Unusual poisons are not that popular as a means of murder in mystery stories these days, but all the same, I just got an idea for an interesting one: injected snake venom with the same symptoms as a poison.
One of the difficulties with poisons is that it’s really hard to have an alibi with one. The benefit to a snake venom is that if people don’t look for injections, they won’t be able to find out how the poison was administered, because it wasn’t. A person who thus had no access to the food of the victim could probably put themselves out of suspicion this way.
As an additional benefit, if the police do not specifically suspect snake venom, it is exceedingly unlikely that the lab will run any assays for snake venom. Even if they did, they would tend to look for the venom of native species rather than rare imports.
This is only a half formed idea so far, but it has some interesting possibilities.