Crystal Structures, Vibrational Spectra, and Fungicidal Activity of 1,5-Diaryl-3-oxypyrazoles
Abstract
:1. Introduction
2. Results and Discussion
2.1. Structural Description
I | II | III | IV | |
---|---|---|---|---|
CCDC | 906894 | 819778 | 918082 | 925316 |
Empirical formula | C24H20N2O4 | C21H18ClN3O3S2 | C20H16ClN3O2S2 | C32H35FN2O10 |
Formula weight | 400.42 | 459.95 | 429.93 | 626.62 |
Temperature | 293(2) | 293(2) | 293(2) | 293(2) |
Wavelength (Å) | 0.71073 | 0.71073 | 0.71073 | 0.71073 |
Crystal system | Triclinic | Triclinic | Orthorhombic | Monoclinic |
Space group | P-1 | P-1 | Pbca | P21 |
a (Å) | 9.3040(19) | 6.0180(12) | 13.698(3) | 11.838(2) |
b (Å) | 10.507(2) | 8.2370(16) | 7.6260(15) | 9.4500(19) |
c (Å) | 12.075(2) | 21.600(4) | 38.908(8) | 14.514(3) |
α (°) | 68.70(3) | 87.08(3) | 90.00 | 90.00 |
β (°) | 81.40(3) | 87.46(3) | 90.00 | 100.41(3) |
γ (°) | 67.99(3) | 82.30(3) | 90.00 | 90.00 |
Volume (Å3) | 1,019.5(4) | 1,058.9(4) | 4,064.4(14) | 1,596.9(6) |
Z | 2 | 2 | 8 | 2 |
Calculated density (Mg/m3) | 1.304 | 1.443 | 1.405 | 1.303 |
Absorption coefficient (mm−1) | 0.090 | 0.406 | 0.414 | 0.101 |
F(000) | 420 | 476 | 1,776 | 660 |
Crystal size (mm) | 0.10 × 0.20 × 0.30 | 0.05 × 0.05 × 0.10 | 0.10 × 0.20 × 0.30 | 0.10 × 0.20 × 0.30 |
θ range for data collection(°) | 1.81–25.36 | 1.89–25.28 | 1.05–25.28 | 1.43–25.25 |
Index ranges | 0 ≤ h ≤ 11 −11 ≤ k ≤ 12 −14 ≤ l ≤ 14 | 0 ≤ h ≤ 7 −9 ≤ k ≤ 9 −25 ≤ l ≤ 25 | 0 ≤ h ≤ 16 0 ≤ k ≤ 9 0 ≤ l ≤ 46 | −14 ≤ h ≤ 13 0 ≤ k ≤ 11 0 ≤ l ≤ 17 |
Reflections collected | 4002 | 4239 | 3688 | 3091 |
Independent reflections [R(int)] | 3750 [R(int) = 0.045] | 3843 [R(int) = 0.061] | 3688 [R(int) = 0.034] | 3091 [R(int) = 0.052] |
Max. and min. transmission | 0.9911 and 0.9736 | 0.9800 and 0.9605 | 0.9597 and 0.8857 | 0.9900 and 0.9704 |
Refinement method on F2 | Full-matrix least-squares | Full-matrix least-squares | Full-matrix least-squares | Full-matrix least-squares |
Data/restraints/parameters | 3750/0/271 | 3843/0/272 | 3688/0/253 | 3091/7/388 |
Goodness-of-fit on F2 | 1.005 | 1.002 | 1.032 | 1.004 |
Final R indices [I > 2σ(I)]; R1, wR2 | R1 = 0.0688 wR2 = 0.1508 | R1 = 0.0854 wR2 = 0.1592 | R1 = 0.0740 wR2 = 0.1616 | R1 = 0.0656 wR2 = 0.1567 |
R1, wR2 (all data) | R1 = 0.1452 wR2 = 0.1835 | R1 = 0.1766 wR2 = 0.1897 | R1 = 0.1359 wR2 = 0.1922 | R1 = 0.1000 wR2 = 0.1798 |
Largest diff. peak and hole (e·Å−3) | 0.149 and −0.169 | 0.451 and −0.266 | 0.325 and −0.358 | 0.226 and −0.577 |
Comp. | Bond lengths (Å) | X-ray | Bond angles/Torsion angles (°) | X-ray |
---|---|---|---|---|
I | C11-O3 | 1.391(4) | C9-C10-C11 | 104.2(3) |
N1-N2 | 1.374(3) | N2-N1-C11-O3 | 173.5(3) | |
C5-C9 | 1.472(4) | N1-N2-C9-C5 | −172.8(3) | |
O3-C18 | 1.360(4) | C1-O1-C8-C7 | 5.0(5) | |
C2-O2-C3-C4 | −2.7(5) | |||
II | C6-O2 | 1.326(8) | C6-C7-C8 | 106.3(5) |
N1-C4 | 1.417(7) | N3-N2-C6-O2 | −179.7(6) | |
C7-Cl | 1.732(6) | N2-N3-C8-C9 | −176.1(6) | |
N2-N3 | 1.357(6) | C15-O3-C12-C11 | 1.1(11) | |
C8-C9 | 1.479(8) | C4-N1-C3-S2 | −1.0(10) | |
O2-C5 | 1.414(7) | |||
III | C15-O1 | 1.351(5) | C13-C14-C15 | 104.9(4) |
N3-C17 | 1.412(6) | N1-N2-C15-O1 | 178.1(4) | |
C11-Cl | 1.730(7) | N2-N1-C13-C7 | 177.8(4) | |
N1-N2 | 1.365(5) | C17-N3-C18-S1 | 9.4(7) | |
C7-C13 | 1.477(7) | |||
O1-C16 | 1.424(5) | |||
IV | C10-O1 | 1.392(6) | C10-C11-C12 | 104.4(5) |
C16-F | 1.380(7) | N2-N1-C10-O1 | 177.4(6) | |
N1-N2 | 1.388(5) | N1-N2-C12-C13 | −176.3(6) | |
C12-C13 | 1.499(7) | O1-C19-O2-C20 | −173.8(4) | |
O1-C19 | 1.404(6) | O2-C19-C23-O10 | −174.2(4) | |
C21-C20-C26-O4 | −61.0(6) | |||
C19-O1-C10-C11 | 160.7(6) |
Comp. | D-H…A | D-H | H···A | D···A | D-H···A |
---|---|---|---|---|---|
(a) Intermolecular and intramolecular hydrogen bond | |||||
I | C10-H10A···O1 a | 0.9300 | 2.5100 | 3.442(5) | 175.00 |
II | C5-H5A···S2 | 0.9700 | 2.5900 | 3.033(8) | 108.00 |
III | C16-H16B···S1 | 0.9700 | 2.5800 | 3.094(5) | 113.00 |
IV | C21-H21A···O4 | 0.9800 | 2.5300 | 2.897(8) | 102.00 |
C21-H21A···O5 | 0.9800 | 2.2700 | 2.645(8) | 102.00 | |
C21-H21A···O7 | 0.9800 | 2.4000 | 2.975(8) | 117.00 | |
C23-H23A···O7 | 0.9800 | 2.4000 | 2.958(7) | 116.00 | |
C23-H23A···O9 | 0.9800 | 2.2600 | 2.659(9) | 103.00 | |
C17-H17A···O3 b | 0.9300 | 2.5200 | 3.440(10) | 170.00 | |
C20-H20A···O3 c | 0.9800 | 2.4100 | 3.363(9) | 163.00 | |
C24-H24B···O9 d | 0.9600 | 2.5100 | 3.375(11) | 150.00 | |
C29-H29C···O7 e | 0.9600 | 2.4200 | 3.320(10) | 155.00 | |
Comp. | C-H···Cg | C-H | H···Cg | C···Cg | C-H···Cg |
(b) C-H…π interactions | |||||
I | C17-H17A···Cg1 f | 0.9300 | 3.2873 | 3.900(4) | 125.39 |
C2-H2B···Cg2 f | 0.9600 | 3.1975 | 4.050(5) | 148.87 | |
C4-H4A···Cg2 f | 0.9300 | 3.3208 | 4.113(4) | 144.40 | |
C24-H24A···Cg2 g | 0.9300 | 3.3983 | 4.143(5) | 138.64 | |
C2-H2C···Cg3 a | 0.9600 | 2.9016 | 3.706(5) | 142.02 | |
C22-H22A···Cg3 h | 0.9300 | 3.1317 | 3.866(6) | 137.15 | |
II | C2-H2C···Cg4 i | 0.9700 | 3.0259 | 3.812(8) | 139.03 |
C1-H1A···Cg2 i | 0.9700 | 3.2864 | 3.927(8) | 125.25 | |
C14-H14A···Cg2 j | 0.9300 | 3.0647 | 3.906(7) | 151.31 | |
C17-H17A···Cg1 k | 0.9300 | 3.2738 | 3.550(7) | 99.63 | |
C18-H18A···Cg1 k | 0.9300 | 3.0448 | 3.418(9) | 105.87 | |
III | C19-H19B···Cg2 l | 0.9700 | 3.3425 | 4.032(6) | 129.74 |
C14-H14A···Cg1 m | 0.9300 | 2.8623 | 3.725(6) | 154.68 | |
C19-H19C···Cg1 n | 0.9700 | 3.3978 | 3.940(6) | 117.46 | |
IV | C14-H14A···Cg1 o | 0.9300 | 3.2004 | 3.780(9) | 122.32 |
C18-H18A···Cg1 p | 0.9300 | 3.3184 | 3.865(7) | 119.69 | |
C27-H27A···Cg2 c | 0.9600 | 3.0282 | 3.571(9) | 117.24 | |
C27-H27C···Cg2 c | 0.9600 | 3.2317 | 3.571(9) | 102.94 | |
C27-H27B···Cg3 q | 0.9600 | 2.7786 | 3.647(9) | 150.82 | |
C31-H31C···Cg3 o | 0.9600 | 3.3687 | 4.192(9) | 144.97 |
2.2. Experimental and Theoretical FTIR Results
Vibration | I | II | III | IV | ||||
---|---|---|---|---|---|---|---|---|
Exp. | B3LYP/6-31G * | Exp. | B3LYP/6-31G * | Exp. | B3LYP/6-31G * | Exp. | B3LYP/6-31G * | |
ν =CH | 3069 | 3090 | 3066 | 3076 | 3058 | 3073 | 3069 | 3068 |
νC-H | 2958 | 2953 | 2932 | 2935 | 2927 | 2936 | 2963 | 2958 |
2838 | 2842 | 2842 | 2847 | 2848 | 2845 | 2898 | 2896 | |
νC=O | 1739 | 1737 | 1714 | 1718 | 1708 | 1711 | 1755 | 1752 |
νC=C | 1596 | 1593 | 1616 | 1624 | 1627 | 1623 | 1610 | 1603 |
1549 | 1548 | 1521 | 1521 | 1595 | 1604 | 1556 | 1555 | |
1507 | 1509 | 1456 | 1458 | 1551 | 1552 | 1515 | 1514 | |
1444 | 1440 | 1502 | 1508 | 1466 | 1463 | |||
1466 | 1459 | |||||||
νC-O | 1259 | 1264 | 1280 | 1267 | 1280 | 1266 | 1230 | 1234 |
1167 | 1168 | 1255 | 1267 | 1225 | 1240 | 1161 | 1163 | |
1147 | 1130 | 1226 | 1222 | 1187 | 1183 | 1080 | 1081 | |
1088 | 1095 | 1179 | 1185 | 1054 | 1053 | 1055 | 1054 | |
1066 | 1071 | 1134 | 1147 | |||||
1027 | 1020 | 1027 | 1024 | |||||
γ=C-H | 864 | 869 | 837 | 828 | 881 | 888 | 845 | 846 |
811 | 807 | 773 | 782 | 790 | 787 | 779 | 770 | |
768 | 764 | 698 | 695 | 767 | 774 | |||
703 | 703 | 696 | 701 | |||||
672 | 676 | |||||||
νC-Cl | 734 | 736 | 734 | 737 | ||||
νC-F | 1330 | 1332 |
2.3. Fungicidal Activity
Comp. | X | Y | Inhibition rate (%) | |
---|---|---|---|---|
S. sclerotiorum | G. zeae | |||
I | 3,4-(OCH3)2 | H | 0 | 4 |
II | p-OMe | H | 21 | 32 |
III | m-Cl | H | 14 | 29 |
IV | p-F | p-Me2CH | 29 | 11 |
3. Experimental
3.1. General Information
3.2. Synthesis and Characterization
3.2.1. Preparation of Compound I
3.2.2. Preparation of Compound II
3.2.3. Preparation of Compound III
3.2.4. Preparation of Compound IV
3.3. X-ray Crystallography
3.4. FTIR Spectra
3.5. Fungicidal Activity Assays
4. Conclusions
Acknowledgments
Conflicts of Interest
References
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Li, Y.; Liu, Y.; Xiong, Y.; Xiong, X. Crystal Structures, Vibrational Spectra, and Fungicidal Activity of 1,5-Diaryl-3-oxypyrazoles. Molecules 2014, 19, 1302-1316. https://doi.org/10.3390/molecules19011302
Li Y, Liu Y, Xiong Y, Xiong X. Crystal Structures, Vibrational Spectra, and Fungicidal Activity of 1,5-Diaryl-3-oxypyrazoles. Molecules. 2014; 19(1):1302-1316. https://doi.org/10.3390/molecules19011302
Chicago/Turabian StyleLi, Yi, Yuanyuan Liu, Yihuang Xiong, and Xiaohui Xiong. 2014. "Crystal Structures, Vibrational Spectra, and Fungicidal Activity of 1,5-Diaryl-3-oxypyrazoles" Molecules 19, no. 1: 1302-1316. https://doi.org/10.3390/molecules19011302