First Look at this example :
The C code for a simple C program is given below
struct Foo {
    char a;
    int b;
    double c;
} foo1, foo2;
void foo_assign(void)
{
    foo1 = foo2;
}
int main(/*char *argv[],int argc*/)
{
    foo_assign();
    return 0;
}
The Equivalent ASM Code for foo_assign() is
00401050 <_foo_assign>:
  401050:   55                      push   %ebp
  401051:   89 e5                   mov    %esp,%ebp
  401053:   a1 20 20 40 00          mov    0x402020,%eax
  401058:   a3 30 20 40 00          mov    %eax,0x402030
  40105d:   a1 24 20 40 00          mov    0x402024,%eax
  401062:   a3 34 20 40 00          mov    %eax,0x402034
  401067:   a1 28 20 40 00          mov    0x402028,%eax
  40106c:   a3 38 20 40 00          mov    %eax,0x402038
  401071:   a1 2c 20 40 00          mov    0x40202c,%eax
  401076:   a3 3c 20 40 00          mov    %eax,0x40203c
  40107b:   5d                      pop    %ebp
  40107c:   c3                      ret    
As you can see that a assignment is simply replaced by a "mov" instruction in assembly, the assignment operator simply means  moving data from one memory location to another memory location.
The assignment will only do it for immediate members of a structures and will fail to copy when you have Complex datatypes in a structure. Here COMPLEX means that you cant have array of pointers ,pointing to lists.
An array of characters within a structure will itself not work on most compilers, this is because assignment will simply try to copy without even looking at the datatype to be of complex type.