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What IP address should I assign to Pi-hole?

Pick a static IP outside your router’s DHCP range. For example, if your DHCP pool is 192.168.1.100–192.168.1.200, something like 192.168.1.198 or 192.168.1.10 works well. The important thing is that it doesn’t conflict with another device and won’t be handed out by DHCP.

How to Set Up Pi-hole on a Synology NAS (Container Manager) - WunderTech
Why can’t my Synology NAS reach Pi-hole on the macvlan IP?

Macvlan is a known limitation — the host machine (in this case, the NAS) cannot communicate with containers on a macvlan network. The Docker Compose file in this guide creates a second bridge network (192.168.100.2) specifically so the NAS can reach Pi-hole. Use that IP if you want the NAS itself to use Pi-hole for DNS.

How to Set Up Pi-hole on a Synology NAS (Container Manager) - WunderTech