research communications
Crystal structures of two chiral piperidine derivatives: 1-[(1R)-2-hydroxy-1-phenylethyl]piperidin-4-one and 8-[(1S)-1-phenylethyl]-1,4-dioxa-8-azaspiro[4.5]decane-7-thione
aUniversidad Juárez Autónoma de Tabasco, División Académica de Ciencias Básicas, Km. 1 carretera Cunduacán, Jalpa de Méndez AP 24, Cunduacán, Tabasco, Mexico, bInstituto de Física, Benemérita Universidad Autónoma de Puebla, Av. San Claudio y 18 Sur, 72570 Puebla, Pue., Mexico, and cCentro de Química, Instituto de Ciencias, Benemérita Universidad Autónoma de Puebla, 72570 Puebla, Pue., Mexico
*Correspondence e-mail: sylvain_bernes@hotmail.com
The crystal structures of the two title piperidine derivatives show different conformations for the six-membered heterocycle. The N-substituted 4-piperidinone 1-[(1R)-2-hydroxy-1-phenylethyl]piperidin-4-one, C13H17NO2, (I), has a chair conformation, while the piperidine substituted in position 2 with a thiocarbonyl group, 8-[(1S)-1-phenylethyl]-1,4-dioxa-8-azaspiro[4.5]decane-7-thione, C15H19NO2S, (II), features a half-chair conformation. Comparison of the two structures, and data retrieved from the literature, suggests that the conformational flexibility is mainly related to the state of the C atom α to the piperidinic N atom: a Csp3 atom favours the chair conformer, while a Csp2 atom distorts the ring towards a half-chair conformer. In the of (I), weak C—H⋯O hydrogen bonds link the molecules into supramolecular chains propagating along the b-axis direction. In the crystal of (II), the molecules are linked by weak C—H⋯S contacts into supramolecular chains propagating along the b-axis direction.
Keywords: crystal structure; piperidine; piperidone; thione; ring conformation.
1. Chemical context
The 4-piperidone scaffold has been used as a building block for the synthesis of more complex N-(1-phenethyl-4-piperidyl) propionanilide], a strong agonist of μ-opioid receptors, used for its potent analgesic activity. This industrial synthesis, patented by Janssen Pharmaceutica (Gupta et al., 2010) employs 4-piperidone hydrochloride monohydrate as the starting material. The range of biological activity for 4-piperidone derivatives is quite broad, including anti-inflammatory, anticancer, antibacterial and antifungal properties. For this reason, new synthetic methods are being sought proactively in this field (e.g. Tortolani & Poss, 1999; Davis et al., 2001; Das et al., 2010). For our part, our emphasis is on the synthesis of chiral N-substituted piperidone derivatives (e.g. Romero et al., 2007).
An example is the one-pot three-step synthesis of fentanyl [In this context, X-ray crystallography is a potent tool to assess the conformational modifications experienced by the piperidine heterocycle while its substitution pattern is altered along a synthetic route. The pair of structures reported here illustrates such conformational flexibility in this chemistry.
2. Structural commentary
The first piperidin-4-one derivative [(I), Fig. 1] is a non-sterically hindered molecule, and thus adopts the most stable chair conformation for the six-membered heterocycle. The total puckering amplitude is Q = 0.553 (3) Å, and the Cremer parameters are θ = 168.8 (3)° and φ = 171.8 (18)°. The deviation from the ideal conformation, θ = 180°, may be related to the heterocyclic nature of the ring, with short C—N bond lengths and longer C—C bond lengths, as expected. Moreover, atom C4 has a geometry consistent with its sp2 state, while N1 is essentially tetrahedral, with the lone pair occupying the axial position. The equatorial group substituting this N atom is rigid, as a result of its chiral character. However, the spatial orientation of this group allows the hydroxyl group to interact with the nitrogen lone pair, stabilizing the observed molecular conformation.
The chair conformation for the piperidone in (I) was previously observed in related compounds based on the same heterocycle (Vijayakumar et al., 2010; Rajesh et al., 2010a, 2012). Apparently, the only significant variation allowed for this system is for the N atom, which may approach a planar–trigonal geometry (Shahani et al., 2010; Rajesh et al., 2010b).
The chair conformation of (I) is, however, different from that observed for (II), derived from piperidine-2-thione (Fig. 2). In that case, the half-chair form is found in the characterized by a puckering amplitude Q = 0.513 (3) Å, and Cremer parameters θ = 127.5 (3)° and φ = 29.29 (5)° (ideal values: θ = 129.2° and φ = 30°). The N atom has a planar environment, the sum of angles about this center being 360°. This conformer is identical to one of the stable forms reported for piperidin-2-one (known as δ-valerolatcam): microwave spectroscopy indicated that for δ-valerolatcam, two conformers are stabilized in the gas phase, the half-chair form and the (Kuze et al., 1999). δ-Valerolatcam is actually comparable to (II), because in both molecules C4 has the same sp3 In (II), the C4 is part of the 1,3-dioxolane ring. The slightly twisted half-chair conformation for this ring is common. The two rings are almost perpendicular, as reflected in the dihedral angle between their mean-planes of 76.4 (2)°.
3. Effect of on ring conformation
Since the ring conformation in (II) seems not to be related to any intramolecular strong interaction nor the modification from sp2 to sp3 at C4, it should be a consequence of the presence of the thiocarbonyl functionality at C2. This center is in a state very close to pure sp2 This is reflected in the bond length for the C=S group, 1.677 (3) Å, close to the mean value of 1.669 Å computed from almost 10000 thiocarbonyl bonds retrieved from the organics subset of the CSD (Version 5.36 with all updates; Groom & Allen, 2014. The restriction to sp2-C centers is applied by requiring the C atom to be linked to exactly three atoms and the S atom to be linked to exactly one atom). Indeed, long C=S bonds, above 1.75 Å, are found in compounds including molecules having a propensity to form hydrogen bonds, like thiourea (Weber, 1984), thiourea derivatives (Busschaert et al., 2011; Chumakov et al., 2006), and trithiocarbonic acid (Krebs & Gattow, 1965), among others. In the case of a single C—S bond based on a sp3-hybridized C atom, the bond length is sharply distributed around 1.81 Å.
The other factor contributing to the ring conformation in (II) is the absence of the hydroxyl group in the chiral moiety, making the heterocyclic N atom inert towards potential interactions. The lone pair should thus be oriented randomly above and below the piperidine mean plane, through nitrogen inversion, characterized by a low energy barrier in the gas and solution phases. Both features, the planar N atom and the neighboring sp2-C atom, generate the half-chair conformation observed for the piperidine-2-thione core. In the present case, it is difficult to determine whether one feature dominates, or both are of importance for stabilizing the half-chair conformation. However, for the 25 hits corresponding to piperidine-2-ones deposited in the CSD, 21 of them present the same conformation as in (II), with C4 as the flap atom for the half-chair. In three cases, the puckering amplitude of the half-chair is close to 0 Å (Woydt et al., 1991; Bolla et al., 2014), and in one case, the ring presents a twist-boat conformation (Sanfilippo et al., 1992). In contrast, piperidine derivatives are stabilized almost universally in the chair conformation, with very few exceptions in some disordered structures (Thirumaran et al., 2009). These rules hold regardless of the substituent on the N atom. Applying these general rules to compounds (I) and (II), we thus infer that the ring conformation is mainly determined by the state of the C atom in position α to the piperidinic N atom.
4. Supramolecular features
In the crystal of (I), weak C—H⋯O hydrogen bonds link the molecules into supramolecular chains propagating along the b-axis direction (Table 1).
The is based on weak intermolecular C—H⋯S contacts involving one methylene group of the dioxolane ring and the thiocarbonyl functionality (Table 2), which forms chains along the 21 symmetry axis parallel to [010].
of (II)5. Synthesis and crystallization
Compound (I). The synthesis is illustrated in Fig. 3. A solution of compound (1), (R)-(−)-2-phenylglycinol (5.65 g, 41.2 mmol) with an excess of ethyl acrylate in methanol (60 mL), was stirred overnight at 298 K. The reaction mixture was concentrated, and the crude purified by (SiO2, CH2Cl2:MeOH, 97:3), to afford (2) as a colorless oil (98%). An amount of (2) (40.6 mmol) was added to a mixture of MeONa in anh. benzene. After refluxing the mixture for 5 h, a solid was obtained, which was filtered and dried in air. This solid was treated with AcOH:water (30%, v/v) until pH = 1, initiating the decarboxylation process. The mixture was refluxed until gas evolution stopped. After cooling down to 298 K, pH was adjusted to 7 with NaHCO3, and the mixture was washed with CH2Cl2 (3 × 50 ml). The organic phase was dried over Na2SO4, and concentrated. Compound (I) was purified by (SiO2, CH2Cl2:MeOH, 95:5). Compound (I) was obtained in 80% yield, and was recrystallized from an AcOEt:n-hexane mixture (1:1).
Compound (II). The synthesis is illustrated in Fig. 4. The synthesis of compound (3), (S)-(−)-phenylethylpiperi-2,4-dione, has been reported previously (Romero et al., 2013; see compound 5 in Fig. 1 of this report). To a solution of (3) in 50 mL of dry benzene, was added ethylene glycol (0.2 mL, 3.4 mmol) and a catalytic amount of p-TSA. The mixture was refluxed until water formation, collected with a Dean–Stark trap, stopped. Then, the reaction mixture was cooled down to room temperature, treated with brine, and washed with CH2Cl2 (3 × 50 mL). The organic phase was dried over Na2SO4, and then concentrated under reduced pressure. The crude reaction was purified by (SiO2, AcOEt:petroleum benzine), to afford compound (4) as a white oil, in 95% yield. Next, a suspension of Lawesson's reagent (0.234 g, 0.578 mmol) in dry toluene (60 mL) was refluxed until complete dissolution of the reagent. The solution was cooled to 313 K, and a solution of (4) in anh. toluene (0.151 g, 0.578 mmol, 20 mL) was added (Romero et al., 2007). The reaction mixture was stirred for 1 h to give (II) in 90% yield, after purification by (SiO2, petroleum ether:dicloromethane). The product was recrystallized from CH2Cl2:n-hexane (1:1).
6. Refinement
Crystal data, data collection and structure . All C-bound H atoms were placed in calculated positions, and refined as riding on their carrier atoms, and with C—H bond lengths fixed at 0.93 (aromatic CH), 0.96 (methyl CH3), 0.97 (methylene CH2), or 0.98 Å (methine CH). For (I), the hydroxyl H atom, H2, was first found in a difference map. Its position was fixed in the last least-squares cycles, with O2—H2 = 0.91 Å. For all H atoms, the isotropic displacement parameters were calculated as Uiso(H) = xUeq(carrier atom), where x = 1.5 for methyl and hydroxyl H atoms, and x = 1.2 otherwise. The for chiral centers C7 in (I) and (II) was assumed from the of starting materials used for the synthesis (see previous section). In the case of (II), which contains one site producing the expected enantiomer was confirmed by the of the (Parsons et al., 2013).
details are summarized in Table 3Supporting information
10.1107/S2056989015017119/xu5868sup1.cif
contains datablocks I, II, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989015017119/xu5868Isup2.hkl
Structure factors: contains datablock II. DOI: 10.1107/S2056989015017119/xu5868IIsup3.hkl
Supporting information file. DOI: 10.1107/S2056989015017119/xu5868Isup4.cml
Supporting information file. DOI: 10.1107/S2056989015017119/xu5868IIsup5.cml
The 4-piperidone scaffold has been used as a building block for the synthesis of more complex
An example is the one-pot three-step synthesis of fentanyl [N-(1-phenethyl-4-piperidyl) propionanilide], a strong agonist of µ-opioid receptors, used for its potent analgesic activity. This industrial synthesis, patented by Janssen Pharmaceutica (Gupta et al., 2010) employs 4-piperidone hydrochloride monohydrate as the starting material. The range of biological activity for 4-piperidone derivatives is quite broad, including anti-inflammatory, anticancer, antibacterial and antifungal properties. For this reason, new synthetic methods are being sought proactively in this field (e.g. Tortolani & Poss, 1999; Davis et al., 2001; Das et al., 2010). For our part, our emphasis is on the synthesis of chiral N-substituted piperidone derivatives (e.g. Romero et al., 2007).In this context, X-ray crystallography is a potent tool to assess the conformational modifications experienced by the piperidine heterocycle while its substitution pattern is altered along a synthetic route. The pair of structures reported here illustrates such conformational flexibility in this chemistry.
The first piperidin-4-one derivative [(I), Fig. 1] is a non-sterically hindered molecule, and thus adopts the most stable chair conformation for the six-membered heterocycle. The total puckering amplitude is Q = 0.553 (3) Å, and the Cremer parameters are θ = 168.8 (3)° and φ = 171.8 (18)°. The deviation from the ideal conformation, θ = 180°, may be related to the heterocyclic nature of the ring, with short C—N bond lengths and longer C—C bond lengths, as expected. Moreover, atom C4 has a geometry consistent with its sp2 state, while N1 is essentially tetrahedral, with the lone pair occupying the axial position. The equatorial group substituting this N atom is rigid, as a result of its chiral character. However, the spatial orientation of this group allows the hydroxyl group to interact with the nitrogen lone pair, stabilizing the observed molecular conformation.
The chair conformation for the piperidone in (I) was previously observed in related compounds based on the same heterocycle (Vijayakumar et al., 2010; Rajesh et al., 2010a, 2012). Apparently, the only significant variation allowed for this system is for the N atom, which may approach a planar–trigonal geometry (Shahani et al., 2010; Rajesh et al., 2010b).
The chair conformation of (I) is, however ,different from that observed for (II), derived from piperidine-2-thione (Fig. 2). In that case, the half-chair form is found in the θ = 127.5 (3)° and φ = 29.29 (5)° (ideal values: θ = 129.2° and φ = 30°). The N atom has a planar environment, the sum of angles about this center being 360°. This conformer is identical to one of the stable forms reported for piperidin-2-one (known as δ-valerolatcam): microwave spectroscopy indicated that for δ-valerolatcam, two conformers are stabilized in the gas phase, the half-chair form and the (Kuze et al., 1999). δ-Valerolatcam is actually comparable to (II), because in both molecules C4 has the same sp3 In (II), the C4 is part of the 1,3-dioxolane ring. The slightly twisted half-chair conformation for this ring is common. The two rings are almost perpendicular, as reflected in the dihedral angle between their mean-planes of 76.4 (2)°.
characterized by a puckering amplitude Q = 0.513 (3) Å, and Cremer parametersSince the ring conformation in (II) seems not to be related to any intramolecular strong interaction nor the ═S group, 1.677 (3) Å, close to the mean value of 1.669 Å computed from almost 10000 thiocarbonyl bonds retrieved from the organics subset of the CSD (Version 5.36 with all updates; Groom & Allen, 2014. The restriction to sp2-C centers is applied by requiring the C atom to be linked to exactly three atoms and the S atom to be linked to exactly one atom). Indeed, long C═S bonds, above 1.75 Å, are found in compounds including molecules having a propensity to form hydrogen bonds, like thiourea (Weber, 1984), thiourea derivatives (Busschaert et al., 2011; Chumakov et al., 2006), and trithiocarbonic acid (Krebs & Gattow, 1965), among others. In the case of a single C–S bond based on a sp3 hybridized C atom, the bond length is sharply distributed around 1.81 Å.
modification from sp2 to sp3 at C4, it should be a consequence of the presence of the thiocarbonyl functionality at C2. This center is in a state very close to pure sp2 This is reflected in the bond length for the CThe other factor contributing to the ring conformation in (II) is the absence of the hydroxyl group in the chiral moiety, making the heterocyclic N atom inert towards potential interactions. The lone pair should thus be oriented randomly above and below the piperidine mean plane, through nitrogen inversion, characterized by a low energy barrier in the gas and solution phases. Both features, the planar N atom and the neighboring sp2-C atom, generate the half-chair conformation observed for the piperidine-2-thione core. In the present case, it is difficult to determine whether one feature dominates, or both are of importance for stabilizing the half-chair conformation. However, for the 25 hits corresponding to piperidine-2-ones deposited in the CSD, 21 of them present the same conformation as in (II), with C4 as the flap atom for the half-chair. In three cases, the puckering amplitude of the half-chair is close to 0 Å (Woydt et al., 1991; Bolla et al., 2014), and in one case, the ring presents a twist-boat conformation (Sanfilippo et al., 1992). In contrast, piperidine derivatives are stabilized almost universally in the chair conformation, with very few exceptions in some disordered structures (Thirumaran et al., 2009). These rules hold regardless of the substituent on the N atom. Applying these general rules to compounds (I) and (II), we thus infer that the ring conformation is mainly determined by the α to the piperidinic N atom.
state of the C atom in positionIn the crystal of (I), weak C—H···O hydrogen bonds link the molecules into supramolecular chains propagating along the b-axis direction (Table 1).
The
of (II) is based on weak intermolecular C—H···S contacts involving one methylene group of the dioxolane ring and the thiocarbonyl functionality (Table 2), which forms chains along the 21 symmetry axis parallel to [010].Compound (I). The synthesis is illustrated in Fig. 3. A solution of compound (1), (R)-(–)-2-phenylglycinol (5.65 g, 41.2 mmol) with an excess of ethyl acrylate in methanol (60 mL), was stirred overnight at 298 K. The reaction mixture was concentrated, and the crude purified by
(SiO2, CH2Cl2:MeOH, 97:3), to afford (2) as a colorless oil (98 %). An amount of (2) (40.6 mmol) was added to a mixture of MeONa in anh. benzene. After refluxing the mixture for 5 h, a solid was obtained, which was filtered and dried in air. This solid was treated with AcOH:water (30%, v/v) until pH = 1, initiating the decarboxylation process. The mixture was refluxed until gas evolution stopped. After cooling down to 298 K, pH was adjusted to 7 with NaHCO3, and the mixture was washed with CH2Cl2 (3 × 50 ml). The organic phase was dried over Na2SO4, and concentrated. Compound (I) was purified by (SiO2, CH2Cl2:MeOH, 95:5). Compound (I) was obtained in 80% yield, and was recrystallized from an AcOEt:n-hexane mixture (1:1).Compound (II). The synthesis is illustrated in Fig. 4. The synthesis of compound (3), (S)-(–)-phenylethylpiperi-2,4-dione, has been reported previously (Romero et al., 2013; see compound 5 in Fig. 1 of this report). To a solution of (3) in 50 mL of dry benzene, was added ethylene glycol (0.2 mL, 3.4 mmol) and a catalytic amount of p-TSA. The mixture was refluxed until water formation, collected with a Dean–Stark trap, stopped. Then, the reaction mixture was cooled down to room temperature, treated with brine, and washed with CH2Cl2 (3 × 50 mL). The organic phase was dried over Na2SO4, and then concentrated under reduced pressure. The crude reaction was purified by
(SiO2, AcOEt:petroleum benzine), to afford compound (4) as a white oil, in 95 % yield. Next, a suspension of Lawesson's reagent (0.234 g, 0.578 mmol) in dry toluene (60 mL) was refluxed until complete dissolution of the reagent. The solution was cooled to 313 K, and a solution of (4) in anh. toluene (0.151 g, 0.578 mmol, 20 mL) was added (Romero et al., 2007). The reaction mixture was stirred for 1 h to give (II) in 90% yield, after purification by (SiO2, petroleum ether:dicloromethane). The product was recrystallized from CH2Cl2:n-hexane (1:1).Crystal data, data collection and structure
details are summarized in Table 3. All C-bound H atoms were placed in calculated positions, and refined as riding on their carrier atoms, and with C—H bond lengths fixed at 0.93 (aromatic CH), 0.96 (methyl CH3), 0.97 (methylene CH2), or 0.98 Å (methine CH). For (I), the hydroxyl H atom, H2, was first found in a difference map. Its position was fixed in the last least-squares cycles, with O2—H2 = 0.91 Å. For all H atoms, the isotropic displacement parameters were calculated as Uiso(H) = xUeq(carrier atom), where x = 1.5 for methyl and hydroxyl H atoms, and x = 1.2 otherwise. The for chiral centers C7 in (I) and (II) was assumed from the of starting materials used for the synthesis (see previous section). In the case of (II), which contains one site producing the expected enantiomer was confirmed by the of the (Parsons et al., 2013).For both compounds, data collection: XSCANS (Fait, 1996); cell
XSCANS (Fait, 1996); data reduction: XSCANS (Fait, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).Fig. 1. The molecular structure of (I), with displacement ellipsoids for non-H atoms at the 30% probability level. | |
Fig. 2. The molecular structure of (II), with displacement ellipsoids for non-H atoms at the 30% probability level. | |
Fig. 3. Synthesis of (I). Reaction conditions: (i) ethyl acrylate, MeOH, 298 K, 12 h; (ii) Na/MeOH, benzene, reflux, 5 h; (iii) AcOH/H2O (30% v/v), reflux. | |
Fig. 4. Synthesis of (II). Reaction conditions: (i) ethylene glycol, p-TSA, anhydrous benzene, reflux, 4 h; (ii) Lawesson's reagent in anhydrous toluene, 313 K, 1 h. |
C13H17NO2 | F(000) = 236 |
Mr = 219.27 | Dx = 1.212 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.7590 (11) Å | Cell parameters from 53 reflections |
b = 6.8952 (10) Å | θ = 3.7–11.1° |
c = 9.7980 (14) Å | µ = 0.08 mm−1 |
β = 114.348 (9)° | T = 296 K |
V = 600.67 (15) Å3 | Plate, pale yellow |
Z = 2 | 0.60 × 0.17 × 0.12 mm |
Bruker P4 diffractometer | Rint = 0.021 |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 2.3° |
Graphite monochromator | h = −11→4 |
2θ/ω scans | k = −1→8 |
2700 measured reflections | l = −10→11 |
1341 independent reflections | 3 standard reflections every 97 reflections |
1050 reflections with I > 2σ(I) | intensity decay: 0.5% |
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)] = 0.036 | H-atom parameters constrained |
wR(F2) = 0.083 | w = 1/[σ2(Fo2) + (0.0372P)2 + 0.0246P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
1341 reflections | Δρmax = 0.11 e Å−3 |
146 parameters | Δρmin = −0.11 e Å−3 |
1 restraint | Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 constraints | Extinction coefficient: 0.040 (6) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Assigned from the synthesis |
C13H17NO2 | V = 600.67 (15) Å3 |
Mr = 219.27 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 9.7590 (11) Å | µ = 0.08 mm−1 |
b = 6.8952 (10) Å | T = 296 K |
c = 9.7980 (14) Å | 0.60 × 0.17 × 0.12 mm |
β = 114.348 (9)° |
Bruker P4 diffractometer | Rint = 0.021 |
2700 measured reflections | 3 standard reflections every 97 reflections |
1341 independent reflections | intensity decay: 0.5% |
1050 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.036 | 1 restraint |
wR(F2) = 0.083 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.11 e Å−3 |
1341 reflections | Δρmin = −0.11 e Å−3 |
146 parameters | Absolute structure: Assigned from the synthesis |
x | y | z | Uiso*/Ueq | ||
N1 | 0.8276 (2) | 0.3211 (3) | 0.1078 (2) | 0.0427 (5) | |
O1 | 0.9225 (3) | 0.7423 (5) | 0.4197 (3) | 0.1214 (11) | |
O2 | 0.7952 (2) | −0.0767 (3) | 0.0760 (3) | 0.0797 (7) | |
H2 | 0.8389 | 0.0052 | 0.1543 | 0.120* | |
C2 | 0.9480 (3) | 0.4619 (4) | 0.1324 (3) | 0.0502 (7) | |
H2B | 0.9068 | 0.5750 | 0.0700 | 0.060* | |
H2C | 1.0229 | 0.4047 | 0.1036 | 0.060* | |
C3 | 1.0222 (3) | 0.5237 (5) | 0.2969 (3) | 0.0629 (9) | |
H3A | 1.0773 | 0.4150 | 0.3575 | 0.075* | |
H3B | 1.0934 | 0.6273 | 0.3082 | 0.075* | |
C4 | 0.9084 (4) | 0.5914 (6) | 0.3506 (3) | 0.0708 (10) | |
C5 | 0.7746 (3) | 0.4646 (5) | 0.3102 (3) | 0.0613 (9) | |
H5A | 0.6983 | 0.5313 | 0.3318 | 0.074* | |
H5B | 0.8025 | 0.3476 | 0.3705 | 0.074* | |
C6 | 0.7102 (3) | 0.4101 (4) | 0.1448 (2) | 0.0491 (7) | |
H6A | 0.6277 | 0.3196 | 0.1226 | 0.059* | |
H6B | 0.6716 | 0.5252 | 0.0840 | 0.059* | |
C7 | 0.7704 (3) | 0.2371 (4) | −0.0447 (3) | 0.0461 (7) | |
H7A | 0.8596 | 0.2074 | −0.0631 | 0.055* | |
C8 | 0.6978 (3) | 0.0421 (4) | −0.0420 (3) | 0.0626 (8) | |
H8A | 0.6054 | 0.0634 | −0.0296 | 0.075* | |
H8B | 0.6726 | −0.0237 | −0.1368 | 0.075* | |
C9 | 0.6741 (3) | 0.3692 (4) | −0.1714 (2) | 0.0460 (7) | |
C10 | 0.7397 (3) | 0.4820 (5) | −0.2455 (3) | 0.0570 (8) | |
H10A | 0.8428 | 0.4733 | −0.2180 | 0.068* | |
C11 | 0.6544 (4) | 0.6079 (6) | −0.3602 (3) | 0.0737 (9) | |
H11A | 0.7010 | 0.6837 | −0.4072 | 0.088* | |
C12 | 0.5013 (4) | 0.6203 (6) | −0.4042 (3) | 0.0786 (10) | |
H12A | 0.4440 | 0.7028 | −0.4819 | 0.094* | |
C13 | 0.4338 (4) | 0.5101 (5) | −0.3326 (3) | 0.0684 (9) | |
H13A | 0.3304 | 0.5181 | −0.3620 | 0.082* | |
C14 | 0.5188 (3) | 0.3872 (4) | −0.2169 (3) | 0.0541 (7) | |
H14A | 0.4716 | 0.3151 | −0.1684 | 0.065* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0361 (11) | 0.0413 (12) | 0.0519 (12) | 0.0012 (11) | 0.0192 (9) | 0.0002 (11) |
O1 | 0.130 (2) | 0.119 (2) | 0.104 (2) | −0.022 (2) | 0.0365 (16) | −0.062 (2) |
O2 | 0.0924 (15) | 0.0412 (12) | 0.1027 (14) | 0.0085 (13) | 0.0374 (12) | 0.0124 (13) |
C2 | 0.0445 (14) | 0.0492 (17) | 0.0558 (14) | −0.0064 (15) | 0.0194 (11) | 0.0027 (14) |
C3 | 0.0533 (16) | 0.068 (2) | 0.0566 (15) | −0.0138 (18) | 0.0114 (13) | 0.0026 (17) |
C4 | 0.080 (2) | 0.077 (3) | 0.0418 (14) | 0.003 (2) | 0.0114 (15) | −0.0097 (18) |
C5 | 0.0580 (16) | 0.080 (2) | 0.0481 (14) | 0.0064 (19) | 0.0243 (13) | −0.0025 (17) |
C6 | 0.0442 (13) | 0.0563 (18) | 0.0487 (13) | 0.0012 (16) | 0.0210 (11) | −0.0009 (15) |
C7 | 0.0480 (14) | 0.0403 (14) | 0.0555 (15) | 0.0030 (14) | 0.0270 (12) | −0.0042 (14) |
C8 | 0.0660 (19) | 0.0403 (16) | 0.0795 (19) | −0.0022 (16) | 0.0281 (16) | −0.0061 (16) |
C9 | 0.0559 (15) | 0.0404 (17) | 0.0435 (13) | −0.0022 (15) | 0.0222 (12) | −0.0068 (14) |
C10 | 0.0677 (17) | 0.0555 (18) | 0.0520 (15) | −0.0106 (17) | 0.0287 (14) | −0.0061 (16) |
C11 | 0.104 (3) | 0.061 (2) | 0.0584 (17) | −0.011 (2) | 0.0357 (18) | 0.0015 (19) |
C12 | 0.101 (3) | 0.065 (2) | 0.0548 (17) | 0.008 (2) | 0.0177 (19) | 0.0020 (19) |
C13 | 0.0633 (18) | 0.071 (2) | 0.0594 (17) | 0.0094 (19) | 0.0132 (15) | −0.0004 (18) |
C14 | 0.0546 (15) | 0.0540 (19) | 0.0515 (14) | −0.0038 (16) | 0.0195 (13) | −0.0051 (15) |
N1—C2 | 1.466 (3) | C6—H6B | 0.9700 |
N1—C6 | 1.469 (3) | C7—C9 | 1.514 (4) |
N1—C7 | 1.481 (3) | C7—C8 | 1.525 (4) |
O1—C4 | 1.217 (4) | C7—H7A | 0.9800 |
O2—C8 | 1.416 (3) | C8—H8A | 0.9700 |
O2—H2 | 0.9051 | C8—H8B | 0.9700 |
C2—C3 | 1.530 (4) | C9—C10 | 1.387 (4) |
C2—H2B | 0.9700 | C9—C14 | 1.398 (3) |
C2—H2C | 0.9700 | C10—C11 | 1.392 (5) |
C3—C4 | 1.487 (5) | C10—H10A | 0.9300 |
C3—H3A | 0.9700 | C11—C12 | 1.376 (4) |
C3—H3B | 0.9700 | C11—H11A | 0.9300 |
C4—C5 | 1.483 (5) | C12—C13 | 1.373 (5) |
C5—C6 | 1.524 (3) | C12—H12A | 0.9300 |
C5—H5A | 0.9700 | C13—C14 | 1.385 (4) |
C5—H5B | 0.9700 | C13—H13A | 0.9300 |
C6—H6A | 0.9700 | C14—H14A | 0.9300 |
C2—N1—C6 | 109.7 (2) | N1—C7—C9 | 116.1 (2) |
C2—N1—C7 | 111.57 (19) | N1—C7—C8 | 108.1 (2) |
C6—N1—C7 | 113.85 (17) | C9—C7—C8 | 114.2 (2) |
C8—O2—H2 | 104.7 | N1—C7—H7A | 105.9 |
N1—C2—C3 | 110.9 (2) | C9—C7—H7A | 105.9 |
N1—C2—H2B | 109.5 | C8—C7—H7A | 105.9 |
C3—C2—H2B | 109.5 | O2—C8—C7 | 111.4 (2) |
N1—C2—H2C | 109.5 | O2—C8—H8A | 109.4 |
C3—C2—H2C | 109.5 | C7—C8—H8A | 109.4 |
H2B—C2—H2C | 108.0 | O2—C8—H8B | 109.4 |
C4—C3—C2 | 111.2 (2) | C7—C8—H8B | 109.4 |
C4—C3—H3A | 109.4 | H8A—C8—H8B | 108.0 |
C2—C3—H3A | 109.4 | C10—C9—C14 | 117.2 (2) |
C4—C3—H3B | 109.4 | C10—C9—C7 | 120.1 (2) |
C2—C3—H3B | 109.4 | C14—C9—C7 | 122.7 (2) |
H3A—C3—H3B | 108.0 | C9—C10—C11 | 121.4 (3) |
O1—C4—C5 | 122.6 (3) | C9—C10—H10A | 119.3 |
O1—C4—C3 | 122.3 (4) | C11—C10—H10A | 119.3 |
C5—C4—C3 | 115.1 (3) | C12—C11—C10 | 120.2 (3) |
C4—C5—C6 | 111.1 (2) | C12—C11—H11A | 119.9 |
C4—C5—H5A | 109.4 | C10—C11—H11A | 119.9 |
C6—C5—H5A | 109.4 | C13—C12—C11 | 119.5 (3) |
C4—C5—H5B | 109.4 | C13—C12—H12A | 120.2 |
C6—C5—H5B | 109.4 | C11—C12—H12A | 120.2 |
H5A—C5—H5B | 108.0 | C12—C13—C14 | 120.4 (3) |
N1—C6—C5 | 110.09 (19) | C12—C13—H13A | 119.8 |
N1—C6—H6A | 109.6 | C14—C13—H13A | 119.8 |
C5—C6—H6A | 109.6 | C13—C14—C9 | 121.4 (3) |
N1—C6—H6B | 109.6 | C13—C14—H14A | 119.3 |
C5—C6—H6B | 109.6 | C9—C14—H14A | 119.3 |
H6A—C6—H6B | 108.2 | ||
C6—N1—C2—C3 | 61.7 (3) | N1—C7—C8—O2 | −50.9 (3) |
C7—N1—C2—C3 | −171.2 (2) | C9—C7—C8—O2 | 178.2 (2) |
N1—C2—C3—C4 | −52.6 (4) | N1—C7—C9—C10 | 91.9 (3) |
C2—C3—C4—O1 | −131.9 (3) | C8—C7—C9—C10 | −141.3 (2) |
C2—C3—C4—C5 | 46.5 (4) | N1—C7—C9—C14 | −86.8 (3) |
O1—C4—C5—C6 | 130.5 (3) | C8—C7—C9—C14 | 40.1 (3) |
C3—C4—C5—C6 | −47.9 (4) | C14—C9—C10—C11 | 0.1 (4) |
C2—N1—C6—C5 | −62.8 (3) | C7—C9—C10—C11 | −178.6 (3) |
C7—N1—C6—C5 | 171.4 (2) | C9—C10—C11—C12 | −1.1 (5) |
C4—C5—C6—N1 | 55.1 (4) | C10—C11—C12—C13 | 1.0 (5) |
C2—N1—C7—C9 | −73.2 (3) | C11—C12—C13—C14 | 0.0 (5) |
C6—N1—C7—C9 | 51.5 (3) | C12—C13—C14—C9 | −1.0 (5) |
C2—N1—C7—C8 | 157.0 (2) | C10—C9—C14—C13 | 1.0 (4) |
C6—N1—C7—C8 | −78.3 (3) | C7—C9—C14—C13 | 179.6 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···N1 | 0.91 | 2.22 | 2.764 (3) | 118 |
C2—H2B···O2i | 0.97 | 2.65 | 3.460 (4) | 142 |
C3—H3A···O1ii | 0.97 | 2.49 | 3.246 (4) | 135 |
Symmetry codes: (i) x, y+1, z; (ii) −x+2, y−1/2, −z+1. |
C15H19NO2S | Dx = 1.279 Mg m−3 |
Mr = 277.37 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 58 reflections |
a = 5.9731 (13) Å | θ = 4.7–12.5° |
b = 14.948 (3) Å | µ = 0.22 mm−1 |
c = 16.127 (3) Å | T = 296 K |
V = 1439.9 (5) Å3 | Irregular, colourless |
Z = 4 | 0.60 × 0.38 × 0.36 mm |
F(000) = 592 |
Bruker P4 diffractometer | 2007 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.029 |
Graphite monochromator | θmax = 27.5°, θmin = 1.9° |
2θ/ω scans | h = −7→3 |
Absorption correction: ψ scan (XSCANS; Fait, 1996) | k = −19→19 |
Tmin = 0.760, Tmax = 0.922 | l = −20→20 |
3886 measured reflections | 3 standard reflections every 97 reflections |
2631 independent reflections | intensity decay: 1.5% |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.044 | w = 1/[σ2(Fo2) + (0.0668P)2 + 0.0631P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.120 | (Δ/σ)max < 0.001 |
S = 1.06 | Δρmax = 0.19 e Å−3 |
2631 reflections | Δρmin = −0.24 e Å−3 |
174 parameters | Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.014 (4) |
0 constraints | Absolute structure: Flack x determined using 483 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.08 (7) |
Secondary atom site location: difference Fourier map |
C15H19NO2S | V = 1439.9 (5) Å3 |
Mr = 277.37 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 5.9731 (13) Å | µ = 0.22 mm−1 |
b = 14.948 (3) Å | T = 296 K |
c = 16.127 (3) Å | 0.60 × 0.38 × 0.36 mm |
Bruker P4 diffractometer | 2007 reflections with I > 2σ(I) |
Absorption correction: ψ scan (XSCANS; Fait, 1996) | Rint = 0.029 |
Tmin = 0.760, Tmax = 0.922 | 3 standard reflections every 97 reflections |
3886 measured reflections | intensity decay: 1.5% |
2631 independent reflections |
R[F2 > 2σ(F2)] = 0.044 | H-atom parameters constrained |
wR(F2) = 0.120 | Δρmax = 0.19 e Å−3 |
S = 1.06 | Δρmin = −0.24 e Å−3 |
2631 reflections | Absolute structure: Flack x determined using 483 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
174 parameters | Absolute structure parameter: 0.08 (7) |
0 restraints |
x | y | z | Uiso*/Ueq | ||
S1 | 0.90206 (18) | 0.38336 (6) | 0.64284 (6) | 0.0676 (3) | |
N1 | 0.5705 (4) | 0.49810 (13) | 0.61607 (13) | 0.0409 (6) | |
C2 | 0.7114 (5) | 0.46066 (19) | 0.66903 (18) | 0.0435 (7) | |
C3 | 0.6996 (6) | 0.4875 (2) | 0.75975 (18) | 0.0522 (8) | |
H3A | 0.6350 | 0.4383 | 0.7909 | 0.063* | |
H3B | 0.8509 | 0.4964 | 0.7800 | 0.063* | |
C4 | 0.5660 (6) | 0.57054 (18) | 0.77730 (17) | 0.0459 (7) | |
C5 | 0.3483 (6) | 0.5637 (2) | 0.73219 (19) | 0.0532 (8) | |
H5A | 0.2547 | 0.6147 | 0.7456 | 0.064* | |
H5B | 0.2702 | 0.5098 | 0.7490 | 0.064* | |
C6 | 0.3927 (6) | 0.5612 (2) | 0.63970 (17) | 0.0564 (8) | |
H6A | 0.2557 | 0.5447 | 0.6113 | 0.068* | |
H6B | 0.4342 | 0.6207 | 0.6213 | 0.068* | |
C7 | 0.5849 (6) | 0.47717 (17) | 0.52588 (16) | 0.0454 (7) | |
H7A | 0.7363 | 0.4545 | 0.5156 | 0.054* | |
C8 | 0.4240 (8) | 0.40247 (19) | 0.5035 (2) | 0.0663 (10) | |
H8A | 0.4611 | 0.3498 | 0.5346 | 0.099* | |
H8B | 0.4353 | 0.3898 | 0.4453 | 0.099* | |
H8C | 0.2738 | 0.4205 | 0.5164 | 0.099* | |
C9 | 0.5595 (6) | 0.56255 (18) | 0.47498 (16) | 0.0434 (7) | |
C10 | 0.3737 (6) | 0.5799 (2) | 0.42688 (18) | 0.0525 (8) | |
H10A | 0.2566 | 0.5390 | 0.4250 | 0.063* | |
C11 | 0.3612 (8) | 0.6593 (2) | 0.38083 (18) | 0.0635 (10) | |
H11A | 0.2348 | 0.6712 | 0.3490 | 0.076* | |
C12 | 0.5336 (8) | 0.7192 (2) | 0.3824 (2) | 0.0689 (11) | |
H12A | 0.5256 | 0.7714 | 0.3512 | 0.083* | |
C13 | 0.7186 (8) | 0.7023 (2) | 0.4302 (2) | 0.0684 (11) | |
H13A | 0.8356 | 0.7433 | 0.4319 | 0.082* | |
C14 | 0.7310 (6) | 0.6238 (2) | 0.4760 (2) | 0.0559 (8) | |
H14A | 0.8576 | 0.6125 | 0.5079 | 0.067* | |
O15 | 0.6883 (5) | 0.64740 (15) | 0.75095 (14) | 0.0743 (8) | |
C16 | 0.6637 (12) | 0.7128 (3) | 0.8120 (3) | 0.120 (2) | |
H16A | 0.5799 | 0.7632 | 0.7902 | 0.144* | |
H16B | 0.8095 | 0.7341 | 0.8297 | 0.144* | |
C17 | 0.5447 (8) | 0.6734 (2) | 0.8821 (2) | 0.0666 (11) | |
H17A | 0.6241 | 0.6845 | 0.9335 | 0.080* | |
H17B | 0.3948 | 0.6979 | 0.8865 | 0.080* | |
O18 | 0.5371 (4) | 0.57972 (13) | 0.86428 (12) | 0.0553 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0725 (6) | 0.0688 (6) | 0.0615 (5) | 0.0339 (5) | −0.0020 (5) | −0.0005 (4) |
N1 | 0.0465 (14) | 0.0369 (11) | 0.0393 (11) | 0.0038 (12) | 0.0012 (12) | 0.0018 (10) |
C2 | 0.0438 (16) | 0.0412 (14) | 0.0456 (15) | 0.0002 (14) | −0.0005 (14) | 0.0061 (12) |
C3 | 0.0563 (19) | 0.0588 (18) | 0.0414 (15) | 0.0078 (18) | −0.0023 (15) | 0.0039 (14) |
C4 | 0.0578 (19) | 0.0404 (14) | 0.0393 (13) | −0.0059 (16) | 0.0102 (15) | 0.0043 (12) |
C5 | 0.054 (2) | 0.0551 (17) | 0.0501 (16) | 0.0096 (17) | 0.0064 (16) | 0.0031 (14) |
C6 | 0.065 (2) | 0.0605 (18) | 0.0440 (15) | 0.0239 (18) | 0.0021 (18) | 0.0016 (14) |
C7 | 0.0583 (19) | 0.0392 (13) | 0.0386 (13) | 0.0007 (16) | 0.0001 (16) | 0.0003 (11) |
C8 | 0.093 (3) | 0.0462 (17) | 0.0593 (18) | −0.013 (2) | −0.008 (2) | 0.0002 (13) |
C9 | 0.0552 (19) | 0.0385 (13) | 0.0365 (12) | 0.0012 (15) | 0.0025 (14) | −0.0025 (11) |
C10 | 0.059 (2) | 0.0548 (16) | 0.0431 (14) | −0.0025 (17) | −0.0062 (17) | 0.0039 (13) |
C11 | 0.074 (3) | 0.071 (2) | 0.0461 (16) | 0.010 (2) | −0.0115 (18) | 0.0122 (16) |
C12 | 0.099 (3) | 0.0540 (18) | 0.0543 (17) | 0.003 (2) | 0.008 (2) | 0.0160 (16) |
C13 | 0.084 (3) | 0.0496 (19) | 0.072 (2) | −0.015 (2) | 0.003 (2) | 0.0105 (16) |
C14 | 0.0551 (19) | 0.0547 (18) | 0.0580 (18) | −0.0086 (18) | −0.0075 (17) | 0.0077 (16) |
O15 | 0.108 (2) | 0.0544 (12) | 0.0601 (13) | −0.0289 (14) | 0.0275 (15) | −0.0022 (11) |
C16 | 0.200 (7) | 0.062 (2) | 0.097 (3) | −0.060 (4) | 0.057 (4) | −0.022 (2) |
C17 | 0.100 (3) | 0.0484 (17) | 0.0516 (17) | −0.005 (2) | 0.006 (2) | −0.0045 (14) |
O18 | 0.0793 (17) | 0.0454 (10) | 0.0412 (10) | −0.0079 (12) | 0.0118 (11) | 0.0009 (8) |
S1—C2 | 1.677 (3) | C8—H8B | 0.9600 |
N1—C2 | 1.323 (4) | C8—H8C | 0.9600 |
N1—C6 | 1.471 (4) | C9—C14 | 1.375 (5) |
N1—C7 | 1.490 (3) | C9—C10 | 1.379 (5) |
C2—C3 | 1.519 (4) | C10—C11 | 1.402 (4) |
C3—C4 | 1.503 (4) | C10—H10A | 0.9300 |
C3—H3A | 0.9700 | C11—C12 | 1.365 (6) |
C3—H3B | 0.9700 | C11—H11A | 0.9300 |
C4—O18 | 1.420 (3) | C12—C13 | 1.370 (6) |
C4—O15 | 1.426 (3) | C12—H12A | 0.9300 |
C4—C5 | 1.493 (5) | C13—C14 | 1.388 (5) |
C5—C6 | 1.515 (4) | C13—H13A | 0.9300 |
C5—H5A | 0.9700 | C14—H14A | 0.9300 |
C5—H5B | 0.9700 | O15—C16 | 1.395 (4) |
C6—H6A | 0.9700 | C16—C17 | 1.459 (5) |
C6—H6B | 0.9700 | C16—H16A | 0.9700 |
C7—C8 | 1.517 (4) | C16—H16B | 0.9700 |
C7—C9 | 1.525 (4) | C17—O18 | 1.430 (3) |
C7—H7A | 0.9800 | C17—H17A | 0.9700 |
C8—H8A | 0.9600 | C17—H17B | 0.9700 |
C2—N1—C6 | 124.3 (2) | C7—C8—H8B | 109.5 |
C2—N1—C7 | 120.3 (3) | H8A—C8—H8B | 109.5 |
C6—N1—C7 | 115.4 (2) | C7—C8—H8C | 109.5 |
N1—C2—C3 | 118.7 (3) | H8A—C8—H8C | 109.5 |
N1—C2—S1 | 124.1 (2) | H8B—C8—H8C | 109.5 |
C3—C2—S1 | 117.1 (2) | C14—C9—C10 | 118.8 (3) |
C4—C3—C2 | 115.1 (2) | C14—C9—C7 | 118.5 (3) |
C4—C3—H3A | 108.5 | C10—C9—C7 | 122.7 (3) |
C2—C3—H3A | 108.5 | C9—C10—C11 | 120.0 (3) |
C4—C3—H3B | 108.5 | C9—C10—H10A | 120.0 |
C2—C3—H3B | 108.5 | C11—C10—H10A | 120.0 |
H3A—C3—H3B | 107.5 | C12—C11—C10 | 120.3 (4) |
O18—C4—O15 | 106.2 (2) | C12—C11—H11A | 119.8 |
O18—C4—C5 | 112.5 (3) | C10—C11—H11A | 119.8 |
O15—C4—C5 | 110.8 (3) | C11—C12—C13 | 119.9 (3) |
O18—C4—C3 | 109.3 (2) | C11—C12—H12A | 120.0 |
O15—C4—C3 | 109.7 (3) | C13—C12—H12A | 120.0 |
C5—C4—C3 | 108.3 (3) | C12—C13—C14 | 119.8 (4) |
C4—C5—C6 | 109.2 (3) | C12—C13—H13A | 120.1 |
C4—C5—H5A | 109.8 | C14—C13—H13A | 120.1 |
C6—C5—H5A | 109.8 | C9—C14—C13 | 121.1 (3) |
C4—C5—H5B | 109.8 | C9—C14—H14A | 119.4 |
C6—C5—H5B | 109.8 | C13—C14—H14A | 119.4 |
H5A—C5—H5B | 108.3 | C16—O15—C4 | 107.5 (3) |
N1—C6—C5 | 113.4 (2) | O15—C16—C17 | 108.3 (3) |
N1—C6—H6A | 108.9 | O15—C16—H16A | 110.0 |
C5—C6—H6A | 108.9 | C17—C16—H16A | 110.0 |
N1—C6—H6B | 108.9 | O15—C16—H16B | 110.0 |
C5—C6—H6B | 108.9 | C17—C16—H16B | 110.0 |
H6A—C6—H6B | 107.7 | H16A—C16—H16B | 108.4 |
N1—C7—C8 | 110.5 (3) | O18—C17—C16 | 104.8 (3) |
N1—C7—C9 | 110.1 (2) | O18—C17—H17A | 110.8 |
C8—C7—C9 | 115.2 (3) | C16—C17—H17A | 110.8 |
N1—C7—H7A | 106.9 | O18—C17—H17B | 110.8 |
C8—C7—H7A | 106.9 | C16—C17—H17B | 110.8 |
C9—C7—H7A | 106.9 | H17A—C17—H17B | 108.9 |
C7—C8—H8A | 109.5 | C4—O18—C17 | 106.8 (2) |
C6—N1—C2—C3 | −3.5 (4) | C8—C7—C9—C14 | −163.6 (3) |
C7—N1—C2—C3 | 176.7 (3) | N1—C7—C9—C10 | −110.5 (3) |
C6—N1—C2—S1 | 175.5 (2) | C8—C7—C9—C10 | 15.2 (4) |
C7—N1—C2—S1 | −4.3 (4) | C14—C9—C10—C11 | −0.6 (5) |
N1—C2—C3—C4 | −14.3 (4) | C7—C9—C10—C11 | −179.4 (3) |
S1—C2—C3—C4 | 166.7 (2) | C9—C10—C11—C12 | 0.9 (5) |
C2—C3—C4—O18 | 170.4 (3) | C10—C11—C12—C13 | −0.9 (6) |
C2—C3—C4—O15 | −73.6 (4) | C11—C12—C13—C14 | 0.8 (6) |
C2—C3—C4—C5 | 47.6 (4) | C10—C9—C14—C13 | 0.5 (5) |
O18—C4—C5—C6 | 175.7 (2) | C7—C9—C14—C13 | 179.3 (3) |
O15—C4—C5—C6 | 57.1 (3) | C12—C13—C14—C9 | −0.5 (5) |
C3—C4—C5—C6 | −63.4 (3) | O18—C4—O15—C16 | −19.9 (5) |
C2—N1—C6—C5 | −13.5 (4) | C5—C4—O15—C16 | 102.5 (4) |
C7—N1—C6—C5 | 166.3 (3) | C3—C4—O15—C16 | −137.9 (4) |
C4—C5—C6—N1 | 47.2 (4) | C4—O15—C16—C17 | 6.2 (6) |
C2—N1—C7—C8 | 94.8 (4) | O15—C16—C17—O18 | 9.6 (6) |
C6—N1—C7—C8 | −85.0 (3) | O15—C4—O18—C17 | 26.1 (4) |
C2—N1—C7—C9 | −136.8 (3) | C5—C4—O18—C17 | −95.3 (3) |
C6—N1—C7—C9 | 43.4 (4) | C3—C4—O18—C17 | 144.4 (3) |
N1—C7—C9—C14 | 70.7 (4) | C16—C17—O18—C4 | −21.9 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7A···S1 | 0.98 | 2.51 | 3.019 (3) | 112 |
C16—H16B···S1i | 0.97 | 2.85 | 3.709 (5) | 148 |
Symmetry code: (i) −x+2, y+1/2, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3A···O1i | 0.97 | 2.49 | 3.246 (4) | 135.0 |
Symmetry code: (i) −x+2, y−1/2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C16—H16B···S1i | 0.97 | 2.85 | 3.709 (5) | 147.6 |
Symmetry code: (i) −x+2, y+1/2, −z+3/2. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C13H17NO2 | C15H19NO2S |
Mr | 219.27 | 277.37 |
Crystal system, space group | Monoclinic, P21 | Orthorhombic, P212121 |
Temperature (K) | 296 | 296 |
a, b, c (Å) | 9.7590 (11), 6.8952 (10), 9.7980 (14) | 5.9731 (13), 14.948 (3), 16.127 (3) |
α, β, γ (°) | 90, 114.348 (9), 90 | 90, 90, 90 |
V (Å3) | 600.67 (15) | 1439.9 (5) |
Z | 2 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.08 | 0.22 |
Crystal size (mm) | 0.60 × 0.17 × 0.12 | 0.60 × 0.38 × 0.36 |
Data collection | ||
Diffractometer | Bruker P4 diffractometer | Bruker P4 diffractometer |
Absorption correction | – | ψ scan (XSCANS; Fait, 1996) |
Tmin, Tmax | – | 0.760, 0.922 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2700, 1341, 1050 | 3886, 2631, 2007 |
Rint | 0.021 | 0.029 |
(sin θ/λ)max (Å−1) | 0.595 | 0.650 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.083, 1.04 | 0.044, 0.120, 1.06 |
No. of reflections | 1341 | 2631 |
No. of parameters | 146 | 174 |
No. of restraints | 1 | 0 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.11, −0.11 | 0.19, −0.24 |
Absolute structure | Assigned from the synthesis | Flack x determined using 483 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
Absolute structure parameter | ? | 0.08 (7) |
Computer programs: XSCANS (Fait, 1996), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), SHELXTL (Sheldrick, 2008).
Acknowledgements
The authors thank the `Programa de Fortalecimiento a la Investigación' of the Universidad Juárez Autónoma de Tabasco for financial support via the project UJAT-2013-IB-13.
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