Some definite integrals, such as $\int_0^\infty e^{-x^2}\,dx$, are known despite the fact that there is no closed-form antiderivative. However, the method I know of calculating this particular integral (square it, and integrate over the first quadrant in polar coordinates) is not dependent on the Riemann sum definition. What I thought might be interesting is a definite integral $\int_a^bf(x)\,dx$ for which the limit of the Riemann sums happens to be calculable, but for which no closed-form antiderivative of $f$ exists. Of course there are some obvious uninteresting examples, like integrating odd functions over symmetric intervals, but one doesn't need Riemann sums to calculate these uninteresting examples.
Edit: To make this a bit clearer, it would be nice to have a "natural" continuous function $f(x)$ where by some miracle $\lim_{n\to\infty} \sum_{i=1}^nf(x_i)\Delta x$ is computable (for some interval $[a,b]$) using series trickery, but for which no antiderivative exists composed of elementary functions.