Logon to SharePoint Server which is hosting the SharePoint Site.
Go to Command Prompt as Admin
Now run the below command and provide details as mentioned below. SiteCollection Admin UserName should also be like Domain\UserName
stsadm -o adduser -url "SharePoint Site URL" -userlogin "domain\username" -useremail "username@domain.com" -group "group name" -username [SiteCollection Admin UserName]
Go to Command Prompt as Admin
Now run the below command and provide details as mentioned below. SiteCollection Admin UserName should also be like Domain\UserName
stsadm -o adduser -url "SharePoint Site URL" -userlogin "domain\username" -useremail "username@domain.com" -group "group name" -username [SiteCollection Admin UserName]