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A/N: After reading a fantastic Byakuya/ Rukia story where they married out of duty, I wanted to try writing something similar. Please R&R, usual disclaimers apply
Timeline: post Aizen probably

Their wedding had occurred in a daze for both of them, practically forced on them by the elders. Despite the shock of disbelief and the protests of some of their friends the wedding was celebrated in great splendor, as it befitted the foremost noble clan. Before the reality could sink in, Rukia found herself in the master bed room dressed in a flimsy flowered yukata by the female members of the clan for her wedding night. Still in shock she stared at the elegantly decorated room that would be their nuptial chambers. It had been restored for her and ni-sa…., Byakuya-sama to share after the wedding. It was situated in a wing of the mansion that had been in disuse since long and it gave on a small private garden.
The wing was restored according to Byakuya-sama’s, request as it would have seem weird to share the same room that he had shared with her sister. Thinking of Hisana, brought a fresh wave of anguish. Was her resemblance to the former Kuchiki lady the reason he had consented to this union? She had not been given much choice in the matter, it was either marrying Byakuya or a man from a noble clan chosen by the elders, but he could have refused and marry her off to anyone else. To the general surprise, he had consented and relieved at finally getting him to take a wife, the elders had rushed the wedding as much they could.
The sliding noise of the bedroom door interrupted her musings and her new husband walked in still in his traditional black kimono. Despite looking slightly weary, his extraordinary physical beauty had never been more apparent, his pale skin seemed to almost glow in his black attire. Even though he had adopted her as sister they had never been like siblings, more like strangers brought together by circumstances and now married too. He gave her a brief smile, “I’m going to take a shower, you can go to bed if you wish, we’ll talk tomorrow”, and he proceeded to the bathroom attached to their room. Rukia only managed to nod as her heart had started to pound as soon as he entered the room. After a few seconds she heard water running and she went to sit on her bed,…their bed. She shivered as she realised what was expected of them tonight after all the whole wedding was pressed on them to produce an heir. She had never been intimate with a man but in all her nearly 150 years, she had gathered a picture of what was to happen. As all young women, she had daydreamed about this night but now that she had reached the moment, she was feeling slightly sick with apprehension, instead of the nervous excitement she thought she would feel.
Before she even knew, the sound of running water had stopped and Byakuya stepped in the room dressed in sleeping robes. “ You should sleep Rukia, we’ve both had a tough day”, he said as he made way towards the bed. “ I’m not that tired” she managed to say without stuttering while glancing nervously towards the bed, he followed her gaze and smiled, “ don’t worry Rukia, I won’t ask anything of you that you feel uncomfortable with.”
“ Why did you marry me? How are we going to live through this marriage? Are we going to continue to live side by side like strangers, coming close time to time only to produce children? Is it because of my resemblance to her….” She trailed off in a whisper
He sighed and came to sit by her side. She was suddenly very conscious of her flimsy clothes but she forced herself to stay calm as she drank in his presence, she had forgotten what soothing effect his presence always had on her, as if his strength could dispel all her worries . They sat in silence for a while, enjoying a calm moment after the storm of their wedding flew by. He finally spoke, “I didn’t marry you to produce an heir.”
She looked up at him in surprise, he looked at herin the eyes and continued, “ Neither because you look like Hisana. You were being backed in a corner by the elders, I agreed to marry you so that you were not forced into a loveless marriage with a stranger..’
“ So we are just going to pretend to be married?”
‘ No, I intend this marriage to be real in every sense of the word, but I won’t force you into anything, we’ll take our time and try to build a relationship.”

Unexpectedly her eyes filled with tears, of relief, gratitude and perhaps joy and she could only nod in assent, and much to her surprise he pulled her in his arms and kissed her on her temple. They spent their first night together like this, in each others arms chastely like children. Despite this the first few days were awkward, they were both unsure about how to act around each other and their respective busy schedule didn’t help a lot. At night, they slept on separate sides with their backs to each other but she could not avoid teasing from female colleagues about sharing the bed of one of the most gorgeous men in the sereitei.
Slowly but surely, things began falling together. It all began simply, with her proposal one night to help him with his kenseikan and his unexpected agreement. He sat down on a chair as she stood behind him. At first hesitant, her hands became surer as she lovingly unraveled each strand from the apparel, drawing great pleasure in running her hands through his silky hair. She felt him relax under her touch and once she had removed the apparel, she brushed his hair gently marveling at its softness. He thanked her and stood up, his eyes looking at her with an intensity that made her stomach flip. This soon became a routine between them and she enjoyed doing it. One night as she finished brushing his hair, he caught her hand and gently kissed her hand knuckle by knuckle. Her pulse started racing and her breath caught in her throat.
Their relationship had been changing, a sort of comfort had grown between them as well as a certain tenseness. The accidental brushing of hands that sent a jolt through them, the conspirating looks they exchanged during the boring family reunions, secret smiles and looks. However they were both afraid to take the first step, afraid to break the ice.
One night nearly 3 months after their wedding, as they were taking a nighttime walk, another growing habit of theirs, they kissed for the first time.
His lips on hers were gentle but firm as he coaxed her into permitting entrance. Due to her short stature, he had to lift her up to continue kissing her and she instinctively wrapped her legs around his slim waist. The soft tentative kisses grew more heated, as he supported her with one hand and buried the other in her hair. She moaned as his mouth moved to trail her jaw line and down her neck.
He suddenly stopped and looked at her intently, “Rukia, are you sure about this?”, he asked
“Yes, I’m sure”

He then put her down and let her lead them back to their room, both in a pleasurable haze of anticipation. As soon as they reached the room, he started kissing her again with renewed ardor and Rukia lost the sense of reality as she drowned in his passionate embrace. Her mind was fuzzed and she had the sensation of moving backwards and she toppled on the bed with a hot hungry mouth down her throat and gentle hands tugging at her clothing. When she was finally naked he stepped back to admire her, his appraising looking making her blush scarlet and he started undressing. Despite her embarrassment she could not tear her eyes away as more of his body was revealed. He was slender but well toned, and numerous scars marred his milky skin but they only added to his beauty.
He had always seemed so cold and distant to her all those years but that night she had an inkling of all the passion he hid inside his seemingly icy heart. The expressionless eyes watched her every expression with such tenderness, his hands and mouth were gentle but eager as he explored her body and he gently soothed away her fears away as he joined with her for the first time, kissing away the tears that the unexpected pain had brought.
As she woke up the next morning, cradled protectively in his arms, memories of their passionate trysts flooded back and she could not help thinking that her marriage had every chance of being a very happy one.