P2N2S(OCl3)2 is alpha U structured and crystallizes in the monoclinic P2_1/c space group. The structure is zero-dimensional and consists of four P2N2S(OCl3)2 clusters. There are two inequivalent P sites. In the first P site, P(1) is bonded to one N(1), one Cl(1), one Cl(2), and one Cl(3) atom to form PNCl3 tetrahedra that share  a cornercorner with one S(1)N2O2 tetrahedra. In the second P site, P(2) is bonded to one N(2), one Cl(4), one Cl(5), and one Cl(6) atom to form PNCl3 tetrahedra that share  a cornercorner with one S(1)N2O2 tetrahedra. There are two inequivalent N sites. In the first N site, N(1) is bonded in a bent 120 degrees geometry to one P(1) and one S(1) atom. In the second N site, N(2) is bonded in a distorted bent 120 degrees geometry to one P(2) and one S(1) atom. S(1) is bonded to one N(1), one N(2), one O(1), and one O(2) atom to form SN2O2 tetrahedra that share  a cornercorner with one P(1)NCl3 tetrahedra and  a cornercorner with one P(2)NCl3 tetrahedra. There are two inequivalent O sites. In the first O site, O(1) is bonded in a single-bond geometry to one S(1) atom. In the second O site, O(2) is bonded in a single-bond geometry to one S(1) atom. There are six inequivalent Cl sites. In the first Cl site, Cl(4) is bonded in a single-bond geometry to one P(2) atom. In the second Cl site, Cl(5) is bonded in a single-bond geometry to one P(2) atom. In the third Cl site, Cl(6) is bonded in a single-bond geometry to one P(2) atom. In the fourth Cl site, Cl(1) is bonded in a single-bond geometry to one P(1) atom. In the fifth Cl site, Cl(2) is bonded in a single-bond geometry to one P(1) atom. In the sixth Cl site, Cl(3) is bonded in a single-bond geometry to one P(1) atom.
P2N2S(OCl3)2 is alpha U structured and crystallizes in the monoclinic P2_1/c space group. The structure is zero-dimensional and consists of four P2N2S(OCl3)2 clusters. There are two inequivalent P sites. In the first P site, P(1) is bonded to one N(1), one Cl(1), one Cl(2), and one Cl(3) atom to form PNCl3 tetrahedra that share  a cornercorner with one S(1)N2O2 tetrahedra. The P(1)-N(1) bond length is 1.55 Å. The P(1)-Cl(1) bond length is 2.01 Å. The P(1)-Cl(2) bond length is 2.01 Å. The P(1)-Cl(3) bond length is 1.99 Å. In the second P site, P(2) is bonded to one N(2), one Cl(4), one Cl(5), and one Cl(6) atom to form PNCl3 tetrahedra that share  a cornercorner with one S(1)N2O2 tetrahedra. The P(2)-N(2) bond length is 1.55 Å. The P(2)-Cl(4) bond length is 2.01 Å. The P(2)-Cl(5) bond length is 2.01 Å. The P(2)-Cl(6) bond length is 1.99 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded in a bent 120 degrees geometry to one P(1) and one S(1) atom. The N(1)-S(1) bond length is 1.63 Å. In the second N site, N(2) is bonded in a distorted bent 120 degrees geometry to one P(2) and one S(1) atom. The N(2)-S(1) bond length is 1.62 Å. S(1) is bonded to one N(1), one N(2), one O(1), and one O(2) atom to form SN2O2 tetrahedra that share  a cornercorner with one P(1)NCl3 tetrahedra and  a cornercorner with one P(2)NCl3 tetrahedra. The S(1)-O(1) bond length is 1.44 Å. The S(1)-O(2) bond length is 1.45 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a single-bond geometry to one S(1) atom. In the second O site, O(2) is bonded in a single-bond geometry to one S(1) atom. There are six inequivalent Cl sites. In the first Cl site, Cl(4) is bonded in a single-bond geometry to one P(2) atom. In the second Cl site, Cl(5) is bonded in a single-bond geometry to one P(2) atom. In the third Cl site, Cl(6) is bonded in a single-bond geometry to one P(2) atom. In the fourth Cl site, Cl(1) is bonded in a single-bond geometry to one P(1) atom. In the fifth Cl site, Cl(2) is bonded in a single-bond geometry to one P(1) atom. In the sixth Cl site, Cl(3) is bonded in a single-bond geometry to one P(1) atom.