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access5-Bromophthalazine hemihydrate
aDepartment of Chemistry, Tangshan Normal University, Tangshan 063000, People's Republic of China
*Correspondence e-mail: cmj_1237@yahoo.com.cn
The title compound, C8H5BrN2·0.5H2O, is a phthalazine derivative synthesized from 3-bromobenzene-1,2-dicarbaldehyde and hydrazine. The molecule is essentially planar, the deviation from the mean plane of the phthalazine ring being 0.015 (3) Å. The O atom of the solvent water molecule is situated on a twofold rotation axis. In the crystal, O—H⋯N hydrogen bonds and short N⋯Br [2.980 (3) Å] contacts lead to the formation of a two-dimensional network parallel to (101).
Related literature
For general background on applications of phthalazines, see: Caira et al. (2011![[Caira, M. R., Georgescu, E., Georgescu, F., Albota, F., Dumitrascu, F. & Lorea, D. (2011). Monatsh. Chem. 142, 743-748.]](../../../../../../logos/arrows/e_arr.gif "Caira, M. R., Georgescu, E., Georgescu, F., Albota, F., Dumitrascu, F. & Lorea, D. (2011). Monatsh. Chem. 142, 743-748.")
); Musa et al. (2012).
![[Scheme 1]](im2382scheme1.gif)
Experimental
Crystal data
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Data collection: CrystalClear (Rigaku/MSC, 2002); cell CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Crystal Impact, 2009); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2006).
Supporting information
contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812030358/im2382sup1.cif
Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812030358/im2382Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536812030358/im2382Isup3.cml
A solution of 0.1 mol of 3-bromo-benzene-1,2-dicarboxaldehyde is dissolved in 100 ml of ethanol and added dropwise with constant stirring, under a blanket of nitrogen, to an ice-cooled solution of 0.3 mol of hydrazine hydrate in 100 ml of ethanol. The light yellowish reaction mixture is kept with constant stirring for an additional three hours. Ethanol and excess hydrazine are removed under reduced pressure. The remaining yellowish solid may be purified by recrystallization from diethyl ether to yield the yellowish title compound (yield 48%). Finally, the title compound was dissolved in a small amount of methanol and the solution was kept for 10 days at ambient temperature to give rise to white flake crystals due to slow evaporation of the solvent.
The H atom of the solvent water was located in a difference fourier map and refined as a riding atom with Uiso(H) = 1.2Ueq(O). Remaining H atoms were positioned geometrically with C—H = 0.93–0.98 Å and constrained to ride on their parent atoms with Uiso(H) = 1.2Ueq(C).
Phthalazine derivatives have played an important role in the development of corrosion science as they can inhibit the corrosion of mild steel (Musa et al., 2012). Moreover, they are of particular interest owing to their biological activity and optical properties (Caira, et al., 2011).
In this paper, the title new phthalazine derivative derived from the condensation of 3-bromo-benzene-1,2-dicarboxaldehyde with hydrazine is reported. The molecular structure of the title compound (Fig.1) is essentially planar with a deviation from the mean plane of the phthalazine ring of 0.0115 (3) Å. All bond lengths have normal values.The oxygen atom of the solvent water molecule is situated on a twofold rotation axis. In the crystal, O—H···N hydrogen bonds and short N···Br contacts lead to the formation of a two dimensional network structure (Fig.2).
For general background on applications of phthalazines, see: Caira et al. (2011); Musa et al. (2012).
Data collection: CrystalClear (Rigaku/MSC, 2002); cell CrystalClear (Rigaku/MSC, 2002); data reduction: CrystalClear (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Crystal Impact, 2009); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2006).
![[Figure 1]](./im2382fig1thm.gif) | Fig. 1. Molecular structure of the title compound showing 30% probability displacement ellipsoids. |
![[Figure 2]](./im2382fig2thm.gif) | Fig. 2. Molecular packing of the title compound with hydrogen bonds and N···Br contacts shown as dashed lines. |
| C8H5BrN2·0.5H2O | F(000) = 1712 |
| Mr = 218.06 | Dx = 1.895 Mg m−3 |
| Orthorhombic, Fdd2 | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: F 2 -2d | Cell parameters from 2874 reflections |
| a = 13.5000 (18) Å | θ = 1.4–28.0° |
| b = 29.964 (5) Å | µ = 5.31 mm−1 |
| c = 7.5565 (5) Å | T = 113 K |
| V = 3056.7 (7) Å3 | Prism, colorless |
| Z = 16 | 0.30 × 0.22 × 0.18 mm |
| Rigaku Saturn724 CCD diffractometer | 1819 independent reflections |
| Radiation source: rotating anode | 1781 reflections with I > 2σ(I) |
| Multilayer monochromator | Rint = 0.064 |
| Detector resolution: 14.22 pixels mm-1 | θmax = 27.8°, θmin = 2.7° |
| ω and φ scans | h = −17→17 |
| Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2002) | k = −37→39 |
| Tmin = 0.299, Tmax = 0.448 | l = −9→9 |
| 7799 measured reflections |
| 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)] = 0.029 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.074 | w = 1/[σ2(Fo2) + (0.0496P)2] where P = (Fo2 + 2Fc2)/3 |
| S = 1.06 | (Δ/σ)max = 0.001 |
| 1819 reflections | Δρmax = 0.74 e Å−3 |
| 109 parameters | Δρmin = −0.77 e Å−3 |
| 2 restraints | Absolute structure: Flack (1983), 839 Friedel pairs |
| Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.002 (10) |
| C8H5BrN2·0.5H2O | V = 3056.7 (7) Å3 |
| Mr = 218.06 | Z = 16 |
| Orthorhombic, Fdd2 | Mo Kα radiation |
| a = 13.5000 (18) Å | µ = 5.31 mm−1 |
| b = 29.964 (5) Å | T = 113 K |
| c = 7.5565 (5) Å | 0.30 × 0.22 × 0.18 mm |
| Rigaku Saturn724 CCD diffractometer | 1819 independent reflections |
| Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2002) | 1781 reflections with I > 2σ(I) |
| Tmin = 0.299, Tmax = 0.448 | Rint = 0.064 |
| 7799 measured reflections |
| R[F2 > 2σ(F2)] = 0.029 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.074 | Δρmax = 0.74 e Å−3 |
| S = 1.06 | Δρmin = −0.77 e Å−3 |
| 1819 reflections | Absolute structure: Flack (1983), 839 Friedel pairs |
| 109 parameters | Absolute structure parameter: −0.002 (10) |
| 2 restraints |
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 | ||
| Br1 | 0.655288 (19) | 0.300585 (8) | 0.53761 (6) | 0.02108 (10) | |
| N1 | 0.65121 (19) | 0.45112 (8) | 0.5432 (5) | 0.0234 (5) | |
| N2 | 0.71705 (19) | 0.47790 (9) | 0.6304 (4) | 0.0256 (6) | |
| C1 | 0.6599 (2) | 0.40781 (10) | 0.5487 (6) | 0.0204 (6) | |
| H1 | 0.6127 | 0.3904 | 0.4862 | 0.024* | |
| C2 | 0.7360 (2) | 0.38513 (10) | 0.6426 (4) | 0.0176 (5) | |
| C3 | 0.7467 (2) | 0.33818 (10) | 0.6536 (4) | 0.0184 (6) | |
| C4 | 0.8227 (2) | 0.32011 (10) | 0.7484 (4) | 0.0220 (6) | |
| H4 | 0.8286 | 0.2886 | 0.7578 | 0.026* | |
| C5 | 0.8923 (2) | 0.34786 (12) | 0.8323 (4) | 0.0245 (7) | |
| H5 | 0.9461 | 0.3348 | 0.8946 | 0.029* | |
| C6 | 0.8843 (2) | 0.39313 (11) | 0.8259 (4) | 0.0228 (7) | |
| H6 | 0.9313 | 0.4115 | 0.8846 | 0.027* | |
| C7 | 0.8049 (2) | 0.41233 (10) | 0.7306 (4) | 0.0189 (6) | |
| C8 | 0.7888 (2) | 0.45888 (11) | 0.7189 (5) | 0.0255 (7) | |
| H8 | 0.8337 | 0.4778 | 0.7801 | 0.031* | |
| O1 | 0.5000 | 0.5000 | 0.3550 (5) | 0.0295 (8) | |
| H1A | 0.543 (2) | 0.4874 (15) | 0.413 (5) | 0.045 (14)* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Br1 | 0.02422 (15) | 0.01764 (14) | 0.02139 (15) | −0.00117 (9) | −0.00086 (12) | −0.00143 (13) |
| N1 | 0.0232 (12) | 0.0237 (12) | 0.0231 (13) | 0.0039 (8) | 0.0011 (11) | 0.0018 (14) |
| N2 | 0.0291 (14) | 0.0195 (12) | 0.0281 (15) | 0.0028 (10) | 0.0021 (12) | −0.0008 (12) |
| C1 | 0.0179 (12) | 0.0221 (13) | 0.0211 (15) | 0.0007 (10) | 0.0008 (12) | −0.0016 (16) |
| C2 | 0.0202 (14) | 0.0169 (13) | 0.0157 (14) | 0.0005 (11) | 0.0021 (11) | −0.0001 (12) |
| C3 | 0.0226 (13) | 0.0184 (14) | 0.0141 (12) | −0.0010 (10) | 0.0015 (11) | −0.0028 (11) |
| C4 | 0.0273 (14) | 0.0201 (14) | 0.0185 (15) | 0.0043 (12) | 0.0017 (12) | 0.0000 (12) |
| C5 | 0.0232 (15) | 0.0290 (16) | 0.0214 (17) | 0.0063 (13) | 0.0003 (11) | 0.0005 (12) |
| C6 | 0.0212 (14) | 0.0255 (14) | 0.0215 (18) | −0.0005 (12) | −0.0004 (11) | −0.0018 (12) |
| C7 | 0.0193 (13) | 0.0220 (14) | 0.0154 (13) | 0.0011 (11) | 0.0036 (10) | −0.0018 (11) |
| C8 | 0.0265 (16) | 0.0216 (14) | 0.0284 (16) | −0.0023 (11) | 0.0020 (13) | −0.0067 (13) |
| O1 | 0.0263 (18) | 0.0323 (18) | 0.0298 (18) | 0.0044 (14) | 0.000 | 0.000 |
| Br1—C3 | 1.887 (3) | C4—C5 | 1.406 (5) |
| N1—C1 | 1.304 (4) | C4—H4 | 0.9500 |
| N1—N2 | 1.367 (4) | C5—C6 | 1.362 (5) |
| N2—C8 | 1.308 (4) | C5—H5 | 0.9500 |
| C1—C2 | 1.421 (4) | C6—C7 | 1.413 (4) |
| C1—H1 | 0.9500 | C6—H6 | 0.9500 |
| C2—C7 | 1.405 (4) | C7—C8 | 1.414 (4) |
| C2—C3 | 1.417 (4) | C8—H8 | 0.9500 |
| C3—C4 | 1.363 (4) | O1—H1A | 0.82 (2) |
| C1—N1—N2 | 120.7 (3) | C5—C4—H4 | 119.8 |
| C8—N2—N1 | 118.2 (3) | C6—C5—C4 | 121.3 (3) |
| N1—C1—C2 | 123.9 (3) | C6—C5—H5 | 119.3 |
| N1—C1—H1 | 118.1 | C4—C5—H5 | 119.3 |
| C2—C1—H1 | 118.1 | C5—C6—C7 | 118.9 (3) |
| C7—C2—C3 | 118.7 (3) | C5—C6—H6 | 120.5 |
| C7—C2—C1 | 115.9 (3) | C7—C6—H6 | 120.5 |
| C3—C2—C1 | 125.3 (3) | C2—C7—C6 | 120.5 (3) |
| C4—C3—C2 | 120.2 (3) | C2—C7—C8 | 116.2 (3) |
| C4—C3—Br1 | 119.9 (2) | C6—C7—C8 | 123.3 (3) |
| C2—C3—Br1 | 119.9 (2) | N2—C8—C7 | 125.1 (3) |
| C3—C4—C5 | 120.3 (3) | N2—C8—H8 | 117.4 |
| C3—C4—H4 | 119.8 | C7—C8—H8 | 117.4 |
| C1—N1—N2—C8 | 0.1 (5) | C4—C5—C6—C7 | −1.0 (5) |
| N2—N1—C1—C2 | 0.0 (6) | C3—C2—C7—C6 | 1.0 (4) |
| N1—C1—C2—C7 | −0.9 (5) | C1—C2—C7—C6 | −179.1 (3) |
| N1—C1—C2—C3 | 178.9 (4) | C3—C2—C7—C8 | −178.3 (3) |
| C7—C2—C3—C4 | 0.1 (4) | C1—C2—C7—C8 | 1.6 (4) |
| C1—C2—C3—C4 | −179.8 (3) | C5—C6—C7—C2 | −0.6 (4) |
| C7—C2—C3—Br1 | 179.8 (2) | C5—C6—C7—C8 | 178.7 (3) |
| C1—C2—C3—Br1 | 0.0 (4) | N1—N2—C8—C7 | 0.7 (5) |
| C2—C3—C4—C5 | −1.6 (5) | C2—C7—C8—N2 | −1.6 (5) |
| Br1—C3—C4—C5 | 178.7 (2) | C6—C7—C8—N2 | 179.1 (3) |
| C3—C4—C5—C6 | 2.0 (5) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1A···N1 | 0.82 (2) | 2.07 (3) | 2.887 (3) | 175 (5) |
Experimental details
| Crystal data | |
| Chemical formula | C8H5BrN2·0.5H2O |
| Mr | 218.06 |
| Crystal system, space group | Orthorhombic, Fdd2 |
| Temperature (K) | 113 |
| a, b, c (Å) | 13.5000 (18), 29.964 (5), 7.5565 (5) |
| V (Å3) | 3056.7 (7) |
| Z | 16 |
| Radiation type | Mo Kα |
| µ (mm−1) | 5.31 |
| Crystal size (mm) | 0.30 × 0.22 × 0.18 |
| Data collection | |
| Diffractometer | Rigaku Saturn724 CCD |
| Absorption correction | Multi-scan (CrystalClear; Rigaku/MSC, 2002) |
| Tmin, Tmax | 0.299, 0.448 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 7799, 1819, 1781 |
| Rint | 0.064 |
| (sin θ/λ)max (Å−1) | 0.657 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.074, 1.06 |
| No. of reflections | 1819 |
| No. of parameters | 109 |
| No. of restraints | 2 |
| H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
| Δρmax, Δρmin (e Å−3) | 0.74, −0.77 |
| Absolute structure | Flack (1983), 839 Friedel pairs |
| Absolute structure parameter | −0.002 (10) |
Computer programs: CrystalClear (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Crystal Impact, 2009), CrystalStructure (Rigaku/MSC, 2006).
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1A···N1 | 0.82 (2) | 2.07 (3) | 2.887 (3) | 175 (5) |
Acknowledgements
The authors thank Professor Wang, Department of Chemistry, Nankai University, for providing experimental facilities.
References
Caira, M. R., Georgescu, E., Georgescu, F., Albota, F., Dumitrascu, F. & Lorea, D. (2011). Monatsh. Chem. 142, 743–748. Web of Science CSD CrossRef CAS Google Scholar
Crystal Impact (2009). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Musa, A. Y., Jalgham, R. T. T. & Mohamad, A. B. (2012). Corros. Sci. 56, 175–183. Web of Science CrossRef Google Scholar
Rigaku/MSC (2002). CrystalClear. Rigaku/MSC, The Woodlands, Texas, USA, and Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2006). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA, and Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
Phthalazine derivatives have played an important role in the development of corrosion science as they can inhibit the corrosion of mild steel (Musa et al., 2012). Moreover, they are of particular interest owing to their biological activity and optical properties (Caira, et al., 2011).
In this paper, the title new phthalazine derivative derived from the condensation of 3-bromo-benzene-1,2-dicarboxaldehyde with hydrazine is reported. The molecular structure of the title compound (Fig.1) is essentially planar with a deviation from the mean plane of the phthalazine ring of 0.0115 (3) Å. All bond lengths have normal values.The oxygen atom of the solvent water molecule is situated on a twofold rotation axis. In the crystal, O—H···N hydrogen bonds and short N···Br contacts lead to the formation of a two dimensional network structure (Fig.2).