Interaction Dependence and Similarity in Thermal Expansion of a

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Interaction Dependence and Similarity in Thermal Expansion of a Dimorphic 1D Hydrogen-Bonded Organic Complex Binoy Krishna Saha, and Suman Bhattacharya Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/cg4009174 • Publication Date (Web): 26 Jul 2013 Downloaded from http://pubs.acs.org on July 28, 2013

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Crystal Growth & Design

Interaction Dependence and Similarity in Thermal Expansion of a Dimorphic 1D Hydrogen-Bonded Organic Complex Suman Bhattacharya, and Binoy K. Saha* Department of Chemistry, Pondicherry University, Pondicherry, India. 605014

Keywords: Thermal expansion, Hydrogen bond, Polymorphs, Cocrystals. Abstract

The thermal expansion trends for the two 1D hydrogen bonded 1:2 cocrystal polymorphs of 1,2,3,4-cyclobutanetetracarboxylic acid and 4,4′−bipyridylethylene have been studied. The expansion modes were found to be highly anisotropic but similar in these two forms. The mode of expansions along different directions is found to depend on the nature of the interactions and contacts that are present along those directions.

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An increase in temperature of a material is expected to bring about an expansion in the material. However the nature of expansion could be highly anisotropic or even contract upon increasing temperature in one or more directions, causing negative thermal expansion (NTE) along those directions.1 Materials exhibiting volumetric NTE are known for their potential applications especially in the designing of materials which would exhibit a zero thermal expansion (ZTE) on heating.2 On the other hand, the materials with very high uniaxial PTE might be useful in the designing of thermomechanical actuators.3 The reasons for this anomalous expnasion are numerous as well as quite complex and various theories have come up over the years to explain many of such phenomena.4 One of the many such reasons for anisotropic thermal expansion is believed to be the different types of interactions that are present in the materials. Stronger interactions in general are found to be less affected by the temperature change whereas weaker interactions cause larger thermal expansion with increasing temperature.5 Various materials have been reported to exhibit such anomalous expansion behaviour. In this regard, however, the organic molecules6,3a,5b,c have drawn less attention compared to the inorganic and metal─organic componuds7,1b,3b. Given the fact, more and more organic based molecules are being employed for material designing,8 various types of organic solids could be employed for their thermal expansion behaviour to understand the property and then design new materials. Polymorphs9 are known to be a very good choice for the study of structure ─ property relationship, because many parameters remain unchanged and hence there are only few parameters to deal with in the comparative study. Even though, owing to their different solid state packing, polymorphs are known to exhibit distinguishable solid-state behaviour in melting point, solubility, reactivity, etc.,10 differences in thermal expansion


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behaviour are not that well studied11. Herein we report the thermal expansion behaviours of two polymorphs of an organic cocrystal with similar hydrogen bonding topologies. 1:2 molar stoichiometric mixture of 1,2,3,4-cyclobutanetetracarboxylic acid (CBTA) and 4,4′−bipyridylethylene (BPE) exists in two distinct solid-state forms. The [2 + 2] photodimerization studies on these two polymorphs have been previously reported by us.12 Owing to the topological similarity in hydrogen bond, the two forms mainly differ in weak interactions and this feature prompted us to study the influence of these weak interactions on their comparative thermal expansion behaviours. Crystallization of 1:2 molar stoichiometric mixture of CBTA and BPE from a 1:1 mixture of methanol and DMSO produced plate shaped crystals of Form I. The Form I was solved in P21/c space group with half molecule of CBTA and one molecule of BPE in the asymmetric unit making it a 1:2 cocrystal of the formers. The topology is primarily hydrogen bonded parallel chains where the BPE molecules are bound to the CBTA moiety via the robust acid−pyridine heterosynthon (Figure 1a). A crystallization attempt of 1:2 mixture of the formers from 1:1 DMSO-ethanol solvent mixture yielded the second polymorph, Form II, which was solved in 1 space group with two half molecules of the acid and two molecules of BPE in the asymmetric unit. The ethylene group in one of these two BPE molecules is disordered over two orientations. This architecture is also comprised of similar one dimensional parallel chains of CBTA molecules linked via BPE moieties through hydrogen bonds (Figure 1b). But the relative 3D arrangement of these parallel chains is different from the Form I structure. As a result the weak interactions holding the parallel chains in the crystal packing are different in these two polymorphic solids. A diffraction quality single crystal of Form I (Figure S1a) was chosen and variable temperature single crystal X-ray diffraction data collection was performed within the range of


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298 – 120 K by gradual cooling of the crystal at a 36 K interval with the help of a cryojet. Calculation using PASCal program13 reveals that within this temperature range the system undergoes a volumetric contraction with the thermal expansion coefficient value of 183(14) × 106

K-1, whereas along the three principal axes, X1 (203), X2 (010) and X3 (100), the coefficients

of thermal expansion are 4(5), 25(4) and 147(8) × 10-6 K-1 respectively (Figure 2 and S3). On the other hand, the Form II exhibits thermal expansion close to ZTE along the X1 (122) principal axis with a coefficient of −4(5) × 10-6 K-1, whereas along X2 (252) and X3 (721) the coefficients of expansion are respectively 18(5) and 136(5) × 10-6 K-1 (Figure 2 and S3). The overall volumetric expansion coefficient (158(15) × 10-6 K-1) is found to be only slightly smaller than the other form. In both the systems, the expansion along X1 and X2 directions are very small and only marginally different but along X3 it is quite high. Therefore these polymorphs exhibit a very similar thermal expansion trend. As a result, the Aspherism index14 of these two forms are very similar, 0.5203 and 0.5887 respectively. It should be noted here that for the isotropic system the Aspherism index is 0, whereas for a system with biaxial ZTE and uniaxial PTE or NTE this values is 0.67.14 The present result is in contrary to the reported systems where the polymorphs show quite distinguishable thermal expansion properties.11 It should also be noted that below room temperature the density of the monoclinic structure is higher than the triclinic structure (Table S1). To understand the origin of similarity in thermal expansion of the two forms, we have analysed the crystal structures in terms of packing and interactions that are present in these two solids. An analysis of the monoclinic structure (Form I) shows that each chain is surrounded by six other parallel chains which could be classified into two types based on their distances (Figure 3a). During the course of thermal treatment, a relative realignment of the chains takes place with


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respect to each other, resulting in an anisotropic expansion in the material. D1′ and D2′ depict the distances between the central chain and the surrounding chains as shown in Figure 3a. Along D1′ and D2′, the coefficients of thermal expansion of the distances between the chains are about 145(10) × 10-6 K-1 and 59(5) × 10-6 K-1 respectively (Figure 3c). On the other hand, along the hydrogen bonded chain direction, the structure experiences a very small change due to the lowering in temperature with an expansion coefficient of only 5(6) × 10-6 K-1 (Figure 3c). Similar to the monoclinic structure, each hydrogen bonded chain in Form II is surrounded by six other chains, but there are three different distances between the central chain and the surrounding chains instead of two (Figure 3b). Along D1′′, D2′′ and D3′′ the thermal expansion coefficients are 115(9), 15(4) and 114(7) × 10-6 K-1 respectively (Figure 3c). Similar to the Form I, the expansion is negligible (−2(7) × 10-6 K-1) along the hydrogen bonded chain direction. After a scrutiny of the structures, a plausible cause for this anisotropic expansion could be accounted in terms of the types of interactions that are present between the neighbouring chains (Table S3 and S4). Along D1′ (Form I) and D1′′ (Form II) the contacts are weak van derv Waals type and the contact distances are around the van der Waals sum of the contact atoms (Table S3 and S4). The interactions present along D3′′ in Form II are also weak (π...π type) in nature. Thus along these directions there is a substantial contraction as the temperature decreases from 298 to 120 K. As a result, in Form I the major principal axis (X3) is aligned close to the D1′ direction and in Form II it is aligned approximately in between D1′′ and D3′′ directions (Figure 3a & b). On the contrary, along D2′ (Form I) and D2′′ (Form II) the contacts are made of comparatively stronger C−H···O type of interactions (Figure S4a & b) and that results into relatively smaller contraction along these directions compared to the D1′, D1′′ and D3′′ directions in the structures. The medium principal axis (X2) is passing through these two D2′ directions in Form I but close to the


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D2′′ direction in Form II (Figure 3a & b). The strongest interaction in these two crystal structures is present along the chain direction due to the presence of robust COOH···N hydrogen bonds (Figure S4c & d). As a result the thermal expansion along this direction is least compared to the inter-chain directions and the smallest principal axis (X1) is close to this direction in both the structures. It is known that along the strong hydrogen bond direction the expansion could be very small or even negative due the presence of libration/transverse vibration effect.5 Therefore the origin of similarity in their thermal expansion behaviour lies in the similarity in their crystal structures. The principal interaction present is COOH···N hydrogen bond in these two structures and both of them primarily form similar 1D hydrogen bonded chain. Each of these chains is surrounded by six other chains and the inter-chain interactions are more or less of similar types in these two solids. We have made an attempt to explain the anomalous but similar thermal expansion modes in two topologically similar hydrogen bonded polymorphs of an organic binary complex. Both polymorphs exhibit a great degree of anisotropy in their thermal expansion behaviour. Due to similarities in the structures, the thermal expansion properties in these two lattices are found to be quite similar. One advantage of this type of solids is that, if they are used as materials, their thermal expansion properties will remain unchanged even if there is a phase transformation due to change in pressure, temperature or by other means. The mode of expansion in these two forms has been explained in a supramolecular context. The magnitude of modification in the structures seems to depend on the interactions and contacts that control the crystal packing along various directions. Overall, it could be concluded that the higher expansion was found to occur in the direction along which the interactions are weak in nature. This interaction based thermal


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expansion concept would be helpful to design new solids with desired expansion properties. This work would also prompt to study different polymorphs in terms of their thermal expansion. FIGURES

(a)

(b) Figure 1. Hydrogen bonded chains in (a) Form I and (b) Form II polymorphs of CBTA•BPE cocrystals.

Figure 2. Thermal expansion coefficients along the principal axes and in volume for Form I and Form II.


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(a)

(b)


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(c) Figure 3. View down the chain direction in the crystal structure of (a) Form I and (b) Form II. The approximate directions of the X3 and X2 axes are shown. X1 axis (not shown in figure) is close to the chain direction in these two forms. (c) Percentage change in the inter chain distances and the chain lengths for the Form I (purple) and Form II (green) systems. Supporting Information: Experimental and X-Ray crystallography, ORTEP diagrams for Form I and II at various temperatures, variation of the cell parameters with temperature, crystallographic table for the systems, hydrogen bond table, interactions at different directions at various temperatures. CCDC numbers: 933090 – 933101. See DOI: 10.1039/b000000x/. This material is available free of charge via the internet at http://pubs.acs.org. Corresponding Author Department of Chemistry, Pondicherry University, Pondicherry, India. 605014 Fax: E-mail: [email protected]


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Funding Sources B.K.S. thanks Council of Scientific and Industrial Research, India (No. 02(0026)/ 11/ EMR-II) for financial support and SB thanks Pondicherry University for fellowship. Acknowledgement BKS thanks DST-FIST for single crystal X-ray Diffractometer. References: (1) (a) Oh, W.; Ree, M. Langmuir 2004, 20, 6932−6939. (b) Ogborn, J. M.; Collings, I. E.; Moggach, S. A.; Thompson, A. L.; Goodwin, A. L. Chem. Sci. 2012, 3, 3011−3017. (2) (a) Sleight, A. W. US Patent, 1994, 5, 322,559. (b) Roy, R.; Agrawal, D. K.; McKinstry, H. A. Annu. Rev. Mater. Sci. 1989, 19, 59−81.(c) Hu, P.; Chen, J.; Sun, X.; Deng, J.; Chen, X.; Yu, R.; Qiao, L.; Xing, X. J. Mater. Chem. 2009, 19, 1648–1652. (d) Matsuda, T.; Tokoro, H.; Hashimoto, K.; Ohkoshi, S. Dalton Trans. 2006, 5046–5050. (3) (a) Das, D.; Jacobs, T.; Barbour, L. J. Nat. Mater. 2010, 9, 36−39. (b) Grobler, I.; Smith, V. J.; Bhatt, P. M.; Herbert, S. A.; Barbour, L. J. J. Am. Chem. Soc. 2013, 135, 6411−6414. (4) (a) Sleight, A. W. Annu. Rev. Mater. Sci. 1998, 28, 29−43.(b) Evans, J. S. O. J. Chem. Soc. Dalton. Trans. 1999, 3317−3326.(c) Yamamura, Y.; Horikoshi, A.; Yasuzuka,S.; Saitoh, H.; Saito, K. Dalton Trans. 2011, 40, 2242−2248.(d) Wang,X.; Huang, Q.; Deng, J.; Yu, R.; Chen, J.; Xing, X. Inorg. Chem. 2011, 50, 2685−2690.(e) Li, J.; Yokochi, A.; Amos, T. G.; Sleight, A. W. Chem. Mater. 2002, 14, 2602−2606. (f) Mclaughlin, A. C.; Sher, F.; Attfield, J. P. Nature 2005, 436, 829−832. (g) Hu, F. X.; Shen, B. G.; Sun, J. R.; Cheng, Z. H. Appl.Phys.Lett. 2001,


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Graphical Abstract

Two 1D hydrogen bonded 1:2 cocrystal polymorphs of 1,2,3,4-cyclobutanetetracarboxylic acid and 4,4′−bipyridylethylene exhibit very similar thermal expansion behaviors. Thermal expansions along different directions in the materials depend upon the types of interactions present along those directions.


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Interaction Dependence and Similarity in Thermal Expansion of a

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