What have temps been like where you are? If the temp is below 37 °F the A/C won't operate; once the temp gets above that it will. 
AC Compressor and Cooling Fan won't turn on (low temp limit)
I have a 2014 Smart ForTwo Pure and when I press the AC switch, it is not turning on the compressor nor cooling fan. This problem is not 100% of the time, but a large majority of the time. Just yesterday, the AC switch functioned while going to work, but after work wouldn't activate. Fuses 14 and 20 are good so I'm unsure if there's a weak connection somewhere or some other relay or wiring/switch that I should check. Any suggestions would be appreciated.
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Since the A/C won't operate below 37 F I don't see how the defrost would override that. Could be wrong.....
Here's how smart describes the defrost function:
Here's how smart describes the defrost function:
For safety reasons, if the air distribution lever is
moved precisely to "Windshield Defrost", the air
conditioning switches itself on automatically with no
action by the occupants in order to ensure that the
windshield is defrosted and dried as quickly as
possible.
In this case the function LED does not light up to indi-
cate that the air conditioning has been activated
automatically.
When the air distribution lever is moved away from the
Defrost position, this function is canceled. This
happens regardless of the programmed temperature
or blower stage. In addition, air recirculation mode is
deactivated if it is on.
The air recirculation flap and the temperature blend
flap are actuated via electric actuator motors.
The cooling output of the refrigerant compressor is
controlled by means of an appropriate CAN signal
from the SAM control unit.
The interior temperature is measured by an integral
interior temperature sensor located on the bottom of
the heater/air conditioning operating unit.
Air recirculation mode.
i Note
The air conditioning cannot be operated in
temperatures below 37 °F (3 °C).
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