PokéBase - Pokémon Q&A
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Once you've beat the elite 4, and entered Team Plasma's castle, you will be given the chance to battle and catch Reshiram right before your final battle with N. After catching Reshiram the game will ask if you want to add it to your party and send another Pokemon to the box so that the two heros with opposing ideals can have a true face off both using their respective legendary Pokemon

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Before. As soon as you enter the chamber where N is in the plasma castle the stone in your bag will transform into the dragon and N will tell you that the dragon is saying to prove your strength to it and make it a part of your team.

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You catch Reshiram then battle N right after
Source: Experience

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