Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102005735/na1564sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102005735/na1564Isup2.hkl |
CCDC reference: 187934
Isoamyl nitrite (1.65 ml, 12 mmol) was added to a solution of 4-amino-6-benzyloxy-2-(methylthio)pyrimidine (2.47 g, 10 mmol) in dimethyl sulfoxide (DMSO, 25 ml). The reaction mixture was stirred at room temperature and monitored by thin-layer chromatography (eluent CH2Cl2/MeOH, 9:1 v/v) until the starting pyrimidine was no longer detected (24 h). Addition of water (50 ml) precipitated product (I). The product was filtered, washed with water and dried, and then recrystallized from acetonitrile–dimethyl sulfoxide (5:1, v/v) [yield 2.10 g, 76%; m.p. 420 K]. 1H NMR (DMSO-d6) δ: 10.02 (bs, 1H, NH2), 8.80 (bs, 1H, NH2), 7.55–7.58 (m, 2H), 7.40–7.46 (m, 5H), 5.70 (s, 2H, CH2O), 2.57 (s, 3H, CH 3S); 13C NMR (DMSO-d6) δ: 177.8, 168.5, 145.7, 140.2, 135.9, 128.6, 128.5, 128.4, 69.1, 14.1. Crystals of (I) suitable for single-crystal X-ray diffraction analysis were selected directly from the analytical sample.
H atoms were treated as riding, with C—H distances in the range 0.95–0.99 Å and N—H distances of 0.88 Å.
Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SHELXTL (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2002); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).
C12H12N4O2S | F(000) = 1152 |
Mr = 276.32 | Dx = 1.439 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 6223 reflections |
a = 15.6152 (10) Å | θ = 1.3–29.0° |
b = 9.1842 (6) Å | µ = 0.26 mm−1 |
c = 17.7920 (11) Å | T = 120 K |
β = 90.830 (2)° | Block, colourless |
V = 2551.3 (3) Å3 | 0.50 × 0.35 × 0.20 mm |
Z = 8 |
Bruker-SMART-1000 CCD diffractometer | 6223 independent reflections |
Radiation source: fine-focus sealed X-ray tube | 4840 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
ϕ scans, and ω scans with κ offsets | θmax = 29.0°, θmin = 1.3° |
Absorption correction: multi-scan (SADABS; Bruker, 1997) | h = −20→20 |
Tmin = 0.882, Tmax = 0.950 | k = −12→12 |
24010 measured reflections | l = −23→23 |
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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.101 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.058P)2 + 0.327P] where P = (Fo2 + 2Fc2)/3 |
6223 reflections | (Δ/σ)max = 0.001 |
345 parameters | Δρmax = 0.35 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
C12H12N4O2S | V = 2551.3 (3) Å3 |
Mr = 276.32 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 15.6152 (10) Å | µ = 0.26 mm−1 |
b = 9.1842 (6) Å | T = 120 K |
c = 17.7920 (11) Å | 0.50 × 0.35 × 0.20 mm |
β = 90.830 (2)° |
Bruker-SMART-1000 CCD diffractometer | 6223 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1997) | 4840 reflections with I > 2σ(I) |
Tmin = 0.882, Tmax = 0.950 | Rint = 0.023 |
24010 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.101 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.35 e Å−3 |
6223 reflections | Δρmin = −0.25 e Å−3 |
345 parameters |
x | y | z | Uiso*/Ueq | ||
N11 | 0.26619 (7) | 0.57631 (12) | 0.38289 (6) | 0.0256 (2) | |
C12 | 0.34204 (8) | 0.50920 (15) | 0.39377 (7) | 0.0251 (3) | |
S12 | 0.37614 (2) | 0.38279 (4) | 0.32777 (2) | 0.03292 (10) | |
C121 | 0.29268 (10) | 0.3893 (2) | 0.25706 (9) | 0.0404 (4) | |
N13 | 0.39803 (7) | 0.52625 (12) | 0.45058 (6) | 0.0253 (2) | |
C14 | 0.37771 (8) | 0.62629 (15) | 0.50305 (7) | 0.0250 (3) | |
N14 | 0.43291 (7) | 0.64343 (14) | 0.55976 (7) | 0.0315 (3) | |
C15 | 0.29961 (8) | 0.70870 (15) | 0.49700 (8) | 0.0261 (3) | |
N15 | 0.27135 (8) | 0.81465 (14) | 0.54536 (7) | 0.0363 (3) | |
O15 | 0.31865 (7) | 0.84115 (13) | 0.60181 (6) | 0.0432 (3) | |
C16 | 0.24639 (8) | 0.67458 (15) | 0.43399 (8) | 0.0255 (3) | |
O16 | 0.17207 (6) | 0.74563 (11) | 0.42737 (6) | 0.0298 (2) | |
C167 | 0.11727 (9) | 0.70483 (16) | 0.36374 (8) | 0.0312 (3) | |
C161 | 0.04088 (9) | 0.80449 (16) | 0.36150 (8) | 0.0288 (3) | |
C162 | 0.00075 (10) | 0.85356 (16) | 0.42541 (8) | 0.0330 (3) | |
C163 | −0.07137 (10) | 0.94235 (17) | 0.42015 (9) | 0.0355 (3) | |
C164 | −0.10439 (10) | 0.98162 (19) | 0.35154 (9) | 0.0410 (4) | |
C165 | −0.06544 (12) | 0.9315 (2) | 0.28700 (10) | 0.0558 (5) | |
C166 | 0.00637 (11) | 0.8434 (2) | 0.29205 (9) | 0.0479 (5) | |
N21 | 0.23421 (7) | 0.27186 (13) | 0.50043 (6) | 0.0264 (2) | |
C22 | 0.15755 (8) | 0.30913 (15) | 0.46994 (7) | 0.0261 (3) | |
S22 | 0.12166 (2) | 0.21882 (4) | 0.38943 (2) | 0.03311 (10) | |
C221 | 0.20532 (10) | 0.09006 (17) | 0.37297 (10) | 0.0390 (4) | |
N23 | 0.10250 (7) | 0.40863 (13) | 0.49387 (6) | 0.0273 (3) | |
C24 | 0.12322 (8) | 0.47877 (16) | 0.55858 (8) | 0.0281 (3) | |
N24 | 0.06825 (8) | 0.57627 (15) | 0.58339 (7) | 0.0383 (3) | |
C25 | 0.20171 (9) | 0.44616 (16) | 0.59792 (8) | 0.0293 (3) | |
N25 | 0.22988 (8) | 0.50434 (16) | 0.66500 (7) | 0.0407 (3) | |
O25 | 0.18349 (8) | 0.60084 (15) | 0.69388 (7) | 0.0528 (3) | |
C26 | 0.25442 (8) | 0.34040 (15) | 0.56363 (8) | 0.0270 (3) | |
O26 | 0.32842 (6) | 0.31138 (11) | 0.59831 (5) | 0.0303 (2) | |
C267 | 0.38374 (9) | 0.20328 (17) | 0.56463 (9) | 0.0335 (3) | |
C261 | 0.45856 (9) | 0.18088 (17) | 0.61798 (9) | 0.0337 (3) | |
C262 | 0.50491 (11) | 0.0520 (2) | 0.61235 (12) | 0.0511 (5) | |
C263 | 0.57526 (12) | 0.0281 (2) | 0.65882 (14) | 0.0668 (6) | |
C264 | 0.60074 (11) | 0.1306 (2) | 0.71148 (13) | 0.0611 (6) | |
C265 | 0.55452 (10) | 0.2569 (2) | 0.71799 (10) | 0.0480 (5) | |
C266 | 0.48365 (9) | 0.28248 (19) | 0.67110 (9) | 0.0389 (4) | |
H12A | 0.2367 | 0.3832 | 0.2812 | 0.061* | |
H12B | 0.2992 | 0.3072 | 0.2224 | 0.061* | |
H12C | 0.2966 | 0.4809 | 0.2291 | 0.061* | |
H14A | 0.4800 | 0.5909 | 0.5618 | 0.038* | |
H14B | 0.4224 | 0.7073 | 0.5953 | 0.038* | |
H16A | 0.0983 | 0.6026 | 0.3692 | 0.037* | |
H16B | 0.1494 | 0.7133 | 0.3164 | 0.037* | |
H162 | 0.0226 | 0.8264 | 0.4735 | 0.040* | |
H163 | −0.0979 | 0.9759 | 0.4647 | 0.043* | |
H164 | −0.1534 | 1.0426 | 0.3481 | 0.049* | |
H165 | −0.0881 | 0.9576 | 0.2391 | 0.067* | |
H166 | 0.0323 | 0.8092 | 0.2474 | 0.058* | |
H22A | 0.2597 | 0.1417 | 0.3671 | 0.059* | |
H22B | 0.1922 | 0.0349 | 0.3271 | 0.059* | |
H22C | 0.2099 | 0.0230 | 0.4157 | 0.059* | |
H24A | 0.0205 | 0.5933 | 0.5581 | 0.046* | |
H24B | 0.0794 | 0.6242 | 0.6252 | 0.046* | |
H26A | 0.4040 | 0.2378 | 0.5153 | 0.040* | |
H26B | 0.3523 | 0.1107 | 0.5570 | 0.040* | |
H262 | 0.4882 | −0.0197 | 0.5765 | 0.061* | |
H263 | 0.6066 | −0.0601 | 0.6545 | 0.080* | |
H264 | 0.6496 | 0.1137 | 0.7427 | 0.073* | |
H265 | 0.5708 | 0.3273 | 0.7546 | 0.058* | |
H266 | 0.4524 | 0.3707 | 0.6758 | 0.047* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N11 | 0.0202 (5) | 0.0290 (6) | 0.0275 (6) | −0.0012 (4) | −0.0042 (4) | 0.0013 (5) |
C12 | 0.0214 (6) | 0.0269 (7) | 0.0270 (6) | −0.0037 (5) | −0.0007 (5) | 0.0006 (5) |
S12 | 0.02645 (18) | 0.0395 (2) | 0.03268 (19) | 0.00186 (15) | −0.00430 (14) | −0.01012 (15) |
C121 | 0.0306 (8) | 0.0596 (11) | 0.0308 (8) | −0.0036 (7) | −0.0061 (6) | −0.0118 (7) |
N13 | 0.0195 (5) | 0.0288 (6) | 0.0276 (6) | 0.0006 (5) | −0.0034 (4) | −0.0007 (5) |
C14 | 0.0203 (6) | 0.0276 (7) | 0.0269 (6) | −0.0028 (5) | −0.0033 (5) | 0.0012 (5) |
N14 | 0.0239 (6) | 0.0381 (7) | 0.0324 (6) | 0.0051 (5) | −0.0090 (5) | −0.0083 (5) |
C15 | 0.0212 (6) | 0.0265 (7) | 0.0306 (7) | 0.0000 (5) | −0.0036 (5) | −0.0001 (5) |
N15 | 0.0306 (7) | 0.0371 (7) | 0.0409 (7) | 0.0034 (5) | −0.0065 (5) | −0.0090 (6) |
O15 | 0.0353 (6) | 0.0503 (7) | 0.0437 (6) | 0.0053 (5) | −0.0125 (5) | −0.0178 (5) |
C16 | 0.0193 (6) | 0.0267 (7) | 0.0305 (7) | −0.0018 (5) | −0.0033 (5) | 0.0050 (5) |
O16 | 0.0218 (5) | 0.0331 (5) | 0.0343 (5) | 0.0042 (4) | −0.0099 (4) | −0.0013 (4) |
C167 | 0.0249 (7) | 0.0363 (8) | 0.0320 (7) | 0.0017 (6) | −0.0106 (6) | 0.0006 (6) |
C161 | 0.0205 (6) | 0.0345 (8) | 0.0314 (7) | −0.0026 (6) | −0.0053 (5) | 0.0046 (6) |
C162 | 0.0348 (8) | 0.0348 (8) | 0.0293 (7) | −0.0004 (6) | −0.0072 (6) | 0.0022 (6) |
C163 | 0.0311 (8) | 0.0387 (8) | 0.0367 (8) | −0.0016 (6) | 0.0002 (6) | −0.0033 (6) |
C164 | 0.0260 (8) | 0.0500 (10) | 0.0467 (9) | 0.0080 (7) | −0.0078 (7) | −0.0018 (7) |
C165 | 0.0461 (10) | 0.0865 (15) | 0.0344 (9) | 0.0268 (10) | −0.0097 (8) | 0.0083 (9) |
C166 | 0.0390 (9) | 0.0765 (13) | 0.0283 (8) | 0.0208 (9) | 0.0005 (7) | 0.0071 (8) |
N21 | 0.0193 (5) | 0.0307 (6) | 0.0293 (6) | 0.0015 (5) | −0.0019 (4) | 0.0056 (5) |
C22 | 0.0218 (6) | 0.0307 (7) | 0.0257 (6) | −0.0005 (5) | −0.0009 (5) | 0.0060 (5) |
S22 | 0.02616 (18) | 0.0416 (2) | 0.03141 (19) | 0.00181 (15) | −0.00467 (14) | −0.00393 (15) |
C221 | 0.0344 (8) | 0.0364 (8) | 0.0463 (9) | 0.0017 (7) | 0.0016 (7) | −0.0075 (7) |
N23 | 0.0205 (5) | 0.0354 (6) | 0.0259 (6) | 0.0033 (5) | −0.0050 (4) | 0.0024 (5) |
C24 | 0.0199 (6) | 0.0362 (8) | 0.0281 (7) | 0.0027 (6) | −0.0042 (5) | 0.0029 (6) |
N24 | 0.0266 (6) | 0.0523 (8) | 0.0358 (7) | 0.0138 (6) | −0.0112 (5) | −0.0106 (6) |
C25 | 0.0197 (6) | 0.0397 (8) | 0.0282 (7) | 0.0034 (6) | −0.0057 (5) | 0.0027 (6) |
N25 | 0.0291 (7) | 0.0567 (9) | 0.0361 (7) | 0.0086 (6) | −0.0080 (5) | −0.0073 (6) |
O25 | 0.0370 (6) | 0.0748 (9) | 0.0460 (7) | 0.0187 (6) | −0.0140 (5) | −0.0226 (6) |
C26 | 0.0192 (6) | 0.0328 (7) | 0.0287 (7) | 0.0000 (5) | −0.0025 (5) | 0.0102 (6) |
O26 | 0.0196 (5) | 0.0387 (6) | 0.0324 (5) | 0.0063 (4) | −0.0053 (4) | 0.0053 (4) |
C267 | 0.0231 (7) | 0.0353 (8) | 0.0420 (8) | 0.0065 (6) | −0.0030 (6) | 0.0043 (6) |
C261 | 0.0173 (6) | 0.0391 (8) | 0.0447 (8) | 0.0025 (6) | 0.0001 (6) | 0.0159 (7) |
C262 | 0.0294 (8) | 0.0452 (10) | 0.0787 (13) | 0.0099 (7) | −0.0015 (8) | 0.0112 (9) |
C263 | 0.0315 (9) | 0.0584 (13) | 0.1103 (18) | 0.0178 (9) | −0.0063 (11) | 0.0271 (12) |
C264 | 0.0215 (8) | 0.0762 (14) | 0.0852 (15) | −0.0004 (9) | −0.0142 (9) | 0.0438 (12) |
C265 | 0.0275 (8) | 0.0641 (12) | 0.0520 (10) | −0.0124 (8) | −0.0118 (7) | 0.0252 (9) |
C266 | 0.0242 (7) | 0.0445 (9) | 0.0476 (9) | −0.0001 (6) | −0.0066 (6) | 0.0177 (7) |
N11—C12 | 1.347 (2) | N21—C22 | 1.351 (2) |
C12—N13 | 1.336 (2) | C22—N23 | 1.329 (2) |
N13—C14 | 1.351 (2) | N23—C24 | 1.354 (2) |
C14—C15 | 1.438 (2) | C24—C25 | 1.434 (2) |
C15—C16 | 1.421 (2) | C25—C26 | 1.417 (2) |
C16—N11 | 1.321 (2) | C26—N21 | 1.323 (2) |
C12—S12 | 1.740 (2) | C22—S22 | 1.741 (2) |
S12—C121 | 1.799 (2) | S22—C221 | 1.789 (2) |
C121—H12A | 0.9800 | C221—H22A | 0.9800 |
C121—H12B | 0.9800 | C221—H22B | 0.9800 |
C121—H12C | 0.9800 | C221—H22C | 0.9800 |
C14—N14 | 1.327 (2) | C24—N24 | 1.321 (2) |
N14—H14A | 0.8800 | N24—H24A | 0.8800 |
N14—H14B | 0.8800 | N24—H24B | 0.8800 |
C15—N15 | 1.376 (2) | C25—N25 | 1.374 (2) |
N15—O15 | 1.262 (2) | N25—O25 | 1.259 (2) |
C16—O16 | 1.335 (2) | C26—O26 | 1.329 (2) |
O16—C167 | 1.458 (2) | O26—C267 | 1.451 (2) |
C167—C161 | 1.504 (2) | C267—C261 | 1.509 (2) |
C167—H16A | 0.9900 | C267—H26A | 0.9900 |
C167—H16B | 0.9900 | C267—H26B | 0.9900 |
C161—C162 | 1.382 (2) | C261—C266 | 1.381 (2) |
C161—C166 | 1.388 (2) | C261—C262 | 1.392 (2) |
C162—C163 | 1.392 (2) | C262—C263 | 1.383 (3) |
C162—H162 | 0.9500 | C262—H262 | 0.9500 |
C163—C164 | 1.367 (2) | C263—C264 | 1.382 (3) |
C163—H163 | 0.9500 | C263—H263 | 0.9500 |
C164—C165 | 1.386 (2) | C264—C265 | 1.372 (3) |
C164—H164 | 0.9500 | C264—H264 | 0.9500 |
C165—C166 | 1.384 (2) | C265—C266 | 1.396 (2) |
C165—H165 | 0.9500 | C265—H265 | 0.9500 |
C166—H166 | 0.9500 | C266—H266 | 0.9500 |
C16—N11—C12 | 115.3 (2) | C26—N21—C22 | 114.8 (2) |
N13—C12—N11 | 128.3 (2) | N23—C22—N21 | 128.3 (2) |
N13—C12—S12 | 112.67 (9) | N23—C22—S22 | 112.91 (9) |
N11—C12—S12 | 119.04 (9) | N21—C22—S22 | 118.9 (2) |
C12—S12—C121 | 102.95 (7) | C22—S22—C221 | 102.85 (7) |
S12—C121—H12A | 109.5 | S22—C221—H22A | 109.5 |
S12—C121—H12B | 109.5 | S22—C221—H22B | 109.5 |
H12A—C121—H12B | 109.5 | H22A—C221—H22B | 109.5 |
S12—C121—H12C | 109.5 | S22—C221—H22C | 109.5 |
H12A—C121—H12C | 109.5 | H22A—C221—H22C | 109.5 |
H12B—C121—H12C | 109.5 | H22B—C221—H22C | 109.5 |
C12—N13—C14 | 116.4 (2) | C22—N23—C24 | 116.9 (2) |
N14—C14—N13 | 116.7 (2) | N24—C24—N23 | 117.3 (2) |
N14—C14—C15 | 122.4 (2) | N24—C24—C25 | 122.2 (2) |
N13—C14—C15 | 120.9 (2) | N23—C24—C25 | 120.5 (2) |
C14—N14—H14A | 120.0 | C24—N24—H24A | 120.0 |
C14—N14—H14B | 120.0 | C24—N24—H24B | 120.0 |
H14A—N14—H14B | 120.0 | H24A—N24—H24B | 120.0 |
N15—C15—C16 | 117.4 (2) | N25—C25—C26 | 117.4 (2) |
N15—C15—C14 | 127.2 (2) | N25—C25—C24 | 127.1 (2) |
C16—C15—C14 | 115.4 (2) | C26—C25—C24 | 115.5 (2) |
O15—N15—C15 | 116.4 (2) | O25—N25—C25 | 116.7 (2) |
N11—C16—O16 | 119.0 (2) | N21—C26—O26 | 119.6 (2) |
N11—C16—C15 | 123.6 (2) | N21—C26—C25 | 124.0 (2) |
O16—C16—C15 | 117.4 (2) | O26—C26—C25 | 116.4 (2) |
C16—O16—C167 | 116.3 (2) | C26—O26—C267 | 117.7 (2) |
O16—C167—C161 | 108.7 (2) | O26—C267—C261 | 107.1 (2) |
O16—C167—H16A | 110.0 | O26—C267—H26A | 110.3 |
C161—C167—H16A | 110.0 | C261—C267—H26A | 110.3 |
O16—C167—H16B | 110.0 | O26—C267—H26B | 110.3 |
C161—C167—H16B | 110.0 | C261—C267—H26B | 110.3 |
H16A—C167—H16B | 108.3 | H26A—C267—H26B | 108.6 |
C162—C161—C166 | 118.3 (2) | C266—C261—C262 | 118.8 (2) |
C162—C161—C167 | 123.1 (2) | C266—C261—C267 | 123.2 (2) |
C166—C161—C167 | 118.6 (2) | C262—C261—C267 | 118.0 (2) |
C161—C162—C163 | 120.8 (2) | C263—C262—C261 | 120.1 (2) |
C161—C162—H162 | 119.6 | C263—C262—H262 | 120.0 |
C163—C162—H162 | 119.6 | C261—C262—H262 | 120.0 |
C164—C163—C162 | 120.6 (2) | C264—C263—C262 | 121.1 (2) |
C164—C163—H163 | 119.7 | C264—C263—H263 | 119.5 |
C162—C163—H163 | 119.7 | C262—C263—H263 | 119.5 |
C163—C164—C165 | 119.2 (2) | C265—C264—C263 | 119.1 (2) |
C163—C164—H164 | 120.4 | C265—C264—H264 | 120.5 |
C165—C164—H164 | 120.4 | C263—C264—H264 | 120.5 |
C166—C165—C164 | 120.3 (2) | C264—C265—C266 | 120.3 (2) |
C166—C165—H165 | 119.8 | C264—C265—H265 | 119.8 |
C164—C165—H165 | 119.8 | C266—C265—H265 | 119.8 |
C165—C166—C161 | 120.8 (2) | C261—C266—C265 | 120.7 (2) |
C165—C166—H166 | 119.6 | C261—C266—H266 | 119.7 |
C161—C166—H166 | 119.6 | C265—C266—H266 | 119.7 |
C121—S12—C12—N13 | −177.1 (1) | C221—S22—C22—N23 | −178.0 (1) |
O15—N15—C15—C16 | 178.5 (1) | O25—N25—C25—C26 | 178.3 (1) |
D—H···A | D—H | H···A | D···A | D—H···A |
N14—H14A···N13i | 0.88 | 2.20 | 3.073 (2) | 171 |
N14—H14B···O15 | 0.88 | 2.04 | 2.661 (2) | 127 |
N24—H24A···N23ii | 0.88 | 2.12 | 2.985 (2) | 168 |
N24—H24B···O25 | 0.88 | 2.03 | 2.655 (2) | 127 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C12H12N4O2S |
Mr | 276.32 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 120 |
a, b, c (Å) | 15.6152 (10), 9.1842 (6), 17.7920 (11) |
β (°) | 90.830 (2) |
V (Å3) | 2551.3 (3) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.26 |
Crystal size (mm) | 0.50 × 0.35 × 0.20 |
Data collection | |
Diffractometer | Bruker-SMART1000 CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1997) |
Tmin, Tmax | 0.882, 0.950 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 24010, 6223, 4840 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.682 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.101, 1.05 |
No. of reflections | 6223 |
No. of parameters | 345 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.35, −0.25 |
Computer programs: SMART (Bruker, 1997), SMART, SHELXTL (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2002), SHELXL97 and PRPKAPPA (Ferguson, 1999).
N11—C12 | 1.347 (2) | N21—C22 | 1.351 (2) |
C12—N13 | 1.336 (2) | C22—N23 | 1.329 (2) |
N13—C14 | 1.351 (2) | N23—C24 | 1.354 (2) |
C14—C15 | 1.438 (2) | C24—C25 | 1.434 (2) |
C15—C16 | 1.421 (2) | C25—C26 | 1.417 (2) |
C16—N11 | 1.321 (2) | C26—N21 | 1.323 (2) |
C12—S12 | 1.740 (2) | C22—S22 | 1.741 (2) |
S12—C121 | 1.799 (2) | S22—C221 | 1.789 (2) |
C14—N14 | 1.327 (2) | C24—N24 | 1.321 (2) |
C15—N15 | 1.376 (2) | C25—N25 | 1.374 (2) |
N15—O15 | 1.262 (2) | N25—O25 | 1.259 (2) |
C16—O16 | 1.335 (2) | C26—O26 | 1.329 (2) |
C121—S12—C12—N13 | −177.1 (1) | C221—S22—C22—N23 | −178.0 (1) |
O15—N15—C15—C16 | 178.5 (1) | O25—N25—C25—C26 | 178.3 (1) |
D—H···A | D—H | H···A | D···A | D—H···A |
N14—H14A···N13i | 0.88 | 2.20 | 3.073 (2) | 171 |
N14—H14B···O15 | 0.88 | 2.04 | 2.661 (2) | 127 |
N24—H24A···N23ii | 0.88 | 2.12 | 2.985 (2) | 168 |
N24—H24B···O25 | 0.88 | 2.03 | 2.655 (2) | 127 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z+1. |
Alkoxy- and amino-substituted O6-benzyloxy-5-nitrosopyrimidines (Marchal et al., 2000, 2002; Quesada et al., 2000) are important as potential, or proven, in vitro inhibitors of the human DNA-repair protein O6-alkylguanine-DNA-transferase (Chae et al., 1995; Quesada et al., 2002). We report here the molecular and supramolecular structure of a closely-related analogue (I) containing a (methylthio) substituent.
The title compound, (I), crystallizes in space group P21/c with two independent molecules in the asymmetric unit, i.e. with Z' = 2 (Fig. 1), but no additional symmetry could be detected. The intramolecular dimensions of the two independent molecules are very similar (Table 1), and show a number of features typical of 5-nitrosopyrimidines (Low et al., 2000; Low, Cannon et al., 2001; Low, Moreno et al., 2001; Quesada et al., 2002); in particular, there is marked fixation of the C—C and C—N bonds, with bonds Cn2—Nn3, Cn4—Nn4 and Cn6—Nn1 (n = 1 or 2) being short, despite the Cn4—Nn4 bond being formally a single bond in the classical representation of (I); in addition, the C—N and N—O distances in each C-nitroso fragment differ by only ca 0.11 Å, whereas in simple neutral compounds, where there is no possibility of significant electronic delocalization, these distances normally differ by at least 0.20 Å (Talberg, 1977; Schlemper et al., 1986) and the NO distance rarely exceeds 1.25 Å (Davis et al., 1965; Bauer & Andreassen, 1972; Talberg, 1977; Schlemper et al., 1986). The dimensions all point to the importance of the charge-separated form (Ia) (see Scheme) as an important contributor. In this respect, the electronic structure of (I) resembles that of the 2-benzyloxy analogue (II) (Quesada et al., 2002). Although the Cn2—Sn2 (n = 1 or 2) distances are significantly shorter than typical Car—S distances (Allen et al., 1987), there is no other support for a significant contribution from form (Ib), although the atoms concerned in (Ib) are almost coplanar (Table 1); the methyl–S distances are entirely normal.
In each of the independent molecules of (I), there is an intramolecular N—H···O hydrogen bond (Table 2) generating S(6) motifs; it is this motif which emphasizes the close similarity in overall molecular shape between 4-amino-5-nitroso pyrimidines, (III), and purines, (IV), which may indeed influence the biochemical activity of compounds of type (III). In addition, the molecules of each type are linked by paired N—H···N hydrogen bonds into centrosymmetric dimers (Fig. 2), in which the ring atoms N13 and N23 act as the acceptors (Table 2); molecules of type 1 (containing atom S12) form a dimer centred at (1/2, 1/2, 1/2), while molecules of type 2 (containing atom S22) form a dimer centred at (0, 1/2, 1/2).
The formation of hydrogen-bonded dimers which themselves form no other hydrogen bonds is unusual in this type of pyrimidine (Quesada et al., 2002); however, there are aromatic π–π-stacking interactions between the dimer units formed by (I). Within the asymmetric unit, the two pyrimidine planes make an angle of 0.57 (6)°; the centroid separation is 3.4421 (8) Å and the interplanar spacing ca 3.35 Å. Thus, the hydrogen-bonded dimer centred at (1/2, 1/2, 1/2) and formed by molecules of type 1 forms π–π-stacking interactions with the type 2 dimers centred at (0, 1/2, 1/2) and (1, 1/2, 1/2), and propagation of these interactions generates a chain running parallel to the [100] direction in which type 1 and type 2 dimers alternate (Fig. 3).