Methyl 2-[4-(tri­fluoro­meth­yl)phenyl­sulfan­yl]benzoate

Thammarse S Yamuna; Jerry P Jasinski; Brian J Anderson; H S Yathirajan; Manpreet Kaur

doi:10.1107/S1600536813028146

. 2013 Oct 19;69(Pt 11):o1670. doi: 10.1107/S1600536813028146

Methyl 2-[4-(trifluoromethyl)phenylsulfanyl]benzoate

Thammarse S Yamuna ^a, Jerry P Jasinski ^b,^*, Brian J Anderson ^b, H S Yathirajan ^a, Manpreet Kaur ^a

PMCID: PMC3884328 PMID: 24454104

Abstract

In the title compound, C₁₅H₁₃F₃O₂S, the dihedral angle between the benzene rings is 79.5 (1)°. The ester group is twisted by 7.6 (1)° from the mean plane of the adjacent benzene ring. Disorder was modeled over two sites for one F atom of the trifluoromethyl group with an occupancy ratio of 0.54 (6):0.46 (6). In the crystal, molecules are linked via weak C—H⋯O hydrogen bonds, forming two-dimensional networks lying parallel to (101). The networks are linked via C—H⋯π interactions, leading to the formation of a three-dimensional supramolecular structure.

Related literature

For general background and pharmacological properties of the neuroleptic agent flupentixol [systematic name: (EZ)-2-[4-[3-[2-(trifluoromethyl)thioxanthen-9-ylidene]propyl]piperazin-1-yl]ethanol] and related compounds, see: Ovhed (1976 ▶); Robertson & Trimble (1981 ▶); Valle-Jones & Swarbrick (1981 ▶); Young et al. (1976 ▶). For related structures, see: Post et al. (1975a ▶,b ▶); Siddegowda et al. (2011a ▶,b ▶). For standard bond lengths, see: Allen et al. (1987 ▶). graphic file with name e-69-o1670-scheme1.jpg

Experimental

Crystal data

C₁₅H₁₁F₃O₂S
M _r = 312.30
Monoclinic,
a = 11.0675 (5) Å
b = 8.0429 (3) Å
c = 15.6614 (7) Å
β = 96.654 (5)°
V = 1384.70 (11) Å³
Z = 4
Cu Kα radiation
μ = 2.44 mm⁻¹
T = 173 K
0.28 × 0.22 × 0.12 mm

Data collection

Agilent Gemini EOS diffractometer
Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012 ▶) T _min = 0.715, T _max = 1.000
8110 measured reflections
2705 independent reflections
2224 reflections with I > 2σ(I)
R _int = 0.039

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.123
S = 1.03
2705 reflections
201 parameters
H-atom parameters constrained
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Agilent, 2012 ▶); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007 ▶); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2008 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: OLEX2.

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536813028146/su2658sup1.cif

e-69-o1670-sup1.cif^{(22.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813028146/su2658Isup2.hkl

e-69-o1670-Isup2.hkl^{(148.6KB, hkl)}

Click here for additional data file.^{(5.2KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813028146/su2658Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

Cg is the centroid of the C2–C7 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C15—H15C⋯O2ⁱ	0.96	2.45	3.221 (3)	138
C12—H12⋯Cg ⁱⁱ	0.93	2.70	3.558 (2)	154

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

Acknowledgments

TSY thanks the University of Mysore for research facilities and is also grateful to the Principal, Maharani’s Science College for women, Mysore, for giving permission to do research. JPJ acknowledges the NSF–MRI program (grant No. CHE-1039027) for funds to purchase the X-ray diffractometer.

supplementary crystallographic information

1. Comment

The title compound,C₁₅H₁₃F₃O₂S, is a methyl ester derivative of the starting material for the synthesis of the flupentixol [systematic name: (EZ)-2-[4-[3-[2-(trifluoromethyl)thioxanthen-9-ylidene]propyl]piperazin-1-yl]ethanol], a well documented neuroleptic. There have been many controlled studies that compared it with a placebo (Ovhed, 1976) and classical antidepressants (Young et al., 1976). Low-dose neuroleptics have been applied increasingly in recent years to treat anxiety and depression (Robertson & Trimble, 1981; Valle-Jones & Swarbrick, 1981). The crystal structures of α-flupenthixol (Post et al., 1975a) and β-flupenthixol (Post et al., 1975b) have been reported. The crystal structures of some related compounds reported by our group are: 1-(2-Hydroxyethyl)-4-[3-(2-trifluoromethyl-9H-thioxanthen- 9-ylidene)propyl]piperazine-1,4-diium dichloride: the dihydrochloride salt of flupentixol (Siddegowda et al., 2011a), and 1-(2-Hydroxyethyl) -4-{3-[(E)-2-(trifluoromethyl)-9H-thioxanthen-9-ylidene]propyl}piperazine-1,4-diium bis(3-carboxyprop-2-enoate) (Siddegowda et al., 2011b). In view of the importance of flupentixol, we report herein on the crystal structure of the title compound a methyl ester derivative of the starting material for the synthesis of the flupentixol.

In the title molecule, Fig. 1, the dihedral angle between the two benzene rings, (C2-C7) and (C8-C13) is 79.5 (1)°. The ester group (O1/C1/C2/O2) is twisted by 7.6 (1)° from the mean plane of the adjacent benzene ring (C2–C7). Disorder was modeled over two sets of sites for fluorine atom, F3/F3A of the trifluoromethyl group, with an occupancy ratio of 0.54 (6) : 0.46 (6). Bond lengths are in normal ranges (Allen et al., 1987).

In the crystal, molecules are linked via C—H···O hydrogen bonds forming two-dimensional networks lying parallel to (101). These networks are linked via C-H···π interactions leading to the formation of a three-dimensional supramolecular structure (Table 1 and Fig. 2).

2. Experimental

The reactant 2-(4-Trifluoromethylphenylsulfanyl)benzoic acid (I) was obtained as a gift sample from R. L. Fine Chem, Bengaluru, India. 10 g of (I) [0.0335 mol] was dissolved in 50 ml of methanol, followed by the addition of 1 ml of 98% sulphuric acid and the mixture was refluxed for 8 hours at 338 K. The methanol was distilled off and 100 ml of 10% Na₂CO₃ solution was added and the mixture stirred for 5 min. This was then extracted with dichloromethane and then the solvent was removed by distillation. The product formed was recrystallized from methanol giving colourless block-like crystals of the title compound (M.p. = 413-418 K).