JavaScript (ES6),  160 158  146 bytes

n=>(g=(e,v,p)=>[...Array(N=2*n),N-1,1,n].reduce((s,x,i)=>(m=1<<(x=i<N?i:(p+x)%N))&v?s:s+g((i>=N)/p?[...e,1<<p|m]:e,v|m,x),g[e.sort()]^(g[e]=1)))``

Try it online!

Notes:

• This is quite inefficient and will time-out on TIO for \$n>4\$.
• \$a(5) = 10204\$ was found in a bit less than 3 minutes on my laptop.

Commented

n => (                        // n = input
  g = (                       // g = recursive function taking:
    e,                        //   e[] = array holding visited edges
    v,                        //   v   = bitmask holding visited vertices
    p                         //   p   = previous vertex
  ) =>                        // we iterate over an array of N + 3 entries, where N = 2n:
    [ ...Array(N = 2 * n),    //   - 0...N-1: each vertex of the N-gon (starting points)
      N - 1,                  //   - N      : previous vertex \
      1,                      //   - N+1    : next vertex      }-- connected to p
      n                       //   - N+2    : opposite vertex /
    ].reduce((s, x, i) =>     // reduce() loop with s = accumulator, x = vertex, i = index:
      ( m = 1 << (            //   m is a bitmask where only the x-th bit is set
          x = i < N           //   and x is either:
              ? i             //   - i if i < N
              : (p + x) % N   //   - or (p + x) mod N otherwise
      )) & v ?                //   if this vertex was already visited:
        s                     //     leave s unchanged
      :                       //   else:
        s +                   //     add to s
        g(                    //     the result of a recursive call:
          (i >= N) / p ?      //       if p and x are connected (i >= N and p is defined):
            [ ...e,           //         append to e[]:
              1 << p | m      //           the edge formed by p and x
            ]                 //           and uniquely identified by 1 << p | 1 << x
          :                   //       else:
            e,                //         leave e[] unchanged
          v | m,              //       mark the vertex x as visited
          x                   //       previous vertex = x
        ),                    //     end of recursive call
      g[e.sort()] ^           //   sort the edges and yield 1 if this list of edges has not
      (g[e] = 1)              //   already been encountered; either way, save it in g
    )                         // end of reduce()
)``                           // initial call to g with e = ['']