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The molecular structure of the title compound, C17H20N4OS2, does not show any intramolecular aromatic π–π interactions, but the crystal packing reveals the presence of intermolecular C—H...O and C—H...π interactions. The C—H...O interactions generate chains of mol­ecules that are linked into sheets by C—H...π interactions about inversion centres.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103015324/fg1701sup1.cif
Contains datablocks global, paper, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270103015324/fg1701Isup2.hkl
Contains datablock I

CCDC reference: 221072

Comment top

Arene interactions are known to play an important role in chemistry (Hunter & Sanders, 1990; Hunter et al., 2001; Tsuzuki et al., 2002) and biology. These interactions play a significant role in molecular recognition, stabilization of DNA/RNA structures (Hobza & Sponer, 1999), crystal engineering (Desiraju, 1995) and drug development (Meyer et al., 2003). Use of a polymethylene, especially a trimethylene (propylene), linker for studying intramolecular ππ interactions was pioneered by Browne et al. (1968), and early work has been reviewed by Leonard (1979). In 1995 we reported the synthesis (Avasthi et al., 1995) and X-ray structure (Biswas et al., 1995) of a `trimethylene linker' molecule that exhibits intramolecular stacking based on a pyrazolo[3,4-d]pyrimidine core, which is isomeric with the biologically important purine system. The robustness of the unusual U-motif formed as a result of the intramolecular stacking has been further demonstrated by X-ray diffraction of other closely related "propylene linker" compounds (Maulik et al., 1998; Avasthi, Aswal & Maulik, 2001; Avasthi, Rawat et al., 2001). Interestingly, no intramolecular stacking is observed by X-ray diffraction when the `trimethylene linker' is replaced by an `ethylene linker' (Avasthi, Rawat et al., 2001), a `tetramethylene linker' (Maulik et al., 2000) or a `pentamethylene linker' (Avasthi et al., 2003). All of these compounds have pyrazolo[3,4-d]pyrimidine-derived moieties at both ends of the polymethylene linker.

We report here the structure of the dissymmetric title compound, (I) (Fig. 1), which has normal dimensions and which has the same pyrazolo[3,4-d]pyrimidine core as reported in previous work on a `propylene linker' dissymmetric compound, (II) (Avasthi et al., 2002). Compound (I) has a `tetramethylene linker' flanked by pyrazolo[3,4-d]pyrimidinyl and electron-rich phenoxy moieties. It was anticipated that this configuration might have facilitated intramolecular stacking between the electron-rich phenoxy moiety and the electron-deficient pyrimidine portion, but Fig. 1 and various geometry calculations do not show any intramolecular stacking between the pyrazolo[3,4-d]pyrimidinyl and phenoxy moieties.

In the crystal structure, the molecules are linked by C—H···O hydrogen bonds (Table 2 and Fig. 2a) and chains of molecules are developed in the c direction by the operation of a c-glide plane. There are also C—H···π interactions between inversion-related molecules, as shown in Fig. 2(b), between C11—H11A and the centroid of the C13–C18 phenyl ring at (1 − x,1 − y,1 − z) [H11···Cg = 2.87 and C11—H11A···Cg = 146°; Cg is the centroid of the C13–C18 phenyl ring at (1 − x,1 − y,1 − z)]. These interactions link the chains of molecules into sheets.

Experimental top

Compound (I) was prepared by stirring an equimolar mixture of 4,6-bis- (methylsulfanyl)-1H-pyrazolo[3,4-d]pyrimidine and 4-phenoxybutyl bromide in DMF/K2CO3 solution. A diffraction-quality crystal was prepared from a solution of (I) in ethyl acetate and methanol by slow evaporation at room temperature.

Refinement top

All H atoms were placed in idealized positions and allowed to ride on their parent atoms for the final cycles of refinement, with C—H distances in the range 0.93–0.97 Å

Computing details top

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.

Figures top
[Figure 1]
[Figure 2]
Fig. 1. A displacement ellipsoid plot (30% probability level), showing the molecular structure of (I) and the atomic labelling scheme.

Fig. 2a. Part of a crystal-packing diagram of (I), showing chains of molecules extending in the c direction via C—H···O hydrogen bonding and the c-glide translation. Atoms marked with an asterisk (*) or hash (#) are at the symmetry positions (x,1/2 − y,z − 1/2) and (x,1/2 − y,1/2 + z), respectively.

Fig. 2 b. A view of pairs of C—H···π interactions linking molecules about the inversion centre at (1/2,1/2,1/2). Atoms marked with a dollar symbol are at the symmetry position (1 − x,1 − y,1 − z).
4,6-Bis(methylsulfanyl)-1-(4-phenoxybutyl)-1H-pyrazolo[3,4-d]pyrimidine top
Crystal data top
C17H20N4OS2F(000) = 760
Mr = 360.49Dx = 1.360 Mg m3
Monoclinic, P21/cMelting point: 355 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 17.966 (1) ÅCell parameters from 40 reflections
b = 10.089 (1) Åθ = 5.0–12.5°
c = 10.055 (1) ŵ = 0.31 mm1
β = 104.97 (1)°T = 293 K
V = 1760.7 (3) Å3Block, colourless
Z = 40.30 × 0.25 × 0.20 mm
Data collection top
Bruker P4
diffractometer
Rint = 0.023
Radiation source: fine-focus sealed tubeθmax = 26.0°, θmin = 2.3°
Graphite monochromatorh = 2221
θ–2θ scansk = 112
4550 measured reflectionsl = 112
3468 independent reflections3 standard reflections every 97 reflections
2333 reflections with I > 2σ(I) intensity decay: none
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.041H-atom parameters constrained
wR(F2) = 0.105 w = 1/[σ2(Fo2) + (0.0313P)2 + 0.9524P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.001
3468 reflectionsΔρmax = 0.23 e Å3
220 parametersΔρmin = 0.23 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0064 (6)
Crystal data top
C17H20N4OS2V = 1760.7 (3) Å3
Mr = 360.49Z = 4
Monoclinic, P21/cMo Kα radiation
a = 17.966 (1) ŵ = 0.31 mm1
b = 10.089 (1) ÅT = 293 K
c = 10.055 (1) Å0.30 × 0.25 × 0.20 mm
β = 104.97 (1)°
Data collection top
Bruker P4
diffractometer
Rint = 0.023
4550 measured reflections3 standard reflections every 97 reflections
3468 independent reflections intensity decay: none
2333 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0410 restraints
wR(F2) = 0.105H-atom parameters constrained
S = 1.05Δρmax = 0.23 e Å3
3468 reflectionsΔρmin = 0.23 e Å3
220 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
xyzUiso*/Ueq
S10.18353 (4)0.04247 (6)0.03747 (8)0.0517 (2)
S20.02684 (4)0.33764 (7)0.19747 (8)0.0551 (2)
N10.23616 (11)0.42670 (19)0.0444 (2)0.0413 (5)
N20.28677 (12)0.3486 (2)0.0906 (2)0.0488 (5)
C30.27068 (14)0.2253 (3)0.0649 (3)0.0487 (6)
H30.29610.15150.08700.058*
C3A0.20969 (13)0.2193 (2)0.0005 (2)0.0397 (5)
C40.16530 (13)0.1266 (2)0.0511 (2)0.0407 (6)
N50.11045 (11)0.16672 (19)0.1088 (2)0.0424 (5)
C60.09928 (13)0.3001 (2)0.1153 (2)0.0413 (6)
N70.13496 (11)0.39740 (19)0.0698 (2)0.0418 (5)
C7A0.18985 (12)0.3516 (2)0.0124 (2)0.0381 (5)
C80.24105 (14)0.5703 (2)0.0463 (2)0.0452 (6)
H8A0.19250.60730.03860.054*
H8B0.24890.59820.13400.054*
C90.30577 (14)0.6254 (2)0.0689 (2)0.0425 (6)
H9A0.35480.59770.05430.051*
H9B0.30390.72150.06520.051*
C100.30141 (14)0.5804 (3)0.2106 (2)0.0453 (6)
H10A0.25370.61220.22730.054*
H10B0.30060.48430.21300.054*
C110.36802 (14)0.6299 (2)0.3234 (2)0.0416 (6)
H11A0.41650.60600.30410.050*
H11B0.36580.72550.33090.050*
O120.36153 (9)0.56835 (16)0.44844 (16)0.0448 (4)
C130.41914 (13)0.5879 (2)0.5664 (2)0.0377 (5)
C140.40921 (15)0.5258 (3)0.6833 (2)0.0465 (6)
H140.36570.47420.67860.056*
C150.46360 (15)0.5406 (3)0.8062 (3)0.0528 (7)
H150.45660.49910.88470.063*
C160.52859 (15)0.6165 (3)0.8148 (3)0.0532 (7)
H160.56540.62580.89840.064*
C170.53846 (14)0.6782 (3)0.6983 (3)0.0512 (7)
H170.58200.72980.70360.061*
C180.48385 (14)0.6642 (2)0.5731 (3)0.0454 (6)
H180.49080.70570.49460.055*
C190.10826 (16)0.1177 (3)0.0982 (3)0.0617 (8)
H19A0.11090.08680.18960.092*
H19B0.11430.21230.09940.092*
H19C0.05920.09440.03820.092*
C200.02897 (16)0.5155 (3)0.2001 (3)0.0575 (7)
H20A0.07920.54520.25000.086*
H20B0.00890.54800.24410.086*
H20C0.01770.54840.10740.086*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0517 (4)0.0389 (3)0.0685 (5)0.0015 (3)0.0229 (3)0.0055 (3)
S20.0544 (4)0.0478 (4)0.0733 (5)0.0022 (3)0.0351 (4)0.0039 (4)
N10.0427 (11)0.0436 (12)0.0390 (11)0.0036 (9)0.0131 (9)0.0026 (9)
N20.0500 (12)0.0540 (13)0.0479 (12)0.0016 (10)0.0227 (10)0.0071 (11)
C30.0495 (15)0.0474 (14)0.0537 (16)0.0005 (12)0.0218 (13)0.0092 (13)
C3A0.0384 (12)0.0417 (13)0.0400 (13)0.0021 (11)0.0119 (11)0.0050 (11)
C40.0397 (13)0.0397 (13)0.0398 (14)0.0002 (10)0.0053 (11)0.0061 (11)
N50.0418 (11)0.0393 (11)0.0488 (12)0.0011 (9)0.0165 (9)0.0021 (10)
C60.0381 (12)0.0429 (14)0.0434 (14)0.0004 (10)0.0114 (11)0.0045 (11)
N70.0425 (11)0.0387 (11)0.0462 (12)0.0026 (9)0.0150 (10)0.0023 (9)
C7A0.0356 (12)0.0423 (13)0.0358 (13)0.0019 (10)0.0082 (10)0.0019 (11)
C80.0519 (14)0.0441 (14)0.0391 (14)0.0020 (12)0.0107 (12)0.0075 (12)
C90.0480 (14)0.0378 (13)0.0432 (14)0.0038 (11)0.0141 (12)0.0039 (11)
C100.0481 (14)0.0489 (14)0.0406 (14)0.0078 (12)0.0144 (11)0.0011 (12)
C110.0492 (14)0.0405 (13)0.0363 (13)0.0044 (11)0.0135 (11)0.0005 (11)
O120.0496 (10)0.0497 (10)0.0355 (9)0.0091 (8)0.0117 (8)0.0024 (8)
C130.0457 (13)0.0334 (12)0.0345 (13)0.0034 (10)0.0110 (11)0.0039 (10)
C140.0516 (14)0.0467 (14)0.0430 (15)0.0003 (12)0.0156 (12)0.0014 (12)
C150.0636 (17)0.0567 (16)0.0376 (15)0.0113 (14)0.0121 (13)0.0033 (13)
C160.0536 (16)0.0547 (16)0.0459 (16)0.0130 (13)0.0030 (13)0.0091 (13)
C170.0436 (14)0.0467 (15)0.0610 (18)0.0004 (12)0.0094 (13)0.0088 (14)
C180.0520 (14)0.0405 (13)0.0455 (15)0.0000 (11)0.0158 (12)0.0018 (12)
C190.0597 (17)0.0469 (16)0.082 (2)0.0051 (13)0.0243 (16)0.0007 (15)
C200.0622 (17)0.0491 (16)0.0660 (19)0.0066 (13)0.0254 (15)0.0088 (14)
Geometric parameters (Å, º) top
S1—C41.749 (2)C10—H10A0.9700
S1—C191.790 (3)C10—H10B0.9700
S2—C61.754 (2)C11—O121.434 (3)
S2—C201.794 (3)C11—H11A0.9700
N1—C7A1.356 (3)C11—H11B0.9700
N1—N21.371 (3)O12—C131.372 (3)
N1—C81.452 (3)C13—C181.381 (3)
N2—C31.318 (3)C13—C141.383 (3)
C3—C3A1.418 (3)C14—C151.371 (3)
C3—H30.9300C14—H140.9300
C3A—C7A1.394 (3)C15—C161.380 (4)
C3A—C41.407 (3)C15—H150.9300
C4—N51.329 (3)C16—C171.378 (4)
N5—C61.365 (3)C16—H160.9300
C6—N71.317 (3)C17—C181.389 (3)
N7—C7A1.346 (3)C17—H170.9300
C8—C91.519 (3)C18—H180.9300
C8—H8A0.9700C19—H19A0.9600
C8—H8B0.9700C19—H19B0.9600
C9—C101.517 (3)C19—H19C0.9600
C9—H9A0.9700C20—H20A0.9600
C9—H9B0.9700C20—H20B0.9600
C10—C111.505 (3)C20—H20C0.9600
C6—S2—C20101.95 (12)C9—C10—H10B109.1
C4—S1—C19102.34 (12)H10A—C10—H10B107.8
C7A—N1—N2110.74 (19)O12—C11—C10106.77 (18)
C7A—N1—C8127.5 (2)O12—C11—H11A110.4
N2—N1—C8121.41 (19)C10—C11—H11A110.4
C3—N2—N1106.15 (19)O12—C11—H11B110.4
N2—C3—C3A111.4 (2)C10—C11—H11B110.4
N2—C3—H3124.3H11A—C11—H11B108.6
C3A—C3—H3124.3C13—O12—C11118.82 (18)
C7A—C3A—C4115.1 (2)O12—C13—C18124.0 (2)
C7A—C3A—C3104.2 (2)O12—C13—C14115.8 (2)
C4—C3A—C3140.7 (2)C18—C13—C14120.1 (2)
N5—C4—C3A120.6 (2)C15—C14—C13119.9 (2)
N5—C4—S1120.41 (18)C15—C14—H14120.0
C3A—C4—S1119.02 (18)C13—C14—H14120.0
C4—N5—C6117.1 (2)C14—C15—C16120.7 (3)
N7—C6—N5128.8 (2)C14—C15—H15119.6
N7—C6—S2119.34 (18)C16—C15—H15119.6
N5—C6—S2111.81 (17)C17—C16—C15119.3 (2)
C6—N7—C7A111.7 (2)C17—C16—H16120.3
N7—C7A—N1125.8 (2)C15—C16—H16120.3
N7—C7A—C3A126.7 (2)C16—C17—C18120.5 (2)
N1—C7A—C3A107.48 (19)C16—C17—H17119.7
N1—C8—C9113.1 (2)C18—C17—H17119.7
N1—C8—H8A109.0C13—C18—C17119.3 (2)
C9—C8—H8A109.0C13—C18—H18120.3
N1—C8—H8B109.0C17—C18—H18120.3
C9—C8—H8B109.0S1—C19—H19A109.5
H8A—C8—H8B107.8S1—C19—H19B109.5
C10—C9—C8113.05 (19)H19A—C19—H19B109.5
C10—C9—H9A109.0S1—C19—H19C109.5
C8—C9—H9A109.0H19A—C19—H19C109.5
C10—C9—H9B109.0H19B—C19—H19C109.5
C8—C9—H9B109.0S2—C20—H20A109.5
H9A—C9—H9B107.8S2—C20—H20B109.5
C11—C10—C9112.62 (19)H20A—C20—H20B109.5
C11—C10—H10A109.1S2—C20—H20C109.5
C9—C10—H10A109.1H20A—C20—H20C109.5
C11—C10—H10B109.1H20B—C20—H20C109.5
C7A—N1—N2—C31.3 (3)N2—N1—C7A—C3A1.3 (3)
C8—N1—N2—C3175.2 (2)C8—N1—C7A—C3A174.7 (2)
N1—N2—C3—C3A0.8 (3)C4—C3A—C7A—N71.9 (4)
N2—C3—C3A—C7A0.1 (3)C3—C3A—C7A—N7179.2 (2)
N2—C3—C3A—C4178.5 (3)C4—C3A—C7A—N1178.17 (19)
C7A—C3A—C4—N51.8 (3)C3—C3A—C7A—N10.7 (3)
C3—C3A—C4—N5179.9 (3)C7A—N1—C8—C996.0 (3)
C7A—C3A—C4—S1178.39 (17)N2—N1—C8—C976.7 (3)
C3—C3A—C4—S10.1 (4)N1—C8—C9—C1055.2 (3)
C19—S1—C4—N55.7 (2)C8—C9—C10—C11177.0 (2)
C19—S1—C4—C3A174.5 (2)C9—C10—C11—O12173.54 (19)
C3A—C4—N5—C60.5 (3)C10—C11—O12—C13174.57 (19)
S1—C4—N5—C6179.72 (17)C11—O12—C13—C180.2 (3)
C4—N5—C6—N71.2 (4)C11—O12—C13—C14179.9 (2)
C4—N5—C6—S2178.59 (16)O12—C13—C14—C15179.5 (2)
C20—S2—C6—N73.1 (2)C18—C13—C14—C150.3 (4)
C20—S2—C6—N5176.73 (19)C13—C14—C15—C160.3 (4)
N5—C6—N7—C7A1.1 (4)C14—C15—C16—C170.3 (4)
S2—C6—N7—C7A178.60 (17)C15—C16—C17—C180.3 (4)
C6—N7—C7A—N1179.6 (2)O12—C13—C18—C17179.5 (2)
C6—N7—C7A—C3A0.5 (3)C14—C13—C18—C170.3 (3)
N2—N1—C7A—N7178.6 (2)C16—C17—C18—C130.3 (4)
C8—N1—C7A—N75.3 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C3—H3···O12i0.932.493.368 (3)157
Symmetry code: (i) x, y+1/2, z1/2.

Experimental details

Crystal data
Chemical formulaC17H20N4OS2
Mr360.49
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)17.966 (1), 10.089 (1), 10.055 (1)
β (°) 104.97 (1)
V3)1760.7 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.31
Crystal size (mm)0.30 × 0.25 × 0.20
Data collection
DiffractometerBruker P4
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
4550, 3468, 2333
Rint0.023
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.105, 1.05
No. of reflections3468
No. of parameters220
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.23, 0.23

Computer programs: XSCANS (Siemens, 1996), XSCANS, SHELXTL (Bruker, 1997), SHELXTL.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C3—H3···O12i0.932.493.368 (3)157
Symmetry code: (i) x, y+1/2, z1/2.
 

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