Voting was underway to elect the 11 members of the new "political assembly" at the conclusion of the 60-member coalition's first full meeting, delegates said.
The "political assembly" will be headed by moderate preacher Moaz al-Khatib, the current president of the coalition, and will include his two vice presidents and the coalition's secretary general, Qatari-backed businessman Mustafa Sabbagh, who has emerged as one of the most powerful figures in the new structure.
The changes are part of an internal constitution that also requires a transitional government and parallel structures to be ready to fill the political and security void if President Bashar al-Assad falls from power.
But hardball politics have overshadowed the three-day proceedings in Cairo, with the Brotherhood becoming an overwhelmingly powerful kingmaker.
Since the coalition was set up in Qatar earlier this month with Gulf and Western support the Brotherhood has swiftly assembled a de facto majority bloc, according to insiders keeping track of changes in the membership of the coalition.
The revolt against four decades of autocratic rule by Assad and his late father revived the Brotherhood's fortunes after decades of repression that killed many thousands of its members and opened more sources of financing for the organisation from exiled conservative Syrians.
France, Britain, Turkey and Gulf Arab states have already recognised the coalition as the legitimate representative of the Syrian people. The United States has been more cautious.
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