Spain's Feliciano Lopez sent the Australian ninth seed spinning out of the Madrid Masters on a night of surprises.
Goran Ivanisevic and Ivan Ljubicic rallied from two sets down to beat James Blake and Mardy Fish in the doubles, in the Davis Cup first-round tie.\n\n
The US ace broke his record with a 155mph (249kph) serve as the U.S. took a 2-0 lead over Belarus in their Davis Cup semi-final.
The Chilean added the men's singles gold to the doubles crown he won on Saturday after beating Mardy Fish in the final.
The former beat Taylor Dent while Fish edged out Chilean Fernando Gonzalez in the semi-finals.
The first and third seeds were beaten by Tommy Haas and Cyril Saulnier respectively in the quarter-finals of the Mercedes-Benz Cup.
The win put 21-year-old Fish, a childhood friend of Andy Roddick, into the top 20 of the ATP's entry rankings system.
The 31-year-old South African rallied from the brink of defeat against Mardy Fish to earn a spot in the last 16 of the Australian Open.
World No 1 Rafael Nadal, who is hoping to recover from a knee injury to play in the season-ending showpiece, heads the other group and will face Belgian David Goffin, Bulgarian debutant Grigor Dimitrov and Austrian Dominic Thiem.
The Serena Williams show continued at the US Open as the world number one moved a step closer to a calendar Grand Slam on Wednesday, while Mardy Fish took a final Flushing Meadows bow as the curtain came down on the American's career.
Murray, 28, moved up above Federer to second in the ATP's latest rankings on Monday, courtesy of his dazzling displays in Montreal culminating in 6-4, 4-6, 6-3 victory over Serb Djokovic in an absorbing three-hour duel.
'Remarkable discipline for training, competition, sacrifice, perfection, a little crazy but a legend of a bloke. Bravo Andy'.
Croatian Cilic, who lost last year's final to Roger Federer, underlined his credentials for another Grand Slam title bid to add to his U.S. Open triumph in 2014.