A molecular salt of tricyanomethanide anion and a N,N9- dianisylphenazinium dication forms extended supramolecular assemblies that consist of unusual methoxy…methoxy and CMN…N+ intermolecular contacts

Blackstock, Silas C.

McKay, Scott E.

Wheeler, Kraig A.

English

Eastern Illinois University

Eastern Illinois UniversityThe KeepFaculty Research and Creative Activity ChemistryJanuary 2006A molecular salt of tricyanomethanide anion and aN,N9- dianisylphenazinium dication: cooperativeaffects of methoxy…methoxy and CMN…N+intermolecular contactsScott E. McKayCentral Missouri State UniversityKraig A. WheelerEastern Illinois University, kawheeler@eiu.eduSilas C. BlackstockUniversity of Alabama - TuscaloosaFollow this and additional works at: http://thekeep.eiu.edu/chemistry_facPart of the Organic Chemistry CommonsThis Article is brought to you for free and open access by the Chemistry at The Keep. It has been accepted for inclusion in Faculty Research andCreative Activity by an authorized administrator of The Keep. For more information, please contact tabruns@eiu.edu.Recommended CitationMcKay, Scott E.; Wheeler, Kraig A.; and Blackstock, Silas C., "A molecular salt of tricyanomethanide anion and a N,N9-dianisylphenazinium dication: cooperative affects of methoxy…methoxy and CMN…N+ intermolecular contacts" (2006). FacultyResearch and Creative Activity. 7.http://thekeep.eiu.edu/chemistry_fac/7A molecular salt of tricyanomethanide anion and a N,N9-dianisylphenazinium dication: cooperative affects ofmethoxy…methoxy and CMN…N+ intermolecular contactsScott E. McKay,*a Kraig A. Wheelerb and Silas C. BlackstockcReceived 24th November 2005, Accepted 6th January 2006First published as an Advance Article on the web 12th January 2006DOI: 10.1039/b516674hA molecular salt of tricyanomethanide anion and a N,N9-dianisylphenazinium dication forms extended supramolecularassemblies that consist of unusual methoxy…methoxy andCMN…N+ intermolecular contacts.Since collections of non-bonded contacts influence the formationof molecular crystals, it is not surprising that identifying therecognition profile of individual chemical functions attached toa variety of chemical frameworks remains an active topic ofmaterials research. One possible indication of progress realised inthis area is the direct use of information gathered from fundmentalstudies of supramolecular synthons to the development ofmaterials with practical functions.1–4 The list of notable applica-tions5,6 of crystal engineering continues to grow and serves asmotivation for future work. Another area of developmentalimportance is the search for new supramolecular synthons.Although a path less trodden, investigations that seek to uncovernew venues of intermolecular contacts provide a valuable resourceby adding to the current understanding of structural featuresresponsible for crystal cohesion. Most additions to the extantdatabase of molecular interactions often occur serendipitously, andthus progress in this area is measured by small, usuallyunmethodical, advances. Herein we report the surprising structureof molecular salt 1 formed from tricyanomethanide (TCM) and aphenazinium dication.Our recent investigations of the crystal packing behavior ofthe N-oxide group have demonstrated the importance ofN–O2…donor interactions as a structural tool for bimolecularassembly.7–10 Due to the strong hydrogen bond acceptor abilityof the N–O2 group, we have successfully generated cocrystallineassemblages with a variety of organic donors. The present workreports one such investigation. However, unlike our previousstudies where cocrystallization resulted in bimolecular arraysconstructed from the expected fundamental building-blocks, thecurrent study revealed a surprising chemical transformationresulting from low-temperature cocrystallization of an equimolarmixture of dianisyl nitroxide and tetracyanoethylene (TCNE). Thistransformation of TCNE to TCM has been previously reported inthe literature.11 Spectroscopic and crystallographic{ investigationsof the sample obtained from this slow evaporation processshowed 1 as the product.Inspection of the crystal structure of 1 revealed a blend ofunusual non-bonded contacts. As shown in Fig. 1, the structure of1 is constructed from a 1 : 2 ratio of N,N9-dianisylphenaziniumand TCM ions positioned on inversion and two-fold symmetryoperators, respectively. The conformation of the phenaziniumdication is planar with the pendant orthogonal p-anisyl groups(C3–N1–C7–C8 5 80.23u) covalently attached to each N+ atom.Closer inspection of the pyrazinium core reveals bond distancesand angles consistent with an aromatic species (C–N+ave 51.394(4) A˚; sum of C–N1+–C angles 5 359.9(2)u).12,13 The planarTCM anion possesses local C2v symmetry with a central sp2hybridized trivalent C16 atom.Each phenazinium dication is associated with neighboring TCManions via C15MN2…N1+ electrostatic interactions (N2…N1+ 53.172(3) A˚; C15MN2…N1+ 5 147.6(2)u) as shown in Fig. 2. Thismotif propogates in the crystal to form catemeric molecular chains.Although the two symmetry related cyano groups are involved inthe construction of this motif, the third cyano group (C17MN3)lacks any discernable intermolecular close contacts within van derWaals radii. Another interesting structural feature of 1 is theoccurance of methoxy…methoxy connections (C13…O1 53.187(3) A˚; O1–C13…O1 5 157.7(2)u). These apparent attractionsappear to further stabilize the structure and result in 2-D molecularnetworks in the ac plane (Fig. 3).The observed phenazinium…TCM and methoxy…methoxypacking motifs prompted us to explore the frequency of thesepatterns and their potential usefulness as supramolecular synthons.Surprisingly, a search of the CSD14 (version 5.26 with August2005) failed to uncover any additional structures with thephenazinium…TCM motif. Closer inspection of the retrievedaDepartment of Chemistry and Physics, Central Missouri StateUniversity, Warrensburg, Missouri, USA.E-mail: mckay@cmsu1.cmsu.edu; Fax: +1 660 543 4843;Tel: +1 660 543 4949bDepartment of Chemistry, Eastern Illinois University, Charleston,Illinois, USA. E-mail: cfkaw@eiu.educ; Fax: +1 217 581 6613;Tel: +1 205 34810748cDepartment of Chemistry, The University of Alabama, Tuscaloosa,Alabama, USA. E-mail: blackstock@ua.edu; Fax: +1 205 348 9104;Tel: +1 217 581 3119COMMUNICATION www.rsc.org/crystengcomm | CrystEngCommThis journal is  The Royal Society of Chemistry 2006 CrystEngComm, 2006, 8, 129–131 | 129Downloaded by Northwestern University on 02 November 2012Published on 12 January 2006 on http://pubs.rsc.org | doi:10.1039/B516674HView Online / Journal Homepage / Table of Contents for this issuestructures only revealed two additional examples with thepyrazinium dication core (DAYBIO and JUXLAP) and fivestructures with the TCM anion (AMCYME, CUQZAP01,KADGUR01, SEJJUM, TOKXIA). Only in the case of theammonium salt of TCM (AMCYME) are CMN…N+sp3 contactsobserved (N…N+ 5 2.924–3.080 A˚).Although the methoxy…methoxy interaction has been pre-viously reported in the literature,15–17 to our knowledge the degreeof motif persistence and preferred geometry of this pattern remainsrelatively undiscovered. Inspection of the the CSD resulted in97 organic structures (217 fragments) consisting of anisyl groupswith intermolecular methoxy…methoxy contacts less than the sumof van der Waals radii (3.22 A˚; ref. 18). Fig. 4 shows a correlationplot of this interaction with a significant concentration of dataFig. 2 View of the molecular packing of 1 projected down the aaxis showing CMN…N+ interactions. Intermolecular contacts depicted asdotted lines. Symmetry codes: i 2x, y, 5/2 2 z; iiK 2 x,K 2 y, 2 2 z.Fig. 3 View of the molecular packing of 1 showing methoxy…methoxyinteractions. TCM molecules removed for clarity. Symmetry codes: i x,1 2 y, K + z, ii x, 1 2 y, z 2 K.Fig. 4 Correlation plot of the intermolecular bond distances and anglesof anisyl methoxy…methoxy contacts retrieved from the CSD.Fig. 1 The molecular structure and labeling scheme of 1 showing 50%probability displacement ellipsoids for the asymmetric unit.130 | CrystEngComm, 2006, 8, 129–131 This journal is  The Royal Society of Chemistry 2006Downloaded by Northwestern University on 02 November 2012Published on 12 January 2006 on http://pubs.rsc.org | doi:10.1039/B516674HView Online(27%) near 140¡ O–C…O¡ 180u and 2.84¡ C…O¡ 3.12 A˚favoring a linear alignment of methoxy…methoxy contacts. Thesedata provide compelling evidence for the alignment of methoxygroups which would appear to originate from complementaryattractive forces rather than just the consequence of close packing.While the catalog of known non-bonded contacts continues toincrease each year, one must wonder how many additional usefulsupramolecular synthons remain to be discovered? This structuralstudy draws attention to the need for exploration of new or lessrecognized intermolecular contacts that may be practically usefulin controlling the geomtery of molecular arrays. In the case of 1,little or no information is known about the organizationalbehavior of the methoxy…methoxy or phenazinium…TCMinteractions. Additional work is necessary to realize thestructural preferences and transferabilty of CMN…N+ andmethoxy…methoxy motifs as viable supramolecular building-blocks for future supramolecular studies.Notes and references{ Crystal data for 1: C32H26N5O4, M 5 544.58, monoclinic, space groupC2/c, a5 16.4791(9) A˚, b5 21.8079(12) A˚, c5 7.8598(4) A˚, b5 104.85(3)u,V5 2730.2(3) A˚3, Z5 4, Dc5 1.325, m(Mo-Ka)5 0.090 mm21, T5 173 K.2497 unique reflections (Rint 5 0.034. Final R1 [1834 I . 2s(I)] 5 0.0574,wR2 (all data) 5 0.1652. CCDC reference number 290608. For crystal-lographic data in CIF or other electronic format see DOI: 10.1039/b516674h. Synthesis: To a 10 mL round-bottom flask was added 0.050 g(0.22 mmol) of dianisyl amine and 3 mL of a 1 : 1 methylene chloride :acetone solution. To this was added 0.1624 g (0.23 mmol) of oxone. Theheterogeneous mixture was stirred vigorously at room temperature undernitrogen for 4 h and to the resulting dark solution was added 50 mL ofdiethyl ether and 50 mL of hexane. Dianisyl nitroxide was collected as ared-purple solid (0.25 g, 0.10 mmol, 46%). An equimolar ratio of dianisylnitroxide and tetracyanoethylene was disolved in acetonitrile. The darkpurple solution was placed in the freezer (25 uC) with ether diffusion andafter several days afforded dark purple plate-like crystals of 1.1 Frontiers in Crystal Engineering, ed. E. R. Tiekink and J. Vittal, Wiley,Chichester, 2006.2 Molecular Machines and Motors, ed. J.-P. Sauvage, Springer, New York,2001, vol. 99.3 Structure and Bonding: Supramolecular Assembly via Hydrogen Bonds II,ed. D. M. P. Mingos, Springer, New York, 2004, vol. 111.4 Proceedings of the 8th International Summer School of Biophysics:Supramolecular Structure and Function, ed. G. Pifat-Mrzljak, Springer,New York, 2004.5 Supramolecular Chemistry, ed. P. D. Beer, P. A. Gale and D. K. Smith,Oxford University Press, New York, 2003.6 Supramolecular Chemistry, ed. J. W. Steed and J. L. Atwood, Wiley,New York, 2000.7 J. R. Bowers, G. W. Hopkins, G. P. A. Yap and K. A. Wheeler, Cryst.Growth Des., 2005, 4, 727–736.8 S. G. Bodige, T. D. Selby, S. E. McKay and S. C. Blackstock, Trans.Am. Crystallogr. Assoc., 1998, 33, 135.9 M. L. Greer, B. J. McGee, R. D. Rogers and S. C. Blackstock, Angew.Chem., Int. Ed. Engl., 1997, 36, 1864–1866.10 B. J. McGee, L. J. Sherwood, M. L. Greer and S. C. Blackstock, Org.Lett., 2000, 2, 1181–1184.11 T. V. Baukova, D. N. Kravtsov, L. G. Kuz’mina, N. V. Dvortsova,M. A. Poray-Koshits and E. G. Perevalova, J. Organomet. Chem., 1989,372, 465–71.12 F. Turksoy, G. Hughes, A. S. Batsanov and M. R. Bryce, J. Mater.Chem., 2003, 13, 1554–1557.13 H.-D. Hausen, A. Schulz and W. Kaim, J. Chem. Soc., Perkin Trans. 2,1993, 343–345.14 F. H. Allen, Acta Crystallogr., Sect. B, 2002, 58, 380–388.15 M.-L. Liu, J.-M. Dou, D.-Q. Wang and D.-C. Li, Acta Crystallogr.,Sect. E, 2005, 61, o3876–o3878.16 C. M. L. Vande Velde, H. J. Geise and F. Blockhuys, Acta Crystallogr.,Sect. E, 2004, 60, o1031–o1033.17 C. M. L. Vande Velde, H. J. Geise and F. Blockhuys, Cryst. GrowthDes., 2006, 6, 241–246.18 A. Bondi, J. Phys. Chem., 1964, 68, 441–451.This journal is  The Royal Society of Chemistry 2006 CrystEngComm, 2006, 8, 129–131 | 131Downloaded by Northwestern University on 02 November 2012Published on 12 January 2006 on http://pubs.rsc.org | doi:10.1039/B516674HView Online

A molecular salt of tricyanomethanide anion and a N,N9- dianisylphenazinium dication: cooperative affects of methoxy…methoxy and CMN…N+ intermolecular contacts

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A molecular salt of tricyanomethanide anion and a N,N9- dianisylphenazinium dication: cooperative affects of methoxy…methoxy and CMN…N+ intermolecular contacts

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