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Use this EV spread for Skarmory: 224 HP/32 Def/252 SDef; this spread gives Skarmory a Leftovers number.
A specially defensive spread is better for Rotom-W, since its resistances are often specially-based; change the nature to Calm and the EV spread to 248 HP/28 SAtk/232 SDef. Volt Switch is the better option over Thunderbolt because of its ability to damage while switching out; if Rotom-W takes a hit, it can get its next teammate in battle unscathed.