It depends on the round length that the commissioner set up. If the round length is set to 1 week (which is what it will likely be for our league), then any games within that week can be played. So if you want, you can play all of your games for the week in one day I believe.
You don't have to show up at a specific time to play a specific game, but you do have to make sure you're both online if you want to play against another person's team. If not then you'll just be playing/coaching against his AI.
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