Vienna to Zagreb & Ljubljana to Vienna

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Hi, I'm still trying to sort out my actual route and note that I should be able to book the Vienna-Zagreb train (day) trip online at the OEBB site but how far in advance can I do that?  Also what is the best fare to ask for?  We intend joining a small tour in Zagreb going to Dubrovnik, spend some time there, and then eventually make our way (by bus and/or ferry?) along the coast and onto Ljubljana in Slovenia which brings me to the next question.  Can a train fare be booked online for the Ljubljana to Vienna leg or is it better to buy it at the station?  What sort of fare should I ask for and approx. how much would it be?  Thanks.

I just wanted to add the fact that I have just gone onto the OEBB website to have a practice run at selecting a ticket and after entering the info re departure and destination stations and no. of passengers, I was advised that 'only Business tickets could be purchased for this route and to take note of the order no'.  So, obviously I was doing something wrong, but what?  Do you have any step-by-step instructions anywhere on your site for dodos like me?!!  Also, how do you ask or select for a discount such as 2 people travelling together or seniors (over 60s) for instance?  Not sure if that applied to Austria but I have read that somewhere!!  Thanks again.

Hmm... it looks that OEBB has this specific problem with Zagreb only, for example "Ljubljana" works ok. So probably the best way to go here is to write to OEBB and request your Spar ticket via email (they give you code and you print the ticket at any OEBB ticket machine).
Concerning discounts - those available only with regular standard price tickets and not Spar ticket. And usually such discounts are much lower than difference between Spar and standard fare, so here you've got a choice - either purchase discounted Spar ticket in advance or to purchase regular ticket with group, senior etc. discount (these tickets can be bought any time - even 10 minutes before departure)
Concerning Ljubljana-Wien - cheapest option is 29 euro Spar ticket (http://www.slo-zeleznice.si/en/passengers/abroad/austria), but SZ doesn't sell international tickets online, so... no real option here