Katniss chose Rue as an ally.
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They think that he'll lead them to Katniss.
In The Hunger Games, Katniss's name is entered in the reaping 20 times. Her name never gets chosen in the first book, her sister's Prim name does. Katniss then volunteers as tribute to compete in place of Prim.
Because that's where Rue and Thresh were from. Rue was her ally in the games and was killed by a spear piercing her stomach and Rue reminds Katniss of her younger sister Prim. Thresh could have killed Katniss, but when he heard about what she did for Rue, he decided to let her go just once. But he was killed shortly thereafter, which made Katniss sad, for he saved her life
Katniss and her family were dressing up for the reaping. The families dress up for the reaping for their children to look good in case they get chosen which means being broadcasted all over Panem.
At the Feast Clove attacks Katniss, but before killing her she makes a foment about Rue. Thresh hears her and grabs Clove. Enraged he hits her with a rock and she slowly dies. He doesn't kill Katniss though because she was Rue's ally and feels that he owes her. Being from the Seam Katniss understands perfectly. She feels the same debt to Peeta since he gave her the bread when they were little.