Single-crystal conventional-tube and synchrotron X-ray diffraction studies of the anions in [NMe(4)][arachno-B(9)H(12)-4,8-Br(2)] 1 and K[arachno-B(9)H(14)] 2, and also of the series of adducts [arachno-B(9)H(13)-4-L], where L is P(CCH)(3) (3), NHEt(2) (4), NC(5)H(5) (5), or NH(2)CH(2)Ph (6), are reported. Structural studies of 1-6, determined at low temperatures, located all atoms, including bridging and endo-terminal hydrogen atoms. The basic boron-hydride clusters of these, and of all the other known species with the arachno nine-vertex i-nonanborane geometry reported in the literature, are isostructural and feature three bridging and two endo-terminal hydrogen atoms on the open face. This arrangement is different from that previously reported for Cs[arachno-B(9)H(14)] 7 and for [arachno-B(9)H(13)-4-(NCMe)] 9. However, a new X-ray diffraction data set and refinement experimentally confirm the [3 x mu-H, 2 x endo] arrangement for 9 also. The experimental results for 1-6 support recently reported calculations for [B(9)H(14)](-), which predict both the structures and the (11)B NMR chemical shifts. These conclusions are also supported by calculations for 3, 4, and 9 and also for the [arachno-B(9)H(13)-4-(NCS)](-) anion in [NMe(4)][B(9)H(13)(NCS)] 8.

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