Touraj
Manifar
a,
Sohrab
Rohani
a,
Michael
Jennings
b,
Douglas
Hairsine
b and
Ian
Dance
*c
aCrystallization and Control Laboratory, Department of Chemical and Biochemical Engineering, University of Western Ontario, London, Ontario, Canada
bDepartment of Chemistry, University of Western Ontario, London, Ontario, Canada
cSchool of Chemistry, University of New South Wales, Sydney, NSW 2052, Australia. E-mail: I.Dance@unsw.edu.au
First published on 13th January 2006
Molecules NAr3 with planar stereochemistry at N and canted Ar rings can form the intermolecular sixfold aryl embrace (6AE). The presence of 3-methyl groups on the aryl groups enhances the stabilisation of the 6AE, by contributing to the EF motifs which comprise it. Analysis of the crystal packing of four tritolylamines, N,N,N-tris(4-methylphenyl)amine [444TTA], N-(3-methylphenyl)-N,N-bis(4-methylphenyl)amine [344TTA], N,N-bis-(3-methylphenyl)-N-(4-methylphenyl)amine [334TTA] and N,N,N-tris(3-methylphenyl)amine [333TTA], reveals the presence of (333TTA)2 dimers maintained by an excellent 6AE, an unprecedented almost linear chain of repeated 6AE in 334TTA (cryst), and poorly formed embrace motifs in 344TTA (cryst), and 444TTA (cryst). Calculated intermolecular potentials for the actual or possible 6AE embraces formed by 333TTA, 334TTA and 444TTA confirm the stabilisation of the 6AE by 3-methyl groups, and it is estimated that each such methyl group augments the stabilisation of the underlying 6AE embrace by ca 5 kJ mol−1. The dominant dimerisation that occurs in crystalline 333TTA is reflected in the phase change enthalpies for the four isomers. The enthalpy of sublimation of 333TTA (51 kJ mol−1) is ca 45 kJ mol−1 less than the enthalpies of sublimation of 334TTA (97 kJ mol−1), 344TTA (98 kJ mol−1) and 444TTA (93 kJ mol−1), which leads to the hypothesis that (333TTA)2 dimers occur in the gas phase at ambient pressure. Mass spectrometric attempts to detect (333TTA)2(g), as [(333TTA)2]+, were unsuccessful, possibly due to dissociation under high vacuum. The unknown crystal packing of tris(3,5-dimethylphenyl)amine is predicted to be dominated by linear chains of methyl-stabilised 6AE.
In this context, the availability of crystal structures and phase-change enthalpies for a set of four isomeric tritolylamines (444TTA, 344TTA, 334TTA, 333TTA)3 prompted us to analyse relationships between crystal packing and thermochemical data for these related compounds. These compounds constitute an informative set, in which the intermolecular interactions are not complicated by hydrogen bonding or ion association.
The enthalpy of sublimation of one compound, 333TTA, is distinctly different from those of the other three, and therefore we sought explanation of this through examination of the crystal packing. This analysis, supplemented by calculations of relevant intermolecular potentials, led to a prediction that a stable embracing dimer of 333TTA might exist in the gas phase, and we attempted to detect this dimer by mass spectrometric measurements.
Intermolecular interactions between molecules containing aryl groups are based on two fundamental geometrical motifs, the offset-face-to-face (OFF) and edge-to-face (EF) arrangements.2,4 In molecules containing multiple aryl groups these pairwise primary motifs may operate in concert to form intermolecular embraces. Molecules containing triaryl entities Ar3E are well-known to form intermolecular embrace motifs in crystals: the two most common embraces are the sixfold phenyl/aryl embrace (6PE/6AE) which is an (EF)6 concert involving all six aryl groups (Fig. 1(b)), and the (OFF)(EF)2 concert involving four aryl groups, named the parallel fourfold phenyl/aryl embrace (P4PE/P4AE, Fig. 1(c))
Fig. 1 (a) The common edge-to-face (EF) and offset-face-to-face (OFF) interactions between a pair of aromatic groups. (b) The centrosymmetric sixfold phenyl embrace (6PE), or (EF)6 embrace, between a pair of Ph4P+ molecules (colour-differentiated C atoms). The six vectorial EF interactions (those visible are marked with arrows) alternate between the molecules around the embrace. (c) The centrosymmetric parallel fourfold phenyl embrace (P4PE) or (OFF)(EF)2 embrace between a pair of Ph4P+ molecules: the double-ended arrow is the OFF interaction. |
In almost all of the molecules known to form these embraces the Ar3E moieties are pyramidal at E (usually P or As), and for the sixfold embraces the Ar3E moieties are threefold rotors.5 The triarylamines (E = N) are essentially planar at N, but the inclinations of the aryl groups to the C3N plane permit embrace motifs, although these had not been investigated prior to this work.
The crystallographic data for these compounds is available in the literature.7
Fig. 2 Skeletal and space-filling representations of the centrosymmetric sixfold aryl embrace (EF)6 between a pair of 333TTA molecules, viewed along and normal to the N⋯N vector. The three rings on each molecule are coloured green, orange and magenta, and all methyl C atoms are black: N blue. The symmetry of the embrace is close to . Each of the six EF local interactions that comprise the embrace involves 2-C–H and 3-methyl C–H of one tolyl group directed towards the face of a tolyl ring on the other molecule: the three EF interactions evident on the lower right picture are marked with grey arrows. |
The embracing pairs of molecules are loosely stacked along the c-axis of the crystal, as illustrated in Fig. 3. Apart from one CH3 to tolyl face motif, the lateral interactions between embrace pairs in adjacent stacks are non-specific van der Waals stabilisation (Fig. 4).
Fig. 3 The relationship between adjacent pairs of embracing 333TTA molecules stacked along the c-axis. |
Fig. 5 Projection along the chains of molecules in crystalline 334TTA. Twofold axes pass through the 4-tolyl substituents, coloured orange, with both disorder components of the 4-methyl groups included. Note that the methyl groups (C black) are segregated. |
Fig. 6 Aspects of the interactions between four contiguous 334TTA molecules along the dominant chains in the crystal. (a) Skeletal view. The blue/white stripes are the N–N separations across centres of inversion: N–N 4.48 Å, N–N–N 176°; twofold axes pass though the orange tolyl groups. (b) Space-filling representation, emphasising the approach (red enclosures) of the 2-C–H and 3-methyl C–H atoms of the green ligands to the faces of green ligands in the next molecule. Edge (green) to face (orange) and edge (orange) to face (green) motifs are also visible. (c) Space-filling view showing how two edges of the orange ligand interact with the faces of green ligands of the two contiguous molecules (red enclosures). |
As far as we know this sequence of continuous sixfold aryl embraces has not been observed previously.
Fig. 7 The approximate sixfold aryl centrosymmetric embrace between two 344TTA molecules: the N–N separation (obscured) is 5.0 Å. The methyl group of the 3-tolyl molecule (C brown) is not part of the embrace. Inclinations of the aryl planes to the C3N core plane are 31, 35 and 63°. |
Fig. 8 The crystal packing of 444TTA (space-group P), conceptualised as alternating corrugated layers of the two independent molecules (coloured green and orange). |
Fig. 9 The local motifs in the crystal structure of 444TTA, illustrated for four contiguous molecules, differentiated by C atom colour. A centrosymmetric offset-face-to-face interaction is marked with the yellow enclosure; the red enclosures and the blue enclosures mark centrosymmetric pairs of edge-to-face interactions involving the 3-C–H and 4-CH2 donors. |
To summarise the crystal packing and intermolecular interactions in these four crystals: (a) 333TTA molecules occur as pairs maintained by a well-formed 6AE in which all of the 3-methyl groups are involved, and van der Waals interactions of these (333TTA)2 pairs with neighbours are apparently less significant; (b) 334TTA molecules form a continuous chain of 6AE embraces, in which the 4-methyl group is not involved, and the EF local motifs are not as well developed as those in 333TTA; (c) 344TTA molecules pack with poor geometrical efficiency, with only one in three molecules occurring in a concerted motif which is a less well developed 6AE involving none of the tolyl methyl groups; (d) 444TTA molecules do not form sixfold aryl embraces in the crystal, but do engage in some (EF)2 and OFF intermolecular interactions.
The preceding analysis of intermolecular motifs has been based solely on geometric juxtaposition, but of course it is the energies of these interactions that are determinative. We next describe our measurements of the phase-change thermochemical properties of these crystals, and their relationships with the crystal packing.
Compound | 333TTA | 334TTA | 344TTA | 444TTA |
---|---|---|---|---|
Mp/°C | 39.8 | 89.5 | 56.7 | 115.6 |
ΔHfus/kJ mol−1 | 13.07 | 26.39 | 21.71 | 19.95 |
Bp/°C | 294.8 | 274.2 | 315.9 | 300.9 |
ΔHvap/kJ mol−1 | 37.59 | 69.29 | 75.93 | 72.57 |
ΔHsub/kJ mol−1 | 50.66 | 95.69 | 97.64 | 92.53 |
These data prompt the hypothesis that the favourable 6AE evident in crystalline 333TTA might be retained in a dimeric molecule in the gas phase: the hypothesis is that eqn (1) is the sublimation process for 333TTA, while the other three compounds dissociate according to eqn (2). The reduced value of ΔHsub for 333TTA is proposed to occur because the [(tolyl)3N]2 dimer is not dissociated.
(tolyl)3N (cryst) ⇒ [(tolyl)3N]2 (g) | (1) |
(tolyl)3N (cryst) ⇒ (tolyl)3N (g) | (2) |
This interpretation of the ΔHsub data is summarised in Scheme 1.
Scheme 1 |
The differentiation of 333TTA from the other compounds occurs also for the enthalpies of fusion and vapourisation, and so the hypothesis is also that the [(tolyl)3N]2 dimer occurs in the liquid phase more so for 333TTA than for the other isomers.
In order to explore this idea that the 6AE association of 333TTA is special, and to assess the merits of the observed and unobserved 6AE pairings of TTA isomers, intermolecular potentials have been calculated, by two independent methods. Details of the methods and the resulting potentials are provided in the supplementary material.† The energy of the 6AE in (333TTA)2 is estimated to be 65 ± 10 kJ mol−1, and in (334TTA)2 about 50 ± 10 kJ mol−1. The unobserved 6AE for (444TTA)2 is estimated to have an energy of 35 ± 10 kJ mol−1. From the participation of the tolyl methyl groups in the EF motifs of these embraces—6 methyl groups per 6AE in (333TTA)2, 2 methyl groups per 6AE in (334TTA)2, none in (444TTA)2—it could be concluded that each methyl group augments the stabilisation of the underlying embrace by ca 5 kJ mol−1. The calculated dissociation potential energy of the (333TTA)2 dimer, ca 65 kJ mol−1, is of similar magnitude to the deficit in ΔHsub for 333TTA, ca 45 kJ mol−1 (Scheme 1).
Since paired 333TTA molecules are postulated to exist in the gas phase, we made mass spectrometric measurements in attempt to detect them. Since it is known that the intermolecular stabilisation of positively charged benzene pairs [(C6H6)2]+ is much larger than that of uncharged pairs—experimental measurements for [(C6H6)2]+ range 35 to 90 kJ mol−1,8,9 compared with 7 to 10 kJ mol−1 for (C6H6)2—it was expected that ionized [(333TTA)2]+ would be strongly stabilised in the gas phase. Solutions of the four isomeric TTA molecules in either toluene or methanol were investigated by electrospray ionisation techniques using ranges of sample cone voltages and capillary voltages, but no evidence of dimer cations was found in the resulting spectra. Experiments with the solids on a solid probe and electron ionisation also yielded no evidence of dimers. We suspect that the failure to observe the predicted dimer cations is due to the high vacuum conditions which favour dissociation, and believe that detection of the dimer in the gas phase should be attempted at ambient pressure.
As far as we know, the almost linear chain of repeated 6AE in 334TTA is unprecedented. It cannot occur with pyramidal EAr3 molecules. Tetrahedral EAr4 molecules can form zig-zag chains of repeated 6AE,10 but these do not use both edges of all aryl rings as occurs in the 334TTA crystals. The principles developed above lead to the expectation that the molecule (tris(3,5-dimethylphenyl)amine) which has correctly placed methyl groups on both edges of the phenyl substituents will be able to form two of the favourable 6AE motifs demonstrated by 333TTA. Therefore we predict that tris(3,5-dimethylphenyl)amine will crystallise with the formation of linear chains repeating the most stable 6AE, illustrated in Fig. 10: this is an infinite extension of the 6AE that occurs in 333TTA (Fig. 2).
Fig. 10 A four molecule segment of an infinite chain, predicted to be the principal intermolecular feature in crystalline tris(3,5-dimethylphenyl)amine. Ring C atoms are coloured green and orange in alternating molecules, and all methyl C atoms are black. Each molecule is involved in a complete 6AE with its neighbours: the 2-CH, 3-CH3, 5-CH3 and 6-CH of each ring are EF donors, and all ring faces are EF acceptors. |
For these four isomers of TTA there is good general agreement between the observed crystal packing and the experimental phase change enthalpies.11 The isomer with optimally located 3-methyl groups and able to form the most energetically stabilised 6AE, occurs as such in the crystal. With diminishing energy of the 6AE as the methyl groups are relocated to 4-positions, the integrity of this 6AE motif in the crystals also diminishes.
Footnote |
† Electronic supplementary information (ESI) available: Calculations of intermolecular potentials. See DOI: 10.1039/b516210f |
This journal is © The Royal Society of Chemistry 2006 |