He met her at the River Achelous and fell in love with her straightaway. However, he had to wrestle Achelous in order to win her hand in marriage.
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The four wives of Hercules were Megara, Deianira, Iole, and Hebe. Megara was his first wife, whom he killed in a fit of madness. Deianira was his second wife, whose unintentional actions led to Hercules' death. Iole was a princess whom Hercules fell in love with, and Hebe was his final wife, whom he married after his ascension to Mount Olympus.
Hercules actually has 3 wives. His first wife was Megara and he killed her and their children in a fit of rage brought on by Hera. After he completed all his labors to atone for his sins, he married his second wife, the Princess Deianira which he had to wrestle a river god for. She eventually ended up unintentionally killing Hercules. After Hercules died and became a god, he married the immortal Hebe who was his third wife.
A river.
Eventually, Juno, his jealous stepmother, drove Hercules insane. Due to his insanity, Hercules killed his wife, Megara, and their three children. Hercules exiled himself because of the shame that he had brought on himself through his lack of sanity. Later in life Hercules went to the town of Thebes and married Deianira. She bore him many children.
In Greek mythology, Nessus, the centaur, swore on Mount Erymanthus that he would help Heracles (Hercules) and protect his wife, Deianira. However, after attempting to abduct her, he was killed by Heracles. Before dying, Nessus tricked Deianira into taking his blood, claiming it would ensure Heracles' love, ultimately leading to tragic consequences. His oath became part of this deceptive legacy.