Planarity of benzoyldithiocarbazate tuberculostatics. II. Diesters of benzoyldithiocarbazic acid
Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229615024201/sk3609sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615024201/sk3609G1sup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615024201/sk3609G2sup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615024201/sk3609G3sup4.hkl | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229615024201/sk3609G1sup5.cml | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229615024201/sk3609G2sup6.cml | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229615024201/sk3609G3sup7.cml |
CCDC references: 1442946; 1442945; 1442944
The emergence of drug-resistant strains of Mycobacterium tuberculosis intensified efforts made in order to identify new lead tuberculostatics. In our earlier studies, the structures of six series of compounds (denoted A–F in Scheme 1) were reported with the aim of identifying structural features responsible for tuberculostatic activity (Olczak et al., 2007, 2011; Szczesio et al., 2011, 2012a,b). As a result, it was concluded that planarity of the molecules correlates well with their activity. According to our hypothesis, only derivatives whose molecules are capable of adopting a planar conformation may show tuberculostatic activity (Olczak et al., 2007).
In this study, five more crystal structures (denoted G in Scheme 1) are described, three of which are reported for the first time (denoted G1, G2 and G3 in Scheme 2) and two have been deposited in the Cambridge Structural Database (CSD; Version ????; Groom & Allen, 2014) (denoted G4 and G5 in Scheme 2). Basic crystallographic information on the latter two structures, namely N'-[bis(methylsulfanyl)methylidene]-2-nitrobenzohydrazide (G4) and N'-[bis(methylsulfanyl)methylidene]-4-nitrobenzohydrazide (G5), were presented in our earlier report (Gobis et al., 2012). As G5 turned out to show tuberculostatic activity, we decided to determine the structures of other nitro derivatives with the aim of evaluating the influence of aromatic ring substituents on the activity and to further test the `planarity hypothesis'.
The syntheses of G1, G2 and G3 was described by Gobis et al. (2012). Single crystals of G1, G2 and G3 suitable for X-ray diffraction analysis were obtained from methanol solutions by slow evaporation of the solvent at room temperature.
Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms were located in difference Fourier maps and subsequently geometrically optimized and allowed for as riding atoms, with C—H = 0.95 Å for aromatic CH groups, 0.97 Å for secondary CH2 groups and 0.96 Å for methyl groups, and N—H = 0.86 Å, with Uiso(H) = 1.2Ueq(C,N). In G1, the C3 methyl group was refined with two conformations about the N3—C3 bond with six half-occupied H atoms 60° apart. For both G1 and G2, an extinction parameter was refined.
Ab initio calculations were performed using the GAMESS-US quantum computing package (Gordon & Schmidt, 2005), using DFT/M06-2X functional (Zhao & Truhlar, 2008) with base functions 6-311 G(d,p). The MOLDEN package was used for the preparation of input files and visualization purposes (Schaftenaar & Noordik, 2000).
The molecular structures of compounds G1–G3 are shown in Fig. 1. One of the factors affecting the general conformation of the studied molecules is the methyl substitution at the N3 atom. This substitution determines the conformation around the N3—C4 bond. In the N3-substituted derivatives G1 and G2, the torsion angle C3—N3—C4—O5 is -11.3 (2) (G1), 10.5 (3) (G2, molecule A) and 9.3 (3)° (G2, molecule B), indicating a syn conformation, whereas for G3 and G5, the respective torsion angle H3—N3—C4—O5 is -177 (G3) and -161° (G5) (anti conformation). The G5 structure for which the angle H3—N3—C4—O5 is -1° is an exception. The reason for this less common conformation may be the presence of the NO2 group in the ortho position, which enforces a different hydrogen-bond system (Table 2), packing and significant twist of the phenyl ring. Among the eight analogous compounds found in the CSD with a methyl substituent on atom N3, only one exhibits an anti conformation (Fig. 2a), while as many as 848 fragments in 872 N3—H derivatives show this conformation (Fig. 2b).
As for the aromatic ring orientation, similar to chloro derivatives (Szczesio et al., 2012a,b), the twist of the ring relative to the C(═ O)—N fragment is more than 30° [37.1 (1)° in G1, 51.3 (1) and 66.7 (1)° in the two molecules of G2, and 31.7 (1)° in G3]. In G2, a unique part of the unit cell is formed by two independent molecules interacting only by weak C—H···O contacts (Table 3). As a consequence of very weak dispersion interactions, the benzyl substituents at the S atoms reveal large libration motion with the displacement parameter reaching a value of 0.31 Å2 for the C25A atom. The molecular packing in G3 is determined mainly by N3—H···O5 hydrogen bonds (Fig. 3 and Table 4), owing to which infinite C(4) chains (according to the graph-set definition of Bernstein et al., 1995) are formed parallel to the [101] direction. In addition, the intramolecular weak N3—H···S1 hydrogen bond labelled as S(5) favours flattening of the molecule. The molecular packing in G5 is determined by a similar hydrogen bond (N3—H···O5). In G1 and G2, only weak contacts of the C—H···O type exist (Tables 5 and 3, respectively). In G5, molecular dimers [R22(8)] are formed as a result of N3—H···O5 hydrogen bonds (Fig. 4).
Basic crystallographic parameters of two analogous structures (G4 and G5; Scheme 2), differing only in the position of the nitro group in the aromatic ring, were given in our earlier work (Gobis et al., 2012).
Among the compounds presented in this study, G5 (Scheme 2) shows the highest tuberculostatic activity (Gobis et al. 2011). Molecules of this compound are almost planar. Methyl groups at the S atoms are small enough to allow planar due to the weak intramolecular N—H···S hydrogen bond. The relatively high activity of this compound confirms our hypothesis on the importance of the planarity for the tuberculostatic activity of this group of compounds.
The conformation of G5 (the most active compound) was also optimized with the density functional theory (DFT) method. The resulting geometry (with an anti conformation for O5—C4—N3—H3) was very similar to that found in the crystal state (Fig. 5). The largest difference for these geometries is observed for the C1—N2—N3—C4 torsion angle, which amount to 21.4° (Table 6). This suggests that intermolecular interactions in the crystal do not affect the geometry of the molecule significantly.
Additionally, a G5 molecule with a modified O5—C4—N3—H torsion angle (19.5°) to the syn conformation was optimized with the same method. Interestingly, the energy minimum for this conformation, (the O5—C4—N3—H torsion angle after optimization approximately equals -5°) (Table 6) is almost the same (only 1 kcal mol-1 lower), which suggests that among the two energetically equivalent syn/anti conformations, the latter is preferred in the crystalline state due to intermolecular interactions.
Another important factor influencing the activity is the position of the nitro group substituted in the aromatic ring. For G5 (Scheme 2) the twist of the aromatic ring in regard to the C(═O)—N group equals 57.9 (1)° due to the steric repulsion introduced by the nitro group. The above findings are in agreement with the hypothesis that planarity of the whole molecule is crucial for tuberculostatic activity and that the substituents at sulfur atoms should be small.
The emergence of drug-resistant strains of Mycobacterium tuberculosis intensified efforts made in order to identify new lead tuberculostatics. In our earlier studies, the structures of six series of compounds (denoted A–F in Scheme 1) were reported with the aim of identifying structural features responsible for tuberculostatic activity (Olczak et al., 2007, 2011; Szczesio et al., 2011, 2012a,b). As a result, it was concluded that planarity of the molecules correlates well with their activity. According to our hypothesis, only derivatives whose molecules are capable of adopting a planar conformation may show tuberculostatic activity (Olczak et al., 2007).
In this study, five more crystal structures (denoted G in Scheme 1) are described, three of which are reported for the first time (denoted G1, G2 and G3 in Scheme 2) and two have been deposited in the Cambridge Structural Database (CSD; Version ????; Groom & Allen, 2014) (denoted G4 and G5 in Scheme 2). Basic crystallographic information on the latter two structures, namely N'-[bis(methylsulfanyl)methylidene]-2-nitrobenzohydrazide (G4) and N'-[bis(methylsulfanyl)methylidene]-4-nitrobenzohydrazide (G5), were presented in our earlier report (Gobis et al., 2012). As G5 turned out to show tuberculostatic activity, we decided to determine the structures of other nitro derivatives with the aim of evaluating the influence of aromatic ring substituents on the activity and to further test the `planarity hypothesis'.
Ab initio calculations were performed using the GAMESS-US quantum computing package (Gordon & Schmidt, 2005), using DFT/M06-2X functional (Zhao & Truhlar, 2008) with base functions 6-311 G(d,p). The MOLDEN package was used for the preparation of input files and visualization purposes (Schaftenaar & Noordik, 2000).
The molecular structures of compounds G1–G3 are shown in Fig. 1. One of the factors affecting the general conformation of the studied molecules is the methyl substitution at the N3 atom. This substitution determines the conformation around the N3—C4 bond. In the N3-substituted derivatives G1 and G2, the torsion angle C3—N3—C4—O5 is -11.3 (2) (G1), 10.5 (3) (G2, molecule A) and 9.3 (3)° (G2, molecule B), indicating a syn conformation, whereas for G3 and G5, the respective torsion angle H3—N3—C4—O5 is -177 (G3) and -161° (G5) (anti conformation). The G5 structure for which the angle H3—N3—C4—O5 is -1° is an exception. The reason for this less common conformation may be the presence of the NO2 group in the ortho position, which enforces a different hydrogen-bond system (Table 2), packing and significant twist of the phenyl ring. Among the eight analogous compounds found in the CSD with a methyl substituent on atom N3, only one exhibits an anti conformation (Fig. 2a), while as many as 848 fragments in 872 N3—H derivatives show this conformation (Fig. 2b).
As for the aromatic ring orientation, similar to chloro derivatives (Szczesio et al., 2012a,b), the twist of the ring relative to the C(═ O)—N fragment is more than 30° [37.1 (1)° in G1, 51.3 (1) and 66.7 (1)° in the two molecules of G2, and 31.7 (1)° in G3]. In G2, a unique part of the unit cell is formed by two independent molecules interacting only by weak C—H···O contacts (Table 3). As a consequence of very weak dispersion interactions, the benzyl substituents at the S atoms reveal large libration motion with the displacement parameter reaching a value of 0.31 Å2 for the C25A atom. The molecular packing in G3 is determined mainly by N3—H···O5 hydrogen bonds (Fig. 3 and Table 4), owing to which infinite C(4) chains (according to the graph-set definition of Bernstein et al., 1995) are formed parallel to the [101] direction. In addition, the intramolecular weak N3—H···S1 hydrogen bond labelled as S(5) favours flattening of the molecule. The molecular packing in G5 is determined by a similar hydrogen bond (N3—H···O5). In G1 and G2, only weak contacts of the C—H···O type exist (Tables 5 and 3, respectively). In G5, molecular dimers [R22(8)] are formed as a result of N3—H···O5 hydrogen bonds (Fig. 4).
Basic crystallographic parameters of two analogous structures (G4 and G5; Scheme 2), differing only in the position of the nitro group in the aromatic ring, were given in our earlier work (Gobis et al., 2012).
Among the compounds presented in this study, G5 (Scheme 2) shows the highest tuberculostatic activity (Gobis et al. 2011). Molecules of this compound are almost planar. Methyl groups at the S atoms are small enough to allow planar due to the weak intramolecular N—H···S hydrogen bond. The relatively high activity of this compound confirms our hypothesis on the importance of the planarity for the tuberculostatic activity of this group of compounds.
The conformation of G5 (the most active compound) was also optimized with the density functional theory (DFT) method. The resulting geometry (with an anti conformation for O5—C4—N3—H3) was very similar to that found in the crystal state (Fig. 5). The largest difference for these geometries is observed for the C1—N2—N3—C4 torsion angle, which amount to 21.4° (Table 6). This suggests that intermolecular interactions in the crystal do not affect the geometry of the molecule significantly.
Additionally, a G5 molecule with a modified O5—C4—N3—H torsion angle (19.5°) to the syn conformation was optimized with the same method. Interestingly, the energy minimum for this conformation, (the O5—C4—N3—H torsion angle after optimization approximately equals -5°) (Table 6) is almost the same (only 1 kcal mol-1 lower), which suggests that among the two energetically equivalent syn/anti conformations, the latter is preferred in the crystalline state due to intermolecular interactions.
Another important factor influencing the activity is the position of the nitro group substituted in the aromatic ring. For G5 (Scheme 2) the twist of the aromatic ring in regard to the C(═O)—N group equals 57.9 (1)° due to the steric repulsion introduced by the nitro group. The above findings are in agreement with the hypothesis that planarity of the whole molecule is crucial for tuberculostatic activity and that the substituents at sulfur atoms should be small.
The syntheses of G1, G2 and G3 was described by Gobis et al. (2012). Single crystals of G1, G2 and G3 suitable for X-ray diffraction analysis were obtained from methanol solutions by slow evaporation of the solvent at room temperature.
Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms were located in difference Fourier maps and subsequently geometrically optimized and allowed for as riding atoms, with C—H = 0.95 Å for aromatic CH groups, 0.97 Å for secondary CH2 groups and 0.96 Å for methyl groups, and N—H = 0.86 Å, with Uiso(H) = 1.2Ueq(C,N). In G1, the C3 methyl group was refined with two conformations about the N3—C3 bond with six half-occupied H atoms 60° apart. For both G1 and G2, an extinction parameter was refined.
Data collection: CrysAlis CCD (Oxford Diffraction, 2007) for G1, G2; APEX2 (Bruker, 2002) for G3. Cell refinement: CrysAlis RED (Oxford Diffraction, 2007) for G1, G2; SAINT-Plus (Bruker, 2003) for G3. Data reduction: CrysAlis RED (Oxford Diffraction, 2007) for G1, G2; SAINT-Plus (Bruker, 2003) for G3. For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008). Program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015) for G1; SHELXL97 (Sheldrick, 2008) for G2, G3. For all compounds, molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2006); software used to prepare material for publication: PLATON (Spek, 2009).
C11H13N3O3S2 | F(000) = 624 |
Mr = 299.36 | Dx = 1.438 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 6.5716 (2) Å | Cell parameters from 17780 reflections |
b = 16.3193 (5) Å | θ = 1.6–35.9° |
c = 12.8982 (4) Å | µ = 0.39 mm−1 |
β = 91.219 (3)° | T = 295 K |
V = 1382.94 (7) Å3 | , yellow |
Z = 4 | 0.6 × 0.2 × 0.1 mm |
Kuma KM-4 CCD diffractometer | 4223 independent reflections |
Radiation source: fine-focus sealed tube | 3242 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
ω scan | θmax = 30.5°, θmin = 2.0° |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007) | h = −9→7 |
Tmin = 0.817, Tmax = 1.000 | k = −23→23 |
28663 measured reflections | l = −17→18 |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.031 | w = 1/[σ2(Fo2) + (0.0648P)2]
where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.110 | (Δ/σ)max = 0.001 |
S = 1.18 | Δρmax = 0.23 e Å−3 |
4223 reflections | Δρmin = −0.22 e Å−3 |
175 parameters | Extinction correction: SHELXL2013 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.017 (2) |
C11H13N3O3S2 | V = 1382.94 (7) Å3 |
Mr = 299.36 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 6.5716 (2) Å | µ = 0.39 mm−1 |
b = 16.3193 (5) Å | T = 295 K |
c = 12.8982 (4) Å | 0.6 × 0.2 × 0.1 mm |
β = 91.219 (3)° |
Kuma KM-4 CCD diffractometer | 4223 independent reflections |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007) | 3242 reflections with I > 2σ(I) |
Tmin = 0.817, Tmax = 1.000 | Rint = 0.024 |
28663 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | 0 restraints |
wR(F2) = 0.110 | H-atom parameters constrained |
S = 1.18 | Δρmax = 0.23 e Å−3 |
4223 reflections | Δρmin = −0.22 e Å−3 |
175 parameters |
Experimental. Absorption correction: CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.32.37 (release 24-10-2008 CrysAlis171 .NET) (compiled Oct 24 2008,09:44:38) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C1 | 0.45999 (16) | 0.94423 (6) | 0.24776 (8) | 0.0371 (2) | |
C3 | 0.22718 (18) | 0.94937 (8) | 0.04218 (9) | 0.0473 (3) | |
H3A | 0.1801 | 0.9857 | 0.0951 | 0.071* | 0.5 |
H3B | 0.1186 | 0.9134 | 0.0207 | 0.071* | 0.5 |
H3C | 0.2707 | 0.9808 | −0.0162 | 0.071* | 0.5 |
H3D | 0.1995 | 0.9343 | −0.0287 | 0.071* | 0.5 |
H3E | 0.2610 | 1.0065 | 0.0457 | 0.071* | 0.5 |
H3F | 0.1089 | 0.9391 | 0.0826 | 0.071* | 0.5 |
C4 | 0.48662 (15) | 0.84521 (6) | 0.01905 (8) | 0.0351 (2) | |
C11 | 0.7949 (2) | 1.04207 (8) | 0.26835 (12) | 0.0597 (4) | |
H11A | 0.7346 | 1.0747 | 0.2139 | 0.089* | |
H11B | 0.8762 | 0.9996 | 0.2387 | 0.089* | |
H11C | 0.8792 | 1.0761 | 0.3122 | 0.089* | |
C21 | 0.1970 (2) | 0.92306 (10) | 0.41437 (11) | 0.0649 (4) | |
H21A | 0.1732 | 0.9811 | 0.4150 | 0.097* | |
H21B | 0.3134 | 0.9105 | 0.4577 | 0.097* | |
H21C | 0.0798 | 0.8952 | 0.4401 | 0.097* | |
C41 | 0.67875 (15) | 0.80449 (6) | 0.05568 (8) | 0.0333 (2) | |
C42 | 0.81936 (16) | 0.78550 (7) | −0.01969 (8) | 0.0406 (3) | |
H42 | 0.7949 | 0.8015 | −0.0880 | 0.049* | |
C43 | 0.99551 (17) | 0.74301 (7) | 0.00619 (9) | 0.0435 (3) | |
H43 | 1.0898 | 0.7300 | −0.0440 | 0.052* | |
C44 | 1.02768 (16) | 0.72050 (6) | 0.10773 (9) | 0.0382 (2) | |
C45 | 0.89217 (17) | 0.73786 (7) | 0.18471 (9) | 0.0400 (2) | |
H45 | 0.9179 | 0.7217 | 0.2529 | 0.048* | |
C46 | 0.71627 (17) | 0.78018 (6) | 0.15740 (8) | 0.0382 (2) | |
H46 | 0.6221 | 0.7925 | 0.2079 | 0.046* | |
N2 | 0.52847 (13) | 0.94327 (5) | 0.15544 (7) | 0.0383 (2) | |
N3 | 0.39838 (13) | 0.90080 (5) | 0.08326 (7) | 0.0370 (2) | |
N44 | 1.21279 (15) | 0.67409 (6) | 0.13526 (9) | 0.0484 (3) | |
O5 | 0.40735 (13) | 0.82678 (5) | −0.06438 (6) | 0.0492 (2) | |
O441 | 1.31884 (16) | 0.64989 (7) | 0.06538 (9) | 0.0730 (3) | |
O442 | 1.25053 (17) | 0.66016 (8) | 0.22582 (9) | 0.0825 (4) | |
S1 | 0.59742 (5) | 0.99673 (2) | 0.34386 (3) | 0.05254 (12) | |
S2 | 0.24283 (5) | 0.89009 (2) | 0.28382 (2) | 0.04930 (12) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0399 (6) | 0.0339 (5) | 0.0373 (6) | 0.0043 (4) | −0.0029 (4) | −0.0040 (4) |
C3 | 0.0413 (6) | 0.0546 (7) | 0.0457 (7) | 0.0081 (5) | −0.0070 (5) | 0.0018 (5) |
C4 | 0.0347 (5) | 0.0426 (5) | 0.0279 (5) | −0.0046 (4) | 0.0003 (4) | −0.0002 (4) |
C11 | 0.0464 (7) | 0.0566 (8) | 0.0754 (10) | −0.0054 (6) | −0.0099 (6) | −0.0144 (7) |
C21 | 0.0807 (10) | 0.0710 (9) | 0.0437 (7) | 0.0072 (7) | 0.0179 (7) | 0.0019 (6) |
C41 | 0.0342 (5) | 0.0336 (5) | 0.0321 (5) | −0.0044 (4) | −0.0005 (4) | −0.0026 (4) |
C42 | 0.0428 (6) | 0.0495 (6) | 0.0297 (5) | −0.0026 (4) | 0.0030 (4) | −0.0010 (4) |
C43 | 0.0384 (6) | 0.0521 (6) | 0.0403 (6) | −0.0013 (5) | 0.0084 (5) | −0.0056 (5) |
C44 | 0.0347 (5) | 0.0350 (5) | 0.0446 (6) | −0.0024 (4) | −0.0015 (4) | −0.0053 (4) |
C45 | 0.0452 (6) | 0.0392 (5) | 0.0356 (5) | 0.0000 (4) | −0.0031 (4) | 0.0003 (4) |
C46 | 0.0398 (6) | 0.0431 (5) | 0.0318 (5) | 0.0015 (4) | 0.0048 (4) | −0.0020 (4) |
N2 | 0.0385 (5) | 0.0387 (4) | 0.0375 (5) | −0.0009 (3) | −0.0030 (4) | −0.0053 (4) |
N3 | 0.0332 (5) | 0.0441 (5) | 0.0336 (5) | 0.0012 (3) | −0.0046 (3) | −0.0029 (4) |
N44 | 0.0411 (6) | 0.0447 (5) | 0.0594 (7) | 0.0039 (4) | −0.0022 (5) | −0.0071 (4) |
O5 | 0.0463 (5) | 0.0665 (5) | 0.0346 (4) | 0.0000 (4) | −0.0082 (3) | −0.0097 (3) |
O441 | 0.0591 (6) | 0.0830 (7) | 0.0776 (7) | 0.0283 (5) | 0.0194 (5) | 0.0072 (6) |
O442 | 0.0756 (7) | 0.1120 (9) | 0.0589 (7) | 0.0425 (6) | −0.0224 (5) | −0.0135 (6) |
S1 | 0.0561 (2) | 0.0567 (2) | 0.0444 (2) | 0.00030 (13) | −0.00951 (14) | −0.01615 (13) |
S2 | 0.0526 (2) | 0.0531 (2) | 0.04251 (19) | −0.00774 (13) | 0.00746 (14) | −0.00318 (12) |
C1—N2 | 1.2820 (14) | C21—H21A | 0.9600 |
C1—S1 | 1.7431 (11) | C21—H21B | 0.9600 |
C1—S2 | 1.7497 (11) | C21—H21C | 0.9600 |
C3—N3 | 1.4660 (14) | C41—C46 | 1.3877 (14) |
C3—H3A | 0.9600 | C41—C42 | 1.3905 (14) |
C3—H3B | 0.9600 | C42—C43 | 1.3840 (17) |
C3—H3C | 0.9600 | C42—H42 | 0.9300 |
C3—H3D | 0.9600 | C43—C44 | 1.3724 (16) |
C3—H3E | 0.9600 | C43—H43 | 0.9300 |
C3—H3F | 0.9600 | C44—C45 | 1.3772 (16) |
C4—O5 | 1.2231 (12) | C44—N44 | 1.4701 (15) |
C4—N3 | 1.3658 (13) | C45—C46 | 1.3857 (15) |
C4—C41 | 1.4945 (14) | C45—H45 | 0.9300 |
C11—S1 | 1.7983 (14) | C46—H46 | 0.9300 |
C11—H11A | 0.9600 | N2—N3 | 1.4297 (12) |
C11—H11B | 0.9600 | N44—O442 | 1.2104 (15) |
C11—H11C | 0.9600 | N44—O441 | 1.2169 (14) |
C21—S2 | 1.7992 (14) | ||
N2—C1—S1 | 118.67 (8) | S2—C21—H21A | 109.5 |
N2—C1—S2 | 123.03 (9) | S2—C21—H21B | 109.5 |
S1—C1—S2 | 118.19 (6) | H21A—C21—H21B | 109.5 |
N3—C3—H3A | 109.5 | S2—C21—H21C | 109.5 |
N3—C3—H3B | 109.5 | H21A—C21—H21C | 109.5 |
H3A—C3—H3B | 109.5 | H21B—C21—H21C | 109.5 |
N3—C3—H3C | 109.5 | C46—C41—C42 | 119.34 (10) |
H3A—C3—H3C | 109.5 | C46—C41—C4 | 123.91 (9) |
H3B—C3—H3C | 109.5 | C42—C41—C4 | 116.59 (9) |
N3—C3—H3D | 109.5 | C43—C42—C41 | 120.52 (10) |
H3A—C3—H3D | 141.1 | C43—C42—H42 | 119.7 |
H3B—C3—H3D | 56.3 | C41—C42—H42 | 119.7 |
H3C—C3—H3D | 56.3 | C44—C43—C42 | 118.38 (10) |
N3—C3—H3E | 109.5 | C44—C43—H43 | 120.8 |
H3A—C3—H3E | 56.3 | C42—C43—H43 | 120.8 |
H3B—C3—H3E | 141.1 | C43—C44—C45 | 122.96 (11) |
H3C—C3—H3E | 56.3 | C43—C44—N44 | 118.58 (10) |
H3D—C3—H3E | 109.5 | C45—C44—N44 | 118.44 (11) |
N3—C3—H3F | 109.5 | C44—C45—C46 | 117.91 (11) |
H3A—C3—H3F | 56.3 | C44—C45—H45 | 121.0 |
H3B—C3—H3F | 56.3 | C46—C45—H45 | 121.0 |
H3C—C3—H3F | 141.1 | C45—C46—C41 | 120.88 (10) |
H3D—C3—H3F | 109.5 | C45—C46—H46 | 119.6 |
H3E—C3—H3F | 109.5 | C41—C46—H46 | 119.6 |
O5—C4—N3 | 121.23 (10) | C1—N2—N3 | 113.20 (9) |
O5—C4—C41 | 120.66 (9) | C4—N3—N2 | 117.46 (8) |
N3—C4—C41 | 118.06 (9) | C4—N3—C3 | 118.19 (9) |
S1—C11—H11A | 109.5 | N2—N3—C3 | 114.64 (9) |
S1—C11—H11B | 109.5 | O442—N44—O441 | 123.02 (11) |
H11A—C11—H11B | 109.5 | O442—N44—C44 | 118.77 (10) |
S1—C11—H11C | 109.5 | O441—N44—C44 | 118.18 (11) |
H11A—C11—H11C | 109.5 | C1—S1—C11 | 100.72 (6) |
H11B—C11—H11C | 109.5 | C1—S2—C21 | 104.57 (7) |
O5—C4—C41—C46 | −139.25 (11) | S2—C1—N2—N3 | 6.12 (12) |
N3—C4—C41—C46 | 38.07 (14) | O5—C4—N3—N2 | −155.53 (10) |
O5—C4—C41—C42 | 36.12 (15) | C41—C4—N3—N2 | 27.16 (13) |
N3—C4—C41—C42 | −146.56 (10) | O5—C4—N3—C3 | −11.28 (15) |
C46—C41—C42—C43 | −0.21 (16) | C41—C4—N3—C3 | 171.42 (10) |
C4—C41—C42—C43 | −175.80 (10) | C1—N2—N3—C4 | −132.55 (10) |
C41—C42—C43—C44 | −0.19 (17) | C1—N2—N3—C3 | 81.95 (12) |
C42—C43—C44—C45 | 0.39 (17) | C43—C44—N44—O442 | 173.79 (12) |
C42—C43—C44—N44 | 178.93 (10) | C45—C44—N44—O442 | −7.61 (16) |
C43—C44—C45—C46 | −0.17 (16) | C43—C44—N44—O441 | −7.80 (16) |
N44—C44—C45—C46 | −178.71 (9) | C45—C44—N44—O441 | 170.81 (11) |
C44—C45—C46—C41 | −0.25 (16) | N2—C1—S1—C11 | 4.95 (10) |
C42—C41—C46—C45 | 0.44 (16) | S2—C1—S1—C11 | −178.85 (7) |
C4—C41—C46—C45 | 175.68 (10) | N2—C1—S2—C21 | −172.74 (10) |
S1—C1—N2—N3 | −177.87 (7) | S1—C1—S2—C21 | 11.24 (9) |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3C···N2i | 0.96 | 2.57 | 3.5099 (15) | 166 |
C21—H21C···O441ii | 0.96 | 2.49 | 3.4046 (16) | 158 |
C42—H42···O442iii | 0.93 | 2.49 | 3.4209 (16) | 176 |
C45—H45···O5iv | 0.93 | 2.49 | 3.4034 (14) | 167 |
Symmetry codes: (i) −x+1, −y+2, −z; (ii) x−3/2, −y+3/2, z+1/2; (iii) x−1/2, −y+3/2, z−1/2; (iv) x+1/2, −y+3/2, z+1/2. |
C23H21N3O3S2 | F(000) = 1888 |
Mr = 451.55 | Dx = 1.330 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 14105 reflections |
a = 28.5519 (16) Å | θ = 1.9–35.8° |
b = 7.9549 (4) Å | µ = 0.27 mm−1 |
c = 21.3930 (12) Å | T = 296 K |
β = 111.841 (5)° | , yellow |
V = 4510.2 (4) Å3 | 0.3 × 0.15 × 0.1 mm |
Z = 8 |
Kuma KM-4 CCD diffractometer | 7966 independent reflections |
Radiation source: fine-focus sealed tube | 5304 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.050 |
ω scan | θmax = 25.0°, θmin = 2.3° |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007) | h = −33→33 |
Tmin = 0.721, Tmax = 1.000 | k = −9→9 |
45186 measured reflections | l = −25→25 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.034 | H-atom parameters constrained |
wR(F2) = 0.089 | w = 1/[σ2(Fo2) + (0.0557P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.90 | (Δ/σ)max = 0.001 |
7966 reflections | Δρmax = 0.31 e Å−3 |
562 parameters | Δρmin = −0.24 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0051 (3) |
C23H21N3O3S2 | V = 4510.2 (4) Å3 |
Mr = 451.55 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 28.5519 (16) Å | µ = 0.27 mm−1 |
b = 7.9549 (4) Å | T = 296 K |
c = 21.3930 (12) Å | 0.3 × 0.15 × 0.1 mm |
β = 111.841 (5)° |
Kuma KM-4 CCD diffractometer | 7966 independent reflections |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007) | 5304 reflections with I > 2σ(I) |
Tmin = 0.721, Tmax = 1.000 | Rint = 0.050 |
45186 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.089 | H-atom parameters constrained |
S = 0.90 | Δρmax = 0.31 e Å−3 |
7966 reflections | Δρmin = −0.24 e Å−3 |
562 parameters |
Experimental. Absorption correction: CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.32.37 (release 24-10-2008 CrysAlis171 .NET) (compiled Oct 24 2008,09:44:38) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.42581 (7) | 0.3466 (2) | 0.35136 (8) | 0.0454 (4) | |
C3 | 0.51319 (8) | 0.5526 (2) | 0.32397 (10) | 0.0671 (6) | |
H3A | 0.5098 | 0.4597 | 0.2940 | 0.101* | |
H3B | 0.5406 | 0.5315 | 0.3658 | 0.101* | |
H3C | 0.5198 | 0.6535 | 0.3040 | 0.101* | |
C4 | 0.43604 (7) | 0.7026 (2) | 0.31302 (8) | 0.0440 (4) | |
C11 | 0.44199 (9) | 0.2740 (3) | 0.48319 (8) | 0.0708 (6) | |
H11A | 0.4779 | 0.2772 | 0.4924 | 0.085* | |
H11B | 0.4310 | 0.3865 | 0.4886 | 0.085* | |
C12 | 0.43134 (9) | 0.1550 (2) | 0.53067 (8) | 0.0559 (5) | |
C13 | 0.38626 (10) | 0.1544 (3) | 0.53809 (11) | 0.0753 (6) | |
H13 | 0.3609 | 0.2276 | 0.5127 | 0.090* | |
C14 | 0.37765 (11) | 0.0465 (4) | 0.58286 (13) | 0.0933 (8) | |
H14 | 0.3467 | 0.0465 | 0.5879 | 0.112* | |
C15 | 0.41488 (14) | −0.0603 (3) | 0.61972 (11) | 0.0900 (8) | |
H15 | 0.4093 | −0.1336 | 0.6500 | 0.108* | |
C16 | 0.45950 (12) | −0.0606 (3) | 0.61268 (11) | 0.0823 (7) | |
H16 | 0.4848 | −0.1336 | 0.6383 | 0.099* | |
C17 | 0.46807 (9) | 0.0457 (2) | 0.56813 (9) | 0.0660 (6) | |
H17 | 0.4991 | 0.0440 | 0.5632 | 0.079* | |
C21 | 0.35690 (9) | 0.1534 (2) | 0.25117 (9) | 0.0675 (6) | |
H21A | 0.3777 | 0.0560 | 0.2706 | 0.081* | |
H21B | 0.3330 | 0.1677 | 0.2733 | 0.081* | |
C22 | 0.32931 (8) | 0.1272 (2) | 0.17775 (9) | 0.0591 (5) | |
C23 | 0.28526 (11) | 0.2078 (3) | 0.14347 (13) | 0.0999 (9) | |
H23 | 0.2725 | 0.2851 | 0.1656 | 0.120* | |
C24 | 0.25939 (13) | 0.1757 (5) | 0.07598 (16) | 0.1291 (12) | |
H24 | 0.2294 | 0.2321 | 0.0527 | 0.155* | |
C25 | 0.27732 (14) | 0.0639 (4) | 0.04408 (13) | 0.1084 (10) | |
H25 | 0.2594 | 0.0408 | −0.0012 | 0.130* | |
C26 | 0.32114 (12) | −0.0157 (3) | 0.07702 (12) | 0.0900 (8) | |
H26 | 0.3337 | −0.0924 | 0.0544 | 0.108* | |
C27 | 0.34711 (9) | 0.0163 (3) | 0.14371 (10) | 0.0688 (6) | |
H27 | 0.3775 | −0.0388 | 0.1662 | 0.083* | |
C41 | 0.39456 (7) | 0.72637 (18) | 0.33849 (8) | 0.0408 (4) | |
C42 | 0.34684 (7) | 0.7557 (2) | 0.29309 (9) | 0.0489 (4) | |
H42 | 0.3405 | 0.7490 | 0.2473 | 0.059* | |
C43 | 0.30850 (7) | 0.7944 (2) | 0.31368 (9) | 0.0556 (5) | |
H43 | 0.2761 | 0.8142 | 0.2826 | 0.067* | |
C44 | 0.31885 (7) | 0.8035 (2) | 0.38120 (10) | 0.0542 (5) | |
C45 | 0.36597 (8) | 0.7754 (2) | 0.42832 (9) | 0.0552 (5) | |
H45 | 0.3721 | 0.7836 | 0.4741 | 0.066* | |
C46 | 0.40378 (7) | 0.7349 (2) | 0.40670 (8) | 0.0473 (4) | |
H46 | 0.4360 | 0.7128 | 0.4379 | 0.057* | |
C1A | 0.06914 (7) | 0.1697 (2) | 0.42161 (8) | 0.0453 (4) | |
C3A | −0.01471 (8) | −0.0481 (3) | 0.30743 (9) | 0.0682 (6) | |
H3A1 | −0.0126 | 0.0467 | 0.2809 | 0.102* | |
H3A2 | −0.0425 | −0.0330 | 0.3218 | 0.102* | |
H3A3 | −0.0198 | −0.1486 | 0.2809 | 0.102* | |
C4A | 0.06407 (7) | −0.1878 (2) | 0.37417 (8) | 0.0472 (4) | |
C11A | 0.05874 (9) | 0.2213 (3) | 0.54322 (10) | 0.0711 (6) | |
H11C | 0.0224 | 0.2133 | 0.5209 | 0.085* | |
H11D | 0.0722 | 0.1094 | 0.5569 | 0.085* | |
C12A | 0.07213 (8) | 0.3344 (2) | 0.60311 (9) | 0.0570 (5) | |
C13A | 0.11866 (10) | 0.3283 (3) | 0.65334 (11) | 0.0799 (7) | |
H13A | 0.1426 | 0.2523 | 0.6507 | 0.096* | |
C14A | 0.13030 (12) | 0.4342 (4) | 0.70786 (11) | 0.1003 (9) | |
H14A | 0.1621 | 0.4301 | 0.7421 | 0.120* | |
C15A | 0.09538 (16) | 0.5443 (4) | 0.71149 (13) | 0.1014 (10) | |
H15A | 0.1030 | 0.6155 | 0.7484 | 0.122* | |
C16A | 0.04966 (14) | 0.5510 (3) | 0.66197 (16) | 0.0981 (9) | |
H16A | 0.0257 | 0.6266 | 0.6649 | 0.118* | |
C17A | 0.03802 (9) | 0.4484 (3) | 0.60757 (11) | 0.0741 (6) | |
H17A | 0.0065 | 0.4562 | 0.5731 | 0.089* | |
C21A | 0.13819 (8) | 0.3704 (2) | 0.39231 (10) | 0.0657 (6) | |
H21C | 0.1186 | 0.4722 | 0.3882 | 0.079* | |
H21D | 0.1588 | 0.3540 | 0.4395 | 0.079* | |
C22A | 0.17097 (8) | 0.3877 (2) | 0.35292 (10) | 0.0617 (5) | |
C23A | 0.21322 (11) | 0.2920 (3) | 0.36772 (14) | 0.0914 (8) | |
H23A | 0.2211 | 0.2111 | 0.4014 | 0.110* | |
C24A | 0.24448 (13) | 0.3165 (5) | 0.3320 (2) | 0.1363 (14) | |
H24A | 0.2734 | 0.2518 | 0.3414 | 0.164* | |
C25A | 0.23233 (19) | 0.4359 (5) | 0.2831 (2) | 0.1478 (18) | |
H25A | 0.2535 | 0.4541 | 0.2596 | 0.177* | |
C26A | 0.18985 (17) | 0.5286 (4) | 0.26811 (17) | 0.1275 (13) | |
H26A | 0.1815 | 0.6083 | 0.2339 | 0.153* | |
C27A | 0.15985 (11) | 0.5045 (3) | 0.30300 (12) | 0.0860 (7) | |
H27A | 0.1308 | 0.5692 | 0.2928 | 0.103* | |
C41A | 0.10633 (7) | −0.19892 (19) | 0.44148 (8) | 0.0431 (4) | |
C42A | 0.09680 (7) | −0.2396 (2) | 0.49826 (9) | 0.0546 (5) | |
H42A | 0.0637 | −0.2532 | 0.4952 | 0.065* | |
C43A | 0.13546 (8) | −0.2601 (3) | 0.55883 (9) | 0.0607 (5) | |
H43A | 0.1293 | −0.2923 | 0.5968 | 0.073* | |
C44A | 0.18308 (8) | −0.2324 (3) | 0.56214 (9) | 0.0604 (5) | |
C45A | 0.19377 (8) | −0.1908 (3) | 0.50731 (10) | 0.0678 (6) | |
H45A | 0.2268 | −0.1714 | 0.5111 | 0.081* | |
C46A | 0.15465 (7) | −0.1781 (2) | 0.44613 (9) | 0.0571 (5) | |
H46A | 0.1613 | −0.1551 | 0.4076 | 0.069* | |
N2 | 0.45932 (6) | 0.45536 (17) | 0.38155 (7) | 0.0487 (4) | |
N3 | 0.46689 (6) | 0.57237 (17) | 0.33617 (7) | 0.0482 (4) | |
N44 | 0.27818 (8) | 0.8461 (3) | 0.40323 (12) | 0.0825 (6) | |
N2A | 0.03810 (6) | 0.05206 (17) | 0.41962 (7) | 0.0501 (4) | |
N3A | 0.03177 (6) | −0.06251 (17) | 0.36597 (7) | 0.0489 (4) | |
N44A | 0.22477 (9) | −0.2473 (3) | 0.62686 (10) | 0.0907 (7) | |
O5 | 0.44087 (5) | 0.80144 (15) | 0.27225 (6) | 0.0604 (3) | |
O441 | 0.23726 (8) | 0.8798 (3) | 0.36268 (10) | 0.1084 (6) | |
O442 | 0.28724 (8) | 0.8478 (4) | 0.46296 (11) | 0.1523 (10) | |
O443 | 0.26424 (8) | −0.1797 (3) | 0.63436 (10) | 0.1253 (8) | |
O444 | 0.21712 (8) | −0.3280 (3) | 0.67050 (9) | 0.1312 (8) | |
O5A | 0.06050 (5) | −0.28860 (16) | 0.33003 (6) | 0.0674 (4) | |
S1 | 0.40815 (2) | 0.20008 (5) | 0.39877 (2) | 0.05526 (15) | |
S2 | 0.39600 (2) | 0.33777 (6) | 0.26385 (2) | 0.05906 (15) | |
S1A | 0.08603 (2) | 0.31211 (6) | 0.48767 (2) | 0.05795 (15) | |
S2A | 0.09650 (2) | 0.19357 (6) | 0.36155 (2) | 0.05478 (14) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0550 (12) | 0.0334 (9) | 0.0458 (9) | 0.0028 (9) | 0.0164 (9) | 0.0035 (8) |
C3 | 0.0657 (15) | 0.0660 (13) | 0.0810 (14) | 0.0038 (11) | 0.0404 (12) | −0.0010 (11) |
C4 | 0.0500 (11) | 0.0391 (10) | 0.0425 (9) | −0.0096 (9) | 0.0168 (8) | −0.0028 (8) |
C11 | 0.0934 (18) | 0.0617 (12) | 0.0447 (10) | −0.0138 (12) | 0.0112 (11) | 0.0060 (9) |
C12 | 0.0787 (15) | 0.0454 (10) | 0.0388 (9) | −0.0010 (10) | 0.0162 (10) | −0.0017 (8) |
C13 | 0.0926 (19) | 0.0733 (14) | 0.0652 (13) | 0.0158 (13) | 0.0354 (13) | −0.0020 (11) |
C14 | 0.109 (2) | 0.116 (2) | 0.0779 (16) | −0.0044 (18) | 0.0613 (16) | −0.0177 (16) |
C15 | 0.149 (3) | 0.0774 (17) | 0.0560 (13) | −0.0170 (18) | 0.0523 (17) | 0.0013 (12) |
C16 | 0.117 (2) | 0.0641 (14) | 0.0612 (13) | 0.0103 (14) | 0.0272 (14) | 0.0152 (11) |
C17 | 0.0800 (16) | 0.0620 (12) | 0.0518 (11) | 0.0038 (12) | 0.0196 (11) | 0.0034 (10) |
C21 | 0.0883 (17) | 0.0528 (11) | 0.0524 (11) | −0.0206 (11) | 0.0157 (11) | −0.0003 (9) |
C22 | 0.0643 (14) | 0.0514 (11) | 0.0535 (11) | −0.0145 (10) | 0.0126 (10) | −0.0003 (9) |
C23 | 0.093 (2) | 0.0967 (19) | 0.0877 (17) | 0.0164 (17) | 0.0078 (16) | −0.0127 (15) |
C24 | 0.101 (3) | 0.133 (3) | 0.100 (2) | 0.020 (2) | −0.0240 (19) | −0.001 (2) |
C25 | 0.127 (3) | 0.100 (2) | 0.0623 (15) | −0.023 (2) | −0.0065 (17) | −0.0034 (15) |
C26 | 0.123 (2) | 0.0792 (16) | 0.0632 (14) | −0.0218 (17) | 0.0287 (16) | −0.0099 (13) |
C27 | 0.0787 (16) | 0.0618 (13) | 0.0589 (12) | −0.0101 (11) | 0.0176 (11) | 0.0010 (10) |
C41 | 0.0478 (11) | 0.0304 (8) | 0.0427 (9) | −0.0066 (8) | 0.0152 (8) | 0.0021 (7) |
C42 | 0.0502 (12) | 0.0490 (10) | 0.0436 (9) | −0.0078 (9) | 0.0129 (9) | 0.0029 (8) |
C43 | 0.0444 (12) | 0.0572 (11) | 0.0595 (11) | −0.0059 (9) | 0.0127 (9) | 0.0057 (9) |
C44 | 0.0502 (12) | 0.0514 (11) | 0.0683 (12) | −0.0042 (9) | 0.0307 (10) | 0.0031 (9) |
C45 | 0.0613 (14) | 0.0609 (12) | 0.0465 (10) | −0.0045 (10) | 0.0235 (10) | 0.0016 (9) |
C46 | 0.0462 (11) | 0.0484 (10) | 0.0442 (9) | −0.0024 (9) | 0.0132 (8) | 0.0045 (8) |
C1A | 0.0519 (12) | 0.0387 (9) | 0.0434 (9) | 0.0072 (9) | 0.0156 (8) | 0.0007 (7) |
C3A | 0.0613 (14) | 0.0719 (13) | 0.0525 (11) | 0.0024 (11) | −0.0005 (10) | 0.0043 (10) |
C4A | 0.0518 (12) | 0.0466 (10) | 0.0423 (9) | −0.0065 (9) | 0.0166 (8) | −0.0043 (8) |
C11A | 0.0866 (17) | 0.0687 (13) | 0.0744 (13) | −0.0099 (12) | 0.0489 (12) | −0.0144 (11) |
C12A | 0.0722 (15) | 0.0544 (11) | 0.0552 (11) | −0.0019 (11) | 0.0362 (11) | −0.0010 (9) |
C13A | 0.0906 (19) | 0.0851 (16) | 0.0641 (13) | 0.0170 (14) | 0.0292 (13) | 0.0090 (12) |
C14A | 0.122 (3) | 0.118 (2) | 0.0480 (13) | −0.015 (2) | 0.0163 (14) | 0.0069 (14) |
C15A | 0.175 (3) | 0.0819 (18) | 0.0630 (16) | −0.021 (2) | 0.063 (2) | −0.0171 (14) |
C16A | 0.143 (3) | 0.0758 (17) | 0.103 (2) | 0.0083 (18) | 0.077 (2) | −0.0153 (16) |
C17A | 0.0802 (17) | 0.0724 (14) | 0.0789 (14) | 0.0070 (12) | 0.0402 (13) | −0.0081 (12) |
C21A | 0.0784 (15) | 0.0568 (11) | 0.0704 (12) | −0.0142 (11) | 0.0376 (12) | −0.0154 (10) |
C22A | 0.0688 (15) | 0.0556 (12) | 0.0690 (12) | −0.0186 (11) | 0.0352 (11) | −0.0220 (10) |
C23A | 0.087 (2) | 0.0885 (18) | 0.1083 (19) | 0.0001 (15) | 0.0469 (16) | −0.0215 (14) |
C24A | 0.105 (3) | 0.128 (3) | 0.213 (4) | −0.020 (2) | 0.102 (3) | −0.066 (3) |
C25A | 0.196 (5) | 0.107 (3) | 0.219 (4) | −0.076 (3) | 0.168 (4) | −0.069 (3) |
C26A | 0.204 (4) | 0.088 (2) | 0.144 (3) | −0.039 (2) | 0.126 (3) | −0.0188 (19) |
C27A | 0.118 (2) | 0.0644 (14) | 0.0955 (17) | −0.0200 (14) | 0.0632 (17) | −0.0084 (13) |
C41A | 0.0464 (11) | 0.0375 (9) | 0.0435 (9) | 0.0015 (8) | 0.0144 (8) | −0.0045 (7) |
C42A | 0.0474 (12) | 0.0624 (12) | 0.0535 (11) | −0.0032 (9) | 0.0183 (9) | −0.0012 (9) |
C43A | 0.0634 (15) | 0.0735 (13) | 0.0431 (10) | 0.0051 (11) | 0.0173 (10) | 0.0017 (9) |
C44A | 0.0514 (13) | 0.0736 (13) | 0.0447 (10) | 0.0152 (11) | 0.0045 (9) | −0.0095 (9) |
C45A | 0.0415 (12) | 0.0936 (16) | 0.0677 (13) | 0.0051 (11) | 0.0197 (10) | −0.0064 (11) |
C46A | 0.0528 (13) | 0.0698 (13) | 0.0521 (10) | 0.0062 (10) | 0.0235 (10) | −0.0009 (9) |
N2 | 0.0548 (10) | 0.0399 (8) | 0.0497 (8) | −0.0005 (7) | 0.0174 (7) | 0.0041 (7) |
N3 | 0.0506 (10) | 0.0418 (8) | 0.0569 (8) | −0.0024 (7) | 0.0254 (7) | 0.0032 (7) |
N44 | 0.0659 (15) | 0.1038 (15) | 0.0903 (14) | −0.0005 (12) | 0.0436 (12) | 0.0026 (12) |
N2A | 0.0533 (10) | 0.0457 (9) | 0.0495 (8) | 0.0016 (8) | 0.0169 (7) | −0.0041 (7) |
N3A | 0.0514 (10) | 0.0448 (8) | 0.0421 (8) | 0.0000 (7) | 0.0075 (7) | −0.0049 (7) |
N44A | 0.0707 (16) | 0.1283 (18) | 0.0551 (11) | 0.0279 (14) | 0.0025 (11) | −0.0153 (12) |
O5 | 0.0731 (10) | 0.0565 (8) | 0.0601 (7) | −0.0036 (7) | 0.0346 (7) | 0.0143 (6) |
O441 | 0.0727 (13) | 0.1356 (16) | 0.1255 (15) | 0.0265 (12) | 0.0469 (12) | 0.0071 (13) |
O442 | 0.0944 (16) | 0.284 (3) | 0.1038 (15) | 0.0167 (18) | 0.0664 (13) | 0.0045 (17) |
O443 | 0.0648 (13) | 0.172 (2) | 0.1005 (14) | 0.0022 (14) | −0.0137 (11) | −0.0190 (13) |
O444 | 0.1093 (17) | 0.206 (2) | 0.0555 (10) | 0.0244 (15) | 0.0045 (11) | 0.0157 (13) |
O5A | 0.0800 (11) | 0.0623 (8) | 0.0512 (7) | 0.0034 (7) | 0.0145 (7) | −0.0192 (7) |
S1 | 0.0716 (4) | 0.0445 (3) | 0.0444 (2) | −0.0083 (2) | 0.0155 (2) | 0.0077 (2) |
S2 | 0.0851 (4) | 0.0443 (3) | 0.0430 (2) | −0.0153 (3) | 0.0183 (2) | 0.0007 (2) |
S1A | 0.0772 (4) | 0.0484 (3) | 0.0556 (3) | −0.0049 (2) | 0.0331 (3) | −0.0117 (2) |
S2A | 0.0708 (4) | 0.0499 (3) | 0.0469 (2) | −0.0079 (2) | 0.0256 (2) | −0.0063 (2) |
C1—N2 | 1.273 (2) | C3A—N3A | 1.451 (2) |
C1—S1 | 1.7382 (17) | C3A—H3A1 | 0.9600 |
C1—S2 | 1.7460 (17) | C3A—H3A2 | 0.9600 |
C3—N3 | 1.448 (2) | C3A—H3A3 | 0.9600 |
C3—H3A | 0.9600 | C4A—O5A | 1.2137 (19) |
C3—H3B | 0.9600 | C4A—N3A | 1.325 (2) |
C3—H3C | 0.9600 | C4A—C41A | 1.498 (2) |
C4—O5 | 1.2197 (18) | C11A—C12A | 1.494 (3) |
C4—N3 | 1.330 (2) | C11A—S1A | 1.797 (2) |
C4—C41 | 1.488 (2) | C11A—H11C | 0.9700 |
C11—C12 | 1.500 (3) | C11A—H11D | 0.9700 |
C11—S1 | 1.8007 (18) | C12A—C17A | 1.360 (3) |
C11—H11A | 0.9700 | C12A—C13A | 1.364 (3) |
C11—H11B | 0.9700 | C13A—C14A | 1.376 (3) |
C12—C13 | 1.354 (3) | C13A—H13A | 0.9300 |
C12—C17 | 1.368 (3) | C14A—C15A | 1.351 (4) |
C13—C14 | 1.375 (3) | C14A—H14A | 0.9300 |
C13—H13 | 0.9300 | C15A—C16A | 1.342 (4) |
C14—C15 | 1.360 (4) | C15A—H15A | 0.9300 |
C14—H14 | 0.9300 | C16A—C17A | 1.358 (3) |
C15—C16 | 1.337 (4) | C16A—H16A | 0.9300 |
C15—H15 | 0.9300 | C17A—H17A | 0.9300 |
C16—C17 | 1.363 (3) | C21A—C22A | 1.481 (3) |
C16—H16 | 0.9300 | C21A—S2A | 1.8020 (19) |
C17—H17 | 0.9300 | C21A—H21C | 0.9700 |
C21—C22 | 1.487 (2) | C21A—H21D | 0.9700 |
C21—S2 | 1.8016 (19) | C22A—C23A | 1.360 (3) |
C21—H21A | 0.9700 | C22A—C27A | 1.361 (3) |
C21—H21B | 0.9700 | C23A—C24A | 1.388 (4) |
C22—C27 | 1.357 (3) | C23A—H23A | 0.9300 |
C22—C23 | 1.358 (3) | C24A—C25A | 1.360 (5) |
C23—C24 | 1.379 (4) | C24A—H24A | 0.9300 |
C23—H23 | 0.9300 | C25A—C26A | 1.352 (5) |
C24—C25 | 1.334 (4) | C25A—H25A | 0.9300 |
C24—H24 | 0.9300 | C26A—C27A | 1.343 (4) |
C25—C26 | 1.344 (4) | C26A—H26A | 0.9300 |
C25—H25 | 0.9300 | C27A—H27A | 0.9300 |
C26—C27 | 1.365 (3) | C41A—C46A | 1.356 (3) |
C26—H26 | 0.9300 | C41A—C42A | 1.379 (2) |
C27—H27 | 0.9300 | C42A—C43A | 1.364 (2) |
C41—C42 | 1.367 (2) | C42A—H42A | 0.9300 |
C41—C46 | 1.385 (2) | C43A—C44A | 1.353 (3) |
C42—C43 | 1.359 (3) | C43A—H43A | 0.9300 |
C42—H42 | 0.9300 | C44A—C45A | 1.358 (3) |
C43—C44 | 1.364 (2) | C44A—N44A | 1.457 (3) |
C43—H43 | 0.9300 | C45A—C46A | 1.372 (3) |
C44—C45 | 1.367 (3) | C45A—H45A | 0.9300 |
C44—N44 | 1.446 (3) | C46A—H46A | 0.9300 |
C45—C46 | 1.362 (3) | N2—N3 | 1.4184 (18) |
C45—H45 | 0.9300 | N44—O441 | 1.198 (2) |
C46—H46 | 0.9300 | N44—O442 | 1.206 (2) |
C1A—N2A | 1.278 (2) | N2A—N3A | 1.4234 (18) |
C1A—S1A | 1.7339 (17) | N44A—O443 | 1.204 (3) |
C1A—S2A | 1.7448 (17) | N44A—O444 | 1.218 (3) |
N2—C1—S1 | 119.08 (12) | O5A—C4A—N3A | 122.77 (16) |
N2—C1—S2 | 123.07 (12) | O5A—C4A—C41A | 120.89 (16) |
S1—C1—S2 | 117.85 (10) | N3A—C4A—C41A | 116.34 (14) |
N3—C3—H3A | 109.5 | C12A—C11A—S1A | 106.82 (14) |
N3—C3—H3B | 109.5 | C12A—C11A—H11C | 110.4 |
H3A—C3—H3B | 109.5 | S1A—C11A—H11C | 110.4 |
N3—C3—H3C | 109.5 | C12A—C11A—H11D | 110.4 |
H3A—C3—H3C | 109.5 | S1A—C11A—H11D | 110.4 |
H3B—C3—H3C | 109.5 | H11C—C11A—H11D | 108.6 |
O5—C4—N3 | 122.18 (16) | C17A—C12A—C13A | 118.8 (2) |
O5—C4—C41 | 119.81 (16) | C17A—C12A—C11A | 120.0 (2) |
N3—C4—C41 | 118.00 (14) | C13A—C12A—C11A | 121.2 (2) |
C12—C11—S1 | 107.76 (13) | C12A—C13A—C14A | 120.2 (2) |
C12—C11—H11A | 110.2 | C12A—C13A—H13A | 119.9 |
S1—C11—H11A | 110.2 | C14A—C13A—H13A | 119.9 |
C12—C11—H11B | 110.2 | C15A—C14A—C13A | 119.7 (3) |
S1—C11—H11B | 110.2 | C15A—C14A—H14A | 120.2 |
H11A—C11—H11B | 108.5 | C13A—C14A—H14A | 120.2 |
C13—C12—C17 | 118.95 (19) | C16A—C15A—C14A | 120.2 (2) |
C13—C12—C11 | 121.5 (2) | C16A—C15A—H15A | 119.9 |
C17—C12—C11 | 119.5 (2) | C14A—C15A—H15A | 119.9 |
C12—C13—C14 | 120.5 (2) | C15A—C16A—C17A | 120.6 (3) |
C12—C13—H13 | 119.7 | C15A—C16A—H16A | 119.7 |
C14—C13—H13 | 119.7 | C17A—C16A—H16A | 119.7 |
C15—C14—C13 | 119.3 (3) | C16A—C17A—C12A | 120.5 (2) |
C15—C14—H14 | 120.3 | C16A—C17A—H17A | 119.8 |
C13—C14—H14 | 120.3 | C12A—C17A—H17A | 119.8 |
C16—C15—C14 | 120.5 (2) | C22A—C21A—S2A | 109.64 (13) |
C16—C15—H15 | 119.7 | C22A—C21A—H21C | 109.7 |
C14—C15—H15 | 119.7 | S2A—C21A—H21C | 109.7 |
C15—C16—C17 | 120.3 (2) | C22A—C21A—H21D | 109.7 |
C15—C16—H16 | 119.9 | S2A—C21A—H21D | 109.7 |
C17—C16—H16 | 119.9 | H21C—C21A—H21D | 108.2 |
C16—C17—C12 | 120.4 (2) | C23A—C22A—C27A | 119.5 (2) |
C16—C17—H17 | 119.8 | C23A—C22A—C21A | 120.6 (2) |
C12—C17—H17 | 119.8 | C27A—C22A—C21A | 119.8 (2) |
C22—C21—S2 | 109.18 (13) | C22A—C23A—C24A | 119.3 (3) |
C22—C21—H21A | 109.8 | C22A—C23A—H23A | 120.3 |
S2—C21—H21A | 109.8 | C24A—C23A—H23A | 120.3 |
C22—C21—H21B | 109.8 | C25A—C24A—C23A | 119.3 (3) |
S2—C21—H21B | 109.8 | C25A—C24A—H24A | 120.3 |
H21A—C21—H21B | 108.3 | C23A—C24A—H24A | 120.3 |
C27—C22—C23 | 118.3 (2) | C26A—C25A—C24A | 120.8 (3) |
C27—C22—C21 | 120.1 (2) | C26A—C25A—H25A | 119.6 |
C23—C22—C21 | 121.6 (2) | C24A—C25A—H25A | 119.6 |
C22—C23—C24 | 120.4 (3) | C27A—C26A—C25A | 119.5 (3) |
C22—C23—H23 | 119.8 | C27A—C26A—H26A | 120.2 |
C24—C23—H23 | 119.8 | C25A—C26A—H26A | 120.2 |
C25—C24—C23 | 120.1 (3) | C26A—C27A—C22A | 121.5 (3) |
C25—C24—H24 | 120.0 | C26A—C27A—H27A | 119.3 |
C23—C24—H24 | 120.0 | C22A—C27A—H27A | 119.3 |
C24—C25—C26 | 120.4 (3) | C46A—C41A—C42A | 119.53 (17) |
C24—C25—H25 | 119.8 | C46A—C41A—C4A | 119.81 (15) |
C26—C25—H25 | 119.8 | C42A—C41A—C4A | 120.55 (16) |
C25—C26—C27 | 119.9 (3) | C43A—C42A—C41A | 120.66 (18) |
C25—C26—H26 | 120.1 | C43A—C42A—H42A | 119.7 |
C27—C26—H26 | 120.1 | C41A—C42A—H42A | 119.7 |
C22—C27—C26 | 121.0 (2) | C44A—C43A—C42A | 118.21 (18) |
C22—C27—H27 | 119.5 | C44A—C43A—H43A | 120.9 |
C26—C27—H27 | 119.5 | C42A—C43A—H43A | 120.9 |
C42—C41—C46 | 119.26 (17) | C43A—C44A—C45A | 122.60 (18) |
C42—C41—C4 | 118.68 (15) | C43A—C44A—N44A | 119.1 (2) |
C46—C41—C4 | 121.79 (16) | C45A—C44A—N44A | 118.3 (2) |
C43—C42—C41 | 121.23 (17) | C44A—C45A—C46A | 118.48 (19) |
C43—C42—H42 | 119.4 | C44A—C45A—H45A | 120.8 |
C41—C42—H42 | 119.4 | C46A—C45A—H45A | 120.8 |
C42—C43—C44 | 118.16 (18) | C41A—C46A—C45A | 120.40 (17) |
C42—C43—H43 | 120.9 | C41A—C46A—H46A | 119.8 |
C44—C43—H43 | 120.9 | C45A—C46A—H46A | 119.8 |
C43—C44—C45 | 122.57 (18) | C1—N2—N3 | 112.08 (13) |
C43—C44—N44 | 118.25 (19) | C4—N3—N2 | 121.15 (14) |
C45—C44—N44 | 119.18 (18) | C4—N3—C3 | 122.68 (14) |
C46—C45—C44 | 118.39 (16) | N2—N3—C3 | 115.72 (14) |
C46—C45—H45 | 120.8 | O441—N44—O442 | 122.1 (2) |
C44—C45—H45 | 120.8 | O441—N44—C44 | 120.1 (2) |
C45—C46—C41 | 120.37 (17) | O442—N44—C44 | 117.8 (2) |
C45—C46—H46 | 119.8 | C1A—N2A—N3A | 111.97 (14) |
C41—C46—H46 | 119.8 | C4A—N3A—N2A | 120.12 (13) |
N2A—C1A—S1A | 118.99 (13) | C4A—N3A—C3A | 122.80 (15) |
N2A—C1A—S2A | 123.36 (13) | N2A—N3A—C3A | 116.51 (14) |
S1A—C1A—S2A | 117.64 (11) | O443—N44A—O444 | 124.0 (2) |
N3A—C3A—H3A1 | 109.5 | O443—N44A—C44A | 118.9 (3) |
N3A—C3A—H3A2 | 109.5 | O444—N44A—C44A | 117.1 (3) |
H3A1—C3A—H3A2 | 109.5 | C1—S1—C11 | 101.68 (9) |
N3A—C3A—H3A3 | 109.5 | C1—S2—C21 | 102.81 (8) |
H3A1—C3A—H3A3 | 109.5 | C1A—S1A—C11A | 102.63 (9) |
H3A2—C3A—H3A3 | 109.5 | C1A—S2A—C21A | 103.42 (9) |
S1—C11—C12—C13 | −74.1 (2) | C23A—C22A—C27A—C26A | −0.4 (3) |
S1—C11—C12—C17 | 106.70 (18) | C21A—C22A—C27A—C26A | 177.2 (2) |
C17—C12—C13—C14 | 0.4 (3) | O5A—C4A—C41A—C46A | 63.8 (2) |
C11—C12—C13—C14 | −178.75 (19) | N3A—C4A—C41A—C46A | −115.65 (19) |
C12—C13—C14—C15 | −0.1 (3) | O5A—C4A—C41A—C42A | −112.5 (2) |
C13—C14—C15—C16 | 0.1 (4) | N3A—C4A—C41A—C42A | 68.1 (2) |
C14—C15—C16—C17 | −0.4 (4) | C46A—C41A—C42A—C43A | −0.4 (3) |
C15—C16—C17—C12 | 0.7 (3) | C4A—C41A—C42A—C43A | 175.86 (17) |
C13—C12—C17—C16 | −0.7 (3) | C41A—C42A—C43A—C44A | 2.8 (3) |
C11—C12—C17—C16 | 178.48 (18) | C42A—C43A—C44A—C45A | −2.3 (3) |
S2—C21—C22—C27 | 97.8 (2) | C42A—C43A—C44A—N44A | 177.68 (19) |
S2—C21—C22—C23 | −84.4 (2) | C43A—C44A—C45A—C46A | −0.6 (3) |
C27—C22—C23—C24 | 0.6 (4) | N44A—C44A—C45A—C46A | 179.42 (19) |
C21—C22—C23—C24 | −177.3 (3) | C42A—C41A—C46A—C45A | −2.6 (3) |
C22—C23—C24—C25 | 0.6 (5) | C4A—C41A—C46A—C45A | −178.88 (17) |
C23—C24—C25—C26 | −1.4 (5) | C44A—C45A—C46A—C41A | 3.1 (3) |
C24—C25—C26—C27 | 0.9 (5) | S1—C1—N2—N3 | −175.93 (11) |
C23—C22—C27—C26 | −1.0 (3) | S2—C1—N2—N3 | 3.6 (2) |
C21—C22—C27—C26 | 176.85 (19) | O5—C4—N3—N2 | −177.49 (15) |
C25—C26—C27—C22 | 0.3 (4) | C41—C4—N3—N2 | 2.7 (2) |
O5—C4—C41—C42 | 48.1 (2) | O5—C4—N3—C3 | 10.5 (3) |
N3—C4—C41—C42 | −132.04 (16) | C41—C4—N3—C3 | −169.32 (15) |
O5—C4—C41—C46 | −125.91 (18) | C1—N2—N3—C4 | 81.10 (19) |
N3—C4—C41—C46 | 54.0 (2) | C1—N2—N3—C3 | −106.40 (18) |
C46—C41—C42—C43 | 0.6 (2) | C43—C44—N44—O441 | −3.4 (3) |
C4—C41—C42—C43 | −173.55 (15) | C45—C44—N44—O441 | 176.1 (2) |
C41—C42—C43—C44 | 0.0 (3) | C43—C44—N44—O442 | 177.3 (2) |
C42—C43—C44—C45 | 0.0 (3) | C45—C44—N44—O442 | −3.2 (3) |
C42—C43—C44—N44 | 179.50 (17) | S1A—C1A—N2A—N3A | −174.63 (11) |
C43—C44—C45—C46 | −0.7 (3) | S2A—C1A—N2A—N3A | 4.4 (2) |
N44—C44—C45—C46 | 179.79 (17) | O5A—C4A—N3A—N2A | −179.74 (16) |
C44—C45—C46—C41 | 1.4 (3) | C41A—C4A—N3A—N2A | −0.3 (2) |
C42—C41—C46—C45 | −1.3 (2) | O5A—C4A—N3A—C3A | 9.3 (3) |
C4—C41—C46—C45 | 172.62 (16) | C41A—C4A—N3A—C3A | −171.33 (16) |
S1A—C11A—C12A—C17A | 99.1 (2) | C1A—N2A—N3A—C4A | 84.21 (19) |
S1A—C11A—C12A—C13A | −79.5 (2) | C1A—N2A—N3A—C3A | −104.24 (18) |
C17A—C12A—C13A—C14A | 1.0 (3) | C43A—C44A—N44A—O443 | −159.6 (2) |
C11A—C12A—C13A—C14A | 179.6 (2) | C45A—C44A—N44A—O443 | 20.4 (3) |
C12A—C13A—C14A—C15A | 0.1 (4) | C43A—C44A—N44A—O444 | 20.0 (3) |
C13A—C14A—C15A—C16A | −0.4 (4) | C45A—C44A—N44A—O444 | −160.0 (2) |
C14A—C15A—C16A—C17A | −0.4 (4) | N2—C1—S1—C11 | 6.45 (17) |
C15A—C16A—C17A—C12A | 1.5 (4) | S2—C1—S1—C11 | −173.11 (12) |
C13A—C12A—C17A—C16A | −1.8 (3) | C12—C11—S1—C1 | −178.50 (15) |
C11A—C12A—C17A—C16A | 179.5 (2) | N2—C1—S2—C21 | 176.02 (16) |
S2A—C21A—C22A—C23A | −81.9 (2) | S1—C1—S2—C21 | −4.45 (14) |
S2A—C21A—C22A—C27A | 100.6 (2) | C22—C21—S2—C1 | −179.05 (15) |
C27A—C22A—C23A—C24A | 0.6 (3) | N2A—C1A—S1A—C11A | 8.70 (17) |
C21A—C22A—C23A—C24A | −177.0 (2) | S2A—C1A—S1A—C11A | −170.40 (12) |
C22A—C23A—C24A—C25A | 0.2 (5) | C12A—C11A—S1A—C1A | 178.98 (15) |
C23A—C24A—C25A—C26A | −1.2 (6) | N2A—C1A—S2A—C21A | −177.36 (15) |
C24A—C25A—C26A—C27A | 1.4 (5) | S1A—C1A—S2A—C21A | 1.70 (13) |
C25A—C26A—C27A—C22A | −0.6 (4) | C22A—C21A—S2A—C1A | 170.06 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
C21A—H21C···O5Ai | 0.97 | 2.53 | 3.443 (3) | 157 |
C43—H43···O444ii | 0.93 | 2.37 | 3.212 (3) | 151 |
C45A—H45A···O442iii | 0.93 | 2.32 | 3.162 (3) | 150 |
Symmetry codes: (i) x, y+1, z; (ii) x, −y+1/2, z−1/2; (iii) x, y−1, z. |
C16H15N3O3S2 | F(000) = 752 |
Mr = 361.43 | Dx = 1.373 Mg m−3 |
Monoclinic, P21/n | Cu Kα radiation, λ = 1.54178 Å |
Hall symbol: -P 2yn | Cell parameters from 7846 reflections |
a = 7.3383 (2) Å | θ = 2.8–69.3° |
b = 31.5484 (8) Å | µ = 2.93 mm−1 |
c = 8.0521 (2) Å | T = 290 K |
β = 110.253 (1)° | Needle, white |
V = 1748.90 (8) Å3 | 0.3 × 0.05 × 0.05 mm |
Z = 4 |
Bruker SMART APEXII CCD diffractometer | 3246 independent reflections |
Radiation source: fine-focus sealed tube | 2834 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
ω scan | θmax = 70.1°, θmin = 2.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −8→8 |
Tmin = 0.813, Tmax = 1.000 | k = −37→38 |
20093 measured reflections | l = −9→9 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.105 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0496P)2 + 0.4477P] where P = (Fo2 + 2Fc2)/3 |
3246 reflections | (Δ/σ)max < 0.001 |
218 parameters | Δρmax = 0.24 e Å−3 |
0 restraints | Δρmin = −0.19 e Å−3 |
C16H15N3O3S2 | V = 1748.90 (8) Å3 |
Mr = 361.43 | Z = 4 |
Monoclinic, P21/n | Cu Kα radiation |
a = 7.3383 (2) Å | µ = 2.93 mm−1 |
b = 31.5484 (8) Å | T = 290 K |
c = 8.0521 (2) Å | 0.3 × 0.05 × 0.05 mm |
β = 110.253 (1)° |
Bruker SMART APEXII CCD diffractometer | 3246 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2834 reflections with I > 2σ(I) |
Tmin = 0.813, Tmax = 1.000 | Rint = 0.028 |
20093 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.105 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.24 e Å−3 |
3246 reflections | Δρmin = −0.19 e Å−3 |
218 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.0604 (2) | 0.15839 (6) | 0.3466 (2) | 0.0577 (4) | |
C4 | 0.1417 (2) | 0.26386 (6) | 0.2760 (2) | 0.0569 (4) | |
C11 | −0.0032 (4) | 0.08002 (6) | 0.1613 (3) | 0.0824 (6) | |
H11A | 0.1237 | 0.0693 | 0.2323 | 0.099* | |
H11B | −0.0941 | 0.0733 | 0.2208 | 0.099* | |
C12 | −0.0684 (4) | 0.06033 (6) | −0.0193 (3) | 0.0856 (7) | |
C13 | −0.2608 (5) | 0.05188 (10) | −0.1059 (5) | 0.1221 (11) | |
H13 | −0.3517 | 0.0588 | −0.0536 | 0.147* | |
C14 | −0.3204 (7) | 0.03310 (12) | −0.2710 (6) | 0.1528 (16) | |
H14 | −0.4514 | 0.0271 | −0.3285 | 0.183* | |
C15 | −0.1923 (9) | 0.02340 (11) | −0.3492 (5) | 0.1496 (18) | |
H15 | −0.2344 | 0.0110 | −0.4610 | 0.179* | |
C16 | −0.0017 (8) | 0.03158 (10) | −0.2660 (6) | 0.1366 (14) | |
H16 | 0.0876 | 0.0248 | −0.3204 | 0.164* | |
C17 | 0.0608 (5) | 0.04996 (8) | −0.0998 (4) | 0.1085 (9) | |
H17 | 0.1923 | 0.0553 | −0.0426 | 0.130* | |
C21 | 0.1133 (4) | 0.15898 (10) | 0.6988 (3) | 0.0951 (8) | |
H21A | 0.2321 | 0.1742 | 0.7187 | 0.143* | |
H21B | 0.1215 | 0.1434 | 0.8036 | 0.143* | |
H21C | 0.0070 | 0.1786 | 0.6711 | 0.143* | |
C41 | 0.1102 (2) | 0.29170 (6) | 0.1184 (2) | 0.0567 (4) | |
C42 | 0.0938 (3) | 0.33488 (6) | 0.1418 (3) | 0.0645 (5) | |
H42 | 0.1031 | 0.3453 | 0.2526 | 0.077* | |
C43 | 0.0637 (3) | 0.36251 (7) | 0.0025 (3) | 0.0738 (5) | |
H43 | 0.0506 | 0.3914 | 0.0174 | 0.089* | |
C44 | 0.0534 (3) | 0.34648 (8) | −0.1584 (3) | 0.0725 (5) | |
C45 | 0.0744 (3) | 0.30431 (8) | −0.1861 (3) | 0.0757 (6) | |
H45 | 0.0696 | 0.2944 | −0.2964 | 0.091* | |
C46 | 0.1034 (3) | 0.27650 (7) | −0.0449 (3) | 0.0668 (5) | |
H46 | 0.1181 | 0.2476 | −0.0604 | 0.080* | |
N2 | 0.0866 (2) | 0.19767 (5) | 0.38177 (18) | 0.0597 (4) | |
N3 | 0.0685 (2) | 0.22441 (5) | 0.24002 (18) | 0.0571 (4) | |
H3 | 0.0123 | 0.2161 | 0.1327 | 0.069* | |
N44 | 0.0194 (3) | 0.37648 (9) | −0.3085 (3) | 0.0941 (6) | |
O5 | 0.2302 (2) | 0.27647 (5) | 0.42616 (17) | 0.0781 (4) | |
O441 | 0.0167 (3) | 0.41441 (8) | −0.2765 (3) | 0.1288 (8) | |
O442 | −0.0070 (3) | 0.36199 (8) | −0.4537 (3) | 0.1248 (8) | |
S1 | 0.00760 (9) | 0.137011 (15) | 0.13261 (6) | 0.07046 (17) | |
S2 | 0.07452 (8) | 0.12289 (2) | 0.51793 (7) | 0.07755 (19) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0494 (9) | 0.0687 (11) | 0.0510 (9) | 0.0066 (8) | 0.0124 (7) | 0.0085 (8) |
C4 | 0.0476 (8) | 0.0594 (10) | 0.0495 (9) | 0.0062 (7) | −0.0013 (7) | −0.0058 (7) |
C11 | 0.1110 (18) | 0.0554 (11) | 0.0815 (14) | 0.0049 (11) | 0.0340 (13) | 0.0055 (10) |
C12 | 0.125 (2) | 0.0463 (10) | 0.0873 (15) | 0.0036 (11) | 0.0383 (15) | 0.0033 (10) |
C13 | 0.130 (3) | 0.096 (2) | 0.120 (2) | 0.0130 (18) | 0.018 (2) | −0.0261 (18) |
C14 | 0.174 (4) | 0.113 (3) | 0.132 (3) | 0.011 (2) | 0.002 (3) | −0.038 (2) |
C15 | 0.260 (6) | 0.078 (2) | 0.100 (2) | 0.000 (3) | 0.048 (3) | −0.0165 (17) |
C16 | 0.237 (5) | 0.0768 (19) | 0.132 (3) | −0.013 (2) | 0.109 (3) | −0.0107 (19) |
C17 | 0.158 (3) | 0.0665 (14) | 0.123 (2) | −0.0125 (15) | 0.077 (2) | −0.0081 (14) |
C21 | 0.0941 (16) | 0.136 (2) | 0.0566 (12) | 0.0100 (15) | 0.0276 (12) | 0.0156 (13) |
C41 | 0.0420 (8) | 0.0642 (10) | 0.0539 (10) | −0.0037 (7) | 0.0040 (7) | −0.0040 (8) |
C42 | 0.0568 (10) | 0.0646 (11) | 0.0638 (11) | −0.0037 (8) | 0.0104 (8) | −0.0028 (8) |
C43 | 0.0631 (11) | 0.0668 (12) | 0.0849 (15) | −0.0045 (9) | 0.0172 (11) | 0.0083 (10) |
C44 | 0.0537 (10) | 0.0870 (15) | 0.0721 (13) | −0.0092 (9) | 0.0158 (9) | 0.0146 (11) |
C45 | 0.0624 (11) | 0.1048 (17) | 0.0603 (11) | −0.0124 (11) | 0.0218 (9) | −0.0039 (11) |
C46 | 0.0612 (10) | 0.0740 (12) | 0.0612 (11) | −0.0056 (9) | 0.0162 (9) | −0.0067 (9) |
N2 | 0.0583 (8) | 0.0690 (10) | 0.0435 (7) | 0.0050 (7) | 0.0071 (6) | 0.0041 (6) |
N3 | 0.0585 (8) | 0.0594 (8) | 0.0397 (7) | −0.0014 (6) | −0.0003 (6) | −0.0015 (6) |
N44 | 0.0705 (11) | 0.1181 (19) | 0.0900 (15) | −0.0077 (11) | 0.0232 (11) | 0.0288 (14) |
O5 | 0.0802 (9) | 0.0710 (8) | 0.0528 (7) | 0.0030 (7) | −0.0156 (7) | −0.0111 (6) |
O441 | 0.1451 (19) | 0.1056 (16) | 0.1267 (17) | −0.0046 (13) | 0.0355 (14) | 0.0437 (14) |
O442 | 0.1220 (16) | 0.172 (2) | 0.0833 (13) | −0.0042 (14) | 0.0399 (12) | 0.0322 (14) |
S1 | 0.0978 (4) | 0.0538 (3) | 0.0556 (3) | 0.0024 (2) | 0.0212 (3) | 0.00350 (18) |
S2 | 0.0785 (3) | 0.0905 (4) | 0.0651 (3) | 0.0068 (3) | 0.0268 (3) | 0.0250 (3) |
C1—N2 | 1.271 (2) | C17—H17 | 0.9300 |
C1—S2 | 1.7519 (18) | C21—S2 | 1.792 (3) |
C1—S1 | 1.7641 (18) | C21—H21A | 0.9600 |
C4—O5 | 1.224 (2) | C21—H21B | 0.9600 |
C4—N3 | 1.347 (2) | C21—H21C | 0.9600 |
C4—C41 | 1.494 (2) | C41—C46 | 1.385 (3) |
C11—C12 | 1.499 (3) | C41—C42 | 1.386 (3) |
C11—S1 | 1.818 (2) | C42—C43 | 1.377 (3) |
C11—H11A | 0.9700 | C42—H42 | 0.9300 |
C11—H11B | 0.9700 | C43—C44 | 1.368 (3) |
C12—C17 | 1.361 (4) | C43—H43 | 0.9300 |
C12—C13 | 1.367 (4) | C44—C45 | 1.367 (3) |
C13—C14 | 1.381 (5) | C44—N44 | 1.487 (3) |
C13—H13 | 0.9300 | C45—C46 | 1.393 (3) |
C14—C15 | 1.335 (6) | C45—H45 | 0.9300 |
C14—H14 | 0.9300 | C46—H46 | 0.9300 |
C15—C16 | 1.350 (6) | N2—N3 | 1.388 (2) |
C15—H15 | 0.9300 | N3—H3 | 0.8600 |
C16—C17 | 1.383 (5) | N44—O442 | 1.207 (3) |
C16—H16 | 0.9300 | N44—O441 | 1.226 (3) |
N2—C1—S2 | 119.00 (14) | H21A—C21—H21B | 109.5 |
N2—C1—S1 | 123.75 (13) | S2—C21—H21C | 109.5 |
S2—C1—S1 | 117.25 (11) | H21A—C21—H21C | 109.5 |
O5—C4—N3 | 123.29 (17) | H21B—C21—H21C | 109.5 |
O5—C4—C41 | 121.40 (16) | C46—C41—C42 | 119.55 (18) |
N3—C4—C41 | 115.30 (14) | C46—C41—C4 | 123.19 (17) |
C12—C11—S1 | 107.46 (15) | C42—C41—C4 | 117.22 (16) |
C12—C11—H11A | 110.2 | C43—C42—C41 | 120.55 (19) |
S1—C11—H11A | 110.2 | C43—C42—H42 | 119.7 |
C12—C11—H11B | 110.2 | C41—C42—H42 | 119.7 |
S1—C11—H11B | 110.2 | C44—C43—C42 | 118.6 (2) |
H11A—C11—H11B | 108.5 | C44—C43—H43 | 120.7 |
C17—C12—C13 | 118.5 (3) | C42—C43—H43 | 120.7 |
C17—C12—C11 | 121.4 (3) | C45—C44—C43 | 122.8 (2) |
C13—C12—C11 | 120.2 (3) | C45—C44—N44 | 118.9 (2) |
C12—C13—C14 | 120.1 (4) | C43—C44—N44 | 118.3 (2) |
C12—C13—H13 | 119.9 | C44—C45—C46 | 118.3 (2) |
C14—C13—H13 | 119.9 | C44—C45—H45 | 120.9 |
C15—C14—C13 | 120.8 (4) | C46—C45—H45 | 120.9 |
C15—C14—H14 | 119.6 | C41—C46—C45 | 120.2 (2) |
C13—C14—H14 | 119.6 | C41—C46—H46 | 119.9 |
C14—C15—C16 | 119.9 (4) | C45—C46—H46 | 119.9 |
C14—C15—H15 | 120.0 | C1—N2—N3 | 116.44 (14) |
C16—C15—H15 | 120.0 | C4—N3—N2 | 117.83 (14) |
C15—C16—C17 | 120.0 (4) | C4—N3—H3 | 121.1 |
C15—C16—H16 | 120.0 | N2—N3—H3 | 121.1 |
C17—C16—H16 | 120.0 | O442—N44—O441 | 124.4 (3) |
C12—C17—C16 | 120.6 (4) | O442—N44—C44 | 118.2 (3) |
C12—C17—H17 | 119.7 | O441—N44—C44 | 117.4 (3) |
C16—C17—H17 | 119.7 | C1—S1—C11 | 104.98 (10) |
S2—C21—H21A | 109.5 | C1—S2—C21 | 100.57 (11) |
S2—C21—H21B | 109.5 | ||
S1—C11—C12—C17 | 86.7 (2) | C43—C44—C45—C46 | 1.4 (3) |
S1—C11—C12—C13 | −94.2 (3) | N44—C44—C45—C46 | −179.09 (17) |
C17—C12—C13—C14 | 0.2 (5) | C42—C41—C46—C45 | −1.9 (3) |
C11—C12—C13—C14 | −178.9 (3) | C4—C41—C46—C45 | −179.67 (16) |
C12—C13—C14—C15 | −0.8 (6) | C44—C45—C46—C41 | 0.0 (3) |
C13—C14—C15—C16 | 0.6 (6) | S2—C1—N2—N3 | −178.29 (12) |
C14—C15—C16—C17 | 0.0 (6) | S1—C1—N2—N3 | 1.0 (2) |
C13—C12—C17—C16 | 0.4 (4) | O5—C4—N3—N2 | 3.3 (3) |
C11—C12—C17—C16 | 179.6 (2) | C41—C4—N3—N2 | −177.49 (14) |
C15—C16—C17—C12 | −0.6 (5) | C1—N2—N3—C4 | −163.56 (16) |
O5—C4—C41—C46 | 146.87 (19) | C45—C44—N44—O442 | 7.0 (3) |
N3—C4—C41—C46 | −32.3 (2) | C43—C44—N44—O442 | −173.5 (2) |
O5—C4—C41—C42 | −31.0 (2) | C45—C44—N44—O441 | −174.3 (2) |
N3—C4—C41—C42 | 149.81 (16) | C43—C44—N44—O441 | 5.2 (3) |
C46—C41—C42—C43 | 2.4 (3) | N2—C1—S1—C11 | 177.33 (17) |
C4—C41—C42—C43 | −179.69 (16) | S2—C1—S1—C11 | −3.33 (14) |
C41—C42—C43—C44 | −1.0 (3) | C12—C11—S1—C1 | 174.15 (17) |
C42—C43—C44—C45 | −1.0 (3) | N2—C1—S2—C21 | 3.01 (18) |
C42—C43—C44—N44 | 179.56 (17) | S1—C1—S2—C21 | −176.36 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O5i | 0.86 | 2.17 | 2.8648 (17) | 137 |
Symmetry code: (i) x−1/2, −y+1/2, z−1/2. |
Experimental details
(G1) | (G2) | (G3) | |
Crystal data | |||
Chemical formula | C11H13N3O3S2 | C23H21N3O3S2 | C16H15N3O3S2 |
Mr | 299.36 | 451.55 | 361.43 |
Crystal system, space group | Monoclinic, P21/n | Monoclinic, P21/c | Monoclinic, P21/n |
Temperature (K) | 295 | 296 | 290 |
a, b, c (Å) | 6.5716 (2), 16.3193 (5), 12.8982 (4) | 28.5519 (16), 7.9549 (4), 21.3930 (12) | 7.3383 (2), 31.5484 (8), 8.0521 (2) |
β (°) | 91.219 (3) | 111.841 (5) | 110.253 (1) |
V (Å3) | 1382.94 (7) | 4510.2 (4) | 1748.90 (8) |
Z | 4 | 8 | 4 |
Radiation type | Mo Kα | Mo Kα | Cu Kα |
µ (mm−1) | 0.39 | 0.27 | 2.93 |
Crystal size (mm) | 0.6 × 0.2 × 0.1 | 0.3 × 0.15 × 0.1 | 0.3 × 0.05 × 0.05 |
Data collection | |||
Diffractometer | Kuma KM-4 CCD | Kuma KM-4 CCD | Bruker SMART APEXII CCD |
Absorption correction | Multi-scan (CrysAlis RED; Oxford Diffraction, 2007) | Multi-scan (CrysAlis RED; Oxford Diffraction, 2007) | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.817, 1.000 | 0.721, 1.000 | 0.813, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 28663, 4223, 3242 | 45186, 7966, 5304 | 20093, 3246, 2834 |
Rint | 0.024 | 0.050 | 0.028 |
(sin θ/λ)max (Å−1) | 0.714 | 0.595 | 0.610 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.110, 1.18 | 0.034, 0.089, 0.90 | 0.038, 0.105, 1.03 |
No. of reflections | 4223 | 7966 | 3246 |
No. of parameters | 175 | 562 | 218 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.23, −0.22 | 0.31, −0.24 | 0.24, −0.19 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2007), APEX2 (Bruker, 2002), CrysAlis RED (Oxford Diffraction, 2007), SAINT-Plus (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL2013 (Sheldrick, 2015), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and Mercury (Macrae et al., 2006), PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A | |
G4 | N3—H3···O5i | 0.86 | 2.08 | 2.889 (3) | 157 |
G5 | N3—H3···O5ii | 0.82 (2) | 2.08 (2) | 2.884 (3) | 167 (2) |
Symmetry codes: (i) -x+1, -y, -z+2; (ii) x-1, y, z-1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C21A—H21C···O5Ai | 0.97 | 2.53 | 3.443 (3) | 157 |
C43—H43···O444ii | 0.93 | 2.37 | 3.212 (3) | 151 |
C45A—H45A···O442iii | 0.93 | 2.32 | 3.162 (3) | 150 |
Symmetry codes: (i) x, y+1, z; (ii) x, −y+1/2, z−1/2; (iii) x, y−1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O5i | 0.86 | 2.17 | 2.8648 (17) | 137 |
Symmetry code: (i) x−1/2, −y+1/2, z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3C···N2i | 0.96 | 2.57 | 3.5099 (15) | 166 |
C21—H21C···O441ii | 0.96 | 2.49 | 3.4046 (16) | 158 |
C42—H42···O442iii | 0.93 | 2.49 | 3.4209 (16) | 176 |
C45—H45···O5iv | 0.93 | 2.49 | 3.4034 (14) | 167 |
Symmetry codes: (i) −x+1, −y+2, −z; (ii) x−3/2, −y+3/2, z+1/2; (iii) x−1/2, −y+3/2, z−1/2; (iv) x+1/2, −y+3/2, z+1/2. |
`G5 optimized' denotes the molecule whose geometry was optimized from crystal geometry and `G5 modified optimized' the molecule whose geometry was optimized from syn conformation |
G5 crystal state | G5 optimized | G5 modified optimized | |
C1—N2—N3—C4 | 158.8 | -178.8 | 173.3 |
N2—N3—C4—C41 | 177.7 | 176.7 | 23.4 |
N3—C4—C5—C42 | -148.8 | -158.0 | -150.7 |
O5—C4—N3—H3 | -161 | -161.2 | -4.7 |