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2. Second to bottom option is Settings, open it
3. On the left side look for "In-Game" section
4. Scroll down and you will find Screenshots, assign your button there.
another way is to look ingame settings to see if there is screen shot button what you can change
are you doing the steps given?
from google - To take a screenshot in Dota 2, the default Steam hotkey is F12. If you want to change this button, you can do so in the Steam settings by going to Steam > Settings > In-Game and modifying the screenshot hotkey. You can also use the Windows Snipping Tool (Windows Key + Shift + S) or the Print Screen (PrtSc) key, though F12 is generally preferred for Steam-integrated games like Dota 2.
another from youtube - https://www.youtube.com/watch?v=7-kNGqxG3Rc
I couldn't reach F12 comfortably during those, without my hands leaving either the left part of the keyboard or the mouse to take a shot, which resulted to death in most cases.
So I switched it to F3.
Ah, OK. The overlay shouldn't cause disconnections in Dota, but maybe there is a bug that I don't know about. Steam can't take screenshots without the overlay though.