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For some reason I've always assumed the older formats (Office 2007/XP) DOC/XLS were the safest to maintain compatibility with Office simply due to them being aged and likely more mature, however I've recently been told one of the reasons/benefits for DOCX/XLSX is that the old formats are actually an abomination. This has thrown my whole decision of which suite/format to focus on into disarray!

I hope this question isn't seen as breaking any of the SE rules in asking for a recommendation, I more looking for statistical or absolute proof of the best combination rather than personal preference.

Thanks!

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If the other Office suite (you probably meant MS-Office) can read your OpenDocument Format files, then aiming for the ODF format would probably be the best plan because it's an open format that will likely see support from an ever-increasing number of products in the future, many of which will likely also be open source.

  OpenDocument Format (ODF)
  http://www.fsf.org/campaigns/opendocument

The most common reason for choosing older file formats is to ensure compatibility with a minimum version number of a given product. You'll have to determine if this is an important factor, but do keep in mind that since OpenOffice, LibreOffice, and potentially other similar products are free software, the justification for supporting the older versions may actually be a lot less important since cost is no longer a barrier.

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Agreed. Office 2007 and above natively supports .odt documents for both reading and writing (although the exactness of the implementation is worth testing). – harrymc May 16 '11 at 10:36
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The main purpose is to try and provide compatible documents with external sources like clients who are likely unaware or incapable of working with various formats that don't work out of the box with Office. There was a time when Doc files still seemed to get sent, but nowadays I almost never see anything that isn't Docx sent to me. – DanH May 16 '11 at 14:08
@DanH: Great comment (I also like @harrymc's comment)! I see lots of .PDF but .doc/.docx are extremely rare these days. I suspect that each person gets different experiences, with this since it's dependent on what they do and who they communicate with, but as for web sites I've also noticed that .doc/.docx have pretty much disappeared almost completely and .PDF has basically taken their place. I think it would be nice to see ODF download options along with the .PDF options though since this would encourage further support of the open source movement. – Randolf Richardson May 18 '11 at 8:34
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Actually I shouldn't forget to emphasize XLS/XLSX which I tend to see more of than DOC/DOCX/PDF in fact. Although spreadsheets formatting is generally much less important, just as long as the numbers are all correct, and rarely, functions too. – DanH May 18 '11 at 8:40
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