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

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 2| February 2011| Pages m236-m237

doi:10.1107/S1600536811002054

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Redetermination of cyclo-tetrakis(μ-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

(Received 2 December 2010; accepted 13 January 2011; online 22 January 2011)

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—H⋯N 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 IμS 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 Kα radiation
μ = 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 > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.108
S = 1.04
7723 reflections
442 parameters
H-atom parameters constrained
Δρ_max = 0.59 e Å⁻³
Δρ_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—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯N151ⁱⁱ	0.95	2.65	3.583 (4)	167
C17—H17⋯N51ⁱⁱⁱ	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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811002054/bv2170sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811002054/bv2170Isup2.hkl

checkCIF report

Comment top

5,10,15,20-Tetra(4-pyridyl)porphyrin has been widely used as ligand for the construction of coordination polymers (DeVries & Choe, 2009). We and others have reported on the solid-state supramolecular chemistry of the self-complementary [5,10,15,20-tetra(4-pyridyl)porphyrinato]zinc(II) (ZnTPyP) building block (Lipstman & Goldberg, 2010; Seidel et al., 2010 and references cited therein). Recently, we reported the title structure of [ZnTPyP]₄.

The small dark red plate-shaped crystals of the title compound were subjected to diffraction experiments using a Bruker AXS X8 PROSPECTOR diffractometer equipped with an INCOATEC microfocus X-ray source (IµS) for Cu radiation (Graf, 2008). Such microfocus X-ray sources use multilayer mirrors to focus the X-ray beam onto the crystal and, therefore, lead to a significant reduction of the background and an increase in diffracted intensities. It has already been demonstrated that the Mo IµS gives data of significantly higher quality than a 2 kW Mo fine focus sealed tube, when small crystals are examined (Schulz et al., 2009). The data collection presented here, using the Cu IµS, resulted in intensity data of surprisingly good quality and, hence, indicated a re-refinement of the crystal structure. The crystals investigated in the original work were significantly larger than those examined in the present study and split on cooling to 100 K. For this reason, the data were collected at 200 K with a Cu rotating anode system at that time. Using small crystals has the advantage that these are less likely to split on flash cooling.

The molecular structure of [ZnTPyP]₄ is depicted in Fig. 1. The asymmetric unit contains one ZnTPyP unit (Fig 2.) and the S₄ symmetric tetramer is generated by crystallographic fourfold rotoinversion symmetry. One peripheral pyridyl group binds to the central Zn atom of an adjacent symmetry related ZnTPyP unit. Zn1 is pentacoordinated and is displaced from the N₄ mean plane by 0.3196 (9) Å. The coordination geometry parameters about Zn1 are given in Table 1. The three remaining pyridyl groups are non-coordinating. Even at 100 K, the pyridyl groups attached to C5 and C15 show elongated ellipsoids, which cause a checkCIF B level alert (Spek, 2009) due to large U_eq(max)/U_eq(min) ratio. This reveals that the disorder is rather of static than dynamic nature. Attempts were made to describe the electron density of the pyridyl ring attached to C15 (Fig. 3) by a split model. However, the refinement results could not be improved thereby. Thus, both pyridyl rings were finally described with large displacement parameters.

In the crystal, the [ZnTPyP]₄ entities are stacked into columns located at x = 1/4, y = 1/4 and x = 3/4, y = 3/4 (Fig 4). The stacking propagates via C_β—H···N_py interactions (see Table 2) by translational symmetry in the c axis direction. Within a column, the distance between the centroids of the pyridyl rings attached to C5 and C15ⁱⁱⁱ is 4.0714 (1) Å. Adjacent columns of [ZnTPyP]₄ are arranged with an offset of c/2 (ca 7.49 Å). Interstitial channels are formed parallel to the c axis direction centred at x = 1/4, y = 3/4 and x = 3/4, y = 1/4 (Fig 5). The potential solvent accessible void estimated with PLATON / SOLV (Spek, 2009) is 33.2% of the unit cell volume. On cooling to 100 K, the a lattice vector is shortened by approximately 0.27 Å in comparison to the tetragonal unit cell at 200 K (a = 23.958 (2) Å), whereas the length of c lattice vector remains relatively unaffected (c = 15.0646 (16) Å at 200 K; Seidel et al., 2010).

Despite intensive efforts, the disordered solvent molecules filling the voids within the columns of [ZnTPyP]₄ and the interstitial channels could not be modeled reasonably with the data collected at 100 K. Nevertheless, residual electron density was visible in a difference Fourier synthesis calculated for the solvent regions (Fig. 6) with phases based on the model using COOT (Emsley et al., 2010). For the visualization of the surface of the (difference) electron density using a three-dimensional mesh, the electron densities should be read into COOT in terms of structure factors. To obtain a structure factor (.fcf) file containg the informations necessary for the calculation of electron density maps and suitable for COOT, the LIST 6 instruction of SHELXL-97 was used. The atomic model of the framework was read into COOT by means of the SHELXL-97. res file. The visual inspection of the difference electron density map indicates that four molecules of dimethylformamide (DMF) plus one water molecule are located within the voids in the columns approximately centred at (1/4,1/4,0), whereas another four molecules of DMF and two water molecules are clustered around the 4₂ screw axes running through the interstitial channels parallel to the c axis direction. The compound can, therefore, probably best be described as [ZnTPyP]₄. 8 DMF. 3 H₂O. The compound was originally formulated as being a pure DMF solvate (Seidel et al., 2010). To improve the fit of the model to the data and, hence, the precision of the main part of the structure, the contributions of the disordered solvent molecules were removed from the diffraction data with PLATON / SQUEEZE (van der Sluis & Spek, 1990; Spek, 2009). SQUEEZE estimated the electron counts in the voids within the columns and interstitial channels of [ZnTPyP]₄ to be 182 and 207, respectively. These values are relatively close to those based on the proposed chemical formula (178 and 196).

Related literature top

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-tetra(4-pyridyl)porphyrin 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 IµS 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 top

Small dark red plate-shaped crystals of the title compound were obtained similarly as reported previously (Seidel et al., 2010); 12 mg of ZnTPyP (Aldrich) and 11 mg of [Pd(NO₃)₂(en)] (en = 1,2-diaminoethane) were placed in an ampoule and 4 ml of DMF were added. The ampoule was sealed and placed in a heater. The sample was heated to 150 °C in 24 h and held for five days at this temperature. Subsequently, the sample was cooled down to room temperature in 100 h. Noteworthy, the crystals of the title compound were accompanied by crystals of the triclinic phase, containing a polymeric one-dimensional ladder structure of ZnTPyP, as observed previously (Seidel et al., 2010).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); 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).

Figures top

	Fig. 1. Molecular structure of the title compound. H atoms are omitted for clarity.
	Fig. 2. Displacement ellipsoid plot of one repeat unit of cyclic [ZnTPyP]₄ drawn at 50% probability. H atoms are omitted for clarity. Symmetry code: (i) y, -x + 1/2, -z + 1/2.
	Fig. 3. Contour plot of the F_o electron density map in the plane of the pyridyl group attached to C15, calculated with phases from F_c. Contours are drawn at 0.50 e Å^-3 starting at 6.00 e Å^-3. The contour plot was generated with PLATON (Spek, 2009).
	Fig. 4. Stacking of the [ZnTPyP]₄ entities viewed along the a axis direction. H atoms are omitted for clarity. C_β—H···N_py interactions are represented by dashed lines.
	Fig. 5. Packing diagram of the title compound projected along the c axis direction. H atoms are omitted for clarity.
	Fig. 6. The tetragonal unit cell of the title compound viewed approximately along the c axis direction showing the F_o-F_c map of the disordered solvent regions (contoured at 3.0σ level). The figure was created with COOT (Emsley et al., 2010) using F_o including the contributions of the disordered solvent with phases from F_c based on the model.

cyclo-tetrakis(µ-5,10,15,20-tetra-4-pyridylporphyrinato)tetrazinc(II) dimethylformamide octasolvate top

Crystal data top

[Zn₄(C₄₀H₂₄N₈)₄]·8C₃H₇NO·3H₂O	D_x = 1.329 Mg m⁻³
M_r = 3366.98	Cu Kα radiation, λ = 1.54178 Å
Tetragonal, P4₂/n	Cell parameters from 130 reflections
Hall symbol: -P 4bc	θ = 3.5–31.5°
a = 23.6897 (5) Å	µ = 1.24 mm⁻¹
c = 14.9876 (7) Å	T = 100 K
V = 8411.1 (5) Å³	Plate, dark red
Z = 2	0.16 × 0.04 × 0.02 mm
F(000) = 3500

Data collection top

Bruker X8 PROSPECTOR goniometer diffractometer	7723 independent reflections
Radiation source: Incoatec IµS microfocus X-ray source	6768 reflections with I > 2σ(I)
Incoatec Quazar Multilayer Mirror monochromator	R_int = 0.018
Detector resolution: 8.33 pixels mm^-1	θ_max = 69.2°, θ_min = 2.6°
ω scans	h = −28→25
Absorption correction: multi-scan (SADABS; Bruker, 2008)	k = −24→28
T_min = 0.827, T_max = 0.976	l = −17→14
44415 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.108	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0472P)² + 5.0454P] where P = (F_o² + 2F_c²)/3
7723 reflections	(Δ/σ)_max < 0.001
442 parameters	Δρ_max = 0.59 e Å⁻³
0 restraints	Δρ_min = −0.42 e Å⁻³

Crystal data top

[Zn₄(C₄₀H₂₄N₈)₄]·8C₃H₇NO·3H₂O	Z = 2
M_r = 3366.98	Cu Kα radiation
Tetragonal, P4₂/n	µ = 1.24 mm⁻¹
a = 23.6897 (5) Å	T = 100 K
c = 14.9876 (7) Å	0.16 × 0.04 × 0.02 mm
V = 8411.1 (5) Å³

Data collection top

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

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.108	H-atom parameters constrained
S = 1.04	Δρ_max = 0.59 e Å⁻³
7723 reflections	Δρ_min = −0.42 e Å⁻³
442 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Zn1	0.350673 (11)	0.520064 (11)	0.185590 (16)	0.03823 (9)
N21	0.38601 (8)	0.54998 (7)	0.06850 (10)	0.0433 (4)
N22	0.27781 (7)	0.50134 (7)	0.11541 (10)	0.0404 (4)
N23	0.41242 (7)	0.56428 (7)	0.25451 (10)	0.0404 (4)
N24	0.30440 (7)	0.51392 (7)	0.30222 (10)	0.0377 (4)
C1	0.46288 (9)	0.58336 (8)	0.22081 (13)	0.0420 (4)
C2	0.50033 (10)	0.59793 (10)	0.29314 (14)	0.0532 (6)
H2	0.5379	0.6115	0.2880	0.064*
C3	0.47175 (10)	0.58861 (10)	0.36945 (15)	0.0534 (6)
H3	0.4853	0.5949	0.4283	0.064*
C4	0.41675 (9)	0.56739 (9)	0.34544 (13)	0.0428 (5)
C5	0.37497 (9)	0.55138 (9)	0.40720 (13)	0.0442 (5)
C6	0.32280 (9)	0.52641 (9)	0.38657 (12)	0.0411 (4)
C7	0.28126 (9)	0.50864 (9)	0.45108 (13)	0.0451 (5)
H7	0.2835	0.5130	0.5140	0.054*
C8	0.23852 (9)	0.48459 (9)	0.40491 (13)	0.0422 (4)
H8	0.2052	0.4684	0.4292	0.051*
C9	0.25323 (8)	0.48825 (8)	0.31165 (12)	0.0362 (4)
C10	0.21846 (8)	0.46994 (8)	0.24113 (12)	0.0360 (4)
C11	0.22974 (8)	0.47834 (8)	0.14991 (12)	0.0376 (4)
C12	0.19052 (9)	0.46543 (9)	0.07858 (13)	0.0460 (5)
H12	0.1543	0.4486	0.0845	0.055*
C13	0.21544 (10)	0.48202 (10)	0.00230 (14)	0.0526 (6)
H13	0.1998	0.4794	−0.0559	0.063*
C14	0.26979 (9)	0.50435 (10)	0.02480 (13)	0.0477 (5)
C15	0.30923 (11)	0.52569 (10)	−0.03612 (14)	0.0545 (6)
C16	0.36281 (10)	0.54737 (10)	−0.01508 (13)	0.0515 (5)
C17	0.40164 (12)	0.57099 (11)	−0.07905 (15)	0.0636 (7)
H17	0.3959	0.5743	−0.1416	0.076*
C18	0.44735 (11)	0.58736 (10)	−0.03328 (15)	0.0581 (6)
H18	0.4801	0.6046	−0.0575	0.070*
C19	0.43790 (9)	0.57411 (9)	0.05937 (13)	0.0455 (5)
C20	0.47569 (9)	0.58754 (8)	0.12914 (13)	0.0429 (5)
N51	0.40921 (10)	0.58630 (15)	0.68340 (15)	0.0812 (8)
C52	0.38597 (16)	0.62318 (17)	0.6300 (2)	0.0945 (11)
H52	0.3762	0.6589	0.6542	0.113*
C53	0.37466 (15)	0.61389 (13)	0.54115 (18)	0.0816 (9)
H53	0.3581	0.6429	0.5060	0.098*
C54	0.38735 (9)	0.56279 (11)	0.50349 (14)	0.0513 (5)
C55	0.41194 (13)	0.52451 (15)	0.55825 (18)	0.0792 (8)
H55	0.4222	0.4884	0.5360	0.095*
C56	0.42214 (14)	0.53814 (18)	0.6469 (2)	0.0885 (10)
H56	0.4397	0.5105	0.6834	0.106*
N101	0.06117 (6)	0.38923 (7)	0.30189 (10)	0.0355 (3)
C102	0.06574 (8)	0.44515 (8)	0.29549 (13)	0.0403 (4)
H102	0.0327	0.4673	0.3038	0.048*
C103	0.11567 (8)	0.47254 (8)	0.27747 (13)	0.0406 (4)
H103	0.1167	0.5126	0.2740	0.049*
C104	0.16441 (8)	0.44146 (8)	0.26451 (11)	0.0339 (4)
C105	0.16034 (9)	0.38345 (9)	0.27246 (17)	0.0506 (5)
H105	0.1928	0.3604	0.2652	0.061*
C106	0.10845 (9)	0.35925 (9)	0.29112 (16)	0.0490 (5)
H106	0.1064	0.3194	0.2965	0.059*
N151	0.2660 (2)	0.5329 (2)	−0.3142 (2)	0.1294 (17)
C152	0.2458 (3)	0.5685 (2)	−0.2569 (3)	0.155 (2)
H152	0.2211	0.5972	−0.2780	0.185*
C153	0.2581 (2)	0.56707 (18)	−0.1666 (2)	0.1290 (18)
H153	0.2421	0.5945	−0.1278	0.155*
C154	0.29319 (12)	0.52625 (14)	−0.13291 (16)	0.0729 (8)
C155	0.31337 (15)	0.4886 (2)	−0.19209 (18)	0.1009 (13)
H155	0.3375	0.4591	−0.1726	0.121*
C156	0.29872 (18)	0.4931 (2)	−0.2832 (2)	0.1174 (17)
H156	0.3133	0.4659	−0.3237	0.141*
N201	0.63736 (10)	0.65387 (10)	0.05085 (15)	0.0695 (6)
C202	0.60235 (13)	0.68222 (12)	0.1038 (2)	0.0742 (8)
H202	0.6140	0.7184	0.1241	0.089*
C203	0.55016 (12)	0.66270 (10)	0.13114 (18)	0.0635 (7)
H203	0.5271	0.6852	0.1689	0.076*
C204	0.53176 (10)	0.61002 (9)	0.10312 (14)	0.0474 (5)
C205	0.56798 (10)	0.58046 (10)	0.04725 (15)	0.0548 (6)
H205	0.5577	0.5442	0.0255	0.066*
C206	0.61911 (11)	0.60416 (12)	0.02354 (17)	0.0645 (7)
H206	0.6429	0.5831	−0.0153	0.077*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.04778 (16)	0.04374 (16)	0.02318 (14)	−0.00756 (11)	0.00168 (10)	−0.00080 (10)
N21	0.0579 (10)	0.0455 (9)	0.0266 (8)	−0.0116 (8)	0.0027 (7)	0.0007 (7)
N22	0.0485 (9)	0.0476 (9)	0.0251 (8)	−0.0020 (7)	−0.0005 (7)	0.0025 (7)
N23	0.0531 (10)	0.0414 (9)	0.0266 (8)	−0.0084 (7)	0.0028 (7)	−0.0033 (6)
N24	0.0438 (9)	0.0446 (9)	0.0247 (8)	−0.0010 (7)	0.0004 (6)	−0.0035 (6)
C1	0.0521 (12)	0.0395 (10)	0.0342 (10)	−0.0129 (9)	0.0034 (8)	−0.0050 (8)
C2	0.0581 (14)	0.0608 (14)	0.0408 (12)	−0.0204 (11)	0.0039 (10)	−0.0108 (10)
C3	0.0599 (14)	0.0649 (14)	0.0354 (11)	−0.0209 (11)	−0.0001 (10)	−0.0111 (10)
C4	0.0522 (12)	0.0473 (11)	0.0290 (10)	−0.0094 (9)	0.0010 (8)	−0.0072 (8)
C5	0.0520 (12)	0.0531 (12)	0.0275 (10)	−0.0066 (9)	−0.0019 (8)	−0.0055 (8)
C6	0.0479 (11)	0.0494 (11)	0.0259 (10)	0.0000 (9)	0.0024 (8)	−0.0038 (8)
C7	0.0494 (12)	0.0603 (13)	0.0256 (10)	−0.0036 (10)	0.0010 (8)	−0.0026 (9)
C8	0.0458 (11)	0.0528 (12)	0.0279 (10)	0.0012 (9)	0.0035 (8)	−0.0002 (8)
C9	0.0410 (10)	0.0403 (10)	0.0274 (9)	0.0045 (8)	0.0019 (7)	−0.0024 (7)
C10	0.0421 (10)	0.0373 (10)	0.0286 (9)	0.0047 (8)	0.0014 (7)	−0.0020 (7)
C11	0.0428 (10)	0.0414 (10)	0.0287 (10)	0.0024 (8)	−0.0018 (8)	−0.0010 (8)
C12	0.0457 (11)	0.0623 (13)	0.0300 (10)	−0.0037 (10)	−0.0036 (8)	−0.0017 (9)
C13	0.0565 (13)	0.0725 (15)	0.0289 (11)	−0.0093 (11)	−0.0068 (9)	0.0036 (10)
C14	0.0566 (13)	0.0600 (13)	0.0264 (10)	−0.0071 (10)	−0.0044 (9)	0.0036 (9)
C15	0.0687 (15)	0.0670 (15)	0.0279 (11)	−0.0171 (12)	−0.0035 (10)	0.0076 (9)
C16	0.0697 (15)	0.0574 (13)	0.0273 (10)	−0.0158 (11)	0.0024 (9)	0.0052 (9)
C17	0.0816 (18)	0.0817 (17)	0.0276 (11)	−0.0288 (14)	0.0023 (11)	0.0087 (11)
C18	0.0723 (16)	0.0672 (15)	0.0347 (12)	−0.0260 (12)	0.0053 (10)	0.0071 (10)
C19	0.0595 (13)	0.0455 (11)	0.0314 (10)	−0.0118 (9)	0.0050 (9)	0.0012 (8)
C20	0.0570 (12)	0.0366 (10)	0.0351 (10)	−0.0118 (9)	0.0066 (9)	−0.0009 (8)
N51	0.0633 (14)	0.145 (3)	0.0359 (12)	−0.0305 (15)	−0.0006 (10)	−0.0144 (14)
C52	0.126 (3)	0.113 (3)	0.0447 (17)	−0.011 (2)	−0.0056 (17)	−0.0286 (17)
C53	0.126 (3)	0.0787 (19)	0.0403 (14)	−0.0017 (18)	−0.0102 (15)	−0.0181 (13)
C54	0.0499 (12)	0.0755 (16)	0.0286 (11)	−0.0147 (11)	0.0009 (9)	−0.0067 (10)
C55	0.096 (2)	0.100 (2)	0.0419 (15)	0.0139 (17)	−0.0143 (14)	−0.0037 (14)
C56	0.082 (2)	0.135 (3)	0.0486 (17)	0.002 (2)	−0.0152 (14)	0.0081 (18)
N101	0.0379 (8)	0.0442 (9)	0.0244 (8)	0.0040 (7)	−0.0013 (6)	−0.0035 (6)
C102	0.0418 (11)	0.0434 (11)	0.0358 (10)	0.0092 (8)	0.0059 (8)	−0.0024 (8)
C103	0.0466 (11)	0.0392 (10)	0.0360 (10)	0.0058 (8)	0.0063 (8)	0.0009 (8)
C104	0.0386 (10)	0.0412 (10)	0.0218 (8)	0.0052 (8)	−0.0005 (7)	−0.0033 (7)
C105	0.0376 (11)	0.0436 (12)	0.0707 (15)	0.0078 (9)	0.0018 (10)	−0.0042 (10)
C106	0.0422 (11)	0.0384 (11)	0.0665 (15)	0.0038 (9)	−0.0002 (10)	−0.0022 (10)
N151	0.157 (4)	0.182 (4)	0.0499 (18)	−0.092 (3)	−0.022 (2)	0.029 (2)
C152	0.267 (7)	0.130 (4)	0.067 (3)	−0.043 (4)	−0.074 (3)	0.028 (3)
C153	0.218 (5)	0.105 (3)	0.064 (2)	−0.016 (3)	−0.068 (3)	0.026 (2)
C154	0.0797 (18)	0.108 (2)	0.0312 (13)	−0.0441 (16)	−0.0058 (12)	0.0136 (13)
C155	0.088 (2)	0.180 (4)	0.0349 (15)	−0.029 (2)	0.0018 (13)	−0.0193 (18)
C156	0.098 (3)	0.210 (5)	0.0446 (19)	−0.059 (3)	0.0097 (17)	−0.011 (2)
N201	0.0714 (14)	0.0754 (15)	0.0616 (13)	−0.0299 (12)	0.0153 (11)	−0.0022 (11)
C202	0.0847 (19)	0.0592 (15)	0.0786 (19)	−0.0325 (14)	0.0173 (16)	−0.0085 (14)
C203	0.0751 (17)	0.0495 (13)	0.0658 (16)	−0.0190 (12)	0.0165 (13)	−0.0104 (11)
C204	0.0627 (13)	0.0454 (11)	0.0340 (11)	−0.0135 (10)	0.0057 (9)	0.0004 (8)
C205	0.0693 (15)	0.0540 (13)	0.0410 (12)	−0.0153 (11)	0.0148 (10)	−0.0076 (10)
C206	0.0700 (16)	0.0752 (17)	0.0482 (14)	−0.0173 (13)	0.0177 (12)	−0.0064 (12)

Geometric parameters (Å, º) top

Zn1—N24	2.0684 (15)	C19—C20	1.413 (3)
Zn1—N21	2.0695 (16)	C20—C204	1.483 (3)
Zn1—N22	2.0695 (17)	N51—C56	1.302 (5)
Zn1—N23	2.0747 (16)	N51—C52	1.306 (5)
Zn1—N101ⁱ	2.1385 (16)	C52—C53	1.376 (4)
N21—C19	1.363 (3)	C52—H52	0.9500
N21—C16	1.369 (3)	C53—C54	1.369 (4)
N22—C11	1.364 (3)	C53—H53	0.9500
N22—C14	1.373 (2)	C54—C55	1.355 (4)
N23—C4	1.369 (3)	C55—C56	1.389 (4)
N23—C1	1.374 (3)	C55—H55	0.9500
N24—C9	1.363 (3)	C56—H56	0.9500
N24—C6	1.370 (2)	N101—C102	1.333 (3)
C1—C20	1.411 (3)	N101—C106	1.336 (3)
C1—C2	1.443 (3)	N101—Zn1ⁱⁱ	2.1385 (16)
C2—C3	1.347 (3)	C102—C103	1.376 (3)
C2—H2	0.9500	C102—H102	0.9500
C3—C4	1.442 (3)	C103—C104	1.383 (3)
C3—H3	0.9500	C103—H103	0.9500
C4—C5	1.407 (3)	C104—C105	1.383 (3)
C5—C6	1.404 (3)	C105—C106	1.385 (3)
C5—C54	1.497 (3)	C105—H105	0.9500
C6—C7	1.442 (3)	C106—H106	0.9500
C7—C8	1.352 (3)	N151—C152	1.294 (7)
C7—H7	0.9500	N151—C156	1.307 (6)
C8—C9	1.443 (3)	C152—C153	1.385 (5)
C8—H8	0.9500	C152—H152	0.9500
C9—C10	1.408 (3)	C153—C154	1.372 (5)
C10—C11	1.407 (3)	C153—H153	0.9500
C10—C104	1.489 (3)	C154—C155	1.345 (5)
C11—C12	1.449 (3)	C155—C156	1.413 (5)
C12—C13	1.345 (3)	C155—H155	0.9500
C12—H12	0.9500	C156—H156	0.9500
C13—C14	1.432 (3)	N201—C206	1.320 (3)
C13—H13	0.9500	N201—C202	1.330 (4)
C14—C15	1.401 (3)	C202—C203	1.382 (4)
C15—C16	1.405 (3)	C202—H202	0.9500
C15—C154	1.500 (3)	C203—C204	1.387 (3)
C16—C17	1.442 (3)	C203—H203	0.9500
C17—C18	1.339 (3)	C204—C205	1.388 (3)
C17—H17	0.9500	C205—C206	1.382 (3)
C18—C19	1.441 (3)	C205—H205	0.9500
C18—H18	0.9500	C206—H206	0.9500

N24—Zn1—N21	162.77 (7)	C17—C18—H18	126.1
N24—Zn1—N22	88.42 (6)	C19—C18—H18	126.1
N21—Zn1—N22	88.84 (7)	N21—C19—C20	126.29 (18)
N24—Zn1—N23	89.34 (6)	N21—C19—C18	109.15 (18)
N21—Zn1—N23	87.94 (6)	C20—C19—C18	124.46 (19)
N22—Zn1—N23	161.70 (7)	C1—C20—C19	124.66 (19)
N24—Zn1—N101ⁱ	95.10 (6)	C1—C20—C204	118.30 (18)
N21—Zn1—N101ⁱ	102.11 (6)	C19—C20—C204	116.97 (18)
N22—Zn1—N101ⁱ	102.00 (6)	C56—N51—C52	115.3 (3)
N23—Zn1—N101ⁱ	96.29 (6)	N51—C52—C53	124.6 (3)
C19—N21—C16	106.82 (16)	N51—C52—H52	117.7
C19—N21—Zn1	126.42 (13)	C53—C52—H52	117.7
C16—N21—Zn1	126.72 (14)	C54—C53—C52	119.8 (3)
C11—N22—C14	106.27 (17)	C54—C53—H53	120.1
C11—N22—Zn1	126.10 (13)	C52—C53—H53	120.1
C14—N22—Zn1	127.37 (14)	C55—C54—C53	115.9 (2)
C4—N23—C1	106.45 (16)	C55—C54—C5	123.2 (2)
C4—N23—Zn1	125.15 (13)	C53—C54—C5	120.9 (2)
C1—N23—Zn1	126.61 (13)	C54—C55—C56	119.9 (3)
C9—N24—C6	106.48 (15)	C54—C55—H55	120.0
C9—N24—Zn1	126.17 (12)	C56—C55—H55	120.0
C6—N24—Zn1	126.59 (13)	N51—C56—C55	124.4 (3)
N23—C1—C20	124.64 (18)	N51—C56—H56	117.8
N23—C1—C2	109.72 (17)	C55—C56—H56	117.8
C20—C1—C2	125.64 (19)	C102—N101—C106	116.85 (17)
C3—C2—C1	106.8 (2)	C102—N101—Zn1ⁱⁱ	120.26 (13)
C3—C2—H2	126.6	C106—N101—Zn1ⁱⁱ	122.55 (14)
C1—C2—H2	126.6	N101—C102—C103	123.56 (18)
C2—C3—C4	107.42 (19)	N101—C102—H102	118.2
C2—C3—H3	126.3	C103—C102—H102	118.2
C4—C3—H3	126.3	C102—C103—C104	119.61 (18)
N23—C4—C5	126.00 (18)	C102—C103—H103	120.2
N23—C4—C3	109.56 (18)	C104—C103—H103	120.2
C5—C4—C3	124.42 (18)	C105—C104—C103	117.31 (18)
C6—C5—C4	125.98 (18)	C105—C104—C10	122.03 (17)
C6—C5—C54	117.43 (18)	C103—C104—C10	120.65 (17)
C4—C5—C54	116.59 (18)	C104—C105—C106	119.38 (19)
N24—C6—C5	125.05 (18)	C104—C105—H105	120.3
N24—C6—C7	109.78 (17)	C106—C105—H105	120.3
C5—C6—C7	125.15 (18)	N101—C106—C105	123.3 (2)
C8—C7—C6	106.91 (17)	N101—C106—H106	118.4
C8—C7—H7	126.5	C105—C106—H106	118.4
C6—C7—H7	126.5	C152—N151—C156	117.0 (4)
C7—C8—C9	106.83 (18)	N151—C152—C153	123.7 (5)
C7—C8—H8	126.6	N151—C152—H152	118.2
C9—C8—H8	126.6	C153—C152—H152	118.2
N24—C9—C10	125.42 (17)	C154—C153—C152	120.3 (5)
N24—C9—C8	110.00 (16)	C154—C153—H153	119.9
C10—C9—C8	124.54 (18)	C152—C153—H153	119.9
C11—C10—C9	125.06 (18)	C155—C154—C153	116.1 (3)
C11—C10—C104	117.12 (16)	C155—C154—C15	122.8 (3)
C9—C10—C104	117.77 (16)	C153—C154—C15	121.1 (3)
N22—C11—C10	125.68 (17)	C154—C155—C156	120.0 (4)
N22—C11—C12	109.87 (17)	C154—C155—H155	120.0
C10—C11—C12	124.42 (18)	C156—C155—H155	120.0
C13—C12—C11	106.50 (19)	N151—C156—C155	122.9 (5)
C13—C12—H12	126.7	N151—C156—H156	118.6
C11—C12—H12	126.7	C155—C156—H156	118.6
C12—C13—C14	107.59 (19)	C206—N201—C202	115.6 (2)
C12—C13—H13	126.2	N201—C202—C203	124.5 (2)
C14—C13—H13	126.2	N201—C202—H202	117.8
N22—C14—C15	124.8 (2)	C203—C202—H202	117.8
N22—C14—C13	109.76 (18)	C202—C203—C204	119.5 (2)
C15—C14—C13	125.41 (19)	C202—C203—H203	120.3
C14—C15—C16	126.03 (19)	C204—C203—H203	120.3
C14—C15—C154	117.7 (2)	C203—C204—C205	116.2 (2)
C16—C15—C154	116.28 (19)	C203—C204—C20	121.7 (2)
N21—C16—C15	125.76 (19)	C205—C204—C20	122.07 (19)
N21—C16—C17	109.5 (2)	C206—C205—C204	119.5 (2)
C15—C16—C17	124.7 (2)	C206—C205—H205	120.3
C18—C17—C16	106.7 (2)	C204—C205—H205	120.3
C18—C17—H17	126.6	N201—C206—C205	124.8 (2)
C16—C17—H17	126.6	N201—C206—H206	117.6
C17—C18—C19	107.8 (2)	C205—C206—H206	117.6

Symmetry codes: (i) y, −x+1/2, −z+1/2; (ii) −y+1/2, x, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···N151ⁱⁱⁱ	0.95	2.65	3.583 (4)	167
C17—H17···N51^iv	0.95	2.66	3.583 (3)	165

Symmetry codes: (iii) x, y, z+1; (iv) x, y, z−1.

Experimental details

Crystal data
Chemical formula	[Zn₄(C₄₀H₂₄N₈)₄]·8C₃H₇NO·3H₂O
M_r	3366.98
Crystal system, space group	Tetragonal, P4₂/n
Temperature (K)	100
a, c (Å)	23.6897 (5), 14.9876 (7)
V (Å³)	8411.1 (5)
Z	2
Radiation type	Cu Kα
µ (mm⁻¹)	1.24
Crystal size (mm)	0.16 × 0.04 × 0.02

Data collection
Diffractometer	Bruker X8 PROSPECTOR goniometer diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.827, 0.976
No. of measured, independent and observed [I > 2σ(I)] reflections	44415, 7723, 6768
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.108, 1.04
No. of reflections	7723
No. of parameters	442
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.59, −0.42

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2010), enCIFer (Allen et al., 2004).

Selected geometric parameters (Å, º) top

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

N24—Zn1—N21	162.77 (7)	N22—Zn1—N23	161.70 (7)
N24—Zn1—N22	88.42 (6)	N24—Zn1—N101ⁱ	95.10 (6)
N21—Zn1—N22	88.84 (7)	N21—Zn1—N101ⁱ	102.11 (6)
N24—Zn1—N23	89.34 (6)	N22—Zn1—N101ⁱ	102.00 (6)
N21—Zn1—N23	87.94 (6)	N23—Zn1—N101ⁱ	96.29 (6)

Symmetry code: (i) y, −x+1/2, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···N151ⁱⁱ	0.95	2.65	3.583 (4)	167.1
C17—H17···N51ⁱⁱⁱ	0.95	2.66	3.583 (3)	164.9

Symmetry codes: (ii) x, y, z+1; (iii) x, y, z−1.

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

Allen, F. H., Johnson, O., Shields, G. P., Smith, B. R. & Towler, M. (2004). J. Appl. Cryst. 37, 335–338. Web of Science CrossRef CAS IUCr Journals Google Scholar
Brandenburg, K. (2010). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2008). APEX2 and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2010). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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Volume 67| Part 2| February 2011| Pages m236-m237

doi:10.1107/S1600536811002054

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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

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