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

Mathias O Senge; Katja Dahms

doi:10.1107/S1600536811002960

. 2011 Jan 29;67(Pt 2):m265. doi: 10.1107/S1600536811002960

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

Mathias O Senge ^a,^*, Katja Dahms ^a

PMCID: PMC3051756 PMID: 21522916

Abstract

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.

Related literature

For related literature on the conformation of porphyrins, see: Senge (2000 ▶). For the chemistry of porphyrins with mixed meso substituents, see: Dahms et al. (2007 ▶); Senge et al. (2010 ▶). For Ni(II) porphyrin structures, see: Fleischer et al. (1964 ▶); Gallucci et al. (1982 ▶); Hoard (1973 ▶); Lee & Scheidt (1987 ▶), Senge (2000 ▶) and Senge et al. (2000 ▶). For handling of the crystals, see: Hope (1994 ▶).

Experimental

Crystal data

[Ni(C₄₀H₂₈N₄O)]
M _r = 639.37
Triclinic,
a = 10.869 (2) Å
b = 11.984 (2) Å
c = 12.332 (3) Å
α = 72.356 (6)°
β = 85.305 (8)°
γ = 74.219 (7)°
V = 1473.0 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.70 mm⁻¹
T = 123 K
0.20 × 0.20 × 0.20 mm

Data collection

Rigaku Saturn724 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2007 ▶) T _min = 0.873, T _max = 0.873
29300 measured reflections
7270 independent reflections
6754 reflections with I > 2σ(I)
R _int = 0.040

Refinement

R[F ² > 2σ(F ²)] = 0.053
wR(F ²) = 0.108
S = 1.10
7270 reflections
436 parameters
H-atom parameters constrained
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.52 e Å⁻³

Data collection: CrystalClear (Rigaku, 2007 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811002960/go2001sup1.cif

e-67-0m265-sup1.cif^{(31.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811002960/go2001Isup2.hkl

e-67-0m265-Isup2.hkl^{(355.7KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This work was supported by a grant from Science Foundation Ireland (SFI P·I. 09/IN.1/B2650).

supplementary crystallographic information

Comment

The title compound (I) crystallized as the racemic form in the triclinic space group P1. It was obtained from a Grignard reaction of the respective formylporphyrin to yield {5-[hydroxy(phenyl)methyl]-10,20-diphenylporphyrinato}nickel(II), (II) (Fig. 2), followed by crystallization from methylene chloride/methanol. I.e., substitution of the hydroxy group by a methoxy group occurred during the crystallization. The stucture of the title compound, (I), is shown below. Dimensions are available in the archived CIF.

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 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.

Experimental

The title compound I was obtained from II (Dahms et al., 2007) upon crystallization from CH₂Cl₂/CH₃OH. Porphyrin II in turn was prepared via Grignard reaction of (5-formyl-10,20-diphenylporphyrinato)nickel(II) with phenyl magnesium bromide.