During the "If I Were The King of the Forest" sequence, notice Tinman breaking a flowerpot and placing it directly on Lion's head. Then there's a close-up of Lion, and the crown is placed jauntily over one ear!
You'll also notice that when the guard re-enters the scene, the crown falls from the Lion's head onto the floor and by some miracle does not break, despite the seemingly marble floor of the palace. In fact, if I'm not mistaken it seems to bounce the slightest bit.
About this: I don't think that this is considered a slip-up, because if you notice, the lion is moving his head while he is singing. So, if the tin man put the crown on the top, it is not impossible (actually its very likely) that the crown would move. And it found the lion's ear to rest on!
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