Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807035532/cf2126sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807035532/cf2126Isup2.hkl |
CCDC reference: 657849
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean (C-C) = 0.005 Å
- R factor = 0.059
- wR factor = 0.150
- Data-to-parameter ratio = 15.9
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT220_ALERT_2_B Large Non-Solvent C Ueq(max)/Ueq(min) ... 3.53 Ratio
Alert level C RINTA01_ALERT_3_C The value of Rint is greater than 0.10 Rint given 0.108 PLAT020_ALERT_3_C The value of Rint is greater than 0.10 ......... 0.11 PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ? PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.84 Ratio PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for O1 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C16 PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 5
Alert level G PLAT793_ALERT_1_G Check the Absolute Configuration of C15 = ... R
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 8 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 ALERT type 2 Indicator that the structure model may be wrong or deficient 4 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
Many derivatives of pyrazolotriazolopyrimidines have been prepared, and their biological and pharmaceutical activities have been studied by Gatta et al. (1993) and Baraldi et al. (1996, 1998). For bond-length comparisons, see Sasada (1984) and Wang et al. (1998).
A solution of ethyl N-4-cyano-1-((diethoxyphosphoryl)(phenyl)methyl)- 3-(methylthio)-1H-pyrazol-5-ylformimidate (0.87 g, 2 mmol) and 2-(4-chlorophenoxy)acetohydrazide (0.41 g, 2 mmol) in ethylene glycol monomethyl ether (20 ml) was refluxed for 4 h, cooled briefly and evaporated. The residue was purified by chromatography on a silica gel column by eluting with petroleum ether/acetone (6:1, v/v) to give the title compound (yield 61%). Colorless crystals of (I) suitable for X-ray structure analysis were grown from petroleum ether and acetone (6:1, v/v).
H atoms bonded to C were placed at calculated positions, with C—H distances of 0.97 and 0.93Å for H atoms bonded to sp3 and sp2 C atoms, respectively. They were refined using a riding model, with Uiso(H) = 1.2Ueq(C).
Pyrazolotriazolopyrimidine derivatives have been reported to retain high affinity for adenosine receptors (Gatta et al., 1993). A series of pyrazolo[4,3-e]-1,2,4-triazolo[1,5-c]-pyrimidines has been synthesized with the aim of finding potent and selective adenosine A2A antagonists (Baraldi et al., 1996, 1998). Organic phosphorus compounds play an important role in pesticidal science because of their significant biological properties. The title compound, (I), has been prepared as part of our work in the search for novel biologically active heterocyclic compounds. We report here the crystal structure of (I). In the molecule of (I) (Fig. 1), the pyrazolotriazolopyrimidine ring system is almost planar, with a maximum deviation of 0.023 (2) Å, for N2, forming a fully delocalized system. The dihedral angles between the pyrimidine and the triazole and pyrazole rings are 1.31 (1) and 1.1 (1)°, respectively. In the pyrazolotriazolopyrimidine ring system, the the C—N bonds are significantly shorter than a normal single C—N bond (1.47 Å; Sasada, 1984) and close to the value for a C=N bond (1.28 Å; Wang et al., 1998). This indicates significant electron delocalization in the pyrazolotriazolopyrimidine system. The O2—P1—O4, O2—P1—O3 and O2—P1—C15 bond angles are larger than the O4—P1—O3, O4—P1—C15 and O3—P1—C15 bond angles, indicating a distorted tetrahedral configuration for the phosphorus atom.
Intra- and intermolecular C—H···O and C—H···N hydrogen bonds contribute strongly to the stability of the crystal structure (Fig. 2 and Table 1). Strong π—π stacking interactions also occur between C1—C6 and N1—N3/C8/C9, N5/N6/C10/C11/C13, N3/N4/C9—C12 rings of neighboring molecules. Centroid-centroid distances are 3.990 (2), 3.909 (2) and 3.509 (2) Å, dihedral angles are 7.76, 7.35 and 8.26°, and shortest interplanar distances are 3.312, 3.567 and 3.439 Å, respectively.
Many derivatives of pyrazolotriazolopyrimidines have been prepared, and their biological and pharmaceutical activities have been studied by Gatta et al. (1993) and Baraldi et al. (1996, 1998). For bond-length comparisons, see Sasada (1984) and Wang et al. (1998).
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.
C25H26ClN6O4PS | F(000) = 1192 |
Mr = 573.00 | Dx = 1.360 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 13.8732 (12) Å | Cell parameters from 4496 reflections |
b = 13.5760 (11) Å | θ = 2.2–21.0° |
c = 16.2034 (14) Å | µ = 0.31 mm−1 |
β = 113.515 (2)° | T = 294 K |
V = 2798.4 (4) Å3 | Plate, colorless |
Z = 4 | 0.20 × 0.20 × 0.10 mm |
Bruker SMART CCD diffractometer | 5485 independent reflections |
Radiation source: fine-focus sealed tube | 3386 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.108 |
φ and ω scans | θmax = 26.0°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | h = −17→17 |
Tmin = 0.941, Tmax = 0.970 | k = −15→16 |
26250 measured reflections | l = −19→19 |
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) = 0.150 | H-atom parameters constrained |
S = 0.94 | w = 1/[σ2(Fo2) + (0.0775P)2] where P = (Fo2 + 2Fc2)/3 |
5485 reflections | (Δ/σ)max < 0.001 |
346 parameters | Δρmax = 0.51 e Å−3 |
0 restraints | Δρmin = −0.27 e Å−3 |
C25H26ClN6O4PS | V = 2798.4 (4) Å3 |
Mr = 573.00 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.8732 (12) Å | µ = 0.31 mm−1 |
b = 13.5760 (11) Å | T = 294 K |
c = 16.2034 (14) Å | 0.20 × 0.20 × 0.10 mm |
β = 113.515 (2)° |
Bruker SMART CCD diffractometer | 5485 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | 3386 reflections with I > 2σ(I) |
Tmin = 0.941, Tmax = 0.970 | Rint = 0.108 |
26250 measured reflections |
R[F2 > 2σ(F2)] = 0.059 | 0 restraints |
wR(F2) = 0.150 | H-atom parameters constrained |
S = 0.94 | Δρmax = 0.51 e Å−3 |
5485 reflections | Δρmin = −0.27 e Å−3 |
346 parameters |
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 | ||
C1 | −0.1149 (2) | 0.5777 (2) | 0.75100 (19) | 0.0508 (7) | |
C2 | −0.0868 (2) | 0.5265 (2) | 0.6910 (2) | 0.0557 (8) | |
H2 | −0.0980 | 0.4589 | 0.6843 | 0.067* | |
C3 | −0.0417 (2) | 0.57556 (19) | 0.64043 (19) | 0.0508 (7) | |
H3 | −0.0210 | 0.5412 | 0.6006 | 0.061* | |
C4 | −0.0279 (2) | 0.6763 (2) | 0.64991 (18) | 0.0451 (7) | |
C5 | −0.0550 (2) | 0.72648 (19) | 0.71144 (19) | 0.0518 (7) | |
H5 | −0.0433 | 0.7940 | 0.7189 | 0.062* | |
C6 | −0.0990 (2) | 0.6773 (2) | 0.7617 (2) | 0.0522 (7) | |
H6 | −0.1180 | 0.7113 | 0.8028 | 0.063* | |
C7 | 0.0502 (2) | 0.68771 (19) | 0.5432 (2) | 0.0487 (7) | |
H7A | −0.0041 | 0.6472 | 0.5000 | 0.058* | |
H7B | 0.1097 | 0.6460 | 0.5769 | 0.058* | |
C8 | 0.08293 (19) | 0.76692 (19) | 0.49599 (18) | 0.0408 (6) | |
C9 | 0.15006 (18) | 0.83186 (18) | 0.41392 (17) | 0.0383 (6) | |
C10 | 0.19804 (18) | 0.86846 (17) | 0.35807 (17) | 0.0372 (6) | |
C11 | 0.19344 (18) | 0.96985 (18) | 0.34508 (17) | 0.0379 (6) | |
C12 | 0.1020 (2) | 1.00255 (18) | 0.42829 (19) | 0.0456 (7) | |
H12 | 0.0675 | 1.0450 | 0.4526 | 0.055* | |
C13 | 0.2525 (2) | 0.83244 (19) | 0.30701 (18) | 0.0441 (7) | |
C14 | 0.3413 (3) | 0.7131 (3) | 0.2211 (3) | 0.0995 (14) | |
H14A | 0.2925 | 0.7369 | 0.1639 | 0.149* | |
H14B | 0.3643 | 0.6482 | 0.2140 | 0.149* | |
H14C | 0.4008 | 0.7565 | 0.2441 | 0.149* | |
C15 | 0.2671 (2) | 1.08765 (18) | 0.26658 (18) | 0.0421 (6) | |
H15 | 0.2141 | 1.1318 | 0.2722 | 0.051* | |
C16 | 0.3721 (2) | 1.1259 (2) | 0.33355 (19) | 0.0453 (7) | |
C17 | 0.4588 (3) | 1.0674 (2) | 0.3706 (2) | 0.0709 (10) | |
H17 | 0.4548 | 1.0014 | 0.3543 | 0.085* | |
C18 | 0.5531 (3) | 1.1053 (3) | 0.4323 (3) | 0.0866 (12) | |
H18 | 0.6115 | 1.0645 | 0.4573 | 0.104* | |
C19 | 0.5600 (3) | 1.2017 (3) | 0.4563 (2) | 0.0765 (10) | |
H19 | 0.6231 | 1.2273 | 0.4973 | 0.092* | |
C20 | 0.4743 (3) | 1.2605 (3) | 0.4199 (3) | 0.0808 (11) | |
H20 | 0.4788 | 1.3266 | 0.4362 | 0.097* | |
C21 | 0.3804 (2) | 1.2231 (2) | 0.3590 (2) | 0.0699 (10) | |
H21 | 0.3220 | 1.2640 | 0.3350 | 0.084* | |
C22 | 0.3442 (4) | 0.9654 (3) | 0.0871 (3) | 0.0991 (14) | |
H22A | 0.2788 | 0.9305 | 0.0742 | 0.119* | |
H22B | 0.4015 | 0.9218 | 0.1218 | 0.119* | |
C23 | 0.3527 (4) | 0.9898 (3) | 0.0029 (3) | 0.1031 (14) | |
H23A | 0.2944 | 1.0306 | −0.0328 | 0.155* | |
H23B | 0.3520 | 0.9303 | −0.0294 | 0.155* | |
H23C | 0.4172 | 1.0246 | 0.0154 | 0.155* | |
C24 | 0.2595 (3) | 1.2565 (3) | 0.0636 (2) | 0.0849 (11) | |
H24A | 0.1950 | 1.2935 | 0.0339 | 0.102* | |
H24B | 0.2643 | 1.2079 | 0.0214 | 0.102* | |
C25 | 0.3491 (4) | 1.3229 (4) | 0.0895 (3) | 0.1304 (18) | |
H25A | 0.3501 | 1.3646 | 0.1377 | 0.196* | |
H25B | 0.3434 | 1.3628 | 0.0388 | 0.196* | |
H25C | 0.4129 | 1.2853 | 0.1091 | 0.196* | |
Cl1 | −0.17098 (9) | 0.51602 (7) | 0.81553 (7) | 0.0888 (4) | |
N1 | 0.13835 (16) | 0.74467 (15) | 0.44512 (15) | 0.0419 (5) | |
N2 | 0.05817 (17) | 0.86038 (15) | 0.49857 (15) | 0.0461 (6) | |
N3 | 0.10306 (16) | 0.90381 (14) | 0.44590 (14) | 0.0401 (5) | |
N4 | 0.14721 (16) | 1.03871 (15) | 0.37903 (15) | 0.0430 (5) | |
N5 | 0.24196 (17) | 0.99000 (14) | 0.28979 (15) | 0.0423 (5) | |
N6 | 0.28024 (17) | 0.90563 (15) | 0.26614 (16) | 0.0482 (6) | |
O1 | 0.01191 (16) | 0.73385 (14) | 0.60181 (14) | 0.0632 (6) | |
O2 | 0.14870 (16) | 1.04858 (16) | 0.08870 (14) | 0.0684 (6) | |
O3 | 0.25682 (18) | 1.20711 (13) | 0.14157 (14) | 0.0650 (6) | |
O4 | 0.34735 (17) | 1.05220 (16) | 0.13979 (15) | 0.0686 (6) | |
P1 | 0.24715 (6) | 1.09311 (5) | 0.14878 (5) | 0.0484 (2) | |
S1 | 0.27892 (8) | 0.70881 (5) | 0.29756 (6) | 0.0705 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0521 (17) | 0.0527 (19) | 0.0503 (18) | −0.0048 (14) | 0.0232 (15) | 0.0076 (15) |
C2 | 0.072 (2) | 0.0378 (16) | 0.061 (2) | −0.0079 (14) | 0.0303 (18) | 0.0005 (15) |
C3 | 0.0659 (18) | 0.0376 (16) | 0.0561 (19) | −0.0010 (14) | 0.0318 (16) | −0.0004 (14) |
C4 | 0.0496 (16) | 0.0401 (16) | 0.0487 (18) | 0.0053 (13) | 0.0228 (14) | 0.0107 (13) |
C5 | 0.0699 (19) | 0.0324 (15) | 0.059 (2) | 0.0051 (14) | 0.0320 (17) | 0.0057 (14) |
C6 | 0.0608 (18) | 0.0460 (18) | 0.0562 (19) | 0.0099 (14) | 0.0300 (16) | 0.0065 (14) |
C7 | 0.0570 (17) | 0.0395 (16) | 0.0583 (19) | 0.0033 (13) | 0.0324 (16) | 0.0073 (14) |
C8 | 0.0436 (15) | 0.0338 (15) | 0.0470 (17) | 0.0005 (12) | 0.0202 (14) | 0.0035 (12) |
C9 | 0.0370 (14) | 0.0326 (14) | 0.0433 (16) | 0.0013 (11) | 0.0138 (13) | −0.0004 (12) |
C10 | 0.0395 (14) | 0.0273 (14) | 0.0450 (16) | −0.0008 (11) | 0.0173 (13) | −0.0014 (12) |
C11 | 0.0382 (14) | 0.0340 (14) | 0.0405 (16) | −0.0038 (11) | 0.0146 (13) | 0.0010 (12) |
C12 | 0.0528 (16) | 0.0316 (15) | 0.0586 (19) | 0.0044 (12) | 0.0286 (15) | 0.0002 (13) |
C13 | 0.0521 (16) | 0.0343 (15) | 0.0495 (17) | −0.0034 (13) | 0.0241 (14) | −0.0005 (13) |
C14 | 0.145 (4) | 0.067 (2) | 0.135 (4) | 0.019 (2) | 0.108 (3) | 0.003 (2) |
C15 | 0.0487 (15) | 0.0297 (14) | 0.0545 (18) | −0.0009 (12) | 0.0275 (14) | 0.0027 (13) |
C16 | 0.0493 (16) | 0.0399 (16) | 0.0519 (18) | −0.0064 (13) | 0.0258 (15) | 0.0022 (14) |
C17 | 0.065 (2) | 0.0445 (19) | 0.089 (3) | 0.0003 (16) | 0.015 (2) | 0.0056 (18) |
C18 | 0.060 (2) | 0.069 (3) | 0.102 (3) | 0.0019 (19) | 0.003 (2) | 0.010 (2) |
C19 | 0.062 (2) | 0.081 (3) | 0.074 (3) | −0.017 (2) | 0.013 (2) | −0.008 (2) |
C20 | 0.065 (2) | 0.060 (2) | 0.108 (3) | −0.0165 (19) | 0.025 (2) | −0.030 (2) |
C21 | 0.058 (2) | 0.050 (2) | 0.098 (3) | −0.0006 (16) | 0.026 (2) | −0.0136 (19) |
C22 | 0.149 (4) | 0.060 (2) | 0.138 (4) | 0.013 (2) | 0.109 (3) | 0.000 (2) |
C23 | 0.131 (4) | 0.100 (3) | 0.089 (3) | 0.027 (3) | 0.055 (3) | −0.007 (2) |
C24 | 0.128 (3) | 0.061 (2) | 0.073 (3) | −0.011 (2) | 0.048 (2) | 0.0154 (19) |
C25 | 0.153 (4) | 0.118 (4) | 0.149 (5) | −0.041 (3) | 0.090 (4) | 0.015 (3) |
Cl1 | 0.1260 (8) | 0.0782 (7) | 0.0883 (7) | −0.0364 (6) | 0.0703 (7) | −0.0041 (5) |
N1 | 0.0457 (12) | 0.0331 (12) | 0.0509 (14) | 0.0003 (10) | 0.0234 (11) | 0.0048 (10) |
N2 | 0.0529 (13) | 0.0383 (14) | 0.0559 (15) | −0.0023 (11) | 0.0311 (12) | 0.0022 (11) |
N3 | 0.0461 (12) | 0.0306 (12) | 0.0495 (14) | 0.0009 (10) | 0.0252 (11) | 0.0011 (10) |
N4 | 0.0484 (13) | 0.0332 (12) | 0.0528 (15) | 0.0003 (10) | 0.0260 (12) | 0.0005 (11) |
N5 | 0.0503 (13) | 0.0312 (12) | 0.0526 (15) | −0.0011 (10) | 0.0281 (12) | 0.0025 (10) |
N6 | 0.0592 (14) | 0.0358 (13) | 0.0593 (16) | 0.0009 (11) | 0.0338 (13) | −0.0003 (11) |
O1 | 0.0972 (16) | 0.0402 (12) | 0.0766 (15) | −0.0045 (11) | 0.0603 (14) | 0.0021 (10) |
O2 | 0.0690 (14) | 0.0707 (15) | 0.0536 (13) | −0.0144 (12) | 0.0119 (12) | 0.0025 (11) |
O3 | 0.1016 (16) | 0.0395 (12) | 0.0639 (14) | −0.0030 (11) | 0.0434 (13) | 0.0087 (10) |
O4 | 0.0833 (15) | 0.0649 (14) | 0.0787 (16) | 0.0024 (11) | 0.0547 (13) | −0.0039 (12) |
P1 | 0.0607 (5) | 0.0382 (4) | 0.0514 (5) | −0.0034 (4) | 0.0277 (4) | 0.0035 (4) |
S1 | 0.1130 (7) | 0.0354 (4) | 0.0902 (7) | 0.0041 (4) | 0.0692 (6) | −0.0014 (4) |
C1—C6 | 1.370 (4) | C15—N5 | 1.458 (3) |
C1—C2 | 1.372 (4) | C15—C16 | 1.519 (4) |
C1—Cl1 | 1.745 (3) | C15—P1 | 1.818 (3) |
C2—C3 | 1.384 (4) | C15—H15 | 0.980 |
C2—H2 | 0.930 | C16—C17 | 1.364 (4) |
C3—C4 | 1.381 (4) | C16—C21 | 1.373 (4) |
C3—H3 | 0.930 | C17—C18 | 1.389 (4) |
C4—O1 | 1.366 (3) | C17—H17 | 0.930 |
C4—C5 | 1.377 (4) | C18—C19 | 1.358 (5) |
C5—C6 | 1.371 (4) | C18—H18 | 0.930 |
C5—H5 | 0.930 | C19—C20 | 1.356 (5) |
C6—H6 | 0.930 | C19—H19 | 0.930 |
C7—O1 | 1.407 (3) | C20—C21 | 1.380 (4) |
C7—C8 | 1.492 (3) | C20—H20 | 0.930 |
C7—H7A | 0.970 | C21—H21 | 0.930 |
C7—H7B | 0.970 | C22—O4 | 1.446 (4) |
C8—N2 | 1.320 (3) | C22—C23 | 1.453 (5) |
C8—N1 | 1.367 (3) | C22—H22A | 0.970 |
C9—N1 | 1.322 (3) | C22—H22B | 0.970 |
C9—N3 | 1.385 (3) | C23—H23A | 0.960 |
C9—C10 | 1.411 (3) | C23—H23B | 0.960 |
C10—C11 | 1.390 (3) | C23—H23C | 0.960 |
C10—C13 | 1.412 (3) | C24—O3 | 1.444 (4) |
C11—N5 | 1.346 (3) | C24—C25 | 1.456 (5) |
C11—N4 | 1.367 (3) | C24—H24A | 0.970 |
C12—N4 | 1.293 (3) | C24—H24B | 0.970 |
C12—N3 | 1.369 (3) | C25—H25A | 0.960 |
C12—H12 | 0.930 | C25—H25B | 0.960 |
C13—N6 | 1.333 (3) | C25—H25C | 0.960 |
C13—S1 | 1.738 (3) | N2—N3 | 1.374 (3) |
C14—S1 | 1.772 (3) | N5—N6 | 1.380 (3) |
C14—H14A | 0.960 | O2—P1 | 1.455 (2) |
C14—H14B | 0.960 | O3—P1 | 1.5619 (19) |
C14—H14C | 0.960 | O4—P1 | 1.557 (2) |
C6—C1—C2 | 120.8 (3) | C16—C17—H17 | 119.6 |
C6—C1—Cl1 | 119.0 (2) | C18—C17—H17 | 119.6 |
C2—C1—Cl1 | 120.2 (2) | C19—C18—C17 | 120.1 (3) |
C1—C2—C3 | 120.0 (3) | C19—C18—H18 | 120.0 |
C1—C2—H2 | 120.0 | C17—C18—H18 | 120.0 |
C3—C2—H2 | 120.0 | C20—C19—C18 | 119.6 (3) |
C4—C3—C2 | 119.1 (3) | C20—C19—H19 | 120.2 |
C4—C3—H3 | 120.5 | C18—C19—H19 | 120.2 |
C2—C3—H3 | 120.5 | C19—C20—C21 | 120.5 (3) |
O1—C4—C5 | 114.8 (2) | C19—C20—H20 | 119.8 |
O1—C4—C3 | 124.9 (2) | C21—C20—H20 | 119.8 |
C5—C4—C3 | 120.3 (2) | C16—C21—C20 | 120.7 (3) |
C6—C5—C4 | 120.3 (3) | C16—C21—H21 | 119.6 |
C6—C5—H5 | 119.9 | C20—C21—H21 | 119.6 |
C4—C5—H5 | 119.9 | O4—C22—C23 | 111.9 (3) |
C1—C6—C5 | 119.5 (3) | O4—C22—H22A | 109.2 |
C1—C6—H6 | 120.2 | C23—C22—H22A | 109.2 |
C5—C6—H6 | 120.2 | O4—C22—H22B | 109.2 |
O1—C7—C8 | 107.4 (2) | C23—C22—H22B | 109.2 |
O1—C7—H7A | 110.2 | H22A—C22—H22B | 107.9 |
C8—C7—H7A | 110.2 | C22—C23—H23A | 109.5 |
O1—C7—H7B | 110.2 | C22—C23—H23B | 109.5 |
C8—C7—H7B | 110.2 | H23A—C23—H23B | 109.5 |
H7A—C7—H7B | 108.5 | C22—C23—H23C | 109.5 |
N2—C8—N1 | 116.6 (2) | H23A—C23—H23C | 109.5 |
N2—C8—C7 | 122.7 (2) | H23B—C23—H23C | 109.5 |
N1—C8—C7 | 120.6 (2) | O3—C24—C25 | 110.6 (3) |
N1—C9—N3 | 109.9 (2) | O3—C24—H24A | 109.5 |
N1—C9—C10 | 136.2 (2) | C25—C24—H24A | 109.5 |
N3—C9—C10 | 113.9 (2) | O3—C24—H24B | 109.5 |
C11—C10—C9 | 116.2 (2) | C25—C24—H24B | 109.5 |
C11—C10—C13 | 104.9 (2) | H24A—C24—H24B | 108.1 |
C9—C10—C13 | 138.9 (2) | C24—C25—H25A | 109.5 |
N5—C11—N4 | 124.6 (2) | C24—C25—H25B | 109.5 |
N5—C11—C10 | 107.3 (2) | H25A—C25—H25B | 109.5 |
N4—C11—C10 | 128.1 (2) | C24—C25—H25C | 109.5 |
N4—C12—N3 | 122.2 (2) | H25A—C25—H25C | 109.5 |
N4—C12—H12 | 118.9 | H25B—C25—H25C | 109.5 |
N3—C12—H12 | 118.9 | C9—N1—C8 | 102.5 (2) |
N6—C13—C10 | 111.2 (2) | C8—N2—N3 | 101.81 (19) |
N6—C13—S1 | 124.3 (2) | C12—N3—N2 | 125.4 (2) |
C10—C13—S1 | 124.5 (2) | C12—N3—C9 | 125.5 (2) |
S1—C14—H14A | 109.5 | N2—N3—C9 | 109.12 (19) |
S1—C14—H14B | 109.5 | C12—N4—C11 | 114.2 (2) |
H14A—C14—H14B | 109.5 | C11—N5—N6 | 111.5 (2) |
S1—C14—H14C | 109.5 | C11—N5—C15 | 126.2 (2) |
H14A—C14—H14C | 109.5 | N6—N5—C15 | 121.7 (2) |
H14B—C14—H14C | 109.5 | C13—N6—N5 | 105.2 (2) |
N5—C15—C16 | 112.8 (2) | C4—O1—C7 | 118.6 (2) |
N5—C15—P1 | 110.86 (17) | C24—O3—P1 | 123.9 (2) |
C16—C15—P1 | 115.91 (17) | C22—O4—P1 | 121.9 (2) |
N5—C15—H15 | 105.4 | O2—P1—O4 | 115.10 (13) |
C16—C15—H15 | 105.4 | O2—P1—O3 | 116.57 (13) |
P1—C15—H15 | 105.4 | O4—P1—O3 | 103.89 (12) |
C17—C16—C21 | 118.3 (3) | O2—P1—C15 | 113.24 (12) |
C17—C16—C15 | 122.8 (3) | O4—P1—C15 | 108.43 (12) |
C21—C16—C15 | 119.0 (3) | O3—P1—C15 | 97.89 (11) |
C16—C17—C18 | 120.8 (3) | C13—S1—C14 | 102.04 (15) |
C6—C1—C2—C3 | 0.0 (5) | N4—C12—N3—N2 | 179.0 (2) |
Cl1—C1—C2—C3 | −179.5 (2) | N4—C12—N3—C9 | −0.6 (4) |
C1—C2—C3—C4 | −1.5 (4) | C8—N2—N3—C12 | −178.5 (2) |
C2—C3—C4—O1 | −177.5 (3) | C8—N2—N3—C9 | 1.2 (3) |
C2—C3—C4—C5 | 2.5 (4) | N1—C9—N3—C12 | 178.7 (2) |
O1—C4—C5—C6 | 177.8 (3) | C10—C9—N3—C12 | −0.9 (4) |
C3—C4—C5—C6 | −2.1 (4) | N1—C9—N3—N2 | −0.9 (3) |
C2—C1—C6—C5 | 0.4 (4) | C10—C9—N3—N2 | 179.5 (2) |
Cl1—C1—C6—C5 | 179.9 (2) | N3—C12—N4—C11 | 1.4 (4) |
C4—C5—C6—C1 | 0.7 (4) | N5—C11—N4—C12 | 177.7 (3) |
O1—C7—C8—N2 | −12.1 (4) | C10—C11—N4—C12 | −0.7 (4) |
O1—C7—C8—N1 | 169.8 (2) | N4—C11—N5—N6 | −179.5 (2) |
N1—C9—C10—C11 | −178.0 (3) | C10—C11—N5—N6 | −0.8 (3) |
N3—C9—C10—C11 | 1.4 (3) | N4—C11—N5—C15 | 9.3 (4) |
N1—C9—C10—C13 | 2.6 (6) | C10—C11—N5—C15 | −172.0 (2) |
N3—C9—C10—C13 | −178.0 (3) | C16—C15—N5—C11 | 86.7 (3) |
C9—C10—C11—N5 | −179.4 (2) | P1—C15—N5—C11 | −141.5 (2) |
C13—C10—C11—N5 | 0.2 (3) | C16—C15—N5—N6 | −83.7 (3) |
C9—C10—C11—N4 | −0.7 (4) | P1—C15—N5—N6 | 48.2 (3) |
C13—C10—C11—N4 | 178.9 (2) | C10—C13—N6—N5 | −0.9 (3) |
C11—C10—C13—N6 | 0.4 (3) | S1—C13—N6—N5 | 178.5 (2) |
C9—C10—C13—N6 | 179.9 (3) | C11—N5—N6—C13 | 1.1 (3) |
C11—C10—C13—S1 | −178.9 (2) | C15—N5—N6—C13 | 172.7 (2) |
C9—C10—C13—S1 | 0.5 (5) | C5—C4—O1—C7 | 174.5 (3) |
N5—C15—C16—C17 | 40.2 (4) | C3—C4—O1—C7 | −5.6 (4) |
P1—C15—C16—C17 | −89.0 (3) | C8—C7—O1—C4 | 176.9 (2) |
N5—C15—C16—C21 | −138.9 (3) | C25—C24—O3—P1 | −128.6 (3) |
P1—C15—C16—C21 | 91.8 (3) | C23—C22—O4—P1 | 106.1 (3) |
C21—C16—C17—C18 | −0.1 (5) | C22—O4—P1—O2 | −10.1 (3) |
C15—C16—C17—C18 | −179.3 (3) | C22—O4—P1—O3 | −138.8 (3) |
C16—C17—C18—C19 | −0.4 (6) | C22—O4—P1—C15 | 117.8 (3) |
C17—C18—C19—C20 | 0.4 (6) | C24—O3—P1—O2 | −66.4 (3) |
C18—C19—C20—C21 | 0.1 (6) | C24—O3—P1—O4 | 61.3 (3) |
C17—C16—C21—C20 | 0.6 (5) | C24—O3—P1—C15 | 172.6 (3) |
C15—C16—C21—C20 | 179.8 (3) | N5—C15—P1—O2 | 45.4 (2) |
C19—C20—C21—C16 | −0.5 (6) | C16—C15—P1—O2 | 175.57 (18) |
N3—C9—N1—C8 | 0.2 (3) | N5—C15—P1—O4 | −83.64 (19) |
C10—C9—N1—C8 | 179.7 (3) | C16—C15—P1—O4 | 46.5 (2) |
N2—C8—N1—C9 | 0.6 (3) | N5—C15—P1—O3 | 168.81 (17) |
C7—C8—N1—C9 | 178.8 (2) | C16—C15—P1—O3 | −61.0 (2) |
N1—C8—N2—N3 | −1.2 (3) | N6—C13—S1—C14 | −2.3 (3) |
C7—C8—N2—N3 | −179.3 (2) | C10—C13—S1—C14 | 177.0 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C22—H22A···O2 | 0.97 | 2.49 | 2.948 (4) | 109 |
C17—H17···N6 | 0.93 | 2.61 | 3.238 (4) | 125 |
C15—H15···N4 | 0.98 | 2.60 | 2.991 (3) | 104 |
C7—H7A···O2i | 0.97 | 2.36 | 3.324 (4) | 171 |
C12—H12···N2ii | 0.93 | 2.53 | 3.450 (3) | 169 |
Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) −x, −y+2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C25H26ClN6O4PS |
Mr | 573.00 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 294 |
a, b, c (Å) | 13.8732 (12), 13.5760 (11), 16.2034 (14) |
β (°) | 113.515 (2) |
V (Å3) | 2798.4 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.31 |
Crystal size (mm) | 0.20 × 0.20 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2001) |
Tmin, Tmax | 0.941, 0.970 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 26250, 5485, 3386 |
Rint | 0.108 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.059, 0.150, 0.94 |
No. of reflections | 5485 |
No. of parameters | 346 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.51, −0.27 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
C22—H22A···O2 | 0.97 | 2.49 | 2.948 (4) | 109 |
C17—H17···N6 | 0.93 | 2.61 | 3.238 (4) | 125 |
C15—H15···N4 | 0.98 | 2.60 | 2.991 (3) | 104 |
C7—H7A···O2i | 0.97 | 2.36 | 3.324 (4) | 171 |
C12—H12···N2ii | 0.93 | 2.53 | 3.450 (3) | 169 |
Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) −x, −y+2, −z+1. |
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Pyrazolotriazolopyrimidine derivatives have been reported to retain high affinity for adenosine receptors (Gatta et al., 1993). A series of pyrazolo[4,3-e]-1,2,4-triazolo[1,5-c]-pyrimidines has been synthesized with the aim of finding potent and selective adenosine A2A antagonists (Baraldi et al., 1996, 1998). Organic phosphorus compounds play an important role in pesticidal science because of their significant biological properties. The title compound, (I), has been prepared as part of our work in the search for novel biologically active heterocyclic compounds. We report here the crystal structure of (I). In the molecule of (I) (Fig. 1), the pyrazolotriazolopyrimidine ring system is almost planar, with a maximum deviation of 0.023 (2) Å, for N2, forming a fully delocalized system. The dihedral angles between the pyrimidine and the triazole and pyrazole rings are 1.31 (1) and 1.1 (1)°, respectively. In the pyrazolotriazolopyrimidine ring system, the the C—N bonds are significantly shorter than a normal single C—N bond (1.47 Å; Sasada, 1984) and close to the value for a C=N bond (1.28 Å; Wang et al., 1998). This indicates significant electron delocalization in the pyrazolotriazolopyrimidine system. The O2—P1—O4, O2—P1—O3 and O2—P1—C15 bond angles are larger than the O4—P1—O3, O4—P1—C15 and O3—P1—C15 bond angles, indicating a distorted tetrahedral configuration for the phosphorus atom.
Intra- and intermolecular C—H···O and C—H···N hydrogen bonds contribute strongly to the stability of the crystal structure (Fig. 2 and Table 1). Strong π—π stacking interactions also occur between C1—C6 and N1—N3/C8/C9, N5/N6/C10/C11/C13, N3/N4/C9—C12 rings of neighboring molecules. Centroid-centroid distances are 3.990 (2), 3.909 (2) and 3.509 (2) Å, dihedral angles are 7.76, 7.35 and 8.26°, and shortest interplanar distances are 3.312, 3.567 and 3.439 Å, respectively.