organic compounds
2-[4-(Benzyloxy)benzylidene]malononitrile
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
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 see: Zhu et al. (2007).
Experimental
Crystal data
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Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell 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
10.1107/S1600536812020053/pv2535sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812020053/pv2535Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812020053/pv2535Isup3.cml
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.
All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 and 0.97 Å, for aryl and methylene H-atoms, respectively. The Uiso(H) were allowed at 1.2Ueq(C).
Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell
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).C17H12N2O | Z = 2 |
Mr = 260.29 | F(000) = 272 |
Triclinic, P1 | Dx = 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 |
Enraf–Nonius CAD-4 diffractometer | 1664 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.022 |
Graphite monochromator | θmax = 25.4°, θmin = 2.0° |
ω/2θ scans | h = 0→8 |
Absorption correction: ψ scan (North et al., 1968) | k = −11→11 |
Tmin = 0.976, Tmax = 0.992 | l = −12→12 |
2722 measured reflections | 3 standard reflections every 200 reflections |
2496 independent reflections | intensity decay: 1% |
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(Fo2) + (0.1P)2 + 0.110P] where P = (Fo2 + 2Fc2)/3 |
2496 reflections | (Δ/σ)max < 0.001 |
181 parameters | Δρmax = 0.22 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
C17H12N2O | γ = 94.26 (3)° |
Mr = 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)° |
Enraf–Nonius CAD-4 diffractometer | 1664 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.022 |
Tmin = 0.976, Tmax = 0.992 | 3 standard reflections every 200 reflections |
2722 measured reflections | intensity decay: 1% |
2496 independent reflections |
R[F2 > 2σ(F2)] = 0.061 | 0 restraints |
wR(F2) = 0.176 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.22 e Å−3 |
2496 reflections | Δρmin = −0.18 e Å−3 |
181 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
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) |
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) |
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 |
Mr | 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) |
Tmin, Tmax | 0.976, 0.992 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2722, 2496, 1664 |
Rint | 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 |
Δρmax, Δρmin (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
Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Kharas, G. B., Russell, S. M., Tran, V., Tolefree, Q. L., Tulewicz, D. M., Gora, A., Bajgoric, J., Balco, M. T., Dickey, G. A. & Kladis, G. (2007). J. Macromol. Sci. Part A Pure Appl. Chem., 45, 5–8. CrossRef Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhu, N., Tran, P., Bell, N. & Stevens, C. L. K. (2007). J. Chem. Crystallogr. 37, 670–683. Web of Science CSD CrossRef Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
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).