A Microsoft extension to the ANSI SQL language that includes procedural programming, local variables, and various support functions.
You need to explicitly cast the string literal to datetime2, because the default conversion is to datetime, which only handles three decimals.
SELECT FORMAT(DATEADD(dd, 0, cast('2021-04-02 18:54:13.4966667' as datetime2(7))), 'HHmmss')