Matrices have two diagonals: main diagonal and anti-diagonal. The main diagonal runs from top-left to bottom-right. For square matrix A:
// main diagonal:
for (size_t xy=0; xy<A.size(); ++xy)
cin >> A[xy][xy];
// anti-diagonal
for (size_t x = A.size()-1, y=0; y<A.size(); --x; ++y
cin >> A[x][y];