2-[1-(1-Phenyl­eth­yl)imidazolidin-2-yl­idene]malononitrile

Liu, X.-W.; Xu, L.-Z.

doi:10.1107/S1600536812010823

organic compounds

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ISSN: 2056-9890

Volume 68| Part 4| April 2012| Page o1203

doi:10.1107/S1600536812010823

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2-[1-(1-Phenylethyl)imidazolidin-2-ylidene]malononitrile

Xiao-Wei Liu ^a and Liang-Zhong Xu ^a ^*

^aCollege of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042, People's Republic of China
^*Correspondence e-mail: qknhs@yahoo.com.cn

(Received 18 February 2012; accepted 12 March 2012; online 28 March 2012)

In the title compound, C₁₄H₁₄N₄, the imidazolidine moiety is nearly planar, having an N—C—N—C torsion angle of 4.43 (3)°. The crystal structure is characterized by classical N—H⋯N hydrogen bonds, which form inversion dimers.

Related literature

For the biological activity of compounds containing a 2-(imidazolidin-2-ylidene)malononitrile group, see: Hense et al. (2002 ). For a related structure, see: Feng et al. (2008 ). For the synthesis of the title compound, see: Jeschke et al. (2002 ).

Experimental

Crystal data

C₁₄H₁₄N₄
M_r = 238.29
Triclinic, $[P \overline 1]$
a = 6.6446 (13) Å
b = 8.0106 (16) Å
c = 12.847 (3) Å
α = 90.51 (3)°
β = 101.85 (3)°
γ = 107.76 (3)°
V = 635.5 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 295 K
0.46 × 0.41 × 0.11 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.965, T_max = 0.992
6293 measured reflections
2898 independent reflections
2112 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.145
S = 1.15
2898 reflections
164 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯N4ⁱ	0.86	2.27	3.032 (2)	148
Symmetry code: (i) -x+2, -y, -z+2.

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812010823/rk2338sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812010823/rk2338Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812010823/rk2338Isup3.cml

checkCIF report

Comment top

Recently, imidazolidin is an important kind of group in organic chemistry. Compounds containing the 2-(imidazolidin-2-ylidene)malononitrile group have attracted much interest because compounds containing a imidazole ring system are well known as efficient insecticide in pesticides, and have good plant-growth regulatory activity for a wide variety of crops (Hense, et al., 2002). We report herein the crystal structure of title compound.

In title molecule (Fig. 1), the bond lengths and angles of the imidazolidin rings are in agreement with those in previous reports (Feng et al., 2008). The imidazolidin moiety has a small torsion angle N1–C11–N2–C10 = 4.43 (3)° which is nearly closed to a plane. The main plane of imidazolidin ring and the benzene ring make a dihedral angle of 87.18 (2)°. The crystal structure is characterized by N2–H2A···N4ⁱ classical intermolecular hydrogen bonds and centosymmetrical dimers with using these. H-bonds parameters: N2–H2A = 0.86Å, H2A···N4ⁱ = 2.27Å, N2···N4ⁱ = 3.032 (2)Å and angle N2–H2A···N4ⁱ = 147.6°. Symmetry code: (i) -x+2, -y, -z+2.

Related literature top

For the biological activity of thiazole componds, see: Hense et al. (2002). Fora related structure, see: Feng et al. (2008). For the synthesis of the title compound, see: Jeschke et al. (2002).

Experimental top

The title compound was prepared according Jeschke et al., 2002. Single crystals suitable for X-ray measurement were obtained by recrystallization from the mixture of acetone and methanol at room temperature.

Structure description top

For the biological activity of thiazole componds, see: Hense et al. (2002). Fora related structure, see: Feng et al. (2008). For the synthesis of the title compound, see: Jeschke et al. (2002).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. View of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as a small spheres of arbitrary radius.

2-[1-(1-Phenylethyl)imidazolidin-2-ylidene]propanedinitrile top

Crystal data top

C₁₄H₁₄N₄	Z = 2
M_r = 238.29	F(000) = 252
Triclinic, P1	D_x = 1.245 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.6446 (13) Å	Cell parameters from 4704 reflections
b = 8.0106 (16) Å	θ = 6.1–55.0°
c = 12.847 (3) Å	µ = 0.08 mm⁻¹
α = 90.51 (3)°	T = 295 K
β = 101.85 (3)°	Block, colourless
γ = 107.76 (3)°	0.46 × 0.41 × 0.11 mm
V = 635.5 (3) Å³

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	2898 independent reflections
Radiation source: Rotating Anode	2112 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
φ and ω scans	θ_max = 27.5°, θ_min = 3.0°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	h = −8→8
T_min = 0.965, T_max = 0.992	k = −10→10
6293 measured reflections	l = −16→16

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)] = 0.044	H-atom parameters constrained
wR(F²) = 0.145	w = 1/[σ²(F_o²) + (0.063P)² + 0.0913P] where P = (F_o² + 2F_c²)/3
S = 1.15	(Δ/σ)_max < 0.001
2898 reflections	Δρ_max = 0.21 e Å⁻³
164 parameters	Δρ_min = −0.19 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.210 (17)

Crystal data top

C₁₄H₁₄N₄	γ = 107.76 (3)°
M_r = 238.29	V = 635.5 (3) Å³
Triclinic, P1	Z = 2
a = 6.6446 (13) Å	Mo Kα radiation
b = 8.0106 (16) Å	µ = 0.08 mm⁻¹
c = 12.847 (3) Å	T = 295 K
α = 90.51 (3)°	0.46 × 0.41 × 0.11 mm
β = 101.85 (3)°

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	2898 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2112 reflections with I > 2σ(I)
T_min = 0.965, T_max = 0.992	R_int = 0.019
6293 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.145	H-atom parameters constrained
S = 1.15	Δρ_max = 0.21 e Å⁻³
2898 reflections	Δρ_min = −0.19 e Å⁻³
164 parameters

Special details top

Geometry. All s.u.'s (except the s.u.' in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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	0.43363 (19)	0.16514 (14)	0.79468 (10)	0.0520 (3)
N2	0.72640 (19)	0.19909 (15)	0.91821 (10)	0.0536 (3)
H2A	0.8196	0.1712	0.9659	0.064*
N3	0.1806 (3)	−0.35508 (19)	0.77933 (15)	0.0898 (6)
N4	0.8269 (3)	−0.20051 (18)	0.96591 (14)	0.0808 (5)
C1	0.4326 (3)	0.1738 (3)	0.56429 (16)	0.0782 (5)
H1A	0.5353	0.1251	0.5998	0.094*
C2	0.4528 (5)	0.2430 (4)	0.4674 (2)	0.1102 (9)
H2B	0.5692	0.2406	0.4384	0.132*
C3	0.3038 (7)	0.3147 (3)	0.41400 (19)	0.1218 (12)
H3A	0.3166	0.3591	0.3482	0.146*
C4	0.1366 (5)	0.3208 (3)	0.45755 (19)	0.1070 (9)
H4A	0.0360	0.3716	0.4219	0.128*
C5	0.1144 (3)	0.2526 (2)	0.55405 (15)	0.0762 (5)
H5A	−0.0013	0.2578	0.5828	0.091*
C6	0.2612 (2)	0.17651 (18)	0.60873 (12)	0.0535 (4)
C7	0.2351 (2)	0.09009 (18)	0.71185 (12)	0.0521 (4)
H7A	0.2186	−0.0345	0.6984	0.063*
C8	0.0397 (3)	0.0987 (3)	0.75267 (16)	0.0819 (6)
H8A	0.0358	0.0410	0.8177	0.123*
H8B	−0.0899	0.0411	0.7003	0.123*
H8C	0.0495	0.2194	0.7658	0.123*
C9	0.5134 (3)	0.35393 (18)	0.82776 (14)	0.0637 (4)
H9A	0.4198	0.3861	0.8676	0.076*
H9B	0.5236	0.4237	0.7666	0.076*
C10	0.7356 (3)	0.3781 (2)	0.89770 (15)	0.0652 (5)
H10A	0.8496	0.4324	0.8606	0.078*
H10B	0.7582	0.4487	0.9633	0.078*
C11	0.5563 (2)	0.08185 (16)	0.85453 (10)	0.0427 (3)
C12	0.5237 (2)	−0.10079 (17)	0.85565 (11)	0.0463 (3)
C13	0.3310 (3)	−0.23639 (18)	0.81102 (13)	0.0571 (4)
C14	0.6899 (2)	−0.15619 (17)	0.91645 (12)	0.0544 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0518 (7)	0.0364 (6)	0.0600 (7)	0.0146 (5)	−0.0060 (5)	0.0044 (5)
N2	0.0505 (7)	0.0411 (6)	0.0607 (7)	0.0139 (5)	−0.0058 (5)	0.0029 (5)
N3	0.0747 (10)	0.0488 (8)	0.1153 (13)	0.0034 (7)	−0.0228 (9)	0.0179 (8)
N4	0.0751 (10)	0.0476 (7)	0.1022 (11)	0.0227 (7)	−0.0245 (8)	0.0060 (7)
C1	0.0797 (12)	0.0727 (11)	0.0818 (12)	0.0196 (10)	0.0231 (10)	0.0037 (9)
C2	0.138 (2)	0.0916 (17)	0.0893 (16)	−0.0008 (16)	0.0555 (16)	−0.0052 (14)
C3	0.193 (3)	0.0721 (14)	0.0601 (12)	−0.0100 (18)	0.0169 (18)	0.0092 (11)
C4	0.146 (2)	0.0751 (14)	0.0712 (13)	0.0233 (14)	−0.0239 (15)	0.0214 (11)
C5	0.0804 (12)	0.0661 (10)	0.0737 (11)	0.0273 (9)	−0.0090 (9)	0.0156 (9)
C6	0.0550 (8)	0.0407 (7)	0.0575 (8)	0.0128 (6)	−0.0004 (6)	0.0030 (6)
C7	0.0453 (7)	0.0438 (7)	0.0607 (8)	0.0137 (6)	−0.0025 (6)	0.0071 (6)
C8	0.0537 (10)	0.1076 (16)	0.0791 (12)	0.0189 (10)	0.0124 (8)	0.0145 (11)
C9	0.0651 (10)	0.0386 (7)	0.0789 (10)	0.0170 (7)	−0.0038 (8)	0.0042 (7)
C10	0.0620 (9)	0.0405 (7)	0.0816 (11)	0.0122 (7)	−0.0036 (8)	0.0037 (7)
C11	0.0420 (6)	0.0404 (6)	0.0454 (7)	0.0135 (5)	0.0080 (5)	0.0068 (5)
C12	0.0472 (7)	0.0380 (6)	0.0505 (7)	0.0140 (5)	0.0028 (5)	0.0086 (5)
C13	0.0573 (9)	0.0399 (7)	0.0659 (9)	0.0141 (6)	−0.0029 (7)	0.0128 (6)
C14	0.0563 (8)	0.0363 (7)	0.0627 (9)	0.0132 (6)	−0.0024 (7)	0.0064 (6)

Geometric parameters (Å, º) top

N1—C11	1.3356 (16)	C5—C6	1.381 (2)
N1—C9	1.4682 (18)	C5—H5A	0.9300
N1—C7	1.4702 (18)	C6—C7	1.517 (2)
N2—C11	1.3371 (18)	C7—C8	1.516 (2)
N2—C10	1.4452 (19)	C7—H7A	0.9800
N2—H2A	0.8600	C8—H8A	0.9600
N3—C13	1.147 (2)	C8—H8B	0.9600
N4—C14	1.1496 (19)	C8—H8C	0.9600
C1—C6	1.380 (3)	C9—C10	1.517 (2)
C1—C2	1.382 (3)	C9—H9A	0.9700
C1—H1A	0.9300	C9—H9B	0.9700
C2—C3	1.362 (4)	C10—H10A	0.9700
C2—H2B	0.9300	C10—H10B	0.9700
C3—C4	1.355 (4)	C11—C12	1.4129 (18)
C3—H3A	0.9300	C12—C14	1.4062 (19)
C4—C5	1.377 (3)	C12—C13	1.410 (2)
C4—H4A	0.9300

C11—N1—C9	110.32 (12)	C8—C7—H7A	107.2
C11—N1—C7	128.66 (11)	C6—C7—H7A	107.2
C9—N1—C7	120.86 (11)	C7—C8—H8A	109.5
C11—N2—C10	112.21 (12)	C7—C8—H8B	109.5
C11—N2—H2A	123.9	H8A—C8—H8B	109.5
C10—N2—H2A	123.9	C7—C8—H8C	109.5
C6—C1—C2	120.6 (2)	H8A—C8—H8C	109.5
C6—C1—H1A	119.7	H8B—C8—H8C	109.5
C2—C1—H1A	119.7	N1—C9—C10	103.10 (12)
C3—C2—C1	120.6 (3)	N1—C9—H9A	111.1
C3—C2—H2B	119.7	C10—C9—H9A	111.1
C1—C2—H2B	119.7	N1—C9—H9B	111.1
C4—C3—C2	119.5 (2)	C10—C9—H9B	111.1
C4—C3—H3A	120.3	H9A—C9—H9B	109.1
C2—C3—H3A	120.3	N2—C10—C9	102.14 (12)
C3—C4—C5	120.6 (2)	N2—C10—H10A	111.3
C3—C4—H4A	119.7	C9—C10—H10A	111.3
C5—C4—H4A	119.7	N2—C10—H10B	111.3
C4—C5—C6	121.0 (2)	C9—C10—H10B	111.3
C4—C5—H5A	119.5	H10A—C10—H10B	109.2
C6—C5—H5A	119.5	N1—C11—N2	109.74 (11)
C1—C6—C5	117.79 (17)	N1—C11—C12	128.42 (12)
C1—C6—C7	119.56 (14)	N2—C11—C12	121.84 (12)
C5—C6—C7	122.59 (16)	C14—C12—C13	115.29 (12)
N1—C7—C8	110.06 (13)	C14—C12—C11	117.82 (12)
N1—C7—C6	109.75 (12)	C13—C12—C11	126.52 (12)
C8—C7—C6	115.10 (13)	N3—C13—C12	174.86 (15)
N1—C7—H7A	107.2	N4—C14—C12	179.51 (18)

C6—C1—C2—C3	−0.1 (3)	C5—C6—C7—C8	−2.0 (2)
C1—C2—C3—C4	1.2 (4)	C11—N1—C9—C10	13.82 (18)
C2—C3—C4—C5	−1.1 (4)	C7—N1—C9—C10	−170.38 (14)
C3—C4—C5—C6	0.0 (3)	C11—N2—C10—C9	12.63 (19)
C2—C1—C6—C5	−1.0 (3)	N1—C9—C10—N2	−15.03 (18)
C2—C1—C6—C7	176.36 (17)	C9—N1—C11—N2	−6.47 (17)
C4—C5—C6—C1	1.0 (3)	C7—N1—C11—N2	178.16 (14)
C4—C5—C6—C7	−176.22 (17)	C9—N1—C11—C12	173.57 (15)
C11—N1—C7—C8	106.76 (18)	C7—N1—C11—C12	−1.8 (2)
C9—N1—C7—C8	−68.19 (19)	C10—N2—C11—N1	−4.43 (18)
C11—N1—C7—C6	−125.59 (15)	C10—N2—C11—C12	175.54 (14)
C9—N1—C7—C6	59.46 (18)	N1—C11—C12—C14	172.25 (14)
C1—C6—C7—N1	56.03 (18)	N2—C11—C12—C14	−7.7 (2)
C5—C6—C7—N1	−126.78 (16)	N1—C11—C12—C13	−15.1 (2)
C1—C6—C7—C8	−179.18 (16)	N2—C11—C12—C13	164.94 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···N4ⁱ	0.86	2.27	3.032 (2)	148

Symmetry code: (i) −x+2, −y, −z+2.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₄N₄
M_r	238.29
Crystal system, space group	Triclinic, P1
Temperature (K)	295
a, b, c (Å)	6.6446 (13), 8.0106 (16), 12.847 (3)
α, β, γ (°)	90.51 (3), 101.85 (3), 107.76 (3)
V (Å³)	635.5 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.46 × 0.41 × 0.11

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.965, 0.992
No. of measured, independent and observed [I > 2σ(I)] reflections	6293, 2898, 2112
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.145, 1.15
No. of reflections	2898
No. of parameters	164
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.19

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···N4ⁱ	0.86	2.27	3.032 (2)	147.6

Symmetry code: (i) −x+2, −y, −z+2.

References

Feng, X.-Z., Yan, F.-F. & Li, Z.-P. (2008). Acta Cryst. E64, o1120. Web of Science CSD CrossRef IUCr Journals Google Scholar
Hense, A., Fischer, A. & Gesing, E. R. (2002). WO Patent 2002096872. Google Scholar
Jeschke, P., Beck, M. E. & Kraemer, W. (2002). German Patent 10119423. Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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