When I double click on the LibreOffice_4.1.4_Win_x86.msi file, I get the message - installation package cannot be opened, Contact the Application vendor to verify that this is a valid Windows Installer package
Unfortunately, in the absence of more information, this is awfully hard to diagnose. My first suspicion is that your download was somehow corrupted.
When you download a file, you are effectively copying that file from another computer. The normal web protocol (http:// - that prefix at the beginning of URLs) has no error checking built-in, so if a few bytes get corrupted in transport, that’s it.
Bittorrent is another method of download that breaks up large files into “manageable chunks”. Each chunk is “signed” such that if a chunk is corrupted in transport, Bittorrent knows and can correct the issue.
So, to at least rule out a corrupted download, you could:
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Try downloading the MSI file again and hope it works.
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Install a Bittorrent application, and then download the “Torrent” description, rather than the “Main installer”. Open that file with the Bittorrent application and wait until the download completes. This will at least ensure that your copy is not corrupted.