Abstract
In an attempt to modify the dimensions of the hydrogen-bonded helical canal host structure of crystalline exo-2,exo-6-dihydroxy-2,6-dimethylbicyclo[3.3.1]nonane (2), the title compounds which involve a minor substituent change at the 2,6 positions were synthesised. Crystals of exo-2,exo-6-dihydroxybicyclo[3.3.1]nonane (1) and exo-2,exo-6-dihydroxy-2,6-diethylbicyclo[3.3.1]nonane (3) represent two fully hydrogen-bonded structure types distinctly different from the canal structure of (2) and from each other. Stereochemical analysis has not revealed any significant correlation of crystal structure with molecular structure in these compounds: crystal data, (1)P21/c, a 1 297.0(2), b 1 359.1 (2), c 1 115.0(2) pm, β 118.68(2)°, Z 8(×C9H16O2), R 0.046 (3 049 data); (3)Fdd2, a 1 275.6(2), b 1 666.1(2), c 2 326.6(3) pm, Z 16(× C13H24O2), R 0.050 (1 083 data).

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