.0225 (7)	0.0260 (9)	0.0215 (8)	0.0026 (6)	0.0030 (6)	0.0032 (6)
C11	0.0220 (7)	0.0182 (7)	0.0170 (7)	0.0033 (6)	0.0053 (6)	0.0021 (6)
C12	0.0220 (7)	0.0228 (8)	0.0162 (7)	0.0034 (6)	0.0061 (6)	0.0008 (6)
C13	0.0198 (7)	0.0231 (8)	0.0221 (8)	0.0012 (6)	0.0067 (6)	0.0048 (6)
C14	0.0280 (8)	0.0240 (8)	0.0202 (8)	−0.0027 (6)	0.0004 (6)	0.0010 (6)
C15	0.0337 (8)	0.0259 (8)	0.0159 (7)	−0.0028 (7)	0.0063 (6)	0.0000 (6)
C16	0.0267 (8)	0.0241 (8)	0.0173 (8)	−0.0004 (6)	0.0095 (6)	0.0027 (6)

Geometric parameters (Å, º) top

Cl1—C13	1.7386 (15)	C6—C7	1.397 (2)
S1—C4	1.7360 (15)	C6—H6	0.9500
S1—C2	1.7459 (14)	C7—C8	1.378 (2)
O1—C1	1.2216 (18)	C7—H7	0.9500
N1—C1	1.3696 (18)	C8—H8	0.9500
N1—C2	1.3794 (18)	C11—C16	1.389 (2)
N1—H1	0.94 (2)	C11—C12	1.392 (2)
C1—C11	1.491 (2)	C12—C13	1.378 (2)
N2—C2	1.3008 (19)	C12—H12	0.9500
N2—C3	1.3912 (18)	C13—C14	1.380 (2)
C3—C8	1.395 (2)	C14—C15	1.388 (2)
C3—C4	1.400 (2)	C14—H14	0.9500
C4—C5	1.397 (2)	C15—C16	1.383 (2)
C5—C6	1.378 (2)	C15—H15	0.9500
C5—H5	0.9500	C16—H16	0.9500

C4—S1—C2	88.03 (7)	C8—C7—H7	119.4
C1—N1—C2	122.53 (12)	C6—C7—H7	119.4
C1—N1—H1	125.0 (11)	C7—C8—C3	118.64 (14)
C2—N1—H1	111.8 (11)	C7—C8—H8	120.7
O1—C1—N1	120.63 (13)	C3—C8—H8	120.7
O1—C1—C11	121.46 (13)	C16—C11—C12	119.59 (14)
N1—C1—C11	117.86 (12)	C16—C11—C1	124.15 (13)
C2—N2—C3	109.98 (12)	C12—C11—C1	116.03 (12)
N2—C2—N1	120.53 (13)	C13—C12—C11	119.64 (13)
N2—C2—S1	117.01 (11)	C13—C12—H12	120.2
N1—C2—S1	122.45 (11)	C11—C12—H12	120.2
N2—C3—C8	125.53 (13)	C12—C13—C14	121.49 (14)
N2—C3—C4	114.62 (13)	C12—C13—Cl1	118.93 (12)
C8—C3—C4	119.85 (14)	C14—C13—Cl1	119.52 (12)
C5—C4—C3	121.38 (14)	C13—C14—C15	118.48 (14)
C5—C4—S1	128.30 (12)	C13—C14—H14	120.8
C3—C4—S1	110.32 (11)	C15—C14—H14	120.8
C6—C5—C4	117.87 (15)	C16—C15—C14	121.08 (14)
C6—C5—H5	121.1	C16—C15—H15	119.5
C4—C5—H5	121.1	C14—C15—H15	119.5
C5—C6—C7	121.06 (14)	C15—C16—C11	119.71 (13)
C5—C6—H6	119.5	C15—C16—H16	120.1
C7—C6—H6	119.5	C11—C16—H16	120.1
C8—C7—C6	121.19 (15)

C2—N1—C1—O1	−2.6 (2)	C5—C6—C7—C8	−1.2 (2)
C2—N1—C1—C11	174.90 (12)	C6—C7—C8—C3	0.3 (2)
C3—N2—C2—N1	−177.62 (12)	N2—C3—C8—C7	−178.45 (14)
C3—N2—C2—S1	1.43 (16)	C4—C3—C8—C7	0.9 (2)
C1—N1—C2—N2	−171.57 (13)	O1—C1—C11—C16	165.51 (14)
C1—N1—C2—S1	9.43 (19)	N1—C1—C11—C16	−11.9 (2)
C4—S1—C2—N2	−1.80 (12)	O1—C1—C11—C12	−8.9 (2)
C4—S1—C2—N1	177.23 (12)	N1—C1—C11—C12	173.61 (12)
C2—N2—C3—C8	179.29 (14)	C16—C11—C12—C13	0.5 (2)
C2—N2—C3—C4	−0.12 (18)	C1—C11—C12—C13	175.22 (13)
N2—C3—C4—C5	178.08 (13)	C11—C12—C13—C14	−1.1 (2)
C8—C3—C4—C5	−1.4 (2)	C11—C12—C13—Cl1	−178.45 (11)
N2—C3—C4—S1	−1.19 (16)	C12—C13—C14—C15	0.7 (2)
C8—C3—C4—S1	179.37 (11)	Cl1—C13—C14—C15	178.04 (12)
C2—S1—C4—C5	−177.64 (15)	C13—C14—C15—C16	0.3 (2)
C2—S1—C4—C3	1.56 (11)	C14—C15—C16—C11	−0.8 (2)
C3—C4—C5—C6	0.5 (2)	C12—C11—C16—C15	0.4 (2)
S1—C4—C5—C6	179.62 (12)	C1—C11—C16—C15	−173.83 (14)
C4—C5—C6—C7	0.8 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N2ⁱ	0.94 (2)	2.02 (2)	2.9429 (18)	168.9 (17)

Symmetry code: (i) −x+1, y, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₁₄H₉ClN₂OS
M_r	288.74
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	173
a, b, c (Å)	26.6613 (19), 7.5766 (5), 12.6729 (10)
β (°)	99.729 (6)
V (Å³)	2523.1 (3)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.46
Crystal size (mm)	0.39 × 0.38 × 0.35

Data collection
Diffractometer	Stoe IPDS II two-circle diffractometer
Absorption correction	Multi-scan [MULABS (Spek, 2009); Blessing, 1995)]
T_min, T_max	0.841, 0.856
No. of measured, independent and observed [I > 2σ(I)] reflections	9132, 2352, 2084
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.608

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.079, 1.03
No. of reflections	2352
No. of parameters	177
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.23

Computer programs: X-AREA (Stoe & Cie, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and XP in SHELXTL-Plus (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N2ⁱ	0.94 (2)	2.02 (2)	2.9429 (18)	168.9 (17)

Symmetry code: (i) −x+1, y, −z+3/2.

Acknowledgements

MKR is grateful to the HEC, Pakistan, for financial support of the PhD program under scholarship No. ILC-0363104.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Blessing, R. H. (1995). Acta Cryst. A51, 33–38. CrossRef CAS Web of Science IUCr Journals Google Scholar
Garden, S. J., Glidewell, C., Low, J. N., Skakle, J. M. S. & Wardell, J. L. (2005). Acta Cryst. C61, o450–o451. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stoe & Cie (2001). X-AREA. Stoe & Cie, Darmstadt, Germany. Google Scholar
Wardell, J. L., Skakle, J. M. S., Low, J. N. & Glidewell, C. (2005). Acta Cryst. C61, o634–o638. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar