5-(4-Methyl­piperazin-1-yl)-2-nitro­aniline

Luan, C.; Guo, C.; Wang, W.; Wang, J.; Du, R.

doi:10.1107/S1600536810015953

organic compounds

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ISSN: 2056-9890

Volume 66| Part 6| June 2010| Page o1268

https://doi.org/10.1107/S1600536810015953

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5-(4-Methylpiperazin-1-yl)-2-nitroaniline

Chang-jun Luan,^a Cheng Guo,^a ^* Wei Wang,^a Jian-qiang Wang ^a and Ren-jun Du ^a

^aDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: guocheng@njut.edu.cn

(Received 7 April 2010; accepted 30 April 2010; online 8 May 2010)

In the title compound, C₁₁H₁₆N₄O₂, the dihedral angle between the benzene ring and the plane of the four carbon atoms in the piperazine ring is 12.17 (3)°; the latter ring adopts a chair conformation. An intramolecular N—H⋯O hydrogen bond generates an S(6) ring. In the crystal, the molecules are linked by N—H⋯N hydrogen bonds, forming chains.

Related literature

For bond-length data, see: Allen et al. (1987 ). For the synthetic procedure and use of the title compound as an intermediate in the synthesis of tyrosine kinase inhibitors, see: Renhowe et al. (2009 ).

Experimental

Crystal data

C₁₁H₁₆N₄O₂
M_r = 236.28
Monoclinic, P 2₁ /c
a = 11.027 (2) Å
b = 6.121 (1) Å
c = 17.524 (4) Å
β = 103.79 (3)°
V = 1148.7 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.05 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.971, T_max = 0.995
2205 measured reflections
2090 independent reflections
1358 reflections with I > 2σ(I)
R_int = 0.042
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.064
wR(F²) = 0.192
S = 1.01
2090 reflections
155 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3C⋯N1ⁱ	0.86	2.39	3.156 (4)	148
N3—H3D⋯O1	0.86	2.06	2.669 (4)	127
Symmetry code: (i) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CAD-4 Software (Enraf–Nonius, 1985 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810015953/im2192sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810015953/im2192Isup2.hkl

checkCIF report

Comment top

The title compound, (I), has been reported as an intermediate for the synthesis of novel tyrosine kinase inhibitors (Renhowe, P. A. et al., 2009). We herein report its crystal structure.

In the molecular structure of (I), (Fig.1), bond lengths (Allen et al., 1987) and angles are within normal ranges. N2, N3 and N4 atoms are almost coplanar with the benzene ring to which they are bonded [deviations of 0.078 (1), 0.052 (1) and 0.078 (1) Å]. The plane of C2—C3—C4—C5 is nearly parallel with the benzene ring plane (the torsion angle is 12.17 (3) °). By contrast, due to the piperazine moiety adopting a chair conformation N1—C2—C5 and N2—C3—C4 form two separate planes with torsion angle of 45.87 (2) ° and 25.92 (3) °, respectively, with respect to the benzene ring. The crystal structure of the title compound exhibits N—H···O, C—H···O, and N—H···N intra- and intermolecular hydrogen bonds to form a three dimensional network.

As can be seen from the packing diagram, (Fig. 2), the molecules are stacked along the b axis.

Related literature top

For bond-length data, see: Allen et al. (1987). For the synthetic procedure and use of the title compound as an intermediate in the synthesis of tyrosine kinase inhibitors, see: Renhowe et al. (2009).

Experimental top

The title compound, (I) was prepared by a literature method (Renhowe, P. A. et al., 2009). Crystals suitable for X-ray analysis were obtained by dissolving (I) (0.5 g) in methanol (20 ml) and evaporating the solvent slowly at room temperature for about 7 d.

Structure description top

The title compound, (I), has been reported as an intermediate for the synthesis of novel tyrosine kinase inhibitors (Renhowe, P. A. et al., 2009). We herein report its crystal structure.

As can be seen from the packing diagram, (Fig. 2), the molecules are stacked along the b axis.

For bond-length data, see: Allen et al. (1987). For the synthetic procedure and use of the title compound as an intermediate in the synthesis of tyrosine kinase inhibitors, see: Renhowe et al. (2009).

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell refinement: CAD-4 Software (Enraf–Nonius, 1985); data reduction: XCAD4 (Harms & Wocadlo, 1995); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A packing diagram of (I). Hydrogen bonds are shown as dashed lines.

5-(4-Methylpiperazin-1-yl)-2-nitroaniline top

Crystal data top

C₁₁H₁₆N₄O₂	D_x = 1.366 Mg m⁻³
M_r = 236.28	Melting point: 428 K
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.027 (2) Å	Cell parameters from 25 reflections
b = 6.121 (1) Å	θ = 9–13°
c = 17.524 (4) Å	µ = 0.10 mm⁻¹
β = 103.79 (3)°	T = 293 K
V = 1148.7 (4) Å³	Block, yellow
Z = 4	0.30 × 0.20 × 0.05 mm
F(000) = 504

Data collection top

Enraf–Nonius CAD-4 diffractometer	1358 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.042
Graphite monochromator	θ_max = 25.3°, θ_min = 1.9°
ω/2θ scans	h = 0→13
Absorption correction: ψ scan (North et al., 1968)	k = 0→7
T_min = 0.971, T_max = 0.995	l = −21→20
2205 measured reflections	3 standard reflections every 200 reflections
2090 independent reflections	intensity decay: 1%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.064	H-atom parameters constrained
wR(F²) = 0.192	w = 1/[σ²(F_o²) + (0.1P)² + 0.3P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
2090 reflections	Δρ_max = 0.25 e Å⁻³
155 parameters	Δρ_min = −0.18 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.038 (6)

Crystal data top

C₁₁H₁₆N₄O₂	V = 1148.7 (4) Å³
M_r = 236.28	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.027 (2) Å	µ = 0.10 mm⁻¹
b = 6.121 (1) Å	T = 293 K
c = 17.524 (4) Å	0.30 × 0.20 × 0.05 mm
β = 103.79 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1358 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.042
T_min = 0.971, T_max = 0.995	3 standard reflections every 200 reflections
2205 measured reflections	intensity decay: 1%
2090 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.064	0 restraints
wR(F²) = 0.192	H-atom parameters constrained
S = 1.01	Δρ_max = 0.25 e Å⁻³
2090 reflections	Δρ_min = −0.18 e Å⁻³
155 parameters

Special details top

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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.6711 (2)	0.0465 (4)	0.16875 (13)	0.0438 (6)
O1	1.3775 (2)	−0.0656 (4)	0.56703 (14)	0.0774 (8)
C1	0.5525 (3)	0.1090 (6)	0.11543 (19)	0.0603 (9)
H1A	0.5683	0.2064	0.0760	0.090*
H1B	0.5007	0.1809	0.1447	0.090*
H1C	0.5107	−0.0193	0.0907	0.090*
N2	0.8586 (2)	0.0019 (4)	0.31264 (13)	0.0397 (6)
O2	1.2787 (2)	−0.3532 (4)	0.58981 (13)	0.0662 (7)
C2	0.7330 (3)	0.2397 (5)	0.20898 (17)	0.0484 (8)
H2A	0.6826	0.3007	0.2422	0.058*
H2B	0.7409	0.3493	0.1705	0.058*
C3	0.8606 (3)	0.1827 (5)	0.25841 (16)	0.0466 (8)
H3A	0.9143	0.1440	0.2240	0.056*
H3B	0.8960	0.3103	0.2883	0.056*
N3	1.2683 (2)	0.2156 (4)	0.45524 (16)	0.0613 (8)
H3C	1.2595	0.3315	0.4267	0.074*
H3D	1.3359	0.1954	0.4909	0.074*
C4	0.7741 (3)	−0.1801 (5)	0.28094 (18)	0.0478 (8)
H4A	0.7577	−0.2645	0.3242	0.057*
H4B	0.8149	−0.2755	0.2506	0.057*
N4	1.2841 (2)	−0.1869 (5)	0.55073 (15)	0.0527 (7)
C5	0.6513 (3)	−0.1026 (5)	0.22932 (17)	0.0506 (8)
H5A	0.6035	−0.2276	0.2048	0.061*
H5B	0.6033	−0.0292	0.2615	0.061*
C6	0.9667 (2)	−0.0433 (4)	0.36840 (15)	0.0367 (7)
C7	1.0669 (2)	0.1023 (5)	0.38534 (15)	0.0398 (7)
H7A	1.0610	0.2307	0.3563	0.048*
C8	1.1758 (2)	0.0647 (5)	0.44396 (16)	0.0415 (7)
C9	1.1820 (2)	−0.1317 (5)	0.48727 (15)	0.0422 (7)
C10	1.0839 (3)	−0.2817 (5)	0.46870 (17)	0.0475 (8)
H10A	1.0901	−0.4120	0.4966	0.057*
C11	0.9799 (3)	−0.2428 (5)	0.41112 (17)	0.0444 (7)
H11A	0.9169	−0.3471	0.3995	0.053*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0385 (13)	0.0422 (14)	0.0464 (13)	−0.0004 (11)	0.0017 (10)	0.0030 (11)
O1	0.0545 (14)	0.0794 (18)	0.0820 (17)	−0.0125 (13)	−0.0158 (12)	0.0122 (14)
C1	0.0411 (17)	0.067 (2)	0.065 (2)	0.0050 (16)	−0.0025 (15)	0.0064 (18)
N2	0.0357 (12)	0.0346 (12)	0.0458 (13)	−0.0029 (10)	0.0040 (10)	0.0048 (11)
O2	0.0610 (15)	0.0616 (15)	0.0674 (15)	0.0125 (12)	−0.0015 (12)	0.0190 (12)
C2	0.0527 (18)	0.0375 (16)	0.0502 (17)	0.0004 (14)	0.0030 (14)	0.0085 (14)
C3	0.0449 (17)	0.0396 (16)	0.0503 (17)	−0.0067 (14)	0.0016 (14)	0.0084 (14)
N3	0.0486 (15)	0.0509 (16)	0.0724 (17)	−0.0149 (13)	−0.0094 (13)	0.0073 (14)
C4	0.0440 (16)	0.0354 (15)	0.0605 (18)	−0.0053 (13)	0.0057 (14)	0.0075 (14)
N4	0.0484 (15)	0.0537 (17)	0.0516 (15)	0.0041 (14)	0.0033 (12)	0.0020 (13)
C5	0.0383 (16)	0.0456 (17)	0.0636 (19)	−0.0060 (14)	0.0036 (14)	0.0058 (16)
C6	0.0354 (14)	0.0369 (15)	0.0393 (14)	0.0018 (12)	0.0118 (12)	−0.0007 (12)
C7	0.0414 (15)	0.0320 (15)	0.0443 (15)	0.0013 (12)	0.0071 (12)	0.0025 (12)
C8	0.0391 (15)	0.0386 (16)	0.0455 (16)	−0.0015 (13)	0.0075 (13)	−0.0057 (13)
C9	0.0398 (15)	0.0469 (17)	0.0377 (15)	0.0063 (13)	0.0051 (12)	0.0029 (13)
C10	0.0470 (17)	0.0444 (18)	0.0510 (17)	0.0014 (14)	0.0116 (14)	0.0123 (14)
C11	0.0391 (15)	0.0395 (16)	0.0527 (17)	−0.0031 (13)	0.0071 (13)	0.0101 (14)

Geometric parameters (Å, º) top

N1—C5	1.455 (3)	N3—H3C	0.8600
N1—C2	1.460 (4)	N3—H3D	0.8600
N1—C1	1.466 (3)	C4—C5	1.514 (4)
O1—N4	1.246 (3)	C4—H4A	0.9700
C1—H1A	0.9600	C4—H4B	0.9700
C1—H1B	0.9600	N4—C9	1.422 (4)
C1—H1C	0.9600	C5—H5A	0.9700
N2—C6	1.377 (3)	C5—H5B	0.9700
N2—C3	1.462 (3)	C6—C7	1.395 (4)
N2—C4	1.473 (3)	C6—C11	1.421 (4)
O2—N4	1.236 (3)	C7—C8	1.401 (4)
C2—C3	1.507 (4)	C7—H7A	0.9300
C2—H2A	0.9700	C8—C9	1.415 (4)
C2—H2B	0.9700	C9—C10	1.396 (4)
C3—H3A	0.9700	C10—C11	1.356 (4)
C3—H3B	0.9700	C10—H10A	0.9300
N3—C8	1.355 (3)	C11—H11A	0.9300

C5—N1—C2	106.8 (2)	N2—C4—H4B	109.1
C5—N1—C1	111.2 (2)	C5—C4—H4B	109.1
C2—N1—C1	109.8 (2)	H4A—C4—H4B	107.8
N1—C1—H1A	109.5	O2—N4—O1	120.6 (3)
N1—C1—H1B	109.5	O2—N4—C9	119.7 (3)
H1A—C1—H1B	109.5	O1—N4—C9	119.7 (3)
N1—C1—H1C	109.5	N1—C5—C4	111.3 (2)
H1A—C1—H1C	109.5	N1—C5—H5A	109.4
H1B—C1—H1C	109.5	C4—C5—H5A	109.4
C6—N2—C3	118.0 (2)	N1—C5—H5B	109.4
C6—N2—C4	118.6 (2)	C4—C5—H5B	109.4
C3—N2—C4	115.7 (2)	H5A—C5—H5B	108.0
N1—C2—C3	110.8 (2)	N2—C6—C7	122.0 (2)
N1—C2—H2A	109.5	N2—C6—C11	120.6 (2)
C3—C2—H2A	109.5	C7—C6—C11	117.4 (2)
N1—C2—H2B	109.5	C6—C7—C8	123.2 (3)
C3—C2—H2B	109.5	C6—C7—H7A	118.4
H2A—C2—H2B	108.1	C8—C7—H7A	118.4
N2—C3—C2	113.1 (2)	N3—C8—C7	118.6 (3)
N2—C3—H3A	109.0	N3—C8—C9	124.2 (2)
C2—C3—H3A	109.0	C7—C8—C9	117.2 (2)
N2—C3—H3B	109.0	C10—C9—C8	119.9 (2)
C2—C3—H3B	109.0	C10—C9—N4	116.8 (3)
H3A—C3—H3B	107.8	C8—C9—N4	123.3 (3)
C8—N3—H3C	120.0	C11—C10—C9	121.9 (3)
C8—N3—H3D	120.0	C11—C10—H10A	119.0
H3C—N3—H3D	120.0	C9—C10—H10A	119.0
N2—C4—C5	112.5 (2)	C10—C11—C6	120.3 (3)
N2—C4—H4A	109.1	C10—C11—H11A	119.8
C5—C4—H4A	109.1	C6—C11—H11A	119.8

C5—N1—C2—C3	64.5 (3)	C6—C7—C8—N3	179.3 (3)
C1—N1—C2—C3	−174.7 (2)	C6—C7—C8—C9	−0.1 (4)
C6—N2—C3—C2	−170.8 (2)	N3—C8—C9—C10	−177.0 (3)
C4—N2—C3—C2	40.4 (3)	C7—C8—C9—C10	2.4 (4)
N1—C2—C3—N2	−53.1 (3)	N3—C8—C9—N4	3.6 (4)
C6—N2—C4—C5	171.8 (2)	C7—C8—C9—N4	−177.1 (2)
C3—N2—C4—C5	−39.5 (3)	O2—N4—C9—C10	−5.1 (4)
C2—N1—C5—C4	−64.2 (3)	O1—N4—C9—C10	175.8 (3)
C1—N1—C5—C4	175.9 (3)	O2—N4—C9—C8	174.4 (3)
N2—C4—C5—N1	52.0 (3)	O1—N4—C9—C8	−4.8 (4)
C3—N2—C6—C7	13.8 (4)	C8—C9—C10—C11	−1.8 (4)
C4—N2—C6—C7	161.8 (2)	N4—C9—C10—C11	177.7 (3)
C3—N2—C6—C11	−166.2 (2)	C9—C10—C11—C6	−1.2 (5)
C4—N2—C6—C11	−18.2 (4)	N2—C6—C11—C10	−176.7 (3)
N2—C6—C7—C8	177.3 (2)	C7—C6—C11—C10	3.3 (4)
C11—C6—C7—C8	−2.7 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3C···N1ⁱ	0.86	2.39	3.156 (4)	148
N3—H3D···O1	0.86	2.06	2.669 (4)	127
C10—H10A···O2	0.93	2.35	2.671 (4)	100

Symmetry code: (i) −x+2, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₆N₄O₂
M_r	236.28
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	11.027 (2), 6.121 (1), 17.524 (4)
β (°)	103.79 (3)
V (Å³)	1148.7 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.30 × 0.20 × 0.05

Data collection
Diffractometer	Enraf–Nonius CAD-4
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.971, 0.995
No. of measured, independent and observed [I > 2σ(I)] reflections	2205, 2090, 1358
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.064, 0.192, 1.01
No. of reflections	2090
No. of parameters	155
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.18

Computer programs: CAD-4 Software (Enraf–Nonius, 1985), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3C···N1ⁱ	0.8600	2.3900	3.156 (4)	148.00
N3—H3D···O1	0.8600	2.0600	2.669 (4)	127.00
C10—H10A···O2	0.9300	2.3500	2.671 (4)	100.00

Symmetry code: (i) −x+2, y+1/2, −z+1/2.

Acknowledgements

The authors thank the Center of Test and Analysis, Nanjing University, for support.

References

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