Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109028017/fa3197sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109028017/fa3197Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109028017/fa3197IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109028017/fa3197IIIsup4.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109028017/fa3197IVsup5.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109028017/fa3197Vsup6.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109028017/fa3197VIsup7.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109028017/fa3197VIIsup8.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109028017/fa3197VIIIsup9.hkl |
CCDC references: 746096; 746097; 746098; 746099; 746100; 746101; 746102; 746103
For related literature, see: Acosta et al. (2009); Bernstein et al. (1995); Castillo et al. (2009); Cremer & Pople (1975); Elguero (1984, 1996); Flack (1983).
A mixture of the corresponding 5-arylmethylamino-3-tert-butyl-1-phenyl-1H-pyrazole (0.29 mmol), ethanol (0.5 cm3), acetic acid (0.5 cm3) and formaldehyde (0.9 mmol, as an aqueous solution) was heated at 328 K for 10–16 h. After each reaction was complete the solvent was reduced to one-third of the initial volume and the resulting solid was collected by filtration and washed with cold ethanol. The products thus obtained were crystallized from ethanol except for (I) which was crystallized from hexane, to give colourless crystals suitable for single-crystal X-ray diffraction. 7-Benzyl-3-tert-butyl-1,4,6,7-tetrahydro-1-phenylpyrazolo[3,4-d][1,3]oxazine, (I); yield 81%, m,p, 405–406 K; MS (70 eV) m/z (%) = 347 (100) [M+], 316 (11), 302 (12), 256 (29), 228 (9), 91 (16), 77 (9) [Ph]; analysis found C 75.8, H 7.5, N 12.3%, C22H25N3O requires C 76.0, H 7.3, N 12.1%. 3-Tert-butyl-1,4,6,7-tetrahydro-7-(4-methylbenzyl)-1 -phenylpyrazolo[3,4-d][1,3]oxazine, (II); yield 86%, m.p. 403–404 K; MS (70 eV) m/z (%) = 361 (51) [M+], 256 (16), 105 (100) [C8H9]; analysis found C 76.2, H 7.5, N 11.5%, C23H27N3O requires C 76.4, H 7.5, N 11.6%. 3-Tert-butyl-1,4,6,7-tetrahydro-7-(4-methoxybenzyl)-1- phenylpyrazolo[3,4-d][1,3]oxazine, (III); yield 83%, m.p. 436–437 K; MS (70 eV) m/z (%) = 377 (10) [M+], 121 (100) [C8H9O]; analysis found C 72.9, H 7.1, N 10.9%, C23H27N3O2 requires C 73.2, H 7.2, N 11.1%. 3-Tert-butyl-7-[4-(Trifluoromethyl)benzyl]-1,4,6,7-tetrahydro- 1-phenylpyrazolo[3,4-d][1,3]oxazine, (IV), yield 87%, m.p. 425–426 K; MS (70 eV) m/z (%) = 415 (100) [M+], 370 (24), 170 (31), 159 (24) [C8H6F3]; analysis found C 66.6, H 5.9, N 9.9%, C23H24F3N3O requires C 66.5, H 5.8, N 10.1%. 3-Tert-butyl-1,4,6,7-tetrahydro-7-(4-nitrobenzyl)-1- phenylpyrazolo[3,4-d][1,3]oxazine, (V); yield 79%, m.p. 408–409 K; MS (70 eV) m/z (%) = 392 (100) [M+], 256 (41), 228 (24), 170 (25); analysis found C 67.1, H 6.3, N 14.1%, C22H24N4O3 requires C 67.3, H 6.2, N 14.3%. 3-Tert-butyl-1,4,6,7-tetrahydro-7-(2,3-Dimethoxybenzyl)-1- phenylpyrazolo[3,4-d][1,3]oxazine, (VI); yield 83%, m.p. 385–386 K; MS (70 eV) m/z (%) = 407 (34) [M+], 151 (100) [C9H11O2], 136 (81), 91 (21), 77 (10) [Ph]; analysis found C 70.5, H 7.3, N 10.2%, C24H29N3O3 requires C 70.7, H 7.2, N 10.3%. 7-[(Benzo[d][1,3]dioxol-5-yl)methyl]-3-tert-butyl-1,4,6,7- tetrahydro-1-phenylpyrazolo[3,4-d][1,3]oxazine, (VII); yield 88%, m.p. 436–437 K; MS: (70 eV) m/z (%) = 391 (11) [M+], 135 (100) [C8H7O2]; analysis found C 70.8, H 6.4, N 10.9%, C23H25N3O3 requires C 70.6, H 6.4, N 10.7%. 7-(3,4,5-Trimethoxybenzyl)-3-tert-butyl-1,4,6,7-tetrahydro-1- phenylpyrazolo[3,4-d][1,3]oxazine, (VIII); yield 79%, m.p. 439–440 K; MS (70 eV) m/z (%) = 437 (5) [M+], 181 (100) [C10H13O3]; analysis found C 68.5, H 7.1, N 9.3%, C25H31N3O4 requires C 68.6, H 7.1, N 9.6%.
All H atoms were located in difference maps and then treated as riding atoms in geometrically idealized positions with C—H distances 0.95 Å (aromatic), 0.98 Å (CH3) or 0.99 Å (CH2), and with Uiso(H) = kUeq(C), where k = 1.5 for methyl groups and 1.2 for all other H atoms. The methyl groups were permitted to rotate about the adjacent C—X (X = C or O) bonds but not to tilt. In the absence of significant resonant scattering, the Flack x parameters (Flack 1983) for compounds (I)–(III) and (VI) were indeterminate; accordingly the Friedel-equivalent reflections were merged, and for these compounds it is not possible to establish the absolute configurations of the molecules in the crystals which were selected for data collection. For all compounds, the reference molecules were selected to have the same absolute configuration (see Figs. 1 and 2).
For all compounds, data collection: COLLECT (Hooft, 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).
C22H25N3O | F(000) = 372 |
Mr = 347.45 | Dx = 1.213 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 2303 reflections |
a = 8.893 (1) Å | θ = 2.8–27.5° |
b = 11.1321 (12) Å | µ = 0.08 mm−1 |
c = 10.2078 (9) Å | T = 120 K |
β = 109.749 (7)° | Block, colourless |
V = 951.11 (18) Å3 | 0.41 × 0.25 × 0.22 mm |
Z = 2 |
Bruker Nonius KappaCCD diffractometer | 2303 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 1768 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.057 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.8° |
ϕ & ω scans | h = −11→11 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −14→13 |
Tmin = 0.885, Tmax = 0.975 | l = −12→13 |
15738 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)] = 0.043 | H-atom parameters constrained |
wR(F2) = 0.103 | w = 1/[σ2(Fo2) + (0.0465P)2 + 0.196P] where P = (Fo2 + 2Fc2)/3 |
S = 1.10 | (Δ/σ)max = 0.001 |
2303 reflections | Δρmax = 0.20 e Å−3 |
239 parameters | Δρmin = −0.26 e Å−3 |
1 restraint | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.066 (6) |
C22H25N3O | V = 951.11 (18) Å3 |
Mr = 347.45 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 8.893 (1) Å | µ = 0.08 mm−1 |
b = 11.1321 (12) Å | T = 120 K |
c = 10.2078 (9) Å | 0.41 × 0.25 × 0.22 mm |
β = 109.749 (7)° |
Bruker Nonius KappaCCD diffractometer | 2303 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 1768 reflections with I > 2σ(I) |
Tmin = 0.885, Tmax = 0.975 | Rint = 0.057 |
15738 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 1 restraint |
wR(F2) = 0.103 | H-atom parameters constrained |
S = 1.10 | Δρmax = 0.20 e Å−3 |
2303 reflections | Δρmin = −0.26 e Å−3 |
239 parameters |
x | y | z | Uiso*/Ueq | ||
N1 | 0.3066 (2) | 0.43662 (19) | 0.5201 (2) | 0.0228 (5) | |
N2 | 0.1674 (2) | 0.3775 (2) | 0.4516 (2) | 0.0241 (5) | |
C3 | 0.1017 (3) | 0.3529 (2) | 0.5472 (3) | 0.0247 (6) | |
C3a | 0.1995 (3) | 0.3938 (3) | 0.6793 (3) | 0.0255 (6) | |
C4 | 0.1927 (3) | 0.3853 (3) | 0.8237 (3) | 0.0330 (7) | |
H41 | 0.1124 | 0.4424 | 0.8347 | 0.040* | |
H42 | 0.1614 | 0.3031 | 0.8412 | 0.040* | |
O5 | 0.3468 (2) | 0.41360 (19) | 0.92027 (18) | 0.0350 (5) | |
C6 | 0.4094 (3) | 0.5179 (3) | 0.8798 (3) | 0.0317 (7) | |
H61 | 0.5030 | 0.5453 | 0.9585 | 0.038* | |
H62 | 0.3277 | 0.5822 | 0.8593 | 0.038* | |
N7 | 0.4573 (2) | 0.5000 (2) | 0.7589 (2) | 0.0251 (5) | |
C7a | 0.3262 (3) | 0.4464 (2) | 0.6573 (3) | 0.0238 (6) | |
C11 | 0.3994 (3) | 0.4817 (2) | 0.4425 (2) | 0.0233 (6) | |
C12 | 0.4834 (3) | 0.5878 (3) | 0.4814 (3) | 0.0267 (6) | |
H12 | 0.4804 | 0.6306 | 0.5610 | 0.032* | |
C13 | 0.5716 (3) | 0.6307 (3) | 0.4034 (3) | 0.0317 (6) | |
H13 | 0.6308 | 0.7030 | 0.4303 | 0.038* | |
C14 | 0.5746 (3) | 0.5703 (3) | 0.2875 (3) | 0.0365 (7) | |
H14 | 0.6351 | 0.6008 | 0.2340 | 0.044* | |
C15 | 0.4895 (3) | 0.4650 (3) | 0.2487 (3) | 0.0350 (7) | |
H15 | 0.4911 | 0.4230 | 0.1682 | 0.042* | |
C16 | 0.4022 (3) | 0.4207 (3) | 0.3265 (2) | 0.0279 (6) | |
H16 | 0.3439 | 0.3480 | 0.3000 | 0.034* | |
C31 | −0.0523 (3) | 0.2849 (3) | 0.5109 (3) | 0.0263 (6) | |
C32 | −0.1357 (3) | 0.2805 (3) | 0.3546 (3) | 0.0363 (7) | |
H32A | −0.0672 | 0.2391 | 0.3112 | 0.054* | |
H32B | −0.1566 | 0.3625 | 0.3180 | 0.054* | |
H32C | −0.2369 | 0.2371 | 0.3334 | 0.054* | |
C33 | −0.0152 (4) | 0.1577 (3) | 0.5670 (3) | 0.0401 (7) | |
H33A | 0.0420 | 0.1605 | 0.6675 | 0.060* | |
H33B | 0.0514 | 0.1176 | 0.5209 | 0.060* | |
H33C | −0.1152 | 0.1130 | 0.5486 | 0.060* | |
C34 | −0.1626 (3) | 0.3444 (3) | 0.5772 (3) | 0.0320 (7) | |
H34A | −0.1810 | 0.4281 | 0.5463 | 0.048* | |
H34B | −0.1132 | 0.3420 | 0.6788 | 0.048* | |
H34C | −0.2648 | 0.3014 | 0.5495 | 0.048* | |
C77 | 0.6042 (3) | 0.4273 (3) | 0.7886 (3) | 0.0290 (6) | |
H771 | 0.6210 | 0.4079 | 0.6999 | 0.035* | |
H772 | 0.5904 | 0.3507 | 0.8326 | 0.035* | |
C71 | 0.7485 (3) | 0.4908 (3) | 0.8825 (3) | 0.0280 (6) | |
C72 | 0.8324 (3) | 0.4444 (3) | 1.0119 (3) | 0.0319 (6) | |
H72 | 0.7962 | 0.3729 | 1.0424 | 0.038* | |
C73 | 0.9686 (3) | 0.5006 (3) | 1.0978 (3) | 0.0371 (7) | |
H73 | 1.0259 | 0.4673 | 1.1863 | 0.045* | |
C74 | 1.0208 (4) | 0.6048 (3) | 1.0551 (3) | 0.0399 (8) | |
H74 | 1.1143 | 0.6438 | 1.1139 | 0.048* | |
C75 | 0.9373 (4) | 0.6523 (3) | 0.9267 (3) | 0.0395 (8) | |
H75 | 0.9726 | 0.7246 | 0.8971 | 0.047* | |
C76 | 0.8025 (3) | 0.5952 (3) | 0.8409 (3) | 0.0347 (7) | |
H76 | 0.7462 | 0.6282 | 0.7520 | 0.042* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0193 (10) | 0.0246 (12) | 0.0227 (11) | −0.0022 (9) | 0.0048 (9) | −0.0021 (9) |
N2 | 0.0212 (10) | 0.0232 (12) | 0.0254 (11) | −0.0019 (9) | 0.0045 (9) | −0.0020 (9) |
C3 | 0.0246 (13) | 0.0219 (14) | 0.0277 (14) | 0.0023 (11) | 0.0088 (11) | −0.0005 (11) |
C3a | 0.0234 (12) | 0.0272 (14) | 0.0253 (13) | −0.0011 (12) | 0.0076 (10) | −0.0013 (11) |
C4 | 0.0302 (14) | 0.0430 (17) | 0.0257 (13) | −0.0082 (14) | 0.0094 (11) | −0.0013 (13) |
O5 | 0.0335 (10) | 0.0457 (13) | 0.0231 (9) | −0.0084 (10) | 0.0060 (8) | 0.0029 (9) |
C6 | 0.0314 (15) | 0.0366 (17) | 0.0261 (14) | −0.0047 (13) | 0.0084 (12) | −0.0056 (13) |
N7 | 0.0232 (11) | 0.0267 (12) | 0.0233 (10) | 0.0003 (10) | 0.0052 (9) | −0.0028 (10) |
C7a | 0.0228 (12) | 0.0247 (14) | 0.0219 (12) | 0.0023 (11) | 0.0051 (10) | 0.0012 (11) |
C11 | 0.0189 (12) | 0.0259 (14) | 0.0236 (12) | 0.0009 (10) | 0.0050 (10) | 0.0057 (11) |
C12 | 0.0248 (13) | 0.0263 (14) | 0.0278 (14) | 0.0013 (11) | 0.0074 (11) | 0.0022 (12) |
C13 | 0.0289 (14) | 0.0295 (15) | 0.0338 (15) | −0.0049 (12) | 0.0069 (12) | 0.0054 (12) |
C14 | 0.0329 (16) | 0.0472 (19) | 0.0303 (15) | −0.0047 (14) | 0.0119 (13) | 0.0068 (14) |
C15 | 0.0352 (15) | 0.0477 (19) | 0.0228 (13) | −0.0051 (14) | 0.0108 (12) | 0.0005 (13) |
C16 | 0.0269 (13) | 0.0334 (15) | 0.0211 (12) | −0.0024 (12) | 0.0050 (10) | −0.0006 (12) |
C31 | 0.0231 (13) | 0.0261 (14) | 0.0301 (14) | −0.0028 (11) | 0.0094 (11) | −0.0027 (12) |
C32 | 0.0277 (14) | 0.0468 (18) | 0.0327 (16) | −0.0115 (14) | 0.0079 (12) | −0.0058 (14) |
C33 | 0.0350 (16) | 0.0301 (16) | 0.054 (2) | −0.0047 (13) | 0.0136 (15) | 0.0000 (15) |
C34 | 0.0258 (14) | 0.0346 (16) | 0.0380 (15) | −0.0021 (12) | 0.0140 (12) | −0.0046 (13) |
C77 | 0.0243 (13) | 0.0267 (14) | 0.0328 (14) | 0.0009 (11) | 0.0056 (11) | −0.0006 (12) |
C71 | 0.0238 (13) | 0.0308 (15) | 0.0273 (13) | 0.0028 (12) | 0.0059 (11) | −0.0027 (12) |
C72 | 0.0307 (14) | 0.0312 (16) | 0.0307 (14) | 0.0001 (12) | 0.0063 (12) | −0.0017 (12) |
C73 | 0.0290 (14) | 0.0445 (18) | 0.0309 (14) | 0.0031 (14) | 0.0011 (12) | −0.0055 (14) |
C74 | 0.0287 (15) | 0.049 (2) | 0.0379 (17) | −0.0047 (14) | 0.0053 (13) | −0.0116 (15) |
C75 | 0.0382 (16) | 0.0376 (17) | 0.0425 (18) | −0.0124 (14) | 0.0134 (14) | −0.0045 (15) |
C76 | 0.0347 (15) | 0.0347 (17) | 0.0314 (14) | −0.0032 (13) | 0.0068 (12) | −0.0008 (13) |
N1—C7a | 1.356 (3) | C16—H16 | 0.9500 |
N1—N2 | 1.367 (3) | C31—C32 | 1.517 (4) |
N1—C11 | 1.415 (3) | C31—C34 | 1.519 (4) |
N2—C3 | 1.324 (3) | C31—C33 | 1.522 (4) |
C3—C3a | 1.410 (4) | C32—H32A | 0.9800 |
C3—C31 | 1.498 (4) | C32—H32B | 0.9800 |
C3a—C7a | 1.354 (4) | C32—H32C | 0.9800 |
C3a—C4 | 1.499 (3) | C33—H33A | 0.9800 |
C4—O5 | 1.427 (3) | C33—H33B | 0.9800 |
C4—H41 | 0.9900 | C33—H33C | 0.9800 |
C4—H42 | 0.9900 | C34—H34A | 0.9800 |
O5—C6 | 1.408 (3) | C34—H34B | 0.9800 |
C6—N7 | 1.449 (3) | C34—H34C | 0.9800 |
C6—H61 | 0.9900 | C77—C71 | 1.494 (4) |
C6—H62 | 0.9900 | C77—H771 | 0.9900 |
N7—C7a | 1.405 (3) | C77—H772 | 0.9900 |
N7—C77 | 1.479 (3) | C71—C76 | 1.378 (4) |
C11—C16 | 1.372 (4) | C71—C72 | 1.379 (4) |
C11—C12 | 1.382 (4) | C72—C73 | 1.381 (4) |
C12—C13 | 1.378 (4) | C72—H72 | 0.9500 |
C12—H12 | 0.9500 | C73—C74 | 1.374 (5) |
C13—C14 | 1.369 (4) | C73—H73 | 0.9500 |
C13—H13 | 0.9500 | C74—C75 | 1.375 (4) |
C14—C15 | 1.378 (4) | C74—H74 | 0.9500 |
C14—H14 | 0.9500 | C75—C76 | 1.378 (4) |
C15—C16 | 1.376 (4) | C75—H75 | 0.9500 |
C15—H15 | 0.9500 | C76—H76 | 0.9500 |
C7a—N1—N2 | 110.2 (2) | C3—C31—C34 | 110.1 (2) |
C7a—N1—C11 | 130.8 (2) | C32—C31—C34 | 108.9 (2) |
N2—N1—C11 | 118.90 (19) | C3—C31—C33 | 108.3 (2) |
C3—N2—N1 | 105.75 (19) | C32—C31—C33 | 109.4 (2) |
N2—C3—C3a | 110.8 (2) | C34—C31—C33 | 109.2 (2) |
N2—C3—C31 | 121.1 (2) | C31—C32—H32A | 109.5 |
C3a—C3—C31 | 128.0 (2) | C31—C32—H32B | 109.5 |
C7a—C3a—C3 | 105.1 (2) | H32A—C32—H32B | 109.5 |
C7a—C3a—C4 | 120.2 (2) | C31—C32—H32C | 109.5 |
C3—C3a—C4 | 134.7 (2) | H32A—C32—H32C | 109.5 |
O5—C4—C3a | 108.5 (2) | H32B—C32—H32C | 109.5 |
O5—C4—H41 | 110.0 | C31—C33—H33A | 109.5 |
C3a—C4—H41 | 110.0 | C31—C33—H33B | 109.5 |
O5—C4—H42 | 110.0 | H33A—C33—H33B | 109.5 |
C3a—C4—H42 | 110.0 | C31—C33—H33C | 109.5 |
H41—C4—H42 | 108.4 | H33A—C33—H33C | 109.5 |
C6—O5—C4 | 111.2 (2) | H33B—C33—H33C | 109.5 |
O5—C6—N7 | 113.3 (2) | C31—C34—H34A | 109.5 |
O5—C6—H61 | 108.9 | C31—C34—H34B | 109.5 |
N7—C6—H61 | 108.9 | H34A—C34—H34B | 109.5 |
O5—C6—H62 | 108.9 | C31—C34—H34C | 109.5 |
N7—C6—H62 | 108.9 | H34A—C34—H34C | 109.5 |
H61—C6—H62 | 107.7 | H34B—C34—H34C | 109.5 |
C7a—N7—C6 | 106.1 (2) | N7—C77—C71 | 112.4 (2) |
C7a—N7—C77 | 112.0 (2) | N7—C77—H771 | 109.1 |
C6—N7—C77 | 113.2 (2) | C71—C77—H771 | 109.1 |
C3a—C7a—N1 | 108.2 (2) | N7—C77—H772 | 109.1 |
C3a—C7a—N7 | 126.2 (2) | C71—C77—H772 | 109.1 |
N1—C7a—N7 | 125.5 (2) | H771—C77—H772 | 107.9 |
C16—C11—C12 | 120.3 (2) | C76—C71—C72 | 118.6 (3) |
C16—C11—N1 | 119.4 (2) | C76—C71—C77 | 121.0 (2) |
C12—C11—N1 | 120.2 (2) | C72—C71—C77 | 120.4 (3) |
C13—C12—C11 | 119.2 (3) | C71—C72—C73 | 120.8 (3) |
C13—C12—H12 | 120.4 | C71—C72—H72 | 119.6 |
C11—C12—H12 | 120.4 | C73—C72—H72 | 119.6 |
C14—C13—C12 | 120.6 (3) | C74—C73—C72 | 119.9 (3) |
C14—C13—H13 | 119.7 | C74—C73—H73 | 120.0 |
C12—C13—H13 | 119.7 | C72—C73—H73 | 120.0 |
C13—C14—C15 | 119.8 (3) | C73—C74—C75 | 119.7 (3) |
C13—C14—H14 | 120.1 | C73—C74—H74 | 120.2 |
C15—C14—H14 | 120.1 | C75—C74—H74 | 120.2 |
C16—C15—C14 | 120.1 (3) | C74—C75—C76 | 120.2 (3) |
C16—C15—H15 | 120.0 | C74—C75—H75 | 119.9 |
C14—C15—H15 | 120.0 | C76—C75—H75 | 119.9 |
C11—C16—C15 | 119.9 (3) | C75—C76—C71 | 120.8 (3) |
C11—C16—H16 | 120.0 | C75—C76—H76 | 119.6 |
C15—C16—H16 | 120.0 | C71—C76—H76 | 119.6 |
C3—C31—C32 | 110.9 (2) | ||
C7a—N1—N2—C3 | 0.8 (3) | C7a—N1—C11—C12 | −30.7 (4) |
C11—N1—N2—C3 | −176.0 (2) | N2—N1—C11—C12 | 145.5 (2) |
N1—N2—C3—C3a | −1.2 (3) | C16—C11—C12—C13 | −0.8 (4) |
N1—N2—C3—C31 | −178.4 (2) | N1—C11—C12—C13 | −179.2 (2) |
N2—C3—C3a—C7a | 1.2 (3) | C11—C12—C13—C14 | 0.9 (4) |
C31—C3—C3a—C7a | 178.1 (3) | C12—C13—C14—C15 | −0.4 (4) |
N2—C3—C3a—C4 | −175.8 (3) | C13—C14—C15—C16 | −0.2 (4) |
C31—C3—C3a—C4 | 1.2 (5) | C12—C11—C16—C15 | 0.3 (4) |
C7a—C3a—C4—O5 | −13.0 (4) | N1—C11—C16—C15 | 178.7 (2) |
C3—C3a—C4—O5 | 163.6 (3) | C14—C15—C16—C11 | 0.3 (4) |
C3a—C4—O5—C6 | 46.8 (3) | N2—C3—C31—C32 | −14.8 (4) |
C4—O5—C6—N7 | −71.5 (3) | C3a—C3—C31—C32 | 168.5 (3) |
O5—C6—N7—C7a | 51.0 (3) | N2—C3—C31—C34 | −135.4 (3) |
O5—C6—N7—C77 | −72.2 (3) | C3a—C3—C31—C34 | 47.9 (4) |
C3—C3a—C7a—N1 | −0.6 (3) | N2—C3—C31—C33 | 105.2 (3) |
C4—C3a—C7a—N1 | 176.9 (2) | C3a—C3—C31—C33 | −71.4 (3) |
C3—C3a—C7a—N7 | −179.5 (2) | C7a—N7—C77—C71 | 172.6 (2) |
C4—C3a—C7a—N7 | −2.0 (4) | C6—N7—C77—C71 | −67.5 (3) |
N2—N1—C7a—C3a | −0.1 (3) | N7—C77—C71—C76 | −64.3 (3) |
C11—N1—C7a—C3a | 176.2 (3) | N7—C77—C71—C72 | 117.1 (3) |
N2—N1—C7a—N7 | 178.8 (2) | C76—C71—C72—C73 | −0.5 (4) |
C11—N1—C7a—N7 | −4.8 (4) | C77—C71—C72—C73 | 178.1 (3) |
C6—N7—C7a—C3a | −15.6 (4) | C71—C72—C73—C74 | 0.6 (4) |
C77—N7—C7a—C3a | 108.3 (3) | C72—C73—C74—C75 | −0.1 (4) |
C6—N7—C7a—N1 | 165.6 (3) | C73—C74—C75—C76 | −0.5 (5) |
C77—N7—C7a—N1 | −70.4 (3) | C74—C75—C76—C71 | 0.6 (5) |
C7a—N1—C11—C16 | 150.9 (3) | C72—C71—C76—C75 | −0.1 (4) |
N2—N1—C11—C16 | −33.0 (3) | C77—C71—C76—C75 | −178.8 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C12—H12···N7 | 0.95 | 2.55 | 3.079 (4) | 115 |
C15—H15···O5i | 0.95 | 2.42 | 3.210 (3) | 140 |
Symmetry code: (i) x, y, z−1. |
C23H27N3O | F(000) = 388 |
Mr = 361.48 | Dx = 1.245 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 2323 reflections |
a = 8.9500 (7) Å | θ = 3.0–27.5° |
b = 11.2146 (10) Å | µ = 0.08 mm−1 |
c = 10.0768 (9) Å | T = 120 K |
β = 107.572 (5)° | Block, colourless |
V = 964.22 (15) Å3 | 0.32 × 0.22 × 0.15 mm |
Z = 2 |
Bruker Nonius KappaCCD diffractometer | 2323 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 1443 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.096 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.0° |
ϕ & ω scans | h = −10→11 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −14→14 |
Tmin = 0.957, Tmax = 0.989 | l = −13→13 |
15494 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)] = 0.052 | H-atom parameters constrained |
wR(F2) = 0.149 | w = 1/[σ2(Fo2) + (0.0767P)2 + 0.189P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max = 0.001 |
2323 reflections | Δρmax = 0.27 e Å−3 |
249 parameters | Δρmin = −0.30 e Å−3 |
1 restraint | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.032 (7) |
C23H27N3O | V = 964.22 (15) Å3 |
Mr = 361.48 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 8.9500 (7) Å | µ = 0.08 mm−1 |
b = 11.2146 (10) Å | T = 120 K |
c = 10.0768 (9) Å | 0.32 × 0.22 × 0.15 mm |
β = 107.572 (5)° |
Bruker Nonius KappaCCD diffractometer | 2323 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 1443 reflections with I > 2σ(I) |
Tmin = 0.957, Tmax = 0.989 | Rint = 0.096 |
15494 measured reflections |
R[F2 > 2σ(F2)] = 0.052 | 1 restraint |
wR(F2) = 0.149 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.27 e Å−3 |
2323 reflections | Δρmin = −0.30 e Å−3 |
249 parameters |
x | y | z | Uiso*/Ueq | ||
N1 | 0.3078 (3) | 0.4332 (3) | 0.5203 (3) | 0.0238 (8) | |
N2 | 0.1722 (4) | 0.3740 (3) | 0.4519 (3) | 0.0253 (8) | |
C3 | 0.1017 (4) | 0.3517 (4) | 0.5478 (4) | 0.0247 (9) | |
C3a | 0.1920 (4) | 0.3949 (4) | 0.6797 (4) | 0.0266 (9) | |
C4 | 0.1777 (5) | 0.3906 (5) | 0.8237 (4) | 0.0322 (11) | |
H41 | 0.0956 | 0.4469 | 0.8315 | 0.039* | |
H42 | 0.1472 | 0.3093 | 0.8439 | 0.039* | |
O5 | 0.3239 (3) | 0.4219 (3) | 0.9210 (3) | 0.0327 (8) | |
C6 | 0.3895 (5) | 0.5233 (5) | 0.8770 (4) | 0.0325 (11) | |
H61 | 0.4783 | 0.5523 | 0.9551 | 0.039* | |
H62 | 0.3096 | 0.5873 | 0.8526 | 0.039* | |
N7 | 0.4445 (4) | 0.5000 (3) | 0.7580 (3) | 0.0254 (8) | |
C7a | 0.3193 (4) | 0.4460 (4) | 0.6571 (4) | 0.0263 (9) | |
C11 | 0.4058 (4) | 0.4750 (4) | 0.4433 (4) | 0.0239 (9) | |
C12 | 0.4847 (5) | 0.5823 (4) | 0.4768 (4) | 0.0283 (10) | |
H12 | 0.4758 | 0.6283 | 0.5532 | 0.034* | |
C13 | 0.5760 (4) | 0.6210 (5) | 0.3979 (4) | 0.0321 (11) | |
H13 | 0.6320 | 0.6939 | 0.4213 | 0.039* | |
C14 | 0.5879 (5) | 0.5567 (5) | 0.2861 (4) | 0.0336 (11) | |
H14 | 0.6514 | 0.5849 | 0.2324 | 0.040* | |
C15 | 0.5073 (4) | 0.4509 (5) | 0.2519 (4) | 0.0309 (11) | |
H15 | 0.5146 | 0.4065 | 0.1737 | 0.037* | |
C16 | 0.4164 (4) | 0.4091 (4) | 0.3303 (4) | 0.0278 (10) | |
H16 | 0.3614 | 0.3358 | 0.3071 | 0.033* | |
C31 | −0.0499 (4) | 0.2846 (4) | 0.5125 (4) | 0.0257 (10) | |
C32 | −0.1238 (5) | 0.2759 (5) | 0.3553 (4) | 0.0355 (11) | |
H32A | −0.1442 | 0.3562 | 0.3157 | 0.053* | |
H32B | −0.2227 | 0.2317 | 0.3348 | 0.053* | |
H32C | −0.0521 | 0.2340 | 0.3145 | 0.053* | |
C33 | −0.0154 (5) | 0.1602 (4) | 0.5737 (5) | 0.0370 (11) | |
H33A | 0.0552 | 0.1191 | 0.5311 | 0.055* | |
H33B | −0.1135 | 0.1153 | 0.5551 | 0.055* | |
H33C | 0.0344 | 0.1660 | 0.6745 | 0.055* | |
C34 | −0.1641 (5) | 0.3483 (4) | 0.5734 (4) | 0.0309 (10) | |
H34A | −0.1186 | 0.3542 | 0.6747 | 0.046* | |
H34B | −0.2624 | 0.3033 | 0.5514 | 0.046* | |
H34C | −0.1849 | 0.4286 | 0.5335 | 0.046* | |
C77 | 0.5865 (4) | 0.4259 (4) | 0.7933 (4) | 0.0303 (10) | |
H771 | 0.6068 | 0.4005 | 0.7063 | 0.036* | |
H772 | 0.5683 | 0.3533 | 0.8421 | 0.036* | |
C71 | 0.7286 (5) | 0.4891 (4) | 0.8836 (4) | 0.0280 (10) | |
C72 | 0.8120 (4) | 0.4434 (4) | 1.0116 (4) | 0.0290 (10) | |
H72 | 0.7737 | 0.3751 | 1.0467 | 0.035* | |
C73 | 0.9511 (5) | 0.4958 (4) | 1.0897 (4) | 0.0286 (10) | |
H73 | 1.0077 | 0.4621 | 1.1768 | 0.034* | |
C74 | 1.0079 (4) | 0.5955 (4) | 1.0428 (4) | 0.0291 (10) | |
C75 | 0.9211 (5) | 0.6440 (4) | 0.9169 (4) | 0.0321 (10) | |
H75 | 0.9563 | 0.7150 | 0.8844 | 0.039* | |
C76 | 0.7843 (5) | 0.5908 (4) | 0.8378 (4) | 0.0307 (10) | |
H76 | 0.7278 | 0.6246 | 0.7506 | 0.037* | |
C78 | 1.1619 (4) | 0.6482 (5) | 1.1232 (4) | 0.0323 (11) | |
H78A | 1.1965 | 0.6130 | 1.2165 | 0.048* | |
H78B | 1.1506 | 0.7347 | 1.1308 | 0.048* | |
H78C | 1.2397 | 0.6316 | 1.0750 | 0.048* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0211 (16) | 0.027 (2) | 0.0233 (17) | −0.0022 (15) | 0.0063 (13) | −0.0043 (16) |
N2 | 0.0231 (17) | 0.026 (2) | 0.0257 (18) | −0.0024 (15) | 0.0060 (14) | −0.0018 (15) |
C3 | 0.026 (2) | 0.023 (2) | 0.027 (2) | 0.0037 (18) | 0.0099 (17) | 0.0018 (19) |
C3a | 0.024 (2) | 0.029 (3) | 0.027 (2) | −0.0038 (19) | 0.0085 (16) | 0.0003 (19) |
C4 | 0.027 (2) | 0.043 (3) | 0.026 (2) | −0.004 (2) | 0.0076 (17) | −0.003 (2) |
O5 | 0.0311 (15) | 0.042 (2) | 0.0228 (14) | −0.0039 (15) | 0.0049 (12) | 0.0018 (14) |
C6 | 0.030 (2) | 0.043 (3) | 0.025 (2) | −0.003 (2) | 0.0078 (18) | −0.005 (2) |
N7 | 0.0220 (17) | 0.031 (2) | 0.0202 (16) | 0.0021 (15) | 0.0014 (14) | −0.0020 (16) |
C7a | 0.028 (2) | 0.027 (2) | 0.022 (2) | 0.0041 (19) | 0.0065 (16) | −0.0012 (19) |
C11 | 0.0202 (19) | 0.027 (2) | 0.022 (2) | 0.0040 (17) | 0.0032 (16) | 0.0033 (18) |
C12 | 0.025 (2) | 0.030 (3) | 0.028 (2) | −0.0012 (18) | 0.0052 (17) | 0.001 (2) |
C13 | 0.023 (2) | 0.038 (3) | 0.031 (2) | −0.004 (2) | 0.0023 (17) | 0.007 (2) |
C14 | 0.028 (2) | 0.045 (3) | 0.027 (2) | 0.000 (2) | 0.0071 (18) | 0.008 (2) |
C15 | 0.025 (2) | 0.044 (3) | 0.024 (2) | 0.003 (2) | 0.0065 (17) | 0.001 (2) |
C16 | 0.024 (2) | 0.033 (3) | 0.026 (2) | 0.0003 (19) | 0.0073 (16) | 0.000 (2) |
C31 | 0.027 (2) | 0.027 (2) | 0.024 (2) | −0.0037 (18) | 0.0079 (16) | −0.0029 (19) |
C32 | 0.028 (2) | 0.045 (3) | 0.031 (2) | −0.009 (2) | 0.0045 (18) | −0.009 (2) |
C33 | 0.035 (2) | 0.032 (3) | 0.045 (3) | 0.000 (2) | 0.014 (2) | −0.001 (2) |
C34 | 0.028 (2) | 0.035 (3) | 0.031 (2) | −0.0017 (19) | 0.0103 (18) | −0.001 (2) |
C77 | 0.026 (2) | 0.030 (3) | 0.032 (2) | 0.0022 (19) | 0.0033 (17) | 0.000 (2) |
C71 | 0.024 (2) | 0.033 (3) | 0.026 (2) | 0.0028 (18) | 0.0051 (17) | −0.007 (2) |
C72 | 0.030 (2) | 0.029 (3) | 0.027 (2) | −0.0049 (19) | 0.0071 (17) | −0.002 (2) |
C73 | 0.027 (2) | 0.034 (3) | 0.021 (2) | −0.0007 (19) | 0.0015 (17) | 0.000 (2) |
C74 | 0.026 (2) | 0.034 (3) | 0.027 (2) | 0.0006 (19) | 0.0086 (18) | −0.006 (2) |
C75 | 0.034 (2) | 0.028 (3) | 0.031 (2) | −0.003 (2) | 0.0065 (19) | 0.000 (2) |
C76 | 0.032 (2) | 0.029 (3) | 0.027 (2) | 0.002 (2) | 0.0024 (18) | 0.001 (2) |
C78 | 0.031 (2) | 0.039 (3) | 0.027 (2) | −0.004 (2) | 0.0081 (18) | −0.004 (2) |
N1—C7a | 1.358 (5) | C31—C34 | 1.520 (6) |
N1—N2 | 1.372 (4) | C31—C32 | 1.524 (6) |
N1—C11 | 1.415 (5) | C32—H32A | 0.9800 |
N2—C3 | 1.328 (5) | C32—H32B | 0.9800 |
C3—C3a | 1.416 (6) | C32—H32C | 0.9800 |
C3—C31 | 1.497 (5) | C33—H33A | 0.9800 |
C3a—C7a | 1.354 (6) | C33—H33B | 0.9800 |
C3a—C4 | 1.496 (5) | C33—H33C | 0.9800 |
C4—O5 | 1.422 (5) | C34—H34A | 0.9800 |
C4—H41 | 0.9900 | C34—H34B | 0.9800 |
C4—H42 | 0.9900 | C34—H34C | 0.9800 |
O5—C6 | 1.411 (6) | C77—C71 | 1.499 (6) |
C6—N7 | 1.450 (5) | C77—H771 | 0.9900 |
C6—H61 | 0.9900 | C77—H772 | 0.9900 |
C6—H62 | 0.9900 | C71—C72 | 1.379 (6) |
N7—C7a | 1.403 (5) | C71—C76 | 1.379 (6) |
N7—C77 | 1.470 (5) | C72—C73 | 1.387 (6) |
C11—C12 | 1.385 (6) | C72—H72 | 0.9500 |
C11—C16 | 1.385 (6) | C73—C74 | 1.370 (6) |
C12—C13 | 1.371 (6) | C73—H73 | 0.9500 |
C12—H12 | 0.9500 | C74—C75 | 1.384 (6) |
C13—C14 | 1.369 (7) | C74—C78 | 1.494 (6) |
C13—H13 | 0.9500 | C75—C76 | 1.379 (6) |
C14—C15 | 1.377 (7) | C75—H75 | 0.9500 |
C14—H14 | 0.9500 | C76—H76 | 0.9500 |
C15—C16 | 1.377 (6) | C78—H78A | 0.9800 |
C15—H15 | 0.9500 | C78—H78B | 0.9800 |
C16—H16 | 0.9500 | C78—H78C | 0.9800 |
C31—C33 | 1.519 (7) | ||
C7a—N1—N2 | 110.2 (3) | C33—C31—C32 | 109.5 (4) |
C7a—N1—C11 | 130.7 (3) | C34—C31—C32 | 108.4 (3) |
N2—N1—C11 | 119.0 (3) | C31—C32—H32A | 109.5 |
C3—N2—N1 | 105.5 (3) | C31—C32—H32B | 109.5 |
N2—C3—C3a | 110.9 (3) | H32A—C32—H32B | 109.5 |
N2—C3—C31 | 121.1 (3) | C31—C32—H32C | 109.5 |
C3a—C3—C31 | 127.9 (3) | H32A—C32—H32C | 109.5 |
C7a—C3a—C3 | 104.9 (3) | H32B—C32—H32C | 109.5 |
C7a—C3a—C4 | 120.0 (4) | C31—C33—H33A | 109.5 |
C3—C3a—C4 | 135.0 (3) | C31—C33—H33B | 109.5 |
O5—C4—C3a | 109.3 (3) | H33A—C33—H33B | 109.5 |
O5—C4—H41 | 109.8 | C31—C33—H33C | 109.5 |
C3a—C4—H41 | 109.8 | H33A—C33—H33C | 109.5 |
O5—C4—H42 | 109.8 | H33B—C33—H33C | 109.5 |
C3a—C4—H42 | 109.8 | C31—C34—H34A | 109.5 |
H41—C4—H42 | 108.3 | C31—C34—H34B | 109.5 |
C6—O5—C4 | 111.4 (3) | H34A—C34—H34B | 109.5 |
O5—C6—N7 | 113.1 (4) | C31—C34—H34C | 109.5 |
O5—C6—H61 | 109.0 | H34A—C34—H34C | 109.5 |
N7—C6—H61 | 109.0 | H34B—C34—H34C | 109.5 |
O5—C6—H62 | 109.0 | N7—C77—C71 | 113.1 (4) |
N7—C6—H62 | 109.0 | N7—C77—H771 | 109.0 |
H61—C6—H62 | 107.8 | C71—C77—H771 | 109.0 |
C7a—N7—C6 | 106.3 (3) | N7—C77—H772 | 109.0 |
C7a—N7—C77 | 112.0 (3) | C71—C77—H772 | 109.0 |
C6—N7—C77 | 112.7 (3) | H771—C77—H772 | 107.8 |
C3a—C7a—N1 | 108.4 (3) | C72—C71—C76 | 118.2 (4) |
C3a—C7a—N7 | 126.1 (4) | C72—C71—C77 | 120.8 (4) |
N1—C7a—N7 | 125.5 (4) | C76—C71—C77 | 120.9 (4) |
C12—C11—C16 | 120.5 (4) | C71—C72—C73 | 120.9 (4) |
C12—C11—N1 | 120.6 (4) | C71—C72—H72 | 119.6 |
C16—C11—N1 | 118.8 (4) | C73—C72—H72 | 119.6 |
C13—C12—C11 | 118.9 (4) | C74—C73—C72 | 120.9 (4) |
C13—C12—H12 | 120.5 | C74—C73—H73 | 119.6 |
C11—C12—H12 | 120.5 | C72—C73—H73 | 119.6 |
C14—C13—C12 | 121.2 (5) | C73—C74—C75 | 118.2 (4) |
C14—C13—H13 | 119.4 | C73—C74—C78 | 120.9 (4) |
C12—C13—H13 | 119.4 | C75—C74—C78 | 120.8 (4) |
C13—C14—C15 | 119.7 (4) | C76—C75—C74 | 121.0 (4) |
C13—C14—H14 | 120.2 | C76—C75—H75 | 119.5 |
C15—C14—H14 | 120.2 | C74—C75—H75 | 119.5 |
C16—C15—C14 | 120.3 (4) | C75—C76—C71 | 120.8 (4) |
C16—C15—H15 | 119.8 | C75—C76—H76 | 119.6 |
C14—C15—H15 | 119.8 | C71—C76—H76 | 119.6 |
C15—C16—C11 | 119.3 (4) | C74—C78—H78A | 109.5 |
C15—C16—H16 | 120.3 | C74—C78—H78B | 109.5 |
C11—C16—H16 | 120.3 | H78A—C78—H78B | 109.5 |
C3—C31—C33 | 107.8 (3) | C74—C78—H78C | 109.5 |
C3—C31—C34 | 109.8 (3) | H78A—C78—H78C | 109.5 |
C33—C31—C34 | 110.3 (4) | H78B—C78—H78C | 109.5 |
C3—C31—C32 | 111.0 (3) | ||
C7a—N1—N2—C3 | 0.3 (4) | N2—N1—C11—C16 | −34.0 (5) |
C11—N1—N2—C3 | −176.7 (4) | C16—C11—C12—C13 | −1.3 (6) |
N1—N2—C3—C3a | −0.8 (4) | N1—C11—C12—C13 | −178.6 (4) |
N1—N2—C3—C31 | −178.5 (4) | C11—C12—C13—C14 | 1.1 (6) |
N2—C3—C3a—C7a | 0.9 (5) | C12—C13—C14—C15 | −0.2 (6) |
C31—C3—C3a—C7a | 178.4 (4) | C13—C14—C15—C16 | −0.7 (6) |
N2—C3—C3a—C4 | −176.2 (5) | C14—C15—C16—C11 | 0.5 (6) |
C31—C3—C3a—C4 | 1.3 (8) | C12—C11—C16—C15 | 0.5 (6) |
C7a—C3a—C4—O5 | −12.1 (6) | N1—C11—C16—C15 | 177.9 (3) |
C3—C3a—C4—O5 | 164.7 (5) | N2—C3—C31—C33 | 106.2 (4) |
C3a—C4—O5—C6 | 45.4 (5) | C3a—C3—C31—C33 | −71.1 (5) |
C4—O5—C6—N7 | −70.5 (4) | N2—C3—C31—C34 | −133.6 (4) |
O5—C6—N7—C7a | 51.7 (4) | C3a—C3—C31—C34 | 49.1 (6) |
O5—C6—N7—C77 | −71.3 (4) | N2—C3—C31—C32 | −13.7 (5) |
C3—C3a—C7a—N1 | −0.7 (5) | C3a—C3—C31—C32 | 169.0 (4) |
C4—C3a—C7a—N1 | 177.0 (4) | C7a—N7—C77—C71 | 171.0 (3) |
C3—C3a—C7a—N7 | −179.0 (4) | C6—N7—C77—C71 | −69.2 (5) |
C4—C3a—C7a—N7 | −1.3 (7) | N7—C77—C71—C72 | 122.1 (4) |
N2—N1—C7a—C3a | 0.2 (5) | N7—C77—C71—C76 | −61.5 (5) |
C11—N1—C7a—C3a | 176.9 (4) | C76—C71—C72—C73 | −2.3 (6) |
N2—N1—C7a—N7 | 178.6 (4) | C77—C71—C72—C73 | 174.2 (4) |
C11—N1—C7a—N7 | −4.8 (7) | C71—C72—C73—C74 | 1.1 (6) |
C6—N7—C7a—C3a | −17.2 (6) | C72—C73—C74—C75 | 1.3 (6) |
C77—N7—C7a—C3a | 106.3 (5) | C72—C73—C74—C78 | −176.7 (4) |
C6—N7—C7a—N1 | 164.7 (4) | C73—C74—C75—C76 | −2.6 (6) |
C77—N7—C7a—N1 | −71.8 (5) | C78—C74—C75—C76 | 175.4 (4) |
C7a—N1—C11—C12 | −32.9 (6) | C74—C75—C76—C71 | 1.4 (7) |
N2—N1—C11—C12 | 143.5 (4) | C72—C71—C76—C75 | 1.0 (6) |
C7a—N1—C11—C16 | 149.7 (4) | C77—C71—C76—C75 | −175.4 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C12—H12···N7 | 0.95 | 2.60 | 3.103 (5) | 113 |
C15—H15···O5i | 0.95 | 2.61 | 3.258 (5) | 126 |
C4—H41···Cg1ii | 0.99 | 2.96 | 3.872 (5) | 154 |
Symmetry codes: (i) x, y, z−1; (ii) x−1, y, z. |
C23H27N3O2 | F(000) = 404 |
Mr = 377.48 | Dx = 1.252 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 2411 reflections |
a = 9.1888 (2) Å | θ = 3.3–27.5° |
b = 11.4499 (3) Å | µ = 0.08 mm−1 |
c = 9.7210 (2) Å | T = 120 K |
β = 101.857 (1)° | Plate, colourless |
V = 1000.93 (4) Å3 | 0.15 × 0.12 × 0.05 mm |
Z = 2 |
Bruker Nonius KappaCCD diffractometer | 2411 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 2237 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.036 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.3° |
ϕ & ω scans | h = −11→11 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −14→14 |
Tmin = 0.980, Tmax = 0.996 | l = −12→12 |
12855 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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.085 | H-atom parameters constrained |
S = 1.19 | w = 1/[σ2(Fo2) + (0.0249P)2 + 0.3009P] where P = (Fo2 + 2Fc2)/3 |
2411 reflections | (Δ/σ)max = 0.001 |
257 parameters | Δρmax = 0.17 e Å−3 |
1 restraint | Δρmin = −0.20 e Å−3 |
C23H27N3O2 | V = 1000.93 (4) Å3 |
Mr = 377.48 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 9.1888 (2) Å | µ = 0.08 mm−1 |
b = 11.4499 (3) Å | T = 120 K |
c = 9.7210 (2) Å | 0.15 × 0.12 × 0.05 mm |
β = 101.857 (1)° |
Bruker Nonius KappaCCD diffractometer | 2411 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2237 reflections with I > 2σ(I) |
Tmin = 0.980, Tmax = 0.996 | Rint = 0.036 |
12855 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 1 restraint |
wR(F2) = 0.085 | H-atom parameters constrained |
S = 1.19 | Δρmax = 0.17 e Å−3 |
2411 reflections | Δρmin = −0.20 e Å−3 |
257 parameters |
x | y | z | Uiso*/Ueq | ||
N1 | 0.30851 (18) | 0.44062 (16) | 0.49961 (18) | 0.0181 (4) | |
N2 | 0.18295 (18) | 0.38394 (16) | 0.42962 (19) | 0.0189 (4) | |
C3 | 0.1054 (2) | 0.35873 (19) | 0.5281 (2) | 0.0184 (4) | |
C3a | 0.1815 (2) | 0.39726 (19) | 0.6624 (2) | 0.0193 (4) | |
C4 | 0.1524 (2) | 0.3901 (2) | 0.8090 (2) | 0.0262 (5) | |
H41 | 0.0730 | 0.4458 | 0.8194 | 0.031* | |
H42 | 0.1188 | 0.3104 | 0.8269 | 0.031* | |
O5 | 0.28733 (18) | 0.41768 (16) | 0.90850 (16) | 0.0274 (4) | |
C6 | 0.3562 (3) | 0.5198 (2) | 0.8664 (2) | 0.0242 (5) | |
H61 | 0.4354 | 0.5461 | 0.9453 | 0.029* | |
H62 | 0.2813 | 0.5829 | 0.8456 | 0.029* | |
N7 | 0.42067 (19) | 0.50000 (17) | 0.74260 (18) | 0.0200 (4) | |
C7a | 0.3087 (2) | 0.44813 (19) | 0.6400 (2) | 0.0188 (4) | |
C11 | 0.4150 (2) | 0.48229 (19) | 0.4231 (2) | 0.0184 (4) | |
C12 | 0.4883 (2) | 0.5878 (2) | 0.4598 (2) | 0.0229 (5) | |
H12 | 0.4694 | 0.6319 | 0.5371 | 0.027* | |
C13 | 0.5892 (2) | 0.6276 (2) | 0.3822 (3) | 0.0274 (5) | |
H13 | 0.6410 | 0.6988 | 0.4076 | 0.033* | |
C14 | 0.6152 (3) | 0.5645 (2) | 0.2679 (3) | 0.0284 (5) | |
H14 | 0.6840 | 0.5924 | 0.2149 | 0.034* | |
C15 | 0.5402 (2) | 0.4604 (2) | 0.2315 (2) | 0.0257 (5) | |
H15 | 0.5574 | 0.4174 | 0.1529 | 0.031* | |
C16 | 0.4403 (2) | 0.4185 (2) | 0.3089 (2) | 0.0224 (5) | |
H16 | 0.3897 | 0.3468 | 0.2840 | 0.027* | |
C31 | −0.0396 (2) | 0.29158 (19) | 0.4906 (2) | 0.0200 (4) | |
C32 | −0.1048 (3) | 0.2980 (3) | 0.3330 (2) | 0.0306 (6) | |
H32A | −0.1230 | 0.3798 | 0.3050 | 0.046* | |
H32B | −0.1987 | 0.2546 | 0.3118 | 0.046* | |
H32C | −0.0346 | 0.2636 | 0.2811 | 0.046* | |
C33 | −0.0074 (3) | 0.1635 (2) | 0.5327 (3) | 0.0297 (5) | |
H33A | 0.0626 | 0.1310 | 0.4792 | 0.045* | |
H33B | −0.1002 | 0.1187 | 0.5123 | 0.045* | |
H33C | 0.0361 | 0.1589 | 0.6334 | 0.045* | |
C34 | −0.1539 (3) | 0.3417 (2) | 0.5702 (3) | 0.0276 (5) | |
H34A | −0.1169 | 0.3322 | 0.6716 | 0.041* | |
H34B | −0.2483 | 0.2999 | 0.5419 | 0.041* | |
H34C | −0.1692 | 0.4248 | 0.5480 | 0.041* | |
C77 | 0.5584 (2) | 0.4281 (2) | 0.7748 (2) | 0.0229 (5) | |
H771 | 0.5843 | 0.4024 | 0.6856 | 0.027* | |
H772 | 0.5395 | 0.3575 | 0.8272 | 0.027* | |
C71 | 0.6879 (2) | 0.4941 (2) | 0.8603 (2) | 0.0211 (4) | |
C72 | 0.7903 (2) | 0.4388 (2) | 0.9637 (2) | 0.0206 (4) | |
H72 | 0.7736 | 0.3599 | 0.9864 | 0.025* | |
C73 | 0.9178 (2) | 0.4956 (2) | 1.0357 (2) | 0.0217 (4) | |
H73 | 0.9872 | 0.4557 | 1.1058 | 0.026* | |
C74 | 0.9419 (2) | 0.6107 (2) | 1.0038 (2) | 0.0217 (4) | |
C75 | 0.8382 (3) | 0.6695 (2) | 0.9034 (3) | 0.0293 (5) | |
H75 | 0.8531 | 0.7493 | 0.8836 | 0.035* | |
C76 | 0.7134 (3) | 0.6111 (2) | 0.8325 (3) | 0.0294 (5) | |
H76 | 0.6435 | 0.6516 | 0.7633 | 0.035* | |
O74 | 1.06483 (17) | 0.67453 (15) | 1.06569 (17) | 0.0273 (4) | |
C78 | 1.1825 (2) | 0.6116 (2) | 1.1548 (2) | 0.0276 (5) | |
H78A | 1.2138 | 0.5464 | 1.1023 | 0.041* | |
H78B | 1.1472 | 0.5812 | 1.2364 | 0.041* | |
H78C | 1.2670 | 0.6640 | 1.1868 | 0.041* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0159 (8) | 0.0201 (9) | 0.0186 (8) | −0.0020 (8) | 0.0043 (7) | −0.0002 (7) |
N2 | 0.0165 (8) | 0.0183 (9) | 0.0223 (9) | −0.0034 (7) | 0.0048 (7) | −0.0019 (7) |
C3 | 0.0170 (9) | 0.0156 (10) | 0.0231 (10) | 0.0005 (8) | 0.0052 (8) | 0.0006 (8) |
C3a | 0.0187 (9) | 0.0185 (10) | 0.0216 (10) | 0.0006 (9) | 0.0057 (8) | 0.0000 (8) |
C4 | 0.0260 (11) | 0.0307 (13) | 0.0223 (11) | −0.0057 (10) | 0.0058 (9) | −0.0024 (10) |
O5 | 0.0317 (8) | 0.0324 (10) | 0.0182 (7) | −0.0060 (8) | 0.0050 (6) | 0.0009 (7) |
C6 | 0.0284 (11) | 0.0246 (12) | 0.0196 (10) | −0.0034 (10) | 0.0054 (9) | −0.0029 (9) |
N7 | 0.0173 (8) | 0.0209 (9) | 0.0204 (9) | −0.0007 (8) | 0.0009 (7) | −0.0023 (8) |
C7a | 0.0205 (10) | 0.0173 (10) | 0.0187 (10) | 0.0007 (9) | 0.0038 (8) | 0.0006 (8) |
C11 | 0.0126 (9) | 0.0216 (11) | 0.0210 (10) | −0.0002 (9) | 0.0033 (7) | 0.0039 (9) |
C12 | 0.0217 (10) | 0.0231 (11) | 0.0233 (11) | −0.0006 (9) | 0.0034 (9) | 0.0023 (9) |
C13 | 0.0196 (10) | 0.0263 (13) | 0.0348 (13) | −0.0049 (10) | 0.0017 (9) | 0.0069 (10) |
C14 | 0.0175 (11) | 0.0397 (14) | 0.0291 (12) | 0.0008 (10) | 0.0070 (9) | 0.0124 (11) |
C15 | 0.0201 (10) | 0.0366 (14) | 0.0211 (10) | 0.0034 (10) | 0.0054 (8) | 0.0018 (10) |
C16 | 0.0191 (10) | 0.0239 (11) | 0.0237 (10) | 0.0009 (9) | 0.0036 (8) | 0.0008 (9) |
C31 | 0.0183 (10) | 0.0190 (10) | 0.0230 (10) | −0.0031 (9) | 0.0048 (8) | −0.0001 (9) |
C32 | 0.0219 (11) | 0.0404 (15) | 0.0286 (12) | −0.0102 (11) | 0.0029 (9) | −0.0019 (11) |
C33 | 0.0264 (11) | 0.0184 (12) | 0.0443 (15) | −0.0047 (10) | 0.0071 (11) | 0.0011 (11) |
C34 | 0.0203 (11) | 0.0274 (12) | 0.0376 (14) | −0.0023 (9) | 0.0118 (10) | −0.0039 (10) |
C77 | 0.0198 (10) | 0.0205 (11) | 0.0266 (11) | 0.0011 (9) | 0.0008 (9) | −0.0012 (9) |
C71 | 0.0199 (10) | 0.0218 (11) | 0.0211 (10) | 0.0008 (10) | 0.0032 (8) | −0.0024 (9) |
C72 | 0.0215 (10) | 0.0184 (11) | 0.0224 (10) | 0.0006 (9) | 0.0060 (8) | 0.0012 (9) |
C73 | 0.0194 (10) | 0.0267 (12) | 0.0186 (10) | 0.0039 (10) | 0.0029 (8) | 0.0005 (9) |
C74 | 0.0196 (10) | 0.0233 (11) | 0.0215 (10) | 0.0008 (9) | 0.0027 (8) | −0.0033 (9) |
C75 | 0.0300 (12) | 0.0175 (11) | 0.0352 (13) | −0.0035 (10) | −0.0052 (10) | 0.0040 (10) |
C76 | 0.0280 (12) | 0.0223 (12) | 0.0316 (12) | −0.0005 (10) | −0.0087 (10) | 0.0048 (10) |
O74 | 0.0204 (8) | 0.0249 (9) | 0.0320 (9) | −0.0018 (7) | −0.0054 (7) | −0.0001 (7) |
C78 | 0.0202 (11) | 0.0325 (13) | 0.0283 (12) | 0.0028 (10) | 0.0005 (9) | −0.0016 (11) |
N1—C7a | 1.367 (3) | C31—C33 | 1.535 (3) |
N1—N2 | 1.376 (2) | C31—C34 | 1.537 (3) |
N1—C11 | 1.428 (3) | C32—H32A | 0.9800 |
N2—C3 | 1.337 (3) | C32—H32B | 0.9800 |
C3—C3a | 1.419 (3) | C32—H32C | 0.9800 |
C3—C31 | 1.517 (3) | C33—H33A | 0.9800 |
C3a—C7a | 1.363 (3) | C33—H33B | 0.9800 |
C3a—C4 | 1.505 (3) | C33—H33C | 0.9800 |
C4—O5 | 1.442 (3) | C34—H34A | 0.9800 |
C4—H41 | 0.9900 | C34—H34B | 0.9800 |
C4—H42 | 0.9900 | C34—H34C | 0.9800 |
O5—C6 | 1.428 (3) | C77—C71 | 1.507 (3) |
C6—N7 | 1.464 (3) | C77—H771 | 0.9900 |
C6—H61 | 0.9900 | C77—H772 | 0.9900 |
C6—H62 | 0.9900 | C71—C72 | 1.382 (3) |
N7—C7a | 1.409 (3) | C71—C76 | 1.397 (3) |
N7—C77 | 1.488 (3) | C72—C73 | 1.396 (3) |
C11—C16 | 1.387 (3) | C72—H72 | 0.9500 |
C11—C12 | 1.393 (3) | C73—C74 | 1.381 (3) |
C12—C13 | 1.387 (3) | C73—H73 | 0.9500 |
C12—H12 | 0.9500 | C74—O74 | 1.376 (3) |
C13—C14 | 1.387 (4) | C74—C75 | 1.389 (3) |
C13—H13 | 0.9500 | C75—C76 | 1.383 (3) |
C14—C15 | 1.385 (4) | C75—H75 | 0.9500 |
C14—H14 | 0.9500 | C76—H76 | 0.9500 |
C15—C16 | 1.387 (3) | O74—C78 | 1.433 (3) |
C15—H15 | 0.9500 | C78—H78A | 0.9800 |
C16—H16 | 0.9500 | C78—H78B | 0.9800 |
C31—C32 | 1.528 (3) | C78—H78C | 0.9800 |
C7a—N1—N2 | 110.62 (16) | C32—C31—C34 | 108.62 (19) |
C7a—N1—C11 | 129.72 (18) | C33—C31—C34 | 109.7 (2) |
N2—N1—C11 | 119.66 (16) | C31—C32—H32A | 109.5 |
C3—N2—N1 | 105.30 (16) | C31—C32—H32B | 109.5 |
N2—C3—C3a | 110.95 (18) | H32A—C32—H32B | 109.5 |
N2—C3—C31 | 120.57 (19) | C31—C32—H32C | 109.5 |
C3a—C3—C31 | 128.40 (19) | H32A—C32—H32C | 109.5 |
C7a—C3a—C3 | 105.20 (18) | H32B—C32—H32C | 109.5 |
C7a—C3a—C4 | 119.99 (19) | C31—C33—H33A | 109.5 |
C3—C3a—C4 | 134.79 (19) | C31—C33—H33B | 109.5 |
O5—C4—C3a | 109.12 (17) | H33A—C33—H33B | 109.5 |
O5—C4—H41 | 109.9 | C31—C33—H33C | 109.5 |
C3a—C4—H41 | 109.9 | H33A—C33—H33C | 109.5 |
O5—C4—H42 | 109.9 | H33B—C33—H33C | 109.5 |
C3a—C4—H42 | 109.9 | C31—C34—H34A | 109.5 |
H41—C4—H42 | 108.3 | C31—C34—H34B | 109.5 |
C6—O5—C4 | 110.95 (17) | H34A—C34—H34B | 109.5 |
O5—C6—N7 | 112.76 (18) | C31—C34—H34C | 109.5 |
O5—C6—H61 | 109.0 | H34A—C34—H34C | 109.5 |
N7—C6—H61 | 109.0 | H34B—C34—H34C | 109.5 |
O5—C6—H62 | 109.0 | N7—C77—C71 | 112.32 (18) |
N7—C6—H62 | 109.0 | N7—C77—H771 | 109.1 |
H61—C6—H62 | 107.8 | C71—C77—H771 | 109.1 |
C7a—N7—C6 | 106.66 (17) | N7—C77—H772 | 109.1 |
C7a—N7—C77 | 112.44 (17) | C71—C77—H772 | 109.1 |
C6—N7—C77 | 112.53 (17) | H771—C77—H772 | 107.9 |
C3a—C7a—N1 | 107.92 (18) | C72—C71—C76 | 117.7 (2) |
C3a—C7a—N7 | 126.35 (19) | C72—C71—C77 | 121.0 (2) |
N1—C7a—N7 | 125.72 (19) | C76—C71—C77 | 121.3 (2) |
C16—C11—C12 | 120.7 (2) | C71—C72—C73 | 121.8 (2) |
C16—C11—N1 | 119.09 (19) | C71—C72—H72 | 119.1 |
C12—C11—N1 | 120.18 (19) | C73—C72—H72 | 119.1 |
C13—C12—C11 | 119.1 (2) | C74—C73—C72 | 119.3 (2) |
C13—C12—H12 | 120.4 | C74—C73—H73 | 120.4 |
C11—C12—H12 | 120.4 | C72—C73—H73 | 120.4 |
C14—C13—C12 | 120.6 (2) | O74—C74—C73 | 124.3 (2) |
C14—C13—H13 | 119.7 | O74—C74—C75 | 115.6 (2) |
C12—C13—H13 | 119.7 | C73—C74—C75 | 120.1 (2) |
C15—C14—C13 | 119.6 (2) | C76—C75—C74 | 119.7 (2) |
C15—C14—H14 | 120.2 | C76—C75—H75 | 120.2 |
C13—C14—H14 | 120.2 | C74—C75—H75 | 120.2 |
C14—C15—C16 | 120.6 (2) | C75—C76—C71 | 121.4 (2) |
C14—C15—H15 | 119.7 | C75—C76—H76 | 119.3 |
C16—C15—H15 | 119.7 | C71—C76—H76 | 119.3 |
C15—C16—C11 | 119.3 (2) | C74—O74—C78 | 116.52 (19) |
C15—C16—H16 | 120.3 | O74—C78—H78A | 109.5 |
C11—C16—H16 | 120.3 | O74—C78—H78B | 109.5 |
C3—C31—C32 | 111.16 (18) | H78A—C78—H78B | 109.5 |
C3—C31—C33 | 107.96 (18) | O74—C78—H78C | 109.5 |
C32—C31—C33 | 109.1 (2) | H78A—C78—H78C | 109.5 |
C3—C31—C34 | 110.31 (18) | H78B—C78—H78C | 109.5 |
C7a—N1—N2—C3 | 1.0 (2) | C16—C11—C12—C13 | −1.1 (3) |
C11—N1—N2—C3 | −178.62 (19) | N1—C11—C12—C13 | −178.8 (2) |
N1—N2—C3—C3a | −0.9 (2) | C11—C12—C13—C14 | 1.1 (3) |
N1—N2—C3—C31 | −177.94 (18) | C12—C13—C14—C15 | −0.4 (3) |
N2—C3—C3a—C7a | 0.5 (3) | C13—C14—C15—C16 | −0.4 (3) |
C31—C3—C3a—C7a | 177.2 (2) | C14—C15—C16—C11 | 0.5 (3) |
N2—C3—C3a—C4 | −177.7 (2) | C12—C11—C16—C15 | 0.3 (3) |
C31—C3—C3a—C4 | −1.0 (4) | N1—C11—C16—C15 | 178.0 (2) |
C7a—C3a—C4—O5 | −13.0 (3) | N2—C3—C31—C32 | −19.9 (3) |
C3—C3a—C4—O5 | 165.0 (2) | C3a—C3—C31—C32 | 163.7 (2) |
C3a—C4—O5—C6 | 46.4 (2) | N2—C3—C31—C33 | 99.7 (2) |
C4—O5—C6—N7 | −70.6 (2) | C3a—C3—C31—C33 | −76.7 (3) |
O5—C6—N7—C7a | 51.0 (2) | N2—C3—C31—C34 | −140.5 (2) |
O5—C6—N7—C77 | −72.7 (2) | C3a—C3—C31—C34 | 43.1 (3) |
C3—C3a—C7a—N1 | 0.1 (2) | C7a—N7—C77—C71 | 167.92 (18) |
C4—C3a—C7a—N1 | 178.65 (19) | C6—N7—C77—C71 | −71.6 (2) |
C3—C3a—C7a—N7 | 179.8 (2) | N7—C77—C71—C72 | 143.1 (2) |
C4—C3a—C7a—N7 | −1.7 (3) | N7—C77—C71—C76 | −40.8 (3) |
N2—N1—C7a—C3a | −0.7 (2) | C76—C71—C72—C73 | −1.9 (3) |
C11—N1—C7a—C3a | 178.9 (2) | C77—C71—C72—C73 | 174.37 (19) |
N2—N1—C7a—N7 | 179.6 (2) | C71—C72—C73—C74 | 0.6 (3) |
C11—N1—C7a—N7 | −0.8 (4) | C72—C73—C74—O74 | −178.5 (2) |
C6—N7—C7a—C3a | −16.3 (3) | C72—C73—C74—C75 | 1.5 (3) |
C77—N7—C7a—C3a | 107.5 (2) | O74—C74—C75—C76 | 177.9 (2) |
C6—N7—C7a—N1 | 163.4 (2) | C73—C74—C75—C76 | −2.1 (4) |
C77—N7—C7a—N1 | −72.8 (3) | C74—C75—C76—C71 | 0.6 (4) |
C7a—N1—C11—C16 | 145.6 (2) | C72—C71—C76—C75 | 1.3 (4) |
N2—N1—C11—C16 | −34.8 (3) | C77—C71—C76—C75 | −175.0 (2) |
C7a—N1—C11—C12 | −36.7 (3) | C73—C74—O74—C78 | 8.4 (3) |
N2—N1—C11—C12 | 142.89 (19) | C75—C74—O74—C78 | −171.6 (2) |
C23H24F3N3O | Z = 2 |
Mr = 415.45 | F(000) = 436 |
Triclinic, P1 | Dx = 1.379 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.0277 (11) Å | Cell parameters from 4601 reflections |
b = 9.8597 (12) Å | θ = 2.8–27.5° |
c = 12.6835 (18) Å | µ = 0.11 mm−1 |
α = 85.531 (11)° | T = 120 K |
β = 74.180 (11)° | Block, colourless |
γ = 67.162 (9)° | 0.27 × 0.17 × 0.14 mm |
V = 1000.6 (2) Å3 |
Bruker Nonius KappaCCD diffractometer | 4601 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 2336 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.099 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.8° |
ϕ & ω scans | h = −11→11 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −12→12 |
Tmin = 0.922, Tmax = 0.986 | l = −16→16 |
24473 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)] = 0.061 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.183 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0897P)2 + 0.1648P] where P = (Fo2 + 2Fc2)/3 |
4601 reflections | (Δ/σ)max = 0.001 |
274 parameters | Δρmax = 0.33 e Å−3 |
0 restraints | Δρmin = −0.37 e Å−3 |
C23H24F3N3O | γ = 67.162 (9)° |
Mr = 415.45 | V = 1000.6 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.0277 (11) Å | Mo Kα radiation |
b = 9.8597 (12) Å | µ = 0.11 mm−1 |
c = 12.6835 (18) Å | T = 120 K |
α = 85.531 (11)° | 0.27 × 0.17 × 0.14 mm |
β = 74.180 (11)° |
Bruker Nonius KappaCCD diffractometer | 4601 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2336 reflections with I > 2σ(I) |
Tmin = 0.922, Tmax = 0.986 | Rint = 0.099 |
24473 measured reflections |
R[F2 > 2σ(F2)] = 0.061 | 0 restraints |
wR(F2) = 0.183 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.33 e Å−3 |
4601 reflections | Δρmin = −0.37 e Å−3 |
274 parameters |
x | y | z | Uiso*/Ueq | ||
N1 | 0.4886 (3) | 0.3492 (2) | 0.64616 (18) | 0.0226 (5) | |
N2 | 0.4261 (3) | 0.2466 (2) | 0.63566 (18) | 0.0238 (5) | |
C3 | 0.2804 (3) | 0.2856 (3) | 0.7110 (2) | 0.0232 (6) | |
C3a | 0.2496 (3) | 0.4115 (3) | 0.7717 (2) | 0.0228 (6) | |
C4 | 0.1138 (3) | 0.4986 (3) | 0.8648 (2) | 0.0305 (7) | |
H41 | 0.0147 | 0.5592 | 0.8389 | 0.037* | |
H42 | 0.0823 | 0.4316 | 0.9206 | 0.037* | |
O5 | 0.1680 (2) | 0.5917 (2) | 0.91230 (16) | 0.0307 (5) | |
C6 | 0.2435 (3) | 0.6668 (3) | 0.8290 (2) | 0.0283 (7) | |
H6A | 0.2586 | 0.7455 | 0.8634 | 0.034* | |
H6B | 0.1677 | 0.7142 | 0.7816 | 0.034* | |
N7 | 0.4048 (3) | 0.5707 (2) | 0.76085 (19) | 0.0246 (5) | |
C7a | 0.3833 (3) | 0.4483 (3) | 0.7286 (2) | 0.0226 (6) | |
C11 | 0.6426 (3) | 0.3405 (3) | 0.5741 (2) | 0.0231 (6) | |
C12 | 0.6744 (3) | 0.4666 (3) | 0.5468 (2) | 0.0257 (6) | |
H12 | 0.5922 | 0.5598 | 0.5754 | 0.031* | |
C13 | 0.8258 (3) | 0.4568 (3) | 0.4780 (2) | 0.0285 (7) | |
H13 | 0.8495 | 0.5430 | 0.4613 | 0.034* | |
C14 | 0.9425 (3) | 0.3229 (3) | 0.4335 (2) | 0.0300 (7) | |
H14 | 1.0465 | 0.3164 | 0.3856 | 0.036* | |
C15 | 0.9082 (4) | 0.1983 (3) | 0.4584 (2) | 0.0313 (7) | |
H15 | 0.9883 | 0.1058 | 0.4267 | 0.038* | |
C16 | 0.7587 (3) | 0.2060 (3) | 0.5289 (2) | 0.0279 (7) | |
H16 | 0.7359 | 0.1194 | 0.5462 | 0.033* | |
C31 | 0.1718 (3) | 0.1983 (3) | 0.7238 (2) | 0.0255 (6) | |
C32 | 0.2356 (4) | 0.0882 (3) | 0.6284 (3) | 0.0321 (7) | |
H32A | 0.2279 | 0.1412 | 0.5602 | 0.048* | |
H32B | 0.1679 | 0.0283 | 0.6405 | 0.048* | |
H32C | 0.3520 | 0.0241 | 0.6230 | 0.048* | |
C33 | 0.1712 (4) | 0.1175 (3) | 0.8312 (2) | 0.0301 (7) | |
H33A | 0.2861 | 0.0566 | 0.8326 | 0.045* | |
H33B | 0.1079 | 0.0546 | 0.8374 | 0.045* | |
H33C | 0.1194 | 0.1893 | 0.8928 | 0.045* | |
C34 | −0.0068 (3) | 0.3020 (3) | 0.7275 (2) | 0.0296 (7) | |
H34A | −0.0508 | 0.3710 | 0.7904 | 0.044* | |
H34B | −0.0763 | 0.2444 | 0.7346 | 0.044* | |
H34C | −0.0079 | 0.3570 | 0.6597 | 0.044* | |
C77 | 0.5422 (3) | 0.5334 (3) | 0.8124 (2) | 0.0247 (6) | |
H771 | 0.6412 | 0.4535 | 0.7686 | 0.030* | |
H772 | 0.5101 | 0.4964 | 0.8865 | 0.030* | |
C71 | 0.5868 (3) | 0.6627 (3) | 0.8219 (2) | 0.0233 (6) | |
C72 | 0.6432 (3) | 0.6755 (3) | 0.9100 (2) | 0.0290 (7) | |
H72 | 0.6514 | 0.6032 | 0.9646 | 0.035* | |
C73 | 0.6875 (3) | 0.7914 (3) | 0.9196 (2) | 0.0296 (7) | |
H73 | 0.7257 | 0.7991 | 0.9808 | 0.036* | |
C74 | 0.6766 (3) | 0.8967 (3) | 0.8407 (2) | 0.0249 (6) | |
C75 | 0.6195 (3) | 0.8858 (3) | 0.7531 (2) | 0.0273 (7) | |
H75 | 0.6099 | 0.9590 | 0.6992 | 0.033* | |
C76 | 0.5760 (3) | 0.7689 (3) | 0.7433 (2) | 0.0281 (7) | |
H76 | 0.5382 | 0.7613 | 0.6819 | 0.034* | |
C78 | 0.7275 (4) | 1.0211 (3) | 0.8486 (2) | 0.0307 (7) | |
F1 | 0.7478 (3) | 1.0370 (2) | 0.94488 (16) | 0.0558 (6) | |
F2 | 0.8712 (3) | 1.0032 (3) | 0.7764 (2) | 0.0760 (8) | |
F3 | 0.6198 (3) | 1.1491 (2) | 0.8290 (2) | 0.0623 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0216 (12) | 0.0219 (12) | 0.0267 (13) | −0.0109 (10) | −0.0053 (10) | −0.0027 (10) |
N2 | 0.0245 (12) | 0.0245 (12) | 0.0262 (13) | −0.0125 (11) | −0.0081 (10) | 0.0008 (10) |
C3 | 0.0242 (14) | 0.0269 (15) | 0.0215 (15) | −0.0115 (12) | −0.0091 (12) | 0.0050 (12) |
C3a | 0.0213 (14) | 0.0247 (15) | 0.0246 (15) | −0.0117 (12) | −0.0052 (12) | 0.0009 (12) |
C4 | 0.0277 (15) | 0.0303 (16) | 0.0339 (17) | −0.0150 (13) | −0.0008 (13) | −0.0078 (13) |
O5 | 0.0303 (11) | 0.0329 (11) | 0.0310 (12) | −0.0180 (9) | 0.0002 (9) | −0.0083 (9) |
C6 | 0.0268 (15) | 0.0212 (15) | 0.0351 (17) | −0.0085 (13) | −0.0046 (13) | −0.0049 (13) |
N7 | 0.0215 (12) | 0.0221 (12) | 0.0317 (14) | −0.0096 (10) | −0.0065 (10) | −0.0031 (10) |
C7a | 0.0233 (14) | 0.0219 (15) | 0.0248 (15) | −0.0103 (12) | −0.0077 (12) | 0.0013 (12) |
C11 | 0.0210 (14) | 0.0294 (16) | 0.0203 (14) | −0.0108 (12) | −0.0061 (11) | 0.0005 (12) |
C12 | 0.0264 (15) | 0.0258 (16) | 0.0261 (15) | −0.0096 (13) | −0.0103 (12) | 0.0036 (12) |
C13 | 0.0321 (16) | 0.0339 (17) | 0.0263 (16) | −0.0183 (14) | −0.0118 (13) | 0.0077 (13) |
C14 | 0.0242 (15) | 0.0397 (18) | 0.0286 (17) | −0.0150 (14) | −0.0074 (13) | 0.0028 (14) |
C15 | 0.0260 (15) | 0.0355 (17) | 0.0304 (17) | −0.0094 (14) | −0.0067 (13) | −0.0025 (13) |
C16 | 0.0272 (15) | 0.0289 (17) | 0.0289 (16) | −0.0122 (13) | −0.0074 (13) | 0.0007 (13) |
C31 | 0.0284 (15) | 0.0268 (16) | 0.0269 (16) | −0.0158 (13) | −0.0084 (12) | 0.0012 (12) |
C32 | 0.0324 (16) | 0.0327 (17) | 0.0351 (18) | −0.0160 (14) | −0.0076 (13) | −0.0063 (14) |
C33 | 0.0340 (16) | 0.0312 (16) | 0.0318 (17) | −0.0183 (14) | −0.0121 (13) | 0.0060 (13) |
C34 | 0.0280 (15) | 0.0310 (17) | 0.0340 (17) | −0.0153 (14) | −0.0096 (13) | 0.0034 (13) |
C77 | 0.0262 (15) | 0.0234 (15) | 0.0283 (16) | −0.0118 (12) | −0.0101 (12) | 0.0024 (12) |
C71 | 0.0228 (14) | 0.0206 (15) | 0.0278 (16) | −0.0092 (12) | −0.0074 (12) | 0.0011 (12) |
C72 | 0.0353 (16) | 0.0285 (16) | 0.0288 (16) | −0.0164 (14) | −0.0128 (13) | 0.0072 (13) |
C73 | 0.0324 (16) | 0.0311 (17) | 0.0320 (17) | −0.0167 (14) | −0.0130 (13) | 0.0034 (13) |
C74 | 0.0241 (14) | 0.0223 (15) | 0.0293 (16) | −0.0103 (12) | −0.0056 (12) | −0.0016 (12) |
C75 | 0.0298 (15) | 0.0241 (15) | 0.0318 (17) | −0.0125 (13) | −0.0111 (13) | 0.0032 (13) |
C76 | 0.0307 (16) | 0.0298 (16) | 0.0292 (17) | −0.0155 (13) | −0.0108 (13) | 0.0013 (13) |
C78 | 0.0322 (16) | 0.0311 (17) | 0.0327 (17) | −0.0149 (14) | −0.0105 (14) | 0.0018 (14) |
F1 | 0.0983 (17) | 0.0503 (12) | 0.0516 (13) | −0.0498 (12) | −0.0422 (12) | 0.0113 (10) |
F2 | 0.0706 (15) | 0.0792 (16) | 0.0866 (17) | −0.0622 (14) | 0.0262 (13) | −0.0350 (13) |
F3 | 0.0826 (16) | 0.0310 (11) | 0.0995 (18) | −0.0281 (11) | −0.0592 (14) | 0.0160 (11) |
N1—C7a | 1.359 (3) | C31—C33 | 1.523 (4) |
N1—N2 | 1.366 (3) | C31—C34 | 1.528 (4) |
N1—C11 | 1.415 (3) | C32—H32A | 0.9800 |
N2—C3 | 1.330 (3) | C32—H32B | 0.9800 |
C3—C3a | 1.405 (4) | C32—H32C | 0.9800 |
C3—C31 | 1.509 (4) | C33—H33A | 0.9800 |
C3a—C7a | 1.356 (4) | C33—H33B | 0.9800 |
C3a—C4 | 1.478 (4) | C33—H33C | 0.9800 |
C4—O5 | 1.429 (3) | C34—H34A | 0.9800 |
C4—H41 | 0.9900 | C34—H34B | 0.9800 |
C4—H42 | 0.9900 | C34—H34C | 0.9800 |
O5—C6 | 1.416 (3) | C77—C71 | 1.500 (4) |
C6—N7 | 1.461 (3) | C77—H771 | 0.9900 |
C6—H6A | 0.9900 | C77—H772 | 0.9900 |
C6—H6B | 0.9900 | C71—C72 | 1.381 (4) |
N7—C7a | 1.401 (3) | C71—C76 | 1.382 (4) |
N7—C77 | 1.467 (3) | C72—C73 | 1.372 (4) |
C11—C16 | 1.378 (4) | C72—H72 | 0.9500 |
C11—C12 | 1.380 (4) | C73—C74 | 1.379 (4) |
C12—C13 | 1.379 (4) | C73—H73 | 0.9500 |
C12—H12 | 0.9500 | C74—C75 | 1.373 (4) |
C13—C14 | 1.373 (4) | C74—C78 | 1.486 (4) |
C13—H13 | 0.9500 | C75—C76 | 1.378 (4) |
C14—C15 | 1.374 (4) | C75—H75 | 0.9500 |
C14—H14 | 0.9500 | C76—H76 | 0.9500 |
C15—C16 | 1.378 (4) | C78—F1 | 1.313 (3) |
C15—H15 | 0.9500 | C78—F3 | 1.316 (3) |
C16—H16 | 0.9500 | C78—F2 | 1.324 (3) |
C31—C32 | 1.521 (4) | ||
C7a—N1—N2 | 110.5 (2) | C32—C31—C34 | 108.8 (2) |
C7a—N1—C11 | 130.3 (2) | C33—C31—C34 | 108.6 (2) |
N2—N1—C11 | 119.1 (2) | C31—C32—H32A | 109.5 |
C3—N2—N1 | 105.3 (2) | C31—C32—H32B | 109.5 |
N2—C3—C3a | 111.1 (2) | H32A—C32—H32B | 109.5 |
N2—C3—C31 | 121.0 (2) | C31—C32—H32C | 109.5 |
C3a—C3—C31 | 127.9 (2) | H32A—C32—H32C | 109.5 |
C7a—C3a—C3 | 105.2 (2) | H32B—C32—H32C | 109.5 |
C7a—C3a—C4 | 120.5 (2) | C31—C33—H33A | 109.5 |
C3—C3a—C4 | 134.3 (2) | C31—C33—H33B | 109.5 |
O5—C4—C3a | 109.6 (2) | H33A—C33—H33B | 109.5 |
O5—C4—H41 | 109.8 | C31—C33—H33C | 109.5 |
C3a—C4—H41 | 109.8 | H33A—C33—H33C | 109.5 |
O5—C4—H42 | 109.8 | H33B—C33—H33C | 109.5 |
C3a—C4—H42 | 109.8 | C31—C34—H34A | 109.5 |
H41—C4—H42 | 108.2 | C31—C34—H34B | 109.5 |
C6—O5—C4 | 109.9 (2) | H34A—C34—H34B | 109.5 |
O5—C6—N7 | 113.4 (2) | C31—C34—H34C | 109.5 |
O5—C6—H6A | 108.9 | H34A—C34—H34C | 109.5 |
N7—C6—H6A | 108.9 | H34B—C34—H34C | 109.5 |
O5—C6—H6B | 108.9 | N7—C77—C71 | 112.4 (2) |
N7—C6—H6B | 108.9 | N7—C77—H771 | 109.1 |
H6A—C6—H6B | 107.7 | C71—C77—H771 | 109.1 |
C7a—N7—C6 | 107.0 (2) | N7—C77—H772 | 109.1 |
C7a—N7—C77 | 114.1 (2) | C71—C77—H772 | 109.1 |
C6—N7—C77 | 113.9 (2) | H771—C77—H772 | 107.9 |
C3a—C7a—N1 | 107.9 (2) | C72—C71—C76 | 118.7 (2) |
C3a—C7a—N7 | 125.6 (2) | C72—C71—C77 | 119.6 (2) |
N1—C7a—N7 | 126.4 (2) | C76—C71—C77 | 121.7 (2) |
C16—C11—C12 | 120.2 (2) | C73—C72—C71 | 120.8 (3) |
C16—C11—N1 | 119.6 (2) | C73—C72—H72 | 119.6 |
C12—C11—N1 | 120.2 (2) | C71—C72—H72 | 119.6 |
C13—C12—C11 | 119.7 (3) | C72—C73—C74 | 120.1 (3) |
C13—C12—H12 | 120.1 | C72—C73—H73 | 119.9 |
C11—C12—H12 | 120.1 | C74—C73—H73 | 119.9 |
C14—C13—C12 | 120.3 (3) | C75—C74—C73 | 119.7 (2) |
C14—C13—H13 | 119.9 | C75—C74—C78 | 119.5 (3) |
C12—C13—H13 | 119.9 | C73—C74—C78 | 120.8 (3) |
C13—C14—C15 | 119.7 (3) | C74—C75—C76 | 120.1 (3) |
C13—C14—H14 | 120.2 | C74—C75—H75 | 120.0 |
C15—C14—H14 | 120.2 | C76—C75—H75 | 120.0 |
C14—C15—C16 | 120.7 (3) | C75—C76—C71 | 120.7 (3) |
C14—C15—H15 | 119.7 | C75—C76—H76 | 119.7 |
C16—C15—H15 | 119.7 | C71—C76—H76 | 119.7 |
C11—C16—C15 | 119.4 (3) | F1—C78—F3 | 105.8 (2) |
C11—C16—H16 | 120.3 | F1—C78—F2 | 106.1 (2) |
C15—C16—H16 | 120.3 | F3—C78—F2 | 106.2 (3) |
C3—C31—C32 | 110.7 (2) | F1—C78—C74 | 113.9 (2) |
C3—C31—C33 | 109.1 (2) | F3—C78—C74 | 113.1 (2) |
C32—C31—C33 | 109.9 (2) | F2—C78—C74 | 111.0 (2) |
C3—C31—C34 | 109.9 (2) | ||
C7a—N1—N2—C3 | 1.1 (3) | C11—C12—C13—C14 | 2.4 (4) |
C11—N1—N2—C3 | −178.1 (2) | C12—C13—C14—C15 | −0.4 (4) |
N1—N2—C3—C3a | −1.1 (3) | C13—C14—C15—C16 | −1.0 (4) |
N1—N2—C3—C31 | 179.3 (2) | C12—C11—C16—C15 | 1.6 (4) |
N2—C3—C3a—C7a | 0.7 (3) | N1—C11—C16—C15 | 179.7 (3) |
C31—C3—C3a—C7a | −179.8 (3) | C14—C15—C16—C11 | 0.4 (4) |
N2—C3—C3a—C4 | −178.1 (3) | N2—C3—C31—C32 | −11.1 (4) |
C31—C3—C3a—C4 | 1.4 (5) | C3a—C3—C31—C32 | 169.4 (3) |
C7a—C3a—C4—O5 | −14.1 (4) | N2—C3—C31—C33 | 109.9 (3) |
C3—C3a—C4—O5 | 164.6 (3) | C3a—C3—C31—C33 | −69.6 (3) |
C3a—C4—O5—C6 | 48.0 (3) | N2—C3—C31—C34 | −131.3 (3) |
C4—O5—C6—N7 | −70.4 (3) | C3a—C3—C31—C34 | 49.3 (4) |
O5—C6—N7—C7a | 49.1 (3) | C7a—N7—C77—C71 | 166.7 (2) |
O5—C6—N7—C77 | −78.1 (3) | C6—N7—C77—C71 | −70.0 (3) |
C3—C3a—C7a—N1 | 0.0 (3) | N7—C77—C71—C72 | 147.0 (3) |
C4—C3a—C7a—N1 | 179.0 (2) | N7—C77—C71—C76 | −34.2 (4) |
C3—C3a—C7a—N7 | 177.6 (3) | C76—C71—C72—C73 | 0.1 (4) |
C4—C3a—C7a—N7 | −3.4 (4) | C77—C71—C72—C73 | 178.9 (3) |
N2—N1—C7a—C3a | −0.7 (3) | C71—C72—C73—C74 | −0.2 (4) |
C11—N1—C7a—C3a | 178.4 (3) | C72—C73—C74—C75 | 0.7 (4) |
N2—N1—C7a—N7 | −178.3 (2) | C72—C73—C74—C78 | −178.7 (3) |
C11—N1—C7a—N7 | 0.9 (4) | C73—C74—C75—C76 | −1.1 (4) |
C6—N7—C7a—C3a | −13.0 (4) | C78—C74—C75—C76 | 178.3 (3) |
C77—N7—C7a—C3a | 114.0 (3) | C74—C75—C76—C71 | 1.0 (4) |
C6—N7—C7a—N1 | 164.1 (3) | C72—C71—C76—C75 | −0.5 (4) |
C77—N7—C7a—N1 | −68.9 (3) | C77—C71—C76—C75 | −179.2 (3) |
C7a—N1—C11—C16 | 153.5 (3) | C75—C74—C78—F1 | 167.1 (3) |
N2—N1—C11—C16 | −27.4 (4) | C73—C74—C78—F1 | −13.5 (4) |
C7a—N1—C11—C12 | −28.5 (4) | C75—C74—C78—F3 | 46.2 (4) |
N2—N1—C11—C12 | 150.6 (2) | C73—C74—C78—F3 | −134.5 (3) |
C16—C11—C12—C13 | −3.0 (4) | C75—C74—C78—F2 | −73.1 (3) |
N1—C11—C12—C13 | 179.0 (2) | C73—C74—C78—F2 | 106.3 (3) |
C22H24N4O3 | F(000) = 832 |
Mr = 392.45 | Dx = 1.350 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4417 reflections |
a = 19.164 (2) Å | θ = 3.0–27.5° |
b = 8.7781 (7) Å | µ = 0.09 mm−1 |
c = 11.7188 (12) Å | T = 120 K |
β = 101.717 (10)° | Block, colourless |
V = 1930.3 (3) Å3 | 0.33 × 0.22 × 0.18 mm |
Z = 4 |
Bruker Nonius KappaCCD diffractometer | 4417 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 2821 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.066 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.0° |
ϕ & ω scans | h = −24→22 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −11→11 |
Tmin = 0.917, Tmax = 0.984 | l = −15→15 |
27769 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)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.116 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0417P)2 + 0.8028P] where P = (Fo2 + 2Fc2)/3 |
4417 reflections | (Δ/σ)max = 0.001 |
265 parameters | Δρmax = 0.24 e Å−3 |
0 restraints | Δρmin = −0.29 e Å−3 |
C22H24N4O3 | V = 1930.3 (3) Å3 |
Mr = 392.45 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 19.164 (2) Å | µ = 0.09 mm−1 |
b = 8.7781 (7) Å | T = 120 K |
c = 11.7188 (12) Å | 0.33 × 0.22 × 0.18 mm |
β = 101.717 (10)° |
Bruker Nonius KappaCCD diffractometer | 4417 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2821 reflections with I > 2σ(I) |
Tmin = 0.917, Tmax = 0.984 | Rint = 0.066 |
27769 measured reflections |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.116 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.24 e Å−3 |
4417 reflections | Δρmin = −0.29 e Å−3 |
265 parameters |
x | y | z | Uiso*/Ueq | ||
N1 | 0.17204 (8) | 0.55410 (16) | 0.23144 (12) | 0.0185 (3) | |
N2 | 0.13203 (8) | 0.44005 (16) | 0.17103 (12) | 0.0199 (3) | |
C3 | 0.17817 (10) | 0.33411 (19) | 0.15485 (15) | 0.0194 (4) | |
C3a | 0.24844 (10) | 0.3789 (2) | 0.20425 (15) | 0.0203 (4) | |
C4 | 0.31945 (10) | 0.3060 (2) | 0.21820 (18) | 0.0260 (4) | |
H4A | 0.3239 | 0.2239 | 0.2772 | 0.031* | |
H4B | 0.3249 | 0.2600 | 0.1433 | 0.031* | |
O5 | 0.37385 (7) | 0.41726 (14) | 0.25414 (12) | 0.0289 (3) | |
C6 | 0.35922 (11) | 0.5099 (2) | 0.34553 (17) | 0.0273 (4) | |
H6A | 0.4017 | 0.5728 | 0.3767 | 0.033* | |
H6B | 0.3503 | 0.4436 | 0.4094 | 0.033* | |
N7 | 0.29830 (8) | 0.60942 (17) | 0.30890 (13) | 0.0222 (3) | |
C7a | 0.24188 (10) | 0.5184 (2) | 0.25078 (15) | 0.0199 (4) | |
C11 | 0.13728 (10) | 0.67668 (19) | 0.27440 (15) | 0.0203 (4) | |
C12 | 0.16550 (11) | 0.7367 (2) | 0.38298 (16) | 0.0240 (4) | |
H12 | 0.2085 | 0.6972 | 0.4281 | 0.029* | |
C13 | 0.13052 (11) | 0.8542 (2) | 0.42479 (17) | 0.0294 (5) | |
H13 | 0.1503 | 0.8984 | 0.4982 | 0.035* | |
C14 | 0.06747 (11) | 0.9080 (2) | 0.36157 (18) | 0.0317 (5) | |
H14 | 0.0432 | 0.9880 | 0.3919 | 0.038* | |
C15 | 0.03906 (11) | 0.8468 (2) | 0.25416 (18) | 0.0296 (5) | |
H15 | −0.0049 | 0.8840 | 0.2107 | 0.035* | |
C16 | 0.07437 (10) | 0.7313 (2) | 0.20947 (17) | 0.0247 (4) | |
H16 | 0.0554 | 0.6900 | 0.1347 | 0.030* | |
C31 | 0.15406 (10) | 0.1929 (2) | 0.08541 (16) | 0.0228 (4) | |
C32 | 0.07403 (11) | 0.1749 (2) | 0.06623 (18) | 0.0309 (5) | |
H32A | 0.0599 | 0.1640 | 0.1416 | 0.046* | |
H32B | 0.0594 | 0.0840 | 0.0188 | 0.046* | |
H32C | 0.0509 | 0.2650 | 0.0258 | 0.046* | |
C33 | 0.17561 (12) | 0.2072 (2) | −0.03238 (17) | 0.0323 (5) | |
H33A | 0.1526 | 0.2969 | −0.0735 | 0.049* | |
H33B | 0.1606 | 0.1157 | −0.0789 | 0.049* | |
H33C | 0.2275 | 0.2181 | −0.0205 | 0.049* | |
C34 | 0.18954 (11) | 0.0537 (2) | 0.14942 (17) | 0.0278 (4) | |
H34A | 0.2412 | 0.0604 | 0.1559 | 0.042* | |
H34B | 0.1716 | −0.0385 | 0.1061 | 0.042* | |
H34C | 0.1787 | 0.0493 | 0.2275 | 0.042* | |
C77 | 0.31303 (11) | 0.7374 (2) | 0.23620 (16) | 0.0255 (4) | |
H77A | 0.2673 | 0.7819 | 0.1955 | 0.031* | |
H77B | 0.3382 | 0.6985 | 0.1762 | 0.031* | |
C71 | 0.35735 (10) | 0.8601 (2) | 0.30497 (16) | 0.0234 (4) | |
C72 | 0.41127 (11) | 0.9289 (2) | 0.26129 (17) | 0.0282 (4) | |
H72 | 0.4218 | 0.8938 | 0.1900 | 0.034* | |
C73 | 0.44993 (10) | 1.0475 (2) | 0.31949 (17) | 0.0278 (4) | |
H73 | 0.4870 | 1.0946 | 0.2893 | 0.033* | |
C74 | 0.43360 (10) | 1.0959 (2) | 0.42199 (16) | 0.0236 (4) | |
C75 | 0.38145 (11) | 1.0289 (2) | 0.46880 (17) | 0.0282 (5) | |
H75 | 0.3717 | 1.0632 | 0.5409 | 0.034* | |
C76 | 0.34339 (11) | 0.9108 (2) | 0.40930 (16) | 0.0281 (4) | |
H76 | 0.3069 | 0.8632 | 0.4406 | 0.034* | |
N74 | 0.47224 (9) | 1.22504 (18) | 0.48294 (14) | 0.0287 (4) | |
O41 | 0.52493 (8) | 1.27042 (17) | 0.45079 (13) | 0.0397 (4) | |
O42 | 0.44975 (8) | 1.28234 (16) | 0.56310 (13) | 0.0382 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0223 (8) | 0.0153 (7) | 0.0175 (7) | 0.0007 (6) | 0.0032 (6) | −0.0025 (6) |
N2 | 0.0269 (9) | 0.0158 (7) | 0.0168 (7) | −0.0011 (7) | 0.0037 (6) | −0.0007 (6) |
C3 | 0.0277 (10) | 0.0152 (8) | 0.0157 (8) | 0.0012 (8) | 0.0053 (7) | 0.0016 (7) |
C3a | 0.0256 (10) | 0.0161 (8) | 0.0193 (9) | 0.0016 (8) | 0.0050 (7) | 0.0020 (7) |
C4 | 0.0255 (10) | 0.0183 (9) | 0.0343 (11) | 0.0002 (8) | 0.0061 (8) | −0.0012 (8) |
O5 | 0.0247 (7) | 0.0232 (7) | 0.0395 (8) | 0.0000 (6) | 0.0080 (6) | −0.0060 (6) |
C6 | 0.0282 (11) | 0.0233 (10) | 0.0286 (10) | 0.0022 (8) | 0.0014 (8) | −0.0017 (8) |
N7 | 0.0250 (9) | 0.0182 (8) | 0.0223 (8) | 0.0000 (7) | 0.0021 (6) | 0.0012 (6) |
C7a | 0.0245 (10) | 0.0175 (9) | 0.0176 (8) | 0.0005 (8) | 0.0042 (7) | 0.0009 (7) |
C11 | 0.0266 (10) | 0.0133 (8) | 0.0227 (9) | 0.0005 (7) | 0.0094 (8) | 0.0008 (7) |
C12 | 0.0311 (11) | 0.0206 (9) | 0.0218 (9) | −0.0012 (8) | 0.0086 (8) | −0.0004 (8) |
C13 | 0.0397 (12) | 0.0241 (10) | 0.0282 (10) | −0.0038 (9) | 0.0157 (9) | −0.0063 (9) |
C14 | 0.0381 (12) | 0.0191 (10) | 0.0443 (12) | 0.0008 (9) | 0.0233 (10) | −0.0045 (9) |
C15 | 0.0271 (11) | 0.0215 (10) | 0.0425 (12) | 0.0040 (8) | 0.0125 (9) | 0.0012 (9) |
C16 | 0.0269 (10) | 0.0216 (9) | 0.0269 (10) | 0.0000 (8) | 0.0084 (8) | −0.0006 (8) |
C31 | 0.0294 (11) | 0.0181 (9) | 0.0209 (9) | 0.0003 (8) | 0.0048 (8) | −0.0013 (8) |
C32 | 0.0316 (11) | 0.0232 (10) | 0.0359 (11) | −0.0025 (9) | 0.0024 (9) | −0.0076 (9) |
C33 | 0.0513 (13) | 0.0244 (10) | 0.0232 (10) | −0.0016 (10) | 0.0121 (9) | −0.0069 (8) |
C34 | 0.0338 (11) | 0.0168 (9) | 0.0318 (10) | 0.0005 (8) | 0.0041 (9) | 0.0001 (8) |
C77 | 0.0309 (11) | 0.0206 (9) | 0.0248 (10) | −0.0021 (8) | 0.0053 (8) | 0.0011 (8) |
C71 | 0.0270 (10) | 0.0187 (9) | 0.0240 (9) | 0.0015 (8) | 0.0037 (8) | 0.0019 (8) |
C72 | 0.0310 (11) | 0.0288 (10) | 0.0260 (10) | 0.0004 (9) | 0.0084 (9) | −0.0022 (9) |
C73 | 0.0245 (10) | 0.0279 (10) | 0.0320 (11) | −0.0029 (8) | 0.0079 (8) | 0.0016 (9) |
C74 | 0.0241 (10) | 0.0182 (9) | 0.0267 (10) | −0.0013 (8) | 0.0010 (8) | 0.0000 (8) |
C75 | 0.0359 (12) | 0.0249 (10) | 0.0250 (10) | −0.0025 (9) | 0.0089 (9) | −0.0034 (8) |
C76 | 0.0336 (11) | 0.0263 (10) | 0.0272 (10) | −0.0074 (9) | 0.0128 (9) | −0.0014 (9) |
N74 | 0.0300 (10) | 0.0239 (8) | 0.0302 (9) | −0.0032 (7) | 0.0015 (8) | 0.0047 (8) |
O41 | 0.0374 (9) | 0.0395 (9) | 0.0419 (9) | −0.0142 (7) | 0.0075 (7) | 0.0012 (7) |
O42 | 0.0473 (9) | 0.0304 (8) | 0.0373 (8) | −0.0077 (7) | 0.0095 (7) | −0.0109 (7) |
N1—C7a | 1.348 (2) | C31—C32 | 1.512 (3) |
N1—N2 | 1.368 (2) | C31—C34 | 1.521 (3) |
N1—C11 | 1.411 (2) | C31—C33 | 1.524 (3) |
N2—C3 | 1.323 (2) | C32—H32A | 0.9800 |
C3—C3a | 1.409 (3) | C32—H32B | 0.9800 |
C3—C31 | 1.503 (2) | C32—H32C | 0.9800 |
C3a—C7a | 1.357 (2) | C33—H33A | 0.9800 |
C3a—C4 | 1.483 (3) | C33—H33B | 0.9800 |
C4—O5 | 1.428 (2) | C33—H33C | 0.9800 |
C4—H4A | 0.9900 | C34—H34A | 0.9800 |
C4—H4B | 0.9900 | C34—H34B | 0.9800 |
O5—C6 | 1.417 (2) | C34—H34C | 0.9800 |
C6—N7 | 1.451 (2) | C77—C71 | 1.501 (3) |
C6—H6A | 0.9900 | C77—H77A | 0.9900 |
C6—H6B | 0.9900 | C77—H77B | 0.9900 |
N7—C7a | 1.404 (2) | C71—C76 | 1.377 (3) |
N7—C77 | 1.472 (2) | C71—C72 | 1.382 (3) |
C11—C16 | 1.375 (3) | C72—C73 | 1.376 (3) |
C11—C12 | 1.382 (3) | C72—H72 | 0.9500 |
C12—C13 | 1.374 (3) | C73—C74 | 1.369 (3) |
C12—H12 | 0.9500 | C73—H73 | 0.9500 |
C13—C14 | 1.367 (3) | C74—C75 | 1.367 (3) |
C13—H13 | 0.9500 | C74—N74 | 1.459 (2) |
C14—C15 | 1.375 (3) | C75—C76 | 1.374 (3) |
C14—H14 | 0.9500 | C75—H75 | 0.9500 |
C15—C16 | 1.380 (3) | C76—H76 | 0.9500 |
C15—H15 | 0.9500 | N74—O41 | 1.214 (2) |
C16—H16 | 0.9500 | N74—O42 | 1.219 (2) |
C7a—N1—N2 | 110.50 (14) | C32—C31—C34 | 109.12 (16) |
C7a—N1—C11 | 129.91 (15) | C3—C31—C33 | 108.22 (15) |
N2—N1—C11 | 119.14 (14) | C32—C31—C33 | 109.09 (16) |
C3—N2—N1 | 105.53 (14) | C34—C31—C33 | 109.66 (16) |
N2—C3—C3a | 110.82 (15) | C31—C32—H32A | 109.5 |
N2—C3—C31 | 121.07 (16) | C31—C32—H32B | 109.5 |
C3a—C3—C31 | 128.00 (16) | H32A—C32—H32B | 109.5 |
C7a—C3a—C3 | 104.97 (16) | C31—C32—H32C | 109.5 |
C7a—C3a—C4 | 120.24 (17) | H32A—C32—H32C | 109.5 |
C3—C3a—C4 | 134.71 (16) | H32B—C32—H32C | 109.5 |
O5—C4—C3a | 109.60 (14) | C31—C33—H33A | 109.5 |
O5—C4—H4A | 109.7 | C31—C33—H33B | 109.5 |
C3a—C4—H4A | 109.7 | H33A—C33—H33B | 109.5 |
O5—C4—H4B | 109.8 | C31—C33—H33C | 109.5 |
C3a—C4—H4B | 109.7 | H33A—C33—H33C | 109.5 |
H4A—C4—H4B | 108.2 | H33B—C33—H33C | 109.5 |
C6—O5—C4 | 111.76 (15) | C31—C34—H34A | 109.5 |
O5—C6—N7 | 113.11 (15) | C31—C34—H34B | 109.5 |
O5—C6—H6A | 109.0 | H34A—C34—H34B | 109.5 |
N7—C6—H6A | 109.0 | C31—C34—H34C | 109.5 |
O5—C6—H6B | 109.0 | H34A—C34—H34C | 109.5 |
N7—C6—H6B | 109.0 | H34B—C34—H34C | 109.5 |
H6A—C6—H6B | 107.8 | N7—C77—C71 | 113.03 (15) |
C7a—N7—C6 | 107.16 (14) | N7—C77—H77A | 109.0 |
C7a—N7—C77 | 111.89 (14) | C71—C77—H77A | 109.0 |
C6—N7—C77 | 113.17 (15) | N7—C77—H77B | 109.0 |
N1—C7a—C3a | 108.17 (16) | C71—C77—H77B | 109.0 |
N1—C7a—N7 | 126.15 (16) | H77A—C77—H77B | 107.8 |
C3a—C7a—N7 | 125.68 (17) | C76—C71—C72 | 118.85 (17) |
C16—C11—C12 | 120.79 (17) | C76—C71—C77 | 121.16 (17) |
C16—C11—N1 | 119.54 (16) | C72—C71—C77 | 119.93 (17) |
C12—C11—N1 | 119.62 (16) | C73—C72—C71 | 121.00 (18) |
C13—C12—C11 | 119.11 (18) | C73—C72—H72 | 119.5 |
C13—C12—H12 | 120.4 | C71—C72—H72 | 119.5 |
C11—C12—H12 | 120.4 | C74—C73—C72 | 118.29 (18) |
C14—C13—C12 | 120.53 (19) | C74—C73—H73 | 120.9 |
C14—C13—H13 | 119.7 | C72—C73—H73 | 120.9 |
C12—C13—H13 | 119.7 | C75—C74—C73 | 122.30 (17) |
C13—C14—C15 | 120.19 (18) | C75—C74—N74 | 118.54 (17) |
C13—C14—H14 | 119.9 | C73—C74—N74 | 119.15 (17) |
C15—C14—H14 | 119.9 | C74—C75—C76 | 118.51 (18) |
C14—C15—C16 | 120.08 (19) | C74—C75—H75 | 120.7 |
C14—C15—H15 | 120.0 | C76—C75—H75 | 120.7 |
C16—C15—H15 | 120.0 | C75—C76—C71 | 121.03 (18) |
C11—C16—C15 | 119.26 (18) | C75—C76—H76 | 119.5 |
C11—C16—H16 | 120.4 | C71—C76—H76 | 119.5 |
C15—C16—H16 | 120.4 | O41—N74—O42 | 123.38 (17) |
C3—C31—C32 | 110.96 (16) | O41—N74—C74 | 118.32 (17) |
C3—C31—C34 | 109.77 (14) | O42—N74—C74 | 118.30 (17) |
C7a—N1—N2—C3 | 0.60 (18) | N1—C11—C12—C13 | −178.85 (17) |
C11—N1—N2—C3 | −172.49 (15) | C11—C12—C13—C14 | 2.0 (3) |
N1—N2—C3—C3a | −0.23 (19) | C12—C13—C14—C15 | −1.2 (3) |
N1—N2—C3—C31 | −176.79 (15) | C13—C14—C15—C16 | −0.4 (3) |
N2—C3—C3a—C7a | −0.2 (2) | C12—C11—C16—C15 | −0.4 (3) |
C31—C3—C3a—C7a | 176.05 (17) | N1—C11—C16—C15 | 177.23 (17) |
N2—C3—C3a—C4 | 176.27 (19) | C14—C15—C16—C11 | 1.2 (3) |
C31—C3—C3a—C4 | −7.5 (3) | N2—C3—C31—C32 | −13.8 (2) |
C7a—C3a—C4—O5 | −15.8 (2) | C3a—C3—C31—C32 | 170.30 (17) |
C3—C3a—C4—O5 | 168.15 (18) | N2—C3—C31—C34 | −134.47 (18) |
C3a—C4—O5—C6 | 46.1 (2) | C3a—C3—C31—C34 | 49.6 (2) |
C4—O5—C6—N7 | −68.28 (19) | N2—C3—C31—C33 | 105.9 (2) |
O5—C6—N7—C7a | 50.6 (2) | C3a—C3—C31—C33 | −70.0 (2) |
O5—C6—N7—C77 | −73.20 (19) | C7a—N7—C77—C71 | 163.49 (15) |
N2—N1—C7a—C3a | −0.75 (19) | C6—N7—C77—C71 | −75.3 (2) |
C11—N1—C7a—C3a | 171.38 (17) | N7—C77—C71—C76 | −44.2 (2) |
N2—N1—C7a—N7 | 179.23 (16) | N7—C77—C71—C72 | 138.65 (18) |
C11—N1—C7a—N7 | −8.6 (3) | C76—C71—C72—C73 | −1.0 (3) |
C3—C3a—C7a—N1 | 0.57 (19) | C77—C71—C72—C73 | 176.26 (17) |
C4—C3a—C7a—N1 | −176.53 (16) | C71—C72—C73—C74 | −0.1 (3) |
C3—C3a—C7a—N7 | −179.41 (17) | C72—C73—C74—C75 | 1.2 (3) |
C4—C3a—C7a—N7 | 3.5 (3) | C72—C73—C74—N74 | −177.83 (17) |
C6—N7—C7a—N1 | 160.40 (17) | C73—C74—C75—C76 | −1.3 (3) |
C77—N7—C7a—N1 | −75.0 (2) | N74—C74—C75—C76 | 177.76 (16) |
C6—N7—C7a—C3a | −19.6 (2) | C74—C75—C76—C71 | 0.2 (3) |
C77—N7—C7a—C3a | 105.0 (2) | C72—C71—C76—C75 | 0.9 (3) |
C7a—N1—C11—C16 | 151.56 (18) | C77—C71—C76—C75 | −176.30 (18) |
N2—N1—C11—C16 | −36.9 (2) | C75—C74—N74—O41 | 169.66 (18) |
C7a—N1—C11—C12 | −30.8 (3) | C73—C74—N74—O41 | −11.3 (3) |
N2—N1—C11—C12 | 140.79 (17) | C75—C74—N74—O42 | −10.7 (3) |
C16—C11—C12—C13 | −1.2 (3) | C73—C74—N74—O42 | 168.33 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
C12—H12···N7 | 0.95 | 2.55 | 3.062 (3) | 114 |
C13—H13···N2i | 0.95 | 2.55 | 3.399 (2) | 148 |
C72—H72···O41ii | 0.95 | 2.37 | 3.293 (3) | 163 |
C75—H75···O5i | 0.95 | 2.50 | 3.409 (2) | 161 |
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) −x+1, y−1/2, −z+1/2. |
C24H29N3O3 | F(000) = 436 |
Mr = 407.50 | Dx = 1.270 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 2560 reflections |
a = 8.8268 (10) Å | θ = 2.9–27.5° |
b = 11.6521 (10) Å | µ = 0.09 mm−1 |
c = 10.3831 (7) Å | T = 120 K |
β = 93.747 (9)° | Block, colourless |
V = 1065.63 (17) Å3 | 0.25 × 0.20 × 0.19 mm |
Z = 2 |
Bruker Nonius KappaCCD diffractometer | 2560 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 2132 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.049 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.9° |
ϕ & ω scans | h = −10→11 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −15→15 |
Tmin = 0.972, Tmax = 0.984 | l = −13→13 |
17934 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) = 0.112 | H-atom parameters constrained |
S = 1.13 | w = 1/[σ2(Fo2) + (0.0582P)2 + 0.2363P] where P = (Fo2 + 2Fc2)/3 |
2560 reflections | (Δ/σ)max = 0.001 |
276 parameters | Δρmax = 0.32 e Å−3 |
1 restraint | Δρmin = −0.27 e Å−3 |
C24H29N3O3 | V = 1065.63 (17) Å3 |
Mr = 407.50 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 8.8268 (10) Å | µ = 0.09 mm−1 |
b = 11.6521 (10) Å | T = 120 K |
c = 10.3831 (7) Å | 0.25 × 0.20 × 0.19 mm |
β = 93.747 (9)° |
Bruker Nonius KappaCCD diffractometer | 2560 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2132 reflections with I > 2σ(I) |
Tmin = 0.972, Tmax = 0.984 | Rint = 0.049 |
17934 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 1 restraint |
wR(F2) = 0.112 | H-atom parameters constrained |
S = 1.13 | Δρmax = 0.32 e Å−3 |
2560 reflections | Δρmin = −0.27 e Å−3 |
276 parameters |
x | y | z | Uiso*/Ueq | ||
N1 | 0.3022 (2) | 0.4490 (2) | 0.4889 (2) | 0.0157 (4) | |
N2 | 0.1865 (2) | 0.3913 (2) | 0.4230 (2) | 0.0174 (5) | |
C3 | 0.0949 (3) | 0.3576 (2) | 0.5109 (3) | 0.0174 (5) | |
C3a | 0.1515 (3) | 0.3914 (2) | 0.6361 (2) | 0.0179 (5) | |
C4 | 0.1027 (3) | 0.3716 (3) | 0.7690 (3) | 0.0240 (6) | |
H41 | 0.0164 | 0.4226 | 0.7856 | 0.029* | |
H42 | 0.0694 | 0.2911 | 0.7782 | 0.029* | |
O5 | 0.2274 (2) | 0.3952 (2) | 0.85908 (18) | 0.0269 (5) | |
C6 | 0.2934 (3) | 0.5015 (3) | 0.8311 (3) | 0.0236 (6) | |
H6A | 0.3637 | 0.5243 | 0.9048 | 0.028* | |
H6B | 0.2125 | 0.5602 | 0.8215 | 0.028* | |
N7 | 0.3762 (2) | 0.5000 (2) | 0.7145 (2) | 0.0182 (5) | |
C7a | 0.2809 (3) | 0.4492 (2) | 0.6175 (2) | 0.0158 (5) | |
C11 | 0.4128 (3) | 0.5039 (2) | 0.4180 (2) | 0.0170 (5) | |
C12 | 0.4874 (3) | 0.6006 (2) | 0.4672 (3) | 0.0212 (6) | |
H12 | 0.4659 | 0.6296 | 0.5495 | 0.025* | |
C13 | 0.5929 (3) | 0.6545 (3) | 0.3959 (3) | 0.0283 (7) | |
H13 | 0.6465 | 0.7194 | 0.4303 | 0.034* | |
C14 | 0.6210 (4) | 0.6144 (3) | 0.2752 (3) | 0.0330 (7) | |
H14 | 0.6917 | 0.6529 | 0.2253 | 0.040* | |
C15 | 0.5466 (4) | 0.5187 (3) | 0.2270 (3) | 0.0312 (7) | |
H15 | 0.5666 | 0.4911 | 0.1437 | 0.037* | |
C16 | 0.4432 (3) | 0.4622 (3) | 0.2981 (3) | 0.0247 (6) | |
H16 | 0.3933 | 0.3952 | 0.2648 | 0.030* | |
C31 | −0.0462 (3) | 0.2893 (3) | 0.4749 (3) | 0.0235 (6) | |
C32 | −0.0813 (4) | 0.2882 (4) | 0.3301 (4) | 0.0504 (11) | |
H32A | 0.0017 | 0.2506 | 0.2882 | 0.076* | |
H32B | −0.0924 | 0.3673 | 0.2985 | 0.076* | |
H32C | −0.1761 | 0.2462 | 0.3099 | 0.076* | |
C33 | −0.0237 (5) | 0.1683 (4) | 0.5229 (5) | 0.0609 (13) | |
H33A | 0.0623 | 0.1336 | 0.4822 | 0.091* | |
H33B | −0.1157 | 0.1235 | 0.5011 | 0.091* | |
H33C | −0.0029 | 0.1691 | 0.6168 | 0.091* | |
C34 | −0.1807 (4) | 0.3434 (4) | 0.5375 (4) | 0.0484 (10) | |
H34A | −0.2737 | 0.3015 | 0.5105 | 0.073* | |
H34B | −0.1910 | 0.4237 | 0.5105 | 0.073* | |
H34C | −0.1637 | 0.3395 | 0.6316 | 0.073* | |
C77 | 0.5243 (3) | 0.4430 (3) | 0.7320 (3) | 0.0214 (6) | |
H771 | 0.5670 | 0.4331 | 0.6468 | 0.026* | |
H772 | 0.5108 | 0.3659 | 0.7695 | 0.026* | |
C71 | 0.6336 (3) | 0.5108 (3) | 0.8188 (2) | 0.0212 (6) | |
C72 | 0.7422 (3) | 0.4524 (3) | 0.8952 (3) | 0.0212 (6) | |
C73 | 0.8490 (3) | 0.5121 (3) | 0.9750 (2) | 0.0228 (6) | |
C74 | 0.8468 (3) | 0.6304 (3) | 0.9762 (3) | 0.0267 (7) | |
H74 | 0.9204 | 0.6718 | 1.0284 | 0.032* | |
C75 | 0.7370 (4) | 0.6881 (3) | 0.9010 (3) | 0.0322 (7) | |
H75 | 0.7339 | 0.7695 | 0.9035 | 0.039* | |
C76 | 0.6325 (4) | 0.6298 (3) | 0.8230 (3) | 0.0294 (7) | |
H76 | 0.5586 | 0.6712 | 0.7711 | 0.035* | |
O72 | 0.7503 (2) | 0.33556 (17) | 0.8866 (2) | 0.0245 (5) | |
O73 | 0.9489 (2) | 0.4453 (2) | 1.04560 (19) | 0.0309 (5) | |
C721 | 0.6800 (5) | 0.2777 (3) | 0.9867 (3) | 0.0417 (9) | |
H72A | 0.7365 | 0.2929 | 1.0693 | 0.063* | |
H72B | 0.6795 | 0.1949 | 0.9696 | 0.063* | |
H72C | 0.5754 | 0.3050 | 0.9904 | 0.063* | |
C731 | 1.0616 (4) | 0.5035 (4) | 1.1260 (3) | 0.0373 (8) | |
H73A | 1.1234 | 0.5516 | 1.0725 | 0.056* | |
H73B | 1.1266 | 0.4470 | 1.1726 | 0.056* | |
H73C | 1.0120 | 0.5518 | 1.1881 | 0.056* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0135 (10) | 0.0169 (11) | 0.0166 (10) | −0.0016 (9) | 0.0008 (8) | −0.0008 (9) |
N2 | 0.0145 (10) | 0.0183 (11) | 0.0190 (11) | −0.0019 (9) | −0.0010 (8) | −0.0031 (9) |
C3 | 0.0158 (12) | 0.0150 (13) | 0.0213 (13) | −0.0010 (10) | 0.0004 (10) | 0.0001 (10) |
C3a | 0.0170 (12) | 0.0158 (13) | 0.0209 (12) | 0.0017 (11) | 0.0027 (10) | 0.0008 (11) |
C4 | 0.0253 (13) | 0.0272 (17) | 0.0200 (13) | −0.0067 (12) | 0.0045 (11) | 0.0003 (11) |
O5 | 0.0301 (10) | 0.0327 (12) | 0.0180 (9) | −0.0027 (10) | 0.0019 (8) | 0.0029 (9) |
C6 | 0.0271 (14) | 0.0257 (15) | 0.0177 (13) | −0.0002 (13) | 0.0008 (11) | −0.0038 (12) |
N7 | 0.0166 (10) | 0.0203 (12) | 0.0175 (10) | 0.0014 (10) | −0.0012 (8) | −0.0033 (10) |
C7a | 0.0167 (12) | 0.0137 (12) | 0.0169 (12) | 0.0010 (11) | 0.0001 (9) | 0.0006 (10) |
C11 | 0.0156 (11) | 0.0175 (13) | 0.0177 (12) | −0.0005 (11) | 0.0001 (9) | 0.0021 (11) |
C12 | 0.0237 (13) | 0.0172 (14) | 0.0229 (14) | −0.0016 (11) | 0.0025 (11) | −0.0019 (11) |
C13 | 0.0239 (14) | 0.0260 (16) | 0.0353 (17) | −0.0055 (12) | 0.0032 (12) | 0.0038 (13) |
C14 | 0.0288 (16) | 0.0359 (18) | 0.0353 (17) | −0.0063 (14) | 0.0106 (13) | 0.0080 (14) |
C15 | 0.0317 (16) | 0.0391 (19) | 0.0239 (14) | −0.0013 (15) | 0.0104 (12) | −0.0044 (14) |
C16 | 0.0205 (14) | 0.0300 (17) | 0.0238 (14) | −0.0027 (12) | 0.0030 (11) | −0.0040 (12) |
C31 | 0.0187 (13) | 0.0232 (16) | 0.0288 (15) | −0.0074 (12) | 0.0021 (11) | −0.0039 (12) |
C32 | 0.042 (2) | 0.071 (3) | 0.0373 (19) | −0.031 (2) | 0.0003 (16) | −0.0133 (19) |
C33 | 0.059 (3) | 0.032 (2) | 0.087 (3) | −0.023 (2) | −0.028 (2) | 0.009 (2) |
C34 | 0.0220 (16) | 0.059 (3) | 0.064 (2) | −0.0087 (16) | 0.0047 (16) | −0.023 (2) |
C77 | 0.0191 (13) | 0.0219 (14) | 0.0222 (13) | −0.0007 (12) | −0.0061 (10) | −0.0006 (12) |
C71 | 0.0208 (13) | 0.0232 (15) | 0.0192 (13) | −0.0039 (12) | −0.0015 (10) | −0.0006 (12) |
C72 | 0.0199 (13) | 0.0262 (15) | 0.0177 (13) | 0.0001 (12) | 0.0021 (10) | −0.0014 (12) |
C73 | 0.0193 (13) | 0.0339 (17) | 0.0151 (12) | 0.0006 (13) | 0.0008 (10) | −0.0001 (12) |
C74 | 0.0263 (15) | 0.0326 (18) | 0.0206 (14) | −0.0117 (13) | −0.0037 (12) | −0.0013 (12) |
C75 | 0.0445 (19) | 0.0215 (16) | 0.0296 (16) | −0.0109 (14) | −0.0047 (14) | −0.0025 (13) |
C76 | 0.0346 (17) | 0.0236 (17) | 0.0284 (16) | −0.0031 (13) | −0.0106 (13) | 0.0017 (12) |
O72 | 0.0250 (10) | 0.0219 (11) | 0.0263 (10) | 0.0042 (8) | −0.0013 (8) | −0.0027 (8) |
O73 | 0.0230 (10) | 0.0419 (13) | 0.0261 (10) | 0.0027 (10) | −0.0107 (8) | −0.0065 (10) |
C721 | 0.064 (2) | 0.0262 (18) | 0.0343 (18) | −0.0009 (17) | 0.0028 (17) | 0.0078 (14) |
C731 | 0.0262 (15) | 0.057 (2) | 0.0270 (15) | −0.0041 (17) | −0.0093 (12) | −0.0048 (17) |
N1—C7a | 1.360 (3) | C32—H32A | 0.9800 |
N1—N2 | 1.368 (3) | C32—H32B | 0.9800 |
N1—C11 | 1.414 (3) | C32—H32C | 0.9800 |
N2—C3 | 1.318 (3) | C33—H33A | 0.9800 |
C3—C3a | 1.417 (4) | C33—H33B | 0.9800 |
C3—C31 | 1.504 (4) | C33—H33C | 0.9800 |
C3a—C7a | 1.351 (4) | C34—H34A | 0.9800 |
C3a—C4 | 1.490 (4) | C34—H34B | 0.9800 |
C4—O5 | 1.424 (3) | C34—H34C | 0.9800 |
C4—H41 | 0.9900 | C77—C71 | 1.501 (4) |
C4—H42 | 0.9900 | C77—H771 | 0.9900 |
O5—C6 | 1.407 (4) | C77—H772 | 0.9900 |
C6—N7 | 1.454 (3) | C71—C72 | 1.383 (4) |
C6—H6A | 0.9900 | C71—C76 | 1.388 (5) |
C6—H6B | 0.9900 | C72—O72 | 1.367 (4) |
N7—C7a | 1.401 (3) | C72—C73 | 1.398 (4) |
N7—C77 | 1.466 (4) | C73—O73 | 1.355 (4) |
C11—C16 | 1.379 (4) | C73—C74 | 1.378 (5) |
C11—C12 | 1.385 (4) | C74—C75 | 1.380 (5) |
C12—C13 | 1.378 (4) | C74—H74 | 0.9500 |
C12—H12 | 0.9500 | C75—C76 | 1.367 (4) |
C13—C14 | 1.375 (5) | C75—H75 | 0.9500 |
C13—H13 | 0.9500 | C76—H76 | 0.9500 |
C14—C15 | 1.371 (5) | O72—C721 | 1.415 (4) |
C14—H14 | 0.9500 | O73—C731 | 1.427 (4) |
C15—C16 | 1.378 (4) | C721—H72A | 0.9800 |
C15—H15 | 0.9500 | C721—H72B | 0.9800 |
C16—H16 | 0.9500 | C721—H72C | 0.9800 |
C31—C33 | 1.504 (5) | C731—H73A | 0.9800 |
C31—C32 | 1.515 (5) | C731—H73B | 0.9800 |
C31—C34 | 1.526 (5) | C731—H73C | 0.9800 |
C7a—N1—N2 | 110.2 (2) | H32A—C32—H32B | 109.5 |
C7a—N1—C11 | 130.9 (2) | C31—C32—H32C | 109.5 |
N2—N1—C11 | 118.7 (2) | H32A—C32—H32C | 109.5 |
C3—N2—N1 | 105.8 (2) | H32B—C32—H32C | 109.5 |
N2—C3—C3a | 110.9 (2) | C31—C33—H33A | 109.5 |
N2—C3—C31 | 121.4 (2) | C31—C33—H33B | 109.5 |
C3a—C3—C31 | 127.7 (2) | H33A—C33—H33B | 109.5 |
C7a—C3a—C3 | 104.9 (2) | C31—C33—H33C | 109.5 |
C7a—C3a—C4 | 120.5 (2) | H33A—C33—H33C | 109.5 |
C3—C3a—C4 | 134.5 (2) | H33B—C33—H33C | 109.5 |
O5—C4—C3a | 108.7 (2) | C31—C34—H34A | 109.5 |
O5—C4—H41 | 109.9 | C31—C34—H34B | 109.5 |
C3a—C4—H41 | 109.9 | H34A—C34—H34B | 109.5 |
O5—C4—H42 | 109.9 | C31—C34—H34C | 109.5 |
C3a—C4—H42 | 109.9 | H34A—C34—H34C | 109.5 |
H41—C4—H42 | 108.3 | H34B—C34—H34C | 109.5 |
C6—O5—C4 | 110.3 (2) | N7—C77—C71 | 111.6 (2) |
O5—C6—N7 | 113.5 (2) | N7—C77—H771 | 109.3 |
O5—C6—H6A | 108.9 | C71—C77—H771 | 109.3 |
N7—C6—H6A | 108.9 | N7—C77—H772 | 109.3 |
O5—C6—H6B | 108.9 | C71—C77—H772 | 109.3 |
N7—C6—H6B | 108.9 | H771—C77—H772 | 108.0 |
H6A—C6—H6B | 107.7 | C72—C71—C76 | 118.7 (3) |
C7a—N7—C6 | 107.0 (2) | C72—C71—C77 | 118.7 (3) |
C7a—N7—C77 | 112.7 (2) | C76—C71—C77 | 122.6 (3) |
C6—N7—C77 | 113.2 (2) | O72—C72—C71 | 119.3 (3) |
C3a—C7a—N1 | 108.2 (2) | O72—C72—C73 | 119.9 (3) |
C3a—C7a—N7 | 125.6 (2) | C71—C72—C73 | 120.7 (3) |
N1—C7a—N7 | 126.3 (2) | O73—C73—C74 | 125.3 (3) |
C16—C11—C12 | 120.2 (3) | O73—C73—C72 | 115.1 (3) |
C16—C11—N1 | 119.5 (2) | C74—C73—C72 | 119.6 (3) |
C12—C11—N1 | 120.3 (2) | C73—C74—C75 | 119.4 (3) |
C13—C12—C11 | 119.6 (3) | C73—C74—H74 | 120.3 |
C13—C12—H12 | 120.2 | C75—C74—H74 | 120.3 |
C11—C12—H12 | 120.2 | C76—C75—C74 | 121.0 (3) |
C14—C13—C12 | 120.2 (3) | C76—C75—H75 | 119.5 |
C14—C13—H13 | 119.9 | C74—C75—H75 | 119.5 |
C12—C13—H13 | 119.9 | C75—C76—C71 | 120.6 (3) |
C15—C14—C13 | 119.9 (3) | C75—C76—H76 | 119.7 |
C15—C14—H14 | 120.1 | C71—C76—H76 | 119.7 |
C13—C14—H14 | 120.1 | C72—O72—C721 | 113.6 (2) |
C14—C15—C16 | 120.7 (3) | C73—O73—C731 | 116.6 (3) |
C14—C15—H15 | 119.6 | O72—C721—H72A | 109.5 |
C16—C15—H15 | 119.6 | O72—C721—H72B | 109.5 |
C15—C16—C11 | 119.3 (3) | H72A—C721—H72B | 109.5 |
C15—C16—H16 | 120.3 | O72—C721—H72C | 109.5 |
C11—C16—H16 | 120.3 | H72A—C721—H72C | 109.5 |
C3—C31—C33 | 108.9 (3) | H72B—C721—H72C | 109.5 |
C3—C31—C32 | 111.3 (3) | O73—C731—H73A | 109.5 |
C33—C31—C32 | 109.6 (3) | O73—C731—H73B | 109.5 |
C3—C31—C34 | 109.3 (3) | H73A—C731—H73B | 109.5 |
C33—C31—C34 | 109.6 (3) | O73—C731—H73C | 109.5 |
C32—C31—C34 | 108.1 (3) | H73A—C731—H73C | 109.5 |
C31—C32—H32A | 109.5 | H73B—C731—H73C | 109.5 |
C31—C32—H32B | 109.5 | ||
C7a—N1—N2—C3 | 0.6 (3) | C12—C13—C14—C15 | −1.7 (5) |
C11—N1—N2—C3 | −174.8 (2) | C13—C14—C15—C16 | 0.3 (5) |
N1—N2—C3—C3a | −1.1 (3) | C14—C15—C16—C11 | 1.1 (5) |
N1—N2—C3—C31 | −179.2 (2) | C12—C11—C16—C15 | −1.0 (4) |
N2—C3—C3a—C7a | 1.2 (3) | N1—C11—C16—C15 | 177.4 (3) |
C31—C3—C3a—C7a | 179.2 (3) | N2—C3—C31—C33 | 109.2 (4) |
N2—C3—C3a—C4 | −175.6 (3) | C3a—C3—C31—C33 | −68.6 (4) |
C31—C3—C3a—C4 | 2.4 (5) | N2—C3—C31—C32 | −11.7 (4) |
C7a—C3a—C4—O5 | −14.6 (4) | C3a—C3—C31—C32 | 170.5 (3) |
C3—C3a—C4—O5 | 161.9 (3) | N2—C3—C31—C34 | −131.1 (3) |
C3a—C4—O5—C6 | 48.6 (3) | C3a—C3—C31—C34 | 51.1 (4) |
C4—O5—C6—N7 | −71.1 (3) | C7a—N7—C77—C71 | 169.9 (2) |
O5—C6—N7—C7a | 48.8 (3) | C6—N7—C77—C71 | −68.5 (3) |
O5—C6—N7—C77 | −76.0 (3) | N7—C77—C71—C72 | 148.5 (3) |
C3—C3a—C7a—N1 | −0.8 (3) | N7—C77—C71—C76 | −33.2 (4) |
C4—C3a—C7a—N1 | 176.6 (2) | C76—C71—C72—O72 | −176.2 (3) |
C3—C3a—C7a—N7 | 179.4 (3) | C77—C71—C72—O72 | 2.1 (4) |
C4—C3a—C7a—N7 | −3.2 (4) | C76—C71—C72—C73 | −0.1 (4) |
N2—N1—C7a—C3a | 0.2 (3) | C77—C71—C72—C73 | 178.2 (2) |
C11—N1—C7a—C3a | 174.8 (3) | O72—C72—C73—O73 | −4.2 (4) |
N2—N1—C7a—N7 | 180.0 (2) | C71—C72—C73—O73 | 179.7 (2) |
C11—N1—C7a—N7 | −5.4 (5) | O72—C72—C73—C74 | 175.4 (3) |
C6—N7—C7a—C3a | −12.7 (4) | C71—C72—C73—C74 | −0.7 (4) |
C77—N7—C7a—C3a | 112.5 (3) | O73—C73—C74—C75 | −178.9 (3) |
C6—N7—C7a—N1 | 167.6 (3) | C72—C73—C74—C75 | 1.5 (4) |
C77—N7—C7a—N1 | −67.3 (3) | C73—C74—C75—C76 | −1.6 (5) |
C7a—N1—C11—C16 | 158.5 (3) | C74—C75—C76—C71 | 0.8 (5) |
N2—N1—C11—C16 | −27.3 (4) | C72—C71—C76—C75 | 0.1 (5) |
C7a—N1—C11—C12 | −23.2 (4) | C77—C71—C76—C75 | −178.2 (3) |
N2—N1—C11—C12 | 151.1 (2) | C71—C72—O72—C721 | −100.0 (3) |
C16—C11—C12—C13 | −0.5 (4) | C73—C72—O72—C721 | 83.8 (3) |
N1—C11—C12—C13 | −178.8 (3) | C74—C73—O73—C731 | −0.9 (4) |
C11—C12—C13—C14 | 1.8 (4) | C72—C73—O73—C731 | 178.7 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C12—H12···N7 | 0.95 | 2.45 | 3.043 (4) | 120 |
C77—H772···O72 | 0.99 | 2.40 | 2.776 (4) | 102 |
C23H25N3O3 | F(000) = 832 |
Mr = 391.46 | Dx = 1.297 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4592 reflections |
a = 9.1164 (14) Å | θ = 2.8–27.5° |
b = 11.3303 (18) Å | µ = 0.09 mm−1 |
c = 19.694 (2) Å | T = 120 K |
β = 99.775 (13)° | Lath, colourless |
V = 2004.7 (5) Å3 | 0.38 × 0.12 × 0.08 mm |
Z = 4 |
Bruker Nonius KappaCCD diffractometer | 4592 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 2768 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.098 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.8° |
ϕ & ω scans | h = −11→11 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −14→14 |
Tmin = 0.977, Tmax = 0.993 | l = −23→25 |
28641 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)] = 0.069 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.165 | H-atom parameters constrained |
S = 1.16 | w = 1/[σ2(Fo2) + (0.0642P)2 + 0.7945P] where P = (Fo2 + 2Fc2)/3 |
4592 reflections | (Δ/σ)max = 0.001 |
265 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.49 e Å−3 |
C23H25N3O3 | V = 2004.7 (5) Å3 |
Mr = 391.46 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.1164 (14) Å | µ = 0.09 mm−1 |
b = 11.3303 (18) Å | T = 120 K |
c = 19.694 (2) Å | 0.38 × 0.12 × 0.08 mm |
β = 99.775 (13)° |
Bruker Nonius KappaCCD diffractometer | 4592 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2768 reflections with I > 2σ(I) |
Tmin = 0.977, Tmax = 0.993 | Rint = 0.098 |
28641 measured reflections |
R[F2 > 2σ(F2)] = 0.069 | 0 restraints |
wR(F2) = 0.165 | H-atom parameters constrained |
S = 1.16 | Δρmax = 0.32 e Å−3 |
4592 reflections | Δρmin = −0.49 e Å−3 |
265 parameters |
x | y | z | Uiso*/Ueq | ||
N1 | 0.6880 (2) | 0.65224 (18) | 0.75042 (11) | 0.0174 (5) | |
N2 | 0.8125 (2) | 0.59907 (19) | 0.78572 (10) | 0.0185 (5) | |
C3 | 0.8975 (3) | 0.5764 (2) | 0.73941 (13) | 0.0181 (5) | |
C3a | 0.8280 (3) | 0.6130 (2) | 0.67377 (13) | 0.0180 (5) | |
C4 | 0.8665 (3) | 0.6095 (3) | 0.60356 (14) | 0.0261 (6) | |
H41 | 0.9418 | 0.6708 | 0.5992 | 0.031* | |
H42 | 0.9093 | 0.5316 | 0.5953 | 0.031* | |
O5 | 0.7352 (2) | 0.62995 (18) | 0.55362 (9) | 0.0294 (5) | |
C6 | 0.6557 (3) | 0.7295 (3) | 0.57158 (14) | 0.0276 (6) | |
H61 | 0.5779 | 0.7507 | 0.5320 | 0.033* | |
H62 | 0.7249 | 0.7972 | 0.5808 | 0.033* | |
N7 | 0.5863 (2) | 0.70945 (19) | 0.63146 (11) | 0.0207 (5) | |
C7a | 0.6956 (3) | 0.6612 (2) | 0.68248 (13) | 0.0174 (5) | |
C11 | 0.5799 (3) | 0.6977 (2) | 0.78769 (13) | 0.0197 (6) | |
C12 | 0.5060 (3) | 0.8012 (2) | 0.76763 (14) | 0.0240 (6) | |
H12 | 0.5248 | 0.8419 | 0.7278 | 0.029* | |
C13 | 0.4047 (3) | 0.8455 (3) | 0.80561 (16) | 0.0325 (7) | |
H13 | 0.3522 | 0.9162 | 0.7916 | 0.039* | |
C14 | 0.3797 (3) | 0.7872 (3) | 0.86379 (16) | 0.0352 (8) | |
H14 | 0.3109 | 0.8181 | 0.8904 | 0.042* | |
C15 | 0.4543 (3) | 0.6840 (3) | 0.88335 (14) | 0.0304 (7) | |
H15 | 0.4367 | 0.6442 | 0.9236 | 0.036* | |
C16 | 0.5546 (3) | 0.6375 (3) | 0.84527 (13) | 0.0231 (6) | |
H16 | 0.6049 | 0.5656 | 0.8585 | 0.028* | |
C31 | 1.0445 (3) | 0.5127 (2) | 0.75995 (14) | 0.0226 (6) | |
C32 | 1.0998 (3) | 0.5242 (3) | 0.83676 (16) | 0.0369 (8) | |
H32A | 1.0267 | 0.4895 | 0.8621 | 0.055* | |
H32B | 1.1136 | 0.6078 | 0.8489 | 0.055* | |
H32C | 1.1950 | 0.4826 | 0.8489 | 0.055* | |
C33 | 1.0191 (3) | 0.3830 (3) | 0.74079 (18) | 0.0374 (8) | |
H33A | 0.9799 | 0.3764 | 0.6914 | 0.056* | |
H33B | 0.9475 | 0.3491 | 0.7672 | 0.056* | |
H33C | 1.1136 | 0.3401 | 0.7514 | 0.056* | |
C34 | 1.1619 (3) | 0.5637 (3) | 0.72167 (17) | 0.0337 (7) | |
H34A | 1.1750 | 0.6479 | 0.7323 | 0.051* | |
H34B | 1.1297 | 0.5535 | 0.6720 | 0.051* | |
H34C | 1.2566 | 0.5224 | 0.7361 | 0.051* | |
C77 | 0.4522 (3) | 0.6343 (2) | 0.61669 (14) | 0.0226 (6) | |
H771 | 0.4241 | 0.6086 | 0.6608 | 0.027* | |
H772 | 0.4761 | 0.5628 | 0.5918 | 0.027* | |
C71 | 0.3221 (3) | 0.6962 (2) | 0.57435 (14) | 0.0224 (6) | |
C72 | 0.2228 (3) | 0.6307 (2) | 0.52777 (13) | 0.0209 (6) | |
H72 | 0.2407 | 0.5499 | 0.5192 | 0.025* | |
C73 | 0.0979 (3) | 0.6874 (2) | 0.49468 (13) | 0.0218 (6) | |
C74 | 0.0700 (3) | 0.8037 (2) | 0.50569 (14) | 0.0231 (6) | |
C75 | 0.1664 (3) | 0.8705 (3) | 0.54975 (16) | 0.0349 (7) | |
H75 | 0.1480 | 0.9517 | 0.5569 | 0.042* | |
C76 | 0.2934 (3) | 0.8146 (3) | 0.58406 (17) | 0.0360 (8) | |
H76 | 0.3629 | 0.8591 | 0.6153 | 0.043* | |
O73 | −0.0175 (2) | 0.63974 (19) | 0.44912 (11) | 0.0373 (5) | |
O74 | −0.0657 (2) | 0.83573 (18) | 0.46884 (10) | 0.0314 (5) | |
C78 | −0.1176 (3) | 0.7352 (3) | 0.42764 (14) | 0.0274 (6) | |
H781 | −0.1194 | 0.7528 | 0.3783 | 0.033* | |
H782 | −0.2197 | 0.7141 | 0.4342 | 0.033* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0166 (10) | 0.0164 (12) | 0.0195 (11) | 0.0031 (8) | 0.0034 (9) | −0.0004 (9) |
N2 | 0.0158 (10) | 0.0185 (12) | 0.0202 (11) | 0.0005 (9) | 0.0004 (9) | −0.0005 (9) |
C3 | 0.0189 (12) | 0.0130 (13) | 0.0235 (13) | −0.0024 (10) | 0.0068 (11) | −0.0011 (10) |
C3a | 0.0206 (12) | 0.0130 (13) | 0.0214 (13) | −0.0026 (10) | 0.0068 (11) | −0.0011 (10) |
C4 | 0.0296 (14) | 0.0243 (15) | 0.0261 (14) | 0.0044 (12) | 0.0100 (12) | −0.0026 (12) |
O5 | 0.0411 (11) | 0.0286 (11) | 0.0189 (9) | 0.0091 (9) | 0.0066 (9) | −0.0011 (8) |
C6 | 0.0348 (15) | 0.0252 (16) | 0.0229 (14) | 0.0060 (12) | 0.0054 (12) | 0.0043 (12) |
N7 | 0.0229 (11) | 0.0205 (12) | 0.0181 (11) | 0.0029 (9) | 0.0017 (9) | 0.0009 (9) |
C7a | 0.0220 (13) | 0.0114 (12) | 0.0193 (13) | −0.0028 (10) | 0.0048 (11) | −0.0020 (10) |
C11 | 0.0143 (11) | 0.0243 (15) | 0.0202 (13) | −0.0036 (10) | 0.0021 (10) | −0.0083 (11) |
C12 | 0.0231 (13) | 0.0224 (15) | 0.0269 (14) | 0.0016 (11) | 0.0055 (12) | −0.0029 (12) |
C13 | 0.0252 (14) | 0.0282 (17) | 0.0444 (18) | 0.0041 (12) | 0.0070 (14) | −0.0134 (14) |
C14 | 0.0232 (14) | 0.047 (2) | 0.0387 (17) | −0.0017 (14) | 0.0130 (13) | −0.0186 (15) |
C15 | 0.0262 (14) | 0.0450 (19) | 0.0214 (14) | −0.0104 (13) | 0.0083 (12) | −0.0090 (13) |
C16 | 0.0192 (13) | 0.0281 (16) | 0.0210 (13) | −0.0042 (11) | 0.0001 (11) | −0.0030 (11) |
C31 | 0.0152 (12) | 0.0221 (15) | 0.0306 (15) | 0.0023 (11) | 0.0044 (11) | 0.0020 (12) |
C32 | 0.0220 (14) | 0.050 (2) | 0.0360 (17) | 0.0099 (14) | −0.0022 (13) | 0.0037 (15) |
C33 | 0.0293 (15) | 0.0226 (16) | 0.058 (2) | 0.0083 (13) | 0.0005 (15) | −0.0014 (15) |
C34 | 0.0193 (13) | 0.0368 (18) | 0.0470 (19) | 0.0051 (12) | 0.0112 (14) | 0.0073 (15) |
C77 | 0.0232 (13) | 0.0169 (14) | 0.0250 (14) | 0.0011 (11) | −0.0037 (11) | −0.0006 (11) |
C71 | 0.0240 (13) | 0.0197 (14) | 0.0227 (13) | 0.0042 (11) | 0.0019 (11) | 0.0002 (11) |
C72 | 0.0247 (13) | 0.0190 (14) | 0.0197 (13) | 0.0056 (11) | 0.0056 (11) | 0.0010 (11) |
C73 | 0.0225 (13) | 0.0271 (15) | 0.0160 (12) | 0.0020 (11) | 0.0042 (11) | −0.0017 (11) |
C74 | 0.0233 (13) | 0.0222 (15) | 0.0236 (14) | 0.0087 (11) | 0.0031 (11) | 0.0048 (11) |
C75 | 0.0419 (17) | 0.0165 (15) | 0.0423 (18) | 0.0090 (13) | −0.0041 (14) | −0.0036 (13) |
C76 | 0.0371 (17) | 0.0223 (16) | 0.0422 (18) | 0.0049 (13) | −0.0121 (14) | −0.0070 (14) |
O73 | 0.0308 (11) | 0.0323 (13) | 0.0413 (12) | 0.0133 (9) | −0.0157 (9) | −0.0089 (10) |
O74 | 0.0286 (11) | 0.0276 (12) | 0.0357 (12) | 0.0132 (9) | −0.0016 (9) | −0.0005 (9) |
C78 | 0.0263 (14) | 0.0299 (16) | 0.0238 (14) | 0.0096 (12) | −0.0020 (12) | 0.0037 (12) |
N1—C7a | 1.355 (3) | C31—C34 | 1.523 (4) |
N1—N2 | 1.366 (3) | C31—C33 | 1.526 (4) |
N1—C11 | 1.421 (3) | C32—H32A | 0.9800 |
N2—C3 | 1.319 (3) | C32—H32B | 0.9800 |
C3—C3a | 1.402 (4) | C32—H32C | 0.9800 |
C3—C31 | 1.516 (4) | C33—H33A | 0.9800 |
C3a—C7a | 1.362 (3) | C33—H33B | 0.9800 |
C3a—C4 | 1.484 (3) | C33—H33C | 0.9800 |
C4—O5 | 1.433 (3) | C34—H34A | 0.9800 |
C4—H41 | 0.9900 | C34—H34B | 0.9800 |
C4—H42 | 0.9900 | C34—H34C | 0.9800 |
O5—C6 | 1.418 (3) | C77—C71 | 1.503 (4) |
C6—N7 | 1.448 (3) | C77—H771 | 0.9900 |
C6—H61 | 0.9900 | C77—H772 | 0.9900 |
C6—H62 | 0.9900 | C71—C76 | 1.386 (4) |
N7—C7a | 1.401 (3) | C71—C72 | 1.390 (4) |
N7—C77 | 1.477 (3) | C72—C73 | 1.372 (4) |
C11—C16 | 1.376 (4) | C72—H72 | 0.9500 |
C11—C12 | 1.377 (4) | C73—C74 | 1.366 (4) |
C12—C13 | 1.378 (4) | C73—O73 | 1.372 (3) |
C12—H12 | 0.9500 | C74—C75 | 1.356 (4) |
C13—C14 | 1.375 (5) | C74—O74 | 1.373 (3) |
C13—H13 | 0.9500 | C75—C76 | 1.390 (4) |
C14—C15 | 1.374 (4) | C75—H75 | 0.9500 |
C14—H14 | 0.9500 | C76—H76 | 0.9500 |
C15—C16 | 1.382 (4) | O73—C78 | 1.432 (3) |
C15—H15 | 0.9500 | O74—C78 | 1.432 (4) |
C16—H16 | 0.9500 | C78—H781 | 0.9900 |
C31—C32 | 1.517 (4) | C78—H782 | 0.9900 |
C7a—N1—N2 | 110.97 (19) | C34—C31—C33 | 109.4 (2) |
C7a—N1—C11 | 129.7 (2) | C31—C32—H32A | 109.5 |
N2—N1—C11 | 119.1 (2) | C31—C32—H32B | 109.5 |
C3—N2—N1 | 105.6 (2) | H32A—C32—H32B | 109.5 |
N2—C3—C3a | 110.7 (2) | C31—C32—H32C | 109.5 |
N2—C3—C31 | 120.3 (2) | H32A—C32—H32C | 109.5 |
C3a—C3—C31 | 128.9 (2) | H32B—C32—H32C | 109.5 |
C7a—C3a—C3 | 105.9 (2) | C31—C33—H33A | 109.5 |
C7a—C3a—C4 | 118.9 (2) | C31—C33—H33B | 109.5 |
C3—C3a—C4 | 135.2 (2) | H33A—C33—H33B | 109.5 |
O5—C4—C3a | 109.5 (2) | C31—C33—H33C | 109.5 |
O5—C4—H41 | 109.8 | H33A—C33—H33C | 109.5 |
C3a—C4—H41 | 109.8 | H33B—C33—H33C | 109.5 |
O5—C4—H42 | 109.8 | C31—C34—H34A | 109.5 |
C3a—C4—H42 | 109.8 | C31—C34—H34B | 109.5 |
H41—C4—H42 | 108.2 | H34A—C34—H34B | 109.5 |
C6—O5—C4 | 111.1 (2) | C31—C34—H34C | 109.5 |
O5—C6—N7 | 113.0 (2) | H34A—C34—H34C | 109.5 |
O5—C6—H61 | 109.0 | H34B—C34—H34C | 109.5 |
N7—C6—H61 | 109.0 | N7—C77—C71 | 112.9 (2) |
O5—C6—H62 | 109.0 | N7—C77—H771 | 109.0 |
N7—C6—H62 | 109.0 | C71—C77—H771 | 109.0 |
H61—C6—H62 | 107.8 | N7—C77—H772 | 109.0 |
C7a—N7—C6 | 106.8 (2) | C71—C77—H772 | 109.0 |
C7a—N7—C77 | 112.4 (2) | H771—C77—H772 | 107.8 |
C6—N7—C77 | 113.0 (2) | C76—C71—C72 | 119.4 (3) |
N1—C7a—C3a | 106.8 (2) | C76—C71—C77 | 121.7 (3) |
N1—C7a—N7 | 126.0 (2) | C72—C71—C77 | 118.8 (2) |
C3a—C7a—N7 | 127.2 (2) | C73—C72—C71 | 117.3 (3) |
C16—C11—C12 | 121.1 (2) | C73—C72—H72 | 121.4 |
C16—C11—N1 | 118.3 (2) | C71—C72—H72 | 121.4 |
C12—C11—N1 | 120.6 (2) | C74—C73—O73 | 109.9 (2) |
C11—C12—C13 | 119.7 (3) | C74—C73—C72 | 122.5 (3) |
C11—C12—H12 | 120.2 | O73—C73—C72 | 127.5 (3) |
C13—C12—H12 | 120.2 | C75—C74—C73 | 121.5 (2) |
C14—C13—C12 | 119.9 (3) | C75—C74—O74 | 128.2 (3) |
C14—C13—H13 | 120.0 | C73—C74—O74 | 110.2 (2) |
C12—C13—H13 | 120.0 | C74—C75—C76 | 116.9 (3) |
C15—C14—C13 | 119.9 (3) | C74—C75—H75 | 121.6 |
C15—C14—H14 | 120.1 | C76—C75—H75 | 121.6 |
C13—C14—H14 | 120.1 | C71—C76—C75 | 122.4 (3) |
C14—C15—C16 | 120.9 (3) | C71—C76—H76 | 118.8 |
C14—C15—H15 | 119.5 | C75—C76—H76 | 118.8 |
C16—C15—H15 | 119.5 | C73—O73—C78 | 106.0 (2) |
C11—C16—C15 | 118.5 (3) | C74—O74—C78 | 105.7 (2) |
C11—C16—H16 | 120.7 | O74—C78—O73 | 107.5 (2) |
C15—C16—H16 | 120.7 | O74—C78—H781 | 110.2 |
C3—C31—C32 | 110.8 (2) | O73—C78—H781 | 110.2 |
C3—C31—C34 | 110.6 (2) | O74—C78—H782 | 110.2 |
C32—C31—C34 | 108.6 (2) | O73—C78—H782 | 110.2 |
C3—C31—C33 | 107.6 (2) | H781—C78—H782 | 108.5 |
C32—C31—C33 | 109.9 (3) | ||
C7a—N1—N2—C3 | 0.6 (3) | C13—C14—C15—C16 | −0.1 (4) |
C11—N1—N2—C3 | −174.2 (2) | C12—C11—C16—C15 | −0.8 (4) |
N1—N2—C3—C3a | −0.9 (3) | N1—C11—C16—C15 | 177.3 (2) |
N1—N2—C3—C31 | −177.8 (2) | C14—C15—C16—C11 | 0.9 (4) |
N2—C3—C3a—C7a | 0.8 (3) | N2—C3—C31—C32 | −21.5 (3) |
C31—C3—C3a—C7a | 177.4 (3) | C3a—C3—C31—C32 | 162.2 (3) |
N2—C3—C3a—C4 | −178.9 (3) | N2—C3—C31—C34 | −141.9 (3) |
C31—C3—C3a—C4 | −2.4 (5) | C3a—C3—C31—C34 | 41.8 (4) |
C7a—C3a—C4—O5 | −15.9 (3) | N2—C3—C31—C33 | 98.6 (3) |
C3—C3a—C4—O5 | 163.8 (3) | C3a—C3—C31—C33 | −77.7 (3) |
C3a—C4—O5—C6 | 48.3 (3) | C7a—N7—C77—C71 | 167.2 (2) |
C4—O5—C6—N7 | −69.9 (3) | C6—N7—C77—C71 | −71.8 (3) |
O5—C6—N7—C7a | 49.2 (3) | N7—C77—C71—C76 | −37.8 (4) |
O5—C6—N7—C77 | −74.9 (3) | N7—C77—C71—C72 | 146.8 (2) |
N2—N1—C7a—C3a | −0.1 (3) | C76—C71—C72—C73 | −1.5 (4) |
C11—N1—C7a—C3a | 174.0 (2) | C77—C71—C72—C73 | 174.0 (2) |
N2—N1—C7a—N7 | 179.0 (2) | C71—C72—C73—C74 | 0.5 (4) |
C11—N1—C7a—N7 | −7.0 (4) | C71—C72—C73—O73 | −177.1 (2) |
C3—C3a—C7a—N1 | −0.4 (3) | O73—C73—C74—C75 | 178.9 (3) |
C4—C3a—C7a—N1 | 179.4 (2) | C72—C73—C74—C75 | 0.9 (4) |
C3—C3a—C7a—N7 | −179.5 (2) | O73—C73—C74—O74 | 1.2 (3) |
C4—C3a—C7a—N7 | 0.3 (4) | C72—C73—C74—O74 | −176.8 (2) |
C6—N7—C7a—N1 | 165.2 (2) | C73—C74—C75—C76 | −1.1 (4) |
C77—N7—C7a—N1 | −70.3 (3) | O74—C74—C75—C76 | 176.1 (3) |
C6—N7—C7a—C3a | −15.9 (3) | C72—C71—C76—C75 | 1.3 (5) |
C77—N7—C7a—C3a | 108.6 (3) | C77—C71—C76—C75 | −174.1 (3) |
C7a—N1—C11—C16 | 150.9 (3) | C74—C75—C76—C71 | 0.0 (5) |
N2—N1—C11—C16 | −35.4 (3) | C74—C73—O73—C78 | 3.8 (3) |
C7a—N1—C11—C12 | −31.0 (4) | C72—C73—O73—C78 | −178.3 (3) |
N2—N1—C11—C12 | 142.7 (2) | C75—C74—O74—C78 | 176.8 (3) |
C16—C11—C12—C13 | −0.1 (4) | C73—C74—O74—C78 | −5.7 (3) |
N1—C11—C12—C13 | −178.2 (2) | C74—O74—C78—O73 | 7.9 (3) |
C11—C12—C13—C14 | 1.0 (4) | C73—O73—C78—O74 | −7.2 (3) |
C12—C13—C14—C15 | −0.9 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C12—H12···N7 | 0.95 | 2.55 | 3.078 (3) | 115 |
C4—H42···O73i | 0.99 | 2.41 | 3.381 (4) | 167 |
C72—H72···O5i | 0.95 | 2.52 | 3.413 (3) | 156 |
C75—H75···O74ii | 0.95 | 2.55 | 3.456 (4) | 160 |
C78—H781···N2iii | 0.99 | 2.48 | 3.338 (4) | 145 |
C4—H41···Cg1iv | 0.99 | 2.91 | 3.799 (3) | 150 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+2, −z+1; (iii) x−1, −y+3/2, z−1/2; (iv) x+1, y, z. |
C25H31N3O4 | Z = 2 |
Mr = 437.53 | F(000) = 468 |
Triclinic, P1 | Dx = 1.333 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.8189 (10) Å | Cell parameters from 4970 reflections |
b = 10.0499 (8) Å | θ = 3.5–27.5° |
c = 12.8130 (14) Å | µ = 0.09 mm−1 |
α = 68.710 (9)° | T = 120 K |
β = 72.537 (8)° | Block, colourless |
γ = 70.982 (8)° | 0.36 × 0.25 × 0.15 mm |
V = 1089.8 (2) Å3 |
Bruker Nonius KappaCCD diffractometer | 4970 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 3754 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.050 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.5° |
ϕ and ω scans | h = −12→12 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −13→13 |
Tmin = 0.958, Tmax = 0.987 | l = −16→16 |
30046 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)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.120 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0557P)2 + 0.4602P] where P = (Fo2 + 2Fc2)/3 |
4970 reflections | (Δ/σ)max = 0.001 |
295 parameters | Δρmax = 0.24 e Å−3 |
0 restraints | Δρmin = −0.32 e Å−3 |
C25H31N3O4 | γ = 70.982 (8)° |
Mr = 437.53 | V = 1089.8 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.8189 (10) Å | Mo Kα radiation |
b = 10.0499 (8) Å | µ = 0.09 mm−1 |
c = 12.8130 (14) Å | T = 120 K |
α = 68.710 (9)° | 0.36 × 0.25 × 0.15 mm |
β = 72.537 (8)° |
Bruker Nonius KappaCCD diffractometer | 4970 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 3754 reflections with I > 2σ(I) |
Tmin = 0.958, Tmax = 0.987 | Rint = 0.050 |
30046 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.120 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.24 e Å−3 |
4970 reflections | Δρmin = −0.32 e Å−3 |
295 parameters |
x | y | z | Uiso*/Ueq | ||
N1 | 0.41871 (14) | 0.34127 (14) | 0.27052 (11) | 0.0161 (3) | |
N2 | 0.33809 (14) | 0.39324 (14) | 0.18740 (11) | 0.0176 (3) | |
C3 | 0.22352 (17) | 0.49451 (17) | 0.21906 (13) | 0.0162 (3) | |
C3a | 0.22777 (16) | 0.50813 (16) | 0.32347 (13) | 0.0153 (3) | |
C4 | 0.12970 (16) | 0.59808 (17) | 0.39998 (13) | 0.0169 (3) | |
H41 | 0.1395 | 0.7009 | 0.3662 | 0.020* | |
H42 | 0.0259 | 0.5986 | 0.4088 | 0.020* | |
O5 | 0.17008 (11) | 0.53654 (12) | 0.50952 (9) | 0.0177 (2) | |
C6 | 0.32479 (16) | 0.50649 (17) | 0.49670 (14) | 0.0174 (3) | |
H61 | 0.3478 | 0.4850 | 0.5722 | 0.021* | |
H62 | 0.3588 | 0.5953 | 0.4449 | 0.021* | |
N7 | 0.40461 (14) | 0.38370 (14) | 0.45118 (11) | 0.0156 (3) | |
C7a | 0.35277 (16) | 0.40948 (16) | 0.35319 (13) | 0.0146 (3) | |
C11 | 0.55964 (16) | 0.24594 (17) | 0.25177 (13) | 0.0169 (3) | |
C12 | 0.67425 (17) | 0.25633 (18) | 0.28799 (14) | 0.0198 (3) | |
H12 | 0.6583 | 0.3252 | 0.3279 | 0.024* | |
C13 | 0.81186 (17) | 0.16513 (18) | 0.26528 (14) | 0.0220 (4) | |
H13 | 0.8911 | 0.1701 | 0.2907 | 0.026* | |
C14 | 0.83531 (18) | 0.06689 (18) | 0.20605 (16) | 0.0255 (4) | |
H14 | 0.9305 | 0.0048 | 0.1901 | 0.031* | |
C15 | 0.72066 (19) | 0.05885 (19) | 0.17004 (17) | 0.0277 (4) | |
H15 | 0.7372 | −0.0087 | 0.1289 | 0.033* | |
C16 | 0.58224 (18) | 0.14747 (18) | 0.19286 (15) | 0.0218 (4) | |
H16 | 0.5031 | 0.1409 | 0.1683 | 0.026* | |
C31 | 0.10797 (17) | 0.57479 (18) | 0.14774 (14) | 0.0189 (3) | |
C32 | 0.16661 (19) | 0.56236 (19) | 0.02701 (14) | 0.0234 (4) | |
H32A | 0.2531 | 0.6036 | −0.0083 | 0.035* | |
H32B | 0.0902 | 0.6169 | −0.0182 | 0.035* | |
H32C | 0.1944 | 0.4585 | 0.0295 | 0.035* | |
C33 | −0.02341 (19) | 0.5062 (2) | 0.20305 (16) | 0.0320 (4) | |
H33A | 0.0074 | 0.4024 | 0.2050 | 0.048* | |
H33B | −0.1006 | 0.5586 | 0.1584 | 0.048* | |
H33C | −0.0615 | 0.5134 | 0.2813 | 0.048* | |
C34 | 0.0626 (2) | 0.7359 (2) | 0.14310 (18) | 0.0372 (5) | |
H34A | 0.0162 | 0.7452 | 0.2202 | 0.056* | |
H34B | −0.0075 | 0.7905 | 0.0924 | 0.056* | |
H34C | 0.1498 | 0.7763 | 0.1137 | 0.056* | |
C77 | 0.39566 (17) | 0.23763 (17) | 0.53557 (14) | 0.0181 (3) | |
H771 | 0.4117 | 0.1661 | 0.4940 | 0.022* | |
H772 | 0.2954 | 0.2454 | 0.5842 | 0.022* | |
C71 | 0.50591 (17) | 0.18036 (16) | 0.61098 (13) | 0.0166 (3) | |
C72 | 0.47634 (17) | 0.22175 (17) | 0.70885 (13) | 0.0179 (3) | |
H72 | 0.3854 | 0.2877 | 0.7289 | 0.021* | |
C73 | 0.57941 (17) | 0.16710 (17) | 0.77793 (13) | 0.0180 (3) | |
C74 | 0.70922 (17) | 0.06779 (17) | 0.75010 (13) | 0.0173 (3) | |
C75 | 0.73793 (17) | 0.02478 (16) | 0.65319 (14) | 0.0171 (3) | |
C76 | 0.63713 (17) | 0.08249 (17) | 0.58253 (13) | 0.0168 (3) | |
H76 | 0.6580 | 0.0550 | 0.5148 | 0.020* | |
O73 | 0.56197 (13) | 0.20001 (13) | 0.87545 (10) | 0.0248 (3) | |
O74 | 0.81068 (12) | 0.01173 (12) | 0.81828 (10) | 0.0215 (3) | |
O75 | 0.86794 (12) | −0.07397 (12) | 0.63558 (10) | 0.0216 (3) | |
C731 | 0.45599 (19) | 0.32985 (18) | 0.89012 (15) | 0.0242 (4) | |
H73A | 0.4758 | 0.4135 | 0.8234 | 0.036* | |
H73B | 0.4612 | 0.3473 | 0.9591 | 0.036* | |
H73C | 0.3575 | 0.3189 | 0.8980 | 0.036* | |
C741 | 0.7812 (2) | −0.1139 (2) | 0.90951 (16) | 0.0294 (4) | |
H74A | 0.6877 | −0.0853 | 0.9608 | 0.044* | |
H74B | 0.8607 | −0.1561 | 0.9522 | 0.044* | |
H74C | 0.7747 | −0.1872 | 0.8787 | 0.044* | |
C751 | 0.89433 (19) | −0.14104 (19) | 0.54920 (15) | 0.0241 (4) | |
H75A | 0.8173 | −0.1923 | 0.5657 | 0.036* | |
H75B | 0.9905 | −0.2119 | 0.5472 | 0.036* | |
H75C | 0.8934 | −0.0654 | 0.4749 | 0.036* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0124 (6) | 0.0176 (6) | 0.0180 (7) | 0.0014 (5) | −0.0069 (5) | −0.0064 (5) |
N2 | 0.0160 (6) | 0.0194 (7) | 0.0180 (7) | −0.0005 (5) | −0.0077 (5) | −0.0062 (5) |
C3 | 0.0142 (7) | 0.0157 (7) | 0.0184 (8) | −0.0028 (6) | −0.0037 (6) | −0.0051 (6) |
C3a | 0.0135 (7) | 0.0157 (7) | 0.0165 (7) | −0.0036 (6) | −0.0037 (6) | −0.0042 (6) |
C4 | 0.0136 (7) | 0.0188 (8) | 0.0181 (8) | −0.0002 (6) | −0.0052 (6) | −0.0068 (6) |
O5 | 0.0135 (5) | 0.0229 (6) | 0.0160 (5) | −0.0011 (4) | −0.0034 (4) | −0.0075 (5) |
C6 | 0.0142 (7) | 0.0209 (8) | 0.0191 (8) | −0.0031 (6) | −0.0047 (6) | −0.0080 (6) |
N7 | 0.0152 (6) | 0.0164 (6) | 0.0156 (6) | −0.0024 (5) | −0.0055 (5) | −0.0045 (5) |
C7a | 0.0129 (7) | 0.0146 (7) | 0.0162 (7) | −0.0040 (6) | −0.0037 (6) | −0.0033 (6) |
C11 | 0.0122 (7) | 0.0163 (7) | 0.0176 (8) | 0.0000 (6) | −0.0024 (6) | −0.0035 (6) |
C12 | 0.0169 (8) | 0.0226 (8) | 0.0195 (8) | −0.0027 (6) | −0.0048 (6) | −0.0067 (7) |
C13 | 0.0139 (8) | 0.0247 (9) | 0.0231 (9) | −0.0027 (6) | −0.0065 (6) | −0.0018 (7) |
C14 | 0.0126 (8) | 0.0190 (8) | 0.0354 (10) | 0.0014 (6) | −0.0003 (7) | −0.0056 (7) |
C15 | 0.0208 (9) | 0.0233 (9) | 0.0397 (11) | −0.0032 (7) | −0.0003 (8) | −0.0167 (8) |
C16 | 0.0159 (8) | 0.0215 (8) | 0.0294 (9) | −0.0035 (6) | −0.0043 (7) | −0.0103 (7) |
C31 | 0.0175 (8) | 0.0204 (8) | 0.0200 (8) | 0.0020 (6) | −0.0089 (6) | −0.0089 (6) |
C32 | 0.0227 (8) | 0.0257 (9) | 0.0198 (8) | −0.0001 (7) | −0.0090 (7) | −0.0059 (7) |
C33 | 0.0176 (8) | 0.0542 (12) | 0.0253 (9) | −0.0071 (8) | −0.0069 (7) | −0.0124 (9) |
C34 | 0.0480 (12) | 0.0254 (10) | 0.0432 (12) | 0.0144 (9) | −0.0331 (10) | −0.0174 (9) |
C77 | 0.0156 (7) | 0.0180 (8) | 0.0207 (8) | −0.0042 (6) | −0.0071 (6) | −0.0030 (6) |
C71 | 0.0154 (7) | 0.0158 (7) | 0.0184 (8) | −0.0049 (6) | −0.0067 (6) | −0.0011 (6) |
C72 | 0.0147 (7) | 0.0175 (8) | 0.0184 (8) | −0.0017 (6) | −0.0043 (6) | −0.0030 (6) |
C73 | 0.0189 (8) | 0.0181 (8) | 0.0163 (8) | −0.0044 (6) | −0.0050 (6) | −0.0034 (6) |
C74 | 0.0158 (7) | 0.0181 (8) | 0.0183 (8) | −0.0044 (6) | −0.0074 (6) | −0.0025 (6) |
C75 | 0.0134 (7) | 0.0152 (7) | 0.0211 (8) | −0.0033 (6) | −0.0033 (6) | −0.0040 (6) |
C76 | 0.0180 (8) | 0.0172 (8) | 0.0160 (8) | −0.0051 (6) | −0.0051 (6) | −0.0040 (6) |
O73 | 0.0266 (6) | 0.0261 (6) | 0.0213 (6) | 0.0037 (5) | −0.0107 (5) | −0.0110 (5) |
O74 | 0.0184 (6) | 0.0239 (6) | 0.0240 (6) | −0.0017 (5) | −0.0118 (5) | −0.0060 (5) |
O75 | 0.0153 (6) | 0.0244 (6) | 0.0260 (6) | 0.0029 (5) | −0.0082 (5) | −0.0121 (5) |
C731 | 0.0256 (9) | 0.0222 (8) | 0.0234 (9) | −0.0016 (7) | −0.0034 (7) | −0.0101 (7) |
C741 | 0.0318 (10) | 0.0272 (9) | 0.0256 (9) | −0.0019 (8) | −0.0158 (8) | −0.0005 (7) |
C751 | 0.0217 (8) | 0.0259 (9) | 0.0266 (9) | 0.0005 (7) | −0.0071 (7) | −0.0138 (7) |
N1—C7a | 1.356 (2) | C32—H32C | 0.9800 |
N1—N2 | 1.3660 (17) | C33—H33A | 0.9800 |
N1—C11 | 1.4121 (19) | C33—H33B | 0.9800 |
N2—C3 | 1.321 (2) | C33—H33C | 0.9800 |
C3—C3a | 1.407 (2) | C34—H34A | 0.9800 |
C3—C31 | 1.505 (2) | C34—H34B | 0.9800 |
C3a—C7a | 1.359 (2) | C34—H34C | 0.9800 |
C3a—C4 | 1.488 (2) | C77—C71 | 1.501 (2) |
C4—O5 | 1.4330 (18) | C77—H771 | 0.9900 |
C4—H41 | 0.9900 | C77—H772 | 0.9900 |
C4—H42 | 0.9900 | C71—C72 | 1.383 (2) |
O5—C6 | 1.4188 (18) | C71—C76 | 1.383 (2) |
C6—N7 | 1.448 (2) | C72—C73 | 1.390 (2) |
C6—H61 | 0.9900 | C72—H72 | 0.9500 |
C6—H62 | 0.9900 | C73—O73 | 1.3545 (19) |
N7—C7a | 1.4014 (19) | C73—C74 | 1.380 (2) |
N7—C77 | 1.4854 (19) | C74—O74 | 1.3682 (18) |
C11—C16 | 1.377 (2) | C74—C75 | 1.381 (2) |
C11—C12 | 1.385 (2) | C75—O75 | 1.3526 (19) |
C12—C13 | 1.379 (2) | C75—C76 | 1.385 (2) |
C12—H12 | 0.9500 | C76—H76 | 0.9500 |
C13—C14 | 1.377 (3) | O73—C731 | 1.413 (2) |
C13—H13 | 0.9500 | O74—C741 | 1.417 (2) |
C14—C15 | 1.373 (2) | O75—C751 | 1.415 (2) |
C14—H14 | 0.9500 | C731—H73A | 0.9800 |
C15—C16 | 1.374 (2) | C731—H73B | 0.9800 |
C15—H15 | 0.9500 | C731—H73C | 0.9800 |
C16—H16 | 0.9500 | C741—H74A | 0.9800 |
C31—C32 | 1.516 (2) | C741—H74B | 0.9800 |
C31—C34 | 1.517 (2) | C741—H74C | 0.9800 |
C31—C33 | 1.522 (2) | C751—H75A | 0.9800 |
C32—H32A | 0.9800 | C751—H75B | 0.9800 |
C32—H32B | 0.9800 | C751—H75C | 0.9800 |
C7a—N1—N2 | 110.66 (12) | H32B—C32—H32C | 109.5 |
C7a—N1—C11 | 130.28 (13) | C31—C33—H33A | 109.5 |
N2—N1—C11 | 118.41 (12) | C31—C33—H33B | 109.5 |
C3—N2—N1 | 105.52 (12) | H33A—C33—H33B | 109.5 |
N2—C3—C3a | 111.01 (13) | C31—C33—H33C | 109.5 |
N2—C3—C31 | 120.42 (14) | H33A—C33—H33C | 109.5 |
C3a—C3—C31 | 128.55 (14) | H33B—C33—H33C | 109.5 |
C7a—C3a—C3 | 105.18 (14) | C31—C34—H34A | 109.5 |
C7a—C3a—C4 | 119.92 (14) | C31—C34—H34B | 109.5 |
C3—C3a—C4 | 134.88 (14) | H34A—C34—H34B | 109.5 |
O5—C4—C3a | 109.09 (12) | C31—C34—H34C | 109.5 |
O5—C4—H41 | 109.9 | H34A—C34—H34C | 109.5 |
C3a—C4—H41 | 109.9 | H34B—C34—H34C | 109.5 |
O5—C4—H42 | 109.9 | N7—C77—C71 | 113.19 (12) |
C3a—C4—H42 | 109.9 | N7—C77—H771 | 108.9 |
H41—C4—H42 | 108.3 | C71—C77—H771 | 108.9 |
C6—O5—C4 | 110.63 (11) | N7—C77—H772 | 108.9 |
O5—C6—N7 | 113.05 (12) | C71—C77—H772 | 108.9 |
O5—C6—H61 | 109.0 | H771—C77—H772 | 107.8 |
N7—C6—H61 | 109.0 | C72—C71—C76 | 120.10 (14) |
O5—C6—H62 | 109.0 | C72—C71—C77 | 120.90 (14) |
N7—C6—H62 | 109.0 | C76—C71—C77 | 118.98 (14) |
H61—C6—H62 | 107.8 | C71—C72—C73 | 120.11 (15) |
C7a—N7—C6 | 106.79 (12) | C71—C72—H72 | 119.9 |
C7a—N7—C77 | 113.15 (12) | C73—C72—H72 | 119.9 |
C6—N7—C77 | 113.82 (12) | O73—C73—C74 | 115.35 (14) |
N1—C7a—C3a | 107.63 (13) | O73—C73—C72 | 125.07 (14) |
N1—C7a—N7 | 126.20 (13) | C74—C73—C72 | 119.55 (15) |
C3a—C7a—N7 | 126.17 (14) | O74—C74—C73 | 120.09 (14) |
C16—C11—C12 | 120.87 (14) | O74—C74—C75 | 119.57 (14) |
C16—C11—N1 | 118.91 (14) | C73—C74—C75 | 120.34 (14) |
C12—C11—N1 | 120.16 (14) | O75—C75—C74 | 114.87 (14) |
C13—C12—C11 | 118.94 (15) | O75—C75—C76 | 125.01 (15) |
C13—C12—H12 | 120.5 | C74—C75—C76 | 120.12 (14) |
C11—C12—H12 | 120.5 | C71—C76—C75 | 119.74 (15) |
C14—C13—C12 | 120.47 (15) | C71—C76—H76 | 120.1 |
C14—C13—H13 | 119.8 | C75—C76—H76 | 120.1 |
C12—C13—H13 | 119.8 | C73—O73—C731 | 117.19 (12) |
C15—C14—C13 | 119.79 (16) | C74—O74—C741 | 111.83 (12) |
C15—C14—H14 | 120.1 | C75—O75—C751 | 117.97 (12) |
C13—C14—H14 | 120.1 | O73—C731—H73A | 109.5 |
C14—C15—C16 | 120.73 (16) | O73—C731—H73B | 109.5 |
C14—C15—H15 | 119.6 | H73A—C731—H73B | 109.5 |
C16—C15—H15 | 119.6 | O73—C731—H73C | 109.5 |
C15—C16—C11 | 119.18 (15) | H73A—C731—H73C | 109.5 |
C15—C16—H16 | 120.4 | H73B—C731—H73C | 109.5 |
C11—C16—H16 | 120.4 | O74—C741—H74A | 109.5 |
C3—C31—C32 | 110.91 (13) | O74—C741—H74B | 109.5 |
C3—C31—C34 | 108.88 (13) | H74A—C741—H74B | 109.5 |
C32—C31—C34 | 109.17 (15) | O74—C741—H74C | 109.5 |
C3—C31—C33 | 108.43 (14) | H74A—C741—H74C | 109.5 |
C32—C31—C33 | 109.05 (14) | H74B—C741—H74C | 109.5 |
C34—C31—C33 | 110.40 (16) | O75—C751—H75A | 109.5 |
C31—C32—H32A | 109.5 | O75—C751—H75B | 109.5 |
C31—C32—H32B | 109.5 | H75A—C751—H75B | 109.5 |
H32A—C32—H32B | 109.5 | O75—C751—H75C | 109.5 |
C31—C32—H32C | 109.5 | H75A—C751—H75C | 109.5 |
H32A—C32—H32C | 109.5 | H75B—C751—H75C | 109.5 |
C7a—N1—N2—C3 | 0.64 (16) | C14—C15—C16—C11 | 0.5 (3) |
C11—N1—N2—C3 | −171.05 (13) | C12—C11—C16—C15 | 0.0 (3) |
N1—N2—C3—C3a | −0.64 (17) | N1—C11—C16—C15 | 177.21 (15) |
N1—N2—C3—C31 | −179.01 (13) | N2—C3—C31—C32 | −19.1 (2) |
N2—C3—C3a—C7a | 0.42 (18) | C3a—C3—C31—C32 | 162.88 (15) |
C31—C3—C3a—C7a | 178.62 (15) | N2—C3—C31—C34 | −139.21 (16) |
N2—C3—C3a—C4 | −177.99 (16) | C3a—C3—C31—C34 | 42.7 (2) |
C31—C3—C3a—C4 | 0.2 (3) | N2—C3—C31—C33 | 100.64 (17) |
C7a—C3a—C4—O5 | −14.00 (19) | C3a—C3—C31—C33 | −77.4 (2) |
C3—C3a—C4—O5 | 164.23 (16) | C7a—N7—C77—C71 | 154.32 (13) |
C3a—C4—O5—C6 | 47.36 (15) | C6—N7—C77—C71 | −83.53 (16) |
C4—O5—C6—N7 | −70.87 (16) | N7—C77—C71—C72 | 84.69 (18) |
O5—C6—N7—C7a | 50.39 (16) | N7—C77—C71—C76 | −96.68 (16) |
O5—C6—N7—C77 | −75.21 (16) | C76—C71—C72—C73 | 1.1 (2) |
N2—N1—C7a—C3a | −0.39 (17) | C77—C71—C72—C73 | 179.70 (14) |
C11—N1—C7a—C3a | 170.02 (14) | C71—C72—C73—O73 | −179.92 (14) |
N2—N1—C7a—N7 | −179.99 (13) | C71—C72—C73—C74 | −2.0 (2) |
C11—N1—C7a—N7 | −9.6 (3) | O73—C73—C74—O74 | −1.1 (2) |
C3—C3a—C7a—N1 | −0.01 (17) | C72—C73—C74—O74 | −179.14 (14) |
C4—C3a—C7a—N1 | 178.69 (13) | O73—C73—C74—C75 | 179.20 (14) |
C3—C3a—C7a—N7 | 179.59 (14) | C72—C73—C74—C75 | 1.1 (2) |
C4—C3a—C7a—N7 | −1.7 (2) | O74—C74—C75—O75 | 0.9 (2) |
C6—N7—C7a—N1 | 164.15 (14) | C73—C74—C75—O75 | −179.39 (13) |
C77—N7—C7a—N1 | −69.84 (19) | O74—C74—C75—C76 | −178.99 (13) |
C6—N7—C7a—C3a | −15.4 (2) | C73—C74—C75—C76 | 0.7 (2) |
C77—N7—C7a—C3a | 110.63 (17) | C72—C71—C76—C75 | 0.8 (2) |
C7a—N1—C11—C16 | 155.10 (16) | C77—C71—C76—C75 | −177.85 (13) |
N2—N1—C11—C16 | −35.1 (2) | O75—C75—C76—C71 | 178.45 (14) |
C7a—N1—C11—C12 | −27.6 (2) | C74—C75—C76—C71 | −1.7 (2) |
N2—N1—C11—C12 | 142.14 (15) | C74—C73—O73—C731 | 161.62 (14) |
C16—C11—C12—C13 | −0.7 (2) | C72—C73—O73—C731 | −20.4 (2) |
N1—C11—C12—C13 | −177.91 (14) | C73—C74—O74—C741 | 86.25 (18) |
C11—C12—C13—C14 | 1.0 (2) | C75—C74—O74—C741 | −94.02 (18) |
C12—C13—C14—C15 | −0.5 (3) | C74—C75—O75—C751 | 169.91 (14) |
C13—C14—C15—C16 | −0.3 (3) | C76—C75—O75—C751 | −10.2 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C12—H12···N7 | 0.95 | 2.53 | 3.071 (2) | 116 |
C4—H42···O5i | 0.99 | 2.47 | 3.354 (2) | 148 |
C13—H13···O75ii | 0.95 | 2.57 | 3.466 (2) | 157 |
C14—H14···O74ii | 0.95 | 2.46 | 3.247 (2) | 140 |
C6—H62···Cg1 | 0.99 | 2.76 | 3.737 (2) | 167 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+2, −y, −z+1. |
Experimental details
(I) | (II) | (III) | (IV) | |
Crystal data | ||||
Chemical formula | C22H25N3O | C23H27N3O | C23H27N3O2 | C23H24F3N3O |
Mr | 347.45 | 361.48 | 377.48 | 415.45 |
Crystal system, space group | Monoclinic, P21 | Monoclinic, P21 | Monoclinic, P21 | Triclinic, P1 |
Temperature (K) | 120 | 120 | 120 | 120 |
a, b, c (Å) | 8.893 (1), 11.1321 (12), 10.2078 (9) | 8.9500 (7), 11.2146 (10), 10.0768 (9) | 9.1888 (2), 11.4499 (3), 9.7210 (2) | 9.0277 (11), 9.8597 (12), 12.6835 (18) |
α, β, γ (°) | 90, 109.749 (7), 90 | 90, 107.572 (5), 90 | 90, 101.857 (1), 90 | 85.531 (11), 74.180 (11), 67.162 (9) |
V (Å3) | 951.11 (18) | 964.22 (15) | 1000.93 (4) | 1000.6 (2) |
Z | 2 | 2 | 2 | 2 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.08 | 0.08 | 0.08 | 0.11 |
Crystal size (mm) | 0.41 × 0.25 × 0.22 | 0.32 × 0.22 × 0.15 | 0.15 × 0.12 × 0.05 | 0.27 × 0.17 × 0.14 |
Data collection | ||||
Diffractometer | Bruker Nonius KappaCCD diffractometer | Bruker Nonius KappaCCD diffractometer | Bruker Nonius KappaCCD diffractometer | Bruker Nonius KappaCCD 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, 0.975 | 0.957, 0.989 | 0.980, 0.996 | 0.922, 0.986 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15738, 2303, 1768 | 15494, 2323, 1443 | 12855, 2411, 2237 | 24473, 4601, 2336 |
Rint | 0.057 | 0.096 | 0.036 | 0.099 |
(sin θ/λ)max (Å−1) | 0.650 | 0.649 | 0.650 | 0.650 |
Refinement | ||||
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.103, 1.10 | 0.052, 0.149, 1.07 | 0.038, 0.085, 1.19 | 0.061, 0.183, 1.04 |
No. of reflections | 2303 | 2323 | 2411 | 4601 |
No. of parameters | 239 | 249 | 257 | 274 |
No. of restraints | 1 | 1 | 1 | 0 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.20, −0.26 | 0.27, −0.30 | 0.17, −0.20 | 0.33, −0.37 |
(V) | (VI) | (VII) | (VIII) | |
Crystal data | ||||
Chemical formula | C22H24N4O3 | C24H29N3O3 | C23H25N3O3 | C25H31N3O4 |
Mr | 392.45 | 407.50 | 391.46 | 437.53 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21 | Monoclinic, P21/c | Triclinic, P1 |
Temperature (K) | 120 | 120 | 120 | 120 |
a, b, c (Å) | 19.164 (2), 8.7781 (7), 11.7188 (12) | 8.8268 (10), 11.6521 (10), 10.3831 (7) | 9.1164 (14), 11.3303 (18), 19.694 (2) | 9.8189 (10), 10.0499 (8), 12.8130 (14) |
α, β, γ (°) | 90, 101.717 (10), 90 | 90, 93.747 (9), 90 | 90, 99.775 (13), 90 | 68.710 (9), 72.537 (8), 70.982 (8) |
V (Å3) | 1930.3 (3) | 1065.63 (17) | 2004.7 (5) | 1089.8 (2) |
Z | 4 | 2 | 4 | 2 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.09 | 0.09 | 0.09 | 0.09 |
Crystal size (mm) | 0.33 × 0.22 × 0.18 | 0.25 × 0.20 × 0.19 | 0.38 × 0.12 × 0.08 | 0.36 × 0.25 × 0.15 |
Data collection | ||||
Diffractometer | Bruker Nonius KappaCCD diffractometer | Bruker Nonius KappaCCD diffractometer | Bruker Nonius KappaCCD diffractometer | Bruker Nonius KappaCCD 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 | 0.917, 0.984 | 0.972, 0.984 | 0.977, 0.993 | 0.958, 0.987 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 27769, 4417, 2821 | 17934, 2560, 2132 | 28641, 4592, 2768 | 30046, 4970, 3754 |
Rint | 0.066 | 0.049 | 0.098 | 0.050 |
(sin θ/λ)max (Å−1) | 0.650 | 0.650 | 0.650 | 0.650 |
Refinement | ||||
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.116, 1.09 | 0.044, 0.112, 1.13 | 0.069, 0.165, 1.16 | 0.047, 0.120, 1.07 |
No. of reflections | 4417 | 2560 | 4592 | 4970 |
No. of parameters | 265 | 276 | 265 | 295 |
No. of restraints | 0 | 1 | 0 | 0 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.24, −0.29 | 0.32, −0.27 | 0.32, −0.49 | 0.24, −0.32 |
Computer programs: COLLECT (Hooft, 1999), DIRAX/LSQ (Duisenberg et al., 2000), EVALCCD (Duisenberg et al., 2003), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
(a) | Ring-puckering parameters | |||
Q | θ | ϕ | ||
(I) | 0.496 (3) | 128.3 (3) | 146.7 (4) | |
(II) | 0.491 (4) | 128.8 (5) | 143.9 (7) | |
(III) | 0.501 (2) | 128.6 (2) | 146.1 (3) | |
(IV) | 0.499 (3) | 127.6 (3) | 150.1 (4) | |
(V) | 0.475 (2) | 132.3 (2) | 145.3 (3) | |
(VI) | 0.498 (3) | 127.7 (3) | 151.3 (4) | |
(VII) | 0.488 (3) | 130.1 (4) | 149.6 (4) | |
(VIII) | 0.498 (2) | 128.6 (2) | 148.1 (2) | |
(b) | Selected torsion angles | |||
N2—N1—C11—C12 | N2—C3—C31—C32 | C6—N7—C77—C71 | N7—C77—C71—C72 | |
(I) | 145.5 (2) | -14.8 (4) | -67.5 (3) | 117.1 (3) |
(II) | 143.5 (4) | -13.7 (5) | -69.2 (5) | 122.1 (4) |
(III) | 142.89 (19) | -19.9 (3) | -71.6 (2) | 143.1 (2) |
(IV) | 150.6 (2) | -11.1 (4) | -70.9 (3) | 147.0 (3) |
(V) | 140.79 (17) | -11.8 (2) | -75.3 (2) | 138.65 (18) |
(VI) | 151.1 (2) | -11.7 (4) | -68.5 (3) | 148.5 (3) |
(VII) | 142.7 (2) | -21.5 (3) | -71.8 (3) | 146.8 (2) |
(VIII) | 142.14 (15) | -19.1 (2) | -83.53 (16) | 84.69 (18) |
Puckering parameters are calculated for the atom sequence O5–C4–C3a–C7a–N7–C6 |
Compound | D—H···A | D—H | H···A | D···A | D—H···A | |
(I) | C12—H12···N7 | 0.95 | 2.55 | 3.079 (4) | 115 | |
C15—H15···O5i | 0.95 | 2.42 | 3.210 (3) | 140 | ||
(II) | C12—H12···N7 | 0.95 | 2.60 | 3.103 (5) | 113 | |
C15—H15···O5i | 0.95 | 2.61 | 3.258 (5) | 126 | ||
C4—H41···Cg1ii | 0.99 | 2.96 | 3.872 (5) | 154 | ||
(III) | C12-H12···N7 | 0.95 | 2.62 | 3.108 (3) | 113 | |
(IV) | C12-H12···N7 | 0.95 | 2.48 | 3.040 (4) | 118 | |
(V) | C12—H12···N7 | 0.95 | 2.55 | 3.062 (3) | 114 | |
C13—H13···N2iii | 0.95 | 2.55 | 3.399 (2) | 148 | ||
C72—H72···O41iv | 0.95 | 2.37 | 3.293 (3) | 163 | ||
C75—H75···O5iii | 0.95 | 2.50 | 3.409 (2) | 161 | ||
(VI) | C12—H12···N7 | 0.95 | 2.45 | 3.043 (4) | 120 | |
C77—H772···O72 | 0.99 | 2.40 | 2.776 (4) | 102 | ||
(VII) | C12—H12···N7 | 0.95 | 2.55 | 3.078 (3) | 115 | |
C4—H42···O73v | 0.99 | 2.41 | 3.381 (4) | 167 | ||
C72—H72···O5v | 0.95 | 2.52 | 3.413 (3) | 156 | ||
C75—H75···O74vi | 0.95 | 2.55 | 3.456 (4) | 160 | ||
C78—H781···N2vii | 0.99 | 2.48 | 3.338 (4) | 145 | ||
C4—H41···Cg1viii | 0.99 | 2.91 | 3.799 (3) | 150 | ||
(VIII) | C12—H12···N7 | 0.95 | 2.53 | 3.071 (2) | 116 | |
C4—H42···O5ix | 0.99 | 2.47 | 3.354 (2) | 148 | ||
C13—H13···O75x | 0.95 | 2.57 | 3.466 (2) | 157 | ||
C14—H14···O74x | 0.95 | 2.46 | 3.247 (2) | 140 | ||
C6—H62···Cg1v | 0.99 | 2.76 | 3.737 (2) | 167 |
Cg1 represents the centroid of the C71–C76 ring. Symmetry codes: (i) x, y, -1+z; (ii) -1+x, y, z; (iii) x, 1.5-y, 0.5+z; (iv) 1-x, -0.5+y, 0.5-z; (v) 1-x, 1-y, 1-z; (vi) -x, 2-y, 1-z; (vii) -1+x, 1.5-y, -0.5+z; (viii) 1+x, y, z; (ix) -x, 1-y, 1-z; (x) 2-x, -y, 1-z. |
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In connection with our wider study of new synthetic routes to fused pyrazole derivatives having potential applications in fields such as drug precursors, pesticides and new materials (Elguero, 1984, 1996), we report here the structures of eight substituted pyrazolooxazines. These derivatives have been prepared following a synthetic sequence based on the condensation of a substituted 5-aminopyrazole with the appropriate aldehyde to provide (E)-3-tert-butyl-5-arylidenamino-1-phenyl-1H-pyrazole derivatives, followed by reduction of these intermediates to the corresponding 5-arylmethylamino-3-tert-butyl-1-phenyl-1H-pyrazoles (Castillo et al., 2009), and finally reaction with formaldehyde under acid catalysis.
Thus, we now report the structures of 7-benzyl-3-tert-butyl-1-phenylpyrazolo-oxazine (I) and of seven derivatives (II)–(VIII) (see scheme and Figs. 1 and2) bearing a range of simple substituents in the phenyl ring of the benzyl unit. Compounds (I) and (II) are isomorphous in space group P21; while compound (III) also crystallizes in P21 with cell dimensions and atomic coordinates similar to those in (I) and (II), it cannot be regarded as either isomorphous or isostructural with (I) and (II). Compound (VI) also crystallizes in P21 but with cell dimensions significantly different from those in compounds (I)–(III).
In each compound, the ring-puckering parameters (Cremer & Pople, 1975) show that the oxazine ring adopts an almost perfect half-chair conformation (Table 1): for this conformation, the idealized values of the puckering angles (calculated assuming equal bond distances throughout the ring) are θ = 129.2° and ϕ = (60n + 30)°, where n represents an integer. The rest of the skeletal conformation, defining the orientation of the pendent substituents relative to the pyrazolooxazine unit, can be defined in terms of just four torsional angles (Table 1). These data show the following: (i) the phenyl ring (C11–C16) adopts a very similar orientation in every compound; (ii) the orientation of the tert-butyl group is always such that one atom, C32, is close to the plane of the pyrazole ring, but always displaced from it with maximum and minimum displacements of 0.413 (3) Å in compound (VII) and 0.186 (2) Å in compound (V), respectively; the orientation of the benzyl substituent shows by far the widest range, although with no obvious systematic variation. In compound (V), the dihedral angle between the nitro group and the adjacent aryl ring is 11.2 (2)°, while the methoxy substituents exhibit different patterns of orientation in compounds (VI) and (VIII). In compound (VI) the methoxy atoms C721 and C731 are displaced from the plane of the ring (C71–C76) by 1.168 (4) and 0.009 (3) Å, respectively, while the displacements of atoms C731, C741 and C751 in compound (VIII) are 0.407 (2), 1.309 (2) and 0.262 (2) Å, respectively. In each compound, there is a short intramolecular C—H···N contact (Table 2) involving the aryl atom C12 and the ring atom N7; in every case, the C—H···N angle is narrow, 120° or less, suggesting that the interaction energy is likely to be small. This contact is probably adventitious, rather than a significant influence on the molecular conformation.
In each of compounds (I)–(VIII), the molecules have no internal symmetry and hence they are all chiral. While compounds (IV), (V), (VII) and (VIII) all crystallize as racemic mixtures of enantiomorphs, the crystals of compounds (I)–(III) and (VI) all contain a single enantiomorph. However, in the absence of significant resonant scattering, the enantiomorphs present in the crystals of compounds (I)–(III) and (VI) which had been selected for data collection cannot be identified. The synthesis of these compounds utilizes no reagents capable of imparting enantiomeric bias, and all are therefore expected to be formed as racemic mixtures, crystallizing as racemates for compounds (IV), (V), (VII) and (VIII), and as conglomerates for compounds (I)–(III) and (VI).
Despite their close similarities in both constitution and conformation, compounds (I)–(VIII) nonetheless show some interesting variations in their supramolecular aggregation, which is dominated by C—H···O and C—H···N hydrogen bonds, along with a single C—H···π(arene) hydrogen bond in each of compounds (II), (VII) and (VIII) (Table 2).
In both (I) and (II), molecules related by translation are linked into simple C(9) (Bernstein et al., 1995) chains running parallel to the [001] direction (Fig. 3). In addition, there is a rather long C—H···π(arene) hydrogen bond in (II), whose effect is to form a weak link between the chains along [001] so forming a sheet parallel to (010). No interaction of this kind can be identified in the structure of (I), so that while compounds (I) and (II) are isomorphous, they are not strictly isostructural (Acosta et al., 2009). In contrast, there are no direction-specific intermolecular interactions in the structures of compounds (III), (IV) or (VI), despite the presence of additional potential hydrogen-bond acceptor atoms in compounds (III) and (VI) [Figs. 1 and 2].
The supramolecular aggregation in compound (V) is two dimensional, in the form of deeply puckered sheets, and the formation of these sheets is readily analysed in terms of two one-dimensional substructures. In the simpler of these two substructures, molecules related by the 21 screw axis along (1/2, y, 1/4) are linked by a single C—H···O hydrogen bond (Table 2) into a simple C(6) chain running parallel to the [010] direction (Fig. 4). In the second substructure, molecules related by the c-glide plane at y = 0.75 are linked by one C—H···N hydrogen bond and one C—H···O hydrogen bond to form a C(6) C(8) [R22(17)] chain of rings running parallel to the [001] direction (Fig. 4). The combination of these two chain motifs generates a sheet parallel to (100).
There are five independent hydrogen bonds in the structure of compound (VII), which together generate a three-dimensional framework structure, whose formation can, however, be readily analysed in terms of three one-dimensional substructures, which involve, respectively, the three C—H···O hydrogen bonds, the C—H···N hydrogen bond and the C—H···π(arene) hydrogen bond. In the first substructure (Fig. 6), pairs of molecules related by inversion are linked by two independent C—H···O hydrogen bonds to form a dimeric unit containing three edge-fused hydrogen-bonded rings, with a centrosymmetric R22(14) ring centred at (1/2, 1/2, 1/2) flanked by two non-centrosymmetric but symmetry-related R22(7) rings. In addition, these units are linked by the third C—H···O hydrogen bond forming a further R22(8) ring motif, this time centrosymmetric and centred at (0, 1, 1/2). Propagation by inversion of these hydrogen bonds then generates a ribbon running parallel to the [110] direction, in which R22(8) rings centred at (n, 1- n, 1/2), where n represents an integer, alternate with R2214) rings centred at (1/2 + n, 1/2- n, 1/2), where n represents an integer (Fig. 6). A symmetry-related chain runs in the [110] direction
In the second substructure in (VII), a single C—H···N hydrogen bond links molecules related by the c-glide plane at y = 0.75 into a simple C(11) chain running parallel to the [201] direction (Fig. 7). Finally, a rather weak C—H···π(arene) hydrogen bond links molecules related by translation into a chain running along [100]. The combination of the one-dimensional substructures parallel to [100], [110], [110] and [201] is sufficient to link the molecules into a single three-dimensional framework.
Although the hydrogen-bonded supramolecular structure of compound (VIII) is only two-dimensional, as opposed to the three-dimensional structure found in compound (VII), it shares with compound (VII) the formation of a ribbon containing three types of ring, two of them centrosymmetric, built from three independent C—H···O hydrogen bonds, even though the details of the ribbon construction for the two compounds are different (Table 2). Pairs of molecules related by inversion are again linked by two C—H···O hydrogen bonds to form a dimer containing three edge-fused rings, but now with a centrosymmetric R22(24) ring flanked by two non-centrosymmetric R22(8) rings (Fig. 8). The third C—H···O hydrogen bond here generates a centrosymmetric R22(6) ring, and the combination of the these motifs generates a ribbon running parallel to the [210] direction, with R22(6) rings centred at (2n, 1/2- n, 1/2), alternating with R22(24) rings centred at (-1 + 2n, 1- n, 1/2), where n represents an integer (Fig. 8).
In the second substructure, a combination of C—H···O and C—H···π(arene) hydrogen bonds generates a chain of edge-fused rings parallel to the [100] direction, where centrosymmetric R22(6) centred at (n, 1/2, 1/2), where n represents an integer, formed by paired C—H···O hydrogen bonds alternate with centrosymmetric rings at (1/2, + n, 1/2, 1/2) formed by paired C—H···π(arene) hydrogen bonds (Fig. 9). The combination of the chains along [100] and the ribbons along [210] generates a sheet parallel to (001).
The structures reported here illustrate the subtle and often unpredictable interplay between intramolecular and intermolecular forces, particularly the interplay between intermolecular hydrogen bonding and molecular conformation, particularly as manifested here in the orientation of the aryl ring in the benzyl unit (Table 1). Thus, in compounds (III), (IV) and (VI) where there are no intermolecular hydrogen bonds, the conformations adopted by the benzyl unit are very similar. Similarly, in the isomorphous pair of compounds (I) and (II), where the chain-forming C—H···O hydrogen bond does not involve the benzyl unit, the overall conformations are very similar: the C—H···π(arene) unit in compound (II), which is to be regarded on geometric grounds as weak, appears to have little influence on the molecular conformation. The structures of compounds (VII) and (VIII) both contain a number of hydrogen bonds which involve the benzyl unit, providing both donors and acceptors in compound (VII) but only acceptors in compound (VIII). While this gives rise to a distinct benzyl ring orientation in compound (VIII), the conformation of compound (VII) is not significantly different from those of compounds (III) and (IV), where there are no direction-specific interactions of any kind between the molecules.