No, it won't exactly work that way because your charitable donations on their own are not deductible.
Charitable donations are part of Schedule A Itemized Deductions. So, in order for any charitable donations to have any effect on your return, you must be able to itemize deductions by exceeding your standard deduction. Then, either your standard deduction or itemized deductions will reduce your taxable income. Once that happens, then your suggested calculation is more valid.
If it is possible in your situation, the most effective way to offset capital gains is to liquidate and asset that will generate a capital loss. The loss will offset the gain and thus reduce the total capital gain tax.
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