A Comparative X-ray Diffraction Study and Ab Initio Calculation on RU60358, a New Pyrethroid
Abstract
:1. Introduction
2. Results and discussion
2.1. Description of the crystal structure
Atom 1 | Atom 2 | Distance (Å) | |
---|---|---|---|
X-ray | B3LYP/6-31G** | ||
C1 | C2 | 1.395 (10) | 1.433 |
C1 | C10 | 1.395 (11) | 1.381 |
C1 | C11 | 1.474 (12) | 1.472 |
C2 | C3 | 1.410 (09) | 1.416 |
C2 | C7 | 1.395 (11) | 1.433 |
C3 | C4 | 1.395 (13) | 1.388 |
C4 | C5 | 1.395 (10) | 1.428 |
C4 | C15 | 1.429 (10) | 1.428 |
C5 | C6 | 1.395 (10) | 1.371 |
C6 | C7 | 1.395 (09) | 1.422 |
C7 | C8 | 1.395 (11) | 1.418 |
C8 | C9 | 1.395 (11) | 1.375 |
C9 | C10 | 1.395 (09) | 1.412 |
C11 | N | 1.278 (13) | 1.290 |
C11 | C12 | 1.514 (15) | 1.497 |
C12 | O1 | 1.292 (10) | 1.351 |
C12 | O2 | 1.152 (10) | 1.210 |
C13 | O1 | 1.439 (12) | 1.436 |
N | O3 | 1.376 (09) | 1.374 |
C14 | O3 | 1.427 (11) | 1.467 |
C15 | C16 | 1.163 (13) | 1.213 |
C16 | C17 | 1.467 (12) | 1.459 |
C17 | C18 | 1.439 (12) | 1.548 |
C17 | C19 | 1.469 (11) | 1.541 |
C17 | C20 | 1.531 (13) | 1.549 |
Atom 1 | Atom 2 | Atom 3 | Angle (°) | |
---|---|---|---|---|
X-ray | B3LYP/6-31G** | |||
C2 | C1 | C10 | 120.0 (8) | 119.8 |
C2 | C1 | C11 | 123.5 (5) | 121.1 |
C10 | C1 | C11 | 116.2 (8) | 119.1 |
C1 | C2 | C3 | 120.2 (6) | 122.6 |
C1 | C2 | C7 | 120.0 (7) | 118.5 |
C3 | C2 | C7 | 119.8 (7) | 118.7 |
C2 | C3 | C4 | 120.0 (5) | 121.5 |
C3 | C4 | C5 | 120.0 (5) | 119.2 |
C3 | C4 | C15 | 122.1 (6) | 120.9 |
C5 | C4 | C15 | 117.9 (8) | 119.9 |
C4 | C5 | C6 | 120.0 (8) | 120.4 |
C5 | C6 | C7 | 120.4 (7) | 121.2 |
C2 | C7 | C6 | 119.8 (9) | 118.8 |
C2 | C7 | C8 | 120.0 (5) | 119.6 |
C6 | C7 | C8 | 120.2 (6) | 121.6 |
C7 | C8 | C9 | 120.0 (5) | 120.6 |
C8 | C9 | C10 | 120.0 (7) | 120.1 |
C16 | C17 | C19 | 111.5 (9) | 109.4 |
C16 | C17 | C20 | 107.7 (9) | 109.3 |
C18 | C17 | C19 | 110.5 (8) | 109.7 |
C18 | C17 | C20 | 107.3 (5) | 109.6 |
C19 | C17 | C20 | 107.2 (4) | 109.5 |
C1 | C10 | C9 | 120.0 (6) | 121.2 |
C1 | C11 | N | 126.9 (8) | 125.7 |
C1 | C11 | C12 | 121.6 (5) | 121.4 |
N | C11 | C12 | 111.5 (4) | 112.9 |
C12 | O1 | C13 | 117.0 (9) | 115.0 |
N | O3 | C14 | 108.5 (5) | 109.2 |
C11 | N | O3 | 110.8 (7) | 112.6 |
C11 | C12 | O1 | 110.6 (7) | 110.5 |
C11 | C12 | O2 | 126.0 (9) | 125.7 |
O1 | C12 | O2 | 123.4 (5) | 123.8 |
C4 | C15 | C16 | 174.8 (9) | 180.5 |
C15 | C16 | C17 | 179.3 (6) | 180.1 |
C16 | C17 | C18 | 112.6 (7) | 109.6 |
2.2. Optimized geometry
2.3. Vibrational wavenumbers
ν (cm-1)* | Assignments | ν (cm-1)* | Assignments |
---|---|---|---|
10.6 | τC17CT, τC1C11, δC4,C15,C16 | 702.1 | νCACA, νC1C11, δCACACA, δCT,O,N |
13.8 | τC1C11 | 723.4 | νsCT(CH3)3 (tBu) |
24.7 | τC11C12 | 738.1 | γCAH, γCACA, τCACA |
30.9 | δCA,C4,C15 | 749.6 | γC12=O2, γC11N, δC12=O2 |
35.4 | τC4C15, τC1C2, δC15,C16,C17 | 752.2 | γC12=O2, δC12=O2, δC12O1CT, νC12O1 |
61.9 | τC1C11, τC1CA, τC4C15 | 778.7 | γCAH, γC1C11, γCACA |
67.2 | τNO, γC11N | 819.0 | γCAH#, γCACA |
98.1 | τC14O, τNO | 825.3 | δCACACA(ring 1), γCAH##, νCACA |
102.4 | δC15,C16,C17, τC6C7 | 832.4 | δCACACA, νC16C17, νC17CT |
108.4 | δC12,C11,N, τO1C13, δC1,C11,C12 | 873.0 | γC3H, τ CACA |
112.8 | τO1C13 | 887.1 | γCAH(ring 1) |
129.4 | δC4,C15,C16, τO1C12 | 897.4 | νO3N, νO3CT, νO1C12, νO1CT,νC17CT |
158.9 | τC2C7, τC2C3, τC7C8 | 897.8 | νC17CT, ρ(tBu) |
163.6 | τO1C12, τO3C14, τON | 899.7 | νC17CT |
173.9 | τON, δC4,C15,C16, τO3C14 | 926.0 | νC17CT, νNO3, νC4CA, δCACACA |
185.2 | τC6C7, τC1C2, τC4C15 | 933.0 | γCAH( all rings) |
218.6 | νC4C15, νC16C17, δC3,C4,C5 | 933.8 | ρ(tBu) |
221.9 | τC17CH3 (tBu) | 942.9 | γCAH(all rings) |
246.0 | δC12,O1,C13, δO1,C12,C11, τC4C15 | 971.6 | νO3N, νCACA, δCACACA, δCAH, δC11,N,O3 |
269.5 | τC17CH3(tBu) | 996.9 | νCTO1, νO3CT |
276.5 | τC17CH3(tBu) | 1013.9 | ρ(tBu) |
279.4 | δC12,O1,C13, νC1C11, δC1,C11,C12 | 1014.1 | ρ(tBu) |
297.8 | τC11N, δC12,O1,C13, τO1C12 | 1045.1 | νCACA, νO3CT, νO3N |
314.3 | δC14,O,N, νC1C11, τC11N, δCACACA | 1060.2 | νO3CT, νCACA, νO3N |
332.4 | δCT,C17,CT(tBu) | 1095.2 | νC12O1, νCTO1, δC11,N,O3, νO3CT |
336.7 | δCT,C17,CT(tBu) | 1130.9 | ρC14H3 |
357.3 | δCT,C17,CT(tBu), δC1,C2,C3, δC6,C7,C8 | 1133.8 | ρC13H3 |
367.4 | νC11C12, δC11,N,O, δC12,C11,N | 1134.5 | δCAH, νCACA(ring 2) |
373.6 | δC11,C12,O2, δC12,O1,C13 | 1148.6 | δCAH, νCACA(ring 1) |
387.9 | τC4C15, τC4CA, γC6C7 | 1163.1 | ρC13H3 |
424.2 | δCT,C17,CT(tBu) | 1172.1 | ρC14H3 |
425.2 | τCACA, γCAH | 1181.6 | ρ(tBu) |
474.6 | δC4,C15,C16, δC16,C17,CT, γC-N | 1183.4 | ρ(tBu) |
501.5 | δC16,C17,CT, δCA,C4,C15, δCACACA | 1184.8 | νO1C12, ρC14H3, νC4C15, ρC13H3, ρ(tBu) |
512.7 | δC16,C17,CT, δC15,C16,C17, τCACA | 1196.4 | νCACA, δCAH |
528.1 | γCACA, τCACA, γC1C11, δC14,O3,N | 1215.3 | δCAH, νO1C12 |
545.3 | τC4C15, δC15,C16,C17, δC16,C17,CT,τCACA, γC4C15 | 1241.2 | δCAH(ring 2) |
550.4 | δC4,C15,C16, δC16,C17,CT | 1266.0 | νC11C12, νC1C11, νO1C12, δCAH(ring 1) |
583.3 | τC11N, νC16C17, δCA,C1,C11, γC11N, γC12=O2 | 1270.9 | νC16C17, νC4C15, δCAH(ring 1) |
590.2 | γC11N, τC11C12, γC12=O2, g C4C15 | 1303.8 | νCACA, δCAH |
616.1 | δCACACA, δCT,O,N, νC17CT | 1352.3 | νCACA |
652.7 | γC4C15, γC1C11, τCACA, γCAH | 1353.7 | dsCH3(tBu) |
1354.4 | dsCH3(tBu) | 2243.4 | νC15C16 |
1364.7 | νCACA, δCAH | 2925.2 | νsCH3 (tBu) |
1384.7 | δsCH3(tBu) | 2925.8 | νsCH3(tBu) |
1416.2 | δsC14H3 | 2931.6 | νsC14H3 |
1421.4 | δsC13H3 | 2931.8 | νsC14H3, nsCH3(tBu) |
1423.3 | δsC13H3 | 2947.1 | νsC13H3 |
1433.6 | δaCH3(tBu) | 2996.8 | νaCH3(tBu) |
1434.7 | δaC14H3 | 2997.4 | νaCH3(tBu) |
1436.2 | νCACA, δCAH | 3002.5 | νaCH3 (tBu) |
1437.8 | δaC13H3 | 3006.2 | νaC14H3 |
1443.9 | δaCH3 (tBu) | 3006.8 | νaCH3(tBu) |
1444.4 | δaCH3(tBu) | 3010.2 | νaCH3(tBu) |
1451.5 | δaC13H3 | 3010.9 | νaCH3(tBu) |
1456.3 | δaCH3(tBu) | 3020.7 | νaC13H3 |
1456.8 | δaCH3(tBu) | 3041.2 | νaC14H3 |
1457.4 | δaC14H3 | 3054.8 | νaC13H3 |
1474.6 | δaCH3(tBu) | 3056.3 | νCAH(all rings) |
1484.6 | νCACA, δCAH | 3059.4 | νCAH(all rings) |
1557.7 | νCACA, δCAH | 3068.8 | νCAH(ring 1) |
1582.1 | νC11N, νCACA | 3083.6 | νCAH(ring 1) |
1593.9 | νC11N, νCACA | 3087.9 | νCAH(ring 2) |
1609.1 | νCACA | 3096.9 | νCAH(ring 2) |
1749.0 | νC12=O2 |
3. Experimental Section
3.1 X-ray structure determination
3.2. Computational methods
Crystal data | |
---|---|
Formula | C20H21NO3 |
Molecular weight | 323.34 |
Crystal system | Orthorhombic |
Space group | P212121 |
Unit cell determination | Least-squares fit from 25 reflections (2° < q < 30°) |
a (Å) | 7.7575 |
b (Å) | 11.3182 |
c (Å) | 21.3529 |
V (Å3) | 1874.80 |
Z | 4 |
dcalc(g. cm-3) | 1.16 |
mu (mm-1) | 0.077 |
Crystal colour | Colourless |
Crystal size | 0.32 ´ 0.27 ´ 0.10 ( mm) |
Experimental data | |
Technique | Four circles diffractometer, CAD4 Enraf Nonius kappa geometry |
Graphite oriented monochromator : Moka | |
λ = 0.71070 Å, ω/2q scan | |
Scanning range for θ | 2.04 ¾ 29.96 |
Number of reflections measured | 3082 |
Number of reflections observed | 1583 (I ≥ 3σ(I)criterion) |
Limiting indices | h 0 ® 10 |
k 0 ® 15 | |
l 0 ® 30 | |
T (K) | 293 |
Refinement data | |
Refinement method | Full-matrix least-squares on F |
Final R indices | R=0.068, wR=0.068 |
S | 1.249 |
H atoms | constrained refinement |
Parameters | 224 |
(Δ/σ)max | 0.380 |
(Δρ)min | -0.271 eÅ-3 |
(Δρ)max | 0.380 eÅ-3 |
Extinction | No extinction correction applied |
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Hamzaoui, F.; Chouaih, A.; Lagant, P.; Belarbi, O.; Vergoten, G. A Comparative X-ray Diffraction Study and Ab Initio Calculation on RU60358, a New Pyrethroid. Int. J. Mol. Sci. 2006, 7, 255-265. https://doi.org/10.3390/i7080255
Hamzaoui F, Chouaih A, Lagant P, Belarbi O, Vergoten G. A Comparative X-ray Diffraction Study and Ab Initio Calculation on RU60358, a New Pyrethroid. International Journal of Molecular Sciences. 2006; 7(8):255-265. https://doi.org/10.3390/i7080255
Chicago/Turabian StyleHamzaoui, Fodil, Abdelkader Chouaih, Philippe Lagant, Ouassila Belarbi, and Gérard Vergoten. 2006. "A Comparative X-ray Diffraction Study and Ab Initio Calculation on RU60358, a New Pyrethroid" International Journal of Molecular Sciences 7, no. 8: 255-265. https://doi.org/10.3390/i7080255