I didn't stay in either of the two hotels. But although the two hotels are close to each other, I would prefer the 25 hours in terms of location.
The 25 hours is in a historic building directly opposite the main train station. Well, the main station is a huge construction site right now, but right next to the hotel is an escalator to the mezzanine of the main station and Schuetzen-street leads directly to Karlsplatz and the pedestrian zones in the city center.
Schiller5 is in Schiller-Strasse which is a bit shabby and the building next door and the building on the other side of the street are currently under construction.
I have been to the restaurant (Neni) and the bar of the 25 hours hotel, both are very stylish and the food at Neni was really good. But you could also go there if you stay at Schiller5.
Don't worry too much. Neither hotel is bad and the impact of this decision on your trip will be minimal.