Crystal structure of N-(4-chloro­phen­yl)benzo­thio­amide

Zhao, G.

doi:10.1107/S2056989015008075

organic compounds

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Volume 71| Part 5| May 2015| Page o353

https://doi.org/10.1107/S2056989015008075

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Crystal structure of N-(4-chlorophenyl)benzothioamide

Ganlin Zhao ^a ^*

^aChangsha Environmental Protection College, Changsha 410004, People's Republic of China
^*Correspondence e-mail: hbxygcx2011@126.com

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 20 April 2015; accepted 23 April 2015; online 30 April 2015)

The title compound, C₁₃H₁₀ClNS, exhibits a trans conformation with regard to the axis of the C—N bond. The benzene and phenyl rings are inclined to one another by 85.06 (8)°. In the crystal, molecules are linked by N—H⋯S=C hydrogen bonds, forming chains along [001].

Keywords: crystal structure; benzothioamide; N—H⋯S hydrogen bonding..

CCDC reference: 1061304

1. Related literature

For hydrogen bonding of amides, see: Taylor et al. (1984 ); Leiserowitz & Schmidt (1969 ). For the preparation and for the use of thioamides as intermediates in chemical transformations, see: Li et al. (2012 , 2015 ). For related structures, see: Omondi et al. (2012 ); Nagasawa et al. (2014 ).

2. Experimental

2.1. Crystal data

C₁₃H₁₀ClNS
M_r = 247.73
Monoclinic, P 2₁ /c
a = 11.943 (2) Å
b = 12.689 (3) Å
c = 7.9764 (16) Å
β = 109.30 (3)°
V = 1140.9 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.49 mm⁻¹
T = 113 K
0.22 × 0.20 × 0.12 mm

2.2. Data collection

Rigaku Saturn CCD area-detector diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ) T_min = 0.901, T_max = 0.944
7517 measured reflections
2010 independent reflections
1701 reflections with I > 2σ(I)
R_int = 0.030

2.3. Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.077
S = 1.05
2010 reflections
150 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 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—H1⋯S1ⁱ	0.89 (1)	2.49 (1)	3.346 (15)	163 (1)
Symmetry code: (i) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

CCDC reference: 1061304

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989015008075/su5123sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015008075/su5123Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989015008075/su5123Isup3.cml

checkCIF report

Comment top

Thioamides are extensively used as extractant for heavy metals in environmental chemistry, as intermediate for important chemical transformations (Li et al., 2015), and also used to replace the amide bonds as isosteres. It's well known that amide units can be connected by a N—H···O=C hydrogen bonds (Taylor et al., 1984; Leiserowitz & Schmidt, 1969), and also the structures of some thioamides have been documented (Omondi et al., 2012; Nagasawa et al., 2014). Herein, we report the crystal structure of the title compound (I).

Figure 1 has shows the molecular structure of the title compound, whose thioamide unit adopts a trans conformation around the central C-N bond. The C=S double bond is deviated from its connected phenyl ring [torsion angles: S1/C7/C8/C9 -145.34 (13)°,S1/C7/C8/C13 33.62 (19)°]. The benzene and phenyl rings are inclined to one another by 85.06 (8) °.

In the crystal, molecules are linked via N—H···S═C hydrogen bonds, forming chains along the c axis direction (Table 1 and Fig. 2).

Related literature top

For hydrogen bonding of amides, see: Taylor et al. (1984); Leiserowitz & Schmidt (1969). For the preparation and for the use of thioamides as intermediates in chemical transformations, see: Li et al. (2012, 2015). For related structures, see: Omondi et al. (2012); Nagasawa et al. (2014).

Experimental top

The title compound was prepared from the Beckmann rearrangement from its corresponding ketoximes following a published procedure (Li et al., 2012). It was isolated by flash chromatography and yellow block-like crystal of the title compound were obtained via natural evaporation from the diluent.

Structure description top

In the crystal, molecules are linked via N—H···S═C hydrogen bonds, forming chains along the c axis direction (Table 1 and Fig. 2).

For hydrogen bonding of amides, see: Taylor et al. (1984); Leiserowitz & Schmidt (1969). For the preparation and for the use of thioamides as intermediates in chemical transformations, see: Li et al. (2012, 2015). For related structures, see: Omondi et al. (2012); Nagasawa et al. (2014).

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A view along the b axis of the crystal packing of the title compound. The N—H···S hydrogen bonds are shown as dashed lines (see Table 1 for details).

N-(4-Chlorophenyl)benzothioamide top

Crystal data top

C₁₃H₁₀ClNS	F(000) = 512
M_r = 247.73	D_x = 1.442 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3499 reflections
a = 11.943 (2) Å	θ = 1.8–27.9°
b = 12.689 (3) Å	µ = 0.49 mm⁻¹
c = 7.9764 (16) Å	T = 113 K
β = 109.30 (3)°	Block, yellow
V = 1140.9 (4) Å³	0.22 × 0.20 × 0.12 mm
Z = 4

Data collection top

Rigaku Saturn CCD area-detector diffractometer	2010 independent reflections
Radiation source: rotating anode	1701 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.030
Detector resolution: 7.31 pixels mm^-1	θ_max = 25.0°, θ_min = 2.4°
ω and φ scans	h = −11→14
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −15→15
T_min = 0.901, T_max = 0.944	l = −9→9
7517 measured reflections

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) = 0.077	w = 1/[σ²(F_o²) + (0.0477P)² + 0.1743P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.002
2010 reflections	Δρ_max = 0.22 e Å⁻³
150 parameters	Δρ_min = −0.18 e Å⁻³
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.050 (4)

Crystal data top

C₁₃H₁₀ClNS	V = 1140.9 (4) Å³
M_r = 247.73	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.943 (2) Å	µ = 0.49 mm⁻¹
b = 12.689 (3) Å	T = 113 K
c = 7.9764 (16) Å	0.22 × 0.20 × 0.12 mm
β = 109.30 (3)°

Data collection top

Rigaku Saturn CCD area-detector diffractometer	2010 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	1701 reflections with I > 2σ(I)
T_min = 0.901, T_max = 0.944	R_int = 0.030
7517 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	1 restraint
wR(F²) = 0.077	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.22 e Å⁻³
2010 reflections	Δρ_min = −0.18 e Å⁻³
150 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
S1	0.94504 (4)	0.58973 (3)	1.20150 (5)	0.01919 (16)
Cl1	1.47747 (4)	0.84240 (4)	1.54329 (6)	0.02760 (17)
N1	1.02619 (11)	0.71403 (10)	0.99722 (17)	0.0160 (3)
C1	1.13474 (13)	0.74209 (12)	1.1311 (2)	0.0159 (3)
C2	1.21244 (14)	0.66609 (13)	1.2321 (2)	0.0201 (4)
H2	1.1936	0.5949	1.2147	0.024*
C3	1.31777 (14)	0.69722 (13)	1.3583 (2)	0.0218 (4)
H3	1.3698	0.6470	1.4264	0.026*
C4	1.34551 (14)	0.80302 (13)	1.3828 (2)	0.0186 (4)
C5	1.26984 (15)	0.87901 (13)	1.2816 (2)	0.0219 (4)
H5	1.2895	0.9501	1.2982	0.026*
C6	1.16448 (15)	0.84782 (13)	1.1550 (2)	0.0194 (4)
H6	1.1134	0.8982	1.0857	0.023*
C7	0.94159 (14)	0.64895 (12)	1.0128 (2)	0.0159 (4)
C8	0.83987 (14)	0.63239 (12)	0.8467 (2)	0.0161 (4)
C9	0.85648 (15)	0.62942 (12)	0.6821 (2)	0.0182 (4)
H9	0.9320	0.6389	0.6751	0.022*
C10	0.76076 (16)	0.61237 (13)	0.5280 (2)	0.0226 (4)
H10	0.7725	0.6106	0.4184	0.027*
C11	0.64826 (16)	0.59810 (13)	0.5376 (2)	0.0249 (4)
H11	0.5842	0.5868	0.4347	0.030*
C12	0.63130 (15)	0.60079 (13)	0.7015 (2)	0.0251 (4)
H12	0.5557	0.5910	0.7082	0.030*
C13	0.72593 (14)	0.61784 (12)	0.8545 (2)	0.0201 (4)
H13	0.7137	0.6197	0.9637	0.024*
H1	1.0058 (16)	0.7552 (13)	0.9013 (17)	0.030 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0205 (2)	0.0192 (2)	0.0179 (3)	−0.00251 (17)	0.00650 (18)	0.00248 (16)
Cl1	0.0174 (2)	0.0353 (3)	0.0268 (3)	−0.00442 (18)	0.00281 (18)	−0.00048 (18)
N1	0.0177 (7)	0.0151 (7)	0.0155 (7)	−0.0010 (6)	0.0057 (6)	0.0010 (6)
C1	0.0158 (8)	0.0181 (8)	0.0164 (8)	−0.0003 (7)	0.0090 (7)	−0.0010 (6)
C2	0.0187 (9)	0.0154 (8)	0.0280 (9)	0.0004 (7)	0.0102 (7)	0.0010 (7)
C3	0.0170 (8)	0.0215 (9)	0.0279 (10)	0.0042 (7)	0.0089 (7)	0.0066 (7)
C4	0.0138 (8)	0.0245 (9)	0.0186 (8)	−0.0014 (7)	0.0070 (7)	−0.0008 (7)
C5	0.0231 (9)	0.0177 (8)	0.0249 (9)	−0.0026 (7)	0.0081 (8)	−0.0024 (7)
C6	0.0192 (9)	0.0175 (8)	0.0211 (9)	0.0029 (7)	0.0063 (7)	0.0016 (6)
C7	0.0173 (8)	0.0118 (7)	0.0210 (9)	0.0028 (6)	0.0096 (7)	−0.0021 (6)
C8	0.0186 (8)	0.0098 (7)	0.0201 (8)	0.0007 (6)	0.0065 (7)	−0.0005 (6)
C9	0.0202 (9)	0.0133 (8)	0.0223 (9)	−0.0018 (7)	0.0085 (7)	0.0000 (7)
C10	0.0300 (10)	0.0194 (8)	0.0186 (9)	−0.0017 (8)	0.0081 (8)	−0.0018 (7)
C11	0.0234 (9)	0.0257 (9)	0.0202 (9)	−0.0010 (8)	0.0001 (7)	−0.0017 (7)
C12	0.0171 (9)	0.0280 (9)	0.0285 (10)	0.0010 (8)	0.0052 (7)	0.0009 (8)
C13	0.0192 (9)	0.0210 (9)	0.0212 (9)	0.0019 (7)	0.0080 (7)	0.0011 (7)

Geometric parameters (Å, º) top

S1—C7	1.6705 (16)	C6—H6	0.9300
Cl1—C4	1.7430 (17)	C7—C8	1.487 (2)
N1—C7	1.342 (2)	C8—C9	1.391 (2)
N1—C1	1.426 (2)	C8—C13	1.395 (2)
N1—H1	0.891 (9)	C9—C10	1.392 (2)
C1—C6	1.385 (2)	C9—H9	0.9300
C1—C2	1.395 (2)	C10—C11	1.383 (2)
C2—C3	1.384 (2)	C10—H10	0.9300
C2—H2	0.9300	C11—C12	1.388 (3)
C3—C4	1.381 (2)	C11—H11	0.9300
C3—H3	0.9300	C12—C13	1.379 (2)
C4—C5	1.384 (2)	C12—H12	0.9300
C5—C6	1.385 (2)	C13—H13	0.9300
C5—H5	0.9300

C7—N1—C1	127.60 (13)	N1—C7—C8	115.00 (13)
C7—N1—H1	116.1 (12)	N1—C7—S1	124.40 (13)
C1—N1—H1	114.8 (12)	C8—C7—S1	120.59 (12)
C6—C1—C2	119.92 (15)	C9—C8—C13	118.95 (15)
C6—C1—N1	118.25 (14)	C9—C8—C7	121.01 (15)
C2—C1—N1	121.77 (14)	C13—C8—C7	120.03 (15)
C3—C2—C1	119.60 (15)	C8—C9—C10	120.42 (16)
C3—C2—H2	120.2	C8—C9—H9	119.8
C1—C2—H2	120.2	C10—C9—H9	119.8
C4—C3—C2	119.90 (15)	C11—C10—C9	120.03 (16)
C4—C3—H3	120.0	C11—C10—H10	120.0
C2—C3—H3	120.0	C9—C10—H10	120.0
C3—C4—C5	120.96 (15)	C10—C11—C12	119.76 (16)
C3—C4—Cl1	119.94 (13)	C10—C11—H11	120.1
C5—C4—Cl1	119.09 (13)	C12—C11—H11	120.1
C4—C5—C6	119.13 (15)	C13—C12—C11	120.34 (16)
C4—C5—H5	120.4	C13—C12—H12	119.8
C6—C5—H5	120.4	C11—C12—H12	119.8
C1—C6—C5	120.46 (15)	C12—C13—C8	120.50 (16)
C1—C6—H6	119.8	C12—C13—H13	119.7
C5—C6—H6	119.8	C8—C13—H13	119.7

C7—N1—C1—C6	−131.37 (16)	C1—N1—C7—S1	2.6 (2)
C7—N1—C1—C2	51.1 (2)	N1—C7—C8—C9	35.2 (2)
C6—C1—C2—C3	1.3 (2)	S1—C7—C8—C9	−145.34 (13)
N1—C1—C2—C3	178.80 (14)	N1—C7—C8—C13	−145.86 (15)
C1—C2—C3—C4	−0.3 (2)	S1—C7—C8—C13	33.62 (19)
C2—C3—C4—C5	−0.7 (2)	C13—C8—C9—C10	0.1 (2)
C2—C3—C4—Cl1	179.35 (12)	C7—C8—C9—C10	179.08 (14)
C3—C4—C5—C6	0.5 (2)	C8—C9—C10—C11	−0.1 (2)
Cl1—C4—C5—C6	−179.46 (12)	C9—C10—C11—C12	0.0 (2)
C2—C1—C6—C5	−1.5 (2)	C10—C11—C12—C13	0.2 (3)
N1—C1—C6—C5	−179.01 (14)	C11—C12—C13—C8	−0.1 (2)
C4—C5—C6—C1	0.5 (2)	C9—C8—C13—C12	0.0 (2)
C1—N1—C7—C8	−177.96 (13)	C7—C8—C13—C12	−178.98 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1ⁱ	0.89 (1)	2.49 (1)	3.346 (15)	163 (1)

Symmetry code: (i) x, −y+3/2, z−1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1ⁱ	0.891 (14)	2.485 (14)	3.346 (15)	162.50 (13)

Symmetry code: (i) x, −y+3/2, z−1/2.

References

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ISSN: 2056-9890

Volume 71| Part 5| May 2015| Page o353

https://doi.org/10.1107/S2056989015008075

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