Crystal structure of 2,3-dimeth­oxy-meso-tetra­kis(penta­fluoro­phen­yl)morpholino­chlorin methyl­ene chloride 0.44-solvate

Churchill, S.B.S.; Sharma, M.; Brückner, C.; Zeller, M.

doi:10.1107/S2056989020009093

research communications

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ISSN: 2056-9890

Volume 76| Part 8| August 2020| Pages 1222-1228

https://doi.org/10.1107/S2056989020009093

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Crystal structure of 2,3-dimethoxy-meso-tetrakis(pentafluorophenyl)morpholinochlorin methylene chloride 0.44-solvate

Serena B. S. Churchill,^a Meenakshi Sharma,^a Christian Brückner ^a and Matthias Zeller ^b ^*

^aDepartment of Chemistry, University of Connecticut, Storrs, Connecticut 06269-3060, USA, and ^bDepartment of Chemistry, Purdue University, 560 Oval Dr., W. Lafayette, IN 47907-2084, USA
^*Correspondence e-mail: zeller4@purdue.edu

Edited by H. Ishida, Okayama University, Japan (Received 19 June 2020; accepted 2 July 2020; online 7 July 2020)

The title morpholinochlorin, C₄₆H₁₆F₂₀N₄O₃, was crystallized from hexane/methylene chloride as its 0.44 methylene chloride solvate, C₄₆H₁₆F₂₀N₄O₃·0.44CH₂Cl₂. The morpholinochlorin was synthesized by stepwise oxygen insertion into a porphyrin using a `breaking and mending strategy': NaIO₄-induced diol cleavage of the corresponding 2,3-dihydroxychlorin with in situ methanol-induced, acid-catalyzed intramolecular ring closure of the intermediate secochlorins bisaldehyde. Formally, one of the pyrrolic building blocks was thus replaced by a 2,3-dimethoxymorpholine moiety. Like other morpholinochlorins, the macrocycle of the title compound adopts a ruffled conformation, and the modulation of the porphyrinic π-system chromophore induces a red-shift of its optical spectrum compared to its corresponding chlorin analog. Packing in the crystal is governed by interactions involving the fluorine atoms of the pentafluorophenyl substituents, dominated by C—H⋯F interactions, and augmented by short fluorine⋯fluorine contacts, C—F⋯π interactions, and one severely slipped π-stacking interaction between two pentafluorophenyl rings. The solvate methylene chloride molecule is disordered over two independent positions around an inversion center with occupancies of two × 0.241 (5) and two × 0.199 (4), for a total site occupancy of 88%.

Keywords: porphyrinoids; pyrrole-modified porphyrins; morpholinochlorins; crystal structure.

CCDC reference: 2013871

1. Chemical context

A major aim in contemporary porphyrin chemistry is the generation of NIR (>650 nm) absorbing or fluorescing chromophores for a variety of biomedical and technical applications, such as photodynamic therapy (Dolmans et al., 2003 ), solar-energy conversion (Hedley et al., 2017 ), or photoacoustic or fluorescence imaging (Gujrati et al., 2017 ; Borg & Rochford, 2018 ). Inter alia, this gave rise to the synthesis of a wide array of porphyrin analogues, including porphyrinoids incorporating non-pyrrolic heterocycles (Brückner et al., 2014 ; Lash, 2017 ; Chatterjee et al., 2017 ).

One member of the family of porphyrinoids incorporating non-pyrrolic heterocycles are the morpholinochlorins (1) (Fig. 1) in which one pyrrolic building block is replaced by a morpholine (Brückner et al., 1998 , 2011 ; McCarthy et al., 2003 ). This formal replacement is achieved by a stepwise oxygen insertion into a porphyrin using a so-called `breaking and mending' strategy (Brückner, 2016 ). As a consequence of the atom insertion, morpholinochlorins are non-planar (McCarthy et al., 2003; Brückner et al., 2011; Sharma et al., 2017 ). The twisted (ruffled) conformation of helimeric chirality of the morpholinochlorins was found to be affected by the size and number of alkoxy substituents, the presence of covalent links between the morpholine unit and the flanking aryl group, and the presence and type of central metal (Daniell & Brückner, 2004 ; Brückner et al., 2011; Sharma et al., 2017). Porphyrinoids containing two morpholine moieties are known (Daniell & Brückner, 2004; Guberman-Pfeffer et al., 2017 ), as well as other porphyrinoids containing morpholine building blocks (Lara et al., 2005 ; Samankumara et al., 2015 ; Akhigbe et al., 2016 ). The modulation of the conformation of the porphyrinic π-system also affects their electronic properties; morpholinochlorins are more red-shifted than a corresponding chlorin (Brückner et al., 2011; Guberman-Pfeffer et al., 2017). The influence of the meso-substituents on the conformation and electronics of the morpholinochlorins has not been investigated.

Figure 1
Structures of select morpholinochlorins

For porphyrinoids at large, the introduction of meso-pentafluorophenyl-groups (or fluorine atoms, in general) has long been known to alter their electronic properties (Spellane et al., 1980 ; Leroy & Bondon, 2008 ; Nardi et al., 2013 ); they often become slightly blue-shifted compared to their non-fluorinated analogues and are harder to oxidize. Also, the meso-pentafluorophenyl-groups are very convenient handles for the further synthetic manipulation of the porphyrinoids (Costa et al., 2011 ; Golf et al., 2015 ; Hewage et al., 2015 ; Bhupathiraju et al., 2016 ). Their effect on the conformation of the molecules, when compared to their hydrogen analogs, has been shown to be frequently minimal (Leroy & Bondon, 2008).

2. Structural commentary

The title compound 1d was obtained in crystalline form from hexane/methylene chloride as its 0.44 methylene chloride solvate (Fig. 2). 1d crystallizes as a racemic mixture of two helimers in the monoclinic space group C2/c, and its structure is generally in line with that of the other three free base morpholinochlorins that have been structurally described (Fig. 1): the meso-tolyl derivative 1b with two ethoxy substituents in the 2,3 positions of the morpholine (McCarthy et al., 2003); the meso-phenyl derivative 1e with a single methoxy substituent (Brückner et al., 2011), and the meso-phenyl derivative 1f lacking any morpholine substitution (Brückner et al., 2011). The macrocycle in all morpholinochlorins is non-planar. In the symmetrically substituted morpholinochlorins, 1b, 1d and 1f, individual molecules are ruffled (Shelnutt et al., 1998 ), feature a chiral axis and are helimeric. Derivative 1e with only a single methoxy substituent on the morpholine (Brückner et al., 2011) features a more saddled conformation of its macrocycle (Brückner et al., 2011). The geometries of the morpholino rings also vary between the four structures. In the two 2,3-substituted derivatives, title compound 1d and meso-tolyl derivative 1b, the substituents are arranged anti to each other, and the morpholino rings adopt a conformation that is best described as half-twist. This stereoselective arrangement had been rationalized on steric and stereoelectronic grounds (Brückner et al., 2011). The morpholine moiety in the mono-alkoxy derivative 1e adopts a half-boat conformation (Brückner et al., 2011).

Figure 2
The structure of 1d with the atom-labeling scheme. Probability ellipsoids are drawn at the 50% level. Symmetry-created atoms are shown in capped-stick mode and are unlabeled. Dashed bonds indicate minor moiety disordered and symmetry-related atoms. Some carbon atom labels are omitted for clarity.

Out-of-plane plots of the macrocycle conformations of 1b and 1d directly compare their ruffled conformation that allows the central nitrogen atoms to remain idealized in the central plane (Fig. 3). The conformation of the C₂₀N₄O morpholinochlorin macrocycle in 1d is slightly more ruffled (r.m.s. = 0.323 Å) (Shelnutt et al., 1998) than in 1b (r.m.s. = 0.276 Å; Sharma et al., 2017). While the tripyrrolic portion of 1d is significantly more ruffled than the corresponding section of 1b, the morpholine moieties are, except for the position of the ring oxygen, rather similar.

Figure 3
Out-of-plane displacement plots of macrocycles of the title compound 1d (black trace) and morpholinochlorin 1b (gray trace).

Similar to other meso-aryl porphyrinoids, the torsion angles in the morpholinochlorins between the meso-aryl substituents and the mean plane of the macrocycle vary with the steric demand of the groups flanking the aryl substituents. The meso-pentafluorophenyl groups neighboring the pyrrolic units (C₅F₆ rings of C27 and C33) face little steric constraints and adopt dihedral angles of 71.92 (2) and 74.95 (3)°, respectively. Those adjacent to the morpholine moiety (C₆F₅ rings of C21 and C39) are more sterically encumbered and are about 10° closer to perpendicular to the macrocycle plane, with values of 82.70 (3) and 81.44 (2)°. The corresponding values for compound 1b are very similar, with values of 71.89 and 73.73°, and 89.55 and 86.32°, respectively.

The close structural relationship between the 2,3-disubstituted derivatives 1b and 1d allows us to investigate how minor conformational changes might affect the optical properties of the morpholinochlorins. The torsion angles between the two C—C bonds in the morpholine units [C_a—C_b–(N)–C_b—C_a, C2—C1—(N1)—C4—C3 in 1d] in the two morpholinochlorins 1b and 1d vary slightly, with this angle being smaller in the title compound [35.2° in 1b and 25.5 (4)° 1d]. This angle is important as it strongly affects the λ_max of the morpholinochlorins (Guberman-Pfeffer et al., 2017), with a larger torsion angle being correlated to a longer λ_max in their UV–vis absorption spectra. However, while the UV–vis spectra of the two species show distinct differences, their λ_max values are essentially the same (680 nm in 1d vs 678 nm in 1b; Fig. 4), likely as the result of the combination of their differing conformation and electron-withdrawing natures of their meso-substituents (phenyl in 1b and pentafluorophenyl in 1d).

Figure 4
Normalized UV–vis spectra (CH₂Cl₂) of the compounds indicated.

3. Supramolecular features

Interactions involving fluorine atoms play a dominant role in facilitating the arrangement of molecules of 1d in the crystal. Dominant are C—H⋯F hydrogen-bond-like interactions, involving both methyl as well as pyrrole moieties as the hydrogen-atom donor. Weak C—H⋯F interactions involving the solvent are also present. The most prominent of these interactions are given in Table 1 and are discussed below. Also present are a number of short fluorine⋯fluorine contacts, C—F⋯π interactions (towards the π system of a the macrocycle), and one severely slipped π-stacking interaction between two pentafluorophenyl rings.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8⋯F18ⁱ	0.95	2.59	3.424 (3)	147
C18—H18⋯F8ⁱⁱ	0.95	2.51	3.319 (3)	143
C45—H45A⋯F12ⁱⁱⁱ	0.98	2.55	3.519 (3)	169
C45—H45B⋯F19^iv	0.98	2.66	3.389 (3)	132
C45—H45A⋯F20	0.98	2.82	3.184 (3)	103
C46—H46A⋯F10^v	0.98	2.63	3.496 (4)	148
C46—H46C⋯F1^vi	0.98	2.60	3.505 (4)	153
C48—H48B⋯F12ⁱⁱⁱ	0.99	2.42	3.25 (5)	141
N2—H2A⋯N1	0.85 (3)	2.56 (3)	3.040 (3)	117 (3)
N2—H2A⋯N3	0.85 (3)	2.33 (3)	2.858 (3)	121 (3)
N4—H4⋯N1	0.79 (3)	2.61 (3)	3.040 (3)	116 (2)
N4—H4⋯N3	0.79 (3)	2.33 (3)	2.852 (3)	125 (3)
Symmetry codes: (i) x, y+1, z; (ii) x, y-1, z; (iii) $[-x+1, y, -z+{\script{1\over 2}}]$ ; (iv) -x+1, -y+1, -z+1; (v) $[x-{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (vi) $[-x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ .

The most prominent C—H⋯F interactions (Levina et al., 2019 ) involve the two methyl groups of the 2,3-dimethoxymorpholino unit (Fig. 5a). Both methoxy substituents are engaged in several of these interactions: C45 exhibits interactions with fluorine atoms from three different pentafluorophenyl groups: with meta fluorine atoms F12ⁱⁱⁱ and F19^iv [symmetry codes: (iii) −x + 1, y, −z + $[{1\over 2}]$ ; (iv) −x + 1, −y + 1, −z + 1], and one intramolecular interaction with F20, an ortho-fluorine atom. Angular and H⋯F distance values for this intramolecular interaction appear quite unfavorable: the C—H⋯F angle is only 103°, and the H⋯F distance is 2.82 Å. However, only a slight rotation of the methyl H atoms is required to create a much more favorable geometry, and the C⋯F distance between C45 and F20 is at 3.184 (3) quite short (the shortest of all C—H⋯F interactions observed in 1d). Interactions involving the methoxy group of C46 involve F10^v and F1^vi, two ortho-fluorine atoms [symmetry codes: (v) x − $[{1\over 2}]$ , y − $[{1\over 2}]$ , z; (vi) −x + $[{1\over 2}]$ , −y + $[{3\over 2}]$ , −z + 1]. Two C—H⋯F interactions originate from pyrrole moieties, involving H atoms at the pyrrole moieties flanking the morpholine unit: H8 towards F18ⁱ, and H18 towards F8ⁱⁱ, with both F8 and F18 being para-fluorine atoms [symmetry codes: (i) x, y + 1, z; (ii) x, y − 1, z]. These two interactions work in tandem with each other and with a severely slipped π–π stacking interaction, between the rings of F6–F10 and F16ⁱ–F20ⁱ, connecting two opposite ends of the morpholinochlorin molecule with its neighbors to create infinite chains connected via C—H⋯F and slipped π–π stacking interactions (Fig. 5b). The centroid-to-centroid distance of the π-stacking interaction is 4.3551 (15) Å, with a ring slippage of 2.795 Å and a centroid-to-mean-plane distance of 3.1661 (12) Å. The last C—H⋯F interaction involves the methylene group of the minor moiety solvate methylene chloride molecule. Given the degree of disorder of the solvate molecules (see Refinement section), this interaction is probably vaguely defined at best and will not be discussed in detail.

Figure 5
(a) C—H⋯F interactions involving the methoxy hydrogen atoms (turquoise dashed lines). Accepting moieties are truncated to their pentafluorophenyl groups, and symmetry-related atoms not directly involved in an interaction are shown in stick mode for clarity. (b) C—H⋯F and slipped π–π stacking interactions (turquoise dashed lines) connecting molecules into infinite chains. Red spheres indicate the centroids of the respective aromatic rings, green dashed lines the distance between centroids (in Å). For symmetry codes, see Table 1

Besides C—H⋯F interactions, which are generally considered as directional interactions similar in strength to the better investigated C—H⋯O interactions, 1d also features a number of short F⋯F contacts. In contrast to halogen⋯halogen bonds involving chlorine, and especially bromine and iodine (the classical halogen bonds), interactions between two fluorine atoms are different and much weaker in nature (Cavallo et al., 2016 ). C—F⋯F—C interactions are generally not directional and do usually not play any structure-directing role. The energy of intermolecular C—F⋯F—C interactions in molecular compounds is estimated at <4 kJ mol⁻¹, substantially lower that of C—H⋯F interactions, which tend to range from 5 to 7 kJ mol⁻¹. They are, however, still regarded as weakly attractive and contributing to the overall stability of the packing arrangement (Levina et al., 2019). Three distinct interactions of this kind with F⋯F distances under 3.0 Å are observed in 1d. Fluorine atom F5 forms close contacts with F7 and F8 located at the C₆F₅ ring of a neighboring molecule. The F⋯F distances are 2.797 (2) Å (F5⋯F7^vii) and 2.828 (3) Å (F5⋯F8^vii) [symmetry code: (vii) $[{1\over 2}]$ − x, − $[{1\over 2}]$ + y, $[{1\over 2}]$ − z]. With the intramolecular distance between F7 and F8 being 2.726 (2) Å, this leads to the formation of a nearly equilateral triangle of F atoms (Fig. 6a). It should be noted that atom F8 of this F₃-triangle also acts as the acceptor of the C18—H18⋯F8ⁱⁱ contact and the backside of the aromatic ring of F8 is involved in the slipped π–π stacking interaction (see discussion above). Fluorine atom F11 features a close contact with a symmetry-created copy of itself, created by a twofold axis. The F⋯Fⁱⁱⁱ distance here is 2.783 (3) Å, and the C—F⋯Fⁱⁱⁱ angle is 125.5 (2)° [symmetry code: (iii) −x + 1, y, −z + $[{1\over 2}]$ ]. F11 also interacts with the π system of the macrocycle created by the same twofold axis, with F⋯C distances towards C14ⁱⁱⁱ and C15ⁱⁱⁱ of 3.046 (3) and 3.035 (3) Å, and F12 acts as the acceptor of the C45—H45C⋯F12ⁱⁱⁱ interaction, thus creating a larger multi-interaction contact between the two neighboring molecules with mutually stabilizing interactions (Fig. 7a). The last clearly recognizable interaction between fluorine atoms is an inversion-symmetric pair of two F⋯F contacts, involving F14 and F15 of one C₆F₅ ring and their symmetry-related counterparts across a crystallographic inversion center (Fig. 6b). The F14⋯F15^viii distance is 7.248 (2) Å. The C37—F14⋯F15^viii angle here is 168.6 (2)° [symmetry code: (viii) $[{1\over 2}]$ − x, $[{3\over 2}]$ − y, −z].

Figure 6
F⋯F interactions (turquoise dashed lines) creating a triangular motif. Symmetry-related moieties are truncated to their pentafluorophenyl groups, and atoms not directly involved in an interaction are shown in stick mode for clarity. Symmetry codes: (vii) −x + $[{1\over 2}]$ , y − $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (viii) −x + $[{1\over 2}]$ , −y + $[{3\over 2}]$ , −z + 1.

Figure 7
F⋯F, C—F⋯π and C—H⋯F interactions (turquoise dashed lines) connecting molecules into dimers. Pentafluorophenyl groups not involved in the shown interactions are shown in wireframe mode for clarity. For symmetry codes, see Table 1

Besides F11, F2 and F3 are also involved in intermolecular C—F⋯π interactions, pointing nearly perpendicularly towards C atoms (C41^vi and C42^vi) of another pentafluorophenyl ring [symmetry code: (vi) −x + $[{1\over 2}]$ , −y + $[{3\over 2}]$ , −z + 1]. The F⋯C distances are 3.034 (3) and 2.978 (3) Å for F2 and F3, respectively. There are two interactions of this kind per molecule, one as the C—F donor and one as the π-density moiety accepting the C—F⋯π bond, connecting molecules into centrosymmetric dimers. One of the methyl C—H⋯F contacts (towards F1) is also involved in the formation of these dimers (Fig. 7b).

4. Database survey

A CSD search (Version 5.41 with updates up to May 2020; Groom et al., 2016 ) for porphyrinic macrocyles of three pyrroles and a single six-membered ring while retaining the porphyrin-like architecture of four central nitrogen atoms reveals 24 structures: six pyriporphyrins (i.e., porphyrinoids containing a pyridine building block), fifteen morpholinochlorins, two thiomorpholines [UCIKOJ and UCILIE (Sharma et al., 2016 )], and a single 1,3-oxazinochlorin (WUDMIT; Meehan et al., 2015 ). Among the 1,4-morpholinochlorins, six are free base structures, the remainder are metal complexes [of Cu^II, Ni^II – most frequently, Zn^II, Ag^II and Pd^II, see Fig. 1 for CSD codes]. Only a single structure, (1b, RUXJUP; McCarthy et al., 2003) is directly comparable to 1d; all the others contain either covalent morpholine-to-meso-aryl linkages (AVICAK; Daniell & Brückner, 2004; Brückner et al., 2011), a reduced pyrrole moiety (KECFEF; Samankumara et al., 2012 ; Guberman-Pfeffer et al., 2017), or both (KECDUT; Samankumara et al., 2012; Guberman-Pfeffer et al., 2017), or only one (1e, AVICEO; Brückner et al., 2011) or no alkoxy substituents (1f, AVICOY; Brückner et al., 2011). These structural factors affect the conformation of the chromophore of evidently large plasticity (Brückner et al., 2011; Guberman-Pfeffer et al., 2017; Sharma et al., 2017).

5. Synthesis and crystallization

We prepared the title compound 1d according to an established strategy from the corresponding 2,3-dihydroxychlorin 2 (Fig. 1) (Brückner et al., 2011): Oxidative diol cleavage is followed, in a one-pot approach, by a nucleophile-induced (methanol), acid-catalyzed intramolecular ring closure and subsequent double-acetalization. Specifically, meso-tetrakis(pentafluorophenyl)-2,3-dihydroxychlorin 2 (Hyland et al., 2012 ) (30 mg, 2.97 × 10 ⁻⁵ mol) was dissolved in a 50 mL two-necked round-bottom flask equipped with a stir bar and gas in/outlets in CHCl₃ (7 mL, amylene stabilized). The vessel was put under a protective atmosphere of N₂. Freshly prepared NaIO₄ heterogenized on silica (Zhong & Shing, 1997 ) (0.30 g) and dry MeOH (∼0.3 mL) were added and the reaction was acidified with the vapors from a conc. aqueous HCl bottle (36%), delivered to the surface of the solution as puffs (3 × ∼1 mL) from a Pasteur pipette topped by a small latex bulb. The reaction was shielded from light by aluminum foil, stirred at ambient temperature and monitored by TLC (silica gel/CH₂Cl₂). After 24 h reaction time, no further reaction was observed; the solution was filtered (glass frit M) and the filtrate reduced to dryness by rotary evaporation. The crude product was dissolved in CH₂Cl₂ (∼1 mL), loaded onto a preparative TLC plate (500 µm silica gel, 10 × 20 cm) that was developed with a 1:1 CH₂Cl₂:hexane mixture as eluent. The main brown band was retrieved, ground into a fine powder, and extracted in a cotton-plugged small column with CH₂Cl₂. The addition of ∼20 vol% MeOH to the filtrate and slow removal of the CH₂Cl₂ by rotary evaporation precipitated the product, which could be isolated by filtration (Kontes microfiltration setup). After vacuum-drying at ambient temperature, 1d was retrieved as a dark-purple powder in 66% yield (21 mg). MW = 1052.63 g mol⁻¹; ¹H NMR (300 MHz, CDCl₃, 300 K): δ 8.62 (d, J = 4.9 Hz, 2H), 8.42 (s, 2H), 8.28 (d, J = 5.4 Hz, 2H), 6.56 (s, 2H), 3.08 (s, 6H), −1.09 (s, 2H). UV–vis (CH₂Cl₂) λ_max nm (log e): 410 (5.20), 515 (4.16), 620 (3.50), 680 (4.33). HR–MS (ESI+, 100% CH₃CN, TOF): m/z calculated for C₄₆H₁₆F₂₀N₄O₃ (MH⁺) 1053.0976; found 1053.0904 (error: 7 ppm). Single crystals suitable for X-ray diffraction were grown in the dark by slow vapor diffusion of hexane into a solution of 1d in CH₂Cl₂.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₄₆H₁₆F₂₀N₄O₃·0.44CH₂Cl₂
M_r	1090.00
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	150
a, b, c (Å)	23.1774 (10), 15.4767 (7), 26.0442 (13)
β (°)	113.1683 (18)
V (Å³)	8588.9 (7)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.22
Crystal size (mm)	0.11 × 0.08 × 0.07

Data collection
Diffractometer	Bruker D8 Quest CMOS
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.671, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	52998, 10495, 6698
R_int	0.082
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.164, 1.03
No. of reflections	10495
No. of parameters	724
No. of restraints	66
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.84, −0.46
Computer programs: APEX3 and SAINT (Bruker, 2016 ), SHELXS97 (Sheldrick, 2008 ), SHELXL2018/3 (Sheldrick, 2015 ), shelXle (Hübschle et al., 2011 ), Mercury (Macrae et al., 2020 ), publCIF (Westrip, 2010 ) and PLATON (Spek, 2020 ).

Crystals for diffraction analysis were taken directly out of the mother liquor (methylene chloride/hexane), mounted immediately on a MiTeGen micromesh mount with the help of a trace of Fomblin oil (a perfluorinated ether), and flash cooled in the cold stream of the diffractometer. Over several hours, no desolvation was observed for crystals remaining immersed in Fomblin oil on the crystal mounting microscope slide.

The solvate methylene chloride molecule is disordered over four positions around an inversion center (each two being symmetry equivalent). The C—Cl and Cl⋯Cl distances were restrained to target values and U^ij components of ADPs for disordered atoms closer to each other than 2.0 Å were restrained to be similar. Occupancies of each of the two symmetry-equivalent sites were freely refined, resulting in a total occupancy slightly below unity [two × 0.241 (5) and two × 0.199 (4), for a total site occupancy of 88%]. Disorder with hexane, the other type of solvent used during crystallization, was excluded as a possibility due to the limited size of the solvate pocket, and it is thus assumed that 12% of void spaces in the crystal structure remained unoccupied during the crystallization process.

N-bound H atoms were located in a difference electron-density map and were freely refined. H atoms attached to carbon atoms were positioned geometrically and constrained to ride on their parent atoms. C—H bond distances were constrained to 0.95 Å for pyrrole CH moieties, and to 1.00, 0.99 and 0.98 Å for aliphatic CH, CH₂ and CH₃ moieties, respectively. Methyl CH₃ groups were allowed to rotate but not to tip to best fit the experimental electron density. U_iso(H) values were set to a multiple of U_eq(C) with 1.5 for CH₃, and 1.2 for CH and CH₂ units, respectively.

Supporting information

CCDC reference: 2013871

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989020009093/is5543sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989020009093/is5543Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015) and shelXle (Hübschle et al., 2011); molecular graphics: Mercury (Macrae et al., 2020); software used to prepare material for publication: publCIF (Westrip, 2010) and PLATON (Spek, 2020).

2,3-Dimethoxy-meso-tetrakis(pentafluorophenyl)morpholinochlorin methylene chloride 0.44-solvate top

Crystal data top

C₄₆H₁₆F₂₀N₄O₃·0.44CH₂Cl₂	F(000) = 4340
M_r = 1090.00	D_x = 1.686 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 23.1774 (10) Å	Cell parameters from 9923 reflections
b = 15.4767 (7) Å	θ = 3.0–28.3°
c = 26.0442 (13) Å	µ = 0.22 mm⁻¹
β = 113.1683 (18)°	T = 150 K
V = 8588.9 (7) Å³	Block, brown
Z = 8	0.11 × 0.08 × 0.07 mm

Data collection top

Bruker D8 Quest CMOS diffractometer	10495 independent reflections
Radiation source: sealed tube X-ray source	6698 reflections with I > 2σ(I)
Triumph curved graphite crystal monochromator	R_int = 0.082
ω and phi scans	θ_max = 28.3°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −30→28
T_min = 0.671, T_max = 0.746	k = −19→20
52998 measured reflections	l = −32→34

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.058	Hydrogen site location: mixed
wR(F²) = 0.164	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0789P)² + 8.847P] where P = (F_o² + 2F_c²)/3
10495 reflections	(Δ/σ)_max < 0.001
724 parameters	Δρ_max = 0.84 e Å⁻³
66 restraints	Δρ_min = −0.46 e Å⁻³

Special details top

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

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.32635 (11)	0.72878 (15)	0.38040 (10)	0.0219 (5)
C2	0.32104 (12)	0.68340 (16)	0.43114 (10)	0.0255 (5)
H2	0.296174	0.629244	0.417471	0.031*
C3	0.24577 (11)	0.79201 (15)	0.42231 (10)	0.0233 (5)
H3	0.229375	0.828639	0.445218	0.028*
C4	0.27686 (11)	0.85048 (15)	0.39362 (10)	0.0227 (5)
C5	0.26559 (12)	0.93899 (15)	0.39395 (11)	0.0247 (5)
C6	0.29046 (12)	1.00692 (16)	0.37303 (11)	0.0272 (5)
C7	0.28844 (13)	1.09651 (16)	0.38542 (12)	0.0321 (6)
H7	0.268250	1.120434	0.407602	0.039*
C8	0.32024 (13)	1.14180 (16)	0.36019 (12)	0.0313 (6)
H8	0.327240	1.202425	0.362572	0.038*
C9	0.34121 (12)	1.08218 (15)	0.32952 (11)	0.0268 (5)
C10	0.37142 (11)	1.10000 (15)	0.29387 (11)	0.0256 (5)
C11	0.38331 (11)	1.03995 (15)	0.25895 (10)	0.0236 (5)
C12	0.40467 (13)	1.06396 (17)	0.21565 (12)	0.0324 (6)
H12	0.417330	1.119836	0.209104	0.039*
C13	0.40309 (13)	0.99144 (17)	0.18644 (11)	0.0321 (6)
H13	0.413110	0.986312	0.154535	0.039*
C14	0.38299 (11)	0.92292 (15)	0.21356 (10)	0.0231 (5)
C15	0.37907 (11)	0.83510 (15)	0.19838 (10)	0.0215 (5)
C16	0.36755 (11)	0.76756 (15)	0.22787 (10)	0.0226 (5)
C17	0.37311 (13)	0.67770 (16)	0.21961 (11)	0.0318 (6)
H17	0.380112	0.652305	0.189355	0.038*
C18	0.36671 (13)	0.63440 (16)	0.26236 (12)	0.0323 (6)
H18	0.369061	0.573502	0.267333	0.039*
C19	0.35586 (11)	0.69561 (15)	0.29864 (10)	0.0231 (5)
C20	0.34768 (11)	0.67585 (14)	0.34804 (10)	0.0214 (5)
C21	0.22315 (12)	0.97069 (15)	0.42126 (11)	0.0271 (5)
C22	0.24512 (13)	0.99038 (17)	0.47767 (12)	0.0320 (6)
C23	0.20658 (14)	1.02359 (18)	0.50208 (12)	0.0360 (6)
C24	0.14432 (15)	1.0389 (2)	0.46966 (13)	0.0405 (7)
C25	0.12069 (14)	1.0214 (2)	0.41347 (13)	0.0417 (7)
C26	0.16036 (13)	0.98641 (18)	0.39028 (12)	0.0333 (6)
C27	0.38931 (12)	1.19202 (15)	0.29033 (11)	0.0256 (5)
C28	0.34468 (12)	1.25553 (16)	0.26532 (10)	0.0263 (5)
C29	0.36086 (13)	1.34043 (16)	0.26142 (11)	0.0287 (5)
C30	0.42335 (13)	1.36344 (15)	0.28171 (11)	0.0300 (6)
C31	0.46876 (13)	1.30227 (18)	0.30576 (13)	0.0338 (6)
C32	0.45121 (12)	1.21796 (16)	0.30977 (12)	0.0299 (6)
C33	0.39339 (11)	0.81235 (15)	0.14862 (10)	0.0229 (5)
C34	0.45380 (11)	0.81801 (17)	0.15011 (10)	0.0282 (5)
C35	0.46780 (12)	0.79981 (18)	0.10433 (11)	0.0313 (6)
C36	0.42068 (13)	0.77496 (19)	0.05528 (11)	0.0337 (6)
C37	0.36041 (13)	0.7670 (2)	0.05249 (11)	0.0365 (6)
C38	0.34730 (12)	0.78505 (17)	0.09886 (11)	0.0301 (6)
C39	0.36233 (11)	0.58285 (15)	0.36504 (10)	0.0219 (5)
C40	0.31708 (12)	0.51876 (16)	0.34665 (11)	0.0270 (5)
C41	0.33125 (13)	0.43302 (16)	0.36056 (11)	0.0291 (6)
C42	0.39189 (14)	0.41008 (15)	0.39319 (11)	0.0311 (6)
C43	0.43823 (13)	0.47182 (17)	0.41231 (11)	0.0302 (6)
C44	0.42281 (11)	0.55716 (15)	0.39797 (11)	0.0254 (5)
C45	0.42137 (13)	0.7312 (2)	0.49423 (12)	0.0377 (6)
H45A	0.431108	0.757883	0.464446	0.057*
H45B	0.460179	0.710236	0.523699	0.057*
H45C	0.401672	0.774104	0.509843	0.057*
C46	0.15720 (16)	0.7051 (3)	0.40359 (14)	0.0538 (9)
H46A	0.119227	0.684073	0.373152	0.081*
H46B	0.145443	0.743803	0.427672	0.081*
H46C	0.180923	0.656005	0.425570	0.081*
N1	0.31243 (9)	0.81349 (13)	0.36912 (9)	0.0229 (4)
N2	0.32301 (10)	1.00102 (14)	0.33927 (9)	0.0263 (5)
H2A	0.3274 (14)	0.954 (2)	0.3242 (13)	0.039 (8)*
N3	0.37108 (9)	0.95377 (12)	0.25756 (8)	0.0210 (4)
N4	0.35551 (9)	0.77493 (13)	0.27530 (9)	0.0211 (4)
H4	0.3538 (13)	0.8197 (19)	0.2894 (12)	0.028 (8)*
O1	0.37925 (9)	0.66032 (12)	0.47187 (8)	0.0325 (4)
O2	0.29008 (8)	0.73396 (11)	0.45788 (7)	0.0258 (4)
O3	0.19528 (8)	0.75125 (12)	0.38073 (8)	0.0309 (4)
F1	0.30561 (9)	0.97758 (13)	0.50994 (7)	0.0508 (5)
F2	0.23007 (9)	1.04108 (13)	0.55689 (7)	0.0536 (5)
F3	0.10730 (9)	1.07298 (14)	0.49265 (8)	0.0587 (5)
F4	0.06062 (9)	1.03781 (17)	0.38111 (9)	0.0701 (7)
F5	0.13564 (8)	0.97084 (13)	0.33525 (7)	0.0483 (5)
F6	0.28370 (7)	1.23508 (10)	0.24473 (7)	0.0360 (4)
F7	0.31630 (7)	1.40025 (10)	0.23865 (7)	0.0377 (4)
F8	0.43987 (8)	1.44566 (10)	0.27921 (8)	0.0423 (4)
F9	0.52959 (8)	1.32485 (11)	0.32567 (9)	0.0519 (5)
F10	0.49729 (7)	1.15998 (10)	0.33406 (8)	0.0446 (4)
F11	0.50098 (7)	0.84265 (13)	0.19692 (6)	0.0448 (4)
F12	0.52687 (7)	0.80701 (13)	0.10779 (7)	0.0463 (4)
F13	0.43327 (8)	0.75890 (13)	0.01025 (7)	0.0493 (5)
F14	0.31452 (8)	0.74177 (15)	0.00464 (7)	0.0586 (6)
F15	0.28789 (7)	0.77668 (12)	0.09439 (7)	0.0429 (4)
F16	0.25774 (7)	0.54003 (10)	0.31493 (7)	0.0408 (4)
F17	0.28647 (8)	0.37195 (10)	0.34199 (8)	0.0424 (4)
F18	0.40620 (9)	0.32672 (9)	0.40659 (7)	0.0430 (4)
F19	0.49691 (8)	0.44860 (11)	0.44487 (8)	0.0477 (5)
F20	0.46884 (7)	0.61620 (9)	0.41722 (7)	0.0355 (4)
C47	0.4785 (12)	0.980 (4)	0.4881 (10)	0.154 (6)	0.241 (5)
H47A	0.476482	0.922171	0.470843	0.184*	0.241 (5)
H47B	0.454112	1.021606	0.458893	0.184*	0.241 (5)
Cl1	0.5576 (3)	1.0144 (6)	0.5239 (4)	0.160 (4)	0.241 (5)
Cl2	0.4511 (5)	0.9757 (6)	0.5439 (5)	0.144 (3)	0.241 (5)
C48	0.508 (3)	0.962 (3)	0.4834 (13)	0.142 (7)	0.199 (4)
H48A	0.553867	0.953404	0.498144	0.171*	0.199 (4)
H48B	0.489108	0.905124	0.468872	0.171*	0.199 (4)
Cl3	0.4912 (6)	1.0246 (8)	0.4255 (4)	0.127 (4)	0.199 (4)
Cl4	0.4918 (11)	0.9784 (13)	0.5413 (7)	0.204 (6)	0.199 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0229 (11)	0.0192 (11)	0.0273 (12)	−0.0013 (9)	0.0139 (10)	0.0007 (9)
C2	0.0324 (13)	0.0225 (12)	0.0275 (13)	0.0032 (10)	0.0180 (11)	0.0033 (10)
C3	0.0278 (12)	0.0205 (11)	0.0256 (12)	0.0020 (9)	0.0150 (10)	−0.0001 (9)
C4	0.0286 (12)	0.0208 (11)	0.0240 (12)	0.0006 (9)	0.0162 (10)	0.0005 (9)
C5	0.0317 (12)	0.0213 (12)	0.0291 (13)	0.0020 (10)	0.0206 (11)	0.0003 (10)
C6	0.0349 (13)	0.0215 (12)	0.0341 (14)	0.0035 (10)	0.0232 (11)	0.0009 (10)
C7	0.0477 (16)	0.0201 (12)	0.0413 (16)	0.0035 (11)	0.0312 (13)	−0.0032 (11)
C8	0.0456 (15)	0.0173 (12)	0.0409 (15)	0.0003 (11)	0.0276 (13)	−0.0024 (11)
C9	0.0332 (13)	0.0195 (12)	0.0341 (14)	−0.0005 (10)	0.0202 (11)	−0.0006 (10)
C10	0.0304 (13)	0.0189 (11)	0.0321 (14)	−0.0009 (10)	0.0174 (11)	0.0009 (10)
C11	0.0264 (12)	0.0220 (12)	0.0266 (13)	0.0007 (10)	0.0149 (10)	0.0025 (10)
C12	0.0484 (16)	0.0232 (13)	0.0366 (15)	−0.0022 (11)	0.0286 (13)	0.0029 (11)
C13	0.0486 (16)	0.0278 (13)	0.0309 (14)	−0.0008 (12)	0.0273 (13)	0.0019 (11)
C14	0.0268 (12)	0.0232 (12)	0.0216 (12)	0.0021 (10)	0.0121 (10)	0.0029 (9)
C15	0.0233 (11)	0.0243 (12)	0.0182 (11)	0.0027 (9)	0.0097 (9)	−0.0012 (9)
C16	0.0258 (11)	0.0221 (11)	0.0217 (12)	0.0008 (9)	0.0112 (10)	−0.0023 (9)
C17	0.0474 (16)	0.0232 (13)	0.0322 (14)	0.0019 (11)	0.0238 (13)	−0.0030 (11)
C18	0.0511 (16)	0.0186 (12)	0.0359 (15)	0.0031 (11)	0.0263 (13)	−0.0012 (11)
C19	0.0278 (12)	0.0170 (11)	0.0264 (13)	0.0023 (9)	0.0128 (10)	0.0005 (9)
C20	0.0240 (11)	0.0171 (11)	0.0242 (12)	0.0004 (9)	0.0108 (10)	0.0004 (9)
C21	0.0405 (14)	0.0181 (11)	0.0333 (14)	0.0028 (10)	0.0260 (12)	0.0015 (10)
C22	0.0390 (15)	0.0302 (13)	0.0330 (14)	0.0031 (11)	0.0209 (12)	0.0024 (11)
C23	0.0560 (18)	0.0325 (14)	0.0324 (15)	−0.0008 (13)	0.0314 (14)	−0.0034 (12)
C24	0.0498 (17)	0.0415 (16)	0.0476 (18)	0.0070 (14)	0.0377 (15)	−0.0023 (14)
C25	0.0423 (16)	0.0501 (18)	0.0452 (18)	0.0093 (14)	0.0306 (14)	−0.0005 (14)
C26	0.0436 (16)	0.0339 (14)	0.0322 (15)	0.0060 (12)	0.0254 (13)	0.0010 (12)
C27	0.0355 (13)	0.0199 (12)	0.0301 (13)	−0.0014 (10)	0.0224 (11)	−0.0004 (10)
C28	0.0307 (12)	0.0275 (13)	0.0247 (13)	−0.0023 (10)	0.0152 (10)	0.0001 (10)
C29	0.0434 (15)	0.0195 (12)	0.0288 (13)	0.0045 (11)	0.0203 (12)	0.0036 (10)
C30	0.0466 (15)	0.0171 (11)	0.0339 (14)	−0.0043 (11)	0.0241 (12)	0.0004 (10)
C31	0.0326 (14)	0.0279 (14)	0.0460 (17)	−0.0065 (11)	0.0209 (12)	−0.0019 (12)
C32	0.0314 (13)	0.0223 (12)	0.0417 (16)	0.0025 (10)	0.0206 (12)	0.0016 (11)
C33	0.0297 (12)	0.0215 (11)	0.0196 (11)	0.0028 (10)	0.0119 (10)	0.0010 (9)
C34	0.0268 (12)	0.0361 (14)	0.0201 (12)	0.0006 (11)	0.0074 (10)	−0.0036 (10)
C35	0.0271 (12)	0.0414 (15)	0.0294 (14)	0.0032 (11)	0.0156 (11)	−0.0019 (12)
C36	0.0384 (14)	0.0458 (16)	0.0228 (13)	0.0008 (12)	0.0183 (11)	−0.0065 (12)
C37	0.0350 (14)	0.0501 (17)	0.0222 (13)	−0.0022 (13)	0.0088 (11)	−0.0097 (12)
C38	0.0268 (12)	0.0374 (15)	0.0266 (13)	−0.0001 (11)	0.0110 (11)	−0.0016 (11)
C39	0.0296 (12)	0.0176 (11)	0.0241 (12)	0.0027 (9)	0.0165 (10)	0.0005 (9)
C40	0.0301 (13)	0.0240 (12)	0.0301 (13)	0.0002 (10)	0.0153 (11)	0.0000 (10)
C41	0.0421 (15)	0.0210 (12)	0.0318 (14)	−0.0065 (11)	0.0227 (12)	−0.0039 (10)
C42	0.0544 (17)	0.0161 (12)	0.0323 (14)	0.0055 (11)	0.0272 (13)	0.0055 (10)
C43	0.0356 (14)	0.0252 (13)	0.0303 (14)	0.0103 (11)	0.0135 (11)	0.0049 (11)
C44	0.0307 (13)	0.0192 (12)	0.0314 (14)	0.0004 (10)	0.0178 (11)	−0.0003 (10)
C45	0.0331 (14)	0.0481 (17)	0.0335 (15)	−0.0003 (13)	0.0148 (12)	0.0001 (13)
C46	0.0450 (17)	0.076 (2)	0.0431 (19)	−0.0305 (17)	0.0199 (15)	−0.0035 (17)
N1	0.0264 (10)	0.0187 (9)	0.0280 (11)	0.0008 (8)	0.0152 (9)	−0.0009 (8)
N2	0.0383 (12)	0.0163 (10)	0.0344 (12)	−0.0005 (9)	0.0251 (10)	−0.0020 (9)
N3	0.0259 (10)	0.0159 (9)	0.0242 (10)	0.0022 (8)	0.0129 (8)	0.0002 (8)
N4	0.0273 (10)	0.0157 (10)	0.0237 (11)	0.0018 (8)	0.0138 (8)	−0.0008 (8)
O1	0.0378 (10)	0.0317 (10)	0.0316 (10)	0.0101 (8)	0.0175 (8)	0.0083 (8)
O2	0.0320 (9)	0.0261 (9)	0.0256 (9)	0.0062 (7)	0.0180 (7)	0.0042 (7)
O3	0.0312 (9)	0.0353 (10)	0.0300 (10)	−0.0064 (8)	0.0162 (8)	−0.0016 (8)
F1	0.0498 (10)	0.0691 (13)	0.0357 (10)	0.0102 (9)	0.0193 (8)	−0.0037 (9)
F2	0.0713 (13)	0.0666 (13)	0.0349 (10)	0.0013 (10)	0.0337 (9)	−0.0103 (9)
F3	0.0654 (12)	0.0743 (14)	0.0595 (12)	0.0142 (10)	0.0494 (11)	−0.0088 (10)
F4	0.0427 (10)	0.1148 (19)	0.0596 (13)	0.0267 (12)	0.0274 (10)	−0.0053 (12)
F5	0.0441 (10)	0.0728 (13)	0.0338 (9)	0.0099 (9)	0.0215 (8)	−0.0069 (9)
F6	0.0310 (8)	0.0342 (8)	0.0413 (9)	−0.0022 (7)	0.0125 (7)	0.0042 (7)
F7	0.0466 (9)	0.0273 (8)	0.0419 (9)	0.0083 (7)	0.0205 (8)	0.0107 (7)
F8	0.0551 (10)	0.0225 (8)	0.0540 (11)	−0.0077 (7)	0.0265 (9)	0.0035 (7)
F9	0.0364 (9)	0.0377 (10)	0.0837 (15)	−0.0099 (8)	0.0257 (9)	0.0041 (9)
F10	0.0337 (9)	0.0302 (8)	0.0734 (13)	0.0042 (7)	0.0248 (8)	0.0083 (8)
F11	0.0279 (8)	0.0814 (13)	0.0246 (8)	−0.0061 (8)	0.0096 (6)	−0.0144 (8)
F12	0.0317 (8)	0.0777 (13)	0.0365 (9)	−0.0014 (8)	0.0209 (7)	−0.0114 (9)
F13	0.0494 (10)	0.0786 (13)	0.0279 (9)	−0.0028 (9)	0.0238 (8)	−0.0149 (9)
F14	0.0414 (10)	0.1027 (17)	0.0276 (9)	−0.0118 (10)	0.0092 (8)	−0.0243 (10)
F15	0.0287 (8)	0.0689 (12)	0.0319 (9)	−0.0071 (8)	0.0127 (7)	−0.0102 (8)
F16	0.0297 (8)	0.0322 (8)	0.0525 (11)	−0.0023 (7)	0.0076 (7)	−0.0015 (7)
F17	0.0542 (10)	0.0242 (8)	0.0542 (11)	−0.0136 (7)	0.0271 (9)	−0.0056 (7)
F18	0.0712 (12)	0.0176 (7)	0.0433 (10)	0.0076 (7)	0.0259 (9)	0.0083 (7)
F19	0.0432 (10)	0.0335 (9)	0.0568 (12)	0.0156 (7)	0.0095 (8)	0.0088 (8)
F20	0.0267 (8)	0.0258 (8)	0.0528 (10)	0.0011 (6)	0.0146 (7)	−0.0007 (7)
C47	0.138 (10)	0.139 (9)	0.151 (9)	−0.007 (9)	0.021 (10)	0.007 (9)
Cl1	0.101 (5)	0.140 (6)	0.162 (8)	−0.006 (5)	−0.030 (5)	0.009 (5)
Cl2	0.108 (6)	0.111 (5)	0.203 (9)	−0.013 (5)	0.051 (6)	−0.024 (5)
C48	0.131 (10)	0.137 (10)	0.135 (10)	−0.007 (10)	0.027 (10)	0.003 (9)
Cl3	0.160 (9)	0.138 (7)	0.074 (5)	0.005 (6)	0.038 (5)	0.033 (5)
Cl4	0.154 (9)	0.190 (9)	0.205 (10)	−0.002 (9)	0.004 (10)	−0.027 (10)

Geometric parameters (Å, º) top

C1—N1	1.354 (3)	C26—F5	1.339 (3)
C1—C20	1.398 (3)	C27—C32	1.380 (4)
C1—C2	1.544 (3)	C27—C28	1.389 (4)
C2—O1	1.395 (3)	C28—F6	1.338 (3)
C2—O2	1.416 (3)	C28—C29	1.381 (3)
C2—H2	1.0000	C29—F7	1.339 (3)
C3—O3	1.394 (3)	C29—C30	1.379 (4)
C3—O2	1.404 (3)	C30—F8	1.338 (3)
C3—C4	1.523 (3)	C30—C31	1.370 (4)
C3—H3	1.0000	C31—F9	1.343 (3)
C4—N1	1.352 (3)	C31—C32	1.383 (4)
C4—C5	1.395 (3)	C32—F10	1.347 (3)
C5—C6	1.408 (3)	C33—C38	1.382 (4)
C5—C21	1.505 (3)	C33—C34	1.388 (3)
C6—N2	1.368 (3)	C34—F11	1.334 (3)
C6—C7	1.429 (3)	C34—C35	1.382 (4)
C7—C8	1.359 (4)	C35—F12	1.341 (3)
C7—H7	0.9500	C35—C36	1.369 (4)
C8—C9	1.425 (3)	C36—F13	1.338 (3)
C8—H8	0.9500	C36—C37	1.376 (4)
C9—N2	1.380 (3)	C37—F14	1.339 (3)
C9—C10	1.393 (3)	C37—C38	1.385 (4)
C10—C11	1.401 (3)	C38—F15	1.342 (3)
C10—C27	1.496 (3)	C39—C44	1.383 (3)
C11—N3	1.361 (3)	C39—C40	1.385 (3)
C11—C12	1.447 (3)	C40—F16	1.337 (3)
C12—C13	1.348 (4)	C40—C41	1.381 (4)
C12—H12	0.9500	C41—F17	1.345 (3)
C13—C14	1.449 (3)	C41—C42	1.372 (4)
C13—H13	0.9500	C42—F18	1.344 (3)
C14—N3	1.366 (3)	C42—C43	1.376 (4)
C14—C15	1.409 (3)	C43—F19	1.338 (3)
C15—C16	1.384 (3)	C43—C44	1.381 (3)
C15—C33	1.501 (3)	C44—F20	1.343 (3)
C16—N4	1.374 (3)	C45—O1	1.432 (3)
C16—C17	1.421 (3)	C45—H45A	0.9800
C17—C18	1.357 (4)	C45—H45B	0.9800
C17—H17	0.9500	C45—H45C	0.9800
C18—C19	1.429 (3)	C46—O3	1.434 (3)
C18—H18	0.9500	C46—H46A	0.9800
C19—N4	1.368 (3)	C46—H46B	0.9800
C19—C20	1.406 (3)	C46—H46C	0.9800
C20—C39	1.505 (3)	N2—H2A	0.85 (3)
C21—C26	1.380 (4)	N4—H4	0.79 (3)
C21—C22	1.386 (4)	C47—Cl1	1.781 (19)
C22—F1	1.336 (3)	C47—Cl2	1.80 (2)
C22—C23	1.383 (4)	C47—H47A	0.9900
C23—F2	1.340 (3)	C47—H47B	0.9900
C23—C24	1.376 (4)	C48—Cl3	1.705 (19)
C24—F3	1.333 (3)	C48—Cl4	1.708 (18)
C24—C25	1.373 (4)	C48—H48A	0.9900
C25—F4	1.338 (4)	C48—H48B	0.9900
C25—C26	1.393 (4)

N1—C1—C20	123.2 (2)	F6—C28—C29	118.1 (2)
N1—C1—C2	122.3 (2)	F6—C28—C27	119.7 (2)
C20—C1—C2	114.6 (2)	C29—C28—C27	122.3 (2)
O1—C2—O2	107.04 (19)	F7—C29—C30	120.1 (2)
O1—C2—C1	112.86 (19)	F7—C29—C28	120.4 (2)
O2—C2—C1	113.33 (19)	C30—C29—C28	119.5 (2)
O1—C2—H2	107.8	F8—C30—C31	119.8 (2)
O2—C2—H2	107.8	F8—C30—C29	120.3 (2)
C1—C2—H2	107.8	C31—C30—C29	119.9 (2)
O3—C3—O2	113.30 (19)	F9—C31—C30	119.8 (2)
O3—C3—C4	107.60 (19)	F9—C31—C32	120.8 (2)
O2—C3—C4	109.84 (19)	C30—C31—C32	119.4 (2)
O3—C3—H3	108.7	F10—C32—C27	119.8 (2)
O2—C3—H3	108.7	F10—C32—C31	117.5 (2)
C4—C3—H3	108.7	C27—C32—C31	122.7 (2)
N1—C4—C5	124.7 (2)	C38—C33—C34	116.4 (2)
N1—C4—C3	118.3 (2)	C38—C33—C15	122.0 (2)
C5—C4—C3	117.0 (2)	C34—C33—C15	121.6 (2)
C4—C5—C6	128.7 (2)	F11—C34—C35	117.4 (2)
C4—C5—C21	118.8 (2)	F11—C34—C33	119.9 (2)
C6—C5—C21	112.5 (2)	C35—C34—C33	122.7 (2)
N2—C6—C5	127.7 (2)	F12—C35—C36	120.3 (2)
N2—C6—C7	106.6 (2)	F12—C35—C34	120.3 (2)
C5—C6—C7	125.6 (2)	C36—C35—C34	119.4 (2)
C8—C7—C6	108.6 (2)	F13—C36—C35	120.1 (2)
C8—C7—H7	125.7	F13—C36—C37	120.3 (2)
C6—C7—H7	125.7	C35—C36—C37	119.7 (2)
C7—C8—C9	107.8 (2)	F14—C37—C36	119.6 (2)
C7—C8—H8	126.1	F14—C37—C38	120.3 (2)
C9—C8—H8	126.1	C36—C37—C38	120.2 (2)
N2—C9—C10	125.0 (2)	F15—C38—C33	119.9 (2)
N2—C9—C8	106.8 (2)	F15—C38—C37	118.3 (2)
C10—C9—C8	128.1 (2)	C33—C38—C37	121.7 (2)
C9—C10—C11	125.5 (2)	C44—C39—C40	117.0 (2)
C9—C10—C27	117.0 (2)	C44—C39—C20	120.9 (2)
C11—C10—C27	117.5 (2)	C40—C39—C20	122.1 (2)
N3—C11—C10	125.1 (2)	F16—C40—C41	118.6 (2)
N3—C11—C12	111.2 (2)	F16—C40—C39	119.5 (2)
C10—C11—C12	123.4 (2)	C41—C40—C39	121.9 (2)
C13—C12—C11	106.5 (2)	F17—C41—C42	119.9 (2)
C13—C12—H12	126.7	F17—C41—C40	120.7 (2)
C11—C12—H12	126.7	C42—C41—C40	119.4 (2)
C12—C13—C14	106.1 (2)	F18—C42—C41	119.8 (2)
C12—C13—H13	127.0	F18—C42—C43	119.7 (2)
C14—C13—H13	127.0	C41—C42—C43	120.5 (2)
N3—C14—C15	124.1 (2)	F19—C43—C42	119.8 (2)
N3—C14—C13	111.3 (2)	F19—C43—C44	121.2 (2)
C15—C14—C13	124.5 (2)	C42—C43—C44	119.0 (2)
C16—C15—C14	125.3 (2)	F20—C44—C43	117.8 (2)
C16—C15—C33	117.3 (2)	F20—C44—C39	119.9 (2)
C14—C15—C33	117.2 (2)	C43—C44—C39	122.3 (2)
N4—C16—C15	126.0 (2)	O1—C45—H45A	109.5
N4—C16—C17	106.3 (2)	O1—C45—H45B	109.5
C15—C16—C17	127.3 (2)	H45A—C45—H45B	109.5
C18—C17—C16	108.3 (2)	O1—C45—H45C	109.5
C18—C17—H17	125.9	H45A—C45—H45C	109.5
C16—C17—H17	125.9	H45B—C45—H45C	109.5
C17—C18—C19	108.6 (2)	O3—C46—H46A	109.5
C17—C18—H18	125.7	O3—C46—H46B	109.5
C19—C18—H18	125.7	H46A—C46—H46B	109.5
N4—C19—C20	128.5 (2)	O3—C46—H46C	109.5
N4—C19—C18	105.8 (2)	H46A—C46—H46C	109.5
C20—C19—C18	125.7 (2)	H46B—C46—H46C	109.5
C1—C20—C19	129.1 (2)	C4—N1—C1	116.4 (2)
C1—C20—C39	118.4 (2)	C6—N2—C9	110.1 (2)
C19—C20—C39	112.42 (19)	C6—N2—H2A	123 (2)
C26—C21—C22	116.4 (2)	C9—N2—H2A	126 (2)
C26—C21—C5	121.1 (2)	C11—N3—C14	104.84 (19)
C22—C21—C5	122.5 (2)	C19—N4—C16	110.9 (2)
F1—C22—C23	118.3 (3)	C19—N4—H4	125 (2)
F1—C22—C21	119.4 (2)	C16—N4—H4	124 (2)
C23—C22—C21	122.3 (3)	C2—O1—C45	114.4 (2)
F2—C23—C24	120.5 (2)	C3—O2—C2	114.19 (18)
F2—C23—C22	120.0 (3)	C3—O3—C46	111.6 (2)
C24—C23—C22	119.5 (3)	Cl1—C47—Cl2	101.8 (12)
F3—C24—C25	120.0 (3)	Cl1—C47—H47A	111.4
F3—C24—C23	119.8 (3)	Cl2—C47—H47A	111.4
C25—C24—C23	120.2 (2)	Cl1—C47—H47B	111.4
F4—C25—C24	120.9 (2)	Cl2—C47—H47B	111.4
F4—C25—C26	120.1 (3)	H47A—C47—H47B	109.3
C24—C25—C26	119.0 (3)	Cl3—C48—Cl4	130 (2)
F5—C26—C21	120.2 (2)	Cl3—C48—H48A	104.7
F5—C26—C25	117.2 (3)	Cl4—C48—H48A	104.7
C21—C26—C25	122.6 (3)	Cl3—C48—H48B	104.7
C32—C27—C28	116.2 (2)	Cl4—C48—H48B	104.7
C32—C27—C10	121.8 (2)	H48A—C48—H48B	105.7
C28—C27—C10	121.9 (2)

N1—C1—C2—O1	−111.2 (2)	C28—C29—C30—F8	−178.8 (2)
C20—C1—C2—O1	67.6 (3)	F7—C29—C30—C31	179.0 (2)
N1—C1—C2—O2	10.7 (3)	C28—C29—C30—C31	−0.3 (4)
C20—C1—C2—O2	−170.5 (2)	F8—C30—C31—F9	−1.3 (4)
O3—C3—C4—N1	−74.8 (3)	C29—C30—C31—F9	−179.8 (2)
O2—C3—C4—N1	49.0 (3)	F8—C30—C31—C32	178.0 (2)
O3—C3—C4—C5	104.3 (2)	C29—C30—C31—C32	−0.5 (4)
O2—C3—C4—C5	−131.9 (2)	C28—C27—C32—F10	−179.4 (2)
N1—C4—C5—C6	−4.2 (4)	C10—C27—C32—F10	−1.8 (4)
C3—C4—C5—C6	176.8 (3)	C28—C27—C32—C31	0.9 (4)
N1—C4—C5—C21	177.9 (2)	C10—C27—C32—C31	178.5 (3)
C3—C4—C5—C21	−1.1 (3)	F9—C31—C32—F10	−0.3 (4)
C4—C5—C6—N2	12.1 (5)	C30—C31—C32—F10	−179.5 (2)
C21—C5—C6—N2	−169.9 (3)	F9—C31—C32—C27	179.4 (3)
C4—C5—C6—C7	−165.1 (3)	C30—C31—C32—C27	0.2 (4)
C21—C5—C6—C7	12.9 (4)	C16—C15—C33—C38	74.6 (3)
N2—C6—C7—C8	−1.1 (3)	C14—C15—C33—C38	−109.9 (3)
C5—C6—C7—C8	176.6 (3)	C16—C15—C33—C34	−105.7 (3)
C6—C7—C8—C9	2.1 (3)	C14—C15—C33—C34	69.8 (3)
C7—C8—C9—N2	−2.3 (3)	C38—C33—C34—F11	−179.0 (2)
C7—C8—C9—C10	174.6 (3)	C15—C33—C34—F11	1.2 (4)
N2—C9—C10—C11	5.7 (4)	C38—C33—C34—C35	1.7 (4)
C8—C9—C10—C11	−170.7 (3)	C15—C33—C34—C35	−178.1 (2)
N2—C9—C10—C27	−178.0 (2)	F11—C34—C35—F12	0.1 (4)
C8—C9—C10—C27	5.6 (4)	C33—C34—C35—F12	179.4 (2)
C9—C10—C11—N3	−4.9 (4)	F11—C34—C35—C36	−179.5 (3)
C27—C10—C11—N3	178.7 (2)	C33—C34—C35—C36	−0.1 (4)
C9—C10—C11—C12	168.7 (3)	F12—C35—C36—F13	−1.0 (4)
C27—C10—C11—C12	−7.6 (4)	C34—C35—C36—F13	178.6 (3)
N3—C11—C12—C13	2.2 (3)	F12—C35—C36—C37	179.3 (3)
C10—C11—C12—C13	−172.2 (2)	C34—C35—C36—C37	−1.1 (4)
C11—C12—C13—C14	−2.1 (3)	F13—C36—C37—F14	1.0 (4)
C12—C13—C14—N3	1.5 (3)	C35—C36—C37—F14	−179.3 (3)
C12—C13—C14—C15	−175.6 (2)	F13—C36—C37—C38	−178.9 (3)
N3—C14—C15—C16	−5.2 (4)	C35—C36—C37—C38	0.8 (5)
C13—C14—C15—C16	171.5 (2)	C34—C33—C38—F15	179.0 (2)
N3—C14—C15—C33	179.7 (2)	C15—C33—C38—F15	−1.3 (4)
C13—C14—C15—C33	−3.5 (4)	C34—C33—C38—C37	−2.0 (4)
C14—C15—C16—N4	2.9 (4)	C15—C33—C38—C37	177.8 (3)
C33—C15—C16—N4	177.9 (2)	F14—C37—C38—F15	0.0 (4)
C14—C15—C16—C17	−169.0 (3)	C36—C37—C38—F15	179.8 (3)
C33—C15—C16—C17	6.1 (4)	F14—C37—C38—C33	−179.1 (3)
N4—C16—C17—C18	−2.1 (3)	C36—C37—C38—C33	0.8 (4)
C15—C16—C17—C18	171.0 (3)	C1—C20—C39—C44	−94.8 (3)
C16—C17—C18—C19	0.9 (3)	C19—C20—C39—C44	87.5 (3)
C17—C18—C19—N4	0.6 (3)	C1—C20—C39—C40	88.2 (3)
C17—C18—C19—C20	−179.1 (2)	C19—C20—C39—C40	−89.5 (3)
N1—C1—C20—C19	−3.4 (4)	C44—C39—C40—F16	179.6 (2)
C2—C1—C20—C19	177.8 (2)	C20—C39—C40—F16	−3.2 (4)
N1—C1—C20—C39	179.3 (2)	C44—C39—C40—C41	0.3 (4)
C2—C1—C20—C39	0.5 (3)	C20—C39—C40—C41	177.4 (2)
N4—C19—C20—C1	12.6 (4)	F16—C40—C41—F17	0.9 (4)
C18—C19—C20—C1	−167.7 (3)	C39—C40—C41—F17	−179.8 (2)
N4—C19—C20—C39	−170.0 (2)	F16—C40—C41—C42	−179.8 (2)
C18—C19—C20—C39	9.7 (3)	C39—C40—C41—C42	−0.5 (4)
C4—C5—C21—C26	−95.9 (3)	F17—C41—C42—F18	−0.2 (4)
C6—C5—C21—C26	85.8 (3)	C40—C41—C42—F18	−179.5 (2)
C4—C5—C21—C22	87.8 (3)	F17—C41—C42—C43	179.7 (2)
C6—C5—C21—C22	−90.4 (3)	C40—C41—C42—C43	0.4 (4)
C26—C21—C22—F1	−179.3 (2)	F18—C42—C43—F19	−1.2 (4)
C5—C21—C22—F1	−2.9 (4)	C41—C42—C43—F19	178.9 (2)
C26—C21—C22—C23	0.3 (4)	F18—C42—C43—C44	179.7 (2)
C5—C21—C22—C23	176.7 (2)	C41—C42—C43—C44	−0.2 (4)
F1—C22—C23—F2	−0.8 (4)	F19—C43—C44—F20	0.8 (4)
C21—C22—C23—F2	179.6 (2)	C42—C43—C44—F20	179.9 (2)
F1—C22—C23—C24	178.8 (3)	F19—C43—C44—C39	−179.1 (2)
C21—C22—C23—C24	−0.8 (4)	C42—C43—C44—C39	0.0 (4)
F2—C23—C24—F3	1.4 (4)	C40—C39—C44—F20	−179.9 (2)
C22—C23—C24—F3	−178.3 (3)	C20—C39—C44—F20	2.9 (3)
F2—C23—C24—C25	179.5 (3)	C40—C39—C44—C43	0.0 (4)
C22—C23—C24—C25	−0.1 (4)	C20—C39—C44—C43	−177.2 (2)
F3—C24—C25—F4	−0.2 (5)	C5—C4—N1—C1	169.9 (2)
C23—C24—C25—F4	−178.4 (3)	C3—C4—N1—C1	−11.1 (3)
F3—C24—C25—C26	179.5 (3)	C20—C1—N1—C4	162.6 (2)
C23—C24—C25—C26	1.3 (5)	C2—C1—N1—C4	−18.7 (3)
C22—C21—C26—F5	178.6 (2)	C5—C6—N2—C9	−178.0 (3)
C5—C21—C26—F5	2.2 (4)	C7—C6—N2—C9	−0.4 (3)
C22—C21—C26—C25	1.0 (4)	C10—C9—N2—C6	−175.4 (3)
C5—C21—C26—C25	−175.5 (3)	C8—C9—N2—C6	1.6 (3)
F4—C25—C26—F5	0.2 (4)	C10—C11—N3—C14	173.1 (2)
C24—C25—C26—F5	−179.5 (3)	C12—C11—N3—C14	−1.2 (3)
F4—C25—C26—C21	177.9 (3)	C15—C14—N3—C11	177.0 (2)
C24—C25—C26—C21	−1.8 (5)	C13—C14—N3—C11	−0.1 (3)
C9—C10—C27—C32	113.0 (3)	C20—C19—N4—C16	177.7 (2)
C11—C10—C27—C32	−70.3 (3)	C18—C19—N4—C16	−2.1 (3)
C9—C10—C27—C28	−69.5 (3)	C15—C16—N4—C19	−170.6 (2)
C11—C10—C27—C28	107.1 (3)	C17—C16—N4—C19	2.6 (3)
C32—C27—C28—F6	179.1 (2)	O2—C2—O1—C45	−66.4 (2)
C10—C27—C28—F6	1.5 (4)	C1—C2—O1—C45	59.0 (3)
C32—C27—C28—C29	−1.8 (4)	O3—C3—O2—C2	64.5 (2)
C10—C27—C28—C29	−179.4 (2)	C4—C3—O2—C2	−55.9 (3)
F6—C28—C29—F7	1.4 (4)	O1—C2—O2—C3	153.83 (19)
C27—C28—C29—F7	−177.8 (2)	C1—C2—O2—C3	28.8 (3)
F6—C28—C29—C30	−179.3 (2)	O2—C3—O3—C46	67.4 (3)
C27—C28—C29—C30	1.5 (4)	C4—C3—O3—C46	−171.0 (2)
F7—C29—C30—F8	0.5 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···F18ⁱ	0.95	2.59	3.424 (3)	147
C18—H18···F8ⁱⁱ	0.95	2.51	3.319 (3)	143
C45—H45A···F12ⁱⁱⁱ	0.98	2.55	3.519 (3)	169
C45—H45B···F19^iv	0.98	2.66	3.389 (3)	132
C45—H45A···F20	0.98	2.82	3.184 (3)	103
C46—H46A···F10^v	0.98	2.63	3.496 (4)	148
C46—H46C···F1^vi	0.98	2.60	3.505 (4)	153
C48—H48B···F12ⁱⁱⁱ	0.99	2.42	3.25 (5)	141
N2—H2A···N1	0.85 (3)	2.56 (3)	3.040 (3)	117 (3)
N2—H2A···N3	0.85 (3)	2.33 (3)	2.858 (3)	121 (3)
N4—H4···N1	0.79 (3)	2.61 (3)	3.040 (3)	116 (2)
N4—H4···N3	0.79 (3)	2.33 (3)	2.852 (3)	125 (3)

Symmetry codes: (i) x, y+1, z; (ii) x, y−1, z; (iii) −x+1, y, −z+1/2; (iv) −x+1, −y+1, −z+1; (v) x−1/2, y−1/2, z; (vi) −x+1/2, −y+3/2, −z+1.

Acknowledgements

This material is based upon work supported by the National Science Foundation through the Major Research Instrumentation Program under grant No. CHE 1625543 (funding for the single-crystal X-ray diffractometer).

Funding information

Funding for this research was provided by: National Science Foundation (grant No. CHE-1625543 to M. Zeller; grant No. CHE-1800361 to C. Brückner).

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