Christina
Taouss
,
Cindy
Döring
,
Peter G.
Jones
*,
Lukas
Pinkert
and
Mark
Strey
Institute of Inorganic and Analytical Chemistry, Technical University of Braunschweig, P.O. Box 3329, D-38023 Braunschweig, Germany. E-mail: p.jones@tu-bs.de; Fax: +49 531 5387; Tel: +49 531 5382
First published on 9th February 2016
Liquid diffusion of n-pentane into a solution of thiourea in 2,5-dimethylpyrazine led to a crystalline 4:3 adduct (1), in which corrugated thiourea layers are crosslinked with pyrazines. Attempts to obtain adducts with other stoichiometries, by crystallizing thiourea from a mixture of 2,5-dimethylpyrazine and methanol, formed the ternary 1:1:1 adduct 2 instead. Adduct 2 displays a layer structure in which parallel thiourea ribbons are linked on the one side by pyrazines and on the other side by methanol and pyrazines, leading to repeating crosslink sequences (⋯thiourea⋯methanol⋯pyrazine⋯methanol⋯thiourea⋯pyrazine⋯); the ribbons within a layer are thus unequally spaced. In inert oil, individual single crystals of 2 spontaneously convert to several smaller crystals, some single, of 1. The process may be regarded as a single-crystal to single-crystal transformation, although not in the usual sense. The 4:3 adduct (3) of thiourea with 2-methylpyrazine is isotypic to 1. In all three structures, the preponderant secondary interactions are classical hydrogen bonds.
Fig. 1 Packing diagram of the 1:1 adduct between urea and 2,6-lutidine (“urea ribbon substructure”), showing two ribbons running horizontally, with the attached lutidines occupying the space between the ribbons. Classical and “weak” hydrogen bonds are drawn as thick or thin dashed lines respectively. Adapted slightly from ref. 3. |
Adducts of urea generally display simpler packing patterns than those of thiourea because the acceptor properties of the urea oxygen atom are more rigid; it generally accepts two hydrogen bonds from D–H donors that effectively lie parallel to the urea molecular plane, so that the packing tends to involve linear or planar groupings. The thiourea sulfur atom, in contrast, often accepts more than two hydrogen bonds, and the D–H vectors can subtend large angles to the thiourea molecular plane; thus the packing patterns are often three-dimensional and complex.8,9
We have now extended our studies to the investigation of adducts between urea or thiourea as component A and various liquid pyrazines as component B, and present here our results for thiourea and 2,5-dimethylpyrazine. Methanol was used as the additional solvent C.
Ternary adduct 2: 54 mg of thiourea was dissolved in a mixture of 1.1 mL 2,5-dimethylpyrazine and 0.9 mL methanol. The solution was distributed over several small ignition tubes and overlayered with n-heptane. Crystals in the form of large (2 mm) colourless laths were obtained.
Structure determination of the laths 2 was made difficult by the fact that they fragmented badly upon cutting. Initial attempts led to crystals of poor quality, for which nonetheless a cell could be determined and was clearly different from that of 1. To our surprise, a crystal of good optical quality was then found and proved to have the same cell as that of 1. A more thorough investigation under the microscope showed that the laths were slowly disappearing, with the concomitant formation of new crystals of 1, some of them being single crystals (Fig. 2). The structure corresponding to the laths was then successfully determined by waiting for a small section to become isolated from the main crystal via formation of 1, then mounting this fragment rapidly. Frustratingly, the crystals also proved to be sensitive to very low temperatures (whereby they shattered and were irretrievably lost), but could be successfully measured at 170 K, revealing the presence of the ternary 1:1:1 adduct 2 between thiourea, 2,5-dimethylpyrazine and methanol (Scheme 1). The sample on the microscope slide had been immersed in a protective layer of inert oil, so the transformation from 2 to 1 presumably occurred via gradual loss of methanol, redissolution of the adduct and then crystallization of 1 as the proportion of 2,5-dimethylpyrazine in the solvent drop increased.
Fig. 2 A lath-shaped crystal of ternary adduct 2 converts to several crystals of the binary adduct 1 at room temperature over a period of ca. 30 min. The length of the original crystal was ca. 2 mm. |
When the study was extended to the adducts of thiourea and 2-methylpyrazine, the 4:3 adduct 3 was obtained and was isotypic to 1; this structure has been deposited but is not discussed any further. A 3:1 adduct was also obtained, but this proved to be a known clathrate structure type in which the guest molecules are severely disordered.10
The packing of 2 (Fig. 4) involves ten classical hydrogen bond systems (Table S2‡), counting the three-centre interaction as one system. Each sulfur atom accepts two hydrogen bonds. Despite the tendency of the thiourea sulfur atom to accept hydrogen bonds from any angle to its molecular plane, all four such hydrogen bonds in 2 do in fact subtend small angles to the relevant planes (Table S2‡). The thiourea molecules thereby form an approximately planar ribbon substructure, topologically identical to the urea ribbon shown in Fig. 1, parallel to the a axis. The crosslinks between the ribbons lead to repeating sequences (⋯thiourea⋯methanol⋯pyrazine⋯methanol⋯thiourea⋯pyrazine⋯), which run diagonally across Fig. 4. The unequal spacing between ribbons of a given layer is clearly recognisable and is attributable to the methanol spacers lying between N4, N6 and N11, N21. The extended structure is a layer parallel to (03).
The 4:3 adduct 1 also crystallizes in P; the asymmetric unit consists of two thioureas, one entire pyrazine and one half pyrazine (Fig. 5). The interplanar angle between the two thioureas is 89.15(4)°.
In the packing of 1, each of the eight potential hydrogen bond donors forms one hydrogen bond (Table S3‡). Each sulfur atom accepts three hydrogen bonds. It is not possible for all three D–H donor systems to lie close to the molecular plane of the corresponding acceptor; instead the simple donors (N1–H02 and N4–H06) subtend small angles to the relevant planes, whereas the bifurcated donor systems (N1–H01/N3–H03 and N4–H05/N6–H07) are approximately perpendicular to the relevant planes (Table S3‡). In this way, the thiourea molecules combine to form a corrugated layer structure parallel to the ac plane at y ≈ 0, 1, etc. (Fig. 6), from which the two remaining hydrogen bond donors project outwards.
The pyrazines occupy the spaces between the layers (Fig. 7) and act thereby as hydrogen bond acceptors (although N11 does not accept any classical hydrogen bonds). The hydrogen bond H04⋯N14 is terminal, whereas H08⋯N21 acts as a bridge between thiourea layers. Closer inspection shows that the pyrazines in fact form two “weak” hydrogen bonds (Table S3‡) and a probable π⋯π interaction (the intercentroid distance for neighbouring pyrazines based on N11 is 3.56 Å), but these are omitted from Fig. 7 for clarity.
We have also observed the same 4:3 stoichiometry for an adduct of thiourea with morpholine,2 but the packing is quite different from that of 1, consisting of an open framework of thiourea molecules forming channels that are occupied with ordered morpholines.
There is no clear evidence for any major conservation of the packing features ongoing from the structure of 2 to that of 1; it seems that the molecules of thiourea and 2,5-dimethylpyrazine are completely redistributed (whereby some of the latter and all of the methanol is lost) during the process of redissolution and recrystallization. Consistent with this, a pool of liquid can be seen to form around the crystals (Fig. 2).
Single-crystal to single-crystal transformations, which may be reversible, are of course a phenomenon that has been widely studied, partly because of potential applications such as molecular switches. In general, the external habit of the crystal is retained. A recent special issue of CrystEngComm was devoted to the theme of single-crystal to single-crystal transformations,14 and the reader can refer to this for general literature references. Spontaneous transformations involving simple organic compounds, adducts or metal complexes appear to be much rarer, although we have observed the spontaneous transformation of one polymorph of cyano(3,5-lutidine)gold(I), consisting of large plates, into small blocks of another polymorph;15 unfortunately we were unable to take suitable photographs because of the small quantity of the available material. Such serendipitously observed processes, although they may be formally regarded as (one)-single-crystal to (several)-single-crystal transformations, do not fit well into the general theme of single-crystal to single-crystal transformations; the crystal habit is not retained, and it is not easy to correlate the packing patterns of the two structures in terms of robust synthons.
Footnotes |
† This paper is dedicated to the memory of Prof. Armand Blaschette (d. 23.9.2015), a highly respected colleague who introduced me to the structural chemistry of urea derivatives. – P. G. J. |
‡ Electronic supplementary information (ESI) available. CCDC 1445109 (1), 1445110 (2) and 1445111 (3) contain the supplementary crystallographic data for this paper. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6ce00100a |
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