research communications
μ-{2-[(5-bromo-2-oxidobenzylidene)amino]ethyl}sulfanido-κ3N,O,S){2,2′-[(3,4-dithiahexane-1,6-diyl)bis(nitrilomethanylylidene)]bis(4-bromophenolato)-κ4O,N,N′,O′}dicobalt(III) dimethylformamide monosolvate
of bis(aDepartment of Chemistry, Taras Shevchenko National University of Kyiv, 64/13, Volodymyrska str., Kyiv 01601, Ukraine
*Correspondence e-mail: rusanova_j@yahoo.com
The title binuclear CoIII complex, [Co2(C9H8BrNOS)2(C18H16Br2N2O2S2)]·C3H7NO, with a Schiff base ligand formed in situ from cysteamine (2-aminoethanethiol) and 5-bromosalicylaldehyde crystallizes in the P21. It was found that during the synthesis the ligand undergoes spontaneous oxidation, forming the new ligand H2L′ having an S—S bond. Thus, the consists of one Co2(L)2(L′) molecule and one DMF solvent molecule. Each CoIII ion has a slightly distorted octahedral S2N2O2 coordination geometry. In the crystal, the components are linked into a three-dimensional network by several S⋯ Br, C⋯ Br, C—H⋯Br, short S⋯C (essentially shorter than the sum of the van der Waals radii for the atoms involved) contacts as well by weak C—H⋯O hydrogen bonds. The crystal studied was refined as an inversion twin.
Keywords: crystal structure; binuclear CoIII complex; Schiff bases; 5-bromosalicylaldehyde; cysteamine (2-aminoethanthiol).
CCDC reference: 1916953
1. Chemical context
et al., 1997; Bera et al., 1998; Prabhakaran et al., 2004; Nesterov et al., 2014). It has been shown that the formation and cleavage of disulfide bonds is important for the biological activity of several sulfur-containing and proteins (Gilbert et al., 1999; Jacob et al., 2003), which makes the study of complexes having a multidentate NSO-containing mixed-ligand environment of considerable interest. Thus, such complexes can be considered as model objects for studying the active sites of biological systems (Halcrow et al., 1994). Despite this, very few studies devoted to the synthesis and investigation of complexes of formed from thioamino alcohol have been reported. In this work we present a novel binuclear CoIII complex with a mixed N,O,S-donor Schiff base ligand derived from the condensation of 5-bromosalicylaldehyde with cysteamine (2-aminoethanthiol) hydrochloride. The synthesis, and spectroscopic characterization are described herein.
represent one of the most widely used organic compounds. The ability to construct novel ligand systems by means of condensation of a variety of readily available and amine makes them and their metal complexes ideal candidates for the construction of novel polynuclear compounds as well for investigation of a large range of properties (Mitra2. Structural commentary
The title compound (Fig. 1) crystallizes in the monoclinic P21. The consists of a binuclear metal complex molecule and a DMF solvent molecule of crystallization. The coordination geometry around each CoIII ion can be described as slightly distorted octahedral with an S2N2O2 coordination sphere, each ligand spanning the metal atom meridionally. The ligand fragments coordinated to the CoIII ions are twisted, as defined by the dihedral angles of 70.41 (2)° between the mean planes of atoms O3/N3/C19/C24/C25 and O4/N4/C28/C33/C34 around Co1, and 64.78 (2)° between the mean planes of atoms O2/N2/C15/C10/C16 and O1/N1/C1/C6/C7 around Co2. During the synthesis, the ligand is partially oxidized with the formation of a –(CH2)2–S–S–(CH2)2– bridge. Thus, in contrast to a closely related complex (Chakraborty et al., 1994), in the title complex the oxidized Schiff base ligand binds to Co1 in a tetradentate fashion while the non-oxidized ligand binds to Co2 in a tridentate fashion, and its thiolate atoms lie in a cis-position, bridging atoms Co1 and Co2. The Co2S2 bridge is almost planar, with a mean deviation of 0.0673 (4) Å. The Co—S distances in the title complex are in the range 2.207 (3)–2.289 (3) Å, which is generally comparable to the range 2.23–2.26 Å observed for other thioether–CoIII complexes published earlier (Chakraborty et al., 1994 and references therein). Contact distances such as for Co⋯Co and S⋯S are also similar.
3. Supramolecular features
In the crystal, the bridging ligands are involved in short S⋯Br(x, y, 1 + z) [3.596 (2) Å] and S⋯ Br(x, y, −1 + z) [3.364 (2) Å] contacts, which connect neighboring structural units into chains along [001] (Fig. 2). The solvent DMF molecules are connected to the complex units by weak C—H⋯O hydrogen bonds (Table 1, Fig. 3). In addition, the components are linked by C—H⋯Br (Table 1), C⋯Br [C10⋯Br = 3 3.443 (8) Å and C15⋯Br3 = 3.506 (7) Å] and short S⋯C contacts. These interatomic C⋯Br distances are in agreement with reported data (Echenique-Errandonea et al., 2018; Tan et al., 2018). The interatomic distances between the aliphatic sulfur atom (S4) and the C16 carbon atom of the ligand of an adjacent molecule (at 1 + x, y, z) are essentially shorter than the sum of the van der Waals radii for the atoms involved [S4⋯C16 = 3.198 (8) Å] (Fig. 4). Analogous short contacts are well known for coordination compounds with the 1,2,3,4,5-dithiadiazolyl radical (Beldjoudi et al., 2013; Boeré, 2016 and references therein).
4. Database survey
A search of the Cambridge Structural Database (Version 5.40; last update February 2019; Groom et al., 2016) for related Co complexes with an aminoethanethiol group gave 15 hits, including two closely related structures, binuclear bis[(μ2-2-(salicylideneamino)ethanethiolato]-N-(3-thiapent-5-enyl)salicylaldiminato-N,O)dicobalt(III) acetonitrile solvate and [1,8-bis(salicylideneamino)-3,6-dithiaoctane)cobalt(III) perchlorate with a disulfide moiety (Chakraborty et al., 1994). Closely related structures with short S⋯C contacts are 4-(4-methylphenyl)-3H-1,2,3,5-dithiadiazole (Beldjoudi et al., 2013) and bis[4-(4-trifluoromethylphenyl)-1,2,3,5-dithiadiazolyl radical] triphenylstibine (Boeré, 2016).
5. Synthesis and crystallization
A solution of KOH (0.12 g, 2 mmol) in a minimum amount of methanol was added to a solution of 2-aminoethanthiol hydrochloride (0.23g, 2 mmol) in methanol (5 ml) and stirred in an ice bath for 10 min. The white precipitate of solid KCl was removed by filtration and 5-bromosalicylaldehyde (0.40 g, 2 mmol) in dimethylformamide (10 ml) were added to the filtrate and stirred on air magnetically for 40 min. Cobalt acetate (0.25 g, 1 mmol) was added to the yellowish solution of the Schiff base formed in situ, and the resulting deep-brown solution was stirred magnetically and heated in air at 323–333 K for 2 h. Crystals suitable for X-ray crystallographic study were formed within ca 1 month after successive addition of i-PrOH into the resulting solution. The crystals were filtered off, washed with dry i-PrOH and finally dried at room temperature (yield: 18%). Analysis calculated for C39H39Br4Co2N5O5S4 (M = 1223.49): C,38.28; N, 5.72; H, 3.21%. Found: C, 38.31; N, 5.79; H, 3.28%. The compound is sparingly soluble in CH3CN and good in DMSO, DMF.
The IR spectrum of the title complex in the 4000–400 cm−1 range shows the characteristic azomethine group (–H—C=N) peak at 1616 cm−1, indicating the formation of the Schiff base. There are no bands assignable to υ(O—H), indicating the loss of the phenolic hydrogen of the free ligand. In addition, all the characteristic peaks are present in the spectrum. Thus, signals in the 3000–3100 cm−1 and 1600–1400 cm−1 regions were assigned to the aromatic C—H and C—C stretches, and weak bands at 544 cm−1 and 684 cm−1 to the S—S and C—S stretches, respectively. The very strong bands at 1454 cm−1 can be attributed to overlapped C—H bending (scissoring) (in the CH3 groups of the solvent molecule) and aromatic –C=C stretching vibrations. Another strong band at 1310 cm−1 can be assigned to C—O vibrations.
The structural assignment of the title compound was supplemented by its 1H NMR spectra, obtained in DMSO-d6 at room temperature using TMS as the internal standard. It revealed an azomethine proton singlet at 8.099 ppm as well the increase in spectroscopic complexity in both the aromatic and aliphatic regions. 1H NMR, DMSO-d6, δ in ppm: –CH=N, 8.099 (s); aromatic protons (C6H3): 7.94–6.52; aliphatic protons (–SCH2CH2N=): 4.44 (m); solvent CH3: 2.96 (s), 2.8 (s). Unfortunately, it could not provide any indication of the dinuclear binding mode, which was revealed only by the X-ray structure determination.
6. Refinement
Crystal data, data collection and structure . The hydrogen atoms bonded to carbon were included at geometrically calculated positions (C—H = 0.93–0.97 Å) and refined using a riding model with Uiso(H) = 1.5Ueq(C-methyl) and 1.2Ueq(C) for other H atom. The crystal studied was refined as an with the ratio of the twin components refining to 0.436 (12):0.564 (12).
details are summarized in Table 2Supporting information
CCDC reference: 1916953
https://doi.org/10.1107/S2056989019007217/lh5903sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019007217/lh5903Isup2.hkl
Data collection: SMART (Bruker, 2008); cell
SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016/4 (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).[Co2(C9H8BrNOS)2C18H16Br2N2O2S2)]·C3H7NO | F(000) = 1212 |
Mr = 1223.49 | Dx = 1.825 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 11.532 (3) Å | Cell parameters from 920 reflections |
b = 17.714 (3) Å | θ = 2.3–18.8° |
c = 12.192 (3) Å | µ = 4.57 mm−1 |
β = 116.609 (6)° | T = 296 K |
V = 2226.9 (8) Å3 | Prizm, brown |
Z = 2 | 0.33 × 0.14 × 0.11 mm |
Bruker SMART APEXII diffractometer | 8890 independent reflections |
Radiation source: sealed tube | 4960 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.067 |
φ and ω scans | θmax = 26.6°, θmin = 1.9° |
Absorption correction: numerical face-indexed | h = −14→14 |
Tmin = 0.314, Tmax = 0.633 | k = −22→22 |
21805 measured reflections | l = −15→13 |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.051 | w = 1/[σ2(Fo2) + (0.033P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.101 | (Δ/σ)max = 0.002 |
S = 0.94 | Δρmax = 0.45 e Å−3 |
8890 reflections | Δρmin = −0.46 e Å−3 |
535 parameters | Absolute structure: Refined as an inversion twin |
1 restraint | Absolute structure parameter: 0.436 (12) |
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. Refined as a two-component inversion twin |
x | y | z | Uiso*/Ueq | ||
BR1 | 0.27868 (16) | 0.76620 (8) | 0.18956 (12) | 0.0773 (5) | |
BR2 | 0.57579 (17) | 0.57341 (10) | 1.36338 (12) | 0.0919 (6) | |
BR3 | 0.93442 (12) | 0.64978 (8) | 0.23531 (9) | 0.0583 (4) | |
BR4 | 1.20396 (17) | 0.42429 (7) | 1.46454 (11) | 0.0774 (5) | |
CO1 | 0.94686 (14) | 0.55635 (7) | 0.82744 (11) | 0.0349 (4) | |
CO2 | 0.67358 (15) | 0.63351 (8) | 0.81416 (12) | 0.0386 (4) | |
S1 | 0.7359 (3) | 0.57089 (15) | 0.6932 (2) | 0.0408 (7) | |
S2 | 0.8872 (3) | 0.63423 (16) | 0.9432 (2) | 0.0424 (7) | |
S3 | 1.2234 (4) | 0.38961 (19) | 0.7811 (3) | 0.0677 (10) | |
S4 | 1.3413 (4) | 0.4697 (2) | 0.8932 (3) | 0.0722 (11) | |
O1 | 0.4946 (7) | 0.6309 (4) | 0.6944 (7) | 0.050 (2) | |
O2 | 0.6291 (8) | 0.6884 (4) | 0.9258 (7) | 0.049 (2) | |
O3 | 0.9688 (7) | 0.6388 (4) | 0.7410 (5) | 0.0390 (18) | |
O4 | 0.9199 (8) | 0.4780 (4) | 0.9197 (6) | 0.046 (2) | |
O5 | 0.177 (3) | 0.8614 (10) | 0.602 (2) | 0.260 (15) | |
N1 | 0.7010 (9) | 0.7301 (5) | 0.7595 (8) | 0.040 (2) | |
N2 | 0.6434 (9) | 0.5376 (4) | 0.8673 (7) | 0.038 (2) | |
N3 | 0.9625 (8) | 0.4804 (5) | 0.7185 (7) | 0.036 (2) | |
N4 | 1.1350 (8) | 0.5635 (5) | 0.9465 (7) | 0.035 (2) | |
N5 | 0.356 (2) | 0.8298 (13) | 0.7453 (17) | 0.143 (8) | |
C1 | 0.4547 (11) | 0.6629 (6) | 0.5875 (11) | 0.044 (3) | |
C2 | 0.3323 (12) | 0.6388 (7) | 0.4908 (13) | 0.059 (3) | |
H2 | 0.285037 | 0.601437 | 0.506436 | 0.071* | |
C3 | 0.2849 (12) | 0.6700 (7) | 0.3769 (13) | 0.065 (4) | |
H3 | 0.207682 | 0.651838 | 0.314888 | 0.078* | |
C4 | 0.3498 (14) | 0.7284 (7) | 0.3514 (12) | 0.057 (4) | |
C5 | 0.4626 (12) | 0.7542 (6) | 0.4398 (10) | 0.050 (3) | |
H5 | 0.505155 | 0.793335 | 0.421852 | 0.060* | |
C6 | 0.5185 (11) | 0.7231 (6) | 0.5601 (10) | 0.042 (3) | |
C7 | 0.6325 (12) | 0.7562 (6) | 0.6516 (10) | 0.045 (3) | |
H7 | 0.660225 | 0.801060 | 0.631401 | 0.055* | |
C8 | 0.8050 (12) | 0.7758 (6) | 0.8552 (10) | 0.053 (3) | |
H8A | 0.776427 | 0.793289 | 0.914552 | 0.064* | |
H8B | 0.823098 | 0.819709 | 0.817832 | 0.064* | |
C9 | 0.9255 (12) | 0.7296 (6) | 0.9187 (10) | 0.051 (3) | |
H9A | 0.981261 | 0.752557 | 0.996978 | 0.061* | |
H9B | 0.972097 | 0.728743 | 0.869323 | 0.061* | |
C10 | 0.6155 (11) | 0.6597 (6) | 1.0181 (9) | 0.038 (3) | |
C11 | 0.5939 (11) | 0.7097 (7) | 1.0972 (10) | 0.053 (3) | |
H11 | 0.586732 | 0.761231 | 1.081041 | 0.063* | |
C12 | 0.5833 (13) | 0.6823 (8) | 1.1993 (11) | 0.062 (4) | |
H12 | 0.571389 | 0.716067 | 1.251758 | 0.074* | |
C13 | 0.5899 (13) | 0.6072 (8) | 1.2237 (10) | 0.054 (3) | |
C14 | 0.6085 (11) | 0.5577 (7) | 1.1483 (9) | 0.050 (3) | |
H14 | 0.612356 | 0.506339 | 1.165184 | 0.060* | |
C15 | 0.6221 (10) | 0.5824 (6) | 1.0453 (8) | 0.033 (3) | |
C16 | 0.6296 (11) | 0.5264 (6) | 0.9648 (10) | 0.042 (3) | |
H16 | 0.623739 | 0.476383 | 0.984981 | 0.051* | |
C17 | 0.6270 (13) | 0.4697 (6) | 0.7917 (10) | 0.060 (4) | |
H17A | 0.541320 | 0.448716 | 0.767656 | 0.071* | |
H17B | 0.690367 | 0.432056 | 0.840066 | 0.071* | |
C18 | 0.6431 (12) | 0.4873 (6) | 0.6793 (10) | 0.050 (3) | |
H18A | 0.558072 | 0.493104 | 0.610353 | 0.060* | |
H18B | 0.685403 | 0.444890 | 0.661665 | 0.060* | |
C19 | 0.9562 (10) | 0.6378 (6) | 0.6297 (9) | 0.034 (2) | |
C20 | 0.9507 (13) | 0.7066 (6) | 0.5724 (10) | 0.052 (3) | |
H20 | 0.951716 | 0.751035 | 0.613426 | 0.062* | |
C21 | 0.9438 (12) | 0.7111 (6) | 0.4553 (10) | 0.052 (3) | |
H21 | 0.940160 | 0.757612 | 0.418564 | 0.062* | |
C22 | 0.9424 (10) | 0.6445 (7) | 0.3951 (9) | 0.042 (3) | |
C23 | 0.9456 (10) | 0.5774 (7) | 0.4461 (8) | 0.041 (3) | |
H23 | 0.943115 | 0.533509 | 0.403245 | 0.049* | |
C24 | 0.9527 (10) | 0.5724 (6) | 0.5641 (8) | 0.038 (3) | |
C25 | 0.9568 (10) | 0.4979 (6) | 0.6133 (9) | 0.036 (3) | |
H25 | 0.955114 | 0.457710 | 0.563470 | 0.043* | |
C26 | 0.9674 (12) | 0.3996 (6) | 0.7432 (10) | 0.047 (3) | |
H26A | 0.941201 | 0.372000 | 0.667030 | 0.057* | |
H26B | 0.906448 | 0.387662 | 0.775484 | 0.057* | |
C27 | 1.1019 (12) | 0.3743 (6) | 0.8341 (11) | 0.057 (3) | |
H27A | 1.099336 | 0.320973 | 0.850905 | 0.068* | |
H27B | 1.127029 | 0.401447 | 0.910528 | 0.068* | |
C28 | 0.9865 (12) | 0.4679 (6) | 1.0383 (10) | 0.039 (3) | |
C29 | 0.9315 (12) | 0.4238 (6) | 1.1010 (9) | 0.050 (3) | |
H29 | 0.849861 | 0.402480 | 1.056680 | 0.060* | |
C30 | 0.9965 (15) | 0.4120 (6) | 1.2256 (11) | 0.056 (4) | |
H30 | 0.958376 | 0.383101 | 1.264395 | 0.067* | |
C31 | 1.1165 (14) | 0.4423 (6) | 1.2924 (10) | 0.049 (3) | |
C32 | 1.1763 (12) | 0.4823 (6) | 1.2377 (10) | 0.049 (3) | |
H32 | 1.260004 | 0.500364 | 1.283822 | 0.059* | |
C33 | 1.1110 (12) | 0.4965 (6) | 1.1100 (9) | 0.039 (3) | |
C34 | 1.1809 (11) | 0.5396 (6) | 1.0563 (10) | 0.040 (3) | |
H34 | 1.267389 | 0.550643 | 1.107427 | 0.048* | |
C35 | 1.2272 (10) | 0.6034 (6) | 0.9148 (9) | 0.043 (3) | |
H35A | 1.304458 | 0.614881 | 0.989742 | 0.051* | |
H35B | 1.188873 | 0.650857 | 0.875868 | 0.051* | |
C36 | 1.2666 (11) | 0.5590 (7) | 0.8294 (10) | 0.054 (3) | |
H36A | 1.326841 | 0.589102 | 0.812178 | 0.065* | |
H36B | 1.190367 | 0.550140 | 0.752367 | 0.065* | |
C41 | 0.303 (2) | 0.7791 (13) | 0.798 (2) | 0.238 (18) | |
H41A | 0.213588 | 0.770237 | 0.742278 | 0.356* | |
H41B | 0.309157 | 0.799792 | 0.873079 | 0.356* | |
H41C | 0.349888 | 0.732326 | 0.814585 | 0.356* | |
C42 | 0.4848 (19) | 0.8462 (12) | 0.8032 (18) | 0.142 (9) | |
H42A | 0.506836 | 0.877992 | 0.751540 | 0.214* | |
H42B | 0.533990 | 0.800281 | 0.820119 | 0.214* | |
H42C | 0.504510 | 0.871953 | 0.878817 | 0.214* | |
C43 | 0.284 (4) | 0.857 (3) | 0.637 (6) | 0.33 (4) | |
H43 | 0.321891 | 0.873753 | 0.588075 | 0.400* |
U11 | U22 | U33 | U12 | U13 | U23 | |
BR1 | 0.0733 (11) | 0.0729 (9) | 0.0560 (8) | 0.0139 (8) | 0.0026 (8) | 0.0018 (8) |
BR2 | 0.1197 (15) | 0.1217 (13) | 0.0522 (8) | 0.0358 (12) | 0.0545 (9) | 0.0168 (9) |
BR3 | 0.0510 (8) | 0.0923 (10) | 0.0329 (6) | 0.0013 (8) | 0.0199 (6) | 0.0129 (7) |
BR4 | 0.1218 (15) | 0.0692 (9) | 0.0374 (7) | 0.0211 (9) | 0.0323 (8) | 0.0133 (7) |
CO1 | 0.0418 (10) | 0.0362 (8) | 0.0277 (7) | −0.0014 (8) | 0.0165 (7) | 0.0009 (7) |
CO2 | 0.0442 (10) | 0.0364 (8) | 0.0394 (8) | −0.0026 (8) | 0.0224 (8) | −0.0026 (7) |
S1 | 0.0432 (19) | 0.0482 (18) | 0.0303 (14) | 0.0017 (15) | 0.0158 (14) | 0.0006 (14) |
S2 | 0.0497 (19) | 0.0478 (17) | 0.0300 (13) | −0.0016 (16) | 0.0181 (14) | −0.0026 (14) |
S3 | 0.074 (3) | 0.061 (2) | 0.073 (2) | 0.019 (2) | 0.037 (2) | 0.0007 (19) |
S4 | 0.050 (3) | 0.077 (3) | 0.081 (2) | 0.012 (2) | 0.021 (2) | 0.009 (2) |
O1 | 0.044 (5) | 0.046 (5) | 0.065 (5) | −0.010 (4) | 0.029 (5) | 0.001 (4) |
O2 | 0.067 (6) | 0.036 (4) | 0.060 (5) | −0.002 (4) | 0.042 (5) | −0.005 (4) |
O3 | 0.056 (5) | 0.035 (4) | 0.026 (4) | −0.008 (4) | 0.019 (4) | −0.010 (3) |
O4 | 0.059 (6) | 0.048 (5) | 0.032 (4) | −0.007 (4) | 0.020 (4) | −0.003 (4) |
O5 | 0.53 (5) | 0.108 (13) | 0.23 (2) | 0.05 (2) | 0.24 (3) | 0.052 (13) |
N1 | 0.040 (6) | 0.042 (5) | 0.039 (5) | −0.011 (5) | 0.018 (5) | −0.007 (5) |
N2 | 0.041 (6) | 0.038 (5) | 0.036 (5) | −0.001 (4) | 0.020 (5) | −0.002 (4) |
N3 | 0.042 (6) | 0.035 (5) | 0.031 (5) | 0.000 (4) | 0.018 (5) | 0.004 (4) |
N4 | 0.037 (6) | 0.035 (5) | 0.031 (5) | −0.013 (5) | 0.014 (4) | −0.007 (4) |
N5 | 0.105 (19) | 0.162 (17) | 0.121 (15) | 0.064 (15) | 0.015 (14) | 0.032 (13) |
C1 | 0.037 (8) | 0.034 (7) | 0.066 (8) | 0.002 (6) | 0.028 (7) | 0.001 (6) |
C2 | 0.036 (8) | 0.050 (8) | 0.086 (10) | −0.005 (7) | 0.021 (8) | 0.000 (8) |
C3 | 0.038 (8) | 0.067 (10) | 0.069 (10) | 0.000 (8) | 0.004 (8) | −0.015 (8) |
C4 | 0.052 (10) | 0.039 (7) | 0.067 (9) | 0.006 (7) | 0.015 (8) | −0.011 (7) |
C5 | 0.051 (9) | 0.039 (7) | 0.047 (7) | 0.006 (7) | 0.010 (7) | 0.001 (6) |
C6 | 0.042 (8) | 0.031 (6) | 0.049 (7) | −0.006 (6) | 0.017 (7) | −0.005 (6) |
C7 | 0.050 (8) | 0.041 (7) | 0.041 (7) | −0.017 (6) | 0.017 (7) | 0.003 (6) |
C8 | 0.069 (10) | 0.037 (7) | 0.048 (7) | −0.016 (7) | 0.021 (7) | −0.001 (6) |
C9 | 0.057 (9) | 0.043 (7) | 0.050 (7) | −0.003 (6) | 0.023 (7) | −0.012 (6) |
C10 | 0.035 (7) | 0.043 (7) | 0.035 (6) | −0.003 (5) | 0.016 (5) | −0.008 (6) |
C11 | 0.044 (9) | 0.056 (8) | 0.054 (8) | −0.006 (7) | 0.017 (7) | −0.019 (7) |
C12 | 0.063 (11) | 0.090 (12) | 0.042 (8) | 0.006 (8) | 0.032 (8) | −0.017 (7) |
C13 | 0.058 (10) | 0.064 (9) | 0.038 (7) | 0.005 (7) | 0.021 (7) | −0.003 (7) |
C14 | 0.045 (8) | 0.062 (8) | 0.045 (7) | 0.005 (7) | 0.022 (6) | 0.004 (7) |
C15 | 0.037 (7) | 0.037 (7) | 0.022 (5) | −0.009 (5) | 0.012 (5) | −0.009 (5) |
C16 | 0.033 (7) | 0.049 (7) | 0.043 (7) | 0.002 (6) | 0.015 (6) | 0.007 (6) |
C17 | 0.079 (11) | 0.050 (8) | 0.068 (8) | −0.013 (7) | 0.050 (8) | −0.019 (7) |
C18 | 0.047 (8) | 0.050 (7) | 0.048 (7) | −0.015 (6) | 0.018 (7) | −0.018 (6) |
C19 | 0.043 (7) | 0.028 (6) | 0.033 (6) | −0.004 (6) | 0.018 (5) | −0.002 (6) |
C20 | 0.072 (10) | 0.037 (7) | 0.038 (7) | −0.014 (6) | 0.016 (7) | −0.014 (6) |
C21 | 0.064 (10) | 0.038 (7) | 0.040 (7) | −0.006 (7) | 0.013 (7) | 0.021 (6) |
C22 | 0.034 (7) | 0.057 (8) | 0.032 (6) | 0.003 (6) | 0.013 (5) | 0.007 (7) |
C23 | 0.050 (8) | 0.045 (7) | 0.027 (6) | 0.001 (6) | 0.018 (6) | −0.002 (6) |
C24 | 0.039 (7) | 0.044 (7) | 0.034 (6) | 0.005 (6) | 0.019 (6) | 0.004 (6) |
C25 | 0.036 (7) | 0.040 (7) | 0.037 (7) | 0.009 (6) | 0.021 (6) | 0.005 (5) |
C26 | 0.060 (10) | 0.040 (7) | 0.043 (7) | −0.009 (6) | 0.023 (7) | −0.004 (6) |
C27 | 0.065 (10) | 0.037 (7) | 0.061 (8) | −0.003 (7) | 0.022 (8) | 0.007 (6) |
C28 | 0.047 (9) | 0.032 (6) | 0.039 (7) | −0.001 (6) | 0.021 (7) | 0.000 (6) |
C29 | 0.062 (9) | 0.046 (7) | 0.040 (7) | 0.000 (7) | 0.021 (7) | 0.009 (6) |
C30 | 0.096 (12) | 0.040 (8) | 0.048 (8) | −0.004 (8) | 0.045 (9) | 0.011 (6) |
C31 | 0.082 (11) | 0.032 (7) | 0.036 (7) | 0.024 (7) | 0.029 (8) | 0.005 (6) |
C32 | 0.061 (9) | 0.047 (7) | 0.041 (7) | 0.019 (7) | 0.024 (7) | 0.007 (6) |
C33 | 0.052 (9) | 0.032 (6) | 0.037 (7) | 0.010 (6) | 0.023 (7) | 0.003 (5) |
C34 | 0.036 (7) | 0.043 (7) | 0.038 (7) | 0.000 (6) | 0.013 (6) | −0.005 (6) |
C35 | 0.031 (7) | 0.045 (7) | 0.048 (7) | −0.004 (6) | 0.013 (6) | 0.002 (6) |
C36 | 0.049 (8) | 0.062 (8) | 0.058 (7) | −0.006 (7) | 0.029 (7) | 0.006 (7) |
C41 | 0.14 (2) | 0.21 (3) | 0.29 (3) | −0.01 (2) | 0.03 (2) | 0.20 (3) |
C42 | 0.072 (16) | 0.21 (2) | 0.118 (16) | 0.041 (15) | 0.014 (13) | −0.031 (15) |
C43 | 0.14 (4) | 0.40 (7) | 0.50 (9) | 0.02 (4) | 0.18 (5) | −0.02 (6) |
BR1—C4 | 1.889 (13) | C10—C11 | 1.411 (14) |
BR2—C13 | 1.880 (12) | C11—C12 | 1.391 (15) |
BR3—C22 | 1.911 (9) | C11—H11 | 0.9300 |
BR4—C31 | 1.904 (10) | C12—C13 | 1.358 (16) |
CO1—O3 | 1.883 (6) | C12—H12 | 0.9300 |
CO1—O4 | 1.898 (7) | C13—C14 | 1.355 (15) |
CO1—N3 | 1.955 (8) | C14—C15 | 1.403 (13) |
CO1—N4 | 2.003 (9) | C14—H14 | 0.9300 |
CO1—S1 | 2.258 (3) | C15—C16 | 1.425 (13) |
CO1—S2 | 2.289 (3) | C16—H16 | 0.9300 |
CO2—N2 | 1.905 (8) | C17—C18 | 1.497 (14) |
CO2—N1 | 1.913 (9) | C17—H17A | 0.9700 |
CO2—O2 | 1.920 (7) | C17—H17B | 0.9700 |
CO2—O1 | 1.922 (8) | C18—H18A | 0.9700 |
CO2—S1 | 2.207 (3) | C18—H18B | 0.9700 |
CO2—S2 | 2.253 (3) | C19—C20 | 1.392 (14) |
S1—C18 | 1.790 (11) | C19—C24 | 1.399 (14) |
S2—C9 | 1.805 (11) | C20—C21 | 1.396 (14) |
S3—C27 | 1.807 (13) | C20—H20 | 0.9300 |
S3—S4 | 2.016 (5) | C21—C22 | 1.385 (15) |
S4—C36 | 1.803 (12) | C21—H21 | 0.9300 |
O1—C1 | 1.302 (12) | C22—C23 | 1.335 (14) |
O2—C10 | 1.306 (11) | C23—C24 | 1.406 (12) |
O3—C19 | 1.299 (10) | C23—H23 | 0.9300 |
O4—C28 | 1.311 (12) | C24—C25 | 1.442 (14) |
O5—C43 | 1.11 (5) | C25—H25 | 0.9300 |
N1—C7 | 1.279 (12) | C26—C27 | 1.515 (15) |
N1—C8 | 1.484 (13) | C26—H26A | 0.9700 |
N2—C16 | 1.283 (12) | C26—H26B | 0.9700 |
N2—C17 | 1.475 (12) | C27—H27A | 0.9700 |
N3—C25 | 1.292 (12) | C27—H27B | 0.9700 |
N3—C26 | 1.459 (12) | C28—C33 | 1.399 (15) |
N4—C34 | 1.271 (11) | C28—C29 | 1.426 (14) |
N4—C35 | 1.465 (12) | C29—C30 | 1.376 (15) |
N5—C43 | 1.30 (6) | C29—H29 | 0.9300 |
N5—C42 | 1.36 (3) | C30—C31 | 1.363 (17) |
N5—C41 | 1.39 (3) | C30—H30 | 0.9300 |
C1—C6 | 1.418 (14) | C31—C32 | 1.355 (16) |
C1—C2 | 1.440 (16) | C32—C33 | 1.415 (14) |
C2—C3 | 1.361 (16) | C32—H32 | 0.9300 |
C2—H2 | 0.9300 | C33—C34 | 1.461 (14) |
C3—C4 | 1.391 (17) | C34—H34 | 0.9300 |
C3—H3 | 0.9300 | C35—C36 | 1.527 (14) |
C4—C5 | 1.344 (16) | C35—H35A | 0.9700 |
C5—C6 | 1.422 (14) | C35—H35B | 0.9700 |
C5—H5 | 0.9300 | C36—H36A | 0.9700 |
C6—C7 | 1.415 (15) | C36—H36B | 0.9700 |
C7—H7 | 0.9300 | C41—H41A | 0.9600 |
C8—C9 | 1.496 (15) | C41—H41B | 0.9600 |
C8—H8A | 0.9700 | C41—H41C | 0.9600 |
C8—H8B | 0.9700 | C42—H42A | 0.9600 |
C9—H9A | 0.9700 | C42—H42B | 0.9600 |
C9—H9B | 0.9700 | C42—H42C | 0.9600 |
C10—C15 | 1.403 (15) | C43—H43 | 0.9300 |
O3—CO1—O4 | 176.0 (3) | C13—C14—C15 | 121.4 (12) |
O3—CO1—N3 | 94.4 (3) | C13—C14—H14 | 119.3 |
O4—CO1—N3 | 89.4 (3) | C15—C14—H14 | 119.3 |
O3—CO1—N4 | 89.0 (3) | C14—C15—C10 | 119.9 (10) |
O4—CO1—N4 | 91.6 (3) | C14—C15—C16 | 117.8 (10) |
N3—CO1—N4 | 97.8 (4) | C10—C15—C16 | 122.0 (9) |
O3—CO1—S1 | 82.9 (2) | N2—C16—C15 | 127.0 (10) |
O4—CO1—S1 | 95.9 (3) | N2—C16—H16 | 116.5 |
N3—CO1—S1 | 89.1 (3) | C15—C16—H16 | 116.5 |
N4—CO1—S1 | 169.8 (3) | N2—C17—C18 | 111.7 (9) |
O3—CO1—S2 | 91.7 (2) | N2—C17—H17A | 109.3 |
O4—CO1—S2 | 84.3 (2) | C18—C17—H17A | 109.3 |
N3—CO1—S2 | 168.1 (3) | N2—C17—H17B | 109.3 |
N4—CO1—S2 | 92.4 (2) | C18—C17—H17B | 109.3 |
S1—CO1—S2 | 81.64 (11) | H17A—C17—H17B | 107.9 |
N2—CO2—N1 | 179.1 (4) | C17—C18—S1 | 113.5 (8) |
N2—CO2—O2 | 93.6 (3) | C17—C18—H18A | 108.9 |
N1—CO2—O2 | 86.2 (3) | S1—C18—H18A | 108.9 |
N2—CO2—O1 | 86.5 (4) | C17—C18—H18B | 108.9 |
N1—CO2—O1 | 92.6 (4) | S1—C18—H18B | 108.9 |
O2—CO2—O1 | 90.8 (3) | H18A—C18—H18B | 107.7 |
N2—CO2—S1 | 86.7 (3) | O3—C19—C20 | 118.1 (9) |
N1—CO2—S1 | 93.6 (3) | O3—C19—C24 | 124.8 (9) |
O2—CO2—S1 | 176.9 (3) | C20—C19—C24 | 117.1 (8) |
O1—CO2—S1 | 92.3 (2) | C19—C20—C21 | 122.1 (10) |
N2—CO2—S2 | 94.4 (3) | C19—C20—H20 | 118.9 |
N1—CO2—S2 | 86.5 (3) | C21—C20—H20 | 118.9 |
O2—CO2—S2 | 93.3 (3) | C22—C21—C20 | 118.4 (9) |
O1—CO2—S2 | 175.7 (2) | C22—C21—H21 | 120.8 |
S1—CO2—S2 | 83.57 (11) | C20—C21—H21 | 120.8 |
C18—S1—CO2 | 96.9 (4) | C23—C22—C21 | 121.3 (9) |
C18—S1—CO1 | 112.2 (4) | C23—C22—BR3 | 119.8 (8) |
CO2—S1—CO1 | 98.07 (11) | C21—C22—BR3 | 118.8 (8) |
C9—S2—CO2 | 99.3 (4) | C22—C23—C24 | 120.6 (10) |
C9—S2—CO1 | 107.4 (4) | C22—C23—H23 | 119.7 |
CO2—S2—CO1 | 95.88 (11) | C24—C23—H23 | 119.7 |
C27—S3—S4 | 105.0 (4) | C19—C24—C23 | 120.4 (10) |
C36—S4—S3 | 106.2 (4) | C19—C24—C25 | 122.2 (8) |
C1—O1—CO2 | 121.8 (7) | C23—C24—C25 | 117.4 (10) |
C10—O2—CO2 | 125.9 (7) | N3—C25—C24 | 127.6 (10) |
C19—O3—CO1 | 126.4 (6) | N3—C25—H25 | 116.2 |
C28—O4—CO1 | 125.7 (7) | C24—C25—H25 | 116.2 |
C7—N1—C8 | 121.4 (9) | N3—C26—C27 | 111.9 (9) |
C7—N1—CO2 | 124.0 (8) | N3—C26—H26A | 109.2 |
C8—N1—CO2 | 114.5 (7) | C27—C26—H26A | 109.2 |
C16—N2—C17 | 114.7 (9) | N3—C26—H26B | 109.2 |
C16—N2—CO2 | 124.8 (8) | C27—C26—H26B | 109.2 |
C17—N2—CO2 | 120.4 (6) | H26A—C26—H26B | 107.9 |
C25—N3—C26 | 114.9 (9) | C26—C27—S3 | 113.4 (8) |
C25—N3—CO1 | 122.0 (7) | C26—C27—H27A | 108.9 |
C26—N3—CO1 | 122.8 (7) | S3—C27—H27A | 108.9 |
C34—N4—C35 | 115.4 (9) | C26—C27—H27B | 108.9 |
C34—N4—CO1 | 123.2 (8) | S3—C27—H27B | 108.9 |
C35—N4—CO1 | 121.2 (6) | H27A—C27—H27B | 107.7 |
C43—N5—C42 | 120 (4) | O4—C28—C33 | 124.8 (10) |
C43—N5—C41 | 120 (4) | O4—C28—C29 | 119.0 (11) |
C42—N5—C41 | 120.0 (19) | C33—C28—C29 | 116.2 (10) |
O1—C1—C6 | 125.1 (11) | C30—C29—C28 | 121.5 (12) |
O1—C1—C2 | 117.9 (10) | C30—C29—H29 | 119.3 |
C6—C1—C2 | 116.9 (11) | C28—C29—H29 | 119.3 |
C3—C2—C1 | 120.9 (12) | C31—C30—C29 | 120.4 (11) |
C3—C2—H2 | 119.6 | C31—C30—H30 | 119.8 |
C1—C2—H2 | 119.6 | C29—C30—H30 | 119.8 |
C2—C3—C4 | 121.3 (12) | C32—C31—C30 | 121.0 (11) |
C2—C3—H3 | 119.4 | C32—C31—BR4 | 119.7 (11) |
C4—C3—H3 | 119.4 | C30—C31—BR4 | 119.2 (10) |
C5—C4—C3 | 119.9 (12) | C31—C32—C33 | 119.8 (12) |
C5—C4—BR1 | 121.9 (10) | C31—C32—H32 | 120.1 |
C3—C4—BR1 | 118.2 (10) | C33—C32—H32 | 120.1 |
C4—C5—C6 | 121.6 (12) | C28—C33—C32 | 121.0 (11) |
C4—C5—H5 | 119.2 | C28—C33—C34 | 121.8 (9) |
C6—C5—H5 | 119.2 | C32—C33—C34 | 117.2 (11) |
C7—C6—C1 | 121.5 (10) | N4—C34—C33 | 126.4 (11) |
C7—C6—C5 | 119.0 (10) | N4—C34—H34 | 116.8 |
C1—C6—C5 | 119.4 (11) | C33—C34—H34 | 116.8 |
N1—C7—C6 | 126.1 (11) | N4—C35—C36 | 113.9 (8) |
N1—C7—H7 | 117.0 | N4—C35—H35A | 108.8 |
C6—C7—H7 | 117.0 | C36—C35—H35A | 108.8 |
N1—C8—C9 | 110.1 (9) | N4—C35—H35B | 108.8 |
N1—C8—H8A | 109.6 | C36—C35—H35B | 108.8 |
C9—C8—H8A | 109.6 | H35A—C35—H35B | 107.7 |
N1—C8—H8B | 109.6 | C35—C36—S4 | 112.8 (7) |
C9—C8—H8B | 109.6 | C35—C36—H36A | 109.0 |
H8A—C8—H8B | 108.1 | S4—C36—H36A | 109.0 |
C8—C9—S2 | 111.0 (8) | C35—C36—H36B | 109.0 |
C8—C9—H9A | 109.4 | S4—C36—H36B | 109.0 |
S2—C9—H9A | 109.4 | H36A—C36—H36B | 107.8 |
C8—C9—H9B | 109.4 | N5—C41—H41A | 109.5 |
S2—C9—H9B | 109.4 | N5—C41—H41B | 109.5 |
H9A—C9—H9B | 108.0 | H41A—C41—H41B | 109.5 |
O2—C10—C15 | 124.6 (9) | N5—C41—H41C | 109.5 |
O2—C10—C11 | 118.1 (10) | H41A—C41—H41C | 109.5 |
C15—C10—C11 | 117.3 (10) | H41B—C41—H41C | 109.5 |
C12—C11—C10 | 120.4 (12) | N5—C42—H42A | 109.5 |
C12—C11—H11 | 119.8 | N5—C42—H42B | 109.5 |
C10—C11—H11 | 119.8 | H42A—C42—H42B | 109.5 |
C13—C12—C11 | 121.3 (11) | N5—C42—H42C | 109.5 |
C13—C12—H12 | 119.4 | H42A—C42—H42C | 109.5 |
C11—C12—H12 | 119.4 | H42B—C42—H42C | 109.5 |
C14—C13—C12 | 119.7 (11) | O5—C43—N5 | 121 (6) |
C14—C13—BR2 | 120.9 (10) | O5—C43—H43 | 119.7 |
C12—C13—BR2 | 119.4 (9) | N5—C43—H43 | 119.7 |
D—H···A | D—H | H···A | D···A | D—H···A |
C42—H42B···O2 | 0.96 | 2.35 | 3.25 (2) | 157 |
C25—H25···O5i | 0.93 | 2.56 | 3.39 (2) | 149 |
C3—H3···Br3ii | 0.93 | 2.85 | 3.633 (13) | 142 |
C17—H17B···Br1i | 0.97 | 3.00 | 3.743 (11) | 134 |
Symmetry codes: (i) −x+1, y−1/2, −z+1; (ii) x−1, y, z. |
Funding information
This work was supported by the Ministry of Education and Science of Ukraine (project No. 19BF037–05).
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