what does .net web service not having web.config entry has to do with sending emails?

I am getting the following errors:
No connection could be made because the target machine actively refused it 127.0.0.1:4455
WebException: Unable to connect to the remote server
 The explanation I got from the seniors is that there is a web service used by the web application. That web service did not have an entry in the web.config file for a specific port. Therefore, in the disco file the web service defaults to 4455.

Why does no web.config entry in a web service manifest itself in a send email problem?
Why does the email target itself to port 4455?  (there is not specific code or config entry to use port 4455).  

Dim client As New SmtpClient
           ' SmtpClient is from System.Net.Mail
 
           ' client.Host = "smtpmail.wegmans.com"
            client.Host = "localhost"
            ' I tried both smtpmail.wegmans.com and localhost. both gave me the same error
             client.Send(myMessage)
            'in the try catch, client.Send result in the error. See attachment for error info
 
PO.disco (sample entry)
<discovery xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance" xmlns:xsd="http://www.w3.org/2001/XMLSchema" xmlns="http://schemas.xmlsoap.org/disco/">
  <contractRef ref="http://localhost:4455/PO.asmx?wsdl" docRef="http://localhost:4455/PO.asmx" xmlns="http://schemas.xmlsoap.org/disco/scl/" />
  <soap address="http://localhost:4455/PO.asmx" xmlns:q1="http://webservices.myCOM.com/PO/" binding="q1:POSoap" xmlns="http://schemas.xmlsoap.org/disco/soap/" />
  <soap address="http://localhost:4455/PO.asmx" xmlns:q2="http://webservices.myCOM.com/PO/" binding="q2:POSoap12" xmlns="http://schemas.xmlsoap.org/disco/soap/" />
</discovery>

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emailProblem.bmp