Hi and welcome to the forum,
From your screenshot I see that you use an external NAS for storage. When NCS is run as a service on a local account Windows do not allow any activities on the network due to security.. You need to change the following in the Service configuration
You need to use a regular account preferably with admin right, but that is not necessary.
Also when you set it up liker that you will not see the free space on the NAS. If you first set a drive letter to the NAS and the use that drive letter in NCS it iwll see tha free space on the NAS:
Last I would recommend you use the latest version NCS 1.4.1 from here http://community.netcamstudio.com/t/netcam-studio-1-4-1-netcam-studio-2-0-beta/1799/3