Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112051049/yf3022sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112051049/yf3022Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112051049/yf3022IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112051049/yf3022IIIsup4.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112051049/yf3022IVsup5.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112051049/yf3022Vsup6.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112051049/yf3022VIsup7.hkl |
CCDC references: 925765; 925766; 925767; 925768; 925769; 925770
For related literature, see: Allen et al. (1987, 2006); Bernstein et al. (1995); Bruno et al. (1999); Cantin (2006); Cobo et al. (2008); Cremer & Pople (1975); Ferguson et al. (1998a, 1998b); Ghorab et al. (2004); Gregson et al. (2000); Low et al. (2007); Melguizo et al. (2003); Min et al. (2008); Murata et al. (2004); Quesada et al. (2003, 2004); Trilleras et al. (2007); Wood et al. (2009).
For the synthesis of the esters (I) and (III)–(VI), the appropriate amino ester hydrochloride (1.3 mmol) and anhydrous potassium carbonate (6.5 mmol) were added to a suspension of the appropriate N4-substituted 2,4-diamino-6-chloropyrimidine-5-carbaldehyde in dry acetonitrile (10 ml). The mixtures were then heated under reflux until thin-layer chromatography (TLC) indicated that the starting pyrimidine had all been consumed. The mixtures were then cooled to ambient temperature and the solvent was removed under reduced pressure. The resulting products were then purified by flash chromatography on silica gel using dichloromethane/acetone mixtures (95:5 to 90:10 v/v) as eluent. Finally, crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation of solutions in methanol at ambient temperature and in air.
Compound (I), from 2-amino-4-chloro-6-[methyl(phenyl)amino]pyrimidine-5-carbaldehyde and glycine ethyl ester hydrochloride. Reaction time 24 h, yield 83%, pale yellow, m.p. 394 K (decomposition). MS (EI, 70 eV) m/z (%): 329 (M+, 92), 328 (100), 312 (51), 200 (41), 254 (68), 238 (43), 226 (66). Analysis, found: C 58.1, H 5.9, N 20.9%; C16H19N5O3 requires: C 58.3, H 5.8, N 21.3%.
Compound (III), from 2-amino-4-chloro-6-[methyl(phenyl)amino]pyrimidine-5-carbaldehyde and β-alanine ethyl ester hydrochloride. Reaction time 20 h, yield 78%, colourless, m.p. >433 K (decomposition). MS (EI, 70 eV) m/z (%): 3443 (M+, 79), 342 (100), 254 (62), 214 (40). Analysis, found: C 59.5, H 5.9, N 19.9%; C17H21N5O3 requires: C 59.5, H 6.2, N 20.4%.
Compound (IV), from 2-amino-6-[benzyl(methyl)amino]-4-chloropyrimidine-5-carbaldehyde and glycine ethyl ester hydrochloride. Reaction time 4 d, yield 87%, colourless, m.p. 388 K (decomposition). MS (EI, 70 eV) m/z (%): 329 (M+, 77), 313 (20), 312 (100), 300 (31), 270 (21), 259 (29), 120 (73), 91 (65).
Compound (V), from 2-amino-6-[benzyl(methyl)amino]-4-chloropyrimidine-5-carbaldehyde and β-alanine ethyl ester hydrochloride. Reaction time 24 h, yield 88%, colourless, m.p. 388 K (decomposition). MS (EI, 70 eV) m/z (%): 357 (M+, 53), 340 (72), 328 (20), 312 (26), 270 (13), 266 (26), 252 (31), 192 (82), 91 (100). Analysis, found: C 60.7, H 6.2, N 19.2%; C18H23N5O3 requires: C 60.5, H 6.5, N 19.6%.
Compound (VI), from 2-amino-4-chloro-6-(piperidin-1-yl)pyrimidine-5-carbaldehyde and β-alanine ethyl ester hydrochloride. Reaction time 21 h, yield 99%, colourless, m.p. 378 K. MS (EI, 70 eV) m/z (%): 321 (M+, 42), 304 (100), 276 (25), 230 (18), 216 (26). Analysis, found: C 55.7, H 7.4, N 21.7%; C15H23N5O3 requires: C 56.1, H 7.2, N 21.8%.
For the synthesis of (II), a sample of (I) (0.3 mmol) was added to a methanol ammonia solution (5 ml of 7 M), and this mixture was then held at 313 K for 6 h. The solvent and the excess ammonia were removed under reduced pressure at ambient temperature and the product was crystallized from methanol [yield 75%, colourless, m.p. >413 K (decomposition)]. MS (EI, 70 eV) m/z (%): 300 (M+, 65), 299 (100), 283 (17), 256 (92), 254 (67), 238 (44), 226 (56), 212 (34), 200 (22), 106 (20). HRMS found: 300.1331; C14H16N6O2 requires 300.1335.
All H atoms were located in difference maps. C-bound H atoms were subsequently treated as riding atoms in geometrically idealized positions, with C—H = 0.93–0.99 Å and Uiso(H) = kUeq(C), where k = 1.5 for the methyl groups, which were permitted to rotate but not to tilt, and 1.2 for all other C-bound H atoms. N-bound H atoms were permitted to ride at the positions deduced from the difference maps, with Uiso(H) = 1.2Ueq(N), giving N—H distances in the range 0.77–1.01 Å (see Table 2).
For all compounds, data collection: COLLECT (Nonius, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
C16H19N5O3 | Z = 2 |
Mr = 329.36 | F(000) = 348 |
Triclinic, P1 | Dx = 1.353 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.3990 (5) Å | Cell parameters from 3718 reflections |
b = 9.609 (3) Å | θ = 3.2–27.5° |
c = 12.449 (3) Å | µ = 0.10 mm−1 |
α = 73.30 (2)° | T = 293 K |
β = 82.680 (14)° | Block, pale yellow |
γ = 72.693 (13)° | 0.41 × 0.25 × 0.22 mm |
V = 808.5 (3) Å3 |
Bruker Nonius KappaCCD area-detector diffractometer | 3006 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 2054 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.042 |
Detector resolution: 9.091 pixels mm-1 | θmax = 25.5°, θmin = 3.2° |
ϕ and ω scans | h = −8→8 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −11→11 |
Tmin = 0.885, Tmax = 0.936 | l = −15→15 |
18365 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.045 | H-atom parameters constrained |
wR(F2) = 0.120 | w = 1/[σ2(Fo2) + (0.0562P)2 + 0.2215P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.001 |
3006 reflections | Δρmax = 0.19 e Å−3 |
220 parameters | Δρmin = −0.17 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.033 (4) |
C16H19N5O3 | γ = 72.693 (13)° |
Mr = 329.36 | V = 808.5 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.3990 (5) Å | Mo Kα radiation |
b = 9.609 (3) Å | µ = 0.10 mm−1 |
c = 12.449 (3) Å | T = 293 K |
α = 73.30 (2)° | 0.41 × 0.25 × 0.22 mm |
β = 82.680 (14)° |
Bruker Nonius KappaCCD area-detector diffractometer | 3006 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2054 reflections with I > 2σ(I) |
Tmin = 0.885, Tmax = 0.936 | Rint = 0.042 |
18365 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.120 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.19 e Å−3 |
3006 reflections | Δρmin = −0.17 e Å−3 |
220 parameters |
x | y | z | Uiso*/Ueq | ||
N1 | 0.1832 (2) | 0.62253 (17) | 0.41032 (12) | 0.0370 (4) | |
C2 | 0.2237 (2) | 0.6088 (2) | 0.51649 (15) | 0.0358 (4) | |
N3 | 0.3581 (2) | 0.65340 (17) | 0.54930 (12) | 0.0372 (4) | |
C4 | 0.4570 (2) | 0.7269 (2) | 0.46709 (15) | 0.0343 (4) | |
C5 | 0.4235 (2) | 0.7561 (2) | 0.35103 (15) | 0.0348 (4) | |
C6 | 0.2866 (2) | 0.6925 (2) | 0.32890 (14) | 0.0341 (4) | |
N21 | 0.1191 (2) | 0.5411 (2) | 0.59954 (13) | 0.0488 (5) | |
H21A | 0.0412 | 0.4884 | 0.5872 | 0.059* | |
H21B | 0.1525 | 0.5227 | 0.6757 | 0.059* | |
N41 | 0.5891 (2) | 0.77684 (18) | 0.49610 (13) | 0.0415 (4) | |
H41 | 0.6471 | 0.8364 | 0.4363 | 0.050* | |
C42 | 0.6239 (3) | 0.7672 (2) | 0.60966 (15) | 0.0414 (5) | |
H42A | 0.6666 | 0.6623 | 0.6520 | 0.050* | |
H42B | 0.5087 | 0.8157 | 0.6465 | 0.050* | |
C43 | 0.7738 (3) | 0.8457 (2) | 0.60362 (16) | 0.0417 (5) | |
O43 | 0.8323 (2) | 0.9156 (2) | 0.51776 (13) | 0.0728 (5) | |
O44 | 0.83342 (19) | 0.82899 (16) | 0.70415 (11) | 0.0464 (4) | |
C45 | 0.9843 (3) | 0.8998 (3) | 0.70299 (19) | 0.0534 (6) | |
H45A | 0.9497 | 1.0036 | 0.6575 | 0.064* | |
H45B | 1.1011 | 0.8458 | 0.6708 | 0.064* | |
C46 | 1.0116 (4) | 0.8957 (3) | 0.8196 (2) | 0.0657 (7) | |
H46A | 1.0490 | 0.7926 | 0.8636 | 0.099* | |
H46B | 0.8951 | 0.9484 | 0.8511 | 0.099* | |
H46C | 1.1086 | 0.9435 | 0.8198 | 0.099* | |
C51 | 0.5014 (3) | 0.8607 (2) | 0.26646 (16) | 0.0421 (5) | |
H51 | 0.4535 | 0.8904 | 0.1954 | 0.050* | |
O51 | 0.6259 (2) | 0.91568 (17) | 0.27831 (11) | 0.0533 (4) | |
N61 | 0.2488 (2) | 0.70546 (19) | 0.22015 (12) | 0.0406 (4) | |
C61 | 0.3994 (3) | 0.6844 (2) | 0.13638 (15) | 0.0387 (5) | |
C62 | 0.5608 (3) | 0.5669 (2) | 0.16096 (17) | 0.0474 (5) | |
H62 | 0.5737 | 0.5000 | 0.2322 | 0.057* | |
C63 | 0.7041 (3) | 0.5488 (3) | 0.0788 (2) | 0.0614 (6) | |
H63 | 0.8151 | 0.4711 | 0.0958 | 0.074* | |
C64 | 0.6842 (4) | 0.6443 (3) | −0.0276 (2) | 0.0664 (7) | |
H64 | 0.7807 | 0.6305 | −0.0825 | 0.080* | |
C65 | 0.5227 (4) | 0.7593 (3) | −0.05232 (18) | 0.0615 (6) | |
H65 | 0.5089 | 0.8240 | −0.1243 | 0.074* | |
C66 | 0.3798 (3) | 0.7799 (2) | 0.02895 (16) | 0.0502 (5) | |
H66 | 0.2696 | 0.8584 | 0.0116 | 0.060* | |
C67 | 0.0719 (3) | 0.6819 (3) | 0.19802 (18) | 0.0557 (6) | |
H67A | −0.0287 | 0.7235 | 0.2462 | 0.084* | |
H67B | 0.0864 | 0.5756 | 0.2123 | 0.084* | |
H67C | 0.0422 | 0.7311 | 0.1210 | 0.084* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0371 (9) | 0.0447 (9) | 0.0343 (9) | −0.0186 (7) | 0.0011 (7) | −0.0121 (7) |
C2 | 0.0368 (10) | 0.0391 (11) | 0.0340 (10) | −0.0141 (9) | 0.0028 (8) | −0.0115 (8) |
N3 | 0.0398 (9) | 0.0449 (9) | 0.0325 (8) | −0.0206 (7) | 0.0019 (7) | −0.0108 (7) |
C4 | 0.0341 (10) | 0.0363 (10) | 0.0352 (10) | −0.0123 (8) | 0.0004 (8) | −0.0119 (8) |
C5 | 0.0347 (10) | 0.0391 (11) | 0.0332 (10) | −0.0147 (8) | −0.0005 (8) | −0.0093 (8) |
C6 | 0.0330 (10) | 0.0370 (10) | 0.0329 (10) | −0.0103 (8) | −0.0014 (8) | −0.0093 (8) |
N21 | 0.0562 (11) | 0.0683 (12) | 0.0347 (9) | −0.0392 (9) | 0.0040 (8) | −0.0130 (8) |
N41 | 0.0466 (9) | 0.0544 (11) | 0.0330 (9) | −0.0302 (8) | 0.0009 (7) | −0.0104 (7) |
C42 | 0.0466 (11) | 0.0520 (12) | 0.0326 (10) | −0.0234 (10) | −0.0010 (8) | −0.0118 (9) |
C43 | 0.0468 (11) | 0.0502 (12) | 0.0346 (11) | −0.0245 (10) | 0.0006 (9) | −0.0108 (9) |
O43 | 0.0944 (12) | 0.1037 (14) | 0.0418 (9) | −0.0740 (11) | −0.0048 (8) | −0.0027 (9) |
O44 | 0.0491 (8) | 0.0653 (9) | 0.0375 (8) | −0.0324 (7) | −0.0011 (6) | −0.0161 (7) |
C45 | 0.0486 (12) | 0.0679 (15) | 0.0591 (14) | −0.0320 (11) | −0.0013 (10) | −0.0242 (11) |
C46 | 0.0748 (16) | 0.0708 (16) | 0.0639 (15) | −0.0337 (13) | −0.0236 (13) | −0.0136 (13) |
C51 | 0.0453 (11) | 0.0471 (12) | 0.0382 (11) | −0.0205 (10) | −0.0031 (9) | −0.0094 (9) |
O51 | 0.0593 (9) | 0.0638 (10) | 0.0450 (8) | −0.0386 (8) | −0.0019 (7) | −0.0046 (7) |
N61 | 0.0369 (9) | 0.0580 (11) | 0.0320 (8) | −0.0202 (8) | −0.0030 (7) | −0.0115 (7) |
C61 | 0.0444 (11) | 0.0453 (11) | 0.0331 (10) | −0.0212 (9) | −0.0015 (8) | −0.0113 (9) |
C62 | 0.0532 (13) | 0.0459 (12) | 0.0433 (12) | −0.0176 (10) | −0.0015 (10) | −0.0084 (9) |
C63 | 0.0535 (14) | 0.0606 (15) | 0.0703 (16) | −0.0134 (12) | 0.0068 (12) | −0.0243 (13) |
C64 | 0.0729 (17) | 0.0821 (19) | 0.0557 (15) | −0.0365 (15) | 0.0245 (13) | −0.0319 (14) |
C65 | 0.0825 (18) | 0.0749 (17) | 0.0341 (12) | −0.0394 (15) | 0.0075 (11) | −0.0109 (11) |
C66 | 0.0589 (13) | 0.0549 (13) | 0.0368 (11) | −0.0195 (11) | −0.0059 (10) | −0.0065 (10) |
C67 | 0.0478 (13) | 0.0859 (17) | 0.0412 (12) | −0.0326 (12) | −0.0075 (9) | −0.0116 (11) |
N1—C6 | 1.335 (2) | C45—H45B | 0.9700 |
N1—C2 | 1.353 (2) | C46—H46A | 0.9600 |
C2—N3 | 1.340 (2) | C46—H46B | 0.9600 |
C2—N21 | 1.342 (2) | C46—H46C | 0.9600 |
N3—C4 | 1.335 (2) | C51—O51 | 1.232 (2) |
C4—N41 | 1.336 (2) | C51—H51 | 0.9300 |
C4—C5 | 1.430 (2) | N61—C61 | 1.436 (2) |
C5—C6 | 1.418 (2) | N61—C67 | 1.464 (2) |
C5—C51 | 1.426 (3) | C61—C62 | 1.374 (3) |
C6—N61 | 1.380 (2) | C61—C66 | 1.385 (3) |
N21—H21A | 0.9242 | C62—C63 | 1.384 (3) |
N21—H21B | 0.9636 | C62—H62 | 0.9300 |
N41—C42 | 1.441 (2) | C63—C64 | 1.375 (3) |
N41—H41 | 0.9409 | C63—H63 | 0.9300 |
C42—C43 | 1.500 (3) | C64—C65 | 1.362 (3) |
C42—H42A | 0.9700 | C64—H64 | 0.9300 |
C42—H42B | 0.9700 | C65—C66 | 1.378 (3) |
C43—O43 | 1.193 (2) | C65—H65 | 0.9300 |
C43—O44 | 1.330 (2) | C66—H66 | 0.9300 |
O44—C45 | 1.467 (2) | C67—H67A | 0.9600 |
C45—C46 | 1.479 (3) | C67—H67B | 0.9600 |
C45—H45A | 0.9700 | C67—H67C | 0.9600 |
C6—N1—C2 | 115.75 (15) | C45—C46—H46A | 109.5 |
N3—C2—N21 | 115.54 (16) | C45—C46—H46B | 109.5 |
N3—C2—N1 | 127.77 (16) | H46A—C46—H46B | 109.5 |
N21—C2—N1 | 116.68 (16) | C45—C46—H46C | 109.5 |
C4—N3—C2 | 115.82 (15) | H46A—C46—H46C | 109.5 |
N3—C4—N41 | 117.83 (16) | H46B—C46—H46C | 109.5 |
N3—C4—C5 | 122.50 (16) | O51—C51—C5 | 126.41 (18) |
N41—C4—C5 | 119.66 (16) | O51—C51—H51 | 116.8 |
C6—C5—C51 | 122.78 (17) | C5—C51—H51 | 116.8 |
C6—C5—C4 | 115.27 (16) | C6—N61—C61 | 120.97 (15) |
C51—C5—C4 | 121.27 (16) | C6—N61—C67 | 119.49 (15) |
N1—C6—N61 | 116.45 (16) | C61—N61—C67 | 115.42 (15) |
N1—C6—C5 | 122.59 (16) | C62—C61—C66 | 119.58 (19) |
N61—C6—C5 | 120.92 (16) | C62—C61—N61 | 120.45 (17) |
C2—N21—H21A | 122.3 | C66—C61—N61 | 119.93 (18) |
C2—N21—H21B | 118.0 | C61—C62—C63 | 119.4 (2) |
H21A—N21—H21B | 117.4 | C61—C62—H62 | 120.3 |
C4—N41—C42 | 124.86 (15) | C63—C62—H62 | 120.3 |
C4—N41—H41 | 115.3 | C64—C63—C62 | 120.7 (2) |
C42—N41—H41 | 119.0 | C64—C63—H63 | 119.6 |
N41—C42—C43 | 107.29 (15) | C62—C63—H63 | 119.6 |
N41—C42—H42A | 110.3 | C65—C64—C63 | 119.7 (2) |
C43—C42—H42A | 110.3 | C65—C64—H64 | 120.1 |
N41—C42—H42B | 110.3 | C63—C64—H64 | 120.1 |
C43—C42—H42B | 110.3 | C64—C65—C66 | 120.2 (2) |
H42A—C42—H42B | 108.5 | C64—C65—H65 | 119.9 |
O43—C43—O44 | 124.00 (18) | C66—C65—H65 | 119.9 |
O43—C43—C42 | 123.37 (18) | C65—C66—C61 | 120.3 (2) |
O44—C43—C42 | 112.62 (15) | C65—C66—H66 | 119.9 |
C43—O44—C45 | 114.96 (15) | C61—C66—H66 | 119.9 |
O44—C45—C46 | 108.72 (17) | N61—C67—H67A | 109.5 |
O44—C45—H45A | 109.9 | N61—C67—H67B | 109.5 |
C46—C45—H45A | 109.9 | H67A—C67—H67B | 109.5 |
O44—C45—H45B | 109.9 | N61—C67—H67C | 109.5 |
C46—C45—H45B | 109.9 | H67A—C67—H67C | 109.5 |
H45A—C45—H45B | 108.3 | H67B—C67—H67C | 109.5 |
C6—N1—C2—N3 | −1.9 (3) | O43—C43—O44—C45 | −1.9 (3) |
C6—N1—C2—N21 | 178.89 (16) | C42—C43—O44—C45 | 178.29 (17) |
N21—C2—N3—C4 | −177.11 (16) | C43—O44—C45—C46 | 170.04 (19) |
N1—C2—N3—C4 | 3.7 (3) | C6—C5—C51—O51 | −176.82 (19) |
C2—N3—C4—N41 | 178.29 (16) | C4—C5—C51—O51 | 13.1 (3) |
C2—N3—C4—C5 | −0.3 (3) | N1—C6—N61—C61 | −139.74 (18) |
N3—C4—C5—C6 | −4.1 (3) | C5—C6—N61—C61 | 42.6 (3) |
N41—C4—C5—C6 | 177.27 (16) | N1—C6—N61—C67 | 16.4 (3) |
N3—C4—C5—C51 | 166.67 (17) | C5—C6—N61—C67 | −161.27 (18) |
N41—C4—C5—C51 | −11.9 (3) | C6—N61—C61—C62 | 43.8 (3) |
C2—N1—C6—N61 | 179.10 (16) | C67—N61—C61—C62 | −113.3 (2) |
C2—N1—C6—C5 | −3.3 (3) | C6—N61—C61—C66 | −138.31 (19) |
C51—C5—C6—N1 | −164.61 (18) | C67—N61—C61—C66 | 64.7 (2) |
C4—C5—C6—N1 | 6.1 (3) | C66—C61—C62—C63 | 2.1 (3) |
C51—C5—C6—N61 | 12.9 (3) | N61—C61—C62—C63 | 180.00 (19) |
C4—C5—C6—N61 | −176.44 (16) | C61—C62—C63—C64 | −1.8 (3) |
N3—C4—N41—C42 | −4.8 (3) | C62—C63—C64—C65 | 0.8 (4) |
C5—C4—N41—C42 | 173.87 (18) | C63—C64—C65—C66 | 0.1 (4) |
C4—N41—C42—C43 | −176.15 (17) | C64—C65—C66—C61 | 0.2 (3) |
N41—C42—C43—O43 | 7.4 (3) | C62—C61—C66—C65 | −1.3 (3) |
N41—C42—C43—O44 | −172.71 (17) | N61—C61—C66—C65 | −179.20 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
N21—H21A···N1i | 0.92 | 2.22 | 3.125 (2) | 167 |
N41—H41···O51 | 0.94 | 1.90 | 2.675 (2) | 138 |
Symmetry code: (i) −x, −y+1, −z+1. |
C14H16N6O2 | F(000) = 1264 |
Mr = 300.33 | Dx = 1.395 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 3290 reflections |
a = 20.045 (4) Å | θ = 2.6–27.5° |
b = 8.6868 (7) Å | µ = 0.10 mm−1 |
c = 17.990 (3) Å | T = 120 K |
β = 114.064 (11)° | Plate, colourless |
V = 2860.3 (8) Å3 | 0.32 × 0.20 × 0.11 mm |
Z = 8 |
Bruker Nonius KappaCCD area-detector diffractometer | 2657 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 1993 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.068 |
Detector resolution: 9.091 pixels mm-1 | θmax = 25.5°, θmin = 2.6° |
ϕ and ω scans | h = −24→24 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −10→10 |
Tmin = 0.969, Tmax = 0.989 | l = −21→21 |
32858 measured reflections |
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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.119 | H-atom parameters constrained |
S = 1.12 | w = 1/[σ2(Fo2) + (0.0427P)2 + 5.1608P] where P = (Fo2 + 2Fc2)/3 |
2657 reflections | (Δ/σ)max = 0.001 |
200 parameters | Δρmax = 0.34 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
C14H16N6O2 | V = 2860.3 (8) Å3 |
Mr = 300.33 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 20.045 (4) Å | µ = 0.10 mm−1 |
b = 8.6868 (7) Å | T = 120 K |
c = 17.990 (3) Å | 0.32 × 0.20 × 0.11 mm |
β = 114.064 (11)° |
Bruker Nonius KappaCCD area-detector diffractometer | 2657 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 1993 reflections with I > 2σ(I) |
Tmin = 0.969, Tmax = 0.989 | Rint = 0.068 |
32858 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.119 | H-atom parameters constrained |
S = 1.12 | Δρmax = 0.34 e Å−3 |
2657 reflections | Δρmin = −0.26 e Å−3 |
200 parameters |
x | y | z | Uiso*/Ueq | ||
N1 | 0.53486 (10) | 0.9198 (2) | 0.40896 (11) | 0.0177 (4) | |
C2 | 0.58234 (12) | 0.8233 (2) | 0.46413 (13) | 0.0176 (5) | |
N3 | 0.57839 (10) | 0.6681 (2) | 0.46616 (11) | 0.0191 (4) | |
C4 | 0.52481 (12) | 0.6035 (2) | 0.40211 (13) | 0.0161 (5) | |
C5 | 0.47362 (11) | 0.6906 (2) | 0.33536 (13) | 0.0157 (5) | |
C6 | 0.48010 (11) | 0.8548 (2) | 0.34637 (12) | 0.0157 (5) | |
N21 | 0.63877 (11) | 0.8895 (2) | 0.52450 (11) | 0.0264 (5) | |
H21A | 0.6428 | 0.9964 | 0.5215 | 0.032* | |
H21B | 0.6728 | 0.8302 | 0.5639 | 0.032* | |
N41 | 0.52083 (10) | 0.4481 (2) | 0.40089 (11) | 0.0199 (4) | |
H41 | 0.4833 | 0.4064 | 0.3586 | 0.024* | |
C42 | 0.56561 (12) | 0.3514 (3) | 0.46820 (13) | 0.0200 (5) | |
H42A | 0.5371 | 0.2578 | 0.4674 | 0.024* | |
H42B | 0.5742 | 0.4071 | 0.5193 | 0.024* | |
C43 | 0.63942 (12) | 0.3004 (2) | 0.47167 (13) | 0.0179 (5) | |
O43 | 0.67776 (9) | 0.21582 (17) | 0.52914 (9) | 0.0228 (4) | |
N44 | 0.66162 (11) | 0.3466 (2) | 0.41535 (11) | 0.0240 (5) | |
H44A | 0.6306 | 0.4195 | 0.3782 | 0.029* | |
H44B | 0.7127 | 0.3321 | 0.4232 | 0.029* | |
C51 | 0.42654 (11) | 0.6197 (2) | 0.26089 (13) | 0.0163 (5) | |
H51 | 0.3990 | 0.6859 | 0.2171 | 0.020* | |
O51 | 0.41838 (8) | 0.47834 (17) | 0.24825 (9) | 0.0208 (4) | |
N61 | 0.43222 (10) | 0.9555 (2) | 0.29196 (11) | 0.0171 (4) | |
C61 | 0.35514 (12) | 0.9229 (2) | 0.24847 (13) | 0.0161 (5) | |
C62 | 0.31485 (12) | 0.8653 (3) | 0.28957 (13) | 0.0199 (5) | |
H62 | 0.3384 | 0.8384 | 0.3455 | 0.024* | |
C63 | 0.23939 (13) | 0.8474 (3) | 0.24764 (14) | 0.0246 (5) | |
H63 | 0.2114 | 0.8079 | 0.2752 | 0.030* | |
C64 | 0.20517 (13) | 0.8868 (3) | 0.16633 (14) | 0.0243 (5) | |
H64 | 0.1537 | 0.8767 | 0.1384 | 0.029* | |
C65 | 0.24613 (12) | 0.9412 (3) | 0.12547 (14) | 0.0228 (5) | |
H65 | 0.2226 | 0.9658 | 0.0692 | 0.027* | |
C66 | 0.32116 (12) | 0.9600 (2) | 0.16621 (13) | 0.0186 (5) | |
H66 | 0.3490 | 0.9978 | 0.1382 | 0.022* | |
C67 | 0.44708 (12) | 1.1210 (2) | 0.30632 (14) | 0.0219 (5) | |
H67A | 0.4990 | 1.1405 | 0.3208 | 0.033* | |
H67B | 0.4344 | 1.1546 | 0.3509 | 0.033* | |
H67C | 0.4177 | 1.1783 | 0.2568 | 0.033* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0172 (10) | 0.0147 (9) | 0.0164 (9) | −0.0011 (7) | 0.0021 (8) | −0.0015 (7) |
C2 | 0.0183 (12) | 0.0169 (12) | 0.0136 (11) | −0.0004 (9) | 0.0023 (9) | −0.0003 (9) |
N3 | 0.0186 (10) | 0.0167 (10) | 0.0156 (9) | −0.0009 (8) | 0.0003 (8) | −0.0004 (8) |
C4 | 0.0179 (11) | 0.0140 (11) | 0.0146 (11) | −0.0002 (9) | 0.0047 (9) | −0.0017 (8) |
C5 | 0.0143 (11) | 0.0154 (11) | 0.0160 (11) | 0.0006 (9) | 0.0047 (9) | 0.0003 (9) |
C6 | 0.0166 (11) | 0.0167 (11) | 0.0135 (11) | −0.0001 (9) | 0.0059 (9) | −0.0013 (9) |
N21 | 0.0270 (11) | 0.0141 (10) | 0.0209 (10) | −0.0020 (8) | −0.0080 (9) | 0.0008 (8) |
N41 | 0.0207 (10) | 0.0155 (10) | 0.0166 (9) | −0.0029 (8) | 0.0006 (8) | −0.0008 (8) |
C42 | 0.0274 (13) | 0.0134 (11) | 0.0162 (11) | −0.0022 (9) | 0.0059 (10) | 0.0015 (9) |
C43 | 0.0227 (12) | 0.0112 (11) | 0.0146 (11) | −0.0046 (9) | 0.0023 (9) | −0.0025 (9) |
O43 | 0.0245 (9) | 0.0186 (8) | 0.0184 (8) | 0.0004 (7) | 0.0017 (7) | 0.0024 (7) |
N44 | 0.0239 (11) | 0.0256 (11) | 0.0187 (10) | 0.0048 (9) | 0.0047 (8) | 0.0043 (8) |
C51 | 0.0127 (11) | 0.0172 (12) | 0.0177 (11) | 0.0017 (9) | 0.0048 (9) | −0.0011 (9) |
O51 | 0.0193 (8) | 0.0163 (8) | 0.0209 (8) | −0.0025 (7) | 0.0022 (7) | −0.0052 (6) |
N61 | 0.0156 (9) | 0.0118 (9) | 0.0185 (9) | −0.0005 (7) | 0.0015 (8) | −0.0002 (7) |
C61 | 0.0148 (11) | 0.0116 (11) | 0.0178 (11) | 0.0014 (8) | 0.0025 (9) | −0.0023 (8) |
C62 | 0.0213 (12) | 0.0195 (12) | 0.0161 (11) | 0.0016 (9) | 0.0047 (9) | −0.0007 (9) |
C63 | 0.0221 (13) | 0.0290 (13) | 0.0243 (12) | −0.0034 (10) | 0.0111 (10) | −0.0029 (10) |
C64 | 0.0151 (12) | 0.0244 (13) | 0.0260 (13) | −0.0009 (10) | 0.0007 (10) | −0.0044 (10) |
C65 | 0.0229 (13) | 0.0188 (12) | 0.0163 (11) | 0.0034 (10) | −0.0027 (9) | 0.0005 (9) |
C66 | 0.0205 (12) | 0.0142 (11) | 0.0185 (11) | 0.0012 (9) | 0.0052 (9) | 0.0020 (9) |
C67 | 0.0197 (12) | 0.0146 (12) | 0.0244 (12) | −0.0013 (9) | 0.0019 (10) | 0.0006 (9) |
N1—C6 | 1.336 (3) | N44—H44B | 0.9820 |
N1—C2 | 1.350 (3) | C51—O51 | 1.247 (3) |
C2—N21 | 1.337 (3) | C51—H51 | 0.9500 |
C2—N3 | 1.352 (3) | N61—C61 | 1.447 (3) |
N3—C4 | 1.336 (3) | N61—C67 | 1.469 (3) |
C4—N41 | 1.352 (3) | C61—C66 | 1.391 (3) |
C4—C5 | 1.436 (3) | C61—C62 | 1.391 (3) |
C5—C51 | 1.426 (3) | C62—C63 | 1.397 (3) |
C5—C6 | 1.438 (3) | C62—H62 | 0.9500 |
C6—N61 | 1.371 (3) | C63—C64 | 1.382 (3) |
N21—H21A | 0.9359 | C63—H63 | 0.9500 |
N21—H21B | 0.9156 | C64—C65 | 1.390 (3) |
N41—C42 | 1.446 (3) | C64—H64 | 0.9500 |
N41—H41 | 0.8995 | C65—C66 | 1.388 (3) |
C42—C43 | 1.521 (3) | C65—H65 | 0.9500 |
C42—H42A | 0.9900 | C66—H66 | 0.9500 |
C42—H42B | 0.9900 | C67—H67A | 0.9800 |
C43—O43 | 1.246 (3) | C67—H67B | 0.9800 |
C43—N44 | 1.324 (3) | C67—H67C | 0.9800 |
N44—H44A | 0.9463 | ||
C6—N1—C2 | 116.60 (18) | H44A—N44—H44B | 122.3 |
N21—C2—N1 | 116.09 (19) | O51—C51—C5 | 125.7 (2) |
N21—C2—N3 | 116.49 (19) | O51—C51—H51 | 117.1 |
N1—C2—N3 | 127.4 (2) | C5—C51—H51 | 117.1 |
C4—N3—C2 | 115.49 (18) | C6—N61—C61 | 122.89 (18) |
N3—C4—N41 | 117.01 (19) | C6—N61—C67 | 117.80 (17) |
N3—C4—C5 | 123.3 (2) | C61—N61—C67 | 112.46 (17) |
N41—C4—C5 | 119.69 (19) | C66—C61—C62 | 120.7 (2) |
C51—C5—C4 | 122.08 (19) | C66—C61—N61 | 118.8 (2) |
C51—C5—C6 | 123.08 (19) | C62—C61—N61 | 120.42 (19) |
C4—C5—C6 | 114.43 (19) | C61—C62—C63 | 119.2 (2) |
N1—C6—N61 | 115.29 (19) | C61—C62—H62 | 120.4 |
N1—C6—C5 | 122.18 (19) | C63—C62—H62 | 120.4 |
N61—C6—C5 | 122.49 (19) | C64—C63—C62 | 120.3 (2) |
C2—N21—H21A | 116.4 | C64—C63—H63 | 119.8 |
C2—N21—H21B | 120.2 | C62—C63—H63 | 119.8 |
H21A—N21—H21B | 123.2 | C63—C64—C65 | 119.9 (2) |
C4—N41—C42 | 123.65 (19) | C63—C64—H64 | 120.0 |
C4—N41—H41 | 116.1 | C65—C64—H64 | 120.0 |
C42—N41—H41 | 119.6 | C66—C65—C64 | 120.5 (2) |
N41—C42—C43 | 117.69 (19) | C66—C65—H65 | 119.8 |
N41—C42—H42A | 107.9 | C64—C65—H65 | 119.8 |
C43—C42—H42A | 107.9 | C65—C66—C61 | 119.3 (2) |
N41—C42—H42B | 107.9 | C65—C66—H66 | 120.3 |
C43—C42—H42B | 107.9 | C61—C66—H66 | 120.3 |
H42A—C42—H42B | 107.2 | N61—C67—H67A | 109.5 |
O43—C43—N44 | 121.9 (2) | N61—C67—H67B | 109.5 |
O43—C43—C42 | 117.8 (2) | H67A—C67—H67B | 109.5 |
N44—C43—C42 | 120.34 (19) | N61—C67—H67C | 109.5 |
C43—N44—H44A | 114.4 | H67A—C67—H67C | 109.5 |
C43—N44—H44B | 120.4 | H67B—C67—H67C | 109.5 |
C6—N1—C2—N21 | 177.1 (2) | N41—C42—C43—N44 | 1.3 (3) |
C6—N1—C2—N3 | −4.5 (3) | C4—C5—C51—O51 | 8.3 (4) |
N21—C2—N3—C4 | −175.1 (2) | C6—C5—C51—O51 | −179.4 (2) |
N1—C2—N3—C4 | 6.4 (3) | N1—C6—N61—C61 | −146.9 (2) |
C2—N3—C4—N41 | 177.8 (2) | C5—C6—N61—C61 | 35.4 (3) |
C2—N3—C4—C5 | −0.8 (3) | N1—C6—N61—C67 | 1.9 (3) |
N3—C4—C5—C51 | 167.3 (2) | C5—C6—N61—C67 | −175.8 (2) |
N41—C4—C5—C51 | −11.3 (3) | C6—N61—C61—C66 | −137.5 (2) |
N3—C4—C5—C6 | −5.7 (3) | C67—N61—C61—C66 | 72.2 (3) |
N41—C4—C5—C6 | 175.8 (2) | C6—N61—C61—C62 | 46.9 (3) |
C2—N1—C6—N61 | 179.15 (19) | C67—N61—C61—C62 | −103.4 (2) |
C2—N1—C6—C5 | −3.2 (3) | C66—C61—C62—C63 | −1.1 (3) |
C51—C5—C6—N1 | −165.2 (2) | N61—C61—C62—C63 | 174.5 (2) |
C4—C5—C6—N1 | 7.7 (3) | C61—C62—C63—C64 | −0.1 (3) |
C51—C5—C6—N61 | 12.4 (3) | C62—C63—C64—C65 | 1.5 (4) |
C4—C5—C6—N61 | −174.8 (2) | C63—C64—C65—C66 | −1.6 (4) |
N3—C4—N41—C42 | 7.0 (3) | C64—C65—C66—C61 | 0.4 (3) |
C5—C4—N41—C42 | −174.3 (2) | C62—C61—C66—C65 | 1.0 (3) |
C4—N41—C42—C43 | −88.6 (3) | N61—C61—C66—C65 | −174.65 (19) |
N41—C42—C43—O43 | −179.29 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
N21—H21A···O43i | 0.94 | 2.02 | 2.933 (2) | 166 |
N41—H41···O51 | 0.90 | 1.98 | 2.689 (2) | 135 |
N44—H44A···O51ii | 0.95 | 2.14 | 2.949 (2) | 143 |
N44—H44B···O43iii | 0.98 | 2.05 | 3.006 (3) | 164 |
C62—H62···O43iv | 0.95 | 2.45 | 3.280 (3) | 146 |
Symmetry codes: (i) x, y+1, z; (ii) −x+1, y, −z+1/2; (iii) −x+3/2, −y+1/2, −z+1; (iv) −x+1, −y+1, −z+1. |
C17H21N5O3 | F(000) = 1456 |
Mr = 343.39 | Dx = 1.340 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 3916 reflections |
a = 16.707 (6) Å | θ = 2.7–27.5° |
b = 10.218 (2) Å | µ = 0.10 mm−1 |
c = 20.733 (5) Å | T = 120 K |
β = 105.929 (19)° | Plate, colourless |
V = 3403.5 (16) Å3 | 0.29 × 0.22 × 0.10 mm |
Z = 8 |
Bruker Nonius KappaCCD area-detector diffractometer | 3160 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 2239 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.063 |
Detector resolution: 9.091 pixels mm-1 | θmax = 25.5°, θmin = 2.7° |
ϕ and ω scans | h = −20→20 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −12→12 |
Tmin = 0.973, Tmax = 0.991 | l = −25→25 |
21914 measured reflections |
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)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.095 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0345P)2 + 2.178P] where P = (Fo2 + 2Fc2)/3 |
3160 reflections | (Δ/σ)max = 0.001 |
228 parameters | Δρmax = 0.17 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
C17H21N5O3 | V = 3403.5 (16) Å3 |
Mr = 343.39 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 16.707 (6) Å | µ = 0.10 mm−1 |
b = 10.218 (2) Å | T = 120 K |
c = 20.733 (5) Å | 0.29 × 0.22 × 0.10 mm |
β = 105.929 (19)° |
Bruker Nonius KappaCCD area-detector diffractometer | 3160 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2239 reflections with I > 2σ(I) |
Tmin = 0.973, Tmax = 0.991 | Rint = 0.063 |
21914 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.095 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.17 e Å−3 |
3160 reflections | Δρmin = −0.23 e Å−3 |
228 parameters |
x | y | z | Uiso*/Ueq | ||
N1 | 0.40872 (10) | 0.17214 (14) | 0.28821 (7) | 0.0177 (3) | |
C2 | 0.46275 (11) | 0.23317 (17) | 0.34084 (8) | 0.0168 (4) | |
N3 | 0.44497 (9) | 0.28871 (14) | 0.39387 (7) | 0.0171 (3) | |
C4 | 0.36591 (11) | 0.27637 (17) | 0.39697 (8) | 0.0163 (4) | |
C5 | 0.30520 (11) | 0.20093 (17) | 0.34921 (9) | 0.0174 (4) | |
C6 | 0.33077 (12) | 0.15698 (17) | 0.29255 (9) | 0.0177 (4) | |
N21 | 0.54146 (9) | 0.24174 (15) | 0.33734 (7) | 0.0222 (4) | |
H21A | 0.5558 | 0.2094 | 0.3016 | 0.027* | |
H21B | 0.5819 | 0.2860 | 0.3731 | 0.027* | |
N41 | 0.34415 (10) | 0.33671 (15) | 0.44718 (7) | 0.0200 (4) | |
H41 | 0.2882 | 0.3264 | 0.4506 | 0.024* | |
C42 | 0.39948 (12) | 0.42037 (18) | 0.49688 (9) | 0.0219 (4) | |
H42A | 0.4561 | 0.4159 | 0.4908 | 0.026* | |
H42B | 0.4024 | 0.3869 | 0.5423 | 0.026* | |
C43 | 0.37086 (12) | 0.56410 (18) | 0.49202 (9) | 0.0238 (5) | |
H43A | 0.4176 | 0.6195 | 0.5174 | 0.029* | |
H43B | 0.3565 | 0.5919 | 0.4445 | 0.029* | |
C44 | 0.29701 (12) | 0.58623 (18) | 0.51876 (9) | 0.0224 (4) | |
O44 | 0.29875 (9) | 0.64666 (14) | 0.56953 (7) | 0.0312 (4) | |
O45 | 0.22837 (8) | 0.52993 (13) | 0.48012 (6) | 0.0233 (3) | |
C46 | 0.15224 (12) | 0.5431 (2) | 0.50101 (10) | 0.0268 (5) | |
H46A | 0.1341 | 0.6357 | 0.4983 | 0.032* | |
H46B | 0.1612 | 0.5124 | 0.5477 | 0.032* | |
C47 | 0.08790 (13) | 0.4597 (2) | 0.45338 (10) | 0.0309 (5) | |
H47A | 0.0789 | 0.4926 | 0.4075 | 0.046* | |
H47B | 0.0355 | 0.4633 | 0.4659 | 0.046* | |
H47C | 0.1075 | 0.3690 | 0.4557 | 0.046* | |
C51 | 0.22888 (12) | 0.16081 (18) | 0.36199 (9) | 0.0223 (4) | |
H51 | 0.1971 | 0.0960 | 0.3332 | 0.027* | |
O51 | 0.20072 (8) | 0.20319 (13) | 0.40731 (6) | 0.0281 (3) | |
N61 | 0.27576 (10) | 0.09496 (14) | 0.23933 (7) | 0.0198 (4) | |
C67 | 0.30784 (13) | 0.0352 (2) | 0.18652 (9) | 0.0259 (5) | |
H67A | 0.3126 | 0.1025 | 0.1541 | 0.039* | |
H67B | 0.2695 | −0.0333 | 0.1636 | 0.039* | |
H67C | 0.3627 | −0.0032 | 0.2069 | 0.039* | |
C61 | 0.19051 (12) | 0.13782 (18) | 0.21516 (9) | 0.0208 (4) | |
C62 | 0.17252 (13) | 0.2689 (2) | 0.19992 (10) | 0.0298 (5) | |
H62 | 0.2162 | 0.3310 | 0.2059 | 0.036* | |
C63 | 0.09012 (14) | 0.3083 (2) | 0.17591 (11) | 0.0379 (6) | |
H63 | 0.0776 | 0.3980 | 0.1660 | 0.045* | |
C64 | 0.02607 (14) | 0.2183 (2) | 0.16628 (10) | 0.0332 (5) | |
H64 | −0.0302 | 0.2461 | 0.1505 | 0.040* | |
C65 | 0.04448 (13) | 0.0876 (2) | 0.17972 (10) | 0.0286 (5) | |
H65 | 0.0008 | 0.0251 | 0.1723 | 0.034* | |
C66 | 0.12634 (13) | 0.04734 (19) | 0.20402 (9) | 0.0243 (5) | |
H66 | 0.1386 | −0.0427 | 0.2131 | 0.029* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0166 (9) | 0.0197 (8) | 0.0161 (8) | −0.0019 (7) | 0.0032 (7) | −0.0008 (6) |
C2 | 0.0157 (11) | 0.0172 (9) | 0.0165 (9) | 0.0023 (8) | 0.0027 (8) | 0.0029 (8) |
N3 | 0.0158 (9) | 0.0198 (8) | 0.0158 (8) | 0.0005 (7) | 0.0042 (7) | −0.0007 (6) |
C4 | 0.0173 (10) | 0.0153 (9) | 0.0161 (9) | 0.0016 (8) | 0.0043 (8) | 0.0035 (8) |
C5 | 0.0177 (11) | 0.0167 (9) | 0.0174 (9) | −0.0010 (8) | 0.0040 (8) | −0.0003 (7) |
C6 | 0.0191 (11) | 0.0137 (9) | 0.0184 (9) | −0.0012 (8) | 0.0019 (8) | 0.0016 (7) |
N21 | 0.0154 (9) | 0.0330 (9) | 0.0185 (8) | 0.0004 (8) | 0.0050 (7) | −0.0074 (7) |
N41 | 0.0169 (9) | 0.0256 (9) | 0.0184 (8) | −0.0036 (7) | 0.0064 (7) | −0.0059 (7) |
C42 | 0.0162 (11) | 0.0292 (11) | 0.0200 (10) | −0.0025 (9) | 0.0047 (8) | −0.0071 (8) |
C43 | 0.0206 (11) | 0.0264 (11) | 0.0249 (10) | −0.0054 (9) | 0.0071 (9) | −0.0073 (9) |
C44 | 0.0229 (12) | 0.0200 (10) | 0.0229 (10) | −0.0003 (9) | 0.0039 (9) | −0.0021 (8) |
O44 | 0.0261 (9) | 0.0387 (9) | 0.0284 (8) | −0.0022 (7) | 0.0069 (6) | −0.0152 (7) |
O45 | 0.0171 (8) | 0.0299 (7) | 0.0231 (7) | −0.0034 (6) | 0.0057 (6) | −0.0063 (6) |
C46 | 0.0200 (12) | 0.0330 (12) | 0.0289 (11) | 0.0026 (10) | 0.0091 (9) | −0.0043 (9) |
C47 | 0.0220 (12) | 0.0389 (12) | 0.0325 (12) | −0.0034 (10) | 0.0088 (10) | −0.0035 (10) |
C51 | 0.0227 (11) | 0.0246 (10) | 0.0185 (10) | −0.0053 (9) | 0.0038 (9) | −0.0016 (8) |
O51 | 0.0227 (8) | 0.0387 (8) | 0.0256 (7) | −0.0064 (7) | 0.0114 (6) | −0.0071 (6) |
N61 | 0.0194 (9) | 0.0221 (8) | 0.0173 (8) | −0.0024 (7) | 0.0042 (7) | −0.0050 (7) |
C67 | 0.0253 (12) | 0.0315 (11) | 0.0216 (10) | −0.0059 (10) | 0.0075 (9) | −0.0091 (9) |
C61 | 0.0198 (11) | 0.0251 (11) | 0.0155 (9) | −0.0030 (9) | 0.0017 (8) | −0.0023 (8) |
C62 | 0.0275 (13) | 0.0260 (11) | 0.0290 (11) | −0.0064 (10) | −0.0036 (9) | −0.0001 (9) |
C63 | 0.0366 (14) | 0.0264 (12) | 0.0392 (13) | 0.0024 (11) | −0.0086 (11) | 0.0008 (10) |
C64 | 0.0252 (13) | 0.0342 (13) | 0.0325 (12) | 0.0044 (11) | −0.0048 (10) | −0.0041 (10) |
C65 | 0.0239 (12) | 0.0310 (12) | 0.0280 (11) | −0.0068 (10) | 0.0022 (9) | −0.0057 (9) |
C66 | 0.0256 (12) | 0.0213 (10) | 0.0243 (10) | −0.0031 (9) | 0.0039 (9) | −0.0044 (8) |
N1—C6 | 1.339 (2) | C46—H46A | 0.9900 |
N1—C2 | 1.361 (2) | C46—H46B | 0.9900 |
C2—N21 | 1.340 (2) | C47—H47A | 0.9800 |
C2—N3 | 1.341 (2) | C47—H47B | 0.9800 |
N3—C4 | 1.346 (2) | C47—H47C | 0.9800 |
C4—N41 | 1.343 (2) | C51—O51 | 1.239 (2) |
C4—C5 | 1.433 (2) | C51—H51 | 0.9500 |
C5—C6 | 1.428 (2) | N61—C61 | 1.442 (2) |
C5—C51 | 1.432 (3) | N61—C67 | 1.477 (2) |
C6—N61 | 1.381 (2) | C67—H67A | 0.9800 |
N21—H21A | 0.9013 | C67—H67B | 0.9800 |
N21—H21B | 0.9681 | C67—H67C | 0.9800 |
N41—C42 | 1.458 (2) | C61—C66 | 1.386 (3) |
N41—H41 | 0.9621 | C61—C62 | 1.390 (3) |
C42—C43 | 1.539 (3) | C62—C63 | 1.389 (3) |
C42—H42A | 0.9900 | C62—H62 | 0.9500 |
C42—H42B | 0.9900 | C63—C64 | 1.384 (3) |
C43—C44 | 1.502 (3) | C63—H63 | 0.9500 |
C43—H43A | 0.9900 | C64—C65 | 1.381 (3) |
C43—H43B | 0.9900 | C64—H64 | 0.9500 |
C44—O44 | 1.214 (2) | C65—C66 | 1.384 (3) |
C44—O45 | 1.336 (2) | C65—H65 | 0.9500 |
O45—C46 | 1.458 (2) | C66—H66 | 0.9500 |
C46—C47 | 1.508 (3) | ||
C6—N1—C2 | 116.26 (15) | O45—C46—H46B | 110.5 |
N21—C2—N3 | 117.27 (16) | C47—C46—H46B | 110.5 |
N21—C2—N1 | 115.56 (15) | H46A—C46—H46B | 108.7 |
N3—C2—N1 | 127.13 (17) | C46—C47—H47A | 109.5 |
C2—N3—C4 | 116.14 (15) | C46—C47—H47B | 109.5 |
N41—C4—N3 | 118.17 (16) | H47A—C47—H47B | 109.5 |
N41—C4—C5 | 119.46 (16) | C46—C47—H47C | 109.5 |
N3—C4—C5 | 122.37 (16) | H47A—C47—H47C | 109.5 |
C6—C5—C51 | 123.02 (17) | H47B—C47—H47C | 109.5 |
C6—C5—C4 | 115.02 (16) | O51—C51—C5 | 125.68 (18) |
C51—C5—C4 | 121.59 (16) | O51—C51—H51 | 117.2 |
N1—C6—N61 | 116.47 (16) | C5—C51—H51 | 117.2 |
N1—C6—C5 | 122.34 (17) | C6—N61—C61 | 121.03 (15) |
N61—C6—C5 | 121.18 (17) | C6—N61—C67 | 119.00 (16) |
C2—N21—H21A | 120.5 | C61—N61—C67 | 113.12 (15) |
C2—N21—H21B | 118.6 | N61—C67—H67A | 109.5 |
H21A—N21—H21B | 120.9 | N61—C67—H67B | 109.5 |
C4—N41—C42 | 124.28 (16) | H67A—C67—H67B | 109.5 |
C4—N41—H41 | 118.8 | N61—C67—H67C | 109.5 |
C42—N41—H41 | 116.9 | H67A—C67—H67C | 109.5 |
N41—C42—C43 | 112.82 (16) | H67B—C67—H67C | 109.5 |
N41—C42—H42A | 109.0 | C66—C61—C62 | 119.71 (19) |
C43—C42—H42A | 109.0 | C66—C61—N61 | 120.02 (17) |
N41—C42—H42B | 109.0 | C62—C61—N61 | 120.20 (17) |
C43—C42—H42B | 109.0 | C63—C62—C61 | 119.50 (19) |
H42A—C42—H42B | 107.8 | C63—C62—H62 | 120.2 |
C44—C43—C42 | 113.03 (16) | C61—C62—H62 | 120.2 |
C44—C43—H43A | 109.0 | C64—C63—C62 | 120.7 (2) |
C42—C43—H43A | 109.0 | C64—C63—H63 | 119.7 |
C44—C43—H43B | 109.0 | C62—C63—H63 | 119.7 |
C42—C43—H43B | 109.0 | C65—C64—C63 | 119.5 (2) |
H43A—C43—H43B | 107.8 | C65—C64—H64 | 120.2 |
O44—C44—O45 | 123.48 (18) | C63—C64—H64 | 120.2 |
O44—C44—C43 | 124.76 (18) | C64—C65—C66 | 120.27 (19) |
O45—C44—C43 | 111.76 (16) | C64—C65—H65 | 119.9 |
C44—O45—C46 | 117.21 (14) | C66—C65—H65 | 119.9 |
O45—C46—C47 | 106.03 (15) | C65—C66—C61 | 120.27 (19) |
O45—C46—H46A | 110.5 | C65—C66—H66 | 119.9 |
C47—C46—H46A | 110.5 | C61—C66—H66 | 119.9 |
C6—N1—C2—N21 | 176.77 (15) | O44—C44—O45—C46 | 0.0 (3) |
C6—N1—C2—N3 | −5.7 (3) | C43—C44—O45—C46 | 179.43 (16) |
N21—C2—N3—C4 | −178.63 (15) | C44—O45—C46—C47 | −174.16 (16) |
N1—C2—N3—C4 | 3.8 (3) | C6—C5—C51—O51 | −174.25 (18) |
C2—N3—C4—N41 | −176.31 (15) | C4—C5—C51—O51 | 13.2 (3) |
C2—N3—C4—C5 | 4.2 (2) | N1—C6—N61—C61 | −141.21 (17) |
N41—C4—C5—C6 | 171.17 (16) | C5—C6—N61—C61 | 39.4 (2) |
N3—C4—C5—C6 | −9.3 (2) | N1—C6—N61—C67 | 7.8 (2) |
N41—C4—C5—C51 | −15.7 (3) | C5—C6—N61—C67 | −171.57 (16) |
N3—C4—C5—C51 | 163.79 (17) | C6—N61—C61—C66 | −131.94 (18) |
C2—N1—C6—N61 | −179.91 (15) | C67—N61—C61—C66 | 77.4 (2) |
C2—N1—C6—C5 | −0.5 (2) | C6—N61—C61—C62 | 51.1 (2) |
C51—C5—C6—N1 | −165.64 (17) | C67—N61—C61—C62 | −99.6 (2) |
C4—C5—C6—N1 | 7.4 (2) | C66—C61—C62—C63 | 2.3 (3) |
C51—C5—C6—N61 | 13.7 (3) | N61—C61—C62—C63 | 179.22 (17) |
C4—C5—C6—N61 | −173.28 (16) | C61—C62—C63—C64 | −0.8 (3) |
N3—C4—N41—C42 | 3.2 (3) | C62—C63—C64—C65 | −1.0 (3) |
C5—C4—N41—C42 | −177.28 (16) | C63—C64—C65—C66 | 1.4 (3) |
C4—N41—C42—C43 | 114.35 (19) | C64—C65—C66—C61 | 0.1 (3) |
N41—C42—C43—C44 | 74.4 (2) | C62—C61—C66—C65 | −1.9 (3) |
C42—C43—C44—O44 | 111.1 (2) | N61—C61—C66—C65 | −178.87 (16) |
C42—C43—C44—O45 | −68.3 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N21—H21A···N1i | 0.90 | 2.14 | 3.027 (2) | 169 |
N21—H21B···O44ii | 0.97 | 2.14 | 3.054 (2) | 158 |
N41—H41···O51 | 0.96 | 1.95 | 2.683 (2) | 131 |
Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x+1, −y+1, −z+1. |
C16H19N5O3 | F(000) = 696 |
Mr = 329.36 | Dx = 1.339 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3733 reflections |
a = 15.636 (4) Å | θ = 2.8–27.5° |
b = 6.5674 (18) Å | µ = 0.10 mm−1 |
c = 17.336 (5) Å | T = 120 K |
β = 113.440 (18)° | Block, colourless |
V = 1633.3 (8) Å3 | 0.29 × 0.27 × 0.15 mm |
Z = 4 |
Bruker Nonius KappaCCD area-detector diffractometer | 3013 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 2209 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.072 |
Detector resolution: 9.091 pixels mm-1 | θmax = 25.5°, θmin = 2.8° |
ϕ and ω scans | h = −18→18 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −7→7 |
Tmin = 0.973, Tmax = 0.986 | l = −20→20 |
21188 measured reflections |
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)] = 0.059 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.165 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0897P)2 + 1.0498P] where P = (Fo2 + 2Fc2)/3 |
3013 reflections | (Δ/σ)max = 0.001 |
219 parameters | Δρmax = 0.35 e Å−3 |
0 restraints | Δρmin = −0.36 e Å−3 |
C16H19N5O3 | V = 1633.3 (8) Å3 |
Mr = 329.36 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 15.636 (4) Å | µ = 0.10 mm−1 |
b = 6.5674 (18) Å | T = 120 K |
c = 17.336 (5) Å | 0.29 × 0.27 × 0.15 mm |
β = 113.440 (18)° |
Bruker Nonius KappaCCD area-detector diffractometer | 3013 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2209 reflections with I > 2σ(I) |
Tmin = 0.973, Tmax = 0.986 | Rint = 0.072 |
21188 measured reflections |
R[F2 > 2σ(F2)] = 0.059 | 0 restraints |
wR(F2) = 0.165 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.35 e Å−3 |
3013 reflections | Δρmin = −0.36 e Å−3 |
219 parameters |
x | y | z | Uiso*/Ueq | ||
N1 | 0.76191 (13) | 0.7943 (3) | 0.53404 (12) | 0.0198 (5) | |
C2 | 0.82036 (15) | 0.6345 (4) | 0.56416 (14) | 0.0182 (5) | |
N3 | 0.85110 (13) | 0.5052 (3) | 0.52088 (11) | 0.0186 (5) | |
C4 | 0.83019 (15) | 0.5560 (4) | 0.44062 (13) | 0.0170 (5) | |
C5 | 0.77674 (15) | 0.7337 (4) | 0.40234 (14) | 0.0191 (5) | |
C6 | 0.73816 (16) | 0.8387 (4) | 0.45326 (14) | 0.0184 (5) | |
N21 | 0.84767 (14) | 0.5969 (3) | 0.64650 (12) | 0.0227 (5) | |
H21A | 0.8254 | 0.6764 | 0.6840 | 0.027* | |
H21B | 0.8675 | 0.4707 | 0.6640 | 0.027* | |
N41 | 0.86339 (14) | 0.4372 (3) | 0.39645 (12) | 0.0216 (5) | |
H41 | 0.8525 | 0.4819 | 0.3409 | 0.026* | |
C42 | 0.92283 (16) | 0.2643 (4) | 0.43330 (14) | 0.0206 (5) | |
H42A | 0.8894 | 0.1646 | 0.4540 | 0.025* | |
H42B | 0.9793 | 0.3093 | 0.4816 | 0.025* | |
C43 | 0.94983 (16) | 0.1673 (4) | 0.36808 (14) | 0.0193 (5) | |
O43 | 0.91642 (11) | 0.2078 (3) | 0.29407 (10) | 0.0231 (4) | |
O44 | 1.01581 (12) | 0.0275 (3) | 0.40347 (10) | 0.0258 (4) | |
C45 | 1.04556 (18) | −0.0855 (4) | 0.34677 (16) | 0.0268 (6) | |
H45A | 1.0646 | 0.0098 | 0.3131 | 0.040* | |
H45B | 0.9939 | −0.1696 | 0.3095 | 0.040* | |
H45C | 1.0983 | −0.1731 | 0.3794 | 0.040* | |
C51 | 0.77698 (15) | 0.8161 (4) | 0.32669 (14) | 0.0200 (5) | |
H51 | 0.7535 | 0.9504 | 0.3121 | 0.024* | |
O51 | 0.80517 (12) | 0.7278 (3) | 0.27814 (10) | 0.0262 (4) | |
N61 | 0.67418 (14) | 0.9937 (3) | 0.42083 (12) | 0.0220 (5) | |
C67 | 0.59484 (17) | 0.9692 (4) | 0.33873 (15) | 0.0246 (6) | |
H67A | 0.6164 | 0.8947 | 0.3001 | 0.029* | |
H67B | 0.5735 | 1.1055 | 0.3143 | 0.029* | |
C61 | 0.51365 (17) | 0.8562 (4) | 0.34467 (15) | 0.0221 (5) | |
C62 | 0.52537 (18) | 0.6637 (4) | 0.38099 (16) | 0.0285 (6) | |
H62 | 0.5858 | 0.6047 | 0.4040 | 0.034* | |
C63 | 0.45071 (19) | 0.5564 (5) | 0.38425 (17) | 0.0320 (6) | |
H63 | 0.4601 | 0.4251 | 0.4093 | 0.038* | |
C64 | 0.36207 (18) | 0.6408 (5) | 0.35094 (17) | 0.0327 (7) | |
H64 | 0.3106 | 0.5678 | 0.3531 | 0.039* | |
C65 | 0.34922 (18) | 0.8310 (5) | 0.31483 (18) | 0.0360 (7) | |
H65 | 0.2886 | 0.8891 | 0.2919 | 0.043* | |
C66 | 0.42394 (17) | 0.9384 (5) | 0.31163 (16) | 0.0292 (6) | |
H66 | 0.4140 | 1.0698 | 0.2866 | 0.035* | |
C68 | 0.65143 (18) | 1.1154 (4) | 0.48056 (16) | 0.0283 (6) | |
H68A | 0.7090 | 1.1536 | 0.5280 | 0.042* | |
H68B | 0.6119 | 1.0356 | 0.5012 | 0.042* | |
H68C | 0.6181 | 1.2386 | 0.4526 | 0.042* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0178 (10) | 0.0224 (11) | 0.0180 (10) | 0.0019 (8) | 0.0059 (8) | 0.0006 (8) |
C2 | 0.0139 (11) | 0.0219 (13) | 0.0185 (11) | −0.0020 (10) | 0.0062 (9) | −0.0016 (10) |
N3 | 0.0181 (10) | 0.0218 (11) | 0.0152 (10) | 0.0001 (8) | 0.0061 (8) | −0.0007 (8) |
C4 | 0.0122 (11) | 0.0216 (13) | 0.0153 (11) | −0.0016 (9) | 0.0037 (9) | −0.0005 (9) |
C5 | 0.0132 (11) | 0.0233 (13) | 0.0187 (11) | −0.0012 (10) | 0.0043 (9) | 0.0004 (10) |
C6 | 0.0156 (11) | 0.0196 (13) | 0.0186 (11) | −0.0025 (9) | 0.0052 (9) | −0.0009 (9) |
N21 | 0.0268 (11) | 0.0249 (12) | 0.0166 (10) | 0.0053 (9) | 0.0090 (8) | 0.0016 (8) |
N41 | 0.0231 (11) | 0.0256 (12) | 0.0156 (9) | 0.0056 (9) | 0.0071 (8) | 0.0023 (8) |
C42 | 0.0201 (12) | 0.0231 (13) | 0.0168 (11) | 0.0016 (10) | 0.0052 (9) | −0.0011 (10) |
C43 | 0.0191 (12) | 0.0175 (13) | 0.0206 (12) | −0.0016 (10) | 0.0072 (10) | −0.0007 (9) |
O43 | 0.0254 (9) | 0.0269 (10) | 0.0166 (8) | 0.0016 (7) | 0.0079 (7) | −0.0002 (7) |
O44 | 0.0280 (10) | 0.0291 (10) | 0.0190 (8) | 0.0097 (8) | 0.0079 (7) | 0.0003 (7) |
C45 | 0.0275 (13) | 0.0291 (15) | 0.0238 (12) | 0.0077 (11) | 0.0102 (11) | −0.0031 (11) |
C51 | 0.0125 (11) | 0.0251 (14) | 0.0194 (11) | 0.0003 (10) | 0.0031 (9) | 0.0021 (10) |
O51 | 0.0284 (10) | 0.0332 (11) | 0.0195 (8) | 0.0013 (8) | 0.0121 (7) | 0.0041 (8) |
N61 | 0.0182 (10) | 0.0239 (12) | 0.0202 (10) | 0.0030 (9) | 0.0037 (8) | −0.0002 (8) |
C67 | 0.0209 (13) | 0.0276 (15) | 0.0210 (12) | 0.0059 (11) | 0.0039 (10) | 0.0057 (10) |
C61 | 0.0199 (12) | 0.0270 (14) | 0.0164 (11) | 0.0012 (10) | 0.0040 (9) | −0.0020 (10) |
C62 | 0.0206 (13) | 0.0313 (16) | 0.0293 (13) | 0.0005 (11) | 0.0054 (11) | 0.0013 (12) |
C63 | 0.0286 (14) | 0.0346 (16) | 0.0292 (13) | −0.0062 (12) | 0.0078 (11) | −0.0005 (12) |
C64 | 0.0235 (14) | 0.0464 (19) | 0.0289 (14) | −0.0103 (13) | 0.0111 (11) | −0.0123 (13) |
C65 | 0.0167 (13) | 0.054 (2) | 0.0329 (15) | 0.0023 (12) | 0.0051 (11) | −0.0084 (14) |
C66 | 0.0227 (13) | 0.0344 (16) | 0.0267 (13) | 0.0076 (11) | 0.0057 (11) | 0.0017 (11) |
C68 | 0.0239 (13) | 0.0282 (15) | 0.0286 (13) | 0.0077 (11) | 0.0061 (11) | −0.0033 (11) |
N1—C6 | 1.331 (3) | C45—H45C | 0.9800 |
N1—C2 | 1.353 (3) | C51—O51 | 1.239 (3) |
C2—N21 | 1.340 (3) | C51—H51 | 0.9500 |
C2—N3 | 1.342 (3) | N61—C68 | 1.459 (3) |
N3—C4 | 1.339 (3) | N61—C67 | 1.479 (3) |
C4—N41 | 1.334 (3) | C67—C61 | 1.509 (4) |
C4—C5 | 1.436 (3) | C67—H67A | 0.9900 |
C5—C51 | 1.420 (3) | C67—H67B | 0.9900 |
C5—C6 | 1.429 (3) | C61—C62 | 1.392 (4) |
C6—N61 | 1.381 (3) | C61—C66 | 1.396 (4) |
N21—H21A | 0.9984 | C62—C63 | 1.383 (4) |
N21—H21B | 0.8951 | C62—H62 | 0.9500 |
N41—C42 | 1.445 (3) | C63—C64 | 1.387 (4) |
N41—H41 | 0.9547 | C63—H63 | 0.9500 |
C42—C43 | 1.497 (3) | C64—C65 | 1.376 (5) |
C42—H42A | 0.9900 | C64—H64 | 0.9500 |
C42—H42B | 0.9900 | C65—C66 | 1.385 (4) |
C43—O43 | 1.207 (3) | C65—H65 | 0.9500 |
C43—O44 | 1.334 (3) | C66—H66 | 0.9500 |
O44—C45 | 1.448 (3) | C68—H68A | 0.9800 |
C45—H45A | 0.9800 | C68—H68B | 0.9800 |
C45—H45B | 0.9800 | C68—H68C | 0.9800 |
C6—N1—C2 | 116.0 (2) | O51—C51—C5 | 125.5 (2) |
N21—C2—N3 | 116.5 (2) | O51—C51—H51 | 117.2 |
N21—C2—N1 | 115.7 (2) | C5—C51—H51 | 117.2 |
N3—C2—N1 | 127.8 (2) | C6—N61—C68 | 117.2 (2) |
C4—N3—C2 | 115.4 (2) | C6—N61—C67 | 120.4 (2) |
N41—C4—N3 | 117.4 (2) | C68—N61—C67 | 113.3 (2) |
N41—C4—C5 | 119.9 (2) | N61—C67—C61 | 113.2 (2) |
N3—C4—C5 | 122.7 (2) | N61—C67—H67A | 108.9 |
C51—C5—C6 | 122.9 (2) | C61—C67—H67A | 108.9 |
C51—C5—C4 | 121.5 (2) | N61—C67—H67B | 108.9 |
C6—C5—C4 | 114.7 (2) | C61—C67—H67B | 108.9 |
N1—C6—N61 | 116.3 (2) | H67A—C67—H67B | 107.7 |
N1—C6—C5 | 122.3 (2) | C62—C61—C66 | 117.8 (2) |
N61—C6—C5 | 121.3 (2) | C62—C61—C67 | 121.0 (2) |
C2—N21—H21A | 123.5 | C66—C61—C67 | 121.1 (2) |
C2—N21—H21B | 116.9 | C63—C62—C61 | 121.3 (3) |
H21A—N21—H21B | 115.2 | C63—C62—H62 | 119.3 |
C4—N41—C42 | 122.29 (19) | C61—C62—H62 | 119.3 |
C4—N41—H41 | 116.4 | C62—C63—C64 | 119.9 (3) |
C42—N41—H41 | 120.8 | C62—C63—H63 | 120.0 |
N41—C42—C43 | 108.99 (18) | C64—C63—H63 | 120.0 |
N41—C42—H42A | 109.9 | C65—C64—C63 | 119.5 (3) |
C43—C42—H42A | 109.9 | C65—C64—H64 | 120.2 |
N41—C42—H42B | 109.9 | C63—C64—H64 | 120.2 |
C43—C42—H42B | 109.9 | C64—C65—C66 | 120.5 (3) |
H42A—C42—H42B | 108.3 | C64—C65—H65 | 119.7 |
O43—C43—O44 | 124.7 (2) | C66—C65—H65 | 119.7 |
O43—C43—C42 | 125.2 (2) | C65—C66—C61 | 120.8 (3) |
O44—C43—C42 | 110.13 (19) | C65—C66—H66 | 119.6 |
C43—O44—C45 | 116.03 (18) | C61—C66—H66 | 119.6 |
O44—C45—H45A | 109.5 | N61—C68—H68A | 109.5 |
O44—C45—H45B | 109.5 | N61—C68—H68B | 109.5 |
H45A—C45—H45B | 109.5 | H68A—C68—H68B | 109.5 |
O44—C45—H45C | 109.5 | N61—C68—H68C | 109.5 |
H45A—C45—H45C | 109.5 | H68A—C68—H68C | 109.5 |
H45B—C45—H45C | 109.5 | H68B—C68—H68C | 109.5 |
C6—N1—C2—N21 | 176.8 (2) | O43—C43—O44—C45 | −2.2 (4) |
C6—N1—C2—N3 | −6.0 (4) | C42—C43—O44—C45 | 177.2 (2) |
N21—C2—N3—C4 | −174.1 (2) | C6—C5—C51—O51 | −176.2 (2) |
N1—C2—N3—C4 | 8.8 (4) | C4—C5—C51—O51 | 15.3 (4) |
C2—N3—C4—N41 | 176.7 (2) | N1—C6—N61—C68 | 10.2 (3) |
C2—N3—C4—C5 | −1.4 (3) | C5—C6—N61—C68 | −169.3 (2) |
N41—C4—C5—C51 | −15.8 (3) | N1—C6—N61—C67 | −134.4 (2) |
N3—C4—C5—C51 | 162.2 (2) | C5—C6—N61—C67 | 46.0 (3) |
N41—C4—C5—C6 | 174.8 (2) | C6—N61—C67—C61 | 83.0 (3) |
N3—C4—C5—C6 | −7.2 (3) | C68—N61—C67—C61 | −63.0 (3) |
C2—N1—C6—N61 | 176.2 (2) | N61—C67—C61—C62 | −55.3 (3) |
C2—N1—C6—C5 | −4.2 (3) | N61—C67—C61—C66 | 126.7 (2) |
C51—C5—C6—N1 | −159.1 (2) | C66—C61—C62—C63 | 0.1 (4) |
C4—C5—C6—N1 | 10.1 (3) | C67—C61—C62—C63 | −177.9 (2) |
C51—C5—C6—N61 | 20.4 (4) | C61—C62—C63—C64 | −0.1 (4) |
C4—C5—C6—N61 | −170.3 (2) | C62—C63—C64—C65 | 0.0 (4) |
N3—C4—N41—C42 | −2.4 (3) | C63—C64—C65—C66 | −0.1 (4) |
C5—C4—N41—C42 | 175.7 (2) | C64—C65—C66—C61 | 0.2 (4) |
C4—N41—C42—C43 | −178.5 (2) | C62—C61—C66—C65 | −0.2 (4) |
N41—C42—C43—O43 | −10.1 (3) | C67—C61—C66—C65 | 177.9 (2) |
N41—C42—C43—O44 | 170.47 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
N21—H21A···O51i | 1.00 | 1.89 | 2.860 (3) | 163 |
N21—H21B···O43ii | 0.89 | 2.38 | 3.085 (3) | 136 |
N41—H41···O51 | 0.96 | 1.92 | 2.682 (3) | 135 |
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) x, −y+1/2, z+1/2. |
C18H23N5O3 | F(000) = 1520 |
Mr = 357.41 | Dx = 1.355 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 4039 reflections |
a = 24.8226 (5) Å | θ = 3.0–27.5° |
b = 7.1379 (14) Å | µ = 0.10 mm−1 |
c = 20.601 (2) Å | T = 120 K |
β = 106.213 (8)° | Block, colourless |
V = 3505.0 (8) Å3 | 0.26 × 0.21 × 0.14 mm |
Z = 8 |
Bruker Nonius KappaCCD area-detector diffractometer | 3269 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 2276 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.073 |
Detector resolution: 9.091 pixels mm-1 | θmax = 25.5°, θmin = 3.0° |
ϕ and ω scans | h = −30→30 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −8→8 |
Tmin = 0.976, Tmax = 0.987 | l = −24→24 |
22384 measured reflections |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.104 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.039P)2 + 2.9368P] where P = (Fo2 + 2Fc2)/3 |
3269 reflections | (Δ/σ)max = 0.001 |
237 parameters | Δρmax = 0.21 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
C18H23N5O3 | V = 3505.0 (8) Å3 |
Mr = 357.41 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 24.8226 (5) Å | µ = 0.10 mm−1 |
b = 7.1379 (14) Å | T = 120 K |
c = 20.601 (2) Å | 0.26 × 0.21 × 0.14 mm |
β = 106.213 (8)° |
Bruker Nonius KappaCCD area-detector diffractometer | 3269 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2276 reflections with I > 2σ(I) |
Tmin = 0.976, Tmax = 0.987 | Rint = 0.073 |
22384 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.104 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.21 e Å−3 |
3269 reflections | Δρmin = −0.25 e Å−3 |
237 parameters |
x | y | z | Uiso*/Ueq | ||
N1 | 0.69278 (6) | 0.7477 (2) | 0.66478 (8) | 0.0163 (4) | |
C2 | 0.70537 (8) | 0.6127 (3) | 0.71219 (10) | 0.0154 (4) | |
N3 | 0.67234 (6) | 0.4705 (2) | 0.72058 (8) | 0.0166 (4) | |
C4 | 0.62542 (8) | 0.4445 (3) | 0.66962 (10) | 0.0159 (4) | |
C5 | 0.61274 (8) | 0.5559 (3) | 0.60889 (10) | 0.0169 (4) | |
C6 | 0.64576 (8) | 0.7221 (3) | 0.61344 (9) | 0.0157 (4) | |
N21 | 0.75599 (6) | 0.6237 (2) | 0.75782 (8) | 0.0188 (4) | |
H21A | 0.7798 | 0.7296 | 0.7585 | 0.023* | |
H21B | 0.7679 | 0.5267 | 0.7903 | 0.023* | |
N41 | 0.59084 (7) | 0.3046 (2) | 0.67526 (8) | 0.0200 (4) | |
H41 | 0.5572 | 0.2751 | 0.6363 | 0.024* | |
C42 | 0.59488 (8) | 0.1981 (3) | 0.73683 (10) | 0.0202 (5) | |
H42A | 0.5670 | 0.2466 | 0.7588 | 0.024* | |
H42B | 0.6326 | 0.2161 | 0.7685 | 0.024* | |
C43 | 0.58472 (8) | −0.0093 (3) | 0.72265 (10) | 0.0202 (5) | |
H43A | 0.6123 | −0.0571 | 0.7001 | 0.024* | |
H43B | 0.5907 | −0.0769 | 0.7660 | 0.024* | |
C44 | 0.52655 (8) | −0.0493 (3) | 0.67878 (10) | 0.0191 (5) | |
O44 | 0.49263 (6) | 0.0690 (2) | 0.65309 (9) | 0.0387 (4) | |
O45 | 0.51667 (6) | −0.23223 (19) | 0.67155 (7) | 0.0267 (4) | |
C46 | 0.46236 (9) | −0.2905 (3) | 0.62757 (11) | 0.0288 (5) | |
H46A | 0.4650 | −0.3114 | 0.5810 | 0.035* | |
H46B | 0.4339 | −0.1924 | 0.6262 | 0.035* | |
C47 | 0.44631 (9) | −0.4687 (3) | 0.65593 (12) | 0.0328 (6) | |
H47A | 0.4763 | −0.5613 | 0.6606 | 0.049* | |
H47B | 0.4115 | −0.5174 | 0.6254 | 0.049* | |
H47C | 0.4406 | −0.4438 | 0.7003 | 0.049* | |
C51 | 0.57391 (8) | 0.4903 (3) | 0.54831 (10) | 0.0210 (5) | |
H51 | 0.5723 | 0.5570 | 0.5079 | 0.025* | |
O51 | 0.54207 (6) | 0.35380 (19) | 0.54367 (7) | 0.0249 (4) | |
N61 | 0.63127 (6) | 0.8638 (2) | 0.56785 (8) | 0.0173 (4) | |
C67 | 0.67035 (8) | 1.0176 (3) | 0.56761 (10) | 0.0199 (5) | |
H67A | 0.7071 | 0.9885 | 0.5999 | 0.024* | |
H67B | 0.6560 | 1.1337 | 0.5831 | 0.024* | |
C61 | 0.67824 (8) | 1.0504 (3) | 0.49824 (10) | 0.0197 (5) | |
C62 | 0.68991 (9) | 0.9001 (3) | 0.46137 (11) | 0.0258 (5) | |
H62 | 0.6899 | 0.7762 | 0.4782 | 0.031* | |
C63 | 0.70159 (9) | 0.9299 (4) | 0.40034 (11) | 0.0333 (6) | |
H63 | 0.7097 | 0.8266 | 0.3756 | 0.040* | |
C64 | 0.70148 (9) | 1.1090 (4) | 0.37540 (11) | 0.0343 (6) | |
H64 | 0.7095 | 1.1290 | 0.3335 | 0.041* | |
C65 | 0.68969 (9) | 1.2590 (3) | 0.41123 (11) | 0.0318 (6) | |
H65 | 0.6894 | 1.3824 | 0.3939 | 0.038* | |
C66 | 0.67813 (8) | 1.2301 (3) | 0.47289 (11) | 0.0243 (5) | |
H66 | 0.6701 | 1.3338 | 0.4976 | 0.029* | |
C68 | 0.57405 (8) | 0.8987 (3) | 0.52501 (10) | 0.0215 (5) | |
H68A | 0.5714 | 0.8621 | 0.4784 | 0.032* | |
H68B | 0.5653 | 1.0323 | 0.5264 | 0.032* | |
H68C | 0.5474 | 0.8251 | 0.5417 | 0.032* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0162 (8) | 0.0174 (9) | 0.0144 (9) | 0.0005 (7) | 0.0028 (7) | 0.0001 (8) |
C2 | 0.0154 (10) | 0.0149 (10) | 0.0159 (11) | 0.0020 (8) | 0.0042 (9) | −0.0031 (9) |
N3 | 0.0153 (8) | 0.0175 (9) | 0.0157 (9) | 0.0010 (7) | 0.0024 (7) | 0.0005 (7) |
C4 | 0.0151 (10) | 0.0141 (10) | 0.0190 (11) | 0.0031 (8) | 0.0054 (9) | −0.0038 (9) |
C5 | 0.0163 (10) | 0.0163 (10) | 0.0174 (10) | 0.0016 (8) | 0.0037 (8) | 0.0007 (9) |
C6 | 0.0164 (10) | 0.0174 (11) | 0.0147 (10) | 0.0022 (8) | 0.0064 (8) | −0.0017 (9) |
N21 | 0.0172 (9) | 0.0170 (9) | 0.0187 (9) | −0.0023 (7) | −0.0008 (7) | 0.0034 (8) |
N41 | 0.0197 (9) | 0.0184 (9) | 0.0192 (9) | −0.0027 (7) | 0.0010 (7) | 0.0029 (8) |
C42 | 0.0221 (11) | 0.0207 (11) | 0.0179 (11) | −0.0028 (9) | 0.0057 (9) | 0.0007 (9) |
C43 | 0.0194 (10) | 0.0214 (11) | 0.0201 (11) | 0.0007 (9) | 0.0063 (9) | 0.0022 (9) |
C44 | 0.0239 (11) | 0.0160 (11) | 0.0192 (11) | −0.0015 (9) | 0.0092 (9) | 0.0002 (9) |
O44 | 0.0252 (8) | 0.0215 (8) | 0.0587 (12) | 0.0003 (7) | −0.0059 (8) | 0.0012 (8) |
O45 | 0.0260 (8) | 0.0172 (8) | 0.0320 (9) | −0.0039 (6) | 0.0002 (7) | 0.0003 (7) |
C46 | 0.0284 (12) | 0.0281 (13) | 0.0265 (13) | −0.0098 (10) | 0.0018 (10) | −0.0015 (11) |
C47 | 0.0292 (12) | 0.0231 (13) | 0.0433 (15) | −0.0040 (10) | 0.0057 (11) | 0.0028 (11) |
C51 | 0.0218 (11) | 0.0167 (11) | 0.0217 (11) | 0.0049 (9) | 0.0017 (9) | 0.0019 (10) |
O51 | 0.0244 (8) | 0.0170 (8) | 0.0266 (9) | −0.0045 (6) | −0.0040 (7) | −0.0007 (7) |
N61 | 0.0167 (8) | 0.0172 (9) | 0.0164 (9) | −0.0020 (7) | 0.0021 (7) | 0.0032 (8) |
C67 | 0.0217 (10) | 0.0201 (11) | 0.0167 (11) | −0.0035 (9) | 0.0032 (9) | −0.0006 (9) |
C61 | 0.0138 (10) | 0.0246 (12) | 0.0184 (11) | −0.0025 (9) | 0.0006 (8) | 0.0036 (10) |
C62 | 0.0259 (11) | 0.0276 (13) | 0.0239 (12) | 0.0003 (10) | 0.0069 (10) | 0.0003 (10) |
C63 | 0.0277 (12) | 0.0487 (15) | 0.0252 (13) | −0.0016 (11) | 0.0102 (10) | −0.0055 (12) |
C64 | 0.0243 (12) | 0.0607 (18) | 0.0190 (12) | −0.0039 (12) | 0.0076 (10) | 0.0082 (12) |
C65 | 0.0211 (11) | 0.0412 (15) | 0.0309 (13) | −0.0026 (11) | 0.0034 (10) | 0.0187 (12) |
C66 | 0.0180 (10) | 0.0260 (12) | 0.0274 (12) | −0.0004 (9) | 0.0040 (9) | 0.0054 (10) |
C68 | 0.0193 (11) | 0.0190 (11) | 0.0234 (12) | 0.0011 (9) | 0.0012 (9) | 0.0023 (9) |
N1—C2 | 1.346 (2) | C46—H46B | 0.9900 |
N1—C6 | 1.351 (2) | C47—H47A | 0.9800 |
C2—N21 | 1.345 (2) | C47—H47B | 0.9800 |
C2—N3 | 1.346 (2) | C47—H47C | 0.9800 |
N3—C4 | 1.346 (2) | C51—O51 | 1.241 (2) |
C4—N41 | 1.343 (2) | C51—H51 | 0.9500 |
C4—C5 | 1.441 (3) | N61—C67 | 1.466 (2) |
C5—C51 | 1.426 (3) | N61—C68 | 1.469 (2) |
C5—C6 | 1.430 (3) | C67—C61 | 1.514 (3) |
C6—N61 | 1.359 (2) | C67—H67A | 0.9900 |
N21—H21A | 0.9568 | C67—H67B | 0.9900 |
N21—H21B | 0.9506 | C61—C66 | 1.384 (3) |
N41—C42 | 1.458 (2) | C61—C62 | 1.391 (3) |
N41—H41 | 1.0067 | C62—C63 | 1.383 (3) |
C42—C43 | 1.516 (3) | C62—H62 | 0.9500 |
C42—H42A | 0.9900 | C63—C64 | 1.377 (3) |
C42—H42B | 0.9900 | C63—H63 | 0.9500 |
C43—C44 | 1.501 (3) | C64—C65 | 1.378 (3) |
C43—H43A | 0.9900 | C64—H64 | 0.9500 |
C43—H43B | 0.9900 | C65—C66 | 1.394 (3) |
C44—O44 | 1.205 (2) | C65—H65 | 0.9500 |
C44—O45 | 1.330 (2) | C66—H66 | 0.9500 |
O45—C46 | 1.459 (2) | C68—H68A | 0.9800 |
C46—C47 | 1.499 (3) | C68—H68B | 0.9800 |
C46—H46A | 0.9900 | C68—H68C | 0.9800 |
C2—N1—C6 | 116.49 (16) | C46—C47—H47A | 109.5 |
N21—C2—N1 | 116.59 (17) | C46—C47—H47B | 109.5 |
N21—C2—N3 | 115.99 (17) | H47A—C47—H47B | 109.5 |
N1—C2—N3 | 127.38 (17) | C46—C47—H47C | 109.5 |
C4—N3—C2 | 115.43 (16) | H47A—C47—H47C | 109.5 |
N41—C4—N3 | 118.03 (17) | H47B—C47—H47C | 109.5 |
N41—C4—C5 | 119.71 (17) | O51—C51—C5 | 125.83 (19) |
N3—C4—C5 | 122.21 (17) | O51—C51—H51 | 117.1 |
C51—C5—C6 | 124.40 (18) | C5—C51—H51 | 117.1 |
C51—C5—C4 | 120.58 (18) | C6—N61—C67 | 120.81 (16) |
C6—C5—C4 | 114.74 (17) | C6—N61—C68 | 124.49 (16) |
N1—C6—N61 | 116.39 (17) | C67—N61—C68 | 113.63 (15) |
N1—C6—C5 | 121.19 (17) | N61—C67—C61 | 112.29 (16) |
N61—C6—C5 | 122.41 (17) | N61—C67—H67A | 109.1 |
C2—N21—H21A | 120.6 | C61—C67—H67A | 109.1 |
C2—N21—H21B | 119.7 | N61—C67—H67B | 109.1 |
H21A—N21—H21B | 119.8 | C61—C67—H67B | 109.1 |
C4—N41—C42 | 124.93 (17) | H67A—C67—H67B | 107.9 |
C4—N41—H41 | 119.7 | C66—C61—C62 | 119.17 (19) |
C42—N41—H41 | 115.2 | C66—C61—C67 | 120.82 (19) |
N41—C42—C43 | 111.95 (16) | C62—C61—C67 | 119.84 (18) |
N41—C42—H42A | 109.2 | C63—C62—C61 | 120.4 (2) |
C43—C42—H42A | 109.2 | C63—C62—H62 | 119.8 |
N41—C42—H42B | 109.2 | C61—C62—H62 | 119.8 |
C43—C42—H42B | 109.2 | C64—C63—C62 | 120.2 (2) |
H42A—C42—H42B | 107.9 | C64—C63—H63 | 119.9 |
C44—C43—C42 | 112.44 (17) | C62—C63—H63 | 119.9 |
C44—C43—H43A | 109.1 | C63—C64—C65 | 120.0 (2) |
C42—C43—H43A | 109.1 | C63—C64—H64 | 120.0 |
C44—C43—H43B | 109.1 | C65—C64—H64 | 120.0 |
C42—C43—H43B | 109.1 | C64—C65—C66 | 120.1 (2) |
H43A—C43—H43B | 107.8 | C64—C65—H65 | 119.9 |
O44—C44—O45 | 123.66 (19) | C66—C65—H65 | 119.9 |
O44—C44—C43 | 124.59 (19) | C61—C66—C65 | 120.1 (2) |
O45—C44—C43 | 111.75 (17) | C61—C66—H66 | 119.9 |
C44—O45—C46 | 117.33 (16) | C65—C66—H66 | 119.9 |
O45—C46—C47 | 107.45 (17) | N61—C68—H68A | 109.5 |
O45—C46—H46A | 110.2 | N61—C68—H68B | 109.5 |
C47—C46—H46A | 110.2 | H68A—C68—H68B | 109.5 |
O45—C46—H46B | 110.2 | N61—C68—H68C | 109.5 |
C47—C46—H46B | 110.2 | H68A—C68—H68C | 109.5 |
H46A—C46—H46B | 108.5 | H68B—C68—H68C | 109.5 |
C6—N1—C2—N21 | 170.68 (16) | O44—C44—O45—C46 | 2.7 (3) |
C6—N1—C2—N3 | −11.6 (3) | C43—C44—O45—C46 | −177.40 (16) |
N21—C2—N3—C4 | −170.86 (16) | C44—O45—C46—C47 | −147.25 (18) |
N1—C2—N3—C4 | 11.4 (3) | C6—C5—C51—O51 | −174.98 (18) |
C2—N3—C4—N41 | −179.97 (16) | C4—C5—C51—O51 | 11.5 (3) |
C2—N3—C4—C5 | 2.7 (3) | N1—C6—N61—C67 | 11.4 (2) |
N41—C4—C5—C51 | −17.6 (3) | C5—C6—N61—C67 | −170.05 (17) |
N3—C4—C5—C51 | 159.69 (18) | N1—C6—N61—C68 | −156.05 (17) |
N41—C4—C5—C6 | 168.26 (16) | C5—C6—N61—C68 | 22.5 (3) |
N3—C4—C5—C6 | −14.5 (3) | C6—N61—C67—C61 | 128.48 (18) |
C2—N1—C6—N61 | 176.14 (16) | C68—N61—C67—C61 | −62.8 (2) |
C2—N1—C6—C5 | −2.5 (3) | N61—C67—C61—C66 | 135.72 (19) |
C51—C5—C6—N1 | −159.69 (18) | N61—C67—C61—C62 | −49.1 (2) |
C4—C5—C6—N1 | 14.2 (3) | C66—C61—C62—C63 | 0.4 (3) |
C51—C5—C6—N61 | 21.8 (3) | C67—C61—C62—C63 | −174.87 (19) |
C4—C5—C6—N61 | −164.31 (17) | C61—C62—C63—C64 | −0.3 (3) |
N3—C4—N41—C42 | 11.0 (3) | C62—C63—C64—C65 | 0.0 (3) |
C5—C4—N41—C42 | −171.62 (17) | C63—C64—C65—C66 | 0.3 (3) |
C4—N41—C42—C43 | −138.69 (18) | C62—C61—C66—C65 | −0.1 (3) |
N41—C42—C43—C44 | −63.1 (2) | C67—C61—C66—C65 | 175.10 (18) |
C42—C43—C44—O44 | 5.3 (3) | C64—C65—C66—C61 | −0.2 (3) |
C42—C43—C44—O45 | −174.63 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
N21—H21A···N3i | 0.96 | 2.07 | 3.008 (2) | 168 |
N21—H21B···N1ii | 0.95 | 2.30 | 3.199 (2) | 158 |
N41—H41···O44 | 1.01 | 2.27 | 2.891 (2) | 119 |
N41—H41···O51 | 1.01 | 1.92 | 2.666 (2) | 128 |
C46—H46A···O51iii | 0.99 | 2.54 | 3.528 (3) | 172 |
Symmetry codes: (i) −x+3/2, y+1/2, −z+3/2; (ii) −x+3/2, y−1/2, −z+3/2; (iii) −x+1, −y, −z+1. |
C15H23N5O3 | Z = 2 |
Mr = 321.38 | F(000) = 344 |
Triclinic, P1 | Dx = 1.366 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.040 (4) Å | Cell parameters from 3583 reflections |
b = 10.391 (3) Å | θ = 2.9–27.5° |
c = 10.458 (8) Å | µ = 0.10 mm−1 |
α = 109.16 (3)° | T = 120 K |
β = 98.19 (5)° | Block, colourless |
γ = 103.10 (3)° | 0.41 × 0.25 × 0.22 mm |
V = 781.2 (8) Å3 |
Bruker Nonius KappaCCD area-detector diffractometer | 3227 independent reflections |
Radiation source: Bruker–Nonius FR591 rotating anode | 2384 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.059 |
Detector resolution: 9.091 pixels mm-1 | θmax = 26.5°, θmin = 2.9° |
ϕ and ω scans | h = −10→10 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −13→13 |
Tmin = 0.885, Tmax = 0.936 | l = −13→13 |
17622 measured reflections |
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)] = 0.051 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.134 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0571P)2 + 0.5988P] where P = (Fo2 + 2Fc2)/3 |
3227 reflections | (Δ/σ)max = 0.001 |
209 parameters | Δρmax = 0.25 e Å−3 |
0 restraints | Δρmin = −0.32 e Å−3 |
C15H23N5O3 | γ = 103.10 (3)° |
Mr = 321.38 | V = 781.2 (8) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.040 (4) Å | Mo Kα radiation |
b = 10.391 (3) Å | µ = 0.10 mm−1 |
c = 10.458 (8) Å | T = 120 K |
α = 109.16 (3)° | 0.41 × 0.25 × 0.22 mm |
β = 98.19 (5)° |
Bruker Nonius KappaCCD area-detector diffractometer | 3227 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2384 reflections with I > 2σ(I) |
Tmin = 0.885, Tmax = 0.936 | Rint = 0.059 |
17622 measured reflections |
R[F2 > 2σ(F2)] = 0.051 | 0 restraints |
wR(F2) = 0.134 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.25 e Å−3 |
3227 reflections | Δρmin = −0.32 e Å−3 |
209 parameters |
x | y | z | Uiso*/Ueq | ||
N1 | 0.2067 (2) | 0.99862 (17) | 0.39947 (17) | 0.0181 (4) | |
C2 | 0.1344 (3) | 0.8952 (2) | 0.2717 (2) | 0.0178 (4) | |
N3 | 0.0811 (2) | 0.75376 (17) | 0.23960 (17) | 0.0177 (4) | |
C4 | 0.0706 (3) | 0.7141 (2) | 0.3481 (2) | 0.0171 (4) | |
C5 | 0.1156 (3) | 0.8157 (2) | 0.48841 (19) | 0.0172 (4) | |
C6 | 0.2032 (3) | 0.9578 (2) | 0.5067 (2) | 0.0178 (4) | |
N21 | 0.1241 (2) | 0.93797 (18) | 0.16430 (17) | 0.0221 (4) | |
H21A | 0.1448 | 1.0307 | 0.1857 | 0.027* | |
H21B | 0.0549 | 0.8723 | 0.0841 | 0.027* | |
N41 | 0.0112 (2) | 0.57444 (17) | 0.32114 (17) | 0.0186 (4) | |
H41 | 0.0086 | 0.5442 | 0.3960 | 0.022* | |
C42 | −0.0436 (3) | 0.4661 (2) | 0.18126 (19) | 0.0182 (4) | |
H42A | −0.1151 | 0.4985 | 0.1199 | 0.022* | |
H42B | −0.1192 | 0.3776 | 0.1834 | 0.022* | |
C43 | 0.1089 (3) | 0.4326 (2) | 0.1192 (2) | 0.0212 (4) | |
H43A | 0.0686 | 0.3906 | 0.0164 | 0.025* | |
H43B | 0.2036 | 0.5225 | 0.1446 | 0.025* | |
C44 | 0.1820 (3) | 0.3315 (2) | 0.1681 (2) | 0.0196 (4) | |
O44 | 0.10635 (19) | 0.20552 (14) | 0.12956 (14) | 0.0223 (3) | |
O45 | 0.34111 (19) | 0.39256 (14) | 0.25435 (14) | 0.0222 (3) | |
C46 | 0.4207 (3) | 0.2999 (2) | 0.3051 (2) | 0.0257 (5) | |
H46A | 0.4186 | 0.2144 | 0.2260 | 0.031* | |
H46B | 0.3549 | 0.2685 | 0.3679 | 0.031* | |
C47 | 0.6066 (3) | 0.3843 (2) | 0.3820 (3) | 0.0312 (5) | |
H47A | 0.6071 | 0.4713 | 0.4567 | 0.047* | |
H47B | 0.6722 | 0.4097 | 0.3174 | 0.047* | |
H47C | 0.6618 | 0.3270 | 0.4223 | 0.047* | |
C51 | 0.0490 (3) | 0.7813 (2) | 0.5944 (2) | 0.0192 (4) | |
H51 | 0.0596 | 0.8579 | 0.6784 | 0.023* | |
O51 | −0.02206 (19) | 0.65980 (14) | 0.58706 (14) | 0.0216 (3) | |
N61 | 0.2857 (2) | 1.05882 (17) | 0.63761 (17) | 0.0199 (4) | |
C62 | 0.3611 (3) | 1.2063 (2) | 0.6514 (2) | 0.0218 (5) | |
H62A | 0.2834 | 1.2294 | 0.5853 | 0.026* | |
H62B | 0.4769 | 1.2169 | 0.6275 | 0.026* | |
C63 | 0.3831 (3) | 1.3095 (2) | 0.7991 (2) | 0.0248 (5) | |
H63A | 0.2658 | 1.3073 | 0.8187 | 0.030* | |
H63B | 0.4419 | 1.4074 | 0.8071 | 0.030* | |
C64 | 0.4915 (3) | 1.2721 (2) | 0.9069 (2) | 0.0257 (5) | |
H64A | 0.6140 | 1.2870 | 0.8961 | 0.031* | |
H64B | 0.4935 | 1.3350 | 1.0019 | 0.031* | |
C65 | 0.4114 (3) | 1.1178 (2) | 0.8867 (2) | 0.0264 (5) | |
H65A | 0.4866 | 1.0916 | 0.9517 | 0.032* | |
H65B | 0.2941 | 1.1056 | 0.9080 | 0.032* | |
C66 | 0.3942 (3) | 1.0207 (2) | 0.7381 (2) | 0.0216 (5) | |
H66A | 0.5125 | 1.0283 | 0.7191 | 0.026* | |
H66B | 0.3396 | 0.9207 | 0.7262 | 0.026* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0212 (9) | 0.0155 (8) | 0.0162 (8) | 0.0040 (7) | 0.0016 (7) | 0.0064 (7) |
C2 | 0.0191 (10) | 0.0160 (9) | 0.0169 (10) | 0.0048 (8) | 0.0016 (8) | 0.0059 (8) |
N3 | 0.0197 (9) | 0.0163 (8) | 0.0169 (8) | 0.0038 (7) | 0.0021 (7) | 0.0077 (7) |
C4 | 0.0170 (10) | 0.0168 (9) | 0.0184 (10) | 0.0061 (8) | 0.0021 (8) | 0.0078 (8) |
C5 | 0.0202 (10) | 0.0155 (9) | 0.0146 (9) | 0.0042 (8) | 0.0001 (8) | 0.0061 (8) |
C6 | 0.0186 (10) | 0.0161 (9) | 0.0186 (10) | 0.0062 (8) | 0.0015 (8) | 0.0066 (8) |
N21 | 0.0298 (10) | 0.0152 (8) | 0.0179 (8) | 0.0024 (7) | −0.0006 (7) | 0.0072 (7) |
N41 | 0.0266 (9) | 0.0144 (8) | 0.0144 (8) | 0.0053 (7) | 0.0021 (7) | 0.0063 (7) |
C42 | 0.0222 (10) | 0.0155 (9) | 0.0150 (10) | 0.0040 (8) | 0.0009 (8) | 0.0056 (8) |
C43 | 0.0290 (11) | 0.0174 (10) | 0.0165 (10) | 0.0048 (8) | 0.0034 (8) | 0.0075 (8) |
C44 | 0.0248 (11) | 0.0186 (10) | 0.0140 (9) | 0.0051 (8) | 0.0054 (8) | 0.0047 (8) |
O44 | 0.0281 (8) | 0.0156 (7) | 0.0195 (7) | 0.0038 (6) | 0.0004 (6) | 0.0057 (6) |
O45 | 0.0235 (8) | 0.0193 (7) | 0.0223 (7) | 0.0050 (6) | 0.0019 (6) | 0.0082 (6) |
C46 | 0.0277 (12) | 0.0228 (11) | 0.0271 (11) | 0.0087 (9) | 0.0009 (9) | 0.0112 (9) |
C47 | 0.0244 (12) | 0.0315 (12) | 0.0334 (13) | 0.0098 (10) | 0.0018 (10) | 0.0076 (10) |
C51 | 0.0210 (10) | 0.0188 (10) | 0.0166 (10) | 0.0066 (8) | 0.0017 (8) | 0.0059 (8) |
O51 | 0.0265 (8) | 0.0189 (7) | 0.0201 (7) | 0.0041 (6) | 0.0049 (6) | 0.0099 (6) |
N61 | 0.0244 (9) | 0.0140 (8) | 0.0172 (8) | 0.0025 (7) | −0.0005 (7) | 0.0050 (7) |
C62 | 0.0272 (11) | 0.0149 (10) | 0.0187 (10) | 0.0018 (8) | 0.0003 (9) | 0.0055 (8) |
C63 | 0.0299 (12) | 0.0166 (10) | 0.0209 (11) | 0.0027 (9) | 0.0007 (9) | 0.0032 (8) |
C64 | 0.0306 (12) | 0.0205 (10) | 0.0176 (10) | 0.0026 (9) | −0.0014 (9) | 0.0030 (8) |
C65 | 0.0327 (12) | 0.0242 (11) | 0.0183 (10) | 0.0042 (9) | 0.0006 (9) | 0.0078 (9) |
C66 | 0.0239 (11) | 0.0185 (10) | 0.0201 (10) | 0.0055 (8) | −0.0007 (8) | 0.0074 (8) |
N1—C6 | 1.324 (3) | C46—H46A | 0.9900 |
N1—C2 | 1.353 (3) | C46—H46B | 0.9900 |
C2—N21 | 1.336 (3) | C47—H47A | 0.9800 |
C2—N3 | 1.344 (3) | C47—H47B | 0.9800 |
N3—C4 | 1.335 (3) | C47—H47C | 0.9800 |
C4—N41 | 1.339 (3) | C51—O51 | 1.234 (2) |
C4—C5 | 1.434 (3) | C51—H51 | 0.9500 |
C5—C51 | 1.409 (3) | N61—C62 | 1.465 (3) |
C5—C6 | 1.421 (3) | N61—C66 | 1.481 (3) |
C6—N61 | 1.378 (3) | C62—C63 | 1.522 (3) |
N21—H21A | 0.8843 | C62—H62A | 0.9900 |
N21—H21B | 0.8932 | C62—H62B | 0.9900 |
N41—C42 | 1.453 (3) | C63—C64 | 1.530 (3) |
N41—H41 | 0.9356 | C63—H63A | 0.9900 |
C42—C43 | 1.522 (3) | C63—H63B | 0.9900 |
C42—H42A | 0.9900 | C64—C65 | 1.517 (3) |
C42—H42B | 0.9900 | C64—H64A | 0.9900 |
C43—C44 | 1.502 (3) | C64—H64B | 0.9900 |
C43—H43A | 0.9900 | C65—C66 | 1.516 (3) |
C43—H43B | 0.9900 | C65—H65A | 0.9900 |
C44—O44 | 1.212 (2) | C65—H65B | 0.9900 |
C44—O45 | 1.335 (3) | C66—H66A | 0.9900 |
O45—C46 | 1.461 (2) | C66—H66B | 0.9900 |
C46—C47 | 1.500 (3) | ||
C6—N1—C2 | 116.23 (17) | C46—C47—H47A | 109.5 |
N21—C2—N3 | 116.10 (18) | C46—C47—H47B | 109.5 |
N21—C2—N1 | 116.28 (18) | H47A—C47—H47B | 109.5 |
N3—C2—N1 | 127.51 (18) | C46—C47—H47C | 109.5 |
C4—N3—C2 | 115.03 (17) | H47A—C47—H47C | 109.5 |
N3—C4—N41 | 117.39 (18) | H47B—C47—H47C | 109.5 |
N3—C4—C5 | 122.16 (18) | O51—C51—C5 | 125.40 (19) |
N41—C4—C5 | 120.43 (18) | O51—C51—H51 | 117.3 |
C51—C5—C6 | 122.24 (18) | C5—C51—H51 | 117.3 |
C51—C5—C4 | 121.52 (18) | C6—N61—C62 | 118.51 (17) |
C6—C5—C4 | 115.25 (18) | C6—N61—C66 | 119.36 (16) |
N1—C6—N61 | 117.61 (18) | C62—N61—C66 | 111.47 (16) |
N1—C6—C5 | 121.51 (18) | N61—C62—C63 | 111.02 (17) |
N61—C6—C5 | 120.87 (18) | N61—C62—H62A | 109.4 |
C2—N21—H21A | 115.9 | C63—C62—H62A | 109.4 |
C2—N21—H21B | 114.8 | N61—C62—H62B | 109.4 |
H21A—N21—H21B | 123.6 | C63—C62—H62B | 109.4 |
C4—N41—C42 | 123.41 (17) | H62A—C62—H62B | 108.0 |
C4—N41—H41 | 118.7 | C62—C63—C64 | 111.73 (18) |
C42—N41—H41 | 117.9 | C62—C63—H63A | 109.3 |
N41—C42—C43 | 113.62 (17) | C64—C63—H63A | 109.3 |
N41—C42—H42A | 108.8 | C62—C63—H63B | 109.3 |
C43—C42—H42A | 108.8 | C64—C63—H63B | 109.3 |
N41—C42—H42B | 108.8 | H63A—C63—H63B | 107.9 |
C43—C42—H42B | 108.8 | C65—C64—C63 | 109.64 (18) |
H42A—C42—H42B | 107.7 | C65—C64—H64A | 109.7 |
C44—C43—C42 | 112.97 (17) | C63—C64—H64A | 109.7 |
C44—C43—H43A | 109.0 | C65—C64—H64B | 109.7 |
C42—C43—H43A | 109.0 | C63—C64—H64B | 109.7 |
C44—C43—H43B | 109.0 | H64A—C64—H64B | 108.2 |
C42—C43—H43B | 109.0 | C66—C65—C64 | 110.45 (18) |
H43A—C43—H43B | 107.8 | C66—C65—H65A | 109.6 |
O44—C44—O45 | 122.99 (19) | C64—C65—H65A | 109.6 |
O44—C44—C43 | 123.36 (19) | C66—C65—H65B | 109.6 |
O45—C44—C43 | 113.62 (17) | C64—C65—H65B | 109.6 |
C44—O45—C46 | 116.48 (16) | H65A—C65—H65B | 108.1 |
O45—C46—C47 | 107.34 (18) | N61—C66—C65 | 111.06 (17) |
O45—C46—H46A | 110.2 | N61—C66—H66A | 109.4 |
C47—C46—H46A | 110.2 | C65—C66—H66A | 109.4 |
O45—C46—H46B | 110.2 | N61—C66—H66B | 109.4 |
C47—C46—H46B | 110.2 | C65—C66—H66B | 109.4 |
H46A—C46—H46B | 108.5 | H66A—C66—H66B | 108.0 |
C6—N1—C2—N21 | 174.38 (18) | C42—C43—C44—O44 | 72.8 (3) |
C6—N1—C2—N3 | −9.8 (3) | C42—C43—C44—O45 | −109.4 (2) |
N21—C2—N3—C4 | −171.57 (18) | O44—C44—O45—C46 | −1.7 (3) |
N1—C2—N3—C4 | 12.6 (3) | C43—C44—O45—C46 | −179.55 (17) |
C2—N3—C4—N41 | 177.37 (17) | C44—O45—C46—C47 | 171.90 (18) |
C2—N3—C4—C5 | −0.8 (3) | C6—C5—C51—O51 | −177.03 (19) |
N3—C4—C5—C51 | 157.28 (19) | C4—C5—C51—O51 | 14.9 (3) |
N41—C4—C5—C51 | −20.9 (3) | N1—C6—N61—C62 | 4.2 (3) |
N3—C4—C5—C6 | −11.6 (3) | C5—C6—N61—C62 | −174.97 (18) |
N41—C4—C5—C6 | 170.27 (18) | N1—C6—N61—C66 | −137.42 (19) |
C2—N1—C6—N61 | 175.91 (17) | C5—C6—N61—C66 | 43.4 (3) |
C2—N1—C6—C5 | −5.0 (3) | C6—N61—C62—C63 | 158.54 (18) |
C51—C5—C6—N1 | −154.2 (2) | C66—N61—C62—C63 | −57.0 (2) |
C4—C5—C6—N1 | 14.6 (3) | N61—C62—C63—C64 | 55.0 (2) |
C51—C5—C6—N61 | 24.9 (3) | C62—C63—C64—C65 | −53.9 (3) |
C4—C5—C6—N61 | −166.31 (18) | C63—C64—C65—C66 | 55.0 (3) |
N3—C4—N41—C42 | −0.9 (3) | C6—N61—C66—C65 | −156.94 (19) |
C5—C4—N41—C42 | 177.40 (18) | C62—N61—C66—C65 | 59.0 (2) |
C4—N41—C42—C43 | 78.2 (2) | C64—C65—C66—N61 | −58.0 (2) |
N41—C42—C43—C44 | 81.2 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N21—H21A···O44i | 0.88 | 2.15 | 2.951 (3) | 150 |
N21—H21B···O44ii | 0.89 | 2.20 | 3.036 (3) | 156 |
N41—H41···O51 | 0.94 | 2.05 | 2.700 (3) | 125 |
N41—H41···O51iii | 0.94 | 2.21 | 2.909 (3) | 131 |
C43—H43A···N3ii | 0.99 | 2.55 | 3.524 (4) | 169 |
Symmetry codes: (i) x, y+1, z; (ii) −x, −y+1, −z; (iii) −x, −y+1, −z+1. |
Experimental details
(I) | (II) | (III) | (IV) | |
Crystal data | ||||
Chemical formula | C16H19N5O3 | C14H16N6O2 | C17H21N5O3 | C16H19N5O3 |
Mr | 329.36 | 300.33 | 343.39 | 329.36 |
Crystal system, space group | Triclinic, P1 | Monoclinic, C2/c | Monoclinic, C2/c | Monoclinic, P21/c |
Temperature (K) | 293 | 120 | 120 | 120 |
a, b, c (Å) | 7.3990 (5), 9.609 (3), 12.449 (3) | 20.045 (4), 8.6868 (7), 17.990 (3) | 16.707 (6), 10.218 (2), 20.733 (5) | 15.636 (4), 6.5674 (18), 17.336 (5) |
α, β, γ (°) | 73.30 (2), 82.680 (14), 72.693 (13) | 90, 114.064 (11), 90 | 90, 105.929 (19), 90 | 90, 113.440 (18), 90 |
V (Å3) | 808.5 (3) | 2860.3 (8) | 3403.5 (16) | 1633.3 (8) |
Z | 2 | 8 | 8 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.10 | 0.10 | 0.10 | 0.10 |
Crystal size (mm) | 0.41 × 0.25 × 0.22 | 0.32 × 0.20 × 0.11 | 0.29 × 0.22 × 0.10 | 0.29 × 0.27 × 0.15 |
Data collection | ||||
Diffractometer | Bruker Nonius KappaCCD area-detector diffractometer | Bruker Nonius KappaCCD area-detector diffractometer | Bruker Nonius KappaCCD area-detector diffractometer | Bruker Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.885, 0.936 | 0.969, 0.989 | 0.973, 0.991 | 0.973, 0.986 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 18365, 3006, 2054 | 32858, 2657, 1993 | 21914, 3160, 2239 | 21188, 3013, 2209 |
Rint | 0.042 | 0.068 | 0.063 | 0.072 |
(sin θ/λ)max (Å−1) | 0.606 | 0.606 | 0.606 | 0.606 |
Refinement | ||||
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.120, 1.02 | 0.049, 0.119, 1.12 | 0.044, 0.095, 1.09 | 0.059, 0.165, 1.09 |
No. of reflections | 3006 | 2657 | 3160 | 3013 |
No. of parameters | 220 | 200 | 228 | 219 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.19, −0.17 | 0.34, −0.26 | 0.17, −0.23 | 0.35, −0.36 |
(V) | (VI) | |
Crystal data | ||
Chemical formula | C18H23N5O3 | C15H23N5O3 |
Mr | 357.41 | 321.38 |
Crystal system, space group | Monoclinic, C2/c | Triclinic, P1 |
Temperature (K) | 120 | 120 |
a, b, c (Å) | 24.8226 (5), 7.1379 (14), 20.601 (2) | 8.040 (4), 10.391 (3), 10.458 (8) |
α, β, γ (°) | 90, 106.213 (8), 90 | 109.16 (3), 98.19 (5), 103.10 (3) |
V (Å3) | 3505.0 (8) | 781.2 (8) |
Z | 8 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.10 | 0.10 |
Crystal size (mm) | 0.26 × 0.21 × 0.14 | 0.41 × 0.25 × 0.22 |
Data collection | ||
Diffractometer | Bruker Nonius KappaCCD area-detector diffractometer | Bruker Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.976, 0.987 | 0.885, 0.936 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 22384, 3269, 2276 | 17622, 3227, 2384 |
Rint | 0.073 | 0.059 |
(sin θ/λ)max (Å−1) | 0.606 | 0.628 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.104, 1.06 | 0.051, 0.134, 1.05 |
No. of reflections | 3269 | 3227 |
No. of parameters | 237 | 209 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.21, −0.25 | 0.25, −0.32 |
Computer programs: COLLECT (Nonius, 1999), DIRAX/LSQ (Duisenberg et al., 2000), EVALCCD (Duisenberg et al., 2003), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
(i) | Bond lengths | |||||
Parameter | (I) | (II) | (III) | (IV) | (V) | (VI) |
N1—C2 | 1.353 (2) | 1.350 (3) | 1.361 (2) | 1.353 (3) | 1.346 (2) | 1.353 (3) |
C2—N3 | 1.340 (2) | 1.352 (3) | 1.341 (2) | 1.342 (3) | 1.346 (2) | 1.344 (2) |
N3—C4 | 1.335 (2) | 1.336 (3) | 1.346 (2) | 1.339 (3) | 1.346 (2) | 1.335 (3) |
C4—C5 | 1.430 (2) | 1.436 (3) | 1.433 (2) | 1.436 (3) | 1.441 (3) | 1.434 (3) |
C5—C6 | 1.418 (2) | 1.438 (3) | 1.428 (2) | 1.429 (3) | 1.430 (3) | 1.421 (3) |
C6—N1 | 1.335 (2) | 1.336 (3) | 1.339 (2) | 1.331 (3) | 1.351 (2) | 1.324 (3) |
C2—N21 | 1.342 (2) | 1.337 (3) | 1.340 (2) | 1.340 (3) | 1.345 (2) | 1.336 (3) |
C4—N41 | 1.336 (2) | 1.352 (3) | 1.343 (2) | 1.334 (3) | 1.343 (2) | 1.339 (3) |
C5—C51 | 1.426 (3) | 1.426 (3) | 1.432 (3) | 1.420 (3) | 1.426 (3) | 1.409 (3) |
C51—O51 | 1.232 (2) | 1.247 (3) | 1.239 (2) | 1.239 (3) | 1.241 (2) | 1.234 (2) |
C6—N61 | 1.380 (2) | 1.371 (3) | 1.381 (2) | 1.381 (3) | 1.359 (2) | 1.378 (3) |
(ii) | Torsion angles | |||||
N3—C4—N41—C42 | -4.8 (2) | 7.0 (3) | 3.2 (3) | -2.4 (3) | 11.0 (3) | -0.9 (3) |
C4—N41—C42—C43 | -196.15 (17) | -88.6 (3) | 114.35 (19) | -178.5 (2) | -138.69 (18) | 78.2 (2) |
N41—C42—C43—C44 | 74.4 (2) | -63.1 (2) | 81.2 (2) | |||
N41—C42—C43—N44 | 1.3 (3) | |||||
N41—C42—C43—O44 | -172.71 (17) | 170.47 (19) | ||||
C42—C43—C44—O45 | -68.3 (2) | -174.63 (16) | -109.4 (2) | |||
C43—C44—O45—C46 | 179.43 (16) | -177.40 (16) | -179.55 (17) | |||
C44—O45—C46—C47 | -174.16 (16) | -147.25 (18) | 171.90 (18) | |||
C42—C43—O44—C45 | 178.29 (17) | 177.2 (2) | ||||
C43—O44—C45—C46 | 170.04 (19) | |||||
C4—C5—C51—O51 | 13.1 (3) | 8.3 (4) | 13.2 (3) | 15.3 (4) | 11.5 (3) | 14.9 (3) |
C5—C6—N61—C61 | 42.6 (3) | 35.4 (3) | 39.4 (2) | |||
C5—C6—N61—C62 | -174.97 (18) | |||||
C5—C6—N61—C66 | 43.4 (3) | |||||
C5—C6—N61—C67 | -161.27 (18) | -175.8 (2) | -171.57 (16) | 46.0 (3) | -170.05 (17) | |
C5—C6—C61—C68 | -169.3 (2) | 22.5 (3) | ||||
(iii) | Substituent displacement from mean pyrimidine plane | |||||
Compound | N21 | N41 | C51 | O51 | N61 | |
(I) | 0.077 (2) | -0.015 (2) | 0.319 (2) | 0.334 (2) | -0.071 (2) | |
(II) | 0.132 (2) | -0.035 (2) | 0.321 (2) | 0.391 (2) | -0.101 (2) | |
(III) | 0.106 (2) | -0.162 (2) | 0.353 (2) | 0.331 (2) | -0.084 (2) | |
(IV) | 0.161 (2) | -0.037 (2) | 0.444 (3) | 0.487 (2) | -0.190 (2) | |
(V) | 0.300 (2) | -0.172 (2) | 0.493 (2) | 0.548 (2) | -0.256 (2) | |
(VI) | 0.245 (2) | -0.104 (2) | 0.564 (2) | 0.670 (2) | -0.251 (2) | |
(iv) | Ring-puckering parameters | |||||
Compound | Q | θ | ϕ | |||
(IV) | 0.100 (3) | 97.0 (17) | 76.9 (14) | |||
(V) | 0.156 (3) | 98.5 (7) | 59.8 (7) | |||
(VI) | 0.149 (2) | 96.9 (8) | 71.8 (8) | |||
Idealized boat | 90.0 | 60n |
Compound | D—H···A | D—H | H···A | D···A | D—H···A |
(I) | N21—H21A···N1i | 0.92 | 2.22 | 3.125 (2) | 167 |
N41—H41···O51 | 0.94 | 1.90 | 2.675 (2) | 138 | |
(II) | N21—H21A···O43ii | 0.94 | 2.02 | 2.933 (2) | 166 |
N41—H41···O51 | 0.90 | 1.98 | 2.689 (2) | 135 | |
N44—H44A···O51iii | 0.95 | 2.14 | 2.949 (2) | 143 | |
N44—H44B···O43iv | 0.98 | 2.05 | 3.006 (3) | 164 | |
C62—H62···O43v | 0.95 | 2.45 | 3.280 (3) | 146 | |
(III) | N21—H21A···N1iii | 0.90 | 2.14 | 3.027 (2) | 169 |
N21—H21B···O44v | 0.97 | 2.14 | 3.054 (2) | 158 | |
N41—H41···O51 | 0.96 | 1.95 | 2.683 (2) | 131 | |
(IV) | N21—H21A···O51vi | 1.00 | 1.89 | 2.860 (3) | 163 |
N21—H21B···O43vii | 0.89 | 2.38 | 3.085 (3) | 136 | |
N41—H41···O51 | 0.96 | 1.92 | 2.682 (3) | 135 | |
(V) | N21—H21A···N3viii | 0.96 | 2.07 | 3.008 (2) | 168 |
N21—H21B···N1ix | 0.95 | 2.30 | 3.199 (2) | 158 | |
N41—H41···O44 | 1.01 | 2.27 | 2.891 (2) | 119 | |
N41—H41···O51 | 1.01 | 1.92 | 2.666 (2) | 128 | |
C46—H46A···O51x | 0.99 | 2.54 | 3.528 (3) | 172 | |
(VI) | N21—H21A···O44ii | 0.88 | 2.15 | 2.951 (3) | 150 |
N21—H21B···O44xi | 0.89 | 2.20 | 3.036 (3) | 156 | |
N41—H41···O51 | 0.94 | 2.05 | 2.700 (3) | 125 | |
N41—H41···O51i | 0.94 | 2.21 | 2.909 (3) | 131 | |
C43—H43A···N3xi | 0.99 | 2.55 | 3.524 (4) | 169 |
Symmetry codes: (i) -x, -y + 1, -z + 1; (ii) x, y + 1, z; (iii) -x + 1, y, -z + 1/2; (iv) -x + 3/2, -y + 1/2, -z + 1; (v) -x + 1, -y + 1, -z + 1; (vi) x, -y + 3/2, z + 1/2; (vii) x, -y + 1/2, z + 1/2; (viii) -x + 3/2, y + 1/2, -z + 3/2; (ix) -x + 3/2, y - 1/2, -z + 3/2; (x) -x + 1, -y, -z + 1; (xi) -x, -y + 1, -z. |
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When heterocyclic species are covalently linked to biomolecules such as amino acids and peptides, carbohydrates, DNA or steroids, this type of combination can enhance the bioactivity of both components. For example, pyrimidine derivatives have been used in this way, particularly when linked to essential amino acids, in searches for new potentially bioactive agents, including anti-inflammatory agents (Bruno et al., 1999), antimicrobials (Ghorab et al., 2004), antidiabetic agents (Cantin et al., 2006) and agents for the treatment of urinary tract disease (Murata et al., 2004). Such combinations have also been investigated as potential intermediates for the synthesis of poly-fused pyrimidines of possible biological value (Min et al., 2008). Here, we report the molecular and supramolecular structures of six compounds of this type, (I)–(VI) (Fig. 1 and scheme), all having a simple amino substituent at position 6 of the pyrimidine ring, while position 4 of said ring carries, in each case, an amino substituent derived from a simple amino acid derivative. The present work is a development of an earlier study (Cobo et al., 2008) which reported the structures of 12 N6-substituted 2-amino-4-chloro-5-formylpyrimidines.
Minor variations in one or other of the substituents at positions 4 and 6 in these compounds can lead to significant differences, both in the molecular conformations and in the hydrogen-bonded supramolecular assemblies. None of the molecules of (I)–(VI) exhibits any internal symmetry and they are all conformationally chiral, although all of them crystallize in centrosymmetric space groups. The reference molecules were selected so that all have the same sign for the torsion angle C4—C5—C51—O51 (Table 1). In each structure, formyl atom O51 is involved in an intramolecular N—H···O hydrogen bond (Table 2), forming an S(6) motif (Bernstein et al., 1995).
Compounds (I)–(III) (Fig. 1) all have an N-methyl-N-phenyl substituent at position 6 of the pyrimidine ring with slightly different substituents at position 4 (Fig. 1), viz. a glycinate ester and a glycinamide substituent in (I) and (II), respectively, and a 3-aminopropionate ester substituent in (III), and in each of (I)–(III) the pyrimidine ring is effectively planar. Compounds (IV) and (V) both have an N-benzyl-N-methyl substituent at position 6, with different amino acid ester substituents at position 4; the orientation of the 6-substituent is different, as indicated by the torsion angles C5—C6—N61—C67 and C5—C6—N61—C68 (Table 1 and Fig. 1). In addition, the pyrimidine ring in each of (IV)–(VI) is slightly distorted from planarity into a boat conformation, as indicated by the ring-puckering parameters (Cremer & Pople, 1975) for the atom sequence N1—C2—N3—C4—C5—C6 (Table 1). Thus, the ring-puckering parameters for compounds (IV)-(VI) are all very similar, and in each case the boat conformation has atoms C2 and C5 as the prow and stern of the boat, respectively, displaced to one side of the mean plane through the ring atoms, with atoms N1, N3, C4 and C6 all displaced to the opposite side of this plane, indicated schematically as (A) in the scheme. Where three substituents are present at the 4-, 5- and 6-positions in pyrimidines, the ring is often found to be quite markedly nonplanar, leading to boat (Quesada et al., 2004; Low et al., 2007; Trilleras et al., 2007; Cobo et al., 2008), twist-boat (Melguizo et al., 2003; Quesada et al., 2003; Cobo et al., 2008) or screw-boat (Low et al., 2007) conformations, as well as a variety of intermediate forms (Cobo et al., 2008). The conformations of (IV)–(VI) reported here are thus fully consistent with some of the examples reported earlier. However, even when the pyrimidine ring is effectively planar, as in (I)–(III), the ring substituent atoms are not always coplanar with the ring, with atom C51 always markedly displaced from the mean plane (Table 1).
While the glycinate ester side chains at position 4 in (I) and (IV) both adopt all-transoid extended-chain conformations, as demonstrated by the relevant torsion angles, which all lie within 10° of 180°, the corresponding aminopropionate substituents in (III), (V) and (VI) show a considerable variation in their conformations (Table 1 and Fig. 1). In particular, the values of the three torsion angles C4—N41—C42—C43, N41—C42—C43—C44 and C42—C43—C44—O45 show wide variations among these compounds. While it is tempting to associate these variations with the different patterns of hydrogen bonds involving this substituent in (III), (V) and (VI), such an approach could not readily be reconciled with the similarity in the conformations of the 4-substituent in (I) and (IV), where the hydrogen bonds involving the 4-substituent are also different, with no involvement at all in (I), but participation of atom O43 in (IV) (Table 2).
There are some interesting patterns in the bond distances in (I)–(VI) (Table 1) which suggest that the polarized form (C) (see scheme) is a significant contributor to the overall electronic structure, in addition to the classical aromatic form (B). Within the formyl fragments, the C—O distance is, in every case, long for its type [mean 1.192 Å and upper quartile 1.197 Å; Allen et al. (1987, 2006)], while the C5—C51 bond between the formyl group and the pyrimidine ring is short for its type (mean 1.470 Å and lower quartile 1.463 Å). The N21—C2, C2—N3, N3—C4 and C4—N41 bond lengths (Fig. 1) are all very similar in each compound, despite the fact that the C2—N3 and N3—C4 bonds are formally of heteroaromatic type, while the exocyclic N21—C2 and C4—N41 bonds are formally single bonds. It may also be noted here that the N1—C2 bond is usually the longest of the ring N—C bonds, while the C6—N61 bond is consistently longer than the C4—N41 bond, and this may be associated with the fact that, in general, the substituents at N61 are usually displaced well away from the mean pyrimidine plane by a rotation about the C6—N61 bond. Moreover, the geometry at N61 is always slightly pyramidal, with a mean sum of the bond angles of 353.6 (2) Å, while atom N41 is always effectively planar.
The supramolecular assembly is dominated by N—H···N and N—H···O hydrogen bonds, with C—H···O hydrogen bonds also present in the structures of (II) and (V) and a C—H···N hydrogen bond present in the structure of (VI). C—H···O interactions involving C—H bonds in methyl groups, and those having D—H···A angles significantly less than 140°, have been discounted (cf. Wood et al., 2009). However, N—H···π(arene) and C—H···π(arene) hydrogen bonds are absent, while the polarized pyrimidine rings are far from being aromatic. Despite the rather similar constitutions of (I)–(VI), the patterns of their hydrogen-bonded supramolecular assemblies vary widely, from simple dimeric units in (I), via chains and sheets, to a three-dimensional framework structure in (II). It is convenient to consider the hydrogen-bonded structures in order of increasing complexity.
In the structure of (I), there is only a single intermolecular hydrogen bond, of N—H···N type, and pairs of such bonds link inversion-related pairs of molecules into dimers characterized by a centrosymmetric R22(8) (Bernstein et al., 1995) motif (Fig. 2).
The molecules of (III) are linked into a chain of edge-fused rings by a combination of N—H···N and N—H···O hydrogen bonds. A pair of molecules related by the twofold rotation axis along (1/2, y, 1/4) are linked by symmetry-related N—H···N hydrogen bonds, using the same donor and acceptor as in (I) and forming an R22(8) ring, while a pair of molecules related by inversion are linked by symmetry-related N—H···O hydrogen bonds to form an R22(20) motif centred at (1/2, 1/2, 1/2). The combination of these two motifs, propagated by rotation and inversion, generates a chain of edge-fused rings running parallel to the [001] direction, with R22(20) rings centred at (1/2, 1/2, n/2), where n represents an integer, alternating with R22(8) rings lying across the twofold axes along (1/2, y, 1/4 + n/2), where n again represents an integer (Fig. 3).
Compounds (IV), (V) and (VI) all form sheets, of increasing complexity and built using two, three and four hydrogen bonds, respectively (Table 2). There is no obvious correlation between the complexity of the supramolecular assemblies and the complexity, specifically the number of symmetry operators, of the space groups concerned, P21/c, C2/c and P1, respectively. In (IV), amino atom N21 in the molecule at (x, y, z) acts as hydrogen-bond donor, via atom H21A, to formyl atom O51 in the molecule at (x, -y + 3/2, z + 1/2), so forming a C(9) chain running parallel to the [001] direction and built from molecules related by the 21 screw axis along (0, 3/4, z). This same atom, N21, also acts as hydrogen-bond donor, this time via atom H21B, to ester atom O43 in the molecule at (x, -y + 1/2, z + 1/2), forming a C(9) chain, also parallel to [001] and containing molecules related by the 21 screw axis along (0, 1/4, z). The combination of these two chain motifs generates a sheet lying parallel to (100), in the form of a (4,4) net containing a single type of R44(28) ring (Fig. 4).
While the sheet in (IV) is built from two N—H···O hydrogen bonds, intermolecular hydrogen bonds of this type are absent from the structure of (V). Instead, the supramolecular assembly depends upon two hydrogen bonds of N—H···N type and one of C—H···O type (Table 2), and the formation of the sheet is most readily analysed in terms of two one-dimensional substructures (Ferguson et al., 1998a,b; Gregson et al., 2000). In the first substructure, the two N—H···N hydrogen bonds, acting in isolation, each form a C(4) chain running parallel to the [010] direction, and in combination they generate a chain of edge-fused rings containing molecules related by the 21 screw axis along (3/4, y, 3/4) (Fig. 5). The C—H···O hydrogen bond links inversion-related pairs of molecules to form a centrosymmetric R22(22) motif. The molecule at (x, y, z) lies in the chain of edge-fused rings along (3/4, y, 3/4), while that at (-x + 1, -y + 1, -z + 1) forms part of a similar chain along (1/4, y, 1/4). The combination of all three hydrogen bonds generates a chain of rings running parallel to the [111] direction in which R22(8) and R22(22) rings alternate (Fig. 6). The combination of the [101] and [111] substructural chains then generates a complex sheet lying parallel to (101).
Hydrogen bonds of N—H···N type are absent from the structure of (VI), where the sheet structure is generated by N—H···O hydrogen bonds (Table 2). As for (V), it is convenient to describe the formation of the sheet structure in (VI) in terms of two one-dimensional substructures. In one substructure, amino atom N21 acts as hydrogen-bond donor, via atoms H21A and H21B, to ester atoms O44 in the molecules at (x, y + 1, z) and (-x, -y + 1, -z), respectively, and these interactions generate a chain of edge-fused centrosymmetric rings running parallel to the [010] direction, within which R42(8) rings centred at (0, n, 0) alternate with R22(20) rings centred at (0, 1/2 + n, 0), where n represents an integer in both cases (Fig. 7). There is an intermolecular C—H···N contact in the structure, involving the α-CH2 group of the carboxylate unit as donor. If this is regarded as structurally significant, its role is modestly to reinforce the chain along [010]. Amino atom N41 participates in a planar three-centre N—H···(O)2 hydrogen bond, where the acceptors are two formyl atoms O51 at (x, y, z) and (-x, -y + 1, -z + 1) (Table 2), forming, respectively, S(6) and R22(4) motifs. The combination of these motifs with the R22(20) motif produces a second substructure in the form of a chain of rings running parallel to the [001] direction, with R22(20) rings centred at (0, 1/2, n) alternating with R22(4) rings centred at (0, 1/2, 1/2+n), where n represents an integer (Fig. 8). The combination of the substructures parallel to [010] and [001] generates a sheet lying parallel to (100) (Fig. 9).
Compound (II) is the only example amongst those discussed here in which the hydrogen-bonded supramolecular assembly is three-dimensional. The formation of this three-dimensional framework is most conveniently analysed in terms of the linking of sheets generated solely by N—H···O hydrogen bonds, and the formation of the sheet structure in turn is most readily analysed in terms of two substructures in the form of chains. In the simpler of the two chain motifs comprising the sheet, molecules related by translation are linked into a C(9) chain running parallel to the [010] direction (Fig. 10). It is interesting to note that only one of the N—H bonds in the amide unit containing atom N21 participates in the hydrogen bonding.
The second chain motif in (II) involves the two N—H bonds of the amide unit containing atom N44. This atom, in the reference molecule at (x, y, z), acts as hydrogen-bond donor, via atom H44A, to formyl atom O51 at (-x + 1, y, -z + 1/2), so forming an R22(18) ring containing two molecules related by the twofold rotation axis along (1/2, y, 1/4). Atom N44 at (x, y, z) also acts as donor, this time via atom H44B, to amide atom O43 at (-x + 3/2, -y + 1/2, -z + 1), so forming an R22(8) ring containing two molecules related by inversion across (3/4, 1/4, 1/2). The combination of these two motifs generates a chain of edge-fused rings running parallel to the [101] direction, with R22(8) rings centred at (1/4 + n/2, 1/4, n/2) alternating with R22(8) rings lying across the twofold rotation axes along (n/2, y, -1/4 + n/2), where n represents an integer in each case (Fig. 11).
The combination of the simple chain along [010] and the chain of rings along [101] generates a sheet lying parallel to (101). Two sheets of this type, related to one another by inversion, pass through each unit cell, and adjacent sheets are linked by the third substructural motif, so generating a three-dimensional framework structure. Aryl atom C62 in the molecule at (x, y, z) acts as hydrogen-bond donor to amide atom O43 at (-x + 1, -y + 1, -z + 1), so forming a centrosymmetric R22(22) ring (Fig. 12) in which the two component molecules lie in different (101) sheets. Propagation of this interaction by the space-group symmetry operators serves to link all of the sheets into a single continuous structure.
In summary, we have shown that the hydrogen-bonded assembly of six very closely related pyrimidine derivatives varies widely, emcompassing a simple dimeric unit, chains, sheets and a three-dimensional framework structure.