If the API says to use HTTP Basic authentication, then you need to add an Authorization header to your request. I’d alter your code to look like this:
WebRequest req = WebRequest.Create(@"https://sub.domain.com/api/operations?param=value¶m2=value");
req.Method = "GET";
req.Headers["Authorization"] = "Basic " + Convert.ToBase64String(Encoding.Default.GetBytes("username:password"));
//req.Credentials = new NetworkCredential("username", "password");
HttpWebResponse resp = req.GetResponse() as HttpWebResponse;
Replacing "username" and "password" with the correct values, of course.