If he divorced while she was pure, but had sex with her as well during that time, prior to reciting the divorce, or after, the divorce would not have been valid.
Divorce needs to take place after a wife has her cycle, and is pure (fi tuhr ghayr muwaqa'ah).
It is not wajib to immediately do ghusl, and is permissible to postpone, as long as it will be done before the next wajib prayer, or in the case of the month of Ramadhan, before fajr.
However, it definitely is not a good thing to do, based on our ahadeeth. Hadiths say to do it immediately. Why would one choose to stay in the state of inner impurity? You cannot enter the mosque, recite parts of the Quran, touch the Quran. It is makruh to eat, or drink, or sleep, and all the other things that are makruh.
Why would one deprive himself/herself of many blessings of being tahir?
Therefore, best thing is to become accustomed to do ghusl straight away, and always try to be in state of taharah.
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