N-Benzyl­carbamothioyl-2-chloro­benzamide

Zheng, X.; Li, B.; Wang, Q.; Guo, L.

doi:10.1107/S1600536810023822

organic compounds

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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Page o1774

doi:10.1107/S1600536810023822

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N-Benzylcarbamothioyl-2-chlorobenzamide

Xi Zheng,^a Bo Li,^a Qiang Wang ^a and Li Guo ^a ^*

^aKey Laboratory of Drug Targeting and Drug Delivery Systems, Ministry of Education, West China School of Pharmacy, Sichuan University, Chengdu 610041, People's Republic of China
^*Correspondence e-mail: rosaguoli@163.com

(Received 3 June 2010; accepted 19 June 2010; online 26 June 2010)

In the title compound, C₁₅H₁₃ClN₂OS, the dihedral angles between the sulfourea group and the benzene ring and the chlorobenzene ring are 35.8 (6) and 81.6 (6)° respectively. An intramolecular N—H⋯O interaction occurs. In the crystal, a combination of intermolecular π–π stacking interactions [centroid–centroid distance = 4.0616 (16) Å] and N—H⋯S hydrogen bonds stabilizes the structure.

Related literature

For general background to the chemistry and biological activity of thiourea derivatives and their use, see: Jain & Rao (2003 ); Zeng et al. (2003 ); Xu et al. (2004 ); Zheng et al. (2004 ); D'hooghe et al. (2005 ); Saeed et al. (2008 , 2009 , 2010 ).

Experimental

Crystal data

C₁₅H₁₃ClN₂OS
M_r = 304.78
Triclinic, $[P \overline 1]$
a = 7.347 (2) Å
b = 9.658 (3) Å
c = 11.003 (3) Å
α = 110.150 (5)°
β = 90.767 (3)°
γ = 104.058 (3)°
V = 707.0 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.41 mm⁻¹
T = 153 K
0.40 × 0.30 × 0.30 mm

Data collection

Rigaku AFC10/Saturn724+ diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.852, T_max = 0.886
5691 measured reflections
2481 independent reflections
2194 reflections with I > 2σ(I)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.073
S = 1.01
2481 reflections
189 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯S1ⁱ	0.86 (2)	2.53 (2)	3.3698 (18)	166.2 (18)
N2—H2N⋯O1	0.82 (2)	2.01 (2)	2.669 (2)	137 (2)
Symmetry code: (i) -x+2, -y+1, -z.

Data collection: CrystalClear (Rigaku/MSC, 2005 ); 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: ORTEPIII (Burnett & Johnson, 1996 ); software used to prepare material for publication: PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810023822/pk2248sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810023822/pk2248Isup2.hkl

checkCIF report

Comment top

N-(benzylcarbamothioyl)-2-chlorobenzamide derivatives are of great importance owing to their wide-ranging biological properties (Zeng et al. (2003)). The title compound is one of the key intermediates in our synthetic investigations of antiviral drugs. We report here its crystal structure. As shown in Fig. 1, the dihedral angle of 35.8 (6)° and 81.6 (6)° between the connecting sulfourea unit and the benzene ring, and between the 2-chloro-benzene ring and the connecting sulfourea group, respectively. A combination of intermolecular π-π packing interaction, N—H···O and N—H···S hydrogen bonds help stabilize the structure. In addition, weak C—H···π interactions are also present.

Related literature top

For general background to the chemistry and biological activity of thiourea derivatives and their use, see: Jain & Rao (2003); Zeng et al. (2003); Xu et al. (2004); Zheng et al. (2004); D'hooghe et al. (2005); Saeed et al. (2008, 2009, 2010).

Experimental top

A solution of 0.23 g (3 mmol) of ammonium thiocyanate in 7 ml of acetonitrile was added to a solution of 0.52 g (3 mmol) of 2-chlorobenzoyl chloride in 2.5 ml of toluene. The mixture was heated for 5 min at 40°C and filtered from ammonium chloride, the filtrate was added to a solution of 0.32 g (3 mmol) of phenylmethanamine in 5 ml of acetonitrile, the mixture was stirred for 3 h at room temperature and evaporated, and the residue was washed with ethanol and recrystallized from ethanol. Yield 0.77 g (85%). Crystals suitable for X-ray analysis were obtained by slow evaporation from a solution of dichloromethane.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level.

N-Benzylcarbamothioyl-2-chlorobenzamide top

Crystal data top

C₁₅H₁₃ClN₂OS	Z = 2
M_r = 304.78	F(000) = 316
Triclinic, P1	D_x = 1.432 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.347 (2) Å	Cell parameters from 2259 reflections
b = 9.658 (3) Å	θ = 3.2–27.5°
c = 11.003 (3) Å	µ = 0.41 mm⁻¹
α = 110.150 (5)°	T = 153 K
β = 90.767 (3)°	Block, colorless
γ = 104.058 (3)°	0.40 × 0.30 × 0.30 mm
V = 707.0 (4) Å³

Data collection top

Rigaku AFC10/Saturn724+ diffractometer	2481 independent reflections
Radiation source: Rotating Anode	2194 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
Detector resolution: 28.6 pixels mm^-1	θ_max = 25.3°, θ_min = 3.2°
ϕ and ω scans	h = −8→8
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −11→11
T_min = 0.852, T_max = 0.886	l = −13→13
5691 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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.073	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ²(F_o²) + (0.0368P)² + 0.265P] where P = (F_o² + 2F_c²)/3
2481 reflections	(Δ/σ)_max < 0.001
189 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₁₅H₁₃ClN₂OS	γ = 104.058 (3)°
M_r = 304.78	V = 707.0 (4) Å³
Triclinic, P1	Z = 2
a = 7.347 (2) Å	Mo Kα radiation
b = 9.658 (3) Å	µ = 0.41 mm⁻¹
c = 11.003 (3) Å	T = 153 K
α = 110.150 (5)°	0.40 × 0.30 × 0.30 mm
β = 90.767 (3)°

Data collection top

Rigaku AFC10/Saturn724+ diffractometer	2481 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	2194 reflections with I > 2σ(I)
T_min = 0.852, T_max = 0.886	R_int = 0.017
5691 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.073	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.23 e Å⁻³
2481 reflections	Δρ_min = −0.18 e Å⁻³
189 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	0.69955 (6)	0.10088 (5)	0.08296 (4)	0.03365 (14)
S1	0.81096 (6)	0.64421 (5)	0.00524 (4)	0.02590 (13)
O1	0.71779 (16)	0.46704 (14)	0.34073 (11)	0.0283 (3)
N1	0.84005 (19)	0.48399 (15)	0.15434 (13)	0.0203 (3)
N2	0.62797 (19)	0.63073 (16)	0.20842 (13)	0.0219 (3)
C1	0.9133 (2)	0.18430 (18)	0.18156 (14)	0.0202 (3)
C2	1.0373 (2)	0.09656 (19)	0.18009 (15)	0.0243 (4)
H2	1.0062	−0.0087	0.1267	0.029*
C3	1.2074 (2)	0.1651 (2)	0.25780 (16)	0.0264 (4)
H3	1.2953	0.1069	0.2562	0.032*
C4	1.2512 (2)	0.3177 (2)	0.33806 (16)	0.0261 (4)
H4	1.3678	0.3632	0.3919	0.031*
C5	1.1247 (2)	0.40367 (18)	0.33975 (15)	0.0226 (3)
H5	1.1539	0.5079	0.3956	0.027*
C6	0.9550 (2)	0.33762 (17)	0.25978 (14)	0.0181 (3)
C7	0.8239 (2)	0.43410 (17)	0.25728 (15)	0.0192 (3)
C8	0.7526 (2)	0.58559 (17)	0.12955 (14)	0.0193 (3)
C9	0.5298 (2)	0.74124 (19)	0.19805 (16)	0.0254 (4)
H9A	0.4528	0.6995	0.1126	0.030*
H9B	0.6234	0.8366	0.2031	0.030*
C10	0.4041 (2)	0.77650 (17)	0.30540 (15)	0.0201 (3)
C11	0.4601 (2)	0.79494 (18)	0.43245 (15)	0.0227 (3)
H11	0.5805	0.7838	0.4530	0.027*
C12	0.3419 (2)	0.82945 (18)	0.52955 (16)	0.0253 (4)
H12	0.3805	0.8400	0.6158	0.030*
C13	0.1679 (2)	0.84838 (18)	0.50053 (17)	0.0279 (4)
H13	0.0868	0.8722	0.5668	0.033*
C14	0.1120 (2)	0.83262 (19)	0.37480 (17)	0.0285 (4)
H14	−0.0065	0.8474	0.3552	0.034*
C15	0.2287 (2)	0.79521 (19)	0.27727 (16)	0.0248 (4)
H15	0.1884	0.7823	0.1907	0.030*
H1N	0.924 (3)	0.459 (2)	0.1044 (18)	0.030 (5)*
H2N	0.605 (3)	0.593 (2)	0.2644 (19)	0.032 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0275 (2)	0.0300 (2)	0.0343 (3)	0.00316 (18)	−0.00924 (18)	0.00382 (19)
S1	0.0321 (2)	0.0347 (3)	0.0234 (2)	0.01932 (19)	0.01270 (17)	0.01826 (19)
O1	0.0315 (7)	0.0388 (7)	0.0274 (6)	0.0197 (6)	0.0153 (5)	0.0201 (6)
N1	0.0235 (7)	0.0238 (7)	0.0197 (7)	0.0131 (6)	0.0087 (6)	0.0103 (6)
N2	0.0253 (7)	0.0261 (7)	0.0240 (7)	0.0137 (6)	0.0106 (6)	0.0158 (6)
C1	0.0195 (8)	0.0234 (8)	0.0171 (8)	0.0041 (6)	0.0018 (6)	0.0077 (7)
C2	0.0319 (9)	0.0219 (8)	0.0223 (8)	0.0115 (7)	0.0074 (7)	0.0086 (7)
C3	0.0250 (9)	0.0334 (9)	0.0304 (9)	0.0158 (7)	0.0087 (7)	0.0176 (8)
C4	0.0183 (8)	0.0344 (9)	0.0298 (9)	0.0058 (7)	0.0004 (7)	0.0175 (8)
C5	0.0233 (8)	0.0213 (8)	0.0228 (8)	0.0030 (7)	0.0018 (6)	0.0095 (7)
C6	0.0194 (8)	0.0211 (8)	0.0171 (8)	0.0062 (6)	0.0062 (6)	0.0103 (7)
C7	0.0193 (8)	0.0198 (8)	0.0187 (8)	0.0041 (6)	0.0027 (6)	0.0080 (7)
C8	0.0200 (8)	0.0195 (8)	0.0189 (8)	0.0065 (6)	0.0025 (6)	0.0066 (7)
C9	0.0302 (9)	0.0292 (9)	0.0269 (9)	0.0174 (7)	0.0105 (7)	0.0157 (8)
C10	0.0223 (8)	0.0159 (7)	0.0248 (8)	0.0066 (6)	0.0066 (6)	0.0095 (7)
C11	0.0216 (8)	0.0228 (8)	0.0262 (9)	0.0071 (7)	0.0036 (6)	0.0108 (7)
C12	0.0308 (9)	0.0222 (8)	0.0226 (8)	0.0061 (7)	0.0059 (7)	0.0082 (7)
C13	0.0293 (9)	0.0228 (9)	0.0325 (10)	0.0089 (7)	0.0150 (7)	0.0094 (8)
C14	0.0207 (9)	0.0278 (9)	0.0393 (10)	0.0115 (7)	0.0066 (7)	0.0114 (8)
C15	0.0259 (9)	0.0256 (8)	0.0259 (9)	0.0109 (7)	0.0029 (7)	0.0101 (7)

Geometric parameters (Å, º) top

Cl1—C1	1.7409 (16)	C5—C6	1.390 (2)
S1—C8	1.6752 (16)	C5—H5	0.9500
O1—C7	1.2207 (19)	C6—C7	1.500 (2)
N1—C7	1.371 (2)	C9—C10	1.506 (2)
N1—C8	1.3913 (19)	C9—H9A	0.9900
N1—H1N	0.85 (2)	C9—H9B	0.9900
N2—C8	1.318 (2)	C10—C15	1.389 (2)
N2—C9	1.459 (2)	C10—C11	1.390 (2)
N2—H2N	0.82 (2)	C11—C12	1.388 (2)
C1—C2	1.383 (2)	C11—H11	0.9500
C1—C6	1.386 (2)	C12—C13	1.383 (2)
C2—C3	1.382 (2)	C12—H12	0.9500
C2—H2	0.9500	C13—C14	1.384 (3)
C3—C4	1.386 (2)	C13—H13	0.9500
C3—H3	0.9500	C14—C15	1.387 (2)
C4—C5	1.385 (2)	C14—H14	0.9500
C4—H4	0.9500	C15—H15	0.9500

C7—N1—C8	127.85 (13)	N2—C8—N1	116.48 (14)
C7—N1—H1N	116.5 (13)	N2—C8—S1	124.11 (12)
C8—N1—H1N	115.2 (13)	N1—C8—S1	119.41 (11)
C8—N2—C9	122.95 (14)	N2—C9—C10	110.88 (13)
C8—N2—H2N	117.3 (13)	N2—C9—H9A	109.5
C9—N2—H2N	119.8 (13)	C10—C9—H9A	109.5
C2—C1—C6	121.61 (15)	N2—C9—H9B	109.5
C2—C1—Cl1	119.44 (13)	C10—C9—H9B	109.5
C6—C1—Cl1	118.95 (12)	H9A—C9—H9B	108.1
C3—C2—C1	118.67 (15)	C15—C10—C11	118.98 (14)
C3—C2—H2	120.7	C15—C10—C9	118.94 (14)
C1—C2—H2	120.7	C11—C10—C9	122.06 (14)
C2—C3—C4	120.76 (15)	C12—C11—C10	120.64 (15)
C2—C3—H3	119.6	C12—C11—H11	119.7
C4—C3—H3	119.6	C10—C11—H11	119.7
C5—C4—C3	119.94 (15)	C13—C12—C11	119.88 (16)
C5—C4—H4	120.0	C13—C12—H12	120.1
C3—C4—H4	120.0	C11—C12—H12	120.1
C4—C5—C6	120.07 (15)	C12—C13—C14	119.91 (15)
C4—C5—H5	120.0	C12—C13—H13	120.0
C6—C5—H5	120.0	C14—C13—H13	120.0
C1—C6—C5	118.92 (14)	C13—C14—C15	120.18 (15)
C1—C6—C7	121.51 (14)	C13—C14—H14	119.9
C5—C6—C7	119.54 (14)	C15—C14—H14	119.9
O1—C7—N1	124.11 (14)	C14—C15—C10	120.39 (15)
O1—C7—C6	122.83 (13)	C14—C15—H15	119.8
N1—C7—C6	113.03 (13)	C10—C15—H15	119.8

C6—C1—C2—C3	−0.7 (2)	C5—C6—C7—N1	98.18 (17)
Cl1—C1—C2—C3	179.23 (12)	C9—N2—C8—N1	177.65 (14)
C1—C2—C3—C4	1.6 (2)	C9—N2—C8—S1	−1.7 (2)
C2—C3—C4—C5	−0.8 (2)	C7—N1—C8—N2	−5.7 (2)
C3—C4—C5—C6	−0.8 (2)	C7—N1—C8—S1	173.68 (13)
C2—C1—C6—C5	−0.9 (2)	C8—N2—C9—C10	−177.02 (15)
Cl1—C1—C6—C5	179.18 (11)	N2—C9—C10—C15	−141.11 (15)
C2—C1—C6—C7	177.52 (14)	N2—C9—C10—C11	40.6 (2)
Cl1—C1—C6—C7	−2.4 (2)	C15—C10—C11—C12	0.9 (2)
C4—C5—C6—C1	1.6 (2)	C9—C10—C11—C12	179.12 (15)
C4—C5—C6—C7	−176.77 (14)	C10—C11—C12—C13	−1.1 (2)
C8—N1—C7—O1	4.5 (3)	C11—C12—C13—C14	0.1 (2)
C8—N1—C7—C6	−173.81 (14)	C12—C13—C14—C15	1.1 (3)
C1—C6—C7—O1	101.52 (19)	C13—C14—C15—C10	−1.4 (3)
C5—C6—C7—O1	−80.1 (2)	C11—C10—C15—C14	0.4 (2)
C1—C6—C7—N1	−80.19 (18)	C9—C10—C15—C14	−177.92 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···S1ⁱ	0.86 (2)	2.53 (2)	3.3698 (18)	166.2 (18)
N2—H2N···O1	0.82 (2)	2.01 (2)	2.669 (2)	137 (2)

Symmetry code: (i) −x+2, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₃ClN₂OS
M_r	304.78
Crystal system, space group	Triclinic, P1
Temperature (K)	153
a, b, c (Å)	7.347 (2), 9.658 (3), 11.003 (3)
α, β, γ (°)	110.150 (5), 90.767 (3), 104.058 (3)
V (Å³)	707.0 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.41
Crystal size (mm)	0.40 × 0.30 × 0.30

Data collection
Diffractometer	Rigaku AFC10/Saturn724+ diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.852, 0.886
No. of measured, independent and observed [I > 2σ(I)] reflections	5691, 2481, 2194
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.073, 1.01
No. of reflections	2481
No. of parameters	189
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.18

Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···S1ⁱ	0.86 (2)	2.53 (2)	3.3698 (18)	166.2 (18)
N2—H2N···O1	0.82 (2)	2.01 (2)	2.669 (2)	137 (2)

Symmetry code: (i) −x+2, −y+1, −z.

Acknowledgements

We thank the Analytical and Testing Center of Sichuan University for the X-ray measurements.

References

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