Resuming the second session on 358 for 6, India batted for another 14.2 overs before being all out for 421 in 120.4 overs in their second innings.
After lunch, captain Mahendra Singh Dhoni and R Ashwin tried to increase the scoring rate, but the latter was out caught at cover off Vernon Philander, for seven runs, soon after the visitors reached 350.
Zaheer Khan and Ishant Sharma then added 21 crucial runs for the ninth wicket, taking India past the 400-run mark in the 118th over. The tail-enders tried their best to give momentum to India in the dying stages of the innings. Zaheer smacked the first six of the Test in the 117th over of the innings and added another hitting Dale Steyn for one over long-off in the 120th over. He remained unbeaten on 29 runs off 31 balls with three fours and two sixes.
For South Africa, Vernon Philander (28-10-68-3) and Jacques Kallis (20-5-68-3) were the most successful bowlers, as Morne Morkel (2-1-4-0) was rendered out of action after twisting his ankle on day three.
Steyn (30-5-104-0) did not have a single wicket to show for in his 30 overs. Duminy picked up 2/87, while A B de Villiers (0/9) had bowled an over for fun just ahead of tea on day three.
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