Alpar Pöllnitz

New Organophosphorus Proligands and Amide Precursors: Crystal and Molecular Structures of Ph2P(X)NH(C6H3Pri 2-2,6) (X = O, S) and (OPPh2)(O2SMe)N(C6H3Pri 2-2,6)

The new organophosphorus proligand (OPPh2)(O2SMe)NR (R = C6H3Pri 2–2,6) (3) was prepared as a white crystalline solid by reacting the lithiated compound Li[Ph2P(O)NR] with MeSO2Cl in a 1:1 molar ratio. The precursor Ph2P(O)NHR (1), as well as its thio analogue Ph2P(S)NHR (2), were obtained in the reaction between the lithiated amine RNHLi and the corresponding organophosphorus chloride. All compounds were characterized by multinuclear (1H, 13C, and 31P) NMR spectroscopy. The molecular structures of 1–3 were established by single-crystal X-ray diffraction. A zigzag polymeric chain is formed in the crystals of 1 and 2 by hydrogen N–H···X (X = O, S) bonding, while the crystal of 3 contains discrete monomeric units with a syn–syn conformation of the O˭P(C)2–N–S(C)(˭O)2 skeleton. Supplemental materials are available for this article. Go to the publishers online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.

A new ortho­rhom­bic polymorph of 1,1′-seleno­bis­(N,N-diethyl­sulfanecarbothio­amide)

The title compound [systematic name: N,N-diethyl({[(diethylcarbamothioyl)sulfanyl]selanyl}sulfanyl)carbothioamide], C10H20N2S4Se, crystallizes in a new form in the space group Pca21: the previously reported polymorph crystallizes in the space group P212121. The new phase contains two independent molecules in the asymmetric unit. The Se atoms are tetracoordinated, with a distorted square-planar geometry. The ligands coordinate asymmetrically to the Se atoms, with one strong Se—S bond [range 2.2833 (13)–2.3041 (15) Å] and one weaker bond [range 2.7318 (14)–2.7873 (12) Å].