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

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.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.042
• wR factor = 0.090
• Data-to-parameter ratio = 13.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT340_ALERT_3_C Low Bond Precision on  C-C Bonds ...............     0.0070 Ang.
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          3 Report
PLAT915_ALERT_3_C Low Friedel Pair Coverage ......................         76 %

Alert level G
PLAT199_ALERT_1_G Reported _cell_measurement_temperature ..... (K)        293 Check
PLAT200_ALERT_1_G Reported   _diffrn_ambient_temperature ..... (K)        293 Check
PLAT792_ALERT_1_G The Model has Chirality at C8      .............          S Verify
PLAT910_ALERT_3_G Missing # of FCF Reflections Below Th(Min) .....          2 Report

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   3 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   4 ALERT level G = General information/check it is not something unexpected

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check


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Alert level A
PUBL024_ALERT_1_A The number of authors is greater than 5.
              Please specify the role of each of the co-authors
              for your paper.

Author Response: The contribution of the authors to this submission is as follows: Julio Zukerman-Schpector Analysis and write-up Paulo R.Olivato Supervisor Henrique J.Traesel Student/synthesis/crystallization J\'essica Valen\,ca Student/synthesis Daniel N. S.Rodrigues Student/synthesis/crystallization Edward R. T. Tiekink ([e-mail]) Analysis and write-up

   1 ALERT level A = Data missing that is essential or data in wrong format
   0 ALERT level G = General alerts. Data that may be required is missing

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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).

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).

Structure description

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.

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).

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.

Refinement details

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).

Computing details

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); 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).

Figures

	Fig. 1. The molecular structure of the title compound showing the atom-labelling scheme and displacement ellipsoids at the 35% probability level.
	Fig. 2. A view of the supramolecular chain along the c axis mediated by C—H···O interactions (bluee dashed lines).
	Fig. 3. A view in projection down the c axis of the unit-cell contents. The C—H···O interactions are shown as blue dashed lines.

(I)

Crystal data

C16H16O2S	Dx = 1.268 Mg m^−3
Mr = 272.35	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pca21	Cell parameters from 1023 reflections
a = 17.8579 (9) Å	θ = 3.1–18.7°
b = 8.1257 (4) Å	µ = 0.22 mm^−1
c = 9.8317 (5) Å	T = 293 K
V = 1426.66 (12) Å^3	Irregular, colourless
Z = 4	0.41 × 0.14 × 0.08 mm
F(000) = 576

Data collection

Bruker APEXII CCD diffractometer	1648 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.031
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	θmax = 25.4°, θmin = 2.8°
Tmin = 0.690, Tmax = 0.745	h = −21→21
5399 measured reflections	k = −9→9
2337 independent reflections	l = −10→11

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.042	w = 1/[σ^2(Fo^2) + (0.0294P)^2 + 0.2164P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.090	(Δ/σ)max < 0.001
S = 1.02	Δρmax = 0.14 e Å^−3
2337 reflections	Δρmin = −0.15 e Å^−3
174 parameters	Absolute structure: Flack x determined using 552 quotients [(I^+)-(I^-)]/[(I^+)+(I^-)] (Parsons et al., 2013)
1 restraint	Absolute structure parameter: 0.02 (6)
Primary atom site location: structure-invariant direct methods

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.3662 (3)	0.6856 (7)	1.3764 (5)	0.0916 (18)
H1A	0.3249	0.7532	1.4046	0.137*
H1B	0.4106	0.7185	1.4243	0.137*
H1C	0.3553	0.5725	1.3964	0.137*
C2	0.3784 (3)	0.7055 (6)	1.2258 (5)	0.0642 (13)
C3	0.3285 (3)	0.7876 (6)	1.1440 (6)	0.0737 (14)
H3	0.2850	0.8300	1.1823	0.088*
C4	0.3411 (3)	0.8094 (6)	1.0061 (5)	0.0683 (13)
H4	0.3066	0.8670	0.9537	0.082*
C5	0.4049 (2)	0.7455 (5)	0.9462 (5)	0.0564 (11)
C6	0.4553 (2)	0.6622 (5)	1.0273 (5)	0.0615 (12)
H6	0.4987	0.6186	0.9893	0.074*
C7	0.4416 (3)	0.6434 (5)	1.1643 (5)	0.0635 (13)
H7	0.4763	0.5868	1.2171	0.076*
C8	0.4839 (2)	0.9437 (5)	0.7603 (5)	0.0576 (10)
H8	0.4930	0.9708	0.6646	0.069*
C9	0.6015 (3)	0.8116 (6)	0.7474 (6)	0.0834 (15)
H9A	0.6139	0.8637	0.6627	0.125*
H9B	0.5771	0.7085	0.7299	0.125*
H9C	0.6465	0.7927	0.7987	0.125*
C10	0.4468 (2)	1.0888 (5)	0.8275 (5)	0.0559 (11)
C11	0.3852 (2)	1.1782 (5)	0.7587 (5)	0.0539 (10)
C12	0.3573 (2)	1.3181 (5)	0.8205 (5)	0.0674 (13)
H12	0.3767	1.3519	0.9037	0.081*
C13	0.3007 (3)	1.4083 (5)	0.7595 (7)	0.0793 (14)
H13	0.2828	1.5027	0.8021	0.095*
C14	0.2709 (3)	1.3608 (6)	0.6381 (7)	0.0781 (14)
H14	0.2325	1.4212	0.5983	0.094*
C15	0.2984 (3)	1.2225 (7)	0.5754 (5)	0.0840 (16)
H15	0.2780	1.1887	0.4930	0.101*
C16	0.3556 (3)	1.1333 (6)	0.6325 (5)	0.0736 (13)
H16	0.3748	1.0423	0.5868	0.088*
O1	0.55239 (15)	0.9162 (4)	0.8235 (3)	0.0666 (9)
O2	0.46803 (18)	1.1328 (4)	0.9400 (3)	0.0727 (9)
S	0.41986 (7)	0.76542 (13)	0.76791 (16)	0.0711 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.090 (4)	0.115 (5)	0.070 (4)	−0.030 (3)	0.006 (3)	0.005 (3)
C2	0.065 (3)	0.064 (3)	0.064 (4)	−0.020 (2)	0.006 (3)	0.000 (3)
C3	0.061 (3)	0.077 (3)	0.084 (4)	−0.004 (3)	0.011 (3)	0.002 (3)
C4	0.064 (3)	0.064 (3)	0.077 (4)	−0.001 (2)	−0.007 (3)	0.006 (3)
C5	0.061 (3)	0.048 (2)	0.060 (3)	−0.011 (2)	−0.001 (2)	−0.003 (2)
C6	0.061 (3)	0.056 (3)	0.067 (3)	0.000 (2)	−0.001 (2)	−0.001 (3)
C7	0.066 (3)	0.058 (3)	0.066 (4)	−0.006 (2)	−0.008 (3)	0.009 (3)
C8	0.070 (3)	0.058 (2)	0.045 (2)	−0.0025 (19)	−0.003 (3)	0.003 (3)
C9	0.084 (3)	0.095 (3)	0.072 (4)	0.024 (3)	−0.003 (3)	0.000 (4)
C10	0.070 (3)	0.052 (3)	0.046 (3)	−0.009 (2)	0.007 (2)	0.002 (2)
C11	0.061 (2)	0.051 (2)	0.049 (3)	−0.0077 (18)	0.012 (3)	0.003 (3)
C12	0.066 (3)	0.065 (3)	0.071 (3)	−0.009 (2)	0.012 (3)	−0.013 (3)
C13	0.069 (3)	0.065 (3)	0.104 (4)	0.006 (2)	0.013 (4)	−0.008 (4)
C14	0.064 (3)	0.077 (3)	0.094 (4)	0.009 (3)	0.013 (3)	0.013 (3)
C15	0.085 (3)	0.102 (4)	0.065 (4)	0.014 (3)	−0.011 (3)	0.010 (3)
C16	0.090 (3)	0.078 (3)	0.053 (3)	0.017 (3)	−0.004 (3)	−0.007 (3)
O1	0.0665 (18)	0.077 (2)	0.057 (2)	0.0086 (16)	−0.0038 (16)	−0.0012 (16)
O2	0.094 (2)	0.076 (2)	0.048 (2)	−0.0017 (17)	−0.0047 (18)	−0.0078 (19)
S	0.0948 (8)	0.0600 (6)	0.0583 (7)	−0.0129 (6)	−0.0079 (8)	−0.0055 (8)

Geometric parameters (Å, º)

C1—C2	1.505 (7)	C8—H8	0.9800
C1—H1A	0.9600	C9—O1	1.432 (5)
C1—H1B	0.9600	C9—H9A	0.9600
C1—H1C	0.9600	C9—H9B	0.9600
C2—C3	1.373 (7)	C9—H9C	0.9600
C2—C7	1.376 (6)	C10—O2	1.224 (5)
C3—C4	1.385 (7)	C10—C11	1.480 (6)
C3—H3	0.9300	C11—C12	1.382 (6)
C4—C5	1.383 (6)	C11—C16	1.398 (7)
C4—H4	0.9300	C12—C13	1.384 (6)
C5—C6	1.379 (6)	C12—H12	0.9300
C5—S	1.781 (5)	C13—C14	1.363 (8)
C6—C7	1.378 (6)	C13—H13	0.9300
C6—H6	0.9300	C14—C15	1.373 (6)
C7—H7	0.9300	C14—H14	0.9300
C8—O1	1.390 (4)	C15—C16	1.372 (6)
C8—C10	1.505 (5)	C15—H15	0.9300
C8—S	1.847 (4)	C16—H16	0.9300
C2—C1—H1A	109.5	O1—C9—H9A	109.5
C2—C1—H1B	109.5	O1—C9—H9B	109.5
H1A—C1—H1B	109.5	H9A—C9—H9B	109.5
C2—C1—H1C	109.5	O1—C9—H9C	109.5
H1A—C1—H1C	109.5	H9A—C9—H9C	109.5
H1B—C1—H1C	109.5	H9B—C9—H9C	109.5
C3—C2—C7	116.9 (5)	O2—C10—C11	120.0 (4)
C3—C2—C1	122.3 (5)	O2—C10—C8	119.2 (4)
C7—C2—C1	120.8 (5)	C11—C10—C8	120.7 (4)
C2—C3—C4	122.0 (5)	C12—C11—C16	117.9 (4)
C2—C3—H3	119.0	C12—C11—C10	118.1 (4)
C4—C3—H3	119.0	C16—C11—C10	123.9 (4)
C5—C4—C3	120.2 (5)	C11—C12—C13	120.6 (5)
C5—C4—H4	119.9	C11—C12—H12	119.7
C3—C4—H4	119.9	C13—C12—H12	119.7
C6—C5—C4	118.4 (5)	C14—C13—C12	120.9 (5)
C6—C5—S	121.0 (4)	C14—C13—H13	119.5
C4—C5—S	120.6 (4)	C12—C13—H13	119.5
C7—C6—C5	120.2 (5)	C13—C14—C15	119.0 (5)
C7—C6—H6	119.9	C13—C14—H14	120.5
C5—C6—H6	119.9	C15—C14—H14	120.5
C2—C7—C6	122.3 (5)	C16—C15—C14	121.0 (5)
C2—C7—H7	118.8	C16—C15—H15	119.5
C6—C7—H7	118.8	C14—C15—H15	119.5
O1—C8—C10	108.5 (4)	C15—C16—C11	120.4 (5)
O1—C8—S	113.6 (3)	C15—C16—H16	119.8
C10—C8—S	108.9 (3)	C11—C16—H16	119.8
O1—C8—H8	108.6	C8—O1—C9	113.7 (3)
C10—C8—H8	108.6	C5—S—C8	101.8 (2)
S—C8—H8	108.6
C7—C2—C3—C4	−0.8 (7)	O2—C10—C11—C16	−177.7 (4)
C1—C2—C3—C4	178.2 (4)	C8—C10—C11—C16	2.3 (6)
C2—C3—C4—C5	1.0 (7)	C16—C11—C12—C13	1.2 (6)
C3—C4—C5—C6	−0.7 (6)	C10—C11—C12—C13	178.7 (4)
C3—C4—C5—S	177.5 (4)	C11—C12—C13—C14	0.5 (7)
C4—C5—C6—C7	0.3 (6)	C12—C13—C14—C15	−0.8 (7)
S—C5—C6—C7	−177.9 (4)	C13—C14—C15—C16	−0.6 (8)
C3—C2—C7—C6	0.3 (7)	C14—C15—C16—C11	2.4 (8)
C1—C2—C7—C6	−178.7 (4)	C12—C11—C16—C15	−2.7 (7)
C5—C6—C7—C2	0.0 (7)	C10—C11—C16—C15	180.0 (4)
O1—C8—C10—O2	−18.2 (5)	C10—C8—O1—C9	−164.3 (3)
S—C8—C10—O2	105.9 (4)	S—C8—O1—C9	74.4 (4)
O1—C8—C10—C11	161.7 (3)	C6—C5—S—C8	−83.1 (4)
S—C8—C10—C11	−74.1 (4)	C4—C5—S—C8	98.8 (4)
O2—C10—C11—C12	4.9 (6)	O1—C8—S—C5	63.2 (4)
C8—C10—C11—C12	−175.0 (4)	C10—C8—S—C5	−57.9 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1B···O2^i	0.96	2.49	3.366 (6)	152
C8—H8···O2^ii	0.98	2.46	3.323 (6)	146

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