metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoIUCrDATA
ISSN: 2414-3146

Construction of a supra­molecule comprising [2,3,9,10,16,17,23,24-octa­kis­(2,6-di­methyl­phen­­oxy)phthalocyaninato]zinc(II) and (5,10,15,20-tetra­phenyl­porphyrinato)zinc(II)

aShimane Institute for Industrial Technology, 1-Hokuryo, Matsue, Shimane 690-0816, Japan, and bJapan Synchrotron Radiation Research Institute (JASRI/SPring-8), 1-1-1 Kouto, Sayo, Hyogo 679-5198, Japan
*Correspondence e-mail: makino-masatomo@shimane-iit.jp

Edited by M. Weil, Vienna University of Technology, Austria (Received 15 November 2018; accepted 9 December 2018; online 14 December 2018)

The supra­molecular features in the title compound, [2,3,9,10,16,17,23,24-octa­kis­(2,6-di­methyl­phen­oxy)phthalocyaninato]zinc(II) bis­[(5,10,15,20-tetra­phenyl­porphyrinato)zinc(II)] chloro­form tetra­solvate, [Zn(C96H80N8O8)][Zn(C44H28N4)]2·4CHCl3 or [Zn(Pc)][Zn(TPP)]2·4CHCl3, result from a self-assembly of one mol­ecule of [2,3,9,10,16,17,23,24-octa­kis­(2,6-di­methyl­phen­oxy)phthalocyaninato]zinc(II) (ZnPc) and two mol­ecules of (5,10,15,20-tetra­phenyl­porphyrinato)zinc(II) (ZnTPP). One half ZnPc, one ZnTPP and two chloro­form mol­ecules define the asymmetric unit, with the zinc(II) cation of ZnPc situated on an inversion centre. In the supra­molecule, the central ZnPc moiety is sandwiched between two ZnTPPs moieties in a co-facial conformation with a π-conjugated system, leading to a nearly H-type aggregate with a distance of 3.4967 (5) Å between adjacent zinc sites. The ZnTPP units are slightly glided away to form a partial ecliptic arrangement. Each phenyl group of the TPP ligand is anchored above the N atom of the iso­indole linker of the Pc ligand through weak C—H⋯N hydrogen bonds and is held into the crevice between the two di­methyl­phen­oxy groups of phthalocyanine via van der Waals inter­actions. In the crystal, chloro­form solvent mol­ecules are situated between the supra­molecules. There is another solvent-accessible void of 341 (2) Å3. The contribution of disordered solvent mol­ecules situated in this void was removed from the diffraction data using SQUEEZE in PLATON [Spek (2015[Spek, A. L. (2015). Acta Cryst. C71, 9-18.]). Acta Cryst. C71, 9–18]. The given chemical formula and other crystal data do not consider this unknown solvent mol­ecule(s).

3D view (loading...)
[Scheme 3D1]
Chemical scheme
[Scheme 1]

Structure description

Phthalocyanine, porphyrin and their metal complexes have attracted great attention because their characteristic physico­chemical properties are derived from their extended π-conjugation systems. Phthalocyanine and porphyrin comprise an intensive Q band of approximately 600–900 nm and a Soret band of approximately 400–500 nm. Thus, the combination of these two π-conjugated systems could cover the entire range of the visible region, which is a promising strategy for the development of photo-functional materials, such as dye-sensitized solar cells (DSCs), or for efficient light-energy conversion (O'Regan & Grätzel, 1991[O'Regan, B. & Grätzel, M. (1991). Nature, 353, 737-740.]; Walter et al., 2010[Walter, M. G., Rudine, A. B. & Wamser, C. C. (2010). J. Porphyrins Phthalocyanines, 14, 759-792.]). As part of our efforts to design more efficient dyes for DSCs (Noda et al., 2009[Noda, S., Nagano, K., Inoue, E., Egi, T., Nakashima, T., Imawaka, N., Kanayama, M., Iwata, S., Toshima, K., Nakada, K. & Yoshino, K. (2009). Synth. Met. 159, 2355-2357.]; Iwata et al., 2018[Iwata, S., Shibakawa, S., Imawaka, N. & Yoshino, K. (2018). Energ. Rep. 4, 8-12.]), we discovered that 2,3,9,10,16,17,23,24-octa­kis­(2,6-di­methyl­phen­oxy)phthalo­cyanine (Pc) with zinc(II) as the central metal cation (ZnPc) and 5,10,15,20-tetra­phenyl­porphyrin (TPP) with another central zinc(II) cation (ZnTPP) formed a supra­molecular self-assembly as analysed both by photometric and NMR titration studies. Here, we report the structural analysis of the resulting solvated ZnPc–ZnTPP complex, [Zn(PC)][Zn(TPP)2]·4CHCl3 (I).

The asymmetric unit of (I) comprises of one half of ZnPc, one ZnTPP and two chloro­form mol­ecules. The Zn(II) cation bound to Pc occupies an inversion centre, and therefore complete complexes are generated using an inversion symmetry operation [symmetry code: (i) −x + 1, −y + 1, −z + 1] (Figs. 1[link] and 2[link]). Neither ZnPc nor ZnTPP have axial ligands; Zn—N bond lengths (Table 1[link]) are in the usual range. The Pc and TPP ligands are held together not only through ππ inter­actions between phthalocyanine and porphyrin aromatic cores but also via weak C—H⋯N hydrogen bonds between nitro­gen atoms linked to the iso­indole unit of Pc and hydrogen atoms of the phenyl group of ZnTPP (Table 2[link]). The ZnTPP core plane is nearly parallel to the Pc core with a dihedral angle between the two central N4 core planes of 4.76 (6)° but slightly glided along the N2—N2i line of the iso­indole unit, forming an eclipsed arrangement with an N3Pc—ZnPc—ZnTPP angle of 61.15 (4)°, and with a distance of 3.4967 (5) Å between adjacent metal sites. Each di­methyl­phen­oxy group lies outside the macrocycle, which may prohibit the formation of columnar stacks of Pc by steric hindrance. The phenyl groups of TPP also lie outside the macrocycle and above the nitro­gen atoms linked to the iso­indole units of Pc. However, they fit into the crevice between two di­methyl­phen­oxy groups of Pc. This particular side chain conformation could be responsible for the self-assembled supra­molecular arrangement. The Zn(II) cation bound to TPP is displaced from the central N4 core by 0.0475 (9) Å whereas that bound to Pc lies in the phthalocyanine macrocycle plane due to inversion symmetry. The two chloro­form mol­ecules are situated in the voids of the packed supra­molecules (Fig. 2[link]).

Table 1
Selected bond lengths (Å)

Zn1—N1 1.9700 (14) Zn2—N6 2.0332 (15)
Zn1—N3 1.9920 (14) Zn2—N7 2.0524 (15)
Zn2—N5 2.0234 (15) Zn2—N8 2.0269 (14)

Table 2
Hydrogen-bond geometry and centroid–centroid distances for ππ interactions (Å, °)

Cg1–Cg12 are the centroids of the five- or six-membered rings, where Cg1: N1–C8–C20–C10–C9, Cg2: N3–C7–C18–C13–C11, Cg3: Zn1–N1–C9–N2–C11–N3, Cg4: Zn1–N1–C8–N4–C7i–N3i, Cg5: N5–C52–C63–C54–C61, Cg6: N6–C51–C59–C56–C55, Cg7: N8–C65–C50–C66–C83, Cg8: N7–C67–C49–C73–C69, Cg9: Zn2–N5–C52–C60–C83–N8, Cg10: Zn2–N6–C51–C62–C67–N7, Cg11: Zn2–N5–C61–C57–C69–N7, Cg12: Zn2–N6–C55–C70–C65–N8.

D—H⋯A D—H H⋯A DA D—H⋯A
C89—H89⋯N4 0.95 2.35 3.245 (3) 157
C91—H91⋯N2i 0.95 2.38 3.263 (3) 154
Cg1⋯Cg5     3.6115 (13)  
Cg2⋯Cg7     3.5271 (13)  
Cg3⋯Cg9     3.4996 (11)  
Cg4⋯Cg11     3.6264 (11)  
Cg1iCg6     3.5162 (13)  
Cg2iCg8     3.6819 (13)  
Cg3iCg10     3.6105 (13)  
Cg4iCg12     3.4785 (1)  
Symmetry code: (i) -x+1, -y+1, -z+1.
[Figure 1]
Figure 1
The expanded asymmetric unit of the title supra­molecule in a view from the ZnPc macrocycle, with displacement ellipsoids drawn at the 50% probability level. Atom labels of ZnPc and ZnTPP are black and grey, respectively. ZnTPP and chloro­form mol­ecules generated by inversion operation through the origin at Zn1 have been omitted for clarity [symmetry code: (i) −x + 1, −y + 1, −z + 1].
[Figure 2]
Figure 2
A view along the b axis of the crystal, showing the packing of the title compound.

A structure survey using CSD web inter­face (Groom et al., 2016[Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171-179.]) returned one entry of a phthalocyanine–TPP complex (CCDC entry 621715), and six compounds similar to the Pc moiety of the title compound that were further divided into two groups (CCDC entries 946716, 946717, 946718 and 279644, 761420, 76142, respectively). The phthalocyanine–TPP complex of CCDC 621715 is a (Mn–Cr) μ-hydroxido-bridged complex (Donzello et al., 2006[Donzello, M. P., Bartolino, L., Ercolani, C. & Rizzoli, C. (2006). Inorg. Chem. 45, 6988-6995.]). Conversely, compounds in the first group, which are similar to Pc, differ from Pc only in the types of metal ions (PrIII, NdIII and SmIII; Li et al., 2014[Li, X., Qi, D., Chen, C., Yang, L., Sun, J., Wang, H., Li, X. & Bian, Y. (2014). Dyes Pigments, 101, 179-185.]). Here, one metal ion is situated between two Pc planes, leading to shallow cone-shaped Pc and double-decker complexes. Compounds in the second group crystallized with cubic symmetry (space group Pn[\overline{3}]n) and comprise of isopropyl groups instead of methyl groups on each phen­oxy group, forming a shallow cone shape. Moreover, the compound of CCDC 279644 of the second group has a water mol­ecule as the fifth ligand of ZnII in an axial position (McKeown et al., 2005[McKeown, N. B., Makhseed, S., Msayib, K. J., Ooi, L.-L., Helliwell, M. & Warren, J. E. (2005). Angew. Chem. Int. Ed. 44, 7546-7549.]), and the remaining structures comprise of two macrocycles that are bound together by rigid bridging ligands (Bezzu et al., 2010[Bezzu, C. G., Helliwell, M., Warren, J. E., Allan, D. R. & McKeown, N. B. (2010). Science, 327, 1627-1630.]).

Synthesis and crystallization

n-Hexane (96%), chloro­form (CHCl3, 99.8%), zinc(II) chloride and ZnTPP were obtained from Sigma–Aldrich Japan (Tokyo, Japan). Other reagents were purchased from Tokyo Kasei Kogyo Co., Ltd (Tokyo, Japan). A di­methyl­formamide solution (10 ml) of 4,5-di­chloro­phthalo­nitrile (5 mmol), 2,6-di­methyl­phenol (15 mmol) and potassium carbonate (18 mmol) was prepared and stirred at 373 K for 16 h in a nitro­gen atmosphere. After cooling down to room temperature, the solution was poured into 300 ml of water, and the precipitate was filtered off. The crude product was purified by normal-phase chromatography and recrystallized from ethyl acetate by vaporization to obtain 4,5-di(2,6-di­methyl­phen­oxy)phthalo­nitrile (approximately 70% yield). Subsequently, a di­methyl­amino­ethanol solution (22 ml) of 4,5-di(2,6-di­methyl­phen­oxy)phthalo­nitrile (2.7 mmol) and zinc(II) chloride (1.4 mmol) was stirred at 413 K for 4 h. After cooling down to room temperature, the solution was evaporated under reduced pressure. The crude product was further purified by the same procedure used for synthesis of 4,5-di(2,6-di­methyl­phen­oxy)phthalo­nitrile. The yield of ZnPc was approximately 25%. Both ZnPc and ZnTPP were dissolved in chloro­form with a final concentration of 1 mg ml−1 and were mixed at equal volumes. Single crystals were grown by slow diffusion of n-hexane into a chloro­form solution.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3[link]. Two chloro­form mol­ecules are present in the asymmetric unit, with one of them being disordered. Disorder was modelled over two sets of sites with occupancies of 0.723 (16):0.277 (6) and restrained with the RIGU option in SHELXL. Additional electron density assignable to disordered (chloro­form) mol­ecules near an inversion centre was observed. For the final refinement, the contributions of the disordered solvent mol­ecules were removed from the diffraction data using SQUEEZE in PLATON (Spek, 2015[Spek, A. L. (2015). Acta Cryst. C71, 9-18.]). SQUEEZE estimated the electron counts in each of the four voids (volume 316 Å3) to be 118 electrons.

Table 3
Experimental details

Crystal data
Chemical formula [Zn(C96H80N8O8)][Zn(C44H28N4)]2·4CHCl3
Mr 3372.66
Crystal system, space group Monoclinic, P21/n
Temperature (K) 100
a, b, c (Å) 20.216 (4), 21.275 (2), 20.8210 (17)
β (°) 115.414 (13)
V3) 8088 (2)
Z 2
Radiation type Synchrotron, λ = 0.700 Å
μ (mm−1) 0.70
Crystal size (mm) 0.31 × 0.27 × 0.25
 
Data collection
Diffractometer SPring-8 BL26B1 CCD
No. of measured, independent and observed [I > 2σ(I)] reflections 61759, 16900, 15721
Rint 0.022
(sin θ/λ)max−1) 0.634
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.095, 1.06
No. of reflections 16900
No. of parameters 1061
No. of restraints 42
H-atom treatment H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 0.73, −0.70
Computer programs: BSS (Ueno et al., 2005[Ueno, G., Kanda, H., Kumasaka, T. & Yamamoto, M. (2005). J. Synchrotron Rad. 12, 380-384.]), XDS (Kabsch, 2010[Kabsch, W. (2010). Acta Cryst. D66, 125-132.]), SHELXT (Sheldrick, 2015a[Sheldrick, G. M. (2015a). Acta Cryst. A71, 3-8.]), SHELXL2018 (Sheldrick, 2015b[Sheldrick, G. M. (2015b). Acta Cryst. C71, 3-8.]) and OLEX2 (Dolomanov et al., 2009[Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339-341.]).

Structural data


Computing details top

Data collection: BSS (Ueno et al., 2005); cell refinement: XDS (Kabsch, 2010); data reduction: XDS (Kabsch, 2010); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

[2,3,9,10,16,17,23,24-octakis(2,6-dimethylphenoxy)phthalocyaninato]zinc(II) bis[(5,10,15,20-tetraphenylporphyrinato)zinc(II)] chloroform tetrasolvate top
Crystal data top
[Zn(C96H80N8O8)][Zn(C44H28N4)]2·4CHCl3F(000) = 3476
Mr = 3372.66Dx = 1.385 Mg m3
Monoclinic, P21/nSynchrotron radiation, λ = 0.700 Å
a = 20.216 (4) ÅCell parameters from 54508 reflections
b = 21.275 (2) Åθ = 2.1–26.4°
c = 20.8210 (17) ŵ = 0.70 mm1
β = 115.414 (13)°T = 100 K
V = 8088 (2) Å3Block, dark red
Z = 20.31 × 0.27 × 0.25 mm
Data collection top
SPring-8 BL26B1 CCD
diffractometer
Rint = 0.022
Radiation source: synchrotronθmax = 26.4°, θmin = 2.1°
ω scanh = 2525
61759 measured reflectionsk = 2626
16900 independent reflectionsl = 2625
15721 reflections with I > 2σ(I)
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.038 w = 1/[σ2(Fo2) + (0.0376P)2 + 10.9858P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.095(Δ/σ)max = 0.002
S = 1.06Δρmax = 0.73 e Å3
16900 reflectionsΔρmin = 0.70 e Å3
1061 parametersExtinction correction: SHELXL2018 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
42 restraintsExtinction coefficient: 0.00138 (19)
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.

Refinement. Hydrogen atoms were placed at calculated positions and included in a riding-motion approximation with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(Cmethyl).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Zn10.5000000.5000000.5000000.00998 (7)
O10.68081 (7)0.16815 (6)0.54821 (7)0.0157 (3)
O20.74682 (7)0.22143 (6)0.48340 (8)0.0164 (3)
O30.73646 (8)0.62773 (6)0.30964 (8)0.0203 (2)
O40.67847 (8)0.72992 (6)0.32347 (8)0.0188 (3)
N10.55163 (8)0.54354 (6)0.45134 (8)0.0085 (3)
N20.61527 (8)0.45604 (6)0.42897 (8)0.0089 (3)
N30.53736 (8)0.41834 (6)0.48214 (8)0.0093 (3)
N40.51002 (8)0.64975 (6)0.45427 (8)0.0095 (3)
C10.60331 (11)0.09610 (8)0.57114 (11)0.0172 (4)
C20.56284 (12)0.08463 (10)0.49289 (11)0.0244 (4)
H2A0.5406020.1239800.4688480.037*
H2B0.5244170.0532580.4841080.037*
H2C0.5970080.0691350.4744580.037*
C30.76046 (13)0.20000 (11)0.69371 (13)0.0309 (5)
H3A0.7418220.2398050.6687930.046*
H3B0.8008530.1850400.6835750.046*
H3C0.7780960.2064560.7450190.046*
C40.86945 (13)0.59944 (12)0.42521 (13)0.0323 (5)
H4A0.9207900.5880360.4538430.048*
H4B0.8417450.5938570.4535700.048*
H4C0.8665280.6434630.4103610.048*
C50.67099 (14)0.56114 (13)0.18184 (14)0.0390 (6)
H5A0.6316530.5591140.1973960.058*
H5B0.6589490.5337270.1404940.058*
H5C0.6763340.6044920.1688740.058*
C60.60826 (10)0.67840 (8)0.37815 (10)0.0124 (3)
H60.5857210.7163660.3824070.015*
C70.53128 (9)0.36277 (8)0.51247 (9)0.0089 (3)
C80.54841 (9)0.60672 (8)0.43861 (9)0.0090 (3)
C90.59685 (9)0.51641 (8)0.42595 (9)0.0088 (3)
C100.62535 (9)0.56540 (8)0.39548 (9)0.0101 (3)
C110.59012 (9)0.41191 (8)0.45775 (9)0.0091 (3)
C120.63395 (11)0.78305 (8)0.30971 (11)0.0180 (4)
C130.61861 (9)0.34791 (8)0.47169 (9)0.0093 (3)
C140.59961 (9)0.25684 (8)0.53264 (9)0.0105 (3)
H140.5740430.2365170.5558750.013*
C150.83975 (14)0.26771 (12)0.37508 (15)0.0356 (6)
H150.8352820.2625740.3280610.043*
C160.67474 (9)0.31761 (8)0.46164 (9)0.0112 (3)
H160.6996650.3376810.4376240.013*
C170.69253 (9)0.25743 (8)0.48797 (10)0.0120 (3)
C180.58185 (9)0.31771 (8)0.50616 (9)0.0092 (3)
C190.68995 (10)0.62091 (9)0.34140 (10)0.0147 (4)
C200.59341 (9)0.62155 (8)0.40222 (9)0.0097 (3)
C210.56708 (12)0.78316 (9)0.24985 (11)0.0203 (4)
C220.67449 (10)0.56435 (8)0.36482 (10)0.0129 (3)
H220.6965640.5262530.3601660.016*
C230.78749 (12)0.24107 (10)0.39372 (12)0.0245 (4)
C240.79648 (10)0.25088 (8)0.46278 (11)0.0173 (3)
C250.65682 (10)0.67750 (8)0.34796 (10)0.0139 (3)
C260.90587 (13)0.30882 (10)0.49253 (17)0.0372 (6)
H260.9467920.3313610.5258040.045*
C270.68390 (13)0.11697 (10)0.71670 (11)0.0247 (4)
H270.7108980.1237950.7663230.030*
C280.65937 (10)0.13984 (8)0.59692 (10)0.0141 (3)
C290.65563 (9)0.22739 (8)0.52379 (9)0.0112 (3)
C300.77244 (11)0.57341 (9)0.30418 (12)0.0203 (2)
C310.77862 (14)0.48609 (11)0.23673 (14)0.0335 (5)
H310.7597170.4618470.1943080.040*
C320.72481 (13)0.20312 (11)0.34278 (13)0.0309 (5)
H32A0.6787280.2247890.3331550.046*
H32B0.7248290.1617450.3634740.046*
H32C0.7297390.1979150.2982650.046*
C330.89774 (14)0.30136 (12)0.42371 (18)0.0421 (7)
H330.9324640.3196140.4097850.051*
C340.55033 (13)0.88975 (10)0.27993 (13)0.0284 (5)
H340.5210640.9266040.2700460.034*
C350.53963 (13)0.72610 (10)0.20334 (12)0.0256 (4)
H35A0.5809430.7043650.2003240.038*
H35B0.5045370.7390020.1556400.038*
H35C0.5155100.6977230.2237410.038*
C360.84235 (14)0.46768 (11)0.29304 (15)0.0348 (6)
H360.8661280.4301560.2896510.042*
C370.74147 (12)0.53981 (10)0.24115 (13)0.0261 (5)
C380.87213 (12)0.50315 (11)0.35443 (14)0.0296 (5)
H380.9164180.4900240.3927240.035*
C390.58867 (12)0.06231 (9)0.62096 (12)0.0232 (4)
H390.5504780.0319890.6052770.028*
C400.73327 (14)0.83225 (11)0.41917 (13)0.0300 (5)
H40A0.7433830.7890810.4371990.045*
H40B0.7314990.8598640.4560750.045*
H40C0.7721060.8464290.4062800.045*
C410.86128 (13)0.29108 (12)0.58786 (14)0.0355 (6)
H41A0.8202100.3162500.5867770.053*
H41B0.9074760.3123090.6172720.053*
H41C0.8605210.2495970.6079940.053*
C420.83776 (11)0.55809 (10)0.36072 (12)0.0217 (4)
C430.61742 (13)0.88815 (9)0.33805 (12)0.0260 (5)
H430.6342430.9244060.3672320.031*
C440.70021 (11)0.15212 (9)0.66883 (11)0.0193 (4)
C450.52537 (12)0.83797 (10)0.23591 (13)0.0256 (4)
H450.4792320.8397420.1956700.031*
C460.62920 (14)0.07252 (10)0.69297 (12)0.0269 (5)
H460.6191810.0486350.7263320.032*
C470.66128 (12)0.83436 (9)0.35504 (11)0.0215 (4)
C480.85460 (12)0.28359 (9)0.51394 (13)0.0261 (5)
Zn20.39384 (2)0.41679 (2)0.34482 (2)0.01065 (6)
N50.44485 (8)0.46055 (7)0.29229 (8)0.0120 (3)
N60.33761 (8)0.37279 (7)0.39268 (8)0.0115 (3)
N70.34715 (8)0.50037 (7)0.35269 (8)0.0135 (3)
N80.43642 (8)0.33343 (7)0.33379 (8)0.0111 (3)
C490.26457 (10)0.57107 (9)0.35957 (11)0.0172 (4)
H490.2272230.5886220.3702250.021*
C500.47186 (10)0.22969 (8)0.34670 (10)0.0149 (4)
H500.4751680.1864510.3590780.018*
C510.28889 (9)0.39896 (8)0.41481 (9)0.0117 (3)
C520.49125 (10)0.43348 (8)0.26774 (10)0.0137 (3)
C530.15067 (11)0.54246 (9)0.48395 (11)0.0194 (4)
H530.1563270.5738530.5183770.023*
C540.48444 (10)0.53517 (9)0.23714 (10)0.0165 (4)
H540.4911020.5746530.2194220.020*
C550.34195 (10)0.31005 (8)0.40990 (9)0.0122 (3)
C560.29622 (10)0.29738 (8)0.44533 (10)0.0147 (3)
H560.2898530.2578740.4631930.018*
C570.39476 (10)0.56733 (8)0.28496 (10)0.0135 (3)
C580.68766 (14)0.35076 (12)0.25550 (16)0.0384 (6)
H580.7363940.3663450.2771220.046*
C590.26398 (10)0.35196 (8)0.44858 (10)0.0143 (3)
H590.2308620.3581310.4694010.017*
C600.51101 (10)0.37011 (8)0.27394 (10)0.0137 (3)
C610.43923 (10)0.52288 (8)0.27309 (10)0.0132 (3)
C620.26551 (9)0.46168 (8)0.40480 (10)0.0126 (3)
C630.51580 (10)0.48024 (9)0.23310 (10)0.0165 (4)
H630.5480930.4737100.2114090.020*
C640.38693 (10)0.63029 (8)0.25032 (10)0.0147 (3)
C650.42708 (10)0.27640 (8)0.35929 (9)0.0122 (3)
C660.50811 (10)0.25898 (8)0.31407 (10)0.0160 (4)
H660.5421750.2403510.2995040.019*
C670.29288 (10)0.50837 (8)0.37522 (10)0.0136 (3)
C680.40533 (13)0.17957 (10)0.48381 (12)0.0257 (5)
H680.4311880.2087230.5206660.031*
C690.35181 (10)0.55631 (8)0.32160 (10)0.0145 (3)
C700.38248 (10)0.26475 (8)0.39374 (9)0.0122 (3)
C710.20302 (10)0.47882 (8)0.42156 (10)0.0129 (3)
C720.54560 (13)0.30721 (10)0.19119 (12)0.0260 (5)
H720.4965530.2925310.1682330.031*
C730.30072 (10)0.60051 (8)0.32697 (11)0.0171 (4)
H730.2937160.6427360.3105480.021*
C740.13501 (10)0.45010 (9)0.38492 (10)0.0159 (4)
H740.1295020.4180360.3512400.019*
C750.56506 (11)0.34988 (9)0.24672 (11)0.0187 (4)
C760.37610 (10)0.19836 (8)0.41340 (11)0.0159 (4)
C770.33078 (14)0.09330 (10)0.37734 (17)0.0365 (6)
H770.3054620.0637800.3407340.044*
C780.35706 (11)0.63429 (9)0.17654 (11)0.0194 (4)
H780.3449490.5970010.1487550.023*
C790.63663 (12)0.37220 (10)0.27855 (13)0.0259 (5)
H790.6505680.4020680.3159980.031*
C800.36249 (12)0.74687 (9)0.18325 (12)0.0244 (4)
H800.3531640.7866290.1602620.029*
C810.07529 (10)0.46782 (9)0.39709 (11)0.0187 (4)
H810.0292430.4478870.3718960.022*
C820.33932 (12)0.15473 (9)0.36025 (13)0.0248 (4)
H820.3198770.1671790.3117780.030*
C830.48548 (10)0.32396 (8)0.30539 (10)0.0128 (3)
C840.34491 (12)0.69239 (10)0.14341 (11)0.0248 (4)
H840.3243650.6947440.0930010.030*
C850.08297 (11)0.51469 (10)0.44613 (11)0.0209 (4)
H850.0419300.5276780.4537270.025*
C860.59716 (17)0.28581 (11)0.16889 (15)0.0382 (6)
H860.5834360.2564090.1310070.046*
C870.35910 (16)0.07514 (10)0.44756 (18)0.0419 (7)
H870.3527020.0331950.4595110.050*
C880.66842 (16)0.30727 (13)0.20178 (17)0.0443 (7)
H880.7040520.2919840.1872850.053*
C890.40584 (10)0.68551 (9)0.29003 (10)0.0165 (4)
H890.4272930.6834050.3404830.020*
C900.39654 (16)0.11762 (12)0.50021 (15)0.0388 (6)
H900.4167570.1046020.5485140.047*
C910.21007 (10)0.52464 (9)0.47175 (10)0.0164 (4)
H910.2563070.5439460.4979960.020*
C920.39367 (11)0.74352 (9)0.25663 (11)0.0206 (4)
H920.4067440.7809520.2841540.025*
Cl40.94297 (4)0.42044 (3)0.74187 (4)0.04808 (18)
Cl51.05152 (3)0.36172 (2)0.70601 (3)0.02959 (12)
Cl61.09747 (5)0.43513 (3)0.83329 (4)0.05050 (19)
C941.03091 (15)0.42686 (10)0.74552 (13)0.0305 (5)
H941.0322480.4652640.7184060.037*
Cl1A0.30848 (13)0.45766 (13)0.12147 (9)0.0351 (6)0.723 (16)
Cl2A0.26359 (17)0.47673 (18)0.02796 (16)0.0601 (7)0.723 (16)
Cl3A0.3838 (2)0.39087 (17)0.0532 (3)0.0748 (11)0.723 (16)
Cl1B0.3008 (6)0.4644 (5)0.1130 (7)0.078 (3)0.277 (16)
Cl2B0.2766 (9)0.4592 (8)0.0305 (5)0.106 (4)0.277 (16)
Cl3B0.3892 (5)0.3947 (5)0.0654 (8)0.082 (3)0.277 (16)
C930.30061 (13)0.42107 (10)0.04345 (13)0.0283 (5)
H930.2651800.3854600.0328880.034*0.723 (16)
H93A0.2675420.3839990.0352550.034*0.277 (16)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.01549 (14)0.00335 (12)0.01945 (15)0.00120 (10)0.01545 (12)0.00138 (10)
O10.0217 (7)0.0078 (6)0.0249 (7)0.0085 (5)0.0169 (6)0.0070 (5)
O20.0166 (6)0.0091 (5)0.0318 (7)0.0071 (4)0.0182 (5)0.0042 (5)
O30.0258 (6)0.0145 (5)0.0367 (6)0.0008 (4)0.0286 (5)0.0039 (4)
O40.0239 (7)0.0097 (6)0.0348 (8)0.0000 (5)0.0239 (6)0.0064 (5)
N10.0097 (6)0.0049 (6)0.0148 (7)0.0005 (5)0.0090 (6)0.0012 (5)
N20.0100 (6)0.0066 (6)0.0133 (7)0.0007 (5)0.0082 (6)0.0007 (5)
N30.0118 (7)0.0053 (6)0.0148 (7)0.0011 (5)0.0096 (6)0.0017 (5)
N40.0103 (6)0.0057 (6)0.0147 (7)0.0013 (5)0.0076 (6)0.0017 (5)
C10.0247 (10)0.0087 (8)0.0223 (10)0.0043 (7)0.0141 (8)0.0011 (7)
C20.0321 (11)0.0184 (10)0.0238 (11)0.0023 (8)0.0130 (9)0.0026 (8)
C30.0290 (11)0.0256 (11)0.0291 (12)0.0014 (9)0.0040 (9)0.0000 (9)
C40.0314 (12)0.0334 (12)0.0349 (13)0.0038 (10)0.0170 (10)0.0014 (10)
C50.0360 (13)0.0460 (15)0.0369 (14)0.0124 (11)0.0174 (11)0.0031 (11)
C60.0158 (8)0.0067 (7)0.0195 (9)0.0001 (6)0.0121 (7)0.0018 (6)
C70.0097 (7)0.0064 (7)0.0119 (8)0.0009 (6)0.0058 (6)0.0010 (6)
C80.0095 (7)0.0065 (7)0.0126 (8)0.0001 (6)0.0064 (6)0.0018 (6)
C90.0091 (7)0.0080 (7)0.0128 (8)0.0007 (6)0.0081 (6)0.0015 (6)
C100.0112 (8)0.0079 (7)0.0138 (8)0.0001 (6)0.0078 (7)0.0016 (6)
C110.0095 (7)0.0079 (8)0.0120 (8)0.0009 (6)0.0065 (6)0.0002 (6)
C120.0267 (10)0.0103 (8)0.0288 (10)0.0010 (7)0.0232 (9)0.0073 (7)
C130.0108 (8)0.0065 (7)0.0118 (8)0.0010 (6)0.0061 (6)0.0005 (6)
C140.0132 (8)0.0066 (7)0.0152 (8)0.0013 (6)0.0094 (7)0.0015 (6)
C150.0375 (13)0.0341 (13)0.0553 (16)0.0186 (10)0.0391 (13)0.0178 (11)
C160.0125 (8)0.0085 (8)0.0170 (8)0.0010 (6)0.0104 (7)0.0007 (6)
C170.0110 (8)0.0090 (8)0.0183 (9)0.0038 (6)0.0086 (7)0.0004 (6)
C180.0094 (7)0.0074 (7)0.0132 (8)0.0003 (6)0.0072 (6)0.0009 (6)
C190.0165 (9)0.0146 (9)0.0212 (9)0.0005 (7)0.0159 (8)0.0021 (7)
C200.0102 (7)0.0083 (8)0.0138 (8)0.0004 (6)0.0082 (7)0.0012 (6)
C210.0288 (10)0.0137 (9)0.0287 (11)0.0027 (8)0.0222 (9)0.0059 (8)
C220.0140 (8)0.0093 (8)0.0213 (9)0.0014 (6)0.0131 (7)0.0010 (7)
C230.0257 (10)0.0211 (10)0.0373 (12)0.0134 (8)0.0235 (10)0.0084 (9)
C240.0161 (7)0.0095 (7)0.0344 (8)0.0077 (6)0.0184 (6)0.0051 (6)
C250.0165 (8)0.0089 (8)0.0210 (9)0.0010 (6)0.0126 (7)0.0037 (7)
C260.0212 (11)0.0167 (10)0.082 (2)0.0026 (8)0.0299 (12)0.0019 (11)
C270.0370 (12)0.0200 (10)0.0163 (10)0.0110 (9)0.0106 (9)0.0045 (8)
C280.0203 (9)0.0072 (8)0.0192 (9)0.0082 (6)0.0127 (7)0.0053 (6)
C290.0138 (8)0.0048 (7)0.0153 (8)0.0017 (6)0.0066 (7)0.0012 (6)
C300.0257 (6)0.0145 (5)0.0366 (7)0.0008 (4)0.0286 (5)0.0039 (5)
C310.0445 (14)0.0272 (11)0.0459 (14)0.0101 (10)0.0357 (12)0.0128 (10)
C320.0334 (12)0.0341 (12)0.0307 (12)0.0112 (10)0.0188 (10)0.0034 (9)
C330.0358 (13)0.0283 (12)0.088 (2)0.0104 (10)0.0504 (15)0.0155 (13)
C340.0428 (13)0.0123 (9)0.0447 (14)0.0059 (9)0.0325 (11)0.0113 (9)
C350.0309 (11)0.0198 (10)0.0306 (11)0.0035 (8)0.0175 (10)0.0030 (8)
C360.0459 (14)0.0204 (10)0.0625 (17)0.0034 (10)0.0466 (14)0.0032 (10)
C370.0299 (11)0.0247 (10)0.0360 (12)0.0083 (9)0.0259 (10)0.0031 (9)
C380.0234 (11)0.0288 (11)0.0488 (14)0.0056 (9)0.0272 (11)0.0070 (10)
C390.0336 (11)0.0115 (9)0.0320 (11)0.0013 (8)0.0211 (10)0.0016 (8)
C400.0396 (13)0.0257 (11)0.0302 (12)0.0049 (9)0.0201 (10)0.0001 (9)
C410.0244 (11)0.0313 (12)0.0460 (15)0.0024 (9)0.0105 (10)0.0116 (11)
C420.0230 (10)0.0198 (10)0.0337 (11)0.0026 (8)0.0229 (9)0.0006 (8)
C430.0449 (13)0.0118 (9)0.0348 (12)0.0024 (8)0.0299 (11)0.0023 (8)
C440.0219 (10)0.0135 (9)0.0207 (10)0.0072 (7)0.0075 (8)0.0020 (7)
C450.0279 (11)0.0186 (10)0.0362 (12)0.0015 (8)0.0193 (10)0.0127 (9)
C460.0462 (13)0.0167 (9)0.0275 (11)0.0074 (9)0.0250 (10)0.0090 (8)
C470.0341 (11)0.0141 (9)0.0276 (11)0.0033 (8)0.0239 (9)0.0040 (8)
C480.0210 (10)0.0138 (9)0.0480 (14)0.0062 (8)0.0193 (10)0.0003 (9)
Zn20.01339 (10)0.00573 (10)0.01621 (11)0.00043 (7)0.00956 (8)0.00065 (7)
N50.0139 (7)0.0077 (7)0.0171 (7)0.0003 (5)0.0092 (6)0.0001 (5)
N60.0127 (7)0.0087 (7)0.0159 (7)0.0002 (5)0.0087 (6)0.0010 (5)
N70.0161 (7)0.0081 (7)0.0195 (8)0.0017 (5)0.0106 (6)0.0005 (6)
N80.0131 (7)0.0069 (7)0.0158 (7)0.0000 (5)0.0086 (6)0.0011 (5)
C490.0180 (9)0.0118 (8)0.0252 (10)0.0044 (7)0.0125 (8)0.0000 (7)
C500.0179 (9)0.0088 (8)0.0201 (9)0.0023 (7)0.0101 (7)0.0010 (7)
C510.0116 (8)0.0108 (8)0.0134 (8)0.0007 (6)0.0059 (7)0.0023 (6)
C520.0139 (8)0.0120 (8)0.0171 (9)0.0010 (6)0.0084 (7)0.0016 (7)
C530.0210 (9)0.0155 (9)0.0256 (10)0.0025 (7)0.0136 (8)0.0045 (7)
C540.0195 (9)0.0105 (8)0.0223 (10)0.0030 (7)0.0116 (8)0.0013 (7)
C550.0126 (8)0.0097 (8)0.0146 (8)0.0011 (6)0.0061 (7)0.0010 (6)
C560.0163 (8)0.0112 (8)0.0189 (9)0.0011 (7)0.0097 (7)0.0004 (7)
C570.0161 (8)0.0080 (8)0.0156 (9)0.0011 (6)0.0062 (7)0.0001 (6)
C580.0269 (12)0.0345 (13)0.0681 (18)0.0104 (10)0.0338 (13)0.0236 (12)
C590.0140 (8)0.0137 (8)0.0185 (9)0.0008 (7)0.0101 (7)0.0010 (7)
C600.0130 (8)0.0129 (8)0.0177 (9)0.0001 (6)0.0090 (7)0.0024 (7)
C610.0153 (8)0.0095 (8)0.0151 (9)0.0018 (6)0.0068 (7)0.0005 (6)
C620.0115 (8)0.0104 (8)0.0168 (9)0.0004 (6)0.0069 (7)0.0026 (6)
C630.0180 (9)0.0154 (9)0.0213 (9)0.0020 (7)0.0133 (8)0.0003 (7)
C640.0133 (8)0.0111 (8)0.0208 (9)0.0019 (6)0.0084 (7)0.0038 (7)
C650.0134 (8)0.0080 (8)0.0152 (8)0.0003 (6)0.0061 (7)0.0016 (6)
C660.0185 (9)0.0112 (8)0.0220 (9)0.0021 (7)0.0122 (8)0.0014 (7)
C670.0134 (8)0.0114 (8)0.0178 (9)0.0020 (6)0.0083 (7)0.0013 (7)
C680.0344 (12)0.0222 (10)0.0310 (11)0.0125 (9)0.0241 (10)0.0088 (9)
C690.0171 (9)0.0092 (8)0.0177 (9)0.0012 (7)0.0081 (7)0.0001 (7)
C700.0139 (8)0.0078 (8)0.0152 (8)0.0005 (6)0.0065 (7)0.0003 (6)
C710.0127 (8)0.0100 (8)0.0184 (9)0.0016 (6)0.0090 (7)0.0015 (7)
C720.0362 (12)0.0181 (10)0.0353 (12)0.0033 (8)0.0265 (10)0.0003 (8)
C730.0197 (9)0.0088 (8)0.0245 (10)0.0038 (7)0.0110 (8)0.0022 (7)
C740.0167 (9)0.0133 (8)0.0190 (9)0.0004 (7)0.0089 (7)0.0011 (7)
C750.0223 (9)0.0128 (8)0.0298 (11)0.0042 (7)0.0197 (9)0.0048 (7)
C760.0185 (9)0.0091 (8)0.0277 (10)0.0045 (7)0.0172 (8)0.0036 (7)
C770.0346 (13)0.0110 (10)0.0717 (19)0.0015 (9)0.0304 (13)0.0027 (10)
C780.0205 (9)0.0157 (9)0.0219 (10)0.0017 (7)0.0089 (8)0.0016 (7)
C790.0218 (10)0.0203 (10)0.0404 (13)0.0041 (8)0.0179 (9)0.0105 (9)
C800.0244 (10)0.0138 (9)0.0324 (12)0.0003 (8)0.0099 (9)0.0119 (8)
C810.0132 (9)0.0202 (9)0.0241 (10)0.0005 (7)0.0094 (8)0.0005 (8)
C820.0250 (10)0.0131 (9)0.0382 (12)0.0004 (8)0.0153 (9)0.0019 (8)
C830.0127 (8)0.0110 (8)0.0168 (9)0.0001 (6)0.0083 (7)0.0034 (6)
C840.0258 (11)0.0248 (11)0.0194 (10)0.0016 (8)0.0056 (8)0.0075 (8)
C850.0161 (9)0.0217 (10)0.0305 (11)0.0036 (7)0.0153 (8)0.0003 (8)
C860.0651 (18)0.0256 (12)0.0484 (15)0.0146 (11)0.0476 (15)0.0081 (10)
C870.0523 (16)0.0116 (10)0.086 (2)0.0099 (10)0.0528 (16)0.0161 (12)
C880.0531 (16)0.0394 (14)0.0713 (19)0.0250 (12)0.0560 (16)0.0260 (14)
C890.0174 (9)0.0123 (8)0.0204 (9)0.0025 (7)0.0086 (7)0.0023 (7)
C900.0547 (16)0.0332 (13)0.0514 (16)0.0240 (12)0.0444 (14)0.0260 (12)
C910.0139 (8)0.0136 (8)0.0229 (10)0.0003 (7)0.0089 (7)0.0021 (7)
C920.0197 (9)0.0106 (8)0.0306 (11)0.0013 (7)0.0097 (8)0.0023 (8)
Cl40.0584 (4)0.0354 (3)0.0707 (5)0.0144 (3)0.0470 (4)0.0157 (3)
Cl50.0397 (3)0.0218 (2)0.0354 (3)0.0050 (2)0.0238 (2)0.0027 (2)
Cl60.0830 (5)0.0337 (3)0.0291 (3)0.0021 (3)0.0187 (3)0.0034 (2)
C940.0502 (14)0.0162 (10)0.0321 (12)0.0002 (9)0.0243 (11)0.0047 (8)
Cl1A0.0421 (9)0.0356 (9)0.0267 (11)0.0191 (6)0.0139 (8)0.0112 (6)
Cl2A0.0692 (10)0.0636 (14)0.0447 (9)0.0085 (10)0.0218 (9)0.0216 (8)
Cl3A0.0617 (17)0.0321 (10)0.170 (3)0.0161 (9)0.087 (2)0.0255 (12)
Cl1B0.094 (5)0.038 (3)0.143 (7)0.017 (3)0.091 (5)0.043 (4)
Cl2B0.133 (7)0.076 (6)0.043 (3)0.055 (5)0.027 (3)0.025 (3)
Cl3B0.029 (3)0.060 (4)0.149 (6)0.000 (2)0.029 (3)0.044 (3)
C930.0300 (11)0.0226 (10)0.0375 (13)0.0135 (9)0.0196 (10)0.0088 (9)
Geometric parameters (Å, º) top
Zn1—N1i1.9700 (14)C43—H430.9500
Zn1—N11.9700 (14)C43—C471.397 (3)
Zn1—N31.9920 (14)C45—H450.9500
Zn1—N3i1.9919 (14)C46—H460.9500
O1—C281.399 (2)Zn2—N52.0234 (15)
O1—C291.372 (2)Zn2—N62.0332 (15)
O2—C171.375 (2)Zn2—N72.0524 (15)
O2—C241.398 (2)Zn2—N82.0269 (14)
O3—C191.370 (2)N5—C521.373 (2)
O3—C301.396 (2)N5—C611.376 (2)
O4—C121.396 (2)N6—C511.372 (2)
O4—C251.374 (2)N6—C551.375 (2)
N1—C81.366 (2)N7—C671.376 (2)
N1—C91.365 (2)N7—C691.377 (2)
N2—C91.331 (2)N8—C651.370 (2)
N2—C111.327 (2)N8—C831.370 (2)
N3—C71.370 (2)C49—H490.9500
N3—C111.371 (2)C49—C671.433 (2)
N4—C7i1.321 (2)C49—C731.346 (3)
N4—C81.328 (2)C50—H500.9500
C1—C21.496 (3)C50—C651.442 (2)
C1—C281.384 (3)C50—C661.347 (3)
C1—C391.394 (3)C51—C591.432 (2)
C2—H2A0.9800C51—C621.401 (2)
C2—H2B0.9800C52—C601.396 (2)
C2—H2C0.9800C52—C631.436 (2)
C3—H3A0.9800C53—H530.9500
C3—H3B0.9800C53—C851.385 (3)
C3—H3C0.9800C53—C911.383 (3)
C3—C441.499 (3)C54—H540.9500
C4—H4A0.9800C54—C611.432 (3)
C4—H4B0.9800C54—C631.349 (3)
C4—H4C0.9800C55—C561.434 (2)
C4—C421.500 (3)C55—C701.396 (2)
C5—H5A0.9800C56—H560.9500
C5—H5B0.9800C56—C591.347 (3)
C5—H5C0.9800C57—C611.398 (3)
C5—C371.500 (4)C57—C641.497 (2)
C6—H60.9500C57—C691.400 (3)
C6—C201.390 (2)C58—H580.9500
C6—C251.374 (2)C58—C791.388 (3)
C7—C181.448 (2)C58—C881.373 (4)
C8—C201.447 (2)C59—H590.9500
C9—C101.461 (2)C60—C751.494 (2)
C10—C201.393 (2)C60—C831.396 (3)
C10—C221.393 (2)C62—C671.402 (3)
C11—C131.458 (2)C62—C711.493 (2)
C12—C211.391 (3)C63—H630.9500
C12—C471.393 (3)C64—C781.391 (3)
C13—C161.397 (2)C64—C891.392 (3)
C13—C181.392 (2)C65—C701.394 (2)
C14—H140.9500C66—H660.9500
C14—C181.393 (2)C66—C831.443 (2)
C14—C291.374 (2)C68—H680.9500
C15—H150.9500C68—C761.384 (3)
C15—C231.393 (3)C68—C901.392 (3)
C15—C331.376 (4)C69—C731.436 (2)
C16—H160.9500C70—C761.492 (2)
C16—C171.378 (2)C71—C741.395 (3)
C17—C291.414 (2)C71—C911.391 (3)
C19—C221.383 (2)C72—H720.9500
C19—C251.413 (2)C72—C751.388 (3)
C21—C351.503 (3)C72—C861.387 (3)
C21—C451.395 (3)C73—H730.9500
C22—H220.9500C74—H740.9500
C23—C241.385 (3)C74—C811.388 (3)
C23—C321.493 (3)C75—C791.391 (3)
C24—C481.387 (3)C76—C821.390 (3)
C26—H260.9500C77—H770.9500
C26—C331.380 (4)C77—C821.385 (3)
C26—C481.399 (3)C77—C871.377 (4)
C27—H270.9500C78—H780.9500
C27—C441.394 (3)C78—C841.385 (3)
C27—C461.376 (3)C79—H790.9500
C28—C441.389 (3)C80—H800.9500
C30—C371.386 (3)C80—C841.380 (3)
C30—C421.379 (3)C80—C921.382 (3)
C31—H310.9500C81—H810.9500
C31—C361.375 (4)C81—C851.387 (3)
C31—C371.392 (3)C82—H820.9500
C32—H32A0.9800C84—H840.9500
C32—H32B0.9800C85—H850.9500
C32—H32C0.9800C86—H860.9500
C33—H330.9500C86—C881.381 (4)
C34—H340.9500C87—H870.9500
C34—C431.377 (4)C87—C901.371 (4)
C34—C451.383 (3)C88—H880.9500
C35—H35A0.9800C89—H890.9500
C35—H35B0.9800C89—C921.386 (3)
C35—H35C0.9800C90—H900.9500
C36—H360.9500C91—H910.9500
C36—C381.380 (4)C92—H920.9500
C38—H380.9500Cl4—C941.752 (3)
C38—C421.394 (3)Cl5—C941.751 (2)
C39—H390.9500Cl6—C941.752 (3)
C39—C461.383 (3)C94—H941.0000
C40—H40A0.9800Cl1A—C931.746 (3)
C40—H40B0.9800Cl2A—C931.794 (4)
C40—H40C0.9800Cl3A—C931.729 (4)
C40—C471.495 (3)Cl1B—C931.715 (8)
C41—H41A0.9800Cl2B—C931.621 (9)
C41—H41B0.9800Cl3B—C931.741 (9)
C41—H41C0.9800C93—H931.0000
C41—C481.495 (4)C93—H93A1.0000
N1i—Zn1—N1180.0C27—C46—C39120.55 (19)
N1—Zn1—N389.26 (6)C27—C46—H46119.7
N1i—Zn1—N390.74 (6)C39—C46—H46119.7
N1i—Zn1—N3i89.26 (6)C12—C47—C40122.19 (19)
N1—Zn1—N3i90.74 (6)C12—C47—C43116.5 (2)
N3i—Zn1—N3180.0C43—C47—C40121.3 (2)
C29—O1—C28118.87 (13)C24—C48—C26116.5 (2)
C17—O2—C24118.13 (13)C24—C48—C41121.1 (2)
C19—O3—C30116.18 (14)C26—C48—C41122.4 (2)
C25—O4—C12116.97 (14)N5—Zn2—N6176.94 (6)
C8—N1—Zn1124.80 (11)N5—Zn2—N790.18 (6)
C9—N1—Zn1126.24 (11)N5—Zn2—N890.09 (6)
C9—N1—C8108.95 (13)N6—Zn2—N789.24 (6)
C11—N2—C9123.40 (14)N8—Zn2—N690.38 (6)
C7—N3—Zn1123.38 (11)N8—Zn2—N7177.84 (6)
C7—N3—C11108.81 (13)C52—N5—Zn2126.62 (12)
C11—N3—Zn1125.02 (11)C52—N5—C61106.29 (15)
C7i—N4—C8123.87 (15)C61—N5—Zn2127.09 (12)
C28—C1—C2120.39 (17)C51—N6—Zn2127.64 (12)
C28—C1—C39117.26 (19)C51—N6—C55106.32 (14)
C39—C1—C2122.31 (19)C55—N6—Zn2126.03 (12)
C1—C2—H2A109.5C67—N7—Zn2126.55 (12)
C1—C2—H2B109.5C67—N7—C69106.18 (14)
C1—C2—H2C109.5C69—N7—Zn2125.77 (12)
H2A—C2—H2B109.5C65—N8—Zn2126.53 (12)
H2A—C2—H2C109.5C65—N8—C83106.42 (14)
H2B—C2—H2C109.5C83—N8—Zn2126.79 (12)
H3A—C3—H3B109.5C67—C49—H49126.3
H3A—C3—H3C109.5C73—C49—H49126.3
H3B—C3—H3C109.5C73—C49—C67107.31 (16)
C44—C3—H3A109.5C65—C50—H50126.5
C44—C3—H3B109.5C66—C50—H50126.5
C44—C3—H3C109.5C66—C50—C65107.03 (16)
H4A—C4—H4B109.5N6—C51—C59109.63 (15)
H4A—C4—H4C109.5N6—C51—C62125.55 (16)
H4B—C4—H4C109.5C62—C51—C59124.80 (16)
C42—C4—H4A109.5N5—C52—C60125.79 (16)
C42—C4—H4B109.5N5—C52—C63109.57 (15)
C42—C4—H4C109.5C60—C52—C63124.63 (17)
H5A—C5—H5B109.5C85—C53—H53119.9
H5A—C5—H5C109.5C91—C53—H53119.9
H5B—C5—H5C109.5C91—C53—C85120.19 (18)
C37—C5—H5A109.5C61—C54—H54126.4
C37—C5—H5B109.5C63—C54—H54126.4
C37—C5—H5C109.5C63—C54—C61107.26 (16)
C20—C6—H6121.3N6—C55—C56109.48 (15)
C25—C6—H6121.3N6—C55—C70125.84 (16)
C25—C6—C20117.37 (16)C70—C55—C56124.66 (16)
N3—C7—C18108.84 (14)C55—C56—H56126.4
N4i—C7—N3128.13 (15)C59—C56—C55107.24 (16)
N4i—C7—C18122.95 (15)C59—C56—H56126.4
N1—C8—C20109.14 (14)C61—C57—C64117.59 (16)
N4—C8—N1127.93 (15)C61—C57—C69125.41 (16)
N4—C8—C20122.91 (15)C69—C57—C64116.77 (16)
N1—C9—C10108.73 (14)C79—C58—H58119.7
N2—C9—N1127.57 (15)C88—C58—H58119.7
N2—C9—C10123.67 (15)C88—C58—C79120.7 (2)
C20—C10—C9106.37 (14)C51—C59—H59126.3
C22—C10—C9132.80 (16)C56—C59—C51107.30 (16)
C22—C10—C20120.83 (15)C56—C59—H59126.3
N2—C11—N3127.34 (15)C52—C60—C75118.03 (16)
N2—C11—C13123.74 (15)C83—C60—C52125.01 (16)
N3—C11—C13108.85 (14)C83—C60—C75116.94 (16)
C21—C12—O4118.59 (18)N5—C61—C54109.66 (15)
C21—C12—C47123.79 (18)N5—C61—C57125.44 (16)
C47—C12—O4117.53 (19)C57—C61—C54124.88 (16)
C16—C13—C11132.69 (15)C51—C62—C67124.67 (16)
C18—C13—C11106.32 (14)C51—C62—C71117.58 (16)
C18—C13—C16120.79 (15)C67—C62—C71117.57 (15)
C18—C14—H14121.4C52—C63—H63126.4
C29—C14—H14121.4C54—C63—C52107.20 (16)
C29—C14—C18117.25 (15)C54—C63—H63126.4
C23—C15—H15119.5C78—C64—C57119.53 (17)
C33—C15—H15119.5C78—C64—C89118.85 (17)
C33—C15—C23121.0 (2)C89—C64—C57121.56 (17)
C13—C16—H16121.3N8—C65—C50109.77 (15)
C17—C16—C13117.34 (15)N8—C65—C70125.74 (16)
C17—C16—H16121.3C70—C65—C50124.48 (16)
O2—C17—C16124.74 (16)C50—C66—H66126.4
O2—C17—C29113.73 (15)C50—C66—C83107.13 (16)
C16—C17—C29121.53 (15)C83—C66—H66126.4
C13—C18—C7107.16 (14)N7—C67—C49109.67 (16)
C13—C18—C14121.97 (15)N7—C67—C62125.79 (16)
C14—C18—C7130.67 (15)C62—C67—C49124.42 (16)
O3—C19—C22124.61 (16)C76—C68—H68120.3
O3—C19—C25114.11 (15)C76—C68—C90119.5 (2)
C22—C19—C25121.27 (16)C90—C68—H68120.3
C6—C20—C8131.30 (16)N7—C69—C57125.77 (16)
C6—C20—C10121.91 (15)N7—C69—C73109.43 (16)
C10—C20—C8106.77 (14)C57—C69—C73124.60 (17)
C12—C21—C35121.60 (18)C55—C70—C76117.30 (16)
C12—C21—C45117.15 (19)C65—C70—C55125.25 (16)
C45—C21—C35121.2 (2)C65—C70—C76117.43 (15)
C10—C22—H22121.3C74—C71—C62119.97 (16)
C19—C22—C10117.46 (16)C91—C71—C62121.50 (16)
C19—C22—H22121.3C91—C71—C74118.50 (16)
C15—C23—C32122.4 (2)C75—C72—H72119.7
C24—C23—C15116.8 (2)C86—C72—H72119.7
C24—C23—C32120.81 (19)C86—C72—C75120.6 (2)
C23—C24—O2117.35 (18)C49—C73—C69107.38 (16)
C23—C24—C48124.27 (19)C49—C73—H73126.3
C48—C24—O2118.17 (18)C69—C73—H73126.3
O4—C25—C6124.22 (16)C71—C74—H74119.6
O4—C25—C19114.60 (15)C81—C74—C71120.77 (18)
C6—C25—C19121.17 (16)C81—C74—H74119.6
C33—C26—H26119.6C72—C75—C60120.85 (18)
C33—C26—C48120.8 (2)C72—C75—C79119.02 (19)
C48—C26—H26119.6C79—C75—C60120.10 (19)
C44—C27—H27119.6C68—C76—C70121.09 (18)
C46—C27—H27119.6C68—C76—C82119.34 (19)
C46—C27—C44120.8 (2)C82—C76—C70119.57 (18)
C1—C28—O1117.72 (17)C82—C77—H77120.1
C1—C28—C44123.59 (17)C87—C77—H77120.1
C44—C28—O1118.34 (17)C87—C77—C82119.8 (2)
O1—C29—C14124.40 (16)C64—C78—H78119.8
O1—C29—C17114.49 (15)C84—C78—C64120.31 (19)
C14—C29—C17121.10 (15)C84—C78—H78119.8
C37—C30—O3117.7 (2)C58—C79—C75119.9 (2)
C42—C30—O3117.88 (19)C58—C79—H79120.1
C42—C30—C37124.37 (19)C75—C79—H79120.1
C36—C31—H31119.6C84—C80—H80120.0
C36—C31—C37120.8 (2)C84—C80—C92119.91 (18)
C37—C31—H31119.6C92—C80—H80120.0
C23—C32—H32A109.5C74—C81—H81120.1
C23—C32—H32B109.5C85—C81—C74119.88 (18)
C23—C32—H32C109.5C85—C81—H81120.1
H32A—C32—H32B109.5C76—C82—H82119.7
H32A—C32—H32C109.5C77—C82—C76120.6 (2)
H32B—C32—H32C109.5C77—C82—H82119.7
C15—C33—C26120.6 (2)N8—C83—C60125.50 (16)
C15—C33—H33119.7N8—C83—C66109.64 (15)
C26—C33—H33119.7C60—C83—C66124.85 (16)
C43—C34—H34119.9C78—C84—H84119.8
C43—C34—C45120.3 (2)C80—C84—C78120.3 (2)
C45—C34—H34119.9C80—C84—H84119.8
C21—C35—H35A109.5C53—C85—C81119.76 (17)
C21—C35—H35B109.5C53—C85—H85120.1
C21—C35—H35C109.5C81—C85—H85120.1
H35A—C35—H35B109.5C72—C86—H86120.0
H35A—C35—H35C109.5C88—C86—C72120.0 (3)
H35B—C35—H35C109.5C88—C86—H86120.0
C31—C36—H36119.7C77—C87—H87120.0
C31—C36—C38120.7 (2)C90—C87—C77120.0 (2)
C38—C36—H36119.7C90—C87—H87120.0
C30—C37—C5120.5 (2)C58—C88—C86119.8 (2)
C30—C37—C31116.7 (2)C58—C88—H88120.1
C31—C37—C5122.9 (2)C86—C88—H88120.1
C36—C38—H38119.7C64—C89—H89119.7
C36—C38—C42120.6 (2)C92—C89—C64120.60 (18)
C42—C38—H38119.7C92—C89—H89119.7
C1—C39—H39119.7C68—C90—H90119.6
C46—C39—C1120.6 (2)C87—C90—C68120.9 (2)
C46—C39—H39119.7C87—C90—H90119.6
H40A—C40—H40B109.5C53—C91—C71120.87 (18)
H40A—C40—H40C109.5C53—C91—H91119.6
H40B—C40—H40C109.5C71—C91—H91119.6
C47—C40—H40A109.5C80—C92—C89119.96 (19)
C47—C40—H40B109.5C80—C92—H92120.0
C47—C40—H40C109.5C89—C92—H92120.0
H41A—C41—H41B109.5Cl4—C94—Cl6111.33 (13)
H41A—C41—H41C109.5Cl4—C94—H94108.2
H41B—C41—H41C109.5Cl5—C94—Cl4111.07 (13)
C48—C41—H41A109.5Cl5—C94—Cl6109.78 (14)
C48—C41—H41B109.5Cl5—C94—H94108.2
C48—C41—H41C109.5Cl6—C94—H94108.2
C30—C42—C4120.69 (19)Cl1A—C93—Cl2A108.41 (18)
C30—C42—C38116.8 (2)Cl1A—C93—H93108.3
C38—C42—C4122.5 (2)Cl2A—C93—H93108.2
C34—C43—H43119.3Cl3A—C93—Cl1A111.1 (2)
C34—C43—C47121.4 (2)Cl3A—C93—Cl2A112.4 (2)
C47—C43—H43119.3Cl3A—C93—H93108.2
C27—C44—C3121.6 (2)Cl1B—C93—Cl3B108.8 (6)
C28—C44—C3121.26 (19)Cl1B—C93—H93A109.1
C28—C44—C27117.13 (19)Cl2B—C93—Cl1B115.1 (6)
C21—C45—H45119.6Cl2B—C93—Cl3B105.4 (8)
C34—C45—C21120.8 (2)Cl2B—C93—H93A109.1
C34—C45—H45119.6Cl3B—C93—H93A109.1
Symmetry code: (i) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
Cg1–Cg12 are the centroids of the five- or six-membered rings, where Cg1: N1–C8–C20–C10–C9, Cg2: N3–C7–C18–C13–C11, Cg3: Zn1–N1–C9–N2–C11–N3, Cg4: Zn1–N1–C8–N4–C7i–N3i, Cg5: N5–C52–C63–C54–C61, Cg6: N6–C51–C59–C56–C55, Cg7: N8–C65–C50–C66–C83, Cg8: N7–C67–C49–C73–C69, Cg9: Zn2–N5–C52–C60–C83–N8, Cg10: Zn2–N6–C51–C62–C67–N7, Cg11: Zn2–N5–C61–C57–C69–N7, Cg12: Zn2–N6–C55–C70–C65–N8.
D—H···AD—HH···AD···AD—H···A
C89—H89···N40.952.353.245 (3)157
C91—H91···N2i0.952.383.263 (3)154
Cg1···Cg53.6115 (13)
Cg2···Cg73.5271 (13)
Cg3···Cg93.4996 (11)
Cg4···Cg113.6264 (11)
Cg1i···Cg63.5162 (13)
Cg2i···Cg83.6819 (13)
Cg3i···Cg103.6105 (13)
Cg4i···Cg123.4785 (1)
Symmetry code: (i) x+1, y+1, z+1.
 

Acknowledgements

We would like to thank Go Ueno, Hironori Murakami and beamline staff of BL26B1 at SPring-8 for the data collection. The experiments were conducted at beamline BL26B1 with the approval (Proposal No 2014 A1862) of JASRI/SPring-8.

References

First citationBezzu, C. G., Helliwell, M., Warren, J. E., Allan, D. R. & McKeown, N. B. (2010). Science, 327, 1627–1630.  Web of Science CrossRef CAS PubMed Google Scholar
First citationDolomanov, 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
First citationDonzello, M. P., Bartolino, L., Ercolani, C. & Rizzoli, C. (2006). Inorg. Chem. 45, 6988–6995.  CrossRef Google Scholar
First citationGroom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179.  Web of Science CrossRef IUCr Journals Google Scholar
First citationIwata, S., Shibakawa, S., Imawaka, N. & Yoshino, K. (2018). Energ. Rep. 4, 8–12.  CrossRef Google Scholar
First citationKabsch, W. (2010). Acta Cryst. D66, 125–132.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationLi, X., Qi, D., Chen, C., Yang, L., Sun, J., Wang, H., Li, X. & Bian, Y. (2014). Dyes Pigments, 101, 179–185.  CrossRef Google Scholar
First citationMcKeown, N. B., Makhseed, S., Msayib, K. J., Ooi, L.-L., Helliwell, M. & Warren, J. E. (2005). Angew. Chem. Int. Ed. 44, 7546–7549.  CrossRef Google Scholar
First citationNoda, S., Nagano, K., Inoue, E., Egi, T., Nakashima, T., Imawaka, N., Kanayama, M., Iwata, S., Toshima, K., Nakada, K. & Yoshino, K. (2009). Synth. Met. 159, 2355–2357.  CrossRef Google Scholar
First citationO'Regan, B. & Grätzel, M. (1991). Nature, 353, 737–740.  Google Scholar
First citationSheldrick, G. M. (2015a). Acta Cryst. A71, 3–8.  Web of Science CrossRef IUCr Journals Google Scholar
First citationSheldrick, G. M. (2015b). Acta Cryst. C71, 3–8.  Web of Science CrossRef IUCr Journals Google Scholar
First citationSpek, A. L. (2015). Acta Cryst. C71, 9–18.  Web of Science CrossRef IUCr Journals Google Scholar
First citationUeno, G., Kanda, H., Kumasaka, T. & Yamamoto, M. (2005). J. Synchrotron Rad. 12, 380–384.  Web of Science CrossRef IUCr Journals Google Scholar
First citationWalter, M. G., Rudine, A. B. & Wamser, C. C. (2010). J. Porphyrins Phthalocyanines, 14, 759–792.  CrossRef 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.

Journal logoIUCrDATA
ISSN: 2414-3146
Follow IUCr Journals
Sign up for e-alerts
Follow IUCr on Twitter
Follow us on facebook
Sign up for RSS feeds