Is it safe to have sexual intercourse on 19th day of menstrual cycle?

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You are right in contemplating the fact that tomorrow she will be on her day 19 of her cycle, which is her unsafe period if her menses have been regular, so chances of pregnancy with unprotected intercourse would definitely be higher. So, the best way to have protection would still be barrier contraception with condoms with additional use of spermicidal jelly over it to reduce the chances of failure due to rupture condoms during intercourse. Also, practice ejaculation outside the vagina, that would further reduce the chances of any misadventure. The second method is to ask her to use a cervical diaphragm, which is a female condom and needs to be inserted before intercourse and removed post intercourse along with you using barrier contraception. The failure rate of condoms is 3.3 percent which can be increased by either using double condoms with or without spermicidal jelly or with a female condom.