Well, you could do:
DateTime now = DateTime.Now;
if (now.Hour < 8 || now.Hour >= 17)
Note that I generally prefer to only use the DateTime.Now
property once, copying the result into the local variable as above - that way you don't get odd possibilities due to the time changing between calls. Not a problem here, but it could be in other cases.
Another possibility is to use DateTime.TimeOfDay
if you want to handle things that way. I think the above is about as simple as it gets though.
EDIT: Steven pointed out that I changed the && in your original logic to || - your original logic can never work, as it can never be before 8am and after 5pm. The above works for "if it's not in the working day" - if you want "if it is in the working day" you just need:
DateTime now = DateTime.Now;
if (now.Hour >= 8 && now.Hour < 17)