organic compounds
1-(1H-1,2,3-Benzotriazol-1-yl)-2-(4-methoxyphenyl)ethanone
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: aasiri2@kau.edu.sa, hafizshafique@hotmail.com
In the title compound, C15H13N3O2, the dihedral angle between the benzotriazole ring system (r.m.s. deviation = 0.0124 Å) and the benzene ring is 76.21 (3)°. The methoxy C atom deviates from its benzene ring plane by 0.063 (2)Å. In the crystal, inversion dimers linked by pairs of C—H⋯O hydrogen bonds generate R22(12) loops.
Related literature
For chemical background, see: Katritzky et al. (1996a,b, 2005, 2010). For a related structure, see: Selvarathy Grace et al. (2012). For related literature, see: Zou et al. (2006).
Experimental
Crystal data
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Refinement
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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/S1600536812043759/hb6975sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812043759/hb6975Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812043759/hb6975Isup3.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. 2-(4-methoxypheny)acetic acid (0.83 g., 5 mmol) was then added and the heterogeneous mixture was stirred for 2 hr. The solid was filtered and methylene chloride (50mL) was added to the filtrate. The organic layer was extracted with saturated Na2CO3 (3 × 15 ml), brine (2 × 5 ml) and dried over anhyd. Na2SO4. Evaporation of methylene chloride solution afforded colourless prisms (1.21 g., 90% yield).
All the C—H and H-atoms were positioned with idealized geometry with C—H = 0.93 Å for aromatic, C—H = 0.97 Å for methylene & C—H = 0.96 Å for methyl groups. H-atoms were refined as riding with Uiso(H) = kUeq(C, N), where k = 1.2 for aromatic & methylene and k = 1.5 for methyl H-atoms.
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).C15H13N3O2 | F(000) = 560 |
Mr = 267.28 | Dx = 1.345 Mg m−3 |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.54184 Å |
Hall symbol: -P 2ybc | Cell parameters from 3661 reflections |
a = 5.4209 (1) Å | θ = 4.4–76.0° |
b = 24.4894 (5) Å | µ = 0.75 mm−1 |
c = 10.0555 (2) Å | T = 296 K |
β = 98.552 (2)° | Prismatic, colorless |
V = 1320.07 (4) Å3 | 0.34 × 0.17 × 0.16 mm |
Z = 4 |
Agilent SuperNova (Dual, Cu at zero, Atlas CCD) diffractometer | 2707 independent reflections |
Radiation source: SuperNova (Cu) X-ray Source | 2340 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.019 |
ω scans | θmax = 76.2°, θmin = 4.8° |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012) | h = −6→4 |
Tmin = 0.784, Tmax = 0.889 | k = −29→30 |
6122 measured reflections | l = −12→12 |
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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.109 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0527P)2 + 0.1534P] where P = (Fo2 + 2Fc2)/3 |
2707 reflections | (Δ/σ)max < 0.001 |
182 parameters | Δρmax = 0.14 e Å−3 |
0 restraints | Δρmin = −0.16 e Å−3 |
C15H13N3O2 | V = 1320.07 (4) Å3 |
Mr = 267.28 | Z = 4 |
Monoclinic, P21/c | Cu Kα radiation |
a = 5.4209 (1) Å | µ = 0.75 mm−1 |
b = 24.4894 (5) Å | T = 296 K |
c = 10.0555 (2) Å | 0.34 × 0.17 × 0.16 mm |
β = 98.552 (2)° |
Agilent SuperNova (Dual, Cu at zero, Atlas CCD) diffractometer | 2707 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012) | 2340 reflections with I > 2σ(I) |
Tmin = 0.784, Tmax = 0.889 | Rint = 0.019 |
6122 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.109 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.14 e Å−3 |
2707 reflections | Δρmin = −0.16 e Å−3 |
182 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 | ||
O1 | 0.2197 (2) | 0.47488 (5) | 0.37631 (10) | 0.0750 (3) | |
O2 | 0.5718 (2) | 0.24790 (4) | 0.49538 (12) | 0.0737 (3) | |
N1 | 0.17264 (19) | 0.52715 (4) | 0.19212 (9) | 0.0463 (2) | |
N2 | 0.2345 (2) | 0.54066 (5) | 0.06808 (11) | 0.0581 (3) | |
N3 | 0.1096 (2) | 0.58305 (5) | 0.02364 (12) | 0.0640 (3) | |
C1 | −0.0418 (2) | 0.59893 (5) | 0.11725 (13) | 0.0517 (3) | |
C2 | −0.2135 (3) | 0.64152 (6) | 0.11304 (15) | 0.0647 (4) | |
H2 | −0.2396 | 0.6657 | 0.0410 | 0.078* | |
C3 | −0.3418 (3) | 0.64602 (7) | 0.21992 (16) | 0.0680 (4) | |
H3 | −0.4572 | 0.6741 | 0.2207 | 0.082* | |
C4 | −0.3036 (3) | 0.60952 (6) | 0.32785 (15) | 0.0639 (4) | |
H4 | −0.3955 | 0.6139 | 0.3982 | 0.077* | |
C5 | −0.1351 (3) | 0.56739 (6) | 0.33368 (13) | 0.0538 (3) | |
H5 | −0.1104 | 0.5431 | 0.4056 | 0.065* | |
C6 | −0.0036 (2) | 0.56326 (5) | 0.22524 (11) | 0.0445 (3) | |
C7 | 0.2792 (2) | 0.48237 (5) | 0.26753 (12) | 0.0482 (3) | |
C8 | 0.4576 (2) | 0.44711 (5) | 0.20553 (13) | 0.0522 (3) | |
H8A | 0.6154 | 0.4661 | 0.2081 | 0.063* | |
H8B | 0.3910 | 0.4401 | 0.1122 | 0.063* | |
C9 | 0.5001 (2) | 0.39358 (5) | 0.28009 (12) | 0.0463 (3) | |
C10 | 0.7140 (2) | 0.38340 (6) | 0.36909 (14) | 0.0553 (3) | |
H10 | 0.8398 | 0.4096 | 0.3802 | 0.066* | |
C11 | 0.7477 (2) | 0.33526 (6) | 0.44275 (14) | 0.0559 (3) | |
H11 | 0.8941 | 0.3294 | 0.5020 | 0.067* | |
C12 | 0.5628 (2) | 0.29645 (5) | 0.42717 (13) | 0.0501 (3) | |
C13 | 0.3460 (2) | 0.30573 (6) | 0.33780 (14) | 0.0548 (3) | |
H13 | 0.2207 | 0.2795 | 0.3265 | 0.066* | |
C14 | 0.3161 (2) | 0.35371 (5) | 0.26571 (13) | 0.0515 (3) | |
H14 | 0.1698 | 0.3595 | 0.2063 | 0.062* | |
C15 | 0.7849 (3) | 0.23650 (8) | 0.59061 (19) | 0.0839 (5) | |
H15A | 0.9308 | 0.2370 | 0.5469 | 0.126* | |
H15B | 0.7676 | 0.2011 | 0.6293 | 0.126* | |
H15C | 0.8010 | 0.2637 | 0.6602 | 0.126* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.1114 (9) | 0.0677 (7) | 0.0547 (6) | 0.0257 (6) | 0.0415 (6) | 0.0192 (5) |
O2 | 0.0810 (7) | 0.0529 (6) | 0.0814 (7) | −0.0002 (5) | −0.0071 (6) | 0.0172 (5) |
N1 | 0.0552 (5) | 0.0463 (5) | 0.0402 (5) | −0.0011 (4) | 0.0166 (4) | 0.0041 (4) |
N2 | 0.0705 (7) | 0.0606 (7) | 0.0485 (6) | 0.0056 (5) | 0.0264 (5) | 0.0127 (5) |
N3 | 0.0781 (8) | 0.0648 (7) | 0.0534 (6) | 0.0118 (6) | 0.0244 (6) | 0.0174 (5) |
C1 | 0.0591 (7) | 0.0498 (7) | 0.0473 (6) | −0.0008 (5) | 0.0118 (5) | 0.0039 (5) |
C2 | 0.0755 (9) | 0.0577 (8) | 0.0610 (8) | 0.0103 (7) | 0.0102 (7) | 0.0080 (7) |
C3 | 0.0720 (9) | 0.0591 (9) | 0.0735 (10) | 0.0127 (7) | 0.0128 (7) | −0.0067 (7) |
C4 | 0.0719 (9) | 0.0647 (9) | 0.0591 (8) | 0.0034 (7) | 0.0230 (7) | −0.0109 (7) |
C5 | 0.0671 (8) | 0.0536 (7) | 0.0432 (6) | −0.0022 (6) | 0.0168 (6) | −0.0032 (5) |
C6 | 0.0509 (6) | 0.0425 (6) | 0.0409 (6) | −0.0059 (5) | 0.0092 (5) | −0.0029 (5) |
C7 | 0.0583 (7) | 0.0450 (6) | 0.0438 (6) | −0.0031 (5) | 0.0160 (5) | 0.0044 (5) |
C8 | 0.0561 (7) | 0.0517 (7) | 0.0525 (7) | −0.0008 (5) | 0.0203 (5) | 0.0058 (5) |
C9 | 0.0460 (6) | 0.0478 (6) | 0.0475 (6) | 0.0016 (5) | 0.0149 (5) | 0.0007 (5) |
C10 | 0.0427 (6) | 0.0570 (8) | 0.0664 (8) | −0.0075 (5) | 0.0089 (5) | 0.0013 (6) |
C11 | 0.0431 (6) | 0.0616 (8) | 0.0608 (8) | 0.0038 (5) | 0.0007 (5) | 0.0016 (6) |
C12 | 0.0540 (6) | 0.0449 (6) | 0.0513 (7) | 0.0041 (5) | 0.0075 (5) | −0.0001 (5) |
C13 | 0.0527 (7) | 0.0493 (7) | 0.0603 (7) | −0.0088 (5) | 0.0008 (6) | 0.0007 (6) |
C14 | 0.0473 (6) | 0.0539 (7) | 0.0514 (6) | −0.0020 (5) | 0.0011 (5) | 0.0014 (5) |
C15 | 0.0787 (10) | 0.0842 (12) | 0.0863 (11) | 0.0217 (9) | 0.0046 (9) | 0.0308 (10) |
O1—C7 | 1.1997 (14) | C7—C8 | 1.4997 (18) |
O2—C12 | 1.3700 (16) | C8—C9 | 1.5106 (17) |
O2—C15 | 1.414 (2) | C8—H8A | 0.9700 |
N1—C6 | 1.3785 (16) | C8—H8B | 0.9700 |
N1—N2 | 1.3792 (13) | C9—C10 | 1.3783 (18) |
N1—C7 | 1.4075 (16) | C9—C14 | 1.3879 (17) |
N2—N3 | 1.2829 (16) | C10—C11 | 1.3898 (19) |
N3—C1 | 1.3928 (17) | C10—H10 | 0.9300 |
C1—C6 | 1.3849 (17) | C11—C12 | 1.3732 (18) |
C1—C2 | 1.394 (2) | C11—H11 | 0.9300 |
C2—C3 | 1.368 (2) | C12—C13 | 1.3878 (18) |
C2—H2 | 0.9300 | C13—C14 | 1.3775 (18) |
C3—C4 | 1.398 (2) | C13—H13 | 0.9300 |
C3—H3 | 0.9300 | C14—H14 | 0.9300 |
C4—C5 | 1.373 (2) | C15—H15A | 0.9600 |
C4—H4 | 0.9300 | C15—H15B | 0.9600 |
C5—C6 | 1.3924 (17) | C15—H15C | 0.9600 |
C5—H5 | 0.9300 | ||
C12—O2—C15 | 118.34 (13) | C9—C8—H8A | 109.5 |
C6—N1—N2 | 109.58 (10) | C7—C8—H8B | 109.5 |
C6—N1—C7 | 127.83 (10) | C9—C8—H8B | 109.5 |
N2—N1—C7 | 122.59 (10) | H8A—C8—H8B | 108.1 |
N3—N2—N1 | 108.80 (10) | C10—C9—C14 | 117.56 (12) |
N2—N3—C1 | 108.91 (10) | C10—C9—C8 | 122.04 (11) |
C6—C1—N3 | 108.63 (11) | C14—C9—C8 | 120.32 (11) |
C6—C1—C2 | 121.12 (12) | C9—C10—C11 | 122.05 (12) |
N3—C1—C2 | 130.24 (12) | C9—C10—H10 | 119.0 |
C3—C2—C1 | 116.83 (13) | C11—C10—H10 | 119.0 |
C3—C2—H2 | 121.6 | C12—C11—C10 | 119.37 (12) |
C1—C2—H2 | 121.6 | C12—C11—H11 | 120.3 |
C2—C3—C4 | 121.63 (14) | C10—C11—H11 | 120.3 |
C2—C3—H3 | 119.2 | O2—C12—C11 | 124.94 (12) |
C4—C3—H3 | 119.2 | O2—C12—C13 | 115.46 (12) |
C5—C4—C3 | 122.31 (13) | C11—C12—C13 | 119.60 (12) |
C5—C4—H4 | 118.8 | C14—C13—C12 | 120.17 (12) |
C3—C4—H4 | 118.8 | C14—C13—H13 | 119.9 |
C4—C5—C6 | 115.84 (13) | C12—C13—H13 | 119.9 |
C4—C5—H5 | 122.1 | C13—C14—C9 | 121.25 (12) |
C6—C5—H5 | 122.1 | C13—C14—H14 | 119.4 |
N1—C6—C1 | 104.08 (10) | C9—C14—H14 | 119.4 |
N1—C6—C5 | 133.61 (12) | O2—C15—H15A | 109.5 |
C1—C6—C5 | 122.28 (12) | O2—C15—H15B | 109.5 |
O1—C7—N1 | 117.76 (11) | H15A—C15—H15B | 109.5 |
O1—C7—C8 | 124.65 (12) | O2—C15—H15C | 109.5 |
N1—C7—C8 | 117.59 (10) | H15A—C15—H15C | 109.5 |
C7—C8—C9 | 110.69 (10) | H15B—C15—H15C | 109.5 |
C7—C8—H8A | 109.5 | ||
C6—N1—N2—N3 | 0.65 (15) | C6—N1—C7—O1 | −2.9 (2) |
C7—N1—N2—N3 | −179.84 (12) | N2—N1—C7—O1 | 177.64 (13) |
N1—N2—N3—C1 | −0.39 (16) | C6—N1—C7—C8 | 176.55 (11) |
N2—N3—C1—C6 | 0.00 (16) | N2—N1—C7—C8 | −2.87 (17) |
N2—N3—C1—C2 | −178.46 (15) | O1—C7—C8—C9 | 14.73 (19) |
C6—C1—C2—C3 | −0.3 (2) | N1—C7—C8—C9 | −164.72 (11) |
N3—C1—C2—C3 | 178.03 (15) | C7—C8—C9—C10 | −103.08 (14) |
C1—C2—C3—C4 | −0.3 (2) | C7—C8—C9—C14 | 73.62 (15) |
C2—C3—C4—C5 | 0.4 (3) | C14—C9—C10—C11 | −0.1 (2) |
C3—C4—C5—C6 | 0.1 (2) | C8—C9—C10—C11 | 176.70 (12) |
N2—N1—C6—C1 | −0.62 (13) | C9—C10—C11—C12 | −0.1 (2) |
C7—N1—C6—C1 | 179.91 (12) | C15—O2—C12—C11 | 0.8 (2) |
N2—N1—C6—C5 | 177.24 (13) | C15—O2—C12—C13 | −178.41 (14) |
C7—N1—C6—C5 | −2.2 (2) | C10—C11—C12—O2 | −178.87 (13) |
N3—C1—C6—N1 | 0.38 (14) | C10—C11—C12—C13 | 0.3 (2) |
C2—C1—C6—N1 | 179.01 (13) | O2—C12—C13—C14 | 178.92 (12) |
N3—C1—C6—C5 | −177.78 (12) | C11—C12—C13—C14 | −0.3 (2) |
C2—C1—C6—C5 | 0.8 (2) | C12—C13—C14—C9 | 0.1 (2) |
C4—C5—C6—N1 | −178.29 (13) | C10—C9—C14—C13 | 0.06 (19) |
C4—C5—C6—C1 | −0.75 (19) | C8—C9—C14—C13 | −176.78 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···O1i | 0.93 | 2.40 | 3.1912 (16) | 143 |
Symmetry code: (i) −x, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C15H13N3O2 |
Mr | 267.28 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 296 |
a, b, c (Å) | 5.4209 (1), 24.4894 (5), 10.0555 (2) |
β (°) | 98.552 (2) |
V (Å3) | 1320.07 (4) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 0.75 |
Crystal size (mm) | 0.34 × 0.17 × 0.16 |
Data collection | |
Diffractometer | Agilent SuperNova (Dual, Cu at zero, Atlas CCD) diffractometer |
Absorption correction | Multi-scan (CrysAlis PRO; Agilent, 2012) |
Tmin, Tmax | 0.784, 0.889 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6122, 2707, 2340 |
Rint | 0.019 |
(sin θ/λ)max (Å−1) | 0.630 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.109, 1.08 |
No. of reflections | 2707 |
No. of parameters | 182 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.14, −0.16 |
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 | 2.40 | 3.1912 (16) | 143 |
Symmetry code: (i) −x, −y+1, −z+1. |
Acknowledgements
The authors thank the Deanship of Scientific Research at King Abdulaziz University for support of this research via Research Group Track of grant No. (3-102/428).
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N-Acylbenzotriazoles are mild, regioselective and regiospecific reagents for N-, O-, C-, and S-acylation (Katritzky et al., 2010), & (Katritzky et al., 1996a). The title compound was previously converted into of a 1,3-diarylacetone (Katritzky et al., 2005) and an aryl benzyl sulfoxide (Katritzky et al., 1996b).
The title coompound is related in structure with 1-benzyl-1H-benzotriazole (Selvarathy Grace et al., 2012). The benzotriazole ring is almost planer with r.m.s. deviation of fitted non-hydrogen atoms (C1—C6/N1/N2/N3) is 0.0124 Å. The oxygen atom of carbonyl group is displaced at 0.0724 (2) Å with respect to benzotriazole. The methoxy benzene ring (C9—C14) is orientedted at dihedral angle of 76.21 (3)° with respect to benzotriazole rings. The C—H···O type weak hydrogen bonding interaction results in dimers about inversion center and generate twelve membered ring motif R22(12) (Table. 1, Fig. 2).