2-(3-Nitro­phen­yl)-3-phenyl-2,3-di­hydro-4H-1,3-benzo­thia­zin-4-one

Yennawar, H.P.; Silverberg, L.J.; Minehan, M.J.; Tierney, J.

doi:10.1107/S1600536813028389

organic compounds

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ISSN: 2056-9890

Volume 69| Part 11| November 2013| Page o1679

doi:10.1107/S1600536813028389

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2-(3-Nitrophenyl)-3-phenyl-2,3-dihydro-4H-1,3-benzothiazin-4-one

Hemant P. Yennawar,^a Lee J. Silverberg,^b ^* Michael J. Minehan ^b and John Tierney ^c

^aDepartment of Chemistry, Pennsylvania State University, University Park, PA 16802, USA, ^bPennsylvania State University, Schuylkill Campus, 200 University Drive, Schuylkill Haven, PA 17972, USA, and ^cPennsylvania State University, Brandywine Campus, 312 M Main Building, 25 Yearsley Mill Rd., Media, PA 19063, USA
^*Correspondence e-mail: ljs43@psu.edu

(Received 13 September 2013; accepted 15 October 2013; online 23 October 2013)

The title compound, C₂₀H₁₄N₂O₃S, has three aromatic rings, viz. (i) a phenyl ring, (ii) a 3-nitrophenyl and (iii) a 1,3-benzothiazine fused-ring system. The dihedral angle between (i) and (ii) is 85.31 (15)°, between (ii) and (iii) is 81.33 (15)° and between (i) and (iii) is 75.73 (15)°. The six-membered 1,3-thiazine ring has an envelope conformation with the C atom in the 2-position forming the flap. In the crystal, molecules are linked by weak C—H⋯O interactions, forming a three-dimensional network.

CCDC reference: 966653

Related literature

For amide bond formation using 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphorinane-2,4,6-trioxide (T3P), see: Dunetz et al. (2011 ). For preparation of various heterocycles using imines and T3P, see: Unsworth et al. (2013 ). For a review of 1,3-thiazin-4-ones, see: Ryabukhin et al. (1996 ). For other 2,3-diaryl-2,3-dihydro-1,3-benzothiazin-4-ones, see: Kamel et al. (2010 ); Kollenz & Ziegler (1970 ); Oae & Numata (1974 ); Ponci et al. (1963 ); Zarghi et al. (2009 ).

Experimental

Crystal data

C₂₀H₁₄N₂O₃S
M_r = 362.39
Monoclinic, P 2₁ /n
a = 9.8741 (13) Å
b = 13.0544 (18) Å
c = 13.365 (2) Å
β = 100.878 (4)°
V = 1691.7 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.22 mm⁻¹
T = 298 K
0.27 × 0.25 × 0.24 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.945, T_max = 0.951
9929 measured reflections
2904 independent reflections
2578 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.088
S = 1.04
2904 reflections
235 parameters
H-atom parameters not refined
Δρ_max = 0.16 e Å⁻³
Δρ_min = −2.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C19—H19⋯O3ⁱ	0.93	2.67	3.334 (8)	129
C7—H7⋯O2ⁱⁱ	0.98	2.58	3.424 (8)	145
C11—H11⋯O3ⁱⁱⁱ	0.93	2.71	3.362 (6)	128
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XSHELL (Bruker, 2001); software used to prepare material for publication: ORTEP-3 for Windows (Farrugia, 2012 ).

Supporting information

CCDC reference: 966653

Crystal structure: contains datablock I. DOI: 10.1107/S1600536813028389/fy2105sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813028389/fy2105Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813028389/fy2105Isup3.mol

Supporting information file. DOI: 10.1107/S1600536813028389/fy2105Isup4.cml

checkCIF report

Comment top

The six-membered 1,3-thiazin-4-one ring system has often been investigated for its biological activity and is of potential medicinal use (Ryabukhin et al., 1996)). As part of our studies of cyclic 1,3-thiaza-4-one compounds, we wished to form 2,3-diaryl-2,3-dihydro-1,3-benzothiazin-4-ones, of which only a small number have been reported (Kamel et al., 2010; Kollenz et al., 1970; Oae et al., 1974; Ponci et al., 1963; Zarghi et al., 2009). The title molecule was synthesized by condensation of 1-(3-nitrophenyl)-N-phenylmethanimine with thiosalicylic acid in the presence of 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphorinane-2,4,6-trioxide (T3P) and pyridine (Dunetz et al., 2011). A similar preparation of a 2,3-dialkyl-2,3-dihydro-1,3-benzothiazin-4-one was recently reported (Unsworth et al., 2013). We report here the crystal structure (Fig. 1) of the title compound, which has three aromatic rings: i) phenyl, ii) nitrophenyl and iii) phenyl, fused to a thiazine ring. The dihedral angle between (i) and (ii) is 85.31 (15)°, between (ii) and (iii) is 81.33 (15)° and between (i) and (iii) is 75.73 (15)°. The thiazine ring has an envelope conformation with the C atom in the 2-position forming the flap. In the crystal packing (Fig. 2), molecules are linked by weak C—H···O interactions (Table 1), resulting in a three-dimensional network.

Related literature top

For amide bond formation using 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphorinane-2,4,6-trioxide (T3P), see: Dunetz et al. (2011). For preparation of various heterocycles using imines and T3P, see: Unsworth et al. (2013). For a review of 1,3-thiazin-4-ones, see: Ryabukhin et al. (1996). For other 2,3-diaryl-2,3-dihydro-1,3-benzothiazin-4-ones, see: Kamel et al. (2010); Kollenz & Ziegler (1970); Oae & Numata (1974); Ponci et al. (1963); Zarghi et al. (2009).

Experimental top

A two-necked 25 ml roundbottom flask was oven-dried, cooled under N₂, and charged with a stir bar and 1-(3-nitrophenyl)-N-phenylmethanimine (1.3577 g, 6 mmol). Tetrahydrofuran (2.3 ml) was added, the solid dissolved, and the solution was stirred. Pyridine (1.95 ml, 24 mmol) was added and then thiosalicylic acid (0.9311 g, 6 mmol) was added. Finally, 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphorinane-2,4,6-trioxide in 2-methyltetrahydrofuran (50 weight percent; 7.1 ml, 12 mmol) was added. The reaction was stirred at room temperature for 46 h, then poured into a separatory funnel with dichloromethane. The mixture was washed with saturated sodium bicarbonate. The aqueous was then extracted three times with dichloromethane. The organics were combined and washed with saturated sodium bicarbonate, water, and saturated sodium chloride. The organic was dried over sodium sulfate, concentrated in vacuo and chromatographed on 30 g flash silica gel, eluting with 20–50% mixtures of ethyl acetate and hexanes. The product eluted with 30–40% EtOAc/hexanes and was concentrated in vacuo to a light yellow solid (1.0659 g). Recrystallization from ethyl acetate/hexanes gave light yellow crystals (0.8659 g, 39.8%). m.p.: 163–165°C. R_f = 0.62 (50% EtOAc/hexanes). Crystals for X-ray crystallography were grown by slow evaporation from ethanol.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XSHELL (Bruker, 2001); software used to prepare material for publication: ORTEP-3 for Windows (Farrugia, 2012).

Figures top

	Fig. 1. ORTEP view of the title comound. Thermal ellipsoids are drawn at 50% probability.
	Fig. 2. Crystal packing. C—H···O interactions are shown as dashed lines.

2-(3-Nitrophenyl)-3-phenyl-2,3-dihydro-4H-1,3-benzothiazin-4-one top

Crystal data top

C₂₀H₁₄N₂O₃S	D_x = 1.423 Mg m⁻³
M_r = 362.39	Melting point: 436 K
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.8741 (13) Å	Cell parameters from 3778 reflections
b = 13.0544 (18) Å	θ = 2.2–28.2°
c = 13.365 (2) Å	µ = 0.22 mm⁻¹
β = 100.878 (4)°	T = 298 K
V = 1691.7 (4) Å³	Block, colorless
Z = 4	0.27 × 0.25 × 0.24 mm
F(000) = 752

Data collection top

Bruker SMART-APEX CCD diffractometer	2904 independent reflections
Radiation source: fine-focus sealed tube	2572 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
Detector resolution: 8.34 pixels mm^-1	θ_max = 25.0°, θ_min = 2.2°
ϕ and ω scans	h = −11→10
Absorption correction: multi-scan (SADABS; Bruker, 2001)	k = −14→15
T_min = 0.944, T_max = 0.950	l = −15→15
9929 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.088	H-atom parameters not refined
S = 1.04	w = 1/[σ²(F_o²) + (0.0455P)² + 0.3773P] where P = (F_o² + 2F_c²)/3
2904 reflections	(Δ/σ)_max < 0.001
235 parameters	Δρ_max = 0.16 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₂₀H₁₄N₂O₃S	V = 1691.7 (4) Å³
M_r = 362.39	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.8741 (13) Å	µ = 0.22 mm⁻¹
b = 13.0544 (18) Å	T = 298 K
c = 13.365 (2) Å	0.27 × 0.25 × 0.24 mm
β = 100.878 (4)°

Data collection top

Bruker SMART-APEX CCD diffractometer	2904 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	2572 reflections with I > 2σ(I)
T_min = 0.944, T_max = 0.950	R_int = 0.023
9929 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.088	H-atom parameters not refined
S = 1.04	Δρ_max = 0.16 e Å⁻³
2904 reflections	Δρ_min = −0.22 e Å⁻³
235 parameters

Special details top

Experimental. The data collection nominally covered a full sphere of reciprocal space by a combination of 4 sets of ω scans each set at different ϕ and/or 2θ angles and each scan (10 s exposure) covering -0.300° degrees in ω. The crystal to detector distance was 5.82 cm. SADABS was used for absorption correction. R(int) was 0.0320 before and 0.0220 after correction. The Ratio of minimum to maximum transmission is 0.8417. The λ/2 correction factor is 0.0015.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.14364 (16)	0.21740 (11)	0.36136 (10)	0.0386 (3)
C2	0.22760 (15)	0.17463 (11)	0.30037 (10)	0.0360 (3)
H2	0.3208	0.1912	0.3105	0.043*
C3	0.17090 (14)	0.10692 (11)	0.22415 (10)	0.0342 (3)
C4	0.03139 (16)	0.08233 (13)	0.21336 (12)	0.0457 (4)
H4	−0.0081	0.0371	0.1624	0.055*
C5	−0.04918 (17)	0.12405 (15)	0.27706 (14)	0.0538 (4)
H5	−0.1415	0.1054	0.2696	0.065*
C6	0.00665 (17)	0.19323 (13)	0.35175 (12)	0.0477 (4)
H6	−0.0471	0.2225	0.3943	0.057*
C7	0.25569 (14)	0.05832 (12)	0.15304 (10)	0.0362 (3)
H7	0.2442	−0.0160	0.1579	0.043*
C8	0.49204 (14)	−0.00021 (11)	0.23007 (10)	0.0346 (3)
C9	0.45797 (17)	−0.05383 (13)	0.31141 (12)	0.0436 (4)
H9	0.3771	−0.0386	0.3344	0.052*
C10	0.54491 (18)	−0.13033 (13)	0.35838 (12)	0.0504 (4)
H10	0.5214	−0.1671	0.4122	0.060*
C11	0.66539 (18)	−0.15198 (13)	0.32568 (12)	0.0493 (4)
H11	0.7248	−0.2019	0.3585	0.059*
C12	0.69799 (16)	−0.09922 (13)	0.24379 (12)	0.0464 (4)
H12	0.7790	−0.1147	0.2211	0.056*
C13	0.61167 (16)	−0.02387 (12)	0.19526 (11)	0.0402 (3)
H13	0.6338	0.0107	0.1396	0.048*
C14	0.45482 (14)	0.17527 (11)	0.16948 (10)	0.0345 (3)
C15	0.36533 (15)	0.24938 (11)	0.10216 (10)	0.0357 (3)
C16	0.40628 (17)	0.35182 (12)	0.10646 (12)	0.0445 (4)
H16	0.4810	0.3725	0.1556	0.053*
C17	0.3380 (2)	0.42271 (14)	0.03930 (13)	0.0535 (4)
H17	0.3657	0.4909	0.0437	0.064*
C18	0.2281 (2)	0.39235 (15)	−0.03486 (13)	0.0560 (5)
H18	0.1839	0.4399	−0.0818	0.067*
C19	0.18368 (17)	0.29236 (15)	−0.03962 (11)	0.0502 (4)
H19	0.1089	0.2728	−0.0892	0.060*
C20	0.25026 (15)	0.22016 (12)	0.02946 (10)	0.0393 (4)
N1	0.20361 (17)	0.29450 (10)	0.43715 (10)	0.0481 (3)
N2	0.40305 (12)	0.07868 (9)	0.17982 (9)	0.0355 (3)
O1	0.12985 (17)	0.33388 (12)	0.48963 (10)	0.0775 (4)
O2	0.32476 (15)	0.31730 (11)	0.44327 (11)	0.0690 (4)
O3	0.57097 (11)	0.19924 (8)	0.21252 (8)	0.0449 (3)
S1	0.19079 (4)	0.09311 (3)	0.02046 (3)	0.04701 (15)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0458 (9)	0.0348 (8)	0.0366 (7)	0.0022 (6)	0.0111 (6)	0.0069 (6)
C2	0.0328 (7)	0.0382 (8)	0.0374 (7)	−0.0008 (6)	0.0076 (6)	0.0051 (6)
C3	0.0313 (7)	0.0341 (8)	0.0371 (7)	−0.0008 (6)	0.0063 (6)	0.0042 (6)
C4	0.0368 (8)	0.0472 (10)	0.0530 (9)	−0.0085 (7)	0.0088 (7)	−0.0021 (7)
C5	0.0349 (8)	0.0632 (11)	0.0672 (11)	−0.0059 (8)	0.0193 (8)	0.0036 (9)
C6	0.0474 (9)	0.0488 (10)	0.0524 (9)	0.0053 (8)	0.0236 (7)	0.0068 (7)
C7	0.0315 (8)	0.0348 (8)	0.0413 (7)	−0.0033 (6)	0.0041 (6)	−0.0027 (6)
C8	0.0318 (7)	0.0348 (8)	0.0365 (7)	0.0003 (6)	0.0050 (6)	−0.0026 (6)
C9	0.0398 (8)	0.0447 (9)	0.0491 (8)	0.0002 (7)	0.0158 (7)	0.0032 (7)
C10	0.0570 (10)	0.0462 (10)	0.0491 (9)	−0.0009 (8)	0.0130 (8)	0.0109 (7)
C11	0.0498 (10)	0.0430 (10)	0.0522 (9)	0.0100 (8)	0.0020 (7)	0.0033 (7)
C12	0.0369 (8)	0.0503 (10)	0.0525 (9)	0.0082 (7)	0.0102 (7)	−0.0031 (7)
C13	0.0384 (8)	0.0446 (9)	0.0387 (7)	0.0032 (7)	0.0101 (6)	0.0016 (6)
C14	0.0341 (8)	0.0385 (8)	0.0316 (7)	−0.0021 (6)	0.0082 (6)	−0.0016 (6)
C15	0.0362 (8)	0.0400 (9)	0.0323 (7)	0.0016 (6)	0.0103 (6)	−0.0007 (6)
C16	0.0483 (9)	0.0422 (9)	0.0445 (8)	0.0014 (7)	0.0126 (7)	−0.0003 (7)
C17	0.0640 (11)	0.0416 (10)	0.0594 (10)	0.0098 (8)	0.0227 (9)	0.0079 (7)
C18	0.0591 (11)	0.0615 (12)	0.0504 (9)	0.0228 (9)	0.0185 (8)	0.0185 (8)
C19	0.0417 (9)	0.0724 (13)	0.0366 (8)	0.0123 (8)	0.0071 (7)	0.0065 (7)
C20	0.0358 (8)	0.0519 (10)	0.0315 (7)	0.0048 (7)	0.0101 (6)	−0.0012 (6)
N1	0.0650 (10)	0.0413 (8)	0.0393 (7)	0.0036 (7)	0.0134 (7)	0.0025 (6)
N2	0.0288 (6)	0.0365 (7)	0.0411 (6)	0.0009 (5)	0.0064 (5)	0.0003 (5)
O1	0.0956 (11)	0.0797 (10)	0.0658 (8)	0.0015 (8)	0.0373 (8)	−0.0239 (7)
O2	0.0631 (9)	0.0687 (9)	0.0741 (9)	−0.0121 (7)	0.0103 (7)	−0.0241 (7)
O3	0.0368 (6)	0.0479 (7)	0.0465 (6)	−0.0081 (5)	−0.0013 (5)	0.0042 (5)
S1	0.0444 (2)	0.0576 (3)	0.0362 (2)	−0.00628 (18)	0.00036 (17)	−0.00963 (16)

Geometric parameters (Å, º) top

C1—C6	1.371 (2)	C11—C12	1.382 (2)
C1—C2	1.385 (2)	C11—H11	0.9300
C1—N1	1.471 (2)	C12—C13	1.381 (2)
C2—C3	1.385 (2)	C12—H12	0.9300
C2—H2	0.9300	C13—H13	0.9300
C3—C4	1.395 (2)	C14—O3	1.2227 (17)
C3—C7	1.519 (2)	C14—N2	1.3773 (19)
C4—C5	1.382 (2)	C14—C15	1.492 (2)
C4—H4	0.9300	C15—C16	1.395 (2)
C5—C6	1.381 (3)	C15—C20	1.401 (2)
C5—H5	0.9300	C16—C17	1.374 (2)
C6—H6	0.9300	C16—H16	0.9300
C7—N2	1.4558 (18)	C17—C18	1.383 (3)
C7—S1	1.8242 (14)	C17—H17	0.9300
C7—H7	0.9800	C18—C19	1.375 (3)
C8—C13	1.384 (2)	C18—H18	0.9300
C8—C9	1.387 (2)	C19—C20	1.394 (2)
C8—N2	1.4356 (18)	C19—H19	0.9300
C9—C10	1.387 (2)	C20—S1	1.7560 (17)
C9—H9	0.9300	N1—O1	1.2163 (19)
C10—C11	1.372 (2)	N1—O2	1.2203 (19)
C10—H10	0.9300

C6—C1—C2	122.79 (15)	C12—C11—H11	120.2
C6—C1—N1	118.93 (14)	C13—C12—C11	120.79 (15)
C2—C1—N1	118.24 (14)	C13—C12—H12	119.6
C3—C2—C1	119.11 (14)	C11—C12—H12	119.6
C3—C2—H2	120.4	C12—C13—C8	119.45 (14)
C1—C2—H2	120.4	C12—C13—H13	120.3
C2—C3—C4	118.50 (14)	C8—C13—H13	120.3
C2—C3—C7	122.20 (13)	O3—C14—N2	121.34 (13)
C4—C3—C7	119.29 (13)	O3—C14—C15	120.92 (13)
C5—C4—C3	121.17 (15)	N2—C14—C15	117.73 (12)
C5—C4—H4	119.4	C16—C15—C20	118.70 (14)
C3—C4—H4	119.4	C16—C15—C14	117.55 (13)
C6—C5—C4	120.34 (15)	C20—C15—C14	123.51 (14)
C6—C5—H5	119.8	C17—C16—C15	121.06 (16)
C4—C5—H5	119.8	C17—C16—H16	119.5
C1—C6—C5	118.05 (15)	C15—C16—H16	119.5
C1—C6—H6	121.0	C16—C17—C18	119.82 (17)
C5—C6—H6	121.0	C16—C17—H17	120.1
N2—C7—C3	114.41 (11)	C18—C17—H17	120.1
N2—C7—S1	110.18 (10)	C19—C18—C17	120.38 (16)
C3—C7—S1	111.69 (10)	C19—C18—H18	119.8
N2—C7—H7	106.7	C17—C18—H18	119.8
C3—C7—H7	106.7	C18—C19—C20	120.32 (16)
S1—C7—H7	106.7	C18—C19—H19	119.8
C13—C8—C9	119.98 (14)	C20—C19—H19	119.8
C13—C8—N2	119.27 (13)	C19—C20—C15	119.63 (15)
C9—C8—N2	120.74 (13)	C19—C20—S1	118.90 (12)
C8—C9—C10	119.81 (15)	C15—C20—S1	121.43 (11)
C8—C9—H9	120.1	O1—N1—O2	122.98 (15)
C10—C9—H9	120.1	O1—N1—C1	118.64 (16)
C11—C10—C9	120.25 (15)	O2—N1—C1	118.37 (14)
C11—C10—H10	119.9	C14—N2—C8	119.85 (11)
C9—C10—H10	119.9	C14—N2—C7	121.01 (12)
C10—C11—C12	119.69 (15)	C8—N2—C7	118.63 (12)
C10—C11—H11	120.2	C20—S1—C7	96.72 (7)

C6—C1—C2—C3	2.1 (2)	C16—C17—C18—C19	2.2 (3)
N1—C1—C2—C3	−175.83 (12)	C17—C18—C19—C20	−0.9 (3)
C1—C2—C3—C4	−1.6 (2)	C18—C19—C20—C15	−1.8 (2)
C1—C2—C3—C7	178.93 (13)	C18—C19—C20—S1	−179.74 (12)
C2—C3—C4—C5	−0.1 (2)	C16—C15—C20—C19	3.0 (2)
C7—C3—C4—C5	179.38 (15)	C14—C15—C20—C19	−171.23 (13)
C3—C4—C5—C6	1.5 (3)	C16—C15—C20—S1	−179.07 (11)
C2—C1—C6—C5	−0.7 (2)	C14—C15—C20—S1	6.68 (19)
N1—C1—C6—C5	177.16 (14)	C6—C1—N1—O1	0.6 (2)
C4—C5—C6—C1	−1.0 (3)	C2—C1—N1—O1	178.58 (14)
C2—C3—C7—N2	7.31 (19)	C6—C1—N1—O2	−178.18 (14)
C4—C3—C7—N2	−172.17 (13)	C2—C1—N1—O2	−0.2 (2)
C2—C3—C7—S1	−118.72 (13)	O3—C14—N2—C8	−8.7 (2)
C4—C3—C7—S1	61.80 (16)	C15—C14—N2—C8	170.05 (12)
C13—C8—C9—C10	0.7 (2)	O3—C14—N2—C7	162.90 (13)
N2—C8—C9—C10	179.50 (14)	C15—C14—N2—C7	−18.30 (18)
C8—C9—C10—C11	1.0 (2)	C13—C8—N2—C14	−55.44 (18)
C9—C10—C11—C12	−1.8 (3)	C9—C8—N2—C14	125.78 (15)
C10—C11—C12—C13	0.9 (3)	C13—C8—N2—C7	132.72 (14)
C11—C12—C13—C8	0.8 (2)	C9—C8—N2—C7	−46.06 (18)
C9—C8—C13—C12	−1.6 (2)	C3—C7—N2—C14	−69.47 (16)
N2—C8—C13—C12	179.58 (13)	S1—C7—N2—C14	57.35 (15)
O3—C14—C15—C16	−12.9 (2)	C3—C7—N2—C8	102.28 (14)
N2—C14—C15—C16	168.26 (13)	S1—C7—N2—C8	−130.90 (11)
O3—C14—C15—C20	161.39 (14)	C19—C20—S1—C7	−155.36 (12)
N2—C14—C15—C20	−17.4 (2)	C15—C20—S1—C7	26.72 (13)
C20—C15—C16—C17	−1.7 (2)	N2—C7—S1—C20	−54.94 (11)
C14—C15—C16—C17	172.90 (14)	C3—C7—S1—C20	73.38 (11)
C15—C16—C17—C18	−0.9 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C19—H19···O3ⁱ	0.93	2.63	3.2912 (19)	129
C7—H7···O2ⁱⁱ	0.98	2.59	3.435 (2)	145
C11—H11···O3ⁱⁱⁱ	0.93	2.71	3.363 (2)	128

Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) −x+1/2, y−1/2, −z+1/2; (iii) −x+3/2, y−1/2, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C19—H19···O3ⁱ	0.93	2.63	3.2912 (19)	128.5
C7—H7···O2ⁱⁱ	0.98	2.59	3.435 (2)	145.2
C11—H11···O3ⁱⁱⁱ	0.93	2.71	3.363 (2)	127.8

Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) −x+1/2, y−1/2, −z+1/2; (iii) −x+3/2, y−1/2, −z+1/2.

Acknowledgements

We acknowledge NSF funding (CHEM-0131112) for the X-ray diffractometer. We also express gratitude to Euticals for the gift of T3P in 2-methyltetrahydrofuran.

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