organic compounds
1-[1-(2,1,3-Benzoxadiazol-5-ylmethyl)-1H-1,2,3-triazol-4-yl]hexan-1-one
aAlberta Glycomics Centre, Department of Chemistry, University of Alberta, Edmonton, AB T6G 2G2, Canada, and bX-ray Crystallography Laboratory, Department of Chemistry, University of Alberta, Edmonton, AB T6G 2G2, Canada
*Correspondence e-mail: Bob.McDonald@ualberta.ca
The title compound, C15H17N5O2, was synthesized as part of a series of benzoxadiazole analogs which were examined for fluorescent properties by Cu-catalysed azide–alkyne cycloaddition (CuAAC) of a 4-azidomethyl-benzoxadiazole substrate. The structure shows a nearly coplanar orientation of the hexanone keto group and the 1,2,3-triazole ring [dihedral angle = 4.3 (3)°], while the benzoxadiazole and triazole groups are much more severely inclined [dihedral angle = 70.87 (4)°]. In the crystal, weak C—H⋯N interactions connect translationally-related triazole rings, while another set of C—H⋯N interactions is formed between inversion-related benzoxadiazole units, forming a three-dimensional network. The crystal studied was a non-merohedral twin with refined value of the twin fraction of 0.2289 (16).
Related literature
For the synthesis of similar benzoxadiazole compounds, see: Key & Cairo (2011); Li et al. (2010). For two related benzoxadiazole-triazole structures, see: Key, Cairo & Ferguson (2012); Key, Cairo & McDonald (2012). For structures of 1-(aryl)methyl-1,2,3-triazole compounds with 4-carbonyl substituents [RC(O) or ROC(O)], see: Harju et al. (2003); Huang et al. (2010); Dong & Cheng (2011); Jia & Lu (2011); Menendez et al. (2012).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2008); cell SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXD (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).
Supporting information
10.1107/S1600536812041839/mw2084sup1.cif
contains datablocks I, New_Global_Publ_Block. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812041839/mw2084Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812041839/mw2084Isup3.cml
4-(Azidomethyl)benz-[2,1,3-d]-oxadiazole (II) (40 mg, 0.23 mmol, 1 equiv) was dissolved in 1:1 water/methanol (5 mL). To this solution was added n-octyne (0.17 mL, 1.14 mmol, 5 equiv), which also contained oct-1-yn-3-one as an impurity. Copper sulfate (7 mg, 0.046 mmol, 0.2 equiv) and ascorbic acid (12 mg, 0.068 mmol, 0.3 equiv) were then added to the solution. The reaction mixture was allowed to stir at room temperature for approximately 1 h, forming a red precipitate. The precipitate was filtered off and the product was obtained after purification by δ 8.16 (s, 1H), 7.89 (d, 1H, 3J = 9.2 Hz), 7.51 (s, 1H), 7.32 (dd, 1H, 4J = 1.2 Hz, 3J = 9.2 Hz), 5.70 (s, 2H), 3.11(t, 2H, 3J = 7.2 Hz), 1.74 (m, 2H), 1.36 (m, 4H), 0.89 (m, 3H); 13C NMR (100 MHz, CDCl3): δ 195.5, 149.1, 148.9, 148.8, 138.1, 131.1, 126.0, 118.5, 116.0, 54.1, 39.8, 31.6, 23.8, 22.7, 14.2; IR (microscope): ν = 3098, 2954, 2930, 1691, 1531 cm-1; ES-HRMS calculated for C15H17N5O2Na [M+Na]+: 322.1279; observed: 322.1279. Rf = 0.45 (1:1 EtOAc/hexanes).
(EtOAc/hexanes) (35 mg, 51% yield). 1H NMR (400 MHz, CDCl3):The crystal used for data collection was found to display non-merohedral
Both components of the twin were indexed with the program CELL_NOW (Bruker, 2008). The second twin component can be related to the first component by 180° rotation about the [-1 0 2] axis in both real and A raw data file was produced by the data integration program SAINT (Bruker, 2008), using the two-component orientation matrix file that had been produced by CELL_NOW. Integrated intensities for the reflections from the two components were written into a SHELXL-97 HKLF 5 reflection file with the program TWINABS (Bruker, 2008), using all reflection data (exactly overlapped, partially overlapped and non-overlapped). The reflection (1 0 0) was found to have an excessively high disagreement between Fo and Fc, and was omitted from the The refined value of the twin fraction (SHELXL-97 BASF parameter) was 0.2289 (16). All H atoms were generated in idealized positions and refined using a riding model with fixed C-H distances (C-Haromatic = 0.95 Å, C-Hmethylene = 0.99 Å, C-Hmethyl = 0.98 Å) and with Uiso(H) = 1.2Ueq(C).Data collection: APEX2 (Bruker, 2008); cell
SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXD (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).C15H17N5O2 | F(000) = 632 |
Mr = 299.34 | Dx = 1.333 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 5974 reflections |
a = 16.5752 (16) Å | θ = 2.5–24.3° |
b = 5.5429 (5) Å | µ = 0.09 mm−1 |
c = 16.2452 (16) Å | T = 173 K |
β = 91.3612 (13)° | Rod, colourless |
V = 1492.1 (2) Å3 | 0.74 × 0.14 × 0.06 mm |
Z = 4 |
Bruker APEXII CCD diffractometer | 3079 independent reflections |
Radiation source: fine-focus sealed tube | 2413 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.051 |
Detector resolution: 8.26 pixels mm-1 | θmax = 26.5°, θmin = 1.2° |
ω scans | h = −20→20 |
Absorption correction: multi-scan (TWINABS; Bruker, 2008) | k = −6→6 |
Tmin = 0.935, Tmax = 0.995 | l = −20→20 |
45733 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)] = 0.040 | H-atom parameters constrained |
wR(F2) = 0.091 | w = 1/[σ2(Fo2) + (0.0331P)2 + 0.4646P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
3079 reflections | Δρmax = 0.19 e Å−3 |
201 parameters | Δρmin = −0.17 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0114 (15) |
C15H17N5O2 | V = 1492.1 (2) Å3 |
Mr = 299.34 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 16.5752 (16) Å | µ = 0.09 mm−1 |
b = 5.5429 (5) Å | T = 173 K |
c = 16.2452 (16) Å | 0.74 × 0.14 × 0.06 mm |
β = 91.3612 (13)° |
Bruker APEXII CCD diffractometer | 3079 independent reflections |
Absorption correction: multi-scan (TWINABS; Bruker, 2008) | 2413 reflections with I > 2σ(I) |
Tmin = 0.935, Tmax = 0.995 | Rint = 0.051 |
45733 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.091 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.19 e Å−3 |
3079 reflections | Δρmin = −0.17 e Å−3 |
201 parameters |
Geometry. All standard uncertainties (s.u.'s) (except the s.u. in the dihedral angle between two least-squares planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving least-squares 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 | ||
O1 | −0.07380 (7) | 0.1919 (2) | 0.16041 (7) | 0.0409 (3) | |
O2 | 0.51268 (8) | 0.0088 (2) | 0.11538 (10) | 0.0593 (4) | |
N1 | −0.03444 (8) | −0.0165 (3) | 0.18558 (9) | 0.0382 (4) | |
N2 | −0.03404 (8) | 0.3110 (3) | 0.09850 (9) | 0.0363 (3) | |
N3 | 0.29027 (7) | 0.1559 (2) | 0.00229 (8) | 0.0272 (3) | |
N4 | 0.29675 (8) | 0.3994 (2) | 0.00904 (9) | 0.0317 (3) | |
N5 | 0.36597 (7) | 0.4428 (2) | 0.04758 (9) | 0.0309 (3) | |
C1 | 0.02958 (9) | −0.0270 (3) | 0.13892 (9) | 0.0287 (4) | |
C2 | 0.02964 (8) | 0.1752 (3) | 0.08476 (9) | 0.0272 (3) | |
C3 | 0.09143 (9) | 0.2061 (3) | 0.02610 (9) | 0.0278 (3) | |
H3 | 0.0918 | 0.3406 | −0.0101 | 0.033* | |
C4 | 0.14968 (9) | 0.0339 (3) | 0.02451 (9) | 0.0256 (3) | |
C5 | 0.14964 (9) | −0.1700 (3) | 0.07982 (10) | 0.0289 (3) | |
H5 | 0.1919 | −0.2850 | 0.0766 | 0.035* | |
C6 | 0.09180 (9) | −0.2039 (3) | 0.13617 (10) | 0.0311 (4) | |
H6 | 0.0927 | −0.3392 | 0.1721 | 0.037* | |
C7 | 0.21712 (9) | 0.0526 (3) | −0.03636 (10) | 0.0314 (4) | |
H7A | 0.2294 | −0.1098 | −0.0580 | 0.038* | |
H7B | 0.1994 | 0.1553 | −0.0833 | 0.038* | |
C8 | 0.35461 (9) | 0.0453 (3) | 0.03618 (10) | 0.0293 (4) | |
H8 | 0.3646 | −0.1233 | 0.0395 | 0.035* | |
C9 | 0.40295 (9) | 0.2287 (3) | 0.06506 (10) | 0.0288 (4) | |
C10 | 0.48268 (9) | 0.2074 (3) | 0.10742 (10) | 0.0330 (4) | |
C11 | 0.52284 (9) | 0.4320 (3) | 0.13876 (11) | 0.0331 (4) | |
H11A | 0.4886 | 0.5057 | 0.1811 | 0.040* | |
H11B | 0.5268 | 0.5484 | 0.0928 | 0.040* | |
C12 | 0.60693 (9) | 0.3892 (3) | 0.17585 (11) | 0.0349 (4) | |
H12A | 0.6029 | 0.2767 | 0.2229 | 0.042* | |
H12B | 0.6409 | 0.3117 | 0.1341 | 0.042* | |
C13 | 0.64772 (9) | 0.6203 (3) | 0.20530 (10) | 0.0320 (4) | |
H13A | 0.6496 | 0.7355 | 0.1588 | 0.038* | |
H13B | 0.6149 | 0.6941 | 0.2488 | 0.038* | |
C14 | 0.73289 (10) | 0.5801 (3) | 0.23904 (12) | 0.0422 (4) | |
H14A | 0.7665 | 0.5154 | 0.1946 | 0.051* | |
H14B | 0.7315 | 0.4576 | 0.2833 | 0.051* | |
C15 | 0.77195 (11) | 0.8090 (4) | 0.27312 (11) | 0.0450 (5) | |
H15A | 0.8265 | 0.7723 | 0.2939 | 0.054* | |
H15B | 0.7397 | 0.8722 | 0.3180 | 0.054* | |
H15C | 0.7748 | 0.9300 | 0.2293 | 0.054* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0309 (6) | 0.0481 (8) | 0.0440 (7) | 0.0059 (6) | 0.0048 (5) | −0.0042 (6) |
O2 | 0.0466 (8) | 0.0264 (7) | 0.1034 (13) | 0.0055 (6) | −0.0278 (8) | −0.0033 (7) |
N1 | 0.0341 (7) | 0.0428 (9) | 0.0379 (8) | 0.0016 (7) | 0.0028 (6) | −0.0012 (7) |
N2 | 0.0316 (7) | 0.0373 (8) | 0.0400 (8) | 0.0036 (6) | −0.0019 (6) | −0.0019 (7) |
N3 | 0.0270 (6) | 0.0249 (7) | 0.0297 (7) | −0.0020 (5) | 0.0035 (5) | −0.0010 (6) |
N4 | 0.0301 (7) | 0.0256 (7) | 0.0395 (8) | −0.0010 (6) | 0.0011 (6) | 0.0004 (6) |
N5 | 0.0277 (7) | 0.0242 (7) | 0.0409 (8) | −0.0001 (5) | 0.0004 (6) | 0.0006 (6) |
C1 | 0.0264 (8) | 0.0317 (9) | 0.0279 (8) | −0.0042 (7) | −0.0016 (6) | −0.0018 (7) |
C2 | 0.0244 (7) | 0.0258 (8) | 0.0310 (8) | −0.0003 (6) | −0.0061 (6) | −0.0037 (7) |
C3 | 0.0304 (8) | 0.0248 (8) | 0.0281 (8) | −0.0035 (7) | −0.0041 (6) | 0.0008 (7) |
C4 | 0.0254 (7) | 0.0259 (8) | 0.0254 (8) | −0.0039 (6) | −0.0045 (6) | −0.0033 (6) |
C5 | 0.0281 (8) | 0.0250 (8) | 0.0334 (8) | 0.0024 (6) | −0.0024 (6) | −0.0016 (7) |
C6 | 0.0354 (8) | 0.0256 (8) | 0.0323 (9) | −0.0004 (7) | −0.0019 (7) | 0.0037 (7) |
C7 | 0.0311 (8) | 0.0339 (9) | 0.0292 (9) | −0.0043 (7) | −0.0012 (6) | −0.0042 (7) |
C8 | 0.0288 (8) | 0.0235 (8) | 0.0359 (9) | 0.0006 (6) | 0.0040 (6) | 0.0007 (7) |
C9 | 0.0277 (8) | 0.0228 (8) | 0.0359 (9) | 0.0004 (6) | 0.0036 (6) | −0.0001 (7) |
C10 | 0.0290 (8) | 0.0258 (9) | 0.0442 (10) | 0.0011 (7) | −0.0009 (7) | 0.0014 (8) |
C11 | 0.0287 (8) | 0.0285 (9) | 0.0422 (10) | −0.0003 (7) | −0.0007 (7) | −0.0011 (7) |
C12 | 0.0323 (8) | 0.0312 (9) | 0.0410 (10) | −0.0020 (7) | −0.0037 (7) | 0.0050 (8) |
C13 | 0.0295 (8) | 0.0344 (9) | 0.0321 (9) | −0.0017 (7) | −0.0005 (7) | 0.0001 (7) |
C14 | 0.0370 (9) | 0.0402 (11) | 0.0488 (11) | −0.0043 (8) | −0.0115 (8) | 0.0055 (9) |
C15 | 0.0410 (10) | 0.0518 (12) | 0.0418 (11) | −0.0113 (9) | −0.0077 (8) | 0.0025 (9) |
O1—N2 | 1.3831 (18) | C7—H7B | 0.9900 |
O1—N1 | 1.3835 (18) | C8—C9 | 1.370 (2) |
O2—C10 | 1.214 (2) | C8—H8 | 0.9500 |
N1—C1 | 1.320 (2) | C9—C10 | 1.480 (2) |
N2—C2 | 1.320 (2) | C10—C11 | 1.495 (2) |
N3—C8 | 1.3376 (19) | C11—C12 | 1.524 (2) |
N3—N4 | 1.3581 (18) | C11—H11A | 0.9900 |
N3—C7 | 1.4682 (19) | C11—H11B | 0.9900 |
N4—N5 | 1.3160 (17) | C12—C13 | 1.520 (2) |
N5—C9 | 1.3627 (19) | C12—H12A | 0.9900 |
C1—C2 | 1.425 (2) | C12—H12B | 0.9900 |
C1—C6 | 1.425 (2) | C13—C14 | 1.519 (2) |
C2—C3 | 1.426 (2) | C13—H13A | 0.9900 |
C3—C4 | 1.358 (2) | C13—H13B | 0.9900 |
C3—H3 | 0.9500 | C14—C15 | 1.523 (2) |
C4—C5 | 1.444 (2) | C14—H14A | 0.9900 |
C4—C7 | 1.513 (2) | C14—H14B | 0.9900 |
C5—C6 | 1.354 (2) | C15—H15A | 0.9800 |
C5—H5 | 0.9500 | C15—H15B | 0.9800 |
C6—H6 | 0.9500 | C15—H15C | 0.9800 |
C7—H7A | 0.9900 | ||
N2—O1—N1 | 112.57 (11) | N5—C9—C10 | 123.94 (14) |
C1—N1—O1 | 104.30 (13) | C8—C9—C10 | 127.49 (14) |
C2—N2—O1 | 104.33 (13) | O2—C10—C9 | 118.73 (15) |
C8—N3—N4 | 111.20 (12) | O2—C10—C11 | 122.74 (14) |
C8—N3—C7 | 129.75 (13) | C9—C10—C11 | 118.53 (14) |
N4—N3—C7 | 119.02 (13) | C10—C11—C12 | 113.64 (14) |
N5—N4—N3 | 106.65 (12) | C10—C11—H11A | 108.8 |
N4—N5—C9 | 108.83 (12) | C12—C11—H11A | 108.8 |
N1—C1—C2 | 109.40 (14) | C10—C11—H11B | 108.8 |
N1—C1—C6 | 129.85 (15) | C12—C11—H11B | 108.8 |
C2—C1—C6 | 120.73 (14) | H11A—C11—H11B | 107.7 |
N2—C2—C1 | 109.39 (14) | C13—C12—C11 | 112.92 (14) |
N2—C2—C3 | 129.38 (15) | C13—C12—H12A | 109.0 |
C1—C2—C3 | 121.22 (14) | C11—C12—H12A | 109.0 |
C4—C3—C2 | 116.78 (14) | C13—C12—H12B | 109.0 |
C4—C3—H3 | 121.6 | C11—C12—H12B | 109.0 |
C2—C3—H3 | 121.6 | H12A—C12—H12B | 107.8 |
C3—C4—C5 | 121.82 (14) | C14—C13—C12 | 113.13 (14) |
C3—C4—C7 | 120.05 (14) | C14—C13—H13A | 109.0 |
C5—C4—C7 | 118.13 (14) | C12—C13—H13A | 109.0 |
C6—C5—C4 | 122.70 (15) | C14—C13—H13B | 109.0 |
C6—C5—H5 | 118.6 | C12—C13—H13B | 109.0 |
C4—C5—H5 | 118.6 | H13A—C13—H13B | 107.8 |
C5—C6—C1 | 116.74 (15) | C13—C14—C15 | 113.11 (15) |
C5—C6—H6 | 121.6 | C13—C14—H14A | 109.0 |
C1—C6—H6 | 121.6 | C15—C14—H14A | 109.0 |
N3—C7—C4 | 111.25 (12) | C13—C14—H14B | 109.0 |
N3—C7—H7A | 109.4 | C15—C14—H14B | 109.0 |
C4—C7—H7A | 109.4 | H14A—C14—H14B | 107.8 |
N3—C7—H7B | 109.4 | C14—C15—H15A | 109.5 |
C4—C7—H7B | 109.4 | C14—C15—H15B | 109.5 |
H7A—C7—H7B | 108.0 | H15A—C15—H15B | 109.5 |
N3—C8—C9 | 104.76 (14) | C14—C15—H15C | 109.5 |
N3—C8—H8 | 127.6 | H15A—C15—H15C | 109.5 |
C9—C8—H8 | 127.6 | H15B—C15—H15C | 109.5 |
N5—C9—C8 | 108.57 (13) | ||
N2—O1—N1—C1 | −0.28 (17) | C2—C1—C6—C5 | −0.3 (2) |
N1—O1—N2—C2 | 0.55 (16) | C8—N3—C7—C4 | 94.95 (19) |
C8—N3—N4—N5 | 0.04 (18) | N4—N3—C7—C4 | −82.78 (18) |
C7—N3—N4—N5 | 178.17 (12) | C3—C4—C7—N3 | 98.31 (16) |
N3—N4—N5—C9 | 0.00 (17) | C5—C4—C7—N3 | −81.66 (17) |
O1—N1—C1—C2 | −0.09 (16) | N4—N3—C8—C9 | −0.05 (17) |
O1—N1—C1—C6 | −178.92 (15) | C7—N3—C8—C9 | −177.93 (14) |
O1—N2—C2—C1 | −0.58 (16) | N4—N5—C9—C8 | −0.03 (18) |
O1—N2—C2—C3 | 178.43 (14) | N4—N5—C9—C10 | 179.26 (15) |
N1—C1—C2—N2 | 0.45 (18) | N3—C8—C9—N5 | 0.05 (17) |
C6—C1—C2—N2 | 179.40 (14) | N3—C8—C9—C10 | −179.21 (15) |
N1—C1—C2—C3 | −178.66 (14) | N5—C9—C10—O2 | −175.34 (17) |
C6—C1—C2—C3 | 0.3 (2) | C8—C9—C10—O2 | 3.8 (3) |
N2—C2—C3—C4 | −178.81 (15) | N5—C9—C10—C11 | 4.8 (2) |
C1—C2—C3—C4 | 0.1 (2) | C8—C9—C10—C11 | −176.09 (16) |
C2—C3—C4—C5 | −0.4 (2) | O2—C10—C11—C12 | 4.1 (3) |
C2—C3—C4—C7 | 179.59 (13) | C9—C10—C11—C12 | −176.03 (15) |
C3—C4—C5—C6 | 0.4 (2) | C10—C11—C12—C13 | 178.46 (14) |
C7—C4—C5—C6 | −179.61 (14) | C11—C12—C13—C14 | −177.59 (15) |
C4—C5—C6—C1 | 0.0 (2) | C12—C13—C14—C15 | −176.65 (15) |
N1—C1—C6—C5 | 178.39 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···N2i | 0.95 | 2.58 | 3.475 (2) | 158 |
C8—H8···N5ii | 0.95 | 2.41 | 3.350 (2) | 171 |
Symmetry codes: (i) −x, −y+1, −z; (ii) x, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | C15H17N5O2 |
Mr | 299.34 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 173 |
a, b, c (Å) | 16.5752 (16), 5.5429 (5), 16.2452 (16) |
β (°) | 91.3612 (13) |
V (Å3) | 1492.1 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.74 × 0.14 × 0.06 |
Data collection | |
Diffractometer | Bruker APEXII CCD diffractometer |
Absorption correction | Multi-scan (TWINABS; Bruker, 2008) |
Tmin, Tmax | 0.935, 0.995 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 45733, 3079, 2413 |
Rint | 0.051 |
(sin θ/λ)max (Å−1) | 0.627 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.091, 1.03 |
No. of reflections | 3079 |
No. of parameters | 201 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.19, −0.17 |
Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXD (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2010).
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···N2i | 0.95 | 2.58 | 3.475 (2) | 158 |
C8—H8···N5ii | 0.95 | 2.41 | 3.350 (2) | 171 |
Symmetry codes: (i) −x, −y+1, −z; (ii) x, y−1, z. |
Acknowledgements
We acknowledge the University of Alberta, the Natural Sciences and Engineering Research Council of Canada and the Alberta Glycomics Centre for funding of this work.
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In an effort to explore benzoxadiazole derivatives with interesting spectroscopic properties, we generated the title compound, I, for comparison to its parent 4-azidomethyl-benzoxadiazole (II). Although we observed large changes in the spectra of substrates with an azido group conjugated to the chromophore, derivatives with an intervening methylene group tended to have only small changes upon triazole formation (Key & Cairo, 2011). Compound I was synthesized unintentionally through the use of an oxidized sample of n-octyne which also contained oct-1-yn-3-one as an impurity. The hexanone product was isolated by column chromatography and used for structural studies. (λmaxABS EtOH: 278, 289 nm, Absorption coefficient: 12,300 M-1cm-1)
In the crystal the 1,2,3-triazole ring and hexan-1-on-1-yl groups are nearly coplanar; the angle between the ketonic fragment (O2-C10-C11) and the 1,2,3-triazole ring is 4.3 (3)°. The rings of the benzoxadiazole and triazole groups are much more severely inclined (70.87 (4)°). Weak C-H···N interactions are observed between triazole moieties related via translation parallel to the b axis (2.41 Å for H8···N5[x, -1+y, z]). A further set of weak C-H···N interactions is seen between benzoxadiazole groups related by the inversion center (0, 1/2, 0) (2.58 Å for H3···N2[-x, 1-y, -z]). A parallel-stacking interaction is observed between benzoxadiazole rings related by inversion through the origin (interplanar spacing = 3.328 Å).