Crystal engineering using bisphenols: interwoven ladders, sheet and framework structures in the binary adducts of 4,4′-sulfonyldiphenol with pyrazine (2/1), 4,4′-bipyridyl (1/1), trans-1,2-bis(4-pyridyl)ethene (1/1), 1,2-bis(4-pyridyl)ethane (1/1) and 4,4′-trimethylenedipyridine (1/1), and in 4,4′-sulfonyldiphenol–4,4′-trimethylenedipiperidine–water (2/2/1)
Authors: Ferguson George , Glidewell Christopher , Gregson Richard M. , Lavender Emma S. 
Published: July 2002

The structures of six hydrogen-bonded adducts of 4,4′-sulfonyldiphenol with heteroaromatic amines have been determined. In 4,4′-sulfonyldiphenol–pyrazine (2/1) the pyrazine molecules lie across centres of inversion. The bisphenol molecules are linked into C(8) chains parallel to [100] by means of O—H...O=S hydrogen bonds, and antiparallel pairs of these chains are cross-linked by the pyrazine molecules, via O—H...N hydrogen bonds, to form molecular ladders containing R_6^6(50) rings between the rungs of the ladders. Each ladder is interwoven with two neighbouring ladders, thus producing a continuous two-dimensional sheet. The structure of 4,4′-sulfonyldiphenol–4,4′-bipyridyl (1/1) consists of spiral C_2^2(21) chains parallel to [010] containing alternating bisphenol and bipyridyl molecules linked by O—H...N hydrogen bonds: these chains are linked by two types of C—H...O hydrogen bonds which form C(5) chains along [001] and C_2^2(10) chains along [101], thus generating two interconnected nets characterized in the one case by a chequerboard pattern of R_6^6(44) and R_6^6(52) rings, and in the other by a single type of R_6^6(46) ring. 4,4′-Sulfonyldiphenol–trans-1,2-bis(4-pyridyl)ethene (1/1) [systematic name: 4,4′-sulfonyldiphenol–trans-4,4′-vinylenedipyridine (1/1)] and 4,4′-sulfonyldiphenol–1,2-bis(4-pyridyl)ethane (1/1) [systematic name: 4,4′-sulfonyldiphenol–trans-4,4′-ethylenedipyridine (1/1)] are isomorphous: the 1,2-bis(4-pyridyl)ethene component exhibits orientational disorder, corresponding approximately to a 180° rotation of ca 23% of the molecules about the N...N vector; in each compound the structure is built from C_2^2(23) chains of alternating bisphenol and bis(pyridyl) molecules connected by O—H...N hydrogen bonds, running parallel to [112] and generated by translation. The [112] chains are linked by C—H...O hydrogen bonds which generate C_2^2(12) chains parallel to [101], so forming a two-dimensional net built from R_6^6(50) rings. The structure of 4,4′-sulfonyldiphenol–4,4′-trimethylenedipyridine (1/1) consists of C_2^2(24) chains parallel to [100] generated by translation and consisting of alternating bisphenol and bis(pyridyl) molecules linked by O—H...N hydrogen bonds. Pairs of such chains are coiled together to form double helices, and pairs of such double helices, of opposite hand, are linked together by paired C—H...O hydrogen bonds in R_2^2(10) rings to form pairs of interwoven ladders in which the C_2^2(24) chains form the uprights and the R_2^2(10) rings form the rungs, between which are R_6^6(50) rings: an R_2^2(10) ring belonging to one ladder lies at the centre of an R_6^6(50) ring belonging to the other. 4,4′-Sulfonyldiphenol–4,4′-trimethylenedipiperidine–water (2/2/1) is a salt, 2C13H27N_2^+·2C12H9O4S−·H2O, containing two independent singly protonated diamine cations, two independent bisphenolate anions, and neutral water molecules. The two independent diamine cations are linked by N—H...N hydrogen bonds into C_2^2(24) chains running parallel to [001] and generated by translation, and each type of bisphenolate anion forms an independent spiral C(12) chain, also parallel to [001]. The three types of chain are linked by the water molecules: the two types of bisphenolate chain are linked by water molecules acting as double donors in O—H...O− hydrogen bonds in a C_6^4(32) chain parallel to [100], thus generating a two-dimensional net built from R_8^6(56) rings; the diamine chains are linked to these nets by means of N—H...O hydrogen bonds in which the water molecules act as acceptors and further hydrogen bonds, of N—H...O− and N—H...O=S types, link these two-dimensional nets into a continuous three-dimensional framework.