research communications
E)-N′-[4-(piperidin-1-yl)benzylidene]arylsulfonohydrazides
and Hirshfeld surface analysis of (aDepartment of Chemistry, Mangalore University, Mangalagangotri-574 199, Mangalore, India, bInstitute of Materials Science, Darmstadt University of Technology, Alarich-Weiss-Str. 2, D-64287, Darmstadt, Germany, and cKarnataka State Rural Development and Panchayat Raj University, Gadag-582 101, India
*Correspondence e-mail: gowdabt@yahoo.com
The crystal structures and Hirshfeld surface analyses of three E)-N′-[4-(piperidin-1-yl)benzylidene]benzenesulfonohydrazide, C18H21N3O2S, (I), (E)-4-methyl-N′-[4-(piperidin-1-yl)benzylidene]benzenesulfonohydrazide, C19H23N3O2S, (II), and (E)-4-chloro-N′-[4-(piperidin-1-yl)benzylidene]benzenesulfonohydrazide, C18H20ClN3O2S, (III), derived from arylsulfonohydrazides and 4-(piperidin-4-yl)benzaldehyde have been analysed to investigate the effect of substituents on the structural parameters. All three structures crystallize in monoclinic crystal systems, in the space groups P21/c for (I) and (II), and C2/c for (III). Compound (III) contains two independent molecules in the and sixteen molecules per while (I) and (II) both have one and four molecules, respectively, in their asymmetric units and unit cells. In all cases, the central part of the molecule is twisted at the S atom. In the crystals, the molecules are linked via N—H⋯O hydrogen bonds, forming chains. Two-dimensional fingerprint plots of various interatomic contacts show that the major contributions are from H⋯H interactions.
namely (1. Chemical context
Piperidine is very common in many natural and synthetic N-containing medicaments and is present in the basic skeleton of many pharmacologically active compounds (Sampath, 2017). Compounds with a piperidine are intermediates in the synthesis of various (Wang & Wuorola, 1992; Grishina et al., 1995). They are reported to be cholesterol-lowering (Comins et al., 2001) and to display antiviral (Kang et al., 2015), anti-inflammatory, antioxidant (Tharini & Sangeetha, 2015), anti-epileptic (Kiasalari et al., 2014), antimicrobial, antitumor and antifungal (Sahu et al., 1979; Shah et al., 1992) activities. Furthermore, find applications in the pharmacological field and are important in designing medicines (Parekh et al., 2005). Thus the crystal structures of and piperidine derivatives have always been interesting, especially with regard to the stereochemistry across C=N and the conformation of the six-membered heterocyclic ring. We were interested in exploring the effect of the substituents on the structural parameters of compounds containing these moieties. Thus we report herein the synthesis, characterization and crystal structures of (E)-N′-[4-(piperidin-1-yl)benzylidene]benzenesulfonohydrazide, C18H21N3O2S, (I), and its 4-methyl- and 4-chloro-derivatives, namely, (E)-4-methyl-N′-[4-(piperidin-1-yl)benzylidene]benzenesulfonohydrazide, C19H23N3O2S, (II), and (E)-4-chloro-N′-[4-(piperidin-1-yl)benzylidene]benzenesulfonohydrazide, C18H20ClN3O2S, (III).
2. Structural commentary
All three of the title compounds (Figs. 1–3) crystallize in the monoclinic but in P21/c for (I) and (II), and C2/c for (III). The asymmetric units of compounds (I) and (II) each contain one molecule whereas there are two independent molecules in the of (III). All the three compounds display an E-configuration about the C=N bond (Purandara et al., 2017; Gu et al., 2012), and a chair conformation of the piperidine ring.
In compounds (I) and (II) (Figs. 1 and 2), the sulfonamide bonds are found to be synclinal and the torsion angles of the sulfonamide moieties are −66.0 (2) and 63.5 (2)°, respectively (Moss, 1996). The dihedral angles between the phenyl ring (C1–C6/S1) and the mean plane of the N1/N2/C7–C9 hydrazone fragment are 85.3 (1) and 80.5 (1)° in (I) and (II), respectively, indicating that the hydrazone portion of the molecules (C=N—N—S—C group) is not coplanar with the sulfonyl phenyl ring. The C7=N2 bond lengths of 1.271 (3) Å in (I) and 1.269 (3) Å in (II) are in agreement with double-bond character. In both compounds, the piperidine group is not sterically hindered. Thus the six-membered heterocyclic ring adopts the most stable chair conformation. The total puckering amplitude is 0.531 (3) Å in (I) and 0.465 (4) Å in (II), the puckering parameters are 173.7 (3), and 8.0 (5)° in (I) and (II), respectively, and the phase angles are 13.0 (3) in (I) and 184.0 (4)° in (II), respectively (Cremer & Pople, 1975; Nardelli, 1983). The C15—C14—N3—C11 torsion angles of −172.2 (2)° and 175.2 (3)° in (I) and (II), respectively, signify that the phenyl ring at the N atom of the piperidine ring is in an equatorial position (Nallini et al., 2003).
The contains two independent molecules and the contains 16 molecules. The torsion angles for the sulfonamide moieties in the two molecules [C1—S1–N1–N2 = 59.7 (4)° and C19—S2—N4—N5 = 67.9 (4)°] signify a synclinal conformation (Moss, 1996). The hydrazone moiety (C=N—N—S—C group) and arylsulfonyl ring are not coplanar, with dihedral angles between the two planes of 87.3 (1) and 79.4 (1)°, respectively, in the first and second molecules. The C7=N2 and C25=N5 bond lengths of 1.272 (5) and 1.269 (5) Å, respectively, are consistent with double-bond character. As in compounds (I) and (II), the piperidine group in (III) adopts a chair conformation, with the total puckering amplitude of QT = 0.283 (7) and 0.475 (1) Å in the first and second molecules, respectively, θ = 2.7 (14), 175.5 (8)° and phase angles φ = 220 (22)° and 353 (10)° in the two molecules, respectively. The phenyl ring at the piperidine N atom is equatorial, as is evident from C15—C14—N3—C11 and C33—C32—N6—C29 torsion angles of 174.4 (7) and −168.9 (5)°, respectively.
of (III)3. Supramolecular features
In all the three crystal structures, the amino H atom of the sulfonohydrazide segment acts as a donor and the sulfonyl O atom acts as an acceptor in N—H⋯O hydrogen-bonding interactions that generate C4 chains propagating parallel to the b axis (Tables 1–3, Figs. 4–9). Substitution at the para position by a methyl or chloro group to produce compounds (II) and (III) has no remarkable effect on the hydrogen-bonding pattern.
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4. Database survey
Although there are several reports on the crystal structures of piperidine or sulfonylhydrazides derivatives, reports on the crystal structures of 4-(piperidin-1-yl)benzaldehyde functionalized with sulfonylhydrazides are very few. Comparison of the present data with those of thiophene/phenyl-piperidine hybrid et al., 2014) reveals that the compounds also adopt E configuration around the C=N bond and the piperidine rings exhibit a chair conformation. A chair conformation of the piperidine ring is also found in 5-nitro-2-(piperidin-1-yl)benzaldehyde (N'Gouan et al., 2009) and (5-nitro-2-piperidino)benzylidene p-toluenesulfonylhydrazone (Yapo et al., 2008).
(Parvez5. Hirshfeld surface analysis
Hirshfeld surfaces (HS) and 2D fingerprint plots were generated using CrystalExplorer17 (Turner et al., 2017; McKinnon et al., 2007; Spackman & Jayatilaka, 2009). The terms such as dnorm, di and de are defined in the usual way (Shit et al., 2016). The function dnorm is a ratio enclosing the distances of any surface point to the nearest interior (di) and exterior (de) atom and the van der Waals radii of the atoms (Hirshfeld, 1977; Soman et al., 2014). The function dnorm will be equal to zero when intermolecular distances are close to van der Waals contacts. They are indicated by a white colour on the HS, while contacts longer than the sum of van der Waals radii with positive dnorm values are coloured in blue. The surface images and plots for dnorm (Fig. 10) were generated using a high standard surface resolution over a colour scale of −0.3495 to 1.3559, −0.4124 to 1.6768 and −0.3876 to 1.5649 a.u. for (I), (II) and (III), respectively.
Hirshfeld fingerprint plots for various interactions show differences in the percentage contributions to the Hirshfeld surfaces. H⋯H contacts make the maximum contribution to the Hirshfeld surfaces in all three compounds. The contributions of significant contacts in the three compounds are in the following order: H⋯H, C⋯H/H⋯C and O⋯H/H⋯O. In compound (I), these interactions cover a region of 52.0% (di = de = 1.5 Å), 22.5% (di + de = 3.2 Å), and 15.3% (di + de = 2.4 Å) (Fig. 11), respectively. The other interatomic contacts and percentages of contributions to the Hirshfeld surface are N⋯H/H⋯N (6.7%), C⋯O/O⋯C (3.1%). In compound (II), the contributions of the various contacts are: H⋯H 52.3% (di = de =1.5 Å), C⋯H/H⋯C 23.6% (di + de = 3.2 Å), and O⋯H/H⋯O 18.0% (di + de = 2.4 Å) (Fig. 11). Among the minor contributions observed, N⋯H/H⋯N interaction cover a region of 6.1%. In the case of compound (III), the major contributions are H⋯H 41.0% (di = de = 1.0 Å), C⋯H/H⋯C 22.3% (3.2 Å) and O⋯H/H⋯O, 19.3% (di + de = 2.4 Å) along with minor contributions from Cl⋯H/H⋯Cl (9.5%) and N⋯H/H⋯N (5.1%) interactions (Fig. 11).
6. Synthesis and crystallization
Synthesis of benzenesulfonohydrazide and 4-methyl and 4-chloro-benzenesulfonohydrazides
To solutions of hydrazine hydrate (99%) (0.03mol) in THF at 273 K under stirring, a solution of benzenesulfonyl chloride, 4-methylbenzenesulfonyl chloride or 4-chlorobenzenesulfonyl chloride (0.02 mol) in THF was added dropwise. Three separate reaction mixtures were kept under stirring at 273 K for 1 h and stirring continued for 24 h at room temperature. The formation of the products was monitored by TLC. After completion of the reactions, the reaction mixtures were poured separately onto ice-cold water. The separated solids, benzenesulfonohydrazide, 4-methylbenzenesulfonohydrazide or 4-chlorobenzenesulfonohydrazide, were filtered off and dried. The products were recrystallized from ethanol solution to get the pure products.
The purity of the compounds was checked by TLC and they were characterized by their IR spectra. They were further characterized by 1H and 13C NMR spectra. The characteristic IR absorptions and 1H and 13C NMR signals are as follows:
Benzenesulfonohydrazide: m.p. 374–376 K; FT–IR (ATR, νmax, cm−1): 3254.4 (s, NH2 str), 3198.3 (s, N—H str), 1325.1 (s, S=O asym str) and 1140.8 (vs, S=O sym str).
1H and 13C NMR spectra: 1H (400 MHz, DMSO-d6, δ, ppm): 7.93–7.42 (m, 5H, Ar—H), 5.85 (t, 1H), 3.43 (d, 2H). 13C NMR (100 MHz, DMSO-d6, δ, ppm); 134.57, 130.15, 129.12, 125.63.
4-Methylbenzenesulfonohydrazide: m.p. 382–385 K; FT–IR (ATR, νmax, cm−1): 3245.1 (s, NH2 str), 3193.8 (s, N—H str), 1330.5 (s, S=O asym str) and 1126.5 (vs, S=O sym str).
1H and 13C NMR spectra: 1H (400 MHz, DMSO-d6, δ, ppm); 7.71–7.31 (m, 4H, Ar—H), 5.91 (t, 1H), 3.48 (d, 2H), 2.19 (s, 3H, CH3). 13C NMR (100 MHz, DMSO-d6, δ, ppm); 142.36, 136.90, 128.13, 126.71, 22.11.
4-Chlorobenzenesulfonohydrazide: m.p. 388–90 K; FT–IR (ATR, νmax, cm−1): 3259.4 (s, NH2 str), 3195.1 (s, N—H str), 1341.7 (s, S=O asym str) and 1138.5 (vs, S=O sym str).
1H and 13C NMR spectra: 1H (400 MHz, DMSO-d6, δ, ppm); 7.58–7.67 (m, 5H, Ar—H), 5.87 (t, 1H), 3.41 (d, 2H). 13C NMR (100 MHz, DMSO-d6, δ, ppm); 137.90, 137.29, 130.30, 128.42.
Synthesis of the title compounds (I), (II) and (III):
Mixtures of 4-(piperidin-1-yl)benzaldehyde (0.001 mol) and benzenesulfonohydrazide, 4-methylbenzenesulfonohydrazide or 4-chlorobenzenesulfonohydrazide (0.001 mol) in ethanol (10 ml) and two drops of glacial acetic acid were stirred at room temperature for 2 h. The formation of the products was monitored by TLC. The reaction mixtures were separately poured on crushed ice and the solids that formed were washed and dried. The products were recrystallized to constant melting points from an acetonitrile:DMF (5:1 v:v) mixture. The purity of the compounds was checked by TLC and they were characterized by their IR spectra. They were further characterized by 1H and 13C NMR spectra. The characteristic IR absorptions and 1H and 13C NMR signals are as follows
Compound (I): m.p. 417–419 K; FT–IR (ATR, νmax, cm−1): 3219.2 (s, N—H str), 1609.3 (s, C=N str), 1363.7 (s, S=O asym str) and 1165.0 (vs, S=O sym str).
1H and 13C NMR spectra: 1H (400 MHz, DMSO-d6, δ, ppm); 9.41 (s, 1H, N—H), 8.39 (s, 1H, =C—H), 7.76–7.59 (m, 5H, Ar—H), 7.54–6.54 (m, 4H, Ar—H), 3.46–1.82 (m, 4H), 1.47–1.39 (m, 6H). 13C NMR (100 MHz, DMSO-d6, δ, ppm); 151.34, 147.31, 138.89, 133.62, 130.94, 129.91, 128.27, 124.97, 112.76, 48.54, 24.82, 23.93.
Compound (II): m.p. 439 − 441 K; FT–IR (ATR, νmax, cm−1): 3214.3 (s, N—H, str), 1606.7 (s, C=N str), 1359.82 (s, S=O asym) and 1163.08cm−1 (vs, S=O sym).
1H and 13C spectra: 1H (400 MHz, DMSO-d6, δ, ppm); 10.98 (s, 1H, N—H), 7.77–7.75 (m, 3H, Ar—H, =C—H), 7.37–7.34 (m, 4H, Ar—H), 3.29–2.36 (m, 4H), 2.37 (s, 3H, CH3), 1.56–1.47 (m, 6H); 13C NMR (100 MHz, DMSO-d6 δ, ppm); 152.28, 147.48, 142.92, 136.34, 129.28, 127.89, 127.17, 114.45, 48.51, 24.92, 23.87, 21.0.
Compound (III): m.p. 429–431 K; FT–IR (ATR, νmax, cm−1): 3213.4 (s, N—H, str), 1608.9 (s, C=N, str), 1365.6 (s, S=O asym str) and 1166.9 (vs, S=O sym str).
1H and 13C spectra: 1H (400 MHz, DMSO-d6, δ, ppm); 8.18 (s, 1H, N-H), 7.91–7.88 (m, 2H, Ar—H), 7.70 (s, 1H, =C—H), 7.45–7.40 (m, 4H), 6.82 (d, 2H, Ar—H), 3.26–3.23 (m, 4H), 1.69–1.60 (m, 6H). 13C NMR (100 MHz, DMSO-d6, δ, ppm); 153.13, 150.03, 139.68, 136.87, 129.41, 129.27, 128.88, 122.65, 114.85, 49.29, 25.41, 24.28.
Prismatic single crystals of the compounds used in X-ray diffraction studies were grown from their solutions in a acetonitrile–DMF (5:1 v:v) mixture by slow evaporation of the solvent.
7. Refinement
Crystal data, data collection and structure . H atoms bonded to C were positioned with idealized geometry and refined using a riding model with the aromatic C—H = 0.93, 0.96 (methyl), or 0.97 Å (methylene). H atoms of the NH groups were located in a difference map and their positions refined. All H atoms were refined with Uiso(H) = 1.2Ueq(C-aromatic, C-methylene, N) or 1.5Ueq(C-methyl). In compound (III), the Uij components of atoms C14, C15, C17, and C18 were restrained to approximate isotropic behaviour.
details are summarized in Table 4Supporting information
https://doi.org/10.1107/S2056989018016237/tx2009sup1.cif
contains datablocks I, II, III, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018016237/tx2009Isup2.hkl
Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989018016237/tx2009IIsup3.hkl
Structure factors: contains datablock III. DOI: https://doi.org/10.1107/S2056989018016237/tx2009IIIsup4.hkl
For all structures, data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell
CrysAlis RED (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS2013/1 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/6 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL2014/6 (Sheldrick, 2015).C18H21N3O2S | F(000) = 728 |
Mr = 343.44 | Dx = 1.323 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 19.221 (2) Å | Cell parameters from 2039 reflections |
b = 5.4270 (7) Å | θ = 2.8–27.8° |
c = 17.143 (2) Å | µ = 0.20 mm−1 |
β = 105.45 (2)° | T = 293 K |
V = 1723.6 (4) Å3 | Prism, colourless |
Z = 4 | 0.44 × 0.32 × 0.28 mm |
Oxford Diffraction Xcalibur diffractometer with Sapphire CCD | 2475 reflections with I > 2σ(I) |
Radiation source: Enhance (Mo) X-ray Source | Rint = 0.019 |
Rotation method data acquisition using ω scans. | θmax = 25.4°, θmin = 2.8° |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009) | h = −23→20 |
Tmin = 0.916, Tmax = 0.945 | k = −4→6 |
6052 measured reflections | l = −19→20 |
3164 independent reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.043 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.108 | w = 1/[σ2(Fo2) + (0.0438P)2 + 0.7956P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max = 0.001 |
3164 reflections | Δρmax = 0.24 e Å−3 |
220 parameters | Δρmin = −0.31 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.60577 (10) | 0.1520 (4) | 0.46537 (12) | 0.0384 (5) | |
C2 | 0.63592 (13) | −0.0066 (5) | 0.42141 (15) | 0.0553 (6) | |
H2 | 0.6625 | −0.1422 | 0.4460 | 0.066* | |
C3 | 0.62614 (16) | 0.0387 (6) | 0.33995 (17) | 0.0720 (8) | |
H3 | 0.6459 | −0.0684 | 0.3093 | 0.086* | |
C4 | 0.58782 (15) | 0.2386 (6) | 0.30389 (15) | 0.0699 (8) | |
H4 | 0.5821 | 0.2681 | 0.2491 | 0.084* | |
C5 | 0.55771 (13) | 0.3960 (6) | 0.34822 (16) | 0.0692 (8) | |
H5 | 0.5311 | 0.5309 | 0.3232 | 0.083* | |
C6 | 0.56663 (12) | 0.3554 (5) | 0.42987 (14) | 0.0551 (6) | |
H6 | 0.5467 | 0.4627 | 0.4603 | 0.066* | |
C7 | 0.79265 (11) | 0.4355 (4) | 0.63390 (11) | 0.0403 (5) | |
H7 | 0.7761 | 0.5782 | 0.6531 | 0.048* | |
C8 | 0.86830 (11) | 0.4209 (4) | 0.63351 (11) | 0.0378 (5) | |
C9 | 0.89690 (11) | 0.2255 (4) | 0.59921 (12) | 0.0434 (5) | |
H9 | 0.8667 | 0.0973 | 0.5749 | 0.052* | |
C10 | 0.96855 (11) | 0.2183 (4) | 0.60049 (12) | 0.0431 (5) | |
H10 | 0.9857 | 0.0851 | 0.5770 | 0.052* | |
C11 | 1.01676 (10) | 0.4064 (4) | 0.63636 (11) | 0.0353 (4) | |
C12 | 0.98802 (11) | 0.5993 (4) | 0.67192 (12) | 0.0428 (5) | |
H12 | 1.0181 | 0.7265 | 0.6972 | 0.051* | |
C13 | 0.91592 (12) | 0.6049 (4) | 0.67031 (12) | 0.0435 (5) | |
H13 | 0.8987 | 0.7361 | 0.6947 | 0.052* | |
C14 | 1.10674 (12) | 0.2969 (5) | 0.56571 (14) | 0.0529 (6) | |
H14A | 1.0889 | 0.4113 | 0.5214 | 0.063* | |
H14B | 1.0816 | 0.1418 | 0.5511 | 0.063* | |
C15 | 1.18625 (13) | 0.2563 (5) | 0.57619 (18) | 0.0657 (7) | |
H15A | 1.2026 | 0.1212 | 0.6137 | 0.079* | |
H15B | 1.1941 | 0.2101 | 0.5245 | 0.079* | |
C16 | 1.22997 (12) | 0.4823 (5) | 0.60752 (15) | 0.0558 (6) | |
H16A | 1.2810 | 0.4462 | 0.6174 | 0.067* | |
H16B | 1.2178 | 0.6135 | 0.5678 | 0.067* | |
C17 | 1.21388 (12) | 0.5618 (5) | 0.68471 (14) | 0.0595 (7) | |
H17A | 1.2402 | 0.7120 | 0.7040 | 0.071* | |
H17B | 1.2302 | 0.4356 | 0.7256 | 0.071* | |
C18 | 1.13426 (12) | 0.6062 (5) | 0.67295 (15) | 0.0573 (6) | |
H18A | 1.1257 | 0.6457 | 0.7248 | 0.069* | |
H18B | 1.1195 | 0.7471 | 0.6376 | 0.069* | |
N1 | 0.67909 (9) | 0.2983 (4) | 0.61782 (11) | 0.0422 (4) | |
H1N | 0.6650 (12) | 0.444 (4) | 0.6160 (14) | 0.051* | |
N2 | 0.74846 (9) | 0.2602 (3) | 0.60892 (10) | 0.0412 (4) | |
N3 | 1.09002 (9) | 0.3935 (3) | 0.63815 (9) | 0.0387 (4) | |
O1 | 0.64512 (9) | −0.1391 (3) | 0.58934 (10) | 0.0571 (4) | |
O2 | 0.55362 (8) | 0.1803 (3) | 0.59001 (9) | 0.0547 (4) | |
S1 | 0.61709 (3) | 0.10285 (10) | 0.56935 (3) | 0.04091 (17) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0281 (10) | 0.0418 (12) | 0.0442 (11) | −0.0031 (9) | 0.0075 (8) | −0.0030 (9) |
C2 | 0.0554 (14) | 0.0543 (14) | 0.0594 (15) | 0.0026 (12) | 0.0210 (11) | −0.0046 (12) |
C3 | 0.0813 (19) | 0.083 (2) | 0.0578 (16) | −0.0118 (17) | 0.0297 (14) | −0.0194 (16) |
C4 | 0.0640 (16) | 0.102 (2) | 0.0386 (13) | −0.0277 (17) | 0.0046 (12) | −0.0034 (15) |
C5 | 0.0536 (15) | 0.089 (2) | 0.0564 (16) | 0.0059 (15) | −0.0001 (12) | 0.0206 (15) |
C6 | 0.0480 (13) | 0.0631 (16) | 0.0524 (14) | 0.0131 (12) | 0.0103 (10) | 0.0074 (12) |
C7 | 0.0473 (12) | 0.0377 (12) | 0.0347 (11) | 0.0034 (10) | 0.0089 (9) | 0.0014 (9) |
C8 | 0.0426 (11) | 0.0356 (11) | 0.0324 (10) | −0.0006 (9) | 0.0050 (8) | 0.0045 (9) |
C9 | 0.0443 (12) | 0.0349 (11) | 0.0459 (12) | −0.0086 (10) | 0.0033 (9) | −0.0063 (10) |
C10 | 0.0465 (12) | 0.0318 (11) | 0.0483 (12) | −0.0028 (10) | 0.0079 (10) | −0.0092 (10) |
C11 | 0.0432 (11) | 0.0312 (10) | 0.0278 (9) | −0.0037 (9) | 0.0027 (8) | 0.0018 (8) |
C12 | 0.0503 (12) | 0.0339 (11) | 0.0415 (11) | −0.0107 (10) | 0.0073 (9) | −0.0086 (9) |
C13 | 0.0523 (12) | 0.0352 (11) | 0.0430 (11) | −0.0014 (10) | 0.0126 (9) | −0.0063 (10) |
C14 | 0.0505 (13) | 0.0579 (15) | 0.0492 (13) | −0.0097 (11) | 0.0116 (10) | −0.0172 (12) |
C15 | 0.0519 (14) | 0.0626 (17) | 0.0857 (19) | −0.0081 (13) | 0.0235 (13) | −0.0283 (15) |
C16 | 0.0453 (13) | 0.0577 (15) | 0.0657 (15) | −0.0070 (12) | 0.0171 (11) | −0.0130 (12) |
C17 | 0.0481 (13) | 0.0739 (18) | 0.0535 (14) | −0.0195 (13) | 0.0082 (11) | −0.0148 (13) |
C18 | 0.0536 (14) | 0.0606 (16) | 0.0598 (15) | −0.0205 (12) | 0.0191 (11) | −0.0261 (12) |
N1 | 0.0397 (10) | 0.0413 (10) | 0.0444 (10) | 0.0028 (8) | 0.0089 (8) | −0.0016 (9) |
N2 | 0.0382 (9) | 0.0433 (10) | 0.0393 (9) | 0.0021 (8) | 0.0055 (7) | 0.0022 (8) |
N3 | 0.0422 (9) | 0.0387 (10) | 0.0330 (9) | −0.0091 (8) | 0.0062 (7) | −0.0053 (7) |
O1 | 0.0619 (10) | 0.0391 (9) | 0.0689 (11) | 0.0043 (8) | 0.0147 (8) | 0.0115 (8) |
O2 | 0.0444 (9) | 0.0671 (11) | 0.0572 (9) | 0.0011 (8) | 0.0216 (7) | 0.0009 (8) |
S1 | 0.0378 (3) | 0.0397 (3) | 0.0456 (3) | 0.0016 (2) | 0.0118 (2) | 0.0042 (2) |
C1—C2 | 1.370 (3) | C12—H12 | 0.9300 |
C1—C6 | 1.383 (3) | C13—H13 | 0.9300 |
C1—S1 | 1.758 (2) | C14—N3 | 1.460 (3) |
C2—C3 | 1.381 (4) | C14—C15 | 1.507 (3) |
C2—H2 | 0.9300 | C14—H14A | 0.9700 |
C3—C4 | 1.363 (4) | C14—H14B | 0.9700 |
C3—H3 | 0.9300 | C15—C16 | 1.503 (3) |
C4—C5 | 1.370 (4) | C15—H15A | 0.9700 |
C4—H4 | 0.9300 | C15—H15B | 0.9700 |
C5—C6 | 1.382 (3) | C16—C17 | 1.500 (3) |
C5—H5 | 0.9300 | C16—H16A | 0.9700 |
C6—H6 | 0.9300 | C16—H16B | 0.9700 |
C7—N2 | 1.271 (3) | C17—C18 | 1.509 (3) |
C7—C8 | 1.458 (3) | C17—H17A | 0.9700 |
C7—H7 | 0.9300 | C17—H17B | 0.9700 |
C8—C13 | 1.387 (3) | C18—N3 | 1.463 (3) |
C8—C9 | 1.395 (3) | C18—H18A | 0.9700 |
C9—C10 | 1.372 (3) | C18—H18B | 0.9700 |
C9—H9 | 0.9300 | N1—N2 | 1.397 (2) |
C10—C11 | 1.406 (3) | N1—S1 | 1.6458 (19) |
C10—H10 | 0.9300 | N1—H1N | 0.84 (2) |
C11—C12 | 1.397 (3) | O1—S1 | 1.4258 (16) |
C11—N3 | 1.402 (2) | O2—S1 | 1.4216 (15) |
C12—C13 | 1.379 (3) | ||
C2—C1—C6 | 121.3 (2) | C15—C14—H14A | 108.9 |
C2—C1—S1 | 120.43 (17) | N3—C14—H14B | 108.9 |
C6—C1—S1 | 118.24 (17) | C15—C14—H14B | 108.9 |
C1—C2—C3 | 118.8 (2) | H14A—C14—H14B | 107.7 |
C1—C2—H2 | 120.6 | C16—C15—C14 | 112.1 (2) |
C3—C2—H2 | 120.6 | C16—C15—H15A | 109.2 |
C4—C3—C2 | 120.8 (3) | C14—C15—H15A | 109.2 |
C4—C3—H3 | 119.6 | C16—C15—H15B | 109.2 |
C2—C3—H3 | 119.6 | C14—C15—H15B | 109.2 |
C3—C4—C5 | 120.1 (2) | H15A—C15—H15B | 107.9 |
C3—C4—H4 | 119.9 | C17—C16—C15 | 108.8 (2) |
C5—C4—H4 | 119.9 | C17—C16—H16A | 109.9 |
C4—C5—C6 | 120.4 (3) | C15—C16—H16A | 109.9 |
C4—C5—H5 | 119.8 | C17—C16—H16B | 109.9 |
C6—C5—H5 | 119.8 | C15—C16—H16B | 109.9 |
C5—C6—C1 | 118.6 (2) | H16A—C16—H16B | 108.3 |
C5—C6—H6 | 120.7 | C16—C17—C18 | 111.60 (19) |
C1—C6—H6 | 120.7 | C16—C17—H17A | 109.3 |
N2—C7—C8 | 122.39 (19) | C18—C17—H17A | 109.3 |
N2—C7—H7 | 118.8 | C16—C17—H17B | 109.3 |
C8—C7—H7 | 118.8 | C18—C17—H17B | 109.3 |
C13—C8—C9 | 116.90 (19) | H17A—C17—H17B | 108.0 |
C13—C8—C7 | 119.79 (19) | N3—C18—C17 | 112.8 (2) |
C9—C8—C7 | 123.29 (19) | N3—C18—H18A | 109.0 |
C10—C9—C8 | 121.45 (19) | C17—C18—H18A | 109.0 |
C10—C9—H9 | 119.3 | N3—C18—H18B | 109.0 |
C8—C9—H9 | 119.3 | C17—C18—H18B | 109.0 |
C9—C10—C11 | 121.9 (2) | H18A—C18—H18B | 107.8 |
C9—C10—H10 | 119.1 | N2—N1—S1 | 115.68 (14) |
C11—C10—H10 | 119.1 | N2—N1—H1N | 116.4 (17) |
C12—C11—N3 | 122.65 (18) | S1—N1—H1N | 114.2 (16) |
C12—C11—C10 | 116.36 (19) | C7—N2—N1 | 115.09 (18) |
N3—C11—C10 | 120.96 (18) | C11—N3—C14 | 116.53 (15) |
C13—C12—C11 | 121.31 (19) | C11—N3—C18 | 116.14 (17) |
C13—C12—H12 | 119.3 | C14—N3—C18 | 113.21 (17) |
C11—C12—H12 | 119.3 | O2—S1—O1 | 120.46 (10) |
C12—C13—C8 | 122.1 (2) | O2—S1—N1 | 103.75 (10) |
C12—C13—H13 | 119.0 | O1—S1—N1 | 107.20 (10) |
C8—C13—H13 | 119.0 | O2—S1—C1 | 108.99 (9) |
N3—C14—C15 | 113.40 (18) | O1—S1—C1 | 108.67 (10) |
N3—C14—H14A | 108.9 | N1—S1—C1 | 106.95 (9) |
C6—C1—C2—C3 | −0.5 (3) | C15—C16—C17—C18 | −56.4 (3) |
S1—C1—C2—C3 | −179.69 (19) | C16—C17—C18—N3 | 54.7 (3) |
C1—C2—C3—C4 | 0.6 (4) | C8—C7—N2—N1 | 176.43 (17) |
C2—C3—C4—C5 | −0.8 (4) | S1—N1—N2—C7 | 167.78 (14) |
C3—C4—C5—C6 | 0.8 (4) | C12—C11—N3—C14 | −142.9 (2) |
C4—C5—C6—C1 | −0.7 (4) | C10—C11—N3—C14 | 39.3 (3) |
C2—C1—C6—C5 | 0.5 (3) | C12—C11—N3—C18 | −5.6 (3) |
S1—C1—C6—C5 | 179.75 (18) | C10—C11—N3—C18 | 176.68 (19) |
N2—C7—C8—C13 | −172.29 (19) | C15—C14—N3—C11 | −172.2 (2) |
N2—C7—C8—C9 | 6.1 (3) | C15—C14—N3—C18 | 49.3 (3) |
C13—C8—C9—C10 | −1.2 (3) | C17—C18—N3—C11 | 170.97 (18) |
C7—C8—C9—C10 | −179.67 (19) | C17—C18—N3—C14 | −50.3 (3) |
C8—C9—C10—C11 | 0.1 (3) | N2—N1—S1—O2 | 178.88 (14) |
C9—C10—C11—C12 | 1.1 (3) | N2—N1—S1—O1 | 50.42 (17) |
C9—C10—C11—N3 | 178.96 (18) | N2—N1—S1—C1 | −65.99 (16) |
N3—C11—C12—C13 | −178.92 (18) | C2—C1—S1—O2 | −145.87 (18) |
C10—C11—C12—C13 | −1.1 (3) | C6—C1—S1—O2 | 34.91 (19) |
C11—C12—C13—C8 | −0.1 (3) | C2—C1—S1—O1 | −12.9 (2) |
C9—C8—C13—C12 | 1.2 (3) | C6—C1—S1—O1 | 167.93 (16) |
C7—C8—C13—C12 | 179.73 (19) | C2—C1—S1—N1 | 102.56 (19) |
N3—C14—C15—C16 | −52.5 (3) | C6—C1—S1—N1 | −76.65 (18) |
C14—C15—C16—C17 | 55.3 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O1i | 0.84 (2) | 2.32 (2) | 3.133 (3) | 165 (2) |
Symmetry code: (i) x, y+1, z. |
C19H23N3O2S | F(000) = 760 |
Mr = 357.46 | Dx = 1.272 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 18.442 (2) Å | Cell parameters from 1748 reflections |
b = 5.3250 (4) Å | θ = 2.6–28.0° |
c = 19.412 (2) Å | µ = 0.19 mm−1 |
β = 101.74 (1)° | T = 293 K |
V = 1866.5 (3) Å3 | Prism, light pink |
Z = 4 | 0.48 × 0.24 × 0.10 mm |
Oxford Diffraction Xcalibur diffractometer with Sapphire CCD | 2166 reflections with I > 2σ(I) |
Radiation source: Enhance (Mo) X-ray Source | Rint = 0.026 |
Rotation method data acquisition using ω scans. | θmax = 25.4°, θmin = 2.6° |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009) | h = −22→13 |
Tmin = 0.914, Tmax = 0.981 | k = −6→2 |
6735 measured reflections | l = −21→23 |
3422 independent reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.051 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.137 | w = 1/[σ2(Fo2) + (0.0561P)2 + 0.7083P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max < 0.001 |
3422 reflections | Δρmax = 0.21 e Å−3 |
230 parameters | Δρmin = −0.22 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.87009 (13) | 0.2262 (5) | 0.74497 (13) | 0.0464 (6) | |
C2 | 0.85130 (16) | 0.0568 (6) | 0.69097 (15) | 0.0610 (8) | |
H2 | 0.8189 | −0.0742 | 0.6944 | 0.073* | |
C3 | 0.88094 (18) | 0.0827 (6) | 0.63160 (16) | 0.0716 (9) | |
H3 | 0.8682 | −0.0331 | 0.5953 | 0.086* | |
C4 | 0.92855 (15) | 0.2738 (6) | 0.62451 (15) | 0.0640 (8) | |
C5 | 0.94574 (15) | 0.4437 (6) | 0.67864 (16) | 0.0635 (8) | |
H5 | 0.9775 | 0.5760 | 0.6746 | 0.076* | |
C6 | 0.91734 (15) | 0.4236 (5) | 0.73839 (15) | 0.0579 (7) | |
H6 | 0.9296 | 0.5414 | 0.7742 | 0.070* | |
C7 | 0.65696 (15) | 0.5049 (5) | 0.75489 (14) | 0.0549 (7) | |
H7 | 0.6648 | 0.6537 | 0.7804 | 0.066* | |
C8 | 0.58859 (14) | 0.4736 (5) | 0.70327 (14) | 0.0497 (7) | |
C9 | 0.57536 (16) | 0.2675 (5) | 0.65812 (16) | 0.0606 (8) | |
H9 | 0.6120 | 0.1463 | 0.6600 | 0.073* | |
C10 | 0.50985 (16) | 0.2394 (5) | 0.61123 (16) | 0.0603 (8) | |
H10 | 0.5032 | 0.0999 | 0.5818 | 0.072* | |
C11 | 0.45234 (15) | 0.4149 (5) | 0.60617 (14) | 0.0508 (7) | |
C12 | 0.46593 (15) | 0.6186 (5) | 0.65168 (15) | 0.0570 (7) | |
H12 | 0.4293 | 0.7396 | 0.6503 | 0.068* | |
C13 | 0.53232 (15) | 0.6458 (5) | 0.69881 (15) | 0.0567 (7) | |
H13 | 0.5392 | 0.7848 | 0.7284 | 0.068* | |
C14 | 0.38983 (18) | 0.2897 (8) | 0.48900 (18) | 0.0869 (11) | |
H14A | 0.4194 | 0.1377 | 0.4942 | 0.104* | |
H14B | 0.4156 | 0.4144 | 0.4665 | 0.104* | |
C15 | 0.3168 (2) | 0.2351 (7) | 0.44174 (19) | 0.0947 (12) | |
H15A | 0.3246 | 0.2074 | 0.3944 | 0.114* | |
H15B | 0.2970 | 0.0811 | 0.4573 | 0.114* | |
C16 | 0.2620 (2) | 0.4358 (7) | 0.43997 (19) | 0.0892 (11) | |
H16A | 0.2143 | 0.3791 | 0.4139 | 0.107* | |
H16B | 0.2767 | 0.5809 | 0.4159 | 0.107* | |
C17 | 0.25546 (19) | 0.5082 (9) | 0.5121 (2) | 0.1010 (13) | |
H17A | 0.2317 | 0.3727 | 0.5326 | 0.121* | |
H17B | 0.2239 | 0.6550 | 0.5095 | 0.121* | |
C18 | 0.32853 (18) | 0.5650 (8) | 0.55932 (19) | 0.0931 (12) | |
H18A | 0.3460 | 0.7256 | 0.5456 | 0.112* | |
H18B | 0.3210 | 0.5817 | 0.6071 | 0.112* | |
C19 | 0.9621 (2) | 0.2953 (9) | 0.56057 (18) | 0.1048 (13) | |
H19A | 1.0151 | 0.2897 | 0.5744 | 0.157* | |
H19B | 0.9474 | 0.4515 | 0.5372 | 0.157* | |
H19C | 0.9453 | 0.1585 | 0.5292 | 0.157* | |
N1 | 0.76763 (13) | 0.3858 (4) | 0.81973 (13) | 0.0564 (6) | |
H1N | 0.7786 (17) | 0.529 (6) | 0.8265 (15) | 0.068* | |
N2 | 0.70639 (12) | 0.3358 (4) | 0.76625 (12) | 0.0541 (6) | |
N3 | 0.38501 (12) | 0.3803 (4) | 0.55849 (12) | 0.0592 (6) | |
O1 | 0.89223 (11) | 0.2837 (4) | 0.87969 (10) | 0.0729 (6) | |
O2 | 0.80891 (11) | −0.0554 (4) | 0.82456 (11) | 0.0711 (6) | |
S1 | 0.83734 (4) | 0.19279 (14) | 0.82295 (4) | 0.0548 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0376 (13) | 0.0478 (15) | 0.0508 (15) | 0.0021 (12) | 0.0023 (11) | 0.0067 (13) |
C2 | 0.0635 (18) | 0.0558 (18) | 0.0625 (19) | −0.0139 (15) | 0.0102 (15) | −0.0011 (16) |
C3 | 0.078 (2) | 0.075 (2) | 0.0595 (19) | −0.0078 (19) | 0.0097 (16) | −0.0107 (17) |
C4 | 0.0498 (17) | 0.081 (2) | 0.0595 (19) | 0.0021 (17) | 0.0074 (14) | 0.0110 (17) |
C5 | 0.0476 (16) | 0.073 (2) | 0.069 (2) | −0.0149 (15) | 0.0094 (15) | 0.0132 (17) |
C6 | 0.0514 (16) | 0.0578 (17) | 0.0609 (18) | −0.0082 (14) | 0.0027 (14) | −0.0007 (15) |
C7 | 0.0570 (17) | 0.0475 (16) | 0.0638 (18) | −0.0020 (15) | 0.0205 (14) | 0.0029 (14) |
C8 | 0.0489 (16) | 0.0415 (15) | 0.0630 (17) | 0.0007 (13) | 0.0212 (13) | 0.0071 (13) |
C9 | 0.0555 (18) | 0.0483 (18) | 0.081 (2) | 0.0126 (14) | 0.0214 (15) | −0.0012 (15) |
C10 | 0.0601 (18) | 0.0470 (17) | 0.075 (2) | 0.0066 (14) | 0.0166 (15) | −0.0100 (14) |
C11 | 0.0536 (16) | 0.0468 (16) | 0.0575 (17) | 0.0041 (13) | 0.0244 (14) | 0.0025 (14) |
C12 | 0.0540 (17) | 0.0523 (17) | 0.0678 (18) | 0.0154 (14) | 0.0196 (15) | −0.0018 (14) |
C13 | 0.0601 (18) | 0.0447 (16) | 0.0673 (19) | 0.0057 (14) | 0.0178 (15) | −0.0046 (14) |
C14 | 0.075 (2) | 0.106 (3) | 0.080 (2) | 0.018 (2) | 0.0142 (18) | −0.019 (2) |
C15 | 0.094 (3) | 0.100 (3) | 0.082 (3) | 0.014 (2) | −0.003 (2) | −0.026 (2) |
C16 | 0.080 (2) | 0.087 (3) | 0.092 (3) | 0.008 (2) | −0.004 (2) | −0.012 (2) |
C17 | 0.062 (2) | 0.146 (4) | 0.092 (3) | 0.024 (2) | 0.0066 (19) | −0.027 (3) |
C18 | 0.062 (2) | 0.120 (3) | 0.091 (3) | 0.027 (2) | 0.0031 (18) | −0.037 (2) |
C19 | 0.096 (3) | 0.157 (4) | 0.068 (2) | −0.011 (3) | 0.034 (2) | 0.010 (2) |
N1 | 0.0554 (15) | 0.0502 (14) | 0.0646 (15) | −0.0005 (12) | 0.0141 (12) | 0.0008 (13) |
N2 | 0.0468 (13) | 0.0513 (14) | 0.0650 (15) | −0.0022 (12) | 0.0133 (11) | 0.0058 (12) |
N3 | 0.0522 (14) | 0.0670 (16) | 0.0603 (15) | 0.0086 (12) | 0.0161 (11) | −0.0056 (12) |
O1 | 0.0673 (13) | 0.0926 (16) | 0.0530 (12) | 0.0007 (12) | −0.0013 (10) | 0.0053 (11) |
O2 | 0.0852 (15) | 0.0493 (12) | 0.0840 (15) | −0.0002 (11) | 0.0293 (12) | 0.0194 (10) |
S1 | 0.0529 (4) | 0.0546 (4) | 0.0558 (4) | 0.0012 (4) | 0.0083 (3) | 0.0101 (4) |
C1—C2 | 1.373 (4) | C13—H13 | 0.9300 |
C1—C6 | 1.388 (4) | C14—N3 | 1.452 (4) |
C1—S1 | 1.749 (3) | C14—C15 | 1.496 (4) |
C2—C3 | 1.379 (4) | C14—H14A | 0.9700 |
C2—H2 | 0.9300 | C14—H14B | 0.9700 |
C3—C4 | 1.369 (4) | C15—C16 | 1.466 (5) |
C3—H3 | 0.9300 | C15—H15A | 0.9700 |
C4—C5 | 1.374 (4) | C15—H15B | 0.9700 |
C4—C19 | 1.499 (4) | C16—C17 | 1.481 (5) |
C5—C6 | 1.370 (4) | C16—H16A | 0.9700 |
C5—H5 | 0.9300 | C16—H16B | 0.9700 |
C6—H6 | 0.9300 | C17—C18 | 1.498 (4) |
C7—N2 | 1.269 (3) | C17—H17A | 0.9700 |
C7—C8 | 1.452 (4) | C17—H17B | 0.9700 |
C7—H7 | 0.9300 | C18—N3 | 1.435 (4) |
C8—C13 | 1.374 (4) | C18—H18A | 0.9700 |
C8—C9 | 1.395 (4) | C18—H18B | 0.9700 |
C9—C10 | 1.365 (4) | C19—H19A | 0.9600 |
C9—H9 | 0.9300 | C19—H19B | 0.9600 |
C10—C11 | 1.402 (4) | C19—H19C | 0.9600 |
C10—H10 | 0.9300 | N1—N2 | 1.395 (3) |
C11—C12 | 1.389 (4) | N1—S1 | 1.637 (3) |
C11—N3 | 1.402 (3) | N1—H1N | 0.79 (3) |
C12—C13 | 1.379 (4) | O1—S1 | 1.421 (2) |
C12—H12 | 0.9300 | O2—S1 | 1.424 (2) |
C2—C1—C6 | 119.5 (3) | H14A—C14—H14B | 107.6 |
C2—C1—S1 | 121.1 (2) | C16—C15—C14 | 113.7 (3) |
C6—C1—S1 | 119.4 (2) | C16—C15—H15A | 108.8 |
C1—C2—C3 | 119.4 (3) | C14—C15—H15A | 108.8 |
C1—C2—H2 | 120.3 | C16—C15—H15B | 108.8 |
C3—C2—H2 | 120.3 | C14—C15—H15B | 108.8 |
C4—C3—C2 | 122.0 (3) | H15A—C15—H15B | 107.7 |
C4—C3—H3 | 119.0 | C15—C16—C17 | 110.9 (3) |
C2—C3—H3 | 119.0 | C15—C16—H16A | 109.5 |
C3—C4—C5 | 117.7 (3) | C17—C16—H16A | 109.5 |
C3—C4—C19 | 121.4 (3) | C15—C16—H16B | 109.5 |
C5—C4—C19 | 120.9 (3) | C17—C16—H16B | 109.5 |
C6—C5—C4 | 121.9 (3) | H16A—C16—H16B | 108.1 |
C6—C5—H5 | 119.1 | C16—C17—C18 | 113.2 (3) |
C4—C5—H5 | 119.1 | C16—C17—H17A | 108.9 |
C5—C6—C1 | 119.5 (3) | C18—C17—H17A | 108.9 |
C5—C6—H6 | 120.3 | C16—C17—H17B | 108.9 |
C1—C6—H6 | 120.3 | C18—C17—H17B | 108.9 |
N2—C7—C8 | 122.1 (3) | H17A—C17—H17B | 107.7 |
N2—C7—H7 | 119.0 | N3—C18—C17 | 114.8 (3) |
C8—C7—H7 | 119.0 | N3—C18—H18A | 108.6 |
C13—C8—C9 | 116.9 (3) | C17—C18—H18A | 108.6 |
C13—C8—C7 | 120.4 (3) | N3—C18—H18B | 108.6 |
C9—C8—C7 | 122.7 (2) | C17—C18—H18B | 108.6 |
C10—C9—C8 | 121.5 (3) | H18A—C18—H18B | 107.5 |
C10—C9—H9 | 119.2 | C4—C19—H19A | 109.5 |
C8—C9—H9 | 119.2 | C4—C19—H19B | 109.5 |
C9—C10—C11 | 121.9 (3) | H19A—C19—H19B | 109.5 |
C9—C10—H10 | 119.1 | C4—C19—H19C | 109.5 |
C11—C10—H10 | 119.1 | H19A—C19—H19C | 109.5 |
C12—C11—N3 | 122.9 (2) | H19B—C19—H19C | 109.5 |
C12—C11—C10 | 116.1 (3) | N2—N1—S1 | 114.78 (19) |
N3—C11—C10 | 121.0 (3) | N2—N1—H1N | 117 (2) |
C13—C12—C11 | 121.7 (2) | S1—N1—H1N | 115 (2) |
C13—C12—H12 | 119.2 | C7—N2—N1 | 116.0 (2) |
C11—C12—H12 | 119.2 | C11—N3—C18 | 116.7 (2) |
C8—C13—C12 | 121.9 (3) | C11—N3—C14 | 116.3 (2) |
C8—C13—H13 | 119.0 | C18—N3—C14 | 114.8 (2) |
C12—C13—H13 | 119.0 | O1—S1—O2 | 120.42 (13) |
N3—C14—C15 | 114.6 (3) | O1—S1—N1 | 104.23 (13) |
N3—C14—H14A | 108.6 | O2—S1—N1 | 107.07 (13) |
C15—C14—H14A | 108.6 | O1—S1—C1 | 108.61 (12) |
N3—C14—H14B | 108.6 | O2—S1—C1 | 107.88 (13) |
C15—C14—H14B | 108.6 | N1—S1—C1 | 108.05 (12) |
C6—C1—C2—C3 | 1.3 (4) | C14—C15—C16—C17 | −51.1 (5) |
S1—C1—C2—C3 | −177.0 (2) | C15—C16—C17—C18 | 51.3 (5) |
C1—C2—C3—C4 | −0.3 (5) | C16—C17—C18—N3 | −48.4 (5) |
C2—C3—C4—C5 | −0.7 (4) | C8—C7—N2—N1 | −176.9 (2) |
C2—C3—C4—C19 | 178.2 (3) | S1—N1—N2—C7 | −168.48 (19) |
C3—C4—C5—C6 | 0.7 (4) | C12—C11—N3—C18 | −1.2 (4) |
C19—C4—C5—C6 | −178.2 (3) | C10—C11—N3—C18 | 177.5 (3) |
C4—C5—C6—C1 | 0.3 (4) | C12—C11—N3—C14 | 139.5 (3) |
C2—C1—C6—C5 | −1.3 (4) | C10—C11—N3—C14 | −41.8 (4) |
S1—C1—C6—C5 | 177.1 (2) | C17—C18—N3—C11 | −174.8 (3) |
N2—C7—C8—C13 | 171.5 (3) | C17—C18—N3—C14 | 43.9 (4) |
N2—C7—C8—C9 | −6.2 (4) | C15—C14—N3—C11 | 175.2 (3) |
C13—C8—C9—C10 | 0.6 (4) | C15—C14—N3—C18 | −43.4 (4) |
C7—C8—C9—C10 | 178.4 (3) | N2—N1—S1—O1 | 178.95 (18) |
C8—C9—C10—C11 | −0.4 (4) | N2—N1—S1—O2 | −52.4 (2) |
C9—C10—C11—C12 | −0.1 (4) | N2—N1—S1—C1 | 63.5 (2) |
C9—C10—C11—N3 | −178.9 (3) | C2—C1—S1—O1 | 146.9 (2) |
N3—C11—C12—C13 | 179.0 (3) | C6—C1—S1—O1 | −31.4 (2) |
C10—C11—C12—C13 | 0.2 (4) | C2—C1—S1—O2 | 14.9 (2) |
C9—C8—C13—C12 | −0.5 (4) | C6—C1—S1—O2 | −163.5 (2) |
C7—C8—C13—C12 | −178.3 (3) | C2—C1—S1—N1 | −100.6 (2) |
C11—C12—C13—C8 | 0.1 (4) | C6—C1—S1—N1 | 81.1 (2) |
N3—C14—C15—C16 | 47.7 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O2i | 0.79 (3) | 2.29 (3) | 3.068 (3) | 170 (3) |
Symmetry code: (i) x, y+1, z. |
C18H20ClN3O2S | F(000) = 3168 |
Mr = 377.88 | Dx = 1.346 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 33.052 (6) Å | Cell parameters from 1174 reflections |
b = 5.258 (1) Å | θ = 2.5–27.8° |
c = 43.026 (8) Å | µ = 0.33 mm−1 |
β = 94.05 (2)° | T = 293 K |
V = 7459 (2) Å3 | Prism, red |
Z = 16 | 0.50 × 0.26 × 0.14 mm |
Oxford Diffraction Xcalibur diffractometer with Sapphire CCD | 2999 reflections with I > 2σ(I) |
Radiation source: Enhance (Mo) X-ray Source | Rint = 0.042 |
Rotation method data acquisition using ω scans. | θmax = 25.4°, θmin = 2.7° |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009) | h = −39→39 |
Tmin = 0.851, Tmax = 0.955 | k = −6→6 |
14002 measured reflections | l = −42→51 |
6833 independent reflections |
Refinement on F2 | 31 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.075 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.172 | w = 1/[σ2(Fo2) + (0.0483P)2 + 15.4136P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max < 0.001 |
6833 reflections | Δρmax = 0.27 e Å−3 |
457 parameters | Δρmin = −0.30 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
Cl1 | 0.47550 (5) | 0.3259 (4) | 0.18187 (4) | 0.1273 (7) | |
S1 | 0.31044 (4) | 0.0442 (3) | 0.11230 (3) | 0.0657 (4) | |
O1 | 0.27796 (10) | 0.1162 (6) | 0.13046 (7) | 0.0779 (10) | |
O2 | 0.31308 (11) | −0.2078 (6) | 0.10041 (8) | 0.0797 (10) | |
N1 | 0.30660 (14) | 0.2366 (8) | 0.08245 (9) | 0.0636 (12) | |
H1N | 0.2999 (15) | 0.387 (9) | 0.0854 (11) | 0.076* | |
N2 | 0.33782 (12) | 0.2115 (8) | 0.06209 (9) | 0.0625 (11) | |
N3 | 0.45666 (13) | 0.3870 (8) | −0.04820 (10) | 0.0770 (12) | |
C1 | 0.35682 (15) | 0.1126 (9) | 0.13273 (10) | 0.0563 (13) | |
C2 | 0.39197 (19) | −0.0048 (11) | 0.12540 (13) | 0.0843 (17) | |
H2 | 0.3912 | −0.1276 | 0.1098 | 0.101* | |
C3 | 0.42848 (19) | 0.0587 (12) | 0.14107 (15) | 0.0940 (19) | |
H3 | 0.4523 | −0.0232 | 0.1365 | 0.113* | |
C4 | 0.42913 (17) | 0.2419 (12) | 0.16323 (12) | 0.0763 (16) | |
C5 | 0.3948 (2) | 0.3541 (12) | 0.17136 (13) | 0.0895 (18) | |
H5 | 0.3958 | 0.4727 | 0.1874 | 0.107* | |
C6 | 0.35822 (17) | 0.2929 (11) | 0.15586 (12) | 0.0813 (16) | |
H6 | 0.3346 | 0.3735 | 0.1610 | 0.098* | |
C7 | 0.34159 (15) | 0.3963 (10) | 0.04343 (11) | 0.0619 (13) | |
H7 | 0.3245 | 0.5362 | 0.0445 | 0.074* | |
C8 | 0.37184 (15) | 0.3948 (9) | 0.02046 (10) | 0.0565 (13) | |
C9 | 0.40063 (17) | 0.2080 (10) | 0.01923 (12) | 0.0733 (15) | |
H9 | 0.4013 | 0.0785 | 0.0340 | 0.088* | |
C10 | 0.42840 (16) | 0.2054 (10) | −0.00296 (12) | 0.0726 (15) | |
H10 | 0.4473 | 0.0747 | −0.0031 | 0.087* | |
C11 | 0.42853 (15) | 0.3964 (10) | −0.02534 (11) | 0.0589 (13) | |
C12 | 0.39956 (16) | 0.5837 (10) | −0.02398 (11) | 0.0686 (14) | |
H12 | 0.3986 | 0.7135 | −0.0387 | 0.082* | |
C13 | 0.37211 (16) | 0.5843 (9) | −0.00157 (11) | 0.0689 (14) | |
H13 | 0.3533 | 0.7155 | −0.0012 | 0.083* | |
C14 | 0.49585 (19) | 0.3073 (16) | −0.04105 (16) | 0.143 (3) | |
H14A | 0.4943 | 0.1452 | −0.0304 | 0.172* | |
H14B | 0.5081 | 0.4269 | −0.0260 | 0.172* | |
C15 | 0.5239 (2) | 0.2760 (15) | −0.06531 (18) | 0.139 (3) | |
H15A | 0.5512 | 0.3004 | −0.0560 | 0.166* | |
H15B | 0.5220 | 0.1017 | −0.0727 | 0.166* | |
C16 | 0.5182 (2) | 0.4427 (14) | −0.09203 (15) | 0.118 (2) | |
H16A | 0.5346 | 0.5939 | −0.0881 | 0.142* | |
H16B | 0.5282 | 0.3573 | −0.1100 | 0.142* | |
C17 | 0.4780 (2) | 0.5174 (17) | −0.09945 (16) | 0.150 (3) | |
H17A | 0.4658 | 0.3929 | −0.1139 | 0.180* | |
H17B | 0.4787 | 0.6774 | −0.1106 | 0.180* | |
C18 | 0.45054 (18) | 0.5500 (13) | −0.07439 (13) | 0.115 (2) | |
H18A | 0.4528 | 0.7243 | −0.0671 | 0.138* | |
H18B | 0.4230 | 0.5263 | −0.0832 | 0.138* | |
Cl2 | 0.22664 (5) | 0.4803 (4) | 0.02015 (4) | 0.1245 (7) | |
S2 | 0.13541 (5) | 0.7140 (3) | 0.13800 (3) | 0.0696 (4) | |
O3 | 0.09541 (11) | 0.6126 (7) | 0.13364 (8) | 0.0883 (11) | |
O4 | 0.14190 (11) | 0.9734 (6) | 0.14659 (7) | 0.0845 (11) | |
N4 | 0.15747 (15) | 0.5383 (8) | 0.16570 (10) | 0.0702 (13) | |
H4N | 0.1518 (16) | 0.384 (9) | 0.1629 (12) | 0.084* | |
N5 | 0.19715 (14) | 0.6102 (8) | 0.17526 (9) | 0.0654 (11) | |
N6 | 0.37521 (14) | 0.6426 (8) | 0.24681 (10) | 0.0726 (12) | |
C19 | 0.16088 (15) | 0.6564 (9) | 0.10444 (10) | 0.0576 (13) | |
C20 | 0.19395 (16) | 0.7992 (11) | 0.09801 (12) | 0.0746 (15) | |
H20 | 0.2028 | 0.9306 | 0.1113 | 0.090* | |
C21 | 0.21407 (16) | 0.7463 (12) | 0.07161 (13) | 0.0823 (17) | |
H21 | 0.2361 | 0.8446 | 0.0666 | 0.099* | |
C22 | 0.20116 (18) | 0.5481 (12) | 0.05306 (11) | 0.0748 (16) | |
C23 | 0.16849 (19) | 0.4049 (11) | 0.05942 (13) | 0.0823 (17) | |
H23 | 0.1600 | 0.2722 | 0.0462 | 0.099* | |
C24 | 0.14812 (17) | 0.4565 (10) | 0.08532 (12) | 0.0771 (16) | |
H24 | 0.1259 | 0.3583 | 0.0900 | 0.093* | |
C25 | 0.21791 (15) | 0.4430 (10) | 0.19052 (10) | 0.0606 (13) | |
H25 | 0.2068 | 0.2826 | 0.1932 | 0.073* | |
C26 | 0.25843 (15) | 0.4968 (9) | 0.20382 (10) | 0.0551 (12) | |
C27 | 0.28111 (17) | 0.7029 (10) | 0.19542 (10) | 0.0654 (14) | |
H27 | 0.2704 | 0.8106 | 0.1798 | 0.078* | |
C28 | 0.31893 (17) | 0.7547 (10) | 0.20933 (11) | 0.0692 (14) | |
H28 | 0.3333 | 0.8946 | 0.2028 | 0.083* | |
C29 | 0.33619 (16) | 0.5996 (10) | 0.23328 (11) | 0.0609 (13) | |
C30 | 0.31319 (16) | 0.3937 (10) | 0.24176 (11) | 0.0675 (14) | |
H30 | 0.3235 | 0.2879 | 0.2577 | 0.081* | |
C31 | 0.27607 (16) | 0.3414 (10) | 0.22745 (11) | 0.0665 (14) | |
H31 | 0.2621 | 0.1985 | 0.2335 | 0.080* | |
C32 | 0.39719 (19) | 0.8645 (12) | 0.23767 (15) | 0.104 (2) | |
H32A | 0.3844 | 1.0147 | 0.2457 | 0.125* | |
H32B | 0.3951 | 0.8759 | 0.2151 | 0.125* | |
C33 | 0.4411 (2) | 0.8653 (14) | 0.24890 (18) | 0.123 (2) | |
H33A | 0.4553 | 0.7399 | 0.2372 | 0.148* | |
H33B | 0.4525 | 1.0307 | 0.2447 | 0.148* | |
C34 | 0.44807 (19) | 0.8091 (14) | 0.28267 (17) | 0.110 (2) | |
H34A | 0.4769 | 0.7871 | 0.2879 | 0.132* | |
H34B | 0.4388 | 0.9514 | 0.2946 | 0.132* | |
C35 | 0.42629 (19) | 0.5767 (14) | 0.29094 (15) | 0.117 (2) | |
H35A | 0.4279 | 0.5591 | 0.3134 | 0.140* | |
H35B | 0.4395 | 0.4302 | 0.2824 | 0.140* | |
C36 | 0.38288 (17) | 0.5786 (13) | 0.27912 (12) | 0.099 (2) | |
H36A | 0.3716 | 0.4115 | 0.2825 | 0.119* | |
H36B | 0.3685 | 0.6990 | 0.2914 | 0.119* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0949 (12) | 0.1716 (18) | 0.1116 (13) | −0.0191 (13) | −0.0185 (10) | −0.0055 (13) |
S1 | 0.0844 (10) | 0.0535 (9) | 0.0593 (8) | −0.0097 (8) | 0.0064 (7) | 0.0000 (7) |
O1 | 0.077 (2) | 0.083 (3) | 0.076 (2) | −0.012 (2) | 0.022 (2) | 0.000 (2) |
O2 | 0.108 (3) | 0.045 (2) | 0.086 (2) | −0.013 (2) | 0.002 (2) | −0.0052 (18) |
N1 | 0.083 (3) | 0.054 (3) | 0.054 (2) | 0.005 (3) | 0.003 (2) | 0.007 (2) |
N2 | 0.080 (3) | 0.058 (3) | 0.050 (2) | −0.004 (2) | 0.004 (2) | −0.002 (2) |
N3 | 0.077 (2) | 0.077 (3) | 0.077 (3) | 0.010 (2) | 0.003 (2) | 0.017 (2) |
C1 | 0.076 (4) | 0.048 (3) | 0.046 (3) | −0.007 (3) | 0.014 (2) | −0.001 (2) |
C2 | 0.093 (4) | 0.080 (4) | 0.081 (4) | 0.011 (4) | 0.010 (4) | −0.025 (3) |
C3 | 0.080 (4) | 0.105 (5) | 0.098 (5) | 0.019 (4) | 0.010 (4) | −0.016 (4) |
C4 | 0.077 (4) | 0.089 (5) | 0.062 (3) | −0.009 (4) | 0.004 (3) | 0.000 (3) |
C5 | 0.092 (5) | 0.101 (5) | 0.075 (4) | −0.002 (4) | 0.001 (4) | −0.031 (3) |
C6 | 0.083 (4) | 0.090 (4) | 0.071 (4) | 0.006 (4) | 0.009 (3) | −0.023 (3) |
C7 | 0.073 (4) | 0.058 (3) | 0.053 (3) | −0.001 (3) | −0.004 (3) | 0.001 (3) |
C8 | 0.070 (3) | 0.050 (3) | 0.048 (3) | −0.005 (3) | −0.006 (3) | 0.001 (3) |
C9 | 0.093 (4) | 0.062 (4) | 0.064 (3) | 0.011 (4) | 0.001 (3) | 0.021 (3) |
C10 | 0.081 (4) | 0.063 (4) | 0.074 (4) | 0.021 (3) | 0.008 (3) | 0.015 (3) |
C11 | 0.062 (3) | 0.059 (3) | 0.056 (3) | 0.000 (3) | 0.000 (3) | 0.002 (3) |
C12 | 0.079 (4) | 0.065 (4) | 0.062 (3) | 0.014 (3) | 0.005 (3) | 0.019 (3) |
C13 | 0.080 (4) | 0.059 (3) | 0.068 (3) | 0.017 (3) | 0.011 (3) | 0.013 (3) |
C14 | 0.100 (3) | 0.204 (7) | 0.128 (5) | 0.073 (5) | 0.031 (4) | 0.061 (5) |
C15 | 0.114 (5) | 0.156 (6) | 0.152 (6) | 0.052 (5) | 0.049 (5) | 0.043 (5) |
C16 | 0.119 (4) | 0.127 (6) | 0.113 (5) | 0.031 (5) | 0.047 (4) | 0.026 (5) |
C17 | 0.122 (4) | 0.220 (7) | 0.115 (4) | 0.048 (5) | 0.054 (3) | 0.062 (5) |
C18 | 0.108 (4) | 0.149 (5) | 0.091 (4) | 0.041 (4) | 0.032 (3) | 0.054 (3) |
Cl2 | 0.1149 (13) | 0.1825 (19) | 0.0782 (10) | 0.0329 (13) | 0.0209 (9) | −0.0211 (12) |
S2 | 0.0840 (11) | 0.0686 (10) | 0.0560 (8) | 0.0118 (9) | 0.0033 (7) | 0.0047 (7) |
O3 | 0.069 (2) | 0.107 (3) | 0.088 (3) | 0.003 (2) | 0.003 (2) | 0.009 (2) |
O4 | 0.122 (3) | 0.062 (2) | 0.070 (2) | 0.019 (2) | 0.012 (2) | −0.0044 (19) |
N4 | 0.083 (3) | 0.068 (3) | 0.058 (3) | −0.002 (3) | −0.001 (2) | 0.008 (2) |
N5 | 0.080 (3) | 0.064 (3) | 0.051 (2) | 0.005 (3) | −0.002 (2) | 0.002 (2) |
N6 | 0.078 (3) | 0.074 (3) | 0.067 (3) | −0.002 (3) | 0.015 (2) | 0.013 (2) |
C19 | 0.068 (3) | 0.054 (3) | 0.049 (3) | 0.001 (3) | −0.006 (2) | 0.001 (3) |
C20 | 0.081 (4) | 0.080 (4) | 0.062 (4) | −0.008 (4) | −0.004 (3) | −0.014 (3) |
C21 | 0.076 (4) | 0.097 (5) | 0.074 (4) | −0.011 (4) | 0.004 (3) | 0.006 (4) |
C22 | 0.080 (4) | 0.090 (4) | 0.053 (3) | 0.020 (4) | −0.002 (3) | −0.006 (3) |
C23 | 0.105 (5) | 0.070 (4) | 0.070 (4) | 0.000 (4) | −0.005 (4) | −0.012 (3) |
C24 | 0.104 (4) | 0.065 (4) | 0.063 (3) | −0.019 (3) | 0.005 (3) | 0.001 (3) |
C25 | 0.072 (4) | 0.056 (3) | 0.056 (3) | 0.002 (3) | 0.016 (3) | 0.000 (3) |
C26 | 0.072 (4) | 0.047 (3) | 0.048 (3) | 0.005 (3) | 0.017 (3) | 0.000 (2) |
C27 | 0.085 (4) | 0.064 (4) | 0.047 (3) | 0.006 (3) | 0.007 (3) | 0.005 (3) |
C28 | 0.090 (4) | 0.058 (3) | 0.062 (3) | −0.007 (3) | 0.021 (3) | 0.013 (3) |
C29 | 0.070 (4) | 0.064 (4) | 0.049 (3) | 0.008 (3) | 0.015 (3) | −0.005 (3) |
C30 | 0.071 (4) | 0.069 (4) | 0.064 (3) | 0.007 (3) | 0.009 (3) | 0.021 (3) |
C31 | 0.069 (4) | 0.060 (3) | 0.073 (3) | 0.006 (3) | 0.017 (3) | 0.015 (3) |
C32 | 0.097 (5) | 0.100 (5) | 0.114 (5) | −0.016 (4) | −0.001 (4) | 0.014 (4) |
C33 | 0.090 (5) | 0.136 (6) | 0.143 (7) | −0.024 (5) | 0.007 (5) | 0.022 (5) |
C34 | 0.092 (5) | 0.110 (6) | 0.127 (6) | −0.009 (5) | −0.009 (4) | −0.012 (5) |
C35 | 0.103 (5) | 0.138 (6) | 0.107 (5) | −0.017 (5) | −0.015 (4) | 0.029 (5) |
C36 | 0.086 (4) | 0.143 (6) | 0.068 (4) | −0.025 (4) | 0.000 (3) | 0.006 (4) |
Cl1—C4 | 1.736 (5) | Cl2—C22 | 1.735 (5) |
S1—O1 | 1.423 (3) | S2—O4 | 1.425 (3) |
S1—O2 | 1.425 (3) | S2—O3 | 1.426 (4) |
S1—N1 | 1.633 (4) | S2—N4 | 1.638 (4) |
S1—C1 | 1.750 (5) | S2—C19 | 1.748 (5) |
N1—N2 | 1.406 (5) | N4—N5 | 1.399 (5) |
N1—H1N | 0.83 (4) | N4—H4N | 0.84 (5) |
N2—C7 | 1.272 (5) | N5—C25 | 1.269 (5) |
N3—C14 | 1.375 (6) | N6—C29 | 1.395 (6) |
N3—C11 | 1.401 (6) | N6—C36 | 1.435 (6) |
N3—C18 | 1.419 (6) | N6—C32 | 1.444 (6) |
C1—C2 | 1.371 (6) | C19—C20 | 1.371 (6) |
C1—C6 | 1.373 (6) | C19—C24 | 1.382 (6) |
C2—C3 | 1.381 (7) | C20—C21 | 1.384 (7) |
C2—H2 | 0.9300 | C20—H20 | 0.9300 |
C3—C4 | 1.355 (7) | C21—C22 | 1.363 (7) |
C3—H3 | 0.9300 | C21—H21 | 0.9300 |
C4—C5 | 1.347 (7) | C22—C23 | 1.360 (7) |
C5—C6 | 1.377 (7) | C23—C24 | 1.369 (7) |
C5—H5 | 0.9300 | C23—H23 | 0.9300 |
C6—H6 | 0.9300 | C24—H24 | 0.9300 |
C7—C8 | 1.455 (6) | C25—C26 | 1.447 (6) |
C7—H7 | 0.9300 | C25—H25 | 0.9300 |
C8—C9 | 1.371 (6) | C26—C27 | 1.380 (6) |
C8—C13 | 1.376 (6) | C26—C31 | 1.399 (6) |
C9—C10 | 1.370 (6) | C27—C28 | 1.374 (6) |
C9—H9 | 0.9300 | C27—H27 | 0.9300 |
C10—C11 | 1.392 (6) | C28—C29 | 1.403 (6) |
C10—H10 | 0.9300 | C28—H28 | 0.9300 |
C11—C12 | 1.378 (6) | C29—C30 | 1.386 (6) |
C12—C13 | 1.370 (6) | C30—C31 | 1.361 (6) |
C12—H12 | 0.9300 | C30—H30 | 0.9300 |
C13—H13 | 0.9300 | C31—H31 | 0.9300 |
C14—C15 | 1.453 (7) | C32—C33 | 1.497 (7) |
C14—H14A | 0.9700 | C32—H32A | 0.9700 |
C14—H14B | 0.9700 | C32—H32B | 0.9700 |
C15—C16 | 1.447 (8) | C33—C34 | 1.484 (8) |
C15—H15A | 0.9700 | C33—H33A | 0.9700 |
C15—H15B | 0.9700 | C33—H33B | 0.9700 |
C16—C17 | 1.403 (8) | C34—C35 | 1.475 (8) |
C16—H16A | 0.9700 | C34—H34A | 0.9700 |
C16—H16B | 0.9700 | C34—H34B | 0.9700 |
C17—C18 | 1.467 (7) | C35—C36 | 1.488 (7) |
C17—H17A | 0.9700 | C35—H35A | 0.9700 |
C17—H17B | 0.9700 | C35—H35B | 0.9700 |
C18—H18A | 0.9700 | C36—H36A | 0.9700 |
C18—H18B | 0.9700 | C36—H36B | 0.9700 |
O1—S1—O2 | 120.8 (2) | O4—S2—O3 | 120.9 (2) |
O1—S1—N1 | 104.3 (2) | O4—S2—N4 | 107.5 (2) |
O2—S1—N1 | 107.3 (2) | O3—S2—N4 | 104.2 (2) |
O1—S1—C1 | 109.7 (2) | O4—S2—C19 | 107.9 (2) |
O2—S1—C1 | 107.3 (2) | O3—S2—C19 | 108.8 (2) |
N1—S1—C1 | 106.5 (2) | N4—S2—C19 | 106.7 (2) |
N2—N1—S1 | 114.3 (3) | N5—N4—S2 | 114.9 (3) |
N2—N1—H1N | 114 (4) | N5—N4—H4N | 120 (4) |
S1—N1—H1N | 118 (3) | S2—N4—H4N | 111 (4) |
C7—N2—N1 | 115.5 (4) | C25—N5—N4 | 115.2 (4) |
C14—N3—C11 | 121.0 (5) | C29—N6—C36 | 117.4 (4) |
C14—N3—C18 | 116.2 (5) | C29—N6—C32 | 119.0 (5) |
C11—N3—C18 | 118.1 (4) | C36—N6—C32 | 113.3 (5) |
C2—C1—C6 | 119.4 (5) | C20—C19—C24 | 120.7 (5) |
C2—C1—S1 | 121.2 (4) | C20—C19—S2 | 120.6 (4) |
C6—C1—S1 | 119.3 (4) | C24—C19—S2 | 118.6 (4) |
C1—C2—C3 | 120.3 (5) | C19—C20—C21 | 119.5 (5) |
C1—C2—H2 | 119.9 | C19—C20—H20 | 120.3 |
C3—C2—H2 | 119.9 | C21—C20—H20 | 120.3 |
C4—C3—C2 | 119.0 (5) | C22—C21—C20 | 119.1 (5) |
C4—C3—H3 | 120.5 | C22—C21—H21 | 120.5 |
C2—C3—H3 | 120.5 | C20—C21—H21 | 120.5 |
C5—C4—C3 | 121.5 (5) | C23—C22—C21 | 121.7 (5) |
C5—C4—Cl1 | 120.1 (5) | C23—C22—Cl2 | 119.2 (5) |
C3—C4—Cl1 | 118.4 (5) | C21—C22—Cl2 | 119.0 (5) |
C4—C5—C6 | 119.9 (5) | C22—C23—C24 | 119.8 (5) |
C4—C5—H5 | 120.0 | C22—C23—H23 | 120.1 |
C6—C5—H5 | 120.0 | C24—C23—H23 | 120.1 |
C1—C6—C5 | 119.7 (5) | C23—C24—C19 | 119.2 (5) |
C1—C6—H6 | 120.1 | C23—C24—H24 | 120.4 |
C5—C6—H6 | 120.1 | C19—C24—H24 | 120.4 |
N2—C7—C8 | 121.8 (5) | N5—C25—C26 | 121.4 (5) |
N2—C7—H7 | 119.1 | N5—C25—H25 | 119.3 |
C8—C7—H7 | 119.1 | C26—C25—H25 | 119.3 |
C9—C8—C13 | 117.0 (5) | C27—C26—C31 | 116.3 (5) |
C9—C8—C7 | 122.8 (5) | C27—C26—C25 | 123.7 (5) |
C13—C8—C7 | 120.2 (5) | C31—C26—C25 | 120.0 (5) |
C10—C9—C8 | 122.3 (5) | C28—C27—C26 | 122.4 (5) |
C10—C9—H9 | 118.8 | C28—C27—H27 | 118.8 |
C8—C9—H9 | 118.8 | C26—C27—H27 | 118.8 |
C9—C10—C11 | 120.6 (5) | C27—C28—C29 | 121.0 (5) |
C9—C10—H10 | 119.7 | C27—C28—H28 | 119.5 |
C11—C10—H10 | 119.7 | C29—C28—H28 | 119.5 |
C12—C11—C10 | 116.8 (5) | C30—C29—N6 | 121.7 (5) |
C12—C11—N3 | 123.6 (5) | C30—C29—C28 | 116.4 (5) |
C10—C11—N3 | 119.6 (5) | N6—C29—C28 | 121.9 (5) |
C13—C12—C11 | 121.9 (5) | C31—C30—C29 | 122.2 (5) |
C13—C12—H12 | 119.1 | C31—C30—H30 | 118.9 |
C11—C12—H12 | 119.1 | C29—C30—H30 | 118.9 |
C12—C13—C8 | 121.3 (5) | C30—C31—C26 | 121.8 (5) |
C12—C13—H13 | 119.3 | C30—C31—H31 | 119.1 |
C8—C13—H13 | 119.3 | C26—C31—H31 | 119.1 |
N3—C14—C15 | 120.8 (6) | N6—C32—C33 | 114.2 (5) |
N3—C14—H14A | 107.1 | N6—C32—H32A | 108.7 |
C15—C14—H14A | 107.1 | C33—C32—H32A | 108.7 |
N3—C14—H14B | 107.1 | N6—C32—H32B | 108.7 |
C15—C14—H14B | 107.1 | C33—C32—H32B | 108.7 |
H14A—C14—H14B | 106.8 | H32A—C32—H32B | 107.6 |
C16—C15—C14 | 116.7 (6) | C34—C33—C32 | 113.3 (6) |
C16—C15—H15A | 108.1 | C34—C33—H33A | 108.9 |
C14—C15—H15A | 108.1 | C32—C33—H33A | 108.9 |
C16—C15—H15B | 108.1 | C34—C33—H33B | 108.9 |
C14—C15—H15B | 108.1 | C32—C33—H33B | 108.9 |
H15A—C15—H15B | 107.3 | H33A—C33—H33B | 107.7 |
C17—C16—C15 | 114.7 (6) | C35—C34—C33 | 110.9 (6) |
C17—C16—H16A | 108.6 | C35—C34—H34A | 109.5 |
C15—C16—H16A | 108.6 | C33—C34—H34A | 109.5 |
C17—C16—H16B | 108.6 | C35—C34—H34B | 109.5 |
C15—C16—H16B | 108.6 | C33—C34—H34B | 109.5 |
H16A—C16—H16B | 107.6 | H34A—C34—H34B | 108.1 |
C16—C17—C18 | 119.4 (6) | C34—C35—C36 | 112.8 (6) |
C16—C17—H17A | 107.5 | C34—C35—H35A | 109.0 |
C18—C17—H17A | 107.5 | C36—C35—H35A | 109.0 |
C16—C17—H17B | 107.5 | C34—C35—H35B | 109.0 |
C18—C17—H17B | 107.5 | C36—C35—H35B | 109.0 |
H17A—C17—H17B | 107.0 | H35A—C35—H35B | 107.8 |
N3—C18—C17 | 116.9 (5) | N6—C36—C35 | 115.6 (5) |
N3—C18—H18A | 108.1 | N6—C36—H36A | 108.4 |
C17—C18—H18A | 108.1 | C35—C36—H36A | 108.4 |
N3—C18—H18B | 108.1 | N6—C36—H36B | 108.4 |
C17—C18—H18B | 108.1 | C35—C36—H36B | 108.4 |
H18A—C18—H18B | 107.3 | H36A—C36—H36B | 107.4 |
O1—S1—N1—N2 | 175.8 (3) | O4—S2—N4—N5 | −47.7 (4) |
O2—S1—N1—N2 | −55.0 (4) | O3—S2—N4—N5 | −177.1 (3) |
C1—S1—N1—N2 | 59.7 (4) | C19—S2—N4—N5 | 67.8 (4) |
S1—N1—N2—C7 | −163.0 (3) | S2—N4—N5—C25 | −162.9 (3) |
O1—S1—C1—C2 | 159.7 (4) | O4—S2—C19—C20 | 26.0 (5) |
O2—S1—C1—C2 | 26.7 (5) | O3—S2—C19—C20 | 158.8 (4) |
N1—S1—C1—C2 | −87.9 (4) | N4—S2—C19—C20 | −89.3 (4) |
O1—S1—C1—C6 | −22.4 (5) | O4—S2—C19—C24 | −156.9 (4) |
O2—S1—C1—C6 | −155.4 (4) | O3—S2—C19—C24 | −24.1 (4) |
N1—S1—C1—C6 | 90.0 (4) | N4—S2—C19—C24 | 87.8 (4) |
C6—C1—C2—C3 | −0.3 (8) | C24—C19—C20—C21 | 1.7 (7) |
S1—C1—C2—C3 | 177.6 (4) | S2—C19—C20—C21 | 178.7 (4) |
C1—C2—C3—C4 | −1.4 (9) | C19—C20—C21—C22 | −1.9 (8) |
C2—C3—C4—C5 | 3.3 (9) | C20—C21—C22—C23 | 1.5 (8) |
C2—C3—C4—Cl1 | −178.1 (5) | C20—C21—C22—Cl2 | −179.5 (4) |
C3—C4—C5—C6 | −3.5 (9) | C21—C22—C23—C24 | −1.0 (8) |
Cl1—C4—C5—C6 | 177.9 (4) | Cl2—C22—C23—C24 | −180.0 (4) |
C2—C1—C6—C5 | 0.1 (8) | C22—C23—C24—C19 | 0.8 (8) |
S1—C1—C6—C5 | −177.9 (4) | C20—C19—C24—C23 | −1.1 (7) |
C4—C5—C6—C1 | 1.8 (9) | S2—C19—C24—C23 | −178.2 (4) |
N1—N2—C7—C8 | −178.4 (4) | N4—N5—C25—C26 | −175.5 (4) |
N2—C7—C8—C9 | −6.3 (7) | N5—C25—C26—C27 | −15.6 (7) |
N2—C7—C8—C13 | 172.8 (4) | N5—C25—C26—C31 | 161.8 (4) |
C13—C8—C9—C10 | −0.7 (7) | C31—C26—C27—C28 | −0.1 (7) |
C7—C8—C9—C10 | 178.5 (5) | C25—C26—C27—C28 | 177.4 (4) |
C8—C9—C10—C11 | 0.4 (8) | C26—C27—C28—C29 | −0.7 (7) |
C9—C10—C11—C12 | −0.3 (7) | C36—N6—C29—C30 | −35.3 (7) |
C9—C10—C11—N3 | −178.7 (5) | C32—N6—C29—C30 | −178.2 (5) |
C14—N3—C11—C12 | 142.9 (6) | C36—N6—C29—C28 | 148.0 (5) |
C18—N3—C11—C12 | −11.8 (7) | C32—N6—C29—C28 | 5.1 (7) |
C14—N3—C11—C10 | −38.8 (8) | C27—C28—C29—C30 | 0.3 (7) |
C18—N3—C11—C10 | 166.4 (5) | C27—C28—C29—N6 | 177.3 (4) |
C10—C11—C12—C13 | 0.6 (7) | N6—C29—C30—C31 | −176.1 (4) |
N3—C11—C12—C13 | 178.9 (5) | C28—C29—C30—C31 | 0.9 (7) |
C11—C12—C13—C8 | −1.0 (8) | C29—C30—C31—C26 | −1.7 (8) |
C9—C8—C13—C12 | 1.0 (7) | C27—C26—C31—C30 | 1.3 (7) |
C7—C8—C13—C12 | −178.2 (5) | C25—C26—C31—C30 | −176.3 (4) |
C11—N3—C14—C15 | 174.4 (7) | C29—N6—C32—C33 | −168.9 (5) |
C18—N3—C14—C15 | −30.4 (10) | C36—N6—C32—C33 | 46.7 (7) |
N3—C14—C15—C16 | 30.9 (12) | N6—C32—C33—C34 | −49.6 (8) |
C14—C15—C16—C17 | −30.7 (11) | C32—C33—C34—C35 | 50.7 (8) |
C15—C16—C17—C18 | 32.7 (12) | C33—C34—C35—C36 | −50.0 (8) |
C14—N3—C18—C17 | 30.2 (9) | C29—N6—C36—C35 | 168.0 (5) |
C11—N3—C18—C17 | −173.8 (6) | C32—N6—C36—C35 | −47.1 (8) |
C16—C17—C18—N3 | −32.9 (11) | C34—C35—C36—N6 | 49.5 (8) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O2i | 0.83 (4) | 2.26 (5) | 3.025 (5) | 153 (5) |
N4—H4N···O4ii | 0.84 (5) | 2.29 (5) | 3.115 (6) | 169 (5) |
Symmetry codes: (i) x, y+1, z; (ii) x, y−1, z. |
Acknowledgements
The authors thank SAIF Panjab University for extending the services of the NMR facility.
Funding information
NP thanks the Department of Science and Technology, Government of India, New Delhi, for a research fellowship under its PURSE Program and BTG thanks the University Grants Commission, Government of India, New Delhi, for a special grant under a UGC-BSR one-time grant to faculty.
References
Comins, D. L., Brooks, C. A. & Ingalls, C. L. (2001). J. Org. Chem. 66, 2181–2182. Web of Science CrossRef PubMed CAS Google Scholar
Cremer, D. & Pople, A. J. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef Google Scholar
Grishina, G. V., Gaidatova, F. L. & Zefirov, N. S. (1995). Chem. Heterocycl. Com. 30, 1401–1426. CrossRef Google Scholar
Gu, W., Wu, R., Qi, S., Gu, C., Si, F. & Chen, Z. (2012). Molecules, 17, 4634–4650. Web of Science CrossRef CAS PubMed Google Scholar
Hirshfeld, F. L. (1977). Theor. Chim. Acta, 44, 129–138. CrossRef CAS Web of Science Google Scholar
Kang, D., Fang, Z., Huang, B., Zhang, L., Liu, U., Pannecouque, C., Naesens, L., De Clercq, E., Zhan, P. & Liu, X. (2015). Chem. Biol. Drug Des. 86, 568–577. CrossRef Google Scholar
Kiasalari, Z., Khalili, M., Roghani, M., Ahmadi, A. & Mireie, M. (2014). Iran J. Pathol. 9, 138–148. Google Scholar
McKinnon, J. J., Jayatilaka, D. & Spackman, M. A. (2007). Chem. Commun. 3814–3816. Google Scholar
Moss, G. P. (1996). Pure Appl. Chem. 68, 2193–2222. CrossRef CAS Web of Science Google Scholar
Nallini, A., Saraboji, K., Ponnuswamy, M. N., Venkatraj, M. & Jeyaraman, R. (2003). Mol. Cryst. Liq. Cryst. 403, 57–65. CrossRef Google Scholar
Nardelli, M. (1983). Comput. Chem. 7, 95–98. CrossRef CAS Web of Science Google Scholar
N'Gouan, A. J., Mansilla-Koblavi, F., Timotou, A., Adjou, A. & Ebby, N. (2009). Acta Cryst. E65, o2880. CrossRef IUCr Journals Google Scholar
Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd., Abingdon, England. Google Scholar
Parekh, J., Inamdhar, P., Nair, R., Baluja, S. & Chanda, S. (2005). J. Serb. Chem. Soc. 70, 1155–1162. Web of Science CrossRef CAS Google Scholar
Parvez, M., Bakhtiar, M., Baqir, M. & Zia-ur-Rehman, M. (2014). J. Chem. Crystallogr. 44, 580–585. CrossRef Google Scholar
Purandara, H., Foro, S. & Thimme Gowda, B. (2017). Acta Cryst. E73, 1946–1951. CrossRef IUCr Journals Google Scholar
Sahu, K., Behera, K., Pathaik, R. C., Nayak, A. & Behera, G. B. (1979). Indian J. Chem. Sect. B, 18, 557–561. Google Scholar
Sampath, N. (2017). J. Struct. Chem. 58, 804–808. CrossRef Google Scholar
Shah, S., Vyas, R. & Mehta, R. H. (1992). J. Indian Chem. Soc. 69, 590–596. CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Shit, S., Marschner, C. & Mitra, S. (2016). Acta Chim. Slov. 63, 129–137. Google Scholar
Soman, R., Sujatha, S. & Arunkumar, C. (2014). J. Fluor. Chem. 163, 16–22. Web of Science CrossRef CAS Google Scholar
Spackman, M. A. & Jayatilaka, D. (2009). CrystEngComm, 11, 19–32. Web of Science CrossRef CAS Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tharini, K. & Sangeetha, P. (2015). Int. J. Chem. Sci. 13, 1794–1804. Google Scholar
Turner, M. J., McKinnon, J. J., Wolff, S. K., Grimwood, D. J., Spackman, P. R., Jayatilaka, D. & Spackman, M. A. (2017). CrystalExplorer17. University of Western Australia. Google Scholar
Wang, C. L. & Wuorola, M. A. (1992). Org. Prep. Proceed. Int. 24, 585–621. Google Scholar
Yapo, Y. M., Kakou Yao, R., Timotou, A., N'Gouan, A. J. & Tenon, A. J. (2008). Phys. Chem. News 40, 77–80. Google Scholar
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