Let $0 < x < y < z$. Then we have:
$$\pi = \arccos\left(-\frac{\frac{x^{2}}{y^{2}} + \frac{x^{2}}{z^{2}} - \frac{y^{2}}{z^{2}} - 1}{2 \, \sqrt{-\frac{x^{2}}{y^{2}} + 1} \sqrt{-\frac{x^{2}}{z^{2}} + 1}}\right) + \arccos\left(-\frac{\frac{x^{2}}{y^{2}} - \frac{x^{2}}{z^{2}} + \frac{y^{2}}{z^{2}} - 1}{2 \, \sqrt{-\frac{x^{2}}{y^{2}} + 1} \sqrt{-\frac{y^{2}}{z^{2}} + 1}}\right) + \arccos\left(\frac{\frac{x^{2}}{y^{2}} - \frac{x^{2}}{z^{2}} - \frac{y^{2}}{z^{2}} + 1}{2 \, \sqrt{-\frac{x^{2}}{z^{2}} + 1} \sqrt{-\frac{y^{2}}{z^{2}} + 1}}\right)$$
I have a proof for this, but I would like to know if there are other proofs for this.
Here are some formulas I derived using the technique above, which I find amusing:
$$\pi = \arccos\left(\frac{1}{12} \, \sqrt{5} \sqrt{3}\right) + \arccos\left(\frac{5}{32} \, \sqrt{5} \sqrt{2}\right) + \arccos\left(\frac{13}{48} \, \sqrt{3} \sqrt{2}\right)$$
$$\pi = \arccos\left(\frac{1}{24} \, \sqrt{7} \sqrt{5}\right) + \arccos\left(\frac{13}{108} \, \sqrt{7} \sqrt{3}\right) + \arccos\left(\frac{25}{144} \, \sqrt{5} \sqrt{3}\right)$$
$$\pi = \arccos\left(\frac{75}{128}\right) + \arccos\left(\frac{41}{160} \, \sqrt{7}\right) + \arccos\left(\frac{3}{40} \, \sqrt{7}\right)$$
$$\pi = \arccos\left(\frac{41}{500} \, \sqrt{11} \sqrt{5}\right) + \arccos\left(\frac{1}{20} \, \sqrt{11}\right) + \arccos\left(\frac{61}{200} \, \sqrt{5}\right)$$
$$\pi = \arccos\left(\frac{1}{84} \, \sqrt{13} \sqrt{11}\right) + \arccos\left(\frac{61}{864} \, \sqrt{13} \sqrt{6}\right) + \arccos\left(\frac{85}{1008} \, \sqrt{11} \sqrt{6}\right)$$
$$\pi = \arccos\left(\frac{1}{112} \, \sqrt{15} \sqrt{13}\right) + \arccos\left(\frac{85}{1372} \, \sqrt{15} \sqrt{7}\right) + \arccos\left(\frac{113}{1568} \, \sqrt{13} \sqrt{7}\right)$$
$$\pi = \arccos\left(\frac{1}{144} \, \sqrt{17} \sqrt{15}\right) + \arccos\left(\frac{113}{1024} \, \sqrt{17} \sqrt{2}\right) + \arccos\left(\frac{145}{1152} \, \sqrt{15} \sqrt{2}\right)$$
$$\pi = \arccos\left(\frac{1}{180} \, \sqrt{19} \sqrt{17}\right) + \arccos\left(\frac{145}{972} \, \sqrt{19}\right) + \arccos\left(\frac{181}{1080} \, \sqrt{17}\right)$$
$$\pi = \arccos\left(\frac{1}{220} \, \sqrt{21} \sqrt{19}\right) + \arccos\left(\frac{181}{4000} \, \sqrt{21} \sqrt{10}\right) + \arccos\left(\frac{221}{4400} \, \sqrt{19} \sqrt{10}\right)$$
Edit: The proof is based on noticing that every $3$ point metric space can be embedded in $\mathbb{R}^2$ as a triangle and then using trigonometry. (See Whats the name of this surface $a^2+b^2+c^2+2abc-1=0$? )
The metric space I am considering is a Hilbert space:
$$k(x,y) = \frac{\min(x,y)^2}{\max(x,y)^2}$$
with metric:
$$ d(x,y) = \sqrt{2(1-k(x,y))}$$
For three points $x,y,z$ in a metric space, we can define (using the law of cosines) the following quantity:
$$s(x,y,z) = \frac{d(x,y)^2+d(y,z)^2-d(x,z)^2}{2d(x,y)d(y,z)}$$
Then we can embedd $X \times X \times X$ to the Cayleys surface ( https://mathcurve.com/surfaces.gb/cayley/cayley.shtml ) through the mapping:
$$f(x,y,z) = (s(x,y,z), s(z,x,y),s(y,z,x))$$
We then have:
$$\pi = \arccos(s(x,y,z))+\arccos(s(z,x,y))+\arccos(s(y,z,x))$$
which proves the claim.