organic compounds
of 2-[2-(benzyloxy)benzylidene]malononitrile
aH.E.J. Research Institute of Chemistry, International Center for Chemical and Biological Sciences, University of Karachi, Karachi 75270, Pakistan
*Correspondence e-mail: dr.sammer.yousuf@gmail.com
In the title benzylidenemalononitrile derivative, C17H12N2O, the dihedral angles between the central benzene ring and the Y-shaped C=C(CN)2 group (r.m.s. deviation = 0.006 Å) and the terminal benzene ring are 12.72 (8) and 37.60 (11)°, respectively. The Car—O—Csp3—Car torsion angle is −174.52 (13)° and the major twist between the aromatic rings occurs about the Csp3—Car bond. Weak aromatic π–π stacking [centroid–centroid separation = 3.7784 (13) Å; slippage = 1.21 Å] between inversion-related pairs of the central benzene rings is observed in the crystal.
CCDC reference: 1409734
1. Related literature
For the applications and biological activities of benzylidenemalononitrile derivatives, see: Turpaev et al. (2011); Sagara et al. (2002); Novogrodsky et al. (1994); Gazit et al. (1989). For the of a related compound, see: Gan et al. (2012).
2. Experimental
2.1. Crystal data
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2.3. Refinement
|
Data collection: SMART (Bruker, 2000); cell SAINT (Bruker, 2000); data reduction: SAINT; 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
CCDC reference: 1409734
https://doi.org/10.1107/S2056989015012608/hb7442sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015012608/hb7442Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989015012608/hb7442Isup3.cml
In a round-bottomed flask 2-benzyloxybenzaldehyde (1 mmol) and a catalytic amount (3 mol%) of Bi(NO3)3 in water/ethanol (10 ml) were stirred for 2 minutes at room temperature followed by the additon of malononitrile (1.1 mmol). The reaction mixture was refluxed for 20 minutes. After completion of the reaction (TLC analysis), Bi(NO3)3 was filtered for the next use and the filtrate was kept at room temperature over night to obtain crystals. Crystals were filtered, washed with water, dried, and re-crystallized from hot ethanol as colourless plates. Thin layer
was carried out on aluminium plates pre-coated with silica gel (Kieselgel 60, E. Merck, Darmstadt, Germany). UV light at 254 and 365 nm was used for chromatograms visualization.H atoms on phenyl and methine were positioned geometrically with C—H = 0.93 Å (CH phenyl) and 0.97 Å (CH) and constrained to ride on their parent atoms with Uiso(H)=1.2Ueq(CH).
Malononitriles and their benzylidene derivative represent a wide group of organic compounds having a number of pharmacological activities including inhibition of epidermal growth factor protein tyrosine kinas (Turpaev et al., 2011, Gazit et al., 1989), expression of iNOS and COX-2 pro-inflammatory agents. Structural analogues of benzylidenemalononitrile are also known to have α release) (Novogrodsky et al., 1994). The title compound was obtained as a part of our ongoing resaerch to synthesize and evaluate the biological activities of structural analogues having benzylidenemalononitrile as basic nucleus.
scavenging (Sagara et al., 2002) and antiinflammatory properties (suppression of TNFThe structure of title compound is similar to that of previously published 2-[4-(benzyloxy)benzylidene]malononitrile (Gan et al., 2012) with the difference that the benzyloxy (O1/C1–C7) group found to be attached at ortho position on benzylidenemalononitrile (N1/N2/C8–C16) moiety (Fig. 1) in contrast to para position, as observed in previously published 2-[4-(Benzyloxy)benzylidene]malononitrile. The dihedral angles between two planner phenyl rings phenyl(C1–C6)and (C8–C13) is 37.60 (11)°. Dicyanoethylene (N1–N2/C14–C17) group found to be coplanar with the benzene ring (C8–C13) to which it is attached. The bond lengths and angle were found to be similar as in structurally related 2-[4-(benzyloxy)benzylidene]malononitrile (Gan et al., 2012).
For the applications and biological activities of benzylidenemalononitrile derivatives, see: Turpaev et al. (2011); Sagara et al. (2002); Novogrodsky et al. (1994); Gazit et al. (1989). For the
of a related compound, see: Gan et al. (2012).Data collection: SMART (Bruker, 2000); cell
SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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).Fig. 1. The molecular structure of (I) with displacement ellipsoids drawn at 30% probability level. | |
Fig. 2. The crystal packing of the title compound (I). |
C17H12N2O | Z = 2 |
Mr = 260.29 | F(000) = 272 |
Triclinic, P1 | Dx = 1.267 Mg m−3 |
a = 7.2959 (9) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.4963 (12) Å | Cell parameters from 1299 reflections |
c = 11.0280 (14) Å | θ = 2.3–20.8° |
α = 97.709 (3)° | µ = 0.08 mm−1 |
β = 107.953 (3)° | T = 293 K |
γ = 105.155 (3)° | Plate, colourless |
V = 682.13 (15) Å3 | 0.34 × 0.11 × 0.07 mm |
Bruker SMART APEX CCD diffractometer | 2545 independent reflections |
Radiation source: fine-focus sealed tube | 1722 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
ω scan | θmax = 25.5°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −8→8 |
Tmin = 0.973, Tmax = 0.994 | k = −11→11 |
7776 measured reflections | l = −13→13 |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.112 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0495P)2 + 0.016P] where P = (Fo2 + 2Fc2)/3 |
2545 reflections | (Δ/σ)max < 0.001 |
181 parameters | Δρmax = 0.11 e Å−3 |
0 restraints | Δρmin = −0.17 e Å−3 |
C17H12N2O | γ = 105.155 (3)° |
Mr = 260.29 | V = 682.13 (15) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.2959 (9) Å | Mo Kα radiation |
b = 9.4963 (12) Å | µ = 0.08 mm−1 |
c = 11.0280 (14) Å | T = 293 K |
α = 97.709 (3)° | 0.34 × 0.11 × 0.07 mm |
β = 107.953 (3)° |
Bruker SMART APEX CCD diffractometer | 2545 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 1722 reflections with I > 2σ(I) |
Tmin = 0.973, Tmax = 0.994 | Rint = 0.032 |
7776 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.112 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.11 e Å−3 |
2545 reflections | Δρmin = −0.17 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 | ||
O1 | 0.37248 (18) | 0.70351 (12) | 0.15139 (10) | 0.0558 (3) | |
N1 | −0.0533 (3) | 0.06530 (19) | 0.15041 (17) | 0.0861 (6) | |
N2 | 0.2682 (3) | 0.38995 (18) | 0.52272 (16) | 0.0799 (6) | |
C1 | 0.6578 (3) | 0.9358 (2) | 0.36642 (19) | 0.0682 (6) | |
H1A | 0.6704 | 0.8409 | 0.3666 | 0.082* | |
C2 | 0.7541 (3) | 1.0476 (3) | 0.4799 (2) | 0.0840 (7) | |
H2A | 0.8300 | 1.0276 | 0.5565 | 0.101* | |
C3 | 0.7382 (4) | 1.1883 (3) | 0.4800 (2) | 0.0864 (7) | |
H3A | 0.8036 | 1.2639 | 0.5565 | 0.104* | |
C4 | 0.6260 (3) | 1.2171 (2) | 0.3675 (2) | 0.0816 (7) | |
H4A | 0.6163 | 1.3127 | 0.3670 | 0.098* | |
C5 | 0.5273 (3) | 1.1043 (2) | 0.2549 (2) | 0.0653 (5) | |
H5A | 0.4487 | 1.1241 | 0.1792 | 0.078* | |
C6 | 0.5432 (3) | 0.96316 (18) | 0.25284 (17) | 0.0501 (4) | |
C7 | 0.4489 (3) | 0.84695 (18) | 0.12655 (17) | 0.0573 (5) | |
H7A | 0.3388 | 0.8708 | 0.0666 | 0.069* | |
H7B | 0.5495 | 0.8453 | 0.0863 | 0.069* | |
C8 | 0.2956 (2) | 0.57991 (18) | 0.05089 (15) | 0.0459 (4) | |
C9 | 0.2793 (3) | 0.5848 (2) | −0.07670 (16) | 0.0545 (5) | |
H9A | 0.3218 | 0.6764 | −0.0978 | 0.065* | |
C10 | 0.2002 (3) | 0.4537 (2) | −0.17214 (17) | 0.0607 (5) | |
H10A | 0.1902 | 0.4575 | −0.2577 | 0.073* | |
C11 | 0.1356 (3) | 0.3172 (2) | −0.14330 (17) | 0.0609 (5) | |
H11A | 0.0824 | 0.2293 | −0.2088 | 0.073* | |
C12 | 0.1501 (3) | 0.31157 (19) | −0.01748 (16) | 0.0539 (5) | |
H12A | 0.1061 | 0.2189 | 0.0016 | 0.065* | |
C13 | 0.2296 (2) | 0.44161 (17) | 0.08304 (15) | 0.0440 (4) | |
C14 | 0.2524 (2) | 0.44280 (18) | 0.21768 (15) | 0.0478 (4) | |
H14A | 0.3315 | 0.5343 | 0.2765 | 0.057* | |
C15 | 0.1784 (2) | 0.33340 (18) | 0.27265 (15) | 0.0473 (4) | |
C16 | 0.0496 (3) | 0.1845 (2) | 0.20382 (17) | 0.0568 (5) | |
C17 | 0.2273 (3) | 0.36414 (19) | 0.41193 (19) | 0.0569 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0745 (8) | 0.0390 (7) | 0.0461 (7) | 0.0046 (6) | 0.0232 (6) | 0.0091 (5) |
N1 | 0.1044 (15) | 0.0552 (11) | 0.0784 (12) | −0.0080 (10) | 0.0388 (11) | 0.0033 (9) |
N2 | 0.1137 (15) | 0.0664 (11) | 0.0508 (11) | 0.0125 (10) | 0.0309 (10) | 0.0144 (9) |
C1 | 0.0809 (14) | 0.0509 (12) | 0.0639 (13) | 0.0202 (10) | 0.0152 (11) | 0.0126 (10) |
C2 | 0.0897 (17) | 0.0751 (16) | 0.0632 (14) | 0.0207 (13) | 0.0055 (12) | 0.0023 (12) |
C3 | 0.0827 (16) | 0.0622 (15) | 0.0862 (17) | 0.0083 (12) | 0.0189 (13) | −0.0159 (12) |
C4 | 0.0847 (16) | 0.0464 (12) | 0.1071 (19) | 0.0192 (11) | 0.0332 (14) | 0.0030 (13) |
C5 | 0.0673 (13) | 0.0491 (12) | 0.0790 (14) | 0.0183 (10) | 0.0248 (11) | 0.0177 (10) |
C6 | 0.0521 (10) | 0.0404 (10) | 0.0562 (11) | 0.0086 (8) | 0.0221 (9) | 0.0121 (8) |
C7 | 0.0675 (12) | 0.0448 (10) | 0.0564 (11) | 0.0114 (9) | 0.0205 (9) | 0.0190 (9) |
C8 | 0.0448 (10) | 0.0475 (10) | 0.0404 (9) | 0.0099 (8) | 0.0146 (8) | 0.0060 (8) |
C9 | 0.0587 (11) | 0.0578 (11) | 0.0459 (10) | 0.0130 (9) | 0.0207 (9) | 0.0156 (9) |
C10 | 0.0634 (12) | 0.0778 (14) | 0.0382 (10) | 0.0178 (10) | 0.0198 (9) | 0.0113 (10) |
C11 | 0.0663 (12) | 0.0603 (12) | 0.0443 (11) | 0.0099 (10) | 0.0189 (9) | −0.0025 (9) |
C12 | 0.0577 (11) | 0.0464 (10) | 0.0484 (11) | 0.0070 (9) | 0.0179 (9) | 0.0039 (8) |
C13 | 0.0444 (9) | 0.0430 (9) | 0.0389 (9) | 0.0090 (7) | 0.0128 (7) | 0.0066 (7) |
C14 | 0.0526 (10) | 0.0394 (9) | 0.0424 (10) | 0.0084 (8) | 0.0124 (8) | 0.0044 (7) |
C15 | 0.0540 (10) | 0.0416 (10) | 0.0410 (9) | 0.0092 (8) | 0.0163 (8) | 0.0068 (8) |
C16 | 0.0674 (12) | 0.0461 (11) | 0.0522 (11) | 0.0064 (10) | 0.0250 (9) | 0.0108 (9) |
C17 | 0.0716 (13) | 0.0442 (11) | 0.0508 (12) | 0.0083 (9) | 0.0242 (10) | 0.0123 (9) |
O1—C8 | 1.3580 (18) | C7—H7B | 0.9700 |
O1—C7 | 1.4277 (18) | C8—C9 | 1.383 (2) |
N1—C16 | 1.138 (2) | C8—C13 | 1.408 (2) |
N2—C17 | 1.140 (2) | C9—C10 | 1.374 (2) |
C1—C6 | 1.375 (2) | C9—H9A | 0.9300 |
C1—C2 | 1.378 (3) | C10—C11 | 1.374 (2) |
C1—H1A | 0.9300 | C10—H10A | 0.9300 |
C2—C3 | 1.371 (3) | C11—C12 | 1.368 (2) |
C2—H2A | 0.9300 | C11—H11A | 0.9300 |
C3—C4 | 1.366 (3) | C12—C13 | 1.397 (2) |
C3—H3A | 0.9300 | C12—H12A | 0.9300 |
C4—C5 | 1.377 (3) | C13—C14 | 1.440 (2) |
C4—H4A | 0.9300 | C14—C15 | 1.348 (2) |
C5—C6 | 1.373 (2) | C14—H14A | 0.9300 |
C5—H5A | 0.9300 | C15—C16 | 1.427 (2) |
C6—C7 | 1.494 (2) | C15—C17 | 1.435 (2) |
C7—H7A | 0.9700 | ||
C8—O1—C7 | 118.82 (13) | O1—C8—C13 | 115.91 (14) |
C6—C1—C2 | 120.69 (18) | C9—C8—C13 | 120.32 (15) |
C6—C1—H1A | 119.7 | C10—C9—C8 | 119.76 (17) |
C2—C1—H1A | 119.7 | C10—C9—H9A | 120.1 |
C3—C2—C1 | 120.0 (2) | C8—C9—H9A | 120.1 |
C3—C2—H2A | 120.0 | C9—C10—C11 | 121.12 (16) |
C1—C2—H2A | 120.0 | C9—C10—H10A | 119.4 |
C4—C3—C2 | 119.8 (2) | C11—C10—H10A | 119.4 |
C4—C3—H3A | 120.1 | C12—C11—C10 | 119.45 (16) |
C2—C3—H3A | 120.1 | C12—C11—H11A | 120.3 |
C3—C4—C5 | 119.9 (2) | C10—C11—H11A | 120.3 |
C3—C4—H4A | 120.0 | C11—C12—C13 | 121.61 (16) |
C5—C4—H4A | 120.0 | C11—C12—H12A | 119.2 |
C6—C5—C4 | 121.0 (2) | C13—C12—H12A | 119.2 |
C6—C5—H5A | 119.5 | C12—C13—C8 | 117.74 (15) |
C4—C5—H5A | 119.5 | C12—C13—C14 | 124.20 (15) |
C5—C6—C1 | 118.55 (17) | C8—C13—C14 | 118.05 (14) |
C5—C6—C7 | 119.67 (17) | C15—C14—C13 | 130.76 (15) |
C1—C6—C7 | 121.64 (16) | C15—C14—H14A | 114.6 |
O1—C7—C6 | 109.28 (14) | C13—C14—H14A | 114.6 |
O1—C7—H7A | 109.8 | C14—C15—C16 | 125.63 (15) |
C6—C7—H7A | 109.8 | C14—C15—C17 | 119.51 (15) |
O1—C7—H7B | 109.8 | C16—C15—C17 | 114.86 (14) |
C6—C7—H7B | 109.8 | N1—C16—C15 | 179.11 (19) |
H7A—C7—H7B | 108.3 | N2—C17—C15 | 179.2 (2) |
O1—C8—C9 | 123.76 (15) | ||
C6—C1—C2—C3 | −0.7 (3) | C9—C10—C11—C12 | 0.1 (3) |
C1—C2—C3—C4 | 0.2 (4) | C10—C11—C12—C13 | −0.1 (3) |
C2—C3—C4—C5 | 0.8 (4) | C11—C12—C13—C8 | −0.3 (2) |
C3—C4—C5—C6 | −1.4 (3) | C11—C12—C13—C14 | −178.75 (16) |
C4—C5—C6—C1 | 0.9 (3) | O1—C8—C13—C12 | −179.77 (14) |
C4—C5—C6—C7 | −174.84 (18) | C9—C8—C13—C12 | 0.6 (2) |
C2—C1—C6—C5 | 0.2 (3) | O1—C8—C13—C14 | −1.2 (2) |
C2—C1—C6—C7 | 175.84 (19) | C9—C8—C13—C14 | 179.23 (15) |
C8—O1—C7—C6 | −174.52 (13) | C12—C13—C14—C15 | −12.2 (3) |
C5—C6—C7—O1 | −144.67 (16) | C8—C13—C14—C15 | 169.29 (17) |
C1—C6—C7—O1 | 39.7 (2) | C13—C14—C15—C16 | −1.5 (3) |
C7—O1—C8—C9 | −2.6 (2) | C13—C14—C15—C17 | 179.08 (17) |
C7—O1—C8—C13 | 177.82 (14) | C14—C15—C16—N1 | −176 (100) |
O1—C8—C9—C10 | 179.76 (15) | C17—C15—C16—N1 | 3 (14) |
C13—C8—C9—C10 | −0.7 (2) | C14—C15—C17—N2 | −22 (16) |
C8—C9—C10—C11 | 0.3 (3) | C16—C15—C17—N2 | 159 (16) |
Experimental details
Crystal data | |
Chemical formula | C17H12N2O |
Mr | 260.29 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 7.2959 (9), 9.4963 (12), 11.0280 (14) |
α, β, γ (°) | 97.709 (3), 107.953 (3), 105.155 (3) |
V (Å3) | 682.13 (15) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.34 × 0.11 × 0.07 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.973, 0.994 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7776, 2545, 1722 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.112, 1.01 |
No. of reflections | 2545 |
No. of parameters | 181 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.11, −0.17 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Acknowledgements
The authors acknowledge the financial support of the Higher Education Commission of Pakistan (HEC)through research project No. 20–2073 20–2216 and under the National Research Program for Universities.
References
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Malononitriles and their benzylidene derivative represent a wide group of organic compounds having a number of pharmacological activities including inhibition of epidermal growth factor protein tyrosine kinas (Turpaev et al., 2011, Gazit et al., 1989), expression of iNOS and COX-2 pro-inflammatory agents. Structural analogues of benzylidenemalononitrile are also known to have free radical scavenging (Sagara et al., 2002) and antiinflammatory properties (suppression of TNFα release) (Novogrodsky et al., 1994). The title compound was obtained as a part of our ongoing resaerch to synthesize and evaluate the biological activities of structural analogues having benzylidenemalononitrile as basic nucleus.
The structure of title compound is similar to that of previously published 2-[4-(benzyloxy)benzylidene]malononitrile (Gan et al., 2012) with the difference that the benzyloxy (O1/C1–C7) group found to be attached at ortho position on benzylidenemalononitrile (N1/N2/C8–C16) moiety (Fig. 1) in contrast to para position, as observed in previously published 2-[4-(Benzyloxy)benzylidene]malononitrile. The dihedral angles between two planner phenyl rings phenyl(C1–C6)and (C8–C13) is 37.60 (11)°. Dicyanoethylene (N1–N2/C14–C17) group found to be coplanar with the benzene ring (C8–C13) to which it is attached. The bond lengths and angle were found to be similar as in structurally related 2-[4-(benzyloxy)benzylidene]malononitrile (Gan et al., 2012).