3-(2-Hy­droxy-4-meth­oxy­phen­yl)-N-(2-meth­oxy­phen­yl)-5-(naphthalen-1-yl)-4,5-di­hydro-1H-pyrazole-1-carbo­thio­amide

Ahn, S.; Lim, Y.; Sung, J.; Koh, D.

doi:10.1107/S2414314617007325

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 5| May 2017| x170732

https://doi.org/10.1107/S2414314617007325

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3-(2-Hydroxy-4-methoxyphenyl)-N-(2-methoxyphenyl)-5-(naphthalen-1-yl)-4,5-dihydro-1H-pyrazole-1-carbothioamide

Seunghyun Ahn,^a Yoongho Lim,^a Jiha Sung ^b and Dongsoo Koh ^b ^*

^aDivision of Bioscience and Biotechnology, BMIC, Konkuk University, Seoul 143-701, Republic of Korea, and ^bDepartment of Applied Chemistry, Dongduk Women's University, Seoul 136-714, Republic of Korea
^*Correspondence e-mail: dskoh@dongduk.ac.kr

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 7 May 2017; accepted 17 May 2017; online 31 May 2017)

In the title molecule, C₂₈H₂₅N₃O₃S, the dihedral angles formed by the naphthalene ring system and the benzene rings are 73.03 (13) and 74.04 (11)°. The benzene rings attached to the central pyrazoline ring are almost coplanar, as indicated by the dihedral angle of 2.22 (10)° between them. The C atom of the methoxy group of the phenol ring is essentially coplanar with the ring [C—C—O—C = −0.3 (3)°], whereas the C atom of the methoxy group of the thioamide benzene ring is slightly twisted [C—C—O—C = 5.4 (3)°]. An intramolecular O—H⋯N hydrogen bond generates an S(6) ring motif. In the crystal, pairs of very weak C—H⋯S interactions form inversion dimers with an R₂²(18) motif.

Keywords: crystal structure; pyrazoline; thioamide.

CCDC reference: 1550731

Structure description

Pyrazolines show a broad spectrum of biological activities including the dual function of antimalarial and antimicrobial (Mishra, et al., 2017 ), antibacterial (Viveka et al., 2015 ), anti-inflammatory (Kharbanda, et al., 2014 ) and antitumor activities (Bashir et al., 2011 ). In continuation of our studies of new pyrazoline derivatives which may show broad range of biological activities (Jung et al. 2015 ), the title compound I was synthesized and its crystal structure was determined. For related structures, see: Abdel-Wahab et al. (2013 ); Koh et al. (2014 ).

The molecular structure of I is shown in Fig. 1. The benzene ring and naphthalene ring system are attached at the C1 and C3 position of central pyrazoline ring and another benzene ring is attached at N1 by a carbothioamide linkage. The dihedral angles formed by the naphthalene ring system at C3 and the benzene rings at C1 and N1 are 73.03 (13) and 74.04 (11)°, respectively. The benzene rings attached to the pyrazoline ring at C1 and N1 are almost in the same plane [dihedral angle = 2.22 (10)°]. The C atom of the methoxy group of the phenol ring is essentially co-planar with the ring [C8—C7—O2—C10 = −0.3 (3)°], whereas the C atom of the methoxy group at the thioamide benzene ring is slightly twisted from the ring plane [C24—C23—O3—C28 = 5.4 (3)°]. An intramolecular O1—H1O⋯N1 hydrogen bond forms an S(6) ring motif (Table 1). In the crystal, pairs of week C—H⋯S interactions form inversion dimers (Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N2	0.84	1.96	2.6889 (19)	145
C18—H18⋯S1ⁱ	0.95	2.96	3.712 (2)	137
Symmetry code: (i) -x+2, -y+1, -z+2.

Figure 1
The molecular structure of the title compound, showing displacement ellipsoids drawn at the 50% probability level

Figure 2
A view of an inversion dimer formed by a pair of C—H⋯S interactions in the crystal structure of the title compound.

Synthesis and crystallization

By the previously reported method (Jung et al. 2015), chalcone intermediate III was prepared and converted into pyrazoline intermediate IV via imine formation followed by Michael addition of hydrazine. The reaction between IV and isothiocyanate V gave the desired pyrazoline carbothiamide (see Fig. 3).

Figure 3
The synthetic procedure for the title compound.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₂₈H₂₅N₃O₃S
M_r	483.57
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	6.8521 (4), 23.1503 (13), 15.0422 (8)
β (°)	99.365 (1)
V (Å³)	2354.3 (2)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.17
Crystal size (mm)	0.22 × 0.16 × 0.10

Data collection
Diffractometer	Bruker SMART CCD
No. of measured, independent and observed [I > 2σ(I)] reflections	17230, 5827, 3091
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.147, 0.96
No. of reflections	5827
No. of parameters	319
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.24
Computer programs: SMART and SAINT (Bruker, 2000 ) and SHELXTL (Sheldrick, 2008 ).

Structural data

CCDC reference: 1550731

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314617007325/hb4146sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617007325/hb4146Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617007325/hb4146Isup3.cml

checkCIF report

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

3-(2-Hydroxy-4-methoxyphenyl)-N-(2-methoxyphenyl)-5-(naphthalen-1-yl)-4,5-dihydro-1H-pyrazole-1-carbothioamide top

Crystal data top

C₂₈H₂₅N₃O₃S	F(000) = 1016
M_r = 483.57	D_x = 1.364 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5750 reflections
a = 6.8521 (4) Å	θ = 2.2–27.9°
b = 23.1503 (13) Å	µ = 0.17 mm⁻¹
c = 15.0422 (8) Å	T = 173 K
β = 99.365 (1)°	Block, yellow
V = 2354.3 (2) Å³	0.22 × 0.16 × 0.10 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	3091 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.044
Graphite monochromator	θ_max = 28.3°, θ_min = 1.8°
phi and ω scans	h = −8→9
17230 measured reflections	k = −23→30
5827 independent reflections	l = −20→17

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.147	H-atom parameters constrained
S = 0.96	w = 1/[σ²(F_o²) + (0.0716P)²] where P = (F_o² + 2F_c²)/3
5827 reflections	(Δ/σ)_max = 0.001
319 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Special details top

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
N1	0.6669 (2)	0.68425 (6)	0.92398 (10)	0.0466 (4)
N2	0.7136 (2)	0.74261 (6)	0.93947 (10)	0.0443 (4)
C1	0.8947 (3)	0.74602 (8)	0.98041 (11)	0.0405 (4)
C2	0.9924 (3)	0.68823 (7)	0.99689 (12)	0.0431 (4)
H2A	1.0532	0.6837	1.0609	0.052*
H2B	1.0951	0.6826	0.9584	0.052*
C3	0.8196 (3)	0.64595 (8)	0.97126 (12)	0.0437 (5)
H3	0.8551	0.6155	0.9296	0.052*
C4	0.9887 (3)	0.80096 (8)	1.00541 (12)	0.0406 (4)
C5	0.8889 (3)	0.85421 (8)	0.99168 (12)	0.0448 (5)
O1	0.69489 (19)	0.85814 (6)	0.95457 (10)	0.0583 (4)
H1	0.6497	0.8249	0.9416	0.087*
C6	0.9869 (3)	0.90568 (8)	1.01527 (13)	0.0478 (5)
H6	0.9175	0.9413	1.0064	0.057*
C7	1.1853 (3)	0.90539 (8)	1.05168 (12)	0.0457 (5)
C8	1.2875 (3)	0.85359 (8)	1.06688 (13)	0.0490 (5)
H8	1.4235	0.8533	1.0928	0.059*
C9	1.1890 (3)	0.80279 (8)	1.04382 (12)	0.0456 (5)
H9	1.2594	0.7675	1.0543	0.055*
O2	1.2692 (2)	0.95858 (5)	1.06886 (9)	0.0563 (4)
C10	1.4744 (3)	0.96092 (9)	1.10511 (15)	0.0614 (6)
H10A	1.4972	0.9425	1.1645	0.092*
H10B	1.5173	1.0013	1.1109	0.092*
H10C	1.5500	0.9406	1.0648	0.092*
C11	0.7552 (3)	0.61868 (8)	1.05338 (13)	0.0477 (5)
C12	0.5914 (3)	0.63734 (10)	1.08515 (15)	0.0646 (6)
H12	0.5114	0.6666	1.0533	0.078*
C13	0.5384 (4)	0.61442 (16)	1.1636 (2)	0.1038 (11)
H13	0.4251	0.6287	1.1855	0.125*
C14	0.6474 (5)	0.57218 (16)	1.2083 (2)	0.1130 (12)
H14	0.6082	0.5565	1.2611	0.136*
C15	0.8173 (4)	0.55059 (11)	1.17942 (17)	0.0820 (9)
C16	0.8761 (3)	0.57470 (8)	1.10030 (14)	0.0574 (6)
C17	1.0517 (4)	0.55469 (8)	1.07327 (16)	0.0678 (7)
H17	1.0942	0.5709	1.0217	0.081*
C18	1.1624 (5)	0.51184 (10)	1.1209 (2)	0.0945 (10)
H18	1.2799	0.4984	1.1018	0.113*
C19	1.1014 (6)	0.48799 (11)	1.1980 (2)	0.1073 (14)
H19	1.1788	0.4588	1.2312	0.129*
C20	0.9358 (6)	0.50619 (14)	1.2246 (2)	0.1161 (14)
H20	0.8958	0.4887	1.2759	0.139*
C21	0.4949 (3)	0.66760 (9)	0.87116 (12)	0.0486 (5)
S1	0.43887 (9)	0.59834 (2)	0.85550 (4)	0.0700 (2)
N3	0.3851 (2)	0.71315 (7)	0.83677 (11)	0.0572 (5)
H3A	0.4489	0.7463	0.8429	0.069*
C22	0.1887 (3)	0.71777 (9)	0.79305 (12)	0.0484 (5)
C23	0.1202 (3)	0.77489 (9)	0.78290 (12)	0.0491 (5)
C24	−0.0711 (3)	0.78644 (9)	0.74395 (13)	0.0547 (5)
H24	−0.1168	0.8252	0.7370	0.066*
C25	−0.1979 (3)	0.74061 (10)	0.71471 (14)	0.0604 (6)
H25	−0.3308	0.7482	0.6880	0.073*
C26	−0.1321 (3)	0.68513 (10)	0.72435 (13)	0.0584 (6)
H26	−0.2202	0.6543	0.7046	0.070*
C27	0.0604 (3)	0.67287 (9)	0.76234 (13)	0.0550 (5)
H27	0.1051	0.6340	0.7675	0.066*
O3	0.2590 (2)	0.81574 (6)	0.81542 (9)	0.0614 (4)
C28	0.1973 (3)	0.87432 (9)	0.81590 (14)	0.0618 (6)
H28A	0.1587	0.8878	0.7538	0.093*
H28B	0.3065	0.8981	0.8463	0.093*
H28C	0.0843	0.8775	0.8480	0.093*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0468 (10)	0.0413 (9)	0.0474 (9)	−0.0097 (7)	−0.0052 (7)	0.0015 (7)
N2	0.0457 (10)	0.0427 (9)	0.0416 (8)	−0.0089 (7)	−0.0018 (7)	0.0023 (7)
C1	0.0398 (11)	0.0484 (11)	0.0330 (9)	−0.0060 (8)	0.0049 (8)	−0.0007 (8)
C2	0.0391 (11)	0.0472 (11)	0.0425 (10)	−0.0044 (8)	0.0052 (8)	−0.0030 (8)
C3	0.0443 (12)	0.0426 (10)	0.0416 (10)	−0.0029 (8)	−0.0011 (8)	−0.0047 (8)
C4	0.0375 (10)	0.0453 (11)	0.0390 (9)	−0.0053 (8)	0.0062 (8)	0.0010 (8)
C5	0.0374 (11)	0.0499 (11)	0.0462 (11)	−0.0061 (8)	0.0045 (8)	−0.0007 (9)
O1	0.0385 (8)	0.0512 (8)	0.0806 (10)	−0.0040 (6)	−0.0037 (7)	−0.0002 (8)
C6	0.0466 (12)	0.0451 (11)	0.0511 (11)	−0.0032 (8)	0.0060 (9)	−0.0033 (9)
C7	0.0474 (12)	0.0442 (11)	0.0455 (11)	−0.0113 (8)	0.0072 (9)	−0.0056 (8)
C8	0.0390 (11)	0.0533 (12)	0.0517 (11)	−0.0077 (9)	−0.0016 (9)	−0.0039 (9)
C9	0.0418 (11)	0.0448 (11)	0.0485 (11)	−0.0020 (8)	0.0028 (8)	−0.0011 (8)
O2	0.0505 (9)	0.0485 (8)	0.0671 (9)	−0.0129 (6)	0.0012 (7)	−0.0081 (7)
C10	0.0521 (14)	0.0600 (13)	0.0706 (14)	−0.0201 (10)	0.0055 (11)	−0.0133 (11)
C11	0.0416 (11)	0.0451 (11)	0.0510 (11)	−0.0138 (9)	−0.0082 (9)	0.0026 (9)
C12	0.0386 (13)	0.0925 (17)	0.0606 (14)	−0.0154 (11)	0.0019 (10)	0.0154 (12)
C13	0.0488 (16)	0.177 (3)	0.0843 (19)	−0.0222 (18)	0.0083 (14)	0.044 (2)
C14	0.068 (2)	0.168 (3)	0.097 (2)	−0.049 (2)	−0.0050 (17)	0.068 (2)
C15	0.0709 (18)	0.0750 (17)	0.0855 (18)	−0.0386 (14)	−0.0308 (14)	0.0361 (14)
C16	0.0543 (13)	0.0409 (11)	0.0670 (13)	−0.0190 (10)	−0.0199 (11)	0.0028 (10)
C17	0.0742 (17)	0.0421 (12)	0.0733 (14)	0.0039 (11)	−0.0293 (12)	−0.0160 (11)
C18	0.105 (2)	0.0466 (14)	0.108 (2)	0.0161 (14)	−0.0562 (18)	−0.0294 (15)
C19	0.125 (3)	0.0394 (14)	0.124 (3)	−0.0210 (16)	−0.082 (2)	0.0112 (15)
C20	0.114 (3)	0.080 (2)	0.127 (3)	−0.056 (2)	−0.061 (2)	0.0490 (19)
C21	0.0492 (12)	0.0522 (12)	0.0403 (10)	−0.0096 (9)	−0.0050 (9)	0.0028 (9)
S1	0.0692 (4)	0.0499 (3)	0.0790 (4)	−0.0112 (3)	−0.0234 (3)	−0.0076 (3)
N3	0.0526 (11)	0.0499 (10)	0.0607 (10)	−0.0181 (8)	−0.0158 (8)	0.0122 (8)
C22	0.0467 (12)	0.0584 (13)	0.0360 (10)	−0.0129 (9)	−0.0055 (8)	0.0083 (9)
C23	0.0503 (12)	0.0588 (13)	0.0358 (10)	−0.0164 (10)	−0.0002 (8)	0.0081 (9)
C24	0.0514 (13)	0.0651 (13)	0.0459 (11)	−0.0063 (10)	0.0028 (9)	0.0078 (10)
C25	0.0412 (12)	0.0847 (17)	0.0532 (12)	−0.0121 (11)	0.0010 (9)	0.0001 (11)
C26	0.0512 (13)	0.0697 (15)	0.0507 (12)	−0.0208 (11)	−0.0028 (10)	−0.0012 (11)
C27	0.0540 (13)	0.0604 (13)	0.0466 (11)	−0.0157 (10)	−0.0042 (9)	0.0019 (10)
O3	0.0631 (10)	0.0515 (9)	0.0618 (9)	−0.0154 (7)	−0.0130 (7)	0.0138 (7)
C28	0.0714 (16)	0.0558 (14)	0.0570 (13)	−0.0106 (11)	0.0066 (11)	0.0007 (10)

Geometric parameters (Å, º) top

N1—C21	1.365 (2)	C13—C14	1.343 (4)
N1—N2	1.399 (2)	C13—H13	0.9500
N1—N2	1.399 (2)	C14—C15	1.400 (4)
N1—C3	1.464 (2)	C14—H14	0.9500
N2—C1	1.295 (2)	C15—C20	1.414 (4)
C1—N2	1.295 (2)	C15—C16	1.430 (3)
C1—C4	1.448 (2)	C16—C17	1.410 (3)
C1—C2	1.499 (2)	C17—C18	1.377 (3)
C2—C3	1.536 (2)	C17—H17	0.9500
C2—H2A	0.9900	C18—C19	1.408 (5)
C2—H2B	0.9900	C18—H18	0.9500
C3—C11	1.515 (3)	C19—C20	1.332 (5)
C3—H3	1.0000	C19—H19	0.9500
C4—C9	1.400 (2)	C20—H20	0.9500
C4—C5	1.409 (2)	C21—N3	1.349 (2)
C5—O1	1.359 (2)	C21—S1	1.657 (2)
C5—C6	1.385 (2)	N3—C22	1.403 (2)
O1—H1	0.8400	N3—H3A	0.8800
C6—C7	1.380 (3)	C22—C27	1.391 (3)
C6—H6	0.9500	C22—C23	1.403 (3)
C7—O2	1.366 (2)	C23—C24	1.372 (3)
C7—C8	1.389 (3)	C23—O3	1.374 (2)
C8—C9	1.372 (2)	C24—C25	1.396 (3)
C8—H8	0.9500	C24—H24	0.9500
C9—H9	0.9500	C25—C26	1.361 (3)
O2—C10	1.424 (2)	C25—H25	0.9500
C10—H10A	0.9800	C26—C27	1.379 (3)
C10—H10B	0.9800	C26—H26	0.9500
C10—H10C	0.9800	C27—H27	0.9500
C11—C12	1.360 (3)	O3—C28	1.421 (2)
C11—C16	1.425 (3)	C28—H28A	0.9800
C12—C13	1.395 (3)	C28—H28B	0.9800
C12—H12	0.9500	C28—H28C	0.9800

C21—N1—N2	121.46 (15)	C14—C13—C12	120.0 (3)
C21—N1—N2	121.46 (15)	C14—C13—H13	120.0
C21—N1—C3	126.33 (15)	C12—C13—H13	120.0
N2—N1—C3	112.20 (13)	C13—C14—C15	121.8 (3)
N2—N1—C3	112.20 (13)	C13—C14—H14	119.1
C1—N2—N1	108.27 (14)	C15—C14—H14	119.1
N2—C1—C4	121.93 (16)	C14—C15—C20	123.5 (3)
N2—C1—C4	121.93 (16)	C14—C15—C16	118.7 (2)
N2—C1—C2	113.09 (15)	C20—C15—C16	117.8 (3)
N2—C1—C2	113.09 (15)	C17—C16—C11	123.1 (2)
C4—C1—C2	124.98 (15)	C17—C16—C15	118.7 (2)
C1—C2—C3	102.81 (14)	C11—C16—C15	118.1 (2)
C1—C2—H2A	111.2	C18—C17—C16	120.7 (3)
C3—C2—H2A	111.2	C18—C17—H17	119.7
C1—C2—H2B	111.2	C16—C17—H17	119.7
C3—C2—H2B	111.2	C17—C18—C19	119.9 (3)
H2A—C2—H2B	109.1	C17—C18—H18	120.0
N1—C3—C11	111.62 (16)	C19—C18—H18	120.0
N1—C3—C2	101.35 (14)	C20—C19—C18	120.4 (3)
C11—C3—C2	112.06 (14)	C20—C19—H19	119.8
N1—C3—H3	110.5	C18—C19—H19	119.8
C11—C3—H3	110.5	C19—C20—C15	122.4 (3)
C2—C3—H3	110.5	C19—C20—H20	118.8
C9—C4—C5	116.99 (16)	C15—C20—H20	118.8
C9—C4—C1	119.93 (16)	N3—C21—N1	112.16 (16)
C5—C4—C1	123.08 (16)	N3—C21—S1	126.88 (14)
O1—C5—C6	116.67 (17)	N1—C21—S1	120.95 (15)
O1—C5—C4	122.55 (16)	C21—N3—C22	132.25 (16)
C6—C5—C4	120.77 (17)	C21—N3—H3A	113.9
C5—O1—H1	109.5	C22—N3—H3A	113.9
C7—C6—C5	120.16 (18)	C27—C22—N3	127.24 (19)
C7—C6—H6	119.9	C27—C22—C23	119.08 (18)
C5—C6—H6	119.9	N3—C22—C23	113.67 (16)
O2—C7—C6	115.31 (17)	C24—C23—O3	125.16 (19)
O2—C7—C8	124.18 (17)	C24—C23—C22	120.62 (18)
C6—C7—C8	120.49 (17)	O3—C23—C22	114.21 (17)
C9—C8—C7	118.95 (18)	C23—C24—C25	119.3 (2)
C9—C8—H8	120.5	C23—C24—H24	120.4
C7—C8—H8	120.5	C25—C24—H24	120.4
C8—C9—C4	122.63 (18)	C26—C25—C24	120.3 (2)
C8—C9—H9	118.7	C26—C25—H25	119.8
C4—C9—H9	118.7	C24—C25—H25	119.8
C7—O2—C10	117.75 (16)	C25—C26—C27	121.11 (19)
O2—C10—H10A	109.5	C25—C26—H26	119.4
O2—C10—H10B	109.5	C27—C26—H26	119.4
H10A—C10—H10B	109.5	C26—C27—C22	119.6 (2)
O2—C10—H10C	109.5	C26—C27—H27	120.2
H10A—C10—H10C	109.5	C22—C27—H27	120.2
H10B—C10—H10C	109.5	C23—O3—C28	118.02 (16)
C12—C11—C16	120.0 (2)	O3—C28—H28A	109.5
C12—C11—C3	121.35 (18)	O3—C28—H28B	109.5
C16—C11—C3	118.59 (19)	H28A—C28—H28B	109.5
C11—C12—C13	121.3 (2)	O3—C28—H28C	109.5
C11—C12—H12	119.3	H28A—C28—H28C	109.5
C13—C12—H12	119.3	H28B—C28—H28C	109.5

C21—N1—N2—N2	0.00 (19)	C2—C3—C11—C16	−75.0 (2)
C3—N1—N2—N2	0.0 (2)	C16—C11—C12—C13	0.2 (3)
C21—N1—N2—C1	−170.99 (17)	C3—C11—C12—C13	−176.4 (2)
N2—N1—N2—C1	0 (100)	C11—C12—C13—C14	−1.5 (4)
C3—N1—N2—C1	9.8 (2)	C12—C13—C14—C15	1.1 (5)
N1—N2—C1—N2	0 (100)	C13—C14—C15—C20	−180.0 (3)
N2—N2—C1—C4	0.0 (9)	C13—C14—C15—C16	0.4 (4)
N1—N2—C1—C4	179.45 (15)	C12—C11—C16—C17	−177.63 (18)
N2—N2—C1—C2	0.0 (8)	C3—C11—C16—C17	−0.9 (3)
N1—N2—C1—C2	0.3 (2)	C12—C11—C16—C15	1.3 (3)
N2—C1—C2—C3	−9.4 (2)	C3—C11—C16—C15	177.99 (17)
N2—C1—C2—C3	−9.4 (2)	C14—C15—C16—C17	177.4 (2)
C4—C1—C2—C3	171.51 (16)	C20—C15—C16—C17	−2.3 (3)
C21—N1—C3—C11	−74.5 (2)	C14—C15—C16—C11	−1.6 (3)
N2—N1—C3—C11	104.57 (16)	C20—C15—C16—C11	178.78 (19)
N2—N1—C3—C11	104.57 (16)	C11—C16—C17—C18	−179.67 (18)
C21—N1—C3—C2	166.01 (18)	C15—C16—C17—C18	1.4 (3)
N2—N1—C3—C2	−14.88 (18)	C16—C17—C18—C19	−0.6 (3)
N2—N1—C3—C2	−14.88 (18)	C17—C18—C19—C20	0.8 (4)
C1—C2—C3—N1	13.60 (17)	C18—C19—C20—C15	−1.7 (4)
C1—C2—C3—C11	−105.54 (17)	C14—C15—C20—C19	−177.1 (3)
N2—C1—C4—C9	−175.47 (17)	C16—C15—C20—C19	2.5 (4)
N2—C1—C4—C9	−175.47 (17)	N2—N1—C21—N3	1.1 (3)
C2—C1—C4—C9	3.6 (3)	N2—N1—C21—N3	1.1 (3)
N2—C1—C4—C5	3.4 (3)	C3—N1—C21—N3	−179.84 (17)
N2—C1—C4—C5	3.4 (3)	N2—N1—C21—S1	−178.43 (13)
C2—C1—C4—C5	−177.52 (17)	N2—N1—C21—S1	−178.43 (13)
C9—C4—C5—O1	179.67 (17)	C3—N1—C21—S1	0.6 (3)
C1—C4—C5—O1	0.7 (3)	N1—C21—N3—C22	−167.46 (19)
C9—C4—C5—C6	0.2 (3)	S1—C21—N3—C22	12.1 (3)
C1—C4—C5—C6	−178.75 (17)	C21—N3—C22—C27	−9.8 (4)
O1—C5—C6—C7	−178.71 (18)	C21—N3—C22—C23	168.6 (2)
C4—C5—C6—C7	0.8 (3)	C27—C22—C23—C24	0.6 (3)
C5—C6—C7—O2	177.29 (16)	N3—C22—C23—C24	−177.93 (17)
C5—C6—C7—C8	−1.4 (3)	C27—C22—C23—O3	−179.93 (17)
O2—C7—C8—C9	−177.58 (17)	N3—C22—C23—O3	1.6 (2)
C6—C7—C8—C9	1.0 (3)	O3—C23—C24—C25	−179.18 (18)
C7—C8—C9—C4	0.0 (3)	C22—C23—C24—C25	0.3 (3)
C5—C4—C9—C8	−0.6 (3)	C23—C24—C25—C26	−0.3 (3)
C1—C4—C9—C8	178.38 (17)	C24—C25—C26—C27	−0.5 (3)
C6—C7—O2—C10	−178.99 (17)	C25—C26—C27—C22	1.3 (3)
C8—C7—O2—C10	−0.3 (3)	N3—C22—C27—C26	176.93 (18)
N1—C3—C11—C12	−11.2 (2)	C23—C22—C27—C26	−1.4 (3)
C2—C3—C11—C12	101.7 (2)	C24—C23—O3—C28	5.4 (3)
N1—C3—C11—C16	172.14 (15)	C22—C23—O3—C28	−174.03 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N2	0.84	1.96	2.6889 (19)	145
C18—H18···S1ⁱ	0.95	2.96	3.712 (2)	137

Symmetry code: (i) −x+2, −y+1, −z+2.

Funding information

Funding for this research was provided by: the Basic Science Research Program (award No. NRF-2016R1D1A1B03931623).

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