To determine the bond angles, we apply VSEPR theory and consider steric hindrance as well as electronegativity:
- ClO2: The central chlorine atom is sp2 hybridised and possesses one lone pair along with an odd electron. Because the repulsion caused by an odd electron is less than that of a lone pair or a bond pair, the bond angle remains relatively large, approximately 118∘.
- Cl2O: The central oxygen atom is sp3 hybridised with two bond pairs and two lone pairs. Normally, the angle would be around 104.5∘ (like water), but due to the large size of the terminal chlorine atoms, severe steric hindrance (repulsion between Cl atoms) pushes the bonds apart, widening the angle to approximately 111∘.
- ClO2−: The central chlorine atom is sp3 hybridised with two bond pairs and two lone pairs. The terminal oxygen atoms are smaller than chlorine, leading to less steric hindrance than in Cl2O. Additionally, oxygen is more electronegative than chlorine, drawing the bond pairs away from the central atom, which decreases bond pair-bond pair repulsion. This results in a slightly smaller bond angle than Cl2O.
Therefore, the correct increasing order of bond angles is ClO2−<Cl2O<ClO2.