2-(3-Chloro­phen­yl)-4,5-dihydro-1H-imidazole

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

doi:10.1107/S1600536809001214

organic compounds

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ISSN: 2056-9890

Volume 65| Part 2| February 2009| Pages o338-o339

doi:10.1107/S1600536809001214

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2-(3-Chlorophenyl)-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 6 January 2009; accepted 10 January 2009; online 17 January 2009)

In the title compound, C₉H₉ClN₂, a substituted imidazoline, the six- and five-membered rings are twisted from each other, making a dihedral angle of 17.07 (5)°. In the crystal structure, a short Cl⋯Cl [3.3540 (3) Å] interaction is observed. Neighbouring molecules are linked together by intermolecular N—H⋯N hydrogen bonds into a one-dimensional infinite chain along the [101] direction and short Cl⋯Cl contacts link the chains into a three-dimensional network. There is also a significant π-stacking interaction between the planar sections of the six- and five-membered rings.

Related literature

For bond-length data, see: Allen et al. (1987 ). For a related structure and the synthesis, see: Stibrany et al. (2004 ); Kia et al. (2008 ). For the biological and pharmacological activities 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

C₉H₉ClN₂
M_r = 180.63
Orthorhombic, F d d 2
a = 19.7329 (8) Å
b = 39.1479 (18) Å
c = 4.3493 (2) Å
V = 3359.8 (3) Å³
Z = 16
Mo Kα radiation
μ = 0.39 mm⁻¹
T = 100.0 (1) K
0.51 × 0.50 × 0.09 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.825, T_max = 0.964
14166 measured reflections
3438 independent reflections
3224 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.072
S = 1.10
3438 reflections
113 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.15 e Å⁻³
Absolute structure: Flack (1983 ), 1429 Friedel pairs
Flack parameter: −0.05 (4)

Table 1
Selected interatomic distances (Å)

Cl1⋯Cl1ⁱ	3.3540 (3)
C1⋯C3ⁱⁱ	3.3945 (12)
C1⋯C4ⁱⁱ	3.3301 (15)
C4⋯C6ⁱⁱⁱ	3.3997 (15)
C5⋯C7ⁱⁱⁱ	3.3716 (12)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z]$ ; (ii) x, y, z+1; (iii) x, y, z-1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯N2^iv	0.896 (16)	2.118 (16)	3.0113 (11)	174.5 (15)
Symmetry code: (iv) $[x-{\script{1\over 4}}, -y+{\script{1\over 4}}, z-{\script{1\over 4}}]$ .

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/S1600536809001214/is2379sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809001214/is2379Isup2.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 (Ueno et al., 1995) properties. 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 (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 six- and five-membered rings are not coplanar and are twisted from each other by a dihedral angle of 18.07 (5)°. The interesting feature of the crystal structure is the short Cl···Cl [3.3540 (3) Å] (Table 1) which is shorter than the sum of the van der Waals radius of this atom. In the crystal structure (Fig. 2), neighbouring molecules are linked together by intermolecular N—H···N hydrogen bonds (Table 2) into 1-D infinite chains along the [1 0 1] direction and short Cl···Cl contacts link these chains into a 3-D network. There is also a significant π-stacking interaction between the planar sections associated with C1–C3–C4–C5–C6 and C7 of the six- and five-membered rings respectively (Table 1).

Related literature top

For bond-length data, see: Allen et al. (1987). For a related structure and the synthesis, see: Stibrany et al. (2004); Kia et al. (2008). For the biological and pharmacological activities, 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 3-chloro-2-cyanobenzene and 40 mmol of ethylenediamine were used. Single crystals suitable for X-ray diffraction were obtained by evaporation of an acetonitrile 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 c-axis showing linking of molecules through intermolecular N—H···N hydrogen bonds and short Cl···Cl interactions. The intermolecular interactions are shown as dashed lines.

2-(3-Chlorophenyl)-4,5-dihydro-1H-imidazole top

Crystal data top

C₉H₉ClN₂	F(000) = 1504
M_r = 180.63	D_x = 1.428 Mg m⁻³
Orthorhombic, Fdd2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2d	Cell parameters from 8962 reflections
a = 19.7329 (8) Å	θ = 2.9–36.7°
b = 39.1479 (18) Å	µ = 0.39 mm⁻¹
c = 4.3493 (2) Å	T = 100 K
V = 3359.8 (3) Å³	Block, colourless
Z = 16	0.51 × 0.50 × 0.09 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	3438 independent reflections
Radiation source: fine-focus sealed tube	3224 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ϕ and ω scans	θ_max = 35.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −31→25
T_min = 0.825, T_max = 0.964	k = −60→60
14166 measured reflections	l = −6→6

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.027	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.072	w = 1/[σ²(F_o²) + (0.037P)² + 1.1492P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max = 0.001
3438 reflections	Δρ_max = 0.33 e Å⁻³
113 parameters	Δρ_min = −0.15 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1429 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.05 (4)

Crystal data top

C₉H₉ClN₂	V = 3359.8 (3) Å³
M_r = 180.63	Z = 16
Orthorhombic, Fdd2	Mo Kα radiation
a = 19.7329 (8) Å	µ = 0.39 mm⁻¹
b = 39.1479 (18) Å	T = 100 K
c = 4.3493 (2) Å	0.51 × 0.50 × 0.09 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	3438 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	3224 reflections with I > 2σ(I)
T_min = 0.825, T_max = 0.964	R_int = 0.025
14166 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.072	Δρ_max = 0.33 e Å⁻³
S = 1.10	Δρ_min = −0.15 e Å⁻³
3438 reflections	Absolute structure: Flack (1983), 1429 Friedel pairs
113 parameters	Absolute structure parameter: −0.05 (4)
1 restraint

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
Cl1	0.165233 (12)	0.246951 (6)	0.02330 (7)	0.02846 (7)
N1	0.00209 (4)	0.10678 (2)	0.1715 (2)	0.01782 (15)
N2	0.11053 (4)	0.11676 (2)	0.3205 (2)	0.01792 (15)
C1	0.10570 (4)	0.18532 (2)	0.0803 (2)	0.01732 (16)
H1A	0.1405	0.1803	0.2172	0.021*
C2	0.10314 (4)	0.21685 (2)	−0.0634 (2)	0.01837 (17)
C3	0.05234 (5)	0.22529 (2)	−0.2708 (2)	0.01901 (17)
H3A	0.0517	0.2465	−0.3667	0.023*
C4	0.00232 (5)	0.20104 (3)	−0.3313 (3)	0.01959 (17)
H4A	−0.0323	0.2062	−0.4686	0.024*
C5	0.00358 (5)	0.16926 (2)	−0.1890 (2)	0.01739 (16)
H5A	−0.0301	0.1533	−0.2313	0.021*
C6	0.05544 (4)	0.16118 (2)	0.0174 (2)	0.01498 (14)
C7	0.05755 (4)	0.12791 (2)	0.1766 (2)	0.01505 (15)
C8	0.01553 (5)	0.07848 (3)	0.3841 (3)	0.02052 (18)
H8A	0.0053	0.0566	0.2907	0.025*
H8B	−0.0102	0.0809	0.5728	0.025*
C9	0.09225 (5)	0.08268 (3)	0.4421 (3)	0.02013 (18)
H9A	0.1021	0.0813	0.6602	0.024*
H9B	0.1175	0.0650	0.3364	0.024*
H1N1	−0.0392 (8)	0.1159 (4)	0.148 (4)	0.036 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.01974 (10)	0.01899 (11)	0.04665 (16)	−0.00554 (8)	−0.00483 (11)	0.00392 (11)
N1	0.0124 (3)	0.0167 (4)	0.0244 (4)	−0.0016 (3)	−0.0022 (3)	0.0014 (3)
N2	0.0132 (3)	0.0161 (3)	0.0245 (4)	0.0007 (3)	−0.0013 (3)	0.0019 (3)
C1	0.0122 (3)	0.0165 (4)	0.0232 (4)	0.0008 (3)	−0.0002 (3)	−0.0003 (3)
C2	0.0139 (3)	0.0166 (4)	0.0246 (4)	−0.0010 (3)	0.0019 (3)	−0.0004 (3)
C3	0.0189 (4)	0.0171 (4)	0.0210 (4)	0.0013 (3)	0.0025 (3)	0.0013 (3)
C4	0.0180 (4)	0.0211 (4)	0.0196 (4)	0.0016 (3)	−0.0018 (3)	0.0000 (3)
C5	0.0148 (3)	0.0192 (4)	0.0181 (4)	0.0000 (3)	−0.0006 (3)	−0.0007 (3)
C6	0.0120 (3)	0.0149 (4)	0.0180 (4)	0.0012 (3)	0.0018 (3)	−0.0014 (3)
C7	0.0117 (3)	0.0158 (4)	0.0177 (4)	−0.0003 (3)	0.0011 (3)	−0.0016 (3)
C8	0.0164 (4)	0.0188 (4)	0.0264 (4)	−0.0021 (3)	−0.0011 (3)	0.0042 (3)
C9	0.0159 (4)	0.0184 (4)	0.0260 (5)	0.0002 (3)	−0.0008 (3)	0.0039 (3)

Geometric parameters (Å, º) top

Cl1—C2	1.7413 (10)	C3—H3A	0.9300
N1—C7	1.3719 (12)	C4—C5	1.3897 (14)
N1—C8	1.4675 (13)	C4—H4A	0.9300
N1—H1N1	0.896 (16)	C5—C6	1.3976 (13)
N2—C7	1.2942 (12)	C5—H5A	0.9300
N2—C9	1.4799 (13)	C6—C7	1.4759 (13)
C1—C2	1.3844 (14)	C8—C9	1.5436 (13)
C1—C6	1.3969 (12)	C8—H8A	0.9700
C1—H1A	0.9300	C8—H8B	0.9700
C2—C3	1.3884 (14)	C9—H9A	0.9700
C3—C4	1.3944 (14)	C9—H9B	0.9700

Cl1···Cl1ⁱ	3.3540 (3)	C4···C6ⁱⁱⁱ	3.3997 (15)
C1···C3ⁱⁱ	3.3945 (12)	C5···C7ⁱⁱⁱ	3.3716 (12)
C1···C4ⁱⁱ	3.3301 (15)

C7—N1—C8	107.50 (7)	C1—C6—C5	119.51 (8)
C7—N1—H1N1	119.1 (10)	C1—C6—C7	119.03 (8)
C8—N1—H1N1	122.5 (11)	C5—C6—C7	121.45 (8)
C7—N2—C9	106.25 (7)	N2—C7—N1	116.68 (8)
C2—C1—C6	119.26 (9)	N2—C7—C6	123.17 (8)
C2—C1—H1A	120.4	N1—C7—C6	120.13 (8)
C6—C1—H1A	120.4	N1—C8—C9	101.53 (7)
C1—C2—C3	122.13 (9)	N1—C8—H8A	111.5
C1—C2—Cl1	118.68 (7)	C9—C8—H8A	111.5
C3—C2—Cl1	119.19 (8)	N1—C8—H8B	111.5
C2—C3—C4	118.15 (9)	C9—C8—H8B	111.5
C2—C3—H3A	120.9	H8A—C8—H8B	109.3
C4—C3—H3A	120.9	N2—C9—C8	106.06 (8)
C5—C4—C3	120.84 (9)	N2—C9—H9A	110.5
C5—C4—H4A	119.6	C8—C9—H9A	110.5
C3—C4—H4A	119.6	N2—C9—H9B	110.5
C4—C5—C6	120.12 (8)	C8—C9—H9B	110.5
C4—C5—H5A	119.9	H9A—C9—H9B	108.7
C6—C5—H5A	119.9

C6—C1—C2—C3	−0.48 (14)	C9—N2—C7—C6	−179.11 (8)
C6—C1—C2—Cl1	178.76 (7)	C8—N1—C7—N2	9.55 (12)
C1—C2—C3—C4	0.66 (14)	C8—N1—C7—C6	−171.73 (8)
Cl1—C2—C3—C4	−178.58 (8)	C1—C6—C7—N2	−15.38 (13)
C2—C3—C4—C5	−0.37 (15)	C5—C6—C7—N2	166.02 (9)
C3—C4—C5—C6	−0.09 (15)	C1—C6—C7—N1	165.98 (9)
C2—C1—C6—C5	0.00 (13)	C5—C6—C7—N1	−12.62 (13)
C2—C1—C6—C7	−178.62 (8)	C7—N1—C8—C9	−13.33 (10)
C4—C5—C6—C1	0.28 (14)	C7—N2—C9—C8	−8.35 (11)
C4—C5—C6—C7	178.87 (9)	N1—C8—C9—N2	13.08 (10)
C9—N2—C7—N1	−0.43 (11)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···N2^iv	0.896 (16)	2.118 (16)	3.0113 (11)	174.5 (15)

Symmetry code: (iv) x−1/4, −y+1/4, z−1/4.

Experimental details

Crystal data
Chemical formula	C₉H₉ClN₂
M_r	180.63
Crystal system, space group	Orthorhombic, Fdd2
Temperature (K)	100
a, b, c (Å)	19.7329 (8), 39.1479 (18), 4.3493 (2)
V (Å³)	3359.8 (3)
Z	16
Radiation type	Mo Kα
µ (mm⁻¹)	0.39
Crystal size (mm)	0.51 × 0.50 × 0.09

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.825, 0.964
No. of measured, independent and observed [I > 2σ(I)] reflections	14166, 3438, 3224
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.807

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.072, 1.10
No. of reflections	3438
No. of parameters	113
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)	0.33, −0.15
Absolute structure	Flack (1983), 1429 Friedel pairs
Absolute structure parameter	−0.05 (4)

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

Selected interatomic distances (Å) top

Cl1···Cl1ⁱ	3.3540 (3)	C4···C6ⁱⁱⁱ	3.3997 (15)
C1···C3ⁱⁱ	3.3945 (12)	C5···C7ⁱⁱⁱ	3.3716 (12)
C1···C4ⁱⁱ	3.3301 (15)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···N2^iv	0.896 (16)	2.118 (16)	3.0113 (11)	174.5 (15)

Symmetry code: (iv) x−1/4, −y+1/4, z−1/4.

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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