High-Pressure Crystallizations of meta-Dichlorobenzene and

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High-pressure crystallizations of meta dichlorobenzene and dibromobenzene and their solid solutions Michalina Anio#a, Karolina Kwa#na, Weizhao Cai, and Andrzej Katrusiak Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.6b00905 • Publication Date (Web): 10 Oct 2016 Downloaded from http://pubs.acs.org on October 15, 2016

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Crystal Growth & Design

High-pressure crystallizations of meta dichlorobenzene and dibromobenzene and their solid solutions

Michalina Anioła, Karolina Kwaśna, Weizhao Cai and Andrzej Katrusiak

Faculty of Chemistry, Adam Mickiewicz University, Umultowska 89 b , 61-614 Poznań, Poland. KEYWORDS high-pressure, halogen bonds, solid solution

Similar halobenzene derivatives, 1,3-dichlorobenzene, m-C6H4Br2, and 1,3-dibromobenzene, mC6H4Cl2, form crystals remarkably similar in the unit-cell dimensions, in two symmetryindependent molecules (Z’=2) and in their atomic positions along plane (yz). However the atomic x-coordinates are different and the space-group symmetry of m-C6H4Cl2 is P21/c and that of m-C6H4Br2 is P212121. These symmetries are not changed by isochoric recrystallizations at least to 2.7 and 1.6 GPa, respectively. The 1-dimensional structural differences originate from one additional Br···Br halogen bond in otherwise very similar halogen···halogen bonds patterns. Of the m-C6H4Br2 : m-C6H4Cl2 1:1 mixture a solid solution (symmetry of space-group P21/c) is formed at 0.5 GPa. However, an addition of methanol to the mixture counteract the formation of

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the solid solution and at 0.45 GPa the pristine m-C6H4Cl2 crystals precipitate. For the 1:1:6 mixture with methanol, pressure of 1.0 GPa is required for the formation of solid solution with the major contests of m-C6H4Cl2 and minor contents of m-C6H4Br2. It is characteristic for the obtained solid solution that intermolecular interactions discriminate the occupation of two symmetry-independent sites in the crystal by molecules dClB and dBrB.

Introduction Crystal structures and thermodynamic properties of 1,3-dichlorobenzene (dClB) and 1,3dibromobenzene (dBrB), shown in Scheme 1, are most intriguing in several respects. Their crystals have similar unit-cells (Table 1), very similar structures in two dimensions, the same Z’ equal 2, but the space-group symmetry different, P21/c and P212121 respectively. Both these structures are governed by halogen···halogen1 and CH···halogen2 bonds, of which Br···Br and CH···Br are generally stronger than corresponding Cl···Cl and CH···Cl bonds.3 In the series of meta and para isomers of dichlorobenzene and dibromobenzene, isomers dClB melt and boil at lower temperature than the dBrB counterparts, however at 296 K the pressure of isothermal crystallization of the dClB isomers is lower than the pressure of the corresponding dBrB isomers. Moreover, in this series only in the crystal structures of dClB and dBrB meta isomers there are two independent molecules (Z’ = 2) in asymmetric part of the unit cell. The occurrence of multiple independent molecules in crystal is relatively rare.4 It usually indicates some inability of the molecules to pack closely in the crystal. It was shown for several compounds that at high pressure they crystallize in new phases with a reduced Z’ number.5-7 On the other hand there are compounds for which high pressure increases the Z’ number.8-11 Thus it appeared plausible that


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one of these crystals, dClB or dBrB, could be destabilized and transformed into another structure, which would reveal the high-pressure preference for one of the halogen-halogen bonding schemes, either that present in dClB or that in dBrB. Therefore we varied the thermodynamic conditions for crystallizing dClB and dBrB separately, as well as for their 1:1 mixture. We wanted to check if these exceptional compounds transform one into the structure of the other and also if the different environments of independent molecules (Z’=2) could destabilize the structures. It was recently established that high pressure favors CH···halogen contacts and destabilizes halogen···halogen bonds in bromomethane CH3Br.12 Its low-pressure phase α is isostructural with CH3I, dominated by halogen bonds I···I, while at high-pressure CH3Br is isostructural with CH3Cl, governed mainly by CH···Cl contacts. Analogues transformations could occur in one or both partly isostructural crystals dClB and dBrB. But most importantly, the coincidence of similar molecular shape and crystal structure of dClB and dBrB, could promote the co-crystallization of these compounds. The crystals of centrosymmetric dClB and non-centrosymmetric dBrB and their mixture appeared ideal for studying the mechanism of molecular aggregation, essential for predicting the structure, symmetry and properties of crystals, necessary in the search for new functional materials and their practical applications. The molecular aggregation in crystals is generally associated with the close packing, also known as Kitaigorodskii’s rule, electrostatic forces between ions and atomic charges, dispersion forces as well as specific interactions such as hydrogen and halogen bonds. Their role is essential for understanding the most fundamental features of materials chemistry such as the occurrence of isostructural crystals of different compounds,13,14 polymorphs of one compound,15 their crystal and molecular symmetries, as well as different number of symmetry-independent molecules.16


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Scheme 1. Atomic labels in the symmetry-independent molecules (labeled A and B) of 1,3dichlorobenzene and 1,3-dibromobenzene, m-C6H4X2 (X=Cl, Br).

The formation of very similar crystal structures by different compounds can have effect for their possible mixing and for the formation of multicomponent crystals.17 Such crystals, in turn, can be applied for tuning the properties of materials, for example for obtaining more soluble or more stable forms of active pharmaceutical ingredients (APIs).18,19 Although the formation of polymorphs of neat compounds, their solvates and co-crystals is intensely studied,20-23 there are still few reports describing the effect of pressure. On the other hand, there are still relatively few solid solutions of organic compounds and their importance and practical applications are not fully explored. Therefore new methods for obtaining solid solutions of organic compounds are intensely sought by material chemists.24-26 Table 1. Selected crystal data of dClB, dBrB and their solid solution at high-pressure. The full crystallographic information of all each compound are listed in Tables S1, S2, S3 and S4. m-C6H4Cl2

m-C6H4Br2

m-C6H4Cl1.2Br0.8a m-C6H4Cl1.4Br0.6b

Pressure (GPa)

0.45(2)

0.41(2)

0.50 (2)

1.05(2)

Mr (g·mol-1)

147

236

181.5

181.5

m.p. (K)

250

266

-

-

b.p. (K)

445

491

-

-

Crystal system

Monoclinic

Orthorhombic

Monoclinic

Monoclinic

Formula


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Space group

P21/c

P212121

P21/c

P21/c

a (Å)

3.8523(3)

4.0169(5)

3.9454(3)

3.8198(11)

b

12.400(4)

12.708(3)

12.511(12)

12.57(2)

c

25.607(9)

25.90(2)

26.120(3)

25.19(7)

β(°)

93.377(8)

90

93.463(7)

94.35

Volume (Å3)

1221.0(6)

1321.9(13)

1287.0(12)

1206(4)

Z/Z’

8/2

8/2

8/2

8/2

Dx (g·cm-3)

1.599

2.371

1.868

2.109

Final R1

0.0400

0.0465

1.868

0.0753

a

Solid solution m-C6H4Cl1.2Br0.8 was obtained from the 1:1 dClB:dBrB mixture.

b

Solid solution m-C6H4Cl1.4Br0.6 was obtained 1:1:6 dClB:dBrB:methanol mixture.

Experimental The crystals of dClB and dBrB were in situ grown in a diamond-anvil cell (DAC) of the Merrill-Bassett type,27 modified by mounting the diamond anvils directly on steel supports with conical window. Pressure in the DAC chamber was calibrated by the ruby-fluorescence method,28 using a Photon Control spectrometer affording an accuracy of 0.03 GPa. Gaskets were made of tungsten foil 0.3 mm thick with a spark-eroded hole 0.40 mm in diameter. The DAC chamber was filled with the mixtures of methanol with either dClB or dBrB. Pressure was increased till the polycrystalline precipitate filled the chamber. Then the DAC was heated up to 533 K, and then slowly cooled down in order to obtain a single crystal (Fig. 1). The X-ray diffraction measurements were carried out with a KUMA KM4-CCD diffractometer.29 After the diffraction measurement the pressure was gradually increased and every time after increasing the pressure a new single crystal was grown. Also, mixed dClB and dBrB (1:1 vol., Fig.1c), as well as their mixture with methanol (vol. 1:1:6, Fig. 1d) were loaded into the DAC chamber. From the mixture of neat dClB and dBrB a precipitate formed at about 0.3 GPa and the single crystal data


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showed that it was a solid solution of the two compounds. However, below 1.0 GPa of the dClB:dBrB:methanol mixture only dClB crystallized, which was clear from the unit-cell dimensions, the crystal symmetry and its well refined structure (Table S1). Above 1.0 GPa solidsolution crystals of somewhat different contents of dClB and dBrB were obtained. All the sold solutions crystallized in the space-group symmetry P21/c and with a significant excess of the dClB depending on the crystallization conditions. Noteworthy, the isochoric crystallizations proceeded easily for the dClB:dBrB, dClB:methanol and dBrB:methanol mixtures, but the crystallization was much more difficult for the dClB:dBrB:methanol mixture (Fig. 1). The previously published structures of dClB30 and dBrB31 were used as starting models for refining high-pressure data. All atoms were assigned anisotropic thermal parameters, except H-atoms located at idealized positions and assigned Uiso equal to 1.2·Ueq of their carriers. The single crystals of solid solution d[ClxBr1-x]B were of much lower quality. In the refinements of the solid-solution structures, the x parameter was the average of site occupation factors defined separately for the independent molecules and refined as free variables. These refinements of solid solutions included constrained idealized benzene rings and isotropic thermal parameters of all atoms. The final crystal structures data and refinement parameters are listed in Table S1 and deposited in the CIF format in the Cambridge Structural Database as Supplementary publications CCDC 1485293-1485302, 1485310 (for solid solution d[Cl1.4Br0.6]B at 1.05 GPa), and 1500950 (for solid solution d[Cl1.2Br0.8]B solid solution at 0.5 GPa). Their copies can be obtained free of charge from www.ccdc.cam.ac.uk/cif.


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Fig. 1. Isochoric in situ crystallizations of (a) dClB from its mixture with methanol (vol. 1:1) at 533 K, 463 K and 296 K/0.45 GPa; (b) dBrB from its mixture with methanol (vol.1:2) at 503 K, 453 K and 296 K/0.41 GPa; (c) solid solution m-C6H4Cl1.2Br0.8 from the mixture dClB:dBrB (vol. 1:1) at 533 K, 443 K and 296 K/0.50 GPa; and (d) solid solution m-C6H4Cl1.4Br0.6 from the dClB:dBrB:methanol mixture (vol.1:1:6) at 493 K, 423 K and 296 K/1.05 GPa. Ruby chips and ruby powder for pressure calibration are scattered in the DAC chambers. Discussion High-pressure efficiently compresses the volume of molecular crystals and intermolecular interactions in their structures.32 In many molecular crystals the pressure of few GPa induces phase transitions11 and change preferences for co-crystallization and solvate formation.33


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However, the crystals of dClB and dBrB recrystallized up to 2.6 and 2.8 GPa are compressed monotonically and no sign of phase transitions have been detected neither in the volume compression nor in the unit-cell dimensions (Fig. 2). At 0.1 MPa the molecular volume of dClB is by about 10% smaller than that of dBrB, but on approaching 3 GPa they become nearly equal (Fig. 2). Of the mixed neat dClB and dBrB the solid solution d[Cl1.2Br0.8]B precipitated at about 0.3 GPa. However, from the dCl:dBrB:methanol mixture (1:1:6 vol.) only the dClB crystals were obtained up to 1.02 GPa. At this pressure, the solid solution of formula C6H4(Cl1.4Br0.6) was obtained. The space-group symmetry P21/c of these mixed crystals corresponds to that of dClB, and their unit-cell dimensions are intermediate between those of dClB and dBrB (Figs. 3 and 4). Then in the repeated recrystallizations at still higher pressure and changed temperature also other solid solutions of different ratio of dClB and dBrB, but always with a significant excess of dClB, were obtained.


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Fig. 2. Pressure dependence of the molecular volume calculated as V/Z of dClB (green full circles), dBrB (brown full circles) and their solid solution (black crosses). The ambient-pressure (0.1 MPa) volumes of dClB and dBrB were measured at 260 K and 220 K, respectively (open circles). The dotted lines are drawn for guiding the eye only. The solution ratio (x) depends on the crystallization conditions of temperature and pressure, as well as also on other parameters, like the composition of the solution used for crystallizations and speed of the crystal growth. These relations have not been investigated in detail because of the difficult crystallization of the solid solutions d[ClxBr1-x]B. It was essential to obtain good quality single crystals for refining the ratio parameter x, however the single crystals obtained in about 15 experiments were of poor quality and only for four of them reliable structural models could be refined. Basing on this information it has been established that there is no simple relation between the compression of parameter x and pressure. The crystallization of the dClB:dBrB mixture resulted in the solid solution with the smallest x parameter (Fig. 3), however the magnitude of x (i.e. the contents of dClB) increased when methanol was added to the dClB:dBrB mixture. The solid solutions crystallized of the dClB:dBrB:methanol mixture at 1.05 GPa and 1.37 GPa had a similar x parameter, but it was larger in the solid solution obtained at 1.2 GPa.


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Fig. 3. Factors xA and xB at independent sites A and B, respectively, occupied by molecules dClB (green) and dBrB (brown) in the solid-solution crystals. The lines are drawn for guiding the eye only, as the magnitude of pressure of the points indicate the precipitation of the crystals from the mixtures depend on the contents of methanol (1:1 dClB:dBrB at 0.5 GPa and 1:1:6 dClB:dBrB:CH3OH above 1 GPa) and temperature (533 K for 0.5 GPa, 493 K at 1.0 GPa, 503 K at 1.2 GPa and 523 K at 1.37 GPa).

In the series of dichlorobenzene and dibromobenzene ortho, meta and para isomers, the lower melting and boiling points of dClB than those of dBrB are consistent with the molecular weight of these compounds. The considerable increase of the melting points of the para analogues is also consistent with their higher molecular symmetry, in accordance to Carnelley’s rule.34-36 However, the isothermally crystallized dClB meta isomer precipitates easier, at 0.17 GPa, compared to 0.30 GPa freezing pressure for the dBrB meta isomer at 296 K. Similarly, easier isothermal crystallization of 1,2-dichlorobenzene than 1,2-dbromobenzene has been observed for the ortho analogues, at 0.18 and 0.20 GPa respectively. The puzzling easier isothermal crystallization of lighter dClB than of heavier dBrB molecules, despite that the Br···Br halogen


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bonds are usually stronger than Cl···Cl bonds, can be correlated with the angles associated with halogen···halogen bonds in these crystals. The Cl···Cl bonds in dClB nearly ideally correspond to type I (C9-Cl4···Cl4’-C9’) and to type II (C3-Cl3···Cl2’-C7’), whereas in dBrB in the type I bond C3-Be2···Br4’-C9’ one of the angles is significantly less than 80º, in bond C1-Br1···Br4’C9’ one of the angels is characteristic of type I and the other of type II bonds (144º and 88º, respectively), and angles 158º and 127º in bond C7-Br3···Br3’-C7’ do not match any of the halogen-bond types (Fig.4). It can be concluded that the nearly ideal type I and type II halogen bonds in dClB are further stabilized by high pressure, whereas the mismatched contacts C1Br1···Br4’-C9’ and C7-Br3···Br3’-C7’ in dBrB are destabilized at high-pressure conditions. It is also characteristic for the solid solution crystals, that the independent site B has the occupation by dBrB molecules systematically by about 0.13 higher than for site A. This means that the site B of molecules involved in two halogen bonds in the structure of dClB is more favored by the dBrB molecules than site A.

Fig. 4. The C-X···X angles in dClB and dBrB as a function of pressure. The primes at atomic labels indicate the intermolecular interactions.


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In all the pressure range investigated the intermolecular contacts are monotonically compressed (Fig. 5, Tables S5 and S6 of Supporting Information), consistently with no phase transitions detected.

Fig. 5. Halogen···halogen and H···halogen contacts in dClB (green) and dBrB (brown) as a function of pressure. Also, the shortest contacts Cl···Cl and Br···Br in the solid solution d(Cl,Br)B at 0.50 GPa have been indicated by two green crosses (one cross corresponds to contact Cl2···Cl3’ lying nearly in the line drawn for contacts Cl2···Cl3’ in neat dClB, while the other cross corresponds to contact Cl4···Cl4’, the longest one in this plot) and two brown crosses (nearly exactly superimposed), respectively. The remarkable similarity of the dClB and dBrB structures includes the aggregation of molecules by halogen···halogen bonds, as shown in Fig. 6. It appears, when viewed down crystal axis [x], that the molecules are halogen···halogen bonded into tetramers nearly identical in dClB and dBrB. However, the positions of terminal molecules A are clearly different along the [x] direction. In dClB indeed a centrosymmetric tetramer is formed of two molecules A lying on the


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opposite sides of the central dimer formed by two molecules B (this central dimer of molecules B lies between molecules A along all directions, including [x]). In dBrB it is only an impression that analogous tetramers are formed, when the structure is viewed along [x]. In fact the central molecules (B) are Br3···Br3’ halogen bonded into 21-symmetric zigzag chains and molecules A are Br4···Br2’ halogen bonded to the molecules B in one sense along [x]. Thus in dBrB each pair of Br···Br bonded molecules A···B is involved in two tetramer-like intervals: A···B···B’···A’ (primes indicate symmetry code x+0.5, 0.5-y, 1-z); and A···B···B”···A” (double primes indicate symmetry code x-0.5, 0.5-y, 1-z). Three such Br···Br bonded tetramer-intervals connected by Br···Br bonds into a zigzag chain are shown in Fig. S1b and the corresponding three Cl···Cl bonded separate tetramers are shown in Fig. S1a (Supporting Information). In dClB each Cl atom is involved in one halogen bond Cl···Cl, except atom Cl1 which forms CH···Cl contacts only. In dBrB atom Br3 is involved in two halogen bonds Br3’···Br3···Br3’’ along the zigzag chain; atoms Br2···Br4 are involved each in one halogen bond, between molecules A and B, while atom Br1 does not form halogen···halogen contacts. Thus three Cl···Cl bonds bind molecules into a tetramer in dClB, whereas in dBrB there are four Br···Br bonds per each corresponding tetramer interval. Another prominent type of cohesion forces in these structures are CH···X hydrogen bonds. In dClB at 0.1 MPa there is one CH···Cl bond shorter than 2.95 Å (the sum of van der Waals radii of atoms H and Cl according to Bondi37). In both dClB and dBrB there are three CH···halogen bonds per two independent molecules (Fig. 6 and Fig S2). Both these networks of halogen···halogen and CH···halogen bonds in dClB and dBrB persist in all the pressure range investigated. These intermolecular contacts are compressed monotonically, as shown in Fig. 5, and the C-X···X and C-H···X angles hardly change with pressure (Fig. 4). It is characteristic that


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at 0.1 MPa the shortest of Cl···Cl bonds is shorter than the corresponding Br···Br bond by over 0.2 Å, consistently with the lower b.p. and m.p. of dClB compared to dBrB. This preference for shorter Cl···Cl bonds persists to 1.5 GPa at least. The shortest (of three independent) CH···Cl bonds is marginally shorter compared to the CH···Br bonds (when the difference of 0.1 Å between the van der Waals radii of Cl and Br is taken into account). However, pressure strongly decreases the difference in length of CH···Cl and CH···Br bonds (Fig. 5).


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Fig. 6. The shortest halogen···halogen contacts in dClB and dBrB. The halogen···halogen bonded aggregates: (a) one tetramer in dClB; and (b) one chain of tetramers in dBrB, marked by coloring the rings. Letters ‘I’ and ‘Z’ denote the ‘interval’ and ‘zigzag’ patterns of halogen···halogen bonds, respectively. Conclusion It is plausible that the differences between partly similar dClB and dBrB structures mainly originate from the capacity of Br atoms to be involved in two halogen bonds Br···Br, which result in the zigzag chains, and from the binding of dClB molecules by halogen bonds consistent with the halogen···halogen bonds geometry of types I and II. The different geometries of halogen···halogen bonds are preserved in the compressed crystals, however in the solid-solution crystals obtained at high pressure the dClB structure prevails, most likely due to its halogen···halogen contacts more consistent with types I and II geometries corresponding the optimized polarization and electrostatic interactions, respectively. It appears that two independent molecules present in both dClB and dBrB are required for achieving the close packing arrangements. Consequently, the high-pressure conditions do not destabilize these crystals. However, there are also structures where pressure reduces the number of independent molecules. Such different effects of pressure can be the indication of different reasons leading to the presence of multiple independent molecules. It was found that high-pressure crystallization of the dClB:dBrB mixture promotes the formation of the solid solution with the excess of dClB, and that the solid solution formation from the dClB:dBrB:methanol mixture requires the considerably higher pressure and reduces the dBrB contents.


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ACKNOWLEDGMENTS We are grateful to the Wielkopolskie Centrum Zaawansowanych Technologii, Poznań, for the experimental support. WC’s present address is Department of Physics and Astronomy, University of Utah, 115S 1400E, Salt Lake City, Utah 84112, USA. References (1) Awwadi, F. F.; Willett, R. D.; Peterson, K. A.; Twamley B. The Nature of Halogen···Halogen Synthons: Crystallographic and Theoretical Studies. Chem. – Eur. J. 2006, 12, 8952-8960. (2) Riley, K.; Ford, C. L.; Demouchet, K. Comparison of hydrogen bonds, halogen bonds, CH···ᴨ interactions, and C-X···ᴨ interactions using high-level ab initio methods. Chem. Phys. Lett. 2015, 621, 165-170. (3) Podsiadło, M.; Olejniczak, A.; Katrusiak, A. Halogen···halogen contra C-H···halogen interactions. CrystEngComm 2014, 16, 8279-8285. (4) Bernstein, J.; Dunitz, J. D.; Gavezzotti, A. Polymorphic Perversity: Crystal Structures with Many Symmetry-Independent Molecules in the Unit Cell. Cryst. Growth Des. 2008, 8, 2011-2018. (5) Roszak, K.; Katrusiak, A.; Katrusiak, A. High-Pressure Preference for the Low Z' Polymorph of a Molecular Crystal. Cryst. Growth Des. 2016 16 3947-3953. (6) Marciniak, J.; Bąkowicz, J.; Dobrowolski, M.A.; Dziubek, K.F.; Kaźmierczak, M.; Paliwoda, D.; Rajewski, K. W.; Sobczak, S.; Stachowicz, M.; Katrusiak, A. Most Frequent Organic Interactions Compressed in Toluene. Cryst. Growth Des. 2016, 16, 1435-1441.


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(7) Patyk, E.; Podsiadło, M.; Katrusiak, A. CH···N bonds and dynamics in isostructural pyrimidine polymorphs. Cryst. Growth Des. 2015, 15, 4049-4044. (8) Dziubek, K.F.; Podsiadło, M.; Katrusiak, A. Nearly Isostructural Polymorphs of Ethynylbenzene:

Resolution

of

≡CH···π(arene)

and

Cooperative

≡CH···π(C≡C)

Interactions by Pressure Freezing J. Am. Chem. Soc. 2007, 129, 12620-12621. (9) Patyk, P.; Podsiadło, M.; Katrusiak, A. Discrete CH···N Bonded Patterns Modified by Temperature and Pressure in Four Pyrazine Polymorphs Cryst. Growth Des. 2015, 15, 5670-5674. (10) Seryotkin, Y. V.; Drebushchak, T. N.;Boldyreva, E. V. A high-pressure polymorph of chlorpropamide formed on hydrostatic compression of the α-form in saturated ethanol solution. Acta Crystallogr., Sect. B: Struct. Sci., Cryst. Eng. Mater. 2013, 69, 77-85. (11) Olejniczak, A.; Ostrowska, K.; Katrusiak, A. H-Bond Breaking in High-Pressure Urea. J. Phys. Chem. C 2009, 113,15761-15767. (12) Wardell, S. M. S. V.; de Lima Ferreira, M.; de Souza, M. V. N.; Wardell, J. L.; Lowc, J. N.;

Glidewelld,

C.

2,4-Difluorobenzaldehyde

benzoylhydrazone

and

2,4-

dichlorobenzaldehyde benzoylhydrazone are isostructural at 120 K with Z’ = 2: complex sheets built from N-H···O, C-H···O and C-H···ᴨ(arene) hydrogen bonds. Acta Cryst., 2006, C62, 118-121. (13) Pfrunder, M. C.; Micallef, A. S.; Rintoul, L.; Arnold, D. P.; Davy, K. J. P.; McMurtrie, J. Isostructural Co-crystals Derived from Molecules with Different Supramolecular Topologies. Cryst. Growth Des., 2014, 14 (11), 6041-6047.


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(21) Wang, Q.; Yan, T.; Wang, K.; Zhu, H.; Cui, Q.; Zou, B. Pressure-induced reversible phase transition in thiourea dioxide crystal. J. Chem. Phys. 2015, 142, 244701. (22) Granero-García, R., Lahoz, F. J., Paulmann, C., Saoaune, S. and Fabbiani, F. P. A. A novel hydrate of alpha-cyclodextrin crystallised under high-pressure conditions. CrystEngComm 2012, 14, 8664-8670. (23) Fisch, M.; Lanza, A.; Boldyreva, E.; Macchi, P.; Casati, N. Kinetic Control of HighPressure Solid-State Phase Transitions: A Case Study on l-Serine. J.Phys.Chem. 2015, C119, 18611-18617. (24) Zhen, Y.; Tanaka, H.; Harano, K.; Okada, S.; Matsuo, Y.; Nakamura, E. Organic Solid Solution Composed of Two Structurally Similar Porphyrins for Organic Solar Cells. J. Am. Chem. Soc., 2015, 137, 2247–2252. (25) Bhatt, P. M.; Desiraju G. R. Tautomeric polymorphism in omeprazole. Chem. Commun., 2007, 2057-2059. (26) Radu, N. S.; Hollander, F. J.; Tilley, T. D.; Rheingold, A. L.; Samarium-mediated redistribution of silanes and formation of trinuclear samarium–silicon clusters. Chem. Commun., 1996, 2459-2460. (27) Merrill, L.; Bassett, W. A. Miniature diamond-anvil cell for X-ray diffraction studies. Rev. Sci. Instrum. 1974, 45, 290. (28) Piermarini, G. J.; Block, S.; Barnett, J. D.; Forman, R. A. Calibration of pressuredependence of the R1 ruby fluorescence line to 195 kbar. J. Appl. Phys. 1975, 46, 27742780.


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Supporting Information. Crystal data and structure-refinements details for high-pressure measurements of dClB, dBrB and their solid solution ( Tables S1, S2, S3 and S4), the shortest intermolecular interactions in dClB and dBrB (Tables S5 and S6), the shortest halogen···halogen contacts in dClB and dBrB ( Figs. S1 and S2). This material is available free of charge via the Internet at http://pubs.acs.org. Corresponding Author *E-mail: [email protected]


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For Table of Contents Use Only

High-pressure crystallizations of meta dichlorobenzene and dibromobenzene and their solid solutions Michalina Anioła, Karolina Kwaśna, Weizhao Cai and Andrzej Katrusiak*

Very similar crystals of monoclinic m-dichlorobenzene and orthorhombic m-dibromobenzene, both with Z’=2, compress monotonically to about 3 GPa. When mixed, a monoclinic solid solution is formed at 0.5 GPa.


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High-Pressure Crystallizations of meta-Dichlorobenzene and

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