C:\Documents and Settings\ is a hidden folder. As you see in the following commandprompt, it is a
junction to C:\Users\ to stay backwards compatible. Just disable the view of
hidden files and folders (
Tools ->
Folder Options ->
View in
Windows Explorer), and it won't bother you again!

Code:
Microsoft Windows [Version 6.0.6001]
Copyright (c) 2006 Microsoft Corporation. All rights reserved.
C:\Users\Administrator>dir c:\ /a:h
Volume in drive C is WIN2008
Volume Serial Number is B098-05D1
Directory of c:\
01/19/2008 11:33 AM <DIR> $Recycle.Bin
03/16/2008 01:58 AM <DIR> Boot
01/19/2008 09:45 AM 333,203 bootmgr
01/19/2008 04:21 PM <JUNCTION> Documents and Settings [C:\Users]
03/17/2008 12:42 AM <DIR> MSOCache
03/29/2008 02:42 PM 4,607,066,112 pagefile.sys
03/31/2008 11:11 PM <DIR> ProgramData
03/16/2008 01:00 AM <DIR> System Volume Information
2 File(s) 4,607,399,315 bytes
6 Dir(s) 46,130,495,488 bytes free
C:\Users\Administrator>