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

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 67| Part 2| February 2011| Pages m236-m237

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

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[Seidel, R. W., Goddard, R., Föcker, K. & Oppel, I. M. (2010). CrystEngComm, 12, 387-394.]). For the 2-chloro­phenol solvate of cyclic tetra­meric ZnTPyP, see: Lipstman & Goldberg (2010[Lipstman, S. & Goldberg, I. (2010). CrystEngComm, 12, 52-54.]). For a review article on structural motifs in coordination polymers of the 5,10,15,20-tetra­4-pyrid­ylporphyrin ligand, see: DeVries & Choe (2009[DeVries, L. D. & Choe, W. (2009). J. Chem. Crystallogr. 39, 229-240.]). For the supra­molecular chemistry of ZnTPyP in the solid-state, see: Lipstman & Goldberg (2010[Lipstman, S. & Goldberg, I. (2010). CrystEngComm, 12, 52-54.]); Seidel et al. (2010[Seidel, R. W., Goddard, R., Föcker, K. & Oppel, I. M. (2010). CrystEngComm, 12, 387-394.]) and references cited therein. For a description of the IμS microfocus X-ray source used in the present study, see: Graf (2008[Graf, J. (2008). Nachr. Chem. 56, 1050-1052.]); Schulz et al. (2009[Schulz, T., Meindl, K., Leusser, D., Stern, D., Graf, J., Michaelsen, C., Ruf, M., Sheldrick, G. M. & Stalke, D. (2009). J. Appl. Cryst. 42, 885-891.]). For PLATON / SQUEEZE, see: van der Sluis & Spek (1990[Sluis, P. van der & Spek, A. L. (1990). Acta Cryst. A46, 194-201.]); Spek (2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]). For a description of the program COOT, see: Emsley et al. (2010[Emsley, P., Lohkamp, B., Scott, W. G. & Cowtan, K. (2010). Acta Cryst. D66, 486-501.]).

[Scheme 1]

Experimental

Crystal data
  • [Zn4(C40H24N8)4]·8C3H7NO·3H2O

  • Mr = 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[Bruker (2008). APEX2 and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.827, Tmax = 0.976

  • 44415 measured reflections

  • 7723 independent reflections

  • 6768 reflections with I > 2σ(I)

  • Rint = 0.018

Refinement
  • R[F2 > 2σ(F2)] = 0.042

  • wR(F2) = 0.108

  • S = 1.04

  • 7723 reflections

  • 442 parameters

  • H-atom parameters constrained

  • Δρmax = 0.59 e Å−3

  • Δρmin = −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 DA 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[Bruker (2008). APEX2 and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2010[Bruker (2010). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: DIAMOND (Brandenburg, 2010[Brandenburg, K. (2010). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: enCIFer (Allen et al., 2004[Allen, F. H., Johnson, O., Shields, G. P., Smith, B. R. & Towler, M. (2004). J. Appl. Cryst. 37, 335-338.]).

Supporting information


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 Ueq(max)/Ueq(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 Cβ—H···Npy 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).

Refinement top

For the final refinement, the contributions of severely disordered DMF and water molecules of crystallization were removed from the diffraction data with PLATON / SQUEEZE (van der Sluis & Spek, 1990; Spek, 2009), see comment. H atoms were placed at geometrically calculated positions and refined with constrained C—H bond length of 0.95 Å and Uiso(H) = 1.2 Ueq(C) allowing them to ride on the parent C atom.

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
[Figure 1] Fig. 1. Molecular structure of the title compound. H atoms are omitted for clarity.
[Figure 2] 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.
[Figure 3] Fig. 3. Contour plot of the Fo electron density map in the plane of the pyridyl group attached to C15, calculated with phases from Fc. 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).
[Figure 4] Fig. 4. Stacking of the [ZnTPyP]4 entities viewed along the a axis direction. H atoms are omitted for clarity. Cβ—H···Npy interactions are represented by dashed lines.
[Figure 5] Fig. 5. Packing diagram of the title compound projected along the c axis direction. H atoms are omitted for clarity.
[Figure 6] Fig. 6. The tetragonal unit cell of the title compound viewed approximately along the c axis direction showing the Fo-Fc map of the disordered solvent regions (contoured at 3.0σ level). The figure was created with COOT (Emsley et al., 2010) using Fo including the contributions of the disordered solvent with phases from Fc 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·3H2ODx = 1.329 Mg m3
Mr = 3366.98Cu Kα radiation, λ = 1.54178 Å
Tetragonal, P42/nCell parameters from 130 reflections
Hall symbol: -P 4bcθ = 3.5–31.5°
a = 23.6897 (5) ŵ = 1.24 mm1
c = 14.9876 (7) ÅT = 100 K
V = 8411.1 (5) Å3Plate, dark red
Z = 20.16 × 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 source6768 reflections with I > 2σ(I)
Incoatec Quazar Multilayer Mirror monochromatorRint = 0.018
Detector resolution: 8.33 pixels mm-1θmax = 69.2°, θmin = 2.6°
ω scansh = 2825
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
k = 2428
Tmin = 0.827, Tmax = 0.976l = 1714
44415 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.108H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0472P)2 + 5.0454P]
where P = (Fo2 + 2Fc2)/3
7723 reflections(Δ/σ)max < 0.001
442 parametersΔρmax = 0.59 e Å3
0 restraintsΔρmin = 0.42 e Å3
Crystal data top
[Zn4(C40H24N8)4]·8C3H7NO·3H2OZ = 2
Mr = 3366.98Cu Kα radiation
Tetragonal, P42/nµ = 1.24 mm1
a = 23.6897 (5) ÅT = 100 K
c = 14.9876 (7) Å0.16 × 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)
Tmin = 0.827, Tmax = 0.976Rint = 0.018
44415 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0420 restraints
wR(F2) = 0.108H-atom parameters constrained
S = 1.04Δρmax = 0.59 e Å3
7723 reflectionsΔρmin = 0.42 e Å3
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
xyzUiso*/Ueq
Zn10.350673 (11)0.520064 (11)0.185590 (16)0.03823 (9)
N210.38601 (8)0.54998 (7)0.06850 (10)0.0433 (4)
N220.27781 (7)0.50134 (7)0.11541 (10)0.0404 (4)
N230.41242 (7)0.56428 (7)0.25451 (10)0.0404 (4)
N240.30440 (7)0.51392 (7)0.30222 (10)0.0377 (4)
C10.46288 (9)0.58336 (8)0.22081 (13)0.0420 (4)
C20.50033 (10)0.59793 (10)0.29314 (14)0.0532 (6)
H20.53790.61150.28800.064*
C30.47175 (10)0.58861 (10)0.36945 (15)0.0534 (6)
H30.48530.59490.42830.064*
C40.41675 (9)0.56739 (9)0.34544 (13)0.0428 (5)
C50.37497 (9)0.55138 (9)0.40720 (13)0.0442 (5)
C60.32280 (9)0.52641 (9)0.38657 (12)0.0411 (4)
C70.28126 (9)0.50864 (9)0.45108 (13)0.0451 (5)
H70.28350.51300.51400.054*
C80.23852 (9)0.48459 (9)0.40491 (13)0.0422 (4)
H80.20520.46840.42920.051*
C90.25323 (8)0.48825 (8)0.31165 (12)0.0362 (4)
C100.21846 (8)0.46994 (8)0.24113 (12)0.0360 (4)
C110.22974 (8)0.47834 (8)0.14991 (12)0.0376 (4)
C120.19052 (9)0.46543 (9)0.07858 (13)0.0460 (5)
H120.15430.44860.08450.055*
C130.21544 (10)0.48202 (10)0.00230 (14)0.0526 (6)
H130.19980.47940.05590.063*
C140.26979 (9)0.50435 (10)0.02480 (13)0.0477 (5)
C150.30923 (11)0.52569 (10)0.03612 (14)0.0545 (6)
C160.36281 (10)0.54737 (10)0.01508 (13)0.0515 (5)
C170.40164 (12)0.57099 (11)0.07905 (15)0.0636 (7)
H170.39590.57430.14160.076*
C180.44735 (11)0.58736 (10)0.03328 (15)0.0581 (6)
H180.48010.60460.05750.070*
C190.43790 (9)0.57411 (9)0.05937 (13)0.0455 (5)
C200.47569 (9)0.58754 (8)0.12914 (13)0.0429 (5)
N510.40921 (10)0.58630 (15)0.68340 (15)0.0812 (8)
C520.38597 (16)0.62318 (17)0.6300 (2)0.0945 (11)
H520.37620.65890.65420.113*
C530.37466 (15)0.61389 (13)0.54115 (18)0.0816 (9)
H530.35810.64290.50600.098*
C540.38735 (9)0.56279 (11)0.50349 (14)0.0513 (5)
C550.41194 (13)0.52451 (15)0.55825 (18)0.0792 (8)
H550.42220.48840.53600.095*
C560.42214 (14)0.53814 (18)0.6469 (2)0.0885 (10)
H560.43970.51050.68340.106*
N1010.06117 (6)0.38923 (7)0.30189 (10)0.0355 (3)
C1020.06574 (8)0.44515 (8)0.29549 (13)0.0403 (4)
H1020.03270.46730.30380.048*
C1030.11567 (8)0.47254 (8)0.27747 (13)0.0406 (4)
H1030.11670.51260.27400.049*
C1040.16441 (8)0.44146 (8)0.26451 (11)0.0339 (4)
C1050.16034 (9)0.38345 (9)0.27246 (17)0.0506 (5)
H1050.19280.36040.26520.061*
C1060.10845 (9)0.35925 (9)0.29112 (16)0.0490 (5)
H1060.10640.31940.29650.059*
N1510.2660 (2)0.5329 (2)0.3142 (2)0.1294 (17)
C1520.2458 (3)0.5685 (2)0.2569 (3)0.155 (2)
H1520.22110.59720.27800.185*
C1530.2581 (2)0.56707 (18)0.1666 (2)0.1290 (18)
H1530.24210.59450.12780.155*
C1540.29319 (12)0.52625 (14)0.13291 (16)0.0729 (8)
C1550.31337 (15)0.4886 (2)0.19209 (18)0.1009 (13)
H1550.33750.45910.17260.121*
C1560.29872 (18)0.4931 (2)0.2832 (2)0.1174 (17)
H1560.31330.46590.32370.141*
N2010.63736 (10)0.65387 (10)0.05085 (15)0.0695 (6)
C2020.60235 (13)0.68222 (12)0.1038 (2)0.0742 (8)
H2020.61400.71840.12410.089*
C2030.55016 (12)0.66270 (10)0.13114 (18)0.0635 (7)
H2030.52710.68520.16890.076*
C2040.53176 (10)0.61002 (9)0.10312 (14)0.0474 (5)
C2050.56798 (10)0.58046 (10)0.04725 (15)0.0548 (6)
H2050.55770.54420.02550.066*
C2060.61911 (11)0.60416 (12)0.02354 (17)0.0645 (7)
H2060.64290.58310.01530.077*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.04778 (16)0.04374 (16)0.02318 (14)0.00756 (11)0.00168 (10)0.00080 (10)
N210.0579 (10)0.0455 (9)0.0266 (8)0.0116 (8)0.0027 (7)0.0007 (7)
N220.0485 (9)0.0476 (9)0.0251 (8)0.0020 (7)0.0005 (7)0.0025 (7)
N230.0531 (10)0.0414 (9)0.0266 (8)0.0084 (7)0.0028 (7)0.0033 (6)
N240.0438 (9)0.0446 (9)0.0247 (8)0.0010 (7)0.0004 (6)0.0035 (6)
C10.0521 (12)0.0395 (10)0.0342 (10)0.0129 (9)0.0034 (8)0.0050 (8)
C20.0581 (14)0.0608 (14)0.0408 (12)0.0204 (11)0.0039 (10)0.0108 (10)
C30.0599 (14)0.0649 (14)0.0354 (11)0.0209 (11)0.0001 (10)0.0111 (10)
C40.0522 (12)0.0473 (11)0.0290 (10)0.0094 (9)0.0010 (8)0.0072 (8)
C50.0520 (12)0.0531 (12)0.0275 (10)0.0066 (9)0.0019 (8)0.0055 (8)
C60.0479 (11)0.0494 (11)0.0259 (10)0.0000 (9)0.0024 (8)0.0038 (8)
C70.0494 (12)0.0603 (13)0.0256 (10)0.0036 (10)0.0010 (8)0.0026 (9)
C80.0458 (11)0.0528 (12)0.0279 (10)0.0012 (9)0.0035 (8)0.0002 (8)
C90.0410 (10)0.0403 (10)0.0274 (9)0.0045 (8)0.0019 (7)0.0024 (7)
C100.0421 (10)0.0373 (10)0.0286 (9)0.0047 (8)0.0014 (7)0.0020 (7)
C110.0428 (10)0.0414 (10)0.0287 (10)0.0024 (8)0.0018 (8)0.0010 (8)
C120.0457 (11)0.0623 (13)0.0300 (10)0.0037 (10)0.0036 (8)0.0017 (9)
C130.0565 (13)0.0725 (15)0.0289 (11)0.0093 (11)0.0068 (9)0.0036 (10)
C140.0566 (13)0.0600 (13)0.0264 (10)0.0071 (10)0.0044 (9)0.0036 (9)
C150.0687 (15)0.0670 (15)0.0279 (11)0.0171 (12)0.0035 (10)0.0076 (9)
C160.0697 (15)0.0574 (13)0.0273 (10)0.0158 (11)0.0024 (9)0.0052 (9)
C170.0816 (18)0.0817 (17)0.0276 (11)0.0288 (14)0.0023 (11)0.0087 (11)
C180.0723 (16)0.0672 (15)0.0347 (12)0.0260 (12)0.0053 (10)0.0071 (10)
C190.0595 (13)0.0455 (11)0.0314 (10)0.0118 (9)0.0050 (9)0.0012 (8)
C200.0570 (12)0.0366 (10)0.0351 (10)0.0118 (9)0.0066 (9)0.0009 (8)
N510.0633 (14)0.145 (3)0.0359 (12)0.0305 (15)0.0006 (10)0.0144 (14)
C520.126 (3)0.113 (3)0.0447 (17)0.011 (2)0.0056 (17)0.0286 (17)
C530.126 (3)0.0787 (19)0.0403 (14)0.0017 (18)0.0102 (15)0.0181 (13)
C540.0499 (12)0.0755 (16)0.0286 (11)0.0147 (11)0.0009 (9)0.0067 (10)
C550.096 (2)0.100 (2)0.0419 (15)0.0139 (17)0.0143 (14)0.0037 (14)
C560.082 (2)0.135 (3)0.0486 (17)0.002 (2)0.0152 (14)0.0081 (18)
N1010.0379 (8)0.0442 (9)0.0244 (8)0.0040 (7)0.0013 (6)0.0035 (6)
C1020.0418 (11)0.0434 (11)0.0358 (10)0.0092 (8)0.0059 (8)0.0024 (8)
C1030.0466 (11)0.0392 (10)0.0360 (10)0.0058 (8)0.0063 (8)0.0009 (8)
C1040.0386 (10)0.0412 (10)0.0218 (8)0.0052 (8)0.0005 (7)0.0033 (7)
C1050.0376 (11)0.0436 (12)0.0707 (15)0.0078 (9)0.0018 (10)0.0042 (10)
C1060.0422 (11)0.0384 (11)0.0665 (15)0.0038 (9)0.0002 (10)0.0022 (10)
N1510.157 (4)0.182 (4)0.0499 (18)0.092 (3)0.022 (2)0.029 (2)
C1520.267 (7)0.130 (4)0.067 (3)0.043 (4)0.074 (3)0.028 (3)
C1530.218 (5)0.105 (3)0.064 (2)0.016 (3)0.068 (3)0.026 (2)
C1540.0797 (18)0.108 (2)0.0312 (13)0.0441 (16)0.0058 (12)0.0136 (13)
C1550.088 (2)0.180 (4)0.0349 (15)0.029 (2)0.0018 (13)0.0193 (18)
C1560.098 (3)0.210 (5)0.0446 (19)0.059 (3)0.0097 (17)0.011 (2)
N2010.0714 (14)0.0754 (15)0.0616 (13)0.0299 (12)0.0153 (11)0.0022 (11)
C2020.0847 (19)0.0592 (15)0.0786 (19)0.0325 (14)0.0173 (16)0.0085 (14)
C2030.0751 (17)0.0495 (13)0.0658 (16)0.0190 (12)0.0165 (13)0.0104 (11)
C2040.0627 (13)0.0454 (11)0.0340 (11)0.0135 (10)0.0057 (9)0.0004 (8)
C2050.0693 (15)0.0540 (13)0.0410 (12)0.0153 (11)0.0148 (10)0.0076 (10)
C2060.0700 (16)0.0752 (17)0.0482 (14)0.0173 (13)0.0177 (12)0.0064 (12)
Geometric parameters (Å, º) top
Zn1—N242.0684 (15)C19—C201.413 (3)
Zn1—N212.0695 (16)C20—C2041.483 (3)
Zn1—N222.0695 (17)N51—C561.302 (5)
Zn1—N232.0747 (16)N51—C521.306 (5)
Zn1—N101i2.1385 (16)C52—C531.376 (4)
N21—C191.363 (3)C52—H520.9500
N21—C161.369 (3)C53—C541.369 (4)
N22—C111.364 (3)C53—H530.9500
N22—C141.373 (2)C54—C551.355 (4)
N23—C41.369 (3)C55—C561.389 (4)
N23—C11.374 (3)C55—H550.9500
N24—C91.363 (3)C56—H560.9500
N24—C61.370 (2)N101—C1021.333 (3)
C1—C201.411 (3)N101—C1061.336 (3)
C1—C21.443 (3)N101—Zn1ii2.1385 (16)
C2—C31.347 (3)C102—C1031.376 (3)
C2—H20.9500C102—H1020.9500
C3—C41.442 (3)C103—C1041.383 (3)
C3—H30.9500C103—H1030.9500
C4—C51.407 (3)C104—C1051.383 (3)
C5—C61.404 (3)C105—C1061.385 (3)
C5—C541.497 (3)C105—H1050.9500
C6—C71.442 (3)C106—H1060.9500
C7—C81.352 (3)N151—C1521.294 (7)
C7—H70.9500N151—C1561.307 (6)
C8—C91.443 (3)C152—C1531.385 (5)
C8—H80.9500C152—H1520.9500
C9—C101.408 (3)C153—C1541.372 (5)
C10—C111.407 (3)C153—H1530.9500
C10—C1041.489 (3)C154—C1551.345 (5)
C11—C121.449 (3)C155—C1561.413 (5)
C12—C131.345 (3)C155—H1550.9500
C12—H120.9500C156—H1560.9500
C13—C141.432 (3)N201—C2061.320 (3)
C13—H130.9500N201—C2021.330 (4)
C14—C151.401 (3)C202—C2031.382 (4)
C15—C161.405 (3)C202—H2020.9500
C15—C1541.500 (3)C203—C2041.387 (3)
C16—C171.442 (3)C203—H2030.9500
C17—C181.339 (3)C204—C2051.388 (3)
C17—H170.9500C205—C2061.382 (3)
C18—C191.441 (3)C205—H2050.9500
C18—H180.9500C206—H2060.9500
N24—Zn1—N21162.77 (7)C17—C18—H18126.1
N24—Zn1—N2288.42 (6)C19—C18—H18126.1
N21—Zn1—N2288.84 (7)N21—C19—C20126.29 (18)
N24—Zn1—N2389.34 (6)N21—C19—C18109.15 (18)
N21—Zn1—N2387.94 (6)C20—C19—C18124.46 (19)
N22—Zn1—N23161.70 (7)C1—C20—C19124.66 (19)
N24—Zn1—N101i95.10 (6)C1—C20—C204118.30 (18)
N21—Zn1—N101i102.11 (6)C19—C20—C204116.97 (18)
N22—Zn1—N101i102.00 (6)C56—N51—C52115.3 (3)
N23—Zn1—N101i96.29 (6)N51—C52—C53124.6 (3)
C19—N21—C16106.82 (16)N51—C52—H52117.7
C19—N21—Zn1126.42 (13)C53—C52—H52117.7
C16—N21—Zn1126.72 (14)C54—C53—C52119.8 (3)
C11—N22—C14106.27 (17)C54—C53—H53120.1
C11—N22—Zn1126.10 (13)C52—C53—H53120.1
C14—N22—Zn1127.37 (14)C55—C54—C53115.9 (2)
C4—N23—C1106.45 (16)C55—C54—C5123.2 (2)
C4—N23—Zn1125.15 (13)C53—C54—C5120.9 (2)
C1—N23—Zn1126.61 (13)C54—C55—C56119.9 (3)
C9—N24—C6106.48 (15)C54—C55—H55120.0
C9—N24—Zn1126.17 (12)C56—C55—H55120.0
C6—N24—Zn1126.59 (13)N51—C56—C55124.4 (3)
N23—C1—C20124.64 (18)N51—C56—H56117.8
N23—C1—C2109.72 (17)C55—C56—H56117.8
C20—C1—C2125.64 (19)C102—N101—C106116.85 (17)
C3—C2—C1106.8 (2)C102—N101—Zn1ii120.26 (13)
C3—C2—H2126.6C106—N101—Zn1ii122.55 (14)
C1—C2—H2126.6N101—C102—C103123.56 (18)
C2—C3—C4107.42 (19)N101—C102—H102118.2
C2—C3—H3126.3C103—C102—H102118.2
C4—C3—H3126.3C102—C103—C104119.61 (18)
N23—C4—C5126.00 (18)C102—C103—H103120.2
N23—C4—C3109.56 (18)C104—C103—H103120.2
C5—C4—C3124.42 (18)C105—C104—C103117.31 (18)
C6—C5—C4125.98 (18)C105—C104—C10122.03 (17)
C6—C5—C54117.43 (18)C103—C104—C10120.65 (17)
C4—C5—C54116.59 (18)C104—C105—C106119.38 (19)
N24—C6—C5125.05 (18)C104—C105—H105120.3
N24—C6—C7109.78 (17)C106—C105—H105120.3
C5—C6—C7125.15 (18)N101—C106—C105123.3 (2)
C8—C7—C6106.91 (17)N101—C106—H106118.4
C8—C7—H7126.5C105—C106—H106118.4
C6—C7—H7126.5C152—N151—C156117.0 (4)
C7—C8—C9106.83 (18)N151—C152—C153123.7 (5)
C7—C8—H8126.6N151—C152—H152118.2
C9—C8—H8126.6C153—C152—H152118.2
N24—C9—C10125.42 (17)C154—C153—C152120.3 (5)
N24—C9—C8110.00 (16)C154—C153—H153119.9
C10—C9—C8124.54 (18)C152—C153—H153119.9
C11—C10—C9125.06 (18)C155—C154—C153116.1 (3)
C11—C10—C104117.12 (16)C155—C154—C15122.8 (3)
C9—C10—C104117.77 (16)C153—C154—C15121.1 (3)
N22—C11—C10125.68 (17)C154—C155—C156120.0 (4)
N22—C11—C12109.87 (17)C154—C155—H155120.0
C10—C11—C12124.42 (18)C156—C155—H155120.0
C13—C12—C11106.50 (19)N151—C156—C155122.9 (5)
C13—C12—H12126.7N151—C156—H156118.6
C11—C12—H12126.7C155—C156—H156118.6
C12—C13—C14107.59 (19)C206—N201—C202115.6 (2)
C12—C13—H13126.2N201—C202—C203124.5 (2)
C14—C13—H13126.2N201—C202—H202117.8
N22—C14—C15124.8 (2)C203—C202—H202117.8
N22—C14—C13109.76 (18)C202—C203—C204119.5 (2)
C15—C14—C13125.41 (19)C202—C203—H203120.3
C14—C15—C16126.03 (19)C204—C203—H203120.3
C14—C15—C154117.7 (2)C203—C204—C205116.2 (2)
C16—C15—C154116.28 (19)C203—C204—C20121.7 (2)
N21—C16—C15125.76 (19)C205—C204—C20122.07 (19)
N21—C16—C17109.5 (2)C206—C205—C204119.5 (2)
C15—C16—C17124.7 (2)C206—C205—H205120.3
C18—C17—C16106.7 (2)C204—C205—H205120.3
C18—C17—H17126.6N201—C206—C205124.8 (2)
C16—C17—H17126.6N201—C206—H206117.6
C17—C18—C19107.8 (2)C205—C206—H206117.6
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···AD—HH···AD···AD—H···A
C7—H7···N151iii0.952.653.583 (4)167
C17—H17···N51iv0.952.663.583 (3)165
Symmetry codes: (iii) x, y, z+1; (iv) x, y, z1.

Experimental details

Crystal data
Chemical formula[Zn4(C40H24N8)4]·8C3H7NO·3H2O
Mr3366.98
Crystal system, space groupTetragonal, P42/n
Temperature (K)100
a, c (Å)23.6897 (5), 14.9876 (7)
V3)8411.1 (5)
Z2
Radiation typeCu Kα
µ (mm1)1.24
Crystal size (mm)0.16 × 0.04 × 0.02
Data collection
DiffractometerBruker X8 PROSPECTOR goniometer
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2008)
Tmin, Tmax0.827, 0.976
No. of measured, independent and
observed [I > 2σ(I)] reflections
44415, 7723, 6768
Rint0.018
(sin θ/λ)max1)0.606
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.108, 1.04
No. of reflections7723
No. of parameters442
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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—N242.0684 (15)Zn1—N232.0747 (16)
Zn1—N212.0695 (16)Zn1—N101i2.1385 (16)
Zn1—N222.0695 (17)
N24—Zn1—N21162.77 (7)N22—Zn1—N23161.70 (7)
N24—Zn1—N2288.42 (6)N24—Zn1—N101i95.10 (6)
N21—Zn1—N2288.84 (7)N21—Zn1—N101i102.11 (6)
N24—Zn1—N2389.34 (6)N22—Zn1—N101i102.00 (6)
N21—Zn1—N2387.94 (6)N23—Zn1—N101i96.29 (6)
Symmetry code: (i) y, x+1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C7—H7···N151ii0.952.653.583 (4)167.1
C17—H17···N51iii0.952.663.583 (3)164.9
Symmetry codes: (ii) x, y, z+1; (iii) x, y, z1.
 

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