5,15-Bis(4-pentyl­oxyphen­yl)porphyrin

Mathias O Senge

doi:10.1107/S160053681301550X

. 2013 Jun 8;69(Pt 7):o1048. doi: 10.1107/S160053681301550X

5,15-Bis(4-pentyloxyphenyl)porphyrin

Mathias O Senge ^a,^*

PMCID: PMC3772480 PMID: 24046623

Abstract

In the title compound, C₄₂H₄₂N₄O₂, the complete molecule is generated by a crystallographic inversion centre. The porphyrin system exhibits a near planar macrocycle conformation with an average deviation from the least-squares plane of the 24 macrocycle atoms of 0.037 (5) Å. The phenyl ipso C atoms are positioned above and below the porphyrin plane by 0.35 (1) Å and the macrocycle shows evidence of in-plane rectangular elongation with N⋯N separations of 3.032 (5) and 2.803 (5) Å. Two intramolecular N—H⋯N hydrogen bonds occur.

Related literature

For the conformation of porphyrins, see: Scheidt & Lee (1987 ▶); Senge et al. (1997 ▶); Senge (2006 ▶). For the synthesis of such compounds, see: Wiehe et al. (2005 ▶). graphic file with name e-69-o1048-scheme1.jpg

Experimental

Crystal data

C₄₂H₄₂N₄O₂
M _r = 634.80
Triclinic,
a = 9.5222 (6) Å
b = 9.5799 (6) Å
c = 10.2195 (6) Å
α = 67.777 (1)°
β = 88.063 (1)°
γ = 72.464 (1)°
V = 819.49 (9) Å³
Z = 1
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 90 K
0.30 × 0.10 × 0.08 mm

Data collection

Bruker SMART APEXII diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.97, T _max = 0.99
9093 measured reflections
3606 independent reflections
2489 reflections with I > 2σ(I)
R _int = 0.039

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.109
S = 1.04
3606 reflections
219 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: XP in SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) I, 2R. DOI: 10.1107/S160053681301550X/zl2552sup1.cif

e-69-o1048-sup1.cif^{(26.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681301550X/zl2552Isup2.hkl

e-69-o1048-Isup2.hkl^{(176.8KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N21—H21⋯N24	0.88	2.50	3.033 (2)	119
N21—H21⋯N24ⁱ	0.88	2.22	2.804 (2)	123

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Symmetry code: (i) Inline graphic .

Acknowledgments

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

supplementary crystallographic information

Comment

Many porphyrin structures with four meso substituents have been reported (Scheidt & Lee, 1987). The available number of structures for systems with only two meso residues is much smaller. In the context of an ongoing program on the conformational flexibilty of porphyrins (Senge, 2006) we are interested in a comparative analysis of 5,10-A₂– and 5,15-A₂-disubstituted porphyrins. The title compound is an example for the latter and exhibits a planar macrocycle with an average deviation from the least-squares-plane of the 24 macrocycle atoms of Δ24 = 0.037 (5) Å. The phenyl ipso carbon atoms are positioned above and below the porphyrin plane by 0.35 Å and the macrocycle shows evidence for in-plane distortion with N···N separations of 3.032 (5) and 2.803 (5) Å. This is similar to the situation found in 2,3,5,7,8,12,13,15, 17,18- decasubstituted porphyrins (Senge et al., 1997) where peri interaction between the meso and beta substituents occur. The molecules pack in parallel layers with the alkyl chains separating the macrocycles and only minimal π-aggregation.

Experimental

The compound was prepared as described by Wiehe et al. (2005) and crystallized from CH₂Cl₂/CH₃OH.