An old Perry Mason show, the Case of the Bogus Books (first aired 9-27-62), has a murder caused by natural gas or methane. It seems the criminal turned off the gas to kill the pilot light and then turned the gas on again so it would kill the occupant of the room as gas from the heater poisoned the victim.
One problem is that methane isn’t a poison. “Methane is not toxic below the lower explosive limit of 5% (50000 ppm). However, when methane is present at high concentrations, it acts as an asphyxiant.” (Health Effects of Methane). It would take a long time to displace the oxygen in a room with enough methane and the victim would likely wake up with headache and nausea first (e.g. like in sleep apnea). “There is no stronger signal to the brain than low blood oxygen. That means, quite literally, that death is imminent and all hades breaks loose.” (Sleep Guide)
Then there’s the problem of the pilot light going out and no safeties on the heater. The history of thermocouples and their application as a safety device in pilot light operated devices should go way back – the thermocouple principle was discovered in 1821 (wikipedia). If the gas goes off, the heater shuts off the gas and it requires resetting the safety to get it going again.
Then there’s the smell. That goes back to Germany in the 1880’s by Von Quaglio.
Now, if the victim woke up due to low oxygen, ignored the hiss and the smell, and lit a cigarette …
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