$E$ is a nonempty finite subset of $\mathbb{R}$ and it is well known that such a subset has a smallest and a largest element.
Of course, this is not true for any infinite subset. Consider for example the interval $(0,1)$, which has no smallest and no largest element. It has nevertheless a "largest lower bound" = 0 and a "smallest upper bound" = 1.
Now, let's go back to :
$$E=\{\frac{n}{q}-1;\,1\le q\le n\}$$
The smallest element of $E$ is reached by choosing the largest value of $q$; and the largest element of $E$ is reached by choosing the smallest value of $q$. So we have :
$$\inf(E)=\min(E)=0\qquad\mathrm{and}\qquad\sup(E)=\max(E)=n-1$$
Note : I consider that $\mathbb{N}$ is the set of all natural numbers, including $0$. If you consider that $\mathbb{N}$ is the set of positive integers (1, 2, etc ...) then you have to adapt slightly what I wrote :
$$E=\{\frac{n}{q}-1;\,1\le q\le n-1\}$$
and the conclusion becomes :
$$\inf(E)=\min(E)=\frac{1}{n-1}\qquad\mathrm{and}\qquad\sup(E)=\max(E)=n-1$$