Clathrate solvates of tetra­kis(4-methoxy­carbonyl­phenyl)porphyrin and its zinc(II)–pyridine complex, in which the porphyrin host structures are stabilized by porphyrin–porphyrin stacking and C—H...O attractions

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.

S1. Comment

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 C—H(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)].

S2. Experimental

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.

S3. Refinement

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 U_iso(H) = 1.2 or 1.5U_eq(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

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

	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.
	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.
	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.
	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).
	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.
	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

Crystal data

C52H38N4O8·1.904C6H5NO2	F(000) = 2255.4
Mr = 1081.27	Dx = 1.347 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 5804 reflections
a = 32.6249 (8) Å	θ = 1.4–28.2°
b = 7.0657 (2) Å	µ = 0.09 mm^−1
c = 23.5160 (8) Å	T = 110 K
β = 100.2918 (9)°	Prism, purple
V = 5333.6 (3) Å^3	0.35 × 0.20 × 0.15 mm
Z = 4

Data collection

Nonius KappaCCD area-detector diffractometer	3904 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.054
Graphite monochromator	θmax = 28.2°, θmin = 2.5°
Detector resolution: 56 microns pixels mm^-1	h = −41→42
1° ϕ scans	k = −9→9
20139 measured reflections	l = −30→30
6404 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.158	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0865P)^2] where P = (Fo^2 + 2Fc^2)/3
6404 reflections	(Δ/σ)max < 0.001
374 parameters	Δρmax = 0.30 e Å^−3
0 restraints	Δρmin = −0.31 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.01794 (6)	0.8569 (2)	0.57609 (8)	0.0225 (4)
C2	0.05179 (6)	0.9743 (2)	0.60418 (8)	0.0268 (4)
H2	0.0498	1.0753	0.6302	0.032*
C3	0.08700 (6)	0.9141 (3)	0.58675 (8)	0.0267 (4)
H3	0.1142	0.9654	0.5980	0.032*
C4	0.07533 (6)	0.7559 (2)	0.54757 (8)	0.0219 (4)
C5	0.10327 (6)	0.6434 (2)	0.52340 (8)	0.0214 (4)
C6	0.09243 (6)	0.4807 (2)	0.48956 (8)	0.0225 (4)
C7	0.12050 (6)	0.3752 (2)	0.46072 (8)	0.0263 (4)
H7	0.1494	0.3992	0.4627	0.032*
C8	0.09816 (6)	0.2353 (2)	0.43024 (8)	0.0253 (4)
H8	0.1085	0.1434	0.4070	0.030*
C9	0.05584 (6)	0.2511 (2)	0.43945 (8)	0.0218 (4)
C10	0.02313 (6)	0.1327 (2)	0.41470 (7)	0.0209 (4)
N21	0.03333 (5)	0.7275 (2)	0.54152 (6)	0.0219 (3)
H21	0.0187	0.6419	0.5194	0.026*	0.42 (3)
N22	0.05349 (5)	0.40154 (19)	0.47576 (6)	0.0213 (3)
H22	0.0310	0.4403	0.4880	0.026*	0.58 (3)
C25	0.14841 (6)	0.6943 (2)	0.53676 (8)	0.0234 (4)
C26	0.16281 (6)	0.8703 (2)	0.52233 (8)	0.0262 (4)
H26	0.1437	0.9602	0.5028	0.031*
C27	0.20474 (6)	0.9158 (3)	0.53610 (8)	0.0282 (4)
H27	0.2141	1.0366	0.5261	0.034*
C28	0.23312 (6)	0.7851 (3)	0.56453 (8)	0.0269 (4)
C29	0.21900 (6)	0.6082 (3)	0.57865 (9)	0.0302 (5)
H29	0.2382	0.5180	0.5979	0.036*
C30	0.17714 (6)	0.5630 (3)	0.56483 (8)	0.0286 (4)
H30	0.1678	0.4417	0.5745	0.034*
C31	0.27768 (6)	0.8404 (3)	0.58030 (9)	0.0312 (5)
O32	0.29167 (4)	0.98904 (19)	0.56696 (6)	0.0371 (4)
O33	0.30050 (4)	0.7072 (2)	0.61223 (6)	0.0391 (4)
C34	0.34423 (6)	0.7499 (3)	0.63104 (10)	0.0427 (6)
H34A	0.3579	0.7594	0.5973	0.064*
H34B	0.3573	0.6488	0.6565	0.064*
H34C	0.3470	0.8704	0.6520	0.064*
C35	0.03307 (6)	−0.0104 (2)	0.37180 (8)	0.0215 (4)
C36	0.03409 (6)	−0.2035 (2)	0.38326 (8)	0.0251 (4)
H36	0.0274	−0.2487	0.4185	0.030*
C37	0.04484 (6)	−0.3303 (2)	0.34361 (8)	0.0265 (4)
H37	0.0457	−0.4619	0.3520	0.032*
C38	0.05444 (6)	−0.2671 (2)	0.29147 (8)	0.0224 (4)
C39	0.05297 (6)	−0.0736 (2)	0.27937 (8)	0.0256 (4)
H39	0.0592	−0.0286	0.2438	0.031*
C40	0.04238 (6)	0.0523 (2)	0.31945 (8)	0.0256 (4)
H40	0.0415	0.1839	0.3111	0.031*
C41	0.06699 (6)	−0.4071 (3)	0.25037 (8)	0.0273 (4)
O42	0.07392 (6)	−0.57220 (19)	0.26153 (7)	0.0516 (5)
O43	0.07053 (5)	−0.33006 (17)	0.19992 (6)	0.0337 (4)
C44	0.08314 (8)	−0.4569 (3)	0.15782 (9)	0.0414 (6)
H44A	0.1118	−0.4989	0.1715	0.062*
H44B	0.0815	−0.3906	0.1209	0.062*
H44C	0.0646	−0.5670	0.1525	0.062*
C45	0.23717 (10)	0.2379 (3)	0.22574 (10)	0.0476 (7)	0.952 (3)
H45	0.2539	0.2300	0.1967	0.057*	0.952 (3)
C46	0.19467 (10)	0.2266 (3)	0.21152 (12)	0.0536 (8)	0.952 (3)
H46	0.1817	0.2119	0.1722	0.064*	0.952 (3)
C47	0.17029 (10)	0.2366 (3)	0.25463 (14)	0.0597 (8)	0.952 (3)
H47	0.1408	0.2262	0.2449	0.072*	0.952 (3)
C48	0.18949 (13)	0.2618 (4)	0.31166 (13)	0.0663 (10)	0.952 (3)
H48	0.1730	0.2704	0.3410	0.080*	0.952 (3)
C49	0.23192 (12)	0.2744 (3)	0.32625 (12)	0.0608 (9)	0.952 (3)
H49	0.2450	0.2921	0.3653	0.073*	0.952 (3)
C50	0.25522 (10)	0.2611 (3)	0.28302 (11)	0.0482 (7)	0.952 (3)
N51	0.30073 (9)	0.2699 (3)	0.29829 (11)	0.0588 (7)	0.952 (3)
O52	0.32147 (7)	0.2423 (3)	0.26037 (10)	0.0733 (7)	0.952 (3)
O53	0.31635 (8)	0.3072 (3)	0.34878 (8)	0.0768 (8)	0.952 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0238 (11)	0.0217 (9)	0.0225 (10)	−0.0009 (7)	0.0058 (8)	0.0005 (7)
C2	0.0253 (11)	0.0284 (10)	0.0276 (11)	−0.0042 (8)	0.0071 (8)	−0.0060 (8)
C3	0.0234 (11)	0.0296 (10)	0.0271 (10)	−0.0049 (8)	0.0044 (8)	−0.0064 (8)
C4	0.0191 (10)	0.0246 (9)	0.0215 (9)	−0.0020 (7)	0.0026 (7)	0.0002 (7)
C5	0.0184 (10)	0.0247 (9)	0.0206 (10)	−0.0009 (7)	0.0021 (7)	0.0005 (7)
C6	0.0200 (10)	0.0233 (9)	0.0239 (10)	−0.0006 (7)	0.0031 (8)	0.0019 (7)
C7	0.0175 (10)	0.0278 (10)	0.0343 (11)	−0.0001 (7)	0.0063 (8)	−0.0021 (8)
C8	0.0210 (11)	0.0261 (9)	0.0296 (11)	0.0031 (7)	0.0069 (8)	−0.0016 (7)
C9	0.0207 (10)	0.0226 (9)	0.0226 (10)	0.0011 (7)	0.0052 (8)	−0.0004 (7)
C10	0.0206 (10)	0.0216 (9)	0.0203 (9)	0.0008 (7)	0.0037 (8)	0.0011 (7)
N21	0.0197 (9)	0.0231 (8)	0.0231 (8)	−0.0008 (6)	0.0043 (6)	−0.0025 (6)
N22	0.0175 (8)	0.0224 (7)	0.0240 (8)	−0.0009 (6)	0.0035 (6)	−0.0024 (6)
C25	0.0202 (10)	0.0276 (9)	0.0232 (10)	−0.0027 (7)	0.0057 (8)	−0.0044 (7)
C26	0.0223 (11)	0.0283 (10)	0.0277 (10)	0.0000 (8)	0.0036 (8)	−0.0038 (8)
C27	0.0247 (11)	0.0319 (10)	0.0289 (11)	−0.0061 (8)	0.0069 (8)	−0.0031 (8)
C28	0.0192 (10)	0.0347 (10)	0.0271 (10)	−0.0029 (8)	0.0050 (8)	−0.0066 (8)
C29	0.0220 (11)	0.0342 (10)	0.0325 (11)	0.0018 (8)	−0.0003 (9)	−0.0012 (8)
C30	0.0267 (11)	0.0268 (9)	0.0311 (11)	−0.0028 (8)	0.0022 (9)	−0.0017 (8)
C31	0.0227 (11)	0.0380 (11)	0.0338 (12)	−0.0025 (9)	0.0077 (9)	−0.0081 (9)
O32	0.0233 (8)	0.0446 (9)	0.0436 (9)	−0.0081 (6)	0.0069 (7)	−0.0072 (7)
O33	0.0206 (8)	0.0514 (9)	0.0428 (9)	−0.0031 (6)	−0.0013 (7)	0.0017 (7)
C34	0.0195 (12)	0.0577 (14)	0.0478 (14)	−0.0021 (10)	−0.0022 (10)	−0.0044 (11)
C35	0.0165 (10)	0.0236 (9)	0.0241 (10)	0.0004 (7)	0.0024 (8)	−0.0015 (7)
C36	0.0271 (11)	0.0261 (9)	0.0229 (10)	0.0006 (8)	0.0066 (8)	0.0022 (7)
C37	0.0281 (11)	0.0200 (9)	0.0319 (11)	0.0021 (7)	0.0067 (9)	0.0010 (7)
C38	0.0193 (10)	0.0254 (9)	0.0225 (10)	0.0008 (7)	0.0037 (8)	−0.0010 (7)
C39	0.0280 (11)	0.0242 (9)	0.0252 (10)	0.0008 (8)	0.0068 (8)	0.0000 (7)
C40	0.0289 (11)	0.0198 (9)	0.0285 (10)	0.0005 (7)	0.0062 (8)	0.0013 (7)
C41	0.0310 (12)	0.0227 (10)	0.0294 (11)	0.0007 (8)	0.0085 (9)	−0.0011 (8)
O42	0.0894 (14)	0.0248 (8)	0.0501 (10)	0.0082 (8)	0.0386 (10)	0.0015 (7)
O43	0.0497 (10)	0.0284 (7)	0.0246 (7)	0.0099 (6)	0.0109 (7)	−0.0004 (6)
C44	0.0641 (17)	0.0343 (11)	0.0294 (12)	0.0109 (10)	0.0182 (11)	−0.0051 (9)
C45	0.071 (2)	0.0384 (13)	0.0329 (14)	0.0148 (12)	0.0091 (13)	0.0008 (10)
C46	0.072 (2)	0.0428 (14)	0.0467 (16)	0.0114 (13)	0.0111 (15)	0.0081 (11)
C47	0.073 (2)	0.0370 (14)	0.073 (2)	0.0147 (13)	0.0249 (17)	0.0118 (13)
C48	0.115 (3)	0.0404 (15)	0.0529 (19)	0.0184 (16)	0.040 (2)	0.0068 (12)
C49	0.111 (3)	0.0346 (14)	0.0390 (16)	0.0191 (15)	0.0178 (17)	0.0026 (11)
C50	0.080 (2)	0.0271 (12)	0.0361 (14)	0.0147 (12)	0.0080 (14)	0.0018 (9)
N51	0.090 (2)	0.0366 (12)	0.0431 (15)	0.0131 (11)	−0.0056 (14)	0.0034 (10)
O52	0.0781 (17)	0.0744 (14)	0.0641 (15)	0.0183 (11)	0.0039 (13)	−0.0056 (11)
O53	0.118 (2)	0.0535 (12)	0.0458 (13)	0.0017 (11)	−0.0214 (12)	0.0056 (9)

Geometric parameters (Å, º)

C1—N21	1.376 (2)	O33—C34	1.448 (2)
C1—C10^i	1.397 (3)	C34—H34A	0.9800
C1—C2	1.443 (3)	C34—H34B	0.9800
C2—C3	1.355 (3)	C34—H34C	0.9800
C2—H2	0.9500	C35—C36	1.390 (2)
C3—C4	1.455 (2)	C35—C40	1.392 (3)
C3—H3	0.9500	C36—C37	1.383 (3)
C4—N21	1.367 (2)	C36—H36	0.9500
C4—C5	1.404 (3)	C37—C38	1.392 (3)
C5—C6	1.407 (2)	C37—H37	0.9500
C5—C25	1.494 (3)	C38—C39	1.395 (2)
C6—N22	1.373 (2)	C38—C41	1.491 (3)
C6—C7	1.441 (3)	C39—C40	1.384 (3)
C7—C8	1.355 (3)	C39—H39	0.9500
C7—H7	0.9500	C40—H40	0.9500
C8—C9	1.440 (3)	C41—O42	1.208 (2)
C8—H8	0.9500	C41—O43	1.329 (2)
C9—N22	1.374 (2)	O43—C44	1.448 (2)
C9—C10	1.398 (2)	C44—H44A	0.9800
C10—C1^i	1.397 (3)	C44—H44B	0.9800
C10—C35	1.504 (2)	C44—H44C	0.9800
N21—H21	0.8800	C45—C46	1.369 (4)
N22—H22	0.8800	C45—C50	1.380 (4)
C25—C26	1.393 (3)	C45—H45	0.9500
C25—C30	1.398 (3)	C46—C47	1.398 (4)
C26—C27	1.386 (3)	C46—H46	0.9500
C26—H26	0.9500	C47—C48	1.387 (4)
C27—C28	1.392 (3)	C47—H47	0.9500
C27—H27	0.9500	C48—C49	1.368 (5)
C28—C29	1.393 (3)	C48—H48	0.9500
C28—C31	1.487 (3)	C49—C50	1.377 (4)
C29—C30	1.383 (3)	C49—H49	0.9500
C29—H29	0.9500	C50—N51	1.465 (4)
C30—H30	0.9500	N51—O52	1.228 (3)
C31—O32	1.209 (2)	N51—O53	1.234 (3)
C31—O33	1.343 (2)
N21—C1—C10^i	126.00 (16)	C31—O33—C34	116.27 (16)
N21—C1—C2	108.78 (16)	O33—C34—H34A	109.5
C10^i—C1—C2	125.13 (16)	O33—C34—H34B	109.5
C3—C2—C1	107.57 (16)	H34A—C34—H34B	109.5
C3—C2—H2	126.2	O33—C34—H34C	109.5
C1—C2—H2	126.2	H34A—C34—H34C	109.5
C2—C3—C4	106.99 (17)	H34B—C34—H34C	109.5
C2—C3—H3	126.5	C36—C35—C40	118.84 (16)
C4—C3—H3	126.5	C36—C35—C10	122.03 (16)
N21—C4—C5	125.87 (16)	C40—C35—C10	119.12 (15)
N21—C4—C3	108.84 (16)	C37—C36—C35	120.35 (17)
C5—C4—C3	125.15 (17)	C37—C36—H36	119.8
C4—C5—C6	125.15 (17)	C35—C36—H36	119.8
C4—C5—C25	117.76 (15)	C36—C37—C38	120.67 (16)
C6—C5—C25	117.02 (16)	C36—C37—H37	119.7
N22—C6—C5	126.53 (16)	C38—C37—H37	119.7
N22—C6—C7	108.48 (15)	C37—C38—C39	119.28 (16)
C5—C6—C7	124.90 (17)	C37—C38—C41	119.27 (15)
C8—C7—C6	107.41 (17)	C39—C38—C41	121.44 (16)
C8—C7—H7	126.3	C40—C39—C38	119.64 (18)
C6—C7—H7	126.3	C40—C39—H39	120.2
C7—C8—C9	107.69 (16)	C38—C39—H39	120.2
C7—C8—H8	126.2	C39—C40—C35	121.22 (16)
C9—C8—H8	126.2	C39—C40—H40	119.4
N22—C9—C10	126.74 (17)	C35—C40—H40	119.4
N22—C9—C8	108.35 (15)	O42—C41—O43	123.15 (18)
C10—C9—C8	124.90 (16)	O42—C41—C38	124.24 (18)
C1^i—C10—C9	125.86 (16)	O43—C41—C38	112.61 (15)
C1^i—C10—C35	117.84 (15)	C41—O43—C44	115.92 (15)
C9—C10—C35	116.20 (16)	O43—C44—H44A	109.5
C4—N21—C1	107.80 (14)	O43—C44—H44B	109.5
C4—N21—H21	126.1	H44A—C44—H44B	109.5
C1—N21—H21	126.1	O43—C44—H44C	109.5
C6—N22—C9	108.06 (15)	H44A—C44—H44C	109.5
C6—N22—H22	126.0	H44B—C44—H44C	109.5
C9—N22—H22	126.0	C46—C45—C50	118.8 (3)
C26—C25—C30	118.74 (17)	C46—C45—H45	120.6
C26—C25—C5	121.75 (16)	C50—C45—H45	120.6
C30—C25—C5	119.51 (16)	C45—C46—C47	120.2 (3)
C27—C26—C25	120.81 (17)	C45—C46—H46	119.9
C27—C26—H26	119.6	C47—C46—H46	119.9
C25—C26—H26	119.6	C48—C47—C46	119.4 (3)
C26—C27—C28	120.15 (17)	C48—C47—H47	120.3
C26—C27—H27	119.9	C46—C47—H47	120.3
C28—C27—H27	119.9	C49—C48—C47	120.8 (3)
C27—C28—C29	119.35 (18)	C49—C48—H48	119.6
C27—C28—C31	118.83 (17)	C47—C48—H48	119.6
C29—C28—C31	121.80 (18)	C48—C49—C50	118.5 (3)
C30—C29—C28	120.40 (18)	C48—C49—H49	120.7
C30—C29—H29	119.8	C50—C49—H49	120.7
C28—C29—H29	119.8	C49—C50—C45	122.2 (3)
C29—C30—C25	120.55 (17)	C49—C50—N51	119.0 (3)
C29—C30—H30	119.7	C45—C50—N51	118.8 (3)
C25—C30—H30	119.7	O52—N51—O53	123.1 (3)
O32—C31—O33	123.81 (19)	O52—N51—C50	118.8 (2)
O32—C31—C28	124.16 (19)	O53—N51—C50	118.1 (3)
O33—C31—C28	112.02 (17)

Symmetry code: (i) −x, −y+1, −z+1.

(II) pyridine(tetramethyl 4,4',4'',4'''-porphyrin-5,10,15,20- tetrabenzoato)zinc(II)

Crystal data

[Zn(C52H36N4O8)(C5H5N)]	F(000) = 2048
Mr = 989.32	Dx = 1.079 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 7893 reflections
a = 17.4965 (4) Å	θ = 1.4–28.3°
b = 18.2617 (2) Å	µ = 0.45 mm^−1
c = 19.0558 (4) Å	T = 110 K
V = 6088.6 (2) Å^3	Prism, purple
Z = 4	0.45 × 0.40 × 0.30 mm

Data collection

Nonius KappaCCD area-detector diffractometer	9268 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.085
Graphite monochromator	θmax = 28.2°, θmin = 2.4°
Detector resolution: 56 microns pixels mm^-1	h = −23→23
1° ϕ and ω scans	k = −24→24
52179 measured reflections	l = −25→25
14686 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.053	H-atom parameters constrained
wR(F^2) = 0.131	w = 1/[σ^2(Fo^2) + (0.0727P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.90	(Δ/σ)max = 0.001
14686 reflections	Δρmax = 0.32 e Å^−3
649 parameters	Δρmin = −0.40 e Å^−3
0 restraints	Absolute structure: Flack (1983), with how many Friedel pairs?
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.259 (9)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Zn	0.89994 (2)	0.124742 (18)	0.850035 (19)	0.03341 (10)
C1	0.9702 (2)	0.27857 (16)	0.87265 (17)	0.0374 (8)
C2	0.9499 (2)	0.35456 (16)	0.87342 (18)	0.0393 (8)
H2	0.9842	0.3947	0.8769	0.047*
C3	0.8729 (2)	0.35870 (16)	0.86829 (18)	0.0412 (9)
H3	0.8431	0.4022	0.8667	0.049*
C4	0.8443 (2)	0.28425 (16)	0.86561 (16)	0.0363 (8)
C5	0.76666 (19)	0.26481 (16)	0.86173 (17)	0.0344 (7)
C6	0.73857 (18)	0.19248 (15)	0.86094 (17)	0.0325 (7)
C7	0.65873 (19)	0.17407 (16)	0.86533 (16)	0.0348 (7)
H7	0.6171	0.2075	0.8660	0.042*
C8	0.65413 (19)	0.09917 (17)	0.86845 (17)	0.0371 (8)
H8	0.6090	0.0706	0.8729	0.045*
C9	0.73235 (17)	0.07228 (16)	0.86347 (17)	0.0322 (7)
C10	0.75197 (19)	−0.00252 (16)	0.86438 (17)	0.0321 (7)
C11	0.82782 (18)	−0.02942 (15)	0.86372 (17)	0.0330 (7)
C12	0.8487 (2)	−0.10593 (16)	0.86056 (18)	0.0391 (8)
H12	0.8149	−0.1466	0.8582	0.047*
C13	0.92585 (19)	−0.10818 (16)	0.86155 (18)	0.0380 (8)
H13	0.9565	−0.1511	0.8593	0.046*
C14	0.95339 (19)	−0.03466 (16)	0.86656 (17)	0.0346 (8)
C15	1.02955 (19)	−0.01377 (17)	0.87538 (17)	0.0341 (7)
C16	1.05769 (18)	0.05742 (17)	0.88255 (17)	0.0330 (7)
C17	1.1377 (2)	0.07517 (19)	0.89241 (19)	0.0424 (8)
H17	1.1789	0.0417	0.8972	0.051*
C18	1.1416 (2)	0.14954 (17)	0.89340 (18)	0.0401 (8)
H18	1.1867	0.1781	0.8987	0.048*
C19	1.0646 (2)	0.17725 (18)	0.88490 (18)	0.0375 (8)
C20	1.04438 (19)	0.25132 (17)	0.88055 (18)	0.0363 (8)
N21	0.90461 (16)	0.23682 (13)	0.86736 (13)	0.0339 (6)
N22	0.78224 (14)	0.13053 (13)	0.85949 (13)	0.0314 (5)
N23	0.89268 (16)	0.01251 (13)	0.86612 (13)	0.0350 (6)
N24	1.01446 (14)	0.11919 (14)	0.87833 (13)	0.0332 (6)
C25	0.70989 (19)	0.32599 (16)	0.85815 (18)	0.0361 (7)
C26	0.67003 (19)	0.33975 (16)	0.79708 (17)	0.0352 (7)
H26	0.6748	0.3070	0.7586	0.042*
C27	0.62323 (18)	0.40040 (16)	0.79090 (19)	0.0364 (7)
H27	0.5976	0.4100	0.7479	0.044*
C28	0.61381 (18)	0.44695 (15)	0.84728 (18)	0.0365 (7)
C29	0.6505 (2)	0.43180 (19)	0.91001 (18)	0.0458 (9)
H29	0.6425	0.4625	0.9496	0.055*
C30	0.6986 (2)	0.37253 (19)	0.91518 (17)	0.0435 (8)
H30	0.7245	0.3632	0.9581	0.052*
C31	0.56715 (19)	0.51575 (17)	0.84285 (19)	0.0386 (7)
O32	0.55594 (16)	0.55700 (13)	0.89032 (14)	0.0534 (7)
O33	0.53937 (15)	0.52526 (12)	0.77811 (13)	0.0478 (6)
C34	0.4947 (3)	0.5902 (2)	0.7689 (2)	0.0685 (12)
H34A	0.4425	0.5814	0.7857	0.103*
H34B	0.4932	0.6032	0.7190	0.103*
H34C	0.5176	0.6304	0.7957	0.103*
C35	0.68918 (18)	−0.05729 (15)	0.87038 (16)	0.0323 (7)
C36	0.63378 (18)	−0.06445 (16)	0.81869 (17)	0.0342 (7)
H36	0.6362	−0.0341	0.7783	0.041*
C37	0.57539 (18)	−0.11467 (16)	0.82469 (16)	0.0358 (7)
H37	0.5377	−0.1184	0.7890	0.043*
C38	0.57195 (18)	−0.16001 (16)	0.88350 (17)	0.0337 (7)
C39	0.62810 (18)	−0.15483 (17)	0.93490 (17)	0.0360 (8)
H39	0.6270	−0.1867	0.9743	0.043*
C40	0.6855 (2)	−0.10329 (16)	0.92871 (18)	0.0361 (8)
H40	0.7229	−0.0991	0.9646	0.043*
C41	0.5083 (2)	−0.21362 (17)	0.88923 (18)	0.0375 (7)
O42	0.46463 (14)	−0.22907 (13)	0.84207 (15)	0.0525 (6)
O43	0.50618 (14)	−0.24527 (13)	0.95289 (13)	0.0481 (6)
C44	0.4476 (2)	−0.2999 (2)	0.9623 (2)	0.0550 (10)
H44A	0.3974	−0.2780	0.9536	0.083*
H44B	0.4496	−0.3187	1.0105	0.083*
H44C	0.4561	−0.3403	0.9293	0.083*
C45	1.08636 (17)	−0.07629 (16)	0.87878 (17)	0.0334 (7)
C46	1.10970 (19)	−0.10357 (15)	0.94311 (16)	0.0349 (7)
H46	1.0921	−0.0816	0.9853	0.042*
C47	1.1593 (2)	−0.16357 (17)	0.94580 (18)	0.0395 (8)
H47	1.1764	−0.1816	0.9899	0.047*
C48	1.18389 (19)	−0.19698 (16)	0.88388 (18)	0.0362 (7)
C49	1.1608 (2)	−0.16852 (19)	0.81970 (18)	0.0432 (8)
H49	1.1782	−0.1904	0.7774	0.052*
C50	1.1128 (2)	−0.10860 (18)	0.81715 (18)	0.0499 (9)
H50	1.0976	−0.0892	0.7730	0.060*
C51	1.23154 (19)	−0.26405 (17)	0.88868 (19)	0.0368 (7)
O52	1.25322 (14)	−0.29130 (13)	0.94280 (13)	0.0462 (6)
O53	1.24663 (14)	−0.29217 (12)	0.82525 (12)	0.0442 (6)
C54	1.2889 (2)	−0.3603 (2)	0.8260 (2)	0.0533 (10)
H54A	1.3395	−0.3521	0.8465	0.080*
H54B	1.2945	−0.3784	0.7778	0.080*
H54C	1.2611	−0.3966	0.8541	0.080*
C55	1.1088 (2)	0.30510 (16)	0.88496 (18)	0.0395 (8)
C56	1.1415 (3)	0.3229 (3)	0.9488 (2)	0.0734 (14)
H56	1.1210	0.3026	0.9907	0.088*
C57	1.2037 (3)	0.3699 (3)	0.9530 (2)	0.0759 (14)
H57	1.2239	0.3828	0.9975	0.091*
C58	1.2362 (2)	0.39784 (16)	0.89312 (18)	0.0392 (8)
C59	1.2031 (2)	0.38239 (18)	0.82961 (18)	0.0474 (9)
H59	1.2236	0.4032	0.7880	0.057*
C60	1.1395 (2)	0.33632 (19)	0.82566 (19)	0.0477 (9)
H60	1.1171	0.3264	0.7813	0.057*
C61	1.3056 (2)	0.44488 (17)	0.89395 (18)	0.0405 (8)
O62	1.33303 (16)	0.47399 (13)	0.84440 (14)	0.0589 (7)
O63	1.3199 (3)	0.4710 (3)	0.9587 (3)	0.0366 (16)*	0.459 (8)
C64	1.3872 (5)	0.5155 (4)	0.9640 (5)	0.050 (2)*	0.459 (8)
H64A	1.4324	0.4857	0.9541	0.076*	0.459 (8)
H64B	1.3910	0.5357	1.0116	0.076*	0.459 (8)
H64C	1.3842	0.5557	0.9300	0.076*	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)
H64D	1.4462	0.4699	0.9176	0.079*	0.541 (8)
H64E	1.4468	0.4592	1.0009	0.079*	0.541 (8)
H64F	1.4058	0.5291	0.9671	0.079*	0.541 (8)
N65	0.91784 (14)	0.11949 (14)	0.73862 (13)	0.0364 (6)
C66	0.9470 (2)	0.1751 (2)	0.7035 (2)	0.0542 (10)
H66	0.9570	0.2192	0.7282	0.065*
C67	0.9637 (3)	0.1724 (2)	0.6329 (2)	0.0617 (12)
H67	0.9838	0.2142	0.6097	0.074*
C68	0.9512 (2)	0.1092 (2)	0.5967 (2)	0.0570 (11)
H68	0.9640	0.1056	0.5484	0.068*
C69	0.9193 (3)	0.0506 (2)	0.6321 (2)	0.0623 (12)
H69	0.9084	0.0062	0.6081	0.075*
C70	0.9038 (3)	0.0576 (2)	0.70255 (19)	0.0550 (10)
H70	0.8823	0.0170	0.7267	0.066*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn	0.03308 (18)	0.03430 (17)	0.03285 (19)	−0.00200 (16)	0.00086 (17)	0.00002 (16)
C1	0.045 (2)	0.0358 (17)	0.0314 (19)	−0.0079 (14)	0.0030 (15)	−0.0031 (13)
C2	0.046 (2)	0.0327 (17)	0.039 (2)	−0.0066 (13)	0.0066 (16)	0.0030 (13)
C3	0.055 (2)	0.0286 (16)	0.040 (2)	−0.0019 (13)	0.0044 (16)	0.0002 (12)
C4	0.0440 (19)	0.0391 (16)	0.0259 (18)	−0.0016 (14)	0.0016 (15)	−0.0003 (13)
C5	0.0392 (18)	0.0353 (16)	0.0286 (19)	0.0022 (13)	0.0037 (15)	0.0046 (13)
C6	0.0335 (17)	0.0336 (15)	0.0305 (18)	0.0021 (12)	−0.0003 (14)	0.0003 (13)
C7	0.0343 (17)	0.0380 (16)	0.0321 (19)	0.0070 (13)	0.0012 (15)	−0.0009 (13)
C8	0.0301 (17)	0.0465 (17)	0.035 (2)	−0.0018 (14)	0.0010 (15)	0.0002 (13)
C9	0.0284 (16)	0.0345 (15)	0.0337 (19)	0.0017 (12)	0.0022 (14)	0.0022 (13)
C10	0.0281 (16)	0.0365 (15)	0.0318 (18)	−0.0059 (12)	−0.0011 (14)	0.0008 (13)
C11	0.0357 (18)	0.0282 (15)	0.0352 (19)	−0.0039 (12)	0.0055 (15)	−0.0021 (12)
C12	0.0433 (19)	0.0328 (16)	0.041 (2)	−0.0019 (13)	0.0005 (17)	0.0004 (13)
C13	0.0425 (19)	0.0333 (16)	0.038 (2)	0.0044 (12)	0.0004 (15)	0.0025 (13)
C14	0.0314 (17)	0.0379 (16)	0.035 (2)	0.0051 (13)	0.0022 (14)	0.0022 (13)
C15	0.0357 (19)	0.0398 (17)	0.0269 (17)	0.0045 (13)	0.0008 (14)	−0.0020 (13)
C16	0.0235 (17)	0.0456 (18)	0.0299 (17)	0.0015 (13)	0.0009 (14)	−0.0028 (14)
C17	0.0324 (19)	0.054 (2)	0.041 (2)	0.0000 (15)	−0.0011 (16)	−0.0038 (16)
C18	0.036 (2)	0.0500 (19)	0.0341 (19)	−0.0115 (15)	−0.0013 (16)	−0.0047 (14)
C19	0.040 (2)	0.0434 (18)	0.0286 (17)	−0.0064 (15)	−0.0033 (15)	−0.0079 (14)
C20	0.0334 (18)	0.0424 (18)	0.0331 (19)	−0.0099 (14)	−0.0003 (15)	−0.0048 (14)
N21	0.0347 (14)	0.0374 (13)	0.0296 (15)	−0.0009 (12)	−0.0009 (13)	0.0021 (10)
N22	0.0317 (13)	0.0325 (12)	0.0300 (14)	−0.0029 (11)	0.0002 (11)	0.0035 (12)
N23	0.0346 (15)	0.0382 (13)	0.0322 (15)	−0.0008 (11)	0.0057 (13)	0.0016 (10)
N24	0.0299 (13)	0.0347 (13)	0.0352 (14)	−0.0026 (12)	−0.0009 (11)	−0.0009 (12)
C25	0.0389 (18)	0.0335 (15)	0.0359 (19)	−0.0003 (13)	0.0012 (16)	0.0043 (14)
C26	0.0356 (19)	0.0402 (16)	0.0299 (17)	0.0012 (14)	0.0011 (15)	−0.0026 (13)
C27	0.0309 (18)	0.0381 (16)	0.0402 (19)	0.0026 (13)	−0.0049 (14)	−0.0001 (13)
C28	0.0357 (18)	0.0370 (15)	0.0367 (17)	0.0012 (12)	−0.0014 (16)	−0.0027 (14)
C29	0.055 (2)	0.0507 (19)	0.0313 (19)	0.0060 (18)	0.0012 (17)	−0.0055 (15)
C30	0.056 (2)	0.0404 (17)	0.0340 (18)	0.0073 (18)	−0.0056 (16)	0.0032 (16)
C31	0.0333 (17)	0.0445 (17)	0.038 (2)	0.0029 (13)	0.0007 (16)	−0.0041 (15)
O32	0.0625 (18)	0.0527 (14)	0.0451 (16)	0.0179 (12)	−0.0035 (13)	−0.0131 (12)
O33	0.0474 (15)	0.0560 (14)	0.0400 (15)	0.0216 (12)	−0.0080 (12)	−0.0082 (11)
C34	0.069 (3)	0.075 (3)	0.061 (3)	0.045 (2)	−0.012 (2)	−0.001 (2)
C35	0.0337 (18)	0.0313 (15)	0.0320 (19)	0.0018 (13)	0.0036 (14)	−0.0033 (12)
C36	0.0346 (18)	0.0360 (16)	0.0321 (17)	−0.0018 (13)	−0.0019 (14)	0.0039 (13)
C37	0.0345 (17)	0.0427 (18)	0.0302 (16)	−0.0019 (13)	−0.0046 (13)	−0.0006 (13)
C38	0.0319 (17)	0.0383 (16)	0.0309 (17)	0.0000 (13)	0.0011 (14)	0.0002 (13)
C39	0.0343 (18)	0.0460 (17)	0.0278 (18)	−0.0093 (14)	−0.0023 (14)	0.0044 (13)
C40	0.0371 (18)	0.0395 (17)	0.0316 (18)	−0.0082 (14)	−0.0009 (15)	0.0006 (13)
C41	0.0353 (19)	0.0426 (18)	0.0345 (19)	−0.0048 (14)	0.0009 (16)	0.0004 (14)
O42	0.0498 (15)	0.0597 (14)	0.0482 (16)	−0.0191 (12)	−0.0098 (14)	0.0058 (13)
O43	0.0460 (15)	0.0564 (14)	0.0420 (15)	−0.0182 (12)	−0.0024 (12)	0.0089 (11)
C44	0.046 (2)	0.068 (2)	0.051 (2)	−0.0219 (19)	0.0032 (19)	0.0079 (19)
C45	0.0258 (18)	0.0388 (16)	0.0355 (18)	0.0008 (12)	0.0031 (14)	−0.0067 (13)
C46	0.0406 (19)	0.0375 (16)	0.0267 (16)	−0.0039 (14)	0.0035 (15)	−0.0036 (12)
C47	0.046 (2)	0.0401 (17)	0.0325 (19)	−0.0008 (15)	−0.0085 (16)	−0.0006 (14)
C48	0.0322 (17)	0.0395 (17)	0.0369 (19)	−0.0001 (13)	0.0015 (15)	0.0040 (14)
C49	0.041 (2)	0.062 (2)	0.0271 (17)	0.0157 (17)	0.0079 (16)	−0.0010 (15)
C50	0.058 (2)	0.060 (2)	0.0325 (18)	0.0224 (18)	−0.0007 (18)	0.0059 (15)
C51	0.0278 (17)	0.0450 (18)	0.037 (2)	−0.0021 (14)	0.0015 (15)	0.0003 (15)
O52	0.0457 (15)	0.0579 (14)	0.0350 (14)	0.0153 (12)	−0.0004 (12)	0.0083 (11)
O53	0.0453 (15)	0.0510 (13)	0.0363 (14)	0.0173 (11)	0.0004 (11)	−0.0018 (10)
C54	0.045 (2)	0.065 (2)	0.050 (2)	0.0247 (18)	0.0048 (18)	−0.0038 (17)
C55	0.040 (2)	0.0388 (16)	0.0397 (18)	−0.0040 (15)	0.0029 (17)	−0.0048 (14)
C56	0.084 (3)	0.108 (3)	0.028 (2)	−0.060 (3)	0.010 (2)	−0.008 (2)
C57	0.088 (3)	0.109 (3)	0.031 (2)	−0.062 (3)	0.002 (2)	−0.004 (2)
C58	0.043 (2)	0.0386 (17)	0.0355 (19)	−0.0113 (14)	0.0059 (16)	−0.0062 (13)
C59	0.060 (2)	0.0467 (19)	0.0354 (19)	−0.0172 (18)	−0.0042 (16)	0.0058 (15)
C60	0.058 (2)	0.0516 (19)	0.034 (2)	−0.0120 (17)	−0.0080 (17)	0.0046 (15)
C61	0.046 (2)	0.0430 (18)	0.0322 (19)	−0.0125 (15)	0.0015 (16)	−0.0052 (15)
O62	0.0722 (19)	0.0656 (15)	0.0389 (15)	−0.0358 (14)	0.0041 (15)	0.0011 (12)
N65	0.0322 (15)	0.0391 (13)	0.0378 (14)	0.0027 (12)	−0.0015 (11)	0.0006 (12)
C66	0.069 (3)	0.047 (2)	0.046 (2)	−0.0076 (18)	0.010 (2)	0.0018 (17)
C67	0.089 (3)	0.055 (2)	0.042 (3)	−0.003 (2)	0.014 (2)	0.0078 (18)
C68	0.063 (3)	0.071 (3)	0.037 (2)	0.020 (2)	0.0033 (19)	0.0030 (18)
C69	0.086 (3)	0.060 (2)	0.040 (2)	−0.003 (2)	0.001 (2)	−0.0131 (17)
C70	0.073 (3)	0.054 (2)	0.038 (2)	−0.015 (2)	0.006 (2)	−0.0044 (16)

Geometric parameters (Å, º)

Zn—N22	2.070 (2)	C36—H36	0.9500
Zn—N21	2.075 (2)	C37—C38	1.395 (4)
Zn—N23	2.076 (2)	C37—H37	0.9500
Zn—N24	2.077 (3)	C38—C39	1.390 (4)
Zn—N65	2.148 (3)	C38—C41	1.487 (4)
C1—N21	1.381 (4)	C39—C40	1.381 (4)
C1—C20	1.399 (5)	C39—H39	0.9500
C1—C2	1.433 (4)	C40—H40	0.9500
C2—C3	1.353 (5)	C41—O42	1.212 (4)
C2—H2	0.9500	C41—O43	1.344 (4)
C3—C4	1.449 (4)	O43—C44	1.442 (4)
C3—H3	0.9500	C44—H44A	0.9800
C4—N21	1.365 (4)	C44—H44B	0.9800
C4—C5	1.406 (5)	C44—H44C	0.9800
C5—C6	1.409 (4)	C45—C46	1.385 (4)
C5—C25	1.497 (4)	C45—C50	1.393 (5)
C6—N22	1.365 (4)	C46—C47	1.399 (4)
C6—C7	1.439 (5)	C46—H46	0.9500
C7—C8	1.371 (4)	C47—C48	1.396 (5)
C7—H7	0.9500	C47—H47	0.9500
C8—C9	1.457 (4)	C48—C49	1.389 (5)
C8—H8	0.9500	C48—C51	1.484 (4)
C9—N22	1.378 (4)	C49—C50	1.381 (5)
C9—C10	1.408 (4)	C49—H49	0.9500
C10—C11	1.415 (5)	C50—H50	0.9500
C10—C35	1.490 (4)	C51—O52	1.206 (4)
C11—N23	1.370 (4)	C51—O53	1.339 (4)
C11—C12	1.446 (4)	O53—C54	1.447 (4)
C12—C13	1.350 (5)	C54—H54A	0.9800
C12—H12	0.9500	C54—H54B	0.9800
C13—C14	1.430 (4)	C54—H54C	0.9800
C13—H13	0.9500	C55—C60	1.375 (5)
C14—N23	1.368 (4)	C55—C56	1.384 (5)
C14—C15	1.396 (5)	C56—C57	1.386 (5)
C15—C16	1.397 (4)	C56—H56	0.9500
C15—C45	1.515 (4)	C57—C58	1.373 (5)
C16—N24	1.361 (4)	C57—H57	0.9500
C16—C17	1.449 (4)	C58—C59	1.371 (5)
C17—C18	1.360 (5)	C58—C61	1.487 (5)
C17—H17	0.9500	C59—C60	1.397 (5)
C18—C19	1.449 (5)	C59—H59	0.9500
C18—H18	0.9500	C60—H60	0.9500
C19—N24	1.382 (4)	C61—O62	1.185 (4)
C19—C20	1.401 (5)	C61—O63	1.346 (6)
C20—C55	1.497 (4)	C61—O63'	1.398 (6)
C25—C26	1.380 (5)	O63—C64	1.435 (9)
C25—C30	1.394 (5)	C64—H64A	0.9800
C26—C27	1.383 (4)	C64—H64B	0.9800
C26—H26	0.9500	C64—H64C	0.9800
C27—C28	1.380 (4)	O63'—C64'	1.438 (8)
C27—H27	0.9500	C64'—H64D	0.9800
C28—C29	1.385 (5)	C64'—H64E	0.9800
C28—C31	1.501 (4)	C64'—H64F	0.9800
C29—C30	1.374 (5)	N65—C66	1.318 (4)
C29—H29	0.9500	N65—C70	1.345 (4)
C30—H30	0.9500	C66—C67	1.377 (6)
C31—O32	1.193 (4)	C66—H66	0.9500
C31—O33	1.337 (4)	C67—C68	1.361 (6)
O33—C34	1.432 (4)	C67—H67	0.9500
C34—H34A	0.9800	C68—C69	1.383 (6)
C34—H34B	0.9800	C68—H68	0.9500
C34—H34C	0.9800	C69—C70	1.376 (5)
C35—C36	1.388 (4)	C69—H69	0.9500
C35—C40	1.395 (4)	C70—H70	0.9500
C36—C37	1.378 (4)
N22—Zn—N21	88.57 (10)	H34A—C34—H34C	109.5
N22—Zn—N23	88.66 (10)	H34B—C34—H34C	109.5
N21—Zn—N23	162.31 (9)	C36—C35—C40	118.4 (3)
N22—Zn—N24	159.97 (10)	C36—C35—C10	121.6 (3)
N21—Zn—N24	88.21 (10)	C40—C35—C10	120.0 (3)
N23—Zn—N24	88.42 (11)	C37—C36—C35	121.4 (3)
N22—Zn—N65	103.49 (10)	C37—C36—H36	119.3
N21—Zn—N65	101.28 (10)	C35—C36—H36	119.3
N23—Zn—N65	96.36 (10)	C36—C37—C38	119.6 (3)
N24—Zn—N65	96.53 (10)	C36—C37—H37	120.2
N21—C1—C20	125.6 (3)	C38—C37—H37	120.2
N21—C1—C2	109.3 (3)	C39—C38—C37	119.7 (3)
C20—C1—C2	125.0 (3)	C39—C38—C41	121.5 (3)
C3—C2—C1	107.4 (3)	C37—C38—C41	118.8 (3)
C3—C2—H2	126.3	C40—C39—C38	120.0 (3)
C1—C2—H2	126.3	C40—C39—H39	120.0
C2—C3—C4	107.1 (3)	C38—C39—H39	120.0
C2—C3—H3	126.5	C39—C40—C35	120.8 (3)
C4—C3—H3	126.5	C39—C40—H40	119.6
N21—C4—C5	126.0 (3)	C35—C40—H40	119.6
N21—C4—C3	109.2 (3)	O42—C41—O43	123.5 (3)
C5—C4—C3	124.9 (3)	O42—C41—C38	124.8 (3)
C4—C5—C6	125.0 (3)	O43—C41—C38	111.7 (3)
C4—C5—C25	117.1 (3)	C41—O43—C44	115.4 (3)
C6—C5—C25	117.9 (3)	O43—C44—H44A	109.5
N22—C6—C5	125.6 (3)	O43—C44—H44B	109.5
N22—C6—C7	110.5 (2)	H44A—C44—H44B	109.5
C5—C6—C7	123.8 (3)	O43—C44—H44C	109.5
C8—C7—C6	107.0 (3)	H44A—C44—H44C	109.5
C8—C7—H7	126.5	H44B—C44—H44C	109.5
C6—C7—H7	126.5	C46—C45—C50	119.7 (3)
C7—C8—C9	106.2 (3)	C46—C45—C15	120.2 (3)
C7—C8—H8	126.9	C50—C45—C15	120.1 (3)
C9—C8—H8	126.9	C45—C46—C47	119.8 (3)
N22—C9—C10	126.5 (3)	C45—C46—H46	120.1
N22—C9—C8	109.8 (2)	C47—C46—H46	120.1
C10—C9—C8	123.7 (3)	C48—C47—C46	120.2 (3)
C9—C10—C11	124.4 (3)	C48—C47—H47	119.9
C9—C10—C35	118.2 (3)	C46—C47—H47	119.9
C11—C10—C35	117.3 (3)	C49—C48—C47	119.4 (3)
N23—C11—C10	125.6 (3)	C49—C48—C51	121.7 (3)
N23—C11—C12	109.4 (3)	C47—C48—C51	118.8 (3)
C10—C11—C12	125.0 (3)	C50—C49—C48	120.3 (3)
C13—C12—C11	106.4 (3)	C50—C49—H49	119.8
C13—C12—H12	126.8	C48—C49—H49	119.8
C11—C12—H12	126.8	C49—C50—C45	120.5 (3)
C12—C13—C14	108.0 (3)	C49—C50—H50	119.7
C12—C13—H13	126.0	C45—C50—H50	119.7
C14—C13—H13	126.0	O52—C51—O53	123.5 (3)
N23—C14—C15	124.7 (3)	O52—C51—C48	124.7 (3)
N23—C14—C13	109.2 (3)	O53—C51—C48	111.8 (3)
C15—C14—C13	125.9 (3)	C51—O53—C54	114.9 (3)
C14—C15—C16	127.0 (3)	O53—C54—H54A	109.5
C14—C15—C45	115.2 (3)	O53—C54—H54B	109.5
C16—C15—C45	117.8 (3)	H54A—C54—H54B	109.5
N24—C16—C15	124.7 (3)	O53—C54—H54C	109.5
N24—C16—C17	111.1 (3)	H54A—C54—H54C	109.5
C15—C16—C17	124.2 (3)	H54B—C54—H54C	109.5
C18—C17—C16	105.9 (3)	C60—C55—C56	117.6 (3)
C18—C17—H17	127.0	C60—C55—C20	121.3 (3)
C16—C17—H17	127.0	C56—C55—C20	121.0 (3)
C17—C18—C19	107.5 (3)	C55—C56—C57	121.3 (4)
C17—C18—H18	126.3	C55—C56—H56	119.3
C19—C18—H18	126.3	C57—C56—H56	119.3
N24—C19—C20	125.1 (3)	C58—C57—C56	120.6 (4)
N24—C19—C18	109.4 (3)	C58—C57—H57	119.7
C20—C19—C18	125.4 (3)	C56—C57—H57	119.7
C1—C20—C19	125.8 (3)	C59—C58—C57	118.7 (3)
C1—C20—C55	118.1 (3)	C59—C58—C61	118.2 (3)
C19—C20—C55	116.1 (3)	C57—C58—C61	123.0 (3)
C4—N21—C1	107.1 (2)	C58—C59—C60	120.5 (3)
C4—N21—Zn	126.3 (2)	C58—C59—H59	119.7
C1—N21—Zn	126.1 (2)	C60—C59—H59	119.7
C6—N22—C9	106.5 (2)	C55—C60—C59	121.1 (3)
C6—N22—Zn	126.9 (2)	C55—C60—H60	119.4
C9—N22—Zn	126.55 (19)	C59—C60—H60	119.4
C14—N23—C11	107.0 (2)	O62—C61—O63	119.7 (3)
C14—N23—Zn	125.1 (2)	O62—C61—O63'	121.4 (3)
C11—N23—Zn	126.7 (2)	O62—C61—C58	125.5 (3)
C16—N24—C19	106.1 (3)	O63—C61—C58	111.5 (3)
C16—N24—Zn	126.3 (2)	O63'—C61—C58	111.4 (3)
C19—N24—Zn	126.8 (2)	C61—O63—C64	114.7 (5)
C26—C25—C30	118.4 (3)	C61—O63'—C64'	115.6 (5)
C26—C25—C5	120.7 (3)	O63'—C64'—H64D	109.5
C30—C25—C5	120.9 (3)	O63'—C64'—H64E	109.5
C25—C26—C27	121.1 (3)	H64D—C64'—H64E	109.5
C25—C26—H26	119.4	O63'—C64'—H64F	109.5
C27—C26—H26	119.4	H64D—C64'—H64F	109.5
C28—C27—C26	119.9 (3)	H64E—C64'—H64F	109.5
C28—C27—H27	120.1	C66—N65—C70	117.2 (3)
C26—C27—H27	120.1	C66—N65—Zn	121.6 (2)
C27—C28—C29	119.6 (3)	C70—N65—Zn	121.1 (2)
C27—C28—C31	122.5 (3)	N65—C66—C67	123.4 (4)
C29—C28—C31	117.9 (3)	N65—C66—H66	118.3
C30—C29—C28	120.2 (3)	C67—C66—H66	118.3
C30—C29—H29	119.9	C68—C67—C66	119.3 (4)
C28—C29—H29	119.9	C68—C67—H67	120.3
C29—C30—C25	120.7 (3)	C66—C67—H67	120.3
C29—C30—H30	119.6	C67—C68—C69	118.3 (4)
C25—C30—H30	119.6	C67—C68—H68	120.8
O32—C31—O33	123.9 (3)	C69—C68—H68	120.8
O32—C31—C28	125.1 (3)	C70—C69—C68	118.9 (4)
O33—C31—C28	111.0 (3)	C70—C69—H69	120.6
C31—O33—C34	114.8 (3)	C68—C69—H69	120.6
O33—C34—H34A	109.5	N65—C70—C69	122.7 (4)
O33—C34—H34B	109.5	N65—C70—H70	118.6
H34A—C34—H34B	109.5	C69—C70—H70	118.6
O33—C34—H34C	109.5