Characterizing the \(6\times 6\) complex Hadamard matrices (CHMs) is an open problem in linear algebra and quantum information. We name the \(6\times 6\) CHMs except the \(H_2\) -reducible matrices and the Tao matrix as the non- \(H_2\) -reducible matrices. As far as we know, no non- \(H_2\) -reducible matrices with analytic form have been found. In this paper, we find some non- \(H_2\) -reducible matrices with analytic form. We also characterize some special \(6\times 6\) CHMs. Using our result one can further narrow the range of MUB trio (a set of four MUBs in \(\mathbb {C}^6\) consists of an MUB trio and the identity). Our results may lead to the complete classification of \(6\times 6\) CHMs and the solution of MUB problem in \(\mathbb {C}^6\) .