Acta Cryst. (2007). E63, o3982 [ doi:10.1107/S1600536807042870 ]
The title compound, C16H14Cl2N2O2, was synthesized by the reaction of 1-(5-chloro-2-hydroxyphenyl)ethanone with hydrazine hydrate. The molecule sits on a crystallographic center of symmetry at the mid-point of the central N-N bond and both N atoms are acceptors in an intramolecular hydrogen bond. In the crystal structure, the planar molecules are arranged in a sheet-like motif with one C-H
O bond linking molecules within the sheets and a second C-HO interaction between neighboring sheets. There is also a close ClCl intermolecular approach of 3.54 (1) Å within the sheets.
An ethanol solution (50 ml) of hydrazine (0.02 mol) and 1-(5-chloro-2-hydroxyphenyl)ethanone(0.04 mol) was refluxed and stirred for 3 h. The mixture was cooled and the resulting solid product, (I), was collected by filtration. Crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation of a solution in acetone.
All H atoms were positioned geometrically and treated as riding on their parent atoms,with C—H(methyl) = 0.96 Å, C—H(aromatic) = 0.93 Å,O—H = 0.82 Å and with Uiso(H) = 1.5Ueq(Cmethyl,O) anddn3057 1.2Ueq(Caromatic).
Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).
![[Figure 1]](./fl2158fig1thm.gif)
| Fig. 1. The molecular structure of compound (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level·Dashed lines show intramolecular hydrogen bonds. |
![[Figure 2]](./fl2158fig2thm.gif)
| Fig. 2. Packing diagram of (I), showing intermolecular C—H···O hydrogen bonds.(dashed lines). |
| C16H14Cl2N2O2 | Z = 1 |
| Mr = 337.19 | F000 = 174 |
| Triclinic, P1 | Dx = 1.504 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation λ = 0.71073 Å |
| a = 3.9105 (2) Å | Cell parameters from 1047 reflections |
| b = 6.2985 (4) Å | θ = 2.7–23.0º |
| c = 15.1479 (9) Å | µ = 0.44 mm−1 |
| α = 89.520 (2)º | T = 273 (2) K |
| β = 88.792 (1)º | Plate, colorless |
| γ = 86.164 (2)º | 0.25 × 0.18 × 0.12 mm |
| V = 372.17 (4) Å3 |
| Bruker APEX II CCD area-detector diffractometer | 1315 independent reflections |
| Radiation source: fine-focus sealed tube | 1010 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.025 |
| T = 273(2) K | θmax = 25.0º |
| phi and ω scans | θmin = 1.3º |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −4→4 |
| Tmin = 0.897, Tmax = 0.949 | k = −7→7 |
| 4295 measured reflections | l = −17→18 |
| 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)] = 0.036 | H-atom parameters constrained |
| wR(F2) = 0.081 | w = 1/[σ2(Fo2) + (0.0223P)2 + 0.229P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.00 | (Δ/σ)max = 0.003 |
| 1315 reflections | Δρmax = 0.21 e Å−3 |
| 102 parameters | Δρmin = −0.18 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| C16H14Cl2N2O2 | γ = 86.164 (2)º |
| Mr = 337.19 | V = 372.17 (4) Å3 |
| Triclinic, P1 | Z = 1 |
| a = 3.9105 (2) Å | Mo Kα |
| b = 6.2985 (4) Å | µ = 0.44 mm−1 |
| c = 15.1479 (9) Å | T = 273 (2) K |
| α = 89.520 (2)º | 0.25 × 0.18 × 0.12 mm |
| β = 88.792 (1)º |
| Bruker APEX II CCD area-detector diffractometer | 1315 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 1010 reflections with I > 2σ(I) |
| Tmin = 0.897, Tmax = 0.949 | Rint = 0.025 |
| 4295 measured reflections |
| R[F2 > 2σ(F2)] = 0.036 | 102 parameters |
| wR(F2) = 0.081 | H-atom parameters constrained |
| S = 1.00 | Δρmax = 0.21 e Å−3 |
| 1315 reflections | Δρmin = −0.18 e Å−3 |
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 > 2sigma(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 | ||
| Cl1 | 0.07776 (19) | 0.29780 (11) | 0.07597 (4) | 0.0668 (3) | |
| O1 | 0.6578 (4) | −0.3076 (2) | 0.33622 (10) | 0.0531 (4) | |
| H1 | 0.6553 | −0.2565 | 0.3859 | 0.080* | |
| N1 | 0.5071 (4) | −0.0325 (3) | 0.45587 (10) | 0.0392 (4) | |
| C1 | 0.5138 (5) | −0.1637 (3) | 0.27931 (13) | 0.0408 (5) | |
| C2 | 0.3675 (5) | 0.0368 (3) | 0.30718 (13) | 0.0357 (5) | |
| C3 | 0.2340 (5) | 0.1759 (3) | 0.24204 (13) | 0.0409 (5) | |
| H3 | 0.1387 | 0.3095 | 0.2581 | 0.049* | |
| C4 | 0.2415 (6) | 0.1185 (4) | 0.15515 (14) | 0.0458 (6) | |
| C5 | 0.3773 (6) | −0.0796 (4) | 0.12886 (14) | 0.0525 (6) | |
| H5 | 0.3771 | −0.1182 | 0.0697 | 0.063* | |
| C6 | 0.5124 (6) | −0.2187 (4) | 0.19101 (14) | 0.0509 (6) | |
| H6 | 0.6046 | −0.3521 | 0.1736 | 0.061* | |
| C7 | 0.3551 (5) | 0.0988 (3) | 0.40064 (12) | 0.0347 (5) | |
| C8 | 0.1725 (6) | 0.3052 (3) | 0.42815 (14) | 0.0450 (6) | |
| H8A | 0.0690 | 0.2888 | 0.4856 | 0.068* | |
| H8B | −0.0020 | 0.3455 | 0.3864 | 0.068* | |
| H8C | 0.3335 | 0.4136 | 0.4300 | 0.068* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cl1 | 0.0850 (5) | 0.0718 (5) | 0.0411 (3) | 0.0148 (4) | −0.0136 (3) | 0.0121 (3) |
| O1 | 0.0727 (12) | 0.0382 (9) | 0.0462 (9) | 0.0140 (8) | −0.0056 (8) | 0.0026 (7) |
| N1 | 0.0479 (11) | 0.0350 (10) | 0.0339 (8) | 0.0045 (8) | −0.0053 (8) | 0.0026 (7) |
| C1 | 0.0436 (13) | 0.0364 (12) | 0.0418 (12) | 0.0005 (10) | −0.0021 (10) | 0.0051 (9) |
| C2 | 0.0367 (12) | 0.0343 (11) | 0.0360 (11) | −0.0007 (9) | −0.0035 (9) | 0.0029 (9) |
| C3 | 0.0423 (13) | 0.0381 (12) | 0.0415 (12) | 0.0042 (10) | −0.0050 (9) | 0.0025 (9) |
| C4 | 0.0487 (14) | 0.0502 (14) | 0.0380 (12) | 0.0026 (11) | −0.0061 (10) | 0.0068 (10) |
| C5 | 0.0630 (16) | 0.0585 (16) | 0.0356 (12) | 0.0004 (12) | −0.0030 (11) | −0.0049 (11) |
| C6 | 0.0621 (16) | 0.0440 (13) | 0.0453 (13) | 0.0068 (12) | −0.0010 (11) | −0.0057 (10) |
| C7 | 0.0344 (12) | 0.0312 (11) | 0.0383 (11) | −0.0005 (9) | −0.0034 (9) | 0.0038 (9) |
| C8 | 0.0510 (14) | 0.0393 (12) | 0.0432 (12) | 0.0099 (10) | −0.0053 (10) | 0.0017 (10) |
| Cl1—C4 | 1.743 (2) | C3—H3 | 0.9300 |
| O1—C1 | 1.350 (2) | C4—C5 | 1.382 (3) |
| O1—H1 | 0.8200 | C5—C6 | 1.370 (3) |
| N1—C7 | 1.297 (2) | C5—H5 | 0.9300 |
| N1—N1i | 1.400 (3) | C6—H6 | 0.9300 |
| C1—C6 | 1.385 (3) | C7—C8 | 1.499 (3) |
| C1—C2 | 1.415 (3) | C8—H8A | 0.9600 |
| C2—C3 | 1.400 (3) | C8—H8B | 0.9600 |
| C2—C7 | 1.471 (3) | C8—H8C | 0.9600 |
| C3—C4 | 1.367 (3) | ||
| C1—O1—H1 | 109.5 | C6—C5—H5 | 120.4 |
| C7—N1—N1i | 115.28 (19) | C4—C5—H5 | 120.4 |
| O1—C1—C6 | 117.51 (19) | C5—C6—C1 | 121.1 (2) |
| O1—C1—C2 | 122.30 (18) | C5—C6—H6 | 119.5 |
| C6—C1—C2 | 120.19 (19) | C1—C6—H6 | 119.5 |
| C3—C2—C1 | 117.37 (18) | N1—C7—C2 | 116.84 (17) |
| C3—C2—C7 | 120.79 (18) | N1—C7—C8 | 123.10 (18) |
| C1—C2—C7 | 121.85 (17) | C2—C7—C8 | 120.06 (17) |
| C4—C3—C2 | 121.11 (19) | C7—C8—H8A | 109.5 |
| C4—C3—H3 | 119.4 | C7—C8—H8B | 109.5 |
| C2—C3—H3 | 119.4 | H8A—C8—H8B | 109.5 |
| C3—C4—C5 | 121.08 (19) | C7—C8—H8C | 109.5 |
| C3—C4—Cl1 | 119.64 (17) | H8A—C8—H8C | 109.5 |
| C5—C4—Cl1 | 119.27 (17) | H8B—C8—H8C | 109.5 |
| C6—C5—C4 | 119.2 (2) | ||
| O1—C1—C2—C3 | 178.2 (2) | C4—C5—C6—C1 | 0.2 (4) |
| C6—C1—C2—C3 | −1.9 (3) | O1—C1—C6—C5 | −178.6 (2) |
| O1—C1—C2—C7 | −1.7 (3) | C2—C1—C6—C5 | 1.4 (4) |
| C6—C1—C2—C7 | 178.2 (2) | N1i—N1—C7—C2 | 179.4 (2) |
| C1—C2—C3—C4 | 0.8 (3) | N1i—N1—C7—C8 | −0.7 (3) |
| C7—C2—C3—C4 | −179.3 (2) | C3—C2—C7—N1 | −174.95 (19) |
| C2—C3—C4—C5 | 0.8 (4) | C1—C2—C7—N1 | 4.9 (3) |
| C2—C3—C4—Cl1 | −179.15 (17) | C3—C2—C7—C8 | 5.1 (3) |
| C3—C4—C5—C6 | −1.3 (4) | C1—C2—C7—C8 | −175.0 (2) |
| Cl1—C4—C5—C6 | 178.66 (19) |
| Symmetry codes: (i) −x+1, −y, −z+1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1···N1 | 0.82 | 1.83 | 2.551 (2) | 146 |
| C8—H8B···O1ii | 0.96 | 2.60 | 3.368 (2) | 137 |
| C8—H8C···O1iii | 0.96 | 2.63 | 3.455 (3) | 145 |
| Symmetry codes: (ii) x−1, y+1, z; (iii) x, y+1, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1···N1 | 0.82 | 1.83 | 2.551 (2) | 146 |
| C8—H8B···O1i | 0.96 | 2.60 | 3.368 (2) | 137 |
| C8—H8C···O1ii | 0.96 | 2.63 | 3.455 (3) | 145 |
| Symmetry codes: (i) x−1, y+1, z; (ii) x, y+1, z. |
The authors thank the Education Office of Shandong Province, China, for research grant No. J06D59 and Taishan University for research grant No. Y05–2-09.
Bruker (2005). APEX2 (Version 1.27) and SAINT (Version 7.12). Bruker AXS Inc., Madison, Wisconsin, USA.
Glaser, R., Chen, G. S., Anthamatten, M. & Barnes, C. L. (1995). J. Chem. Soc. Perkin Trans. 2, pp. 1449–1458.
Hunig, S., Kemmer, M. & Wenner, H. (2000). Chem. Eur. J. 6, 2618–2632.
Kesslen, E. C., Euler, W. B. & Foxman, B. M. (1999). Chem. Mater. 11, 336–340.
Kundu, N., Chatterjee, P. B., Chaudhury, M. & Tiekink, E. R. T. (2005). Acta Cryst. E61, m1583–m1585.
Sheldrick, G. M. (1997a). SHELXS97 and SHELXL97. University of Göttingen, Germany.
Sheldrick, G. M. (1997b). SHELXTL. Version 5.10. Bruker AXS Inc., Madison, Wisconsin, USA.
Sheldrick, G. M. (2003). SADABS. Version 2.10. Bruker AXS Inc., Madison, Wisconsin, USA.
Recently, a number of azine compounds containing both a diimine linkage and N—N bonding have been investigated in terms of their crystallography and coordination chemistry (Kundu et al., 2005; Kesslen et al., 1999;). As an extension of work on the structural characterization of azine derivatives,the title compound, (I),was synthesized and its crystal structure is reported here.
In the title compound, there is a crystallographic center of symmetry at the midpoint of the N—N bond (Fig. 1.). The molecule displays an (E, E) conformation with respect to the symmetry related C=N double bonds. This configuration agrees with those commonly found in similar compounds (Glaser et al., 1995; Hunig et al., 2000). In the crystal the planar molecules are arranged in a sheet like motif with one C—H···O bond linking molecules within the sheets and a second C—H···O interaction between neighboring sheets. There is also a close Cl—Cl intermolecular approach of 3.54 (1) Å within the sheets. (Table 1 and Fig. 2).