Crystal structure of (diethyl ether-κO)[5,10,15,20-tetra-kis-(2-iso-thio-cyanato-phen-yl)porphyrinato-κ4 N]zinc diethyl ether solvate.

The crystal structure of the title compound, [Zn(C48H24N8S4)(C4H10O)]·C4H10O, consists of discrete porphyrin complexes that are located on a twofold rotation axis. The ZnII cation is fivefold coordinated by four N atoms of the porphyrin moiety and one O atom of a diethyl ether mol-ecule in a slightly distorted square-pyramidal environment with the diethyl ether mol-ecule in the apical position. The porphyrin backbone is nearly planar with the metal cation slightly shifted out of the plane towards the coordinating diethyl ether mol-ecule. All four iso-thio-cyanato groups of the phenyl substituents at the meso-positions face the same side of the porphyrin, as is characteristic for picket fence porphyrins. In the crystal structure, the discrete porphyrin complexes are arranged in such a way that cavities are formed in which additional diethyl ether solvate mol-ecules are located around a twofold rotation axis. The O atom of the solvent mol-ecule is not positioned exactly on the twofold rotation axis, thus making the whole mol-ecule equally disordered over two symmetry-related positions.

Chemical context

Iso­thio­cyanates serve as versatile starting materials for a variety of functional groups (Batey & Powell, 2000 ▸; Ding et al., 2011 ▸; Serra et al., 2014 ▸; Guo et al., 2010 ▸; Shin et al., 2000 ▸; Kosurkar et al., 2014 ▸; Alizadeh et al., 2016 ▸; Rao et al., 2015 ▸). Included in porphyrin scaffolds, iso­thio­cyanates may serve as precursors for the synthesis of tetra­topic ligands with fourfold symmetry. In the case where all four ortho-substituents of the meso-phenyl groups face the same side of the porphyrin plane, these porphyrins are denominated picket fence porphyrins. These compounds are widely used as model compounds for hemoproteins (Collman et al., 1975 ▸; Tabushi et al., 1985 ▸; Schappacher et al., 1989 ▸). With a bulky ortho-substituent and ZnII as the central metal cation, the rotational barriers are sufficiently high to isolate the different atropisomers (Freitag & Whitten, 1983 ▸). A variety of picket fence porphyrins has been reported (Collman et al., 1975 ▸; Mansour et al., 2017 ▸; Cormode et al., 2006 ▸; Le Maux et al., 1993 ▸; Wuenschell et al., 1992 ▸). In most cases, amides are used as functional groups in the ortho-positions of the meso-phenyl groups, which hampers further functionalization. The title compound now opens new avenues for the synthesis of functionalized picket fence porphyrins and is a promising starting material for the design of anion binding ligands. The title compound can be obtained in one step using a method reported by Jha et al. (Fig. 1 ▸), starting from the all-α isomer of the amino derivative we have published previously (Jha et al., 2007 ▸; Leben et al., 2018 ▸). It is important to note that the reaction has to be carried out at 273 K, because at room temperature a mixture of the atrop­isomers is obtained. After dissolving the tetra­kis­(iso­thio­cyanato­phen­yl) porphyrin in acetone and precipitating with diethyl ether, single crystals were obtained, which were characterized by single crystal X-ray diffraction.

Figure 1

Reaction scheme for the synthesis of the title compound.

Structural commentary

The asymmetric unit of the title compound, Zn(C48H24N8S4)(C4H10O)·C4H10O, comprises one ZnII cation, one half of the porphyrin mol­ecule and one half of a coordinating diethyl ether mol­ecule as well as one half of a diethyl ether solvate mol­ecule. The complex porphyrin mol­ecule and the coordinating diethyl ether mol­ecule are located on a twofold rotation axis whereas the solvent diethyl ether mol­ecule is in a general position and is equally disordered around a twofold rotation axis (Fig. 2 ▸). The four iso­thio­cyanate substituents of the phenyl groups at the meso-positions point to the same side of the porphyrin moiety, which proves that the tetra-α isomer has formed. The porphyrin plane is close to planar with a maximum deviation from the mean plane of 0.276 (3) Å. The phenyl rings are rotated out of the porphyrin plane by 63.16 (5) and 82.06 (6)°. The ZnII cation is fivefold coordinated by the four N atoms of the porphyrin mol­ecule in the basal positions and by one O atom of a diethyl ether mol­ecule in the apical position, leading to a distorted square-pyramidal coordination environment (Table 1 ▸, Fig. 3 ▸). The Zn—N distances of 2.0622 (13) and 2.0684 (14) Å and the Zn—O distance of 2.1352 (19) Å are in characteristic ranges. The angles around the ZnII cation range from 88.54 (6) to 99.69 (4)° for the basal N4 plane and from 160.61 (8) to 164.44 (8)° involving the apical O atom, demonstrating that the square pyramid is slightly distorted (Table 1 ▸). The ZnII cation is located 0.4052 (9) Å out of the mean porphyrin plane and is shifted towards the coordinating diethyl ether mol­ecule (Fig. 4 ▸).

Figure 2

The mol­ecular entities of the title compound with the atom labelling and displacement ellipsoids drawn at the 50% probability level. Only one orientation of the disordered diethyl ether solvent is given. [Symmetry code: (i) −x + 2, y, −z + .]

Table 1

Selected geometric parameters (Å, °)

Zn1—N2	2.0622 (13)	Zn1—N1	2.0685 (14)
Zn1—N2i	2.0622 (13)	Zn1—O1	2.1352 (19)
Zn1—N1i	2.0684 (14)
N2—Zn1—N2i	164.44 (8)	N1i—Zn1—N1	160.61 (8)
N2—Zn1—N1i	88.85 (6)	N2i—Zn1—O1	97.78 (4)
N2i—Zn1—N1i	88.54 (6)	N1i—Zn1—O1	99.69 (4)
N2—Zn1—N1	88.54 (6)	N1—Zn1—O1	99.69 (4)
N2i—Zn1—N1	88.85 (6)

Symmetry code: (i) .

Figure 3

Mol­ecular structure of the discrete complex in a view onto the porphyrin plane.

Figure 4

Mol­ecular structure of the discrete complex in a view parallel to the porphyrin plane.

Supra­molecular features

In the crystal structure of the title compound, each two discrete complexes form centrosymmetric pairs with the coordinating diethyl ether mol­ecules pointing in opposite directions (Fig. 5 ▸). The complexes are arranged into columns along [001]. This arrangement leads to the formation of cavities between two neighbouring coordinating diethyl ether mol­ecules, in which the disordered diethyl ether solvate mol­ecules are embedded (Fig. 5 ▸). There are no notable inter­molecular inter­actions between the mol­ecular moieties in the crystal structure.

Figure 5

Crystal structure of the title compound viewed along [001].

Database survey

The synthesis of the metal-free oxygen derivative 5,10,15,20-tetra­kis α,α,α,α 2-iso­cyanato­phenyl porphyrin has been known for several years (Collman et al., 1998 ▸). However, the crystal structure of this compound has not yet been reported. A CSD database search (Version 5.39; Groom et al., 2016 ▸) revealed the crystal structures of several metal porphyrins with iso­thio­cyanate entities as axial ligands (Dhifet et al., 2010 ▸; Scheidt et al., 1982 ▸; Ezzayani et al., 2014 ▸; Denden et al., 2015 ▸). In addition, the crystal structure of a para-iso­thio­cyanato­phenyl porphyrin has been reported (Sibrian-Vazquez et al., 2005 ▸).

Synthesis and crystallization

The metal-free all-α isomer of 2-amino­phenyl porphyrin was synthesized according to reported procedures (Collman et al., 1975 ▸; Lindsey, 1980 ▸). Metallation followed standard metallation conditions as reported previously (Strohmeier et al., 1997 ▸; Leben et al., 2018 ▸). For the introduction of the iso­thio­cyanato groups, a modified synthesis was used (Jha et al., 2007 ▸). 5,10,15,20-Tetra­kis(α,α,α,α 2-amino­phen­yl)zinc(II) porphyrin (150 mg, 203 µmol) was dissolved in 30 ml of di­chloro­methane and cooled to 273 K. 1,1′-Thio­carbonyldi-2,2′-pyridone (TDP, 377 mg, 1.62 mmol) was added and the mixture stirred for 50 minutes at 273 K. Removing the solvent and filtration over silica gel (cyclo­hexa­ne/ethyl acetate, v:v = 1:1) gave the title compound in qu­anti­tative yield. For crystallization, a small amount was dissolved in acetone and crystallized by adding diethyl ether.

1H NMR (500 MHz, CDCl3, 300 K): δ = 8.80 (s, 8H, H-β), 8.21 (dd, 3 J = 7.5 Hz, 4 J = 1.2 Hz, 4H, H-6), 7.78 (dt, 3 J = 7.9 Hz, 4 J = 1.5 Hz, 4H, H-4), 7.68 (dt, 3 J = 7.6 Hz, 4 J = 1.3 Hz, 4H, H-5), 7.61 (dd, 3 J = 8.2 Hz, 4 J = 1.0 Hz, 4H, H-3) ppm. 13C NMR (125 MHz, CDCl3, 300 K): δ = 149.9 (C-α), 141.0 (C1), 134.8 (C6), 134.5 (C2), 131.6 (C-β), 129.3 (C4), 125.7 (C5), 124.4 (C3), 115.7 (C-meso) ppm. EI–MS (70 eV): m/z (%) = 904.1 (100) [M]+.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. The C—H hydrogen atoms were positioned with idealized geometries (C—H = 0.95–0.99 Å; methyl H atoms of the coordinating diethyl ether mol­ecule were allowed to rotate but not to tip) and were refined with U iso(H) = 1.2U eq(C) (1.5 for methyl H atoms) using a riding model. The O atom of the diethyl ether solvate mol­ecule is not located exactly on the twofold rotation axis and thus the complete mol­ecule is equally disordered over two sets of sites because of symmetry. Therefore for each atom the occupancy was set to 0.5, and atoms were treated with SADI and SIMU commands (Sheldrick, 2015b ▸) to achieve similar displacement ellipsoids.

Table 2

Experimental details

Crystal data
Chemical formula	[Zn(C48H24N8S4)(C4H10O)]·C4H10O
M r	1054.60
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	200
a, b, c (Å)	19.8830 (4), 17.1781 (3), 14.8684 (3)
β (°)	91.667 (1)
V (Å3)	5076.18 (17)
Z	4
Radiation type	Mo Kα
μ (mm−1)	0.70
Crystal size (mm)	0.14 × 0.11 × 0.07
Data collection
Diffractometer	Stoe IPDS2
Absorption correction	Numerical (X-RED and X-SHAPE; Stoe, 2008 ▸)
T min, T max	0.807, 0.951
No. of measured, independent and observed [I > 2σ(I)] reflections	39705, 5530, 5042
R int	0.039
(sin θ/λ)max (Å−1)	0.639
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.036, 0.103, 1.05
No. of reflections	5530
No. of parameters	346
No. of restraints	26
H-atom treatment	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	0.39, −0.35

Computer programs: X-AREA (Stoe, 2008 ▸), SHELXT (Sheldrick, 2015a ▸), SHELXL2014 (Sheldrick, 2015b ▸), XP (Sheldrick, 2008 ▸), DIAMOND (Brandenburg, 2014 ▸) and publCIF (Westrip, 2010 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989018014238/wm5466sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989018014238/wm5466Isup2.hkl

CCDC reference: 1872076

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Zn(C48H24N8S4)(C4H10O)]·C4H10O	F(000) = 2184
Mr = 1054.60	Dx = 1.380 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 19.8830 (4) Å	Cell parameters from 39705 reflections
b = 17.1781 (3) Å	θ = 1.6–27.0°
c = 14.8684 (3) Å	µ = 0.70 mm−1
β = 91.667 (1)°	T = 200 K
V = 5076.18 (17) Å3	Block, red
Z = 4	0.14 × 0.11 × 0.07 mm

Stoe IPDS-2 diffractometer	5042 reflections with I > 2σ(I)
ω scans	Rint = 0.039
Absorption correction: numerical (X-Red and X-Shape; Stoe, 2008)	θmax = 27.0°, θmin = 1.6°
Tmin = 0.807, Tmax = 0.951	h = −25→25
39705 measured reflections	k = −21→21
5530 independent reflections	l = −18→18

Refinement on F2	Hydrogen site location: mixed
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.036	w = 1/[σ2(Fo2) + (0.0603P)2 + 2.7141P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.103	(Δ/σ)max = 0.001
S = 1.05	Δρmax = 0.39 e Å−3
5530 reflections	Δρmin = −0.35 e Å−3
346 parameters	Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
26 restraints	Extinction coefficient: 0.0011 (2)

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Zn1	0.5000	0.64166 (2)	0.7500	0.03835 (10)
N1	0.40708 (7)	0.62138 (9)	0.68826 (9)	0.0400 (3)
N2	0.54332 (7)	0.62541 (9)	0.62706 (9)	0.0392 (3)
C1	0.34674 (8)	0.61377 (10)	0.72962 (11)	0.0405 (3)
C2	0.29355 (9)	0.60302 (11)	0.66268 (12)	0.0460 (4)
H2	0.2471	0.5962	0.6736	0.055*
C3	0.32240 (9)	0.60449 (12)	0.58175 (12)	0.0464 (4)
H3	0.3001	0.5983	0.5248	0.056*
C4	0.39333 (8)	0.61718 (10)	0.59772 (11)	0.0407 (3)
C5	0.44062 (9)	0.62460 (10)	0.53022 (11)	0.0408 (3)
C6	0.51067 (9)	0.62744 (10)	0.54465 (11)	0.0405 (3)
C7	0.55953 (9)	0.62818 (12)	0.47508 (12)	0.0472 (4)
H7	0.5503	0.6310	0.4121	0.057*
C8	0.62118 (9)	0.62418 (12)	0.51605 (12)	0.0473 (4)
H8	0.6632	0.6226	0.4873	0.057*
C9	0.61077 (8)	0.62273 (10)	0.61146 (11)	0.0407 (3)
C10	0.66219 (8)	0.61682 (10)	0.67757 (11)	0.0406 (3)
C11	0.41493 (9)	0.62820 (11)	0.43487 (11)	0.0423 (4)
C12	0.37604 (9)	0.69080 (12)	0.40320 (12)	0.0479 (4)
C13	0.35525 (11)	0.69580 (14)	0.31334 (13)	0.0578 (5)
H13	0.3294	0.7392	0.2928	0.069*
C14	0.37198 (10)	0.63815 (14)	0.25443 (13)	0.0578 (5)
H14	0.3579	0.6417	0.1929	0.069*
C15	0.40929 (10)	0.57473 (13)	0.28425 (13)	0.0539 (5)
H15	0.4204	0.5345	0.2435	0.065*
C16	0.43038 (9)	0.57010 (12)	0.37372 (12)	0.0474 (4)
H16	0.4559	0.5263	0.3937	0.057*
N3	0.35733 (9)	0.75046 (11)	0.46079 (11)	0.0581 (4)
C17	0.33979 (10)	0.77941 (12)	0.52739 (14)	0.0531 (4)
S1	0.31534 (3)	0.82304 (4)	0.61376 (4)	0.07149 (18)
C18	0.73280 (8)	0.61190 (11)	0.64634 (11)	0.0422 (4)
C19	0.76769 (9)	0.67895 (11)	0.62281 (12)	0.0456 (4)
C20	0.83405 (10)	0.67559 (14)	0.59531 (14)	0.0564 (5)
H20	0.8569	0.7217	0.5787	0.068*
C21	0.86599 (10)	0.60474 (15)	0.59256 (15)	0.0617 (5)
H21	0.9114	0.6020	0.5748	0.074*
C22	0.83267 (11)	0.53773 (14)	0.61539 (16)	0.0629 (5)
H22	0.8551	0.4890	0.6131	0.075*
C23	0.76637 (10)	0.54120 (12)	0.64176 (14)	0.0529 (4)
H23	0.7436	0.4946	0.6569	0.063*
N4	0.73517 (9)	0.75053 (11)	0.62762 (13)	0.0587 (4)
C24	0.72587 (9)	0.81716 (12)	0.63222 (14)	0.0510 (4)
S2	0.71060 (3)	0.90666 (3)	0.63860 (5)	0.07015 (18)
O1	0.5000	0.76596 (11)	0.7500	0.0511 (4)
C31	0.54792 (10)	0.81107 (12)	0.70173 (15)	0.0555 (5)
H31A	0.5892	0.7798	0.6939	0.067*
H31B	0.5604	0.8578	0.7374	0.067*
C32	0.52032 (14)	0.83590 (17)	0.61075 (17)	0.0761 (7)
H32A	0.5068	0.7898	0.5759	0.114*
H32B	0.5550	0.8644	0.5788	0.114*
H32C	0.4812	0.8697	0.6184	0.114*
O2	0.9968 (9)	0.5749 (3)	0.7693 (6)	0.092 (3)	0.5
C41	1.0756 (8)	0.5710 (9)	0.6491 (11)	0.155 (6)	0.5
H41A	1.0997	0.6007	0.6059	0.233*	0.5
H41B	1.1070	0.5431	0.6873	0.233*	0.5
H41C	1.0464	0.5346	0.6182	0.233*	0.5
C42	1.0345 (7)	0.6237 (9)	0.7061 (9)	0.114 (4)	0.5
H42A	1.0636	0.6605	0.7364	0.136*	0.5
H42B	1.0035	0.6521	0.6679	0.136*	0.5
C43	0.9492 (8)	0.6115 (8)	0.8328 (10)	0.124 (5)	0.5
H43A	0.9091	0.6246	0.7988	0.148*	0.5
H43B	0.9660	0.6586	0.8600	0.148*	0.5
C44	0.9249 (6)	0.5580 (6)	0.8994 (8)	0.117 (3)	0.5
H44A	0.8920	0.5822	0.9363	0.176*	0.5
H44B	0.9064	0.5111	0.8736	0.176*	0.5
H44C	0.9642	0.5455	0.9356	0.176*	0.5

	U11	U22	U33	U12	U13	U23
Zn1	0.03477 (15)	0.04689 (17)	0.03351 (15)	0.000	0.00291 (10)	0.000
N1	0.0356 (7)	0.0494 (8)	0.0350 (7)	−0.0013 (6)	0.0024 (5)	0.0005 (6)
N2	0.0361 (7)	0.0477 (8)	0.0339 (7)	0.0002 (6)	0.0028 (5)	0.0001 (5)
C1	0.0360 (8)	0.0453 (9)	0.0404 (8)	−0.0008 (6)	0.0033 (6)	0.0012 (7)
C2	0.0384 (8)	0.0556 (10)	0.0440 (9)	−0.0045 (7)	0.0012 (7)	−0.0001 (8)
C3	0.0407 (9)	0.0590 (11)	0.0394 (8)	−0.0046 (7)	−0.0009 (7)	−0.0013 (7)
C4	0.0387 (8)	0.0468 (9)	0.0364 (8)	−0.0011 (7)	−0.0008 (6)	−0.0003 (7)
C5	0.0408 (8)	0.0458 (9)	0.0359 (8)	−0.0009 (7)	0.0016 (6)	−0.0009 (6)
C6	0.0419 (8)	0.0465 (9)	0.0332 (8)	−0.0009 (7)	0.0032 (6)	0.0005 (6)
C7	0.0429 (9)	0.0639 (11)	0.0350 (8)	−0.0039 (8)	0.0049 (7)	0.0007 (7)
C8	0.0408 (9)	0.0634 (11)	0.0382 (9)	−0.0031 (8)	0.0074 (7)	−0.0001 (8)
C9	0.0384 (8)	0.0464 (9)	0.0377 (8)	−0.0012 (7)	0.0066 (6)	−0.0003 (7)
C10	0.0380 (8)	0.0440 (8)	0.0401 (8)	−0.0010 (6)	0.0052 (6)	−0.0005 (7)
C11	0.0395 (8)	0.0507 (10)	0.0365 (8)	−0.0032 (7)	0.0013 (6)	−0.0006 (7)
C12	0.0472 (9)	0.0573 (11)	0.0393 (8)	0.0030 (8)	0.0031 (7)	−0.0016 (7)
C13	0.0524 (11)	0.0778 (14)	0.0431 (10)	0.0109 (10)	−0.0023 (8)	0.0054 (9)
C14	0.0482 (10)	0.0903 (16)	0.0346 (9)	0.0001 (10)	−0.0016 (7)	−0.0027 (9)
C15	0.0495 (10)	0.0705 (13)	0.0418 (9)	−0.0087 (9)	0.0040 (7)	−0.0132 (9)
C16	0.0465 (9)	0.0516 (10)	0.0443 (9)	−0.0033 (7)	0.0032 (7)	−0.0037 (7)
N3	0.0655 (10)	0.0604 (10)	0.0485 (9)	0.0124 (8)	0.0023 (7)	−0.0006 (8)
C17	0.0506 (10)	0.0545 (11)	0.0540 (11)	0.0066 (8)	−0.0021 (8)	0.0003 (9)
S1	0.0758 (4)	0.0729 (4)	0.0663 (4)	0.0059 (3)	0.0115 (3)	−0.0197 (3)
C18	0.0377 (8)	0.0522 (9)	0.0368 (8)	−0.0008 (7)	0.0036 (6)	−0.0005 (7)
C19	0.0423 (9)	0.0526 (10)	0.0417 (8)	−0.0045 (7)	−0.0004 (7)	−0.0002 (7)
C20	0.0430 (9)	0.0734 (13)	0.0529 (10)	−0.0128 (9)	0.0049 (8)	0.0062 (9)
C21	0.0389 (9)	0.0876 (16)	0.0592 (12)	0.0013 (10)	0.0104 (8)	0.0032 (11)
C22	0.0483 (10)	0.0702 (14)	0.0707 (13)	0.0137 (10)	0.0129 (9)	0.0031 (11)
C23	0.0463 (10)	0.0548 (11)	0.0579 (11)	0.0035 (8)	0.0105 (8)	0.0038 (8)
N4	0.0569 (10)	0.0526 (10)	0.0665 (11)	−0.0068 (8)	0.0004 (8)	0.0012 (8)
C24	0.0418 (9)	0.0569 (12)	0.0543 (10)	−0.0058 (8)	0.0004 (7)	0.0018 (8)
S2	0.0700 (4)	0.0529 (3)	0.0870 (4)	0.0033 (2)	−0.0071 (3)	−0.0033 (3)
O1	0.0499 (10)	0.0455 (10)	0.0586 (11)	0.000	0.0160 (8)	0.000
C31	0.0510 (10)	0.0541 (11)	0.0620 (12)	−0.0087 (8)	0.0112 (9)	0.0022 (9)
C32	0.0862 (18)	0.0802 (16)	0.0623 (14)	−0.0162 (14)	0.0082 (12)	0.0123 (12)
O2	0.073 (3)	0.087 (2)	0.116 (8)	0.005 (3)	−0.004 (7)	−0.006 (3)
C41	0.152 (10)	0.135 (10)	0.179 (13)	0.050 (8)	−0.008 (10)	−0.063 (9)
C42	0.091 (7)	0.125 (8)	0.122 (9)	−0.016 (5)	−0.039 (6)	0.025 (7)
C43	0.125 (11)	0.099 (8)	0.145 (13)	0.046 (7)	−0.036 (9)	−0.035 (8)
C44	0.108 (6)	0.071 (5)	0.175 (11)	−0.013 (4)	0.030 (7)	−0.002 (6)

Zn1—N2	2.0622 (13)	C20—C21	1.374 (3)
Zn1—N2i	2.0622 (13)	C20—H20	0.9500
Zn1—N1i	2.0684 (14)	C21—C22	1.376 (3)
Zn1—N1	2.0685 (14)	C21—H21	0.9500
Zn1—O1	2.1352 (19)	C22—C23	1.387 (3)
N1—C4	1.368 (2)	C22—H22	0.9500
N1—C1	1.370 (2)	C23—H23	0.9500
N2—C9	1.368 (2)	N4—C24	1.162 (3)
N2—C6	1.370 (2)	C24—S2	1.571 (2)
C1—C10i	1.397 (2)	O1—C31	1.436 (2)
C1—C2	1.443 (2)	O1—C31i	1.436 (2)
C2—C3	1.348 (2)	C31—C32	1.507 (3)
C2—H2	0.9500	C31—H31A	0.9900
C3—C4	1.440 (2)	C31—H31B	0.9900
C3—H3	0.9500	C32—H32A	0.9800
C4—C5	1.401 (2)	C32—H32B	0.9800
C5—C6	1.404 (2)	C32—H32C	0.9800
C5—C11	1.494 (2)	O2—C42ii	1.11 (2)
C6—C7	1.440 (2)	O2—C42	1.479 (12)
C7—C8	1.355 (3)	O2—C43	1.495 (11)
C7—H7	0.9500	O2—C41ii	1.912 (18)
C8—C9	1.440 (2)	C41—C44ii	0.755 (17)
C8—H8	0.9500	C41—C43ii	0.900 (18)
C9—C10	1.401 (2)	C41—C42	1.499 (14)
C10—C1i	1.397 (2)	C41—O2ii	1.912 (18)
C10—C18	1.494 (2)	C41—H41A	0.9600
C11—C16	1.391 (3)	C41—H41B	0.9599
C11—C12	1.398 (3)	C41—H41C	0.9600
C12—C13	1.390 (3)	C42—C43ii	0.703 (16)
C12—N3	1.393 (2)	C42—O2ii	1.11 (2)
C13—C14	1.370 (3)	C42—C42ii	1.92 (3)
C13—H13	0.9500	C42—H42A	0.9601
C14—C15	1.384 (3)	C42—H42B	0.9599
C14—H14	0.9500	C43—C42ii	0.703 (16)
C15—C16	1.385 (3)	C43—C41ii	0.900 (18)
C15—H15	0.9500	C43—C44	1.446 (14)
C16—H16	0.9500	C43—H43A	0.9599
N3—C17	1.170 (3)	C43—H43B	0.9600
C17—S1	1.576 (2)	C44—C41ii	0.755 (17)
C18—C23	1.389 (3)	C44—H44A	0.9600
C18—C19	1.394 (3)	C44—H44B	0.9600
C19—N4	1.392 (3)	C44—H44C	0.9599
C19—C20	1.394 (3)
N2—Zn1—N2i	164.44 (8)	C31—O1—Zn1	122.65 (11)
N2—Zn1—N1i	88.85 (6)	C31i—O1—Zn1	122.65 (11)
N2i—Zn1—N1i	88.54 (6)	O1—C31—C32	111.82 (17)
N2—Zn1—N1	88.54 (6)	O1—C31—H31A	109.3
N2i—Zn1—N1	88.85 (6)	C32—C31—H31A	109.3
N1i—Zn1—N1	160.61 (8)	O1—C31—H31B	109.3
N2—Zn1—O1	97.78 (4)	C32—C31—H31B	109.3
N2i—Zn1—O1	97.78 (4)	H31A—C31—H31B	107.9
N1i—Zn1—O1	99.69 (4)	C31—C32—H32A	109.5
N1—Zn1—O1	99.69 (4)	C31—C32—H32B	109.5
C4—N1—C1	106.50 (14)	H32A—C32—H32B	109.5
C4—N1—Zn1	126.59 (11)	C31—C32—H32C	109.5
C1—N1—Zn1	126.82 (11)	H32A—C32—H32C	109.5
C9—N2—C6	106.88 (13)	H32B—C32—H32C	109.5
C9—N2—Zn1	126.26 (11)	C42ii—O2—C42	94.7 (13)
C6—N2—Zn1	126.16 (11)	C42ii—O2—C43	26.4 (9)
N1—C1—C10i	125.29 (15)	C42—O2—C43	120.3 (9)
N1—C1—C2	109.66 (14)	C42ii—O2—C41ii	51.6 (8)
C10i—C1—C2	125.05 (16)	C42—O2—C41ii	146.0 (10)
C3—C2—C1	106.91 (15)	C43—O2—C41ii	27.3 (8)
C3—C2—H2	126.5	C44ii—C41—C43ii	122 (3)
C1—C2—H2	126.5	C44ii—C41—C42	137 (3)
C2—C3—C4	107.20 (15)	C43ii—C41—C42	18.1 (13)
C2—C3—H3	126.4	C44ii—C41—O2ii	129 (2)
C4—C3—H3	126.4	C43ii—C41—O2ii	49.6 (12)
N1—C4—C5	125.53 (15)	C42—C41—O2ii	35.6 (7)
N1—C4—C3	109.70 (14)	C44ii—C41—H41A	60.7
C5—C4—C3	124.76 (16)	C43ii—C41—H41A	94.4
C4—C5—C6	125.25 (16)	C42—C41—H41A	110.3
C4—C5—C11	117.74 (15)	O2ii—C41—H41A	143.7
C6—C5—C11	116.99 (15)	C44ii—C41—H41B	114.2
N2—C6—C5	125.30 (15)	C43ii—C41—H41B	124.1
N2—C6—C7	109.32 (15)	C42—C41—H41B	108.7
C5—C6—C7	125.28 (16)	O2ii—C41—H41B	97.5
C8—C7—C6	107.28 (16)	H41A—C41—H41B	109.5
C8—C7—H7	126.4	C44ii—C41—H41C	50.2
C6—C7—H7	126.4	C43ii—C41—H41C	108.5
C7—C8—C9	106.85 (15)	C42—C41—H41C	109.4
C7—C8—H8	126.6	O2ii—C41—H41C	82.6
C9—C8—H8	126.6	H41A—C41—H41C	109.5
N2—C9—C10	125.61 (15)	H41B—C41—H41C	109.5
N2—C9—C8	109.64 (15)	C43ii—C42—O2ii	109 (2)
C10—C9—C8	124.73 (16)	C43ii—C42—O2	127 (2)
C1i—C10—C9	125.76 (16)	O2ii—C42—O2	20.8 (8)
C1i—C10—C18	116.90 (15)	C43ii—C42—C41	23 (2)
C9—C10—C18	117.33 (15)	O2ii—C42—C41	92.9 (12)
C16—C11—C12	117.55 (16)	O2—C42—C41	108.1 (13)
C16—C11—C5	120.98 (17)	C43ii—C42—C42ii	156 (3)
C12—C11—C5	121.45 (16)	O2ii—C42—C42ii	50.1 (8)
C13—C12—N3	117.92 (18)	O2—C42—C42ii	35.3 (7)
C13—C12—C11	121.16 (18)	C41—C42—C42ii	142.7 (10)
N3—C12—C11	120.92 (16)	C43ii—C42—H42A	107.4
C14—C13—C12	119.9 (2)	O2ii—C42—H42A	132.6
C14—C13—H13	120.0	O2—C42—H42A	112.6
C12—C13—H13	120.0	C41—C42—H42A	109.5
C13—C14—C15	120.15 (18)	C42ii—C42—H42A	96.5
C13—C14—H14	119.9	C43ii—C42—H42B	88.1
C15—C14—H14	119.9	O2ii—C42—H42B	102.7
C14—C15—C16	119.83 (18)	O2—C42—H42B	109.6
C14—C15—H15	120.1	C41—C42—H42B	108.8
C16—C15—H15	120.1	C42ii—C42—H42B	86.7
C15—C16—C11	121.34 (19)	H42A—C42—H42B	108.1
C15—C16—H16	119.3	C42ii—C43—C41ii	138 (3)
C11—C16—H16	119.3	C42ii—C43—C44	158 (2)
C17—N3—C12	157.6 (2)	C41ii—C43—C44	26.4 (16)
N3—C17—S1	176.6 (2)	C42ii—C43—O2	44.9 (18)
C23—C18—C19	117.82 (16)	C41ii—C43—O2	103.2 (17)
C23—C18—C10	121.48 (16)	C44—C43—O2	113.4 (10)
C19—C18—C10	120.68 (17)	C42ii—C43—H43A	83.7
N4—C19—C20	119.79 (18)	C41ii—C43—H43A	83.3
N4—C19—C18	118.78 (16)	C44—C43—H43A	102.7
C20—C19—C18	121.44 (19)	O2—C43—H43A	107.3
C21—C20—C19	119.2 (2)	C42ii—C43—H43B	86.1
C21—C20—H20	120.4	C41ii—C43—H43B	135.5
C19—C20—H20	120.4	C44—C43—H43B	111.5
C20—C21—C22	120.49 (18)	O2—C43—H43B	113.6
C20—C21—H21	119.8	H43A—C43—H43B	107.3
C22—C21—H21	119.8	C41ii—C44—C43	32.0 (18)
C21—C22—C23	120.1 (2)	C41ii—C44—H44A	115.3
C21—C22—H22	119.9	C43—C44—H44A	111.3
C23—C22—H22	119.9	C41ii—C44—H44B	82.6
C22—C23—C18	120.90 (19)	C43—C44—H44B	113.0
C22—C23—H23	119.5	H44A—C44—H44B	109.5
C18—C23—H23	119.5	C41ii—C44—H44C	126.1
C24—N4—C19	161.5 (2)	C43—C44—H44C	104.0
N4—C24—S2	178.01 (19)	H44A—C44—H44C	109.5
C31—O1—C31i	114.7 (2)	H44B—C44—H44C	109.5