Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229614016301/cu3059sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229614016301/cu30593asup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229614016301/cu30593bsup3.hkl | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229614016301/cu30593asup4.cml | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229614016301/cu30593bsup5.cml |
CCDC references: 985799; 971919
The presence of a piperidine ring is a characteristic feature of antihistaminic agents, oral anaesthetics, narcotic analgesics, tranquilizers and hypotensive agents (Robinson, 1973). Many piperidine derivatives also form the skeleton of several alkaloids (Hootele et al., 1980). A large variety of 4-piperidones with different substituents in the 1-, 2-, 3-, 5- and 6-positions and further substitutions in the 2- and 6-substituent phenyl rings have been reported elsewhere (Jia et al., 1989a,b; Cheer et al., 1984; Sekar et al., 1990, 1993; Sukumar et al., 1994; Díaz et al., 1997). Derivatives of oxopiperidine carboxylic acid are an important class of compounds, which can be used as starting materials for several classes of synthetic drugs, such as enzyme inhibitors (Perumattam et al., 1991), immunosuppressors (Jones et al., 1989), antibiotics (Sehgal et al., 1983) and mycotoxic agents (Martens & Scheunemann, 1991).
Several 2,6-disubstituted piperidines have been found to be useful as tranquilisers (Bochringer & Soehne, 1961) and to possess hypotensive activity (Severs et al., 1965) and a combination of stimulant and depressant effects on the central nervous system (Ganellin & Spickett, 1965), as well as bactericidal, fungicidal and herbicidal activities (Mobio et al., 1990).
Nitrogen heterocycles, in particular piperidone alkaloids, occur in both plants and animals, and some of them possess a variety of biological activities, including cytotoxic and anticancer properties (Dimmock et al., 1990; Mutus et al., 1989). As part of our studies of substituent effects on these structures, we present here the results of X-ray crystallographic analysis of the title compounds, (3a) and (3b). Views of the independent molecules with the atom-numbering schemes are shown in Figs. 1 and 2.
Due to the problems evidently encountered during the synthetic procedure described in the patent for the preparation of substituted enantiopure N-arylmethyl-6-oxopiperidine-2-carboxylic acids (Beswick et al., 2008), we decided to resort to our original procedure, but using aminoadipic acid, (1), instead of glutamic acid.
As highlighted in Scheme 1, synthesis of (3a) began with reductive amination of benzaldehyde with (S)-2-aminoadipic acid, (1). Compound (1) was condensed with freshly distilled thiophene-2-carboxaldehyde to give the expected Schiff base, which upon treatment with NaBH4 for 2 h at 273 K and concentrated hydrochloric acid at same temperature [For how long?] gave (S)-2-[(thiophen-2-ylmethyl)amino]hexanedioic acid, (2a). Water treatment of the aminodicarboxylic acid at reflux for 4 h formed (S)-6-oxo-1-(thiophen-2-ylmethyl)piperidine-2-carboxylic acid, (3a), in 79% yield. This method starting directly from (1) appears to be generally applicable to substrates with a wide range of substituents. By using (1) and thiophene-3-carboxaldehyde under the same conditions we obtained the optically pure N-thienylmethyl derivative, (3b), in good yield (76%).
The structures of compounds (3a) and (3b) were established by spectroscopic methods, mainly by 1H and 13C NMR methods (HMBC, HSQC, COSY and TOCSY) and HRMS analysis.
Melting points were determined with aStuart SMP-30 melting-point apparatus. Analytical thin-layer chromatography (TLC) was performed on TLC silica gel 60 F254 glass plates (2.5 × 7.5 cm, Merck), followed by dipping of the plates into an aqueous solution of KMnO4, K2CO3 and NaOH (150:1.5:10:2.5) and charring with a heat gun. Optical rotations were measured with a P-2000 Polarimeter (PTC-203, Jasco), with a water-jacketed 10 cm cell at the wavelength of the sodium D line (λ = 589 nm). The optical purity of our synthetic compounds was assesed by NMR analysis of the diastereomeric salts, obtained by reaction of (3a) or (3b) with (R)-(+)-alpha-methylbenzylamine directly in the NMR tube. 1H and 13C NMR spectra were recorded with Inova 600 Varian spectrometers in CD3OD or DMSO-d6. Solvents and chemical shifts (δ) are quoted in p.p.m. and are referenced to trimethyl siloxane (TMS) as the internal standard. The HSQC and HMBC techniques were used throughout for the assignment of the 1H–13C relationships. The IR spectra were recorded using a Nicolet 5700 FT–IR spectrometer as KBr discs (denoted KBr) or as thin films on KBr plates (denoted film). High-resolution spectrometry was performed using a Waters UPLC system on a Micromass Q-Tof Micro MS system with ESI+ ionization (measured mass represents M+H+). The electronic structures of (3a) and (3b) were calculated by ab initio quantum chemistry at the DFT/B3LYP level, with a 6-311G basis set. The net charges on the individual atoms and the values of the Wiberg bond indices Iw (Frisch et al., 2004) are given in Tables 2 and 3.
For the preparation of (S)-6-oxo-1-(thiophen-2-ylmethyl)piperidine-2-carboxylic acid, (3a), (S)-2-aminoadipic acid, (1) (16.1 g, 0.1 mol), was added at room temperature to a freshly prepared solution of NaOH (2 M, 90 ml) in EtOH (20 ml). To this mixture a solution of freshly distilled thiophene-2-carboxaldehyde (12.3 g, 0.11 mol) in EtOH (20 ml) was added dropwise over 6 h and the reaction mixture was then stirred overnight. It was then cooled to 273 K and sodium borohydride (4.56 g, 0.12 mol) was added in small portions, and the resulting mixture was stirred for 3.5 h, allowing the temperature to rise to room temperature. The clear solution was extracted with ether (3 × 50 ml) and the aqueous layer was acidified to pH 3 at 273–278 K with HCl (1:1). The crystalline precipitate was collected, washed carefully with cooled water (10 ml) and dried to give a solid. A suspension of crude (S)-2-[(thiophen-2-ylmethyl)amino]hexanedioic acid, (2a) (22.7 g, 88.3 mmol), in water (250 ml) was heated at reflux for 4 h and then cooled to 273 K for 5 h. The precipitate which formed was collected and washed with cold water to give acid (2a) (18.9 g, 79%) as colourless crystals. Analysis: m.p. 451.65–452.95 K (H2O), [α]D22 = 108.6 (c 1.06, MeOH); 1H NMR (600 MHz, DMSO-d6, δ, p.p.m.): 13.02 (bs, 1H, COOH), 7.48 (dd, J = 5.0 and 3.0 Hz, 1H), 7.33–7.29 (m, 1H), 6.97 (dd, J = 4.9 and 1.3 Hz, 1H), 5.16 (d, J = 15.2 Hz, 1H), 3.99 (dd, J = 5.8 and 3.0 Hz, 1H), 3.69 (d, J = 15.2 Hz, 1H), 2.36–2.27 (m, 2H), 2.12 (dd, 1H, J = 13.8 and 3.4 Hz), 1.89 (tdd, 1H, J = 13.5, 5.9 and 3.6 Hz), 1.70 (ddt, 1H, J = 10.0, 7.2 and 4.2 Hz), 1.65–1.54 (m, 1H); 13C NMR (150 MHz, DMSO-d6, δ, p.p.m.): 173.01, 168.80, 138.03, 127.62, 126.53, 122.70, 58.22, 44.09, 31.36, 25.87, 18.14; HRMS, calculated for C11H13NO3S (239.06) [M+1]+: 240.0616; found: 240.0611.
(S)-6-Oxo-1-(thiophen-3-ylmethyl)piperidine-2-carboxylic acid, (3b), was obtained from thiophene-3-carboxaldehyde (12.3 g, 0.11 mol) and (S)-2-aminoadipic acid, (1) (16.1 g, 0.1 mol), in the same way as for (3a) (yield 18.2 g, 76%) as colourless crystals. Analysis: m.p. 437.25–437.85 K; [α]D24 = 94.7 (c 1.02, MeOH); 1H NMR (600 MHz, DMSO-d6, δ, p.p.m.): 13.02 (bs, 1H, COOH), 7.42 (d, 1H, J = 5.1 Hz), 7.00 (d, 1H, J = 3.5 Hz), 6.95 (t, 1H, J = 4.3 Hz), 5.29 (d, 1H, J = 15.3 Hz), 4.05 (dd, 1H, J = 6.1 and 3.1 Hz), 3.91 (d, 1H, J = 15.3 Hz), 2.06 (dd, 1H, J = 13.3 and 2.2 Hz), 1.87–1.80 (m, 1H), 1.68 (dt, 1H, J = 8.9 and 4.5 Hz), 1.60 (dt, 1H, J = 13.0 and 8.8 Hz); 13C NMR (150 MHz, DMSO-d6, δ, p.p.m.): 172.80, 168.71, 139.69, 126.85, 126.52, 125.94, 58.05, 43.57, 31.31, 25.01, 18.08; HRMS, calculated for C11H13NO3S (239.06) [M+1]+: 240.0616; found 240.0611.
Crystal data, data collection and structure refinement details are summarized in Table 1. C-bound H atoms were positioned geometrically and treated as riding atoms, with C—H = 0.93–0.98 Å and Uiso(H) = 1.2Ueq(C). In both molecules, the O-bound H atoms were taken from difference Fourier syntheses and their coordinates and isotropic displacement parameters were refined freely. The positions of the atoms in the major and minor components were determined initially by location of the major component and subsequent refinement of these sites at less than full occupancy, enhancing the difference Fourier map which displayed the location of the minor component atoms. The occupancies of the major and minor components were refined and summed to unity, yielding a ratio of 0.815 (3):0.185 (3). The C—C and C—S bonds involving the disordered C and S atoms were restrained to 1.350 (5) and 1.720 (5) Å, respectively. The major and minor components were both refined with anistropic displacement parameters. The atomic displacement parameters of the minor position for each disordered atom were restrained to have similar Uij values.
Despite their similar molecular constitutions, (3a) and (3b) crystallize in very different space groups. Compound (3a) crystallizes in the monoclinic space group P21 with Z = 2, whereas (3b) crystallizes in the orthorhombic space group P212121 with Z = 4 in the unit cell. Although the density of (3a) (1.393 Mg m-3) is very similar to that of (3b) (1.390 Mg m-3), it is perhaps surprising that this is not in accordance with the observed stronger intermolecular hydrogen bonding in (3b) (see below). The absolute configuration of atom C1 in each compound was assumed from anomalous dispersion effects of the S atom (Flack, 1983) in diffraction measurements on the crystals. The expected stereochemistry of atom C1 was confirmed as S (Figs. 1 and 2).
The thiophene ring of (3a) exhibits ring disorder over two positions [occupancy factors of 0.815 (3) for the major disorder component and 0.185 (3) for the minor disorder component]. In the following, only the major disorder component of (3a) will be discussed. The structures of (3a) and (3b) have similar six-membered piperidine ring conformations, close to a half-chair. The C atom at the 2-position is displaced by -0.620 (2) and -0.639 (3) Å, respectively, from the mean plane defined by the other five atoms of the ring (N1/C1–C5). For both structures, the piperidine ring-puckering parameters (Cremer & Pople, 1975) are very similar. The overall puckering amplitude Q = 0.464 (2) Å [0.445 (2) Å in (3b)], θ = 41.7 (2)° [42.0 (3)° in (3b)] and ϕ = -131.7 (1)° [115.7 (4)° in (3b)]. The dihedral angle between the plane of the central piperidine ring and that of the thiophene ring in (3a) is 64.6 (1)°, whereas in (3b) this angle is 75.9 (1)°. Apart from the pendent thiophene ring, the non-H atoms in both molecules do not deviate markedly from coplanarity; the maximum deviations from the mean planes of these atoms are exhibited by atom C9A [-0.012 (1) Å in (3a)] and atom C9 [-0.004 (2) Å in (3b)]. In both compounds, atom N1 is sp2-hybridized, as evidenced by the sum of the valence angles around this atom [359.0° in (3a) and 359.7° in (3b)]. These data are consistent with conjugation of the lone-pair electrons of an N atom with an adjacent carbonyl group, similar to what is observed for amides. The bond lengths of the carbonyl group C5═O1 in both compounds [1.240 (2) Å in (3a) and 1.243 (2)° in (3b)] are somewhat longer than typical carbonyl bonds. This may be due to the fact that atom O1 participates in a strong intermolecular hydrogen bond.
Calculation of the electronic structure of a compound provides several indices which characterize the distribution of electron density in the molecule and the multiplicity of atomic bonds. The net charges give a picture of the distribution of electron density in the molecule and the values of the Wiberg bond indices enable one to estimate the multiplicity of individual atomic bonds. By evaluating the experimental interactions of the structures of (3a) and (3b) in the solid phase in this work, it was found that the intermolecular interactions are the most important in the carboxylate part of the molecule, primarily between atoms O1 and H2. It follows from the calculations that atom O1 in (3a) carries quite a large negative charge [-0.435; -0.449 in (3b)], while atom H2 in (3a) has a positive charge [0.358; 0.389 in (3b)]. The charge distribution in the thiophene ring indicates that the large positive charge is localized only at the S atom [0.425 in (3a) and 0.343 in (3b)], whereas the most negative net charges are located on atoms C7 and C10A in (3a) and C9 and C10 in (3b) (see Tables 2 and 3). This charge distribution and the spatial arrangement (geometry) of the molecule govern its biological activity and are important for the overall stabilization of the crystal. It follows from the Wiberg index values that the C5═O1 bond in both compounds is not a pure double bond but that π-electrons are also delocalized in the region of the C5—N1 bond. The other bonds of the central piperidine ring have the character of single bonds. The values of the Wiberg indices for the bonds S1A—C7 (Iw = 1.210) and S1A—C10A (Iw = 1.226) in (3a), and S1—C9 (Iw = 1.216) and S1—C10 (Iw = 1.199) in (3b) indicate the character of partial single or conjugated bonds. These results of the calculations are in a good agreement with the experimental values of the bond lengths found by X-ray structure analysis.
There are a number of strong and weak intra- and intermolecular contacts within the crystal structures of (3a) and (3b) (Tables 4 and 5). The rules governing the crystal packing of (3a) and (3b) are similar. Strong intermolecular O—H···O hydrogen bonds, involving the carboxylate group at the 2-position as H-atom donor and the carbonyl group at the 6-position as H-atom acceptor, link the molecules into infinite C(7) (Bernstein et al., 1995) zigzag chains of molecules along the b axis in (3a), and zigzag chains of molecules along the c axis in (3b) (Figs. 3 and 4). An additional weak C—H···O interaction between adjacent chains in (3a) prompts the formation of a hydrogen-bonded R44(20) sheet motif (Bernstein et al., 1995) (Fig. 5). Finally, a very weak C═O···π contact in (3a) might exist between the carbonyl O atom of the acid group and the centroid Cg of the thiophene ring, with a C11═O3···Cg1(x, y, z) distance of 3.751 (3) Å. Aromatic π–π stacking forces are an important factor in the stabilization of such a molecular formation. For (3b), the combination of a strong O—H···O hydrogen bond and two C—H···O interactions yields a three-dimensional supramolecular R44(21) framework (Fig. 6), and an intramolecular C6—H6B···O1 hydrogen bond generates an S(5) motif. Such an interaction is not present in (3a). [Original text was unclear in several places. Please check and confirm that the intended meaning has not been altered.]
For both compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2009). Cell refinement: CrysAlis CCD (Oxford Diffraction, 2009) for (3a); CrysAlis CCD (Oxford Diffraction, 2009 for (3b). For both compounds, data reduction: CrysAlis RED (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXS97 (Sheldrick, 2008); molecular graphics: SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and WinGX (Farrugia, 2012).
C11H13NO3S | F(000) = 252 |
Mr = 239.28 | Dx = 1.393 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 3643 reflections |
a = 5.3473 (11) Å | θ = 3.9–28.0° |
b = 13.073 (2) Å | µ = 0.28 mm−1 |
c = 8.408 (5) Å | T = 295 K |
β = 103.88 (3)° | Needle, colourless |
V = 570.6 (4) Å3 | 0.50 × 0.30 × 0.10 mm |
Z = 2 |
Oxford Xcalibur Gemini diffractometer with Ruby CCD area-detector | 2091 independent reflections |
Radiation source: fine-focus sealed tube | 1964 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
Detector resolution: 5.2170 pixels mm-1 | θmax = 25.3°, θmin = 3.1° |
ω scans | h = −6→6 |
Absorption correction: analytical [CrysAlis RED (Oxford Diffraction, 2009), based on expressions derived by Clark & Reid (1995)] | k = −15→15 |
Tmin = 0.812, Tmax = 0.991 | l = −10→10 |
8967 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.024 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.059 | w = 1/[σ2(Fo2) + (0.0342P)2 + 0.0127P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
2091 reflections | Δρmax = 0.09 e Å−3 |
186 parameters | Δρmin = −0.14 e Å−3 |
39 restraints | Absolute structure: Flack (1983), with 995 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.01 (6) |
C11H13NO3S | V = 570.6 (4) Å3 |
Mr = 239.28 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 5.3473 (11) Å | µ = 0.28 mm−1 |
b = 13.073 (2) Å | T = 295 K |
c = 8.408 (5) Å | 0.50 × 0.30 × 0.10 mm |
β = 103.88 (3)° |
Oxford Xcalibur Gemini diffractometer with Ruby CCD area-detector | 2091 independent reflections |
Absorption correction: analytical [CrysAlis RED (Oxford Diffraction, 2009), based on expressions derived by Clark & Reid (1995)] | 1964 reflections with I > 2σ(I) |
Tmin = 0.812, Tmax = 0.991 | Rint = 0.025 |
8967 measured reflections |
R[F2 > 2σ(F2)] = 0.024 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.059 | Δρmax = 0.09 e Å−3 |
S = 1.05 | Δρmin = −0.14 e Å−3 |
2091 reflections | Absolute structure: Flack (1983), with 995 Friedel pairs |
186 parameters | Absolute structure parameter: −0.01 (6) |
39 restraints |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C1 | 0.3869 (2) | 0.43625 (11) | 0.59643 (18) | 0.0392 (3) | |
H1 | 0.5561 | 0.4078 | 0.5954 | 0.047* | |
C2 | 0.4069 (3) | 0.49264 (12) | 0.75780 (19) | 0.0507 (4) | |
H2B | 0.4540 | 0.4449 | 0.8484 | 0.061* | |
H2A | 0.5400 | 0.5446 | 0.7715 | 0.061* | |
C3 | 0.1499 (4) | 0.54250 (13) | 0.7585 (2) | 0.0551 (4) | |
H3B | 0.0248 | 0.4897 | 0.7640 | 0.066* | |
H3A | 0.1702 | 0.5850 | 0.8554 | 0.066* | |
C4 | 0.0500 (3) | 0.60726 (12) | 0.60787 (19) | 0.0480 (4) | |
H4B | −0.1365 | 0.6079 | 0.5858 | 0.058* | |
H4A | 0.1084 | 0.6769 | 0.6339 | 0.058* | |
C5 | 0.1234 (3) | 0.57691 (10) | 0.45254 (18) | 0.0384 (3) | |
C6 | 0.4003 (3) | 0.48498 (11) | 0.3103 (2) | 0.0458 (4) | |
H6B | 0.5810 | 0.4664 | 0.3434 | 0.055* | |
H6A | 0.3878 | 0.5474 | 0.2464 | 0.055* | |
C7 | 0.2590 (3) | 0.40224 (11) | 0.20299 (18) | 0.0419 (3) | |
C8A | 0.3475 (13) | 0.3102 (4) | 0.1668 (9) | 0.0632 (13) | 0.815 (3) |
H8A | 0.5143 | 0.2882 | 0.2136 | 0.076* | 0.815 (3) |
C9A | 0.1760 (11) | 0.2517 (4) | 0.0572 (8) | 0.0668 (10) | 0.815 (3) |
H9A | 0.2118 | 0.1864 | 0.0248 | 0.080* | 0.815 (3) |
C10A | −0.0510 (10) | 0.2998 (3) | 0.0017 (8) | 0.0601 (11) | 0.815 (3) |
H10A | −0.1892 | 0.2732 | −0.0763 | 0.072* | 0.815 (3) |
C11 | 0.1945 (3) | 0.34852 (10) | 0.58451 (18) | 0.0378 (3) | |
N1 | 0.3079 (2) | 0.50624 (8) | 0.45863 (15) | 0.0381 (3) | |
O1 | 0.0246 (2) | 0.62161 (8) | 0.32251 (14) | 0.0515 (3) | |
O2 | 0.3007 (2) | 0.26855 (8) | 0.66988 (15) | 0.0514 (3) | |
H2 | 0.185 (4) | 0.2225 (18) | 0.662 (3) | 0.072 (6)* | |
O3 | −0.02835 (19) | 0.35488 (8) | 0.51293 (16) | 0.0494 (3) | |
S1A | −0.05077 (15) | 0.41712 (6) | 0.09413 (9) | 0.0543 (3) | 0.815 (3) |
C8B | 0.033 (2) | 0.4040 (19) | 0.0893 (19) | 0.094 (7) | 0.185 (3) |
H8B | −0.0562 | 0.4649 | 0.0609 | 0.113* | 0.185 (3) |
C9B | −0.059 (5) | 0.3148 (19) | 0.018 (4) | 0.090 (8) | 0.185 (3) |
H9B | −0.2302 | 0.3029 | −0.0342 | 0.108* | 0.185 (3) |
C10B | 0.132 (3) | 0.245 (2) | 0.033 (3) | 0.063 (5) | 0.185 (3) |
H10B | 0.1245 | 0.1854 | −0.0285 | 0.075* | 0.185 (3) |
S1B | 0.3899 (15) | 0.2854 (5) | 0.1847 (11) | 0.0602 (16) | 0.185 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0306 (6) | 0.0384 (7) | 0.0462 (8) | 0.0022 (5) | 0.0046 (6) | 0.0036 (6) |
C2 | 0.0552 (9) | 0.0473 (9) | 0.0421 (9) | −0.0047 (7) | −0.0031 (8) | −0.0006 (7) |
C3 | 0.0719 (11) | 0.0520 (9) | 0.0418 (9) | 0.0022 (8) | 0.0144 (8) | −0.0044 (8) |
C4 | 0.0538 (9) | 0.0432 (8) | 0.0483 (9) | 0.0046 (7) | 0.0148 (7) | −0.0028 (7) |
C5 | 0.0415 (7) | 0.0305 (6) | 0.0434 (9) | −0.0019 (6) | 0.0104 (7) | 0.0006 (6) |
C6 | 0.0408 (7) | 0.0491 (9) | 0.0522 (9) | −0.0021 (6) | 0.0202 (7) | 0.0011 (7) |
C7 | 0.0413 (7) | 0.0479 (8) | 0.0405 (8) | 0.0029 (7) | 0.0176 (6) | 0.0044 (7) |
C8A | 0.053 (3) | 0.068 (3) | 0.069 (2) | 0.0148 (19) | 0.0161 (18) | 0.016 (2) |
C9A | 0.095 (3) | 0.0486 (17) | 0.059 (3) | −0.0002 (17) | 0.023 (2) | −0.0063 (17) |
C10A | 0.077 (3) | 0.0629 (19) | 0.040 (2) | −0.0207 (17) | 0.0143 (18) | −0.0106 (16) |
C11 | 0.0361 (8) | 0.0363 (7) | 0.0408 (9) | 0.0020 (6) | 0.0089 (7) | −0.0006 (6) |
N1 | 0.0365 (6) | 0.0369 (6) | 0.0421 (7) | −0.0005 (5) | 0.0120 (5) | 0.0018 (5) |
O1 | 0.0639 (7) | 0.0446 (6) | 0.0445 (6) | 0.0125 (5) | 0.0102 (5) | 0.0049 (5) |
O2 | 0.0489 (6) | 0.0399 (6) | 0.0595 (7) | −0.0026 (5) | 0.0011 (5) | 0.0120 (5) |
O3 | 0.0343 (6) | 0.0467 (6) | 0.0629 (8) | −0.0025 (4) | 0.0030 (5) | 0.0031 (5) |
S1A | 0.0446 (4) | 0.0679 (5) | 0.0459 (3) | 0.0026 (3) | 0.0020 (3) | 0.0004 (3) |
C8B | 0.063 (9) | 0.117 (11) | 0.100 (11) | 0.046 (9) | 0.015 (7) | −0.010 (9) |
C9B | 0.057 (9) | 0.137 (16) | 0.060 (14) | 0.003 (9) | −0.015 (8) | 0.001 (12) |
C10B | 0.071 (9) | 0.095 (10) | 0.030 (7) | −0.009 (8) | 0.029 (7) | −0.022 (7) |
S1B | 0.051 (2) | 0.055 (2) | 0.072 (3) | 0.0135 (18) | 0.0099 (18) | −0.007 (3) |
C1—N1 | 1.4570 (18) | C7—C8B | 1.348 (5) |
C1—C2 | 1.525 (2) | C7—C8A | 1.354 (4) |
C1—C11 | 1.528 (2) | C7—S1A | 1.7006 (16) |
C1—H1 | 0.9800 | C7—S1B | 1.702 (4) |
C2—C3 | 1.522 (2) | C8A—C9A | 1.367 (4) |
C2—H2B | 0.9700 | C8A—H8A | 0.9300 |
C2—H2A | 0.9700 | C9A—C10A | 1.347 (4) |
C3—C4 | 1.511 (2) | C9A—H9A | 0.9300 |
C3—H3B | 0.9700 | C10A—S1A | 1.719 (4) |
C3—H3A | 0.9700 | C10A—H10A | 0.9300 |
C4—C5 | 1.504 (2) | C11—O3 | 1.2020 (18) |
C4—H4B | 0.9700 | C11—O2 | 1.3173 (17) |
C4—H4A | 0.9700 | O2—H2 | 0.86 (2) |
C5—O1 | 1.2403 (18) | C8B—C9B | 1.349 (5) |
C5—N1 | 1.3439 (18) | C8B—H8B | 0.9300 |
C6—N1 | 1.474 (2) | C9B—C10B | 1.349 (5) |
C6—C7 | 1.493 (2) | C9B—H9B | 0.9300 |
C6—H6B | 0.9700 | C10B—S1B | 1.724 (5) |
C6—H6A | 0.9700 | C10B—H10B | 0.9300 |
N1—C1—C2 | 110.42 (12) | C8A—C7—C6 | 128.8 (3) |
N1—C1—C11 | 110.91 (11) | C8B—C7—S1A | 13.0 (8) |
C2—C1—C11 | 108.88 (13) | C8A—C7—S1A | 109.2 (3) |
N1—C1—H1 | 108.9 | C6—C7—S1A | 121.93 (11) |
C2—C1—H1 | 108.9 | C8B—C7—S1B | 105.6 (9) |
C11—C1—H1 | 108.9 | C8A—C7—S1B | 7.7 (5) |
C3—C2—C1 | 109.86 (13) | C6—C7—S1B | 123.0 (2) |
C3—C2—H2B | 109.7 | S1A—C7—S1B | 115.0 (2) |
C1—C2—H2B | 109.7 | C7—C8A—C9A | 115.8 (4) |
C3—C2—H2A | 109.7 | C7—C8A—H8A | 122.1 |
C1—C2—H2A | 109.7 | C9A—C8A—H8A | 122.1 |
H2B—C2—H2A | 108.2 | C10A—C9A—C8A | 112.0 (4) |
C4—C3—C2 | 112.01 (15) | C10A—C9A—H9A | 124.0 |
C4—C3—H3B | 109.2 | C8A—C9A—H9A | 124.0 |
C2—C3—H3B | 109.2 | C9A—C10A—S1A | 110.9 (4) |
C4—C3—H3A | 109.2 | C9A—C10A—H10A | 124.5 |
C2—C3—H3A | 109.2 | S1A—C10A—H10A | 124.5 |
H3B—C3—H3A | 107.9 | O3—C11—O2 | 125.01 (14) |
C5—C4—C3 | 117.82 (13) | O3—C11—C1 | 123.52 (13) |
C5—C4—H4B | 107.8 | O2—C11—C1 | 111.36 (12) |
C3—C4—H4B | 107.9 | C5—N1—C1 | 122.16 (12) |
C5—C4—H4A | 107.9 | C5—N1—C6 | 119.31 (12) |
C3—C4—H4A | 107.8 | C1—N1—C6 | 117.54 (12) |
H4B—C4—H4A | 107.2 | C11—O2—H2 | 107.9 (14) |
O1—C5—N1 | 120.72 (14) | C7—S1A—C10A | 92.07 (19) |
O1—C5—C4 | 119.77 (13) | C7—C8B—C9B | 118.0 (18) |
N1—C5—C4 | 119.36 (13) | C7—C8B—H8B | 121.0 |
N1—C6—C7 | 115.11 (12) | C9B—C8B—H8B | 121.0 |
N1—C6—H6B | 108.5 | C10B—C9B—C8B | 111 (2) |
C7—C6—H6B | 108.5 | C10B—C9B—H9B | 124.5 |
N1—C6—H6A | 108.5 | C8B—C9B—H9B | 124.5 |
C7—C6—H6A | 108.5 | C9B—C10B—S1B | 108.3 (15) |
H6B—C6—H6A | 107.5 | C9B—C10B—H10B | 125.9 |
C8B—C7—C8A | 99.1 (10) | S1B—C10B—H10B | 125.9 |
C8B—C7—C6 | 130.8 (10) | C7—S1B—C10B | 93.9 (9) |
N1—C1—C2—C3 | 57.46 (16) | C4—C5—N1—C6 | −173.14 (12) |
C11—C1—C2—C3 | −64.52 (15) | C2—C1—N1—C5 | −41.96 (17) |
C1—C2—C3—C4 | −51.94 (18) | C11—C1—N1—C5 | 78.81 (16) |
C2—C3—C4—C5 | 29.3 (2) | C2—C1—N1—C6 | 149.56 (12) |
C3—C4—C5—O1 | 172.73 (15) | C11—C1—N1—C6 | −89.66 (15) |
C3—C4—C5—N1 | −11.6 (2) | C7—C6—N1—C5 | −90.49 (15) |
N1—C6—C7—C8B | 81.2 (13) | C7—C6—N1—C1 | 78.33 (16) |
N1—C6—C7—C8A | −115.0 (5) | C8B—C7—S1A—C10A | 40 (5) |
N1—C6—C7—S1A | 69.32 (17) | C8A—C7—S1A—C10A | −0.6 (5) |
N1—C6—C7—S1B | −108.7 (5) | C6—C7—S1A—C10A | 175.9 (3) |
C8B—C7—C8A—C9A | −9.0 (12) | S1B—C7—S1A—C10A | −6.0 (5) |
C6—C7—C8A—C9A | −176.7 (5) | C9A—C10A—S1A—C7 | 1.6 (5) |
S1A—C7—C8A—C9A | −0.6 (8) | C8A—C7—C8B—C9B | 17 (3) |
S1B—C7—C8A—C9A | 140 (6) | C6—C7—C8B—C9B | −175 (2) |
C7—C8A—C9A—C10A | 1.9 (11) | S1A—C7—C8B—C9B | −124 (6) |
C8A—C9A—C10A—S1A | −2.2 (9) | S1B—C7—C8B—C9B | 13 (3) |
N1—C1—C11—O3 | −25.7 (2) | C7—C8B—C9B—C10B | −21 (4) |
C2—C1—C11—O3 | 96.03 (18) | C8B—C9B—C10B—S1B | 17 (4) |
N1—C1—C11—O2 | 157.98 (12) | C8B—C7—S1B—C10B | −2.1 (15) |
C2—C1—C11—O2 | −80.33 (14) | C8A—C7—S1B—C10B | −34 (5) |
O1—C5—N1—C1 | −165.84 (13) | C6—C7—S1B—C10B | −174.3 (10) |
C4—C5—N1—C1 | 18.58 (19) | S1A—C7—S1B—C10B | 7.5 (12) |
O1—C5—N1—C6 | 2.4 (2) | C9B—C10B—S1B—C7 | −9 (3) |
Cg1 is the centroid of the [WHICH?] benzene ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1i | 0.86 (2) | 1.75 (2) | 2.6027 (16) | 171 (2) |
C1—H1···O3ii | 0.98 | 2.58 | 3.5289 (19) | 164 |
C11—O3···Cg1 | 1.20 (1) | 3.75 (1) | 3.975 (4) | 92 (1) |
Symmetry codes: (i) −x, y−1/2, −z+1; (ii) x+1, y, z. |
C11H13NO3S | F(000) = 504 |
Mr = 239.28 | Dx = 1.390 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 5924 reflections |
a = 7.9560 (4) Å | θ = 3.5–27.5° |
b = 10.3710 (5) Å | µ = 0.27 mm−1 |
c = 13.8612 (6) Å | T = 295 K |
V = 1143.71 (9) Å3 | Needle, colourless |
Z = 4 | 0.40 × 0.30 × 0.20 mm |
Oxford Xcalibur Gemini diffractometer with Ruby CCD area-detector | 2098 independent reflections |
Radiation source: fine-focus sealed tube | 1921 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
Detector resolution: 5.2170 pixels mm-1 | θmax = 25.3°, θmin = 2.5° |
ω scans | h = −9→9 |
Absorption correction: analytical [CrysAlis RED (Oxford Diffraction, 2009), based on expressions derived by Clark & Reid (1995)] | k = −12→12 |
Tmin = 0.907, Tmax = 1.000 | l = −16→16 |
17583 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.029 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.077 | w = 1/[σ2(Fo2) + (0.0393P)2 + 0.1785P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max < 0.001 |
2098 reflections | Δρmax = 0.14 e Å−3 |
149 parameters | Δρmin = −0.18 e Å−3 |
0 restraints | Absolute structure: Flack (1983), with 867 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.03 (9) |
C11H13NO3S | V = 1143.71 (9) Å3 |
Mr = 239.28 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 7.9560 (4) Å | µ = 0.27 mm−1 |
b = 10.3710 (5) Å | T = 295 K |
c = 13.8612 (6) Å | 0.40 × 0.30 × 0.20 mm |
Oxford Xcalibur Gemini diffractometer with Ruby CCD area-detector | 2098 independent reflections |
Absorption correction: analytical [CrysAlis RED (Oxford Diffraction, 2009), based on expressions derived by Clark & Reid (1995)] | 1921 reflections with I > 2σ(I) |
Tmin = 0.907, Tmax = 1.000 | Rint = 0.028 |
17583 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.077 | Δρmax = 0.14 e Å−3 |
S = 1.06 | Δρmin = −0.18 e Å−3 |
2098 reflections | Absolute structure: Flack (1983), with 867 Friedel pairs |
149 parameters | Absolute structure parameter: −0.03 (9) |
0 restraints |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.6922 (2) | 0.32225 (17) | 0.35749 (12) | 0.0403 (4) | |
H1 | 0.6137 | 0.2585 | 0.3838 | 0.048* | |
C2 | 0.8390 (3) | 0.2513 (2) | 0.31209 (15) | 0.0571 (6) | |
H2A | 0.9016 | 0.2061 | 0.3617 | 0.069* | |
H2B | 0.7973 | 0.1880 | 0.2665 | 0.069* | |
C3 | 0.9534 (3) | 0.3451 (3) | 0.26087 (18) | 0.0707 (7) | |
H3A | 1.0097 | 0.3986 | 0.3083 | 0.085* | |
H3B | 1.0388 | 0.2973 | 0.2260 | 0.085* | |
C4 | 0.8591 (3) | 0.4302 (2) | 0.19122 (17) | 0.0614 (6) | |
H4A | 0.9214 | 0.5102 | 0.1845 | 0.074* | |
H4B | 0.8596 | 0.3883 | 0.1287 | 0.074* | |
C5 | 0.6814 (3) | 0.46351 (19) | 0.21545 (13) | 0.0437 (4) | |
C6 | 0.4227 (2) | 0.42019 (19) | 0.30277 (12) | 0.0422 (4) | |
H6A | 0.3710 | 0.3370 | 0.3150 | 0.051* | |
H6B | 0.3732 | 0.4547 | 0.2442 | 0.051* | |
C7 | 0.3812 (2) | 0.50915 (17) | 0.38516 (12) | 0.0372 (4) | |
C8 | 0.4385 (3) | 0.63819 (18) | 0.39409 (14) | 0.0481 (5) | |
H8 | 0.5112 | 0.6774 | 0.3505 | 0.058* | |
C9 | 0.3753 (3) | 0.6981 (2) | 0.47339 (16) | 0.0551 (5) | |
H9 | 0.4003 | 0.7826 | 0.4906 | 0.066* | |
C10 | 0.2762 (3) | 0.47663 (19) | 0.45799 (13) | 0.0491 (5) | |
H10 | 0.2262 | 0.3960 | 0.4644 | 0.059* | |
C11 | 0.7557 (3) | 0.40650 (17) | 0.44019 (11) | 0.0425 (4) | |
N1 | 0.60297 (18) | 0.40086 (14) | 0.28663 (9) | 0.0368 (3) | |
O1 | 0.6042 (2) | 0.54376 (16) | 0.16569 (9) | 0.0630 (4) | |
O2 | 0.7624 (3) | 0.34112 (13) | 0.52135 (9) | 0.0684 (5) | |
H2 | 0.819 (4) | 0.392 (3) | 0.570 (2) | 0.095 (9)* | |
O3 | 0.7990 (2) | 0.51594 (13) | 0.43041 (10) | 0.0596 (4) | |
S1 | 0.24644 (8) | 0.60102 (6) | 0.53662 (4) | 0.06240 (18) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0488 (10) | 0.0370 (9) | 0.0352 (8) | −0.0021 (8) | −0.0054 (7) | −0.0013 (7) |
C2 | 0.0638 (14) | 0.0574 (13) | 0.0501 (11) | 0.0161 (11) | −0.0091 (10) | −0.0131 (10) |
C3 | 0.0458 (12) | 0.105 (2) | 0.0609 (13) | 0.0127 (14) | 0.0025 (11) | −0.0090 (14) |
C4 | 0.0518 (13) | 0.0718 (16) | 0.0606 (12) | −0.0055 (11) | 0.0153 (11) | −0.0040 (11) |
C5 | 0.0500 (11) | 0.0469 (10) | 0.0342 (9) | −0.0024 (9) | 0.0042 (8) | −0.0037 (8) |
C6 | 0.0393 (10) | 0.0536 (11) | 0.0337 (8) | −0.0028 (9) | −0.0032 (7) | −0.0023 (8) |
C7 | 0.0354 (9) | 0.0421 (9) | 0.0340 (8) | 0.0031 (8) | −0.0039 (8) | 0.0025 (7) |
C8 | 0.0485 (11) | 0.0448 (10) | 0.0512 (11) | 0.0006 (9) | 0.0049 (9) | 0.0059 (9) |
C9 | 0.0547 (12) | 0.0441 (10) | 0.0665 (13) | 0.0084 (9) | −0.0067 (11) | −0.0114 (10) |
C10 | 0.0515 (12) | 0.0516 (11) | 0.0443 (10) | −0.0013 (9) | 0.0065 (10) | 0.0019 (8) |
C11 | 0.0489 (10) | 0.0412 (9) | 0.0375 (8) | 0.0048 (10) | −0.0060 (9) | −0.0054 (7) |
N1 | 0.0401 (8) | 0.0417 (8) | 0.0287 (6) | −0.0006 (7) | −0.0012 (6) | −0.0026 (7) |
O1 | 0.0746 (11) | 0.0712 (9) | 0.0432 (7) | 0.0140 (8) | 0.0143 (8) | 0.0196 (7) |
O2 | 0.1193 (14) | 0.0489 (8) | 0.0370 (7) | −0.0004 (10) | −0.0238 (9) | −0.0028 (6) |
O3 | 0.0762 (11) | 0.0443 (8) | 0.0584 (8) | −0.0113 (7) | −0.0163 (8) | −0.0069 (6) |
S1 | 0.0592 (3) | 0.0781 (4) | 0.0499 (3) | 0.0089 (3) | 0.0125 (3) | −0.0118 (3) |
C1—N1 | 1.461 (2) | C6—N1 | 1.466 (2) |
C1—C2 | 1.517 (3) | C6—C7 | 1.505 (2) |
C1—C11 | 1.527 (2) | C6—H6A | 0.9700 |
C1—H1 | 0.9800 | C6—H6B | 0.9700 |
C2—C3 | 1.509 (3) | C7—C10 | 1.353 (3) |
C2—H2A | 0.9700 | C7—C8 | 1.419 (3) |
C2—H2B | 0.9700 | C8—C9 | 1.359 (3) |
C3—C4 | 1.508 (3) | C8—H8 | 0.9300 |
C3—H3A | 0.9700 | C9—S1 | 1.683 (2) |
C3—H3B | 0.9700 | C9—H9 | 0.9300 |
C4—C5 | 1.494 (3) | C10—S1 | 1.705 (2) |
C4—H4A | 0.9700 | C10—H10 | 0.9300 |
C4—H4B | 0.9700 | C11—O3 | 1.194 (2) |
C5—O1 | 1.243 (2) | C11—O2 | 1.315 (2) |
C5—N1 | 1.336 (2) | O2—H2 | 0.96 (3) |
N1—C1—C2 | 111.47 (15) | N1—C6—C7 | 114.49 (14) |
N1—C1—C11 | 110.25 (13) | N1—C6—H6A | 108.6 |
C2—C1—C11 | 109.53 (16) | C7—C6—H6A | 108.6 |
N1—C1—H1 | 108.5 | N1—C6—H6B | 108.6 |
C2—C1—H1 | 108.5 | C7—C6—H6B | 108.6 |
C11—C1—H1 | 108.5 | H6A—C6—H6B | 107.6 |
C3—C2—C1 | 110.31 (18) | C10—C7—C8 | 111.62 (17) |
C3—C2—H2A | 109.6 | C10—C7—C6 | 123.29 (17) |
C1—C2—H2A | 109.6 | C8—C7—C6 | 125.01 (17) |
C3—C2—H2B | 109.6 | C9—C8—C7 | 112.51 (19) |
C1—C2—H2B | 109.6 | C9—C8—H8 | 123.7 |
H2A—C2—H2B | 108.1 | C7—C8—H8 | 123.7 |
C4—C3—C2 | 112.24 (18) | C8—C9—S1 | 111.89 (15) |
C4—C3—H3A | 109.2 | C8—C9—H9 | 124.1 |
C2—C3—H3A | 109.2 | S1—C9—H9 | 124.1 |
C4—C3—H3B | 109.2 | C7—C10—S1 | 111.96 (15) |
C2—C3—H3B | 109.2 | C7—C10—H10 | 124.0 |
H3A—C3—H3B | 107.9 | S1—C10—H10 | 124.0 |
C5—C4—C3 | 117.53 (19) | O3—C11—O2 | 125.15 (17) |
C5—C4—H4A | 107.9 | O3—C11—C1 | 123.65 (15) |
C3—C4—H4A | 107.9 | O2—C11—C1 | 111.14 (15) |
C5—C4—H4B | 107.9 | C5—N1—C1 | 122.76 (15) |
C3—C4—H4B | 107.9 | C5—N1—C6 | 120.22 (15) |
H4A—C4—H4B | 107.2 | C1—N1—C6 | 116.70 (14) |
O1—C5—N1 | 120.32 (18) | C11—O2—H2 | 109.3 (16) |
O1—C5—C4 | 119.83 (19) | C9—S1—C10 | 92.02 (10) |
N1—C5—C4 | 119.72 (19) | ||
N1—C1—C2—C3 | 54.3 (2) | N1—C1—C11—O2 | 150.07 (17) |
C11—C1—C2—C3 | −68.0 (2) | C2—C1—C11—O2 | −86.9 (2) |
C1—C2—C3—C4 | −52.1 (2) | O1—C5—N1—C1 | −169.47 (17) |
C2—C3—C4—C5 | 31.1 (3) | C4—C5—N1—C1 | 14.8 (3) |
C3—C4—C5—O1 | 172.6 (2) | O1—C5—N1—C6 | 3.9 (3) |
C3—C4—C5—N1 | −11.6 (3) | C4—C5—N1—C6 | −171.89 (17) |
N1—C6—C7—C10 | −126.88 (19) | C2—C1—N1—C5 | −36.6 (2) |
N1—C6—C7—C8 | 56.6 (2) | C11—C1—N1—C5 | 85.2 (2) |
C10—C7—C8—C9 | 0.2 (2) | C2—C1—N1—C6 | 149.83 (16) |
C6—C7—C8—C9 | 177.09 (17) | C11—C1—N1—C6 | −88.31 (18) |
C7—C8—C9—S1 | −0.5 (2) | C7—C6—N1—C5 | −101.45 (18) |
C8—C7—C10—S1 | 0.1 (2) | C7—C6—N1—C1 | 72.3 (2) |
C6—C7—C10—S1 | −176.79 (13) | C8—C9—S1—C10 | 0.48 (17) |
N1—C1—C11—O3 | −32.5 (3) | C7—C10—S1—C9 | −0.35 (16) |
C2—C1—C11—O3 | 90.5 (2) |
Cg1 is the centroid of the thiophene ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1i | 0.96 (3) | 1.61 (3) | 2.560 (2) | 168 (3) |
C9—H9···O3ii | 0.93 | 2.49 | 3.308 (2) | 147 |
C10—H10···O2iii | 0.93 | 2.48 | 3.310 (2) | 148 |
Symmetry codes: (i) −x+3/2, −y+1, z+1/2; (ii) x−1/2, −y+3/2, −z+1; (iii) x−1/2, −y+1/2, −z+1. |
Experimental details
(3a) | (3b) | |
Crystal data | ||
Chemical formula | C11H13NO3S | C11H13NO3S |
Mr | 239.28 | 239.28 |
Crystal system, space group | Monoclinic, P21 | Orthorhombic, P212121 |
Temperature (K) | 295 | 295 |
a, b, c (Å) | 5.3473 (11), 13.073 (2), 8.408 (5) | 7.9560 (4), 10.3710 (5), 13.8612 (6) |
α, β, γ (°) | 90, 103.88 (3), 90 | 90, 90, 90 |
V (Å3) | 570.6 (4) | 1143.71 (9) |
Z | 2 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.28 | 0.27 |
Crystal size (mm) | 0.50 × 0.30 × 0.10 | 0.40 × 0.30 × 0.20 |
Data collection | ||
Diffractometer | Oxford Xcalibur Gemini diffractometer with Ruby CCD area-detector | Oxford Xcalibur Gemini diffractometer with Ruby CCD area-detector |
Absorption correction | Analytical [CrysAlis RED (Oxford Diffraction, 2009), based on expressions derived by Clark & Reid (1995)] | Analytical [CrysAlis RED (Oxford Diffraction, 2009), based on expressions derived by Clark & Reid (1995)] |
Tmin, Tmax | 0.812, 0.991 | 0.907, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8967, 2091, 1964 | 17583, 2098, 1921 |
Rint | 0.025 | 0.028 |
(sin θ/λ)max (Å−1) | 0.602 | 0.602 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.024, 0.059, 1.05 | 0.029, 0.077, 1.06 |
No. of reflections | 2091 | 2098 |
No. of parameters | 186 | 149 |
No. of restraints | 39 | 0 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.09, −0.14 | 0.14, −0.18 |
Absolute structure | Flack (1983), with 995 Friedel pairs | Flack (1983), with 867 Friedel pairs |
Absolute structure parameter | −0.01 (6) | −0.03 (9) |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2009), CrysAlis CCD (Oxford Diffraction, 2009, CrysAlis RED (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and WinGX (Farrugia, 2012).
Atom | Charge, q | Bond | Iw |
C1 | -0.162 | C1—C2 | 0.974 |
C2 | -0.380 | C2—C3 | 1.000 |
C3 | -0.427 | C3—C4 | 0.997 |
C4 | -0.480 | C4—C5 | 0.980 |
C5 | 0.561 | C6—C7 | 1.015 |
C6 | -0.299 | C7—C8A | 1.554 |
C7 | -0.391 | C8A—C9A | 1.278 |
C8A | -0.009 | C9A—C10A | 1.595 |
C9A | -0.111 | C11—C1 | 0.938 |
C10A | -0.493 | N1—C1 | 0.952 |
C11 | 0.429 | N1—C5 | 1.180 |
N1 | -0.499 | N1—C6 | 0.923 |
O1 | -0.435 | O1—C5 | 1.630 |
O2 | -0.522 | O2—C11 | 1.058 |
O3 | -0.342 | O3—C11 | 1.772 |
S1A | 0.425 | S1A—C7 | 1.210 |
S1A—C10A | 1.226 |
Cg1 is the centroid of the [WHICH?] benzene ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1i | 0.86 (2) | 1.75 (2) | 2.6027 (16) | 171 (2) |
C1—H1···O3ii | 0.98 | 2.58 | 3.5289 (19) | 164.1 |
C11—O3···Cg1 | 1.203 (2) | 3.751 (3) | 3.975 (4) | 91.8 (1) |
Symmetry codes: (i) −x, y−1/2, −z+1; (ii) x+1, y, z. |
Atom | Charge, q | Bond | Iw |
C1 | -0.144 | C1—C2 | 0.976 |
C2 | -0.395 | C2—C3 | 1.001 |
C3 | -0.417 | C3—C4 | 0.996 |
C4 | -0.484 | C4—C5 | 0.983 |
C5 | 0.566 | C6—C7 | 0.990 |
C6 | -0.325 | C7—C8 | 1.237 |
C7 | 0.073 | C7—C10 | 1.595 |
C8 | 0.026 | C8—C9 | 1.620 |
C9 | -0.517 | C11—C1 | 0.932 |
C10 | -0.508 | N1—C1 | 0.948 |
C11 | 0.540 | N1—C5 | 1.191 |
N1 | -0.518 | N1—C6 | 0.928 |
O1 | -0.449 | O1—C5 | 1.618 |
O2 | -0.530 | O2—C11 | 1.065 |
O3 | -0.347 | O3—C11 | 1.766 |
S1 | 0.343 | S1—C9 | 1.216 |
S1—C10 | 1.199 |
Cg1 is the centroid of the thiophene ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1i | 0.96 (3) | 1.61 (3) | 2.560 (2) | 168 (3) |
C9—H9···O3ii | 0.93 | 2.49 | 3.308 (2) | 146.5 |
C10—H10···O2iii | 0.93 | 2.48 | 3.310 (2) | 148.0 |
Symmetry codes: (i) −x+3/2, −y+1, z+1/2; (ii) x−1/2, −y+3/2, −z+1; (iii) x−1/2, −y+1/2, −z+1. |