Yeah, you are right that it's very easy to break apart nitro groups, but it's not much to do with the (O-N-O) bond angle. The bonds themselves in -NO2 groups are very weak, because nitrogen doesn't provide enough bonds to make things stable. Remember oxygen wants to "hold on with two hands" as we said in high school chemistry, that is to make a double bond or two single bonds. In NO2 each oxygen only gets one and a half bond (quantum mechanically it is in a superposition between having single bond to the first oxygen and double bond to the second, and vice versa). So this part becomes electronegative. Nitrogen, on the other hand, wants to have three bonds in total, but is forced to have four: 2x 1.5 to the oxygens, and one to the rest of the molecule. So this part becomes electropositive. Chemists will speak here of a resonance structure, which you can imagine is something that it is quite easy to excite.
When the nitro group breaks apart, the nitrogen finds another nitrogen from another NO2 and forms N2 gas, which is highly stable due to its triple bond, so this part of the reaction releases a lot of energy and produces a lot of gas, and is very fast since it does not depend on any other sub-reactions. And stuffing lots of just nitrogen (without oxygen) into a molecule is in itself a way to make it very explosive - see azidotetrazolate salts.
In NO2 decomposition, the oxygen then goes on to find carbon to make CO2, and hydrogen to make H2O, releasing more energy and producing more gas. But this first requires breaking down the relatively stable bonds in the hydrocarbon, so it actually consumes energy from the NO2 decompostion, before it releases more energy than it consumed.
Then stoichiometrically you want to ensure that you have enough oxygen for all your carbon and (ideally) hydrogen, or you'll end up producing a lot of "unburnt" stuff which is inefficient. Notice that for each carbon in a linear hydrocarbon chain (-CH2-) you need 1.5 NO2 groups to get a complete reaction into CO2 and H2O. If you only have 1 NO2 group, CO2 will be formed and you will have excess H2 which is not combusted.
Now as you say there are some stressed rings or cages that are hideously sensitive explosives, precisely because the hydrocarbon bonds have also had their stability reduced. But these typically are not practical explosives. For that you want the stuff to be a solid at a wide range of temperatures, you want it to be non-sensitive to friction and impact, and you want it to have a low vapor pressure. These are all details which depend strongly on the internal structure of the molecule.
When the nitro group breaks apart, the nitrogen finds another nitrogen from another NO2 and forms N2 gas, which is highly stable due to its triple bond, so this part of the reaction releases a lot of energy and produces a lot of gas, and is very fast since it does not depend on any other sub-reactions. And stuffing lots of just nitrogen (without oxygen) into a molecule is in itself a way to make it very explosive - see azidotetrazolate salts.
In NO2 decomposition, the oxygen then goes on to find carbon to make CO2, and hydrogen to make H2O, releasing more energy and producing more gas. But this first requires breaking down the relatively stable bonds in the hydrocarbon, so it actually consumes energy from the NO2 decompostion, before it releases more energy than it consumed.
Then stoichiometrically you want to ensure that you have enough oxygen for all your carbon and (ideally) hydrogen, or you'll end up producing a lot of "unburnt" stuff which is inefficient. Notice that for each carbon in a linear hydrocarbon chain (-CH2-) you need 1.5 NO2 groups to get a complete reaction into CO2 and H2O. If you only have 1 NO2 group, CO2 will be formed and you will have excess H2 which is not combusted.
Now as you say there are some stressed rings or cages that are hideously sensitive explosives, precisely because the hydrocarbon bonds have also had their stability reduced. But these typically are not practical explosives. For that you want the stuff to be a solid at a wide range of temperatures, you want it to be non-sensitive to friction and impact, and you want it to have a low vapor pressure. These are all details which depend strongly on the internal structure of the molecule.