organic compounds
Diaminomesitylene
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
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
Structure description
Aromatic et al., 1999; DeBruin & Josephy (2002).
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 (DeBruinThe structure of dibromomesitylene (DBM) was resolved by neutron diffraction at 120 and 14 K. It crystallizes in the 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 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).
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 .
details are summarized in Table 2Structural data
CCDC reference: 1456540
10.1107/S2414314616003515/hb4017sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2414314616003515/hb4017Isup2.hkl
Supporting information file. DOI: 10.1107/S2414314616003515/hb4017Isup3.cml
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.
Aromatic
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
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 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).
Data collection: XCALIBUR (Oxford Diffraction, 2002); cell
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).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). |
C9H14N2 | F(000) = 328 |
Mr = 150.22 | Dx = 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 |
Oxford Diffraction Xcalibur diffractometer | Rint = 0.017 |
Graphite monochromator | θmax = 28.7°, θmin = 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 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/[A0*T0(x) + A1*T1(x) ··· + An-1]*Tn-1(x)] where Ai are the Chebychev coefficients listed below and x = F /Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)2]2 Ai are: 0.191E + 04 0.570E + 04 0.179E + 04 0.189E + 04 |
968 reflections | (Δ/σ)max = 0.0002 |
101 parameters | Δρmax = 0.13 e Å−3 |
0 restraints | Δρmin = −0.12 e Å−3 |
C9H14N2 | V = 887.83 (13) Å3 |
Mr = 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)° |
Oxford Diffraction Xcalibur diffractometer | 1153 reflections with I > 3.0σ(I) |
3794 measured reflections | Rint = 0.017 |
1953 independent reflections |
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.103 | H-atom parameters constrained |
S = 0.88 | Δρmax = 0.13 e Å−3 |
968 reflections | Δρmin = −0.12 e Å−3 |
101 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
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* |
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) |
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 |
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. |
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 |
Mr | 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 |
Rint | 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 |
Δρmax, Δρmin (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.
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