Structural investigation of 5,10-A₂B₂-type porphyrins: palladium(II) and zinc(II) complexes of 5,10-di­bromo-15,20-bis­(4-methyl­phen­yl)porphyrin

The analysis of [5,10-di­bromo-15,20-bis­(4-methyl­phen­yl)por­phyrinato]palladium(II), [Pd(C₃₄H₂₂Br₂N₄)], and [5,10-di­bromo-15,20-bis­(4-methyl­phen­yl)porphyrinato](methan­ol)zinc(II), [Zn(C₃₄H₂₂Br₂N₄)(CH₄O)], reveals a small but localized influence of the bromine residues on the conformation of the macrocycle. A comparison of the 5,10-di­bromo substituent pattern with literature data for 5,15-di­bromo­porphyrins shows similar in-plane distortions in both but a different mix of out-of-plane distortion modes for the different regiochemical arrangements.

S1. Introduction

The structural chemistry of porphyrins is one of best investigated areas of coordination chemistry. Many studies are available on metal coordination (Scheidt, 2008), aspects of macrocycle modification (Chmielewski & Latos-Grazynski, 2005), supra­molecular chemistry (Beletskaya et al., 2009) and nonplanar systems (Senge, 2006). The latter have been the focus of conformational analyses which highlighted the flexible character of the porphyrins macrocycle, especially in the case of highly substituted systems, i.e. porphyrins with large or sterically hindered substituents. For the simple symmetric meso-5,10,15,20-tetra­substituted porphyrins (A₄-type), several thousand crystal structures are available (Senge, 2000). Yet much less is known about the structural chemistry of porphyrins with few meso substituents or the impact of different regiochemical arrangements thereof. In part, this has been hampered by the only recently overcome synthetic inaccessibility of components of the A_x- and ABCD-type porphyrins, (I) (where ABCD refers to meso substituents) (Senge, 2011).

For example, the structural impact of a 5,10- versus a 5,15-disubstitution pattern has not been investigated in detail. This has now become possible with the advent of general syntheses for 5,10-disubstituted porphyrins (Ryppa et al., 2005). These have been used to develop 5,10-A₂-10,20-B₂-type porphyrins, (II) (see Scheme), for optical applications due to the altered orientation of the intra­molecular dipole moment compared to the well-known 5,15-A₂-10,20-B₂ systems, (III) (Senge et al., 2011; Zawadzka et al., 2013a). Here, we use 5,10-di­bromo-15,20-bis­(4-methyl­phenyl)­porphyrin, (IV), and its palladium(II), (V), and zinc(II), (VI), complexes for a comparative analysis of their structural properties.

S2. Experimental

S2.1. Synthesis and crystallization

Compounds (V) and (VI) were prepared via metallation of the respective free base (III) (Senge et al., 2011), as described previously (Zawadzka et al., 2013b). Crystals were grown by liquid diffusion of methanol into a solution of the porphyrins in methyl­ene chloride using crystallization tubes (5 × 200 mm). Crystals formed within two weeks at room temperature and were handled as outlined by Hope (1994).

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms, except for the methanol -OH hydrogen in (VI), were located in a difference map and then treated as riding in geometrically idealized positions, with C—H = 0.95 (aromatic) or 0.98 Å (methyl), and with U_iso(H) = kU_eq(C), where k = 1.5 for the methyl groups and 1.2 for all other H atoms. For palladium(II) complex (V), the residual electron density was located close to the metal centre. In the refinement of (VI), no H atom was included for the –OH group of the axial methanol molecule. The methyl group exhibited high librational movement.

S3. Results and discussion

Views of the molecular structures of the palladium(II) porphyrinate complex (V) and the zinc(II) porphyrinate complex (VI) are shown in Figs. 1 and 2, respectively. The structure of the free base (IV) was reported previously (Senge et al., 2011). Both compounds crystallized in the triclinic space group P1 with one molecule in the asymmetric unit. The palladium complex is characterized by a typical four-coordinate Pd centre with an average Pd—N bond length of 2.009 (3) Å. The Pd1—N21 bond [2.001 (6) Å] is slightly shorter than the other three [average 2.012 (6) Å]. A similar situation is encountered in the zinc(II) complex. Compound (VI) crystallized as the methanol adduct, which a methanol molecule coordinated as the axial ligand to the Zn^II ion [Zn1—O1A = 2.207 (3) Å], which is penta­coordinated. Here the Zn1—N24 bond length is 2.033 (3) Å, compared to an average value of 2.059 (3) Å for the other three Zn—N bonds. Note, that Zn1—N22 is also somewhat shorter than Zn1—N23 and Zn1—N24.

Further evidence for structural differences between the meso-bromo quadrants and the meso-tolyl quadrants can be derived from an inspection of the relevant C_a—C_m—C_a angles (Table 2). In both, the metal complexes and the free base the C_a—C_m(Br)—C_a angles are larger than the C_a—C_m(tolyl)—C_a ones. This is most pronounced in the case of the palladium(II) complex where the respective average values are 128.1 (7) versus 123.3 (7)°. Thus, the presence of the bromo residues results in a partial flattening of this bond, which is in agreement with a localized conformational effect of the Br atoms (Senge, 2000).

Packing forces can only partially account for these differences. Both the palladium(II) complex (Fig. 3) and the zinc(II) complex (Fig. 4) form layers of porphyrins molecules with only minimal π-overlap. For example, in (V), the inter­planar separation of the two N₄ planes of the porphyrin rings is 3.87 (1) Å and the closest inter­molecular contact observed was a Pd···Br inter­action [3.734 (6) Å]. In addition, atoms H15C and Br2ⁱ form a close contact [C15E···Br2ⁱ = 3.759 (6) Å and C15E—H15C···Br2ⁱ = 149°; symmetry code: (i) x-1, y-1, z]. In the case of compound (VI), the closest intra­molecular contacts observed were Zn1···Br1 [3.578 (4) Å] and Br1···H20D [3.053 (4) Å].

In order to investigate the conformation in more detail, the compounds were analysed using the normal-structural-decomposition (NSD) method (Jentzen et al., 1997). This method allows an identification of the major out-of-plane and in-plane distortion modes and their individual contributions. An overall measure of the degree of conformational distortion, if any, is obtained by the determination of the average of in-plane distortion (Dip) and of out-of-plane distortion (Doop). As listed in Table 2, all three compounds are nonplanar, i.e. have significant Doop values, and the free base and zinc(II) complex have measurable in-plane distortions. Fig. 5 shows a graphical representation of the individual contributions of the main distortion modes. The pattern and degree of out-of-plane distortion is very similar in all three compounds. They all have B_2u, B_1u and A_2u contributions, which in descriptive terms mean saddling, ruffling and doming contributions. The latter is atypical for (IV) and (V), as it is mostly observed in porphyrins with penta­coordinated metal centres. Only one in-plane distortion mode (A_1g) contributes significantly in the free base and zinc(II) complex. This one is related to the macrocycle breathing.

In order to investigate the influence of the regiochemistry, i.e. the 5,10-di­bromo substituent pattern on the conformation, we tried to identify suitable compounds for comparison. Only three other crystal structures with meso-bromo residues were found. One, namely (5-bromo-10,20-di­phenyl­porphyrinato)nickel(II) (Arnold et al., 1997), was omitted due to the nickel-induced ruffling and the absence of a comparative structure in our analysis here. Two more related structures are the free bases (VII) and (VIII) (see Scheme). Both are 5,15-di­bromo-substituted porphyrins with a hexyl and tri­meth­oxy­phenyl residue (Senge et al., 2010). Their NSD analysis (Fig. 5) indicates a similar overall degree of in-plane distortion (Dip ~0.21 Å for both) and different degrees of out-of-plane distortion [Doop = 0.353 and 0.893 Å for (VII) and (VIII), respectively]. In terms of the contributions of individual distortion modes, both are characterized by an A_1g contribution for the in-plane distortion, similar to the compounds reported here. More differences between the 5,10- and 5,15-di­bromo substituent pattern are observed in the out-of-plane distortion modes. The doming contribution is almost absent in the latter, the degree of ruffling is significantly reduced, while minor contributions of wave distortions (E_g) are present. Thus, differences in the `mix' of distortion modes are associated with the two substituent patterns.

Related literature

For related literature, see: Arnold et al. (1997); Beletskaya et al. (2009); Chmielewski & Latos-Grazynski (2005); Hope (1994); Jentzen et al. (1997); Ryppa et al. (2005); Scheidt (2008); Senge (2000, 2006, 2011); Senge et al. (2010); Senge, Ryppa, Fazekas, Zawadzka & Dahms (2011); Zawadzka et al. (2013a, 2013b).

Computing details

Data collection: APEX2 (Bruker, 2005) for (V); CrystalClear (Rigaku/MSC, 2005) for (VI). Cell refinement: SAINT (Bruker, 2005) for (V); CrystalClear (Rigaku/MSC, 2005) for (VI). Data reduction: SAINT (Bruker, 2005) for (V); CrystalClear (Rigaku/MSC, 2005) for (VI). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008). Molecular graphics: SHELXTL (Sheldrick, 2008) for (V); SHELXL97 (Sheldrick, 2008) for (VI). For both compounds, software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. View of the molecular structure of (V) in the crystal. H atoms have been omitted for clarity and displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. View of the molecular structure of (VI) in the crystal. H atoms have been omitted for clarity and displacement ellipsoids are drawn at the 50% probability level.
	Fig. 3. View of the molecular packing of (V) in the crystal. H atoms have been omitted for clarity.
	Fig. 4. View of the molecular packing of (VI) in the crystal. H atoms have been omitted for clarity.
	Fig. 5. Graphical representation of the displacements along the lowest-frequency coordinates that best simulate the free base (IV), palladium(II) complex(V) and zinc(II) complex (VI), and a comparison with structures (VII) and (VIII) (see Scheme) (normal structural decomposition analysis).

(V) [5,10-Dibromo-15,20-bis(4-methylphenyl)porphyrinato]palladium(II)

Crystal data

[Pd(C34H22Br2N4)]	Z = 2
Mr = 752.78	F(000) = 740
Triclinic, P1	Dx = 1.817 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.396 (4) Å	Cell parameters from 871 reflections
b = 10.558 (5) Å	θ = 2.4–28.4°
c = 15.129 (7) Å	µ = 3.61 mm^−1
α = 95.157 (8)°	T = 123 K
β = 103.433 (8)°	Plate, red
γ = 107.007 (8)°	0.35 × 0.25 × 0.07 mm
V = 1375.7 (10) Å^3

Data collection

Bruker APEXII CCD diffractometer	4833 independent reflections
Radiation source: sealed tube	3628 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.041
ϕ and ω scans	θmax = 25.0°, θmin = 1.4°
Absorption correction: empirical (using intensity measurements) (SADABS; Bruker, 2005)	h = −11→11
Tmin = 0.365, Tmax = 0.786	k = −12→12
10757 measured reflections	l = −17→17

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.180	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.1228P)^2] where P = (Fo^2 + 2Fc^2)/3
4833 reflections	(Δ/σ)max = 0.017
372 parameters	Δρmax = 2.50 e Å^−3
0 restraints	Δρmin = −1.36 e Å^−3

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. Residual electron density is located close to the metal center.

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

	x	y	z	Uiso*/Ueq
Pd1	0.23463 (6)	0.46454 (5)	0.10846 (4)	0.0289 (2)
N21	0.1743 (7)	0.4455 (5)	−0.0291 (4)	0.0331 (14)
N22	0.4339 (7)	0.6082 (6)	0.1146 (4)	0.0376 (15)
N23	0.2916 (7)	0.4876 (6)	0.2469 (4)	0.0320 (13)
N24	0.0386 (6)	0.3170 (5)	0.1024 (4)	0.0274 (12)
C1	0.0497 (8)	0.3479 (7)	−0.0893 (5)	0.0336 (16)
C2	0.0461 (9)	0.3694 (8)	−0.1834 (5)	0.0422 (19)
H2A	−0.0277	0.3168	−0.2383	0.051*
C3	0.1668 (10)	0.4771 (8)	−0.1772 (6)	0.045 (2)
H3A	0.1932	0.5164	−0.2277	0.054*
C4	0.2498 (9)	0.5243 (8)	−0.0831 (5)	0.0390 (18)
C5	0.3897 (9)	0.6266 (7)	−0.0475 (6)	0.0402 (19)
C6	0.4781 (9)	0.6657 (7)	0.0433 (6)	0.0417 (19)
C7	0.6269 (9)	0.7643 (8)	0.0776 (7)	0.049 (2)
H7A	0.6827	0.8188	0.0422	0.058*
C8	0.6744 (9)	0.7669 (8)	0.1680 (7)	0.050 (2)
H8A	0.7695	0.8237	0.2087	0.060*
C9	0.5560 (9)	0.6690 (7)	0.1922 (6)	0.0422 (19)
C10	0.5530 (9)	0.6415 (7)	0.2804 (6)	0.0425 (19)
C11	0.4329 (8)	0.5669 (7)	0.3078 (5)	0.0375 (18)
C12	0.4259 (9)	0.5542 (8)	0.3996 (5)	0.045 (2)
H12A	0.5066	0.5980	0.4540	0.054*
C13	0.2864 (9)	0.4700 (8)	0.3965 (5)	0.0404 (18)
H13A	0.2503	0.4432	0.4478	0.048*
C14	0.2006 (8)	0.4273 (7)	0.2998 (5)	0.0337 (16)
C15	0.0563 (8)	0.3310 (7)	0.2691 (5)	0.0307 (16)
C16	−0.0167 (8)	0.2761 (6)	0.1751 (4)	0.0286 (15)
C17	−0.1583 (8)	0.1671 (7)	0.1422 (5)	0.0307 (15)
H17A	−0.2215	0.1230	0.1783	0.037*
C18	−0.1852 (8)	0.1383 (7)	0.0488 (5)	0.0319 (16)
H18A	−0.2685	0.0680	0.0076	0.038*
C19	−0.0633 (8)	0.2345 (6)	0.0251 (5)	0.0286 (15)
C20	−0.0576 (8)	0.2434 (6)	−0.0657 (5)	0.0298 (15)
Br1	0.47722 (11)	0.71886 (9)	−0.13457 (7)	0.0570 (3)
Br2	0.74249 (11)	0.72204 (11)	0.37495 (7)	0.0689 (4)
C15A	−0.0199 (8)	0.2728 (7)	0.3400 (4)	0.0326 (16)
C15B	−0.0669 (9)	0.3541 (8)	0.3960 (5)	0.0405 (18)
H15A	−0.0577	0.4436	0.3866	0.049*
C15C	−0.1275 (10)	0.3046 (9)	0.4659 (6)	0.053 (2)
H15B	−0.1596	0.3612	0.5038	0.063*
C15D	−0.1426 (10)	0.1755 (9)	0.4817 (5)	0.050 (2)
C15E	−0.0932 (11)	0.0992 (9)	0.4251 (6)	0.055 (2)
H15C	−0.1006	0.0100	0.4347	0.066*
C15F	−0.0330 (10)	0.1460 (8)	0.3548 (5)	0.045 (2)
H15D	−0.0010	0.0892	0.3169	0.054*
C15G	−0.2072 (13)	0.1235 (12)	0.5578 (7)	0.078 (3)
H15E	−0.2494	0.0252	0.5436	0.118*
H15F	−0.2897	0.1603	0.5637	0.118*
H15G	−0.1250	0.1510	0.6158	0.118*
C20A	−0.1696 (8)	0.1341 (7)	−0.1408 (4)	0.0300 (15)
C20B	−0.1484 (9)	0.0106 (7)	−0.1496 (5)	0.0379 (17)
H20A	−0.0638	−0.0031	−0.1079	0.046*
C20C	−0.2478 (9)	−0.0937 (8)	−0.2182 (5)	0.0403 (18)
H20B	−0.2309	−0.1782	−0.2223	0.048*
C20D	−0.3714 (9)	−0.0779 (7)	−0.2809 (5)	0.0368 (17)
C20E	−0.3929 (9)	0.0475 (8)	−0.2703 (6)	0.048 (2)
H20C	−0.4773	0.0620	−0.3118	0.058*
C20F	−0.2934 (9)	0.1513 (8)	−0.2004 (5)	0.045 (2)
H20D	−0.3116	0.2352	−0.1940	0.054*
C20G	−0.4733 (11)	−0.1885 (9)	−0.3571 (6)	0.058 (2)
H20E	−0.4357	−0.2658	−0.3546	0.087*
H20F	−0.4724	−0.1579	−0.4164	0.087*
H20G	−0.5790	−0.2147	−0.3509	0.087*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pd1	0.0314 (3)	0.0193 (3)	0.0410 (4)	0.0156 (2)	0.0084 (2)	0.0088 (2)
N21	0.042 (3)	0.024 (3)	0.044 (4)	0.021 (3)	0.016 (3)	0.016 (3)
N22	0.036 (3)	0.025 (3)	0.058 (4)	0.015 (3)	0.016 (3)	0.012 (3)
N23	0.035 (3)	0.027 (3)	0.033 (3)	0.015 (3)	0.002 (3)	0.003 (2)
N24	0.029 (3)	0.020 (3)	0.035 (3)	0.012 (2)	0.005 (2)	0.010 (2)
C1	0.045 (4)	0.042 (4)	0.027 (4)	0.028 (4)	0.014 (3)	0.013 (3)
C2	0.050 (5)	0.051 (5)	0.038 (4)	0.031 (4)	0.014 (4)	0.015 (4)
C3	0.066 (6)	0.043 (5)	0.046 (5)	0.034 (4)	0.027 (4)	0.026 (4)
C4	0.049 (5)	0.039 (4)	0.046 (5)	0.028 (4)	0.022 (4)	0.024 (3)
C5	0.047 (5)	0.035 (4)	0.063 (5)	0.027 (4)	0.034 (4)	0.036 (4)
C6	0.047 (5)	0.023 (4)	0.066 (5)	0.020 (3)	0.019 (4)	0.022 (3)
C7	0.036 (4)	0.035 (4)	0.078 (7)	0.012 (4)	0.019 (4)	0.019 (4)
C8	0.034 (4)	0.029 (4)	0.086 (7)	0.009 (3)	0.015 (4)	0.014 (4)
C9	0.034 (4)	0.026 (4)	0.068 (6)	0.015 (3)	0.011 (4)	0.006 (4)
C10	0.035 (4)	0.026 (4)	0.060 (5)	0.011 (3)	0.001 (4)	0.000 (3)
C11	0.035 (4)	0.020 (3)	0.053 (5)	0.013 (3)	0.000 (3)	0.001 (3)
C12	0.043 (5)	0.040 (4)	0.043 (5)	0.015 (4)	−0.005 (4)	−0.005 (3)
C13	0.042 (4)	0.038 (4)	0.041 (4)	0.022 (4)	0.002 (3)	−0.003 (3)
C14	0.041 (4)	0.024 (4)	0.037 (4)	0.020 (3)	0.002 (3)	0.001 (3)
C15	0.039 (4)	0.027 (4)	0.030 (4)	0.022 (3)	0.004 (3)	0.004 (3)
C16	0.037 (4)	0.027 (3)	0.029 (4)	0.024 (3)	0.004 (3)	0.006 (3)
C17	0.035 (4)	0.030 (4)	0.032 (4)	0.018 (3)	0.005 (3)	0.012 (3)
C18	0.031 (4)	0.026 (4)	0.040 (4)	0.015 (3)	0.003 (3)	0.009 (3)
C19	0.035 (4)	0.025 (3)	0.032 (4)	0.020 (3)	0.005 (3)	0.007 (3)
C20	0.033 (4)	0.026 (3)	0.038 (4)	0.021 (3)	0.007 (3)	0.009 (3)
Br1	0.0591 (6)	0.0552 (6)	0.0867 (7)	0.0359 (5)	0.0412 (5)	0.0468 (5)
Br2	0.0462 (6)	0.0632 (7)	0.0708 (7)	−0.0011 (5)	−0.0046 (5)	−0.0039 (5)
C15A	0.039 (4)	0.031 (4)	0.023 (3)	0.015 (3)	−0.002 (3)	−0.004 (3)
C15B	0.048 (5)	0.036 (4)	0.039 (4)	0.019 (4)	0.007 (4)	0.004 (3)
C15C	0.045 (5)	0.069 (6)	0.039 (5)	0.020 (4)	0.007 (4)	−0.009 (4)
C15D	0.051 (5)	0.057 (6)	0.033 (4)	0.011 (4)	0.003 (4)	0.012 (4)
C15E	0.074 (6)	0.043 (5)	0.042 (5)	0.016 (4)	0.007 (4)	0.010 (4)
C15F	0.067 (6)	0.044 (5)	0.033 (4)	0.028 (4)	0.013 (4)	0.008 (3)
C15G	0.070 (7)	0.105 (9)	0.055 (6)	0.017 (6)	0.016 (5)	0.024 (6)
C20A	0.038 (4)	0.034 (4)	0.026 (3)	0.021 (3)	0.010 (3)	0.009 (3)
C20B	0.041 (4)	0.042 (4)	0.043 (4)	0.032 (4)	0.008 (3)	0.013 (3)
C20C	0.047 (5)	0.033 (4)	0.049 (5)	0.025 (4)	0.012 (4)	0.004 (3)
C20D	0.044 (4)	0.036 (4)	0.036 (4)	0.017 (3)	0.016 (3)	0.008 (3)
C20E	0.043 (4)	0.050 (5)	0.053 (5)	0.030 (4)	−0.003 (4)	0.008 (4)
C20F	0.057 (5)	0.039 (4)	0.051 (5)	0.035 (4)	0.011 (4)	0.007 (4)
C20G	0.075 (7)	0.051 (5)	0.047 (5)	0.028 (5)	0.007 (5)	0.004 (4)

Geometric parameters (Å, º)

Pd1—N21	2.001 (6)	C15—C15A	1.502 (10)
Pd1—N23	2.012 (6)	C16—C17	1.426 (10)
Pd1—N22	2.012 (6)	C17—C18	1.366 (10)
Pd1—N24	2.011 (5)	C17—H17A	0.9500
N21—C1	1.375 (9)	C18—C19	1.430 (10)
N21—C4	1.382 (9)	C18—H18A	0.9500
N22—C6	1.372 (10)	C19—C20	1.399 (10)
N22—C9	1.384 (10)	C20—C20A	1.492 (9)
N23—C14	1.367 (10)	C15A—C15F	1.352 (11)
N23—C11	1.398 (9)	C15A—C15B	1.384 (10)
N24—C19	1.361 (8)	C15B—C15C	1.385 (12)
N24—C16	1.373 (9)	C15B—H15A	0.9500
C1—C20	1.396 (10)	C15C—C15D	1.377 (13)
C1—C2	1.456 (10)	C15C—H15B	0.9500
C2—C3	1.329 (12)	C15D—C15E	1.370 (13)
C2—H2A	0.9500	C15D—C15G	1.496 (13)
C3—C4	1.419 (11)	C15E—C15F	1.381 (12)
C3—H3A	0.9500	C15E—H15C	0.9500
C4—C5	1.386 (11)	C15F—H15D	0.9500
C5—C6	1.384 (12)	C15G—H15E	0.9800
C5—Br1	1.904 (7)	C15G—H15F	0.9800
C6—C7	1.422 (11)	C15G—H15G	0.9800
C7—C8	1.331 (12)	C20A—C20F	1.366 (10)
C7—H7A	0.9500	C20A—C20B	1.375 (9)
C8—C9	1.423 (11)	C20B—C20C	1.380 (11)
C8—H8A	0.9500	C20B—H20A	0.9500
C9—C10	1.396 (12)	C20C—C20D	1.381 (11)
C10—C11	1.350 (11)	C20C—H20B	0.9500
C10—Br2	1.911 (7)	C20D—C20E	1.398 (10)
C11—C12	1.423 (11)	C20D—C20G	1.483 (11)
C12—C13	1.339 (11)	C20E—C20F	1.388 (11)
C12—H12A	0.9500	C20E—H20C	0.9500
C13—C14	1.453 (10)	C20F—H20D	0.9500
C13—H13A	0.9500	C20G—H20E	0.9800
C14—C15	1.380 (10)	C20G—H20F	0.9800
C15—C16	1.413 (9)	C20G—H20G	0.9800
N21—Pd1—N23	178.3 (2)	N24—C16—C15	125.5 (7)
N21—Pd1—N22	89.9 (3)	N24—C16—C17	110.1 (6)
N23—Pd1—N22	90.2 (2)	C15—C16—C17	124.4 (7)
N21—Pd1—N24	90.2 (2)	C18—C17—C16	106.7 (6)
N23—Pd1—N24	89.7 (2)	C18—C17—H17A	126.6
N22—Pd1—N24	178.4 (2)	C16—C17—H17A	126.6
C1—N21—C4	106.0 (6)	C17—C18—C19	106.6 (6)
C1—N21—Pd1	126.4 (5)	C17—C18—H18A	126.7
C4—N21—Pd1	127.6 (5)	C19—C18—H18A	126.7
C6—N22—C9	105.5 (7)	N24—C19—C20	126.2 (6)
C6—N22—Pd1	127.6 (6)	N24—C19—C18	110.4 (6)
C9—N22—Pd1	126.8 (5)	C20—C19—C18	123.4 (6)
C14—N23—C11	106.6 (6)	C1—C20—C19	123.2 (6)
C14—N23—Pd1	126.7 (5)	C1—C20—C20A	118.5 (6)
C11—N23—Pd1	126.7 (5)	C19—C20—C20A	118.2 (6)
C19—N24—C16	106.2 (6)	C15F—C15A—C15B	119.2 (7)
C19—N24—Pd1	126.6 (5)	C15F—C15A—C15	121.4 (6)
C16—N24—Pd1	127.2 (5)	C15B—C15A—C15	119.2 (6)
N21—C1—C20	126.3 (6)	C15A—C15B—C15C	119.8 (8)
N21—C1—C2	109.3 (6)	C15A—C15B—H15A	120.1
C20—C1—C2	124.4 (7)	C15C—C15B—H15A	120.1
C3—C2—C1	106.2 (7)	C15D—C15C—C15B	121.8 (8)
C3—C2—H2A	126.9	C15D—C15C—H15B	119.1
C1—C2—H2A	126.9	C15B—C15C—H15B	119.1
C2—C3—C4	109.2 (7)	C15E—C15D—C15C	116.3 (8)
C2—C3—H3A	125.4	C15E—C15D—C15G	122.4 (9)
C4—C3—H3A	125.4	C15C—C15D—C15G	121.3 (9)
N21—C4—C5	123.2 (7)	C15D—C15E—C15F	123.0 (8)
N21—C4—C3	109.2 (7)	C15D—C15E—H15C	118.5
C5—C4—C3	127.5 (7)	C15F—C15E—H15C	118.5
C6—C5—C4	127.9 (7)	C15A—C15F—C15E	119.8 (8)
C6—C5—Br1	115.6 (6)	C15A—C15F—H15D	120.1
C4—C5—Br1	116.3 (6)	C15E—C15F—H15D	120.1
N22—C6—C5	123.3 (7)	C15D—C15G—H15E	109.5
N22—C6—C7	109.5 (8)	C15D—C15G—H15F	109.5
C5—C6—C7	127.1 (8)	H15E—C15G—H15F	109.5
C8—C7—C6	108.1 (8)	C15D—C15G—H15G	109.5
C8—C7—H7A	125.9	H15E—C15G—H15G	109.5
C6—C7—H7A	125.9	H15F—C15G—H15G	109.5
C7—C8—C9	107.2 (8)	C20F—C20A—C20B	118.6 (7)
C7—C8—H8A	126.4	C20F—C20A—C20	122.6 (6)
C9—C8—H8A	126.4	C20B—C20A—C20	118.7 (6)
N22—C9—C10	123.2 (7)	C20A—C20B—C20C	121.1 (7)
N22—C9—C8	109.6 (8)	C20A—C20B—H20A	119.4
C10—C9—C8	127.1 (8)	C20C—C20B—H20A	119.4
C11—C10—C9	128.4 (7)	C20D—C20C—C20B	121.4 (7)
C11—C10—Br2	115.8 (6)	C20D—C20C—H20B	119.3
C9—C10—Br2	115.9 (6)	C20B—C20C—H20B	119.3
C10—C11—N23	123.7 (7)	C20C—C20D—C20E	116.9 (7)
C10—C11—C12	127.5 (7)	C20C—C20D—C20G	121.1 (7)
N23—C11—C12	108.8 (7)	C20E—C20D—C20G	122.0 (7)
C13—C12—C11	108.5 (7)	C20F—C20E—C20D	121.3 (7)
C13—C12—H12A	125.8	C20F—C20E—H20C	119.4
C11—C12—H12A	125.8	C20D—C20E—H20C	119.4
C12—C13—C14	107.1 (8)	C20A—C20F—C20E	120.6 (7)
C12—C13—H13A	126.4	C20A—C20F—H20D	119.7
C14—C13—H13A	126.4	C20E—C20F—H20D	119.7
N23—C14—C15	127.0 (6)	C20D—C20G—H20E	109.5
N23—C14—C13	109.0 (6)	C20D—C20G—H20F	109.5
C15—C14—C13	123.7 (7)	H20E—C20G—H20F	109.5
C14—C15—C16	123.3 (7)	C20D—C20G—H20G	109.5
C14—C15—C15A	118.0 (6)	H20E—C20G—H20G	109.5
C16—C15—C15A	118.5 (6)	H20F—C20G—H20G	109.5

(VI) [5,10-Dibromo-15,20-bis(4-methylphenyl)porphyrinato](methanol)zinc(II)

Crystal data

[Zn(C34H22Br2N4)(CH4O)]	Z = 2
Mr = 743.79	F(000) = 744
Triclinic, P1	Dx = 1.664 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71075 Å
a = 10.280 (3) Å	Cell parameters from 4552 reflections
b = 11.637 (4) Å	θ = 2.0–31.4°
c = 14.052 (4) Å	µ = 3.56 mm^−1
α = 110.195 (2)°	T = 108 K
β = 95.785 (2)°	Block, red
γ = 105.564 (4)°	0.60 × 0.40 × 0.30 mm
V = 1484.6 (8) Å^3

Data collection

Rigaku Saturn724 (2x2 bin mode) diffractometer	5140 independent reflections
Radiation source: Sealed Tube	4320 reflections with I > 2σ(I)
Graphite Monochromator monochromator	Rint = 0.086
Detector resolution: 28.5714 pixels mm^-1	θmax = 25.0°, θmin = 2.9°
ϕ and ω scans	h = −12→12
Absorption correction: ψ scan (North et al., 1968)	k = −13→13
Tmin = 0.224, Tmax = 0.415	l = −16→16
22765 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.110	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0553P)^2] where P = (Fo^2 + 2Fc^2)/3
5140 reflections	(Δ/σ)max = 0.014
391 parameters	Δρmax = 0.90 e Å^−3
0 restraints	Δρmin = −0.94 e Å^−3

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. No hydrogen atom was included in the refinement for the OH group of the axial methanol molecule. High thermal motion of the axial methanol molecule.

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

	x	y	z	Uiso*/Ueq
Zn1	0.03286 (4)	0.75655 (4)	0.29939 (3)	0.02211 (14)
N21	0.1691 (3)	0.8666 (3)	0.4403 (2)	0.0216 (7)
N22	−0.0258 (3)	0.9139 (3)	0.3056 (2)	0.0237 (7)
N23	−0.1290 (3)	0.6412 (3)	0.1739 (2)	0.0230 (7)
N24	0.0611 (3)	0.5942 (3)	0.3089 (2)	0.0221 (7)
C1	0.2469 (4)	0.8233 (4)	0.4963 (3)	0.0248 (9)
C2	0.3438 (4)	0.9328 (4)	0.5824 (3)	0.0277 (9)
H2A	0.4098	0.9297	0.6331	0.033*
C3	0.3230 (4)	1.0397 (4)	0.5771 (3)	0.0303 (10)
H3A	0.3724	1.1264	0.6231	0.036*
C4	0.2120 (4)	0.9990 (4)	0.4890 (3)	0.0246 (9)
C5	0.1503 (4)	1.0772 (4)	0.4571 (3)	0.0247 (9)
C6	0.0404 (4)	1.0399 (4)	0.3738 (3)	0.0262 (9)
C7	−0.0245 (4)	1.1233 (4)	0.3481 (3)	0.0290 (9)
H7A	0.0018	1.2146	0.3830	0.035*
C8	−0.1285 (4)	1.0493 (4)	0.2665 (3)	0.0296 (10)
H8A	−0.1895	1.0783	0.2323	0.036*
C9	−0.1316 (4)	0.9169 (4)	0.2395 (3)	0.0258 (9)
C10	−0.2233 (4)	0.8069 (4)	0.1596 (3)	0.0267 (9)
C11	−0.2212 (4)	0.6799 (4)	0.1251 (3)	0.0252 (9)
C12	−0.3047 (4)	0.5728 (4)	0.0323 (3)	0.0299 (9)
H12A	−0.3772	0.5735	−0.0150	0.036*
C13	−0.2613 (4)	0.4721 (4)	0.0250 (3)	0.0293 (9)
H13A	−0.2956	0.3887	−0.0297	0.035*
C14	−0.1535 (4)	0.5127 (4)	0.1144 (3)	0.0222 (8)
C15	−0.0883 (4)	0.4323 (4)	0.1415 (3)	0.0220 (8)
C16	0.0078 (4)	0.4705 (4)	0.2342 (3)	0.0218 (8)
C17	0.0579 (4)	0.3841 (4)	0.2682 (3)	0.0246 (9)
H17A	0.0363	0.2936	0.2310	0.030*
C18	0.1415 (4)	0.4557 (4)	0.3630 (3)	0.0240 (9)
H18A	0.1885	0.4247	0.4055	0.029*
C19	0.1460 (4)	0.5869 (4)	0.3874 (3)	0.0216 (8)
C20	0.2311 (4)	0.6927 (4)	0.4760 (3)	0.0235 (8)
Br1	0.21914 (4)	1.25772 (4)	0.54326 (3)	0.03094 (14)
Br2	−0.36981 (4)	0.83434 (4)	0.08457 (4)	0.03688 (15)
C15A	−0.1294 (4)	0.2928 (4)	0.0681 (3)	0.0224 (8)
C15B	−0.2640 (4)	0.2095 (4)	0.0433 (3)	0.0263 (9)
H15A	−0.3325	0.2402	0.0742	0.032*
C15C	−0.2995 (4)	0.0826 (4)	−0.0258 (3)	0.0307 (10)
H15B	−0.3928	0.0277	−0.0433	0.037*
C15D	−0.1998 (4)	0.0336 (4)	−0.0703 (3)	0.0305 (10)
C15E	−0.0649 (4)	0.1168 (4)	−0.0431 (3)	0.0313 (10)
H15C	0.0047	0.0852	−0.0713	0.038*
C15F	−0.0297 (4)	0.2453 (4)	0.0245 (3)	0.0280 (9)
H15D	0.0630	0.3009	0.0410	0.034*
C15G	−0.2387 (5)	−0.1045 (4)	−0.1467 (4)	0.0447 (12)
H15E	−0.1904	−0.1074	−0.2038	0.067*
H15F	−0.3388	−0.1387	−0.1744	0.067*
H15G	−0.2123	−0.1571	−0.1117	0.067*
C20A	0.3132 (4)	0.6617 (4)	0.5519 (3)	0.0230 (8)
C20B	0.2476 (4)	0.6073 (4)	0.6153 (3)	0.0300 (9)
H20A	0.1520	0.5950	0.6128	0.036*
C20C	0.3196 (5)	0.5707 (4)	0.6820 (3)	0.0313 (10)
H20B	0.2728	0.5350	0.7254	0.038*
C20D	0.4584 (4)	0.5851 (4)	0.6869 (3)	0.0284 (9)
C20E	0.5247 (4)	0.6423 (4)	0.6251 (3)	0.0341 (10)
H20C	0.6208	0.6562	0.6288	0.041*
C20F	0.4528 (4)	0.6796 (4)	0.5580 (3)	0.0332 (10)
H20D	0.5000	0.7177	0.5161	0.040*
C20G	0.5351 (5)	0.5398 (5)	0.7563 (3)	0.0416 (12)
H20E	0.4745	0.5102	0.7986	0.062*
H20F	0.6171	0.6114	0.8018	0.062*
H20G	0.5636	0.4682	0.7136	0.062*
C1A	0.3335 (5)	0.8294 (8)	0.2530 (4)	0.100 (3)
H1AA	0.3867	0.8079	0.1991	0.149*
H1AB	0.3514	0.7911	0.3029	0.149*
H1AC	0.3611	0.9237	0.2889	0.149*
O1A	0.1919 (3)	0.7802 (3)	0.2069 (2)	0.0319 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0248 (3)	0.0197 (2)	0.0237 (3)	0.0070 (2)	0.00448 (19)	0.0109 (2)
N21	0.0251 (17)	0.0187 (16)	0.0218 (17)	0.0053 (14)	0.0063 (14)	0.0097 (14)
N22	0.0254 (18)	0.0210 (17)	0.0267 (18)	0.0080 (14)	0.0075 (14)	0.0108 (15)
N23	0.0271 (18)	0.0226 (17)	0.0234 (17)	0.0105 (14)	0.0045 (14)	0.0122 (14)
N24	0.0216 (17)	0.0201 (17)	0.0244 (17)	0.0062 (14)	0.0037 (14)	0.0092 (14)
C1	0.027 (2)	0.025 (2)	0.022 (2)	0.0088 (17)	0.0074 (17)	0.0079 (17)
C2	0.025 (2)	0.027 (2)	0.027 (2)	0.0056 (18)	0.0008 (17)	0.0082 (18)
C3	0.032 (2)	0.022 (2)	0.031 (2)	0.0027 (18)	0.0048 (19)	0.0086 (18)
C4	0.022 (2)	0.023 (2)	0.027 (2)	0.0033 (17)	0.0084 (17)	0.0105 (17)
C5	0.025 (2)	0.0171 (19)	0.032 (2)	0.0047 (16)	0.0115 (18)	0.0096 (17)
C6	0.029 (2)	0.021 (2)	0.035 (2)	0.0091 (17)	0.0167 (19)	0.0161 (18)
C7	0.034 (2)	0.022 (2)	0.036 (2)	0.0115 (19)	0.011 (2)	0.0147 (19)
C8	0.029 (2)	0.028 (2)	0.042 (2)	0.0141 (19)	0.013 (2)	0.021 (2)
C9	0.024 (2)	0.029 (2)	0.032 (2)	0.0116 (18)	0.0113 (18)	0.0182 (19)
C10	0.022 (2)	0.035 (2)	0.032 (2)	0.0122 (18)	0.0091 (18)	0.0210 (19)
C11	0.025 (2)	0.028 (2)	0.027 (2)	0.0075 (17)	0.0061 (17)	0.0166 (18)
C12	0.027 (2)	0.034 (2)	0.030 (2)	0.0073 (19)	−0.0012 (18)	0.0180 (19)
C13	0.031 (2)	0.025 (2)	0.025 (2)	0.0002 (18)	−0.0036 (18)	0.0096 (18)
C14	0.022 (2)	0.023 (2)	0.0205 (19)	0.0040 (17)	0.0028 (16)	0.0110 (17)
C15	0.023 (2)	0.0183 (19)	0.025 (2)	0.0040 (16)	0.0067 (16)	0.0094 (16)
C16	0.021 (2)	0.026 (2)	0.0219 (19)	0.0077 (17)	0.0048 (16)	0.0124 (17)
C17	0.028 (2)	0.020 (2)	0.030 (2)	0.0110 (17)	0.0092 (18)	0.0111 (17)
C18	0.026 (2)	0.025 (2)	0.028 (2)	0.0116 (17)	0.0048 (17)	0.0158 (18)
C19	0.020 (2)	0.023 (2)	0.025 (2)	0.0065 (16)	0.0070 (16)	0.0129 (17)
C20	0.019 (2)	0.027 (2)	0.027 (2)	0.0061 (17)	0.0043 (16)	0.0141 (18)
Br1	0.0368 (3)	0.0191 (2)	0.0350 (3)	0.00582 (18)	0.01124 (19)	0.00970 (18)
Br2	0.0335 (3)	0.0394 (3)	0.0457 (3)	0.0165 (2)	0.0032 (2)	0.0238 (2)
C15A	0.029 (2)	0.022 (2)	0.0162 (18)	0.0064 (17)	−0.0001 (16)	0.0096 (16)
C15B	0.028 (2)	0.025 (2)	0.030 (2)	0.0091 (18)	0.0070 (18)	0.0139 (18)
C15C	0.032 (2)	0.026 (2)	0.031 (2)	0.0046 (19)	0.0038 (19)	0.0112 (19)
C15D	0.039 (3)	0.026 (2)	0.026 (2)	0.0078 (19)	0.0057 (19)	0.0108 (18)
C15E	0.038 (3)	0.034 (2)	0.028 (2)	0.016 (2)	0.0129 (19)	0.0142 (19)
C15F	0.028 (2)	0.029 (2)	0.030 (2)	0.0076 (18)	0.0102 (18)	0.0161 (18)
C15G	0.055 (3)	0.027 (2)	0.042 (3)	0.008 (2)	0.013 (2)	0.004 (2)
C20A	0.024 (2)	0.020 (2)	0.022 (2)	0.0050 (17)	0.0033 (16)	0.0070 (16)
C20B	0.029 (2)	0.034 (2)	0.030 (2)	0.0102 (19)	0.0088 (18)	0.0145 (19)
C20C	0.043 (3)	0.028 (2)	0.024 (2)	0.009 (2)	0.0076 (19)	0.0127 (18)
C20D	0.033 (2)	0.025 (2)	0.025 (2)	0.0068 (18)	−0.0010 (18)	0.0096 (18)
C20E	0.022 (2)	0.049 (3)	0.041 (3)	0.016 (2)	0.0066 (19)	0.026 (2)
C20F	0.030 (2)	0.041 (3)	0.035 (2)	0.012 (2)	0.0089 (19)	0.022 (2)
C20G	0.040 (3)	0.050 (3)	0.039 (3)	0.011 (2)	0.000 (2)	0.027 (2)
C1A	0.031 (3)	0.190 (9)	0.037 (3)	−0.011 (4)	0.001 (3)	0.032 (4)
O1A	0.0264 (16)	0.0405 (18)	0.0328 (16)	0.0101 (14)	0.0103 (13)	0.0183 (14)

Geometric parameters (Å, º)

Zn1—N24	2.033 (3)	C17—C18	1.352 (5)
Zn1—N22	2.053 (3)	C17—H17A	0.9500
Zn1—N21	2.061 (3)	C18—C19	1.431 (5)
Zn1—N23	2.063 (3)	C18—H18A	0.9500
Zn1—O1A	2.207 (3)	C19—C20	1.405 (5)
N21—C1	1.371 (5)	C20—C20A	1.492 (5)
N21—C4	1.372 (5)	C15A—C15B	1.387 (5)
N22—C9	1.373 (5)	C15A—C15F	1.389 (5)
N22—C6	1.376 (5)	C15B—C15C	1.381 (5)
N23—C11	1.372 (5)	C15B—H15A	0.9500
N23—C14	1.375 (5)	C15C—C15D	1.401 (6)
N24—C16	1.376 (5)	C15C—H15B	0.9500
N24—C19	1.378 (5)	C15D—C15E	1.387 (6)
C1—C20	1.406 (5)	C15D—C15G	1.508 (5)
C1—C2	1.446 (5)	C15E—C15F	1.389 (6)
C2—C3	1.343 (6)	C15E—H15C	0.9500
C2—H2A	0.9500	C15F—H15D	0.9500
C3—C4	1.441 (6)	C15G—H15E	0.9800
C3—H3A	0.9500	C15G—H15F	0.9800
C4—C5	1.402 (5)	C15G—H15G	0.9800
C5—C6	1.399 (6)	C20A—C20F	1.382 (6)
C5—Br1	1.911 (4)	C20A—C20B	1.390 (6)
C6—C7	1.434 (5)	C20B—C20C	1.382 (5)
C7—C8	1.333 (6)	C20B—H20A	0.9500
C7—H7A	0.9500	C20C—C20D	1.383 (6)
C8—C9	1.444 (5)	C20C—H20B	0.9500
C8—H8A	0.9500	C20D—C20E	1.391 (6)
C9—C10	1.391 (6)	C20D—C20G	1.508 (5)
C10—C11	1.394 (6)	C20E—C20F	1.392 (6)
C10—Br2	1.911 (4)	C20E—H20C	0.9500
C11—C12	1.438 (5)	C20F—H20D	0.9500
C12—C13	1.338 (6)	C20G—H20E	0.9800
C12—H12A	0.9500	C20G—H20F	0.9800
C13—C14	1.435 (5)	C20G—H20G	0.9800
C13—H13A	0.9500	C1A—O1A	1.405 (6)
C14—C15	1.413 (5)	C1A—H1AA	0.9800
C15—C16	1.406 (5)	C1A—H1AB	0.9800
C15—C15A	1.505 (5)	C1A—H1AC	0.9800
C16—C17	1.437 (5)
N24—Zn1—N22	168.66 (13)	C15—C16—C17	124.9 (4)
N24—Zn1—N21	89.77 (12)	C18—C17—C16	107.2 (3)
N22—Zn1—N21	89.85 (12)	C18—C17—H17A	126.4
N24—Zn1—N23	89.12 (12)	C16—C17—H17A	126.4
N22—Zn1—N23	89.27 (13)	C17—C18—C19	107.1 (3)
N21—Zn1—N23	169.90 (12)	C17—C18—H18A	126.5
N24—Zn1—O1A	93.27 (12)	C19—C18—H18A	126.5
N22—Zn1—O1A	98.06 (12)	N24—C19—C20	125.5 (3)
N21—Zn1—O1A	94.45 (12)	N24—C19—C18	110.0 (3)
N23—Zn1—O1A	95.64 (12)	C20—C19—C18	124.4 (4)
C1—N21—C4	106.9 (3)	C1—C20—C19	125.2 (4)
C1—N21—Zn1	126.3 (3)	C1—C20—C20A	118.5 (3)
C4—N21—Zn1	126.3 (3)	C19—C20—C20A	116.3 (3)
C9—N22—C6	106.3 (3)	C15B—C15A—C15F	118.8 (4)
C9—N22—Zn1	127.5 (3)	C15B—C15A—C15	122.0 (3)
C6—N22—Zn1	126.1 (3)	C15F—C15A—C15	119.2 (4)
C11—N23—C14	106.4 (3)	C15C—C15B—C15A	120.8 (4)
C11—N23—Zn1	127.3 (3)	C15C—C15B—H15A	119.6
C14—N23—Zn1	125.8 (2)	C15A—C15B—H15A	119.6
C16—N24—C19	105.9 (3)	C15B—C15C—C15D	120.9 (4)
C16—N24—Zn1	126.8 (2)	C15B—C15C—H15B	119.6
C19—N24—Zn1	127.1 (2)	C15D—C15C—H15B	119.6
N21—C1—C20	125.4 (3)	C15E—C15D—C15C	117.9 (4)
N21—C1—C2	109.3 (3)	C15E—C15D—C15G	121.2 (4)
C20—C1—C2	125.3 (4)	C15C—C15D—C15G	120.9 (4)
C3—C2—C1	107.1 (4)	C15D—C15E—C15F	121.3 (4)
C3—C2—H2A	126.5	C15D—C15E—H15C	119.3
C1—C2—H2A	126.5	C15F—C15E—H15C	119.3
C2—C3—C4	107.6 (4)	C15E—C15F—C15A	120.3 (4)
C2—C3—H3A	126.2	C15E—C15F—H15D	119.9
C4—C3—H3A	126.2	C15A—C15F—H15D	119.9
N21—C4—C5	123.3 (3)	C15D—C15G—H15E	109.5
N21—C4—C3	109.1 (3)	C15D—C15G—H15F	109.5
C5—C4—C3	127.5 (4)	H15E—C15G—H15F	109.5
C6—C5—C4	128.6 (4)	C15D—C15G—H15G	109.5
C6—C5—Br1	115.7 (3)	H15E—C15G—H15G	109.5
C4—C5—Br1	115.6 (3)	H15F—C15G—H15G	109.5
N22—C6—C5	124.0 (4)	C20F—C20A—C20B	118.2 (4)
N22—C6—C7	109.5 (4)	C20F—C20A—C20	122.0 (4)
C5—C6—C7	126.4 (4)	C20B—C20A—C20	119.7 (4)
C8—C7—C6	107.5 (4)	C20C—C20B—C20A	120.9 (4)
C8—C7—H7A	126.2	C20C—C20B—H20A	119.5
C6—C7—H7A	126.2	C20A—C20B—H20A	119.5
C7—C8—C9	107.5 (4)	C20D—C20C—C20B	121.3 (4)
C7—C8—H8A	126.2	C20D—C20C—H20B	119.3
C9—C8—H8A	126.2	C20B—C20C—H20B	119.3
N22—C9—C10	123.4 (4)	C20C—C20D—C20E	117.7 (4)
N22—C9—C8	109.1 (4)	C20C—C20D—C20G	121.2 (4)
C10—C9—C8	127.5 (4)	C20E—C20D—C20G	121.1 (4)
C9—C10—C11	128.9 (4)	C20D—C20E—C20F	121.2 (4)
C9—C10—Br2	115.5 (3)	C20D—C20E—H20C	119.4
C11—C10—Br2	115.5 (3)	C20F—C20E—H20C	119.4
N23—C11—C10	123.3 (4)	C20A—C20F—C20E	120.6 (4)
N23—C11—C12	109.5 (3)	C20A—C20F—H20D	119.7
C10—C11—C12	127.1 (4)	C20E—C20F—H20D	119.7
C13—C12—C11	107.1 (4)	C20D—C20G—H20E	109.5
C13—C12—H12A	126.4	C20D—C20G—H20F	109.5
C11—C12—H12A	126.4	H20E—C20G—H20F	109.5
C12—C13—C14	107.7 (4)	C20D—C20G—H20G	109.5
C12—C13—H13A	126.1	H20E—C20G—H20G	109.5
C14—C13—H13A	126.1	H20F—C20G—H20G	109.5
N23—C14—C15	124.8 (3)	O1A—C1A—H1AA	109.5
N23—C14—C13	109.2 (3)	O1A—C1A—H1AB	109.5
C15—C14—C13	125.9 (4)	H1AA—C1A—H1AB	109.5
C16—C15—C14	125.2 (4)	O1A—C1A—H1AC	109.5
C16—C15—C15A	116.8 (3)	H1AA—C1A—H1AC	109.5
C14—C15—C15A	117.9 (3)	H1AB—C1A—H1AC	109.5
N24—C16—C15	125.3 (3)	C1A—O1A—Zn1	121.5 (3)
N24—C16—C17	109.8 (3)
N24—Zn1—N21—C1	6.1 (3)	C9—C10—C11—N23	6.1 (7)
N22—Zn1—N21—C1	174.8 (3)	Br2—C10—C11—N23	−175.7 (3)
N23—Zn1—N21—C1	89.8 (7)	C9—C10—C11—C12	−169.4 (4)
O1A—Zn1—N21—C1	−87.2 (3)	Br2—C10—C11—C12	8.8 (6)
N24—Zn1—N21—C4	177.2 (3)	N23—C11—C12—C13	−1.0 (5)
N22—Zn1—N21—C4	−14.1 (3)	C10—C11—C12—C13	175.0 (4)
N23—Zn1—N21—C4	−99.2 (7)	C11—C12—C13—C14	2.0 (5)
O1A—Zn1—N21—C4	83.9 (3)	C11—N23—C14—C15	−174.6 (4)
N24—Zn1—N22—C9	−84.5 (7)	Zn1—N23—C14—C15	13.1 (5)
N21—Zn1—N22—C9	−172.6 (3)	C11—N23—C14—C13	1.6 (4)
N23—Zn1—N22—C9	−2.6 (3)	Zn1—N23—C14—C13	−170.6 (3)
O1A—Zn1—N22—C9	93.0 (3)	C12—C13—C14—N23	−2.3 (5)
N24—Zn1—N22—C6	100.3 (7)	C12—C13—C14—C15	173.9 (4)
N21—Zn1—N22—C6	12.2 (3)	N23—C14—C15—C16	2.0 (6)
N23—Zn1—N22—C6	−177.8 (3)	C13—C14—C15—C16	−173.6 (4)
O1A—Zn1—N22—C6	−82.2 (3)	N23—C14—C15—C15A	178.8 (3)
N24—Zn1—N23—C11	171.4 (3)	C13—C14—C15—C15A	3.2 (6)
N22—Zn1—N23—C11	2.6 (3)	C19—N24—C16—C15	177.7 (4)
N21—Zn1—N23—C11	87.7 (8)	Zn1—N24—C16—C15	−7.0 (6)
O1A—Zn1—N23—C11	−95.4 (3)	C19—N24—C16—C17	1.5 (4)
N24—Zn1—N23—C14	−18.0 (3)	Zn1—N24—C16—C17	176.8 (2)
N22—Zn1—N23—C14	173.3 (3)	C14—C15—C16—N24	−5.5 (6)
N21—Zn1—N23—C14	−101.7 (7)	C15A—C15—C16—N24	177.7 (3)
O1A—Zn1—N23—C14	75.2 (3)	C14—C15—C16—C17	170.2 (4)
N22—Zn1—N24—C16	97.0 (7)	C15A—C15—C16—C17	−6.6 (6)
N21—Zn1—N24—C16	−174.9 (3)	N24—C16—C17—C18	−0.1 (4)
N23—Zn1—N24—C16	15.1 (3)	C15—C16—C17—C18	−176.4 (4)
O1A—Zn1—N24—C16	−80.5 (3)	C16—C17—C18—C19	−1.2 (4)
N22—Zn1—N24—C19	−88.7 (7)	C16—N24—C19—C20	174.5 (4)
N21—Zn1—N24—C19	−0.6 (3)	Zn1—N24—C19—C20	−0.8 (5)
N23—Zn1—N24—C19	−170.5 (3)	C16—N24—C19—C18	−2.2 (4)
O1A—Zn1—N24—C19	93.9 (3)	Zn1—N24—C19—C18	−177.5 (3)
C4—N21—C1—C20	176.5 (4)	C17—C18—C19—N24	2.2 (4)
Zn1—N21—C1—C20	−11.0 (6)	C17—C18—C19—C20	−174.5 (4)
C4—N21—C1—C2	−1.0 (4)	N21—C1—C20—C19	9.0 (6)
Zn1—N21—C1—C2	171.5 (2)	C2—C1—C20—C19	−173.9 (4)
N21—C1—C2—C3	0.1 (5)	N21—C1—C20—C20A	−172.9 (3)
C20—C1—C2—C3	−177.4 (4)	C2—C1—C20—C20A	4.2 (6)
C1—C2—C3—C4	0.8 (5)	N24—C19—C20—C1	−2.6 (6)
C1—N21—C4—C5	−176.3 (4)	C18—C19—C20—C1	173.6 (4)
Zn1—N21—C4—C5	11.2 (5)	N24—C19—C20—C20A	179.2 (3)
C1—N21—C4—C3	1.5 (4)	C18—C19—C20—C20A	−4.6 (6)
Zn1—N21—C4—C3	−171.0 (3)	C16—C15—C15A—C15B	116.4 (4)
C2—C3—C4—N21	−1.5 (5)	C14—C15—C15A—C15B	−60.7 (5)
C2—C3—C4—C5	176.2 (4)	C16—C15—C15A—C15F	−62.9 (5)
N21—C4—C5—C6	−0.8 (6)	C14—C15—C15A—C15F	120.0 (4)
C3—C4—C5—C6	−178.2 (4)	C15F—C15A—C15B—C15C	−1.9 (6)
N21—C4—C5—Br1	175.6 (3)	C15—C15A—C15B—C15C	178.8 (4)
C3—C4—C5—Br1	−1.8 (5)	C15A—C15B—C15C—C15D	1.8 (6)
C9—N22—C6—C5	176.6 (4)	C15B—C15C—C15D—C15E	−0.3 (6)
Zn1—N22—C6—C5	−7.4 (5)	C15B—C15C—C15D—C15G	−179.2 (4)
C9—N22—C6—C7	−1.0 (4)	C15C—C15D—C15E—C15F	−1.2 (6)
Zn1—N22—C6—C7	175.0 (3)	C15G—C15D—C15E—C15F	177.7 (4)
C4—C5—C6—N22	−1.2 (7)	C15D—C15E—C15F—C15A	1.2 (6)
Br1—C5—C6—N22	−177.6 (3)	C15B—C15A—C15F—C15E	0.4 (6)
C4—C5—C6—C7	175.9 (4)	C15—C15A—C15F—C15E	179.7 (4)
Br1—C5—C6—C7	−0.5 (5)	C1—C20—C20A—C20F	−75.5 (5)
N22—C6—C7—C8	0.4 (5)	C19—C20—C20A—C20F	102.8 (5)
C5—C6—C7—C8	−177.1 (4)	C1—C20—C20A—C20B	107.7 (4)
C6—C7—C8—C9	0.4 (5)	C19—C20—C20A—C20B	−74.0 (5)
C6—N22—C9—C10	−179.5 (4)	C20F—C20A—C20B—C20C	−0.7 (6)
Zn1—N22—C9—C10	4.6 (6)	C20—C20A—C20B—C20C	176.2 (4)
C6—N22—C9—C8	1.2 (4)	C20A—C20B—C20C—C20D	−1.0 (6)
Zn1—N22—C9—C8	−174.7 (3)	C20B—C20C—C20D—C20E	2.4 (6)
C7—C8—C9—N22	−1.0 (5)	C20B—C20C—C20D—C20G	−177.3 (4)
C7—C8—C9—C10	179.7 (4)	C20C—C20D—C20E—C20F	−2.2 (6)
N22—C9—C10—C11	−6.1 (7)	C20G—C20D—C20E—C20F	177.5 (4)
C8—C9—C10—C11	173.0 (4)	C20B—C20A—C20F—C20E	0.8 (6)
N22—C9—C10—Br2	175.7 (3)	C20—C20A—C20F—C20E	−176.0 (4)
C8—C9—C10—Br2	−5.2 (6)	C20D—C20E—C20F—C20A	0.6 (7)
C14—N23—C11—C10	−176.6 (4)	N24—Zn1—O1A—C1A	−76.6 (5)
Zn1—N23—C11—C10	−4.5 (6)	N22—Zn1—O1A—C1A	103.9 (5)
C14—N23—C11—C12	−0.4 (4)	N21—Zn1—O1A—C1A	13.4 (5)
Zn1—N23—C11—C12	171.7 (3)	N23—Zn1—O1A—C1A	−166.1 (5)