Here is a pretty effective Defensive core that I have used on a few teams. I don't post often or play too competitively so please have mercy but I think I found a pretty nice core here.
Rotom-W + Clefable + Excadrill
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At first glance, this seems like a very uncommon defensive core. However, the three actually function well together with a few exceptions (which I will go over later). On paper, this core resists 12/18 attack types as well as 4 immunities. This core is primary based on setting/removing hazards and crippling opponents. This core does have some inherent weaknesses such as Iron Head Kyurem, Mold Breaker Excadrill and Serperior. For EV spreads and sets, Clefable and Rotom-W have their standard defensive sets. You can opt for a Wish Pass Clefable as well if you already have a dedicated Stealth Rock setter on your team as it really helps the longevity of Excadrill and Rotom-W.
AV Excadrill is the only thing (slightly) innovative here. With the EV's below, Excadrill can take out many Flying and/or Electric types in the game by soaking up their coverage moves and hitting hard back with Earthquake and Rock Slide. Below are a few calcs showing how Excadrill can pave the way for Flying teammates such as Mega Pinsir, Talonflame or any Pokemon weak to Stealth Rock/Spikes.
- 252 SpA Mega Manectric Flamethrower vs. 0 HP / 224 SpD Assault Vest Excadrill: 144-170 (39.8 - 47%) -- guaranteed 3HKO
- 252 SpA Mega Manectric Overheat vs. 0 HP / 224 SpD Assault Vest Excadrill: 208-246 (57.6 - 68.1%) -- guaranteed 2HKO
- 252 SpA Life Orb Thundurus Focus Blast vs. 0 HP / 224 SpD Assault Vest Excadrill: 234-278 (64.8 - 77%) -- guaranteed 2HKO
- 160 SpA Tornadus-T Focus Blast vs. 0 HP / 224 SpD Assault Vest Excadrill: 154-182 (42.6 - 50.4%) -- 1.2% chance to 2HKO
- 252 SpA Choice Specs Raikou Shadow Ball vs. 0 HP / 224 SpD Assault Vest Excadrill: 85-101 (23.5 - 27.9%) -- 84.3% chance to 4HKO
- 0 SpA Rotom-W Hydro Pump vs. 0 HP / 224 SpD Assault Vest Excadrill: 176-210 (48.7 - 58.1%) -- 95.7% chance to 2HKORotom-Wash @ Leftovers
Ability: Levitate
EVs: 248 HP / 252 Def / 8 Spe
Bold Nature
- Volt Switch
- Hydro Pump
- Pain Split
- Will-O-Wisp
Clefable @ Leftovers
Ability: Magic Guard
EVs: 252 HP / 172 Def / 84 SpD
Calm Nature
- Stealth Rock
- Moonblast
- Thunder Wave
- Soft-Boiled
Excadrill @ Assault Vest
Ability: Mold Breaker
EVs: 252 Atk / 224 SpD / 32 Spe
Adamant Nature
- Earthquake
- Iron Head
- Rapid Spin
- Rock Slide
Not trying to hate on this core or anything (I like it in-fact), but I think you'd have much better success by switching the sets around slightly. Assault Vest Excadrill is simply not good at all. 4 Attack Excadrill is only good for Life Orb sets and using AV on a set that desperately needs Leftovers gets it worn down. So change AV to Leftovers and replace Rock Slide with either Toxic (For Mega Sableye) or SR to set up against Mega Sable or Mega Diancie. This frees up Clefable to use CM > SR, which gives this core a solid win condition. P.S: If you go Toxic on Exca, you can stick SR somewhere else on your team.
Tl;Dr:
Leftovers > AV and Toxic / SR > Rock Slide on Excadrill
Calm Mind > SR on Clefable.
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