Di-μ-azido-bis­(μ-1,4,7,10,13,16-hexa­oxacyclo­octa­deca­ne)bis­(5,10,15,20-tetra­phenyl­porphyrinato)dicadmium­disodium

Toumi, H.; Amiri, N.; Belkhiria, M.S.; Daran, J.-C.; Nasri, H.

doi:10.1107/S1600536812048052

Volume 68
Part 12
Pages m1557-m1558
December 2012

Received 3 November 2012
Accepted 22 November 2012
Online 30 November 2012

Key indicators
Single-crystal X-ray study
T = 180 K
Mean (C-C) = 0.003 Å
R = 0.027
wR = 0.071
Data-to-parameter ratio = 19.3
Details

Di--azido-bis(-1,4,7,10,13,16-hexaoxacyclooctadecane)bis(5,10,15,20-tetraphenylporphyrinato)dicadmiumdisodium

Hamza Toumi,^a Nesrine Amiri,^a Mohamed Salah Belkhiria,^a Jean-Claude Daran ^b and Habib Nasri ^a ^*

^aLaboratoire de Physico-chimie des Matériaux, Université de Monastir, Faculté des Sciences de Monastir, Avenue de l'environnement, 5019 Monastir, Tunisia, and ^bLaboratoire de Chimie de Coordination CNRS UPR 8241, 205 Route de Norbone, 31077 Toulouse Cedex 04, France
Correspondence e-mail: hnasri1@gmail.com

The asymmetric unit of the title compound, [Cd₂Na₂(N₃)₂(C₄₄H₂₈N₄)₂(C₁₂H₂₄O₆)₂], consists of one half of the dimeric complex; the tetranuclear molecule lies about an inversion centre. The Cd^II atom is coordinated by the four pyrrole N atoms of the 5,10,15,20-tetraphenylporphyrinate ligand and one N atom of the axial azide ligand in a square-pyramidal geometry. The azide group is also linked to the Na^I atom, which is surrounded by one 18-crown-6 molecule and additionally bonded to a second 18-crown-6 molecule trans to the azide group. The porphyrin core exhibits a major doming distortion (40%) and the crystal structure is stabilized by weak C-H [pi] interactions. The molecular structure features weak intramolecular hydrogen bonds: two O-HO interactions within the 18-crown-6 molecule and one C-H(18-crown-6)N(azido) contact.

Related literature

For the synthesis of [Cd(TPP)] (TPP = 5,10,15,20-tetraphenylporphyrinato), see: Rodesiler et al. (1985). For related structures, see: Byrn et al. (1991); Mansour et al. (2010); Liu et al. (2009). For further details of geometric distortions in related compounds, see: Jentzen et al. (1997).

Experimental

Crystal data

[Cd₂Na₂(N₃)₂(C₄₄H₂₈N₄)₂(C₁₂H₂₄O₆)₂]
M_r = 2108.90
Monoclinic, P 2₁ /n
a = 11.4175 (3) Å
b = 19.5363 (4) Å
c = 22.6086 (6) Å
= 102.683 (2)°
V = 4919.9 (2) Å³
Z = 2
Mo K radiation
= 0.51 mm^-1
T = 180 K
0.48 × 0.42 × 0.28 mm

Data collection

Oxford Diffraction Xcalibur (Sapphire1) diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrystAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.791, T_max = 0.870
44385 measured reflections
12338 independent reflections
9493 reflections with I > 2(I)
R_int = 0.030

Refinement

R[F² > 2(F²)] = 0.027
wR(F²) = 0.071
S = 1.02
12338 reflections
640 parameters
H-atom parameters constrained
_max = 0.54 e Å^-3
_min = -0.39 e Å^-3

Table 1
Hydrogen-bond geometry (Å, °)

Cg1, Cg2, Cg3 and Cg11 are the centroids of the N1/C11-C14, N2/C21-C24, N3/C31-C34 and C351-C356 rings, respectively.

D-HA	D-H	HA	DA	D-HA
C62-H62AN6	0.99	2.51	3.303 (3)	137
C63-H63BO3ⁱ	0.99	2.56	3.489 (2)	156
C65-H65BO6ⁱ	0.99	2.47	3.257 (2)	136
C62-H62BCg1	0.99	2.90	3.555 (2)	124
C63-H63ACg11ⁱⁱ	0.99	2.75	3.662 (2)	154
C71-H71ACg3ⁱⁱⁱ	0.99	2.88	3.535 (2)	124
C353-H353Cg2^iv	0.95	2.62	3.459 (2)	147
C454-H454Cg11ⁱⁱⁱ	0.95	2.82	3.697 (3)	153
Symmetry codes: (i) -x+1, -y+1, -z; (ii) x-1, y, z; (iii) $[x-{\script{3\over 2}}, -y-{\script{1\over 2}}, z-{\script{3\over 2}}]$ ; (iv) x+1, y, z.

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrystAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrystAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97.

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NG5303 ).

Acknowledgements

The authors gratefully acknowledge financial support from the Ministry of Higher Education and Scientific Research of Tunisia.

References

Burla, M. C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G. L., De Caro, L., Giacovazzo, C., Polidori, G. & Spagna, R. (2005). J. Appl. Cryst. 38, 381-388.
Burnett, M. N. & Johnson, C. K. (1996). ORTEPII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA.
Byrn, M. P., Curtis, C. J., Goldberg, I., Hsiou, Y., Khan, S. I., Sawin, P. A., Tendick, S. K. & Strouse, C. E. (1991). J. Am. Chem. Soc. 113, 6549-6557.
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.
Jentzen, W., Song, X. & Shelnutt, J. A. (1997). J. Phys. Chem. B, 101, 1684-1699.
Liu, J.-J., He, X., Shao, M. & Li, M.-X. (2009). Inorg. Chem. Commun. 12, 972-974.
Mansour, A., Belkhiria, M. S., Daran, J.-C. & Nasri, H. (2010). Acta Cryst. E66, m509-m510.
Oxford Diffraction (2009). CrystAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.
Rodesiler, P. F., Griffith, E. A. H., Charles, N. G., Lebioda, L. & Amma, E. L. (1985). Inorg. Chem. 24, 4595-4600.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.

metal-organic compounds