Extremely long range firing was not necessarily against massed troops or even visible targets. Prior to the use of machineguns, armies envisioned employment of rifle fire for interdiction firing. The target could be a staging area, a cross roads, a railway station, an artillery emplacement, or some other relatively large area. The target could be behind a tree line, or even on the other side of a hill. An aiming point, visible to the shooter, was chosen, the sights adjusted for the selected range, and a massed unit, even as large as a regiment, fired all at once on command, hence the term "volley firing".
It almost goes without saying that anyone actually hit by such firing was just plain unlucky, but the idea was to affect morale and disturb the enemy's activities, not necessarily to kill anyone. Still, a thousand or so bullets landing in an area every few seconds would tend to give troops on the receiving end the "willies".
At least that was the theory. Was it ever used in combat? I have found no mention of such firing in any battle history, but that does not mean it wasn't used. In any case, it was possible and the military wanted rifles that could do it if necessary.
The rifle fire at the battle of Mons was not volley firing; it was not especially long range and was aimed fire. Its accuracy and rapidity was what caused the Germans to believe machineguns were in use, rather than rifles.
Jim
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