StructureâProperty Relations and Polymorphism in ... - ACS Publications

Subscriber access provided by UB + Fachbibliothek Chemie | (FU-Bibliothekssystem)

Article

Structure-property relations and polymorphism in compressed methylamines Marcin Podsiadlo, Anna Olejniczak, and Andrzej Katrusiak Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.7b00203 • Publication Date (Web): 14 Mar 2017 Downloaded from http://pubs.acs.org on March 19, 2017

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

Crystal Growth & Design is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 28

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Crystal Growth & Design

Structure-property relations and polymorphism in compressed methylamines Marcin Podsiadło,* Anna Olejniczak and Andrzej Katrusiak** Faculty of Chemistry, Adam Mickiewicz University, Umultowska 89b, 61-614 Poznań, Poland

ABSTRACT: The structures of a series of the simplest aliphatic amines determined at high pressure by single crystal X-ray diffraction reveal systematic structure property relations involving intermolecular interactions and molecular symmetries. Five new polymorphs have been found: one of methylamine (phase II, space group Fdd2), two of dimethylamine (phase I, space group C2/c and phase II, P21/c) and two of trimethylamine (phase II, space group P21/n and phase III, P21/m). The methylamine and dimethylamine molecules are arranged according to the NH···N hydrogen bonds. The phase diagrams of methylamines have been outlined up to 6 GPa.

ACS Paragon Plus Environment

1


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 2 of 28

INTRODUCTION Hydrogen bonds governing the molecular arrangements of crystals are well known and widely studied.1 They often contribute to physical and chemical properties of substances.2 The directional preferences of NH···N hydrogen bonds can be employed in crystal engineering or in understanding physical properties of molecular compounds. For example very weak coupling between the H+-site and ionic displacements in dabco NH+···N bonded complexes is connected with the ferroelectric and relaxor-like behaviour of these compounds.3 Due to the relatively weak energy of hydrogen bonds,4 they can transform at elevated pressure. The mechanism and origin of such transformations are invaluable in designing or predicting of crystal structures. Ammonia and methylamines can be described by the general formula CnH2n+3N, where n = 0,1,2,3, respectively. Their molecular mass is equal to (17+n·12) g/mol. In the series of ammonia and its methylated derivatives the physical properties of boiling and melting are regulated by the formation of NH···N bonds. The largest difference is observed in the freezing pressure: of about 1 GPa for NH3 and N(CH3)3, and 3.4 GPa for NH2CH3 at 295 K. In this paper the NH···N and CH···N hydrogen bond transformations have been compared in the group of the simplest aliphatic amines (methylamines): methylamine (MA), dimethylamine (DMA) and trimethylamine (TMA). They all, including analogous ammonia NH3, are gaseous at ambient conditions and represent an important class of compounds widely used in organic chemistry and in industry. For this group of analogous compounds we have investigated systematic changes of their properties related to the molecular arrangement and NH···N and CH···N hydrogen bonds. The structures of compounds NH3, MA and TMA were determined at ambient pressure and low temperature. Liquid MA freezes at 179.7 K and the crystal structure of its phase I has been determined at 123 K; the MA crystal is orthorhombic, of space group Pcab, with Z=8 and Z'=1.5 DMA at ambient pressure freezes at 181.0 K, however its structure was not reported. TMA has


2

Page 3 of 28

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


the lowest melting point, of 156.1 K, and its crystal structure at 143 K and 118 K was reported as trigonal phase I, of space group P 3 , with Z=2 and Z'=0.333.6,7 Presently we have found new crystal forms: MA phase II, DMA phases I and II, as well as TMA phases II and III, and we have determined their structures by single-crystal X-ray diffraction. We have measured the compression of these methylamines up to 6 GPa and charted the phase boundaries in their P/T phase diagrams in this pressure range (Figure 1).

Figure 1. Phase diagram P/T of methylamines: MA (red), DMA (green) and TMA (blue), with inset magnifying the gas-liquid region. The literature data5-8 incorporated in the diagram are explained in the Supporting Information. EXPERIMENTAL SECTION Methylamine (MA), ≥99.0% pure, dimethylamine (DMA), ≥99.8% pure, from Sigma-Aldrich and trimethylamine (TMA), 99.0% pure, from Linde Gaz Polska were compressed and loaded into a modified high-pressure Merrill-Bassett9 diamond-anvil cells (DACs) at cryogenic conditions and in situ crystallized. At 295 K MA, DMA and TMA froze at 3.40, 2.50 and


3


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 4 of 28

1.10 GPa, respectively, in the form of polycrystalline mass filling the whole volume of the highpressure chamber. Single-crystals were obtained at isochoric conditions (Figure 2): the DAC with the polycrystalline mass was heated with a hot-air gun till all but one grain melted. Then the DAC was slowly cooled to room temperature and the single crystal grew and eventually filled the entire volume of the chamber. MA, DMA and TMA showed exceptionally beautiful intense colours in the polarized light (Figure 2). The experimental details and progress in growing the single crystals are shown in Figures S1-S14 in the Supporting Information.

Figure 2. Single crystals of methylamines grown in situ in the diamond-anvil cell viewed with polarized-light: (a) MA phase II at 3.65 GPa/316 K, (b) at 4.90 GPa/369 K, (c) at 5.45 GPa/397 K; (d) DMA phase I at 2.90 GPa/337 K, (e) at 4.80 GPa/398 K, (f) DMA phase II at 5.60 GPa/438 K; (g) TMA phase II at 1.50 GPa/368 K, (h) at 2.40 GPa/449 K, and (i) TMA phase III at 3.35 GPa/508 K. Diffractometers KUMA KM4-CCD and Xcalibur EOS were used for high-pressure studies. The DAC was centred by the gasket-shadow method.10 The CrysAlisPro program suite was used


4

Page 5 of 28

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


for data collections, determination of the UB-matrices and initial data reduction.11 The intensity of reflections have been accounted for the absorption of X-rays by the DAC, shadowing of the beams by the gasket edges, and absorption of the sample crystal itself.12,13 The crystal structures of methylamines were solved by direct methods and the H-atoms were located from molecular geometry.14 The crystal data of methylamines are summarized in Table 1. Other crystal data and experimental details are listed in Tables S1-S3 in the Supporting Information. Program CrystalExplorer15 was used for calculating the electrostatic potential;16 it was mapped onto the molecular surfaces defined as 0.001 a.u. electron-density envelope.17 Table 1. Selected crystal data of methylamine (MA), dimethylamine (DMA) and trimethylamine (TMA). MA

MA

DMA

DMA

TMA

TMA

TMA

phase Ia

phase IIb

phase Ib

phase IIb

phase Ic

phase IIb

phase IIIb

P (GPa)

0.0001

3.65(2)

2.90(2)

4.90(2)

0.0001

1.50(2)

2.55(2)

T (K)

123(5)

295(2)

295(2)

295(2)

143

295(2)

295(2)

orthorhombic

orthorhombic

monoclinic

monoclinic

trigonal

monoclinic

monoclinic

Pcab

Fdd2

C2/c

P21/c

P3

P 2 1 /n

P 2 1 /m

a (Å)

5.75(3)

12.013(2)

14.870(6)

6.8781(5)

6.143(2)

5.7015(7)

5.4764(18)

b (Å)

6.17(7)

12.745(20)

3.947(3)

7.603(6)

6.143(2)

9.407(19)

8.979(4)

c (Å)

13.61(2)

4.6287(6)

10.128(5)

14.3993(10)

6.979(2)

7.5667(7)

3.8829(15)

β (°)

−

−

112.86(3)

91.104(6)

−

106.913(11)

109.40(3)

482.85

708.6(11)

547.7(5)

752.9(6)

228.08

388.3(8)

180.09(12)

8, 1

16, 1

8, 1

12, 3

2, 0.333

4, 1

2, 0.5

0.852

1.165

1.094

1.193

0.861

1.011

1.090

−

0.0221

0.0475

0.0484

−

0.0303

0.0472

0.1310

0.0242

0.0555

0.0718

0.0454

0.0388

0.0543

Crystal system Space group

Volume (Å3)

Z, Z' Dx (g cm-3) R1 (I > 2σ(I)) R1 (all data) a

Ref. 5;

b

This work;


5


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

c

Page 6 of 28

Ref. 7.

DISCUSSION The single crystal X-ray diffraction data of methylamines have been recorded from the lowest possible pressure point to ensure stability of the crystals during measurements (just above the freezing pressure) to the maximum pressure point allowed by the thermal limitations of DAC when growing the single crystals. MA phase II compresses monotonically at high pressure and its structure has been determined in four pressure points from 3.65 to 5.45 GPa. DMA exhibits polymorphism at high pressure: phase I determined from 2.90 GPa transforms at 4.85 GPa to phase II stable to at least 5.60 GPa. TMA phase II determined from 1.50 GPa transforms at 2.48 GPa to phase III stable to 3.35 GPa at least. The molecular volume of methylamines as a function of pressure has been plotted in Figure 3.

Figure 3. The molecular volume (V/Z) of methylamines plotted as a function of pressure. The dashed lines joining the points of different phases, temperature and pressure is for guiding the eye only.


6

Page 7 of 28

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


MA at 0.10 MPa/123 K crystallizes in centrosymmetric phase I of space group Pcab5 with the molecules arranged into NH···N bonded sheets involving two layers of molecules perpendicular to [001] (Figure 4a). These sheets are related by the inversion centres. Within the sheets each Natom is a double donor and double acceptor of H-atoms forming NH···N bonded rings described by symbol R43 (8) according to the graph notation of H-bonds.18 Within the ring two pairs of four methyl groups are oriented at the opposite directions. One N-atom is a double donor, one is a double acceptor of H-atoms and two remained N-atoms are a single donor and acceptor of Hatoms. At 3.40 GPa/295 K MA freezes into a non-centrosymmetric phase II of space group Fdd2. All molecules are oriented in one direction and form an NH···N bonded 3-D network (Figure 4b). Within this network molecules form R42 (8) rings perpendicular to [001] and helices C11 (2) . Within the ring two N-atom are a double donor and two are a double acceptor of H-atoms. DMA at 2.50 GPa/295 K crystallizes in monoclinic phase I of space group C2/c with Z'=1. Molecules are linked with C11 (2) NH···N bonded zig-zag chains (Figure 5a). At 4.85 GPa DMA transforms to phase II of space group P21/c with Z'=3. These three symmetry-independent molecules form NH···N bonded helices C11 (2) (Figure 5b).


7


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 8 of 28

Figure 4. Crystal structures of MA phase I (a) and MA phase II (b) with calculated electrostatic potential in the colour scale ranging from –0.064 a.u. (red) to 0.037 a.u. (blue) mapped onto the surfaces of molecules; the molecular packing of the NH···N bonded sheet in MA phase I (a) and the NH···N bonded 3-D network in MA phase II (b). The spiral arrows in phase II indicate the handiness of C11 (2) helices.


8

Page 9 of 28

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Figure 5. DMA unit-cell contents (top) viewed along NH···N bonded helices and (bottom) these helices viewed horizontally in: (a) phase I; and (b) phase II. TMA at 0.10 MPa/143 K7 and at 0.10 MPa/118 K6 crystallizes in phase I of trigonal space group P 3 . At 1.10 GPa/295 K TMA freezes into phase II of monoclinic space group P21/n and at 2.48 GPa it transforms to phase III of space group P21/m. Their structures are shown in Figure 6. It can be noted that at the absence of NH···N clearly the CH···N take over their role for the crystal cohesion forces. This can be observed from the CH···N contacts significantly shorter than those in all other methylamine analogues (Figure 7). It is also characteristic that the molecular arrangement is influenced by the shape of C3v symmetric molecules. Despite significantly different intermolecular forces between TMA and CHBr3, their crystals of ambient pressure phases are isostructural and their molecular symmetry is reflected in space group P 3 of their crystals. It is also characteristic that high pressure, enhancing the intermolecular interactions, favour different structures of TMA and CHBr3.19


9


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 10 of 28

Figure 6. The molecular arrangements of TMA phase I (a), phase II (b) and phase III (c).


10

Page 11 of 28

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Figure 7. Intermolecular H···N distances plotted as a function of pressure in methylamines. Two shortest distances are presented from two possible kind of interactions: circles represent N−H···N and squares C−H···N. Black horizontal line shows sum of van der Waals radii of H and N of 2.75 Å.20 The estimated standard deviations are either smaller than the plotted symbols (cf. Figure S16) or not applicable to the distances involving H-atoms. It is characteristic of methylamines MA and DMA, but also of ammonia, that each molecule is capable of forming two NH···N bonds; in one of the H-bonds the molecule participates as an Hdonor and in the other as the H-acceptor. This is due to the presence of only one H-acceptor site in all these molecules. In the series of ammonia, MA, DMA and TMA the number of H-donors is reduced from 3 in ammonia to 0 in TMA. It appears that these weak NH···N bonds have some effect on the melting point of the amines at 0.1 MPa: the highest for ammonia, approximately equal for MA and DMA, and the lowest for TMA (Figure 8). Their boiling point, gradually increasing from ammonia (240 K), MA (267 K) to DMA (280 K), apparently depends on the


11


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 12 of 28

molecular mass; the boiling point of TMA (276 K) is somewhat lower due to the absence of NH···N bonds between TMA molecules.

Figure 8. Isobaric (at 0.1 MPa) boiling (b.p.) and melting (m.p.) points, as well as critical temperature (c.T.) of ammonia (NH3), methylamine (MA), dimethylamine (DMA) and trimethylamine (TMA) as a function of their molecular mass. The series of amines display a remarkably different pressure magnitudes for isothermal freezing at 295 K plotted in Figure 9: ammonia and TMA freeze at the lowest pressure of about 1 GPa, DMA at 2.5 GPa and MA at the highest pressure of 3.4 GPa. Two of these molecules, ammonia and TMA are C3v symmetric, so Carnelley’s rule21 can be directly applied. Carnelley’s rule states that isomers of higher molecular symmetry melt at higher temperature, and in the more general form,22 that the compounds with similar intermolecular interactions of higher molecular symmetry usually melt at higher temperature and lower pressure, mainly because these molecules are capable of forming more intermolecular bonds than the less symmetric molecules. In the series of ammonia and methylamines several effects can result in the observed low m.p. of NH3


12

Page 13 of 28

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


and TMA, and high m.p. of MA. The increased mass and moment of inertia of MA compared to NH3 reduces the temperature-activated tumbling of the molecules, and the dynamical process of breaking NH···N bonds, which would increase the m.p. The tumbling of ammonia molecules, on the other hand, rearranges the NH···N bonds, but does not lead to the configurations where these H bonds cannot be formed. The freezing of ammonia and methylamines can be considered as a competition of NH···N bonding and close-packing interactions. In this respect, the tighter crystal packing favoured by high pressure can be inconsistent with the formation of NH···N bonds. Such a competition does not apply to ammonia, where the NH···N bonds are formed irrespective of the orientation of molecules, and to TMA where no NH···N bonds are possible.

Figure 9. Freezing pressure of ammonia, MA, DMA and TMA plotted as a function of the molecular mass. The insets show the stick-and-ball drawings of the molecules with their symmetry indicated, as well as the number of the compound phase which melts at 295 K. This reasoning is supported by the observed pressure effect on the NH···N bonds. Intermolecular H···N distances as a function of pressure in methylamines are plotted in Figure 7.


13


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 14 of 28

It is characteristic that H···N distances of the high-pressure MA phase II are longer than those in MA phase I at ambient pressure. This counterintuitive result can be explained by the Hbonds − packing competition and by much stronger compressed contacts CH···N. Likewise, the significant shortening of CH···N contacts is responsible for the compression of the DMA and MA crystals. The competition between different cohesion forces affects also other thermodynamic properties of these crystals, such as their freezing pressure.

CONCLUSIONS We have shown that the phase diagrams of the simples amines contain at least two solid phases (NH3, MA, DMA), and that TMA has three solid phases up to about 6 GPa. The intermolecular interactions of NH···N bonds and electrostatic forces in their crystal structures, as well as the mass and symmetry of molecules in conjunction with their packing in the crystal, play an important role for the formation of these polymorphic forms, phase transitions and also for the macroscopic properties of these compounds, including their melting and boiling temperature and pressure. In this series of polymorphic structures of simple methylamine derivatives only one noncentrosymmetric and polar phase II of MA has been found. Owing to the polar symmetry, the MA phase II is likely to display interesting dielectric properties, for example it can be ferroelectric. However further studies are required for determining the dielectric properties of these simple compounds. It can be also noted, that the hydrogen bonding and other types of intermolecular interactions are essential for understanding the molecular aggregation, motifs, conformation and properties of molecular crystals and the application of pressure is particularly useful for changing the balance of these different effects and for illustrating their role for the formation and transformations of crystals.23-28


14

Page 15 of 28

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


ASSOCIATED CONTENT

Supporting Information: detailed experiment and structures description. This material is available free of charge via the Internet at http://pubs.acs.org. AUTHOR INFORMATION

Corresponding Author *E-mail: [email protected] **E-mail: [email protected] ACKNOWLEDGMENT Financial support received from the Polish Ministry of Higher Education and Science (Project Iuventus Plus No. IP2014 037873) is gratefully acknowledged. REFERENCES (1)

Jeffrey, G. A.; Saenger, W. Hydrogen Bonding in Biological Structures. Springer-Verlag,

Berlin, 1991. (2)

Mascetta, J. A. Chemistry, the easy way, fourth edition, Barron's Educational Series Inc.,

New York, 2003. (3)

Katrusiak, A. Engineering of Crystalline Materials Properties, edited by J. J. Novoa; D.

Braga; L. Addadi, pp. 231-250. Dordrecht: Springer, 2008. (4)

Desiraju, G.; Steiner, T. The Weak Hydrogen Bond. International Union of

Crystallography: Monographs on Crystallography, 2001. (5)

Atoji, M.; Lipscomb, W. N. Acta Cryst. 1953, 6, 770-774.


15


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 16 of 28

(6)

Blake, A. J.; Ebsworth, E. A. V.; Welch, A. J. Acta Cryst. 1984, C40, 413-415.

(7)

Boese, R.; Blaser, D.; Antipin, M. Y.; Chaplinski, V.; de Meijere, A. Chem. Comm. 1998,

781-782. (8)

Lide, D. R. CRC Handbook of Chemistry and Physics, 90th ed., CRC Press Inc., Boca

Raton, FL, 2010. (9)

Bassett, W. A. High Press. Res. 2009, 29, 163-186.

(10)

Budzianowski, A.; Katrusiak, A. High-Pressure Crystallography, edited by A. Katrusiak;

P. F. McMillan, pp. 101-112. Dordrecht: Kluwer Academic Publishers, 2004. (11)

Oxford Diffraction Ltd., Xcalibur CCD system, CrysAlis Software system, Version

1.171, 2004. (12)

Katrusiak, A. REDSHABS – program for correcting reflections intensities for DAC

absorption, gasket shadowing and sample crystal absorption. Adam Mickiewicz University, Poznań, Poland, 2003. (13)

Katrusiak, A. Z. Kristallogr. 2004, 219, 461-467.

(14)

Sheldrick, G. M. Acta Cryst. 2008, A64, 112-122.

(15)

Grimwood, D. J.; Jayatilaka, D.; McKinnon, J. J.; Spackman, M. A.; Wolff, S. K.

CrystalExplorer, University of Western Australia, Crowley, ver. 2.1, 2008. (16)

Murray, J. N.; Sen, K. D. Molecular Electrostatic Potential: Concepts and Applications;

Elsevier: New York, 1996.


16

Page 17 of 28

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(17)

Bader, R. F. W.; Carroll, M. T.; Cheeseman, J. R.; Chang, C. J. Am. Chem. Soc. 1987,

109, 7968-7979. (18)

Etter, M. C.; MacDonald, J. C.; Bernstein, J. Acta Cryst. 1990, B46, 256-262.

(19)

Dziubek, K. F.; Katrusiak, A. J. Phys. Chem. B. 2008, 112, 12001-12009.

(20)

Bondi, A. J. Phys. Chem. 1964, 68, 441-451.

(21)

Carnelley, T. Philos. Mag. 5th series, 1882, 13, 112-130 and 180-193.

(22)

Podsiadło, M.; Bujak, M.; Katrusiak, A. CrystEngComm. 2012, 14, 4496-4500.

(23)

Kapustin, E. A.; Minkov, V. S.; Boldyreva, E. V. Acta Cryst. 2014, B70, 517-532.

(24)

Kapustin, E. A.; Minkov, V. S.; Stare, J.; Boldyreva, E. V. Cryst. Growth Des. 2014, 14,

1851-1864. (25)

Kapustin, E. A.; Minkov, V. S.; Boldyreva, E. V. Phys.Chem.Chem.Phys. 2015, 17,

3534-3543. (26)

Rajewski, K. W.; Andrzejewski, M.; Katrusiak, A. Cryst. Growth Des. 2016, 16, 3869-

3874. (27)

Sobczak, S.; Katrusiak, A. J. Phys. Chem. C. 2017, 121, 2539-2545.

(28)

Yan, T.; Wang, K.; Tan, X.; Yang, K.; Liu, B.; Zou, B. J. Phys. Chem. C. 2014, 118,

15162-15168.


17


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 18 of 28

For Table of Contents Use Only Structure-property relations and polymorphism in compressed methylamines Marcin Podsiadło,* Anna Olejniczak and Andrzej Katrusiak**

Single crystals of the simplest aliphatic amines, gaseous at normal conditions, have been grown at high pressure and the structures of five new polymorphs have been determined.


18

Page 19 of 28

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


83x81mm (300 x 300 DPI)



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

85x85mm (300 x 300 DPI)


Page 20 of 28

Page 21 of 28

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


82x79mm (300 x 300 DPI)



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

152x145mm (300 x 300 DPI)


Page 22 of 28

Page 23 of 28

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


76x36mm (300 x 300 DPI)



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

189x224mm (300 x 300 DPI)


Page 24 of 28

Page 25 of 28

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


83x81mm (300 x 300 DPI)



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

83x82mm (300 x 300 DPI)


Page 26 of 28

Page 27 of 28

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


84x83mm (300 x 300 DPI)



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

44x23mm (300 x 300 DPI)


Page 28 of 28

StructureâProperty Relations and Polymorphism in ... - ACS Publications

Recommend Documents

StructureâProperty Relations and Polymorphism in ... - ACS Publications