The Synapse compartments are designed to flex according to their loaded contents -- so the actual shape and distribution of weight, center of gravity, etc. depends on the details of how you pack the bag. This ability to adjust relative size of side and bottom compartments along with the main compartment according to what is carried is one of the things that makes it a "TARDIS" bag in terms of what it can carry, but it also makes it difficult to answer your question if it will stand by itself -- especially given the depth of the bottom front pocket. (It's easier for me to say that my Synapse 19 generally stands, especially since a 13" laptop is designed to fit so well in that bag).
Here are some pictures of the Synapse 25 with different loads:
As for the tightness of the cache, with a 13" laptop you have more options. For example, either the cache for the 13" MacBook Air or the 6Z (cache for old 13" MacBooks) is looser than the cache for my 13" Retina MacBook Pro. I really wouldn't get a Cache for a very different sized laptop -- such as a 15" one -- to use instead. And I wouldn't try to get a much larger size cache than is optimal, since Idon't find it hard to pull out the laptop from its cache.
If having your backpack stand up by itself is a high priority, consider the Smart Alec, with its flat, padded bottom and open bucket design, instead of the Synapse.
HTH
Moriond
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