N′-[(1Z)-1-(3-Methyl-5-oxo-1-phenyl-4,5-di­hydro-1H-pyrazol-4-yl­idene)eth­yl]-2-[(4-methyl­phen­yl)sulfan­yl]acetohydrazide

Mohamed, S.K.; Mague, J.T.; Akkurt, M.; Abbady, M.S.; Bakhite, E.A.; Albayati, M.R.

doi:10.1107/S2414314617016662

organic compounds

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ISSN: 2414-3146

Volume 2| Part 11| November 2017| x171666

https://doi.org/10.1107/S2414314617016662

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N′-[(1Z)-1-(3-Methyl-5-oxo-1-phenyl-4,5-dihydro-1H-pyrazol-4-ylidene)ethyl]-2-[(4-methylphenyl)sulfanyl]acetohydrazide

Shaaban K. Mohamed,^a,^b Joel T. Mague,^c Mehmet Akkurt,^d Mohamed S. Abbady,^e Etify A. Bakhite ^e and Mustafa R. Albayati ^f ^*

^aChemistry and Environmental Division, Manchester Metropolitan University, Manchester M1 5GD, England, ^bChemistry Department, Faculty of Science, Minia University, 61519 El-Minia, Egypt, ^cDepartment of Chemistry, Tulane University, New Orleans, LA 70118, USA, ^dDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey, ^eChemistry Department, Faculty of Science, Assiut University, 71516 Assiut, Egypt, and ^fKirkuk University, College of Education, Department of Chemistry, Kirkuk, Iraq
^*Correspondence e-mail: shaabankamel@yahoo.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 15 November 2017; accepted 19 November 2017; online 28 November 2017)

In the title compound, C₂₁H₂₂N₄O₂S, the dihedral angle between the pyrazole ring and adjacent benzene ring is 6.4 (1)°. The molecular conformation is influenced by intramolecular N—H⋯O and C—H⋯O hydrogen bonds. In the crystal, N—H⋯O hydrogen bonds plus C—H⋯π and π–π stacking interactions form chains extending in the a-axis direction. The chains are linked by complementary pairs of C—H⋯π interactions.

Keywords: crystal structure; hydrogen bond; π-stacking; pyrazolones; Schiff bases.

CCDC reference: 1586428

Structure description

Pyrazolone derivatives are important components of numerous pharmaceuticals, agrochemicals, dyes and pigments, chelating and extracting agents (e.g. Himly et al., 2003 ; Shweta et al., 2013 ). As part of our studies in this area, we now describe the synthesis and structure of the title compound. A related compound, (Z)-4-[1-(4-acetylanilino) ethylidene]-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one derived from acyl pyrazolone and aromatic amine was reported to possess the keto–amine tautomer in the solid state (Mahfouz et al. 2015 ).

The conformation of the substituents on the 5-membered heterocyclic ring in the title compound is determined, in part, by the intramolecular N3—H3A⋯O1 hydrogen bond and, to a lesser extent, the intramolecular C2—H2⋯O1 hydrogen bond (Table 1 and Fig. 1). The dihedral angle between the mean planes of the C1–C6 and the N1/N2/C7–C9 rings is thus 6.4 (1)°, while that between the latter ring and the C15–C20 ring is 2.4 (1)°. Despite this, the molecule is not entirely planar as indicated by the C11—N3—N4—C13 torsion angle of 138.79 (19)°.

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg3 are the centroids of the N1/N2/C7–C9 and C15–C20 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O1	0.95 (3)	1.82 (3)	2.627 (2)	141 (2)
N4—H4A⋯O2ⁱ	0.90 (3)	1.96 (3)	2.858 (2)	174 (2)
C2—H2⋯O1	0.96 (2)	2.30 (2)	2.937 (2)	123.1 (18)
C10—H10B⋯Cg1ⁱ	0.99 (3)	2.80 (3)	3.740 (2)	159 (2)
C14—H14A⋯Cg3ⁱⁱ	1.00 (2)	2.99 (2)	3.947 (3)	161 (2)
C16—H16⋯O2ⁱⁱⁱ	0.94 (3)	2.65 (3)	3.436 (3)	143 (2)
Symmetry codes: (i) x-1, y, z; (ii) -x, -y+1, -z; (iii) -x+1, -y+1, -z+1.

Figure 1
The molecular structure, with 50% probability displacement ellipsoids. The intramolecular N—H⋯O and C—H⋯O hydrogen bonds are shown as blue and black dashed lines, respectively.

In the crystal, N4—H4A⋯O2 hydrogen bonds accompanied by C—H⋯π (C10—H10B⋯Cg1; Table 1 and Fig. 2) and π–π-stacking interactions [Cg1⋯Cg2(−1 + x, y, z) = 3.667 (1) Å, Cg1 and Cg2 are the centroids of the N1/N2/C7–C9 and C1–C6 rings, respectively] form chains propagating along the a-axis direction (Fig. 2). These chains are linked through pairwise C—H⋯π [C14—H14A⋯Cg3; Cg3 is the centroid of the C15–C20 ring at −x, −y + 1, −z] interactions (Fig. 3 and Table 1).

Figure 2
Plan view of the packing, showing the layers formed by intermolecular N—H⋯O hydrogen bonds (blue dashed lines) and C—H⋯π and π–π stacking interactions (green and orange dashed lines respectively).

Figure 3
Elevation view of the packing along the a-axis direction, showing the connecting of two layers through C—H⋯π interactions.

Synthesis and crystallization

The title compound was obtained by refluxing equimolar quantities of 4-acetyl-3-methyl-1-phenyl-2-pyrazolin-5-one (1.081 g m, 5 mmol) and 2-(4-tolylthio)acethydrazide (0.981 g m, 5 mmol) in 30 ml ethanol for 2 h. On cooling, the yellow precipitate was collected by filtration and recrystallized from dimethylformamide (DMF) solution as colourless plates. Yield (89%); m.p. 443–445 K; IR (KBr, cm⁻¹); 3232 (NH), 1656,1633 (2 C=O).

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₂₁H₂₂N₄O₂S
M_r	394.48
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	150
a, b, c (Å)	4.8687 (2), 46.7634 (16), 8.4173 (3)
β (°)	100.232 (1)
V (Å³)	1885.95 (12)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	1.73
Crystal size (mm)	0.19 × 0.08 × 0.04

Data collection
Diffractometer	Bruker D8 VENTURE PHOTON 100 CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2016 )
T_min, T_max	0.78, 0.94
No. of measured, independent and observed [I > 2σ(I)] reflections	16199, 3723, 3404
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.103, 1.12
No. of reflections	3723
No. of parameters	341
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.27
Computer programs: APEX3 and SAINT (Bruker, 2016), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), DIAMOND (Brandenburg & Putz, 2012 ) and SHELXTL (Sheldrick, 2008 ).

Structural data

CCDC reference: 1586428

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314617016662/hb4182sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617016662/hb4182Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617016662/hb4182Isup3.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

N'-[(1Z)-1-(3-Methyl-5-oxo-1-phenyl-4,5-dihydro-1H-pyrazol-4-ylidene)ethyl]-2-[(4-methylphenyl)sulfanyl]acetohydrazide top

Crystal data top

C₂₁H₂₂N₄O₂S	F(000) = 832
M_r = 394.48	D_x = 1.389 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54178 Å
a = 4.8687 (2) Å	Cell parameters from 9883 reflections
b = 46.7634 (16) Å	θ = 3.8–74.5°
c = 8.4173 (3) Å	µ = 1.73 mm⁻¹
β = 100.232 (1)°	T = 150 K
V = 1885.95 (12) Å³	Plate, colourless
Z = 4	0.19 × 0.08 × 0.04 mm

Data collection top

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer	3723 independent reflections
Radiation source: INCOATEC IµS micro-focus source	3404 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.044
Detector resolution: 10.4167 pixels mm^-1	θ_max = 74.5°, θ_min = 3.8°
ω scans	h = −6→5
Absorption correction: multi-scan (SADABS; Bruker, 2016)	k = −57→53
T_min = 0.78, T_max = 0.94	l = −10→9
16199 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)] = 0.044	Hydrogen site location: difference Fourier map
wR(F²) = 0.103	All H-atom parameters refined
S = 1.12	w = 1/[σ²(F_o²) + (0.023P)² + 1.718P] where P = (F_o² + 2F_c²)/3
3723 reflections	(Δ/σ)_max = 0.002
341 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.27 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
S1	0.23101 (10)	0.51189 (2)	0.34557 (6)	0.03032 (14)
O1	0.4863 (3)	0.63157 (3)	0.66802 (17)	0.0278 (3)
O2	0.3695 (3)	0.57155 (3)	0.37885 (19)	0.0324 (3)
N1	0.4559 (3)	0.68151 (3)	0.69106 (19)	0.0229 (3)
N2	0.2746 (3)	0.70331 (3)	0.6214 (2)	0.0247 (3)
N3	0.0537 (3)	0.61217 (3)	0.4649 (2)	0.0268 (4)
H3A	0.222 (6)	0.6101 (5)	0.541 (3)	0.043 (7)*
N4	−0.0633 (3)	0.58791 (3)	0.3844 (2)	0.0262 (4)
H4A	−0.243 (6)	0.5838 (5)	0.388 (3)	0.036 (6)*
C1	0.6842 (4)	0.68887 (4)	0.8128 (2)	0.0231 (4)
C2	0.8821 (4)	0.66859 (4)	0.8780 (2)	0.0275 (4)
H2	0.869 (5)	0.6493 (5)	0.840 (3)	0.034 (6)*
C3	1.1042 (4)	0.67684 (5)	0.9954 (3)	0.0312 (4)
H3	1.244 (6)	0.6623 (6)	1.040 (3)	0.045 (7)*
C4	1.1317 (5)	0.70485 (5)	1.0504 (3)	0.0337 (5)
H4	1.298 (5)	0.7096 (5)	1.136 (3)	0.037 (6)*
C5	0.9319 (5)	0.72481 (5)	0.9863 (3)	0.0335 (5)
H5	0.944 (5)	0.7449 (5)	1.026 (3)	0.039 (6)*
C6	0.7097 (4)	0.71708 (4)	0.8682 (3)	0.0295 (4)
H6	0.569 (5)	0.7305 (5)	0.821 (3)	0.035 (6)*
C7	0.3680 (4)	0.65506 (4)	0.6301 (2)	0.0224 (4)
C8	0.1170 (4)	0.66065 (4)	0.5138 (2)	0.0227 (4)
C9	0.0774 (4)	0.69108 (4)	0.5178 (2)	0.0233 (4)
C10	−0.1466 (4)	0.70947 (5)	0.4262 (3)	0.0301 (4)
H10A	−0.149 (6)	0.7090 (6)	0.308 (3)	0.046 (7)*
H10B	−0.334 (6)	0.7035 (6)	0.443 (3)	0.047 (7)*
H10C	−0.110 (5)	0.7297 (6)	0.467 (3)	0.043 (7)*
C11	−0.0348 (4)	0.63867 (4)	0.4278 (2)	0.0234 (4)
C12	−0.2844 (4)	0.64281 (5)	0.2995 (3)	0.0310 (4)
H12A	−0.263 (7)	0.6320 (7)	0.200 (4)	0.071 (10)*
H12B	−0.449 (8)	0.6345 (7)	0.331 (4)	0.078 (10)*
H12C	−0.326 (7)	0.6624 (8)	0.279 (4)	0.081 (11)*
C13	0.1168 (4)	0.56754 (4)	0.3541 (2)	0.0242 (4)
C14	−0.0179 (4)	0.54011 (4)	0.2839 (3)	0.0277 (4)
H14A	−0.052 (5)	0.5424 (5)	0.164 (3)	0.029 (6)*
H14B	−0.189 (5)	0.5365 (5)	0.317 (3)	0.036 (6)*
C15	0.0623 (4)	0.48142 (4)	0.2500 (2)	0.0258 (4)
C16	0.1980 (5)	0.45551 (5)	0.2878 (3)	0.0356 (5)
H16	0.366 (6)	0.4553 (6)	0.362 (3)	0.052 (8)*
C17	0.0904 (5)	0.43032 (5)	0.2146 (3)	0.0367 (5)
H17	0.191 (6)	0.4126 (6)	0.243 (3)	0.044 (7)*
C18	−0.1533 (5)	0.43025 (4)	0.1019 (2)	0.0315 (4)
C19	−0.2882 (5)	0.45609 (5)	0.0662 (3)	0.0402 (5)
H19	−0.460 (6)	0.4568 (6)	−0.013 (3)	0.051 (8)*
C20	−0.1826 (5)	0.48153 (5)	0.1387 (3)	0.0373 (5)
H20	−0.279 (6)	0.4986 (6)	0.113 (3)	0.054 (8)*
C21	−0.2696 (7)	0.40302 (5)	0.0196 (3)	0.0431 (6)
H21A	−0.323 (7)	0.3891 (7)	0.093 (4)	0.074 (10)*
H21B	−0.123 (8)	0.3934 (7)	−0.028 (4)	0.077 (11)*
H21C	−0.433 (8)	0.4066 (8)	−0.065 (5)	0.087 (12)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0232 (2)	0.0279 (3)	0.0363 (3)	0.00029 (18)	−0.00429 (19)	−0.00213 (19)
O1	0.0256 (7)	0.0216 (7)	0.0337 (8)	0.0005 (5)	−0.0012 (6)	0.0002 (5)
O2	0.0155 (7)	0.0340 (8)	0.0468 (9)	−0.0025 (5)	0.0032 (6)	−0.0049 (6)
N1	0.0211 (8)	0.0218 (7)	0.0256 (8)	−0.0012 (6)	0.0033 (6)	0.0003 (6)
N2	0.0233 (8)	0.0231 (8)	0.0287 (9)	0.0026 (6)	0.0073 (7)	0.0027 (6)
N3	0.0207 (8)	0.0256 (8)	0.0321 (9)	−0.0032 (6)	−0.0010 (7)	−0.0045 (7)
N4	0.0142 (8)	0.0265 (8)	0.0373 (10)	−0.0043 (6)	0.0033 (7)	−0.0062 (7)
C1	0.0206 (9)	0.0269 (9)	0.0231 (10)	−0.0049 (7)	0.0071 (7)	−0.0016 (7)
C2	0.0260 (10)	0.0278 (10)	0.0285 (10)	−0.0025 (8)	0.0039 (8)	−0.0015 (8)
C3	0.0251 (10)	0.0383 (11)	0.0292 (11)	−0.0022 (8)	0.0022 (8)	−0.0012 (8)
C4	0.0272 (11)	0.0459 (12)	0.0277 (11)	−0.0100 (9)	0.0037 (9)	−0.0069 (9)
C5	0.0332 (11)	0.0328 (11)	0.0363 (12)	−0.0103 (9)	0.0109 (9)	−0.0102 (9)
C6	0.0281 (10)	0.0272 (10)	0.0344 (11)	−0.0032 (8)	0.0092 (9)	−0.0044 (8)
C7	0.0206 (9)	0.0235 (9)	0.0237 (9)	−0.0020 (7)	0.0057 (7)	0.0006 (7)
C8	0.0187 (9)	0.0261 (9)	0.0239 (9)	0.0005 (7)	0.0060 (7)	0.0012 (7)
C9	0.0212 (9)	0.0262 (9)	0.0246 (10)	0.0003 (7)	0.0094 (7)	0.0026 (7)
C10	0.0261 (10)	0.0305 (11)	0.0346 (12)	0.0058 (8)	0.0078 (9)	0.0065 (8)
C11	0.0164 (8)	0.0285 (9)	0.0265 (10)	0.0006 (7)	0.0074 (7)	0.0002 (7)
C12	0.0242 (10)	0.0363 (11)	0.0307 (11)	0.0002 (8)	−0.0003 (9)	−0.0018 (9)
C13	0.0171 (9)	0.0279 (9)	0.0268 (10)	−0.0016 (7)	0.0021 (7)	−0.0002 (7)
C14	0.0154 (9)	0.0295 (10)	0.0369 (12)	−0.0006 (7)	0.0013 (8)	−0.0065 (8)
C15	0.0249 (9)	0.0271 (10)	0.0259 (10)	−0.0005 (7)	0.0056 (8)	−0.0001 (7)
C16	0.0378 (12)	0.0315 (11)	0.0330 (12)	0.0008 (9)	−0.0065 (10)	0.0052 (9)
C17	0.0452 (13)	0.0262 (10)	0.0368 (12)	0.0037 (9)	0.0022 (10)	0.0049 (8)
C18	0.0410 (12)	0.0272 (10)	0.0269 (10)	−0.0028 (9)	0.0079 (9)	−0.0007 (8)
C19	0.0380 (12)	0.0323 (11)	0.0437 (14)	−0.0003 (9)	−0.0109 (11)	−0.0037 (9)
C20	0.0299 (11)	0.0275 (11)	0.0494 (14)	0.0037 (9)	−0.0068 (10)	−0.0049 (9)
C21	0.0645 (17)	0.0283 (11)	0.0348 (13)	−0.0053 (11)	0.0037 (12)	−0.0030 (9)

Geometric parameters (Å, º) top

S1—C15	1.765 (2)	C8—C9	1.437 (3)
S1—C14	1.805 (2)	C9—C10	1.492 (3)
O1—C7	1.255 (2)	C10—H10A	0.99 (3)
O2—C13	1.225 (2)	C10—H10B	0.99 (3)
N1—C7	1.378 (2)	C10—H10C	1.01 (3)
N1—N2	1.407 (2)	C11—C12	1.488 (3)
N1—C1	1.414 (2)	C12—H12A	1.00 (3)
N2—C9	1.308 (3)	C12—H12B	0.97 (4)
N3—C11	1.331 (2)	C12—H12C	0.95 (4)
N3—N4	1.391 (2)	C13—C14	1.512 (3)
N3—H3A	0.95 (3)	C14—H14A	1.00 (2)
N4—C13	1.349 (2)	C14—H14B	0.94 (3)
N4—H4A	0.90 (3)	C15—C20	1.380 (3)
C1—C2	1.393 (3)	C15—C16	1.390 (3)
C1—C6	1.397 (3)	C16—C17	1.388 (3)
C2—C3	1.384 (3)	C16—H16	0.94 (3)
C2—H2	0.96 (2)	C17—C18	1.382 (3)
C3—C4	1.388 (3)	C17—H17	0.97 (3)
C3—H3	0.98 (3)	C18—C19	1.383 (3)
C4—C5	1.387 (3)	C18—C21	1.511 (3)
C4—H4	1.01 (3)	C19—C20	1.393 (3)
C5—C6	1.381 (3)	C19—H19	0.97 (3)
C5—H5	1.00 (2)	C20—H20	0.93 (3)
C6—H6	0.96 (3)	C21—H21A	0.96 (4)
C7—C8	1.448 (3)	C21—H21B	0.99 (4)
C8—C11	1.391 (3)	C21—H21C	0.98 (4)

C15—S1—C14	103.00 (9)	H10B—C10—H10C	109 (2)
C7—N1—N2	111.40 (15)	N3—C11—C8	116.50 (17)
C7—N1—C1	129.83 (16)	N3—C11—C12	118.68 (18)
N2—N1—C1	118.70 (15)	C8—C11—C12	124.83 (18)
C9—N2—N1	107.04 (15)	C11—C12—H12A	110.4 (19)
C11—N3—N4	123.90 (17)	C11—C12—H12B	111 (2)
C11—N3—H3A	117.1 (15)	H12A—C12—H12B	104 (3)
N4—N3—H3A	118.5 (15)	C11—C12—H12C	112 (2)
C13—N4—N3	116.36 (16)	H12A—C12—H12C	113 (3)
C13—N4—H4A	121.5 (16)	H12B—C12—H12C	106 (3)
N3—N4—H4A	118.3 (16)	O2—C13—N4	121.79 (17)
C2—C1—C6	119.79 (19)	O2—C13—C14	123.27 (17)
C2—C1—N1	121.30 (17)	N4—C13—C14	114.92 (16)
C6—C1—N1	118.91 (18)	C13—C14—S1	106.59 (13)
C3—C2—C1	119.33 (19)	C13—C14—H14A	106.7 (13)
C3—C2—H2	119.8 (15)	S1—C14—H14A	110.7 (13)
C1—C2—H2	120.9 (15)	C13—C14—H14B	112.5 (15)
C2—C3—C4	121.2 (2)	S1—C14—H14B	111.4 (15)
C2—C3—H3	118.4 (16)	H14A—C14—H14B	109 (2)
C4—C3—H3	120.4 (16)	C20—C15—C16	118.48 (19)
C5—C4—C3	119.1 (2)	C20—C15—S1	125.64 (16)
C5—C4—H4	123.2 (14)	C16—C15—S1	115.83 (16)
C3—C4—H4	117.7 (14)	C17—C16—C15	120.8 (2)
C6—C5—C4	120.6 (2)	C17—C16—H16	120.2 (17)
C6—C5—H5	118.6 (15)	C15—C16—H16	119.0 (17)
C4—C5—H5	120.8 (15)	C18—C17—C16	121.2 (2)
C5—C6—C1	119.9 (2)	C18—C17—H17	119.9 (16)
C5—C6—H6	122.5 (15)	C16—C17—H17	118.9 (16)
C1—C6—H6	117.5 (15)	C17—C18—C19	117.6 (2)
O1—C7—N1	126.39 (18)	C17—C18—C21	121.6 (2)
O1—C7—C8	128.62 (17)	C19—C18—C21	120.8 (2)
N1—C7—C8	104.99 (15)	C18—C19—C20	121.8 (2)
C11—C8—C9	133.06 (18)	C18—C19—H19	119.8 (16)
C11—C8—C7	121.66 (17)	C20—C19—H19	118.4 (16)
C9—C8—C7	105.27 (16)	C15—C20—C19	120.1 (2)
N2—C9—C8	111.30 (17)	C15—C20—H20	119.8 (18)
N2—C9—C10	118.37 (17)	C19—C20—H20	120.1 (18)
C8—C9—C10	130.34 (18)	C18—C21—H21A	113 (2)
C9—C10—H10A	112.6 (16)	C18—C21—H21B	109 (2)
C9—C10—H10B	111.7 (16)	H21A—C21—H21B	104 (3)
H10A—C10—H10B	107 (2)	C18—C21—H21C	112 (2)
C9—C10—H10C	107.2 (15)	H21A—C21—H21C	108 (3)
H10A—C10—H10C	109 (2)	H21B—C21—H21C	109 (3)

C7—N1—N2—C9	−0.5 (2)	C7—C8—C9—N2	0.1 (2)
C1—N1—N2—C9	−177.73 (15)	C11—C8—C9—C10	−0.7 (3)
C11—N3—N4—C13	138.79 (19)	C7—C8—C9—C10	−179.26 (19)
C7—N1—C1—C2	8.0 (3)	N4—N3—C11—C8	−175.98 (17)
N2—N1—C1—C2	−175.34 (16)	N4—N3—C11—C12	4.0 (3)
C7—N1—C1—C6	−171.82 (18)	C9—C8—C11—N3	−174.60 (19)
N2—N1—C1—C6	4.8 (2)	C7—C8—C11—N3	3.8 (3)
C6—C1—C2—C3	−1.0 (3)	C9—C8—C11—C12	5.4 (3)
N1—C1—C2—C3	179.13 (18)	C7—C8—C11—C12	−176.18 (18)
C1—C2—C3—C4	0.7 (3)	N3—N4—C13—O2	−8.4 (3)
C2—C3—C4—C5	0.1 (3)	N3—N4—C13—C14	173.28 (17)
C3—C4—C5—C6	−0.6 (3)	O2—C13—C14—S1	29.7 (2)
C4—C5—C6—C1	0.3 (3)	N4—C13—C14—S1	−152.02 (15)
C2—C1—C6—C5	0.6 (3)	C15—S1—C14—C13	−177.22 (14)
N1—C1—C6—C5	−179.58 (18)	C14—S1—C15—C20	8.0 (2)
N2—N1—C7—O1	179.70 (17)	C14—S1—C15—C16	−174.65 (17)
C1—N1—C7—O1	−3.5 (3)	C20—C15—C16—C17	0.3 (3)
N2—N1—C7—C8	0.57 (19)	S1—C15—C16—C17	−177.29 (18)
C1—N1—C7—C8	177.41 (17)	C15—C16—C17—C18	0.3 (4)
O1—C7—C8—C11	1.7 (3)	C16—C17—C18—C19	−0.9 (3)
N1—C7—C8—C11	−179.19 (16)	C16—C17—C18—C21	179.0 (2)
O1—C7—C8—C9	−179.53 (18)	C17—C18—C19—C20	0.9 (4)
N1—C7—C8—C9	−0.42 (19)	C21—C18—C19—C20	−179.0 (2)
N1—N2—C9—C8	0.2 (2)	C16—C15—C20—C19	−0.3 (4)
N1—N2—C9—C10	179.68 (16)	S1—C15—C20—C19	177.05 (19)
C11—C8—C9—N2	178.71 (19)	C18—C19—C20—C15	−0.3 (4)

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg3 are the centroids of the N1/N2/C7–C9 and C15–C20 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O1	0.95 (3)	1.82 (3)	2.627 (2)	141 (2)
N4—H4A···O2ⁱ	0.90 (3)	1.96 (3)	2.858 (2)	174 (2)
C2—H2···O1	0.96 (2)	2.30 (2)	2.937 (2)	123.1 (18)
C10—H10B···Cg1ⁱ	0.99 (3)	2.80 (3)	3.740 (2)	159 (2)
C14—H14A···Cg3ⁱⁱ	1.00 (2)	2.99 (2)	3.947 (3)	161 (2)
C16—H16···O2ⁱⁱⁱ	0.94 (3)	2.65 (3)	3.436 (3)	143 (2)

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

Acknowledgements

The support of NSF–MRI Grant No. 1228232 for the purchase of the diffractometer and Tulane University for support of the Tulane Crystallography Laboratory are gratefully acknowledged.

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