Note the following excerpts from MSYS2 documentation:
Name        Prefix        Toolchain    Architecture    C Library    C++ Library
MINGW64  /mingw64  gcc            x86_64            msvcrt       libstdc++
UCRT64     /ucrt64      gcc            x86_64            ucrt           libstdc++
CLANG64   /clang64    llvm           x86_64            ucrt           libc++
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GCC vs LLVM/Clang:
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GCC based environments:
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While there also exists a Clang package in the MINGW environments, that one still uses the GNU linker and the GNU C++ library.
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LLVM/Clang based environments:
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Only uses LLVM tools, LLD as a linker, LIBC++ as a C++ standard library.
Also note the following from the README.md file at
https://github.com/mstorsjo/llvm-mingwwhich is where Mingw-w64 seems to get it's clang/llvm implementations:
Clang on its own can also be used as compiler in the normal GNU binutils based environments though, so the main difference lies in replacing binutils with LLVM based tools.