Does your data look something like this:
Jan12, Tom, 1, a
Jan12, Tom, 2, b
Jan13, Bob, 3, a
Jan14, Sue, 4, b
I think you saying that you want to run (Query 1):
SELECT C3 from TBL WHERE C1=<Datetime> and C4='a' and C3 is not null
However, if no record is found, you want to then run (Query 2):
SELECT C3 from TBL WHERE C1=<Datetime> and C4='b'
If that your objective, consider the second query. To leave out anything that would have returned a record via the first query, you could do this (note modified second query only) (Query 2A):
SELECT C3 from TBL WHERE C1=<Datetime> and C4='b'
and NOT EXISTS (SELECT * from TBL WHERE C1=<Datetime> and C4='a')
So, you now have two queries, with mutually-exclusive results. You can simply UNION them together and run them as one (Final, combined query).
SELECT C3 from TBL WHERE C1=<Datetime> and C4='a' and C3 is not null
UNION ALL
SELECT C3 from TBL WHERE C1=<Datetime> and C4='b'
and NOT EXISTS (SELECT * from TBL WHERE C1=<Datetime> and C4='a')