No, every 802.15.4 network should have a PAN coordinator and all the other nodes either they are internal nodes (routers) or leaf nodes should work on the same frequency as in PAN coordinator.
Therotically it is yes.so you can set different frequencies to each cluster in NS2.but it is difficult to implement it. In fact we usually define that one wirless network has one frequncy,there are two networks if there are two frequencies.in another word,different frequncies is correspond different wirless network. This view is from the second layer of OSI/RM.
What kind of clustering are u using in your network? actually you may set different frequesny to each node, but since the clustering of nodes is dynamic during network life time, you can not set a specific frequesny to each cluster every moment!
But if your clustering is static, means the cluster head and the form of the clsuter will be the same from the begining until end, or its under your control to set the clusters, then yes, you may do it.
I am using static clustering. And I want to maximize the throughput of my network which has same resources as that of ZigBee by adjusting the Center Frequency Distance by using an approach DCN(Dynamic Clear Channel Assessment for non orthogonal design).