Hi,
I think you have to check in "Attributes for main and sub transactions" view for mapping your settings.
As I understand from your issue details is that you are trying to create SD at CA level i.e. without division (before contract creation). Standard SAP provides SD mapping details at division level (with contract) so if you wish to create SD at CA level then you have extend setting at above view (for without division) and provide appropriate main and sub at EK01 and EK02 (without division).
Hope this helps.
Regards,
Paresh