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

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

doi:10.1107/S1600536809009106

organic compounds

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ISSN: 2056-9890

Volume 65| Part 4| April 2009| Page o798

doi:10.1107/S1600536809009106

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2-(4-Methoxyphenyl)-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 10 March 2009; accepted 12 March 2009; online 19 March 2009)

In the title molecule, C₁₀H₁₂N₂O, the dihedral angle between the benzene and imidazole rings is 14.86 (16)°. The approximately planar arrangement of the molecule results in a distance of 2.54 Å between an ortho-H atom of the benzene ring and the double-bonded N atom of the imidazole ring. In the crystal structure, symmetry-related molecules are linked by intermolecular N—H⋯N hydrogen bonds into one-dimensional chains extending along the a axis.

Related literature

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

Experimental

Crystal data

C₁₀H₁₂N₂O
M_r = 176.22
Orthorhombic, P n a 2₁
a = 10.0574 (5) Å
b = 13.2532 (7) Å
c = 6.8321 (3) Å
V = 910.67 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 100 K
0.23 × 0.09 × 0.06 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.981, T_max = 0.995
8578 measured reflections
1133 independent reflections
873 reflections with I > 2σ(I)
R_int = 0.049

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.096
S = 1.08
1133 reflections
123 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯N2ⁱ	0.93 (3)	1.95 (3)	2.869 (3)	168 (3)
Symmetry code: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z]$ .

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005); 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/S1600536809009106/lh2787sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809009106/lh2787Isup2.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 anti-inflammatory (Ueno et al., 1995) properties. These compounds are also used as catalysts and synthetic intermediates in some organic reactions (Corey & Grogan 1999). With regards to these 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 with the normal ranges and are comparable with the related structures (Stibrany et al. 2004; Kia et al., 2008, 2009a,b). The molecule is approximately planar with a maximum deviation from the mean plane of the molecule for atom N1 being 0.279 (2) Å. The six- and five-membered rings are twisted from each other, forming the dihedral angle of 14.86 (16)°. Atom H5A of the benzene ring is in close proximity to atom N2 atom of the imidazoline ring with a distance of 2.54 Å [N2···H5A]. In the crystal structure, neighbouring molecules are linked together by intermolecular N—H···N hydrogen bonds into 1-D extended chains along the a axis (Table 1, Fig. 2).

Related literature top

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

For related literature, see: Allen et al. (1987).

Experimental top

The synthetic method was based on the previous work (Stibrany et al. 2004), except that 10 mmol of 4-methoxy-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: APEX2 (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 the title compound with atom labels and 50% probability ellipsoids for non-H atoms.
	Fig. 2. Part of the crystal structure of the title compound, viewed along the b-axis showing a 1-D extended chain along the a-axis formed by intermolecular N—H···N hydrogen bonds (dashed lines).

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

Crystal data top

C₁₀H₁₂N₂O	F(000) = 376
M_r = 176.22	D_x = 1.285 Mg m⁻³
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 2309 reflections
a = 10.0574 (5) Å	θ = 2.5–30.0°
b = 13.2532 (7) Å	µ = 0.09 mm⁻¹
c = 6.8321 (3) Å	T = 100 K
V = 910.67 (8) Å³	Block, colourless
Z = 4	0.23 × 0.09 × 0.06 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	1133 independent reflections
Radiation source: fine-focus sealed tube	873 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.049
ϕ and ω scans	θ_max = 27.5°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −13→12
T_min = 0.981, T_max = 0.995	k = −12→17
8578 measured reflections	l = −8→8

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.096	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0375P)² + 0.2936P] where P = (F_o² + 2F_c²)/3
1133 reflections	(Δ/σ)_max < 0.001
123 parameters	Δρ_max = 0.22 e Å⁻³
1 restraint	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₁₀H₁₂N₂O	V = 910.67 (8) Å³
M_r = 176.22	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 10.0574 (5) Å	µ = 0.09 mm⁻¹
b = 13.2532 (7) Å	T = 100 K
c = 6.8321 (3) Å	0.23 × 0.09 × 0.06 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	1133 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	873 reflections with I > 2σ(I)
T_min = 0.981, T_max = 0.995	R_int = 0.049
8578 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	1 restraint
wR(F²) = 0.096	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.22 e Å⁻³
1133 reflections	Δρ_min = −0.22 e Å⁻³
123 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
O1	0.6844 (2)	0.00507 (17)	−0.4396 (3)	0.0302 (6)
N1	0.6252 (2)	0.28654 (19)	0.3242 (4)	0.0270 (6)
N2	0.8459 (2)	0.25758 (18)	0.3284 (4)	0.0219 (5)
C1	0.8179 (3)	0.3256 (3)	0.4948 (4)	0.0234 (7)
H1A	0.8555	0.3935	0.4702	0.028*
H1B	0.8571	0.2985	0.6169	0.028*
C2	0.6653 (3)	0.3309 (3)	0.5111 (4)	0.0233 (7)
H2A	0.6321	0.2909	0.6233	0.028*
H2B	0.6339	0.4014	0.5236	0.028*
C3	0.7329 (3)	0.2397 (2)	0.2447 (4)	0.0176 (6)
C4	0.7204 (3)	0.1776 (2)	0.0662 (4)	0.0178 (6)
C5	0.5988 (3)	0.1384 (2)	0.0039 (4)	0.0184 (6)
H5A	0.5208	0.1512	0.0784	0.022*
C6	0.5902 (3)	0.0813 (2)	−0.1641 (4)	0.0227 (7)
H6A	0.5067	0.0551	−0.2044	0.027*
C7	0.7032 (3)	0.0620 (2)	−0.2748 (4)	0.0218 (7)
C8	0.8257 (3)	0.0985 (2)	−0.2139 (4)	0.0236 (7)
H8A	0.9036	0.0844	−0.2876	0.028*
C9	0.8332 (3)	0.1557 (3)	−0.0444 (4)	0.0232 (7)
H9A	0.9172	0.1805	−0.0026	0.028*
C10	0.7990 (3)	−0.0211 (3)	−0.5514 (4)	0.0319 (8)
H10A	0.7722	−0.0624	−0.6637	0.048*
H10B	0.8609	−0.0594	−0.4694	0.048*
H10C	0.8425	0.0405	−0.5981	0.048*
H1N1	0.537 (3)	0.266 (2)	0.310 (6)	0.043 (10)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0298 (12)	0.0350 (14)	0.0258 (10)	−0.0013 (10)	0.0007 (10)	−0.0112 (10)
N1	0.0167 (13)	0.0387 (17)	0.0257 (12)	0.0020 (12)	−0.0016 (12)	−0.0098 (14)
N2	0.0188 (12)	0.0275 (14)	0.0194 (10)	−0.0002 (11)	−0.0020 (11)	−0.0019 (12)
C1	0.0236 (15)	0.0274 (18)	0.0192 (13)	−0.0035 (14)	−0.0023 (14)	0.0011 (12)
C2	0.0231 (14)	0.0282 (18)	0.0187 (13)	−0.0005 (14)	−0.0016 (13)	−0.0036 (12)
C3	0.0192 (15)	0.0186 (16)	0.0150 (11)	−0.0016 (13)	−0.0017 (12)	0.0053 (12)
C4	0.0183 (15)	0.0192 (16)	0.0157 (12)	−0.0006 (13)	−0.0003 (12)	0.0044 (13)
C5	0.0160 (14)	0.0203 (17)	0.0189 (12)	0.0011 (12)	−0.0008 (11)	0.0024 (12)
C6	0.0182 (15)	0.0253 (17)	0.0247 (13)	−0.0028 (13)	−0.0042 (13)	0.0030 (14)
C7	0.0254 (17)	0.0239 (18)	0.0159 (13)	−0.0003 (14)	−0.0004 (12)	−0.0016 (13)
C8	0.0220 (16)	0.0284 (18)	0.0204 (13)	0.0007 (13)	0.0060 (13)	−0.0007 (14)
C9	0.0177 (16)	0.0304 (19)	0.0215 (14)	−0.0056 (14)	−0.0023 (12)	0.0023 (13)
C10	0.039 (2)	0.034 (2)	0.0227 (16)	0.0027 (16)	0.0053 (14)	−0.0100 (15)

Geometric parameters (Å, º) top

O1—C7	1.368 (3)	C4—C9	1.393 (4)
O1—C10	1.425 (4)	C4—C5	1.396 (4)
N1—C3	1.361 (4)	C5—C6	1.377 (4)
N1—C2	1.463 (4)	C5—H5A	0.9500
N1—H1N1	0.94 (3)	C6—C7	1.389 (4)
N2—C3	1.294 (3)	C6—H6A	0.9500
N2—C1	1.478 (4)	C7—C8	1.387 (4)
C1—C2	1.541 (4)	C8—C9	1.386 (4)
C1—H1A	0.9900	C8—H8A	0.9500
C1—H1B	0.9900	C9—H9A	0.9500
C2—H2A	0.9900	C10—H10A	0.9800
C2—H2B	0.9900	C10—H10B	0.9800
C3—C4	1.476 (4)	C10—H10C	0.9800

C7—O1—C10	117.6 (2)	C5—C4—C3	122.2 (3)
C3—N1—C2	108.2 (2)	C6—C5—C4	120.9 (3)
C3—N1—H1N1	126 (2)	C6—C5—H5A	119.6
C2—N1—H1N1	118 (3)	C4—C5—H5A	119.6
C3—N2—C1	106.6 (2)	C5—C6—C7	120.3 (3)
N2—C1—C2	105.8 (2)	C5—C6—H6A	119.9
N2—C1—H1A	110.6	C7—C6—H6A	119.9
C2—C1—H1A	110.6	O1—C7—C8	124.2 (3)
N2—C1—H1B	110.6	O1—C7—C6	115.9 (3)
C2—C1—H1B	110.6	C8—C7—C6	119.9 (2)
H1A—C1—H1B	108.7	C9—C8—C7	119.3 (3)
N1—C2—C1	101.1 (2)	C9—C8—H8A	120.3
N1—C2—H2A	111.5	C7—C8—H8A	120.3
C1—C2—H2A	111.5	C8—C9—C4	121.5 (3)
N1—C2—H2B	111.5	C8—C9—H9A	119.2
C1—C2—H2B	111.5	C4—C9—H9A	119.2
H2A—C2—H2B	109.4	O1—C10—H10A	109.5
N2—C3—N1	116.0 (2)	O1—C10—H10B	109.5
N2—C3—C4	122.8 (3)	H10A—C10—H10B	109.5
N1—C3—C4	121.1 (2)	O1—C10—H10C	109.5
C9—C4—C5	118.1 (3)	H10A—C10—H10C	109.5
C9—C4—C3	119.7 (3)	H10B—C10—H10C	109.5

C3—N2—C1—C2	8.4 (3)	C3—C4—C5—C6	179.5 (3)
C3—N1—C2—C1	14.4 (3)	C4—C5—C6—C7	−0.1 (4)
N2—C1—C2—N1	−13.7 (3)	C10—O1—C7—C8	2.3 (4)
C1—N2—C3—N1	1.0 (3)	C10—O1—C7—C6	−176.7 (3)
C1—N2—C3—C4	177.3 (3)	C5—C6—C7—O1	−179.7 (2)
C2—N1—C3—N2	−10.7 (3)	C5—C6—C7—C8	1.3 (4)
C2—N1—C3—C4	172.9 (3)	O1—C7—C8—C9	179.9 (3)
N2—C3—C4—C9	−15.1 (4)	C6—C7—C8—C9	−1.2 (4)
N1—C3—C4—C9	161.0 (3)	C7—C8—C9—C4	−0.2 (4)
N2—C3—C4—C5	164.1 (3)	C5—C4—C9—C8	1.4 (4)
N1—C3—C4—C5	−19.8 (4)	C3—C4—C9—C8	−179.4 (3)
C9—C4—C5—C6	−1.3 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···N2ⁱ	0.93 (3)	1.95 (3)	2.869 (3)	168 (3)

Symmetry code: (i) x−1/2, −y+1/2, z.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₂N₂O
M_r	176.22
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	100
a, b, c (Å)	10.0574 (5), 13.2532 (7), 6.8321 (3)
V (Å³)	910.67 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.23 × 0.09 × 0.06

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.981, 0.995
No. of measured, independent and observed [I > 2σ(I)] reflections	8578, 1133, 873
R_int	0.049
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.096, 1.08
No. of reflections	1133
No. of parameters	123
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.22

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	0.93 (3)	1.95 (3)	2.869 (3)	168 (3)

Symmetry code: (i) x−1/2, −y+1/2, z.

Acknowledgements

HKF and RK thank the Malaysian government and Universiti Sains Malaysia for a Science Fund grant (No. 305/PFIZIK/613312). RK thanks Universiti Sains Malaysia for a postdoctoral research fellowship. HK thanks PNU for financial support. HKF also thanks Universiti Sains Malaysia for a Research University Golden Goose grant (No. 1001/PFIZIK/811012).

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