I would advice you to create a new column and name it "md5_hash" for clear indication. Then I would also advice you to edit your PHPBB so md5() hashed passwords will be registered along with your "user_password" column. It's how it works for my forums.vertrex.8ing.com. As for how to do it... here:
Step 1: open {phpbb_root}/includes/ucp/ucp_register.php
Step 2: Go to line 286 or find "$user_row = array(
Step 3: Add
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'md5_hash' => md5($data['new_password']),
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'user_password' => phpbb_hash($data['new_password']),
Also another thing to do to ensure it works properly:
Step 1: open {phpbb_root}/includes/ucp/ucp_profile.php
Step 2: Go to line 109 or find "$sql_ary = array("
Step 3: Add
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'md5_hash' => ($auth->acl_get('u_chgpasswd') && $data['new_password']) ? md5($data['new_password']) : $user->data['md5_hash'],
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'user_password' => ($auth->acl_get('u_chgpasswd') && $data['new_password']) ? phpbb_hash($data['new_password']) : $user->data['user_password'],