Network Access permissions - Access Denied

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I run a Desktop running Windows XP Pro and a laptop running Windows 8.1 Pro and want to synchronise various files and programs between the two.

For historic reasons the only user on the desktop is the Administrator.

I installed VV on the desktop and had no difficult syncing files that were kept in the documents and settings\Administrator\folder on desktop with the equivalent but differently named user folders on laptop.

I cold not however access any folders in the root directory on the laptop. I just cannot even see it. It is not shared as I think that is unsafe on a travelling computer. I was surprised how easy it was to access the supposedly more secure user files. Theyseem to be wide open.

I therefore tried Installing Vv on the laptop. Now could access root directory folders on both machines but no way could I access the \documents and settings\Administrator\documents\ on the desktop even though Drive c: on the desktop is shared with other users of the Network.

The windows help file always just tells you to ask the Network Administrator for permission in these circumstances but does not tell you how to grant permission.

Questions

1. How do I access drive c on laptop without sharing it

2. How do I grant permission to access the Administrator folder from another computer.

I have tried putting various configurations of the username and password in the Network configuration in VV but to no avail. maybe I just do not understand the correct format.

In Windows Xp on the desktop I found a setting for change my network password to give access to the laptop but it does not make drive c: any more visible. I am surprised I could get access to the user folders without I believe ever putting in the different password I have for the laptop. In Windows 8.1 on the laptop I have found manage my Credentials but cannot seem to input the information in a way that works. I think this is the same data as is used by the Network configuration within VV

The message when I test connection is folder is not accessable usung the credentials entered. Access is denied. That is with Computername\Administrator. With \\Computername\Administrator or \Computername\Administrator I get specified username invalid). None work