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Connect Substructures
Substructures can be joined by simply drawing a bond between their connecting atoms. For example, to draw biphenyl you could first draw a benzene ring, and then use Shift-Click to draw a second, separate benzene ring. To connect the two rings, select the single-bond object ( / ) and draw a bond from a carbon atom (vertex) in one ring to the target connecting atom in the other ring.
Alternatively, you could add a methyl group to one carbon atom of the first benzene ring, and then merge a second benzene ring with the methyl group to again generate the biphenyl structure.