Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102006649/de1182sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102006649/de1182VIsup2.hkl |
CCDC reference: 169806
Compound (VI) was synthesized (Avasthi & Rawat, 2001) by the reaction of 4,6-bis(methylithio)-1H-pyrazolo[3,4-d]pyrimidine (Taylor et al., 1966) with commercial 1-bromo-3-phenylpropane using the general methodology described earlier by Avasthi et al. (1993). Diffraction quality crystals of (VI) were obtained by slow evaporation of an ethyl acetate-hexane solution at room temperature.
Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: MolEN (Fair, 1990); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXTL-NT (Bruker, 1997); molecular graphics: SHELXTL-NT; software used to prepare material for publication: SHELXTL-NT.
C15H16N4OS | Dx = 1.322 Mg m−3 |
Mr = 300.38 | Melting point: 140 K |
Orthorhombic, Pbca | Cu Kα radiation, λ = 1.54180 Å |
a = 9.4742 (8) Å | Cell parameters from 25 reflections |
b = 19.287 (1) Å | θ = 9.1–11.9° |
c = 33.032 (2) Å | µ = 1.94 mm−1 |
V = 6035.8 (7) Å3 | T = 293 K |
Z = 16 | Block, colourless |
F(000) = 2528 | 0.35 × 0.25 × 0.15 mm |
Enraf-Nonius CAD-4 diffractometer | 4176 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.000 |
Graphite monochromator | θmax = 67.9°, θmin = 2.7° |
ω/2θ scans | h = 0→11 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→20 |
Tmin = 0.703, Tmax = 0.747 | l = 0→39 |
5179 measured reflections | 2 standard reflections every 60 min |
5179 independent reflections | intensity decay: none |
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)] = 0.049 | H-atom parameters constrained |
wR(F2) = 0.190 | w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.52 | (Δ/σ)max < 0.001 |
5179 reflections | Δρmax = 0.26 e Å−3 |
380 parameters | Δρmin = −0.39 e Å−3 |
0 restraints | Extinction correction: SHELXTL-NT (Bruker, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00029 (8) |
C15H16N4OS | V = 6035.8 (7) Å3 |
Mr = 300.38 | Z = 16 |
Orthorhombic, Pbca | Cu Kα radiation |
a = 9.4742 (8) Å | µ = 1.94 mm−1 |
b = 19.287 (1) Å | T = 293 K |
c = 33.032 (2) Å | 0.35 × 0.25 × 0.15 mm |
Enraf-Nonius CAD-4 diffractometer | 4176 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.000 |
Tmin = 0.703, Tmax = 0.747 | 2 standard reflections every 60 min |
5179 measured reflections | intensity decay: none |
5179 independent reflections |
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.190 | H-atom parameters constrained |
S = 1.52 | Δρmax = 0.26 e Å−3 |
5179 reflections | Δρmin = −0.39 e Å−3 |
380 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 | ||
N1 | 0.2822 (2) | 0.33991 (12) | 0.11592 (6) | 0.0455 (5) | |
N2 | 0.4246 (2) | 0.35495 (13) | 0.11624 (8) | 0.0565 (6) | |
C3 | 0.4826 (3) | 0.31210 (15) | 0.09012 (9) | 0.0517 (7) | |
H3 | 0.5783 | 0.3113 | 0.0839 | 0.062* | |
C3a | 0.3820 (2) | 0.26788 (13) | 0.07285 (7) | 0.0417 (6) | |
C4 | 0.3809 (3) | 0.21321 (14) | 0.04388 (8) | 0.0430 (6) | |
N5 | 0.2442 (2) | 0.18970 (12) | 0.03596 (7) | 0.0458 (5) | |
H5 | 0.2342 | 0.1581 | 0.0178 | 0.055* | |
C6 | 0.1238 (3) | 0.21341 (14) | 0.05514 (7) | 0.0423 (6) | |
N7 | 0.1229 (2) | 0.26261 (11) | 0.08221 (6) | 0.0427 (5) | |
C7a | 0.2539 (2) | 0.28811 (13) | 0.08987 (6) | 0.0371 (5) | |
C8 | 0.1846 (3) | 0.37719 (15) | 0.14171 (7) | 0.0470 (6) | |
H8A | 0.0887 | 0.3651 | 0.1342 | 0.056* | |
H8B | 0.1964 | 0.4266 | 0.1374 | 0.056* | |
C9 | 0.2068 (3) | 0.36094 (15) | 0.18616 (7) | 0.0464 (6) | |
H9A | 0.2987 | 0.3779 | 0.1946 | 0.056* | |
H9B | 0.2052 | 0.3111 | 0.1901 | 0.056* | |
C10 | 0.0926 (3) | 0.39443 (14) | 0.21223 (7) | 0.0486 (6) | |
H10A | 0.1158 | 0.3877 | 0.2406 | 0.058* | |
H10B | 0.0910 | 0.4439 | 0.2070 | 0.058* | |
C11 | −0.0523 (3) | 0.36461 (13) | 0.20406 (7) | 0.0446 (6) | |
C12 | −0.0857 (3) | 0.29841 (16) | 0.21683 (10) | 0.0644 (8) | |
H12 | −0.0198 | 0.2733 | 0.2317 | 0.077* | |
C13 | −0.2144 (4) | 0.26888 (18) | 0.20804 (11) | 0.0750 (10) | |
H13 | −0.2352 | 0.2243 | 0.2170 | 0.090* | |
C14 | −0.3122 (3) | 0.30563 (18) | 0.18584 (10) | 0.0677 (9) | |
H14 | −0.3983 | 0.2854 | 0.1792 | 0.081* | |
C15 | −0.2832 (3) | 0.37149 (17) | 0.17356 (9) | 0.0607 (8) | |
H15 | −0.3499 | 0.3967 | 0.1591 | 0.073* | |
C16 | −0.1541 (3) | 0.40058 (15) | 0.18278 (8) | 0.0520 (7) | |
H16 | −0.1351 | 0.4457 | 0.1744 | 0.062* | |
O17 | 0.48290 (19) | 0.18646 (11) | 0.02673 (6) | 0.0561 (5) | |
S18 | −0.02817 (8) | 0.17018 (4) | 0.03995 (3) | 0.0611 (3) | |
C19 | −0.1617 (3) | 0.21925 (17) | 0.06514 (11) | 0.0663 (9) | |
H19A | −0.2527 | 0.2000 | 0.0590 | 0.099* | |
H19B | −0.1582 | 0.2665 | 0.0561 | 0.099* | |
H19C | −0.1461 | 0.2176 | 0.0938 | 0.099* | |
N1' | −0.0789 (2) | 0.56639 (11) | 0.11247 (6) | 0.0457 (5) | |
N2' | −0.2208 (2) | 0.56850 (14) | 0.12000 (7) | 0.0547 (6) | |
C3' | −0.2767 (3) | 0.52026 (15) | 0.09685 (8) | 0.0513 (7) | |
H3' | −0.3726 | 0.5102 | 0.0958 | 0.062* | |
C3a' | −0.1730 (2) | 0.48589 (13) | 0.07400 (7) | 0.0411 (6) | |
C4' | −0.1706 (2) | 0.43280 (13) | 0.04412 (7) | 0.0427 (6) | |
N5' | −0.0347 (2) | 0.41993 (11) | 0.03054 (6) | 0.0419 (5) | |
H5' | −0.0242 | 0.3883 | 0.0124 | 0.050* | |
C6' | 0.0845 (3) | 0.45369 (13) | 0.04365 (7) | 0.0375 (5) | |
N7' | 0.0847 (2) | 0.50337 (11) | 0.07034 (6) | 0.0401 (5) | |
C7a' | −0.0478 (2) | 0.51738 (13) | 0.08453 (7) | 0.0382 (5) | |
C8' | 0.0168 (3) | 0.61338 (14) | 0.13331 (8) | 0.0508 (7) | |
H8'1 | 0.0027 | 0.6601 | 0.1232 | 0.061* | |
H8'2 | 0.1135 | 0.6001 | 0.1275 | 0.061* | |
C9' | −0.0059 (3) | 0.61272 (15) | 0.17835 (8) | 0.0512 (7) | |
H9'1 | −0.0031 | 0.5652 | 0.1880 | 0.061* | |
H9'2 | −0.0988 | 0.6313 | 0.1843 | 0.061* | |
C10' | 0.1056 (3) | 0.65540 (16) | 0.20097 (10) | 0.0599 (8) | |
H10C | 0.1090 | 0.7017 | 0.1896 | 0.072* | |
H10D | 0.0785 | 0.6594 | 0.2292 | 0.072* | |
C11' | 0.2498 (3) | 0.62321 (14) | 0.19838 (8) | 0.0460 (6) | |
C12' | 0.2850 (3) | 0.56601 (16) | 0.22123 (9) | 0.0608 (8) | |
H12' | 0.2206 | 0.5492 | 0.2401 | 0.073* | |
C13' | 0.4137 (3) | 0.53284 (18) | 0.21689 (10) | 0.0717 (9) | |
H13' | 0.4345 | 0.4939 | 0.2324 | 0.086* | |
C14' | 0.5093 (4) | 0.5576 (2) | 0.18989 (10) | 0.0722 (9) | |
H14' | 0.5961 | 0.5356 | 0.1869 | 0.087* | |
C15' | 0.4784 (4) | 0.6144 (2) | 0.16716 (11) | 0.0740 (10) | |
H15' | 0.5442 | 0.6311 | 0.1487 | 0.089* | |
C16' | 0.3510 (3) | 0.64706 (15) | 0.17132 (9) | 0.0598 (8) | |
H16' | 0.3317 | 0.6861 | 0.1557 | 0.072* | |
O17' | −0.27226 (19) | 0.40046 (11) | 0.03006 (6) | 0.0566 (5) | |
S18' | 0.23859 (7) | 0.42363 (4) | 0.02114 (2) | 0.0510 (2) | |
C19' | 0.3685 (3) | 0.47813 (18) | 0.04405 (9) | 0.0627 (8) | |
H19D | 0.4602 | 0.4661 | 0.0339 | 0.094* | |
H19E | 0.3666 | 0.4719 | 0.0729 | 0.094* | |
H19F | 0.3484 | 0.5257 | 0.0377 | 0.094* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0469 (11) | 0.0514 (14) | 0.0384 (11) | 0.0035 (10) | −0.0006 (8) | −0.0107 (9) |
N2 | 0.0520 (13) | 0.0596 (16) | 0.0578 (14) | −0.0010 (11) | −0.0025 (10) | −0.0152 (12) |
C3 | 0.0458 (14) | 0.0496 (18) | 0.0598 (17) | 0.0001 (12) | −0.0015 (12) | −0.0141 (13) |
C3a | 0.0442 (13) | 0.0384 (15) | 0.0424 (13) | 0.0041 (10) | −0.0002 (10) | −0.0005 (11) |
C4 | 0.0462 (13) | 0.0374 (15) | 0.0454 (13) | 0.0010 (11) | 0.0003 (10) | −0.0032 (11) |
N5 | 0.0468 (11) | 0.0427 (13) | 0.0478 (12) | −0.0016 (9) | 0.0005 (9) | −0.0132 (10) |
C6 | 0.0452 (12) | 0.0422 (15) | 0.0396 (12) | 0.0023 (11) | −0.0019 (10) | 0.0011 (11) |
N7 | 0.0447 (11) | 0.0431 (14) | 0.0405 (11) | −0.0003 (9) | 0.0006 (8) | 0.0012 (9) |
C7a | 0.0477 (12) | 0.0351 (14) | 0.0286 (10) | 0.0017 (10) | −0.0004 (9) | 0.0018 (10) |
C8 | 0.0559 (14) | 0.0482 (16) | 0.0370 (12) | 0.0098 (12) | 0.0006 (11) | −0.0034 (11) |
C9 | 0.0541 (14) | 0.0466 (16) | 0.0385 (12) | 0.0056 (12) | −0.0073 (11) | −0.0052 (11) |
C10 | 0.0613 (15) | 0.0508 (17) | 0.0338 (12) | −0.0003 (13) | −0.0008 (11) | −0.0088 (11) |
C11 | 0.0584 (15) | 0.0423 (16) | 0.0330 (12) | 0.0037 (12) | 0.0032 (10) | −0.0050 (10) |
C12 | 0.076 (2) | 0.0508 (19) | 0.0665 (19) | −0.0048 (15) | −0.0080 (16) | 0.0197 (15) |
C13 | 0.093 (2) | 0.055 (2) | 0.077 (2) | −0.0220 (18) | −0.0115 (19) | 0.0230 (17) |
C14 | 0.0636 (18) | 0.072 (2) | 0.0675 (19) | −0.0188 (17) | −0.0037 (15) | 0.0033 (17) |
C15 | 0.0651 (18) | 0.059 (2) | 0.0583 (17) | −0.0001 (15) | −0.0114 (14) | 0.0037 (15) |
C16 | 0.0625 (16) | 0.0392 (16) | 0.0544 (15) | −0.0018 (13) | −0.0059 (13) | 0.0013 (12) |
O17 | 0.0444 (10) | 0.0534 (12) | 0.0703 (13) | 0.0036 (9) | 0.0036 (8) | −0.0210 (10) |
S18 | 0.0466 (4) | 0.0589 (5) | 0.0779 (6) | −0.0057 (3) | −0.0027 (3) | −0.0153 (4) |
C19 | 0.0455 (15) | 0.063 (2) | 0.090 (2) | −0.0005 (14) | 0.0087 (15) | 0.0009 (17) |
N1' | 0.0460 (11) | 0.0490 (14) | 0.0421 (11) | 0.0005 (10) | −0.0018 (9) | −0.0109 (10) |
N2' | 0.0459 (12) | 0.0651 (17) | 0.0533 (13) | 0.0043 (11) | −0.0002 (10) | −0.0162 (12) |
C3' | 0.0434 (13) | 0.063 (2) | 0.0480 (14) | 0.0052 (12) | −0.0061 (11) | −0.0130 (13) |
C3a' | 0.0410 (12) | 0.0419 (16) | 0.0403 (12) | 0.0030 (10) | −0.0024 (9) | −0.0030 (10) |
C4' | 0.0452 (13) | 0.0416 (15) | 0.0413 (12) | 0.0001 (11) | −0.0026 (10) | −0.0025 (11) |
N5' | 0.0456 (11) | 0.0377 (12) | 0.0422 (11) | 0.0005 (9) | 0.0023 (8) | −0.0092 (9) |
C6' | 0.0462 (12) | 0.0331 (13) | 0.0331 (11) | −0.0002 (10) | 0.0005 (9) | 0.0048 (9) |
N7' | 0.0456 (10) | 0.0418 (12) | 0.0329 (10) | 0.0004 (9) | −0.0003 (8) | 0.0011 (9) |
C7a' | 0.0455 (12) | 0.0354 (15) | 0.0338 (11) | 0.0019 (10) | −0.0027 (9) | 0.0017 (9) |
C8' | 0.0599 (15) | 0.0433 (16) | 0.0492 (15) | −0.0099 (13) | 0.0013 (12) | −0.0086 (12) |
C9' | 0.0514 (15) | 0.0534 (18) | 0.0488 (15) | −0.0028 (12) | 0.0047 (11) | −0.0149 (13) |
C10' | 0.0602 (17) | 0.0545 (19) | 0.0650 (18) | 0.0012 (14) | −0.0030 (13) | −0.0309 (15) |
C11' | 0.0550 (14) | 0.0385 (16) | 0.0446 (13) | −0.0074 (11) | −0.0029 (11) | −0.0159 (12) |
C12' | 0.0684 (18) | 0.067 (2) | 0.0467 (15) | −0.0135 (15) | −0.0035 (13) | 0.0046 (14) |
C13' | 0.085 (2) | 0.065 (2) | 0.065 (2) | 0.0041 (18) | −0.0252 (17) | 0.0080 (17) |
C14' | 0.0646 (19) | 0.085 (3) | 0.067 (2) | 0.0122 (18) | −0.0060 (16) | −0.0163 (19) |
C15' | 0.071 (2) | 0.083 (3) | 0.068 (2) | −0.0036 (18) | 0.0206 (17) | −0.0025 (19) |
C16' | 0.0707 (18) | 0.0471 (18) | 0.0617 (18) | −0.0046 (14) | 0.0087 (15) | 0.0047 (14) |
O17' | 0.0478 (10) | 0.0632 (14) | 0.0588 (11) | −0.0071 (9) | 0.0010 (8) | −0.0214 (10) |
S18' | 0.0478 (4) | 0.0524 (5) | 0.0530 (4) | 0.0045 (3) | 0.0071 (3) | −0.0030 (3) |
C19' | 0.0480 (15) | 0.073 (2) | 0.0675 (19) | −0.0062 (14) | 0.0029 (13) | 0.0043 (16) |
N1—C7a | 1.345 (3) | N1'—C7a' | 1.354 (3) |
N1—N2 | 1.380 (3) | N1'—N2' | 1.368 (3) |
N1—C8 | 1.449 (3) | N1'—C8' | 1.455 (3) |
N2—C3 | 1.315 (3) | N2'—C3' | 1.315 (3) |
C3—C3a | 1.400 (4) | C3'—C3a' | 1.405 (3) |
C3—H3 | 0.9300 | C3'—H3' | 0.9300 |
C3a—C7a | 1.393 (3) | C3a'—C7a' | 1.377 (3) |
C3a—C4 | 1.424 (3) | C3a'—C4' | 1.422 (3) |
C4—O17 | 1.233 (3) | C4'—O17' | 1.238 (3) |
C4—N5 | 1.397 (3) | C4'—N5' | 1.385 (3) |
N5—C6 | 1.383 (3) | N5'—C6' | 1.374 (3) |
N5—H5 | 0.8600 | N5'—H5' | 0.8600 |
C6—N7 | 1.304 (3) | C6'—N7' | 1.302 (3) |
C6—S18 | 1.738 (3) | C6'—S18' | 1.737 (2) |
N7—C7a | 1.359 (3) | N7'—C7a' | 1.367 (3) |
C8—C9 | 1.516 (3) | C8'—C9' | 1.503 (4) |
C8—H8A | 0.9700 | C8'—H8'1 | 0.9700 |
C8—H8B | 0.9700 | C8'—H8'2 | 0.9700 |
C9—C10 | 1.526 (3) | C9'—C10' | 1.534 (4) |
C9—H9A | 0.9700 | C9'—H9'1 | 0.9700 |
C9—H9B | 0.9700 | C9'—H9'2 | 0.9700 |
C10—C11 | 1.513 (3) | C10'—C11' | 1.503 (4) |
C10—H10A | 0.9700 | C10'—H10C | 0.9700 |
C10—H10B | 0.9700 | C10'—H10D | 0.9700 |
C11—C16 | 1.380 (4) | C11'—C12' | 1.378 (4) |
C11—C12 | 1.381 (4) | C11'—C16' | 1.389 (4) |
C12—C13 | 1.377 (4) | C12'—C13' | 1.384 (4) |
C12—H12 | 0.9300 | C12'—H12' | 0.9300 |
C13—C14 | 1.378 (5) | C13'—C14' | 1.358 (5) |
C13—H13 | 0.9300 | C13'—H13' | 0.9300 |
C14—C15 | 1.362 (5) | C14'—C15' | 1.360 (5) |
C14—H14 | 0.9300 | C14'—H14' | 0.9300 |
C15—C16 | 1.379 (4) | C15'—C16' | 1.369 (4) |
C15—H15 | 0.9300 | C15'—H15' | 0.9300 |
C16—H16 | 0.9300 | C16'—H16' | 0.9300 |
S18—C19 | 1.786 (3) | S18'—C19' | 1.787 (3) |
C19—H19A | 0.9600 | C19'—H19D | 0.9600 |
C19—H19B | 0.9600 | C19'—H19E | 0.9600 |
C19—H19C | 0.9600 | C19'—H19F | 0.9600 |
C7a—N1—N2 | 110.8 (2) | C7a'—N1'—N2' | 111.0 (2) |
C7a—N1—C8 | 128.1 (2) | C7a'—N1'—C8' | 128.5 (2) |
N2—N1—C8 | 121.0 (2) | N2'—N1'—C8' | 120.5 (2) |
C3—N2—N1 | 105.7 (2) | C3'—N2'—N1' | 105.6 (2) |
N2—C3—C3a | 111.5 (2) | N2'—C3'—C3a' | 111.4 (2) |
N2—C3—H3 | 124.3 | N2'—C3'—H3' | 124.3 |
C3a—C3—H3 | 124.3 | C3a'—C3'—H3' | 124.3 |
C7a—C3a—C3 | 104.9 (2) | C7a'—C3a'—C3' | 105.0 (2) |
C7a—C3a—C4 | 118.2 (2) | C7a'—C3a'—C4' | 118.6 (2) |
C3—C3a—C4 | 136.9 (2) | C3'—C3a'—C4' | 136.4 (2) |
O17—C4—N5 | 120.3 (2) | O17'—C4'—N5' | 120.7 (2) |
O17—C4—C3a | 127.8 (2) | O17'—C4'—C3a' | 127.6 (2) |
N5—C4—C3a | 111.9 (2) | N5'—C4'—C3a' | 111.7 (2) |
C6—N5—C4 | 124.9 (2) | C6'—N5'—C4' | 125.2 (2) |
C6—N5—H5 | 117.6 | C6'—N5'—H5' | 117.4 |
C4—N5—H5 | 117.6 | C4'—N5'—H5' | 117.4 |
N7—C6—N5 | 124.1 (2) | N7'—C6'—N5' | 124.2 (2) |
N7—C6—S18 | 122.79 (19) | N7'—C6'—S18' | 122.32 (19) |
N5—C6—S18 | 113.11 (18) | N5'—C6'—S18' | 113.44 (17) |
C6—N7—C7a | 112.6 (2) | C6'—N7'—C7a' | 112.1 (2) |
N1—C7a—N7 | 124.7 (2) | N1'—C7a'—N7' | 124.8 (2) |
N1—C7a—C3a | 107.0 (2) | N1'—C7a'—C3a' | 107.0 (2) |
N7—C7a—C3a | 128.3 (2) | N7'—C7a'—C3a' | 128.1 (2) |
N1—C8—C9 | 112.2 (2) | N1'—C8'—C9' | 111.9 (2) |
N1—C8—H8A | 109.2 | N1'—C8'—H8'1 | 109.2 |
C9—C8—H8A | 109.2 | C9'—C8'—H8'1 | 109.2 |
N1—C8—H8B | 109.2 | N1'—C8'—H8'2 | 109.2 |
C9—C8—H8B | 109.2 | C9'—C8'—H8'2 | 109.2 |
H8A—C8—H8B | 107.9 | H8'1—C8'—H8'2 | 107.9 |
C8—C9—C10 | 111.1 (2) | C8'—C9'—C10' | 112.3 (2) |
C8—C9—H9A | 109.4 | C8'—C9'—H9'1 | 109.2 |
C10—C9—H9A | 109.4 | C10'—C9'—H9'1 | 109.2 |
C8—C9—H9B | 109.4 | C8'—C9'—H9'2 | 109.2 |
C10—C9—H9B | 109.4 | C10'—C9'—H9'2 | 109.2 |
H9A—C9—H9B | 108.0 | H9'1—C9'—H9'2 | 107.9 |
C11—C10—C9 | 112.5 (2) | C11'—C10'—C9' | 112.1 (2) |
C11—C10—H10A | 109.1 | C11'—C10'—H10C | 109.2 |
C9—C10—H10A | 109.1 | C9'—C10'—H10C | 109.2 |
C11—C10—H10B | 109.1 | C11'—C10'—H10D | 109.2 |
C9—C10—H10B | 109.1 | C9'—C10'—H10D | 109.2 |
H10A—C10—H10B | 107.8 | H10C—C10'—H10D | 107.9 |
C16—C11—C12 | 117.4 (3) | C12'—C11'—C16' | 116.8 (3) |
C16—C11—C10 | 122.3 (2) | C12'—C11'—C10' | 121.3 (3) |
C12—C11—C10 | 120.3 (2) | C16'—C11'—C10' | 121.8 (3) |
C11—C12—C13 | 121.4 (3) | C11'—C12'—C13' | 121.8 (3) |
C11—C12—H12 | 119.3 | C11'—C12'—H12' | 119.1 |
C13—C12—H12 | 119.3 | C13'—C12'—H12' | 119.1 |
C14—C13—C12 | 119.7 (3) | C14'—C13'—C12' | 119.6 (3) |
C14—C13—H13 | 120.2 | C14'—C13'—H13' | 120.2 |
C12—C13—H13 | 120.2 | C12'—C13'—H13' | 120.2 |
C15—C14—C13 | 120.2 (3) | C15'—C14'—C13' | 120.1 (3) |
C15—C14—H14 | 119.9 | C15'—C14'—H14' | 119.9 |
C13—C14—H14 | 119.9 | C13'—C14'—H14' | 119.9 |
C14—C15—C16 | 119.5 (3) | C14'—C15'—C16' | 120.4 (3) |
C14—C15—H15 | 120.2 | C14'—C15'—H15' | 119.8 |
C16—C15—H15 | 120.2 | C16'—C15'—H15' | 119.8 |
C15—C16—C11 | 121.8 (3) | C15'—C16'—C11' | 121.4 (3) |
C15—C16—H16 | 119.1 | C15'—C16'—H16' | 119.3 |
C11—C16—H16 | 119.1 | C11'—C16'—H16' | 119.3 |
C6—S18—C19 | 101.44 (13) | C6'—S18'—C19' | 101.60 (13) |
S18—C19—H19A | 109.5 | S18'—C19'—H19D | 109.5 |
S18—C19—H19B | 109.5 | S18'—C19'—H19E | 109.5 |
H19A—C19—H19B | 109.5 | H19D—C19'—H19E | 109.5 |
S18—C19—H19C | 109.5 | S18'—C19'—H19F | 109.5 |
H19A—C19—H19C | 109.5 | H19D—C19'—H19F | 109.5 |
H19B—C19—H19C | 109.5 | H19E—C19'—H19F | 109.5 |
C7a—N1—N2—C3 | 0.2 (3) | N2'—C3'—C3a'—C7a' | −0.7 (3) |
C8—N1—N2—C3 | 179.4 (2) | N2'—C3'—C3a'—C4' | −177.8 (3) |
N1—N2—C3—C3a | −1.0 (3) | C7a'—C3a'—C4'—O17' | −177.6 (3) |
N2—C3—C3a—C7a | 1.4 (3) | C3'—C3a'—C4'—O17' | −0.8 (5) |
N2—C3—C3a—C4 | 179.8 (3) | C7a'—C3a'—C4'—N5' | 1.4 (3) |
C7a—C3a—C4—O17 | −177.1 (3) | C3'—C3a'—C4'—N5' | 178.2 (3) |
C3—C3a—C4—O17 | 4.8 (5) | O17'—C4'—N5'—C6' | 178.8 (2) |
C7a—C3a—C4—N5 | 2.3 (3) | C3a'—C4'—N5'—C6' | −0.2 (3) |
C3—C3a—C4—N5 | −175.9 (3) | C4'—N5'—C6'—N7' | −1.2 (4) |
O17—C4—N5—C6 | 176.2 (3) | C4'—N5'—C6'—S18' | 178.7 (2) |
C3a—C4—N5—C6 | −3.2 (4) | N5'—C6'—N7'—C7a' | 1.2 (3) |
C4—N5—C6—N7 | 2.4 (4) | S18'—C6'—N7'—C7a' | −178.71 (17) |
C4—N5—C6—S18 | −177.0 (2) | N2'—N1'—C7a'—N7' | 179.2 (2) |
N5—C6—N7—C7a | −0.4 (4) | C8'—N1'—C7a'—N7' | −0.4 (4) |
S18—C6—N7—C7a | 178.88 (18) | N2'—N1'—C7a'—C3a' | −1.0 (3) |
N2—N1—C7a—N7 | −178.6 (2) | C8'—N1'—C7a'—C3a' | 179.4 (2) |
C8—N1—C7a—N7 | 2.3 (4) | C6'—N7'—C7a'—N1' | 179.9 (2) |
N2—N1—C7a—C3a | 0.7 (3) | C6'—N7'—C7a'—C3a' | 0.1 (4) |
C8—N1—C7a—C3a | −178.5 (2) | C3'—C3a'—C7a'—N1' | 1.0 (3) |
C6—N7—C7a—N1 | 178.7 (2) | C4'—C3a'—C7a'—N1' | 178.7 (2) |
C6—N7—C7a—C3a | −0.4 (4) | C3'—C3a'—C7a'—N7' | −179.2 (2) |
C3—C3a—C7a—N1 | −1.2 (3) | C4'—C3a'—C7a'—N7' | −1.5 (4) |
C4—C3a—C7a—N1 | −179.9 (2) | C7a'—N1'—C8'—C9' | −130.1 (3) |
C3—C3a—C7a—N7 | 178.0 (3) | N2'—N1'—C8'—C9' | 50.3 (4) |
C4—C3a—C7a—N7 | −0.7 (4) | N1'—C8'—C9'—C10' | 173.2 (2) |
C7a—N1—C8—C9 | 110.9 (3) | C8'—C9'—C10'—C11' | −67.7 (4) |
N2—N1—C8—C9 | −68.2 (3) | C9'—C10'—C11'—C12' | −76.0 (3) |
N1—C8—C9—C10 | −173.7 (2) | C9'—C10'—C11'—C16' | 100.3 (3) |
C8—C9—C10—C11 | 65.4 (3) | C16'—C11'—C12'—C13' | −1.4 (4) |
C9—C10—C11—C16 | −106.1 (3) | C10'—C11'—C12'—C13' | 175.1 (3) |
C9—C10—C11—C12 | 71.8 (3) | C11'—C12'—C13'—C14' | 1.0 (5) |
C16—C11—C12—C13 | 1.2 (5) | C12'—C13'—C14'—C15' | −0.3 (5) |
C10—C11—C12—C13 | −176.8 (3) | C13'—C14'—C15'—C16' | 0.1 (5) |
C11—C12—C13—C14 | 0.4 (5) | C14'—C15'—C16'—C11' | −0.5 (5) |
C12—C13—C14—C15 | −1.7 (5) | C12'—C11'—C16'—C15' | 1.1 (4) |
C13—C14—C15—C16 | 1.3 (5) | C10'—C11'—C16'—C15' | −175.3 (3) |
C14—C15—C16—C11 | 0.3 (5) | N7'—C6'—S18'—C19' | −0.8 (2) |
C12—C11—C16—C15 | −1.6 (4) | N5'—C6'—S18'—C19' | 179.30 (19) |
C10—C11—C16—C15 | 176.4 (3) | N5—H5—O17'i—C4'i | 78.5 |
N7—C6—S18—C19 | 7.2 (3) | N5'i—H5'i—O17—C4 | 32.4 |
N5—C6—S18—C19 | −173.4 (2) | N5'—H5'—O17ii—C4ii | 32.4 |
C7a'—N1'—N2'—C3' | 0.5 (3) | N5ii—H5ii—O17'—C4' | 78.5 |
C8'—N1'—N2'—C3' | −179.8 (2) | N5—C6—S18—C19 | −173.4 (2) |
N1'—N2'—C3'—C3a' | 0.1 (3) | N7—C6—S18—C19 | 7.2 (3) |
Symmetry codes: (i) x+1/2, −y+1/2, −z; (ii) x−1/2, −y+1/2, −z. |
Experimental details
Crystal data | |
Chemical formula | C15H16N4OS |
Mr | 300.38 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 293 |
a, b, c (Å) | 9.4742 (8), 19.287 (1), 33.032 (2) |
V (Å3) | 6035.8 (7) |
Z | 16 |
Radiation type | Cu Kα |
µ (mm−1) | 1.94 |
Crystal size (mm) | 0.35 × 0.25 × 0.15 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.703, 0.747 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5179, 5179, 4176 |
Rint | 0.000 |
(sin θ/λ)max (Å−1) | 0.601 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.190, 1.52 |
No. of reflections | 5179 |
No. of parameters | 380 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.26, −0.39 |
Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, MolEN (Fair, 1990), SHELXS97 (Sheldrick, 1990), SHELXTL-NT (Bruker, 1997), SHELXTL-NT.
C7a—N1—C8—C9 | 110.9 (3) | C7a'—N1'—C8'—C9' | −130.1 (3) |
N2—N1—C8—C9 | −68.2 (3) | N2'—N1'—C8'—C9' | 50.3 (4) |
N1—C8—C9—C10 | −173.7 (2) | N1'—C8'—C9'—C10' | 173.2 (2) |
C8—C9—C10—C11 | 65.4 (3) | C8'—C9'—C10'—C11' | −67.7 (4) |
C9—C10—C11—C16 | −106.1 (3) | C9'—C10'—C11'—C12' | −76.0 (3) |
C9—C10—C11—C12 | 71.8 (3) | C9'—C10'—C11'—C16' | 100.3 (3) |
Interactions between aromatic units play a significant role in chemistry (Hunter, 1994), crystal engineering (Desiraju, 1995) and biology. Recently, we have reported the convenient syntheses of 1,3-bis(4,6-dimethylthio-1H-pyrazolo[3,4-d]pyrimidin-1-yl)propane, (I) (Avasthi et al., 1995) and 1,1'-(1,3-propanediyl)bis(5-methyl-6-methylthio-4,5-dihydro-1H- pyrazolo[3,4-d]pyrimidin-4-one, (II) (Avasthi et al., 1998), and X-ray studies (Biswas et al., 1995; Maulik et al., 1998) of two novel `propylene linker' compounds based on pyrazolo[3,4-d]pyrimidines. More recently, the ethyl analogues 1,3-bis(4,6-diethylthio-1H-pyrazolo[3,4-d]pyrimidin-1-yl)propane, (III), and 1,1'-(1,3-propanediyl)bis(5-ethyl-6-methylthio-4,5-dihydro-1H- pyrazolo[3,4-d]pyrimidin-4-one, (IV), of compounds (I) and (II) have been synthesized, and X-ray crystallography of these compounds also showed inter- and intramolecular stacking (Avasthi, Rawat et al., 2001; Avasthi, Aswal & Maulik, 2001).
Efforts to crystallize the intermediate compound, (V), obtained during the transformation of (I) to (II) or (I) to (IV), were not successful. This common intermediate, (V), is a cyclic amide (lactam) and capable of intermolecular dimerization similar to that of 2(1H)-pyridone (Gallant et al., 1991) and 4(3H)-pyrimidone (Vaillancourt et al., 1998). Due to the fact that all four compounds, (I)-(IV), showed inter- and intramolecular stacking, it became important to obtain more structural information about the common intermediate, (V). In this communication, we present an indirect strategy for the structural analysis of intermediate (V).
Since hydrogen bonding is a much stronger non-covalent interaction than stacking interactions (Muller-Dethlefs & Hobza, 2000; Desiraju & Steiner, 1999), synthesis of the title new compound, (VI), was envisioned. This compound is capable of hydrogen bonding similar to that of intermediate (V), from a crystal engineering point of view (Desiraju, 1995). Structurally, the new compound, (VI) is obtained by the replacement of one pyrazolo[3,4-d]pyrimidinyl moiety in intermediate (V) by another typical aromatic moiety, namely phenyl, which is well known for its stacking interactions (Desiraju & Steiner, 1999). \sch
Fig. 1 shows the molecular structure and conformation of (VI) with the atomic numbering scheme. There are two molecules in the asymmetric unit. Selected torsion angles are listed in Table 1. The planar phenyl rings make angles of 70.7 (1) and 80.7 (1)°, respectively, with the heterocyclic ring systems in the two molecules. The central angles at the trimethylene bridge, C8—C9—C10 111.1 (2) and C8'-C9'-C10' 112.3 (2)°, are quite similar in the two molecules. For comparison, these angles for the intramolecularly stacked (folded) compounds (I)-(IV) are 114.1 (2), 115.2 (2), 113.5 (2) and 114.9 (2)°, respectively.
In the molecule of (VI), intramolecular stacking is absent. However, the molecule is not fully extended. The phenyl ring is somewhat tilted towards the heterocyclic ring, due to C—H···π and C—H···N interactions (Fig. 1). One H atom on C8 shares hydrogen bonding with atoms C11 and C16 of the phenyl ring, due to C—H···π interactions (H8A···C11 2.67 and H8A···C16 2.89 Å).
The molecule of (VI) can be visualized as consisting of one polar end (with the lactam moiety as the head group) capable of strong intermolecular hydrogen bonding, and the other non-polar end (with the phenyl moiety as the tail group) capable of stacking interactions. Strong intermolecular hydrogen bonding of the type N—H···O═C [N5—H5···O17, with N···O distances of 2.794 (3) and 2.796 (3) Å, and angles of 168.9 and 174.8°, respectively] among the lactam moieties of the two molecules results in the formation of a dimeric structure (Fig. 2). At the non-polar end, phenyl C atoms interact with neighbouring phenyl C atoms (minimum C—C distance 3.94 Å) and a methylene H atom (C10—H10A···C14 3.88 Å, H10A···C14 2.98 Å and C10—H10A—C14 155.4°) through a C—H···π interaction. Thus, strong intermolecular hydrogen bonding among the polar lactam moieties and weak intermolecular C—H···π interactions in the non-polar moieties result in the formation of a layered structure with head-to-head and tail-to-tail packing arrangements (Fig. 3). To the best of our knowledge, this is first such example based on the pyrazolo[3,4-d]pyrimidine heterocycle, where a layered structure is formed by involvement of a bilayer-type structure.
In conclusion, the crystal structure of (VI) clearly shows that the simultaneous presence of inter- and/or intramolecular stacking interactions, along with hydrogen bonding in intermediate (V), are the most likely reasons for not allowing the formation of a single-crystal for crystallography. As compound (VI) does not have competing intramolecular stacking interactions, stronger hydrogen-bonding interactions take full control during crystallization, resulting in the formation of a beautiful dimeric layered structure. It is also important to mention here that the observation of such a dimeric structure for (VI) is significant, due to its isomeric relationship with purines and pyrimidines, which play a critical biological role in the self-association of nucleic acids.