Not unusable. More of slightly limited use.
Windows uses a default Partitioning system known as MBR, and that includes both the data specifics and the format of the Partition Table written at the beginning of a HDD unit. When it goes to boot from a hard drive, the BIOS needs to know two things about that device: exactly where is the Partition Table, and how is the data in it organized so it can find the actual boot files on that HDD unit. Until recently, all BIOS's assumed that the HDD unit would have an MBR-type BIOS and it looked for data in that form. Using that, it could load the required files and boot Windows.
The problem that leaves, though, is that the MBR system allows for enough space to lay out up to 2 TB of data on a drive. It cannot be used for a Partition larger than that. So in your case, you could create and use a Partition of up to 2 TB on that 3 TB HDD, with the 2 TB being an MBR-type Partition. Windows would be happy to use that, and your machine's BIOS can boot from that just fine. However, the rest of the space on that HDD cannot be accessed that way.
The "proper" solution for this is to have a newer machine with a UEFI BIOS. These machines' BIOS code allow you to choose whether your HDD is Partitioned using MBR (as above) or using the new GPT system that allows much larger HDD units, and much larger Partitions on them. Using that, a you can create one or more Partitions on an HDD unit larger than 2 TB and the BIOS CAN read that form of Partition Table and boot from it. Moreover, the Partition(s) you create can be larger than 2 TB if you wish. That way you can use the whole large HDD as one "drive".
BUT you also need the correct version of Windows to do this. M$ decided not to implement support for (ability to use) HDD units partitioned in the GPT style in any of its 32-bit versions of Operating Systems. So you MUST install a 64-bit Windows version if you wish to use all of a HDD Partitioned in this new way.
In your case, there's an intermediate configuration you might consider, although maybe not exactly what you want. I believe it is possible to Install a 64-bit version of Windows in a 2TB Partition on a 3 TB HDD unit, and it will boot from that. You will still have about 760 GB of Unallocated Space on the HDD unit. But since you have a 64-bit Windows installed, you can then Create in that Unallocated Space a second Partition to be used as a separate "drive", with its own letter name, for data storage. Your BIOS that lacks UEFI support can boot from the first Partition into the 64-bit version of Windows you have installed and you will be able to use all the space of the 3 TB unit. It's just that not ALL of the 3 TB of space will be in ONE "drive" or volume. It will be in two separate "drives".