Are you saying that 大きい and 小さい are the only -い adjectives that can also end in -な?
A little more clarification.
大きな is not "i-adjective that can also en in-な", 大きい and 大きな are two different things, and the difference are already explained by Toritoribe san and myself.
大きな is neither "a variation of i-adjective(形容詞 keiyou-shi)" nor "na-adjective (形容動詞 keiyou doushi)", it is 連体詞 (rentaishi) which does not conjugate.
Maybe my previous post is rather confusing, to be more precise I should have said that 大きな and 小さな are the only 連体詞 I can think of which has similar i-adjectives with almost the same meaning.
There are some more 連体詞 (which is to be placed in front of noun to modify it, but does not conjugate and cannot be used as complement) in various endings:
な: 大きな (big)、小さな(small/little)、いろいろな(various)
が: わが (my)
た: たいした(big, good, great, awsome, etc.)
の: この、その、あの、どの
る: あらゆる (all/every)、いわゆる (so-called)、ある (certain)、来る(きたる, coming)
But you do not have to remember them all - just remember that 大きな and 小さな look very similar to 大きい and 小さい but they are different.