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According to the following formula:

Type of hybridisation/steric no. = (no. of sigma bonds + no. of lone pairs)

it should be $\ce{sp^3d^3}$, however according to my textbook it is $\ce{sp^3d^2}$ in solid state. That is how it was written (in my textbook), emphasising on the fact that "in solid state it is $\ce{sp^3d^2}$". How does solid state of a compound change its hybridisation?

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  1. Forget about applying hybridization outside the second row, especially in 'hypervalent' compounds. I know, that it is common to use and sometimes works, but it is incorrect.

  2. The $\ce{XeF6}$ molecule is a hard spot. While, indeed, experimental data suggest that it adopts distorted octahedral geometry in the gas phase, there is evidence that the minimum is very shallow.

  3. The octahedral structure of $\ce{XeF6}$ (which is probably a local minimum, or at least found to be one in more than one calculation) can be pretty easily described in terms of three-center four-electron bonds.

  4. There is no good agreement on the nature of the stereo-active electron pair in $\ce{XeF6}$. It seems, that repulsion with core d-shells is important, but the recent articles I could get my hands on has little to no rationalization on the fact. Still, it must be noted that the minimum is very shallow, meaning that rough qualitative theories like VSEPR and MO LCAO are too rough for a good rationalization anyway.

  5. The solid state typically involves a lot more interaction, and, as result, compounds may adopt very different structures. The simplest one example I can think of, I could point to $\ce{SbF5}$ for example. A monomer adopts trigonal-bipyramidal structure. However, in the solid state, a tetramer with octahedrally coordinated antimony and four bridging fluorines is formed. In terms of VSEPR, it is a move from $\mathrm{sp^3d}$ to $\mathrm{sp^3d^2}$. Similarly, $\ce{XeF6}$ has a crystal phase (one of six) that involve bridging atoms.

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Solid state does have an effect on the hybridization. Inorganic compounds generally split into cationic and anionic parts to form a lattice and the lattice energy compensates for the energy lost. For example

$$\ce{2PCl5 -> [PCl4]+ + [PCl6]-}$$

Such is the case with $\ce{XeF6}$. In the solid state, this occurs:

$$\ce{XeF6 -> [XeF5]+ + [F]-}$$

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  • $\begingroup$ Are you sure $\ce{XeF6(s)}$ exists as $\ce{[XeF5+][XeF7-]}$? Because that's what your last sentence implies. $\endgroup$
    – orthocresol
    Aug 9, 2017 at 13:51
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    $\begingroup$ @orthocresol Actually, this is one of the early proposed crystal compositions. Later was considered that depending on modification $n$-meric $\ce{(XeF5^+F^-)_n}$ ($n=2..6$) units are present. So it makes sense to review square pyramidal $\ce{XeF5^+}$ ions instead of $\ce{XeF6}$(Hoyer, S.; Emmler, T.; Seppelt, K. Journal of Fluorine Chemistry 2006, 127 (10), 1415–1422. DOI 10.1016/j.jfluchem.2006.04.014). $\endgroup$
    – andselisk ♦
    Aug 10, 2017 at 15:13
  • $\begingroup$ You should edit to make that clear. I downvoted because it looks to me like you are proposing $\ce{[XeF5]^+[XeF7]^-}$. $\endgroup$
    – Jan
    Aug 11, 2017 at 9:30
  • $\begingroup$ Oh, I agree that $\ce{[XeF5+][F-]}$ (or polymers thereof) is OK. I just don't ever recall seeing $\ce{[XeF5+][XeF7-]}$ and the way I'm reading it, that's what your last sentence implies, by drawing the analogy to $\ce{PCl5}$. (cc @andselisk - maybe you know something I don't) $\endgroup$
    – orthocresol
    Sep 9, 2017 at 14:07

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