Since 2007[1], Special:UserRights has relied on a delimiter to separate the username input into a username and a wiki, allowing for interwiki user rights management. This delimiter was hard-coded as @ until 2009[2], when it was made configurable via $wgUserrightsInterwikiDelimiter.
For usernames that contain the delimiter, Special:UserRights cannot be used normally. At the same time the delimiter was made configurable, $wgInvalidUsernameCharacters was added to prevent registration of new accounts with specific characters, including (by default) @, the default delimiter.
However, accounts that were created before 2009 (or on non-WMF wikis where the configuration was changed) still cannot be modified normally via Special:GlobalRights. Example:
https://en.wikipedia.org/wiki/Special:UserRights/Rms125a@hotmail.com
It is possible to use the user id[3], which can be retrieved via the api[4], but ideally it would be possible to change the user groups of such users without needing to look up their user ids
[1] https://gerrit.wikimedia.org/r/plugins/gitiles/mediawiki/core/+/c3ef834c0400b18ecc75e9ff9a98ec2e240b34df
[2] https://gerrit.wikimedia.org/r/plugins/gitiles/mediawiki/core/+/c75197371c81cfe35b0c29e3cd8ea3219e3a6bd1
[3] In this case, https://en.wikipedia.org/w/index.php?title=Special%3AUserRights&user=%23376014
[4] In this case, https://en.wikipedia.org/w/api.php?action=query&list=users&ususers=Rms125a@hotmail.com