research communications
of 2-(methylamino)tropone
aDepartment of Chemistry, PO Box 339, University of the Free State, Bloemfontein, 9301, South Africa
*Correspondence e-mail: SchutteM@ufs.ac.za
The title compound, 2-(methylamino)cyclohepta-2,4,6-trien-1-one, C8H9NO, crystallizes in the monoclinic P21/c, with three independent molecules in the The planarity of the molecules is indicated by planes fitted through the seven ring carbon atoms. Small deviations from the planes, with an extremal r.m.s. deviation of 0.0345 Å, are present. In complexes of transition metals with similar ligands, the large planar seven-membered aromatic rings have shown to improve the stability of the complex. Two types of hydrogen-bonding interactions, C—H⋯O and N—H⋯O, are observed, as well as bifurcation of these interactions. The N—H⋯O interactions link molecules to form infinite chains. The packing of molecules in the shows a pattern of overlapping aromatic rings, forming column-like formations. π–π interactions are observed between the overlapping aromatic rings at 3.4462 (19) Å from each other.
Keywords: crystal structure; 2-(methylamino)tropone; tropolone.
CCDC reference: 1937929
1. Chemical context
Tropolone and other troponoids, non-benzenoid compounds, have great pharmacological potential (Guo et al., 2019). They display a wide range of bioactivities, including antimicrobial (Saleh et al., 1988), antiviral (Tavis & Lomonosova, 2015) and antitumor (Ononye et al., 2013) activities. Many tropolone-related compounds have proved to be possible antiproliferative agents against a variety of cancer cell lines, including lung, prostate and T-cell malignancies (Liu & Yamauchi, 2006; Hsiao et al., 2012). Tropolone has important medical applications in radiopharmacy (Nepveu et al., 1993) and as catalyst precursor (Crous et al., 2005; Roodt et al., 2003).
Tropolone and its derivatives are versatile ligands used in inorganic and organometallic chemistry (Roesky, 2000; Dias et al., 1995; Nozoe et al., 1997; Schutte et al., 2010; Steyl et al., 2010). The carbonyl oxygen and vicinal coordinating substituent, specifically nitrogen in this study, impart a metal-chelating ability to these types of ligands. The complexes of these ligands with first and second row transition elements have increased over the past few decades. The ligands of importance in this study and future work, namely 2-(alkylamino)tropones and aminotroponimines, are N,O and N,N′ bidentate, monoanionic ligands containing a ten π-electron backbone (Roesky, 2000). The π-conjugated backbone is characteristic of these ligands (Nishinaga et al., 2010). Considering the above-mentioned characteristics, tropolone could be considered analogous to the O-donor κ2-O,O′ acetylacetonate ligand (acac-O,O′). The tropolone bidentate ligand differs from the acac-O,O′ ligand in a few ways. Of importance to our study is the larger aromatic delocalization, which could afford greater polarizability. Tropolone is also more acidic than the acac-O,O′ ligand. The acidity of the O,N and N,N′ bidentate ligands used in our study and the effect thereof on the chelating ability could be compared to these O,O′ bidentate ligands described in the literature. The ligand–metal–ligand angle, better known as the `bite angle', would also be smaller for a tropolone-derived complex, since it would form a five-membered metallocycle instead of a six-membered one as with acac-O,O′ (Bhalla et al., 2005). This could show interesting steric and electronic influences at the metal centre and could be further compared to the steric and electronic studies conveyed on β-diketone moieties in similar metal complexes by Manicum et al. (2018). These ligands, including the title compound, 2-(methylamino)tropone, will form part of the synthesis of water-soluble complexes of rhenium(I) tricarbonyl, gallium(III) and copper(II). Rhenium(I) (Schutte-Smith et al., 2019), gallium(III) (Green & Welch, 1989) and copper(II) (Boschi et al., 2018) are highly utilized radioisotopes in the radiopharmaceutical industry.
When designing diagnostic or therapeutic radiopharmaceuticals, certain mechanistic aspects are very important, as it is the basis on which some predictions are made regarding the in vivo behaviour. Kinetic studies, utilizing different techniques, are executed to determine the reaction mechanisms by which the proposed radiopharmaceutical complexes will form and react. Results of such studies are important in nuclear medicine as it gives indications regarding the in vivo stability, uptake and excretion as well as the pharmacokinetics of the compounds. Kinetic investigations by Schutte et al. (2011, 2012), Schutte-Smith et al. (2019) and Manicum et al. (2019) were done on rhenium(I) tricarbonyl tropolonato complexes with satisfying results and conclusions. In the study, methanol substitution was studied using entering nucleophiles in fac-[Re(Trop)(CO)3(MeOH)]. The kinetic study performed at high pressure indicated positive volumes of activation for all of the reactions studied. This was a clear indication towards a dissociative interchange mechanism.
The application of these ligands in coordination chemistry could be further increased by adding electron donating or withdrawing moieties to the nitrogen atom.
2. Structural commentary
2-(Methylamino)tropone crystallizes in the monoclinic P21/c with three independent molecules, A, B and C, in the (Fig. 1). The bond distances and angles of the three molecules agree well with each other and with those in similar structures (Barret et al., 2014; Dwivedi et al., 2016; Roesky & Bürgstein, 1999; Shimanouchi & Sasada, 1973; Siwatch et al., 2011). The largest differences in bond distances are of the C8B—N1B [1.4470 (18) Å], N1B—C2B [1.3444 (17) Å] and O1B—C1B [1.2561 (15) Å] bonds with the corresponding bonds in 2-(t-butylamino)tropone [1.472 (4) Å; Siwatch et al., 2011], 2-(isopropylamino)tropone [1.330 (4) Å; Roesky & Bürgstein, 1999] and 2-(t-butylamino)tropone [1.242 (4) Å; Siwatch et al., 2011], respectively. Compared to the starting material molecule, tropolone (Shimanouchi & Sasada, 1973), the O1B—C1B [1.2561 (15) Å] bond distance is slightly shorter than that of tropolone [1.261 (3) Å], both being in the range of normal C=O bond distance. The C2—N1—C8 bond angle in molecules A [125.69 (13)°], B [125.27 (13)°] and C [125.07 (12)°] are slightly larger than the usual 120° for trigonal-planar bond angles, because of the steric influence of the methyl group. These angles are close to the same angle in 2-(benzylamino)tropone [125.09 (12)°; Barret et al., 2014]. This could be compared to the large angle in 2-(t-butylamino)tropone [131.9 (2)°; Siwatch et al., 2011], which deviates even more from 120° due to the highly steric tertiary butyl group. A plane fitted through the seven ring carbon atoms of the three molecules in the indicates that the molecules are planar. The root-mean-square deviations of molecules A, B and C from the planes are 0.0141 (12), 0.0261 (11) and 0.0345 (11) Å, respectively. The C8—N1—C2—C3 torsion angle, which involves the methyl group, differs for molecule A [−0.8 (2)°], molecule B [2.3 (2)°] and molecule C [7.7 (2)°]. The small deviations from planarity could possibly be ascribed to the intermolecular hydrogen-bonding interactions.
3. Supramolecular features
Nine hydrogen-bonding interactions, three C—H⋯O and six N—H⋯O, are observed (Table 1 and Fig. 2). Infinite chains are formed along [001]. These supramolecular chains are formed through N—H⋯O interactions linking the molecules together. As in the of tropolone (Shimanouchi & Sasada, 1973), bifurcation of the hydrogen bonds take place. Bifurcation, also known as the over-coordination of a hydrogen bond, creates both inter- and intramolecular branches, which might contribute to the stability of the structures. This is an interesting phenomenon seen in the orientation of water molecules, where the distribution of acceptor hydrogen bonds, terminating at the lone pairs of the oxygen, is higher (Markovitch & Agmon, 2008). This forms over-coordinated oxygens and could also be seen in this (Fig. 2). These interactions clearly contribute to the array of the molecules in the (Fig. 2). The molecules show an interesting packing format in the `Column'-like structures are formed by molecule B packing in a head-to-tail pattern with the aromatic rings overlapping (Fig. 3). A π-interaction is observed, with a perpendicular distance of 3.4462 (19) Å between the overlapping aromatic rings of two inversion-related B molecules (Fig. 4). These π-interactions could not only possibly contribute to the packing format of the molecules in the but could also assist in the formation of one-dimensional infinite chains, as Wong et al. (2018) have found in water-soluble platinum (II) salts.
4. Database survey
A search of the Cambridge Structural Database (CSD, Version 5.40, update of February 2019; Groom et al., 2016) using a C7H5ONH fragment yielded four hits of 2-(alkylamino)tropones. These include 2-(isopropylamino)tropone (LIGVOM: Roesky & Bürgstein, 1999), 2-(benzylamino)tropone (NOPRUH: Barret et al., 2014), 2-(t-butylamino)tropone (OZINUH: Siwatch et al., 2011) and 2-(cyclohexylamino)tropone (OTIMUB: Dwivedi et al., 2016). Of the four structures, only the 2-(isopropylamino)tropone and the 2-(benzylamino)tropone crystallize in the P21/c space group.
5. Synthesis and crystallization
Tropolone (505 mg, 4.132 mmol) was dissolved in 20 mL of a 40% methylamine solution. The reaction mixture was stirred at room temperature for 7 d. The product was extracted three times with 30 mL of chloroform, and the organic layer was washed with 50 mL of water. The organic layer was dried with Na2SO4 and the solvent removed under reduced pressure. A 46.03% yield (257.1 mg, 1.902 mmol) was obtained. Crystals suitable for single crystal X-ray diffraction data collection were obtained by recrystallization from hexane with slow evaporation. Yield: 0.2571 g, 46.03%. IR (cm−1): νNH = 3304, νCO = 1597. UV/Vis: λmax = 269 nm (∊ = 1.1885 × 105 Lmol−1cm−1). 1H NMR (300 MHz, CDCl3): δ = 7.201 (m, 4H), 6.682 (t, 1H, J = 9.6 Hz), 6.501 (d, 1H, J = 10.5 Hz), 3.056 (d, 3H, J = 5.4 Hz). 13C NMR (300MHz, CDCl3): δ = 177, 157, 137, 136, 129, 122, 108, 29.
6. Refinement
Crystal data, data collection and structure . Methyl and aromatic hydrogen atoms were placed in geometrically idealized positions (C—H = 0.95–0.98 Å) and constrained to ride on their parent atoms [Uiso(H) = 1.5Ueq(C) and 1.2Ueq(C)], while N—H hydrogens were freely refined.
details are summarized in Table 2
|
Supporting information
CCDC reference: 1937929
https://doi.org/10.1107/S2056989019009502/pk2619sup1.cif
contains datablocks global, I. DOI:Supporting information file. DOI: https://doi.org/10.1107/S2056989019009502/pk2619Isup2.cml
Data collection: APEX2 (Bruker, 2012); cell
SAINT-Plus (Bruker, 2012); data reduction: SAINT-Plus (Bruker, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: WinGX (Farrugia, 2012).C8H9NO | F(000) = 864 |
Mr = 135.16 | Dx = 1.249 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 6617 reflections |
a = 17.635 (5) Å | θ = 3.5–23.7° |
b = 7.817 (2) Å | µ = 0.08 mm−1 |
c = 16.718 (4) Å | T = 100 K |
β = 110.639 (9)° | Cuboid, yellow |
V = 2156.8 (10) Å3 | 0.58 × 0.30 × 0.28 mm |
Z = 12 |
Bruker X8 APEXII 4K Kappa CCD diffractometer | 5192 independent reflections |
Radiation source: fine-focus sealed tube | 3575 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.046 |
ω scans | θmax = 28.0°, θmin = 3.7° |
Absorption correction: multi-scan SADABS (Krause et al., 2015) | h = −23→23 |
Tmin = 0.970, Tmax = 0.977 | k = −10→10 |
33879 measured reflections | l = −20→22 |
Refinement on F2 | Secondary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.039 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.104 | w = 1/[σ2(Fo2) + (0.0361P)2 + 0.437P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
5192 reflections | Δρmax = 0.17 e Å−3 |
287 parameters | Δρmin = −0.13 e Å−3 |
0 restraints | Extinction correction: SHELXL2018 (Sheldrick, 2015) |
0 constraints | Extinction coefficient: 0.0113 (9) |
Primary atom site location: structure-invariant direct methods |
Experimental. The intensity data was collected on a Bruker X8 ApexII 4K Kappa CCD diffractometer using an exposure time of 10 seconds/frame. A total of 1436 frames was collected with a frame width of 0.5° covering up to θ = 27.99° with 99.7% completeness accomplished. |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
C8A | 0.12323 (10) | 0.5412 (2) | 0.21119 (10) | 0.0626 (4) | |
H8A1 | 0.113602 | 0.421239 | 0.221702 | 0.094* | |
H8A2 | 0.172571 | 0.549845 | 0.197169 | 0.094* | |
H8A3 | 0.077051 | 0.584932 | 0.163359 | 0.094* | |
C8B | 0.49672 (10) | 0.4930 (2) | 0.26816 (10) | 0.0586 (4) | |
H8B1 | 0.530729 | 0.588791 | 0.263364 | 0.088* | |
H8B2 | 0.47058 | 0.440852 | 0.2118 | 0.088* | |
H8B3 | 0.530411 | 0.407538 | 0.307747 | 0.088* | |
C8C | 0.19718 (11) | 0.2656 (2) | −0.10383 (9) | 0.0588 (4) | |
H8C1 | 0.234672 | 0.189118 | −0.117954 | 0.088* | |
H8C2 | 0.187004 | 0.367098 | −0.140513 | 0.088* | |
H8C3 | 0.145975 | 0.20569 | −0.113027 | 0.088* | |
N1A | 0.13282 (7) | 0.64142 (16) | 0.28726 (8) | 0.0460 (3) | |
N1B | 0.43536 (8) | 0.55487 (16) | 0.29999 (8) | 0.0454 (3) | |
N1C | 0.23250 (7) | 0.31715 (16) | −0.01509 (7) | 0.0450 (3) | |
O1A | 0.17457 (6) | 0.83578 (13) | 0.41777 (6) | 0.0530 (3) | |
O1B | 0.30974 (5) | 0.61826 (14) | 0.33715 (6) | 0.0515 (3) | |
O1C | 0.28810 (7) | 0.46038 (12) | 0.13314 (6) | 0.0574 (3) | |
HN1A | 0.1803 (10) | 0.689 (2) | 0.3149 (10) | 0.064 (5)* | |
HN1B | 0.3829 (9) | 0.5397 (19) | 0.2695 (10) | 0.052 (4)* | |
HN1C | 0.2345 (9) | 0.428 (2) | −0.0016 (10) | 0.056 (5)* | |
C1B | 0.37461 (8) | 0.67009 (17) | 0.39220 (8) | 0.0379 (3) | |
C2B | 0.44995 (7) | 0.63079 (16) | 0.37612 (8) | 0.0379 (3) | |
C3B | 0.52868 (8) | 0.66224 (19) | 0.43132 (9) | 0.0476 (3) | |
H3B | 0.569782 | 0.625712 | 0.410663 | 0.057* | |
C4B | 0.55733 (9) | 0.7385 (2) | 0.51194 (10) | 0.0545 (4) | |
H4B | 0.614666 | 0.74095 | 0.538203 | 0.065* | |
C5B | 0.51628 (9) | 0.8101 (2) | 0.55919 (10) | 0.0553 (4) | |
H5B | 0.548086 | 0.855301 | 0.613404 | 0.066* | |
C6B | 0.43262 (9) | 0.82372 (19) | 0.53599 (9) | 0.0510 (4) | |
H6B | 0.414495 | 0.882838 | 0.575565 | 0.061* | |
C7B | 0.37249 (8) | 0.76418 (18) | 0.46432 (8) | 0.0437 (3) | |
H7B | 0.319314 | 0.790761 | 0.462424 | 0.052* | |
C1C | 0.27959 (8) | 0.30140 (16) | 0.13520 (8) | 0.0396 (3) | |
C2C | 0.25275 (7) | 0.21032 (16) | 0.05204 (8) | 0.0346 (3) | |
C3C | 0.24942 (8) | 0.03409 (16) | 0.03938 (9) | 0.0406 (3) | |
H3C | 0.236584 | −0.000441 | −0.018381 | 0.049* | |
C4C | 0.26179 (8) | −0.09981 (17) | 0.09743 (9) | 0.0460 (3) | |
H4C | 0.257336 | −0.210933 | 0.073189 | 0.055* | |
C5C | 0.27941 (9) | −0.09661 (19) | 0.18414 (10) | 0.0495 (4) | |
H5C | 0.283417 | −0.204059 | 0.211879 | 0.059* | |
C6C | 0.29204 (8) | 0.0487 (2) | 0.23568 (9) | 0.0491 (4) | |
H6C | 0.301651 | 0.026655 | 0.294322 | 0.059* | |
C7C | 0.29278 (8) | 0.21802 (19) | 0.21506 (9) | 0.0458 (3) | |
H7C | 0.304073 | 0.293672 | 0.262311 | 0.055* | |
C1A | 0.10733 (8) | 0.76484 (17) | 0.40289 (8) | 0.0411 (3) | |
C2A | 0.07897 (8) | 0.65224 (16) | 0.32681 (8) | 0.0395 (3) | |
C3A | 0.00556 (8) | 0.56527 (19) | 0.29566 (10) | 0.0538 (4) | |
H3A | −0.003564 | 0.505768 | 0.243542 | 0.065* | |
C4A | −0.05654 (9) | 0.5510 (2) | 0.32809 (13) | 0.0647 (5) | |
H4A | −0.100588 | 0.48099 | 0.295409 | 0.078* | |
C5A | −0.06451 (10) | 0.6213 (2) | 0.39924 (13) | 0.0702 (5) | |
H5A | −0.112064 | 0.59234 | 0.410595 | 0.084* | |
C6A | −0.01009 (11) | 0.7312 (3) | 0.45709 (12) | 0.0707 (5) | |
H6A | −0.026039 | 0.768486 | 0.502906 | 0.085* | |
C7A | 0.06298 (10) | 0.7941 (2) | 0.45827 (10) | 0.0584 (4) | |
H7A | 0.088461 | 0.870606 | 0.504039 | 0.07* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C8A | 0.0635 (10) | 0.0735 (11) | 0.0479 (9) | −0.0028 (9) | 0.0162 (8) | −0.0172 (8) |
C8B | 0.0646 (10) | 0.0627 (10) | 0.0585 (10) | 0.0095 (8) | 0.0343 (8) | 0.0034 (8) |
C8C | 0.0758 (11) | 0.0571 (9) | 0.0380 (8) | 0.0003 (8) | 0.0132 (7) | 0.0016 (7) |
N1A | 0.0412 (7) | 0.0501 (7) | 0.0437 (7) | −0.0052 (6) | 0.0114 (5) | −0.0085 (6) |
N1B | 0.0432 (7) | 0.0527 (7) | 0.0421 (7) | 0.0019 (6) | 0.0171 (6) | 0.0013 (5) |
N1C | 0.0587 (7) | 0.0373 (6) | 0.0384 (6) | −0.0010 (5) | 0.0164 (5) | −0.0014 (5) |
O1A | 0.0484 (6) | 0.0480 (6) | 0.0582 (6) | −0.0073 (5) | 0.0132 (5) | −0.0137 (5) |
O1B | 0.0353 (5) | 0.0712 (7) | 0.0441 (6) | −0.0060 (5) | 0.0091 (4) | −0.0063 (5) |
O1C | 0.0861 (8) | 0.0361 (5) | 0.0494 (6) | −0.0083 (5) | 0.0230 (6) | −0.0073 (5) |
C1B | 0.0360 (7) | 0.0408 (7) | 0.0354 (7) | −0.0023 (5) | 0.0106 (5) | 0.0074 (5) |
C2B | 0.0385 (7) | 0.0371 (7) | 0.0388 (7) | −0.0007 (5) | 0.0146 (6) | 0.0094 (6) |
C3B | 0.0355 (7) | 0.0566 (9) | 0.0517 (8) | 0.0001 (6) | 0.0166 (6) | 0.0091 (7) |
C4B | 0.0353 (7) | 0.0669 (10) | 0.0522 (9) | −0.0082 (7) | 0.0042 (6) | 0.0085 (8) |
C5B | 0.0516 (9) | 0.0634 (10) | 0.0422 (8) | −0.0135 (7) | 0.0056 (7) | −0.0022 (7) |
C6B | 0.0576 (9) | 0.0530 (9) | 0.0425 (8) | −0.0058 (7) | 0.0177 (7) | −0.0046 (7) |
C7B | 0.0409 (7) | 0.0497 (8) | 0.0417 (7) | −0.0007 (6) | 0.0158 (6) | 0.0021 (6) |
C1C | 0.0402 (7) | 0.0381 (7) | 0.0416 (7) | −0.0022 (5) | 0.0158 (6) | −0.0058 (6) |
C2C | 0.0327 (6) | 0.0361 (6) | 0.0365 (7) | 0.0003 (5) | 0.0141 (5) | −0.0009 (5) |
C3C | 0.0445 (7) | 0.0367 (7) | 0.0417 (7) | −0.0003 (6) | 0.0164 (6) | −0.0054 (6) |
C4C | 0.0478 (8) | 0.0337 (7) | 0.0571 (9) | 0.0026 (6) | 0.0192 (7) | −0.0010 (6) |
C5C | 0.0486 (8) | 0.0423 (8) | 0.0561 (9) | 0.0042 (6) | 0.0165 (7) | 0.0120 (7) |
C6C | 0.0462 (8) | 0.0590 (9) | 0.0393 (8) | −0.0020 (7) | 0.0117 (6) | 0.0074 (7) |
C7C | 0.0492 (8) | 0.0502 (8) | 0.0372 (7) | −0.0054 (6) | 0.0143 (6) | −0.0050 (6) |
C1A | 0.0396 (7) | 0.0367 (7) | 0.0420 (7) | 0.0057 (6) | 0.0080 (6) | 0.0033 (6) |
C2A | 0.0368 (7) | 0.0347 (7) | 0.0417 (7) | 0.0039 (5) | 0.0072 (6) | 0.0032 (6) |
C3A | 0.0406 (8) | 0.0510 (8) | 0.0620 (10) | −0.0038 (6) | 0.0086 (7) | −0.0062 (7) |
C4A | 0.0392 (8) | 0.0596 (10) | 0.0907 (13) | −0.0038 (7) | 0.0170 (8) | 0.0064 (9) |
C5A | 0.0445 (9) | 0.0794 (12) | 0.0920 (14) | 0.0088 (9) | 0.0308 (9) | 0.0247 (11) |
C6A | 0.0661 (11) | 0.0884 (13) | 0.0683 (11) | 0.0241 (10) | 0.0372 (10) | 0.0169 (10) |
C7A | 0.0603 (10) | 0.0643 (10) | 0.0504 (9) | 0.0113 (8) | 0.0194 (8) | −0.0021 (8) |
C8A—N1A | 1.4518 (19) | C4B—H4B | 0.95 |
C8A—H8A1 | 0.98 | C5B—C6B | 1.391 (2) |
C8A—H8A2 | 0.98 | C5B—H5B | 0.95 |
C8A—H8A3 | 0.98 | C6B—C7B | 1.3716 (19) |
C8B—N1B | 1.4470 (18) | C6B—H6B | 0.95 |
C8B—H8B1 | 0.98 | C7B—H7B | 0.95 |
C8B—H8B2 | 0.98 | C1C—C7C | 1.4293 (19) |
C8B—H8B3 | 0.98 | C1C—C2C | 1.4832 (18) |
C8C—N1C | 1.4492 (18) | C2C—C3C | 1.3919 (18) |
C8C—H8C1 | 0.98 | C3C—C4C | 1.3913 (19) |
C8C—H8C2 | 0.98 | C3C—H3C | 0.95 |
C8C—H8C3 | 0.98 | C4C—C5C | 1.372 (2) |
N1A—C2A | 1.3376 (18) | C4C—H4C | 0.95 |
N1A—HN1A | 0.884 (17) | C5C—C6C | 1.395 (2) |
N1B—C2B | 1.3444 (17) | C5C—H5C | 0.95 |
N1B—HN1B | 0.893 (15) | C6C—C7C | 1.369 (2) |
N1C—C2C | 1.3423 (16) | C6C—H6C | 0.95 |
N1C—HN1C | 0.890 (16) | C7C—H7C | 0.95 |
O1A—O1A | 0.000 (3) | C1A—C7A | 1.426 (2) |
O1A—C1A | 1.2519 (16) | C1A—C2A | 1.4812 (19) |
O1B—O1B | 0.0000 (19) | C2A—C3A | 1.3906 (19) |
O1B—C1B | 1.2561 (15) | C3A—C4A | 1.387 (2) |
O1C—O1C | 0.000 (3) | C3A—H3A | 0.95 |
O1C—C1C | 1.2537 (16) | C4A—C5A | 1.362 (3) |
C1B—C7B | 1.4240 (19) | C4A—H4A | 0.95 |
C1B—C2B | 1.4777 (18) | C5A—C6A | 1.393 (3) |
C2B—C3B | 1.3917 (19) | C5A—H5A | 0.95 |
C3B—C4B | 1.395 (2) | C6A—C7A | 1.373 (2) |
C3B—H3B | 0.95 | C6A—H6A | 0.95 |
C4B—C5B | 1.366 (2) | C7A—H7A | 0.95 |
N1A—C8A—H8A1 | 109.5 | C6B—C7B—C1B | 132.22 (14) |
N1A—C8A—H8A2 | 109.5 | C6B—C7B—H7B | 113.9 |
H8A1—C8A—H8A2 | 109.5 | C1B—C7B—H7B | 113.9 |
N1A—C8A—H8A3 | 109.5 | O1C—C1C—O1C | 0.00 (10) |
H8A1—C8A—H8A3 | 109.5 | O1C—C1C—C7C | 119.73 (12) |
H8A2—C8A—H8A3 | 109.5 | O1C—C1C—C7C | 119.73 (12) |
N1B—C8B—H8B1 | 109.5 | O1C—C1C—C2C | 116.86 (12) |
N1B—C8B—H8B2 | 109.5 | O1C—C1C—C2C | 116.86 (12) |
H8B1—C8B—H8B2 | 109.5 | C7C—C1C—C2C | 123.36 (12) |
N1B—C8B—H8B3 | 109.5 | N1C—C2C—C3C | 120.28 (12) |
H8B1—C8B—H8B3 | 109.5 | N1C—C2C—C1C | 112.83 (11) |
H8B2—C8B—H8B3 | 109.5 | C3C—C2C—C1C | 126.87 (12) |
N1C—C8C—H8C1 | 109.5 | C4C—C3C—C2C | 130.60 (13) |
N1C—C8C—H8C2 | 109.5 | C4C—C3C—H3C | 114.7 |
H8C1—C8C—H8C2 | 109.5 | C2C—C3C—H3C | 114.7 |
N1C—C8C—H8C3 | 109.5 | C5C—C4C—C3C | 130.16 (13) |
H8C1—C8C—H8C3 | 109.5 | C5C—C4C—H4C | 114.9 |
H8C2—C8C—H8C3 | 109.5 | C3C—C4C—H4C | 114.9 |
C2A—N1A—C8A | 125.69 (13) | C4C—C5C—C6C | 126.51 (13) |
C2A—N1A—HN1A | 115.0 (11) | C4C—C5C—H5C | 116.7 |
C8A—N1A—HN1A | 118.8 (11) | C6C—C5C—H5C | 116.7 |
C2B—N1B—C8B | 125.27 (13) | C7C—C6C—C5C | 130.18 (14) |
C2B—N1B—HN1B | 114.4 (10) | C7C—C6C—H6C | 114.9 |
C8B—N1B—HN1B | 120.3 (10) | C5C—C6C—H6C | 114.9 |
C2C—N1C—C8C | 125.07 (12) | C6C—C7C—C1C | 131.55 (13) |
C2C—N1C—HN1C | 114.7 (10) | C6C—C7C—H7C | 114.2 |
C8C—N1C—HN1C | 119.5 (10) | C1C—C7C—H7C | 114.2 |
O1A—O1A—C1A | 0 (10) | O1A—C1A—O1A | 0.00 (9) |
O1B—O1B—C1B | 0 (10) | O1A—C1A—C7A | 119.86 (13) |
O1C—O1C—C1C | 0 (10) | O1A—C1A—C7A | 119.86 (13) |
O1B—C1B—O1B | 0.00 (15) | O1A—C1A—C2A | 116.32 (12) |
O1B—C1B—C7B | 119.87 (12) | O1A—C1A—C2A | 116.32 (12) |
O1B—C1B—C7B | 119.87 (12) | C7A—C1A—C2A | 123.82 (13) |
O1B—C1B—C2B | 116.40 (12) | N1A—C2A—C3A | 120.88 (13) |
O1B—C1B—C2B | 116.40 (12) | N1A—C2A—C1A | 112.23 (11) |
C7B—C1B—C2B | 123.72 (12) | C3A—C2A—C1A | 126.88 (13) |
N1B—C2B—C3B | 121.26 (12) | C4A—C3A—C2A | 130.67 (16) |
N1B—C2B—C1B | 112.32 (11) | C4A—C3A—H3A | 114.7 |
C3B—C2B—C1B | 126.40 (13) | C2A—C3A—H3A | 114.7 |
C2B—C3B—C4B | 130.76 (14) | C5A—C4A—C3A | 130.39 (16) |
C2B—C3B—H3B | 114.6 | C5A—C4A—H4A | 114.8 |
C4B—C3B—H3B | 114.6 | C3A—C4A—H4A | 114.8 |
C5B—C4B—C3B | 130.44 (14) | C4A—C5A—C6A | 126.67 (16) |
C5B—C4B—H4B | 114.8 | C4A—C5A—H5A | 116.7 |
C3B—C4B—H4B | 114.8 | C6A—C5A—H5A | 116.7 |
C4B—C5B—C6B | 126.62 (14) | C7A—C6A—C5A | 130.12 (17) |
C4B—C5B—H5B | 116.7 | C7A—C6A—H6A | 114.9 |
C6B—C5B—H5B | 116.7 | C5A—C6A—H6A | 114.9 |
C7B—C6B—C5B | 129.43 (15) | C6A—C7A—C1A | 131.32 (16) |
C7B—C6B—H6B | 115.3 | C6A—C7A—H7A | 114.3 |
C5B—C6B—H6B | 115.3 | C1A—C7A—H7A | 114.3 |
O1B—O1B—C1B—C7B | 0.00 (7) | N1C—C2C—C3C—C4C | −174.98 (13) |
O1B—O1B—C1B—C2B | 0.00 (11) | C1C—C2C—C3C—C4C | 7.0 (2) |
C8B—N1B—C2B—C3B | 2.3 (2) | C2C—C3C—C4C—C5C | 1.4 (3) |
C8B—N1B—C2B—C1B | −176.57 (13) | C3C—C4C—C5C—C6C | −2.5 (3) |
O1B—C1B—C2B—N1B | 4.66 (16) | C4C—C5C—C6C—C7C | −2.3 (3) |
O1B—C1B—C2B—N1B | 4.66 (16) | C5C—C6C—C7C—C1C | 1.4 (3) |
C7B—C1B—C2B—N1B | −174.08 (12) | O1C—C1C—C7C—C6C | −175.92 (15) |
O1B—C1B—C2B—C3B | −174.13 (13) | O1C—C1C—C7C—C6C | −175.92 (15) |
O1B—C1B—C2B—C3B | −174.13 (13) | C2C—C1C—C7C—C6C | 6.6 (2) |
C7B—C1B—C2B—C3B | 7.1 (2) | O1A—O1A—C1A—C7A | 0.00 (3) |
N1B—C2B—C3B—C4B | 179.84 (15) | O1A—O1A—C1A—C2A | 0.00 (2) |
C1B—C2B—C3B—C4B | −1.5 (2) | C8A—N1A—C2A—C3A | −0.8 (2) |
C2B—C3B—C4B—C5B | −2.6 (3) | C8A—N1A—C2A—C1A | 179.80 (13) |
C3B—C4B—C5B—C6B | −0.1 (3) | O1A—C1A—C2A—N1A | 1.88 (17) |
C4B—C5B—C6B—C7B | 3.1 (3) | O1A—C1A—C2A—N1A | 1.88 (17) |
C5B—C6B—C7B—C1B | 0.8 (3) | C7A—C1A—C2A—N1A | −177.78 (13) |
O1B—C1B—C7B—C6B | 174.25 (15) | O1A—C1A—C2A—C3A | −177.44 (13) |
O1B—C1B—C7B—C6B | 174.25 (15) | O1A—C1A—C2A—C3A | −177.44 (13) |
C2B—C1B—C7B—C6B | −7.1 (2) | C7A—C1A—C2A—C3A | 2.9 (2) |
O1C—O1C—C1C—C7C | 0.0 (2) | N1A—C2A—C3A—C4A | 176.30 (16) |
O1C—O1C—C1C—C2C | 0.0 (2) | C1A—C2A—C3A—C4A | −4.4 (3) |
C8C—N1C—C2C—C3C | 7.7 (2) | C2A—C3A—C4A—C5A | 1.6 (3) |
C8C—N1C—C2C—C1C | −174.00 (13) | C3A—C4A—C5A—C6A | 1.5 (3) |
O1C—C1C—C2C—N1C | −7.16 (17) | C4A—C5A—C6A—C7A | −0.6 (3) |
O1C—C1C—C2C—N1C | −7.16 (17) | C5A—C6A—C7A—C1A | −1.8 (3) |
C7C—C1C—C2C—N1C | 170.43 (12) | O1A—C1A—C7A—C6A | −178.88 (16) |
O1C—C1C—C2C—C3C | 171.01 (13) | O1A—C1A—C7A—C6A | −178.88 (16) |
O1C—C1C—C2C—C3C | 171.01 (13) | C2A—C1A—C7A—C6A | 0.8 (3) |
C7C—C1C—C2C—C3C | −11.4 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—HN1A···O1A | 0.884 (17) | 2.099 (16) | 2.5453 (16) | 110.3 (13) |
N1A—HN1A···O1B | 0.884 (17) | 2.248 (17) | 2.9375 (17) | 134.6 (14) |
N1B—HN1B···O1B | 0.893 (15) | 2.085 (15) | 2.5513 (16) | 111.5 (12) |
N1B—HN1B···O1C | 0.893 (15) | 2.385 (15) | 3.1566 (18) | 144.7 (13) |
N1C—HN1C···O1C | 0.890 (16) | 2.130 (15) | 2.5775 (16) | 110.3 (12) |
N1C—HN1C···O1Ai | 0.890 (16) | 2.313 (16) | 2.9759 (17) | 131.3 (13) |
C5C—H5C···O1Bii | 0.95 | 2.42 | 3.2914 (19) | 153 |
C7B—H7B···O1A | 0.95 | 2.42 | 3.3446 (19) | 165 |
C8C—H8C2···O1Ai | 0.98 | 2.56 | 3.178 (2) | 121 |
Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) x, y−1, z. |
Acknowledgements
This work is based on the research supported in part by the National Research Foundation of South Africa. We would also like to thank the University of the Free State.
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