4-[(4-Methyl­phen­yl)sulfan­yl]butan-2-one

Novaković, S.B.; Leka, Z.; Stevanović, D.; Muškinja, J.; Bogdanović, G.A.

doi:10.1107/S1600536813026895

organic compounds

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Volume 69| Part 11| November 2013| Page o1625

doi:10.1107/S1600536813026895

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4-[(4-Methylphenyl)sulfanyl]butan-2-one

Sladjana B. Novaković,^a Zorica Leka,^b ^* Dragana Stevanović,^c Jovana Muškinja ^c and Goran A. Bogdanović ^a

^aVinča Institute of Nuclear Sciences, Laboratory of Theoretical Physics and Condensed Matter Physics, PO Box 522, University of Belgrade, 11001 Belgrade, Serbia, ^bFaculty of Metallurgy and Technology, University of Montenegro, Cetinjski put bb, 81000 Podgorica, Montenegro, and ^cFaculty of Sciences, Department of Chemistry, University of Kragujevac, R. Domanovića 12, 34000 Kragujevac, Serbia
^*Correspondence e-mail: zorica@ac.me

(Received 24 September 2013; accepted 30 September 2013; online 9 October 2013)

In the title compound, C₁₁H₁₄OS, all non-H atoms are essentially coplanar, with a mean deviation of 0.023 Å. In the crystal, centrosymmetrically related molecules are weakly connected into dimers by pairs of C—H⋯O interactions. The dimers are further linked along the a axis by weak C—H⋯π and C—H⋯S interactions.

CCDC reference: 963883

Related literature

For the physico-chemical properties of organosulfur compounds, see: Page (1999 ). For the synthetic procedure, see: Stevanović et al. (2012 ). For the role of sulfur in hydrogen bonding, see: Francuski et al. (2011 ).

Experimental

Crystal data

C₁₁H₁₄OS
M_r = 194.28
Triclinic, $[P \overline 1]$
a = 7.2703 (11) Å
b = 7.3226 (7) Å
c = 11.7615 (11) Å
α = 88.232 (8)°
β = 79.343 (10)°
γ = 61.350 (13)°
V = 538.80 (13) Å³
Z = 2
Cu Kα radiation
μ = 2.33 mm⁻¹
T = 293 K
0.50 × 0.26 × 0.14 mm

Data collection

Agilent Gemini S diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013 ) T_min = 0.444, T_max = 1.000
3254 measured reflections
2052 independent reflections
1731 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.170
S = 1.07
2052 reflections
120 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C4–C9 phenyl ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10c⋯O1ⁱ	0.96	2.67	3.579 (4)	158
C3—H3a⋯S1ⁱⁱ	0.97	2.99	3.855 (3)	149
C3—H3b⋯S1ⁱⁱⁱ	0.97	3.02	3.870 (3)	147
C2—H2a⋯Cgⁱⁱ	0.97	2.86	3.628 (4)	137
C2—H2b⋯Cg^iv	0.97	2.95	3.678 (4)	133
Symmetry codes: (i) -x+1, -y, -z-1; (ii) -x, -y, -z; (iii) -x+1, -y, -z; (iv) -x+1, -y+1, -z+1.

Data collection: CrysAlis PRO (Agilent, 2013); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 2012 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: WinGX (Farrugia, 2012), PLATON (Spek, 2009 ) and PARST (Nardelli, 1995 ).

Supporting information

CCDC reference: 963883

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813026895/rz5084sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813026895/rz5084Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813026895/rz5084Isup3.cml

checkCIF report

Comment top

Sulfides containing a carbonyl group are versatile precursors for the synthesis of wide range of biologically interesting compounds (Page, 1999). The main approach to β-thiaketones is the addition of compounds containing an SH group to conjugated carbonyls (the thia-Michael reaction). We recently published a versatile method for electrochemical generation of the catalyst for this addition (Stevanović et al., 2012) and herein we report the structure of 4-(o-tolylthio)butan-2-one.

The molecule of the title compound (Fig. 1) is essentially planar with a mean deviation of all non-H atoms of 0.023 Å. Atoms O1 and C10 exhibit the highest deviation from the mean molecular plane of 0.047 (3) and -0.057 (2) Å, respectively. The crystal packing displays no classical hydrogen bonding. The carbonyl O1 acceptor is engaged only in a weak C10—H10c···O1 interaction (Table 1) which associates the centrosymmetric molecules into dimers (Fig. 2a). Pairs of C—H···π and C—H···S interactions (Table 1) connect the molecules along the a axis (Figure 2b). In the absence of more relevant hydrogen bonding the weak C—H···S interactions can be considered important for the stabilization of the crystal structure (Francuski et al., 2011).

Related literature top

For the physico-chemical properties of organosulfur compounds, see: Page (1999). For the synthetic procedure see: Stevanović et al. (2012). For the role of sulfur in hydrogen bonding see: Francuski et al. (2011).

Experimental top

The title compound was obtained by treating methyl vinyl ketone with the corresponding thiophenol in the presence of an electrochemically generated zirconium catalyst, following the reported procedure (Stevanović et al., 2012).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2013); cell refinement: CrysAlis PRO (Agilent, 2013); data reduction: CrysAlis PRO (Agilent, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 2012) and Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 2012), PLATON (Spek, 2009) and PARST (Nardelli, 1995).

Figures top

	Fig. 1. The molecular structure of the title compound, with atom labels and 40% probability displacement ellipsoids for non-H atoms.
	Fig. 2. Intermolecular interactions in the title compound: (a) C—H···O interactions (dashed lines) connecting centrosymmetrically related molecules into dimers; (b) C—H···π (dotted lines) and C—H···S interactions (dashed lines) connecting the molecules along a axis. H-atoms not involved in hydrogen interactions are omitted.

4-[(4-Methylphenyl)sulfanyl]butan-2-one top

Crystal data top

C₁₁H₁₄OS	Z = 2
M_r = 194.28	F(000) = 208
Triclinic, P1	D_x = 1.198 Mg m⁻³
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54180 Å
a = 7.2703 (11) Å	Cell parameters from 1309 reflections
b = 7.3226 (7) Å	θ = 7.0–72.1°
c = 11.7615 (11) Å	µ = 2.33 mm⁻¹
α = 88.232 (8)°	T = 293 K
β = 79.343 (10)°	Prismatic, colourless
γ = 61.350 (13)°	0.50 × 0.26 × 0.14 mm
V = 538.80 (13) Å³

Data collection top

Agilent Gemini S diffractometer	2052 independent reflections
Radiation source: Enhance (Cu) X-ray Source	1731 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
Detector resolution: 16.3280 pixels mm^-1	θ_max = 72.9°, θ_min = 3.8°
ω scans	h = −8→8
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	k = −9→5
T_min = 0.444, T_max = 1.000	l = −14→14
3254 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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.170	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.1046P)² + 0.083P] where P = (F_o² + 2F_c²)/3
2052 reflections	(Δ/σ)_max < 0.001
120 parameters	Δρ_max = 0.34 e Å⁻³
0 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

C₁₁H₁₄OS	γ = 61.350 (13)°
M_r = 194.28	V = 538.80 (13) Å³
Triclinic, P1	Z = 2
a = 7.2703 (11) Å	Cu Kα radiation
b = 7.3226 (7) Å	µ = 2.33 mm⁻¹
c = 11.7615 (11) Å	T = 293 K
α = 88.232 (8)°	0.50 × 0.26 × 0.14 mm
β = 79.343 (10)°

Data collection top

Agilent Gemini S diffractometer	2052 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	1731 reflections with I > 2σ(I)
T_min = 0.444, T_max = 1.000	R_int = 0.027
3254 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	0 restraints
wR(F²) = 0.170	H-atom parameters constrained
S = 1.07	Δρ_max = 0.34 e Å⁻³
2052 reflections	Δρ_min = −0.33 e Å⁻³
120 parameters

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

	x	y	z	U_iso*/U_eq
S1	0.31244 (10)	−0.14778 (8)	0.03374 (5)	0.0640 (3)
O1	0.2948 (4)	0.0791 (3)	−0.32862 (19)	0.0927 (7)
C1	0.3882 (4)	−0.1053 (4)	−0.3166 (2)	0.0643 (6)
C2	0.4007 (4)	−0.1919 (4)	−0.2004 (2)	0.0596 (6)
H2A	0.5496	−0.2765	−0.1949	0.072*
H2B	0.3359	−0.2818	−0.1924	0.072*
C3	0.2892 (4)	−0.0231 (4)	−0.1015 (2)	0.0576 (6)
H3A	0.1398	0.0627	−0.1058	0.069*
H3B	0.3552	0.0656	−0.1070	0.069*
C4	0.1796 (3)	0.0637 (3)	0.14013 (19)	0.0524 (5)
C5	0.1709 (4)	0.0158 (4)	0.2556 (2)	0.0598 (6)
C6	0.0713 (5)	0.1782 (4)	0.3408 (2)	0.0709 (7)
H6	0.0662	0.1474	0.4182	0.085*
C7	−0.0202 (4)	0.3834 (4)	0.3140 (2)	0.0714 (7)
H7	−0.0864	0.4896	0.3728	0.086*
C8	−0.0132 (4)	0.4303 (4)	0.2004 (2)	0.0687 (7)
H8	−0.0762	0.5690	0.1819	0.082*
C9	0.0874 (4)	0.2723 (4)	0.1125 (2)	0.0639 (6)
H9	0.0935	0.3050	0.0353	0.077*
C10	0.4997 (5)	−0.2615 (5)	−0.4198 (2)	0.0793 (8)
H10A	0.4179	−0.3296	−0.4283	0.119*
H10B	0.6391	−0.3635	−0.4083	0.119*
H10C	0.5132	−0.1911	−0.4884	0.119*
C11	0.2678 (6)	−0.2074 (4)	0.2878 (3)	0.0811 (8)
H11A	0.2357	−0.2111	0.3705	0.122*
H11B	0.4198	−0.2749	0.2614	0.122*
H11C	0.2095	−0.2787	0.2519	0.122*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0807 (5)	0.0453 (4)	0.0554 (4)	−0.0233 (3)	−0.0076 (3)	−0.0088 (2)
O1	0.1279 (18)	0.0579 (11)	0.0675 (12)	−0.0307 (12)	−0.0024 (11)	−0.0022 (9)
C1	0.0754 (15)	0.0555 (13)	0.0581 (13)	−0.0312 (12)	−0.0025 (11)	−0.0110 (10)
C2	0.0651 (14)	0.0516 (12)	0.0570 (13)	−0.0263 (11)	−0.0029 (10)	−0.0126 (10)
C3	0.0650 (13)	0.0497 (12)	0.0524 (12)	−0.0248 (10)	−0.0043 (10)	−0.0106 (9)
C4	0.0569 (12)	0.0455 (11)	0.0511 (11)	−0.0225 (9)	−0.0066 (9)	−0.0084 (8)
C5	0.0675 (14)	0.0561 (13)	0.0554 (12)	−0.0299 (11)	−0.0101 (10)	−0.0004 (10)
C6	0.0868 (18)	0.0749 (17)	0.0496 (13)	−0.0406 (14)	−0.0041 (12)	−0.0053 (11)
C7	0.0769 (16)	0.0612 (15)	0.0637 (15)	−0.0276 (13)	0.0019 (12)	−0.0204 (12)
C8	0.0773 (16)	0.0463 (12)	0.0700 (15)	−0.0221 (11)	−0.0061 (12)	−0.0092 (11)
C9	0.0798 (16)	0.0493 (12)	0.0549 (13)	−0.0258 (11)	−0.0104 (11)	−0.0016 (10)
C10	0.106 (2)	0.0705 (17)	0.0544 (14)	−0.0401 (16)	−0.0038 (14)	−0.0132 (12)
C11	0.113 (2)	0.0628 (16)	0.0651 (16)	−0.0389 (16)	−0.0217 (15)	0.0098 (12)

Geometric parameters (Å, º) top

S1—C4	1.771 (2)	C6—C7	1.375 (4)
S1—C3	1.804 (2)	C6—H6	0.9300
O1—C1	1.204 (3)	C7—C8	1.367 (4)
C1—C2	1.488 (4)	C7—H7	0.9300
C1—C10	1.506 (3)	C8—C9	1.388 (3)
C2—C3	1.522 (3)	C8—H8	0.9300
C2—H2A	0.9700	C9—H9	0.9300
C2—H2B	0.9700	C10—H10A	0.9600
C3—H3A	0.9700	C10—H10B	0.9600
C3—H3B	0.9700	C10—H10C	0.9600
C4—C5	1.390 (3)	C11—H11A	0.9600
C4—C9	1.398 (3)	C11—H11B	0.9600
C5—C6	1.386 (3)	C11—H11C	0.9600
C5—C11	1.506 (3)

C4—S1—C3	103.72 (11)	C7—C6—H6	119.1
O1—C1—C2	122.4 (2)	C5—C6—H6	119.1
O1—C1—C10	121.3 (3)	C8—C7—C6	119.5 (2)
C2—C1—C10	116.4 (2)	C8—C7—H7	120.2
C1—C2—C3	112.78 (19)	C6—C7—H7	120.2
C1—C2—H2A	109.0	C7—C8—C9	120.4 (2)
C3—C2—H2A	109.0	C7—C8—H8	119.8
C1—C2—H2B	109.0	C9—C8—H8	119.8
C3—C2—H2B	109.0	C8—C9—C4	119.9 (2)
H2A—C2—H2B	107.8	C8—C9—H9	120.1
C2—C3—S1	108.38 (16)	C4—C9—H9	120.1
C2—C3—H3A	110.0	C1—C10—H10A	109.5
S1—C3—H3A	110.0	C1—C10—H10B	109.5
C2—C3—H3B	110.0	H10A—C10—H10B	109.5
S1—C3—H3B	110.0	C1—C10—H10C	109.5
H3A—C3—H3B	108.4	H10A—C10—H10C	109.5
C5—C4—C9	119.8 (2)	H10B—C10—H10C	109.5
C5—C4—S1	117.25 (18)	C5—C11—H11A	109.5
C9—C4—S1	122.96 (18)	C5—C11—H11B	109.5
C6—C5—C4	118.5 (2)	H11A—C11—H11B	109.5
C6—C5—C11	120.6 (2)	C5—C11—H11C	109.5
C4—C5—C11	120.9 (2)	H11A—C11—H11C	109.5
C7—C6—C5	121.9 (2)	H11B—C11—H11C	109.5

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C4–C9 phenyl ring.

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10c···O1ⁱ	0.96	2.67	3.579 (4)	158
C3—H3a···S1ⁱⁱ	0.97	2.99	3.855 (3)	149
C3—H3b···S1ⁱⁱⁱ	0.97	3.02	3.870 (3)	147
C2—H2a···Cgⁱⁱ	0.97	2.86	3.628 (4)	137
C2—H2b···Cg^iv	0.97	2.95	3.678 (4)	133

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

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C4–C9 phenyl ring.

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10c···O1ⁱ	0.96	2.67	3.579 (4)	158
C3—H3a···S1ⁱⁱ	0.97	2.99	3.855 (3)	149
C3—H3b···S1ⁱⁱⁱ	0.97	3.02	3.870 (3)	147
C2—H2a···Cgⁱⁱ	0.97	2.86	3.628 (4)	137
C2—H2b···Cg^iv	0.97	2.95	3.678 (4)	133

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

Acknowledgements

This work was supported by the Ministry of Education, Science and Technological Development of the Republic of Serbia (Projects No. 172014, 172035 and 172034).

References

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 11| November 2013| Page o1625

doi:10.1107/S1600536813026895

Open

access