Ring-strain release in neutral and dicationic 7,8,17,18-tetra­bromo-5,10,15,20-tetra­phenyl­porphyrin: crystal structures of C44H26Br4N4 and C44H28Br4N42+·2ClO4−·3CH2Cl2

Scheidt, W.R.; Duval, H.F.; Oliver, A.G.

doi:10.1107/S2056989016007349

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 72| Part 6| June 2016| Pages 824-828

https://doi.org/10.1107/S2056989016007349

Open

access

Ring-strain release in neutral and dicationic 7,8,17,18-tetrabromo-5,10,15,20-tetraphenylporphyrin: crystal structures of C₄₄H₂₆Br₄N₄ and C₄₄H₂₈Br₄N₄²⁺·2ClO₄⁻·3CH₂Cl₂

W. Robert Scheidt,^a ^* Hugues F. Duval ^a and Allen G. Oliver ^a

^a235 Nieuwland Science Hall, Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556, USA
^*Correspondence e-mail: scheidt.1@nd.edu

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 22 April 2016; accepted 2 May 2016; online 20 May 2016)

Two porphyrin complexes were studied to determine the effects of protonation on ring deformation within the porphyrin. The porphyrin 7,8,17,18-tetrabromo-5,10,15,20-tetraphenylporphyrin, C₄₄H₂₆Br₄N₄, was selected because the neutral species is readily doubly protonated to yield a dication, which was crystallized here with perchlorate counter-ions as a dichloromethane trisolvate, C₄₄H₂₈Br₄N₄²⁺·2ClO₄⁻·3CH₂Cl₂. The centrosymmetric neutral species is observed to have a mild `ruffling' of the pyrrole rings and is essentially planar throughout; intramolecular N—H⋯N hydrogen bonds occur. In contrast, the dication exhibits considerable deformation, with the pyrrole rings oriented well out of the plane of the porphyrin, resulting in a `saddle' conformation of the ring. The charged species forms N—H⋯O hydrogen bonds to the perchlorate anions, which lie above and below the plane of the porphyrin ring. Distortions to the planarity of the pyrrole rings in both cases are very minor. The characterization of the neutral species represents a low-temperature redetermination of the previous room-temperature analyses [Zou et al. (1995 ). Acta Cryst. C51, 760–761; Rayati et al. (2008 ). Polyhedron, pp. 2285–2290], which showed disorder and physically unrealistic displacement parameters.

Keywords: crystal structure; prophyrin; hydrogen bonding; ring puckering.

CCDC references: 1477658; 1477657

1. Chemical context

Ring folding in porphyrins has long been of interest with characteristics such as ruffling, doming and saddling resulting in strain relief about the ring. In particular, the interactions within the constrained environment of the tetra-pyrrole core predominantly affect the orientation of the pyrrole rings. Two porphyrin molecules were studied to examine the effects of protonation of the pyrrole nitrogen atoms upon the overall geometry of the porphyrin ring systems. The porphyrin: 7,8,17,18-tetrabromo-5,10,15,20-tetraphenylporphyrin (I), H₂TPPBr₄ was adopted for this study. It readily accepts two protons forming a dicationic species (II), [H₄TPPBr₄]²⁺. The neutral porphyrin (I) has previously been reported in two different, room-temperature determinations (Zou et al., 1995; Rayati et al., 2008). However, those two structures display disorder that is not present in the low-temperature determination provided herein.

2. Structural commentary

The neutral porphyrin (I) was found to crystallize about the center of symmetry at the origin (Fig. 1). Distinctly different, the dicationic porphyrin (II) was found to crystallize with one complete porphyrin dication, two perchlorate ions and three molecules of dichloromethane solvent of crystallization in the asymmetric unit (Fig. 2). Thus, the geometry of (I) is influenced by symmetry, while the geometry of (II) is independent of such constraints. In both studies, we elected to use the meta-carbon atoms of the porphyrin ring (labeled as CMn in the Figures; n = atom number) as the basis for an arbitrary mean plane for analyzing distortions.

Figure 1
Structure and labeling scheme of (I)

. Atomic displacement parameters are depicted at 50% probability. H atoms are depicted as spheres of an arbitrary radius. [Symmetry code: (i) −x, −y, −z.]

Figure 2
Structure and labelling scheme of (II)

. Atomic displacement parameters are depicted at 50% probability. H atoms are depicted as spheres of an arbitrary radius. Hydrogen bonds are represented as light-blue dashed lines.

The neutral compound (I) exhibits very mild `ruffling' of the pyrrole rings. The two independent pyrrole rings form periplanar angles of 3.0 (3) and 6.5 (3)° with the four porphyrin meta-carbon atoms (Table 1). This is largely influenced by the lack of steric hindrance of the two hydrogen atoms within the core of the porphyrin ring (Fig. 3). This lack of hindrance is also reflected in the intramolecular N—H⋯N hydrogen bonds formed in the core that have typical D⋯A distances (Table 2). However, these intramolecular hydrogen bonds are not well directed, as demonstrated by the relatively constrained N—H⋯N angles. The pyrrole rings experience very little distortion, with the greatest deviation from the mean-plane being −0.018 (3) Å for CB2 (Table 3). The ruffling of the ring is reflected more so in the deviations of the bromine and ipso-carbon atoms of the phenyl groups from the mean plane (Table 4). It should be noted that due to the center of symmetry, the transannular pairs of pyrrole rings are tilted in opposite directions with respect to the mean plane. Presumably this also plays a role in reducing steric hindrance of the pyrrole hydrogen atoms.

Table 1
Pyrrole periplanar angles (°)

Angles with respect to the mean four atom meta-carbon plane. A `negative' angle represents an arbitrary orientation with the pyrrole N atom below the mean porphyrin plane.

Pyrrole Ring	(I)	(II)
N1—CA1—CB1—CB2—CA2	3.0 (3)	31.0 (5)
N2—CA3—CB3—CB4—CA4	6.5 (3)	−30.1 (5)
N3—CA5—CB5—CB6—CA6		33.6 (4)
N4—CA7—CB7—CB8—CA8		−23.2 (3)

Table 2
Hydrogen-bond geometry (Å, °) for (I)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯N1	0.88	2.47	2.973 (5)	117
N2—H2⋯N1ⁱ	0.88	2.40	2.921 (5)	118
Symmetry code: (i) -x, -y, -z.

Table 3
Deviations from pyrrole planes for (I) and (II) (Å)

Atom	(I)	(II)
N1	−0.008 (3)	−0.012 (7)
CA1	−0.004 (3)	0.006 (7)
CA2	0.015 (3)	0.013 (7)
CB1	0.014 (3)	0.002 (7)
CB2	−0.018 (3)	−0.009 (7)
Br1	−0.117 (8)	−0.28 (2)
Br2	0.403 (7)	−0.28 (2)

N2	0.006 (3)	0.021 (7)
CA3	−0.001 (3)	−0.006 (7)
CA4	−0.009 (3)	−0.027 (7)
CB3	−0.005 (3)	−0.011 (7)
CB4	0.008 (3)	0.023 (7)

N3		−0.015 (6)
CA5		0.017 (6)
CA6		0.007 (7)
CB5		−0.013 (7)
CB6		0.004 (7)
Br3		−0.283 (18)
Br4		−0.114 (19)

N4		0.005 (8)
CA7		0.000 (7)
CA8		−0.007 (8)
CB7		−0.004 (8)
CB8		0.006 (8)

Table 4
Deviations of peripheral atoms from mean meta-carbon plane for (I) and (II) (Å)

Atom	(I)	(II)
C11	−0.240 (7)	−0.038 (19)
C21	0.205 (8)	0.194 (18)
C31		0.061 (18)
C41		0.232 (19)

Figure 3
View through the porphyrin plane of (I)

showing ring `ruffling'. H atoms, except pyrrole H atoms, have been omitted for clarity.

In contrast the dicationic porphyrin (II) relieves strain by adopting a `saddled' conformation (Fig. 4). In this fashion, steric repulsion between the four hydrogen atoms intruding on the core of the porphyrin is significantly reduced. Furthermore, due to the presence of charge-balancing perchlorate anions, each pair of transannular pyrrole nitrogen atoms form hydrogen bonds to one oxygen atom of either perchlorate anion (N1/N3⋯O21, N2/N4⋯O25, Fig. 2, Table 5).

Table 5
Hydrogen-bond geometry (Å, °) for (II)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N2	0.88	2.57	3.018 (12)	113
N1—H1⋯O21	0.88	2.12	2.956 (14)	158
N2—H2⋯N1	0.88	2.60	3.018 (12)	110
N2—H2⋯N3	0.88	2.59	3.026 (12)	111
N2—H2⋯O11	0.88	2.07	2.896 (12)	157
N3—H3⋯O21	0.88	2.08	2.932 (13)	162
N4—H4⋯N3	0.88	2.62	3.034 (12)	110
N4—H4⋯O11	0.88	2.01	2.844 (13)	159

Figure 4
View through the porphyrin plane of (II)

demonstrating ring `saddling'. H atoms, except pyrrole H atoms, have been omitted for clarity.

Surprisingly, the pyrrole rings in (II) do not adopt any crystallographic symmetry. Crystallographically, each pair of rings oriented `up' and `down' (arbitrarily defined) form different angles with respect to the meta-carbon plane. Inspection of the structure shows that the bromo-pyrrole rings are inclined in the same fashion (we have arbitrarily defined this as `down' or a negative periplanar angle with regards to the pyrrole nitrogen atoms with respect to the porphyrin mean plane). In contrast with (I), the pyrrole rings in (II) form angles ±30° with respect to the mean porphyrin plane (Table 1). Compared with (I) wherein one bromine atom is deformed `above' the pyrrole plane and the other `below', the bromine atoms in (II) are all oriented out of the mean plane of their respective pyrrole rings in the same fashion (i.e. all of the deviations from the mean pyrrole plane are negative). The atoms of the pyrrole rings are essentially co-planar with the largest deviation from the mean plane for any pyrrole atom being −0.027 (7) Å for CA4 (Table 3).

Comparing bond distances around the neutral and dicationic porphyrin ring systems reveals little change in the bond distances associated with the pyrrole rings or backbone (see CIF files). Thus, in either a neutral or charged state the porphyrin consists largely of delocalized bonds, rather than the single-bond/double-bond formalism.

3. Supramolecular features

The neutral compound (I) packs with typical van der Waals contacts. Potential close contacts from C16 to the pyrrole of an adjacent molecule have the shortest heavy-atom contact around 3.45 Å.

In contrast, compound (II) is formed with hydrogen bonds from the pyrrole nitrogen atoms to perchlorate oxygen atoms (Fig. 2, Table 5 for details). Remaining intermolecular contacts throughout the structure are all usual van der Waals interactions.

4. Database survey

Inspection of the Cambridge Structure Database (Version 5.38 plus 1 update; Groom et al., 2016 ) reveals three structures that incorporate the H₂TPPBr₄ moiety. Two structures (GOGNIA: Rayati et al., 2008; LINPON: Zou et al., 1995) are room-temperature determinations of the low-temperature structure (I) reported herein. Examination of those two structures reveals several underlying problems, such as disorder and unreasonable atomic displacement parameters that are not present in this study. The third compound that incorporates H₂TPPBr₄ is a co-crystallant with C60 fullerene (TUBPAJ: Karunanithi & Bhyrappa, 2015 ). To the best of our knowledge, the dicationic species (II) has not been structurally characterized in any form.

5. Synthesis and crystallization

Compound (I) was prepared following literature procedures (Callot, 1973 ; Crossley et al., 1991 ). Compound (II) was prepared with procedures as previously described (Cheng et al., 1997 ).

6. Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 6. All non-hydrogen atoms were refined with anisotropic atomic displacement parameters. C-bound hydrogen atoms were included in geometrically calculated positions. N-bound hydrogen atoms were initially located from a difference Fourier map and subsequently included using a riding model. U_iso(H) = 1.2U_eq(C/N); C—H distances were set at 0.95 Å and N—H set at 0.88 Å for (I) and (II). Due to the age of the data and an infelicity in data archiving, only the printed structure-factor tables and final residuals file were available. Data were reconstituted from these tables into an h k l F σ(F) format file and the atomic models refined against these to result in the structures contained herein. It was not considered reasonable to attempt to resynthesize and recrystallize the compounds and collect new intensity data.

Table 6
Experimental details

	(I)	(II)
Crystal data
Chemical formula	C₄₄H₂₆Br₄N₄	C₄₄H₂₈Br₄N₄²⁺·2ClO₄⁻·3CH₂Cl₂
M_r	930.33	1386.02
Crystal system, space group	Monoclinic, P2₁/n	Monoclinic, Pn
Temperature (K)	130	130
a, b, c (Å)	13.883 (3), 6.7448 (13), 19.110 (4)	12.903 (3), 13.761 (3), 14.876 (3)
β (°)	102.00 (3)	96.67 (3)
V (Å³)	1750.3 (7)	2623.5 (10)
Z	2	2
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	4.64	3.53
Crystal size (mm)	0.15 × 0.10 × 0.05	0.33 × 0.17 × 0.06

Data collection
Diffractometer	Enraf–Nonius fast area-detector	Enraf–Nonius fast area-detector
Absorption correction	Part of the refinement model (ΔF) (DIFABS; Walker & Stuart, 1983 )	Part of the refinement model (ΔF) (DIFABS; Walker & Stuart, 1983)
T_min, T_max	0.72, 1.00	0.65, 1.00
No. of measured, independent and observed [I > 2σ(I)] reflections	4589, 4589, 3439	11251, 11251, 8745
(sin θ/λ)_max (Å⁻¹)	0.701	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.156, 1.08	0.060, 0.185, 1.06
No. of reflections	4589	11251
No. of parameters	235	640
No. of restraints	0	2
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.17, −1.41	1.03, −1.05
Absolute structure	–	Classical Flack method preferred over Parsons because s.u. lower (Flack, 1983 )
Absolute structure parameter	–	−0.032 (14)
Computer programs: MADNES (Pflugrath & Messerschmidt, 1989 ), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), OLEX2 (Dolomanov et al., 2009 ), Mercury (Macrae et al., 2008 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC references: 1477658; 1477657

Crystal structure: contains datablocks I, II, global. DOI: https://doi.org/10.1107/S2056989016007349/hb7580sup1.cif

Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989016007349/hb7580IIsup3.hkl

checkCIF report

Computing details top

For both compounds, data collection: MADNES (Pflugrath & Messerschmidt, 1989); cell refinement: MADNES (Pflugrath & Messerschmidt, 1989); data reduction: MADNES (Pflugrath & Messerschmidt, 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

(I) 7,8,17,18-Tetrabromo-5,10,15,20-tetraphenylporphyrin top

Crystal data top

C₄₄H₂₆Br₄N₄	F(000) = 916
M_r = 930.33	D_x = 1.765 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 13.883 (3) Å	Cell parameters from 250 reflections
b = 6.7448 (13) Å	θ = 2.5–20.5°
c = 19.110 (4) Å	µ = 4.64 mm⁻¹
β = 102.00 (3)°	T = 130 K
V = 1750.3 (7) Å³	Prism, dark blue
Z = 2	0.15 × 0.10 × 0.05 mm

Data collection top

Enraf–Nonius fast area-detector diffractometer	4589 measured reflections
Radiation source: ROTATING ANODE	4589 independent reflections
Graphite monochromator	3439 reflections with I > 2σ(I)
Detector resolution: 8.53 pixels mm^-1	θ_max = 29.9°, θ_min = 3.0°
ELLIPSOID–MASK FITTING scans	h = −19→18
Absorption correction: part of the refinement model (ΔF) (DIFABS; Walker & Stuart, 1983)	k = 0→9
T_min = 0.72, T_max = 1.00	l = 0→26

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.156	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0649P)² + 9.9345P] where P = (F_o² + 2F_c²)/3
4589 reflections	(Δ/σ)_max < 0.001
235 parameters	Δρ_max = 1.17 e Å⁻³
0 restraints	Δρ_min = −1.41 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
N1	0.1162 (3)	0.2085 (6)	0.02369 (19)	0.0155 (7)
N2	−0.0795 (3)	0.1542 (6)	0.0612 (2)	0.0176 (7)
H2	−0.0527	0.1021	0.0276	0.021*
CA1	0.2010 (3)	0.2138 (6)	−0.0031 (2)	0.0163 (8)
CA2	0.1182 (3)	0.3683 (6)	0.0676 (2)	0.0148 (8)
CA3	−0.0411 (3)	0.3106 (7)	0.1040 (2)	0.0156 (8)
CA4	−0.1664 (3)	0.0898 (7)	0.0785 (2)	0.0183 (8)
CB1	0.2583 (3)	0.3860 (7)	0.0253 (2)	0.0178 (8)
CB2	0.2072 (3)	0.4848 (7)	0.0667 (2)	0.0172 (8)
CB3	−0.1091 (3)	0.3476 (7)	0.1503 (3)	0.0204 (9)
HB3	−0.1024	0.4471	0.1862	0.025*
CB4	−0.1835 (3)	0.2172 (7)	0.1340 (3)	0.0223 (9)
HB4	−0.2389	0.2110	0.1560	0.027*
CM1	0.0469 (3)	0.4092 (6)	0.1078 (2)	0.0151 (8)
CM2	0.2222 (3)	0.0767 (6)	−0.0529 (2)	0.0161 (8)
C11	0.0682 (3)	0.5628 (7)	0.1657 (2)	0.0161 (8)
C12	0.1363 (3)	0.5217 (7)	0.2295 (2)	0.0198 (9)
H12	0.1702	0.3985	0.2345	0.024*
C13	0.1550 (4)	0.6569 (7)	0.2854 (3)	0.0218 (9)
H13	0.2013	0.6278	0.3283	0.026*
C14	0.1035 (4)	0.8386 (8)	0.2771 (3)	0.0258 (10)
H14	0.1149	0.9329	0.3148	0.031*
C15	0.0370 (4)	0.8803 (8)	0.2150 (3)	0.0265 (10)
H15	0.0033	1.0037	0.2101	0.032*
C16	0.0185 (4)	0.7440 (7)	0.1589 (3)	0.0244 (10)
H16	−0.0279	0.7743	0.1163	0.029*
C21	0.3085 (3)	0.1125 (7)	−0.0877 (3)	0.0202 (9)
C22	0.3923 (4)	−0.0027 (8)	−0.0723 (3)	0.0242 (10)
H22	0.3978	−0.1064	−0.0380	0.029*
C23	0.4683 (4)	0.0344 (9)	−0.1075 (3)	0.0330 (12)
H23	0.5257	−0.0462	−0.0973	0.040*
C24	0.4629 (4)	0.1832 (9)	−0.1563 (3)	0.0299 (11)
H24	0.5167	0.2083	−0.1787	0.036*
C25	0.3791 (4)	0.2968 (9)	−0.1728 (3)	0.0309 (11)
H25	0.3749	0.4005	−0.2069	0.037*
C26	0.3000 (4)	0.2606 (8)	−0.1398 (3)	0.0261 (10)
H26	0.2411	0.3357	−0.1526	0.031*
Br2	0.24434 (4)	0.73342 (7)	0.10682 (2)	0.02175 (14)
Br1	0.38509 (4)	0.46336 (8)	0.01738 (3)	0.02782 (16)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0159 (17)	0.0179 (18)	0.0124 (16)	−0.0043 (14)	0.0023 (13)	−0.0017 (13)
N2	0.0131 (16)	0.0218 (19)	0.0163 (16)	−0.0018 (14)	−0.0005 (14)	−0.0062 (14)
CA1	0.021 (2)	0.0157 (19)	0.0128 (18)	0.0005 (16)	0.0049 (16)	0.0029 (15)
CA2	0.0117 (18)	0.0167 (19)	0.0135 (17)	−0.0008 (14)	−0.0031 (15)	−0.0017 (15)
CA3	0.0146 (19)	0.019 (2)	0.0132 (18)	0.0013 (15)	0.0018 (15)	−0.0031 (15)
CA4	0.0163 (19)	0.020 (2)	0.019 (2)	−0.0044 (16)	0.0054 (17)	−0.0036 (17)
CB1	0.0152 (19)	0.023 (2)	0.0158 (19)	−0.0011 (16)	0.0039 (15)	0.0018 (16)
CB2	0.017 (2)	0.018 (2)	0.0145 (19)	−0.0030 (16)	−0.0015 (16)	0.0002 (16)
CB3	0.020 (2)	0.022 (2)	0.021 (2)	0.0066 (17)	0.0058 (18)	−0.0029 (17)
CB4	0.017 (2)	0.023 (2)	0.026 (2)	−0.0001 (17)	0.0023 (18)	−0.0072 (18)
CM1	0.0182 (19)	0.0144 (19)	0.0106 (18)	−0.0013 (15)	−0.0019 (15)	−0.0013 (14)
CM2	0.0170 (19)	0.017 (2)	0.0146 (18)	0.0008 (15)	0.0030 (16)	0.0007 (15)
C11	0.0137 (18)	0.020 (2)	0.0120 (18)	0.0034 (15)	−0.0036 (15)	0.0001 (15)
C12	0.023 (2)	0.023 (2)	0.0120 (18)	−0.0046 (17)	−0.0002 (17)	−0.0020 (16)
C13	0.025 (2)	0.020 (2)	0.018 (2)	−0.0052 (17)	−0.0025 (18)	−0.0005 (17)
C14	0.029 (2)	0.025 (2)	0.023 (2)	−0.007 (2)	0.005 (2)	−0.0124 (19)
C15	0.027 (2)	0.022 (2)	0.028 (2)	0.0071 (19)	0.000 (2)	−0.009 (2)
C16	0.021 (2)	0.026 (2)	0.022 (2)	0.0019 (18)	−0.0048 (18)	−0.0073 (18)
C21	0.0147 (19)	0.024 (2)	0.023 (2)	−0.0047 (17)	0.0060 (17)	−0.0086 (18)
C22	0.021 (2)	0.026 (2)	0.026 (2)	0.0004 (18)	0.0040 (19)	0.0017 (19)
C23	0.020 (2)	0.044 (3)	0.035 (3)	0.002 (2)	0.006 (2)	−0.003 (2)
C24	0.021 (2)	0.042 (3)	0.032 (3)	−0.009 (2)	0.017 (2)	−0.004 (2)
C25	0.038 (3)	0.038 (3)	0.020 (2)	−0.002 (2)	0.014 (2)	0.007 (2)
C26	0.023 (2)	0.035 (3)	0.022 (2)	0.002 (2)	0.0089 (19)	0.008 (2)
Br2	0.0263 (3)	0.0177 (2)	0.0210 (2)	−0.00664 (17)	0.00424 (18)	−0.00363 (16)
Br1	0.0226 (3)	0.0307 (3)	0.0331 (3)	−0.01189 (19)	0.0126 (2)	−0.0098 (2)

Geometric parameters (Å, º) top

N1—CA2	1.363 (5)	C11—C16	1.396 (6)
N1—CA1	1.378 (6)	C11—C12	1.407 (6)
N2—CA3	1.372 (6)	C12—C13	1.387 (6)
N2—CA4	1.385 (5)	C12—H12	0.9500
N2—H2	0.8800	C13—C14	1.411 (7)
CA1—CM2	1.402 (6)	C13—H13	0.9500
CA1—CB1	1.447 (6)	C14—C15	1.372 (7)
CA2—CM1	1.400 (6)	C14—H14	0.9500
CA2—CB2	1.467 (6)	C15—C16	1.395 (7)
CA3—CM1	1.380 (6)	C15—H15	0.9500
CA3—CB3	1.444 (6)	C16—H16	0.9500
CA4—CM2ⁱ	1.395 (6)	C21—C22	1.378 (7)
CA4—CB4	1.422 (6)	C21—C26	1.398 (7)
CB1—CB2	1.344 (6)	C22—C23	1.387 (7)
CB1—Br1	1.872 (4)	C22—H22	0.9500
CB2—Br2	1.871 (4)	C23—C24	1.361 (8)
CB3—CB4	1.344 (7)	C23—H23	0.9500
CB3—HB3	0.9500	C24—C25	1.375 (8)
CB4—HB4	0.9500	C24—H24	0.9500
CM1—C11	1.500 (6)	C25—C26	1.397 (7)
CM2—CA4ⁱ	1.395 (6)	C25—H25	0.9500
CM2—C21	1.505 (6)	C26—H26	0.9500

CA2—N1—CA1	107.4 (3)	C16—C11—CM1	121.2 (4)
CA3—N2—CA4	110.4 (4)	C12—C11—CM1	119.8 (4)
CA3—N2—H2	124.8	C13—C12—C11	121.5 (5)
CA4—N2—H2	124.8	C13—C12—H12	119.2
N1—CA1—CM2	123.5 (4)	C11—C12—H12	119.2
N1—CA1—CB1	109.1 (4)	C12—C13—C14	118.3 (4)
CM2—CA1—CB1	127.4 (4)	C12—C13—H13	120.8
N1—CA2—CM1	124.5 (4)	C14—C13—H13	120.8
N1—CA2—CB2	109.0 (4)	C15—C14—C13	120.6 (4)
CM1—CA2—CB2	126.5 (4)	C15—C14—H14	119.7
N2—CA3—CM1	129.2 (4)	C13—C14—H14	119.7
N2—CA3—CB3	106.0 (4)	C14—C15—C16	120.9 (5)
CM1—CA3—CB3	124.7 (4)	C14—C15—H15	119.6
N2—CA4—CM2ⁱ	128.1 (4)	C16—C15—H15	119.6
N2—CA4—CB4	106.2 (4)	C15—C16—C11	119.8 (4)
CM2ⁱ—CA4—CB4	125.5 (4)	C15—C16—H16	120.1
CB2—CB1—CA1	107.6 (4)	C11—C16—H16	120.1
CB2—CB1—Br1	121.9 (4)	C22—C21—C26	119.8 (4)
CA1—CB1—Br1	130.3 (3)	C22—C21—CM2	121.9 (5)
CB1—CB2—CA2	106.9 (4)	C26—C21—CM2	118.1 (4)
CB1—CB2—Br2	123.5 (3)	C21—C22—C23	119.2 (5)
CA2—CB2—Br2	129.5 (3)	C21—C22—H22	120.4
CB4—CB3—CA3	108.2 (4)	C23—C22—H22	120.4
CB4—CB3—HB3	125.9	C24—C23—C22	121.7 (5)
CA3—CB3—HB3	125.9	C24—C23—H23	119.1
CB3—CB4—CA4	109.2 (4)	C22—C23—H23	119.1
CB3—CB4—HB4	125.4	C23—C24—C25	119.5 (5)
CA4—CB4—HB4	125.4	C23—C24—H24	120.3
CA3—CM1—CA2	126.5 (4)	C25—C24—H24	120.3
CA3—CM1—C11	114.1 (4)	C24—C25—C26	120.4 (5)
CA2—CM1—C11	119.1 (4)	C24—C25—H25	119.8
CA4ⁱ—CM2—CA1	126.1 (4)	C26—C25—H25	119.8
CA4ⁱ—CM2—C21	114.2 (4)	C25—C26—C21	119.2 (5)
CA1—CM2—C21	119.5 (4)	C25—C26—H26	120.4
C16—C11—C12	118.9 (4)	C21—C26—H26	120.4

CA2—N1—CA1—CM2	−177.1 (4)	N1—CA2—CM1—C11	166.8 (4)
CA2—N1—CA1—CB1	−0.4 (5)	CB2—CA2—CM1—C11	−11.9 (6)
CA1—N1—CA2—CM1	−176.8 (4)	N1—CA1—CM2—CA4ⁱ	−4.9 (7)
CA1—N1—CA2—CB2	2.2 (5)	CB1—CA1—CM2—CA4ⁱ	179.0 (4)
CA4—N2—CA3—CM1	175.2 (5)	N1—CA1—CM2—C21	170.5 (4)
CA4—N2—CA3—CB3	−0.7 (5)	CB1—CA1—CM2—C21	−5.6 (7)
CA3—N2—CA4—CM2ⁱ	−172.8 (5)	CA3—CM1—C11—C16	−74.4 (6)
CA3—N2—CA4—CB4	1.4 (5)	CA2—CM1—C11—C16	110.5 (5)
N1—CA1—CB1—CB2	−1.7 (5)	CA3—CM1—C11—C12	102.8 (5)
CM2—CA1—CB1—CB2	174.9 (4)	CA2—CM1—C11—C12	−72.3 (6)
N1—CA1—CB1—Br1	173.1 (3)	C16—C11—C12—C13	−0.2 (7)
CM2—CA1—CB1—Br1	−10.4 (7)	CM1—C11—C12—C13	−177.4 (4)
CA1—CB1—CB2—CA2	2.9 (5)	C11—C12—C13—C14	0.3 (7)
Br1—CB1—CB2—CA2	−172.4 (3)	C12—C13—C14—C15	−0.4 (8)
CA1—CB1—CB2—Br2	−172.8 (3)	C13—C14—C15—C16	0.4 (8)
Br1—CB1—CB2—Br2	11.9 (6)	C14—C15—C16—C11	−0.3 (8)
N1—CA2—CB2—CB1	−3.2 (5)	C12—C11—C16—C15	0.1 (8)
CM1—CA2—CB2—CB1	175.6 (4)	CM1—C11—C16—C15	177.3 (5)
N1—CA2—CB2—Br2	172.1 (3)	CA4ⁱ—CM2—C21—C22	−74.0 (6)
CM1—CA2—CB2—Br2	−9.0 (7)	CA1—CM2—C21—C22	110.1 (5)
N2—CA3—CB3—CB4	−0.3 (5)	CA4ⁱ—CM2—C21—C26	102.5 (5)
CM1—CA3—CB3—CB4	−176.5 (4)	CA1—CM2—C21—C26	−73.5 (6)
CA3—CB3—CB4—CA4	1.2 (6)	C26—C21—C22—C23	2.0 (8)
N2—CA4—CB4—CB3	−1.6 (6)	CM2—C21—C22—C23	178.4 (5)
CM2ⁱ—CA4—CB4—CB3	172.8 (5)	C21—C22—C23—C24	0.7 (9)
N2—CA3—CM1—CA2	−0.3 (8)	C22—C23—C24—C25	−1.8 (9)
CB3—CA3—CM1—CA2	174.9 (4)	C23—C24—C25—C26	0.2 (9)
N2—CA3—CM1—C11	−175.0 (4)	C24—C25—C26—C21	2.5 (9)
CB3—CA3—CM1—C11	0.2 (6)	C22—C21—C26—C25	−3.5 (8)
N1—CA2—CM1—CA3	−7.6 (7)	CM2—C21—C26—C25	179.9 (5)
CB2—CA2—CM1—CA3	173.6 (4)

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N1	0.88	2.47	2.973 (5)	117
N2—H2···N1ⁱ	0.88	2.40	2.921 (5)	118

Symmetry code: (i) −x, −y, −z.

(II) 7,8,17,18-Tetrabromo-5,10,15,20-tetraphenylporphyrin(2+) bis(perchlorate) dichloromethane trisolvate top

Crystal data top

C₄₄H₂₈Br₄N₄²⁺·2ClO₄⁻·3CH₂Cl₂	F(000) = 1368
M_r = 1386.02	D_x = 1.755 Mg m⁻³
Monoclinic, Pn	Mo Kα radiation, λ = 0.71073 Å
a = 12.903 (3) Å	Cell parameters from 250 reflections
b = 13.761 (3) Å	θ = 1.1–20.5°
c = 14.876 (3) Å	µ = 3.53 mm⁻¹
β = 96.67 (3)°	T = 130 K
V = 2623.5 (10) Å³	Prism, blue-green
Z = 2	0.33 × 0.17 × 0.06 mm

Data collection top

Enraf–Nonius fast area-detector diffractometer	11251 measured reflections
Radiation source: ROTATING ANODE	11251 independent reflections
Graphite monochromator	8745 reflections with I > 2σ(I)
Detector resolution: 8.53 pixels mm^-1	θ_max = 30.0°, θ_min = 2.5°
ELLIPSOID–MASK FITTING scans	h = −16→16
Absorption correction: part of the refinement model (ΔF) (DIFABS; Walker & Stuart, 1983)	k = 0→19
T_min = 0.65, T_max = 1.00	l = −19→18

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.060	H-atom parameters constrained
wR(F²) = 0.185	w = 1/[σ²(F_o²) + (0.0886P)² + 17.5195P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
11251 reflections	Δρ_max = 1.03 e Å⁻³
640 parameters	Δρ_min = −1.05 e Å⁻³
2 restraints	Absolute structure: Classical Flack method preferred over Parsons because s.u. lower (Flack, 1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.032 (14)

Special details top

Experimental. Diffraction data were measured with an Enraf-Nonius FAST area detector to 55.56 deg in 2 theta. With the hardware and software supplied for the diffractometer, the data collection process provides substantial redundancy but not necessarily completion up to the limiting resolution. At a resolution of 0.83 Å (52 deg in 2 theta) essentially full coverage of data were met. Successful and suitable refinement of the structure supports this.

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

	x	y	z	U_iso*/U_eq
Br1	0.21338 (9)	1.56160 (8)	0.81718 (9)	0.0297 (3)
Br2	−0.02997 (9)	1.55748 (8)	0.89049 (9)	0.0301 (3)
Br3	0.03558 (8)	0.82412 (7)	0.99749 (8)	0.0252 (3)
Br4	0.28295 (8)	0.82050 (7)	0.92686 (8)	0.0265 (3)
N1	0.1827 (7)	1.3717 (6)	1.0200 (7)	0.0230 (19)
H1	0.2019	1.3221	1.0555	0.028*
N2	0.0484 (7)	1.2123 (6)	1.0839 (6)	0.0204 (18)
H2	0.0886	1.2076	1.0402	0.024*
N3	0.2148 (7)	1.0609 (6)	1.0661 (6)	0.0167 (16)
H3	0.2260	1.1203	1.0869	0.020*
N4	0.3381 (7)	1.2157 (6)	0.9795 (7)	0.0222 (19)
H4	0.2697	1.2093	0.9724	0.027*
CA1	0.2450 (8)	1.4179 (7)	0.9635 (8)	0.022 (2)
CA2	0.0851 (8)	1.4144 (7)	1.0124 (8)	0.020 (2)
CA3	0.0030 (8)	1.2964 (7)	1.1094 (8)	0.019 (2)
CA4	0.0213 (8)	1.1366 (7)	1.1364 (7)	0.0183 (19)
CA5	0.1262 (8)	1.0075 (7)	1.0743 (8)	0.0193 (19)
CA6	0.2834 (8)	1.0081 (7)	1.0211 (7)	0.0178 (19)
CA7	0.4088 (8)	1.1407 (7)	0.9972 (8)	0.022 (2)
CA8	0.3906 (8)	1.3014 (7)	0.9749 (8)	0.021 (2)
CB1	0.1808 (9)	1.4904 (8)	0.9173 (8)	0.025 (2)
CB2	0.0831 (8)	1.4884 (7)	0.9456 (9)	0.023 (2)
C11	−0.0765 (10)	1.4564 (8)	1.0813 (9)	0.027 (2)
CB3	−0.0511 (8)	1.2742 (6)	1.1835 (8)	0.018 (2)
HB3	−0.0902	1.3188	1.2147	0.021*
C12	−0.0536 (10)	1.5524 (8)	1.1070 (9)	0.029 (3)
H12	0.0171	1.5727	1.1175	0.035*
CB4	−0.0378 (8)	1.1765 (7)	1.2033 (8)	0.020 (2)
HB4	−0.0630	1.1425	1.2518	0.024*
C13	−0.1339 (12)	1.6199 (9)	1.1176 (11)	0.038 (3)
H13	−0.1173	1.6847	1.1358	0.045*
CB5	0.1381 (7)	0.9188 (7)	1.0280 (7)	0.0163 (18)
C14	−0.2362 (13)	1.5906 (11)	1.1012 (12)	0.044 (4)
H14	−0.2905	1.6356	1.1082	0.052*
CB6	0.2333 (9)	0.9172 (7)	0.9968 (8)	0.022 (2)
C15	−0.2605 (11)	1.4969 (10)	1.0750 (11)	0.039 (3)
H15	−0.3316	1.4778	1.0640	0.047*
CB7	0.5103 (8)	1.1810 (7)	1.0048 (8)	0.019 (2)
HB7	0.5738	1.1459	1.0165	0.023*
C16	−0.1826 (10)	1.4296 (9)	1.0642 (10)	0.031 (3)
H16	−0.2008	1.3653	1.0453	0.037*
CB8	0.5011 (8)	1.2787 (8)	0.9925 (8)	0.023 (2)
HB8	0.5569	1.3240	0.9949	0.028*
CM1	0.0064 (9)	1.3882 (7)	1.0662 (8)	0.021 (2)
CM2	0.0454 (8)	1.0384 (7)	1.1241 (7)	0.0180 (19)
CM3	0.3822 (9)	1.0421 (8)	1.0052 (8)	0.023 (2)
CM4	0.3474 (9)	1.3949 (7)	0.9573 (8)	0.022 (2)
C21	−0.0149 (9)	0.9650 (7)	1.1696 (8)	0.023 (2)
C22	−0.1224 (9)	0.9712 (8)	1.1722 (9)	0.026 (2)
H22	−0.1601	1.0230	1.1416	0.031*
C23	−0.1751 (10)	0.9040 (9)	1.2179 (10)	0.032 (3)
H23	−0.2481	0.9103	1.2202	0.038*
C24	−0.1207 (11)	0.8276 (8)	1.2602 (10)	0.031 (3)
H24	−0.1567	0.7800	1.2909	0.038*
C25	−0.0156 (12)	0.8192 (8)	1.2585 (10)	0.032 (3)
H25	0.0203	0.7661	1.2887	0.039*
C26	0.0404 (9)	0.8866 (7)	1.2135 (8)	0.022 (2)
H26	0.1136	0.8800	1.2125	0.026*
C31	0.4696 (9)	0.9730 (7)	0.9965 (8)	0.021 (2)
C32	0.5005 (9)	0.9087 (7)	1.0679 (9)	0.026 (2)
H32	0.4619	0.9049	1.1184	0.031*
C33	0.5880 (9)	0.8506 (8)	1.0642 (9)	0.026 (2)
H33	0.6103	0.8077	1.1126	0.031*
C34	0.6427 (8)	0.8558 (8)	0.9893 (10)	0.028 (3)
H34	0.7027	0.8163	0.9871	0.033*
C35	0.6114 (9)	0.9172 (8)	0.9182 (10)	0.028 (3)
H35	0.6485	0.9183	0.8666	0.034*
C36	0.5244 (9)	0.9785 (7)	0.9218 (9)	0.024 (2)
H36	0.5037	1.0226	0.8740	0.029*
C41	0.4185 (9)	1.4724 (7)	0.9340 (9)	0.025 (2)
C42	0.4811 (10)	1.4640 (8)	0.8651 (9)	0.028 (3)
H42	0.4788	1.4062	0.8299	0.034*
C43	0.5470 (10)	1.5388 (9)	0.8468 (10)	0.031 (3)
H43	0.5915	1.5309	0.8007	0.038*
C44	0.5490 (9)	1.6256 (8)	0.8951 (10)	0.030 (3)
H44	0.5921	1.6778	0.8804	0.036*
C45	0.4872 (11)	1.6347 (8)	0.9650 (11)	0.037 (3)
H45	0.4896	1.6930	0.9994	0.044*
C46	0.4211 (9)	1.5588 (7)	0.9858 (10)	0.030 (3)
H46	0.3789	1.5654	1.0337	0.036*
Cl1	0.0799 (2)	1.22478 (18)	0.8343 (2)	0.0237 (5)
O11	0.1277 (7)	1.1716 (5)	0.9135 (6)	0.0240 (16)
O12	0.1604 (8)	1.2791 (7)	0.7995 (8)	0.041 (2)
O13	0.0358 (9)	1.1571 (7)	0.7677 (7)	0.045 (3)
O14	0.0026 (8)	1.2868 (8)	0.8638 (8)	0.046 (3)
Cl2	0.2813 (2)	1.26950 (19)	1.2481 (2)	0.0262 (6)
O21	0.2935 (8)	1.2403 (7)	1.1561 (7)	0.036 (2)
O22	0.3723 (8)	1.2469 (10)	1.3065 (9)	0.055 (3)
O23	0.1930 (9)	1.2212 (9)	1.2770 (8)	0.050 (3)
O24	0.2607 (13)	1.3723 (8)	1.2457 (11)	0.071 (4)
Cl21	−0.2688 (4)	1.3297 (5)	0.6411 (4)	0.0755 (15)
Cl22	−0.2737 (5)	1.3405 (5)	0.8337 (4)	0.0818 (17)
C20	−0.201 (2)	1.357 (3)	0.7458 (17)	0.110 (11)
H20A	−0.1377	1.3155	0.7555	0.132*
H20B	−0.1771	1.4256	0.7455	0.132*
Cl31	0.6956 (2)	1.2315 (2)	1.1840 (2)	0.0347 (7)
Cl32	0.5739 (4)	1.0744 (3)	1.2483 (3)	0.0546 (11)
C30	0.5833 (10)	1.2005 (9)	1.2365 (9)	0.030 (3)
H30A	0.5874	1.2315	1.2968	0.037*
H30B	0.5201	1.2252	1.1994	0.037*
Cl41	−0.1911 (3)	1.0330 (4)	0.7629 (3)	0.0619 (12)
Cl42	−0.1778 (4)	1.1044 (4)	0.9474 (4)	0.0691 (13)
C40	−0.1286 (14)	1.0241 (13)	0.8713 (14)	0.056 (5)
H40A	−0.0534	1.0373	0.8702	0.068*
H40B	−0.1357	0.9567	0.8932	0.068*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0310 (6)	0.0282 (5)	0.0307 (7)	0.0011 (4)	0.0075 (5)	0.0114 (5)
Br2	0.0270 (6)	0.0289 (5)	0.0346 (8)	0.0086 (4)	0.0039 (5)	0.0105 (5)
Br3	0.0235 (5)	0.0230 (5)	0.0293 (7)	−0.0065 (4)	0.0046 (5)	−0.0061 (4)
Br4	0.0252 (5)	0.0233 (5)	0.0317 (7)	−0.0004 (4)	0.0056 (5)	−0.0104 (4)
N1	0.025 (4)	0.016 (4)	0.027 (6)	0.000 (3)	−0.002 (4)	0.004 (3)
N2	0.026 (4)	0.020 (4)	0.018 (5)	0.004 (3)	0.012 (4)	0.002 (3)
N3	0.015 (4)	0.017 (3)	0.020 (5)	0.000 (3)	0.005 (3)	0.000 (3)
N4	0.020 (4)	0.021 (4)	0.025 (6)	0.000 (3)	0.002 (4)	0.004 (3)
CA1	0.016 (5)	0.017 (4)	0.033 (7)	−0.009 (3)	0.006 (4)	0.002 (4)
CA2	0.018 (5)	0.019 (4)	0.025 (6)	0.001 (3)	0.003 (4)	0.000 (4)
CA3	0.018 (4)	0.019 (4)	0.020 (6)	−0.002 (3)	0.006 (4)	−0.003 (4)
CA4	0.021 (5)	0.019 (4)	0.015 (6)	−0.002 (3)	0.003 (4)	0.002 (4)
CA5	0.020 (5)	0.022 (4)	0.016 (6)	0.002 (4)	0.001 (4)	−0.001 (4)
CA6	0.018 (4)	0.020 (4)	0.016 (6)	0.004 (3)	0.003 (4)	0.004 (4)
CA7	0.020 (5)	0.015 (4)	0.031 (7)	0.000 (3)	0.006 (4)	−0.003 (4)
CA8	0.018 (5)	0.017 (4)	0.027 (7)	−0.006 (3)	0.001 (4)	−0.004 (4)
CB1	0.032 (6)	0.025 (5)	0.019 (6)	−0.003 (4)	0.005 (5)	0.004 (4)
CB2	0.013 (4)	0.020 (4)	0.036 (7)	−0.003 (3)	0.005 (4)	0.008 (4)
C11	0.037 (6)	0.019 (5)	0.025 (7)	−0.001 (4)	0.006 (5)	−0.004 (4)
CB3	0.018 (4)	0.014 (4)	0.022 (6)	0.006 (3)	0.002 (4)	−0.002 (3)
C12	0.029 (6)	0.026 (5)	0.032 (8)	−0.007 (4)	0.005 (5)	−0.009 (5)
CB4	0.022 (5)	0.019 (5)	0.021 (6)	0.003 (3)	0.007 (4)	−0.003 (4)
C13	0.045 (7)	0.024 (5)	0.044 (9)	0.012 (5)	0.008 (6)	−0.013 (5)
CB5	0.015 (4)	0.017 (4)	0.017 (6)	−0.005 (3)	0.001 (4)	−0.003 (3)
C14	0.046 (8)	0.038 (7)	0.048 (10)	0.015 (6)	0.010 (7)	−0.005 (6)
CB6	0.027 (5)	0.014 (4)	0.026 (6)	0.004 (4)	0.006 (4)	0.006 (4)
C15	0.034 (7)	0.041 (7)	0.043 (9)	0.008 (5)	0.004 (6)	0.002 (6)
CB7	0.017 (5)	0.020 (4)	0.019 (6)	−0.001 (3)	−0.002 (4)	0.002 (4)
C16	0.027 (6)	0.035 (6)	0.029 (8)	0.002 (5)	0.001 (5)	−0.003 (5)
CB8	0.016 (5)	0.027 (5)	0.026 (7)	−0.003 (4)	0.003 (4)	0.005 (4)
CM1	0.028 (5)	0.019 (4)	0.016 (6)	−0.002 (4)	0.004 (4)	−0.003 (4)
CM2	0.022 (5)	0.022 (4)	0.010 (5)	−0.001 (4)	0.006 (4)	−0.001 (3)
CM3	0.023 (5)	0.025 (5)	0.022 (6)	−0.001 (4)	0.005 (4)	0.005 (4)
CM4	0.024 (5)	0.019 (4)	0.026 (7)	−0.001 (4)	0.010 (4)	−0.004 (4)
C21	0.022 (5)	0.023 (5)	0.025 (7)	−0.006 (4)	0.011 (4)	−0.005 (4)
C22	0.026 (6)	0.029 (5)	0.024 (7)	−0.007 (4)	0.005 (5)	−0.004 (4)
C23	0.021 (5)	0.042 (6)	0.033 (8)	−0.016 (5)	0.006 (5)	−0.007 (5)
C24	0.042 (7)	0.029 (6)	0.024 (7)	−0.013 (5)	0.006 (5)	0.002 (5)
C25	0.049 (8)	0.024 (5)	0.027 (8)	−0.014 (5)	0.015 (6)	0.001 (4)
C26	0.029 (5)	0.018 (4)	0.016 (6)	−0.003 (4)	−0.006 (4)	−0.002 (4)
C31	0.023 (5)	0.017 (4)	0.023 (6)	−0.005 (4)	−0.001 (4)	−0.005 (4)
C32	0.034 (6)	0.013 (4)	0.030 (7)	0.000 (4)	0.003 (5)	0.006 (4)
C33	0.026 (5)	0.019 (4)	0.033 (7)	0.002 (4)	0.004 (5)	0.003 (4)
C34	0.017 (5)	0.020 (5)	0.046 (8)	0.001 (4)	0.003 (5)	−0.006 (5)
C35	0.022 (5)	0.024 (5)	0.041 (8)	0.006 (4)	0.010 (5)	−0.009 (5)
C36	0.025 (5)	0.020 (4)	0.027 (7)	0.006 (4)	0.007 (4)	0.004 (4)
C41	0.022 (5)	0.020 (5)	0.032 (7)	0.004 (4)	0.004 (5)	0.006 (4)
C42	0.034 (6)	0.023 (5)	0.030 (7)	0.001 (4)	0.009 (5)	0.004 (4)
C43	0.025 (6)	0.038 (6)	0.032 (8)	−0.001 (5)	0.004 (5)	0.005 (5)
C44	0.029 (6)	0.023 (5)	0.036 (8)	−0.007 (4)	−0.011 (5)	0.013 (5)
C45	0.042 (7)	0.019 (5)	0.049 (9)	−0.012 (5)	0.005 (6)	−0.001 (5)
C46	0.025 (5)	0.018 (5)	0.047 (8)	−0.003 (4)	0.007 (5)	−0.002 (5)
Cl1	0.0233 (12)	0.0263 (11)	0.0214 (16)	0.0024 (9)	0.0024 (10)	−0.0023 (9)
O11	0.034 (4)	0.022 (4)	0.015 (4)	0.001 (3)	0.000 (3)	−0.002 (3)
O12	0.038 (5)	0.040 (5)	0.046 (7)	−0.005 (4)	0.014 (5)	0.014 (4)
O13	0.064 (7)	0.038 (5)	0.030 (6)	−0.007 (5)	−0.008 (5)	−0.012 (4)
O14	0.031 (5)	0.069 (7)	0.039 (7)	0.027 (5)	0.003 (4)	−0.006 (5)
Cl2	0.0264 (12)	0.0276 (12)	0.0252 (16)	−0.0027 (10)	0.0049 (11)	−0.0046 (10)
O21	0.049 (6)	0.033 (4)	0.027 (6)	−0.001 (4)	0.009 (4)	−0.001 (4)
O22	0.027 (5)	0.092 (9)	0.045 (8)	0.010 (5)	−0.003 (5)	−0.003 (6)
O23	0.038 (6)	0.067 (7)	0.046 (7)	−0.016 (5)	0.011 (5)	0.006 (5)
O24	0.111 (12)	0.032 (5)	0.075 (10)	0.011 (6)	0.039 (9)	−0.009 (6)
Cl21	0.055 (3)	0.124 (5)	0.046 (3)	−0.012 (3)	−0.002 (2)	0.004 (3)
Cl22	0.067 (3)	0.131 (5)	0.047 (3)	0.025 (3)	0.006 (2)	−0.015 (3)
C20	0.078 (17)	0.21 (3)	0.034 (15)	−0.017 (19)	−0.016 (11)	0.014 (17)
Cl31	0.0267 (14)	0.0446 (16)	0.0337 (19)	−0.0082 (12)	0.0071 (12)	−0.0090 (13)
Cl32	0.059 (2)	0.0410 (18)	0.068 (3)	−0.0209 (16)	0.024 (2)	−0.0156 (18)
C30	0.030 (6)	0.034 (6)	0.028 (7)	−0.005 (5)	0.009 (5)	−0.006 (5)
Cl41	0.036 (2)	0.105 (4)	0.044 (3)	0.005 (2)	−0.0038 (17)	−0.008 (2)
Cl42	0.070 (3)	0.087 (3)	0.049 (3)	−0.023 (3)	0.002 (2)	−0.008 (2)
C40	0.047 (9)	0.054 (9)	0.065 (13)	0.004 (7)	−0.009 (8)	0.012 (8)

Geometric parameters (Å, º) top

Br1—CB1	1.872 (11)	CM4—C41	1.475 (14)
Br2—CB2	1.851 (11)	C21—C22	1.395 (16)
Br3—CB5	1.874 (9)	C21—C26	1.411 (16)
Br4—CB6	1.849 (11)	C22—C23	1.373 (16)
N1—CA2	1.383 (13)	C22—H22	0.9500
N1—CA1	1.383 (13)	C23—C24	1.38 (2)
N1—H1	0.8807	C23—H23	0.9500
N2—CA3	1.369 (12)	C24—C25	1.36 (2)
N2—CA4	1.372 (13)	C24—H24	0.9500
N2—H2	0.8799	C25—C26	1.393 (15)
N3—CA5	1.377 (13)	C25—H25	0.9500
N3—CA6	1.377 (12)	C26—H26	0.9500
N3—H3	0.8800	C31—C36	1.386 (16)
N4—CA8	1.365 (12)	C31—C32	1.404 (16)
N4—CA7	1.382 (13)	C32—C33	1.389 (15)
N4—H4	0.8810	C32—H32	0.9500
CA1—CM4	1.371 (15)	C33—C34	1.387 (18)
CA1—CB1	1.422 (16)	C33—H33	0.9500
CA2—CM1	1.411 (15)	C34—C35	1.378 (19)
CA2—CB2	1.421 (15)	C34—H34	0.9500
CA3—CB3	1.405 (15)	C35—C36	1.410 (14)
CA3—CM1	1.420 (14)	C35—H35	0.9500
CA4—CM2	1.403 (14)	C36—H36	0.9500
CA4—CB4	1.432 (14)	C41—C42	1.382 (17)
CA5—CM2	1.413 (14)	C41—C46	1.415 (16)
CA5—CB5	1.419 (13)	C42—C43	1.382 (17)
CA6—CM3	1.403 (14)	C42—H42	0.9500
CA6—CB6	1.435 (15)	C43—C44	1.392 (19)
CA7—CM3	1.409 (14)	C43—H43	0.9500
CA7—CB7	1.414 (14)	C44—C45	1.39 (2)
CA8—CM4	1.414 (14)	C44—H44	0.9500
CA8—CB8	1.453 (15)	C45—C46	1.404 (15)
CB1—CB2	1.374 (15)	C45—H45	0.9500
C11—C12	1.397 (15)	C46—H46	0.9500
C11—C16	1.413 (18)	Cl1—O14	1.420 (9)
C11—CM1	1.460 (15)	Cl1—O12	1.425 (9)
CB3—CB4	1.382 (13)	Cl1—O13	1.429 (10)
CB3—HB3	0.9500	Cl1—O11	1.461 (9)
C12—C13	1.413 (17)	Cl2—O22	1.411 (12)
C12—H12	0.9500	Cl2—O23	1.428 (10)
CB4—HB4	0.9500	Cl2—O24	1.439 (11)
C13—C14	1.37 (2)	Cl2—O21	1.453 (10)
C13—H13	0.9500	Cl21—C20	1.74 (3)
CB5—CB6	1.363 (14)	Cl22—C20	1.71 (3)
C14—C15	1.37 (2)	C20—H20A	0.9900
C14—H14	0.9500	C20—H20B	0.9900
C15—C16	1.390 (18)	Cl31—C30	1.776 (12)
C15—H15	0.9500	Cl32—C30	1.749 (13)
CB7—CB8	1.361 (14)	C30—H30A	0.9900
CB7—HB7	0.9500	C30—H30B	0.9900
C16—H16	0.9500	Cl41—C40	1.72 (2)
CB8—HB8	0.9500	Cl42—C40	1.75 (2)
CM2—C21	1.485 (14)	C40—H40A	0.9900
CM3—C31	1.493 (15)	C40—H40B	0.9900

CA2—N1—CA1	110.1 (9)	CA1—CM4—CA8	124.0 (9)
CA2—N1—H1	124.6	CA1—CM4—C41	118.6 (9)
CA1—N1—H1	125.2	CA8—CM4—C41	117.4 (9)
CA3—N2—CA4	109.8 (8)	C22—C21—C26	119.0 (10)
CA3—N2—H2	125.0	C22—C21—CM2	123.1 (11)
CA4—N2—H2	125.1	C26—C21—CM2	117.9 (10)
CA5—N3—CA6	110.4 (8)	C23—C22—C21	121.6 (12)
CA5—N3—H3	124.7	C23—C22—H22	119.2
CA6—N3—H3	124.9	C21—C22—H22	119.2
CA8—N4—CA7	109.5 (9)	C22—C23—C24	119.0 (12)
CA8—N4—H4	125.2	C22—C23—H23	120.5
CA7—N4—H4	125.3	C24—C23—H23	120.5
CM4—CA1—N1	124.5 (10)	C25—C24—C23	120.8 (11)
CM4—CA1—CB1	129.9 (10)	C25—C24—H24	119.6
N1—CA1—CB1	105.5 (9)	C23—C24—H24	119.6
N1—CA2—CM1	123.6 (10)	C24—C25—C26	121.7 (13)
N1—CA2—CB2	107.7 (9)	C24—C25—H25	119.2
CM1—CA2—CB2	128.7 (10)	C26—C25—H25	119.2
N2—CA3—CB3	107.5 (8)	C25—C26—C21	117.9 (11)
N2—CA3—CM1	126.1 (9)	C25—C26—H26	121.0
CB3—CA3—CM1	126.3 (9)	C21—C26—H26	121.0
N2—CA4—CM2	125.7 (9)	C36—C31—C32	121.0 (10)
N2—CA4—CB4	107.1 (8)	C36—C31—CM3	119.7 (10)
CM2—CA4—CB4	127.2 (9)	C32—C31—CM3	119.2 (10)
N3—CA5—CM2	123.9 (9)	C33—C32—C31	119.5 (11)
N3—CA5—CB5	106.2 (8)	C33—C32—H32	120.2
CM2—CA5—CB5	129.9 (10)	C31—C32—H32	120.2
N3—CA6—CM3	123.6 (9)	C34—C33—C32	119.6 (11)
N3—CA6—CB6	106.6 (8)	C34—C33—H33	120.2
CM3—CA6—CB6	129.7 (9)	C32—C33—H33	120.2
N4—CA7—CM3	125.0 (10)	C35—C34—C33	121.2 (10)
N4—CA7—CB7	107.9 (8)	C35—C34—H34	119.4
CM3—CA7—CB7	127.1 (10)	C33—C34—H34	119.4
N4—CA8—CM4	127.4 (10)	C34—C35—C36	120.0 (11)
N4—CA8—CB8	106.7 (9)	C34—C35—H35	120.0
CM4—CA8—CB8	125.8 (9)	C36—C35—H35	120.0
CB2—CB1—CA1	110.1 (9)	C31—C36—C35	118.7 (11)
CB2—CB1—Br1	123.5 (9)	C31—C36—H36	120.6
CA1—CB1—Br1	125.4 (8)	C35—C36—H36	120.6
CB1—CB2—CA2	106.6 (9)	C42—C41—C46	119.7 (10)
CB1—CB2—Br2	123.9 (8)	C42—C41—CM4	123.2 (10)
CA2—CB2—Br2	128.8 (7)	C46—C41—CM4	117.1 (10)
C12—C11—C16	117.7 (11)	C41—C42—C43	120.7 (12)
C12—C11—CM1	121.0 (11)	C41—C42—H42	119.7
C16—C11—CM1	121.1 (10)	C43—C42—H42	119.7
CB4—CB3—CA3	108.5 (8)	C42—C43—C44	120.8 (12)
CB4—CB3—HB3	125.7	C42—C43—H43	119.6
CA3—CB3—HB3	125.7	C44—C43—H43	119.6
C11—C12—C13	121.2 (12)	C45—C44—C43	119.1 (11)
C11—C12—H12	119.4	C45—C44—H44	120.5
C13—C12—H12	119.4	C43—C44—H44	120.5
CB3—CB4—CA4	106.8 (9)	C44—C45—C46	120.9 (12)
CB3—CB4—HB4	126.6	C44—C45—H45	119.5
CA4—CB4—HB4	126.6	C46—C45—H45	119.5
C14—C13—C12	119.3 (12)	C45—C46—C41	118.8 (12)
C14—C13—H13	120.4	C45—C46—H46	120.6
C12—C13—H13	120.4	C41—C46—H46	120.6
CB6—CB5—CA5	109.4 (9)	O14—Cl1—O12	111.4 (7)
CB6—CB5—Br3	123.0 (8)	O14—Cl1—O13	111.6 (7)
CA5—CB5—Br3	127.1 (7)	O12—Cl1—O13	109.7 (7)
C15—C14—C13	120.6 (13)	O14—Cl1—O11	107.3 (6)
C15—C14—H14	119.7	O12—Cl1—O11	107.4 (6)
C13—C14—H14	119.7	O13—Cl1—O11	109.3 (5)
CB5—CB6—CA6	107.3 (9)	O22—Cl2—O23	110.4 (8)
CB5—CB6—Br4	126.0 (8)	O22—Cl2—O24	111.7 (9)
CA6—CB6—Br4	126.4 (8)	O23—Cl2—O24	108.3 (8)
C14—C15—C16	120.9 (14)	O22—Cl2—O21	110.2 (7)
C14—C15—H15	119.5	O23—Cl2—O21	109.3 (7)
C16—C15—H15	119.5	O24—Cl2—O21	106.7 (7)
CB8—CB7—CA7	108.1 (9)	Cl22—C20—Cl21	112.8 (16)
CB8—CB7—HB7	126.0	Cl22—C20—H20A	109.0
CA7—CB7—HB7	126.0	Cl21—C20—H20A	109.0
C15—C16—C11	120.3 (12)	Cl22—C20—H20B	109.0
C15—C16—H16	119.8	Cl21—C20—H20B	109.0
C11—C16—H16	119.8	H20A—C20—H20B	107.8
CB7—CB8—CA8	107.8 (9)	Cl32—C30—Cl31	110.6 (7)
CB7—CB8—HB8	126.1	Cl32—C30—H30A	109.5
CA8—CB8—HB8	126.1	Cl31—C30—H30A	109.5
CA2—CM1—CA3	123.1 (9)	Cl32—C30—H30B	109.5
CA2—CM1—C11	120.7 (9)	Cl31—C30—H30B	109.5
CA3—CM1—C11	116.2 (9)	H30A—C30—H30B	108.1
CA4—CM2—CA5	123.1 (9)	Cl41—C40—Cl42	113.2 (10)
CA4—CM2—C21	117.4 (9)	Cl41—C40—H40A	108.9
CA5—CM2—C21	119.5 (9)	Cl42—C40—H40A	108.9
CA6—CM3—CA7	124.8 (10)	Cl41—C40—H40B	108.9
CA6—CM3—C31	120.8 (9)	Cl42—C40—H40B	108.9
CA7—CM3—C31	114.4 (9)	H40A—C40—H40B	107.7

CA2—N1—CA1—CM4	177.8 (11)	CB3—CA3—CM1—C11	−19.5 (17)
CA2—N1—CA1—CB1	−1.8 (13)	C12—C11—CM1—CA2	−48.1 (18)
CA1—N1—CA2—CM1	−175.3 (11)	C16—C11—CM1—CA2	127.4 (14)
CA1—N1—CA2—CB2	2.5 (13)	C12—C11—CM1—CA3	131.2 (13)
CA4—N2—CA3—CB3	2.7 (13)	C16—C11—CM1—CA3	−53.3 (17)
CA4—N2—CA3—CM1	−174.8 (11)	N2—CA4—CM2—CA5	19.9 (18)
CA3—N2—CA4—CM2	173.8 (11)	CB4—CA4—CM2—CA5	−162.0 (12)
CA3—N2—CA4—CB4	−4.6 (13)	N2—CA4—CM2—C21	−162.9 (11)
CA6—N3—CA5—CM2	174.2 (10)	CB4—CA4—CM2—C21	15.1 (17)
CA6—N3—CA5—CB5	−3.0 (12)	N3—CA5—CM2—CA4	29.0 (17)
CA5—N3—CA6—CM3	−177.8 (10)	CB5—CA5—CM2—CA4	−154.4 (12)
CA5—N3—CA6—CB6	2.1 (12)	N3—CA5—CM2—C21	−148.1 (11)
CA8—N4—CA7—CM3	−179.1 (11)	CB5—CA5—CM2—C21	28.5 (18)
CA8—N4—CA7—CB7	0.5 (14)	N3—CA6—CM3—CA7	−27.5 (18)
CA7—N4—CA8—CM4	179.4 (12)	CB6—CA6—CM3—CA7	152.6 (13)
CA7—N4—CA8—CB8	−1.1 (14)	N3—CA6—CM3—C31	151.6 (11)
CM4—CA1—CB1—CB2	−179.2 (12)	CB6—CA6—CM3—C31	−28.2 (19)
N1—CA1—CB1—CB2	0.4 (13)	N4—CA7—CM3—CA6	−18 (2)
CM4—CA1—CB1—Br1	12.1 (19)	CB7—CA7—CM3—CA6	162.1 (12)
N1—CA1—CB1—Br1	−168.4 (8)	N4—CA7—CM3—C31	162.4 (11)
CA1—CB1—CB2—CA2	1.1 (14)	CB7—CA7—CM3—C31	−17.1 (18)
Br1—CB1—CB2—CA2	170.1 (9)	N1—CA1—CM4—CA8	28.0 (19)
CA1—CB1—CB2—Br2	−170.3 (9)	CB1—CA1—CM4—CA8	−152.5 (13)
Br1—CB1—CB2—Br2	−1.3 (15)	N1—CA1—CM4—C41	−149.8 (11)
N1—CA2—CB2—CB1	−2.2 (13)	CB1—CA1—CM4—C41	29.6 (19)
CM1—CA2—CB2—CB1	175.5 (12)	N4—CA8—CM4—CA1	17 (2)
N1—CA2—CB2—Br2	168.6 (9)	CB8—CA8—CM4—CA1	−162.9 (13)
CM1—CA2—CB2—Br2	−13.7 (19)	N4—CA8—CM4—C41	−165.5 (12)
N2—CA3—CB3—CB4	0.4 (13)	CB8—CA8—CM4—C41	15.0 (19)
CM1—CA3—CB3—CB4	177.9 (11)	CA4—CM2—C21—C22	42.4 (16)
C16—C11—C12—C13	1 (2)	CA5—CM2—C21—C22	−140.3 (12)
CM1—C11—C12—C13	177.1 (13)	CA4—CM2—C21—C26	−136.4 (11)
CA3—CB3—CB4—CA4	−3.2 (13)	CA5—CM2—C21—C26	40.9 (16)
N2—CA4—CB4—CB3	4.8 (12)	C26—C21—C22—C23	1.4 (18)
CM2—CA4—CB4—CB3	−173.6 (11)	CM2—C21—C22—C23	−177.4 (11)
C11—C12—C13—C14	−1 (2)	C21—C22—C23—C24	−1.7 (19)
N3—CA5—CB5—CB6	2.8 (12)	C22—C23—C24—C25	1 (2)
CM2—CA5—CB5—CB6	−174.2 (11)	C23—C24—C25—C26	−1 (2)
N3—CA5—CB5—Br3	−168.8 (8)	C24—C25—C26—C21	0.3 (19)
CM2—CA5—CB5—Br3	14.2 (18)	C22—C21—C26—C25	−0.7 (17)
C12—C13—C14—C15	0 (3)	CM2—C21—C26—C25	178.2 (11)
CA5—CB5—CB6—CA6	−1.6 (13)	CA6—CM3—C31—C36	127.8 (12)
Br3—CB5—CB6—CA6	170.4 (8)	CA7—CM3—C31—C36	−53.0 (15)
CA5—CB5—CB6—Br4	−176.5 (8)	CA6—CM3—C31—C32	−57.4 (16)
Br3—CB5—CB6—Br4	−4.4 (14)	CA7—CM3—C31—C32	121.8 (12)
N3—CA6—CB6—CB5	−0.3 (12)	C36—C31—C32—C33	0.8 (17)
CM3—CA6—CB6—CB5	179.6 (11)	CM3—C31—C32—C33	−173.9 (10)
N3—CA6—CB6—Br4	174.6 (8)	C31—C32—C33—C34	−1.1 (17)
CM3—CA6—CB6—Br4	−5.5 (18)	C32—C33—C34—C35	−0.3 (17)
C13—C14—C15—C16	0 (3)	C33—C34—C35—C36	2.0 (18)
N4—CA7—CB7—CB8	0.3 (14)	C32—C31—C36—C35	0.8 (17)
CM3—CA7—CB7—CB8	179.9 (12)	CM3—C31—C36—C35	175.5 (10)
C14—C15—C16—C11	1 (2)	C34—C35—C36—C31	−2.2 (17)
C12—C11—C16—C15	−1 (2)	CA1—CM4—C41—C42	−128.5 (13)
CM1—C11—C16—C15	−177.1 (13)	CA8—CM4—C41—C42	53.5 (18)
CA7—CB7—CB8—CA8	−1.0 (14)	CA1—CM4—C41—C46	51.5 (17)
N4—CA8—CB8—CB7	1.3 (14)	CA8—CM4—C41—C46	−126.5 (12)
CM4—CA8—CB8—CB7	−179.2 (11)	C46—C41—C42—C43	1 (2)
N1—CA2—CM1—CA3	−23.0 (18)	CM4—C41—C42—C43	−179.4 (12)
CB2—CA2—CM1—CA3	159.7 (12)	C41—C42—C43—C44	−2 (2)
N1—CA2—CM1—C11	156.2 (11)	C42—C43—C44—C45	3 (2)
CB2—CA2—CM1—C11	−21.1 (19)	C43—C44—C45—C46	−2 (2)
N2—CA3—CM1—CA2	−23.3 (19)	C44—C45—C46—C41	0 (2)
CB3—CA3—CM1—CA2	159.7 (11)	C42—C41—C46—C45	0.5 (19)
N2—CA3—CM1—C11	157.5 (11)	CM4—C41—C46—C45	−179.5 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N2	0.88	2.57	3.018 (12)	113
N1—H1···O21	0.88	2.12	2.956 (14)	158
N2—H2···N1	0.88	2.60	3.018 (12)	110
N2—H2···N3	0.88	2.59	3.026 (12)	111
N2—H2···O11	0.88	2.07	2.896 (12)	157
N3—H3···O21	0.88	2.08	2.932 (13)	162
N4—H4···N3	0.88	2.62	3.034 (12)	110
N4—H4···O11	0.88	2.01	2.844 (13)	159

Pyrrole periplanar angles (°) top

Angles with respect to the mean four atom meta-carbon plane. A `negative' angle represents an arbitrary orientation with the pyrrole N atom below the mean porphyrin plane.

Pyrrole Ring	(I)	(II)
N1—CA1—CB1—CB2—CA2	3.0 (3)	31.0 (5)
N2—CA3—CB3—CB4—CA4	6.5 (3)	-30.1 (5)
N3—CA5—CB5—CB6—CA6		33.6 (4)
N4—CA7—CB7—CB8—CA8		-23.2 (3)

Deviations from pyrrole planes for (I) and (II) (Å) top

Atom	(I)	(II)
N1	-0.008 (3)	-0.012 (7)
CA1	-0.004 (3)	0.006 (7)
CA2	0.015 (3)	0.013 (7)
CB1	0.014 (3)	0.002 (7)
CB2	-0.018 (3)	-0.009 (7)
Br1	-0.117 (8)	-0.28 (2)
Br2	0.403 (7)	-0.28 (2)

N2	0.006 (3)	0.021 (7)
CA3	-0.001 (3)	-0.006 (7)
CA4	-0.009 (3)	-0.027 (7)
CB3	-0.005 (3)	-0.011 (7)
CB4	0.008 (3)	0.023 (7)

N3		-0.015 (6)
CA5		0.017 (6)
CA6		0.007 (7)
CB5		-0.013 (7)
CB6		0.004 (7)
Br3		-0.283 (18)
Br4		-0.114 (19)

N4		0.005 (8)
CA7		0.000 (7)
CA8		-0.007 (8)
CB7		-0.004 (8)
CB8		0.006 (8)

Deviations of peripheral atoms from mean meta-carbon plane for (I) and (II) (Å) top

Atom	(I)	(II)
C11	-0.240 (7)	-0.038 (19)
C21	0.205 (8)	0.194 (18)
C31		0.061 (18)
C41		0.232 (19)

References

Callot, H. J. (1973). Tetrahedron Lett. 14, 4987–4990. CrossRef Google Scholar
Cheng, B., Munro, O. Q., Marques, H. M. & Scheidt, W. R. (1997). J. Am. Chem. Soc. 119, 10732–10742. CSD CrossRef CAS Web of Science Google Scholar
Crossley, M. J., Burn, P. L., Chew, S. S., Cuttance, F. B. & Newsom, I. A. (1991). J. Chem. Soc. Chem. Commun. pp. 1564–1566. CrossRef Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CSD CrossRef IUCr Journals Google Scholar
Karunanithi, K. & Bhyrappa, P. (2015). Inorg. Chim. Acta, 427, 41–51. CSD CrossRef CAS Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Pflugrath, J. W. & Messerschmidt, A. (1989). MADNES. Delft Instruments, The Netherlands. Google Scholar
Rayati, S., Zakavi, S., Motlagh, S. H., Noroozi, V., Razmjoo, M., Wojtczak, A. & Kozakiewicz, A. (2008). Polyhedron, pp. 2285–2290. CSD CrossRef Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Walker, N. & Stuart, D. (1983). Acta Cryst. A39, 158–166. CrossRef CAS Web of Science IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zou, J.-Z., Xu, Z., Li, M., You, X.-Z. & Wang, H.-Q. (1995). Acta Cryst. C51, 760–761. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.