You need to add a so called Area to the template used by the 404-page. Without an Area you won't be able to add the block to the 404-page.
If you use the default concrete5 Elemental theme and you haven't copied the theme to your application folder:
Once you've copied the theme to your application folder and it has been activated, do the following:
<?php
defined('C5_EXECUTE') or die("Access Denied.");
$this->inc('elements/header.php'); ?>
<main>
<div class="container">
<div class="row">
<div class="col-sm-9 col-sm-offset-3">
<div class="jumbo">
<h1><?php echo t('404 Error')?></h1>
<p><?php echo t('Page not found.')?></p>
<?php
$a = new Area('Content');
$a->display($c);
?>
</div>
</div>
</div>
</div>
</main>
<?php $this->inc('elements/footer.php'); ?>
Now you can add the block to the 404-page!