Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801016907/wn6059sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801016907/wn6059Isup2.hkl |
CCDC reference: 176015
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.003 Å
- R factor = 0.047
- wR factor = 0.130
- Data-to-parameter ratio = 14.4
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry General Notes
REFLT_03 From the CIF: _diffrn_reflns_theta_max 28.00 From the CIF: _reflns_number_total 3364 From the CIF: _diffrn_reflns_limit_ max hkl 14. 12. 22. From the CIF: _diffrn_reflns_limit_ min hkl -14. -11. 0. TEST1: Expected hkl limits for theta max Calculated maximum hkl 13. 11. 20. Calculated minimum hkl -13. -11. -20. ALERT: Expected hkl max differ from CIF values
The title compound was synthesized as described by Gundersen et al. (1994). Crystals suitable for X-ray diffraction studies were obtained by slow evaporation at room temperature from a mixture of ethanol, acetone and chloroform (1:1:1).
All H atoms, except for H21, were located from a difference Fourier synthesis and refined isotropically. H21, attached to C21, was positioned geometrically and not refined. Bond distances to H atoms range from 0.90 to 1.00 Å.
Data collection: COLLECT (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1999); software used to prepare material for publication: SHELXL97.
C16H12N4S | F(000) = 608 |
Mr = 292.36 | Dx = 1.388 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71070 Å |
a = 10.1130 (4) Å | Cell parameters from 7690 reflections |
b = 8.9101 (2) Å | θ = 3.2–28° |
c = 15.6434 (7) Å | µ = 0.23 mm−1 |
β = 96.8550 (17)° | T = 293 K |
V = 1399.52 (9) Å3 | Trigonal prism, pale yellow |
Z = 4 | 0.48 × 0.43 × 0.12 mm |
Nonius KappaCCD area-detector diffractometer | 2745 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.024 |
Graphite monochromator | θmax = 28.0°, θmin = 3.2° |
ϕ and ω scans | h = −14→14 |
7690 measured reflections | k = −11→12 |
3364 independent reflections | l = 0→22 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.047 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.130 | w = 1/[σ2(Fo2) + (0.055P)2 + 0.536P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max = 0.001 |
3364 reflections | Δρmax = 0.26 e Å−3 |
234 parameters | Δρmin = −0.45 e Å−3 |
0 restraints |
C16H12N4S | V = 1399.52 (9) Å3 |
Mr = 292.36 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.1130 (4) Å | µ = 0.23 mm−1 |
b = 8.9101 (2) Å | T = 293 K |
c = 15.6434 (7) Å | 0.48 × 0.43 × 0.12 mm |
β = 96.8550 (17)° |
Nonius KappaCCD area-detector diffractometer | 2745 reflections with I > 2σ(I) |
7690 measured reflections | Rint = 0.024 |
3364 independent reflections |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.130 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.09 | Δρmax = 0.26 e Å−3 |
3364 reflections | Δρmin = −0.45 e Å−3 |
234 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 | 0.01986 (15) | 0.27529 (16) | 0.09057 (9) | 0.0391 (3) | |
C2 | 0.11782 (18) | 0.3725 (2) | 0.08096 (11) | 0.0420 (4) | |
N3 | 0.16244 (14) | 0.41884 (16) | 0.00861 (9) | 0.0396 (3) | |
C4 | 0.09648 (15) | 0.35270 (18) | −0.06002 (10) | 0.0340 (3) | |
C5 | −0.00681 (15) | 0.24882 (18) | −0.06038 (10) | 0.0333 (3) | |
C6 | −0.04605 (16) | 0.21114 (17) | 0.01955 (10) | 0.0336 (3) | |
N7 | −0.05253 (14) | 0.20673 (18) | −0.14425 (9) | 0.0433 (4) | |
C8 | 0.02187 (18) | 0.2851 (2) | −0.19068 (11) | 0.0450 (4) | |
N9 | 0.11296 (13) | 0.37573 (17) | −0.14485 (9) | 0.0385 (3) | |
C10 | 0.20579 (19) | 0.4814 (2) | −0.17829 (14) | 0.0466 (4) | |
C11 | 0.34095 (16) | 0.41421 (18) | −0.18361 (11) | 0.0374 (4) | |
C12 | 0.4409 (2) | 0.4256 (3) | −0.11572 (14) | 0.0551 (5) | |
C13 | 0.5655 (2) | 0.3646 (3) | −0.12139 (18) | 0.0679 (6) | |
C14 | 0.5904 (2) | 0.2905 (3) | −0.19447 (18) | 0.0666 (6) | |
C15 | 0.4923 (3) | 0.2775 (3) | −0.26193 (16) | 0.0659 (6) | |
C16 | 0.3678 (2) | 0.3392 (2) | −0.25677 (13) | 0.0497 (4) | |
C17 | −0.15485 (16) | 0.10996 (18) | 0.03064 (11) | 0.0367 (4) | |
S18 | −0.20660 (6) | 0.08415 (6) | 0.13018 (3) | 0.05740 (19) | |
C19 | −0.3269 (2) | −0.0386 (2) | 0.08988 (16) | 0.0593 (5) | |
C20 | −0.3277 (2) | −0.0602 (2) | 0.00512 (16) | 0.0586 (5) | |
C21 | −0.23094 (18) | 0.0247 (2) | −0.03142 (12) | 0.0445 (4) | |
H21 | −0.2195 | 0.0237 | −0.0895 | 0.050* | |
H2 | 0.159 (2) | 0.415 (2) | 0.1349 (14) | 0.053 (6)* | |
H8 | 0.018 (2) | 0.283 (2) | −0.2517 (15) | 0.053 (6)* | |
H10A | 0.165 (2) | 0.511 (3) | −0.2339 (16) | 0.063 (6)* | |
H10B | 0.214 (2) | 0.568 (3) | −0.1370 (14) | 0.055 (6)* | |
H12 | 0.420 (2) | 0.483 (3) | −0.0655 (17) | 0.076 (8)* | |
H13 | 0.633 (3) | 0.377 (3) | −0.0774 (19) | 0.096 (9)* | |
H14 | 0.679 (3) | 0.249 (3) | −0.1960 (18) | 0.088 (8)* | |
H15 | 0.510 (3) | 0.225 (3) | −0.3129 (19) | 0.087 (9)* | |
H16 | 0.297 (2) | 0.326 (3) | −0.3025 (16) | 0.063 (6)* | |
H19 | −0.384 (3) | −0.082 (3) | 0.1281 (18) | 0.085 (8)* | |
H20 | −0.386 (2) | −0.123 (3) | −0.0251 (16) | 0.071 (7)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0448 (8) | 0.0444 (8) | 0.0282 (7) | 0.0016 (6) | 0.0051 (6) | 0.0000 (6) |
C2 | 0.0451 (9) | 0.0482 (9) | 0.0320 (8) | −0.0008 (7) | 0.0019 (7) | −0.0030 (7) |
N3 | 0.0393 (8) | 0.0433 (8) | 0.0362 (7) | −0.0004 (6) | 0.0042 (6) | −0.0009 (6) |
C4 | 0.0323 (8) | 0.0390 (8) | 0.0311 (8) | 0.0077 (6) | 0.0055 (6) | 0.0030 (6) |
C5 | 0.0300 (7) | 0.0413 (8) | 0.0286 (8) | 0.0054 (6) | 0.0033 (6) | 0.0001 (6) |
C6 | 0.0340 (8) | 0.0370 (8) | 0.0301 (8) | 0.0069 (6) | 0.0050 (6) | 0.0011 (6) |
N7 | 0.0381 (8) | 0.0630 (10) | 0.0287 (7) | 0.0002 (7) | 0.0033 (6) | −0.0032 (6) |
C8 | 0.0401 (9) | 0.0685 (12) | 0.0264 (8) | 0.0056 (8) | 0.0044 (7) | 0.0014 (8) |
N9 | 0.0344 (7) | 0.0518 (8) | 0.0305 (7) | 0.0060 (6) | 0.0082 (5) | 0.0074 (6) |
C10 | 0.0476 (10) | 0.0481 (10) | 0.0470 (10) | 0.0085 (8) | 0.0172 (8) | 0.0146 (9) |
C11 | 0.0374 (8) | 0.0384 (8) | 0.0381 (9) | −0.0018 (6) | 0.0116 (7) | 0.0069 (7) |
C12 | 0.0513 (11) | 0.0642 (12) | 0.0494 (11) | −0.0023 (9) | 0.0043 (9) | −0.0105 (10) |
C13 | 0.0420 (11) | 0.0836 (16) | 0.0751 (16) | −0.0032 (11) | −0.0055 (11) | 0.0019 (13) |
C14 | 0.0442 (12) | 0.0749 (15) | 0.0845 (17) | 0.0106 (10) | 0.0234 (11) | 0.0164 (13) |
C15 | 0.0719 (15) | 0.0709 (14) | 0.0603 (14) | 0.0184 (11) | 0.0294 (12) | −0.0001 (11) |
C16 | 0.0516 (11) | 0.0588 (11) | 0.0393 (10) | 0.0043 (9) | 0.0081 (8) | −0.0001 (8) |
C17 | 0.0375 (8) | 0.0387 (8) | 0.0348 (8) | 0.0063 (6) | 0.0082 (6) | 0.0039 (7) |
S18 | 0.0642 (4) | 0.0670 (4) | 0.0442 (3) | −0.0131 (2) | 0.0195 (2) | 0.0027 (2) |
C19 | 0.0536 (12) | 0.0560 (12) | 0.0716 (15) | −0.0071 (9) | 0.0206 (11) | 0.0122 (11) |
C20 | 0.0494 (11) | 0.0527 (11) | 0.0725 (15) | −0.0097 (9) | 0.0024 (10) | 0.0007 (10) |
C21 | 0.0422 (9) | 0.0461 (9) | 0.0458 (10) | −0.0021 (7) | 0.0074 (8) | −0.0001 (8) |
N1—C2 | 1.338 (2) | C11—C16 | 1.380 (3) |
N1—C6 | 1.352 (2) | C12—C13 | 1.385 (3) |
C2—N3 | 1.333 (2) | C12—H12 | 0.98 (3) |
C2—H2 | 0.97 (2) | C13—C14 | 1.369 (4) |
N3—C4 | 1.332 (2) | C13—H13 | 0.92 (3) |
C4—N9 | 1.372 (2) | C14—C15 | 1.364 (4) |
C4—C5 | 1.395 (2) | C14—H14 | 0.97 (3) |
C5—N7 | 1.390 (2) | C15—C16 | 1.385 (3) |
C5—C6 | 1.397 (2) | C15—H15 | 0.96 (3) |
C6—C17 | 1.449 (2) | C16—H16 | 0.95 (2) |
N7—C8 | 1.308 (2) | C17—C21 | 1.391 (3) |
C8—N9 | 1.363 (2) | C17—S18 | 1.7164 (17) |
C8—H8 | 0.95 (2) | S18—C19 | 1.700 (2) |
N9—C10 | 1.469 (2) | C19—C20 | 1.339 (3) |
C10—C11 | 1.504 (2) | C19—H19 | 0.96 (3) |
C10—H10A | 0.95 (2) | C20—C21 | 1.411 (3) |
C10—H10B | 1.01 (2) | C20—H20 | 0.91 (3) |
C11—C12 | 1.380 (3) | C21—H21 | 0.9300 |
C2—N1—C6 | 118.71 (14) | C16—C11—C10 | 120.58 (17) |
N3—C2—N1 | 128.76 (16) | C11—C12—C13 | 120.7 (2) |
N3—C2—H2 | 117.6 (12) | C11—C12—H12 | 116.5 (14) |
N1—C2—H2 | 113.6 (12) | C13—C12—H12 | 122.7 (14) |
C4—N3—C2 | 111.09 (15) | C14—C13—C12 | 120.1 (2) |
N3—C4—N9 | 127.33 (15) | C14—C13—H13 | 119.2 (19) |
N3—C4—C5 | 126.83 (15) | C12—C13—H13 | 120.6 (19) |
N9—C4—C5 | 105.82 (14) | C15—C14—C13 | 119.9 (2) |
N7—C5—C4 | 110.33 (14) | C15—C14—H14 | 122.3 (17) |
N7—C5—C6 | 133.00 (15) | C13—C14—H14 | 117.9 (17) |
C4—C5—C6 | 116.64 (14) | C14—C15—C16 | 120.2 (2) |
N1—C6—C5 | 117.96 (15) | C14—C15—H15 | 119.8 (17) |
N1—C6—C17 | 118.13 (14) | C16—C15—H15 | 120.0 (17) |
C5—C6—C17 | 123.89 (15) | C11—C16—C15 | 120.7 (2) |
C8—N7—C5 | 103.39 (15) | C11—C16—H16 | 118.7 (14) |
N7—C8—N9 | 114.93 (15) | C15—C16—H16 | 120.5 (14) |
N7—C8—H8 | 126.1 (13) | C21—C17—C6 | 128.41 (15) |
N9—C8—H8 | 119.0 (13) | C21—C17—S18 | 110.91 (13) |
C8—N9—C4 | 105.52 (14) | C6—C17—S18 | 120.67 (13) |
C8—N9—C10 | 127.80 (15) | C19—S18—C17 | 91.83 (10) |
C4—N9—C10 | 126.63 (15) | C20—C19—S18 | 112.27 (16) |
N9—C10—C11 | 112.85 (14) | C20—C19—H19 | 128.7 (17) |
N9—C10—H10A | 105.8 (14) | S18—C19—H19 | 119.0 (17) |
C11—C10—H10A | 111.0 (14) | C19—C20—C21 | 113.7 (2) |
N9—C10—H10B | 105.9 (12) | C19—C20—H20 | 122.1 (16) |
C11—C10—H10B | 109.6 (12) | C21—C20—H20 | 124.2 (16) |
H10A—C10—H10B | 111.7 (19) | C17—C21—C20 | 111.28 (18) |
C12—C11—C16 | 118.39 (17) | C17—C21—H21 | 124.4 |
C12—C11—C10 | 121.03 (17) | C20—C21—H21 | 124.4 |
C6—N1—C2—N3 | 0.3 (3) | C8—N9—C10—C11 | −94.6 (2) |
N1—C2—N3—C4 | −0.9 (3) | C4—N9—C10—C11 | 88.3 (2) |
C2—N3—C4—N9 | 178.20 (15) | N9—C10—C11—C12 | −91.0 (2) |
C2—N3—C4—C5 | 0.4 (2) | N9—C10—C11—C16 | 88.9 (2) |
N3—C4—C5—N7 | 178.93 (15) | C16—C11—C12—C13 | 0.7 (3) |
N9—C4—C5—N7 | 0.73 (18) | C10—C11—C12—C13 | −179.4 (2) |
N3—C4—C5—C6 | 0.6 (2) | C11—C12—C13—C14 | −0.8 (4) |
N9—C4—C5—C6 | −177.59 (13) | C12—C13—C14—C15 | 0.3 (4) |
C2—N1—C6—C5 | 0.8 (2) | C13—C14—C15—C16 | 0.1 (4) |
C2—N1—C6—C17 | −177.95 (15) | C12—C11—C16—C15 | −0.3 (3) |
N7—C5—C6—N1 | −179.02 (16) | C10—C11—C16—C15 | 179.84 (19) |
C4—C5—C6—N1 | −1.2 (2) | C14—C15—C16—C11 | −0.1 (4) |
N7—C5—C6—C17 | −0.4 (3) | N1—C6—C17—C21 | −175.69 (16) |
C4—C5—C6—C17 | 177.47 (14) | C5—C6—C17—C21 | 5.7 (3) |
C4—C5—N7—C8 | −0.40 (19) | N1—C6—C17—S18 | 5.0 (2) |
C6—C5—N7—C8 | 177.54 (17) | C5—C6—C17—S18 | −173.64 (12) |
C5—N7—C8—N9 | −0.1 (2) | C21—C17—S18—C19 | 0.25 (15) |
N7—C8—N9—C4 | 0.5 (2) | C6—C17—S18—C19 | 179.66 (14) |
N7—C8—N9—C10 | −177.00 (16) | C17—S18—C19—C20 | 0.36 (18) |
N3—C4—N9—C8 | −178.92 (16) | S18—C19—C20—C21 | −0.9 (3) |
C5—C4—N9—C8 | −0.73 (17) | C6—C17—C21—C20 | 179.88 (17) |
N3—C4—N9—C10 | −1.3 (3) | S18—C17—C21—C20 | −0.8 (2) |
C5—C4—N9—C10 | 176.85 (15) | C19—C20—C21—C17 | 1.1 (3) |
Experimental details
Crystal data | |
Chemical formula | C16H12N4S |
Mr | 292.36 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 10.1130 (4), 8.9101 (2), 15.6434 (7) |
β (°) | 96.8550 (17) |
V (Å3) | 1399.52 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.23 |
Crystal size (mm) | 0.48 × 0.43 × 0.12 |
Data collection | |
Diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7690, 3364, 2745 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.661 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.130, 1.09 |
No. of reflections | 3364 |
No. of parameters | 234 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.26, −0.45 |
Computer programs: COLLECT (Nonius, 1997), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 1999), SHELXL97.
C6—C17 | 1.449 (2) | C17—S18 | 1.7164 (17) |
N9—C10 | 1.469 (2) | S18—C19 | 1.700 (2) |
C10—C11 | 1.504 (2) | C19—C20 | 1.339 (3) |
C17—C21 | 1.391 (3) | C20—C21 | 1.411 (3) |
N1—C6—C17 | 118.13 (14) | C21—C17—C6 | 128.41 (15) |
C5—C6—C17 | 123.89 (15) | C21—C17—S18 | 110.91 (13) |
N9—C10—C11 | 112.85 (14) | C6—C17—S18 | 120.67 (13) |
N7—C5—C6—N1 | −179.02 (16) | N9—C10—C11—C16 | 88.9 (2) |
N7—C5—C6—C17 | −0.4 (3) | N1—C6—C17—C21 | −175.69 (16) |
C4—C5—C6—C17 | 177.47 (14) | C5—C6—C17—C21 | 5.7 (3) |
C8—N9—C10—C11 | −94.6 (2) | N1—C6—C17—S18 | 5.0 (2) |
C4—N9—C10—C11 | 88.3 (2) | C5—C6—C17—S18 | −173.64 (12) |
N9—C10—C11—C12 | −91.0 (2) |
Tuberculosis (TB) is the major cause of death, from a single infectious agent, among adults in developing countries and there has been an unfortunate revival of TB in the industrialized world. There are ca 8 million new cases of TB each year and it has been estimated that ca 30 million people will die from tuberculosis within about 10 years (Duncan, 1997). Thus, there is an urgent need for new antimycobacterial agents and various 9-benzylpurines, including the title compound, (I), have shown high inhibitory activity against Mycobacterium tuberculosis (Bakkestuen et al., 2000). Hence, we undertook the present study to examine the effect of the thiophene substituent at the 6-position.
The molecular geometry is illustrated in Fig. 1 and the bond lengths and angles are listed in Table 1. The values are in agreement with those found in other structures containing the purine ring system (Stewart & Jensen, 1964; Lai & Marsh, 1972; Wilson et al., 1986; Low et al., 1987; Flensburg, 1994).
The benzene ring is inclined at an angle of 64.03 (5)° to the purine ring system and at an angle of 60.23 (6)° to the thiophene ring at the 6-position. The thiophene ring is nearly coplanar with the purine ring, the dihedral angle being only 6.39 (4)°. The base is not exactly planar; the two rings are rotated by 1.46 (6)° about the C4—C5 bond.
The bond distance N9—C10 [1.469 (2) Å] is longer than that found in the case of adenin-9-ylacetate [1.451 (1) Å] and the C8—N9—C10—C11 torsion angle of -94.6 (2)° also differs from the value of 104.65 (13)° reported by Flensburg (1994). The bond distances and angles in the thiophene ring are, by and large, normal. The bond angles C5—C6—C17 [123.89 (15)°] and N1—C6—C17 [118.13 (14)°] are comparable to corresponding angles of 124.21 (10)° and 118.29 (10)° in the case of NH2 substitution at the 6-position, indicating that the thiophene ring has no great effect on the bond angles.
The N1—C6 bond distance of 1.352 (2) Å is slightly greater than a C═N distance of 1.282 (2) Å in 2-[(4-hydroxyphenyl)iminomethyl]thiophene (Kazak et al., 2000) due to the aromaticity of the purine ring system. However, the C6—C17 bond distance of 1.449 (2) Å is not affected.
As is evident from Fig. 2, a hydrophobic region is created due to interactions between the benzene rings. The molecular packing is stabilize d by segregation of alternate hydrophobic and hydrophilic zones.