Praise be to Allah.
If a man comes in after Fajr or ‘Asr, and he has missed the (congregational) prayer, there is nothing wrong with another man praying with him and giving him “charity” in this way. The rule is that every naafil prayer that is done for a specific reason may be done at a time when naafil prayers are otherwise not allowed, such as Tahiyyat al-masjid (greeting the mosque), sujood al-tilaawah (prostration when reciting Qur’aan) and Salaat al-Istikhaarah when the matter is urgent and a decision must be reached before the end of the time when naafil prayer is not allowed, giving “charity” to someone who comes in after ‘Asr or Fajr, and similar cases.
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