I haven't read one in years (and I don't usually read "TV" sf books), but I do remember fondly and can recommend the following original series books:
The Final Reflection by John M. Ford
Yesterday's Son (Star Trek, No 11) by A.C. Crispin
Ishmael (Star Trek, No 23) by Barbara Hambly
The first is a bit of pre-history, involving early human-klingon relations from the klingon point of view. The other two are time-travel stories with Spock as a central character.
I'm a Barbara Hambly fan anyway, which is why I picked up Ishmael, but the book stood on its own quite well. None of these are dependent on any others, but familiarity with the original Trek universe is probably best to be able to appreciate what's going on in them.
Happy reading,
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