Abstract
The structure of cubane-1,3,5,7-tetracarboxylic acid dihydrate (1) has been determined. It crystallizes in the space groupP21/c with cell dimensionsa=6.503(1),b=19.173(1),c=10.527(1) Å, β=101.60(1). The details of this structure have reaffirmed the fact that the cubane skeleton is a flexible entity which reflects its steric and electronic environment. Of the four carboxylic acid groups three adopt asyn conformation while the fourth adopts ananti conformation. The orientation of these groups with respect to the cubane skeleton is reflected in the C−C bond lengths. Those C−C bonds which are perpendicular to the carboxylic acid groups are the longest and those which are most nearly eclipsed are the shortest in the cubane skeleton. In all cases it is the C=O rather than the C−O bond which is most nearly eclipsed with a C−C bond. The tetrahedral orientation of the substitutents does not express itself in a three dimensional supramolecular assembly; however, all four carboxylic acid groups are involved in very strong donor hydrogen bonds which result in a two dimensional array parallel to (100). An additional surprising results is the fact that none of the four substituents participate in traditional hydrogen bonded carboxylic acid dimeric moieties.
Similar content being viewed by others
References
Eaton, P.E.,Angew. Chem. Int. Ed. Engl. 1992,31, 1421.
Bashir-Hashemi, A.; Iyer, S.; Alster, J.; Slagg, N.Chem. Ind. 1995,14 533
Lex, J.; Ermer, O.Angew. Chem. Int. Ed. Engl. 1987,26, 447.
Desiraju, G.R.,Crystal Engineering of Organic Solids, Elsevier, Amsterdam, 1989.
Zaworotko, M.J.,Chem Soc. Rev. 1994, 283.
Craig, D.C.; Dance, I.G.; Garbutt, R.Angew. Chem. Int. Ed. Engl. 1986,25, 165.
Emer, O.J. Am. Chem. Soc. 1988,110, 3747.
Hoskins, B.F.; Robson, R.J. Am. Chem. Soc. 1990,112, 1546.
Simard, M.; Su, D.; Wuest, J.D.J. Am. Chem. Soc. 1991,113, 4696.
Clerk, M.D.; Zaworotko, M.J.J. Chem. Soc. Chem. Comm. 1991, 1607.
Copp, S.B., Subramanian, S.; Zaworotko, M.J.,J. Am. Chem. Soc. 1992,114, 8719.
Clerk M.D.; Copp, S.B.; Subramanian, S.; Zaworotko, M.J.,Supramol. Chem. 1992,1, 7.
Copp, S.B.; Subramanian, S.; Zaworotko, M.J.Angew. Chem. Int. Ed. Engl. 1993,32, 706.
Reddy, D.S.; Craig, D.C.; Desiraju, G.R.J. Chem. Soc. Chem. Commun. 1994, 1457.
Copp, S.B.; Holman, T.K.; Sangster, J.O.S.; Subramanian, S. Zaworotko, M.J.J. Chem. Soc. Dalton Trans. 1995 2233.
Abourahma, H.; Copp, S.B.; MacDonald, M-A.; Melendez, R.E.; Batchilder, S.D.; Zaworotko, M.J.J. Chem. Crystallogr. 1995,25, 731.
Schwiebert, K.E.; Chin, D.N.; MacDonald, J.C.; Whitesides, G.M.J. Am. Chem. Soc. 1996,118, 4018.
Reddy, D.S.; Ovchinnikov, Y.E.; Shishkin, O.V.; Struchkov, Y.T.; Desiraju, G.R.J. Am. Chem. Soc. 1996,118, 4085.
Allen, F.H.; Howard, J.A.K.; Hoy, V.J.; Desiraju, G.R.; Reddy, D.S.; Wilson, C.C.J. Am. Chem. Soc. 1996,118, 4081.
Reddy, D.S.; Craig, D.C.; Desiraju, G.R.J. Am. Chem. Soc. 1996,118, 4090.
Bashir-Hashemi, A.Angew. Chem. Int. Ed. Engl. 1993,32, 612.
Sheldrick, G.M.1986, SHELXTL, Crystallographic System (Siemens Analytical Instrument Division, Madison, Wis).
Cromer, D.T.; Waber J.T.1974 International Tables for X-Ray Grystallography, Vol IV. The Kynoch Press, Birmingham, England.
Cromer, D.T.1974 International Tables for X-Ray Crystallography, Vol IV, The Kynoch Press, Birmingham, England.
Sheldrick, G.M.; Schneider, T.R.;Methods in Enz. in press. This is a full-matrix least-squares refinement package that uses all data and refines on F2 rather than the traditional F. The various parameters used in this refinement process are defined as follows: R1=Σ|Fo−Fc|/Σ Fo wR2={Σ[w(Fo 2−Fc 2)2]/[w(Fo 2)2]}1/2 where w=1/[o2(Fo)+(aP)2+bP] and a and b are variable parameters whose optimal values are usually suggested by the program during the refinement process. The goodness-of-fit parameter (S) is based on F2 and defined as: s={Σ[w(F 2o −F 2c )2]/[n−p]}1/2, where n is the number of reflections and p is the total number of parameters refined.
Butcher, R.J.; Bashir-Hashemi; Gilardi, R.D.J. Chem. Crystallog. 1995,25, 661.
1.596(3) Å in 1,2,4,7-tetra(carboxymethyl)cubane; reference 21. (b) 1.598(3) Å int-butylcubylcubane: Gilardi, R.G.; Maggini, M.; Eaton, P.E.J. Am. Chem. Soc. 1988,110, 7232. (c) 1.604(7) Å in 1,4-cubanedicarboxylicdi(2,2-dinitro-2-fluoroethylester): Eremenko, L.T.; Romanova, L.B.; Ivanova, M.E.; Eremenko, I.L.; Nefedov, S.E.; Struchkov, Yu. T.Russ. Chem. Bull. 1994,43, 619. (d) 1.607(4) Å in 1,4-bis(diisopropylamino)-methyl-2,7-diphenylcubane: Bashir-Hashemi, A.; Ammon, H.L.; Choi, C.S.J. Org. Chem. 1990,55, 416.
Allen, F.H.; Davies, J.E.; Johnson, O.J.; Kennard, O.; Macrae, C.F.; Mitchell, E.M.; Mitchell, G.F.; Smith, J.M. Watson, D.J. Chem. Inf. Comput. Sci. 1991,31, 187–204.
Eaton, P.E.; Xiong, Y.; Gilardi, R.J. Am. Chem. Soc. 1993,115, 10195.
Frankenbach, G.M.; Etter, M.C.Chem. Mater. 1992 4, 272.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Butcher, R.J., Bashir-Hashemi, A. & Gilardi, R.D. Network hydrogen bonding: the crystal and molecular structure of cubane-1,3,5,7-tetracarboxylic acid dihydrate. J Chem Crystallogr 27, 99–107 (1997). https://doi.org/10.1007/BF02575902
Received:
Issue Date:
DOI: https://doi.org/10.1007/BF02575902