The tms structure predates 4BSD
https://www.tuhs.org/cgi-bin/utree.pl?file=V7/usr/include/sys/times.h
and the order of the data was earlier still
https://www.tuhs.org/cgi-bin/utree.pl?file=V3/man/man2/times.2
https://www.tuhs.org/cgi-bin/utree.pl?file=V4/man/man2/times.2

Though I don't see the point in documenting the history of the struct.

Index: lib/libc/gen/times.3
===================================================================
RCS file: /cvs/src/lib/libc/gen/times.3,v
diff -u -p -r1.16 times.3
--- lib/libc/gen/times.3	11 Sep 2022 06:38:10 -0000	1.16
+++ lib/libc/gen/times.3	30 Jun 2024 04:22:36 -0000
@@ -142,11 +142,3 @@ A
 .Fn times
 function first appeared in
 .At v3 .
-The tms structure first appeared in
-.Bx 4.0
-and was changed to use
-.Vt clock_t
-instead of
-.Vt time_t
-for its members in
-.Bx 4.3 Net/2 .