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access(E)-2-Bromobenzaldehyde oxime
aDepartment of Chemistry, College of Science, University of Tehran, PO Box 14155-6455 Tehran, Iran, bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and cChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
*Correspondence e-mail: seikweng@um.edu.my
The configuration of the C=N double bond of the title compound, C7H6BrNO, is E; the non-H atoms are approximately coplanar (r.m.s. deviation = 0.038 Å). In the crystal, pairs of molecules are linked by a pair of O—H⋯N hydrogen bonds about a center of inversion, generating hydrogen-bonded dimers.
Related literature
For the synthesis, see: Jin et al. (2010![[Jin, J., Li, Y., Wang, Z.-J., Qian, W.-X. & Bao, W.-L. (2010). Eur. J. Org. Chem. pp. 1235-1238.]](../../../../../../logos/arrows/e_arr.gif "Jin, J., Li, Y., Wang, Z.-J., Qian, W.-X. & Bao, W.-L. (2010). Eur. J. Org. Chem. pp. 1235-1238.")
). For the spectroscopic differentiation between E and Z isomers, see: Schnekenburger (1973). For reactions that produce 5-isoxazolpenicillins, see: Wang et al. (2007).
![[Scheme 1]](bt5606scheme1.gif)
Experimental
Crystal data
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Refinement
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Data collection: CrysAlis PRO (Agilent, 2010); cell CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).
Supporting information
contains datablocks global, I. DOI: 10.1107/S1600536811032211/bt5606sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S1600536811032211/bt5606Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536811032211/bt5606Isup3.cml
2-Bromobenzaldehyde (1.0 mmol, 184 mg), 50% hydroxylamine (3.0 mmol, 0.18 ml) and hydrated zinc chloride (0.2 mmol) were heated at 373 K for half an hour. The progress of reaction was monitored by TLC (ethyl acetate / n- hexane 1/3). The product was purified by on silica gel, with ethanyl acetate/n-hexane (1/4) as co-solvent. Colorless were obtained by using ethyl acetate as solvent for recrystallization, m.p. 363 K (yield 90%).
Carbon-bound H-atoms were placed in calculated positions [C—H 0.95 Å, Uiso(H) 1.2Ueq(C)] and were included in the in the riding model approximation.
The hydroxy H-atom was located in a difference Fouier map and was refined.
Data collection: CrysAlis PRO (Agilent, 2010); cell CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).
![[Figure 1]](./bt5606fig1thm.gif) | Fig. 1. Anisotropic displacement ellipsoid plot (Barbour, 2001) of C7H6BrNO at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. |
| C7H6BrNO | F(000) = 392 |
| Mr = 200.04 | Dx = 1.866 Mg m−3 |
| Monoclinic, P21/c | Cu Kα radiation, λ = 1.54184 Å |
| Hall symbol: -P 2ybc | Cell parameters from 3601 reflections |
| a = 7.7403 (2) Å | θ = 3.8–74.0° |
| b = 4.0012 (1) Å | µ = 7.25 mm−1 |
| c = 23.2672 (5) Å | T = 100 K |
| β = 98.810 (2)° | Block, colorless |
| V = 712.09 (3) Å3 | 0.20 × 0.15 × 0.10 mm |
| Z = 4 |
| Agilent SuperNova Dual diffractometer with an Atlas detector | 1421 independent reflections |
| Radiation source: SuperNova (Cu) X-ray Source | 1411 reflections with I > 2σ(I) |
| Mirror monochromator | Rint = 0.017 |
| Detector resolution: 10.4041 pixels mm-1 | θmax = 74.2°, θmin = 3.9° |
| ω scans | h = −8→9 |
| Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010) | k = −4→4 |
| Tmin = 0.325, Tmax = 0.531 | l = −28→26 |
| 4949 measured reflections |
| 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)] = 0.022 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.059 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.06 | w = 1/[σ2(Fo2) + (0.0373P)2 + 0.6889P] where P = (Fo2 + 2Fc2)/3 |
| 1421 reflections | (Δ/σ)max = 0.001 |
| 95 parameters | Δρmax = 0.39 e Å−3 |
| 0 restraints | Δρmin = −0.49 e Å−3 |
| C7H6BrNO | V = 712.09 (3) Å3 |
| Mr = 200.04 | Z = 4 |
| Monoclinic, P21/c | Cu Kα radiation |
| a = 7.7403 (2) Å | µ = 7.25 mm−1 |
| b = 4.0012 (1) Å | T = 100 K |
| c = 23.2672 (5) Å | 0.20 × 0.15 × 0.10 mm |
| β = 98.810 (2)° |
| Agilent SuperNova Dual diffractometer with an Atlas detector | 1421 independent reflections |
| Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010) | 1411 reflections with I > 2σ(I) |
| Tmin = 0.325, Tmax = 0.531 | Rint = 0.017 |
| 4949 measured reflections |
| R[F2 > 2σ(F2)] = 0.022 | 0 restraints |
| wR(F2) = 0.059 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.06 | Δρmax = 0.39 e Å−3 |
| 1421 reflections | Δρmin = −0.49 e Å−3 |
| 95 parameters |
| x | y | z | Uiso*/Ueq | ||
| Br1 | 0.14837 (3) | 0.15858 (5) | 0.213462 (8) | 0.02034 (10) | |
| O1 | −0.1279 (2) | 0.8670 (4) | 0.04381 (7) | 0.0247 (3) | |
| H1 | −0.132 (4) | 0.989 (9) | 0.0131 (14) | 0.042 (8)* | |
| N1 | 0.0488 (2) | 0.7706 (5) | 0.05189 (7) | 0.0192 (3) | |
| C1 | 0.3131 (3) | 0.2643 (5) | 0.16293 (8) | 0.0181 (4) | |
| C2 | 0.4830 (3) | 0.1467 (5) | 0.17939 (9) | 0.0207 (4) | |
| H2 | 0.5131 | 0.0239 | 0.2144 | 0.025* | |
| C3 | 0.6078 (3) | 0.2117 (6) | 0.14383 (10) | 0.0226 (4) | |
| H3 | 0.7241 | 0.1334 | 0.1545 | 0.027* | |
| C4 | 0.5625 (3) | 0.3910 (6) | 0.09268 (10) | 0.0228 (4) | |
| H4 | 0.6480 | 0.4358 | 0.0684 | 0.027* | |
| C5 | 0.3930 (3) | 0.5045 (5) | 0.07699 (8) | 0.0210 (4) | |
| H5 | 0.3634 | 0.6248 | 0.0417 | 0.025* | |
| C6 | 0.2639 (3) | 0.4463 (5) | 0.11190 (8) | 0.0175 (4) | |
| C7 | 0.0852 (3) | 0.5747 (5) | 0.09540 (8) | 0.0188 (4) | |
| H7 | −0.0037 | 0.5116 | 0.1172 | 0.023* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Br1 | 0.02289 (14) | 0.02016 (15) | 0.01905 (14) | 0.00002 (7) | 0.00669 (9) | 0.00319 (7) |
| O1 | 0.0177 (7) | 0.0297 (9) | 0.0269 (8) | 0.0036 (6) | 0.0038 (6) | 0.0083 (6) |
| N1 | 0.0174 (8) | 0.0186 (8) | 0.0213 (8) | 0.0010 (7) | 0.0028 (6) | −0.0004 (7) |
| C1 | 0.0213 (9) | 0.0153 (9) | 0.0184 (9) | −0.0018 (8) | 0.0054 (7) | −0.0017 (8) |
| C2 | 0.0233 (10) | 0.0184 (10) | 0.0200 (10) | 0.0003 (7) | 0.0015 (8) | −0.0002 (7) |
| C3 | 0.0163 (9) | 0.0227 (10) | 0.0282 (11) | 0.0013 (8) | 0.0012 (8) | −0.0048 (8) |
| C4 | 0.0217 (10) | 0.0243 (11) | 0.0237 (10) | −0.0050 (8) | 0.0081 (8) | −0.0046 (8) |
| C5 | 0.0239 (10) | 0.0200 (10) | 0.0193 (9) | −0.0017 (8) | 0.0041 (7) | 0.0001 (8) |
| C6 | 0.0194 (9) | 0.0146 (9) | 0.0183 (9) | −0.0023 (7) | 0.0023 (7) | −0.0028 (7) |
| C7 | 0.0200 (9) | 0.0183 (9) | 0.0184 (9) | −0.0020 (8) | 0.0038 (7) | −0.0004 (8) |
| Br1—C1 | 1.9093 (19) | C3—C4 | 1.388 (3) |
| O1—N1 | 1.406 (2) | C3—H3 | 0.9500 |
| O1—H1 | 0.86 (3) | C4—C5 | 1.384 (3) |
| N1—C7 | 1.277 (3) | C4—H4 | 0.9500 |
| C1—C2 | 1.394 (3) | C5—C6 | 1.400 (3) |
| C1—C6 | 1.395 (3) | C5—H5 | 0.9500 |
| C2—C3 | 1.389 (3) | C6—C7 | 1.471 (3) |
| C2—H2 | 0.9500 | C7—H7 | 0.9500 |
| N1—O1—H1 | 100 (2) | C5—C4—H4 | 120.0 |
| C7—N1—O1 | 111.47 (16) | C3—C4—H4 | 120.0 |
| C2—C1—C6 | 122.18 (18) | C4—C5—C6 | 121.63 (19) |
| C2—C1—Br1 | 116.55 (15) | C4—C5—H5 | 119.2 |
| C6—C1—Br1 | 121.26 (15) | C6—C5—H5 | 119.2 |
| C3—C2—C1 | 119.08 (19) | C5—C6—C1 | 117.05 (18) |
| C3—C2—H2 | 120.5 | C5—C6—C7 | 121.12 (18) |
| C1—C2—H2 | 120.5 | C1—C6—C7 | 121.83 (18) |
| C2—C3—C4 | 120.03 (19) | N1—C7—C6 | 120.37 (18) |
| C2—C3—H3 | 120.0 | N1—C7—H7 | 119.8 |
| C4—C3—H3 | 120.0 | C6—C7—H7 | 119.8 |
| C5—C4—C3 | 120.0 (2) | ||
| C6—C1—C2—C3 | −0.2 (3) | C2—C1—C6—C5 | 0.7 (3) |
| Br1—C1—C2—C3 | 179.03 (15) | Br1—C1—C6—C5 | −178.50 (15) |
| C1—C2—C3—C4 | −0.1 (3) | C2—C1—C6—C7 | −178.85 (19) |
| C2—C3—C4—C5 | −0.2 (3) | Br1—C1—C6—C7 | 2.0 (3) |
| C3—C4—C5—C6 | 0.7 (3) | O1—N1—C7—C6 | −179.41 (17) |
| C4—C5—C6—C1 | −0.9 (3) | C5—C6—C7—N1 | −7.1 (3) |
| C4—C5—C6—C7 | 178.62 (19) | C1—C6—C7—N1 | 172.4 (2) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1···N1i | 0.86 (3) | 1.98 (3) | 2.802 (2) | 159 (3) |
| Symmetry code: (i) −x, −y+2, −z. |
Experimental details
| Crystal data | |
| Chemical formula | C7H6BrNO |
| Mr | 200.04 |
| Crystal system, space group | Monoclinic, P21/c |
| Temperature (K) | 100 |
| a, b, c (Å) | 7.7403 (2), 4.0012 (1), 23.2672 (5) |
| β (°) | 98.810 (2) |
| V (Å3) | 712.09 (3) |
| Z | 4 |
| Radiation type | Cu Kα |
| µ (mm−1) | 7.25 |
| Crystal size (mm) | 0.20 × 0.15 × 0.10 |
| Data collection | |
| Diffractometer | Agilent SuperNova Dual diffractometer with an Atlas detector |
| Absorption correction | Multi-scan (CrysAlis PRO; Agilent, 2010) |
| Tmin, Tmax | 0.325, 0.531 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 4949, 1421, 1411 |
| Rint | 0.017 |
| (sin θ/λ)max (Å−1) | 0.624 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.022, 0.059, 1.06 |
| No. of reflections | 1421 |
| No. of parameters | 95 |
| H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
| Δρmax, Δρmin (e Å−3) | 0.39, −0.49 |
Computer programs: CrysAlis PRO (Agilent, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1···N1i | 0.86 (3) | 1.98 (3) | 2.802 (2) | 159 (3) |
| Symmetry code: (i) −x, −y+2, −z. |
Acknowledgements
We thank the Iran National Science Foundation and the University of Malaya for supporting this study.
References
Agilent (2010). CrysAlis PRO. Agilent Technologies, Yarnton, England. Google Scholar
Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Jin, J., Li, Y., Wang, Z.-J., Qian, W.-X. & Bao, W.-L. (2010). Eur. J. Org. Chem. pp. 1235–1238. Google Scholar
Schnekenburger, J. (1973). Fresenius Z. Anal. Chem. 263, 23–26. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, X.-Z., Jia, J., Zhang, Y., Xu, W.-R., Liu, W., Shi, F.-N. & Wang, J.-W. (2007). J. Chin. Chem. Soc. (Taipei, Taiwan), 54, 643–652. Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
(2-Bromophenyl)methanoxime can be converted to 5-isoxazolpenicillins (Wang et al., 2007); the compound exists into a E and a Z configuration with respect to the carbon-nitrogen double-bond; mixtures can be differentiated by their UV spectra (Schnekenburger, 1973). A recent study reported the synthesis of the E isomer (Scheme I) without the use of a metal-salt catalyst (Jin et al., 2010). Zinc chloride is used in this study to give the compound in high yield. The non-H atoms are co-planar (Fig. 1); two molecules are linked by an O–H···N bond about a center-of-inversion to generate a hydrogen-bonded dimer (Table 1).