4-Phenyl-1,2,4-tri­aza­spiro­[4.6]undec-1-ene-3-thione

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

doi:10.1107/S1600536814009817

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 70| Part 6| June 2014| Page o640

doi:10.1107/S1600536814009817

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4-Phenyl-1,2,4-triazaspiro[4.6]undec-1-ene-3-thione

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

^aChemistry and Environmental Division, Manchester Metropolitan University, Manchester M1 5GD, England, ^bChemistry Department, Faculty of Science, Mini 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, and ^eKirkuk University, College of Science, Department of Chemistry, Kirkuk, Iraq
^*Correspondence e-mail: shaabankamel@yahoo.com

Edited by P. C. Healy, Griffith University, Australia (Received 29 April 2014; accepted 1 May 2014; online 10 May 2014)

In the title compound, C₁₄H₁₇N₃S, the plane of the phenyl ring makes a dihedral angle of 74.90 (4)° with that of the triazathione ring (r.m.s. deviation = 0.001 Å), while the seven-membered ring adopts a twist-chair conformation. No specific intermolecular interactions are discerned in the crystal packing.

CCDC reference: 1000439

Related literature

For various pharmaceutical properties of spiro compounds, see: Chin et al. (2008 ); Thadhaney et al. (2010 ). For industrial uses of heterocyclic spiro compounds, see: Sarma et al. (2010 ). For the crystal structures of two similar compounds, see: Akkurt et al. (2013 ); Mague et al. (2014 ). For ring-puckering parameters, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₁₄H₁₇N₃S
M_r = 259.36
Triclinic, $[P \overline 1]$
a = 9.0578 (5) Å
b = 9.1324 (5) Å
c = 9.4637 (5) Å
α = 88.2940 (8)°
β = 79.0690 (7)°
γ = 61.6640 (6)°
V = 674.89 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 150 K
0.28 × 0.23 × 0.06 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2013 ) T_min = 0.85, T_max = 0.98
12510 measured reflections
3508 independent reflections
3125 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.096
S = 1.04
3508 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT; program(s) used to solve structure: SHELXT (Bruker, 2013); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008 ); molecular graphics: DIAMOND (Brandenburg & Putz, 2012 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

CCDC reference: 1000439

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536814009817/hg5394sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814009817/hg5394Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814009817/hg5394Isup3.cml

checkCIF report

Comment top

Spiro-compounds are a significant class of of organic compounds due to their wide spectrum of pharmaceutical and applied chemistry aspects. They showed very promising biological activities such as anticancer agents (Chin et al., 2008) and antimicrobial agents (Thadhaney et al., 2010). Some spiro-compounds have also been recently used as antioxidants (Sarma et al., 2010). In this context and as part of our on-going study in synthesis of spiro-compounds for the purpose of biological potential, we report in this study the synthesis and crystal structure determination of the title compound.

In the title compound (I, Fig. 1), a Cremer-Pople analysis of the conformation of the 7-membered ring (C2/C9/C10–C14) gave puckering parameters Q(2) = 0.5606 (14) Å, Q(3) = 0.6549 (15) Å, ϕ(2) = 272.80 (15)° and ϕ(3) = 272.01 (12)° (Cremer & Pople, 1975). The total puckerin amplitude is 0.8620 (14) Å.

The phenyl ring (C3–C8) makes a dihedral angle of 74.90 (4)° with the triazathione ring (C1/C2/N1–N3). All bond lengths and bond angles in (I) are comparable with those for the similar compounds that we have reported previously (Akkurt et al., 2013; Mague et al., 2014).

Related literature top

For various pharmaceutical properties of spiro-compounds, see: Chin et al. (2008); Thadhaney et al. (2010). For industrial uses of heterocyclic spiro compounds, see: Sarma et al. (2010). For the crystal structures of two similar compounds, see: Akkurt et al. (2013); Mague et al. (2014). For ring-puckering parameters, see: Cremer & Pople (1975).

Experimental top

A mixture of 1 mmol (261 mg) of cycloheptan-1-one N-phenylthiosemicarbazone and 1 mmol (246 mg) of 2,3,5,6-tetrachloro-1,4-benzoquinone (DDQ) in 30 ml of ethyl acetate was stirred at room temperature. The reaction was monitored by TLC until completion. The precipitated DDQ-H₂ was filtered off and the filtrate was concentrated by slow evaporation in air to afford the corresponding product. The crude product was recrystallized from ethanol to furnish orange block crystals suitable for X-ray diffraction.

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXT (Bruker, 2013); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. Title compound with 50% probability displacement ellipsoids for non-H atoms.

4-Phenyl-1,2,4-triazaspiro[4.6]undec-1-ene-3-thione top

Crystal data top

C₁₄H₁₇N₃S	Z = 2
M_r = 259.36	F(000) = 276
Triclinic, P1	D_x = 1.276 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.0578 (5) Å	Cell parameters from 9063 reflections
b = 9.1324 (5) Å	θ = 2.2–29.1°
c = 9.4637 (5) Å	µ = 0.23 mm⁻¹
α = 88.2940 (8)°	T = 150 K
β = 79.0690 (7)°	Plate, orange
γ = 61.6640 (6)°	0.28 × 0.23 × 0.06 mm
V = 674.89 (6) Å³

Data collection top

Bruker SMART APEX CCD diffractometer	3508 independent reflections
Radiation source: fine-focus sealed tube	3125 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
Detector resolution: 8.3660 pixels mm^-1	θ_max = 29.1°, θ_min = 2.2°
ϕ and ω scans	h = −12→12
Absorption correction: multi-scan (SADABS; Bruker, 2013)	k = −12→12
T_min = 0.85, T_max = 0.98	l = −12→12
12510 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) = 0.096	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0469P)² + 0.2315P] where P = (F_o² + 2F_c²)/3
3508 reflections	(Δ/σ)_max < 0.001
163 parameters	Δρ_max = 0.44 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₁₄H₁₇N₃S	γ = 61.6640 (6)°
M_r = 259.36	V = 674.89 (6) Å³
Triclinic, P1	Z = 2
a = 9.0578 (5) Å	Mo Kα radiation
b = 9.1324 (5) Å	µ = 0.23 mm⁻¹
c = 9.4637 (5) Å	T = 150 K
α = 88.2940 (8)°	0.28 × 0.23 × 0.06 mm
β = 79.0690 (7)°

Data collection top

Bruker SMART APEX CCD diffractometer	3508 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2013)	3125 reflections with I > 2σ(I)
T_min = 0.85, T_max = 0.98	R_int = 0.032
12510 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.096	H-atom parameters constrained
S = 1.04	Δρ_max = 0.44 e Å⁻³
3508 reflections	Δρ_min = −0.20 e Å⁻³
163 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs 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	1.18135 (4)	0.44697 (4)	0.80140 (3)	0.0246 (1)
N1	0.85249 (12)	0.58855 (11)	0.76728 (10)	0.0161 (2)
N2	0.75975 (13)	0.84504 (12)	0.87544 (11)	0.0222 (3)
N3	0.91495 (13)	0.75963 (13)	0.87953 (11)	0.0223 (3)
C1	0.98219 (14)	0.59098 (14)	0.81285 (12)	0.0180 (3)
C2	0.69598 (14)	0.75078 (13)	0.80402 (12)	0.0169 (3)
C3	0.85298 (13)	0.44117 (13)	0.71782 (12)	0.0165 (3)
C4	0.85413 (15)	0.32566 (14)	0.81669 (13)	0.0205 (3)
C5	0.84438 (16)	0.18734 (15)	0.77211 (14)	0.0255 (3)
C6	0.83537 (18)	0.16576 (16)	0.63011 (15)	0.0292 (4)
C7	0.83794 (18)	0.28004 (17)	0.53131 (14)	0.0294 (4)
C8	0.84735 (15)	0.41916 (15)	0.57489 (12)	0.0219 (3)
C9	0.55281 (15)	0.73871 (14)	0.91260 (12)	0.0202 (3)
C10	0.42376 (16)	0.71324 (16)	0.84612 (13)	0.0238 (3)
C11	0.27415 (16)	0.87693 (17)	0.81639 (14)	0.0267 (3)
C12	0.31779 (16)	0.96808 (17)	0.69115 (14)	0.0273 (3)
C13	0.46872 (15)	0.99887 (15)	0.69690 (13)	0.0232 (3)
C14	0.64134 (14)	0.83880 (14)	0.66771 (12)	0.0192 (3)
H4	0.86150	0.34080	0.91350	0.0250*
H5	0.84390	0.10770	0.83880	0.0310*
H6	0.82740	0.07180	0.60030	0.0350*
H7	0.83330	0.26350	0.43400	0.0350*
H8	0.84990	0.49780	0.50780	0.0260*
H9A	0.60640	0.64490	0.97310	0.0240*
H9B	0.48930	0.84220	0.97700	0.0240*
H10A	0.48410	0.64340	0.75450	0.0280*
H10B	0.37790	0.65200	0.91250	0.0280*
H11A	0.18390	0.85290	0.79680	0.0320*
H11B	0.22550	0.95280	0.90490	0.0320*
H12A	0.21550	1.07700	0.68880	0.0330*
H12B	0.34380	0.90240	0.59990	0.0330*
H13A	0.45120	1.05050	0.79330	0.0280*
H13B	0.47140	1.07860	0.62450	0.0280*
H14A	0.73050	0.86640	0.61770	0.0230*
H14B	0.63500	0.76060	0.60190	0.0230*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0207 (2)	0.0261 (2)	0.0266 (2)	−0.0094 (1)	−0.0087 (1)	0.0025 (1)
N1	0.0189 (4)	0.0140 (4)	0.0172 (4)	−0.0087 (3)	−0.0049 (3)	0.0000 (3)
N2	0.0285 (5)	0.0188 (5)	0.0241 (5)	−0.0141 (4)	−0.0079 (4)	−0.0009 (4)
N3	0.0278 (5)	0.0208 (5)	0.0241 (5)	−0.0148 (4)	−0.0090 (4)	0.0004 (4)
C1	0.0234 (5)	0.0190 (5)	0.0158 (5)	−0.0129 (4)	−0.0058 (4)	0.0023 (4)
C2	0.0203 (5)	0.0136 (5)	0.0185 (5)	−0.0089 (4)	−0.0049 (4)	−0.0011 (4)
C3	0.0177 (5)	0.0148 (5)	0.0185 (5)	−0.0092 (4)	−0.0026 (4)	−0.0023 (4)
C4	0.0234 (5)	0.0192 (5)	0.0199 (5)	−0.0112 (4)	−0.0037 (4)	0.0006 (4)
C5	0.0301 (6)	0.0187 (5)	0.0303 (6)	−0.0149 (5)	−0.0033 (5)	0.0030 (5)
C6	0.0374 (7)	0.0225 (6)	0.0336 (7)	−0.0193 (5)	−0.0051 (5)	−0.0056 (5)
C7	0.0412 (7)	0.0293 (7)	0.0226 (6)	−0.0205 (6)	−0.0059 (5)	−0.0058 (5)
C8	0.0290 (6)	0.0212 (5)	0.0176 (5)	−0.0141 (5)	−0.0033 (4)	−0.0003 (4)
C9	0.0230 (5)	0.0207 (5)	0.0161 (5)	−0.0102 (4)	−0.0024 (4)	0.0002 (4)
C10	0.0254 (6)	0.0265 (6)	0.0236 (6)	−0.0168 (5)	−0.0015 (5)	−0.0014 (5)
C11	0.0209 (5)	0.0338 (7)	0.0259 (6)	−0.0137 (5)	−0.0034 (5)	−0.0030 (5)
C12	0.0221 (6)	0.0311 (6)	0.0259 (6)	−0.0093 (5)	−0.0082 (5)	0.0009 (5)
C13	0.0248 (6)	0.0188 (5)	0.0246 (6)	−0.0085 (4)	−0.0076 (5)	0.0031 (4)
C14	0.0214 (5)	0.0182 (5)	0.0191 (5)	−0.0100 (4)	−0.0050 (4)	0.0032 (4)

Geometric parameters (Å, º) top

S1—C1	1.6364 (13)	C13—C14	1.5325 (18)
N1—C1	1.3357 (18)	C4—H4	0.9500
N1—C2	1.4750 (15)	C5—H5	0.9500
N1—C3	1.4359 (15)	C6—H6	0.9500
N2—N3	1.2506 (17)	C7—H7	0.9500
N2—C2	1.4786 (17)	C8—H8	0.9500
N3—C1	1.4707 (15)	C9—H9A	0.9900
C2—C9	1.5406 (19)	C9—H9B	0.9900
C2—C14	1.5356 (16)	C10—H10A	0.9900
C3—C4	1.3867 (16)	C10—H10B	0.9900
C3—C8	1.3874 (16)	C11—H11A	0.9900
C4—C5	1.3904 (18)	C11—H11B	0.9900
C5—C6	1.387 (2)	C12—H12A	0.9900
C6—C7	1.3859 (19)	C12—H12B	0.9900
C7—C8	1.392 (2)	C13—H13A	0.9900
C9—C10	1.537 (2)	C13—H13B	0.9900
C10—C11	1.532 (2)	C14—H14A	0.9900
C11—C12	1.5264 (19)	C14—H14B	0.9900
C12—C13	1.531 (2)

C1—N1—C2	110.52 (10)	C6—C7—H7	120.00
C1—N1—C3	124.94 (10)	C8—C7—H7	120.00
C2—N1—C3	123.30 (11)	C3—C8—H8	120.00
N3—N2—C2	112.14 (10)	C7—C8—H8	121.00
N2—N3—C1	110.00 (11)	C2—C9—H9A	108.00
S1—C1—N1	131.05 (9)	C2—C9—H9B	108.00
S1—C1—N3	122.55 (10)	C10—C9—H9A	108.00
N1—C1—N3	106.39 (10)	C10—C9—H9B	108.00
N1—C2—N2	100.93 (10)	H9A—C9—H9B	107.00
N1—C2—C9	112.71 (9)	C9—C10—H10A	109.00
N1—C2—C14	111.24 (9)	C9—C10—H10B	109.00
N2—C2—C9	108.93 (9)	C11—C10—H10A	109.00
N2—C2—C14	107.14 (9)	C11—C10—H10B	109.00
C9—C2—C14	114.78 (11)	H10A—C10—H10B	108.00
N1—C3—C4	118.50 (10)	C10—C11—H11A	108.00
N1—C3—C8	120.00 (10)	C10—C11—H11B	108.00
C4—C3—C8	121.47 (11)	C12—C11—H11A	108.00
C3—C4—C5	119.06 (11)	C12—C11—H11B	108.00
C4—C5—C6	119.93 (12)	H11A—C11—H11B	107.00
C5—C6—C7	120.60 (13)	C11—C12—H12A	109.00
C6—C7—C8	119.93 (12)	C11—C12—H12B	109.00
C3—C8—C7	118.98 (11)	C13—C12—H12A	108.00
C2—C9—C10	115.55 (10)	C13—C12—H12B	108.00
C9—C10—C11	113.31 (11)	H12A—C12—H12B	108.00
C10—C11—C12	115.62 (12)	C12—C13—H13A	109.00
C11—C12—C13	115.09 (12)	C12—C13—H13B	109.00
C12—C13—C14	112.85 (11)	C14—C13—H13A	109.00
C2—C14—C13	114.07 (9)	C14—C13—H13B	109.00
C3—C4—H4	120.00	H13A—C13—H13B	108.00
C5—C4—H4	120.00	C2—C14—H14A	109.00
C4—C5—H5	120.00	C2—C14—H14B	109.00
C6—C5—H5	120.00	C13—C14—H14A	109.00
C5—C6—H6	120.00	C13—C14—H14B	109.00
C7—C6—H6	120.00	H14A—C14—H14B	108.00

C2—N1—C1—S1	179.77 (9)	N1—C2—C9—C10	−93.43 (12)
C2—N1—C1—N3	−1.29 (12)	N2—C2—C9—C10	155.42 (10)
C3—N1—C1—S1	12.16 (18)	C14—C2—C9—C10	35.32 (14)
C3—N1—C1—N3	−168.90 (10)	N1—C2—C14—C13	173.50 (11)
C1—N1—C2—N2	0.83 (12)	N2—C2—C14—C13	−77.06 (14)
C1—N1—C2—C9	−115.21 (11)	C9—C2—C14—C13	44.03 (14)
C1—N1—C2—C14	114.23 (11)	N1—C3—C4—C5	176.23 (12)
C3—N1—C2—N2	168.68 (9)	C8—C3—C4—C5	−1.9 (2)
C3—N1—C2—C9	52.64 (14)	N1—C3—C8—C7	−176.32 (13)
C3—N1—C2—C14	−77.92 (14)	C4—C3—C8—C7	1.8 (2)
C1—N1—C3—C4	67.68 (16)	C3—C4—C5—C6	0.6 (2)
C1—N1—C3—C8	−114.17 (14)	C4—C5—C6—C7	0.7 (2)
C2—N1—C3—C4	−98.41 (14)	C5—C6—C7—C8	−0.9 (2)
C2—N1—C3—C8	79.74 (15)	C6—C7—C8—C3	−0.4 (2)
C2—N2—N3—C1	−0.83 (13)	C2—C9—C10—C11	−87.16 (13)
N3—N2—C2—N1	0.05 (13)	C9—C10—C11—C12	71.74 (14)
N3—N2—C2—C9	118.86 (11)	C10—C11—C12—C13	−52.16 (16)
N3—N2—C2—C14	−116.42 (11)	C11—C12—C13—C14	70.85 (14)
N2—N3—C1—S1	−179.60 (9)	C12—C13—C14—C2	−91.21 (13)
N2—N3—C1—N1	1.35 (13)

Acknowledgements

Manchester Metropolitan University, Tulane University and Erciyes University are gratefully acknowledged for supporting this study.

References

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