The users per hour do not sum up to the users during the day. Each hour, Google Anaytics tells you how many users there were on the site during that hour. If Tom visited your site at 9:00am and also at 11:00am, he would count 1 one user for both the rows 9 and 11 in your spreadsheet. But, he would only count as 1 user for the day.
Works the same way for days and weeks. If you add up the users each day, it will typically be less than the users for the week. Because some users likely visited your site on more than one day.