High-Pressure Transformations and the Resonance Structure of

Article Cite This: J. Phys. Chem. C 2018, 122, 5064−5070

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High-Pressure Transformations and the Resonance Structure of Thiourea Hanna Tomkowiak and Andrzej Katrusiak* Faculty of Chemistry, Adam Mickiewicz University, Umultowska 89 b, 61-614 Poznań, Poland S Supporting Information *

ABSTRACT: High pressure increases intermolecular interactions in the crystal environment and affects the molecular dimensions of thiourea, CS(NH2)2, consistently with changing contributions of the thione and zwitterionic mesomers. The ambient-pressure phase V (space-group Pnma, Z = 4) at 0.34 GPa transforms to phase VI, of the same spacegroup symmetry, but with the larger unit-cell trifold (Z = 12). Another pressure-induced transition to phase VII was previously postulated for thiourea at 0.54 GPa; however, no associated structural transformations were identified. Our high-pressure single-crystal X-ray diffraction study reveals that following the transition at 0.34 GPa the lattice parameters and crystal structure strongly and monotonically change to about 0.65 GPa while the crystal symmetry is retained.

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INTRODUCTION Thiourea is usually considered as a hybrid of three resonance mesomers, one thione and two zwitterions (Figure 1), with the

orthorhombic phase V remaining stable at normal conditions (space-group Pnma, Z = 4) at 0.34 GPa transforms into phase VI with the unit-cell parameter b tripled and the space-group Pnma retained; hence, Z in phase VI increases to 12. Another pressure-induced transition in thiourea at 0.54 GPa to phase VII was postulated by Gesi,27 but X-ray diffraction study revealed no significant changes of the unit-cell dimensions, and the transition was associated mainly with a dielectric anomaly. In another study,23 the observation of phase VII has been connected with the properties of kerosene, isopentane, and silicon oil used as the pressure-transmitting medium employed in that experiment. Recently, we reported the effect of pressureinduced transformations on the mesomeric contributions of urea.37 Presently, we have investigated the effects of high pressure on the mesomeric forms of thiourea. We also intended to resolve the structural transformations and the crystalsymmetry change associated with the previously postulated phase-transition between phases VI and VII at 0.54 GPa.

Figure 1. Zwitterionic (a,c) and thione (b) mesomeric forms of thiourea.

smallest contribution of the thione form.1−3 This resonance form can be established from molecular dimensions: bond C−S of 1.808 Å significantly longer than the double CS thione bond, an average of 1.681 Å for the structures deposited in the Cambridge Crystallographic Database4 and bond length CN of 1.34 Å, significantly shorter than the single C−N bond of 1.47 Å.5 According to the bond length,6 the contribution of the thione mesomer in thiourea is even smaller than the O C(NH2)2 keto form of the urea analog. Despite similar molecular structures of thiourea and urea, their crystal structures and properties are very different. Under atmospheric pressure, only one crystal phase of urea is known, whereas five solid phases of thiourea were determined, four of them modulated.7−12 The crystal structure of thiourea at ambient conditions was determined by Wyckoff and Corey in 1932.13 They concluded that the molecules are present in the resonance form. The phase diagram of thiourea is shown in Figure S1. Apart from the five ambient-pressure thiourea phases I−V,7−20 the structure of phase VI was determined by X-ray diffraction, powder X-ray diffraction, and neutron diffraction.21−26 Similar to urea, thiourea transforms at high pressure:12,23−37 the © 2018 American Chemical Society

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EXPERIMENTAL SECTION A series of high-pressure experiments were performed on the samples in situ crystallized in a Merrill-Bassett diamond anvil cell (DAC),38 modified by mounting the anvils directly on steel supports with conical windows. Pressure in the DAC chamber was calibrated by the ruby-fluorescence method,39,40 with a Photon Control Inc. spectrometer of enhanced resolution, affording the accuracy of 0.02 GPa; the calibration was repeated before and after each diffraction measurement. The crystallization of thiourea from methanol solution, aqueous solution (under 0.55 GPa), and methanol/ethanol/water mixtures leads Received: January 15, 2018 Revised: February 8, 2018 Published: February 12, 2018 5064

DOI: 10.1021/acs.jpcc.8b00452 J. Phys. Chem. C 2018, 122, 5064−5070

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The Journal of Physical Chemistry C

without recrystallization (Figure 2). About 40 X-ray diffraction data sets were collected for several sample crystals, and then the most accurate ones have been selected for plotting the compression. The experiments were concentrated around the pressure points of the transition to phase VI at 0.34 GPa and around the postulated transition to phase VII.27

Table 1. Selected Crystal Data in the Pressure Ranges of Thiourea Phases V, VI, and Postulated VII at 296 K pressure (GPa) crystal system space group unit cell a (Å) b (Å) c (Å) volume (Å3) Z/Z′ Dcalc (g/cm3) Rint final R1/wR2 (all Ihkl)

phase V

phase VI

phase VII

0.17(2) orthorhombic Pnma 7.5791(9) 8.533(8) 5.4655(4) 353.5(3) 4/0.5 1.430 0.1131 0.0731/0.2095



Figure 2. Thiourea single crystal grown at ambient conditions fixed with a cellulose fiber in the DAC chamber and compressed in Fluorinert 3M. Several small ruby chips for the pressure calibration are also visible.

Figure 4. Crystal environments of independent thiourea molecules in: (a) phase V at 0.1 MPa (the molecules are Cs-symmetric); as well as (b) two independent molecules, one Cs-symmetric (top) and the other in a general position (bottom), in phase VI at 0.50 GPa. The hydrogen bonds are indicated by cyan lines and their H···S distances (Å) are given. Figure 3. Compression of unit-cell dimensions related to the 0.1 MPa/ 296 K values of thiourea in the range of transitions (marked by vertical dashed lines) between phases V, VI, and the previously postulated phase VII. The lines joining the points are for guiding the eye only. Estimated standard deviations (ESDs) are smaller than the plotted symbols.

The single-crystal data were measured with diffractometers KUMA KM4-CCD and Xcalibur EOS. The CrysAlis software41 was used for the high-pressure data collection42 and the preliminary reduction of data. Reflections intensities were corrected for the DAC absorption, the gasket shadows, the sample absorption,41 and the sample reflections overlapping with reflections of the diamonds were eliminated. The structures of phases V, VI, and VII were solved straightforwardly by direct methods, and these models were used for refining all measured structures by full-matrix least-squares.43 Selected high-pressure crystal and experimental data are listed in Table 1, whereas detailed information has been given in

to the pure nonsolvated forms of thiourea (NH2)2CS. Single crystals of (NH2)2CS were grown in situ at isochoric conditions (Figure S2), and the X-ray diffraction data were measured after each crystallization. Another series of the measurements were performed for the single crystals obtained at ambient conditions and compressed in hydrostatic fluid (solution) 5065


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Figure 5. Structure of thiourea in phases V at 0.1 MPa (left) and VI at 0.50 GPa (right). Corresponding H···S distances (Å) in NH···S bonds and similar longer contacts are marked in blue. The NH···S bonded aggregates are viewed in two projections. Gray vertical links represent mirror planes perpendicular to [y] and to the drawing. Projections of the indicated sections of the structure in phase V at 0.1 MPa (down left) and in phase VI at 0.5 GPa (down right) are viewed along the molecular planes in direction [010].

at somewhat higher pressure than previously postulated 0.54 GPa.27 The strongest anomaly in compression is along direction [y], as the crystal elongates by nearly 1% (Figure 3). No clear discontinuities along other directions of the crystal have been observed, but their compression rate changes can be noted around 0.65 GPa. Intermolecular Contacts. Hydrogen bonds NH···S play an important role in the structural transformations of thiourea. Figure 4 shows two main motives of NH···S bonds present in phases V and VI. In phase V, the shortest NH···S bonds, of about 2.4 Å, form double H-bonded ribbons extending along the crystal direction [010]. The double links in the ribbon can be described by graph R22(8).46 These H-bonds involve the syn-H atoms (with respect to the S atom). The two anti-H atoms form two NH···S bonds, of ca. 2.8 Å, to one S atom, aggregating the molecules along the crystal plane (010). The ring descriptor of these H-bonds is R21(6). Thus, each S atom is the H-acceptor in four NH···S hydrogen bonds. In this respect, and in the H-bonds graph descriptors, thiourea is similar to the structure of urea phase I. However, in thiourea, there are also other, albeit considerably longer, even somewhat longer than the sum of van der Waals radii of atoms H and S, contacts NH···S, involving anti-H atoms and extending along plane (010). These other contacts at 0.34 GPa, when thiourea transforms to phase VI, become much shorter for each third molecule along [y], whereas the hydrogen bonds involving anti-H atoms in phase V and phase VI become longer than the sum of van der Waals radii, as illustrated in Figure 5. Thus, the number of short NH···S bonds, their motives, and the H-accepting capability of S atoms remains the same, but the unit-cell parameter b (the translation along

Table S1 in the Supporting Information and deposited in the CIF format at the Cambridge Crystallographic Centre Database as supplementary publications CCDC 1581730−1581740 (their copies can be obtained free of charge from the Web site http://www.ccdc.cam.ac.uk/conts/retrieving.html) and in the Crystallographic Open Database (COD) 3000152− 3000162 (http://www.crystallograohy.net/cod/).

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RESULTS AND DISCUSSION Apart from the well-documented pressure-induced phase transition between thiourea phases V and VI at 0.34 GPa, in the literature, there are three reports on another transition at 0.54 GPa to phase VII.23,27,32 The transition to phase VII is based on a subtle anomaly detected by dielectric measurements, whereas no change of the crystal lattice or space group were found. Such phase transitions are described as isostructural ones.44,45 No mechanism explaining the origin of the transition between phases VI and VII was suggested, either. Thiourea Compression. We have compressed thiourea at 296 K up to 1.75 GPa (Figures 3 and S3). It is characteristic that parameter a is the most compressed parameter in all of this range of pressure; it appears that the least compressed parameter c initially becomes somewhat longer within phase V (negative linear compression to about 0.2 GPa), and then it weakly shortens. At 0.34 GPa at the transition to phase VI, the unit-cell volume increases threefold because of the tripled b parameter, and the Z number increases from 4 to 12; the crystal parameter b noncontinuously shrinks by ca. 2%, whereas parameter c increases its length by ca. 2%. It appears that there is some anomalous compression at 0.65 GPa, which would support the previously suggested transition to phase VII, albeit 5066


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The Journal of Physical Chemistry C [010]) increases threefold. These transformations lead to the closely related crystal structures and lattices of phases V and VI. Thus, at the transition to phase VI, the H-accepting capacity of the S atoms, in phase V, involved in four S···H−N bonds (two of them, S···H1B−N, of ca. 2.4 Å are shorter by ca. 0.4 Å than the two others, S···H1A−N) is retained for both symmetry-independent S atoms. There is a clear indication within phase V that its structure is destabilized by pressure. The longer S···H1A bonds become even longer with the increasing pressure: the S···H1A distance is 2.75 Å at 0.1 MPa and it increases to over 3.21 Å at 0.32 GPa (Figure 6). This elongation of the S···H1A−N bonds precedes their breaking (two out of six, that is, in one of three molecules) and the subsequent formation of two other hydrogen bonds involving H1A atoms above the phase transition. In all hydrogen bonds, the increasing pressure reduces the S···H−N angle: in bond S···H1B−N from 165° to 150° and in S···H1A− N from 135° to 110°, which is a typical effect for the directional hydrogen bonds playing a lesser role in the high-pressure phase than the close-packing of molecules. Although the transition between phases V and VI is clearly visible in the compression of NH···S distances, there are no such apparent changes about the postulated transition to phase VII. There are, however, changes in the rate of compression of N···S distances: the strongest for Niii···S2 (strong negative compression to 0.65 GPa) and N2ii···S2 (strong positive compression to 0.65 GPa). It can be assumed that within the 0.34−0.65 GPa range, the molecules strongly adjust their positions to better fill the confining space. Similar changes as for the NH···S bonds can be also observed for distances H···N and N···N (Figure S4 in the Supporting Information). Only one of H···N distances becomes commensurate with the sum of van der Waals radii of H and N (2.75 Å according to Bondi47) at about 1.4 GPa. Pressure Effect on Z′. Thiourea is one of the relatively few structures increasing its Z′ number in the high-pressure phase.48−53 Compared to phase V, the structure of phase VI has three times more degrees of freedom available to closely pack the molecules, and it is possible that within a few tenths of one GPa after transforming to phase VI, the molecules strongly adjust their positions. These structural close-packing adjustments may involve shifts and rotations of molecules, which can also significantly change the crystal properties in this pressure range. The regions of such strong changes can occur both within one phase or between two separate phases. Presently, no calorimetric information on the compression of thiourea about 0.65 GPa is available, and some anomalies in the crystal compression close to the previously postulated transition between phases VI and VII (0.54 GPa) can result of strong structural rearrangements in this region. Mesomeric Contributions in Thiourea versus Pressure. It appears that the resonance structure of thiourea molecules is affected by pressure in the crystal. On the transition to phase VI, the bond lengths of two independent molecules differentiate; also two corresponding groups N2H2 and N3H2 become different (Figure 7). As expected, the changes in bond lengths are small compared to intermolecular contacts.54 Indeed, the observed changes in our experiment are of about 0.05 Å for bonds C−S and of ca. 0.15 Å for bonds C− N. It can be noted that the corresponding ESDs are of ca. 0.01 and 0.02 Å, and the experimental uncertainty at 0.995 probability level, estimated as 3·ESDs, is equal to 0.03 and 0.06 Å. Thus, the observed bond length differences, equal to

Figure 6. Distances NH···S (top) and N···S (middle), as well as angles NH···S (bottom) plotted as a function of pressure. Lines joining the points are for guiding the eye only. Letter A indicates the H atom in position anti, and letter B the H atom in position syn. The vertical dashed lines indicate the observed and postulated phase transitions. Symmetry codes: (i) x, 1.5 − y, 1 + z; (ii) 0.5 + x, y, 1.5 − z; (iii) 1 − x, 1 − y, 1 − z; (iv) −0.5 + x, 1.5 + y, 1.5 − z; (v) 0.5 + x, 1.5 − y, 1.5 − z; and (vi) x, y, 1 + z.

about 5·ESDs for bond C−S and 8·ESDs for C−N, can be considered statistically significant. Moreover, the observed changes are consistent with the transforming mesomeric structures of thiourea, as shown in Figure 1. In particular, the 5067


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Crystal data and structure-refinement details of thiourea structures; phase diagram of thiourea; crystal samples of thiourea at various pressures; unit-cell parameters of thiourea as a function of pressure; intermolecular NH···N and N···N contacts, and NH···N angle as a function of pressure; angles S−C−N and N−C−N in thiourea as a function of pressure; and structures of thiourea phases V and VI (Figures S6−S8) (PDF)

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Andrzej Katrusiak: 0000-0002-1439-7278 Notes

The authors declare no competing financial interest.

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Figure 7. Bond lengths C−S and C−N in thiourea molecules as a function of pressure. The vertical dashed lines indicate the boundaries between phases V, VI, and postulated VII. Note independent molecules above 0.34 GPa. The lines joining the points are for guiding the eye only.

ACKNOWLEDGMENTS This study was performed within the scheme of statutory research financed by the Ministry of Science and Higher Education in the Faculty of Chemistry, Adam Mickiewicz University in Poznań, Poland. We are grateful to the Wielkopolska Centre for Advanced Technologies for the experimental support.

differentiation of bonds CNH2+ and C−NH2 is combined with the elongation of the C−S− bond, compared to bond C S; these changes observed in the molecular dimensions correspond to increased contribution of the zwitterionic mesomer.

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(1) Pauling, L. Interatomic Distances in Covalent Molecules and Resonance Between Two or More Lewis Electronic Structures. Proc. Natl. Acad. Sci. U.S.A. 1932, 18, 293−297. (2) Pauling, L.; Sherman, J. The Nature of the Chemical Bond. VI. The Calculation from Thermochemical Data of the Energy of Resonance of Molecules Among Several Electronic Structures. J. Chem. Phys. 1933, 1, 606−617. (3) Pauling, L. The Nature of the Chemical Bond, 2nd ed.; Cornell University Press: Ithaca, NY, 1940. (4) Allen, F. H.; Kennard, O.; Watson, D. G.; Brammer, L.; Orpen, A. G.; Taylor, R. Tables of Bond Lengths Determined by X-Ray and Neutron Diffraction. Part 1. Bond Lengths in Organic Compounds. J. Chem. Soc., Perkin Trans. 2 1987, S1−S19. (5) Allen, F. H. The Cambridge Structural Database: a Quarter of a Million Crystal Structures and Rising. Acta Crystallogr., Sect. B: Struct. Sci. 2002, 58, 380−388. (6) Allmann, R. Homoatomic Rings, Chains and Macromolecules of the Main Group Elements; Rheingold, A., Ed.; Elsevier: Amsterdam, 1977; pp 25−58. (7) Shiozaki, Y. Satellite X-Ray Scattering and Structural Modulation of Thiourea. Ferroelectrics 1971, 2, 245−260. (8) Futama, H. Hysteresis and Thermal Studies on Ferroelectric Transitions in Thiourea. J. Phys. Soc. Jpn. 1962, 17, 434−441. (9) Tanisaki, S.; Mashiyama, H.; Hasebe, K. Commensurately Modulated Structure of Thiourea at 170 K. Acta Crystallogr., Sect. B: Struct. Sci. 1988, 44, 441−445. (10) Mashiyama, H.; Hasebe, K.; Tanisaki, S. Phenomenological Theory on Incommensurate and Commensurate Phases and Electric Field-Temperature Phase Diagram in Thiourea. J. Phys. Soc. Jpn. 1988, 57, 166−175. (11) Elcombe, M. M.; Taylor, J. C. A Neutron Diffraction Determination of the Crystal Structures of Thiourea and Deuterated Thiourea Above and Below the Ferroelectric Transition. Acta Crystallogr., Sect. A: Cryst. Phys., Diffr., Theor. Gen. Crystallogr. 1968, 24, 410−420. (12) Denoyer, F.; Moudden, A. H.; Currat, R.; Vettier, C.; Bellamy, A.; Lambert, M. Effect of Hydrostatic Pressure on Modulated Structures in Thiourea. Phys. Rev. B: Condens. Matter Mater. Phys. 1982, 25, 1697−1702.

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CONCLUSIONS The structural data determined in this study show some anomalous compression-changing molecular positions around 0.65 GPa, which is close to the pressure of 0.54 GPa previously postulated for the transition between phases VI and VII. However, the observed anomalies are subtle, and they may be associated with the reduced role of directional hydrogen bonds NH···S compared to the close-packing effects and strong, albeit continuous, adjustments of molecular positions above the transition to phase VI. Consequently, the presence of separate phase VII has not been unequivocally confirmed. We have established that the increased complication of the thiourea structure between phases V and VI is connected with the rearrangement of NH···S hydrogen bonds allowing the reduction of the crystal volume. The observed changes in the molecular dimensions are consistent with the changing contributions of the mesomers in the resonance structures of independent molecules strongly interacting with their different crystal environments. It appears that the contribution of mesomers in compressed compounds changes with pressure, which can lead to their new properties and chemical transformations specific for high-pressure conditions. Presently, a considerable number of pressure-induced transformations have been reported, for example, piezochromic,55 dielectric,56 magnetic,57 as well as pressure-induced amorphization,58−60 and polymorphism;61−67 however, the mesomeric transformations of the studied compounds are usually not considered.

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REFERENCES

ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpcc.8b00452. 5068


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