4-Methyl-N-(4-nitro­benzyl­idene)piperazin-1-amine

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

doi:10.1107/S1600536813028493

. 2013 Oct 23;69(Pt 11):o1687–o1688. doi: 10.1107/S1600536813028493

4-Methyl-N-(4-nitrobenzylidene)piperazin-1-amine

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

PMCID: PMC3884341 PMID: 24454117

Abstract

In the title compound, C₁₂H₁₆N₄O₂, the piperazine ring is in a slightly distorted chair conformation. In the molecule, the mean plane of the nitro group is twisted by 8.0 (3)° from that of the benzene ring. Also, the mean plane of the 2-nitrobenzyl ring is twisted slightly from that of the piperazine ring, with an N—N=C—C torsion angle of −176.24 (11)°. In the crystal, pairs of weak C—H⋯O interactions link the molecules into dimers approximately along [010].

Related literature

For the biological activity of Schiff base piperzine derivatives, see: Kharb et al. (2012 ▶); Savaliya et al. (2010 ▶); Xu et al. (2009 ▶); Zhou et al. (2011 ▶). For therapeutic areas related to piperazines as drug molecules, see: Bogatcheva et al. (2006 ▶); Brockunier et al. (2004 ▶); Cai et al. (2009 ▶); Choudhary et al. (2006 ▶); Upadhayaya et al. (2004 ▶). For a review of current pharmacological and toxicological information for piperazine derivatives, see: Elliott (2011 ▶). For the synthesis of related piperazine compounds and their medicinal and pharmaceutical activity, see: Capuano et al. (2002 ▶); Contreras et al. (2001 ▶). For related structures, see: Guo (2007 ▶); Ming-Lin et al. (2007 ▶); Xu et al. (2012 ▶); Zhou et al. (2011 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶). For standard bond lengths, see: Allen et al. (1987 ▶). graphic file with name e-69-o1687-scheme1.jpg

Experimental

Crystal data

C₁₂H₁₆N₄O₂
M _r = 248.29
Monoclinic,
a = 27.9353 (14) Å
b = 5.9247 (3) Å
c = 18.7763 (7) Å
β = 126.527 (3)°
V = 2497.2 (2) Å³
Z = 8
Cu Kα radiation
μ = 0.77 mm⁻¹
T = 173 K
0.38 × 0.32 × 0.22 mm

Data collection

Agilent Xcalibur (Eos, Gemini) diffractometer
Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012 ▶) T _min = 0.868, T _max = 1.000
7200 measured reflections
2439 independent reflections
2022 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.119
S = 1.02
2439 reflections
165 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.18 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/S1600536813028493/zl2568sup1.cif

e-69-o1687-sup1.cif^{(22.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813028493/zl2568Isup2.hkl

e-69-o1687-Isup2.hkl^{(134.2KB, hkl)}

Click here for additional data file.^{(5.1KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813028493/zl2568Isup3.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
C2—H2B⋯O1ⁱ	0.99	2.47	3.4052 (19)	158

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Symmetry code: (i) Inline graphic .

Acknowledgments

CNK thanks 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

Schiff base ligands derived from 1-amino-4-methylpiperazine have attracted interest due to diverse biological activities associated with the piperazine moiety. Schiff base piperazine derivatives have been designed to study their antimicrobial (Savaliya et al., 2010; Kharb et al., 2012)) and antibacterial activity (Xu et al., 2012). In addition, many drugs contain a piperazine ring as part of their molecular structure (Cai et al., 2009). 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) such as antifungal (Upadhayaya et al., 2004), anti-bacterial, antimalarial activity and as in antipsychotic agents (Choudhary et al., 2006). A review on the current pharmacological and toxicological information for piperazine derivatives has been recently presented (Elliott, 2011). The synthesis of related piperazine compounds and their medicinal and pharmaceutical activity have also been reported (Contreras et al., 2001; Capuano et al., 2002). The crystal structures of some related compounds, viz., 2-[(4-methylpiperazin-1-yl)iminomethyl]phenol (Guo, 2007), 1,4-bis{3-[4-(dimethylamino)benzylideneamino] propyl}piperazine (Xu et al., 2009), 2-methoxy-4-[(4-methylpiperazin-1-yl)- iminomethyl]phenol (Zhou et al., 2011) and 2,4-dibromo-6- [(4-methylpiperazin-1-yl)iminomethyl]phenol (Ming-Lin et al., 2007) have been reported. In view of the above importance of N-piperazinyl Schiff bases, the title compound, (I), C₁₂H₁₆N₄O₂ has been synthesized and the crystal structure is reported herin.

In the title compound, (I), the piperazine ring is in a slightly distorted chair conformation with puckering parameters Q, θ, and φ = 0.5646Å, 170.8 (5)° and 187.961 (8)° (Cremer & Pople, 1975) (Fig. 1). In the molecule, the mean plane of the nitro group is twisted by 8.0 (3)° from that of the phenyl ring. Also, the mean plane of the 2-nitrobenzyl ring is twisted slightly from that of the piperazine ring with an N1/N2/C5/C6 torsion angle of -176.24 (11)°. Bond lengths are in normal ranges (Allen et al., 1987). Weak C—H···O intermolecular interactions are observed which lead to formation of dimers approximately along [010] and influence crystal packing (Fig. 2).

2. Experimental

To a solution of o-nitrobenzaldehyde (0.75 g, 0.005 mol) in 10 ml of methanol, an equimolar amount of (1-amino-4-methyl)piperazine (0.57 g, 0.005 mol) is added dropwise with constant stirring. The mixture was refluxed for 8 hours to obtain an orange solution. The solution was evaporated to a small volume at room temperature and allowed to stand. Yellow crystals were formed in one day (m.p.: 358–360 K) and were used as such for x-ray diffraction studies.