






Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536810028588/lh5086sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536810028588/lh5086Isup2.hkl |
CCDC reference: 788265
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean
(C-C) = 0.005 Å
- Disorder in main residue
- R factor = 0.040
- wR factor = 0.097
- Data-to-parameter ratio = 15.6
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT201_ALERT_2_B Isotropic non-H Atoms in Main Residue(s) ....... 6 PLAT220_ALERT_2_B Large Non-Solvent C Ueq(max)/Ueq(min) ... 4.68 Ratio PLAT242_ALERT_2_B Check Low Ueq as Compared to Neighbors for S3
Alert level C PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for S1 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C5A PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L= 0.600 20
Alert level G PLAT301_ALERT_3_G Note: Main Residue Disorder ................... 14.00 Perc. PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 16 PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels .......... 10 PLAT811_ALERT_5_G No ADDSYM Analysis: Too Many Excluded Atoms .... !
0 ALERT level A = In general: serious problem 3 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 4 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 5 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
checkCIF publication errors
Alert level A PUBL024_ALERT_1_A The number of authors is greater than 5. Please specify the role of each of the co-authors for your paper.
Author Response: N.Y. Coskun, F.A. Kilicaslan, S.M. Yalcin and A. Gul - did the synthesis, crystalized the title complex and prepared the chemical sections of the manuscript. M. Akkurt - solved and refined the crystal structure of the title complex, and prepared the manuscript. O. Buyukgungor - collected the XRD data. |
1 ALERT level A = Data missing that is essential or data in wrong format 0 ALERT level G = General alerts. Data that may be required is missing
All starting materials and reagents used were of standard analytical grade from Merck, Fluka and Aldrich. The title complex were synthesized according to literature (Ricciardi et al., 2000; Belviso et al., 2000).
2,3,7,8,13,17,18-Octakis(ethylsulfanyl)-5,10,15,20-porphyrazine (0.1 g, 0.12 mmol) was dissolved in CHCl3 and added to the solution of Zn(CH3COO)2.4H2O (0.306 g, 1.2 mmol) in EtOH. The mixture was refluxed under argon for 1 h. After cooling to room temperature, insoluble excess Zn(CH3COO)2 was separeted by filtering. The filtrate was evaporated and the resulting deep blue solid was purified by chromatography on silica gel using CHCl3. For single-crystal, compound (I) has been crystalized at CHCl3/ MeOH (1/9).
H atoms were positioned geometrically with C—H = 0.96 and 0.97 Å and refined using a riding model with Uiso(H) = 1.2 or 1.5Ueq(C). The three ethyl groups of the title molecule are disordered over two sites in the 0.841 (10):0.159 (10) for C5A/C6A:C5B/C6B, 0.802 (10):0.198 (10) for C13A/C14A:C13B/C14B and 0.457 (13):0.543 (13) for C32A/C33A:C32B/C33B ratios and they were refined isotropicaly for a stable refinement. The S (S8A:S8B) atom with the third ethyl group (C32A/C33A:C32B/C33B) and the C atom (C27A:C27B) of the pyrrole ring attached to are also disorder over two sites in a 0.457 (13):0.543 (13) ratio. In the disorder segments of (I), the DFIX instructions were used to constrain the bond lengths to reasonable values.
The synthesis and characterization of porphyrazines (tetrapyrrole macrocycles) and their metal complexes are a topic of growing interest (Schramm & Hoffman, 1980). They have high symmetry, planarity, thermal stability and electronic delocalization. So, these types of compounds have potential applications for interesting optical, electrical, medical and catalytic properties. One synthetic route to octakis-functionalized porphyrazine is the cyclization of the functionalized dicyano precursor in the presence of magnesium alkoxide (Sakellariou et al., 2000; Ramirez et al., 2004). Their properties can be easily modified by attachment of diverse peripheral substituents, heteroatoms or alternation of the cetral metal ion.
The Zr(IV), Mn(III), Fe(III), Cu(II), Ni(II) and some lantanides complexes of (ethylsulfanyl) porphyrazines have been investigated (Ricciardi et al., 1996a,b; 1998; 1999). In this present work, we report the crystal structure of the title compound (I).
In the molecule of (I) shown in Fig. 1, the Zn—N bond distances range from from 1.994 (2) to 2.004 (2) Å. The intermolecular Zn—S distance [2.6364 (9) Å] which leads to a pseudo-square-pyramidal coordination around the ZnII ion, is shorter than the Co—S distances [alternatively 2.789 (5) and 2.842 (5) Å] in ((ethylsulfanyl)porphyrazinato)cobalt(II) (Ricciardi et al., 1999).
The molecular conformation of (I) is stabilized by weak intramolecular C—H···N and C—H···S interactions. In the crystal structure, intermolecular C—H···S contacts (Fig. 2), weak C—H···π interactions and π-π stacking interactions [Cg3···Cg4ii = 3.832 (4) Å and Cg3···Cg5ii = 3.850 (5) Å; symmetry code: (ii) 1/2 + x, y, 1/2 - z; Cg3, Cg4 and Cg5 are the centroids of the N5/C17–C20, N7/C25/C26/C27B/C28 and N7/C25/C26/C27A/C28 rings, respectively] contribute to the stabilization of the crystal structure.
For the synthesis of the title complex, see: Ricciardi et al. (2000); Belviso et al. (2000). For the synthesis and characterization of porphyrazines and their metal complexes, see: Schramm & Hoffman (1980); Sakellariou et al. (2000); Ramirez et al. (2004). For the Zr(IV), Mn(III), Fe(III), Cu(II), Ni(II) and some lantanides complexes of (ethylsulfanyl) porphyrazines, see: Ricciardi et al.(1996a,b, 1998, 1999).
Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
[Zn(C32H40N8S8)] | F(000) = 3568 |
Mr = 858.67 | Dx = 1.481 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 86381 reflections |
a = 8.7973 (1) Å | θ = 1.3–26.2° |
b = 27.2813 (3) Å | µ = 1.11 mm−1 |
c = 32.0903 (6) Å | T = 295 K |
V = 7701.73 (19) Å3 | Prism, black |
Z = 8 | 0.60 × 0.37 × 0.13 mm |
Stoe IPDS 2 diffractometer | 7282 independent reflections |
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus | 5696 reflections with I > 2σ(I) |
Plane graphite monochromator | Rint = 0.000 |
Detector resolution: 6.67 pixels mm-1 | θmax = 25.7°, θmin = 1.3° |
ω scans | h = 0→10 |
Absorption correction: part of the refinement model (ΔF) (XABS2; Parkin et al., 1995) | k = 0→33 |
Tmin = 0.620, Tmax = 0.866 | l = 0→38 |
7282 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.097 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0526P)2 + 1.401P] where P = (Fo2 + 2Fc2)/3 |
7282 reflections | (Δ/σ)max = 0.001 |
466 parameters | Δρmax = 0.44 e Å−3 |
16 restraints | Δρmin = −0.30 e Å−3 |
[Zn(C32H40N8S8)] | V = 7701.73 (19) Å3 |
Mr = 858.67 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 8.7973 (1) Å | µ = 1.11 mm−1 |
b = 27.2813 (3) Å | T = 295 K |
c = 32.0903 (6) Å | 0.60 × 0.37 × 0.13 mm |
Stoe IPDS 2 diffractometer | 7282 independent reflections |
Absorption correction: part of the refinement model (ΔF) (XABS2; Parkin et al., 1995) | 5696 reflections with I > 2σ(I) |
Tmin = 0.620, Tmax = 0.866 | Rint = 0.000 |
7282 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 16 restraints |
wR(F2) = 0.097 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.44 e Å−3 |
7282 reflections | Δρmin = −0.30 e Å−3 |
466 parameters |
Experimental. (XABS2; Parkin et al., 1995; Cubic fit to sin(theta)/lambda - 24 parameters) |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Zn1 | 0.62155 (4) | 0.18388 (1) | 0.32349 (1) | 0.0401 (1) | |
S1 | 0.56218 (12) | 0.06894 (3) | 0.47611 (3) | 0.0617 (3) | |
S2 | 0.79562 (12) | 0.16274 (3) | 0.50015 (2) | 0.0623 (3) | |
S3 | 1.05348 (11) | 0.31228 (3) | 0.40786 (3) | 0.0598 (3) | |
S4 | 1.05456 (10) | 0.34318 (3) | 0.30195 (3) | 0.0579 (3) | |
S5 | 0.88817 (9) | 0.24250 (3) | 0.16339 (2) | 0.0441 (2) | |
S6 | 0.60435 (10) | 0.14544 (3) | 0.14841 (2) | 0.0541 (3) | |
S7 | 0.27372 (11) | 0.03081 (3) | 0.23777 (3) | 0.0579 (3) | |
S8B | 0.3114 (11) | −0.0068 (2) | 0.33482 (16) | 0.0732 (15) | 0.543 (13) |
N1 | 0.6525 (3) | 0.15882 (8) | 0.38158 (7) | 0.0413 (8) | |
N2 | 0.8203 (3) | 0.22106 (8) | 0.40843 (7) | 0.0410 (8) | |
N3 | 0.7915 (3) | 0.23069 (8) | 0.33388 (7) | 0.0389 (7) | |
N4 | 0.8438 (3) | 0.25778 (8) | 0.26365 (7) | 0.0385 (7) | |
N5 | 0.6573 (3) | 0.19305 (8) | 0.26230 (7) | 0.0381 (7) | |
N6 | 0.5007 (3) | 0.12757 (8) | 0.23537 (7) | 0.0400 (7) | |
N7 | 0.5143 (3) | 0.12142 (8) | 0.31024 (7) | 0.0406 (7) | |
N8 | 0.4965 (3) | 0.08565 (8) | 0.37884 (7) | 0.0433 (8) | |
C1 | 0.5853 (3) | 0.11832 (10) | 0.39820 (9) | 0.0418 (9) | |
C2 | 0.7336 (3) | 0.18153 (10) | 0.41229 (9) | 0.0421 (9) | |
C3 | 0.7156 (3) | 0.15368 (11) | 0.45124 (9) | 0.0446 (9) | |
C4 | 0.6246 (4) | 0.11465 (11) | 0.44202 (8) | 0.0451 (9) | |
C5A | 0.6702 (6) | 0.01709 (18) | 0.45794 (17) | 0.0751 (18)* | 0.841 (10) |
C6A | 0.8372 (8) | 0.0233 (3) | 0.4623 (3) | 0.120 (3)* | 0.841 (10) |
C7 | 0.8662 (6) | 0.22413 (16) | 0.50147 (13) | 0.0883 (18) | |
C8 | 0.9413 (6) | 0.2340 (2) | 0.54207 (13) | 0.101 (2) | |
C9 | 0.8469 (3) | 0.24323 (10) | 0.37194 (9) | 0.0407 (9) | |
C10 | 0.8562 (3) | 0.26070 (10) | 0.30526 (9) | 0.0389 (8) | |
C11 | 0.9524 (3) | 0.29630 (10) | 0.32636 (9) | 0.0424 (9) | |
C12 | 0.9476 (3) | 0.28539 (10) | 0.36767 (9) | 0.0438 (9) | |
C13A | 0.9045 (6) | 0.33738 (18) | 0.44078 (16) | 0.0690 (17)* | 0.802 (10) |
C14A | 0.8356 (9) | 0.3835 (3) | 0.4200 (3) | 0.107 (2)* | 0.802 (10) |
C15 | 0.9011 (4) | 0.37875 (13) | 0.27885 (13) | 0.0690 (14) | |
C16 | 0.9640 (6) | 0.41584 (14) | 0.24931 (16) | 0.092 (2) | |
C17 | 0.7582 (3) | 0.22486 (10) | 0.24441 (8) | 0.0372 (8) | |
C18 | 0.5973 (3) | 0.16502 (10) | 0.23179 (8) | 0.0387 (8) | |
C19 | 0.6603 (3) | 0.17977 (10) | 0.19120 (8) | 0.0384 (8) | |
C20 | 0.7609 (3) | 0.21698 (10) | 0.19924 (8) | 0.0385 (8) | |
C21 | 0.9468 (4) | 0.30188 (11) | 0.18359 (11) | 0.0552 (11) | |
C22 | 1.0154 (5) | 0.33019 (14) | 0.14801 (12) | 0.0753 (16) | |
C23 | 0.6966 (4) | 0.17078 (13) | 0.10339 (10) | 0.0573 (11) | |
C24 | 0.6649 (5) | 0.13667 (17) | 0.06641 (12) | 0.0817 (16) | |
C25 | 0.4650 (3) | 0.10740 (10) | 0.27176 (9) | 0.0394 (9) | |
C26 | 0.4646 (3) | 0.08733 (10) | 0.33842 (9) | 0.0403 (9) | |
C27B | 0.364 (3) | 0.0494 (5) | 0.3159 (4) | 0.041 (4) | 0.543 (13) |
C28 | 0.3731 (3) | 0.06272 (10) | 0.27547 (9) | 0.0416 (9) | |
C29 | 0.3727 (5) | 0.03955 (17) | 0.18997 (12) | 0.0837 (16) | |
C30 | 0.3176 (6) | 0.00225 (19) | 0.15882 (14) | 0.0970 (19) | |
C31B | 0.3468 (12) | −0.0166 (3) | 0.3838 (2) | 0.080 (3)* | 0.543 (13) |
C32B | 0.2550 (14) | −0.0561 (4) | 0.4038 (3) | 0.085 (3)* | 0.543 (13) |
C31A | 0.2574 (14) | 0.0014 (4) | 0.3878 (3) | 0.076 (3)* | 0.457 (13) |
C32A | 0.1888 (19) | −0.0470 (5) | 0.4029 (4) | 0.103 (4)* | 0.457 (13) |
C13B | 0.960 (3) | 0.3675 (9) | 0.4188 (14) | 0.174 (18)* | 0.198 (10) |
C5B | 0.721 (3) | 0.0346 (12) | 0.4914 (8) | 0.112 (14)* | 0.159 (10) |
C6B | 0.815 (4) | 0.0050 (19) | 0.4767 (16) | 0.145 (19)* | 0.159 (10) |
S8A | 0.2570 (7) | 0.0047 (3) | 0.3375 (2) | 0.0643 (14) | 0.457 (13) |
C14B | 0.804 (2) | 0.3711 (8) | 0.4367 (7) | 0.062 (6)* | 0.198 (10) |
C27A | 0.386 (3) | 0.0512 (7) | 0.3183 (4) | 0.044 (5) | 0.457 (13) |
H6A1 | 0.88780 | −0.00550 | 0.45220 | 0.1800* | 0.841 (10) |
H8B | 0.99020 | 0.26540 | 0.54110 | 0.1520* | |
H6A2 | 0.86220 | 0.02840 | 0.49110 | 0.1800* | 0.841 (10) |
H6A3 | 0.86940 | 0.05120 | 0.44630 | 0.1800* | 0.841 (10) |
H7A | 0.93860 | 0.22890 | 0.47900 | 0.1060* | |
H7B | 0.78290 | 0.24690 | 0.49750 | 0.1060* | |
H8A | 0.86650 | 0.23390 | 0.56380 | 0.1520* | |
H5A1 | 0.63920 | −0.01180 | 0.47340 | 0.0900* | 0.841 (10) |
H5A2 | 0.64620 | 0.01140 | 0.42880 | 0.0900* | 0.841 (10) |
H15B | 0.84410 | 0.39520 | 0.30060 | 0.0820* | |
H16A | 1.03170 | 0.43740 | 0.26400 | 0.1380* | |
H16B | 0.88230 | 0.43450 | 0.23750 | 0.1380* | |
H16C | 1.01860 | 0.39940 | 0.22750 | 0.1380* | |
H21A | 0.85990 | 0.31930 | 0.19480 | 0.0660* | |
H21B | 1.02090 | 0.29770 | 0.20570 | 0.0660* | |
H22A | 1.09790 | 0.31180 | 0.13630 | 0.1130* | |
H22B | 1.05250 | 0.36110 | 0.15800 | 0.1130* | |
H22C | 0.93940 | 0.33570 | 0.12710 | 0.1130* | |
H23A | 0.65740 | 0.20330 | 0.09770 | 0.0690* | |
H23B | 0.80520 | 0.17330 | 0.10820 | 0.0690* | |
H24A | 0.71200 | 0.10550 | 0.07130 | 0.1230* | |
H24B | 0.70560 | 0.15090 | 0.04140 | 0.1230* | |
H24C | 0.55720 | 0.13230 | 0.06340 | 0.1230* | |
H29A | 0.35430 | 0.07240 | 0.17950 | 0.1000* | |
H29B | 0.48110 | 0.03570 | 0.19440 | 0.1000* | |
H30A | 0.34790 | −0.02990 | 0.16760 | 0.1450* | |
H30B | 0.36100 | 0.00920 | 0.13200 | 0.1450* | |
H30C | 0.20880 | 0.00370 | 0.15700 | 0.1450* | |
H31C | 0.45350 | −0.02490 | 0.38670 | 0.0950* | 0.543 (13) |
H31D | 0.32970 | 0.01370 | 0.39900 | 0.0950* | 0.543 (13) |
H32D | 0.15860 | −0.04310 | 0.41240 | 0.1280* | 0.543 (13) |
H32E | 0.30830 | −0.06850 | 0.42770 | 0.1280* | 0.543 (13) |
H32F | 0.23910 | −0.08220 | 0.38420 | 0.1280* | 0.543 (13) |
H8C | 1.01560 | 0.20900 | 0.54750 | 0.1520* | |
H13A | 0.82570 | 0.31300 | 0.44490 | 0.0830* | 0.802 (10) |
H13B | 0.94620 | 0.34590 | 0.46780 | 0.0830* | 0.802 (10) |
H14A | 0.91020 | 0.40920 | 0.41940 | 0.1610* | 0.802 (10) |
H14B | 0.74860 | 0.39420 | 0.43570 | 0.1610* | 0.802 (10) |
H14C | 0.80510 | 0.37580 | 0.39200 | 0.1610* | 0.802 (10) |
H15A | 0.83230 | 0.35700 | 0.26410 | 0.0820* | |
H5B1 | 0.78610 | 0.05950 | 0.50330 | 0.1350* | 0.159 (10) |
H5B2 | 0.68140 | 0.01670 | 0.51520 | 0.1350* | 0.159 (10) |
H6B1 | 0.88970 | −0.00250 | 0.49740 | 0.2170* | 0.159 (10) |
H6B2 | 0.86300 | 0.01930 | 0.45280 | 0.2170* | 0.159 (10) |
H6B3 | 0.76310 | −0.02450 | 0.46860 | 0.2170* | 0.159 (10) |
H13C | 1.02560 | 0.38560 | 0.43760 | 0.2080* | 0.198 (10) |
H13D | 0.95750 | 0.38580 | 0.39290 | 0.2080* | 0.198 (10) |
H14D | 0.78010 | 0.34120 | 0.45120 | 0.0930* | 0.198 (10) |
H14E | 0.73190 | 0.37610 | 0.41470 | 0.0930* | 0.198 (10) |
H14F | 0.79960 | 0.39810 | 0.45580 | 0.0930* | 0.198 (10) |
H31A | 0.36090 | 0.00410 | 0.39790 | 0.0920* | 0.457 (13) |
H31B | 0.19940 | 0.02850 | 0.39920 | 0.0920* | 0.457 (13) |
H32A | 0.09080 | −0.05150 | 0.39030 | 0.1550* | 0.457 (13) |
H32B | 0.17820 | −0.04620 | 0.43260 | 0.1550* | 0.457 (13) |
H32C | 0.25440 | −0.07360 | 0.39510 | 0.1550* | 0.457 (13) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0468 (2) | 0.0382 (2) | 0.0354 (2) | −0.0078 (2) | −0.0025 (1) | 0.0019 (1) |
S1 | 0.0823 (6) | 0.0590 (5) | 0.0437 (4) | −0.0114 (5) | 0.0107 (4) | 0.0101 (4) |
S2 | 0.0815 (7) | 0.0699 (6) | 0.0356 (4) | −0.0123 (5) | −0.0052 (4) | 0.0005 (4) |
S3 | 0.0621 (5) | 0.0587 (5) | 0.0586 (5) | −0.0113 (4) | −0.0147 (4) | −0.0084 (4) |
S4 | 0.0507 (5) | 0.0533 (5) | 0.0696 (5) | −0.0140 (4) | −0.0031 (4) | 0.0120 (4) |
S5 | 0.0476 (4) | 0.0468 (4) | 0.0379 (3) | −0.0042 (3) | 0.0024 (3) | 0.0048 (3) |
S6 | 0.0644 (5) | 0.0564 (5) | 0.0416 (4) | −0.0071 (4) | −0.0033 (4) | −0.0026 (3) |
S7 | 0.0627 (5) | 0.0569 (5) | 0.0542 (5) | −0.0169 (4) | −0.0044 (4) | −0.0068 (4) |
S8B | 0.115 (4) | 0.0484 (19) | 0.0562 (13) | −0.032 (2) | 0.008 (2) | −0.0002 (13) |
N1 | 0.0487 (15) | 0.0380 (13) | 0.0371 (12) | −0.0066 (11) | −0.0021 (11) | 0.0024 (10) |
N2 | 0.0461 (14) | 0.0394 (13) | 0.0375 (12) | −0.0025 (11) | −0.0038 (11) | −0.0004 (10) |
N3 | 0.0404 (14) | 0.0378 (12) | 0.0385 (12) | −0.0053 (10) | −0.0021 (10) | 0.0020 (10) |
N4 | 0.0402 (13) | 0.0365 (12) | 0.0389 (12) | −0.0016 (10) | 0.0015 (10) | 0.0020 (9) |
N5 | 0.0409 (13) | 0.0369 (12) | 0.0365 (12) | −0.0035 (10) | 0.0002 (10) | 0.0004 (9) |
N6 | 0.0431 (13) | 0.0378 (12) | 0.0390 (13) | −0.0019 (11) | −0.0014 (10) | −0.0007 (10) |
N7 | 0.0483 (14) | 0.0354 (12) | 0.0380 (12) | −0.0060 (11) | 0.0005 (11) | 0.0008 (10) |
N8 | 0.0494 (15) | 0.0392 (13) | 0.0414 (13) | −0.0053 (11) | 0.0014 (11) | 0.0021 (10) |
C1 | 0.0440 (17) | 0.0424 (16) | 0.0389 (14) | 0.0007 (13) | 0.0022 (12) | 0.0033 (12) |
C2 | 0.0455 (17) | 0.0425 (16) | 0.0382 (14) | 0.0020 (13) | −0.0013 (12) | −0.0011 (12) |
C3 | 0.0503 (18) | 0.0477 (16) | 0.0359 (15) | 0.0008 (14) | 0.0029 (13) | −0.0002 (12) |
C4 | 0.0557 (18) | 0.0447 (16) | 0.0349 (14) | −0.0032 (14) | 0.0040 (14) | 0.0034 (12) |
C7 | 0.123 (4) | 0.082 (3) | 0.060 (2) | −0.027 (3) | −0.024 (2) | −0.004 (2) |
C8 | 0.105 (4) | 0.133 (4) | 0.066 (3) | −0.039 (3) | −0.008 (3) | −0.020 (3) |
C9 | 0.0412 (16) | 0.0390 (15) | 0.0418 (15) | −0.0005 (12) | −0.0030 (12) | −0.0025 (12) |
C10 | 0.0366 (15) | 0.0373 (14) | 0.0429 (15) | 0.0003 (12) | −0.0003 (12) | 0.0022 (12) |
C11 | 0.0407 (16) | 0.0375 (14) | 0.0491 (17) | −0.0036 (13) | −0.0026 (13) | 0.0031 (13) |
C12 | 0.0434 (17) | 0.0410 (16) | 0.0471 (16) | −0.0044 (13) | −0.0080 (14) | −0.0040 (12) |
C15 | 0.072 (2) | 0.052 (2) | 0.083 (3) | 0.0030 (18) | 0.005 (2) | 0.0121 (18) |
C16 | 0.106 (4) | 0.060 (2) | 0.109 (4) | 0.005 (2) | 0.012 (3) | 0.026 (2) |
C17 | 0.0372 (15) | 0.0372 (14) | 0.0373 (14) | 0.0019 (12) | 0.0020 (12) | 0.0051 (11) |
C18 | 0.0392 (16) | 0.0392 (14) | 0.0376 (14) | 0.0037 (12) | −0.0016 (12) | 0.0006 (12) |
C19 | 0.0423 (16) | 0.0403 (15) | 0.0325 (13) | 0.0042 (12) | −0.0015 (11) | 0.0013 (11) |
C20 | 0.0395 (15) | 0.0390 (15) | 0.0371 (14) | 0.0010 (12) | 0.0007 (12) | 0.0033 (11) |
C21 | 0.063 (2) | 0.0427 (17) | 0.060 (2) | −0.0037 (16) | 0.0114 (17) | −0.0012 (14) |
C22 | 0.098 (3) | 0.055 (2) | 0.073 (3) | −0.013 (2) | 0.014 (2) | 0.0118 (18) |
C23 | 0.062 (2) | 0.067 (2) | 0.0428 (17) | 0.0045 (17) | 0.0014 (15) | −0.0003 (15) |
C24 | 0.088 (3) | 0.105 (3) | 0.052 (2) | 0.001 (3) | −0.010 (2) | −0.017 (2) |
C25 | 0.0410 (16) | 0.0350 (14) | 0.0423 (15) | 0.0007 (12) | −0.0010 (12) | −0.0026 (12) |
C26 | 0.0427 (16) | 0.0365 (15) | 0.0418 (15) | −0.0008 (13) | 0.0006 (13) | 0.0010 (12) |
C27B | 0.034 (6) | 0.033 (6) | 0.057 (7) | −0.004 (4) | −0.010 (4) | −0.016 (5) |
C28 | 0.0418 (16) | 0.0386 (15) | 0.0445 (17) | −0.0021 (13) | −0.0020 (13) | −0.0014 (12) |
C29 | 0.091 (3) | 0.101 (3) | 0.059 (2) | −0.031 (3) | 0.007 (2) | −0.021 (2) |
C30 | 0.100 (3) | 0.117 (4) | 0.074 (3) | −0.020 (3) | −0.006 (3) | −0.033 (3) |
S8A | 0.063 (2) | 0.058 (3) | 0.072 (2) | −0.0233 (17) | −0.0153 (19) | 0.021 (2) |
C27A | 0.043 (9) | 0.048 (8) | 0.040 (7) | −0.017 (5) | 0.002 (6) | 0.021 (6) |
Zn1—N1 | 2.004 (2) | C27A—C28 | 1.415 (14) |
Zn1—N3 | 1.994 (2) | C27B—C28 | 1.350 (13) |
Zn1—N5 | 2.004 (2) | C29—C30 | 1.507 (7) |
Zn1—N7 | 1.994 (2) | C31A—C32A | 1.531 (18) |
Zn1—S5i | 2.6364 (9) | C31B—C32B | 1.492 (14) |
S1—C4 | 1.747 (3) | C5A—H5A1 | 0.9700 |
S1—C5A | 1.801 (5) | C5A—H5A2 | 0.9700 |
S1—C5B | 1.75 (3) | C5B—H5B1 | 0.9700 |
S2—C3 | 1.738 (3) | C5B—H5B2 | 0.9700 |
S2—C7 | 1.787 (5) | C6A—H6A3 | 0.9600 |
S3—C12 | 1.752 (3) | C6A—H6A1 | 0.9600 |
S3—C13A | 1.817 (5) | C6A—H6A2 | 0.9600 |
S3—C13B | 1.75 (3) | C6B—H6B2 | 0.9600 |
S4—C11 | 1.748 (3) | C6B—H6B1 | 0.9600 |
S4—C15 | 1.820 (4) | C6B—H6B3 | 0.9600 |
S5—C20 | 1.750 (3) | C7—H7B | 0.9700 |
S5—C21 | 1.820 (3) | C7—H7A | 0.9700 |
S6—C19 | 1.734 (3) | C8—H8B | 0.9600 |
S6—C23 | 1.796 (3) | C8—H8A | 0.9600 |
S7—C28 | 1.728 (3) | C8—H8C | 0.9600 |
S7—C29 | 1.780 (4) | C13A—H13B | 0.9700 |
S8A—C27A | 1.81 (2) | C13A—H13A | 0.9700 |
S8A—C31A | 1.617 (12) | C13B—H13C | 0.9700 |
S8B—C27B | 1.713 (16) | C13B—H13D | 0.9700 |
S8B—C31B | 1.625 (9) | C14A—H14C | 0.9600 |
N1—C2 | 1.365 (4) | C14A—H14A | 0.9600 |
N1—C1 | 1.362 (4) | C14A—H14B | 0.9600 |
N2—C2 | 1.327 (4) | C14B—H14E | 0.9600 |
N2—C9 | 1.339 (4) | C14B—H14D | 0.9600 |
N3—C10 | 1.356 (4) | C14B—H14F | 0.9600 |
N3—C9 | 1.359 (4) | C15—H15A | 0.9700 |
N4—C17 | 1.325 (4) | C15—H15B | 0.9700 |
N4—C10 | 1.342 (4) | C16—H16B | 0.9600 |
N5—C17 | 1.368 (4) | C16—H16C | 0.9600 |
N5—C18 | 1.350 (3) | C16—H16A | 0.9600 |
N6—C25 | 1.329 (4) | C21—H21B | 0.9700 |
N6—C18 | 1.334 (4) | C21—H21A | 0.9700 |
N7—C25 | 1.364 (4) | C22—H22A | 0.9600 |
N7—C26 | 1.369 (4) | C22—H22B | 0.9600 |
N8—C1 | 1.338 (4) | C22—H22C | 0.9600 |
N8—C26 | 1.328 (4) | C23—H23B | 0.9700 |
C1—C4 | 1.452 (4) | C23—H23A | 0.9700 |
C2—C3 | 1.471 (4) | C24—H24B | 0.9600 |
C3—C4 | 1.365 (4) | C24—H24A | 0.9600 |
C5A—C6A | 1.486 (9) | C24—H24C | 0.9600 |
C5B—C6B | 1.25 (5) | C29—H29B | 0.9700 |
C7—C8 | 1.485 (6) | C29—H29A | 0.9700 |
C9—C12 | 1.458 (4) | C30—H30C | 0.9600 |
C10—C11 | 1.455 (4) | C30—H30A | 0.9600 |
C11—C12 | 1.359 (4) | C30—H30B | 0.9600 |
C13A—C14A | 1.548 (10) | C31A—H31B | 0.9700 |
C13B—C14B | 1.49 (3) | C31A—H31A | 0.9700 |
C15—C16 | 1.493 (6) | C31B—H31D | 0.9700 |
C17—C20 | 1.466 (4) | C31B—H31C | 0.9700 |
C18—C19 | 1.472 (4) | C32A—H32B | 0.9600 |
C19—C20 | 1.371 (4) | C32A—H32C | 0.9600 |
C21—C22 | 1.505 (5) | C32A—H32A | 0.9600 |
C23—C24 | 1.534 (5) | C32B—H32D | 0.9600 |
C25—C28 | 1.468 (4) | C32B—H32E | 0.9600 |
C26—C27B | 1.542 (19) | C32B—H32F | 0.9600 |
C26—C27A | 1.37 (2) | ||
Zn1···H23Bi | 3.5500 | C21···N4 | 2.978 (4) |
S1···S2 | 3.3706 (13) | C21···S4i | 3.660 (4) |
S1···N8 | 3.207 (2) | C23···S5 | 3.221 (4) |
S2···C5B | 3.57 (3) | C25···S7iv | 3.440 (3) |
S2···S3ii | 3.7036 (13) | C25···C18i | 3.598 (4) |
S2···N2 | 3.353 (2) | C25···C19i | 3.535 (4) |
S2···S1 | 3.3706 (13) | C26···S6i | 3.569 (3) |
S3···S4 | 3.5017 (14) | C27B···S6i | 3.66 (2) |
S3···N2 | 3.225 (3) | C28···S7iv | 3.655 (3) |
S3···S2iii | 3.7036 (13) | C29···S8Aiv | 3.621 (8) |
S4···C21iv | 3.660 (4) | C29···N6 | 3.026 (5) |
S4···S3 | 3.5017 (14) | C31A···N8 | 3.129 (12) |
S4···N4 | 3.221 (3) | C31B···N8 | 3.089 (9) |
S5···C23 | 3.221 (4) | C32B···C13Bvi | 3.30 (3) |
S5···N4 | 3.268 (2) | C32B···C5Bv | 3.42 (3) |
S5···S6 | 3.6711 (12) | C1···H23Bi | 2.8900 |
S6···S5 | 3.6711 (12) | C2···H8Bii | 2.9900 |
S6···C27Biv | 3.66 (2) | C2···H7A | 3.0800 |
S6···N6 | 2.976 (2) | C3···H24Civ | 3.1000 |
S6···C26iv | 3.569 (3) | C3···H8Bii | 2.9800 |
S6···C9i | 3.560 (3) | C4···H6A3 | 2.7700 |
S7···C25i | 3.440 (3) | C5B···H32Ev | 2.7700 |
S7···S8A | 3.282 (7) | C6A···H30Biv | 3.0600 |
S7···S8B | 3.296 (5) | C6B···H6B1viii | 2.7300 |
S7···N6 | 3.311 (3) | C7···H13A | 3.0500 |
S7···C28i | 3.655 (3) | C9···H23Aiv | 3.1000 |
S8A···S7 | 3.282 (7) | C9···H13A | 3.0200 |
S8A···N8 | 3.328 (8) | C9···H22Ai | 2.8900 |
S8A···C29i | 3.621 (8) | C10···H15A | 2.9500 |
S8B···S7 | 3.296 (5) | C12···H14C | 2.8700 |
S8B···N8 | 3.318 (7) | C13B···H32Eix | 2.7000 |
S1···H13Bii | 3.1100 | C14A···H6B3ix | 3.0800 |
S1···H5A1v | 2.8600 | C21···H16C | 3.0800 |
S1···H5B2v | 3.1800 | C22···H14Eiv | 3.0400 |
S1···H13Cii | 3.0500 | C26···H31D | 3.0400 |
S2···H5B1 | 2.8200 | C32B···H5B2v | 2.8700 |
S2···H24Civ | 3.1800 | C32B···H13Cvi | 2.7300 |
S3···H23Aiv | 3.1200 | C32B···H5B1v | 3.0000 |
S3···H8Aiii | 3.1600 | C32B···H13Dvi | 3.0100 |
S4···H21Aiv | 2.7700 | H5A1···S1v | 2.8600 |
S5···H23A | 3.1200 | H5A2···N8 | 2.9000 |
S5···H23B | 2.6900 | H6A3···C4 | 2.7700 |
S6···H29A | 3.1300 | H5B1···C32Bv | 3.0000 |
S7···H16Avi | 3.1800 | H5B1···S2 | 2.8200 |
S7···H16Bvii | 3.0700 | H5B1···H32Ev | 2.3800 |
S8A···H29Bi | 2.7700 | H5B2···C32Bv | 2.8700 |
S8B···H16Avi | 3.0600 | H5B2···H32Ev | 2.3200 |
N1···N3 | 2.772 (3) | H5B2···S1v | 3.1800 |
N1···N7 | 2.786 (3) | H7A···N2 | 2.5000 |
N1···C9 | 2.885 (4) | H7A···C2 | 3.0800 |
N1···C26 | 2.908 (4) | H7B···H13A | 2.5000 |
N2···S3 | 3.225 (3) | H6B1···H6B1viii | 1.9500 |
N2···C7 | 3.014 (5) | H6B1···C6Bviii | 2.7300 |
N2···S2 | 3.353 (2) | H8A···S3ii | 3.1600 |
N2···C13A | 3.420 (5) | H8B···C3iii | 2.9800 |
N3···N5 | 2.779 (3) | H8B···C2iii | 2.9900 |
N3···C2 | 2.896 (4) | H6B3···H14Bvi | 2.4600 |
N3···C17 | 2.890 (3) | H6B3···C14Avi | 3.0800 |
N3···N1 | 2.772 (3) | H13A···C7 | 3.0500 |
N4···S4 | 3.221 (3) | H13A···N2 | 2.7700 |
N4···S5 | 3.268 (2) | H13A···C9 | 3.0200 |
N4···C21 | 2.978 (4) | H13A···H7B | 2.5000 |
N4···C18iv | 3.376 (4) | H13B···S1iii | 3.1100 |
N4···C15 | 3.374 (4) | H13C···S1iii | 3.0500 |
N5···C25 | 2.901 (4) | H13C···C32Bix | 2.7300 |
N5···N3 | 2.779 (3) | H13C···H32Eix | 1.9500 |
N5···C10 | 2.893 (4) | H13D···C32Bix | 3.0100 |
N5···N7 | 2.787 (3) | H13D···H31Cix | 2.5700 |
N6···S7 | 3.311 (3) | H14B···H6B3ix | 2.4600 |
N6···S6 | 2.976 (2) | H14C···C12 | 2.8700 |
N6···C29 | 3.026 (5) | H14E···C22i | 3.0400 |
N7···C18 | 2.879 (3) | H15A···C10 | 2.9500 |
N7···N5 | 2.787 (3) | H15A···N4 | 2.7100 |
N7···C1 | 2.892 (4) | H15A···H21A | 2.4600 |
N7···N1 | 2.786 (3) | H16A···S8Bix | 3.0600 |
N7···C20i | 3.444 (4) | H16A···S7ix | 3.1800 |
N8···S8B | 3.318 (7) | H16B···S7x | 3.0700 |
N8···S8A | 3.328 (8) | H16C···C21 | 3.0800 |
N8···S1 | 3.207 (2) | H16C···H22B | 2.4800 |
N8···C31B | 3.089 (9) | H21A···N4 | 2.7800 |
N8···C31A | 3.129 (12) | H21A···H15A | 2.4600 |
N2···H13A | 2.7700 | H21A···S4i | 2.7700 |
N2···H7A | 2.5000 | H21B···N4 | 2.6600 |
N4···H15A | 2.7100 | H22A···C9iv | 2.8900 |
N4···H21B | 2.6600 | H22B···H16C | 2.4800 |
N4···H21A | 2.7800 | H23A···S3i | 3.1200 |
N6···H29B | 2.8400 | H23A···C9i | 3.1000 |
N6···H29A | 2.6700 | H23A···S5 | 3.1200 |
N8···H31D | 2.5300 | H23B···Zn1iv | 3.5500 |
N8···H5A2 | 2.9000 | H23B···C1iv | 2.8900 |
N8···H31A | 2.6000 | H23B···S5 | 2.6900 |
C5B···C32Bv | 3.42 (3) | H24A···H31Biv | 2.3100 |
C5B···S2 | 3.57 (3) | H24C···S2i | 3.1800 |
C6B···C6Bviii | 3.59 (5) | H24C···C3i | 3.1000 |
C7···N2 | 3.014 (5) | H29A···S6 | 3.1300 |
C9···S6iv | 3.560 (3) | H29A···N6 | 2.6700 |
C10···C18iv | 3.567 (4) | H29B···N6 | 2.8400 |
C10···C19iv | 3.471 (4) | H29B···S8Aiv | 2.7700 |
C11···C20iv | 3.567 (4) | H30B···C6Ai | 3.0600 |
C13A···N2 | 3.420 (5) | H31A···N8 | 2.6000 |
C13B···C32Bix | 3.30 (3) | H31B···H24Ai | 2.3100 |
C15···N4 | 3.374 (4) | H31C···H13Dvi | 2.5700 |
C17···C18iv | 3.485 (4) | H31D···N8 | 2.5300 |
C18···C17i | 3.485 (4) | H31D···C26 | 3.0400 |
C18···C25iv | 3.598 (4) | H32E···H5B1v | 2.3800 |
C18···C10i | 3.567 (4) | H32E···H5B2v | 2.3200 |
C18···N4i | 3.376 (4) | H32E···C13Bvi | 2.7000 |
C19···C25iv | 3.535 (4) | H32E···H13Cvi | 1.9500 |
C19···C10i | 3.471 (4) | H32E···C5Bv | 2.7700 |
C20···C11i | 3.567 (4) | ||
N1—Zn1—N3 | 87.77 (10) | S1—C5B—H5B2 | 102.00 |
N1—Zn1—N5 | 158.84 (10) | S1—C5B—H5B1 | 102.00 |
N1—Zn1—N7 | 88.35 (9) | H6A1—C6A—H6A3 | 109.00 |
S5i—Zn1—N1 | 99.45 (7) | H6A1—C6A—H6A2 | 110.00 |
N3—Zn1—N5 | 88.07 (10) | C5A—C6A—H6A1 | 109.00 |
N3—Zn1—N7 | 159.68 (10) | C5A—C6A—H6A2 | 109.00 |
S5i—Zn1—N3 | 99.71 (7) | C5A—C6A—H6A3 | 109.00 |
N5—Zn1—N7 | 88.40 (9) | H6A2—C6A—H6A3 | 109.00 |
S5i—Zn1—N5 | 101.71 (7) | C5B—C6B—H6B2 | 109.00 |
S5i—Zn1—N7 | 100.60 (8) | C5B—C6B—H6B3 | 109.00 |
C4—S1—C5A | 101.1 (2) | C5B—C6B—H6B1 | 109.00 |
C4—S1—C5B | 107.8 (9) | H6B1—C6B—H6B3 | 110.00 |
C3—S2—C7 | 107.19 (17) | H6B2—C6B—H6B3 | 109.00 |
C12—S3—C13A | 101.67 (19) | H6B1—C6B—H6B2 | 110.00 |
C12—S3—C13B | 105.0 (12) | C8—C7—H7A | 110.00 |
C11—S4—C15 | 101.02 (15) | H7A—C7—H7B | 108.00 |
C20—S5—C21 | 107.54 (15) | S2—C7—H7B | 110.00 |
Zn1iv—S5—C20 | 98.74 (9) | C8—C7—H7B | 110.00 |
Zn1iv—S5—C21 | 105.22 (11) | S2—C7—H7A | 110.00 |
C19—S6—C23 | 107.52 (15) | C7—C8—H8A | 109.00 |
C28—S7—C29 | 106.76 (17) | H8B—C8—H8C | 110.00 |
C27A—S8A—C31A | 112.2 (7) | C7—C8—H8B | 109.00 |
C27B—S8B—C31B | 116.0 (7) | C7—C8—H8C | 109.00 |
Zn1—N1—C2 | 125.99 (18) | H8A—C8—H8B | 110.00 |
C1—N1—C2 | 108.2 (2) | H8A—C8—H8C | 109.00 |
Zn1—N1—C1 | 125.59 (19) | S3—C13A—H13B | 110.00 |
C2—N2—C9 | 123.3 (2) | C14A—C13A—H13A | 110.00 |
Zn1—N3—C9 | 125.48 (19) | S3—C13A—H13A | 110.00 |
Zn1—N3—C10 | 126.03 (19) | H13A—C13A—H13B | 108.00 |
C9—N3—C10 | 107.8 (2) | C14A—C13A—H13B | 110.00 |
C10—N4—C17 | 123.4 (2) | S3—C13B—H13D | 106.00 |
Zn1—N5—C17 | 126.32 (18) | C14B—C13B—H13C | 106.00 |
Zn1—N5—C18 | 125.35 (19) | H13C—C13B—H13D | 107.00 |
C17—N5—C18 | 108.0 (2) | C14B—C13B—H13D | 106.00 |
C18—N6—C25 | 122.9 (2) | S3—C13B—H13C | 106.00 |
Zn1—N7—C25 | 125.69 (18) | H14A—C14A—H14C | 109.00 |
C25—N7—C26 | 107.8 (2) | C13A—C14A—H14A | 110.00 |
Zn1—N7—C26 | 126.23 (19) | C13A—C14A—H14B | 109.00 |
C1—N8—C26 | 123.6 (2) | C13A—C14A—H14C | 110.00 |
N1—C1—C4 | 109.4 (2) | H14A—C14A—H14B | 109.00 |
N8—C1—C4 | 122.9 (3) | H14B—C14A—H14C | 110.00 |
N1—C1—N8 | 127.7 (3) | C13B—C14B—H14D | 109.00 |
N1—C2—N2 | 127.0 (3) | C13B—C14B—H14E | 110.00 |
N2—C2—C3 | 124.1 (3) | C13B—C14B—H14F | 110.00 |
N1—C2—C3 | 108.8 (2) | H14D—C14B—H14E | 109.00 |
S2—C3—C2 | 130.6 (2) | H14D—C14B—H14F | 109.00 |
C2—C3—C4 | 106.4 (2) | H14E—C14B—H14F | 110.00 |
S2—C3—C4 | 123.0 (2) | S4—C15—H15B | 110.00 |
S1—C4—C1 | 125.5 (2) | C16—C15—H15A | 110.00 |
S1—C4—C3 | 127.3 (2) | S4—C15—H15A | 110.00 |
C1—C4—C3 | 107.2 (2) | H15A—C15—H15B | 108.00 |
S1—C5A—C6A | 113.7 (4) | C16—C15—H15B | 110.00 |
S1—C5B—C6B | 140 (3) | C15—C16—H16B | 109.00 |
S2—C7—C8 | 110.2 (3) | C15—C16—H16A | 109.00 |
N3—C9—C12 | 109.4 (2) | C15—C16—H16C | 109.00 |
N2—C9—C12 | 123.0 (3) | H16A—C16—H16B | 109.00 |
N2—C9—N3 | 127.6 (2) | H16A—C16—H16C | 109.00 |
N3—C10—C11 | 109.4 (2) | H16B—C16—H16C | 110.00 |
N3—C10—N4 | 127.2 (2) | H21A—C21—H21B | 108.00 |
N4—C10—C11 | 123.4 (2) | C22—C21—H21A | 110.00 |
S4—C11—C12 | 127.8 (2) | C22—C21—H21B | 110.00 |
S4—C11—C10 | 125.4 (2) | S5—C21—H21A | 110.00 |
C10—C11—C12 | 106.8 (2) | S5—C21—H21B | 110.00 |
S3—C12—C11 | 127.6 (2) | C21—C22—H22A | 109.00 |
C9—C12—C11 | 106.5 (2) | C21—C22—H22B | 110.00 |
S3—C12—C9 | 125.7 (2) | C21—C22—H22C | 109.00 |
S3—C13A—C14A | 109.8 (4) | H22A—C22—H22B | 109.00 |
S3—C13B—C14B | 124.5 (18) | H22A—C22—H22C | 110.00 |
S4—C15—C16 | 110.2 (3) | H22B—C22—H22C | 109.00 |
N4—C17—N5 | 127.1 (2) | S6—C23—H23A | 110.00 |
N5—C17—C20 | 109.4 (2) | S6—C23—H23B | 110.00 |
N4—C17—C20 | 123.5 (2) | C24—C23—H23B | 110.00 |
N6—C18—C19 | 121.7 (2) | H23A—C23—H23B | 108.00 |
N5—C18—N6 | 128.4 (2) | C24—C23—H23A | 110.00 |
N5—C18—C19 | 109.9 (2) | H24A—C24—H24B | 110.00 |
S6—C19—C18 | 116.5 (2) | H24A—C24—H24C | 109.00 |
S6—C19—C20 | 137.1 (2) | C23—C24—H24A | 109.00 |
C18—C19—C20 | 106.2 (2) | C23—C24—H24B | 109.00 |
S5—C20—C17 | 127.0 (2) | C23—C24—H24C | 109.00 |
S5—C20—C19 | 125.7 (2) | H24B—C24—H24C | 110.00 |
C17—C20—C19 | 106.5 (2) | S7—C29—H29B | 110.00 |
S5—C21—C22 | 107.5 (2) | S7—C29—H29A | 110.00 |
S6—C23—C24 | 107.9 (3) | H29A—C29—H29B | 108.00 |
N6—C25—N7 | 127.2 (2) | C30—C29—H29A | 110.00 |
N6—C25—C28 | 123.1 (3) | C30—C29—H29B | 110.00 |
N7—C25—C28 | 109.6 (2) | C29—C30—H30A | 109.00 |
N8—C26—C27B | 123.8 (5) | C29—C30—H30C | 109.00 |
N8—C26—C27A | 122.9 (7) | H30A—C30—H30B | 109.00 |
N7—C26—N8 | 127.0 (2) | C29—C30—H30B | 109.00 |
N7—C26—C27B | 109.3 (5) | H30B—C30—H30C | 109.00 |
N7—C26—C27A | 109.9 (7) | H30A—C30—H30C | 109.00 |
S8A—C27A—C28 | 115.9 (14) | S8A—C31A—H31B | 109.00 |
S8A—C27A—C26 | 131.5 (10) | S8A—C31A—H31A | 109.00 |
C26—C27A—C28 | 109.9 (13) | C32A—C31A—H31B | 109.00 |
C26—C27B—C28 | 103.6 (11) | H31A—C31A—H31B | 108.00 |
S8B—C27B—C28 | 126.7 (10) | C32A—C31A—H31A | 109.00 |
S8B—C27B—C26 | 126.2 (10) | S8B—C31B—H31C | 108.00 |
S7—C28—C27A | 127.5 (9) | S8B—C31B—H31D | 108.00 |
S7—C28—C25 | 129.8 (2) | H31C—C31B—H31D | 107.00 |
S7—C28—C27B | 120.5 (8) | C32B—C31B—H31C | 108.00 |
C25—C28—C27B | 109.5 (8) | C32B—C31B—H31D | 108.00 |
C25—C28—C27A | 102.7 (9) | C31A—C32A—H32A | 109.00 |
S7—C29—C30 | 108.9 (3) | C31A—C32A—H32B | 109.00 |
S8A—C31A—C32A | 111.3 (9) | C31A—C32A—H32C | 109.00 |
S8B—C31B—C32B | 115.6 (7) | H32A—C32A—H32B | 110.00 |
S1—C5A—H5A1 | 109.00 | H32B—C32A—H32C | 110.00 |
S1—C5A—H5A2 | 109.00 | H32A—C32A—H32C | 109.00 |
C6A—C5A—H5A1 | 109.00 | C31B—C32B—H32E | 109.00 |
C6A—C5A—H5A2 | 109.00 | C31B—C32B—H32F | 109.00 |
H5A1—C5A—H5A2 | 108.00 | H32D—C32B—H32F | 109.00 |
C6B—C5B—H5B1 | 102.00 | H32E—C32B—H32F | 109.00 |
C6B—C5B—H5B2 | 102.00 | H32D—C32B—H32E | 109.00 |
H5B1—C5B—H5B2 | 105.00 | C31B—C32B—H32D | 110.00 |
N1iv—Zn1iv—S5—C20 | 123.48 (11) | C9—N3—C10—N4 | 173.3 (3) |
N3iv—Zn1iv—S5—C20 | −147.19 (11) | Zn1—N3—C10—C11 | 167.87 (18) |
N5iv—Zn1iv—S5—C20 | −57.16 (12) | Zn1—N3—C10—N4 | −15.6 (4) |
N7iv—Zn1iv—S5—C20 | 33.40 (11) | Zn1—N3—C9—N2 | 13.3 (4) |
N1iv—Zn1iv—S5—C21 | −125.55 (14) | C9—N3—C10—C11 | −3.2 (3) |
N3iv—Zn1iv—S5—C21 | −36.22 (13) | C10—N4—C17—N5 | 8.1 (5) |
N5iv—Zn1iv—S5—C21 | 53.81 (14) | C17—N4—C10—N3 | 2.8 (5) |
N7iv—Zn1iv—S5—C21 | 144.37 (13) | C17—N4—C10—C11 | 178.9 (3) |
N3—Zn1—N1—C1 | −170.8 (2) | C10—N4—C17—C20 | −171.0 (3) |
N5—Zn1—N1—C1 | −92.0 (4) | C17—N5—C18—N6 | 176.0 (3) |
N7—Zn1—N1—C1 | −10.8 (2) | Zn1—N5—C17—C20 | 174.37 (18) |
S5i—Zn1—N1—C1 | 89.7 (2) | Zn1—N5—C17—N4 | −4.8 (4) |
N3—Zn1—N1—C2 | 15.2 (2) | Zn1—N5—C18—N6 | 2.4 (4) |
N5—Zn1—N1—C2 | 94.0 (3) | C18—N5—C17—C20 | 0.9 (3) |
N7—Zn1—N1—C2 | 175.3 (2) | C18—N5—C17—N4 | −178.3 (3) |
S5i—Zn1—N1—C2 | −84.2 (2) | C17—N5—C18—C19 | −1.1 (3) |
N1—Zn1—N3—C9 | −17.4 (2) | Zn1—N5—C18—C19 | −174.63 (18) |
N5—Zn1—N3—C9 | −176.7 (2) | C18—N6—C25—C28 | −172.6 (3) |
N7—Zn1—N3—C9 | −96.6 (3) | C18—N6—C25—N7 | 2.0 (5) |
S5i—Zn1—N3—C9 | 81.8 (2) | C25—N6—C18—C19 | 166.6 (3) |
N1—Zn1—N3—C10 | 173.0 (2) | C25—N6—C18—N5 | −10.2 (5) |
N5—Zn1—N3—C10 | 13.7 (2) | C26—N7—C25—N6 | −172.9 (3) |
N7—Zn1—N3—C10 | 93.9 (3) | Zn1—N7—C25—N6 | 12.7 (4) |
S5i—Zn1—N3—C10 | −87.8 (2) | Zn1—N7—C26—N8 | −10.3 (4) |
N1—Zn1—N5—C17 | −83.4 (3) | C25—N7—C26—C27B | −4.2 (9) |
N3—Zn1—N5—C17 | −4.6 (2) | Zn1—N7—C25—C28 | −172.11 (19) |
N7—Zn1—N5—C17 | −164.6 (2) | Zn1—N7—C26—C27B | 170.3 (9) |
S5i—Zn1—N5—C17 | 94.9 (2) | C25—N7—C26—N8 | 175.3 (3) |
N1—Zn1—N5—C18 | 89.1 (4) | C26—N7—C25—C28 | 2.3 (3) |
N3—Zn1—N5—C18 | 167.8 (2) | C26—N8—C1—C4 | −177.1 (3) |
N7—Zn1—N5—C18 | 7.8 (2) | C1—N8—C26—N7 | −0.1 (5) |
S5i—Zn1—N5—C18 | −92.7 (2) | C26—N8—C1—N1 | 2.7 (5) |
N1—Zn1—N7—C25 | −173.6 (2) | C1—N8—C26—C27B | 179.2 (11) |
N3—Zn1—N7—C25 | −94.6 (3) | N1—C1—C4—C3 | 0.3 (3) |
N5—Zn1—N7—C25 | −14.5 (2) | N8—C1—C4—S1 | −1.1 (4) |
S5i—Zn1—N7—C25 | 87.1 (2) | N1—C1—C4—S1 | 179.1 (2) |
N1—Zn1—N7—C26 | 13.0 (2) | N8—C1—C4—C3 | −179.9 (3) |
N3—Zn1—N7—C26 | 92.0 (3) | N1—C2—C3—C4 | 0.6 (3) |
N5—Zn1—N7—C26 | 172.1 (2) | N1—C2—C3—S2 | 177.3 (2) |
S5i—Zn1—N7—C26 | −86.3 (2) | N2—C2—C3—C4 | −177.0 (3) |
C4—S1—C5A—C6A | 62.8 (5) | N2—C2—C3—S2 | −0.3 (4) |
C5A—S1—C4—C1 | 72.1 (3) | C2—C3—C4—S1 | −179.4 (2) |
C5A—S1—C4—C3 | −109.2 (3) | S2—C3—C4—S1 | 3.6 (4) |
C3—S2—C7—C8 | −178.1 (3) | S2—C3—C4—C1 | −177.5 (2) |
C7—S2—C3—C4 | −166.6 (3) | C2—C3—C4—C1 | −0.5 (3) |
C7—S2—C3—C2 | 17.2 (3) | N2—C9—C12—C11 | 177.1 (3) |
C13A—S3—C12—C11 | 119.6 (3) | N3—C9—C12—S3 | −176.2 (2) |
C12—S3—C13A—C14A | −74.0 (4) | N2—C9—C12—S3 | 2.4 (4) |
C13A—S3—C12—C9 | −66.8 (3) | N3—C9—C12—C11 | −1.4 (3) |
C15—S4—C11—C10 | 62.0 (3) | N3—C10—C11—S4 | −178.3 (2) |
C11—S4—C15—C16 | −169.2 (3) | N4—C10—C11—C12 | −174.3 (3) |
C15—S4—C11—C12 | −118.8 (3) | N3—C10—C11—C12 | 2.4 (3) |
Zn1iv—S5—C20—C19 | −89.6 (2) | N4—C10—C11—S4 | 5.0 (4) |
C21—S5—C20—C19 | 161.3 (3) | C10—C11—C12—C9 | −0.5 (3) |
Zn1iv—S5—C20—C17 | 79.2 (2) | C10—C11—C12—S3 | 174.1 (2) |
C20—S5—C21—C22 | −162.9 (2) | S4—C11—C12—S3 | −5.2 (4) |
C21—S5—C20—C17 | −29.9 (3) | S4—C11—C12—C9 | −179.8 (2) |
Zn1iv—S5—C21—C22 | 92.6 (2) | N5—C17—C20—C19 | −0.4 (3) |
C23—S6—C19—C20 | −6.1 (4) | N5—C17—C20—S5 | −170.9 (2) |
C23—S6—C19—C18 | −179.9 (2) | N4—C17—C20—S5 | 8.3 (4) |
C19—S6—C23—C24 | 172.6 (2) | N4—C17—C20—C19 | 178.9 (3) |
C28—S7—C29—C30 | 164.8 (3) | N6—C18—C19—C20 | −176.5 (3) |
C29—S7—C28—C27B | −154.9 (11) | N5—C18—C19—C20 | 0.8 (3) |
C29—S7—C28—C25 | 30.2 (3) | N5—C18—C19—S6 | 176.49 (19) |
C27B—S8B—C31B—C32B | 158.9 (12) | N6—C18—C19—S6 | −0.8 (4) |
C31B—S8B—C27B—C26 | 11 (2) | C18—C19—C20—C17 | −0.3 (3) |
C31B—S8B—C27B—C28 | 166.6 (17) | S6—C19—C20—S5 | −3.8 (5) |
C2—N1—C1—C4 | 0.2 (3) | C18—C19—C20—S5 | 170.4 (2) |
Zn1—N1—C2—N2 | −8.1 (4) | S6—C19—C20—C17 | −174.6 (2) |
Zn1—N1—C1—N8 | 5.5 (4) | N7—C25—C28—C27B | 0.7 (11) |
Zn1—N1—C1—C4 | −174.7 (2) | N7—C25—C28—S7 | 176.0 (2) |
C2—N1—C1—N8 | −179.6 (3) | N6—C25—C28—C27B | 176.1 (11) |
Zn1—N1—C2—C3 | 174.35 (19) | N6—C25—C28—S7 | −8.6 (4) |
C1—N1—C2—N2 | 177.1 (3) | N7—C26—C27B—C28 | 4.5 (15) |
C1—N1—C2—C3 | −0.5 (3) | N8—C26—C27B—C28 | −175.0 (7) |
C2—N2—C9—N3 | 1.0 (5) | N8—C26—C27B—S8B | −15 (2) |
C9—N2—C2—C3 | 173.4 (3) | N7—C26—C27B—S8B | 164.4 (13) |
C9—N2—C2—N1 | −3.8 (5) | S8B—C27B—C28—C25 | −162.7 (16) |
C2—N2—C9—C12 | −177.3 (3) | C26—C27B—C28—S7 | −178.8 (6) |
Zn1—N3—C9—C12 | −168.27 (18) | C26—C27B—C28—C25 | −3.0 (15) |
C10—N3—C9—C12 | 2.9 (3) | S8B—C27B—C28—S7 | 22 (2) |
C10—N3—C9—N2 | −175.6 (3) |
Symmetry codes: (i) x−1/2, y, −z+1/2; (ii) x−1/2, −y+1/2, −z+1; (iii) x+1/2, −y+1/2, −z+1; (iv) x+1/2, y, −z+1/2; (v) −x+1, −y, −z+1; (vi) −x+3/2, y−1/2, z; (vii) −x+1, y−1/2, −z+1/2; (viii) −x+2, −y, −z+1; (ix) −x+3/2, y+1/2, z; (x) −x+1, y+1/2, −z+1/2. |
Cg1, Cg2 and Cg3 are the centroids of the N3/C9–C12, Zn1/N1/N7/N8/C1/C26 and Zn1/N3/N4/N5/C10/C17 rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
C5A—H5A1···S1v | 0.97 | 2.86 | 3.764 (5) | 155 |
C7—H7A···N2 | 0.97 | 2.50 | 3.014 (5) | 113 |
C21—H21A···S4i | 0.97 | 2.77 | 3.660 (4) | 154 |
C23—H23B···S5 | 0.97 | 2.69 | 3.221 (4) | 115 |
C31B—H31D···N8 | 0.97 | 2.53 | 3.089 (9) | 116 |
C21—H21B···Cg3iv | 0.97 | 2.86 | 3.536 (3) | 128 |
C22—H22A···Cg1iv | 0.96 | 2.90 | 3.699 (4) | 142 |
C23—H23B···Cg2iv | 0.97 | 2.81 | 3.641 (4) | 144 |
Symmetry codes: (i) x−1/2, y, −z+1/2; (iv) x+1/2, y, −z+1/2; (v) −x+1, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C32H40N8S8)] |
Mr | 858.67 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 295 |
a, b, c (Å) | 8.7973 (1), 27.2813 (3), 32.0903 (6) |
V (Å3) | 7701.73 (19) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 1.11 |
Crystal size (mm) | 0.60 × 0.37 × 0.13 |
Data collection | |
Diffractometer | Stoe IPDS 2 |
Absorption correction | Part of the refinement model (ΔF) (XABS2; Parkin et al., 1995) |
Tmin, Tmax | 0.620, 0.866 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7282, 7282, 5696 |
Rint | 0.000 |
(sin θ/λ)max (Å−1) | 0.609 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.097, 1.05 |
No. of reflections | 7282 |
No. of parameters | 466 |
No. of restraints | 16 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.44, −0.30 |
Computer programs: X-AREA (Stoe & Cie, 2002), X-RED32 (Stoe & Cie, 2002), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).
Zn1—N1 | 2.004 (2) | Zn1—N7 | 1.994 (2) |
Zn1—N3 | 1.994 (2) | Zn1—S5i | 2.6364 (9) |
Zn1—N5 | 2.004 (2) |
Symmetry code: (i) x−1/2, y, −z+1/2. |
Cg1, Cg2 and Cg3 are the centroids of the N3/C9–C12, Zn1/N1/N7/N8/C1/C26 and Zn1/N3/N4/N5/C10/C17 rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
C5A—H5A1···S1ii | 0.97 | 2.86 | 3.764 (5) | 155 |
C7—H7A···N2 | 0.97 | 2.50 | 3.014 (5) | 113 |
C21—H21A···S4i | 0.97 | 2.77 | 3.660 (4) | 154 |
C23—H23B···S5 | 0.97 | 2.69 | 3.221 (4) | 115 |
C31B—H31D···N8 | 0.97 | 2.53 | 3.089 (9) | 116 |
C21—H21B···Cg3iii | 0.97 | 2.86 | 3.536 (3) | 128 |
C22—H22A···Cg1iii | 0.96 | 2.90 | 3.699 (4) | 142 |
C23—H23B···Cg2iii | 0.97 | 2.81 | 3.641 (4) | 144 |
Symmetry codes: (i) x−1/2, y, −z+1/2; (ii) −x+1, −y, −z+1; (iii) x+1/2, y, −z+1/2. |
The synthesis and characterization of porphyrazines (tetrapyrrole macrocycles) and their metal complexes are a topic of growing interest (Schramm & Hoffman, 1980). They have high symmetry, planarity, thermal stability and electronic delocalization. So, these types of compounds have potential applications for interesting optical, electrical, medical and catalytic properties. One synthetic route to octakis-functionalized porphyrazine is the cyclization of the functionalized dicyano precursor in the presence of magnesium alkoxide (Sakellariou et al., 2000; Ramirez et al., 2004). Their properties can be easily modified by attachment of diverse peripheral substituents, heteroatoms or alternation of the cetral metal ion.
The Zr(IV), Mn(III), Fe(III), Cu(II), Ni(II) and some lantanides complexes of (ethylsulfanyl) porphyrazines have been investigated (Ricciardi et al., 1996a,b; 1998; 1999). In this present work, we report the crystal structure of the title compound (I).
In the molecule of (I) shown in Fig. 1, the Zn—N bond distances range from from 1.994 (2) to 2.004 (2) Å. The intermolecular Zn—S distance [2.6364 (9) Å] which leads to a pseudo-square-pyramidal coordination around the ZnII ion, is shorter than the Co—S distances [alternatively 2.789 (5) and 2.842 (5) Å] in ((ethylsulfanyl)porphyrazinato)cobalt(II) (Ricciardi et al., 1999).
The molecular conformation of (I) is stabilized by weak intramolecular C—H···N and C—H···S interactions. In the crystal structure, intermolecular C—H···S contacts (Fig. 2), weak C—H···π interactions and π-π stacking interactions [Cg3···Cg4ii = 3.832 (4) Å and Cg3···Cg5ii = 3.850 (5) Å; symmetry code: (ii) 1/2 + x, y, 1/2 - z; Cg3, Cg4 and Cg5 are the centroids of the N5/C17–C20, N7/C25/C26/C27B/C28 and N7/C25/C26/C27A/C28 rings, respectively] contribute to the stabilization of the crystal structure.