Crystal structure of flucetosulfuron

Park, H.; Kim, J.; Kwon, E.; Kim, T.H.

doi:10.1107/S2056989017012737

research communications

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ISSN: 2056-9890

Volume 73| Part 10| October 2017| Pages 1439-1442

https://doi.org/10.1107/S2056989017012737

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Crystal structure of flucetosulfuron

Hyunjin Park,^a Jineun Kim,^a ^* Eunjin Kwon ^a and Tae Ho Kim ^a ^*

^aDepartment of Chemistry (BK21 plus) and Research Institute of Natural Sciences, Gyeongsang National University, Jinju 52828, Republic of Korea
^*Correspondence e-mail: thkim@gnu.ac.kr, jekim@gnu.ac.kr

Edited by P. C. Healy, Griffith University, Australia (Received 4 September 2017; accepted 6 September 2017; online 12 September 2017)

The title compound, {systematic name: 1-[3-({[(4,6-dimethoxypyrimidin-2-yl)carbamoyl]amino}sulfonyl)pyridin-2-yl]-2-fluoropropyl 2-methoxyacetate}, C₁₈H₂₂FN₅O₈S, is used as a herbicide (pyrimidinylsulfonylurea herbicide). The dihedral angle between the mean planes of the pyridine and pyrimidine rings is 86.90 (7)°. In the crystal, N/C—H⋯O hydrogen bonds, C—H⋯F and C—H⋯π interactions link adjacent molecules, forming a chain along [020]. A further two C—H⋯O hydrogen bonds together with weak π–π interactions [ring centroid separation = 3.7584 (12) Å] further aggregate the structure into a three-dimensional architecture.

Keywords: crystal structure; herbicides; pyrimidinylsulfonylurea herbicide; flucetosulfuron.

CCDC reference: 1572854

1. Chemical context

Flucetosulfuron, a relatively new herbicide, inhibits acetolactate synthase (ALS) in plants, as do other ALS inhibitors such as imidazolinones, pyrimidinyloxybenzoates, triazolopyrimidines, and sulfonylaminocarbonyltriazolinones (Lee et al., 2014 ). It is a novel post-emergence sulfonylurea herbicide providing excellent control of Galium aparine and other important broadleaf weeds with good safety to cereal crops, wheat and barley (Kim, Lee et al., 2003 ) In rice, the herbicide provides excellent control of Echinochloa crus-galli, which is not or only marginally controlled by common sulfonylurea products, and also controls annual broadleaf weeds, sedges and perennial weeds of rice with similar efficacy to other sulfonylurea rice herbicides (Kim, Koo et al., 2003 ). Until now, its crystal structure had not been reported and we describe it herein.

2. Structural commentary

The structure of flucetosulfuron is shown in Fig. 1. The dihedral angle between the mean planes of the pyridine and pyrimidine rings is 86.90 (7)°. All bond lengths and angles are normal and comparable to those observed in similar crystal structures (Jeon et al., 2015 ; Chopra et al., 2004 ).

Figure 1
The molecular structure of the title compound with the atom labelling and displacement ellipsoids drawn at the 50% probability level. H atoms are shown as small spheres of arbitrary radius.

3. Supramolecular features

In the crystal, molecules are linked by C1—H1A⋯O3ⁱ, N3—H3N⋯O8ⁱ and C2—H2B⋯F1ⁱⁱ hydrogen bonds [H⋯O = 2.58, 2.01 and H⋯F = 2.53 Å; Table 1] and C1—H1B⋯Cg1ⁱ interactions [H⋯π = 2.74 Å], forming a chain structure along [020] (yellow dashed lines in Fig. 2). In addition, the chains are linked by C12—H12⋯O2ⁱⁱⁱ hydrogen bonds [H⋯O =2.42 Å], forming a two-dimensional network structure parallel to (020) (red dashed lines in Fig. 2). The C17—H17⋯O5^iv hydrogen bond [H⋯O =2.55 Å] and weak π–π interactions (N1–N2/C3–C6) [Cg2⋯Cg2^v= 3.7584 (12) Å; symmetry code: (v) −x + 2, −y + 1, −z + 1] generate a three-dimensional architecture with molecules stacked along the a-axis direction (black dashed lines in Fig. 3).

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the N5/C8–C12 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3N⋯O8ⁱ	0.88	2.01	2.885 (2)	174
C1—H1A⋯O3ⁱ	0.98	2.58	3.368 (3)	137
C2—H2B⋯F1ⁱⁱ	0.98	2.53	3.161 (2)	122
C12—H12⋯O2ⁱⁱⁱ	0.95	2.42	3.229 (3)	143
C17—H17A⋯O5^iv	0.99	2.55	3.367 (3)	139
C1—H1B⋯Cg1ⁱ	0.98	2.74	3.488 (2)	134
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x+1, -y+1, -z; (iii) x-1, y-1, z; (iv) x, y+1, z.

Figure 2
The N/C—H⋯O hydrogen bond, C—H⋯F and C—H⋯π interactions (yellow dashed lines) link adjacent molecules, forming chains along [020]. The chains are further linked by C—H⋯O hydrogen bonds (red dashed lines), forming a two-dimensional network parallel to (020). H atoms have been omitted for clarity.

Figure 3
A packing diagram showing the three-dimensional architecture formed by intermolecular C—H⋯O hydrogen bonds (red dashed lines) and π–π interactions (black dashed lines). H atoms have been omitted for clarity.

4. Database survey

We have reported the crystal structures of several pesticides including compounds with pyrimidinylsulfonylurea, dimethoxypyrimidin and sulfonylurea ring (Kang et al., 2015 ; Jeon et al., 2015; Kwon et al., 2016 ). Moreover, a database search (CSD Version 5.27, last update February 2017; Groom et al., 2016 ) yielded other comparable structures, methyl 2-{[3-(4,6-dimethoxypyrimidin-2-yl)ureido]sulfonylmethyl}benzoate (Xia et al., 2008 ), 2-amino-4,6-dimethoxypyrimidin-1-ium 2,2-dichloroacetate (Lin et al., 2012 ), N-[(perhydrocyclopenta[c]pyrrol-2-yl)aminocarbonyl]-o-toluenesulfonamide (Wu et al., 2012 ) and 4-{4-[N-(5,6-dimethoxypyrimidin-4-yl)sulfamoyl]phenylcarbamoyl}-2,6-dimethoxyphenyl acetate (Pan et al., 2012 ).

5. Synthesis and crystallization

The title compound was purchased from Dr Ehrenstorfer GmbH. Colourless single crystals suitable for X-ray diffraction were obtained from a CH₃CN solution by slow evaporation at room temperature.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All H atoms were positioned geometrically and refined using a riding model with d(N—H) = 0.88 Å, U_iso = 1.2U_eq(C) for urea N—H, d(C—H) = 0.95 Å, U_iso = 1.2U_eq(C) for aromatic C—H, d(C—H) = 0.98 Å, U_iso = 1.5U_eq(C) for methyl groups, d(C—H) = 0.99 Å, U_iso = 1.2U_eq(C) for CH₂ group, d(C—H) = 1.00 Å, U_iso = 1.5U_eq(C) for Csp³—H.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₈H₂₂FN₅O₈S
M_r	487.46
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	173
a, b, c (Å)	8.3993 (3), 9.1030 (3), 15.6862 (5)
α, β, γ (°)	92.116 (2), 101.113 (2), 112.810 (2)
V (Å³)	1076.53 (6)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.22
Crystal size (mm)	0.36 × 0.06 × 0.05

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.702, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	10919, 3773, 3081
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.099, 1.06
No. of reflections	3773
No. of parameters	302
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.39
Computer programs: APEX2 and SAINT (Bruker, 2014), SHELXS97 and SHELXTL (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), DIAMOND (Brandenburg, 2010 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1572854

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: https://doi.org/10.1107/S2056989017012737/hg5495sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017012737/hg5495Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2010); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).

1-[3-({[(4,6-Dimethoxypyrimidin-2-yl)carbamoyl]amino}sulfonyl)pyridin-2-yl]-2-fluoropropyl 2-methoxyacetate top

Crystal data top

C₁₈H₂₂FN₅O₈S	Z = 2
M_r = 487.46	F(000) = 508
Triclinic, P1	D_x = 1.504 Mg m⁻³
a = 8.3993 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.1030 (3) Å	Cell parameters from 3325 reflections
c = 15.6862 (5) Å	θ = 2.5–26.9°
α = 92.116 (2)°	µ = 0.22 mm⁻¹
β = 101.113 (2)°	T = 173 K
γ = 112.810 (2)°	Needle, colourless
V = 1076.53 (6) Å³	0.36 × 0.06 × 0.05 mm

Data collection top

Bruker APEXII CCD diffractometer	3081 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.031
Absorption correction: multi-scan (SADABS; Bruker, 2014)	θ_max = 25.0°, θ_min = 1.3°
T_min = 0.702, T_max = 0.746	h = −9→9
10919 measured reflections	k = −10→10
3773 independent reflections	l = −18→18

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.039	H-atom parameters constrained
wR(F²) = 0.099	w = 1/[σ²(F_o²) + (0.0439P)² + 0.337P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
3773 reflections	Δρ_max = 0.45 e Å⁻³
302 parameters	Δρ_min = −0.39 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.39351 (7)	0.10312 (6)	0.18674 (3)	0.02316 (15)
F1	0.2117 (2)	0.35690 (17)	−0.01327 (8)	0.0529 (4)
O1	1.0327 (2)	0.78934 (17)	0.56837 (9)	0.0345 (4)
O2	0.97933 (18)	0.63951 (17)	0.27393 (9)	0.0268 (3)
O3	0.34138 (19)	0.08587 (18)	0.37121 (9)	0.0309 (4)
O4	0.48165 (18)	0.18107 (17)	0.12133 (9)	0.0278 (4)
O5	0.3822 (2)	−0.05369 (17)	0.20150 (10)	0.0330 (4)
O6	0.26027 (17)	0.48834 (16)	0.21292 (8)	0.0226 (3)
O7	0.55822 (19)	0.62252 (18)	0.24672 (9)	0.0302 (4)
O8	0.53183 (18)	0.72872 (16)	0.41130 (9)	0.0262 (4)
N1	0.8060 (2)	0.5524 (2)	0.49899 (11)	0.0227 (4)
N2	0.7821 (2)	0.4766 (2)	0.34862 (10)	0.0213 (4)
N3	0.5794 (2)	0.3194 (2)	0.42532 (11)	0.0249 (4)
H3N	0.5538	0.3064	0.4771	0.030*
N4	0.4990 (2)	0.2289 (2)	0.27617 (10)	0.0252 (4)
H4N	0.5839	0.3209	0.2718	0.030*
N5	−0.0364 (2)	0.2072 (2)	0.11793 (12)	0.0310 (4)
C1	0.9641 (3)	0.7561 (3)	0.64590 (14)	0.0356 (6)
H1A	0.8389	0.7393	0.6326	0.053*
H1B	1.0313	0.8472	0.6918	0.053*
H1C	0.9752	0.6593	0.6662	0.053*
C2	0.8773 (3)	0.5257 (3)	0.19662 (13)	0.0285 (5)
H2A	0.8717	0.4188	0.2079	0.043*
H2B	0.9342	0.5588	0.1475	0.043*
H2C	0.7571	0.5224	0.1821	0.043*
C3	0.9464 (3)	0.6843 (2)	0.49563 (13)	0.0238 (5)
C4	0.7292 (3)	0.4557 (2)	0.42344 (13)	0.0207 (4)
C5	0.9225 (3)	0.6125 (2)	0.34821 (13)	0.0215 (5)
C6	1.0123 (3)	0.7244 (2)	0.42113 (13)	0.0253 (5)
H6	1.1113	0.8211	0.4205	0.030*
C7	0.4640 (3)	0.2007 (2)	0.35825 (13)	0.0234 (5)
C8	0.1749 (3)	0.0953 (2)	0.16496 (12)	0.0209 (5)
C9	0.1326 (3)	0.2238 (2)	0.13956 (13)	0.0229 (5)
C10	−0.1640 (3)	0.0645 (3)	0.12140 (15)	0.0358 (6)
H10	−0.2836	0.0525	0.1041	0.043*
C11	−0.1331 (3)	−0.0655 (3)	0.14834 (15)	0.0356 (6)
H11	−0.2283	−0.1633	0.1518	0.043*
C12	0.0406 (3)	−0.0500 (3)	0.17037 (14)	0.0303 (5)
H12	0.0674	−0.1376	0.1889	0.036*
C13	0.2671 (3)	0.3930 (2)	0.13829 (12)	0.0219 (5)
H13	0.3884	0.3942	0.1447	0.026*
C14	0.2184 (3)	0.4629 (3)	0.05544 (13)	0.0320 (5)
H14	0.0981	0.4629	0.0509	0.038*
C15	0.3463 (3)	0.6282 (3)	0.04812 (15)	0.0416 (6)
H15A	0.3513	0.7036	0.0959	0.062*
H15B	0.3069	0.6609	−0.0082	0.062*
H15C	0.4642	0.6286	0.0519	0.062*
C16	0.4167 (3)	0.5958 (2)	0.26289 (13)	0.0210 (5)
C17	0.3826 (3)	0.6730 (3)	0.34038 (12)	0.0240 (5)
H17A	0.3527	0.7642	0.3228	0.029*
H17B	0.2799	0.5939	0.3590	0.029*
C18	0.6598 (3)	0.8857 (3)	0.40752 (15)	0.0316 (5)
H18A	0.7041	0.8858	0.3541	0.047*
H18B	0.7587	0.9161	0.4588	0.047*
H18C	0.6045	0.9628	0.4071	0.047*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0254 (3)	0.0223 (3)	0.0209 (3)	0.0097 (2)	0.0034 (2)	0.0019 (2)
F1	0.0876 (12)	0.0416 (9)	0.0248 (7)	0.0235 (8)	0.0082 (7)	−0.0018 (6)
O1	0.0420 (10)	0.0256 (9)	0.0233 (8)	0.0007 (7)	0.0076 (7)	−0.0027 (6)
O2	0.0279 (8)	0.0261 (8)	0.0212 (8)	0.0035 (7)	0.0090 (6)	0.0038 (6)
O3	0.0267 (8)	0.0276 (9)	0.0286 (8)	0.0001 (7)	0.0071 (7)	0.0052 (7)
O4	0.0300 (8)	0.0334 (9)	0.0232 (8)	0.0144 (7)	0.0096 (6)	0.0055 (6)
O5	0.0405 (9)	0.0229 (8)	0.0371 (9)	0.0164 (7)	0.0046 (7)	0.0044 (7)
O6	0.0216 (7)	0.0217 (8)	0.0199 (7)	0.0049 (6)	0.0032 (6)	−0.0016 (6)
O7	0.0216 (8)	0.0325 (9)	0.0329 (9)	0.0077 (7)	0.0056 (7)	−0.0022 (7)
O8	0.0252 (8)	0.0225 (8)	0.0203 (7)	0.0007 (6)	0.0004 (6)	0.0015 (6)
N1	0.0227 (9)	0.0216 (9)	0.0217 (9)	0.0069 (8)	0.0043 (7)	0.0032 (7)
N2	0.0211 (9)	0.0224 (9)	0.0186 (9)	0.0070 (8)	0.0040 (7)	0.0049 (7)
N3	0.0247 (9)	0.0261 (10)	0.0169 (9)	0.0028 (8)	0.0044 (7)	0.0040 (7)
N4	0.0259 (10)	0.0240 (10)	0.0191 (9)	0.0034 (8)	0.0038 (7)	0.0039 (7)
N5	0.0226 (10)	0.0291 (11)	0.0374 (11)	0.0090 (9)	0.0027 (8)	−0.0029 (8)
C1	0.0451 (14)	0.0327 (13)	0.0241 (12)	0.0103 (11)	0.0094 (10)	−0.0029 (10)
C2	0.0318 (12)	0.0303 (12)	0.0216 (11)	0.0106 (10)	0.0060 (9)	0.0018 (9)
C3	0.0255 (11)	0.0194 (11)	0.0240 (11)	0.0079 (9)	0.0028 (9)	0.0022 (9)
C4	0.0201 (10)	0.0211 (11)	0.0212 (11)	0.0088 (9)	0.0034 (8)	0.0062 (9)
C5	0.0217 (11)	0.0226 (11)	0.0218 (11)	0.0098 (9)	0.0061 (8)	0.0072 (9)
C6	0.0242 (11)	0.0212 (11)	0.0256 (11)	0.0042 (9)	0.0046 (9)	0.0047 (9)
C7	0.0228 (11)	0.0234 (12)	0.0231 (11)	0.0088 (10)	0.0039 (9)	0.0045 (9)
C8	0.0233 (11)	0.0186 (11)	0.0166 (10)	0.0054 (9)	0.0018 (8)	−0.0006 (8)
C9	0.0230 (11)	0.0237 (11)	0.0178 (10)	0.0059 (9)	0.0030 (8)	−0.0018 (8)
C10	0.0206 (12)	0.0335 (14)	0.0439 (14)	0.0042 (11)	0.0030 (10)	−0.0089 (11)
C11	0.0285 (13)	0.0265 (13)	0.0412 (14)	0.0001 (11)	0.0088 (10)	−0.0034 (11)
C12	0.0348 (13)	0.0212 (12)	0.0303 (12)	0.0062 (10)	0.0077 (10)	0.0018 (9)
C13	0.0267 (11)	0.0214 (11)	0.0187 (10)	0.0104 (9)	0.0063 (8)	0.0004 (8)
C14	0.0467 (14)	0.0288 (13)	0.0205 (11)	0.0157 (11)	0.0065 (10)	0.0016 (9)
C15	0.0630 (18)	0.0304 (14)	0.0261 (13)	0.0128 (12)	0.0096 (12)	0.0091 (10)
C16	0.0221 (11)	0.0171 (10)	0.0213 (11)	0.0061 (9)	0.0024 (9)	0.0063 (8)
C17	0.0206 (11)	0.0246 (11)	0.0199 (11)	0.0028 (9)	0.0026 (8)	0.0019 (9)
C18	0.0281 (12)	0.0224 (12)	0.0343 (13)	0.0002 (10)	0.0058 (10)	0.0007 (10)

Geometric parameters (Å, º) top

S1—O5	1.4242 (15)	C1—H1C	0.9800
S1—O4	1.4295 (15)	C2—H2A	0.9800
S1—N4	1.6369 (17)	C2—H2B	0.9800
S1—C8	1.774 (2)	C2—H2C	0.9800
F1—C14	1.397 (2)	C3—C6	1.389 (3)
O1—C3	1.343 (2)	C5—C6	1.379 (3)
O1—C1	1.437 (3)	C6—H6	0.9500
O2—C5	1.338 (2)	C8—C12	1.385 (3)
O2—C2	1.448 (2)	C8—C9	1.398 (3)
O3—C7	1.207 (2)	C9—C13	1.520 (3)
O6—C16	1.359 (2)	C10—C11	1.371 (3)
O6—C13	1.455 (2)	C10—H10	0.9500
O7—C16	1.197 (2)	C11—C12	1.383 (3)
O8—C17	1.412 (2)	C11—H11	0.9500
O8—C18	1.429 (2)	C12—H12	0.9500
N1—C3	1.329 (3)	C13—C14	1.522 (3)
N1—C4	1.336 (2)	C13—H13	1.0000
N2—C4	1.328 (2)	C14—C15	1.497 (3)
N2—C5	1.339 (2)	C14—H14	1.0000
N3—C7	1.388 (3)	C15—H15A	0.9800
N3—C4	1.389 (2)	C15—H15B	0.9800
N3—H3N	0.8800	C15—H15C	0.9800
N4—C7	1.386 (3)	C16—C17	1.510 (3)
N4—H4N	0.8800	C17—H17A	0.9900
N5—C10	1.337 (3)	C17—H17B	0.9900
N5—C9	1.341 (3)	C18—H18A	0.9800
C1—H1A	0.9800	C18—H18B	0.9800
C1—H1B	0.9800	C18—H18C	0.9800

O5—S1—O4	119.31 (9)	C12—C8—S1	116.68 (16)
O5—S1—N4	110.36 (9)	C9—C8—S1	123.71 (15)
O4—S1—N4	103.89 (9)	N5—C9—C8	121.03 (18)
O5—S1—C8	107.60 (9)	N5—C9—C13	113.94 (18)
O4—S1—C8	109.39 (9)	C8—C9—C13	124.95 (18)
N4—S1—C8	105.49 (9)	N5—C10—C11	124.2 (2)
C3—O1—C1	117.99 (17)	N5—C10—H10	117.9
C5—O2—C2	117.95 (16)	C11—C10—H10	117.9
C16—O6—C13	117.59 (15)	C10—C11—C12	118.0 (2)
C17—O8—C18	114.20 (16)	C10—C11—H11	121.0
C3—N1—C4	114.61 (17)	C12—C11—H11	121.0
C4—N2—C5	116.32 (17)	C11—C12—C8	118.9 (2)
C7—N3—C4	130.02 (17)	C11—C12—H12	120.5
C7—N3—H3N	115.0	C8—C12—H12	120.5
C4—N3—H3N	115.0	O6—C13—C9	105.26 (15)
C7—N4—S1	124.61 (15)	O6—C13—C14	108.51 (16)
C7—N4—H4N	117.7	C9—C13—C14	111.96 (17)
S1—N4—H4N	117.7	O6—C13—H13	110.3
C10—N5—C9	118.31 (19)	C9—C13—H13	110.3
O1—C1—H1A	109.5	C14—C13—H13	110.3
O1—C1—H1B	109.5	F1—C14—C15	108.89 (18)
H1A—C1—H1B	109.5	F1—C14—C13	105.03 (17)
O1—C1—H1C	109.5	C15—C14—C13	115.37 (19)
H1A—C1—H1C	109.5	F1—C14—H14	109.1
H1B—C1—H1C	109.5	C15—C14—H14	109.1
O2—C2—H2A	109.5	C13—C14—H14	109.1
O2—C2—H2B	109.5	C14—C15—H15A	109.5
H2A—C2—H2B	109.5	C14—C15—H15B	109.5
O2—C2—H2C	109.5	H15A—C15—H15B	109.5
H2A—C2—H2C	109.5	C14—C15—H15C	109.5
H2B—C2—H2C	109.5	H15A—C15—H15C	109.5
N1—C3—O1	119.08 (18)	H15B—C15—H15C	109.5
N1—C3—C6	124.73 (19)	O7—C16—O6	124.13 (18)
O1—C3—C6	116.20 (18)	O7—C16—C17	126.38 (18)
N2—C4—N1	126.77 (18)	O6—C16—C17	109.49 (17)
N2—C4—N3	117.95 (17)	O8—C17—C16	111.44 (17)
N1—C4—N3	115.28 (17)	O8—C17—H17A	109.3
O2—C5—N2	118.40 (17)	C16—C17—H17A	109.3
O2—C5—C6	118.68 (18)	O8—C17—H17B	109.3
N2—C5—C6	122.91 (18)	C16—C17—H17B	109.3
C5—C6—C3	114.59 (19)	H17A—C17—H17B	108.0
C5—C6—H6	122.7	O8—C18—H18A	109.5
C3—C6—H6	122.7	O8—C18—H18B	109.5
O3—C7—N4	123.77 (18)	H18A—C18—H18B	109.5
O3—C7—N3	121.97 (18)	O8—C18—H18C	109.5
N4—C7—N3	114.23 (18)	H18A—C18—H18C	109.5
C12—C8—C9	119.55 (19)	H18B—C18—H18C	109.5

O5—S1—N4—C7	−48.10 (19)	O4—S1—C8—C9	−42.99 (19)
O4—S1—N4—C7	−177.12 (16)	N4—S1—C8—C9	68.21 (18)
C8—S1—N4—C7	67.84 (19)	C10—N5—C9—C8	0.1 (3)
C4—N1—C3—O1	179.93 (18)	C10—N5—C9—C13	−176.75 (18)
C4—N1—C3—C6	0.4 (3)	C12—C8—C9—N5	−1.9 (3)
C1—O1—C3—N1	−2.3 (3)	S1—C8—C9—N5	175.19 (15)
C1—O1—C3—C6	177.23 (18)	C12—C8—C9—C13	174.60 (19)
C5—N2—C4—N1	−3.1 (3)	S1—C8—C9—C13	−8.3 (3)
C5—N2—C4—N3	177.34 (17)	C9—N5—C10—C11	2.1 (3)
C3—N1—C4—N2	2.1 (3)	N5—C10—C11—C12	−2.4 (3)
C3—N1—C4—N3	−178.32 (17)	C10—C11—C12—C8	0.5 (3)
C7—N3—C4—N2	−4.5 (3)	C9—C8—C12—C11	1.6 (3)
C7—N3—C4—N1	175.92 (19)	S1—C8—C12—C11	−175.75 (16)
C2—O2—C5—N2	4.5 (3)	C16—O6—C13—C9	137.43 (16)
C2—O2—C5—C6	−176.37 (17)	C16—O6—C13—C14	−102.57 (19)
C4—N2—C5—O2	−179.30 (17)	N5—C9—C13—O6	70.7 (2)
C4—N2—C5—C6	1.6 (3)	C8—C9—C13—O6	−106.1 (2)
O2—C5—C6—C3	−178.55 (17)	N5—C9—C13—C14	−47.0 (2)
N2—C5—C6—C3	0.6 (3)	C8—C9—C13—C14	136.2 (2)
N1—C3—C6—C5	−1.6 (3)	O6—C13—C14—F1	−174.62 (16)
O1—C3—C6—C5	178.85 (17)	C9—C13—C14—F1	−58.9 (2)
S1—N4—C7—O3	−6.7 (3)	O6—C13—C14—C15	65.5 (2)
S1—N4—C7—N3	175.33 (14)	C9—C13—C14—C15	−178.77 (19)
C4—N3—C7—O3	177.7 (2)	C13—O6—C16—O7	4.0 (3)
C4—N3—C7—N4	−4.4 (3)	C13—O6—C16—C17	−175.72 (16)
O5—S1—C8—C12	3.21 (18)	C18—O8—C17—C16	85.3 (2)
O4—S1—C8—C12	134.21 (16)	O7—C16—C17—O8	−25.1 (3)
N4—S1—C8—C12	−114.60 (16)	O6—C16—C17—O8	154.58 (15)
O5—S1—C8—C9	−173.98 (16)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the N5/C8–C12 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···O8ⁱ	0.88	2.01	2.885 (2)	174
C1—H1A···O3ⁱ	0.98	2.58	3.368 (3)	137
C2—H2B···F1ⁱⁱ	0.98	2.53	3.161 (2)	122
C12—H12···O2ⁱⁱⁱ	0.95	2.42	3.229 (3)	143
C17—H17A···O5^iv	0.99	2.55	3.367 (3)	139
C1—H1B···Cg1ⁱ	0.98	2.74	3.488 (2)	134

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

Funding information

This research was supported by the Basic Science Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (No. 2015R1D1A4A01020317 and 2017R1D1A3A03000534).

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