(2.2.2-Cryptand)potassium bis(cyanato-κN)(5,10,15,20-tetraphenylporphyrinato-κ4 N)cobaltate(III) chlorobenzene hemisolvate

In the title compound, [K(C18H36N2O6)][Co(NCO)2(C44H28N4)]·0.5C6H5Cl or [K(2,2,2-crypt)+][CoIII(NCO)2(TPP)−]·0.5C6H5Cl, the CoIII ion is octahedrally coordinated by two axial N-bonded NCO− anions and four pyrrole N atoms of the porphyrin. There is a major ruffling distortion of the porphyrin: the dihedral angles between trans pyrrole rings are 34.32 (14) and 34.72 (14)°. The potassium ion is coordinated by the six O atoms and two N atoms of the cryptand-222 molecule and a weak K—O [3.407 (3) Å] bond to one of the cyanate O atoms also occurs. The packing also features weak C—H⋯O and C—H⋯π interactions. The contribution to the scattering of the disordered chlorobenzene solvent molecules was removed with the SQUEEZE function in PLATON [Spek (2009 ▶). Acta Cryst. D65, 148–155].

In the title compound, [K(C 18 H 36 N 2 O 6 )][Co(NCO) 2 (C 44 H 28 -N 4 )]Á0.5C 6 H 5 Cl or [K(2,2,2-crypt) + ][Co III (NCO) 2 (TPP) À ]Á-0.5C 6 H 5 Cl, the Co III ion is octahedrally coordinated by two axial N-bonded NCO À anions and four pyrrole N atoms of the porphyrin. There is a major ruffling distortion of the porphyrin: the dihedral angles between trans pyrrole rings are 34.32 (14) and 34.72 (14) . The potassium ion is coordinated by the six O atoms and two N atoms of the cryptand-222 molecule and a weak K-O [3.407 (3) Å ] bond to one of the cyanate O atoms also occurs. The packing also features weak C-HÁ Á ÁO and C-HÁ Á Á interactions. The contribution to the scattering of the disordered chlorobenzene solvent molecules was removed with the SQUEEZE function in PLATON [Spek (2009). Acta Cryst. D65, 148-155].
Cg2 and Cg4 are the centroids of the N2/C6-C9 and N4/C16-C19 rings, respectively. As seen in figure 1, the oxygen atom O2 of one cyanato-N axial ligand is weakly bonded to the potassium of the counterion [K(2,2,2-crypt)] + with a distance of 3.407 (3) Å. The average K-O(2,2,2-crypt) distance is 2.831 (2) Å and the average K-N(2,2,2-crypt) bond length is 3.016 (2) Å.The porphyrin core is far from being planar, with deviations of atoms from the least-squares plane of CoN 4 C 20 , ranging from -0.586 (2) to 0.607 (2) Å. It is noteworthy the relationship between the ruffling of the porphyrin core and the mean equatorial Co-N p distance; the CoN 4 C 20 moiety is ruffled as the Co-N p distance decreases, (Iimuna et al., 1988). Thus, the practically planar porphyrin core of the ion complex

Refinement
Hydrogen atoms were placed using assumed geometrically idealized positions (C-H aromatic = 0.95 Å) and constrained to ride on their parent atoms, with U(H) = 1.2 U eq (C). There are four cavities of 224 Å 3 each. PLATON estimated that each cavity contains 33 electrons which may correspond to a half solvent molecule of chlorobenzene by asymmetric unit as suggested by chemical analyses. These residual electron density was difficult to modelize and therefore, the SQUEEZE function of PLATON (Spek, 2009) was used to eliminate the contribution of the electron density in the solvent region from the intensity data, and the solvent-free model was employed for the final refinement.

Computing details
Data

Figure 1
A view of the structure of (I). Displacement ellipsoids are drawn at 50% and H atoms have been omitted for clarity.

Figure 2
A unit-cell packing of (I Special details Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes. Refinement. Refinement of F\^2\^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F\^2\^, conventional R-factors R are based on F, with F set to zero for negative F\^2\^. The threshold expression of F\^2\^ > σ(F\^2\^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F\^2\^ are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.