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Find 4 words all 8 letters, that go around the outside of an 8 sided square.
Using all these letters==ADCALUONNOTIMASIVASIRODE
Left side downward ==? ? A D ? ? ? ?
Right side downward == ? ? ? ? ? ? ? ?
Bottom row ==? ? ? ? ? ? ? ?
Top row ==? ? ? ? ? ? ? ? , and is a Villainous female
I think the left side downwards maybe R O A D S I D E
if so top row starts with R O

Since you only have 24 letters, I presume that the pairs of letters in each corner are shared. The villain could be Tatiana ROMANOVA (From Russia, with Love). If the pairs are shared in the same order, that would leave DELUSION and VACATION.

Thank you SPOFFY, you are truly brilliant.
I have been toying with that puzzle for 2 days and only come to this marvellous forum as a last resort.