3-Methyl­benzene-1,2-diamine

Yang, X.-L.; Feng, Z.-Q.; Hao, L.-Y.

doi:10.1107/S1600536812046120

organic compounds

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Volume 68| Part 12| December 2012| Page o3346

doi:10.1107/S1600536812046120

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3-Methylbenzene-1,2-diamine

Xiao-Li Yang,^a ^* Zhi-Qiang Feng ^a and Ling-Yun Hao ^a

^aSchool of Material Engineering, Jinling Institute of Technology, Nanjing 211169, People's Republic of China
^*Correspondence e-mail: yangjianming7706@sina.com

(Received 27 October 2012; accepted 8 November 2012; online 14 November 2012)

The title compound, C₇H₁₀N₂, was synthesized from 2-methyl-6-nitroaniline by a reduction reaction. In the crystal, molecules are linked via N—H⋯N hydrogen bonds, forming two-dimensional networks lying parallel to (100). These networks are stabilized by C—H⋯π and N—H⋯π interactions.

Related literature

The title compound is an important organic synthesis intermediate. For background to its applications, see: Wen et al. (2009 ). For the synthetic procedure, see: Li et al. (2011 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₇H₁₀N₂
M_r = 122.17
Monoclinic, P 2₁ /c
a = 11.836 (2) Å
b = 7.7160 (15) Å
c = 7.7430 (15) Å
β = 90.72 (3)°
V = 707.1 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 291 K
0.3 × 0.2 × 0.1 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.979, T_max = 0.993
2693 measured reflections
1300 independent reflections
962 reflections with I > 2σ(I)
R_int = 0.060
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.124
S = 1.00
1300 reflections
110 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.12 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯N2ⁱ	0.91 (2)	2.36 (2)	3.237 (2)	163.5 (16)
N2—H2A⋯N1ⁱⁱ	0.84 (2)	2.48 (2)	3.248 (2)	152.2 (19)
C2—H2⋯Cg1ⁱⁱⁱ	0.93	2.85	3.6713 (18)	148
N2—H2B⋯Cg1^iv	0.90 (2)	2.776 (18)	3.5192 (17)	141.2 (16)
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z+1; (iii) $[x, -y+{\script{1\over 2}}, z-{\script{3\over 2}}]$ ; (iv) $[x, -y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

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: 10.1107/S1600536812046120/bq2378sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812046120/bq2378Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812046120/bq2378Isup3.cml

checkCIF report

Comment top

Aromatic amines are important organic intermediates and widely used in chemical, pharmaceutical, agricultural and photographic chemicals. Aromatic amines are mainly synthesized by the reduction of aromatic nitro compounds. Compared with other reduction methods, catalytic transfer hydrogenation (CTH) is environmentally friendly, high yield and good selectivity (Wen et al., 2009), in which hydrogen gas is replaced by a hydrogen donor such as hydrazine hydrate. Here, the title compound, (I), was synthesized by the CTH of 2-methyl-6-nitroaniline, and we report the crystal structure of (I).

In the molecule of (I), (Fig.1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. In the crystal, there are two C—H···Cg1 and N—H···Cg1 interactions (Cg1 is the centroid of C1-C6 ring). The molecules are linked each other by the two intermolecular N—H···N hydrogen bonds to form a three-dimensional network, which seem to be very effective in the stabilization of the crystal structure (Fig. 2.).

Related literature top

The title compound is an important organic synthesis intermediate. For background to its applications, see: Wen et al. (2009). For the synthetic procedure, see: Li et al. (2011). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound, (I) was prepared by the literature method (Li et al., 2011). Crystals suitable for X-ray analysis were obtained by dissolving (I) (0.5 g) in ethyl acetate (20 ml) and evaporating the solvent slowly at room temperature for about 7 d.

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 by dashed lines.

3-Methylbenzene-1,2-diamine top

Crystal data top

C₇H₁₀N₂	F(000) = 264
M_r = 122.17	D_x = 1.148 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 11.836 (2) Å	θ = 9–13°
b = 7.7160 (15) Å	µ = 0.07 mm⁻¹
c = 7.7430 (15) Å	T = 291 K
β = 90.72 (3)°	Needle, colourless
V = 707.1 (2) Å³	0.3 × 0.2 × 0.1 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	962 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.060
Graphite monochromator	θ_max = 25.4°, θ_min = 1.7°
ω/2θ scans	h = −14→14
Absorption correction: ψ scan (North et al., 1968)	k = −9→9
T_min = 0.979, T_max = 0.993	l = 0→9
2693 measured reflections	3 standard reflections every 200 reflections
1300 independent reflections	intensity decay: 1%

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.124	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.073P)²] where P = (F_o² + 2F_c²)/3
1300 reflections	(Δ/σ)_max < 0.001
110 parameters	Δρ_max = 0.13 e Å⁻³
0 restraints	Δρ_min = −0.12 e Å⁻³

Crystal data top

C₇H₁₀N₂	V = 707.1 (2) Å³
M_r = 122.17	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.836 (2) Å	µ = 0.07 mm⁻¹
b = 7.7160 (15) Å	T = 291 K
c = 7.7430 (15) Å	0.3 × 0.2 × 0.1 mm
β = 90.72 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	962 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.060
T_min = 0.979, T_max = 0.993	3 standard reflections every 200 reflections
2693 measured reflections	intensity decay: 1%
1300 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.124	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.13 e Å⁻³
1300 reflections	Δρ_min = −0.12 e Å⁻³
110 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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
C1	0.15863 (14)	0.55588 (19)	0.1128 (2)	0.0551 (5)
H1	0.0829	0.5612	0.0799	0.066*
C2	0.23534 (15)	0.6592 (2)	0.0300 (2)	0.0578 (5)
H2	0.2116	0.7340	−0.0573	0.069*
C3	0.34751 (13)	0.65096 (18)	0.07727 (19)	0.0493 (4)
H3	0.3996	0.7206	0.0211	0.059*
C4	0.38402 (12)	0.54018 (16)	0.20768 (17)	0.0408 (4)
C5	0.30472 (12)	0.43631 (17)	0.29360 (17)	0.0399 (4)
C6	0.19124 (12)	0.44367 (18)	0.2446 (2)	0.0478 (4)
C7	0.10562 (18)	0.3339 (3)	0.3346 (3)	0.0760 (6)
N1	0.49730 (11)	0.5349 (2)	0.26271 (18)	0.0508 (4)
N2	0.34528 (14)	0.32174 (18)	0.42184 (19)	0.0525 (4)
H1A	0.5472 (17)	0.596 (3)	0.199 (3)	0.072 (6)*
H1B	0.5231 (14)	0.430 (3)	0.290 (2)	0.066 (6)*
H2A	0.4043 (19)	0.350 (3)	0.478 (3)	0.086 (7)*
H2B	0.2929 (18)	0.257 (2)	0.474 (3)	0.074 (6)*
H7A	0.031 (2)	0.350 (3)	0.279 (3)	0.097 (7)*
H7B	0.127 (2)	0.211 (3)	0.323 (3)	0.111 (8)*
H7C	0.1046 (18)	0.375 (3)	0.458 (3)	0.091 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0485 (9)	0.0534 (9)	0.0630 (10)	0.0031 (7)	−0.0144 (8)	−0.0054 (8)
C2	0.0675 (11)	0.0475 (9)	0.0578 (10)	−0.0018 (8)	−0.0169 (8)	0.0077 (8)
C3	0.0583 (10)	0.0435 (8)	0.0461 (9)	−0.0086 (7)	−0.0023 (7)	0.0014 (7)
C4	0.0458 (8)	0.0359 (7)	0.0408 (8)	−0.0009 (6)	0.0020 (6)	−0.0065 (6)
C5	0.0445 (8)	0.0354 (7)	0.0398 (7)	0.0032 (6)	0.0025 (6)	−0.0045 (6)
C6	0.0424 (8)	0.0444 (8)	0.0566 (9)	−0.0021 (6)	0.0008 (7)	−0.0062 (7)
C7	0.0493 (11)	0.0862 (16)	0.0926 (17)	−0.0115 (10)	0.0066 (11)	0.0150 (13)
N1	0.0437 (8)	0.0531 (9)	0.0558 (8)	−0.0016 (6)	0.0033 (6)	0.0063 (7)
N2	0.0482 (8)	0.0534 (8)	0.0557 (8)	0.0009 (7)	0.0021 (7)	0.0128 (7)

Geometric parameters (Å, º) top

C1—C2	1.373 (2)	C5—N2	1.4092 (19)
C1—C6	1.389 (2)	C6—C7	1.499 (2)
C1—H1	0.9300	C7—H7A	0.98 (2)
C2—C3	1.374 (2)	C7—H7B	0.99 (2)
C2—H2	0.9300	C7—H7C	1.01 (2)
C3—C4	1.388 (2)	N1—H1A	0.91 (2)
C3—H3	0.9300	N1—H1B	0.89 (2)
C4—N1	1.4023 (19)	N2—H2A	0.84 (2)
C4—C5	1.408 (2)	N2—H2B	0.90 (2)
C5—C6	1.392 (2)

C2—C1—C6	121.70 (15)	C1—C6—C5	118.94 (14)
C2—C1—H1	119.2	C1—C6—C7	120.69 (16)
C6—C1—H1	119.2	C5—C6—C7	120.37 (15)
C1—C2—C3	119.44 (15)	C6—C7—H7A	109.4 (13)
C1—C2—H2	120.3	C6—C7—H7B	108.7 (16)
C3—C2—H2	120.3	H7A—C7—H7B	108.3 (19)
C2—C3—C4	120.86 (15)	C6—C7—H7C	106.2 (12)
C2—C3—H3	119.6	H7A—C7—H7C	110.6 (19)
C4—C3—H3	119.6	H7B—C7—H7C	113 (2)
C3—C4—N1	121.78 (14)	C4—N1—H1A	116.5 (12)
C3—C4—C5	119.42 (14)	C4—N1—H1B	115.0 (11)
N1—C4—C5	118.72 (13)	H1A—N1—H1B	112.1 (17)
C6—C5—C4	119.64 (13)	C5—N2—H2A	118.1 (14)
C6—C5—N2	122.45 (14)	C5—N2—H2B	115.9 (12)
C4—C5—N2	117.83 (14)	H2A—N2—H2B	118.8 (19)

C6—C1—C2—C3	0.5 (2)	N1—C4—C5—N2	−5.00 (19)
C1—C2—C3—C4	−0.2 (2)	C2—C1—C6—C5	0.1 (2)
C2—C3—C4—N1	−177.35 (13)	C2—C1—C6—C7	179.18 (17)
C2—C3—C4—C5	−0.6 (2)	C4—C5—C6—C1	−0.9 (2)
C3—C4—C5—C6	1.19 (19)	N2—C5—C6—C1	−177.77 (13)
N1—C4—C5—C6	178.00 (12)	C4—C5—C6—C7	179.99 (16)
C3—C4—C5—N2	178.19 (12)	N2—C5—C6—C7	3.1 (2)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N2ⁱ	0.91 (2)	2.36 (2)	3.237 (2)	163.5 (16)
N2—H2A···N1ⁱⁱ	0.84 (2)	2.48 (2)	3.248 (2)	152.2 (19)
C2—H2···Cg1ⁱⁱⁱ	0.93	2.85	3.6713 (18)	148
N2—H2B···Cg1^iv	0.90 (2)	2.776 (18)	3.5192 (17)	141.2 (16)

Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+1, −y+1, −z+1; (iii) x, −y+1/2, z−3/2; (iv) x, −y−1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₇H₁₀N₂
M_r	122.17
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	291
a, b, c (Å)	11.836 (2), 7.7160 (15), 7.7430 (15)
β (°)	90.72 (3)
V (Å³)	707.1 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.3 × 0.2 × 0.1

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.979, 0.993
No. of measured, independent and observed [I > 2σ(I)] reflections	2693, 1300, 962
R_int	0.060
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.124, 1.00
No. of reflections	1300
No. of parameters	110
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.13, −0.12

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

Cg1 is the centroid of C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N2ⁱ	0.91 (2)	2.36 (2)	3.237 (2)	163.5 (16)
N2—H2A···N1ⁱⁱ	0.84 (2)	2.48 (2)	3.248 (2)	152.2 (19)
C2—H2···Cg1ⁱⁱⁱ	0.9300	2.8487	3.6713 (18)	148.16
N2—H2B···Cg1^iv	0.90 (2)	2.776 (18)	3.5192 (17)	141.2 (16)

Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+1, −y+1, −z+1; (iii) x, −y+1/2, z−3/2; (iv) x, −y−1/2, z−1/2.

Acknowledgements

This work was supported by the Doctoral Fund of Jinling Institute of Technology (jit-b-201227). The authors thank the Center of Test and Analysis, Nanjing University, for the data collection.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
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Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 12| December 2012| Page o3346

doi:10.1107/S1600536812046120

Open

access