Try to run wireshark before sending a file in order to capture all the packets when the transfer will begin. Then find something common in all transfers that identify them and make rules using that.
For example, using wireshark I have found how to block the msn advertisements. There are transfered via an XML file. So I blocked this file. I have created that for 2.9.32 version.
6891 - 6900 (used for filetransfer), If you detect that are used other ports, it is that assurance that using alternative messengers as Gaim, Pidgin, amsn, etc. Microsoft respects these ports for the transference. .
1863 TCP, is primarily used for chat messages
443 TCP, is used for the transfer of the XML file that carries the contact file(backup), extra tabs, advertisement url’s
UDP Ports, should be used for video and talk
I do not think that they use UDP for file transfer, it is ridiculous!