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The emergence of drug-resistant strains of Mycobacterium tuberculosis has intensified efforts to identify new lead tuberculostatics. Our earlier studies concluded that the planarity of a mol­ecule correlates well with its tuberculostatic activity. According to our hypothesis, only derivatives whose mol­ecules are capable of adopting a planar conformation may show tuberculostatic activity. The structures of three new potentially tuberculostatic compounds, namely N'-[bis­(methyl­sulfan­yl)methyl­idene]-N-methyl-4-nitro­benzohydrazide (denoted G1), C11H13N3O3S2, N'-[bis­(benzyl­sulfan­yl)methyl­idene]-N-methyl-4-nitro­ben­zo­hydrazide (denoted G2), C23H21N3O3S2, and N'-[(benzyl­sulfanyl)(methyl­sulfanyl)methyl­idene]-4-nitro­benzohydrazide (denoted G3), C16H15N3O3S2, were determined by X-ray diffraction. The significant distortion from planarity caused by the methyl substituent at the N atom of the hydrazide group or the NO2 substituent in the aromatic ring leads to the loss of tuberculostatic activity for G1, G2 and G4 {systematic name: N'-[bis­(methyl­sulfan­yl)methyl­idene]-2-nitro­benzohydrazide}. A similar effect is observed when there are large sub­stituents at the S atoms (G2 and G3).

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229615024201/sk3609sup1.cif
Contains datablocks G1, G2, G3, New_Global_Publ_Block

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229615024201/sk3609G1sup2.hkl
Contains datablock G1

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229615024201/sk3609G2sup3.hkl
Contains datablock G2

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229615024201/sk3609G3sup4.hkl
Contains datablock G3

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229615024201/sk3609G1sup5.cml
Supplementary material

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229615024201/sk3609G2sup6.cml
Supplementary material

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229615024201/sk3609G3sup7.cml
Supplementary material

CCDC references: 1442946; 1442945; 1442944

Introduction top

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 AF 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'.

Experimental top

Synthesis and crystallization top

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.

Refinement top

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 top

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).

Results and discussion top

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.

Structure description top

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 AF 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.

Synthesis and crystallization top

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.

Refinement details top

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.

Computing details top

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).

Figures top
[Figure 1] Fig. 1. The molecular structures of G1, G2 and G3, showing the atom-labelling schemes. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. To show clearly the labelling in the two independent molecules of G2, the structures are not displayed in their crystallographic mutual orientation.
[Figure 2] Fig. 2. Distribution of (a) torsion angle C3—N3—C4—O5 and (b) torsion angle H—N3—C4—O5 for structures deposited in the CSD and containing benzoic acid hydrazide derivatives.
[Figure 3] Fig. 3. Intermolecular hydrogen bonds in compound G3. [Symmetry code: (i) x - 1/2, -y + 1/2, z - 1/2.]
[Figure 4] Fig. 4. Intermolecular hydrogen bonds forming the R22(8) ring in compound G4.
[Figure 5] Fig. 5. Overlay of the G5 molecule, as determined in the crystal state with the molecule optimized by the DFT method.
(G1) N'-[Bis(methylsulfanyl)methylidene]-N-methyl-4-nitrobenzohydrazide top
Crystal data top
C11H13N3O3S2F(000) = 624
Mr = 299.36Dx = 1.438 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 6.5716 (2) ÅCell parameters from 17780 reflections
b = 16.3193 (5) Åθ = 1.6–35.9°
c = 12.8982 (4) ŵ = 0.39 mm1
β = 91.219 (3)°T = 295 K
V = 1382.94 (7) Å3, yellow
Z = 40.6 × 0.2 × 0.1 mm
Data collection top
Kuma KM-4 CCD
diffractometer
4223 independent reflections
Radiation source: fine-focus sealed tube3242 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.024
ω scanθmax = 30.5°, θmin = 2.0°
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2007)
h = 97
Tmin = 0.817, Tmax = 1.000k = 2323
28663 measured reflectionsl = 1718
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-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 = 1.18Δρmax = 0.23 e Å3
4223 reflectionsΔρmin = 0.22 e Å3
175 parametersExtinction correction: SHELXL2013 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.017 (2)
Crystal data top
C11H13N3O3S2V = 1382.94 (7) Å3
Mr = 299.36Z = 4
Monoclinic, P21/nMo Kα radiation
a = 6.5716 (2) ŵ = 0.39 mm1
b = 16.3193 (5) ÅT = 295 K
c = 12.8982 (4) Å0.6 × 0.2 × 0.1 mm
β = 91.219 (3)°
Data collection top
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 = 1.000Rint = 0.024
28663 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0310 restraints
wR(F2) = 0.110H-atom parameters constrained
S = 1.18Δρmax = 0.23 e Å3
4223 reflectionsΔρmin = 0.22 e Å3
175 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
C10.45999 (16)0.94423 (6)0.24776 (8)0.0371 (2)
C30.22718 (18)0.94937 (8)0.04218 (9)0.0473 (3)
H3A0.18010.98570.09510.071*0.5
H3B0.11860.91340.02070.071*0.5
H3C0.27070.98080.01620.071*0.5
H3D0.19950.93430.02870.071*0.5
H3E0.26101.00650.04570.071*0.5
H3F0.10890.93910.08260.071*0.5
C40.48662 (15)0.84521 (6)0.01905 (8)0.0351 (2)
C110.7949 (2)1.04207 (8)0.26835 (12)0.0597 (4)
H11A0.73461.07470.21390.089*
H11B0.87620.99960.23870.089*
H11C0.87921.07610.31220.089*
C210.1970 (2)0.92306 (10)0.41437 (11)0.0649 (4)
H21A0.17320.98110.41500.097*
H21B0.31340.91050.45770.097*
H21C0.07980.89520.44010.097*
C410.67875 (15)0.80449 (6)0.05568 (8)0.0333 (2)
C420.81936 (16)0.78550 (7)0.01969 (8)0.0406 (3)
H420.79490.80150.08800.049*
C430.99551 (17)0.74301 (7)0.00619 (9)0.0435 (3)
H431.08980.73000.04400.052*
C441.02768 (16)0.72050 (6)0.10773 (9)0.0382 (2)
C450.89217 (17)0.73786 (7)0.18471 (9)0.0400 (2)
H450.91790.72170.25290.048*
C460.71627 (17)0.78018 (6)0.15740 (8)0.0382 (2)
H460.62210.79250.20790.046*
N20.52847 (13)0.94327 (5)0.15544 (7)0.0383 (2)
N30.39838 (13)0.90080 (5)0.08326 (7)0.0370 (2)
N441.21279 (15)0.67409 (6)0.13526 (9)0.0484 (3)
O50.40735 (13)0.82678 (5)0.06438 (6)0.0492 (2)
O4411.31884 (16)0.64989 (7)0.06538 (9)0.0730 (3)
O4421.25053 (17)0.66016 (8)0.22582 (9)0.0825 (4)
S10.59742 (5)0.99673 (2)0.34386 (3)0.05254 (12)
S20.24283 (5)0.89009 (2)0.28382 (2)0.04930 (12)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0399 (6)0.0339 (5)0.0373 (6)0.0043 (4)0.0029 (4)0.0040 (4)
C30.0413 (6)0.0546 (7)0.0457 (7)0.0081 (5)0.0070 (5)0.0018 (5)
C40.0347 (5)0.0426 (5)0.0279 (5)0.0046 (4)0.0003 (4)0.0002 (4)
C110.0464 (7)0.0566 (8)0.0754 (10)0.0054 (6)0.0099 (6)0.0144 (7)
C210.0807 (10)0.0710 (9)0.0437 (7)0.0072 (7)0.0179 (7)0.0019 (6)
C410.0342 (5)0.0336 (5)0.0321 (5)0.0044 (4)0.0005 (4)0.0026 (4)
C420.0428 (6)0.0495 (6)0.0297 (5)0.0026 (4)0.0030 (4)0.0010 (4)
C430.0384 (6)0.0521 (6)0.0403 (6)0.0013 (5)0.0084 (5)0.0056 (5)
C440.0347 (5)0.0350 (5)0.0446 (6)0.0024 (4)0.0015 (4)0.0053 (4)
C450.0452 (6)0.0392 (5)0.0356 (5)0.0000 (4)0.0031 (4)0.0003 (4)
C460.0398 (6)0.0431 (5)0.0318 (5)0.0015 (4)0.0048 (4)0.0020 (4)
N20.0385 (5)0.0387 (4)0.0375 (5)0.0009 (3)0.0030 (4)0.0053 (4)
N30.0332 (5)0.0441 (5)0.0336 (5)0.0012 (3)0.0046 (3)0.0029 (4)
N440.0411 (6)0.0447 (5)0.0594 (7)0.0039 (4)0.0022 (5)0.0071 (4)
O50.0463 (5)0.0665 (5)0.0346 (4)0.0000 (4)0.0082 (3)0.0097 (3)
O4410.0591 (6)0.0830 (7)0.0776 (7)0.0283 (5)0.0194 (5)0.0072 (6)
O4420.0756 (7)0.1120 (9)0.0589 (7)0.0425 (6)0.0224 (5)0.0135 (6)
S10.0561 (2)0.0567 (2)0.0444 (2)0.00030 (13)0.00951 (14)0.01615 (13)
S20.0526 (2)0.0531 (2)0.04251 (19)0.00774 (13)0.00746 (14)0.00318 (12)
Geometric parameters (Å, º) top
C1—N21.2820 (14)C21—H21A0.9600
C1—S11.7431 (11)C21—H21B0.9600
C1—S21.7497 (11)C21—H21C0.9600
C3—N31.4660 (14)C41—C461.3877 (14)
C3—H3A0.9600C41—C421.3905 (14)
C3—H3B0.9600C42—C431.3840 (17)
C3—H3C0.9600C42—H420.9300
C3—H3D0.9600C43—C441.3724 (16)
C3—H3E0.9600C43—H430.9300
C3—H3F0.9600C44—C451.3772 (16)
C4—O51.2231 (12)C44—N441.4701 (15)
C4—N31.3658 (13)C45—C461.3857 (15)
C4—C411.4945 (14)C45—H450.9300
C11—S11.7983 (14)C46—H460.9300
C11—H11A0.9600N2—N31.4297 (12)
C11—H11B0.9600N44—O4421.2104 (15)
C11—H11C0.9600N44—O4411.2169 (14)
C21—S21.7992 (14)
N2—C1—S1118.67 (8)S2—C21—H21A109.5
N2—C1—S2123.03 (9)S2—C21—H21B109.5
S1—C1—S2118.19 (6)H21A—C21—H21B109.5
N3—C3—H3A109.5S2—C21—H21C109.5
N3—C3—H3B109.5H21A—C21—H21C109.5
H3A—C3—H3B109.5H21B—C21—H21C109.5
N3—C3—H3C109.5C46—C41—C42119.34 (10)
H3A—C3—H3C109.5C46—C41—C4123.91 (9)
H3B—C3—H3C109.5C42—C41—C4116.59 (9)
N3—C3—H3D109.5C43—C42—C41120.52 (10)
H3A—C3—H3D141.1C43—C42—H42119.7
H3B—C3—H3D56.3C41—C42—H42119.7
H3C—C3—H3D56.3C44—C43—C42118.38 (10)
N3—C3—H3E109.5C44—C43—H43120.8
H3A—C3—H3E56.3C42—C43—H43120.8
H3B—C3—H3E141.1C43—C44—C45122.96 (11)
H3C—C3—H3E56.3C43—C44—N44118.58 (10)
H3D—C3—H3E109.5C45—C44—N44118.44 (11)
N3—C3—H3F109.5C44—C45—C46117.91 (11)
H3A—C3—H3F56.3C44—C45—H45121.0
H3B—C3—H3F56.3C46—C45—H45121.0
H3C—C3—H3F141.1C45—C46—C41120.88 (10)
H3D—C3—H3F109.5C45—C46—H46119.6
H3E—C3—H3F109.5C41—C46—H46119.6
O5—C4—N3121.23 (10)C1—N2—N3113.20 (9)
O5—C4—C41120.66 (9)C4—N3—N2117.46 (8)
N3—C4—C41118.06 (9)C4—N3—C3118.19 (9)
S1—C11—H11A109.5N2—N3—C3114.64 (9)
S1—C11—H11B109.5O442—N44—O441123.02 (11)
H11A—C11—H11B109.5O442—N44—C44118.77 (10)
S1—C11—H11C109.5O441—N44—C44118.18 (11)
H11A—C11—H11C109.5C1—S1—C11100.72 (6)
H11B—C11—H11C109.5C1—S2—C21104.57 (7)
O5—C4—C41—C46139.25 (11)S2—C1—N2—N36.12 (12)
N3—C4—C41—C4638.07 (14)O5—C4—N3—N2155.53 (10)
O5—C4—C41—C4236.12 (15)C41—C4—N3—N227.16 (13)
N3—C4—C41—C42146.56 (10)O5—C4—N3—C311.28 (15)
C46—C41—C42—C430.21 (16)C41—C4—N3—C3171.42 (10)
C4—C41—C42—C43175.80 (10)C1—N2—N3—C4132.55 (10)
C41—C42—C43—C440.19 (17)C1—N2—N3—C381.95 (12)
C42—C43—C44—C450.39 (17)C43—C44—N44—O442173.79 (12)
C42—C43—C44—N44178.93 (10)C45—C44—N44—O4427.61 (16)
C43—C44—C45—C460.17 (16)C43—C44—N44—O4417.80 (16)
N44—C44—C45—C46178.71 (9)C45—C44—N44—O441170.81 (11)
C44—C45—C46—C410.25 (16)N2—C1—S1—C114.95 (10)
C42—C41—C46—C450.44 (16)S2—C1—S1—C11178.85 (7)
C4—C41—C46—C45175.68 (10)N2—C1—S2—C21172.74 (10)
S1—C1—N2—N3177.87 (7)S1—C1—S2—C2111.24 (9)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C3—H3C···N2i0.962.573.5099 (15)166
C21—H21C···O441ii0.962.493.4046 (16)158
C42—H42···O442iii0.932.493.4209 (16)176
C45—H45···O5iv0.932.493.4034 (14)167
Symmetry codes: (i) x+1, y+2, z; (ii) x3/2, y+3/2, z+1/2; (iii) x1/2, y+3/2, z1/2; (iv) x+1/2, y+3/2, z+1/2.
(G2) N'-[Bis(benzylsulfanyl)methylidene]-N-methyl-4-nitrobenzohydrazide top
Crystal data top
C23H21N3O3S2F(000) = 1888
Mr = 451.55Dx = 1.330 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 14105 reflections
a = 28.5519 (16) Åθ = 1.9–35.8°
b = 7.9549 (4) ŵ = 0.27 mm1
c = 21.3930 (12) ÅT = 296 K
β = 111.841 (5)°, yellow
V = 4510.2 (4) Å30.3 × 0.15 × 0.1 mm
Z = 8
Data collection top
Kuma KM-4 CCD
diffractometer
7966 independent reflections
Radiation source: fine-focus sealed tube5304 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.050
ω scanθmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2007)
h = 3333
Tmin = 0.721, Tmax = 1.000k = 99
45186 measured reflectionsl = 2525
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.034H-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 reflectionsΔρmax = 0.31 e Å3
562 parametersΔρmin = 0.24 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0051 (3)
Crystal data top
C23H21N3O3S2V = 4510.2 (4) Å3
Mr = 451.55Z = 8
Monoclinic, P21/cMo Kα radiation
a = 28.5519 (16) ŵ = 0.27 mm1
b = 7.9549 (4) ÅT = 296 K
c = 21.3930 (12) Å0.3 × 0.15 × 0.1 mm
β = 111.841 (5)°
Data collection top
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 = 1.000Rint = 0.050
45186 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0340 restraints
wR(F2) = 0.089H-atom parameters constrained
S = 0.90Δρmax = 0.31 e Å3
7966 reflectionsΔρmin = 0.24 e Å3
562 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.42581 (7)0.3466 (2)0.35136 (8)0.0454 (4)
C30.51319 (8)0.5526 (2)0.32397 (10)0.0671 (6)
H3A0.50980.45970.29400.101*
H3B0.54060.53150.36580.101*
H3C0.51980.65350.30400.101*
C40.43604 (7)0.7026 (2)0.31302 (8)0.0440 (4)
C110.44199 (9)0.2740 (3)0.48319 (8)0.0708 (6)
H11A0.47790.27720.49240.085*
H11B0.43100.38650.48860.085*
C120.43134 (9)0.1550 (2)0.53067 (8)0.0559 (5)
C130.38626 (10)0.1544 (3)0.53809 (11)0.0753 (6)
H130.36090.22760.51270.090*
C140.37765 (11)0.0465 (4)0.58286 (13)0.0933 (8)
H140.34670.04650.58790.112*
C150.41488 (14)0.0603 (3)0.61972 (11)0.0900 (8)
H150.40930.13360.65000.108*
C160.45950 (12)0.0606 (3)0.61268 (11)0.0823 (7)
H160.48480.13360.63830.099*
C170.46807 (9)0.0457 (2)0.56813 (9)0.0660 (6)
H170.49910.04400.56320.079*
C210.35690 (9)0.1534 (2)0.25117 (9)0.0675 (6)
H21A0.37770.05600.27060.081*
H21B0.33300.16770.27330.081*
C220.32931 (8)0.1272 (2)0.17775 (9)0.0591 (5)
C230.28526 (11)0.2078 (3)0.14347 (13)0.0999 (9)
H230.27250.28510.16560.120*
C240.25939 (13)0.1757 (5)0.07598 (16)0.1291 (12)
H240.22940.23210.05270.155*
C250.27732 (14)0.0639 (4)0.04408 (13)0.1084 (10)
H250.25940.04080.00120.130*
C260.32114 (12)0.0157 (3)0.07702 (12)0.0900 (8)
H260.33370.09240.05440.108*
C270.34711 (9)0.0163 (3)0.14371 (10)0.0688 (6)
H270.37750.03880.16620.083*
C410.39456 (7)0.72637 (18)0.33849 (8)0.0408 (4)
C420.34684 (7)0.7557 (2)0.29309 (9)0.0489 (4)
H420.34050.74900.24730.059*
C430.30850 (7)0.7944 (2)0.31368 (9)0.0556 (5)
H430.27610.81420.28260.067*
C440.31885 (7)0.8035 (2)0.38120 (10)0.0542 (5)
C450.36597 (8)0.7754 (2)0.42832 (9)0.0552 (5)
H450.37210.78360.47410.066*
C460.40378 (7)0.7349 (2)0.40670 (8)0.0473 (4)
H460.43600.71280.43790.057*
C1A0.06914 (7)0.1697 (2)0.42161 (8)0.0453 (4)
C3A0.01471 (8)0.0481 (3)0.30743 (9)0.0682 (6)
H3A10.01260.04670.28090.102*
H3A20.04250.03300.32180.102*
H3A30.01980.14860.28090.102*
C4A0.06407 (7)0.1878 (2)0.37417 (8)0.0472 (4)
C11A0.05874 (9)0.2213 (3)0.54322 (10)0.0711 (6)
H11C0.02240.21330.52090.085*
H11D0.07220.10940.55690.085*
C12A0.07213 (8)0.3344 (2)0.60311 (9)0.0570 (5)
C13A0.11866 (10)0.3283 (3)0.65334 (11)0.0799 (7)
H13A0.14260.25230.65070.096*
C14A0.13030 (12)0.4342 (4)0.70786 (11)0.1003 (9)
H14A0.16210.43010.74210.120*
C15A0.09538 (16)0.5443 (4)0.71149 (13)0.1014 (10)
H15A0.10300.61550.74840.122*
C16A0.04966 (14)0.5510 (3)0.66197 (16)0.0981 (9)
H16A0.02570.62660.66490.118*
C17A0.03802 (9)0.4484 (3)0.60757 (11)0.0741 (6)
H17A0.00650.45620.57310.089*
C21A0.13819 (8)0.3704 (2)0.39231 (10)0.0657 (6)
H21C0.11860.47220.38820.079*
H21D0.15880.35400.43950.079*
C22A0.17097 (8)0.3877 (2)0.35292 (10)0.0617 (5)
C23A0.21322 (11)0.2920 (3)0.36772 (14)0.0914 (8)
H23A0.22110.21110.40140.110*
C24A0.24448 (13)0.3165 (5)0.3320 (2)0.1363 (14)
H24A0.27340.25180.34140.164*
C25A0.23233 (19)0.4359 (5)0.2831 (2)0.1478 (18)
H25A0.25350.45410.25960.177*
C26A0.18985 (17)0.5286 (4)0.26811 (17)0.1275 (13)
H26A0.18150.60830.23390.153*
C27A0.15985 (11)0.5045 (3)0.30300 (12)0.0860 (7)
H27A0.13080.56920.29280.103*
C41A0.10633 (7)0.19892 (19)0.44148 (8)0.0431 (4)
C42A0.09680 (7)0.2396 (2)0.49826 (9)0.0546 (5)
H42A0.06370.25320.49520.065*
C43A0.13546 (8)0.2601 (3)0.55883 (9)0.0607 (5)
H43A0.12930.29230.59680.073*
C44A0.18308 (8)0.2324 (3)0.56214 (9)0.0604 (5)
C45A0.19377 (8)0.1908 (3)0.50731 (10)0.0678 (6)
H45A0.22680.17140.51110.081*
C46A0.15465 (7)0.1781 (2)0.44613 (9)0.0571 (5)
H46A0.16130.15510.40760.069*
N20.45932 (6)0.45536 (17)0.38155 (7)0.0487 (4)
N30.46689 (6)0.57237 (17)0.33617 (7)0.0482 (4)
N440.27818 (8)0.8461 (3)0.40323 (12)0.0825 (6)
N2A0.03810 (6)0.05206 (17)0.41962 (7)0.0501 (4)
N3A0.03177 (6)0.06251 (17)0.36597 (7)0.0489 (4)
N44A0.22477 (9)0.2473 (3)0.62686 (10)0.0907 (7)
O50.44087 (5)0.80144 (15)0.27225 (6)0.0604 (3)
O4410.23726 (8)0.8798 (3)0.36268 (10)0.1084 (6)
O4420.28724 (8)0.8478 (4)0.46296 (11)0.1523 (10)
O4430.26424 (8)0.1797 (3)0.63436 (10)0.1253 (8)
O4440.21712 (8)0.3280 (3)0.67050 (9)0.1312 (8)
O5A0.06050 (5)0.28860 (16)0.33003 (6)0.0674 (4)
S10.40815 (2)0.20008 (5)0.39877 (2)0.05526 (15)
S20.39600 (2)0.33777 (6)0.26385 (2)0.05906 (15)
S1A0.08603 (2)0.31211 (6)0.48767 (2)0.05795 (15)
S2A0.09650 (2)0.19357 (6)0.36155 (2)0.05478 (14)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0550 (12)0.0334 (9)0.0458 (9)0.0028 (9)0.0164 (9)0.0035 (8)
C30.0657 (15)0.0660 (13)0.0810 (14)0.0038 (11)0.0404 (12)0.0010 (11)
C40.0500 (11)0.0391 (10)0.0425 (9)0.0096 (9)0.0168 (8)0.0028 (8)
C110.0934 (18)0.0617 (12)0.0447 (10)0.0138 (12)0.0112 (11)0.0060 (9)
C120.0787 (15)0.0454 (10)0.0388 (9)0.0010 (10)0.0162 (10)0.0017 (8)
C130.0926 (19)0.0733 (14)0.0652 (13)0.0158 (13)0.0354 (13)0.0020 (11)
C140.109 (2)0.116 (2)0.0779 (16)0.0044 (18)0.0613 (16)0.0177 (16)
C150.149 (3)0.0774 (17)0.0560 (13)0.0170 (18)0.0523 (17)0.0013 (12)
C160.117 (2)0.0641 (14)0.0612 (13)0.0103 (14)0.0272 (14)0.0152 (11)
C170.0800 (16)0.0620 (12)0.0518 (11)0.0038 (12)0.0196 (11)0.0034 (10)
C210.0883 (17)0.0528 (11)0.0524 (11)0.0206 (11)0.0157 (11)0.0003 (9)
C220.0643 (14)0.0514 (11)0.0535 (11)0.0145 (10)0.0126 (10)0.0003 (9)
C230.093 (2)0.0967 (19)0.0877 (17)0.0164 (17)0.0078 (16)0.0127 (15)
C240.101 (3)0.133 (3)0.100 (2)0.020 (2)0.0240 (19)0.001 (2)
C250.127 (3)0.100 (2)0.0623 (15)0.023 (2)0.0065 (17)0.0034 (15)
C260.123 (2)0.0792 (16)0.0632 (14)0.0218 (17)0.0287 (16)0.0099 (13)
C270.0787 (16)0.0618 (13)0.0589 (12)0.0101 (11)0.0176 (11)0.0010 (10)
C410.0478 (11)0.0304 (8)0.0427 (9)0.0066 (8)0.0152 (8)0.0021 (7)
C420.0502 (12)0.0490 (10)0.0436 (9)0.0078 (9)0.0129 (9)0.0029 (8)
C430.0444 (12)0.0572 (11)0.0595 (11)0.0059 (9)0.0127 (9)0.0057 (9)
C440.0502 (12)0.0514 (11)0.0683 (12)0.0042 (9)0.0307 (10)0.0031 (9)
C450.0613 (14)0.0609 (12)0.0465 (10)0.0045 (10)0.0235 (10)0.0016 (9)
C460.0462 (11)0.0484 (10)0.0442 (9)0.0024 (9)0.0132 (8)0.0045 (8)
C1A0.0519 (12)0.0387 (9)0.0434 (9)0.0072 (9)0.0156 (8)0.0007 (7)
C3A0.0613 (14)0.0719 (13)0.0525 (11)0.0024 (11)0.0005 (10)0.0043 (10)
C4A0.0518 (12)0.0466 (10)0.0423 (9)0.0065 (9)0.0166 (8)0.0043 (8)
C11A0.0866 (17)0.0687 (13)0.0744 (13)0.0099 (12)0.0489 (12)0.0144 (11)
C12A0.0722 (15)0.0544 (11)0.0552 (11)0.0019 (11)0.0362 (11)0.0010 (9)
C13A0.0906 (19)0.0851 (16)0.0641 (13)0.0170 (14)0.0292 (13)0.0090 (12)
C14A0.122 (3)0.118 (2)0.0480 (13)0.015 (2)0.0163 (14)0.0069 (14)
C15A0.175 (3)0.0819 (18)0.0630 (16)0.021 (2)0.063 (2)0.0171 (14)
C16A0.143 (3)0.0758 (17)0.103 (2)0.0083 (18)0.077 (2)0.0153 (16)
C17A0.0802 (17)0.0724 (14)0.0789 (14)0.0070 (12)0.0402 (13)0.0081 (12)
C21A0.0784 (15)0.0568 (11)0.0704 (12)0.0142 (11)0.0376 (12)0.0154 (10)
C22A0.0688 (15)0.0556 (12)0.0690 (12)0.0186 (11)0.0352 (11)0.0220 (10)
C23A0.087 (2)0.0885 (18)0.1083 (19)0.0001 (15)0.0469 (16)0.0215 (14)
C24A0.105 (3)0.128 (3)0.213 (4)0.020 (2)0.102 (3)0.066 (3)
C25A0.196 (5)0.107 (3)0.219 (4)0.076 (3)0.168 (4)0.069 (3)
C26A0.204 (4)0.088 (2)0.144 (3)0.039 (2)0.126 (3)0.0188 (19)
C27A0.118 (2)0.0644 (14)0.0955 (17)0.0200 (14)0.0632 (17)0.0084 (13)
C41A0.0464 (11)0.0375 (9)0.0435 (9)0.0015 (8)0.0144 (8)0.0045 (7)
C42A0.0474 (12)0.0624 (12)0.0535 (11)0.0032 (9)0.0183 (9)0.0012 (9)
C43A0.0634 (15)0.0735 (13)0.0431 (10)0.0051 (11)0.0173 (10)0.0017 (9)
C44A0.0514 (13)0.0736 (13)0.0447 (10)0.0152 (11)0.0045 (9)0.0095 (9)
C45A0.0415 (12)0.0936 (16)0.0677 (13)0.0051 (11)0.0197 (10)0.0064 (11)
C46A0.0528 (13)0.0698 (13)0.0521 (10)0.0062 (10)0.0235 (10)0.0009 (9)
N20.0548 (10)0.0399 (8)0.0497 (8)0.0005 (7)0.0174 (7)0.0041 (7)
N30.0506 (10)0.0418 (8)0.0569 (8)0.0024 (7)0.0254 (7)0.0032 (7)
N440.0659 (15)0.1038 (15)0.0903 (14)0.0005 (12)0.0436 (12)0.0026 (12)
N2A0.0533 (10)0.0457 (9)0.0495 (8)0.0016 (8)0.0169 (7)0.0041 (7)
N3A0.0514 (10)0.0448 (8)0.0421 (8)0.0000 (7)0.0075 (7)0.0049 (7)
N44A0.0707 (16)0.1283 (18)0.0551 (11)0.0279 (14)0.0025 (11)0.0153 (12)
O50.0731 (10)0.0565 (8)0.0601 (7)0.0036 (7)0.0346 (7)0.0143 (6)
O4410.0727 (13)0.1356 (16)0.1255 (15)0.0265 (12)0.0469 (12)0.0071 (13)
O4420.0944 (16)0.284 (3)0.1038 (15)0.0167 (18)0.0664 (13)0.0045 (17)
O4430.0648 (13)0.172 (2)0.1005 (14)0.0022 (14)0.0137 (11)0.0190 (13)
O4440.1093 (17)0.206 (2)0.0555 (10)0.0244 (15)0.0045 (11)0.0157 (13)
O5A0.0800 (11)0.0623 (8)0.0512 (7)0.0034 (7)0.0145 (7)0.0192 (7)
S10.0716 (4)0.0445 (3)0.0444 (2)0.0083 (2)0.0155 (2)0.0077 (2)
S20.0851 (4)0.0443 (3)0.0430 (2)0.0153 (3)0.0183 (2)0.0007 (2)
S1A0.0772 (4)0.0484 (3)0.0556 (3)0.0049 (2)0.0331 (3)0.0117 (2)
S2A0.0708 (4)0.0499 (3)0.0469 (2)0.0079 (2)0.0256 (2)0.0063 (2)
Geometric parameters (Å, º) top
C1—N21.273 (2)C3A—N3A1.451 (2)
C1—S11.7382 (17)C3A—H3A10.9600
C1—S21.7460 (17)C3A—H3A20.9600
C3—N31.448 (2)C3A—H3A30.9600
C3—H3A0.9600C4A—O5A1.2137 (19)
C3—H3B0.9600C4A—N3A1.325 (2)
C3—H3C0.9600C4A—C41A1.498 (2)
C4—O51.2197 (18)C11A—C12A1.494 (3)
C4—N31.330 (2)C11A—S1A1.797 (2)
C4—C411.488 (2)C11A—H11C0.9700
C11—C121.500 (3)C11A—H11D0.9700
C11—S11.8007 (18)C12A—C17A1.360 (3)
C11—H11A0.9700C12A—C13A1.364 (3)
C11—H11B0.9700C13A—C14A1.376 (3)
C12—C131.354 (3)C13A—H13A0.9300
C12—C171.368 (3)C14A—C15A1.351 (4)
C13—C141.375 (3)C14A—H14A0.9300
C13—H130.9300C15A—C16A1.342 (4)
C14—C151.360 (4)C15A—H15A0.9300
C14—H140.9300C16A—C17A1.358 (3)
C15—C161.337 (4)C16A—H16A0.9300
C15—H150.9300C17A—H17A0.9300
C16—C171.363 (3)C21A—C22A1.481 (3)
C16—H160.9300C21A—S2A1.8020 (19)
C17—H170.9300C21A—H21C0.9700
C21—C221.487 (2)C21A—H21D0.9700
C21—S21.8016 (19)C22A—C23A1.360 (3)
C21—H21A0.9700C22A—C27A1.361 (3)
C21—H21B0.9700C23A—C24A1.388 (4)
C22—C271.357 (3)C23A—H23A0.9300
C22—C231.358 (3)C24A—C25A1.360 (5)
C23—C241.379 (4)C24A—H24A0.9300
C23—H230.9300C25A—C26A1.352 (5)
C24—C251.334 (4)C25A—H25A0.9300
C24—H240.9300C26A—C27A1.343 (4)
C25—C261.344 (4)C26A—H26A0.9300
C25—H250.9300C27A—H27A0.9300
C26—C271.365 (3)C41A—C46A1.356 (3)
C26—H260.9300C41A—C42A1.379 (2)
C27—H270.9300C42A—C43A1.364 (2)
C41—C421.367 (2)C42A—H42A0.9300
C41—C461.385 (2)C43A—C44A1.353 (3)
C42—C431.359 (3)C43A—H43A0.9300
C42—H420.9300C44A—C45A1.358 (3)
C43—C441.364 (2)C44A—N44A1.457 (3)
C43—H430.9300C45A—C46A1.372 (3)
C44—C451.367 (3)C45A—H45A0.9300
C44—N441.446 (3)C46A—H46A0.9300
C45—C461.362 (3)N2—N31.4184 (18)
C45—H450.9300N44—O4411.198 (2)
C46—H460.9300N44—O4421.206 (2)
C1A—N2A1.278 (2)N2A—N3A1.4234 (18)
C1A—S1A1.7339 (17)N44A—O4431.204 (3)
C1A—S2A1.7448 (17)N44A—O4441.218 (3)
N2—C1—S1119.08 (12)O5A—C4A—N3A122.77 (16)
N2—C1—S2123.07 (12)O5A—C4A—C41A120.89 (16)
S1—C1—S2117.85 (10)N3A—C4A—C41A116.34 (14)
N3—C3—H3A109.5C12A—C11A—S1A106.82 (14)
N3—C3—H3B109.5C12A—C11A—H11C110.4
H3A—C3—H3B109.5S1A—C11A—H11C110.4
N3—C3—H3C109.5C12A—C11A—H11D110.4
H3A—C3—H3C109.5S1A—C11A—H11D110.4
H3B—C3—H3C109.5H11C—C11A—H11D108.6
O5—C4—N3122.18 (16)C17A—C12A—C13A118.8 (2)
O5—C4—C41119.81 (16)C17A—C12A—C11A120.0 (2)
N3—C4—C41118.00 (14)C13A—C12A—C11A121.2 (2)
C12—C11—S1107.76 (13)C12A—C13A—C14A120.2 (2)
C12—C11—H11A110.2C12A—C13A—H13A119.9
S1—C11—H11A110.2C14A—C13A—H13A119.9
C12—C11—H11B110.2C15A—C14A—C13A119.7 (3)
S1—C11—H11B110.2C15A—C14A—H14A120.2
H11A—C11—H11B108.5C13A—C14A—H14A120.2
C13—C12—C17118.95 (19)C16A—C15A—C14A120.2 (2)
C13—C12—C11121.5 (2)C16A—C15A—H15A119.9
C17—C12—C11119.5 (2)C14A—C15A—H15A119.9
C12—C13—C14120.5 (2)C15A—C16A—C17A120.6 (3)
C12—C13—H13119.7C15A—C16A—H16A119.7
C14—C13—H13119.7C17A—C16A—H16A119.7
C15—C14—C13119.3 (3)C16A—C17A—C12A120.5 (2)
C15—C14—H14120.3C16A—C17A—H17A119.8
C13—C14—H14120.3C12A—C17A—H17A119.8
C16—C15—C14120.5 (2)C22A—C21A—S2A109.64 (13)
C16—C15—H15119.7C22A—C21A—H21C109.7
C14—C15—H15119.7S2A—C21A—H21C109.7
C15—C16—C17120.3 (2)C22A—C21A—H21D109.7
C15—C16—H16119.9S2A—C21A—H21D109.7
C17—C16—H16119.9H21C—C21A—H21D108.2
C16—C17—C12120.4 (2)C23A—C22A—C27A119.5 (2)
C16—C17—H17119.8C23A—C22A—C21A120.6 (2)
C12—C17—H17119.8C27A—C22A—C21A119.8 (2)
C22—C21—S2109.18 (13)C22A—C23A—C24A119.3 (3)
C22—C21—H21A109.8C22A—C23A—H23A120.3
S2—C21—H21A109.8C24A—C23A—H23A120.3
C22—C21—H21B109.8C25A—C24A—C23A119.3 (3)
S2—C21—H21B109.8C25A—C24A—H24A120.3
H21A—C21—H21B108.3C23A—C24A—H24A120.3
C27—C22—C23118.3 (2)C26A—C25A—C24A120.8 (3)
C27—C22—C21120.1 (2)C26A—C25A—H25A119.6
C23—C22—C21121.6 (2)C24A—C25A—H25A119.6
C22—C23—C24120.4 (3)C27A—C26A—C25A119.5 (3)
C22—C23—H23119.8C27A—C26A—H26A120.2
C24—C23—H23119.8C25A—C26A—H26A120.2
C25—C24—C23120.1 (3)C26A—C27A—C22A121.5 (3)
C25—C24—H24120.0C26A—C27A—H27A119.3
C23—C24—H24120.0C22A—C27A—H27A119.3
C24—C25—C26120.4 (3)C46A—C41A—C42A119.53 (17)
C24—C25—H25119.8C46A—C41A—C4A119.81 (15)
C26—C25—H25119.8C42A—C41A—C4A120.55 (16)
C25—C26—C27119.9 (3)C43A—C42A—C41A120.66 (18)
C25—C26—H26120.1C43A—C42A—H42A119.7
C27—C26—H26120.1C41A—C42A—H42A119.7
C22—C27—C26121.0 (2)C44A—C43A—C42A118.21 (18)
C22—C27—H27119.5C44A—C43A—H43A120.9
C26—C27—H27119.5C42A—C43A—H43A120.9
C42—C41—C46119.26 (17)C43A—C44A—C45A122.60 (18)
C42—C41—C4118.68 (15)C43A—C44A—N44A119.1 (2)
C46—C41—C4121.79 (16)C45A—C44A—N44A118.3 (2)
C43—C42—C41121.23 (17)C44A—C45A—C46A118.48 (19)
C43—C42—H42119.4C44A—C45A—H45A120.8
C41—C42—H42119.4C46A—C45A—H45A120.8
C42—C43—C44118.16 (18)C41A—C46A—C45A120.40 (17)
C42—C43—H43120.9C41A—C46A—H46A119.8
C44—C43—H43120.9C45A—C46A—H46A119.8
C43—C44—C45122.57 (18)C1—N2—N3112.08 (13)
C43—C44—N44118.25 (19)C4—N3—N2121.15 (14)
C45—C44—N44119.18 (18)C4—N3—C3122.68 (14)
C46—C45—C44118.39 (16)N2—N3—C3115.72 (14)
C46—C45—H45120.8O441—N44—O442122.1 (2)
C44—C45—H45120.8O441—N44—C44120.1 (2)
C45—C46—C41120.37 (17)O442—N44—C44117.8 (2)
C45—C46—H46119.8C1A—N2A—N3A111.97 (14)
C41—C46—H46119.8C4A—N3A—N2A120.12 (13)
N2A—C1A—S1A118.99 (13)C4A—N3A—C3A122.80 (15)
N2A—C1A—S2A123.36 (13)N2A—N3A—C3A116.51 (14)
S1A—C1A—S2A117.64 (11)O443—N44A—O444124.0 (2)
N3A—C3A—H3A1109.5O443—N44A—C44A118.9 (3)
N3A—C3A—H3A2109.5O444—N44A—C44A117.1 (3)
H3A1—C3A—H3A2109.5C1—S1—C11101.68 (9)
N3A—C3A—H3A3109.5C1—S2—C21102.81 (8)
H3A1—C3A—H3A3109.5C1A—S1A—C11A102.63 (9)
H3A2—C3A—H3A3109.5C1A—S2A—C21A103.42 (9)
S1—C11—C12—C1374.1 (2)C23A—C22A—C27A—C26A0.4 (3)
S1—C11—C12—C17106.70 (18)C21A—C22A—C27A—C26A177.2 (2)
C17—C12—C13—C140.4 (3)O5A—C4A—C41A—C46A63.8 (2)
C11—C12—C13—C14178.75 (19)N3A—C4A—C41A—C46A115.65 (19)
C12—C13—C14—C150.1 (3)O5A—C4A—C41A—C42A112.5 (2)
C13—C14—C15—C160.1 (4)N3A—C4A—C41A—C42A68.1 (2)
C14—C15—C16—C170.4 (4)C46A—C41A—C42A—C43A0.4 (3)
C15—C16—C17—C120.7 (3)C4A—C41A—C42A—C43A175.86 (17)
C13—C12—C17—C160.7 (3)C41A—C42A—C43A—C44A2.8 (3)
C11—C12—C17—C16178.48 (18)C42A—C43A—C44A—C45A2.3 (3)
S2—C21—C22—C2797.8 (2)C42A—C43A—C44A—N44A177.68 (19)
S2—C21—C22—C2384.4 (2)C43A—C44A—C45A—C46A0.6 (3)
C27—C22—C23—C240.6 (4)N44A—C44A—C45A—C46A179.42 (19)
C21—C22—C23—C24177.3 (3)C42A—C41A—C46A—C45A2.6 (3)
C22—C23—C24—C250.6 (5)C4A—C41A—C46A—C45A178.88 (17)
C23—C24—C25—C261.4 (5)C44A—C45A—C46A—C41A3.1 (3)
C24—C25—C26—C270.9 (5)S1—C1—N2—N3175.93 (11)
C23—C22—C27—C261.0 (3)S2—C1—N2—N33.6 (2)
C21—C22—C27—C26176.85 (19)O5—C4—N3—N2177.49 (15)
C25—C26—C27—C220.3 (4)C41—C4—N3—N22.7 (2)
O5—C4—C41—C4248.1 (2)O5—C4—N3—C310.5 (3)
N3—C4—C41—C42132.04 (16)C41—C4—N3—C3169.32 (15)
O5—C4—C41—C46125.91 (18)C1—N2—N3—C481.10 (19)
N3—C4—C41—C4654.0 (2)C1—N2—N3—C3106.40 (18)
C46—C41—C42—C430.6 (2)C43—C44—N44—O4413.4 (3)
C4—C41—C42—C43173.55 (15)C45—C44—N44—O441176.1 (2)
C41—C42—C43—C440.0 (3)C43—C44—N44—O442177.3 (2)
C42—C43—C44—C450.0 (3)C45—C44—N44—O4423.2 (3)
C42—C43—C44—N44179.50 (17)S1A—C1A—N2A—N3A174.63 (11)
C43—C44—C45—C460.7 (3)S2A—C1A—N2A—N3A4.4 (2)
N44—C44—C45—C46179.79 (17)O5A—C4A—N3A—N2A179.74 (16)
C44—C45—C46—C411.4 (3)C41A—C4A—N3A—N2A0.3 (2)
C42—C41—C46—C451.3 (2)O5A—C4A—N3A—C3A9.3 (3)
C4—C41—C46—C45172.62 (16)C41A—C4A—N3A—C3A171.33 (16)
S1A—C11A—C12A—C17A99.1 (2)C1A—N2A—N3A—C4A84.21 (19)
S1A—C11A—C12A—C13A79.5 (2)C1A—N2A—N3A—C3A104.24 (18)
C17A—C12A—C13A—C14A1.0 (3)C43A—C44A—N44A—O443159.6 (2)
C11A—C12A—C13A—C14A179.6 (2)C45A—C44A—N44A—O44320.4 (3)
C12A—C13A—C14A—C15A0.1 (4)C43A—C44A—N44A—O44420.0 (3)
C13A—C14A—C15A—C16A0.4 (4)C45A—C44A—N44A—O444160.0 (2)
C14A—C15A—C16A—C17A0.4 (4)N2—C1—S1—C116.45 (17)
C15A—C16A—C17A—C12A1.5 (4)S2—C1—S1—C11173.11 (12)
C13A—C12A—C17A—C16A1.8 (3)C12—C11—S1—C1178.50 (15)
C11A—C12A—C17A—C16A179.5 (2)N2—C1—S2—C21176.02 (16)
S2A—C21A—C22A—C23A81.9 (2)S1—C1—S2—C214.45 (14)
S2A—C21A—C22A—C27A100.6 (2)C22—C21—S2—C1179.05 (15)
C27A—C22A—C23A—C24A0.6 (3)N2A—C1A—S1A—C11A8.70 (17)
C21A—C22A—C23A—C24A177.0 (2)S2A—C1A—S1A—C11A170.40 (12)
C22A—C23A—C24A—C25A0.2 (5)C12A—C11A—S1A—C1A178.98 (15)
C23A—C24A—C25A—C26A1.2 (6)N2A—C1A—S2A—C21A177.36 (15)
C24A—C25A—C26A—C27A1.4 (5)S1A—C1A—S2A—C21A1.70 (13)
C25A—C26A—C27A—C22A0.6 (4)C22A—C21A—S2A—C1A170.06 (15)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C21A—H21C···O5Ai0.972.533.443 (3)157
C43—H43···O444ii0.932.373.212 (3)151
C45A—H45A···O442iii0.932.323.162 (3)150
Symmetry codes: (i) x, y+1, z; (ii) x, y+1/2, z1/2; (iii) x, y1, z.
(G3) N'-[(Benzylsulfanyl)(methylsulfanyl)methylidene]-4-nitrobenzohydrazide top
Crystal data top
C16H15N3O3S2F(000) = 752
Mr = 361.43Dx = 1.373 Mg m3
Monoclinic, P21/nCu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ynCell parameters from 7846 reflections
a = 7.3383 (2) Åθ = 2.8–69.3°
b = 31.5484 (8) ŵ = 2.93 mm1
c = 8.0521 (2) ÅT = 290 K
β = 110.253 (1)°Needle, white
V = 1748.90 (8) Å30.3 × 0.05 × 0.05 mm
Z = 4
Data collection top
Bruker SMART APEXII CCD
diffractometer
3246 independent reflections
Radiation source: fine-focus sealed tube2834 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.028
ω scanθmax = 70.1°, θmin = 2.8°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
h = 88
Tmin = 0.813, Tmax = 1.000k = 3738
20093 measured reflectionsl = 99
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.105H-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 parametersΔρmax = 0.24 e Å3
0 restraintsΔρmin = 0.19 e Å3
Crystal data top
C16H15N3O3S2V = 1748.90 (8) Å3
Mr = 361.43Z = 4
Monoclinic, P21/nCu Kα radiation
a = 7.3383 (2) ŵ = 2.93 mm1
b = 31.5484 (8) ÅT = 290 K
c = 8.0521 (2) Å0.3 × 0.05 × 0.05 mm
β = 110.253 (1)°
Data collection top
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 = 1.000Rint = 0.028
20093 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0380 restraints
wR(F2) = 0.105H-atom parameters constrained
S = 1.03Δρmax = 0.24 e Å3
3246 reflectionsΔρmin = 0.19 e Å3
218 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.0604 (2)0.15839 (6)0.3466 (2)0.0577 (4)
C40.1417 (2)0.26386 (6)0.2760 (2)0.0569 (4)
C110.0032 (4)0.08002 (6)0.1613 (3)0.0824 (6)
H11A0.12370.06930.23230.099*
H11B0.09410.07330.22080.099*
C120.0684 (4)0.06033 (6)0.0193 (3)0.0856 (7)
C130.2608 (5)0.05188 (10)0.1059 (5)0.1221 (11)
H130.35170.05880.05360.147*
C140.3204 (7)0.03310 (12)0.2710 (6)0.1528 (16)
H140.45140.02710.32850.183*
C150.1923 (9)0.02340 (11)0.3492 (5)0.1496 (18)
H150.23440.01100.46100.179*
C160.0017 (8)0.03158 (10)0.2660 (6)0.1366 (14)
H160.08760.02480.32040.164*
C170.0608 (5)0.04996 (8)0.0998 (4)0.1085 (9)
H170.19230.05530.04260.130*
C210.1133 (4)0.15898 (10)0.6988 (3)0.0951 (8)
H21A0.23210.17420.71870.143*
H21B0.12150.14340.80360.143*
H21C0.00700.17860.67110.143*
C410.1102 (2)0.29170 (6)0.1184 (2)0.0567 (4)
C420.0938 (3)0.33488 (6)0.1418 (3)0.0645 (5)
H420.10310.34530.25260.077*
C430.0637 (3)0.36251 (7)0.0025 (3)0.0738 (5)
H430.05060.39140.01740.089*
C440.0534 (3)0.34648 (8)0.1584 (3)0.0725 (5)
C450.0744 (3)0.30431 (8)0.1861 (3)0.0757 (6)
H450.06960.29440.29640.091*
C460.1034 (3)0.27650 (7)0.0449 (3)0.0668 (5)
H460.11810.24760.06040.080*
N20.0866 (2)0.19767 (5)0.38177 (18)0.0597 (4)
N30.0685 (2)0.22441 (5)0.24002 (18)0.0571 (4)
H30.01230.21610.13270.069*
N440.0194 (3)0.37648 (9)0.3085 (3)0.0941 (6)
O50.2302 (2)0.27647 (5)0.42616 (17)0.0781 (4)
O4410.0167 (3)0.41441 (8)0.2765 (3)0.1288 (8)
O4420.0070 (3)0.36199 (8)0.4537 (3)0.1248 (8)
S10.00760 (9)0.137011 (15)0.13261 (6)0.07046 (17)
S20.07452 (8)0.12289 (2)0.51793 (7)0.07755 (19)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0494 (9)0.0687 (11)0.0510 (9)0.0066 (8)0.0124 (7)0.0085 (8)
C40.0476 (8)0.0594 (10)0.0495 (9)0.0062 (7)0.0013 (7)0.0058 (7)
C110.1110 (18)0.0554 (11)0.0815 (14)0.0049 (11)0.0340 (13)0.0055 (10)
C120.125 (2)0.0463 (10)0.0873 (15)0.0036 (11)0.0383 (15)0.0033 (10)
C130.130 (3)0.096 (2)0.120 (2)0.0130 (18)0.018 (2)0.0261 (18)
C140.174 (4)0.113 (3)0.132 (3)0.011 (2)0.002 (3)0.038 (2)
C150.260 (6)0.078 (2)0.100 (2)0.000 (3)0.048 (3)0.0165 (17)
C160.237 (5)0.0768 (19)0.132 (3)0.013 (2)0.109 (3)0.0107 (19)
C170.158 (3)0.0665 (14)0.123 (2)0.0125 (15)0.077 (2)0.0081 (14)
C210.0941 (16)0.136 (2)0.0566 (12)0.0100 (15)0.0276 (12)0.0156 (13)
C410.0420 (8)0.0642 (10)0.0539 (10)0.0037 (7)0.0040 (7)0.0040 (8)
C420.0568 (10)0.0646 (11)0.0638 (11)0.0037 (8)0.0104 (8)0.0028 (8)
C430.0631 (11)0.0668 (12)0.0849 (15)0.0045 (9)0.0172 (11)0.0083 (10)
C440.0537 (10)0.0870 (15)0.0721 (13)0.0092 (9)0.0158 (9)0.0146 (11)
C450.0624 (11)0.1048 (17)0.0603 (11)0.0124 (11)0.0218 (9)0.0039 (11)
C460.0612 (10)0.0740 (12)0.0612 (11)0.0056 (9)0.0162 (9)0.0067 (9)
N20.0583 (8)0.0690 (10)0.0435 (7)0.0050 (7)0.0071 (6)0.0041 (6)
N30.0585 (8)0.0594 (8)0.0397 (7)0.0014 (6)0.0003 (6)0.0015 (6)
N440.0705 (11)0.1181 (19)0.0900 (15)0.0077 (11)0.0232 (11)0.0288 (14)
O50.0802 (9)0.0710 (8)0.0528 (7)0.0030 (7)0.0156 (7)0.0111 (6)
O4410.1451 (19)0.1056 (16)0.1267 (17)0.0046 (13)0.0355 (14)0.0437 (14)
O4420.1220 (16)0.172 (2)0.0833 (13)0.0042 (14)0.0399 (12)0.0322 (14)
S10.0978 (4)0.0538 (3)0.0556 (3)0.0024 (2)0.0212 (3)0.00350 (18)
S20.0785 (3)0.0905 (4)0.0651 (3)0.0068 (3)0.0268 (3)0.0250 (3)
Geometric parameters (Å, º) top
C1—N21.271 (2)C17—H170.9300
C1—S21.7519 (18)C21—S21.792 (3)
C1—S11.7641 (18)C21—H21A0.9600
C4—O51.224 (2)C21—H21B0.9600
C4—N31.347 (2)C21—H21C0.9600
C4—C411.494 (2)C41—C461.385 (3)
C11—C121.499 (3)C41—C421.386 (3)
C11—S11.818 (2)C42—C431.377 (3)
C11—H11A0.9700C42—H420.9300
C11—H11B0.9700C43—C441.368 (3)
C12—C171.361 (4)C43—H430.9300
C12—C131.367 (4)C44—C451.367 (3)
C13—C141.381 (5)C44—N441.487 (3)
C13—H130.9300C45—C461.393 (3)
C14—C151.335 (6)C45—H450.9300
C14—H140.9300C46—H460.9300
C15—C161.350 (6)N2—N31.388 (2)
C15—H150.9300N3—H30.8600
C16—C171.383 (5)N44—O4421.207 (3)
C16—H160.9300N44—O4411.226 (3)
N2—C1—S2119.00 (14)H21A—C21—H21B109.5
N2—C1—S1123.75 (13)S2—C21—H21C109.5
S2—C1—S1117.25 (11)H21A—C21—H21C109.5
O5—C4—N3123.29 (17)H21B—C21—H21C109.5
O5—C4—C41121.40 (16)C46—C41—C42119.55 (18)
N3—C4—C41115.30 (14)C46—C41—C4123.19 (17)
C12—C11—S1107.46 (15)C42—C41—C4117.22 (16)
C12—C11—H11A110.2C43—C42—C41120.55 (19)
S1—C11—H11A110.2C43—C42—H42119.7
C12—C11—H11B110.2C41—C42—H42119.7
S1—C11—H11B110.2C44—C43—C42118.6 (2)
H11A—C11—H11B108.5C44—C43—H43120.7
C17—C12—C13118.5 (3)C42—C43—H43120.7
C17—C12—C11121.4 (3)C45—C44—C43122.8 (2)
C13—C12—C11120.2 (3)C45—C44—N44118.9 (2)
C12—C13—C14120.1 (4)C43—C44—N44118.3 (2)
C12—C13—H13119.9C44—C45—C46118.3 (2)
C14—C13—H13119.9C44—C45—H45120.9
C15—C14—C13120.8 (4)C46—C45—H45120.9
C15—C14—H14119.6C41—C46—C45120.2 (2)
C13—C14—H14119.6C41—C46—H46119.9
C14—C15—C16119.9 (4)C45—C46—H46119.9
C14—C15—H15120.0C1—N2—N3116.44 (14)
C16—C15—H15120.0C4—N3—N2117.83 (14)
C15—C16—C17120.0 (4)C4—N3—H3121.1
C15—C16—H16120.0N2—N3—H3121.1
C17—C16—H16120.0O442—N44—O441124.4 (3)
C12—C17—C16120.6 (4)O442—N44—C44118.2 (3)
C12—C17—H17119.7O441—N44—C44117.4 (3)
C16—C17—H17119.7C1—S1—C11104.98 (10)
S2—C21—H21A109.5C1—S2—C21100.57 (11)
S2—C21—H21B109.5
S1—C11—C12—C1786.7 (2)C43—C44—C45—C461.4 (3)
S1—C11—C12—C1394.2 (3)N44—C44—C45—C46179.09 (17)
C17—C12—C13—C140.2 (5)C42—C41—C46—C451.9 (3)
C11—C12—C13—C14178.9 (3)C4—C41—C46—C45179.67 (16)
C12—C13—C14—C150.8 (6)C44—C45—C46—C410.0 (3)
C13—C14—C15—C160.6 (6)S2—C1—N2—N3178.29 (12)
C14—C15—C16—C170.0 (6)S1—C1—N2—N31.0 (2)
C13—C12—C17—C160.4 (4)O5—C4—N3—N23.3 (3)
C11—C12—C17—C16179.6 (2)C41—C4—N3—N2177.49 (14)
C15—C16—C17—C120.6 (5)C1—N2—N3—C4163.56 (16)
O5—C4—C41—C46146.87 (19)C45—C44—N44—O4427.0 (3)
N3—C4—C41—C4632.3 (2)C43—C44—N44—O442173.5 (2)
O5—C4—C41—C4231.0 (2)C45—C44—N44—O441174.3 (2)
N3—C4—C41—C42149.81 (16)C43—C44—N44—O4415.2 (3)
C46—C41—C42—C432.4 (3)N2—C1—S1—C11177.33 (17)
C4—C41—C42—C43179.69 (16)S2—C1—S1—C113.33 (14)
C41—C42—C43—C441.0 (3)C12—C11—S1—C1174.15 (17)
C42—C43—C44—C451.0 (3)N2—C1—S2—C213.01 (18)
C42—C43—C44—N44179.56 (17)S1—C1—S2—C21176.36 (12)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3···O5i0.862.172.8648 (17)137
Symmetry code: (i) x1/2, y+1/2, z1/2.

Experimental details

(G1)(G2)(G3)
Crystal data
Chemical formulaC11H13N3O3S2C23H21N3O3S2C16H15N3O3S2
Mr299.36451.55361.43
Crystal system, space groupMonoclinic, P21/nMonoclinic, P21/cMonoclinic, P21/n
Temperature (K)295296290
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)
V3)1382.94 (7)4510.2 (4)1748.90 (8)
Z484
Radiation typeMo KαMo KαCu Kα
µ (mm1)0.390.272.93
Crystal size (mm)0.6 × 0.2 × 0.10.3 × 0.15 × 0.10.3 × 0.05 × 0.05
Data collection
DiffractometerKuma KM-4 CCDKuma KM-4 CCDBruker SMART APEXII CCD
Absorption correctionMulti-scan
(CrysAlis RED; Oxford Diffraction, 2007)
Multi-scan
(CrysAlis RED; Oxford Diffraction, 2007)
Multi-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.817, 1.0000.721, 1.0000.813, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
28663, 4223, 3242 45186, 7966, 5304 20093, 3246, 2834
Rint0.0240.0500.028
(sin θ/λ)max1)0.7140.5950.610
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 reflections422379663246
No. of parameters175562218
H-atom treatmentH-atom parameters constrainedH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.23, 0.220.31, 0.240.24, 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).

Hydrogen-bond geometry (Å, °) for G4 and G5 top
D—H···AD—HH···AD···AD—H···A
G4N3—H3···O5i0.862.082.889 (3)157
G5N3—H3···O5ii0.82 (2)2.08 (2)2.884 (3)167 (2)
Symmetry codes: (i) -x+1, -y, -z+2; (ii) x-1, y, z-1.
Hydrogen-bond geometry (Å, º) for (G2) top
D—H···AD—HH···AD···AD—H···A
C21A—H21C···O5Ai0.972.533.443 (3)157
C43—H43···O444ii0.932.373.212 (3)151
C45A—H45A···O442iii0.932.323.162 (3)150
Symmetry codes: (i) x, y+1, z; (ii) x, y+1/2, z1/2; (iii) x, y1, z.
Hydrogen-bond geometry (Å, º) for (G3) top
D—H···AD—HH···AD···AD—H···A
N3—H3···O5i0.862.172.8648 (17)137
Symmetry code: (i) x1/2, y+1/2, z1/2.
Hydrogen-bond geometry (Å, º) for (G1) top
D—H···AD—HH···AD···AD—H···A
C3—H3C···N2i0.962.573.5099 (15)166
C21—H21C···O441ii0.962.493.4046 (16)158
C42—H42···O442iii0.932.493.4209 (16)176
C45—H45···O5iv0.932.493.4034 (14)167
Symmetry codes: (i) x+1, y+2, z; (ii) x3/2, y+3/2, z+1/2; (iii) x1/2, y+3/2, z1/2; (iv) x+1/2, y+3/2, z+1/2.
Selected torsion angles (%) showing differences in the crystal and calculated geometries of the G5 molecule top
`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 stateG5 optimizedG5 modified optimized
C1—N2—N3—C4158.8-178.8173.3
N2—N3—C4—C41177.7176.723.4
N3—C4—C5—C42-148.8-158.0-150.7
O5—C4—N3—H3-161-161.2-4.7

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