
mardaddy |

Option - The demon did not "kill" the family members, she has their souls captured, and has been torturing them for the "misdeeds" of the PC's thwarting her.
The PC's either find out about this through XXXX, or has no idea until the confrontation.
Either way has its way to play up, possibly even taking a cue from a Drizzt novel and have a freed soul strike a killing blow on her in retribution.
(granted in the novel that was a "captured" Wulfgar when everyone thought he was dead, and now he was free in body and spirit, but for your game an unbound soul can still strike because rule of cool.)

Pizza Lord |
I think what I'd really want to know is this: Gathering her allies for an attack on the players is the most logical course of action for her.
If she gathers her allies now and confronts the PCs, the likely outcome is a TPK. Since it would be a TPK very much driven by an NPC's actions (As opposed to the PCs proactively biting off more than they can chew), how would you feel about it as a player if this happened to you? In normal games a TPK is a very significant event, but there a couple of factors in my game that would serve to lessen its impact:
In that case, you should probably hold off on a full-scale assault unless you have a scenario to make it an enjoyable or forward-progressing event.
I think you need to actually get the PCs to commit, so why not build off your soul binding plan, only incorporate the BBEG's lieutenants and minions on it. For instance, you say it would take her time to gather those gems, make it obvious that that is what she's doing (or at least diverting resources to finding such valuable gemstones). Definitely don't say why though, let the PCs come up with their own ideas (doomsday device, using them to raise a powerful undead, etc.) if they guess she plans to trap their souls on their own, that's fine too. At least now the PCs are going to dungeons or interesting locations/planes and trying to 'stop' the BBEG's forces (while she continues with her other plans).
Have a small ambush party assault the PCs at home. Have some good tactics that make it memorable but not super deadly. I don't know your PC builds, but do stuff like webs and aqueous orbs rolling around. The web will give cover from far away while the aqueous orb rolls back and forth, keeping the PCs from burning the webs. Thunderstones, nets, stuff you never get to use. Just have a few minions popping in through windows as some get axed (or a couple just throwing window patches from robes of useful items just screwing up the PCs' walls and decor; throwing out pits and guard dogs.) Obviously the PCs win, but they find a note on one of the attackers telling them to deal with the PCs and then go to some cave/mine/dungeon/ruin and find the Gem of [whatever].
The BBEG doesn't expect the minions to win, but she needs to collect the stones eventually. So she figures while she has her men gathering the others, she sends the PCs after one of them in one of the tougher locations or guarded by a real nasty. If they die, they die. If they succeed, they've got the gem with them until she needs it anyway. What PC is going to destroy a 14k+ gemstone? (Probably worth more, since the BBEG might expect them to level a bit.) If they do sell it... she can likely easily steal it or buy it herself from whoever they gave it to (assuming she can't charm them.)
So the PCs start seeking out or researching the locations of valuable gemstones, finding out where they're at or tracking down minions who are excavating dangerous ruins and all they're really doing is bringing all the gems to one place (close to themselves, which is where the BBEG will want them anyway.)
Finally, the BBEG decides that instead of soul bind she'll use trap the soul on one her own gems that she's recovered (and likely knows a couple of the PCs names) and either places one in a dungeon or lures a PC into touching it, possibly by using a merchant-prince who approached to sell the gemstone, since he's heard they're seeking them and no one else can afford it ("And it would be a crime to split it into smaller stone, look at its unique beauty," and the gem maybe has history or significance.)
This works great if she can have it done on a plane other than the Prime Material, since then the PCs are considered a creature from another plane (and powerful) and can be compelled to perform a service even if freed immediately.
This should at least get the PCs to be more proactive until they tire of chasing down BBEG gemstone-search parties and decide to attack the BBEG themselves... at which point, the fight is their choice.

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We are not creatures of pure and perfect reason and neither should the NPCs be
The Succubus does not exist in a vacuum. There are reasons why she plays those schemes and those reasons might justify not acting so strongly against the PCs
Maybe going all-out on mere mortals would cost her too much prestige in the eyes of other demons, and she cannot tolerate the mere thought. Or maybe they would see it as a sign of weakness and attack her, something she cannot currently afford
As a player, I would hate to have my PC die just so a NPC gets its story right and the GM should REALLY be convincing that there was absolutely zero choice
Really, Claymade's post above is made of absolute wisdom

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White Hat, Black Hat
As a GM you have two hats.
The black hat is when you run villains. They have goals, they know things, they have abilities. They're going to use them in a way that makes sense. If this demon has been thwarted by the PCs once too many times and she has plenty of free time, no big distractions, and plenty of unused resources, then she could hit them for the big time. You're doing what makes sense based on the facts.
The white hat is when you make villains. And setting. You're creating the "facts" that you go off on when you put on the black hat. And one of the important parts of making facts is: you can add facts later, as long as they don't contradict what your players already known. If you need a reason why your demon can't throw everything she's got at the players, invent an enemy that she needs to be on guard against. She's not going to take all her minions with her because then her rival could storm her lair. You can add that fact as long as you've never told the players "she has absolutely no enemies". Now your villain is still being reasonable when she doesn't bring everything she's got, because now she needs those resources elsewhere too.
And let's talk about verisimilitude. Your villain is ambitious? Ambitious people usually don't have tons of unused resources lying around. Because if you weren't using all those resources, you weren't expanding your power base as much as you could have if you did. Which means that your rival villains, who are using their resources, are getting ahead of you in the game. Who's the ambitious villain now?

UnArcaneElection |
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{. . .} FYI - the demon actually is a succubus with class levels (16th level oracle). {. . .}
{. . .} The BBEG is not an idiot and not going to sit back anymore like some passive villain. She is officially done screwing around with the PCs; putting a stop to them will become her #1 priority.
I would think that even with high Intelligence, the former might have some psychological trouble actually putting the latter into practice . . . .

Hugo Rune |
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I've read many of the comments and replies, but not all of them so apologies if I repeat what somebody else has said or go over ground that has already been covered.
To the OP: So you say that the BBEG has made eliminating the PCs her number 1 priority and if playing the role fully that would result in a TPK. To me it seems as though you need to create a reason that has so far been off-stage that means she can't.
Demon's are all about the survival of the fittest. The stronger rule the weaker. The BBEG has a plot that the PCs are successfully foiling, surely her rivals have noticed. She may want to attack the party. But in so doing she is opening herself up to an attack by one of her rivals so can't. She is instead focusing on defending herself/network/estate etc from rivals and despite how much she wants to destroy the party she literally can't.
This allows you to introduce a new dimension to your game. Perhaps one of the rivals starts to aid the PCs - indirectly of course, at least initially. The party are now drawn into an abyssal or infernal-abyssal political power struggle. Once the party realise what is happening they might have to be measured in their attacks so that one side does not win.
It takes a fair bit of work to setup but ultimately can be very rewarding. It also means that regardless of what happens the competing BBEGS should provide some shelter for the PCs against the full onslaught of the other.
EDIT: Just read Ascalaphus's sound advice. He said what I tried to say but in a clearer way.

Scott Wilhelm |
If your evil noblewoman has just been "apprehended" so that the party was able to rummage through her house, it would not at all strain verisimilitude that it might be some time before she rebuilds in her power to the point where she is in any position to act against the party.
Evil creatures are not loyal to each other. The BBEG Demon may well sever its ties with the evil noblewoman, or even kill her to prevent the spread of compromising information, or replace her with some other evil noble. This might put the evil noblewoman in a position where it serves her interest to help the party while scheming her terrible, bloody revenge at some future date, but first she has to take care of matters at hand, and anyway, how to do it?...