Theducks is absolutely correct and he mentions the optimal way to handle things. Basically in any field, a blank or un-assigned value means null, non-applicable, non-existent.
If it is your intention to have an easy way to find stand-alone books, you can either click on the Series header in the Book/Table view of calibre. Or enter series:false into the search field.
However, if for some reason you don't want to leave the series field blank, you could use something like "None" or "--" (use two dashes so you know it's not simply a typo).
However, doing this would cause the series index to want a number entered. Resulting in "None [1]" or "--[1]" showing up. Further if you haven't changed things in Preferences>Tweaks, additional books edited to show series: None will increment this number. Making it look more and more like a legitimate series.
Worse, doing so creates an artificial connection between the books. So if you had three wildly different books in calibre (say a Bible, a Romance and an Accounting textbook) they would now all be part of the "None" series - despite having nothing to do with each other.
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