Sunday, 21 February 2016

molecular structure - Why is the H−C−H bond angle in сhloromethane larger than 109.5°?


Symmetrical tetrahedral molecules (like CHX4) have a bond angle of 109.5. Those with lone pairs in place of one atom (like NHX3) have bond angles less than 109.5.


The standard explanation for why is that the lone pairs are "larger" than the hydrogens, creating repulsive forces that push the hydrogens down, decreasing the bond angle.


However, this explanation fails when confronted with CHX3Cl. According to the above logic, the Cl, which is much bigger than the hydrogens, should repel the hydrogens just like a lone pair, making the HCH bond angle smaller than 109.5. However, the HCH bond angle is actually 110.5 (see here, I could not find a more authoritative source).


Why is this (or is my source wrong)?




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