The Nationals will hold a news conference Friday to introduce Williams as the team's fifth manager since it moved to Washington from Montreal in 2005. He replaces Davey Johnson, who is retiring.
It is Williams' first job as a big-league manager. He has only brief managerial experience, having spent time in the Arizona Fall League and five weeks at Double-A in the minors.
He's been the Arizona Diamondbacks third-base coach the past three seasons.
The 47-year-old Williams was a five-time All-Star and a four-time Gold Glove recipient during 17 years as a player for the Giants, Indians and Diamondbacks.
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