Piperidinium 4-(4-chloro­phen­yl)-3-cyano-5-eth­oxy­carbonyl-6-methyl­pyridine-2-thiol­ate

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

doi:10.1107/S2414314616006519

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 4| April 2016| x160651

doi:10.1107/S2414314616006519

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Piperidinium 4-(4-chlorophenyl)-3-cyano-5-ethoxycarbonyl-6-methylpyridine-2-thiolate

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

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

Edited by D.-J. Xu, Zhejiang University (Yuquan Campus), China (Received 15 April 2016; accepted 18 April 2016; online 22 April 2016)

In the crystal of the title salt, C₅H₁₂N⁺·C₁₆H₁₂ClN₂O₂S⁻, the cation adopts a chair conformation, and N—H⋯N and N—H⋯S hydrogen bonds form chains of alternating cations and anions running parallel to the c axis. The crystal structure contains a solvent-accessible void of 50 Å³, but no solvent molecule is located there.

Keywords: crystal structure; pyridines; piperidinium salts.

CCDC reference: 1474600

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Chemical scheme

Structure description

Pyridine derivatives continue to attract great interest due to the wide variety of interesting biological activities observed for these compounds, such as anticancer, analgesic, antimicrobial and antidepressant activities (Kumar et al., 2011 ). In addition, pyridines are used in the pharmaceutical industry as raw materials for the synthesis of various drugs, vitamins and fungicides (Kumar et al., 2011). These facts prompted us to synthesize the title compound, which contains both pyridine and piperidine moieties, and confirm its crystal structure by X-ray analysis.

In the anion (Fig. 1), the dihedral angle between the pyridine and chlorobenze rings is 69.48 (7)°. The cation has a chair conformation with puckering parameters of Q_T = 0.5684 (16) Å, θ = 176.46 (16) and φ = 199 (3)°.

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

In the crystal, the cations and anions are linked by N—H⋯N and N—H⋯S hydrogen bonds (Table 1), forming chains of alternating cations and anions parallel to the c axis (Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯N1	0.92 (2)	2.01 (2)	2.9288 (17)	174.5 (17)
N3—H3B⋯S1ⁱ	0.93 (2)	2.64 (2)	3.4249 (12)	142.6 (15)
Symmetry code: (i) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Figure 2
Packing viewed along the a axis with N—H⋯N and N—H⋯S hydrogen bonds shown as blue and brown dashed lines, respectively.

Synthesis and crystallization

The title compound was prepared by refluxing equimolar quantities of ethyl 3-cyano-1,2-dihydro-6-methyl-4-(4-chlorophenyl)-2-thioxopyridine-5-carboxylate and piperidine (10 mmol) in absolute ethanol (25 ml) for 5 min. The product that formed on cooling was collected and recrystallized from ethanol (95%) as yellow needles. Yield: 83%, m. p. 433–435 K.

IR: 3410, 2520, 2400 (N⁺H₂), 2964 (C—H, aliphatic), 2217 (C N), 1713 (C=O) cm^{-1. 1}H NMR (CDCl₃) δ: 7.35 (s, 2H, N⁺H₂), 7.19–7.33 (m, 4H, Ar—H), 3.89–3.90 (q, 2H, OCH₂), 3.17 (t, 4H, CH₂NCH₂), 2.41 (s, 3H, CH₃), 1.79 (m, 2H, CH₂), 1.61 (m, 2H, CH₂), 1.19–1.25 (m, 2H, CH₂), 0.84 (t, 3H, CH₃). Elemental analysis calculated for C₂₁H₂₄ClN₃O₂S (%): C, 60.35; H, 5.79; N, 10.05; S, 7.67. Found (%): C, 60.28; H, 5.68; N, 10.09; S, 7.33.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₅H₁₂N⁺·C₁₆H₁₂ClN₂O₂S⁻
M_r	417.94
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	150
a, b, c (Å)	7.2363 (2), 24.2600 (7), 12.9049 (4)
β (°)	105.603 (1)
V (Å³)	2182.00 (11)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	2.61
Crystal size (mm)	0.26 × 0.14 × 0.13

Data collection
Diffractometer	Bruker D8 VENTURE PHOTON 100 CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2016 )
T_min, T_max	0.61, 0.72
No. of measured, independent and observed [I > 2σ(I)] reflections	16665, 4350, 3985
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.097, 1.04
No. of reflections	4350
No. of parameters	263
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.46
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: 1474600

Crystal structure: contains datablocks global, I. DOI: 10.1107/S2414314616006519/xu4007sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616006519/xu4007Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616006519/xu4007Isup3.cml

checkCIF report

Experimental top

IR: 3410, 2520, 2400 (N⁺H₂), 2964 (C—H, aliphatic), 2217 (C≡N), 1713 (C=O) cm^{-1. 1}H NMR (CDCl₃) δ: 7.35 (s, 2H, N⁺H₂), 7.19–7.33 (m, 4H, Ar—H), 3.89–3.90 (q, 2H, OCH₂), 3.17 (t, 4H, CH₂NCH₂), 2.41 (s, 3H, CH₃), 1.79 (m, 2H, CH₂), 1.61 (m, 2H, CH₂), 1.19–1.25 (m, 2H, CH₂), 0.84 (t, 3H, CH₃). Elemental analysis calculated for C₂₁H₂₄ClN₃O₂S (%): C, 60.35; H, 5.79; N, 10.05; S, 7.67. Found (%): C, 60.28; H, 5.68; N, 10.09; S, 7.33.

Structure description top

Pyridine derivatives continue to attract great interest due to the wide variety of interesting biological activities observed for these compounds, such as anticancer, analgesic, antimicrobial and antidepressant activities (Kumar et al., 2011). In addition, pyridines are used in the pharmaceutical industry as raw materials for various drugs, vitamins and fungicides (Kumar et al., 2011). These facts promoted us to synthesize the title compound, which contains both pyridine and piperidine moieties, and confirm its crystal structure by X-ray analysis.

In the crystal, the cations and anions are linked by N—H···N and N—H···S hydrogen bonds (Table 1), forming chains of alternating cations and anions parallel to the c axis (Fig. 2).

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).

Figures top

	Fig. 1. The title molecule with labeling scheme and 50% probability ellipsoids.
	Fig. 2. Packing viewed down the a axis with N—H···N and N—H···S hydrogen bonds shown as blue and brown dashed lines, respectively.

Piperidin-1-ium [4-(4-chlorophenyl)-3-cyano-5-(ethoxycarbonyl)-6-methylpyridin-2-yl]sulfanide top

Crystal data top

C₅H₁₂N⁺·C₁₆H₁₂ClN₂O₂S⁻	F(000) = 880
M_r = 417.94	D_x = 1.272 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54178 Å
a = 7.2363 (2) Å	Cell parameters from 9892 reflections
b = 24.2600 (7) Å	θ = 3.6–74.3°
c = 12.9049 (4) Å	µ = 2.61 mm⁻¹
β = 105.603 (1)°	T = 150 K
V = 2182.00 (11) Å³	Block, colourless
Z = 4	0.26 × 0.14 × 0.13 mm

Data collection top

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer	4350 independent reflections
Radiation source: INCOATEC IµS micro–focus source	3985 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.028
Detector resolution: 10.4167 pixels mm^-1	θ_max = 74.6°, θ_min = 3.6°
ω scans	h = −9→8
Absorption correction: multi-scan (SADABS; Bruker, 2016)	k = −30→29
T_min = 0.61, T_max = 0.72	l = −16→16
16665 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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.097	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0538P)² + 0.8348P] where P = (F_o² + 2F_c²)/3
4350 reflections	(Δ/σ)_max = 0.001
263 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.46 e Å⁻³

Crystal data top

C₅H₁₂N⁺·C₁₆H₁₂ClN₂O₂S⁻	V = 2182.00 (11) Å³
M_r = 417.94	Z = 4
Monoclinic, P2₁/c	Cu Kα radiation
a = 7.2363 (2) Å	µ = 2.61 mm⁻¹
b = 24.2600 (7) Å	T = 150 K
c = 12.9049 (4) Å	0.26 × 0.14 × 0.13 mm
β = 105.603 (1)°

Data collection top

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer	4350 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2016)	3985 reflections with I > 2σ(I)
T_min = 0.61, T_max = 0.72	R_int = 0.028
16665 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.097	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.26 e Å⁻³
4350 reflections	Δρ_min = −0.46 e Å⁻³
263 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
Cl1	−0.39999 (7)	0.47748 (2)	0.81495 (4)	0.04801 (14)
S1	0.59234 (5)	0.72882 (2)	0.82912 (3)	0.02541 (11)
O1	−0.01709 (18)	0.59943 (6)	0.41297 (10)	0.0469 (3)
O2	−0.21430 (15)	0.63592 (5)	0.50149 (9)	0.0366 (3)
N1	0.37767 (17)	0.71321 (5)	0.62901 (9)	0.0245 (2)
N2	0.3246 (2)	0.63295 (6)	0.96028 (10)	0.0395 (3)
C1	0.4064 (2)	0.69910 (6)	0.73433 (11)	0.0226 (3)
C2	0.2804 (2)	0.66016 (6)	0.76156 (10)	0.0230 (3)
C3	0.13227 (19)	0.63537 (6)	0.68331 (10)	0.0223 (3)
C4	0.1123 (2)	0.64998 (6)	0.57583 (10)	0.0231 (3)
C5	0.2355 (2)	0.68969 (6)	0.55271 (11)	0.0246 (3)
C6	0.2084 (2)	0.71053 (7)	0.43991 (11)	0.0333 (3)
H6A	0.2103	0.6794	0.3918	0.050*
H6B	0.3123	0.7361	0.4382	0.050*
H6C	0.0849	0.7297	0.4161	0.050*
C7	0.3071 (2)	0.64525 (6)	0.87240 (11)	0.0270 (3)
C8	0.0020 (2)	0.59527 (6)	0.71526 (10)	0.0229 (3)
C9	−0.1251 (2)	0.61412 (6)	0.77162 (11)	0.0270 (3)
H9	−0.1268	0.6521	0.7891	0.032*
C10	−0.2488 (2)	0.57806 (6)	0.80233 (12)	0.0300 (3)
H10	−0.3361	0.5910	0.8401	0.036*
C11	−0.2431 (2)	0.52261 (6)	0.77703 (12)	0.0295 (3)
C12	−0.1176 (2)	0.50282 (6)	0.72201 (12)	0.0291 (3)
H12	−0.1150	0.4647	0.7057	0.035*
C13	0.0050 (2)	0.53949 (6)	0.69076 (11)	0.0261 (3)
H13	0.0914	0.5264	0.6524	0.031*
C14	−0.0433 (2)	0.62493 (6)	0.48768 (11)	0.0265 (3)
C15	−0.3827 (3)	0.61023 (9)	0.42940 (14)	0.0456 (4)
H15A	−0.3432	0.5850	0.3789	0.055*
H15B	−0.4682	0.6388	0.3870	0.055*
C16	−0.4853 (3)	0.57877 (8)	0.49676 (16)	0.0458 (4)
H16A	−0.6079	0.5652	0.4512	0.069*
H16B	−0.5090	0.6030	0.5526	0.069*
H16C	−0.4062	0.5475	0.5307	0.069*
N3	0.65498 (18)	0.79520 (5)	0.59790 (9)	0.0248 (3)
H3A	0.572 (3)	0.7694 (8)	0.6125 (15)	0.038 (5)*
H3B	0.604 (3)	0.8040 (8)	0.5259 (16)	0.036 (5)*
C17	0.6606 (2)	0.84628 (6)	0.66329 (11)	0.0286 (3)
H17A	0.7135	0.8375	0.7405	0.034*
H17B	0.5288	0.8607	0.6527	0.034*
C18	0.7836 (2)	0.88953 (6)	0.63022 (13)	0.0323 (3)
H18A	0.7904	0.9226	0.6761	0.039*
H18B	0.7241	0.9005	0.5547	0.039*
C19	0.9854 (2)	0.86807 (7)	0.64069 (13)	0.0343 (3)
H19A	1.0520	0.8624	0.7176	0.041*
H19B	1.0586	0.8957	0.6115	0.041*
C20	0.9797 (2)	0.81383 (7)	0.57999 (13)	0.0333 (3)
H20A	0.9329	0.8209	0.5017	0.040*
H20B	1.1113	0.7987	0.5947	0.040*
C21	0.8506 (2)	0.77161 (6)	0.61209 (12)	0.0299 (3)
H21A	0.8424	0.7382	0.5670	0.036*
H21B	0.9054	0.7609	0.6882	0.036*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0480 (3)	0.0416 (2)	0.0606 (3)	−0.01460 (19)	0.0251 (2)	0.00572 (19)
S1	0.02572 (18)	0.02913 (19)	0.02096 (17)	−0.00411 (13)	0.00555 (13)	−0.00248 (12)
O1	0.0394 (7)	0.0654 (9)	0.0355 (6)	−0.0050 (6)	0.0094 (5)	−0.0263 (6)
O2	0.0245 (5)	0.0521 (7)	0.0311 (5)	−0.0041 (5)	0.0038 (4)	−0.0120 (5)
N1	0.0267 (6)	0.0266 (6)	0.0211 (5)	−0.0012 (5)	0.0080 (5)	−0.0011 (4)
N2	0.0400 (8)	0.0512 (9)	0.0247 (7)	−0.0119 (7)	0.0044 (6)	0.0053 (6)
C1	0.0240 (7)	0.0237 (6)	0.0210 (6)	0.0028 (5)	0.0076 (5)	−0.0017 (5)
C2	0.0249 (7)	0.0249 (6)	0.0197 (6)	0.0011 (5)	0.0070 (5)	0.0000 (5)
C3	0.0230 (7)	0.0228 (6)	0.0219 (6)	0.0022 (5)	0.0073 (5)	−0.0017 (5)
C4	0.0241 (7)	0.0256 (6)	0.0194 (6)	0.0007 (5)	0.0056 (5)	−0.0029 (5)
C5	0.0265 (7)	0.0274 (7)	0.0206 (6)	0.0008 (6)	0.0073 (5)	−0.0015 (5)
C6	0.0392 (9)	0.0400 (8)	0.0206 (7)	−0.0076 (7)	0.0079 (6)	0.0014 (6)
C7	0.0257 (7)	0.0302 (7)	0.0240 (7)	−0.0046 (6)	0.0049 (5)	−0.0006 (6)
C8	0.0236 (7)	0.0255 (6)	0.0189 (6)	−0.0001 (5)	0.0043 (5)	0.0004 (5)
C9	0.0300 (7)	0.0253 (7)	0.0275 (7)	−0.0014 (6)	0.0107 (6)	−0.0037 (5)
C10	0.0297 (7)	0.0341 (8)	0.0292 (7)	−0.0012 (6)	0.0131 (6)	−0.0017 (6)
C11	0.0290 (7)	0.0300 (7)	0.0288 (7)	−0.0053 (6)	0.0066 (6)	0.0045 (6)
C12	0.0336 (8)	0.0225 (6)	0.0296 (7)	−0.0002 (6)	0.0057 (6)	0.0011 (5)
C13	0.0277 (7)	0.0264 (7)	0.0245 (6)	0.0020 (6)	0.0074 (5)	−0.0005 (5)
C14	0.0292 (7)	0.0290 (7)	0.0209 (6)	−0.0022 (6)	0.0059 (5)	−0.0013 (5)
C15	0.0298 (8)	0.0668 (12)	0.0345 (8)	−0.0117 (8)	−0.0014 (7)	−0.0086 (8)
C16	0.0367 (9)	0.0450 (10)	0.0478 (10)	−0.0083 (8)	−0.0021 (8)	0.0044 (8)
N3	0.0275 (6)	0.0272 (6)	0.0200 (5)	−0.0009 (5)	0.0069 (5)	−0.0001 (5)
C17	0.0329 (8)	0.0297 (7)	0.0233 (6)	0.0028 (6)	0.0078 (6)	−0.0046 (5)
C18	0.0369 (8)	0.0273 (7)	0.0306 (7)	−0.0002 (6)	0.0058 (6)	−0.0031 (6)
C19	0.0333 (8)	0.0364 (8)	0.0322 (8)	−0.0066 (7)	0.0069 (6)	−0.0037 (6)
C20	0.0292 (8)	0.0393 (8)	0.0332 (8)	−0.0001 (7)	0.0113 (6)	−0.0062 (6)
C21	0.0306 (8)	0.0291 (7)	0.0295 (7)	0.0044 (6)	0.0070 (6)	−0.0023 (6)

Geometric parameters (Å, º) top

Cl1—C11	1.7398 (15)	C12—H12	0.9500
S1—C1	1.7150 (14)	C13—H13	0.9500
O1—C14	1.2027 (18)	C15—C16	1.496 (3)
O2—C14	1.3238 (19)	C15—H15A	0.9900
O2—C15	1.4591 (19)	C15—H15B	0.9900
N1—C5	1.3447 (18)	C16—H16A	0.9800
N1—C1	1.3623 (17)	C16—H16B	0.9800
N2—C7	1.146 (2)	C16—H16C	0.9800
C1—C2	1.4212 (19)	N3—C21	1.4918 (19)
C2—C3	1.3957 (19)	N3—C17	1.4937 (18)
C2—C7	1.4371 (19)	N3—H3A	0.92 (2)
C3—C4	1.4009 (18)	N3—H3B	0.93 (2)
C3—C8	1.4877 (19)	C17—C18	1.510 (2)
C4—C5	1.399 (2)	C17—H17A	0.9900
C4—C14	1.4973 (19)	C17—H17B	0.9900
C5—C6	1.5031 (19)	C18—C19	1.522 (2)
C6—H6A	0.9800	C18—H18A	0.9900
C6—H6B	0.9800	C18—H18B	0.9900
C6—H6C	0.9800	C19—C20	1.526 (2)
C8—C13	1.3912 (19)	C19—H19A	0.9900
C8—C9	1.3945 (19)	C19—H19B	0.9900
C9—C10	1.383 (2)	C20—C21	1.517 (2)
C9—H9	0.9500	C20—H20A	0.9900
C10—C11	1.387 (2)	C20—H20B	0.9900
C10—H10	0.9500	C21—H21A	0.9900
C11—C12	1.381 (2)	C21—H21B	0.9900
C12—C13	1.391 (2)

C14—O2—C15	118.59 (13)	C16—C15—H15A	110.1
C5—N1—C1	120.36 (12)	O2—C15—H15B	110.1
N1—C1—C2	118.54 (12)	C16—C15—H15B	110.1
N1—C1—S1	119.07 (10)	H15A—C15—H15B	108.4
C2—C1—S1	122.38 (10)	C15—C16—H16A	109.5
C3—C2—C1	121.77 (12)	C15—C16—H16B	109.5
C3—C2—C7	118.90 (13)	H16A—C16—H16B	109.5
C1—C2—C7	119.32 (12)	C15—C16—H16C	109.5
C2—C3—C4	117.52 (13)	H16A—C16—H16C	109.5
C2—C3—C8	120.11 (12)	H16B—C16—H16C	109.5
C4—C3—C8	122.37 (12)	C21—N3—C17	111.59 (11)
C5—C4—C3	118.92 (12)	C21—N3—H3A	111.3 (12)
C5—C4—C14	120.65 (12)	C17—N3—H3A	111.6 (12)
C3—C4—C14	120.39 (12)	C21—N3—H3B	108.7 (12)
N1—C5—C4	122.83 (12)	C17—N3—H3B	108.5 (12)
N1—C5—C6	116.19 (13)	H3A—N3—H3B	104.8 (17)
C4—C5—C6	120.91 (13)	N3—C17—C18	110.21 (12)
C5—C6—H6A	109.5	N3—C17—H17A	109.6
C5—C6—H6B	109.5	C18—C17—H17A	109.6
H6A—C6—H6B	109.5	N3—C17—H17B	109.6
C5—C6—H6C	109.5	C18—C17—H17B	109.6
H6A—C6—H6C	109.5	H17A—C17—H17B	108.1
H6B—C6—H6C	109.5	C17—C18—C19	111.20 (13)
N2—C7—C2	178.55 (16)	C17—C18—H18A	109.4
C13—C8—C9	119.36 (13)	C19—C18—H18A	109.4
C13—C8—C3	121.55 (12)	C17—C18—H18B	109.4
C9—C8—C3	119.09 (12)	C19—C18—H18B	109.4
C10—C9—C8	120.70 (14)	H18A—C18—H18B	108.0
C10—C9—H9	119.7	C18—C19—C20	110.88 (13)
C8—C9—H9	119.7	C18—C19—H19A	109.5
C9—C10—C11	118.89 (14)	C20—C19—H19A	109.5
C9—C10—H10	120.6	C18—C19—H19B	109.5
C11—C10—H10	120.6	C20—C19—H19B	109.5
C12—C11—C10	121.56 (14)	H19A—C19—H19B	108.1
C12—C11—Cl1	119.68 (12)	C21—C20—C19	112.07 (13)
C10—C11—Cl1	118.76 (12)	C21—C20—H20A	109.2
C11—C12—C13	119.07 (14)	C19—C20—H20A	109.2
C11—C12—H12	120.5	C21—C20—H20B	109.2
C13—C12—H12	120.5	C19—C20—H20B	109.2
C12—C13—C8	120.41 (13)	H20A—C20—H20B	107.9
C12—C13—H13	119.8	N3—C21—C20	109.95 (12)
C8—C13—H13	119.8	N3—C21—H21A	109.7
O1—C14—O2	124.49 (14)	C20—C21—H21A	109.7
O1—C14—C4	124.71 (14)	N3—C21—H21B	109.7
O2—C14—C4	110.78 (12)	C20—C21—H21B	109.7
O2—C15—C16	107.90 (14)	H21A—C21—H21B	108.2
O2—C15—H15A	110.1

C5—N1—C1—C2	−1.5 (2)	C13—C8—C9—C10	−0.6 (2)
C5—N1—C1—S1	178.60 (10)	C3—C8—C9—C10	179.78 (13)
N1—C1—C2—C3	1.5 (2)	C8—C9—C10—C11	0.6 (2)
S1—C1—C2—C3	−178.53 (11)	C9—C10—C11—C12	−0.1 (2)
N1—C1—C2—C7	−179.30 (13)	C9—C10—C11—Cl1	−179.55 (12)
S1—C1—C2—C7	0.63 (19)	C10—C11—C12—C13	−0.4 (2)
C1—C2—C3—C4	0.4 (2)	Cl1—C11—C12—C13	179.03 (11)
C7—C2—C3—C4	−178.80 (13)	C11—C12—C13—C8	0.4 (2)
C1—C2—C3—C8	−179.31 (12)	C9—C8—C13—C12	0.1 (2)
C7—C2—C3—C8	1.5 (2)	C3—C8—C13—C12	179.68 (13)
C2—C3—C4—C5	−2.29 (19)	C15—O2—C14—O1	7.8 (2)
C8—C3—C4—C5	177.38 (12)	C15—O2—C14—C4	−173.92 (14)
C2—C3—C4—C14	179.91 (12)	C5—C4—C14—O1	59.9 (2)
C8—C3—C4—C14	−0.4 (2)	C3—C4—C14—O1	−122.30 (17)
C1—N1—C5—C4	−0.5 (2)	C5—C4—C14—O2	−118.34 (15)
C1—N1—C5—C6	176.48 (13)	C3—C4—C14—O2	59.42 (18)
C3—C4—C5—N1	2.5 (2)	C14—O2—C15—C16	123.12 (17)
C14—C4—C5—N1	−179.73 (13)	C21—N3—C17—C18	59.88 (15)
C3—C4—C5—C6	−174.38 (13)	N3—C17—C18—C19	−56.81 (16)
C14—C4—C5—C6	3.4 (2)	C17—C18—C19—C20	53.36 (17)
C2—C3—C8—C13	−111.09 (15)	C18—C19—C20—C21	−52.65 (18)
C4—C3—C8—C13	69.24 (18)	C17—N3—C21—C20	−58.50 (15)
C2—C3—C8—C9	68.53 (18)	C19—C20—C21—N3	54.82 (17)
C4—C3—C8—C9	−111.14 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N1	0.92 (2)	2.01 (2)	2.9288 (17)	174.5 (17)
N3—H3B···S1ⁱ	0.93 (2)	2.64 (2)	3.4249 (12)	142.6 (15)

Symmetry code: (i) x, −y+3/2, z−1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N1	0.92 (2)	2.01 (2)	2.9288 (17)	174.5 (17)
N3—H3B···S1ⁱ	0.93 (2)	2.64 (2)	3.4249 (12)	142.6 (15)

Symmetry code: (i) x, −y+3/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₅H₁₂N⁺·C₁₆H₁₂ClN₂O₂S⁻
M_r	417.94
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	150
a, b, c (Å)	7.2363 (2), 24.2600 (7), 12.9049 (4)
β (°)	105.603 (1)
V (Å³)	2182.00 (11)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	2.61
Crystal size (mm)	0.26 × 0.14 × 0.13

Data collection
Diffractometer	Bruker D8 VENTURE PHOTON 100 CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2016)
T_min, T_max	0.61, 0.72
No. of measured, independent and observed [I > 2σ(I)] reflections	16665, 4350, 3985
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.097, 1.04
No. of reflections	4350
No. of parameters	263
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.46

Computer programs: APEX3 (Bruker, 2016), SAINT (Bruker, 2016), SHELXT (Sheldrick, 2015a), SHELXL2014 (Sheldrick, 2015b), DIAMOND (Brandenburg & Putz, 2012), SHELXTL (Sheldrick, 2008).

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.

References

Brandenburg, K. & Putz, H. (2012). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2016). APEX3, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Kumar, S., Sharma, P. K., Dudhe, R. & Kumar, N. (2011). J. Chronother. Drug Deliv. 2, 71–78. CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar

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