Synthon Modularity in 4-HydroxybenzamideâDicarboxylic Acid

Article pubs.acs.org/crystal

Synthon Modularity in 4‑Hydroxybenzamide−Dicarboxylic Acid Cocrystals Srinu Tothadi and Gautam R. Desiraju* Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560 012, India S Supporting Information *

ABSTRACT: A family of 4-hydroxybenzamide−dicarboxylic acid cocrystals has been designed and subsequently isolated and characterized. The design strategy follows from an understanding of synthon modularity in crystal structures of monocomponent crystals such as γ-quinol, 4,4′-biphenol and 4-hydroxybenzoic acid. These monocomponent structures contain infinite O−H···O−H···O−H··· cooperative synthons linked with molecular connectors such as phenyl and biphenyl, and supramolecular connectors such as the acid dimer in 4-hydroxybenzoic acid. The cocrystal design was influenced by the anticipation that dicarboxylic acids can form a supramolecular connector mediated by acid−amide synthons with 4-hydroxybenzamide, which can then form the phenol O−H···O−H···O−H··· infinite synthon. Effectively, the acid−amide and phenol synthons are insulated. The short axis of such a structure will be around 5.12 Å and this is borne out in 2:1 cocrystals of 4-hydroxybenzamide with oxalic, succinic, fumaric, glutaric (two forms) and pimelic acids. Hydrated variations of this structure type are seen in the cocrystals obtained with adipic and sebacic acids.

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INTRODUCTION Insulation of molecular functionality1 is a key element in the use of synthon theory2 to design increasingly complex structures. Given a molecular framework with functionalities M1, M2, M3 .... Mn, one would ideally like to consistently and preferentially obtain synthons such as, say, {M 1···M5} and {M2···M3}, with adventitious synthons such as, say, {M2···M5}, being avoided.1,3 Given the current (and expected) preference for the use of hydrogen bonding4 as the major design interaction in crystal engineering,5 there is an inevitable occurrence of several competing hydrogen bond donors and acceptors in any system that attempts to obtain crystal structures of even moderate complexity.6 Structural interference, in other words, the appearance of extraneous synthons, is therefore a real possibility.7 Accordingly, the identification of new hydrogen bonded systems in which a high degree of structural fidelity is obtained in a whole series of crystal structures is valuable for the systematic development of design strategies.8 Well insulated synthons lead to modular crystal structures, and in order to obtain synthon modularity,9 one needs a full knowledge of existing crystal structures and of the intermolecular interactions present in them. This knowledge may be used in the design or synthesis of a new structure or structures. A proper understanding of the way in which functional groups behave in the presence of other (competing) functional groups and a clear idea about the hydrogen bond donors and acceptors in the compound is almost implied in any rational design of a desired crystal packing. Multicomponent molecular crystals (cocrystals)10 provide a ready template to test new design strategies11 because they offer the possibility of large chemical variety in terms of functional groups without the need for laborious molecular synthesis. The present paper describes a series © XXXX American Chemical Society

of cocrystals of 4-hydroxybenzamide. It may be mentioned that this compound has been not well studied in the context of crystal engineering.5 Just nine hits may be seen in the CSD corresponding to the pure compound, a hydrate and five cocrystals.12

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EXPERIMENTAL SECTION

Single Crystal X-ray Diffraction. Except one cocrystal, single crystal X-ray data for all cocrystals were collected on a Rigaku Mercury375/M CCD (XtaLAB mini) diffractometer using graphite monochromated Mo−Kα radiation at 150 K. The data were processed with the Rigaku Crystal clear software.13 For one cocrystal, data were collected at ambient temperature (CrysAlis CCD Xcalibur, Eos (Nova), Oxford Diffractometer).14 Structure solution and refinements were executed using SHELX-9715a using the WinGX15b suite of programs. Refinement of coordinates and anisotropic thermal parameters of nonhydrogen atoms were performed with the full-matrix least-squares method. The different treatment of H in D−H in any structure depends on the data quality. All hydrogen atoms in NH2 are located from difference Fourier maps, and most of hydrogen atoms in OH are located from difference Fourier maps. Now with respect to concerns about the hydrogen atoms in CH, if the data are good, they are located from difference Fourier map. If they are some problems in the C−H distance then there are calculated using riding model. PLATON16 software was used to prepare material for publication, and Mercury17 version 3.0 was utilized for molecular representations and packing diagrams. Crystallization of Samples. 4-Hydroxybenzamide/Oxalic Acid 2:1 Cocrystal (1). 4-Hydroxybenzamide and oxalic acid were taken in a 2:1 mmol ratio and ground in a mortar with a pestle after adding 2−3 Received: September 20, 2012 Revised: October 19, 2012

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dx.doi.org/10.1021/cg3013766 | Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design

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Figure 1. O−H···O−H···O−H··· cooperative hydrogen bonding in (a) γ-quinol; (b) 4,4′-biphenol; (c) 2,2′,6,6′-tetramethyl-4,4′-terphenyldiol; (d) 4-hydroxybenzoic acid. drops of EtOH (solvent drop grinding).18 The ground sample was dissolved in a minimum amount of i-PrOH. Good quality crystals, suitable for diffraction, were obtained after one week.

4-Hydroxybenzamide/Succinic Acid 2:1 Cocrystal (2). 4-Hydroxybenzamide and succinic acid were taken in a 2:1 mmol ratio and ground with 2−3 drops of EtOH. The ground sample was dissolved in a B



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Figure 2. (a) Crystal structure of 4-hydroxybenzamide. Notice the infinite zigzag supramolecular N−H··· O−H··· OC synthon. (b) Second polymorph of 4-hydroxybenzamide. Notice the fused distorted ladder synthon made up of N−H···O and N−H···O hydrogen bonds. On either side, there are O−H···O−H···O−H··· infinite cooperative synthons. 4-Hydroxybenzamide/Pimelic Acid 2:1 Cocrystal (7). 4-Hydroxybenzamide and pimelic acid were taken in a 2:1 mmol ratio and ground after adding 2−3 drops of EtOH. The ground sample was dissolved in a minimum amount of MeOH. Good quality crystals, suitable for diffraction, were obtained after four days. 4-Hydroxybenzamide/Sebacic Acid 2:1 Cocrystal Dihydrate (8). 4Hydroxybenzamide and sebacic acid were taken in a 2:1 mmol ratio and ground after adding 2−3 drops of EtOH. The ground sample was dissolved in 1:1 CHCl3−MeOH. Good quality crystals, suitable for diffraction, were obtained after four days. 4-Hydroxybenzamide/Fumaric Acid 2:1 Cocrystal Dihydrate (9). 4Hydroxybenzamide and fumaric acid were taken in a 2:1 mmol ratio and ground after adding 2−3 drops of EtOH. The ground sample was dissolved in THF. Good quality crystals, suitable for diffraction, were obtained after five days.

minimum amount of MeOH. Diffraction quality crystals were obtained after five days. 4-Hydroxybenzamide/Fumaric Acid 2:1 Cocrystal (3). 4-Hydroxybenzamide and fumaric acid were taken in a 2:1 mmol ratio and ground after adding 2−3 drops of EtOH. The ground sample was dissolved in a minimum amount of EtOAc. Good quality crystals were obtained after five days. 4-Hydroxybenzamide/Glutaric Acid 2:1 Cocrystal Form I (4). 4Hydroxybenzamide and glutaric acid were taken in a 2:1 mmol ratio and ground after adding 2−3 drops of EtOH. The ground sample was dissolved in a minimum amount of 1,4-dioxane. Good quality crystals, suitable for diffraction, were obtained after one week. 4-Hydroxybenzamide/Glutaric Acid 2:1 Cocrystal Form II (5). 4Hydroxybenzamide and glutaric acid were taken in a 2:1 mmol ratio and ground after adding 2−3 drops of EtOH. The ground sample was dissolved in a minimum amount of EtOAc. Good quality crystals, suitable for diffraction, were obtained after five days. 4-Hydroxybenzamide/Adipic Acid 2:1 Cocrystal Dihydrate (6). 4Hydroxybenzamide and adipic acid were taken in a 2:1 mmol ratio and ground after adding 2−3 drops of EtOH. The ground sample was dissolved in a minimum amount of THF. Good quality crystals, suitable for diffraction, were obtained after four days.

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RESULTS AND DISCUSSION Design Strategy. The use of 4-hydroxybenzamide in the design strategy was made after an initial consideration of the crystal structures of γ-quinol,19 4,4′-biphenol20 and 4-hydroxybenzoic acid.21 In each of these homologous structures22 (schematics in Figure 1) there is an infinite cooperative pattern of C



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Figure 3. Design strategy for cocrystal. Acid−amide heterosynthon in cocrystals facilitates the retention of O−H···O−H···O−H··· hydrogen bonding. Notice the repeat distance of ∼5.12 Å in this packing.

Figure 4. Design strategy. Schematic of ladder synthon in (a) Monocomponent diphenol crystal; (b) acid-amide cocrystals. Color coding: Dark blue, ladder length, O−H···O−H···O−H synthon; purple, ladder rung, aromatic ring; Green, ladder rung, diacid. See Figure 3.

Figure 5. O−H···O−H···O−H··· Synthon and acid−amide heterosynthon in 4-hydroxybenzamide/oxalic acid cocrystal.

O−H···O−H···O−H··· hydrogen bonds, and the short axis of such structures are around 5.12 Å. In γ-quinol, these hydrogen

bond patterns are connected with 1,4-disubstituted phenyl rings in a ladder-like manner. In 4,4′-biphenol the rungs are biphenyl D


(C7H7NO2)·0.5 (C4H6O4)

(C7H7NO2)·0.5 (C2H2O4)

182.15

formula

formula weight

5.120(7)

23.07(3)

90

98.82(4)

90

a (Å)

b (Å)

c (Å)

α (°)

β (°)

γ (°)

E

1515

observed ref (I > 2σ(I))

a

892261

1.10

0.1282

0.0420

1896

2015

8846

150

0.118

412.0

1.482

4

878.9(8)

90

113.321(18)

90

21.046(10)

5.118(3)

3

892262

1.13

0.1228

0.0389

1820

1941

8514

150

0.120

408.0

1.505

4

861.3(2)

90

114.787(8)

90

20.630(3)

5.2395(9)

8.7771(14)

P21/c

monoclinic

195.10

(C7H7NO2)·0.5 (C4H4O4)

4HBZ:FA

4

892263

1.07

0.2231

0.0656

1569

2178

9611

150

0.113

856.0

1.429

8

1887.7(18)

90

121.71(3)

90

25.609(12)

5.077(2)

17.067(12)

C2/c

monoclinic

203.10

(C7H7 NO2)·0.5 (C5H8O4)

4HBZ:GA−I

5

892264

1.09

0.2287

0.0849

2908

4460

15658

150

0.110

1712.0

1.392

8

3875.7(14)

90

92.33(3)

90

33.690(7)

5.170(1)

22.270(5)

C2/c

monoclinic

406.21

2(C7H7NO2)·(C5H8O4)

4HBZ:GA−II

6

7

892265

1.09

0.1531

0.0481

2170

2515

5813

150

0.112

242.0

1.393

2

543.7(14)

100.638(8)

90.332(13)

115.05(2)

11.747(18)

10.102(16)

5.169(7)

892266

1.05

0.2505

0.0710

1115

2577

9946

293

0.106

920.0

1.367

8

2109.8(5)

90

102.752(17)

90

24.296(3)

5.0774(6)

17.535(3)

monoclinic C2/c

triclinic

217.12

(C7H7NO2)·0.5 (C7H12O4)

4HBZ:PA

P1̅

228.22

(C7H7NO2)·0.5 (C6H10O4)·(H2O)

4HBZ:AA: H2O

8

892267

1.14

0.1945

0.0627

2179

2989

13219

150

0.102

548.0

1.310

4

1298.5(5)

90

115.675(13)

90

23.609(5)

5.0649(10)

12.049(3)

P21/c

monoclinic

256.13

(C7 H7NO2)·0.5 (C10H18O4)·(H2O)

4HBZ:SBA:H2O

Note: 4-Hydroxybenzamide (4HBZ), oxalic acid (OA), succinic acid (SA), fumaric acid (FA), glutaric acid (GA), adipic acid (AA), pimelic acid (PA), sebacic acid (SBA).

892260

1822

unique ref.

1.15

7647

total ref.

CCDC no.

150

temp (K)

S

0.126

μ (mm)

0.0513

380.0

F(000)

0.1865

1.547

ρ calc (g cm−3)

wR2

4

R

781.7(18)

V (Å )

Z

3

6.697(9)

space group

8.886(5)

monoclinic

P21/c

monoclinic

P21/c

crystal system

196.18

2

4HBZ:SA

1

4HBZ:OA

Table 1. Crystallographic Data and Structure Refinement Parametersa 9

898058

0.965

0.1177

0.0450

1599

2154

5004

150

0.119

224.0

1.440

2

491.6(9)

97.80(4)

108.96(2)

97.40(4)

10.452(10)

7.257(8)

7.038(8)

P1̅

triclinic

213.10

(C7H7NO2)·0.5 (C4 H4 O4)·(H2O)

4HBZ:FA:H2O

Crystal Growth & Design Article



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Figure 6. O−H···O−H···O−H··· Synthon and acid−amide heterosynthon in 4-hydroxybenzamide/succinic acid cocrystal.

Figure 7. (a) 4-Hydroxybenzamide/fumaric acid cocrystal. Notice that the structure is analogous to 4-hydroxybenzamide/succinic acid (Figure 6), illustrating −CHCH− and −CH2−CH2− homology. (b) Retention of acid−amide synthon in 4-hydroxybenzamide/fumaric acid hydrate. The phenol OH groups form hydrogen bonded cyclic tetramers with water.

can one restore the cooperative synthon by making an amide−acid cocrystal?25 It is well-known that acids and amides form cocrystals mediated by the acid−amide heterosynthon.26 Formation of such a synthon would free the phenol OH group in 4-hydroxybenzamide, enabling it to form the cooperative O−H···O−H···O−H··· pattern seen in 4-hydroxybenzoic acid and elsewhere (Figure 3). Figure 4 illustrates the strategy in the form of a cartoon. The structures of the diphenols and of the 4-hydroxybenzamide cocrystals are shown as ladders. But the rungs in the cocrystals are supramolecular connectors while those in the diphenols are molecular in nature. In an interesting aside, it was observed (during the course of the present study) that 4-hydroxybenzamide actually forms a second polymorphic structure in which the O−H···O−H···O− H··· infinite synthon is present.27 This unusual structure was obtained during a cocrystallization experiment (MeOH) involving 4-hydroxybenzamide and 2-picolinic acid, and it was

fragments. 2,2′,6,6′-Tetramethyl-4,4′-terphenyldiol also has a similar packing with the corresponding terphenyl linker (Figure 1).23 In 4-hydroxybenzoic acid, the linkages are “benzoic acid dimers”. Note the modularity of this last structure. This particular acid is prone to synthon polymorphism,6b,24 and the possibility of Ar−O− H···OC hydrogen bonding cannot be ruled out. Therefore, it is noteworthy that the phenol hydroxyl group does not interfere with the formation of the carboxyl dimer. However, this type of insulation, which allows for the formation of both O−H···O−H···O−H··· and carboxyl dimer synthons in the same structure, is not observed in the crystal structure of the related 4-hydroxybenzamide; here, the hydroxyl group donates a hydrogen bond to the amide carbonyl thereby disrupting the formation of the corresponding amide homodimer synthon (Figure 2). Obviously, there is no cooperative O−H···O−H···O−H··· synthon here as in the above-mentioned phenols in Figure 1. This observation leads to the design strategy: F



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Figure 8. (a) O−H···O−H···O−H··· Synthon and acid−amide heterosynthon in 4-hydroxybenzamide/glutaric acid cocrystal (form I). (b) Synthon polymorph of 4-hydroxybenzamide/glutaric acid cocrystal (form II). Notice the cooperative O−H···O−H···O−H··· synthon on one side of the pattern only.

4-Hydroxybenzamide/Oxalic Acid (2:1) (1). The structure takes the P21/c space group with one molecule of the amide and 0.5 molecule of the acid in the asymmetric unit (Z″ = 1.5).33 The acid−amide heterosynthon is observed (Figure 5) and the acid molecules effectively link the 4-hydroxybenzamide molecules. The O−H···O−H···O−H··· synthon is formed on either side and the structure takes a ladder-like appearance.34 Characteristic of this structure type is the unique axis value of 5.12 Å (Table 1) which is the distance between the first and the third phenol along the O−H···O−H···O−H···synthon direction. 4-Hydroxybenzamide/Succinic Acid (2:1), (2). The structure is very similar to that of cocrystal 1 (Figure 6). The space group is P21/c with Z″ = 1.5. The b-axis value is 5.12 Å. 4-Hydroxybenzamide/Fumaric Acid (2:1), (3). Notice the similarity to cocrystal 2 (Figures 6 and 7a).35 This structure illustrates the close homology in structures that differ in terms of −CH2−CH2− versus −CHCH− replacement.6a36, These fragments are good mimics for one another. The design strategy is confirmed. The short axis is 5.24 Å. Also obtained is a monohydrate wherein the diacid−amide synthon is retained, but the phenol OH groups form hydrogen bonded cyclic tetramers with water (Figure 7b).37 This structure may be compared with the hydrates obtained with adipic and sebacic acids, described later. 4-Hydroxybenzamide/Glutaric Acid Form I (2:1), (4). The space group is C2/c with Z″ = 1.5 (Figure 8a). We note that the formation of acid−amide heterosynthons is possible on both sides of the acid molecules although glutaric acid is an oddcarbon dicarboxylic acid, in other words there does not seem to be any noticeable even−odd effect. The b-axis is 5.08 Å.

obtained just once, even in these experiments. In this case (Figure 2b), the formation of the cooperative O−H···O−H···O− H··· synthon is perhaps facilitated by fortuitous size matching with an uncommon (36 CSD occurrences) zigzag amide−amide synthon.28 The structure of the original polymorph (without the O−H···O−H···O−H··· synthon) is, however, more often obtained especially when the pure amide is crystallized. In any case, no structure was ever obtained that contains both the O−H···O− H···O−H··· synthon and the classical amide−amide homosynthon,29 thereby justifying our design strategy (Figures 3 and 4). The final aspect of the design strategy is the choice of the coformer acids. By analogy with γ-quinol, 4,4′-biphenol and 2,2′,6,6′-tetramethyl-4,4′-terphenyldiol, we selected both even and odd dicarboxylic acids up to C10, in the anticipation of symmetrical hydrogen bonded patterns (Figure 3). Cocrystals were not obtained with malonic, azelaic and suberic acids; rather a hemihydrate30 and a dioxane solvate of 4-hydroxybenzamide31 were obtained in several experiments. A cocrystal with maleic acid32 was obtained, but this does not correspond to the structure envisaged in Figure 3. Cocrystals with oxalic, succinic, fumaric, glutaric (form I only), adipic, pimelic and sebacic acids broadly conform to our design strategy and are described below. Glutaric acid forms a polymorphic cocrystal with 4-hydroxybenzamide (form II) which, in part, resembles the target structure in Figure 3. As a matter of clarification, the even-carbon diacids (oxalic, succinic, fumaric, adipic, sebacic) always lie on an inversion center. There are two polymorphs of 4- hydroxybenzamide glutaric acid cocrystals. In form I, the acid molecule is bisected by a 2-fold axis (C2/c). In form II, the acid molecule occupies a general position. G



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Figure 9. Acid−amide heterosynthon in 4-hydroxybenzamide/adipic acid dihydrate. Notice the tetramer hydrogen bond pattern with OH groups.

Figure 10. O−H···O−H···O−H··· Synthon and acid−amide heterosynthon in 4-hydroxybenzamide/pimelic acid cocrystal.

Figure 11. Water is incorporated in the O−H···O−H···O−H··· infinite cooperative synthon in 4-hydroxybenzamide/sebacic acid dihydrate cocrystal. The acid−amide heterosynthon is retained.

4-Hydroxybenzamide/Pimelic Acid (2:1), (7). The crystals were very small and of marginal quality; the R-factor is correspondingly high, but the main features of the packing are clear enough and show that the design strategy has been successful (Figure 10). The space group is C2/c with Z″ = 1.5. The short axis is 5.08 Å. 4-Hydroxybenzamide/Sebacic Acid Dihydrate, (8). While the stoichiometry is the same as in cocrystal 6, the packing conforms more nearly to the design strategy in that the water molecules merely insert themselves into the infinite phenol OH hydrogen bond pattern (Figure 11). The space group is P21/c with Z″ = 2.5 with the short axis being 5.07 Å. We note that in all the above cases, the acid−amide heterosynthon is formed. In most of the cases the phenol O−H···O− H···O−H··· synthon is observed in an undistorted fashion. The acid−amide synthon is indeed a favorable occurrence. A CSD38 analysis of crystal structures containing acid−acid,

4-Hydroxybenzamide/Glutaric Acid Form II (2:1), (5). This synthon polymorph of cocrystal 4 warrants attention. The space group is again C2/c space group but now Z″ = 3. This is apparent from Figure 8b which shows that the design strategy outlined by us is successful on only one side of the pattern O−H···O− H···O−H (D = 3.4 Å, d = 2.638 Å). On the other side there is a finite O−H···O−H···OC (D = 3.347 Å, d = 2.531 Å; D = 2.540 Å, d = 1.746 Å) synthon which is constituted with OH groups from phenol and carboxyl fragments, and amide carbonyl. This is a rare pattern with only 15 examples in the CSD. 4-Hydroxybenzamide/Adipic Acid Dihydrate (2:1:2), (6). The space group is P1̅ with Z″ = 2.5. The acid−amide heterosynthon is obtained as before but instead of an infinite O−H···O−H···O−H··· synthon from phenol OH groups, water interrupts the pattern and forms a complex hydrogen bonded sheet as shown in Figure 9. Broadly speaking, however, the design strategy seems to have been fulfilled. H



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Figure 12. Could one design the acid−amide cocrystal based on the second polymorph of 4-hydroxybenzamide?

amide−amide and acid−amide dimers shows that of a total of 15116 organic acids, the probability of formation of the acid−acid dimer is only 3190 (21%). Similarly, in the 3145 primary amides present, the amide homodimer is seen in 1022 structures (33%). However, in the 421 structures that contain both CO2H and CONH2 groups, the acid−amide synthon is seen as many as 162 times (38.5%) with the occurrence of the amide−amide and acid− acid synthons being 30% and 5% respectively. This is the basis for our prediction that cocrystals of 4-hydroxybenzamide with dicarboxylic acids will contain this heterosynthon.

It is also interesting to speculate as to whether our design strategy would have been altered if we had known about the polymorphic structure of 4-hydroxybenzamide earlier on in the course of this study. Figure 12 is a schematic of this structure (see also Figure 2b), and it is possible to conceive of a molecule of a dicarboxylic acid inserting between the amide functionalities to yield the desired pattern. However, it is much easier to conceive of the design strategy from the more commonly obtained structure of 4-hydroxybenzamide shown in Figure 2a. I



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CONCLUSIONS In this design strategy of an insulated cocrystal, synthon modularity has been exploited in the generation of a family of related structures of 2:1 cocrystals of 4-hydroxybenzamide with aliphatic diacids. The role of the diacid is to link amide molecules with acid−amide heterosynthons, and the “free” phenolic groups hydrogen bond in a manner that is reminiscent of pure dihydric phenols forming infinite cooperative O−H···O−H···O−H··· synthons. In both single component and multicomponent crystals, the monoclinic axis is ∼5.12 Å, a characteristic of the infinite synthon above.

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ASSOCIATED CONTENT

S Supporting Information *

ORTEP of all crystals are available free of charge via the Internet at http://pubs.acs.org.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Fax: (+91) 80-23602306. Telephone: (+91) 80-22933311. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS S.T. thanks UGC for a SRF. G.R.D. thanks the DST for the award of a J. C. Bose fellowship. We thank the Rigaku Corporation,Tokyo, for their support through a generous loan of a Rigaku Mercury 375R/M CCD (XtaLAB mini) diffractometer.

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REFERENCES

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