4-Benzyl-1,2,4-tri­aza­spiro­[4.5]dec-1-ene-3-thione

Mohamed, S.K.; Akkurt, M.; Jasinski, J.P.; Hassan, A.A.; Abdel-Aziz, A.T.; Albayati, M.R.

doi:10.1107/S2414314616019684

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 12| December 2016| x161968

https://doi.org/10.1107/S2414314616019684

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4-Benzyl-1,2,4-triazaspiro[4.5]dec-1-ene-3-thione

Shaaban K. Mohamed,^a,^b Mehmet Akkurt,^c Jerry P. Jasinski,^d Alaa A. Hassan,^b Ahmed T. Abdel-Aziz ^b and Mustafa R. Albayati ^e ^*

^aChemistry and Environmental Division, Manchester Metropolitan University, Manchester M1 5GD, England, ^bChemistry Department, Faculty of Science, Minia University, 61519 El-Minia, Egypt, ^cDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey, ^dDepartment of Chemistry, Keene State College, 229 Main Street, Keene, NH 03435-2001, USA, and ^eKirkuk 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 7 December 2016; accepted 9 December 2016; online 16 December 2016)

In the title compound, C₁₄H₁₇N₃S, the cyclohexane ring adopts a chair conformation. The dihedral angle between the triazole and phenyl ring is 77.2 (3)°. In the crystal structure, C—H⋯S hydrogen link molecules into C(7) chains along the b-axis direction. The crystal studied was refined as as an inversion twin.

Keywords: crystal structure; triazole ring; cyclohexane ring; spiro-compounds; C—H⋯S hydrogen bonds.

CCDC reference: 1521677

Structure description

Heterocyclic 1,2,4-triazoline-5-thione derivatives exhibit a variety of biological properties including analgesic (Mekuskiene et al., 1998 ), anti-inflammatory (Sahin et al., 2001 ), bacteriostatic (Eweiss et al., 1986 ) and antimitotic (Wujec et al., 2004 ) activities. As part of our studies in this area, we determined the crystal structure of the title triazathione compound (Fig. 1).

Figure 1
The title molecule, shown with 50% probability displacement ellipsoids.

The cyclohexane ring adopts a chair conformation with puckering parameters Q_T = 0.540 (5) Å, θ = 176.6 (5) ° and φ = 350 (9)°. The triazole ring is essentially planar (r.m.s. deviation = 0.004 Å) and makes a dihedral angle of 77.2 (3)° with the phenyl ring. The values of all geometric parameters are within normal ranges and comparable with the values for the related compound 4-allyl-1,2,4-triazaspiro[4.5]dec-1-ene-3-thione (Hassan et al., 2016 ).

In the crystal, C10—H10⋯S1 hydrogen bonds link the molecules in a zigzag fashion into C(7) chains along the b-axis direction (Table 1 and Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10⋯S1ⁱ	0.93	2.87	3.779 (6)	166
Symmetry code: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 2
Packing of the title molecule, viewed along the a axis. Hydrogen bonds are drawn as dashed lines.

Synthesis and crystallization

The title compound was prepared according to our previously reported method (Hassan et al., 2016). Colourless crystals suitable for X-ray diffraction were obtained from ethanol in 80% yield, using the slow evaporation method. M.p. 435–436 K.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The crystal studied was refined as as an inversion twin.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₄H₁₇N₃S
M_r	259.36
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	173
a, b, c (Å)	7.3730 (6), 10.7698 (7), 17.1056 (12)
V (Å³)	1358.28 (17)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	1.99
Crystal size (mm)	0.34 × 0.32 × 0.22

Data collection
Diffractometer	Rigaku Oxford Diffraction
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2014 )
T_min, T_max	0.531, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	8805, 2607, 1974
R_int	0.071
(sin θ/λ)_max (Å⁻¹)	0.616

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.138, 1.02
No. of reflections	2607
No. of parameters	164
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.28
Absolute structure	Flack (1983 ), 1097 Friedel pairs; refined as an inversion twin
Absolute structure parameter	0.32 (4)
Computer programs: CrysAlis PRO (Agilent, 2014), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), PLATON (Spek, 2009 ) and WinGX (Farrugia, 2012 ).

Structural data

CCDC reference: 1521677

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314616019684/sj4077sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616019684/sj4077Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616019684/sj4077Isup3.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: SHELXL (Sheldrick, 2015b); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 2012).

4-Benzyl-1,2,4-triazaspiro[4.5]dec-1-ene-3-thione top

Crystal data top

C₁₄H₁₇N₃S	D_x = 1.268 Mg m⁻³
M_r = 259.36	Cu Kα radiation, λ = 1.54184 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 1528 reflections
a = 7.3730 (6) Å	θ = 4.8–68.8°
b = 10.7698 (7) Å	µ = 1.99 mm⁻¹
c = 17.1056 (12) Å	T = 173 K
V = 1358.28 (17) Å³	Irregular, colourless
Z = 4	0.34 × 0.32 × 0.22 mm
F(000) = 552

Data collection top

Rigaku Oxford Diffraction diffractometer	2607 independent reflections
Radiation source: Enhance (Cu) X-ray Source	1974 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.071
Detector resolution: 16.0416 pixels mm^-1	θ_max = 71.7°, θ_min = 4.9°
ω scans	h = −9→8
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −11→13
T_min = 0.531, T_max = 1.000	l = −20→20
8805 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.056	w = 1/[σ²(F_o²) + (0.062P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.138	(Δ/σ)_max < 0.001
S = 1.02	Δρ_max = 0.29 e Å⁻³
2607 reflections	Δρ_min = −0.28 e Å⁻³
164 parameters	Absolute structure: Flack (1983), 1097 Friedel pairs; refined as an inversion twin
0 restraints	Absolute structure parameter: 0.32 (4)

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. Refined as a two-component inversion twin

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

	x	y	z	U_iso*/U_eq
C1	0.5544 (7)	0.2039 (4)	0.4292 (2)	0.0379 (10)
C2	0.5495 (7)	0.4171 (4)	0.4180 (2)	0.0341 (9)
C3	0.7193 (7)	0.4963 (4)	0.4071 (3)	0.0384 (11)
H3A	0.823318	0.452406	0.428091	0.046*
H3B	0.740128	0.509365	0.351664	0.046*
C4	0.7017 (8)	0.6217 (5)	0.4477 (3)	0.0433 (13)
H4A	0.699621	0.609261	0.503813	0.052*
H4B	0.806647	0.672345	0.435208	0.052*
C5	0.5310 (7)	0.6895 (4)	0.4229 (3)	0.0446 (12)
H5A	0.521308	0.766687	0.451853	0.053*
H5B	0.538792	0.709806	0.367735	0.053*
C6	0.3633 (8)	0.6119 (5)	0.4372 (3)	0.0471 (13)
H6A	0.257830	0.656208	0.418029	0.056*
H6B	0.348178	0.599756	0.493036	0.056*
C7	0.3741 (7)	0.4850 (4)	0.3969 (3)	0.0405 (12)
H7A	0.271087	0.434823	0.412623	0.049*
H7B	0.368257	0.496254	0.340741	0.049*
C8	0.5758 (7)	0.2799 (4)	0.2940 (2)	0.0386 (11)
H8A	0.493986	0.337892	0.268686	0.046*
H8B	0.535983	0.196663	0.280833	0.046*
C9	0.7632 (7)	0.2991 (4)	0.2621 (3)	0.0356 (11)
C10	0.7936 (8)	0.3828 (4)	0.2015 (3)	0.0418 (12)
H10	0.696770	0.427247	0.180833	0.050*
C11	0.9654 (9)	0.4006 (5)	0.1718 (3)	0.0486 (14)
H11	0.983486	0.456565	0.131170	0.058*
C12	1.1088 (8)	0.3366 (5)	0.2017 (3)	0.0525 (15)
H12	1.224866	0.349381	0.182015	0.063*
C13	1.0808 (7)	0.2528 (5)	0.2612 (3)	0.0588 (15)
H13	1.178518	0.208316	0.281210	0.071*
C14	0.9102 (7)	0.2340 (5)	0.2915 (3)	0.0455 (12)
H14	0.893503	0.177266	0.331846	0.055*
N1	0.5623 (6)	0.2963 (3)	0.37830 (19)	0.0346 (8)
N2	0.5381 (6)	0.3770 (3)	0.5009 (2)	0.0423 (10)
N3	0.5407 (6)	0.2617 (4)	0.5075 (2)	0.0455 (10)
S1	0.5585 (2)	0.05329 (10)	0.41790 (8)	0.0495 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.036 (2)	0.039 (2)	0.039 (2)	0.000 (2)	0.001 (3)	−0.0023 (19)
C2	0.040 (3)	0.034 (2)	0.028 (2)	0.0020 (19)	0.006 (2)	−0.0013 (16)
C3	0.040 (3)	0.039 (2)	0.036 (3)	0.000 (2)	0.001 (2)	−0.002 (2)
C4	0.057 (4)	0.034 (3)	0.039 (3)	−0.008 (2)	0.001 (2)	0.000 (2)
C5	0.062 (3)	0.026 (2)	0.045 (3)	0.000 (2)	0.003 (3)	−0.003 (2)
C6	0.053 (3)	0.037 (3)	0.051 (3)	0.011 (2)	0.010 (3)	−0.001 (2)
C7	0.043 (3)	0.038 (2)	0.041 (3)	−0.001 (2)	0.003 (2)	0.001 (2)
C8	0.039 (3)	0.043 (3)	0.033 (2)	0.002 (2)	−0.007 (2)	−0.0043 (19)
C9	0.041 (3)	0.034 (2)	0.032 (2)	−0.001 (2)	0.000 (2)	−0.0073 (19)
C10	0.056 (3)	0.037 (3)	0.033 (3)	0.006 (2)	−0.007 (2)	0.000 (2)
C11	0.067 (4)	0.048 (3)	0.031 (2)	−0.013 (3)	0.005 (3)	−0.001 (2)
C12	0.046 (4)	0.062 (4)	0.050 (3)	−0.007 (3)	0.014 (3)	−0.003 (3)
C13	0.036 (3)	0.062 (3)	0.079 (4)	0.010 (3)	0.000 (3)	0.013 (3)
C14	0.043 (3)	0.047 (3)	0.046 (3)	0.005 (2)	0.004 (2)	0.011 (2)
N1	0.041 (2)	0.0309 (18)	0.0317 (18)	−0.0008 (19)	0.0009 (19)	−0.0007 (14)
N2	0.058 (3)	0.037 (2)	0.0324 (19)	−0.001 (2)	0.005 (2)	−0.0029 (17)
N3	0.060 (3)	0.041 (2)	0.036 (2)	−0.002 (2)	0.006 (2)	−0.0008 (17)
S1	0.0572 (8)	0.0316 (6)	0.0597 (8)	−0.0043 (6)	0.0020 (8)	−0.0025 (6)

Geometric parameters (Å, º) top

C1—N1	1.324 (5)	C7—H7A	0.9700
C1—N3	1.481 (5)	C7—H7B	0.9700
C1—S1	1.634 (4)	C8—N1	1.456 (5)
C2—N1	1.470 (5)	C8—C9	1.500 (7)
C2—N2	1.485 (5)	C8—H8A	0.9700
C2—C3	1.527 (7)	C8—H8B	0.9700
C2—C7	1.528 (7)	C9—C14	1.386 (7)
C3—C4	1.524 (6)	C9—C10	1.391 (6)
C3—H3A	0.9700	C10—C11	1.378 (8)
C3—H3B	0.9700	C10—H10	0.9300
C4—C5	1.516 (7)	C11—C12	1.362 (8)
C4—H4A	0.9700	C11—H11	0.9300
C4—H4B	0.9700	C12—C13	1.376 (7)
C5—C6	1.512 (7)	C12—H12	0.9300
C5—H5A	0.9700	C13—C14	1.375 (7)
C5—H5B	0.9700	C13—H13	0.9300
C6—C7	1.533 (6)	C14—H14	0.9300
C6—H6A	0.9700	N2—N3	1.247 (5)
C6—H6B	0.9700

N1—C1—N3	106.4 (4)	C2—C7—H7A	109.4
N1—C1—S1	131.9 (3)	C6—C7—H7A	109.4
N3—C1—S1	121.7 (3)	C2—C7—H7B	109.4
N1—C2—N2	100.8 (3)	C6—C7—H7B	109.4
N1—C2—C3	112.6 (4)	H7A—C7—H7B	108.0
N2—C2—C3	109.0 (4)	N1—C8—C9	113.9 (4)
N1—C2—C7	111.6 (4)	N1—C8—H8A	108.8
N2—C2—C7	108.4 (4)	C9—C8—H8A	108.8
C3—C2—C7	113.4 (3)	N1—C8—H8B	108.8
C4—C3—C2	111.7 (4)	C9—C8—H8B	108.8
C4—C3—H3A	109.3	H8A—C8—H8B	107.7
C2—C3—H3A	109.3	C14—C9—C10	118.1 (5)
C4—C3—H3B	109.3	C14—C9—C8	121.3 (4)
C2—C3—H3B	109.3	C10—C9—C8	120.6 (4)
H3A—C3—H3B	107.9	C11—C10—C9	120.9 (5)
C5—C4—C3	111.7 (4)	C11—C10—H10	119.6
C5—C4—H4A	109.3	C9—C10—H10	119.6
C3—C4—H4A	109.3	C12—C11—C10	120.3 (5)
C5—C4—H4B	109.3	C12—C11—H11	119.9
C3—C4—H4B	109.3	C10—C11—H11	119.9
H4A—C4—H4B	107.9	C11—C12—C13	119.6 (5)
C6—C5—C4	111.5 (4)	C11—C12—H12	120.2
C6—C5—H5A	109.3	C13—C12—H12	120.2
C4—C5—H5A	109.3	C14—C13—C12	120.8 (5)
C6—C5—H5B	109.3	C14—C13—H13	119.6
C4—C5—H5B	109.3	C12—C13—H13	119.6
H5A—C5—H5B	108.0	C13—C14—C9	120.3 (5)
C5—C6—C7	112.2 (4)	C13—C14—H14	119.8
C5—C6—H6A	109.2	C9—C14—H14	119.8
C7—C6—H6A	109.2	C1—N1—C8	124.3 (4)
C5—C6—H6B	109.2	C1—N1—C2	111.0 (3)
C7—C6—H6B	109.2	C8—N1—C2	124.7 (3)
H6A—C6—H6B	107.9	N3—N2—C2	112.1 (3)
C2—C7—C6	111.4 (4)	N2—N3—C1	109.7 (4)

N1—C2—C3—C4	179.1 (4)	C8—C9—C14—C13	179.8 (5)
N2—C2—C3—C4	−69.9 (5)	N3—C1—N1—C8	−179.6 (4)
C7—C2—C3—C4	51.1 (5)	S1—C1—N1—C8	0.7 (9)
C2—C3—C4—C5	−53.4 (5)	N3—C1—N1—C2	−1.6 (6)
C3—C4—C5—C6	56.1 (5)	S1—C1—N1—C2	178.8 (4)
C4—C5—C6—C7	−55.7 (6)	C9—C8—N1—C1	−101.8 (6)
N1—C2—C7—C6	−178.9 (4)	C9—C8—N1—C2	80.4 (6)
N2—C2—C7—C6	71.0 (5)	N2—C2—N1—C1	1.5 (5)
C3—C2—C7—C6	−50.3 (5)	C3—C2—N1—C1	117.6 (5)
C5—C6—C7—C2	52.4 (6)	C7—C2—N1—C1	−113.4 (5)
N1—C8—C9—C14	54.4 (6)	N2—C2—N1—C8	179.6 (4)
N1—C8—C9—C10	−126.1 (4)	C3—C2—N1—C8	−64.4 (6)
C14—C9—C10—C11	−0.2 (7)	C7—C2—N1—C8	64.6 (6)
C8—C9—C10—C11	−179.8 (4)	N1—C2—N2—N3	−0.9 (5)
C9—C10—C11—C12	−0.3 (7)	C3—C2—N2—N3	−119.6 (5)
C10—C11—C12—C13	0.8 (8)	C7—C2—N2—N3	116.5 (5)
C11—C12—C13—C14	−0.8 (9)	C2—N2—N3—C1	0.0 (6)
C12—C13—C14—C9	0.3 (9)	N1—C1—N3—N2	1.0 (6)
C10—C9—C14—C13	0.2 (7)	S1—C1—N3—N2	−179.3 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···S1ⁱ	0.93	2.87	3.779 (6)	166

Symmetry code: (i) −x+1, y+1/2, −z+1/2.

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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