I found The Sparrow simultaneously excellent and annoying. The character arcs and examination of the human condition were excellent. The aliens were... irritatingly vague. We were barely given a physical description of them, much less a deep and insightful view of their culture and economy.
(Also, it's very sad, so readers who like happy endings should watch out.)
Timothy Zahn's Conqueror's Saga describes humanity's first encounter with an alien race and the tragic misunderstandings that can occur when two different kinds of biology interact.
And of course there's Dune.
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