Di­amino­mesitylene

Brihi, O.; Hamdouni, N.; Boulcina, R.; Medjani, M.; Meinnel, J.; Boudjada, A.

doi:10.1107/S2414314616003515

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 3| March 2016| x160351

doi:10.1107/S2414314616003515

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access

Diaminomesitylene

Ouarda Brihi,^a ^* Noudjoud Hamdouni,^a Raouf Boulcina,^b Meriem Medjani,^a Jean Meinnel ^c and Ali Boudjada ^a

^aLaboratoire de Cristallographie, Département de Physique, Université Frères Mentouri-Constantine, 25000 Constantine, Algeria, ^bLaboratoire de Synthèse des Molécules d'intérêts Biologiques, Département de Chimie, Faculté des Sciences Exactes, Université de Constantine 1, 25000 Constantine, Algeria, and ^cUMR 6226 CNRS–Université Rennes 1 `Sciences Chimiques de Rennes', Equipe `Matière Condensée et Systèmes Electroactifs', 263 Avenue du Général Leclerc, F-35042 Rennes, France
^*Correspondence e-mail: ouardabrihi@yahoo.fr

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 24 January 2016; accepted 29 February 2016; online 8 March 2016)

The title compound, C₉H₁₄N₂ (systematic name: 2,4,6-trimethylbenzene-1,3-diamine), is almost planar (r.m.s. deviation = 0.025 Å). In the crystal, molecules are linked via N—H⋯N hydrogen bonds, forming zigzag chains along the b-axis direction. Only one of the four N-bonded H atoms forms a hydrogen bond, perhaps due to steric crowding. The chains are linked by C—H⋯π interactions, forming sheets lying parallel to the bc plane

Keywords: crystal structure; N—H⋯N hydrogen bonds; C—H⋯π interactions.

CCDC reference: 1456540

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Chemical scheme

Structure description

Aromatic amines are a class of chemicals found in the plastic and chemical industries as byproducts of the manufacture of compounds such as polyurethane foams, dyes, pesticides, pharmaceuticals and semiconductors. They are also found in environmental pollution from diesel exhausts, the combustion of wood chips and rubber, tobacco smoke and substances in grilled meats and fish (DeBruin et al., 1999 ; DeBruin & Josephy (2002 ).

The structure of dibromomesitylene (DBM) was resolved by neutron diffraction at 120 and 14 K. It crystallizes in the space group P21/n (Hernandez et al., 2003 ). As part of our project which aims to study new substituted mesitylene or 1,3,5-trimethylbenzene compounds, for example 1,3,5-trimethyl-2,4-dinitrobenzene (Brihi et al., 2015 ), we report herein on the synthesis and crystal structure of the title compound.

The molecular structure of the title compound, also know as diaminomesitylene (DAM), is illustrated in the Fig. 1. The non-H atoms are almost coplanar, r.m.s. deviation = 0.025 Å, with a maximum deviation of 0.044 (2) Å for atom C11, which lies between the amine groups. The crystal packing is illustrated in Fig. 2, which shows the zigzag N—H⋯N hydrogen-bonded chains along [010], which are linked via C—H⋯π interactions forming sheets parallel to the bc plane (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C1–C6 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H22⋯N6ⁱ	0.89	2.37	3.170 (3)	150
N6—H61⋯Cgⁱⁱ	0.90	2.62	3.355 (2)	140
C11—H112⋯Cgⁱⁱⁱ	0.92	2.82	3.665 (2)	152
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) -x, -y, -z+2.

Figure 1
The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level.

Figure 2
The crystal packing of the title compound viewed along the a axis.

Synthesis and crystallization

In a round-bottom flask were placed 1 mmol (210 mg) of 2,4-dinitromesitylene and 1.52 mmol (180 mg) of granulated tin. 10 ml of HCl was added in three equal parts to the mixture that was kept cool for 20–30 min. NaOH was added to the mixture until there was no further precipitation of tin hydroxide. The resulting amine was extracted with ether that was then evacuated by distillation. The title compound was obtained as colourless crystals on recrystallization from ethanol solution.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₉H₁₄N₂
M_r	150.22
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	8.1735 (7), 12.9313 (9), 8.7300 (8)
β (°)	105.803 (9)
V (Å³)	887.83 (13)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.07
Crystal size (mm)	0.10 × 0.08 × 0.07

Data collection
Diffractometer	Oxford Diffraction Xcalibur
No. of measured, independent and observed [I > 3.0σ(I)] reflections	3794, 1953, 1153
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.676

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.103, 0.88
No. of reflections	968
No. of parameters	101
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.13, −0.12
Computer programs: XCALIBUR (Oxford Diffraction, 2002 $[Oxford Diffraction (2002). XCALIBUR. Oxford Diffraction Ltd, Abingdon, England.]$ ), CrysAlis PRO (Agilent, 2004 ), SIR2002 (Burla et al., 2005 ), CRYSTALS (Betteridge et al., 2003 ), CAMERON (Watkin et al., 1996 ).

Structural data

CCDC reference: 1456540

Crystal structure: contains datablocks global, I. DOI: 10.1107/S2414314616003515/hb4017sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616003515/hb4017Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616003515/hb4017Isup3.cml

checkCIF report

Experimental top

Structure description top

The structure of dibromomesitylene (DBM) was resolved by neutron diffraction at 120 and 14 K. It crystallizes in the space group P21/n (Hernandez et al., 2003). As part of our project which aims to study new substituted mesitylene or 1,3,5-trimethylbenzene compounds, for example 1,3,5-trimethyl-2,4-dinitrobenzene (Brihi et al., 2015), we report herein on the synthesis and crystal structure of the title compound.

The molecular structure of the title compound, also know as diaminomesitylene (DAM), is illustrated in the Fig. 1. The non-H atoms are almost coplanar, r.m.s. deviation = 0.025 Å, with a maximum deviation of 0.044 (2) Å for atom C11, which lies between the amine groups. The crystal packing is illustrated in Fig. 2, which shows the zigzag N—H···N hydrogen-bonded chains along [010], which are linked via C—H···π interactions forming sheets parallel to the bc plane (Table 1).

Computing details top

Data collection: XCALIBUR (Oxford Diffraction, 2002); cell refinement: CrysAlis PRO (Agilent, 2004); data reduction: CrysAlis PRO (Agilent, 2004); program(s) used to solve structure: SIR2002 (Burla et al., 2005); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: CAMERON (Watkin et al., 1996); software used to prepare material for publication: CRYSTALS (Betteridge et al., 2003).

Figures top

	Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. The crystal packing of the title compound viewed along the a axis. Hydrogen bonds are shown as dotted lines (see Table 1).

2,4,6-Trimethylbenzene-1,3-diamine top

Crystal data top

C₉H₁₄N₂	F(000) = 328
M_r = 150.22	D_x = 1.124 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.1735 (7) Å	Cell parameters from 2457 reflections
b = 12.9313 (9) Å	θ = 4.0–27.9°
c = 8.7300 (8) Å	µ = 0.07 mm⁻¹
β = 105.803 (9)°	T = 293 K
V = 887.83 (13) Å³	Needle, colourless
Z = 4	0.10 × 0.08 × 0.07 mm

Data collection top

Oxford Diffraction Xcalibur diffractometer	R_int = 0.017
Graphite monochromator	θ_max = 28.7°, θ_min = 3.4°
ω/2θ scans	h = −10→11
3794 measured reflections	k = −16→15
1953 independent reflections	l = −11→11
1153 reflections with I > 3.0σ(I)

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.103	H-atom parameters constrained
S = 0.88	Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] = 1.0/[A₀T₀(x) + A₁T₁(x) ··· + A_n-1]T_n-1(x)] where A_i are the Chebychev coefficients listed below and x = F /Fmax Method = Robust Weighting (Prince, 1982) W = [weight] [1-(deltaF/6*sigmaF)²]² A_i are: 0.191E + 04 0.570E + 04 0.179E + 04 0.189E + 04
968 reflections	(Δ/σ)_max = 0.0002
101 parameters	Δρ_max = 0.13 e Å⁻³
0 restraints	Δρ_min = −0.12 e Å⁻³

Crystal data top

C₉H₁₄N₂	V = 887.83 (13) Å³
M_r = 150.22	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.1735 (7) Å	µ = 0.07 mm⁻¹
b = 12.9313 (9) Å	T = 293 K
c = 8.7300 (8) Å	0.10 × 0.08 × 0.07 mm
β = 105.803 (9)°

Data collection top

Oxford Diffraction Xcalibur diffractometer	1153 reflections with I > 3.0σ(I)
3794 measured reflections	R_int = 0.017
1953 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.103	H-atom parameters constrained
S = 0.88	Δρ_max = 0.13 e Å⁻³
968 reflections	Δρ_min = −0.12 e Å⁻³
101 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.

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

	x	y	z	U_iso*/U_eq
N2	−0.0520 (3)	−0.04877 (17)	0.7012 (2)	0.0722
N6	0.0592 (3)	0.25972 (15)	1.0272 (2)	0.0605
C1	0.0030 (2)	0.10506 (16)	0.8621 (2)	0.0432
C2	0.0612 (3)	0.02612 (16)	0.7813 (2)	0.0461
C3	0.2327 (3)	0.02171 (16)	0.7811 (2)	0.0492
C4	0.3405 (2)	0.09757 (18)	0.8639 (3)	0.0516
C5	0.2888 (3)	0.17661 (17)	0.9470 (2)	0.0490
C6	0.1174 (2)	0.17840 (16)	0.9474 (2)	0.0443
C11	−0.1830 (3)	0.1110 (2)	0.8552 (3)	0.0628
C31	0.2977 (4)	−0.0630 (2)	0.6941 (3)	0.0751
C51	0.4127 (3)	0.2583 (2)	1.0309 (3)	0.0725
H41	0.4600	0.0935	0.8640	0.0617*
H111	−0.2178	0.1723	0.8870	0.0980*
H112	−0.2227	0.0616	0.9125	0.0981*
H113	−0.2567	0.0986	0.7456	0.0980*
H311	0.4211	−0.0544	0.7091	0.1203*
H312	0.2793	−0.1332	0.7340	0.1205*
H313	0.2428	−0.0622	0.5781	0.1206*
H511	0.3719	0.3262	1.0041	0.1103*
H512	0.4348	0.2551	1.1498	0.1097*
H513	0.5238	0.2444	1.0147	0.1102*
H21	−0.1497	−0.0530	0.7222	0.0861*
H22	−0.0121	−0.0969	0.6483	0.0861*
H61	0.1413	0.2892	1.1051	0.0743*
H62	−0.0261	0.2420	1.0560	0.0743*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N2	0.0724 (14)	0.0698 (14)	0.0755 (14)	−0.0162 (11)	0.0223 (11)	−0.0161 (11)
N6	0.0629 (12)	0.0598 (12)	0.0616 (11)	0.0055 (9)	0.0215 (10)	−0.0052 (9)
C1	0.0396 (10)	0.0477 (12)	0.0420 (10)	0.0041 (9)	0.0106 (9)	0.0138 (9)
C2	0.0513 (11)	0.0441 (11)	0.0413 (10)	−0.0009 (10)	0.0102 (9)	0.0076 (10)
C3	0.0545 (12)	0.0477 (12)	0.0475 (11)	0.0072 (11)	0.0171 (10)	0.0068 (10)
C4	0.0399 (10)	0.0604 (14)	0.0557 (13)	0.0049 (10)	0.0150 (9)	0.0093 (11)
C5	0.0467 (11)	0.0495 (12)	0.0481 (12)	0.0017 (10)	0.0087 (9)	0.0056 (10)
C6	0.0490 (11)	0.0440 (12)	0.0410 (10)	0.0079 (9)	0.0140 (9)	0.0086 (9)
C11	0.0424 (11)	0.0740 (16)	0.0732 (16)	0.0037 (11)	0.0177 (11)	0.0107 (13)
C31	0.0810 (18)	0.0716 (17)	0.0778 (19)	0.0186 (14)	0.0302 (15)	−0.0083 (14)
C51	0.0580 (14)	0.0710 (16)	0.0834 (18)	−0.0109 (13)	0.0104 (13)	−0.0121 (14)

Geometric parameters (Å, º) top

N2—C2	1.390 (3)	C4—H41	0.978
N2—H21	0.868	C5—C6	1.401 (3)
N2—H22	0.888	C5—C51	1.508 (3)
N6—C6	1.414 (3)	C11—H111	0.911
N6—H61	0.899	C11—H112	0.924
N6—H62	0.835	C11—H113	0.996
C1—C2	1.396 (3)	C31—H311	0.987
C1—C6	1.396 (3)	C31—H312	0.998
C1—C11	1.507 (3)	C31—H313	0.989
C2—C3	1.403 (3)	C51—H511	0.947
C3—C4	1.384 (3)	C51—H512	1.005
C3—C31	1.510 (3)	C51—H513	0.973
C4—C5	1.384 (3)

C2—N2—H21	117.6	N6—C6—C5	119.0 (2)
C2—N2—H22	117.5	N6—C6—C1	120.11 (18)
H21—N2—H22	123.7	C5—C6—C1	120.81 (19)
C6—N6—H61	113.9	C1—C11—H111	115.4
C6—N6—H62	111.4	C1—C11—H112	116.3
H61—N6—H62	113.6	H111—C11—H112	104.6
C2—C1—C6	119.69 (17)	C1—C11—H113	111.7
C2—C1—C11	119.8 (2)	H111—C11—H113	106.0
C6—C1—C11	120.6 (2)	H112—C11—H113	101.5
C1—C2—N2	119.47 (18)	C3—C31—H311	109.8
C1—C2—C3	120.54 (19)	C3—C31—H312	112.1
N2—C2—C3	120.0 (2)	H311—C31—H312	107.6
C2—C3—C4	117.71 (19)	C3—C31—H313	112.5
C2—C3—C31	121.2 (2)	H311—C31—H313	107.3
C4—C3—C31	121.1 (2)	H312—C31—H313	107.3
C3—C4—C5	123.71 (19)	C5—C51—H511	112.6
C3—C4—H41	117.1	C5—C51—H512	112.4
C5—C4—H41	119.1	H511—C51—H512	104.2
C4—C5—C6	117.5 (2)	C5—C51—H513	109.3
C4—C5—C51	120.7 (2)	H511—C51—H513	114.6
C6—C5—C51	121.8 (2)	H512—C51—H513	103.4

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of benzene ring C1–C6.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H22···N6ⁱ	0.89	2.37	3.170 (3)	150
N6—H61···Cgⁱⁱ	0.90	2.62	3.355 (2)	140
C11—H112···Cgⁱⁱⁱ	0.92	2.82	3.665 (2)	152

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

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of benzene ring C1–C6.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H22···N6ⁱ	0.89	2.37	3.170 (3)	150
N6—H61···Cgⁱⁱ	0.90	2.62	3.355 (2)	140
C11—H112···Cgⁱⁱⁱ	0.92	2.82	3.665 (2)	152

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

Experimental details

Crystal data
Chemical formula	C₉H₁₄N₂
M_r	150.22
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	8.1735 (7), 12.9313 (9), 8.7300 (8)
β (°)	105.803 (9)
V (Å³)	887.83 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.10 × 0.08 × 0.07

Data collection
Diffractometer	Oxford Diffraction Xcalibur
Absorption correction	–
No. of measured, independent and observed [I > 3.0σ(I)] reflections	3794, 1953, 1153
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.676

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.103, 0.88
No. of reflections	968
No. of parameters	101
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.13, −0.12

Computer programs: XCALIBUR (Oxford Diffraction, 2002), CrysAlis PRO (Agilent, 2004), SIR2002 (Burla et al., 2005), CRYSTALS (Betteridge et al., 2003), CAMERON (Watkin et al., 1996).

Acknowledgements

This work was supported by the Laboratoire de Cristallographie Département de Physique, Université Fréres Mentouri-Constantine, Algeria. We would also like to thank Mr F. Saidi, Engineer at the Université Mentouri-Constantine, for assistance during the data collection on the Xcalibur X-ray diffractometer.

References

Agilent (2004). CrysAlis PRO. Agilent Technologies, Yarnton, England. Google Scholar
Betteridge, P. W., Carruthers, J. R., Cooper, R. I., Prout, K. & Watkin, D. J. (2003). J. Appl. Cryst. 36, 1487. Web of Science CrossRef IUCr Journals Google Scholar
Brihi, O., Hamdouni, N., Boudjada, A. & Meinnel, J. (2015). Acta Cryst. E71, o670–o671. Web of Science CSD CrossRef IUCr Journals Google Scholar
Burla, M. C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G. L., De Caro, L., Giacovazzo, C., Polidori, G. & Spagna, R. (2005). J. Appl. Cryst. 38, 381–388. Web of Science CrossRef CAS IUCr Journals Google Scholar
DeBruin, L. & Josephy, P. (2002). Environ. Health Perspect. 110, 119–128. CrossRef PubMed CAS Google Scholar
DeBruin, L., Pawliszyn, J. & Josephy, P. (1999). Chem. Res. Toxicol. 12, 78–82. Web of Science CrossRef CAS PubMed Google Scholar
Hernandez, O., Cousson, A., Plazanet, M., Nierlich, M. & Meinnel, J. (2003). Acta Cryst. C59, o445–o450. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Oxford Diffraction (2002). XCALIBUR. Oxford Diffraction Ltd, Abingdon, England. Google Scholar
Watkin, D. J., Prout, C. K. & Pearce, L. J. (1996). CAMERON. Chemical Crystallography Laboratory, Oxford, England. Google Scholar

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ISSN: 2414-3146

Volume 1| Part 3| March 2016| x160351

doi:10.1107/S2414314616003515

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Di­amino­mesitylene

Structure description

Synthesis and crystallization

Refinement

Structural data

Acknowledgements

References

organic compounds

Diaminomesitylene