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As you probably know when you're reading this question, an .odt file is just a .zip file containing some folders and .xml files.

I used to appreciate this, for I could make a document with keywords in OpenOffice (2010), and generate for example different documents with address data online using a PHP script.

The interesting file is content.xml, where you can change the contents of the text. Afterwards, you zip everything together and you got yourself a working .odt.

However, when I make new templates using LibreOffice (2012), the resulting document is corrupted and Writer will try to recover it, but fails and leaves me with an empty document.

The file structure of the .zip (.odf) file looks the same to me. It doesn't look like something has changed, but it must have. Funny thing, when I use the 2012 content.xml from the corrupt document and zip it in a working 2010 document, it suddenly works again.

What has changed in the document format? Is there a way I can still 'automate' my files this way? Why would they change something that is nothing but nice for super users?

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Most likely this will depend on exact versions. So for the sake of your question you should really add the versions you want compared to get meaningful answers. –  0xC0000022L May 19 '12 at 14:26
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I did this often with different versions of Open Office. Can't for the life of me recall which ones, but if there is a 'version' string in the document, I can look at an old template and get back to you. –  Redsandro May 19 '12 at 14:31
    
all I'm saying is that if LO and OOo are diverging w.r.t. the file format, the differences will be relevant per version, not only on a global scale. –  0xC0000022L May 19 '12 at 14:33

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