Ingrid Williams had three of the couple's five children with her in an SUV when the vehicle was struck head-on by a car travelling in the opposite direction that veered across the median, according to The Oklahoman. The children were not harmed. The driver of the other car was pronounced dead at the scene.
"The Thunder organisation has heavy hearts tonight with the news of Ingrid's passing," the Thunder said in a statement.
Monty Williams is a former NBA player and well-regarded coach around the league. He met Ingrid when he was a freshman at Notre Dame, and the couple had been together for more than 25 years. He joined Oklahoma City's staff this season after serving as head coach of the New Orleans Pelicans the preceding five years.
The Pelicans learned of Ingrid Williams' death shortly before tip-off of their four-point win over the Jazz.
Pelicans coach Alvin Gentry said the team said a prayer for Williams' family in the locker room before the game and the arena's public address announcer asked for a moment of silence.
Pelicans star Anthony Davis, who became close to Williams during his first three NBA seasons - and also during the Olympics and the FIBA World Cup, with Williams serving as a Team USA assistant - "respectfully" declined to comment on Ingrid Williams' death.
However, he said in a tweet: "Completely devastated. Ingrid Williams was like a 2nd mother to me when I got to NOLA. My thoughts & prayers are with Monty & the family."
Jrue Holiday, who played two seasons for Williams, said the news weighed heavily on the Pelicans during the game.
"The players that were here with Monty and their family definitely felt it," Holiday said. "Obviously we're all blessed to play the game of basketball but family comes before that. And I know most of the guys were thinking about our families, thinking about his family."
The Portland Trail Blazers, for whom Williams worked as an assistant coach before taking over the Pelicans, also held a moment of silence before their game against the Rockets.