organic compounds
Di-tert-butyl N-{[1-(pyridin-4-yl)-1H-1,2,3-triazol-4-yl]methyl}iminodiacetate
aLSPCMIB, UMR-CNRS 5068, Université de Toulouse, 118 route de Narbonne, F-31062 Toulouse cedex 9, and bUniversité de Toulouse, UPS and CNRS, Institut de Chimie de Toulouse, FR2599, 118 route de Narbonne, F-31062 Toulouse cedex 9, France
*Correspondence e-mail: benoist@chimie.ups-tlse.fr
In the title compound, C20H29N5O4, the pyridine ring makes a dihedral angle of 10.41 (16)° with the triazole ring, which exhibits an azo-like character. In the crystal, molecules are linked by C—H⋯O and C—H⋯N hydrogen bonds, and C—H⋯π interactions involving a methyl group and the pyridine ring of a neighbouring molecule, leading to the formation of a three-dimensional network.
Related literature
For 4-pyridyl-1,2,3-triazoles as building blocks in the synthesis of chelating agents for biomedical applications, see: Bonnet et al. (2012); Pellegatti et al. (2008). For the crystal structures of structural isomers such as 2-pyridyl-1,2,3-triazoles, see: Obata et al. (2008); Schweinfurth et al. (2008); Boulay et al. (2010); Seridi et al. (2011); Crowley et al. (2010); Kilpin et al. (2011).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2008); cell APEX2 and SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX publication routines (Farrugia, 2012) and publCIF (Westrip, 2010).
Supporting information
10.1107/S1600536812042596/su2510sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812042596/su2510Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812042596/su2510Isup3.cml
Freshly prepared 4-azidopyridine (0.4 g, 3.3 mmol), 3-[bis(tert-butoxycarbonylmeth-yl) amino]-prop-1-yne (0.94 g, 3.3 mmol), copper(II) acetate monohydrate (130 mg, 0.66 mmol) and sodium ascorbate (260 mg, 1.32 mmol) were mixed in acetonitrile (5 ml) and stirred overnight at 303 K. The resulting brown solution was cooled then diluted with chloroform (10 ml) and washed twice with saturated Na2edta solution (2x15 ml). The aqueous solutions were extracted with chloroform (3x7 ml). The organic extracts were combined, dried over Na2SO4 and the solvent was taken off under reduce pressure. The crude product was purified by
on neutral alumina (eluent: CH2Cl2) to give 1.03 g of the title compound [Yield: 77%]. Analysis calculated for C20H29N5O4: C 59.54, H 7.24, N 17.36%; found: C 59.24, H 7.32, N 17.44%. Plate-like colourless crystals, suitable for X-ray were obtained by slow evaporation of a methanol-dichloromethane (1:1 / v:v) solution. Further spectroscopic data for the title compound are available in the archived CIF.All the H atoms were included in calculated positions and treated as riding atoms: C—H = 0.95 Å (aromatic), 0.99 Å (methylene) and 0.98 Å (methyl) with Uiso(H) = 1.2Ueq(aromatic, methylene) or Uiso(H) = 1.5Ueq(methyl). In the final cycles of
in the absence of significant effects, 2547 Friedel pairs were merged and \Df " set to zero.Data collection: APEX2 (Bruker, 2008); cell
APEX2 and SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX publication routines (Farrugia, 2012) and publCIF (Westrip, 2010).C20H29N5O4 | F(000) = 432 |
Mr = 403.48 | Dx = 1.19 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 1261 reflections |
a = 9.1568 (8) Å | θ = 2.4–21.3° |
b = 11.4452 (10) Å | µ = 0.09 mm−1 |
c = 11.4928 (11) Å | T = 193 K |
β = 110.840 (4)° | Plate, colourless |
V = 1125.66 (18) Å3 | 0.2 × 0.1 × 0.04 mm |
Z = 2 |
Bruker Kappa APEXII Quazar diffractometer | 3530 independent reflections |
Radiation source: microfocus sealed tube | 1947 reflections with I > 2σ(I) |
Multilayer optics monochromator | Rint = 0.077 |
phi and ω scans | θmax = 30.6°, θmin = 3.0° |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −13→11 |
Tmin = 0.989, Tmax = 0.997 | k = −14→16 |
11329 measured reflections | l = −16→16 |
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)] = 0.059 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.122 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0464P)2] where P = (Fo2 + 2Fc2)/3 |
3530 reflections | (Δ/σ)max = 0.001 |
268 parameters | Δρmax = 0.18 e Å−3 |
1 restraint | Δρmin = −0.18 e Å−3 |
C20H29N5O4 | V = 1125.66 (18) Å3 |
Mr = 403.48 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 9.1568 (8) Å | µ = 0.09 mm−1 |
b = 11.4452 (10) Å | T = 193 K |
c = 11.4928 (11) Å | 0.2 × 0.1 × 0.04 mm |
β = 110.840 (4)° |
Bruker Kappa APEXII Quazar diffractometer | 3530 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | 1947 reflections with I > 2σ(I) |
Tmin = 0.989, Tmax = 0.997 | Rint = 0.077 |
11329 measured reflections |
R[F2 > 2σ(F2)] = 0.059 | 1 restraint |
wR(F2) = 0.122 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.18 e Å−3 |
3530 reflections | Δρmin = −0.18 e Å−3 |
268 parameters |
Experimental. Spectroscopic data for the title compound: 1H NMR (300 MHz, CDCl3): δ/p.p.m. = 1.45 (s, 18H, CH3); 3.49 (s, 4H, CH2); 4.12 (s, 2H, CH2); 7.72 (m, 2H, CHAr); 8.24 (s, 1H, CHta); 8.75 (m, 2H, CHAr); 13C NMR (75 MHz, CDCl3): δ/p.p.m. = 28.1 (9CH3); 49.0 (CH2); 55.5 (2CH2); 81.3 (2CIV); 113.6, 151.6 (4CHAr); 120.7 (CHta); 143.1, 147.5 (2CIV); 170.3 (2CO); IR (KBr): νC=O = 1735 cm-1; MS (DCI/NH3): m/z 404, [M+]; 426, [M+Na+]; 443, [M+K+]. |
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 | ||
O2 | 0.8574 (2) | 0.02696 (19) | 0.4779 (2) | 0.0380 (5) | |
N1 | 1.0194 (3) | 0.7418 (2) | 0.9730 (2) | 0.0392 (7) | |
O3 | 0.6055 (3) | 0.0266 (2) | 0.8927 (2) | 0.0521 (7) | |
O4 | 0.5024 (3) | −0.13966 (19) | 0.7905 (2) | 0.0378 (6) | |
N5 | 0.6572 (3) | 0.1115 (2) | 0.6817 (2) | 0.0276 (6) | |
N3 | 0.5993 (3) | 0.5068 (2) | 0.6577 (2) | 0.0407 (7) | |
N4 | 0.5251 (3) | 0.4092 (3) | 0.6151 (2) | 0.0393 (7) | |
C4 | 0.9274 (3) | 0.5441 (3) | 0.9510 (3) | 0.0342 (8) | |
H4 | 0.9346 | 0.4682 | 0.9859 | 0.041* | |
C17 | 0.4539 (4) | −0.1904 (3) | 0.8901 (3) | 0.0442 (9) | |
C6 | 0.7207 (4) | 0.3635 (3) | 0.7862 (3) | 0.0293 (7) | |
H6 | 0.7926 | 0.3216 | 0.8537 | 0.035* | |
C7 | 0.5962 (3) | 0.3197 (3) | 0.6918 (3) | 0.0278 (7) | |
C10 | 0.8501 (4) | 0.0438 (3) | 0.5901 (3) | 0.0323 (7) | |
C9 | 0.7146 (3) | 0.1245 (3) | 0.5787 (3) | 0.0290 (7) | |
H9A | 0.7481 | 0.2064 | 0.576 | 0.035* | |
H9B | 0.6281 | 0.1081 | 0.4993 | 0.035* | |
N2 | 0.7201 (3) | 0.4797 (2) | 0.7634 (2) | 0.0277 (6) | |
C5 | 0.8218 (3) | 0.5684 (3) | 0.8340 (3) | 0.0279 (7) | |
C8 | 0.5345 (3) | 0.1981 (3) | 0.6690 (3) | 0.0335 (8) | |
H8A | 0.4823 | 0.1794 | 0.7288 | 0.04* | |
H8B | 0.4551 | 0.1931 | 0.584 | 0.04* | |
O1 | 0.9358 (3) | 0.0025 (2) | 0.6860 (2) | 0.0511 (7) | |
C16 | 0.5703 (4) | −0.0346 (3) | 0.8019 (3) | 0.0339 (7) | |
C15 | 0.5930 (4) | −0.0054 (3) | 0.6821 (3) | 0.0299 (7) | |
H15A | 0.6644 | −0.0636 | 0.6672 | 0.036* | |
H15B | 0.4912 | −0.0113 | 0.6128 | 0.036* | |
C2 | 0.9161 (4) | 0.7613 (3) | 0.8589 (3) | 0.0408 (8) | |
H2 | 0.9119 | 0.8378 | 0.8258 | 0.049* | |
C3 | 1.0224 (4) | 0.6337 (3) | 1.0161 (3) | 0.0393 (8) | |
H3 | 1.0948 | 0.6169 | 1.097 | 0.047* | |
C11 | 0.9656 (4) | −0.0587 (3) | 0.4568 (3) | 0.0440 (9) | |
C14 | 0.9375 (5) | −0.1775 (3) | 0.5026 (5) | 0.0735 (14) | |
H14A | 0.9729 | −0.177 | 0.5937 | 0.11* | |
H14B | 0.9957 | −0.2369 | 0.4755 | 0.11* | |
H14C | 0.8256 | −0.1957 | 0.4682 | 0.11* | |
C19 | 0.3794 (6) | −0.3030 (4) | 0.8319 (4) | 0.0722 (13) | |
H19A | 0.2924 | −0.2864 | 0.7542 | 0.108* | |
H19B | 0.34 | −0.3444 | 0.8893 | 0.108* | |
H19C | 0.4569 | −0.3516 | 0.814 | 0.108* | |
C1 | 0.8158 (4) | 0.6794 (3) | 0.7858 (3) | 0.0380 (8) | |
H1 | 0.7448 | 0.6984 | 0.705 | 0.046* | |
C12 | 1.1312 (4) | −0.0187 (4) | 0.5169 (4) | 0.0566 (11) | |
H12A | 1.1436 | 0.0581 | 0.484 | 0.085* | |
H12B | 1.2012 | −0.0749 | 0.499 | 0.085* | |
H12C | 1.1573 | −0.0133 | 0.6072 | 0.085* | |
C18 | 0.5965 (5) | −0.2123 (4) | 1.0045 (4) | 0.0658 (12) | |
H18A | 0.6712 | −0.2602 | 0.9821 | 0.099* | |
H18B | 0.5658 | −0.2534 | 1.067 | 0.099* | |
H18C | 0.6451 | −0.1375 | 1.0386 | 0.099* | |
C20 | 0.3373 (5) | −0.1108 (4) | 0.9149 (4) | 0.0656 (12) | |
H20A | 0.3908 | −0.0407 | 0.9584 | 0.098* | |
H20B | 0.2886 | −0.1516 | 0.9667 | 0.098* | |
H20C | 0.2567 | −0.0884 | 0.8357 | 0.098* | |
C13 | 0.9166 (5) | −0.0569 (4) | 0.3165 (4) | 0.0776 (15) | |
H13A | 0.8057 | −0.0775 | 0.279 | 0.116* | |
H13B | 0.9791 | −0.1135 | 0.2904 | 0.116* | |
H13C | 0.933 | 0.0215 | 0.2892 | 0.116* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O2 | 0.0374 (12) | 0.0399 (14) | 0.0433 (13) | 0.0053 (11) | 0.0224 (10) | 0.0003 (11) |
N1 | 0.0382 (15) | 0.0331 (17) | 0.0403 (16) | −0.0034 (14) | 0.0067 (12) | −0.0002 (13) |
O3 | 0.0732 (17) | 0.0544 (16) | 0.0345 (13) | −0.0248 (14) | 0.0262 (12) | −0.0158 (12) |
O4 | 0.0505 (13) | 0.0322 (13) | 0.0355 (12) | −0.0114 (11) | 0.0213 (10) | 0.0007 (10) |
N5 | 0.0300 (13) | 0.0248 (14) | 0.0315 (13) | −0.0036 (12) | 0.0151 (11) | −0.0047 (10) |
N3 | 0.0432 (15) | 0.0378 (17) | 0.0291 (14) | 0.0000 (14) | −0.0020 (12) | 0.0014 (12) |
N4 | 0.0437 (16) | 0.0287 (16) | 0.0354 (15) | −0.0019 (14) | 0.0015 (13) | 0.0022 (12) |
C4 | 0.0378 (18) | 0.0237 (17) | 0.0341 (17) | 0.0005 (15) | 0.0044 (14) | 0.0039 (14) |
C17 | 0.058 (2) | 0.043 (2) | 0.043 (2) | −0.012 (2) | 0.0311 (18) | 0.0024 (16) |
C6 | 0.0325 (16) | 0.0212 (16) | 0.0337 (17) | 0.0046 (14) | 0.0112 (13) | 0.0041 (13) |
C7 | 0.0296 (16) | 0.0232 (17) | 0.0307 (16) | 0.0021 (14) | 0.0107 (13) | −0.0003 (13) |
C10 | 0.0341 (16) | 0.0273 (18) | 0.0374 (18) | −0.0035 (15) | 0.0150 (14) | 0.0013 (14) |
C9 | 0.0305 (15) | 0.0227 (17) | 0.0354 (17) | −0.0017 (14) | 0.0136 (13) | 0.0010 (13) |
N2 | 0.0302 (12) | 0.0239 (15) | 0.0259 (13) | 0.0025 (12) | 0.0061 (10) | 0.0020 (11) |
C5 | 0.0308 (15) | 0.0259 (17) | 0.0280 (15) | −0.0020 (14) | 0.0118 (13) | −0.0014 (13) |
C8 | 0.0284 (15) | 0.034 (2) | 0.0391 (18) | −0.0007 (15) | 0.0129 (14) | −0.0032 (14) |
O1 | 0.0452 (13) | 0.0633 (18) | 0.0441 (14) | 0.0205 (14) | 0.0151 (11) | 0.0161 (13) |
C16 | 0.0348 (17) | 0.0346 (19) | 0.0352 (18) | −0.0056 (15) | 0.0160 (14) | −0.0026 (14) |
C15 | 0.0347 (16) | 0.0261 (17) | 0.0297 (15) | −0.0065 (15) | 0.0124 (13) | −0.0057 (13) |
C2 | 0.051 (2) | 0.0250 (18) | 0.0391 (19) | −0.0054 (17) | 0.0077 (16) | 0.0046 (15) |
C3 | 0.0398 (18) | 0.033 (2) | 0.0362 (19) | −0.0009 (16) | 0.0027 (15) | 0.0052 (15) |
C11 | 0.041 (2) | 0.037 (2) | 0.063 (2) | 0.0023 (17) | 0.0302 (18) | −0.0075 (17) |
C14 | 0.075 (3) | 0.035 (2) | 0.129 (4) | 0.000 (2) | 0.060 (3) | −0.011 (3) |
C19 | 0.098 (3) | 0.058 (3) | 0.074 (3) | −0.034 (3) | 0.047 (3) | 0.001 (2) |
C1 | 0.0471 (18) | 0.0270 (19) | 0.0316 (17) | −0.0006 (17) | 0.0039 (14) | 0.0083 (14) |
C12 | 0.039 (2) | 0.054 (3) | 0.087 (3) | 0.006 (2) | 0.035 (2) | −0.001 (2) |
C18 | 0.079 (3) | 0.077 (3) | 0.046 (2) | 0.002 (3) | 0.029 (2) | 0.019 (2) |
C20 | 0.067 (3) | 0.082 (3) | 0.067 (3) | −0.006 (3) | 0.048 (2) | 0.005 (2) |
C13 | 0.074 (3) | 0.106 (4) | 0.065 (3) | 0.016 (3) | 0.041 (2) | −0.023 (3) |
O2—C10 | 1.328 (4) | C8—H8B | 0.99 |
O2—C11 | 1.474 (4) | C16—C15 | 1.501 (4) |
N1—C3 | 1.329 (4) | C15—H15A | 0.99 |
N1—C2 | 1.335 (4) | C15—H15B | 0.99 |
O3—C16 | 1.202 (4) | C2—C1 | 1.371 (4) |
O4—C16 | 1.339 (4) | C2—H2 | 0.95 |
O4—C17 | 1.486 (4) | C3—H3 | 0.95 |
N5—C15 | 1.461 (4) | C11—C12 | 1.497 (5) |
N5—C9 | 1.464 (4) | C11—C13 | 1.512 (5) |
N5—C8 | 1.466 (4) | C11—C14 | 1.513 (5) |
N3—N4 | 1.308 (4) | C14—H14A | 0.98 |
N3—N2 | 1.356 (3) | C14—H14B | 0.98 |
N4—C7 | 1.358 (4) | C14—H14C | 0.98 |
C4—C5 | 1.377 (4) | C19—H19A | 0.98 |
C4—C3 | 1.379 (4) | C19—H19B | 0.98 |
C4—H4 | 0.95 | C19—H19C | 0.98 |
C17—C19 | 1.499 (5) | C1—H1 | 0.95 |
C17—C20 | 1.506 (5) | C12—H12A | 0.98 |
C17—C18 | 1.508 (5) | C12—H12B | 0.98 |
C6—N2 | 1.355 (4) | C12—H12C | 0.98 |
C6—C7 | 1.359 (4) | C18—H18A | 0.98 |
C6—H6 | 0.95 | C18—H18B | 0.98 |
C7—C8 | 1.489 (4) | C18—H18C | 0.98 |
C10—O1 | 1.200 (4) | C20—H20A | 0.98 |
C10—C9 | 1.514 (4) | C20—H20B | 0.98 |
C9—H9A | 0.99 | C20—H20C | 0.98 |
C9—H9B | 0.99 | C13—H13A | 0.98 |
N2—C5 | 1.421 (4) | C13—H13B | 0.98 |
C5—C1 | 1.380 (4) | C13—H13C | 0.98 |
C8—H8A | 0.99 | ||
C10—O2—C11 | 121.7 (2) | H15A—C15—H15B | 107.8 |
C3—N1—C2 | 115.8 (3) | N1—C2—C1 | 125.0 (3) |
C16—O4—C17 | 122.2 (2) | N1—C2—H2 | 117.5 |
C15—N5—C9 | 110.9 (2) | C1—C2—H2 | 117.5 |
C15—N5—C8 | 109.0 (2) | N1—C3—C4 | 124.4 (3) |
C9—N5—C8 | 109.5 (2) | N1—C3—H3 | 117.8 |
N4—N3—N2 | 106.8 (2) | C4—C3—H3 | 117.8 |
N3—N4—C7 | 109.6 (2) | O2—C11—C12 | 110.5 (3) |
C5—C4—C3 | 117.9 (3) | O2—C11—C13 | 101.8 (3) |
C5—C4—H4 | 121 | C12—C11—C13 | 110.8 (3) |
C3—C4—H4 | 121 | O2—C11—C14 | 109.4 (3) |
O4—C17—C19 | 101.9 (3) | C12—C11—C14 | 112.6 (3) |
O4—C17—C20 | 109.6 (3) | C13—C11—C14 | 111.1 (4) |
C19—C17—C20 | 111.3 (3) | C11—C14—H14A | 109.5 |
O4—C17—C18 | 109.4 (3) | C11—C14—H14B | 109.5 |
C19—C17—C18 | 111.2 (3) | H14A—C14—H14B | 109.5 |
C20—C17—C18 | 112.8 (3) | C11—C14—H14C | 109.5 |
N2—C6—C7 | 105.3 (3) | H14A—C14—H14C | 109.5 |
N2—C6—H6 | 127.4 | H14B—C14—H14C | 109.5 |
C7—C6—H6 | 127.4 | C17—C19—H19A | 109.5 |
N4—C7—C6 | 108.2 (3) | C17—C19—H19B | 109.5 |
N4—C7—C8 | 121.8 (3) | H19A—C19—H19B | 109.5 |
C6—C7—C8 | 130.0 (3) | C17—C19—H19C | 109.5 |
O1—C10—O2 | 126.3 (3) | H19A—C19—H19C | 109.5 |
O1—C10—C9 | 124.6 (3) | H19B—C19—H19C | 109.5 |
O2—C10—C9 | 109.1 (2) | C2—C1—C5 | 117.5 (3) |
N5—C9—C10 | 112.8 (2) | C2—C1—H1 | 121.2 |
N5—C9—H9A | 109 | C5—C1—H1 | 121.2 |
C10—C9—H9A | 109 | C11—C12—H12A | 109.5 |
N5—C9—H9B | 109 | C11—C12—H12B | 109.5 |
C10—C9—H9B | 109 | H12A—C12—H12B | 109.5 |
H9A—C9—H9B | 107.8 | C11—C12—H12C | 109.5 |
C6—N2—N3 | 110.1 (3) | H12A—C12—H12C | 109.5 |
C6—N2—C5 | 129.3 (2) | H12B—C12—H12C | 109.5 |
N3—N2—C5 | 120.5 (2) | C17—C18—H18A | 109.5 |
C4—C5—C1 | 119.4 (3) | C17—C18—H18B | 109.5 |
C4—C5—N2 | 120.3 (3) | H18A—C18—H18B | 109.5 |
C1—C5—N2 | 120.3 (3) | C17—C18—H18C | 109.5 |
N5—C8—C7 | 112.6 (2) | H18A—C18—H18C | 109.5 |
N5—C8—H8A | 109.1 | H18B—C18—H18C | 109.5 |
C7—C8—H8A | 109.1 | C17—C20—H20A | 109.5 |
N5—C8—H8B | 109.1 | C17—C20—H20B | 109.5 |
C7—C8—H8B | 109.1 | H20A—C20—H20B | 109.5 |
H8A—C8—H8B | 107.8 | C17—C20—H20C | 109.5 |
O3—C16—O4 | 125.4 (3) | H20A—C20—H20C | 109.5 |
O3—C16—C15 | 125.8 (3) | H20B—C20—H20C | 109.5 |
O4—C16—C15 | 108.8 (2) | C11—C13—H13A | 109.5 |
N5—C15—C16 | 113.2 (2) | C11—C13—H13B | 109.5 |
N5—C15—H15A | 108.9 | H13A—C13—H13B | 109.5 |
C16—C15—H15A | 108.9 | C11—C13—H13C | 109.5 |
N5—C15—H15B | 108.9 | H13A—C13—H13C | 109.5 |
C16—C15—H15B | 108.9 | H13B—C13—H13C | 109.5 |
Cg1 is the centroid of the N1/C1–C5 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O1i | 0.95 | 2.54 | 3.443 (4) | 160 |
C6—H6···N1ii | 0.95 | 2.31 | 3.252 (4) | 173 |
C9—H9B···N3iii | 0.99 | 2.50 | 3.449 (4) | 160 |
C18—H18A···Cg1iv | 0.98 | 2.91 | 3.864 (4) | 166 |
Symmetry codes: (i) x, y+1, z; (ii) −x+2, y−1/2, −z+2; (iii) −x+1, y−1/2, −z+1; (iv) x, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | C20H29N5O4 |
Mr | 403.48 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 193 |
a, b, c (Å) | 9.1568 (8), 11.4452 (10), 11.4928 (11) |
β (°) | 110.840 (4) |
V (Å3) | 1125.66 (18) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.2 × 0.1 × 0.04 |
Data collection | |
Diffractometer | Bruker Kappa APEXII Quazar diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2008) |
Tmin, Tmax | 0.989, 0.997 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11329, 3530, 1947 |
Rint | 0.077 |
(sin θ/λ)max (Å−1) | 0.716 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.059, 0.122, 1.00 |
No. of reflections | 3530 |
No. of parameters | 268 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.18, −0.18 |
Computer programs: APEX2 (Bruker, 2008), APEX2 and SAINT (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), WinGX publication routines (Farrugia, 2012) and publCIF (Westrip, 2010).
Cg1 is the centroid of the N1/C1–C5 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O1i | 0.95 | 2.54 | 3.443 (4) | 160 |
C6—H6···N1ii | 0.95 | 2.31 | 3.252 (4) | 173 |
C9—H9B···N3iii | 0.99 | 2.50 | 3.449 (4) | 160 |
C18—H18A···Cg1iv | 0.98 | 2.91 | 3.864 (4) | 166 |
Symmetry codes: (i) x, y+1, z; (ii) −x+2, y−1/2, −z+2; (iii) −x+1, y−1/2, −z+1; (iv) x, y−1, z. |
Acknowledgements
We gratefully acknowledge the French Ministère de l'Education Nationale, de la Recherche et de la Technologie for financial support.
References
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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.
If 1,2,3-Triazoles are well known for their biological properties, particular attention has been recently devoted to the development of 2-pyridyl-1,2,3-triazole derivatives (or pyta) as alternative ligands to 2,2'-bipyridines. This interest is explained by the easy preparation of such ligands using a click chemistry strategy (Obata et al., 2008; Schweinfurth et al., 2008), and the use of pyta derivatives as efficient chelator systems for Tc(CO)3+ or Re(CO)3+ organometallic cores (Boulay et al., 2010; Seridi et al., 2011). Recently, structural pyta isomers like 4-pyridyl-1,2,3-triazole have been described as building blocks in the synthesis of chelating agents for biomedical applications (Bonnet et al., 2012; Pellegatti et al., 2008). In this paper, we report on the first X-ray structure analysis of a 4-pyridyl-1,2,3-triazole derivative.
The title molecule, Fig. 1, can be considered as a ditopic ligand with two distinct transition metal complexing sites, the iminodiacetate (IDA) pincer and the 4-pyridine moiety. Bond lengths and angles are within normal ranges, and comparable with values found for structural isomers, such as 2-pyridyl-1,2,3-triazole derivatives (Obata et al. 2008; Schweinfurth et al., 2008; Seridi et al., 2011; Boulay et al., 2010). As is often observed in these ligand systems, the pyridyl and triazole units are coplanar (Crowley et al., 2010; Kilpin et al., 2011). Unarguably, the structure exhibits a practically planar geometry with slight deviation of the pyridyl moiety, which makes a dihedral angle of 10.41 (16)° with the mean plane of the triazole ring. As expected, the N3–N4 distance of the 1,2,3-triazole at 1.308 (4) Å is shorter than the N4–C7 and N2–N3 bonds, 1.358 (4) and 1.356 (3) Å respectively, confirming the azo character of the triazolyl entity.
In the crystal, molecules are linked by C–H···O and C–H···N hydrogen bonds (Table 1 and Fig. 2). It is noteworthy that a C–H···π interaction between of the hydrogen H18A of one methyl group and the π cloud of the pyridine ring was also observed, this interaction participates in the cohesion of the crystal.