I searched the forum for similar problems. The resolution seemed to be either (a) reset Plex Web customization, or (b) re-claim the server.
You can reset Plex Web customization in Settings → Plex Web → General (https://app.plex.tv/desktop#!/settings/web/general), then go to http://ip.addr.of.syno:32400/web?secure=0.
Synology FAQ #15 has instructions on claiming a troublesome server.
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