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)

Abstract

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 degrees 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, 2C(13)H(27)N(2)(+).2C(12)H(9)O(4)S(-).H(2)O, 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 [0...

On the Reliability of C−H···O Interactions in Crystal Engineering: Synthesis and Structure of Two Hydrogen Bonded Phosphonium Bis(aryloxide) Salts

“…In light of our previous results, and the rich supramolecular chemistry of neutral bisphenols which have been shown to polymerize via strong hydrogen bonds, − we reasoned that the structures of these phosphonium bisaryloxides would shed further light on the current debate concerning the suitability of C−H···O interactions in crystal engineering. Specifically, we expected to generate either monomeric [Figure a] or polymeric [Figure b] supramolecular structures, depending on the steric requirements of the cation and anion.…”

Organic Complexes Built by Halogenated Molecules: Unexpected in Situ C–N Bond Formation in Metal-Free Solvothermal Conditions

“…The supramolecular chemistry of bis(4-hydroxyphenyl)sulphone (BPS, 1 ) was investigated and showed efficient and robust ability to form organic complexes with a series of organoamines via charge-assisted O hydroxyl ···H···N hydrogen bonds with or without proton transfer . We target on the halogenated BPS as modeling molecules based on the following considerations: (i) the ability of the hydroxyl groups on halogenated BPS to form hydrogen bonds can be boosted due to the substitution of electron-withdrawing halogen atoms; (ii) H-bond strengths of the halogenated BPS molecules can be carefully tuned through relatively simple covalent modifications with different halogen atoms, which, we believe, may endow some superiority in directing the molecular assembly and recognition; (iii) the halogenated BPS molecules are able to generate secondary halogen bonds due to the introduction of X-bond donors, which may result in new and interesting supramolecular assemblies.…”

“…However, the reaction of parent BPS ( 1 ) with PZ ( 4 ) afforded a 2:1 salt (complex 9 ) having 1D ring chain subunits, in which the doubly protonated PZ molecules connect the rings formed by face-to-face half deprotonated BPS moieties via two types of strong hydrogen bonds, O hydroxyl ···H–N (2.579 Å) and O hydroxyl ···H–O hydroxyl (2.560 Å), respectively (Figure S3a, Supporting Information). The ring chains are further extended by week O sulfuryl ···H–N (2.918 Å and 2.985 Å) and O sulfuryl ···H–C (2.975 Å) hydrogen bonds into a 3D supramolecular structure (Figure S3b, Supporting Information). The structure of complex 9 is somewhat straightforward and significantly different from those of complexes 6 and 8 built by halogenated modules with PZ.…”

Rare Case of a Triple-Stranded Molecular Braid in an Organic Cocrystal

“…However, the transitional aromatic rings between the half turns of different handedness have a dihedral angle of 38.7°, which is considered as mismatching segments and responsible for the formation of meso -helical (rather than helical) strings. The bromination of TBBPS may also have subtle influence for the formation of the meso -helical string, due to the enhanced ability of the hydroxyl groups to form hydrogen bonds, which can be tentatively demonstrated by the helical chain structure built by parent BPS ( 1 ) with BPP ( 3 ) …”