research communications
E,5′E,6Z,6′Z)-6,6′-[ethane-1,2-diylbis(azanylylidene)]bis{5-[2-(4-fluorophenyl)hydrazono]-3,3-dimethylcyclohexanone} 2.5-hydrate
Hirshfeld surface analysis and DFT study of (5aBaku State University, Organic Chemistry Department, Z. Khalilov 23, Baku, AZ, 1148, Azerbaijan, bPG Department of Chemistry, Langat Singh College, B. R. A. Bihar University, Muzaffarpur, Bihar-842001, India, cDepartment of Physics, Faculty of Arts and Sciences, Ondokuz Mayıs University, Samsun, 55200, Türkiye, dDepartment of Physics, Faculty of Sciences, Ondokuz Mayıs University, Samsun, 55200, Türkiye, and eFaculty of Chemistry, Karte-e-chahar, Kabul, Afghanistan
*Correspondence e-mail: tahera.nabi@ku.edu.af
The title compound, C30H34F2N6O2·2.5H2O, was obtained by condensation of 2-[2-(4-fluorophenyl)hydrazono]-5,5-dimethylcyclohexan-1,3-dione with ethylenediamine in ethanol and crystallized as a 1:2.5 hydrate in C2/c. The two independent molecules, with approximate crystallographic C2 symmetries, have different conformations and packing environments, are stabilized by intramolecular N—H⋯N hydrogen bonds and linked by O—H⋯O hydrogen bonds involving the water molecules. A Hirshfeld surface analysis showed that H⋯H contacts make by far the largest (48–50%) contribution to the crystal packing. From DFT calculations, the LUMO–HOMO energy gap of the molecule is 0.827 eV.
Keywords: crystal structure; condensation; crystal packing; density functional theory; Hirshfeld surface analysis; hydrogen bonding.
CCDC reference: 2153643
1. Chemical context
Diketones are versatile starting materials in the synthesis of organic and coordination compounds (Mahmudov et al., 2017), used as shift reagents (Hinckley, 1969), chemical and photochemical catalysts or as biologically active derivatives to treat inflammatory diseases. β-Diketones can be isolated from natural sources such as bacteria, plants or fungi, and can also be obtained synthetically (Shokova et al., 2015). More recently, 1,2-bis(3,5-difluorophenyl)ethane-1,2-dione has been used to synthesize various polymers for use as photovoltaics (Cai et al., 2019) or stationary phases (Liu et al., 2019). Non-covalent interactions, such as halogen, hydrogen, chalcogen, pnicogen, aerogen, tetrel and icosagen bonds, as well as π–cation, π–anion, n–π, π–π* stacking and hydrophobic contacts may organize or arrange the conformation and aggregation of molecules, their stabilization and particular properties (Desiraju 1995; Akbari Afkhami et al., 2017; Hazra et al., 2018; Gurbanov et al., 2018; Kvyatkovskaya et al., 2017; Jlassi et al., 2014). Herein we report the synthesis, and density functional theory (DFT) calculation of the title compound (II), obtained by the condensation reaction between ethylenediamine and 2-[2-(4-fluorophenyl)hydrazone]-5,5-dimethylcyclohexan-1,3-dione (I) in a 2:1 ratio, in the presence of catalytic hydrochloric acid. A series of similar compounds was synthesized (but not characterized crystallographically) by Rema et al. (1997) by the condensation of 2-phenylhydrazones of acetylacetone, benzoylacetone and 1,3-cyclohexanedione with ethylenediamine, as well as 1,3-diaminopropane and 1,6-diaminohexane.
2. Structural commentary
The A) of (II) in a general position and one-half of another molecule (B), which lies on a crystallographic twofold axis, as well as three ordered water molecules (O1W, O2W, O3W) and one that is disordered over three positions (O4W, O5W and O6W) with occupancies of 0.5, 0.125 and 0.125, respectively. Thus the crystal composition is (II)·2.5H2O.
contains one full molecule (Molecule A has an approximate non-crystallographic C2 symmetry. Each molecule comprises two approximately planar halves, whose planarity is stabilized by intramolecular N—H⋯N hydrogen bonds, arranged in an `open-book' mode. The connecting bridges, N3—C25—C24—N2 in molecule A and N9—C13—C13i—N9i in B, have gauche conformations, with torsion angles of −59.1 (3) and 63.7 (3)°, respectively. However, in other respects the conformations of molecules A and B are drastically different (Fig. 1). It is noteworthy that although crystal structures with Z′ > 1 are common, two substantially different conformers rarely co-exist in the same structure (Sona & Gautham, 1992). The bond lengths in molecules A and B are similar, and close to those reported earlier (Turkoglu et al., 2015; Shikhaliyev et al., 2019) for analogous compounds (see also Section 6).
3. Supramolecular features
In the crystal, molecules of (II) are linked directly through weak C—H⋯O and C—H⋯F hydrogen bonds and indirectly through water molecules of crystallization and strong O—H⋯O hydrogen bonds formed by the latter (Fig. 2, Table 1).
4. Hirshfeld surface analysis
In order to visualize the intermolecular interactions, a Hirshfeld surface (HS) analysis (Hirshfeld, 1977) was carried out using Crystal Explorer 17.5 (Turner et al., 2017). The Hirshfeld surfaces of molecules A and B, mapped over dnorm, are shown in Fig. 3. The red spots, indicating short intermolecular contacts, correspond to O—H⋯O hydrogen bonds donated by the water molecules, and C—H⋯F contacts. The Hirshfeld surface of molecule B is smaller than that of A, both in terms of area (527.8 vs 532.1 Å2) and the enclosed volume (684.6 vs 694.0 Å3), and has a higher asphericity factor (0.211 vs 0.085), as a result of the difference in conformations (see above).
Two-dimensional fingerprint plots (Fig. 4) show the contributions of various contacts to the Hirshfeld surface. Thus, for both molecules A and B, by far the largest contributions are by H⋯H contacts, 49.9% (A) and 47.9% (B). Given that H atoms comprise ca 70% of the molecular surface, a similar share would be expected if the contact distribution were entirely random. The O⋯H/H⋯O contacts, i.e. strong and weak hydrogen bonds, contribute 14.9% (A) and 13.8% (B), and H⋯C/C⋯H contacts, i.e. σ–π interactions, 14.1% (A) and 11.8% (B). Most remarkable is the different role of the fluorine atoms. In molecule B, F⋯H/H⋯F contacts contribute 16.8%, much more than the 6.4% in A or the 6% expected for a random distribution. In contrast, F⋯C/C⋯F contacts are more common in A (5.1%) than in B (1.2%). The contributions of all other contacts are negligible, except H⋯N/N⋯H (4.0% for A, 3.8% for B). Thus, the fingerprint plots reveal that molecules A and B have substantially different packing environments.
5. Frontier molecular orbital analysis
The frontier molecular orbitals (FMOs), i.e. the highest occupied MO (HOMO) and the lowest unoccupied MO (LUMO) play the most significant role in defining the molecular properties (Hoffmann et al., 1965; Fukui, 1982). The HOMO is associated with electron-donating and LUMO with the electron-accepting capability, their energies approximating the negative of the (first) and the of the molecule, respectively, from where useful information regarding donor–acceptor interactions can be obtained (Demir et al., 2016), and the degree of the or nucleophilicity of the molecule estimated (Parr et al., 1999; Chattaraj et al., 2006).
The (Fig. 5) were calculated at the DFT-B3LYP/6-311G(d,p) level of theory as implemented in Gaussian09 (Frisch et al., 2009). The X-ray-determined structure of molecule A was taken as the starting molecular geometry. This gave the energies of HOMO as −4.8164 eV and LUMO as −3.9894 eV, with a LUMO–HOMO gap of 0.827 eV, from which the (μ = −4.40 eV), global hardness η (= 0.41 eV), softness (S = 1.21) and the global index (ω = 23.4 eV) can be derived. Thus molecule (II) can be regarded as a good (Domingo et al., 2002) and rather soft.
of molecule (II)6. Database survey
A search of the Cambridge Database (CSD Version 5.42, update of September 2021; Groom et al., 2016) did not yield any close analogue of compound (II). However, various similar compounds have been reported, viz. 7-(5-bromo-2-hydroxyphenyl)-6-(4-bromophenyl)-3,3,10,10-tetramethyl-3,4,10,11-tetrahydroindolo[1,2-a]quinoxaline-1,8[2H,9H]-dione (ELIBIM; Fang & Yan, 2016), 6,6-dimethyl-1-(4-nitrophenyl)-1,5,6,7-tetrahydro-4H-benzotriazol-4-one (EMOLEZ; Singh et al., 2016), 3-(3-methoxyphenylamino)-5,5-dimethyl-2-nitroso-2-cyclohexan-1-one (GOYFOP; Gilli et al., 2000), 3-hydroxy-6,6-dimethyl-2-(4-oxo-4H-chromen-3-yl)-1,5,6,7-tetrahydro-4H-3,1-benzimidazol-4-one methanol solvate (ZEVJUH; Nikitina et al., 2013), 1-[2,2-dichloro-1-(4-chlorophenyl)ethenyl]-2-(4-fluorophenyl)diazene (XAJZIV; Nenajdenko et al., 2020), 1-[(5-chloro-2-phenoxyphenyl)(4-methoxyphenyl)carbonohydrazonoyl]-2-(4-fluorophenyl)diazene (QOWNOH; Turkoglu et al., 2015), (Z)-4-[(E)-(4-fluorophenyl)diazenyl]-6-[(3-hydroxypropylamino)methylene]-2-methoxycyclohexa-2,4-dienone (KARFAM; Albayrak et al., 2012), N-(4-fluorophenyl)-N′-{1-[(4-fluorophenyl)diazenyl]-2-(methylimino)-2-phenylethylidene}-2,2-dimethylpropanehydrazide (SIDKOH; Simunek et al., 2013) and 2-[2-(3-chloro-4-fluorophenyl)hydrazono]-5,5-dimethylcyclohexane-1,3-dione (CAXPIE; Subhasri et al., 2022).
7. Synthesis and crystallization
2 mmol of (I) were dissolved in 15–20 ml of ethanol in a three-necked flask, 1 drop of HCl was added and the solution was heated to 323 K. Then 1 mmol of ethylenediamine was added and the mixture stirred for 1 h at the same temperature. The product (II) was filtered off and purified by recrystallization from ethanol (yield 59%). The reaction and the purity of the substances were monitored by TLC (Sorbil, RF:0.72, 2-propanol).
8. Refinement
Crystal data, data collection and structure . H atoms were positioned geometrically and refined using a riding model [O—H = 0.85, N—H = 0.86, Csp2—H = 0.93 and Csp3—H = 0.97 Å, Uiso(H) = 1.5Ueq(C) for methyl groups or 1.2Ueq(O, N, C)].
details are summarized in Table 2
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Supporting information
CCDC reference: 2153643
https://doi.org/10.1107/S2056989023001895/zv2022sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989023001895/zv2022Isup3.hkl
Data collection: APEX2 (Bruker, 2008); cell
SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXT2013/1 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).C30H34F2N6O2·2.5H2O | F(000) = 3780 |
Mr = 593.67 | Dx = 1.267 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 22.7715 (19) Å | Cell parameters from 2620 reflections |
b = 17.2794 (15) Å | θ = 2.5–18.8° |
c = 25.640 (3) Å | µ = 0.10 mm−1 |
β = 112.297 (1)° | T = 296 K |
V = 9334.2 (16) Å3 | Prism, colourless |
Z = 12 | 0.16 × 0.14 × 0.11 mm |
Bruker APEXII CCD diffractometer | Rint = 0.070 |
φ and ω scans | θmax = 25.1°, θmin = 1.9° |
37069 measured reflections | h = −27→27 |
8249 independent reflections | k = −20→20 |
4099 reflections with I > 2σ(I) | l = −30→30 |
Refinement on F2 | 25 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.058 | H-atom parameters constrained |
wR(F2) = 0.193 | w = 1/[σ2(Fo2) + (0.0988P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.99 | (Δ/σ)max < 0.001 |
8249 reflections | Δρmax = 0.20 e Å−3 |
601 parameters | Δρmin = −0.29 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
F2 | 1.09554 (9) | 0.57702 (14) | 0.53005 (9) | 0.0952 (7) | |
O6 | 0.89907 (11) | 0.85004 (13) | 0.36530 (9) | 0.0707 (7) | |
N9 | 0.95271 (11) | 0.63828 (14) | 0.27726 (10) | 0.0497 (6) | |
H9 | 0.914706 | 0.638997 | 0.252226 | 0.060* | |
F3 | 0.76710 (10) | 0.32116 (12) | 0.48211 (10) | 0.1025 (8) | |
N10 | 0.86237 (11) | 0.75960 (14) | 0.27290 (10) | 0.0519 (6) | |
N2 | 0.75280 (11) | 0.67741 (14) | 0.31652 (10) | 0.0521 (6) | |
H2 | 0.791352 | 0.677251 | 0.340527 | 0.063* | |
N3 | 0.78027 (11) | 0.76386 (14) | 0.41673 (10) | 0.0530 (7) | |
H3 | 0.771048 | 0.715792 | 0.417904 | 0.064* | |
N1 | 0.84455 (11) | 0.71070 (15) | 0.23249 (10) | 0.0539 (7) | |
N7 | 0.83957 (12) | 0.55075 (15) | 0.32396 (11) | 0.0557 (7) | |
N6 | 0.85905 (12) | 0.60375 (15) | 0.36126 (11) | 0.0550 (7) | |
N4 | 0.82821 (12) | 0.67186 (16) | 0.51854 (11) | 0.0588 (7) | |
O7 | 0.79621 (12) | 0.44357 (15) | 0.24172 (11) | 0.0846 (8) | |
N5 | 0.79668 (12) | 0.63644 (15) | 0.47308 (11) | 0.0581 (7) | |
F4 | 0.60711 (11) | 0.74370 (16) | 0.06565 (10) | 0.1250 (9) | |
O3 | 0.89386 (14) | 0.75091 (17) | 0.61336 (10) | 0.0977 (9) | |
C12 | 0.96907 (13) | 0.69768 (16) | 0.31285 (11) | 0.0446 (7) | |
C7 | 0.92362 (13) | 0.75336 (17) | 0.31220 (12) | 0.0460 (7) | |
C8 | 0.93933 (15) | 0.80892 (17) | 0.35815 (12) | 0.0492 (7) | |
C20 | 0.73494 (14) | 0.61741 (17) | 0.28199 (12) | 0.0499 (8) | |
C10 | 1.05603 (13) | 0.78558 (17) | 0.37729 (12) | 0.0509 (8) | |
C13 | 0.99160 (14) | 0.57224 (16) | 0.27573 (12) | 0.0514 (8) | |
H13A | 0.968891 | 0.524959 | 0.276294 | 0.062* | |
H13B | 1.030349 | 0.572808 | 0.309210 | 0.062* | |
C11 | 1.03605 (13) | 0.70393 (17) | 0.35377 (12) | 0.0498 (7) | |
H11A | 1.063950 | 0.686857 | 0.335369 | 0.060* | |
H11B | 1.041915 | 0.669060 | 0.385002 | 0.060* | |
C40 | 0.92104 (14) | 0.59354 (18) | 0.40252 (13) | 0.0524 (8) | |
C21 | 0.77828 (15) | 0.55750 (17) | 0.28450 (13) | 0.0526 (8) | |
C31 | 0.83760 (14) | 0.75046 (19) | 0.51517 (12) | 0.0538 (8) | |
C26 | 0.81638 (13) | 0.79584 (17) | 0.46495 (13) | 0.0506 (8) | |
C4 | 0.78281 (14) | 0.72419 (19) | 0.19112 (12) | 0.0523 (8) | |
C34 | 0.79058 (14) | 0.55572 (19) | 0.47871 (14) | 0.0556 (8) | |
C39 | 0.76263 (15) | 0.5143 (2) | 0.42909 (14) | 0.0607 (9) | |
H39 | 0.749549 | 0.540146 | 0.394719 | 0.073* | |
C25 | 0.75416 (15) | 0.80125 (18) | 0.36141 (12) | 0.0580 (8) | |
H25A | 0.788441 | 0.819537 | 0.350919 | 0.070* | |
H25B | 0.728565 | 0.845438 | 0.362886 | 0.070* | |
C24 | 0.71388 (14) | 0.74392 (18) | 0.31816 (12) | 0.0559 (8) | |
H24A | 0.678742 | 0.726986 | 0.327934 | 0.067* | |
H24B | 0.696646 | 0.768255 | 0.281344 | 0.067* | |
C9 | 1.00665 (14) | 0.81378 (18) | 0.39906 (12) | 0.0544 (8) | |
H9A | 1.010664 | 0.783819 | 0.432237 | 0.065* | |
H9B | 1.015934 | 0.867263 | 0.410773 | 0.065* | |
C22 | 0.75933 (17) | 0.4957 (2) | 0.24298 (14) | 0.0634 (9) | |
C45 | 0.96325 (16) | 0.53591 (19) | 0.40083 (14) | 0.0595 (9) | |
H45 | 0.951641 | 0.500797 | 0.371137 | 0.071* | |
C41 | 0.93867 (14) | 0.64476 (19) | 0.44682 (14) | 0.0581 (8) | |
H41 | 0.910566 | 0.683324 | 0.447703 | 0.070* | |
C35 | 0.80994 (15) | 0.5166 (2) | 0.53017 (14) | 0.0626 (9) | |
H35 | 0.828554 | 0.543580 | 0.563835 | 0.075* | |
C36 | 0.80127 (16) | 0.4373 (2) | 0.53080 (17) | 0.0724 (10) | |
H36 | 0.813723 | 0.410494 | 0.564756 | 0.087* | |
C44 | 1.02267 (16) | 0.5316 (2) | 0.44389 (16) | 0.0675 (10) | |
H44 | 1.051675 | 0.494183 | 0.443113 | 0.081* | |
C19 | 0.66830 (15) | 0.61617 (18) | 0.23968 (13) | 0.0621 (9) | |
H19A | 0.665624 | 0.649403 | 0.208368 | 0.075* | |
H19B | 0.640637 | 0.637650 | 0.256904 | 0.075* | |
C43 | 1.03795 (16) | 0.5828 (2) | 0.48728 (16) | 0.0666 (10) | |
C30 | 0.87277 (17) | 0.7878 (2) | 0.56849 (15) | 0.0678 (9) | |
C28 | 0.89082 (16) | 0.90513 (19) | 0.51674 (14) | 0.0659 (9) | |
C27 | 0.83332 (15) | 0.87873 (17) | 0.46489 (13) | 0.0607 (9) | |
H27A | 0.796896 | 0.909788 | 0.462471 | 0.073* | |
H27B | 0.842091 | 0.888947 | 0.431352 | 0.073* | |
C18 | 0.64399 (16) | 0.5357 (2) | 0.21674 (14) | 0.0680 (10) | |
C38 | 0.75398 (16) | 0.4358 (2) | 0.42995 (16) | 0.0693 (10) | |
H38 | 0.734767 | 0.408362 | 0.396538 | 0.083* | |
C42 | 0.99769 (16) | 0.6397 (2) | 0.49014 (14) | 0.0666 (9) | |
H42 | 1.009572 | 0.674041 | 0.520310 | 0.080* | |
C3 | 0.74440 (16) | 0.7869 (2) | 0.19078 (14) | 0.0655 (9) | |
H3A | 0.758677 | 0.824248 | 0.218897 | 0.079* | |
C5 | 0.76179 (16) | 0.6708 (2) | 0.14840 (14) | 0.0672 (9) | |
H5 | 0.787844 | 0.629339 | 0.148330 | 0.081* | |
C15 | 1.06016 (17) | 0.83952 (19) | 0.33173 (14) | 0.0701 (10) | |
H15A | 1.088826 | 0.818125 | 0.316115 | 0.105* | |
H15B | 1.075407 | 0.889248 | 0.347916 | 0.105* | |
H15C | 1.018841 | 0.845162 | 0.302490 | 0.105* | |
C29 | 0.88290 (17) | 0.8731 (2) | 0.56898 (14) | 0.0710 (10) | |
H29A | 0.920447 | 0.886039 | 0.601720 | 0.085* | |
H29B | 0.847052 | 0.898716 | 0.573198 | 0.085* | |
C37 | 0.77395 (16) | 0.3988 (2) | 0.48037 (19) | 0.0713 (10) | |
C23 | 0.69345 (16) | 0.4967 (2) | 0.19936 (14) | 0.0726 (10) | |
H23A | 0.680241 | 0.443726 | 0.188760 | 0.087* | |
H23B | 0.694256 | 0.522801 | 0.166131 | 0.087* | |
C14 | 1.12089 (15) | 0.7801 (2) | 0.42564 (14) | 0.0742 (10) | |
H14A | 1.118189 | 0.745758 | 0.454065 | 0.111* | |
H14B | 1.133661 | 0.830553 | 0.441640 | 0.111* | |
H14C | 1.151542 | 0.760639 | 0.411575 | 0.111* | |
C46 | 0.66604 (18) | 0.7378 (3) | 0.10724 (16) | 0.0812 (11) | |
C6 | 0.70266 (19) | 0.6772 (3) | 0.10544 (15) | 0.0791 (11) | |
H6 | 0.688639 | 0.641151 | 0.076380 | 0.095* | |
C33 | 0.95173 (17) | 0.8743 (2) | 0.51310 (16) | 0.0831 (11) | |
H33A | 0.949259 | 0.818939 | 0.509510 | 0.125* | |
H33B | 0.987162 | 0.888138 | 0.546644 | 0.125* | |
H33C | 0.957199 | 0.896237 | 0.480848 | 0.125* | |
C17 | 0.63175 (18) | 0.4872 (2) | 0.26157 (17) | 0.0875 (12) | |
H17A | 0.670640 | 0.481196 | 0.293764 | 0.131* | |
H17B | 0.616002 | 0.437181 | 0.246323 | 0.131* | |
H17C | 0.600946 | 0.512764 | 0.272725 | 0.131* | |
C2 | 0.68508 (18) | 0.7934 (2) | 0.14860 (16) | 0.0795 (11) | |
H2A | 0.658518 | 0.834447 | 0.148160 | 0.095* | |
C16 | 0.58150 (18) | 0.5454 (2) | 0.16554 (17) | 0.0996 (14) | |
H16A | 0.550401 | 0.569113 | 0.177259 | 0.149* | |
H16B | 0.566489 | 0.495546 | 0.149430 | 0.149* | |
H16C | 0.588558 | 0.577506 | 0.137932 | 0.149* | |
C32 | 0.8926 (2) | 0.9931 (2) | 0.51835 (18) | 0.0964 (13) | |
H32A | 0.896750 | 1.012411 | 0.484791 | 0.145* | |
H32B | 0.928180 | 1.010059 | 0.550779 | 0.145* | |
H32C | 0.854080 | 1.012447 | 0.520502 | 0.145* | |
O2W | 0.85971 (16) | 0.5119 (2) | 0.17268 (14) | 0.1381 (12) | |
H2WA | 0.840883 | 0.493144 | 0.192778 | 0.207* | |
H2WB | 0.879123 | 0.473704 | 0.165798 | 0.207* | |
O1W | 0.93443 (17) | 0.6011 (2) | 0.65403 (17) | 0.1587 (15) | |
H1WA | 0.970580 | 0.620651 | 0.672785 | 0.238* | |
H1WB | 0.910130 | 0.639951 | 0.641847 | 0.238* | |
O3W | 0.92308 (17) | 0.3840 (2) | 0.2815 (2) | 0.1847 (19) | |
H3WA | 0.935932 | 0.338346 | 0.279348 | 0.277* | |
H3WB | 0.882892 | 0.380027 | 0.269188 | 0.277* | |
O4W | 0.9769 (4) | 0.2282 (5) | 0.2984 (4) | 0.180 (3) | 0.5 |
H4WA | 0.985140 | 0.227073 | 0.268724 | 0.270* | 0.5 |
H4WB | 0.962601 | 0.273503 | 0.298895 | 0.270* | 0.5 |
O5W | 0.9411 (16) | 0.241 (2) | 0.2313 (14) | 0.175 (4) | 0.125 |
H5WA | 0.911013 | 0.265707 | 0.236069 | 0.263* | 0.125 |
H5WB | 0.969813 | 0.275397 | 0.236599 | 0.263* | 0.125 |
O6W | 0.9656 (16) | 0.1682 (18) | 0.2174 (11) | 0.152 (11) | 0.125 |
H6WA | 0.942959 | 0.192682 | 0.187885 | 0.229* | 0.125 |
H6WB | 0.949669 | 0.123032 | 0.212835 | 0.229* | 0.125 |
U11 | U22 | U33 | U12 | U13 | U23 | |
F2 | 0.0492 (12) | 0.1286 (19) | 0.0893 (15) | 0.0052 (12) | 0.0055 (12) | 0.0275 (14) |
O6 | 0.0634 (15) | 0.0765 (16) | 0.0659 (15) | 0.0190 (13) | 0.0174 (12) | −0.0113 (12) |
N9 | 0.0451 (14) | 0.0494 (15) | 0.0520 (15) | −0.0007 (12) | 0.0157 (12) | −0.0013 (13) |
F3 | 0.0878 (16) | 0.0592 (13) | 0.133 (2) | −0.0079 (11) | 0.0110 (14) | 0.0246 (13) |
N10 | 0.0481 (16) | 0.0540 (16) | 0.0504 (16) | 0.0013 (13) | 0.0153 (14) | 0.0014 (13) |
N2 | 0.0465 (15) | 0.0554 (16) | 0.0465 (15) | −0.0008 (13) | 0.0088 (12) | −0.0035 (13) |
N3 | 0.0575 (16) | 0.0460 (15) | 0.0480 (15) | −0.0019 (12) | 0.0114 (13) | 0.0015 (12) |
N1 | 0.0471 (16) | 0.0600 (17) | 0.0506 (16) | −0.0003 (13) | 0.0141 (14) | 0.0011 (14) |
N7 | 0.0548 (17) | 0.0560 (17) | 0.0556 (16) | −0.0069 (13) | 0.0200 (15) | −0.0017 (14) |
N6 | 0.0489 (16) | 0.0614 (17) | 0.0512 (16) | −0.0062 (13) | 0.0150 (14) | −0.0006 (14) |
N4 | 0.0586 (17) | 0.0617 (19) | 0.0545 (17) | 0.0017 (14) | 0.0194 (14) | 0.0029 (14) |
O7 | 0.0789 (18) | 0.0724 (17) | 0.100 (2) | −0.0005 (14) | 0.0314 (16) | −0.0241 (15) |
N5 | 0.0596 (17) | 0.0575 (18) | 0.0527 (17) | −0.0005 (14) | 0.0162 (14) | −0.0002 (14) |
F4 | 0.0794 (16) | 0.154 (2) | 0.0920 (17) | 0.0178 (15) | −0.0236 (14) | 0.0128 (16) |
O3 | 0.123 (2) | 0.098 (2) | 0.0496 (15) | −0.0072 (17) | 0.0072 (16) | 0.0027 (15) |
C12 | 0.0480 (18) | 0.0432 (18) | 0.0428 (17) | −0.0026 (14) | 0.0174 (15) | 0.0015 (14) |
C7 | 0.0442 (18) | 0.0466 (17) | 0.0447 (17) | 0.0040 (14) | 0.0141 (15) | 0.0048 (14) |
C8 | 0.0532 (19) | 0.0493 (18) | 0.0453 (18) | 0.0078 (16) | 0.0189 (16) | 0.0036 (15) |
C20 | 0.0531 (19) | 0.0517 (19) | 0.0415 (17) | −0.0090 (16) | 0.0143 (15) | 0.0034 (15) |
C10 | 0.0459 (18) | 0.0524 (19) | 0.0500 (18) | −0.0059 (15) | 0.0134 (15) | −0.0055 (15) |
C13 | 0.0559 (19) | 0.0392 (16) | 0.0572 (19) | −0.0019 (15) | 0.0193 (16) | 0.0004 (14) |
C11 | 0.0439 (18) | 0.0504 (18) | 0.0518 (18) | 0.0026 (15) | 0.0146 (15) | 0.0012 (15) |
C40 | 0.0451 (19) | 0.056 (2) | 0.056 (2) | −0.0016 (16) | 0.0188 (17) | 0.0053 (16) |
C21 | 0.0502 (19) | 0.0482 (19) | 0.056 (2) | −0.0041 (16) | 0.0163 (17) | −0.0007 (16) |
C31 | 0.0536 (19) | 0.060 (2) | 0.0438 (18) | 0.0015 (16) | 0.0141 (16) | −0.0051 (16) |
C26 | 0.0447 (18) | 0.0520 (19) | 0.055 (2) | 0.0034 (15) | 0.0194 (16) | −0.0079 (16) |
C4 | 0.0476 (19) | 0.065 (2) | 0.0389 (17) | 0.0007 (17) | 0.0104 (15) | 0.0049 (16) |
C34 | 0.0494 (19) | 0.057 (2) | 0.061 (2) | 0.0031 (16) | 0.0225 (17) | 0.0116 (17) |
C39 | 0.058 (2) | 0.062 (2) | 0.056 (2) | 0.0010 (17) | 0.0154 (17) | 0.0074 (18) |
C25 | 0.062 (2) | 0.0522 (19) | 0.0497 (19) | 0.0048 (16) | 0.0101 (17) | 0.0060 (16) |
C24 | 0.0528 (19) | 0.057 (2) | 0.0486 (18) | 0.0060 (16) | 0.0086 (16) | 0.0040 (16) |
C9 | 0.057 (2) | 0.0558 (19) | 0.0472 (18) | −0.0013 (16) | 0.0162 (16) | −0.0041 (15) |
C22 | 0.067 (2) | 0.056 (2) | 0.065 (2) | −0.0082 (19) | 0.023 (2) | −0.0040 (18) |
C45 | 0.061 (2) | 0.061 (2) | 0.061 (2) | 0.0007 (18) | 0.0274 (19) | 0.0072 (17) |
C41 | 0.0442 (19) | 0.060 (2) | 0.065 (2) | 0.0024 (16) | 0.0155 (18) | 0.0031 (18) |
C35 | 0.057 (2) | 0.074 (2) | 0.056 (2) | 0.0042 (18) | 0.0200 (17) | 0.0082 (18) |
C36 | 0.062 (2) | 0.072 (3) | 0.079 (3) | 0.003 (2) | 0.022 (2) | 0.030 (2) |
C44 | 0.051 (2) | 0.071 (2) | 0.084 (3) | 0.0148 (18) | 0.028 (2) | 0.024 (2) |
C19 | 0.054 (2) | 0.062 (2) | 0.056 (2) | −0.0027 (16) | 0.0051 (17) | −0.0009 (17) |
C43 | 0.044 (2) | 0.082 (3) | 0.066 (2) | −0.002 (2) | 0.0114 (19) | 0.021 (2) |
C30 | 0.067 (2) | 0.077 (3) | 0.055 (2) | 0.006 (2) | 0.0184 (19) | −0.005 (2) |
C28 | 0.065 (2) | 0.061 (2) | 0.066 (2) | −0.0066 (18) | 0.0187 (19) | −0.0158 (18) |
C27 | 0.064 (2) | 0.053 (2) | 0.061 (2) | 0.0050 (16) | 0.0187 (18) | −0.0070 (16) |
C18 | 0.057 (2) | 0.067 (2) | 0.063 (2) | −0.0098 (18) | 0.0033 (18) | −0.0026 (18) |
C38 | 0.062 (2) | 0.062 (2) | 0.072 (2) | −0.0038 (18) | 0.013 (2) | 0.004 (2) |
C42 | 0.052 (2) | 0.075 (2) | 0.065 (2) | −0.0087 (19) | 0.0135 (19) | −0.0012 (19) |
C3 | 0.067 (2) | 0.068 (2) | 0.055 (2) | 0.0049 (19) | 0.0147 (19) | 0.0068 (17) |
C5 | 0.060 (2) | 0.081 (2) | 0.054 (2) | 0.0016 (19) | 0.0142 (19) | −0.0019 (19) |
C15 | 0.079 (2) | 0.058 (2) | 0.081 (2) | −0.0153 (18) | 0.039 (2) | 0.0003 (19) |
C29 | 0.073 (2) | 0.076 (3) | 0.057 (2) | 0.006 (2) | 0.0171 (19) | −0.0179 (19) |
C37 | 0.054 (2) | 0.055 (2) | 0.095 (3) | −0.0012 (18) | 0.017 (2) | 0.009 (2) |
C23 | 0.075 (3) | 0.065 (2) | 0.067 (2) | −0.009 (2) | 0.014 (2) | −0.0092 (18) |
C14 | 0.057 (2) | 0.077 (3) | 0.077 (2) | −0.0035 (19) | 0.0117 (19) | −0.016 (2) |
C46 | 0.061 (2) | 0.102 (3) | 0.058 (2) | 0.002 (2) | −0.004 (2) | 0.012 (2) |
C6 | 0.072 (3) | 0.095 (3) | 0.052 (2) | −0.005 (2) | 0.004 (2) | −0.005 (2) |
C33 | 0.063 (2) | 0.104 (3) | 0.077 (3) | −0.010 (2) | 0.021 (2) | −0.019 (2) |
C17 | 0.077 (3) | 0.082 (3) | 0.098 (3) | −0.018 (2) | 0.027 (2) | 0.005 (2) |
C2 | 0.070 (3) | 0.085 (3) | 0.076 (3) | 0.024 (2) | 0.018 (2) | 0.020 (2) |
C16 | 0.075 (3) | 0.091 (3) | 0.091 (3) | −0.010 (2) | −0.016 (2) | −0.018 (2) |
C32 | 0.118 (4) | 0.063 (3) | 0.099 (3) | −0.015 (2) | 0.031 (3) | −0.025 (2) |
O2W | 0.137 (3) | 0.153 (3) | 0.134 (3) | 0.008 (2) | 0.062 (2) | 0.002 (2) |
O1W | 0.130 (3) | 0.116 (3) | 0.188 (4) | −0.014 (2) | 0.013 (3) | 0.049 (2) |
O3W | 0.111 (3) | 0.134 (3) | 0.298 (6) | −0.003 (2) | 0.066 (3) | 0.025 (3) |
O4W | 0.160 (6) | 0.137 (6) | 0.170 (6) | −0.040 (5) | −0.019 (5) | 0.015 (5) |
O5W | 0.157 (7) | 0.138 (7) | 0.166 (7) | −0.038 (6) | −0.011 (6) | 0.015 (6) |
O6W | 0.19 (3) | 0.13 (2) | 0.12 (2) | 0.05 (2) | 0.05 (2) | 0.050 (18) |
F2—C43 | 1.357 (4) | C36—C37 | 1.375 (5) |
O6—C8 | 1.227 (3) | C36—H36 | 0.9300 |
N9—C12 | 1.329 (3) | C44—C43 | 1.360 (5) |
N9—C13 | 1.454 (4) | C44—H44 | 0.9300 |
N9—H9 | 0.8600 | C19—C18 | 1.529 (4) |
F3—C37 | 1.353 (4) | C19—H19A | 0.9700 |
N10—N1 | 1.278 (3) | C19—H19B | 0.9700 |
N10—C7 | 1.380 (3) | C43—C42 | 1.365 (5) |
N2—C20 | 1.323 (3) | C30—C29 | 1.491 (5) |
N2—C24 | 1.461 (4) | C28—C32 | 1.521 (5) |
N2—H2 | 0.8600 | C28—C33 | 1.522 (5) |
N3—C26 | 1.319 (3) | C28—C29 | 1.522 (5) |
N3—C25 | 1.464 (3) | C28—C27 | 1.539 (4) |
N3—H3 | 0.8600 | C27—H27A | 0.9700 |
N1—C4 | 1.423 (4) | C27—H27B | 0.9700 |
N7—N6 | 1.276 (3) | C18—C23 | 1.517 (5) |
N7—C21 | 1.383 (4) | C18—C17 | 1.531 (5) |
N6—C40 | 1.418 (4) | C18—C16 | 1.536 (4) |
N4—N5 | 1.270 (3) | C38—C37 | 1.357 (5) |
N4—C31 | 1.383 (4) | C38—H38 | 0.9300 |
O7—C22 | 1.240 (4) | C42—H42 | 0.9300 |
N5—C34 | 1.414 (4) | C3—C2 | 1.378 (5) |
F4—C46 | 1.365 (4) | C3—H3A | 0.9300 |
O3—C30 | 1.242 (4) | C5—C6 | 1.383 (5) |
C12—C7 | 1.409 (4) | C5—H5 | 0.9300 |
C12—C11 | 1.491 (4) | C15—H15A | 0.9600 |
C7—C8 | 1.455 (4) | C15—H15B | 0.9600 |
C8—C9 | 1.496 (4) | C15—H15C | 0.9600 |
C20—C21 | 1.415 (4) | C29—H29A | 0.9700 |
C20—C19 | 1.494 (4) | C29—H29B | 0.9700 |
C10—C9 | 1.513 (4) | C23—H23A | 0.9700 |
C10—C15 | 1.525 (4) | C23—H23B | 0.9700 |
C10—C14 | 1.529 (4) | C14—H14A | 0.9600 |
C10—C11 | 1.534 (4) | C14—H14B | 0.9600 |
C13—C13i | 1.507 (6) | C14—H14C | 0.9600 |
C13—H13A | 0.9700 | C46—C6 | 1.350 (5) |
C13—H13B | 0.9700 | C46—C2 | 1.373 (5) |
C11—H11A | 0.9700 | C6—H6 | 0.9300 |
C11—H11B | 0.9700 | C33—H33A | 0.9600 |
C40—C41 | 1.374 (4) | C33—H33B | 0.9600 |
C40—C45 | 1.396 (4) | C33—H33C | 0.9600 |
C21—C22 | 1.453 (4) | C17—H17A | 0.9600 |
C31—C26 | 1.426 (4) | C17—H17B | 0.9600 |
C31—C30 | 1.448 (4) | C17—H17C | 0.9600 |
C26—C27 | 1.483 (4) | C2—H2A | 0.9300 |
C4—C5 | 1.372 (4) | C16—H16A | 0.9600 |
C4—C3 | 1.390 (4) | C16—H16B | 0.9600 |
C34—C39 | 1.386 (4) | C16—H16C | 0.9600 |
C34—C35 | 1.397 (4) | C32—H32A | 0.9600 |
C39—C38 | 1.374 (4) | C32—H32B | 0.9600 |
C39—H39 | 0.9300 | C32—H32C | 0.9600 |
C25—C24 | 1.510 (4) | O2W—H2WA | 0.8500 |
C25—H25A | 0.9700 | O2W—H2WB | 0.8497 |
C25—H25B | 0.9700 | O1W—H1WA | 0.8499 |
C24—H24A | 0.9700 | O1W—H1WB | 0.8500 |
C24—H24B | 0.9700 | O3W—H3WA | 0.8500 |
C9—H9A | 0.9700 | O3W—H3WB | 0.8500 |
C9—H9B | 0.9700 | O4W—H4WA | 0.8503 |
C22—C23 | 1.493 (4) | O4W—H4WB | 0.8499 |
C45—C44 | 1.386 (4) | O5W—H5WA | 0.8501 |
C45—H45 | 0.9300 | O5W—H5WB | 0.8501 |
C41—C42 | 1.384 (4) | O6W—O6Wi | 1.80 (6) |
C41—H41 | 0.9300 | O6W—H6WA | 0.8499 |
C35—C36 | 1.385 (5) | O6W—H6WB | 0.8500 |
C35—H35 | 0.9300 | ||
C12—N9—C13 | 127.6 (3) | C18—C19—H19B | 108.7 |
C12—N9—H9 | 116.2 | H19A—C19—H19B | 107.6 |
C13—N9—H9 | 116.2 | F2—C43—C44 | 118.8 (3) |
N1—N10—C7 | 117.5 (2) | F2—C43—C42 | 118.2 (4) |
C20—N2—C24 | 126.8 (3) | C44—C43—C42 | 123.0 (3) |
C20—N2—H2 | 116.6 | O3—C30—C31 | 121.8 (3) |
C24—N2—H2 | 116.6 | O3—C30—C29 | 119.7 (3) |
C26—N3—C25 | 127.1 (3) | C31—C30—C29 | 118.5 (3) |
C26—N3—H3 | 116.5 | C32—C28—C33 | 109.7 (3) |
C25—N3—H3 | 116.5 | C32—C28—C29 | 110.5 (3) |
N10—N1—C4 | 114.6 (3) | C33—C28—C29 | 110.0 (3) |
N6—N7—C21 | 117.1 (3) | C32—C28—C27 | 109.0 (3) |
N7—N6—C40 | 115.8 (3) | C33—C28—C27 | 109.9 (3) |
N5—N4—C31 | 117.6 (3) | C29—C28—C27 | 107.8 (3) |
N4—N5—C34 | 115.1 (3) | C26—C27—C28 | 114.9 (3) |
N9—C12—C7 | 120.4 (3) | C26—C27—H27A | 108.5 |
N9—C12—C11 | 119.0 (3) | C28—C27—H27A | 108.5 |
C7—C12—C11 | 120.6 (3) | C26—C27—H27B | 108.5 |
N10—C7—C12 | 126.6 (3) | C28—C27—H27B | 108.5 |
N10—C7—C8 | 114.2 (3) | H27A—C27—H27B | 107.5 |
C12—C7—C8 | 119.2 (3) | C23—C18—C19 | 108.4 (3) |
O6—C8—C7 | 122.3 (3) | C23—C18—C17 | 110.1 (3) |
O6—C8—C9 | 119.2 (3) | C19—C18—C17 | 110.6 (3) |
C7—C8—C9 | 118.5 (3) | C23—C18—C16 | 110.3 (3) |
N2—C20—C21 | 120.7 (3) | C19—C18—C16 | 108.2 (3) |
N2—C20—C19 | 117.8 (3) | C17—C18—C16 | 109.1 (3) |
C21—C20—C19 | 121.4 (3) | C37—C38—C39 | 118.9 (3) |
C9—C10—C15 | 110.9 (3) | C37—C38—H38 | 120.6 |
C9—C10—C14 | 110.2 (2) | C39—C38—H38 | 120.6 |
C15—C10—C14 | 109.7 (3) | C43—C42—C41 | 118.0 (3) |
C9—C10—C11 | 106.8 (2) | C43—C42—H42 | 121.0 |
C15—C10—C11 | 110.9 (2) | C41—C42—H42 | 121.0 |
C14—C10—C11 | 108.3 (2) | C2—C3—C4 | 119.7 (3) |
N9—C13—C13i | 112.5 (2) | C2—C3—H3A | 120.1 |
N9—C13—H13A | 109.1 | C4—C3—H3A | 120.1 |
C13i—C13—H13A | 109.1 | C4—C5—C6 | 121.4 (3) |
N9—C13—H13B | 109.1 | C4—C5—H5 | 119.3 |
C13i—C13—H13B | 109.1 | C6—C5—H5 | 119.3 |
H13A—C13—H13B | 107.8 | C10—C15—H15A | 109.5 |
C12—C11—C10 | 114.5 (2) | C10—C15—H15B | 109.5 |
C12—C11—H11A | 108.6 | H15A—C15—H15B | 109.5 |
C10—C11—H11A | 108.6 | C10—C15—H15C | 109.5 |
C12—C11—H11B | 108.6 | H15A—C15—H15C | 109.5 |
C10—C11—H11B | 108.6 | H15B—C15—H15C | 109.5 |
H11A—C11—H11B | 107.6 | C30—C29—C28 | 114.9 (3) |
C41—C40—C45 | 119.8 (3) | C30—C29—H29A | 108.5 |
C41—C40—N6 | 115.6 (3) | C28—C29—H29A | 108.5 |
C45—C40—N6 | 124.6 (3) | C30—C29—H29B | 108.5 |
N7—C21—C20 | 126.0 (3) | C28—C29—H29B | 108.5 |
N7—C21—C22 | 114.2 (3) | H29A—C29—H29B | 107.5 |
C20—C21—C22 | 119.8 (3) | F3—C37—C38 | 119.8 (4) |
N4—C31—C26 | 126.1 (3) | F3—C37—C36 | 117.7 (4) |
N4—C31—C30 | 115.0 (3) | C38—C37—C36 | 122.5 (3) |
C26—C31—C30 | 118.9 (3) | C22—C23—C18 | 115.6 (3) |
N3—C26—C31 | 119.6 (3) | C22—C23—H23A | 108.4 |
N3—C26—C27 | 118.3 (3) | C18—C23—H23A | 108.4 |
C31—C26—C27 | 122.2 (3) | C22—C23—H23B | 108.4 |
C5—C4—C3 | 119.4 (3) | C18—C23—H23B | 108.4 |
C5—C4—N1 | 115.6 (3) | H23A—C23—H23B | 107.4 |
C3—C4—N1 | 125.0 (3) | C10—C14—H14A | 109.5 |
C39—C34—C35 | 119.2 (3) | C10—C14—H14B | 109.5 |
C39—C34—N5 | 116.3 (3) | H14A—C14—H14B | 109.5 |
C35—C34—N5 | 124.5 (3) | C10—C14—H14C | 109.5 |
C38—C39—C34 | 120.9 (3) | H14A—C14—H14C | 109.5 |
C38—C39—H39 | 119.5 | H14B—C14—H14C | 109.5 |
C34—C39—H39 | 119.5 | C6—C46—F4 | 117.9 (4) |
N3—C25—C24 | 109.4 (2) | C6—C46—C2 | 123.4 (3) |
N3—C25—H25A | 109.8 | F4—C46—C2 | 118.7 (4) |
C24—C25—H25A | 109.8 | C46—C6—C5 | 117.6 (4) |
N3—C25—H25B | 109.8 | C46—C6—H6 | 121.2 |
C24—C25—H25B | 109.8 | C5—C6—H6 | 121.2 |
H25A—C25—H25B | 108.2 | C28—C33—H33A | 109.5 |
N2—C24—C25 | 109.3 (2) | C28—C33—H33B | 109.5 |
N2—C24—H24A | 109.8 | H33A—C33—H33B | 109.5 |
C25—C24—H24A | 109.8 | C28—C33—H33C | 109.5 |
N2—C24—H24B | 109.8 | H33A—C33—H33C | 109.5 |
C25—C24—H24B | 109.8 | H33B—C33—H33C | 109.5 |
H24A—C24—H24B | 108.3 | C18—C17—H17A | 109.5 |
C8—C9—C10 | 115.5 (2) | C18—C17—H17B | 109.5 |
C8—C9—H9A | 108.4 | H17A—C17—H17B | 109.5 |
C10—C9—H9A | 108.4 | C18—C17—H17C | 109.5 |
C8—C9—H9B | 108.4 | H17A—C17—H17C | 109.5 |
C10—C9—H9B | 108.4 | H17B—C17—H17C | 109.5 |
H9A—C9—H9B | 107.5 | C46—C2—C3 | 118.5 (4) |
O7—C22—C21 | 122.5 (3) | C46—C2—H2A | 120.7 |
O7—C22—C23 | 119.2 (3) | C3—C2—H2A | 120.7 |
C21—C22—C23 | 118.3 (3) | C18—C16—H16A | 109.5 |
C44—C45—C40 | 119.3 (3) | C18—C16—H16B | 109.5 |
C44—C45—H45 | 120.4 | H16A—C16—H16B | 109.5 |
C40—C45—H45 | 120.4 | C18—C16—H16C | 109.5 |
C40—C41—C42 | 120.9 (3) | H16A—C16—H16C | 109.5 |
C40—C41—H41 | 119.6 | H16B—C16—H16C | 109.5 |
C42—C41—H41 | 119.6 | C28—C32—H32A | 109.5 |
C36—C35—C34 | 119.7 (3) | C28—C32—H32B | 109.5 |
C36—C35—H35 | 120.2 | H32A—C32—H32B | 109.5 |
C34—C35—H35 | 120.2 | C28—C32—H32C | 109.5 |
C37—C36—C35 | 118.9 (3) | H32A—C32—H32C | 109.5 |
C37—C36—H36 | 120.6 | H32B—C32—H32C | 109.5 |
C35—C36—H36 | 120.6 | H2WA—O2W—H2WB | 104.5 |
C43—C44—C45 | 119.1 (3) | H1WA—O1W—H1WB | 104.5 |
C43—C44—H44 | 120.5 | H3WA—O3W—H3WB | 104.5 |
C45—C44—H44 | 120.5 | H4WA—O4W—H4WB | 104.5 |
C20—C19—C18 | 114.3 (3) | H5WA—O5W—H5WB | 104.5 |
C20—C19—H19A | 108.7 | O6Wi—O6W—H6WA | 147.7 |
C18—C19—H19A | 108.7 | O6Wi—O6W—H6WB | 107.6 |
C20—C19—H19B | 108.7 | H6WA—O6W—H6WB | 104.5 |
C7—N10—N1—C4 | −175.2 (2) | N7—C21—C22—C23 | 178.6 (3) |
C21—N7—N6—C40 | 177.4 (2) | C20—C21—C22—C23 | −1.3 (4) |
C31—N4—N5—C34 | 177.7 (3) | C41—C40—C45—C44 | −0.4 (4) |
C13—N9—C12—C7 | −173.7 (2) | N6—C40—C45—C44 | −179.7 (3) |
C13—N9—C12—C11 | 5.7 (4) | C45—C40—C41—C42 | −0.5 (5) |
N1—N10—C7—C12 | −0.6 (4) | N6—C40—C41—C42 | 178.9 (3) |
N1—N10—C7—C8 | −177.4 (2) | C39—C34—C35—C36 | 0.4 (5) |
N9—C12—C7—N10 | −8.4 (4) | N5—C34—C35—C36 | 179.5 (3) |
C11—C12—C7—N10 | 172.2 (3) | C34—C35—C36—C37 | 0.4 (5) |
N9—C12—C7—C8 | 168.2 (2) | C40—C45—C44—C43 | 1.2 (5) |
C11—C12—C7—C8 | −11.2 (4) | N2—C20—C19—C18 | −158.9 (3) |
N10—C7—C8—O6 | 9.6 (4) | C21—C20—C19—C18 | 22.5 (4) |
C12—C7—C8—O6 | −167.4 (3) | C45—C44—C43—F2 | 178.3 (3) |
N10—C7—C8—C9 | −172.5 (2) | C45—C44—C43—C42 | −1.1 (5) |
C12—C7—C8—C9 | 10.4 (4) | N4—C31—C30—O3 | 1.6 (5) |
C24—N2—C20—C21 | 178.8 (3) | C26—C31—C30—O3 | −178.1 (3) |
C24—N2—C20—C19 | 0.2 (4) | N4—C31—C30—C29 | −177.7 (3) |
C12—N9—C13—C13i | −111.6 (3) | C26—C31—C30—C29 | 2.7 (5) |
N9—C12—C11—C10 | 159.0 (3) | N3—C26—C27—C28 | −161.6 (3) |
C7—C12—C11—C10 | −21.6 (4) | C31—C26—C27—C28 | 18.7 (4) |
C9—C10—C11—C12 | 51.5 (3) | C32—C28—C27—C26 | −166.1 (3) |
C15—C10—C11—C12 | −69.4 (3) | C33—C28—C27—C26 | 73.8 (4) |
C14—C10—C11—C12 | 170.2 (3) | C29—C28—C27—C26 | −46.1 (4) |
N7—N6—C40—C41 | −171.5 (3) | C20—C19—C18—C23 | −48.5 (4) |
N7—N6—C40—C45 | 7.8 (4) | C20—C19—C18—C17 | 72.4 (4) |
N6—N7—C21—C20 | −0.6 (4) | C20—C19—C18—C16 | −168.1 (3) |
N6—N7—C21—C22 | 179.5 (3) | C34—C39—C38—C37 | −0.7 (5) |
N2—C20—C21—N7 | 5.5 (5) | F2—C43—C42—C41 | −179.1 (3) |
C19—C20—C21—N7 | −175.9 (3) | C44—C43—C42—C41 | 0.3 (5) |
N2—C20—C21—C22 | −174.6 (3) | C40—C41—C42—C43 | 0.5 (5) |
C19—C20—C21—C22 | 4.0 (4) | C5—C4—C3—C2 | 1.9 (5) |
N5—N4—C31—C26 | −1.5 (5) | N1—C4—C3—C2 | −179.4 (3) |
N5—N4—C31—C30 | 178.8 (3) | C3—C4—C5—C6 | −1.1 (5) |
C25—N3—C26—C31 | 179.9 (3) | N1—C4—C5—C6 | −179.9 (3) |
C25—N3—C26—C27 | 0.1 (4) | O3—C30—C29—C28 | 146.9 (3) |
N4—C31—C26—N3 | 5.5 (5) | C31—C30—C29—C28 | −33.8 (4) |
C30—C31—C26—N3 | −174.9 (3) | C32—C28—C29—C30 | 173.0 (3) |
N4—C31—C26—C27 | −174.8 (3) | C33—C28—C29—C30 | −65.8 (4) |
C30—C31—C26—C27 | 4.8 (4) | C27—C28—C29—C30 | 54.0 (4) |
N10—N1—C4—C5 | −177.7 (3) | C39—C38—C37—F3 | −178.6 (3) |
N10—N1—C4—C3 | 3.6 (4) | C39—C38—C37—C36 | 1.5 (5) |
N4—N5—C34—C39 | −173.0 (3) | C35—C36—C37—F3 | 178.8 (3) |
N4—N5—C34—C35 | 7.8 (4) | C35—C36—C37—C38 | −1.3 (5) |
C35—C34—C39—C38 | −0.2 (5) | O7—C22—C23—C18 | 153.5 (3) |
N5—C34—C39—C38 | −179.4 (3) | C21—C22—C23—C18 | −28.2 (5) |
C26—N3—C25—C24 | −178.3 (3) | C19—C18—C23—C22 | 51.9 (4) |
C20—N2—C24—C25 | −176.4 (3) | C17—C18—C23—C22 | −69.2 (4) |
N3—C25—C24—N2 | −59.1 (3) | C16—C18—C23—C22 | 170.2 (3) |
O6—C8—C9—C10 | −158.5 (3) | F4—C46—C6—C5 | −178.7 (3) |
C7—C8—C9—C10 | 23.6 (4) | C2—C46—C6—C5 | 1.3 (6) |
C15—C10—C9—C8 | 68.3 (3) | C4—C5—C6—C46 | −0.5 (5) |
C14—C10—C9—C8 | −170.0 (3) | C6—C46—C2—C3 | −0.5 (6) |
C11—C10—C9—C8 | −52.6 (3) | F4—C46—C2—C3 | 179.5 (3) |
N7—C21—C22—O7 | −3.2 (5) | C4—C3—C2—C46 | −1.2 (5) |
C20—C21—C22—O7 | 176.8 (3) |
Symmetry code: (i) −x+2, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N9—H9···N1 | 0.86 | 1.93 | 2.609 (3) | 135 |
N2—H2···N6 | 0.86 | 1.91 | 2.585 (3) | 134 |
N3—H3···N5 | 0.86 | 1.90 | 2.582 (3) | 136 |
C13—H13B···O2Wi | 0.97 | 2.59 | 3.302 (4) | 130 |
C25—H25A···O6 | 0.97 | 2.46 | 3.370 (4) | 156 |
C24—H24A···O3ii | 0.97 | 2.65 | 3.518 (4) | 149 |
C24—H24A···O5Wiii | 0.97 | 2.58 | 3.27 (4) | 128 |
C27—H27B···O6 | 0.97 | 2.58 | 3.451 (4) | 149 |
C42—H42···F4iv | 0.93 | 2.52 | 3.218 (4) | 132 |
C5—H5···O2W | 0.93 | 2.53 | 3.441 (5) | 166 |
C23—H23A···O6v | 0.97 | 2.43 | 3.311 (4) | 151 |
O2W—H2WA···O7 | 0.85 | 2.08 | 2.926 (4) | 178 |
O2W—H2WB···O1Wvi | 0.85 | 1.91 | 2.749 (5) | 171 |
O1W—H1WA···O3Wvii | 0.85 | 2.26 | 3.042 (5) | 154 |
O1W—H1WB···O3 | 0.85 | 2.03 | 2.812 (4) | 152 |
O3W—H3WA···O4W | 0.85 | 2.09 | 2.921 (10) | 164 |
O3W—H3WA···O5W | 0.85 | 2.11 | 2.88 (4) | 151 |
O3W—H3WB···O7 | 0.85 | 2.13 | 2.866 (4) | 144 |
O4W—H4WA···O4Wi | 0.85 | 2.20 | 3.04 (2) | 170 |
O4W—H4WB···O3W | 0.85 | 2.08 | 2.921 (10) | 168 |
O5W—H5WA···O3W | 0.85 | 2.32 | 2.88 (4) | 124 |
O5W—H5WB···O5Wi | 0.85 | 1.97 | 2.48 (7) | 118 |
O6W—H6WA···O3vi | 0.85 | 2.06 | 2.90 (2) | 175 |
Symmetry codes: (i) −x+2, y, −z+1/2; (ii) −x+3/2, −y+3/2, −z+1; (iii) −x+3/2, y+1/2, −z+1/2; (iv) x+1/2, −y+3/2, z+1/2; (v) −x+3/2, y−1/2, −z+1/2; (vi) x, −y+1, z−1/2; (vii) −x+2, −y+1, −z+1. |
Acknowledgements
The authors thank Ondokuz Mayıs University (Turkey) for single-crystal X-ray experiment.
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