High-Pressure Structure and Properties of N,N-Dimethylformamide

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High-Pressure Structure and Properties of N,N-Dimethylformamide (DMF) Paulina Ratajczyk, Szymon Sobczak, and Andrzej Katrusiak Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.8b01452 • Publication Date (Web): 10 Dec 2018 Downloaded from http://pubs.acs.org on December 11, 2018

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Crystal Growth & Design

High-Pressure Structure and Properties of N,N-Dimethylformamide (DMF) Paulina Ratajczyk,‡ Szymon Sobczak‡ and Andrzej Katrusiak* Faculty of Chemistry, Adam Mickiewicz University, Umultowska 89b, 61-614 Poznań, Poland.

ABSTRACT:

Intermolecular

interactions

and

aggregation

in

compressed

N,N-

dimethylformamide (DMF, C3H7NO, mp 212.7 K) have been determined in the solid state by single-crystal X-ray diffraction. The crystals of DMF were obtained at high-pressure isochoric conditions (the structure was determined up to 1.7 GPa) and at low-temperature isobaric conditions (the structure was determined down to 100 K). The exceptional stability of the DMF structure has been connected with its large number of degrees of freedom, due to low triclinic symmetry of the crystal and two symmetry-independent molecules. Consequently, the distortions of different CH···O bonds linking the molecules into one-dimensional aggregates, and their mutual displacements, efficiently compensate the structural strains generated by pressure.

1. INTRODUCTION N,N-dimethylformamide (DMF) is one of the simplest amides, widely applied as an aprotonic solvent,1 as well as a multipurpose reagent for various kinds of reactions.2 It favorably forms solvates with various substances and presently nearly 12000 structures, either DMF solvates of organic compounds or coordination complexes have been deposited in the Cambridge Structural

ACS Paragon Plus Environment

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Database.3 This considerable number of about 1% of all known organic crystals incorporating DMF illustrates the exceptional preference for aggregation as well as the wide applications of DMF in chemical practice. However, relatively little is known about the preferential aggregations of DMF molecules between themselves. In our study the intermolecular interactions in the crystalline DMF, either frozen below 212.7 K by isobaric cooling or above 0.78 GPa by isochoric compression, have been investigated. We have observed that all the isobaric, isochoric and isothermal nucleation lead to the triclinic crystal, of the same symmetry as that previously determined at 90 K/0.1 MPa.4 There are two symmetry-independent molecules (Z’=2), and we also intended to investigate the effect of pressure on Z’. In most crystals of organic compounds Z’=1 (currently about 81% of all structures deposited in the Crystallographic Structural Database)5–7 and several reasons of the occurrence of larger Z’ numbers are considered.8–17 High temperature usually leads to phase transitions reducing Z’,18–27 although reverse changes are also known.28–35 The effects of pressure on various properties of crystals are often inverse than those of temperature, hence the rule of inverse effects of pressure and temperature was formulated.36 However, there are many exempts from the inverse-effects. For examples a similar number of pressure-induced phase transitions increasing Z’37–43 and decreasing Z’ were known.9,28,44 Hence different pressure effects relevant to Z’ are considered. It can be assumed that high pressure increases the energy of intermolecular interactions, which increases the difference in the potential energy of independent molecules and eventually leads to a structural rearrangement to the equal optimum environment for each molecule. On the other hand, it is also possible that the interactions between molecules are incompatible with their close packing into a Z’=1 structure and that high pressure increases the interactions and further stabilize the compressed structure. Also, the differentiated molecules (in


2

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interactions, conformation and volume) may be packed more densely than identical ones. Such different interactions and subtle conformational changes are present in the DMF structure (Figure 1) and we have investigated the pressure effects on the DMF crystal built of relatively small weakly-interacting and conformationally-flexible molecules. The high-pressure behavior of DMF with those of has been compared with other aprotonic solvents, dimethyl sulfoxide (DMSO)27 and formamide (CHONH2).45

Figure 1. Four DMF molecules CH···O bonded into a cyclic tetramer. H-Bonds are represented as blue dashed lines. Atomic labels applied for discriminating independent molecules are shown for the symmetry-independent unit. 2. EXPERIMENTAL METHODS Single crystals of DMF, analytical grade of 99.9% purity, purchased from POCH and used as delivered, were grown in situ in a Merrill-Bassett diamond anvil cell (DAC) modified by mounting the anvils directly on steel backing plates with conical windows.46 Steel gaskets 0.2 mm thick with the hole 0.45 mm in diameter was used. The DAC chamber was filled with DMF and a single crystal was grown in situ isothermally, by gently increasing pressure to 0.78 GPa


3


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(Figure 2). The pressure was calibrated by the ruby-fluorescence method affording the accuracy of 0.03 GPa.47,48 Crystals at still higher pressures were grown at isochoric conditions. X-Ray diffraction data was measured at 0.78, 0.92, 1.24 and 1.7 GPa. A single-crystal 4-circle diffractometer equipped in a CCD detector and MoKα X-ray source (λ=0.71073 Å) was used. The data were collected with the CrysAlisPro software suite version 1.171.39.49 The crystal structure of DMF was solved by direct methods and refined with full-matrix least squares using SHELXS and SHELXL50 implemented in Olex2.51 All hydrogen atoms were located from molecular geometry and induced into the structural model with isotropic temperature factors related to the Ueq of their-carriers. Structural drawings were prepared with program Mercury CSD 3.8.52 The crystal data, summarized in Table 1 (cf. Table S1 in Supplementary Information), are consistent with the previously reported low-temperature triclinic DMF structure determined at 90 K for a single crystal on a four-circle diffractometer with the AgKα (λ= 0.56086 Å) source of radiation.4 Table 1. Selected crystallographic data of DMF. p/T (GPa/K)

0.78/296

1.7/296

0.0001/100

0.0001/192

Space group

P-1

P-1

P-1

P-1

a (Å)

5.943(6)

5.838(5)

5.9474(8)

6.0008(12)

b (Å)

6.966(4)

6.7183(17)

7.0212(8)

7.1672(11)

c (Å)

10.311(11)

10.1330(17)

10.4205(11)

10.4798(15)

α (°)

77.63(7)

77.520(17)

77.255(9)

77.387(12)

β (°)

88.73(9)

88.39(3)

88.179(10)

88.309(13)

γ (°)

75.01(7)

75.47(4)

75.311(11)

74.948(15)

V (Å3)

402.5(7)

375.5(4)

410.411

424.58

Z/Z’

4/2

4/2

4/2

4/2

Density (g/cm3)

1.206

1.293

1.183

1.144

Unit cell:


4

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We have also measured the compressibility of DMF in the piston-and-cylinder press up to 1.8 GPa.53 The initial volume of the DMF sample was 9.5 mL. The molecular volume (Vm) for the liquid was then calculated as one mole volume divided by the Avogadro number (NA). For the solid state Vm equal to the unit-cell volume (V) divided by Z was assumed. For low-temperature single crystal measurements a drop of DMF trapped in a glass capillary froze in the form of powder at about 212 K (Figure S1). Then, by oscillating temperature close to melting point and few degrees below its gradually a single crystal was grown. The first structural experiment was performed near the freezing point, at 192 K, and after that a series of 9 measurements from 190 to 100 K were collected. Selected crystal data of the low-temperature DMF are summarized in Tables 1 and S1. The X-ray diffraction data were processed as described above for the high-pressure experiments, but the H-atoms in the low-temperature structures were located from the difference Fourier maps and refined with the isotropic Uiso thermal parameter. 3. RESULTS AND DISCUSSION Both the isothermal freezing at 296 K/0.78 GPa and isobaric freezing at 0.1 MPa/212.7 K, as well as isochoric crystallizations, lead to the same DMF phase of triclinic space-group P-1 (Figure 3 and Figure S2) with two symmetry independent molecules (Z’ = 2). Non of our experiments produced the elusive metastable phase, previously obtained between 158 and 178 K on warming the amorphous sample.4 When its crystal structure was first determined at 0.1 MPa/90 K, it was concluded that the molecular arrangement in the solid and liquid phases does not depend strongly on cooperative hydrogen bonding. According to that study the formyl proton afforded only the very weak


5


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hydrogen bonds in the solid state, comparable in strength with the interactions between the methyl protons and oxygen atoms.4

Figure 3. The crystal structure of DMF at 0.78 GPa with CH···O bonds included. Cyclic tetramers have been marked by yellow and dimers by blue. Under increasing pressure liquid DMF is monotonically compressed to 0.78 GPa, when the molecular volume abruptly drops by about 35 Å3, marking the isothermal freezing (Figure 4). Such a substantial volume drop, by about -10%, can be associated with an efficient close packing of molecules in the crystal. As expected, the compression of the solid phase is smaller than of the liquid. In DMF the compressibility of the liquid is approximately four-fold stronger than of the crystal to 1.60 GPa, which can be an indication of small void space in the structure.


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Figure 4. Molecular volume (cf. Experimental Section) of DMF as a function of pressure, measured in a piston-and-cylinder chamber (blue circles) and as a single crystal in a diamond anvil cell (red circles). The dashed vertical line indicate the freezing pressure of 0.78 GPa. The estimated standard deviations (ESDs) are smaller than the symbols. The thermal expansion and compression of the DMF crystal are consistent with the inverse effects rule: the strongest expansion along [y] corresponds to the strongest compression in this direction; the compression and expansion of the crystal along [x] and [z] are similar (Figure 5 and cf. Figures S3 and S4). The inverse relationship rule valid to the volume and to the linear dimensions is consistent with the absence of strong directional interactions in the DMF crystal. A negative linear compression along [c] (Figure 5) may be due to a network of weak CH···O bonds (Figure 6), but also an effect of non-hydroscopic strain in the relatively soft sample crystal confined in the rigid DAC chamber.54


7


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It is apparent that the smallest (parallel to [001]) and largest (perpendicular to [001]) strain of compressed and expanding crystals cannot be directly connected with the CH···O aggregates extending along the [011] crystal direction (see Figure 3).

Figure 5. Thermal expansion (left) and compression (right) of DMF, in relation to the average unit-cell dimensions (ao, bo, co, Vmo) calculated of the room-temperature lowest-pressure (0.78 GPa) data with the graphical representations of thermal expansion and compressibility, shown in the insets.55 The ESDs are smaller than the symbols.


8

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Figure 6. Closest C···O and C···N distances plotted as a function of temperature (left) and pressure (right). For the low-temperature measurements, ESDs are smaller than the symbols. The systematic difference of about 2º in torsion angle O1-C1-N1-C2 and its corresponding angle in independent molecules suggest a considerable flexibility of the conformation (Figure 7). Highpressure data show a considerable spread of the torsion angle, suggesting a strong effect of pressure on the conformation, but at the highest investigated pressure the torsion angles are similar to those at the low-temperature structures. On the other hand, the conformational difference in the low temperature structures is induced by the crystal environment of independent molecules, and the energy of interactions with environment are increased in high-pressure. Thus the initial pressure-increased difference between τ1 and τ2 is consistent with this reasoning.


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Figure 7. Torsion angles O1=C1-N1-C2 (τ1), (blue) and O2=C4-N2-C5 (τ2), (red) in independent DMF molecules have been marked. For the low temperature data the ESDs are smaller than the symbols. 4. CONCLUSIONS The puzzling stability of the crystal structure of DMF has been connected with the dense packing of molecules both in the low-temperature and high-pressure conditions. The dense packing is consistent with the CH···O bonds, but it involves significantly different crystal environments of independent molecules, which affords systematic differences in their conformations. It appears that the increased number Z’, of independent molecules, is favorable for the dense packing in the DMF structure. It can be explained by the increased number of degrees of freedom for the structure with large Z’. Owing to the large number of degrees of freedom, the structure is capable of compensating strains generated in the compressed crystal. In a series of high-pressure studies on natural sugars, only the structure of α-D-mannose with two independent molecules displayed


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no phase transition.57 Additionally, the triclinic symmetry of the DMF crystal imposes no restrictions on the shape of the unit cell. The negative linear compressibility region along [z] immediately above freezing at Pc to about 0.9 GPa requires a further investigation, in order to eliminate the possible effects of non-hydrostatic strain.54

ASSOCIATED CONTENT Supporting Information. Photographs of DMF single crystal frozen in glass capillary; arrangement of DMF molecules in the unit cell; differently represented thermal expansion/compression of DMF; graphical representations of the thermal expansion and compressibility tensors along with numeric details from program Pascal; a survey of CSD deposits of torsion angle τ for solvated DMF molecules; short O···H contacts and detailed crystallographic data, including low- temperature and highpressure measurements. Accession Codes CCDC 1869635-1869638 contains the supplementary crystallographic high-pressure data for this paper and CCDC 1869744-1869752 contains supplementary crystallographic data for lowtemperature

measurements.

These

data

can

be

obtained

free

of

charge

via

ww.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12, Union Road. AUTHOR INFORMATION Corresponding Author


11


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* E-mail: [email protected]. Phone: +48 61 829 1590

Author Contributions The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. ‡These authors contributed equally. Funding Sources This study was supported by project OPUS 10 UMO-2015/19/B/ST5/00262 from the Polish National Science Center. ACKNOWLEDGMENT The authors would like to thank Mrs. Dominika Czerwonka and Aleksandra Półrolniczak for their support. REFERENCES (1)

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High-Pressure Structure and Properties of N,N-Dimethylformamide (DMF)

Paulina Ratajczyk, Szymon Sobczak and Andrzej Katrusiak

SYNOPSIS Strains generated by pressure and temperature changes in CH···O bonded aggregates of DMF are compensated by multiple degrees of freedom of asymmetric molecules in the triclinic crystal.


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High-Pressure Structure and Properties of N,N-Dimethylformamide

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