Download citation
Download citation
link to html
Tetra­kis(4-methoxy­carbonyl­phenyl)porphyrin, or tetra­methyl 4,4′,4′′,4′′′-porphyrin-5,10,15,20-tetra­benzoate, crystallizes as a nitro­benzene 1.9-solvate, C52H38N4O8·1.9C6H5NO2, (I). The solvent mol­ecules are contained in extended channels which propagate through the host lattice between parallel screw/glide-related columns of offset-stacked porphyrin entities. Side packing of these columns involves π–π inter­actions between the methoxy­carbonyl­phenyl residues. Mol­ecules of the porphyrin host lie on crystallographic inversion centres. The zinc(II)–pyridine derivative pyridine­(tetra­methyl 4,4′,4′′,4′′′-porphyrin-5,10,15,20-tetra­benzoato)zinc(II), [Zn(C52H36N4O8)(C5H5N)], (II), is a square-pyramidal five-coordinate complex with pyridine as an apical ligand, which crystallizes as a chloro­form–pyridine solvate. The metallo­porphyrin–pyridine units form an open layered arrangement, occluding the non-coordinated solvent moieties within the intra­layer inter­porphyrin voids. Within such arrays, the host porphyrin mol­ecules are in contact with one another through the peripheral methoxy­carbonyl substituents. The crystal packing consists of a bilayered arrangement of inversion-related porphyrin layers, with the axial ligands mutually penetrating into the voids of neighbouring arrays and tight offset stacking of these bilayers.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010600641X/gd3004sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827010600641X/gd3004Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827010600641X/gd3004IIsup3.hkl
Contains datablock II

CCDC references: 605707; 605708

Comment top

Tetraaryl-porphyrins and -metalloporphyrins are extremely versatile host scaffolds for the formation of crystalline inclusion compounds with a large number of guest species (Byrn et al., 1993; Krishna Kumar et al., 1998; Goldberg, 2005). This involves genuine lattice clathrates (without specific bonds between the porphyrin hosts; Byrn et al., 1993), as well as structures wherein functionalized porphyrins are interlinked in two or three dimensions by hydrogen bonding of coordination polymerization (Goldberg, 2005). In this study, we characterize the supramolecular organization of the title compounds, (I) (the free base porphyrin) and (II) (its zinc pyridyl complex), which have not been reported before, and describe examples of their clathration behaviour. In relation to the basic tetraphenylporphyrin clathrate host (Byrn et al., 1993), these two compounds have slightly extended arms, bearing an additional carbomethoxy group on the para-positions of the four phenyl substituents, and thus an increased propensity, due to their elongated arms, for the formation of solvates and clathrates (Krishna Kumar et al., 1998). The two structures were analysed at ca 110 K.

Compound (I) crystallizes as a bis(nitrobenzene) solvate (Fig. 1), with the porphyrin species located on crystallographic centres of inversion. The macrocyclic core 24-membered ring is planar to within ±0.053 Å, except for atom N21, which deviates by 0.118 (2) Å from this plane. The four aryl substituents are oriented roughly perpendicular to the macro-ring in a typical manner, the dihedral angles between their mean planes and that of the macro-ring being 60.80 (3)° for the C25–C30 phenyl group and 69.96 (5)° for the C35–C40 phenyl group. Moreover, at every site, the carbomethoxy fragments are nearly coplanar with the corresponding phenyl ring they are bound to, the dihedral angles between their mean planes being only 8.8 (1) and 5.7 (1)°. The two inner pyrrole N-bound H atoms are disordered between the four N-atom sites.

The crystal structure of (I) can be best described as consisting of offset-stacked porphyrin columns aligned parallel to the b axis of the crystal (Fig. 2). The mean distance between the planes of successive porphyrin macrocycles is 4.15 (5) Å. Sideways, the columns are arranged in an approximately square-grid array. The porphyrin molecules in a given column are tilted by about 45° with respect to the stacking axis (Fig. 3). This intermolecular organization is associated with the presence of channel voids between the porphyrin columns, which are accommodated by the nitrobenzene guest components. The latter are aligned perpendicular to the channel axis, exhibiting antiparallel orientation between successive species in every channel [related by inversion at (1/2 − x, −y − 1/2, 1/2 − z)]. As shown in Fig. 3, the porphyrin columns are arranged in a herringbone fashion, and their side packing is characterized by stacking interactions between partly overlapping carbomethoxyphenyl fragments of adjacent molecules related by the glide/screw symmetry, at about 3.7 Å. Some relatively short intermolecular C—H···O contacts, which may represent attractive interactions, are listed in Table 1. These involve host···host contacts within as well as between the porphyrin columns, and a porphyrin–nitrobenzene contact.

The molecular structure of (II) is shown in Fig. 4. Note that the O63–C64 methoxy substituent exhibits orientational disorder. Compound (II) represents a square-pyramidal five-coordinate complex of the porphyrin species, with the inner pyrrole N atoms deviating alternately ±0.021 (1) Å from their mean plane. The central Zn ion is displaced by 0.340 (1) Å from this N4 plane towards the axial ligand, imparting a domed structure to the metalloporphyrin entity. This is a characteristic of many five-coordinate complexes of metallated tetraarylporphyrins with a single axial ligand [How many hits?; Cambridge Structural Database (CSD), Version?; Allen, 2002; Lipstman et al., 2006; Lipstman & Goldberg, 2006]. Otherwise, the intramolecular conformational features of (II) are similar to those observed in (I). Thus, the dihedral angles between the mean planes of the phenyl substituents and the plane of the four pyrrole N atoms are 67.8 (1), 58.4 (1), 85.4 (1) and 82.1 (1)°, respectively, for the C25–C30, C35–C40, C45–C50 and C55–C60 phenyl rings. The mean planes of the corresponding carbomethoxy fragments deviate only slightly from coplanarity with their adjacent phenyl rings, as indicated by the dihedral angles between the respective phenyl and carbomethoxy residues of (in the same order as above) 5.4 (3), 10.2 (3), 7.0 (3) and 7.0 (5)/15.4 (4)°.

The molecules of (II) are arranged in the crystal in a square-layered fashion approximately perpendicular to the c axis. Adjacent units in a layer contact one another in all four directions through the peripheral cis-related carbomethoxy fragments. The corresponding non-bonding contacts between the carbonyl O atoms of one porphyrin to the methyl C atoms are O32···C64(x − 1, y, z) = 3.356 (5) Å and O32···C64'(x − 1, y, z) = 3.141 (6) Å, O42···C44(x, y − 1, z) = 3.621 (5) Å, O52···C44(x + 1, y, z) = 4.425 (5) Å and O62···C54(x, y + 1, z) = 3.143 (5) Å. Additional intermolecular CH(phenyl)···O(carbonyl) weak hydrogen-bond type attractions between neighbouring porphyrin species are also observed (Table 1). Such supramolecular organization is associated with the creation of void space between neighbouring porphyrin molecules. A given node of the open square-grid porphyrin array is a contact point for the carbomethoxy groups of four different molecules, which are related to one another by a lattice translation along a or b. Inversion-related layers pack in a lock-and-key mode, by inserting the axial ligands of one layer into, and partly occupying, half of the interporphyrin voids of a neighbouring layer (Fig. 5). The remaining void space in these layers, and the other half of the interporphyrin voids in every layer, is accommodated in a disordered manner and with partial occupancies by molecules of the pyridine and chloroform solvents. The approximate positions of the solvent moieties are illustrated in Fig. 6. The bilayer domains thus formed also stack in an offset manner in order to optimize van der Waals interactions, by placing the aryl substituents of one bilayer close to the concave porphyrin surfaces of adjacent bilayers (Fig. 5).

The above-described porphyrin supramolecular organization and solvent clathration features are consistent with earlier observations in related tetraarylporphyrin materials, which lack specific hydrogen-bonding or coordination interactions between the porphyrin units [Byrn et al., 1993; Krishna Kumar et al., 1998; CSD, How many hits? (Allen, 2002)].

Experimental top

Compound (I) was synthesized using the Lindsey method (Lindsey et al., 1987), by condensation of pyrrole with (4-methoxcarbonylphenyl) aldehyde. The crude product was purified by silica-gel column chromatography using 2% acetone in chloroform as eluent. Compound (I) was metallated with zinc(II) by reacting (I) (50 mg, 0.06 mmol) with zinc(II) bis(acetate) (133 mg, 0.06 mmol) in methanol (Volume?), affording the metalloporphyrin derivative, zinc-(I). The products were confirmed by 1H NMR and UV–vis (in tetrahydrofuran) spectra. Diffraction-quality crystals of (I) were obtained by dissolving 5 mg (0.006 mmol) of the compound in a minimal amount of chloroform and a few drops of nitrobenzene, followed by slow evaporation over two weeks. Single crystals of (II) were prepared by dissolving zinc-(I) (6 mg, 0.0065 mmol) in a small amount (Volume?) of a 9:1 (v/v) chloroform–pyridine mixture with a few drops of nitrobenzene, followed by slow evaporation in air for 10 d.

Refinement top

The H atoms were located in calculated positions and were constrained to ride on their parent atoms, with C—H distances in the range 0.95–0.98 Å and with Uiso(H) = 1.2 or 1.5Ueq(C). The positional disorder of the pyrrole H atoms in (I) is characterized by occupancy factors of 0.42 (3) and 0.58 (3) for atoms H21 and H22, respectively. Molecules of the nitrobenzene guest occluded in the channels of (I) were refined to have an occupancy of 0.95 at each site. The O63–C64 methoxy group in (II) reveals orientational disorder, which was reasonably well characterized. The relative occupancies are 0.459 (8) for the O63–C64 fragment and 0.541 (8) for the O63'–C64' fragment. The structure of (II) was then refined as a 1:3 twin. It was found to contain pyridine and chloroform solvent, which could not be modelled reliably. Conventional refinement converged at R = 0.088, showing recognisable frameworks of the solvent species with partial occupancies at well defined sites, but with very high anisotropic displacement parameters for the corresponding atoms and with distorted geometries. Correspondingly, it was preferable to subtract the contribution of this solvent from the diffraction data using the SQUEEZE procedure in PLATON (Spek, 2003). The modified calculations coverged smoothly at a considerably lower R factor, resulting in a structural model of good precision for the porphyrin lattice, as discussed in this paper. Standard refinement calculations of the entire structure in this case served to locate the guest components in the lattice. The solvent-accessible voids were estimated to be 31% of the crystal volume. The residual electron-density count was assessed as 202 electrons per unit cell, which is consistent with approximately two molecules of pyridine and two molecules of chloroform.

Computing details top

For both compounds, data collection: COLLECT (Nonius, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO; program(s) used to solve structure: SIR97 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and Mercury (Bruno et al., 2002); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level at ca 110 K. The porphyrin molecules are located on centres of inversion at (−x, 1 − y, 1 − z). H atoms have been omitted.
[Figure 2] Fig. 2. The crystal packing of (I), stereoviewed approximately down the b axis. Note the offset stacked arrangement of the porphyrin molecules that form the host lattice, and the antiparallel arrangement of the nitrobenzene solvent incorporated into the channel voids. H atoms have been omitted. N and O atoms are denoted by shaded circles.
[Figure 3] Fig. 3. A perspective side view (stereo) of three neighbouring porphyrin columns of (I) related to one another by the glide/screw symmetry, showing the herring-bone organization and the stacking interaction between the carboxymethyl fragments of adjacent columns (see text). H atoms have been omitted for clarity. N and O atoms are denoted by shaded circles.
[Figure 4] Fig. 4. The molecular structure of host (II), showing its domed shape and the atom-labelling scheme. Displacement ellipsoids are drawn at the 40% probability level at ca 110 K. Note the orientational disorder of the C61–C64 carbomethoxy group (primed atoms).
[Figure 5] Fig. 5. A stereoview of the crystal packing of host molecules in (II) (approximately down a), showing their layered organization edge-on and the tight packing of the offset-stacked layers along the c axis. Zn, N and O atoms are denoted by shaded circles. H atoms have been omitted.
[Figure 6] Fig. 6. A face-on view of two overlapping layers in (II), in the form of a crystal structure projection down the c axis (a horizontal, b vertical). The upper layer is shown in a space-filling mode, which also illustrates the attractive contacts between the terminal carbomethoxy groups of neighbouring porphyrin molecules. The lower porphyrin layer is represented by a stick framework (except for the Zn ions, which are denoted by small spheres). Note that the axial ligands of the lower porphyrin layer penetrate into one set of interporphyrin voids in the upper porphyrin layer. The approximate sites of the solvent molecules in the voids of the upper layer (as derived from the conventional refinement) are represented by discrete spheres: pyridine is represented by the larger spheres, and chloroform by the smaller spheres.
(I) Tetramethyl 4,4',4'',4'''-porphyrin-5,10,15,20-tetrabenzoate top
Crystal data top
C52H38N4O8·1.904C6H5NO2F(000) = 2255.4
Mr = 1081.27Dx = 1.347 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 5804 reflections
a = 32.6249 (8) Åθ = 1.4–28.2°
b = 7.0657 (2) ŵ = 0.09 mm1
c = 23.5160 (8) ÅT = 110 K
β = 100.2918 (9)°Prism, purple
V = 5333.6 (3) Å30.35 × 0.20 × 0.15 mm
Z = 4
Data collection top
Nonius KappaCCD area-detector
diffractometer
3904 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.054
Graphite monochromatorθmax = 28.2°, θmin = 2.5°
Detector resolution: 56 microns pixels mm-1h = 4142
ϕ scansk = 99
20139 measured reflectionsl = 3030
6404 independent 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)] = 0.057Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.158H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.0865P)2]
where P = (Fo2 + 2Fc2)/3
6404 reflections(Δ/σ)max < 0.001
374 parametersΔρmax = 0.30 e Å3
0 restraintsΔρmin = 0.31 e Å3
Crystal data top
C52H38N4O8·1.904C6H5NO2V = 5333.6 (3) Å3
Mr = 1081.27Z = 4
Monoclinic, C2/cMo Kα radiation
a = 32.6249 (8) ŵ = 0.09 mm1
b = 7.0657 (2) ÅT = 110 K
c = 23.5160 (8) Å0.35 × 0.20 × 0.15 mm
β = 100.2918 (9)°
Data collection top
Nonius KappaCCD area-detector
diffractometer
3904 reflections with I > 2σ(I)
20139 measured reflectionsRint = 0.054
6404 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0570 restraints
wR(F2) = 0.158H-atom parameters constrained
S = 1.02Δρmax = 0.30 e Å3
6404 reflectionsΔρmin = 0.31 e Å3
374 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*/UeqOcc. (<1)
C10.01794 (6)0.8569 (2)0.57609 (8)0.0225 (4)
C20.05179 (6)0.9743 (2)0.60418 (8)0.0268 (4)
H20.04981.07530.63020.032*
C30.08700 (6)0.9141 (3)0.58675 (8)0.0267 (4)
H30.11420.96540.59800.032*
C40.07533 (6)0.7559 (2)0.54757 (8)0.0219 (4)
C50.10327 (6)0.6434 (2)0.52340 (8)0.0214 (4)
C60.09243 (6)0.4807 (2)0.48956 (8)0.0225 (4)
C70.12050 (6)0.3752 (2)0.46072 (8)0.0263 (4)
H70.14940.39920.46270.032*
C80.09816 (6)0.2353 (2)0.43024 (8)0.0253 (4)
H80.10850.14340.40700.030*
C90.05584 (6)0.2511 (2)0.43945 (8)0.0218 (4)
C100.02313 (6)0.1327 (2)0.41470 (7)0.0209 (4)
N210.03333 (5)0.7275 (2)0.54152 (6)0.0219 (3)
H210.01870.64190.51940.026*0.42 (3)
N220.05349 (5)0.40154 (19)0.47576 (6)0.0213 (3)
H220.03100.44030.48800.026*0.58 (3)
C250.14841 (6)0.6943 (2)0.53676 (8)0.0234 (4)
C260.16281 (6)0.8703 (2)0.52233 (8)0.0262 (4)
H260.14370.96020.50280.031*
C270.20474 (6)0.9158 (3)0.53610 (8)0.0282 (4)
H270.21411.03660.52610.034*
C280.23312 (6)0.7851 (3)0.56453 (8)0.0269 (4)
C290.21900 (6)0.6082 (3)0.57865 (9)0.0302 (5)
H290.23820.51800.59790.036*
C300.17714 (6)0.5630 (3)0.56483 (8)0.0286 (4)
H300.16780.44170.57450.034*
C310.27768 (6)0.8404 (3)0.58030 (9)0.0312 (5)
O320.29167 (4)0.98904 (19)0.56696 (6)0.0371 (4)
O330.30050 (4)0.7072 (2)0.61223 (6)0.0391 (4)
C340.34423 (6)0.7499 (3)0.63104 (10)0.0427 (6)
H34A0.35790.75940.59730.064*
H34B0.35730.64880.65650.064*
H34C0.34700.87040.65200.064*
C350.03307 (6)0.0104 (2)0.37180 (8)0.0215 (4)
C360.03409 (6)0.2035 (2)0.38326 (8)0.0251 (4)
H360.02740.24870.41850.030*
C370.04484 (6)0.3303 (2)0.34361 (8)0.0265 (4)
H370.04570.46190.35200.032*
C380.05444 (6)0.2671 (2)0.29147 (8)0.0224 (4)
C390.05297 (6)0.0736 (2)0.27937 (8)0.0256 (4)
H390.05920.02860.24380.031*
C400.04238 (6)0.0523 (2)0.31945 (8)0.0256 (4)
H400.04150.18390.31110.031*
C410.06699 (6)0.4071 (3)0.25037 (8)0.0273 (4)
O420.07392 (6)0.57220 (19)0.26153 (7)0.0516 (5)
O430.07053 (5)0.33006 (17)0.19992 (6)0.0337 (4)
C440.08314 (8)0.4569 (3)0.15782 (9)0.0414 (6)
H44A0.11180.49890.17150.062*
H44B0.08150.39060.12090.062*
H44C0.06460.56700.15250.062*
C450.23717 (10)0.2379 (3)0.22574 (10)0.0476 (7)0.952 (3)
H450.25390.23000.19670.057*0.952 (3)
C460.19467 (10)0.2266 (3)0.21152 (12)0.0536 (8)0.952 (3)
H460.18170.21190.17220.064*0.952 (3)
C470.17029 (10)0.2366 (3)0.25463 (14)0.0597 (8)0.952 (3)
H470.14080.22620.24490.072*0.952 (3)
C480.18949 (13)0.2618 (4)0.31166 (13)0.0663 (10)0.952 (3)
H480.17300.27040.34100.080*0.952 (3)
C490.23192 (12)0.2744 (3)0.32625 (12)0.0608 (9)0.952 (3)
H490.24500.29210.36530.073*0.952 (3)
C500.25522 (10)0.2611 (3)0.28302 (11)0.0482 (7)0.952 (3)
N510.30073 (9)0.2699 (3)0.29829 (11)0.0588 (7)0.952 (3)
O520.32147 (7)0.2423 (3)0.26037 (10)0.0733 (7)0.952 (3)
O530.31635 (8)0.3072 (3)0.34878 (8)0.0768 (8)0.952 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0238 (11)0.0217 (9)0.0225 (10)0.0009 (7)0.0058 (8)0.0005 (7)
C20.0253 (11)0.0284 (10)0.0276 (11)0.0042 (8)0.0071 (8)0.0060 (8)
C30.0234 (11)0.0296 (10)0.0271 (10)0.0049 (8)0.0044 (8)0.0064 (8)
C40.0191 (10)0.0246 (9)0.0215 (9)0.0020 (7)0.0026 (7)0.0002 (7)
C50.0184 (10)0.0247 (9)0.0206 (10)0.0009 (7)0.0021 (7)0.0005 (7)
C60.0200 (10)0.0233 (9)0.0239 (10)0.0006 (7)0.0031 (8)0.0019 (7)
C70.0175 (10)0.0278 (10)0.0343 (11)0.0001 (7)0.0063 (8)0.0021 (8)
C80.0210 (11)0.0261 (9)0.0296 (11)0.0031 (7)0.0069 (8)0.0016 (7)
C90.0207 (10)0.0226 (9)0.0226 (10)0.0011 (7)0.0052 (8)0.0004 (7)
C100.0206 (10)0.0216 (9)0.0203 (9)0.0008 (7)0.0037 (8)0.0011 (7)
N210.0197 (9)0.0231 (8)0.0231 (8)0.0008 (6)0.0043 (6)0.0025 (6)
N220.0175 (8)0.0224 (7)0.0240 (8)0.0009 (6)0.0035 (6)0.0024 (6)
C250.0202 (10)0.0276 (9)0.0232 (10)0.0027 (7)0.0057 (8)0.0044 (7)
C260.0223 (11)0.0283 (10)0.0277 (10)0.0000 (8)0.0036 (8)0.0038 (8)
C270.0247 (11)0.0319 (10)0.0289 (11)0.0061 (8)0.0069 (8)0.0031 (8)
C280.0192 (10)0.0347 (10)0.0271 (10)0.0029 (8)0.0050 (8)0.0066 (8)
C290.0220 (11)0.0342 (10)0.0325 (11)0.0018 (8)0.0003 (9)0.0012 (8)
C300.0267 (11)0.0268 (9)0.0311 (11)0.0028 (8)0.0022 (9)0.0017 (8)
C310.0227 (11)0.0380 (11)0.0338 (12)0.0025 (9)0.0077 (9)0.0081 (9)
O320.0233 (8)0.0446 (9)0.0436 (9)0.0081 (6)0.0069 (7)0.0072 (7)
O330.0206 (8)0.0514 (9)0.0428 (9)0.0031 (6)0.0013 (7)0.0017 (7)
C340.0195 (12)0.0577 (14)0.0478 (14)0.0021 (10)0.0022 (10)0.0044 (11)
C350.0165 (10)0.0236 (9)0.0241 (10)0.0004 (7)0.0024 (8)0.0015 (7)
C360.0271 (11)0.0261 (9)0.0229 (10)0.0006 (8)0.0066 (8)0.0022 (7)
C370.0281 (11)0.0200 (9)0.0319 (11)0.0021 (7)0.0067 (9)0.0010 (7)
C380.0193 (10)0.0254 (9)0.0225 (10)0.0008 (7)0.0037 (8)0.0010 (7)
C390.0280 (11)0.0242 (9)0.0252 (10)0.0008 (8)0.0068 (8)0.0000 (7)
C400.0289 (11)0.0198 (9)0.0285 (10)0.0005 (7)0.0062 (8)0.0013 (7)
C410.0310 (12)0.0227 (10)0.0294 (11)0.0007 (8)0.0085 (9)0.0011 (8)
O420.0894 (14)0.0248 (8)0.0501 (10)0.0082 (8)0.0386 (10)0.0015 (7)
O430.0497 (10)0.0284 (7)0.0246 (7)0.0099 (6)0.0109 (7)0.0004 (6)
C440.0641 (17)0.0343 (11)0.0294 (12)0.0109 (10)0.0182 (11)0.0051 (9)
C450.071 (2)0.0384 (13)0.0329 (14)0.0148 (12)0.0091 (13)0.0008 (10)
C460.072 (2)0.0428 (14)0.0467 (16)0.0114 (13)0.0111 (15)0.0081 (11)
C470.073 (2)0.0370 (14)0.073 (2)0.0147 (13)0.0249 (17)0.0118 (13)
C480.115 (3)0.0404 (15)0.0529 (19)0.0184 (16)0.040 (2)0.0068 (12)
C490.111 (3)0.0346 (14)0.0390 (16)0.0191 (15)0.0178 (17)0.0026 (11)
C500.080 (2)0.0271 (12)0.0361 (14)0.0147 (12)0.0080 (14)0.0018 (9)
N510.090 (2)0.0366 (12)0.0431 (15)0.0131 (11)0.0056 (14)0.0034 (10)
O520.0781 (17)0.0744 (14)0.0641 (15)0.0183 (11)0.0039 (13)0.0056 (11)
O530.118 (2)0.0535 (12)0.0458 (13)0.0017 (11)0.0214 (12)0.0056 (9)
Geometric parameters (Å, º) top
C1—N211.376 (2)O33—C341.448 (2)
C1—C10i1.397 (3)C34—H34A0.9800
C1—C21.443 (3)C34—H34B0.9800
C2—C31.355 (3)C34—H34C0.9800
C2—H20.9500C35—C361.390 (2)
C3—C41.455 (2)C35—C401.392 (3)
C3—H30.9500C36—C371.383 (3)
C4—N211.367 (2)C36—H360.9500
C4—C51.404 (3)C37—C381.392 (3)
C5—C61.407 (2)C37—H370.9500
C5—C251.494 (3)C38—C391.395 (2)
C6—N221.373 (2)C38—C411.491 (3)
C6—C71.441 (3)C39—C401.384 (3)
C7—C81.355 (3)C39—H390.9500
C7—H70.9500C40—H400.9500
C8—C91.440 (3)C41—O421.208 (2)
C8—H80.9500C41—O431.329 (2)
C9—N221.374 (2)O43—C441.448 (2)
C9—C101.398 (2)C44—H44A0.9800
C10—C1i1.397 (3)C44—H44B0.9800
C10—C351.504 (2)C44—H44C0.9800
N21—H210.8800C45—C461.369 (4)
N22—H220.8800C45—C501.380 (4)
C25—C261.393 (3)C45—H450.9500
C25—C301.398 (3)C46—C471.398 (4)
C26—C271.386 (3)C46—H460.9500
C26—H260.9500C47—C481.387 (4)
C27—C281.392 (3)C47—H470.9500
C27—H270.9500C48—C491.368 (5)
C28—C291.393 (3)C48—H480.9500
C28—C311.487 (3)C49—C501.377 (4)
C29—C301.383 (3)C49—H490.9500
C29—H290.9500C50—N511.465 (4)
C30—H300.9500N51—O521.228 (3)
C31—O321.209 (2)N51—O531.234 (3)
C31—O331.343 (2)
N21—C1—C10i126.00 (16)C31—O33—C34116.27 (16)
N21—C1—C2108.78 (16)O33—C34—H34A109.5
C10i—C1—C2125.13 (16)O33—C34—H34B109.5
C3—C2—C1107.57 (16)H34A—C34—H34B109.5
C3—C2—H2126.2O33—C34—H34C109.5
C1—C2—H2126.2H34A—C34—H34C109.5
C2—C3—C4106.99 (17)H34B—C34—H34C109.5
C2—C3—H3126.5C36—C35—C40118.84 (16)
C4—C3—H3126.5C36—C35—C10122.03 (16)
N21—C4—C5125.87 (16)C40—C35—C10119.12 (15)
N21—C4—C3108.84 (16)C37—C36—C35120.35 (17)
C5—C4—C3125.15 (17)C37—C36—H36119.8
C4—C5—C6125.15 (17)C35—C36—H36119.8
C4—C5—C25117.76 (15)C36—C37—C38120.67 (16)
C6—C5—C25117.02 (16)C36—C37—H37119.7
N22—C6—C5126.53 (16)C38—C37—H37119.7
N22—C6—C7108.48 (15)C37—C38—C39119.28 (16)
C5—C6—C7124.90 (17)C37—C38—C41119.27 (15)
C8—C7—C6107.41 (17)C39—C38—C41121.44 (16)
C8—C7—H7126.3C40—C39—C38119.64 (18)
C6—C7—H7126.3C40—C39—H39120.2
C7—C8—C9107.69 (16)C38—C39—H39120.2
C7—C8—H8126.2C39—C40—C35121.22 (16)
C9—C8—H8126.2C39—C40—H40119.4
N22—C9—C10126.74 (17)C35—C40—H40119.4
N22—C9—C8108.35 (15)O42—C41—O43123.15 (18)
C10—C9—C8124.90 (16)O42—C41—C38124.24 (18)
C1i—C10—C9125.86 (16)O43—C41—C38112.61 (15)
C1i—C10—C35117.84 (15)C41—O43—C44115.92 (15)
C9—C10—C35116.20 (16)O43—C44—H44A109.5
C4—N21—C1107.80 (14)O43—C44—H44B109.5
C4—N21—H21126.1H44A—C44—H44B109.5
C1—N21—H21126.1O43—C44—H44C109.5
C6—N22—C9108.06 (15)H44A—C44—H44C109.5
C6—N22—H22126.0H44B—C44—H44C109.5
C9—N22—H22126.0C46—C45—C50118.8 (3)
C26—C25—C30118.74 (17)C46—C45—H45120.6
C26—C25—C5121.75 (16)C50—C45—H45120.6
C30—C25—C5119.51 (16)C45—C46—C47120.2 (3)
C27—C26—C25120.81 (17)C45—C46—H46119.9
C27—C26—H26119.6C47—C46—H46119.9
C25—C26—H26119.6C48—C47—C46119.4 (3)
C26—C27—C28120.15 (17)C48—C47—H47120.3
C26—C27—H27119.9C46—C47—H47120.3
C28—C27—H27119.9C49—C48—C47120.8 (3)
C27—C28—C29119.35 (18)C49—C48—H48119.6
C27—C28—C31118.83 (17)C47—C48—H48119.6
C29—C28—C31121.80 (18)C48—C49—C50118.5 (3)
C30—C29—C28120.40 (18)C48—C49—H49120.7
C30—C29—H29119.8C50—C49—H49120.7
C28—C29—H29119.8C49—C50—C45122.2 (3)
C29—C30—C25120.55 (17)C49—C50—N51119.0 (3)
C29—C30—H30119.7C45—C50—N51118.8 (3)
C25—C30—H30119.7O52—N51—O53123.1 (3)
O32—C31—O33123.81 (19)O52—N51—C50118.8 (2)
O32—C31—C28124.16 (19)O53—N51—C50118.1 (3)
O33—C31—C28112.02 (17)
Symmetry code: (i) x, y+1, z+1.
(II) pyridine(tetramethyl 4,4',4'',4'''-porphyrin-5,10,15,20- tetrabenzoato)zinc(II) top
Crystal data top
[Zn(C52H36N4O8)(C5H5N)]F(000) = 2048
Mr = 989.32Dx = 1.079 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 7893 reflections
a = 17.4965 (4) Åθ = 1.4–28.3°
b = 18.2617 (2) ŵ = 0.45 mm1
c = 19.0558 (4) ÅT = 110 K
V = 6088.6 (2) Å3Prism, purple
Z = 40.45 × 0.40 × 0.30 mm
Data collection top
Nonius KappaCCD area-detector
diffractometer
9268 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.085
Graphite monochromatorθmax = 28.2°, θmin = 2.4°
Detector resolution: 56 microns pixels mm-1h = 2323
ϕ and ω scansk = 2424
52179 measured reflectionsl = 2525
14686 independent reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.053H-atom parameters constrained
wR(F2) = 0.131 w = 1/[σ2(Fo2) + (0.0727P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.90(Δ/σ)max = 0.001
14686 reflectionsΔρmax = 0.32 e Å3
649 parametersΔρmin = 0.40 e Å3
0 restraintsAbsolute structure: Flack (1983), with how many Friedel pairs?
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.259 (9)
Crystal data top
[Zn(C52H36N4O8)(C5H5N)]V = 6088.6 (2) Å3
Mr = 989.32Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 17.4965 (4) ŵ = 0.45 mm1
b = 18.2617 (2) ÅT = 110 K
c = 19.0558 (4) Å0.45 × 0.40 × 0.30 mm
Data collection top
Nonius KappaCCD area-detector
diffractometer
9268 reflections with I > 2σ(I)
52179 measured reflectionsRint = 0.085
14686 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.053H-atom parameters constrained
wR(F2) = 0.131Δρmax = 0.32 e Å3
S = 0.90Δρmin = 0.40 e Å3
14686 reflectionsAbsolute structure: Flack (1983), with how many Friedel pairs?
649 parametersAbsolute structure parameter: 0.259 (9)
0 restraints
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.

The crystal structure contains pyridine and chloroform solvent which could not be modelled reliably. Correspondingly, the contribution of this solvent was subtracted from the diffraction data by the SQUEEZE procedure, with the aid of the PLATON software (Spek, 2003). The solvent-accessible voids were estimated to be 31% of the crystal volume, and the residual electron-density count was assessed as 202 electrons per unit cell, consistent with approximately one molecule of pyridine and one molecule of chloroform.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Zn0.89994 (2)0.124742 (18)0.850035 (19)0.03341 (10)
C10.9702 (2)0.27857 (16)0.87265 (17)0.0374 (8)
C20.9499 (2)0.35456 (16)0.87342 (18)0.0393 (8)
H20.98420.39470.87690.047*
C30.8729 (2)0.35870 (16)0.86829 (18)0.0412 (9)
H30.84310.40220.86670.049*
C40.8443 (2)0.28425 (16)0.86561 (16)0.0363 (8)
C50.76666 (19)0.26481 (16)0.86173 (17)0.0344 (7)
C60.73857 (18)0.19248 (15)0.86094 (17)0.0325 (7)
C70.65873 (19)0.17407 (16)0.86533 (16)0.0348 (7)
H70.61710.20750.86600.042*
C80.65413 (19)0.09917 (17)0.86845 (17)0.0371 (8)
H80.60900.07060.87290.045*
C90.73235 (17)0.07228 (16)0.86347 (17)0.0322 (7)
C100.75197 (19)0.00252 (16)0.86438 (17)0.0321 (7)
C110.82782 (18)0.02942 (15)0.86372 (17)0.0330 (7)
C120.8487 (2)0.10593 (16)0.86056 (18)0.0391 (8)
H120.81490.14660.85820.047*
C130.92585 (19)0.10818 (16)0.86155 (18)0.0380 (8)
H130.95650.15110.85930.046*
C140.95339 (19)0.03466 (16)0.86656 (17)0.0346 (8)
C151.02955 (19)0.01377 (17)0.87538 (17)0.0341 (7)
C161.05769 (18)0.05742 (17)0.88255 (17)0.0330 (7)
C171.1377 (2)0.07517 (19)0.89241 (19)0.0424 (8)
H171.17890.04170.89720.051*
C181.1416 (2)0.14954 (17)0.89340 (18)0.0401 (8)
H181.18670.17810.89870.048*
C191.0646 (2)0.17725 (18)0.88490 (18)0.0375 (8)
C201.04438 (19)0.25132 (17)0.88055 (18)0.0363 (8)
N210.90461 (16)0.23682 (13)0.86736 (13)0.0339 (6)
N220.78224 (14)0.13053 (13)0.85949 (13)0.0314 (5)
N230.89268 (16)0.01251 (13)0.86612 (13)0.0350 (6)
N241.01446 (14)0.11919 (14)0.87833 (13)0.0332 (6)
C250.70989 (19)0.32599 (16)0.85815 (18)0.0361 (7)
C260.67003 (19)0.33975 (16)0.79708 (17)0.0352 (7)
H260.67480.30700.75860.042*
C270.62323 (18)0.40040 (16)0.79090 (19)0.0364 (7)
H270.59760.41000.74790.044*
C280.61381 (18)0.44695 (15)0.84728 (18)0.0365 (7)
C290.6505 (2)0.43180 (19)0.91001 (18)0.0458 (9)
H290.64250.46250.94960.055*
C300.6986 (2)0.37253 (19)0.91518 (17)0.0435 (8)
H300.72450.36320.95810.052*
C310.56715 (19)0.51575 (17)0.84285 (19)0.0386 (7)
O320.55594 (16)0.55700 (13)0.89032 (14)0.0534 (7)
O330.53937 (15)0.52526 (12)0.77811 (13)0.0478 (6)
C340.4947 (3)0.5902 (2)0.7689 (2)0.0685 (12)
H34A0.44250.58140.78570.103*
H34B0.49320.60320.71900.103*
H34C0.51760.63040.79570.103*
C350.68918 (18)0.05729 (15)0.87038 (16)0.0323 (7)
C360.63378 (18)0.06445 (16)0.81869 (17)0.0342 (7)
H360.63620.03410.77830.041*
C370.57539 (18)0.11467 (16)0.82469 (16)0.0358 (7)
H370.53770.11840.78900.043*
C380.57195 (18)0.16001 (16)0.88350 (17)0.0337 (7)
C390.62810 (18)0.15483 (17)0.93490 (17)0.0360 (8)
H390.62700.18670.97430.043*
C400.6855 (2)0.10329 (16)0.92871 (18)0.0361 (8)
H400.72290.09910.96460.043*
C410.5083 (2)0.21362 (17)0.88923 (18)0.0375 (7)
O420.46463 (14)0.22907 (13)0.84207 (15)0.0525 (6)
O430.50618 (14)0.24527 (13)0.95289 (13)0.0481 (6)
C440.4476 (2)0.2999 (2)0.9623 (2)0.0550 (10)
H44A0.39740.27800.95360.083*
H44B0.44960.31871.01050.083*
H44C0.45610.34030.92930.083*
C451.08636 (17)0.07629 (16)0.87878 (17)0.0334 (7)
C461.10970 (19)0.10357 (15)0.94311 (16)0.0349 (7)
H461.09210.08160.98530.042*
C471.1593 (2)0.16357 (17)0.94580 (18)0.0395 (8)
H471.17640.18160.98990.047*
C481.18389 (19)0.19698 (16)0.88388 (18)0.0362 (7)
C491.1608 (2)0.16852 (19)0.81970 (18)0.0432 (8)
H491.17820.19040.77740.052*
C501.1128 (2)0.10860 (18)0.81715 (18)0.0499 (9)
H501.09760.08920.77300.060*
C511.23154 (19)0.26405 (17)0.88868 (19)0.0368 (7)
O521.25322 (14)0.29130 (13)0.94280 (13)0.0462 (6)
O531.24663 (14)0.29217 (12)0.82525 (12)0.0442 (6)
C541.2889 (2)0.3603 (2)0.8260 (2)0.0533 (10)
H54A1.33950.35210.84650.080*
H54B1.29450.37840.77780.080*
H54C1.26110.39660.85410.080*
C551.1088 (2)0.30510 (16)0.88496 (18)0.0395 (8)
C561.1415 (3)0.3229 (3)0.9488 (2)0.0734 (14)
H561.12100.30260.99070.088*
C571.2037 (3)0.3699 (3)0.9530 (2)0.0759 (14)
H571.22390.38280.99750.091*
C581.2362 (2)0.39784 (16)0.89312 (18)0.0392 (8)
C591.2031 (2)0.38239 (18)0.82961 (18)0.0474 (9)
H591.22360.40320.78800.057*
C601.1395 (2)0.33632 (19)0.82566 (19)0.0477 (9)
H601.11710.32640.78130.057*
C611.3056 (2)0.44488 (17)0.89395 (18)0.0405 (8)
O621.33303 (16)0.47399 (13)0.84440 (14)0.0589 (7)
O631.3199 (3)0.4710 (3)0.9587 (3)0.0366 (16)*0.459 (8)
C641.3872 (5)0.5155 (4)0.9640 (5)0.050 (2)*0.459 (8)
H64A1.43240.48570.95410.076*0.459 (8)
H64B1.39100.53571.01160.076*0.459 (8)
H64C1.38420.55570.93000.076*0.459 (8)
O63'1.3464 (3)0.4368 (3)0.9566 (2)0.0428 (15)*0.541 (8)
C64'1.4169 (4)0.4769 (4)0.9609 (4)0.053 (2)*0.541 (8)
H64D1.44620.46990.91760.079*0.541 (8)
H64E1.44680.45921.00090.079*0.541 (8)
H64F1.40580.52910.96710.079*0.541 (8)
N650.91784 (14)0.11949 (14)0.73862 (13)0.0364 (6)
C660.9470 (2)0.1751 (2)0.7035 (2)0.0542 (10)
H660.95700.21920.72820.065*
C670.9637 (3)0.1724 (2)0.6329 (2)0.0617 (12)
H670.98380.21420.60970.074*
C680.9512 (2)0.1092 (2)0.5967 (2)0.0570 (11)
H680.96400.10560.54840.068*
C690.9193 (3)0.0506 (2)0.6321 (2)0.0623 (12)
H690.90840.00620.60810.075*
C700.9038 (3)0.0576 (2)0.70255 (19)0.0550 (10)
H700.88230.01700.72670.066*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn0.03308 (18)0.03430 (17)0.03285 (19)0.00200 (16)0.00086 (17)0.00002 (16)
C10.045 (2)0.0358 (17)0.0314 (19)0.0079 (14)0.0030 (15)0.0031 (13)
C20.046 (2)0.0327 (17)0.039 (2)0.0066 (13)0.0066 (16)0.0030 (13)
C30.055 (2)0.0286 (16)0.040 (2)0.0019 (13)0.0044 (16)0.0002 (12)
C40.0440 (19)0.0391 (16)0.0259 (18)0.0016 (14)0.0016 (15)0.0003 (13)
C50.0392 (18)0.0353 (16)0.0286 (19)0.0022 (13)0.0037 (15)0.0046 (13)
C60.0335 (17)0.0336 (15)0.0305 (18)0.0021 (12)0.0003 (14)0.0003 (13)
C70.0343 (17)0.0380 (16)0.0321 (19)0.0070 (13)0.0012 (15)0.0009 (13)
C80.0301 (17)0.0465 (17)0.035 (2)0.0018 (14)0.0010 (15)0.0002 (13)
C90.0284 (16)0.0345 (15)0.0337 (19)0.0017 (12)0.0022 (14)0.0022 (13)
C100.0281 (16)0.0365 (15)0.0318 (18)0.0059 (12)0.0011 (14)0.0008 (13)
C110.0357 (18)0.0282 (15)0.0352 (19)0.0039 (12)0.0055 (15)0.0021 (12)
C120.0433 (19)0.0328 (16)0.041 (2)0.0019 (13)0.0005 (17)0.0004 (13)
C130.0425 (19)0.0333 (16)0.038 (2)0.0044 (12)0.0004 (15)0.0025 (13)
C140.0314 (17)0.0379 (16)0.035 (2)0.0051 (13)0.0022 (14)0.0022 (13)
C150.0357 (19)0.0398 (17)0.0269 (17)0.0045 (13)0.0008 (14)0.0020 (13)
C160.0235 (17)0.0456 (18)0.0299 (17)0.0015 (13)0.0009 (14)0.0028 (14)
C170.0324 (19)0.054 (2)0.041 (2)0.0000 (15)0.0011 (16)0.0038 (16)
C180.036 (2)0.0500 (19)0.0341 (19)0.0115 (15)0.0013 (16)0.0047 (14)
C190.040 (2)0.0434 (18)0.0286 (17)0.0064 (15)0.0033 (15)0.0079 (14)
C200.0334 (18)0.0424 (18)0.0331 (19)0.0099 (14)0.0003 (15)0.0048 (14)
N210.0347 (14)0.0374 (13)0.0296 (15)0.0009 (12)0.0009 (13)0.0021 (10)
N220.0317 (13)0.0325 (12)0.0300 (14)0.0029 (11)0.0002 (11)0.0035 (12)
N230.0346 (15)0.0382 (13)0.0322 (15)0.0008 (11)0.0057 (13)0.0016 (10)
N240.0299 (13)0.0347 (13)0.0352 (14)0.0026 (12)0.0009 (11)0.0009 (12)
C250.0389 (18)0.0335 (15)0.0359 (19)0.0003 (13)0.0012 (16)0.0043 (14)
C260.0356 (19)0.0402 (16)0.0299 (17)0.0012 (14)0.0011 (15)0.0026 (13)
C270.0309 (18)0.0381 (16)0.0402 (19)0.0026 (13)0.0049 (14)0.0001 (13)
C280.0357 (18)0.0370 (15)0.0367 (17)0.0012 (12)0.0014 (16)0.0027 (14)
C290.055 (2)0.0507 (19)0.0313 (19)0.0060 (18)0.0012 (17)0.0055 (15)
C300.056 (2)0.0404 (17)0.0340 (18)0.0073 (18)0.0056 (16)0.0032 (16)
C310.0333 (17)0.0445 (17)0.038 (2)0.0029 (13)0.0007 (16)0.0041 (15)
O320.0625 (18)0.0527 (14)0.0451 (16)0.0179 (12)0.0035 (13)0.0131 (12)
O330.0474 (15)0.0560 (14)0.0400 (15)0.0216 (12)0.0080 (12)0.0082 (11)
C340.069 (3)0.075 (3)0.061 (3)0.045 (2)0.012 (2)0.001 (2)
C350.0337 (18)0.0313 (15)0.0320 (19)0.0018 (13)0.0036 (14)0.0033 (12)
C360.0346 (18)0.0360 (16)0.0321 (17)0.0018 (13)0.0019 (14)0.0039 (13)
C370.0345 (17)0.0427 (18)0.0302 (16)0.0019 (13)0.0046 (13)0.0006 (13)
C380.0319 (17)0.0383 (16)0.0309 (17)0.0000 (13)0.0011 (14)0.0002 (13)
C390.0343 (18)0.0460 (17)0.0278 (18)0.0093 (14)0.0023 (14)0.0044 (13)
C400.0371 (18)0.0395 (17)0.0316 (18)0.0082 (14)0.0009 (15)0.0006 (13)
C410.0353 (19)0.0426 (18)0.0345 (19)0.0048 (14)0.0009 (16)0.0004 (14)
O420.0498 (15)0.0597 (14)0.0482 (16)0.0191 (12)0.0098 (14)0.0058 (13)
O430.0460 (15)0.0564 (14)0.0420 (15)0.0182 (12)0.0024 (12)0.0089 (11)
C440.046 (2)0.068 (2)0.051 (2)0.0219 (19)0.0032 (19)0.0079 (19)
C450.0258 (18)0.0388 (16)0.0355 (18)0.0008 (12)0.0031 (14)0.0067 (13)
C460.0406 (19)0.0375 (16)0.0267 (16)0.0039 (14)0.0035 (15)0.0036 (12)
C470.046 (2)0.0401 (17)0.0325 (19)0.0008 (15)0.0085 (16)0.0006 (14)
C480.0322 (17)0.0395 (17)0.0369 (19)0.0001 (13)0.0015 (15)0.0040 (14)
C490.041 (2)0.062 (2)0.0271 (17)0.0157 (17)0.0079 (16)0.0010 (15)
C500.058 (2)0.060 (2)0.0325 (18)0.0224 (18)0.0007 (18)0.0059 (15)
C510.0278 (17)0.0450 (18)0.037 (2)0.0021 (14)0.0015 (15)0.0003 (15)
O520.0457 (15)0.0579 (14)0.0350 (14)0.0153 (12)0.0004 (12)0.0083 (11)
O530.0453 (15)0.0510 (13)0.0363 (14)0.0173 (11)0.0004 (11)0.0018 (10)
C540.045 (2)0.065 (2)0.050 (2)0.0247 (18)0.0048 (18)0.0038 (17)
C550.040 (2)0.0388 (16)0.0397 (18)0.0040 (15)0.0029 (17)0.0048 (14)
C560.084 (3)0.108 (3)0.028 (2)0.060 (3)0.010 (2)0.008 (2)
C570.088 (3)0.109 (3)0.031 (2)0.062 (3)0.002 (2)0.004 (2)
C580.043 (2)0.0386 (17)0.0355 (19)0.0113 (14)0.0059 (16)0.0062 (13)
C590.060 (2)0.0467 (19)0.0354 (19)0.0172 (18)0.0042 (16)0.0058 (15)
C600.058 (2)0.0516 (19)0.034 (2)0.0120 (17)0.0080 (17)0.0046 (15)
C610.046 (2)0.0430 (18)0.0322 (19)0.0125 (15)0.0015 (16)0.0052 (15)
O620.0722 (19)0.0656 (15)0.0389 (15)0.0358 (14)0.0041 (15)0.0011 (12)
N650.0322 (15)0.0391 (13)0.0378 (14)0.0027 (12)0.0015 (11)0.0006 (12)
C660.069 (3)0.047 (2)0.046 (2)0.0076 (18)0.010 (2)0.0018 (17)
C670.089 (3)0.055 (2)0.042 (3)0.003 (2)0.014 (2)0.0078 (18)
C680.063 (3)0.071 (3)0.037 (2)0.020 (2)0.0033 (19)0.0030 (18)
C690.086 (3)0.060 (2)0.040 (2)0.003 (2)0.001 (2)0.0131 (17)
C700.073 (3)0.054 (2)0.038 (2)0.015 (2)0.006 (2)0.0044 (16)
Geometric parameters (Å, º) top
Zn—N222.070 (2)C36—H360.9500
Zn—N212.075 (2)C37—C381.395 (4)
Zn—N232.076 (2)C37—H370.9500
Zn—N242.077 (3)C38—C391.390 (4)
Zn—N652.148 (3)C38—C411.487 (4)
C1—N211.381 (4)C39—C401.381 (4)
C1—C201.399 (5)C39—H390.9500
C1—C21.433 (4)C40—H400.9500
C2—C31.353 (5)C41—O421.212 (4)
C2—H20.9500C41—O431.344 (4)
C3—C41.449 (4)O43—C441.442 (4)
C3—H30.9500C44—H44A0.9800
C4—N211.365 (4)C44—H44B0.9800
C4—C51.406 (5)C44—H44C0.9800
C5—C61.409 (4)C45—C461.385 (4)
C5—C251.497 (4)C45—C501.393 (5)
C6—N221.365 (4)C46—C471.399 (4)
C6—C71.439 (5)C46—H460.9500
C7—C81.371 (4)C47—C481.396 (5)
C7—H70.9500C47—H470.9500
C8—C91.457 (4)C48—C491.389 (5)
C8—H80.9500C48—C511.484 (4)
C9—N221.378 (4)C49—C501.381 (5)
C9—C101.408 (4)C49—H490.9500
C10—C111.415 (5)C50—H500.9500
C10—C351.490 (4)C51—O521.206 (4)
C11—N231.370 (4)C51—O531.339 (4)
C11—C121.446 (4)O53—C541.447 (4)
C12—C131.350 (5)C54—H54A0.9800
C12—H120.9500C54—H54B0.9800
C13—C141.430 (4)C54—H54C0.9800
C13—H130.9500C55—C601.375 (5)
C14—N231.368 (4)C55—C561.384 (5)
C14—C151.396 (5)C56—C571.386 (5)
C15—C161.397 (4)C56—H560.9500
C15—C451.515 (4)C57—C581.373 (5)
C16—N241.361 (4)C57—H570.9500
C16—C171.449 (4)C58—C591.371 (5)
C17—C181.360 (5)C58—C611.487 (5)
C17—H170.9500C59—C601.397 (5)
C18—C191.449 (5)C59—H590.9500
C18—H180.9500C60—H600.9500
C19—N241.382 (4)C61—O621.185 (4)
C19—C201.401 (5)C61—O631.346 (6)
C20—C551.497 (4)C61—O63'1.398 (6)
C25—C261.380 (5)O63—C641.435 (9)
C25—C301.394 (5)C64—H64A0.9800
C26—C271.383 (4)C64—H64B0.9800
C26—H260.9500C64—H64C0.9800
C27—C281.380 (4)O63'—C64'1.438 (8)
C27—H270.9500C64'—H64D0.9800
C28—C291.385 (5)C64'—H64E0.9800
C28—C311.501 (4)C64'—H64F0.9800
C29—C301.374 (5)N65—C661.318 (4)
C29—H290.9500N65—C701.345 (4)
C30—H300.9500C66—C671.377 (6)
C31—O321.193 (4)C66—H660.9500
C31—O331.337 (4)C67—C681.361 (6)
O33—C341.432 (4)C67—H670.9500
C34—H34A0.9800C68—C691.383 (6)
C34—H34B0.9800C68—H680.9500
C34—H34C0.9800C69—C701.376 (5)
C35—C361.388 (4)C69—H690.9500
C35—C401.395 (4)C70—H700.9500
C36—C371.378 (4)
N22—Zn—N2188.57 (10)H34A—C34—H34C109.5
N22—Zn—N2388.66 (10)H34B—C34—H34C109.5
N21—Zn—N23162.31 (9)C36—C35—C40118.4 (3)
N22—Zn—N24159.97 (10)C36—C35—C10121.6 (3)
N21—Zn—N2488.21 (10)C40—C35—C10120.0 (3)
N23—Zn—N2488.42 (11)C37—C36—C35121.4 (3)
N22—Zn—N65103.49 (10)C37—C36—H36119.3
N21—Zn—N65101.28 (10)C35—C36—H36119.3
N23—Zn—N6596.36 (10)C36—C37—C38119.6 (3)
N24—Zn—N6596.53 (10)C36—C37—H37120.2
N21—C1—C20125.6 (3)C38—C37—H37120.2
N21—C1—C2109.3 (3)C39—C38—C37119.7 (3)
C20—C1—C2125.0 (3)C39—C38—C41121.5 (3)
C3—C2—C1107.4 (3)C37—C38—C41118.8 (3)
C3—C2—H2126.3C40—C39—C38120.0 (3)
C1—C2—H2126.3C40—C39—H39120.0
C2—C3—C4107.1 (3)C38—C39—H39120.0
C2—C3—H3126.5C39—C40—C35120.8 (3)
C4—C3—H3126.5C39—C40—H40119.6
N21—C4—C5126.0 (3)C35—C40—H40119.6
N21—C4—C3109.2 (3)O42—C41—O43123.5 (3)
C5—C4—C3124.9 (3)O42—C41—C38124.8 (3)
C4—C5—C6125.0 (3)O43—C41—C38111.7 (3)
C4—C5—C25117.1 (3)C41—O43—C44115.4 (3)
C6—C5—C25117.9 (3)O43—C44—H44A109.5
N22—C6—C5125.6 (3)O43—C44—H44B109.5
N22—C6—C7110.5 (2)H44A—C44—H44B109.5
C5—C6—C7123.8 (3)O43—C44—H44C109.5
C8—C7—C6107.0 (3)H44A—C44—H44C109.5
C8—C7—H7126.5H44B—C44—H44C109.5
C6—C7—H7126.5C46—C45—C50119.7 (3)
C7—C8—C9106.2 (3)C46—C45—C15120.2 (3)
C7—C8—H8126.9C50—C45—C15120.1 (3)
C9—C8—H8126.9C45—C46—C47119.8 (3)
N22—C9—C10126.5 (3)C45—C46—H46120.1
N22—C9—C8109.8 (2)C47—C46—H46120.1
C10—C9—C8123.7 (3)C48—C47—C46120.2 (3)
C9—C10—C11124.4 (3)C48—C47—H47119.9
C9—C10—C35118.2 (3)C46—C47—H47119.9
C11—C10—C35117.3 (3)C49—C48—C47119.4 (3)
N23—C11—C10125.6 (3)C49—C48—C51121.7 (3)
N23—C11—C12109.4 (3)C47—C48—C51118.8 (3)
C10—C11—C12125.0 (3)C50—C49—C48120.3 (3)
C13—C12—C11106.4 (3)C50—C49—H49119.8
C13—C12—H12126.8C48—C49—H49119.8
C11—C12—H12126.8C49—C50—C45120.5 (3)
C12—C13—C14108.0 (3)C49—C50—H50119.7
C12—C13—H13126.0C45—C50—H50119.7
C14—C13—H13126.0O52—C51—O53123.5 (3)
N23—C14—C15124.7 (3)O52—C51—C48124.7 (3)
N23—C14—C13109.2 (3)O53—C51—C48111.8 (3)
C15—C14—C13125.9 (3)C51—O53—C54114.9 (3)
C14—C15—C16127.0 (3)O53—C54—H54A109.5
C14—C15—C45115.2 (3)O53—C54—H54B109.5
C16—C15—C45117.8 (3)H54A—C54—H54B109.5
N24—C16—C15124.7 (3)O53—C54—H54C109.5
N24—C16—C17111.1 (3)H54A—C54—H54C109.5
C15—C16—C17124.2 (3)H54B—C54—H54C109.5
C18—C17—C16105.9 (3)C60—C55—C56117.6 (3)
C18—C17—H17127.0C60—C55—C20121.3 (3)
C16—C17—H17127.0C56—C55—C20121.0 (3)
C17—C18—C19107.5 (3)C55—C56—C57121.3 (4)
C17—C18—H18126.3C55—C56—H56119.3
C19—C18—H18126.3C57—C56—H56119.3
N24—C19—C20125.1 (3)C58—C57—C56120.6 (4)
N24—C19—C18109.4 (3)C58—C57—H57119.7
C20—C19—C18125.4 (3)C56—C57—H57119.7
C1—C20—C19125.8 (3)C59—C58—C57118.7 (3)
C1—C20—C55118.1 (3)C59—C58—C61118.2 (3)
C19—C20—C55116.1 (3)C57—C58—C61123.0 (3)
C4—N21—C1107.1 (2)C58—C59—C60120.5 (3)
C4—N21—Zn126.3 (2)C58—C59—H59119.7
C1—N21—Zn126.1 (2)C60—C59—H59119.7
C6—N22—C9106.5 (2)C55—C60—C59121.1 (3)
C6—N22—Zn126.9 (2)C55—C60—H60119.4
C9—N22—Zn126.55 (19)C59—C60—H60119.4
C14—N23—C11107.0 (2)O62—C61—O63119.7 (3)
C14—N23—Zn125.1 (2)O62—C61—O63'121.4 (3)
C11—N23—Zn126.7 (2)O62—C61—C58125.5 (3)
C16—N24—C19106.1 (3)O63—C61—C58111.5 (3)
C16—N24—Zn126.3 (2)O63'—C61—C58111.4 (3)
C19—N24—Zn126.8 (2)C61—O63—C64114.7 (5)
C26—C25—C30118.4 (3)C61—O63'—C64'115.6 (5)
C26—C25—C5120.7 (3)O63'—C64'—H64D109.5
C30—C25—C5120.9 (3)O63'—C64'—H64E109.5
C25—C26—C27121.1 (3)H64D—C64'—H64E109.5
C25—C26—H26119.4O63'—C64'—H64F109.5
C27—C26—H26119.4H64D—C64'—H64F109.5
C28—C27—C26119.9 (3)H64E—C64'—H64F109.5
C28—C27—H27120.1C66—N65—C70117.2 (3)
C26—C27—H27120.1C66—N65—Zn121.6 (2)
C27—C28—C29119.6 (3)C70—N65—Zn121.1 (2)
C27—C28—C31122.5 (3)N65—C66—C67123.4 (4)
C29—C28—C31117.9 (3)N65—C66—H66118.3
C30—C29—C28120.2 (3)C67—C66—H66118.3
C30—C29—H29119.9C68—C67—C66119.3 (4)
C28—C29—H29119.9C68—C67—H67120.3
C29—C30—C25120.7 (3)C66—C67—H67120.3
C29—C30—H30119.6C67—C68—C69118.3 (4)
C25—C30—H30119.6C67—C68—H68120.8
O32—C31—O33123.9 (3)C69—C68—H68120.8
O32—C31—C28125.1 (3)C70—C69—C68118.9 (4)
O33—C31—C28111.0 (3)C70—C69—H69120.6
C31—O33—C34114.8 (3)C68—C69—H69120.6
O33—C34—H34A109.5N65—C70—C69122.7 (4)
O33—C34—H34B109.5N65—C70—H70118.6
H34A—C34—H34B109.5C69—C70—H70118.6
O33—C34—H34C109.5

Experimental details

(I)(II)
Crystal data
Chemical formulaC52H38N4O8·1.904C6H5NO2[Zn(C52H36N4O8)(C5H5N)]
Mr1081.27989.32
Crystal system, space groupMonoclinic, C2/cOrthorhombic, P212121
Temperature (K)110110
a, b, c (Å)32.6249 (8), 7.0657 (2), 23.5160 (8)17.4965 (4), 18.2617 (2), 19.0558 (4)
α, β, γ (°)90, 100.2918 (9), 9090, 90, 90
V3)5333.6 (3)6088.6 (2)
Z44
Radiation typeMo KαMo Kα
µ (mm1)0.090.45
Crystal size (mm)0.35 × 0.20 × 0.150.45 × 0.40 × 0.30
Data collection
DiffractometerNonius KappaCCD area-detector
diffractometer
Nonius KappaCCD area-detector
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
20139, 6404, 3904 52179, 14686, 9268
Rint0.0540.085
(sin θ/λ)max1)0.6650.665
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.057, 0.158, 1.02 0.053, 0.131, 0.90
No. of reflections640414686
No. of parameters374649
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.30, 0.310.32, 0.40
Absolute structure?Flack (1983), with how many Friedel pairs?
Absolute structure parameter?0.259 (9)

Computer programs: COLLECT (Nonius, 1999), DENZO (Otwinowski & Minor, 1997), DENZO, SIR97 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996) and Mercury (Bruno et al., 2002), SHELXL97.

Apparent C—H···O interactions (Å, °) top
CompoundContactC—HH···OC···OC—H···O
(I)C2-H2···O43i0.952.453.357 (2)160
(I)C7-H7···O32ii0.952.303.197 (2)157
(I)C30-H30···O53iii0.952.513.296 (3)141
(I)C40-H40···O42iv0.952.433.233 (3)143
(II)C36-H36···O62v0.952.403.293 (4)147
(II)C46-H46···O32vi0.952.493.418 (4)164
 

Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds