RESUMO
Investigations of the reactivity of the thio-crown [14]aneS(4) (1,4,8,11-tetrathiacyclotetradecane) towards the aminating agent o-mesitylsulfonylhydroxylamine have lead to the crystallization of 1lambda(4),4lambda(4),8lambda(4),11lambda(4)-tetrathiacyclotetradecane-1,4,7,10-tetraylidenetetraaminium tetrakis(2,4,6-trimethylbenzenesulfonate), C10H28N4S(4)4+.4C9H11O3S-. The compound crystallizes in a centrosymmetric space group, with half a formula unit in the asymmetric unit. All S atoms within the cationic component are aminated, with the four NH(2) substituents arranged in pairs on neighbouring S atoms on opposite faces of the crown. The macrocyclic cation in the compound forms hydrogen bonds with the 2,4,6-trimethylbenzenesulfonate anions to create chains, which are further linked into thick two-dimensional sheets.
RESUMO
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.
RESUMO
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.
RESUMO
The title compound, (C30H25NPS)2[Pd2Br6] or (Ph3PNSPh2)2[Pd2Br6], was crystallized from the reaction of (Ph3PNSPh2)[BPh4] with (PPh4)2[Pd2Br6], giving a salt rather than the intended coordination complex [PdBr3(Ph3PNSPh2)]. The compound crystallizes in the non-centrosymmetric space group Cc with one complete formula unit in the asymmetric unit. One of the two independent cations is disordered. The geometry of the two cations is compared with that of the only previously crystallized example of this cation, viz. its [SbCl6]- salt [Reck et al. (1982). Chem. Ber. 115, 2981-2996]. The bond angles within the P-N-S triad in the two cations in the title compound are narrower than those observed in the literature example, while the S-N bond lengths are slightly longer in the title compound. The P-N bond length in the ordered cation shows excellent agreement with that determined by Reck and co-workers, but the P-N bond lengths are lengthened slightly in the disordered cation. Weak C-H...Br interactions create a three-dimensional network, with cations and anions alternating along the crystallographic c direction.
RESUMO
Pt(IV)-mediated addition of the sulfimide Ph2S = NH and the mixed sulfide/sulfimides o- and p-[PhS(=NH)](PhS)-C6H4 by the S=NH group to the metal-bound nitriles in the platinum(IV) complexes [PtCl4(RCN)2] proceeds smoothly at room temperature in CH2Cl2 and results in the formation of the heterodiazadiene compounds [PtCl4[NH=C(R)N=SR'Ph]2] (R' = Ph, R = Me, Et, CH2Ph, Ph; R' = o- and p-(PhS)C6H4; R = Et). While trans-[PtCl4(RCN)2] (R = Et, CH2Ph, Ph) reacting with Ph2S=NH leads exclusively to trans-[PtCl4[NH=C(R)N=SPh2]2], cis/trans-[PtCl4(MeCN)2] leads to cis/trans mixtures of [PtCl4[NH=C(Me)N=SPh2]2] and the latter have been separated by column chromatography. Theoretical calculations at both HF/HF and MP2//HF levels for the cis and trans isomers of [PtCl4[NH=C(Me)N=SMe2]2] indicate a higher stability for the latter. Compounds trans-[PtCl4[E-NH=C(R)N=SPh2]2] (R = Me, Et) and cis-[PtCl4[E-NH=C(Me)N=SPh2][Z-NH=C(Me)N=SPh2]] have been characterized by X-ray crystallography. The complexes [PtCl4[NH=C(R)N=SPh2]2] undergo hydrolysis when treated with HCl in nondried CH2Cl2 to achieve the amidines [PtCl4[NH=C(NH2)R]2] the compound with R = Et has been structurally characterized) and Ph2SO. The heterodiazadiene ligands, formed upon Pt(IV)-mediated RCN/sulfimide coupling, can be liberated from their platinum(IV) complexes [PtCl4[NH=C(R)N=SR'Ph]2] by reaction with Ph2PCH2CH2PPh2 (dppe) giving free NH=C(R)=SR'Ph and the dppe oxides, which constitutes a novel route for such rare types of heterodiazadienes whose number has also been extended. The hybrid sulfide/sulfimide species o- and p-[PhS(=NH)](PhS)C6H4 also react with the Pt(II) nitrile complex [PtCl2(MeCN)2] but the coupling--in contrast to the Pt(IV) species--gives the chelates [PtCl2[M-I=C(Me)N=S(Ph)C6H4SPh]]. The X-ray crystal structure of [PtCl2[M-I=C(Me)N=S(Ph)C6H4SPh-o]] reveals the bond parameters within the metallacycle and shows an unusual close interaction of the sulfide sulfur atom with the platinum.
