2-(2-Thien­yl)-4,5-dihydro-1H-imidazole

Kia, R.; Fun, H.-K.; Kargar, H.

doi:10.1107/S1600536809001068

organic compounds

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ISSN: 2056-9890

Volume 65| Part 2| February 2009| Page o301

doi:10.1107/S1600536809001068

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ADDENDA AND ERRATA

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2-(2-Thienyl)-4,5-dihydro-1H-imidazole

Reza Kia,^a Hoong-Kun Fun ^a ^* and Hadi Kargar ^b

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^bDepartment of Chemistry, School of Science, Payame Noor University (PNU), Ardakan, Yazd, Iran
^*Correspondence e-mail: hkfun@usm.my

(Received 8 January 2009; accepted 9 January 2009; online 14 January 2009)

In title compound, C₇H₈N₂S, the five-membered rings are twisted by a dihedral angle of 5.17 (10)°. Two intermolecular N—H⋯N and C—H⋯N hydrogen bonds to the same acceptor N atom form seven-membered rings, producing R₂¹(7) ring motifs. These interactions link neighbouring molecules into one-dimensional chains extended along the c axis. The crystal structure is further stabilized by weak intermolecular C—H⋯π interactions.

Related literature

For reference geometrical data, see: Allen et al. (1987 ). For details of hydrogen-bond motifs, see: Bernstein et al. (1995 ). For a related structure and the synthesis, see, Kia et al. (2008 ); Stibrany et al. (2004 ). For the applications of imidazoline derivatives, see, for example: Blancafort (1978 ); Chan (1993 ); Vizi (1986 ); Li et al. (1996 ); Ueno et al. (1995 ); Corey & Grogan (1999 ).

Experimental

Crystal data

C₇H₈N₂S
M_r = 152.21
Monoclinic, P 2₁ /c
a = 6.1321 (2) Å
b = 11.5663 (3) Å
c = 10.0098 (3) Å
β = 90.154 (1)°
V = 709.95 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.37 mm⁻¹
T = 100.0 (1) K
0.54 × 0.28 × 0.22 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.825, T_max = 0.922
27675 measured reflections
3100 independent reflections
3040 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.128
S = 1.24
3100 reflections
91 parameters
H-atom parameters constrained
Δρ_max = 0.62 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯N2ⁱ	0.75	2.23	2.977 (2)	171
C3—H3A⋯N2ⁱ	0.95	2.60	3.482 (2)	155
C6—H6A⋯Cg1ⁱⁱ	0.99	2.89	3.539 (2)	124
C6—H6B⋯Cg1ⁱⁱⁱ	0.99	2.83	3.691 (2)	146
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[-x, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) x-1, y, z. Cg1 is the centroid of the S1/C1–C4 (thiophen) ring.

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809001068/at2706sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809001068/at2706Isup2.hkl

checkCIF report

Comment top

Imidazoline derivatives are of great importance because they exhibit significant biological and pharmacological activities including antihypertensive (Blancafort 1978), antihyperglycemic (Chan 1993), antidepressive (Vizi 1986), antihypercholesterolemic (Li et al., 1996) and antiinflammatory properties (Ueno et al., 1995). These compounds are also used as catalysts and synthetic intermediates in some organic reactions (Corey & Grogan 1999). Due to these important applications of imidazolines, here we report the crystal structure of the title compound (I).

In the title compound (I) (Fig. 1), bond lengths (Allen et al. 1987) and angles are within the normal ranges and are comparable with the related structures (Stibrany et al. 2004; Kia et al., 2008). The two five-membered rings are not coplanar to each other and twisted by a dihedral angle of 5.17 (10)°. Two intermolecular N—H···N and C—H···N hydrogen bonds involving a nitrogen atom as an acceptor form seven-membered rings, producing, R¹₂(7) ring motifs (Table 1). These interactions link neighbouring molecules into 1-D extended chains along the c axis (, Fig. 2). The crystal structure is further stabilized by weak intermolecular C—H···π interactions [C6—H6A···Cg1ⁱ and C6—H6B···Cg1ⁱⁱ: (i) -x, 1/2 + y, 3/2 - z, (ii) -1 + x, y, z; Cg1 is the centroid of the S1/C1–C4 thiophene ring.

Related literature top

For the values of bond lengths, see: Allen et al. (1987). For details of hydrogen-bond motifs, see: Bernstein et al. (1995). For a related structure and the synthesis, see, Kia et al. (2008); Stibrany et al. (2004). For the applications of imidazoline derivatives, see, for example: Blancafort (1978); Chan (1993); Vizi (1986); Li et al. (1996); Ueno et al. (1995); Corey & Grogan (1999).

Experimental top

The synthetic method was based on the previous work (Stibrany et al. 2004), except that 10 mmol of 2-cyano-thiophene and 40 mmol of ethylenediamine was used. Single crystals suitable for X-ray diffraction were obtained by evaporation of a toluene solution at room temperature.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).

Figures top

	Fig. 1. The molecular structure of (I) with atom labels and 50% probability ellipsoids for non-H atoms.
	Fig. 2. The crystal packing of (I), viewed down the b-axis showing 1-D infinite chain along the c-axis by intermolecular N—H···N and C—H···N interactions. The intermolecular interactions are shown as dashed lines.

2-(2-Thienyl)-4,5-dihydro-1H-imidazole top

Crystal data top

C₇H₈N₂S	F(000) = 320
M_r = 152.21	D_x = 1.424 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9869 reflections
a = 6.1321 (2) Å	θ = 2.5–34.3°
b = 11.5663 (3) Å	µ = 0.37 mm⁻¹
c = 10.0098 (3) Å	T = 100 K
β = 90.154 (1)°	Block, colourless
V = 709.95 (4) Å³	0.54 × 0.28 × 0.22 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	3100 independent reflections
Radiation source: fine-focus sealed tube	3040 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ϕ and ω scans	θ_max = 35.0°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −9→9
T_min = 0.825, T_max = 0.922	k = −18→17
27675 measured reflections	l = −15→15

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.128	H-atom parameters constrained
S = 1.24	w = 1/[σ²(F_o²) + 1.7551P] where P = (F_o² + 2F_c²)/3
3100 reflections	(Δ/σ)_max < 0.001
91 parameters	Δρ_max = 0.62 e Å⁻³
0 restraints	Δρ_min = −0.39 e Å⁻³

Crystal data top

C₇H₈N₂S	V = 709.95 (4) Å³
M_r = 152.21	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.1321 (2) Å	µ = 0.37 mm⁻¹
b = 11.5663 (3) Å	T = 100 K
c = 10.0098 (3) Å	0.54 × 0.28 × 0.22 mm
β = 90.154 (1)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	3100 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	3040 reflections with I > 2σ(I)
T_min = 0.825, T_max = 0.922	R_int = 0.021
27675 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.128	H-atom parameters constrained
S = 1.24	Δρ_max = 0.62 e Å⁻³
3100 reflections	Δρ_min = −0.39 e Å⁻³
91 parameters

Special details top

Experimental. The low-temperature data was collected with the Oxford Cyrosystem Cobra low-temperature attachment.

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	0.46967 (8)	0.14161 (4)	0.59514 (4)	0.01548 (10)
N2	0.0669 (2)	0.29635 (14)	0.61122 (15)	0.0137 (2)
N1	0.0460 (2)	0.30376 (14)	0.83746 (14)	0.0133 (2)
H1N1	0.0584	0.2724	0.9026	0.016*
C1	0.6387 (3)	0.05389 (17)	0.6858 (2)	0.0180 (3)
H1A	0.7542	0.0100	0.6482	0.022*
C2	0.5888 (3)	0.05418 (16)	0.81838 (19)	0.0169 (3)
H2A	0.6655	0.0103	0.8835	0.020*
C3	0.4092 (3)	0.12742 (15)	0.84860 (17)	0.0136 (3)
H3A	0.3530	0.1385	0.9360	0.016*
C4	0.3260 (3)	0.18060 (14)	0.73589 (16)	0.0117 (3)
C5	0.1427 (3)	0.26052 (14)	0.72556 (16)	0.0109 (3)
C6	−0.1543 (3)	0.36276 (17)	0.79447 (17)	0.0154 (3)
H6A	−0.1724	0.4380	0.8403	0.018*
H6B	−0.2849	0.3144	0.8101	0.018*
C7	−0.1097 (3)	0.37874 (16)	0.64419 (17)	0.0151 (3)
H7A	−0.2423	0.3615	0.5912	0.018*
H7B	−0.0634	0.4591	0.6252	0.018*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.01727 (19)	0.01847 (19)	0.01071 (17)	0.00446 (15)	0.00185 (13)	−0.00026 (14)
N2	0.0153 (6)	0.0161 (6)	0.0098 (6)	0.0027 (5)	0.0003 (4)	0.0009 (5)
N1	0.0148 (6)	0.0170 (6)	0.0080 (5)	0.0029 (5)	0.0016 (4)	0.0004 (5)
C1	0.0166 (7)	0.0181 (8)	0.0192 (8)	0.0057 (6)	−0.0001 (6)	−0.0015 (6)
C2	0.0186 (7)	0.0155 (7)	0.0167 (7)	0.0029 (6)	−0.0034 (6)	0.0009 (6)
C3	0.0164 (7)	0.0129 (7)	0.0113 (6)	−0.0001 (5)	−0.0002 (5)	0.0004 (5)
C4	0.0131 (6)	0.0120 (6)	0.0100 (6)	0.0005 (5)	−0.0003 (5)	−0.0005 (5)
C5	0.0120 (6)	0.0113 (6)	0.0094 (6)	−0.0011 (5)	0.0005 (5)	−0.0004 (5)
C6	0.0143 (7)	0.0186 (7)	0.0132 (7)	0.0030 (6)	0.0019 (5)	0.0007 (6)
C7	0.0152 (7)	0.0181 (7)	0.0120 (7)	0.0035 (6)	0.0000 (5)	0.0018 (5)

Geometric parameters (Å, º) top

S1—C1	1.7099 (19)	C2—H2A	0.9500
S1—C4	1.7239 (17)	C3—C4	1.381 (2)
N2—C5	1.302 (2)	C3—H3A	0.9500
N2—C7	1.480 (2)	C4—C5	1.459 (2)
N1—C5	1.364 (2)	C6—C7	1.541 (2)
N1—C6	1.468 (2)	C6—H6A	0.9900
N1—H1N1	0.7501	C6—H6B	0.9900
C1—C2	1.362 (3)	C7—H7A	0.9900
C1—H1A	0.9500	C7—H7B	0.9900
C2—C3	1.423 (3)

C1—S1—C4	91.82 (9)	C5—C4—S1	120.22 (12)
C5—N2—C7	105.57 (14)	N2—C5—N1	116.78 (15)
C5—N1—C6	107.14 (14)	N2—C5—C4	122.49 (15)
C5—N1—H1N1	119.6	N1—C5—C4	120.71 (14)
C6—N1—H1N1	124.2	N1—C6—C7	101.03 (13)
C2—C1—S1	112.21 (14)	N1—C6—H6A	111.6
C2—C1—H1A	123.9	C7—C6—H6A	111.6
S1—C1—H1A	123.9	N1—C6—H6B	111.6
C1—C2—C3	112.63 (16)	C7—C6—H6B	111.6
C1—C2—H2A	123.7	H6A—C6—H6B	109.4
C3—C2—H2A	123.7	N2—C7—C6	105.80 (14)
C4—C3—C2	112.08 (15)	N2—C7—H7A	110.6
C4—C3—H3A	124.0	C6—C7—H7A	110.6
C2—C3—H3A	124.0	N2—C7—H7B	110.6
C3—C4—C5	128.52 (15)	C6—C7—H7B	110.6
C3—C4—S1	111.26 (13)	H7A—C7—H7B	108.7

C4—S1—C1—C2	−0.16 (16)	C6—N1—C5—N2	11.9 (2)
S1—C1—C2—C3	−0.2 (2)	C6—N1—C5—C4	−169.73 (15)
C1—C2—C3—C4	0.5 (2)	C3—C4—C5—N2	−173.27 (18)
C2—C3—C4—C5	179.52 (17)	S1—C4—C5—N2	6.9 (2)
C2—C3—C4—S1	−0.60 (19)	C3—C4—C5—N1	8.5 (3)
C1—S1—C4—C3	0.44 (14)	S1—C4—C5—N1	−171.36 (13)
C1—S1—C4—C5	−179.67 (15)	C5—N1—C6—C7	−17.79 (18)
C7—N2—C5—N1	0.6 (2)	C5—N2—C7—C6	−12.26 (19)
C7—N2—C5—C4	−177.67 (15)	N1—C6—C7—N2	18.12 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···N2ⁱ	0.75	2.23	2.977 (2)	171
C3—H3A···N2ⁱ	0.95	2.60	3.482 (2)	155
C6—H6A···Cg1ⁱⁱ	0.99	2.89	3.539 (2)	124
C6—H6B···Cg1ⁱⁱⁱ	0.99	2.83	3.691 (2)	146

Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x, y+1/2, −z+3/2; (iii) x−1, y, z.

Experimental details

Crystal data
Chemical formula	C₇H₈N₂S
M_r	152.21
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	6.1321 (2), 11.5663 (3), 10.0098 (3)
β (°)	90.154 (1)
V (Å³)	709.95 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.37
Crystal size (mm)	0.54 × 0.28 × 0.22

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.825, 0.922
No. of measured, independent and observed [I > 2σ(I)] reflections	27675, 3100, 3040
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.807

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.128, 1.24
No. of reflections	3100
No. of parameters	91
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.62, −0.39

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···N2ⁱ	0.7500	2.2300	2.977 (2)	171.00
C3—H3A···N2ⁱ	0.9500	2.6000	3.482 (2)	155.00
C6—H6A···Cg1ⁱⁱ	0.9900	2.8900	3.539 (2)	124.00
C6—H6B···Cg1ⁱⁱⁱ	0.9900	2.8300	3.691 (2)	146.00

Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x, y+1/2, −z+3/2; (iii) x−1, y, z.

Acknowledgements

HKF and RK thanks the Malaysian Government and Universiti Sains Malaysia for the Science Fund grant No. 305/PFIZIK/613312. RK thanks Universiti Sains Malaysia for a post-doctoral research fellowship. HK thanks PNU for the financial support. HKF also thanks Universiti Sains Malaysia for the Research University Golden Goose grant No. 1001/PFIZIK/811012.

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