I don’t know if it’s looking only at the 172.x network, or the 192.x network the NAS is on.
I have WeMo and TP-Link devices up and running, linked through Google Assistant. However, HomeAssistant is unable to find any of these plugs. Philips Hue, however, is working.
Via the CLI, you use --net=host to set the network to host. Via docker-compose, you use network_mode: host on your service. I do not believe you can do this within the Synology UI.