I recently finished a casual read of Joseph & Ben Albahari's good book C# 3.0 In a NutShell (by "nutshell" they mean 800+ pages).
They do a good job of including two audiences - those new to programming (who need C# syntax and the basics of an array explained), and those familiar with C# who just want to see the new stuff. I found the chapters on Linq and Ling-to-Xml very instructive.
They also then give a healthy chapter to each of the main parts of the framework. To be able to jump from language design to Linq to System.Net to Reflection to Xml to Serialization and beyond is an impressive feat. I think having that kind of broad knowledge gives the developer a powerful tool belt. Besides the basics (like xml), there are simply cool tools and process that you can never create unless you understand reflection, diagnostics, networking, streams, and even threading.