1-Piperonylpiperazinium 4-nitro­benzoate monohydrate

Channappa N Kavitha; Manpreet Kaur; Brian J Anderson; Jerry P Jasinski; H S Yathirajan

doi:10.1107/S160053681400261X

. 2014 Feb 12;70(Pt 3):o270–o271. doi: 10.1107/S160053681400261X

1-Piperonylpiperazinium 4-nitrobenzoate monohydrate

Channappa N Kavitha ^a, Manpreet Kaur ^a, Brian J Anderson ^b, Jerry P Jasinski ^b,^*, H S Yathirajan ^a

PMCID: PMC3998489 PMID: 24764985

Abstract

In the title hydrated salt [systematic name: 1-(1,3-benzodioxol-5-ylmethyl)piperazin-1-ium 4-nitrobenzoate monohydrate], C₁₂H₁₇N₂O₂ ⁺·C₇H₄NO₄ ⁻·H₂O, the piperazinium ring of the cation adopts a slightly distorted chair conformation. The piperonyl and piperazine rings are rotated with respect to each other with an N—C—C—C torsion angle of 45.6 (2)°. In the anion, the nitro group is almost coplanar with the adjacent benzene ring, forming a dihedral angle of only 3.9 (4)°. In the crystal, the cations, anions and water molecules are linked through N—H⋯O and O—H⋯O hydrogen bonds into chains along the a axis. In addition, weaker intermolecular C—H⋯O interactions are also observed within the chains. The anions form centrosymmetric couples through π-stacking interactions, with an intercentroid distance of 3.681 (4) Å between the benzene rings.

Related literature

For the drug, piribedil {systematic name: 2-[4-(benzo[1,3]dioxol-5-ylmethyl)piperazin-1-yl]pyrimidine}, an antiparkinsonian agent, see: Millan et al. (2001 ▶). For piperonylpiperazine derivatives with α-adrenergic antagonist and vasodilator properties, see: Gobert et al. (2003 ▶); Gilbert et al. (1968 ▶). For the use of piperazine in the construction of various bioactive molecules, see: Choudhary et al. (2006 ▶). For the antimicrobial activity of piperazine derivatives, see: Kharb et al. (2012 ▶). For related biologically active compounds, see: Brockunier et al. (2004 ▶); Bogatcheva et al. (2006 ▶). For a review on the current pharmacological and toxicological information for piperazine derivatives, see: Elliott (2011 ▶). For a related structure, see: Capuano et al. (2000 ▶). For puckering parameters, see Cremer & Pople (1975 ▶). For standard bond lengths, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₁₂H₁₇N₂O₂ ⁺·C₇H₄NO₄ ⁻·H₂O
M _r = 405.40
Triclinic,
a = 6.0745 (5) Å
b = 12.0617 (11) Å
c = 13.4817 (10) Å
α = 92.561 (7)°
β = 98.753 (7)°
γ = 93.326 (7)°
V = 973.20 (14) Å³
Z = 2
Cu Kα radiation
μ = 0.90 mm⁻¹
T = 173 K
0.42 × 0.36 × 0.24 mm

Data collection

Agilent Xcalibur (Eos, Gemini) diffractometer
Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012 ▶) T _min = 0.882, T _max = 1.000
6403 measured reflections
3761 independent reflections
3196 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.120
S = 1.03
3761 reflections
263 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.20 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 ▶; Palatinus & van der Lee, 2008 ▶; Palatinus et al., 2012 ▶); program(s) used to refine structure: SHELXL97 (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/S160053681400261X/ld2118sup1.cif

e-70-0o270-sup1.cif^{(29.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681400261X/ld2118Isup2.hkl

e-70-0o270-Isup2.hkl^{(206.3KB, hkl)}

Click here for additional data file.^{(7.9KB, cml)}

Supporting information file. DOI: 10.1107/S160053681400261X/ld2118Isup3.cml

CCDC reference: http://scripts.iucr.org/cgi-bin/cr.cgi?rm=csd&csdid=985155

Additional supporting information: crystallographic information; 3D view; checkCIF report

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2A—H2AA⋯O1W ⁱ	0.94	1.84	2.7800 (16)	172
N2A—H2AB⋯O1B ⁱⁱ	0.93	1.80	2.7262 (16)	175
C9A—H9AA⋯O2A ⁱⁱⁱ	0.99	2.58	3.3260 (19)	132
C10A—H10A⋯O1W ^iv	0.99	2.51	3.2833 (19)	135
O1W—H1WA⋯O2B ^v	0.90	1.76	2.6526 (16)	170
O1W—H1WB⋯O1B ⁱⁱ	0.92	1.90	2.7867 (16)	163

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

Acknowledgments

CNK 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 undertake research. JPJ acknowledges the NSF–MRI program (grant No. CHE-1039027) for funds to purchase the X-ray diffractometer.

supplementary crystallographic information

1. Comment

1-(3,4-Methylenedioxybenzyl)piperazine or 1-piperonylpiperazine is a psychoactive drug of the piperazine class and is used to synthesise the drug, piribedil, an antiparkinsonian agent (Millan et al., 2001). Piperonylpiperazine derivatives also has α-adrenergic antagonist properties (Gobert et al., 2003) and peripheral vasodilator properties (Gilbert et al., 1968). The piperazine moiety is extensively employed to construct various bioactive molecules with anti-bacterial, antimalarial activity and as antipsychotic agents (Choudhary et al., 2006). A valuable insight into recent advances on antimicrobial activity of piperazine derivatives is reported (Kharb et al., 2012). Piperazines are among the most important building blocks in today's drug discovery and are found in biologically active compounds across a number of different therapeutic areas (Brockunier et al., 2004; Bogatcheva et al., 2006). A review on the current pharmacological and toxicological information for piperazine derivatives is available (Elliott, 2011). The crystal structure of an N-piperonyl analogue of the atypical antipsychotic clozapine (Capuano et al., 2000) is reported. In continuation of our work on salts of piperonylpiperazines, this paper reports the crystal structure of the title compound, (I), C₁₂H₁₇N₂O₂⁺ . C₇H₄NO₄^- . H₂O.

The asymmetric unit of the title compound, (I), contains one independent 1-piperonylpiperazinium monocation, one 4-nitrobenzoate monoanion and one water molecule (Fig. 1). The piperazine ring in the cation adopts a slightly disordered chair conformation (puckering parameters Q, θ, and φ = 0.590 (2)Å, 3.8 (6)° and 1.68 (4)°; (Cremer & Pople, 1975). The piperonyl and piperazine rings are twisted with respect to each other with an N1A/C1A/C2A/C8A torsion angle of 45.6 (2)°. In the anion, the nitro substituent is slightly twisted from the mean plane of the phenyl ring with a dihedral angle of 3.9 (4)°. Bond lengths are in normal ranges (Allen et al., 1987). In the crystal, the cations and anions interact through N—H···O intermolecular hydrogen bonds while weak C—H···O intermolecular interactions are observed between the cations (Fig. 2). The crystal packing is stabilized by these N—H···O and O—H···O intermolecular hydrogen bonds and weak C—H···O intermolecular interactions (Table 1) involving the water molecules which form 1D chains along [1 0 0]. In addition, weak Cg5–Cg5 π–π stacking interactions with an intercentroid distance of 3.681 (4)Å (Symmetry operation 2-x, -y, -z; Cg5 is the centroid between the phenyl rings, C1B–C6B, of the anions) contribute to the crystal packing.

2. Experimental

1-piperonylpiperazine ( 2.2g, 0.01 mol) and p-nitrobenzoic acid (1.67 g, 0.01 mol) were dissolved in hot N,N-dimethylformamide and stirred for 10 mins at 323 K. The resulting solution was allowed to cool slowly at room temperature. The crystals of the title salt appeared after a few days was used as such for x-ray studies (m. p:448-451 K).