Hmm. The Manual specifies a supply voltage of 2.8-3.4V, so you’d be quite a bit over that. I don’t see a “do not exceed” table, but 4.2V sounds excessive to me.
In addition, I’m not sure you’d get reliable operation just sending a battery voltage into the XBee’s VIN even if it were an appropriate voltage level. I guess I don’t know for sure that it won’t work, but I’ve never seen a project in which someone just plugged a battery into the VIN pin. There’s always a real power supply - a regulator and a capacitor or two to provide a smooth and appropriate power source. If I were you, I’d plan to attach a Vreg and the capacitors that go with it (read the regulator’s datasheet for the full circuit).