(4-Amino­pyridine-κN¹)(phthalo­cyan­inato-κ⁴N)zinc(II) tetra­hydro­furan disolvate

The title compound, [Zn(C₃₂H₁₆N₈)(C₅H₆N₂)]·2C₄H₈O, con­sists of one (phthalocyaninato)zinc (ZnPc) unit, a coordinated 4-amino­pyridine (4-ap) mol­ecule and two tetra­hydro­furan (THF) solvent mol­ecules. The central Zn atom is (4+1)-coordinated by four isoindole N atoms of the Pc core and by the pyridine N atom of 4-amino­pyridine. The Zn atom is displaced by 0.4464 (8) Å from the isoindole N₄ plane towards the pyridine N atom. The crystal structure is stabilized by inter­molecular amine–phthalocyaninate N—H...N hydrogen bonds and π–π inter­actions between the aggregated Pc rings, which form mol­ecular layers, and by weak van der Waals inter­actions between the layers. As well as hindering the aggregation of ZnPc mol­ecules by occupying an axial position, the amino group will add new inter­actions which will favor applications of ZnPc, for example, as a sensitizer of photo­dynamic therapy.

S1. Comment

It is well known that phthalocyanines exhibit interesting optical, electrical, magnetic and catalytic properties, and they are widely used in many fields, such as dyes, catalysts, molecular materials, chemical sensors, nonlinear optical materials, etc. (Kadish et al., 2003; Mckeown, 1998; Torre et al., 2001). Among those phthalocyanine compounds, the phthalocyaninatozinc (ZnPc) derivatives are particularly interesting owing to their unique photosensitizing properties for photodynamic therapy (PDT) (Lukyanets, 1999; Tabata et al., 2000; Milgrom, 1977; Bonnett, 1995), magnetic circularly polarized luminescence (MCPL) and magnetic circular dichroism (MCD) spectra. Our interest in ZnPc derivatives is due to their photodynamic activity. Some crystal structures of (4+1)-coordinated ZnPc derivatives, such as ZnPc(n-hexylamine), ZnPcCl, ZnPc(dipy–pra) (dipy-pra is 1,3-di-4-pyridylpropane), ZnPc[(di/tetra/hexa/octaphenyl-py)], [ZnPc(H₂O)].2DMF (DMF is dimethylformamide) and ZnPc(4-Mepy) (4-Mepy is ?) have been reported (Kobayashi et al., 1971; Deneux et al., 1985; Zeng et al., 2005; Fukuda et al., 2005; Cui et al., 2007; Kubiak et al., 2007). In this paper, we report the structure of the title compound, (I), produced by the reaction of 4-aminopyridine with zinc phthalocyanine in tetrahydrofuran (THF) solution. UV–vis and fluorescence spectral measurements and thermal gravimetric analysis were also applied to characterize this complex.

The asymmetric unit of (I) consists of a (4-aminopyridine-κN¹)(phthalocyaninato-κ⁴N)zinc(II) unit, denoted ZnPc(4-ap), and two THF solvent molecules (one of the THF molecules shows disorder) (Fig. 1). The central Zn^II atom exhibits (4+1)-coordination by four isoindole N atoms of the Pc ring system and one pyridine N atom of the 4-aminopyridine molecule, forming a distorted pyramid (Table 1). The Zn atom in this coordination environment assumes an sp²d² hybridization. The bond distances from the azamethine N atoms of the Pc ring to the central Zn atom range from 2.0275 (15) to 2.0343 (15)Å, whereas that from the pyridine N atom of the axial ligand is somewhat longer at 2.0917 (16)Å. The angle between the basal Pc plane defined by the four isoindole N atoms (the N₄ plane) and the plane of the coordinated 4-aminopyridine molecule is 87.7(?)°, thus the 4-aminopyridine molecule is almost perpendicular to the Pc plane. The central Zn atom is significantly displaced (by about 0.45Å) from the N₄ plane towards the axially coordinated N atom of the 4-aminopyridine molecule.

For axially coordinated ZnPc complexes, a range of values have been observed for the distance between the Zn^II cation and the N₄ plane, and is related to the bond strength between the metal cation and the axial ligand. For example, the Zn atom is displaced from the N₄ plane as follows: 0.2Å in ZnPc(dipy–pra), 0.35Å in ZnPc(4-Mepy), 0.38Å in ZnPc(H₂O).2DMF, 0.48Å in ZnPc(n-hexylamine) and 0.59Å in ZnPcCl (Zeng et al., 2005; Kubiak et al., 2007; Cui et al., 2007; Kobayashi et al., 1971; Deneux et al., 1985); the displacement is 0.45Å in compound (I). Additionally, the Pc ring is distorted from planarity, with small angles between the benzene rings and the N₄ plane of 8.30 (13), 4.55 (10), 4.22 (10) and 7.56 (12)° for the C2/C3/C17–C20, C6/C7/C21–C24, C10/C11/C25–C28 and C14/C15/C29–C32 rings, respectively. The small differences of these angles are related to the aggregation of the Pc rings, where the less overlapped benzene rings have slightly larger distortion angles.

The crystal structure of (I) is stabilized by hydrogen bonds and π–π interactions between Pc rings. The hydrogen-bonding interactions occur between the azamethine N2 and N6 atoms of the Pc ring as acceptors and the amino group of the 4-aminopyridine molecule as donor (Fig. 2 and Table 2). These intermolecular hydrogen bonds construct an infinite two-dimensional layer in the bc plane. Concurrently, in the two-dimensional layer, the Pc rings are aggregated in a back-to-back fashion, with a distance of 3.56Å and centre offset of 3.15Å of the two stacked N₄ planes, which indicates a strong intermolecular π–π interaction (Pauling, 1960). Finally, the THF molecules occupy the space around the axial 4-aminopyridine ligands (Figs. 1 and 3).

As further characterizations of compound (I), the electronic absorption spectrum was recorded in DMF solution. It showed intense absorption in the UV region (B band, 343 nm) and visible–IR region (Q band, 669 nm). Compared with the corresponding bands of ZnPc (340 and 669 nm), a slight red shift in the B band occurs in compound (I), but the Q band is at the same position which indicates the axial ligand has less influence on the Pc π system. In the UV–visible diffuse reflectance spectra of the solid sample, bands at 570 and 649 nm appeared and correspond to the dimeric aggregate of molecules.

ZnPc derivatives all display strong fluorescences. Compound (I) in DMF solution exhibits two emission peaks at about 679 and 739 nm (λ_ex = 617 nm). In contrast to the emission wavelength (676 and 743 nm) of unsubstituted ZnPc, the small red (3 nm) and blue (4 nm) shifts can be related to the presence of the axial ligand (Ogunsipe et al., 2003; Yslas et al., 2005; Nitschke et al., 2004).

The thermogravimetric analysis shows two characteristic steps, the first at about 339 K corresponds to the loss of the THF molecules (12.26%) and the second at about 448 K correlates with the loss of 4-aminopyridine. Finally, above 571 K, the sample decomposes.

Related literature

For related literature, see: Bonnett (1995); Cui et al. (2007); Deneux et al. (1985); Kadish et al. (2003); Kobayashi et al. (1968, 1971); Kubiak et al. (2007); Lukyanets (1999); Mckeown (1998); Milgrom (1977); Nitschke et al. (2004); Ogunsipe et al. (2003); Pauling (1960); Tabata et al. (2000); Torre et al. (2001); Yslas et al. (2005); Zeng et al. (2005).

S2. Experimental

Pure zinc(II) phthalocyanine was prepared according to the procedure of Kobayashi et al. (1968). ZnPc powder was reacted with 4-aminopyridine (2:3 molar ratio) in THF solution at about 338 K for 6 h. When the solvent was evaporated slowly at room temperature, violet crystals were obtained in various sizes.

S3. Refinement

All H atoms bound to C and N atoms of the ZnPc(4-ap) unit were located in difference Fourier syntheses and refined. The H atoms of THF solvent molecules were refined as riding, with C—H = 0.97Å and U_iso(H) = 1.2U_eq(C). One THF molecule (C42–C46/O2A–O2E) was disordered and treated statistically with the site-occupancy factors of the C atoms at each of the five sites equal to 0.8 and the site-occupancy factors of the O atoms to equal 0.2.

Computing details

Data collection: CrystalClear (Rigaku, 2007); cell refinement: CrystalClear (Rigaku, 2007); data reduction: CrystalClear (Rigaku, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEX (McArdle, 1995); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The crystal structure of compound (I), drawn with 50% probability displacement ellipsoids. H atoms are shown as spheres of arbitrary radii.
	Fig. 2. A view of the hydrogen-bonded structure of compound (I) and the back-to-back π–π interactions between the ZnPc(4-ap) molecules. All H atoms attached to the C atoms and the THF solvent molecules have been omitted for clarity. [Symmetry codes: (i) -x+1, y-1/2, -z+1/2; (ii) -x+1, -y+1, -z.] [Atom labels should relate to atoms as they appear in the coordinate list; if there are duplicate atom labels (here N10, then symmetry codes should be given]
	Fig. 3. The molecular packing of compound (I), showing the positions of the THF solvent molecules around the 4-aminopyridine ligands. H atoms have been omitted for clarity.

(4-Aminopyridine-κN¹)(phthalocyaninato-κ⁴N)zinc(II) tetrahydrofuran disolvate

Crystal data

[Zn(C32H16N8)(C5H6N2)]·2C4H8O	F(000) = 1696
Mr = 816.22	Dx = 1.405 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -p2ybc	Cell parameters from 11377 reflections
a = 13.5385 (17) Å	θ = 3.1–27.5°
b = 15.0756 (19) Å	µ = 0.69 mm^−1
c = 19.224 (3) Å	T = 298 K
β = 100.420 (3)°	Block, purple
V = 3858.9 (9) Å^3	0.72 × 0.70 × 0.20 mm
Z = 4

Data collection

Rigaku Saturn 724 CCD area-detector diffractometer	8842 independent reflections
Radiation source: Sealed Tube	8208 reflections with I > 2σ(I)
Graphite Monochromator monochromator	Rint = 0.028
Detector resolution: 28.5714 pixels mm^-1	θmax = 27.5°, θmin = 3.1°
dtprofit.ref scans	h = −17→17
Absorption correction: numerical (NUMABS; Higashi, 2000)	k = −19→15
Tmin = 0.636, Tmax = 0.874	l = −24→24
30133 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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.121	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0691P)^2 + 1.4255P] where P = (Fo^2 + 2Fc^2)/3
8842 reflections	(Δ/σ)max < 0.001
611 parameters	Δρmax = 0.37 e Å^−3
0 restraints	Δρmin = −0.44 e Å^−3

Special details

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

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

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Zn1	0.494339 (15)	0.814615 (13)	0.007637 (10)	0.03414 (8)
N1	0.60057 (11)	0.89636 (10)	0.06164 (8)	0.0366 (3)
N2	0.49768 (12)	0.98717 (10)	0.12432 (8)	0.0371 (3)
N3	0.39134 (12)	0.89932 (10)	0.03483 (8)	0.0368 (3)
N4	0.24176 (12)	0.84110 (11)	−0.04029 (8)	0.0396 (3)
N5	0.38907 (12)	0.77725 (10)	−0.07659 (8)	0.0375 (3)
N6	0.49267 (13)	0.69864 (11)	−0.14683 (9)	0.0411 (3)
N7	0.59833 (12)	0.77482 (10)	−0.05010 (8)	0.0377 (3)
N8	0.74782 (12)	0.83266 (11)	0.02523 (9)	0.0398 (3)
N9	0.49501 (13)	0.70958 (11)	0.07882 (8)	0.0394 (3)
N10	0.50518 (17)	0.49473 (13)	0.21647 (10)	0.0494 (4)
H1	0.6517 (19)	0.6260 (17)	−0.2210 (14)	0.055 (7)*
H2	0.824 (3)	0.607 (2)	−0.219 (2)	0.098 (11)*
H3	0.948 (3)	0.658 (2)	−0.1287 (19)	0.096 (11)*
H4	0.9000 (19)	0.7376 (17)	−0.0362 (14)	0.052 (7)*
H5	0.904 (2)	0.9301 (18)	0.1226 (15)	0.064 (8)*
H6	0.956 (2)	1.0338 (19)	0.2076 (14)	0.059 (7)*
H7	0.836 (2)	1.1111 (18)	0.2594 (14)	0.062 (7)*
H8	0.6617 (18)	1.0850 (15)	0.2224 (13)	0.049 (6)*
H9	0.3413 (18)	1.0897 (15)	0.1806 (13)	0.047 (6)*
H10	0.1682 (19)	1.1180 (18)	0.1749 (14)	0.059 (7)*
H11	0.042 (2)	1.0512 (19)	0.0915 (16)	0.071 (8)*
H12	0.0845 (19)	0.9411 (16)	0.0155 (14)	0.052 (6)*
H13	0.087 (2)	0.7601 (19)	−0.1469 (15)	0.065 (8)*
H14	0.034 (3)	0.680 (2)	−0.250 (2)	0.091 (11)*
H15	0.156 (2)	0.6099 (19)	−0.3072 (16)	0.069 (8)*
H16	0.326 (2)	0.6251 (18)	−0.2585 (15)	0.064 (8)*
H18	0.4943 (19)	0.607 (2)	0.0078 (15)	0.070 (9)*
H19	0.510 (2)	0.4937 (18)	0.0836 (17)	0.071 (9)*
H20	0.504 (2)	0.6622 (19)	0.2484 (16)	0.066 (8)*
H21	0.4953 (17)	0.7831 (17)	0.1657 (13)	0.049 (6)*
H22	0.5053 (18)	0.4447 (19)	0.1987 (14)	0.052 (7)*
H23	0.5023 (19)	0.5051 (14)	0.2583 (15)	0.043 (6)*
C1	0.58133 (15)	0.72320 (12)	−0.10938 (10)	0.0390 (4)
C2	0.67786 (16)	0.69605 (13)	−0.12667 (12)	0.0451 (4)
C3	0.75222 (15)	0.73163 (13)	−0.07361 (11)	0.0440 (4)
C4	0.69970 (14)	0.78330 (13)	−0.02784 (10)	0.0385 (4)
C5	0.70146 (13)	0.88605 (12)	0.06430 (9)	0.0365 (4)
C6	0.75602 (14)	0.94474 (13)	0.11841 (10)	0.0391 (4)
C7	0.68352 (15)	0.99013 (12)	0.14787 (9)	0.0380 (4)
C8	0.58565 (14)	0.95808 (12)	0.11073 (9)	0.0361 (4)
C9	0.40856 (14)	0.96048 (12)	0.08796 (9)	0.0361 (4)
C10	0.31258 (15)	0.99527 (12)	0.10078 (10)	0.0383 (4)
C11	0.23774 (14)	0.95227 (13)	0.05241 (10)	0.0388 (4)
C12	0.29005 (14)	0.89225 (12)	0.01157 (9)	0.0372 (4)
C13	0.28828 (14)	0.79021 (13)	−0.08109 (10)	0.0381 (4)
C14	0.23424 (15)	0.74082 (13)	−0.14152 (10)	0.0430 (4)
C15	0.30755 (16)	0.70100 (14)	−0.17432 (11)	0.0437 (4)
C16	0.40432 (15)	0.72503 (12)	−0.13171 (9)	0.0387 (4)
C17	0.7034 (2)	0.64863 (18)	−0.18321 (15)	0.0634 (7)
C18	0.8045 (2)	0.6356 (2)	−0.18268 (18)	0.0789 (9)
C19	0.8781 (2)	0.6678 (2)	−0.12830 (19)	0.0745 (9)
C20	0.85346 (19)	0.71677 (17)	−0.07302 (15)	0.0576 (6)
C21	0.85777 (16)	0.96046 (16)	0.13991 (11)	0.0468 (5)
C22	0.88577 (18)	1.02301 (17)	0.19271 (12)	0.0531 (5)
C23	0.81376 (18)	1.06793 (15)	0.22266 (11)	0.0522 (5)
C24	0.71187 (17)	1.05294 (14)	0.20101 (11)	0.0455 (4)
C25	0.28706 (17)	1.05824 (14)	0.14744 (11)	0.0454 (4)
C26	0.18597 (18)	1.07645 (16)	0.14411 (12)	0.0519 (5)
C27	0.11215 (17)	1.03436 (17)	0.09559 (12)	0.0514 (5)
C28	0.13663 (16)	0.97115 (16)	0.04904 (11)	0.0468 (4)
C29	0.13270 (18)	0.73232 (16)	−0.16919 (13)	0.0536 (5)
C30	0.1063 (2)	0.68400 (18)	−0.23102 (17)	0.0683 (7)
C31	0.1791 (2)	0.6457 (2)	−0.26458 (15)	0.0712 (8)
C32	0.2801 (2)	0.65378 (18)	−0.23701 (13)	0.0584 (6)
C33	0.49547 (16)	0.72070 (13)	0.14844 (10)	0.0420 (4)
C34	0.49830 (16)	0.65237 (14)	0.19593 (10)	0.0428 (4)
C35	0.50135 (14)	0.56446 (13)	0.17249 (10)	0.0390 (4)
C36	0.5012 (2)	0.55329 (14)	0.10033 (11)	0.0518 (5)
C37	0.4983 (2)	0.62568 (15)	0.05711 (11)	0.0522 (5)
O1	0.9274 (3)	0.6289 (3)	0.1933 (2)	0.1560 (15)
C38	0.8636 (4)	0.6944 (3)	0.1720 (4)	0.147 (2)
H38A	0.8839	0.7261	0.1329	0.177*
H38B	0.8622	0.7359	0.2103	0.177*
C39	0.7646 (4)	0.6545 (5)	0.1495 (5)	0.187 (4)
H39A	0.7254	0.6578	0.1870	0.224*
H39B	0.7281	0.6842	0.1080	0.224*
C40	0.7848 (5)	0.5645 (6)	0.1340 (5)	0.216 (4)
H40A	0.7473	0.5243	0.1589	0.259*
H40B	0.7667	0.5532	0.0836	0.259*
C41	0.8897 (5)	0.5539 (5)	0.1575 (5)	0.208 (4)
H41A	0.9023	0.5027	0.1884	0.250*
H41B	0.9225	0.5443	0.1173	0.250*
C42	0.0725 (5)	0.6335 (7)	0.0275 (5)	0.206 (4)	0.80
H42A	0.0092	0.6206	0.0424	0.247*	0.80
H42B	0.0584	0.6532	−0.0213	0.247*	0.80
C43	0.1259 (9)	0.5667 (8)	0.0331 (9)	0.380 (11)	0.80
H43A	0.1232	0.5418	−0.0137	0.456*	0.80
H43B	0.0971	0.5233	0.0609	0.456*	0.80
C44	0.2250 (6)	0.5784 (7)	0.0634 (8)	0.289 (6)	0.80
H44A	0.2683	0.5740	0.0285	0.346*	0.80
H44B	0.2463	0.5354	0.1007	0.346*	0.80
C45	0.2252 (5)	0.6685 (6)	0.0920 (4)	0.185 (3)	0.80
H45A	0.2425	0.6688	0.1432	0.222*	0.80
H45B	0.2712	0.7069	0.0727	0.222*	0.80
C46	0.1209 (5)	0.6945 (4)	0.0675 (6)	0.199 (4)	0.80
H46A	0.0887	0.7045	0.1080	0.239*	0.80
H46B	0.1188	0.7496	0.0412	0.239*	0.80
O2A	0.0725 (5)	0.6335 (7)	0.0275 (5)	0.206 (4)	0.20
O2B	0.1259 (9)	0.5667 (8)	0.0331 (9)	0.380 (11)	0.20
O2C	0.2250 (6)	0.5784 (7)	0.0634 (8)	0.289 (6)	0.20
O2D	0.2252 (5)	0.6685 (6)	0.0920 (4)	0.185 (3)	0.20
O2E	0.1209 (5)	0.6945 (4)	0.0675 (6)	0.199 (4)	0.20

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.03702 (13)	0.03550 (13)	0.03001 (12)	−0.00072 (7)	0.00635 (8)	−0.00258 (7)
N1	0.0385 (8)	0.0379 (8)	0.0341 (7)	−0.0023 (6)	0.0079 (6)	−0.0028 (6)
N2	0.0427 (8)	0.0374 (8)	0.0312 (7)	−0.0009 (6)	0.0068 (6)	−0.0014 (6)
N3	0.0400 (8)	0.0370 (8)	0.0334 (7)	0.0013 (6)	0.0063 (6)	−0.0027 (6)
N4	0.0405 (8)	0.0418 (8)	0.0359 (8)	−0.0017 (7)	0.0052 (6)	−0.0016 (6)
N5	0.0415 (8)	0.0401 (8)	0.0304 (7)	−0.0017 (6)	0.0052 (6)	−0.0039 (6)
N6	0.0495 (9)	0.0410 (8)	0.0336 (8)	−0.0022 (7)	0.0097 (7)	−0.0057 (6)
N7	0.0410 (8)	0.0416 (8)	0.0315 (7)	−0.0018 (6)	0.0092 (6)	−0.0038 (6)
N8	0.0395 (8)	0.0433 (8)	0.0377 (8)	−0.0020 (6)	0.0099 (6)	−0.0018 (6)
N9	0.0497 (9)	0.0368 (7)	0.0321 (7)	−0.0015 (7)	0.0084 (6)	0.0008 (6)
N10	0.0706 (13)	0.0404 (10)	0.0377 (9)	−0.0017 (8)	0.0111 (9)	0.0041 (7)
C1	0.0476 (10)	0.0365 (9)	0.0351 (8)	−0.0016 (7)	0.0136 (7)	−0.0036 (7)
C2	0.0495 (11)	0.0423 (10)	0.0475 (11)	−0.0049 (8)	0.0191 (9)	−0.0078 (8)
C3	0.0472 (10)	0.0407 (10)	0.0477 (10)	−0.0014 (8)	0.0182 (8)	−0.0051 (8)
C4	0.0402 (9)	0.0400 (9)	0.0371 (9)	0.0001 (7)	0.0119 (7)	0.0003 (7)
C5	0.0383 (9)	0.0385 (9)	0.0331 (8)	−0.0053 (7)	0.0077 (7)	0.0007 (7)
C6	0.0429 (9)	0.0413 (9)	0.0331 (8)	−0.0079 (7)	0.0069 (7)	0.0014 (7)
C7	0.0443 (10)	0.0381 (9)	0.0311 (8)	−0.0077 (7)	0.0056 (7)	0.0011 (7)
C8	0.0429 (9)	0.0352 (9)	0.0307 (8)	−0.0041 (7)	0.0081 (7)	−0.0009 (6)
C9	0.0435 (9)	0.0346 (9)	0.0309 (8)	0.0026 (7)	0.0088 (7)	0.0000 (6)
C10	0.0443 (10)	0.0379 (9)	0.0334 (8)	0.0048 (7)	0.0088 (7)	0.0027 (7)
C11	0.0416 (9)	0.0414 (9)	0.0344 (8)	0.0042 (7)	0.0091 (7)	0.0034 (7)
C12	0.0401 (9)	0.0400 (9)	0.0316 (8)	0.0018 (7)	0.0072 (7)	0.0022 (7)
C13	0.0407 (9)	0.0391 (9)	0.0336 (8)	−0.0035 (7)	0.0045 (7)	0.0001 (7)
C14	0.0476 (10)	0.0391 (9)	0.0398 (9)	−0.0050 (8)	0.0012 (8)	−0.0023 (7)
C15	0.0490 (11)	0.0415 (10)	0.0386 (10)	−0.0017 (8)	0.0025 (8)	−0.0038 (8)
C16	0.0478 (10)	0.0364 (9)	0.0310 (8)	−0.0017 (7)	0.0050 (7)	−0.0024 (7)
C17	0.0639 (15)	0.0660 (15)	0.0673 (15)	−0.0122 (12)	0.0307 (12)	−0.0283 (13)
C18	0.0701 (17)	0.0806 (19)	0.097 (2)	−0.0120 (14)	0.0456 (16)	−0.0448 (17)
C19	0.0558 (14)	0.0710 (17)	0.107 (2)	−0.0051 (12)	0.0417 (16)	−0.0308 (16)
C20	0.0488 (12)	0.0564 (13)	0.0714 (16)	−0.0033 (10)	0.0211 (11)	−0.0130 (12)
C21	0.0445 (10)	0.0541 (12)	0.0421 (10)	−0.0114 (9)	0.0089 (8)	0.0004 (9)
C22	0.0502 (12)	0.0636 (13)	0.0440 (11)	−0.0214 (10)	0.0046 (9)	−0.0006 (10)
C23	0.0632 (13)	0.0518 (12)	0.0401 (10)	−0.0207 (10)	0.0050 (9)	−0.0062 (9)
C24	0.0558 (12)	0.0422 (10)	0.0388 (9)	−0.0105 (9)	0.0093 (8)	−0.0054 (8)
C25	0.0550 (12)	0.0439 (10)	0.0380 (9)	0.0067 (9)	0.0099 (9)	−0.0028 (8)
C26	0.0601 (13)	0.0534 (12)	0.0451 (11)	0.0164 (10)	0.0173 (10)	0.0000 (9)
C27	0.0464 (11)	0.0608 (13)	0.0495 (11)	0.0136 (10)	0.0153 (9)	0.0058 (10)
C28	0.0431 (10)	0.0557 (12)	0.0419 (10)	0.0054 (9)	0.0089 (8)	0.0038 (9)
C29	0.0455 (11)	0.0537 (13)	0.0582 (13)	−0.0059 (9)	0.0003 (10)	−0.0087 (10)
C30	0.0546 (14)	0.0703 (17)	0.0718 (17)	−0.0057 (11)	−0.0100 (13)	−0.0217 (13)
C31	0.0713 (17)	0.0733 (17)	0.0603 (15)	−0.0037 (13)	−0.0112 (13)	−0.0276 (13)
C32	0.0627 (14)	0.0597 (14)	0.0483 (12)	0.0004 (11)	−0.0017 (10)	−0.0179 (11)
C33	0.0541 (11)	0.0378 (10)	0.0348 (9)	0.0004 (8)	0.0095 (8)	−0.0031 (7)
C34	0.0537 (11)	0.0432 (10)	0.0320 (9)	−0.0007 (8)	0.0093 (8)	−0.0036 (7)
C35	0.0420 (9)	0.0397 (9)	0.0353 (9)	−0.0014 (7)	0.0072 (7)	0.0010 (7)
C36	0.0841 (16)	0.0357 (10)	0.0372 (10)	−0.0012 (10)	0.0154 (10)	−0.0045 (8)
C37	0.0827 (16)	0.0433 (11)	0.0321 (9)	−0.0032 (10)	0.0147 (9)	−0.0030 (8)
O1	0.108 (2)	0.160 (3)	0.178 (4)	−0.001 (2)	−0.031 (2)	0.046 (3)
C38	0.100 (3)	0.120 (4)	0.216 (7)	0.004 (3)	0.009 (4)	0.045 (4)
C39	0.072 (3)	0.182 (6)	0.294 (9)	0.004 (3)	0.001 (4)	0.136 (7)
C40	0.123 (5)	0.190 (7)	0.297 (11)	−0.014 (5)	−0.065 (6)	−0.020 (7)
C41	0.124 (5)	0.145 (5)	0.332 (12)	0.010 (4)	−0.021 (6)	−0.058 (7)
C42	0.114 (5)	0.246 (9)	0.222 (7)	−0.017 (5)	−0.066 (5)	0.017 (7)
C43	0.182 (10)	0.255 (13)	0.65 (3)	0.013 (9)	−0.070 (14)	−0.153 (15)
C44	0.104 (5)	0.232 (9)	0.52 (2)	0.021 (6)	0.020 (8)	−0.012 (11)
C45	0.121 (5)	0.244 (8)	0.179 (6)	−0.067 (5)	−0.003 (4)	0.055 (6)
C46	0.108 (4)	0.168 (6)	0.321 (11)	−0.017 (4)	0.038 (6)	0.010 (6)
O2A	0.114 (5)	0.246 (9)	0.222 (7)	−0.017 (5)	−0.066 (5)	0.017 (7)
O2B	0.182 (10)	0.255 (13)	0.65 (3)	0.013 (9)	−0.070 (14)	−0.153 (15)
O2C	0.104 (5)	0.232 (9)	0.52 (2)	0.021 (6)	0.020 (8)	−0.012 (11)
O2D	0.121 (5)	0.244 (8)	0.179 (6)	−0.067 (5)	−0.003 (4)	0.055 (6)
O2E	0.108 (4)	0.168 (6)	0.321 (11)	−0.017 (4)	0.038 (6)	0.010 (6)

Geometric parameters (Å, º)

Zn1—N3	2.0278 (15)	C22—C23	1.394 (4)
Zn1—N1	2.0311 (15)	C22—H6	0.96 (3)
Zn1—N5	2.0335 (15)	C23—C24	1.385 (3)
Zn1—N7	2.0345 (15)	C23—H7	0.97 (3)
Zn1—N9	2.0917 (16)	C24—H8	0.98 (2)
N1—C8	1.366 (2)	C25—C26	1.386 (3)
N1—C5	1.366 (2)	C25—H9	1.00 (2)
N2—C8	1.339 (2)	C26—C27	1.391 (4)
N2—C9	1.342 (2)	C26—H10	0.92 (3)
N3—C9	1.364 (2)	C27—C28	1.388 (3)
N3—C12	1.367 (2)	C27—H11	0.98 (3)
N4—C13	1.334 (3)	C28—H12	0.98 (3)
N4—C12	1.334 (2)	C29—C30	1.385 (4)
N5—C16	1.365 (2)	C29—H13	0.92 (3)
N5—C13	1.366 (2)	C30—C31	1.397 (4)
N6—C1	1.335 (3)	C30—H14	0.99 (4)
N6—C16	1.341 (3)	C31—C32	1.380 (4)
N7—C1	1.365 (2)	C31—H15	0.98 (3)
N7—C4	1.368 (2)	C32—H16	0.92 (3)
N8—C5	1.333 (2)	C33—C34	1.372 (3)
N8—C4	1.334 (2)	C33—H21	1.00 (2)
N9—C37	1.335 (3)	C34—C35	1.403 (3)
N9—C33	1.348 (2)	C34—H20	1.01 (3)
N10—C35	1.344 (3)	C35—C36	1.397 (3)
N10—H22	0.83 (3)	C36—C37	1.368 (3)
N10—H23	0.83 (3)	C36—H19	0.97 (3)
C1—C2	1.464 (3)	C37—H18	0.98 (3)
C2—C17	1.396 (3)	O1—C38	1.327 (5)
C2—C3	1.404 (3)	O1—C41	1.373 (7)
C3—C20	1.387 (3)	C38—C39	1.462 (7)
C3—C4	1.454 (3)	C38—H38A	0.9700
C5—C6	1.460 (2)	C38—H38B	0.9700
C6—C21	1.385 (3)	C39—C40	1.426 (9)
C6—C7	1.398 (3)	C39—H39A	0.9700
C7—C24	1.395 (3)	C39—H39B	0.9700
C7—C8	1.469 (3)	C40—C41	1.420 (7)
C9—C10	1.463 (3)	C40—H40A	0.9700
C10—C25	1.392 (3)	C40—H40B	0.9700
C10—C11	1.404 (3)	C41—H41A	0.9700
C11—C28	1.388 (3)	C41—H41B	0.9700
C11—C12	1.462 (3)	C42—C43	1.233 (11)
C13—C14	1.460 (3)	C42—C46	1.299 (10)
C14—C29	1.387 (3)	C42—H42A	0.9700
C14—C15	1.403 (3)	C42—H42B	0.9700
C15—C32	1.391 (3)	C43—C44	1.375 (10)
C15—C16	1.460 (3)	C43—H43A	0.9700
C17—C18	1.381 (4)	C43—H43B	0.9700
C17—H1	0.97 (3)	C44—C45	1.465 (10)
C18—C19	1.394 (4)	C44—H44A	0.9700
C18—H2	0.91 (4)	C44—H44B	0.9700
C19—C20	1.383 (4)	C45—C46	1.459 (8)
C19—H3	0.96 (4)	C45—H45A	0.9700
C20—H4	0.91 (3)	C45—H45B	0.9700
C21—C22	1.387 (3)	C46—H46A	0.9700
C21—H5	0.89 (3)	C46—H46B	0.9700
N3—Zn1—N1	86.70 (6)	C24—C23—H7	119.6 (16)
N3—Zn1—N5	87.94 (6)	C22—C23—H7	118.5 (16)
N1—Zn1—N5	154.77 (6)	C23—C24—C7	117.3 (2)
N3—Zn1—N7	154.46 (6)	C23—C24—H8	121.3 (14)
N1—Zn1—N7	87.81 (6)	C7—C24—H8	121.4 (14)
N5—Zn1—N7	86.47 (6)	C26—C25—C10	117.6 (2)
N3—Zn1—N9	103.29 (6)	C26—C25—H9	122.7 (14)
N1—Zn1—N9	101.89 (6)	C10—C25—H9	119.7 (14)
N5—Zn1—N9	103.34 (6)	C25—C26—C27	121.6 (2)
N7—Zn1—N9	102.25 (6)	C25—C26—H10	118.3 (16)
C8—N1—C5	108.87 (15)	C27—C26—H10	120.0 (16)
C8—N1—Zn1	125.94 (12)	C28—C27—C26	121.3 (2)
C5—N1—Zn1	124.11 (12)	C28—C27—H11	118.0 (17)
C8—N2—C9	123.22 (16)	C26—C27—H11	120.6 (17)
C9—N3—C12	108.84 (15)	C27—C28—C11	117.3 (2)
C9—N3—Zn1	125.89 (12)	C27—C28—H12	121.0 (15)
C12—N3—Zn1	124.21 (12)	C11—C28—H12	121.7 (15)
C13—N4—C12	123.51 (17)	C30—C29—C14	117.5 (2)
C16—N5—C13	108.84 (15)	C30—C29—H13	123.3 (17)
C16—N5—Zn1	126.52 (13)	C14—C29—H13	119.1 (17)
C13—N5—Zn1	124.00 (12)	C29—C30—C31	121.3 (2)
C1—N6—C16	123.41 (16)	C29—C30—H14	116 (2)
C1—N7—C4	108.83 (15)	C31—C30—H14	123 (2)
C1—N7—Zn1	126.50 (13)	C32—C31—C30	121.3 (2)
C4—N7—Zn1	123.78 (12)	C32—C31—H15	120.8 (17)
C5—N8—C4	123.60 (17)	C30—C31—H15	117.9 (17)
C37—N9—C33	115.70 (17)	C31—C32—C15	118.0 (2)
C37—N9—Zn1	120.61 (13)	C31—C32—H16	119.6 (17)
C33—N9—Zn1	123.66 (13)	C15—C32—H16	122.3 (17)
C35—N10—H22	117.2 (19)	N9—C33—C34	124.18 (18)
C35—N10—H23	117.4 (15)	N9—C33—H21	116.6 (14)
H22—N10—H23	125 (2)	C34—C33—H21	119.2 (14)
N6—C1—N7	127.42 (17)	C33—C34—C35	119.62 (18)
N6—C1—C2	123.53 (17)	C33—C34—H20	122.9 (16)
N7—C1—C2	109.05 (17)	C35—C34—H20	117.3 (16)
C17—C2—C3	121.0 (2)	N10—C35—C36	121.55 (19)
C17—C2—C1	132.6 (2)	N10—C35—C34	122.46 (18)
C3—C2—C1	106.29 (17)	C36—C35—C34	115.98 (18)
C20—C3—C2	121.5 (2)	C37—C36—C35	120.11 (19)
C20—C3—C4	132.3 (2)	C37—C36—H19	122.1 (19)
C2—C3—C4	106.24 (17)	C35—C36—H19	117.6 (19)
N8—C4—N7	127.97 (17)	N9—C37—C36	124.40 (19)
N8—C4—C3	122.50 (17)	N9—C37—H18	125.0 (19)
N7—C4—C3	109.48 (16)	C36—C37—H18	110.4 (19)
N8—C5—N1	128.10 (16)	C38—O1—C41	107.2 (5)
N8—C5—C6	122.56 (17)	O1—C38—C39	107.2 (5)
N1—C5—C6	109.34 (16)	O1—C38—H38A	110.3
C21—C6—C7	121.92 (18)	C39—C38—H38A	110.3
C21—C6—C5	131.59 (19)	O1—C38—H38B	110.3
C7—C6—C5	106.46 (16)	C39—C38—H38B	110.3
C24—C7—C6	120.58 (19)	H38A—C38—H38B	108.5
C24—C7—C8	133.15 (19)	C40—C39—C38	104.7 (5)
C6—C7—C8	106.26 (16)	C40—C39—H39A	110.8
N2—C8—N1	127.30 (16)	C38—C39—H39A	110.8
N2—C8—C7	123.63 (17)	C40—C39—H39B	110.8
N1—C8—C7	109.07 (16)	C38—C39—H39B	110.8
N2—C9—N3	127.47 (16)	H39A—C39—H39B	108.9
N2—C9—C10	123.16 (16)	C41—C40—C39	105.0 (6)
N3—C9—C10	109.37 (16)	C41—C40—H40A	110.7
C25—C10—C11	120.55 (19)	C39—C40—H40A	110.7
C25—C10—C9	133.21 (19)	C41—C40—H40B	110.7
C11—C10—C9	106.23 (16)	C39—C40—H40B	110.7
C28—C11—C10	121.59 (18)	H40A—C40—H40B	108.8
C28—C11—C12	132.15 (19)	O1—C41—C40	109.1 (6)
C10—C11—C12	106.25 (16)	O1—C41—H41A	109.9
N4—C12—N3	128.05 (17)	C40—C41—H41A	109.9
N4—C12—C11	122.64 (17)	O1—C41—H41B	109.9
N3—C12—C11	109.31 (16)	C40—C41—H41B	109.9
N4—C13—N5	128.15 (17)	H41A—C41—H41B	108.3
N4—C13—C14	122.63 (17)	C43—C42—C46	107.5 (7)
N5—C13—C14	109.19 (16)	C43—C42—H42A	110.2
C29—C14—C15	121.36 (19)	C46—C42—H42A	110.2
C29—C14—C13	132.2 (2)	C43—C42—H42B	110.2
C15—C14—C13	106.40 (17)	C46—C42—H42B	110.2
C32—C15—C14	120.5 (2)	H42A—C42—H42B	108.5
C32—C15—C16	133.3 (2)	C42—C43—C44	116.4 (10)
C14—C15—C16	106.11 (17)	C42—C43—H43A	108.2
N6—C16—N5	127.23 (17)	C44—C43—H43A	108.2
N6—C16—C15	123.35 (17)	C42—C43—H43B	108.2
N5—C16—C15	109.41 (17)	C44—C43—H43B	108.2
C18—C17—C2	116.9 (2)	H43A—C43—H43B	107.3
C18—C17—H1	122.3 (15)	C43—C44—C45	102.3 (7)
C2—C17—H1	120.9 (15)	C43—C44—H44A	111.3
C17—C18—C19	121.9 (2)	C45—C44—H44A	111.3
C17—C18—H2	120 (2)	C43—C44—H44B	111.3
C19—C18—H2	118 (2)	C45—C44—H44B	111.3
C20—C19—C18	121.6 (2)	H44A—C44—H44B	109.2
C20—C19—H3	117 (2)	C46—C45—C44	101.1 (6)
C18—C19—H3	121 (2)	C46—C45—H45A	111.6
C19—C20—C3	117.0 (2)	C44—C45—H45A	111.6
C19—C20—H4	123.4 (16)	C46—C45—H45B	111.6
C3—C20—H4	119.5 (16)	C44—C45—H45B	111.6
C6—C21—C22	117.4 (2)	H45A—C45—H45B	109.4
C6—C21—H5	122.0 (18)	C42—C46—C45	110.9 (7)
C22—C21—H5	120.5 (18)	C42—C46—H46A	109.5
C21—C22—C23	120.9 (2)	C45—C46—H46A	109.5
C21—C22—H6	117.3 (17)	C42—C46—H46B	109.5
C23—C22—H6	121.8 (17)	C45—C46—H46B	109.5
C24—C23—C22	122.0 (2)	H46A—C46—H46B	108.0

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N10—H23···N2^i	0.83 (3)	2.27 (3)	3.070 (2)	162 (2)
N10—H22···N6^ii	0.83 (3)	2.38 (3)	3.210 (3)	179 (3)

Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x+1, −y+1, −z.