The original scourging of Sansha's Nation probably counts - I think it's mentioned in a couple of places that many of their planets were bombarded from orbit in a sterilization campaign.
Not sure the Caldari Prime bombardment counts; I've always seen it as an attempt to systematically destroy every military or military-supporting installation rather than an indiscriminate attempt to wipe out every thing on the surface (although they certainly hit some civilian targets, either because they were providing support to military installations or because of collateral damage, it's my understanding that they weren't the primary targets of the Gallente fleet).
On the other hand, I'd include Admiral Tovil-Toba's use of his carrier as a suicide vessel - he certainly couldn't guide the thing, especially once it started breaking up, so it's pretty indiscriminate.