Polymorphism in a Sulfamethoxazole Derivative: Coexistence of Five

Subscriber access provided by UNIV OF NEBRASKA - LINCOLN

Communication

Polymorphism in a Sulfamethoxazole Derivative: Coexistence of Five Polymorphs in Methanol at Room Temperature Muhammad Nawaz Tahir, Zahid Shafiq, Hazoor Ahmad Shad, Zia ur Rehman, Abdul Karim, and Muhammad Moazzam Naseer Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.5b01126 • Publication Date (Web): 10 Sep 2015 Downloaded from http://pubs.acs.org on September 10, 2015

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

Crystal Growth & Design is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 18

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Crystal Growth & Design

Polymorphism in a Sulfamethoxazole Derivative: Coexistence of Five Polymorphs in Methanol at Room Temperature Muhammad Nawaz Tahir,† Zahid Shafiqδ, Hazoor Ahmad Shadǁ, Zia-ur-Rehman‡, Abdul Karimǁ and Muhammad Moazzam Naseer‡,* †

Department of Physics, University of Sargodha, Sargodha, Pakistan Institute of Chemical Sciences, Organic Chemistry Division, Bahauddin Zakariya University, Multan 60800, Pakistan ǁ Department of Chemistry, University of Sargodha, Sargodha, Pakistan ‡ Department of Chemistry, Quaid-i-Azam University, Islamabad 45320, Pakistan δ

ABSTRACT: N O

CHO OH +

H2N

HN S O O

RT

Methanol

1

A Schiff base derived from 2-hydroxy-1-naphthaldehyde and a well-known antibiotic sulfamethoxazole affords seven different conformational isomers which are present in five polymorphic forms in methanol solvent at room temperature. An exclusive preference for one of the four possible pairs of sulfonamide-sulphonimide and phenolimine-ketoenamine tautomeric structures has been observed in the crystal structures of these polymorphs. This represents the first example of coexistence of five polymorphs in solution for any of the known compounds so far. *

Corresponding author: Fax: +92 51 90642241. Tel.; +92 51 90642129; E-mail: [email protected] (M.M. Naseer)

1 ACS Paragon Plus Environment


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 2 of 18

Over the last many decades, polymorphism has been the subject of main concern due to its importance in medicinal chemistry and material science.1-12 Generally, the phenomena occur due to the possibility of various combinations of 13-15

interactions such as hydrogen bonds,

multiple intermolecular weak noncovalent

CH/π interactions,16-18 π/π interactions,19-21 which are

usually affected by nature of solvent,22-24 temperature,25-27 and other factors28-30 involved in the crystal-growth process. As a result, different polymorphs of the same molecule show different physical and chemical properties due to the different packing modes of the component molecules. So far, several theories have been proposed regarding the polymorph growth process. According to Ostwald’s law of stages,31 the crystallization of least stable polymorph takes place first, followed by its conversion to the relatively stable polymorph and this process continues until the formation of most stable polymorph is reached. Other theories include the nucleation theories; one of which involves the mechanism of homogenous nucealtion of crystal growth, states that different polymorphs can nucleate independently and can simultaneously be observed, leading to multiple polymorphic forms competing for crystallization.31 The other nucleation theory is relatively new and more recent, which states that the cross-nucleation between polymorphs is the possible mechanism of nucleation in polymorphic systems.32 According to this theory, the heterogeneous nucleation of one polymorph by another can take place without polymorphic inter-conversion and the newly formed polymorph can either be more or less thermodynamically stable than the initial one. The mechanism of this cross-nucleation theory is still observed in very few molecules that include D-mannitol, D-sorbitol32 and ROY.33 Despite the presence of above mentioned theories and plethora of literature, the polymorphism related crystal growth process still remains poorly understood. Herein, we present a unique example of coexistence of five crystalline polymorphs in methanol solvent at room temperature for a Schiff base derivative of sulfamethoxazole (1) which is a well-known member of sulfonamide family. Interestingly, the parent sulfamethaoxazole exist in four different polymorphic forms (I, II, III, IV) and a hemihydrate,34,

35

all of which were

discovered in different conditions. Therefore, the compound 1 is an attractive candidate and may provide an ideal platform for complete understanding of crystal drowth process after in depth polymorphism studies due to its possible abilty of existing in four different tautomeric forms in both solution and in the solid state (Figure 1). This tautomeric phenomena namely sulfonamidesulphonimide tautomerism in sulphonamides and phenolimine-ketoenamine tautomerism in 2 ACS Paragon Plus Environment

Page 3 of 18

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Schiff base derivative of 2-hydroxy-1-naphthaldehyde independently has been the subject of many recent studies.36-38 O H N

O O S

O H N

N H phenolimine

O O S N

N O

Sulfonamide

ketoenamine

N O H

Sulfonimide

Figure 1. The possible sulfonamide-sulphonimide and phenolimine-ketoenamine tautomerism in 2-hydroxy-1-naphthaldehyde-sulfamethoxazole Schiff base (1)

The 2-hydroxy-1-naphthaldehyde-sulfamethoxazole Schiff base 1 was prepared by the straightforward condensation reaction of equimolar quantities of 2-hydroxy-1-naphthaldehyde and sulfamethoxazole in methanol under reflux conditions. The clear dark-red solution obtained after two hours of reflux was put at room temperature for crystallization; from which five different types of stable crystals were isolated after two days and analysed by X-ray crystallographic technique. The solid state structure of 1 was infact aimed to see its tautomeric preferences and explore its possible desmotrops in context to the tremendous biological and photophysical properties39, 40 of similar 2-hydroxy-1-naphthaldehyde Schiff bases. The structure of both polymorphic forms I and II was solved and refined in monoclinic crystal lattice with P21/c and C2/c space groups, respectively, whereas the other three forms, III, IV and V were obtained in triclinic crystal lattice with P¯1 space group (Table S1, supporting information). Both forms IV and V consists of two crystallographically independent molecules, whose geometric parameters are slightly different. The molecular structures of five polymorphs of 1 along with crystallographic numbering schemes are illustrated in Fig. S1, whereas the selected geometric parameters for all five polymorphs are presented in Table 1. Interestingly, in all the five polymorphic forms of 1, the ketoenamine and sulphonamide tautomers are observed (Figure 1). The assignment of ketoenamine structures for forms I-V in the solid state is supported by the short C-O bond lengths (1.264-1.281 Å) accompanied by long C-N bonds (1.315-1.325 Å). Similarly, the long C-N bond lengths (1.387-1.406 Å) as compared to the short C-N bonds of isoxazole ring (1.292-1.308 Å) indicates the preference of sulfonamide structure in all the discovered polymorphic forms (Table 1). Furthermore, the refined position of the hydrogen 3 ACS Paragon Plus Environment


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 4 of 18

atoms linked to the nitrogens in all five polymorphs also confirm the ketoenamine and sulphonamide tautomers. The central aryl ring and 2-hydroxy-1-naphthaldehyde are nearly planar in all the polymorphs. This planarity with slight distortion of two neighbouring aryl rings can be attributed to the extended conjugation and intramolecular hydrogen bonding between keto and enamine moiety [N-H···O 1.80-1.91 Å] (Table S2). The presence of nitrogen between sulfonyl and isoxazole ring is the main reason of conformational flexibility and polymorphism in 1. Due to its different levels of conjugation with the neighbouring systems, the nitrogen can regulate the electron density of the linking moities, leading to the different structural conformations as well as strength of intermolecular interactions (See Table 1 for selected bond lengths, bond angles and torsion angles). Table 1. Selected geometric parameters, bond lengths (Å), bond angles (°) and torsion angles (°) for polymorphic forms 1-V of 1 Polymorphs S1-N2 S2-N5 N2- C18 N5- C39 C18-N3 C39-N6 N1-C11 N4-C32 C11-C10 C32-C31 C10-C1 C31-C22 C1-O1 C22-O5 N2-S1-C15 N5-S2-C36 C18-N2-S1 C39-N5-S2 N2-S1-C15-C14 N5-S2-C36-C35 C15-S1- N2-C18 C36-S2-N5-C39 S1-N2-C18-N3 S2-N5-C39-N6 O1-C1-C10-C11 O5-C22-C31-C32

I 1.620(2) 1.396(3) 1.303(3) 1.317(3) 1.395(3) 1.431(4) 1.273(3) 107.14(10) 123.14(18) -86.4(2) -69.6(2) 151.99(19) -5.5(4) -

II 1.618(2) 1.401(3) 1.292(3) 1.322(3) 1.389(3) 1.433(4) 1.271(3) 104.98(12) 122.37(18) -53.3(2) -62.1(2) 146.0(2) 7.1(4) -

III 1.6301(19) 1.393(3) 1.293(3) 1.323(3) 1.383(3) 1.441(3) 1.277(3) 105.11(9) 121.81(14) -98.89(18) 65.72(18) -149.1(2) 1.8(3) -

IV A 1.629(2) 1.392(3) 1.307(3) 1.322(3) 1.386(4) 1.440(4) 1.281(3) 105.21(13) 125.4(2) 98.8(2) 60.5(3) 24.0(4) 0.8(4) -


V B 1.630(2) 1.406(3) 1.308(3) 1.315(3) 1.394(4) 1.438(4) 1.280(3) 106.51(13) 126.47(19) 100.5(2) 81.3(3) -21.5(4) -2.7(4)

A 1.6305(15) 1.391(2) 1.304(2) 1.315(2) 1.389(2) 1.440(3) 1.265(2) 106.41(8) 122.87(12) -118.09(15) 62.25(16) -150.89(15) 1.3(3) -

B 1.6213(16) 1.387(2) 1.297(2) 1.325(2) 1.388(2) 1.445(2) 1.264(2) 107.86(8) 125.60(12) -101.92(15) 75.49(16) -177.10(14) -3.0(2)

Page 5 of 18

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


C11-N1-C12-C17 C32-N5-C33-C38

176.7(2) -

-173.2(2) -

179.94(19) -

11.0(4) -

6.5(4)

-167.99(18) -

174.56(17)

As illustrated in Figure 2, eleven different types of hydrogen bond based cyclic motifs (type A-K) has been observed and interestingly only one of them (type A) is common in form I and II (See also Figure S2). The polymorphic form I has three of different types of these cyclic motifs, type A [C19-H19···O3 2.56 Å], type B [C17-H17···N3 2.58 Å, N2-H2A···O1 1.91 Å] and type C [C11-H11···O2 2.63Å], form II has three, type A [C19-H19···O3 2.60 Å], type D [C17H17···O2 2.40 Å, N2-H2A···O1 2.12 Å] and type E [C8-H8···O4 2.54Å, C13-H13···O4 Å], form III has two, type F [C14-H14···O3 2.49 Å] and type H [C8-H8···O4 2.62 Å, C8-H8···N3 2.75 Å, C13-H13···N3 2.68 Å], form IV has cyclic motif of type I [N4-H4A···O1 2.04 Å, C40H40···O1 2.69 Å] and form V has cyclic motif of type J [C32-H32···O3 2.68 Å, C34-H34···O3 2.58 Å] and type K [N2-H2A···O5 2.04 Å, C38-H38···N3 2.50 Å, C38-H38···O4 2.61 Å]. The hydrogen bonds other than these cyclic motifs, present in the packing of these polymorphic form I-V can be seen in Table S2. Another important interaction which has been found in the packing of all five polymorphic forms I-V is the π-π stacking of conjugated and planar aryl rings [C11···C11 3.41 Å in form I, C11···C11 3.27 Å in form II, C1···C12 3.276 Å in form III, C6···C13 3.41 Å in form IV-A, C26···C35 3.37 Å in form IV-B, C5···C14 3.45 Å in form V-A, C22···C33 3.28 Å in form V-B] (Figure 3). However, the nature, strength and mode of these interactions is different depending on the different conformations of the sulphonamide-isoxazole pendant. It is also pertinent to mention here, that two different types of π-π stacking has been observed in each crystal structures of form IV (stacking between form IV-A and form IV-A, and stacking between form IV-B and form IV-B) and form V (stacking between form V-A and form V-A, and stacking between form V-B and form V-B) (See Figure 3).



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 6 of 18

O O S

O

O N

H

H N

H

N H H

N O

O

O N

H HN

H

O

O

O S O

(type A)

O N

H

O

N

O S (type D)

O

O N

H

HN H

O (type C)

H

N

NH

S O

(type B)

O S O

N O

H

N H

S O

O S O

H N

H

NH

O O (type E) S O

O S O

O

H N

H

N H

H

O S

H

N O (type F)

H

O N O

N

H

O S O N H

O H

NH

NH

O

H

O S O

H N

S O

H

N O

O (type H)

O

N

(type I)

S O

N H

H O (type J)

O

S

O

N

H N O

O H N H

(type K)

Figure 2. Hydrogen bond driven cyclic motifs (homo- and heterosynthons) observed in polymorphic form I-V of 1.


Page 7 of 18

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(form I)

(form II)

(form III)

(form IV-B)

(form IV-A)

(form V-A)

(form V-B)

Figure 3. Showing π-π stacking interactions observed between conjugated, planar aryl rings and different conformations of sulphonamide-isoxazole pendant in polymorphic forms of 1. Consequently, as a result of different modes of hydrogen bonding, π-π stacking interactions and in the presence of a number of other weak CH-π and π-π interactions41-43, 7 ACS Paragon Plus Environment


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

different packing has been observed in all five polymorphic forms. As shown in Figure 4, the structure of form I is composed of various 1D-chains that are formed by the sideways arrangement of π-π stacked aryl rings. These chains are then connected to the neighboring chains by means of multiple non-covalent interaction to form a 2D-sheet and these sheets are then stacked upon one another in antiparallel fashion to form a 3D-network structure. In contrast to the structure of form I, the 3D network structure of form II contains two different types of 1Dchains, one in which π-π stacked aryl rings are connected sideways just similar to form I, while the other in which these are arranged on top of each other. Each type of 1D-chain is further connected to the neighboring chains forming two different types of 2D-sheets and each sheet is then sandwiched among the others to form a 3D-network of form II. Similar 2D-sheets, composed of 1D-chains of π-π stacked aryl rings are observed in 3D-network of form III which are also stacked on each other. In form IV, the 1D-chains of π-π stacked aryl rings are connected with the neighboring chains in a zig-zag manner. The form V, similar to 3D-netwrok of form II, has two different types of chains, one where π-π stacked aryl rings are sideways connected and the other in which they are arranged on top of each other. These two different types of 1D-chains are connected with each other in a zig-zag manner to form 2D-structures, which are stacked on each other to form a 3D-network of form V (Figure 4). The formation of five different polymorphic forms of 1 and apparent differences in the nature of non-covalent interactions in their solid state packing can be credited to the different degree of conjugation of nitrogen lone pairs with the neighbouring conjugated systems in both sulfonamide tautomer and ketoenamine tautomer leading to seemingly different conformational isomers as is quite clear from the Figure 5.


Page 8 of 18

Page 9 of 18

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(form I)

(form II)



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

(form III)

(form IV)


Page 10 of 18

Page 11 of 18

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(form V) Figure 4. View of the crystal packing observed in form I (along a-axis), form II (along a-axis), form III (along c-axis). form-IV (along b-axis) and form V (along a-axis) of 1. Circles indicate the 1D-chains composed of π-π stacked conjugated and planar aryl rings



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 12 of 18

Figure 5. Overlay of molecular conformations of 1: form I = green; form II = orange; form III = red; form IV-A = pink; form IV-B = blue; form V-A = black; form V-B = violet. In summary, we have synthesized a new Schiff base by the simple condensation reaction of 2-hydroxy-1-naphthaldehyde and a well known antibiotic sulfamethoxazole, for which five new polymorphs are discovered from methanol at room temperature and characterized by x-ray crystallographic technique. This represents the first example of the coexistence and discovery of five polymorphs from the same solvent under identical conditions.44 In the crystal structures of these polymorphs, an exclusive preference for one of the four possible pairs of sulfonamidesulphonimide and phenolimine-ketoenamine tautomeric structures has been observed, despite the loss of aromatic character of one of the benzene ring. However, the slightly different conjugation levels of nitrogens with the neighbouring systems resulted in different structural conformations and intermolecular interactions. The possibility of desmotrops, great conformational mobility (Figure 5), diverse intermolecular interactions and remarkable property to provide many stable


Page 13 of 18

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


polymorphs at room temperature make this compound an ideal candidate for further polymorphism studies, and to explore and understand crystal growth process. ASSOCIATED CONTENT Supporting Information Figures S1, Tables S1, Table S2 and Figure S2, and all crystallographic information files (CIF). "This material is available free of charge via the Internet at http://pubs.acs.org"

ACKNOWLEDGMENTS We are highly grateful to the Higher Education Commission (HEC), Govt. of Pakistan for financial support. REFERENCES (1)

Cruz-Cabeza, A. J.; Bernstein, J., Conformational Polymorphism. Chem. Rev. 2014, 114,

2170-2191. (2)

Wang, J. G.; Gao, Y.; Xiang, J. C.; Wang, M.; Wu, A. X., X-ray studies of conformation:

observation of conformational polymorphism of a glycoluril clip. CrystEngComm 2015, 17, 2245-2249. (3)

Rodriguez-Molina, B.; Ochoa, M. E.; Romero, M.; Khan, S. I.; Farfan, N.; Santillan, R.;

Garcia-Garibay, M. A., Conformational Polymorphism and Isomorphism of Molecular Rotors with Fluoroaromatic Rotators and Mestranol Stators. Cryst. Growth Des. 2013, 13, 5107-5115. (4)

Negrier, P.; Barrio, M.; Tamarit, J. L.; Mondieig, D.; Zuriaga, M. J.; Perez, S. C.,

Conformational Polymorphism: The Missing Phase of 1,1,2,2-Tetrachloroethane (Cl2HCCHCl2). Cryst. Growth Des. 2013, 13, 2143-2148. (5)

Khavasi, H. R.; Tehrani, A. A., Halogen bonding synthon crossover in conformational

polymorphism. CrystEngComm 2013, 15, 5813-5820. (6)

SeethaLekshmi, S.; Row, T. N. G., Conformational Polymorphism in a Non-steroidal

Anti-inflammatory Drug, Mefenamic Acid. Cryst. Growth Des. 2012, 12, 4283-4289.



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

(7)

Page 14 of 18

Rubcic, M.; Milic, D.; Pavlovic, G.; Cindric, M., Conformational Diversity of

Thiosemicarbazonatovanadium(V) Complexes in the Solid State: From Polymorphism to Isostructurality. Cryst. Growth Des. 2011, 11, 5227-5240. (8)

Zhang, R.; Yan, Q. F.; Shen, Y. T.; Gan, L. H.; Zeng, Q. D.; Zhao, D. H.; Wang, C.,

Conformational polymorphism of multimeric perylene derivatives observed by using scanning tunneling microscopy. CrystEngComm 2011, 13, 5566-5570. (9)

Helttunen, K.; Nauha, E.; Kurronen, A.; Shahgaldian, P.; Nissinen, M., Conformational

polymorphism and amphiphilic properties of resorcinarene octapodands. Org. Biomol. Chem. 2011, 9, 906-914. (10)

Yuan, G. Z.; Zhu, C. F.; Liu, Y.; Xuan, W. M.; Cui, Y., Anion-Driven Conformational

Polymorphism in Homochiral Helical Coordination Polymers. J. Am. Chem. Soc. 2009, 131, 10452-10460. (11)

Nangia, A., Conformational polymorphism in organic crystals. Acc. Chem. Res. 2008, 41,

595-604. (12)

Griesser, U. J.; Jetti, R. K. R.; Haddow, M. F.; Brehmer, T.; Apperley, D. C.; King, A.;

Harris, R. K., Conformational Polymorphism in Oxybuprocaine Hydrochloride. Cryst. Growth Des. 2008, 8, 44-56. (13)

Gorbitz, C. H., Crystal structures of amino acids: from bond lengths in glycine to metal

complexes and high-pressure polymorphs. Cryst. Rev. 2015, 21, 160-212. (14)

Long, S. H.; Zhou, P. P.; Parkin, S.; Li, T. L., Polymorphism and solid-to-solid phase

transitions of a simple organic molecule, 3-chloroisonicotinic acid. CrystEngComm 2015, 17, 2389-2397. (15)

Edkins, R. M.; Hayden, E.; Steed, J. W.; Fucke, K., Conserved hydrogen bonding in

tetrahydrocarbazolone derivatives: influence of solution-state assembly on crystal form nucleation. Chem. Commun. 2015, 51, 5314-5317. (16)

Mondal, P.; Karmakar, A.; Singh, W. M.; Baruah, J. B., Crystal packing in some flexible

carboxylic acids and esters attached to a naphthalene ring. CrystEngComm 2008, 10, 1550-1559. (17)

Terada, S.; Katagiri, K.; Masu, H.; Danjo, H.; Se, Y.; Kawahata, M.; Tominaga, M.;

Yamaguchi, K.; Azumaya, I., Polymorphism of Aromatic Sulfonamides with Fluorine Groups. Cryst. Growth Des. 2012, 12, 2908-2916.


Page 15 of 18

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(18)

Xie, Z. Q.; Liu, L. L.; Yang, B.; Yang, G. D.; Ye, L.; Li, M.; Ma, Y. G., Polymorphism

of 2,5-diphenyl-1,4-distyrylbenzene with two cis double bonds: The essential role of aromatic CH/π hydrogen bonds. Cryst. Growth Des. 2005, 5, 1959-1964. (19)

Huang, H. L.; Wang, S. L., Nanoribbon-Structured Organo Zinc Phosphite Polymorphs

with White-Light Photoluminescence. Angew. Chem. Int. Ed. 2015, 54, 965-968. (20)

Peebles, C.; Alvey, P. M.; Lynch, V.; Iverson, B. L., Time-Dependent Solid-State

Polymorphism of a Series of Donor-Acceptor Dyads. Cryst. Growth Des. 2014, 14, 290-299. (21)

Li, R. H.; Xiao, S. Z.; Li, Y.; Lin, Q. F.; Zhang, R. H.; Zhao, J.; Yang, C. Y.; Zou, K.; Li,

D. S.; Yi, T., Polymorphism-dependent and piezochromic luminescence based on molecular packing of a conjugated molecule. Chem. Sci. 2014, 5, 3922-3928. (22)

Berzins, A.; Skarbulis, E.; Actins, A., Structural Characterization and Rationalization of

Formation, Stability, and Transformations of Benperidol Solvates. Cryst. Growth Des. 2015, 15, 2337-2351. (23)

Han, G. J.; Chow, P. S.; Tan, R. B. H., Growth Behaviors of Two Similar Crystals: The

Great Difference. Cryst. Growth Des. 2015, 15, 1082-1088. (24)

Schur, E.; Nauha, E.; Lusi, M.; Bernstein, J., Kitaigorodsky Revisited: Polymorphism and

Mixed Crystals of Acridine/Phenazine. Chem.- Eur. J. 2015, 21, 1735-1742. (25)

Mizzi, J. E.; Staples, R. J.; LaDuca, R. L., Temperature-dependent polymorphism and

magnetic properties of three-dimensional copper pyromellitate coordination polymers containing 4,4 '-dipyridylamine. J. Solid State Chem. 2015, 225, 222-230. (26)

Stevens, L. A.; Goetz, K. P.; Fonari, A.; Shu, Y.; Williamson, R. M.; Bredas, J. L.;

Coropceanu, V.; Jurchescu, O. D.; Collis, G. E., Temperature-Mediated Polymorphism in Molecular Crystals: The Impact on Crystal Packing and Charge Transport. Chem. Mat. 2015, 27, 112-118. (27)

Wen, H. R.; Bao, J.; Liu, S. J.; Liu, C. M.; Zhang, C. W.; Tang, Y. Z., Temperature-

controlled polymorphism of chiral Cu-II-Ln(III) dinuclear complexes exhibiting slow magnetic relaxation. Dalton Trans. 2015, 44, 11191-11201. (28)

David, W. I. F.; Shankland, K.; Pulham, C. R.; Blagden, N.; Davey, R. J.; Song, M.,

Polymorphism in benzamide. Angew. Chem. Int. Ed. 2005, 44, 7032-7035.



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

(29)

Page 16 of 18

Li, T. L.; Ayers, P. W.; Liu, S. B.; Swadley, M. J.; Aubrey-Medendorp, C.,

Crystallization Force-A Density Functional Theory Concept for Revealing Intermolecular Interactions and Molecular Packing in Organic Crystals. Chem.- Eur. J. 2009, 15, 361-371. (30)

Erdemir, D.; Lee, A. Y.; Myerson, A. S., Nucleation of Crystals from Solution: Classical

and Two-Step Models. Acc. Chem. Res. 2009, 42, 621-629. (31)

Ostwald, W., Studien über die Bildung und Umwandlung fester Körper. Z. Phys. Chem.

1897, 22, 289-330. (32)

Yu, L., Nucleation of one polymorph by another. J. Am. Chem. Soc. 2003, 125, 6380-

6381. (33)

Chen, S. A.; Xi, H. M.; Yu, L., Cross-nucleation between ROY polymorphs. J. Am.

Chem. Soc. 2005, 127, 17439-17444. (34)

Price, C. P.; Grzesiak, A. L.; Matzger, A. J., Crystalline polymorph selection and

discovery with polymer heteronuclei. J. Am. Chem. Soc. 2005, 127, 5512-5517. (35)

Takasuka, M.; Nakai, H., IR and Raman spectral and X-ray structural studies of

polymorphic forms of sulfamethoxazole. Vib. Spectrosc. 2001, 25, 197-204. (36)

Lill, S. O. N.; Broo, A., Molecule VI: Sulfonimide or Sulfonamide? Cryst. Growth Des.

2014, 14, 3704-3710. (37)

Martinez, R. F.; Avalos, M.; Babiano, R.; Cintas, P.; Jimenez, J. L.; Light, M. E.;

Palacios, J. C., Tautomerism in Schiff bases. The cases of 2-hydroxy-1-naphthaldehyde and 1hydroxy-2-naphthaldehyde investigated in solution and the solid state. Org. Biomol. Chem. 2011, 9, 8268-8275. (38)

Ali, S. T.; Antonov, L.; Fabian, W. M. F., Phenol-Quinone Tautomerism in

(Arylazo)naphthols and the Analogous Schiff Bases: Benchmark Calculations. J. Phy. Chem. A 2014, 118, 778-789. (39)

Przybylski, P.; Huczynski, A.; Pyta, K.; Brzezinski, B.; Bartl, F., Biological Properties of

Schiff Bases and Azo Derivatives of Phenols. Curr. Org. Chem. 2009, 13, 124-148. (40)

Satam, M. A.; Telore, R. D.; Sekar, N., Photophysical properties of Schiff's bases from 3-

(1,3-benzothiazol-2-yl)-2-hydroxy naphthalene-1-carbaldehyde. Spectrochim. Acta A 2014, 132, 678-686. (41)

Naseer, M. M.; Hameed, S., Layer-by-layer assembly of supramolecular hexagonal

blocks driven by CH-pi and pi-pi interactions. CrystEngComm 2012, 14, 4247-4250. 16 ACS Paragon Plus Environment

Page 17 of 18

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(42)

Jawaria, R.; Hussain, M.; Shafiq, Z.; Ahmad, H. B.; Tahir, M. N.; Shad, H. A.; Naseer,

M. M., Robustness of thioamide dimer synthon, carbon bonding and thioamide-thioamide stacking in ferrocene-based thiosemicarbazones. CrystEngComm 2015, 17, 2553-2561. (43)

Anam, F.; Abbas, A.; Lo, K. M.; Zia-ur-Rehman; Hameed, S.; Naseer, M. M.,

Homologous 1,3,5-triarylpyrazolines: synthesis, CH···π interactions guided self-assembly and effect of alkyloxy chain length on DNA binding properties. New J. Chem. 2014, 38, 5617-5625. (44)

Chen, S.; Guzei, I. A.; Yu, L., New polymorphs of ROY and new record for coexisting

polymorphs of solved structures. J. Am. Chem. Soc. 2005, 127, 9881-9885.



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 18 of 18

For Table of Contents Use Only

Polymorphism in a Sulfamethoxazole Derivative: Coexistence of Five Polymorphs in Methanol at Room Temperature Muhammad Nawaz Tahir,† Zahid Shafiqδ, Hazoor Ahmad Shadǁ, Zia-ur-Rehman‡, Abdul Karimǁ and Muhammad Moazzam Naseer‡,* †

Department of Physics, University of Sargodha, Sargodha, Pakistan Institute of Chemical Sciences, Organic Chemistry Division, Bahauddin Zakariya University, Multan 60800, Pakistan ǁ Department of Chemistry, University of Sargodha, Sargodha, Pakistan ‡ Department of Chemistry, Quaid-i-Azam University, Islamabad 45320, Pakistan δ

A Schiff base derived from 2-hydroxy-1-naphthaldehyde and a well-known antibiotic sulfamethoxazole affords seven different conformational isomers which are present in five polymorphic forms in methanol solvent at room temperature. An exclusive preference for one of the four possible pairs of sulfonamide-sulphonimide and phenolimine-ketoenamine tautomeric structures has been observed in the crystal structures of these polymorphs. This represents the first example of coexistence of five polymorphs in solution for any of the known compounds so far. N O

CHO OH +

H2N

HN S O O

RT

Methanol

1


Polymorphism in a Sulfamethoxazole Derivative: Coexistence of Five

Recommend Documents