Crystal structure of ethyl 2-(3-amino-5-oxo-2-tosyl-2,5-di­hydro-1H-pyrazol-1-yl)acetate

Metwally, N.H.; Elgemeie, G.H.; Jones, P.G.

doi:10.1107/S2056989021004795

research communications

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ISSN: 2056-9890

Volume 77| Part 6| June 2021| Pages 615-617

https://doi.org/10.1107/S2056989021004795

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Crystal structure of ethyl 2-(3-amino-5-oxo-2-tosyl-2,5-dihydro-1H-pyrazol-1-yl)acetate

Nadia H. Metwally,^a Galal H. Elgemeie ^b and Peter G. Jones ^c ^*

^aChemistry Department, Faculty of Science, Cairo University, Giza, Egypt, ^bChemistry Department, Faculty of Science, Helwan University, Cairo, Egypt, and ^cInstitut für Anorganische und Analytische Chemie, Technische Universität Braunschweig, Hagenring 30, D-38106 Braunschweig, Germany
^*Correspondence e-mail: p.jones@tu-bs.de

Edited by M. Zeller, Purdue University, USA (Received 3 May 2021; accepted 6 May 2021; online 14 May 2021)

In the title compound, C₁₄H₁₇N₃O₅S, the five-membered ring is essentially planar. The substituents at the nitrogen atoms subtend a C—N—N—S torsion angle of −95.52 (6)°. The amino group forms an intramolecular hydrogen bond to a sulfonyl oxygen atom; two intermolecular hydrogen bonds from the amino group, to the other S=O group and to the oxo substituent, form a layer structure parallel to the ab plane. The structure determination confirms that the title compound is N- rather than O-alkylated.

Keywords: pyrazole; tosyl; hydrogen bond; crystal structure.

CCDC reference: 2082046

1. Chemical context

Recently we have been attempting to develop synthetic strategies for heterocyclic ring systems containing N-sulfonylamino- and N-sulfonyl moieties. The products may be biologically active, displaying for instance anti-viral activity (Azzam et al., 2017 , 2019 , 2020 ; Zhu et al., 2013 ; Elgemeie et al., 2017 , 2019 ). Also, some of our reported N-arylsulfonylpyrazole derivatives (Elgemeie et al., 1998 , 2013 ; Elgemeie & Hanfy, 1999 ) proved to be inhibitors of the NS2B-NS3 virus and the enzyme cathepsin B16 (Myers et al., 2007 ; Sidique et al., 2009 ). In a continuation of our research investigating new approaches to other new derivatives of N-sulfonylpyrazoles, seeking various scaffolds for use as encouraging chemotherapeutics (Zhang et al., 2020 ; Elgemeie & Jones, 2002 ), we have now synthesized the N1-substituted derivative of N-sulfonylpyrazole 1 (the structure of which we have reported; Elgemeie et al., 2013).

The reaction of 1 with ethyl bromoacetate 2 in dry N,N-dimethylformamide containing anhydrous potassium carbonate at room temperature afforded a product for which two possible isomeric structures, the N-alkylated or O-alkylated N-sulfonylpyrazoles 3 or 4, were feasible. The ¹H NMR spectrum of the product showed four singlet signals at δ = 2.41, 4.31, 4.40 and 7.15 ppm assigned to CH₃, pyrazole-CH, CH₂ and NH₂ protons, along with triplet and quartet signals at δ = 1.17 and 4.09 ppm, assigned to ethyl groups. The spectroscopic data cannot differentiate between structures 3 and 4. We therefore determined the X-ray structure of this product, which proved to be the N-alkylated-N-sulfonylpyrazole 4.

2. Structural commentary

The molecule of compound 4 is shown in Fig. 1. Molecular dimensions, a selection of which are presented in Table 1, may be considered normal (e.g. the N1—N2 bond length corresponds to a single bond and these atoms display a pyramidal geometry). The substituents S1 and C6 of the five-membered ring, which is effectively planar (r.m.s. deviation 0.026 Å) lie significantly outside the ring plane [by 1.2344 (8) and 0.8468 (19) Å, respectively] in opposite directions; the corresponding torsion angle C6—N1—N2—S1 is −95.52 (6)°. The side chain at N1 exhibits an extended conformation. An intramolecular hydrogen bond is formed from the amino group to the sulfonyl oxygen atom O4 (Table 2). The ring planes subtend an interplanar angle of 57.01 (3)°.

Table 1
Selected geometric parameters (Å, °)

N1—C5	1.4157 (9)	N2—S1	1.7154 (6)
N1—N2	1.4296 (8)	C3—C4	1.3661 (9)
N1—C6	1.4549 (9)	C4—C5	1.4203 (10)
N2—C3	1.4273 (8)

C5—N1—N2	107.67 (5)	C4—C3—N2	110.21 (6)
C5—N1—C6	117.34 (6)	C3—C4—C5	107.94 (6)
N2—N1—C6	115.11 (5)	O1—C5—N1	120.24 (7)
C3—N2—N1	105.89 (5)	O1—C5—C4	131.82 (7)
C3—N2—S1	116.65 (4)	N1—C5—C4	107.90 (6)
N1—N2—S1	109.25 (4)

C6—N1—N2—S1	−95.52 (6)	C6—C7—O3—C8	−179.18 (6)
N1—C6—C7—O3	170.80 (6)	C9—C8—O3—C7	−168.27 (7)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H01⋯O1ⁱ	0.913 (13)	1.897 (13)	2.7884 (8)	164.7 (12)
N3—H02⋯O4	0.861 (13)	2.394 (13)	2.8291 (8)	111.8 (10)
N3—H02⋯O5ⁱⁱ	0.861 (13)	2.294 (13)	3.0139 (8)	141.3 (12)
C6—H6B⋯O4ⁱⁱⁱ	0.99	2.50	3.2642 (9)	133
C8—H8B⋯O1^iv	0.99	2.43	3.2663 (11)	142
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) .

Figure 1
The structure of compound 4 in the crystal. Ellipsoids represent 50% probability levels. The dashed line indicates an intramolecular hydrogen bond.

3. Supramolecular features

The molecules of 4 are linked by two classical hydrogen bonds, from the NH₂ hydrogen atoms H01 and H02 to the acceptors O5=S1 and O1=C5, to form layers parallel to the ab plane (Fig. 2, Table 2). The hydrogen atom H02 is thus involved in a three-centre hydrogen bond, taking the above-mentioned intramolecular interaction into account. The additional `weak' interactions H6B⋯O4 (within the layers; operator −x + 2, y − $[{1\over 2}]$ , −z + $[{1\over 2}]$ ) and H8B⋯O1 (between layers; operator −x + 1, −y + 1, −z) are not shown in the Figure. The shortest distance between ring centroids is 3.97 Å for the ring C10–C15 (operator 2 − x, 1 − y, 1 − z).

Figure 2
Packing diagram of compound 4 viewed perpendicular to the ab plane in the region z ≃ 0.25. Dashed lines indicate hydrogen bonds. Hydrogen atoms not involved in hydrogen bonding are omitted for clarity.

4. Database survey

A database search (CSD Version 5.41) for the same ring system as in 4, and bearing the same substituents at C5 (oxo) and C3 (amino), gave eight hits involving uncharged species. However, none of these was substituted at both ring nitrogen atoms. Two (our previous structures: Elgemeie et al., 1998, 2013) have a hydrogen atom at N1, while the other six have a hydrogen at N2; the other N-substituents are 9-thioxanthenyl (DOJKIW; Kimura, 1986 ), C(=S)NHEt (LUPDUW; Pitucha et al., 2010 ), C(=O)NHCH₂COOEt (MAVJUK) and C(=O)NH-ⁿBu (MAVKAX; Pitucha et al., 2011 ), C(=O)NHCH(Ph)CH₃ (TIRVAT; Kaczor et al., 2013 ) and C(O)NH-1-naphthyl (VOQGOZ; Kaczor et al., 2014 ). It is notable that the X—N—N—X (X = H or substituent atom) torsion angles are very variable; in four cases the absolute value lies between 0 and 11°, whereas for the bulky substituents in DOJKIW and VOQGOZ the values are 63.7 and 32.1°, respectively.

5. Synthesis and crystallization

A mixture of 5-amino-1-tosyl-1,2-dihydro-3H-pyrazol-3-one 1 (0.01 mol), ethyl bromoacetate 2 (0.01 mol) and anhydrous potassium carbonate (0.01 mol) in N,N-dimethylformamide (5 mL) was stirred at room temperature for 3 h. The mixture was poured onto ice–water; the solid thus formed was filtered off and recrystallized from ethanol to give pale yellow crystals in 64% yield, m.p. = 415–416 K. IR (KBr, cm⁻¹): ν 3460, 3297 (NH₂), 1752 (ester C=O), 1700 (ring C=O); ¹H NMR (DMSO-d₆): δ = 1.17 (t, 3H, J = 7.2 Hz, CH₃), 2.41 (s, 3H, CH₃), 4.09 (q, 2H, J = 7.2 Hz, CH₂), 4.31 (s, 1H, CH pyrazole), 4.40 (s, 2H, CH₂), 7.15 (s, 2H, NH₂), 7.45 (d, 2H, J = 8.4 Hz, Ar), 7.73 (d, 2H, J = 8.4 Hz, Ar). Analysis: calculated C₁₄H₁₇N₃O₅S (339.36); C, 49.55; H, 5.05; N, 12.38; S, 9.45. Found: C, 49.38; H, 5.23; N, 12.59; S, 9.27%.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. The hydrogen atoms of the NH₂ group were refined freely. The methyl groups were refined as idealized rigid groups allowed to rotate but not tip (AFIX 137; C—H = 0.98 Å, H—C—H = 109.5°). Other hydrogens were included using a riding model starting from calculated positions (C—H_aromatic = 0.95, C—H_methylene = 0.99 Å). The U_iso(H) values were fixed at 1.5 (for the methyl H) or 1.2 times the equivalent U_eq value of the parent carbon atoms.

Table 3
Experimental details

Crystal data
Chemical formula	C₁₄H₁₇N₃O₅S
M_r	339.36
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	9.1398 (2), 11.1525 (2), 16.3795 (3)
β (°)	97.081 (2)
V (Å³)	1656.85 (6)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.22
Crystal size (mm)	0.24 × 0.20 × 0.08

Data collection
Diffractometer	XtaLAB Synergy, Single source at offset/far, HyPix
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2021 $[Rigaku OD (2021). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.805, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	128543, 7466, 6502
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.825

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.094, 1.05
No. of reflections	7466
No. of parameters	218
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.58, −0.30
Computer programs: CrysAlis PRO (Rigaku OD, 2021 $[Rigaku OD (2021). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ) and XP (Siemens, 1994 ).

Supporting information

CCDC reference: 2082046

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989021004795/zl5011sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989021004795/zl5011Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989021004795/zl5011Isup3.cml

checkCIF report

Computing details top

Cell refinement: CrysAlis PRO (Rigaku OD, 2021); data reduction: CrysAlis PRO (Rigaku OD, 2021); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXL2018/3 (Sheldrick, 2015b).

Ethyl 2-[3-amino-2-(4-methylbenzenesulfonyl)-5-oxo-2,5-dihydro-1H-pyrazol-1-yl]acetate top

Crystal data top

C₁₄H₁₇N₃O₅S	F(000) = 712
M_r = 339.36	D_x = 1.360 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.1398 (2) Å	Cell parameters from 78897 reflections
b = 11.1525 (2) Å	θ = 2.2–36.1°
c = 16.3795 (3) Å	µ = 0.22 mm⁻¹
β = 97.081 (2)°	T = 100 K
V = 1656.85 (6) Å³	Tablet, colourless
Z = 4	0.24 × 0.20 × 0.08 mm

Data collection top

XtaLAB Synergy, Single source at offset/far, HyPix diffractometer	7466 independent reflections
Radiation source: micro-focus sealed X-ray tube	6502 reflections with I > 2σ(I)
Detector resolution: 10.0000 pixels mm^-1	R_int = 0.040
ω scans	θ_max = 35.9°, θ_min = 2.2°
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2021)	h = −14→15
T_min = 0.805, T_max = 1.000	k = −17→18
128543 measured reflections	l = −26→26

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.031	Hydrogen site location: mixed
wR(F²) = 0.094	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0543P)² + 0.3217P] where P = (F_o² + 2F_c²)/3
7466 reflections	(Δ/σ)_max = 0.001
218 parameters	Δρ_max = 0.58 e Å⁻³
0 restraints	Δρ_min = −0.30 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.

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

- 0.4791 (0.0031) x - 2.3604 (0.0036) y + 15.9693 (0.0013) z = 2.0024 (0.0032)

* 0.0342 (0.0004) N1 * -0.0209 (0.0004) N2 * -0.0003 (0.0004) C3 * 0.0215 (0.0004) C4 * -0.0345 (0.0004) C5 -0.8468 (0.0010) C6 0.0094 (0.0011) N3 -0.1626 (0.0011) O1 1.2344 (0.0008) S1

Rms deviation of fitted atoms = 0.0255

7.3350 (0.0016) x - 0.2526 (0.0037) y + 8.0701 (0.0042) z = 9.4209 (0.0022)

Angle to previous plane (with approximate esd) = 57.006 ( 0.025 )

* -0.0031 (0.0005) C10 * -0.0009 (0.0005) C11 * 0.0057 (0.0006) C12 * -0.0065 (0.0005) C13 * 0.0025 (0.0005) C14 * 0.0022 (0.0005) C15 -0.0668 (0.0010) S1 -0.0236 (0.0012) C16

Rms deviation of fitted atoms = 0.0040

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

	x	y	z	U_iso*/U_eq
N1	0.71924 (7)	0.51318 (5)	0.22496 (4)	0.01525 (10)
N2	0.80727 (6)	0.61874 (5)	0.23976 (3)	0.01313 (9)
C3	0.70693 (7)	0.71323 (6)	0.25200 (4)	0.01349 (10)
C4	0.56556 (7)	0.67098 (6)	0.24288 (4)	0.01709 (11)
H4	0.479736	0.716052	0.249768	0.021*
C5	0.56954 (8)	0.54779 (6)	0.22128 (4)	0.01753 (12)
O1	0.47057 (7)	0.47513 (6)	0.19955 (4)	0.02624 (12)
N3	0.75894 (7)	0.82301 (5)	0.27039 (4)	0.01797 (11)
H01	0.6933 (15)	0.8832 (12)	0.2762 (8)	0.029 (3)*
H02	0.8476 (15)	0.8402 (12)	0.2619 (8)	0.029 (3)*
C6	0.75926 (9)	0.43604 (6)	0.15959 (4)	0.01874 (12)
H6A	0.692061	0.366114	0.153801	0.022*
H6B	0.860733	0.405756	0.174982	0.022*
C7	0.75148 (8)	0.50043 (6)	0.07754 (4)	0.01746 (12)
C8	0.81058 (10)	0.48513 (7)	−0.05858 (5)	0.02349 (14)
H8A	0.884230	0.550504	−0.056465	0.028*
H8B	0.712342	0.518726	−0.078401	0.028*
O2	0.70022 (8)	0.59873 (5)	0.06371 (4)	0.02588 (12)
O3	0.80980 (7)	0.43200 (5)	0.02284 (3)	0.02152 (11)
C9	0.84936 (12)	0.38700 (8)	−0.11506 (5)	0.02858 (17)
H9A	0.856512	0.420399	−0.169766	0.043*
H9B	0.772657	0.325136	−0.119119	0.043*
H9C	0.944187	0.351494	−0.093111	0.043*
S1	0.94519 (2)	0.59188 (2)	0.31853 (2)	0.01400 (4)
O4	1.02319 (6)	0.70299 (5)	0.33031 (4)	0.02030 (10)
O5	1.01852 (6)	0.48758 (5)	0.29250 (3)	0.01987 (10)
C10	0.85810 (7)	0.55582 (6)	0.40445 (4)	0.01440 (10)
C11	0.83563 (9)	0.43557 (6)	0.42138 (4)	0.01902 (12)
H11	0.869968	0.374683	0.387917	0.023*
C12	0.76214 (9)	0.40563 (7)	0.48806 (5)	0.02152 (13)
H12	0.747436	0.323625	0.500452	0.026*
C13	0.70971 (8)	0.49456 (7)	0.53699 (4)	0.01845 (12)
C14	0.73476 (9)	0.61451 (7)	0.51909 (5)	0.02110 (13)
H14	0.700833	0.675486	0.552637	0.025*
C15	0.80858 (9)	0.64644 (6)	0.45295 (4)	0.01932 (12)
H15	0.824955	0.728372	0.441058	0.023*
C16	0.62816 (9)	0.46037 (9)	0.60792 (5)	0.02581 (15)
H16A	0.699167	0.440717	0.655867	0.039*
H16B	0.565744	0.390460	0.592686	0.039*
H16C	0.566462	0.527646	0.621388	0.039*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0188 (2)	0.0120 (2)	0.0151 (2)	−0.00278 (17)	0.00269 (18)	−0.00152 (17)
N2	0.0136 (2)	0.0110 (2)	0.0147 (2)	−0.00006 (16)	0.00156 (16)	−0.00001 (16)
C3	0.0135 (2)	0.0126 (2)	0.0146 (2)	0.00057 (18)	0.00261 (18)	0.00023 (18)
C4	0.0130 (2)	0.0188 (3)	0.0197 (3)	−0.0009 (2)	0.0032 (2)	−0.0015 (2)
C5	0.0173 (3)	0.0193 (3)	0.0161 (3)	−0.0050 (2)	0.0029 (2)	−0.0004 (2)
O1	0.0242 (3)	0.0283 (3)	0.0262 (3)	−0.0140 (2)	0.0030 (2)	−0.0038 (2)
N3	0.0167 (2)	0.0115 (2)	0.0261 (3)	−0.00030 (18)	0.0040 (2)	−0.00131 (19)
C6	0.0296 (3)	0.0122 (2)	0.0145 (3)	0.0014 (2)	0.0028 (2)	−0.0007 (2)
C7	0.0228 (3)	0.0151 (3)	0.0142 (3)	0.0014 (2)	0.0011 (2)	−0.0009 (2)
C8	0.0373 (4)	0.0182 (3)	0.0157 (3)	0.0052 (3)	0.0060 (3)	0.0023 (2)
O2	0.0418 (3)	0.0172 (2)	0.0188 (2)	0.0097 (2)	0.0042 (2)	0.00153 (18)
O3	0.0327 (3)	0.0179 (2)	0.0144 (2)	0.0073 (2)	0.00453 (19)	0.00122 (17)
C9	0.0462 (5)	0.0220 (3)	0.0196 (3)	0.0069 (3)	0.0121 (3)	0.0011 (3)
S1	0.01253 (7)	0.01380 (7)	0.01577 (7)	0.00071 (4)	0.00218 (5)	0.00157 (5)
O4	0.0162 (2)	0.0189 (2)	0.0251 (2)	−0.00522 (17)	−0.00029 (18)	0.00314 (18)
O5	0.0189 (2)	0.0205 (2)	0.0210 (2)	0.00769 (18)	0.00564 (18)	0.00221 (18)
C10	0.0165 (3)	0.0128 (2)	0.0139 (2)	0.00007 (19)	0.00173 (19)	−0.00002 (19)
C11	0.0266 (3)	0.0136 (3)	0.0178 (3)	0.0004 (2)	0.0068 (2)	0.0007 (2)
C12	0.0293 (4)	0.0174 (3)	0.0188 (3)	−0.0025 (2)	0.0070 (3)	0.0021 (2)
C13	0.0172 (3)	0.0239 (3)	0.0141 (3)	−0.0017 (2)	0.0014 (2)	−0.0004 (2)
C14	0.0251 (3)	0.0207 (3)	0.0182 (3)	0.0013 (2)	0.0052 (2)	−0.0039 (2)
C15	0.0255 (3)	0.0142 (3)	0.0187 (3)	0.0004 (2)	0.0045 (2)	−0.0026 (2)
C16	0.0223 (3)	0.0393 (4)	0.0165 (3)	−0.0045 (3)	0.0053 (2)	0.0009 (3)

Geometric parameters (Å, º) top

N1—C5	1.4157 (9)	C13—C14	1.3944 (11)
N1—N2	1.4296 (8)	C13—C16	1.5046 (10)
N1—C6	1.4549 (9)	C14—C15	1.3913 (11)
N2—C3	1.4273 (8)	C4—H4	0.9500
N2—S1	1.7154 (6)	N3—H01	0.913 (13)
C3—N3	1.3343 (8)	N3—H02	0.861 (13)
C3—C4	1.3661 (9)	C6—H6A	0.9900
C4—C5	1.4203 (10)	C6—H6B	0.9900
C5—O1	1.2337 (8)	C8—H8A	0.9900
C6—C7	1.5177 (10)	C8—H8B	0.9900
C7—O2	1.2027 (8)	C9—H9A	0.9800
C7—O3	1.3367 (9)	C9—H9B	0.9800
C8—O3	1.4601 (9)	C9—H9C	0.9800
C8—C9	1.5033 (11)	C11—H11	0.9500
S1—O4	1.4308 (6)	C12—H12	0.9500
S1—O5	1.4334 (5)	C14—H14	0.9500
S1—C10	1.7470 (7)	C15—H15	0.9500
C10—C11	1.3899 (9)	C16—H16A	0.9800
C10—C15	1.3950 (9)	C16—H16B	0.9800
C11—C12	1.3914 (10)	C16—H16C	0.9800
C12—C13	1.3966 (11)

C5—N1—N2	107.67 (5)	C3—C4—H4	126.0
C5—N1—C6	117.34 (6)	C5—C4—H4	126.0
N2—N1—C6	115.11 (5)	C3—N3—H01	118.5 (8)
C3—N2—N1	105.89 (5)	C3—N3—H02	119.0 (9)
C3—N2—S1	116.65 (4)	H01—N3—H02	119.8 (12)
N1—N2—S1	109.25 (4)	N1—C6—H6A	109.1
N3—C3—C4	130.31 (6)	C7—C6—H6A	109.1
N3—C3—N2	119.47 (6)	N1—C6—H6B	109.1
C4—C3—N2	110.21 (6)	C7—C6—H6B	109.1
C3—C4—C5	107.94 (6)	H6A—C6—H6B	107.8
O1—C5—N1	120.24 (7)	O3—C8—H8A	110.3
O1—C5—C4	131.82 (7)	C9—C8—H8A	110.3
N1—C5—C4	107.90 (6)	O3—C8—H8B	110.3
N1—C6—C7	112.54 (6)	C9—C8—H8B	110.3
O2—C7—O3	124.92 (7)	H8A—C8—H8B	108.5
O2—C7—C6	124.94 (7)	C8—C9—H9A	109.5
O3—C7—C6	110.15 (6)	C8—C9—H9B	109.5
O3—C8—C9	107.14 (6)	H9A—C9—H9B	109.5
C7—O3—C8	115.33 (6)	C8—C9—H9C	109.5
O4—S1—O5	119.96 (4)	H9A—C9—H9C	109.5
O4—S1—N2	104.95 (3)	H9B—C9—H9C	109.5
O5—S1—N2	104.19 (3)	C10—C11—H11	120.5
O4—S1—C10	111.08 (3)	C12—C11—H11	120.5
O5—S1—C10	109.21 (3)	C11—C12—H12	119.6
N2—S1—C10	106.30 (3)	C13—C12—H12	119.6
C11—C10—C15	121.27 (6)	C15—C14—H14	119.4
C11—C10—S1	118.43 (5)	C13—C14—H14	119.4
C15—C10—S1	120.27 (5)	C14—C15—H15	120.6
C10—C11—C12	119.05 (6)	C10—C15—H15	120.6
C11—C12—C13	120.87 (7)	C13—C16—H16A	109.5
C14—C13—C12	118.93 (6)	C13—C16—H16B	109.5
C14—C13—C16	121.02 (7)	H16A—C16—H16B	109.5
C12—C13—C16	120.05 (7)	C13—C16—H16C	109.5
C15—C14—C13	121.14 (7)	H16A—C16—H16C	109.5
C14—C15—C10	118.72 (7)	H16B—C16—H16C	109.5

C5—N1—N2—C3	5.12 (7)	C3—N2—S1—O4	−58.13 (5)
C6—N1—N2—C3	138.08 (6)	N1—N2—S1—O4	−178.12 (4)
C5—N1—N2—S1	131.52 (5)	C3—N2—S1—O5	174.95 (5)
C6—N1—N2—S1	−95.52 (6)	N1—N2—S1—O5	54.96 (5)
N1—N2—C3—N3	177.46 (6)	C3—N2—S1—C10	59.64 (5)
S1—N2—C3—N3	55.69 (7)	N1—N2—S1—C10	−60.35 (5)
N1—N2—C3—C4	−1.86 (7)	O4—S1—C10—C11	−151.48 (6)
S1—N2—C3—C4	−123.63 (5)	O5—S1—C10—C11	−16.96 (7)
N3—C3—C4—C5	178.65 (7)	N2—S1—C10—C11	94.90 (6)
N2—C3—C4—C5	−2.13 (8)	O4—S1—C10—C15	30.51 (7)
N2—N1—C5—O1	171.51 (6)	O5—S1—C10—C15	165.03 (6)
C6—N1—C5—O1	39.75 (9)	N2—S1—C10—C15	−83.11 (6)
N2—N1—C5—C4	−6.48 (7)	C15—C10—C11—C12	0.06 (11)
C6—N1—C5—C4	−138.24 (6)	S1—C10—C11—C12	−177.93 (6)
C3—C4—C5—O1	−172.33 (8)	C10—C11—C12—C13	0.78 (12)
C3—C4—C5—N1	5.35 (8)	C11—C12—C13—C14	−1.31 (12)
C5—N1—C6—C7	69.88 (8)	C11—C12—C13—C16	178.92 (7)
N2—N1—C6—C7	−58.40 (8)	C12—C13—C14—C15	1.01 (12)
N1—C6—C7—O2	−9.23 (11)	C16—C13—C14—C15	−179.22 (7)
N1—C6—C7—O3	170.80 (6)	C13—C14—C15—C10	−0.20 (11)
O2—C7—O3—C8	0.85 (12)	C11—C10—C15—C14	−0.35 (11)
C6—C7—O3—C8	−179.18 (6)	S1—C10—C15—C14	177.60 (6)
C9—C8—O3—C7	−168.27 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H01···O1ⁱ	0.913 (13)	1.897 (13)	2.7884 (8)	164.7 (12)
N3—H02···O4	0.861 (13)	2.394 (13)	2.8291 (8)	111.8 (10)
N3—H02···O5ⁱⁱ	0.861 (13)	2.294 (13)	3.0139 (8)	141.3 (12)
C6—H6B···O4ⁱⁱⁱ	0.99	2.50	3.2642 (9)	133
C8—H8B···O1^iv	0.99	2.43	3.2663 (11)	142

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

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