Colossal Positive and Negative Axial Thermal Expansion Induced by

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Colossal Positive and Negative Axial Thermal Expansion Induced by Scissor-like Motion of 2D Hydrogen Bonded Network in an Organic Salt Bhavna Dwivedi, Ashutosh Shrivastava, Lalita Negi, and Dinabandhu Das Cryst. Growth Des., Just Accepted Manuscript • Publication Date (Web): 25 Mar 2019 Downloaded from http://pubs.acs.org on March 25, 2019

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Crystal Growth & Design

Colossal Positive and Negative Axial Thermal Expansion Induced by Scissor-like Motion of 2D Hydrogen Bonded Network in an Organic Salt

Bhavna Dwivedi, Ashutosh Shrivastava, Lalita Negi and Dinabandhu Das* School of Physical Sciences, Jawaharlal Nehru University, New Delhi-110067, India [email protected] KYWORDS: Negative thermal expansion, Organic salt, Scissor motion, Hydrogen bonded network, Variable temperature single crystal X-ray Diffraction

Abstract: Variable Temperature Single Crystal X-ray Diffraction study revealed unusual thermal expansion property of an organic salt, imidazolium 4-hydroxy benzene carboxylate which exhibits colossal negative and positive axial thermal expansion along the crystallographic b axis and approximately along a axis respectively. Hydrogen bonded 2D square grid type of flexible network in the crystal structure of the salt resembles with fencing structure which undergoes scissor-like motion resulting the abnormal thermal behavior. Thermal expansion induced by scissor motion of hydrogen bonded network in multi-component crystalline organic compound has not been reported

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before, although this mechanism is mentioned to elucidate colossal thermal expansion in some inorganic framework materials.

Thermal expansion is an important contributing factor for structural safety and accuracy in many engineering field such as aerospace, civil, electronic engineering and precision instruments as well. Therefore, materials with controlled thermal expansion property is highly desired in varieties of technological applications.1,2 However, design of molecule with controlled thermal expansion is very much challenging because, positive thermal expansion (PTE) of materials is a normal phenomenon in which most of the materials expand upon heating owing to the increasing of anharmonic vibration of bonds. There are some materials which contract upon heating or vice versa – this phenomenon is commonly known as negative thermal expansion (NTE).1,3,4 Recent development in NTE material has attracted significant interest due its potential applications in various field such as thermo-mechanical actuator, cookware, sensors and other applications.1,3 In addition NTE materials have been used to achieve controlled thermal expansion property in composite materials by mixing of NTE with PTE materials in a certain stoichiometric ratio.5-7 Although NTE has been mostly observed in a number of oxide-based compounds,1,8,9 framework materials including some metal cyanides,10-25 3D and isotropic NTE has not been found in any organic material till date. Very few single-component organic materials are known for one or two dimensional NTE.26-31 The fundamental problem to design new molecules with NTE property is the understanding of underlying mechanism which varies from material to material. Among the several mechanisms known for NTE property, transverse vibration of atoms is the most common.1,10-13 Recently ‘elevator platform’ mechanism has been reported to explain area NTE in a mixed metal mixed organic MOF.20 ‘Colossal’ thermal expansion in some 3D framework


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materials have been explained by fencing mechanism which is induced by hinge-like motion due to framework flexibility.11,14,17-19 In addition, 1D NTE occurs in some porous framework materials induced by scissor motion due to intake and release of guest molecule.32,33 Indeed, NTE in organic material induced by scissor motion is very rare34 probably due to instability of the framework structure at elevated temperature. Multi-component crystals have grown significant interest in pharmaceutical industry because these materials provide advantages to improve physicochemical properties such as dissolution rate, bioavailability, thermal stability, hygroscopicity, particle size, flow, filterability, density and taste of active pharmaceutical ingredients (API).35-37 These materials, are being extensively used not only in pharmaceuticals but also in the preparation of functional materials to incorporate new functionality which cannot be achieved in single component material.38-41 In addition thermal expansion property of multi-component organic materials can be very interesting.28,42-52 Manipulation of thermal expansion property has been achieved by co-crystallization technique.45,48,49 Furthermore large thermal expansion has been observed in some co-crystals.28,50 Survey of literature revealed that among various multi-component organic materials, study of thermal expansion property is very rare in organic salt.43,46 In this study we report colossal PTE and NTE exhibited by an organic salt imidazolium 4hydroxybenzoate (IMD-HBC). The salt shows co-efficient of thermal expansion (CTE) of -115 MK-1 and +210 MK-1 along crystallographic b axis and approximately along a axis respectively within the temperature range of 100 K to 360 K. 2D hydrogen bonded flexible square grid type network in IMD-HBC salt motivated us to investigate thermal expansion property of the multicomponent organic compound. The unusual thermal expansion of IMD-HBC salt has been



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rationalized by scissor-like motion of hydrogen bonded network observed in the crystal structure of the organic salt. Co-crystal of IMD and HBC was first reported by Ren et al.53 Synthesis of IMD-HBC salt has been carried out by slightly modified procedure reported in the literature.54,

55

Grinding of

imidazole and 4-hydroxy benzoic acid together in 1:1 ratio upon addition of 2-3 drops of ethanol followed by crystallization in methanol produced colorless block shaped crystals within a week.

(a)

(b)

Figure 1. (a) Thermal ellipsoid plot of asymmetric unit in the crystal structure of IMD-HBC salt determined at 100K. Ellipsoids are shown in 70% probability. (b) Scissor-like arrangement of HBC and IMD ions connected through hydrogen bonding viewed down c axis. Hydrogen bonded nodes are compared with the hinge of the scissor. Hydrogen bonding are shown in red dotted lines.

The crystals were characterized by FT-IR, NMR, Powder X-ray diffraction (PXRD) and DSC (See the Supporting Information). Ultimately the structure was confirmed by Single Crystal X-ray Diffraction (SCXRD). The salt crystallizes in monoclinic lattice with the P21/n space group. The asymmetric unit of the crystal structure contains one of each of 4-hydroxy benzene carboxylate (HBC) and imidazolium (IMD) ion (Fig.1a). Packing of the ions in the crystal structure is mainly directed by multiple hydrogen bonding interactions where both the N-H groups of IMD ions and oxygen atoms of HBC ions participate in the formation of hydrogen bonding interaction. Every


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HBC ion is connected with two IMD ions via N–H···O hydrogen bond and also with another HBC ion through bifurcated O–H···O hydrogen bond. Two of each of neighboring HBC and IMD ions form a node through hydrogen bonding which is analogous to a scissor (Fig.1b). Extension of hydrogen bonding interaction between HBC and IMD ions generates 2D square grid type networks parallel to ab plane (Fig. 2a). 3D packing of HBC and IMD ions are completed by stacking of 2D networks along c axis. While 2D networks are stacked together along crystallographic c axis with a two-layer repeat unit which can be represented as ‘…ABABA...’. Adjacent layers are shifted from each other to avoid the steric hindrance between the ionic components and subsequently fill the voids generated in the hydrogen bonded networks (Fig. 2b, Fig. S5). Packing is further stabilized by π···π interactions between benzenoid and imidazole rings of adjacent network (Fig. S6).

(a)

(b)

Figure 2. (a) 2D Square grid type network formed by of HBC and IMD ions through O–H···O and N–H···O hydrogen bonding in the crystal structure viewed down the c axis. (b) Stacking of two adjacent hydrogen bonded 2D networks shown in blue and pink. Hydrogen bonding are shown in red dotted line.



Thermal expansion property of IMD-HBC salt has been studied by variable temperature single crystal X-ray diffraction (VT-SCXRD) by mounting a suitable single crystal on a glass fiber. Although DSC analysis of the salt shows the thermal stability up to around 430 K, SCXRD study shows the deformation of the single crystal above 360 K which is possiblly due to large thermal vibration. Hence, the temperature range for variable temperature diffraction study has been restricted from 100 K to 360 K. Diffraction data were measured at a regular interval of 20 K starting from 100 K to 360 K. Crystal structure of the salt at each temperature was solved and refined. The detail of the crystallographic information are given in Table S1 and S2 in the Supporting Information. Analysis of unit cell parameters reveals biaxial PTE and uniaxial NTE as both a and c axes increases and b axis decreases with increasing temperature (Fig. 3). Since the salt was crystallized in monoclinic system, the CTE were calculated using PASCal program56 which shows colossal NTE and PTE along principal axis X1 and X3 with the CTE of -115 MK-1 and +210 MK1

along the direction of [010] and approximately [100] respectively. While the third principal axis

X2 shows relatively small expansion with CTE of +18 MK-1 along approximate direction [102] resulting in overall volumetric expansion with CTE +110 MK-1. Expansivity indicatrix and principal component of expansivity tensor are shown in Fig. 4. Indeed, axial NTE observed in IMD-HBC salt over wide range of temperature is among the highest of multi-component organic crystals excluding solvates reported till date (See Table S10 in the Supporting Information). The reversibility of the phenomenon has been verified by determining crystal structure at regular interval of 40K by reducing temperature from 360K to 120K and then back to 100K. Analysis of the unit cell parameters indeed show contraction of both a and c axes upon cooling while the b axis increases with decreasing temperature (see crystallographic information for reversible study


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in Table S2 in the Supporting Information). This study clearly established the reversibility of unusual thermal expansion of IMD-HBC salt.

Figure 3. Change of the unit cell axes with temperature. Analysis of the crystal structures determined at different temperature and Finger print plot in Crystal Explorer57 shows no significant changes in O–H···O and N–H···O hydrogen bonding with increasing temperature (Fig. 5, Fig. S10, S11, Table S3 and S4 in the Supporting Information). The mechanism of colossal PTE and NTE of the IMD-HBC salt can be elucidated by systematic comparison of the crystal structures determined at each temperature in VT-SCXRD experiment.



Figure 4. Expansivity indicatrix along principal axes X1, X2 and X3. NTE shown in blue and PTE in red. The hydrogen bonded 2D square grid type of flexible network in the crystal structure of the salt viewed down the c axis has close resemblance with fencing network which has been shown schematically in Fig. 6a. In order to represent the 2D network similar to fence structure in simplified manner, the scheme is depicted by connecting each O(1) atoms of HBC ions related by translational symmetry, oriented in similar direction within a 2D network. The scheme can be seen as a planar square grid structure in which O(1) atoms along with other intersection points are acting as nodes (Fig. 6a). Analysis of the crystal structures revealed that diagonal distance x between these nodes along a axis increases and concertedly the distance y between the nodes along b axis decreases with increasing temperature (Fig. 6b and 6c). Concurrently angles between the nodes, θ and φ (Fig. 6b) are also adjusted by decreasing the angle θ while the angle φ increases with increasing temperature (Fig. 6d).


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(a)

(b)

Figure 5. (a) Change of O–O and O–N hydrogen bonding distances with temperature. (b) Change of angle O–H···O and O–H···N with temperature.

(a)

(b)

(c)

(d)



Figure 6. (a) 2D square grid network constructed from crystal structure viewed down the c-axis by connecting O(1) atoms of HBC ions oriented in same direction and also related by translation symmetry. (b) Schematic representation of scissor motion of 2D layer of square grid network. (c) Change of distances x and y with increasing tempeature as shown in Fig. 6b. (d) Change of angles θ and φ with increasing temperature as shown in Fig. 6b. x and y can be correlated with the unit cell axes a and b respectively.

The change of distances (x and y) and angle (θ and φ) occurs reversibly in similar manner when the temperature was decreased from 360 K to 100 K (See Table S7 and S8 in the Supporting Information). The reversible phenomenon has been shown schematically in Fig. 6b. Increasing of distance between nodes along a axis accompanied by decreasing of same along b axis with increasing temperature and vice versa justifies the PTE and NTE along [100] and [010] direction respectively. It is necessary to mention here that, as the temperature changes structural adjustment occurs without disturbing the periodic arrangement of the constituent ions of IMD and HBC. This is also possible due to flexibility of the hydrogen bonding interactions present in the crystal structure of IMD-HBC salt although no conformational change has been observed in the moiety of IMD and HBC over the wide range of temperature. Systematic comparison of the change of distances and angles between the nodes in 2D hydrogen bonded networks at different temperature can be viewed as a motion of the components of IMD-HBC salt over the whole range of temperature (from 100 K to 360 K and back to 100 K). This motion in IMD-HBC salt can be compared with scissor motion as shown in video S1 in the Supporting Information. Nevertheless, unusual thermal expansion induced by scissor motion has not been observed before in any multicomponent crystalline organic material. Relatively low thermal expansion along the principal


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axis X2 (CTE = +18 MK-1) can be explained by close packing of the adjacent 2D hydrogen bonded network. Voids created in the network are filled by the benzenoid and imidazole rings of the adjacent network as if these are locked with each other (See Fig. S5 and S6). Due to locking arrangement which is happened to be along the direction of the principal axis X2, the movement of the IMD and HBC ions are very much restricted resulting low thermal expansion. In summary, study of thermal expansion property of an organic salt by VT-SCXRD shows colossal axial PTE and NTE. The unusual thermal expansion in the organic salt originates from scissor-like motion of the 2D flexible hydrogen bonded network observed in the crystal structure. Present study will assist to design and synthesize new multi-component organic materials of which thermal expansion property can be manipulated by varying flexibility of the different component as well as the functional group present in those. Furthermore, multi-component organic materials with stable 3D network similar to hinged lattice fence will be very useful to study unusual thermal expansion property.

Supporting Information Available: Synthesis, VT-SCXRD, PXRD, Thermal ellipsoid plots, PXRD patterns, DSC plots, Finger print plots, Crystallographic information of CCDC number 1891039 – 1891059, Thermal expansion co-efficient. This material is available free of charge on the World Wide Web at http://pubs.acs.org.

AUTHOR INFORMATION Corresponding Author School of Physical Sciences, Jawaharlal Nehru University, New Delhi-110067, India. Tel: +912673-8813; E-mail: [email protected].



Funding Sources This work was supported by UPE-II at JNU sponsored by University Grant Commission (UGC), India and PURSE project sponsored by DST, India.

Notes Authors declear no conflict of interest

Acknowledgement BD is thankful to JNU for financial support, AS is grateful to SERB, DST, India for JRF, LN acknowledges UGC for JRF scholarship, DD thanks UPE-II and DST-PURSE for financial support. We are grateful to DST for providing Single Crystal XRD and DSC facilities in SPS, JNU.

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Colossal Positive and Negative Axial Thermal Expansion Induced by

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