Jim, I would give yourself a bit more of a buffer, but it's really up to you. If you're giving your backups a 6 hour window, also remember that that is just their START window. If they take 10 hours to run, as long as they get started before 6 in your case, they'll run for most of the day. Personally, I'm a fan of the calendar-based scheduling and then controlling when things kick off by the start windows.....but again, be careful of that if your backups straddle midnight, because it confuses the calendar-based stuff and your backups will run kind of crazy, possibly skipping days.
I also definitely agree about the multiplexing. Depending on your particular situation, you may or may not want to enable multiple data streams from the host (you don't want to saturate the connection on the HOST side, just the master server side), but I would definitely run multiplexing.
As an example, where I am now, they were not running multiplexing before I got here and they could barely keep their backups inside of a 12 hour window. After I got some rough multiplexing and a little bit of policy tuning done, the vast majority of our backups ran between 4 and 10 (the others couldn't start till after midnight anyways). Multiplexing really can help that much. Additionally, we just got in a new fibre-channel attatched i500, I disabled multiple data streams but kicked my mulitiplexing up to about 20 jobs per drive (only two drives currently given to the master server...just got our SSO licenses last week and will be doing that as soon as the zoning is done), and last night I was averaging 53% utilization of the gigabit connection on my master server without any noticible effects on the client end. Now THAT is good stuff!