Ethyl 3-amino-2-carbamoyl-4-(4-meth­oxy­phen­yl)-6-methyl­thieno[2,3-b]pyridine-5-carboxyl­ate dimethyl sulfoxide monosolvate

Bakhite, E.A.; Kaur, M.; Mohamed, S.K.; Akkurt, M.; Jasinski, J.P.; Albayati, M.R.

doi:10.1107/S2414314616014747

organic compounds

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ISSN: 2414-3146

Volume 1| Part 9| September 2016| x161474

doi:10.1107/S2414314616014747

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Ethyl 3-amino-2-carbamoyl-4-(4-methoxyphenyl)-6-methylthieno[2,3-b]pyridine-5-carboxylate dimethyl sulfoxide monosolvate

Etify A. Bakhite,^a Manpreet Kaur,^b Shaaban K. Mohamed,^c,^d Mehmet Akkurt,^e Jerry P. Jasinski ^b and Mustafa R. Albayati ^f ^*

^aChemistry Department, Faculty of Science, Assiut University, 71516 Assiut, Egypt, ^bDepartment of Chemistry, Keene State College, 229 Main Street, Keene, NH 03435-2001, USA, ^cChemistry and Environmental Division, Manchester Metropolitan University, Manchester M1 5GD, England, ^dChemistry Department, Faculty of Science, Mini University, 61519 El-Minia, Egypt, ^eDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey, and ^fKirkuk University, College of Science, Department of Chemistry, Kirkuk, Iraq
^*Correspondence e-mail: shaabankamel@yahoo.com

Edited by P. C. Healy, Griffith University, Australia (Received 12 September 2016; accepted 18 September 2016; online 23 September 2016)

The conformation of the title molecule, C₁₉H₁₉N₃O₄S·C₂H₆OS, which crystallized as a DMSO solvate, is partially determined by an intramolecular N—H⋯O hydrogen bond, forming an S(6) loop. The thienopyridine bicyclic system is almost planar, with an r.m.s. deviation of 0.002 Å. The benzene ring makes a dihedral angle of 65.44 (8)° with the mean plane of the thienopyridine bicyclic system. In the crystal, molecules are linked by pairs of N—H⋯O hydrogen bonds, forming inversion dimers with an R₂²(8) ring motif. Within the dimers, which stack along the a-axis direction, there is a weak π–π interaction [centroid-to-centroid distance = 3.5428 (11) Å] involving inversion-related thiophene rings. In addition, N—H⋯O and C—H⋯O hydrogen bonds help to consolidate the packing, via the solvent molecules.

Keywords: crystal structure; dimethyl sulfoxide; thienopyridine derivative.

CCDC reference: 1504924

Structure description

Nowadays, after a lapse of more than one century, the chemistry of thieno[2,3-b]pyridines is well known. This is associated primarily with the great practical importance of many derivatives of thieno[2,3-b]pyridine (Litvinov et al., 2005 ). The spectrum of biological activities of this class of compounds is rather broad and includes antiviral (Attaby et al., 2007 ), antidiabetic (Bahekar et al. 2007 ) and antimicrobial (Abdel-Rahman et al., 2003 ). As part of our studies in this area, we undertook the synthesis of the title compound in order to establish its crystal structure.

The conformation of the title molecule (Fig. 1) is partially determined by an intramolecular N2—H2A⋯O1 hydrogen bond, forming an S(6) loop (Table 1). The thienopyridine bicyclic system (S1/N3/C2–C8) is almost planar, with an r.m.s. deviation of 0.002 Å. The benzene ring (C9–C14) makes a dihedral angle of 65.44 (8)° with the mean plane of the thienopyridine bicyclic system.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯O1ⁱ	0.87 (2)	2.07 (2)	2.916 (2)	165 (2)
N1—H1A⋯O1Sⁱⁱ	0.88 (2)	2.08 (2)	2.918 (3)	158 (2)
N2—H2A⋯O1	0.86 (2)	2.10 (2)	2.719 (2)	129 (2)
C14—H14⋯O3ⁱⁱⁱ	0.95	2.50	3.381 (2)	155
C16—H16A⋯O2^iv	0.99	2.48	3.254 (3)	134
C19—H19C⋯O1^v	0.98	2.75	3.474 (3)	131
C19—H19A⋯O1S^vi	0.98	2.84	3.483 (3)	124
Symmetry codes: (i) -x+1, -y+1, -z; (ii) x, y, z-1; (iii) -x+1, -y+2, -z+1; (iv) -x+1, -y+2, -z+2; (v) -x+1, -y+1, -z+1; (vi) -x, -y+1, -z+2.

Figure 1
The molecular structure of the title molecule, shown with 50% probability displacement ellipsoids.

In the crystal, molecules are linked by pairs of N1—H1A⋯O1 hydrogen bonds, forming inversion dimers with an $[R_{2}^{2}]$ (8) ring motif (Table 1). Within the dimers, which stack along the a-axis direction, there is a weak π–π interaction [centroid-to-centroid distance = 3.5428 (11) Å] involving inversion-related thiophene rings. In addition, N1—H1A⋯O1S(x, y, z − 1) and C19—H19A⋯O1S(−x, −y + 1, −z + 2) hydrogen bonds help to establish the packin (Fig. 2 and Table 1).

Figure 2
The packing of the title molecule, viewed down the a axis, with the hydrogen bonds shown by dotted lines.

Synthesis and crystallization

The title compound was prepared by heating equimolar quantities of ethyl 3-cyano-6-methyl-4-(4-methoxyphenyl)-2-thioxo-1,2-dihydropyridine-5-carboxylate (10 mmol) and chloroacetamide (10 mmol) in absolute ethanol (25 ml) containing dissolved sodium (0.40 g) on a steam bath for 30 min. The product that formed on cooling was collected and recrystallized from DMSO solution to give yellow crystals of the title compound (yield 75%; m.p. 487–488 K). IR (KBr, cm⁻¹) ν = 3490, 3450, 3300, 3200 (2 NH₂), 1720(C=O, ester), 1650 (C=O, amide). ¹H NMR (DMSO-d₆): δ7.0–7.3 (m, 6H, NH₂ and ArH's), 5.6 (s, 2H, NH₂), 3.5–4.2 (m, 5H, OCH₂ and OCH₃), 2.6 (s, 3H, CH₃), 0.9–1.1 (t, 3H, CH₃ of ester).

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₁₉H₁₉N₃O₄S·C₂H₆OS
M_r	463.56
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	173
a, b, c (Å)	9.9950 (7), 10.1492 (5), 11.2620 (8)
α, β, γ (°)	90.656 (5), 92.291 (5), 101.925 (5)
V (Å³)	1116.66 (13)
Z	2
Radiation type	Cu Kα
μ (mm⁻¹)	2.49
Crystal size (mm)	0.34 × 0.18 × 0.12

Data collection
Diffractometer	Rigaku Oxford Diffraction
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2014 )
No. of measured, independent and observed [I > 2σ(I)] reflections	6959, 4247, 3706
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.615

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.139, 1.06
No. of reflections	4247
No. of parameters	298
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.45
Computer programs: CrysAlis PRO (Agilent, 2014), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 1504924

Crystal structure: contains datablocks global, I. DOI: 10.1107/S2414314616014747/hg4013sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616014747/hg4013Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616014747/hg4013Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Ethyl 3-amino-2-carbamoyl-4-(4-methoxyphenyl)-6-methylthieno[2,3-b]pyridine-5-carboxylate dimethyl sulfoxide monosolvate top

Crystal data top

C₁₉H₁₉N₃O₄S·C₂H₆OS	Z = 2
M_r = 463.56	F(000) = 488
Triclinic, P1	D_x = 1.379 Mg m⁻³
a = 9.9950 (7) Å	Cu Kα radiation, λ = 1.54184 Å
b = 10.1492 (5) Å	Cell parameters from 3206 reflections
c = 11.2620 (8) Å	θ = 3.9–71.4°
α = 90.656 (5)°	µ = 2.49 mm⁻¹
β = 92.291 (5)°	T = 173 K
γ = 101.925 (5)°	Prism, yellow
V = 1116.66 (13) Å³	0.34 × 0.18 × 0.12 mm

Data collection top

Rigaku Oxford Diffraction diffractometer	4247 independent reflections
Radiation source: Enhance (Cu) X-ray Source	3706 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
Detector resolution: 16.0416 pixels mm^-1	θ_max = 71.4°, θ_min = 3.9°
ω scans	h = −11→12
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −12→8
	l = −11→13
6959 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.049	w = 1/[σ²(F_o²) + (0.0879P)² + 0.1101P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.139	(Δ/σ)_max = 0.001
S = 1.06	Δρ_max = 0.40 e Å⁻³
4247 reflections	Δρ_min = −0.45 e Å⁻³
298 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
4 restraints	Extinction coefficient: 0.0058 (7)

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
C1	0.4772 (2)	0.54248 (19)	0.17912 (17)	0.0186 (4)
C1S	0.1585 (3)	0.1551 (3)	0.9746 (3)	0.0492 (7)
H1S1	0.241592	0.221202	0.957889	0.074*
H1S2	0.126523	0.099851	0.903084	0.074*
H1S3	0.178572	0.097249	1.039111	0.074*
C2	0.45367 (19)	0.57636 (18)	0.30206 (17)	0.0174 (4)
C2S	0.0347 (3)	0.3450 (3)	0.8908 (3)	0.0513 (7)
H2S1	−0.027459	0.407176	0.899931	0.077*
H2S2	0.006674	0.288510	0.819296	0.077*
H2S3	0.128268	0.396611	0.883296	0.077*
C3	0.54673 (19)	0.66430 (18)	0.37518 (16)	0.0154 (4)
C4	0.49047 (18)	0.68700 (18)	0.48843 (16)	0.0149 (4)
C5	0.35832 (19)	0.60709 (18)	0.49757 (17)	0.0165 (4)
C6	0.3323 (2)	0.68041 (18)	0.68476 (17)	0.0187 (4)
C7	0.4619 (2)	0.76783 (18)	0.68325 (16)	0.0181 (4)
C8	0.54318 (19)	0.77362 (18)	0.58518 (17)	0.0164 (4)
C9	0.67405 (19)	0.87524 (18)	0.58362 (16)	0.0169 (4)
C10	0.7836 (2)	0.87283 (19)	0.66376 (17)	0.0210 (4)
H10	0.778935	0.800126	0.716865	0.025*
C11	0.8990 (2)	0.9754 (2)	0.66657 (18)	0.0234 (4)
H11	0.973988	0.971543	0.720067	0.028*
C12	0.9058 (2)	1.08446 (19)	0.59123 (18)	0.0219 (4)
C13	0.7987 (2)	1.08628 (19)	0.50918 (18)	0.0214 (4)
H13	0.803726	1.158816	0.455849	0.026*
C14	0.6846 (2)	0.98204 (19)	0.50535 (17)	0.0194 (4)
H14	0.612227	0.983306	0.448360	0.023*
C15	0.5046 (2)	0.8659 (2)	0.78571 (17)	0.0205 (4)
C16	0.5193 (3)	1.0959 (2)	0.84395 (19)	0.0306 (5)
H16A	0.492045	1.059334	0.922553	0.037*
H16B	0.466229	1.165710	0.824692	0.037*
C17	0.6686 (3)	1.1581 (3)	0.8497 (3)	0.0513 (8)
H17A	0.720710	1.091136	0.876167	0.077*
H17B	0.686200	1.234740	0.905894	0.077*
H17C	0.696878	1.189203	0.770682	0.077*
C18	1.0181 (2)	1.3070 (2)	0.5402 (3)	0.0349 (6)
H18A	1.019823	1.288610	0.454779	0.052*
H18B	1.098354	1.376174	0.565212	0.052*
H18C	0.934616	1.339043	0.557130	0.052*
C19	0.2440 (2)	0.6782 (2)	0.7903 (2)	0.0295 (5)
H19A	0.151364	0.627493	0.769318	0.044*
H19B	0.240061	0.770723	0.813381	0.044*
H19C	0.282981	0.635101	0.856858	0.044*
N1	0.37300 (19)	0.47179 (19)	0.11272 (16)	0.0261 (4)
H1A	0.2873 (19)	0.443 (2)	0.132 (2)	0.031*
H1B	0.392 (3)	0.445 (2)	0.0427 (17)	0.031*
N2	0.67459 (17)	0.72257 (17)	0.34414 (15)	0.0209 (4)
H2A	0.704 (2)	0.691 (2)	0.2818 (17)	0.025*
H2B	0.734 (2)	0.778 (2)	0.385 (2)	0.025*
N3	0.27964 (16)	0.60146 (16)	0.59184 (15)	0.0195 (4)
O1	0.59216 (15)	0.58235 (15)	0.13776 (12)	0.0248 (3)
O1S	0.08790 (18)	0.3310 (2)	1.12153 (16)	0.0446 (5)
O2	0.54367 (19)	0.83839 (15)	0.88281 (13)	0.0336 (4)
O3	0.48721 (16)	0.98795 (14)	0.75431 (12)	0.0252 (3)
O4	1.02006 (15)	1.18517 (14)	0.60450 (15)	0.0291 (4)
S1	0.29893 (5)	0.51409 (4)	0.36893 (4)	0.01890 (17)
S1S	0.02868 (6)	0.24091 (6)	1.01773 (6)	0.0356 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0185 (9)	0.0198 (9)	0.0166 (9)	0.0024 (7)	0.0007 (7)	−0.0055 (7)
C1S	0.0440 (16)	0.0411 (14)	0.0611 (19)	0.0072 (12)	−0.0024 (14)	−0.0080 (13)
C2	0.0158 (9)	0.0199 (9)	0.0153 (9)	0.0008 (7)	0.0021 (7)	−0.0017 (7)
C2S	0.063 (2)	0.0492 (16)	0.0415 (16)	0.0117 (14)	−0.0065 (14)	0.0055 (13)
C3	0.0137 (9)	0.0175 (8)	0.0143 (9)	0.0015 (7)	0.0015 (7)	−0.0015 (7)
C4	0.0129 (9)	0.0171 (8)	0.0140 (9)	0.0016 (7)	0.0010 (7)	−0.0018 (7)
C5	0.0163 (9)	0.0155 (8)	0.0163 (9)	0.0004 (7)	0.0021 (7)	−0.0015 (7)
C6	0.0204 (10)	0.0191 (9)	0.0166 (9)	0.0030 (8)	0.0053 (7)	0.0011 (7)
C7	0.0216 (10)	0.0188 (9)	0.0135 (9)	0.0033 (8)	0.0019 (7)	−0.0014 (7)
C8	0.0163 (9)	0.0177 (9)	0.0153 (9)	0.0034 (7)	0.0003 (7)	0.0001 (7)
C9	0.0165 (9)	0.0199 (9)	0.0133 (9)	0.0014 (7)	0.0019 (7)	−0.0057 (7)
C10	0.0241 (10)	0.0213 (9)	0.0170 (9)	0.0035 (8)	−0.0009 (8)	−0.0016 (7)
C11	0.0193 (10)	0.0267 (10)	0.0226 (10)	0.0023 (8)	−0.0060 (8)	−0.0029 (8)
C12	0.0154 (9)	0.0217 (9)	0.0264 (11)	−0.0014 (8)	0.0019 (8)	−0.0053 (8)
C13	0.0203 (10)	0.0210 (9)	0.0214 (10)	0.0005 (8)	0.0026 (8)	0.0004 (8)
C14	0.0171 (9)	0.0229 (9)	0.0168 (9)	0.0014 (8)	−0.0003 (7)	−0.0018 (7)
C15	0.0224 (10)	0.0233 (10)	0.0154 (9)	0.0037 (8)	0.0043 (8)	−0.0030 (7)
C16	0.0520 (15)	0.0245 (10)	0.0171 (10)	0.0133 (10)	−0.0010 (10)	−0.0077 (8)
C17	0.0543 (18)	0.0345 (13)	0.0632 (19)	0.0106 (13)	−0.0226 (15)	−0.0208 (13)
C18	0.0190 (11)	0.0234 (10)	0.0582 (16)	−0.0056 (9)	0.0013 (10)	0.0043 (10)
C19	0.0282 (11)	0.0350 (11)	0.0244 (11)	0.0024 (9)	0.0139 (9)	−0.0012 (9)
N1	0.0212 (9)	0.0340 (10)	0.0186 (9)	−0.0044 (7)	0.0027 (7)	−0.0124 (7)
N2	0.0147 (8)	0.0279 (9)	0.0166 (8)	−0.0038 (7)	0.0044 (6)	−0.0081 (7)
N3	0.0165 (8)	0.0206 (8)	0.0208 (8)	0.0010 (6)	0.0070 (6)	0.0015 (6)
O1	0.0205 (7)	0.0330 (8)	0.0176 (7)	−0.0025 (6)	0.0041 (6)	−0.0084 (6)
O1S	0.0257 (9)	0.0666 (12)	0.0361 (10)	−0.0024 (8)	0.0035 (7)	−0.0127 (9)
O2	0.0574 (11)	0.0298 (8)	0.0155 (7)	0.0153 (8)	−0.0053 (7)	−0.0035 (6)
O3	0.0395 (9)	0.0218 (7)	0.0146 (7)	0.0076 (6)	−0.0019 (6)	−0.0039 (5)
O4	0.0172 (7)	0.0231 (7)	0.0427 (9)	−0.0050 (6)	−0.0038 (6)	0.0015 (6)
S1	0.0145 (3)	0.0207 (3)	0.0183 (3)	−0.00379 (18)	0.00207 (18)	−0.00517 (18)
S1S	0.0216 (3)	0.0423 (4)	0.0372 (4)	−0.0064 (2)	−0.0002 (2)	0.0015 (3)

Geometric parameters (Å, º) top

C1—O1	1.247 (2)	C11—C12	1.394 (3)
C1—N1	1.332 (3)	C11—H11	0.9500
C1—C2	1.463 (3)	C12—O4	1.368 (2)
C1S—S1S	1.784 (3)	C12—C13	1.389 (3)
C1S—H1S1	0.9800	C13—C14	1.385 (3)
C1S—H1S2	0.9800	C13—H13	0.9500
C1S—H1S3	0.9800	C14—H14	0.9500
C2—C3	1.385 (3)	C15—O2	1.202 (2)
C2—S1	1.7489 (19)	C15—O3	1.335 (2)
C2S—S1S	1.783 (3)	C16—O3	1.458 (2)
C2S—H2S1	0.9800	C16—C17	1.494 (4)
C2S—H2S2	0.9800	C16—H16A	0.9900
C2S—H2S3	0.9800	C16—H16B	0.9900
C3—N2	1.354 (2)	C17—H17A	0.9800
C3—C4	1.449 (2)	C17—H17B	0.9800
C4—C8	1.407 (2)	C17—H17C	0.9800
C4—C5	1.408 (3)	C18—O4	1.443 (3)
C5—N3	1.341 (2)	C18—H18A	0.9800
C5—S1	1.7351 (19)	C18—H18B	0.9800
C6—N3	1.333 (3)	C18—H18C	0.9800
C6—C7	1.412 (3)	C19—H19A	0.9800
C6—C19	1.507 (3)	C19—H19B	0.9800
C7—C8	1.391 (3)	C19—H19C	0.9800
C7—C15	1.505 (3)	N1—H1A	0.883 (17)
C8—C9	1.490 (3)	N1—H1B	0.872 (17)
C9—C14	1.395 (3)	N2—H2A	0.856 (16)
C9—C10	1.395 (3)	N2—H2B	0.849 (17)
C10—C11	1.384 (3)	O1S—S1S	1.4997 (19)
C10—H10	0.9500

O1—C1—N1	121.43 (18)	C13—C12—C11	119.54 (18)
O1—C1—C2	119.93 (17)	C14—C13—C12	119.80 (18)
N1—C1—C2	118.62 (18)	C14—C13—H13	120.1
S1S—C1S—H1S1	109.5	C12—C13—H13	120.1
S1S—C1S—H1S2	109.5	C13—C14—C9	121.21 (18)
H1S1—C1S—H1S2	109.5	C13—C14—H14	119.4
S1S—C1S—H1S3	109.5	C9—C14—H14	119.4
H1S1—C1S—H1S3	109.5	O2—C15—O3	124.74 (18)
H1S2—C1S—H1S3	109.5	O2—C15—C7	125.44 (18)
C3—C2—C1	124.40 (17)	O3—C15—C7	109.77 (16)
C3—C2—S1	113.21 (14)	O3—C16—C17	111.1 (2)
C1—C2—S1	122.33 (14)	O3—C16—H16A	109.4
S1S—C2S—H2S1	109.5	C17—C16—H16A	109.4
S1S—C2S—H2S2	109.5	O3—C16—H16B	109.4
H2S1—C2S—H2S2	109.5	C17—C16—H16B	109.4
S1S—C2S—H2S3	109.5	H16A—C16—H16B	108.0
H2S1—C2S—H2S3	109.5	C16—C17—H17A	109.5
H2S2—C2S—H2S3	109.5	C16—C17—H17B	109.5
N2—C3—C2	123.98 (17)	H17A—C17—H17B	109.5
N2—C3—C4	124.14 (17)	C16—C17—H17C	109.5
C2—C3—C4	111.89 (16)	H17A—C17—H17C	109.5
C8—C4—C5	117.15 (17)	H17B—C17—H17C	109.5
C8—C4—C3	131.66 (17)	O4—C18—H18A	109.5
C5—C4—C3	111.17 (16)	O4—C18—H18B	109.5
N3—C5—C4	126.23 (18)	H18A—C18—H18B	109.5
N3—C5—S1	120.69 (15)	O4—C18—H18C	109.5
C4—C5—S1	113.06 (14)	H18A—C18—H18C	109.5
N3—C6—C7	122.10 (17)	H18B—C18—H18C	109.5
N3—C6—C19	116.99 (18)	C6—C19—H19A	109.5
C7—C6—C19	120.84 (18)	C6—C19—H19B	109.5
C8—C7—C6	121.53 (18)	H19A—C19—H19B	109.5
C8—C7—C15	120.07 (17)	C6—C19—H19C	109.5
C6—C7—C15	118.10 (17)	H19A—C19—H19C	109.5
C7—C8—C4	116.71 (17)	H19B—C19—H19C	109.5
C7—C8—C9	119.62 (17)	C1—N1—H1A	128.2 (17)
C4—C8—C9	123.53 (17)	C1—N1—H1B	116.7 (18)
C14—C9—C10	118.48 (18)	H1A—N1—H1B	115 (2)
C14—C9—C8	119.18 (17)	C3—N2—H2A	116.7 (17)
C10—C9—C8	122.19 (17)	C3—N2—H2B	127.3 (17)
C11—C10—C9	120.59 (18)	H2A—N2—H2B	115 (2)
C11—C10—H10	119.7	C6—N3—C5	116.20 (16)
C9—C10—H10	119.7	C15—O3—C16	117.63 (15)
C10—C11—C12	120.30 (18)	C12—O4—C18	116.62 (16)
C10—C11—H11	119.9	C5—S1—C2	90.56 (9)
C12—C11—H11	119.9	O1S—S1S—C2S	106.93 (13)
O4—C12—C13	123.92 (18)	O1S—S1S—C1S	106.65 (12)
O4—C12—C11	116.53 (18)	C2S—S1S—C1S	96.36 (15)

O1—C1—C2—C3	7.7 (3)	C7—C8—C9—C10	64.7 (2)
N1—C1—C2—C3	−170.64 (18)	C4—C8—C9—C10	−119.9 (2)
O1—C1—C2—S1	−175.41 (14)	C14—C9—C10—C11	1.1 (3)
N1—C1—C2—S1	6.2 (3)	C8—C9—C10—C11	−174.31 (18)
C1—C2—C3—N2	−4.7 (3)	C9—C10—C11—C12	1.7 (3)
S1—C2—C3—N2	178.22 (15)	C10—C11—C12—O4	176.32 (18)
C1—C2—C3—C4	174.97 (17)	C10—C11—C12—C13	−3.2 (3)
S1—C2—C3—C4	−2.1 (2)	O4—C12—C13—C14	−177.50 (18)
N2—C3—C4—C8	4.5 (3)	C11—C12—C13—C14	1.9 (3)
C2—C3—C4—C8	−175.14 (18)	C12—C13—C14—C9	0.8 (3)
N2—C3—C4—C5	−176.73 (17)	C10—C9—C14—C13	−2.3 (3)
C2—C3—C4—C5	3.6 (2)	C8—C9—C14—C13	173.22 (17)
C8—C4—C5—N3	−2.9 (3)	C8—C7—C15—O2	−109.9 (2)
C3—C4—C5—N3	178.15 (17)	C6—C7—C15—O2	76.3 (3)
C8—C4—C5—S1	175.38 (13)	C8—C7—C15—O3	72.7 (2)
C3—C4—C5—S1	−3.6 (2)	C6—C7—C15—O3	−101.1 (2)
N3—C6—C7—C8	−1.6 (3)	C7—C6—N3—C5	1.7 (3)
C19—C6—C7—C8	−178.25 (18)	C19—C6—N3—C5	178.43 (17)
N3—C6—C7—C15	172.07 (17)	C4—C5—N3—C6	0.6 (3)
C19—C6—C7—C15	−4.6 (3)	S1—C5—N3—C6	−177.53 (13)
C6—C7—C8—C4	−0.8 (3)	O2—C15—O3—C16	0.6 (3)
C15—C7—C8—C4	−174.30 (16)	C7—C15—O3—C16	178.10 (17)
C6—C7—C8—C9	175.02 (16)	C17—C16—O3—C15	84.1 (2)
C15—C7—C8—C9	1.5 (3)	C13—C12—O4—C18	8.8 (3)
C5—C4—C8—C7	2.7 (2)	C11—C12—O4—C18	−170.63 (19)
C3—C4—C8—C7	−178.55 (18)	N3—C5—S1—C2	−179.58 (16)
C5—C4—C8—C9	−172.84 (16)	C4—C5—S1—C2	2.04 (14)
C3—C4—C8—C9	5.9 (3)	C3—C2—S1—C5	0.10 (15)
C7—C8—C9—C14	−110.7 (2)	C1—C2—S1—C5	−177.08 (16)
C4—C8—C9—C14	64.8 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O1ⁱ	0.87 (2)	2.07 (2)	2.916 (2)	165 (2)
N1—H1A···O1Sⁱⁱ	0.88 (2)	2.08 (2)	2.918 (3)	158 (2)
N2—H2A···O1	0.86 (2)	2.10 (2)	2.719 (2)	129 (2)
C14—H14···O3ⁱⁱⁱ	0.95	2.50	3.381 (2)	155
C16—H16A···O2^iv	0.99	2.48	3.254 (3)	134
C19—H19C···O1^v	0.98	2.75	3.474 (3)	131
C19—H19A···O1S^vi	0.98	2.84	3.483 (3)	124

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

Acknowledgements

JPJ would like to acknowledge the NSF–MRI program (grant No. CHE-1039027) for funds to purchase the X-ray diffractometer.

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