Comparison Between the Acidification of Acidic and Alkalic Groups

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Cite This: Cryst. Growth Des. XXXX, XXX, XXX−XXX

Comparison Between the Acidification of Acidic and Alkalic Groups Xiao-Tong He,† Dan-Li Hong,† Chen Chen,† Fang-Hui Chen,† Li-Hai Zhai,‡ Li-Hong Guo,‡ Yang-Hui Luo,*,† and Bai-Wang Sun*,† †

School of Chemistry and Chemical Engineering, Southeast University, Nanjing, Jiangsu 211189, P.R. China Lunan Pharmaceutical Co. Ltd., Linyi, Shandong 276000, China

‡

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S Supporting Information *

ABSTRACT: The protonation of different functional acidic and alkalic groups is of utmost importance for the crystal engineering field. By using hydrochloric acid, in this work, the amine group of 3-aminobenzoic acid (1, C7H7NO2) and the hydroxy group of (E)-4-hydroxy-3,5-dimethoxybenzaldehyde oxime (2, C9H11NO4) have been protonated, giving birth to the organic salts [C7H8NO2]+·[Cl]− ([1H]+·[Cl]−) and [C9H12NO4]+·[Cl]− ([2H]+·[Cl]−). Results revealed that both salts display similar 1D “stair-like” ribbon models via the formation of intermolecular hydrogen bonding contacts between chloride ion and the protonated groups into fourmembered squares. Note that the protonated acidic groups have shown much closer and stronger intermolecular interactions than the alkalic groups. In addition, 3D Hirshfeld surfaces, 2D fingerprint plots, and crystal void calculations have been performed, which have suggested 21.4% and 17.5% interactions around the protonated acidic and alkalic groups, respectively. This work will provide a new insight into the rational design and control of molecular crystal with protonated functional groups.

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INTRODUCTION Co-crystal, coming into academic research in the early 1990s,1 has been given a great deal of attention due to its prominent performance in the fields of material science2−4 and pharmaceutical,5−8 agrochemical,9−11 and other industrial applications. A refined definition of co-crystal12−14 is a system where at least two different entities form a crystalline solid in a certain stoichiometric ratio via intermolecular interactions, including hydrogen bonding, π−π stacking, and halogen bonding.15−18 Among these intermolecular interactions, the hydrogen bond, which possesses the characteristics of directionality and selectivity, plays a pivotal function in the formation of distinctive and predictable aggregations in the solid state; in addition, co-crystallization19−21 of the hydrogen bond as a steering force has been considered as the most crucial approach in crystal engineering. Protonation is ubiquitous in co-crystallization,22−30 in which the negatively charged ions derived from acids like HCl, H2SO4, and HClO4 appearing as connectors interact with protonated moieties to build up co-crystal through intermolecular hydrogen bonds, and is able to provide unexpectedly good results in properties including catalytic activity, spin crossover, optical properties, and so on in the way of changing electronic state, redox properties, and charge mobility.31 More recently, Ma and coworkers presented symmetrical and asymmetrical protonation states induced by introducing H2SO4 and HCl, respectively, into 9,10-bis((E)-2-(pyridin-4-yl)vinyl)-anthracene with extraordinary optical properties compared with neutral crystal.32 © XXXX American Chemical Society

Thus, it is crucial to research detailedly the protonation effects of compounds in many branches of chemistry. To figure out the role of protonation states during the bonding process, hydrogen bond formation can be postulated to consist of three steps. The first is identification: donor moieties and acceptor moieties seek each other in a chemical environment. The second is electron transfer: the electronic cloud of H approaches the donor with electronegativity to form a covalent bond. The third is interaction: after the two steps of preparation, the acceptors possess lone pair electrons and H equipped with an empty orbital must be oriented properly in the way that their contacts point toward each other to produce electrostatic attraction. Then, aggregation is shaped by multiple intermolecular hydrogen bonds. Therefore, when there is the existence of a great deal of protons in solution by introducing acid, donor with lone pair electrons readily attracts protons resulting in unbalanced charge distribution, which makes the molecule have stronger electrophilicity and electrostatic attraction to interact with the remaining negatively charged radicals in the form of hydrogen bonds. Herein, we report two molecular crystals with the protonation of alkalic amine groups in 3-aminobenzoic acid (1) and acidic hydroxy groups in (E)-4-hydroxy-3,5-dimethoxybenzaldehyde oxime (2, Scheme 1), and we obtained two Received: October 11, 2018 Revised: November 19, 2018 Published: December 3, 2018 A

DOI: 10.1021/acs.cgd.8b01532 Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design

Article

Scheme 1. Molecular Structure of Compounds 1 and 2 As Well As Complexes [1H]+·[Cl]− and [2H]+·[Cl]−

Figure 1. Connecting environment around (a) [1H]+ and (b) chloride ion in crystal [1H]+·[Cl]−. (c) The connection diagram of the 1D and 2D “stair-like” bond along the a-axis. (d) The stacking of 2D layers.

complexes [C 7 H 8 NO 2 ] + ·[Cl] − ([1H] + ·[Cl] − ) and [C9H12NO4]+·[Cl]− ([2H]+·[Cl]−). Protonation of the amine group has been found in many studies; for example, protonation of lysine in aqueous solution has caused a chemical shift in XPS,33 and protonation of the spin-crossover complex Fe(H2Bpz2)2(bipy-NH2) (H2Bpz2 = dihydrobis(1pyrazolyl)borate, bipy-NH2 = 4,4-diamino-2,2-bipyridine) with CF3SO3H has alerted the magnetism from paramagnetic to

spin crossover.34 The hydroxy moiety as proton binding site remains unreported. Confirmed by the analysis of single-crystal X-ray diffraction data of complexes [1H]+·[Cl]− and [2H]+· [Cl]−, these two distinctively different compounds (1 and 2) have been protonated by HCl to form the similar 1D “stairlike” ribbon consisting of four-member rings. For both complexes, the chloride ions bridged the protonated groups through intermolecular hydrogen bonds; however, the B



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connects to four chloride ions through three O−H···Cl (O···Cl distances of 2.729−3.037 Å, Table 1) hydrogen bonding contacts and one O···Cl halogen bonding contact (O···Cl distances of 2.861 Å) (Figure 2a), while for each chloride ion, it is located in the middle of a square consisting of four [2H]+ cations (Figure 2b). Hydroxy groups have played a dominant position in shaping interactions; each hydroxy group derived from the [2H]+ cation directly connects to three chloride ions through two O−H···Cl hydrogen bonding contacts and one O···Cl halogen bonding contact, affording a “stair-like” 1D infinite ribbon construction that is similar to [1H]+·[Cl]− where the [2H]+ cations are cross distributed in the 1D ribbon construction (Figure 2c). Interestingly, these 1D ribbon motifs are further connected into the “honeycomb-like” 3D framework along the crystallographic a-axis via O−H···Cl hydrogen bonding (O···Cl distances of 2.753 Å) contacts involving oxime groups and chloride ions (Figure 2d). It is intriguing that two [2H]+ cations with different molecule orientations connect to four chloride ions and display a conterminous “lantern-like” motif along the crystallographic b-axis, while the two methyl moieties are similar to lantern spikes and the rest of the [2H]+ cations act as the lantern body. In the crystal, the conterminous “lantern-like” motifs interact with each other through C−H···O hydrogen bonding contacts (C···O distances of 3.102 Å) (Figure 2e). Comparison between the Four-Membered Squares. Complexes [1H]+·[Cl]− and [2H]+·[Cl]− were prepared by using a slow evaporation technique in solution crystallization via assembly of hydrochloric acid with 1 and 2, respectively, affording different molecular lattices and stacking modes. In the crystal structure, chloride ions connect to protonated amino groups and hydroxy groups via intermolecular hydrogen bonding contacts into a different crystal system. However, it is notable that the different intermolecular interactions including hydrogen bonding and halogen bonding contacts offer semblable 1D infinite ribbon models; the side lengths and angle of the four-membered squares are found to be 3.163 Å, 3.177 Å, and 93.63° and 3.037 Å, 2.861 Å, and 86.37°, respectively (Figure 3). As a consequence, the acidic hydroxy groups, which possess a stronger ability than alkalic amino groups for proton capture, form stronger charge supported [H−O−H]+ hydrogen bonds with a short O···Cl distance of 2.729 Å, which is quite rare in the crystalline solid state. In addition, it should be noted that great differences exist in the shape of the 3D architecture. As for [1H]+·[Cl]−, the adjacent 1D ribbon structures are connected into 2D layer structures, and the 2D layer structures are further connected into 3D stacking structures. For [2H]+·[Cl]−, the adjacent 1D ribbon structures are directly connected into the 3D stacking framework. It is thought that the structure of the molecular crystal may be regulated through protonated acidic and alkalic groups in aromatic compounds. Hirshfeld Surface Analysis. To further compare the differences of protonation of the acidic and alkalic groups with hydrochloric acid, molecular calculations for [1H]+ and [2H]+ have been performed. Hirshfeld surface analysis36−39 directly concerns a given molecular surrounding; it can enable a rapid visual comparison with respect to the role of independent molecules in the crystal structure and the characteristics of packing motif. 3D dnorm values are constructed by partitioning the space within a crystal structure mapped onto a red−blue− white surface: red regions represent a short de range with closer contacts; blue regions represent a long de range with the longer

protonated acidic groups have shown much closer and stronger intermolecular interactions than the alkalic groups. These differences in intermolecular interactions induced by protonation are also confirmed by investigation of Hirshfeld surfaces, 2D fingerprint plots, and crystal void calculations, which have suggested 21.4% and 17.5% interactions around protonated acidic and alkalic groups, respectively. Our study contributes to a detailed knowledge of the effect of protonation upon aggregation structure and intermolecular interactions, which will open new avenues for the rational design and control of molecular crystal with protonated functional groups.

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RESULTS AND DISCUSSION Crystal Structure of Complex [1H]+·[Cl]−. The crystal structure of [1H]+·[Cl]− was first reported in 1973;35 however, the crystal structure presented in this work is more precise than the reported one, especially for the geometry of N−H···Cl hydrogen bond squares (Figure S1). A colorless single crystal of [1H]+·[Cl]− crystallizes in a triclinic space P1̅ (Table S1). As shown in Figure 1a,b, each [1H]+ cation connects to three chloride ions through strong N−H···Cl hydrogen bonding contacts (N···Cl distances of 3.163−3.188 Å, Table 1) and vice Table 1. Geometrical Parameters for Hydrogen Bonding Contacts in Complexes [1H]+·[Cl]− and [2H]+·[Cl]− D−H···A

D−H (Å)

N1−H1···Cl1 N1−H2···Cl2 N1−H3···Cl3 O1−H4···O2

0.890 0.890 0.890 0.821

O1−H1···Cl1 O1−H2···Cl2 O3−H3···Cl3

0.930 0.930 0.820

H···A (Å) [1H]+·[Cl]− 2.316 2.332 2.282 1.836 [2H]+·[Cl]− 1.982 2.349 2.018

D···A (Å)

∠D−H···A (deg)

3.188 3.177 3.163 2.643

166.38 158.46 170.13 167.16

2.729 3.037 2.753

136.08 130.57 148.87

versa for each chloride ion. The [1H]+ cations acting as a tridentate ligand via one alkalic amino group and three chloride ions bridge adjacent nitrogen atoms with a distance of 5.853 Å. Interestingly, the chloride ions act as connectors that interact with [1H]+ cations, forming a “stair-like” onedimensional (1D) ribbon that was constructed through N− H···Cl hydrogen bonding contacts along the crystallographic aaxis (Figure 1c). In addition, two crystallographic different adjacent planar phenyl moieties involved in the single chain are nearly parallel with the same molecular orientation, whereas planar phenyl is distributed in the two sides of 1D ribbon construction with opposite orientation, with the centroids− centroids distance between adjacent phenyl of 5.853 and 8.494 Å, respectively (Figure S3). Note that these adjacent 1D “stairlike” ribbons were further connected into two-dimensional (2D) layers via stronger O−H···O hydrogen bonding contacts between carboxyl groups (O···O distance of 2.643 Å). The 2D layers interact with each other through face-to-face π−π interaction with an interlayer distance of 3.36 Å, providing an interesting three-dimensional (3D) framework (Figure 2d). Crystal Structure of [2H]+·[Cl]−. Similar to [1H]+·[Cl]−, where the alkalic amino groups have been protonated, for the first time, the acidic hydroxy groups in compound 2 have been protonated, which give birth to complex [2H]+·[Cl]−. The latter crystallizes in monoclinic space group P2(1)/c (Table S1). Different from complex [1H]+·[Cl]−, each [2H]+ cation C



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Figure 2. Connecting environment around (a) [2H]+ and (b) chloride ion in crystal [2H]+·[Cl]−. (c) The connection motif between [2H]+ cations. (d) The formation of “honeycomb-like” aggregation structures along the a-axis. (e) The 3D “lantern-like” framework along the b-axis.

Figure 3. Comparison between the 1D infinite ribbon models of (a) [1H]+·[Cl]− and (c) [2H]+·[Cl]−. The bridging geometry of chloride ions with (b) amino groups and (d) hydroxy groups of the fourmembered squares.

contacts; white regions correspond to the distance of contact which is equal to vdW separation. Hirshfeld surfaces of [1H]+ and [2H]+ reflected in the 3D dnorm map (Figure 4a,b), curvedness, and shape index (Figures S4 and S5) have been investigated. For [1H]+, the four large deep-red round regions represent significant hydrogen bonding contacts. The symmetrical deep-red round regions labeled 1a on the upper left of the 3D dnorm surfaces correspond to strong N−H···Cl hydrogen

Figure 4. (a, b) Comparison between the 3D dnorm surfaces, (c, d) crystal voids, and (e, f) percentage contribution from individual intermolecular interactions to the total Hirshfeld surfaces of [1H]+ (left) and [2H]+ (right), respectively.

D



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Figure 5. Comparison between the 2D fingerprint plots for [1H]+ (upper) and [2H]+ (lower).

[Cl]−, and scatter points in the middle of fingerprint plots at higher de and di values for [2H]+·[Cl]−. On the contrary, the contribution of H···H interactions is dramatically increased from 27.9% to 37.6% in the similar form of diffuse points in the middle of the surfaces, at around de = 1 Å to di = 1 Å for [1H]+·[Cl]− and de = 1.2 Å to di = 1.3 Å for [2H]+·[Cl]−. Remarkably, C···Cl interactions (Figure S6) only exist in [1H]+·[Cl]− at the region of de = 2.1 Å to di = 2.0 Å, corresponding to at least a contribution of 0.5%. O···Cl interactions are only discovered in [2H]+·[Cl]− at the region of de = 1.6 Å to di = 1.4 Å, which can be attributed to the presence of halogen bonding contacts observed on 3D dnorm surfaces (Figure 4b) and with a contribution of 3.0%. Apart from the above, the other molecular interactions are summarized in Table S2 and Figure S7. Furthermore, as shown in Figure 4c,d, crystal voids undergo an increase, from V = 29.69 Å3 and A = 137.6 7 Å2 to V = 115.14 Å3 and A = 380.18 Å2 for [1H]+·[Cl]− and [2H]+·[Cl]−, owing to the existence of stronger steric bulk between methyl groups of [2H]+. Hence, there are distinctive differences between the effect of protonation on acidic and alkalic groups, despite the formation of similar 1D infinite ribbon models.

bonding contacts comprising distinctive 1D ribbon motif. The paralleled deep-red round regions labeled 1b on the upper right of 3D dnorm surfaces are attributed to O−H···O hydrogen bonding contacts, resulting from intermolecular interactions between adjacent cations of [1H]+ connecting 1D ribbons into 2D layers. Weak C−H···Cl hydrogen bonding contacts are displayed as small red round regions labeled 1c on the bottom left of the 3D dnorm surfaces, while for [2H]+, the large deepred round regions all represent O−H···Cl hydrogen bonding contacts, which are reflected in the upper and bottom left of 3D dnorm surfaces, respectively. The upper deep-red round regions labeled 2a are associated with O−H···Cl as a necessary connection of forming the ribbon model involving the hydroxy group and chlorine ions, and the other labeled 2b is due to molecular interactions contributing to the connection of the interchain involving the oxime group and chlorine ions. The small red round regions labeled 2c and 2d correspond to weaker hydrogen bonding contacts; C−H···N hydrogen bonding contacts are reflected on the right and C−H···O hydrogen bonding contacts are reflected on the bottom right of 3D dnorm surfaces, respectively. The O···Cl halogen bonding contacts are also presented as small red round regions labeled 2e on the upper left of 3D dnorm surfaces, with O atom as the donor and Cl atom as the acceptor. At last, the H···H interactions are mapped as blue regions dispersing most of the 3D dnorm surfaces of [1H]+ and [2H]+, which are in agreement with the crystal structures. 2D fingerprint plots are transformed from 3D dnorm surfaces, which summarize quantitatively the characteristics of intermolecular contacts and indicate some significant differences of protonation on alkalic and acidic groups. As shown in Figure 5, for [1H]+·[Cl]−, H···Cl interactions appear as a single sharp at de = 1.4 Å to di = 0.8 Å, which have a significant contribution to 3D dnorm surfaces with fraction of 17% (Figure 4e). A notable pair of wings at de = 1.8 Å to di = 1.4 Å and de = 1.4 Å to di = 1.8 Å are associated with C···H interactions, which further strengthen the stability of interchains, with a high contribution of 22%. For [2H]+·[Cl]−, the proportion of H··· Cl interactions and C···H interactions are deceased to 16.4% and 20.5% (Figure 4f), respectively, accompanying the lower de and di values. The proportion of O···H interactions also declines greatly from 24.1% to 15.1%, which is indicated by the different shapes reflected in the fingerprint plots, a pair of spikes with equal length at low de and di values for [1H]+·

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CONCLUSION In summary, semblable intermolecular interactions are realized through protonation of different functional groups derived from different molecules. By using HCl, on the one hand, the alkalic amino groups have been protonated to display 1D “stair-like” ribbon models via formation of N−H···Cl intermolecular hydrogen bonding contacts. On the other hand, the acidic hydroxy moieties also have been protonated into similar 1D ribbon models through stronger O−H···C intermolecular hydrogen bonding contacts. Note that the protonated acidic groups, which have rarely been previously studied, have shown much closer and stronger intermolecular interactions than the alkalic groups. Meanwhile, 3D Hirshfeld surfaces, 2D fingerprint plots, and crystal void calculation have provided a deepening understanding of the effect of protonation on the intermolecular interactions, which have suggested 21.4% and 17.5% interactions around protonated acidic and alkalic groups, respectively. The present results not only provide a new insight into understanding of the effect of protonation but also open new avenues for rational design and E



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ACKNOWLEDGMENTS This research was supported by the Natural Science Foundation of China (Grant No. 21701023), Natural Science Foundation of Jiangsu Province (Grant No. BK20170660), Fundamental Research Funds for the Central Universities (No. 3207048427), and PAPD of Jiangsu Higher Education Institutions.

control of molecular crystals with protonated functional groups.

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EXPERIMENTAL SECTION

Materials. All reagents were available commercially and directly used without further purification. (E)-4-Hydroxy-3,5-dimethoxybenzaldehyde oxime, 3-aminobenzoic acid (98%), and polyaniline (98%) were purchased from MACLIN, and others were purchased from Nanjing Wanqing Chemical Glassware Instrument Co., Ltd. All of these were used as received. Synthesis of [1H]+·[Cl]− and [2H]+·[Cl]−. The crystal obtained was conducted by using a slow evaporation technique in solution crystallization. 3-Aminobenzoic acid (2 mmol) in deionized water (55 mL) was added dropwise to hydrochloric solution under continuous stirring. After stirring for 1 h, the resulting solution was filtered off before being left to evaporate slowly at room temperature. [2H]+· [Cl]− is synthesized in the light of a similar method. X-ray Crystallographic Study. The single-crystal X-ray diffraction data of complexes 1 and 2 were collected at 298 K with graphite-monochromated Mo Kα radiation (λ = 0.071073); a RigakuSCXmini diffractometer with the ω-scan technique was used. The lattice parameters were integrated using vector analysis and refined from the diffraction matrix; the absorption correction was carried out by using a Bruker SADABS program with the multiscan method. The structures were solved by full-matrix least-squares methods on all F2 data and using the SHELX-2014 and SHELXL2014 program for structure solution and structure refinement, respectively. The crystallographic data, data collection, and refinement parameters for [1H]+·[Cl]− and [2H]+·[Cl]− are summarized in Table S1. The molecular graphics were prepared by a mercury program. CCDC Nos. 1856004 for [1H]+·[Cl]− and 1856005 for [2H]+·[Cl]− contain the supplementary crystallographic data.

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REFERENCES

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.cgd.8b01532. Comparison between the 1D infinite ribbon models of 3-aminobenzoic acid hydrochloride and [1H]+·[Cl]−; crystal data and structure refinement details and aditional crystal structures for [1H]+·[Cl]− and [2H]+· [Cl]−; comparison between curvedness, di, de, shape index, and summary of the percentage contributions to the Hirshfeld surfaces for [1H]+ and [2H]+ (PDF) Accession Codes

CCDC 1856004−1856005 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 Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: + 44 1223 336033.

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AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected] (Y.-H.L.). *E-mail: [email protected] (B.-W.S.). ORCID

Yang-Hui Luo: 0000-0002-5555-2510 Bai-Wang Sun: 0000-0001-8724-0055 Notes

The authors declare no competing financial interest. F



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