Unsolvated 5,10,15,20-tetra-4-pyridyl­porphyrin, its sesquihydrate and its 2-chloro­phenol disolvate: conformational versatility of the ligand

Unsolvated 5,10,15,20-tetra-4-pyridylporphyrin, C₄₀H₂₆N₈, (I), its sesquihydrate, C₄₀H₂₆N₈·1.514H₂O, (II), and its 2-chloro­phenol disolvate, C₄₀H₂₆N₈·2C₆H₅ClO, (III), reveal different conformational features of the porphyrin core. In (I), the latter is severely deformed from planarity, apparently in order to optimize the inter­molecular inter­actions and efficient crystal packing of the mol­ecular entities. The mol­ecular framework has a C₁ symmetry. In (II), the porphyrin mol­ecules are located on symmetry axes, preserving the marked deformation from planarity of the porphyrin core. The mol­ecular units are inter­linked into a single-framework supra­molecular architecture by hydrogen bonding to one another via mol­ecules of water, which lie on twofold rotation axes. In (III), the porphyrin mol­ecules are located across centres of inversion and are characterized by a planar conformation of the 24-membered macrocyclic porphyrin ring. Two trans-related pyridyl substituents are hydrogen bonded to the 2-chloro­phenol solvent mol­ecules. The inter­porphyrin organization in (III) is similar to that observed for many other tetra­aryl­porphyrin compounds. However, the organization observed in (I) and (II) is different and of a type rarely observed before. This study reports for the first time the crystal structure of the unsolvated tetra­pyridylporphyrin.

S1. Comment

Tetrapyridylporphyrin (TPyP; Fleischer, 1962) is one of the most widely studied porphyrin ligands in materials chemistry. It bears laterally diverging pyridyl functions which can readily interact in a cooperative manner with complementary entities through either coordination or hydrogen bonding. Moreover, it can form organometallic complexes with various transition metal ions inserted into the macrocyclic core, the latter potentially providing additional binding sites for further intermolecular coordination. Self-coordination of the Zn-TPyP complex into one-, two- and three-dimensional coordination polymers has been widely reported (Fleischer & Shachter, 1991; Krupitsky et al., 1994, Diskin-Posner et al., 2001; Ring et al., 2005). Facile formation of diverse coordination networks and frameworks of TPyP and M-TPyP via metal ions as bridging nodes between the peripheral pyridyl functions of adjacent species has also been reported (Goldberg, 2000, 2005, 2008, and references therein). More recently, the capacity of this porphyrin to engage in networking by supramolecular hydrogen bonding through complementary components has been demonstrated (Koner & Goldberg, 2009). The molecular framework of TPyP/Zn–TPyP is relatively rigid, and the central core of the porphyrin has an aromatic nature. However, the detailed conformation of this ligand is affected to some extent by the requirement to optimize the intermolecular interactions, and minimize the enthalpy, within the formed supramolecular assembly in a given case. Correspondingly, the macrocyclic framework of TPyP may reveal in most cases either flat or slightly ruffled conformations, as has been observed for various tetrapyrrole macrocycles (Scheidt & Lee, 1987). Like many other tetraarylporphyrins, the TPyP/M–TPyP framework exhibits shape complementarity only in two dimensions (Byrn et al., 1993, and references therein), and therefore it commonly tends to crystallize as a solvate (because of this feature such compounds were nicknamed `porphyrin sponges'), where molecules of the solvent fill the interporphyrin voids in the lattice. This may explain why the crystal structure of unsolvated TPyP has not been characterized before.

We report here for the first time the crystal structure of pure TPyP, (I), and relate it to the unique conformational features of the porphyrin ligand in this case. We also describe the structure of the non-stoichiometric hydrate TPyP.1.514(H₂O), (II), in which unusually large deformation of the porphyrin core has again been observed, apparently also in order to facilitate multiple supramolecular hydrogen bonding between the porphyrin and water components. Then, another variant, 2-chlorophenol solvated TPyP, is described, (III), in which, however, the porphyrin macrocycle is characterized by a nearly planar conformation. The molecular structure of (I) is shown in Figs. 1 and 2(a). Of particular interest is the severe deformation of the porphyrin core from planarity, resulting from the optimization of the intermolecular packing in the crystals of pure TPyP. Fig. 2(a) gives the deviations of the individual atoms from the mean plane of the 24-membered porphyrin core, which range from -0.394 Å (for atom C7) to +0.393 Å (C12). The relatively large dihedral angles between the planes of the five-membered pyrrole rings provide further evidence for the severe ruffling of this porphyrin macrocycle. Thus, the torsion angles between the corresponding adjacent pyrrole rings (those containing atoms N22/N21, N23/N22, N24/N23 and N21/N24) are 18.19 (6), 20.20 (10), 20.34 (11) and 17.25 (9)°, respectively. The torsion angles between pyrrole rings located across the macrocycle are even larger [27.44 (9)° for N23/N21 and 26.41 (8)° for N24/N22]. The molecular symmetry of TPyP in this structure is C₁. The conformationally distorted porphyrin molecules pack tightly in the crystal structure of (I), without the need to incorporate crystallization solvent into the lattice, as shown in Fig. 3. The intermolecular organization is stabilized effectively by van der Waals forces. The porphyrin core of a given molecule is approached from above and below by edge-on-oriented pyridyl substituents of neighbouring species. Nearly parallel overlap between the pyridyl rings of the laterally displaced units is indicative of possible π–π interactions between them. However, no direction-specific intermolecular contacts, such as those of C—H···N type, significantly shorter than the corresponding sums of the van der Waals radii are present.

The porphyrin molecule in (II) is also characterized by a distorted conformation of the central core (Figs. 2b and 4). In this structure the porphyrin molecular unit is located on the 4 axis of symmetry, while the water species reside on twofold axes. The torsion angles between the adjacent pyrrole rings are 18.27 (8)°; those between the pyrroles across the macrocycle are 25.95 (7)°. The deviations of the individual atoms in the 24-membered macroring are quite significant, as in (I), ranging from -0.382 to +0.382 Å (Fig. 2b). Water molecules located on twofold rotation axes, and with site occupancy 0.757 (10), form hydrogen bonds to the peripheral pyridyl N atoms of two adjacent porphyrin units located at different z-coordinate levels (Fig. 5 and Table 1). These interactions operate at the four corners of the ligand, throughout the crystal, thus creating a continuous three-dimensional hydrogen-bonded architecture. Fig. 6 illustrates the crystal packing of (II) viewed roughly perpendicular to the tetragonal axis, depicting the distorted nature of the porphyrin macrocycle. The TPyP molecules are arranged along the c axis is an offset manner, so that the macrocyclic ring of a given unit is approached from above and below by two pyridyl groups of adjacent porphyrins on each side. The tight arrangement lacks intermolecular contacts that are significantly shorter than common van der Waals diameters, reflecting on further (to the hydrogen bonding interactions) stabilization of the entire structure by common dispersion forces.

While TPyP reveals similarly distorted conformations in the two previous examples, this is not the case in the structure of its 2-chlorophenol disolvate (III) (Fig. 7). The porphyrin molecule is located on the inversion centre at (1/2, 1/2, 1/2), and its two trans-related pyridyl groups are hydrogen bonded to the o-chlorophenol solvent. The macrocyclic core is essentially planar, and the TPyP molecules are stacked in an offset manner along the a axis of the crystal at a mean interplanar distance of 3.55 (2) Å (Fig. 8). In this offset stacked geometry, each porphyrin core is sandwiched between two pyridyl arms of adjacent species from above and below, which are displaced by ±b. Porphyrin stacks displaced along the c axis form a tightly packed layered zones parallel to the ac face of the unit cell. With this zone, the trans-related pyridyl groups of neighboring coplanar porphyrins overlap effectively, stabilizing the layered arrangement by favourable dipolar and dispersive interactions. The other pyridyl substituents directed outwards (perpendicular to the layered porphyrin arrays) are hydrogen bonded to the o-chlorophenol species via O—H···N hydrogen bonds (Table 2). This intermolecular organization is similar to that reported before for the 1:2 TPyP solvates with guaiacol and benzyl alcohol (Krupitsky et al., 1994), and is frequently found in solvates of other tetraarylporphyrins (Byrn et al., 1993, and references therein). The interporphyrin offset stacking geometry is a fundamental property of the porphyrin–porphyrin interaction (Leighton et al., 1988), and structure (III) is in agreement with this principle. It favors in crystals stacked organization of the tetraarylporphyrin molecules with flat cores, and tight packing of these stacks into two-dimensional layers. The crystalline organization of the two-dimensional porphyrin layers along the third dimension is facilitated by solvation of the layers along the interfaces between them.

This study characterizes for the first time the structure of unsolvated TPyP, revealing an unusually distorted conformation of this ligand. This observation is even more striking when compared with the structure of the solvent-free tetraphenylporphyrin analog (TPP), which reveals a planar conformation of the porphyrin core and the common offset stacking arrangement as in (III) (Kano et al., 2000). It is possible that the electron-withdrawing effect of the pyridyl substituents weakens the aromaticity of the porphyrin macrocycle in TPyP (as compared with that in TPP), allowing more readily its deformation from planarity by more dominant crystal packing forces. It appears that this feature is conserved even in the presence of small solvents such as water [as in (II)], while with larger solvent such as 2-chlorophenol the more abundant offset-stacked organization of TPyP is formed. It remains to be seen whether a flat polymorph of unsolvated TPyP will be found in the future.

Related literature

For related literature, see: Byrn et al. (1993); Diskin-Posner, Patra & Goldberg (2001); Fleischer (1962); Fleischer & Shachter (1991); Goldberg (2000, 2005, 2008); Kano et al. (2000); Koner & Goldberg (2009); Krupitsky et al. (1994); Leighton et al. (1988); Ring et al. (2005); Scheidt & Lee (1987).

S2. Experimental

The porphyrin compound, as well as all the other reactants and solvents (see below) were obtained commercially. Crystals of (I) and (II) were obtained as by-products during attempts to synthesize coordination networks of the porphyrin moiety with lanthanide ions. Crystals of (I) were obtained by slow diffusion between layers: TPyP (0.011 mmol) was dissolved in 2 ml of a 1:1 (v/v) methanol:tetrachloroethane mixture, which was heated under reflux for 2 h and then filtered. A solution of lanthanum chloride heptahydrate (0.9 mmol) in 5 ml of a 5:3 (v/v) mixture of methanol and dimethylformamide was carefully layered on top of the TPyP solution. Crystals were obtained in the porphyrin phase after 12 d. Compound (I) was obtained in a similar experiment while using gadolinium nitrate hexahydrate instead of the lanthanum salt. For (II), TPyP (0.013 mmol) and lanthanum nitrate hexahydrate (0.092 mmol) dissolved in 15 ml of a 1:1 (v/v) mixture of methanol and 1,2-dichlorobenzene. The resulting solution was heated under reflux, filtered and the solute was kept for crystallization by slow evaporation. X-ray quality crystals were obtained after one month. In the third case, an attempt to synthesize hydrogen-bonding supramolecular networks by reacting TPyP with 2,5-thiophenedicarboxylic acid (TPDA) failed, yielding instead compound (III). TPyP (0.006 mmol) and TPDA (0.02 mmol) were dissolved in 5 ml of MeOH containing a few drops of 2-chlorophenol. The resulting solution was heated under reflux for 10 min and then filtered. Using the slow vapour diffusion method, an open vial of the solute was placed in a closed vessel with diethyl ether. Crystals of (III) appeared after one day.

S3. Refinement

In all three compounds, H atoms bound to C atoms were located in calculated positions and were constrained to ride on their parent atoms with C—H distances of 0.95 Å and with U_iso(H) values of 1.2 U_eq(C). The two N(pyrrole)-bound H atoms were found to be disordered between the four pyrrole sites. They were located also in calculated positions, constrained to ride on their parent atoms with N—H distances of 0.88 Å and with U_iso(H) of 1.2U_eq(N). The H atom bound to O32 in (III) was located in a difference Fourier map, but its position was not refined. The water H atom in the asymmetric unit of (II) could not be located reliably, as the residual electron density peaks which could correspond to this H atom were very low. One of these peaks was assigned as the H atom, and its position was restrained in the refinement at an O—H distance of 0.95 (s.u.value?) Å. These H atoms were assigned U_iso(H) values of 1.5 or 1.2 times U_eq(O), in (II) and (III), respectively. The refined site occupancy of the water molecule in (II) was 0.757 (10) for the crystal selected for data collection, which corresponds approximately to the sesquihydrate with a 1:1.5 porphyrin:water stoichiometry. 14 reflections in (I) and 1 reflection in (II) were omitted from the final structure factors calculations because of poor assessment of the intensities (oversaturated or overlapping reflections).

Computing details

For all compounds, data collection: Collect (Nonius, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of (I), showing the atom labeling scheme. The atom ellipsoids represent displacement parameters at the 50% probability level at ca 110 K. H atoms have been omitted.
	Fig. 2. Deviations of the individual atoms (Å) from the mean plane of the 24-membered porphyrin core in (a) (I) and (b) (II), indicative of similar severe ruffling of the macrocycle in the two compounds. [Symmetry codes: (i) x, y, z; (ii) -y, x, -z + 1; (iii) -x, -y, z; (iv) y, -x, -z + 1.]
	Fig. 3. The crystal packing of (I). Note that the porphyrin core of porphyrin A is approached from above and below by nearly parallel pairs of the pyridyl arms of molecules B and C (above) and D and E (below). [Symmetry codes: (A) x, y, z; (B) x + 1/2, -y + 1/2, z + 1/2; (C) x, -y + 1, z - 1/2; (D) x - 1/2, -y + 1/2, z - 1/2; (E) x, -y + 1, z + 1/2; (F) x - 1/2, y + 1/2, z - 1.]
	Fig. 4. The molecular structure of (II), showing the atom labeling scheme. The porphyrin molecules are located on 4 symmetry axes, and only atoms of the asymmetric unit are labeled. The atom ellipsoids represent displacement parameters at the 50% probability level at ca 110 K. All but the water H atoms have been omitted. The hydrogen bonding of the water molecule to the pyridyl group is denoted by dashed lines.
	Fig. 5. The hydrogen-bonding interactions in (II), indicated by dashed lines. The water molecules are depicted as small spheres; H atoms have been omitted. The viewing perspective is nearly down the tetragonal axis. Note that the central porphyrin molecule is hydrogen bonded to four other porphyrin units located at either higher or lower z-coordinate levels of the structure.
	Fig. 6. A wireframe illustration of the crystal structure of (II). The water molecules are depicted as small spheres; H atoms have been omitted.
	Fig. 7. The molecular structure of (III), showing the atom labeling scheme. The porphyrin molecules are located on inversion centers, and only atoms of the asymmetric unit are labeled. The atom ellipsoids represent displacement parameters at the 50% probability level at ca 110 K. All but the hydroxy H atoms have been omitted. The hydrogen bonding of the o-chlorophenol molecule to the pyridyl group is denoted by dashed lines.
	Fig. 8. (a) The crystal structure of (III), showing nine parallel stacks of TPyP molecules displaced by ±b and ±c, and interspaced by the o-chlorobenzene solvent molecule. (b) A parallel view of the overlapping mode between neighboring porphyrin species in the stack [at (x, y, z) and (x ± 1, y, z)]. Note the offset of the molecular frameworks, which allows the pyridyl group of one unit to perch on the porphyrin center of an adjacent unit. The mean distance between the overlapping 11-atom fragments of the relevant porphyrin rings is 3.55 (4) Å. [Symmetry codes: (i) x, y, z; (ii) -x + 1, -y + 1, -z + 1; (iii) x - 1, y, z; (iv) -x, -y + 1, -z + 1.]

(I) 5,10,15,20-tetra-4-pyridylporphyrin

Crystal data

C40H26N8	F(000) = 1288
Mr = 618.69	Dx = 1.409 Mg m^−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 4891 reflections
a = 13.6042 (2) Å	θ = 2.0–27.9°
b = 20.8734 (4) Å	µ = 0.09 mm^−1
c = 11.4525 (2) Å	T = 110 K
β = 116.2786 (11)°	Prism, red
V = 2916.02 (9) Å^3	0.40 × 0.40 × 0.30 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer	3032 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.057
Graphite monochromator	θmax = 27.9°, θmin = 2.0°
Detector resolution: 12.8 pixels mm^-1	h = −17→17
1 deg. ϕ and ω scans	k = −26→27
16180 measured reflections	l = −14→14
3456 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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.127	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0818P)^2 + 0.7758P] where P = (Fo^2 + 2Fc^2)/3
3456 reflections	(Δ/σ)max < 0.001
433 parameters	Δρmax = 0.38 e Å^−3
2 restraints	Δρmin = −0.28 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.

The Friedel opposites were merged.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.0339 (2)	0.24370 (14)	−0.2566 (3)	0.0202 (6)
C2	0.0474 (2)	0.31233 (14)	−0.2507 (3)	0.0212 (6)
H2	0.0304	0.3405	−0.3223	0.025*
C3	0.0891 (3)	0.32897 (14)	−0.1234 (3)	0.0220 (6)
H3	0.1051	0.3712	−0.0890	0.026*
C4	0.1048 (3)	0.27065 (14)	−0.0497 (3)	0.0201 (6)
C5	0.1562 (2)	0.26725 (13)	0.0868 (3)	0.0187 (6)
C6	0.1961 (2)	0.21059 (14)	0.1593 (3)	0.0200 (6)
C7	0.2548 (3)	0.20409 (15)	0.2989 (3)	0.0226 (6)
H7	0.2692	0.2372	0.3613	0.027*
C8	0.2858 (2)	0.14173 (14)	0.3243 (3)	0.0211 (6)
H8	0.3281	0.1238	0.4080	0.025*
C9	0.2437 (2)	0.10768 (14)	0.2032 (3)	0.0187 (6)
C10	0.2487 (2)	0.04133 (14)	0.1888 (3)	0.0201 (6)
C11	0.1829 (3)	0.00596 (15)	0.0776 (3)	0.0215 (6)
C12	0.1829 (3)	−0.06329 (14)	0.0671 (3)	0.0231 (6)
H12	0.2313	−0.0922	0.1305	0.028*
C13	0.1009 (3)	−0.07875 (14)	−0.0501 (3)	0.0232 (6)
H13	0.0781	−0.1208	−0.0828	0.028*
C14	0.0542 (2)	−0.01921 (14)	−0.1167 (3)	0.0197 (6)
C15	−0.0269 (2)	−0.01431 (14)	−0.2459 (3)	0.0202 (6)
C16	−0.0536 (2)	0.04217 (14)	−0.3198 (3)	0.0209 (6)
C17	−0.1245 (3)	0.04743 (15)	−0.4573 (3)	0.0231 (6)
H17	−0.1688	0.0143	−0.5125	0.028*
C18	−0.1163 (3)	0.10833 (14)	−0.4936 (3)	0.0220 (6)
H18	−0.1517	0.1251	−0.5795	0.026*
C19	−0.0445 (2)	0.14280 (14)	−0.3792 (3)	0.0190 (6)
C20	−0.0180 (2)	0.20798 (13)	−0.3725 (3)	0.0183 (6)
N21	0.0704 (2)	0.21949 (12)	−0.1329 (2)	0.0200 (5)
H21	0.0715	0.1789	−0.1114	0.024*	0.50
N22	0.1889 (2)	0.15073 (12)	0.1047 (2)	0.0191 (5)
H22	0.1551	0.1417	0.0211	0.023*	0.50
N23	0.1046 (2)	0.03168 (12)	−0.0365 (2)	0.0209 (5)
H23	0.0898	0.0726	−0.0543	0.025*	0.50
N24	−0.0074 (2)	0.10116 (11)	−0.2752 (2)	0.0200 (5)
H24	0.0381	0.1107	−0.1942	0.024*	0.50
C25	0.1744 (3)	0.32853 (14)	0.1604 (3)	0.0205 (6)
C26	0.0863 (3)	0.36891 (15)	0.1400 (3)	0.0256 (6)
H26	0.0139	0.3575	0.0797	0.031*
C27	0.1060 (3)	0.42579 (16)	0.2090 (3)	0.0306 (7)
H27	0.0450	0.4524	0.1943	0.037*
N28	0.2055 (3)	0.44571 (13)	0.2949 (3)	0.0320 (6)
C29	0.2892 (3)	0.40652 (16)	0.3130 (3)	0.0290 (7)
H29	0.3608	0.4194	0.3733	0.035*
C30	0.2783 (3)	0.34868 (15)	0.2499 (3)	0.0245 (6)
H30	0.3408	0.3229	0.2673	0.029*
C31	0.3313 (2)	0.00532 (14)	0.3037 (3)	0.0209 (6)
C32	0.4426 (3)	0.01395 (15)	0.3427 (3)	0.0266 (6)
H32	0.4675	0.0436	0.2987	0.032*
C33	0.5172 (3)	−0.02154 (17)	0.4470 (3)	0.0311 (7)
H33	0.5930	−0.0163	0.4704	0.037*
N34	0.4889 (2)	−0.06267 (14)	0.5166 (3)	0.0304 (6)
C35	0.3813 (3)	−0.07006 (17)	0.4785 (3)	0.0301 (7)
H35	0.3589	−0.0989	0.5263	0.036*
C36	0.3000 (3)	−0.03804 (16)	0.3729 (3)	0.0272 (7)
H36	0.2246	−0.0458	0.3489	0.033*
C37	−0.0888 (2)	−0.07341 (14)	−0.3114 (3)	0.0202 (6)
C38	−0.0404 (3)	−0.12450 (15)	−0.3452 (3)	0.0251 (6)
H38	0.0350	−0.1229	−0.3259	0.030*
C39	−0.1030 (3)	−0.17750 (16)	−0.4070 (3)	0.0275 (7)
H39	−0.0682	−0.2119	−0.4284	0.033*
N40	−0.2097 (2)	−0.18314 (13)	−0.4383 (3)	0.0273 (6)
C41	−0.2552 (3)	−0.13438 (15)	−0.4046 (3)	0.0248 (6)
H41	−0.3307	−0.1376	−0.4246	0.030*
C42	−0.1997 (2)	−0.07922 (14)	−0.3421 (3)	0.0220 (6)
H42	−0.2366	−0.0460	−0.3206	0.026*
C43	−0.0491 (3)	0.24248 (14)	−0.4984 (3)	0.0207 (6)
C44	−0.1560 (3)	0.25976 (16)	−0.5808 (3)	0.0286 (7)
H44	−0.2139	0.2490	−0.5594	0.034*
C45	−0.1778 (3)	0.29275 (18)	−0.6945 (3)	0.0347 (8)
H45	−0.2518	0.3036	−0.7498	0.042*
N46	−0.1013 (3)	0.31039 (15)	−0.7317 (3)	0.0347 (7)
C47	0.0012 (3)	0.29286 (17)	−0.6517 (3)	0.0331 (8)
H47	0.0574	0.3043	−0.6756	0.040*
C48	0.0314 (3)	0.25937 (15)	−0.5369 (3)	0.0260 (6)
H48	0.1059	0.2480	−0.4850	0.031*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0192 (14)	0.0203 (14)	0.0187 (13)	−0.0015 (11)	0.0062 (11)	0.0014 (11)
C2	0.0239 (15)	0.0188 (14)	0.0188 (13)	0.0002 (11)	0.0075 (11)	0.0027 (11)
C3	0.0256 (15)	0.0168 (13)	0.0222 (14)	−0.0024 (11)	0.0094 (12)	0.0006 (11)
C4	0.0216 (15)	0.0187 (14)	0.0198 (13)	0.0013 (11)	0.0090 (12)	0.0000 (10)
C5	0.0206 (15)	0.0167 (14)	0.0177 (13)	−0.0028 (11)	0.0075 (11)	−0.0016 (10)
C6	0.0214 (15)	0.0208 (14)	0.0169 (13)	−0.0037 (11)	0.0077 (11)	−0.0021 (11)
C7	0.0272 (16)	0.0207 (14)	0.0165 (13)	−0.0013 (12)	0.0065 (12)	−0.0013 (10)
C8	0.0223 (15)	0.0210 (14)	0.0162 (13)	0.0003 (11)	0.0051 (11)	−0.0009 (11)
C9	0.0200 (14)	0.0185 (13)	0.0161 (13)	0.0009 (11)	0.0067 (11)	0.0028 (10)
C10	0.0237 (15)	0.0196 (13)	0.0168 (13)	0.0016 (11)	0.0088 (12)	0.0024 (11)
C11	0.0231 (15)	0.0210 (14)	0.0193 (13)	0.0003 (11)	0.0086 (11)	0.0028 (11)
C12	0.0275 (16)	0.0189 (14)	0.0188 (14)	0.0016 (12)	0.0067 (12)	0.0010 (11)
C13	0.0281 (16)	0.0172 (13)	0.0217 (14)	0.0021 (12)	0.0087 (12)	0.0005 (11)
C14	0.0172 (13)	0.0193 (14)	0.0202 (13)	−0.0008 (11)	0.0061 (11)	−0.0002 (11)
C15	0.0217 (14)	0.0172 (13)	0.0193 (13)	−0.0014 (11)	0.0068 (11)	−0.0024 (11)
C16	0.0213 (15)	0.0192 (14)	0.0207 (14)	0.0001 (11)	0.0079 (12)	−0.0009 (11)
C17	0.0258 (16)	0.0214 (15)	0.0186 (13)	−0.0014 (12)	0.0068 (12)	−0.0045 (11)
C18	0.0250 (16)	0.0205 (14)	0.0160 (13)	−0.0006 (12)	0.0050 (11)	−0.0003 (11)
C19	0.0227 (14)	0.0168 (13)	0.0164 (13)	−0.0012 (10)	0.0078 (11)	0.0004 (10)
C20	0.0190 (14)	0.0173 (13)	0.0162 (13)	0.0005 (11)	0.0058 (11)	0.0024 (10)
N21	0.0245 (13)	0.0179 (12)	0.0153 (11)	0.0004 (10)	0.0066 (9)	0.0001 (9)
N22	0.0209 (12)	0.0163 (12)	0.0168 (11)	−0.0003 (9)	0.0053 (10)	0.0008 (9)
N23	0.0213 (12)	0.0205 (12)	0.0170 (11)	−0.0007 (10)	0.0051 (10)	0.0001 (9)
N24	0.0240 (13)	0.0166 (12)	0.0175 (11)	−0.0021 (9)	0.0074 (10)	−0.0014 (9)
C25	0.0298 (16)	0.0170 (14)	0.0171 (13)	−0.0026 (11)	0.0125 (12)	−0.0008 (10)
C26	0.0292 (17)	0.0253 (16)	0.0219 (14)	0.0032 (12)	0.0110 (13)	0.0008 (12)
C27	0.047 (2)	0.0236 (16)	0.0263 (16)	0.0078 (14)	0.0212 (15)	0.0022 (12)
N28	0.0527 (19)	0.0211 (13)	0.0256 (14)	−0.0026 (13)	0.0205 (13)	−0.0014 (11)
C29	0.0398 (19)	0.0257 (16)	0.0212 (14)	−0.0081 (14)	0.0133 (14)	−0.0036 (12)
C30	0.0303 (16)	0.0227 (14)	0.0195 (14)	−0.0058 (12)	0.0102 (12)	−0.0012 (11)
C31	0.0275 (16)	0.0171 (13)	0.0153 (13)	0.0031 (11)	0.0071 (12)	−0.0005 (10)
C32	0.0280 (17)	0.0226 (15)	0.0246 (14)	0.0018 (12)	0.0076 (13)	0.0013 (12)
C33	0.0288 (17)	0.0302 (17)	0.0273 (16)	0.0049 (14)	0.0060 (14)	0.0019 (13)
N34	0.0358 (16)	0.0285 (15)	0.0215 (13)	0.0075 (12)	0.0078 (12)	0.0010 (11)
C35	0.039 (2)	0.0309 (18)	0.0245 (15)	0.0105 (14)	0.0176 (15)	0.0072 (13)
C36	0.0283 (17)	0.0303 (16)	0.0236 (14)	0.0073 (13)	0.0121 (13)	0.0066 (13)
C37	0.0231 (14)	0.0170 (13)	0.0181 (13)	−0.0011 (11)	0.0068 (11)	−0.0001 (10)
C38	0.0230 (15)	0.0218 (15)	0.0294 (16)	0.0016 (12)	0.0106 (13)	−0.0028 (12)
C39	0.0273 (16)	0.0195 (14)	0.0312 (16)	0.0031 (12)	0.0088 (13)	−0.0039 (12)
N40	0.0290 (14)	0.0212 (13)	0.0275 (13)	−0.0035 (11)	0.0087 (11)	−0.0015 (10)
C41	0.0234 (15)	0.0237 (15)	0.0267 (15)	−0.0018 (12)	0.0104 (12)	0.0011 (12)
C42	0.0226 (15)	0.0192 (14)	0.0207 (14)	0.0020 (11)	0.0063 (12)	0.0003 (11)
C43	0.0246 (16)	0.0190 (14)	0.0149 (12)	−0.0025 (11)	0.0055 (11)	0.0002 (11)
C44	0.0222 (16)	0.0298 (17)	0.0284 (16)	−0.0026 (13)	0.0063 (13)	0.0063 (13)
C45	0.036 (2)	0.0320 (18)	0.0226 (16)	−0.0071 (15)	0.0007 (14)	0.0066 (13)
N46	0.0494 (18)	0.0299 (15)	0.0178 (12)	−0.0110 (13)	0.0084 (12)	0.0011 (11)
C47	0.044 (2)	0.0324 (18)	0.0271 (16)	−0.0095 (15)	0.0196 (16)	0.0000 (13)
C48	0.0303 (17)	0.0240 (15)	0.0252 (15)	−0.0037 (12)	0.0137 (13)	−0.0004 (12)

Geometric parameters (Å, º)

C1—N21	1.373 (4)	N23—H23	0.8800
C1—C20	1.409 (4)	N24—H24	0.8800
C1—C2	1.442 (4)	C25—C30	1.393 (4)
C2—C3	1.355 (4)	C25—C26	1.398 (4)
C2—H2	0.9500	C26—C27	1.385 (4)
C3—C4	1.442 (4)	C26—H26	0.9500
C3—H3	0.9500	C27—N28	1.339 (5)
C4—N21	1.369 (4)	C27—H27	0.9500
C4—C5	1.403 (4)	N28—C29	1.342 (5)
C5—C6	1.408 (4)	C29—C30	1.381 (4)
C5—C25	1.491 (4)	C29—H29	0.9500
C6—N22	1.381 (4)	C30—H30	0.9500
C6—C7	1.443 (4)	C31—C36	1.388 (4)
C7—C8	1.359 (4)	C31—C32	1.389 (5)
C7—H7	0.9500	C32—C33	1.390 (4)
C8—C9	1.433 (4)	C32—H32	0.9500
C8—H8	0.9500	C33—N34	1.339 (5)
C9—N22	1.375 (4)	C33—H33	0.9500
C9—C10	1.400 (4)	N34—C35	1.338 (5)
C10—C11	1.399 (4)	C35—C36	1.396 (5)
C10—C31	1.500 (4)	C35—H35	0.9500
C11—N23	1.378 (4)	C36—H36	0.9500
C11—C12	1.451 (4)	C37—C38	1.394 (4)
C12—C13	1.351 (4)	C37—C42	1.395 (4)
C12—H12	0.9500	C38—C39	1.384 (4)
C13—C14	1.449 (4)	C38—H38	0.9500
C13—H13	0.9500	C39—N40	1.336 (4)
C14—N23	1.373 (4)	C39—H39	0.9500
C14—C15	1.404 (4)	N40—C41	1.335 (4)
C15—C16	1.403 (4)	C41—C42	1.389 (4)
C15—C37	1.495 (4)	C41—H41	0.9500
C16—N24	1.374 (4)	C42—H42	0.9500
C16—C17	1.441 (4)	C43—C44	1.385 (4)
C17—C18	1.357 (4)	C43—C48	1.396 (4)
C17—H17	0.9500	C44—C45	1.384 (4)
C18—C19	1.433 (4)	C44—H44	0.9500
C18—H18	0.9500	C45—N46	1.338 (5)
C19—N24	1.377 (4)	C45—H45	0.9500
C19—C20	1.401 (4)	N46—C47	1.337 (5)
C20—C43	1.496 (4)	C47—C48	1.381 (5)
N21—H21	0.8800	C47—H47	0.9500
N22—H22	0.8800	C48—H48	0.9500
N21—C1—C20	125.3 (3)	C11—N23—H23	126.9
N21—C1—C2	109.7 (2)	C16—N24—C19	108.1 (2)
C20—C1—C2	124.8 (3)	C16—N24—H24	125.9
C3—C2—C1	106.8 (3)	C19—N24—H24	125.9
C3—C2—H2	126.6	C30—C25—C26	117.1 (3)
C1—C2—H2	126.6	C30—C25—C5	122.4 (3)
C2—C3—C4	107.2 (3)	C26—C25—C5	120.5 (3)
C2—C3—H3	126.4	C27—C26—C25	119.1 (3)
C4—C3—H3	126.4	C27—C26—H26	120.4
N21—C4—C5	125.8 (3)	C25—C26—H26	120.4
N21—C4—C3	109.5 (2)	N28—C27—C26	124.3 (3)
C5—C4—C3	124.5 (3)	N28—C27—H27	117.9
C4—C5—C6	124.8 (3)	C26—C27—H27	117.9
C4—C5—C25	117.5 (3)	C27—N28—C29	115.9 (3)
C6—C5—C25	117.6 (2)	N28—C29—C30	124.4 (3)
N22—C6—C5	124.2 (3)	N28—C29—H29	117.8
N22—C6—C7	108.0 (3)	C30—C29—H29	117.8
C5—C6—C7	127.7 (3)	C29—C30—C25	119.2 (3)
C8—C7—C6	107.1 (3)	C29—C30—H30	120.4
C8—C7—H7	126.4	C25—C30—H30	120.4
C6—C7—H7	126.4	C36—C31—C32	117.9 (3)
C7—C8—C9	108.3 (3)	C36—C31—C10	121.9 (3)
C7—C8—H8	125.8	C32—C31—C10	120.2 (3)
C9—C8—H8	125.8	C31—C32—C33	119.0 (3)
N22—C9—C10	126.0 (3)	C31—C32—H32	120.5
N22—C9—C8	108.0 (2)	C33—C32—H32	120.5
C10—C9—C8	125.8 (3)	N34—C33—C32	124.1 (3)
C9—C10—C11	125.7 (3)	N34—C33—H33	118.0
C9—C10—C31	116.7 (2)	C32—C33—H33	118.0
C11—C10—C31	117.6 (3)	C33—N34—C35	116.2 (3)
N23—C11—C10	124.9 (3)	N34—C35—C36	124.1 (3)
N23—C11—C12	109.7 (3)	N34—C35—H35	118.0
C10—C11—C12	125.3 (3)	C36—C35—H35	118.0
C13—C12—C11	106.9 (3)	C31—C36—C35	118.7 (3)
C13—C12—H12	126.6	C31—C36—H36	120.6
C11—C12—H12	126.6	C35—C36—H36	120.6
C12—C13—C14	107.1 (3)	C38—C37—C42	117.0 (3)
C12—C13—H13	126.4	C38—C37—C15	122.8 (3)
C14—C13—H13	126.4	C42—C37—C15	120.2 (3)
N23—C14—C15	125.1 (3)	C39—C38—C37	119.6 (3)
N23—C14—C13	109.8 (3)	C39—C38—H38	120.2
C15—C14—C13	125.0 (3)	C37—C38—H38	120.2
C14—C15—C16	124.8 (3)	N40—C39—C38	123.8 (3)
C14—C15—C37	118.3 (3)	N40—C39—H39	118.1
C16—C15—C37	116.9 (2)	C38—C39—H39	118.1
N24—C16—C15	125.1 (3)	C39—N40—C41	116.3 (3)
N24—C16—C17	108.2 (3)	N40—C41—C42	124.4 (3)
C15—C16—C17	126.4 (3)	N40—C41—H41	117.8
C18—C17—C16	107.5 (3)	C42—C41—H41	117.8
C18—C17—H17	126.3	C41—C42—C37	118.8 (3)
C16—C17—H17	126.3	C41—C42—H42	120.6
C17—C18—C19	107.8 (3)	C37—C42—H42	120.6
C17—C18—H18	126.1	C44—C43—C48	116.9 (3)
C19—C18—H18	126.1	C44—C43—C20	123.1 (3)
N24—C19—C20	125.3 (3)	C48—C43—C20	120.0 (3)
N24—C19—C18	108.3 (2)	C45—C44—C43	119.6 (3)
C20—C19—C18	126.3 (3)	C45—C44—H44	120.2
C19—C20—C1	125.1 (3)	C43—C44—H44	120.2
C19—C20—C43	117.3 (3)	N46—C45—C44	124.3 (3)
C1—C20—C43	117.6 (2)	N46—C45—H45	117.8
C4—N21—C1	106.7 (2)	C44—C45—H45	117.8
C4—N21—H21	126.6	C47—N46—C45	115.4 (3)
C1—N21—H21	126.6	N46—C47—C48	124.9 (3)
C9—N22—C6	108.5 (2)	N46—C47—H47	117.5
C9—N22—H22	125.8	C48—C47—H47	117.5
C6—N22—H22	125.8	C47—C48—C43	118.9 (3)
C14—N23—C11	106.3 (3)	C47—C48—H48	120.5
C14—N23—H23	126.9	C43—C48—H48	120.5

(II) 5,10,15,20-tetra-4-pyridylporphyrin 1.514-hydrate

Crystal data

C40H26N8·1.514H2O	Dx = 1.369 Mg m^−3
Mr = 645.96	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I42d	Cell parameters from 4891 reflections
Hall symbol: I -4 2bw	θ = 2.0–27.9°
a = 15.2155 (4) Å	µ = 0.09 mm^−1
c = 13.5388 (6) Å	T = 110 K
V = 3134.39 (18) Å^3	Prism, red
Z = 4	0.35 × 0.25 × 0.15 mm
F(000) = 1348.9

Data collection

Nonius KappaCCD diffractometer	757 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.067
Graphite monochromator	θmax = 27.9°, θmin = 2.7°
Detector resolution: 12.8 pixels mm^-1	h = −19→19
1 deg. ω scans	k = −16→18
16180 measured reflections	l = −16→17
1042 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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.115	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0618P)^2 + 0.3277P] where P = (Fo^2 + 2Fc^2)/3
757 reflections	(Δ/σ)max < 0.001
118 parameters	Δρmax = 0.13 e Å^−3
1 restraint	Δρmin = −0.16 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.

The Friedel opposites were merged.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.19666 (18)	0.03473 (17)	0.5178 (2)	0.0401 (7)
C2	0.2587 (2)	0.10622 (18)	0.5225 (2)	0.0450 (7)
H2	0.3194	0.1017	0.5379	0.054*
C3	0.21436 (17)	0.18090 (18)	0.5010 (3)	0.0437 (7)
H3	0.2384	0.2384	0.4971	0.052*
C4	0.12407 (18)	0.15699 (17)	0.4854 (2)	0.0385 (7)
C5	0.05459 (18)	0.21687 (17)	0.4719 (2)	0.0381 (7)
N6	0.11491 (15)	0.06812 (15)	0.49667 (19)	0.0390 (6)
H6	0.0658	0.0379	0.4914	0.047*	0.50
C7	0.07877 (18)	0.30931 (19)	0.4471 (2)	0.0412 (7)
C8	0.0751 (2)	0.3755 (2)	0.5170 (3)	0.0613 (9)
H8	0.0556	0.3630	0.5822	0.074*
C9	0.1000 (3)	0.4600 (2)	0.4915 (3)	0.0638 (10)
H9	0.0983	0.5040	0.5412	0.077*
N10	0.12619 (19)	0.48306 (18)	0.4010 (2)	0.0580 (8)
C11	0.1281 (2)	0.4191 (2)	0.3350 (3)	0.0632 (10)
H11	0.1461	0.4337	0.2698	0.076*
C12	0.1060 (2)	0.3323 (2)	0.3534 (3)	0.0542 (9)
H12	0.1095	0.2895	0.3025	0.065*
O13	0.2500	0.6193 (2)	0.3750	0.0443 (14)	0.757 (10)
H13	0.2000 (18)	0.582 (2)	0.380 (4)	0.067*	0.757 (10)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0379 (15)	0.0432 (16)	0.0393 (15)	0.0019 (12)	−0.0012 (14)	−0.0047 (12)
C2	0.0375 (15)	0.0467 (16)	0.0508 (18)	−0.0026 (14)	−0.0039 (13)	−0.0070 (14)
C3	0.0424 (15)	0.0405 (15)	0.0481 (17)	−0.0036 (12)	−0.0004 (14)	0.0006 (14)
C4	0.0386 (15)	0.0390 (15)	0.0378 (16)	−0.0049 (13)	0.0015 (13)	0.0000 (12)
C5	0.0389 (15)	0.0380 (15)	0.0374 (15)	0.0020 (12)	−0.0026 (12)	0.0013 (12)
N6	0.0368 (13)	0.0377 (13)	0.0424 (14)	0.0007 (10)	0.0007 (11)	−0.0024 (11)
C7	0.0343 (15)	0.0385 (15)	0.0508 (18)	0.0000 (12)	−0.0063 (13)	0.0036 (13)
C8	0.093 (3)	0.0459 (18)	0.0449 (18)	−0.0106 (18)	−0.0094 (18)	0.0062 (16)
C9	0.087 (3)	0.0426 (18)	0.062 (2)	−0.0102 (17)	−0.023 (2)	0.0060 (16)
N10	0.0514 (17)	0.0483 (16)	0.074 (2)	−0.0059 (13)	−0.0002 (16)	0.0120 (15)
C11	0.069 (2)	0.053 (2)	0.067 (2)	0.0017 (18)	0.0212 (19)	0.0148 (18)
C12	0.060 (2)	0.0440 (17)	0.058 (2)	0.0023 (15)	0.0120 (17)	0.0037 (15)
O13	0.047 (2)	0.031 (2)	0.055 (3)	0.000	0.0040 (19)	0.000

Geometric parameters (Å, º)

C1—N6	1.374 (4)	C7—C12	1.380 (4)
C1—C5^i	1.400 (4)	C7—C8	1.383 (4)
C1—C2	1.441 (4)	C8—C9	1.384 (4)
C2—C3	1.353 (4)	C8—H8	0.9500
C2—H2	0.9500	C9—N10	1.336 (5)
C3—C4	1.437 (4)	C9—H9	0.9500
C3—H3	0.9500	N10—C11	1.322 (5)
C4—N6	1.368 (3)	C11—C12	1.384 (5)
C4—C5	1.407 (4)	C11—H11	0.9500
C5—C1^ii	1.400 (4)	C12—H12	0.9500
C5—C7	1.492 (4)	O13—H13	0.950 (2)
N6—H6	0.8800
N6—C1—C5^i	125.3 (2)	C1—N6—H6	126.4
N6—C1—C2	108.8 (2)	C12—C7—C8	117.2 (3)
C5^i—C1—C2	125.7 (3)	C12—C7—C5	121.4 (3)
C3—C2—C1	107.3 (3)	C8—C7—C5	121.5 (3)
C3—C2—H2	126.3	C9—C8—C7	119.7 (3)
C1—C2—H2	126.3	C9—C8—H8	120.2
C2—C3—C4	107.2 (2)	C7—C8—H8	120.2
C2—C3—H3	126.4	N10—C9—C8	123.7 (3)
C4—C3—H3	126.4	N10—C9—H9	118.2
N6—C4—C5	125.3 (2)	C8—C9—H9	118.2
N6—C4—C3	109.3 (2)	C11—N10—C9	115.7 (3)
C5—C4—C3	125.0 (2)	N10—C11—C12	125.1 (3)
C1^ii—C5—C4	125.0 (3)	N10—C11—H11	117.5
C1^ii—C5—C7	118.0 (2)	C12—C11—H11	117.5
C4—C5—C7	117.0 (3)	C7—C12—C11	118.7 (3)
C4—N6—C1	107.2 (2)	C7—C12—H12	120.6
C4—N6—H6	126.4	C11—C12—H12	120.6

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O13—H13···N10	0.95 (1)	1.90 (1)	2.823 (3)	163 (4)

(III) 5,10,15,20-tetra-4-pyridylporphyrin 2-chlorophenol disolvate

Crystal data

C40H26N8·2C6H5ClO	Z = 1
Mr = 875.79	F(000) = 454
Triclinic, P1	Dx = 1.418 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.5563 (2) Å	Cell parameters from 3736 reflections
b = 10.0441 (3) Å	θ = 2.6–27.9°
c = 16.1903 (5) Å	µ = 0.21 mm^−1
α = 77.841 (2)°	T = 110 K
β = 88.9097 (19)°	Needles, red
γ = 79.6939 (14)°	0.60 × 0.20 × 0.10 mm
V = 1025.24 (5) Å^3

Data collection

Nonius KappaCCD diffractometer	3617 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.036
Graphite monochromator	θmax = 27.9°, θmin = 2.6°
Detector resolution: 12.8 pixels mm^-1	h = 0→8
1 deg. ϕ and ω scans	k = −12→13
11144 measured reflections	l = −20→21
4834 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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.156	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.064P)^2 + 1.1604P] where P = (Fo^2 + 2Fc^2)/3
4834 reflections	(Δ/σ)max < 0.001
289 parameters	Δρmax = 0.42 e Å^−3
0 restraints	Δρmin = −0.70 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	0.9091 (3)	0.3183 (2)	0.46729 (13)	0.0160 (4)
C2	1.0192 (3)	0.2573 (2)	0.40116 (13)	0.0187 (4)
H2	1.1535	0.2016	0.4057	0.022*
C3	0.8933 (3)	0.2954 (2)	0.33259 (13)	0.0191 (4)
H3	0.9219	0.2727	0.2790	0.023*
C4	0.7045 (3)	0.3783 (2)	0.35631 (13)	0.0165 (4)
C5	0.5302 (3)	0.4298 (2)	0.30212 (13)	0.0177 (4)
C6	0.3418 (3)	0.5064 (2)	0.32100 (13)	0.0163 (4)
C7	0.1741 (3)	0.5711 (2)	0.26300 (14)	0.0200 (4)
H7	0.1660	0.5630	0.2058	0.024*
C8	0.0279 (3)	0.6465 (2)	0.30376 (13)	0.0192 (4)
H8	−0.0992	0.7008	0.2799	0.023*
C9	0.0994 (3)	0.6295 (2)	0.38891 (13)	0.0162 (4)
C10	0.0064 (3)	0.6968 (2)	0.45140 (13)	0.0160 (4)
N11	0.7190 (3)	0.39229 (17)	0.43822 (11)	0.0155 (4)
H11	0.6259	0.4390	0.4662	0.019*	0.50
N12	0.2887 (3)	0.54210 (18)	0.39700 (11)	0.0158 (4)
H12	0.3644	0.5134	0.4438	0.019*	0.50
C13	0.5466 (3)	0.3985 (2)	0.21559 (13)	0.0200 (4)
C14	0.6716 (4)	0.4618 (3)	0.15515 (14)	0.0265 (5)
H14	0.7434	0.5303	0.1666	0.032*
C15	0.6897 (4)	0.4229 (3)	0.07742 (15)	0.0317 (6)
H15	0.7760	0.4664	0.0365	0.038*
N16	0.5926 (3)	0.3278 (2)	0.05711 (13)	0.0313 (5)
C17	0.4674 (4)	0.2702 (3)	0.11446 (16)	0.0297 (5)
H17	0.3942	0.2042	0.1004	0.036*
C18	0.4397 (4)	0.3025 (3)	0.19390 (15)	0.0254 (5)
H18	0.3488	0.2596	0.2329	0.030*
C19	−0.1898 (3)	0.7976 (2)	0.42717 (13)	0.0166 (4)
C20	−0.2005 (3)	0.9376 (2)	0.42684 (13)	0.0199 (4)
H20	−0.0824	0.9702	0.4423	0.024*
C21	−0.3856 (4)	1.0287 (2)	0.40371 (14)	0.0229 (5)
H21	−0.3904	1.1233	0.4052	0.028*
N22	−0.5574 (3)	0.9920 (2)	0.37948 (12)	0.0242 (4)
C23	−0.5444 (3)	0.8573 (2)	0.37953 (15)	0.0237 (5)
H23	−0.6640	0.8280	0.3625	0.028*
C24	−0.3682 (3)	0.7579 (2)	0.40275 (14)	0.0213 (5)
H24	−0.3692	0.6637	0.4020	0.026*
Cl25	1.04786 (11)	0.23131 (8)	−0.01971 (4)	0.0426 (2)
C26	0.9931 (4)	0.1380 (3)	−0.09282 (15)	0.0292 (5)
C27	1.1587 (4)	0.0660 (3)	−0.12998 (17)	0.0382 (6)
H27	1.2972	0.0642	−0.1129	0.046*
C28	1.1202 (5)	−0.0027 (3)	−0.19171 (17)	0.0411 (7)
H28	1.2319	−0.0510	−0.2181	0.049*
C29	0.9168 (5)	−0.0009 (3)	−0.21498 (16)	0.0361 (6)
H29	0.8901	−0.0483	−0.2574	0.043*
C30	0.7536 (4)	0.0687 (3)	−0.17740 (16)	0.0328 (6)
H30	0.6155	0.0688	−0.1942	0.039*
C31	0.7890 (4)	0.1396 (3)	−0.11446 (15)	0.0289 (5)
O32	0.6204 (3)	0.2076 (2)	−0.08230 (12)	0.0404 (5)
H32	0.6511	0.2527	−0.0409	0.048*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0134 (10)	0.0146 (9)	0.0203 (10)	−0.0019 (8)	0.0010 (8)	−0.0046 (8)
C2	0.0151 (10)	0.0189 (10)	0.0212 (10)	0.0007 (8)	0.0019 (8)	−0.0054 (8)
C3	0.0187 (10)	0.0207 (10)	0.0180 (10)	−0.0007 (8)	0.0035 (8)	−0.0074 (8)
C4	0.0161 (10)	0.0160 (10)	0.0176 (10)	−0.0020 (8)	0.0014 (8)	−0.0049 (8)
C5	0.0177 (10)	0.0177 (10)	0.0183 (10)	−0.0025 (8)	0.0004 (8)	−0.0056 (8)
C6	0.0166 (10)	0.0161 (10)	0.0169 (10)	−0.0024 (8)	−0.0007 (8)	−0.0054 (8)
C7	0.0196 (11)	0.0223 (11)	0.0185 (10)	−0.0024 (9)	−0.0021 (8)	−0.0064 (8)
C8	0.0167 (10)	0.0199 (10)	0.0206 (10)	−0.0003 (8)	−0.0026 (8)	−0.0051 (8)
C9	0.0147 (10)	0.0146 (9)	0.0200 (10)	−0.0027 (8)	0.0002 (8)	−0.0051 (8)
C10	0.0132 (10)	0.0147 (10)	0.0196 (10)	−0.0019 (8)	0.0008 (8)	−0.0032 (8)
N11	0.0139 (8)	0.0156 (8)	0.0172 (8)	−0.0011 (7)	0.0005 (7)	−0.0052 (7)
N12	0.0145 (8)	0.0165 (8)	0.0172 (8)	−0.0015 (7)	0.0004 (7)	−0.0060 (7)
C13	0.0169 (10)	0.0230 (11)	0.0183 (10)	0.0045 (9)	−0.0027 (8)	−0.0072 (8)
C14	0.0287 (13)	0.0293 (12)	0.0210 (11)	−0.0026 (10)	0.0013 (9)	−0.0064 (9)
C15	0.0362 (14)	0.0356 (14)	0.0199 (11)	−0.0001 (11)	0.0052 (10)	−0.0044 (10)
N16	0.0337 (12)	0.0365 (12)	0.0224 (10)	0.0042 (10)	−0.0036 (9)	−0.0115 (9)
C17	0.0295 (13)	0.0332 (13)	0.0278 (12)	0.0011 (11)	−0.0053 (10)	−0.0145 (10)
C18	0.0223 (12)	0.0304 (12)	0.0247 (11)	−0.0015 (10)	−0.0021 (9)	−0.0112 (9)
C19	0.0154 (10)	0.0189 (10)	0.0153 (9)	−0.0012 (8)	0.0010 (8)	−0.0045 (8)
C20	0.0200 (11)	0.0198 (10)	0.0202 (10)	−0.0021 (9)	−0.0010 (8)	−0.0063 (8)
C21	0.0243 (12)	0.0177 (10)	0.0254 (11)	0.0006 (9)	0.0002 (9)	−0.0052 (9)
N22	0.0194 (10)	0.0222 (10)	0.0289 (10)	−0.0006 (8)	0.0012 (8)	−0.0033 (8)
C23	0.0158 (11)	0.0242 (11)	0.0305 (12)	−0.0040 (9)	−0.0004 (9)	−0.0040 (9)
C24	0.0174 (11)	0.0181 (10)	0.0280 (11)	−0.0031 (8)	0.0001 (9)	−0.0042 (9)
Cl25	0.0351 (4)	0.0593 (5)	0.0388 (4)	−0.0081 (3)	−0.0019 (3)	−0.0223 (3)
C26	0.0315 (13)	0.0327 (13)	0.0224 (11)	−0.0035 (11)	−0.0001 (10)	−0.0057 (10)
C27	0.0302 (14)	0.0472 (17)	0.0304 (13)	0.0053 (12)	−0.0008 (11)	−0.0030 (12)
C28	0.0425 (16)	0.0418 (16)	0.0312 (14)	0.0123 (13)	0.0035 (12)	−0.0073 (12)
C29	0.0545 (18)	0.0278 (13)	0.0255 (12)	−0.0006 (12)	−0.0026 (12)	−0.0097 (10)
C30	0.0362 (14)	0.0367 (14)	0.0263 (12)	−0.0085 (12)	0.0000 (11)	−0.0065 (11)
C31	0.0293 (13)	0.0332 (13)	0.0241 (12)	−0.0039 (11)	0.0026 (10)	−0.0072 (10)
O32	0.0310 (10)	0.0616 (13)	0.0340 (10)	−0.0035 (9)	0.0048 (8)	−0.0268 (9)

Geometric parameters (Å, º)

C1—N11	1.367 (3)	C15—H15	0.9500
C1—C10^i	1.406 (3)	N16—C17	1.336 (3)
C1—C2	1.460 (3)	C17—C18	1.393 (3)
C2—C3	1.343 (3)	C17—H17	0.9500
C2—H2	0.9500	C18—H18	0.9500
C3—C4	1.456 (3)	C19—C24	1.390 (3)
C3—H3	0.9500	C19—C20	1.394 (3)
C4—N11	1.370 (3)	C20—C21	1.388 (3)
C4—C5	1.407 (3)	C20—H20	0.9500
C5—C6	1.398 (3)	C21—N22	1.336 (3)
C5—C13	1.496 (3)	C21—H21	0.9500
C6—N12	1.374 (3)	N22—C23	1.340 (3)
C6—C7	1.428 (3)	C23—C24	1.385 (3)
C7—C8	1.362 (3)	C23—H23	0.9500
C7—H7	0.9500	C24—H24	0.9500
C8—C9	1.431 (3)	Cl25—C26	1.736 (3)
C8—H8	0.9500	C26—C31	1.386 (4)
C9—N12	1.377 (3)	C26—C27	1.394 (4)
C9—C10	1.403 (3)	C27—C28	1.379 (4)
C10—C1^i	1.406 (3)	C27—H27	0.9500
C10—C19	1.490 (3)	C28—C29	1.388 (4)
N11—H11	0.8800	C28—H28	0.9500
N12—H12	0.8800	C29—C30	1.375 (4)
C13—C14	1.388 (3)	C29—H29	0.9500
C13—C18	1.392 (3)	C30—C31	1.405 (3)
C14—C15	1.391 (3)	C30—H30	0.9500
C14—H14	0.9500	C31—O32	1.348 (3)
C15—N16	1.336 (4)	O32—H32	0.9286
N11—C1—C10^i	126.03 (18)	C14—C15—H15	118.2
N11—C1—C2	110.72 (18)	C15—N16—C17	117.5 (2)
C10^i—C1—C2	123.24 (19)	N16—C17—C18	122.9 (2)
C3—C2—C1	106.49 (18)	N16—C17—H17	118.6
C3—C2—H2	126.8	C18—C17—H17	118.6
C1—C2—H2	126.8	C13—C18—C17	119.3 (2)
C2—C3—C4	106.73 (18)	C13—C18—H18	120.4
C2—C3—H3	126.6	C17—C18—H18	120.4
C4—C3—H3	126.6	C24—C19—C20	117.1 (2)
N11—C4—C5	125.97 (18)	C24—C19—C10	122.16 (19)
N11—C4—C3	110.69 (18)	C20—C19—C10	120.78 (19)
C5—C4—C3	123.28 (18)	C21—C20—C19	119.3 (2)
C6—C5—C4	126.66 (19)	C21—C20—H20	120.4
C6—C5—C13	116.44 (19)	C19—C20—H20	120.4
C4—C5—C13	116.89 (18)	N22—C21—C20	124.2 (2)
N12—C6—C5	126.62 (19)	N22—C21—H21	117.9
N12—C6—C7	106.96 (18)	C20—C21—H21	117.9
C5—C6—C7	126.27 (19)	C21—N22—C23	115.8 (2)
C8—C7—C6	108.28 (19)	N22—C23—C24	124.4 (2)
C8—C7—H7	125.9	N22—C23—H23	117.8
C6—C7—H7	125.9	C24—C23—H23	117.8
C7—C8—C9	107.97 (19)	C23—C24—C19	119.2 (2)
C7—C8—H8	126.0	C23—C24—H24	120.4
C9—C8—H8	126.0	C19—C24—H24	120.4
N12—C9—C10	125.37 (19)	C31—C26—C27	121.8 (2)
N12—C9—C8	106.96 (17)	C31—C26—Cl25	119.94 (19)
C10—C9—C8	127.48 (19)	C27—C26—Cl25	118.2 (2)
C9—C10—C1^i	124.75 (19)	C28—C27—C26	119.5 (3)
C9—C10—C19	116.90 (18)	C28—C27—H27	120.3
C1^i—C10—C19	118.24 (18)	C26—C27—H27	120.3
C1—N11—C4	105.35 (16)	C27—C28—C29	119.5 (2)
C1—N11—H11	127.3	C27—C28—H28	120.2
C4—N11—H11	127.3	C29—C28—H28	120.2
C6—N12—C9	109.80 (17)	C30—C29—C28	120.9 (2)
C6—N12—H12	125.1	C30—C29—H29	119.6
C9—N12—H12	125.1	C28—C29—H29	119.6
C14—C13—C18	117.9 (2)	C29—C30—C31	120.7 (3)
C14—C13—C5	121.3 (2)	C29—C30—H30	119.7
C18—C13—C5	120.8 (2)	C31—C30—H30	119.7
C13—C14—C15	118.7 (2)	O32—C31—C26	125.6 (2)
C13—C14—H14	120.7	O32—C31—C30	116.8 (2)
C15—C14—H14	120.7	C26—C31—C30	117.6 (2)
N16—C15—C14	123.7 (2)	C31—O32—H32	113.8
N16—C15—H15	118.2

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O32—H32···N16	0.93	1.90	2.764 (3)	154