Caffeine is poisonous to us too, so I think it's more accurate to say that humans enjoy the side effects of that particular neurotoxin. It's generally not possible for someone healthy to drink enough coffee to die, but they sell pure caffeine (for research) and even seemingly small amounts of that will kill a person.
You can buy 200mg pure anhydrous caffeine pills at Walmart for like $5. It's abundant and as safe as coffee if you don't go nuts. The max daily recommended dose is 400mg, anything past that could cause harm
What I had in mind is more like this 25kg bucket. That's enough to kill about 2,000 people, which is actually a lot fewer people than I would have guessed before I looked up the LD50.
I've never actually seen caffeine in a bucket myself, but I worked in a lab once that had a big plastic jar of it.
What I read was that it's about 200mg per kg, so for a 70kg human that works out to 14 grams. That actually sounds remarkably high (14 grams is a lot). Did I mess up somewhere?