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It is very difficult to answer your question based on brief information you provided.
In particular, "more accurate" and "more inaccurate" without numerical values and detailed description of measurement method can be understood in a large number of totally different ways. Do you get more jitter? Or larger discrepancy between iPi and Vicon systems? Is it a constant discrepancy for the entire duration of the motion, or a variable discrepancy? How the discrepancy is affected by placement of markers for Vicon system?
You would have to publish a scientific paper to properly explain the results of your measurements.
When comparing mocap systems based on different technologies, it is also important to make sure that you correctly place markers on actor so that you compare "apples to apples" rather then "apples to oranges". For example, Vicon system has very good "nominal" accuracy in a sense that it can measure the location of marker very accurately. When marker is placed on actor clothes, it can move (relative to actor body) with clothes. So in terms of accuracy of measurement of angles between actor's bones Vicon system is not as accurate as one may think from the tech specs of Vicon cameras. Moreover, particular method of placing markers on actor can result in different skeletons and therefore different values for angles between bones.
One can expect that a Kinect-based mocap system is less accurate then Vicon system, for the simple reason that Vicon uses much more advanced and expensive cameras.
As for the difference in accuracy between single-Kinect and dual-Kinect configurations, it is hard to provide an explanation based on info you provided. It is possible that single-Kinect is actually more accurate for legs. It is also possible that there is a flaw somewhere in your measurement methodology.
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