A recent issue of Science announced the discovery of natural quasicrystals, solids whose atomic arrangements have symmetries that are forbidden for periodic crystals. In this case, Bindi et al. (
Vol. 324. no. 5932, pp. 1306 - 1309) describe a naturally occurring icosahedral quasicrystal that includes "six distinct fivefold symmetry axes." This is big news! The picture here is their Figure 4A. I like it because it clearly shows 10-fold symmetry very close to the center (which means that 10-fold symmetry extends fairly far in the actual quasicrystal).

Explorations of five-fold symmetry on the plane go back to Persian artists of the twelfth century. I became aware of this when I read Critchow ("Islamic Patterns" 1976), which presents "demonstrations" of "important shapes that enable the five-fold symmetry to harmonize with the necessary repeats of a two-dimensional surface." The matter of Islamic quasicrystalline tilings was taken up in detail by Lu and Steinhardt (who are also authors on this new paper) in 2007 (
"Decagonal and Quasi-Crystalline Tilings in Medieval Islamic Architecture"). However, it was only in the 1970s that
Penrose tilings, a periodic but infinite tilings with fivefold symmetry, were described.

This is a Penrose tiling showing five-fold symmetry.
More recently, the production of quasicrystals in the laboratory has become something of a cottage industry, but only now have naturally occurring quasicrystals been found.
Most of what I might say is said better in article, so I encourage interested readers to read
the original.