Spacings mostly depend on your product's mains overvoltage category and pollution degree.
Ref. Table 4 IEC 61010. For 120VAC mains, PD2, Cat. II impulse voltage is 1.5kV so minimum clearance is 0.5mm and creepage 1.6mm is typical design minimum.
Connectors with 0.1" spacing offer less than 0.1" due to the
pin PADs' diameter. You can double space, i.e. leave every other pin unused for more space.
Samtec 0.1" headers TSW are UL approved and rated 500VAC and several amps.
If you route full mains to the connector, it needs to be rated for the available current because using a little connector it would just burn up if a fault occurred on the second PCB. Even though the load current is low, if a short happens it's best if the PCB+connector is not part of the bonfire, unless the enclosure can take the heat and no chance of electrocution etc. resulting.
A fuse or resistor is best on signals leading to the connector pins, or use a heftier connector that can clear the defining fuse or circuit breaker.
edit: forgot to mention the pads reduce spacings, it's not just pitch to consider