m-Phenyl­enediamine

Richard Betz; Peter Klüfers; Peter Mayer

doi:10.1107/S1600536808039950

. 2008 Nov 29;64(Pt 12):o2501. doi: 10.1107/S1600536808039950

m-Phenylenediamine

Richard Betz ^a, Peter Klüfers ^a,^*, Peter Mayer ^a

PMCID: PMC2960132 PMID: 21581461

Abstract

In the title compound, C₆H₈N₂, there are four molecules in the asymmetric unit, with each molecule, including the H atoms on the N atoms of the amino groups, showing local C2 symmetry. In the crystal structure, all except one of the NH₂ groups participate in N—H⋯O hydrogen bonding. The identified hydrogen bonds furnish a three-dimensional network. N—H⋯π contacts are observed with H⋯π distances ranging from 2.516 (17) to 2.815 (16) Å. No π-stacking of the aromatic rings is observed.

Related literature

For the crystal structures of a series of meta-phenylenediamine salts derived from mineralic acids, see: Anderson et al. (2006 ▶).

Experimental

Crystal data

C₆H₈N₂
M _r = 108.14
Monoclinic,
a = 8.1350 (4) Å
b = 12.0080 (6) Å
c = 23.9003 (16) Å
β = 90.818 (5)°
V = 2334.5 (2) Å³
Z = 16
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 200 (2) K
0.32 × 0.26 × 0.22 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2005 ▶) T _min = 0.976, T _max = 0.983
13102 measured reflections
4681 independent reflections
2852 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.088
S = 0.96
4681 reflections
354 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2005 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2005 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808039950/ez2150sup1.cif

e-64-o2501-sup1.cif^{(22.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808039950/ez2150Isup2.hkl

e-64-o2501-Isup2.hkl^{(229.3KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N11—H112⋯N33ⁱ	0.876 (17)	2.519 (17)	3.3196 (19)	152.5 (14)
N13—H131⋯N33ⁱⁱ	0.965 (17)	2.471 (18)	3.3312 (19)	148.2 (13)
N13—H132⋯N43ⁱⁱⁱ	0.869 (14)	2.448 (15)	3.3102 (19)	171.4 (13)
N21—H211⋯N11ⁱⁱ	0.847 (16)	2.450 (17)	3.291 (2)	172.0 (13)
N21—H212⋯N41	0.939 (16)	2.435 (17)	3.349 (2)	164.4 (14)
N23—H231⋯N21^iv	0.876 (18)	2.574 (19)	3.443 (2)	171.3 (16)
N31—H312⋯N13^v	0.896 (17)	2.510 (17)	3.2668 (19)	142.4 (13)
N33—H332⋯N23	0.911 (16)	2.314 (16)	3.2025 (18)	164.9 (13)
N41—H412⋯N31^vi	0.897 (18)	2.392 (17)	3.164 (2)	144.3 (15)
N11—H111⋯Cg2ⁱ	0.914 (17)	2.573 (16)	3.4260 (14)	155.8 (14)
N23—H232⋯Cg1	0.887 (18)	2.516 (17)	3.2454 (15)	139.9 (15)
N31—H311⋯Cg4^vii	0.922 (17)	2.815 (16)	3.7205 (16)	166.6 (13)
N33—H331⋯Cg2^iv	0.860 (16)	2.608 (15)	3.2617 (13)	133.8 (13)
N41—H411⋯Cg1^viii	0.868 (18)	2.707 (17)	3.5729 (15)	174.1 (16)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) . C1, Cg2 and Cg4 are the centroids of the C11–C16, C21–C26 and C41–C46 phenyl rings, respectively.

Acknowledgments

The authors thank Professor Thomas M. Klapötke for generous allocation of diffractometer time.

supplementary crystallographic information

Comment

In a program focused on the synthesis of derivatives of phenylarsonic acid, a number of substituted aniline-derivatives were chosen as starting materials. In order to compare the influence of an arsonic group on the geometry of some of these starting materials, the crystal structure of meta-phenylenediamine was elucidated by means of single-crystal X-ray diffraction.

In the molecule (Fig. 1) bond lengths and angles are normal. The H atoms on the nitrogens in each molecule are orientated towards different sides of the aromatic plane. The asymmetric unit contains four molecules (Fig. 2).

In the crystal structure, several of the amino groups participate in a classical hydrogen bonding system. In addition, N–H···π contacts are observed with H···π distances ranging from 2.516 (17)Å to 2.815 (16)Å. Details about distances and angles of these interactions are given in Table 1 (C_gn is the centroid of the Cn1–Cn6 phenyl ring). Summarizing both these interactions, only the amino group on N43 is not involved at all. No π-stacking of the aromatic moieties is obvious. In total, a three-dimensional network is established by these interactions (Fig. 3).

Experimental

The compound was obtained commercially (Fluka). Crystals suitable for X-ray analysis were obtained upon slow evaporation of a solution of the compound in propan-2-ol.