Sister Miyako
ミヤコ
The Second Neck (二の首, Ni no kubi), she is a purple-haired nun who is the first Orochi to appear and attack, having lost her faith due to living through a terrible war (presumed somewhere in South America due to her tanned skin color which is a common stereotype in manga and anime). Although there is little co-operation among the Orochi, she seems to be the closest thing therein to a second-in-command and the most cool-headed of the lot; she can control Girochi and induce some semblance of cooperation among the three other female Necks.
Her influence appears to be what turns Chikane to the Orochi cause, though it is later revealed that the Lunar Miko went to them of her own accord.