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Yes they did. It happened in season 2 the night that Angel and Buffy are ambushed when Angel tries to get on a cargo ship to protect the arm of the judge from getting into Spike and Drucilla's hands. After they sleep together Angel looses his soul and turns bad due to a curse placed on him by Jenny Carpenters people.

I think besides the first time, they also had sex again, maybe once more in the same Angel episode " I Will Remember You" when he turned human. Also, more recently, they did it again in Buffy Season 8. If you have no idea what I'm taking about, try looking up the Buffy comic "Twilight arc" and you will know what I mean.

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