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[P(NPCl3)4]+PCl-6, Mr = 880.02, monoclinic, P21/m, a = 7.720 (2), b = 21.235 (5), c = 8.248 (2) Å, \beta = 91.12 (2)°, V = 1351.9 (6) Å3, Z = 2, Dx = 2.162 Mg m-3, \lambda(Mo K\alpha) = 0.71069 Å, T = 93 K, R = 0.0497, S = 1.007 for 4536 unique observed reflections and 140 parameters. The cations and anions show site symmetries of Cs(m) and Ci(\overline 1), respectively. The P-N bond lengths in the NPCl3 groups are distinctly shorter [1.515 (4)-1.532 (4) Å] than those attached to the central P atom [1.595 (2)-1.611 (4) Å], the P-Cl bond lengths are 1.961 (1)-1.975 (1) Å in the cations and 2.132 (1)-2.142  (1) Å in the anions; the P-N-P angles lie in the range 132.5 (2)-142.9 (3)°. The structure is a derivative of the CsCl structure type showing interionic distances of 3.314 (1)-3.414 (1) Å, between the Cl atoms. The differences between the angles P-Clcation...Clanion [153.38 (5)-168.28 (5)°] and P-Clanion...Clcation [102.30 (3)-116.35 (4)°] are very probably caused by the arrangement of the lone pairs at the Cl atoms. The thermal motion analysis showed that the anion behaves as a rigid body {Ru = [\Sigmaw(\DeltaU)2/\Sigmaw(Uobs)2]1/2 = 0.024}, whereas the cation does not (Ru = 0.347). Allowing three intramolecular torsions the residual index Ru for the cation could be lowered to 0.184.

Supporting information

cif

Crystallographic Information File (CIF)
Contains datablock p50f

fcf

Structure factor file (CIF format)
Contains datablock p50f

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