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Under some additional assumptions, the Nevanlinna family can be interpreted as a Weyl function of a densely defined symmetric operator with some boundary triplet [see \\textit{V.\\,A.\\thinspace Derkach} and \\textit{M.\\,M.\\thinspace Malamud}, J.~Math.\\ Sci., New York 73, No.\\,2, 141--242 (1995; Zbl 0848.47004)].  The authors show here that in the general situation, the Nevanlinna family is a Weyl function of a more general object called a boundary relation, which was introduced in their earlier paper [\\textit{V.\\,Derkach, S.\\,Hassi, M.\\,Malamud} and \\textit{H.\\,De Snoo}, Trans.\\ Am.\\ Math.\\ Soc.\\ 358, No.\\,12, 5351--5400 (2006; Zbl 1123.47004)]. This correspondence is studied in detail; in particular, the authors investigate the conditions under which a Nevanlinna family gives rise to an operator extension (in the general case, one has to deal with relation extensions). 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