2-p-Tolyl-4,5-dihydro-1H-imidazole

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

doi:10.1107/S1600536809008125

organic compounds

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ISSN: 2056-9890

Volume 65| Part 4| April 2009| Page o724

doi:10.1107/S1600536809008125

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2-p-Tolyl-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 3 March 2009; accepted 5 March 2009; online 11 March 2009)

In the molecule of the title compound, C₁₀H₁₂N₂, the six- and five-membered rings are almost co-planar, forming a dihedral angle of 3.56 (8)°. In the crystal structure, neighbouring molecules are linked together by intermolecular N—H⋯N hydrogen bonds into one-dimensional infinite chains along the c axis. The crystal structure, is further stabilized by weak intermolecular C—H⋯π and π–π stacking [centroid–centroid distance = 3.8892 (9) Å] interactions.

Related literature

For bond-length data, see: Allen et al. (1987 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ). For related structures and syntheses, see, Stibrany et al. (2004 ); Kia et al., 2008 , 2009 ). For applications of imidazoline derivatives, see, for example: Blancafort (1978 ); Chan (1993 ); Vizi (1986 ); Li et al. (1996 ); Ueno et al., (1995 ); Corey & Grogan (1999 ). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ).

Experimental

Crystal data

C₁₀H₁₂N₂
M_r = 160.22
Monoclinic, C c
a = 5.1134 (1) Å
b = 16.4020 (4) Å
c = 10.1712 (2) Å
β = 94.293 (1)°
V = 850.66 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 100 K
0.47 × 0.12 × 0.09 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.883, T_max = 0.993
8503 measured reflections
1423 independent reflections
1338 reflections with I > 2˘I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.102
S = 1.08
1423 reflections
114 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯N2ⁱ	0.87 (3)	2.06 (3)	2.9224 (18)	170 (2)
C10—H10B⋯Cg1ⁱⁱ	0.96	2.88	3.8110 (16)	163
Symmetry codes: (i) $[x, -y, z-{\script{1\over 2}}]$ ; (ii) x+1, y, z. Cg1 is the cetroid of the N1/C2/C1/N2/C3 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, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809008125/at2738sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809008125/at2738Isup2.hkl

checkCIF report

Comment top

Imidazoline derivatives are of great importance because they exhibit significant biological and pharmacological activities such as antihypertensive (Blancafort 1978), antihyperglycemic (Chan 1993), antidepressive (Vizi 1986), antihypercholesterolemic (Li et al., 1996) and antiinflammatory (Ueno et al., 1995). These compounds are also used as catalysts and synthetic intermediates in some organic reactions (Corey & Grogan 1999). With regards to the important applications of imidazolines, herein 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, 2009). The molecule is almost planar with a maximum deviation from the mean plane of the molecule for C2 atom being -0.176 (19) Å. The six- and five-membered rings are twisted from each other, forming the dihedral angle of 3.56 (8)°. The interesting feature of the crystal structure is the short C2···C10ⁱ contact [3.368 (2) Å; (i) 1 + x, y, z], which is shorter than the sum of the van der Waals radius of carbon atom. In the crystal structure, neighbouring molecules are linked together by intermolecular N—H···N hydrogen bonds into 1-D infinite chains along the c axis (Table 1, Fig. 2). The crystal structure is further stabilized by weak intermolecular π-π stacking [Cg1···Cg2ⁱⁱⁱ = 3.8892 Å; (iii) -1 + x, y, z] and C—H···π interactions (Cg1 and Cg2 are the centroids of the N1/C2/C1/N2/C3-imidazoline and the benzene rings, respectiverly).

Related literature top

For bond-length data, see: Allen et al. (1987). For hydrogen-bond motifs, see: Bernstein et al. (1995). For related structures and syntheses, see, Stibrany et al. (2004); Kia et al., 2008, 2009). For applications of imidazoline derivatives, see, for example: Blancafort (1978); Chan (1993); Vizi (1986); Li et al. (1996); Ueno et al., (1995); Corey & Grogan (1999). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986). Cg1 is the cetroid of the N1/C2/C1/N2/C3 ring.

Experimental top

The synthetic method was based on the previous work (Stibrany et al. 2004), except that 10 mmol of 4-methyl cyanobenzene and 40 mmol of ethylenediamine was used. Single crystals suitable for X-ray diffraction were obtained by evaporation of an methanol 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, 2009).

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 a 1-D infinite chain along the c-axis by intermolecular N—H···N interactions. The intermolecular interactions are shown as dashed lines.

2-p-Tolyl-4,5-dihydro-1H-imidazole top

Crystal data top

C₁₀H₁₂N₂	F(000) = 344
M_r = 160.22	D_x = 1.251 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 3821 reflections
a = 5.1134 (1) Å	θ = 2.5–31.5°
b = 16.4020 (4) Å	µ = 0.08 mm⁻¹
c = 10.1712 (2) Å	T = 100 K
β = 94.293 (1)°	Needle, colourless
V = 850.66 (3) Å³	0.47 × 0.12 × 0.09 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	1423 independent reflections
Radiation source: fine-focus sealed tube	1338 reflections with I > 2˘I)
Graphite monochromator	R_int = 0.031
ϕ and ω scans	θ_max = 31.5°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −7→7
T_min = 0.883, T_max = 0.993	k = −24→24
8503 measured reflections	l = −14→14

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.102	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0699P)² + 0.0868P] where P = (F_o² + 2F_c²)/3
1423 reflections	(Δ/σ)_max < 0.001
114 parameters	Δρ_max = 0.33 e Å⁻³
2 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₀H₁₂N₂	V = 850.66 (3) Å³
M_r = 160.22	Z = 4
Monoclinic, Cc	Mo Kα radiation
a = 5.1134 (1) Å	µ = 0.08 mm⁻¹
b = 16.4020 (4) Å	T = 100 K
c = 10.1712 (2) Å	0.47 × 0.12 × 0.09 mm
β = 94.293 (1)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	1423 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1338 reflections with I > 2˘I)
T_min = 0.883, T_max = 0.993	R_int = 0.031
8503 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	2 restraints
wR(F²) = 0.102	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.33 e Å⁻³
1423 reflections	Δρ_min = −0.21 e Å⁻³
114 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cyrosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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
N2	−0.2547 (3)	−0.01211 (8)	1.08200 (13)	0.0175 (3)
N1	−0.2444 (3)	−0.02899 (8)	0.86191 (12)	0.0189 (3)
C1	−0.4382 (3)	−0.07930 (9)	1.04580 (15)	0.0190 (3)
H1A	−0.6091	−0.0684	1.0774	0.023*
H1B	−0.3728	−0.1303	1.0837	0.023*
C2	−0.4570 (3)	−0.08371 (9)	0.89368 (15)	0.0181 (3)
H2A	−0.4279	−0.1388	0.8631	0.022*
H2B	−0.6256	−0.0644	0.8561	0.022*
C3	−0.1632 (3)	0.01280 (8)	0.97337 (13)	0.0142 (3)
C4	0.0262 (3)	0.08065 (8)	0.96924 (15)	0.0141 (2)
C5	0.1072 (3)	0.12199 (9)	1.08498 (14)	0.0189 (3)
H5A	0.0404	0.1069	1.1640	0.023*
C6	0.2870 (3)	0.18556 (9)	1.08343 (15)	0.0201 (3)
H6A	0.3393	0.2125	1.1615	0.024*
C7	0.3900 (3)	0.20952 (8)	0.96598 (14)	0.0171 (3)
C8	0.3049 (3)	0.16917 (9)	0.85050 (15)	0.0216 (3)
H8A	0.3690	0.1851	0.7712	0.026*
C9	0.1253 (3)	0.10529 (9)	0.85124 (15)	0.0202 (3)
H9A	0.0712	0.0790	0.7729	0.024*
C10	0.5915 (3)	0.27668 (9)	0.96448 (17)	0.0229 (3)
H10A	0.5467	0.3127	0.8918	0.034*
H10B	0.7613	0.2534	0.9550	0.034*
H10C	0.5946	0.3067	1.0456	0.034*
H1N1	−0.233 (5)	−0.0121 (14)	0.781 (3)	0.031 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N2	0.0216 (6)	0.0188 (5)	0.0123 (5)	−0.0046 (5)	0.0029 (5)	0.0002 (4)
N1	0.0257 (7)	0.0208 (6)	0.0103 (5)	−0.0085 (5)	0.0011 (5)	−0.0010 (4)
C1	0.0227 (7)	0.0211 (6)	0.0134 (6)	−0.0059 (5)	0.0035 (5)	0.0005 (5)
C2	0.0201 (7)	0.0197 (6)	0.0145 (6)	−0.0052 (5)	0.0007 (5)	−0.0002 (5)
C3	0.0157 (6)	0.0148 (6)	0.0123 (6)	0.0002 (5)	0.0014 (5)	−0.0002 (4)
C4	0.0156 (6)	0.0147 (5)	0.0118 (5)	−0.0008 (4)	0.0004 (4)	0.0003 (4)
C5	0.0251 (8)	0.0204 (6)	0.0111 (6)	−0.0053 (6)	0.0009 (5)	0.0015 (5)
C6	0.0252 (8)	0.0224 (6)	0.0122 (6)	−0.0067 (6)	−0.0025 (6)	−0.0001 (5)
C7	0.0169 (7)	0.0173 (6)	0.0171 (6)	−0.0031 (5)	0.0011 (5)	0.0012 (5)
C8	0.0260 (8)	0.0233 (7)	0.0164 (6)	−0.0081 (6)	0.0076 (6)	−0.0009 (5)
C9	0.0257 (8)	0.0219 (6)	0.0134 (6)	−0.0074 (6)	0.0048 (5)	−0.0024 (5)
C10	0.0211 (8)	0.0226 (6)	0.0249 (7)	−0.0078 (6)	0.0008 (6)	0.0013 (6)

Geometric parameters (Å, º) top

N2—C3	1.2976 (17)	C5—C6	1.391 (2)
N2—C1	1.4763 (19)	C5—H5A	0.9300
N1—C3	1.3627 (17)	C6—C7	1.3975 (19)
N1—C2	1.4641 (19)	C6—H6A	0.9300
N1—H1N1	0.87 (3)	C7—C8	1.389 (2)
C1—C2	1.5447 (19)	C7—C10	1.5092 (19)
C1—H1A	0.9700	C8—C9	1.394 (2)
C1—H1B	0.9700	C8—H8A	0.9300
C2—H2A	0.9700	C9—H9A	0.9300
C2—H2B	0.9700	C10—H10A	0.9600
C3—C4	1.4779 (18)	C10—H10B	0.9600
C4—C5	1.394 (2)	C10—H10C	0.9600
C4—C9	1.397 (2)

C3—N2—C1	106.60 (12)	C6—C5—C4	120.66 (13)
C3—N1—C2	108.04 (12)	C6—C5—H5A	119.7
C3—N1—H1N1	125.8 (17)	C4—C5—H5A	119.7
C2—N1—H1N1	120.4 (18)	C5—C6—C7	120.80 (13)
N2—C1—C2	105.98 (12)	C5—C6—H6A	119.6
N2—C1—H1A	110.5	C7—C6—H6A	119.6
C2—C1—H1A	110.5	C8—C7—C6	118.33 (13)
N2—C1—H1B	110.5	C8—C7—C10	120.66 (13)
C2—C1—H1B	110.5	C6—C7—C10	121.01 (13)
H1A—C1—H1B	108.7	C7—C8—C9	121.21 (13)
N1—C2—C1	101.59 (11)	C7—C8—H8A	119.4
N1—C2—H2A	111.5	C9—C8—H8A	119.4
C1—C2—H2A	111.5	C8—C9—C4	120.25 (14)
N1—C2—H2B	111.5	C8—C9—H9A	119.9
C1—C2—H2B	111.5	C4—C9—H9A	119.9
H2A—C2—H2B	109.3	C7—C10—H10A	109.5
N2—C3—N1	116.31 (12)	C7—C10—H10B	109.5
N2—C3—C4	122.68 (12)	H10A—C10—H10B	109.5
N1—C3—C4	120.98 (12)	C7—C10—H10C	109.5
C5—C4—C9	118.72 (12)	H10A—C10—H10C	109.5
C5—C4—C3	119.75 (13)	H10B—C10—H10C	109.5
C9—C4—C3	121.53 (13)

C3—N2—C1—C2	−5.19 (16)	C9—C4—C5—C6	−1.2 (2)
C3—N1—C2—C1	−11.95 (15)	C3—C4—C5—C6	179.46 (14)
N2—C1—C2—N1	10.31 (15)	C4—C5—C6—C7	0.1 (2)
C1—N2—C3—N1	−2.84 (18)	C5—C6—C7—C8	1.1 (2)
C1—N2—C3—C4	179.35 (13)	C5—C6—C7—C10	−178.05 (14)
C2—N1—C3—N2	10.16 (18)	C6—C7—C8—C9	−1.2 (2)
C2—N1—C3—C4	−171.99 (13)	C10—C7—C8—C9	177.91 (14)
N2—C3—C4—C5	−1.8 (2)	C7—C8—C9—C4	0.2 (2)
N1—C3—C4—C5	−179.56 (14)	C5—C4—C9—C8	1.0 (2)
N2—C3—C4—C9	178.80 (15)	C3—C4—C9—C8	−179.62 (14)
N1—C3—C4—C9	1.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···N2ⁱ	0.87 (3)	2.06 (3)	2.9224 (18)	170 (2)
C10—H10B···Cg1ⁱⁱ	0.96	2.88	3.8110 (16)	163

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

Experimental details

Crystal data
Chemical formula	C₁₀H₁₂N₂
M_r	160.22
Crystal system, space group	Monoclinic, Cc
Temperature (K)	100
a, b, c (Å)	5.1134 (1), 16.4020 (4), 10.1712 (2)
β (°)	94.293 (1)
V (Å³)	850.66 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.47 × 0.12 × 0.09

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.883, 0.993
No. of measured, independent and observed [I > 2˘I)] reflections	8503, 1423, 1338
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.735

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.102, 1.08
No. of reflections	1423
No. of parameters	114
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.21

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···N2ⁱ	0.87 (3)	2.06 (3)	2.9224 (18)	170 (2)
C10—H10B···Cg1ⁱⁱ	0.96	2.88	3.8110 (16)	163

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

Acknowledgements

HKF and RK thank 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 financial support. HKF also thanks Universiti Sains Malaysia for the Research University Golden Goose grant No. 1001/PFIZIK/811012.

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