4-(4-Methyl­phenyl­sulfon­yl)piperazin-1-ium tri­fluoro­acetate

S Sreenivasa; N R Mohan; T Madhu Chakrapani Rao; P A Suchetan; B S Palakshamurthy; Vijithkumar

doi:10.1107/S1600536813015900

. 2013 Jun 19;69(Pt 7):o1112. doi: 10.1107/S1600536813015900

4-(4-Methylphenylsulfonyl)piperazin-1-ium trifluoroacetate

S Sreenivasa ^a,^*, N R Mohan ^a, T Madhu Chakrapani Rao ^b, P A Suchetan ^c, B S Palakshamurthy ^d, Vijithkumar ^e

PMCID: PMC3770385 PMID: 24046670

Abstract

In the title salt, C₁₁H₁₇N₂O₂S⁺·CF₃COO⁻, the cation is protonated at the secondary piperazine N atom. The dihedral angle between the benzene ring and the piperazine mean plane is 85.54 (10)°. In the crystal, cations and anions are connected by two types of strong N—H⋯O hydrogen bonds into chains extending along [101]. The chains are further assembled into (10-1) layers via stacking interactions between benzene rings of the cations [centroid–centroid distance = 3.7319 (13) Å] and a C—H⋯O interaction involving a piperazine C—H group and a sulfonyl O atom. Another C—H⋯O interaction between the piperazine ring and the sulfonyl group connects the ions into a three-dimensional network.

Related literature

For the synthesis, characterization and biological activity of piperazine derivatives, see: Gan et al. (2009a ▶,b ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). graphic file with name e-69-o1112-scheme1.jpg

Experimental

Crystal data

C₁₁H₁₇N₂O₂S⁺·C₂F₃O₂ ⁻
M _r = 354.35
Monoclinic,
a = 7.8796 (6) Å
b = 22.5891 (15) Å
c = 9.4626 (7) Å
β = 110.446 (3)°
V = 1578.2 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 100 K
0.24 × 0.22 × 0.20 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.941, T _max = 0.950
11562 measured reflections
2781 independent reflections
2417 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.094
S = 1.04
2781 reflections
217 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.86 e Å⁻³
Δρ_min = −0.55 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: APEX2 and SAINT-Plus (Bruker, 2009 ▶); data reduction: SAINT-Plus and XPREP (Bruker, 2009 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813015900/gk2578sup1.cif

e-69-o1112-sup1.cif^{(25.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813015900/gk2578Isup2.hkl

e-69-o1112-Isup2.hkl^{(136.6KB, hkl)}

Click here for additional data file.^{(6.1KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813015900/gk2578Isup3.cml

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

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N2⋯O4ⁱ	0.87 (3)	1.91 (3)	2.782 (2)	174 (2)
C8—H8B⋯O1ⁱⁱ	0.97	2.45	3.328 (2)	150
C9—H9B⋯O2ⁱⁱⁱ	0.97	2.43	3.146 (2)	130
N2—H2N2⋯O3	0.86 (2)	1.86 (2)	2.690 (2)	163 (2)

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

Acknowledgments

The authors thank Dr S. C. Sharma, Former Vice Chancellor, Tumkur University, Tumkur for his constant encouragement and Professor T. N. Guru Row, Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore, for his help and valuable suggestions. BSPM thanks Dr H. C. Devaraje Gowda, Department of Physics Yuvarajas College (constituent), University of Mysore, for his guidance.

supplementary crystallographic information

Comment

Numerous piperazine derivatives like aryl amide, sulfonamides, Mannich bases, Schiff bases, thiazolidinones, azetidinones, imidazolinones have shown a wide spectrum of biological activities viz. anti-inflammatory, antibacterial, antimalarial, anticonvulsant, antipyretic, antitumor, anthelmintics, analgesic, antidepressant, antifungal, antitubercular, anticancer, antidiabetic (Gan et al., 2009a,b). Keeping this in mind, we synthesized the title compound and here we report its crystal structure.

The title molecular salt, C₁₁H₁₇SO₂N₂⁺.CF₃COO^-, crystallizes in monoclinic crystal system and P2₁/n space group. The cation is protonated at the secondary N atom of the piperazine ring (Fig. 1). The piperazine ring adopts a chair conformation and the dihedral angle between the benzene ring and the piperazine ring (considering the mean plane formed by all the non-hydrogen atoms) in the cation is 85.54 (10)^o. In the crystal, the ions are connected by strong N2—H1(N2)···O4 and N2—H2(N2)···O3 hydrogen bonds (Fig. 2, Table 1). The cations are further connected through weak C8—H8B···O1 and C9—H9B···O2 interactions forming chain C(6) and ring R₂²(8) motifs (Bernstein et al.1995) (Fig. 3, Table 1). The crystal structure is further stabilized by aromatic π-π stacking interactions.

Experimental

A mixture of tert-butyl 4-[(4-methylphenyl)sulfonyl]piperazine-1-carboxylate (0.002 moles, 1 gram) (1), trifluroacetic acid (TFA) (0.013 moles, 1 ml) in 1,2-dichloroethane (10 ml) was refluxed for 2 h. Reaction mixture was then cooled to room temperature and concentrated to get crude pale yellow colored solid 1-[(4-methylphenyl)sulfonyl]piperazine (2). The crude compound (2) was purified by column chromatography using petroleum ether:/ethyl acetate (7:3) as eluent to get white coloured solid (melting point = 518 K), which was further recrystallized from petroleum ether/ dichloromethane (1:1) to obtain colorless crystals suitable for diffraction studies.