CarlB is right in that there are a lot of statistics involved in determining the X-year rainfall event. Although the largest rainfall event in the past may have a bearing on the 100-yr event, there is no real correlation, partly because there are few, if any, events that are exactly 24 hours in length, and there are a lot of stations with fewer than 100 years of record. If you use NWS products (i.e. TP-40, Hydro-35), you'll see that the majority of stations used have far fewer than 100 years of record. (as a side note, NWS will be releasing a new TP-40 in the near future)
One thing to keep in mind is that a 100-yr rainfall event does not automatically mean you will have a 100-yr flood, so be careful in how you make application of the rainfall data.