4-coordinate carbon usually adopts a tetrahedral form, the place the 4 angles on the carbon are all 109.47°. However how massive can that angle get, and might it even get to be 180°?
A search of the CSD (crystal construction database) reveals a spiropentane as having the biggest such angle, VAJHAP with 164°[1]
As a result of crystal buildings may need artefacts corresponding to dysfunction and many others, it’s at all times good to test this with a calculation; therefore ωB97XD/Def2-TZVPP (FAIR knowledge DOI: 10.14469/hpc/11148) for which a calculated angle of 163.8° is reassuring. The smallest angle on this system by the way in which is 58°, fairly regular for three-membered rings.
The localised orbitals present the C-C area defining the massive angle to be very “bent” (a banana bond) however in any other case pretty regular.
So can one “engineer” a fair bigger angle? Changing the C=C of the benzo group with a shorter CH2 group produces the next, which is now nearly linear (nearly a “hemispherical” carbon).
What concerning the smallest angle at 4-coordinate carbon? May or not it’s considerably smaller than the 57° famous above for a 3 membered ring? Looking out the CSD reveals XAQHIH[2] with an angle of 43° however the calculation above now doesn’t verify this, the angle altering from 43° to 59° throughout optimisation. A reminder that when exploring excessive geometric values, at all times test with a calculation!
The following candidate is CAZFUE[3] with an obvious measured angle of 48°. This seems to have C2 symmetry, and a calculation with this provides a worth of 46.6°. However all is just not what it appears. It is a traditional instance of a semibullvalene [3,3] Cope rearrangement, caught within the “center” so to talk (See this submit right here). In reality this geometry is definitely a transition state, and the crystal construction is the thermal common of two positions, making it seem symmetrical. The bottom state for this construction as calculated is completely different! The 2 angles now emerge as 40 and 57° (common 48.6°). On the “transition state”, one of many 4 “bonds” to carbon is unusually lengthy (2.07Å), which is the direct explanation for the small 48° angle. If this isn’t allowed as a “bond”, the angle on the different true 4-coordinate carbon emerges as regular at 57°
So the reply to the smallest angle does appear to be round 57°, nevertheless it may very well be as small as 47° if one permits bonds of two.07Å in a single’s definition of 4-coordinate. The candidate for the biggest bond angle, of virtually 180°, appears an affordable artificial goal!
