Method 1: To directly answer your question, the orthogonal complement of the span of the two dimensional subspace spanned by $(1,0,i)$ and $(1,2,1)$ is a one-dimensional subspace. Assume that this subspace is spanned by the vector $(a,b,c)$. For $(a,b,c)$ to be orthogonal to both $(1,0,i)$ and $(1,2,1)$, the inner (dot) products must be zero. In other words, $(a,b,c)$ must satisfy
$$
a-ci=0\qquad\text{and}\qquad a+2b+c=0.
$$
A nonzero solution to this system is a basis for the orthogonal complement.
Method 2: To get a basis, it is easier to start with a spanning set and reduce it to a basis than to get the basis directly. Observe that $(1,0,0)$, $(0,1,0)$ and $(0,0,1)$ form a basis for $\mathbb{C}^3$. Therefore, the vectors of $\{(1,0,i),(1,2,1),(1,0,0),(0,1,0),(0,0,1)\}$ form a spanning subset of $\mathbb{C}^3$. Consider adding $(1,0,0)$ to $\{(1,0,i),(1,2,1)\}$, either the vectors in this new set $\{(1,0,i),(1,2,1),(1,0,0)\}$ are linearly independent or linearly dependent. If they are independent, then you have a basis. If they are dependent, then the span of the vectors in $\{(1,0,i),(1,2,1)\}$ is the same as the span of the vectors $\{(1,0,i),(1,2,1),(1,0,0)\}$, therefore, throw $(1,0,0)$ out and continue with $(0,1,0)$. You will eventually have a basis because the original set was spanning.