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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 71| Part 1| January 2015| Pages o41-o42
https://doi.org/10.1107/S2056989014026711

Crystal structure of (2S,4R)-ethyl 4-nitro­methyl-1-[(S)-1-phenyl­eth­yl]-6-sulfanyl­­idene­piperidine-2-carboxyl­ate

Araceli Zárate,a David Aparicio,a Angel Palilleroa and Angel Mendozaa*

aCentro de Química, ICUAP, Benemérita Universidad Autónoma de Puebla, 72570, Puebla, Puebla, Mexico
*Correspondence e-mail: angel.mendoza@correo.buap.mx

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 4 December 2014; accepted 4 December 2014; online 1 January 2015)

In the title compound, C17H22N2O4S, a thio­piperidine derivative, the piperidine ring has an envelope conformation with the methyl­ene C atom opposite to the C=S bond as the flap. The nitro­methyl substituent is equatorial while the eth­oxy­carbonyl group is axial. The mean planes of the nitro­methyl group, the carb­oxy group and phenyl ring are inclined to the mean plane through the five planar atoms of the piperidine ring [maximum deviation = 0.070 (4) Å] by 56.8 (2), 83.8 (5) and 87.1 (2)°, respectively. There is an intra­molecular C—H⋯O hydrogen bond involving an H atom of the eth­oxy­carbonyl group and a nitro O atom. In the crystal, mol­ecules are linked by C—H⋯O hydrogen bonds, forming chains along [100]. The chains are linked by further C—H⋯O hydrogen bonds, forming corrugated layers lying parallel to (001).

CCDC reference: 1037775

Similar articles

1. Related literature

For general background on piperidines and their derivatives, see: Poupart et al. (1999[Poupart, M. A., Fazal, G., Goulet, S. & Mar, L. T. (1999). J. Org. Chem. 64, 1356-1361.]); Pinnick et al. (1990[Pinnick, H. W. (1990). Org. React. 38, 655-792.]); Mukaiyama & Hoshino (1960[Mukaiyama, T. & Hoshino, T. J. (1960). J. Am. Chem. Soc. 82, 5339-5342.]); Ballini et al. (2007[Ballini, R., Palmieri, A. & Righi, P. (2007). Tetrahedron, 63, 12099-12121.]); Sośnicki (2009[Sośnicki, J. G. (2009). Tetrahedron, 65, 1336-1348.]). For their biological activity, see: Leung et al. (2000[Leung, D., Abbenante, G. & Fairlie, D. P. (2000). J. Med. Chem. 43, 305-341.]). For their use in organometallic reactions, see: Tamaru et al. (1978[Tamaru, Y., Harada, T., Iwamoto, H. & Yoshida, Z. (1978). J. Am. Chem. Soc. 100, 5221-5223.], 1979[Tamaru, Y., Harada, T. & Yoshida, Z. (1979). J. Am. Chem. Soc. 101, 1316-1318.]). For details of the Cambridge Structural Database, see: Groom & Allen (2014[Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662-671.]).

[Scheme 1]

2. Experimental

2.1. Crystal data

  • C17H22N2O4S

  • Mr = 350.42

  • Orthorhombic, P 21 21 21

  • a = 5.7999 (2) Å

  • b = 10.0103 (6) Å

  • c = 30.4050 (18) Å

  • V = 1765.28 (16) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.21 mm−1

  • T = 293 K

  • 0.20 × 0.09 × 0.05 mm

2.2. Data collection

  • Agilent Xcalibur Atlas Gemini diffractometer

  • Absorption correction: analytical (CrysAlis PRO; Agilent, 2014[Agilent (2014). CrysAlis PRO. Agilent Technologies, Yarnton, England.]) Tmin = 0.979, Tmax = 0.991

  • 8486 measured reflections

  • 3373 independent reflections

  • 2306 reflections with I > 2σ(I)

  • Rint = 0.054

2.3. Refinement

  • R[F2 > 2σ(F2)] = 0.056

  • wR(F2) = 0.104

  • S = 1.04

  • 3373 reflections

  • 219 parameters

  • H-atom parameters constrained

  • Δρmax = 0.18 e Å−3

  • Δρmin = −0.18 e Å−3

  • Absolute structure: Flack x determined using 705 quotients [(I+)−(I−)]/[(I+)+(I−)] (Parsons et al., 2013[Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249-259.])

  • Absolute structure parameter: 0.16 (8)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
C16—H16A⋯O3 0.96 2.49 3.419 (8) 163
C2—H2A⋯O1i 0.97 2.55 3.404 (5) 147
C17—H17B⋯O3ii 0.97 2.58 3.380 (6) 140
Symmetry codes: (i) x+1, y, z; (ii) [-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}].

Data collection: CrysAlis PRO (Agilent, 2014[Agilent (2014). CrysAlis PRO. Agilent Technologies, Yarnton, England.]); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]) and Mercury (Macrae et al., 2008[Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466-470.]); software used to prepare material for publication: WinGX (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]), PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]) and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information

CCDC reference: 1037775

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2056989014026711/su5036sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989014026711/su5036Isup2.hkl

checkCIF report


Comment top

The Michael addition is one of the most important synthetic strategies performed in organic synthesis. Among the many applications, conjugate addition to α,β-unsaturated δ-lactams has been used in the synthesis of functionalized piperidines, due to a wide range of biological activities (Leung et al., 2000). Similar to α,β-unsaturated δ-lactams, α,β-unsaturated δ-thiolactams are promising Michael acceptors affording 4-substituted piperidine-2-thiones (Sośnicki, 2009). They also form C—C bonds in the reaction with organometallics such as alkyllithium, alkylmagnesium (Tamaru et al., 1978) and lithium enolates (Tamaru et al., 1979). Among a broad range of nucleophiles applied to the C—C bond formation, the addition of aliphatic nitrocompounds play a significant role (Ballini et al., 2007). In the presence of a base catalyst, the introduction of a nitroalkyl group into a α,β-unsaturated compound represent a key step in the preparation of chiral molecules due to versatile reactivity of the nitro functionality. The corresponding nitro compounds can be transformed into a wide range of synthetically valuable products such as amines (Poupart et al., 1999), ketones (Pinnick et al., 1990), carboxylic acids, nitrile oxides and other functionalities (Mukaiyama et al., 1960).

In the title compound, Fig. 1, the piperidine ring has an envelope conformation with puckering parameters Q = 0.528 (4) Å, θ = 129.0 (4)°, φ = 314.6 (6)°, q2 = 0.411 (4)° and q3 = -0.332 (4)°. The phenyl-ethyl group linked atom N1 of the piperidine ring, shows a dihedral angle of 101.6 (4)° from the mean plane of the piperidine ring. The carboxyethyl group is placed in a axial position (torsion angle = 15.8 (3)°) and the nitromethyl group in an equatorial position (torsion angle = 73.7 (3)°) on the piperidine ring. The C5═S1 distance is 1.682 (4) Å, similar to that found for other piperidine-2-thiones (CSD; Groom & Allen, 2014). There is an intramolecular C-H···O hydrogen bond present (Table 1).

In the crystal, molecules are linked by C-H···O hydrogen bonds forming chains along [100], which are linked by further C-H···O hydrogen bonds forming corrugated layers lying parallel to (001); see Table 1 and Fig. 2.

Related literature top

For general background on piperidines and their derivatives, see: Poupart et al. (1999); Pinnick et al. (1990); Mukaiyama & Hoshino (1960); Ballini et al. (2007); Sośnicki (2009). For their biological activity, see: Leung et al. (2000). For their use in organometallic reactions, see: Tamaru et al. (1978, 1979). For details of the Cambridge Structural Database, see: Groom & Allen (2014).

Experimental top

α,β-Unsaturated piperidine-2-thione derived from (S)-(-)-phenylethylamine (1.0 mmol) was dissolved in a solution of nitroalkane, and a catalytic amount of DBU was added. The mixture was stirred at room temperature for 2 h. When the reaction was complete, 5 ml of concentrated NH4Cl was added and the solution was extracted twice with ethyl acetate. The organic phase was dried, filtered, and concentrated in vacuo. The crude product was purified by column chromatography on silica (petroleum ether/ethyl acetate 80:20) giving the title compound as a white solid (yield 80%; m.p. 383- 385 K). It was crystallized using petroleum ether/dichloromethane, giving colourless prismatic crystals. [α]D20= -92.3 (c 1.0, CH2Cl2). IR (KBr pellet, cm-1): ν= 3746, 2977, 2929, 1739, 1551, 1461, 1196, 1075, 701, 548. 1H NMR (500 MHz, CDCl3): δ 1.31 (t, J = 7.1 Hz, 3H), 1.33 (m, 1H), 1.52 (d, J = 7.1 Hz, 3H), 2.25 (ddd, J = 1.9, 5.7, 13.7 Hz, 1H), 2.79 (m, 1H), 2.99 (dd, J = 7.2, 18.3 Hz, 1H), 3.37 (ddd, J = 0.6, 7.7, 18.3 Hz, 1H), 4.05 (dd, J = 2.4, 5.4 Hz, 1H), 4.21 (dd, J = 8.4, 12.8 Hz, 1H), 4.27 (m, 2H), 4.35 (dd, J = 6.1, 12.8 Hz, 1H), 7.35 (m, 5H). 13C NMR (100 MHz, CDCl3) δ 14.1, 14.5, 28.5, 29.9, 43.4, 55.6, 58.4, 62.5, 78.8, 127.0–129.0, 138.2, 170.0, 199.1.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2. The C-bound H atoms were placed in idealized positions and refined as riding on their parent atoms, with C–H = 0.93–0.98 Å and with Uiso(H) = 1.5Ueq(C) for methyl H atoms and = 1.2Ueq(C) for other H atoms. In the final cycles of refinement 18 reflections were omitted owing to poor agreement.

Structure description top

The Michael addition is one of the most important synthetic strategies performed in organic synthesis. Among the many applications, conjugate addition to α,β-unsaturated δ-lactams has been used in the synthesis of functionalized piperidines, due to a wide range of biological activities (Leung et al., 2000). Similar to α,β-unsaturated δ-lactams, α,β-unsaturated δ-thiolactams are promising Michael acceptors affording 4-substituted piperidine-2-thiones (Sośnicki, 2009). They also form C—C bonds in the reaction with organometallics such as alkyllithium, alkylmagnesium (Tamaru et al., 1978) and lithium enolates (Tamaru et al., 1979). Among a broad range of nucleophiles applied to the C—C bond formation, the addition of aliphatic nitrocompounds play a significant role (Ballini et al., 2007). In the presence of a base catalyst, the introduction of a nitroalkyl group into a α,β-unsaturated compound represent a key step in the preparation of chiral molecules due to versatile reactivity of the nitro functionality. The corresponding nitro compounds can be transformed into a wide range of synthetically valuable products such as amines (Poupart et al., 1999), ketones (Pinnick et al., 1990), carboxylic acids, nitrile oxides and other functionalities (Mukaiyama et al., 1960).

In the title compound, Fig. 1, the piperidine ring has an envelope conformation with puckering parameters Q = 0.528 (4) Å, θ = 129.0 (4)°, φ = 314.6 (6)°, q2 = 0.411 (4)° and q3 = -0.332 (4)°. The phenyl-ethyl group linked atom N1 of the piperidine ring, shows a dihedral angle of 101.6 (4)° from the mean plane of the piperidine ring. The carboxyethyl group is placed in a axial position (torsion angle = 15.8 (3)°) and the nitromethyl group in an equatorial position (torsion angle = 73.7 (3)°) on the piperidine ring. The C5═S1 distance is 1.682 (4) Å, similar to that found for other piperidine-2-thiones (CSD; Groom & Allen, 2014). There is an intramolecular C-H···O hydrogen bond present (Table 1).

In the crystal, molecules are linked by C-H···O hydrogen bonds forming chains along [100], which are linked by further C-H···O hydrogen bonds forming corrugated layers lying parallel to (001); see Table 1 and Fig. 2.

For general background on piperidines and their derivatives, see: Poupart et al. (1999); Pinnick et al. (1990); Mukaiyama & Hoshino (1960); Ballini et al. (2007); Sośnicki (2009). For their biological activity, see: Leung et al. (2000). For their use in organometallic reactions, see: Tamaru et al. (1978, 1979). For details of the Cambridge Structural Database, see: Groom & Allen (2014).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: WinGX (Farrugia, 2012), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. A view of the molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. A view along the a axis of the crystal packing of the title compound. Hydrogen bonds are shown as dashed lines (see Table 1 for details; H atoms not involved in the intermolecular hydrogen bonding have been omitted for clarity).
4-Nitromethyl-1-[(S)-1-phenylethyl]-6-sulfanylidenepiperidine-2-carboxylate top
Crystal data top
C17H22N2O4SF(000) = 744
Mr = 350.42Dx = 1.319 Mg m−3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 2144 reflections
a = 5.7999 (2) Åθ = 3.6–22.4°
b = 10.0103 (6) ŵ = 0.21 mm−1
c = 30.4050 (18) ÅT = 293 K
V = 1765.28 (16) Å3Prism, colourless
Z = 40.20 × 0.09 × 0.05 mm
Data collection top
Agilent Xcalibur Atlas Gemini
diffractometer		3373 independent reflections
Radiation source: Enhance (Mo) X-ray Source2306 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.054
Detector resolution: 10.5564 pixels mm-1θmax = 26.1°, θmin = 2.9°
w scansh = −7→6
Absorption correction: analytical
(CrysAlis PRO; Agilent, 2014)		k = −12→12
Tmin = 0.979, Tmax = 0.991l = −37→28
8486 measured reflections
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.056 w = 1/[σ2(Fo2) + (0.0336P)2 + 0.2223P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.104(Δ/σ)max < 0.001
S = 1.04Δρmax = 0.18 e Å−3
3373 reflectionsΔρmin = −0.18 e Å−3
219 parametersAbsolute structure: Flack x determined using 705 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
0 restraintsAbsolute structure parameter: 0.16 (8)
Crystal data top
C17H22N2O4SV = 1765.28 (16) Å3
Mr = 350.42Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 5.7999 (2) ŵ = 0.21 mm−1
b = 10.0103 (6) ÅT = 293 K
c = 30.4050 (18) Å0.20 × 0.09 × 0.05 mm
Data collection top
Agilent Xcalibur Atlas Gemini
diffractometer		3373 independent reflections
Absorption correction: analytical
(CrysAlis PRO; Agilent, 2014)		2306 reflections with I > 2σ(I)
Tmin = 0.979, Tmax = 0.991Rint = 0.054
8486 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.056H-atom parameters constrained
wR(F2) = 0.104Δρmax = 0.18 e Å−3
S = 1.04Δρmin = −0.18 e Å−3
3373 reflectionsAbsolute structure: Flack x determined using 705 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
219 parametersAbsolute structure parameter: 0.16 (8)
0 restraints
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.19570 (19)0.59698 (11)0.34603 (4)0.0521 (3)
O10.2788 (5)0.1293 (3)0.35882 (11)0.0613 (9)
C10.5823 (6)0.2794 (4)0.38339 (13)0.0335 (9)
H10.65540.27750.41240.04*
N10.4157 (5)0.3912 (3)0.38245 (10)0.0348 (8)
O30.8838 (6)0.0880 (4)0.27210 (11)0.0706 (10)
C20.7699 (6)0.2959 (4)0.34888 (12)0.0401 (10)
H2A0.87040.21850.34890.048*
H2B0.86220.37430.35540.048*
C60.3122 (7)0.4254 (4)0.42575 (13)0.0424 (10)
H60.19290.49250.420.051*
C30.6547 (7)0.3112 (4)0.30381 (13)0.0387 (10)
H30.55280.23460.29880.046*
O20.6039 (5)0.0483 (3)0.38838 (11)0.0661 (10)
N20.9716 (7)0.1947 (4)0.26262 (12)0.0515 (10)
C70.4909 (7)0.4921 (4)0.45523 (15)0.0411 (10)
C50.3778 (6)0.4662 (4)0.34676 (14)0.0379 (10)
C130.1904 (8)0.3059 (5)0.44649 (14)0.0544 (12)
H13A0.09610.26270.42480.082*
H13B0.09520.33590.47040.082*
H13C0.30310.2440.45740.082*
C140.4629 (7)0.1445 (4)0.37579 (14)0.0410 (10)
C170.8290 (7)0.3186 (4)0.26649 (14)0.0508 (11)
H17A0.74770.33330.2390.061*
H17B0.930.39440.27130.061*
O41.1672 (6)0.2065 (4)0.24925 (12)0.0746 (10)
C40.5101 (7)0.4380 (4)0.30508 (14)0.0441 (11)
H4A0.61140.51320.29950.053*
H4B0.40060.43410.2810.053*
C120.4732 (8)0.4867 (5)0.50057 (16)0.0576 (13)
H120.35350.43880.51340.069*
C80.6741 (8)0.5636 (4)0.43755 (15)0.0524 (12)
H80.69160.56740.40720.063*
C110.6311 (10)0.5515 (5)0.52687 (17)0.0707 (15)
H110.6160.54670.55730.085*
C90.8308 (8)0.6293 (5)0.46405 (19)0.0646 (14)
H90.95050.67780.45140.078*
C100.8102 (10)0.6231 (5)0.50910 (19)0.0708 (15)
H100.91560.66660.52720.085*
C150.5480 (11)−0.0877 (5)0.3739 (3)0.107 (2)
H15A0.5214−0.14350.39950.128*
H15B0.4069−0.08580.35680.128*
C160.7207 (13)−0.1424 (7)0.3491 (2)0.138 (3)
H16A0.7451−0.08860.32330.207*
H16B0.678−0.23130.34040.207*
H16C0.8602−0.14580.3660.207*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0540 (6)0.0423 (6)0.0600 (8)0.0143 (6)0.0054 (6)0.0103 (6)
O10.0488 (17)0.053 (2)0.082 (2)−0.0121 (15)−0.0068 (17)−0.0028 (16)
C10.031 (2)0.034 (2)0.036 (2)0.0039 (18)−0.0003 (19)−0.0017 (18)
N10.0360 (16)0.0332 (19)0.035 (2)0.0034 (15)0.0024 (15)0.0013 (16)
O30.096 (3)0.049 (2)0.067 (2)0.003 (2)0.0215 (19)−0.0059 (18)
C20.034 (2)0.042 (2)0.045 (2)0.0007 (18)−0.005 (2)−0.002 (2)
C60.039 (2)0.042 (2)0.047 (3)0.010 (2)0.004 (2)0.0018 (19)
C30.036 (2)0.041 (2)0.039 (2)−0.0018 (19)0.002 (2)0.0004 (19)
O20.0655 (19)0.0378 (18)0.095 (3)0.0108 (17)0.004 (2)0.0027 (17)
N20.059 (2)0.056 (3)0.039 (2)0.006 (2)0.008 (2)−0.0078 (19)
C70.048 (2)0.032 (2)0.043 (3)0.008 (2)0.003 (2)−0.005 (2)
C50.0345 (19)0.033 (2)0.047 (3)−0.0050 (17)−0.003 (2)0.001 (2)
C130.052 (2)0.063 (3)0.048 (3)−0.011 (3)0.004 (2)0.005 (2)
C140.044 (2)0.038 (2)0.041 (3)0.005 (2)0.012 (2)0.003 (2)
C170.056 (2)0.047 (3)0.049 (3)0.001 (2)0.012 (2)0.003 (2)
O40.0502 (18)0.092 (3)0.082 (2)0.0043 (19)0.014 (2)−0.014 (2)
C40.045 (2)0.045 (3)0.043 (3)0.004 (2)0.005 (2)0.006 (2)
C120.068 (3)0.052 (3)0.053 (3)0.000 (3)−0.001 (3)−0.003 (2)
C80.054 (2)0.048 (3)0.056 (3)−0.001 (2)0.006 (3)−0.011 (2)
C110.098 (4)0.063 (3)0.051 (3)0.007 (3)−0.014 (3)−0.011 (3)
C90.063 (3)0.052 (3)0.079 (4)−0.006 (3)−0.001 (3)−0.018 (3)
C100.077 (3)0.057 (3)0.078 (4)−0.003 (3)−0.019 (3)−0.021 (3)
C150.105 (4)0.032 (3)0.184 (7)0.008 (3)0.034 (5)−0.014 (4)
C160.166 (7)0.073 (4)0.176 (7)−0.028 (5)0.101 (6)−0.048 (4)
Geometric parameters (Å, º) top
S1—C51.682 (4)C5—C41.508 (5)
O1—C141.195 (5)C13—H13A0.96
C1—H10.98C13—H13B0.96
C1—N11.479 (5)C13—H13C0.96
C1—C21.521 (5)C17—H17A0.97
C1—C141.535 (5)C17—H17B0.97
N1—C61.487 (5)C4—H4A0.97
N1—C51.338 (5)C4—H4B0.97
O3—N21.218 (5)C12—H120.93
C2—H2A0.97C12—C111.378 (7)
C2—H2B0.97C8—H80.93
C2—C31.532 (5)C8—C91.381 (6)
C6—H60.98C11—H110.93
C6—C71.524 (6)C11—C101.372 (7)
C6—C131.526 (6)C9—H90.93
C3—H30.98C9—C101.376 (7)
C3—C171.521 (5)C10—H100.93
C3—C41.522 (5)C15—H15A0.97
O2—C141.321 (5)C15—H15B0.97
O2—C151.467 (6)C15—C161.369 (8)
N2—C171.495 (5)C16—H16A0.96
N2—O41.211 (4)C16—H16B0.96
C7—C121.383 (6)C16—H16C0.96
C7—C81.390 (6)
N1—C1—H1108.3O1—C14—C1125.5 (4)
N1—C1—C2111.8 (3)O1—C14—O2125.8 (4)
N1—C1—C14111.6 (3)O2—C14—C1108.6 (3)
C2—C1—H1108.3C3—C17—H17A109.1
C2—C1—C14108.4 (3)C3—C17—H17B109.1
C14—C1—H1108.3N2—C17—C3112.7 (3)
C1—N1—C6114.9 (3)N2—C17—H17A109.1
C5—N1—C1123.2 (3)N2—C17—H17B109.1
C5—N1—C6121.5 (3)H17A—C17—H17B107.8
C1—C2—H2A110C3—C4—H4A108
C1—C2—H2B110C3—C4—H4B108
C1—C2—C3108.4 (3)C5—C4—C3117.3 (3)
H2A—C2—H2B108.4C5—C4—H4A108
C3—C2—H2A110C5—C4—H4B108
C3—C2—H2B110H4A—C4—H4B107.2
N1—C6—H6106.5C7—C12—H12119.7
N1—C6—C7110.3 (3)C11—C12—C7120.7 (5)
N1—C6—C13111.8 (3)C11—C12—H12119.7
C7—C6—H6106.5C7—C8—H8119.2
C7—C6—C13114.5 (3)C9—C8—C7121.5 (4)
C13—C6—H6106.5C9—C8—H8119.2
C2—C3—H3108.9C12—C11—H11119.3
C17—C3—C2112.5 (3)C10—C11—C12121.3 (5)
C17—C3—H3108.9C10—C11—H11119.3
C17—C3—C4110.2 (3)C8—C9—H9119.9
C4—C3—C2107.5 (3)C10—C9—C8120.1 (5)
C4—C3—H3108.9C10—C9—H9119.9
C14—O2—C15117.0 (4)C11—C10—C9118.8 (5)
O3—N2—C17118.5 (4)C11—C10—H10120.6
O4—N2—O3123.8 (4)C9—C10—H10120.6
O4—N2—C17117.6 (4)O2—C15—H15A109.2
C12—C7—C6121.2 (4)O2—C15—H15B109.2
C12—C7—C8117.5 (4)H15A—C15—H15B107.9
C8—C7—C6121.2 (4)C16—C15—O2112.0 (5)
N1—C5—S1123.4 (3)C16—C15—H15A109.2
N1—C5—C4119.5 (3)C16—C15—H15B109.2
C4—C5—S1117.0 (3)C15—C16—H16A109.5
C6—C13—H13A109.5C15—C16—H16B109.5
C6—C13—H13B109.5C15—C16—H16C109.5
C6—C13—H13C109.5H16A—C16—H16B109.5
H13A—C13—H13B109.5H16A—C16—H16C109.5
H13A—C13—H13C109.5H16B—C16—H16C109.5
H13B—C13—H13C109.5
S1—C5—C4—C3−173.4 (3)C6—C7—C12—C11−177.6 (4)
C1—N1—C6—C771.5 (4)C6—C7—C8—C9177.1 (4)
C1—N1—C6—C13−57.2 (4)C7—C12—C11—C10−0.1 (7)
C1—N1—C5—S1−177.7 (3)C7—C8—C9—C101.1 (7)
C1—N1—C5—C4−0.3 (5)C5—N1—C6—C7−101.6 (4)
C1—C2—C3—C17−175.9 (3)C5—N1—C6—C13129.7 (4)
C1—C2—C3—C462.6 (4)C13—C6—C7—C12−27.2 (5)
N1—C1—C2—C3−55.8 (4)C13—C6—C7—C8154.6 (4)
N1—C1—C14—O120.7 (6)C14—C1—N1—C689.9 (4)
N1—C1—C14—O2−163.5 (3)C14—C1—N1—C5−97.1 (4)
N1—C6—C7—C12−154.4 (4)C14—C1—C2—C367.6 (4)
N1—C6—C7—C827.4 (5)C14—O2—C15—C16120.1 (6)
N1—C5—C4—C39.0 (5)C17—C3—C4—C5−162.9 (3)
O3—N2—C17—C332.8 (5)O4—N2—C17—C3−148.7 (4)
C2—C1—N1—C6−148.5 (3)C4—C3—C17—N2−178.1 (3)
C2—C1—N1—C524.4 (5)C12—C7—C8—C9−1.2 (6)
C2—C1—C14—O1−102.9 (4)C12—C11—C10—C9−0.1 (8)
C2—C1—C14—O272.9 (4)C8—C7—C12—C110.7 (7)
C2—C3—C17—N262.0 (5)C8—C9—C10—C11−0.4 (8)
C2—C3—C4—C5−40.0 (4)C15—O2—C14—O110.7 (7)
C6—N1—C5—S1−5.2 (5)C15—O2—C14—C1−165.2 (4)
C6—N1—C5—C4172.2 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C16—H16A···O30.962.493.419 (8)163
C2—H2A···O1i0.972.553.404 (5)147
C17—H17B···O3ii0.972.583.380 (6)140
Symmetry codes: (i) x+1, y, z; (ii) −x+2, y+1/2, −z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C16—H16A···O30.962.493.419 (8)163
C2—H2A···O1i0.972.553.404 (5)147
C17—H17B···O3ii0.972.583.380 (6)140
Symmetry codes: (i) x+1, y, z; (ii) −x+2, y+1/2, −z+1/2.
 

Acknowledgements

We are grateful to CONACyT (project 154104) for financial support and AZ thanks CONACyT for a postdoctoral scholarship (165517).

References

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ISSN: 2056-9890
Volume 71| Part 1| January 2015| Pages o41-o42
https://doi.org/10.1107/S2056989014026711
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