2-[4-(Benz­yloxy)benzyl­idene]malononitrile

Gan, H.; Liu, X.; Fang, Z.; Guo, K.

doi:10.1107/S1600536812020053

organic compounds

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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page o1690

doi:10.1107/S1600536812020053

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2-[4-(Benzyloxy)benzylidene]malononitrile

Hai-feng Gan,^a Xue-wei Liu,^a Zheng Fang ^a and Kai Guo ^a ^*

^aCollege of Life Science and Pharmaceutical Engineering, Nanjing University of Technology, Puzhunan Road No. 30 Nanjing, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: kaiguo@njut.edu.cn

(Received 13 April 2012; accepted 4 May 2012; online 12 May 2012)

In the title molecule, C₁₇H₁₂N₂O, the dihedral angle between the two benzene rings is 84.98 (10)°. The dicyanoethylene group is coplanar with the benzene ring to which it is bonded. No classic hydrogen bonds were found in the crystal.

Related literature

For background information and the synthetic procedure for the title compound, see: Kharas et al. (2007 ). For a related crystal structure, see: Zhu et al. (2007 ).

Experimental

Crystal data

C₁₇H₁₂N₂O
M_r = 260.29
Triclinic, $[P \overline 1]$
a = 6.8470 (14) Å
b = 9.6270 (19) Å
c = 10.544 (2) Å
α = 100.66 (3)°
β = 91.65 (3)°
γ = 94.26 (3)°
V = 680.5 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.976, T_max = 0.992
2722 measured reflections
2496 independent reflections
1664 reflections with I > 2σ(I)
R_int = 0.022
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.061
wR(F²) = 0.176
S = 1.00
2496 reflections
181 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812020053/pv2535sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812020053/pv2535Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812020053/pv2535Isup3.cml

checkCIF report

Comment top

The synthesis of the title compound has been reoprted previously (Kharas et al., 2007). It is a key intermediate in our studies of cardiovascular drugs. In this paper we report the crystal structure of the title compound.

In the title compound (Fig. 1), the dihedral angle between the benzene rings C1–C6 and C8–C13 is 84.98 (10) °. The dicyanoethylene group (N1/N2/C14–C17) is almost coplanar with the benzene ring C8–C13, with a dihedral angles between the two planes being 0.71 (8) °. The structure is devoid of any hydrogen bondinhg interactions (Fig. 2).

Related literature top

For background information and the synthetic procedure for the title compound, see: Kharas et al. (2007). For a related crystal structure, see: Zhu et al. (2007).

Experimental top

To a solution of 4-(benzyloxy)benzaldehyde (10.01 mmol, 2.12 g) and malononitrile (10.14 mmol, 0.67 g) in ethanol (20 ml) was added triethylamine (0.31 ml) and the reaction mixture was heated to 338.15 K for 3 h. The reaction mixture was cooled to room temperature and then filtered to get the title compound (2.43 g) as pure a yellow solid (Kharas et al., 2007). Crystals of the title compound for X-ray diffraction were obtained by slow evaporation of an acetone solution.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); 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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as small spheres of arbitrary radius.
	Fig. 2. A view of the unit cell packing of the title compound.

2-[4-(Benzyloxy)benzylidene]malononitrile top

Crystal data top

C₁₇H₁₂N₂O	Z = 2
M_r = 260.29	F(000) = 272
Triclinic, P1	D_x = 1.270 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.8470 (14) Å	Cell parameters from 25 reflections
b = 9.6270 (19) Å	θ = 9–13°
c = 10.544 (2) Å	µ = 0.08 mm⁻¹
α = 100.66 (3)°	T = 293 K
β = 91.65 (3)°	Block, yellow
γ = 94.26 (3)°	0.30 × 0.20 × 0.10 mm
V = 680.5 (2) Å³

Data collection top

Enraf–Nonius CAD-4 diffractometer	1664 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.022
Graphite monochromator	θ_max = 25.4°, θ_min = 2.0°
ω/2θ scans	h = 0→8
Absorption correction: ψ scan (North et al., 1968)	k = −11→11
T_min = 0.976, T_max = 0.992	l = −12→12
2722 measured reflections	3 standard reflections every 200 reflections
2496 independent reflections	intensity decay: 1%

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)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.176	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.1P)² + 0.110P] where P = (F_o² + 2F_c²)/3
2496 reflections	(Δ/σ)_max < 0.001
181 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₁₇H₁₂N₂O	γ = 94.26 (3)°
M_r = 260.29	V = 680.5 (2) Å³
Triclinic, P1	Z = 2
a = 6.8470 (14) Å	Mo Kα radiation
b = 9.6270 (19) Å	µ = 0.08 mm⁻¹
c = 10.544 (2) Å	T = 293 K
α = 100.66 (3)°	0.30 × 0.20 × 0.10 mm
β = 91.65 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1664 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.022
T_min = 0.976, T_max = 0.992	3 standard reflections every 200 reflections
2722 measured reflections	intensity decay: 1%
2496 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.061	0 restraints
wR(F²) = 0.176	H-atom parameters constrained
S = 1.00	Δρ_max = 0.22 e Å⁻³
2496 reflections	Δρ_min = −0.18 e Å⁻³
181 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
O	0.2390 (3)	0.75384 (16)	0.34116 (15)	0.0569 (5)
N1	0.2812 (4)	1.3682 (3)	0.0440 (2)	0.0787 (8)
C1	0.0380 (4)	0.6905 (3)	0.5996 (3)	0.0660 (7)
H1A	−0.0703	0.7323	0.5729	0.079*
N2	0.2608 (4)	1.1632 (3)	−0.3621 (2)	0.0701 (7)
C2	0.0139 (6)	0.5918 (3)	0.6777 (3)	0.0797 (9)
H2A	−0.1106	0.5677	0.7040	0.096*
C3	0.1676 (7)	0.5300 (3)	0.7164 (3)	0.0851 (10)
H3A	0.1490	0.4633	0.7694	0.102*
C4	0.3527 (7)	0.5639 (4)	0.6788 (3)	0.0929 (11)
H4A	0.4589	0.5201	0.7058	0.111*
C5	0.3809 (5)	0.6648 (3)	0.5994 (3)	0.0763 (9)
H5A	0.5057	0.6885	0.5735	0.092*
C6	0.2224 (4)	0.7285 (2)	0.5601 (2)	0.0538 (6)
C7	0.2449 (4)	0.8328 (3)	0.4716 (2)	0.0596 (7)
H7A	0.1395	0.8955	0.4823	0.072*
H7B	0.3686	0.8899	0.4911	0.072*
C8	0.2438 (3)	0.8250 (2)	0.2424 (2)	0.0459 (6)
C9	0.2554 (4)	0.9733 (2)	0.2554 (2)	0.0502 (6)
H9A	0.2617	1.0303	0.3371	0.060*
C10	0.2575 (4)	1.0339 (2)	0.1472 (2)	0.0503 (6)
H10A	0.2657	1.1321	0.1569	0.060*
C11	0.2476 (3)	0.9510 (2)	0.0223 (2)	0.0453 (6)
C12	0.2362 (4)	0.8023 (2)	0.0131 (2)	0.0518 (6)
H12A	0.2296	0.7444	−0.0682	0.062*
C13	0.2346 (4)	0.7412 (2)	0.1198 (2)	0.0519 (6)
H13A	0.2273	0.6430	0.1104	0.062*
C14	0.2497 (3)	1.0026 (2)	−0.0972 (2)	0.0486 (6)
H14A	0.2429	0.9312	−0.1703	0.058*
C15	0.2598 (3)	1.1353 (3)	−0.1240 (2)	0.0497 (6)
C16	0.2724 (4)	1.2637 (3)	−0.0292 (2)	0.0559 (6)
C17	0.2608 (4)	1.1526 (3)	−0.2562 (3)	0.0538 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O	0.0747 (12)	0.0428 (9)	0.0535 (10)	0.0013 (8)	0.0064 (8)	0.0105 (7)
N1	0.103 (2)	0.0531 (14)	0.0792 (16)	0.0068 (13)	0.0117 (14)	0.0093 (13)
C1	0.0692 (19)	0.0665 (17)	0.0622 (16)	0.0038 (14)	0.0117 (14)	0.0110 (13)
N2	0.0831 (18)	0.0672 (15)	0.0647 (15)	0.0099 (12)	0.0025 (12)	0.0237 (12)
C2	0.104 (3)	0.0676 (18)	0.0684 (18)	−0.0049 (18)	0.0198 (18)	0.0170 (15)
C3	0.139 (4)	0.0565 (17)	0.0603 (18)	0.003 (2)	0.009 (2)	0.0129 (14)
C4	0.119 (3)	0.080 (2)	0.083 (2)	0.029 (2)	−0.021 (2)	0.0185 (18)
C5	0.072 (2)	0.0768 (19)	0.0817 (19)	0.0125 (16)	−0.0042 (16)	0.0169 (17)
C6	0.0641 (17)	0.0455 (13)	0.0498 (13)	0.0016 (12)	0.0016 (12)	0.0050 (11)
C7	0.0664 (17)	0.0526 (14)	0.0582 (15)	−0.0008 (12)	0.0042 (13)	0.0080 (12)
C8	0.0451 (13)	0.0403 (12)	0.0533 (13)	0.0017 (10)	0.0039 (10)	0.0122 (10)
C9	0.0575 (15)	0.0398 (12)	0.0517 (13)	0.0046 (10)	0.0032 (11)	0.0039 (10)
C10	0.0536 (15)	0.0373 (12)	0.0597 (14)	0.0038 (10)	0.0042 (11)	0.0084 (10)
C11	0.0387 (12)	0.0431 (12)	0.0546 (13)	0.0029 (10)	0.0033 (10)	0.0103 (10)
C12	0.0539 (15)	0.0441 (13)	0.0536 (14)	0.0028 (11)	0.0021 (11)	−0.0002 (11)
C13	0.0602 (16)	0.0339 (11)	0.0601 (14)	0.0003 (10)	0.0026 (12)	0.0060 (11)
C14	0.0452 (14)	0.0457 (12)	0.0540 (13)	0.0056 (10)	−0.0004 (11)	0.0068 (10)
C15	0.0439 (13)	0.0522 (14)	0.0543 (14)	0.0073 (11)	0.0045 (11)	0.0119 (11)
C16	0.0590 (16)	0.0521 (15)	0.0595 (15)	0.0054 (12)	0.0057 (12)	0.0170 (13)
C17	0.0525 (15)	0.0530 (14)	0.0597 (16)	0.0086 (11)	0.0005 (12)	0.0191 (12)

Geometric parameters (Å, º) top

O—C8	1.348 (3)	C7—H7B	0.9700
O—C7	1.441 (3)	C8—C13	1.388 (3)
N1—C16	1.146 (3)	C8—C9	1.405 (3)
C1—C2	1.373 (4)	C9—C10	1.374 (3)
C1—C6	1.385 (4)	C9—H9A	0.9300
C1—H1A	0.9300	C10—C11	1.405 (3)
N2—C17	1.140 (3)	C10—H10A	0.9300
C2—C3	1.337 (5)	C11—C12	1.413 (3)
C2—H2A	0.9300	C11—C14	1.437 (3)
C3—C4	1.374 (5)	C12—C13	1.362 (3)
C3—H3A	0.9300	C12—H12A	0.9300
C4—C5	1.401 (5)	C13—H13A	0.9300
C4—H4A	0.9300	C14—C15	1.356 (3)
C5—C6	1.376 (4)	C14—H14A	0.9300
C5—H5A	0.9300	C15—C16	1.434 (4)
C6—C7	1.495 (3)	C15—C17	1.434 (4)
C7—H7A	0.9700

C8—O—C7	119.02 (18)	O—C8—C9	125.1 (2)
C2—C1—C6	120.6 (3)	C13—C8—C9	119.4 (2)
C2—C1—H1A	119.7	C10—C9—C8	119.9 (2)
C6—C1—H1A	119.7	C10—C9—H9A	120.1
C3—C2—C1	120.6 (3)	C8—C9—H9A	120.1
C3—C2—H2A	119.7	C9—C10—C11	121.6 (2)
C1—C2—H2A	119.7	C9—C10—H10A	119.2
C2—C3—C4	120.7 (3)	C11—C10—H10A	119.2
C2—C3—H3A	119.7	C10—C11—C12	116.8 (2)
C4—C3—H3A	119.7	C10—C11—C14	126.4 (2)
C3—C4—C5	119.7 (3)	C12—C11—C14	116.7 (2)
C3—C4—H4A	120.2	C13—C12—C11	122.0 (2)
C5—C4—H4A	120.2	C13—C12—H12A	119.0
C6—C5—C4	119.5 (3)	C11—C12—H12A	119.0
C6—C5—H5A	120.3	C12—C13—C8	120.3 (2)
C4—C5—H5A	120.3	C12—C13—H13A	119.9
C5—C6—C1	119.0 (3)	C8—C13—H13A	119.9
C5—C6—C7	121.2 (3)	C15—C14—C11	132.4 (2)
C1—C6—C7	119.8 (2)	C15—C14—H14A	113.8
O—C7—C6	107.69 (19)	C11—C14—H14A	113.8
O—C7—H7A	110.2	C14—C15—C16	125.0 (2)
C6—C7—H7A	110.2	C14—C15—C17	119.1 (2)
O—C7—H7B	110.2	C16—C15—C17	115.9 (2)
C6—C7—H7B	110.2	N1—C16—C15	178.1 (3)
H7A—C7—H7B	108.5	N2—C17—C15	178.5 (3)
O—C8—C13	115.49 (19)

C6—C1—C2—C3	−0.4 (4)	C13—C8—C9—C10	0.0 (4)
C1—C2—C3—C4	0.0 (5)	C8—C9—C10—C11	0.2 (4)
C2—C3—C4—C5	0.3 (5)	C9—C10—C11—C12	−0.3 (3)
C3—C4—C5—C6	−0.1 (5)	C9—C10—C11—C14	−179.6 (2)
C4—C5—C6—C1	−0.4 (4)	C10—C11—C12—C13	0.1 (3)
C4—C5—C6—C7	−177.8 (2)	C14—C11—C12—C13	179.5 (2)
C2—C1—C6—C5	0.6 (4)	C11—C12—C13—C8	0.1 (4)
C2—C1—C6—C7	178.1 (2)	O—C8—C13—C12	179.3 (2)
C8—O—C7—C6	175.8 (2)	C9—C8—C13—C12	−0.2 (4)
C5—C6—C7—O	84.0 (3)	C10—C11—C14—C15	−0.5 (4)
C1—C6—C7—O	−93.4 (3)	C12—C11—C14—C15	−179.8 (2)
C7—O—C8—C13	−179.1 (2)	C11—C14—C15—C16	0.3 (4)
C7—O—C8—C9	0.4 (3)	C11—C14—C15—C17	179.4 (2)
O—C8—C9—C10	−179.4 (2)

Experimental details

Crystal data
Chemical formula	C₁₇H₁₂N₂O
M_r	260.29
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	6.8470 (14), 9.6270 (19), 10.544 (2)
α, β, γ (°)	100.66 (3), 91.65 (3), 94.26 (3)
V (Å³)	680.5 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.976, 0.992
No. of measured, independent and observed [I > 2σ(I)] reflections	2722, 2496, 1664
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.061, 0.176, 1.00
No. of reflections	2496
No. of parameters	181
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.18

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

This research work was supported financially by the College of Life Science and Pharmaceutical Engineering, Nanjing University of Technology and the `973' project (grant No. 2012CB725204) of the Key Basic Research Program of China.

References

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