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In the crystal structure of 1,1'-(1,3-propanediyl)bis(5-benzyl-6-methylsulfanyl-4,5-dihydro-1
H-pyrazolo[3,4-
d]pyrimidin-4-one), C
29H
28N
8O
2S
2, the pairs of pyrazolo[3,4-
d]pyrimidine rings stack as a result of intramolecular
-
interactions between the heterocyclic rings. The folded molecules are further stacked in pairs, due to intermolecular aromatic
-
interactions and C-H
O hydrogen bonds.
Supporting information
CCDC reference: 193435
Compound (III) was synthesized using the method described by Avasthi et
al. (1998). Diffraction quality crystals of (III) were obtained by slow
evaporation of an ethyl acetate solution at room temperature.
Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXTL (Bruker, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
1,1'-(1,3-propanediyl)bis(5-benzyl-6-methylthio-4,5-dihydro-1
H-pyrazolo
[3,4-
d]pyrimidine-4-one)
top
Crystal data top
C29H28N8O2S2 | Z = 2 |
Mr = 584.71 | F(000) = 612 |
Triclinic, P1 | Dx = 1.379 Mg m−3 |
Hall symbol: -P 1 | Melting point: 433 K |
a = 9.150 (1) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.491 (1) Å | Cell parameters from 38 reflections |
c = 16.839 (2) Å | θ = 4.8–12.5° |
α = 83.01 (1)° | µ = 0.23 mm−1 |
β = 85.26 (1)° | T = 293 K |
γ = 76.39 (1)° | Rectangular, colourless |
V = 1408.5 (3) Å3 | 0.35 × 0.28 × 0.25 mm |
Data collection top
Bruker P4 diffractometer | Rint = 0.021 |
Radiation source: fine-focus sealed tube | θmax = 26.0°, θmin = 2.2° |
Graphite monochromator | h = −1→11 |
θ/2θ scans | k = −11→11 |
6623 measured reflections | l = −20→20 |
5527 independent reflections | 3 standard reflections every 97 reflections |
3716 reflections with I > 2σ(I) | intensity decay: none |
Refinement top
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)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.121 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.047P)2 + 0.5548P] where P = (Fo2 + 2Fc2)/3 |
5527 reflections | (Δ/σ)max < 0.001 |
372 parameters | Δρmax = 0.18 e Å−3 |
0 restraints | Δρmin = −0.28 e Å−3 |
Crystal data top
C29H28N8O2S2 | γ = 76.39 (1)° |
Mr = 584.71 | V = 1408.5 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.150 (1) Å | Mo Kα radiation |
b = 9.491 (1) Å | µ = 0.23 mm−1 |
c = 16.839 (2) Å | T = 293 K |
α = 83.01 (1)° | 0.35 × 0.28 × 0.25 mm |
β = 85.26 (1)° | |
Data collection top
Bruker P4 diffractometer | Rint = 0.021 |
6623 measured reflections | 3 standard reflections every 97 reflections |
5527 independent reflections | intensity decay: none |
3716 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.121 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.18 e Å−3 |
5527 reflections | Δρmin = −0.28 e Å−3 |
372 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S2 | 0.67773 (9) | 0.46166 (7) | 0.33325 (4) | 0.0603 (2) | |
S1 | 0.38237 (8) | 0.11449 (7) | 0.20404 (4) | 0.0616 (2) | |
N1 | 0.7371 (2) | 0.3705 (2) | 0.03235 (11) | 0.0444 (5) | |
N2 | 0.7509 (2) | 0.5115 (2) | 0.01271 (12) | 0.0532 (5) | |
C3 | 0.6415 (3) | 0.5910 (3) | 0.05519 (15) | 0.0520 (6) | |
H3 | 0.6241 | 0.6918 | 0.0541 | 0.062* | |
C4 | 0.5545 (3) | 0.5049 (2) | 0.10221 (13) | 0.0429 (5) | |
C5 | 0.4223 (3) | 0.5301 (3) | 0.15497 (14) | 0.0453 (6) | |
N6 | 0.3744 (2) | 0.3985 (2) | 0.18224 (11) | 0.0431 (5) | |
C7 | 0.4543 (3) | 0.2640 (2) | 0.16165 (13) | 0.0420 (5) | |
N8 | 0.5757 (2) | 0.2405 (2) | 0.11473 (11) | 0.0431 (5) | |
C9 | 0.6195 (3) | 0.3648 (2) | 0.08509 (13) | 0.0397 (5) | |
C10 | 0.8353 (3) | 0.2499 (3) | −0.00598 (14) | 0.0478 (6) | |
H10A | 0.8081 | 0.2555 | −0.0609 | 0.057* | |
H10B | 0.8190 | 0.1586 | 0.0216 | 0.057* | |
C11 | 1.0006 (3) | 0.2504 (3) | −0.00567 (13) | 0.0476 (6) | |
H11A | 1.0598 | 0.1628 | −0.0268 | 0.057* | |
H11B | 1.0198 | 0.3333 | −0.0412 | 0.057* | |
C12 | 1.0529 (3) | 0.2580 (3) | 0.07640 (13) | 0.0471 (6) | |
H12A | 1.1617 | 0.2433 | 0.0732 | 0.056* | |
H12B | 1.0104 | 0.3544 | 0.0928 | 0.056* | |
N13 | 1.0095 (2) | 0.1497 (2) | 0.13662 (11) | 0.0446 (5) | |
N14 | 1.0544 (3) | 0.0044 (2) | 0.12774 (12) | 0.0563 (6) | |
C15 | 0.9861 (3) | −0.0610 (3) | 0.18839 (15) | 0.0560 (7) | |
H15 | 0.9966 | −0.1614 | 0.1978 | 0.067* | |
C16 | 0.8954 (3) | 0.0396 (2) | 0.23711 (13) | 0.0435 (6) | |
C17 | 0.7914 (3) | 0.0338 (3) | 0.30458 (14) | 0.0465 (6) | |
N18 | 0.7237 (2) | 0.1749 (2) | 0.32790 (10) | 0.0425 (5) | |
C19 | 0.7621 (3) | 0.3004 (2) | 0.29037 (13) | 0.0408 (5) | |
N20 | 0.8541 (2) | 0.3057 (2) | 0.22766 (11) | 0.0409 (4) | |
C21 | 0.9151 (3) | 0.1734 (2) | 0.20196 (13) | 0.0397 (5) | |
O22 | 0.3506 (2) | 0.64677 (19) | 0.17553 (10) | 0.0596 (5) | |
C23 | 0.2242 (3) | 0.4163 (3) | 0.22530 (14) | 0.0505 (6) | |
H23A | 0.1740 | 0.3465 | 0.2085 | 0.061* | |
H23B | 0.1652 | 0.5130 | 0.2087 | 0.061* | |
C24 | 0.2233 (3) | 0.3970 (3) | 0.31561 (14) | 0.0465 (6) | |
C25 | 0.1778 (3) | 0.2807 (3) | 0.35928 (16) | 0.0597 (7) | |
H25 | 0.1507 | 0.2114 | 0.3325 | 0.072* | |
C26 | 0.1719 (3) | 0.2650 (4) | 0.44179 (17) | 0.0695 (8) | |
H26 | 0.1429 | 0.1848 | 0.4703 | 0.083* | |
C27 | 0.2089 (3) | 0.3685 (4) | 0.48160 (17) | 0.0711 (8) | |
H27 | 0.2014 | 0.3606 | 0.5373 | 0.085* | |
C28 | 0.2567 (4) | 0.4832 (3) | 0.43936 (18) | 0.0757 (9) | |
H28 | 0.2847 | 0.5516 | 0.4665 | 0.091* | |
C29 | 0.2637 (3) | 0.4982 (3) | 0.35668 (16) | 0.0613 (7) | |
H29 | 0.2960 | 0.5768 | 0.3284 | 0.074* | |
C30 | 0.4974 (4) | −0.0284 (3) | 0.1524 (2) | 0.0816 (10) | |
H30A | 0.4913 | −0.0023 | 0.0957 | 0.122* | |
H30B | 0.4629 | −0.1165 | 0.1673 | 0.122* | |
H30C | 0.5999 | −0.0433 | 0.1664 | 0.122* | |
O31 | 0.7568 (2) | −0.07369 (19) | 0.34170 (11) | 0.0630 (5) | |
C32 | 0.6071 (3) | 0.1810 (3) | 0.39392 (13) | 0.0475 (6) | |
H32A | 0.5521 | 0.1066 | 0.3899 | 0.057* | |
H32B | 0.5363 | 0.2749 | 0.3872 | 0.057* | |
C33 | 0.6653 (3) | 0.1599 (2) | 0.47692 (13) | 0.0420 (5) | |
C34 | 0.5623 (3) | 0.1525 (3) | 0.54158 (14) | 0.0527 (6) | |
H34 | 0.4620 | 0.1580 | 0.5328 | 0.063* | |
C35 | 0.6076 (3) | 0.1371 (3) | 0.61875 (15) | 0.0593 (7) | |
H35 | 0.5373 | 0.1331 | 0.6616 | 0.071* | |
C36 | 0.7550 (3) | 0.1277 (3) | 0.63308 (15) | 0.0564 (7) | |
H36 | 0.7848 | 0.1176 | 0.6854 | 0.068* | |
C37 | 0.8583 (3) | 0.1333 (3) | 0.56950 (16) | 0.0567 (7) | |
H37 | 0.9588 | 0.1260 | 0.5786 | 0.068* | |
C38 | 0.8128 (3) | 0.1499 (3) | 0.49152 (15) | 0.0514 (6) | |
H38 | 0.8833 | 0.1543 | 0.4487 | 0.062* | |
C39 | 0.7735 (4) | 0.5868 (3) | 0.27542 (18) | 0.0750 (9) | |
H39A | 0.8801 | 0.5523 | 0.2801 | 0.112* | |
H39B | 0.7411 | 0.6808 | 0.2949 | 0.112* | |
H39C | 0.7506 | 0.5945 | 0.2202 | 0.112* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S2 | 0.0736 (5) | 0.0494 (4) | 0.0572 (4) | −0.0115 (3) | 0.0108 (4) | −0.0176 (3) |
S1 | 0.0661 (5) | 0.0512 (4) | 0.0691 (5) | −0.0244 (3) | 0.0048 (4) | 0.0034 (3) |
N1 | 0.0502 (12) | 0.0412 (11) | 0.0441 (11) | −0.0156 (9) | −0.0007 (10) | −0.0040 (9) |
N2 | 0.0625 (14) | 0.0466 (12) | 0.0538 (12) | −0.0224 (11) | 0.0039 (11) | −0.0035 (10) |
C3 | 0.0659 (17) | 0.0395 (13) | 0.0533 (15) | −0.0187 (13) | −0.0043 (13) | −0.0019 (11) |
C4 | 0.0492 (14) | 0.0403 (13) | 0.0409 (12) | −0.0132 (11) | −0.0051 (11) | −0.0034 (10) |
C5 | 0.0536 (15) | 0.0414 (14) | 0.0405 (13) | −0.0101 (12) | −0.0083 (11) | −0.0007 (10) |
N6 | 0.0451 (12) | 0.0463 (11) | 0.0391 (10) | −0.0131 (9) | −0.0027 (9) | −0.0033 (8) |
C7 | 0.0477 (14) | 0.0392 (13) | 0.0396 (12) | −0.0111 (11) | −0.0102 (11) | 0.0006 (10) |
N8 | 0.0490 (12) | 0.0371 (10) | 0.0431 (11) | −0.0117 (9) | −0.0010 (10) | −0.0018 (8) |
C9 | 0.0446 (13) | 0.0395 (13) | 0.0369 (12) | −0.0134 (11) | −0.0066 (10) | −0.0012 (9) |
C10 | 0.0532 (15) | 0.0517 (14) | 0.0405 (13) | −0.0134 (12) | −0.0013 (11) | −0.0104 (11) |
C11 | 0.0518 (15) | 0.0568 (15) | 0.0353 (12) | −0.0158 (12) | 0.0055 (11) | −0.0077 (11) |
C12 | 0.0505 (15) | 0.0552 (15) | 0.0387 (12) | −0.0192 (12) | −0.0002 (11) | −0.0053 (11) |
N13 | 0.0544 (12) | 0.0450 (11) | 0.0362 (10) | −0.0132 (9) | 0.0012 (9) | −0.0106 (8) |
N14 | 0.0733 (15) | 0.0474 (12) | 0.0461 (12) | −0.0058 (11) | 0.0008 (11) | −0.0152 (10) |
C15 | 0.081 (2) | 0.0435 (14) | 0.0432 (14) | −0.0125 (14) | −0.0006 (14) | −0.0088 (11) |
C16 | 0.0544 (15) | 0.0392 (13) | 0.0383 (12) | −0.0112 (11) | −0.0057 (11) | −0.0071 (10) |
C17 | 0.0603 (16) | 0.0424 (13) | 0.0405 (13) | −0.0173 (12) | −0.0085 (12) | −0.0037 (11) |
N18 | 0.0496 (12) | 0.0435 (11) | 0.0365 (10) | −0.0156 (9) | 0.0013 (9) | −0.0055 (8) |
C19 | 0.0481 (14) | 0.0406 (12) | 0.0362 (12) | −0.0122 (11) | −0.0080 (11) | −0.0060 (10) |
N20 | 0.0504 (12) | 0.0392 (10) | 0.0355 (10) | −0.0136 (9) | −0.0022 (9) | −0.0069 (8) |
C21 | 0.0467 (14) | 0.0426 (13) | 0.0329 (11) | −0.0139 (11) | −0.0041 (10) | −0.0077 (9) |
O22 | 0.0723 (13) | 0.0427 (10) | 0.0591 (11) | −0.0042 (9) | 0.0022 (9) | −0.0080 (8) |
C23 | 0.0429 (14) | 0.0603 (16) | 0.0485 (14) | −0.0124 (12) | −0.0037 (11) | −0.0044 (12) |
C24 | 0.0386 (13) | 0.0513 (15) | 0.0479 (14) | −0.0066 (11) | 0.0010 (11) | −0.0082 (11) |
C25 | 0.0583 (17) | 0.0747 (19) | 0.0548 (16) | −0.0324 (15) | −0.0010 (13) | −0.0079 (14) |
C26 | 0.0681 (19) | 0.088 (2) | 0.0554 (17) | −0.0338 (17) | 0.0072 (15) | 0.0047 (16) |
C27 | 0.077 (2) | 0.087 (2) | 0.0445 (15) | −0.0102 (18) | 0.0067 (15) | −0.0111 (15) |
C28 | 0.110 (3) | 0.0599 (18) | 0.0581 (18) | −0.0128 (18) | −0.0041 (18) | −0.0234 (15) |
C29 | 0.083 (2) | 0.0482 (15) | 0.0524 (16) | −0.0137 (14) | 0.0005 (14) | −0.0104 (12) |
C30 | 0.108 (3) | 0.0469 (17) | 0.094 (2) | −0.0310 (17) | 0.011 (2) | −0.0091 (16) |
O31 | 0.0846 (14) | 0.0471 (10) | 0.0605 (11) | −0.0279 (10) | 0.0071 (10) | −0.0005 (9) |
C32 | 0.0462 (14) | 0.0553 (15) | 0.0432 (13) | −0.0175 (12) | 0.0038 (11) | −0.0056 (11) |
C33 | 0.0492 (15) | 0.0363 (12) | 0.0413 (12) | −0.0131 (11) | 0.0018 (11) | −0.0029 (9) |
C34 | 0.0468 (15) | 0.0636 (16) | 0.0467 (14) | −0.0158 (13) | 0.0027 (12) | 0.0011 (12) |
C35 | 0.0630 (18) | 0.0670 (18) | 0.0443 (15) | −0.0161 (14) | 0.0101 (13) | 0.0022 (12) |
C36 | 0.075 (2) | 0.0559 (16) | 0.0397 (14) | −0.0177 (14) | −0.0088 (14) | 0.0012 (11) |
C37 | 0.0527 (16) | 0.0631 (17) | 0.0558 (16) | −0.0147 (13) | −0.0097 (13) | −0.0038 (13) |
C38 | 0.0495 (16) | 0.0608 (16) | 0.0440 (14) | −0.0143 (13) | 0.0035 (12) | −0.0063 (12) |
C39 | 0.107 (3) | 0.0441 (16) | 0.076 (2) | −0.0199 (16) | 0.0072 (18) | −0.0157 (14) |
Geometric parameters (Å, º) top
S2—C19 | 1.755 (2) | N18—C32 | 1.473 (3) |
S2—C39 | 1.787 (3) | C19—N20 | 1.299 (3) |
S1—C7 | 1.752 (2) | N20—C21 | 1.356 (3) |
S1—C30 | 1.779 (3) | C23—C24 | 1.509 (3) |
N1—C9 | 1.344 (3) | C23—H23A | 0.9700 |
N1—N2 | 1.371 (3) | C23—H23B | 0.9700 |
N1—C10 | 1.461 (3) | C24—C25 | 1.379 (4) |
N2—C3 | 1.319 (3) | C24—C29 | 1.381 (4) |
C3—C4 | 1.405 (3) | C25—C26 | 1.377 (4) |
C3—H3 | 0.9300 | C25—H25 | 0.9300 |
C4—C9 | 1.378 (3) | C26—C27 | 1.372 (4) |
C4—C5 | 1.431 (3) | C26—H26 | 0.9300 |
C5—O22 | 1.221 (3) | C27—C28 | 1.366 (4) |
C5—N6 | 1.431 (3) | C27—H27 | 0.9300 |
N6—C7 | 1.383 (3) | C28—C29 | 1.380 (4) |
N6—C23 | 1.483 (3) | C28—H28 | 0.9300 |
C7—N8 | 1.300 (3) | C29—H29 | 0.9300 |
N8—C9 | 1.360 (3) | C30—H30A | 0.9600 |
C10—C11 | 1.515 (3) | C30—H30B | 0.9600 |
C10—H10A | 0.9700 | C30—H30C | 0.9600 |
C10—H10B | 0.9700 | C32—C33 | 1.511 (3) |
C11—C12 | 1.514 (3) | C32—H32A | 0.9700 |
C11—H11A | 0.9700 | C32—H32B | 0.9700 |
C11—H11B | 0.9700 | C33—C38 | 1.372 (3) |
C12—N13 | 1.454 (3) | C33—C34 | 1.386 (3) |
C12—H12A | 0.9700 | C34—C35 | 1.377 (4) |
C12—H12B | 0.9700 | C34—H34 | 0.9300 |
N13—C21 | 1.349 (3) | C35—C36 | 1.370 (4) |
N13—N14 | 1.366 (3) | C35—H35 | 0.9300 |
N14—C15 | 1.320 (3) | C36—C37 | 1.373 (4) |
C15—C16 | 1.407 (3) | C36—H36 | 0.9300 |
C15—H15 | 0.9300 | C37—C38 | 1.390 (3) |
C16—C21 | 1.379 (3) | C37—H37 | 0.9300 |
C16—C17 | 1.425 (3) | C38—H38 | 0.9300 |
C17—O31 | 1.223 (3) | C39—H39A | 0.9600 |
C17—N18 | 1.424 (3) | C39—H39B | 0.9600 |
N18—C19 | 1.385 (3) | C39—H39C | 0.9600 |
| | | |
C19—S2—C39 | 100.58 (12) | N13—C21—N20 | 125.2 (2) |
C7—S1—C30 | 101.29 (13) | N13—C21—C16 | 107.4 (2) |
C9—N1—N2 | 110.91 (19) | N20—C21—C16 | 127.4 (2) |
C9—N1—C10 | 127.47 (19) | N6—C23—C24 | 116.1 (2) |
N2—N1—C10 | 121.48 (19) | N6—C23—H23A | 108.3 |
C3—N2—N1 | 105.21 (19) | C24—C23—H23A | 108.3 |
N2—C3—C4 | 111.7 (2) | N6—C23—H23B | 108.3 |
N2—C3—H3 | 124.1 | C24—C23—H23B | 108.3 |
C4—C3—H3 | 124.1 | H23A—C23—H23B | 107.4 |
C9—C4—C3 | 104.3 (2) | C25—C24—C29 | 118.3 (2) |
C9—C4—C5 | 119.2 (2) | C25—C24—C23 | 121.0 (2) |
C3—C4—C5 | 136.4 (2) | C29—C24—C23 | 120.7 (2) |
O22—C5—N6 | 120.5 (2) | C26—C25—C24 | 121.3 (3) |
O22—C5—C4 | 127.4 (2) | C26—C25—H25 | 119.4 |
N6—C5—C4 | 112.1 (2) | C24—C25—H25 | 119.4 |
C7—N6—C5 | 122.22 (19) | C27—C26—C25 | 119.6 (3) |
C7—N6—C23 | 121.31 (19) | C27—C26—H26 | 120.2 |
C5—N6—C23 | 116.03 (19) | C25—C26—H26 | 120.2 |
N8—C7—N6 | 125.8 (2) | C28—C27—C26 | 120.0 (3) |
N8—C7—S1 | 118.57 (17) | C28—C27—H27 | 120.0 |
N6—C7—S1 | 115.64 (17) | C26—C27—H27 | 120.0 |
C7—N8—C9 | 113.07 (19) | C27—C28—C29 | 120.4 (3) |
N1—C9—N8 | 124.6 (2) | C27—C28—H28 | 119.8 |
N1—C9—C4 | 107.81 (19) | C29—C28—H28 | 119.8 |
N8—C9—C4 | 127.5 (2) | C28—C29—C24 | 120.4 (3) |
N1—C10—C11 | 112.93 (19) | C28—C29—H29 | 119.8 |
N1—C10—H10A | 109.0 | C24—C29—H29 | 119.8 |
C11—C10—H10A | 109.0 | S1—C30—H30A | 109.5 |
N1—C10—H10B | 109.0 | S1—C30—H30B | 109.5 |
C11—C10—H10B | 109.0 | H30A—C30—H30B | 109.5 |
H10A—C10—H10B | 107.8 | S1—C30—H30C | 109.5 |
C12—C11—C10 | 113.96 (19) | H30A—C30—H30C | 109.5 |
C12—C11—H11A | 108.8 | H30B—C30—H30C | 109.5 |
C10—C11—H11A | 108.8 | N18—C32—C33 | 115.0 (2) |
C12—C11—H11B | 108.8 | N18—C32—H32A | 108.5 |
C10—C11—H11B | 108.8 | C33—C32—H32A | 108.5 |
H11A—C11—H11B | 107.7 | N18—C32—H32B | 108.5 |
N13—C12—C11 | 112.60 (19) | C33—C32—H32B | 108.5 |
N13—C12—H12A | 109.1 | H32A—C32—H32B | 107.5 |
C11—C12—H12A | 109.1 | C38—C33—C34 | 118.7 (2) |
N13—C12—H12B | 109.1 | C38—C33—C32 | 123.7 (2) |
C11—C12—H12B | 109.1 | C34—C33—C32 | 117.6 (2) |
H12A—C12—H12B | 107.8 | C35—C34—C33 | 120.4 (2) |
C21—N13—N14 | 111.28 (19) | C35—C34—H34 | 119.8 |
C21—N13—C12 | 127.6 (2) | C33—C34—H34 | 119.8 |
N14—N13—C12 | 120.88 (19) | C36—C35—C34 | 120.8 (2) |
C15—N14—N13 | 105.16 (19) | C36—C35—H35 | 119.6 |
N14—C15—C16 | 111.8 (2) | C34—C35—H35 | 119.6 |
N14—C15—H15 | 124.1 | C35—C36—C37 | 119.3 (2) |
C16—C15—H15 | 124.1 | C35—C36—H36 | 120.3 |
C21—C16—C15 | 104.3 (2) | C37—C36—H36 | 120.3 |
C21—C16—C17 | 119.1 (2) | C36—C37—C38 | 120.1 (3) |
C15—C16—C17 | 136.4 (2) | C36—C37—H37 | 120.0 |
O31—C17—N18 | 119.8 (2) | C38—C37—H37 | 120.0 |
O31—C17—C16 | 128.1 (2) | C33—C38—C37 | 120.8 (2) |
N18—C17—C16 | 112.1 (2) | C33—C38—H38 | 119.6 |
C19—N18—C17 | 122.64 (19) | C37—C38—H38 | 119.6 |
C19—N18—C32 | 121.25 (19) | S2—C39—H39A | 109.5 |
C17—N18—C32 | 116.11 (19) | S2—C39—H39B | 109.5 |
N20—C19—N18 | 125.0 (2) | H39A—C39—H39B | 109.5 |
N20—C19—S2 | 119.29 (17) | S2—C39—H39C | 109.5 |
N18—C19—S2 | 115.69 (17) | H39A—C39—H39C | 109.5 |
C19—N20—C21 | 113.46 (19) | H39B—C39—H39C | 109.5 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C10—H10A···O22i | 0.97 | 2.47 | 3.367 (3) | 154 |
Symmetry code: (i) −x+1, −y+1, −z. |
Experimental details
Crystal data |
Chemical formula | C29H28N8O2S2 |
Mr | 584.71 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 9.150 (1), 9.491 (1), 16.839 (2) |
α, β, γ (°) | 83.01 (1), 85.26 (1), 76.39 (1) |
V (Å3) | 1408.5 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.23 |
Crystal size (mm) | 0.35 × 0.28 × 0.25 |
|
Data collection |
Diffractometer | Bruker P4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6623, 5527, 3716 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.617 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.121, 1.01 |
No. of reflections | 5527 |
No. of parameters | 372 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.18, −0.28 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C10—H10A···O22i | 0.97 | 2.47 | 3.367 (3) | 154 |
Symmetry code: (i) −x+1, −y+1, −z. |
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Interactions between aromatic units play a significant role in chemistry (Hunter et al., 2001; Tsuzuki et al., 2002), crystal engineering (Desiraju, 1995) and biology. In recent years, we have reported the convenient syntheses (Avasthi et al., 1995, 1998; Avasthi, Rawat et al., 2001) and the X-ray structures (Biswas et al., 1995; Maulik et al., 1998, 2000; Avasthi, Rawat et al., 2001; Avasthi, Aswal & Maulik, 2001) of several novel `propylene linker' compounds based on the pyrazolo[3,4-d]pyrimidine core, which is isomeric with biologically important purine, as flexible new models for studying aromatic π–π interactions (APPI). Two of these compounds, 1,1'-(1,3-propanediyl)bis(5-methyl-6-methylthio-4,5-dihydro-1H- pyrazolo[3,4-d]pyrimidin-4-one), (I), and 1,1'-(1,3-propanediyl)bis(5-ethyl-6-methylthio-dihydro-1H- pyrazolo[3,4-d]pyrimidin-4-one), (II), show inter- and intramolecular stacking due to APPI (Maulik et al., 1998; Avasthi, Aswal & Maulik, 2001) when studied using X-ray crystallography. Since the X-ray structures of (I) and (II) are quite similar, in having a U-motif for the demonstration of inter- and intramolecular stacking, it was considered worthwhile to replace the N-methyl/ethyl group of (I) and (II) with a bulky N-benzyl group, to determine the robustness of the U-motif and its consequence for the intermolecular stacking from a crystal engineering point of view. In this communication, we report the X-ray structure of 1,1'-(1,3-propanediyl)bis(5-benzyl-6-methylthio-4,5-dihydro-1H-pyrazolo [3,4-d]pyrimidin-4-one), (III), the synthesis of which has been described earlier by Avasthi et al. (1998). \sch
The molecular structure and conformation of (III) are shown in Fig. 1. The structure is folded at the centre of the bridge [C10—C11—C12 114.0 (2)°] due to intramolecular APPI between the pyrazolo[3,4-d]pyrimidine rings. For comparison, the folding angles in (I) and (II) are 115.2 (2) and 114.9 (2)°, respectively. In compound (III), as in (I) and (II), the folded pyrazolo[3,4-d]pyrimidine rings are positioned in such a way that only part of the pyrimidinyl rings overlap. The overlapping six-membered rings are separated by an average distance of 3.428 (3) Å [3.37 (1) Å in (I) and 3.415 (3) Å in (II)], thus confirming the presence of intramolecular APPI.
The pyrazolo[3,4-d]pyrimidine rings in (III) are nearly planar [maximum deviation -0.048 (2) Å] and the angle between the least-squares planes is 14.5 (1)° [12.4 (5)° in (I) and 12.5 (1)° in (II)]. The crystal packing (Fig. 2) shows further independent intermolecular stacking between the pyrazolo[3,4-d]pyrimidine systems due to π–π interactions. Pairs of pyrazolo[3,4-d]pyrimidine rings (related by symmetry code 1 - x, 1 - y, -z) overlap, with an interplanar separation of 3.370 (2) Å in a `parallel displaced' orientation [the dihedral angle of a stacking pair is 1.0 (1)°].
Interestingly, these stacked pyrazolo[3,4-d]pyrimidine rings are also connected by intermolecular C—H···O hydrogen bonding (Table 1; Desiraju & Steiner, 1999). Thus, the combination of intra- and intermolecular APPI and intermolecular hydrogen bonding results in the formation of a stacked-dimeric unit of (III). The continuous intermolecular stacking present in (I) and (II) is absent in (III). The crystal structure of (III) is stabilized mainly by C—H···O bonding, π–π interactions and van der Waals forces.