I guess I'd try representing the space spanned by unit vectors in the five relevant directions as a $\mathbb Q$-vectorspace. Its dimension should be $4$, so there exists a non-trivial linear combination which evaluates to zero (i.e. which closes the pentagon), and the coefficients for that linear combination should be all equal, corresponding to unit length.
Detais (hidden inside a spoiler block, so move mouse over to read):
Suppose your coordinate system is aligned in such a way that one of the edges is oriented with the $x$ axis. Then vectors of unit length in your five edge directions will be:
\begin{align}d_1&=\begin{pmatrix}1\0\end{pmatrix}&d_2&=\begin{pmatrix}\cos72°\\sin72°\end{pmatrix}=\begin{pmatrix}\frac{\sqrt5-1}4\[1ex]\sqrt{\frac{5+\sqrt5}8}\end{pmatrix}&d_3&=\begin{pmatrix}\cos144°\\sin144°\end{pmatrix}=\begin{pmatrix}\frac{-\sqrt5-1}4\[1ex]\sqrt{\frac{5-\sqrt5}8}\end{pmatrix}\&&d_5&=\begin{pmatrix}\cos72°\-\sin72°\end{pmatrix}&d_4&=\begin{pmatrix}\cos144°\-\sin144°\end{pmatrix}\end{align}
Now you can choose a basis for your four-dimensional $\mathbb Q$-vectorspace. One possible choice would be the following:
\begin{align}b_1 &= \begin{pmatrix}\frac14\[1ex]0\end{pmatrix} & b_2 &= \begin{pmatrix}\frac{\sqrt5}4\[1ex]0\end{pmatrix} & b_3 &= \begin{pmatrix}0\[1ex]\sin72°\end{pmatrix} & b_4 &= \begin{pmatrix}0\[1ex]\sin144°\end{pmatrix}\end{align}
To show that they are indeed a basis, you have to show that they are linearily independent over $\mathbb Q$. In other words, their coordinates must be incommensurable:
\begin{equation}\frac{;\frac{\sqrt5}4;}{\frac14} = \sqrt5 \not\in\mathbb Q\qquad\frac{\sin72°}{\sin144°} = \sqrt{\frac{5+\sqrt5}{5-\sqrt5}} = \sqrt{\frac{3+\sqrt5}{2}} = \frac{1+\sqrt5}{2} = \varphi \not\in\mathbb Q\end{equation}
So they are indeed independent. Now we can write our original direction vectors $d_i$ in terms of this basis, as the columns of the following matrix:
\begin{equation} M = \begin{pmatrix} 4 & -1 & -1 & -1 & -1 \ 0 & 1 & -1 & -1 & 1 \ 0 & 1 & 0 & 0 & -1 \ 0 & 0 & 1 & -1 & 0 \end{pmatrix} \qquad \ker(M) = \operatorname{span}\begin{pmatrix}1\1\1\1\1\end{pmatrix} \end{equation}
So the only way to add rational multiples of your direction vectors in such a way that that the sum is zero (i.e. the polygon they describe actually closes) is by taking the same length in each of the directions. Which results in either a regular pentagon or a regular pentagram. Since the problem statement spoke about a pentagon, I assume it meant a simple polygon without self-intersection. So that rules out the pentagram case.