1,3-Bis(1-phenyl­eth­yl)imidazolidine-2-thione

Umar, M.N.; Tahir, M.N.; Shoaib, M.; Ali, A.; Khan, I.

doi:10.1107/S160053681201224X

organic compounds

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ISSN: 2056-9890

Volume 68| Part 4| April 2012| Page o1188

doi:10.1107/S160053681201224X

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1,3-Bis(1-phenylethyl)imidazolidine-2-thione

M. Naveed Umar,^a M. Nawaz Tahir,^b ^* Mohammad Shoaib,^c Akbar Ali ^a and Imran Khan ^d

^aDepartment of Chemistry, University of Malakand, Pakistan, ^bUniversity of Sargodha, Department of Physics, Sargodha, Pakistan, ^cDepartment of Pharmacy, University of Malakand, Pakistan, and ^dDepartment of Biotechnology, University of Malakand, Pakistan
^*Correspondence e-mail: dmntahir_uos@yahoo.com

(Received 18 March 2012; accepted 21 March 2012; online 24 March 2012)

The complete molecule of the title compound, C₁₉H₂₂N₂S, is generated by crystallographic twofold symmetry with the C=S group lying on the rotation axis. The imidazolidine ring adopts a flattened twist conformation. The dihedral angle between the asymmetric part of the imidazolidine-2-thione fragment and the benzene ring is 89.49 (17)°.

Related literature

For a related structure, see: Umar et al. (2012 ).

Experimental

Crystal data

C₁₉H₂₂N₂S
M_r = 310.45
Tetragonal, P 4₃ 2₁ 2
a = 5.8692 (5) Å
c = 50.637 (5) Å
V = 1744.3 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.18 mm⁻¹
T = 296 K
0.28 × 0.24 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.957, T_max = 0.966
18956 measured reflections
1717 independent reflections
1150 reflections with I > 2σ(I)
R_int = 0.062

Refinement

R[F² > 2σ(F²)] = 0.070
wR(F²) = 0.170
S = 1.11
1717 reflections
106 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.17 e Å⁻³
Absolute structure: Flack (1983 ), 569 Friedel pairs
Flack parameter: 0.1 (3)

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681201224X/gk2471sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681201224X/gk2471Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681201224X/gk2471Isup3.cml

checkCIF report

Comment top

The title compound, Fig. 1, has been synthesized as a part of our ongoing project related to imidazolidinethione.

Recently we have reported the crystal structure of 1,3-bis(1-cyclohexylethyl)imidazolidine (Umar et al., 2012) that is related to the title compound.

The molecule has twofold rotation symmetry about the C=S bond of imidazolidinethione fragment and therefore the asymmetric unit consists of half of the molecule. The asymmetric part of imidazolidinethione fragment A (S1/C1/N1/C2) and the benzene ring B (C6/C7/C9/C10) form the dihedral angle of 89.49 (17)°.

Related literature top

For a related structure, see: Umar et al. (2012).

Experimental top

(S)-1-Phenylethanamine (2.5 equiv.) and 1,2-dibromoethane (1 equiv.) were placed in a pressure vessel and heated at 393 K for 5 h, during which the reaction mixture solidified. The system was cooled to room temperature and NaOH (1 N, 20 ml) and ethyl acetate (20 ml) were added into the reaction mixture. After dissolving the reaction mixture, the crude product was extracted with ethyl acetate (3×25 ml). The combined organic layers were concentrated and subjected to column chromatography. The product obtained from column chromatography (1 equiv.) was added to toluene (0.4 M) in pressure vessel and thiocarbonyldiimidazol (1.1 equiv.) was added to it. This mixture was heated at about 373 K for 15 h. Again the extraction with ethyl acetate (3×25 ml) was carried out by using column chromatography to get the required product (yield: 80%).White prisms of of the title compound were obtained by recrystalization from methanol during 48 h (m.p. 416 K).

Structure description top

The title compound, Fig. 1, has been synthesized as a part of our ongoing project related to imidazolidinethione.

Recently we have reported the crystal structure of 1,3-bis(1-cyclohexylethyl)imidazolidine (Umar et al., 2012) that is related to the title compound.

For a related structure, see: Umar et al. (2012).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

Fig. 1. View of the title molecule with displacement ellipsoids drawn at the 50% probability level. H atoms are shown by small circles of arbitrary radii.

1,3-Bis(1-phenylethyl)imidazolidine-2-thione top

Crystal data top

C₁₉H₂₂N₂S	D_x = 1.182 Mg m⁻³
M_r = 310.45	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4₃2₁2	Cell parameters from 1150 reflections
Hall symbol: P 4nw 2abw	θ = 3.2–26.0°
a = 5.8692 (5) Å	µ = 0.18 mm⁻¹
c = 50.637 (5) Å	T = 296 K
V = 1744.3 (3) Å³	Prism, white
Z = 4	0.28 × 0.24 × 0.20 mm
F(000) = 664

Data collection top

Bruker Kappa APEXII CCD diffractometer	1717 independent reflections
Radiation source: fine-focus sealed tube	1150 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.062
Detector resolution: 7.80 pixels mm^-1	θ_max = 26.0°, θ_min = 3.2°
ω scans	h = −3→7
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −7→7
T_min = 0.957, T_max = 0.966	l = −62→62
18956 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.070	w = 1/[σ²(F_o²) + (0.0459P)² + 1.2139P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.170	(Δ/σ)_max < 0.001
S = 1.11	Δρ_max = 0.18 e Å⁻³
1717 reflections	Δρ_min = −0.17 e Å⁻³
106 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.011 (3)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 569 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.1 (3)

Crystal data top

C₁₉H₂₂N₂S	Z = 4
M_r = 310.45	Mo Kα radiation
Tetragonal, P4₃2₁2	µ = 0.18 mm⁻¹
a = 5.8692 (5) Å	T = 296 K
c = 50.637 (5) Å	0.28 × 0.24 × 0.20 mm
V = 1744.3 (3) Å³

Data collection top

Bruker Kappa APEXII CCD diffractometer	1717 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1150 reflections with I > 2σ(I)
T_min = 0.957, T_max = 0.966	R_int = 0.062
18956 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.070	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.170	Δρ_max = 0.18 e Å⁻³
S = 1.11	Δρ_min = −0.17 e Å⁻³
1717 reflections	Absolute structure: Flack (1983), 569 Friedel pairs
106 parameters	Absolute structure parameter: 0.1 (3)
0 restraints

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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	1.12952 (18)	1.12952 (18)	0.0000	0.0805 (6)
N1	0.8146 (6)	0.8492 (6)	0.02136 (5)	0.0692 (10)
C1	0.9276 (6)	0.9276 (6)	0.0000	0.0598 (14)
C2	0.6343 (8)	0.6919 (7)	0.01411 (7)	0.0723 (12)
H2A	0.4858	0.7636	0.0154	0.087*
H2B	0.6367	0.5571	0.0252	0.087*
C3	0.8267 (8)	0.9498 (8)	0.04762 (8)	0.0687 (12)
H3	0.962 (7)	1.038 (7)	0.0469 (8)	0.082*
C4	0.6154 (10)	1.0894 (8)	0.05338 (9)	0.1018 (18)
H4A	0.5884	1.1932	0.0391	0.153*
H4B	0.6372	1.1738	0.0694	0.153*
H4C	0.4868	0.9897	0.0553	0.153*
C5	0.8783 (7)	0.7647 (7)	0.06798 (7)	0.0579 (10)
C6	1.0569 (8)	0.6131 (9)	0.06414 (9)	0.0843 (14)
H6	1.1454	0.6219	0.0489	0.101*
C7	1.1034 (9)	0.4468 (9)	0.08326 (11)	0.0963 (17)
H7	1.2213	0.3437	0.0805	0.116*
C8	0.9810 (11)	0.4343 (9)	0.10538 (10)	0.1002 (19)
H8	1.0161	0.3253	0.1181	0.120*
C9	0.8049 (10)	0.5808 (9)	0.10942 (9)	0.0949 (17)
H9	0.7157	0.5700	0.1246	0.114*
C10	0.7614 (8)	0.7429 (8)	0.09100 (7)	0.0764 (12)
H10	0.6442	0.8456	0.0943	0.092*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0776 (8)	0.0776 (8)	0.0861 (11)	−0.0227 (10)	−0.0077 (7)	0.0077 (7)
N1	0.085 (3)	0.070 (2)	0.0521 (17)	−0.0229 (18)	−0.0062 (16)	0.0039 (17)
C1	0.062 (2)	0.062 (2)	0.056 (3)	−0.002 (3)	−0.007 (2)	0.007 (2)
C2	0.084 (3)	0.073 (3)	0.060 (2)	−0.024 (2)	−0.003 (2)	0.0031 (19)
C3	0.080 (3)	0.063 (3)	0.063 (2)	−0.005 (2)	−0.007 (2)	−0.006 (2)
C4	0.138 (5)	0.081 (4)	0.086 (3)	0.046 (4)	−0.015 (3)	−0.008 (3)
C5	0.057 (2)	0.063 (2)	0.053 (2)	0.001 (2)	−0.005 (2)	−0.0054 (18)
C6	0.070 (3)	0.108 (4)	0.074 (3)	0.012 (3)	0.003 (2)	−0.006 (3)
C7	0.089 (4)	0.090 (4)	0.110 (4)	0.037 (3)	−0.024 (3)	−0.012 (3)
C8	0.140 (5)	0.084 (4)	0.077 (3)	0.021 (4)	−0.034 (3)	−0.002 (3)
C9	0.123 (5)	0.097 (4)	0.065 (3)	0.006 (4)	0.003 (3)	0.006 (3)
C10	0.092 (3)	0.079 (3)	0.058 (2)	0.017 (2)	0.004 (2)	−0.001 (2)

Geometric parameters (Å, º) top

S1—C1	1.676 (5)	C4—H4C	0.9600
N1—C1	1.350 (4)	C5—C10	1.359 (5)
N1—C2	1.451 (5)	C5—C6	1.388 (6)
N1—C3	1.456 (5)	C6—C7	1.402 (7)
C1—N1ⁱ	1.350 (4)	C6—H6	0.9300
C2—C2ⁱ	1.507 (7)	C7—C8	1.333 (7)
C2—H2A	0.9700	C7—H7	0.9300
C2—H2B	0.9700	C8—C9	1.360 (7)
C3—C4	1.515 (6)	C8—H8	0.9300
C3—C5	1.528 (6)	C9—C10	1.357 (6)
C3—H3	0.95 (4)	C9—H9	0.9300
C4—H4A	0.9600	C10—H10	0.9300
C4—H4B	0.9600

C1—N1—C2	111.9 (3)	C3—C4—H4C	109.5
C1—N1—C3	124.7 (3)	H4A—C4—H4C	109.5
C2—N1—C3	121.6 (3)	H4B—C4—H4C	109.5
N1ⁱ—C1—N1	107.9 (4)	C10—C5—C6	116.2 (4)
N1ⁱ—C1—S1	126.1 (2)	C10—C5—C3	123.1 (4)
N1—C1—S1	126.1 (2)	C6—C5—C3	120.7 (4)
N1—C2—C2ⁱ	102.7 (2)	C5—C6—C7	119.8 (4)
N1—C2—H2A	111.2	C5—C6—H6	120.1
C2ⁱ—C2—H2A	111.2	C7—C6—H6	120.1
N1—C2—H2B	111.2	C8—C7—C6	120.9 (5)
C2ⁱ—C2—H2B	111.2	C8—C7—H7	119.5
H2A—C2—H2B	109.1	C6—C7—H7	119.5
N1—C3—C4	110.8 (4)	C7—C8—C9	120.1 (5)
N1—C3—C5	109.7 (3)	C7—C8—H8	120.0
C4—C3—C5	114.6 (4)	C9—C8—H8	120.0
N1—C3—H3	103 (2)	C10—C9—C8	118.9 (5)
C4—C3—H3	113 (3)	C10—C9—H9	120.6
C5—C3—H3	104 (3)	C8—C9—H9	120.6
C3—C4—H4A	109.5	C9—C10—C5	124.1 (5)
C3—C4—H4B	109.5	C9—C10—H10	117.9
H4A—C4—H4B	109.5	C5—C10—H10	117.9

C2—N1—C1—N1ⁱ	−6.1 (2)	C4—C3—C5—C10	−7.4 (6)
C3—N1—C1—N1ⁱ	−171.0 (5)	N1—C3—C5—C6	49.8 (5)
C2—N1—C1—S1	173.9 (2)	C4—C3—C5—C6	175.2 (4)
C3—N1—C1—S1	9.0 (5)	C10—C5—C6—C7	1.4 (7)
C1—N1—C2—C2ⁱ	14.8 (5)	C3—C5—C6—C7	179.1 (4)
C3—N1—C2—C2ⁱ	−179.8 (4)	C5—C6—C7—C8	−1.2 (8)
C1—N1—C3—C4	102.8 (5)	C6—C7—C8—C9	1.5 (8)
C2—N1—C3—C4	−60.7 (5)	C7—C8—C9—C10	−2.0 (8)
C1—N1—C3—C5	−129.6 (4)	C8—C9—C10—C5	2.4 (8)
C2—N1—C3—C5	66.9 (5)	C6—C5—C10—C9	−2.1 (7)
N1—C3—C5—C10	−132.8 (4)	C3—C5—C10—C9	−179.7 (4)

Symmetry code: (i) y, x, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···S1	0.95 (4)	2.63 (4)	3.176 (4)	117 (3)

Experimental details

Crystal data
Chemical formula	C₁₉H₂₂N₂S
M_r	310.45
Crystal system, space group	Tetragonal, P4₃2₁2
Temperature (K)	296
a, c (Å)	5.8692 (5), 50.637 (5)
V (Å³)	1744.3 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.18
Crystal size (mm)	0.28 × 0.24 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.957, 0.966
No. of measured, independent and observed [I > 2σ(I)] reflections	18956, 1717, 1150
R_int	0.062
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.070, 0.170, 1.11
No. of reflections	1717
No. of parameters	106
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.17
Absolute structure	Flack (1983), 569 Friedel pairs
Absolute structure parameter	0.1 (3)

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Acknowledgements

The authors acknowledge the provision of funds for the purchase of the diffractometer and encouragement by Dr Muhammad Akram Chaudhary, Vice Chancellor, University of Sargodha, Pakistan. The authors from Malakand University also gratefully acknowledge the financial support provided by the Higher Education Commission (HEC), Islamabad, Pakistan.

References

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