2-(1,3-Dibenzyl­imidazolidin-2-yl­idene)malononitrile

Feng, X.-Z.; Yan, F.-F.; Li, Z.-P.

doi:10.1107/S1600536808014025

organic compounds

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ISSN: 2056-9890

Volume 64| Part 6| June 2008| Page o1120

doi:10.1107/S1600536808014025

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2-(1,3-Dibenzylimidazolidin-2-ylidene)malononitrile

Xiao-Zhong Feng,^a ^* Fu-Feng Yan ^a and Zhen-Ping Li ^b

^aHenan Provincial Key Laboratory of Surface & Interface Science, Zhengzhou University of Light Industry, Zhengzhou 450002, People's Republic of China, and ^bLight Industry Vocational College, Zhengzhou University of Light Industry, Zhengzhou 450002, People's Republic of China
^*Correspondence e-mail: fengxiaozhong_2008@yahoo.cn

(Received 6 May 2008; accepted 10 May 2008; online 21 May 2008)

In the title molecule, C₂₀H₁₈N₄, the imidazolidine ring makes dihedral angles of 86.74 (2) and 81.18 (3)° with the two phenyl rings. In the absence of classical intermolecular interactions, the crystal packing is stabilized by van der Waals forces.

Related literature

For the crystal structures of related compounds, see: Adhikesavalu & Venkatesan (1982 ). For details of the biological activities of imidazolidine-containing compounds, see: Sasho et al., 1994 . For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₂₀H₁₈N₄
M_r = 314.38
Orthorhombic, P c a 2₁
a = 15.445 (3) Å
b = 9.753 (2) Å
c = 11.411 (2) Å
V = 1718.9 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 293 (2) K
0.24 × 0.14 × 0.08 mm

Data collection

Rigaku R-AXIS RAPID IP area-detector diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.982, T_max = 0.994
12952 measured reflections
1607 independent reflections
1291 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.114
S = 1.13
1607 reflections
218 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Data collection: RAPID-AUTO (Rigaku, 2004 ); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808014025/hg2400sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808014025/hg2400Isup2.hkl

checkCIF report

Comment top

Imidazolidine is an important group in organic chemistry. Many compounds containing imidazolidine groups possess a broad spectrum of biological activities (Sasho et al., 1994). Here, we report the crystal structure of (I).

In (I) (Fig. 1), all bond lengths are normal (Allen et al., 1987) and in a good agreement with those reported previously (Adhikesavalu & Venkatesan., 1982). The imidazolidine ring (C8—C10/N3/N4) makes dihedral angles of 86.74 (2) and 81.18 (3)°, respectively, with two benzene rings (C1—C6; C15—C20). In the absence of classical intermolecular interactions, the crystal packing is stabilized by van der Waals forces.

Related literature top

For the crystal structures of related compounds, see: Adhikesavalu & Venkatesan (1982). For details of the biological activities of Imidazolidine-containing compounds, see: Sasho et al., 1994. For bond-length data, see: Allen et al. (1987).

Experimental top

A solution of 2-(imidazolidin-2-ylidene)malononitrile 1.34 g (10 mmol) and sodium hydride 0.3 g dissolved in anhydrous acetonitrile (20 ml), and dropwise added over a period of 10 min to a solution of 1-(chloromethyl)benzene 2.53 (20 mmol) in acetonitrile (10 ml) at 273 K. The mixture was stirred at 353 K for 3 h. The solvent was removed and the residue was purified by flash chromatography (1:1 cyclohexane:dichloromethane) to give I as a white solid (2.67 g, 85%). Single crystals suitable for X-ray measurements were obtained by recrystallization from ethanol at room temperature.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 2004); cell refinement: RAPID-AUTO (Rigaku, 2004); data reduction: RAPID-AUTO (Rigaku, 2004); 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).

Figures top

Fig. 1. The molecular structure of (I), with atom labels and 40% probability displacement ellipsoids for non-H atoms.

2-(1,3-Dibenzylimidazolidin-2-ylidene)malononitrile top

Crystal data top

C₂₀H₁₈N₄	F(000) = 664
M_r = 314.38	D_x = 1.215 Mg m⁻³
Orthorhombic, Pca2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 2422 reflections
a = 15.445 (3) Å	θ = 2.3–25.1°
b = 9.753 (2) Å	µ = 0.07 mm⁻¹
c = 11.411 (2) Å	T = 293 K
V = 1718.9 (6) Å³	Needle, colorless
Z = 4	0.24 × 0.14 × 0.08 mm

Data collection top

Rigaku R-AXIS RAPID IP area-detector diffractometer	1607 independent reflections
Radiation source: Rotating Anode	1291 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
ω oscillation scans	θ_max = 25.0°, θ_min = 3.1°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −18→18
T_min = 0.982, T_max = 0.994	k = −11→11
12952 measured reflections	l = −12→13

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)] = 0.041	H-atom parameters constrained
wR(F²) = 0.114	w = 1/[σ²(F_o²) + (0.0488P)² + 0.3923P] where P = (F_o² + 2F_c²)/3
S = 1.13	(Δ/σ)_max < 0.001
1607 reflections	Δρ_max = 0.17 e Å⁻³
218 parameters	Δρ_min = −0.15 e Å⁻³
1 restraint	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.028 (3)

Crystal data top

C₂₀H₁₈N₄	V = 1718.9 (6) Å³
M_r = 314.38	Z = 4
Orthorhombic, Pca2₁	Mo Kα radiation
a = 15.445 (3) Å	µ = 0.07 mm⁻¹
b = 9.753 (2) Å	T = 293 K
c = 11.411 (2) Å	0.24 × 0.14 × 0.08 mm

Data collection top

Rigaku R-AXIS RAPID IP area-detector diffractometer	1607 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1291 reflections with I > 2σ(I)
T_min = 0.982, T_max = 0.994	R_int = 0.038
12952 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	1 restraint
wR(F²) = 0.114	H-atom parameters constrained
S = 1.13	Δρ_max = 0.17 e Å⁻³
1607 reflections	Δρ_min = −0.15 e Å⁻³
218 parameters

Special details top

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
N4	0.12629 (16)	0.3089 (3)	0.5140 (3)	0.0547 (7)
N3	0.19406 (17)	0.5004 (3)	0.5604 (3)	0.0552 (7)
C10	0.19739 (18)	0.3857 (3)	0.4962 (3)	0.0486 (7)
C15	0.2983 (2)	0.6672 (3)	0.6431 (3)	0.0554 (8)
C11	0.2649 (2)	0.3501 (3)	0.4181 (3)	0.0563 (8)
C6	0.0325 (2)	0.1189 (4)	0.4561 (4)	0.0645 (10)
C13	0.2496 (2)	0.2696 (4)	0.3185 (4)	0.0604 (9)
C8	0.0718 (2)	0.3705 (4)	0.6057 (4)	0.0651 (10)
H8A	0.0726	0.3157	0.6766	0.078*
H8B	0.0125	0.3805	0.5793	0.078*
C14	0.2426 (3)	0.6261 (3)	0.5409 (3)	0.0628 (9)
H14A	0.2022	0.6997	0.5242	0.075*
H14B	0.2791	0.6142	0.4725	0.075*
C12	0.3498 (2)	0.3964 (5)	0.4360 (4)	0.0730 (11)
N2	0.2371 (3)	0.2064 (3)	0.2348 (3)	0.0805 (10)
C7	0.1204 (2)	0.1601 (3)	0.5002 (4)	0.0633 (9)
H7A	0.1313	0.1161	0.5751	0.076*
H7B	0.1643	0.1293	0.4454	0.076*
C16	0.3438 (2)	0.5709 (4)	0.7070 (3)	0.0606 (9)
H16A	0.3370	0.4782	0.6903	0.073*
C18	0.4101 (3)	0.7463 (5)	0.8220 (4)	0.0808 (12)
H18A	0.4479	0.7731	0.8811	0.097*
C19	0.3648 (3)	0.8422 (5)	0.7607 (4)	0.0882 (14)
H19A	0.3718	0.9345	0.7788	0.106*
C9	0.1137 (2)	0.5087 (4)	0.6255 (4)	0.0648 (9)
H9A	0.0774	0.5820	0.5958	0.078*
H9B	0.1247	0.5241	0.7081	0.078*
C20	0.3079 (3)	0.8040 (4)	0.6708 (4)	0.0746 (11)
H20A	0.2768	0.8704	0.6302	0.089*
C17	0.3997 (2)	0.6111 (5)	0.7963 (3)	0.0688 (10)
H17A	0.4301	0.5454	0.8386	0.083*
C4	−0.0941 (3)	−0.0245 (5)	0.4651 (7)	0.109 (2)
H4A	−0.1243	−0.0959	0.5002	0.130*
N1	0.4199 (2)	0.4303 (5)	0.4518 (4)	0.1066 (15)
C5	−0.0132 (3)	0.0158 (4)	0.5091 (5)	0.0864 (14)
H5A	0.0095	−0.0279	0.5747	0.104*
C1	−0.0043 (3)	0.1819 (5)	0.3600 (5)	0.0978 (15)
H1A	0.0257	0.2515	0.3219	0.117*
C2	−0.0843 (4)	0.1437 (6)	0.3197 (7)	0.124 (2)
H2A	−0.1085	0.1892	0.2561	0.149*
C3	−0.1278 (4)	0.0414 (6)	0.3712 (8)	0.123 (2)
H3A	−0.1817	0.0155	0.3423	0.147*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N4	0.0400 (13)	0.0606 (15)	0.0636 (18)	−0.0039 (12)	0.0008 (14)	−0.0105 (14)
N3	0.0491 (15)	0.0576 (15)	0.0590 (16)	−0.0077 (12)	−0.0039 (13)	−0.0092 (15)
C10	0.0395 (15)	0.0585 (17)	0.0477 (18)	0.0002 (13)	−0.0019 (15)	0.0002 (16)
C15	0.0533 (18)	0.0564 (18)	0.056 (2)	−0.0081 (15)	−0.0014 (17)	−0.0045 (17)
C11	0.0457 (18)	0.069 (2)	0.054 (2)	−0.0041 (15)	0.0006 (16)	−0.0024 (18)
C6	0.059 (2)	0.0561 (19)	0.078 (3)	−0.0091 (17)	0.005 (2)	−0.0164 (19)
C13	0.0567 (19)	0.067 (2)	0.057 (2)	0.0062 (17)	0.0012 (18)	−0.001 (2)
C8	0.0442 (18)	0.083 (2)	0.068 (2)	−0.0025 (17)	0.0070 (17)	−0.014 (2)
C14	0.065 (2)	0.0590 (18)	0.065 (2)	−0.0084 (18)	−0.0123 (18)	0.0010 (19)
C12	0.055 (2)	0.100 (3)	0.064 (2)	−0.010 (2)	0.0075 (19)	−0.012 (2)
N2	0.093 (3)	0.082 (2)	0.067 (2)	0.008 (2)	0.006 (2)	−0.011 (2)
C7	0.0579 (19)	0.0544 (18)	0.078 (2)	−0.0037 (15)	−0.001 (2)	−0.006 (2)
C16	0.056 (2)	0.069 (2)	0.056 (2)	−0.0103 (18)	0.0020 (17)	−0.0012 (19)
C18	0.065 (2)	0.113 (3)	0.065 (2)	−0.026 (2)	0.000 (2)	−0.017 (3)
C19	0.090 (3)	0.083 (3)	0.092 (3)	−0.030 (3)	0.012 (3)	−0.032 (3)
C9	0.057 (2)	0.075 (2)	0.063 (2)	−0.0002 (18)	0.0069 (19)	−0.0148 (19)
C20	0.079 (3)	0.060 (2)	0.084 (3)	−0.0100 (19)	0.003 (2)	−0.012 (2)
C17	0.0524 (19)	0.100 (3)	0.053 (2)	−0.0134 (19)	−0.0046 (17)	−0.002 (2)
C4	0.075 (3)	0.074 (3)	0.177 (6)	−0.023 (2)	0.016 (4)	−0.025 (4)
N1	0.054 (2)	0.153 (4)	0.113 (3)	−0.020 (2)	0.015 (2)	−0.039 (3)
C5	0.076 (3)	0.068 (2)	0.115 (4)	−0.015 (2)	0.016 (3)	−0.011 (3)
C1	0.096 (3)	0.094 (3)	0.103 (4)	−0.023 (3)	−0.034 (3)	0.004 (3)
C2	0.109 (4)	0.110 (4)	0.153 (6)	−0.019 (3)	−0.066 (4)	−0.014 (4)
C3	0.086 (4)	0.089 (4)	0.194 (7)	−0.012 (3)	−0.029 (4)	−0.039 (4)

Geometric parameters (Å, º) top

N4—C10	1.345 (4)	C7—H7A	0.9700
N4—C7	1.463 (4)	C7—H7B	0.9700
N4—C8	1.470 (4)	C16—C17	1.392 (5)
N3—C10	1.339 (4)	C16—H16A	0.9300
N3—C9	1.448 (4)	C18—C17	1.360 (6)
N3—C14	1.453 (4)	C18—C19	1.361 (7)
C10—C11	1.415 (5)	C18—H18A	0.9300
C15—C20	1.379 (5)	C19—C20	1.401 (6)
C15—C16	1.381 (5)	C19—H19A	0.9300
C15—C14	1.504 (5)	C9—H9A	0.9700
C11—C12	1.402 (5)	C9—H9B	0.9700
C11—C13	1.402 (5)	C20—H20A	0.9300
C6—C5	1.370 (5)	C17—H17A	0.9300
C6—C1	1.380 (6)	C4—C3	1.354 (9)
C6—C7	1.503 (5)	C4—C5	1.402 (7)
C13—N2	1.153 (5)	C4—H4A	0.9300
C8—C9	1.512 (5)	C5—H5A	0.9300
C8—H8A	0.9700	C1—C2	1.368 (6)
C8—H8B	0.9700	C1—H1A	0.9300
C14—H14A	0.9700	C2—C3	1.339 (9)
C14—H14B	0.9700	C2—H2A	0.9300
C12—N1	1.146 (5)	C3—H3A	0.9300

C10—N4—C7	125.9 (3)	H7A—C7—H7B	108.0
C10—N4—C8	110.3 (3)	C15—C16—C17	120.6 (4)
C7—N4—C8	116.5 (3)	C15—C16—H16A	119.7
C10—N3—C9	111.1 (3)	C17—C16—H16A	119.7
C10—N3—C14	127.0 (3)	C17—C18—C19	119.7 (4)
C9—N3—C14	118.3 (3)	C17—C18—H18A	120.1
N3—C10—N4	110.6 (3)	C19—C18—H18A	120.1
N3—C10—C11	125.3 (3)	C18—C19—C20	121.0 (4)
N4—C10—C11	124.1 (3)	C18—C19—H19A	119.5
C20—C15—C16	118.9 (4)	C20—C19—H19A	119.5
C20—C15—C14	119.8 (4)	N3—C9—C8	103.9 (3)
C16—C15—C14	121.3 (3)	N3—C9—H9A	111.0
C12—C11—C13	117.2 (3)	C8—C9—H9A	111.0
C12—C11—C10	121.3 (3)	N3—C9—H9B	111.0
C13—C11—C10	121.6 (3)	C8—C9—H9B	111.0
C5—C6—C1	117.7 (4)	H9A—C9—H9B	109.0
C5—C6—C7	120.9 (4)	C15—C20—C19	119.5 (4)
C1—C6—C7	121.3 (4)	C15—C20—H20A	120.3
N2—C13—C11	178.3 (4)	C19—C20—H20A	120.3
N4—C8—C9	103.0 (3)	C18—C17—C16	120.3 (4)
N4—C8—H8A	111.2	C18—C17—H17A	119.9
C9—C8—H8A	111.2	C16—C17—H17A	119.9
N4—C8—H8B	111.2	C3—C4—C5	119.6 (5)
C9—C8—H8B	111.2	C3—C4—H4A	120.2
H8A—C8—H8B	109.1	C5—C4—H4A	120.2
N3—C14—C15	113.7 (3)	C6—C5—C4	120.4 (5)
N3—C14—H14A	108.8	C6—C5—H5A	119.8
C15—C14—H14A	108.8	C4—C5—H5A	119.8
N3—C14—H14B	108.8	C2—C1—C6	121.2 (5)
C15—C14—H14B	108.8	C2—C1—H1A	119.4
H14A—C14—H14B	107.7	C6—C1—H1A	119.4
N1—C12—C11	177.9 (6)	C3—C2—C1	120.6 (7)
N4—C7—C6	110.9 (3)	C3—C2—H2A	119.7
N4—C7—H7A	109.5	C1—C2—H2A	119.7
C6—C7—H7A	109.5	C2—C3—C4	120.5 (6)
N4—C7—H7B	109.5	C2—C3—H3A	119.8
C6—C7—H7B	109.5	C4—C3—H3A	119.8

C9—N3—C10—N4	−2.2 (4)	C1—C6—C7—N4	49.6 (5)
C14—N3—C10—N4	−159.9 (3)	C20—C15—C16—C17	−1.3 (5)
C9—N3—C10—C11	176.5 (3)	C14—C15—C16—C17	175.6 (3)
C14—N3—C10—C11	18.8 (5)	C17—C18—C19—C20	−0.4 (7)
C7—N4—C10—N3	−153.8 (3)	C10—N3—C9—C8	7.8 (4)
C8—N4—C10—N3	−4.8 (4)	C14—N3—C9—C8	167.7 (3)
C7—N4—C10—C11	27.5 (5)	N4—C8—C9—N3	−9.8 (4)
C8—N4—C10—C11	176.5 (3)	C16—C15—C20—C19	1.5 (6)
N3—C10—C11—C12	28.6 (5)	C14—C15—C20—C19	−175.4 (4)
N4—C10—C11—C12	−152.9 (4)	C18—C19—C20—C15	−0.7 (7)
N3—C10—C11—C13	−150.1 (3)	C19—C18—C17—C16	0.7 (6)
N4—C10—C11—C13	28.4 (5)	C15—C16—C17—C18	0.2 (6)
C10—N4—C8—C9	9.3 (4)	C1—C6—C5—C4	0.9 (6)
C7—N4—C8—C9	161.4 (3)	C7—C6—C5—C4	−178.2 (4)
C10—N3—C14—C15	−121.6 (4)	C3—C4—C5—C6	−1.5 (7)
C9—N3—C14—C15	82.0 (4)	C5—C6—C1—C2	0.7 (7)
C20—C15—C14—N3	−143.2 (3)	C7—C6—C1—C2	179.7 (5)
C16—C15—C14—N3	39.9 (5)	C6—C1—C2—C3	−1.7 (9)
C10—N4—C7—C6	−145.9 (3)	C1—C2—C3—C4	1.0 (10)
C8—N4—C7—C6	66.8 (4)	C5—C4—C3—C2	0.5 (9)
C5—C6—C7—N4	−131.3 (4)

Experimental details

Crystal data
Chemical formula	C₂₀H₁₈N₄
M_r	314.38
Crystal system, space group	Orthorhombic, Pca2₁
Temperature (K)	293
a, b, c (Å)	15.445 (3), 9.753 (2), 11.411 (2)
V (Å³)	1718.9 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.24 × 0.14 × 0.08

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP area-detector diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.982, 0.994
No. of measured, independent and observed [I > 2σ(I)] reflections	12952, 1607, 1291
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.114, 1.13
No. of reflections	1607
No. of parameters	218
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.15

Computer programs: RAPID-AUTO (Rigaku, 2004), SHELXTL (Sheldrick, 2008).

References

Adhikesavalu, D. & Venkatesan, K. (1982). Acta Cryst. B38, 855–859. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (2004). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sasho, S., Obase, H., Ichikawa, S., Yoshizaki, R., Ishii, A. & Shuto, K. (1994). Bioorg. Med. Chem. Lett. 4, 615–618. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar