Crystal structure of 5,10,15-triphenyl-20-(4,4,5,5-tetra­methyl-1,3,2-dioxaborolan-2-yl)porphyrin

Mathias O Senge; Hans-Georg Eckhardt

doi:10.1107/S1600536814019680

. 2014 Sep 6;70(Pt 10):o1085–o1086. doi: 10.1107/S1600536814019680

Crystal structure of 5,10,15-triphenyl-20-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)porphyrin

Mathias O Senge ^a,^*, Hans-Georg Eckhardt ^a

PMCID: PMC4257212 PMID: 25484685

Abstract

In the title compound, C₄₄H₃₇BN₄O₂, the dihedral angle between the plane of the porphyrin macrocycle ring system [r.m.s. deviation = 0.159 (1) Å] and those of three phenyl rings are 66.11 (4), 74.75 (4) and 57.00 (4)°. The conformational distortion is characterized by a mixture of ruffled, saddle and in-plane distortion modes. In the crystal, the porphyrin molecules are linked by C—H⋯π interactions into supramolecular chains running along the a-axis direction. A pair of bifurcated N—H⋯(N,N) hydrogen bonds occur across the central region of the macrocycle.

Keywords: crystal structure, porphyrinoid, tetrapyrroles, porphyrins

Related literature

For the structure and conformation of porphyrins, see: Scheidt & Lee (1987 ▶); Jentzen et al. (1997 ▶); Senge (2000 ▶, 2006 ▶). For the synthesis, see: Finnigan et al. (2011 ▶). For the handling of crystals, see Hope (1994 ▶). For related boronyl porphyrin structures, see: Hyslop et al. (1998 ▶); Schwalbe et al. (2012 ▶). For other recent free base porphyrin structures, see: Miranda et al. (2012 ▶); Leonarska et al. (2012 ▶); Senge (2013 ▶). graphic file with name e-70-o1085-scheme1.jpg

Experimental

Crystal data

C₄₄H₃₇BN₄O₂
M _r = 664.59
Monoclinic,
a = 13.0758 (5) Å
b = 10.5245 (4) Å
c = 27.1358 (10) Å
β = 110.353 (2)°
V = 3501.2 (2) Å³
Z = 4
Cu Kα radiation
μ = 0.61 mm⁻¹
T = 100 K
0.50 × 0.50 × 0.35 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.751, T _max = 0.815
25108 measured reflections
5993 independent reflections
5788 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.103
S = 1.03
5993 reflections
464 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.27 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 ▶) and DIAMOND (Brandenburg, 1998 ▶); software used to prepare material for publication: SHELXTL-Plus (Sheldrick, 2008 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536814019680/lx2293sup1.cif

e-70-o1085-sup1.cif^{(779.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814019680/lx2293Isup2.hkl

e-70-o1085-Isup2.hkl^{(293.4KB, hkl)}

Click here for additional data file.^{(420.8KB, tif)}

. DOI: 10.1107/S1600536814019680/lx2293fig1.tif

Molecular structure of the title compound. Thermal ellipsoids are drawn at 50% probability level.

Click here for additional data file.^{(1.5MB, tif)}

x y z x y z . DOI: 10.1107/S1600536814019680/lx2293fig2.tif

A view of the N—H⋯N and C—H⋯π interactions (dotted lines) in the crystal structure of the title compound. H atoms non-participating in hydrogen-bonding were omitted for clarity. [Symmetry code: (i) x − 1, y, z; (ii) x + 1, y, z.]

CCDC reference: 1022040

Additional supporting information: crystallographic information; 3D view; checkCIF report

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

Cg1 is the centroid of the C100–C105 phenyl ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N21—H21⋯N24	0.88	2.35	2.9084 (16)	122
N21—H21⋯N22	0.88	2.38	2.9266 (16)	121
N23—H23⋯N24	0.88	2.34	2.8978 (16)	121
N23—H23⋯N22	0.88	2.35	2.8986 (16)	120
C153—H153⋯Cg1ⁱ	0.95	2.58	3.488 (2)	160

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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

S1. Comment

The compound was prepared via borylation of 5-bromo-10,15,20-triphenylporphyrin with 4,4,5,5-tetramethyl-1,3,2-dioxaborolane under dichlorobis(triphenylphosphine)palladium(II) catalysis (Finnigan et al., 2011). Crystallization from CH₂Cl₂/CH₃OH yielded monoclinic crystals without solvent inclusion.

The compound was investigated with regard to its macrocycle conformation. The porphyrin macrocycle ring system, with a mean deviation of 0.159 (1) Å from the least-squares plane defined by the 24 constituent atoms. Three phenyl rings are essentially planar, with a mean deviation of 0.001 (1) (C100–C105), 0.003 (1) (C150–C155) and 0.007 (1) (C200–C205) Å from the least-squares plane defined by the six constituent atoms. The dihedral angle formed by the porphyrin macrocycle ring system and three phenyl rings are 66.11 (4)(C100–C105), 74.75 (4) (C150–C155) and 57.00 (4) (C200–C205) °, respectively. A conformational analysis was performed using the NSD (normal structural decomposition) method developed by Shelnutt and coworkers (Jentzen et al., 1997). The compound exhibits a moderate degree of conformational distortion. The main contributing out-of-plane distortion modes are ruf, sad and wav. Likewise moderate contributions from macrocycle breathing and N-str are observed for the in-plane distortions. Related Zn(II) complexes, e.g. {5,15-diphenyl-10-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)porphyrinato}zinc(II) (Hyslop et al., 1998; Schwalbe et al., 2012) exhibit more planar conformations. Other recent porphyrin free base structures have been reported by Miranda et al. (2012), Leonarska et al. (2012), and Senge (2013).

In the crystal packing (Fig. 2), the porphyrin molecules are linked by C—H···π interactions (Table 1, Cg1 is the centroid of the C100–C105 phenyl ring) into supramolecular chains running along the a axis. Also intramolecular N—H···N hydrogen bonds occur (Table 1).

S2. Experimental

The title compound was prepared as described by Finnigan et al. (2011).