Crystal structure of 3-({[(morpholin-4-yl)carbono­thio­yl]sulfan­yl}acet­yl)phenyl benzoate

In the title compound, C₂₀H₁₉NO₄S₂, the morpholine ring adopts the expected chair conformation. The central phenyl ring makes dihedral angles of 67.97 (4) and 7.74 (3)°, respectively, with the benzoate phenyl ring and the morpholine mean plane. In the crystal, mol­ecules are linked by C—H⋯O hydrogen bonds, forming zigzag chains along the b-axis direction. C—H⋯π inter­actions link centrosymmetrically related mol­ecules, reinforcing the three-dimensional structure.

1. Chemical context

The title compound is a di­thio­carbamate ester derivative of 3-(2-bromacet­yl) phenyl benzoate, a key starting material used in the synthesis of phenyl­ephrine, (R)-3-[−1-hy­droxy-2-(methyl­amino)­eth­yl] phenol, which is a selective α1-adrenergic receptor agonist used primarily as a decongestant and as an agent to dilate the pupil and to increase blood pressure. Our current research work is aimed at the synthesis of a series of 3-(2-bromacet­yl) phenyl benzoate di­thio­carbamate ester derivatives. Di­thio­carbamate acid esters exhibit a range of biological effects, including anti-bacterial, anti-fungal and anti-oxidant activity (Hirschelman et al., 2002) and inhibition of cardiac hypertrophy (Naoto et al. 2008). Recently, it was found that 5-oxohexyl di­thio­carbamic acid methyl esters are potent phase II enzyme inducers, which could be used as cancer chemo-preventive agents (Scozzafava et al., 2000).

2. Structural commentary

In the mol­ecular structure of the title compound, the morpholine ring adopts the expected chair conformation. The phenyl ring makes dihedral angles of 67.97 (4) and 7.74 (3)° respectively with phenyl ring and the morpholine mean plane. This is also reflected in the deviation of the torsion angles C5—S1—C6—C7 = 175.32 (2) and C12—O3—C14—C15 = −178.91 (3)°. Weak intra­molecular C—H⋯S hydrogen bonds exist within the morpholyl di­thio­carbamate moiety (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C15–C20 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2B⋯S1	0.97	2.41	2.938 (2)	114
C3—H3A⋯S2	0.97	2.56	3.052 (5)	111
C13—H13⋯O4^i	0.93	2.43	3.224 (3)	143
C11—H11⋯Cg^ii	0.93	2.88	3.629 (2)	138
Symmetry codes: (i) x, y+1, z; (ii) -x+1, -y, -z+1.

Figure 1 The mol­ecular structure of the title compound, showing 50% displacement ellipsoids.

3. Supra­molecular features

In the crystal, mol­ecules are linked by weak C—H⋯O hydrogen bonds, forming zigzag chains along the b axis. C—H⋯π inter­actions link centrosymmetrically related mol­ecules, reinforcing the three-dimensional structure (Fig. 2)

Figure 2 Packing diagram of the title compound, with C—H⋯O and C—H⋯π inter­actions indicated by dashed lines.

4. Database survey

A search of the Cambridge Structural Database (Version 5.35, updates February 2014; Groom & Allen, 2014) for 2-(4-meth­oxy­phen­yl)-2-oxoethyl di­thio­carbamate gave one hit, namely GEGGUV01 (Jian et al., 2006). A search for 2-oxoethyl di­thio­formate gave two related structures, viz. 2-oxo-2-(2-oxo-2H-chromen-3-yl)ethyl pyrrolidine-1-carbodi­thio­ate (Kumar et al., 2013) and (6-meth­oxy-2-oxo-2H-chromen-4-yl)methyl morpholine-4-carbodi­thio­ate (Devarajegowda et al., 2013). Inter­estingly, dimer formation via C—H⋯O hydrogen bonds is a feature of the packing in these structures.

5. Synthesis and Crystallization

To a solution of NaOH (1 mmol) in 3 ml water was added to a mixture of morpholine (1 mmol) in ethanol (25 ml). After stirring at room temperature for about 20 min, carbon di­sulfide (1.2 mmol) was added dropwise and the resulting mixture was further stirred at room temperature for 90 min. Then 3-(2-bromacet­yl) phenyl benzoate (1 mmol) was added and stirring was continued. After completion of the reaction (monitored by TLC), the solvent was removed under vacuum and the residue was extracted with di­chloro­methane (2 × 25 ml) and dried over anhydrous MgSO₄. The solvent was evaporated and the compound recrystallized from an ethanol–chloro­form mixture (3:1) to give the title compound as colourless crystals in 81% yield.

Off-white solid, IR (KBr) ν_max/cm⁻¹: 2857, 3073 (C—H aliphatic and aromatic), 1732 (C=O), 1421, 1680 (C=C), 1264 (C—O), 1228 (C=S), 1061 (C—N). ¹H NMR (300 MHz, CDCl₃): δ 3.77–3.80 (t, 4H), 4.23–4.43 (t, 4H), 4.91(s, 2H), 7.26–7.47 (m, 1H), 7.48–7.51 (m, 2H), 7.53–7.60 (m, 1H), 7.63–768 (m, 1H), 7.90–7.91 (t, 1H), 7.99–8.02 (d, 1H), 8.20–8.22 (d, 2H); ¹³C NMR (75 MHz, CDCl₃): δ 44.6 (C6), 49.5 (C2, C3), 65.6 (C1, C4), 121.83 (C13), 126.0 (C9), 127.1 (C11), 128.6 (C10), 129.8 (C17, C19), 130.2 (C15, C16, C20), 137.6 (C18), 151.2 (C8), 154.93 (C12), 182.82 (C14), 192.15 (C7), 195.75 (C5); MS m/z: 402.10 [M + H]⁺. Analysis calculated (%) for C₂₀H₁₉NO₄S₂: C 59.83, H 4.77, N 3.49, S 15.97%; found: C 59.72, H 4.85, N 3.61, S 15.94.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The C-bound H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.93–0.97Å and U_iso(H) = 1.2U_eq(C).

Table 2
Experimental details

Crystal data
Chemical formula	C20H19NO4S2
Mr	401.48
Crystal system, space group	Monoclinic, P21/c
Temperature (K)	296
a, b, c (Å)	19.5521 (7), 5.3649 (2), 18.5142 (6)
β (°)	101.816 (2)
V (Å^3)	1900.90 (12)
Z	4
Radiation type	Mo Kα
μ (mm^−1)	0.31
Crystal size (mm)	0.35 × 0.31 × 0.25
Data collection
Diffractometer	Bruker SMART CCD area detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
Tmin, Tmax	0.887, 0.934
No. of measured, independent and observed [I > 2σ(I)] reflections	12830, 3539, 2613
Rint	0.024
(sin θ/λ)max (Å^−1)	0.606
Refinement
R[F^2 > 2σ(F^2)], wR(F^2), S	0.042, 0.122, 1.06
No. of reflections	3539
No. of parameters	244
H-atom treatment	H-atom parameters constrained
Δρmax, Δρmin (e Å^−3)	0.31, −0.22
Computer programs: SMART and SAINT (Bruker, 1998), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), CAMERON (Watkin et al., 1993), PARST (Nardelli, 1995) and PLATON (Spek, 2009).

Supporting information

S1. Chemical context

The title compound is a di­thio­carbamate ester derivative of 3-(2-bromacetyl) phenyl benzoate, a key starting material used in the synthesis of phenyl­ephrine, (R)-3-[-1-hy­droxy-2-(methyl­amino)­ethyl] phenol, which is a selective α1-adrenergic receptor agonist used primarily as a decongestant and as an agent to dilate the pupil and to increase blood pressure. Our current research work is aimed at the synthesis of a series of 3-(2-bromacetyl) phenyl benzoate di­thio­carbamate ester derivatives. Di­thio­carbamate acid esters exhibit a range of biological effects, including anti-bacterial, anti-fungal and anti-oxidant activity (Hirschelman et al., 2002) and inhibition of cardiac hypertrophy (Naoto et al. 2008). Recently, it was found that 5-oxo­hexyl di­thio­carbamic acid methyl esters are potent phase II enzyme inducers, which could be used as cancer chemo-preventive agents (Scozzafava et al., 2000).

S2. Structural commentary

In the molecular structure of the title compound, the morpholine ring adopts the expected chair conformation. The phenyl ring makes dihedral angles of 67.97 (4) and 7.74 (3)° respectively with phenyl ring and the morpholine mean plane. This is also reflected in the deviation of the torsion angles C5—S1—C6—C7 = 175.32 (2) and C12—O3—C14—C15 = -178.91 (3)°. Weak intra­molecular C—H···S hydrogen bonds exist within the morpholyl di­thio­carbamate moiety (Table 1).

S3. Supra­molecular features

In the crystal, molecules are linked by weak C—H···O hydrogen bonds, forming zigzag chains along the b axis. C—H···π inter­actions link centrosymmetrically related molecules, reinforcing the three-dimensional structure (Fig. 2)

S4. Database survey

A search of the Cambridge Structural Database (Version 5.35, updates February 2014; Groom & Allen, 2014) for 2-(4-meth­oxy­phenyl)-2-oxo­ethyl di­thio­carbamate gave one hit, namely GEGGUV01 (Jian et al., 2006). A search for 2-oxo­ethyl di­thio­formate gave two related structures, viz. 2-oxo-2-(2-oxo-2H-chromen-3-yl)ethyl pyrrolidine-1-carbodi­thio­ate (Kumar et al., 2013) and (6-meth­oxy-2-oxo-2H-chromen-4-yl)methyl morpholine-4-carbodi­thio­ate (Devarajegowda et al., 2013). Inter­estingly, dimer formation via C—H···O hydrogen bonds is a feature of the packing in these structures.

S5. Synthesis and Crystallization

To a solution of NaOH (1 mmol) in 3 ml water was added to a mixture of morpholine (1 mmol) in ethanol (25 ml). After stirring at room temperature for about 20 min, carbon di­sulfide (1.2 mmol) was added dropwise and the resulting mixture was further stirred at room temperature for 90 min. Then 3-(2-bromacetyl) phenyl benzoate (1 mmol) was added and stirring was continued. After completion of the reaction (monitored by TLC), the solvent was removed under vacuum and the residue was extracted with di­chloro­methane (2 × 25 ml) and dried over anhydrous MgSO₄. The solvent was evaporated and the compound recrystallized from an ethanol–chloro­form mixture (3:1) to give the title compound as colourless crystals in 81% yield.

Off-white solid, IR (KBr) ν_max/cm^-1: 2857, 3073 (C—H aliphatic and aromatic), 1732 (C═O), 1421, 1680 (C═C),1264 (C—O), 1228 (C═S), 1061 (C—N). ¹H NMR (300 MHz, CDCl₃): δ 3.77–3.80 (t, 4H), 4.23–4.43 (t, 4H), 4.91(s, 2H), 7.26–7.47 (m, 1H), 7.48–7.51 (m, 2H), 7.53–7.60 (m, 1H), 7.63–768 (m, 1H), 7.90–7.91 (t, 1H), 7.99–8.02 (d, 1H), 8.20–8.22 (d, 2H); ¹³C NMR (75 MHz, CDCl₃): δ 44.6 (C6), 49.5 (C2, C3), 65.6 (C1, C4), 121.83 (C13), 126.0 (C9), 127.1 (C11), 128.6 (C10), 129.8 (C17, C19), 130.2 (C15, C16, C20), 137.6 (C18), 151.2 (C8), 154.93 (C12), 182.82 (C14), 192.15 (C7), 195.75 (C5); MS m/z: 402.10 [M + H]⁺. Analysis calculated (%) for C₂₀H₁₉NO₄S₂: C 59.83, H 4.77, N 3.49, S 15.97%; found: C 59.72, H 4.85, N 3.61, S 15.94.

S6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The C-bound H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.93–0.97Å and U_iso(H) = 1.2U_eq(C).

Related literature

For related literature, see: Groom & Allen (2014); Hirschelman et al. (2002); Jian et al. (2006); Mahesh Kumar, Mahabhaleshwaraiah, Kotresh, Roopashree & Devarajegowda (2013); Naoto et al. (2008); Scozzafava et al. (2000).

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SMART (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and CAMERON (Watkin et al., 1993); software used to prepare material for publication: PARST (Nardelli, 1995) and PLATON (Spek, 2009).

Figures

Fig. 1. The molecular structure of the title compound, showing 50% displacement ellipsoids.

Fig. 2. Packing diagram of the title compound, with C—H···O and C—H···π interactions indicated by dashed lines.

3-({[(Morpholin-4-yl)carbonothioyl]sulfanyl}acetyl)phenyl benzoate

Crystal data

C20H19NO4S2	Z = 4
Mr = 401.48	F(000) = 840
Monoclinic, P21/c	Dx = 1.403 Mg m^−3
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 19.5521 (7) Å	θ = 1.5°
b = 5.3649 (2) Å	µ = 0.31 mm^−1
c = 18.5142 (6) Å	T = 296 K
β = 101.816 (2)°	Block, colourless
V = 1900.90 (12) Å^3	0.35 × 0.31 × 0.25 mm

Data collection

Bruker SMART CCD area-detector diffractometer	3539 independent reflections
Radiation source: fine-focus sealed tube	2613 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
ϕ and ω scans	θmax = 25.5°, θmin = 1.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −23→21
Tmin = 0.887, Tmax = 0.934	k = −6→6
12830 measured reflections	l = −22→22

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.122	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0581P)^2 + 0.4768P] where P = (Fo^2 + 2Fc^2)/3
3539 reflections	(Δ/σ)max = 0.001
244 parameters	Δρmax = 0.31 e Å^−3
0 restraints	Δρmin = −0.22 e Å^−3

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.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	0.13247 (3)	1.07076 (13)	0.54256 (3)	0.0473 (2)
S2	0.23625 (3)	1.18442 (16)	0.68201 (4)	0.0652 (3)
O1	0.00887 (10)	1.6886 (4)	0.68361 (10)	0.0733 (6)
O2	0.14049 (8)	0.7580 (4)	0.42396 (9)	0.0697 (6)
O3	0.42171 (7)	0.3229 (3)	0.54362 (8)	0.0483 (4)
O4	0.39360 (9)	−0.0264 (4)	0.59595 (10)	0.0741 (6)
N1	0.10421 (9)	1.3302 (4)	0.65235 (10)	0.0531 (6)
C1	0.00244 (13)	1.5923 (6)	0.61218 (14)	0.0639 (8)
H1A	0.0271	1.7004	0.5841	0.077*
H1B	−0.0465	1.5919	0.588	0.077*
C2	0.03069 (12)	1.3339 (5)	0.61164 (14)	0.0614 (8)
H2A	0.003	1.2205	0.6347	0.074*
H2B	0.0282	1.2798	0.5612	0.074*
C3	0.11178 (14)	1.4422 (6)	0.72615 (13)	0.0636 (8)
H3A	0.161	1.4564	0.7487	0.076*
H3B	0.0899	1.3352	0.7571	0.076*
C4	0.07911 (14)	1.6908 (6)	0.72117 (15)	0.0684 (8)
H4A	0.0816	1.7552	0.7706	0.082*
H4B	0.1053	1.8027	0.6959	0.082*
C5	0.15653 (11)	1.2086 (5)	0.63120 (11)	0.0413 (5)
C6	0.20694 (11)	0.8751 (5)	0.54092 (12)	0.0456 (6)
H6A	0.2483	0.9771	0.5431	0.055*
H6B	0.215	0.7648	0.5833	0.055*
C7	0.19298 (11)	0.7242 (5)	0.47079 (12)	0.0452 (6)
C8	0.24493 (10)	0.5309 (4)	0.46121 (11)	0.0395 (5)
C9	0.22848 (12)	0.3671 (5)	0.40227 (11)	0.0479 (6)
H9	0.1857	0.3808	0.3696	0.058*
C10	0.27482 (12)	0.1849 (5)	0.39175 (12)	0.0526 (7)
H10	0.263	0.075	0.3523	0.063*
C11	0.33890 (12)	0.1638 (5)	0.43933 (12)	0.0483 (6)
H11	0.3705	0.0409	0.4323	0.058*
C12	0.35499 (10)	0.3272 (5)	0.49695 (11)	0.0419 (6)
C13	0.30942 (10)	0.5091 (4)	0.50962 (11)	0.0414 (5)
H13	0.3214	0.616	0.5498	0.05*
C14	0.43558 (11)	0.1310 (5)	0.59189 (11)	0.0420 (5)
C15	0.50633 (10)	0.1476 (4)	0.63896 (11)	0.0372 (5)
C16	0.52631 (11)	−0.0360 (5)	0.69145 (12)	0.0453 (6)
H16	0.4962	−0.1674	0.695	0.054*
C17	0.59067 (12)	−0.0250 (5)	0.73859 (12)	0.0504 (6)
H17	0.604	−0.149	0.7738	0.061*
C18	0.63503 (12)	0.1690 (5)	0.73352 (13)	0.0513 (6)
H18	0.6783	0.1772	0.7656	0.062*
C19	0.61594 (12)	0.3512 (5)	0.68132 (14)	0.0541 (7)
H19	0.6464	0.4817	0.678	0.065*
C20	0.55158 (11)	0.3418 (5)	0.63371 (12)	0.0469 (6)
H20	0.5388	0.4654	0.5983	0.056*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0349 (3)	0.0585 (5)	0.0456 (3)	0.0066 (3)	0.0015 (2)	−0.0034 (3)
S2	0.0367 (3)	0.0894 (6)	0.0619 (4)	0.0102 (3)	−0.0081 (3)	−0.0198 (4)
O1	0.0666 (12)	0.0761 (15)	0.0765 (12)	0.0228 (11)	0.0129 (10)	−0.0131 (11)
O2	0.0453 (10)	0.0814 (15)	0.0702 (11)	0.0143 (10)	−0.0169 (8)	−0.0206 (10)
O3	0.0345 (8)	0.0437 (11)	0.0624 (9)	−0.0025 (7)	−0.0006 (7)	0.0083 (8)
O4	0.0600 (11)	0.0719 (15)	0.0788 (12)	−0.0315 (11)	−0.0128 (9)	0.0217 (10)
N1	0.0410 (11)	0.0666 (16)	0.0477 (11)	0.0127 (10)	−0.0001 (8)	−0.0080 (10)
C1	0.0484 (15)	0.071 (2)	0.0681 (17)	0.0092 (14)	0.0027 (12)	0.0023 (15)
C2	0.0393 (13)	0.076 (2)	0.0649 (15)	0.0129 (13)	0.0018 (11)	−0.0099 (14)
C3	0.0595 (16)	0.080 (2)	0.0498 (14)	0.0117 (15)	0.0066 (11)	−0.0060 (14)
C4	0.0686 (19)	0.069 (2)	0.0673 (17)	0.0034 (16)	0.0121 (14)	−0.0146 (15)
C5	0.0359 (11)	0.0424 (15)	0.0444 (11)	0.0010 (10)	0.0051 (9)	0.0039 (10)
C6	0.0334 (11)	0.0534 (17)	0.0481 (12)	0.0039 (11)	0.0041 (9)	−0.0035 (11)
C7	0.0341 (12)	0.0490 (17)	0.0492 (12)	−0.0040 (11)	0.0004 (9)	−0.0029 (11)
C8	0.0315 (11)	0.0433 (15)	0.0427 (11)	−0.0051 (10)	0.0049 (9)	−0.0010 (10)
C9	0.0429 (13)	0.0561 (18)	0.0417 (12)	−0.0031 (12)	0.0014 (10)	−0.0037 (11)
C10	0.0560 (15)	0.0570 (19)	0.0434 (12)	0.0016 (13)	0.0064 (11)	−0.0101 (11)
C11	0.0477 (13)	0.0488 (17)	0.0499 (13)	0.0060 (11)	0.0134 (10)	−0.0011 (11)
C12	0.0310 (11)	0.0450 (16)	0.0485 (12)	−0.0035 (10)	0.0055 (9)	0.0031 (10)
C13	0.0357 (11)	0.0413 (15)	0.0447 (12)	−0.0064 (10)	0.0024 (9)	−0.0039 (10)
C14	0.0400 (12)	0.0404 (16)	0.0456 (12)	−0.0030 (11)	0.0089 (9)	−0.0027 (10)
C15	0.0344 (11)	0.0326 (14)	0.0449 (11)	0.0006 (10)	0.0092 (9)	−0.0050 (10)
C16	0.0441 (13)	0.0379 (15)	0.0546 (13)	−0.0026 (11)	0.0121 (10)	0.0023 (11)
C17	0.0482 (14)	0.0488 (18)	0.0527 (13)	0.0085 (12)	0.0066 (11)	0.0091 (11)
C18	0.0379 (13)	0.0547 (18)	0.0571 (14)	0.0041 (12)	0.0004 (10)	−0.0041 (12)
C19	0.0384 (13)	0.0465 (18)	0.0740 (16)	−0.0093 (11)	0.0039 (11)	0.0008 (13)
C20	0.0410 (13)	0.0383 (16)	0.0592 (14)	−0.0014 (11)	0.0054 (10)	0.0063 (11)

Geometric parameters (Å, º)

S1—C5	1.774 (2)	C6—H6B	0.97
S1—C6	1.800 (2)	C7—C8	1.487 (3)
S2—C5	1.653 (2)	C8—C9	1.387 (3)
O1—C1	1.401 (3)	C8—C13	1.394 (3)
O1—C4	1.407 (3)	C9—C10	1.374 (3)
O2—C7	1.214 (2)	C9—H9	0.93
O3—C14	1.354 (3)	C10—C11	1.381 (3)
O3—C12	1.410 (2)	C10—H10	0.93
O4—C14	1.191 (3)	C11—C12	1.367 (3)
N1—C5	1.338 (3)	C11—H11	0.93
N1—C3	1.472 (3)	C12—C13	1.374 (3)
N1—C2	1.480 (3)	C13—H13	0.93
C1—C2	1.493 (4)	C14—C15	1.479 (3)
C1—H1A	0.97	C15—C16	1.382 (3)
C1—H1B	0.97	C15—C20	1.383 (3)
C2—H2A	0.97	C16—C17	1.378 (3)
C2—H2B	0.97	C16—H16	0.93
C3—C4	1.474 (4)	C17—C18	1.370 (3)
C3—H3A	0.97	C17—H17	0.93
C3—H3B	0.97	C18—C19	1.371 (3)
C4—H4A	0.97	C18—H18	0.93
C4—H4B	0.97	C19—C20	1.382 (3)
C6—C7	1.507 (3)	C19—H19	0.93
C6—H6A	0.97	C20—H20	0.93
C5—S1—C6	101.33 (10)	C8—C7—C6	118.02 (18)
C1—O1—C4	111.06 (19)	C9—C8—C13	119.1 (2)
C14—O3—C12	116.89 (17)	C9—C8—C7	118.78 (19)
C5—N1—C3	122.22 (19)	C13—C8—C7	122.1 (2)
C5—N1—C2	125.35 (19)	C10—C9—C8	120.6 (2)
C3—N1—C2	111.70 (18)	C10—C9—H9	119.7
O1—C1—C2	112.8 (2)	C8—C9—H9	119.7
O1—C1—H1A	109	C9—C10—C11	120.4 (2)
C2—C1—H1A	109	C9—C10—H10	119.8
O1—C1—H1B	109	C11—C10—H10	119.8
C2—C1—H1B	109	C12—C11—C10	118.6 (2)
H1A—C1—H1B	107.8	C12—C11—H11	120.7
N1—C2—C1	109.3 (2)	C10—C11—H11	120.7
N1—C2—H2A	109.8	C11—C12—C13	122.4 (2)
C1—C2—H2A	109.8	C11—C12—O3	120.3 (2)
N1—C2—H2B	109.8	C13—C12—O3	117.27 (19)
C1—C2—H2B	109.8	C12—C13—C8	118.9 (2)
H2A—C2—H2B	108.3	C12—C13—H13	120.6
N1—C3—C4	110.6 (2)	C8—C13—H13	120.6
N1—C3—H3A	109.5	O4—C14—O3	122.2 (2)
C4—C3—H3A	109.5	O4—C14—C15	125.4 (2)
N1—C3—H3B	109.5	O3—C14—C15	112.34 (19)
C4—C3—H3B	109.5	C16—C15—C20	119.5 (2)
H3A—C3—H3B	108.1	C16—C15—C14	117.8 (2)
O1—C4—C3	113.0 (2)	C20—C15—C14	122.6 (2)
O1—C4—H4A	109	C17—C16—C15	120.3 (2)
C3—C4—H4A	109	C17—C16—H16	119.8
O1—C4—H4B	109	C15—C16—H16	119.8
C3—C4—H4B	109	C18—C17—C16	119.8 (2)
H4A—C4—H4B	107.8	C18—C17—H17	120.1
N1—C5—S2	124.08 (17)	C16—C17—H17	120.1
N1—C5—S1	113.60 (15)	C17—C18—C19	120.3 (2)
S2—C5—S1	122.32 (13)	C17—C18—H18	119.8
C7—C6—S1	108.88 (15)	C19—C18—H18	119.8
C7—C6—H6A	109.9	C18—C19—C20	120.3 (2)
S1—C6—H6A	109.9	C18—C19—H19	119.9
C7—C6—H6B	109.9	C20—C19—H19	119.9
S1—C6—H6B	109.9	C19—C20—C15	119.7 (2)
H6A—C6—H6B	108.3	C19—C20—H20	120.2
O2—C7—C8	121.2 (2)	C15—C20—H20	120.2
O2—C7—C6	120.8 (2)

Hydrogen-bond geometry (Å, º)

Cg is the centroid of the C15–C20 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2B···S1	0.97	2.41	2.938 (2)	114
C3—H3A···S2	0.97	2.56	3.052 (5)	111
C13—H13···O4^i	0.93	2.43	3.224 (3)	143
C11—H11···Cg^ii	0.93	2.88	3.629 (2)	138

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