supplementary materials
1-[1-(4-Chlorophenyl)ethylidene]carbonohydrazide
The molecular skeleton of the title molecule, C9H11ClN4O, is essentially planar, the dihedral angle between the ring and the and N/N/C plane being 6.7 (3)°. In the crystal, intermolecular N-H
O and N-HN hydrogen bonds link the molecules into ribbons propagated along [010].
p-Chloroacetophenone (5.0 mmol) and carbohydrazide (5.0 mmol) were mixed
in 50 ml flash under sovlent-free condtions After stirring 3 h at 373 K, the
resulting mixture was cooled to room temperature, and recrystalized from
ethanol, and afforded the title compound as a crystalline solid. Elemental
analysis: calculated for C9H11ClN4O: C 47.69, H 4.89, N 24.72%; found: C
47.63, H 4.75, N 24.64%.
All H atoms were placed in geometrically idealized positions (N—H 0.86 and
C—H = 0.93–0.96 Å) and treated as riding on their parent atoms, with
Uiso(H) = 1.2–1.5 Ueq(C) (C,N).
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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).
1-[1-(4-Chlorophenyl)ethylidene]carbonohydrazide
top
Crystal data top
| C9H11ClN4O | F(000) = 472 |
| Mr = 226.67 | Dx = 1.440 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| a = 14.6429 (14) Å | Cell parameters from 963 reflections |
| b = 9.6041 (12) Å | θ = 2.5–22.7° |
| c = 7.4327 (9) Å | µ = 0.34 mm−1 |
| β = 90.102 (1)° | T = 298 K |
| V = 1045.3 (2) Å3 | Needle, colourless |
| Z = 4 | 0.40 × 0.30 × 0.12 mm |
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer | 1837 independent reflections |
| Radiation source: fine-focus sealed tube | 1085 reflections with I > 2σ(I) |
| graphite | Rint = 0.037 |
| φ and ω scans | θmax = 25.0°, θmin = 1.4° |
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996) | h = −11→17 |
| Tmin = 0.875, Tmax = 0.960 | k = −11→11 |
| 4419 measured reflections | l = −7→8 |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.126 | H-atom parameters constrained |
| S = 1.01 | w = 1/[σ2(Fo2) + (0.0508P)2 + 0.3562P]
where P = (Fo2 + 2Fc2)/3 |
| 1837 reflections | (Δ/σ)max = 0.002 |
| 137 parameters | Δρmax = 0.21 e Å−3 |
| 0 restraints | Δρmin = −0.20 e Å−3 |
Crystal data top
| C9H11ClN4O | V = 1045.3 (2) Å3 |
| Mr = 226.67 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 14.6429 (14) Å | µ = 0.34 mm−1 |
| b = 9.6041 (12) Å | T = 298 K |
| c = 7.4327 (9) Å | 0.40 × 0.30 × 0.12 mm |
| β = 90.102 (1)° | |
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer | 1837 independent reflections |
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996) | 1085 reflections with I > 2σ(I) |
| Tmin = 0.875, Tmax = 0.960 | Rint = 0.037 |
| 4419 measured reflections | θmax = 25.0° |
Refinement top
| R[F2 > 2σ(F2)] = 0.045 | H-atom parameters constrained |
| wR(F2) = 0.126 | Δρmax = 0.21 e Å−3 |
| S = 1.01 | Δρmin = −0.20 e Å−3 |
| 1837 reflections | Absolute structure: ? |
| 137 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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 | Uiso*/Ueq | |
| Cl1 | 0.94869 (7) | 1.35122 (11) | 0.60169 (13) | 0.0725 (4) | |
| N1 | 0.57886 (16) | 0.7625 (2) | 0.3769 (3) | 0.0405 (7) | |
| H1 | 0.5945 | 0.6791 | 0.4057 | 0.049* | |
| N2 | 0.63579 (17) | 0.8715 (2) | 0.4127 (3) | 0.0375 (6) | |
| N3 | 0.47946 (16) | 0.9177 (2) | 0.2451 (3) | 0.0429 (7) | |
| H3 | 0.5175 | 0.9828 | 0.2719 | 0.051* | |
| N4 | 0.39947 (16) | 0.9500 (2) | 0.1494 (3) | 0.0434 (7) | |
| H4A | 0.4001 | 0.9058 | 0.0443 | 0.065* | |
| H4B | 0.3513 | 0.9224 | 0.2129 | 0.065* | |
| O1 | 0.44329 (14) | 0.6900 (2) | 0.2677 (3) | 0.0460 (6) | |
| C1 | 0.4970 (2) | 0.7867 (3) | 0.2949 (4) | 0.0358 (7) | |
| C2 | 0.7519 (2) | 0.7025 (3) | 0.5085 (4) | 0.0518 (9) | |
| H2A | 0.7062 | 0.6479 | 0.5682 | 0.078* | |
| H2B | 0.8056 | 0.7075 | 0.5825 | 0.078* | |
| H2C | 0.7669 | 0.6601 | 0.3955 | 0.078* | |
| C3 | 0.7158 (2) | 0.8469 (3) | 0.4762 (4) | 0.0357 (7) | |
| C4 | 0.77306 (19) | 0.9705 (3) | 0.5105 (4) | 0.0353 (7) | |
| C5 | 0.8596 (2) | 0.9605 (3) | 0.5861 (4) | 0.0458 (8) | |
| H5 | 0.8821 | 0.8733 | 0.6173 | 0.055* | |
| C6 | 0.9131 (2) | 1.0768 (4) | 0.6161 (4) | 0.0511 (9) | |
| H6 | 0.9710 | 1.0676 | 0.6663 | 0.061* | |
| C7 | 0.8802 (2) | 1.2056 (3) | 0.5714 (4) | 0.0443 (8) | |
| C8 | 0.7950 (2) | 1.2196 (4) | 0.4976 (4) | 0.0513 (9) | |
| H8 | 0.7729 | 1.3074 | 0.4678 | 0.062* | |
| C9 | 0.7423 (2) | 1.1031 (3) | 0.4676 (4) | 0.0475 (9) | |
| H9 | 0.6845 | 1.1136 | 0.4173 | 0.057* | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| Cl1 | 0.0749 (7) | 0.0666 (7) | 0.0758 (7) | −0.0359 (5) | −0.0187 (5) | 0.0017 (5) |
| N1 | 0.0364 (16) | 0.0234 (14) | 0.0618 (18) | 0.0002 (12) | −0.0087 (13) | 0.0031 (12) |
| N2 | 0.0367 (15) | 0.0287 (15) | 0.0471 (15) | −0.0058 (12) | −0.0022 (12) | −0.0013 (11) |
| N3 | 0.0377 (16) | 0.0238 (15) | 0.0671 (18) | −0.0020 (12) | −0.0125 (13) | 0.0000 (12) |
| N4 | 0.0361 (15) | 0.0335 (15) | 0.0605 (17) | 0.0027 (12) | −0.0060 (12) | 0.0004 (12) |
| O1 | 0.0397 (13) | 0.0231 (12) | 0.0753 (16) | −0.0055 (10) | −0.0085 (11) | 0.0006 (10) |
| C1 | 0.0372 (19) | 0.0216 (18) | 0.0488 (19) | 0.0004 (14) | 0.0016 (15) | −0.0018 (14) |
| C2 | 0.055 (2) | 0.043 (2) | 0.058 (2) | 0.0051 (18) | −0.0117 (17) | −0.0020 (16) |
| C3 | 0.0360 (19) | 0.0370 (18) | 0.0342 (16) | 0.0020 (15) | −0.0013 (14) | −0.0022 (14) |
| C4 | 0.0332 (18) | 0.0379 (19) | 0.0349 (17) | −0.0019 (14) | −0.0016 (14) | −0.0011 (14) |
| C5 | 0.042 (2) | 0.044 (2) | 0.051 (2) | −0.0002 (17) | −0.0057 (16) | 0.0064 (16) |
| C6 | 0.041 (2) | 0.061 (3) | 0.052 (2) | −0.0070 (19) | −0.0125 (16) | 0.0029 (18) |
| C7 | 0.045 (2) | 0.045 (2) | 0.0431 (19) | −0.0125 (17) | −0.0041 (16) | −0.0033 (15) |
| C8 | 0.052 (2) | 0.037 (2) | 0.065 (2) | −0.0075 (17) | −0.0142 (18) | 0.0026 (16) |
| C9 | 0.0366 (19) | 0.042 (2) | 0.064 (2) | −0.0034 (16) | −0.0142 (16) | 0.0021 (17) |
Geometric parameters (Å, °) top
| Cl1—C7 | 1.735 (3) | C2—H2B | 0.9600 |
| N1—C1 | 1.364 (4) | C2—H2C | 0.9600 |
| N1—N2 | 1.364 (3) | C3—C4 | 1.476 (4) |
| N1—H1 | 0.8600 | C4—C5 | 1.388 (4) |
| N2—C3 | 1.285 (4) | C4—C9 | 1.387 (4) |
| N3—C1 | 1.336 (3) | C5—C6 | 1.382 (4) |
| N3—N4 | 1.404 (3) | C5—H5 | 0.9300 |
| N3—H3 | 0.8600 | C6—C7 | 1.368 (4) |
| N4—H4A | 0.8900 | C6—H6 | 0.9300 |
| N4—H4B | 0.8900 | C7—C8 | 1.369 (4) |
| O1—C1 | 1.234 (3) | C8—C9 | 1.378 (4) |
| C2—C3 | 1.502 (4) | C8—H8 | 0.9300 |
| C2—H2A | 0.9600 | C9—H9 | 0.9300 |
| | | |
| C1—N1—N2 | 119.5 (2) | N2—C3—C2 | 123.3 (3) |
| C1—N1—H1 | 120.2 | C4—C3—C2 | 121.1 (3) |
| N2—N1—H1 | 120.3 | C5—C4—C9 | 116.9 (3) |
| C3—N2—N1 | 119.1 (2) | C5—C4—C3 | 122.1 (3) |
| C1—N3—N4 | 120.5 (2) | C9—C4—C3 | 121.0 (3) |
| C1—N3—H3 | 119.7 | C6—C5—C4 | 121.7 (3) |
| N4—N3—H3 | 119.7 | C6—C5—H5 | 119.1 |
| N3—N4—H4A | 109.2 | C4—C5—H5 | 119.1 |
| N3—N4—H4B | 109.1 | C7—C6—C5 | 119.5 (3) |
| H4A—N4—H4B | 109.5 | C7—C6—H6 | 120.2 |
| O1—C1—N3 | 122.8 (3) | C5—C6—H6 | 120.2 |
| O1—C1—N1 | 120.3 (3) | C6—C7—C8 | 120.4 (3) |
| N3—C1—N1 | 116.9 (3) | C6—C7—Cl1 | 119.6 (2) |
| C3—C2—H2A | 109.5 | C8—C7—Cl1 | 119.9 (3) |
| C3—C2—H2B | 109.5 | C7—C8—C9 | 119.7 (3) |
| H2A—C2—H2B | 109.5 | C7—C8—H8 | 120.2 |
| C3—C2—H2C | 109.5 | C9—C8—H8 | 120.2 |
| H2A—C2—H2C | 109.5 | C8—C9—C4 | 121.8 (3) |
| H2B—C2—H2C | 109.5 | C8—C9—H9 | 119.1 |
| N2—C3—C4 | 115.6 (3) | C4—C9—H9 | 119.1 |
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1···N4i | 0.86 | 2.24 | 3.024 (3) | 152 |
| N3—H3···O1ii | 0.86 | 2.09 | 2.850 (3) | 147 |
| N4—H4A···O1iii | 0.89 | 2.34 | 3.206 (3) | 164 |
| Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x+1, y+1/2, −z+1/2; (iii) x, −y+3/2, z−1/2. |
Table 1
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1···N4i | 0.86 | 2.24 | 3.024 (3) | 152 |
| N3—H3···O1ii | 0.86 | 2.09 | 2.850 (3) | 147 |
| N4—H4A···O1iii | 0.89 | 2.34 | 3.206 (3) | 164 |
| Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x+1, y+1/2, −z+1/2; (iii) x, −y+3/2, z−1/2. |
The authors acknowledge financial support by the Science Foundation of China
(grant No. 20877037).
Loncle, C., Brunel, J. M., Vidal, N., Dherbomez, M. & Letourneux, Y. (2004). Eur. J. Med. Chem. 39, 1067–1071.
Meyers, C. Y., Kolb, V. M. & Robinson, P. D. (1995). Acta Cryst. C51, 775–777.
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.
![[Figure 1]](./cv2587fig1thm.gif)
A number of carbonohydrazide derivatives have been claimed to possess a bioactivity such as antibacterial, antifungal, anticonvulsant and anticancer activities (Loncle et al., 2004). We describe in this paper a user-friendly, solvent-free protocol for the synthesis of substituted carbonohydrazide starting from the fragrant ketones and carbohydrazide under solvent-free conditions in this paper. Using this method, which can be considered as a a general method for the synthesis of substituted carbonohydrazides, we obtained the title compound, (I). We present here its crystal structure.
In (I) (Fig. 1), the bond lengths and angles are normal and correspond to those observed in bis(3-fluorophenylmethine)carbonohydrazide (Meyers et al., 1995). The N4/N3/C1 and N2/N1/C1 planes form a dihedral angle of 4.09 (4)°, while ring C4-C9 and N2/N1/C1 plane form a dihedral angle of 2.64 (29)°.
In the crystal, intermolecular N—H···O and N—H···N hydrogen bonds (Table 1) link the molecules into ribbons propagated in direction [010].