Premium
X‐ray, 31 P CP/MAS, and Single‐crystal NMR Studies, and 31 P DFT GIAO Calculations of Inclusion Complexes of Bis[6‐ O ,6‐ O′ ‐(1,2:3,4‐Diisopropylidene‐ α ‐ D ‐galactopyranosyl)thiophosphoryl] Disulfide: The Importance of CH⋅⋅⋅SP Contacts in the Solid State
Author(s) -
Potrzebowski Marek J.,
Grossmann Gisbert,
Ganicz Katarzyna,
Olejniczak Sebastian,
Ciesielski Włodzimierz,
Kozioł Anna E.,
Wawrzycka Irena,
Bujacz Grzegorz,
Haeberlen Ulrich,
Schmitt Heike
Publication year - 2002
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/1521-3765(20020617)8:12<2691::aid-chem2691>3.0.co;2-e
Subject(s) - chemistry , crystallography , hydrogen bond , chemical shift , molecular geometry , crystal structure , intermolecular force , single crystal , principal axis theorem , crystal (programming language) , stereochemistry , computational chemistry , molecule , geometry , organic chemistry , computer science , programming language , mathematics
Bis[6‐ O ,6‐ O′ ‐(1,2:3,4‐diisopropylidene‐ α ‐ D ‐galactopyranosyl)thiophosphoryl] disulfide shows a strong tendency to form inclusion compounds. The crystal and molecular structure of eight different solvates was established by X‐ray analysis. The results indicate three different types of disulfide arrangements in the crystal lattice. By means of 31 P CP/MAS NMR experiments the principal values δ 11 , δ 22 , and δ 33 of the 31 P chemical shift tensor were obtained for each form. The orientation of its principal axes with respect to a molecular frame was investigated by means of 31 P CP and single‐crystal NMR for the complex with propan‐2‐ol. The principal axis 1 of both chemically equivalent phosphorus atoms is nearly parallel to the PS bond and the principal axis 3 is very close to the PS bond. DFT GIAO calculations of the model compound (EtO) 2 (S)P 1 SSP 2 (S)(OEt) 2 allowed assignment of the experimental chemical shift curves to the magnetically nonequivalent atoms P 1 and P 2 . The maximum difference between calculated angles (∢ i PX) calcd and experimental angles (∢ i PX) exptl is 8.3° and the rms distance 3.8° ( i =principal axes 1, 2, 3; X=S, ‐S‐, ‐O1‐, ‐O2‐). The influence of CH⋅⋅⋅S weak hydrogen bonding on phosphorus shielding was tested theoretically ( 31 P DFT GIAO) employing the dimethoxythiophosphoryl disulfide ⋅ CH 4 complex as a model compound. The sensitivity of 31 P δ ii parameters to intermolecular forces is demonstrated.