Run half-life 2 atleast once on both the computers, start steam in offline mode and profit. Anyways for Half-Life 2 co-op I'd recommend the Obsidian Conflict mod it's way better than synergy in my opinion.
You need to purchase a game, not something free. I like it this way. This keeps the huge flood of scammers away from saying HAI DIS IS STEAM ADMIN GIEF ACWOUNT DETALS OR YOU GOT BANT LOL
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