S-Phenyl benzothio­ate

Belay, Y.H.; Kinfe, H.H.; Muller, A.

doi:10.1107/S1600536812037142

organic compounds

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Volume 68| Part 10| October 2012| Page o2825

https://doi.org/10.1107/S1600536812037142

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S-Phenyl benzothioate

Yonas H. Belay,^a Henok H. Kinfe ^a and Alfred Muller ^a ^*

^aResearch Centre for Synthesis and Catalysis, Department of Chemistry, University of Johannesburg (APK Campus), PO Box 524, Auckland Park, Johannesburg, 2006, South Africa
^*Correspondence e-mail: mullera@uj.ac.za

(Received 22 August 2012; accepted 28 August 2012; online 1 September 2012)

In the title compound, C₁₃H₁₀OS, the phenyl rings are inclined to one another by 51.12 (8)°. There is a short C—H⋯S contact in the molecule.In the crystal, molecules are linked via C—H⋯O hydrogen bonds forming chains along the a axis. Molecules are also linked by C—H⋯π and weak π–π interactions [centroid–centroid distance = 3.9543 (10) Å].

Related literature

The title compound was obtained by the reaction of thiophenolyate and benzoyl chloride in an alkaline medium. For background to the title compound, see: Reddy et al. (2010 ); Katritzky et al. (2007 ). For details of the Cambridge Structural Database, see: Allen (2002 ).

Experimental

Crystal data

C₁₃H₁₀OS
M_r = 214.27
Monoclinic, P 2₁ /c
a = 5.7203 (1) Å
b = 15.1315 (3) Å
c = 12.0606 (3) Å
β = 96.867 (1)°
V = 1036.44 (4) Å³
Z = 4
Cu Kα radiation
μ = 2.49 mm⁻¹
T = 100 K
0.25 × 0.12 × 0.12 mm

Data collection

Bruker APEX DUO 4K-CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.575, T_max = 0.754
9164 measured reflections
1759 independent reflections
1702 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.082
S = 1.04
1759 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C2–C7 and C8–C13 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯S1	0.95	2.52	2.9592 (16)	109
C13—H13⋯O1ⁱ	0.95	2.56	3.4889 (18)	167
C10—H10⋯Cg1ⁱⁱ	0.95	2.97	3.506 (2)	117
C5—H5⋯Cg2ⁱⁱⁱ	0.95	2.73	3.5915 (19)	152
Symmetry codes: (i) x-1, y, z; (ii) -x+2, -y+1, -z; (iii) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2011 ); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT and XPREP (Bruker, 2008); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812037142/ds2217sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812037142/ds2217Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812037142/ds2217Isup3.cml

checkCIF report

Comment top

Reaction of thiophenolyate and benzyol chloride in alkaline medium was described previously by Reddy et al., 2010. We have repeated the preparation of this compound to be used as starting material in some of our research. Benzoylation of thiophenol afforded colorless crystals of the title compound (see scheme and Figure 1) suitable for single crystal X-ray analysis of which the structure is reported herein. Molecules of the title compound crystalizes in the P2₁/c (Z=4) space group. All bond lengths are within their normal ranges (Allen, 2002). In the crystal packing several C—H···O/S/π interactions (see table 1, Fig. 2) as well as π-π stacking are observed (centroid to centroid distance = 3.9543 (10) Å, ring slippage = 1.366 Å).

Related literature top

For background to the title compound, see: Reddy et al. (2010); Katritzky et al. (2007). For details of the Cambridge Structural Database, see: Allen (2002).

Experimental top

A mixture of sodium hydroxide (344 mg, 8.61 mmol) and thiophenol (0.9 ml, 8.61 mmol) were dissolved in methanol (22 ml) for about 10 minutes. Benzoyl chloride (1 ml) was added to it. The reaction mixture was stirred overnight and then poured into ice-cold water. Afterwards it was filtered and dried to afford the title compound as white crystals in 63% yield.

Structure description top

For background to the title compound, see: Reddy et al. (2010); Katritzky et al. (2007). For details of the Cambridge Structural Database, see: Allen (2002).

Computing details top

Data collection: APEX2 (Bruker, 2011); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT and XPREP (Bruker, 2008); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. A view of (1). Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Packing diagram of (1) showing the C—H···O/S/π interactions as well as the π-π stacking.

S-Phenyl benzothioate top

Crystal data top

C₁₃H₁₀OS	F(000) = 448
M_r = 214.27	D_x = 1.373 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ybc	Cell parameters from 6683 reflections
a = 5.7203 (1) Å	θ = 4.7–65.8°
b = 15.1315 (3) Å	µ = 2.49 mm⁻¹
c = 12.0606 (3) Å	T = 100 K
β = 96.867 (1)°	Rectangular, colourless
V = 1036.44 (4) Å³	0.25 × 0.12 × 0.12 mm
Z = 4

Data collection top

Bruker APEX DUO 4K-CCD diffractometer	1759 independent reflections
Radiation source: Incoatec IµS microfocus X-ray source	1702 reflections with I > 2σ(I)
Incoatec Quazar Multilayer Mirror monochromator	R_int = 0.022
Detector resolution: 8.4 pixels mm^-1	θ_max = 66.4°, θ_min = 4.7°
φ and ω scans	h = −2→6
Absorption correction: multi-scan (SADABS; Bruker, 2008)	k = −17→17
T_min = 0.575, T_max = 0.754	l = −14→13
9164 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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.082	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0364P)² + 0.7558P] where P = (F_o² + 2F_c²)/3
1759 reflections	(Δ/σ)_max = 0.001
136 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₁₃H₁₀OS	V = 1036.44 (4) Å³
M_r = 214.27	Z = 4
Monoclinic, P2₁/c	Cu Kα radiation
a = 5.7203 (1) Å	µ = 2.49 mm⁻¹
b = 15.1315 (3) Å	T = 100 K
c = 12.0606 (3) Å	0.25 × 0.12 × 0.12 mm
β = 96.867 (1)°

Data collection top

Bruker APEX DUO 4K-CCD diffractometer	1759 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	1702 reflections with I > 2σ(I)
T_min = 0.575, T_max = 0.754	R_int = 0.022
9164 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.082	H-atom parameters constrained
S = 1.04	Δρ_max = 0.35 e Å⁻³
1759 reflections	Δρ_min = −0.26 e Å⁻³
136 parameters

Special details top

Experimental. The intensity data was collected on a Bruker Apex DUO 4 K CCD diffractometer using an exposure time of 5 s/frame. A total of 2274 frames were collected with a frame width of 1° covering up to θ = 66.38° with 96.3% completeness accomplished.

Analytical data: mp: 53–55 °C (Lit. 54–55 °C; Katritzky et al., 2007); ¹H NMR (CDCl₃, 400 MHz): d 8.03 (d, J = 0.8 Hz, 1H), 8.01(d, J = 1.2 Hz, 1H), 7.62–7.58 (m, 1H), 7.52–7.44 (m, 7H), ¹³C NMR (CDCl₃, 400 MHz): d 190.1, 136.6, 135.1, 133.6, 129.5, 129.2, 128.7, 127.5, 127.3.

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	0.66521 (7)	0.44609 (2)	0.09450 (3)	0.02499 (16)
O1	1.05856 (19)	0.36323 (7)	0.17500 (9)	0.0242 (3)
C1	0.9304 (3)	0.42516 (10)	0.18525 (12)	0.0180 (3)
C2	0.9751 (3)	0.49420 (10)	0.27395 (12)	0.0174 (3)
C3	1.1950 (3)	0.49605 (10)	0.33797 (13)	0.0210 (3)
H3	1.3106	0.4531	0.3262	0.025*
C4	1.2443 (3)	0.56059 (11)	0.41871 (14)	0.0237 (4)
H4	1.3943	0.5619	0.462	0.028*
C5	1.0767 (3)	0.62332 (11)	0.43703 (13)	0.0234 (3)
H5	1.1117	0.6673	0.4928	0.028*
C6	0.8580 (3)	0.62174 (11)	0.37383 (13)	0.0239 (4)
H6	0.7429	0.6647	0.3863	0.029*
C7	0.8067 (3)	0.55781 (11)	0.29258 (13)	0.0214 (3)
H7	0.6566	0.5571	0.2493	0.026*
C8	0.6486 (3)	0.35922 (10)	−0.00504 (12)	0.0182 (3)
C9	0.8130 (3)	0.35150 (10)	−0.08087 (13)	0.0211 (3)
H9	0.9497	0.3877	−0.0737	0.025*
C10	0.7749 (3)	0.29047 (11)	−0.16688 (13)	0.0231 (4)
H10	0.8871	0.2843	−0.2184	0.028*
C11	0.5735 (3)	0.23835 (10)	−0.17811 (13)	0.0221 (3)
H11	0.5472	0.1972	−0.2378	0.027*
C12	0.4107 (3)	0.24634 (10)	−0.10217 (13)	0.0210 (3)
H12	0.2734	0.2105	−0.1097	0.025*
C13	0.4483 (3)	0.30674 (10)	−0.01499 (12)	0.0192 (3)
H13	0.3376	0.312	0.0374	0.023*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0287 (3)	0.0191 (2)	0.0243 (2)	0.00622 (15)	−0.00893 (16)	−0.00571 (15)
O1	0.0236 (6)	0.0242 (6)	0.0242 (6)	0.0056 (5)	0.0007 (4)	−0.0028 (5)
C1	0.0190 (7)	0.0164 (7)	0.0181 (8)	−0.0014 (6)	0.0004 (6)	0.0032 (6)
C2	0.0203 (7)	0.0174 (8)	0.0146 (7)	−0.0018 (6)	0.0027 (6)	0.0027 (6)
C3	0.0211 (8)	0.0189 (8)	0.0224 (8)	0.0007 (6)	0.0002 (6)	0.0032 (6)
C4	0.0235 (8)	0.0246 (8)	0.0215 (8)	−0.0034 (6)	−0.0043 (6)	0.0024 (6)
C5	0.0298 (8)	0.0226 (8)	0.0174 (7)	−0.0044 (6)	0.0015 (6)	−0.0019 (6)
C6	0.0245 (8)	0.0247 (8)	0.0233 (8)	0.0008 (6)	0.0055 (6)	−0.0040 (7)
C7	0.0188 (8)	0.0259 (9)	0.0191 (8)	0.0003 (6)	0.0010 (6)	−0.0019 (6)
C8	0.0223 (8)	0.0148 (7)	0.0161 (7)	0.0031 (6)	−0.0030 (6)	0.0010 (6)
C9	0.0203 (8)	0.0205 (8)	0.0220 (8)	−0.0013 (6)	0.0006 (6)	0.0060 (6)
C10	0.0248 (8)	0.0272 (9)	0.0181 (8)	0.0047 (6)	0.0054 (6)	0.0048 (6)
C11	0.0285 (8)	0.0196 (8)	0.0171 (8)	0.0045 (6)	−0.0021 (6)	−0.0021 (6)
C12	0.0195 (7)	0.0187 (8)	0.0242 (8)	−0.0010 (6)	−0.0005 (6)	−0.0006 (6)
C13	0.0202 (8)	0.0191 (8)	0.0184 (7)	0.0030 (6)	0.0024 (6)	0.0010 (6)

Geometric parameters (Å, º) top

S1—C8	1.7751 (15)	C6—H6	0.95
S1—C1	1.7894 (15)	C7—H7	0.95
O1—C1	1.2054 (19)	C8—C13	1.387 (2)
C1—C2	1.495 (2)	C8—C9	1.393 (2)
C2—C3	1.395 (2)	C9—C10	1.386 (2)
C2—C7	1.399 (2)	C9—H9	0.95
C3—C4	1.384 (2)	C10—C11	1.390 (2)
C3—H3	0.95	C10—H10	0.95
C4—C5	1.385 (2)	C11—C12	1.387 (2)
C4—H4	0.95	C11—H11	0.95
C5—C6	1.385 (2)	C12—C13	1.390 (2)
C5—H5	0.95	C12—H12	0.95
C6—C7	1.383 (2)	C13—H13	0.95

C8—S1—C1	104.81 (7)	C6—C7—H7	119.9
O1—C1—C2	124.23 (13)	C2—C7—H7	119.9
O1—C1—S1	123.81 (12)	C13—C8—C9	120.70 (14)
C2—C1—S1	111.96 (10)	C13—C8—S1	117.35 (12)
C3—C2—C7	119.34 (14)	C9—C8—S1	121.36 (12)
C3—C2—C1	118.40 (13)	C10—C9—C8	119.29 (14)
C7—C2—C1	122.24 (13)	C10—C9—H9	120.4
C4—C3—C2	119.85 (15)	C8—C9—H9	120.4
C4—C3—H3	120.1	C9—C10—C11	120.34 (14)
C2—C3—H3	120.1	C9—C10—H10	119.8
C3—C4—C5	120.60 (15)	C11—C10—H10	119.8
C3—C4—H4	119.7	C12—C11—C10	120.02 (15)
C5—C4—H4	119.7	C12—C11—H11	120
C6—C5—C4	119.80 (15)	C10—C11—H11	120
C6—C5—H5	120.1	C11—C12—C13	120.09 (14)
C4—C5—H5	120.1	C11—C12—H12	120
C7—C6—C5	120.21 (15)	C13—C12—H12	120
C7—C6—H6	119.9	C8—C13—C12	119.54 (14)
C5—C6—H6	119.9	C8—C13—H13	120.2
C6—C7—C2	120.20 (14)	C12—C13—H13	120.2

C8—S1—C1—O1	−0.46 (15)	C3—C2—C7—C6	−0.1 (2)
C8—S1—C1—C2	178.75 (10)	C1—C2—C7—C6	−178.42 (14)
O1—C1—C2—C3	10.8 (2)	C1—S1—C8—C13	122.78 (12)
S1—C1—C2—C3	−168.42 (11)	C1—S1—C8—C9	−66.00 (14)
O1—C1—C2—C7	−170.86 (15)	C13—C8—C9—C10	−0.1 (2)
S1—C1—C2—C7	9.93 (18)	S1—C8—C9—C10	−171.00 (11)
C7—C2—C3—C4	−0.1 (2)	C8—C9—C10—C11	0.8 (2)
C1—C2—C3—C4	178.26 (14)	C9—C10—C11—C12	−0.9 (2)
C2—C3—C4—C5	0.3 (2)	C10—C11—C12—C13	0.3 (2)
C3—C4—C5—C6	−0.2 (2)	C9—C8—C13—C12	−0.5 (2)
C4—C5—C6—C7	0.0 (2)	S1—C8—C13—C12	170.75 (11)
C5—C6—C7—C2	0.2 (2)	C11—C12—C13—C8	0.4 (2)

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C2–C7 and C8–C13 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···S1	0.95	2.52	2.9592 (16)	109
C13—H13···O1ⁱ	0.95	2.56	3.4889 (18)	167
C10—H10···Cg1ⁱⁱ	0.95	2.97	3.506 (2)	117
C5—H5···Cg2ⁱⁱⁱ	0.95	2.73	3.5915 (19)	152

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

Experimental details

Crystal data
Chemical formula	C₁₃H₁₀OS
M_r	214.27
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	5.7203 (1), 15.1315 (3), 12.0606 (3)
β (°)	96.867 (1)
V (Å³)	1036.44 (4)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	2.49
Crystal size (mm)	0.25 × 0.12 × 0.12

Data collection
Diffractometer	Bruker APEX DUO 4K-CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.575, 0.754
No. of measured, independent and observed [I > 2σ(I)] reflections	9164, 1759, 1702
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.082, 1.04
No. of reflections	1759
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.26

Computer programs: APEX2 (Bruker, 2011), SAINT (Bruker, 2008), SAINT and XPREP (Bruker, 2008), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2005), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C2–C7 and C8–C13 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···S1	0.95	2.52	2.9592 (16)	108.6
C13—H13···O1ⁱ	0.95	2.56	3.4889 (18)	167.2
C10—H10···Cg1ⁱⁱ	0.95	2.97	3.506 (2)	117
C5—H5···Cg2ⁱⁱⁱ	0.95	2.73	3.5915 (19)	152

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

Acknowledgements

Research funds of the University of Johannesburg and the Research Center for Synthesis and Catalysis are gratefully acknowledged. Mrs Z. H. Phasha is thanked for the data collection.

References

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