There's an anime called
The Legend of Black Heaven that has something to do with rock/metal, though I haven't seen it so I can't comment on it.
And while RahXephon has a lot of connections to music and is otherwise a great series, it's too bad the actual music to the series (i.e. soundtrack) is almost non-existent. From what I recall most of it was just some short cues mixed with a cacophony of piano, cymbal and trumpet noises. Biggest mistake was not hiring Kanno to do the entire soundtrack, could have been so great.

Apparently the score was supposed to be "jazzy" or something but to me it almost sounded like someone was just randomly hitting the instruments now and then. Maybe I'm just an uneducated buffoon.
Princess Tutu has tons of awesome classical music since well it's about ballet mixed with magic and fairy tales. Really excellent show. Don't let the name put you off. Despite the girly name it is very deep and at times very dark.
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I've been meaning to see this for the longest time, it seems really nice. I had the fansubs way back but deleted them once when I quickly needed the disk space and never bothered to download them again. Maybe I'll get to it when the ADV thinpak collection comes out.
Jam it back in, in the dark.