He cambiado el puerto 25 porque me decía que ya estaba ocupado por otro dispositivo.Al cambiarle el puerto por el 1024 se conectaba sin problemas.
En el php.ini ya cambie y puse: 
[mail function]
; For Win32 only.
SMTP = localhost
smtp_port = 1024  
Pero al intentar enviar un mail, por ejemplo a mi mismo 
[email protected] en la consola del programa me aparece el siguiente error:  
05/01/2005 13:30:36   SMTP Server started. Listening on port 1024.
05/01/2005 13:30:36   Local Host : formacion2
05/01/2005 13:30:36   Local IP : 192.168.200.246
05/01/2005 14:15:10   3656 Connect from 127.0.0.1
05/01/2005 14:15:10   3656 New mail received. From:< 
[email protected] > to:< 
[email protected] >
05/01/2005 14:15:10   3656 Close connection.
05/01/2005 14:15:11   Message from:< 
[email protected] > to:< 
[email protected] >   Direct delivery fail! Socket Error # 10051 Network is unreachable. Wait for retry!
05/01/2005 14:16:02   Message from:< 
[email protected] > to:< 
[email protected] >   Direct delivery fail! Socket Error # 10051 Network is unreachable. Wait for retry!
05/01/2005 14:16:53   Message from:< 
[email protected] > to:< 
[email protected] >   Direct delivery fail! Socket Error # 10051 Network is unreachable. Wait for retry!
05/01/2005 14:17:45   Message from:< 
[email protected] > to:< 
[email protected] >   Direct delivery fail! Socket Error # 10051 Network is unreachable. Wait for retry!
05/01/2005 14:18:36   Message from:< 
[email protected] > to:< 
[email protected] >   Direct delivery fail! Socket Error # 10051 Network is unreachable.   
A que se debe??