I have setup a new account and not verified my domain. I would like to test and confirm mail-send before proceeding with verification and adding payment information.
Faced the same issue while sending emails via api by php curl. I solved it by changing API Base URL https://api.mailgun.net/v3/YOUR_DOMAIN_NAME to https://api.mailgun.net/v3/YOUR_DOMAIN_NAME/messages.
It's because their api is not only for sending.
Hope this helps.