metal-organic compounds
Bis{μ-ethyl 4-[(4-hydroxyphenyl)diazenyl]benzoate-κO}bis[aqua(4-{[4-(ethoxycarbonyl)phenyl]diazenyl}phenolato-κO){ethyl 4-[(4-hydroxyphenyl)diazenyl]benzoate-κO}potassium]
aLaboratório de Físico-Química Aplicada e Tecnológica, Escola de Química e Alimentos, Universidade Federal do Rio Grande, Av. Itália km 08, Campus Carreiros, 96203-900, Rio Grande-RS, Brazil, and bLaboratório de Materiais Inorgânicos, Departamento de Química, Universidade Federal de Santa Maria, Av. Roraima, 97105-900, Santa Maria-RS, Brazil
*Correspondence e-mail: julianovicenti@gmail.com
The two potassium cations in the dinuclear molecule of [K2{OC(C14H13ON2)O}2{OC(C14H13ON2)OH}4(H2O)2] are connected through a double bridge involving two centrosymmetrically related ethyl-4-(phenylazophenol)benzoate ligands. Each cation is also bound to a further non-bridging ligand, one ethyl-4-(phenylazophenolate)benzoate anion and a water molecule, leading to a distorted fivefold coordination. The two uncharged ligands are almost planar, whereas in the anionic ligand the aromatic systems display a dihedral angle of 21.14 (11)°. A supramolecular network formed by hydrogen-bonding interactions between phenolate anions, phenol groups and water molecules connects the dimeric species along [001]. Hirshfeld surface calculations revealed the following contributions related to intermolecular interactions: C⋯H (24.4%), O⋯H (13.2%) and N⋯H (7.4%). The azo fragment is disordered over two sets of sites [occupancy ratio 0.824 (15):0.176 (5)].
CCDC reference: 1587513
Structure description
Azo dyes are a well known family of organic dyes including the azo group (—N=N—) bonded to aromatic ring systems (Zhang et al., 2013). There are several compounds reported containing even more than one azo chromophore per molecule, also linked to heterocyclic systems (Patni & Patni, 2016). The compounds are commonly prepared through a coupling reaction between an arenediazonium salt and typically aromatic or although other substituents such as carboxylates or can also be present (Purtas et al., 2017). Besides the wide application of these compounds in both textile and paint industries, the molecular structures of the azo dyes can be modified and tuned to act as ligands in coordination chemistry. For instance, the choice of an appropriate metal ion can lead to new materials with remarkable properties, such as optical active media for lens production, recording of optical holograms or data storage (Davidenko et al., 2008).
The 14H13ON2)O−, two neutral ethyl-4-(phenylazophenol)benzoate ligands OC(C14H13ON2)OH, and one water molecule (Fig. 1). The anion coordinates through the carbonyl oxygen atom, presenting a C44—O6phenolic distance of 1.309 (2) Å shorter than expected but compatible with a phenolate moiety due to resonance effects (Suter & Nonella, 1998). One of the neutral ethyl-4-(phenylazophenol)benzoate ligands is terminal and coordinates exclusively via the ester carbonyl group (C9—O8 = 1.127 (2) Å), whereas the second is bridging and coordinates through both phenol [C24—O3 = 1.325 (2) Å] and ester carbonyl [C3—O2 = 1.215 (2) Å] groups. A double bridge between two cations is formed by a third ethyl-4-(phenylazophenol)benzoate ligand generated by an inversion operation (2 – x, 1 – y, 1 – z), leading to dimeric species (Fig. 2). The fivefold coordination environment of the cation was computed by the method of Addison et al. (1984). The resulting τ5 index was found to be 0.56, indicating a coordination sphere between a trigonal bipyramid (τ5 = 1) and a square pyramid (τ5 = 0).
of the title compound contains one potassium cation, one ethyl-4-(phenylazophenolate)benzoate anion OC(CThe two uncharged ethyl-4-(phenylazophenol)benzoate ligands are almost planar, with r.m.s. deviations of 0.0236 Å (monodentate ligand) and 0.0591 Å (bridging ligand) for all non-hydrogen atoms. The dihedral angles between the phenyl rings are 2.53 (9)° (C51 ring and C61 ring) and 2.49 (9)° (C11 ring and C21 ring). The azo fragment N3/N4 of the ethyl-4-(phenylazophenolate)benzoate anion is disordered over two sets of sites, and the whole anion is not planar (r.m.s. deviation of 0.1696). Notably, the dihedral angle between the phenyl rings (C31 and C41 rings) is 21.14 (11)°.
The dimers follow a zigzag arrangement along [001] (Fig. 2). The dinuclear entities are connected through classical hydrogen bonding interactions involving phenolate anions, phenol groups and coordinating water molecules. Likewise, weak C—H⋯O interactions are also present (Table 1). In order to analyse the hydrogen-bonding contribution quantitatively, a Hirshfeld surface calculation was performed. The contribution of C⋯H is 24.4% for non-classic interactions, whereas classic bonding related to O⋯H and N⋯H correspond to 13.2% and 7.4%, respectively (Fig. 3).
Synthesis and crystallization
To 1.5 g (3.33 mmol) of ethyl-4-(phenylazophenol)benzoate dissolved in 10.0 ml of methanol were added 0.560 g (9.99 mmol) of KOH dissolved in 5.0 m of methanol. The reaction mixture was kept under constant stirring at room temperature for two h. The solvent was then partially evaporated under reduced pressure, affording orange block-like single crystals of the title compound.
Refinement
Crystal data, data collection and structure . The azo fragment comprising atoms N3 and N4 was found to be disordered over two sets of sites [occupancy ratio 0.824 (15):0.176 (5)]. The disorder was treated by using PART instruction in SHELXL (Sheldrick, 2015b).
details are summarized in Table 2
|
Structural data
CCDC reference: 1587513
https://doi.org/10.1107/S2414314617016959/wm4060sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617016959/wm4060Isup2.hkl
Data collection: APEX2 (Bruker, 2014); cell
SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2017 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg, 2006), Mercury (Macrae et al., 2006) and CrystalExplorer17 (Turner et al., 2017); software used to prepare material for publication: publCIF (Westrip, 2010).[K2(C15H14N2O3)4(C15H13N2O3)2(H2O)2] | F(000) = 1816 |
Mr = 1733.91 | Dx = 1.345 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 9.241 (2) Å | Cell parameters from 9137 reflections |
b = 10.241 (2) Å | θ = 2.3–30.6° |
c = 45.261 (9) Å | µ = 0.19 mm−1 |
β = 91.31 (3)° | T = 100 K |
V = 4282.2 (15) Å3 | Block, orange |
Z = 2 | 0.30 × 0.26 × 0.10 mm |
Bruker APEXII CCD diffractometer | 13099 independent reflections |
Radiation source: fine-focus sealed tube | 9788 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.050 |
φ and ω scans | θmax = 30.6°, θmin = 2.2° |
Absorption correction: numerical (SADABS; Bruker, 2014) | h = −13→13 |
Tmin = 0.701, Tmax = 0.746 | k = −14→14 |
89218 measured reflections | l = −64→64 |
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)] = 0.066 | Hydrogen site location: mixed |
wR(F2) = 0.158 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0494P)2 + 6.316P] where P = (Fo2 + 2Fc2)/3 |
13099 reflections | (Δ/σ)max = 0.001 |
594 parameters | Δρmax = 0.93 e Å−3 |
0 restraints | Δρmin = −0.69 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. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. Hydrogen atoms of the water molecule and the phenol OH groups were located from a difference Fourier map, while all other hydrogen atoms were calculated at idealized positions. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
K1 | 1.27684 (5) | 0.37517 (5) | 0.36022 (2) | 0.02488 (11) | |
O1W | 1.20241 (17) | 0.16449 (16) | 0.32369 (3) | 0.0244 (3) | |
O1 | 0.31758 (15) | 0.34718 (14) | 0.60941 (3) | 0.0209 (3) | |
O4 | 1.27370 (15) | 0.70828 (14) | 0.29247 (3) | 0.0228 (3) | |
O8 | 1.28617 (16) | 0.23893 (14) | 0.40874 (3) | 0.0230 (3) | |
O3 | 0.99472 (16) | 0.38866 (16) | 0.37042 (3) | 0.0249 (3) | |
O7 | 1.43811 (16) | 0.07337 (15) | 0.41841 (3) | 0.0242 (3) | |
O2 | 0.48657 (16) | 0.49718 (16) | 0.62057 (3) | 0.0255 (3) | |
O6 | 0.07140 (15) | 0.71962 (16) | 0.16708 (3) | 0.0249 (3) | |
O9 | 0.74694 (18) | 0.07815 (17) | 0.65459 (4) | 0.0310 (4) | |
O5 | 1.23235 (17) | 0.51173 (17) | 0.31213 (4) | 0.0328 (4) | |
N2 | 0.75278 (17) | 0.42064 (16) | 0.48120 (4) | 0.0190 (3) | |
N6 | 0.99329 (18) | 0.14434 (16) | 0.54520 (4) | 0.0198 (3) | |
N1 | 0.64857 (17) | 0.34744 (16) | 0.48747 (4) | 0.0186 (3) | |
N5 | 1.09568 (18) | 0.06925 (16) | 0.53849 (4) | 0.0197 (3) | |
N4 | 0.6031 (5) | 0.6895 (2) | 0.22523 (8) | 0.0190 (8) | 0.824 (15) |
N41 | 0.553 (3) | 0.6257 (12) | 0.2396 (3) | 0.022 (4) | 0.176 (15) |
N3 | 0.6216 (5) | 0.6131 (2) | 0.24702 (8) | 0.0206 (9) | 0.824 (15) |
N31 | 0.665 (3) | 0.6882 (13) | 0.2334 (4) | 0.026 (4) | 0.176 (15) |
C11 | 0.4813 (2) | 0.40352 (18) | 0.57239 (4) | 0.0169 (4) | |
C24 | 0.9343 (2) | 0.38920 (19) | 0.39736 (4) | 0.0186 (4) | |
C14 | 0.5950 (2) | 0.37235 (18) | 0.51635 (4) | 0.0170 (3) | |
C21 | 0.8101 (2) | 0.40234 (18) | 0.45282 (4) | 0.0172 (4) | |
C51 | 1.2699 (2) | 0.12855 (18) | 0.45474 (4) | 0.0183 (4) | |
C23 | 0.8278 (2) | 0.29877 (19) | 0.40525 (4) | 0.0198 (4) | |
H23 | 0.798274 | 0.232722 | 0.391666 | 0.024* | |
C3 | 0.4304 (2) | 0.42201 (19) | 0.60299 (4) | 0.0177 (4) | |
C9 | 1.3302 (2) | 0.15315 (18) | 0.42524 (4) | 0.0194 (4) | |
C61 | 0.9366 (2) | 0.12062 (19) | 0.57348 (4) | 0.0188 (4) | |
C54 | 1.1494 (2) | 0.09357 (18) | 0.50966 (4) | 0.0183 (4) | |
C6 | 1.1915 (2) | 0.6053 (2) | 0.29772 (4) | 0.0215 (4) | |
C22 | 0.7657 (2) | 0.30535 (19) | 0.43269 (4) | 0.0197 (4) | |
H22 | 0.693083 | 0.244393 | 0.437910 | 0.024* | |
C15 | 0.6489 (2) | 0.47054 (19) | 0.53493 (4) | 0.0193 (4) | |
H15 | 0.723888 | 0.526643 | 0.528574 | 0.023* | |
C64 | 0.8110 (2) | 0.0899 (2) | 0.62814 (5) | 0.0224 (4) | |
C12 | 0.4253 (2) | 0.30763 (19) | 0.55331 (4) | 0.0197 (4) | |
H12 | 0.348799 | 0.252746 | 0.559466 | 0.024* | |
C44 | 0.1954 (2) | 0.7087 (2) | 0.18141 (4) | 0.0224 (4) | |
C31 | 1.0441 (2) | 0.6151 (2) | 0.28387 (4) | 0.0221 (4) | |
C52 | 1.3218 (2) | 0.02940 (19) | 0.47333 (4) | 0.0200 (4) | |
H52 | 1.398285 | −0.025634 | 0.467245 | 0.024* | |
C62 | 0.9815 (2) | 0.01903 (19) | 0.59217 (4) | 0.0195 (4) | |
H62 | 1.054992 | −0.039486 | 0.586150 | 0.023* | |
C13 | 0.4819 (2) | 0.29296 (19) | 0.52538 (4) | 0.0200 (4) | |
H13 | 0.443280 | 0.228425 | 0.512349 | 0.024* | |
C26 | 0.9178 (2) | 0.49068 (19) | 0.44501 (5) | 0.0211 (4) | |
H26 | 0.949080 | 0.555584 | 0.458731 | 0.025* | |
C16 | 0.5917 (2) | 0.48523 (19) | 0.56273 (4) | 0.0198 (4) | |
H16 | 0.628111 | 0.551937 | 0.575453 | 0.024* | |
C55 | 1.0957 (2) | 0.19174 (19) | 0.49087 (4) | 0.0207 (4) | |
H55 | 1.018788 | 0.246402 | 0.496915 | 0.025* | |
C56 | 1.1556 (2) | 0.20817 (19) | 0.46357 (4) | 0.0205 (4) | |
H56 | 1.119061 | 0.273976 | 0.450619 | 0.025* | |
C63 | 0.9193 (2) | 0.0038 (2) | 0.61932 (4) | 0.0209 (4) | |
H63 | 0.949862 | −0.065184 | 0.632044 | 0.025* | |
C25 | 0.9794 (2) | 0.4845 (2) | 0.41753 (5) | 0.0225 (4) | |
H25 | 1.052359 | 0.545151 | 0.412380 | 0.027* | |
C53 | 1.2606 (2) | 0.01194 (19) | 0.50075 (4) | 0.0204 (4) | |
H53 | 1.294605 | −0.055795 | 0.513458 | 0.025* | |
C65 | 0.7645 (2) | 0.1902 (2) | 0.60946 (5) | 0.0241 (4) | |
H65 | 0.690645 | 0.248421 | 0.615448 | 0.029* | |
C66 | 0.8266 (2) | 0.2047 (2) | 0.58212 (5) | 0.0225 (4) | |
H66 | 0.794070 | 0.272076 | 0.569165 | 0.027* | |
C2 | 0.2632 (2) | 0.3610 (2) | 0.63923 (4) | 0.0225 (4) | |
H2A | 0.229633 | 0.451580 | 0.642460 | 0.027* | |
H2B | 0.341026 | 0.341377 | 0.653963 | 0.027* | |
C32 | 1.0009 (2) | 0.7238 (2) | 0.26758 (5) | 0.0274 (4) | |
H32 | 1.065267 | 0.794999 | 0.265069 | 0.033* | |
C43 | 0.3165 (2) | 0.7844 (2) | 0.17357 (5) | 0.0288 (5) | |
H43 | 0.308413 | 0.842533 | 0.157251 | 0.035* | |
C5 | 1.4195 (2) | 0.7053 (2) | 0.30541 (5) | 0.0253 (4) | |
H5A | 1.473364 | 0.628960 | 0.297964 | 0.030* | |
H5B | 1.415562 | 0.699049 | 0.327202 | 0.030* | |
C36 | 0.9485 (2) | 0.5108 (3) | 0.28754 (5) | 0.0305 (5) | |
H36 | 0.978309 | 0.436777 | 0.298758 | 0.037* | |
C45 | 0.2121 (2) | 0.6226 (2) | 0.20566 (5) | 0.0279 (5) | |
H45 | 0.132559 | 0.570430 | 0.211465 | 0.033* | |
C8 | 1.4990 (2) | 0.0952 (2) | 0.38945 (5) | 0.0262 (4) | |
H8A | 1.544284 | 0.182640 | 0.388577 | 0.031* | |
H8B | 1.422180 | 0.089838 | 0.373881 | 0.031* | |
C42 | 0.4458 (2) | 0.7755 (3) | 0.18914 (6) | 0.0330 (5) | |
H42 | 0.525225 | 0.828567 | 0.183676 | 0.040* | |
C41 | 0.4612 (2) | 0.6903 (2) | 0.21262 (5) | 0.0310 (5) | |
C46 | 0.3432 (3) | 0.6133 (2) | 0.22108 (5) | 0.0317 (5) | |
H46 | 0.353157 | 0.554977 | 0.237325 | 0.038* | |
C4 | 1.4926 (3) | 0.8298 (2) | 0.29658 (5) | 0.0314 (5) | |
H4A | 1.591417 | 0.831422 | 0.304902 | 0.047* | |
H4B | 1.495816 | 0.834680 | 0.274979 | 0.047* | |
H4C | 1.438273 | 0.904456 | 0.304086 | 0.047* | |
C33 | 0.8616 (3) | 0.7271 (3) | 0.25492 (5) | 0.0333 (5) | |
H33 | 0.830543 | 0.801323 | 0.243896 | 0.040* | |
C34 | 0.7678 (2) | 0.6214 (3) | 0.25847 (5) | 0.0321 (5) | |
C1 | 0.1402 (3) | 0.2674 (2) | 0.64255 (5) | 0.0319 (5) | |
H1A | 0.101783 | 0.274963 | 0.662482 | 0.048* | |
H1B | 0.063604 | 0.287864 | 0.627939 | 0.048* | |
H1C | 0.174590 | 0.178063 | 0.639400 | 0.048* | |
C35 | 0.8103 (3) | 0.5148 (3) | 0.27491 (5) | 0.0344 (5) | |
H35 | 0.745429 | 0.444049 | 0.277624 | 0.041* | |
C7 | 1.6105 (3) | −0.0094 (3) | 0.38500 (6) | 0.0403 (6) | |
H7A | 1.654181 | 0.001927 | 0.365643 | 0.060* | |
H7B | 1.685725 | −0.002989 | 0.400539 | 0.060* | |
H7C | 1.564175 | −0.095371 | 0.385910 | 0.060* | |
H2W | 1.113 (4) | 0.176 (3) | 0.3215 (7) | 0.049 (9)* | |
H1W | 1.232 (3) | 0.183 (3) | 0.3076 (7) | 0.043 (8)* | |
H9 | 0.775 (4) | −0.006 (4) | 0.6632 (7) | 0.059 (10)* | |
H3 | 0.962 (3) | 0.321 (3) | 0.3600 (7) | 0.047 (9)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
K1 | 0.0214 (2) | 0.0310 (2) | 0.0220 (2) | −0.00758 (18) | −0.00356 (16) | 0.00664 (18) |
O1W | 0.0173 (7) | 0.0361 (8) | 0.0199 (7) | 0.0005 (6) | 0.0055 (6) | 0.0033 (6) |
O1 | 0.0178 (6) | 0.0241 (7) | 0.0209 (7) | −0.0035 (5) | 0.0028 (5) | −0.0042 (5) |
O4 | 0.0204 (7) | 0.0252 (7) | 0.0227 (7) | −0.0005 (6) | −0.0035 (6) | 0.0031 (6) |
O8 | 0.0284 (8) | 0.0199 (7) | 0.0205 (7) | −0.0033 (6) | −0.0012 (6) | 0.0041 (5) |
O3 | 0.0211 (7) | 0.0316 (8) | 0.0222 (7) | −0.0040 (6) | 0.0043 (6) | −0.0011 (6) |
O7 | 0.0230 (7) | 0.0248 (7) | 0.0250 (7) | −0.0017 (6) | 0.0041 (6) | 0.0031 (6) |
O2 | 0.0236 (7) | 0.0332 (8) | 0.0198 (7) | −0.0089 (6) | −0.0003 (6) | −0.0053 (6) |
O6 | 0.0173 (7) | 0.0350 (8) | 0.0223 (7) | 0.0013 (6) | −0.0003 (5) | 0.0027 (6) |
O9 | 0.0302 (8) | 0.0347 (9) | 0.0284 (8) | 0.0035 (7) | 0.0091 (7) | −0.0014 (7) |
O5 | 0.0256 (8) | 0.0374 (9) | 0.0352 (9) | −0.0012 (7) | −0.0051 (7) | 0.0185 (7) |
N2 | 0.0174 (8) | 0.0186 (8) | 0.0210 (8) | 0.0007 (6) | 0.0017 (6) | −0.0002 (6) |
N6 | 0.0208 (8) | 0.0185 (8) | 0.0199 (8) | −0.0035 (6) | −0.0029 (6) | 0.0005 (6) |
N1 | 0.0178 (8) | 0.0178 (7) | 0.0201 (8) | 0.0004 (6) | −0.0002 (6) | 0.0000 (6) |
N5 | 0.0207 (8) | 0.0186 (8) | 0.0197 (8) | −0.0040 (6) | −0.0022 (6) | 0.0006 (6) |
N4 | 0.0153 (16) | 0.0230 (11) | 0.0187 (15) | 0.0028 (10) | 0.0029 (12) | 0.0030 (9) |
N41 | 0.027 (10) | 0.028 (5) | 0.011 (5) | 0.009 (5) | −0.003 (6) | −0.006 (4) |
N3 | 0.0190 (19) | 0.0254 (12) | 0.0175 (13) | 0.0021 (10) | 0.0015 (12) | 0.0028 (9) |
N31 | 0.022 (9) | 0.033 (6) | 0.023 (7) | −0.002 (5) | −0.003 (6) | 0.001 (5) |
C11 | 0.0161 (8) | 0.0165 (8) | 0.0180 (9) | 0.0014 (7) | −0.0011 (7) | −0.0009 (7) |
C24 | 0.0135 (8) | 0.0219 (9) | 0.0205 (9) | 0.0023 (7) | 0.0005 (7) | 0.0025 (7) |
C14 | 0.0160 (8) | 0.0160 (8) | 0.0190 (9) | 0.0016 (7) | −0.0012 (7) | 0.0007 (7) |
C21 | 0.0151 (8) | 0.0183 (9) | 0.0182 (9) | 0.0014 (7) | −0.0006 (7) | 0.0003 (7) |
C51 | 0.0208 (9) | 0.0158 (8) | 0.0183 (9) | −0.0057 (7) | −0.0028 (7) | −0.0007 (7) |
C23 | 0.0183 (9) | 0.0205 (9) | 0.0204 (9) | −0.0014 (7) | −0.0014 (7) | −0.0015 (7) |
C3 | 0.0140 (8) | 0.0192 (9) | 0.0200 (9) | 0.0023 (7) | −0.0014 (7) | 0.0002 (7) |
C9 | 0.0201 (9) | 0.0157 (8) | 0.0222 (9) | −0.0065 (7) | −0.0011 (7) | −0.0010 (7) |
C61 | 0.0191 (9) | 0.0176 (8) | 0.0197 (9) | −0.0047 (7) | −0.0029 (7) | −0.0006 (7) |
C54 | 0.0203 (9) | 0.0163 (8) | 0.0181 (9) | −0.0052 (7) | −0.0038 (7) | 0.0008 (7) |
C6 | 0.0210 (9) | 0.0271 (10) | 0.0165 (9) | 0.0005 (8) | 0.0017 (7) | 0.0036 (7) |
C22 | 0.0185 (9) | 0.0202 (9) | 0.0204 (9) | −0.0020 (7) | 0.0000 (7) | 0.0018 (7) |
C15 | 0.0202 (9) | 0.0164 (8) | 0.0212 (9) | −0.0038 (7) | −0.0003 (7) | 0.0008 (7) |
C64 | 0.0190 (9) | 0.0245 (10) | 0.0239 (10) | −0.0047 (7) | 0.0021 (8) | −0.0018 (8) |
C12 | 0.0170 (9) | 0.0206 (9) | 0.0214 (9) | −0.0027 (7) | 0.0012 (7) | −0.0021 (7) |
C44 | 0.0182 (9) | 0.0294 (10) | 0.0197 (9) | 0.0091 (8) | 0.0009 (7) | −0.0046 (8) |
C31 | 0.0186 (9) | 0.0331 (11) | 0.0145 (9) | 0.0025 (8) | 0.0009 (7) | 0.0001 (8) |
C52 | 0.0196 (9) | 0.0178 (9) | 0.0225 (10) | −0.0024 (7) | −0.0021 (7) | 0.0001 (7) |
C62 | 0.0176 (9) | 0.0191 (9) | 0.0216 (9) | −0.0024 (7) | −0.0013 (7) | −0.0001 (7) |
C13 | 0.0190 (9) | 0.0200 (9) | 0.0210 (9) | −0.0032 (7) | −0.0007 (7) | −0.0039 (7) |
C26 | 0.0198 (9) | 0.0188 (9) | 0.0248 (10) | −0.0020 (7) | 0.0006 (7) | −0.0030 (7) |
C16 | 0.0221 (9) | 0.0169 (9) | 0.0202 (9) | −0.0021 (7) | −0.0028 (7) | −0.0003 (7) |
C55 | 0.0228 (9) | 0.0177 (9) | 0.0214 (9) | −0.0002 (7) | −0.0023 (7) | 0.0010 (7) |
C56 | 0.0237 (9) | 0.0164 (8) | 0.0211 (9) | −0.0007 (7) | −0.0032 (8) | 0.0031 (7) |
C63 | 0.0198 (9) | 0.0200 (9) | 0.0228 (10) | −0.0034 (7) | −0.0010 (7) | 0.0019 (7) |
C25 | 0.0189 (9) | 0.0209 (9) | 0.0278 (10) | −0.0043 (7) | 0.0024 (8) | −0.0009 (8) |
C53 | 0.0222 (9) | 0.0169 (9) | 0.0220 (9) | −0.0027 (7) | −0.0036 (7) | 0.0046 (7) |
C65 | 0.0193 (9) | 0.0241 (10) | 0.0287 (11) | 0.0011 (8) | −0.0008 (8) | −0.0029 (8) |
C66 | 0.0209 (9) | 0.0193 (9) | 0.0271 (10) | −0.0017 (7) | −0.0040 (8) | 0.0009 (8) |
C2 | 0.0196 (9) | 0.0289 (10) | 0.0190 (9) | −0.0026 (8) | 0.0016 (7) | −0.0024 (8) |
C32 | 0.0271 (11) | 0.0328 (11) | 0.0223 (10) | 0.0068 (9) | −0.0020 (8) | 0.0006 (9) |
C43 | 0.0200 (10) | 0.0344 (12) | 0.0321 (12) | 0.0049 (9) | 0.0020 (8) | −0.0021 (9) |
C5 | 0.0173 (9) | 0.0330 (11) | 0.0257 (10) | −0.0013 (8) | −0.0009 (8) | 0.0001 (9) |
C36 | 0.0241 (10) | 0.0438 (13) | 0.0237 (11) | −0.0050 (10) | −0.0014 (8) | 0.0053 (9) |
C45 | 0.0254 (10) | 0.0354 (12) | 0.0231 (10) | 0.0082 (9) | 0.0036 (8) | 0.0002 (9) |
C8 | 0.0249 (10) | 0.0271 (10) | 0.0270 (11) | −0.0052 (8) | 0.0063 (8) | 0.0002 (8) |
C42 | 0.0203 (10) | 0.0412 (13) | 0.0375 (13) | 0.0073 (9) | 0.0011 (9) | −0.0058 (10) |
C41 | 0.0219 (10) | 0.0399 (13) | 0.0311 (12) | 0.0105 (9) | −0.0018 (9) | −0.0125 (10) |
C46 | 0.0383 (13) | 0.0377 (12) | 0.0189 (10) | 0.0168 (10) | −0.0029 (9) | −0.0020 (9) |
C4 | 0.0261 (11) | 0.0327 (12) | 0.0355 (12) | −0.0048 (9) | 0.0066 (9) | −0.0038 (10) |
C33 | 0.0368 (13) | 0.0385 (13) | 0.0242 (11) | 0.0185 (10) | −0.0073 (9) | −0.0025 (9) |
C34 | 0.0202 (10) | 0.0500 (14) | 0.0260 (11) | 0.0052 (10) | −0.0006 (8) | −0.0154 (10) |
C1 | 0.0280 (11) | 0.0352 (12) | 0.0330 (12) | −0.0098 (9) | 0.0121 (9) | −0.0082 (10) |
C35 | 0.0240 (11) | 0.0500 (15) | 0.0291 (12) | −0.0063 (10) | −0.0005 (9) | 0.0000 (10) |
C7 | 0.0334 (13) | 0.0367 (13) | 0.0514 (16) | 0.0020 (11) | 0.0182 (12) | 0.0014 (12) |
K1—O8 | 2.6016 (16) | C64—C63 | 1.399 (3) |
K1—O5 | 2.6121 (18) | C12—C13 | 1.387 (3) |
K1—O3 | 2.6614 (16) | C12—H12 | 0.9500 |
K1—O2i | 2.6754 (17) | C44—C43 | 1.413 (3) |
K1—O1W | 2.7947 (19) | C44—C45 | 1.414 (3) |
K1—H2W | 3.07 (3) | C31—C32 | 1.388 (3) |
K1—H3 | 2.96 (3) | C31—C36 | 1.398 (3) |
O1W—H2W | 0.84 (3) | C52—C53 | 1.387 (3) |
O1W—H1W | 0.81 (3) | C52—H52 | 0.9500 |
O1—C3 | 1.331 (2) | C62—C63 | 1.378 (3) |
O1—C2 | 1.458 (2) | C62—H62 | 0.9500 |
O4—C6 | 1.325 (3) | C13—H13 | 0.9500 |
O4—C5 | 1.457 (2) | C26—C25 | 1.381 (3) |
O8—C9 | 1.217 (2) | C26—H26 | 0.9500 |
O3—C24 | 1.353 (2) | C16—H16 | 0.9500 |
O3—H3 | 0.88 (3) | C55—C56 | 1.376 (3) |
O7—C9 | 1.331 (2) | C55—H55 | 0.9500 |
O7—C8 | 1.455 (2) | C56—H56 | 0.9500 |
O2—C3 | 1.215 (2) | C63—H63 | 0.9500 |
O6—C44 | 1.309 (2) | C25—H25 | 0.9500 |
O9—C64 | 1.352 (3) | C53—H53 | 0.9500 |
O9—H9 | 0.98 (4) | C65—C66 | 1.384 (3) |
O5—C6 | 1.214 (3) | C65—H65 | 0.9500 |
N2—N1 | 1.258 (2) | C66—H66 | 0.9500 |
N2—C21 | 1.413 (2) | C2—C1 | 1.498 (3) |
N6—N5 | 1.262 (2) | C2—H2A | 0.9900 |
N6—C61 | 1.415 (3) | C2—H2B | 0.9900 |
N1—C14 | 1.431 (2) | C32—C33 | 1.397 (3) |
N5—C54 | 1.429 (3) | C32—H32 | 0.9500 |
N4—N3 | 1.267 (7) | C43—C42 | 1.377 (3) |
N4—C41 | 1.418 (6) | C43—H43 | 0.9500 |
N41—N31 | 1.25 (3) | C5—C4 | 1.501 (3) |
N41—C41 | 1.61 (2) | C5—H5A | 0.9900 |
N3—C34 | 1.439 (5) | C5—H5B | 0.9900 |
N31—C34 | 1.62 (2) | C36—C35 | 1.387 (3) |
C11—C16 | 1.397 (3) | C36—H36 | 0.9500 |
C11—C12 | 1.399 (3) | C45—C46 | 1.387 (3) |
C11—C3 | 1.485 (3) | C45—H45 | 0.9500 |
C24—C25 | 1.394 (3) | C8—C7 | 1.503 (3) |
C24—C23 | 1.404 (3) | C8—H8A | 0.9900 |
C14—C13 | 1.393 (3) | C8—H8B | 0.9900 |
C14—C15 | 1.395 (3) | C42—C41 | 1.380 (4) |
C21—C26 | 1.397 (3) | C42—H42 | 0.9500 |
C21—C22 | 1.403 (3) | C41—C46 | 1.406 (4) |
C51—C52 | 1.396 (3) | C46—H46 | 0.9500 |
C51—C56 | 1.400 (3) | C4—H4A | 0.9800 |
C51—C9 | 1.480 (3) | C4—H4B | 0.9800 |
C23—C22 | 1.382 (3) | C4—H4C | 0.9800 |
C23—H23 | 0.9500 | C33—C34 | 1.398 (4) |
C61—C66 | 1.395 (3) | C33—H33 | 0.9500 |
C61—C62 | 1.398 (3) | C34—C35 | 1.374 (4) |
C54—C53 | 1.391 (3) | C1—H1A | 0.9800 |
C54—C55 | 1.400 (3) | C1—H1B | 0.9800 |
C6—C31 | 1.490 (3) | C1—H1C | 0.9800 |
C22—H22 | 0.9500 | C35—H35 | 0.9500 |
C15—C16 | 1.384 (3) | C7—H7A | 0.9800 |
C15—H15 | 0.9500 | C7—H7B | 0.9800 |
C64—C65 | 1.393 (3) | C7—H7C | 0.9800 |
O8—K1—O5 | 172.84 (5) | C12—C13—H13 | 119.8 |
O8—K1—O3 | 83.98 (6) | C14—C13—H13 | 119.8 |
O5—K1—O3 | 88.89 (6) | C25—C26—C21 | 120.57 (19) |
O8—K1—O2i | 88.66 (6) | C25—C26—H26 | 119.7 |
O5—K1—O2i | 96.95 (6) | C21—C26—H26 | 119.7 |
O3—K1—O2i | 135.62 (5) | C15—C16—C11 | 121.05 (18) |
O8—K1—O1W | 95.07 (5) | C15—C16—H16 | 119.5 |
O5—K1—O1W | 83.59 (6) | C11—C16—H16 | 119.5 |
O3—K1—O1W | 85.06 (6) | C56—C55—C54 | 119.29 (19) |
O2i—K1—O1W | 139.27 (5) | C56—C55—H55 | 120.4 |
O8—K1—H2W | 97.6 (6) | C54—C55—H55 | 120.4 |
O5—K1—H2W | 79.2 (6) | C55—C56—C51 | 120.44 (18) |
O3—K1—H2W | 70.1 (6) | C55—C56—H56 | 119.8 |
O2i—K1—H2W | 154.2 (6) | C51—C56—H56 | 119.8 |
O1W—K1—H2W | 15.6 (6) | C62—C63—C64 | 119.94 (19) |
O8—K1—H3 | 85.2 (6) | C62—C63—H63 | 120.0 |
O5—K1—H3 | 87.7 (6) | C64—C63—H63 | 120.0 |
O3—K1—H3 | 17.0 (6) | C26—C25—C24 | 119.96 (18) |
O2i—K1—H3 | 152.6 (6) | C26—C25—H25 | 120.0 |
O1W—K1—H3 | 68.0 (6) | C24—C25—H25 | 120.0 |
H2W—K1—H3 | 53.2 (9) | C52—C53—C54 | 120.03 (18) |
K1—O1W—H2W | 101 (2) | C52—C53—H53 | 120.0 |
K1—O1W—H1W | 106 (2) | C54—C53—H53 | 120.0 |
H2W—O1W—H1W | 102 (3) | C66—C65—C64 | 119.56 (19) |
C3—O1—C2 | 115.74 (15) | C66—C65—H65 | 120.2 |
C6—O4—C5 | 116.11 (16) | C64—C65—H65 | 120.2 |
C9—O8—K1 | 155.41 (14) | C65—C66—C61 | 120.30 (19) |
C24—O3—K1 | 125.63 (12) | C65—C66—H66 | 119.9 |
C24—O3—H3 | 110 (2) | C61—C66—H66 | 119.9 |
K1—O3—H3 | 101 (2) | O1—C2—C1 | 108.01 (17) |
C9—O7—C8 | 114.94 (16) | O1—C2—H2A | 110.1 |
C3—O2—K1i | 148.90 (13) | C1—C2—H2A | 110.1 |
C64—O9—H9 | 108 (2) | O1—C2—H2B | 110.1 |
C6—O5—K1 | 155.65 (16) | C1—C2—H2B | 110.1 |
N1—N2—C21 | 115.52 (17) | H2A—C2—H2B | 108.4 |
N5—N6—C61 | 114.10 (17) | C31—C32—C33 | 119.2 (2) |
N2—N1—C14 | 112.48 (16) | C31—C32—H32 | 120.4 |
N6—N5—C54 | 113.08 (16) | C33—C32—H32 | 120.4 |
N3—N4—C41 | 115.1 (4) | C42—C43—C44 | 121.2 (2) |
N31—N41—C41 | 92.4 (16) | C42—C43—H43 | 119.4 |
N4—N3—C34 | 110.7 (4) | C44—C43—H43 | 119.4 |
N41—N31—C34 | 96.0 (16) | O4—C5—C4 | 107.02 (18) |
C16—C11—C12 | 119.33 (18) | O4—C5—H5A | 110.3 |
C16—C11—C3 | 117.68 (17) | C4—C5—H5A | 110.3 |
C12—C11—C3 | 122.99 (17) | O4—C5—H5B | 110.3 |
O3—C24—C25 | 118.05 (18) | C4—C5—H5B | 110.3 |
O3—C24—C23 | 122.22 (18) | H5A—C5—H5B | 108.6 |
C25—C24—C23 | 119.73 (18) | C35—C36—C31 | 120.4 (2) |
C13—C14—C15 | 120.21 (18) | C35—C36—H36 | 119.8 |
C13—C14—N1 | 116.21 (17) | C31—C36—H36 | 119.8 |
C15—C14—N1 | 123.58 (17) | C46—C45—C44 | 120.8 (2) |
C26—C21—C22 | 119.61 (18) | C46—C45—H45 | 119.6 |
C26—C21—N2 | 115.35 (17) | C44—C45—H45 | 119.6 |
C22—C21—N2 | 125.04 (17) | O7—C8—C7 | 106.95 (19) |
C52—C51—C56 | 120.15 (18) | O7—C8—H8A | 110.3 |
C52—C51—C9 | 122.44 (18) | C7—C8—H8A | 110.3 |
C56—C51—C9 | 117.40 (18) | O7—C8—H8B | 110.3 |
C22—C23—C24 | 120.33 (19) | C7—C8—H8B | 110.3 |
C22—C23—H23 | 119.8 | H8A—C8—H8B | 108.6 |
C24—C23—H23 | 119.8 | C43—C42—C41 | 120.6 (2) |
O2—C3—O1 | 123.15 (18) | C43—C42—H42 | 119.7 |
O2—C3—C11 | 123.48 (18) | C41—C42—H42 | 119.7 |
O1—C3—C11 | 113.37 (17) | C42—C41—C46 | 119.8 (2) |
O8—C9—O7 | 122.85 (18) | C42—C41—N4 | 113.1 (2) |
O8—C9—C51 | 123.31 (19) | C46—C41—N4 | 127.1 (2) |
O7—C9—C51 | 113.84 (17) | C42—C41—N41 | 152.5 (7) |
C66—C61—C62 | 119.86 (18) | C46—C41—N41 | 87.7 (6) |
C66—C61—N6 | 115.76 (18) | C45—C46—C41 | 119.9 (2) |
C62—C61—N6 | 124.36 (18) | C45—C46—H46 | 120.1 |
C53—C54—C55 | 120.62 (18) | C41—C46—H46 | 120.1 |
C53—C54—N5 | 115.73 (17) | C5—C4—H4A | 109.5 |
C55—C54—N5 | 123.65 (18) | C5—C4—H4B | 109.5 |
O5—C6—O4 | 123.49 (19) | H4A—C4—H4B | 109.5 |
O5—C6—C31 | 123.3 (2) | C5—C4—H4C | 109.5 |
O4—C6—C31 | 113.17 (18) | H4A—C4—H4C | 109.5 |
C23—C22—C21 | 119.78 (18) | H4B—C4—H4C | 109.5 |
C23—C22—H22 | 120.1 | C34—C33—C32 | 120.1 (2) |
C21—C22—H22 | 120.1 | C34—C33—H33 | 120.0 |
C16—C15—C14 | 119.22 (18) | C32—C33—H33 | 120.0 |
C16—C15—H15 | 120.4 | C35—C34—C33 | 120.5 (2) |
C14—C15—H15 | 120.4 | C35—C34—N3 | 113.8 (2) |
O9—C64—C65 | 117.89 (19) | C33—C34—N3 | 125.7 (2) |
O9—C64—C63 | 121.79 (19) | C35—C34—N31 | 150.8 (6) |
C65—C64—C63 | 120.31 (19) | C33—C34—N31 | 87.1 (6) |
C13—C12—C11 | 119.78 (18) | C2—C1—H1A | 109.5 |
C13—C12—H12 | 120.1 | C2—C1—H1B | 109.5 |
C11—C12—H12 | 120.1 | H1A—C1—H1B | 109.5 |
O6—C44—C43 | 121.2 (2) | C2—C1—H1C | 109.5 |
O6—C44—C45 | 121.1 (2) | H1A—C1—H1C | 109.5 |
C43—C44—C45 | 117.7 (2) | H1B—C1—H1C | 109.5 |
C32—C31—C36 | 120.0 (2) | C34—C35—C36 | 119.7 (2) |
C32—C31—C6 | 121.8 (2) | C34—C35—H35 | 120.2 |
C36—C31—C6 | 118.19 (19) | C36—C35—H35 | 120.2 |
C53—C52—C51 | 119.45 (19) | C8—C7—H7A | 109.5 |
C53—C52—H52 | 120.3 | C8—C7—H7B | 109.5 |
C51—C52—H52 | 120.3 | H7A—C7—H7B | 109.5 |
C63—C62—C61 | 120.00 (19) | C8—C7—H7C | 109.5 |
C63—C62—H62 | 120.0 | H7A—C7—H7C | 109.5 |
C61—C62—H62 | 120.0 | H7B—C7—H7C | 109.5 |
C12—C13—C14 | 120.35 (18) |
Symmetry code: (i) −x+2, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C63—H63···O6ii | 0.95 | 2.49 | 3.427 (3) | 169 |
C8—H8B···O9iii | 0.99 | 2.64 | 3.476 (3) | 142 |
C4—H4C···O9i | 0.98 | 2.57 | 3.301 (3) | 131 |
O1W—H1W···N4iv | 0.81 (3) | 2.15 (3) | 2.895 (3) | 153 (3) |
O1W—H1W···N31iv | 0.81 (3) | 2.11 (4) | 2.898 (13) | 166 (3) |
O9—H9···O1Wiii | 0.98 (4) | 1.74 (4) | 2.709 (3) | 171 (3) |
O1W—H2W···O6v | 0.84 (3) | 1.84 (3) | 2.635 (2) | 156 (3) |
O3—H3···O6v | 0.88 (3) | 1.63 (3) | 2.490 (2) | 163 (3) |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x+1, −y+1/2, z+1/2; (iii) −x+2, −y, −z+1; (iv) −x+2, y−1/2, −z+1/2; (v) −x+1, y−1/2, −z+1/2. |
Funding information
The authors acknowledge CT–Infra (FINEP) and FIPE JUNIOR CCNE/UFSM-2017 for support.
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