organic compounds
1-(Benzotriazol-1-yl)-2-bromoethanone
aChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203, Jeddah 21589, Saudi Arabia, bCenter of Excellence for Advanced Materials Research (CEAMR), Faculty of Science, King Abdulaziz University, PO Box 80203, Jeddah 21589, Saudi Arabia, cDepartment of Pharmaceutical Organic Chemistry, Faculty of Pharmacy, Zagazig University, Zagazig, 44519, Egypt, and dDepartment of Chemistry, Government College University, Faisalabad 38040, Pakistan
*Correspondence e-mail: mnachemist@hotmail.com, hafizshafique@hotmail.com
In the title compound C8H6BrN3O, the benzotriazole ring is essentially planar (r.m.s. deviation = 0.0034 Å) and the bromoacetyl unit is twisted at a dihedral angle of 15.24 (16)° with respect to it. In the crystal, pairs of C—H⋯O hydrogen bondings result in the formation of inversion dimers, forming R22(12) rings, which are connected by further C—H⋯O interactions into chains extending along the b-axis direction.
Related literature
For the biological activity of the title compound, see: Nakagawa et al. (1973). For the of a closely related compound, see: Selvarathy Grace et al. (2012). For graph-set notation, see: Bernstein et al. (1995).
Experimental
Crystal data
|
Refinement
|
Data collection: CrysAlis PRO (Agilent, 2012); 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: PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and X-SEED (Barbour, 2001).
Supporting information
10.1107/S1600536812042900/pv2595sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812042900/pv2595Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812042900/pv2595Isup3.cml
A solution of thionyl chloride (0.4 mL, 5.5 mmol) and benzotriazole (1.79 g., 15 mmol) in methylene chloride (30 mL) was stirred at 293 K for 30 minutes. Bromoacetic acid (0.7 g., 5 mmol) was then added and the heterogeneous mixture was stirred for 2 hr. The solid was filtered and methylene chloride (50 mL) was added to the filtrate. The organic layer was extracted with saturated 4N HCl (3x, 15 mL), brine (2x, 5 mL) and dried over anhydrous Na2SO4. The crystals of the title compound suitable for X-ray crystallographic analysis were obtained by slow evaporation of methylene chloride (1.0 g, 83% yield).
The H-atoms were positioned with idealized geometry with C—H = 0.93 and 0.97 Å for aromatic and methylene H-atoms, respectively, and were refined as riding with Uiso(H) = 1.2Ueq(C).
Three reflections (5 2 15), (6 2 14) & (4 2 16) have been omitted in final refinement.
Data collection: CrysAlis PRO (Agilent, 2012); cell
CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and X-SEED (Barbour, 2001).C8H6BrN3O | F(000) = 472 |
Mr = 240.07 | Dx = 1.798 Mg m−3 |
Monoclinic, P21/n | Cu Kα radiation, λ = 1.54184 Å |
Hall symbol: -P 2yn | Cell parameters from 2295 reflections |
a = 12.4815 (4) Å | θ = 3.6–76.0° |
b = 4.7207 (1) Å | µ = 6.02 mm−1 |
c = 15.4780 (5) Å | T = 296 K |
β = 103.468 (3)° | Plate, colorless |
V = 886.91 (4) Å3 | 0.28 × 0.11 × 0.05 mm |
Z = 4 |
Agilent SuperNova Dual (Cu at zero) Atlas, CCD diffractometer | 1833 independent reflections |
Radiation source: SuperNova (Cu) X-ray Source | 1507 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.034 |
ω scans | θmax = 76.2°, θmin = 4.1° |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012) | h = −15→12 |
Tmin = 0.284, Tmax = 0.753 | k = −5→5 |
4362 measured reflections | l = −19→19 |
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)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.141 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0838P)2 + 0.0945P] where P = (Fo2 + 2Fc2)/3 |
1833 reflections | (Δ/σ)max < 0.001 |
118 parameters | Δρmax = 0.43 e Å−3 |
0 restraints | Δρmin = −0.51 e Å−3 |
C8H6BrN3O | V = 886.91 (4) Å3 |
Mr = 240.07 | Z = 4 |
Monoclinic, P21/n | Cu Kα radiation |
a = 12.4815 (4) Å | µ = 6.02 mm−1 |
b = 4.7207 (1) Å | T = 296 K |
c = 15.4780 (5) Å | 0.28 × 0.11 × 0.05 mm |
β = 103.468 (3)° |
Agilent SuperNova Dual (Cu at zero) Atlas, CCD diffractometer | 1833 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012) | 1507 reflections with I > 2σ(I) |
Tmin = 0.284, Tmax = 0.753 | Rint = 0.034 |
4362 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.141 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.43 e Å−3 |
1833 reflections | Δρmin = −0.51 e Å−3 |
118 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 | ||
Br1 | 0.84802 (3) | 0.99732 (9) | −0.01180 (3) | 0.0947 (2) | |
O1 | 0.63342 (16) | 0.7775 (4) | 0.02369 (12) | 0.0717 (5) | |
N1 | 0.62518 (17) | 1.0238 (4) | 0.14622 (14) | 0.0512 (5) | |
N2 | 0.67298 (17) | 1.2209 (5) | 0.20998 (14) | 0.0603 (5) | |
N3 | 0.61989 (19) | 1.2185 (5) | 0.27134 (14) | 0.0673 (6) | |
C1 | 0.5348 (2) | 1.0227 (5) | 0.25097 (18) | 0.0582 (6) | |
C2 | 0.4553 (3) | 0.9458 (7) | 0.2965 (2) | 0.0774 (8) | |
H2 | 0.4528 | 1.0294 | 0.3504 | 0.093* | |
C3 | 0.3809 (2) | 0.7419 (8) | 0.2586 (2) | 0.0800 (9) | |
H3 | 0.3269 | 0.6862 | 0.2875 | 0.096* | |
C4 | 0.3843 (2) | 0.6154 (7) | 0.1776 (2) | 0.0743 (7) | |
H4 | 0.3320 | 0.4787 | 0.1540 | 0.089* | |
C5 | 0.4624 (2) | 0.6864 (5) | 0.13167 (17) | 0.0608 (6) | |
H5 | 0.4647 | 0.6012 | 0.0780 | 0.073* | |
C6 | 0.53792 (18) | 0.8945 (5) | 0.17058 (14) | 0.0509 (5) | |
C7 | 0.6721 (2) | 0.9628 (5) | 0.07435 (16) | 0.0518 (5) | |
C8 | 0.7682 (2) | 1.1462 (6) | 0.06834 (17) | 0.0614 (6) | |
H8A | 0.8172 | 1.1633 | 0.1268 | 0.074* | |
H8B | 0.7419 | 1.3343 | 0.0489 | 0.074* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0844 (3) | 0.1209 (5) | 0.0895 (4) | 0.00843 (18) | 0.0419 (2) | −0.00526 (18) |
O1 | 0.0855 (12) | 0.0685 (12) | 0.0622 (10) | −0.0108 (9) | 0.0193 (9) | −0.0213 (9) |
N1 | 0.0541 (10) | 0.0483 (10) | 0.0484 (10) | 0.0024 (7) | 0.0065 (8) | −0.0066 (7) |
N2 | 0.0655 (11) | 0.0525 (11) | 0.0594 (11) | 0.0003 (9) | 0.0075 (9) | −0.0128 (9) |
N3 | 0.0805 (13) | 0.0640 (13) | 0.0562 (11) | 0.0053 (11) | 0.0136 (10) | −0.0146 (9) |
C1 | 0.0637 (14) | 0.0573 (14) | 0.0522 (13) | 0.0132 (10) | 0.0110 (11) | −0.0013 (9) |
C2 | 0.087 (2) | 0.0816 (19) | 0.0684 (18) | 0.0213 (16) | 0.0281 (15) | 0.0064 (14) |
C3 | 0.0694 (15) | 0.087 (2) | 0.088 (2) | 0.0074 (15) | 0.0282 (15) | 0.0204 (17) |
C4 | 0.0606 (14) | 0.0732 (18) | 0.0864 (19) | −0.0028 (13) | 0.0115 (13) | 0.0139 (16) |
C5 | 0.0592 (12) | 0.0586 (14) | 0.0600 (13) | −0.0012 (11) | 0.0045 (10) | 0.0011 (11) |
C6 | 0.0535 (11) | 0.0480 (11) | 0.0486 (11) | 0.0085 (9) | 0.0066 (8) | 0.0032 (9) |
C7 | 0.0564 (12) | 0.0495 (12) | 0.0477 (12) | 0.0042 (9) | 0.0080 (9) | −0.0026 (8) |
C8 | 0.0640 (13) | 0.0619 (15) | 0.0586 (13) | 0.0006 (11) | 0.0150 (10) | −0.0016 (11) |
Br1—C8 | 1.897 (3) | C2—H2 | 0.9300 |
O1—C7 | 1.199 (3) | C3—C4 | 1.398 (5) |
N1—C6 | 1.376 (3) | C3—H3 | 0.9300 |
N1—N2 | 1.386 (3) | C4—C5 | 1.374 (4) |
N1—C7 | 1.402 (3) | C4—H4 | 0.9300 |
N2—N3 | 1.279 (3) | C5—C6 | 1.397 (3) |
N3—C1 | 1.388 (4) | C5—H5 | 0.9300 |
C1—C2 | 1.391 (5) | C7—C8 | 1.500 (4) |
C1—C6 | 1.392 (3) | C8—H8A | 0.9700 |
C2—C3 | 1.371 (5) | C8—H8B | 0.9700 |
C6—N1—N2 | 109.9 (2) | C3—C4—H4 | 118.9 |
C6—N1—C7 | 129.1 (2) | C4—C5—C6 | 115.9 (3) |
N2—N1—C7 | 120.8 (2) | C4—C5—H5 | 122.0 |
N3—N2—N1 | 108.2 (2) | C6—C5—H5 | 122.0 |
N2—N3—C1 | 109.8 (2) | N1—C6—C1 | 104.0 (2) |
N3—C1—C2 | 131.0 (3) | N1—C6—C5 | 133.8 (2) |
N3—C1—C6 | 108.2 (2) | C1—C6—C5 | 122.3 (2) |
C2—C1—C6 | 120.7 (3) | O1—C7—N1 | 119.3 (2) |
C3—C2—C1 | 117.3 (3) | O1—C7—C8 | 125.9 (2) |
C3—C2—H2 | 121.4 | N1—C7—C8 | 114.8 (2) |
C1—C2—H2 | 121.4 | C7—C8—Br1 | 112.09 (18) |
C2—C3—C4 | 121.6 (3) | C7—C8—H8A | 109.2 |
C2—C3—H3 | 119.2 | Br1—C8—H8A | 109.2 |
C4—C3—H3 | 119.2 | C7—C8—H8B | 109.2 |
C5—C4—C3 | 122.2 (3) | Br1—C8—H8B | 109.2 |
C5—C4—H4 | 118.9 | H8A—C8—H8B | 107.9 |
C6—N1—N2—N3 | 0.0 (3) | C7—N1—C6—C5 | −6.4 (4) |
C7—N1—N2—N3 | −174.6 (2) | N3—C1—C6—N1 | −0.6 (3) |
N1—N2—N3—C1 | −0.4 (3) | C2—C1—C6—N1 | 179.7 (2) |
N2—N3—C1—C2 | −179.7 (3) | N3—C1—C6—C5 | −179.9 (2) |
N2—N3—C1—C6 | 0.6 (3) | C2—C1—C6—C5 | 0.4 (4) |
N3—C1—C2—C3 | 180.0 (3) | C4—C5—C6—N1 | −179.1 (2) |
C6—C1—C2—C3 | −0.4 (4) | C4—C5—C6—C1 | 0.0 (3) |
C1—C2—C3—C4 | 0.0 (5) | C6—N1—C7—O1 | 1.4 (4) |
C2—C3—C4—C5 | 0.4 (5) | N2—N1—C7—O1 | 174.8 (2) |
C3—C4—C5—C6 | −0.4 (4) | C6—N1—C7—C8 | −179.3 (2) |
N2—N1—C6—C1 | 0.4 (2) | N2—N1—C7—C8 | −5.9 (3) |
C7—N1—C6—C1 | 174.4 (2) | O1—C7—C8—Br1 | −14.7 (3) |
N2—N1—C6—C5 | 179.6 (2) | N1—C7—C8—Br1 | 166.13 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···O1i | 0.93 | 2.50 | 3.266 (3) | 139 |
C8—H8B···O1ii | 0.97 | 2.47 | 3.413 (4) | 163 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) x, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | C8H6BrN3O |
Mr | 240.07 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 296 |
a, b, c (Å) | 12.4815 (4), 4.7207 (1), 15.4780 (5) |
β (°) | 103.468 (3) |
V (Å3) | 886.91 (4) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 6.02 |
Crystal size (mm) | 0.28 × 0.11 × 0.05 |
Data collection | |
Diffractometer | Agilent SuperNova Dual (Cu at zero) Atlas, CCD diffractometer |
Absorption correction | Multi-scan (CrysAlis PRO; Agilent, 2012) |
Tmin, Tmax | 0.284, 0.753 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4362, 1833, 1507 |
Rint | 0.034 |
(sin θ/λ)max (Å−1) | 0.630 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.141, 1.07 |
No. of reflections | 1833 |
No. of parameters | 118 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.43, −0.51 |
Computer programs: CrysAlis PRO (Agilent, 2012), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009), WinGX (Farrugia, 1999) and X-SEED (Barbour, 2001).
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···O1i | 0.93 | 2.50 | 3.266 (3) | 139.2 |
C8—H8B···O1ii | 0.97 | 2.47 | 3.413 (4) | 163.2 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) x, y+1, z. |
Acknowledgements
The authors would like to thank the Deanship of Scientific Research at King Abdulaziz University for the support of this research via the Research Group Track of grant No. (3-102/428).
References
Agilent (2012). CrysAlis PRO. Agilent Technologies, Yarnton, England. Google Scholar
Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Selvarathy Grace, P., Jebas, S. R., Ravindran Durai Nayagam, B. & Schollmeyer, D. (2012). Acta Cryst. E68, o1132. CSD CrossRef IUCr Journals Google Scholar
Nakagawa, Y., Ichihara, S., Niki, T., Suzuki, A., Shimosato, K. & Ogata, K. (1973). Jpn Patent JP48054066A. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
The title compound shows antitumor activity mediated by inhibition of ascites sarcoma 180 in mice (Nakagawa et al., 1973). Herein we report the crystal structure of the title compound.
The molecule of the title compound (Fig. 1) excluding Br1 atom is planer with r.m.s. deviation = 0.0367 Å; the Br1 atom is displaced from this plane by 0.489 (2) Å . The benzotriazole ring (C1–C6/N1–N3) is essentially planar with r.m.s.d = 0.0034 Å. The bromoacetyl moiety (Br1/C8/C7/O1) is twisted at a dihedral angle of 15.24 (16)° with respect to the benzotriazole ring. The structure of the title compound is stabilized by intermolecular hydrogen bonding interactions C5—H5···O1 resulting in dimers about inversion centers forming twelve membered ring motif R22(12) (Bernstein et al., 1995). The dimers are further connected through C8—H8B···O1 hydrogen bonding interactions resulting in chains of molecules extended along the b axis (Table 1 and Fig. 2).