Publisher's version/PDFBis(4,4'-dihydroxyphenyl) sulfone 1 exploits its tetrahedrally disposed complementary hydrogen bonding sites to generate a unique doubly interwoven molecular carpet architecture in the solid state

Davies, Caitlin

Krishnamohan Sharma, C. V.

Langler, Richard F.

Zaworotko, Michael J.

Chemical Communications

Saint Mary's University, Halifax: Institutional Repository

 OH RSOO1 R = OH2 R = ClA supramolecular carpet formed via self-assembly of bis(4,4A-dihydroxyphenyl)sulfone†Caitlin Davies,a Richard F. Langler,*a C. V. Krishnamohan Sharmab and Michael J. Zaworotko*ba Department of Chemistry, Mount Allison University, Sackville, New Brunswick, Canada E0A 3C0b Department of Chemistry, Saint Mary’s University, Halifax, Nova Scotia, Canada B3H 3C3Bis(4,4A-dihydroxyphenyl) sulfone 1 exploits its tetrahed-rally disposed complementary hydrogen bonding sites togenerate a unique doubly interwoven molecular carpetarchitecture in the solid state.The concept of rational design of 2D and 3D frameworks hasevoked considerable interest in recent years as many functionalproperties of solids are dependent on crystal packing.1,2 Aparticularly interesting and relevant problem that has beenaddressed by several groups concerns the preparation of opencage and/or interwoven networks.3–5 While the former isdesired in the context of porous solids, the latter is an associatedphenomenon which invariably occurs if > 50% of a solid wouldotherwise be empty. Such interpenetration (or catenation) isappreciated for its aesthetic appeal and offers potential hostmaterials if guest molecules can be exploited to preventinterpenetration.6 Understanding and predicting interpenetra-tion patterns therefore constitutes an important aspect of crystalengineering.Self-assembly can be an effective strategy for crystalengineering but it requires careful control over molecularsymmetry and functionality.3 In general, tetrahedral moleculeswith rigid complementary hydrogen bonding sites adaptdiamondoid architecture with levels of interpenetration basedon the relative size of superdiamondoid cage and the volume ofthe tecton.7 We report herein an alternate motif for suchcompounds which occurs if there is flexibility present in thetecton: interwoven 2D square grids.8A solution of bis(4-chlorophenyl) sulfone (4.0 g) and sodiumhydroxide (4.0 g) in Me2SO (160 ml) and water (40 ml) wasmaintained at 100 °C for two months. Extractive workup withdiethyl ether furnished a mixture of unchanged chloro sulfone,bis(4-hydroxyphenyl) sulfone 1 and 4-chlorophenyl(4A-hydroxyphenyl) sulfone 2. Chloroform elution on silica gelfurnished pure 1 (2%) and 2 (50%).Non-centrosymmetric crystals of 1 were obtained fromacetone–CHCl3 (mp 247–249 °C). The crystal structure‡reveals an infinite 2D hydrogen bonded network sustained byinteraction between hydroxy and sulfone groups (O···O2.705(7), 2.800(3) Å, Fig. 1). The network generates squarecavities with ca. 8 3 10 Å dimensions, large enough to facilitategeneration of a 2-fold interwoven molecular carpet (Fig. 2). Theentangled 2D grids are stabilized by van der Waals andherringbone interactions. A 3D diamondoid architecture is alsofeasible but presumably packs less efficiently in the absence ofan appropriate guest.The molecular carpet architecture of 1 demonstrates howmolecules with flexible hydrogen bonding sites can self-assemble to yield 2D interwoven networks as an alternative to3D diamondoid architectures. Such networks would be ex-pected to have clay-like intercalation properties and, ifappropriate guests can be used to eschew interpenetration, largecavities within the grid.9 The critical importance of com-plementarity amongst the hydrogen bonding sites is illustratedby what happens if one hydroxy substituent of 1 is replaced bya chloro substituent. 4-chlorophenyl (4A-hydroxyphenyl) sul-fone 2 exhibits a less predictable but nonetheless intriguingcrystal structure.§ Compound 2 crystallizes from CHCl3 (mp150–151 °C) in the non-centrosymmetric space group P1 with,remarkably, four  molecules in the asymmetric unit. There aretwo discrete hydrogen bonding motifs: i, simple linear hydrogenbonding between sulfone and hydroxy groups [2.898(6) Å]; ii,cyclic hydrogen bonding involving two of the sulfone O atomsand three hydroxy groups, possibly with two of the hydroxygroups being disordered [Scheme 1, O···O: 2.838(6), 2.881(6),Fig. 1 ORTEP diagram of 1 illustrating a single hydrogen bondednetworkFig. 2 A space filling diagram of the interwoven supramolecular carpetarchitecture of 1. The two independent grids are colour coded for clarity.Chem. Commun., 1997 567Published on 01 January 1997. Downloaded on 02/02/2015 16:45:57. View Article Online / Journal Homepage / Table of Contents for this issueOOSOOO3.019(6), 2.913(6) Å]. Furthermore, there are two differentkinds of aryl–aryl stacking interactions: between chlorophenyland hydroxyphenyl groups and between adjacent chlorophenylgroups. The mean interplanar distances and dihedral angles ofthese two stacking interactions are 3.74 and 3.60 Å, 2.9 and 3.4°respectively.Compounds 1 and 2 illustrate clearly the importance of self-assembly to crystal engineering. Compound 1 demonstrateshow tetrahedral moieties with complementary hydrogen bond-ing sites are capable of self-assembling into a predictable 2Dmotif if the hydrogen bonding sites are robust and flexible.However, 2 demonstrates how even minor changes in func-tionality can lead to unusual and unpredictable crystal pack-ing.Footnotes† This ChemComm is also available in enhanced multi-media format via theWorld Wide Web: http://chemistry.rsc.org/rsc/cccenha.htm‡ Crystal Data for 1: 4,4A-Dihydroxyphenyl sulfone, M = 249.26,orthorhombic, C2cb, a = 8.1572(10), b = 19.2757(21), c = 15.0471(20)Å, V = 2365.9(5) Å3, Z = 8, Dcalc = 1.40 Mg m23, l = 0.70930 Å,F(000) = 1032.921 reflections with Inet > 3s (Inet) out of 1121 uniquereflections measured at 290 K for a crystal of dimensions 0.3 3 0.2 3 0.4mm on an Enraf-Nonius CAD4 diffractometer using the w scan mode (4 <2q < 50°) afforded, on convergence, final values of Rf = 0.077 andRw = 0.089. The H atom of one of the two OH groups was found viadifference Fourier map inspection. Other H atoms were placed in calculatedpositions (C–H = 1.0 Å). All non-hydrogen atoms were anisotropicallyrefined. The crystallographic calculations were carried out using NRCVAXprogram package. Atomic coordinates, bond lengths and angles, andthermal parameters for both 1 and 2 (see below) have been deposited at theCamrbidge Crystallograpic Centre (CCDC). See Information for Authors,Issue No. 1. Any request to the CCDC for this material should quote the fullliterature citation and the reference number 182/360.Since submission of this article an account of the structure of 1 has beenpublished. See G. Ferguson and C. Glidewell, Acta Crystallogr., Sect. C,1996, 52, 2528.§ Crystal Data for 2: As for 1 but 4-hydroxyphenyl, 4A-chlorophenylsulfone, M = 267.96, triclinic, P1, a = 7.6401(11), b = 9.2850(11),c = 17.6630(13) Å, a = 93.04(2), b = 91.51(3), g = 108.64(2),V = 1184.35(24) Å3, Z = 4, Dcalc = 1.503 Mg m23, l = 0.70930 Å,F(000) = 552. 3591 reflections with Inet > 3s (Inet) out of 4149 uniquereflections measured at 290 K for a crystal of dimensions 0.4 3 0.2 3 0.2mm afforded values of Rf = 0.042 and Rw = 0.047.References1 G. R. Desiraju, Crystal Engineering: The Design of Organic Solids,Elsevier, Amsterdam, 1989.2 B. F. Abrahams, B. F. Hoskins and R. Robson, J. Am. Chem. Soc., 1991,113, 3603.3 M. J. Zaworotko, Chem. Soc. Rev., 1994, 283.4 G. B. Gardner, D. Venkataraman, J. S. Moore and S. Lee, Nature, 1995,374, 792; O. M. Yaghi, G. Li and H. Li, Nature, 1995, 378, 703;M. E. Brown and M. D. Hollingsworth, Nature, 1995, 376, 323;S. V. Kolotuchin, E. E. Fenlon, S. R. Wilson, C. J. Loweth andS. C. Zimmerman, Angew. Chem., Int. Ed. Engl., 1995, 34, 2654;S. Subramanian and M. J. Zaworotko, Angew. Chem., Int. Ed. Engl.,1995, 34, 2127; M. Munakata, L. P. Wu, M. Yamamoto, T. Kuroda-Sowaand M. Maekawa, J. Am. Chem. Soc., 1996, 118, 3117.5 D. B. Amabilino and J. F. Stoddart, Chem. Rev., 1995, 95, 2725;D. S. Reddy, D. C. Craig, A. D. Rae and G. R. Desiraju, J. Chem. Soc.,Chem. Commun., 1994, 1457; D. M. Goodgame, S. Menzer, A. M. Smithand D. J. Williams, J. Chem. Soc., Chem. Commun., 1995, 1975;L. Carlucci, G. Ciani, D. M. Proserpio and A. Sironi, J. Chem. Soc.,Chem. Commun., 1994, 2755; P. M. V. Calcar, M. M. Olmstead andA. Balch, J. Chem. Soc., Chem. Commun., 1995, 1723; L. R.MacGillivray, S. Subramanian and M. J. Zaworotko, J. Chem. Soc.,Chem. Commun., 1994, 1325.6 F. H. Herbstein, M. Kapon and G. M. Reisner, J. Inclusion Phenom.,1987, 5, 211.7 O. Ermer, J. Am. Chem. Soc., 1988, 110, 3747; O. Ermer, Angew. Chem.,Int. Ed. Engl., 1988, 27, 829; X. Wang, M. Simard and J. D. Wuest, J. Am.Chem. Soc., 1994, 116, 12119.8 Supramolecular carpets from multiple components were reported by usearlier: S. B. Copp, S. Subramanian and M. J. Zaworotko, Angew. Chem.,Int. Ed. Engl., 1993, 32, 706; C. V. K. Sharma and M. J. Zaworotko,Chem. Commun., 1996, 2655. Related coordination polymers have alsobeen encountered: D. M. L. Goodgame, S. Menzer, A. M. Smith andD. J. Williams, Angew. Chem., Int. Ed. Engl., 1995, 34, 574.9 A. Muller, H. Reuter and S. Dillinger, Angew. Chem., Int. Ed. Engl.,1995, 34, 2328; S. B. Copp and M. J. Zaworotko, unpublished results.Received, 17th May 1996; Revised manuscript received, 15thJanuary 1997; Com. 7/00363CScheme 1568 Chem. Commun., 1997Published on 01 January 1997. Downloaded on 02/02/2015 16:45:57. View Article Online

A supramolecular carpet formed via self-assembly of bis(4,4'-dihydroxyphenyl) sulfone

http://library2.smu.ca/xmlui/bitstream/01/25936/1/Zaworotko_Michael_J_article_1997.pdf

A supramolecular carpet formed via self-assembly of bis(4,4'-dihydroxyphenyl) sulfone

Abstract

Similar works

Full text

Available Versions

Saint Mary's University, Halifax: Institutional Repository