Her brother complex may be the reason she rarely calls Rito "Onii-chan"; less a lack of respect and more a sign of her wish that their relationship was something other than that of a brother and sister.
By the end of the Darkness manga, Rito earns Haruna's mutual feelings; in addition to Lala, Run, Yami and Momo.
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Mikan grows quite attached to Golden Darkness, perhaps due to Darkness seemingly being the same age as her.
Mikan is very perceptive and seems to be able to read people's emotions, even their reactions, most of which is Rito's obvious anxiety around Haruna and Yui's subtle feelings for him.