Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102020206/na1584sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102020206/na1584Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102020206/na1584IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102020206/na1584IIIsup4.hkl |
CCDC references: 204038; 204039; 204040
A sample of compound (I) was purchased from Aldrich and converted to (II) (m. p. 475 K) using the transalkoxylation and N-benzylation methodology previously described by Low et al. (2002). Compound (III) (m. p. 408 K) was likewise prepared from 4-amino-2-methylthio-6-methoxypyrimidine (Pfleiderer & Liedek, 1958). 1H NMR (DMSO-d6, p.p.m), for (II): δ 2.15 (s, 3H, CH3), 4.47 (d, 2H, N–CH2, J = 6.31 Hz), 5.28 (s, 2H, O—CH2), 5.93 (s, 1H, C5—H), 7.26 (m, 10H, 2 × Ph), 7.55 (br s, 1H, NH, exchanges with D2O); for (III): δ 4.42 (d, 2H, NH–CH2, J = 5.28 Hz), 5.32 (s, 2H, O—CH2), 5.33 (s, 2H, O–CH2), 5.41 (s, 1H, C5–H), 5.43 (br s, 1H, NH exchanges with D2O), 7.29 (m, 15H, 3 × Ph). Crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation of solutions in ethyl acetate [for (I)], ethanol [for (II)] and n-butanol [for (III)].
For compound (I), the systematic absences permitted Pnma (= Pnam) and Pna21 as possible space groups; Pnma was selected and confirmed by the analysis. For both (II) and (III), space group P21/c was uniquely assigned from the systematic absences. All H atoms were treated as riding, with C—H distances of C—H = 0.95 (aromatic), 0.98 (CH3) or 0.99 Å (CH2), and N—H distances of 0.88 Å. The methyl groups in (I) were both modelled using six half-occupancy H-atom sites offset from one another by 60°.
For all compounds, data collection: KappaCCD Server Software (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, 2002); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).
C6H9N3O | F(000) = 296 |
Mr = 139.16 | Dx = 1.411 Mg m−3 |
Orthorhombic, Pnma | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2n | Cell parameters from 797 reflections |
a = 8.1442 (17) Å | θ = 3.0–27.4° |
b = 6.5456 (11) Å | µ = 0.10 mm−1 |
c = 12.285 (2) Å | T = 120 K |
V = 654.9 (2) Å3 | Plate, colourless |
Z = 4 | 0.25 × 0.20 × 0.02 mm |
Nonius KappaCCD diffractometer | 468 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed X-ray tube | Rint = 0.099 |
Graphite monochromator | θmax = 27.4°, θmin = 3.0° |
ϕ scans and ω scans with κ offsets | h = −10→10 |
7372 measured reflections | k = −8→8 |
797 independent reflections | l = −10→15 |
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)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.136 | H-atom parameters constrained |
S = 0.98 | w = 1/[σ2(Fo2) + (0.0795P)2] where P = (Fo2 + 2Fc2)/3 |
797 reflections | (Δ/σ)max < 0.001 |
61 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
C6H9N3O | V = 654.9 (2) Å3 |
Mr = 139.16 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 8.1442 (17) Å | µ = 0.10 mm−1 |
b = 6.5456 (11) Å | T = 120 K |
c = 12.285 (2) Å | 0.25 × 0.20 × 0.02 mm |
Nonius KappaCCD diffractometer | 468 reflections with I > 2σ(I) |
7372 measured reflections | Rint = 0.099 |
797 independent reflections |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.136 | H-atom parameters constrained |
S = 0.98 | Δρmax = 0.32 e Å−3 |
797 reflections | Δρmin = −0.24 e Å−3 |
61 parameters |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
N1 | 0.6539 (2) | 0.2500 | 0.38300 (14) | 0.0247 (5) | |
N2 | 0.50228 (17) | 0.2500 | 0.22581 (14) | 0.0303 (6) | |
C2 | 0.5046 (2) | 0.2500 | 0.33456 (18) | 0.0234 (5) | |
N3 | 0.3588 (2) | 0.2500 | 0.38607 (13) | 0.0246 (5) | |
C4 | 0.3649 (2) | 0.2500 | 0.49404 (18) | 0.0234 (6) | |
O4 | 0.21476 (15) | 0.2500 | 0.54049 (11) | 0.0277 (5) | |
C41 | 0.2082 (2) | 0.2500 | 0.65685 (16) | 0.0301 (6) | |
C5 | 0.5107 (2) | 0.2500 | 0.55251 (18) | 0.0245 (6) | |
C6 | 0.6537 (3) | 0.2500 | 0.49193 (18) | 0.0248 (6) | |
C61 | 0.8176 (2) | 0.2500 | 0.54723 (17) | 0.0300 (6) | |
H1 | 0.4080 | 0.2500 | 0.1909 | 0.036* | |
H2 | 0.5951 | 0.2500 | 0.1891 | 0.036* | |
H41A | 0.0936 | 0.2399 | 0.6806 | 0.045* | 0.50 |
H41B | 0.2562 | 0.3770 | 0.6846 | 0.045* | 0.50 |
H41C | 0.2703 | 0.1331 | 0.6850 | 0.045* | 0.50 |
H5 | 0.5122 | 0.2500 | 0.6298 | 0.029* | |
H61A | 0.8982 | 0.3195 | 0.5009 | 0.045* | 0.50 |
H61B | 0.8529 | 0.1088 | 0.5599 | 0.045* | 0.50 |
H61C | 0.8090 | 0.3217 | 0.6170 | 0.045* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0185 (10) | 0.0332 (11) | 0.0223 (12) | 0.000 | −0.0014 (7) | 0.000 |
N2 | 0.0215 (11) | 0.0485 (13) | 0.0209 (13) | 0.000 | 0.0003 (7) | 0.000 |
C2 | 0.0202 (12) | 0.0267 (13) | 0.0234 (14) | 0.000 | −0.0007 (8) | 0.000 |
N3 | 0.0212 (10) | 0.0323 (11) | 0.0204 (13) | 0.000 | 0.0006 (7) | 0.000 |
C4 | 0.0163 (12) | 0.0283 (13) | 0.0257 (14) | 0.000 | 0.0015 (8) | 0.000 |
O4 | 0.0186 (8) | 0.0438 (10) | 0.0206 (9) | 0.000 | 0.0025 (6) | 0.000 |
C41 | 0.0239 (12) | 0.0445 (15) | 0.0218 (14) | 0.000 | 0.0044 (9) | 0.000 |
C5 | 0.0223 (12) | 0.0310 (13) | 0.0200 (14) | 0.000 | −0.0010 (8) | 0.000 |
C6 | 0.0220 (12) | 0.0256 (13) | 0.0269 (14) | 0.000 | −0.0014 (9) | 0.000 |
C61 | 0.0186 (12) | 0.0424 (15) | 0.0289 (15) | 0.000 | −0.0027 (9) | 0.000 |
N1—C2 | 1.354 (2) | C41—H41B | 0.9800 |
N2—C2 | 1.336 (3) | C41—H41C | 0.9800 |
N2—H1 | 0.8800 | C5—C6 | 1.382 (3) |
N2—H2 | 0.8800 | C5—H5 | 0.9500 |
C2—N3 | 1.346 (2) | C6—N1 | 1.338 (3) |
N3—C4 | 1.327 (3) | C6—C61 | 1.498 (3) |
C4—O4 | 1.349 (2) | C61—H61A | 0.9800 |
C4—C5 | 1.388 (3) | C61—H61B | 0.9800 |
O4—C41 | 1.430 (2) | C61—H61C | 0.9800 |
C41—H41A | 0.9800 | ||
C6—N1—C2 | 116.03 (18) | O4—C41—H41C | 109.5 |
C2—N2—H1 | 120.0 | H41A—C41—H41C | 109.5 |
C2—N2—H2 | 120.0 | H41B—C41—H41C | 109.5 |
H1—N2—H2 | 120.0 | C6—C5—C4 | 116.3 (2) |
N2—C2—N3 | 117.26 (17) | C6—C5—H5 | 121.9 |
N2—C2—N1 | 116.88 (18) | C4—C5—H5 | 121.9 |
N3—C2—N1 | 125.9 (2) | N1—C6—C5 | 122.63 (19) |
C4—N3—C2 | 115.91 (18) | N1—C6—C61 | 116.93 (18) |
N3—C4—O4 | 112.88 (18) | C5—C6—C61 | 120.4 (2) |
N3—C4—C5 | 123.3 (2) | C6—C61—H61A | 109.5 |
O4—C4—C5 | 123.8 (2) | C6—C61—H61B | 109.5 |
C4—O4—C41 | 117.16 (15) | H61A—C61—H61B | 109.5 |
O4—C41—H41A | 109.5 | C6—C61—H61C | 109.5 |
O4—C41—H41B | 109.5 | H61A—C61—H61C | 109.5 |
H41A—C41—H41B | 109.5 | H61B—C61—H61C | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H1···N1i | 0.88 | 2.26 | 3.136 (2) | 175 |
N2—H2···N3ii | 0.88 | 2.34 | 3.212 (2) | 172 |
Symmetry codes: (i) x−1/2, −y+1/2, −z+1/2; (ii) x+1/2, −y+1/2, −z+1/2. |
C19H19N3O | F(000) = 648 |
Mr = 305.38 | Dx = 1.260 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3667 reflections |
a = 5.8932 (2) Å | θ = 2.9–27.5° |
b = 18.2849 (7) Å | µ = 0.08 mm−1 |
c = 15.1175 (7) Å | T = 120 K |
β = 98.704 (2)° | Needle, colourless |
V = 1610.25 (11) Å3 | 0.26 × 0.18 × 0.10 mm |
Z = 4 |
Nonius KappaCCD diffractometer | 3667 independent reflections |
Radiation source: fine-focus sealed X-ray tube | 2371 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.093 |
ϕ scans, and ω scans with κ offsets | θmax = 27.5°, θmin = 2.9° |
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | h = −7→7 |
Tmin = 0.970, Tmax = 0.992 | k = −23→21 |
12340 measured reflections | l = −19→19 |
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)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.125 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0662P)2] where P = (Fo2 + 2Fc2)/3 |
3667 reflections | (Δ/σ)max < 0.001 |
209 parameters | Δρmax = 0.21 e Å−3 |
0 restraints | Δρmin = −0.28 e Å−3 |
C19H19N3O | V = 1610.25 (11) Å3 |
Mr = 305.38 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 5.8932 (2) Å | µ = 0.08 mm−1 |
b = 18.2849 (7) Å | T = 120 K |
c = 15.1175 (7) Å | 0.26 × 0.18 × 0.10 mm |
β = 98.704 (2)° |
Nonius KappaCCD diffractometer | 3667 independent reflections |
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | 2371 reflections with I > 2σ(I) |
Tmin = 0.970, Tmax = 0.992 | Rint = 0.093 |
12340 measured reflections |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.125 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.21 e Å−3 |
3667 reflections | Δρmin = −0.28 e Å−3 |
209 parameters |
x | y | z | Uiso*/Ueq | ||
N1 | 0.3786 (2) | 0.41128 (6) | 0.54274 (8) | 0.0248 (3) | |
C2 | 0.2046 (2) | 0.42351 (8) | 0.47591 (9) | 0.0235 (3) | |
C21 | 0.0557 (2) | 0.45877 (7) | 0.26654 (10) | 0.0247 (3) | |
C22 | 0.2481 (3) | 0.46390 (8) | 0.22397 (11) | 0.0324 (4) | |
C23 | 0.2572 (3) | 0.42769 (9) | 0.14406 (12) | 0.0360 (4) | |
C24 | 0.0755 (3) | 0.38511 (9) | 0.10589 (11) | 0.0356 (4) | |
C25 | −0.1153 (3) | 0.37827 (9) | 0.14836 (11) | 0.0352 (4) | |
C26 | −0.1248 (3) | 0.41521 (8) | 0.22793 (10) | 0.0299 (4) | |
C27 | 0.0400 (3) | 0.50143 (8) | 0.35103 (10) | 0.0278 (4) | |
N2 | 0.2185 (2) | 0.48339 (7) | 0.42474 (8) | 0.0279 (3) | |
N3 | 0.0163 (2) | 0.38143 (6) | 0.45427 (8) | 0.0247 (3) | |
O4 | −0.17951 (17) | 0.27910 (6) | 0.48822 (7) | 0.0299 (3) | |
C4 | 0.0030 (2) | 0.32420 (8) | 0.50671 (10) | 0.0255 (3) | |
C41 | −0.5105 (3) | 0.23401 (8) | 0.39309 (10) | 0.0281 (4) | |
C42 | −0.7263 (3) | 0.24832 (10) | 0.34582 (11) | 0.0365 (4) | |
C43 | −0.8854 (3) | 0.19269 (11) | 0.32694 (13) | 0.0462 (5) | |
C44 | −0.8316 (3) | 0.12265 (11) | 0.35528 (13) | 0.0456 (5) | |
C45 | −0.6168 (3) | 0.10718 (10) | 0.40146 (12) | 0.0417 (4) | |
C46 | −0.4554 (3) | 0.16270 (9) | 0.42006 (10) | 0.0337 (4) | |
C47 | −0.3399 (3) | 0.29512 (8) | 0.40894 (10) | 0.0288 (4) | |
C5 | 0.1674 (3) | 0.30720 (8) | 0.57925 (10) | 0.0279 (4) | |
C6 | 0.3570 (2) | 0.35210 (8) | 0.59406 (10) | 0.0252 (3) | |
C61 | 0.5501 (3) | 0.33671 (9) | 0.66774 (10) | 0.0307 (4) | |
H22 | 0.3752 | 0.4926 | 0.2500 | 0.039* | |
H23 | 0.3893 | 0.4323 | 0.1154 | 0.043* | |
H24 | 0.0813 | 0.3606 | 0.0508 | 0.043* | |
H25 | −0.2401 | 0.3483 | 0.1231 | 0.042* | |
H26 | −0.2572 | 0.4106 | 0.2564 | 0.036* | |
H27A | 0.0488 | 0.5543 | 0.3379 | 0.033* | |
H27B | −0.1114 | 0.4920 | 0.3696 | 0.033* | |
H2 | 0.3389 | 0.5122 | 0.4364 | 0.034* | |
H42 | −0.7653 | 0.2967 | 0.3262 | 0.044* | |
H43 | −1.0325 | 0.2030 | 0.2942 | 0.055* | |
H44 | −0.9424 | 0.0848 | 0.3431 | 0.055* | |
H45 | −0.5792 | 0.0586 | 0.4206 | 0.050* | |
H46 | −0.3069 | 0.1519 | 0.4513 | 0.040* | |
H47A | −0.2574 | 0.3002 | 0.3569 | 0.035* | |
H47B | −0.4200 | 0.3417 | 0.4167 | 0.035* | |
H5 | 0.1503 | 0.2666 | 0.6169 | 0.034* | |
H61A | 0.6953 | 0.3363 | 0.6436 | 0.046* | |
H61B | 0.5263 | 0.2889 | 0.6943 | 0.046* | |
H61C | 0.5553 | 0.3747 | 0.7137 | 0.046* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0253 (7) | 0.0272 (7) | 0.0218 (6) | −0.0004 (5) | 0.0033 (5) | −0.0019 (5) |
C2 | 0.0269 (8) | 0.0232 (7) | 0.0208 (8) | 0.0007 (6) | 0.0049 (6) | −0.0046 (6) |
C21 | 0.0272 (8) | 0.0201 (7) | 0.0250 (8) | 0.0036 (6) | −0.0016 (6) | 0.0030 (6) |
C22 | 0.0288 (8) | 0.0305 (8) | 0.0371 (9) | −0.0018 (7) | 0.0024 (7) | −0.0029 (7) |
C23 | 0.0345 (9) | 0.0371 (9) | 0.0381 (9) | 0.0021 (7) | 0.0111 (7) | −0.0019 (8) |
C24 | 0.0447 (10) | 0.0342 (9) | 0.0273 (9) | 0.0017 (7) | 0.0031 (7) | −0.0033 (7) |
C25 | 0.0360 (9) | 0.0367 (9) | 0.0306 (9) | −0.0086 (7) | −0.0027 (7) | −0.0025 (7) |
C26 | 0.0285 (8) | 0.0334 (8) | 0.0269 (8) | −0.0012 (7) | 0.0015 (7) | 0.0021 (7) |
C27 | 0.0284 (8) | 0.0263 (8) | 0.0276 (8) | 0.0029 (6) | 0.0007 (7) | 0.0006 (7) |
N2 | 0.0304 (7) | 0.0265 (7) | 0.0249 (7) | −0.0035 (5) | −0.0019 (6) | 0.0019 (5) |
N3 | 0.0255 (7) | 0.0252 (7) | 0.0235 (7) | −0.0013 (5) | 0.0038 (5) | −0.0032 (5) |
O4 | 0.0292 (6) | 0.0350 (6) | 0.0240 (6) | −0.0090 (5) | −0.0008 (4) | 0.0001 (5) |
C4 | 0.0267 (8) | 0.0270 (8) | 0.0230 (8) | −0.0047 (6) | 0.0049 (6) | −0.0044 (6) |
C41 | 0.0276 (8) | 0.0355 (9) | 0.0222 (8) | −0.0017 (7) | 0.0064 (6) | −0.0065 (7) |
C42 | 0.0305 (9) | 0.0447 (10) | 0.0341 (9) | 0.0032 (7) | 0.0038 (7) | −0.0118 (8) |
C43 | 0.0280 (9) | 0.0670 (13) | 0.0432 (11) | −0.0039 (9) | 0.0045 (8) | −0.0251 (10) |
C44 | 0.0406 (11) | 0.0589 (13) | 0.0395 (10) | −0.0240 (9) | 0.0127 (8) | −0.0231 (9) |
C45 | 0.0529 (12) | 0.0380 (9) | 0.0357 (10) | −0.0135 (8) | 0.0113 (9) | −0.0065 (8) |
C46 | 0.0374 (9) | 0.0391 (9) | 0.0243 (8) | −0.0047 (7) | 0.0039 (7) | −0.0025 (7) |
C47 | 0.0277 (8) | 0.0327 (9) | 0.0252 (8) | −0.0015 (6) | 0.0018 (6) | −0.0024 (7) |
C5 | 0.0328 (9) | 0.0287 (8) | 0.0221 (8) | −0.0039 (6) | 0.0036 (7) | 0.0018 (6) |
C6 | 0.0284 (8) | 0.0276 (8) | 0.0202 (7) | 0.0001 (6) | 0.0057 (6) | −0.0028 (6) |
C61 | 0.0300 (8) | 0.0360 (9) | 0.0254 (8) | −0.0053 (7) | 0.0017 (7) | 0.0031 (7) |
N1—C2 | 1.3447 (19) | C26—H26 | 0.95 |
C2—N3 | 1.3493 (18) | C27—H27A | 0.99 |
N3—C4 | 1.3223 (19) | C27—H27B | 0.99 |
C4—C5 | 1.384 (2) | N2—H2 | 0.88 |
C5—C6 | 1.377 (2) | C41—C42 | 1.386 (2) |
C6—N1 | 1.3486 (19) | C41—C46 | 1.390 (2) |
C2—N2 | 1.3501 (19) | C41—C47 | 1.498 (2) |
N2—C27 | 1.450 (2) | C42—C43 | 1.383 (2) |
C4—O4 | 1.3505 (18) | C42—H42 | 0.95 |
O4—C47 | 1.4398 (19) | C43—C44 | 1.372 (3) |
C6—C61 | 1.494 (2) | C43—H43 | 0.95 |
C21—C26 | 1.385 (2) | C44—C45 | 1.379 (3) |
C21—C22 | 1.389 (2) | C44—H44 | 0.95 |
C21—C27 | 1.511 (2) | C45—C46 | 1.391 (2) |
C22—C23 | 1.386 (2) | C45—H45 | 0.95 |
C22—H22 | 0.95 | C46—H46 | 0.95 |
C23—C24 | 1.378 (2) | C47—H47A | 0.99 |
C23—H23 | 0.95 | C47—H47B | 0.99 |
C24—C25 | 1.382 (2) | C5—H5 | 0.95 |
C24—H24 | 0.95 | C61—H61A | 0.98 |
C25—C26 | 1.388 (2) | C61—H61B | 0.98 |
C25—H25 | 0.95 | C61—H61C | 0.98 |
C2—N1—C6 | 115.97 (12) | C42—C41—C46 | 118.93 (15) |
N1—C2—N3 | 126.36 (13) | C42—C41—C47 | 118.87 (15) |
N1—C2—N2 | 117.39 (13) | C46—C41—C47 | 122.11 (14) |
N3—C2—N2 | 116.25 (13) | C43—C42—C41 | 120.51 (17) |
C26—C21—C22 | 118.18 (14) | C43—C42—H42 | 119.7 |
C26—C21—C27 | 120.77 (13) | C41—C42—H42 | 119.7 |
C22—C21—C27 | 121.02 (13) | C44—C43—C42 | 120.30 (17) |
C23—C22—C21 | 120.88 (15) | C44—C43—H43 | 119.9 |
C23—C22—H22 | 119.6 | C42—C43—H43 | 119.9 |
C21—C22—H22 | 119.6 | C43—C44—C45 | 120.03 (16) |
C24—C23—C22 | 120.34 (15) | C43—C44—H44 | 120.0 |
C24—C23—H23 | 119.8 | C45—C44—H44 | 120.0 |
C22—C23—H23 | 119.8 | C44—C45—C46 | 120.00 (17) |
C23—C24—C25 | 119.46 (15) | C44—C45—H45 | 120.0 |
C23—C24—H24 | 120.3 | C46—C45—H45 | 120.0 |
C25—C24—H24 | 120.3 | C41—C46—C45 | 120.21 (16) |
C24—C25—C26 | 120.04 (15) | C41—C46—H46 | 119.9 |
C24—C25—H25 | 120.0 | C45—C46—H46 | 119.9 |
C26—C25—H25 | 120.0 | O4—C47—C41 | 108.76 (12) |
C21—C26—C25 | 121.07 (14) | O4—C47—H47A | 109.9 |
C21—C26—H26 | 119.5 | C41—C47—H47A | 109.9 |
C25—C26—H26 | 119.5 | O4—C47—H47B | 109.9 |
N2—C27—C21 | 113.70 (12) | C41—C47—H47B | 109.9 |
N2—C27—H27A | 108.8 | H47A—C47—H47B | 108.3 |
C21—C27—H27A | 108.8 | C6—C5—C4 | 116.62 (14) |
N2—C27—H27B | 108.8 | C6—C5—H5 | 121.7 |
C21—C27—H27B | 108.8 | C4—C5—H5 | 121.7 |
H27A—C27—H27B | 107.7 | N1—C6—C5 | 121.99 (14) |
C2—N2—C27 | 121.68 (13) | N1—C6—C61 | 116.91 (13) |
C2—N2—H2 | 119.2 | C5—C6—C61 | 121.10 (14) |
C27—N2—H2 | 119.2 | C6—C61—H61A | 109.5 |
C4—N3—C2 | 115.30 (12) | C6—C61—H61B | 109.5 |
C4—O4—C47 | 116.74 (11) | H61A—C61—H61B | 109.5 |
N3—C4—O4 | 118.49 (13) | C6—C61—H61C | 109.5 |
N3—C4—C5 | 123.68 (14) | H61A—C61—H61C | 109.5 |
O4—C4—C5 | 117.82 (13) | H61B—C61—H61C | 109.5 |
C6—N1—C2—N3 | −2.0 (2) | N3—C4—O4—C47 | 3.38 (19) |
C6—N1—C2—N2 | 178.36 (12) | C47—O4—C4—C5 | −175.87 (13) |
C26—C21—C22—C23 | 1.4 (2) | C46—C41—C42—C43 | 0.9 (2) |
C27—C21—C22—C23 | −176.65 (14) | C47—C41—C42—C43 | 177.54 (14) |
C21—C22—C23—C24 | −0.8 (2) | C41—C42—C43—C44 | 0.4 (3) |
C22—C23—C24—C25 | −0.5 (2) | C42—C43—C44—C45 | −1.1 (3) |
C23—C24—C25—C26 | 1.2 (2) | C43—C44—C45—C46 | 0.6 (3) |
C22—C21—C26—C25 | −0.7 (2) | C42—C41—C46—C45 | −1.4 (2) |
C27—C21—C26—C25 | 177.32 (14) | C47—C41—C46—C45 | −177.95 (14) |
C24—C25—C26—C21 | −0.6 (2) | C44—C45—C46—C41 | 0.7 (2) |
C26—C21—C27—N2 | 121.32 (15) | C4—O4—C47—C41 | 172.35 (12) |
N3—C2—N2—C27 | 0.31 (19) | O4—C47—C41—C42 | 154.41 (13) |
N1—C2—N2—C27 | 179.97 (12) | C46—C41—C47—O4 | −29.09 (19) |
C2—N2—C27—C21 | −80.49 (17) | N3—C4—C5—C6 | −2.2 (2) |
N2—C27—C21—C22 | −60.71 (18) | O4—C4—C5—C6 | 177.00 (12) |
N1—C2—N3—C4 | 2.2 (2) | C2—N1—C6—C5 | −0.42 (19) |
N2—C2—N3—C4 | −178.20 (12) | C2—N1—C6—C61 | 178.98 (12) |
C2—N3—C4—O4 | −179.11 (11) | C4—C5—C6—N1 | 2.4 (2) |
C2—N3—C4—C5 | 0.1 (2) | C4—C5—C6—C61 | −177.02 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···N1i | 0.88 | 2.16 | 3.039 (2) | 176 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
C25H23N3O2 | F(000) = 840 |
Mr = 397.46 | Dx = 1.273 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4691 reflections |
a = 5.6056 (2) Å | θ = 3.0–27.5° |
b = 18.2446 (5) Å | µ = 0.08 mm−1 |
c = 20.6480 (8) Å | T = 120 K |
β = 100.965 (1)° | Block, colourless |
V = 2073.16 (12) Å3 | 0.50 × 0.30 × 0.15 mm |
Z = 4 |
Nonius KappaCCD diffractometer | 4691 independent reflections |
Radiation source: fine-focus sealed X-ray tube | 2822 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.076 |
ϕ scans, and ω scans with κ offsets | θmax = 27.5°, θmin = 3.0° |
Absorption correction: multi-scan (DENZO–SMN; Otwinowski & Minor, 1997) | h = −7→6 |
Tmin = 0.950, Tmax = 0.987 | k = −23→18 |
16019 measured reflections | l = −26→26 |
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)] = 0.054 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.131 | H-atom parameters constrained |
S = 0.96 | w = 1/[σ2(Fo2) + (0.0684P)2] where P = (Fo2 + 2Fc2)/3 |
4691 reflections | (Δ/σ)max < 0.001 |
271 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.31 e Å−3 |
C25H23N3O2 | V = 2073.16 (12) Å3 |
Mr = 397.46 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 5.6056 (2) Å | µ = 0.08 mm−1 |
b = 18.2446 (5) Å | T = 120 K |
c = 20.6480 (8) Å | 0.50 × 0.30 × 0.15 mm |
β = 100.965 (1)° |
Nonius KappaCCD diffractometer | 4691 independent reflections |
Absorption correction: multi-scan (DENZO–SMN; Otwinowski & Minor, 1997) | 2822 reflections with I > 2σ(I) |
Tmin = 0.950, Tmax = 0.987 | Rint = 0.076 |
16019 measured reflections |
R[F2 > 2σ(F2)] = 0.054 | 0 restraints |
wR(F2) = 0.131 | H-atom parameters constrained |
S = 0.96 | Δρmax = 0.23 e Å−3 |
4691 reflections | Δρmin = −0.31 e Å−3 |
271 parameters |
x | y | z | Uiso*/Ueq | ||
N1 | 1.0799 (2) | 0.40310 (8) | 0.62780 (7) | 0.0219 (4) | |
C2 | 0.8732 (3) | 0.40173 (10) | 0.58335 (8) | 0.0212 (4) | |
C21 | 0.6951 (3) | 0.21091 (10) | 0.58460 (9) | 0.0241 (4) | |
C22 | 0.5821 (3) | 0.17710 (11) | 0.63056 (9) | 0.0309 (5) | |
C23 | 0.4128 (4) | 0.12225 (12) | 0.61258 (10) | 0.0364 (5) | |
C24 | 0.3545 (3) | 0.10049 (11) | 0.54768 (10) | 0.0348 (5) | |
C25 | 0.4638 (4) | 0.13319 (12) | 0.50108 (10) | 0.0408 (5) | |
C26 | 0.6342 (4) | 0.18797 (11) | 0.51939 (10) | 0.0369 (5) | |
C27 | 0.8704 (3) | 0.27252 (10) | 0.60378 (9) | 0.0270 (4) | |
O2 | 0.7589 (2) | 0.33668 (7) | 0.57016 (6) | 0.0253 (3) | |
N3 | 0.7552 (2) | 0.45599 (8) | 0.54943 (7) | 0.0213 (3) | |
N4 | 0.7413 (2) | 0.57865 (8) | 0.52500 (7) | 0.0221 (4) | |
C4 | 0.8585 (3) | 0.52300 (10) | 0.56023 (8) | 0.0207 (4) | |
C41 | 0.7785 (3) | 0.68374 (10) | 0.60319 (9) | 0.0226 (4) | |
C42 | 0.6246 (4) | 0.64959 (12) | 0.63845 (10) | 0.0387 (5) | |
C43 | 0.5943 (4) | 0.67636 (12) | 0.69907 (11) | 0.0431 (6) | |
C44 | 0.7198 (3) | 0.73721 (11) | 0.72561 (10) | 0.0331 (5) | |
C45 | 0.8752 (4) | 0.77118 (12) | 0.69155 (10) | 0.0408 (6) | |
C46 | 0.9047 (4) | 0.74430 (12) | 0.63086 (10) | 0.0369 (5) | |
C47 | 0.8116 (3) | 0.65442 (10) | 0.53648 (9) | 0.0241 (4) | |
C5 | 1.0748 (3) | 0.53260 (10) | 0.60609 (8) | 0.0217 (4) | |
C6 | 1.1744 (3) | 0.47034 (10) | 0.63757 (8) | 0.0219 (4) | |
C61 | 1.6809 (3) | 0.44110 (10) | 0.77412 (9) | 0.0232 (4) | |
C62 | 1.7009 (3) | 0.41495 (11) | 0.83814 (9) | 0.0279 (4) | |
C63 | 1.8945 (3) | 0.43636 (11) | 0.88699 (10) | 0.0321 (5) | |
C64 | 2.0670 (3) | 0.48398 (11) | 0.87229 (10) | 0.0328 (5) | |
C65 | 2.0476 (3) | 0.51062 (11) | 0.80854 (10) | 0.0325 (5) | |
C66 | 1.8547 (3) | 0.48915 (11) | 0.75981 (9) | 0.0282 (5) | |
C67 | 1.4741 (3) | 0.41581 (10) | 0.72120 (9) | 0.0254 (4) | |
O6 | 1.3804 (2) | 0.47949 (7) | 0.68340 (6) | 0.0260 (3) | |
H22 | 0.6217 | 0.1919 | 0.6754 | 0.037* | |
H23 | 0.3369 | 0.0997 | 0.6448 | 0.044* | |
H24 | 0.2383 | 0.0627 | 0.5351 | 0.042* | |
H25 | 0.4226 | 0.1183 | 0.4563 | 0.049* | |
H26 | 0.7103 | 0.2101 | 0.4870 | 0.044* | |
H27A | 0.9010 | 0.2800 | 0.6521 | 0.032* | |
H27B | 1.0269 | 0.2618 | 0.5902 | 0.032* | |
H4 | 0.6162 | 0.5684 | 0.4936 | 0.027* | |
H42 | 0.5381 | 0.6071 | 0.6209 | 0.046* | |
H43 | 0.4860 | 0.6525 | 0.7224 | 0.052* | |
H44 | 0.6990 | 0.7556 | 0.7672 | 0.040* | |
H45 | 0.9631 | 0.8133 | 0.7096 | 0.049* | |
H46 | 1.0142 | 0.7681 | 0.6079 | 0.044* | |
H47A | 0.7144 | 0.6848 | 0.5014 | 0.029* | |
H47B | 0.9845 | 0.6597 | 0.5330 | 0.029* | |
H5 | 1.1482 | 0.5794 | 0.6149 | 0.026* | |
H62 | 1.5817 | 0.3823 | 0.8486 | 0.033* | |
H63 | 1.9077 | 0.4181 | 0.9306 | 0.039* | |
H64 | 2.1993 | 0.4986 | 0.9057 | 0.039* | |
H65 | 2.1664 | 0.5436 | 0.7983 | 0.039* | |
H66 | 1.8418 | 0.5076 | 0.7162 | 0.034* | |
H67A | 1.5324 | 0.3792 | 0.6924 | 0.031* | |
H67B | 1.3454 | 0.3930 | 0.7413 | 0.031* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0233 (8) | 0.0220 (9) | 0.0196 (8) | −0.0025 (6) | 0.0022 (6) | −0.0002 (7) |
C2 | 0.0234 (9) | 0.0219 (11) | 0.0183 (9) | −0.0022 (8) | 0.0041 (7) | −0.0021 (8) |
C21 | 0.0251 (9) | 0.0222 (11) | 0.0240 (10) | 0.0016 (8) | 0.0020 (7) | 0.0013 (8) |
C22 | 0.0343 (10) | 0.0342 (13) | 0.0235 (10) | −0.0032 (9) | 0.0038 (8) | 0.0020 (9) |
C23 | 0.0379 (11) | 0.0399 (14) | 0.0318 (12) | −0.0094 (10) | 0.0074 (9) | 0.0095 (10) |
C24 | 0.0341 (11) | 0.0298 (13) | 0.0368 (12) | −0.0104 (9) | −0.0027 (9) | 0.0053 (10) |
C25 | 0.0557 (13) | 0.0395 (14) | 0.0258 (11) | −0.0172 (11) | 0.0047 (9) | −0.0061 (10) |
C26 | 0.0477 (12) | 0.0355 (13) | 0.0299 (11) | −0.0157 (10) | 0.0132 (9) | −0.0014 (10) |
C27 | 0.0309 (10) | 0.0222 (11) | 0.0254 (10) | −0.0002 (8) | −0.0003 (8) | 0.0041 (8) |
O2 | 0.0276 (6) | 0.0174 (7) | 0.0279 (7) | −0.0024 (5) | −0.0024 (5) | 0.0011 (6) |
N3 | 0.0233 (7) | 0.0193 (9) | 0.0205 (8) | −0.0029 (6) | 0.0018 (6) | −0.0007 (7) |
N4 | 0.0256 (8) | 0.0197 (9) | 0.0182 (8) | −0.0026 (6) | −0.0033 (6) | −0.0008 (6) |
C4 | 0.0235 (9) | 0.0238 (11) | 0.0156 (9) | −0.0010 (8) | 0.0056 (7) | −0.0009 (8) |
C41 | 0.0212 (8) | 0.0214 (11) | 0.0245 (10) | 0.0021 (7) | 0.0023 (7) | 0.0010 (8) |
C42 | 0.0360 (11) | 0.0393 (14) | 0.0446 (13) | −0.0150 (9) | 0.0175 (9) | −0.0167 (11) |
C43 | 0.0460 (12) | 0.0454 (15) | 0.0452 (13) | −0.0160 (10) | 0.0270 (10) | −0.0144 (11) |
C44 | 0.0412 (11) | 0.0328 (13) | 0.0266 (11) | −0.0013 (9) | 0.0101 (9) | −0.0066 (9) |
C45 | 0.0507 (13) | 0.0357 (14) | 0.0376 (13) | −0.0175 (10) | 0.0124 (10) | −0.0142 (10) |
C46 | 0.0460 (12) | 0.0350 (13) | 0.0332 (12) | −0.0182 (10) | 0.0163 (9) | −0.0051 (10) |
C47 | 0.0285 (9) | 0.0208 (11) | 0.0221 (10) | −0.0014 (8) | 0.0030 (7) | 0.0004 (8) |
C5 | 0.0229 (9) | 0.0204 (11) | 0.0219 (9) | −0.0029 (7) | 0.0044 (7) | −0.0008 (8) |
C6 | 0.0215 (9) | 0.0263 (11) | 0.0174 (9) | −0.0024 (8) | 0.0026 (7) | −0.0010 (8) |
C61 | 0.0231 (9) | 0.0209 (11) | 0.0244 (10) | 0.0052 (8) | 0.0015 (7) | −0.0029 (8) |
C62 | 0.0287 (10) | 0.0261 (12) | 0.0278 (11) | 0.0029 (8) | 0.0029 (8) | 0.0025 (8) |
C63 | 0.0376 (11) | 0.0278 (12) | 0.0269 (11) | 0.0082 (9) | −0.0040 (8) | −0.0005 (9) |
C64 | 0.0263 (10) | 0.0318 (13) | 0.0353 (12) | 0.0056 (9) | −0.0068 (8) | −0.0055 (9) |
C65 | 0.0252 (10) | 0.0354 (13) | 0.0372 (12) | −0.0023 (8) | 0.0062 (8) | −0.0062 (10) |
C66 | 0.0258 (9) | 0.0330 (12) | 0.0258 (10) | 0.0024 (8) | 0.0052 (8) | −0.0019 (9) |
C67 | 0.0272 (10) | 0.0226 (11) | 0.0245 (10) | 0.0015 (8) | −0.0002 (7) | 0.0025 (8) |
O6 | 0.0241 (6) | 0.0248 (8) | 0.0254 (7) | −0.0035 (5) | −0.0048 (5) | 0.0023 (6) |
N1—C2 | 1.335 (2) | C41—C42 | 1.379 (3) |
C2—N3 | 1.316 (2) | C41—C47 | 1.522 (3) |
N3—C4 | 1.353 (2) | C42—C43 | 1.384 (3) |
C4—C5 | 1.400 (2) | C42—H42 | 0.95 |
C5—C6 | 1.374 (2) | C43—C44 | 1.371 (3) |
C6—N1 | 1.336 (2) | C43—H43 | 0.95 |
C2—O2 | 1.352 (2) | C44—C45 | 1.368 (3) |
O2—C27 | 1.441 (2) | C44—H44 | 0.95 |
C4—N4 | 1.345 (2) | C45—C46 | 1.384 (3) |
N4—C47 | 1.445 (2) | C45—H45 | 0.95 |
C6—O6 | 1.357 (2) | C46—H46 | 0.95 |
O6—C67 | 1.442 (2) | C47—H47A | 0.99 |
C21—C22 | 1.382 (3) | C47—H47B | 0.99 |
C21—C26 | 1.389 (3) | C5—H5 | 0.95 |
C21—C27 | 1.496 (3) | C61—C66 | 1.384 (3) |
C22—C23 | 1.380 (3) | C61—C62 | 1.390 (2) |
C22—H22 | 0.95 | C61—C67 | 1.506 (2) |
C23—C24 | 1.376 (3) | C62—C63 | 1.389 (3) |
C23—H23 | 0.95 | C62—H62 | 0.95 |
C24—C25 | 1.372 (3) | C63—C64 | 1.376 (3) |
C24—H24 | 0.95 | C63—H63 | 0.95 |
C25—C26 | 1.384 (3) | C64—C65 | 1.388 (3) |
C25—H25 | 0.95 | C64—H64 | 0.95 |
C26—H26 | 0.95 | C65—C66 | 1.386 (3) |
C27—H27A | 0.99 | C65—H65 | 0.95 |
C27—H27B | 0.99 | C66—H66 | 0.95 |
N4—H4 | 0.88 | C67—H67A | 0.99 |
C41—C46 | 1.376 (3) | C67—H67B | 0.99 |
C2—N1—C6 | 112.86 (15) | C45—C44—H44 | 120.3 |
N3—C2—N1 | 129.39 (17) | C43—C44—H44 | 120.3 |
N3—C2—O2 | 112.48 (14) | C44—C45—C46 | 120.15 (19) |
N1—C2—O2 | 118.12 (15) | C44—C45—H45 | 119.9 |
C22—C21—C26 | 118.08 (17) | C46—C45—H45 | 119.9 |
C22—C21—C27 | 121.15 (17) | C41—C46—C45 | 121.32 (18) |
C26—C21—C27 | 120.72 (17) | C41—C46—H46 | 119.3 |
C23—C22—C21 | 121.34 (18) | C45—C46—H46 | 119.3 |
C23—C22—H22 | 119.3 | N4—C47—C41 | 114.11 (15) |
C21—C22—H22 | 119.3 | N4—C47—H47A | 108.7 |
C24—C23—C22 | 119.65 (18) | C41—C47—H47A | 108.7 |
C24—C23—H23 | 120.2 | N4—C47—H47B | 108.7 |
C22—C23—H23 | 120.2 | C41—C47—H47B | 108.7 |
C25—C24—C23 | 120.18 (19) | H47A—C47—H47B | 107.6 |
C25—C24—H24 | 119.9 | C6—C5—C4 | 116.01 (16) |
C23—C24—H24 | 119.9 | C6—C5—H5 | 122.0 |
C24—C25—C26 | 119.96 (19) | C4—C5—H5 | 122.0 |
C24—C25—H25 | 120.0 | N1—C6—O6 | 118.59 (15) |
C26—C25—H25 | 120.0 | N1—C6—C5 | 125.02 (16) |
C25—C26—C21 | 120.78 (18) | O6—C6—C5 | 116.35 (16) |
C25—C26—H26 | 119.6 | C66—C61—C62 | 119.21 (16) |
C21—C26—H26 | 119.6 | C66—C61—C67 | 121.00 (16) |
O2—C27—C21 | 106.25 (14) | C62—C61—C67 | 119.79 (16) |
O2—C27—H27A | 110.5 | C63—C62—C61 | 120.31 (18) |
C21—C27—H27A | 110.5 | C63—C62—H62 | 119.8 |
O2—C27—H27B | 110.5 | C61—C62—H62 | 119.8 |
C21—C27—H27B | 110.5 | C64—C63—C62 | 120.12 (18) |
H27A—C27—H27B | 108.7 | C64—C63—H63 | 119.9 |
C2—O2—C27 | 118.07 (13) | C62—C63—H63 | 119.9 |
C2—N3—C4 | 115.86 (15) | C63—C64—C65 | 119.90 (17) |
C4—N4—C47 | 122.92 (14) | C63—C64—H64 | 120.0 |
C4—N4—H4 | 118.5 | C65—C64—H64 | 120.0 |
C47—N4—H4 | 118.5 | C66—C65—C64 | 119.96 (19) |
N4—C4—N3 | 116.32 (15) | C66—C65—H65 | 120.0 |
N4—C4—C5 | 122.84 (16) | C64—C65—H65 | 120.0 |
N3—C4—C5 | 120.85 (16) | C61—C66—C65 | 120.51 (18) |
C46—C41—C42 | 117.86 (17) | C61—C66—H66 | 119.7 |
C46—C41—C47 | 121.11 (16) | C65—C66—H66 | 119.7 |
C42—C41—C47 | 121.02 (16) | O6—C67—C61 | 107.27 (14) |
C41—C42—C43 | 120.99 (19) | O6—C67—H67A | 110.3 |
C41—C42—H42 | 119.5 | C61—C67—H67A | 110.3 |
C43—C42—H42 | 119.5 | O6—C67—H67B | 110.3 |
C44—C43—C42 | 120.35 (19) | C61—C67—H67B | 110.3 |
C44—C43—H43 | 119.8 | H67A—C67—H67B | 108.5 |
C42—C43—H43 | 119.8 | C6—O6—C67 | 116.91 (13) |
C45—C44—C43 | 119.32 (18) | ||
C6—N1—C2—N3 | −0.2 (3) | C42—C43—C44—C45 | 0.0 (3) |
C6—N1—C2—O2 | −179.01 (14) | C43—C44—C45—C46 | 0.1 (3) |
C26—C21—C22—C23 | −0.2 (3) | C42—C41—C46—C45 | −1.3 (3) |
C27—C21—C22—C23 | 177.32 (18) | C47—C41—C46—C45 | 180.00 (19) |
C21—C22—C23—C24 | 0.0 (3) | C44—C45—C46—C41 | 0.5 (3) |
C22—C23—C24—C25 | −0.1 (3) | C46—C41—C47—N4 | 158.68 (17) |
C23—C24—C25—C26 | 0.3 (3) | N4—C4—C5—C6 | −179.18 (16) |
C24—C25—C26—C21 | −0.5 (3) | N3—C4—C5—C6 | 1.2 (2) |
C22—C21—C26—C25 | 0.5 (3) | C2—N1—C6—O6 | 177.68 (14) |
C27—C21—C26—C25 | −177.08 (19) | C2—N1—C6—C5 | −0.1 (2) |
C26—C21—C27—O2 | 63.4 (2) | C4—C5—C6—N1 | −0.5 (3) |
N3—C2—O2—C27 | 179.54 (14) | C4—C5—C6—O6 | −178.24 (14) |
N1—C2—O2—C27 | −1.4 (2) | C66—C61—C62—C63 | −0.6 (3) |
C2—O2—C27—C21 | 174.90 (15) | C67—C61—C62—C63 | 178.28 (17) |
O2—C27—C21—C22 | −114.06 (18) | C61—C62—C63—C64 | 0.3 (3) |
N1—C2—N3—C4 | 0.9 (3) | C62—C63—C64—C65 | 0.0 (3) |
O2—C2—N3—C4 | 179.79 (14) | C63—C64—C65—C66 | −0.1 (3) |
C47—N4—C4—N3 | 172.32 (14) | C62—C61—C66—C65 | 0.5 (3) |
C5—C4—N4—C47 | −7.3 (2) | C67—C61—C66—C65 | −178.38 (17) |
C4—N4—C47—C41 | −65.7 (2) | C64—C65—C66—C61 | −0.1 (3) |
N4—C47—C41—C42 | −20.0 (2) | C66—C61—C67—O6 | −44.9 (2) |
C2—N3—C4—N4 | 178.97 (15) | N1—C6—O6—C67 | −3.6 (2) |
C2—N3—C4—C5 | −1.4 (2) | C6—O6—C67—C61 | −172.75 (14) |
C46—C41—C42—C43 | 1.4 (3) | O6—C67—C61—C62 | 136.29 (16) |
C47—C41—C42—C43 | −179.89 (19) | C5—C6—O6—C67 | 174.31 (15) |
C41—C42—C43—C44 | −0.8 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4···N3i | 0.88 | 2.15 | 2.980 (2) | 157 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
(I) | (II) | (III) | |
Crystal data | |||
Chemical formula | C6H9N3O | C19H19N3O | C25H23N3O2 |
Mr | 139.16 | 305.38 | 397.46 |
Crystal system, space group | Orthorhombic, Pnma | Monoclinic, P21/c | Monoclinic, P21/c |
Temperature (K) | 120 | 120 | 120 |
a, b, c (Å) | 8.1442 (17), 6.5456 (11), 12.285 (2) | 5.8932 (2), 18.2849 (7), 15.1175 (7) | 5.6056 (2), 18.2446 (5), 20.6480 (8) |
α, β, γ (°) | 90, 90, 90 | 90, 98.704 (2), 90 | 90, 100.965 (1), 90 |
V (Å3) | 654.9 (2) | 1610.25 (11) | 2073.16 (12) |
Z | 4 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.10 | 0.08 | 0.08 |
Crystal size (mm) | 0.25 × 0.20 × 0.02 | 0.26 × 0.18 × 0.10 | 0.50 × 0.30 × 0.15 |
Data collection | |||
Diffractometer | Nonius KappaCCD diffractometer | Nonius KappaCCD diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | – | Multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | Multi-scan (DENZO–SMN; Otwinowski & Minor, 1997) |
Tmin, Tmax | – | 0.970, 0.992 | 0.950, 0.987 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7372, 797, 468 | 12340, 3667, 2371 | 16019, 4691, 2822 |
Rint | 0.099 | 0.093 | 0.076 |
(sin θ/λ)max (Å−1) | 0.648 | 0.650 | 0.649 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.136, 0.98 | 0.050, 0.125, 1.00 | 0.054, 0.131, 0.96 |
No. of reflections | 797 | 3667 | 4691 |
No. of parameters | 61 | 209 | 271 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.32, −0.24 | 0.21, −0.28 | 0.23, −0.31 |
Computer programs: KappaCCD Server Software (Nonius, 1997), DENZO–SMN (Otwinowski & Minor, 1997), DENZO–SMN, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2002), SHELXL97 and PRPKAPPA (Ferguson, 1999).
N1—C2 | 1.354 (2) | C4—C5 | 1.388 (3) |
C2—N3 | 1.346 (2) | C5—C6 | 1.382 (3) |
N3—C4 | 1.327 (3) | C6—N1 | 1.338 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H1···N1i | 0.88 | 2.26 | 3.136 (2) | 175 |
N2—H2···N3ii | 0.88 | 2.34 | 3.212 (2) | 172 |
Symmetry codes: (i) x−1/2, −y+1/2, −z+1/2; (ii) x+1/2, −y+1/2, −z+1/2. |
N1—C2 | 1.3447 (19) | C2—N2 | 1.3501 (19) |
C2—N3 | 1.3493 (18) | N2—C27 | 1.450 (2) |
N3—C4 | 1.3223 (19) | C4—O4 | 1.3505 (18) |
C4—C5 | 1.384 (2) | O4—C47 | 1.4398 (19) |
C5—C6 | 1.377 (2) | C6—C61 | 1.494 (2) |
C6—N1 | 1.3486 (19) | ||
N1—C2—N2—C27 | 179.97 (12) | N3—C4—O4—C47 | 3.38 (19) |
C2—N2—C27—C21 | −80.49 (17) | C4—O4—C47—C41 | 172.35 (12) |
N2—C27—C21—C22 | −60.71 (18) | O4—C47—C41—C42 | 154.41 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···N1i | 0.88 | 2.16 | 3.039 (2) | 176 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
N1—C2 | 1.335 (2) | C2—O2 | 1.352 (2) |
C2—N3 | 1.316 (2) | O2—C27 | 1.441 (2) |
N3—C4 | 1.353 (2) | C4—N4 | 1.345 (2) |
C4—C5 | 1.400 (2) | N4—C47 | 1.445 (2) |
C5—C6 | 1.374 (2) | C6—O6 | 1.357 (2) |
C6—N1 | 1.336 (2) | O6—C67 | 1.442 (2) |
N1—C2—O2—C27 | −1.4 (2) | N4—C47—C41—C42 | −20.0 (2) |
C2—O2—C27—C21 | 174.90 (15) | N1—C6—O6—C67 | −3.6 (2) |
O2—C27—C21—C22 | −114.06 (18) | C6—O6—C67—C61 | −172.75 (14) |
C5—C4—N4—C47 | −7.3 (2) | O6—C67—C61—C62 | 136.29 (16) |
C4—N4—C47—C41 | −65.7 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4···N3i | 0.88 | 2.15 | 2.980 (2) | 157 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Alkoxypyrimidines are key intermediates for the synthesis of a wide range of alkoxy- and amino-substituted O6-benzyloxy-5-nitrosopyrimidines (Marchal et al., 1998, 2000; Quesada et al., 2000), 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 structures of three examples of this class, namely 2-amino-4-methoxy-6-methylpyrimidine, (I), 2-benzylamino-4-benzyloxy-6-methylpyrimidine, (II), and 4-benzylamino-2,6-bis(benzyloxy)pyrimidine, (III).
Compound (I) (Fig. 1) crystallizes in space group Pnma with all non-H atoms lying on mirror planes, with the plane for the reference molecule selected as that at y = 0.25. The molecules are linked by two N—H···N hydrogen bonds (Table 2) into chains of edge-fused rings, which themselves are linked into sheets by π–π-stacking interactions. The amino atom N2 in the reference molecule at (x, 1/4, z) acts as hydrogen-bond donor, via H1 and H2, respectively, to atom N1 in the molecule at (−0.5 + x, 1/4, 0.5 − z) and to atom N3 in that at (0.5 + x, 1/4, 0.5 − z), and propagation of these two hydrogen bonds generates a chain of edge-fused R22(8) rings running parallel to the [100] direction and generated by the a-glide plane at z = 0.25 (Fig. 2). This hydrogen-bonded substructure may alternatively be regarded as a molecular ladder, in which two C22(6) chains, related by the glide plane at z = 1/4, act as the uprights and the C2—N2 bonds act as the rungs.
The π–π-stacking interactions (Fig. 3) link the reference molecule at (x, 1/4, z), which forms part of the hydrogen-bonded chain along (x, 1/4, 1/4), with the two molecules at (1 − x, 3/4, 1 − z) and (1 − x, −0.25, 1 − z), which lie, respectively, in the hydrogen-bonded chains along (-x, 3/4, 3/4) and (-x, −0.25, 3/4). The interplanar spacing is 3.273 (2) Å, the centroid separation is 3.588 (2) Å and the centroid offset is 1.470 (2) Å. By this means, a (001) sheet is formed, centred at z = 0.5 and lying in the domain 0.22 < z < 0.78; a similar sheet, centred at z = 0, lies in the domain −0.28 < z < 0.28, but there are no direction-specific interactions between adjacent sheets.
In both (II) (Fig. 4) and (III) (Fig. 5), there is just a single N—H bond, and a single N—H···N hydrogen bond (Tables 4 and 6) leads to the formation of centrosymmetric R22(8) dimers, centred at (1/2, 1/2, 1/2) (Figs. 6 and 7). In neither of (II) and (III) are there any other hydrogen bonds or any π–π-stacking interactions.
The gross supramolecular structure of (I) resembles that of the 4,6-dimethoxy analogue, (IV) (Low et al., 2002), while differing from it in detail. The chains of edge-fused rings in (IV) contain two different types of R22(8) ring, both centrosymmetric, incorporating only atoms N1 and N2 in one type of ring and only N2 and N3 in the other; by contrast, the chain in (I) contains only one type of ring, and this includes all three N atoms. Moreover, whereas in (I), the chain is generated by a glide plane, in (IV) it is generated by a combination of inversions and twofold rotations. The supramolecular structures of (I) and (IV) also differsin the effects of the π–π stacking, which gives a two-dimensional array in (I), but a three-dimensional structure in (IV). On the other hand, the centrosymmetric dimer structures found for (II) and (III) exactly mimic that observed in (V) (Low et al., 2002), which is a positional isomer of (III).
In each of (I)–(III), the intramolecular distances show no evidence for significant bond fixation involving the pyrimidine rings (Tables 1, 3 and 5); in this respect, the molecular–electronic structure of (I) is markedly different from those in a large number of analogous pyrimidines carrying a 5-nitroso substituent, where highly polarized structures are the norm (Low et al., 2000; Low, Cannon et al., 2001; Low, Moreno et al., 2001; Quesada et al., 2002).
The non-H atoms in (I) are strictly coplanar, and the methoxy-group conformation is such that the methyl C atom is directed away from the amino group [cf. compound (IV) (Low et al., 2002), see Scheme]. In both (II) and (III), the methylene C atoms of the benzyl substituents are all close to the planes of the adjacent pyrimidine rings, but the phenyl groups are twisted well out of these planes (Tables 3 and 5). We note the general similarity between the conformations of (II) and (III), and the fact that the overall conformations of the isomeric compounds (III) and (V) are unchanged by the positional exchange of benzylamino and benzyloxy substituents. The subtle factors underpinning the preferred conformations is systems such as (I)–(V) await investigation.