Cologne remained dangerous on the counters and added another goal to their lead when Zoller chipped into the path of Christian Clemens, who poked home the 3-0 advantage into the open goal in the 64th minute.
Berlin pulled one back five minutes later, as Niklas Stark nodded a rebound to make it 3-1 on the scoreboards. The goal sparked hopes, but Berlin were unable to avoid their elimination from the Cup.
Record-holding champions Bayern Munich follow Cologne into the next round after beating ten-men Leipzig 5-4 on penalties.
Both sides staged a fast-paced and offensively minded encounter with chances at both ends of the pitch. Nevertheless, the spectators had to wait after the restart before action on the pitch would kick-off.
Leipzig's Naby Keita ensured the first negative highlight of the clash as the Guinea international received his marching orders for booking his second yellow card of the game in the 54th minute.
Despite Leipzig's numerical disadvantage, they were able to break the deadlock 14 minutes later when Emil Forsberg converted a controversial foul-play penalty into the bottom left corner of the net.
The German giants responded with the equalizer in the 73rd minute as Thiago Alcantara found Jerome Boateng's cross.
Both sides failed to grab the winner, thus the penalty shootout was needed to bring the decision. All of the players kept their nerves except Leipzig' s Timo Werner, whose crucial shot from the spot was saved by custodian Sven Ulreich.
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