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You might want disable sync for the game folder and have sync only for save game folder. Generally speaking syncing the whole My Documents folder can be bad idea (though cloud save application may recommend it). It's better to sync only data files to the cloud, not files that applications use runtime or the application may act abnormally.
First thing to check would be making sure that the game's folder (in My Documents) is not write protected, including subfolders. You can also check if same happens on all versions, launching the game on both DX9 and DX10/11 modes. Different modes have different settings, so one may work while another does not.
Civ V is an old game, so having a newer game installed after it may sometimes mess it up, but already said you tried to fix those (like DX install), so that might not be the problem.
You could try a clean install, by 1) removing the game from Steam, then 2) delete the game's folder from the My Documents (but backup local game saves first if you want to save those) before 3) reinstalling the game again from Steam. Without the second step the Steam uses old settings from previous installation. You have important knowledge if you do that. You know that it's not the game that is the problem, if you do that and right after that (without installing anything else) the game does not work. In that case it must be something else in your computer.
There is a way to see what that another locking application is. I'm a programmer, and I have that problem of application locking files another application needs more often than I would like. So, I have used small little freeware application called LockHunter (there are most likely other alternatives too) for years to see what is the culprit and to unlock the files. With that application you can see what the locking application is (when you run the Civ V) You could see if it is some Windows' process or a third party application.
I hate to be difficult and act like a broken record but anything Win 10 and later is a problem of itself. Messing with settings that should stay set.
I learned to disallow cloud, google cloud cloud anything among other things.
Steam has been very good over a great many years providing the ability to install games on new builds or replacement rebuilds when necessary which is why I have it.
I was contemplating the recent update on my system from MS that recreated the things I eliminated from my windows. Its almost like sticking a finger in the soup making sure that I am not allowed in a manner of speaking to keep the settings just so.
In any case there will not be a win 12 or win 50 or god only knows what else in the future.
One more thing, when I was reading other posts I remember people talking about two .ini files. I believe one was called config.ini? I remember I searched for that in that folder and it was not there? Maybe when Civ 5 is installing/verifying it still is not putting that file in? (I have no idea what that file does but might be a good shot in the dark).
Thanks again for your help Damsteri I really appreciate it!
Theres a old Redhat on the box, a number of win 7's 32 and 64 bits kept as working boxes and battle spares and theres a XP Pro Which really is old. I suppose if I dug deeper I can dig up a Win Me which was older than that and beloved for what it was. (Gaming in those days with one core CPU's were minimized to just that game process exe and the windows exe only. Nothing else.
The most interesting is a older Knoppix which is forensics, DOS and a few other scary pre windows stuff with commands long forgotten. I finally learned Binary and all that good stuff but pray what do I do with it? Or Basic, HTML etc. Its all rattling around up there.
Sometimes I rejoice in getting old. However....
I have killed most all social media, I have killed medical stuff (Patient Portals and so on which means I dont go to doctors who require it anymore) I have killed legal, smartphone and financial stuff.
Gone back as much as possible to old fashioned face to face purchasing with cash as much as possible. Eliminated all technology except the necessary computer to play a game. Everything else tossed. Even the computer controlled crockpot. Thats gone.
Yes its very interesting getting older. When I live alone, I dont need a nanny, wife or busy body sticking their nose into my home telling me whats what.
AND above all else...
Ended, killed, Shot dead, deleted anything that requires a monthly sub to play games released 20 years ago. No sub anything. Which means the cash stays in the pocket.
Mine.
I try not to be consumed with thoughts of the poor Bairns growing up with this here Internet that will be required as food, water and breathing air to function today.
Config.ini is used for some game setup that normal users don't need to change, but it is also used to save your last game settings, like which civilization, difficulty, map, etc. you used last time.