Redetermination of cyclo-tetra­kis­(μ-5,10,15,20-tetra-4-pyridyl­porphyrinato)tetra­zinc(II) dimethyl­formamide octa­solvate trihydrate at 100 K

Seidel, R.W.; Graf, J.; Goddard, R.; Oppel, I.M.

doi:10.1107/S1600536811002054

Volume 67
Part 2
Pages m236-m237
February 2011

Received 2 December 2010
Accepted 13 January 2011
Online 22 January 2011

Key indicators
Single-crystal X-ray study
T = 100 K
Mean (C-C) = 0.003 Å
Some non-H atoms missing,
R = 0.042
wR = 0.108
Data-to-parameter ratio = 17.5
Details

Redetermination of cyclo-tetrakis(-5,10,15,20-tetra-4-pyridylporphyrinato)tetrazinc(II) dimethylformamide octasolvate trihydrate at 100 K

Rüdiger W. Seidel,^a ^* Jürgen Graf,^b Richard Goddard ^c and Iris M. Oppel ^d

^aLehrstuhl für Analytische Chemie, Ruhr-Universität Bochum, Universitätsstrasse 150, 44780 Bochum, Germany,^bIncoatec GmbH, Max-Planck-Strasse 2, 21502 Geesthacht, Germany,^cMax-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr, Germany, and ^dInstitut für Anorganische Chemie, Rheinisch-Westfälische Technische Hochschule Aachen, Landoltweg 1, 52074 Aachen, Germany
Correspondence e-mail: Ruediger.Seidel@rub.de

The structure of the title compound, [Zn₄(C₄₀H₂₄N₈)₄]·8C₃H₇NO·3H₂O, has been redetermined at 100 K. The redetermination is of significantly higher precision and gives further insight into the disorder of pyridyl groups and solvent molecules. The molecules of (5,10,15,20-tetra-4-pyridylporphyrinato)zinc(II) (ZnTPyP) form homomolecular cyclic tetramers by coordination of a peripheral pyridyl group to the central Zn atom of an adjacent symmetry-related molecule. The tetramer so formed exhibits molecular S₄ symmetry and is located about a crystallographic fourfold rotoinversion axis. Severely disordered dimethylformamide and water molecules are present in the crystal, the contributions of which were omitted from refinement. Intermolecular C-HN hydrogen bonding is observed.

Related literature

For the structure at 200 K, see: Seidel et al. (2010). For the 2-chlorophenol solvate of cyclic tetrameric ZnTPyP, see: Lipstman & Goldberg (2010). For a review article on structural motifs in coordination polymers of the 5,10,15,20-tetra4-pyridylporphyrin ligand, see: DeVries & Choe (2009). For the supramolecular chemistry of ZnTPyP in the solid-state, see: Lipstman & Goldberg (2010); Seidel et al. (2010) and references cited therein. For a description of the I [mu] S microfocus X-ray source used in the present study, see: Graf (2008); Schulz et al. (2009). For PLATON / SQUEEZE, see: van der Sluis & Spek (1990); Spek (2009). For a description of the program COOT, see: Emsley et al. (2010).

Experimental

Crystal data

[Zn₄(C₄₀H₂₄N₈)₄]·8C₃H₇NO·3H₂O
M_r = 3366.98
Tetragonal, P 4₂ /n
a = 23.6897 (5) Å
c = 14.9876 (7) Å
V = 8411.1 (5) Å³
Z = 2
Cu K radiation
= 1.24 mm^-1
T = 100 K
0.16 × 0.04 × 0.02 mm

Data collection

Bruker X8 PROSPECTOR diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008) T_min = 0.827, T_max = 0.976
44415 measured reflections
7723 independent reflections
6768 reflections with I > 2(I)
R_int = 0.018

Refinement

R[F² > 2(F²)] = 0.042
wR(F²) = 0.108
S = 1.04
7723 reflections
442 parameters
H-atom parameters constrained
_max = 0.59 e Å^-3
_min = -0.42 e Å^-3

Table 1
Selected geometric parameters (Å, °)

Zn1-N24	2.0684 (15)
Zn1-N21	2.0695 (16)
Zn1-N22	2.0695 (17)
Zn1-N23	2.0747 (16)
Zn1-N101ⁱ	2.1385 (16)

N24-Zn1-N21	162.77 (7)
N24-Zn1-N22	88.42 (6)
N21-Zn1-N22	88.84 (7)
N24-Zn1-N23	89.34 (6)
N21-Zn1-N23	87.94 (6)
N22-Zn1-N23	161.70 (7)
N24-Zn1-N101ⁱ	95.10 (6)
N21-Zn1-N101ⁱ	102.11 (6)
N22-Zn1-N101ⁱ	102.00 (6)
N23-Zn1-N101ⁱ	96.29 (6)
Symmetry code: (i) $[y, -x+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D-HA	D-H	HA	DA	D-HA
C7-H7N151ⁱⁱ	0.95	2.65	3.583 (4)	167
C17-H17N51ⁱⁱⁱ	0.95	2.66	3.583 (3)	165
Symmetry codes: (ii) x, y, z+1; (iii) x, y, z-1.

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2010); software used to prepare material for publication: enCIFer (Allen et al., 2004).

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BV2170 ).

Acknowledgements

The Deutsche Forschungsgemeinschaft (DFG) is acknowledged for financial support. RWS is grateful to Professor William S. Sheldrick and Professor Christian W. Lehmann for generous support.

References

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metal-organic compounds