{rac-5-[Methoxy(phenyl)methyl]-10,20-diphenylporphyrinato}nickel(II)

The title compound, [Ni(C40H28N4O)], was obtained from a Grignard reaction of the respective formylporphyrin to yield {5-[hydroxy(phenyl)methyl]-10,20-diphenylporphyrinato}nickel(II), followed by crystallization from methylene chloride/methanol. The molecule exhibits a ruffled macrocycle with an average deviation of the 24 macrocycle atoms from their least-squares plane (Δ24) of 0.26 Å and an average Ni—N bond length of 1.931 (2) Å. In line with the asymmetrical substituent pattern, the degree of distortion is slightly larger at point of attachment of the methoxy(phenyl)methyl residue than at the unsubstituted meso position. The methoxy group attached to the chiral C atom is disordered in a 0.534 (4):0.466 (4) ratio.

The title compound, [Ni(C 40 H 28 N 4 O)], was obtained from a Grignard reaction of the respective formylporphyrin to yield {5-[hydroxy(phenyl)methyl]-10,20-diphenylporphyrinato}nickel(II), followed by crystallization from methylene chloride/methanol. The molecule exhibits a ruffled macrocycle with an average deviation of the 24 macrocycle atoms from their least-squares plane (Á24) of 0.26 Å and an average Ni-N bond length of 1.931 (2) Å . In line with the asymmetrical substituent pattern, the degree of distortion is slightly larger at point of attachment of the methoxy(phenyl)methyl residue than at the unsubstituted meso position. The methoxy group attached to the chiral C atom is disordered in a 0.534 (4):0.466 (4) ratio.
The molecule exhibits a ruffled macrocycle with an average deviation of the 24 macrocycle atoms from their leastsquares-plane (Δ24) of 0.26 Å and an average Ni-N bond length of 1.931 (2) Å. In line with the unsymmetrical substituent pattern the degree of distortion is slightly larger at C5 (the methoxyphenylmethyl residue) then at C15 (the unsubstituted meso position). This is indicated by the individual displacements of the C m positions from the least-squares-plane of the four nitrogen atoms. The respective displacement values are -0.64, 0.49, -0.49, 0.47 Å for C5, C10, C15 and C20, respectively.
Similarly, the C a -C m -C a angle for C15 is widened (123.2 (2)°) compared to the other three meso positions (average = 121.3 (2)°). In terms of macrocycle distortion modes, the most significant out-of-plane contributor is B 1u (ruffled) with some degree of B 2u (saddle) mixed in. The most prominent in-plane distortion mode is A 1 g , i.e., macrocycle breathing.
The molecules form a close spaced lattice structure characterized by stacking of the porphyrin macrocycles (not shown).
The closest intramolecular contacts are Ni-H15 (3.034 Å) and Ni-H203 (2.764 Å). The former is a side-on contact and blocks one face of the porphyrin. The latter involves a meta-phenyl hydrogen atom pointing towards the nickel(II) center.

Refinement
The compound crystallized with crystallographic disorder of the methoxy group at the meso carbon (C51) with the site-occupancy factors of 0.533 (3) and 0.467 (3) for part A and B respectively. The H atoms bonded to C58 and C58a atoms were refined with standard distances of 0.97 Å, for methyl groups with U iso (H)=1.5Ueq(C) and the H atom for C51 was refined with 0.98Å with U iso (H)=1.2 U eq (C).
supplementary materials sup-2 Figures Fig. 1. : View of the molecular structure of I in the crystals. Thermal ellipsoids are drawn for 50% occupancy. Only one of the two enantiomeric forms is shown; hydrogen atoms have been omitted for clarity.