You need to use actual instances of your MyStruct, which you can create with the new keyword.
This should work...
struct MyStruct
{
int i, j;
public MyStruct(int a, int b)
{
i = a;
j = b;
}
}
static MyStruct[] myTable = new MyStruct[3]
{
new MyStruct(0, 0),
new MyStruct(1, 1),
new MyStruct(2, 2)
};