Crystal structure of 2-meth­oxy-2-[(4-methyl­phen­yl)sulfan­yl]-1-phenyl­ethan-1-one

Julio Zukerman-Schpector; Paulo R Olivato; Henrique J Traesel; Jéssica Valença; Daniel N S Rodrigues; Edward R T Tiekink

doi:10.1107/S205698901402550X

. 2015 Jan 1;71(Pt 1):o3–o4. doi: 10.1107/S205698901402550X

Crystal structure of 2-methoxy-2-[(4-methylphenyl)sulfanyl]-1-phenylethan-1-one

Julio Zukerman-Schpector ^a,^*, Paulo R Olivato ^b, Henrique J Traesel ^b, Jéssica Valença ^b, Daniel N S Rodrigues ^b, Edward R T Tiekink ^c

PMCID: PMC4331849 PMID: 25705490

Abstract

In the title β-thiocarbonyl compound, C₁₆H₁₆O₂S, the carbonyl and methoxy O atoms are approximately coplanar [O—C—C—O torsion angle = −18.2 (5)°] and syn to each other, and the tolyl ring is orientated to lie over them. The dihedral angle between the planes of the two rings is 44.03 (16)°. In the crystal, supramolecular chains are formed along the c axis mediated by C—H⋯O interactions involving methine and methyl H atoms as donors, with the carbonyl O atom accepting both bonds; these pack with no specific intermolecular interactions between them.

Keywords: crystal structure, β-thiocarbonyl, C—H⋯O interactions

Related literature

For general background to β-thiocarbonyl and β-bis(thiocarbonyl) compounds, see: Vinhato et al. (2013 ▸); Zukerman-Schpector et al. (2008 ▸). For related structures, see: Olivato et al. (2013 ▸); Distefano et al. (1996 ▸). For further synthetic details, see: Ali & McDermott (2002 ▸); Zoretic & Soja (1976 ▸). graphic file with name e-71-000o3-scheme1.jpg

Experimental

Crystal data

C₁₆H₁₆O₂S
M _r = 272.35
Orthorhombic,
a = 17.8579 (9) Å
b = 8.1257 (4) Å
c = 9.8317 (5) Å
V = 1426.66 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.22 mm⁻¹
T = 293 K
0.41 × 0.14 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▸) T _min = 0.690, T _max = 0.745
5399 measured reflections
2337 independent reflections
1648 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.090
S = 1.02
2337 reflections
174 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.15 e Å⁻³
Absolute structure: Flack x determined using 552 quotients [(I ⁺)−(I ⁻)]/[(I ⁺)+(I ⁻)] (Parsons et al., 2013 ▸)
Absolute structure parameter: 0.02 (6)

Data collection: APEX2 (Bruker, 2009 ▸); cell refinement: SAINT (Bruker, 2009 ▸); data reduction: SAINT; program(s) used to solve structure: SIR (Burla et al., 2014 ▸; program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸) and DIAMOND (Brandenburg, 2006 ▸); software used to prepare material for publication: MarvinSketch (ChemAxon, 2010 ▸) and publCIF (Westrip, 2010 ▸).

Supplementary Material

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S205698901402550X/hg5421sup1.cif

e-71-000o3-sup1.cif^{(184.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S205698901402550X/hg5421Isup2.hkl

e-71-000o3-Isup2.hkl^{(128.5KB, hkl)}

Click here for additional data file.^{(5.3KB, cml)}

Supporting information file. DOI: 10.1107/S205698901402550X/hg5421Isup3.cml

Click here for additional data file.^{(1.3MB, tif)}

. DOI: 10.1107/S205698901402550X/hg5421fig1.tif

The molecular structure of the title compound showing the atom-labelling scheme and displacement ellipsoids at the 35% probability level.

Click here for additional data file.^{(1.2MB, tif)}

c . DOI: 10.1107/S205698901402550X/hg5421fig2.tif

A view of the supramolecular chain along the c axis mediated by C—H⋯O interactions (bluee dashed lines).

Click here for additional data file.^{(1.7MB, tif)}

c . DOI: 10.1107/S205698901402550X/hg5421fig3.tif

A view in projection down the c axis of the unit-cell contents. The C—H⋯O interactions are shown as blue dashed lines.

CCDC reference: 1035425

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
C1H1BO2ⁱ	0.96	2.49	3.366(6)	152
C8H8O2ⁱⁱ	0.98	2.46	3.323(6)	146

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

We thank Professor Regina H. A. Santos from IQSC–USP for the X-ray data collection. The Brazilian agencies CNPq (305626/2013-2 to JZS; 301180/2013-0 to PRO) and FAPESP are acknowledged for financial support.

supplementary crystallographic information

S1. Introduction

As part of our on-going research on the conformational and electronic interactions of some β-thio-carbonyl and β-bis-thio-carbonyl compounds, e.g. N,N-diethyl-2-[(4-substituted) phenylthio]acetamides, 1-methyl-3-phenylsulfonyl-2-piperidone, 3,3-bis[(4-substituted)phenylsulfanyl]-1-methyl-2-piperidones, 2-alkylthio-2-alkylsulfinyl-acetophenones, 2-alkylthio-2-phenylsulfonyl-acetophenones and 2-alkylsulfinyl-2-alkylsulfonyl-acetophenones, utilizing spectroscopic , theoretical and X-ray diffraction methods (Vinhato et al., 2013; Zukerman-Schpector et al., 2008; Olivato et al., 2013; Distefano et al., 1996) the title compound was synthesized and its crystal structure determined.

S2. Experimental

S2.1. Synthesis and crystallization

4-Methylthiopenol (5.0 g, 40 mmol) was reacted with bromine (1.1 ml, 20 mmol) in dichloromethane (250 mL) on hydrated silica gel support (25 g of SiO₂ and 12 mL of water) to give 4-methylphenyl disulfide (4.1 g, yield = 83%). A white solid was obtained after filtration and evaporation without further purification (Ali & McDermott, 2002). A solution of 2-methoxy acetophenone (0.4 mL, 2.76 mmol, Sigma-Aldrich) in THF (10 ml) was added drop wise to a cooled (195 K) solution of diisopropylamine (0.42 ml, 3.04 mmol) and butyllithium (2.0 ml, 2.76 mmol) in THF (10 ml). After 30 minutes, a solution of 4-methylphenyl disulfide (0.748 g, 3.04 mmol) with hexamethylphosphoramide (HMPA) (0.5 ml, 2.76 mmol) dissolved in THF (10 ml) was added drop wise to the enolate solution (Zoretic & Soja, 1976). After stirring for 3 h, water (50 ml) was added at room temperature and extraction with diethyl ether was performed. The organic layer was then treated with a saturated solution of ammonium chloride until neutral pH and dried over anhydrous magnesium sulfate. A brown oil was obtained after evaporation of the solvent. Purification through flash chromatography with n-hexane was used to remove the non-polar reactant (disulfide) then acetone to give a mixture of both acetophenones (product and reactant). Crystallization was performed by vapour diffusion of n-hexane into a chloroform solution held at 283 K to give pure product (0.3 g, yield = 40%). Suitable crystals for X-ray diffraction were obtained by same pathway; m.p. 359.3–359.8 K.

¹H NMR (CDCl₃, 500 MHz, ppm): δ 2.33 (s, 3H), 3.67 (s, 3H), 5.81 (s, 1H), 7.08–7.10 (m ,2H), 7.23-7.25 (m, 2H), 7.43–7.46(m, 2H),7.56–7.59 (m, 1H), 7.95–7.96 (m, 2H). HRMS: calcd. for C₁₆H₁₆O₂S [M + H]⁺ 272.0871; found: 272.0864.

S2.2. Refinement

Carbon-bound H-atoms were placed in calculated positions (C—H = 0.93 to 0.98 Å) and were included in the refinement in the riding model approximation, with U_iso(H) = 1.2–1.5U_eq(C).

S3. Results and discussion