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

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).

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.056
• wR factor = 0.104
• Data-to-parameter ratio = 15.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT220_ALERT_2_C Large Non-Solvent  C     Ueq(max)/Ueq(min) Range        4.1 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H    Uiso(max)/Uiso(min) ..        5.2 Ratio
PLAT340_ALERT_3_C Low Bond Precision on  C-C Bonds ...............     0.0066 Ang.
PLAT360_ALERT_2_C Short  C(sp3)-C(sp3) Bond  C15    -   C16    ...       1.37 Ang.
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      3.153 Check
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          7 Report

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF     Please Do !
PLAT199_ALERT_1_G Reported _cell_measurement_temperature ..... (K)        293 Check
PLAT200_ALERT_1_G Reported   _diffrn_ambient_temperature ..... (K)        293 Check
PLAT791_ALERT_4_G The Model has Chirality at C1      .............          R Verify
PLAT791_ALERT_4_G The Model has Chirality at C3      .............          S Verify
PLAT791_ALERT_4_G The Model has Chirality at C6      .............          S Verify
PLAT910_ALERT_3_G Missing # of FCF Reflections Below Th(Min) .....          4 Report

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   6 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   7 ALERT level G = General information/check it is not something unexpected

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   5 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

---

S1. Comment

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

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).

S2. Experimental

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.

S3. Refinement

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 U_iso(H) = 1.5U_eq(C) for methyl H atoms and = 1.2U_eq(C) for other H atoms. In the final cycles of refinement 18 reflections were omitted owing to poor agreement.

Computing details

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

	Fig. 1. A view of the molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 30% probability level.
	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

Crystal data

C17H22N2O4S	F(000) = 744
Mr = 350.42	Dx = 1.319 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2144 reflections
a = 5.7999 (2) Å	θ = 3.6–22.4°
b = 10.0103 (6) Å	µ = 0.21 mm^−1
c = 30.4050 (18) Å	T = 293 K
V = 1765.28 (16) Å^3	Prism, colourless
Z = 4	0.20 × 0.09 × 0.05 mm

Data collection

Agilent Xcalibur Atlas Gemini diffractometer	3373 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2306 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.054
Detector resolution: 10.5564 pixels mm^-1	θmax = 26.1°, θmin = 2.9°
w scans	h = −7→6
Absorption correction: analytical (CrysAlis PRO; Agilent, 2014)	k = −12→12
Tmin = 0.979, Tmax = 0.991	l = −37→28
8486 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.056	w = 1/[σ^2(Fo^2) + (0.0336P)^2 + 0.2223P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.104	(Δ/σ)max < 0.001
S = 1.04	Δρmax = 0.18 e Å^−3
3373 reflections	Δρmin = −0.18 e Å^−3
219 parameters	Absolute structure: Flack x determined using 705 quotients [(I^+)-(I^-)]/[(I^+)+(I^-)] (Parsons et al., 2013)
0 restraints	Absolute structure parameter: 0.16 (8)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
S1	0.19570 (19)	0.59698 (11)	0.34603 (4)	0.0521 (3)
O1	0.2788 (5)	0.1293 (3)	0.35882 (11)	0.0613 (9)
C1	0.5823 (6)	0.2794 (4)	0.38339 (13)	0.0335 (9)
H1	0.6554	0.2775	0.4124	0.04*
N1	0.4157 (5)	0.3912 (3)	0.38245 (10)	0.0348 (8)
O3	0.8838 (6)	0.0880 (4)	0.27210 (11)	0.0706 (10)
C2	0.7699 (6)	0.2959 (4)	0.34888 (12)	0.0401 (10)
H2A	0.8704	0.2185	0.3489	0.048*
H2B	0.8622	0.3743	0.3554	0.048*
C6	0.3122 (7)	0.4254 (4)	0.42575 (13)	0.0424 (10)
H6	0.1929	0.4925	0.42	0.051*
C3	0.6547 (7)	0.3112 (4)	0.30381 (13)	0.0387 (10)
H3	0.5528	0.2346	0.2988	0.046*
O2	0.6039 (5)	0.0483 (3)	0.38838 (11)	0.0661 (10)
N2	0.9716 (7)	0.1947 (4)	0.26262 (12)	0.0515 (10)
C7	0.4909 (7)	0.4921 (4)	0.45523 (15)	0.0411 (10)
C5	0.3778 (6)	0.4662 (4)	0.34676 (14)	0.0379 (10)
C13	0.1904 (8)	0.3059 (5)	0.44649 (14)	0.0544 (12)
H13A	0.0961	0.2627	0.4248	0.082*
H13B	0.0952	0.3359	0.4704	0.082*
H13C	0.3031	0.244	0.4574	0.082*
C14	0.4629 (7)	0.1445 (4)	0.37579 (14)	0.0410 (10)
C17	0.8290 (7)	0.3186 (4)	0.26649 (14)	0.0508 (11)
H17A	0.7477	0.3333	0.239	0.061*
H17B	0.93	0.3944	0.2713	0.061*
O4	1.1672 (6)	0.2065 (4)	0.24925 (12)	0.0746 (10)
C4	0.5101 (7)	0.4380 (4)	0.30508 (14)	0.0441 (11)
H4A	0.6114	0.5132	0.2995	0.053*
H4B	0.4006	0.4341	0.281	0.053*
C12	0.4732 (8)	0.4867 (5)	0.50057 (16)	0.0576 (13)
H12	0.3535	0.4388	0.5134	0.069*
C8	0.6741 (8)	0.5636 (4)	0.43755 (15)	0.0524 (12)
H8	0.6916	0.5674	0.4072	0.063*
C11	0.6311 (10)	0.5515 (5)	0.52687 (17)	0.0707 (15)
H11	0.616	0.5467	0.5573	0.085*
C9	0.8308 (8)	0.6293 (5)	0.46405 (19)	0.0646 (14)
H9	0.9505	0.6778	0.4514	0.078*
C10	0.8102 (10)	0.6231 (5)	0.50910 (19)	0.0708 (15)
H10	0.9156	0.6666	0.5272	0.085*
C15	0.5480 (11)	−0.0877 (5)	0.3739 (3)	0.107 (2)
H15A	0.5214	−0.1435	0.3995	0.128*
H15B	0.4069	−0.0858	0.3568	0.128*
C16	0.7207 (13)	−0.1424 (7)	0.3491 (2)	0.138 (3)
H16A	0.7451	−0.0886	0.3233	0.207*
H16B	0.678	−0.2313	0.3404	0.207*
H16C	0.8602	−0.1458	0.366	0.207*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0540 (6)	0.0423 (6)	0.0600 (8)	0.0143 (6)	0.0054 (6)	0.0103 (6)
O1	0.0488 (17)	0.053 (2)	0.082 (2)	−0.0121 (15)	−0.0068 (17)	−0.0028 (16)
C1	0.031 (2)	0.034 (2)	0.036 (2)	0.0039 (18)	−0.0003 (19)	−0.0017 (18)
N1	0.0360 (16)	0.0332 (19)	0.035 (2)	0.0034 (15)	0.0024 (15)	0.0013 (16)
O3	0.096 (3)	0.049 (2)	0.067 (2)	0.003 (2)	0.0215 (19)	−0.0059 (18)
C2	0.034 (2)	0.042 (2)	0.045 (2)	0.0007 (18)	−0.005 (2)	−0.002 (2)
C6	0.039 (2)	0.042 (2)	0.047 (3)	0.010 (2)	0.004 (2)	0.0018 (19)
C3	0.036 (2)	0.041 (2)	0.039 (2)	−0.0018 (19)	0.002 (2)	0.0004 (19)
O2	0.0655 (19)	0.0378 (18)	0.095 (3)	0.0108 (17)	0.004 (2)	0.0027 (17)
N2	0.059 (2)	0.056 (3)	0.039 (2)	0.006 (2)	0.008 (2)	−0.0078 (19)
C7	0.048 (2)	0.032 (2)	0.043 (3)	0.008 (2)	0.003 (2)	−0.005 (2)
C5	0.0345 (19)	0.033 (2)	0.047 (3)	−0.0050 (17)	−0.003 (2)	0.001 (2)
C13	0.052 (2)	0.063 (3)	0.048 (3)	−0.011 (3)	0.004 (2)	0.005 (2)
C14	0.044 (2)	0.038 (2)	0.041 (3)	0.005 (2)	0.012 (2)	0.003 (2)
C17	0.056 (2)	0.047 (3)	0.049 (3)	0.001 (2)	0.012 (2)	0.003 (2)
O4	0.0502 (18)	0.092 (3)	0.082 (2)	0.0043 (19)	0.014 (2)	−0.014 (2)
C4	0.045 (2)	0.045 (3)	0.043 (3)	0.004 (2)	0.005 (2)	0.006 (2)
C12	0.068 (3)	0.052 (3)	0.053 (3)	0.000 (3)	−0.001 (3)	−0.003 (2)
C8	0.054 (2)	0.048 (3)	0.056 (3)	−0.001 (2)	0.006 (3)	−0.011 (2)
C11	0.098 (4)	0.063 (3)	0.051 (3)	0.007 (3)	−0.014 (3)	−0.011 (3)
C9	0.063 (3)	0.052 (3)	0.079 (4)	−0.006 (3)	−0.001 (3)	−0.018 (3)
C10	0.077 (3)	0.057 (3)	0.078 (4)	−0.003 (3)	−0.019 (3)	−0.021 (3)
C15	0.105 (4)	0.032 (3)	0.184 (7)	0.008 (3)	0.034 (5)	−0.014 (4)
C16	0.166 (7)	0.073 (4)	0.176 (7)	−0.028 (5)	0.101 (6)	−0.048 (4)

Geometric parameters (Å, º)

S1—C5	1.682 (4)	C5—C4	1.508 (5)
O1—C14	1.195 (5)	C13—H13A	0.96
C1—H1	0.98	C13—H13B	0.96
C1—N1	1.479 (5)	C13—H13C	0.96
C1—C2	1.521 (5)	C17—H17A	0.97
C1—C14	1.535 (5)	C17—H17B	0.97
N1—C6	1.487 (5)	C4—H4A	0.97
N1—C5	1.338 (5)	C4—H4B	0.97
O3—N2	1.218 (5)	C12—H12	0.93
C2—H2A	0.97	C12—C11	1.378 (7)
C2—H2B	0.97	C8—H8	0.93
C2—C3	1.532 (5)	C8—C9	1.381 (6)
C6—H6	0.98	C11—H11	0.93
C6—C7	1.524 (6)	C11—C10	1.372 (7)
C6—C13	1.526 (6)	C9—H9	0.93
C3—H3	0.98	C9—C10	1.376 (7)
C3—C17	1.521 (5)	C10—H10	0.93
C3—C4	1.522 (5)	C15—H15A	0.97
O2—C14	1.321 (5)	C15—H15B	0.97
O2—C15	1.467 (6)	C15—C16	1.369 (8)
N2—C17	1.495 (5)	C16—H16A	0.96
N2—O4	1.211 (4)	C16—H16B	0.96
C7—C12	1.383 (6)	C16—H16C	0.96
C7—C8	1.390 (6)
N1—C1—H1	108.3	O1—C14—C1	125.5 (4)
N1—C1—C2	111.8 (3)	O1—C14—O2	125.8 (4)
N1—C1—C14	111.6 (3)	O2—C14—C1	108.6 (3)
C2—C1—H1	108.3	C3—C17—H17A	109.1
C2—C1—C14	108.4 (3)	C3—C17—H17B	109.1
C14—C1—H1	108.3	N2—C17—C3	112.7 (3)
C1—N1—C6	114.9 (3)	N2—C17—H17A	109.1
C5—N1—C1	123.2 (3)	N2—C17—H17B	109.1
C5—N1—C6	121.5 (3)	H17A—C17—H17B	107.8
C1—C2—H2A	110	C3—C4—H4A	108
C1—C2—H2B	110	C3—C4—H4B	108
C1—C2—C3	108.4 (3)	C5—C4—C3	117.3 (3)
H2A—C2—H2B	108.4	C5—C4—H4A	108
C3—C2—H2A	110	C5—C4—H4B	108
C3—C2—H2B	110	H4A—C4—H4B	107.2
N1—C6—H6	106.5	C7—C12—H12	119.7
N1—C6—C7	110.3 (3)	C11—C12—C7	120.7 (5)
N1—C6—C13	111.8 (3)	C11—C12—H12	119.7
C7—C6—H6	106.5	C7—C8—H8	119.2
C7—C6—C13	114.5 (3)	C9—C8—C7	121.5 (4)
C13—C6—H6	106.5	C9—C8—H8	119.2
C2—C3—H3	108.9	C12—C11—H11	119.3
C17—C3—C2	112.5 (3)	C10—C11—C12	121.3 (5)
C17—C3—H3	108.9	C10—C11—H11	119.3
C17—C3—C4	110.2 (3)	C8—C9—H9	119.9
C4—C3—C2	107.5 (3)	C10—C9—C8	120.1 (5)
C4—C3—H3	108.9	C10—C9—H9	119.9
C14—O2—C15	117.0 (4)	C11—C10—C9	118.8 (5)
O3—N2—C17	118.5 (4)	C11—C10—H10	120.6
O4—N2—O3	123.8 (4)	C9—C10—H10	120.6
O4—N2—C17	117.6 (4)	O2—C15—H15A	109.2
C12—C7—C6	121.2 (4)	O2—C15—H15B	109.2
C12—C7—C8	117.5 (4)	H15A—C15—H15B	107.9
C8—C7—C6	121.2 (4)	C16—C15—O2	112.0 (5)
N1—C5—S1	123.4 (3)	C16—C15—H15A	109.2
N1—C5—C4	119.5 (3)	C16—C15—H15B	109.2
C4—C5—S1	117.0 (3)	C15—C16—H16A	109.5
C6—C13—H13A	109.5	C15—C16—H16B	109.5
C6—C13—H13B	109.5	C15—C16—H16C	109.5
C6—C13—H13C	109.5	H16A—C16—H16B	109.5
H13A—C13—H13B	109.5	H16A—C16—H16C	109.5
H13A—C13—H13C	109.5	H16B—C16—H16C	109.5
H13B—C13—H13C	109.5
S1—C5—C4—C3	−173.4 (3)	C6—C7—C12—C11	−177.6 (4)
C1—N1—C6—C7	71.5 (4)	C6—C7—C8—C9	177.1 (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—C10	1.1 (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—C13	129.7 (4)
C1—C2—C3—C4	62.6 (4)	C13—C6—C7—C12	−27.2 (5)
N1—C1—C2—C3	−55.8 (4)	C13—C6—C7—C8	154.6 (4)
N1—C1—C14—O1	20.7 (6)	C14—C1—N1—C6	89.9 (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—C3	67.6 (4)
N1—C6—C7—C8	27.4 (5)	C14—O2—C15—C16	120.1 (6)
N1—C5—C4—C3	9.0 (5)	C17—C3—C4—C5	−162.9 (3)
O3—N2—C17—C3	32.8 (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—C5	24.4 (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—O2	72.9 (4)	C8—C7—C12—C11	0.7 (7)
C2—C3—C17—N2	62.0 (5)	C8—C9—C10—C11	−0.4 (8)
C2—C3—C4—C5	−40.0 (4)	C15—O2—C14—O1	10.7 (7)
C6—N1—C5—S1	−5.2 (5)	C15—O2—C14—C1	−165.2 (4)
C6—N1—C5—C4	172.2 (3)

Hydrogen-bond geometry (Å, º)

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···O1^i	0.97	2.55	3.404 (5)	147
C17—H17B···O3^ii	0.97	2.58	3.380 (6)	140

Symmetry codes: (i) x+1, y, z; (ii) −x+2, y+1/2, −z+1/2.