4-Methyl-N-(4-nitro-benzyl-idene)piperazin-1-amine.

In the title compound, C12H16N4O2, the piperazine ring is in a slightly distorted chair conformation. In the mol-ecule, 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-nitro-benzyl 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 inter-actions link the mol-ecules 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 ▶).

Experimental

Crystal data

C12H16N4O2

M = 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

Δρmax = 0.22 e Å−3

Δρmin = −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.

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536813028493/zl2568sup1.cif

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

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813028493/zl2568Isup3.cml

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

C12H16N4O2	F(000) = 1056
Mr = 248.29	Dx = 1.321 Mg m−3
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54184 Å
a = 27.9353 (14) Å	Cell parameters from 2934 reflections
b = 5.9247 (3) Å	θ = 3.2–72.3°
c = 18.7763 (7) Å	µ = 0.77 mm−1
β = 126.527 (3)°	T = 173 K
V = 2497.2 (2) Å3	Irregular, yellow
Z = 8	0.38 × 0.32 × 0.22 mm

Agilent Xcalibur (Eos, Gemini) diffractometer	2439 independent reflections
Radiation source: Enhance (Cu) X-ray Source	2022 reflections with I > 2σ(I)
Detector resolution: 16.0416 pixels mm-1	Rint = 0.031
ω scans	θmax = 72.3°, θmin = 3.9°
Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012)	h = −34→32
Tmin = 0.868, Tmax = 1.000	k = −7→7
7200 measured reflections	l = −15→22

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.041	w = 1/[σ2(Fo2) + (0.0636P)2 + 0.9105P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.119	(Δ/σ)max = 0.001
S = 1.02	Δρmax = 0.22 e Å−3
2439 reflections	Δρmin = −0.18 e Å−3
165 parameters	Extinction correction: SHELXL2012 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraints	Extinction coefficient: 0.00056 (10)
Primary atom site location: structure-invariant direct methods

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

	x	y	z	Uiso*/Ueq
O1	0.93562 (6)	1.1504 (2)	1.26970 (8)	0.0636 (4)
O2	0.96924 (5)	0.8095 (2)	1.29508 (7)	0.0509 (3)
N1	0.60437 (5)	0.7685 (2)	0.55865 (7)	0.0301 (3)
N2	0.66959 (5)	0.80238 (19)	0.74619 (7)	0.0282 (3)
N3	0.71366 (5)	0.8675 (2)	0.83118 (7)	0.0290 (3)
N4	0.93437 (5)	0.9567 (3)	1.24576 (8)	0.0403 (3)
C1	0.58784 (6)	0.9349 (2)	0.59774 (9)	0.0328 (3)
H1A	0.5570	0.8709	0.6023	0.039*
H1B	0.5710	1.0702	0.5594	0.039*
C2	0.64208 (6)	1.0007 (2)	0.68894 (9)	0.0329 (3)
H2A	0.6714	1.0761	0.6836	0.039*
H2B	0.6302	1.1090	0.7160	0.039*
C3	0.68086 (6)	0.6183 (2)	0.70644 (9)	0.0311 (3)
H3A	0.6928	0.4816	0.7438	0.037*
H3B	0.7140	0.6601	0.7037	0.037*
C4	0.62582 (6)	0.5677 (2)	0.61410 (9)	0.0317 (3)
H4A	0.6352	0.4494	0.5868	0.038*
H4B	0.5941	0.5090	0.6177	0.038*
C5	0.75644 (6)	0.7311 (2)	0.88472 (8)	0.0290 (3)
H5	0.7586	0.5880	0.8640	0.035*
C6	0.80153 (6)	0.7948 (2)	0.97695 (9)	0.0282 (3)
C7	0.80100 (6)	1.0039 (2)	1.01127 (9)	0.0317 (3)
H7	0.7706	1.1101	0.9737	0.038*
C8	0.84416 (6)	1.0572 (3)	1.09893 (9)	0.0336 (3)
H8	0.8438	1.1991	1.1221	0.040*
C9	0.88821 (6)	0.8997 (3)	1.15268 (9)	0.0326 (3)
C10	0.89029 (6)	0.6922 (3)	1.12129 (9)	0.0344 (3)
H10	0.9208	0.5867	1.1594	0.041*
C11	0.84702 (6)	0.6411 (2)	1.03298 (9)	0.0330 (3)
H11	0.8482	0.4998	1.0101	0.040*
C12	0.55353 (7)	0.7136 (3)	0.46826 (9)	0.0387 (4)
H12A	0.5211	0.6537	0.4689	0.058*
H12B	0.5654	0.6002	0.4436	0.058*
H12C	0.5400	0.8502	0.4317	0.058*

	U11	U22	U33	U12	U13	U23
O1	0.0527 (8)	0.0698 (9)	0.0412 (7)	0.0008 (6)	0.0132 (6)	−0.0240 (6)
O2	0.0326 (6)	0.0792 (9)	0.0295 (6)	0.0096 (6)	0.0123 (5)	0.0014 (6)
N1	0.0278 (6)	0.0347 (6)	0.0256 (6)	−0.0026 (5)	0.0146 (5)	−0.0031 (5)
N2	0.0279 (6)	0.0289 (6)	0.0245 (6)	−0.0001 (4)	0.0138 (5)	−0.0035 (4)
N3	0.0278 (6)	0.0326 (6)	0.0257 (6)	−0.0038 (5)	0.0154 (5)	−0.0042 (4)
N4	0.0280 (6)	0.0624 (9)	0.0287 (6)	−0.0011 (6)	0.0159 (6)	−0.0066 (6)
C1	0.0290 (7)	0.0327 (7)	0.0301 (7)	0.0031 (5)	0.0140 (6)	−0.0005 (5)
C2	0.0335 (7)	0.0274 (7)	0.0310 (7)	0.0027 (5)	0.0156 (6)	−0.0022 (6)
C3	0.0312 (7)	0.0286 (7)	0.0284 (7)	0.0021 (5)	0.0150 (6)	−0.0031 (5)
C4	0.0334 (7)	0.0291 (7)	0.0302 (7)	−0.0029 (5)	0.0177 (6)	−0.0061 (5)
C5	0.0291 (7)	0.0304 (7)	0.0290 (7)	−0.0023 (5)	0.0181 (6)	−0.0026 (5)
C6	0.0271 (7)	0.0331 (7)	0.0278 (7)	−0.0036 (5)	0.0183 (6)	−0.0010 (5)
C7	0.0291 (7)	0.0354 (7)	0.0289 (7)	0.0009 (6)	0.0163 (6)	−0.0002 (6)
C8	0.0325 (7)	0.0365 (8)	0.0330 (7)	−0.0035 (6)	0.0202 (6)	−0.0065 (6)
C9	0.0261 (7)	0.0467 (8)	0.0264 (7)	−0.0050 (6)	0.0165 (6)	−0.0041 (6)
C10	0.0282 (7)	0.0437 (8)	0.0295 (7)	0.0037 (6)	0.0161 (6)	0.0037 (6)
C11	0.0325 (7)	0.0341 (7)	0.0334 (7)	0.0004 (6)	0.0201 (6)	−0.0018 (6)
C12	0.0333 (8)	0.0498 (9)	0.0265 (7)	−0.0039 (6)	0.0142 (6)	−0.0052 (6)

O1—N4	1.2253 (19)	C4—H4A	0.9900
O2—N4	1.2219 (18)	C4—H4B	0.9900
N1—C1	1.4586 (17)	C5—H5	0.9500
N1—C4	1.4546 (18)	C5—C6	1.4598 (19)
N1—C12	1.4608 (17)	C6—C7	1.401 (2)
N2—N3	1.3682 (15)	C6—C11	1.400 (2)
N2—C2	1.4639 (17)	C7—H7	0.9500
N2—C3	1.4580 (16)	C7—C8	1.379 (2)
N3—C5	1.2889 (18)	C8—H8	0.9500
N4—C9	1.4657 (18)	C8—C9	1.388 (2)
C1—H1A	0.9900	C9—C10	1.379 (2)
C1—H1B	0.9900	C10—H10	0.9500
C1—C2	1.5137 (19)	C10—C11	1.384 (2)
C2—H2A	0.9900	C11—H11	0.9500
C2—H2B	0.9900	C12—H12A	0.9800
C3—H3A	0.9900	C12—H12B	0.9800
C3—H3B	0.9900	C12—H12C	0.9800
C3—C4	1.5122 (18)
C1—N1—C12	110.78 (11)	C3—C4—H4A	109.4
C4—N1—C1	108.16 (10)	C3—C4—H4B	109.4
C4—N1—C12	110.55 (11)	H4A—C4—H4B	108.0
N3—N2—C2	110.17 (10)	N3—C5—H5	119.7
N3—N2—C3	119.30 (10)	N3—C5—C6	120.54 (13)
C3—N2—C2	113.80 (10)	C6—C5—H5	119.7
C5—N3—N2	120.39 (12)	C7—C6—C5	122.44 (13)
O1—N4—C9	117.78 (14)	C11—C6—C5	118.67 (13)
O2—N4—O1	123.67 (13)	C11—C6—C7	118.89 (13)
O2—N4—C9	118.55 (14)	C6—C7—H7	119.6
N1—C1—H1A	109.7	C8—C7—C6	120.72 (14)
N1—C1—H1B	109.7	C8—C7—H7	119.6
N1—C1—C2	109.86 (11)	C7—C8—H8	120.6
H1A—C1—H1B	108.2	C7—C8—C9	118.76 (13)
C2—C1—H1A	109.7	C9—C8—H8	120.6
C2—C1—H1B	109.7	C8—C9—N4	118.83 (13)
N2—C2—C1	111.02 (11)	C10—C9—N4	118.94 (13)
N2—C2—H2A	109.4	C10—C9—C8	122.22 (13)
N2—C2—H2B	109.4	C9—C10—H10	120.7
C1—C2—H2A	109.4	C9—C10—C11	118.56 (13)
C1—C2—H2B	109.4	C11—C10—H10	120.7
H2A—C2—H2B	108.0	C6—C11—H11	119.6
N2—C3—H3A	109.5	C10—C11—C6	120.84 (13)
N2—C3—H3B	109.5	C10—C11—H11	119.6
N2—C3—C4	110.69 (11)	N1—C12—H12A	109.5
H3A—C3—H3B	108.1	N1—C12—H12B	109.5
C4—C3—H3A	109.5	N1—C12—H12C	109.5
C4—C3—H3B	109.5	H12A—C12—H12B	109.5
N1—C4—C3	111.29 (11)	H12A—C12—H12C	109.5
N1—C4—H4A	109.4	H12B—C12—H12C	109.5
N1—C4—H4B	109.4
O1—N4—C9—C8	−7.5 (2)	C3—N2—N3—C5	−21.56 (18)
O1—N4—C9—C10	171.92 (14)	C3—N2—C2—C1	50.72 (15)
O2—N4—C9—C8	172.30 (13)	C4—N1—C1—C2	62.44 (14)
O2—N4—C9—C10	−8.2 (2)	C5—C6—C7—C8	179.56 (12)
N1—C1—C2—N2	−56.86 (15)	C5—C6—C11—C10	−179.02 (12)
N2—N3—C5—C6	−176.24 (11)	C6—C7—C8—C9	0.0 (2)
N2—C3—C4—N1	55.30 (15)	C7—C6—C11—C10	1.1 (2)
N3—N2—C2—C1	−172.24 (11)	C7—C8—C9—N4	179.59 (12)
N3—N2—C3—C4	177.74 (11)	C7—C8—C9—C10	0.1 (2)
N3—C5—C6—C7	−0.5 (2)	C8—C9—C10—C11	0.4 (2)
N3—C5—C6—C11	179.62 (12)	C9—C10—C11—C6	−1.0 (2)
N4—C9—C10—C11	−179.07 (12)	C11—C6—C7—C8	−0.6 (2)
C1—N1—C4—C3	−62.15 (14)	C12—N1—C1—C2	−176.25 (11)
C2—N2—N3—C5	−155.91 (12)	C12—N1—C4—C3	176.40 (11)
C2—N2—C3—C4	−49.44 (15)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2B···O1i	0.99	2.47	3.4052 (19)	158

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

Symmetry code: (i) .