Thanks, that did it!
/// Look at a target world position.
void Node::LookAt(const Vector3& target, const Vector3& upAxis = Vector3::UP);
/// Construct from the rotation difference between two vectors.
Quaternion(const Vector3& start, const Vector3& end)
node.GetChild("mixamorig_Head", true).rotation = ...
One way to fix is to adjust the rotation after LookAt() by some hack quaternion that corrects the mismatch. You may require trial & error for that.