[5,10,15,20-Tetra­kis(4-chloro­phen­yl)porphyrinato]bis­(tributyl­phosphine)cobalt(III) perchlorate

Bijan Etemadi; Reza Kia; Mozaffar Asadi; Kh Mohammadi

doi:10.1107/S1600536809019163

. 2009 May 29;65(Pt 6):m698–m699. doi: 10.1107/S1600536809019163

[5,10,15,20-Tetrakis(4-chlorophenyl)porphyrinato]bis(tributylphosphine)cobalt(III) perchlorate

Bijan Etemadi ^a,^*, Reza Kia ^a,^‡, Mozaffar Asadi ^b, Kh Mohammadi ^c

PMCID: PMC2969721 PMID: 21583053

Abstract

In the molecule of the title compound, [Co(C₄₄H₂₄Cl₄N₄){(C₄H₉)₃P}₂]ClO₄, the Co^III centre has a slightly distorted octahedral geometry and is coordinated by four N atoms of the tetrapyrrolic ring in the equatorial positions and two phosphine ligands in the axial positions. The dihedral angles between meso-substituted chlorophenyl rings and the basic tetrapyrrolic ring are 82.66 (9), 82.16 (7), 83.97 (11) and 76.87 (8)°. In one of the phosphine ligands, the two terminal methyl groups are disordered over two positions with refined site-occupancy ratios of 0.70 (7):0.30 (7) and 0.66 (2):0.34 (2). In the crystal structure, molecules are linked together along the a axis by intermolecular C—H⋯Cl interactions. The crystal structure is further stabilized by intramolecular C—H⋯O and C—H⋯N interactions and intermolecular C—H⋯O and C—H⋯π interactions.

Related literature

For bond-length data, see Allen et al. (1987 ▶). For applications of metalloporphyrins in organic synthesis, see: Liu et al. (2007 ▶). For the synthesis, see: Mohammadi (2005 ▶).

Experimental

Crystal data

[Co(C₄₄H₂₄Cl₄N₄)(C₁₂H₂₇P)₂]ClO₄
M _r = 1313.46
Monoclinic,
a = 12.4803 (5) Å
b = 21.8192 (8) Å
c = 24.0902 (10) Å
β = 99.542 (3)°
V = 6469.2 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.57 mm⁻¹
T = 120 K
0.50 × 0.20 × 0.14 mm

Data collection

Stoe IPDS-II diffractometer
Absorption correction: numerical shape of crystal determined optically (X-RED32; Stoe & Cie, 2005 ▶)T _min = 0.869, T _max = 0.918
41515 measured reflections
17260 independent reflections
13604 reflections with I > 2σ(I)
R _int = 0.091

Refinement

R[F ² > 2σ(F ²)] = 0.069
wR(F ²) = 0.181
S = 1.08
17260 reflections
773 parameters
4 restraints
H-atom parameters constrained
Δρ_max = 0.74 e Å⁻³
Δρ_min = −0.76 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2005 ▶); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809019163/at2788sup1.cif

e-65-0m698-sup1.cif^{(51.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809019163/at2788Isup2.hkl

e-65-0m698-Isup2.hkl^{(843.5KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

Co1—N4	1.979 (2)
Co1—N2	1.985 (2)
Co1—N1	1.989 (2)
Co1—N3	1.997 (2)
Co1—P2	2.3385 (9)
Co1—P1	2.3395 (8)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C22—H22⋯O3ⁱ	0.95	2.48	3.403 (5)	165
C31—H31⋯O3	0.95	2.55	3.277 (5)	134
C32—H32⋯O1	0.95	2.49	3.407 (5)	163
C34—H34⋯Cl4ⁱⁱ	0.95	2.80	3.643 (4)	148
C50—H50B⋯N4	0.99	2.59	3.359 (4)	134
C67—H67B⋯O1	0.99	2.52	3.376 (6)	145
C66—H66B⋯Cg1	0.99	2.43	3.335 (4)	151
C53—H53A⋯Cg2	0.99	2.89	3.574 (4)	127
C58—H58A⋯Cg3	0.99	2.48	3.431 (4)	161
C50—H50B⋯Cg4	0.99	2.47	3.353 (4)	149
C61—H61B⋯Cg4	0.99	2.77	3.428 (3)	125

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Symmetry codes: (i) Inline graphic ; (ii) . Cg1, Cg2, Cg3, and Cg4 are the centroids of the N1/C2–C5, N2/C7–C10, N3/C12–C15, and N4/C17–C20 rings, respectively.

Acknowledgments

We thank Shiraz and Persian Gulf Universities for the financial support.

supplementary crystallographic information

Comment

Metalloporphyrins exist ubiquitously in nature and have found a broad spectrum of applications. Among the different applications, great efforts have been made to develop new complexes as catalysts in organic transformation reactions (Liu, et al. 2007).

The molecule of the title compound, Fig. 1, is a substituted metallo- porphyrin. In the title compound, the Co atom has a slightly distorted octahedral geometry which is coordinated by four nitrogen atoms in the equatorial position of the tetrapyrrolic ring and two other phosphine ligands in the axial positions with P1–Co1–P2, P1–Co1–N1 and N1–Co1–N3 angles of 179.18 (13), 88.48 (7), and 178.85 (10)°, respectively (Table 1). The dihedral angles between meso- substituted chlorophenyl rings and the basic tetrapyrrol ring are 82.66 (9), 82.16 (7), 83.97 (11), and 76.87 (8)°. In one of the phosphine ligands the two terminal methyl groups are disordered over two positions with a refined site-occupancies ratio of 0.70 (7)/0.3 (7) and 0.66 (2)/0.34 (2). In the crystal structure, the molecules are linked together by the intermolecular C—H···Cl interactions along the a axis (Fig. 2). The crystal structure is further stabilized by the intramolecular C—H···O and C—H···N and the intermolecular C—H···O and C—H···π interactions [Cg1, Cg2, Cg3, and Cg4 are the centroids of the N1/C2–C5, N2/C7–C10, N3/C12–C15, and N4/C17–C20 five-membered pyrrole rings] (Table 2).

Experimental

In a round-bottomed flask the porphyrinatocobalt(II) (1 mol) was dissolved in methanol (100 ml) and then PBu₃ (2 mol) was added to the solution. After heating, the reaction mixture was oxidized by blowing air into the solution for 1 h and the reaction mixture was checked for completing by UV-vis spectrophotometry. After completing, sodium perchlorate (1.2 mol) was added and by evaporating solvent, the resulting brown product was collected. Single crystals suitable for X-ray diffraction were obtained from methanol solution.