S-2-Amino­phenyl phenyl­carbamo­thio­ate

Öztürk Yıldırım, S.; Butcher, R.J.

doi:10.1107/S2414314618000627

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 3| Part 1| January 2018| x180062

https://doi.org/10.1107/S2414314618000627

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S-2-Aminophenyl phenylcarbamothioate

Sema Öztürk Yıldırım ^a ^* and Ray J. Butcher ^b

^aDepartment of Physics, Faculty of Sciences, Erciyes University, Kayseri 38039, Turkey, and ^bDepartment of Chemistry, Howard University, Washington DC 20059, USA
^*Correspondence e-mail: ozturk@erciyes.edu.tr

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 21 December 2017; accepted 10 January 2018; online 12 January 2018)

In the title compound, C₁₃H₁₂N₂OS, which was obtained from the condensation reaction of 2-aminobenzenethiol with isocyanatobenzene, the benzene rings are inclined to one another by 83.5 (1)° and a short intramolecular C—H⋯O contact is observed. In the crystal, molecules are linked by N—H⋯O and N—H⋯N hydrogen bonds, generating (001) sheets.

Keywords: crystal structure; thiol; phenylcarbamothioate.

CCDC reference: 1539765

Structure description

Organic carbamothioates are a class of compounds that play an important role in the synthesis of pharmaceuticals and agricultural chemicals (Torrico-Vallejos et al., 2011 ; Belkhir et al., 2015 ). As part of our studies in this area, the title compound (Fig. 1) was obtained from the condensation reaction of 2-aminobenzenethiol with isocyanatobenzene.

Figure 1
The molecular structure with displacement ellipsoids drawn at the 50% probability level. H atoms are drawn as circles of arbitrary size.

The dihedral angle between the aromatic rings is 83.5 (1)° and the major twist occurs about the C6—S1 bond [C1—C6—S1—C7 = 87.6 (2)°]. The C—S bond distances are comparable with those in related structures [average C—S = 1.778 (6) Å in S-phenyl 4-methoxybenzothioate (El-Azab et al., 2012 ) and 1.7733 (2) Å in ethane-1,2-diyl bis(benzenedithioate) (Abe et al., 2011 )]. The least-squares plane through the S-methyl methylcarbamothioate unit (S1/C7/O1/N2) makes dihedral angles of 88.3 (1) and 6.9 (1)° with the C1–C6 and C8–C13 benzene rings, respectively.

In the crystal, N—H⋯O and N—H⋯N hydrogen bonds connect the molecules into (001) sheets (Fig. 2, Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13A⋯O1	0.95	2.32	2.928 (4)	121
N1—H1N2⋯O1ⁱ	0.87 (4)	2.15 (4)	2.896 (3)	143 (3)
N2—H2N⋯N1ⁱⁱ	0.86 (4)	2.14 (4)	2.993 (3)	173 (4)
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (ii) -x+1, -y+1, -z+1.

Figure 2
A packing diagram viewed along [001]. Hydrogen-bonding interactions are shown with dashed lines.

Synthesis and crystallization

2-Aminobenzenethiol (7.9 mmol, 0.85 ml) was added to an isocyanatobenzene solution (8.7 mmol, 0.9 ml) in 5 ml dimethylformamide (Fig. 3). The mixture was stirred at 0°C until the reaction was complete, and then warmed to room temperature. A precipitate was formed after adding 5 ml water. The precipitate was filtered off and washed with toluene. The resulting residue was purified by recrystallization from Et₂O solution to afford S-(2-aminophenyl) phenylcarbamothioate (1.2 g, 69% yield) as a white solid. Slow evaporation of the solvent resulted in colourless plates. ¹H NMR (400 MHz, DMSO) δ 10.40 (s, 1H, NH), 7.49 (d, J = 7.9 Hz, 2H), 7.29 (t, J = 7.8 Hz, 2H), 7.21 (d, J = 7.6 Hz, 1H), 7.14 (t, J = 7.6 Hz, 1H), 7.08–6.95 (m, 1H), 6.77 (d, J = 8.1 Hz, 1H), 6.55 (t, J = 7.4 Hz, 1H), 5.36 (s, 2H, NH₂).

Figure 3
Reaction scheme.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₃H₁₂N₂OS
M_r	244.31
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	100
a, b, c (Å)	9.448 (5), 10.395 (5), 24.337 (5)
V (Å³)	2390.2 (18)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.26
Crystal size (mm)	0.35 × 0.19 × 0.08

Data collection
Diffractometer	Rigaku OD SuperNova, Dual, Cu at zero, Atlas
Absorption correction	Gaussian (CrysAlis PRO; Rigaku OD, 2015 $[Rigaku OD. (2015). CrysAlis PRO. Rigaku Oxford Diffraction, The Woodlands, Texas, USA.]$ )
T_min, T_max	0.712, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	37562, 5122, 2960
R_int	0.117
(sin θ/λ)_max (Å⁻¹)	0.812

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.094, 0.217, 1.08
No. of reflections	5122
No. of parameters	166
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.89, −0.49
Computer programs: CrysAlis PRO (Rigaku OD, 2015 $[Rigaku OD. (2015). CrysAlis PRO. Rigaku Oxford Diffraction, The Woodlands, Texas, USA.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL2017 (Sheldrick, 2015b ) and SHELXTL (Sheldrick, 2008 ).

Structural data

CCDC reference: 1539765

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314618000627/hb4195sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618000627/hb4195Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314618000627/hb4195Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2017 (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

S-2-Aminophenyl phenylcarbamothioate top

Crystal data top

C₁₃H₁₂N₂OS	D_x = 1.358 Mg m⁻³
M_r = 244.31	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 4641 reflections
a = 9.448 (5) Å	θ = 3.8–33.3°
b = 10.395 (5) Å	µ = 0.26 mm⁻¹
c = 24.337 (5) Å	T = 100 K
V = 2390.2 (18) Å³	Plate, colourless
Z = 8	0.35 × 0.19 × 0.08 mm
F(000) = 1024

Data collection top

Rigaku OD SuperNova, Dual, Cu at zero, Atlas diffractometer	5122 independent reflections
Radiation source: micro-focus sealed X-ray tube	2960 reflections with I > 2σ(I)
Detector resolution: 10.6501 pixels mm^-1	R_int = 0.117
ω scans	θ_max = 35.3°, θ_min = 3.4°
Absorption correction: gaussian (CrysAlis PRO; Rigaku OD, 2015)	h = −14→14
T_min = 0.712, T_max = 1.000	k = −16→16
37562 measured reflections	l = −38→38

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.094	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.217	w = 1/[σ²(F_o²) + (0.0531P)² + 4.6756P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.001
5122 reflections	Δρ_max = 0.89 e Å⁻³
166 parameters	Δρ_min = −0.49 e Å⁻³
0 restraints

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. H atoms on N atoms were located in difference maps and refined isotropically. The remaining H atoms were positioned geometrically and treated as riding, with C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.27820 (6)	0.48071 (7)	0.50003 (3)	0.02546 (16)
O1	0.1937 (2)	0.6451 (2)	0.57835 (9)	0.0342 (5)
N1	0.4537 (2)	0.6976 (3)	0.45289 (11)	0.0285 (5)
H1N1	0.463 (3)	0.675 (3)	0.4882 (13)	0.023 (8)*
H1N2	0.499 (4)	0.770 (4)	0.4493 (15)	0.038 (10)*
N2	0.3466 (2)	0.4836 (2)	0.60304 (9)	0.0268 (5)
H2N	0.398 (4)	0.427 (4)	0.5872 (14)	0.043 (10)*
C1	0.3125 (3)	0.6969 (3)	0.43601 (11)	0.0255 (5)
C2	0.2647 (3)	0.7841 (3)	0.39658 (12)	0.0301 (6)
H2A	0.328614	0.845079	0.381456	0.036*
C3	0.1248 (3)	0.7826 (3)	0.37920 (12)	0.0349 (6)
H3A	0.093855	0.843092	0.352511	0.042*
C4	0.0297 (3)	0.6940 (3)	0.40033 (12)	0.0357 (7)
H4A	−0.066487	0.694576	0.388971	0.043*
C5	0.0770 (3)	0.6045 (3)	0.43822 (11)	0.0301 (6)
H5A	0.012911	0.542076	0.452112	0.036*
C6	0.2175 (2)	0.6044 (3)	0.45646 (10)	0.0232 (5)
C7	0.2669 (3)	0.5517 (3)	0.56763 (11)	0.0255 (5)
C8	0.3536 (3)	0.4943 (3)	0.66088 (11)	0.0271 (5)
C9	0.4367 (3)	0.4039 (3)	0.68797 (13)	0.0364 (7)
H9A	0.484475	0.339339	0.667498	0.044*
C10	0.4502 (4)	0.4074 (4)	0.74440 (14)	0.0484 (9)
H10A	0.507490	0.345560	0.762578	0.058*
C11	0.3807 (5)	0.5005 (4)	0.77457 (14)	0.0528 (10)
H11A	0.388073	0.501948	0.813493	0.063*
C12	0.3004 (4)	0.5915 (4)	0.74748 (14)	0.0489 (9)
H12A	0.254610	0.657016	0.768107	0.059*
C13	0.2851 (3)	0.5895 (3)	0.69083 (12)	0.0363 (7)
H13A	0.228691	0.652233	0.672773	0.044*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0209 (3)	0.0266 (3)	0.0289 (3)	−0.0001 (2)	−0.0013 (2)	−0.0007 (2)
O1	0.0286 (10)	0.0331 (11)	0.0409 (11)	0.0105 (8)	−0.0030 (8)	−0.0033 (9)
N1	0.0193 (9)	0.0277 (12)	0.0386 (13)	−0.0035 (9)	0.0017 (9)	−0.0009 (10)
N2	0.0212 (10)	0.0296 (12)	0.0296 (11)	0.0047 (9)	0.0000 (8)	−0.0016 (9)
C1	0.0207 (10)	0.0246 (13)	0.0312 (12)	0.0027 (9)	0.0021 (9)	−0.0047 (10)
C2	0.0315 (13)	0.0241 (13)	0.0346 (14)	0.0035 (10)	0.0041 (11)	0.0014 (10)
C3	0.0341 (14)	0.0368 (17)	0.0339 (14)	0.0136 (12)	0.0009 (11)	0.0011 (12)
C4	0.0230 (12)	0.0482 (19)	0.0358 (15)	0.0101 (12)	−0.0024 (10)	−0.0005 (13)
C5	0.0182 (10)	0.0398 (16)	0.0324 (13)	0.0001 (10)	0.0003 (9)	−0.0009 (11)
C6	0.0184 (10)	0.0244 (12)	0.0269 (11)	0.0034 (9)	0.0000 (8)	0.0002 (9)
C7	0.0171 (10)	0.0269 (13)	0.0327 (13)	0.0003 (9)	−0.0003 (9)	−0.0012 (10)
C8	0.0232 (11)	0.0285 (14)	0.0298 (12)	−0.0015 (10)	−0.0003 (9)	0.0002 (10)
C9	0.0386 (15)	0.0344 (16)	0.0363 (15)	0.0087 (13)	−0.0023 (12)	0.0001 (12)
C10	0.063 (2)	0.045 (2)	0.0377 (17)	0.0161 (18)	−0.0070 (15)	0.0025 (14)
C11	0.078 (3)	0.053 (2)	0.0274 (15)	0.015 (2)	−0.0036 (16)	−0.0010 (14)
C12	0.063 (2)	0.047 (2)	0.0371 (16)	0.0152 (18)	0.0056 (15)	−0.0054 (15)
C13	0.0364 (15)	0.0365 (18)	0.0361 (15)	0.0083 (13)	0.0017 (12)	0.0006 (12)

Geometric parameters (Å, º) top

S1—C6	1.763 (3)	C4—C5	1.383 (4)
S1—C7	1.806 (3)	C4—H4A	0.9500
O1—C7	1.221 (3)	C5—C6	1.400 (4)
N1—C1	1.397 (3)	C5—H5A	0.9500
N1—H1N1	0.90 (3)	C8—C13	1.389 (4)
N1—H1N2	0.87 (4)	C8—C9	1.391 (4)
N2—C7	1.346 (3)	C9—C10	1.380 (4)
N2—C8	1.414 (3)	C9—H9A	0.9500
N2—H2N	0.86 (4)	C10—C11	1.381 (5)
C1—C2	1.395 (4)	C10—H10A	0.9500
C1—C6	1.406 (4)	C11—C12	1.380 (5)
C2—C3	1.388 (4)	C11—H11A	0.9500
C2—H2A	0.9500	C12—C13	1.387 (5)
C3—C4	1.386 (5)	C12—H12A	0.9500
C3—H3A	0.9500	C13—H13A	0.9500

C6—S1—C7	103.32 (13)	C5—C6—S1	120.0 (2)
C1—N1—H1N1	112 (2)	C1—C6—S1	120.30 (19)
C1—N1—H1N2	116 (2)	O1—C7—N2	126.8 (3)
H1N1—N1—H1N2	106 (3)	O1—C7—S1	123.6 (2)
C7—N2—C8	128.5 (2)	N2—C7—S1	109.58 (19)
C7—N2—H2N	113 (2)	C13—C8—C9	119.7 (3)
C8—N2—H2N	118 (2)	C13—C8—N2	123.8 (3)
C2—C1—N1	120.6 (3)	C9—C8—N2	116.4 (3)
C2—C1—C6	118.8 (2)	C10—C9—C8	120.4 (3)
N1—C1—C6	120.6 (2)	C10—C9—H9A	119.8
C3—C2—C1	120.7 (3)	C8—C9—H9A	119.8
C3—C2—H2A	119.6	C9—C10—C11	120.3 (3)
C1—C2—H2A	119.6	C9—C10—H10A	119.9
C4—C3—C2	120.8 (3)	C11—C10—H10A	119.9
C4—C3—H3A	119.6	C12—C11—C10	119.2 (3)
C2—C3—H3A	119.6	C12—C11—H11A	120.4
C5—C4—C3	119.0 (3)	C10—C11—H11A	120.4
C5—C4—H4A	120.5	C11—C12—C13	121.5 (3)
C3—C4—H4A	120.5	C11—C12—H12A	119.3
C4—C5—C6	121.2 (3)	C13—C12—H12A	119.3
C4—C5—H5A	119.4	C12—C13—C8	119.0 (3)
C6—C5—H5A	119.4	C12—C13—H13A	120.5
C5—C6—C1	119.5 (2)	C8—C13—H13A	120.5

N1—C1—C2—C3	179.2 (3)	C8—N2—C7—S1	−170.7 (2)
C6—C1—C2—C3	2.2 (4)	C6—S1—C7—O1	19.6 (3)
C1—C2—C3—C4	−0.5 (4)	C6—S1—C7—N2	−162.42 (18)
C2—C3—C4—C5	−1.5 (5)	C7—N2—C8—C13	−6.3 (5)
C3—C4—C5—C6	1.7 (4)	C7—N2—C8—C9	174.8 (3)
C4—C5—C6—C1	0.1 (4)	C13—C8—C9—C10	0.7 (5)
C4—C5—C6—S1	−174.4 (2)	N2—C8—C9—C10	179.7 (3)
C2—C1—C6—C5	−2.0 (4)	C8—C9—C10—C11	0.3 (6)
N1—C1—C6—C5	−179.0 (2)	C9—C10—C11—C12	−1.5 (6)
C2—C1—C6—S1	172.4 (2)	C10—C11—C12—C13	1.7 (7)
N1—C1—C6—S1	−4.5 (4)	C11—C12—C13—C8	−0.7 (6)
C7—S1—C6—C5	−98.0 (2)	C9—C8—C13—C12	−0.5 (5)
C7—S1—C6—C1	87.6 (2)	N2—C8—C13—C12	−179.4 (3)
C8—N2—C7—O1	7.2 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13A···O1	0.95	2.32	2.928 (4)	121
N1—H1N2···O1ⁱ	0.87 (4)	2.15 (4)	2.896 (3)	143 (3)
N2—H2N···N1ⁱⁱ	0.86 (4)	2.14 (4)	2.993 (3)	173 (4)

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

Acknowledgements

The title compound was synthesized by Şengül Dilem Doğan, Department of Pharmaceutical Basic Sciences, Faculty of Pharmacy, Erciyes University, Kayseri, 38039, Turkey.

Funding information

RJB is grateful for funding from NSF (award 1205608) and the Partnership for Reduced Dimensional Materials for partial funding of this research, to Howard University Nanoscience Facility for access to liquid nitrogen, and the NSF–MRI program (grant No. CHE0619278) for funds to purchase the X-ray diffractometer.

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