You can place the RC either at the B side or the A side. When components are placed in series the order of them doesn't matter for the working.
About the diodes. When you switch off the relay it will cause a (possibly large) negative voltage on the FET's drain, and a flyback diode is used to limit that voltage to a 0.7 V diode drop. So the diode(s) don't serve to protect the coil, but the FET. Using the zeners will allow this voltage to go to -5.7 V or -15.7 V if you'd use the 15 V zeners. There's no reason for taking risks here, even if the FET can handle -30 V. So I would just use a rectifier or signal diode, or even better a Schottky diode.
edit re your comment
You can indeed use a zener (combined with a common diode, D1 doesn't have to be a zener) to decrease switch-off time, and Tyco also mentions it in this application note, but I don't read it as if they insist on it. The scope images in the first link show a dramatic decrease in switch-off time, but that measures the time between deactivating the relay and the first opening of the contact, not the time between first opening and the return to the rest position, which will change much less.
edit re the 6 V relay and the RC circuit
Like I says in this answer you can operate a relay below its rated voltage, and since its operate voltage is 4.2 V the 6 V version of your relay can also be used at 5 V. If you use a series resistor not higher than 9 Ω you'll have that 4.2 V, and then you don't need the capacitor (keep an eye on the tolerance for the 5 V!). If you want to go lower you're on your own; the datasheet doesn't give a must hold voltage. But let's say this would be 3 V. Then you can use a series resistor of 32 Ω and you'll need the capacitor to get the relay activated.
Operate time is maximum 15 ms (which is long), so as the capacitor charges the relay voltage shouldn't go below 4.2 V until 15 ms after switching on.
Now we have to calculate the RC time for that. R is the parallel of the relay's coil resistance and the series resistance (that's Thévenin's fault), so that's 19.3 Ω. Then
\$ 3 V + 2 V \cdot e^{\dfrac{- 0.015 ms}{19.3 \Omega \text{ C}}} = 4.2 V \$
Solving for \$\text{C}\$ gives us 1500 µF minimum.
Re switching off:
You can't violate Q = CV, it's the Law. Your clamping voltage is 3.3 V + 0.7 V = 4 V. That means that when you switch the FET off the low side of the capacitor momentarily will be pulled to -4 V, and quickly rise again to 0 V. The high side is 2 V higher, and will simply follow that 4 V drop while the capacitor discharges through the parallel resistor. The capacitor won't even notice the drop. The discharge time constant is 1500 µF \$\times\$ 32 Ω = 48 ms, then the capacitor will discharge to 20 mV (1% of its initial value) in 220 ms.
The 62 mA won't charge nor discharge the capacitor. We often apply Kirchhoff's Current Law
(KCL) to nodes, but it also applies to regions:
Draw a boundary around C1 and R1, and you'll see there's only one path to the outer world since the way to the FET is cut off. Since the total current has to be zero there can't be any current through that unique connection. The coil has to take care of the 62 mA on its own, and it does so by using the loop formed by the zeners.
Obvious problems: Well yes. As drawn right now, there is some confusion but:
1: Either you don't get 220V to your secondary relay (The one connected to the Arduino) because the line leaving your primary relay going left is a trigger signal line, rather than a power line OR
2: You DO get 220V to your secondary relay and you cannot trigger your first relay because the line leaving your primary relay going left is a power line, rather than a trigger signal line.
My first recommendation would be to redraw your diagram with clear labels on all wires.
Best Answer
It depends on details. How much current does that relay need (you did not specify the type nor parameters)? If it is higher than LED can handle then you cannot put the LED in series. Another downside is that LED in series will decrease voltage across relay coil.
I think it is much better to put in parallel, exactly as you have it. If LED fails it usually fails as dead short circuit, and relay will trigger even without LED is lit up (because it will be short). So if you would put the LED in series it will not help you at all.
It depends of what type of button you will use. If it is suitable for 24V and level of current that relay coil needs than IMHO it's better to override that MOSFET (that is in the second schematics).
If you would use the first one, you should put some 10k resistor on arduino pin output and it should be fine. It would prevent short circuit from your manual switch to arduino pin.