DATETIME2 has a date range of "0001 / 01 / 01" through "9999 / 12 / 31" while the DATETIME type only supports year 1753-9999.
Also, if you need to, DATETIME2 can be more precise in terms of time; DATETIME is limited to 3 1/3 milliseconds, while DATETIME2 can be accurate down to 100ns.
Both types map to System.DateTime in .NET - no difference there.
If you have the choice, I would recommend using DATETIME2 whenever possible. I don't see any benefits using DATETIME (except for backward compatibility) - you'll have less trouble (with dates being out of range and hassle like that).
Plus: if you only need the date (without time part), use DATE - it's just as good as DATETIME2 and saves you space, too! :-) Same goes for time only - use TIME. That's what these types are there for!
Marc