Crystal and molecular structure of octakis(6-bromo-6-deoxy)-gamma-cyclodextrin. A novel stacking of a distorted macrocycle.
Octakis(6-bromo-6-deoxy)cyclomaltooctaose, perbrominated gamma-cyclodextrin at the primary side, crystallises from methanol in a very unique manner. The macrocycles are quite distorted in contrast to their beta-cyclodextrin analogue, heptakis(6-bromo-6-deoxy)cyclomaltoheptaose. The two monomers, arranged head-to-head, form a completely new kind of dimer by mutually entering into each other, both at the primary and the secondary sides. At the primary, hydrophobic side, they interact by Br...Br interactions and at the secondary, hydrophilic side, by direct H-bonds between hydroxylic groups. The short contacts of the Br atoms contribute to the macrocycle's distortion, which is considerable compared to the few available structures of gamma-CDs persubstituted at the primary side with bulkier and in some occasions charged substituents. Water and methanol molecules are entrapped in the cyclodextrin cavity, mostly in the area of the secondary hydroxylic groups connecting the macrocycles by indirect H-bonds. Thus the solvent molecules strengthen the association of the two monomers and contribute to the stabilisation of the cavity. The monomers stack along the a-axis and form columns that align in parallel lines along the same axis resulting in the formation of alternating hydrophobic and hydrophilic layers perpendicular to the a-axis resembling in this respect, the structure of the analogous perbrominated beta-cyclodextrin.
Paulidou
Anastasia
A
Institute of Physical Chemistry, National Center for Scientific Research 'Demokritos', Aghia Paraskevi 15310, PO Box 60228, Athens, Greece.
Giastas
Petros
P
Mourtzis
Nikolaos
N
Yannakopoulou
Konstantina
K
Mavridis
Irene M
IM
D000818:Animals; D002417:Cattle; D018360:Crystallography, X-Ray; D047028:Macrocyclic Compounds / Q000737:chemistry*; D047408:gamma-Cyclodextrins / Q000737:chemistry*
D047028:Macrocyclic Compounds; D047408:gamma-Cyclodextrins