I also have Mac OSX 10.5.8 and I've tried quite a few different versions of Sigil. Version 0.4.0RC1 is the one I currently use.
If you read the changelog you'll find that as of version 0.4.0 the minimum OSX version was changed to 10.6
So, if you have 10.5.8 you would have to use any version before that.
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