2-[4-(4,5-Dihydro-1H-pyrrol-2-yl)phen­yl]-4,5-dihydro-1H-imidazole

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

doi:10.1107/S160053680803818X

organic compounds

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ISSN: 2056-9890

Volume 64| Part 12| December 2008| Page o2406

doi:10.1107/S160053680803818X

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ADDENDA AND ERRATA

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2-[4-(4,5-Dihydro-1H-pyrrol-2-yl)phenyl]-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 15 November 2008; accepted 17 November 2008; online 22 November 2008)

The molecule of the title compound, C₁₂H₁₄N₄, lies about a crystallographic inversion centre. The five- and six-membered rings are twisted from each other, forming a dihedral angle of 18.06 (7)°. In the crystal structure, neighbouring molecules are linked by intermolecular N—H⋯N hydrogen bonds into one-dimensional infinite chains forming 18-membered rings with R₂²(18) motifs. The crystal structure is further stabilized by weak intermolecular π–π stacking [centroid–centroid distance = 3.8254 (6) Å] and C—H⋯π interactions.

Related literature

For details of hydrogen-bond motifs, see: Bernstein et al. (1995 ). For a related structure and synthesis, see: Stibrany et al. (2004 ). For applications, see: Blancafort (1978 ); Chan (1993 ); Vizi (1986 ); Li et al. (1996 ); Ueno et al. (1995 ); Corey & Grogan (1999 ).

Experimental

Crystal data

C₁₂H₁₄N₄
M_r = 214.27
Triclinic, $[P \overline 1]$
a = 4.8863 (2) Å
b = 5.1472 (2) Å
c = 10.2295 (4) Å
α = 104.414 (2)°
β = 93.885 (2)°
γ = 94.207 (2)°
V = 247.52 (2) Å³
Z = 1
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 100.0 (1) K
0.56 × 0.17 × 0.15 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.950, T_max = 0.986
4616 measured reflections
1296 independent reflections
1208 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.116
S = 1.07
1296 reflections
101 parameters
All H-atom parameters refined
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the N1/C1/C2/N2/C3 imidazoline ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯N2ⁱ	0.87 (2)	2.18 (2)	3.0060 (13)	158.1 (15)
C2—H2B⋯Cg1ⁱⁱ	1.015 (15)	2.980 (15)	3.8882 (11)	149.6 (11)
Symmetry codes: (i) x, y-1, z; (ii) -x, -y+1, -z+1.

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, 2003 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680803818X/tk2331sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680803818X/tk2331Isup2.hkl

checkCIF report

Comment top

Imidazoline derivatives are of great importance because they exhibit significant biological and pharmacological activities including anti-hypertensive (Blancafort 1978), anti-hyperglycemic (Chan 1993), anti-depressive (Vizi 1986), anti-hypercholesterolemic (Li et al., 1996) and anti-inflammatory (Ueno et al., 1995) activities. These compounds are also used as catalysts and synthetic intermediates in some organic reactions (Corey & Grogan 1999). In consideration of the important applications of imidazolines, herein the crystal structure of the title compound, (I), is reported.

In compound (I), Fig. 1, bond lengths and angles are within the normal ranges and are comparable with a related structure (Stibrany et al., 2004). The molecule lies about a crystallographic inversion centre. The five- and six-membered rings are twisted from each other, forming a dihedral angle of 18.06 (7)°. Intermolecular N—H···N hydrogen bonds form 18-membered rings producing R₂²(18) ring motifs to link molecules into one-dimensional infinite chains along the b-axis, Table 1 and Fig. 2. The crystal structure is further stabilized by weak intermolecular π–π stacking [Cg1···Cg2ⁱ = 3.8254 (6) Å; (i) 1 + x, y, z] and C—H···π (Cg1 and Cg2 are the centroids of the N1/C1/C2/N2/C3 imidazoline ring and the benzene ring, respectively) interactions, Table 1.

Related literature top

For details of hydrogen-bond motifs, see: Bernstein et al. (1995). For a related structure and synthesis, see: Stibrany et al. (2004). For applications, see: Blancafort (1978); Chan (1993); Vizi (1986); Li et al. (1996); Ueno et al. (1995); Corey & Grogan (1999).

Experimental top

The synthetic method used for the preparation of (I) was based on previous work (Stibrany et al. 2004), except that 1,4-dicyanobenzene (10 mmol) and ethylenediamine (40 mmol) were used. Single crystals suitable for X-ray diffraction were obtained by evaporation of a methanol solution of (I) held 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, 2003).

Figures top

	Fig. 1. The molecular structure of (I) with atom labels and 50% probability ellipsoids for non-H atoms. Unlabelled atoms are related by -x + 1, -y, -z.
	Fig. 2. Partial crystal packing in (I), viewed down the a-axis showing one-dimensional infinite chains along the b-axis mediated by intermolecular N—H···N interactions (dashed lines).

2-[4-(4,5-Dihydro-1H-pyrrol-2-yl)-phenyl]-4,5-dihydro-1H-imidazole top

Crystal data top

C₁₂H₁₄N₄	Z = 1
M_r = 214.27	F(000) = 114
Triclinic, P1	D_x = 1.437 Mg m⁻³
Hall symbol: -P 1	Melting point: 312 K
a = 4.8863 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 5.1472 (2) Å	Cell parameters from 3789 reflections
c = 10.2295 (4) Å	θ = 2.5–30.3°
α = 104.414 (2)°	µ = 0.09 mm⁻¹
β = 93.885 (2)°	T = 100 K
γ = 94.207 (2)°	Block, colourless
V = 247.52 (2) Å³	0.56 × 0.17 × 0.15 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	1296 independent reflections
Radiation source: fine-focus sealed tube	1208 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
ϕ and ω scans	θ_max = 29.0°, θ_min = 4.1°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −6→6
T_min = 0.950, T_max = 0.986	k = −6→6
4616 measured reflections	l = −13→13

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.116	All H-atom parameters refined
S = 1.07	w = 1/[σ²(F_o²) + (0.0717P)² + 0.0714P] where P = (F_o² + 2F_c²)/3
1296 reflections	(Δ/σ)_max < 0.001
101 parameters	Δρ_max = 0.42 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₁₂H₁₄N₄	γ = 94.207 (2)°
M_r = 214.27	V = 247.52 (2) Å³
Triclinic, P1	Z = 1
a = 4.8863 (2) Å	Mo Kα radiation
b = 5.1472 (2) Å	µ = 0.09 mm⁻¹
c = 10.2295 (4) Å	T = 100 K
α = 104.414 (2)°	0.56 × 0.17 × 0.15 mm
β = 93.885 (2)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	1296 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1208 reflections with I > 2σ(I)
T_min = 0.950, T_max = 0.986	R_int = 0.026
4616 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.116	All H-atom parameters refined
S = 1.07	Δρ_max = 0.42 e Å⁻³
1296 reflections	Δρ_min = −0.24 e Å⁻³
101 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
N1	0.99649 (17)	0.02202 (18)	0.30177 (9)	0.0140 (2)
N2	1.05027 (18)	0.42785 (18)	0.25064 (9)	0.0161 (2)
C1	1.2376 (2)	0.1595 (2)	0.39310 (10)	0.0148 (2)
C2	1.2547 (2)	0.4433 (2)	0.36664 (10)	0.0158 (2)
C3	0.92585 (19)	0.1869 (2)	0.21989 (10)	0.0124 (2)
C4	0.70754 (19)	0.08912 (19)	0.10716 (10)	0.0124 (2)
C5	0.6787 (2)	0.2263 (2)	0.00581 (10)	0.0138 (2)
C6	0.5270 (2)	−0.1391 (2)	0.09997 (10)	0.0135 (2)
H1A	1.402 (3)	0.062 (3)	0.3667 (15)	0.020 (3)*
H1B	1.212 (3)	0.169 (3)	0.4906 (16)	0.024 (4)*
H2A	1.443 (3)	0.498 (3)	0.3429 (16)	0.026 (4)*
H2B	1.214 (3)	0.587 (3)	0.4488 (15)	0.020 (3)*
H5	0.802 (3)	0.383 (3)	0.0096 (16)	0.025 (4)*
H6	0.537 (3)	−0.239 (3)	0.1687 (15)	0.020 (3)*
H1N1	0.989 (3)	−0.151 (4)	0.2656 (17)	0.029 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0135 (4)	0.0131 (4)	0.0147 (4)	−0.0009 (3)	−0.0033 (3)	0.0041 (3)
N2	0.0147 (4)	0.0150 (4)	0.0177 (5)	−0.0009 (3)	−0.0044 (3)	0.0047 (3)
C1	0.0125 (4)	0.0157 (5)	0.0153 (5)	−0.0008 (3)	−0.0030 (3)	0.0037 (4)
C2	0.0144 (5)	0.0153 (5)	0.0167 (5)	−0.0011 (4)	−0.0038 (3)	0.0041 (4)
C3	0.0102 (4)	0.0142 (5)	0.0130 (4)	0.0015 (3)	0.0006 (3)	0.0036 (3)
C4	0.0098 (4)	0.0134 (5)	0.0133 (4)	0.0009 (3)	0.0000 (3)	0.0025 (3)
C5	0.0109 (4)	0.0143 (5)	0.0159 (5)	−0.0009 (3)	0.0001 (3)	0.0041 (3)
C6	0.0128 (4)	0.0140 (5)	0.0142 (5)	0.0002 (3)	0.0003 (3)	0.0049 (3)

Geometric parameters (Å, º) top

N1—C3	1.3780 (13)	C2—H2B	1.015 (15)
N1—C1	1.4700 (12)	C3—C4	1.4787 (13)
N1—H1N1	0.874 (18)	C4—C5	1.3973 (14)
N2—C3	1.2944 (13)	C4—C6	1.4000 (14)
N2—C2	1.4808 (12)	C5—C6ⁱ	1.3881 (13)
C1—C2	1.5479 (14)	C5—H5	0.961 (16)
C1—H1A	0.997 (14)	C6—C5ⁱ	1.3881 (13)
C1—H1B	1.004 (16)	C6—H6	0.970 (15)
C2—H2A	1.006 (16)

C3—N1—C1	107.38 (8)	C1—C2—H2B	112.1 (9)
C3—N1—H1N1	118.4 (11)	H2A—C2—H2B	106.8 (12)
C1—N1—H1N1	119.9 (10)	N2—C3—N1	116.89 (9)
C3—N2—C2	106.43 (8)	N2—C3—C4	123.28 (9)
N1—C1—C2	102.00 (8)	N1—C3—C4	119.77 (9)
N1—C1—H1A	108.9 (8)	C5—C4—C6	118.99 (9)
C2—C1—H1A	112.8 (9)	C5—C4—C3	119.82 (9)
N1—C1—H1B	112.3 (9)	C6—C4—C3	121.19 (9)
C2—C1—H1B	111.4 (9)	C6ⁱ—C5—C4	120.61 (9)
H1A—C1—H1B	109.3 (12)	C6ⁱ—C5—H5	119.7 (9)
N2—C2—C1	106.30 (8)	C4—C5—H5	119.6 (9)
N2—C2—H2A	109.2 (9)	C5ⁱ—C6—C4	120.40 (9)
C1—C2—H2A	111.9 (9)	C5ⁱ—C6—H6	117.6 (9)
N2—C2—H2B	110.6 (8)	C4—C6—H6	122.0 (9)

C3—N1—C1—C2	9.79 (10)	N1—C3—C4—C5	−165.14 (9)
C3—N2—C2—C1	3.06 (11)	N2—C3—C4—C6	−161.93 (10)
N1—C1—C2—N2	−7.84 (10)	N1—C3—C4—C6	15.11 (14)
C2—N2—C3—N1	3.71 (12)	C6—C4—C5—C6ⁱ	0.46 (16)
C2—N2—C3—C4	−179.17 (8)	C3—C4—C5—C6ⁱ	−179.29 (8)
C1—N1—C3—N2	−9.24 (12)	C5—C4—C6—C5ⁱ	−0.46 (16)
C1—N1—C3—C4	173.53 (8)	C3—C4—C6—C5ⁱ	179.29 (8)
N2—C3—C4—C5	17.82 (14)

Symmetry code: (i) −x+1, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···N2ⁱⁱ	0.87 (2)	2.18 (2)	3.0060 (13)	158.1 (15)
C2—H2B···Cg1ⁱⁱⁱ	1.015 (15)	2.980 (15)	3.8882 (11)	149.6 (11)

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₄N₄
M_r	214.27
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	4.8863 (2), 5.1472 (2), 10.2295 (4)
α, β, γ (°)	104.414 (2), 93.885 (2), 94.207 (2)
V (Å³)	247.52 (2)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.56 × 0.17 × 0.15

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.950, 0.986
No. of measured, independent and observed [I > 2σ(I)] reflections	4616, 1296, 1208
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.682

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.116, 1.07
No. of reflections	1296
No. of parameters	101
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.24

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	0.87 (2)	2.18 (2)	3.0060 (13)	158.1 (15)
C2—H2B···Cg1ⁱⁱ	1.015 (15)	2.980 (15)	3.8882 (11)	149.6 (11)

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

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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