4-[(4-Chloro­phen­yl)(phen­yl)­meth­yl]­piperazin-1-ium picrate monohydrate

Yanxi Song; C S Chidan Kumar; S Chandraju; S Naveen; Hongqi Li

doi:10.1107/S1600536812031984

. 2012 Jul 18;68(Pt 8):o2486. doi: 10.1107/S1600536812031984

4-[(4-Chlorophenyl)(phenyl)methyl]piperazin-1-ium picrate monohydrate

Yanxi Song ^a, C S Chidan Kumar ^b, S Chandraju ^c, S Naveen ^d, Hongqi Li ^e,^*

PMCID: PMC3414941 PMID: 22904928

Abstract

The asymmetric unit of the title compound, C₁₇H₂₀ClN₂ ⁺·C₆H₂N₃O₇ ⁻·H₂O, contains a piperazin-1-ium cation, a picrate anion and one solvent water molecule. The piperazene ring is protonated at one N atom and adopts a highly distorted chair conformation with the chloropheny(phenyl)methyl substituent on the second N atom in an equatorial position. The crystal structure is stabilized by O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds.

Related literature

For the biological activity of 1-benzylpiperazine, see: Campbell et al. (1973 ▶). For related structures, see: Jasinski et al. (2011 ▶); Song et al. (2012 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₁₇H₂₀ClN₂ ⁺·C₆H₂N₃O₇ ⁻·H₂O
M _r = 533.92
Monoclinic,
a = 21.144 (2) Å
b = 8.2997 (8) Å
c = 28.528 (3) Å
β = 93.029 (1)°
V = 4999.3 (8) Å³
Z = 8
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 296 K
0.25 × 0.22 × 0.07 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.949, T _max = 0.985
12567 measured reflections
4417 independent reflections
2996 reflections with I > 2σ(I)
R _int = 0.026

Refinement

R[F ² > 2σ(F ²)] = 0.057
wR(F ²) = 0.175
S = 1.04
4417 reflections
334 parameters
H-atom parameters constrained
Δρ_max = 0.63 e Å⁻³
Δρ_min = −0.46 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812031984/sj5246sup1.cif

e-68-o2486-sup1.cif^{(28.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812031984/sj5246Isup2.hkl

e-68-o2486-Isup2.hkl^{(216.5KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812031984/sj5246Isup3.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—H2A⋯O1W ⁱ	0.90	2.03	2.850 (4)	151
N2—H2B⋯O1ⁱⁱ	0.90	1.96	2.819 (3)	160
N2—H2B⋯O2ⁱⁱ	0.90	2.42	3.017 (4)	124
O1W—H1WA⋯O1	0.85	1.97	2.805 (3)	168
C16—H16B⋯O5ⁱⁱⁱ	0.97	2.34	3.166 (4)	143

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

Acknowledgments

This work was supported in part by the Council for the Chemical Sciences of the Netherlands Organization for Scientific Research. YS and HL acknowledge financial support by the Fundamental Research Funds for the Central Universities.

supplementary crystallographic information

Comment

1-Benzylpiperazine was originally synthesized as a potential anthelmintic (Campbell et al., 1973) and its derivatives were found to possess excellent pharmacological activities. These include vasodilator, hypotensive and antiviral activity, the ability to increase cerebral blood flow and broad pharmacological action on central nervous system. In the course of our studies on the salts of piperazines (Jasinski et al., 2011; Song et al., 2012) and in view of the importance of piperazines, the paper reports the crystal and molecular structure of the title piperazin-1-ium salt.

The molecular structure and atom numbering scheme of the title compound are shown in Fig 1. In the title compound, the piperazine group is protonated at the N2 atom and adopts a highly distorted chair conformation with puckering parameters Q, θ and φ having values of 0.595 (3) °, 6.4 (3) ° and 342 (3) °, respectively. For an ideal chair conformation, θ has a value of 0 or 180°. The bond lengths (Allen et al., 1987) and bond angles are in good agreement with standard values. The crystal structure is stabilized by intermolecular O–H···O, N–H···O and C–H···O hydrogen bonds.

Experimental

1-((4-Chlorophenyl)(phenyl)methyl)piperazine (2.88 g, 0.01 mol) and picric acid (2.99 g, 0.01 mol) were dissolved separately in methanol. Both the solutions were mixed together and stirred for a few minutes at room temperature. The precipitate was collected by filtration and purified by recrystallization from methanol. On recrystallization with DMF after 15 days, good quality single crystals were obtained by the slow evaporation method. (M.P.: 441–445 K).