Volume estimates of metric balls in manifolds find diverse applications in information and coding theory. In this paper, some new results for the volume of a metric ball in unitary group are derived via various tools from random matrix theory. The first result is an integral representation of the exact volume, which involves a Toeplitz determinant of Bessel functions. The connection to matrix-variate hypergeometric functions and Szegő's strong limit theorem lead independently from the finite size formula to an asymptotic one. The convergence of the limiting formula is exceptionally fast due to an underlying mock-Gaussian behavior. The proposed volume estimate enables simple but accurate analytical evaluation of coding-theoretic bounds of unitary codes. In particular, the Gilbert-Varshamov lower bound and the Hamming upper bound on cardinality as well as the resulting bounds on code rate and minimum distance are derived. Moreover, bounds on the scaling law of code rate are found. Lastly, a closed-form bound on diversity sum relevant to unitary space-time codes is obtained, which was only computed numerically in literature.