Think of volunteering as an "organized" thing like school or work. Yes, you can meet people at school or work, but there are also many rules and expectations. And just like work and school, there will be unspoken rules and hidden agendas and peer pressure and hypocrisy. You will also have to deal with "seniority" which means you will often be treated like a "newbie". When you volunteer you have a solid commitment and people will react negatively if you cannot show up. They will also tend to pressure you into making more time to volunteer by making changes in your personal life and canceling other commitments outside volunteering. People who volunteer generally have expendable time or income. This usually means old people or rich people. Volunteering has many problems that my next few suggestions do not have.
I would suggest doing things that people do in their "free time". Most people use their free time to join a gym or do other social activities like bowling, miniature golf, etc. Because people have already set this "free time" aside for these activities, they may be more open to talk without having to worry about deadlines. The YMCA has a scholarship program to pay a reduced price for a membership and you do not need to be a student. Your local library may offer free programs as well as post local events. Most libraries let you use other libraries in the library system, so you should try to find the best library in the area. My library has movies and games, as well as museum passes, so look around and don't be afraid to ask the library workers.
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