Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680202175X/om6120sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680202175X/om6120Isup2.hkl |
CCDC reference: 202359
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.005 Å
- R factor = 0.043
- wR factor = 0.151
- Data-to-parameter ratio = 13.9
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
H2SO4 (98%, 0.5 ml) was added dropwise to an ethanol solution (20 ml) containing 2,4-dinitrophenylhydrazine (0.40 g, 0.2 mmol) at 333 K. Then propiophenone (0.27 g, 0.2 mmol) was added slowly to the above solution with continuous stirring. Red crystals of the title compound appeared immediately. The solution was cooled to room temperature and the crystals isolated. Recrystallization was performed twice, from chloroform and acetone in turn, to obtain well shaped single crystals.
The H atoms were placed in calculated positions, with C—H = 0.93—0.97 Å and N—H = 0.86 Å. The torsion angle of the C15-methyl group was refined. All H atoms were included in the final cycles of refinement in the riding mode, with Uiso(H) = 1.2Ueq of carrier atoms.
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1992); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1985); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: WinGX (Farrugia, 1999).
C15H14N4O4 | F(000) = 656 |
Mr = 314.30 | Dx = 1.406 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -P 2ybc | Cell parameters from 25 reflections |
a = 13.976 (2) Å | θ = 4.6–12.5° |
b = 15.380 (4) Å | µ = 0.11 mm−1 |
c = 7.0465 (18) Å | T = 298 K |
β = 101.38 (2)° | Prism, red |
V = 1484.9 (6) Å3 | 0.55 × 0.45 × 0.35 mm |
Z = 4 |
Rigaku AFC-7S diffractometer | Rint = 0.065 |
Radiation source: fine-focus sealed tube | θmax = 26.0°, θmin = 2.6° |
Graphite monochromator | h = −17→16 |
ω/2θ scans | k = −18→0 |
3168 measured reflections | l = 0→8 |
2920 independent reflections | 3 standard reflections every 150 reflections |
1124 reflections with I > 2σ(I) | intensity decay: 0.3% |
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)] = 0.043 | H-atom parameters constrained |
wR(F2) = 0.151 | w = 1/[σ2(Fo2) + (0.0665P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.95 | (Δ/σ)max < 0.001 |
2920 reflections | Δρmax = 0.19 e Å−3 |
210 parameters | Δρmin = −0.17 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0064 (13) |
C15H14N4O4 | V = 1484.9 (6) Å3 |
Mr = 314.30 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.976 (2) Å | µ = 0.11 mm−1 |
b = 15.380 (4) Å | T = 298 K |
c = 7.0465 (18) Å | 0.55 × 0.45 × 0.35 mm |
β = 101.38 (2)° |
Rigaku AFC-7S diffractometer | Rint = 0.065 |
3168 measured reflections | 3 standard reflections every 150 reflections |
2920 independent reflections | intensity decay: 0.3% |
1124 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.151 | H-atom parameters constrained |
S = 0.95 | Δρmax = 0.19 e Å−3 |
2920 reflections | Δρmin = −0.17 e Å−3 |
210 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 | 0.80295 (17) | 0.57586 (17) | 1.1082 (4) | 0.0733 (7) | |
O2 | 0.77758 (16) | 0.44078 (17) | 1.0329 (4) | 0.0724 (7) | |
O3 | 0.55603 (19) | 0.78262 (15) | 0.8974 (4) | 0.0871 (9) | |
O4 | 0.41581 (18) | 0.74987 (14) | 0.7271 (4) | 0.0747 (8) | |
N1 | 0.75102 (19) | 0.5166 (2) | 1.0292 (4) | 0.0552 (7) | |
N2 | 0.4982 (2) | 0.72865 (16) | 0.8146 (4) | 0.0574 (8) | |
N3 | 0.37046 (17) | 0.58812 (15) | 0.6397 (4) | 0.0481 (7) | |
H3 | 0.3466 | 0.6398 | 0.6352 | 0.058* | |
N4 | 0.31422 (18) | 0.51961 (14) | 0.5545 (3) | 0.0455 (7) | |
C1 | 0.4629 (2) | 0.57305 (17) | 0.7298 (4) | 0.0387 (7) | |
C2 | 0.5272 (2) | 0.63907 (17) | 0.8188 (4) | 0.0429 (8) | |
C3 | 0.6211 (2) | 0.62040 (19) | 0.9164 (4) | 0.0463 (8) | |
H3A | 0.6618 | 0.6647 | 0.9750 | 0.056* | |
C4 | 0.6532 (2) | 0.53652 (19) | 0.9255 (4) | 0.0426 (7) | |
C5 | 0.5938 (2) | 0.46978 (18) | 0.8367 (4) | 0.0445 (8) | |
H5 | 0.6171 | 0.4130 | 0.8425 | 0.053* | |
C6 | 0.5013 (2) | 0.48765 (17) | 0.7410 (4) | 0.0420 (7) | |
H6 | 0.4623 | 0.4425 | 0.6814 | 0.050* | |
C7 | 0.2229 (2) | 0.53496 (19) | 0.4898 (4) | 0.0441 (8) | |
C8 | 0.1667 (2) | 0.45925 (19) | 0.3949 (4) | 0.0454 (8) | |
C9 | 0.0727 (2) | 0.4683 (2) | 0.2878 (5) | 0.0614 (10) | |
H9 | 0.0425 | 0.5225 | 0.2789 | 0.074* | |
C10 | 0.0234 (2) | 0.3977 (3) | 0.1944 (5) | 0.0740 (12) | |
H10 | −0.0395 | 0.4048 | 0.1227 | 0.089* | |
C11 | 0.0659 (3) | 0.3180 (3) | 0.2063 (6) | 0.0716 (11) | |
H11 | 0.0326 | 0.2709 | 0.1418 | 0.086* | |
C12 | 0.1582 (3) | 0.3075 (2) | 0.3138 (6) | 0.0710 (11) | |
H12 | 0.1872 | 0.2528 | 0.3239 | 0.085* | |
C13 | 0.2079 (2) | 0.3772 (2) | 0.4068 (5) | 0.0586 (9) | |
H13 | 0.2706 | 0.3692 | 0.4791 | 0.070* | |
C14 | 0.1735 (2) | 0.6207 (2) | 0.5064 (5) | 0.0560 (9) | |
H14A | 0.2011 | 0.6468 | 0.6305 | 0.067* | |
H14B | 0.1047 | 0.6106 | 0.5027 | 0.067* | |
C15 | 0.1842 (3) | 0.6837 (2) | 0.3471 (6) | 0.0745 (11) | |
H15A | 0.2522 | 0.6934 | 0.3488 | 0.089* | |
H15C | 0.1534 | 0.7378 | 0.3671 | 0.089* | |
H15B | 0.1537 | 0.6597 | 0.2241 | 0.089* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0600 (15) | 0.0806 (17) | 0.0711 (17) | −0.0114 (14) | −0.0071 (13) | 0.0024 (15) |
O2 | 0.0606 (15) | 0.0683 (17) | 0.0833 (18) | 0.0227 (13) | 0.0019 (13) | 0.0099 (13) |
O3 | 0.0819 (17) | 0.0361 (12) | 0.129 (2) | −0.0082 (13) | −0.0155 (16) | −0.0100 (15) |
O4 | 0.0651 (16) | 0.0397 (12) | 0.109 (2) | 0.0123 (12) | −0.0085 (15) | −0.0025 (13) |
N1 | 0.0493 (18) | 0.0617 (19) | 0.0535 (18) | 0.0055 (16) | 0.0072 (14) | 0.0082 (15) |
N2 | 0.0607 (19) | 0.0341 (16) | 0.073 (2) | 0.0011 (14) | 0.0029 (16) | −0.0007 (14) |
N3 | 0.0451 (14) | 0.0333 (13) | 0.0617 (17) | 0.0038 (11) | 0.0006 (13) | −0.0041 (13) |
N4 | 0.0455 (16) | 0.0387 (14) | 0.0498 (16) | 0.0005 (13) | 0.0031 (12) | 0.0010 (12) |
C1 | 0.0435 (17) | 0.0332 (16) | 0.0399 (17) | −0.0003 (14) | 0.0093 (14) | 0.0006 (14) |
C2 | 0.0484 (19) | 0.0297 (15) | 0.050 (2) | 0.0025 (14) | 0.0077 (15) | −0.0011 (14) |
C3 | 0.0429 (17) | 0.0428 (18) | 0.052 (2) | −0.0059 (14) | 0.0056 (15) | −0.0010 (15) |
C4 | 0.0391 (16) | 0.0452 (18) | 0.0435 (18) | 0.0054 (14) | 0.0080 (14) | 0.0086 (15) |
C5 | 0.054 (2) | 0.0332 (16) | 0.0471 (19) | 0.0040 (14) | 0.0112 (16) | 0.0019 (14) |
C6 | 0.0500 (18) | 0.0320 (16) | 0.0427 (18) | −0.0017 (14) | 0.0063 (15) | 0.0002 (14) |
C7 | 0.0448 (18) | 0.0464 (19) | 0.0417 (18) | 0.0072 (14) | 0.0104 (14) | 0.0072 (15) |
C8 | 0.0413 (17) | 0.0475 (18) | 0.0476 (19) | −0.0010 (15) | 0.0091 (15) | 0.0085 (16) |
C9 | 0.044 (2) | 0.065 (2) | 0.072 (2) | 0.0037 (17) | 0.0041 (18) | 0.004 (2) |
C10 | 0.041 (2) | 0.096 (3) | 0.078 (3) | −0.012 (2) | −0.0057 (18) | −0.002 (2) |
C11 | 0.059 (2) | 0.075 (3) | 0.078 (3) | −0.018 (2) | 0.007 (2) | −0.015 (2) |
C12 | 0.069 (2) | 0.051 (2) | 0.087 (3) | −0.0094 (19) | −0.001 (2) | −0.003 (2) |
C13 | 0.0478 (19) | 0.053 (2) | 0.067 (2) | −0.0030 (16) | −0.0074 (17) | 0.0008 (18) |
C14 | 0.058 (2) | 0.0491 (19) | 0.062 (2) | 0.0077 (17) | 0.0134 (17) | −0.0013 (17) |
C15 | 0.075 (2) | 0.060 (2) | 0.088 (3) | 0.014 (2) | 0.015 (2) | 0.016 (2) |
O1—N1 | 1.228 (3) | C7—C8 | 1.488 (4) |
O2—N1 | 1.222 (3) | C7—C14 | 1.504 (4) |
O3—N2 | 1.223 (3) | C8—C13 | 1.383 (4) |
O4—N2 | 1.238 (3) | C8—C9 | 1.387 (4) |
N1—C4 | 1.450 (4) | C9—C10 | 1.381 (5) |
N2—C2 | 1.435 (3) | C9—H9 | 0.930 |
N3—C1 | 1.343 (3) | C10—C11 | 1.357 (5) |
N3—N4 | 1.379 (3) | C10—H10 | 0.930 |
N3—H3 | 0.860 | C11—C12 | 1.371 (5) |
N4—C7 | 1.289 (3) | C11—H11 | 0.930 |
C1—C6 | 1.415 (4) | C12—C13 | 1.373 (4) |
C1—C2 | 1.418 (4) | C12—H12 | 0.930 |
C2—C3 | 1.386 (4) | C13—H13 | 0.930 |
C3—C4 | 1.363 (4) | C14—C15 | 1.512 (4) |
C3—H3A | 0.930 | C14—H14A | 0.970 |
C4—C5 | 1.389 (4) | C14—H14B | 0.970 |
C5—C6 | 1.363 (4) | C15—H15A | 0.960 |
C5—H5 | 0.930 | C15—H15C | 0.960 |
C6—H6 | 0.930 | C15—H15B | 0.960 |
O2—N1—O1 | 123.3 (3) | C13—C8—C9 | 117.6 (3) |
O2—N1—C4 | 117.7 (3) | C13—C8—C7 | 120.6 (3) |
O1—N1—C4 | 119.0 (3) | C9—C8—C7 | 121.7 (3) |
O3—N2—O4 | 121.4 (2) | C10—C9—C8 | 120.6 (3) |
O3—N2—C2 | 118.9 (3) | C10—C9—H9 | 119.7 |
O4—N2—C2 | 119.7 (3) | C8—C9—H9 | 119.7 |
C1—N3—N4 | 119.1 (2) | C11—C10—C9 | 120.7 (3) |
C1—N3—H3 | 120.4 | C11—C10—H10 | 119.7 |
N4—N3—H3 | 120.4 | C9—C10—H10 | 119.7 |
C7—N4—N3 | 117.0 (2) | C10—C11—C12 | 119.6 (3) |
N3—C1—C6 | 120.4 (3) | C10—C11—H11 | 120.2 |
N3—C1—C2 | 123.6 (2) | C12—C11—H11 | 120.2 |
C6—C1—C2 | 116.1 (3) | C11—C12—C13 | 120.3 (3) |
C3—C2—C1 | 121.8 (2) | C11—C12—H12 | 119.9 |
C3—C2—N2 | 116.5 (3) | C13—C12—H12 | 119.9 |
C1—C2—N2 | 121.8 (3) | C12—C13—C8 | 121.2 (3) |
C4—C3—C2 | 119.3 (3) | C12—C13—H13 | 119.4 |
C4—C3—H3A | 120.3 | C8—C13—H13 | 119.4 |
C2—C3—H3A | 120.3 | C7—C14—C15 | 112.9 (3) |
C3—C4—C5 | 121.1 (3) | C7—C14—H14A | 109.0 |
C3—C4—N1 | 119.5 (3) | C15—C14—H14A | 109.0 |
C5—C4—N1 | 119.4 (3) | C7—C14—H14B | 109.0 |
C6—C5—C4 | 119.9 (3) | C15—C14—H14B | 109.0 |
C6—C5—H5 | 120.1 | H14A—C14—H14B | 107.8 |
C4—C5—H5 | 120.1 | C14—C15—H15A | 109.5 |
C5—C6—C1 | 121.8 (3) | C14—C15—H15C | 109.5 |
C5—C6—H6 | 119.1 | H15A—C15—H15C | 109.5 |
C1—C6—H6 | 119.1 | C14—C15—H15B | 109.5 |
N4—C7—C8 | 114.5 (3) | H15A—C15—H15B | 109.5 |
N4—C7—C14 | 124.8 (3) | H15C—C15—H15B | 109.5 |
C8—C7—C14 | 120.8 (3) | ||
C1—N3—N4—C7 | 172.1 (3) | N1—C4—C5—C6 | 179.1 (3) |
N4—N3—C1—C6 | −1.5 (4) | C4—C5—C6—C1 | −0.4 (4) |
N4—N3—C1—C2 | 178.9 (3) | N3—C1—C6—C5 | −177.9 (3) |
N3—C1—C2—C3 | 177.7 (3) | C2—C1—C6—C5 | 1.8 (4) |
C6—C1—C2—C3 | −2.0 (4) | N3—N4—C7—C8 | 178.4 (2) |
N3—C1—C2—N2 | −1.6 (5) | N3—N4—C7—C14 | −2.0 (4) |
C6—C1—C2—N2 | 178.7 (3) | N4—C7—C8—C13 | 10.0 (4) |
O3—N2—C2—C3 | −0.8 (4) | C14—C7—C8—C13 | −169.6 (3) |
O4—N2—C2—C3 | 178.8 (3) | N4—C7—C8—C9 | −168.3 (3) |
O3—N2—C2—C1 | 178.5 (3) | C14—C7—C8—C9 | 12.1 (4) |
O4—N2—C2—C1 | −1.9 (5) | C13—C8—C9—C10 | −1.1 (5) |
C1—C2—C3—C4 | 0.8 (4) | C7—C8—C9—C10 | 177.3 (3) |
N2—C2—C3—C4 | −179.9 (3) | C8—C9—C10—C11 | 0.3 (5) |
C2—C3—C4—C5 | 0.8 (5) | C9—C10—C11—C12 | 0.7 (6) |
C2—C3—C4—N1 | −179.3 (3) | C10—C11—C12—C13 | −0.9 (6) |
O2—N1—C4—C3 | −179.4 (3) | C11—C12—C13—C8 | 0.1 (6) |
O1—N1—C4—C3 | 0.5 (4) | C9—C8—C13—C12 | 0.9 (5) |
O2—N1—C4—C5 | 0.5 (4) | C7—C8—C13—C12 | −177.5 (3) |
O1—N1—C4—C5 | −179.7 (3) | N4—C7—C14—C15 | 84.1 (4) |
C3—C4—C5—C6 | −1.0 (4) | C8—C7—C14—C15 | −96.4 (3) |
Experimental details
Crystal data | |
Chemical formula | C15H14N4O4 |
Mr | 314.30 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 13.976 (2), 15.380 (4), 7.0465 (18) |
β (°) | 101.38 (2) |
V (Å3) | 1484.9 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.55 × 0.45 × 0.35 |
Data collection | |
Diffractometer | Rigaku AFC-7S diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3168, 2920, 1124 |
Rint | 0.065 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.151, 0.95 |
No. of reflections | 2920 |
No. of parameters | 210 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.19, −0.17 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1992), MSC/AFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 1985), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 1997), XP (Siemens, 1994), WinGX (Farrugia, 1999).
N1—C4 | 1.450 (4) | N3—N4 | 1.379 (3) |
N2—C2 | 1.435 (3) | N4—C7 | 1.289 (3) |
N3—C1 | 1.343 (3) | ||
O2—N1—O1 | 123.3 (3) | C1—N3—N4 | 119.1 (2) |
O3—N2—O4 | 121.4 (2) | C7—N4—N3 | 117.0 (2) |
As some phenylhydrazone derivatives have been shown to be potentially DNA damaging and mutagenic agents (Okabe et al., 1993), a series of new phenylhydrazone derivatives have been synthesized in the laboratory. In order to investigate the relationship of the biological activity and the molecular structure, the X-ray structure determination of the title compound, (I), was carried out and is presented here.
The molecular structure of (I) is shown in Fig. 1. The molecule has an E configuration. Within the C1-phenyl ring, an appreciable difference in C—C bond distances is observed; this is consistent with the situation in acetophenone 2,4-dinitrophenylhydrazone (Shan et al., 2002). The N3···O4 separation of 2.611 (3) Å and the N3—H3···O4 angle of 128° suggest the existence of intramoleculaar hydrogen bonding between the amino and the neighboring nitro groups.
The C15···O2(1 − x, 1 − y, 1 − z) separation of 3.418 (5) Å suggests there is a van der Waals contact between the C15-methyl group and the N1-nitro group of neighboring molecule. This may be responsible for the twist of the C14/C7/N4 plane from the C8-phenyl ring plane signified by the interplanarangle of 11.2 (2)° and the atomic displacements of 0.302 (2) (C14) and −0.162 (3) Å (N4) from the C8-phenyl plane, as shown in Fig. 2.