meso-[5,10,15,20-Tetra­kis(4-cyano­phen­yl)porphyrinato]zinc

Shuai Dong; Jianzhuang Jiang

doi:10.1107/S160053681100849X

. 2011 Mar 12;67(Pt 4):m431. doi: 10.1107/S160053681100849X

meso-[5,10,15,20-Tetrakis(4-cyanophenyl)porphyrinato]zinc

Shuai Dong ^a, Jianzhuang Jiang ^a,^*

PMCID: PMC3099819 PMID: 21753956

Abstract

In the title compound, [Zn(C₄₈H₂₄N₈)], the coordination environment of the Zn²⁺ ion (site symmetry Inline graphic ) is octahedral, with four indole N atoms forming the equatorial plane and the axial positions being occupied by N atoms from the cyanide groups of neighbouring molecules. In the crystal, adjacent molecules are assembled into a two-dimensional supramolecular framework parallel to ( Inline graphic 01) via the coodination bonding. Topology analysis reveals this compound to be a (4,4)-connected network.

Related literature

For background to the use of porphyrins and derivatives, see: Jiang & Ng (2009 ▶). For the use of their metal complexes as catalysts, see: Chen et al. (2004 ▶). For Zn—N bond lengths in other Zn(II) porphyrin species, see: Muniappan et al. (2006 ▶). For the synthesis of the ligand, see: Kumar et al. (1998 ▶).

Experimental

Crystal data

[Zn(C₄₈H₂₄N₈)]
M _r = 778.12
Monoclinic,
a = 9.7373 (10) Å
b = 9.4468 (10) Å
c = 21.280 (2) Å
β = 101.229 (2)°
V = 1920.0 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.69 mm⁻¹
T = 295 K
0.30 × 0.05 × 0.05 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1995 ▶) T _min = 0.726, T _max = 0.967
9272 measured reflections
3376 independent reflections
2610 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.109
S = 1.05
3376 reflections
259 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT-Plus (Bruker, 2001 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP (Sheldrick, 1998 ▶); software used to prepare material for publication: XP.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681100849X/jh2269sup1.cif

e-67-0m431-sup1.cif^{(18KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053681100849X/jh2269Isup2.hkl

e-67-0m431-Isup2.hkl^{(162.2KB, hkl)}

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

Acknowledgments

This work was supported by the Natural Science Foundation of China.

supplementary crystallographic information

Comment

Porphyrins and derivatives have been an important class of dyes and pigments with extensive applications in the paints, printing, and textile industries ever since last century (Jiang & Ng, 2009). Their metal complexes are well known catalysts for numerous chemical reactions (Chen et al., 2004). Therefore, it is worthy to prepare corresponding metal complex.

As shown in Fig.1, compound I is a mononuclear neutral complex with a two-dimensional supramolecular configuration. Each Zn(II) atom is octa-coordinated completed by four indole nitrogen atoms and two nitrogen atoms of cyanogen groups. The bond length is in line with the distances of Zn—N in other Zn(II) porphyrin species (Muniappan et al., 2006). The neighboring Zn(TCPP) molecules are connected via the coodination bonding, forming a two-dimensional supramolecular network. The Zn(II) ion is treated as a node, this compound is a (4,4)-connected network, Figure 2.

Experimental

The H₂TCPP ligand was synthesized according to the previous literature(Kumar et al., 1998). The synthesis method of the compound I was obtained by allowing the mixure of Zn(OAc)₂ (0.02 g, 0.1 mmol) and H₂TCPP (0.072 g, 0.1 mmol), and 15 mL DMF was sealed in 25 ml Teflon-lined stainless steel reactor, which was heated to 110°C. Purple block-shaped crystals suitable for X-ray diffraction analysis were separated by filtration with the yield of 35%.