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Solvent influence on the crystal structures of new cadmium tri-tert-butoxysilanethiolate complexes with 1,4-bis(3-aminopropyl)piperazine: luminescence and antifungal activity
aDepartment of Inorganic Chemistry, Gdańsk University of Technology, Narutowicza 11/12, Gdańsk 80-233, Poland, bDepartment of Physical Chemistry, Gdańsk University of Technology, Narutowicza 11/12, Gdańsk 80-233, Poland, cDepartment of Rare Earths, Adam Mickiewicz University in Poznań, Uniwersytetu Poznańskiego 8, Poznań 61-614, Poland, dDepartment of General and Coordination Chemistry, Maria Curie-Skłodowska University, PL. M.C. Skłodowska-Curie 2, Lublin 20-031, Poland, and eDepartment of Molecular Biotechnology and Microbiology, Gdańsk University of Technology, Narutowicza 11/12, Gdańsk 80-233, Poland
*Correspondence e-mail: agnieszka.pladzyk@pg.edu.pl
Monocrystals of dinuclear μ-1,4-bis(3-aminopropyl)piperazine-κ4N1,N1′:N4,N4′-bis[bis(tri-tert-butoxysilanethiolato-κS)cadmium(II)], [Cd2(C12H27O3SSi)4(C10H24N4)] or [Cd2{SSi(OtBu)3}4(μ-BAPP)], 1, and polynuclear catena-poly[[bis(tri-tert-butoxysilanethiolato-κS)cadmium(II)]-μ-1,4-bis(3-aminopropyl)piperazine-κ2N1′:N4′], [Cd(C12H27O3SSi)2(C10H24N4)]n or [Cd{SSi(OtBu)3}2(μ-BAPP)]n, 2, with 1,4-bis(3-aminopropyl)piperazine (BAPP) and tri-tert-butoxysilanethiolate ligands, were obtained from the same ratio of reactants, but with different solvents used for the crystallization processes. The structures and properties of both complexes were characterized using elemental analysis, X-ray diffraction and FT–IR, 1H NMR and luminescence spectroscopy. Applied density functional theory (DFT) computational methods and noncovalent interaction (NCI) analysis were used for geometry optimization and visualization of the interactions between the metallic centres and their surroundings. The X-ray analysis revealed four-coordinate CdII centres bound to two S atoms of the silanethiolate groups and two N atoms of the BAPP ligand; however, it chelates to tertiary and primary N atoms in 1, whilst in 2 it does not chelate and bonds only to RNH2. The properties of complexes 1 and 2 result from free-ligand emission and differ significantly from each other with respect to emission intensity. Additionally, antifungal activity was investigated against 18 isolates of fungi. Compound 1 strongly inhibited the growth of three dermatophytes: Epidermophyton floccosum, Microsporum canis and Trichophyton rubrum.
1. Introduction
Piperazine is found to be a structural component of compounds that exhibit interesting properties. Due to its structural similarity to glucose and cyclodextrins, as well as the ability of piperazine N atoms to bind with DNA, this molecule and its derivatives have attracted remarkable interest as ligands in the synthesis of compounds that exhibit anticancer (Nemati et al., 2021; Ragab et al., 2022
), antimicrobial (Niemeyer et al., 1979
; Keypour et al., 2008
) and antimalarial activity (Ryckebusch et al., 2003
; Guillon et al., 2017
). Piperazine derivatives are also used in the synthesis of metal coordination compounds. One of the promising groups of such complexes are based on cadmium. Despite the toxic properties of the metal itself, the compounds are still studied for the purpose of assessing their biological activity. However, this is not the only area in which the applicability of cadmium compounds is under investigation, they have also been assessed for their structural, photochemical and catalytic suitability (Wing-Wah Yam et al., 1999
; Singh et al., 2015
; Keypour et al., 2009
; Półrolniczak et al., 2018
; Buta et al., 2021
).
A detailed analysis of the literature has shown that there are no Cd complexes that contain piperazine derivatives and thiolate residues. This fact is somewhat surprising, as numerous examples show that the presence of thiolate residues in heteroleptic complexes often confers additional physicochemical properties (Henkel et al., 2004; Resta et al., 2010
; Gennari et al., 2020
; Korkola et al., 2023
). Therefore, we have made attempts to synthesize cadmium compounds containing both thiolate and piperazine derivatives as ligands.
Our scientific group is investigating alkoxy- and aryloxysilanethiols, (RO)3SiSH, which are analogues of organic RSH. They contain a C—O—Si—S—H moiety instead of a C—S bond and act as both S-terminal and O,S-chelating ligands in the synthesis of coordination compounds (Pladzyk et al., 2021). The compound commonly used by us in the syntheses of silanethiolates is tri-tert-butoxysilanethiol, (tBuO)3SiSH (TBST). Due to its spatial structure, it shows remarkable resistance towards hydrolysis of the Si—S bonds, allowing for synthesis under atmospheric conditions, giving mono-, di- or polymeric complexes of various metals. Our research focuses on the design and preparation of heteroleptic metal silanethiolates that exhibit luminescence, magnetic and/or catalytic features (Pladzyk et al., 2021
). One group of such derivatives is cadmium silanethiolates and our current research is directed towards recognizing the role of 1,4-bis(3-aminopropyl)piperazine (BAPP) in the structural, spectral and cytotoxic properties of cadmium tri-tert-butoxysilanethiolates containing this ligand. For this purpose, we conducted reactions using the same molar ratios of cadmium silanethiolate, [Cd{SSi(OtBu)3}2]2 (Wojnowski et al., 1992
), and BAPP in two different solvent systems. As a result, two new cadmium(II) complexes were obtained, namely, [Cd2{SSi(OtBu)3}4(μ-BAPP)], 1, and [Cd{SSi(OtBu)3}2(μ-BAPP)]n, 2, and their crystal structures, combined with their theoretical studies, spectral characterization and cytotoxic characteristics, are presented below.
2. Experimental
2.1. General procedures
The elemental analyses (C, H, S and N contents) were performed with a Vario EL Cube CHNS apparatus. The FT–IR spectra were measured for crystalline compounds 1 and 2 in the range 4000–400 cm−1 with a Nicolet iS50 FT–IR spectrometer equipped with a Specac Quest single-reflection diamond attenuated total reflectance (ATR) accessory. 1H NMR spectra were recorded in solution on a Bruker AV400 MHz spectrometer [external standard: tetramethylsilane (TMS)]. Luminescence spectra in the UV–Vis range were recorded at room temperature on a Hitachi F7000 spectrophotometer equipped with a 150 W xenon lamp as the light source. of both cadmium complexes in air was performed by thermogravimetric (TG) and (DSC) methods using a Setsys 16/18 Setaram analyzer. The samples (about 8 mg) were heated in aluminium crucibles in the temperature range 30–1000 °C in flowing air with a heating rate of 10 °C min−1. under a nitrogen atmosphere was performed using a Q5000 TA apparatus. Samples of about 20 mg were heated to 700 °C at a rate of 20 °C min−1 in flowing nitrogen.
2.2. Syntheses
[Cd{SSi(OtBu)3}2]2 was obtained according to procedures described previously (Wojnowski et al., 1992). All other reagents were obtained commercially and were used with no further purification.
2.2.1. [Cd2{SSi(OtBu)3}4(μ-BAPP)], 1
A portion of BAPP (0.082 ml, 0.4 mmol) was added to the solution of [Cd{SSi(OtBu)3}2]2 (0.1 mmol, 0.13 g) in methanol (25 ml). The mixture was left at 4 °C for crystallization and after one week colourless crystals of 1 were obtained (yield 60%; m.p. 163.5–164.9 °C). Analysis calculated (%) for C58H132Cd2N4O12S4Si4: C 45.14, H 8.62, N 3.63, S 8.31; found: C 45.14, H 8.57, N 3.65, S 8.35. IR (solid state): ν 3331 (w), 3246 (w), 3161 (vw), 2971 (vs), 2930 (m), 2903 (m), 2858 (w), 1584 (w), 1471 (w), 1418 (vw), 1386 (m), 1361 (s), 1339 (vw), 1311 (vw), 1285 (vw), 1266 (vw), 1231 (m), 1210 (m), 1175 (s), 1137 (w), 1120 (w), 1091 (vw), 1083 (vw), 1036 (vs), 1012 (s), 1006 (vs), 998 (vs), 993 (vs), 974 (m), 952 (m), 912 (w), 882 (vw), 858 (vw), 813 (m), 793 (w), 734 (vw), 723 (vw), 688 (m), 677 (m), 657 (m), 607 (vw), 535 (m), 502 (w), 479 (w), 470 (w), 422 (w). 1H NMR (CH3OH-d4): δ 4.88 and 3.33 (methanol protons), 2.77 (t, 2H, JHH = 6.9 Hz), 2.49 (t, 2H, JHH = 7.2 Hz) and 1.73 (q, 2H, JHH = 6.8 and 7.1 Hz) – methylene protons of BAPP; 2.62 (br m, NH2 protons of BAPP); 1.42 (s, 54H, tBu protons).
2.2.2. [Cd{SSi(OtBu)3}2(μ-BAPP)]n, 2
[Cd{SSi(OtBu)3}2]2 (0.1 mmol, 0.13 g) in toluene (8 ml) was mixed with BAPP (0.082 ml, 0.4 mmol) dissolved in methanol (2 ml). After gentle stirring, the mixture was allowed to stand for a few days at −20 °C. The obtained white precipitate was filtered off and recrystallized from toluene. Colourless crystals of 2 were obtained after two weeks of crystallization (yield 54%; m.p. 118.4–119.7 °C). Analysis calculated (%) for C34H78CdN4O6S2Si2: C 46.85, H 9.02, N 6.43, S 7.36; found: C 46.71, H 9.14, N 6.44, S 7.12. IR (solid state): ν 3293 (m), 3227 (w), 3152 (w), 2968 (vs), 2944 (m), 2934 (m), 2925 (m), 2872 (w), 2820 (m), 2778 (w), 2743 (vw), 2723 (vw), 2706 (vw), 2673 (vw), 1590 (w), 1492 (vw), 1458 (w), 1449 (w), 1383 (m), 1361 (s), 1347 (w), 1310 (vw), 1301 (w), 1263 (w), 1251 (w), 1239 (m), 1204 (m), 1185 (s), 1146 (w), 1128 (w), 1104 (w), 1074 (w), 1069 (w), 1040 (vs), 1004 (vs), 987 (vs), 961 (m), 940 (w), 910 (w), 882 (vw), 842 (vw), 820 (m), 802 (m), 770 (w), 728 (vw), 683 (m), 650 (s), 544 (m), 500 (w), 485 (w), 477 (w), 461 (w), 427 (vw), 422 (w). 1H NMR (toluene-d6): δ 2.54 (br t, 4H, methylene protons of BAPP), 2.45 (br m, 4H, NH2 protons of BAPP), 2.17 (t, JHH = 6.4 Hz, 4H, methylene protons of BAPP), 1.38 (s, 54H, tBu protons), 1.26 (br m, 4H, methylene protons of BAPP); about 0.9 (very br m, 4H of methylene protons of BAPP).
2.3. X-ray crystallography
Crystal data, data collection and structure . H atoms bonded to C atoms were refined using a riding model. The Uiso(H) values of the methyl H atoms were set to 1.5Ueq(C), while the Uiso(H) values of the H atoms bonded to the remaining C atoms were set to 1.2Ueq(C). All H atoms bonded to N atoms were refined freely. The structure of 1 contained a high residual electron-density peak located near atoms S1, S2 and N2. Both S atoms in 1 were refined as positionally disordered over two positions using the PART 1 and PART 2 commands (occupancies 0.79 and 0.21) and the data was calculated with 21.000 and −21.000.
|
2.4. DFT calculations and NCI analysis
All quantum mechanical calculations were performed with the help of the supercomputers of the Centre of Informatics Tricity Academic Supercomputer & Network Academic Computer Center (TASK, Gdańsk, Poland) with GAUSSIAN2016 software (Frisch et al., 2016). The structures of the Cd complexes obtained from the diffraction studies were optimized at the M-11L/def2SV(P) level of theory (Peverati et al., 2012
; Weigend et al., 2005
) with an ultrafine grid and tight convergence criteria. IR frequencies were calculated with the same level of theory and none of these optimized structures exhibited negative frequencies. The selected M-11L functional is optimal for transition metals, organometallic compounds and the determination of noncovalent interactions (NCIs), while the selected basis set provides qualitatively accurate results within a reasonable calculation time. Larger basis sets were tested but turned out to be inefficient for such large molecular complexes (over 200 atoms). Electron densities, a by-product of every density functional theory (DFT) calculation, have been saved to external files and utilized in the next step of the data analysis. The NCI analysis was performed with the Multiwfn software (Version 3.6; Lu et al., 2012
). The analysis was performed for the direct crystallographic structures of the Cd complexes and for their DFT-optimized counterparts. The electron densities of the former were calculated during a Single Point Energy calculation job type [M-11L/def2SV(P), without geometry optimization], while for the latter, they were calculated at the optimization step. Although, in the first case, electron densities were calculated without any optimization step, these results were used to compare how both experimental and DFT-optimized structures differed or not. The number of visualization points was 27 × 106 or higher. Such a large number provided a clear and unscattered weak interaction picture in each case. The VMD molecular visualization program (Version 1.9.2) was used for visualization of the NCI results (Humphrey et al., 1996
). For better clarity, these interactions were excluded from the results, according to the Multiwfn manual, and only Cd–ligand or ligand–ligand interactions were visualized.
2.5. Antimicrobial activity
The preliminary examination of the antifungal activity of compound 1 was performed with the microdilution plate method. RPMI 1640 supplemented with glucose and 3-(N-morpholino)propanesulfonic acid (MOPS) at a final concentration of 0.165 mol l−1 and pH 7.0 was applied as a culture medium. 18 isolates of fungi from the collection of the Department of Molecular Biotechnology and Microbiology were examined, i.e. Alternaria alternata, Aspergillus flavus, A. fumigatus, A. niger, Candida albicans, C. catenulata, C. haemulonii, C. glabrata, C. kefyr, C. krusei, C. parapsilosis, C. tropicalis, C. utilis, Fusarium oxysporum and F. solani, and the three dermatophyte isolates Epidermophyton floccosum, Microsporum canis and Trichophyton rubrum. All of the isolates were identified by conventional and molecular identification prior to deposition in the collection. The inoculum was prepared by suspending one colony from Sabouraud agar in 3 ml of distilled water. The inoculum was ready after the density reached 0.5 according to the McFarland standard, which is equal to 1–5 × 106 CFU ml−1. 100 µl of the suspension was transferred to each well of columns 1–9 of the microdilution plate with 100 µl twofold dilutions of compound 1 (ranging from 4 to 0.016 mg l−1). The wells in column 10 containing methanol were designed to exclude its influence, as 1 was dissolved in methanol. The wells in column 11 containing 100 µl of sterile drug-free medium containing pure inoculum served as the positive and sterility controls, and the wells in column 12 not containing inoculum served as the negative control. The microdilution plates were incubated for 24 h at 37 °C. The results were judged by eye after 24 h. The lowest concentration of 1 giving any inhibition of growth was regarded as the MIC value.
3. Results and discussion
3.1. Synthesis
We have examined the coordination abilities of 1,4-bis(3-aminopropyl)piperazine (BAPP) in reactions with CdII tri-tert-butoxysilanethiolate, [Cd{SSi(OtBu)3}2]2, under atmospheric conditions. At first, we combined [Cd{SSi(OtBu)3}2]2 with BAPP in a molar ratio of 1:4 in methanol. The reaction yielded colourless crystals of dinuclear [Cd2{SSi(OtBu)3}4(μ-BAPP)], 1, isolated after several days of crystallization at 4 °C (Scheme 1). The reaction of [Cd{SSi(OtBu)3}2]2 with BAPP at the same molar ratio but in a toluene–methanol solvent system also yielded a colourless precipitate of the polynuclear compound [Cd{SSi(OtBu)3}2(μ-BAPP)]n, 2, which was further recrystallized from toluene at low temperature (−20 °C). After two weeks, colourless crystals of 2 suitable for X-ray analysis were obtained (Scheme 1
). To check whether the solvent for the recrystallization influences the final structure of the product, we recorded 1H NMR spectra for the precipitate obtained before recrystallization. The results clearly indicate that there are no free ligands in the precipitated product of the reaction before recrystallization (Figs. S1–S4 in the supporting information). Thus, one can assume that the use of toluene is crucial for obtaining polynuclear complex 2. The obtained compounds were synthesized in fairly high yields and were stable under atmospheric conditions, enabling further tests to be carried out to determine their physicochemical properties.
3.2. Crystal structures
X-ray analysis results have shown that complexes 1 and 2 crystallize in the monoclinic P21/n. Complex 1 is dinuclear with metallic centres connected via the molecule of BAPP, which acts as a tetradentate bridging ligand and leads to the formation of a dimeric compound (Fig. 1 and Fig. S5 in supporting information). Each of the CdII atoms in compound 1 is chelated by two N atoms, i.e. one from the BAPP ring and the second from the amine group of the aminopropyl residues. The tetrahedral coordination sphere of each CdII atom is completed by two tri-tert-butoxysilanethiolate residues acting as S-donor terminal ligands.
![]() | Figure 1 A fragment of the crystal structure of 1, showing the environments of the metal centres, the atom-labelling scheme for the and weak hydrogen bonding (as dashed lines). Displacement ellipsoids are drawn at the 50% probability level and the H atoms of the tert-butyl groups and of the BAAP ligand bonded to C atoms have been omitted for clarity. [Symmetry code: (i) −x + 2, −y + 1, −z + 1.] |
The bond angles around the CdII atoms are in the range 88.42 (11)–135.39 (13)° (Table S1), indicating the presence of slight deviations from tetrahedral geometry, which was confirmed by the values of the structural parameters τ4 and τ4′ (0.77 and 0.70, respectively) (Fig. S7) (Yang et al., 2007; Okuniewski et al., 2015
; Rosiak et al., 2018
). However, these deviations do not affect the Cd—S bond lengths, while one of the Cd—N bonds is slightly longer when compared to those observed in other cadmium(II) silanethiolates with a tetrahedral metallic centre (Table S2) (Dołęga et al., 2006
, 2007
; Pladzyk et al., 2013
, 2015
; Kowalkowska et al., 2017
; Maślewski et al., 2017
). The molecule of 1 is centrosymmetric, with the inversion centre located in the middle of the piperazine ring of the BAPP molecule. The duplication of the of complex 1 by this centre generates the second part of the dimer.
BAPP molecules are involved in the formation of hydrogen bonds, i.e. intramolecular N1(BAPP)—H1B⋯O4(TBST) [D⋯A = 3.115 (4)Å] and intermolecular N1(BAPP)—H1A⋯S1(TBST) [D⋯A = 3.519 (5) Å]. The parameters of these interactions are presented in Table S3. The presence of these intermolecular interactions causes the individual molecules of compound 1 to be interconnected and form one-dimensional chain structures through R 22 rings that join neighbouring molecules (Bernstein et al., 1995). The distances between the CdII atoms in the molecule of 1 and the distances to the metallic centres of neighbouring molecules are almost identical at 6.3474 (6) and 6.3324 (6) Å, respectively.
Compound 2 is a polynuclear complex with a polymeric structure (Fig. 2 and S6). As in complex 1, each CdII atom is coordinated by two S atoms from TBST residues and two N atoms from the RNH2 groups of two BAPP bridging ligands that connect adjacent metallic centres.
![]() | Figure 2 A fragment of the crystal structure of 2, showing the environments of the metal centres, the atom-labelling scheme for the and weak hydrogen bonding (as dashed lines). Displacement ellipsoids are drawn at the 50% probability level and the H atoms of the tert-butyl groups and of the BAAP ligand bonded to C atoms have been omitted for clarity. [Symmetry codes: (i) −x + 1, −y, −z + 1; (ii) −x + 1, −y + 1, −z + 1.] |
The Cd—N and Cd—S bond lengths observed in 2 are similar to those found in other heteroleptic cadmium(II) silanethiolates (Table S1) (Dołęga et al., 2006, 2007
; Pladzyk et al., 2013
, 2015
; Kowalkowska et al., 2017
; Maślewski et al., 2017
), whereas the angles at the CdII atoms range from 99.26 (10) to 120.28 (3)°. This indicates the presence of even smaller deviations from ideal tetrahedral geometry compared to complex 1 (τ4 = 0.91 and τ4′ = 0.88) (Fig. S8 and Table S2) (Yang et al., 2007
; Okuniewski et al., 2015
; Rosiak et al., 2018
). Coordination polymer 2 is also centrosymmetric, with an inversion centre located at the middle of the six-membered piperazine ring of BAPP. The distances between the nearest CdII atoms within a single chain are 10.222 (2) and 11.424 (2) Å, while the distances between atoms belonging to neighbouring chains are shorter at 8.949 (2) and 9.677 (3) Å. The spatial arrangement of the polymeric chains of 2 enables the formation of diverse intramolecular interactions. Atoms N1 and N3 of the amino groups of the BAPP molecules are donors of two types of hydrogen-bonding interactions (Fig. 2
). The first type is N(BAPP)—H⋯N(BAPP ring), between the amino group and an N atom belonging to the piperazine ring from the same BAPP ligand, i.e. N1—H1A⋯N2 [D⋯A = 2.977 (4) Å], as well as N3—H3A⋯N4 [D⋯A = 2.996 (4) Å]. The second type is the N(BAPP)—H⋯O(TBST) hydrogen-bonding interaction between the same amino group and the O atom of the silanethiolate residue, i.e. N1—H1B⋯O3 [D⋯A = 3.200 (4) Å] (Table S3). In addition, atom N1 is a donor in the next interaction, N1—H1B⋯O1, with the O atom of the TBST residue as the acceptor, so that the H1B atom is engaged in the formation of a three-centred hydrogen bond. The crystal packing of 2 shows that the polymer chains are arranged parallel to each other with no further significant interactions.
3.3. FT–IR spectroscopy
The FT–IR spectra were recorded for both complexes in the solid state (Fig. S9 in the supporting information). They are consistent with the crystal structures and confirm the presence of the ligands used in the syntheses (Nakamoto, 1997). The spectra of 1 and 2 contain bands of various intensities in the range from 3161 to 2675 cm−1, characteristic for the symmetric and asymmetric vibrations of the C—H bonds of the methylene groups of BAPP, as well as the methyl groups present in the TBST residues. The number of bands occurring in this range for compound 2 is greater than for complex 1. The bands observed in the range 1100–980 cm−1 for both complexes are characteristic for the Si—O—C bonding present in the (tBuO)3SiS− residues, and their patterns are typical for silanethiolate residues coordinating to metallic centres as terminal S-donor residues (Pladzyk et al., 2021
).
The BAPP ligand may be identified by the presence of the N—H symmetric and asymmetric stretching vibrations present at about 3330 cm−1 (3332 and 3257 cm−1 for 1, and 3293 and 3232 cm−1 for 2), the N—H deformation at 1584 and 1590 cm−1 for 1 and 2, respectively, as well as the in-plane and out-of-plane N—H vibrations in the ranges 1480–1440 (1481 cm−1 for 1, and 1492, 1458, and 1449 cm−1 for 2) and 800–780 cm−1, respectively. Other peaks typical for cyclic are present at 1266, 1238 and 1204 cm−1 for 1, and at 1263, 1251 and 1240 cm−1 for 2, and correspond to C—N vibrations (Prabavathi et al., 2015).
The def2sv(p) functional was applied in GAUSSIAN16 (Frisch et al., 2016) for the calculation of the FT–IR spectra of 1 and 2. A comparison of the experimental and calculated spectra was carried out, together with assignments of the important features concluded from calculations (Table S4 and Fig. S10). Both the experimental and theoretical IR spectra are remarkably consistent. Virtually all vibrations in the experimental spectra can be assigned with the help of the calculated spectra, which confirms that the synthesis of both compounds was successful. Although no IR scale factor for the M11-L/def2sv(p) level of theory was found in the literature, it can be estimated as 0.92–0.93 on the basis of the N—H stretching bands, and mainly concerns higher wavenumber bands (about 3000 cm−1).
The main difference between the experimental spectra of 1 and 2 is the additional N—H stretching band in 2. This phenomenon is also reflected in the theoretical spectra. The reason for this is the inequality of various parts of the BAPP molecule in 2 (see Section 3.4). The inequality of the environments of the BAPP end groups in 2 allows for distinguishable differences in the N—H bond energies and vibration frequencies. Meanwhile, in 1, both ends of the molecule interact symmetrically with two cadmium centres, i.e. they are equal or almost similar in energy and frequency.
3.4. NCI analysis of 1 and 2
The optimization step of the DFT calculations slightly altered the geometry of the initial complexes, and the overall structures of the crystallographic and optimized complexes were very similar. NCI interaction sites were initially determined for both the crystallographic and the DFT-optimized structures of complexes 1 and 2 within 1 nm of the Cd atom to verify if the crystallographic structure could be used directly in the qualitative NCI analysis. The optimized structures exhibited virtually all the interaction sites and properties present in the crystallographic structures; thus, the NCI analysis was performed for the real crystallographic structures. The IR spectra were derived from the optimized structures of both complexes.
Usually, NCI analysis gives information on the type and strength of a weak bond. In this group of interactions, hydrogen bonds are considered the strongest visible in the NCI analysis results and are usually depicted as well-defined blue disks, according to the convention of the Multiwfn software and the developers of the method (Lu et al., 2012). The disk shape reveals its directionality and the darker the blue colour, the stronger the bond. It should be noted that most Cd coordination bonds are stronger than an average hydrogen bond and NCI analysis indicates them not as blue disks (as for strong hydrogen bonds), but as blue/red rings. The hollow centre of such visualizations indicates that their classification as generally weak noncovalent interactions is barely justified.
3.4.1. Weak interactions in the vicinity of Cd
The neighbourhoods of the Cd atoms in 1 and 2 are strikingly different (see Fig. 3). These differences may be directly recognizable in these structures, yet NCI results aid in fully understanding them. The four main interaction sites in 2 are highly symmetrical. Both N—Cd sites are strong and energetically very similar, which is reflected in their almost identical shape and colour of the interaction indicator (blue/red ring). The same can be said for the S—Cd interactions. The overall environment of the Cd centre is open and accessible for other possible interactions.
![]() | Figure 3 Weak interactions in the vicinity of the Cd atom as a result of the NCI analysis, with 1 on the left and 2 on the right. Green/olive irregular patches denote weak van der Waals-type interactions, while blue/red disks or rings denote relatively strong direct coordination interactions. |
Meanwhile, the N—Cd or S—Cd interactions in 1 are not equal. In particular, one of the N—Cd interactions turns out to be significantly weaker than the analogous interaction in 2 (full blue/red disk between Cd and N). The symmetry of the interactions is broken in comparison to 2, probably due to the fact that both N—Cd interactions come from a single BAPP molecule, i.e. three molecules contribute to four Cd interactions. In the case of 2, all four Cd coordination interactions are formed by four different molecules, which allows for more freedom in the spatial orientation of the ligand sites and is closer to the tetrahedral coordination of Cd.
The overall contribution of the van der Waals interactions (green/olive patches) in the case of 1 is significantly higher. The Cd atom in this complex is densely covered with other atoms of the structure, leaving no place for other inter- or intramolecular interactions. In particular, the spatial orientation of S—Si—O allows for weak O—Cd interactions in 1 (green patches between Cd and O), which is not possible in 2. Most probably, these interactions are possible due to the inequality of the N—Cd interactions and the greater deviation of the Cd interaction distribution from the optimal tetrahedral orientation.
3.4.2. Weak interactions of 1,4-bis(3-aminopropyl)piperazine (BAPP)
The better packing of 1 is also reflected in the number of interactions with the BAPP ligand. A visual inspection of the NCI results (see Figs. S11–S14 in the supporting information), focused this time on intermolecular interactions of the ligand with the rest of the structures of 1 or 2, gives the impression that tightly organized complex 1 takes advantage of almost all possible intermolecular interactions involving Cd and the BAPP and TBST ligands. Van der Waals interactions are numerous and relatively large in 1, while in 2, a scattered pattern of these weak interactions is revealed (in both possible variants of the ligand). Even though all interactions other than N—Cd are weak, their co-operativity should make the structure of 1 much more stable and stronger than that of 2.
Moreover, weak but well-oriented C—H hydrogen bonds, symbolized by small green disks in the axis of C—H bonds, may play a significant role in the maintenance of the densely packed 1, while only two such directional interactions can be recognized in both variants of the ligand in 2.
Eight such interactions can be spotted in the case of the BAPP fragment inIt can be argued that these kinds of interactions in 1 can be called true hydrogen bonds, yet such a directional and in-axis character, supported by a relatively large number per BAPP molecule, makes them stronger anyway.
3.5. Luminescence
The solid-state luminescence properties of powder samples of 1 and 2, together with the free BAPP ligand and [Cd{SSi(OtBu)3}2]2, were investigated at ambient temperature. The entire spectroscopic study was carried out under identical experimental conditions. The optical absorption spectra of 1 and 2 have been measured by diffuse-reflectance experiments (see Fig. S15). The diffuse-reflectance spectra show two sharp absorption bands in the UV region at 226 and 257 nm for 1, and at 225 and 252 nm for 2, with a weaker signal region at 280–380 nm. The observed bands in this region of the prepared compounds can be assigned to electronic transitions from the ground-state S0 level to the excited-state Sn levels of the BAPP piperazine ligand. The diagram of the energy levels for complexes [pipH]2[Co(NCS)4] and [pipH]2[Ni(NCS)4] (where pip is piperazine) has been proposed by Bie et al. (2005). Emission spectra were then recorded using these specific ultraviolet wavelengths (Fig. S16). In the case of 1, a weak emission was observed, with a maximum located at about 350 nm, whereas in the case of 2, week emissions located at about 350 and 420 nm were observed. This shows that excitation of the systems to the highest excited levels results in low emission intensities caused by large energy losses due to efficient non-radiative transitions to lower excited levels, from where emission takes place (Bie et al., 2005
).
Irradiation of all the systems with ultraviolet light in the solid state, monitoring the resulting emission at around 420 nm, was performed in order to determine the wavelength causing the greatest emission intensity. The excitation and emission spectra for the free BAPP ligand and compounds 1 and 2 are depicted in Fig. 4. Fig. 4
(a) presents two excitation peaks of almost equal intensities (340 and 366 nm) for the free BAPP ligand. Upon incorporation of the BAPP ligand with CdII ions, excitations are observed at 346 and 370 nm for compound 1, and at 360 nm for compound 2. The maximum luminescence of the BAPP ligand is observed at 423 and 446 nm upon excitation at λex = 366 nm, which corresponds to a blue luminescence. The shapes of the emission spectra of 1 and 2 are similar to the free BAPP emission. As seen in the figure, upon excitation at 346 nm, complex 1 exhibited weak emission peaks at 431 and 453 nm, which showed a small of about 8 nm compared with the BAPP ligand. As in the case of the BAPP ligand, complex 2 shows a strong blue luminescence, with the main peaks at 418 and 439 nm, at an excitation wavelength of 360 nm. Unlike complex 1, these emission bands are blue-shifted relative to the bands observed for the BAPP ligand. Broadband blue emission has been successfully realized in [pipH]2[Co(NCS)4] and [pipH]2[Ni(NCS)4] (Bie et al., 2005
), [Hg(μ2-LH)Cl2]2[Hg2(μ2-Cl)2Cl4]·2H2O and [Hg4(μ3-L)2(μ2-Cl)2Cl6] [L is N-(2-aminoethyl)piperazine] (Li et al., 2007
), [(N-AEPz)ZnCl4]Cl (N-AEPz is N-aminoethylpiperazine) (Zhang et al., 2020
), (CuI)2(N,N′-diethylpiperazine) (Safko et al., 2012
), (CuCN)2(Pip) and (CuCN)2(Me2Pip) (Me2Pip is N,N′-dimethylpiperazine) (Lim et al., 2008
), Ag(L)(ReO4) [L is N-(2-aminoethyl)piperazine] (Kovalev et al., 2015
) and {[Cd(C4H11N2)(μ-Cl)2Cl]·H2O}n (Mabrouk et al., 2015
). According to an earlier report, the free piperazine ligand has an emission band at 418 nm on excitation at 312 nm (Bie et al., 2005
).
![]() | Figure 4 Room-temperature solid-state (a) excitation and (b) emission spectra of the BAPP ligand and compounds 1 and 2. |
The BAPP luminescence emission position is red-shifted to 534 nm upon excitation at 449 nm and is accompanied by the appearance of a green luminescence (Fig. 4). In comparison with the blue luminescence, the green luminescence is characterized by its low intensity. Under 448 nm irradiation, complex 1 displayed a green emission with a peak at 562 nm. When 2 was excited at 449 nm, the luminescence spectrum exhibited an emission peak centred at 565 nm. However, compared to the BAPP ligand, the corresponding emission bands of compounds 1 and 2 have higher emission intensities. Considering the energy diagram proposed by Bie et al. (2005
), the observed green emission is probably the result of a from the lowest of the ligand to its ground-state level.
Admittedly, the TBST residue present in 1 and 2 contains an Si—S bond where both elements have vacant 3d orbitals and, as a result, may participate in the emission process. Previous theoretical studies of the protonation and deprotonation of tri-tert-butoxysilanethiol using DFT and natural bond orbital (NBO) calculations have shown that lone pairs from sulfur in Si—S bonds are delocalized due to interaction with the antibonding σ*Si–O orbitals (Chojnacki, 2008a,b
). Also, because of the polarization effects, these orbitals are strongly positioned on the silicon side. Therefore, the Si—S bonds are unlikely to condition the occurrence of emissions of complexes 1 and 2. To confirm this, we conducted an additional experiment to determine whether the starting substrate [Cd{SSi(OtBu)3}2]2 exhibits emission when excited and we observed no emission. Thus, we can assume that the luminescence differences between the emission properties of 1 and 2 (red and blue shifts relative to BAPP, and different intensities of their emission bands) should be attributed to their different structures, as shown by the X-ray studies.
3.6. Thermal analysis
The thermal behaviour of 1 and 2 was investigated simultaneously by TG–DSC (thermogravimetry–differential scanning calorimetry) and TG–FT–IR (thermogravimetry–Fourier transform infrared) methods. The cadmium complexes show different thermal stabilities under an air atmosphere. The dimeric complex 1 exhibits slightly lower thermal stability (177 °C) in comparison with polymeric complex 2 (187 °C). This observation can be explained in terms of their different crystal structures. In dimeric complex 1, the CdII atoms are chelated by the amine ligand, forming a six-membered ring, which slightly reduces the thermal stability of the metal complex. The decomposition processes of both complexes [Fig. 5(a)] are preceded by the melting processes observed on the DSC curves [Fig. 5
(a)].
![]() | Figure 5 Thermal analysis of complexes 1 and 2 in air, showing (a) the TG curves and (b) the DSC curves. |
The endothermic effects associated with melting were observed at 163.1 and 120.2 °C (peak tops) for 1 and 2, respectively. Further heating results in the decomposition of the complexes connected with the significant mass losses observed on the TG curves. The mass losses of 76.50 (for 1) and 70.41% (for 2) were found in the relatively narrow temperature ranges of 188–317 and 151–308 °C. A detailed analysis of the DSC curve of 1 allows, in the above temperature range, a very weak endothermic effect to be distinguished at 217 °C (peak top). The DSC curves of both complexes are dominated by strong exothermic effects, with a maximum at about 300 °C [Fig. 6(a)]. These effects can be attributed to the burning processes of the organic parts of the cadmium complexes. Further heating of the solid residues causes some mass changes connected with their transformations [Fig. 6
(a)]. The above-mentioned distinct mass losses point most probably to the formation of cadmium thiosilicate (Cd2SiSO3). At higher temperatures, further mass losses of 3.50 (for 1) and 10.45% (for 2) are observed. Taking into account that these mass changes were accompanied by exothermic effects, it can be assumed that the S atom of thiosilicate was oxidized and that the transformation of Cd2SiSO3 into Cd2SiO4 took place (Su et al., 2018
). Cadmium silicate is thermally stable in the temperature range 730–850 °C and, next, its further transformation takes place with the probable formation of cadmium oxide and silica (Kropidłowska et al., 2007
). The total observed mass losses recorded at 1000 °C for 1 and 2 were 82.42 and 84.00%, respectively.
![]() | Figure 6 The FT–IR spectra of the evolved compounds during thermal decomposition of (a) 1 and (b) 2 under nitrogen. |
Under a nitrogen atmosphere, the thermal decomposition of both compounds occurs above 160 °C. The TG curves exhibit significant mass losses of 81.3 and 82.0% up to 300 °C for 1 and 2, respectively. The total recorded mass loss at 700 °C was 85% for both metal complexes. The solid residues of the cadmium complexes heated under an inert atmosphere are composed of some unidentified cadmium compounds and unburnt carbon species.
The FT–IR spectra of the gaseous products of the thermal decomposition of the metal complexes are dominated by bands derived from the evolved Si–alkoxy and tert-butyl compounds (Fig. 6). A very strong band at 1070 cm−1 was assigned to the stretching vibrations of the Si—O groups. The several bands with the strongest maxima at 2980 and 2942 cm−1, as well as those at 1457 cm−1, can be ascribed to the stretching and deformation vibrations of the methyl groups from the evolved moieties. The band at 1188 cm−1 can be assigned to the stretching vibrations of the C—O group from the tertiary alcohol molecules (Holly et al., 1975
; Silverstein & Webster, 1996
). Breaking of the Si—S bonds in the molecules of the investigated cadmium complexes leads to the evolution of sulfur dioxide, which gives diagnostic double bands at 1390 and 1367 cm−1 (Łyszczek et al., 2015
). Heating of the complexes under an inert atmosphere also leads to the evolution of aliphatic hydrocarbons as a result of degradation of the coordinated amine group. The presence of bands in the regions 3000–2700 and 1480–1360 cm−1, as well as those at 860 and 821 cm−1, due to stretching, deformation and rocking vibrations of methyl groups, can indicate the evolution of the ethane/propane molecules. The IR spectra of complex 2 shows a broad weak band in the region 3200–3000 cm−1, with a maximum at 3080 cm−1, and a medium intensity band at 1277 cm−1, which can be ascribed to the C—H, =C—H and C—N stretching vibrations of some aliphatic and/or (Holly et al., 1975
; Silverstein & Webster, 1996
). The formation of volatile species containing carbonyl groups (C=O) during the thermal decomposition of 2 is postulated based on the presence of a band at 1773 cm−1. The FT–IR spectra of volatile compounds recorded above 400 °C also show relatively weak bands at 2341/2341 and 689 cm−1 from stretching and deformation vibrations of carbon dioxide molecules. It is worth mentioning that the intensity of CO2 evolution is greater for compound 2 (Fig. 6
).
3.7. Antimicrobial activity
The 1 was checked from 4 to 0.016 mg l−1. The performed susceptibility tests exhibited a lack of antifungal activity of 1 against 14 of the tested isolates, but for three tested dermatophytes, i.e. Epidermophyton floccosum, Microsporum canis and Trichophyton rubrum, the inhibition of their growth was observed at 0.25 mg l−1 and above. The mechanism of the toxicity of 1 towards the fungal isolates relies on Cd, however, the influence of other groups cannot be excluded thus far. Moreover, the fungal specimens are generally considered to be tolerant to heavy metals due to their presence in soil (Rajapaksha et al., 2004; Bhajbhuje et al., 2013
; Li et al., 2019
). In the case of the influence of cadmium on the dermatophytes, there has been one report confirming its antifungal activity; however, the test was performed with the colony diameter method (Al-Janabi, 2011
). This specific antifungal activity may also be related to the fact that the development and growth of dermatophytes depends strongly on keratin, a hydrophobic protein rich in sulfur-containing amino acids such as cysteine and methionine (Ciesielska et al., 2021
), which, being soft bases, have a particular affinity for soft acids like Cd2+ ions. To address the question of the antidermatophyte effect of 1, further investigations are being considered.
4. Conclusion
In summary, this study has provided detailed insight into the structures of two new heteroleptic cadmium tri-tert-butoxysilanethiolates with 1,4-bis(3-aminopropyl)piperazine synthesized in different solvent systems while maintaining the remaining reaction conditions. The experiments yielded compounds with different structures and the absence of solvent molecules crystallizing in the structures. The structures of the obtained complexes appeared to be crucial for their spectral properties and antifungal activity. Compound 1 inhibits the growth of fungi belonging to the group of dermatophytes. The results of our study show that it is worth extending the study to other metal silanethiolates with the purpose of obtaining compounds with better antimicrobial activity and luminescence.
Supporting information
https://doi.org/10.1107/S2053229623005442/dv3023sup1.cif
contains datablocks dkz2, dkz1, global. DOI:Structure factors: contains datablock dkz1. DOI: https://doi.org/10.1107/S2053229623005442/dv3023dkz1sup2.hkl
Structure factors: contains datablock dkz2. DOI: https://doi.org/10.1107/S2053229623005442/dv3023dkz2sup3.hkl
Additional tables and figures. DOI: https://doi.org/10.1107/S2053229623005442/dv3023sup4.pdf
For both structures, data collection: WinXpose in X-AREA (Stoe & Cie, 2016); cell
Recipe in X-AREA (Stoe & Cie, 2016); data reduction: Integrate and X-RED32 in X-AREA (Stoe & Cie, 2016); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2020); software used to prepare material for publication: WinGX publication routines (Farrugia, 2012) and OLEX2 (Dolomanov et al., 2009).[Cd(C12H27O3SSi)2(C10H24N4)] | F(000) = 1864 |
Mr = 871.7 | Dx = 1.239 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 42943 reflections |
a = 16.424 (5) Å | θ = 2.4–29.6° |
b = 16.876 (4) Å | µ = 0.65 mm−1 |
c = 18.265 (5) Å | T = 120 K |
β = 112.66 (2)° | Prism, colorless |
V = 4672 (2) Å3 | 0.38 × 0.34 × 0.3 mm |
Z = 4 |
Stoe IPDS 2T diffractometer | 9535 independent reflections |
Radiation source: GeniX Mo, 0.05 x 0.05 mm2 microfocus | 8345 reflections with I > 2σ(I) |
Parabolic x-ray mirror monochromator | Rint = 0.045 |
Detector resolution: 6.67 pixels mm-1 | θmax = 26.4°, θmin = 2.4° |
rotation method, ω scans | h = −20→20 |
Absorption correction: multi-scan [LANA (Koziskova et al., 2016) and X-Red32 in X-AREA (Stoe & Cie, 2016)] | k = −21→21 |
Tmin = 0.664, Tmax = 0.970 | l = −22→22 |
33547 measured reflections |
Refinement on F2 | 0 constraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.043 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.107 | w = 1/[σ2(Fo2) + (0.0283P)2 + 12.4766P] where P = (Fo2 + 2Fc2)/3 |
S = 1.14 | (Δ/σ)max = 0.001 |
9535 reflections | Δρmax = 1.32 e Å−3 |
476 parameters | Δρmin = −0.74 e Å−3 |
0 restraints |
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. Single-crystal X-ray diffraction data of compounds 1 and 2 were collected at 120 (2) K with a Stoe IPDS-2T diffractometer equipped with a graphite-monochromated Mo Kα radiation source. Crystals were cooled using a Cryostream 800 open-flow nitrogen cryostat (Oxford Cryosystems). Data collection and image processing was performed with X-AREA 1.75 (Stoe & Cie, 2016). Intensity data were scaled with LANA (part of X-AREA) in order to minimize differences in intensities of symmetry-equivalent reflections (a multi-scan method). The structures of 1 and 2 were solved using intrinsic phasing procedure implemented in SHELXT and all non-hydrogen atoms were refined with anisotropic displacement parameters by full-matrix least squares procedure based on F2 using the SHELX–2014 program package (Sheldrick, 2014; Sheldrick, 2015). The OLEX2 (Dolomanov et al., 2009) and Wingx (Farrugia, 2012) program suites were used to prepare the final version of CIF files. Mercury (Macrae et al., 2020) was used to prepare the figures. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.8273 (2) | 0.0825 (2) | 0.5368 (2) | 0.0258 (7) | |
C2 | 0.7506 (2) | 0.1086 (2) | 0.4622 (2) | 0.0298 (8) | |
H2A | 0.694784 | 0.096941 | 0.467831 | 0.045* | |
H2B | 0.75269 | 0.080076 | 0.416299 | 0.045* | |
H2C | 0.754765 | 0.165737 | 0.454563 | 0.045* | |
C3 | 0.9144 (3) | 0.0959 (3) | 0.5281 (3) | 0.0449 (11) | |
H3C | 0.921048 | 0.15231 | 0.519105 | 0.067* | |
H3D | 0.915393 | 0.065177 | 0.48289 | 0.067* | |
H3E | 0.962928 | 0.078726 | 0.576588 | 0.067* | |
C4 | 0.8171 (3) | −0.0047 (2) | 0.5535 (2) | 0.0392 (10) | |
H4A | 0.866903 | −0.021075 | 0.601462 | 0.059* | |
H4B | 0.815997 | −0.036777 | 0.508446 | 0.059* | |
H4C | 0.761873 | −0.012177 | 0.561413 | 0.059* | |
C5 | 1.0397 (2) | 0.2144 (2) | 0.7307 (2) | 0.0276 (8) | |
C6 | 1.0337 (2) | 0.1353 (2) | 0.7682 (2) | 0.0307 (8) | |
H6A | 0.984744 | 0.136696 | 0.786217 | 0.046* | |
H6B | 1.089016 | 0.125177 | 0.813563 | 0.046* | |
H6C | 1.023566 | 0.092947 | 0.728917 | 0.046* | |
C7 | 1.0519 (3) | 0.2821 (2) | 0.7886 (2) | 0.0440 (11) | |
H7A | 1.05456 | 0.3323 | 0.762738 | 0.066* | |
H7B | 1.106879 | 0.274397 | 0.834991 | 0.066* | |
H7C | 1.002072 | 0.28319 | 0.805555 | 0.066* | |
C8 | 1.1147 (3) | 0.2131 (3) | 0.7022 (3) | 0.0504 (12) | |
H8A | 1.10501 | 0.170413 | 0.663437 | 0.076* | |
H8B | 1.170454 | 0.204094 | 0.747422 | 0.076* | |
H8C | 1.117281 | 0.264013 | 0.677378 | 0.076* | |
C9 | 0.8199 (2) | 0.3511 (2) | 0.5430 (2) | 0.0246 (7) | |
C10 | 0.7397 (2) | 0.3709 (2) | 0.4687 (2) | 0.0338 (8) | |
H10A | 0.735276 | 0.332955 | 0.426703 | 0.051* | |
H10B | 0.745763 | 0.424598 | 0.451106 | 0.051* | |
H10C | 0.686349 | 0.367773 | 0.48042 | 0.051* | |
C11 | 0.9030 (2) | 0.3560 (3) | 0.5256 (2) | 0.0367 (9) | |
H11A | 0.954246 | 0.341715 | 0.573314 | 0.055* | |
H11B | 0.910174 | 0.41016 | 0.50967 | 0.055* | |
H11C | 0.898261 | 0.319272 | 0.482583 | 0.055* | |
C12 | 0.8261 (3) | 0.4054 (2) | 0.6105 (2) | 0.0400 (10) | |
H12A | 0.772479 | 0.400491 | 0.6215 | 0.06* | |
H12B | 0.832473 | 0.46025 | 0.595916 | 0.06* | |
H12C | 0.877505 | 0.390713 | 0.657914 | 0.06* | |
C13 | 0.3820 (2) | 0.0780 (2) | 0.7621 (2) | 0.0276 (7) | |
C14 | 0.3326 (3) | 0.1069 (3) | 0.6770 (2) | 0.0376 (9) | |
H14A | 0.29846 | 0.154435 | 0.677512 | 0.056* | |
H14B | 0.292574 | 0.065275 | 0.646035 | 0.056* | |
H14C | 0.375102 | 0.11964 | 0.653084 | 0.056* | |
C15 | 0.4309 (3) | 0.0022 (2) | 0.7635 (3) | 0.0435 (10) | |
H15A | 0.4732 | 0.010954 | 0.73838 | 0.065* | |
H15B | 0.388797 | −0.039032 | 0.734411 | 0.065* | |
H15C | 0.462507 | −0.014772 | 0.818541 | 0.065* | |
C16 | 0.3172 (3) | 0.0657 (3) | 0.8029 (3) | 0.0384 (9) | |
H16A | 0.349078 | 0.045546 | 0.856713 | 0.058* | |
H16B | 0.271919 | 0.027445 | 0.772557 | 0.058* | |
H16C | 0.289188 | 0.116335 | 0.805485 | 0.058* | |
C17 | 0.4078 (2) | 0.3344 (2) | 0.7516 (2) | 0.0267 (7) | |
C18 | 0.4680 (3) | 0.3998 (2) | 0.7996 (2) | 0.0354 (9) | |
H18A | 0.506218 | 0.379133 | 0.851693 | 0.053* | |
H18B | 0.432303 | 0.443486 | 0.806606 | 0.053* | |
H18C | 0.504369 | 0.419122 | 0.77162 | 0.053* | |
C19 | 0.3536 (3) | 0.3027 (2) | 0.7971 (3) | 0.0419 (10) | |
H19A | 0.314902 | 0.260064 | 0.766515 | 0.063* | |
H19B | 0.317762 | 0.345616 | 0.805227 | 0.063* | |
H19C | 0.393419 | 0.28214 | 0.848633 | 0.063* | |
C20 | 0.3478 (3) | 0.3651 (3) | 0.6702 (3) | 0.0481 (11) | |
H20A | 0.383771 | 0.383942 | 0.641646 | 0.072* | |
H20B | 0.311806 | 0.40888 | 0.676548 | 0.072* | |
H20C | 0.309089 | 0.322257 | 0.640025 | 0.072* | |
C21 | 0.6348 (2) | 0.2116 (2) | 0.9489 (2) | 0.0289 (8) | |
C22 | 0.6266 (3) | 0.2626 (3) | 1.0138 (2) | 0.0504 (12) | |
H22A | 0.635215 | 0.318352 | 1.003503 | 0.076* | |
H22B | 0.671545 | 0.246823 | 1.065081 | 0.076* | |
H22C | 0.567847 | 0.255713 | 1.014838 | 0.076* | |
C23 | 0.6204 (3) | 0.1257 (3) | 0.9648 (3) | 0.0525 (12) | |
H23A | 0.562196 | 0.119827 | 0.967313 | 0.079* | |
H23B | 0.666114 | 0.109211 | 1.015347 | 0.079* | |
H23C | 0.623602 | 0.092573 | 0.921903 | 0.079* | |
C24 | 0.7221 (3) | 0.2236 (5) | 0.9424 (3) | 0.077 (2) | |
H24A | 0.728169 | 0.185755 | 0.904091 | 0.115* | |
H24B | 0.769616 | 0.215035 | 0.994359 | 0.115* | |
H24C | 0.725574 | 0.277721 | 0.924451 | 0.115* | |
C25 | 0.5395 (2) | 0.2581 (2) | 0.4966 (2) | 0.0255 (7) | |
H25A | 0.539003 | 0.259021 | 0.442257 | 0.031* | |
H25B | 0.546612 | 0.313288 | 0.516516 | 0.031* | |
C26 | 0.4524 (2) | 0.2256 (2) | 0.4939 (2) | 0.0312 (8) | |
H26A | 0.406284 | 0.266468 | 0.47104 | 0.037* | |
H26B | 0.457478 | 0.215052 | 0.548752 | 0.037* | |
C27 | 0.4231 (2) | 0.1495 (2) | 0.4452 (2) | 0.0318 (8) | |
H27A | 0.36341 | 0.135042 | 0.441904 | 0.038* | |
H27B | 0.419297 | 0.159601 | 0.390558 | 0.038* | |
C28 | 0.4691 (2) | 0.0206 (2) | 0.4188 (2) | 0.0271 (7) | |
H28A | 0.479269 | 0.042621 | 0.372859 | 0.033* | |
H28B | 0.407371 | 0.001508 | 0.399917 | 0.033* | |
C29 | 0.4686 (2) | 0.0479 (2) | 0.5464 (2) | 0.0261 (7) | |
H29A | 0.406893 | 0.029049 | 0.529066 | 0.031* | |
H29B | 0.478062 | 0.088975 | 0.587529 | 0.031* | |
C30 | 0.6762 (3) | 0.4103 (2) | 0.7398 (2) | 0.0300 (8) | |
H30A | 0.732835 | 0.404701 | 0.73285 | 0.036* | |
H30B | 0.68679 | 0.395558 | 0.795168 | 0.036* | |
C31 | 0.6472 (3) | 0.4975 (2) | 0.7267 (2) | 0.0281 (8) | |
H31A | 0.588634 | 0.502456 | 0.729971 | 0.034* | |
H31B | 0.689433 | 0.529733 | 0.769959 | 0.034* | |
C32 | 0.6415 (3) | 0.5314 (2) | 0.6469 (2) | 0.0281 (8) | |
H32A | 0.628458 | 0.588781 | 0.645733 | 0.034* | |
H32B | 0.699892 | 0.525678 | 0.643409 | 0.034* | |
C33 | 0.5841 (2) | 0.5230 (2) | 0.5043 (2) | 0.0269 (7) | |
H33A | 0.643792 | 0.509774 | 0.506718 | 0.032* | |
H33B | 0.577936 | 0.581444 | 0.5017 | 0.032* | |
C34 | 0.4844 (2) | 0.5131 (2) | 0.5697 (2) | 0.0265 (7) | |
H34A | 0.476718 | 0.571311 | 0.568186 | 0.032* | |
H34B | 0.475586 | 0.492749 | 0.617002 | 0.032* | |
Cd1 | 0.66166 (2) | 0.22716 (2) | 0.68348 (2) | 0.01980 (7) | |
N1 | 0.61539 (19) | 0.20993 (17) | 0.54853 (17) | 0.0213 (6) | |
N2 | 0.48273 (18) | 0.08247 (16) | 0.47839 (16) | 0.0220 (6) | |
N3 | 0.6112 (2) | 0.35403 (17) | 0.68530 (18) | 0.0240 (6) | |
N4 | 0.5745 (2) | 0.49401 (16) | 0.57640 (16) | 0.0241 (6) | |
O1 | 0.82513 (14) | 0.12462 (13) | 0.60513 (12) | 0.0200 (5) | |
O2 | 0.96109 (14) | 0.22811 (14) | 0.66101 (13) | 0.0234 (5) | |
O3 | 0.80536 (14) | 0.26968 (13) | 0.56140 (13) | 0.0199 (4) | |
O4 | 0.44271 (15) | 0.13785 (14) | 0.80805 (14) | 0.0249 (5) | |
O5 | 0.46047 (15) | 0.27295 (13) | 0.73567 (13) | 0.0243 (5) | |
O6 | 0.56721 (16) | 0.23889 (15) | 0.87650 (14) | 0.0285 (5) | |
S1 | 0.82429 (5) | 0.23320 (5) | 0.73707 (5) | 0.02238 (17) | |
S2 | 0.58603 (6) | 0.13526 (5) | 0.74087 (5) | 0.02728 (19) | |
Si1 | 0.85637 (6) | 0.21366 (5) | 0.63890 (5) | 0.01761 (18) | |
Si2 | 0.51154 (6) | 0.19731 (5) | 0.79140 (5) | 0.02019 (18) | |
H1A | 0.602 (3) | 0.160 (3) | 0.532 (2) | 0.027 (10)* | |
H1B | 0.661 (3) | 0.220 (2) | 0.540 (2) | 0.026 (10)* | |
H3A | 0.586 (3) | 0.375 (2) | 0.633 (3) | 0.034 (11)* | |
H3B | 0.563 (3) | 0.348 (3) | 0.698 (3) | 0.040 (12)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0277 (18) | 0.0245 (17) | 0.0218 (16) | 0.0027 (14) | 0.0057 (14) | −0.0044 (13) |
C2 | 0.035 (2) | 0.0280 (18) | 0.0215 (16) | 0.0048 (16) | 0.0051 (15) | −0.0034 (14) |
C3 | 0.033 (2) | 0.066 (3) | 0.039 (2) | 0.000 (2) | 0.0174 (18) | −0.017 (2) |
C4 | 0.051 (2) | 0.0242 (18) | 0.032 (2) | 0.0094 (18) | 0.0044 (18) | −0.0050 (16) |
C5 | 0.0164 (16) | 0.0323 (19) | 0.0258 (17) | −0.0030 (14) | −0.0009 (13) | 0.0096 (14) |
C6 | 0.0209 (17) | 0.0304 (19) | 0.0317 (19) | 0.0011 (15) | 0.0000 (14) | 0.0098 (15) |
C7 | 0.042 (2) | 0.034 (2) | 0.036 (2) | −0.0147 (19) | −0.0067 (18) | 0.0014 (17) |
C8 | 0.0166 (18) | 0.083 (4) | 0.049 (3) | 0.002 (2) | 0.0098 (17) | 0.025 (2) |
C9 | 0.0231 (16) | 0.0236 (16) | 0.0271 (17) | −0.0019 (14) | 0.0097 (14) | 0.0064 (14) |
C10 | 0.0276 (19) | 0.0315 (19) | 0.037 (2) | 0.0060 (16) | 0.0063 (16) | 0.0152 (16) |
C11 | 0.0277 (19) | 0.042 (2) | 0.042 (2) | 0.0026 (17) | 0.0156 (17) | 0.0162 (18) |
C12 | 0.059 (3) | 0.0252 (19) | 0.036 (2) | 0.0011 (19) | 0.019 (2) | 0.0027 (16) |
C13 | 0.0247 (17) | 0.0255 (17) | 0.0349 (19) | −0.0063 (14) | 0.0142 (15) | −0.0076 (15) |
C14 | 0.035 (2) | 0.042 (2) | 0.033 (2) | −0.0111 (18) | 0.0100 (17) | −0.0104 (17) |
C15 | 0.042 (2) | 0.0249 (19) | 0.070 (3) | −0.0004 (18) | 0.028 (2) | −0.0056 (19) |
C16 | 0.035 (2) | 0.038 (2) | 0.050 (2) | −0.0088 (17) | 0.0246 (19) | −0.0039 (18) |
C17 | 0.0226 (16) | 0.0237 (17) | 0.0334 (18) | 0.0040 (14) | 0.0104 (14) | −0.0033 (14) |
C18 | 0.035 (2) | 0.0256 (18) | 0.049 (2) | −0.0029 (16) | 0.0203 (18) | −0.0093 (17) |
C19 | 0.036 (2) | 0.034 (2) | 0.064 (3) | −0.0003 (18) | 0.028 (2) | −0.010 (2) |
C20 | 0.043 (2) | 0.044 (2) | 0.044 (2) | 0.015 (2) | 0.002 (2) | −0.001 (2) |
C21 | 0.0231 (17) | 0.039 (2) | 0.0211 (16) | −0.0025 (15) | 0.0046 (14) | −0.0005 (15) |
C22 | 0.051 (3) | 0.059 (3) | 0.028 (2) | 0.004 (2) | 0.0018 (19) | −0.009 (2) |
C23 | 0.059 (3) | 0.044 (3) | 0.038 (2) | 0.005 (2) | 0.001 (2) | 0.010 (2) |
C24 | 0.027 (2) | 0.162 (7) | 0.038 (3) | −0.004 (3) | 0.010 (2) | 0.019 (3) |
C25 | 0.0274 (17) | 0.0199 (16) | 0.0222 (16) | −0.0024 (14) | 0.0018 (14) | 0.0008 (13) |
C26 | 0.0226 (17) | 0.0175 (16) | 0.045 (2) | 0.0046 (14) | 0.0038 (15) | −0.0010 (15) |
C27 | 0.0235 (17) | 0.0225 (17) | 0.039 (2) | −0.0037 (14) | 0.0011 (15) | 0.0005 (15) |
C28 | 0.0329 (19) | 0.0243 (17) | 0.0214 (16) | −0.0046 (15) | 0.0075 (14) | −0.0025 (14) |
C29 | 0.0288 (18) | 0.0229 (16) | 0.0302 (18) | −0.0030 (14) | 0.0152 (15) | −0.0069 (14) |
C30 | 0.036 (2) | 0.0173 (16) | 0.0264 (17) | 0.0019 (15) | 0.0005 (15) | −0.0006 (14) |
C31 | 0.039 (2) | 0.0192 (16) | 0.0246 (17) | 0.0031 (15) | 0.0102 (15) | −0.0017 (13) |
C32 | 0.039 (2) | 0.0183 (16) | 0.0276 (18) | 0.0043 (15) | 0.0140 (16) | −0.0003 (14) |
C33 | 0.0363 (19) | 0.0208 (16) | 0.0285 (18) | 0.0054 (15) | 0.0180 (15) | 0.0046 (14) |
C34 | 0.038 (2) | 0.0200 (16) | 0.0260 (17) | 0.0087 (15) | 0.0177 (15) | 0.0039 (13) |
Cd1 | 0.02170 (12) | 0.01716 (12) | 0.02166 (12) | 0.00228 (9) | 0.00958 (9) | 0.00049 (9) |
N1 | 0.0194 (14) | 0.0202 (14) | 0.0247 (14) | −0.0017 (11) | 0.0089 (12) | −0.0020 (11) |
N2 | 0.0200 (14) | 0.0194 (13) | 0.0246 (14) | 0.0005 (11) | 0.0063 (11) | −0.0035 (11) |
N3 | 0.0276 (15) | 0.0190 (14) | 0.0252 (15) | 0.0039 (12) | 0.0100 (13) | −0.0007 (12) |
N4 | 0.0334 (16) | 0.0186 (13) | 0.0227 (14) | 0.0048 (12) | 0.0135 (12) | 0.0015 (11) |
O1 | 0.0206 (11) | 0.0215 (11) | 0.0177 (10) | 0.0013 (9) | 0.0073 (9) | 0.0000 (9) |
O2 | 0.0145 (10) | 0.0322 (13) | 0.0203 (11) | −0.0020 (10) | 0.0031 (9) | 0.0062 (10) |
O3 | 0.0175 (10) | 0.0190 (11) | 0.0200 (11) | 0.0000 (9) | 0.0037 (9) | 0.0016 (9) |
O4 | 0.0247 (12) | 0.0251 (12) | 0.0272 (12) | −0.0044 (10) | 0.0126 (10) | −0.0042 (10) |
O5 | 0.0266 (12) | 0.0215 (11) | 0.0246 (11) | 0.0026 (10) | 0.0096 (10) | −0.0013 (10) |
O6 | 0.0271 (12) | 0.0297 (13) | 0.0233 (12) | −0.0008 (11) | 0.0039 (10) | −0.0023 (10) |
S1 | 0.0214 (4) | 0.0263 (4) | 0.0177 (4) | 0.0004 (3) | 0.0057 (3) | −0.0009 (3) |
S2 | 0.0342 (5) | 0.0212 (4) | 0.0345 (5) | 0.0011 (4) | 0.0223 (4) | 0.0012 (3) |
Si1 | 0.0150 (4) | 0.0184 (4) | 0.0168 (4) | −0.0005 (3) | 0.0032 (3) | 0.0011 (3) |
Si2 | 0.0192 (4) | 0.0221 (4) | 0.0194 (4) | −0.0011 (4) | 0.0076 (3) | −0.0011 (3) |
C1—O1 | 1.448 (4) | C20—H20C | 0.98 |
C1—C3 | 1.516 (5) | C21—O6 | 1.436 (4) |
C1—C2 | 1.522 (5) | C21—C24 | 1.497 (6) |
C1—C4 | 1.525 (5) | C21—C22 | 1.512 (6) |
C2—H2A | 0.98 | C21—C23 | 1.515 (6) |
C2—H2B | 0.98 | C22—H22A | 0.98 |
C2—H2C | 0.98 | C22—H22B | 0.98 |
C3—H3C | 0.98 | C22—H22C | 0.98 |
C3—H3D | 0.98 | C23—H23A | 0.98 |
C3—H3E | 0.98 | C23—H23B | 0.98 |
C4—H4A | 0.98 | C23—H23C | 0.98 |
C4—H4B | 0.98 | C24—H24A | 0.98 |
C4—H4C | 0.98 | C24—H24B | 0.98 |
C5—O2 | 1.441 (4) | C24—H24C | 0.98 |
C5—C8 | 1.510 (5) | C25—N1 | 1.484 (4) |
C5—C7 | 1.515 (6) | C25—C26 | 1.514 (5) |
C5—C6 | 1.521 (5) | C25—H25A | 0.99 |
C6—H6A | 0.98 | C25—H25B | 0.99 |
C6—H6B | 0.98 | C26—C27 | 1.531 (5) |
C6—H6C | 0.98 | C26—H26A | 0.99 |
C7—H7A | 0.98 | C26—H26B | 0.99 |
C7—H7B | 0.98 | C27—N2 | 1.465 (4) |
C7—H7C | 0.98 | C27—H27A | 0.99 |
C8—H8A | 0.98 | C27—H27B | 0.99 |
C8—H8B | 0.98 | C28—N2 | 1.462 (4) |
C8—H8C | 0.98 | C28—C29i | 1.512 (5) |
C9—O3 | 1.456 (4) | C28—H28A | 0.99 |
C9—C12 | 1.507 (5) | C28—H28B | 0.99 |
C9—C11 | 1.519 (5) | C29—N2 | 1.470 (4) |
C9—C10 | 1.520 (5) | C29—H29A | 0.99 |
C10—H10A | 0.98 | C29—H29B | 0.99 |
C10—H10B | 0.98 | C30—N3 | 1.488 (4) |
C10—H10C | 0.98 | C30—C31 | 1.537 (5) |
C11—H11A | 0.98 | C30—H30A | 0.99 |
C11—H11B | 0.98 | C30—H30B | 0.99 |
C11—H11C | 0.98 | C31—C32 | 1.535 (5) |
C12—H12A | 0.98 | C31—H31A | 0.99 |
C12—H12B | 0.98 | C31—H31B | 0.99 |
C12—H12C | 0.98 | C32—N4 | 1.474 (5) |
C13—O4 | 1.440 (4) | C32—H32A | 0.99 |
C13—C15 | 1.507 (5) | C32—H32B | 0.99 |
C13—C14 | 1.529 (5) | C33—N4 | 1.469 (4) |
C13—C16 | 1.529 (5) | C33—C34ii | 1.514 (5) |
C14—H14A | 0.98 | C33—H33A | 0.99 |
C14—H14B | 0.98 | C33—H33B | 0.99 |
C14—H14C | 0.98 | C34—N4 | 1.473 (4) |
C15—H15A | 0.98 | C34—H34A | 0.99 |
C15—H15B | 0.98 | C34—H34B | 0.99 |
C15—H15C | 0.98 | Cd1—N3 | 2.301 (3) |
C16—H16A | 0.98 | Cd1—N1 | 2.301 (3) |
C16—H16B | 0.98 | Cd1—S2 | 2.4597 (10) |
C16—H16C | 0.98 | Cd1—S1 | 2.4675 (12) |
C17—O5 | 1.451 (4) | N1—H1A | 0.90 (4) |
C17—C18 | 1.515 (5) | N1—H1B | 0.85 (4) |
C17—C20 | 1.524 (5) | N3—H3A | 0.96 (4) |
C17—C19 | 1.528 (5) | N3—H3B | 0.90 (5) |
C18—H18A | 0.98 | O1—Si1 | 1.630 (2) |
C18—H18B | 0.98 | O2—Si1 | 1.627 (2) |
C18—H18C | 0.98 | O3—Si1 | 1.639 (2) |
C19—H19A | 0.98 | O4—Si2 | 1.625 (2) |
C19—H19B | 0.98 | O5—Si2 | 1.647 (2) |
C19—H19C | 0.98 | O6—Si2 | 1.628 (2) |
C20—H20A | 0.98 | S1—Si1 | 2.0805 (13) |
C20—H20B | 0.98 | S2—Si2 | 2.0773 (13) |
O1—C1—C3 | 110.8 (3) | C24—C21—C23 | 111.6 (4) |
O1—C1—C2 | 110.0 (3) | C22—C21—C23 | 109.1 (4) |
C3—C1—C2 | 110.6 (3) | C21—C22—H22A | 109.5 |
O1—C1—C4 | 105.1 (3) | C21—C22—H22B | 109.5 |
C3—C1—C4 | 110.2 (3) | H22A—C22—H22B | 109.5 |
C2—C1—C4 | 110.0 (3) | C21—C22—H22C | 109.5 |
C1—C2—H2A | 109.5 | H22A—C22—H22C | 109.5 |
C1—C2—H2B | 109.5 | H22B—C22—H22C | 109.5 |
H2A—C2—H2B | 109.5 | C21—C23—H23A | 109.5 |
C1—C2—H2C | 109.5 | C21—C23—H23B | 109.5 |
H2A—C2—H2C | 109.5 | H23A—C23—H23B | 109.5 |
H2B—C2—H2C | 109.5 | C21—C23—H23C | 109.5 |
C1—C3—H3C | 109.5 | H23A—C23—H23C | 109.5 |
C1—C3—H3D | 109.5 | H23B—C23—H23C | 109.5 |
H3C—C3—H3D | 109.5 | C21—C24—H24A | 109.5 |
C1—C3—H3E | 109.5 | C21—C24—H24B | 109.5 |
H3C—C3—H3E | 109.5 | H24A—C24—H24B | 109.5 |
H3D—C3—H3E | 109.5 | C21—C24—H24C | 109.5 |
C1—C4—H4A | 109.5 | H24A—C24—H24C | 109.5 |
C1—C4—H4B | 109.5 | H24B—C24—H24C | 109.5 |
H4A—C4—H4B | 109.5 | N1—C25—C26 | 111.9 (3) |
C1—C4—H4C | 109.5 | N1—C25—H25A | 109.2 |
H4A—C4—H4C | 109.5 | C26—C25—H25A | 109.2 |
H4B—C4—H4C | 109.5 | N1—C25—H25B | 109.2 |
O2—C5—C8 | 105.7 (3) | C26—C25—H25B | 109.2 |
O2—C5—C7 | 109.2 (3) | H25A—C25—H25B | 107.9 |
C8—C5—C7 | 110.2 (4) | C25—C26—C27 | 113.9 (3) |
O2—C5—C6 | 110.3 (3) | C25—C26—H26A | 108.8 |
C8—C5—C6 | 110.2 (3) | C27—C26—H26A | 108.8 |
C7—C5—C6 | 111.2 (3) | C25—C26—H26B | 108.8 |
C5—C6—H6A | 109.5 | C27—C26—H26B | 108.8 |
C5—C6—H6B | 109.5 | H26A—C26—H26B | 107.7 |
H6A—C6—H6B | 109.5 | N2—C27—C26 | 113.4 (3) |
C5—C6—H6C | 109.5 | N2—C27—H27A | 108.9 |
H6A—C6—H6C | 109.5 | C26—C27—H27A | 108.9 |
H6B—C6—H6C | 109.5 | N2—C27—H27B | 108.9 |
C5—C7—H7A | 109.5 | C26—C27—H27B | 108.9 |
C5—C7—H7B | 109.5 | H27A—C27—H27B | 107.7 |
H7A—C7—H7B | 109.5 | N2—C28—C29i | 110.4 (3) |
C5—C7—H7C | 109.5 | N2—C28—H28A | 109.6 |
H7A—C7—H7C | 109.5 | C29i—C28—H28A | 109.6 |
H7B—C7—H7C | 109.5 | N2—C28—H28B | 109.6 |
C5—C8—H8A | 109.5 | C29i—C28—H28B | 109.6 |
C5—C8—H8B | 109.5 | H28A—C28—H28B | 108.1 |
H8A—C8—H8B | 109.5 | N2—C29—C28i | 110.9 (3) |
C5—C8—H8C | 109.5 | N2—C29—H29A | 109.5 |
H8A—C8—H8C | 109.5 | C28i—C29—H29A | 109.5 |
H8B—C8—H8C | 109.5 | N2—C29—H29B | 109.5 |
O3—C9—C12 | 110.6 (3) | C28i—C29—H29B | 109.5 |
O3—C9—C11 | 109.9 (3) | H29A—C29—H29B | 108.1 |
C12—C9—C11 | 110.8 (3) | N3—C30—C31 | 114.0 (3) |
O3—C9—C10 | 104.5 (3) | N3—C30—H30A | 108.7 |
C12—C9—C10 | 111.1 (3) | C31—C30—H30A | 108.7 |
C11—C9—C10 | 109.9 (3) | N3—C30—H30B | 108.7 |
C9—C10—H10A | 109.5 | C31—C30—H30B | 108.7 |
C9—C10—H10B | 109.5 | H30A—C30—H30B | 107.6 |
H10A—C10—H10B | 109.5 | C32—C31—C30 | 114.0 (3) |
C9—C10—H10C | 109.5 | C32—C31—H31A | 108.8 |
H10A—C10—H10C | 109.5 | C30—C31—H31A | 108.8 |
H10B—C10—H10C | 109.5 | C32—C31—H31B | 108.8 |
C9—C11—H11A | 109.5 | C30—C31—H31B | 108.8 |
C9—C11—H11B | 109.5 | H31A—C31—H31B | 107.6 |
H11A—C11—H11B | 109.5 | N4—C32—C31 | 114.9 (3) |
C9—C11—H11C | 109.5 | N4—C32—H32A | 108.5 |
H11A—C11—H11C | 109.5 | C31—C32—H32A | 108.5 |
H11B—C11—H11C | 109.5 | N4—C32—H32B | 108.5 |
C9—C12—H12A | 109.5 | C31—C32—H32B | 108.5 |
C9—C12—H12B | 109.5 | H32A—C32—H32B | 107.5 |
H12A—C12—H12B | 109.5 | N4—C33—C34ii | 111.5 (3) |
C9—C12—H12C | 109.5 | N4—C33—H33A | 109.3 |
H12A—C12—H12C | 109.5 | C34ii—C33—H33A | 109.3 |
H12B—C12—H12C | 109.5 | N4—C33—H33B | 109.3 |
O4—C13—C15 | 109.9 (3) | C34ii—C33—H33B | 109.3 |
O4—C13—C14 | 110.2 (3) | H33A—C33—H33B | 108 |
C15—C13—C14 | 111.0 (3) | N4—C34—C33ii | 111.3 (3) |
O4—C13—C16 | 105.5 (3) | N4—C34—H34A | 109.4 |
C15—C13—C16 | 110.1 (3) | C33ii—C34—H34A | 109.4 |
C14—C13—C16 | 110.0 (3) | N4—C34—H34B | 109.4 |
C13—C14—H14A | 109.5 | C33ii—C34—H34B | 109.4 |
C13—C14—H14B | 109.5 | H34A—C34—H34B | 108 |
H14A—C14—H14B | 109.5 | N3—Cd1—N1 | 99.26 (10) |
C13—C14—H14C | 109.5 | N3—Cd1—S2 | 109.68 (8) |
H14A—C14—H14C | 109.5 | N1—Cd1—S2 | 111.36 (8) |
H14B—C14—H14C | 109.5 | N3—Cd1—S1 | 107.26 (8) |
C13—C15—H15A | 109.5 | N1—Cd1—S1 | 106.89 (8) |
C13—C15—H15B | 109.5 | S2—Cd1—S1 | 120.28 (3) |
H15A—C15—H15B | 109.5 | C25—N1—Cd1 | 117.7 (2) |
C13—C15—H15C | 109.5 | C25—N1—H1A | 105 (2) |
H15A—C15—H15C | 109.5 | Cd1—N1—H1A | 115 (2) |
H15B—C15—H15C | 109.5 | C25—N1—H1B | 111 (3) |
C13—C16—H16A | 109.5 | Cd1—N1—H1B | 103 (3) |
C13—C16—H16B | 109.5 | H1A—N1—H1B | 105 (4) |
H16A—C16—H16B | 109.5 | C28—N2—C27 | 110.9 (3) |
C13—C16—H16C | 109.5 | C28—N2—C29 | 108.4 (3) |
H16A—C16—H16C | 109.5 | C27—N2—C29 | 111.0 (3) |
H16B—C16—H16C | 109.5 | C30—N3—Cd1 | 115.7 (2) |
O5—C17—C18 | 109.3 (3) | C30—N3—H3A | 111 (2) |
O5—C17—C20 | 105.0 (3) | Cd1—N3—H3A | 110 (2) |
C18—C17—C20 | 110.5 (3) | C30—N3—H3B | 112 (3) |
O5—C17—C19 | 112.1 (3) | Cd1—N3—H3B | 105 (3) |
C18—C17—C19 | 109.1 (3) | H3A—N3—H3B | 102 (4) |
C20—C17—C19 | 110.9 (3) | C33—N4—C34 | 107.7 (3) |
C17—C18—H18A | 109.5 | C33—N4—C32 | 109.8 (3) |
C17—C18—H18B | 109.5 | C34—N4—C32 | 111.5 (3) |
H18A—C18—H18B | 109.5 | C1—O1—Si1 | 132.1 (2) |
C17—C18—H18C | 109.5 | C5—O2—Si1 | 134.2 (2) |
H18A—C18—H18C | 109.5 | C9—O3—Si1 | 132.0 (2) |
H18B—C18—H18C | 109.5 | C13—O4—Si2 | 134.4 (2) |
C17—C19—H19A | 109.5 | C17—O5—Si2 | 129.2 (2) |
C17—C19—H19B | 109.5 | C21—O6—Si2 | 133.8 (2) |
H19A—C19—H19B | 109.5 | Si1—S1—Cd1 | 104.26 (5) |
C17—C19—H19C | 109.5 | Si2—S2—Cd1 | 110.61 (5) |
H19A—C19—H19C | 109.5 | O2—Si1—O1 | 112.37 (13) |
H19B—C19—H19C | 109.5 | O2—Si1—O3 | 105.53 (12) |
C17—C20—H20A | 109.5 | O1—Si1—O3 | 102.90 (12) |
C17—C20—H20B | 109.5 | O2—Si1—S1 | 110.91 (10) |
H20A—C20—H20B | 109.5 | O1—Si1—S1 | 108.96 (9) |
C17—C20—H20C | 109.5 | O3—Si1—S1 | 115.98 (9) |
H20A—C20—H20C | 109.5 | O4—Si2—O6 | 105.24 (13) |
H20B—C20—H20C | 109.5 | O4—Si2—O5 | 111.65 (13) |
O6—C21—C24 | 107.9 (3) | O6—Si2—O5 | 102.77 (13) |
O6—C21—C22 | 105.6 (3) | O4—Si2—S2 | 110.06 (10) |
C24—C21—C22 | 111.3 (4) | O6—Si2—S2 | 115.55 (11) |
O6—C21—C23 | 111.1 (3) | O5—Si2—S2 | 111.29 (10) |
N1—C25—C26—C27 | −73.5 (4) | C15—C13—O4—Si2 | 80.1 (4) |
C25—C26—C27—N2 | 64.1 (4) | C14—C13—O4—Si2 | −42.6 (4) |
N3—C30—C31—C32 | −66.8 (4) | C16—C13—O4—Si2 | −161.3 (3) |
C30—C31—C32—N4 | 64.0 (4) | C18—C17—O5—Si2 | 84.9 (4) |
C26—C25—N1—Cd1 | −77.8 (3) | C20—C17—O5—Si2 | −156.6 (3) |
C29i—C28—N2—C27 | 179.5 (3) | C19—C17—O5—Si2 | −36.2 (4) |
C29i—C28—N2—C29 | −58.4 (4) | C24—C21—O6—Si2 | 87.7 (5) |
C26—C27—N2—C28 | −161.7 (3) | C22—C21—O6—Si2 | −153.3 (3) |
C26—C27—N2—C29 | 77.7 (4) | C23—C21—O6—Si2 | −35.1 (5) |
C28i—C29—N2—C28 | 58.7 (4) | C5—O2—Si1—O1 | −87.0 (3) |
C28i—C29—N2—C27 | −179.3 (3) | C5—O2—Si1—O3 | 161.6 (3) |
C31—C30—N3—Cd1 | 167.7 (2) | C5—O2—Si1—S1 | 35.2 (3) |
C34ii—C33—N4—C34 | −57.6 (4) | C1—O1—Si1—O2 | −60.1 (3) |
C34ii—C33—N4—C32 | −179.2 (3) | C1—O1—Si1—O3 | 52.9 (3) |
C33ii—C34—N4—C33 | 57.5 (4) | C1—O1—Si1—S1 | 176.5 (2) |
C33ii—C34—N4—C32 | 177.9 (3) | C9—O3—Si1—O2 | −44.0 (3) |
C31—C32—N4—C33 | −171.8 (3) | C9—O3—Si1—O1 | −162.0 (3) |
C31—C32—N4—C34 | 69.0 (4) | C9—O3—Si1—S1 | 79.2 (3) |
C3—C1—O1—Si1 | 43.1 (4) | C13—O4—Si2—O6 | −172.1 (3) |
C2—C1—O1—Si1 | −79.6 (4) | C13—O4—Si2—O5 | 77.1 (3) |
C4—C1—O1—Si1 | 162.1 (2) | C13—O4—Si2—S2 | −47.0 (3) |
C8—C5—O2—Si1 | 160.0 (3) | C21—O6—Si2—O4 | 72.9 (3) |
C7—C5—O2—Si1 | −81.5 (4) | C21—O6—Si2—O5 | −170.2 (3) |
C6—C5—O2—Si1 | 41.0 (5) | C21—O6—Si2—S2 | −48.8 (3) |
C12—C9—O3—Si1 | −50.6 (4) | C17—O5—Si2—O4 | 61.8 (3) |
C11—C9—O3—Si1 | 72.0 (4) | C17—O5—Si2—O6 | −50.5 (3) |
C10—C9—O3—Si1 | −170.2 (2) | C17—O5—Si2—S2 | −174.8 (2) |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···N2 | 0.90 (4) | 2.24 (4) | 2.977 (4) | 139 (3) |
N3—H3A···N4 | 0.96 (4) | 2.23 (4) | 2.996 (4) | 136 (3) |
N3—H3B···O5 | 0.90 (5) | 2.42 (5) | 3.256 (4) | 154 (4) |
N1—H1B···O3 | 0.85 (4) | 2.39 (4) | 3.200 (4) | 160 (3) |
N1—H1A···N2 | 0.90 (4) | 2.24 (4) | 2.977 (4) | 139 (3) |
N3—H3A···N4 | 0.96 (4) | 2.23 (4) | 2.996 (4) | 136 (3) |
N3—H3B···O5 | 0.90 (5) | 2.42 (5) | 3.256 (4) | 154 (4) |
N1—H1B···O3 | 0.85 (4) | 2.39 (4) | 3.200 (4) | 160 (3) |
[Cd2(C12H27O3SSi)4(C10H24N4)] | F(000) = 1640 |
Mr = 1543.07 | Dx = 1.256 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 67652 reflections |
a = 9.6433 (2) Å | θ = 2.2–29.6° |
b = 29.0546 (4) Å | µ = 0.73 mm−1 |
c = 14.5665 (2) Å | T = 120 K |
β = 91.466 (1)° | Prism, colorless |
V = 4079.94 (12) Å3 | 0.44 × 0.26 × 0.14 mm |
Z = 2 |
Stoe IPDS 2T diffractometer | 8337 independent reflections |
Radiation source: GeniX Mo, 0.05 x 0.05 mm2 microfocus | 7133 reflections with I > 2σ(I) |
Parabolic x-ray mirror monochromator | Rint = 0.028 |
Detector resolution: 6.67 pixels mm-1 | θmax = 26.4°, θmin = 2.2° |
rotation method, ω scans | h = −12→11 |
Absorption correction: multi-scan [LANA (Koziskova et al., 2016) in X-AREA (Stoe & Cie, 2016)] | k = −36→36 |
Tmin = 0.409, Tmax = 1.000 | l = −18→18 |
39464 measured reflections |
Refinement on F2 | 0 constraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.044 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.123 | w = 1/[σ2(Fo2) + (0.0649P)2 + 6.3741P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.002 |
8337 reflections | Δρmax = 1.52 e Å−3 |
424 parameters | Δρmin = −0.70 e Å−3 |
0 restraints |
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. Single-crystal X-ray diffraction data of compounds 1 and 2 were collected at 120 (2) K with a Stoe IPDS-2T diffractometer equipped with a graphite-monochromated Mo Kα radiation source. Crystals were cooled using a Cryostream 800 open-flow nitrogen cryostat (Oxford Cryosystems). Data collection and image processing was performed with X-AREA 1.75 (Stoe & Cie, 2016). Intensity data were scaled with LANA (part of X-AREA) in order to minimize differences in intensities of symmetry-equivalent reflections (a multi-scan method). The structures of 1 and 2 were solved using intrinsic phasing procedure implemented in SHELXT and all non-hydrogen atoms were refined with anisotropic displacement parameters by full-matrix least squares procedure based on F2 using the SHELX–2014 program package (Sheldrick, 2014; Sheldrick, 2015). The OLEX2 (Dolomanov et al., 2009) and Wingx (Farrugia, 2012) program suites were used to prepare the final version of CIF files. Mercury (Macrae et al., 2020) was used to prepare the figures. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C1 | 0.5588 (5) | 0.5996 (2) | 0.8558 (4) | 0.0749 (14) | |
C2 | 0.5340 (5) | 0.63359 (19) | 0.7809 (5) | 0.095 (2) | |
H2A | 0.609754 | 0.65608 | 0.781186 | 0.143* | |
H2B | 0.445922 | 0.649503 | 0.790336 | 0.143* | |
H2C | 0.530017 | 0.617576 | 0.721636 | 0.143* | |
C3 | 0.4417 (5) | 0.5648 (2) | 0.8601 (5) | 0.097 (2) | |
H3A | 0.430415 | 0.549423 | 0.800432 | 0.146* | |
H3B | 0.355367 | 0.580585 | 0.874924 | 0.146* | |
H3C | 0.463855 | 0.541856 | 0.907546 | 0.146* | |
C4 | 0.5806 (7) | 0.6229 (3) | 0.9496 (5) | 0.137 (4) | |
H4A | 0.601812 | 0.599425 | 0.99622 | 0.206* | |
H4B | 0.495935 | 0.639338 | 0.965748 | 0.206* | |
H4C | 0.65784 | 0.644674 | 0.946676 | 0.206* | |
C5 | 0.8052 (5) | 0.47142 (15) | 0.8720 (3) | 0.0618 (11) | |
C6 | 0.7957 (6) | 0.4939 (2) | 0.9672 (3) | 0.0762 (15) | |
H6A | 0.884169 | 0.508724 | 0.983452 | 0.114* | |
H6B | 0.775124 | 0.470267 | 1.012881 | 0.114* | |
H6C | 0.721587 | 0.516991 | 0.965833 | 0.114* | |
C7 | 0.6661 (6) | 0.4510 (2) | 0.8429 (4) | 0.0844 (17) | |
H7A | 0.594647 | 0.474988 | 0.844409 | 0.127* | |
H7B | 0.642219 | 0.426136 | 0.885017 | 0.127* | |
H7C | 0.671514 | 0.438794 | 0.780362 | 0.127* | |
C8 | 0.9188 (7) | 0.43555 (17) | 0.8713 (5) | 0.0875 (18) | |
H8A | 0.921653 | 0.421322 | 0.810427 | 0.131* | |
H8B | 0.900089 | 0.411897 | 0.91736 | 0.131* | |
H8C | 1.008229 | 0.450199 | 0.88585 | 0.131* | |
C9 | 0.9872 (4) | 0.61315 (11) | 0.7731 (2) | 0.0428 (8) | |
C10 | 1.0344 (4) | 0.59065 (14) | 0.8613 (3) | 0.0528 (9) | |
H10A | 0.956481 | 0.588852 | 0.903011 | 0.079* | |
H10B | 1.109331 | 0.608851 | 0.889907 | 0.079* | |
H10C | 1.068212 | 0.559557 | 0.84844 | 0.079* | |
C11 | 1.1119 (5) | 0.61852 (16) | 0.7099 (3) | 0.0619 (11) | |
H11A | 1.157037 | 0.588581 | 0.702246 | 0.093* | |
H11B | 1.178369 | 0.640354 | 0.73735 | 0.093* | |
H11C | 1.079681 | 0.63002 | 0.649773 | 0.093* | |
C12 | 0.9228 (5) | 0.65858 (15) | 0.7876 (4) | 0.0738 (14) | |
H12A | 0.882495 | 0.66984 | 0.729404 | 0.111* | |
H12B | 0.993513 | 0.680319 | 0.810246 | 0.111* | |
H12C | 0.849816 | 0.655759 | 0.832838 | 0.111* | |
C13 | 0.4108 (4) | 0.67627 (13) | 0.4306 (3) | 0.0457 (8) | |
C14 | 0.3193 (5) | 0.65446 (19) | 0.5000 (4) | 0.0782 (15) | |
H14A | 0.325732 | 0.620891 | 0.495232 | 0.117* | |
H14B | 0.22301 | 0.664081 | 0.488269 | 0.117* | |
H14C | 0.349184 | 0.664165 | 0.561803 | 0.117* | |
C15 | 0.3950 (5) | 0.72749 (16) | 0.4309 (5) | 0.0850 (18) | |
H15A | 0.420542 | 0.739487 | 0.491886 | 0.127* | |
H15B | 0.298334 | 0.735542 | 0.415877 | 0.127* | |
H15C | 0.455629 | 0.740988 | 0.38514 | 0.127* | |
C16 | 0.3733 (5) | 0.6568 (2) | 0.3361 (4) | 0.092 (2) | |
H16A | 0.436021 | 0.669522 | 0.290678 | 0.138* | |
H16B | 0.277481 | 0.665102 | 0.319355 | 0.138* | |
H16C | 0.382362 | 0.623194 | 0.337415 | 0.138* | |
C17 | 0.7558 (5) | 0.76129 (14) | 0.5443 (3) | 0.0592 (11) | |
C18 | 0.6874 (6) | 0.73649 (18) | 0.6259 (3) | 0.0728 (13) | |
H18A | 0.586574 | 0.735938 | 0.615913 | 0.109* | |
H18B | 0.710126 | 0.752992 | 0.683023 | 0.109* | |
H18C | 0.722449 | 0.704884 | 0.630356 | 0.109* | |
C19 | 0.9114 (5) | 0.76228 (18) | 0.5556 (5) | 0.0854 (18) | |
H19A | 0.946356 | 0.730801 | 0.563261 | 0.128* | |
H19B | 0.937499 | 0.78054 | 0.609939 | 0.128* | |
H19C | 0.951673 | 0.776141 | 0.501068 | 0.128* | |
C20 | 0.6968 (6) | 0.81000 (16) | 0.5331 (5) | 0.0841 (17) | |
H20A | 0.7371 | 0.824684 | 0.479431 | 0.126* | |
H20B | 0.719876 | 0.828109 | 0.588196 | 0.126* | |
H20C | 0.595816 | 0.808352 | 0.524643 | 0.126* | |
C21 | 0.7964 (5) | 0.70335 (16) | 0.2538 (3) | 0.0589 (11) | |
C22 | 0.7513 (6) | 0.75199 (17) | 0.2354 (4) | 0.0760 (14) | |
H22A | 0.655537 | 0.752091 | 0.211282 | 0.114* | |
H22B | 0.812191 | 0.765916 | 0.190241 | 0.114* | |
H22C | 0.756867 | 0.769709 | 0.292611 | 0.114* | |
C23 | 0.7778 (7) | 0.6750 (2) | 0.1673 (4) | 0.0903 (18) | |
H23A | 0.814866 | 0.64399 | 0.17792 | 0.135* | |
H23B | 0.827675 | 0.68964 | 0.117249 | 0.135* | |
H23C | 0.678949 | 0.673005 | 0.150522 | 0.135* | |
C24 | 0.9449 (5) | 0.7001 (3) | 0.2888 (5) | 0.110 (3) | |
H24A | 0.957238 | 0.719357 | 0.343654 | 0.165* | |
H24B | 1.007119 | 0.710839 | 0.241098 | 0.165* | |
H24C | 0.966823 | 0.668064 | 0.304286 | 0.165* | |
C25 | 0.6447 (5) | 0.56335 (16) | 0.3111 (3) | 0.0597 (11) | |
H25A | 0.68287 | 0.594731 | 0.30369 | 0.072* | |
H25B | 0.567501 | 0.559657 | 0.265539 | 0.072* | |
C26 | 0.8977 (5) | 0.54003 (16) | 0.3355 (3) | 0.0575 (10) | |
H26A | 0.967787 | 0.523448 | 0.299611 | 0.069* | |
H26B | 0.917402 | 0.57335 | 0.330286 | 0.069* | |
C27 | 0.7513 (6) | 0.53043 (17) | 0.2910 (3) | 0.0692 (13) | |
H27A | 0.760771 | 0.529008 | 0.22354 | 0.083* | |
H27B | 0.720132 | 0.499725 | 0.311532 | 0.083* | |
C28 | 0.9024 (4) | 0.47707 (14) | 0.4433 (3) | 0.0513 (9) | |
H28A | 0.96518 | 0.461824 | 0.399961 | 0.062* | |
H28B | 0.806228 | 0.467714 | 0.426877 | 0.062* | |
C29 | 1.0624 (4) | 0.53866 (13) | 0.4609 (3) | 0.0472 (8) | |
H29A | 1.126508 | 0.524071 | 0.417599 | 0.057* | |
H29B | 1.074611 | 0.572426 | 0.456899 | 0.057* | |
Cd1 | 0.75028 (2) | 0.57009 (2) | 0.52053 (2) | 0.03435 (9) | |
O1 | 0.6846 (3) | 0.57472 (10) | 0.84279 (18) | 0.0516 (7) | |
O2 | 0.8463 (3) | 0.50641 (8) | 0.80641 (18) | 0.0471 (6) | |
O3 | 0.8888 (3) | 0.58334 (8) | 0.72319 (16) | 0.0423 (5) | |
O4 | 0.5517 (2) | 0.66226 (8) | 0.45481 (17) | 0.0399 (5) | |
O5 | 0.7181 (3) | 0.73814 (8) | 0.45944 (19) | 0.0468 (6) | |
O6 | 0.7036 (3) | 0.68365 (9) | 0.31954 (17) | 0.0483 (6) | |
N1 | 0.5903 (3) | 0.55928 (12) | 0.4017 (2) | 0.0453 (7) | |
N2 | 0.9149 (3) | 0.52636 (11) | 0.4339 (2) | 0.0495 (7) | |
S1 | 0.6456 (7) | 0.53026 (17) | 0.6479 (3) | 0.0345 (8) | 0.79 (3) |
S1A | 0.607 (3) | 0.5374 (8) | 0.6507 (12) | 0.046 (3) | 0.21 (3) |
S2 | 0.8577 (3) | 0.64623 (17) | 0.4982 (4) | 0.0356 (6) | 0.79 (3) |
S2A | 0.8612 (14) | 0.6350 (10) | 0.468 (3) | 0.049 (6) | 0.21 (3) |
Si1 | 0.76506 (10) | 0.55055 (3) | 0.76074 (6) | 0.0356 (2) | |
Si2 | 0.70303 (9) | 0.68408 (3) | 0.43116 (6) | 0.0353 (2) | |
H1A | 0.535 (5) | 0.5363 (17) | 0.406 (3) | 0.059 (13)* | |
H1B | 0.540 (5) | 0.5817 (16) | 0.415 (3) | 0.055 (13)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.051 (2) | 0.095 (4) | 0.079 (3) | 0.011 (2) | 0.003 (2) | −0.033 (3) |
C2 | 0.058 (3) | 0.066 (3) | 0.162 (6) | 0.023 (2) | −0.010 (3) | −0.021 (4) |
C3 | 0.046 (3) | 0.143 (6) | 0.103 (5) | 0.003 (3) | 0.015 (3) | −0.007 (4) |
C4 | 0.087 (4) | 0.198 (8) | 0.127 (6) | 0.038 (5) | 0.009 (4) | −0.107 (6) |
C5 | 0.060 (2) | 0.051 (2) | 0.074 (3) | −0.0213 (19) | −0.012 (2) | 0.020 (2) |
C6 | 0.077 (3) | 0.093 (4) | 0.057 (3) | −0.024 (3) | −0.012 (2) | 0.027 (3) |
C7 | 0.083 (4) | 0.083 (4) | 0.086 (4) | −0.044 (3) | −0.014 (3) | 0.024 (3) |
C8 | 0.107 (5) | 0.047 (3) | 0.107 (5) | 0.000 (3) | −0.012 (4) | 0.022 (3) |
C9 | 0.051 (2) | 0.0323 (16) | 0.0448 (18) | −0.0139 (15) | −0.0060 (15) | −0.0050 (14) |
C10 | 0.052 (2) | 0.055 (2) | 0.050 (2) | −0.0161 (18) | −0.0107 (17) | 0.0024 (18) |
C11 | 0.068 (3) | 0.064 (3) | 0.054 (2) | −0.032 (2) | 0.007 (2) | −0.011 (2) |
C12 | 0.073 (3) | 0.040 (2) | 0.108 (4) | 0.001 (2) | −0.021 (3) | −0.019 (2) |
C13 | 0.0313 (17) | 0.0438 (19) | 0.062 (2) | 0.0045 (14) | 0.0025 (15) | −0.0015 (17) |
C14 | 0.045 (2) | 0.080 (3) | 0.109 (4) | −0.006 (2) | 0.013 (3) | 0.021 (3) |
C15 | 0.042 (2) | 0.048 (2) | 0.164 (6) | 0.0092 (19) | −0.012 (3) | 0.011 (3) |
C16 | 0.058 (3) | 0.136 (5) | 0.081 (4) | 0.036 (3) | −0.026 (3) | −0.024 (4) |
C17 | 0.062 (3) | 0.039 (2) | 0.075 (3) | 0.0043 (18) | −0.021 (2) | −0.0077 (19) |
C18 | 0.087 (4) | 0.074 (3) | 0.058 (3) | 0.019 (3) | −0.006 (2) | −0.010 (2) |
C19 | 0.061 (3) | 0.057 (3) | 0.136 (5) | −0.007 (2) | −0.036 (3) | 0.001 (3) |
C20 | 0.082 (3) | 0.041 (2) | 0.127 (5) | 0.007 (2) | −0.036 (3) | −0.013 (3) |
C21 | 0.065 (3) | 0.061 (3) | 0.051 (2) | 0.012 (2) | 0.0159 (19) | 0.0226 (19) |
C22 | 0.086 (3) | 0.063 (3) | 0.079 (3) | 0.007 (3) | 0.011 (3) | 0.029 (3) |
C23 | 0.121 (5) | 0.086 (4) | 0.065 (3) | 0.030 (4) | 0.032 (3) | 0.013 (3) |
C24 | 0.050 (3) | 0.160 (6) | 0.121 (5) | 0.013 (3) | 0.031 (3) | 0.079 (5) |
C25 | 0.070 (3) | 0.063 (3) | 0.045 (2) | −0.010 (2) | −0.015 (2) | −0.0003 (19) |
C26 | 0.071 (3) | 0.055 (2) | 0.047 (2) | 0.007 (2) | 0.0044 (19) | −0.0032 (18) |
C27 | 0.095 (4) | 0.066 (3) | 0.045 (2) | 0.007 (3) | −0.020 (2) | −0.009 (2) |
C28 | 0.053 (2) | 0.049 (2) | 0.052 (2) | −0.0096 (17) | −0.0019 (17) | −0.0039 (17) |
C29 | 0.052 (2) | 0.0387 (18) | 0.051 (2) | −0.0152 (16) | 0.0028 (16) | −0.0003 (15) |
Cd1 | 0.03965 (15) | 0.02768 (13) | 0.03571 (14) | 0.00312 (9) | 0.00060 (9) | −0.00117 (9) |
O1 | 0.0463 (14) | 0.0671 (18) | 0.0416 (14) | 0.0015 (12) | 0.0030 (11) | −0.0168 (12) |
O2 | 0.0465 (14) | 0.0386 (13) | 0.0558 (15) | −0.0086 (11) | −0.0031 (12) | 0.0080 (11) |
O3 | 0.0510 (14) | 0.0396 (12) | 0.0361 (12) | −0.0166 (11) | −0.0060 (10) | −0.0016 (10) |
O4 | 0.0325 (12) | 0.0377 (12) | 0.0493 (13) | −0.0004 (9) | −0.0022 (10) | 0.0046 (10) |
O5 | 0.0442 (14) | 0.0365 (13) | 0.0595 (15) | 0.0013 (10) | −0.0041 (12) | 0.0045 (11) |
O6 | 0.0452 (14) | 0.0556 (15) | 0.0443 (14) | 0.0114 (12) | 0.0062 (11) | 0.0106 (12) |
N1 | 0.0406 (16) | 0.0336 (15) | 0.061 (2) | −0.0015 (14) | −0.0073 (14) | −0.0045 (14) |
N2 | 0.0546 (19) | 0.0474 (18) | 0.0461 (17) | 0.0029 (14) | −0.0058 (14) | −0.0028 (14) |
S1 | 0.0320 (17) | 0.0389 (12) | 0.0326 (8) | −0.0092 (10) | −0.0008 (10) | −0.0026 (7) |
S1A | 0.038 (7) | 0.056 (6) | 0.043 (3) | −0.008 (5) | −0.002 (4) | −0.012 (4) |
S2 | 0.0366 (7) | 0.0252 (10) | 0.0446 (14) | 0.0020 (6) | −0.0061 (7) | 0.0023 (9) |
S2A | 0.033 (3) | 0.036 (7) | 0.077 (12) | −0.008 (3) | −0.016 (5) | 0.021 (8) |
Si1 | 0.0413 (5) | 0.0346 (5) | 0.0309 (4) | −0.0071 (4) | 0.0005 (4) | −0.0009 (3) |
Si2 | 0.0327 (4) | 0.0322 (4) | 0.0411 (5) | 0.0022 (3) | 0.0005 (4) | 0.0059 (4) |
C1—O1 | 1.430 (5) | C18—H18B | 0.98 |
C1—C2 | 1.486 (9) | C18—H18C | 0.98 |
C1—C3 | 1.519 (8) | C19—H19A | 0.98 |
C1—C4 | 1.533 (8) | C19—H19B | 0.98 |
C2—H2A | 0.98 | C19—H19C | 0.98 |
C2—H2B | 0.98 | C20—H20A | 0.98 |
C2—H2C | 0.98 | C20—H20B | 0.98 |
C3—H3A | 0.98 | C20—H20C | 0.98 |
C3—H3B | 0.98 | C21—O6 | 1.445 (5) |
C3—H3C | 0.98 | C21—C22 | 1.501 (6) |
C4—H4A | 0.98 | C21—C24 | 1.510 (7) |
C4—H4B | 0.98 | C21—C23 | 1.513 (7) |
C4—H4C | 0.98 | C22—H22A | 0.98 |
C5—O2 | 1.457 (5) | C22—H22B | 0.98 |
C5—C8 | 1.512 (7) | C22—H22C | 0.98 |
C5—C7 | 1.517 (6) | C23—H23A | 0.98 |
C5—C6 | 1.538 (7) | C23—H23B | 0.98 |
C6—H6A | 0.98 | C23—H23C | 0.98 |
C6—H6B | 0.98 | C24—H24A | 0.98 |
C6—H6C | 0.98 | C24—H24B | 0.98 |
C7—H7A | 0.98 | C24—H24C | 0.98 |
C7—H7B | 0.98 | C25—N1 | 1.439 (6) |
C7—H7C | 0.98 | C25—C27 | 1.440 (7) |
C8—H8A | 0.98 | C25—H25A | 0.99 |
C8—H8B | 0.98 | C25—H25B | 0.99 |
C8—H8C | 0.98 | C26—N2 | 1.493 (5) |
C9—O3 | 1.464 (4) | C26—C27 | 1.563 (7) |
C9—C12 | 1.476 (5) | C26—H26A | 0.99 |
C9—C10 | 1.502 (5) | C26—H26B | 0.99 |
C9—C11 | 1.542 (6) | C27—H27A | 0.99 |
C10—H10A | 0.98 | C27—H27B | 0.99 |
C10—H10B | 0.98 | C28—N2 | 1.444 (5) |
C10—H10C | 0.98 | C28—C29i | 1.499 (5) |
C11—H11A | 0.98 | C28—H28A | 0.99 |
C11—H11B | 0.98 | C28—H28B | 0.99 |
C11—H11C | 0.98 | C29—N2 | 1.508 (5) |
C12—H12A | 0.98 | C29—H29A | 0.99 |
C12—H12B | 0.98 | C29—H29B | 0.99 |
C12—H12C | 0.98 | Cd1—S2A | 2.309 (10) |
C13—O4 | 1.453 (4) | Cd1—N1 | 2.310 (3) |
C13—C15 | 1.496 (6) | Cd1—N2 | 2.415 (3) |
C13—C14 | 1.499 (6) | Cd1—S1 | 2.428 (4) |
C13—C16 | 1.523 (6) | Cd1—S2 | 2.468 (5) |
C14—H14A | 0.98 | Cd1—S1A | 2.56 (2) |
C14—H14B | 0.98 | O1—Si1 | 1.603 (3) |
C14—H14C | 0.98 | O2—Si1 | 1.635 (3) |
C15—H15A | 0.98 | O3—Si1 | 1.632 (2) |
C15—H15B | 0.98 | O4—Si2 | 1.636 (2) |
C15—H15C | 0.98 | O5—Si2 | 1.629 (3) |
C16—H16A | 0.98 | O6—Si2 | 1.626 (3) |
C16—H16B | 0.98 | N1—H1A | 0.86 (5) |
C16—H16C | 0.98 | N1—H1B | 0.84 (5) |
C17—O5 | 1.445 (5) | S1—Si1 | 2.068 (4) |
C17—C19 | 1.506 (6) | S1A—Si1 | 2.22 (2) |
C17—C20 | 1.532 (6) | S2—S2A | 0.55 (5) |
C17—C18 | 1.551 (7) | S2—Si2 | 2.077 (3) |
C18—H18A | 0.98 | S2A—Si2 | 2.146 (18) |
O1—C1—C2 | 111.1 (4) | H20A—C20—H20B | 109.5 |
O1—C1—C3 | 107.6 (5) | C17—C20—H20C | 109.5 |
C2—C1—C3 | 111.5 (5) | H20A—C20—H20C | 109.5 |
O1—C1—C4 | 104.1 (4) | H20B—C20—H20C | 109.5 |
C2—C1—C4 | 112.2 (6) | O6—C21—C22 | 108.0 (4) |
C3—C1—C4 | 110.0 (6) | O6—C21—C24 | 110.5 (3) |
C1—C2—H2A | 109.5 | C22—C21—C24 | 112.7 (5) |
C1—C2—H2B | 109.5 | O6—C21—C23 | 105.9 (4) |
H2A—C2—H2B | 109.5 | C22—C21—C23 | 109.6 (4) |
C1—C2—H2C | 109.5 | C24—C21—C23 | 109.8 (5) |
H2A—C2—H2C | 109.5 | C21—C22—H22A | 109.5 |
H2B—C2—H2C | 109.5 | C21—C22—H22B | 109.5 |
C1—C3—H3A | 109.5 | H22A—C22—H22B | 109.5 |
C1—C3—H3B | 109.5 | C21—C22—H22C | 109.5 |
H3A—C3—H3B | 109.5 | H22A—C22—H22C | 109.5 |
C1—C3—H3C | 109.5 | H22B—C22—H22C | 109.5 |
H3A—C3—H3C | 109.5 | C21—C23—H23A | 109.5 |
H3B—C3—H3C | 109.5 | C21—C23—H23B | 109.5 |
C1—C4—H4A | 109.5 | H23A—C23—H23B | 109.5 |
C1—C4—H4B | 109.5 | C21—C23—H23C | 109.5 |
H4A—C4—H4B | 109.5 | H23A—C23—H23C | 109.5 |
C1—C4—H4C | 109.5 | H23B—C23—H23C | 109.5 |
H4A—C4—H4C | 109.5 | C21—C24—H24A | 109.5 |
H4B—C4—H4C | 109.5 | C21—C24—H24B | 109.5 |
O2—C5—C8 | 105.5 (4) | H24A—C24—H24B | 109.5 |
O2—C5—C7 | 110.1 (4) | C21—C24—H24C | 109.5 |
C8—C5—C7 | 111.4 (5) | H24A—C24—H24C | 109.5 |
O2—C5—C6 | 108.6 (3) | H24B—C24—H24C | 109.5 |
C8—C5—C6 | 111.0 (4) | N1—C25—C27 | 114.2 (4) |
C7—C5—C6 | 110.2 (4) | N1—C25—H25A | 108.7 |
C5—C6—H6A | 109.5 | C27—C25—H25A | 108.7 |
C5—C6—H6B | 109.5 | N1—C25—H25B | 108.7 |
H6A—C6—H6B | 109.5 | C27—C25—H25B | 108.7 |
C5—C6—H6C | 109.5 | H25A—C25—H25B | 107.6 |
H6A—C6—H6C | 109.5 | N2—C26—C27 | 115.3 (4) |
H6B—C6—H6C | 109.5 | N2—C26—H26A | 108.4 |
C5—C7—H7A | 109.5 | C27—C26—H26A | 108.4 |
C5—C7—H7B | 109.5 | N2—C26—H26B | 108.4 |
H7A—C7—H7B | 109.5 | C27—C26—H26B | 108.4 |
C5—C7—H7C | 109.5 | H26A—C26—H26B | 107.5 |
H7A—C7—H7C | 109.5 | C25—C27—C26 | 116.1 (4) |
H7B—C7—H7C | 109.5 | C25—C27—H27A | 108.3 |
C5—C8—H8A | 109.5 | C26—C27—H27A | 108.3 |
C5—C8—H8B | 109.5 | C25—C27—H27B | 108.3 |
H8A—C8—H8B | 109.5 | C26—C27—H27B | 108.3 |
C5—C8—H8C | 109.5 | H27A—C27—H27B | 107.4 |
H8A—C8—H8C | 109.5 | N2—C28—C29i | 111.9 (3) |
H8B—C8—H8C | 109.5 | N2—C28—H28A | 109.2 |
O3—C9—C12 | 109.3 (3) | C29i—C28—H28A | 109.2 |
O3—C9—C10 | 110.2 (3) | N2—C28—H28B | 109.2 |
C12—C9—C10 | 112.7 (4) | C29i—C28—H28B | 109.2 |
O3—C9—C11 | 105.6 (3) | H28A—C28—H28B | 107.9 |
C12—C9—C11 | 109.4 (4) | C28i—C29—N2 | 111.1 (3) |
C10—C9—C11 | 109.3 (3) | C28i—C29—H29A | 109.4 |
C9—C10—H10A | 109.5 | N2—C29—H29A | 109.4 |
C9—C10—H10B | 109.5 | C28i—C29—H29B | 109.4 |
H10A—C10—H10B | 109.5 | N2—C29—H29B | 109.4 |
C9—C10—H10C | 109.5 | H29A—C29—H29B | 108 |
H10A—C10—H10C | 109.5 | S2A—Cd1—N1 | 99.7 (8) |
H10B—C10—H10C | 109.5 | S2A—Cd1—N2 | 86.5 (12) |
C9—C11—H11A | 109.5 | N1—Cd1—N2 | 88.42 (11) |
C9—C11—H11B | 109.5 | S2A—Cd1—S1 | 148.0 (13) |
H11A—C11—H11B | 109.5 | N1—Cd1—S1 | 103.01 (15) |
C9—C11—H11C | 109.5 | N2—Cd1—S1 | 116.12 (19) |
H11A—C11—H11C | 109.5 | S2A—Cd1—S2 | 12.7 (12) |
H11B—C11—H11C | 109.5 | N1—Cd1—S2 | 107.32 (14) |
C9—C12—H12A | 109.5 | N2—Cd1—S2 | 96.83 (13) |
C9—C12—H12B | 109.5 | S1—Cd1—S2 | 135.39 (13) |
H12A—C12—H12B | 109.5 | S2A—Cd1—S1A | 144.5 (11) |
C9—C12—H12C | 109.5 | N1—Cd1—S1A | 98.2 (5) |
H12A—C12—H12C | 109.5 | N2—Cd1—S1A | 124.5 (7) |
H12B—C12—H12C | 109.5 | C1—O1—Si1 | 138.5 (3) |
O4—C13—C15 | 111.9 (3) | C5—O2—Si1 | 132.7 (3) |
O4—C13—C14 | 106.3 (3) | C9—O3—Si1 | 130.5 (2) |
C15—C13—C14 | 110.9 (4) | C13—O4—Si2 | 132.4 (2) |
O4—C13—C16 | 108.3 (3) | C17—O5—Si2 | 133.1 (2) |
C15—C13—C16 | 110.5 (5) | C21—O6—Si2 | 132.6 (3) |
C14—C13—C16 | 108.8 (4) | C25—N1—Cd1 | 115.1 (3) |
C13—C14—H14A | 109.5 | C25—N1—H1A | 112 (3) |
C13—C14—H14B | 109.5 | Cd1—N1—H1A | 117 (3) |
H14A—C14—H14B | 109.5 | C25—N1—H1B | 112 (3) |
C13—C14—H14C | 109.5 | Cd1—N1—H1B | 96 (3) |
H14A—C14—H14C | 109.5 | H1A—N1—H1B | 103 (4) |
H14B—C14—H14C | 109.5 | C28—N2—C26 | 110.3 (3) |
C13—C15—H15A | 109.5 | C28—N2—C29 | 106.9 (3) |
C13—C15—H15B | 109.5 | C26—N2—C29 | 105.6 (3) |
H15A—C15—H15B | 109.5 | C28—N2—Cd1 | 114.5 (3) |
C13—C15—H15C | 109.5 | C26—N2—Cd1 | 107.7 (2) |
H15A—C15—H15C | 109.5 | C29—N2—Cd1 | 111.5 (2) |
H15B—C15—H15C | 109.5 | Si1—S1—Cd1 | 103.74 (19) |
C13—C16—H16A | 109.5 | Si1—S1A—Cd1 | 95.6 (9) |
C13—C16—H16B | 109.5 | S2A—S2—Si2 | 89.7 (13) |
H16A—C16—H16B | 109.5 | S2A—S2—Cd1 | 67.0 (14) |
C13—C16—H16C | 109.5 | Si2—S2—Cd1 | 103.75 (19) |
H16A—C16—H16C | 109.5 | S2—S2A—Si2 | 75 (2) |
H16B—C16—H16C | 109.5 | S2—S2A—Cd1 | 100 (2) |
O5—C17—C19 | 109.3 (4) | Si2—S2A—Cd1 | 107.0 (5) |
O5—C17—C20 | 104.7 (4) | O1—Si1—O3 | 111.48 (14) |
C19—C17—C20 | 111.1 (4) | O1—Si1—O2 | 106.02 (15) |
O5—C17—C18 | 109.7 (3) | O3—Si1—O2 | 104.32 (14) |
C19—C17—C18 | 111.5 (4) | O1—Si1—S1 | 116.5 (2) |
C20—C17—C18 | 110.3 (4) | O3—Si1—S1 | 107.29 (16) |
C17—C18—H18A | 109.5 | O2—Si1—S1 | 110.54 (19) |
C17—C18—H18B | 109.5 | O1—Si1—S1A | 106.2 (9) |
H18A—C18—H18B | 109.5 | O3—Si1—S1A | 110.7 (5) |
C17—C18—H18C | 109.5 | O2—Si1—S1A | 118.1 (7) |
H18A—C18—H18C | 109.5 | O6—Si2—O5 | 104.93 (14) |
H18B—C18—H18C | 109.5 | O6—Si2—O4 | 103.50 (14) |
C17—C19—H19A | 109.5 | O5—Si2—O4 | 113.26 (14) |
C17—C19—H19B | 109.5 | O6—Si2—S2 | 116.43 (18) |
H19A—C19—H19B | 109.5 | O5—Si2—S2 | 109.5 (2) |
C17—C19—H19C | 109.5 | O4—Si2—S2 | 109.24 (12) |
H19A—C19—H19C | 109.5 | O6—Si2—S2A | 102.9 (13) |
H19B—C19—H19C | 109.5 | O5—Si2—S2A | 121.3 (10) |
C17—C20—H20A | 109.5 | O4—Si2—S2A | 108.8 (3) |
C17—C20—H20B | 109.5 | S2—Si2—S2A | 14.9 (12) |
N1—C25—C27—C26 | −75.9 (5) | C28i—C29—N2—C26 | −175.1 (3) |
N2—C26—C27—C25 | 79.8 (5) | C28i—C29—N2—Cd1 | 68.2 (3) |
C2—C1—O1—Si1 | −42.7 (7) | Cd1—S2—S2A—Si2 | 105.1 (5) |
C3—C1—O1—Si1 | 79.7 (6) | Si2—S2—S2A—Cd1 | −105.1 (5) |
C4—C1—O1—Si1 | −163.6 (5) | C1—O1—Si1—O3 | 99.8 (5) |
C8—C5—O2—Si1 | 169.5 (3) | C1—O1—Si1—O2 | −147.3 (5) |
C7—C5—O2—Si1 | 49.2 (6) | C1—O1—Si1—S1 | −23.8 (5) |
C6—C5—O2—Si1 | −71.5 (5) | C1—O1—Si1—S1A | −20.8 (7) |
C12—C9—O3—Si1 | −85.6 (4) | C9—O3—Si1—O1 | 39.4 (3) |
C10—C9—O3—Si1 | 38.8 (5) | C9—O3—Si1—O2 | −74.6 (3) |
C11—C9—O3—Si1 | 156.7 (3) | C9—O3—Si1—S1 | 168.1 (3) |
C15—C13—O4—Si2 | −37.4 (5) | C9—O3—Si1—S1A | 157.3 (10) |
C14—C13—O4—Si2 | −158.6 (3) | C5—O2—Si1—O1 | 43.1 (4) |
C16—C13—O4—Si2 | 84.6 (5) | C5—O2—Si1—O3 | 160.9 (3) |
C19—C17—O5—Si2 | 81.9 (5) | C5—O2—Si1—S1 | −84.0 (4) |
C20—C17—O5—Si2 | −159.0 (3) | C5—O2—Si1—S1A | −75.7 (9) |
C18—C17—O5—Si2 | −40.7 (5) | C21—O6—Si2—O5 | 51.6 (3) |
C22—C21—O6—Si2 | −86.2 (4) | C21—O6—Si2—O4 | 170.6 (3) |
C24—C21—O6—Si2 | 37.6 (6) | C21—O6—Si2—S2 | −69.6 (4) |
C23—C21—O6—Si2 | 156.4 (3) | C21—O6—Si2—S2A | −76.2 (6) |
C27—C25—N1—Cd1 | 61.1 (4) | C17—O5—Si2—O6 | −163.3 (3) |
C29i—C28—N2—C26 | 172.5 (3) | C17—O5—Si2—O4 | 84.6 (4) |
C29i—C28—N2—C29 | 58.2 (5) | C17—O5—Si2—S2 | −37.6 (4) |
C29i—C28—N2—Cd1 | −65.9 (4) | C17—O5—Si2—S2A | −47.6 (13) |
C27—C26—N2—C28 | 64.6 (5) | C13—O4—Si2—O6 | −58.9 (3) |
C27—C26—N2—C29 | 179.8 (3) | C13—O4—Si2—O5 | 54.1 (3) |
C27—C26—N2—Cd1 | −61.0 (4) | C13—O4—Si2—S2 | 176.4 (3) |
C28i—C29—N2—C28 | −57.7 (4) | C13—O4—Si2—S2A | −167.9 (15) |
Symmetry code: (i) −x+2, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···S1ii | 0.86 (5) | 2.70 (5) | 3.519 (5) | 159 (4) |
N1—H1B···O4 | 0.84 (5) | 2.41 (5) | 3.115 (4) | 142 (4) |
Symmetry code: (ii) −x+1, −y+1, −z+1. |
Acknowledgements
The research was supported by the `Excellence Initiative – Research University' programs at Gdańsk University of Technology and the Silicium Supporting Core R&D Facilities program (crystallographic measurements). Computations were carried out using the computers of Centre of Informatics Tricity Academic Supercomputer & Network.
Funding information
Funding for the crystallographic measurements was provided by: Gdańsk University of Technology (grant No. DEC-2/2021/IDUB/V.6/Si).
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