View Article Online / Journal Homepage / Table of Contents for this issue PAPER www.rsc.org/crystengcomm | CrystEngComm Inclusion of triphenylmethane derivatives by crown and linear O-containing molecules : selective interactions and crystal structures† Marina S. Fonari,*a Yurii A. Simonov,a Wen-Jwu Wang,b Shang-Wei Tangb and Eduard V. Ganinc Received 13th June 2008, Accepted 12th August 2008 First published as an Advance Article on the web 8th October 2008 DOI: 10.1039/b810076d The sulfamide derivative of triphenylmethanol, 3-[hydroxy(diphenyl)methyl]benzenesulfonamide (H2NSO2Ph)Ph2COH was synthesized and, alongside with the parent triphenylmethanol and triphenylmethylamine, was investigated for selective interactions with crown ethers of different dimensionality (12-18-membered cycles). The molecule of 12-crown-4 (12C4) appeared to be the best candidate for Ph3COH, Ph3CNH2 and Ph3CNH3$NCS, while (H2NSO2Ph)Ph2COH forms the complex exclusively with 18-crown-6 (18C6). The triphenylammonia trifluoroacetate, Ph3CNH3$CF3COO, selectively forms the complex only with 2-methoxyethanol. The crystalline products of the compositions (Ph3COH)2$12C4, (Ph3CNH2)2$12C4, (Ph3CNH3$NCS)2$12C4, [(H2NSO2Ph)Ph2COH]2$18C6 and Ph3CNH3$CF3COO CH3OCH2CH2OH were obtained and studied by X-ray single crystal diffraction. Introduction ion-pair clusters consisting of a wide range of sulfonic acids with an emphasis on the efficiency of the combination of sterically Publication by Charles J. Pedersen of the synthesis of crown hindered triphenylmethylamine and sulfonate ions (comple- ethers and their property to form host–guest complexes with mentarity in hydrogen bonding, steric effects of the substituents, 1,2 cations and comparatively small neutral guest molecules has acidity of the sulfonic acids). In 1998 Hayashi et al.22 showed on initiated the search and investigation of new, functionally fluorosubstituted triphenylmethanol derivatives that the C–H/ 3–11 isomorphous to crown ethers host molecules, like cyclic F(-C) interactions control the packing motif as well as the 12 cryptands, calixarenes and calixcrowns, cyclodextrines, and thermal stability of the crystal, in continuation in the hot Crys- 8 13,14 acyclic molecules like aromatic diols, arylureas, derivatives tEngComm article Schollmeyer et al.23 demonstrated that the 7,9,14 of triphenylmethane (tritane) etc. The numerous studies trityl alcohols bearing three bromine or three iodine atoms at the revealed the low selectivity of triphenylmethanol (tritanol, para-positions of the aromatic units, as well as the fluorosub- Ph3COH) which binds in supramolecular complexes methanol, stituted derivatives of triphenylmethanol may be a very useful Published on 08 October 2008. Downloaded 08/04/2015 03:15:06. acetone, dimethyl formamide, dimethylsulfoxide, 1,4-dioxane, platform for analysing OH/p and halogen–p interactions as 9,15 morpholine, piperidine, N-methylpiperazine, phenoxine, driving forces in crystal packing. 16 tetrahydrofurane. Triphenylsilanol Ph3SiOH, the precise Surprisingly, apart from the two known examples of analogue of triphenylmethanol, in its turn forms stable adducts Ph SiOH24 and Ph CSH25 inclusion by 12-crown-4 (12C4), no / 3 3 with dimethylsulfoxide and 1,4-dioxane due to O–H O and systematic study of crown inclusion into the network of these / 17,18 C–H p(arene) interactions. Similarly, triphenylmethana- bulky molecules has been carried out so far. This has motivated 19 minium chloride forms an inclusion compound with acetone. us to synthesize and study by X-ray diffraction the crystalline Now we are witnesses to the growing numbers of successful inclusion complexes of tritane derivatives with crown ethers of application of bulky host molecules. Thus, using excellent different dimensionality with an emphasis on the selectivity of inclusion properties of bulky bisphenols Cso¨regh and interactions in these binary systems. co-workers20 have stabilized carboxylic acid and ester molecules in a monomeric state for spectroscopic investigation. The recent research of Tohnai et al.21 has demonstrated the triphenyme- Experimental thylamine ability for an efficient and robust fabrication of [4 + 4] Preparation of the crystalline inclusion compounds It has been stated that spontaneous evaporation of solvents from aInstitute of Applied Physics Academy of Sciences of Moldova, Academiei the mixture of coronands I–III with triphenylmethanol (IVa), str., 5, MD-2028 Chisinau, R. Moldova. E-mail: [email protected]. 1,1,1-triphenylmethanamine (IVb) and 1,1,1-triphenylmethana- md; Fax: +373 22 72 58 87; Tel: +373 22 73 81 54 bDepartment of Chemistry Tamkang University, 151 Ying-Chuan Road, minium thiocyanate (IVc) results in the crystalline molecular Tamsui, Taipei, 25137, Taiwan (ROC). E-mail: [email protected]; complexes of compositions (IVa)2.I (complex VI), (IVb)2.I Fax: +886-2-2620-9924; Tel: +886-2-26215656(2530) (complex VII), (IVc)2.I (complex VIII), respectively (Scheme 1). cOdessa State Environmental University, Ministry of Education and The precipitation of VI from methanol solution indicates its Sciences of Ukraine, Lvovskaya str. 15, Odessa, 65016, Ukraine. E-mail: [email protected]; Tel: +38-048-7852711 higher stability in comparison with the triphenylmethanol 9,15 † CCDC reference numbers 690773–690777. For crystallographic data in complex with methanol. The incorporation of the H-donor CIF or other electronic format see DOI : 10.1039/b810076d sulfamide group in the phenyl ring of IVa molecule yielding the 94 | CrystEngComm, 2009, 11, 94–101 This journal is ª The Royal Society of Chemistry 2009 View Article Online Compound VI, triphenylmethanol–1,4,7,10-tetraoxacycl- ododecane, 2 : 1 : triphenylmethanol (260 mg, 1 mmol) and a mixture of 1,4,7,10-tetraoxacyclododecane (176 mg, 1 mmol), 1,4,7,10,13-pentaoxacyclopentadecane (220 mg, 1 mmol) and 1,4,7,10,13,16-hexaoxacyclooctadecane (264 mg, 1 mmol) were dissolved in methanol (10 ml) The colorless, transparent crystals were obtained by slow evaporation of solvents at room temper- ature for several days. Yield: 593 mg (85%), mp 147–148 C, found, %: C 79.28; H 6.94, required for C46H48O6: C 79.33; H 1 6.90. H NMR (CDCl3), d, ppm: 1.62 (s 2H, OH), 3.70 (s, 16H, CH2), 7.24–7.35 (m, 30H, CH). Compound VII, 1,1,1-triphenylmethanamine–1,4,7,10-tet- raoxacyclododecane, 2 : 1 : 1,1,1-triphenylmethanamine (259 mg, 1 mmol) and a mixture of 1,4,7,10-tetraoxacyclododecane (176 mg, 1 mmol), 1,4,7,10,13-pentaoxacyclopentadecane (220 mg, 1 mmol) and 1,4,7,10,13,16-hexaoxacyclooctadecane (264 mg, 1 mmol) were dissolved in a mixture of benzene/diethyl ether (1 : 2, 5 ml). The colorless, transparent crystals were obtained by Scheme 1 Formulae of the substances used. slow evaporation of solvents at room temperature for several days. Yield: 495 mg (71%), mp 94–95 C, found, %: C 79.51; H 7.25; N 4.03, required for C46H50N2O4: C 79.53; H 7.24; N 4.05. 1 3-[hydroxy(diphenyl)methyl]benzenesulfonamide V drastically H NMR (CDCl3), d, ppm: 1.86 (s, 4H, NH), 3.70 (s, 16H, CH2), changes the mode of intermolecular recognition and results in the 7.20–7.32 (m, 30H, CH). extraction of the largest 18C6 from the reaction mixture of I, II, Compound VIII, triphenylmethanaminium thiocyanate–1,4,7, III with the formation of the crystalline molecular complex of the 10-tetraoxacyclododecane, 2 : 1 : triphenylmethanaminium composition (V)2.III (complex IX). In previously reported thiocyanate (318 mg, 1 mmol) and a mixture of 1,4,7,10-tet- studies no selectivity in the interaction of neutral molecules with raoxacyclododecane (176 mg, 1 mmol), 1,4,7,10,13-pentaox- the titled crown ethers was registered.4 Moreover, the bulky acyclopentadecane (220 mg, 1 mmol) and 1,4,7,10,13,16-hexaox- di(benzenesulfonyl)amine HN(SO2C6H5)2 yields crystalline acyclooctadecane (264 mg, 1 mmol) were dissolved in methanol molecular complexes both with I26 and III.27–29 The replacement (15 ml). The colorless, transparent crystals were obtained by slow of the thiocyanate anion (IVc) by trifluoroacetate (IVd) evaporation of solvents at room temperature for several days. dramatically changes the complexation process. From the Yield: 650 mg (80%), mp 170–172 C, found, %: C 70.85; H 6.48; methanolic mixture of I, II, III, compound IVd is reverted in an N 6.93; S 7.89, required for C48H52N4O4S2: C 70.90; H 6.45; 1 invariable form, while from the solution IVd–I–methanol–2- N 6.89; S 7.93. H NMR (CDCl3), d, ppm: 3.70 (s, 16H, CH2), Published on 08 October 2008. Downloaded 08/04/2015 03:15:06. methoxyethanol the crystalline complex of triphenylmethana- 7.09–7.45 (m, 30H, CH). minium trifluoroacetate with 2-methoxyethanol (compound X)is Compound IX, 3-[hydroxy(diphenyl)methyl]benz- precipitated selectively. Thus, herein for the first time the selec- enesulfonamide–1,4,7,10,13,16-hexaoxacyclooctadecane, 2 : 1 : 3- tive interaction of bulky triphenylmethane derivatives with [hydroxy(diphenyl)methyl]benzenesulfonamide (340 mg, 1 mmol) crown ethers is described with an emphasis on the possibility of and a mixture of 1,4,7,10-tetraoxacyclododecane (176 mg, 1 mmol), crown ethers’ separation30 similar to the procedure described 1,4,7,10,13-pentaoxacyclopentadecane (220 mg, 1 mmol) and earlier.31,32 1,4,7,10,13,16-hexaoxacyclooctadecane (264 mg, 1 mmol) were The initial chemicals were used as received from Aldrich dissolved in a mixture of acetone/hexane (1 : 1, 15 ml). The without further purification. The 1H NMR spectra were recorded colorless, transparent crystals were obtained by slow evaporation with a Bruker AC 300 instrument at 300 MHz using tetrame- of solvents at room temperature for several days. Yield: 835 mg thylsilane as an internal reference. Thin-layer chromatography (98%), mp 174–176 C, found, %: C 63.71; H 6.24; N 2.99; S 6.85, was conducted on Silufol plates with 1 : 8 methanol–chloroform required for C50H58N2O12S2: %: C 63.67; H 6.20; N 2.97; S 6.85.