Mr Livingstone spoke to the RMT general secretary today as the 6.30pm deadline loomed, despite telling reporters earlier that he was not a "trained negotiator" and that to intervene in the row would be "great theatre but very bad industrial relations".
A final unsuccessful attempt to break the deadlocked row was made today when London Underground (LU) managers met officials from the RMT, but the union confirmed just before 3.30pm that the strike would go ahead. LU managing director Tim O'Toole had also spoken by telephone to Mr Crow.
The strike is expected to last in effect until Thursday morning, as the underground system will struggle to resume a full service when the 7,500 RMT workers return on Wednesday evening.
Mr Crowe said today: "We send our apologies to travellers, and these are not crocodile tears."
He added that no progress had been made during today's talks and could not rule out further industrial action unless the deadlock was broken.
London Underground said: "The RMT decision to strike is completely unnecessary and would only make travel in London incredibly difficult for millions of Londoners. LU has made a very good offer and strike action will not change it."
At his weekly press conference this morning, Mr Livingstone had urged tube workers to accept the deal on offer, saying it was the best available in either the private or public sector.
But the two sides remained at loggerheads over a pay offer from LU giving a two-year increase worth 6.75% and a guarantee to reduce the working week by two-and-a-half hours by 2006.
But the talks broke up within 20 minutes after the union voiced concerns that an agreement to reduce hours to 35 by 2006 would be "self-financing" and thus not apply to all LU workers.
The improved LU offer includes a 3.5% pay rise this year and the rate of inflation plus 0.5% next year, as well as a "clear commitment" of a 35-hour week for all staff by July 2006.
LU said it had also increased pension contributions to make sure that all staff remained eligible for the company's final salary pension scheme.
LU said that the union had today put forward a proposal for a trial of a four-day week which the company said was "unaffordable".
A spokesman added: "The LU offer matches, if not exceeds, the best deals in the railway industry which the RMT has already accepted."
Mr Crowe attacked comments made by Mr Livingstone raising the prospect of station staff being cut. "With the current threat of terrorist attacks, it would be madness to reduce the number of staff."
Mr Livingstone said at his press conference this morning he wanted to see more "fulfilling" jobs for tube workers, but the union fears the modernisation could lead to up to 800 redundancies.
On comments he made previously about crossing the picket lines, the mayor said: "I'm not advocating telling people what they should do because they've got to work together afterwards.
He added: "I hope that the trade unions will recognise that this is just about the best offer that's actually on the table in any public or private industry and today will accept it and call off the strike."
Mr Livingstone said he hoped there would be "dramatic working changes" on the underground with "dull jobs", such as looking for people wrongly using child tickets, being improved to make them more fulfilling.
"What we would like to do is have a complete rethink about the way forward in the underground so that staff get infinitely more fulfilling daily work.
Extra buses will be mobilised to ease transport problems if the strike goes ahead, Mr Livingstone added.
Mr Crowe, speaking at his union's annual conference in Portsmouth, is expected to travel to London tomorrow to join a picket line.
