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Acta Crystallogr C. Mar 15, 2010; 66(Pt 3): o128–o132.
Published online Feb 24, 2010. doi:  10.1107/S010827011000541X
PMCID: PMC2855568

p-Phenyl­enediamine and its dihydrate: two-dimensional isomorphism and mechanism of the dehydration process, and N—H(...)N and N—H(...)π inter­actions

Abstract

p-Phenyl­enediamine can be obtained as the dihydrate, C6H8N2·2H2O, (I), and in its anhydrous form, C6H8N2, (II). The asymmetric unit of (I) contains one half of the p-phenyl­ene­diamine mol­ecule lying about an inversion centre and two halves of water mol­ecules, one lying on a mirror plane and the other lying across a mirror plane. In (II), the asymmetric unit consists of one mol­ecule in a general position and two half mol­ecules located around inversion centres. In both structures, the p-phenyl­enediamine mol­ecules are arranged in layers stabilized by N—H(...)π inter­actions. The diamine layers in (I) are isostructural with half of the layers in (II). On dehydration, crystals of (I) transform to (II). Comparison of their crystal structures suggests the most plausible mechanism of the transformation process which requires, in addition to translational motion of the diamine mol­ecules, in-plane rotation of every fourth p-phenyl­enediamine mol­ecule by ca 60°. A search of the Cambridge Structural Database shows that the formation of hydrates by aromatic amines should be considered exceptional.

Comment

p-Phenyl­enediamine is a popular reagent in organic and coordination chemistry. This compound is quite soluble in water but is generally known in its anhydrous form. In the course of our work on cocrystal formation by aromatic diamines, amino­phenols and diphenols, the previously unknown hydrated form of p-phenyl­enediamine emerged. To check whether formation of a hydrate by p-phenyl­enediamine can be considered exceptional among aromatic amines, recrystallizations of the two other phenyl­enediamine isomers from water have been carried out, always resulting in the known anhydrous form. The crystal structures of the three (o-, m- and p-) anhydrous phenyl­enediamines have already been published (Betz et al., 2008 [triangle]; Poveteva & Zvonkova, 1975 [triangle]; Stalhandske, 1981 [triangle]), with two of them, the meta (Betz et al., 2008 [triangle]) and para (Poveteva & Zvonkova, 1975 [triangle]; Colapietro et al., 1985 [triangle]) isomers, showing high-Z′ structures. The above observations prompted us to take a closer look at the structures of primary aromatic amines deposited in the Cambridge Structural Database (CSD, Version 5.31; Allen, 2002 [triangle]) and to analyse them from the point of view of hydrate formation. This paper, in addition to the crystal structure of p-phenyl­ene­diamine dihydrate, (I), reports the redetermination of the crystal structure of p-phenyl­enediamine, (II), at 130 K to provide more accurate positions of the amino H atoms.

An external file that holds a picture, illustration, etc.
Object name is c-66-0o128-scheme1.jpg

The numbering scheme for (I) is shown in Fig. 1 [triangle]. The asymmetric unit contains one half of the p-phenyl­enediamine mol­ecule, which is located around an inversion centre, and two halves of the water mol­ecules. One water mol­ecule has all its atoms on a mirror plane, whereas the other mol­ecule lies across a mirror plane. The endocyclic bond angle at C1 of 118.17 (11)° is consistent with the electron-withdrawing character of the amino group. The water mol­ecules are linked via O—H(...)O inter­actions into a C4 chain (Infantes & Motherwell, 2002 [triangle]), with one water mol­ecule acting as a double donor and the other as a double acceptor of hydrogen bonding. p-Phenyl­enediamine mol­ecules bridge these water chains by involving their amino groups as single donors and single acceptors in hydrogen bonding (Fig. 2 [triangle] a and Table 1 [triangle]). All these inter­actions generate a two-dimensional network of hydrogen bonds parallel to (010) and a three-dimensional network of hydrogen-bonded mol­ecules (Fig. 2 [triangle] b). The p-phenyl­ene­diamine mol­ecules in (I) are arranged in a herringbone motif into (010) layers. The amino H atom not involved in strong inter­actions with the water mol­ecules forms an N—H(...)π inter­action with an adjacent benzene ring, with an H(...)π distance of 2.48 (2) Å. Each benzene ring accepts two such inter­actions (Fig. 2 [triangle] c). It should be emphasized here that there is no direct hydrogen-bond inter­action between the amino groups in (I). The crystals of (I) are unstable and in air they lose the water mol­ecules and are transformed into the known anhydrous form of p-phenyl­enediamine; this was confirmed by powder diffractograms of a partially decomposed sample of (I).

Figure 1
The mol­ecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Only the symmetry-unique atoms are labelled (water O ...
Figure 2
(a) The two-dimensional hydrogen-bond network of (I) formed by water mol­ecules and primary amino groups (the ring atoms have been omitted for clarity). Hydrogen bonds are shown as dotted lines. (b) A projection of the crystal structure along ...
Table 1
Hydrogen-bond geometry (Å, °) for (I)

The asymmetric unit of (II) contains one mol­ecule in a general position (mol­ecule A) and two halves of p-phenyl­ene­diamine mol­ecules located on two different sets of inversion centres (mol­ecules B and C) (Fig. 3 [triangle]). The endocyclic bond angles at atoms C1A, C4A, C1B and C1C are all significantly smaller than 120° [117.57 (10)–118.04 (10)°] and the C—N bond lengths are in the range 1.4065 (13)–1.4151 (14) Å. The four symmetry-independent primary amino groups are connected via N—H(...)N hydrogen bonds into a polymeric chain extending along [100] (Table 2 [triangle] and Fig. 4 [triangle] a), with each amino group acting as a single donor and a single acceptor in the hydrogen bonding. These N—H(...)N inter­actions generate a three-dimensional network of p-phenyl­enediamine mol­ecules (Fig. 4 [triangle] b). An alternative depiction of the crystal structure of (II) shows it to be composed of a set of two different (001) mol­ecular layers, one layer composed solely of A mol­ecules and the second layer composed of centrosymmetric B and C mol­ecules. The metric parameters of these layers [a = 8.3020 (2) Å, b = 5.8970 (1) Å and γ = 90°] resemble those of the (010) layers in (I) [a = 8.8599 (8) Å, c = 5.8952 (4) Å and β = 90°], and closer inspection of the two structures reveals that the layers of A mol­ecules in (II) are virtually isostructural with the (010) layers of p-phenyl­enediamine mol­ecules in (I), with the aromatic systems accepting two N—H(...)π inter­actions (Table 2 [triangle]). The layers of B and C mol­ecules have a different structure, with the benzene ring of the C mol­ecules accepting two N—H(...)π inter­actions from the N—H group of the B mol­ecule, whereas the aromatic system of B is not involved in this type of inter­action.

Figure 3
The mol­ecular structure of (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Only the symmetry-unique atoms are labelled. Hydrogen ...
Figure 4
(a) Chains of hydrogen bonds formed by primary amino groups (the ring atoms have been omitted for clarity) in (II). Hydrogen bonds are shown as dotted lines. (b) A projection of the crystal structure along the a axis. [Symmetry code: (i) −x + ...
Table 2
Hydrogen-bond geometry (Å, °) for (II)

As indicated above, the dehydration process of (I) results in form (II) of p-phenyl­enediamine. Taking into account the extent of the structural similarities between the two crystalline forms, we suggest a mechanism of transformation between the hydrated and anhydrous forms. In the most plausible mechanism that we can propose, the structure of every second (010) layer of p-phenyl­enediamine mol­ecules in (I) remains unaltered by the dehydration process. When water mol­ecules start to leave the crystal, hydrogen bonds are broken and the amino groups ‘seek’ new donors and acceptors among the primary amino groups located on the surface of a neighbouring layer. The hydrogen-bond network of (I) cannot be fully reconstructed, as the number of NH2 groups on the surface of the neighbouring layer is half the number of water mol­ecules located in the inter­layer space, and the acceptor–donor abilities of a primary amino group are different from those of water mol­ecules. The proposed mechanism of dehydration of (I) is illustrated in Fig. 5 [triangle]. When the dehydration process begins, the stacks of B mol­ecules running along the a axis move in the direction indicated by the arrow in Fig. 5 [triangle] to replace two water mol­ecules in a chain of hydrogen bonds with their NH2 group. Because each water mol­ecule occupies a special position of multiplicity 2 in the crystal structure, stoichiometrically this means a substitution of one water mol­ecule per one amino group. This movement is accompanied by a concerted reorientation of the C mol­ecules also arranged into stacks along the a axis. All C mol­ecules within one stack rotate in the same direction by ca 60° around the axis approximately perpendicular to their aromatic ring plane. On this rearrangement, their NH2 groups replace another pair of water mol­ecules and a polymeric chain of N—H(...)N hydrogen bonds is formed, extending along the a axis and incorporating all amino groups as single donors and single acceptors. This mechanism requires substantial rearrangement of only 25% of the amine mol­ecules in the crystal structure, whereas the remaining 75% of mol­ecules undergo mainly translational motion. The above transformation should be seen as a co-operative structure reconstruction, with both events, viz. translation and rotation of the diamine mol­ecules, occurring at the same time.

Figure 5
The proposed mechanism for the transformation of (I) into (II). One set of arrows show the direction of rotation of the C mol­ecules, and the other set indicates pairs of water mol­ecules replaced by the amino groups of the B mol­ecules. ...

In recent years, several papers dealing with the factors responsible for the formation of organic crystal hydrates have been published (Infantes & Motherwell, 2002 [triangle]; Infantes et al., 2003 [triangle], 2007 [triangle]). The formation of the hydrate by p-phenyl­ene­diamine should be considered rather exceptional in the light of our survey of the CSD, which gave 80 structures of compounds with at least one primary amino group and with only C and H atoms in the remaining part of the mol­ecule [CnHm(NH2)x]. Among these structures, 48 were formed by aromatic, 27 by aliphatic and four by vinyl amines, and one by a mixed aromatic/aliphatic amine. The same search requesting additionally the presence of a water mol­ecule in the crystal structure gave 23 hydrates but only one of them was formed by an aromatic amine, with one mol­ecule of water included per three tetra­amine mol­ecules (CSD refcode RARROS; Laliberté et al., 2005 [triangle]). The search shows that inclusion of water mol­ecules in the crystal structures of primary aromatic mono- and polyamines is less feasible than in the case of their aliphatic analogues.

It is well known that both aliphatic and aromatic primary amines cocrystallize easily with a variety of mono- and dialcohols (Ermer & Eling 1994 [triangle]; Hanessian et al., 1994 [triangle]; Loehlin et al., 1998 [triangle]; Loehlin & Okasako, 2007 [triangle]), as predicted from the saturated hydrogen-bond principle introduced by Ermer & Eling (1994 [triangle]). In the complementary alcohol/amine system, the total number of donor H atoms matches the number of acceptor lone pairs, whereas primary amines alone show an excess of donor H atoms and a deficit of hydrogen-bond acceptors. The inclusion of self-complementary water mol­ecules into the amine crystal structure leaves the unfavourable balance of donors and acceptors unchanged. However, on inclusion of water mol­ecules into the crystal structures of aliphatic primary amines, stronger O—H(...)N and N—H(...)O hydrogen bonds can be formed substituting for weaker N—H(...)N inter­actions, and thus the enthalpic factor starts to play a promoting role in hydrate formation. In turn, primary aromatic amines are weak bases and have lower proton affinity. Thus, to accept a hydrogen bond their amine N atom has to adopt an sp 3 hybridization at the expense of the conjugation energy of its lone pair with the aromatic ring π-system. Moreover, in aromatic amines the ratio of hydrogen-bond donors to acceptors is improved compared with aliphatic amines, as an aromatic ring with its electron-donating amine substituents becomes almost as good a hydrogen-bond accepting group as the aromatic amino group. Analysis of the inter­molecular inter­actions in 48 aromatic amine structures in the CSD shows that N—H(...)π inter­actions are abundant and often competitive with respect to N—H(...)N hydrogen bonding. For example, 19 of the analysed structures show no N—H(...)N inter­actions, whereas only three of them do not have any short N—H(...)π contacts. By way of contrast, there is only one early structure (CSD refcode MTOLID; Fowweather, 1952 [triangle]) where N—H(...)N hydrogen bonds can be postulated but no N—H(...)π inter­actions are possible, considering the arrangement of mol­ecules within the crystal structure.

In the case of the anhydrous form of p-phenyl­enediamine, (II), only one N—H group of the four symmetry-independent NH2 substituents is not involved in any of the specific inter­actions discussed above. However, cocrystallization of p-phenyl­enediamine with water mol­ecules not only allows this mol­ecule to adopt the packing mode in which stronger O—H(...)O, O—H(...)N and N—H(...)O inter­actions replace weaker N—H(...)N hydrogen bonds, but also all donors and all acceptors, including the electron-rich aromatic π system, contribute to the crystal stabilization energy. In our opinion, this is the explanation for this unusual case of hydrate formation by an aromatic amine.

Experimental

The hydrated form, (I), was obtained by slow evaporation of an aqueous solution of p-phenyl­enediamine to give large colourless tabloid crystals. The crystal used for X-ray measurements was pale-pink and was obtained serendipitously during the cocrystal screening. Crystals of (II) were obtained by evaporation of an ethanol–chloro­form mixture.

Compound (I)

Crystal data

  • C6H8N2·2H2O
  • M r = 144.18
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is c-66-0o128-efi1.jpg
  • a = 8.8599 (8) Å
  • b = 15.0248 (14) Å
  • c = 5.8952 (4) Å
  • V = 784.76 (11) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 130 K
  • 0.5 × 0.4 × 0.2 mm

Data collection

  • Kuma KM-4 CCD κ-geometry diffractometer
  • Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007 [triangle]) T min = 0.929, T max = 0.980
  • 3790 measured reflections
  • 830 independent reflections
  • 662 reflections with I > 2σ(I)
  • R int = 0.025

Refinement

  • R[F 2 > 2σ(F 2)] = 0.032
  • wR(F 2) = 0.086
  • S = 1.06
  • 830 reflections
  • 75 parameters
  • All H-atom parameters refined
  • Δρmax = 0.17 e Å−3
  • Δρmin = −0.17 e Å−3

Compound (II)

Crystal data

  • C6H8N2
  • M r = 108.14
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is c-66-0o128-efi7.jpg
  • a = 8.3020 (2) Å
  • b = 5.8970 (1) Å
  • c = 22.7600 (5) Å
  • β = 93.579 (2)°
  • V = 1112.09 (4) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.08 mm−1
  • T = 130 K
  • 0.45 × 0.4 × 0.25 mm

Data collection

  • Oxford Diffraction Xcalibur E diffractometer
  • Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 [triangle]) T min = 0.973, T max = 0.980
  • 9761 measured reflections
  • 2269 independent reflections
  • 1811 reflections with I > 2σ(I)
  • R int = 0.021

Refinement

  • R[F 2 > 2σ(F 2)] = 0.031
  • wR(F 2) = 0.082
  • S = 1.07
  • 2269 reflections
  • 178 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.21 e Å−3
  • Δρmin = −0.15 e Å−3

In (I), all H atoms were located in electron-density difference maps and freely refined (coordinates and isotropic displacement parameters). In (II), all H atoms were identified in difference Fourier maps, but for the refinement all C-bound H atoms were placed in calculated positions, with C—H = 0.93 Å, and refined as riding on their carrier atoms, with U iso(H) = 1.2U eq(C). All N-bound H atoms were freely refined (coordinates and isotropic displacement parameters).

Data collection: CrysAlis CCD (Oxford Diffraction, 2007 [triangle]) for (I); CrysAlis Pro (Oxford Diffraction, 2009 [triangle]) for (II). Cell refinement: CrysAlis RED (Oxford Diffraction, 2007 [triangle]) for (I); CrysAlis Pro for (II). Data reduction: CrysAlis RED for (I); CrysAlis Pro for (II). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]) and Mercury (Macrae et al., 2006 [triangle]); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I, II. DOI: 10.1107/S010827011000541X/fg3154sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S010827011000541X/fg3154Isup2.hkl

Structure factors: contains datablocks II. DOI: 10.1107/S010827011000541X/fg3154IIsup3.hkl

Footnotes

Supplementary data for this paper are available from the IUCr electronic archives (Reference: FG3154). Services for accessing these data are described at the back of the journal.

References

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  • Colapietro, M., Domenicano, A., Hargittai, I., Portalone, G. & Schultz, G. (1985). 9th European Crystallographic Meeting, 2–6 September 1985, Turin, Italy, Abstracts, p. 273.
  • Ermer, O. & Eling, A. (1994). J. Chem. Soc. Perkin Trans. 2, pp. 925–944.
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  • Oxford Diffraction (2007). CrysAlis CCD and CrysAlis REDOxford Diffraction Ltd, Abingdon, Oxfordshire, England.
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Articles from Acta Crystallographica Section C: Crystal Structure Communications are provided here courtesy of International Union of Crystallography