In Black Books there are 6 in the first 3 seasons.
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Too Many Stars... Season 3 Episode 5
In Episode 14 of Season 2; "Through Many Dangers, Toils and Snares"
Louise and Saito do get married :D Season 4 episode 12. They also get married in Season 2 episode 12 but they had seemed to have forgotten about that just like they forgot they made Louise the Queen's sister.
Demi Lovato has been in three episode thus far. She has been in "Tina In The Sky With Diamonds" (Season 5, Episode 2), "A Katy or A Gaga" (Season 5, Episode 4), and "Puppet Master" (Season 5, Episode 7). She has signed on for a total of 6 episodes this season yet there have been speculations that she might cut it short because of her upcoming tour. As of now, there have been no statements regarding her remaining 3 episode appearances. Hope this helped.