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After openers Neil McKenzie (94) and Graeme Smith (73) set the tone for the day, South Africa dominated all three sessions to finish day one at 304 for four.
The visitors got off to a perfect start with McKenzie and Smith, barely three weeks after their world record opening stand against Bangladesh, forging yet another century partnership to lay the foundation for a big total.
Though their batting mainstay Jacques Kallis, otherwise a familiar India nemesis, returned before he could make a substantial mark in the match, Hashim Amla (85 not out) took it on his able shoulders to build on the platform.
At stumps, Amla (85) and AB de Villiers (10) were in the middle and they would return tomorrow hoping to further swell the tally.
On a day thoroughly dominated by the batsmen, Anil Kumble was the pick of the Indian bowlers, claiming two for 61, while his spin twin Harbhajan Singh got as many for 92 runs.
After winning an important toss, Smith predictably decided to take first strike on M Chidambaram Stadium's flat strip.
With India's new ball attack of RP Singh and S Sreesanth looking pretty pedestrian, even though the Kerala speedster did beat Smith's tentative bat on a couple of occasions, Smith stood vindicated.
Smith and McKenzie looked in a positive frame of mind as they negotiated pace and spin with aplomb, maintaining a healthy run rate of four per over.
Kumble pressed himself into service as early as the 11th over but the breakthrough continued to elude the hosts.
Smith also had his slice of luck when a diving Dhoni could not properly pouch an inside edge off Sreesanth and spilled the ball while getting back to his feet.
The Indians made a vociferous appeal but umpire Asad Rauf was not impressed.
Kumble finally gave the team something to cheer about but not before Smith had cobbled together a 132-run stand with his partner. The Indian skipper induced a drive from his opposite number which found VVS Laxman's outstretched hand at short mid-wicket.
Smith's 73 came off 97 balls and included 13 boundaries.
McKenzie, however, looked unperturbed and continued in the same fashion. His occasional moments of discomfort against Harbhajan Singh notwithstanding, the right-hander was impressive and looked certain for a century before the off-spinner did him in 10 minutes before tea.
McKenzie went on the front foot to defend a delivery only to edge it to Rahul Dravid at the lone slip to fall just six shy of a well-deserved ton.
McKenzie's 156-ball knock was studded with 18 hits to the fence.
Kallis (13) has an impressive record against India but today was not his day as the veteran all-rounder returned via a bad-pad catch at short leg to give Harbhajan his second wicket of the day. South Africa were 244 for three at that stage.
Next man in Ashwell Prince (23) too looked keen to get some runs under the belt and got the start as well.
Kumble, however, ensured that he did not go on when the leg-spinner dived across to take a sharp catch off his own bowling.
All along, Amla remained confidence personified and the right-hander shunned extravagance but never shied away from going after loose deliveries. He played some gorgeous drives off the front foot and negotiated spin quite well.
Amla faced 159 balls and hit 10 boundaries en route to his unbeaten 85.