It may be the plain Biotin.Cut the pill in half and make sure to take it with food,then see if that helps.Other things that may cause headaches are evening primrose oil and fish oil.Make sure to check the expiration dates also....
To cure headaches take feverfew..It is THE BEST REMEDY ever and I can't speak of it enough.I suffered from migraines for years and was on about 12 different meds(at different times),but All natural feverfew works better than all of them.You can buy the capsules at While foods market.
There is also a natural product at Walgreen's.I can't remember the name,but I know that it comes in little tubes that you place it under your tongue.HTH.
ETA..The MSM gave me TERRIBLE headaches..