Does Higher-Dimensional Hydrogen Bonding Guarantee a Smaller

of Chemistry, Pondicherry University, Pondicherry, India 605014. Cryst. Growth Des. , 2016, 16 (1), pp 277–284. DOI: 10.1021/acs.cgd.5b01228. Pu...
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Does Higher-Dimensional Hydrogen Bonding Guarantee a Smaller Thermal Expansion? A Thermal Expansion Study of an Interdigitated 1D and Interpenetrated 3D Hydrogen-Bonded Colored Dimorphic System Suman Bhattacharya, Viswanadha G. Saraswatula, and Binoy K. Saha* Department of Chemistry, Pondicherry University, Pondicherry, India 605014 S Supporting Information *

ABSTRACT: The 1:1:1 complex of benzene-1,3,5-tricarboxylic acid (BTA), 4,4′-methylenebis(2,6-dimethylaniline) (MBDA), and methanol has two polymorphic forms that can be regarded as synthon polymorphs. The hydrogen bond dimensionalities in the crystal structure of the two forms are different, and the forms have their own unique colors. The polymorph, with a three-dimensional hydrogen bond topology (3D form), forms an interpenetrated network and is violet in color, whereas the other polymorph, which is bright yellow in color, forms an interdigitated one-dimensional hydrogen bond topology (1D form). The volumetric expansion of the 3D form is comparable to that of the 1D form, but the anisotropy of expansion is found to be significantly higher in the 3D form than in its 1D counterpart. A structure−property correlation study of the dimorphic complex is presented in the context of their thermal expansion behavior and color.



INTRODUCTION Materials, when heated, generally are seen to expand in all directions. However, there are some materials that undergo contraction when the temperature is increased. Such anomalous thermal expansion phenomena are known as “negative thermal expansion” and involve contraction in overall volume1−3 of the material or just along one (uniaxial)4−7 or two (biaxial)8−10 principal axes of expansion. Materials that exhibit negative thermal expansion have been found to have profound industrial applications.11 Thus, it becomes important to properly understand the reasons behind such anomalous thermal expansion for the successful design of materials with desired thermal properties. It is apparent from previous literature reports that the reasons for such anomalous thermal behavior lie at the molecular level. Hence, proper study and knowledge of crystal structures of materials might be useful in understanding their thermal expansion behavior. Most of the studies, reported on thermal expansion, have been performed on inorganic systems12−16 or metal−organic compounds,17−21 but such studies of purely organic systems22−27 are relatively less common. As the organic systems are vast in number and diverse in terms of their interactions, symmetry, and packing, many interesting thermal expansion properties could be observed in these materials.4,5,10,22−27 Many of the thermal expansion properties of solids could be well explained in terms of the noncovalent interactions that aid in the construction of the crystal. There have been some interesting studies, reported in the literature, of thermal expansion in hydrogen-bonded systems.4,5,22,28−35 It is well© XXXX American Chemical Society

known that stronger interactions lead to smaller expansions.36−38 On the basis of a theoretical study, Lifshits showed that on heating, a molecular crystal contracts along the chains or within the layers, whereas it expands in the perpendicular directions to the chains or the layers.39 We have observed this phenomenon experimentally in a one-dimensional hydrogenbonded dimorphic system in which the molecules are assembled along one direction via weak van der Waals forces, in another direction via C−H···O interactions, and in the third direction via strong O−H···N hydrogen bonds.40 The order of thermal expansion observed along these three directions in these dimorphic systems is as follows: weak van der Waals interactions > C−H···O interactions > strong O−H···N hydrogen bond (the reverse order of their bonding strengths). In the case of covalent solids, such as graphite (twodimensional) and diamond (three-dimensional), along with the zero-dimensional form, fullerenes (C60 and C70), it has been found that the structure, with a higher-dimensional covalent bonded network, exhibits a smaller thermal expansion.41−43 Therefore, one might expect that a higherdimensional hydrogen-bonded system would have a volumetric thermal expansion coefficient smaller than that of a lowerdimensional hydrogen-bonded system. Indeed, this has been shown in a recent report from our group on thermal expansion of tetrolic acid polymorphs; the one-dimensional hydrogenReceived: August 25, 2015 Revised: November 13, 2015

A

DOI: 10.1021/acs.cgd.5b01228 Cryst. Growth Des. XXXX, XXX, XXX−XXX

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Scheme 1. Dimorphic Complex of BTA, MBDA, and MeOH

bonded form exhibits a thermal expansion (265 MK−1) smaller than that of the zero-dimensional (332 MK−1) hydrogenbonded form.30 A similar result was observed in the thermal expansion behaviours of the one dimensional hydrogen bonded and non-hydrogen bonded polymorphs of 4,4′-methylenebis(2,6-dimethylaniline).24 The pertinent question is whether a higher-dimensional hydrogen bonding network guarantees a smaller thermal expansion. Polymorphs with different hydrogen bond dimensionalities are the best systems to be studied to answer this question. Earlier, in the context of structural chemistry, we reported the crystal structures of a dimorphic 1:1:1 organic complex of benzene-1,3,5-tricarboxylic acid (BTA), 4,4′-methylenebis(2,6-dimethylaniline) (MBDA), and methanol (MeOH) (Scheme 1).44 The structure of one of the forms is constructed of a one-dimensional (1D) hydrogenbonded network, whereas the other polymorphic structure is based on a three-dimensional (3D) hydrogen-bonded network. Herein, we present a study of the thermal expansion behavior of the dimorphic complex based on variable-temperature singlecrystal X-ray diffraction experiments.

crystallographic (123) plane. The alternate layers are bridged via AB synthons through MBDA molecules and form a threedimensional hydrogen-bonded network (Figure 2b) that further undergoes a parallel interpenetration.51−55 The 1D polymorph, a yellow-colored, plate-shaped solid (Figure 1b), was obtained by employing a mixture of BTA and MBDA for crystallization from methanol in a 3:2 stoichiometric ratio. The 1D form also crystallizes in the P1̅ space group, and the asymmetric unit contains one molecule each of the three components, similar to form 3D (Figure S1). The BTA molecules form chains via the commonly observed centrosymmetric acid dimer synthon (Figure 2c). The leftover carboxyl acid group of each BTA forms O−H···N and O−H···O hydrogen bonds (Table 1) with MBDA and MeOH, respectively. Only one amino group of each MBDA molecule is involved in a strong O−H···N hydrogen bond with the BTA chain, and the other amino group is found to be free [the two N−H···O interactions (N···O, 3.593 and 3.321 Å at 298 K) of this amino group with the neighboring chains are too weak to be considered as significant hydrogen bonding]. These hydrogen-bonded one-dimensional assemblies are packed in a ziplike motif, mainly via weak van der Waals interactions, to form a corrugated two-dimensional sheet parallel to the crystallographic (122) plane. Synthon Polymorphism. The synthons, responsible for different dimensionality hydrogen-bonded networks, are notably different in these two forms. Hence, the dimorphs may be regarded as synthon polymorphs.56−60 The formula unit (one each of the three components), in the 3D form, is engaged in two O−H···O, two O−H···N, and three N−H···O hydrogen bonds in contrast to only three O−H···O hydrogen bonds and one O−H···N hydrogen bond in the 1D form (Table 1). Comparison of fingerprint plots, using Crystal Explorer,61 of the two structures also suggests that the percentage of polar stabilizing contacts, such as O···H, N···H, C···H, and O···C, is considerably higher in the 3D form than in the 1D form. In contrast, the 1D form contains a percentage of H···H and C···C contacts relatively higher than that of the 3D form (Figure 3). On the other hand, the crystal packing efficacy62 in form 1D (68.8%) is evidently higher than that in form 3D (66.9%). As a result, the 1D form is considerably denser than the 3D form (Figure S2). This is rather expected because the network in the 1D form is less constrained than that in the 3D form, and hence, packing is more efficient in the 1D form. Thermal Expansion of the Polymorphs. A good diffraction quality crystal was chosen for each form, and a set of five data, at a regular interval of 45 K in the range of 118− 298 K, was collected in each case (Table 2 and Table S1). Calculations, using PASCal,63 suggest that the volumetric thermal expansion coefficient (Figure 4 and Figure S3) of the 3D form [165(5) MK−1] is comparable (within the error limit) to that of the 1D form [153(5) MK−1]. This particular observation is well in line with one of our recent reports on a



RESULTS AND DISCUSSION Crystal Structures of the Polymorphic 1:1:1 Complex of BTA, MBDA, and MeOH. The dimorphs were synthesized by crystallizing BTA and MBDA from methanol using a different stoichiometric ratio of the former. The 3D polymorph, a light violet rod-shaped solid (Figure 1a), is produced by

Figure 1. (a) Violet-colored single crystal of the 3D form. (b) Yellowcolored single crystal of the 1D form.

crystallization of a 2:3 mixture of BTA and MBDA from methanol. The system crystallizes in the P1̅ space group with one molecule each of BTA, MBDA, and MeOH in the asymmetric unit (Figure S1). The structure retains the (6,3) hexagonal network that is often observed in BTA-containing crystal structures;45−50 however, the architecture of the network is devoid of any kind of acid···acid hydrogen bonds (Figure 2a). Rather, two acid groups in the network are bridged by hydroxyl groups (via synthon HB) of MeOH or amino groups (via synthon AB) of MBDA (Figure 2b). Each of the hexagons consists of six BTA molecules, two HB synthons, and four AB types of synthons. The hexagonal layer is parallel to the B

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one-dimensional/two-dimensional hydrogen-bonded dimorphic solvate pair that exhibited very similar volumetric expansion.29 Boldyreva et al. reported a thermal expansion study of three glycine polymorphs, although they did not comment on the volumetric expansion of the three polymorphs.64 Our calculation, with PASCal on the cell parameters reported by Boldyreva et al., showed that the volumetric thermal expansion coefficient of the glycine α form [two-dimensional hydrogen-bonded; αv = 99(2) MK−1] is similar to that of the β form [three-dimensional hydrogenbonded; αv = 97(2) MK−1], but it is relatively lower in the case of the γ form [three-dimensional hydrogen-bonded; αv = 83(1) MK−1]. Considering the fact that the packing coefficient of the 1D polymorph (68.8%) is higher than the packing coefficient of the 3D form (66.9%), we conclude that the excess hydrogen bond energy, in the 3D form, is compensated by a better packing in the 1D form that results in comparable volumetric thermal expansions of the dimorphs. This fact is also evident in the trend of the percent change in the Ueq of the different moieties forming the networks in the dimorphs. The percent changes in Ueq of BTA and MBDA moieties, taken together in these two structures, are comparable, which suggests a similar expansion of these moieties (Figure 5 and Figure S4). As expected, the percent change in Ueq of the solvent guest moieties (MeOH) is evidently more pronounced in both structures.29 It is also found that the percent change in Ueq of MeOH is notably higher in the 3D form than in the 1D form, which could be attributed to the higher strain in the network of the 3D form, making the packing of the guest weaker compared to that in the 1D form. Interpenetration and Thermal Expansion. There have been some interesting thermal expansion studies of interpenetrated networks reported in the literature. While some of the reports suggest that interpenetration reduces65,66 the magnitude of NTE, other suggests that it enhances67 NTE in the material. All these reports are based on metal−organic frameworks, and the thermal expansion of the interpenetrated network structures has been compared with that of the noninterpenetrated but similar networks. In contrast, this could be the first report in which thermal expansion has been compared between an interpenetrated and an interdigitated organic dimorphic system with different hydrogen bond topologies. Our interpenetrated 3D network shows a volumetric thermal expansion coefficient that is comparable to that of the 1D hydrogen-bonded noninterpenetrated but interdigitated system. Anisotropy in Thermal Expansion. The linear thermal expansion coefficients, calculated using PASCal, along the minor (X1), medium (X2), and major (X3) principal axes found are −35(1), 43(1), and 155(3) MK−1 and −7(2), 15(2), and 140(4) MK−1 in the 3D and 1D forms, respectively (Figure 4 and Figure S3). In contrast to the 3D form, in which the network is composed of strong hydrogen bonds in all three directions, in the 1D form, the molecules are bound by strong hydrogen bonds in only one direction and the individual interactions are much weaker in nature in the other two directions. Therefore, it was expected that the 1D form might show a larger anisotropy in its thermal expansion. The expectation was in line with our aforementioned report of thermal expansion studies of a one-dimensional/two-dimensional dimorphic pair in which the larger anisotropy indeed was found in the one-dimensional form.29 Interestingly, the study presented here shows that the anisotropy or difference in

Figure 2. (a) Two-dimensional hexagonal hydrogen-bonded network on the (123) plane in the 3D form. Only one layer and the hydrogen bonded aryl group part of the MBDA molecules are shown for the sake of clarity. (b) Schematic diagram of the three-dimensional hydrogenbonded network in the 3D form. The diagram shows how hexagonal layers are built of the BTA molecules, linked via HB and AB synthons. These layers are connected through MBDA molecules to form a threedimensional network. Only two layers of the three-dimensional infinite network are shown. (c) Illustration of crystal packing on a (122) plane in the 1D form. C

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Table 1. Hydrogen Bond Parameters for the Systems at Different Temperatures hydrogen bonds O1−H1···O2

N1−H1A···O3

O4−H4···O3

O5−H5···N2

O7−H7···O6

3D Form N1−H1A···O1

O2−H2···N1

N2−H2A···O3

N2−H2B···O3

O4−H4···N2

O6−H6···O7

O7−H7···O5

118 K

163 K

O−H H···O O···O ∠O−H···O N−H H···O N···O ∠N−H···O O−H H···O O···O ∠O−H···O O−H H···N O···N ∠O−H···N O−H H···O O···O ∠O−H···O

0.88(3) 1.73(3) 2.6079(15) 177(4) 0.870(18) 2.507(18) 3.3104(17) 153.8(15) 0.92(3) 1.66(3) 2.5838(15) 178(3) 0.90(2) 1.73(2) 2.6220(15) 173(2) 0.93(2) 1.95(2) 2.8350(17) 160(2)

1D Form 0.88(3) 1.74(3) 2.6168(16) 176(3) 0.87(2) 2.52(2) 3.3192(19) 153.9(18) 0.92(3) 1.67(3) 2.5912(15) 178(4) 0.88(2) 1.75(2) 2.6265(18) 175(2) 0.94(3) 1.94(3) 2.845(2) 161(3)

N−H H···O N···O ∠N−H···O O−H H···N O···N ∠O−H···N N−H H···O N···O ∠N−H···O N−H H···O N···O ∠N−H···O O−H H···N O···N ∠O−H···N O−H H···N O···N ∠O−H···N O−H H···N O···N ∠O−H···N

0.893(16) 2.227(16) 3.1019(17) 166.3(15) 0.90(2) 1.76(2) 2.6447(17) 166(2) 0.910(15) 2.125(15) 2.9931(15) 159.2(13) 0.895(15) 2.406(17) 3.1240(15) 137.4(14) 0.890(17) 1.783(18) 2.6469(14) 163(2) 0.90(2) 1.68(2) 2.5666(17) 167.1(19) 0.884(19) 1.88(2) 2.7288(17) 161.9(19)

0.879(17) 2.247(17) 3.1099(18) 167.2(17) 0.90(2) 1.76(2) 2.6504(17) 167(2) 0.911(16) 2.126(16) 3.0013(16) 160.7(16) 0.898(15) 2.425(17) 3.1461(16) 137.6(14) 0.888(17) 1.788(18) 2.6515(16) 164(2) 0.89(2) 1.69(2) 2.5664(18) 167(2) 0.87(2) 1.90(2) 2.7300(17) 160(2)

208 K

253 K

298 K

0.88(3) 1.74(3) 2.6162(17) 175(3) 0.87(2) 2.52(2) 3.316(2) 152.3(17) 0.91(3) 1.69(3) 2.5938(17) 176(3) 0.87(2) 1.76(2) 2.6272(18) 178(2) 0.93(3) 1.95(3) 2.848(2) 162(4)

0.87(4) 1.76(4) 2.6262(19) 176(4) 0.88(3) 2.52(3) 3.321(2) 153(2) 0.91(3) 1.69(3) 2.5994(18) 177(4) 0.89(2) 1.75(2) 2.636(2) 176(2) 0.82 2.09 2.863(2) 156

0.88(4) 1.75(4) 2.635(2) 178(5) 0.87(3) 2.55(3) 3.324(3) 149(2) 0.90(3) 1.71(3) 2.607(2) 177(3) 0.88(3) 1.76(2) 2.639(2) 175(3) 0.82 2.11 2.875(3) 155

0.872(18) 2.263(18) 3.1113(19) 164.4(18) 0.90(2) 1.78(2) 2.6515(19) 165(2) 0.91(2) 2.14(2) 3.0105(18) 161.7(17) 0.898(19) 2.44(2) 3.1676(17) 138.2(17) 0.892(17) 1.786(17) 2.6522(16) 163(2) 0.88(3) 1.70(3) 2.568(2) 168(2) 0.86(2) 1.90(3) 2.722(2) 160(2)

0.891(19) 2.25(2) 3.119(2) 165(2) 0.90(2) 1.77(2) 2.660(2) 166(2) 0.913(17) 2.146(17) 3.0231(19) 160.6(17) 0.898(15) 2.483(19) 3.1981(19) 136.9(16) 0.884(19) 1.80(2) 2.6596(18) 165(3) 0.88(3) 1.72(3) 2.577(2) 165(3) 0.86(3) 1.92(3) 2.720(2) 156(4)

0.897(17) 2.252(17) 3.125(2) 164(2) 0.87(2) 1.81(2) 2.667(2) 168(2) 0.904(17) 2.162(17) 3.034(2) 162.2(17) 0.897(16) 2.49(2) 3.223(2) 138.9(18) 0.866(16) 1.813(19) 2.6614(18) 166(3) 0.87(3) 1.73(3) 2.582(3) 166(3) 0.82 1.96 2.720(3) 155

3D form, and this NTE is found to be caused by sliding of the hexagonal layers (Figure S5).5 It has been noticed that in case of 1D, the percents of thermal expansion along the hydrogenbonded chain and across the chain on the (122) plane, where the interactions between two consecutive chains are of weak van der Waals type, are very similar, but it is relatively higher in the perpendicular direction of this plane, which is also controlled by weak van der Waals types of interactions (Figure 6). The similarity in thermal expansion along and across the

thermal expansion coefficients between the major and minor axes is found to be considerably higher in the case of the 3D form than in the case of the 1D form. This is due to the occurrence of larger structural deformation in the case of the 3D form than in the case of the 1D form. This is evident from the aspherism index (AI)37 calculation (Table S2) that suggests a larger structural deformation in the 3D form (AI = 0.6763) compared to that in the 1D form (AI = 0.6217). The relatively higher NTE along the X1 axis causes higher anisotropy in the D

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Figure 4. Plot of comparative linear and volumetric thermal expansion coefficients of the 3D and 1D forms of the BTA·MBDA·MeOH complex. Figure 3. Percent contribution of different types of contacts present in the 3D and 1D forms.

in the structure, is deep yellow. It is known that the two components, BTA and MeOH, do not produce color. Hence, the color of the crystals can be due to only the n → π* transition, which is possible in the MBDA moiety. The molecular conformations of the MBDA moieties in the structures of the dimorphs too are different as could be seen from the overlay diagram (Figure 7a). However, this could not be the reason for the appearance of different colors because the two aromatic rings are not conjugated. It appeared to us that the different colors imparted by MBDA to the systems may be governed by different degrees of involvement in hydrogen bonding of the amine groups of MBDA with the other two components in these two forms. Indeed, in form 3D, both amine groups of MBDA are involved in strong hydrogen bonds, whereas in form 1D, only one of the amine groups is involved in hydrogen bonds. To see the effect of hydrogen bonds on the color imparted by MBDA, we prepared equimolar MBDA

chain could be attributed to the interdigitation of the long branches (i.e., MBDA moieties) as shown in Figure 2c. These MBDA moieties, due to thermal vibration, mostly repel each other along the chain direction, and this causes the unexpected similarity in thermal expansion along those two directions. Structure−Color Correlation. Apart from the dimensionality of the hydrogen bonding networks and anisotropy in thermal expansion, another feature that distinguishes the dimorphs is their unique colors (Figure 1). Several instances of polymorphic materials have been reported in the literature; different polymorphic phases have been found to exhibit different colors, which were explained in terms of interaction properties of molecules in the solid state.68−70 The 3D form, which has a larger number of hydrogen bonds in the structure, is violet, whereas the 1D form, which has fewer hydrogen bonds

Table 2. Crystallographic Parameters of the Systems at Different Temperatures

empirical formula formula weight temperature (K) crystal system space group a (Å) b (Å) c (Å) α (deg) β (deg) γ (deg) volume (Å3) Z ρcalc (g/cm3) μ (mm−1) F(000) crystal size (mm3) no. of reflections collected no. of independent reflections data/restraints/parameters goodness of fit on F2 final R indices [I ≥ 2σ(I)] final R indices (all data) CCDC No.

3D-118

3D-298

1D-118

1D-298

C27H32N2O7 496.54 118(2) triclinic P1̅ 4.7368(2) 16.2029(9) 17.3849(8) 108.221(5) 91.911(4) 93.502(4) 1263.07(12) 2 1.306 0.095 528 0.5 × 0.42 × 0.28 12190 5795 5795/8/362 1.039 R1 = 0.0421 wR2 = 0.1097 1046429

C27H32N2O7 496.54 298(2) triclinic P1̅ 4.8375(2) 16.3535(10) 17.3007(9) 107.360(5) 92.237(4) 94.421(4) 1299.66(13) 2 1.269 0.092 528 0.5 × 0.42 × 0.28 12128 5965 5965/15/359 1.035 R1 = 0.0517 wR2 = 0.1483 1046433

C27H32N2O7 496.54 118(2) triclinic P1̅ 8.2850(4) 8.3115(4) 18.5592(7) 86.234(4) 86.749(4) 75.493(5) 1233.51(10) 2 1.337 0.097 528 0.42 × 0.38 × 0.38 13257 5744 5744/8/362 1.023 R1 = 0.0426 wR2 = 0.1230 1046424

C27H32N2O7 496.54 298(2) triclinic P1̅ 8.2837(8) 8.5154(8) 18.6191(12) 85.817(7) 86.905(7) 75.668(8) 1268.2(2) 2 1.3 0.094 528 0.42 × 0.38 × 0.38 13684 5838 5838/7/359 1.033 R1 = 0.0574 wR2 = 0.1739 1046428

E

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Figure 5. Percent change in Ueq for (BTA + MBDA) and MeOH in the dimorphs with temperature. The change is much more pronounced for MeOH than for (BTA + MBDA).

Figure 7. (a) Overlay diagram of MBDA molecules present in 1D (red) and 3D (green) forms. (b) Colored solutions of MBDA in tetrahydrofuran (THF), ethanol (EtOH), carbon tetrachloride (CCl4), and glacial acetic acid (AcOH).

expansion coefficient comparable to that of the denser onedimensional (1D) hydrogen-bonded system that also contains fewer hydrogen bonds. Hydrogen bond efficiency and packing efficiency compensate for each other in this case. The two forms also exhibit different colors because of the differences in hydrogen bonding of the MBDA moiety in their crystal structures. This study suggests that, though a hydrogen bond is a very important parameter in determining the thermal expansion properties of a material, it may not always be possible to predict the thermal expansion in an organic material based on the hydrogen bonding alone.

Figure 6. Percent thermal expansion along the hydrogen-bonded chain (red), across the chain on the (122) layer (blue), and along the perpendicular direction of this layer (magenta) with respect to temperature in the 1D form.



solutions in four solvents that are different in terms of their hydrogen bond forming ability. We noticed that MBDA in THF (a hydrogen bond acceptor) or ethanol (good hydrogen bond donor as well as acceptor) produces a very pale violet solution, whereas in CCl4 (does not form significant hydrogen bond), it produces a light yellow solution (Figure 7b). However, in glacial acetic acid (a strong hydrogen bond donor as well as acceptor, also a proton donor), it produces a dark violet solution. Thus, we conclude that the unique colors of the two forms are indeed due to the differences in hydrogen bonding of the MBDA moiety observed in these two synthon polymorphs.

ASSOCIATED CONTENT

* Supporting Information S

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.cgd.5b01228. Crystallization and X-ray crystallography, ORTEP plots of the systems at different temperatures at 50% probability, plots showing the change in the densities of the dimorphs with temperature, expansitivity indicatrices, plots showing the change in the mean Ueq of the host (BTA and MBDA) and the guest MeOH molecule in the two dimorphs, sliding of layers in the 3D form, aspherism index calculations, and detailed crystallographic data (PDF)



CONCLUSION In summary, we have attempted to present a structure− property correlation in the context of thermal expansion and color for a dimorphic organic complex of BTA, MBDA, and MeOH. Despite possessing a large number of hydrogen bonds in the crystal structure, the less dense three-dimensional (3D) hydrogen-bonded system exhibits a volumetric thermal

Accession Codes

CCDC 1046424−1046433 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The F

DOI: 10.1021/acs.cgd.5b01228 Cryst. Growth Des. XXXX, XXX, XXX−XXX

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(22) Hutchins, K. M.; Groeneman, R. H.; Reinheimer, E. W.; Swenson, D. C.; MacGillivray, L. R. Chem. Sci. 2015, 6, 4717−4722. (23) Saraswatula, V. G.; Saha, B. K. Chem. Commun. 2015, 51, 9829− 9832. (24) Bhattacharya, S.; Saha, B. K. CrystEngComm 2014, 16, 2340− 2343. (25) Haas, S.; Batlogg, B.; Besnard, C.; Schiltz, M.; Kloc, C.; Siegrist, T. Phys. Rev. B: Condens. Matter Mater. Phys. 2007, 76 (205203), 1−5. (26) Jones, R. H.; Knight, K. S.; Marshall, W. G.; Clews, J.; Darton, R. J.; Pyatt, D.; Coles, S. J.; Horton, P. N. CrystEngComm 2014, 16, 237− 243. (27) Saraswatula, V. G.; Saha, B. K. New J. Chem. 2014, 38, 897−901. (28) Drebushchak, T. N.; Boldyreva, E. V. Z. Kristallogr. - Cryst. Mater. 2004, 219, 506−512. (29) Saraswatula, V. G.; Saha, B. K. Cryst. Growth Des. 2015, 15, 593−601. (30) Saraswatula, V. G.; Bhattacharya, S.; Saha, B. K. New J. Chem. 2015, 39, 3345−3348. (31) Bhattacharya, S.; Saraswatula, V. G.; Saha, B. K. Cryst. Growth Des. 2013, 13, 3651−3656. (32) Das, D.; Jacobs, T.; Pietraszko, A.; Barbour, L. J. Chem. Commun. 2011, 47, 6009−6011. (33) Boldyreva, E. V.; Kolesnik, E. N.; Drebushchak, T. N.; Ahsbahs, H.; Beukes, J. A.; Weber, H. − P. Z. Kristallogr. - Cryst. Mater. 2005, 220, 58−65. (34) Drebushchak, T. N.; Boldyreva, E. V.; Mikhailenko, M. A. J. Struct. Chem. 2008, 49, 84−94. (35) Gallagher, K.; Ubbelohde, A. R.; Woodward, I. Acta Crystallogr. 1955, 8, 561−566. (36) Kitaigorodsky, A. I. Molecular Crystals and Molecules; Physical Chemistry Series No. 29; Loebl, E. M., Ed.; Academic Press: New York, 1973. (37) Weigel, D.; Beguemsi, T.; Garnier, P.; Berar, J. F. J. Solid State Chem. 1978, 23, 241−251. (38) Garnier, P.; Calvarin, G.; Weigel, D. J. Chim. Phys. Phys.-Chim. Biol. 1972, 11−12, 1711−1718. (39) Lifshits, I. M. Zh. Eksp. Teor. Fiz. Q5 1952, 22, 475−486. (40) Bhattacharya, S.; Saha, B. K. Cryst. Growth Des. 2013, 13, 3299− 3302. (41) Nelson, J. B.; Riley, D. P. Proc. Phys. Soc. 1945, 57, 477−486. (42) Mathews, C. K.; Rajagopalan, S.; Kutty, K. V. G.; Asuvathraman, R.; Sivaraman, N.; Srinivasan, T. G.; Vasudeva Rao, P. R. Solid State Commun. 1993, 85, 377−379. (43) Thewlis, J.; Davey, A. R. XL. Philos. Mag. 1956, 1, 409−414. (44) Bhattacharya, S.; Saha, B. K. Cryst. Growth Des. 2011, 11, 2194− 2204. (45) Shattock, T. R.; Vishweshwar, P.; Wang, Z.; Zaworotko, M. J. Cryst. Growth Des. 2005, 5, 2046−2049. (46) Sharma, C. V. K.; Zaworotko, M. J. Chem. Commun. 1996, 2655−2656. (47) Vishweshwar, P.; Beauchamp, D. A.; Zaworotko, M. J. Cryst. Growth Des. 2006, 6, 2429−2431. (48) Melendez, R. E.; Sharma, C. V. K.; Zaworotko, M. J.; Bauer, C.; Rogers, R. D. Angew. Chem., Int. Ed. Engl. 1996, 35, 2213−2215. (49) Santra, R.; Ghosh, N.; Biradha, K. New J. Chem. 2008, 32, 1673−1676. (50) Chen, W. X.; Wu, S. T.; Long, L. S.; Huang, R. B.; Zheng, L. S. Cryst. Growth Des. 2007, 7, 1171−1175. (51) Bhogala, B. R.; Nangia, A. Cryst. Growth Des. 2003, 3, 547−554. (52) Sarkar, M.; Biradha, K. Cryst. Growth Des. 2007, 7, 1318−1331. (53) Bhogala, B. R.; Vishweshwar, P.; Nangia, A. Cryst. Growth Des. 2002, 2, 325−328. (54) Bhogala, B. R.; Basavoju, S.; Nangia, A. Cryst. Growth Des. 2005, 5, 1683−1686. (55) Bhattacharya, S.; Saha, B. K. CrystEngComm 2011, 13, 6941− 6944. (56) Goud, N. R.; Nangia, A. CrystEngComm 2013, 15, 7456−7461. (57) Mukherjee, A.; Desiraju, G. R. Chem. Commun. 2011, 47, 4090− 4092.

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AUTHOR INFORMATION

Corresponding Author

*Department of Chemistry, Pondicherry University, Pondicherry, India 605014. E-mail: [email protected]. Funding

The work has been supported by the Center of Scientific and Industrial Research, India [02(0026)/11/EMR-II to B.K.S., dated December 16, 2011]. The single-crystal X-ray diffraction facility of the Department of Chemistry is supported by the Department of Science and Technology, India. V.G.S. thanks UGC for a fellowship. S.B. thanks CSIR, India, for a Senior Research Fellowship. Notes

The authors declare no competing financial interest.



REFERENCES

(1) Zhao, Y. Y.; Hu, F. X.; Bao, L. F.; Wang, J.; Wu, H.; Huang, Q. Z.; Wu, R. R.; Liu, Y.; Shen, F. R.; Kuang, H.; Zhang, M.; Zuo, W. L.; Zheng, X. Q.; Sun, J. R.; Shen, B. G. J. Am. Chem. Soc. 2015, 137, 1746−1749. (2) Marinkovic, B. A.; Ari, M.; de Avillez, R. R.; Rizzo, F.; Ferreira, F. F.; Miller, K. J.; Johnson, M. B.; White, M. A. Chem. Mater. 2009, 21, 2886−2894. (3) Goodwin, A. L.; Chapman, K. W.; Kepert, C. J. J. Am. Chem. Soc. 2005, 127, 17980−17981. (4) Engel, E. R.; Smith, V. J.; Bezuidenhout, C. X.; Barbour, L. J. Chem. Commun. 2014, 50, 4238−4241. (5) Bhattacharya, S.; Saha, B. K. Cryst. Growth Des. 2012, 12, 4716− 4719. (6) Birkedal, H.; Schwarzenbach, D.; Pattison, P. Angew. Chem. 2002, 114, 780−782. (7) Wang, K. Y.; Feng, M. L.; Zhou, L. J.; Li, J. R.; Qi, X. H.; Huang, X. Y. Chem. Commun. 2014, 50, 14960−14963. (8) Grobler, I.; Smith, V. J.; Bhatt, P. M.; Herbert, S. A.; Barbour, L. J. J. Am. Chem. Soc. 2013, 135, 6411−6414. (9) Das, D.; Jacobs, T.; Barbour, L. J. Nat. Mater. 2010, 9, 36−39. (10) Takahashi, H.; Tamura, R. CrystEngComm 2015, 17, 8888− 8896. (11) Grima, J. N.; Zammit, V.; Gatt, R. Xjenza 2006, 11, 17−29. (12) Hancock, J. C.; Chapman, K. W.; Halder, G. J.; Morelock, C. R.; Kaplan, B. S.; Gallington, L. C.; Bongiorno, A.; Han, C.; Zhou, S.; Wilkinson, A. P. Chem. Mater. 2015, 27, 3912−3918. (13) Yamada, I.; Shiro, K.; Etani, H.; Marukawa, S.; Hayashi, N.; Mizumaki, M.; Kusano, Y.; Ueda, S.; Abe, H.; Irifune, T. Inorg. Chem. 2014, 53, 10563−10569. (14) Li, W.; Huang, R.; Wang, W.; Tan, J.; Zhao, Y.; Li, S.; Huang, C.; Shen, J.; Li, L. Inorg. Chem. 2014, 53, 5869−5873. (15) Tallentire, S. E.; Child, F.; Fall, I.; Vella-Zarb, L.; Evans, I. R.; Tucker, M. G.; Keen, D. A.; Wilson, C.; Evans, J. S. O. J. Am. Chem. Soc. 2013, 135, 12849−12856. (16) Duyker, S. G.; Peterson, V. K.; Kearley, G. J.; Ramirez-Cuesta, A. J.; Kepert, C. J. Angew. Chem., Int. Ed. 2013, 52, 5266−5270. (17) Lock, N.; Wu, Y.; Christensen, M.; Cameron, L. J.; Peterson, V. K.; Bridgeman, A. J.; Kepert, C. J.; Iversen, B. B. J. Phys. Chem. C 2010, 114, 16181−16186. (18) Han, S. S.; Goddard, W. A. J. Phys. Chem. C 2007, 111, 15185− 15191. (19) van Heerden, D. P.; Esterhuysen, C.; Barbour, L. J. Dalton Trans. 2016, DOI: 10.1039/C5DT01927C. (20) Cliffe, M. J.; Hill, J. A.; Murray, C. A.; Coudert, F. X.; Goodwin, A. L. Phys. Chem. Chem. Phys. 2015, 17, 11586−11592. (21) Rimmer, L. H. N.; Dove, M. T.; Goodwin, A. L.; Palmer, D. C. Phys. Chem. Chem. Phys. 2014, 16, 21144−21152. G

DOI: 10.1021/acs.cgd.5b01228 Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design

Article

(58) Babu, N. J.; Cherukuvada, S.; Thakuria, R.; Nangia, A. Cryst. Growth Des. 2010, 10, 1979−1989. (59) Dubey, R.; Desiraju, G. R. Cryst. Growth Des. 2015, 15, 489− 496. (60) Schultheiss, N.; Roe, M.; Boerrigter, S. X. M. CrystEngComm 2011, 13, 611−619. (61) Wolff, S. K.; Grimwood, D. J.; McKinnon, J. J.; Turner, M. J.; Jayatilaka, D.; Spackman, M. A. CrystalExplorer 3.1, University of Western Australia: Crawley, Australia, 2012. (62) Spek, A. L. Acta Crystallogr., Sect. A: Found. Crystallogr. 1990, 46, C34. (63) Cliffe, M. J.; Goodwin, A. L. J. Appl. Crystallogr. 2012, 45, 1321− 1329. (64) Boldyreva, E. V.; Drebushchak, T. N.; Shutova, E. S. Z. Kristallogr. - Cryst. Mater. 2003, 218, 366−376. (65) Chapman, K. W.; Chupas, P. J.; Kepert, C. J. J. Am. Chem. Soc. 2005, 127, 15630−15636. (66) Phillips, A. E.; Goodwin, A. L.; Halder, G. J.; Southon, P. D.; Kepert, C. J. Angew. Chem. 2008, 120, 1418−1421. (67) Wu, Y.; Peterson, V. K.; Luks, E.; Darwish, T. A.; Kepert, C. J. Angew. Chem. 2014, 126, 5275−5278. (68) Chai, W.; Hong, M.; Song, L.; Jia, G.; Shi, H.; Guo, J.; Shu, K.; Guo, B.; Zhang, Y.; You, W.; Chen, X. Inorg. Chem. 2015, 54, 4200− 4207. (69) Braun, D. E.; Gelbrich, T.; Jetti, R. K. R.; Kahlenberg, V.; Price, S. L.; Griesser, U. J. Cryst. Growth Des. 2008, 8, 1977−1989. (70) Yu, L. J. Phys. Chem. A 2002, 106, 544−550.

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DOI: 10.1021/acs.cgd.5b01228 Cryst. Growth Des. XXXX, XXX, XXX−XXX