Kathryn E. Holmes

Reactions of mono- and bis-N-bromosulfimides with thio-ether crowns, phosphines and selenides

The brominated sulfimide Ph2SNBr reacts with diphosphines 1,2-(PPh2)2C2H4 and 1,4-(Ph2P)2(C6H4) to give the bis-N-phosphoniosulfimidium cations [1,2-(Ph2PNSPh2)2C2H4]2+ and [1,4-(Ph2PNSPh2)2(C6H4)]2+, respectively. Treatment of the bis-sulfimide 1,4-[PhSNH]2C6H4 with N-bromosuccinimide results in 1,4-[PhSNBr]2C6H4, which in turn reacts with triphenylphosphine to generate [1,4-(PhS{NSPPh3})2C6H4]Br2. Both Ph2SNBr and 1,4-[PhSNBr]2C6H4 react with the thio-ether crown [9-ane]S3, giving [9[ane]S3NSPh2]Br and [1,4-{[9-ane]S2S(NSPh)2C6H4]Br2, respectively. The first examples of seleniosulfimidium salts have been isolated from the reactions of Ph2SNBr and 1,4(PhS{NBr})2C6H4 with Ph2Se and the structures of the [Ph2SNSePh2]+ and [1,4-(PhSNSePh2)2C6H4]2+ cations confirmed by X-ray crystallography. Reaction of 1,2-PhS(NH)C6H4SPh with one equivalent of N-bromosuccinimide followed by addition of Na[BPh4] results in [1,2-(PhS)2(μ-N)C6H4][BPh4] in which a CCSNS ring is observed; two forms of this material may be isolated upon crystallisation—X-ray crystallography reveals them to differ by the relative orientations of the phenyl rings.

Concomitant polymorphism of [Cu(Ph2SNH)4][PF6]2

The complex [Cu(Ph2SNH)4][PF6]2 crystallises in three different forms, two of these are true polymorphs whilst the third form is a pseudo-polymorph as solvent molecules are incorporated into the lattice. The forms differ in both the geometry of the copper centre and the orientation and form of the supramolecular interactions observed.

The preparation and structure of novel sulfimide systems; X-ray crystal structures of 1,4-(PhS{NH})2C6H4(and dihydrate), 1,2-(PhS{NH})(PhS)C6H4·H2O and of [Ph2SNH] and its hydrate

Treatment of 1,4-(PhS)2C6H4 and 1,2-(PhS)2C6H4 with the appropriate amount of O-mesitylsulfonylhydroxylamine (MSH) yields the corresponding protonated sulfimides, both of which may be deprotonated with DBU to give the hydrated free sulfimides 1,4-(PhS{NH})2C6H4·2H2O 1a and 1-(PhS{NH})-2-(PhS)C6H4·H2O 2a. The X-ray crystal structures of both 1a and 2a, together with that of the well-known sulfimide Ph2SNH·H2O 3a, all reveal extended hydrogen-bonded arrays involving the N–H units and the waters of crystallisation. Crystals of 1b, the dehydrated form of 1a, also readily form, while removal of the water from 3ain vacuo followed by slow evaporation of a solution in diethyl ether under anaerobic conditions leads to crystals of Ph2SNH 3b; the X-ray crystal structures of both 1b and 3b also reveal extended arrays formed from N–H⋯N interactions. In contrast, dehydration of 2a breaks down the extended structure resulting in the formation of an oil.

Structural diversity within the products of the reaction of Ph2SNH with copper(II) tetrafluoroborate

S,S′-diphenylsulfimide Ph2SNH (1) reacts with copper tetrafluoroborate to give a number of different products including two concomitant polymorphs of [Cu(Ph2SNH)4][BF4]2, the interallogon [Cu(Ph2SNH)4]2[BF4]4 and [Cu(Ph2SNH)4][Cu(Ph2SNH)5][BF4]4, an extremely rare example of a homoleptic system exhibiting four- and five-coordinate metal centres in the same unit cell.

New observations of structural diversity in copper(II) complexes of diphenylsulfimide

Reaction of S,S′-diphenylsulfimide, Ph2SNH (1), with Cu[BF4]2 in acetonitrile generates a solution from which six products may be crystallised: two polymorphs of [Cu(Ph2SNH)4][BF4]2, the inter-allogon [Cu(Ph2SNH)4]2[BF4]4, the mixed coordination system [Cu(Ph2SNH)4][Cu(Ph2SNH)5][BF4]4, five-coordinate [Cu(Ph2SNH)5][BF4]4 (2) and the nitrile adduct [Cu(Ph2SNH)3(Ph2SNC(Me)NH)][BF4]2 (3). Great structural diversity is also observed in the perchlorate [Cu(Ph2SNH)4][ClO4]2 (4) and [Cu(Ph2SNH)4]2[ClO4]4 (5) and nitrate [Cu(Ph2SNH)4][NO3]2 (6) and [Cu(Ph2SNH)4][Cu(Ph2SNH)5][NO3]4 (7) salts.

The formation of supramolecular arrays in copper sulfimide complexes via aerial CO2 fixation; the X-ray crystal structures of [Cu(Ph2SNH)4]2(HCO3)2(trans-O2CCHCHCO2)·4H2O, Cu(Ph2SNH)2(η2-CO3) and Cu(Ph2SNH)2(η2-CO3)·H2O

Copper fumarate reacts with Ph2SNH, 1, in water–methanol, in the presence of air, to give [Cu(Ph2SNH)4]2(HCO3)2(trans-O2CCHCHCO2)(H2O)4, 2. X-Ray crystallography reveals that within the structure of 2 the sulfimide N–H groups are linked into hydrogen-bonded arrays by the C–O units of both the fumarate anion and of the [(HCO3)2]2− dimer (which results from fixation of aerial CO2). A similar reaction using copper sulfate results in Cu(Ph2SNH)2(η2-CO3), 3, in ca. 10% yield; higher yields may be obtained by addition of Na2CO3 to the starting mixture. The structure of 3 again consists of an array, in this case generated by interaction of the sulfimides with the uncoordinated C–O of the carbonate ligand. The hydrate Cu(Ph2SNH)2(η2-CO3)·H2O, 3a, can also be crystallised and reveals a honeycomb structure generated by hydrogen-bond linkages from water molecules.

Solvent-mediated variation of the terephthalate coordination mode in copper sulfimide complexes

Reaction of copper(II) terephthalate and S,S′-diphenylsulfimide in MeOH gives a 1-D coordination polymer with inner-sphere terephthalate ligands; addition of H2O to the reaction solution, however, results in a hydrogen bonded array with the terephthalate anion acting as an outer-sphere ligand.

Polymorphism in ammonium 2,4,6-trimethyl­benzene­sulfonate

During investigations into sulfide- and selenide-amination reactions using the aminating agent o-mesitylsulfonylhydroxylamine, the monoclinic, (I), and orthorhombic, (II), polymorphs of ammonium 2,4,6-trimethylbenzenesulfonate, NH4+.C9H11O3S-, have been crystallized. Investigation of the hydrogen-bonding motifs within the two polymorphs shows that both contain N+-H...O- hydrogen bonds between the ammonium cations and the 2,4,6-trimethylbenzenesulfonate anions. Polymorph (I) contains R(4)(4)(12) and R(4)(2)(8) graph-set ring motifs, while polymorph (II) contains the same R(4)(4)(12) ring motif in combination with an R(4)(3)(10) motif. The two hydrogen-bonding patterns result in slightly different packing structures for the two polymorphs, but both are based on a thick-sheet arrangement, in which the NH4+ cations are enveloped between two layers of 2,4,6-trimethylbenzenesulfonate anions. In (I), the aromatic rings of the anions are approximately coplanar, giving parallel sheets, whereas in (II) the sheets are antiparallel and the anions pack in a herring-bone manner within the sheets, with angles of 78.76 (8) degrees between the planes of the aromatic rings.

N-(Diphenyl­selenio)diphenyl­sulfimidium tetraphenyl­borate

The title compound, C24H20NSSe+.C24H20B-, exhibits disorder (S/Se scrambling) of the chalcogen sites within the S-N-Se triad. Similar disorder was observed in the bromide salt [Aucott, Bailey, Elsegood, Gilby, Holmes, Kelly, Papageorgiou & Pedron-Haba (2004). New J. Chem. pp. 959-966]. The S-N and Se-N bond lengths are 1.6735 (15) and 1.8045 (14) A, respectively. Whereas the chalcogens in the bromide salt are involved in S...Br and Se...Br interactions of very similar distances, the scrambled S and Se sites in the title compound are involved in distinct non-bonded interactions. The site predominantly occupied by sulfur is involved in C-H...S/Se interactions, while the site predominantly occupied by selenium is involved in Se/S...pi interactions.

The preparation and crystal structures of derivatised sulfimidium salts

Preparation and protonation of the hydroxy derivatised sulfimides 2- and (4-C6H4OH)(Ph)SNH gives a sulfimidium cation with three hydrogen bond donors, two NH hydrogens and an OH hydrogen. These all interact with the chloride counterion to give extended hydrogen bonded arrays. The effect of the position of the hydroxy group on the network produced is investigated. Also reported is the structure of the bis-sulfimidium salt [1,3-(PhSNH2)2C6H4]Cl2 which also exhibits a hydrogen bonded array.