4-(4-Carboxy­benz­yl)-1-methyl­piperazin-1-ium picrate

Hongqi Li; Q N M Hakim Al-arique; H S Yathirajan; B Narayana; A R Ramesha

doi:10.1107/S1600536809004474

. 2009 Feb 13;65(Pt 3):o518. doi: 10.1107/S1600536809004474

4-(4-Carboxybenzyl)-1-methylpiperazin-1-ium picrate

Hongqi Li ^a,^*, Q N M Hakim Al-arique ^b, H S Yathirajan ^b, B Narayana ^c, A R Ramesha ^d

PMCID: PMC2968640 PMID: 21582181

Abstract

The title compound, C₁₃H₁₉N₂O₂ ⁺·C₆H₂N₃O₇ ⁻, is a salt obtained by cocrystallization of 4-[(4-methylpiperazin-1-yl)methyl]benzoic acid and picric acid. The cations adopt an ‘L-shaped’ conformation and are linked into chains along [010] by O—H⋯N hydrogen bonds. The NH group of each piperazinium ring forms a hydrogen bond to the phenolate O atom of a picrate anion, and the picrate anions form face-to-face contacts with an interplanar separation of 3.023 (1) Å.

Related literature

For general background, see: Druker et al. (2001 ▶). For related structures, see: Swamy et al. (2007 ▶); Bindya et al. (2007 ▶); Sarojini et al. (2007 ▶); Wang & Jia (2008 ▶).

Experimental

Crystal data

C₁₃H₁₉N₂O₂ ⁺·C₆H₂N₃O₇ ⁻
M _r = 463.41
Triclinic,
a = 7.3020 (12) Å
b = 9.5993 (16) Å
c = 15.131 (3) Å
α = 86.448 (2)°
β = 79.145 (2)°
γ = 79.950 (2)°
V = 1025.2 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 296 K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T _min = 0.965, T _max = 0.976
5373 measured reflections
3565 independent reflections
2745 reflections with I > 2σ(I)
R _int = 0.016

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.104
S = 1.06
3565 reflections
305 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); 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 datablocks global, I. DOI: 10.1107/S1600536809004474/bi2341sup1.cif

e-65-0o518-sup1.cif^{(22.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809004474/bi2341Isup2.hkl

e-65-0o518-Isup2.hkl^{(174.8KB, hkl)}

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
O8—H8⋯N4ⁱ	0.82	1.79	2.6006 (19)	172
N5—H5A⋯O1ⁱⁱ	0.89 (2)	1.89 (2)	2.734 (2)	156.9 (18)

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

Acknowledgments

QNMHA thanks R. L. Fine Chem, Bangalore, for a gift sample of 4-[(4-methylpiperazin-1-yl)methyl]benzoic acid. HSY thanks the University of Mysore for research facilities.

supplementary crystallographic information

Comment

4-[(4-Methylpiperazin-1-yl)methyl]benzoic acid is an intermediate in the synthesis of Imatinib, a drug used to treat certain types of cancer. Its mesylate salt is currently marketed by Novartis as Gleevec (Druker et al., 2001). Picric acid forms salts or charge-transfer complexes with many organic compounds. Crystal structures of picrate complexes with organic compounds of pharmaceutical importance viz., desipraminium picrate (Swamy et al., 2007) and amitriptylinium picrate (Bindya et al., 2007) have been reported. A three-dimensional network in piperazine-1,4-diium-picrate-piperazine (1/2/1) is reported recently (Wang & Jia, 2008).

Experimental

The title compound was prepared by taking equimolar quantities of picric acid (0.92 g, 2 mmol) and 4-[(4-methylpiperazin-1-yl)methyl]benzoic acid (0.47 g, 2 mmol) and dissolving them in water. The solution was stirred well at room temperature and slow evaporation of the solution resulted in the formation of the yellow coloured salt (yield 95%). Crystals suitable for single-crystal X-ray diffraction were grown from dimethyl formamide solvent.