In 9800 WLC, you might have observed that although 6 GHz band in US domain supports 320 MHz until channel 221 there is no option to configure this from the WLC webGUI. The last channel that the webGUI will allow us to set for 320 MHz is 189.

6 GHz band in mode 2 supports 320 MHz channel width for higher channels above 189 with center channel index as 191.
Although this cannot be configured from the webGUI, it can be configured from the CLI as follows-

Related Blogs-
Cisco Configuration Guides
How to associate my Wi-Fi 7 client on 6 GHz with 320M CW?
How to configure 9800 WLC for max throughput and max spatial streams?
How to configure WLAN for MLO client association in 9800 WLC?
Wireless Troubleshooting
How to Troubleshoot 6 GHz 320 MHz cw client association?
Cisco Wireless