An Imam stood to offer a fifth Rak`ah in a four-Rak`ah prayer, and he was reminded to sit by those behind him, but he wouldn`t listen. What is the ruling on those who followed his lead knowingly and intentionally?

If the Imam stood to offer a fifth Rak`ah, those praying behind him shouldn`t have approved of that, and the prayer of those who did is considered null and void.

I wish to Pray at the Mosque, but I couldn't because I am a Woman. How can I get such a Reward?

All perfect praise be to Allah The Lord of The Worlds, and may His peace and blessings be upon our Prophet Muhammad and upon all of his family and companions                                                                                                                                                                                                                            Abdullah Ibn Masood (May Allah be Pleased with him) reported that the Prophet (PBUH) said: "Her prayer inside her home is better than its courtyard, and her prayer in her own bedroom is better than inside her home." [Abu Dawood]. Her staying at home, and not going to the mosque in obedience to Allah`s injunctions entails a great reward similar to that bestowed on a man for going to the mosque since the Mercy and Blessings of Allah Prevails. And Allah Knows Best.

What is the ruling on performing voluntary prayers during official working hours?

All perfect praise be to Allah, The Lord of The Worlds, and may His Peace and Blessings be upon our Prophet Muhammad and upon all of his family and companions

There is no harm if  there was break time during official working hours, but if not then it is impermissible. And Allah Knows Best.

Is it permissible for a guardian (Big brother) to unlawfully stop his sister from getting married?

If the guardian denies her right in getting married for an unlawful reason, she should go to court in order to settle that matter, and the guardian is considered sinful in this case.