5-Acetyl-2-{[(1H-benzimidazol-2-yl)meth­yl]sulfan­yl}-4-(4-meth­oxy­phen­yl)-6-methyl­pyridine-3-carbonitrile

Mague, J.T.; Mohamed, S.K.; Akkurt, M.; Ahmed, G.A.-W.; Albayati, M.R.

doi:10.1107/S2414314616004922

organic compounds

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ISSN: 2414-3146

Volume 1| Part 4| April 2016| x160492

doi:10.1107/S2414314616004922

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5-Acetyl-2-{[(1H-benzimidazol-2-yl)methyl]sulfanyl}-4-(4-methoxyphenyl)-6-methylpyridine-3-carbonitrile

Joel T. Mague,^a Shaaban K. Mohamed,^b,^c Mehmet Akkurt,^d Gamal A.-W. Ahmed ^e and Mustafa R. Albayati ^f ^*

^aDepartment of Chemistry, Tulane University, New Orleans, LA 70118, USA, ^bChemistry and Environmental Division, Manchester Metropolitan University, Manchester M1 5GD, England, ^cChemistry Department, Faculty of Science, Minia University, 61519 El-Minia, Egypt, ^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 Science, Department of Chemistry, Kirkuk, Iraq
^*Correspondence e-mail: shaabankamel@yahoo.com

Edited by J. Simpson, University of Otago, New Zealand (Received 20 March 2016; accepted 23 March 2016; online 5 April 2016)

In the title compound, C₂₄H₂₀N₄O₂S, the benzimidiazole moiety is essentially planar within 0.020 (1) Å (r.m.s. deviation = 0.012 Å). Its mean plane makes a dihedral angle of 85.80 (3)° with the plane of the central pyridine ring while the methoxyphenyl ring makes a dihedral angle of 57.28 (4)° with this plane. In the crystal, N—H⋯N hydrogen bonds form sheets parallel to (010).

Keywords: crystal structure; cyanopyridine; benzimidazole.

CCDC reference: 1470245

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Chemical scheme

Structure description

The pharmacological activities exhibited by 3-cyanopyridine-2(1H)-thiones (Litvinov, 2003 ) and benzimidazoles (Ingle & Magar, 2011 ; Alamgir et al., 2007 ) have been reviewed. The benzimidazole scaffold is a useful structural modification for the development of molecules of pharmaceutical or biological interest. Appropriately substituted benzimidazole derivatives have found diverse therapeutic applications such as in anti-ulcer, antihypertensive, antiviral, antifungal, anticancer and antihistaminic agents (Ingle & Magar, 2011). The optimization of benzimidazole-based structures has resulted in various drugs that are currently on the market, such as omeprazole (proton pump inhibitor), pimobendan (ionodilator), and mebendazole (anthelmintic) (Ingle & Magar, 2011). In view of the above observations, we undertook the synthesis of the title compound, which is structurally related to omeprazole, and determine its crystal structure.

In the title compound (Fig. 1), the benzimidiazolyl ring system (N3/N4/C18–C24) is essentially planar (r.m.s. deviation = 0.012 Å) and its mean plane makes a dihedral angle of 85.80 (3)° with that of the central pyridine ring (N1/C1–C5) while the C10—C15 ring makes a dihedral angle of 57.28 (4)° with the pyridine ring plane. The packing consists of layers parallel to (010) which are formed by N3—H3A⋯N4 hydrogen bonds (Table 1 and Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯N4ⁱ	0.92 (2)	1.98 (2)	2.8441 (16)	157.1 (17)
Symmetry code: (i) $[x+{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ .

Figure 1
The title molecule with the atom-labeling scheme and 50% probability ellipsoids.

Figure 2
A portion of one layer projected onto (010), showing the N—H⋯N hydrogen bonds as dotted lines.

Synthesis and crystallization

To a suspension of 5-acetyl-3-cyano-4-(4-methoxyphenyl)-6-methylpyridine-2(1H)-thione (3.0 g, 10 mmol) and 2-chloromethyl-1H-benzimidazole (1.66 g, 10 mmol) in ethanol (30 ml), sodium acetate trihydrate (1.5 g, 11 mmol) was added. The resulting mixture was heated under reflux for 3 h and then allowed to cool. The solid that formed was collected by filtration and recrystallized from ethanol to give the title compound in the form of colourless plates. Yield: (3.6 g) 84%, m.p. 501–503 K. IR: 3200 (NH), 2200 (C N), 1690 (C=O) cm.^{-1 1}H NMR (CDCl₃): δ = 6.9–7.7 (m, 9H, Ar—H and NH), 4.8 (2H, SCH₂) 3.8 (s, 3H, OCH₂), 2.6 (s, 3H, CH₃ at C-6), 1.8 (s, 3H, COCH₃).

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₂₄H₂₀N₄O₂S
M_r	428.50
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	150
a, b, c (Å)	9.8513 (2), 15.0619 (2), 28.9310 (4)
V (Å³)	4292.76 (12)
Z	8
Radiation type	Cu Kα
μ (mm⁻¹)	1.57
Crystal size (mm)	0.24 × 0.15 × 0.06

Data collection
Diffractometer	Bruker D8 VENTURE PHOTON 100 CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2015 )
T_min, T_max	0.79, 0.92
No. of measured, independent and observed [I > 2σ(I)] reflections	31421, 4292, 3787
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.091, 1.02
No. of reflections	4292
No. of parameters	288
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.40
Computer programs: APEX2 and SAINT (Bruker, 2015), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), DIAMOND (Brandenburg & Putz, 2012 ) and SHELXTL (Sheldrick, 2008 ).

Structural data

CCDC reference: 1470245

Crystal structure: contains datablocks global, I. DOI: 10.1107/S2414314616004922/sj4017sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616004922/sj4017Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616004922/sj4017Isup3.cml

checkCIF report

Comment top

In the title compound the benzodiazolyl moiety is planar within 0.02 Å

(rms deviation 0.012) and its mean plane makes a dihedral angle of

85.80 (3)° with the central pyridine ring while the C10-C15 ring makes a

dihedral angle of 57.28 (4)° with the latter. The packing consists of

layers parallel to (010) which are formed by N3—H3A···N4ⁱ (i:

x+1/2, y, -z+1/2) hydrogen bonds (Table 1 and

Fig. 2).

Experimental top

To a suspension of 5-acetyl-3-cyano-4-(4-methoxyphenyl)-6-methylpyridine-2(1H)-thione (3.0 g, 10 mmol) and 2-chloromethyl-1H-benzimidazole (1.66 g, 10 mmol) in ethanol (30 ml), sodium acetate trihydrate (1.5 g, 11 mmol) was added. The resulting mixture was heated under reflux for 3 h and then allowed to cool. The solid that formed was collected by filtration and recrystallized from ethanol to give the title compound in the form of colourless plates. Yield: (3.6 g) 84%, m.p. 501–503 K. IR: 3200 (NH), 2200 (C≡N), 1690 (C=O) cm.^{-1 1}H NMR (CDCl₃): δ = 6.9–7.7 (m, 9H, Ar—H and NH), 4.8 (2H, SCH₂) 3.8 (s, 3H, OCH₂), 2.6 (s, 3H, CH₃ at C-6), 1.8 (s, 3H, COCH₃).

Structure description top

The pharmacological activities exhibited by 3-cyanopyridine-2(1H)-thiones (Litvinov, 2003) and benzimidazoles (Ingle & Magar, 2011; Alamgir et al., 2007) have been reviewed. The benzimidazole scaffold is a useful structural modification for the development of molecules of pharmaceutical or biological interest. Appropriately substituted benzimidazole derivatives have found diverse therapeutic applications such as in anti-ulcer, antihypertensive, antiviral, antifungal, anticancer and antihistaminic agents (Ingle & Magar, 2011). The optimization of benzimidazole-based structures has resulted in various drugs that are currently on the market, such as omeprazole (proton pump inhibitor), pimobendan (ionodilator), and mebendazole (anthelmintic) (Ingle & Magar, 2011). In view of the above observations, we undertook the synthesis of the title compound, which is structurally related to omeprazole, and determine its crystal structure.

In the title compound (Fig.1), the benzimidiazolyl ring system (N3/N4/C18–C24) is essentially planar (r.m.s. deviation = 0.012 Å) and its mean plane makes a dihedral angle of 85.80 (3)° with that of the central pyridine ring (N1/C1–C5) while the C10—C15 ring makes a dihedral angle of 57.28 (4)° with the pyridine ring plane. The packing consists of layers parallel to (010) which are formed by N3—H3A···N4 hydrogen bonds (Table 1 and Fig. 2).

Computing details top

Data collection: APEX2 (Bruker, 2015); cell refinement: SAINT (Bruker, 2015); data reduction: SAINT (Bruker, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The title molecule with the atom-labeling scheme and 50% probability ellipsoids.
	Fig. 2. A portion of one layer projected onto (010), showing the N—H···N hydrogen bonds as dotted lines.

5-Acetyl-2-{[(1H-benzimidazol-2-yl)methyl]sulfanyl}-4-(4-methoxyphenyl)-6-methylpyridine-3-carbonitrile top

Crystal data top

C₂₄H₂₀N₄O₂S	D_x = 1.326 Mg m⁻³
M_r = 428.50	Cu Kα radiation, λ = 1.54178 Å
Orthorhombic, Pbca	Cell parameters from 9822 reflections
a = 9.8513 (2) Å	θ = 4.2–74.4°
b = 15.0619 (2) Å	µ = 1.57 mm⁻¹
c = 28.9310 (4) Å	T = 150 K
V = 4292.76 (12) Å³	Plate, colourless
Z = 8	0.24 × 0.15 × 0.06 mm
F(000) = 1792

Data collection top

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer	4292 independent reflections
Radiation source: INCOATEC IµS micro–focus source	3787 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.037
Detector resolution: 10.4167 pixels mm^-1	θ_max = 74.5°, θ_min = 3.1°
ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Bruker, 2015)	k = −17→15
T_min = 0.79, T_max = 0.92	l = −36→36
31421 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.034	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.091	w = 1/[σ²(F_o²) + (0.0459P)² + 1.5046P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
4292 reflections	Δρ_max = 0.22 e Å⁻³
288 parameters	Δρ_min = −0.40 e Å⁻³
0 restraints	Extinction correction: SHELXL2014 (Sheldrick 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00051 (6)

Crystal data top

C₂₄H₂₀N₄O₂S	V = 4292.76 (12) Å³
M_r = 428.50	Z = 8
Orthorhombic, Pbca	Cu Kα radiation
a = 9.8513 (2) Å	µ = 1.57 mm⁻¹
b = 15.0619 (2) Å	T = 150 K
c = 28.9310 (4) Å	0.24 × 0.15 × 0.06 mm

Data collection top

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer	4292 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2015)	3787 reflections with I > 2σ(I)
T_min = 0.79, T_max = 0.92	R_int = 0.037
31421 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.091	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.22 e Å⁻³
4292 reflections	Δρ_min = −0.40 e Å⁻³
288 parameters

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. H-atoms were placed in

calculated positions (C—H = 0.95 - 0.99 Å) and included as riding

contributions with isotropic displacement parameters 1.2 - 1.5 times those

of the attached carbon atoms.

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

	x	y	z	U_iso*/U_eq
S1	−0.00897 (3)	0.77846 (3)	0.34587 (2)	0.03530 (11)
O1	0.66262 (11)	0.84216 (8)	0.36572 (5)	0.0513 (3)
O2	0.59674 (11)	0.57979 (7)	0.55315 (3)	0.0394 (3)
N1	0.23056 (12)	0.85965 (8)	0.33336 (4)	0.0321 (3)
N2	0.08106 (13)	0.62965 (9)	0.43416 (5)	0.0455 (3)
N3	0.12589 (12)	0.71895 (8)	0.24456 (4)	0.0309 (3)
H3A	0.208 (2)	0.7306 (12)	0.2581 (6)	0.051 (5)*
N4	−0.09632 (11)	0.71505 (8)	0.22875 (4)	0.0293 (2)
C1	0.16353 (14)	0.79895 (9)	0.35781 (4)	0.0296 (3)
C2	0.22340 (13)	0.75185 (9)	0.39439 (5)	0.0287 (3)
C3	0.35819 (13)	0.76988 (8)	0.40657 (5)	0.0283 (3)
C4	0.42723 (13)	0.83401 (9)	0.38087 (5)	0.0298 (3)
C5	0.36018 (14)	0.87725 (9)	0.34441 (5)	0.0316 (3)
C6	0.42829 (16)	0.94884 (11)	0.31656 (6)	0.0425 (4)
H6A	0.3670	0.9688	0.2920	0.064*
H6B	0.5118	0.9253	0.3028	0.064*
H6C	0.4505	0.9990	0.3368	0.064*
C7	0.57174 (14)	0.85996 (9)	0.39216 (5)	0.0355 (3)
C8	0.59363 (16)	0.91238 (11)	0.43550 (6)	0.0453 (4)
H8A	0.6909	0.9236	0.4396	0.068*
H8B	0.5591	0.8788	0.4620	0.068*
H8C	0.5452	0.9691	0.4332	0.068*
C9	0.14601 (14)	0.68374 (9)	0.41719 (5)	0.0332 (3)
C10	0.42457 (13)	0.72017 (8)	0.44466 (5)	0.0284 (3)
C11	0.54249 (14)	0.67169 (9)	0.43662 (5)	0.0300 (3)
H11	0.5826	0.6722	0.4068	0.036*
C12	0.60228 (13)	0.62245 (9)	0.47188 (5)	0.0314 (3)
H12	0.6812	0.5881	0.4659	0.038*
C13	0.54578 (14)	0.62381 (9)	0.51590 (5)	0.0308 (3)
C14	0.42925 (14)	0.67349 (9)	0.52454 (5)	0.0324 (3)
H14	0.3917	0.6752	0.5548	0.039*
C15	0.36845 (14)	0.72015 (9)	0.48920 (5)	0.0312 (3)
H15	0.2876	0.7527	0.4951	0.037*
C16	0.71090 (17)	0.52355 (10)	0.54614 (6)	0.0424 (4)
H16A	0.6868	0.4763	0.5244	0.064*
H16B	0.7382	0.4973	0.5757	0.064*
H16C	0.7863	0.5584	0.5335	0.064*
C17	−0.02451 (15)	0.82366 (10)	0.28796 (5)	0.0354 (3)
H17A	−0.1168	0.8483	0.2836	0.042*
H17B	0.0416	0.8726	0.2839	0.042*
C18	0.00095 (13)	0.75384 (9)	0.25283 (5)	0.0289 (3)
C19	0.10824 (13)	0.65117 (9)	0.21295 (5)	0.0297 (3)
C20	0.19937 (15)	0.59179 (10)	0.19302 (5)	0.0382 (3)
H20	0.2938	0.5939	0.1996	0.046*
C21	0.14543 (17)	0.52975 (10)	0.16320 (5)	0.0416 (4)
H21	0.2043	0.4879	0.1489	0.050*
C22	0.00667 (17)	0.52663 (10)	0.15334 (5)	0.0393 (3)
H22	−0.0265	0.4827	0.1327	0.047*
C23	−0.08347 (15)	0.58610 (10)	0.17298 (5)	0.0345 (3)
H23	−0.1777	0.5840	0.1661	0.041*
C24	−0.03096 (13)	0.64929 (9)	0.20332 (4)	0.0277 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.02532 (18)	0.0480 (2)	0.03263 (19)	0.00303 (13)	−0.00383 (13)	−0.00463 (14)
O1	0.0310 (6)	0.0510 (7)	0.0721 (8)	−0.0016 (5)	0.0109 (5)	−0.0021 (6)
O2	0.0453 (6)	0.0365 (6)	0.0364 (5)	0.0089 (4)	−0.0109 (4)	−0.0001 (4)
N1	0.0295 (6)	0.0365 (6)	0.0303 (5)	0.0066 (5)	0.0001 (5)	−0.0021 (5)
N2	0.0356 (7)	0.0373 (7)	0.0637 (9)	−0.0027 (6)	−0.0052 (6)	0.0071 (6)
N3	0.0204 (6)	0.0363 (6)	0.0359 (6)	0.0033 (4)	−0.0025 (4)	−0.0043 (5)
N4	0.0225 (5)	0.0344 (6)	0.0310 (5)	0.0030 (4)	−0.0022 (4)	−0.0015 (5)
C1	0.0272 (7)	0.0320 (7)	0.0296 (6)	0.0052 (5)	−0.0016 (5)	−0.0067 (5)
C2	0.0271 (7)	0.0265 (6)	0.0326 (6)	0.0032 (5)	−0.0016 (5)	−0.0042 (5)
C3	0.0270 (7)	0.0255 (7)	0.0324 (6)	0.0041 (5)	−0.0021 (5)	−0.0047 (5)
C4	0.0266 (7)	0.0287 (7)	0.0341 (7)	0.0030 (5)	−0.0011 (5)	−0.0029 (5)
C5	0.0302 (7)	0.0316 (7)	0.0330 (7)	0.0052 (5)	0.0012 (5)	−0.0020 (5)
C6	0.0398 (8)	0.0447 (9)	0.0430 (8)	0.0019 (7)	0.0034 (7)	0.0088 (7)
C7	0.0279 (7)	0.0285 (7)	0.0500 (8)	0.0018 (5)	−0.0028 (6)	0.0055 (6)
C8	0.0347 (8)	0.0413 (9)	0.0600 (10)	−0.0014 (6)	−0.0149 (7)	−0.0053 (7)
C9	0.0271 (7)	0.0307 (7)	0.0419 (7)	0.0036 (5)	−0.0049 (6)	−0.0029 (6)
C10	0.0259 (7)	0.0244 (7)	0.0349 (7)	0.0001 (5)	−0.0052 (5)	−0.0030 (5)
C11	0.0283 (7)	0.0277 (7)	0.0340 (6)	0.0006 (5)	−0.0026 (5)	−0.0041 (5)
C12	0.0267 (6)	0.0277 (7)	0.0397 (7)	0.0030 (5)	−0.0063 (5)	−0.0060 (5)
C13	0.0327 (7)	0.0251 (7)	0.0345 (7)	−0.0011 (5)	−0.0086 (5)	−0.0021 (5)
C14	0.0330 (7)	0.0311 (7)	0.0332 (7)	−0.0012 (5)	−0.0019 (5)	−0.0041 (5)
C15	0.0273 (7)	0.0293 (7)	0.0369 (7)	0.0021 (5)	−0.0024 (5)	−0.0044 (5)
C16	0.0447 (9)	0.0339 (8)	0.0486 (9)	0.0090 (6)	−0.0169 (7)	−0.0021 (6)
C17	0.0309 (7)	0.0395 (8)	0.0358 (7)	0.0107 (6)	−0.0077 (6)	−0.0061 (6)
C18	0.0217 (6)	0.0348 (7)	0.0304 (6)	0.0046 (5)	−0.0026 (5)	0.0006 (5)
C19	0.0262 (6)	0.0310 (7)	0.0319 (6)	0.0021 (5)	0.0016 (5)	0.0013 (5)
C20	0.0304 (7)	0.0409 (8)	0.0433 (8)	0.0094 (6)	0.0047 (6)	−0.0003 (6)
C21	0.0503 (9)	0.0339 (8)	0.0405 (8)	0.0109 (7)	0.0088 (7)	−0.0003 (6)
C22	0.0545 (10)	0.0286 (7)	0.0346 (7)	−0.0036 (6)	0.0012 (6)	−0.0016 (6)
C23	0.0342 (7)	0.0342 (7)	0.0352 (7)	−0.0055 (6)	−0.0019 (6)	0.0020 (6)
C24	0.0255 (6)	0.0287 (7)	0.0288 (6)	0.0010 (5)	0.0020 (5)	0.0027 (5)

Geometric parameters (Å, º) top

S1—C1	1.7614 (14)	C8—H8C	0.9800
S1—C17	1.8149 (15)	C10—C11	1.3917 (19)
O1—C7	1.2076 (19)	C10—C15	1.4021 (19)
O2—C13	1.3613 (16)	C11—C12	1.3920 (19)
O2—C16	1.4224 (18)	C11—H11	0.9500
N1—C1	1.3314 (18)	C12—C13	1.390 (2)
N1—C5	1.3427 (18)	C12—H12	0.9500
N2—C9	1.146 (2)	C13—C14	1.393 (2)
N3—C18	1.3596 (17)	C14—C15	1.378 (2)
N3—C19	1.3815 (18)	C14—H14	0.9500
N3—H3A	0.92 (2)	C15—H15	0.9500
N4—C18	1.3209 (18)	C16—H16A	0.9800
N4—C24	1.3917 (17)	C16—H16B	0.9800
C1—C2	1.4039 (19)	C16—H16C	0.9800
C2—C3	1.4004 (19)	C17—C18	1.4838 (19)
C2—C9	1.438 (2)	C17—H17A	0.9900
C3—C4	1.3958 (19)	C17—H17B	0.9900
C3—C10	1.4841 (18)	C19—C20	1.3922 (19)
C4—C5	1.4046 (19)	C19—C24	1.3995 (18)
C4—C7	1.5120 (19)	C20—C21	1.378 (2)
C5—C6	1.504 (2)	C20—H20	0.9500
C6—H6A	0.9800	C21—C22	1.397 (2)
C6—H6B	0.9800	C21—H21	0.9500
C6—H6C	0.9800	C22—C23	1.383 (2)
C7—C8	1.497 (2)	C22—H22	0.9500
C8—H8A	0.9800	C23—C24	1.3942 (19)
C8—H8B	0.9800	C23—H23	0.9500

C1—S1—C17	101.35 (7)	C13—C12—H12	120.2
C13—O2—C16	117.95 (12)	C11—C12—H12	120.2
C1—N1—C5	118.73 (12)	O2—C13—C12	124.79 (13)
C18—N3—C19	106.75 (11)	O2—C13—C14	115.05 (12)
C18—N3—H3A	130.7 (12)	C12—C13—C14	120.16 (12)
C19—N3—H3A	122.3 (12)	C15—C14—C13	119.94 (13)
C18—N4—C24	104.95 (11)	C15—C14—H14	120.0
N1—C1—C2	122.62 (12)	C13—C14—H14	120.0
N1—C1—S1	119.65 (10)	C14—C15—C10	120.71 (13)
C2—C1—S1	117.69 (11)	C14—C15—H15	119.6
C3—C2—C1	119.35 (13)	C10—C15—H15	119.6
C3—C2—C9	121.70 (12)	O2—C16—H16A	109.5
C1—C2—C9	118.91 (12)	O2—C16—H16B	109.5
C4—C3—C2	117.52 (12)	H16A—C16—H16B	109.5
C4—C3—C10	122.00 (12)	O2—C16—H16C	109.5
C2—C3—C10	120.46 (12)	H16A—C16—H16C	109.5
C3—C4—C5	119.45 (12)	H16B—C16—H16C	109.5
C3—C4—C7	121.51 (12)	C18—C17—S1	110.62 (10)
C5—C4—C7	119.02 (12)	C18—C17—H17A	109.5
N1—C5—C4	122.31 (13)	S1—C17—H17A	109.5
N1—C5—C6	115.99 (12)	C18—C17—H17B	109.5
C4—C5—C6	121.66 (13)	S1—C17—H17B	109.5
C5—C6—H6A	109.5	H17A—C17—H17B	108.1
C5—C6—H6B	109.5	N4—C18—N3	113.14 (12)
H6A—C6—H6B	109.5	N4—C18—C17	123.51 (12)
C5—C6—H6C	109.5	N3—C18—C17	123.20 (12)
H6A—C6—H6C	109.5	N3—C19—C20	131.89 (13)
H6B—C6—H6C	109.5	N3—C19—C24	105.67 (11)
O1—C7—C8	122.73 (14)	C20—C19—C24	122.44 (13)
O1—C7—C4	120.25 (14)	C21—C20—C19	116.50 (14)
C8—C7—C4	116.92 (13)	C21—C20—H20	121.8
C7—C8—H8A	109.5	C19—C20—H20	121.8
C7—C8—H8B	109.5	C20—C21—C22	121.85 (14)
H8A—C8—H8B	109.5	C20—C21—H21	119.1
C7—C8—H8C	109.5	C22—C21—H21	119.1
H8A—C8—H8C	109.5	C23—C22—C21	121.49 (14)
H8B—C8—H8C	109.5	C23—C22—H22	119.3
N2—C9—C2	177.63 (16)	C21—C22—H22	119.3
C11—C10—C15	118.86 (12)	C22—C23—C24	117.55 (13)
C11—C10—C3	120.55 (12)	C22—C23—H23	121.2
C15—C10—C3	120.58 (12)	C24—C23—H23	121.2
C10—C11—C12	120.68 (13)	N4—C24—C23	130.31 (12)
C10—C11—H11	119.7	N4—C24—C19	109.49 (11)
C12—C11—H11	119.7	C23—C24—C19	120.17 (13)
C13—C12—C11	119.62 (13)

C5—N1—C1—C2	−0.72 (19)	C10—C11—C12—C13	−1.9 (2)
C5—N1—C1—S1	176.93 (10)	C16—O2—C13—C12	−4.4 (2)
C17—S1—C1—N1	19.43 (12)	C16—O2—C13—C14	176.31 (12)
C17—S1—C1—C2	−162.81 (10)	C11—C12—C13—O2	−178.69 (12)
N1—C1—C2—C3	1.2 (2)	C11—C12—C13—C14	0.6 (2)
S1—C1—C2—C3	−176.50 (10)	O2—C13—C14—C15	−179.48 (12)
N1—C1—C2—C9	−176.39 (12)	C12—C13—C14—C15	1.2 (2)
S1—C1—C2—C9	5.92 (17)	C13—C14—C15—C10	−1.7 (2)
C1—C2—C3—C4	−0.78 (18)	C11—C10—C15—C14	0.4 (2)
C9—C2—C3—C4	176.73 (12)	C3—C10—C15—C14	179.48 (12)
C1—C2—C3—C10	−179.13 (12)	C1—S1—C17—C18	91.64 (11)
C9—C2—C3—C10	−1.62 (19)	C24—N4—C18—N3	0.80 (15)
C2—C3—C4—C5	−0.01 (19)	C24—N4—C18—C17	−174.81 (13)
C10—C3—C4—C5	178.31 (12)	C19—N3—C18—N4	−0.81 (16)
C2—C3—C4—C7	178.31 (12)	C19—N3—C18—C17	174.82 (13)
C10—C3—C4—C7	−3.4 (2)	S1—C17—C18—N4	103.92 (14)
C1—N1—C5—C4	−0.13 (19)	S1—C17—C18—N3	−71.25 (16)
C1—N1—C5—C6	−177.84 (12)	C18—N3—C19—C20	−178.33 (15)
C3—C4—C5—N1	0.5 (2)	C18—N3—C19—C24	0.44 (15)
C7—C4—C5—N1	−177.87 (12)	N3—C19—C20—C21	178.13 (14)
C3—C4—C5—C6	178.07 (13)	C24—C19—C20—C21	−0.5 (2)
C7—C4—C5—C6	−0.3 (2)	C19—C20—C21—C22	0.2 (2)
C3—C4—C7—O1	112.49 (16)	C20—C21—C22—C23	0.2 (2)
C5—C4—C7—O1	−69.18 (19)	C21—C22—C23—C24	−0.3 (2)
C3—C4—C7—C8	−70.98 (18)	C18—N4—C24—C23	177.89 (14)
C5—C4—C7—C8	107.35 (16)	C18—N4—C24—C19	−0.49 (15)
C4—C3—C10—C11	−56.59 (18)	C22—C23—C24—N4	−178.18 (13)
C2—C3—C10—C11	121.69 (14)	C22—C23—C24—C19	0.0 (2)
C4—C3—C10—C15	124.37 (14)	N3—C19—C24—N4	0.02 (15)
C2—C3—C10—C15	−57.35 (17)	C20—C19—C24—N4	178.94 (12)
C15—C10—C11—C12	1.36 (19)	N3—C19—C24—C23	−178.55 (12)
C3—C10—C11—C12	−177.70 (12)	C20—C19—C24—C23	0.4 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N4ⁱ	0.92 (2)	1.98 (2)	2.8441 (16)	157.1 (17)

Symmetry code: (i) x+1/2, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N4ⁱ	0.92 (2)	1.98 (2)	2.8441 (16)	157.1 (17)

Symmetry code: (i) x+1/2, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₂₄H₂₀N₄O₂S
M_r	428.50
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	150
a, b, c (Å)	9.8513 (2), 15.0619 (2), 28.9310 (4)
V (Å³)	4292.76 (12)
Z	8
Radiation type	Cu Kα
µ (mm⁻¹)	1.57
Crystal size (mm)	0.24 × 0.15 × 0.06

Data collection
Diffractometer	Bruker D8 VENTURE PHOTON 100 CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2015)
T_min, T_max	0.79, 0.92
No. of measured, independent and observed [I > 2σ(I)] reflections	31421, 4292, 3787
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.091, 1.02
No. of reflections	4292
No. of parameters	288
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.40

Computer programs: APEX2 (Bruker, 2015), SAINT (Bruker, 2015), SAINT (Bruker, 2015), SHELXT (Sheldrick, 2015a), SHELXL (Sheldrick, 2015b), DIAMOND (Brandenburg & Putz, 2012), SHELXTL (Sheldrick, 2008).

Acknowledgements

The support of NSF–MRI Grant #1228232 for the purchase of the diffractometer and Tulane University for support of the Tulane Crystallography Laboratory are gratefully acknowledged.

References

Alamgir, M., Black, D. St C. & Kumar, N. (2007). Top. Heterocycl. Chem. 9, 87–118. CrossRef CAS Google Scholar
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