We report a family of systems having a planar pentacoordinate carbon (ppC) based on the next heavier analogue of CAl5+, the ppC system par excellence. Although because of the larger size of Ga, the ppC isomer is not even a local minimum in CGa5+, a single isoelectronic substitution of Ga by smaller sized Be maximizes the bonding in the ppC form. Retaining the 18 valence electron rule, the global minimum structures of CGa4Be, CGa3Be2-, CGa2Be32-, and CGaBe43- clusters and their corresponding lithium salts have a ppC.