research communications
Conversion of diarylchalcones into 4,5-dihydropyrazole-1-carbothioamides: molecular and supramolecular structures of two precursors and three products
aDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysuru-570 006, India, bDepartment of Studies in Chemistry, Mangalore University, Mangalagangotri, Mangalore-574 199, India, cDepartment of Bioinformatics, School of Earth, Biological and Environmental Sciences, Central University of South Bihar, Gaya-824236, India, and dSchool of Chemistry, University of St Andrews, St Andrews, Fife KY16 9ST, UK
*Correspondence e-mail: yathirajan@hotmail.com
XC6H4C(O)CH=CHC6H4(OCH2CCH)-4, where X = Cl, Br or MeO, have been converted to the corresponding 4,5-dihydropyrazole-1-carbothioamides using a cyclocondensation reaction with thiosemicarbazide. The 1-(4-chlorophenyl)-3-[4-(prop-2-ynyloxy)phenyl]prop-2-en-1-one, C18H13ClO2, (I), and 1-(4-bromophenyl)-3-[4-(prop-2-ynyloxy)phenyl]prop-2-en-1-one, C18H13BrO2, (II), are isomorphous, and their molecules are linked into sheets by two independent C—H⋯π(arene) interactions, both involving the same aryl ring with one C—H donor approaching each face. In each of the products (RS)-3-(4-chlorophenyl)-5-[4-(prop-2-ynyloxy)phenyl]-4,5-dihydropyrazole-1-carbothioamide, C19H16ClN3OS, (IV), (RS)-3-(4-bromophenyl)-5-[4-(prop-2-ynyloxy)phenyl]-4,5-dihydropyrazole-1-carbothioamide, C19H16BrN3OS, (V), and (RS)-3-(4-methoxyphenyl)-5-[4-(prop-2-ynyloxy)phenyl]-4,5-dihydropyrazole-1-carbothioamide, C20H19N3O2S, (VI), the reduced pyrazole ring adopts an with the C atom bearing the 4-prop-2-ynyloxy)phenyl substituent, which occupies the axial site, displaced from the plane of the four ring atoms. Compounds (IV) and (V) are isomorphous and their molecules are linked into chains of edge-fused rings by a combination of N—H⋯S and C—H⋯S hydrogen bonds. The molecules of (VI) are linked into sheets by a combination of N—H⋯S, N—H⋯N and C—H⋯π(arene) hydrogen bonds. Comparisons are made with the structures of some related compounds.
of type 4-1. Chemical context
Pyrazole derivatives exhibit a wide range of pharmacological activities, including analgesic (Badawey & El-Ashmawey, 1998), antibacterial (Zhang et al., 2017), anticancer (Koca et al., 2013) and anti-inflammatory (Vijesh et al., 2013) activity, and recent work on both the synthesis of pyrazole derivatives and their pharmacological activities has been reviewed recently (Karrouchi et al., 2018). With this background in mind, we have now employed three compounds (I)–(III) as precursors for the synthesis of the corresponding 4,5-dihydropyrazole-1-carbothioamides, compounds (IV)–(VI), and we report here the molecular and supramolecular structures of two of the chalcone precursors, compounds (I) and (II), and of the three reduced pyrazole products (IV)–(VI): unfortunately, we have been unable to obtain satisfactory crystals of the chalcone (III). The were prepared (Fig. 6) by base-promoted condensation (Yuan et al., 2009; Yu et al., 2016; Yadav et al., 2017) of the appropriately substituted acetophenones with 4-(prop-2-ynyloxy)benzaldehye (Hans et al., 2010). Subsequent base-promoted cycloaddition of the (I)–(III) with thiosemicarbazide yielded the products (IV)–(VI).
2. Structural commentary
Compounds (I) and (II) are isomorphous in P21/c (Fig. 1 & 2). In each of these two compounds, the non-H atoms, apart from those of the ring (C11–C16) are almost coplanar: the r.m.s. deviations from the mean planes through the atoms C1 to C39 (Figs. 1 and 2) are 0.0455 Å in (I) and 0.0617 Å in (II), with the maximum deviation from this plane exhibited in each case by atom C1, 0.087 (2) Å in (I) and 0.092 (3) Å in (II). On the other hand, the ring (C11–C16) is twisted out of this plane, making a dihedral angle with it of 44.6 (6)° in (I) and 44.47 (8)° in (II).
Compounds (IV) and (V) are likewise isomorphous, this time in P21/n (Figs. 3 and 4). In each of compounds (IV)–(VI), there is a stereogenic centre at atom C5 (Figs. 3–5) and, in each case, the reference molecule was selected to be the one having the R configuration at this centre: the centrosymmetric space groups confirm that compounds (IV)–(VI) have all crystallized as racemic mixtures. The reduced pyrazole rings all adopt envelope conformations, folded across the line N1⋯C4: the ring-puckering parameters, calculated for the atom sequence (N1,N2,C3,C4,C5) are Q2 = 0.204 (3), 0.285 (4) and 0.217 (3) Å, and φ2 = 15.9 (10), 316.5 (12) and 319.4 (7)°, for (IV)–(VI), respectively. The displacements of the atom C5 from the plane of the other four atoms in the reduced pyrazole ring are 0.330 (5), 0.332 (6) and 0.351 (4) Å in compounds (IV)–(VI), respectively, and, in each case, the aryl substituent at atom C5 occupies the axial site. In compound (VI), the methoxy C atom is displaced from the plane of the adjacent aryl ring by only 0.215 (6) Å: associated with this near planarity, the two exocyclic O—C—C angles at atom C34 differ by almost 10°, as is frequently observed in near-planar alkoxyarene systems (Seip & Seip, 1973; Ferguson et al., 1996).
3. Supramolecular features
Despite the presence of a carbonyl group in compounds (I) and (II), their structures do not contain any C—H⋯O hydrogen bonds (Table 1): there are no intermolecular C⋯H contact distances less than 2.8 Å, well beyond the sum of the van der Waals radii, 2.68 Å (Rowland & Taylor, 1996). The structures do, however, contain two C—H⋯π(arene) hydrogen bonds, both involving the same ring (C31–C36) as the acceptor, with one C—H donor on each face of the ring and with H13i⋯Cg1⋯H35ii angles of 158° in (I) and 157° in (II), where Cg1 represents the centroid of the (C31–C36) ring [symmetry codes: (i) 1 − x, 1 − y, 1 − z; (ii) x, − y, + z]. The combination of these two C—H⋯π hydrogen bonds links the molecules into a sheet lying parallel to (100) and occupying the whole domain 0 < x < 1.0 (Fig. 7).
In each of the reduced pyrazole products (IV)–(VI) there is an intramolecular N—H⋯N hydrogen bond (Table 1). In the isomorphous pair (IV) and (V), the molecules are linked by a combination of N—H⋯S and C—H⋯S hydrogen bonds (Allen et al., 1997) to form a ribbon in the form of a chain of centrosymmetric, edge-fused rings running parallel to the [010] direction, in which R22(8) (Etter, 1990; Etter et al., 1990; Bernstein et al., 1995) rings centred at (, n, ) alternate with R42(18) rings centred at (, n + , ), where n represents an integer in each case (Fig. 8). There is also a short N—H⋯Br contact in the structure of compound (V), but it has been shown from database analyses (Brammer et al., 2001; Thallypally & Nangia, 2001) that halogen atoms bonded to C atoms are extremely poor acceptors of hydrogen bonds, so that this contact should not be regarded as structurally significant.
The molecules of compound (VI) are linked by a combination of N—H⋯S, N—H⋯N and C—H⋯π(arene) hydrogen bonds to form a complex sheet lying parallel to (001) in the domain 0 < z < (Fig. 9): a second sheet, related to the first by inversion lies in the domain ( < z < 1.0). The only direction-specific intermolecular contact between adjacent sheets is of the C—H⋯O type; however, this involves a C—H bond in a methyl group, which is probably undergoing fast rotation about the adjacent C—O bond (Riddell & Rogerson, 1996, 1997) and, in addition, it has a very small D—H⋯A angle, indicating a very small interaction energy (Wood et al., 2009). On both these grounds, this contact can be regarded as having negligible structural significance, so that the supramolecular assembly in (VI) is two-dimensional.
4. Database survey
It is of interest to briefly compare the structures of the reduced pyrazole derivatives (IV)–(VI) reported here with those of some related compounds. Although there are no records of any 4,5-dihydropyrazole-1-carbothioamides recorded in the Cambridge Structural Database (CSD version 5.40, update of December 2019; Groom et al., 2016), there are several examples of 4,5-dihydropyrazole-1-carboxamides which contain a CONH2 substituent, as opposed to the CSNH2 substituent in compounds (IV)–(VI). Both 3-ethyl-5-hydroxy-5- (trifluoromethyl)-4,5-dihydropyrazole-1-carboxamide (VII) (CSD refcode COJQUO; Sauzem et al., 2008) and 5-hydroxy-4-methyl-5-(trifluoromethyl)-4,5-dihydropyrazole-1-carboxamide (VIII) (COJRAV; Sauzem et al., 2008) contain intramolecular N—H⋯N hydrogen bonds analogous to those observed in compounds (IV)–(VI). In (VII), inversion-related pairs of molecules are linked by paired N—H⋯O hydrogen bonds to form cyclic dimers characterized by an R22(8) motif, while in (VIII) a combination of O—H⋯O, N—H⋯O and N—H⋯N hydrogen bonds links the molecules into complex sheets. In the enantiopure disubstituted carboxamide (4S)-N-[4-(difluoromethoxy)phenyl]-4-(4-fluorophenyl)-N-[(1S,4R)-4,7,7-trimethyl-3-oxo-2-oxabicyclo(2.2.1)hept-1-ylcarbonyl]-3-[4-(2,2,2-trifluoroethoxy)phenyl]-4,5-dihydropyrazole-1-carboxamide (IX) (SOTBAE; Bosum-Dybus & Neh, 1991), the only intermolecular hydrogen bonds are of the C—H⋯O type, and these link the molecules into chains. We also note the structures of the simpler 4,5-dihydropyrazoles 3-(2-naphthyl)-5-hydroxy-5-(trifluoromethyl)-4,5-dihydropyrazole (X) (MAFVUL; Yang & Raptis, 2003) and 3-(2,2-dicyanoethenyl)-1-phenyl-4,5-dihydro-1H-pyrazole (XI) (XEHMOM; Cole et al., 2000), which is a non-linear-optical material crystallizing in Cc, and which has been the subject of a variable-temperature study employing both X-ray and neutron diffraction. Finally, we note that structures have been reported for a number of reduced 3,4′-bipyrazoles (Cuartas et al., 2017; Kiran Kumar et al., 2019).
5. Synthesis and crystallization
Samples of the et al., 2010; Yuan et al., 2009; Yu et al., 2016; Yadav et al., 2017): crystals of compounds (I) and (II), which were suitable for single-crystal X-ray diffraction, were grown by slow evaporation, at ambient temperature and in the presence of air from a solution in methanol. Despite repeated attempts, no suitable crystals of (III) could be obtained.
(I)–(III) were prepared using the published methods (HansFor the synthesis of compounds (IV)–(VI), a solution of potassium hydroxide (0.2 g) in ethanol (20 ml) was added to a mixture of thiosemicarbazide (140 mg, 1.5 mol) and the corresponding chalcone (I)–(III) (1 mmol). These mixtures were then heated under reflux for 5 h, when N,N-dimethylformamide (9:1, v/v) to give the products (IV)–(VI).
indicated that the reactions were complete. The mixtures were then allowed to cool to ambient temperature, and the resulting solid products were collected by filtration, washed with water, dried in air and crystallized from a mixture of ethanol andCompound (IV). Yield 81%, m. p. 421 K. Analysis found C 61.7, H 4.4, N 11.4%; C19H16ClN3OS requires C 61.7, H 4.4, N 11.4%. IR (KBr, cm−1) 3440 (NH), 2123 (C≡C). NMR (DMSO-d6) δ(1H) 3.09 (dd, 1H J = 18.0, 3.3 Hz) and 3.84 (dd, J = 18.0, 11.5 Hz) (pyrazole CH2), 3.32 (t, 1H, J = 2.4 Hz, ≡C—H), 4.56 (d, 2H, J = 2.4 Hz OCH2), 5.73 (dd, 1H, J = 11.5, 3.3 Hz, pyrazole CH), 6.65 (d, 2H, J = 8.6 Hz) and 7.10 (d, 2H, J = 8.6 Hz) (C6H4O), 7.2 (m, 4H,C6H4Cl).
Compound (V). Yield 71%, m. p. 455–457 K. Analysis found C 55.2, H 3.9, N 10.1%; C19H16BrN3OS requires C 55.1, H 3.9, N 10.1%. IR (KBr, cm−1) 3414 (NH), 2126 (C≡C). NMR (DMSO-d6) δ(1H) 3.09 (dd, 1H J = 18.0, 3.4 Hz) and 3.80 (dd, J = 18.0, 11.5 Hz) (pyrazole CH2), 3.32 (t, 1H, J = 2.2 Hz, ≡C—H), 4.70 (d, 2H, J = 2.2 Hz OCH2), 5.89 (dd, 1H, J = 11.5, 3.4 Hz, pyrazole CH), 6.88 (d, 2H, J = 8.6 Hz) and 7.07 (d, 2H, J = 8.6 Hz) (C6H4O), 7.58 (d, 2H, J = 8.5 Hz) and 8.56 (d, 2H, J = 8.5 Hz) (C6H4Br).
Compound (VI). Yield 79%, m. p. 422–423 K. Analysis found C 65.8, H 5.2, N 11.5%; C20H19N3O2S requires C 65.7, H 5.2, N 11.5%. IR (KBr, cm−1) 3339 (NH), 2120 (C≡C). NMR (DMSO-d6) δ(1H) 3.09 (dd, 1H J = 17.9, 3.2 Hz) and 3.71 (dd, J = 17.0, 11.5 Hz) (pyrazole CH2), 3.69 (t, 1H, J = 2.3 Hz, ≡C—H), 3.78 (s, 3H, OCh), 4.52 (d, 2H, J = 2.3 Hz OCH2), 5.76 (dd, 1H, J = 11.5, 3.2 Hz, pyrazole CH), 6.75 (d, 2H, J = 8.8 Hz) and 7.02 (d, 2H, J = 8.8 Hz) (C6H4OCH2), 7.13 (d, 2H, J = 8.1 Hz) and 7.63 (d, 2H, J = 8.1 Hz) (C6H4OCH3).
Crystals of compounds (IV)–(VI), which were suitable for single-crystal X-ray
were selected directly from the analytical samples.6. Refinement
Crystal data, data collection and structure . All H atoms were located in difference maps, and then treated as riding atoms in geometrically idealized positions with C—H distances of 0.93 Å (alkenyl, alkynyl and aromatic), 0.96 Å (CH3), 0.97 Å (CH2) or 0.98 Å (aliphatic C—H), and with Uiso(H) = kUeq(C), where k = 1.5 for the methyl group, which was permitted to rotate but not to tilt, and 1.2 for all other H atoms.
details are summarized in Table 2
|
Supporting information
https://doi.org/10.1107/S2056989020001735/zl2770sup1.cif
contains datablocks global, I, II, IV, V, VI. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989020001735/zl2770Isup2.hkl
Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989020001735/zl2770IIsup3.hkl
Structure factors: contains datablock IV. DOI: https://doi.org/10.1107/S2056989020001735/zl2770IVsup4.hkl
Structure factors: contains datablock V. DOI: https://doi.org/10.1107/S2056989020001735/zl2770Vsup5.hkl
Structure factors: contains datablock VI. DOI: https://doi.org/10.1107/S2056989020001735/zl2770VIsup6.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989020001735/zl2770Isup7.cml
Supporting information file. DOI: https://doi.org/10.1107/S2056989020001735/zl2770IIsup8.cml
Supporting information file. DOI: https://doi.org/10.1107/S2056989020001735/zl2770IVsup9.cml
Supporting information file. DOI: https://doi.org/10.1107/S2056989020001735/zl2770Vsup10.cml
Supporting information file. DOI: https://doi.org/10.1107/S2056989020001735/zl2770VIsup11.cml
For all structures, data collection: APEX2 (Bruker, 2012); cell
APEX2/SAINT (Bruker, 2012); data reduction: SAINT/XPREP (Bruker, 2012); program(s) used to solve structure: SHELXT2014/5 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: PLATON (Spek, 2020); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015b) and PLATON (Spek, 2020).C18H13ClO2 | F(000) = 616 |
Mr = 296.73 | Dx = 1.314 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 17.990 (3) Å | Cell parameters from 2914 reflections |
b = 14.2529 (16) Å | θ = 1.1–25.9° |
c = 5.8661 (8) Å | µ = 0.26 mm−1 |
β = 94.419 (4)° | T = 296 K |
V = 1499.7 (3) Å3 | Block, orange |
Z = 4 | 0.20 × 0.20 × 0.15 mm |
Bruker APEXII diffractometer | 2912 independent reflections |
Radiation source: fine focussealed tube | 1777 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.048 |
φ and ω scans | θmax = 25.9°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Bruker, 2012) | h = −21→22 |
Tmin = 0.895, Tmax = 0.962 | k = −17→17 |
20193 measured reflections | l = −7→7 |
Refinement on F2 | Primary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.055 | H-atom parameters constrained |
wR(F2) = 0.132 | w = 1/[σ2(Fo2) + (0.0322P)2 + 1.191P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
2912 reflections | Δρmax = 0.32 e Å−3 |
190 parameters | Δρmin = −0.23 e Å−3 |
0 restraints |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.50644 (15) | 0.37616 (19) | 0.0035 (5) | 0.0454 (7) | |
O1 | 0.49123 (11) | 0.37815 (18) | −0.2039 (3) | 0.0705 (7) | |
C2 | 0.44832 (15) | 0.37402 (19) | 0.1650 (5) | 0.0470 (7) | |
H2 | 0.4612 | 0.3594 | 0.3175 | 0.056* | |
C3 | 0.37764 (15) | 0.39260 (17) | 0.0980 (4) | 0.0422 (6) | |
H3 | 0.3682 | 0.4115 | −0.0532 | 0.051* | |
C11 | 0.58630 (14) | 0.37539 (17) | 0.0931 (4) | 0.0388 (6) | |
C12 | 0.60937 (15) | 0.40870 (18) | 0.3093 (4) | 0.0443 (7) | |
H12 | 0.5742 | 0.4301 | 0.4052 | 0.053* | |
C13 | 0.68450 (16) | 0.41034 (18) | 0.3840 (5) | 0.0464 (7) | |
H13 | 0.7000 | 0.4340 | 0.5277 | 0.056* | |
C14 | 0.73548 (14) | 0.37664 (19) | 0.2428 (5) | 0.0455 (7) | |
Cl14 | 0.82940 (4) | 0.37534 (7) | 0.33965 (16) | 0.0789 (3) | |
C15 | 0.71402 (16) | 0.34316 (19) | 0.0276 (5) | 0.0506 (7) | |
H15 | 0.7494 | 0.3208 | −0.0665 | 0.061* | |
C16 | 0.63951 (15) | 0.34321 (18) | −0.0463 (5) | 0.0463 (7) | |
H16 | 0.6247 | 0.3213 | −0.1921 | 0.056* | |
C31 | 0.31322 (14) | 0.38698 (17) | 0.2325 (4) | 0.0385 (6) | |
C32 | 0.24378 (15) | 0.41655 (19) | 0.1399 (5) | 0.0472 (7) | |
H32 | 0.2398 | 0.4428 | −0.0057 | 0.057* | |
C33 | 0.18022 (16) | 0.4082 (2) | 0.2576 (5) | 0.0542 (8) | |
H33 | 0.1344 | 0.4289 | 0.1926 | 0.065* | |
C34 | 0.18612 (15) | 0.36873 (19) | 0.4728 (5) | 0.0478 (7) | |
C35 | 0.25439 (15) | 0.33836 (18) | 0.5696 (5) | 0.0460 (7) | |
H35 | 0.2580 | 0.3117 | 0.7147 | 0.055* | |
C36 | 0.31671 (15) | 0.34757 (17) | 0.4517 (4) | 0.0429 (7) | |
H36 | 0.3624 | 0.3272 | 0.5187 | 0.052* | |
O34 | 0.12808 (12) | 0.35634 (17) | 0.6100 (4) | 0.0737 (7) | |
C37 | 0.05810 (19) | 0.3821 (3) | 0.5204 (6) | 0.0851 (11) | |
H37A | 0.0428 | 0.3436 | 0.3886 | 0.102* | |
H37B | 0.0579 | 0.4473 | 0.4731 | 0.102* | |
C38 | 0.0066 (2) | 0.3679 (3) | 0.7054 (7) | 0.0920 (13) | |
C39 | −0.0365 (2) | 0.3578 (4) | 0.8370 (9) | 0.1210 (18) | |
H39 | −0.0715 | 0.3496 | 0.9439 | 0.145* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0503 (16) | 0.0486 (16) | 0.0372 (16) | −0.0022 (13) | 0.0016 (13) | 0.0008 (13) |
O1 | 0.0613 (14) | 0.1132 (19) | 0.0362 (12) | −0.0033 (13) | −0.0009 (10) | −0.0013 (12) |
C2 | 0.0497 (17) | 0.0545 (17) | 0.0366 (15) | −0.0013 (14) | 0.0012 (13) | 0.0043 (13) |
C3 | 0.0512 (16) | 0.0407 (15) | 0.0343 (15) | −0.0051 (12) | 0.0010 (12) | 0.0014 (12) |
C11 | 0.0483 (16) | 0.0374 (14) | 0.0308 (14) | −0.0001 (12) | 0.0041 (12) | 0.0018 (12) |
C12 | 0.0509 (17) | 0.0470 (16) | 0.0361 (16) | 0.0048 (13) | 0.0101 (13) | −0.0026 (12) |
C13 | 0.0573 (18) | 0.0476 (16) | 0.0340 (15) | −0.0031 (13) | 0.0018 (13) | −0.0036 (12) |
C14 | 0.0445 (16) | 0.0420 (15) | 0.0496 (17) | −0.0016 (12) | 0.0009 (13) | 0.0031 (14) |
Cl14 | 0.0491 (5) | 0.0928 (7) | 0.0938 (7) | −0.0010 (4) | −0.0009 (4) | −0.0102 (5) |
C15 | 0.0517 (18) | 0.0534 (17) | 0.0487 (18) | −0.0009 (14) | 0.0155 (14) | −0.0081 (14) |
C16 | 0.0573 (18) | 0.0478 (16) | 0.0345 (15) | −0.0058 (13) | 0.0086 (13) | −0.0037 (12) |
C31 | 0.0479 (16) | 0.0349 (14) | 0.0320 (14) | −0.0017 (12) | −0.0011 (12) | −0.0018 (11) |
C32 | 0.0562 (18) | 0.0474 (16) | 0.0373 (16) | 0.0020 (14) | −0.0020 (14) | 0.0041 (12) |
C33 | 0.0449 (17) | 0.0627 (19) | 0.0540 (19) | 0.0079 (14) | −0.0035 (14) | 0.0037 (15) |
C34 | 0.0476 (16) | 0.0528 (17) | 0.0435 (17) | −0.0019 (13) | 0.0077 (13) | −0.0031 (14) |
C35 | 0.0576 (18) | 0.0475 (16) | 0.0326 (15) | 0.0032 (13) | 0.0015 (13) | 0.0022 (12) |
C36 | 0.0466 (16) | 0.0420 (15) | 0.0392 (16) | 0.0014 (12) | −0.0029 (13) | −0.0020 (12) |
O34 | 0.0523 (13) | 0.1029 (18) | 0.0666 (15) | 0.0097 (12) | 0.0101 (11) | 0.0078 (13) |
C37 | 0.065 (2) | 0.111 (3) | 0.079 (3) | 0.008 (2) | 0.002 (2) | 0.019 (2) |
C38 | 0.050 (2) | 0.128 (4) | 0.099 (3) | −0.001 (2) | 0.017 (2) | 0.011 (3) |
C39 | 0.062 (3) | 0.189 (5) | 0.115 (4) | 0.007 (3) | 0.021 (3) | 0.034 (4) |
C1—O1 | 1.226 (3) | C31—C32 | 1.389 (3) |
C1—C2 | 1.465 (4) | C31—C36 | 1.400 (3) |
C1—C11 | 1.491 (4) | C32—C33 | 1.386 (4) |
C2—C3 | 1.328 (3) | C32—H32 | 0.9300 |
C2—H2 | 0.9300 | C33—C34 | 1.379 (4) |
C3—C31 | 1.454 (4) | C33—H33 | 0.9300 |
C3—H3 | 0.9300 | C34—O34 | 1.378 (3) |
C11—C16 | 1.385 (3) | C34—C35 | 1.382 (4) |
C11—C12 | 1.387 (3) | C35—C36 | 1.368 (4) |
C12—C13 | 1.388 (4) | C35—H35 | 0.9300 |
C12—H12 | 0.9300 | C36—H36 | 0.9300 |
C13—C14 | 1.369 (4) | O34—C37 | 1.376 (4) |
C13—H13 | 0.9300 | C37—C38 | 1.494 (5) |
C14—C15 | 1.377 (4) | C37—H37A | 0.9700 |
C14—Cl14 | 1.741 (3) | C37—H37B | 0.9700 |
C15—C16 | 1.377 (4) | C38—C39 | 1.144 (5) |
C15—H15 | 0.9300 | C39—H39 | 0.9300 |
C16—H16 | 0.9300 | ||
O1—C1—C2 | 121.8 (3) | C32—C31—C36 | 117.2 (2) |
O1—C1—C11 | 119.0 (2) | C32—C31—C3 | 120.1 (2) |
C2—C1—C11 | 119.2 (2) | C36—C31—C3 | 122.6 (2) |
C3—C2—C1 | 121.3 (2) | C33—C32—C31 | 122.1 (3) |
C3—C2—H2 | 119.4 | C33—C32—H32 | 119.0 |
C1—C2—H2 | 119.4 | C31—C32—H32 | 119.0 |
C2—C3—C31 | 127.8 (2) | C34—C33—C32 | 118.9 (3) |
C2—C3—H3 | 116.1 | C34—C33—H33 | 120.5 |
C31—C3—H3 | 116.1 | C32—C33—H33 | 120.5 |
C16—C11—C12 | 118.8 (2) | O34—C34—C33 | 125.4 (3) |
C16—C11—C1 | 119.0 (2) | O34—C34—C35 | 114.2 (2) |
C12—C11—C1 | 122.2 (2) | C33—C34—C35 | 120.5 (3) |
C11—C12—C13 | 120.6 (2) | C36—C35—C34 | 119.9 (3) |
C11—C12—H12 | 119.7 | C36—C35—H35 | 120.0 |
C13—C12—H12 | 119.7 | C34—C35—H35 | 120.0 |
C14—C13—C12 | 119.0 (3) | C35—C36—C31 | 121.5 (3) |
C14—C13—H13 | 120.5 | C35—C36—H36 | 119.3 |
C12—C13—H13 | 120.5 | C31—C36—H36 | 119.3 |
C13—C14—C15 | 121.5 (3) | C37—O34—C34 | 117.1 (3) |
C13—C14—Cl14 | 119.0 (2) | O34—C37—C38 | 106.7 (3) |
C15—C14—Cl14 | 119.5 (2) | O34—C37—H37A | 110.4 |
C16—C15—C14 | 119.1 (3) | C38—C37—H37A | 110.4 |
C16—C15—H15 | 120.5 | O34—C37—H37B | 110.4 |
C14—C15—H15 | 120.5 | C38—C37—H37B | 110.4 |
C15—C16—C11 | 121.0 (2) | H37A—C37—H37B | 108.6 |
C15—C16—H16 | 119.5 | C39—C38—C37 | 175.7 (5) |
C11—C16—H16 | 119.5 | C38—C39—H39 | 180.0 |
O1—C1—C2—C3 | −13.4 (4) | C1—C11—C16—C15 | 178.6 (2) |
C11—C1—C2—C3 | 166.9 (2) | C2—C3—C31—C32 | 174.7 (3) |
C1—C2—C3—C31 | 175.3 (2) | C2—C3—C31—C36 | −9.0 (4) |
O1—C1—C11—C16 | −23.3 (4) | C36—C31—C32—C33 | 0.2 (4) |
C2—C1—C11—C16 | 156.4 (2) | C3—C31—C32—C33 | 176.8 (2) |
O1—C1—C11—C12 | 154.6 (3) | C31—C32—C33—C34 | −0.4 (4) |
C2—C1—C11—C12 | −25.7 (4) | C32—C33—C34—O34 | 179.7 (3) |
C16—C11—C12—C13 | 0.4 (4) | C32—C33—C34—C35 | 0.2 (4) |
C1—C11—C12—C13 | −177.5 (2) | O34—C34—C35—C36 | −179.4 (2) |
C11—C12—C13—C14 | −1.4 (4) | C33—C34—C35—C36 | 0.1 (4) |
C12—C13—C14—C15 | 1.4 (4) | C34—C35—C36—C31 | −0.3 (4) |
C12—C13—C14—Cl14 | −178.0 (2) | C32—C31—C36—C35 | 0.1 (4) |
C13—C14—C15—C16 | −0.4 (4) | C3—C31—C36—C35 | −176.3 (2) |
Cl14—C14—C15—C16 | 179.1 (2) | C33—C34—O34—C37 | 2.8 (4) |
C14—C15—C16—C11 | −0.7 (4) | C35—C34—O34—C37 | −177.8 (3) |
C12—C11—C16—C15 | 0.6 (4) | C34—O34—C37—C38 | −176.4 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C13—H13···Cg1i | 0.93 | 2.90 | 3.554 (3) | 128 |
C35—H35···Cg1ii | 0.93 | 2.83 | 3.508 (3) | 131 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, −y+1/2, z+1/2. |
C18H13BrO2 | F(000) = 688 |
Mr = 341.18 | Dx = 1.489 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 18.286 (6) Å | Cell parameters from 2047 reflections |
b = 14.277 (4) Å | θ = 1.1–26.2° |
c = 5.8489 (17) Å | µ = 2.70 mm−1 |
β = 94.521 (7)° | T = 296 K |
V = 1522.2 (8) Å3 | Block, colourless |
Z = 4 | 0.20 × 0.15 × 0.15 mm |
Bruker APEXII diffractometer | 2945 independent reflections |
Radiation source: fine focussealed tube | 1335 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.119 |
φ and ω scans | θmax = 26.2°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2012) | h = −22→22 |
Tmin = 0.491, Tmax = 0.667 | k = −17→17 |
23006 measured reflections | l = −7→7 |
Refinement on F2 | Primary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.043 | H-atom parameters constrained |
wR(F2) = 0.089 | w = 1/[σ2(Fo2) + (0.0262P)2 + 0.1591P] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max = 0.001 |
2945 reflections | Δρmax = 0.43 e Å−3 |
190 parameters | Δρmin = −0.50 e Å−3 |
0 restraints |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.5049 (2) | 0.3768 (3) | 0.0000 (7) | 0.0455 (10) | |
O1 | 0.48975 (14) | 0.3791 (2) | −0.2076 (4) | 0.0658 (8) | |
C2 | 0.4477 (2) | 0.3747 (3) | 0.1628 (6) | 0.0428 (10) | |
H2 | 0.4606 | 0.3605 | 0.3158 | 0.051* | |
C3 | 0.3782 (2) | 0.3926 (2) | 0.0970 (6) | 0.0398 (10) | |
H3 | 0.3689 | 0.4117 | −0.0545 | 0.048* | |
C11 | 0.5835 (2) | 0.3755 (2) | 0.0928 (6) | 0.0355 (9) | |
C12 | 0.6067 (2) | 0.4089 (2) | 0.3083 (6) | 0.0420 (11) | |
H12 | 0.5723 | 0.4309 | 0.4041 | 0.050* | |
C13 | 0.6798 (2) | 0.4103 (2) | 0.3835 (6) | 0.0433 (11) | |
H13 | 0.6948 | 0.4337 | 0.5281 | 0.052* | |
C14 | 0.7306 (2) | 0.3767 (3) | 0.2425 (6) | 0.0431 (10) | |
Br14 | 0.83135 (2) | 0.37416 (4) | 0.34974 (8) | 0.0703 (2) | |
C15 | 0.7097 (2) | 0.3428 (2) | 0.0268 (7) | 0.0458 (11) | |
H15 | 0.7444 | 0.3200 | −0.0668 | 0.055* | |
C16 | 0.6364 (2) | 0.3435 (2) | −0.0474 (6) | 0.0444 (11) | |
H16 | 0.6218 | 0.3223 | −0.1942 | 0.053* | |
C31 | 0.3145 (2) | 0.3864 (2) | 0.2299 (6) | 0.0350 (9) | |
C32 | 0.2465 (2) | 0.4154 (2) | 0.1353 (6) | 0.0448 (11) | |
H32 | 0.2433 | 0.4417 | −0.0107 | 0.054* | |
C33 | 0.1829 (2) | 0.4070 (3) | 0.2489 (7) | 0.0472 (11) | |
H33 | 0.1379 | 0.4273 | 0.1818 | 0.057* | |
C34 | 0.1890 (2) | 0.3672 (3) | 0.4658 (6) | 0.0433 (10) | |
C35 | 0.2557 (2) | 0.3374 (2) | 0.5652 (6) | 0.0404 (10) | |
H35 | 0.2588 | 0.3107 | 0.7107 | 0.049* | |
C36 | 0.3175 (2) | 0.3473 (2) | 0.4488 (6) | 0.0390 (10) | |
H36 | 0.3624 | 0.3275 | 0.5175 | 0.047* | |
O34 | 0.13136 (16) | 0.35477 (19) | 0.6007 (4) | 0.0638 (8) | |
C37 | 0.0619 (2) | 0.3799 (3) | 0.5085 (7) | 0.0726 (13) | |
H37A | 0.0474 | 0.3410 | 0.3766 | 0.087* | |
H37B | 0.0616 | 0.4448 | 0.4596 | 0.087* | |
C38 | 0.0106 (3) | 0.3664 (4) | 0.6897 (9) | 0.0806 (15) | |
C39 | −0.0320 (3) | 0.3582 (4) | 0.8233 (9) | 0.106 (2) | |
H39 | −0.0664 | 0.3516 | 0.9312 | 0.127* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.050 (3) | 0.045 (3) | 0.041 (3) | −0.001 (2) | 0.003 (2) | 0.002 (2) |
O1 | 0.058 (2) | 0.110 (2) | 0.0289 (16) | −0.0013 (18) | −0.0015 (14) | −0.0012 (17) |
C2 | 0.044 (3) | 0.050 (2) | 0.034 (2) | −0.005 (2) | −0.002 (2) | 0.004 (2) |
C3 | 0.051 (3) | 0.035 (3) | 0.032 (2) | −0.008 (2) | −0.002 (2) | 0.0031 (18) |
C11 | 0.044 (3) | 0.033 (2) | 0.030 (2) | 0.002 (2) | 0.005 (2) | 0.004 (2) |
C12 | 0.048 (3) | 0.046 (3) | 0.032 (2) | 0.006 (2) | 0.007 (2) | −0.0007 (18) |
C13 | 0.054 (3) | 0.042 (3) | 0.034 (2) | −0.003 (2) | 0.000 (2) | −0.0056 (18) |
C14 | 0.040 (3) | 0.039 (2) | 0.050 (3) | −0.001 (2) | 0.001 (2) | 0.001 (2) |
Br14 | 0.0455 (3) | 0.0781 (3) | 0.0860 (4) | −0.0015 (3) | −0.0030 (2) | −0.0081 (3) |
C15 | 0.045 (3) | 0.047 (3) | 0.048 (3) | 0.001 (2) | 0.014 (2) | −0.010 (2) |
C16 | 0.058 (3) | 0.043 (3) | 0.032 (2) | −0.005 (2) | 0.003 (2) | −0.0052 (18) |
C31 | 0.044 (3) | 0.033 (2) | 0.028 (2) | −0.001 (2) | 0.000 (2) | −0.0026 (19) |
C32 | 0.051 (3) | 0.047 (3) | 0.034 (2) | 0.006 (2) | −0.008 (2) | 0.0047 (18) |
C33 | 0.037 (3) | 0.057 (3) | 0.047 (3) | 0.010 (2) | −0.001 (2) | 0.004 (2) |
C34 | 0.046 (3) | 0.046 (2) | 0.039 (2) | −0.001 (2) | 0.009 (2) | −0.005 (2) |
C35 | 0.048 (3) | 0.041 (3) | 0.031 (2) | 0.001 (2) | 0.000 (2) | 0.0030 (18) |
C36 | 0.038 (3) | 0.040 (3) | 0.037 (2) | −0.0017 (19) | −0.006 (2) | −0.0015 (18) |
O34 | 0.0415 (19) | 0.091 (2) | 0.0588 (19) | 0.0127 (17) | 0.0053 (16) | 0.0078 (16) |
C37 | 0.060 (4) | 0.088 (4) | 0.070 (3) | 0.009 (3) | 0.000 (3) | 0.008 (3) |
C38 | 0.047 (4) | 0.109 (4) | 0.086 (4) | 0.003 (4) | 0.009 (3) | 0.004 (4) |
C39 | 0.065 (4) | 0.162 (6) | 0.093 (4) | 0.014 (4) | 0.024 (3) | 0.023 (4) |
C1—O1 | 1.225 (4) | C31—C32 | 1.383 (5) |
C1—C2 | 1.470 (5) | C31—C36 | 1.394 (5) |
C1—C11 | 1.496 (5) | C32—C33 | 1.390 (5) |
C2—C3 | 1.323 (5) | C32—H32 | 0.9300 |
C2—H2 | 0.9300 | C33—C34 | 1.386 (5) |
C3—C31 | 1.453 (5) | C33—H33 | 0.9300 |
C3—H3 | 0.9300 | C34—C35 | 1.376 (5) |
C11—C12 | 1.383 (5) | C34—O34 | 1.377 (4) |
C11—C16 | 1.393 (5) | C35—C36 | 1.373 (5) |
C12—C13 | 1.373 (5) | C35—H35 | 0.9300 |
C12—H12 | 0.9300 | C36—H36 | 0.9300 |
C13—C14 | 1.376 (5) | O34—C37 | 1.388 (4) |
C13—H13 | 0.9300 | C37—C38 | 1.483 (6) |
C14—C15 | 1.377 (5) | C37—H37A | 0.9700 |
C14—Br14 | 1.899 (4) | C37—H37B | 0.9700 |
C15—C16 | 1.376 (5) | C38—C39 | 1.152 (6) |
C15—H15 | 0.9300 | C39—H39 | 0.9300 |
C16—H16 | 0.9300 | ||
O1—C1—C2 | 121.7 (4) | C32—C31—C36 | 117.1 (3) |
O1—C1—C11 | 119.8 (3) | C32—C31—C3 | 120.0 (3) |
C2—C1—C11 | 118.5 (3) | C36—C31—C3 | 122.7 (4) |
C3—C2—C1 | 121.6 (3) | C31—C32—C33 | 122.8 (4) |
C3—C2—H2 | 119.2 | C31—C32—H32 | 118.6 |
C1—C2—H2 | 119.2 | C33—C32—H32 | 118.6 |
C2—C3—C31 | 128.6 (3) | C34—C33—C32 | 117.6 (4) |
C2—C3—H3 | 115.7 | C34—C33—H33 | 121.2 |
C31—C3—H3 | 115.7 | C32—C33—H33 | 121.2 |
C12—C11—C16 | 118.1 (4) | C35—C34—O34 | 114.2 (3) |
C12—C11—C1 | 123.0 (3) | C35—C34—C33 | 121.1 (4) |
C16—C11—C1 | 118.8 (3) | O34—C34—C33 | 124.6 (4) |
C13—C12—C11 | 121.2 (3) | C36—C35—C34 | 119.7 (3) |
C13—C12—H12 | 119.4 | C36—C35—H35 | 120.1 |
C11—C12—H12 | 119.4 | C34—C35—H35 | 120.1 |
C12—C13—C14 | 119.3 (3) | C35—C36—C31 | 121.5 (4) |
C12—C13—H13 | 120.4 | C35—C36—H36 | 119.2 |
C14—C13—H13 | 120.4 | C31—C36—H36 | 119.2 |
C13—C14—C15 | 121.3 (4) | C34—O34—C37 | 117.5 (3) |
C13—C14—Br14 | 119.5 (3) | O34—C37—C38 | 107.5 (4) |
C15—C14—Br14 | 119.2 (3) | O34—C37—H37A | 110.2 |
C16—C15—C14 | 118.7 (3) | C38—C37—H37A | 110.2 |
C16—C15—H15 | 120.7 | O34—C37—H37B | 110.2 |
C14—C15—H15 | 120.7 | C38—C37—H37B | 110.2 |
C15—C16—C11 | 121.4 (3) | H37A—C37—H37B | 108.5 |
C15—C16—H16 | 119.3 | C39—C38—C37 | 176.5 (6) |
C11—C16—H16 | 119.3 | C38—C39—H39 | 180.0 |
O1—C1—C2—C3 | −12.7 (6) | C1—C11—C16—C15 | 178.4 (3) |
C11—C1—C2—C3 | 167.6 (4) | C2—C3—C31—C32 | 174.8 (4) |
C1—C2—C3—C31 | 174.6 (3) | C2—C3—C31—C36 | −8.7 (6) |
O1—C1—C11—C12 | 153.8 (4) | C36—C31—C32—C33 | 0.0 (5) |
C2—C1—C11—C12 | −26.5 (6) | C3—C31—C32—C33 | 176.7 (3) |
O1—C1—C11—C16 | −22.9 (6) | C31—C32—C33—C34 | −0.3 (6) |
C2—C1—C11—C16 | 156.8 (3) | C32—C33—C34—C35 | 0.2 (6) |
C16—C11—C12—C13 | −0.4 (5) | C32—C33—C34—O34 | 179.4 (3) |
C1—C11—C12—C13 | −177.1 (3) | O34—C34—C35—C36 | −179.1 (3) |
C11—C12—C13—C14 | −0.8 (5) | C33—C34—C35—C36 | 0.2 (6) |
C12—C13—C14—C15 | 0.8 (5) | C34—C35—C36—C31 | −0.5 (5) |
C12—C13—C14—Br14 | −177.7 (3) | C32—C31—C36—C35 | 0.4 (5) |
C13—C14—C15—C16 | 0.4 (5) | C3—C31—C36—C35 | −176.2 (3) |
Br14—C14—C15—C16 | 178.9 (3) | C35—C34—O34—C37 | −177.6 (3) |
C14—C15—C16—C11 | −1.6 (5) | C33—C34—O34—C37 | 3.1 (6) |
C12—C11—C16—C15 | 1.6 (5) | C34—O34—C37—C38 | −176.1 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C13—H13···Cg1i | 0.93 | 2.95 | 3.602 (4) | 128 |
C35—H35···Cg1ii | 0.93 | 2.80 | 3.484 (3) | 131 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, −y+1/2, z+1/2. |
C19H16ClN3OS | F(000) = 768 |
Mr = 369.86 | Dx = 1.385 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 15.0182 (9) Å | Cell parameters from 4932 reflections |
b = 6.0579 (3) Å | θ = 2.9–29.5° |
c = 20.8286 (12) Å | µ = 0.35 mm−1 |
β = 110.573 (2)° | T = 298 K |
V = 1774.11 (17) Å3 | Needle, colourless |
Z = 4 | 0.20 × 0.15 × 0.10 mm |
Bruker APEXII diffractometer | 3326 independent reflections |
Radiation source: fine focussealed tube | 2571 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.064 |
φ and ω scans | θmax = 25.6°, θmin = 3.5° |
Absorption correction: multi-scan (SADABS; Bruker, 2012) | h = −18→18 |
Tmin = 0.870, Tmax = 0.966 | k = −7→7 |
25833 measured reflections | l = −25→25 |
Refinement on F2 | Primary atom site location: difference Fourier map |
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) = 0.133 | w = 1/[σ2(Fo2) + (0.0304P)2 + 1.7629P] where P = (Fo2 + 2Fc2)/3 |
S = 1.24 | (Δ/σ)max < 0.001 |
3326 reflections | Δρmax = 0.19 e Å−3 |
232 parameters | Δρmin = −0.28 e Å−3 |
0 restraints |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
N1 | 0.5173 (2) | 0.7308 (4) | 0.34225 (14) | 0.0412 (7) | |
N2 | 0.45647 (18) | 0.5533 (4) | 0.31707 (14) | 0.0410 (7) | |
C3 | 0.4545 (2) | 0.5106 (6) | 0.25593 (17) | 0.0409 (8) | |
C4 | 0.5122 (2) | 0.6700 (6) | 0.23130 (17) | 0.0458 (9) | |
H4A | 0.4717 | 0.7751 | 0.1990 | 0.055* | |
H4 | 0.5513 | 0.5935 | 0.2100 | 0.055* | |
C5 | 0.5734 (2) | 0.7840 (6) | 0.29827 (17) | 0.0427 (8) | |
H5 | 0.5753 | 0.9439 | 0.2916 | 0.051* | |
C11 | 0.5230 (2) | 0.8250 (6) | 0.40229 (17) | 0.0402 (8) | |
S11 | 0.59292 (7) | 1.04457 (15) | 0.43338 (5) | 0.0499 (3) | |
N11 | 0.4696 (3) | 0.7346 (6) | 0.43395 (18) | 0.0623 (10) | |
H11B | 0.466 (3) | 0.803 (7) | 0.470 (2) | 0.075* | |
H11A | 0.439 (3) | 0.628 (7) | 0.417 (2) | 0.075* | |
C31 | 0.3970 (2) | 0.3293 (6) | 0.21696 (17) | 0.0411 (8) | |
C32 | 0.3691 (3) | 0.3240 (7) | 0.14614 (19) | 0.0619 (11) | |
H32 | 0.3909 | 0.4320 | 0.1236 | 0.074* | |
C33 | 0.3095 (3) | 0.1608 (8) | 0.1088 (2) | 0.0668 (12) | |
H33 | 0.2907 | 0.1593 | 0.0612 | 0.080* | |
C34 | 0.2781 (2) | 0.0015 (6) | 0.1419 (2) | 0.0531 (10) | |
Cl34 | 0.20074 (7) | −0.2014 (2) | 0.09434 (6) | 0.0773 (4) | |
C35 | 0.3074 (3) | −0.0024 (6) | 0.2126 (2) | 0.0535 (10) | |
H35 | 0.2874 | −0.1146 | 0.2348 | 0.064* | |
C36 | 0.3663 (2) | 0.1615 (6) | 0.24951 (19) | 0.0475 (9) | |
H36 | 0.3861 | 0.1600 | 0.2971 | 0.057* | |
C51 | 0.6726 (2) | 0.6900 (5) | 0.32626 (16) | 0.0397 (8) | |
C52 | 0.6902 (3) | 0.4924 (6) | 0.36169 (18) | 0.0497 (9) | |
H52 | 0.6404 | 0.4210 | 0.3698 | 0.060* | |
C53 | 0.7795 (2) | 0.3978 (6) | 0.38544 (18) | 0.0468 (9) | |
H53 | 0.7896 | 0.2643 | 0.4090 | 0.056* | |
C54 | 0.8535 (2) | 0.5047 (6) | 0.37368 (16) | 0.0417 (8) | |
C55 | 0.8367 (3) | 0.6981 (6) | 0.33696 (17) | 0.0457 (9) | |
H55 | 0.8863 | 0.7672 | 0.3278 | 0.055* | |
C56 | 0.7476 (3) | 0.7905 (6) | 0.31355 (17) | 0.0436 (8) | |
H56 | 0.7374 | 0.9219 | 0.2889 | 0.052* | |
O54 | 0.94624 (17) | 0.4330 (4) | 0.39776 (13) | 0.0540 (7) | |
C57 | 0.9668 (3) | 0.2523 (6) | 0.4444 (2) | 0.0563 (10) | |
H57A | 0.9342 | 0.1209 | 0.4211 | 0.068* | |
H57B | 0.9446 | 0.2847 | 0.4818 | 0.068* | |
C58 | 1.0686 (3) | 0.2143 (6) | 0.47095 (19) | 0.0526 (9) | |
C59 | 1.1497 (3) | 0.1775 (7) | 0.4949 (2) | 0.0631 (11) | |
H59 | 1.2145 | 0.1481 | 0.5141 | 0.076* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0464 (16) | 0.0399 (16) | 0.0436 (16) | −0.0078 (14) | 0.0237 (13) | −0.0016 (13) |
N2 | 0.0408 (16) | 0.0402 (16) | 0.0450 (16) | −0.0051 (14) | 0.0186 (13) | 0.0003 (14) |
C3 | 0.0390 (19) | 0.043 (2) | 0.0432 (19) | 0.0045 (16) | 0.0169 (16) | 0.0046 (16) |
C4 | 0.048 (2) | 0.050 (2) | 0.0420 (19) | 0.0046 (18) | 0.0192 (17) | 0.0044 (17) |
C5 | 0.052 (2) | 0.0373 (19) | 0.047 (2) | −0.0016 (17) | 0.0278 (17) | 0.0068 (16) |
C11 | 0.0413 (19) | 0.0395 (19) | 0.0426 (19) | 0.0000 (16) | 0.0181 (16) | 0.0028 (16) |
S11 | 0.0589 (6) | 0.0428 (5) | 0.0537 (6) | −0.0133 (5) | 0.0268 (5) | −0.0037 (5) |
N11 | 0.079 (3) | 0.068 (2) | 0.057 (2) | −0.0352 (19) | 0.044 (2) | −0.0192 (18) |
C31 | 0.0377 (19) | 0.0428 (19) | 0.0401 (19) | 0.0067 (16) | 0.0103 (15) | 0.0007 (16) |
C32 | 0.072 (3) | 0.066 (3) | 0.045 (2) | −0.010 (2) | 0.017 (2) | 0.001 (2) |
C33 | 0.073 (3) | 0.076 (3) | 0.044 (2) | −0.003 (3) | 0.013 (2) | −0.011 (2) |
C34 | 0.038 (2) | 0.055 (2) | 0.064 (3) | 0.0043 (18) | 0.0144 (19) | −0.016 (2) |
Cl34 | 0.0552 (6) | 0.0823 (8) | 0.0933 (8) | −0.0106 (6) | 0.0247 (6) | −0.0430 (7) |
C35 | 0.051 (2) | 0.047 (2) | 0.066 (3) | 0.0004 (18) | 0.025 (2) | −0.0029 (19) |
C36 | 0.050 (2) | 0.047 (2) | 0.046 (2) | 0.0060 (18) | 0.0171 (17) | 0.0010 (18) |
C51 | 0.047 (2) | 0.0379 (19) | 0.0382 (18) | −0.0054 (16) | 0.0199 (16) | 0.0000 (15) |
C52 | 0.049 (2) | 0.044 (2) | 0.063 (2) | −0.0090 (18) | 0.0285 (19) | 0.0071 (18) |
C53 | 0.049 (2) | 0.0379 (19) | 0.057 (2) | −0.0033 (17) | 0.0227 (18) | 0.0087 (17) |
C54 | 0.042 (2) | 0.046 (2) | 0.0390 (18) | −0.0056 (17) | 0.0177 (16) | −0.0067 (16) |
C55 | 0.048 (2) | 0.050 (2) | 0.047 (2) | −0.0132 (18) | 0.0275 (17) | 0.0027 (18) |
C56 | 0.055 (2) | 0.0383 (19) | 0.0429 (19) | −0.0081 (17) | 0.0241 (17) | 0.0071 (16) |
O54 | 0.0466 (15) | 0.0592 (16) | 0.0609 (16) | 0.0010 (13) | 0.0247 (13) | 0.0083 (14) |
C57 | 0.056 (2) | 0.056 (2) | 0.058 (2) | 0.0017 (19) | 0.022 (2) | −0.003 (2) |
C58 | 0.055 (3) | 0.056 (2) | 0.049 (2) | −0.001 (2) | 0.021 (2) | −0.0060 (19) |
C59 | 0.058 (3) | 0.078 (3) | 0.053 (2) | 0.002 (2) | 0.019 (2) | 0.001 (2) |
N1—C11 | 1.350 (4) | C34—Cl34 | 1.741 (4) |
N1—N2 | 1.389 (4) | C35—C36 | 1.372 (5) |
N1—C5 | 1.481 (4) | C35—H35 | 0.9300 |
N2—C3 | 1.290 (4) | C36—H36 | 0.9300 |
C3—C31 | 1.456 (5) | C51—C52 | 1.382 (5) |
C3—C4 | 1.502 (5) | C51—C56 | 1.385 (4) |
C4—C5 | 1.539 (5) | C52—C53 | 1.380 (5) |
C4—H4A | 0.9700 | C52—H52 | 0.9300 |
C4—H4 | 0.9700 | C53—C54 | 1.380 (4) |
C5—C51 | 1.507 (5) | C53—H53 | 0.9300 |
C5—H5 | 0.9800 | C54—C55 | 1.373 (5) |
C11—N11 | 1.323 (4) | C54—O54 | 1.375 (4) |
C11—S11 | 1.677 (3) | C55—C56 | 1.373 (5) |
N11—H11B | 0.87 (4) | C55—H55 | 0.9300 |
N11—H11A | 0.80 (4) | C56—H56 | 0.9300 |
C31—C32 | 1.385 (5) | O54—C57 | 1.423 (4) |
C31—C36 | 1.387 (5) | C57—C58 | 1.450 (5) |
C32—C33 | 1.376 (6) | C57—H57A | 0.9700 |
C32—H32 | 0.9300 | C57—H57B | 0.9700 |
C33—C34 | 1.364 (6) | C58—C59 | 1.164 (5) |
C33—H33 | 0.9300 | C59—H59 | 0.9300 |
C34—C35 | 1.380 (5) | ||
C11—N1—N2 | 119.7 (3) | C33—C34—Cl34 | 119.5 (3) |
C11—N1—C5 | 128.1 (3) | C35—C34—Cl34 | 119.6 (3) |
N2—N1—C5 | 112.1 (2) | C36—C35—C34 | 119.1 (4) |
C3—N2—N1 | 108.1 (3) | C36—C35—H35 | 120.4 |
N2—C3—C31 | 120.3 (3) | C34—C35—H35 | 120.4 |
N2—C3—C4 | 113.1 (3) | C35—C36—C31 | 121.0 (3) |
C31—C3—C4 | 126.5 (3) | C35—C36—H36 | 119.5 |
C3—C4—C5 | 102.2 (3) | C31—C36—H36 | 119.5 |
C3—C4—H4A | 111.3 | C52—C51—C56 | 117.8 (3) |
C5—C4—H4A | 111.3 | C52—C51—C5 | 120.8 (3) |
C3—C4—H4 | 111.3 | C56—C51—C5 | 121.3 (3) |
C5—C4—H4 | 111.3 | C53—C52—C51 | 122.1 (3) |
H4A—C4—H4 | 109.2 | C53—C52—H52 | 119.0 |
N1—C5—C51 | 112.2 (3) | C51—C52—H52 | 119.0 |
N1—C5—C4 | 100.0 (3) | C54—C53—C52 | 118.9 (3) |
C51—C5—C4 | 112.1 (3) | C54—C53—H53 | 120.6 |
N1—C5—H5 | 110.7 | C52—C53—H53 | 120.6 |
C51—C5—H5 | 110.7 | C55—C54—O54 | 115.9 (3) |
C4—C5—H5 | 110.7 | C55—C54—C53 | 119.9 (3) |
N11—C11—N1 | 115.8 (3) | O54—C54—C53 | 124.2 (3) |
N11—C11—S11 | 122.9 (3) | C54—C55—C56 | 120.7 (3) |
N1—C11—S11 | 121.3 (2) | C54—C55—H55 | 119.7 |
C11—N11—H11B | 117 (3) | C56—C55—H55 | 119.7 |
C11—N11—H11A | 118 (3) | C55—C56—C51 | 120.7 (3) |
H11B—N11—H11A | 124 (4) | C55—C56—H56 | 119.7 |
C32—C31—C36 | 118.4 (3) | C51—C56—H56 | 119.7 |
C32—C31—C3 | 120.6 (3) | C54—O54—C57 | 116.2 (3) |
C36—C31—C3 | 121.0 (3) | O54—C57—C58 | 109.2 (3) |
C33—C32—C31 | 120.8 (4) | O54—C57—H57A | 109.8 |
C33—C32—H32 | 119.6 | C58—C57—H57A | 109.8 |
C31—C32—H32 | 119.6 | O54—C57—H57B | 109.8 |
C34—C33—C32 | 119.6 (4) | C58—C57—H57B | 109.8 |
C34—C33—H33 | 120.2 | H57A—C57—H57B | 108.3 |
C32—C33—H33 | 120.2 | C59—C58—C57 | 176.5 (4) |
C33—C34—C35 | 121.0 (4) | C58—C59—H59 | 180.0 |
C11—N1—N2—C3 | 172.1 (3) | C32—C33—C34—Cl34 | 178.7 (3) |
C5—N1—N2—C3 | −11.1 (4) | C33—C34—C35—C36 | 2.3 (5) |
N1—N2—C3—C31 | 179.3 (3) | Cl34—C34—C35—C36 | −178.3 (3) |
N1—N2—C3—C4 | −3.4 (4) | C34—C35—C36—C31 | −0.2 (5) |
N2—C3—C4—C5 | 15.3 (4) | C32—C31—C36—C35 | −2.1 (5) |
C31—C3—C4—C5 | −167.6 (3) | C3—C31—C36—C35 | 176.1 (3) |
C11—N1—C5—C51 | 77.1 (4) | N1—C5—C51—C52 | 32.9 (4) |
N2—N1—C5—C51 | −99.5 (3) | C4—C5—C51—C52 | −78.7 (4) |
C11—N1—C5—C4 | −164.0 (3) | N1—C5—C51—C56 | −151.4 (3) |
N2—N1—C5—C4 | 19.5 (3) | C4—C5—C51—C56 | 97.0 (4) |
C3—C4—C5—N1 | −19.2 (3) | C56—C51—C52—C53 | 1.4 (5) |
C3—C4—C5—C51 | 99.8 (3) | C5—C51—C52—C53 | 177.3 (3) |
N2—N1—C11—N11 | 1.3 (5) | C51—C52—C53—C54 | 0.3 (5) |
C5—N1—C11—N11 | −175.0 (3) | C52—C53—C54—C55 | −2.1 (5) |
N2—N1—C11—S11 | −178.0 (2) | C52—C53—C54—O54 | 176.5 (3) |
C5—N1—C11—S11 | 5.6 (5) | O54—C54—C55—C56 | −176.7 (3) |
N2—C3—C31—C32 | 158.8 (3) | C53—C54—C55—C56 | 2.1 (5) |
C4—C3—C31—C32 | −18.1 (5) | C54—C55—C56—C51 | −0.3 (5) |
N2—C3—C31—C36 | −19.3 (5) | C52—C51—C56—C55 | −1.5 (5) |
C4—C3—C31—C36 | 163.8 (3) | C5—C51—C56—C55 | −177.3 (3) |
C36—C31—C32—C33 | 2.5 (6) | C55—C54—O54—C57 | 170.8 (3) |
C3—C31—C32—C33 | −175.7 (4) | C53—C54—O54—C57 | −7.9 (5) |
C31—C32—C33—C34 | −0.5 (6) | C54—O54—C57—C58 | −173.3 (3) |
C32—C33—C34—C35 | −1.9 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11A···N2 | 0.80 (4) | 2.23 (4) | 2.614 (5) | 110 (4) |
N11—H11B···S11i | 0.88 (4) | 2.63 (4) | 3.483 (4) | 164 (4) |
C52—H52···S11ii | 0.93 | 2.85 | 3.641 (4) | 144 |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x, y−1, z. |
C19H16BrN3OS | F(000) = 840 |
Mr = 414.31 | Dx = 1.529 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 15.1255 (13) Å | Cell parameters from 3513 reflections |
b = 6.0426 (5) Å | θ = 2.9–26.0° |
c = 21.026 (2) Å | µ = 2.41 mm−1 |
β = 110.555 (3)° | T = 296 K |
V = 1799.4 (3) Å3 | Needle, colourless |
Z = 4 | 0.20 × 0.15 × 0.10 mm |
Bruker APEXII diffractometer | 3365 independent reflections |
Radiation source: fine focussealed tube | 2559 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.053 |
φ and ω scans | θmax = 25.5°, θmin = 2.9° |
Absorption correction: multi-scan (SADABS; Bruker, 2012) | h = −18→18 |
Tmin = 0.584, Tmax = 0.786 | k = −7→7 |
18295 measured reflections | l = −25→25 |
Refinement on F2 | Primary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.055 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.113 | w = 1/[σ2(Fo2) + (0.026P)2 + 3.0352P] where P = (Fo2 + 2Fc2)/3 |
S = 1.16 | (Δ/σ)max < 0.001 |
3365 reflections | Δρmax = 0.50 e Å−3 |
232 parameters | Δρmin = −0.46 e Å−3 |
0 restraints |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
N1 | 0.5170 (2) | 0.7430 (5) | 0.34130 (16) | 0.0407 (8) | |
N2 | 0.4573 (2) | 0.5650 (5) | 0.31602 (17) | 0.0402 (8) | |
C3 | 0.4559 (3) | 0.5230 (7) | 0.2555 (2) | 0.0398 (9) | |
C4 | 0.5136 (3) | 0.6835 (7) | 0.2315 (2) | 0.0451 (10) | |
H4A | 0.4737 | 0.7891 | 0.1994 | 0.054* | |
H4 | 0.5531 | 0.6073 | 0.2108 | 0.054* | |
C5 | 0.5736 (3) | 0.7972 (7) | 0.2985 (2) | 0.0406 (9) | |
H5 | 0.5759 | 0.9575 | 0.2922 | 0.049* | |
C11 | 0.5228 (3) | 0.8343 (6) | 0.4015 (2) | 0.0387 (9) | |
S11 | 0.59333 (9) | 1.05265 (18) | 0.43388 (6) | 0.0490 (3) | |
N11 | 0.4689 (3) | 0.7426 (8) | 0.4319 (2) | 0.0596 (12) | |
H11B | 0.467 (4) | 0.803 (8) | 0.467 (3) | 0.071* | |
H11A | 0.438 (4) | 0.632 (9) | 0.415 (3) | 0.071* | |
C31 | 0.3993 (3) | 0.3401 (7) | 0.2168 (2) | 0.0408 (10) | |
C32 | 0.3746 (4) | 0.3310 (8) | 0.1462 (2) | 0.0583 (13) | |
H32 | 0.3983 | 0.4365 | 0.1243 | 0.070* | |
C33 | 0.3154 (4) | 0.1675 (9) | 0.1088 (2) | 0.0634 (14) | |
H33 | 0.2992 | 0.1628 | 0.0619 | 0.076* | |
C34 | 0.2812 (3) | 0.0132 (8) | 0.1412 (2) | 0.0481 (11) | |
Br34 | 0.19753 (4) | −0.20866 (10) | 0.08901 (3) | 0.0711 (2) | |
C35 | 0.3073 (3) | 0.0108 (8) | 0.2113 (2) | 0.0522 (11) | |
H35 | 0.2854 | −0.0992 | 0.2330 | 0.063* | |
C36 | 0.3664 (3) | 0.1757 (7) | 0.2483 (2) | 0.0469 (11) | |
H36 | 0.3845 | 0.1758 | 0.2953 | 0.056* | |
C51 | 0.6719 (3) | 0.7015 (7) | 0.3267 (2) | 0.0392 (9) | |
C52 | 0.6889 (3) | 0.5033 (7) | 0.3620 (2) | 0.0469 (11) | |
H52 | 0.6393 | 0.4331 | 0.3703 | 0.056* | |
C53 | 0.7771 (3) | 0.4068 (7) | 0.3853 (2) | 0.0478 (11) | |
H53 | 0.7865 | 0.2730 | 0.4086 | 0.057* | |
C54 | 0.8517 (3) | 0.5110 (7) | 0.3737 (2) | 0.0414 (10) | |
C55 | 0.8359 (3) | 0.7055 (7) | 0.3372 (2) | 0.0443 (10) | |
H55 | 0.8855 | 0.7741 | 0.3284 | 0.053* | |
C56 | 0.7474 (3) | 0.7991 (7) | 0.3137 (2) | 0.0425 (10) | |
H56 | 0.7378 | 0.9296 | 0.2887 | 0.051* | |
O54 | 0.9434 (2) | 0.4368 (5) | 0.39764 (15) | 0.0508 (8) | |
C57 | 0.9628 (3) | 0.2555 (7) | 0.4439 (2) | 0.0517 (11) | |
H57A | 0.9304 | 0.1240 | 0.4207 | 0.062* | |
H57B | 0.9402 | 0.2887 | 0.4807 | 0.062* | |
C58 | 1.0635 (3) | 0.2166 (8) | 0.4707 (2) | 0.0501 (11) | |
C59 | 1.1443 (4) | 0.1780 (8) | 0.4958 (2) | 0.0589 (13) | |
H59 | 1.2084 | 0.1474 | 0.5157 | 0.071* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0450 (19) | 0.045 (2) | 0.0376 (19) | −0.0074 (16) | 0.0215 (16) | −0.0019 (16) |
N2 | 0.0406 (19) | 0.0416 (19) | 0.039 (2) | −0.0028 (16) | 0.0142 (16) | −0.0026 (16) |
C3 | 0.039 (2) | 0.044 (2) | 0.035 (2) | 0.0038 (19) | 0.0108 (19) | 0.0046 (19) |
C4 | 0.049 (2) | 0.052 (3) | 0.037 (2) | 0.004 (2) | 0.019 (2) | 0.007 (2) |
C5 | 0.047 (2) | 0.039 (2) | 0.042 (2) | −0.005 (2) | 0.024 (2) | 0.0069 (19) |
C11 | 0.040 (2) | 0.037 (2) | 0.040 (2) | −0.0015 (18) | 0.0150 (19) | 0.0032 (18) |
S11 | 0.0598 (7) | 0.0428 (6) | 0.0489 (7) | −0.0136 (5) | 0.0247 (6) | −0.0035 (5) |
N11 | 0.071 (3) | 0.068 (3) | 0.053 (3) | −0.033 (2) | 0.038 (2) | −0.019 (2) |
C31 | 0.037 (2) | 0.046 (2) | 0.038 (2) | 0.0051 (19) | 0.0122 (19) | −0.0017 (19) |
C32 | 0.067 (3) | 0.067 (3) | 0.040 (3) | −0.008 (3) | 0.018 (2) | 0.002 (2) |
C33 | 0.068 (3) | 0.078 (4) | 0.038 (3) | 0.000 (3) | 0.011 (3) | −0.007 (3) |
C34 | 0.036 (2) | 0.051 (3) | 0.054 (3) | 0.000 (2) | 0.012 (2) | −0.017 (2) |
Br34 | 0.0495 (3) | 0.0782 (4) | 0.0824 (4) | −0.0050 (3) | 0.0191 (3) | −0.0385 (3) |
C35 | 0.052 (3) | 0.050 (3) | 0.059 (3) | −0.003 (2) | 0.024 (2) | −0.006 (2) |
C36 | 0.047 (2) | 0.052 (3) | 0.043 (3) | 0.001 (2) | 0.017 (2) | −0.002 (2) |
C51 | 0.047 (2) | 0.037 (2) | 0.038 (2) | −0.0083 (19) | 0.019 (2) | −0.0013 (18) |
C52 | 0.046 (3) | 0.044 (2) | 0.058 (3) | −0.008 (2) | 0.027 (2) | 0.010 (2) |
C53 | 0.053 (3) | 0.039 (2) | 0.055 (3) | −0.002 (2) | 0.022 (2) | 0.010 (2) |
C54 | 0.045 (2) | 0.045 (2) | 0.038 (2) | −0.006 (2) | 0.019 (2) | −0.0059 (19) |
C55 | 0.046 (2) | 0.051 (3) | 0.042 (2) | −0.011 (2) | 0.023 (2) | 0.000 (2) |
C56 | 0.054 (3) | 0.041 (2) | 0.036 (2) | −0.010 (2) | 0.021 (2) | 0.0056 (19) |
O54 | 0.0446 (17) | 0.061 (2) | 0.0516 (18) | 0.0007 (15) | 0.0223 (15) | 0.0057 (15) |
C57 | 0.053 (3) | 0.049 (3) | 0.055 (3) | −0.002 (2) | 0.021 (2) | −0.003 (2) |
C58 | 0.057 (3) | 0.055 (3) | 0.042 (3) | −0.002 (2) | 0.021 (2) | −0.009 (2) |
C59 | 0.055 (3) | 0.072 (3) | 0.052 (3) | 0.005 (3) | 0.023 (3) | 0.003 (3) |
N1—C11 | 1.354 (5) | C34—Br34 | 1.904 (4) |
N1—N2 | 1.385 (4) | C35—C36 | 1.381 (6) |
N1—C5 | 1.480 (5) | C35—H35 | 0.9300 |
N2—C3 | 1.292 (5) | C36—H36 | 0.9300 |
C3—C31 | 1.458 (6) | C51—C52 | 1.385 (6) |
C3—C4 | 1.505 (5) | C51—C56 | 1.396 (5) |
C4—C5 | 1.542 (6) | C52—C53 | 1.378 (6) |
C4—H4A | 0.9700 | C52—H52 | 0.9300 |
C4—H4 | 0.9700 | C53—C54 | 1.387 (6) |
C5—C51 | 1.509 (6) | C53—H53 | 0.9300 |
C5—H5 | 0.9800 | C54—O54 | 1.374 (5) |
C11—N11 | 1.323 (5) | C54—C55 | 1.378 (6) |
C11—S11 | 1.683 (4) | C55—C56 | 1.375 (6) |
N11—H11B | 0.83 (5) | C55—H55 | 0.9300 |
N11—H11A | 0.82 (5) | C56—H56 | 0.9300 |
C31—C36 | 1.380 (6) | O54—C57 | 1.425 (5) |
C31—C32 | 1.398 (6) | C57—C58 | 1.446 (6) |
C32—C33 | 1.379 (7) | C57—H57A | 0.9700 |
C32—H32 | 0.9300 | C57—H57B | 0.9700 |
C33—C34 | 1.360 (6) | C58—C59 | 1.172 (6) |
C33—H33 | 0.9300 | C59—H59 | 0.9300 |
C34—C35 | 1.387 (6) | ||
C11—N1—N2 | 119.6 (3) | C33—C34—Br34 | 119.2 (4) |
C11—N1—C5 | 128.0 (3) | C35—C34—Br34 | 119.3 (4) |
N2—N1—C5 | 112.1 (3) | C36—C35—C34 | 118.5 (4) |
C3—N2—N1 | 108.2 (3) | C36—C35—H35 | 120.8 |
N2—C3—C31 | 120.1 (4) | C34—C35—H35 | 120.8 |
N2—C3—C4 | 113.1 (4) | C31—C36—C35 | 121.4 (4) |
C31—C3—C4 | 126.7 (4) | C31—C36—H36 | 119.3 |
C3—C4—C5 | 101.9 (3) | C35—C36—H36 | 119.3 |
C3—C4—H4A | 111.4 | C52—C51—C56 | 117.3 (4) |
C5—C4—H4A | 111.4 | C52—C51—C5 | 121.0 (3) |
C3—C4—H4 | 111.4 | C56—C51—C5 | 121.5 (4) |
C5—C4—H4 | 111.4 | C53—C52—C51 | 122.0 (4) |
H4A—C4—H4 | 109.3 | C53—C52—H52 | 119.0 |
N1—C5—C51 | 112.1 (3) | C51—C52—H52 | 119.0 |
N1—C5—C4 | 100.2 (3) | C52—C53—C54 | 119.5 (4) |
C51—C5—C4 | 111.7 (3) | C52—C53—H53 | 120.3 |
N1—C5—H5 | 110.8 | C54—C53—H53 | 120.3 |
C51—C5—H5 | 110.8 | O54—C54—C55 | 116.0 (3) |
C4—C5—H5 | 110.8 | O54—C54—C53 | 124.5 (4) |
N11—C11—N1 | 115.6 (4) | C55—C54—C53 | 119.5 (4) |
N11—C11—S11 | 122.9 (3) | C56—C55—C54 | 120.5 (4) |
N1—C11—S11 | 121.5 (3) | C56—C55—H55 | 119.7 |
C11—N11—H11B | 117 (4) | C54—C55—H55 | 119.7 |
C11—N11—H11A | 119 (4) | C55—C56—C51 | 121.1 (4) |
H11B—N11—H11A | 124 (5) | C55—C56—H56 | 119.5 |
C36—C31—C32 | 118.2 (4) | C51—C56—H56 | 119.5 |
C36—C31—C3 | 121.2 (4) | C54—O54—C57 | 116.1 (3) |
C32—C31—C3 | 120.5 (4) | O54—C57—C58 | 109.1 (4) |
C33—C32—C31 | 120.9 (5) | O54—C57—H57A | 109.9 |
C33—C32—H32 | 119.6 | C58—C57—H57A | 109.9 |
C31—C32—H32 | 119.6 | O54—C57—H57B | 109.9 |
C34—C33—C32 | 119.4 (4) | C58—C57—H57B | 109.9 |
C34—C33—H33 | 120.3 | H57A—C57—H57B | 108.3 |
C32—C33—H33 | 120.3 | C59—C58—C57 | 175.8 (5) |
C33—C34—C35 | 121.5 (4) | C58—C59—H59 | 180.0 |
C11—N1—N2—C3 | 173.1 (4) | C32—C33—C34—Br34 | 178.7 (4) |
C5—N1—N2—C3 | −11.5 (4) | C33—C34—C35—C36 | 2.7 (7) |
N1—N2—C3—C31 | 179.2 (3) | Br34—C34—C35—C36 | −178.7 (3) |
N1—N2—C3—C4 | −3.1 (5) | C32—C31—C36—C35 | −2.7 (6) |
N2—C3—C4—C5 | 15.1 (5) | C3—C31—C36—C35 | 175.3 (4) |
C31—C3—C4—C5 | −167.3 (4) | C34—C35—C36—C31 | 0.1 (6) |
C11—N1—C5—C51 | 76.1 (5) | N1—C5—C51—C52 | 32.2 (5) |
N2—N1—C5—C51 | −98.8 (4) | C4—C5—C51—C52 | −79.4 (5) |
C11—N1—C5—C4 | −165.2 (4) | N1—C5—C51—C56 | −153.0 (4) |
N2—N1—C5—C4 | 19.8 (4) | C4—C5—C51—C56 | 95.5 (4) |
C3—C4—C5—N1 | −19.2 (4) | C56—C51—C52—C53 | 1.6 (6) |
C3—C4—C5—C51 | 99.6 (4) | C5—C51—C52—C53 | 176.6 (4) |
N2—N1—C11—N11 | −0.1 (6) | C51—C52—C53—C54 | 0.5 (7) |
C5—N1—C11—N11 | −174.8 (4) | C52—C53—C54—O54 | 176.2 (4) |
N2—N1—C11—S11 | −179.2 (3) | C52—C53—C54—C55 | −2.1 (6) |
C5—N1—C11—S11 | 6.1 (6) | O54—C54—C55—C56 | −177.0 (4) |
N2—C3—C31—C36 | −17.0 (6) | C53—C54—C55—C56 | 1.5 (6) |
C4—C3—C31—C36 | 165.6 (4) | C54—C55—C56—C51 | 0.7 (6) |
N2—C3—C31—C32 | 161.0 (4) | C52—C51—C56—C55 | −2.2 (6) |
C4—C3—C31—C32 | −16.4 (6) | C5—C51—C56—C55 | −177.2 (4) |
C36—C31—C32—C33 | 2.8 (7) | C55—C54—O54—C57 | 170.7 (4) |
C3—C31—C32—C33 | −175.3 (4) | C53—C54—O54—C57 | −7.6 (6) |
C31—C32—C33—C34 | −0.2 (8) | C54—O54—C57—C58 | −172.7 (3) |
C32—C33—C34—C35 | −2.6 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11A···N2 | 0.82 (5) | 2.24 (6) | 2.611 (5) | 108 (5) |
N11—H11A···Br34i | 0.82 (5) | 2.89 (6) | 3.632 (5) | 152 (5) |
N11—H11B···S11ii | 0.83 (6) | 2.70 (6) | 3.500 (5) | 162 (6) |
C52—H52···S11iii | 0.93 | 2.87 | 3.650 (5) | 143 |
Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) −x+1, −y+2, −z+1; (iii) x, y−1, z. |
C20H19N3O2S | F(000) = 768 |
Mr = 365.44 | Dx = 1.330 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 11.7852 (15) Å | Cell parameters from 3824 reflections |
b = 7.5345 (11) Å | θ = 1.7–26.6° |
c = 20.599 (3) Å | µ = 0.20 mm−1 |
β = 93.555 (4)° | T = 296 K |
V = 1825.6 (4) Å3 | Block, colourless |
Z = 4 | 0.20 × 0.20 × 0.15 mm |
Bruker APEXII diffractometer | 3822 independent reflections |
Radiation source: fine focussealed tube | 1864 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.100 |
φ and ω scans | θmax = 26.6°, θmin = 2.6° |
Absorption correction: multi-scan (SADABS; Bruker, 2012) | h = −14→14 |
Tmin = 0.908, Tmax = 0.971 | k = −9→9 |
20467 measured reflections | l = −23→25 |
Refinement on F2 | Primary atom site location: difference Fourier map |
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) = 0.118 | w = 1/[σ2(Fo2) + (0.0424P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.97 | (Δ/σ)max < 0.001 |
3822 reflections | Δρmax = 0.21 e Å−3 |
242 parameters | Δρmin = −0.24 e Å−3 |
0 restraints |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
N1 | 0.32812 (16) | 0.5906 (3) | 0.30356 (11) | 0.0359 (6) | |
N2 | 0.39265 (16) | 0.4472 (3) | 0.32813 (11) | 0.0359 (6) | |
C3 | 0.3292 (2) | 0.3478 (3) | 0.36206 (13) | 0.0358 (7) | |
C4 | 0.2109 (2) | 0.4218 (4) | 0.36538 (14) | 0.0431 (8) | |
H4A | 0.2006 | 0.4759 | 0.4073 | 0.052* | |
H4B | 0.1538 | 0.3303 | 0.3573 | 0.052* | |
C5 | 0.20546 (19) | 0.5611 (3) | 0.31084 (15) | 0.0396 (7) | |
H5 | 0.1699 | 0.6702 | 0.3257 | 0.047* | |
C11 | 0.3763 (2) | 0.7190 (3) | 0.26933 (13) | 0.0341 (7) | |
S11 | 0.29954 (5) | 0.88567 (9) | 0.23445 (4) | 0.0462 (3) | |
N11 | 0.48918 (18) | 0.7072 (3) | 0.26592 (12) | 0.0398 (7) | |
H11A | 0.529 (2) | 0.614 (3) | 0.2788 (13) | 0.048* | |
H11B | 0.520 (2) | 0.781 (3) | 0.2386 (13) | 0.048* | |
C31 | 0.3722 (2) | 0.1830 (3) | 0.39094 (13) | 0.0375 (7) | |
C32 | 0.3004 (2) | 0.0594 (4) | 0.41761 (14) | 0.0452 (8) | |
H32 | 0.2243 | 0.0881 | 0.4213 | 0.054* | |
C33 | 0.3393 (2) | −0.1033 (4) | 0.43855 (14) | 0.0499 (8) | |
H33 | 0.2898 | −0.1834 | 0.4563 | 0.060* | |
C34 | 0.4514 (3) | −0.1485 (4) | 0.43337 (14) | 0.0456 (8) | |
C35 | 0.5260 (2) | −0.0259 (4) | 0.40995 (14) | 0.0444 (8) | |
H35 | 0.6026 | −0.0541 | 0.4083 | 0.053* | |
C36 | 0.4869 (2) | 0.1379 (3) | 0.38909 (14) | 0.0414 (7) | |
H36 | 0.5376 | 0.2198 | 0.3735 | 0.050* | |
O34 | 0.48126 (17) | −0.3164 (3) | 0.45311 (10) | 0.0614 (6) | |
C37 | 0.5942 (3) | −0.3754 (4) | 0.44406 (16) | 0.0660 (10) | |
H37A | 0.6085 | −0.3691 | 0.3987 | 0.099* | |
H37B | 0.6028 | −0.4958 | 0.4588 | 0.099* | |
H37C | 0.6474 | −0.3010 | 0.4685 | 0.099* | |
C51 | 0.1451 (2) | 0.4974 (3) | 0.24816 (14) | 0.0350 (7) | |
C52 | 0.1993 (2) | 0.4027 (4) | 0.20147 (15) | 0.0476 (8) | |
H52 | 0.2764 | 0.3777 | 0.2083 | 0.057* | |
C53 | 0.1417 (2) | 0.3442 (4) | 0.14482 (15) | 0.0493 (8) | |
H53 | 0.1798 | 0.2815 | 0.1140 | 0.059* | |
C54 | 0.0272 (2) | 0.3798 (3) | 0.13462 (15) | 0.0394 (7) | |
C55 | −0.0289 (2) | 0.4687 (3) | 0.18155 (15) | 0.0408 (8) | |
H55 | −0.1065 | 0.4899 | 0.1754 | 0.049* | |
C56 | 0.0297 (2) | 0.5260 (3) | 0.23739 (15) | 0.0406 (8) | |
H56 | −0.0094 | 0.5855 | 0.2687 | 0.049* | |
O54 | −0.03798 (14) | 0.3313 (3) | 0.07948 (10) | 0.0550 (6) | |
C57 | 0.0190 (3) | 0.2607 (4) | 0.02690 (16) | 0.0612 (9) | |
H57A | 0.0538 | 0.1482 | 0.0395 | 0.073* | |
H57B | 0.0787 | 0.3414 | 0.0154 | 0.073* | |
C58 | −0.0612 (3) | 0.2348 (4) | −0.02888 (19) | 0.0612 (10) | |
C59 | −0.1219 (3) | 0.2176 (5) | −0.0749 (2) | 0.0854 (12) | |
H59 | −0.1707 | 0.2038 | −0.1119 | 0.102* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0287 (12) | 0.0365 (13) | 0.0423 (17) | −0.0015 (10) | 0.0015 (11) | 0.0019 (12) |
N2 | 0.0345 (12) | 0.0368 (13) | 0.0361 (16) | −0.0009 (11) | −0.0003 (11) | 0.0000 (11) |
C3 | 0.0376 (15) | 0.0399 (17) | 0.0298 (19) | −0.0063 (13) | 0.0020 (13) | −0.0049 (14) |
C4 | 0.0382 (16) | 0.0501 (18) | 0.042 (2) | −0.0060 (13) | 0.0076 (14) | −0.0019 (16) |
C5 | 0.0267 (14) | 0.0425 (17) | 0.050 (2) | −0.0007 (13) | 0.0072 (14) | −0.0051 (16) |
C11 | 0.0336 (15) | 0.0344 (15) | 0.0344 (19) | −0.0045 (13) | 0.0017 (13) | −0.0058 (14) |
S11 | 0.0388 (4) | 0.0429 (4) | 0.0565 (6) | 0.0027 (3) | 0.0007 (4) | 0.0048 (4) |
N11 | 0.0334 (14) | 0.0378 (15) | 0.0482 (19) | 0.0000 (11) | 0.0028 (12) | 0.0077 (13) |
C31 | 0.0434 (16) | 0.0404 (17) | 0.0287 (19) | −0.0072 (14) | 0.0021 (13) | 0.0002 (14) |
C32 | 0.0457 (16) | 0.056 (2) | 0.034 (2) | −0.0095 (15) | 0.0025 (15) | 0.0001 (16) |
C33 | 0.062 (2) | 0.0484 (19) | 0.039 (2) | −0.0154 (16) | 0.0031 (16) | 0.0061 (16) |
C34 | 0.061 (2) | 0.0429 (19) | 0.032 (2) | −0.0076 (16) | −0.0019 (15) | 0.0014 (15) |
C35 | 0.0454 (17) | 0.0462 (19) | 0.041 (2) | −0.0009 (15) | −0.0015 (15) | 0.0031 (16) |
C36 | 0.0452 (17) | 0.0422 (18) | 0.037 (2) | −0.0067 (14) | 0.0016 (14) | 0.0024 (15) |
O34 | 0.0796 (15) | 0.0455 (13) | 0.0592 (17) | −0.0021 (11) | 0.0061 (12) | 0.0134 (12) |
C37 | 0.087 (2) | 0.048 (2) | 0.063 (3) | 0.0078 (18) | 0.000 (2) | 0.0058 (18) |
C51 | 0.0295 (14) | 0.0343 (15) | 0.041 (2) | −0.0005 (12) | 0.0029 (14) | 0.0024 (14) |
C52 | 0.0303 (15) | 0.0586 (19) | 0.054 (2) | 0.0087 (14) | 0.0045 (15) | −0.0084 (18) |
C53 | 0.0416 (17) | 0.063 (2) | 0.044 (2) | 0.0055 (15) | 0.0041 (15) | −0.0163 (17) |
C54 | 0.0345 (16) | 0.0405 (17) | 0.043 (2) | −0.0038 (13) | −0.0021 (15) | 0.0003 (15) |
C55 | 0.0283 (14) | 0.0414 (17) | 0.052 (2) | 0.0005 (13) | 0.0005 (15) | −0.0002 (16) |
C56 | 0.0325 (15) | 0.0390 (16) | 0.051 (2) | 0.0005 (13) | 0.0083 (15) | −0.0066 (15) |
O54 | 0.0442 (12) | 0.0752 (15) | 0.0446 (16) | −0.0039 (10) | −0.0042 (11) | −0.0093 (12) |
C57 | 0.067 (2) | 0.063 (2) | 0.053 (3) | 0.0021 (18) | −0.0025 (19) | −0.0076 (19) |
C58 | 0.075 (2) | 0.054 (2) | 0.053 (3) | 0.0026 (18) | −0.009 (2) | −0.0034 (19) |
C59 | 0.111 (3) | 0.075 (3) | 0.066 (3) | 0.001 (2) | −0.029 (2) | −0.005 (2) |
N1—C11 | 1.343 (3) | C35—H35 | 0.9300 |
N1—N2 | 1.398 (3) | C36—H36 | 0.9300 |
N1—C5 | 1.479 (3) | O34—C37 | 1.426 (3) |
N2—C3 | 1.294 (3) | C37—H37A | 0.9600 |
C3—C31 | 1.455 (3) | C37—H37B | 0.9600 |
C3—C4 | 1.507 (3) | C37—H37C | 0.9600 |
C4—C5 | 1.536 (4) | C51—C56 | 1.381 (3) |
C4—H4A | 0.9700 | C51—C52 | 1.385 (3) |
C4—H4B | 0.9700 | C52—C53 | 1.385 (4) |
C5—C51 | 1.513 (4) | C52—H52 | 0.9300 |
C5—H5 | 0.9800 | C53—C54 | 1.379 (3) |
C11—N11 | 1.339 (3) | C53—H53 | 0.9300 |
C11—S11 | 1.683 (3) | C54—C55 | 1.378 (4) |
N11—H11A | 0.88 (2) | C54—O54 | 1.380 (3) |
N11—H11B | 0.89 (3) | C55—C56 | 1.374 (4) |
C31—C32 | 1.394 (3) | C55—H55 | 0.9300 |
C31—C36 | 1.396 (3) | C56—H56 | 0.9300 |
C32—C33 | 1.369 (4) | O54—C57 | 1.413 (3) |
C32—H32 | 0.9300 | C57—C58 | 1.455 (4) |
C33—C34 | 1.375 (4) | C57—H57A | 0.9700 |
C33—H33 | 0.9300 | C57—H57B | 0.9700 |
C34—O34 | 1.368 (3) | C58—C59 | 1.160 (4) |
C34—C35 | 1.383 (3) | C59—H59 | 0.9300 |
C35—C36 | 1.377 (3) | ||
C11—N1—N2 | 120.55 (19) | C34—C35—H35 | 120.0 |
C11—N1—C5 | 127.5 (2) | C35—C36—C31 | 121.0 (2) |
N2—N1—C5 | 111.11 (19) | C35—C36—H36 | 119.5 |
C3—N2—N1 | 108.86 (19) | C31—C36—H36 | 119.5 |
N2—C3—C31 | 121.1 (2) | C34—O34—C37 | 118.3 (2) |
N2—C3—C4 | 112.2 (2) | O34—C37—H37A | 109.5 |
C31—C3—C4 | 126.7 (2) | O34—C37—H37B | 109.5 |
C3—C4—C5 | 102.5 (2) | H37A—C37—H37B | 109.5 |
C3—C4—H4A | 111.3 | O34—C37—H37C | 109.5 |
C5—C4—H4A | 111.3 | H37A—C37—H37C | 109.5 |
C3—C4—H4B | 111.3 | H37B—C37—H37C | 109.5 |
C5—C4—H4B | 111.3 | C56—C51—C52 | 117.4 (3) |
H4A—C4—H4B | 109.2 | C56—C51—C5 | 119.6 (2) |
N1—C5—C51 | 111.8 (2) | C52—C51—C5 | 122.9 (2) |
N1—C5—C4 | 100.4 (2) | C51—C52—C53 | 121.7 (2) |
C51—C5—C4 | 113.8 (2) | C51—C52—H52 | 119.1 |
N1—C5—H5 | 110.2 | C53—C52—H52 | 119.1 |
C51—C5—H5 | 110.2 | C54—C53—C52 | 119.3 (3) |
C4—C5—H5 | 110.2 | C54—C53—H53 | 120.3 |
N11—C11—N1 | 115.7 (2) | C52—C53—H53 | 120.3 |
N11—C11—S11 | 122.4 (2) | C55—C54—C53 | 119.6 (3) |
N1—C11—S11 | 121.85 (18) | C55—C54—O54 | 116.1 (2) |
C11—N11—H11A | 123.2 (16) | C53—C54—O54 | 124.3 (3) |
C11—N11—H11B | 116.0 (16) | C56—C55—C54 | 120.2 (2) |
H11A—N11—H11B | 118 (2) | C56—C55—H55 | 119.9 |
C32—C31—C36 | 117.4 (3) | C54—C55—H55 | 119.9 |
C32—C31—C3 | 121.7 (2) | C55—C56—C51 | 121.6 (3) |
C36—C31—C3 | 120.7 (2) | C55—C56—H56 | 119.2 |
C33—C32—C31 | 121.5 (3) | C51—C56—H56 | 119.2 |
C33—C32—H32 | 119.3 | C54—O54—C57 | 117.6 (2) |
C31—C32—H32 | 119.3 | O54—C57—C58 | 109.9 (3) |
C32—C33—C34 | 120.1 (3) | O54—C57—H57A | 109.7 |
C32—C33—H33 | 119.9 | C58—C57—H57A | 109.7 |
C34—C33—H33 | 119.9 | O54—C57—H57B | 109.7 |
O34—C34—C33 | 115.9 (3) | C58—C57—H57B | 109.7 |
O34—C34—C35 | 124.3 (3) | H57A—C57—H57B | 108.2 |
C33—C34—C35 | 119.8 (3) | C59—C58—C57 | 177.2 (4) |
C36—C35—C34 | 120.0 (3) | C58—C59—H59 | 180.0 |
C36—C35—H35 | 120.0 | ||
C11—N1—N2—C3 | 176.5 (2) | O34—C34—C35—C36 | 177.7 (3) |
C5—N1—N2—C3 | −13.2 (3) | C33—C34—C35—C36 | −3.0 (4) |
N1—N2—C3—C31 | 176.8 (2) | C34—C35—C36—C31 | −0.2 (4) |
N1—N2—C3—C4 | −1.8 (3) | C32—C31—C36—C35 | 3.1 (4) |
N2—C3—C4—C5 | 15.0 (3) | C3—C31—C36—C35 | −172.9 (3) |
C31—C3—C4—C5 | −163.6 (3) | C33—C34—O34—C37 | 175.1 (3) |
C11—N1—C5—C51 | 69.8 (3) | C35—C34—O34—C37 | −5.5 (4) |
N2—N1—C5—C51 | −99.7 (2) | N1—C5—C51—C56 | −155.6 (2) |
C11—N1—C5—C4 | −169.2 (2) | C4—C5—C51—C56 | 91.5 (3) |
N2—N1—C5—C4 | 21.3 (3) | N1—C5—C51—C52 | 27.6 (4) |
C3—C4—C5—N1 | −20.3 (3) | C4—C5—C51—C52 | −85.3 (3) |
C3—C4—C5—C51 | 99.3 (2) | C56—C51—C52—C53 | 2.4 (4) |
N2—N1—C11—N11 | −5.7 (4) | C5—C51—C52—C53 | 179.2 (3) |
C5—N1—C11—N11 | −174.3 (2) | C51—C52—C53—C54 | −0.5 (5) |
N2—N1—C11—S11 | 175.50 (18) | C52—C53—C54—C55 | −1.7 (4) |
C5—N1—C11—S11 | 6.9 (4) | C52—C53—C54—O54 | 178.6 (3) |
N2—C3—C31—C32 | −168.5 (3) | C53—C54—C55—C56 | 1.9 (4) |
C4—C3—C31—C32 | 10.0 (4) | O54—C54—C55—C56 | −178.4 (2) |
N2—C3—C31—C36 | 7.4 (4) | C54—C55—C56—C51 | 0.2 (4) |
C4—C3—C31—C36 | −174.2 (3) | C52—C51—C56—C55 | −2.3 (4) |
C36—C31—C32—C33 | −2.9 (4) | C5—C51—C56—C55 | −179.2 (2) |
C3—C31—C32—C33 | 173.1 (3) | C55—C54—O54—C57 | 172.0 (2) |
C31—C32—C33—C34 | −0.2 (5) | C53—C54—O54—C57 | −8.3 (4) |
C32—C33—C34—O34 | −177.4 (3) | C54—O54—C57—C58 | −174.1 (2) |
C32—C33—C34—C35 | 3.2 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11A···N2 | 0.88 (2) | 2.32 (2) | 2.637 (3) | 101.2 (18) |
N11—H11A···S11i | 0.88 (2) | 2.68 (2) | 3.474 (2) | 151 (2) |
N11—H11B···N2ii | 0.89 (2) | 2.17 (2) | 3.049 (3) | 175 (2) |
C37—H37B···O34iii | 0.96 | 2.55 | 3.302 (4) | 135 |
C56—H56···Cg2iv | 0.93 | 2.93 | 3.717 (3) | 143 |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x+1, y+1/2, −z+1/2; (iii) −x+1, −y−1, −z+1; (iv) −x, y+1/2, −z+1/2. |
Cg1 and Cg2 represent the centroids of the rings (C31–C36) and (C51–C456), respectively |
Compound | D—H···A | D—H | H···A | D···A | D—H···A |
(I) | C13—H13···Cg1i | 0.93 | 2.90 | 3.554 (3) | 128 |
C35—H35···Cg1ii | 0.93 | 2.83 | 3.508 (3) | 131 | |
(II) | C13—H13···Cg1i | 0.93 | 2.95 | 3.602 (4) | 128 |
C35—H35···Cg1ii | 0.93 | 2.80 | 3.484 (3) | 131 | |
(IV) | N11—H11A···N2 | 0.80 (4) | 2.23 (4) | 2.614 (5) | 110 (4) |
N11—H11B···S11iii | 0.88 (4) | 2.63 (4) | 3.483 (4) | 164 (4) | |
C52—H52···S11iv | 0.93 | 2.85 | 3.641 (4) | 144 | |
(V) | N11—H11A···N2 | 0.82 (5) | 2.24 (6) | 2.611 (5) | 108 (5) |
N11—H11A···Br34v | 0.82 (5) | 2.89 (6) | 3.632 (5) | 152 (5) | |
N11—H11B···S11iii | 0.83 (6) | 2.70 (6) | 3.500 (5) | 162 (6) | |
C52—H52···S11iv | 0.93 | 2.87 | 3.650 (4) | 143 | |
(VI) | N11—H11A···N2 | 0.88 (2) | 2.32 (2) | 2.637 (3) | 101.2 (18) |
N11—H11A···S11vi | 0.88 (2) | 2.68 (2) | 3.474 (2) | 151 (2) | |
N11—H11B···N2vii | 0.89 (2) | 2.17 (2) | 3.049 (3) | 175 (2) | |
C37—H37B···O34viii | 0.96 | 2.55 | 3.302 (4) | 135 | |
C56—H56···Cg2ix | 0.93 | 2.93 | 3.717 (3) | 143 |
Symmetry codes: (i) 1 - x, 1 - y, 1 - z; (ii) x, 1/2 - y, 1/2 + z; (iii) 1 - x, 2 - y, 1 - z; (iv) x, -1 + y, z; (v) 1/2 - x, 1/2 + y, 1/2 - z; (vi) 1 - x, -1/2 + y, 1/2 - z; (vii) 1 - x, 1/2 + y, 1/2 - z; (viii) 1 - x, -1 - y, 1 - z; (ix) -x, 1/2 + y, 1/2 - z. |
Acknowledgements
MAES thanks the University of Mysore for research facilities.
Funding information
HSY thanks the University Grants Commission, New Delhi for the award of a BSR Faculty Fellowship for three years.
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