Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108038778/sk3276sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108038778/sk3276Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108038778/sk3276IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108038778/sk3276IIIsup4.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108038778/sk3276IVsup5.hkl |
CCDC references: 718155; 718156; 718157; 718158
Microwave-induced syntheses were carried out using a focused microwave reactor (CEM Discover TM). A mixture of the appropriately-substituted N-benzylaminopyrazole (2 mmol), 5,5-dimethylcyclohexane-1,3-dione (2 mmol) and an excess of paraformaldehyde (80–100 mg) was exposed to microwave radiation at 473 K with a maximum power of 300 W for 25 min. The reaction mixtures were dissolved in hot ethanol. After cooling these solutions, the solid products were collected by filtration and washed with ethanol, and then with hexane (2 × 5 ml) to afford the pure products. Colourless crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation of solutions in ethanol. For (I), yield 75%, m.p. 445–447 K; HRMS found 499.2835, C31H37N3O3 requires 499.2835. For (II), yield 85%, m.p. 503–505 K; HRMS found 529.2941, C32H39N3O4 requires 529.2941. For (III), yield 70%, m.p. 475–477 K; HRMS found 513.2635, C31H35N3O4 requires 513.2628. For (IV), yield 71%, m.p. 456–458 K; HRMS found 559.3032, C33H41N3O5 requires 559.3046.
For compounds (II) and (IV), the space groups P21/c and Pbca, respectively, were uniquely assigned from the systematic absences. Crystals of compounds (I) and (III) are triclinic; for each, the space group P1 was selected, and then confirmed by the structure analysis. All H atoms were located in difference maps and then treated as riding atoms in geometrically idealized positions with C—H distances of 0.95 Å (aromatic), 0.98 Å (CH3) or 0.99 Å (CH2) and O—H of 0.84 Å, and with Uiso(H) = kUeq(carrier), where k = 1.5 for the methyl and hydroxyl H atoms, and k = 1.2 for all other H atoms. In the crystal of compound (IV) selected for data collection, the site occupancy for the ethanol component refined to a value of 0.670 (7). Crystals of compound (III) diffracted rather weakly, even at 120 K, with only 49% of the data labelled `observed'; the merging R index was also fairly high at 0.129.
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: OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PRPKAPPA (Ferguson, 1999).
C31H37N3O3 | Z = 2 |
Mr = 499.64 | F(000) = 536 |
Triclinic, P1 | Dx = 1.272 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.5971 (8) Å | Cell parameters from 5986 reflections |
b = 11.2549 (16) Å | θ = 2.9–27.5° |
c = 12.1452 (14) Å | µ = 0.08 mm−1 |
α = 86.979 (11)° | T = 120 K |
β = 85.487 (10)° | Block, colourless |
γ = 87.216 (7)° | 0.51 × 0.36 × 0.18 mm |
V = 1304.7 (3) Å3 |
Bruker–Nonius KappaCCD diffractometer | 5986 independent reflections |
Radiation source: Bruker-Nonius FR591 rotating anode | 3281 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.081 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.9° |
ϕ & ω scans | h = −12→12 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −14→14 |
Tmin = 0.971, Tmax = 0.985 | l = −15→15 |
36057 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)] = 0.060 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.199 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.097P)2 + 0.8153P] where P = (Fo2 + 2Fc2)/3 |
5986 reflections | (Δ/σ)max < 0.001 |
340 parameters | Δρmax = 0.31 e Å−3 |
0 restraints | Δρmin = −0.39 e Å−3 |
C31H37N3O3 | γ = 87.216 (7)° |
Mr = 499.64 | V = 1304.7 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.5971 (8) Å | Mo Kα radiation |
b = 11.2549 (16) Å | µ = 0.08 mm−1 |
c = 12.1452 (14) Å | T = 120 K |
α = 86.979 (11)° | 0.51 × 0.36 × 0.18 mm |
β = 85.487 (10)° |
Bruker–Nonius KappaCCD diffractometer | 5986 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 3281 reflections with I > 2σ(I) |
Tmin = 0.971, Tmax = 0.985 | Rint = 0.081 |
36057 measured reflections |
R[F2 > 2σ(F2)] = 0.060 | 0 restraints |
wR(F2) = 0.199 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.31 e Å−3 |
5986 reflections | Δρmin = −0.39 e Å−3 |
340 parameters |
x | y | z | Uiso*/Ueq | ||
O51 | 0.4779 (2) | 0.00564 (17) | 0.65960 (16) | 0.0346 (5) | |
O55 | 0.04805 (18) | 0.16760 (17) | 0.72396 (16) | 0.0332 (5) | |
O74 | 0.37110 (19) | 0.67738 (17) | 1.10638 (15) | 0.0322 (5) | |
N1 | 0.2259 (2) | 0.46482 (18) | 0.49574 (17) | 0.0254 (5) | |
N2 | 0.1859 (2) | 0.42601 (18) | 0.39927 (17) | 0.0258 (5) | |
N7 | 0.3035 (2) | 0.38248 (18) | 0.67103 (17) | 0.0247 (5) | |
C3 | 0.1963 (3) | 0.3078 (2) | 0.4093 (2) | 0.0240 (6) | |
C3A | 0.2418 (3) | 0.2687 (2) | 0.5139 (2) | 0.0247 (6) | |
C4 | 0.2708 (3) | 0.1492 (2) | 0.5675 (2) | 0.0243 (6) | |
C5 | 0.2964 (3) | 0.1558 (2) | 0.6900 (2) | 0.0247 (6) | |
C6 | 0.3739 (3) | 0.2723 (2) | 0.7081 (2) | 0.0254 (6) | |
C7A | 0.2588 (3) | 0.3713 (2) | 0.5655 (2) | 0.0240 (6) | |
C11 | 0.2435 (3) | 0.5880 (2) | 0.5041 (2) | 0.0239 (6) | |
C12 | 0.3616 (3) | 0.6248 (2) | 0.5485 (2) | 0.0277 (6) | |
C13 | 0.3805 (3) | 0.7454 (2) | 0.5533 (2) | 0.0295 (6) | |
C14 | 0.2852 (3) | 0.8269 (2) | 0.5111 (2) | 0.0285 (6) | |
C15 | 0.1693 (3) | 0.7892 (2) | 0.4656 (2) | 0.0279 (6) | |
C16 | 0.1462 (3) | 0.6693 (2) | 0.4630 (2) | 0.0263 (6) | |
C31 | 0.1705 (3) | 0.2408 (2) | 0.3091 (2) | 0.0257 (6) | |
C32 | 0.1476 (3) | 0.1094 (2) | 0.3370 (2) | 0.0324 (6) | |
C33 | 0.0434 (3) | 0.2964 (2) | 0.2550 (2) | 0.0294 (6) | |
C34 | 0.2991 (3) | 0.2532 (3) | 0.2274 (2) | 0.0327 (6) | |
C51 | 0.3974 (3) | 0.0536 (2) | 0.7266 (2) | 0.0277 (6) | |
C52 | 0.3976 (3) | 0.0201 (2) | 0.8476 (2) | 0.0293 (6) | |
C53 | 0.2509 (3) | 0.0085 (2) | 0.9040 (2) | 0.0296 (6) | |
C54 | 0.1698 (3) | 0.1276 (2) | 0.8843 (2) | 0.0281 (6) | |
C55 | 0.1601 (3) | 0.1533 (2) | 0.7628 (2) | 0.0267 (6) | |
C71 | 0.2545 (3) | 0.4873 (2) | 0.8472 (2) | 0.0252 (6) | |
C72 | 0.1807 (3) | 0.4782 (2) | 0.9484 (2) | 0.0296 (6) | |
C73 | 0.2158 (3) | 0.5396 (2) | 1.0381 (2) | 0.0301 (6) | |
C74 | 0.3292 (3) | 0.6099 (2) | 1.0259 (2) | 0.0265 (6) | |
C75 | 0.4099 (3) | 0.6151 (2) | 0.9270 (2) | 0.0309 (6) | |
C76 | 0.3719 (3) | 0.5554 (2) | 0.8384 (2) | 0.0304 (6) | |
C77 | 0.1980 (3) | 0.4363 (2) | 0.7496 (2) | 0.0272 (6) | |
C531 | 0.1782 (3) | −0.0920 (2) | 0.8545 (2) | 0.0336 (7) | |
C532 | 0.2587 (3) | −0.0193 (3) | 1.0270 (2) | 0.0354 (7) | |
C741 | 0.2828 (3) | 0.6810 (3) | 1.2059 (2) | 0.0371 (7) | |
H4A | 0.3541 | 0.1110 | 0.5283 | 0.029* | |
H4B | 0.1904 | 0.0989 | 0.5609 | 0.029* | |
H6A | 0.3867 | 0.2760 | 0.7879 | 0.031* | |
H6B | 0.4681 | 0.2666 | 0.6687 | 0.031* | |
H12 | 0.4289 | 0.5679 | 0.5753 | 0.033* | |
H13 | 0.4596 | 0.7718 | 0.5858 | 0.035* | |
H14 | 0.2993 | 0.9096 | 0.5134 | 0.034* | |
H15 | 0.1045 | 0.8462 | 0.4357 | 0.033* | |
H16 | 0.0647 | 0.6434 | 0.4334 | 0.032* | |
H32A | 0.2325 | 0.0714 | 0.3654 | 0.049* | |
H32B | 0.1262 | 0.0707 | 0.2703 | 0.049* | |
H32C | 0.0693 | 0.1015 | 0.3934 | 0.049* | |
H33A | −0.0407 | 0.2849 | 0.3049 | 0.044* | |
H33B | 0.0335 | 0.2584 | 0.1855 | 0.044* | |
H33C | 0.0557 | 0.3818 | 0.2400 | 0.044* | |
H34A | 0.3145 | 0.3378 | 0.2101 | 0.049* | |
H34B | 0.2839 | 0.2141 | 0.1594 | 0.049* | |
H34C | 0.3812 | 0.2156 | 0.2604 | 0.049* | |
H52A | 0.4459 | 0.0813 | 0.8841 | 0.035* | |
H52B | 0.4512 | −0.0566 | 0.8574 | 0.035* | |
H54A | 0.0747 | 0.1241 | 0.9219 | 0.034* | |
H54B | 0.2182 | 0.1923 | 0.9156 | 0.034* | |
H72 | 0.1030 | 0.4284 | 0.9577 | 0.036* | |
H73 | 0.1618 | 0.5329 | 1.1069 | 0.036* | |
H75 | 0.4918 | 0.6599 | 0.9198 | 0.037* | |
H76 | 0.4273 | 0.5610 | 0.7701 | 0.037* | |
H77A | 0.1312 | 0.3750 | 0.7767 | 0.033* | |
H77B | 0.1449 | 0.5004 | 0.7097 | 0.033* | |
H53A | 0.1746 | −0.0755 | 0.7747 | 0.050* | |
H53B | 0.0829 | −0.0972 | 0.8892 | 0.050* | |
H53C | 0.2307 | −0.1676 | 0.8678 | 0.050* | |
H53D | 0.3042 | 0.0451 | 1.0595 | 0.053* | |
H53E | 0.3130 | −0.0944 | 1.0385 | 0.053* | |
H53F | 0.1640 | −0.0268 | 1.0624 | 0.053* | |
H74A | 0.1873 | 0.7057 | 1.1886 | 0.056* | |
H74B | 0.3174 | 0.7381 | 1.2543 | 0.056* | |
H74C | 0.2828 | 0.6017 | 1.2433 | 0.056* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O51 | 0.0351 (11) | 0.0319 (11) | 0.0358 (11) | 0.0085 (9) | −0.0014 (9) | −0.0031 (9) |
O55 | 0.0246 (10) | 0.0374 (11) | 0.0377 (11) | 0.0017 (8) | −0.0069 (8) | 0.0006 (9) |
O74 | 0.0314 (10) | 0.0400 (11) | 0.0260 (10) | −0.0053 (9) | 0.0007 (8) | −0.0086 (8) |
N1 | 0.0332 (12) | 0.0199 (11) | 0.0236 (11) | −0.0015 (9) | −0.0053 (9) | −0.0022 (9) |
N2 | 0.0305 (12) | 0.0226 (11) | 0.0251 (11) | −0.0019 (9) | −0.0038 (9) | −0.0053 (9) |
N7 | 0.0271 (11) | 0.0209 (11) | 0.0263 (11) | 0.0014 (9) | −0.0037 (9) | −0.0040 (9) |
C3 | 0.0244 (13) | 0.0192 (13) | 0.0281 (14) | −0.0031 (10) | 0.0016 (10) | −0.0015 (10) |
C3A | 0.0250 (13) | 0.0221 (13) | 0.0271 (14) | −0.0010 (10) | 0.0002 (10) | −0.0036 (11) |
C4 | 0.0262 (13) | 0.0185 (13) | 0.0287 (14) | −0.0014 (10) | −0.0044 (11) | −0.0015 (10) |
C5 | 0.0239 (13) | 0.0227 (13) | 0.0276 (14) | −0.0007 (10) | −0.0029 (10) | −0.0021 (11) |
C6 | 0.0276 (14) | 0.0215 (13) | 0.0276 (14) | −0.0014 (10) | −0.0040 (11) | −0.0021 (11) |
C7A | 0.0246 (13) | 0.0219 (13) | 0.0255 (13) | −0.0008 (10) | −0.0016 (10) | −0.0030 (11) |
C11 | 0.0280 (13) | 0.0197 (13) | 0.0239 (13) | −0.0016 (10) | 0.0011 (10) | −0.0046 (10) |
C12 | 0.0285 (14) | 0.0255 (14) | 0.0285 (14) | 0.0012 (11) | −0.0014 (11) | −0.0005 (11) |
C13 | 0.0316 (15) | 0.0251 (14) | 0.0323 (15) | −0.0071 (11) | −0.0009 (12) | −0.0041 (12) |
C14 | 0.0367 (15) | 0.0180 (13) | 0.0308 (14) | −0.0029 (11) | −0.0003 (12) | −0.0016 (11) |
C15 | 0.0345 (15) | 0.0217 (13) | 0.0269 (14) | 0.0031 (11) | −0.0010 (11) | −0.0016 (11) |
C16 | 0.0286 (14) | 0.0257 (14) | 0.0248 (13) | −0.0022 (11) | −0.0028 (11) | −0.0010 (11) |
C31 | 0.0244 (13) | 0.0247 (14) | 0.0283 (14) | −0.0011 (10) | −0.0024 (11) | −0.0031 (11) |
C32 | 0.0395 (16) | 0.0263 (15) | 0.0322 (15) | −0.0011 (12) | −0.0047 (12) | −0.0058 (12) |
C33 | 0.0331 (15) | 0.0255 (14) | 0.0301 (14) | −0.0015 (11) | −0.0039 (12) | −0.0048 (11) |
C34 | 0.0349 (16) | 0.0317 (15) | 0.0319 (15) | −0.0013 (12) | −0.0007 (12) | −0.0085 (12) |
C51 | 0.0259 (14) | 0.0201 (13) | 0.0374 (15) | −0.0027 (11) | −0.0047 (12) | −0.0005 (11) |
C52 | 0.0297 (14) | 0.0254 (14) | 0.0333 (15) | 0.0013 (11) | −0.0070 (12) | −0.0004 (12) |
C53 | 0.0308 (15) | 0.0279 (15) | 0.0306 (15) | −0.0024 (11) | −0.0071 (12) | 0.0011 (12) |
C54 | 0.0246 (14) | 0.0278 (14) | 0.0323 (15) | −0.0011 (11) | −0.0038 (11) | −0.0020 (11) |
C55 | 0.0271 (14) | 0.0199 (13) | 0.0330 (15) | 0.0008 (10) | −0.0037 (11) | −0.0013 (11) |
C71 | 0.0292 (14) | 0.0200 (13) | 0.0262 (14) | 0.0016 (10) | −0.0023 (11) | −0.0015 (10) |
C72 | 0.0292 (14) | 0.0308 (15) | 0.0290 (14) | −0.0053 (11) | 0.0001 (11) | −0.0018 (12) |
C73 | 0.0338 (15) | 0.0315 (15) | 0.0245 (14) | −0.0020 (12) | 0.0008 (11) | −0.0018 (12) |
C74 | 0.0302 (14) | 0.0262 (14) | 0.0231 (13) | −0.0016 (11) | −0.0015 (11) | −0.0024 (11) |
C75 | 0.0288 (14) | 0.0341 (15) | 0.0302 (15) | −0.0086 (12) | 0.0033 (11) | −0.0059 (12) |
C76 | 0.0350 (15) | 0.0325 (15) | 0.0235 (14) | −0.0034 (12) | 0.0031 (11) | −0.0041 (12) |
C77 | 0.0295 (14) | 0.0247 (14) | 0.0270 (14) | −0.0006 (11) | 0.0001 (11) | −0.0021 (11) |
C531 | 0.0376 (16) | 0.0298 (15) | 0.0346 (15) | −0.0072 (12) | −0.0070 (12) | −0.0004 (12) |
C532 | 0.0369 (16) | 0.0360 (16) | 0.0337 (16) | −0.0021 (13) | −0.0068 (12) | 0.0011 (13) |
C741 | 0.0352 (16) | 0.0508 (19) | 0.0256 (14) | −0.0020 (14) | 0.0010 (12) | −0.0106 (13) |
O51—C51 | 1.208 (3) | C32—H32C | 0.98 |
O55—C55 | 1.208 (3) | C33—H33A | 0.98 |
O74—C74 | 1.365 (3) | C33—H33B | 0.98 |
O74—C741 | 1.422 (3) | C33—H33C | 0.98 |
N1—C7A | 1.357 (3) | C34—H34A | 0.98 |
N1—N2 | 1.361 (3) | C34—H34B | 0.98 |
N1—C11 | 1.414 (3) | C34—H34C | 0.98 |
N2—C3 | 1.329 (3) | C51—C52 | 1.498 (4) |
N7—C7A | 1.397 (3) | C52—C53 | 1.525 (4) |
N7—C6 | 1.451 (3) | C52—H52A | 0.99 |
N7—C77 | 1.467 (3) | C52—H52B | 0.99 |
C3—C3A | 1.418 (4) | C53—C532 | 1.516 (4) |
C3—C31 | 1.508 (4) | C53—C531 | 1.530 (4) |
C3A—C7A | 1.364 (3) | C53—C54 | 1.535 (4) |
C3A—C4 | 1.487 (3) | C54—C55 | 1.498 (4) |
C4—C5 | 1.533 (3) | C54—H54A | 0.99 |
C4—H4A | 0.99 | C54—H54B | 0.99 |
C4—H4B | 0.99 | C71—C72 | 1.372 (4) |
C5—C55 | 1.521 (4) | C71—C76 | 1.387 (4) |
C5—C51 | 1.538 (4) | C71—C77 | 1.494 (4) |
C5—C6 | 1.572 (4) | C72—C73 | 1.391 (4) |
C6—H6A | 0.99 | C72—H72 | 0.95 |
C6—H6B | 0.99 | C73—C74 | 1.370 (4) |
C11—C16 | 1.379 (4) | C73—H73 | 0.95 |
C11—C12 | 1.383 (4) | C74—C75 | 1.377 (4) |
C12—C13 | 1.383 (4) | C75—C76 | 1.380 (4) |
C12—H12 | 0.95 | C75—H75 | 0.95 |
C13—C14 | 1.372 (4) | C76—H76 | 0.95 |
C13—H13 | 0.95 | C77—H77A | 0.99 |
C14—C15 | 1.375 (4) | C77—H77B | 0.99 |
C14—H14 | 0.95 | C531—H53A | 0.98 |
C15—C16 | 1.380 (4) | C531—H53B | 0.98 |
C15—H15 | 0.95 | C531—H53C | 0.98 |
C16—H16 | 0.95 | C532—H53D | 0.98 |
C31—C32 | 1.522 (4) | C532—H53E | 0.98 |
C31—C33 | 1.523 (4) | C532—H53F | 0.98 |
C31—C34 | 1.528 (4) | C741—H74A | 0.98 |
C32—H32A | 0.98 | C741—H74B | 0.98 |
C32—H32B | 0.98 | C741—H74C | 0.98 |
C74—O74—C741 | 116.4 (2) | C31—C34—H34B | 109.5 |
C7A—N1—N2 | 110.6 (2) | H34A—C34—H34B | 109.5 |
C7A—N1—C11 | 130.2 (2) | C31—C34—H34C | 109.5 |
N2—N1—C11 | 118.7 (2) | H34A—C34—H34C | 109.5 |
C3—N2—N1 | 105.7 (2) | H34B—C34—H34C | 109.5 |
C7A—N7—C6 | 109.9 (2) | O51—C51—C52 | 121.4 (2) |
C7A—N7—C77 | 114.5 (2) | O51—C51—C5 | 120.4 (2) |
C6—N7—C77 | 116.8 (2) | C52—C51—C5 | 118.1 (2) |
N2—C3—C3A | 111.0 (2) | C51—C52—C53 | 113.0 (2) |
N2—C3—C31 | 117.1 (2) | C51—C52—H52A | 109.0 |
C3A—C3—C31 | 131.7 (2) | C53—C52—H52A | 109.0 |
C7A—C3A—C3 | 104.4 (2) | C51—C52—H52B | 109.0 |
C7A—C3A—C4 | 122.1 (2) | C53—C52—H52B | 109.0 |
C3—C3A—C4 | 133.5 (2) | H52A—C52—H52B | 107.8 |
C3A—C4—C5 | 112.3 (2) | C532—C53—C52 | 110.2 (2) |
C3A—C4—H4A | 109.1 | C532—C53—C531 | 109.0 (2) |
C5—C4—H4A | 109.1 | C52—C53—C531 | 109.8 (2) |
C3A—C4—H4B | 109.1 | C532—C53—C54 | 110.2 (2) |
C5—C4—H4B | 109.1 | C52—C53—C54 | 107.5 (2) |
H4A—C4—H4B | 107.9 | C531—C53—C54 | 110.2 (2) |
C55—C5—C4 | 111.4 (2) | C55—C54—C53 | 109.9 (2) |
C55—C5—C51 | 110.1 (2) | C55—C54—H54A | 109.7 |
C4—C5—C51 | 110.8 (2) | C53—C54—H54A | 109.7 |
C55—C5—C6 | 109.8 (2) | C55—C54—H54B | 109.7 |
C4—C5—C6 | 109.9 (2) | C53—C54—H54B | 109.7 |
C51—C5—C6 | 104.6 (2) | H54A—C54—H54B | 108.2 |
N7—C6—C5 | 115.2 (2) | O55—C55—C54 | 121.2 (2) |
N7—C6—H6A | 108.5 | O55—C55—C5 | 121.4 (2) |
C5—C6—H6A | 108.5 | C54—C55—C5 | 117.4 (2) |
N7—C6—H6B | 108.5 | C72—C71—C76 | 117.4 (2) |
C5—C6—H6B | 108.5 | C72—C71—C77 | 119.5 (2) |
H6A—C6—H6B | 107.5 | C76—C71—C77 | 122.8 (2) |
C16—C11—C12 | 121.2 (2) | C71—C72—C73 | 122.1 (3) |
C16—C11—N1 | 119.5 (2) | C71—C72—H72 | 119.0 |
C12—C11—N1 | 119.3 (2) | C73—C72—H72 | 119.0 |
C13—C12—C11 | 119.1 (2) | C74—C73—C72 | 119.3 (2) |
C13—C12—H12 | 120.5 | C74—C73—H73 | 120.4 |
C11—C12—H12 | 120.5 | C72—C73—H73 | 120.4 |
C14—C13—C12 | 120.1 (3) | O74—C74—C73 | 124.7 (2) |
C14—C13—H13 | 120.0 | O74—C74—C75 | 115.6 (2) |
C12—C13—H13 | 120.0 | C73—C74—C75 | 119.8 (2) |
C13—C14—C15 | 120.2 (2) | C74—C75—C76 | 120.1 (3) |
C13—C14—H14 | 119.9 | C74—C75—H75 | 119.9 |
C15—C14—H14 | 119.9 | C76—C75—H75 | 119.9 |
C14—C15—C16 | 120.6 (2) | C75—C76—C71 | 121.2 (2) |
C14—C15—H15 | 119.7 | C75—C76—H76 | 119.4 |
C16—C15—H15 | 119.7 | C71—C76—H76 | 119.4 |
C11—C16—C15 | 118.7 (2) | N7—C77—C71 | 115.1 (2) |
C11—C16—H16 | 120.6 | N7—C77—H77A | 108.5 |
C15—C16—H16 | 120.6 | C71—C77—H77A | 108.5 |
N1—C7A—C3A | 108.3 (2) | N7—C77—H77B | 108.5 |
N1—C7A—N7 | 124.1 (2) | C71—C77—H77B | 108.5 |
C3A—C7A—N7 | 127.6 (2) | H77A—C77—H77B | 107.5 |
C3—C31—C32 | 112.5 (2) | C53—C531—H53A | 109.5 |
C3—C31—C33 | 109.9 (2) | C53—C531—H53B | 109.5 |
C32—C31—C33 | 109.1 (2) | H53A—C531—H53B | 109.5 |
C3—C31—C34 | 107.2 (2) | C53—C531—H53C | 109.5 |
C32—C31—C34 | 109.5 (2) | H53A—C531—H53C | 109.5 |
C33—C31—C34 | 108.6 (2) | H53B—C531—H53C | 109.5 |
C31—C32—H32A | 109.5 | C53—C532—H53D | 109.5 |
C31—C32—H32B | 109.5 | C53—C532—H53E | 109.5 |
H32A—C32—H32B | 109.5 | H53D—C532—H53E | 109.5 |
C31—C32—H32C | 109.5 | C53—C532—H53F | 109.5 |
H32A—C32—H32C | 109.5 | H53D—C532—H53F | 109.5 |
H32B—C32—H32C | 109.5 | H53E—C532—H53F | 109.5 |
C31—C33—H33A | 109.5 | O74—C741—H74A | 109.5 |
C31—C33—H33B | 109.5 | O74—C741—H74B | 109.5 |
H33A—C33—H33B | 109.5 | H74A—C741—H74B | 109.5 |
C31—C33—H33C | 109.5 | O74—C741—H74C | 109.5 |
H33A—C33—H33C | 109.5 | H74A—C741—H74C | 109.5 |
H33B—C33—H33C | 109.5 | H74B—C741—H74C | 109.5 |
C31—C34—H34A | 109.5 | ||
C7A—N1—N2—C3 | −0.9 (3) | C3A—C3—C31—C32 | 20.8 (4) |
C11—N1—N2—C3 | 171.7 (2) | N2—C3—C31—C33 | −43.4 (3) |
N1—N2—C3—C3A | 0.7 (3) | C3A—C3—C31—C33 | 142.5 (3) |
N1—N2—C3—C31 | −174.5 (2) | N2—C3—C31—C34 | 74.5 (3) |
N2—C3—C3A—C7A | −0.3 (3) | C3A—C3—C31—C34 | −99.6 (3) |
C31—C3—C3A—C7A | 174.0 (3) | C55—C5—C51—O51 | 147.2 (2) |
N2—C3—C3A—C4 | −179.8 (3) | C4—C5—C51—O51 | 23.4 (3) |
C31—C3—C3A—C4 | −5.4 (5) | C6—C5—C51—O51 | −94.9 (3) |
C7A—C3A—C4—C5 | 9.6 (3) | C55—C5—C51—C52 | −35.9 (3) |
C3—C3A—C4—C5 | −171.1 (3) | C4—C5—C51—C52 | −159.6 (2) |
C3A—C4—C5—C55 | 87.3 (3) | C6—C5—C51—C52 | 82.0 (3) |
C3A—C4—C5—C51 | −149.7 (2) | O51—C51—C52—C53 | −136.6 (3) |
C3A—C4—C5—C6 | −34.6 (3) | C5—C51—C52—C53 | 46.5 (3) |
C7A—N7—C6—C5 | −46.4 (3) | C51—C52—C53—C532 | −177.2 (2) |
C77—N7—C6—C5 | 86.2 (3) | C51—C52—C53—C531 | 62.8 (3) |
C55—C5—C6—N7 | −66.4 (3) | C51—C52—C53—C54 | −57.1 (3) |
C4—C5—C6—N7 | 56.5 (3) | C532—C53—C54—C55 | −178.9 (2) |
C51—C5—C6—N7 | 175.4 (2) | C52—C53—C54—C55 | 61.1 (3) |
C7A—N1—C11—C16 | −146.0 (3) | C531—C53—C54—C55 | −58.6 (3) |
N2—N1—C11—C16 | 43.1 (3) | C53—C54—C55—O55 | 121.4 (3) |
C7A—N1—C11—C12 | 37.2 (4) | C53—C54—C55—C5 | −56.2 (3) |
N2—N1—C11—C12 | −133.8 (2) | C4—C5—C55—O55 | −12.9 (3) |
C16—C11—C12—C13 | 1.2 (4) | C51—C5—C55—O55 | −136.3 (3) |
N1—C11—C12—C13 | 178.0 (2) | C6—C5—C55—O55 | 109.0 (3) |
C11—C12—C13—C14 | −2.1 (4) | C4—C5—C55—C54 | 164.6 (2) |
C12—C13—C14—C15 | 1.1 (4) | C51—C5—C55—C54 | 41.3 (3) |
C13—C14—C15—C16 | 0.9 (4) | C6—C5—C55—C54 | −73.4 (3) |
C12—C11—C16—C15 | 0.8 (4) | C76—C71—C72—C73 | 3.6 (4) |
N1—C11—C16—C15 | −176.1 (2) | C77—C71—C72—C73 | −169.6 (2) |
C14—C15—C16—C11 | −1.8 (4) | C71—C72—C73—C74 | −1.2 (4) |
N2—N1—C7A—C3A | 0.7 (3) | C741—O74—C74—C73 | −5.3 (4) |
C11—N1—C7A—C3A | −170.8 (2) | C741—O74—C74—C75 | 175.0 (2) |
N2—N1—C7A—N7 | −180.0 (2) | C72—C73—C74—O74 | 177.7 (2) |
C11—N1—C7A—N7 | 8.5 (4) | C72—C73—C74—C75 | −2.6 (4) |
C3—C3A—C7A—N1 | −0.2 (3) | O74—C74—C75—C76 | −176.4 (2) |
C4—C3A—C7A—N1 | 179.3 (2) | C73—C74—C75—C76 | 3.9 (4) |
C3—C3A—C7A—N7 | −179.5 (2) | C74—C75—C76—C71 | −1.3 (4) |
C4—C3A—C7A—N7 | 0.0 (4) | C72—C71—C76—C75 | −2.3 (4) |
C6—N7—C7A—N1 | −160.7 (2) | C77—C71—C76—C75 | 170.7 (2) |
C77—N7—C7A—N1 | 65.6 (3) | C7A—N7—C77—C71 | −159.8 (2) |
C6—N7—C7A—C3A | 18.5 (4) | C6—N7—C77—C71 | 69.7 (3) |
C77—N7—C7A—C3A | −115.2 (3) | C72—C71—C77—N7 | −143.6 (2) |
N2—C3—C31—C32 | −165.1 (2) | C76—C71—C77—N7 | 43.6 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C15—H15···O55i | 0.95 | 2.54 | 3.229 (3) | 130 |
C16—H16···Cg1i | 0.95 | 2.88 | 3.589 (3) | 132 |
Symmetry code: (i) −x, −y+1, −z+1. |
C32H39N3O4 | F(000) = 1136 |
Mr = 529.66 | Dx = 1.260 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 6394 reflections |
a = 12.4683 (15) Å | θ = 3.2–27.5° |
b = 10.2892 (12) Å | µ = 0.08 mm−1 |
c = 21.7635 (16) Å | T = 120 K |
β = 90.843 (10)° | Block, colourless |
V = 2791.7 (5) Å3 | 0.32 × 0.25 × 0.12 mm |
Z = 4 |
Bruker–Nonius KappaCCD diffractometer | 6394 independent reflections |
Radiation source: Bruker-Nonius FR591 rotating anode | 4404 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.065 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.2° |
ϕ & ω scans | h = −16→16 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −13→13 |
Tmin = 0.965, Tmax = 0.990 | l = −28→28 |
45254 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) = 0.138 | H-atom parameters constrained |
S = 1.18 | w = 1/[σ2(Fo2) + (0.0286P)2 + 3.2694P] where P = (Fo2 + 2Fc2)/3 |
6394 reflections | (Δ/σ)max < 0.001 |
359 parameters | Δρmax = 0.28 e Å−3 |
0 restraints | Δρmin = −0.31 e Å−3 |
C32H39N3O4 | V = 2791.7 (5) Å3 |
Mr = 529.66 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.4683 (15) Å | µ = 0.08 mm−1 |
b = 10.2892 (12) Å | T = 120 K |
c = 21.7635 (16) Å | 0.32 × 0.25 × 0.12 mm |
β = 90.843 (10)° |
Bruker–Nonius KappaCCD diffractometer | 6394 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 4404 reflections with I > 2σ(I) |
Tmin = 0.965, Tmax = 0.990 | Rint = 0.065 |
45254 measured reflections |
R[F2 > 2σ(F2)] = 0.061 | 0 restraints |
wR(F2) = 0.138 | H-atom parameters constrained |
S = 1.18 | Δρmax = 0.28 e Å−3 |
6394 reflections | Δρmin = −0.31 e Å−3 |
359 parameters |
x | y | z | Uiso*/Ueq | ||
O51 | 0.87453 (14) | 0.75668 (17) | 0.61797 (8) | 0.0285 (4) | |
O55 | 0.83207 (14) | 0.37125 (17) | 0.70208 (9) | 0.0313 (4) | |
O72 | 0.48952 (13) | 0.35748 (17) | 0.79412 (7) | 0.0247 (4) | |
O73 | 0.32584 (13) | 0.47921 (18) | 0.84955 (8) | 0.0270 (4) | |
N1 | 0.60221 (14) | 0.30765 (19) | 0.54413 (9) | 0.0179 (4) | |
N2 | 0.67439 (14) | 0.25107 (19) | 0.50560 (9) | 0.0173 (4) | |
N7 | 0.59712 (14) | 0.47487 (18) | 0.62258 (9) | 0.0175 (4) | |
C3 | 0.76637 (17) | 0.3113 (2) | 0.51733 (10) | 0.0165 (5) | |
C3A | 0.75543 (17) | 0.4060 (2) | 0.56364 (10) | 0.0184 (5) | |
C4 | 0.83106 (18) | 0.5005 (2) | 0.59254 (11) | 0.0215 (5) | |
C5 | 0.78300 (17) | 0.5648 (2) | 0.64916 (10) | 0.0182 (5) | |
C6 | 0.65969 (17) | 0.5904 (2) | 0.63767 (11) | 0.0188 (5) | |
C7A | 0.65012 (17) | 0.3997 (2) | 0.57969 (10) | 0.0174 (5) | |
C11 | 0.49320 (17) | 0.2708 (2) | 0.53941 (10) | 0.0176 (5) | |
C12 | 0.41355 (18) | 0.3633 (2) | 0.53586 (11) | 0.0208 (5) | |
C13 | 0.30822 (19) | 0.3241 (2) | 0.52898 (11) | 0.0236 (5) | |
C14 | 0.28311 (19) | 0.1946 (3) | 0.52431 (11) | 0.0239 (5) | |
C15 | 0.36305 (18) | 0.1021 (2) | 0.52861 (11) | 0.0242 (5) | |
C16 | 0.46844 (18) | 0.1409 (2) | 0.53686 (11) | 0.0196 (5) | |
C31 | 0.86410 (17) | 0.2769 (2) | 0.48063 (10) | 0.0182 (5) | |
C32 | 0.95863 (19) | 0.2431 (3) | 0.52294 (12) | 0.0270 (6) | |
C33 | 0.84272 (19) | 0.1611 (2) | 0.43891 (11) | 0.0238 (5) | |
C34 | 0.89340 (19) | 0.3941 (2) | 0.44119 (11) | 0.0237 (5) | |
C51 | 0.83268 (18) | 0.6997 (2) | 0.65931 (11) | 0.0195 (5) | |
C52 | 0.8237 (2) | 0.7586 (2) | 0.72212 (11) | 0.0270 (6) | |
C53 | 0.8540 (2) | 0.6655 (3) | 0.77381 (12) | 0.0312 (6) | |
C54 | 0.7830 (2) | 0.5442 (3) | 0.76690 (12) | 0.0298 (6) | |
C55 | 0.80049 (17) | 0.4814 (2) | 0.70631 (11) | 0.0219 (5) | |
C71 | 0.45886 (17) | 0.4772 (2) | 0.70299 (10) | 0.0177 (5) | |
C72 | 0.43340 (18) | 0.4518 (2) | 0.76333 (11) | 0.0193 (5) | |
C73 | 0.34713 (18) | 0.5151 (2) | 0.79076 (11) | 0.0205 (5) | |
C74 | 0.28774 (18) | 0.6041 (2) | 0.75745 (11) | 0.0218 (5) | |
C75 | 0.31304 (19) | 0.6284 (2) | 0.69711 (12) | 0.0244 (5) | |
C76 | 0.39746 (18) | 0.5658 (2) | 0.66993 (11) | 0.0227 (5) | |
C77 | 0.55088 (18) | 0.4043 (2) | 0.67472 (11) | 0.0198 (5) | |
C531 | 0.9715 (2) | 0.6265 (3) | 0.76954 (15) | 0.0418 (7) | |
C532 | 0.8330 (3) | 0.7304 (4) | 0.83507 (14) | 0.0574 (10) | |
C721 | 0.5395 (2) | 0.3965 (3) | 0.85102 (12) | 0.0307 (6) | |
C731 | 0.2419 (2) | 0.5468 (3) | 0.87925 (12) | 0.0294 (6) | |
H4A | 0.8494 | 0.5684 | 0.5622 | 0.026* | |
H4B | 0.8981 | 0.4550 | 0.6046 | 0.026* | |
H6A | 0.6297 | 0.6306 | 0.6750 | 0.023* | |
H6B | 0.6514 | 0.6537 | 0.6037 | 0.023* | |
H12 | 0.4309 | 0.4531 | 0.5381 | 0.025* | |
H13 | 0.2527 | 0.3872 | 0.5275 | 0.028* | |
H14 | 0.2106 | 0.1686 | 0.5181 | 0.029* | |
H15 | 0.3457 | 0.0123 | 0.5259 | 0.029* | |
H16 | 0.5237 | 0.0777 | 0.5408 | 0.024* | |
H32A | 0.9391 | 0.1701 | 0.5494 | 0.040* | |
H32B | 0.9771 | 0.3186 | 0.5484 | 0.040* | |
H32C | 1.0205 | 0.2189 | 0.4982 | 0.040* | |
H33A | 0.7807 | 0.1797 | 0.4121 | 0.036* | |
H33B | 0.8278 | 0.0843 | 0.4640 | 0.036* | |
H33C | 0.9058 | 0.1448 | 0.4137 | 0.036* | |
H34A | 0.9108 | 0.4681 | 0.4679 | 0.036* | |
H34B | 0.8325 | 0.4166 | 0.4142 | 0.036* | |
H34C | 0.9557 | 0.3727 | 0.4162 | 0.036* | |
H52A | 0.7490 | 0.7883 | 0.7279 | 0.032* | |
H52B | 0.8709 | 0.8359 | 0.7247 | 0.032* | |
H54A | 0.8003 | 0.4819 | 0.8002 | 0.036* | |
H54B | 0.7067 | 0.5692 | 0.7704 | 0.036* | |
H74 | 0.2297 | 0.6485 | 0.7760 | 0.026* | |
H75 | 0.2716 | 0.6891 | 0.6740 | 0.029* | |
H76 | 0.4137 | 0.5834 | 0.6282 | 0.027* | |
H77A | 0.6074 | 0.3899 | 0.7064 | 0.024* | |
H77B | 0.5252 | 0.3182 | 0.6605 | 0.024* | |
H53A | 1.0168 | 0.7036 | 0.7749 | 0.063* | |
H53B | 0.9844 | 0.5876 | 0.7292 | 0.063* | |
H53C | 0.9888 | 0.5631 | 0.8018 | 0.063* | |
H53D | 0.7572 | 0.7549 | 0.8371 | 0.086* | |
H53E | 0.8778 | 0.8083 | 0.8391 | 0.086* | |
H53F | 0.8504 | 0.6698 | 0.8685 | 0.086* | |
H72A | 0.4949 | 0.3689 | 0.8854 | 0.046* | |
H72B | 0.5473 | 0.4912 | 0.8517 | 0.046* | |
H72C | 0.6104 | 0.3559 | 0.8548 | 0.046* | |
H73A | 0.1736 | 0.5285 | 0.8581 | 0.044* | |
H73B | 0.2562 | 0.6404 | 0.8781 | 0.044* | |
H73C | 0.2379 | 0.5181 | 0.9221 | 0.044* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O51 | 0.0304 (9) | 0.0218 (9) | 0.0335 (10) | −0.0044 (8) | 0.0112 (8) | −0.0017 (8) |
O55 | 0.0257 (9) | 0.0200 (10) | 0.0481 (12) | −0.0013 (8) | −0.0052 (8) | 0.0060 (8) |
O72 | 0.0298 (9) | 0.0248 (9) | 0.0193 (9) | 0.0085 (8) | −0.0003 (7) | −0.0009 (7) |
O73 | 0.0277 (9) | 0.0325 (10) | 0.0210 (9) | 0.0082 (8) | 0.0069 (7) | −0.0007 (8) |
N1 | 0.0121 (9) | 0.0190 (10) | 0.0225 (10) | −0.0019 (8) | 0.0024 (7) | −0.0029 (8) |
N2 | 0.0137 (9) | 0.0178 (10) | 0.0204 (10) | 0.0002 (8) | 0.0033 (7) | −0.0012 (8) |
N7 | 0.0145 (9) | 0.0174 (10) | 0.0209 (10) | −0.0019 (8) | 0.0041 (7) | −0.0028 (8) |
C3 | 0.0137 (10) | 0.0152 (11) | 0.0206 (12) | −0.0006 (9) | −0.0001 (9) | 0.0024 (9) |
C3A | 0.0157 (11) | 0.0186 (12) | 0.0210 (12) | −0.0007 (9) | 0.0021 (9) | −0.0007 (10) |
C4 | 0.0154 (11) | 0.0214 (12) | 0.0278 (13) | −0.0030 (10) | 0.0047 (9) | −0.0055 (10) |
C5 | 0.0148 (10) | 0.0181 (12) | 0.0216 (12) | −0.0013 (9) | 0.0013 (9) | −0.0019 (10) |
C6 | 0.0168 (11) | 0.0190 (12) | 0.0207 (12) | 0.0006 (9) | 0.0017 (9) | −0.0018 (10) |
C7A | 0.0165 (11) | 0.0160 (11) | 0.0198 (11) | −0.0010 (9) | 0.0014 (9) | 0.0005 (9) |
C11 | 0.0131 (10) | 0.0230 (12) | 0.0166 (11) | −0.0039 (9) | 0.0014 (8) | −0.0008 (9) |
C12 | 0.0205 (12) | 0.0159 (11) | 0.0261 (13) | −0.0005 (10) | 0.0019 (9) | 0.0012 (10) |
C13 | 0.0173 (11) | 0.0252 (13) | 0.0284 (13) | 0.0047 (10) | −0.0005 (10) | 0.0015 (11) |
C14 | 0.0143 (11) | 0.0301 (14) | 0.0274 (13) | −0.0039 (10) | 0.0004 (9) | −0.0022 (11) |
C15 | 0.0195 (12) | 0.0209 (12) | 0.0322 (14) | −0.0063 (10) | 0.0020 (10) | −0.0043 (11) |
C16 | 0.0172 (11) | 0.0173 (11) | 0.0244 (12) | 0.0012 (9) | 0.0025 (9) | −0.0018 (10) |
C31 | 0.0153 (11) | 0.0179 (12) | 0.0215 (12) | −0.0009 (9) | 0.0028 (9) | −0.0025 (10) |
C32 | 0.0177 (12) | 0.0326 (14) | 0.0307 (14) | 0.0059 (11) | 0.0014 (10) | −0.0034 (12) |
C33 | 0.0197 (12) | 0.0225 (13) | 0.0292 (13) | −0.0009 (10) | 0.0066 (10) | −0.0066 (11) |
C34 | 0.0188 (12) | 0.0234 (13) | 0.0290 (13) | −0.0045 (10) | 0.0065 (10) | 0.0000 (11) |
C51 | 0.0149 (11) | 0.0174 (12) | 0.0262 (13) | 0.0016 (9) | −0.0003 (9) | −0.0008 (10) |
C52 | 0.0286 (13) | 0.0228 (13) | 0.0297 (14) | −0.0024 (11) | 0.0000 (11) | −0.0085 (11) |
C53 | 0.0351 (15) | 0.0342 (15) | 0.0241 (13) | −0.0009 (12) | −0.0055 (11) | −0.0049 (12) |
C54 | 0.0247 (13) | 0.0389 (16) | 0.0257 (14) | −0.0011 (12) | 0.0001 (10) | 0.0076 (12) |
C55 | 0.0132 (11) | 0.0215 (13) | 0.0310 (14) | −0.0046 (10) | −0.0019 (9) | 0.0022 (11) |
C71 | 0.0146 (11) | 0.0173 (11) | 0.0212 (12) | −0.0012 (9) | 0.0012 (9) | −0.0035 (9) |
C72 | 0.0181 (11) | 0.0166 (12) | 0.0231 (12) | −0.0006 (9) | −0.0011 (9) | −0.0019 (10) |
C73 | 0.0205 (11) | 0.0206 (12) | 0.0205 (12) | −0.0022 (10) | 0.0028 (9) | −0.0035 (10) |
C74 | 0.0160 (11) | 0.0209 (12) | 0.0287 (13) | 0.0016 (10) | 0.0036 (9) | −0.0038 (10) |
C75 | 0.0196 (12) | 0.0245 (13) | 0.0289 (13) | 0.0036 (10) | −0.0005 (10) | 0.0024 (11) |
C76 | 0.0203 (12) | 0.0262 (13) | 0.0215 (12) | 0.0000 (10) | 0.0030 (9) | 0.0020 (10) |
C77 | 0.0163 (11) | 0.0196 (12) | 0.0236 (12) | −0.0004 (9) | 0.0039 (9) | −0.0010 (10) |
C531 | 0.0315 (15) | 0.0434 (18) | 0.0499 (19) | −0.0051 (14) | −0.0176 (13) | −0.0005 (15) |
C532 | 0.076 (3) | 0.068 (2) | 0.0283 (17) | 0.002 (2) | −0.0061 (16) | −0.0131 (16) |
C721 | 0.0299 (14) | 0.0379 (16) | 0.0241 (13) | 0.0075 (12) | −0.0052 (11) | −0.0014 (12) |
C731 | 0.0327 (14) | 0.0330 (15) | 0.0227 (13) | 0.0046 (12) | 0.0093 (11) | −0.0048 (11) |
O51—C51 | 1.200 (3) | C32—H32C | 0.98 |
O55—C55 | 1.204 (3) | C33—H33A | 0.98 |
O72—C72 | 1.366 (3) | C33—H33B | 0.98 |
O72—C721 | 1.435 (3) | C33—H33C | 0.98 |
O73—C73 | 1.361 (3) | C34—H34A | 0.98 |
O73—C731 | 1.420 (3) | C34—H34B | 0.98 |
N1—C7A | 1.356 (3) | C34—H34C | 0.98 |
N1—N2 | 1.369 (3) | C51—C52 | 1.501 (3) |
N1—C11 | 1.413 (3) | C52—C53 | 1.521 (4) |
N2—C3 | 1.325 (3) | C52—H52A | 0.99 |
N7—C7A | 1.387 (3) | C52—H52B | 0.99 |
N7—C6 | 1.456 (3) | C53—C532 | 1.517 (4) |
N7—C77 | 1.472 (3) | C53—C531 | 1.523 (4) |
C3—C3A | 1.410 (3) | C53—C54 | 1.536 (4) |
C3—C31 | 1.509 (3) | C54—C55 | 1.487 (4) |
C3A—C7A | 1.365 (3) | C54—H54A | 0.99 |
C3A—C4 | 1.488 (3) | C54—H54B | 0.99 |
C4—C5 | 1.529 (3) | C71—C72 | 1.380 (3) |
C4—H4A | 0.99 | C71—C76 | 1.385 (3) |
C4—H4B | 0.99 | C71—C77 | 1.509 (3) |
C5—C55 | 1.524 (3) | C72—C73 | 1.399 (3) |
C5—C51 | 1.534 (3) | C73—C74 | 1.378 (3) |
C5—C6 | 1.576 (3) | C74—C75 | 1.378 (3) |
C6—H6A | 0.99 | C74—H74 | 0.95 |
C6—H6B | 0.99 | C75—C76 | 1.375 (3) |
C11—C16 | 1.373 (3) | C75—H75 | 0.95 |
C11—C12 | 1.377 (3) | C76—H76 | 0.95 |
C12—C13 | 1.380 (3) | C77—H77A | 0.99 |
C12—H12 | 0.95 | C77—H77B | 0.99 |
C13—C14 | 1.372 (4) | C531—H53A | 0.98 |
C13—H13 | 0.95 | C531—H53B | 0.98 |
C14—C15 | 1.381 (3) | C531—H53C | 0.98 |
C14—H14 | 0.95 | C532—H53D | 0.98 |
C15—C16 | 1.383 (3) | C532—H53E | 0.98 |
C15—H15 | 0.95 | C532—H53F | 0.98 |
C16—H16 | 0.95 | C721—H72A | 0.98 |
C31—C33 | 1.519 (3) | C721—H72B | 0.98 |
C31—C32 | 1.525 (3) | C721—H72C | 0.98 |
C31—C34 | 1.527 (3) | C731—H73A | 0.98 |
C32—H32A | 0.98 | C731—H73B | 0.98 |
C32—H32B | 0.98 | C731—H73C | 0.98 |
C72—O72—C721 | 115.93 (19) | C31—C34—H34C | 109.5 |
C73—O73—C731 | 116.75 (19) | H34A—C34—H34C | 109.5 |
C7A—N1—N2 | 111.01 (17) | H34B—C34—H34C | 109.5 |
C7A—N1—C11 | 130.08 (19) | O51—C51—C52 | 121.6 (2) |
N2—N1—C11 | 118.79 (18) | O51—C51—C5 | 120.9 (2) |
C3—N2—N1 | 104.96 (18) | C52—C51—C5 | 117.5 (2) |
C7A—N7—C6 | 110.35 (17) | C51—C52—C53 | 113.5 (2) |
C7A—N7—C77 | 116.10 (18) | C51—C52—H52A | 108.9 |
C6—N7—C77 | 116.30 (18) | C53—C52—H52A | 108.9 |
N2—C3—C3A | 111.61 (19) | C51—C52—H52B | 108.9 |
N2—C3—C31 | 119.5 (2) | C53—C52—H52B | 108.9 |
C3A—C3—C31 | 128.9 (2) | H52A—C52—H52B | 107.7 |
C7A—C3A—C3 | 104.7 (2) | C532—C53—C52 | 109.2 (2) |
C7A—C3A—C4 | 121.9 (2) | C532—C53—C531 | 110.4 (2) |
C3—C3A—C4 | 133.4 (2) | C52—C53—C531 | 110.4 (2) |
C3A—C4—C5 | 111.72 (18) | C532—C53—C54 | 109.7 (3) |
C3A—C4—H4A | 109.3 | C52—C53—C54 | 107.6 (2) |
C5—C4—H4A | 109.3 | C531—C53—C54 | 109.5 (2) |
C3A—C4—H4B | 109.3 | C55—C54—C53 | 110.4 (2) |
C5—C4—H4B | 109.3 | C55—C54—H54A | 109.6 |
H4A—C4—H4B | 107.9 | C53—C54—H54A | 109.6 |
C55—C5—C4 | 111.2 (2) | C55—C54—H54B | 109.6 |
C55—C5—C51 | 109.83 (19) | C53—C54—H54B | 109.6 |
C4—C5—C51 | 110.19 (19) | H54A—C54—H54B | 108.1 |
C55—C5—C6 | 110.54 (18) | O55—C55—C54 | 121.9 (2) |
C4—C5—C6 | 109.71 (18) | O55—C55—C5 | 120.7 (2) |
C51—C5—C6 | 105.24 (18) | C54—C55—C5 | 117.2 (2) |
N7—C6—C5 | 114.70 (18) | C72—C71—C76 | 119.1 (2) |
N7—C6—H6A | 108.6 | C72—C71—C77 | 118.7 (2) |
C5—C6—H6A | 108.6 | C76—C71—C77 | 122.2 (2) |
N7—C6—H6B | 108.6 | O72—C72—C71 | 118.5 (2) |
C5—C6—H6B | 108.6 | O72—C72—C73 | 120.9 (2) |
H6A—C6—H6B | 107.6 | C71—C72—C73 | 120.5 (2) |
N1—C7A—C3A | 107.7 (2) | O73—C73—C74 | 124.3 (2) |
N1—C7A—N7 | 124.28 (19) | O73—C73—C72 | 115.9 (2) |
C3A—C7A—N7 | 128.0 (2) | C74—C73—C72 | 119.7 (2) |
C16—C11—C12 | 120.6 (2) | C73—C74—C75 | 119.5 (2) |
C16—C11—N1 | 118.7 (2) | C73—C74—H74 | 120.2 |
C12—C11—N1 | 120.7 (2) | C75—C74—H74 | 120.2 |
C11—C12—C13 | 119.3 (2) | C76—C75—C74 | 120.9 (2) |
C11—C12—H12 | 120.4 | C76—C75—H75 | 119.6 |
C13—C12—H12 | 120.4 | C74—C75—H75 | 119.6 |
C14—C13—C12 | 120.5 (2) | C75—C76—C71 | 120.4 (2) |
C14—C13—H13 | 119.7 | C75—C76—H76 | 119.8 |
C12—C13—H13 | 119.7 | C71—C76—H76 | 119.8 |
C13—C14—C15 | 120.1 (2) | N7—C77—C71 | 112.22 (19) |
C13—C14—H14 | 120.0 | N7—C77—H77A | 109.2 |
C15—C14—H14 | 120.0 | C71—C77—H77A | 109.2 |
C14—C15—C16 | 119.6 (2) | N7—C77—H77B | 109.2 |
C14—C15—H15 | 120.2 | C71—C77—H77B | 109.2 |
C16—C15—H15 | 120.2 | H77A—C77—H77B | 107.9 |
C11—C16—C15 | 119.9 (2) | C53—C531—H53A | 109.5 |
C11—C16—H16 | 120.0 | C53—C531—H53B | 109.5 |
C15—C16—H16 | 120.0 | H53A—C531—H53B | 109.5 |
C3—C31—C33 | 111.36 (18) | C53—C531—H53C | 109.5 |
C3—C31—C32 | 110.90 (19) | H53A—C531—H53C | 109.5 |
C33—C31—C32 | 108.0 (2) | H53B—C531—H53C | 109.5 |
C3—C31—C34 | 108.31 (19) | C53—C532—H53D | 109.5 |
C33—C31—C34 | 108.93 (19) | C53—C532—H53E | 109.5 |
C32—C31—C34 | 109.28 (19) | H53D—C532—H53E | 109.5 |
C31—C32—H32A | 109.5 | C53—C532—H53F | 109.5 |
C31—C32—H32B | 109.5 | H53D—C532—H53F | 109.5 |
H32A—C32—H32B | 109.5 | H53E—C532—H53F | 109.5 |
C31—C32—H32C | 109.5 | O72—C721—H72A | 109.5 |
H32A—C32—H32C | 109.5 | O72—C721—H72B | 109.5 |
H32B—C32—H32C | 109.5 | H72A—C721—H72B | 109.5 |
C31—C33—H33A | 109.5 | O72—C721—H72C | 109.5 |
C31—C33—H33B | 109.5 | H72A—C721—H72C | 109.5 |
H33A—C33—H33B | 109.5 | H72B—C721—H72C | 109.5 |
C31—C33—H33C | 109.5 | O73—C731—H73A | 109.5 |
H33A—C33—H33C | 109.5 | O73—C731—H73B | 109.5 |
H33B—C33—H33C | 109.5 | H73A—C731—H73B | 109.5 |
C31—C34—H34A | 109.5 | O73—C731—H73C | 109.5 |
C31—C34—H34B | 109.5 | H73A—C731—H73C | 109.5 |
H34A—C34—H34B | 109.5 | H73B—C731—H73C | 109.5 |
C7A—N1—N2—C3 | −1.1 (2) | N2—C3—C31—C34 | 112.8 (2) |
C11—N1—N2—C3 | 175.3 (2) | C3A—C3—C31—C34 | −64.8 (3) |
N1—N2—C3—C3A | 0.6 (2) | C55—C5—C51—O51 | 144.1 (2) |
N1—N2—C3—C31 | −177.38 (19) | C4—C5—C51—O51 | 21.3 (3) |
N2—C3—C3A—C7A | 0.1 (3) | C6—C5—C51—O51 | −96.9 (2) |
C31—C3—C3A—C7A | 177.8 (2) | C55—C5—C51—C52 | −37.7 (3) |
N2—C3—C3A—C4 | −178.5 (2) | C4—C5—C51—C52 | −160.5 (2) |
C31—C3—C3A—C4 | −0.8 (4) | C6—C5—C51—C52 | 81.3 (2) |
C7A—C3A—C4—C5 | 12.0 (3) | O51—C51—C52—C53 | −134.5 (2) |
C3—C3A—C4—C5 | −169.6 (2) | C5—C51—C52—C53 | 47.3 (3) |
C3A—C4—C5—C55 | 85.0 (2) | C51—C52—C53—C532 | −175.1 (2) |
C3A—C4—C5—C51 | −152.9 (2) | C51—C52—C53—C531 | 63.4 (3) |
C3A—C4—C5—C6 | −37.5 (3) | C51—C52—C53—C54 | −56.1 (3) |
C7A—N7—C6—C5 | −44.8 (3) | C532—C53—C54—C55 | 178.5 (2) |
C77—N7—C6—C5 | 90.2 (2) | C52—C53—C54—C55 | 59.8 (3) |
C55—C5—C6—N7 | −65.5 (2) | C531—C53—C54—C55 | −60.3 (3) |
C4—C5—C6—N7 | 57.4 (3) | C53—C54—C55—O55 | 120.2 (3) |
C51—C5—C6—N7 | 175.93 (19) | C53—C54—C55—C5 | −56.4 (3) |
N2—N1—C7A—C3A | 1.1 (3) | C4—C5—C55—O55 | −11.4 (3) |
C11—N1—C7A—C3A | −174.7 (2) | C51—C5—C55—O55 | −133.6 (2) |
N2—N1—C7A—N7 | 179.1 (2) | C6—C5—C55—O55 | 110.7 (2) |
C11—N1—C7A—N7 | 3.2 (4) | C4—C5—C55—C54 | 165.22 (19) |
C3—C3A—C7A—N1 | −0.7 (3) | C51—C5—C55—C54 | 43.0 (3) |
C4—C3A—C7A—N1 | 178.1 (2) | C6—C5—C55—C54 | −72.7 (2) |
C3—C3A—C7A—N7 | −178.5 (2) | C721—O72—C72—C71 | 125.3 (2) |
C4—C3A—C7A—N7 | 0.3 (4) | C721—O72—C72—C73 | −59.2 (3) |
C6—N7—C7A—N1 | −161.0 (2) | C76—C71—C72—O72 | 175.3 (2) |
C77—N7—C7A—N1 | 63.9 (3) | C77—C71—C72—O72 | −2.9 (3) |
C6—N7—C7A—C3A | 16.5 (3) | C76—C71—C72—C73 | −0.3 (3) |
C77—N7—C7A—C3A | −118.6 (3) | C77—C71—C72—C73 | −178.5 (2) |
C7A—N1—C11—C16 | −137.0 (3) | C731—O73—C73—C74 | −5.2 (3) |
N2—N1—C11—C16 | 47.4 (3) | C731—O73—C73—C72 | 177.0 (2) |
C7A—N1—C11—C12 | 44.6 (4) | O72—C72—C73—O73 | 1.8 (3) |
N2—N1—C11—C12 | −130.9 (2) | C71—C72—C73—O73 | 177.3 (2) |
C16—C11—C12—C13 | −0.7 (4) | O72—C72—C73—C74 | −176.0 (2) |
N1—C11—C12—C13 | 177.6 (2) | C71—C72—C73—C74 | −0.5 (3) |
C11—C12—C13—C14 | −1.5 (4) | O73—C73—C74—C75 | −176.6 (2) |
C12—C13—C14—C15 | 2.2 (4) | C72—C73—C74—C75 | 1.0 (4) |
C13—C14—C15—C16 | −0.8 (4) | C73—C74—C75—C76 | −0.7 (4) |
C12—C11—C16—C15 | 2.2 (4) | C74—C75—C76—C71 | −0.2 (4) |
N1—C11—C16—C15 | −176.2 (2) | C72—C71—C76—C75 | 0.6 (4) |
C14—C15—C16—C11 | −1.4 (4) | C77—C71—C76—C75 | 178.8 (2) |
N2—C3—C31—C33 | −7.0 (3) | C7A—N7—C77—C71 | −155.66 (19) |
C3A—C3—C31—C33 | 175.4 (2) | C6—N7—C77—C71 | 72.0 (2) |
N2—C3—C31—C32 | −127.3 (2) | C72—C71—C77—N7 | −156.3 (2) |
C3A—C3—C31—C32 | 55.1 (3) | C76—C71—C77—N7 | 25.6 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C74—H74···O55i | 0.95 | 2.47 | 3.256 (3) | 140 |
Symmetry code: (i) −x+1, y+1/2, −z+3/2. |
C31H35N3O4 | Z = 2 |
Mr = 513.62 | F(000) = 548 |
Triclinic, P1 | Dx = 1.304 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.2691 (14) Å | Cell parameters from 6010 reflections |
b = 11.0898 (11) Å | θ = 2.8–27.5° |
c = 12.802 (2) Å | µ = 0.09 mm−1 |
α = 92.844 (10)° | T = 120 K |
β = 95.185 (12)° | Block, colourless |
γ = 91.070 (11)° | 0.54 × 0.29 × 0.10 mm |
V = 1308.6 (3) Å3 |
Bruker–Nonius KappaCCD diffractometer | 6010 independent reflections |
Radiation source: Bruker-Nonius FR591 rotating anode | 2954 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.129 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.8° |
ϕ & ω scans | h = −12→12 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −14→14 |
Tmin = 0.964, Tmax = 0.991 | l = −16→16 |
36798 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)] = 0.063 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.171 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0718P)2 + 0.282P] where P = (Fo2 + 2Fc2)/3 |
6010 reflections | (Δ/σ)max < 0.001 |
348 parameters | Δρmax = 0.31 e Å−3 |
0 restraints | Δρmin = −0.34 e Å−3 |
C31H35N3O4 | γ = 91.070 (11)° |
Mr = 513.62 | V = 1308.6 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.2691 (14) Å | Mo Kα radiation |
b = 11.0898 (11) Å | µ = 0.09 mm−1 |
c = 12.802 (2) Å | T = 120 K |
α = 92.844 (10)° | 0.54 × 0.29 × 0.10 mm |
β = 95.185 (12)° |
Bruker–Nonius KappaCCD diffractometer | 6010 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2954 reflections with I > 2σ(I) |
Tmin = 0.964, Tmax = 0.991 | Rint = 0.129 |
36798 measured reflections |
R[F2 > 2σ(F2)] = 0.063 | 0 restraints |
wR(F2) = 0.171 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.31 e Å−3 |
6010 reflections | Δρmin = −0.34 e Å−3 |
348 parameters |
x | y | z | Uiso*/Ueq | ||
O51 | 0.5728 (2) | 0.99129 (17) | 0.66461 (16) | 0.0328 (5) | |
O55 | 0.9779 (2) | 0.81602 (18) | 0.74159 (16) | 0.0346 (5) | |
O71 | 0.8475 (2) | 0.3713 (2) | 1.07939 (16) | 0.0436 (6) | |
O72 | 0.6089 (2) | 0.30962 (18) | 1.07474 (16) | 0.0369 (5) | |
N1 | 0.7543 (2) | 0.52473 (19) | 0.48136 (18) | 0.0250 (5) | |
N2 | 0.7985 (2) | 0.57304 (19) | 0.39266 (18) | 0.0256 (6) | |
N7 | 0.6924 (2) | 0.59297 (19) | 0.65551 (17) | 0.0224 (5) | |
C3 | 0.8075 (3) | 0.6912 (2) | 0.4144 (2) | 0.0228 (6) | |
C3A | 0.7729 (3) | 0.7204 (2) | 0.5180 (2) | 0.0228 (6) | |
C4 | 0.7617 (3) | 0.8374 (2) | 0.5794 (2) | 0.0268 (7) | |
C5 | 0.7237 (3) | 0.8208 (2) | 0.6917 (2) | 0.0230 (6) | |
C6 | 0.6305 (3) | 0.7029 (2) | 0.6978 (2) | 0.0229 (6) | |
C7A | 0.7397 (3) | 0.6126 (2) | 0.5571 (2) | 0.0228 (6) | |
C11 | 0.7286 (3) | 0.3986 (2) | 0.4806 (2) | 0.0234 (6) | |
C12 | 0.6249 (3) | 0.3531 (2) | 0.5399 (2) | 0.0256 (6) | |
C13 | 0.6020 (3) | 0.2299 (2) | 0.5392 (2) | 0.0266 (7) | |
C14 | 0.6760 (3) | 0.1533 (2) | 0.4764 (2) | 0.0284 (7) | |
C15 | 0.7764 (3) | 0.2001 (2) | 0.4155 (2) | 0.0281 (7) | |
C16 | 0.8056 (3) | 0.3227 (2) | 0.4184 (2) | 0.0259 (7) | |
C31 | 0.8456 (3) | 0.7739 (2) | 0.3302 (2) | 0.0243 (6) | |
C32 | 0.9729 (4) | 0.8574 (3) | 0.3709 (3) | 0.0426 (8) | |
C33 | 0.8851 (3) | 0.7015 (3) | 0.2335 (2) | 0.0313 (7) | |
C34 | 0.7141 (3) | 0.8502 (3) | 0.3003 (2) | 0.0321 (7) | |
C51 | 0.6276 (3) | 0.9241 (2) | 0.7270 (2) | 0.0244 (6) | |
C52 | 0.6040 (3) | 0.9363 (2) | 0.8408 (2) | 0.0263 (7) | |
C53 | 0.7474 (3) | 0.9441 (3) | 0.9095 (2) | 0.0286 (7) | |
C54 | 0.8336 (3) | 0.8310 (3) | 0.8842 (2) | 0.0268 (7) | |
C55 | 0.8574 (3) | 0.8201 (2) | 0.7704 (2) | 0.0238 (6) | |
C71 | 0.7327 (3) | 0.4784 (2) | 0.8180 (2) | 0.0229 (6) | |
C72 | 0.8276 (3) | 0.4598 (2) | 0.9065 (2) | 0.0270 (7) | |
C73 | 0.7732 (3) | 0.4031 (3) | 0.9874 (2) | 0.0288 (7) | |
C74 | 0.6317 (3) | 0.3668 (2) | 0.9843 (2) | 0.0269 (7) | |
C75 | 0.5366 (3) | 0.3848 (3) | 0.9000 (2) | 0.0303 (7) | |
C76 | 0.5894 (3) | 0.4416 (2) | 0.8164 (2) | 0.0287 (7) | |
C77 | 0.7970 (3) | 0.5315 (2) | 0.7263 (2) | 0.0246 (6) | |
C78 | 0.7372 (3) | 0.3345 (3) | 1.1432 (2) | 0.0389 (8) | |
C531 | 0.8311 (3) | 1.0574 (3) | 0.8871 (2) | 0.0357 (8) | |
C532 | 0.7184 (4) | 0.9491 (3) | 1.0249 (2) | 0.0398 (8) | |
H4A | 0.6866 | 0.8865 | 0.5429 | 0.032* | |
H4B | 0.8553 | 0.8825 | 0.5819 | 0.032* | |
H6A | 0.6148 | 0.6921 | 0.7723 | 0.027* | |
H6B | 0.5344 | 0.7137 | 0.6593 | 0.027* | |
H12 | 0.5701 | 0.4060 | 0.5806 | 0.031* | |
H13 | 0.5345 | 0.1976 | 0.5826 | 0.032* | |
H14 | 0.6579 | 0.0686 | 0.4751 | 0.034* | |
H15 | 0.8260 | 0.1474 | 0.3710 | 0.034* | |
H16 | 0.8774 | 0.3544 | 0.3783 | 0.031* | |
H32A | 1.0584 | 0.8091 | 0.3885 | 0.064* | |
H32B | 0.9486 | 0.9038 | 0.4338 | 0.064* | |
H32C | 0.9936 | 0.9128 | 0.3166 | 0.064* | |
H33A | 0.8031 | 0.6485 | 0.2061 | 0.047* | |
H33B | 0.9695 | 0.6525 | 0.2523 | 0.047* | |
H33C | 0.9082 | 0.7567 | 0.1796 | 0.047* | |
H34A | 0.6875 | 0.8964 | 0.3627 | 0.048* | |
H34B | 0.6325 | 0.7972 | 0.2721 | 0.048* | |
H34C | 0.7378 | 0.9059 | 0.2470 | 0.048* | |
H52A | 0.5463 | 0.8658 | 0.8595 | 0.032* | |
H52B | 0.5482 | 1.0098 | 0.8542 | 0.032* | |
H54A | 0.9284 | 0.8354 | 0.9267 | 0.032* | |
H54B | 0.7800 | 0.7584 | 0.9032 | 0.032* | |
H72 | 0.9264 | 0.4855 | 0.9104 | 0.032* | |
H75 | 0.4379 | 0.3596 | 0.8981 | 0.036* | |
H76 | 0.5250 | 0.4555 | 0.7564 | 0.034* | |
H77A | 0.8753 | 0.5899 | 0.7534 | 0.030* | |
H77B | 0.8414 | 0.4660 | 0.6856 | 0.030* | |
H78A | 0.7667 | 0.2615 | 1.1803 | 0.047* | |
H78B | 0.7201 | 0.3996 | 1.1961 | 0.047* | |
H53A | 0.7754 | 1.1286 | 0.9047 | 0.053* | |
H53B | 0.8474 | 1.0558 | 0.8125 | 0.053* | |
H53C | 0.9246 | 1.0609 | 0.9296 | 0.053* | |
H53D | 0.6627 | 0.8768 | 1.0395 | 0.060* | |
H53E | 0.6631 | 1.0212 | 1.0406 | 0.060* | |
H53F | 0.8108 | 0.9525 | 1.0688 | 0.060* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O51 | 0.0397 (12) | 0.0258 (11) | 0.0334 (13) | 0.0080 (9) | 0.0014 (10) | 0.0062 (9) |
O55 | 0.0254 (11) | 0.0421 (12) | 0.0378 (13) | 0.0024 (9) | 0.0098 (9) | 0.0025 (10) |
O71 | 0.0342 (12) | 0.0713 (16) | 0.0265 (13) | −0.0062 (11) | −0.0019 (10) | 0.0247 (11) |
O72 | 0.0367 (12) | 0.0467 (13) | 0.0283 (12) | −0.0089 (10) | 0.0023 (10) | 0.0167 (10) |
N1 | 0.0341 (14) | 0.0201 (12) | 0.0225 (13) | 0.0002 (10) | 0.0091 (11) | 0.0045 (10) |
N2 | 0.0305 (13) | 0.0247 (13) | 0.0229 (14) | 0.0019 (10) | 0.0067 (10) | 0.0061 (10) |
N7 | 0.0280 (13) | 0.0210 (12) | 0.0194 (13) | 0.0052 (10) | 0.0056 (10) | 0.0054 (10) |
C3 | 0.0215 (14) | 0.0252 (15) | 0.0224 (16) | 0.0042 (11) | 0.0034 (12) | 0.0043 (12) |
C3A | 0.0213 (14) | 0.0234 (14) | 0.0244 (16) | 0.0021 (11) | 0.0027 (12) | 0.0055 (12) |
C4 | 0.0356 (17) | 0.0198 (14) | 0.0261 (16) | 0.0014 (12) | 0.0062 (13) | 0.0053 (12) |
C5 | 0.0258 (15) | 0.0223 (14) | 0.0218 (16) | 0.0006 (12) | 0.0057 (12) | 0.0033 (12) |
C6 | 0.0247 (15) | 0.0218 (14) | 0.0230 (16) | 0.0023 (12) | 0.0046 (12) | 0.0039 (12) |
C7A | 0.0220 (14) | 0.0237 (15) | 0.0228 (16) | 0.0012 (11) | 0.0008 (12) | 0.0051 (12) |
C11 | 0.0268 (15) | 0.0205 (14) | 0.0225 (16) | 0.0008 (12) | −0.0012 (12) | 0.0043 (12) |
C12 | 0.0266 (15) | 0.0254 (15) | 0.0256 (16) | 0.0031 (12) | 0.0067 (12) | −0.0004 (12) |
C13 | 0.0273 (16) | 0.0261 (15) | 0.0271 (17) | −0.0021 (12) | 0.0040 (13) | 0.0051 (13) |
C14 | 0.0326 (17) | 0.0204 (14) | 0.0327 (18) | 0.0020 (12) | 0.0032 (14) | 0.0048 (13) |
C15 | 0.0339 (17) | 0.0227 (15) | 0.0280 (17) | 0.0045 (12) | 0.0040 (13) | 0.0022 (12) |
C16 | 0.0285 (16) | 0.0247 (15) | 0.0257 (16) | 0.0019 (12) | 0.0071 (13) | 0.0055 (12) |
C31 | 0.0273 (15) | 0.0238 (15) | 0.0227 (16) | −0.0003 (12) | 0.0049 (12) | 0.0071 (12) |
C32 | 0.044 (2) | 0.055 (2) | 0.0288 (19) | −0.0183 (16) | 0.0055 (15) | 0.0061 (16) |
C33 | 0.0372 (17) | 0.0332 (16) | 0.0253 (17) | 0.0090 (14) | 0.0092 (13) | 0.0069 (13) |
C34 | 0.0420 (18) | 0.0299 (16) | 0.0268 (17) | 0.0104 (14) | 0.0098 (14) | 0.0102 (13) |
C51 | 0.0226 (15) | 0.0186 (14) | 0.0321 (17) | −0.0037 (11) | 0.0022 (13) | 0.0030 (13) |
C52 | 0.0249 (15) | 0.0249 (15) | 0.0306 (17) | 0.0033 (12) | 0.0083 (13) | 0.0032 (13) |
C53 | 0.0309 (16) | 0.0337 (16) | 0.0221 (16) | −0.0013 (13) | 0.0090 (13) | −0.0008 (13) |
C54 | 0.0242 (15) | 0.0347 (16) | 0.0218 (16) | 0.0011 (13) | 0.0026 (12) | 0.0047 (13) |
C55 | 0.0238 (16) | 0.0205 (14) | 0.0281 (17) | 0.0018 (11) | 0.0046 (13) | 0.0048 (12) |
C71 | 0.0283 (16) | 0.0197 (14) | 0.0211 (16) | 0.0023 (12) | 0.0035 (12) | 0.0030 (12) |
C72 | 0.0252 (15) | 0.0304 (16) | 0.0256 (17) | −0.0025 (12) | 0.0016 (13) | 0.0059 (13) |
C73 | 0.0310 (17) | 0.0322 (16) | 0.0236 (17) | 0.0006 (13) | 0.0013 (13) | 0.0075 (13) |
C74 | 0.0346 (17) | 0.0265 (15) | 0.0212 (16) | 0.0002 (13) | 0.0061 (13) | 0.0110 (13) |
C75 | 0.0274 (16) | 0.0334 (17) | 0.0308 (18) | −0.0027 (13) | 0.0031 (13) | 0.0082 (14) |
C76 | 0.0290 (16) | 0.0320 (16) | 0.0253 (17) | 0.0025 (13) | 0.0013 (13) | 0.0071 (13) |
C77 | 0.0282 (16) | 0.0226 (14) | 0.0235 (16) | 0.0057 (12) | 0.0007 (12) | 0.0062 (12) |
C78 | 0.0367 (18) | 0.055 (2) | 0.0257 (18) | −0.0050 (16) | 0.0020 (14) | 0.0145 (15) |
C531 | 0.0387 (18) | 0.0342 (17) | 0.0338 (19) | −0.0046 (14) | 0.0072 (15) | −0.0068 (14) |
C532 | 0.0412 (19) | 0.051 (2) | 0.0287 (18) | 0.0032 (16) | 0.0110 (15) | −0.0005 (15) |
O51—C51 | 1.204 (3) | C32—H32A | 0.98 |
O55—C55 | 1.208 (3) | C32—H32B | 0.98 |
O71—C73 | 1.374 (3) | C32—H32C | 0.98 |
O71—C78 | 1.431 (4) | C33—H33A | 0.98 |
O72—C74 | 1.378 (3) | C33—H33B | 0.98 |
O72—C78 | 1.425 (4) | C33—H33C | 0.98 |
N1—C7A | 1.357 (3) | C34—H34A | 0.98 |
N1—N2 | 1.371 (3) | C34—H34B | 0.98 |
N1—C11 | 1.414 (3) | C34—H34C | 0.98 |
N2—C3 | 1.326 (3) | C51—C52 | 1.493 (4) |
N7—C7A | 1.397 (3) | C52—C53 | 1.525 (4) |
N7—C6 | 1.458 (3) | C52—H52A | 0.99 |
N7—C77 | 1.468 (3) | C52—H52B | 0.99 |
C3—C3A | 1.415 (4) | C53—C531 | 1.518 (4) |
C3—C31 | 1.511 (4) | C53—C532 | 1.524 (4) |
C3A—C7A | 1.359 (4) | C53—C54 | 1.536 (4) |
C3A—C4 | 1.495 (4) | C54—C55 | 1.493 (4) |
C4—C5 | 1.530 (4) | C54—H54A | 0.99 |
C4—H4A | 0.99 | C54—H54B | 0.99 |
C4—H4B | 0.99 | C71—C76 | 1.380 (4) |
C5—C55 | 1.525 (4) | C71—C72 | 1.396 (4) |
C5—C51 | 1.539 (4) | C71—C77 | 1.504 (4) |
C5—C6 | 1.562 (4) | C72—C73 | 1.367 (4) |
C6—H6A | 0.99 | C72—H72 | 0.95 |
C6—H6B | 0.99 | C73—C74 | 1.362 (4) |
C11—C12 | 1.380 (4) | C74—C75 | 1.356 (4) |
C11—C16 | 1.382 (4) | C75—C76 | 1.389 (4) |
C12—C13 | 1.378 (4) | C75—H75 | 0.95 |
C12—H12 | 0.95 | C76—H76 | 0.95 |
C13—C14 | 1.376 (4) | C77—H77A | 0.99 |
C13—H13 | 0.95 | C77—H77B | 0.99 |
C14—C15 | 1.377 (4) | C78—H78A | 0.99 |
C14—H14 | 0.95 | C78—H78B | 0.99 |
C15—C16 | 1.379 (4) | C531—H53A | 0.98 |
C15—H15 | 0.95 | C531—H53B | 0.98 |
C16—H16 | 0.95 | C531—H53C | 0.98 |
C31—C33 | 1.519 (4) | C532—H53D | 0.98 |
C31—C32 | 1.523 (4) | C532—H53E | 0.98 |
C31—C34 | 1.528 (4) | C532—H53F | 0.98 |
C73—O71—C78 | 104.6 (2) | C31—C34—H34A | 109.5 |
C74—O72—C78 | 105.0 (2) | C31—C34—H34B | 109.5 |
C7A—N1—N2 | 110.8 (2) | H34A—C34—H34B | 109.5 |
C7A—N1—C11 | 130.7 (2) | C31—C34—H34C | 109.5 |
N2—N1—C11 | 118.5 (2) | H34A—C34—H34C | 109.5 |
C3—N2—N1 | 105.1 (2) | H34B—C34—H34C | 109.5 |
C7A—N7—C6 | 109.9 (2) | O51—C51—C52 | 121.7 (2) |
C7A—N7—C77 | 114.2 (2) | O51—C51—C5 | 121.0 (3) |
C6—N7—C77 | 116.7 (2) | C52—C51—C5 | 117.3 (2) |
N2—C3—C3A | 111.3 (2) | C51—C52—C53 | 111.4 (2) |
N2—C3—C31 | 119.2 (2) | C51—C52—H52A | 109.4 |
C3A—C3—C31 | 129.4 (2) | C53—C52—H52A | 109.4 |
C7A—C3A—C3 | 104.8 (2) | C51—C52—H52B | 109.4 |
C7A—C3A—C4 | 122.1 (2) | C53—C52—H52B | 109.4 |
C3—C3A—C4 | 133.0 (2) | H52A—C52—H52B | 108.0 |
C3A—C4—C5 | 112.9 (2) | C531—C53—C532 | 109.1 (3) |
C3A—C4—H4A | 109.0 | C531—C53—C52 | 109.6 (2) |
C5—C4—H4A | 109.0 | C532—C53—C52 | 109.7 (2) |
C3A—C4—H4B | 109.0 | C531—C53—C54 | 110.5 (2) |
C5—C4—H4B | 109.0 | C532—C53—C54 | 109.7 (2) |
H4A—C4—H4B | 107.8 | C52—C53—C54 | 108.2 (2) |
C55—C5—C4 | 112.6 (2) | C55—C54—C53 | 111.1 (2) |
C55—C5—C51 | 107.7 (2) | C55—C54—H54A | 109.4 |
C4—C5—C51 | 110.1 (2) | C53—C54—H54A | 109.4 |
C55—C5—C6 | 110.0 (2) | C55—C54—H54B | 109.4 |
C4—C5—C6 | 110.9 (2) | C53—C54—H54B | 109.4 |
C51—C5—C6 | 105.2 (2) | H54A—C54—H54B | 108.0 |
N7—C6—C5 | 115.3 (2) | O55—C55—C54 | 121.4 (3) |
N7—C6—H6A | 108.4 | O55—C55—C5 | 121.3 (3) |
C5—C6—H6A | 108.4 | C54—C55—C5 | 117.2 (2) |
N7—C6—H6B | 108.4 | C76—C71—C72 | 119.4 (2) |
C5—C6—H6B | 108.4 | C76—C71—C77 | 123.7 (2) |
H6A—C6—H6B | 107.5 | C72—C71—C77 | 116.8 (2) |
N1—C7A—C3A | 108.0 (2) | C73—C72—C71 | 117.5 (3) |
N1—C7A—N7 | 124.7 (2) | C73—C72—H72 | 121.2 |
C3A—C7A—N7 | 127.3 (3) | C71—C72—H72 | 121.2 |
C12—C11—C16 | 120.9 (2) | C74—C73—C72 | 122.3 (3) |
C12—C11—N1 | 119.8 (2) | C74—C73—O71 | 110.2 (2) |
C16—C11—N1 | 119.3 (2) | C72—C73—O71 | 127.5 (3) |
C13—C12—C11 | 119.1 (3) | C75—C74—C73 | 121.5 (3) |
C13—C12—H12 | 120.4 | C75—C74—O72 | 128.9 (3) |
C11—C12—H12 | 120.4 | C73—C74—O72 | 109.5 (2) |
C14—C13—C12 | 120.7 (3) | C74—C75—C76 | 117.4 (3) |
C14—C13—H13 | 119.7 | C74—C75—H75 | 121.3 |
C12—C13—H13 | 119.7 | C76—C75—H75 | 121.3 |
C13—C14—C15 | 119.6 (3) | C71—C76—C75 | 121.9 (3) |
C13—C14—H14 | 120.2 | C71—C76—H76 | 119.1 |
C15—C14—H14 | 120.2 | C75—C76—H76 | 119.0 |
C14—C15—C16 | 120.7 (3) | N7—C77—C71 | 114.1 (2) |
C14—C15—H15 | 119.7 | N7—C77—H77A | 108.7 |
C16—C15—H15 | 119.7 | C71—C77—H77A | 108.7 |
C15—C16—C11 | 119.0 (3) | N7—C77—H77B | 108.7 |
C15—C16—H16 | 120.5 | C71—C77—H77B | 108.7 |
C11—C16—H16 | 120.5 | H77A—C77—H77B | 107.6 |
C3—C31—C33 | 110.8 (2) | O72—C78—O71 | 107.1 (2) |
C3—C31—C32 | 110.4 (2) | O72—C78—H78A | 110.3 |
C33—C31—C32 | 109.0 (2) | O71—C78—H78A | 110.3 |
C3—C31—C34 | 108.4 (2) | O72—C78—H78B | 110.3 |
C33—C31—C34 | 109.2 (2) | O71—C78—H78B | 110.3 |
C32—C31—C34 | 109.1 (2) | H78A—C78—H78B | 108.6 |
C31—C32—H32A | 109.5 | C53—C531—H53A | 109.5 |
C31—C32—H32B | 109.5 | C53—C531—H53B | 109.5 |
H32A—C32—H32B | 109.5 | H53A—C531—H53B | 109.5 |
C31—C32—H32C | 109.5 | C53—C531—H53C | 109.5 |
H32A—C32—H32C | 109.5 | H53A—C531—H53C | 109.5 |
H32B—C32—H32C | 109.5 | H53B—C531—H53C | 109.5 |
C31—C33—H33A | 109.5 | C53—C532—H53D | 109.5 |
C31—C33—H33B | 109.5 | C53—C532—H53E | 109.5 |
H33A—C33—H33B | 109.5 | H53D—C532—H53E | 109.5 |
C31—C33—H33C | 109.5 | C53—C532—H53F | 109.5 |
H33A—C33—H33C | 109.5 | H53D—C532—H53F | 109.5 |
H33B—C33—H33C | 109.5 | H53E—C532—H53F | 109.5 |
C7A—N1—N2—C3 | −1.3 (3) | C3A—C3—C31—C34 | −64.2 (4) |
C11—N1—N2—C3 | 177.3 (2) | C55—C5—C51—O51 | 135.6 (3) |
N1—N2—C3—C3A | 1.5 (3) | C4—C5—C51—O51 | 12.5 (3) |
N1—N2—C3—C31 | −176.5 (2) | C6—C5—C51—O51 | −107.1 (3) |
N2—C3—C3A—C7A | −1.1 (3) | C55—C5—C51—C52 | −45.2 (3) |
C31—C3—C3A—C7A | 176.6 (3) | C4—C5—C51—C52 | −168.3 (2) |
N2—C3—C3A—C4 | −177.7 (3) | C6—C5—C51—C52 | 72.2 (3) |
C31—C3—C3A—C4 | 0.0 (5) | O51—C51—C52—C53 | −126.8 (3) |
C7A—C3A—C4—C5 | 5.3 (4) | C5—C51—C52—C53 | 54.0 (3) |
C3—C3A—C4—C5 | −178.6 (3) | C51—C52—C53—C531 | 63.5 (3) |
C3A—C4—C5—C55 | 94.1 (3) | C51—C52—C53—C532 | −176.8 (2) |
C3A—C4—C5—C51 | −145.7 (2) | C51—C52—C53—C54 | −57.1 (3) |
C3A—C4—C5—C6 | −29.7 (3) | C531—C53—C54—C55 | −62.4 (3) |
C7A—N7—C6—C5 | −47.7 (3) | C532—C53—C54—C55 | 177.2 (2) |
C77—N7—C6—C5 | 84.4 (3) | C52—C53—C54—C55 | 57.6 (3) |
C55—C5—C6—N7 | −71.5 (3) | C53—C54—C55—O55 | 121.9 (3) |
C4—C5—C6—N7 | 53.8 (3) | C53—C54—C55—C5 | −54.9 (3) |
C51—C5—C6—N7 | 172.8 (2) | C4—C5—C55—O55 | −9.6 (4) |
N2—N1—C7A—C3A | 0.7 (3) | C51—C5—C55—O55 | −131.2 (3) |
C11—N1—C7A—C3A | −177.8 (3) | C6—C5—C55—O55 | 114.7 (3) |
N2—N1—C7A—N7 | 178.1 (2) | C4—C5—C55—C54 | 167.3 (2) |
C11—N1—C7A—N7 | −0.3 (5) | C51—C5—C55—C54 | 45.7 (3) |
C3—C3A—C7A—N1 | 0.2 (3) | C6—C5—C55—C54 | −68.4 (3) |
C4—C3A—C7A—N1 | 177.3 (2) | C76—C71—C72—C73 | 1.2 (4) |
C3—C3A—C7A—N7 | −177.1 (3) | C77—C71—C72—C73 | −175.1 (2) |
C4—C3A—C7A—N7 | −0.1 (4) | C71—C72—C73—C74 | −0.9 (4) |
C6—N7—C7A—N1 | −155.6 (3) | C71—C72—C73—O71 | 177.2 (3) |
C77—N7—C7A—N1 | 71.0 (3) | C78—O71—C73—C74 | −11.4 (3) |
C6—N7—C7A—C3A | 21.4 (4) | C78—O71—C73—C72 | 170.3 (3) |
C77—N7—C7A—C3A | −112.1 (3) | C72—C73—C74—C75 | 0.2 (5) |
C7A—N1—C11—C12 | 29.2 (4) | O71—C73—C74—C75 | −178.2 (3) |
N2—N1—C11—C12 | −149.1 (3) | C72—C73—C74—O72 | 178.3 (3) |
C7A—N1—C11—C16 | −152.3 (3) | O71—C73—C74—O72 | −0.1 (3) |
N2—N1—C11—C16 | 29.4 (4) | C78—O72—C74—C75 | −170.5 (3) |
C16—C11—C12—C13 | 2.2 (4) | C78—O72—C74—C73 | 11.6 (3) |
N1—C11—C12—C13 | −179.4 (2) | C73—C74—C75—C76 | 0.2 (4) |
C11—C12—C13—C14 | −3.3 (4) | O72—C74—C75—C76 | −177.5 (3) |
C12—C13—C14—C15 | 1.5 (4) | C72—C71—C76—C75 | −0.9 (4) |
C13—C14—C15—C16 | 1.3 (4) | C77—C71—C76—C75 | 175.2 (3) |
C14—C15—C16—C11 | −2.4 (4) | C74—C75—C76—C71 | 0.2 (4) |
C12—C11—C16—C15 | 0.6 (4) | C7A—N7—C77—C71 | −163.1 (2) |
N1—C11—C16—C15 | −177.8 (3) | C6—N7—C77—C71 | 66.8 (3) |
N2—C3—C31—C33 | −6.5 (4) | C76—C71—C77—N7 | 27.1 (4) |
C3A—C3—C31—C33 | 176.0 (3) | C72—C71—C77—N7 | −156.8 (2) |
N2—C3—C31—C32 | −127.3 (3) | C74—O72—C78—O71 | −18.5 (3) |
C3A—C3—C31—C32 | 55.2 (4) | C73—O71—C78—O72 | 18.3 (3) |
N2—C3—C31—C34 | 113.3 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C13—H13···O51i | 0.95 | 2.58 | 3.182 (3) | 121 |
C15—H15···O55ii | 0.95 | 2.46 | 3.173 (3) | 132 |
C72—H72···O71iii | 0.95 | 2.60 | 3.503 (3) | 160 |
C6—H6A···Cg2iv | 0.99 | 2.69 | 3.670 (3) | 169 |
Symmetry codes: (i) x, y−1, z; (ii) −x+2, −y+1, −z+1; (iii) −x+2, −y+1, −z+2; (iv) −x+1, −y+1, −z+1. |
C33H41N3O5·0.67C2H6O | F(000) = 2539.4 |
Mr = 590.55 | Dx = 1.240 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 7255 reflections |
a = 13.5770 (17) Å | θ = 2.9–27.5° |
b = 17.476 (3) Å | µ = 0.08 mm−1 |
c = 26.670 (3) Å | T = 120 K |
V = 6328.0 (15) Å3 | Block, colourless |
Z = 8 | 0.32 × 0.32 × 0.28 mm |
Bruker–Nonius KappaCCD diffractometer | 7255 independent reflections |
Radiation source: Bruker-Nonius FR591 rotating anode | 4959 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.058 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.9° |
ϕ & ω scans | h = −17→17 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −22→22 |
Tmin = 0.974, Tmax = 0.977 | l = −34→33 |
53340 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)] = 0.087 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.206 | H-atom parameters constrained |
S = 1.17 | w = 1/[σ2(Fo2) + (0.0324P)2 + 20.6148P] where P = (Fo2 + 2Fc2)/3 |
7255 reflections | (Δ/σ)max = 0.001 |
407 parameters | Δρmax = 0.59 e Å−3 |
0 restraints | Δρmin = −0.36 e Å−3 |
C33H41N3O5·0.67C2H6O | V = 6328.0 (15) Å3 |
Mr = 590.55 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 13.5770 (17) Å | µ = 0.08 mm−1 |
b = 17.476 (3) Å | T = 120 K |
c = 26.670 (3) Å | 0.32 × 0.32 × 0.28 mm |
Bruker–Nonius KappaCCD diffractometer | 7255 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 4959 reflections with I > 2σ(I) |
Tmin = 0.974, Tmax = 0.977 | Rint = 0.058 |
53340 measured reflections |
R[F2 > 2σ(F2)] = 0.087 | 0 restraints |
wR(F2) = 0.206 | H-atom parameters constrained |
S = 1.17 | w = 1/[σ2(Fo2) + (0.0324P)2 + 20.6148P] where P = (Fo2 + 2Fc2)/3 |
7255 reflections | Δρmax = 0.59 e Å−3 |
407 parameters | Δρmin = −0.36 e Å−3 |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
O51 | 0.2505 (2) | 0.69729 (13) | 0.25657 (10) | 0.0302 (6) | |
O55 | 0.41600 (19) | 0.49173 (15) | 0.22916 (10) | 0.0312 (6) | |
O73 | 0.28600 (19) | 0.33226 (16) | 0.44498 (9) | 0.0320 (6) | |
O74 | 0.0964 (2) | 0.33718 (17) | 0.46867 (10) | 0.0365 (7) | |
O75 | −0.04206 (19) | 0.34512 (18) | 0.39790 (10) | 0.0374 (7) | |
N1 | 0.1328 (2) | 0.40095 (16) | 0.15897 (11) | 0.0224 (6) | |
N2 | 0.1485 (2) | 0.42596 (17) | 0.11103 (11) | 0.0257 (7) | |
N7 | 0.1632 (2) | 0.44356 (15) | 0.24469 (10) | 0.0193 (6) | |
C3 | 0.1937 (3) | 0.4931 (2) | 0.11628 (13) | 0.0253 (8) | |
C3A | 0.2098 (3) | 0.5104 (2) | 0.16709 (13) | 0.0228 (7) | |
C4 | 0.2593 (3) | 0.5759 (2) | 0.19249 (13) | 0.0246 (8) | |
C5 | 0.2707 (2) | 0.56254 (18) | 0.24859 (13) | 0.0214 (7) | |
C6 | 0.1793 (2) | 0.51708 (19) | 0.26848 (13) | 0.0209 (7) | |
C7A | 0.1702 (2) | 0.45129 (19) | 0.19283 (12) | 0.0197 (7) | |
C11 | 0.0818 (2) | 0.33133 (19) | 0.16553 (13) | 0.0213 (7) | |
C12 | 0.0119 (3) | 0.32487 (19) | 0.20278 (13) | 0.0225 (7) | |
C13 | −0.0392 (3) | 0.2570 (2) | 0.20820 (14) | 0.0262 (8) | |
C14 | −0.0215 (3) | 0.1971 (2) | 0.17613 (15) | 0.0309 (9) | |
C15 | 0.0481 (3) | 0.2042 (2) | 0.13891 (14) | 0.0284 (8) | |
C16 | 0.1005 (3) | 0.2710 (2) | 0.13373 (14) | 0.0261 (8) | |
C31 | 0.2264 (3) | 0.5363 (2) | 0.07028 (14) | 0.0313 (9) | |
C32 | 0.3375 (3) | 0.5263 (3) | 0.06520 (15) | 0.0390 (10) | |
C33 | 0.1755 (4) | 0.5050 (3) | 0.02363 (15) | 0.0426 (11) | |
C34 | 0.2027 (3) | 0.6210 (2) | 0.07521 (15) | 0.0395 (10) | |
C51 | 0.2724 (2) | 0.63847 (19) | 0.27734 (13) | 0.0230 (7) | |
C52 | 0.2993 (3) | 0.6354 (2) | 0.33161 (14) | 0.0269 (8) | |
C53 | 0.3964 (3) | 0.5938 (2) | 0.34064 (13) | 0.0248 (8) | |
C54 | 0.3917 (3) | 0.51472 (19) | 0.31575 (13) | 0.0238 (7) | |
C55 | 0.3647 (2) | 0.51939 (19) | 0.26136 (13) | 0.0223 (7) | |
C71 | 0.1797 (3) | 0.36435 (18) | 0.32065 (13) | 0.0206 (7) | |
C72 | 0.2499 (3) | 0.35259 (19) | 0.35697 (12) | 0.0219 (7) | |
C73 | 0.2215 (3) | 0.3419 (2) | 0.40610 (13) | 0.0260 (8) | |
C74 | 0.1236 (3) | 0.3411 (2) | 0.41890 (13) | 0.0285 (8) | |
C75 | 0.0529 (3) | 0.3497 (2) | 0.38184 (14) | 0.0283 (8) | |
C76 | 0.0808 (3) | 0.3628 (2) | 0.33297 (13) | 0.0244 (8) | |
C77 | 0.2115 (3) | 0.37681 (18) | 0.26748 (12) | 0.0203 (7) | |
C531 | 0.4813 (3) | 0.6393 (2) | 0.31860 (16) | 0.0320 (9) | |
C532 | 0.4122 (3) | 0.5815 (2) | 0.39656 (15) | 0.0382 (10) | |
C731 | 0.3879 (3) | 0.3404 (3) | 0.43396 (15) | 0.0380 (10) | |
C741 | 0.0871 (4) | 0.2629 (3) | 0.48607 (18) | 0.0560 (14) | |
C751 | −0.1170 (3) | 0.3495 (3) | 0.36077 (16) | 0.0397 (10) | |
O81 | 0.1041 (4) | 0.5421 (2) | 0.38922 (17) | 0.0512 (17) | 0.670 (7) |
C81 | 0.1075 (5) | 0.5454 (4) | 0.4395 (3) | 0.0453 (19) | 0.670 (7) |
C82 | 0.1311 (6) | 0.6240 (4) | 0.4569 (3) | 0.053 (2) | 0.670 (7) |
H4A | 0.2202 | 0.6230 | 0.1869 | 0.030* | |
H4B | 0.3251 | 0.5838 | 0.1774 | 0.030* | |
H6A | 0.1874 | 0.5088 | 0.3050 | 0.025* | |
H6B | 0.1197 | 0.5489 | 0.2636 | 0.025* | |
H12 | −0.0010 | 0.3667 | 0.2246 | 0.027* | |
H13 | −0.0867 | 0.2517 | 0.2341 | 0.031* | |
H14 | −0.0574 | 0.1507 | 0.1796 | 0.037* | |
H15 | 0.0600 | 0.1627 | 0.1167 | 0.034* | |
H16 | 0.1493 | 0.2756 | 0.1084 | 0.031* | |
H32A | 0.3529 | 0.4721 | 0.0599 | 0.059* | |
H32B | 0.3699 | 0.5442 | 0.0959 | 0.059* | |
H32C | 0.3613 | 0.5562 | 0.0365 | 0.059* | |
H33A | 0.1041 | 0.5116 | 0.0269 | 0.064* | |
H33B | 0.1908 | 0.4504 | 0.0200 | 0.064* | |
H33C | 0.1988 | 0.5327 | −0.0060 | 0.064* | |
H34A | 0.2365 | 0.6419 | 0.1047 | 0.059* | |
H34B | 0.1315 | 0.6276 | 0.0791 | 0.059* | |
H34C | 0.2250 | 0.6480 | 0.0451 | 0.059* | |
H52A | 0.2462 | 0.6090 | 0.3503 | 0.032* | |
H52B | 0.3043 | 0.6882 | 0.3448 | 0.032* | |
H54A | 0.4566 | 0.4894 | 0.3190 | 0.029* | |
H54B | 0.3425 | 0.4829 | 0.3335 | 0.029* | |
H72 | 0.3177 | 0.3518 | 0.3483 | 0.026* | |
H76 | 0.0323 | 0.3707 | 0.3078 | 0.029* | |
H77A | 0.2838 | 0.3842 | 0.2666 | 0.024* | |
H77B | 0.1958 | 0.3306 | 0.2475 | 0.024* | |
H53A | 0.4838 | 0.6900 | 0.3343 | 0.048* | |
H53B | 0.4717 | 0.6450 | 0.2824 | 0.048* | |
H53C | 0.5433 | 0.6122 | 0.3249 | 0.048* | |
H53D | 0.4139 | 0.6312 | 0.4136 | 0.057* | |
H53E | 0.4747 | 0.5548 | 0.4020 | 0.057* | |
H53F | 0.3580 | 0.5507 | 0.4101 | 0.057* | |
H73A | 0.3993 | 0.3900 | 0.4178 | 0.057* | |
H73B | 0.4086 | 0.2992 | 0.4113 | 0.057* | |
H73C | 0.4260 | 0.3375 | 0.4651 | 0.057* | |
H74A | 0.1499 | 0.2361 | 0.4821 | 0.084* | |
H74B | 0.0360 | 0.2364 | 0.4668 | 0.084* | |
H74C | 0.0686 | 0.2638 | 0.5216 | 0.084* | |
H75A | −0.1058 | 0.3099 | 0.3354 | 0.060* | |
H75B | −0.1153 | 0.4000 | 0.3449 | 0.060* | |
H75C | −0.1814 | 0.3415 | 0.3765 | 0.060* | |
H81 | 0.0903 | 0.4973 | 0.3802 | 0.077* | 0.670 (7) |
H81A | 0.1582 | 0.5094 | 0.4520 | 0.054* | 0.670 (7) |
H81B | 0.0431 | 0.5295 | 0.4535 | 0.054* | 0.670 (7) |
H82A | 0.1002 | 0.6330 | 0.4896 | 0.080* | 0.670 (7) |
H82B | 0.1060 | 0.6613 | 0.4326 | 0.080* | 0.670 (7) |
H82C | 0.2027 | 0.6297 | 0.4600 | 0.080* | 0.670 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O51 | 0.0322 (14) | 0.0175 (12) | 0.0410 (15) | 0.0040 (11) | −0.0003 (12) | 0.0028 (11) |
O55 | 0.0262 (13) | 0.0316 (14) | 0.0359 (15) | 0.0051 (12) | 0.0037 (11) | −0.0082 (12) |
O73 | 0.0301 (14) | 0.0416 (16) | 0.0242 (13) | 0.0055 (13) | −0.0036 (11) | −0.0016 (12) |
O74 | 0.0401 (16) | 0.0436 (17) | 0.0258 (14) | −0.0033 (14) | 0.0061 (12) | 0.0020 (12) |
O75 | 0.0238 (14) | 0.0559 (19) | 0.0326 (15) | −0.0014 (13) | 0.0047 (11) | 0.0107 (13) |
N1 | 0.0234 (15) | 0.0200 (14) | 0.0239 (15) | −0.0041 (12) | 0.0001 (12) | 0.0033 (12) |
N2 | 0.0317 (17) | 0.0238 (15) | 0.0217 (15) | −0.0063 (13) | 0.0000 (13) | 0.0057 (12) |
N7 | 0.0204 (14) | 0.0165 (13) | 0.0210 (14) | −0.0017 (11) | −0.0011 (11) | 0.0012 (11) |
C3 | 0.0266 (19) | 0.0219 (17) | 0.0274 (19) | −0.0038 (15) | −0.0018 (15) | 0.0031 (15) |
C3A | 0.0218 (17) | 0.0229 (17) | 0.0239 (18) | −0.0033 (14) | −0.0004 (14) | 0.0033 (14) |
C4 | 0.0260 (18) | 0.0207 (17) | 0.0273 (18) | −0.0063 (15) | −0.0010 (15) | 0.0026 (14) |
C5 | 0.0209 (17) | 0.0183 (16) | 0.0250 (17) | −0.0023 (14) | 0.0021 (14) | 0.0011 (14) |
C6 | 0.0209 (16) | 0.0179 (16) | 0.0239 (17) | −0.0033 (14) | 0.0018 (14) | −0.0020 (13) |
C7A | 0.0198 (16) | 0.0184 (16) | 0.0210 (17) | −0.0003 (14) | −0.0011 (13) | 0.0008 (13) |
C11 | 0.0197 (16) | 0.0201 (17) | 0.0241 (18) | −0.0027 (14) | −0.0044 (14) | 0.0036 (14) |
C12 | 0.0228 (17) | 0.0181 (16) | 0.0266 (18) | −0.0008 (14) | −0.0024 (14) | 0.0018 (14) |
C13 | 0.0229 (18) | 0.0248 (18) | 0.0307 (19) | −0.0047 (15) | −0.0016 (15) | 0.0067 (15) |
C14 | 0.032 (2) | 0.0217 (18) | 0.039 (2) | −0.0055 (16) | −0.0079 (17) | 0.0049 (16) |
C15 | 0.030 (2) | 0.0197 (17) | 0.035 (2) | 0.0014 (15) | −0.0084 (17) | −0.0025 (15) |
C16 | 0.0229 (18) | 0.0274 (19) | 0.0279 (19) | 0.0005 (15) | −0.0031 (15) | −0.0007 (15) |
C31 | 0.043 (2) | 0.0285 (19) | 0.0220 (19) | −0.0128 (18) | −0.0015 (17) | 0.0086 (15) |
C32 | 0.046 (3) | 0.039 (2) | 0.031 (2) | −0.014 (2) | 0.0077 (19) | 0.0063 (18) |
C33 | 0.060 (3) | 0.043 (2) | 0.025 (2) | −0.019 (2) | −0.0049 (19) | 0.0076 (18) |
C34 | 0.053 (3) | 0.034 (2) | 0.031 (2) | −0.011 (2) | −0.0023 (19) | 0.0159 (18) |
C51 | 0.0173 (16) | 0.0194 (17) | 0.0322 (19) | −0.0006 (14) | 0.0042 (14) | −0.0023 (14) |
C52 | 0.0289 (19) | 0.0186 (17) | 0.033 (2) | −0.0017 (15) | 0.0028 (16) | −0.0055 (15) |
C53 | 0.0275 (19) | 0.0202 (17) | 0.0267 (19) | −0.0005 (15) | −0.0021 (15) | −0.0045 (14) |
C54 | 0.0236 (18) | 0.0178 (16) | 0.0299 (19) | −0.0004 (14) | −0.0010 (15) | −0.0010 (14) |
C55 | 0.0206 (17) | 0.0150 (15) | 0.031 (2) | −0.0010 (14) | 0.0024 (15) | −0.0040 (14) |
C71 | 0.0234 (17) | 0.0141 (15) | 0.0243 (17) | −0.0023 (13) | 0.0000 (14) | −0.0003 (13) |
C72 | 0.0224 (17) | 0.0195 (16) | 0.0239 (17) | 0.0009 (14) | 0.0016 (14) | −0.0015 (14) |
C73 | 0.0281 (19) | 0.0242 (18) | 0.0256 (19) | 0.0022 (15) | −0.0031 (15) | 0.0002 (15) |
C74 | 0.037 (2) | 0.030 (2) | 0.0184 (18) | 0.0024 (17) | 0.0058 (15) | 0.0004 (15) |
C75 | 0.0229 (18) | 0.033 (2) | 0.029 (2) | 0.0009 (16) | 0.0055 (15) | 0.0046 (16) |
C76 | 0.0221 (18) | 0.0279 (18) | 0.0231 (18) | −0.0020 (15) | −0.0016 (14) | 0.0045 (15) |
C77 | 0.0218 (17) | 0.0160 (15) | 0.0232 (17) | −0.0009 (13) | 0.0004 (14) | 0.0018 (13) |
C531 | 0.0258 (19) | 0.0240 (19) | 0.046 (2) | −0.0056 (16) | −0.0030 (17) | −0.0014 (17) |
C532 | 0.047 (3) | 0.035 (2) | 0.032 (2) | 0.001 (2) | −0.0073 (19) | −0.0056 (18) |
C731 | 0.028 (2) | 0.053 (3) | 0.032 (2) | 0.011 (2) | −0.0049 (17) | −0.0032 (19) |
C741 | 0.082 (4) | 0.043 (3) | 0.042 (3) | −0.015 (3) | 0.017 (3) | 0.000 (2) |
C751 | 0.026 (2) | 0.050 (3) | 0.043 (2) | −0.0013 (19) | 0.0014 (18) | 0.008 (2) |
O81 | 0.091 (4) | 0.020 (2) | 0.042 (3) | −0.010 (2) | 0.025 (3) | −0.0026 (19) |
C81 | 0.042 (4) | 0.046 (4) | 0.048 (4) | −0.009 (3) | −0.014 (3) | 0.020 (3) |
C82 | 0.065 (5) | 0.052 (5) | 0.044 (4) | 0.015 (4) | −0.006 (4) | 0.002 (3) |
O51—C51 | 1.205 (4) | C34—H34A | 0.98 |
O55—C55 | 1.207 (4) | C34—H34B | 0.98 |
O73—C73 | 1.368 (4) | C34—H34C | 0.98 |
O73—C731 | 1.421 (5) | C51—C52 | 1.493 (5) |
O74—C74 | 1.379 (4) | C52—C53 | 1.525 (5) |
O74—C741 | 1.384 (5) | C52—H52A | 0.99 |
O75—C75 | 1.361 (4) | C52—H52B | 0.99 |
O75—C751 | 1.422 (5) | C53—C531 | 1.519 (5) |
N1—C7A | 1.359 (4) | C53—C532 | 1.522 (5) |
N1—N2 | 1.368 (4) | C53—C54 | 1.535 (5) |
N1—C11 | 1.411 (4) | C54—C55 | 1.498 (5) |
N2—C3 | 1.331 (4) | C54—H54A | 0.99 |
N7—C7A | 1.393 (4) | C54—H54B | 0.99 |
N7—C6 | 1.449 (4) | C71—C72 | 1.374 (5) |
N7—C77 | 1.470 (4) | C71—C76 | 1.383 (5) |
C3—C3A | 1.405 (5) | C71—C77 | 1.498 (5) |
C3—C31 | 1.507 (5) | C72—C73 | 1.379 (5) |
C3A—C7A | 1.352 (5) | C72—H72 | 0.95 |
C3A—C4 | 1.490 (5) | C73—C74 | 1.372 (5) |
C4—C5 | 1.522 (5) | C74—C75 | 1.386 (5) |
C4—H4A | 0.99 | C75—C76 | 1.376 (5) |
C4—H4B | 0.99 | C76—H76 | 0.95 |
C5—C55 | 1.521 (5) | C77—H77A | 0.99 |
C5—C51 | 1.533 (5) | C77—H77B | 0.99 |
C5—C6 | 1.566 (5) | C531—H53A | 0.98 |
C6—H6A | 0.99 | C531—H53B | 0.98 |
C6—H6B | 0.99 | C531—H53C | 0.98 |
C11—C16 | 1.376 (5) | C532—H53D | 0.98 |
C11—C12 | 1.378 (5) | C532—H53E | 0.98 |
C12—C13 | 1.383 (5) | C532—H53F | 0.98 |
C12—H12 | 0.95 | C731—H73A | 0.98 |
C13—C14 | 1.372 (5) | C731—H73B | 0.98 |
C13—H13 | 0.95 | C731—H73C | 0.98 |
C14—C15 | 1.377 (6) | C741—H74A | 0.98 |
C14—H14 | 0.95 | C741—H74B | 0.98 |
C15—C16 | 1.375 (5) | C741—H74C | 0.98 |
C15—H15 | 0.95 | C751—H75A | 0.98 |
C16—H16 | 0.95 | C751—H75B | 0.98 |
C31—C34 | 1.521 (6) | C751—H75C | 0.98 |
C31—C32 | 1.524 (6) | O81—C81 | 1.344 (8) |
C31—C33 | 1.525 (5) | O81—H81 | 0.84 |
C32—H32A | 0.98 | C81—C82 | 1.485 (10) |
C32—H32B | 0.98 | C81—H81A | 0.99 |
C32—H32C | 0.98 | C81—H81B | 0.99 |
C33—H33A | 0.98 | C82—H82A | 0.98 |
C33—H33B | 0.98 | C82—H82B | 0.98 |
C33—H33C | 0.98 | C82—H82C | 0.98 |
C73—O73—C731 | 117.0 (3) | C51—C52—H52B | 109.1 |
C74—O74—C741 | 113.2 (3) | C53—C52—H52B | 109.1 |
C75—O75—C751 | 117.1 (3) | H52A—C52—H52B | 107.9 |
C7A—N1—N2 | 110.9 (3) | C531—C53—C532 | 110.3 (3) |
C7A—N1—C11 | 131.2 (3) | C531—C53—C52 | 110.3 (3) |
N2—N1—C11 | 117.9 (3) | C532—C53—C52 | 110.1 (3) |
C3—N2—N1 | 104.8 (3) | C531—C53—C54 | 109.6 (3) |
C7A—N7—C6 | 109.8 (3) | C532—C53—C54 | 107.6 (3) |
C7A—N7—C77 | 117.2 (3) | C52—C53—C54 | 108.9 (3) |
C6—N7—C77 | 117.1 (3) | C55—C54—C53 | 112.3 (3) |
N2—C3—C3A | 111.3 (3) | C55—C54—H54A | 109.1 |
N2—C3—C31 | 119.5 (3) | C53—C54—H54A | 109.1 |
C3A—C3—C31 | 129.1 (3) | C55—C54—H54B | 109.1 |
C7A—C3A—C3 | 105.3 (3) | C53—C54—H54B | 109.1 |
C7A—C3A—C4 | 122.4 (3) | H54A—C54—H54B | 107.9 |
C3—C3A—C4 | 132.4 (3) | O55—C55—C54 | 121.7 (3) |
C3A—C4—C5 | 112.0 (3) | O55—C55—C5 | 121.6 (3) |
C3A—C4—H4A | 109.2 | C54—C55—C5 | 116.7 (3) |
C5—C4—H4A | 109.2 | C72—C71—C76 | 120.2 (3) |
C3A—C4—H4B | 109.2 | C72—C71—C77 | 119.3 (3) |
C5—C4—H4B | 109.2 | C76—C71—C77 | 120.5 (3) |
H4A—C4—H4B | 107.9 | C71—C72—C73 | 119.7 (3) |
C55—C5—C4 | 112.4 (3) | C71—C72—H72 | 120.1 |
C55—C5—C51 | 107.7 (3) | C73—C72—H72 | 120.1 |
C4—C5—C51 | 111.1 (3) | O73—C73—C74 | 115.5 (3) |
C55—C5—C6 | 109.7 (3) | O73—C73—C72 | 123.9 (3) |
C4—C5—C6 | 109.3 (3) | C74—C73—C72 | 120.6 (3) |
C51—C5—C6 | 106.4 (3) | C73—C74—O74 | 120.0 (3) |
N7—C6—C5 | 114.9 (3) | C73—C74—C75 | 119.5 (3) |
N7—C6—H6A | 108.5 | O74—C74—C75 | 120.4 (3) |
C5—C6—H6A | 108.5 | O75—C75—C76 | 124.6 (3) |
N7—C6—H6B | 108.5 | O75—C75—C74 | 115.2 (3) |
C5—C6—H6B | 108.5 | C76—C75—C74 | 120.2 (3) |
H6A—C6—H6B | 107.5 | C75—C76—C71 | 119.7 (3) |
C3A—C7A—N1 | 107.8 (3) | C75—C76—H76 | 120.2 |
C3A—C7A—N7 | 127.3 (3) | C71—C76—H76 | 120.2 |
N1—C7A—N7 | 124.9 (3) | N7—C77—C71 | 112.2 (3) |
C16—C11—C12 | 120.6 (3) | N7—C77—H77A | 109.2 |
C16—C11—N1 | 119.5 (3) | C71—C77—H77A | 109.2 |
C12—C11—N1 | 119.9 (3) | N7—C77—H77B | 109.2 |
C11—C12—C13 | 119.4 (3) | C71—C77—H77B | 109.2 |
C11—C12—H12 | 120.3 | H77A—C77—H77B | 107.9 |
C13—C12—H12 | 120.3 | C53—C531—H53A | 109.5 |
C14—C13—C12 | 120.1 (3) | C53—C531—H53B | 109.5 |
C14—C13—H13 | 120.0 | H53A—C531—H53B | 109.5 |
C12—C13—H13 | 120.0 | C53—C531—H53C | 109.5 |
C13—C14—C15 | 120.1 (3) | H53A—C531—H53C | 109.5 |
C13—C14—H14 | 120.0 | H53B—C531—H53C | 109.5 |
C15—C14—H14 | 120.0 | C53—C532—H53D | 109.5 |
C16—C15—C14 | 120.3 (4) | C53—C532—H53E | 109.5 |
C16—C15—H15 | 119.9 | H53D—C532—H53E | 109.5 |
C14—C15—H15 | 119.9 | C53—C532—H53F | 109.5 |
C15—C16—C11 | 119.5 (3) | H53D—C532—H53F | 109.5 |
C15—C16—H16 | 120.2 | H53E—C532—H53F | 109.5 |
C11—C16—H16 | 120.2 | O73—C731—H73A | 109.5 |
C3—C31—C34 | 110.8 (3) | O73—C731—H73B | 109.5 |
C3—C31—C32 | 107.9 (3) | H73A—C731—H73B | 109.5 |
C34—C31—C32 | 109.2 (3) | O73—C731—H73C | 109.5 |
C3—C31—C33 | 110.5 (3) | H73A—C731—H73C | 109.5 |
C34—C31—C33 | 108.9 (3) | H73B—C731—H73C | 109.5 |
C32—C31—C33 | 109.6 (4) | O74—C741—H74A | 109.5 |
C31—C32—H32A | 109.5 | O74—C741—H74B | 109.5 |
C31—C32—H32B | 109.5 | H74A—C741—H74B | 109.5 |
H32A—C32—H32B | 109.5 | O74—C741—H74C | 109.5 |
C31—C32—H32C | 109.5 | H74A—C741—H74C | 109.5 |
H32A—C32—H32C | 109.5 | H74B—C741—H74C | 109.5 |
H32B—C32—H32C | 109.5 | O75—C751—H75A | 109.5 |
C31—C33—H33A | 109.5 | O75—C751—H75B | 109.5 |
C31—C33—H33B | 109.5 | H75A—C751—H75B | 109.5 |
H33A—C33—H33B | 109.5 | O75—C751—H75C | 109.5 |
C31—C33—H33C | 109.5 | H75A—C751—H75C | 109.5 |
H33A—C33—H33C | 109.5 | H75B—C751—H75C | 109.5 |
H33B—C33—H33C | 109.5 | C81—O81—H81 | 109.5 |
C31—C34—H34A | 109.5 | O81—C81—C82 | 111.0 (6) |
C31—C34—H34B | 109.5 | O81—C81—H81A | 109.4 |
H34A—C34—H34B | 109.5 | C82—C81—H81A | 109.4 |
C31—C34—H34C | 109.5 | O81—C81—H81B | 109.4 |
H34A—C34—H34C | 109.5 | C82—C81—H81B | 109.4 |
H34B—C34—H34C | 109.5 | H81A—C81—H81B | 108.0 |
O51—C51—C52 | 122.4 (3) | C81—C82—H82A | 109.5 |
O51—C51—C5 | 120.3 (3) | C81—C82—H82B | 109.5 |
C52—C51—C5 | 117.2 (3) | H82A—C82—H82B | 109.5 |
C51—C52—C53 | 112.4 (3) | C81—C82—H82C | 109.5 |
C51—C52—H52A | 109.1 | H82A—C82—H82C | 109.5 |
C53—C52—H52A | 109.1 | H82B—C82—H82C | 109.5 |
C7A—N1—N2—C3 | −1.4 (4) | C55—C5—C51—O51 | 134.8 (3) |
C11—N1—N2—C3 | 177.5 (3) | C4—C5—C51—O51 | 11.3 (5) |
N1—N2—C3—C3A | 1.7 (4) | C6—C5—C51—O51 | −107.6 (4) |
N1—N2—C3—C31 | 177.5 (3) | C55—C5—C51—C52 | −46.9 (4) |
N2—C3—C3A—C7A | −1.4 (4) | C4—C5—C51—C52 | −170.5 (3) |
C31—C3—C3A—C7A | −176.6 (4) | C6—C5—C51—C52 | 70.7 (4) |
N2—C3—C3A—C4 | 177.8 (4) | O51—C51—C52—C53 | −128.7 (4) |
C31—C3—C3A—C4 | 2.6 (7) | C5—C51—C52—C53 | 53.1 (4) |
C7A—C3A—C4—C5 | 7.4 (5) | C51—C52—C53—C531 | 66.8 (4) |
C3—C3A—C4—C5 | −171.7 (4) | C51—C52—C53—C532 | −171.2 (3) |
C3A—C4—C5—C55 | 87.1 (4) | C51—C52—C53—C54 | −53.5 (4) |
C3A—C4—C5—C51 | −152.1 (3) | C531—C53—C54—C55 | −66.7 (4) |
C3A—C4—C5—C6 | −35.0 (4) | C532—C53—C54—C55 | 173.4 (3) |
C7A—N7—C6—C5 | −47.0 (4) | C52—C53—C54—C55 | 54.0 (4) |
C77—N7—C6—C5 | 89.8 (3) | C53—C54—C55—O55 | 124.4 (4) |
C55—C5—C6—N7 | −65.3 (4) | C53—C54—C55—C5 | −54.0 (4) |
C4—C5—C6—N7 | 58.4 (4) | C4—C5—C55—O55 | −8.4 (4) |
C51—C5—C6—N7 | 178.5 (3) | C51—C5—C55—O55 | −131.2 (3) |
C3—C3A—C7A—N1 | 0.4 (4) | C6—C5—C55—O55 | 113.4 (4) |
C4—C3A—C7A—N1 | −178.9 (3) | C4—C5—C55—C54 | 170.0 (3) |
C3—C3A—C7A—N7 | −176.6 (3) | C51—C5—C55—C54 | 47.3 (4) |
C4—C3A—C7A—N7 | 4.1 (6) | C6—C5—C55—C54 | −68.1 (4) |
N2—N1—C7A—C3A | 0.6 (4) | C76—C71—C72—C73 | −2.3 (5) |
C11—N1—C7A—C3A | −178.2 (3) | C77—C71—C72—C73 | 179.3 (3) |
N2—N1—C7A—N7 | 177.7 (3) | C731—O73—C73—C74 | −173.9 (3) |
C11—N1—C7A—N7 | −1.1 (6) | C731—O73—C73—C72 | 5.5 (5) |
C6—N7—C7A—C3A | 16.1 (5) | C71—C72—C73—O73 | −177.8 (3) |
C77—N7—C7A—C3A | −120.7 (4) | C71—C72—C73—C74 | 1.6 (5) |
C6—N7—C7A—N1 | −160.5 (3) | O73—C73—C74—O74 | 5.2 (5) |
C77—N7—C7A—N1 | 62.8 (4) | C72—C73—C74—O74 | −174.2 (3) |
C7A—N1—C11—C16 | −141.4 (4) | O73—C73—C74—C75 | −179.4 (3) |
N2—N1—C11—C16 | 39.9 (5) | C72—C73—C74—C75 | 1.1 (6) |
C7A—N1—C11—C12 | 40.2 (5) | C741—O74—C74—C73 | −88.9 (5) |
N2—N1—C11—C12 | −138.5 (3) | C741—O74—C74—C75 | 95.7 (5) |
C16—C11—C12—C13 | 0.3 (5) | C751—O75—C75—C76 | 4.1 (6) |
N1—C11—C12—C13 | 178.6 (3) | C751—O75—C75—C74 | −176.6 (4) |
C11—C12—C13—C14 | −1.1 (5) | C73—C74—C75—O75 | 177.5 (3) |
C12—C13—C14—C15 | 0.9 (6) | O74—C74—C75—O75 | −7.1 (5) |
C13—C14—C15—C16 | 0.2 (6) | C73—C74—C75—C76 | −3.2 (6) |
C14—C15—C16—C11 | −1.0 (5) | O74—C74—C75—C76 | 172.2 (3) |
C12—C11—C16—C15 | 0.8 (5) | O75—C75—C76—C71 | −178.3 (4) |
N1—C11—C16—C15 | −177.6 (3) | C74—C75—C76—C71 | 2.5 (6) |
N2—C3—C31—C34 | 136.9 (4) | C72—C71—C76—C75 | 0.3 (5) |
C3A—C3—C31—C34 | −48.2 (5) | C77—C71—C76—C75 | 178.7 (3) |
N2—C3—C31—C32 | −103.7 (4) | C7A—N7—C77—C71 | −166.5 (3) |
C3A—C3—C31—C32 | 71.3 (5) | C6—N7—C77—C71 | 59.8 (4) |
N2—C3—C31—C33 | 16.1 (5) | C72—C71—C77—N7 | −131.5 (3) |
C3A—C3—C31—C33 | −168.9 (4) | C76—C71—C77—N7 | 50.1 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
O81—H81···Cg2 | 0.84 | 2.69 | 3.423 (4) | 147 |
C6—H6A···O81 | 0.99 | 2.58 | 3.406 (6) | 141 |
C52—H52A···O81 | 0.99 | 2.48 | 3.470 (6) | 174 |
C13—H13···O51i | 0.95 | 2.43 | 3.194 (5) | 137 |
C77—H77B···O51ii | 0.99 | 2.45 | 3.193 (4) | 131 |
Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) −x+1/2, y−1/2, z. |
Experimental details
(I) | (II) | (III) | (IV) | |
Crystal data | ||||
Chemical formula | C31H37N3O3 | C32H39N3O4 | C31H35N3O4 | C33H41N3O5·0.67C2H6O |
Mr | 499.64 | 529.66 | 513.62 | 590.55 |
Crystal system, space group | Triclinic, P1 | Monoclinic, P21/c | Triclinic, P1 | Orthorhombic, Pbca |
Temperature (K) | 120 | 120 | 120 | 120 |
a, b, c (Å) | 9.5971 (8), 11.2549 (16), 12.1452 (14) | 12.4683 (15), 10.2892 (12), 21.7635 (16) | 9.2691 (14), 11.0898 (11), 12.802 (2) | 13.5770 (17), 17.476 (3), 26.670 (3) |
α, β, γ (°) | 86.979 (11), 85.487 (10), 87.216 (7) | 90, 90.843 (10), 90 | 92.844 (10), 95.185 (12), 91.070 (11) | 90, 90, 90 |
V (Å3) | 1304.7 (3) | 2791.7 (5) | 1308.6 (3) | 6328.0 (15) |
Z | 2 | 4 | 2 | 8 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.08 | 0.08 | 0.09 | 0.08 |
Crystal size (mm) | 0.51 × 0.36 × 0.18 | 0.32 × 0.25 × 0.12 | 0.54 × 0.29 × 0.10 | 0.32 × 0.32 × 0.28 |
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 | 0.971, 0.985 | 0.965, 0.990 | 0.964, 0.991 | 0.974, 0.977 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 36057, 5986, 3281 | 45254, 6394, 4404 | 36798, 6010, 2954 | 53340, 7255, 4959 |
Rint | 0.081 | 0.065 | 0.129 | 0.058 |
(sin θ/λ)max (Å−1) | 0.650 | 0.650 | 0.650 | 0.650 |
Refinement | ||||
R[F2 > 2σ(F2)], wR(F2), S | 0.060, 0.199, 1.04 | 0.061, 0.138, 1.18 | 0.063, 0.171, 1.06 | 0.087, 0.206, 1.17 |
No. of reflections | 5986 | 6394 | 6010 | 7255 |
No. of parameters | 340 | 359 | 348 | 407 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.097P)2 + 0.8153P] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.0286P)2 + 3.2694P] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.0718P)2 + 0.282P] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.0324P)2 + 20.6148P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 0.31, −0.39 | 0.28, −0.31 | 0.31, −0.34 | 0.59, −0.36 |
Computer programs: COLLECT (Hooft, 1999), DIRAX/LSQ (Duisenberg et al., 2000), EVALCCD (Duisenberg et al., 2003), Sir2004 (Burla et al., 2005), OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003), SHELXL97 (Sheldrick, 2008) and PRPKAPPA (Ferguson, 1999).
(a) | Ring-puckering parameters | ||||
Parameter | (I) | (II) | (III) | (IV) | |
Q | 0.441 (3) | 0.450 (2) | 0.426 (3) | 0.460 (4) | |
θ | 50.5 (4) | 50.3 (3) | 51.6 (4) | 53.6 (5) | |
ϕ | 80.8 (4) | 86.0 (4) | 72.2 (4) | 81.6 (6) | |
(b) | Torsional angles | ||||
Parameter | (I) | (II) | (III) | (IV) | |
N2-C3-C31-C32 | -165.1 (2) | -127.3 (2) | -127.3 (3) | -103.6 (4) | |
N2-C3-C31-C33 | -43.4 (3) | -7.0 (3) | -6.5 (4) | 16.2 (5) | |
N2-C3-C31-C34 | 74.5 (3) | 112.8 (2) | 113.3 (3) | 136.9 (4) | |
N2-N1-C11-C12 | -133.8 (2) | -130.9 (2) | -149.1 (3) | -138.5 (3) | |
C6-N7-C77-C71 | 69.7 (3) | 72.0 (2) | 66.8 (3) | 59.8 (4) | |
N7-C77-C71-C72 | -143.6 (2) | -156.3 (2) | -156.8 (2) | -131.5 (3) | |
C71-C72-O72-C721 | 125.3 (2) | ||||
C72-C73-O73-C731 | 177.0 (2) | 5.6 (5) | |||
C73-C74-O74-C741 | -5.3 (4) | -88.9 (5) | |||
C76-C75-O75-C751 | 4.0 (6) | ||||
C72-C73-O71-C78 | 170.3 (3) | ||||
C75-C74-O72-C78 | -170.5 (3) | ||||
(c) | Bond angles | ||||
Parameter | (I) | (II) | (III) | (IV) | |
C71-C72-O72 | 118.5 (2) | ||||
C73-C72-O72 | 120.9 (2) | ||||
C72-C73-O73 | 115.9 (2) | 123.9 (3) | |||
C74-C73-O73 | 124.3 (2) | 115.5 (3) | |||
C73-C74-O74 | 124.7 (2) | 120.0 (3) | |||
C75-C74-O74 | 115.6 (2) | 120.4 (3) | |||
C74-C75-O75 | 115.2 (3) | ||||
C76-C75-O75 | 124.6 (3) |
Ring-puckering parameters are specified for the atom sequence (N7,C6,C5,C4,C3A,C7A) |
Compound | D-H···A | D-H | H···A | D···A | D-H···A |
(I) | C15-H15···O55i | 0.95 | 2.54 | 3.229 (3) | 130 |
C16-H16···Cg1i,a | 0.95 | 2.88 | 3.589 (3) | 132 | |
(II) | C74-H74···O55ii | 0.95 | 2.47 | 3.256 (3) | 140 |
(III) | C13-H13···O51iii | 0.95 | 2.58 | 3.182 (3) | 121 |
C15-H15···O55iv | 0.95 | 2.46 | 3.173 (3) | 132 | |
C72-H72···O71v | 0.95 | 2.60 | 3.503 (3) | 160 | |
C6-H6A···Cg2vi,b | 0.99 | 2.69 | 3.670 (3) | 169 | |
(IV) | O81-H81···Cg2b | 0.84 | 2.69 | 3.423 (4) | 147 |
C6-H6A···O81 | 0.99 | 2.58 | 3.406 (6) | 141 | |
C52-H52A···O81 | 0.99 | 2.48 | 3.470 (6) | 174 | |
C13-H13···O51vii | 0.95 | 2.43 | 3.194 (5) | 137 | |
C77-H77B···O51viii | 0.99 | 2.45 | 3.193 (4) | 131 |
a Cg1 represents the centroid of the ring (N1,N2,C3,C3A,C7A). b Cg2 represents the centroid of the ring (C71-C76). Symmetry codes: i (-x, 1 - y, 1 - z), ii (1 - x, 0.5 + y, 1.5 - z), iii (x, -1 + y, z), iv (2 - x, 1 - y, 1 - z), v (2 - x, 1 - y, 2 - z), vi (1 - x, 1 - y, 1 - z), vii (-x, -0.5 + y, 0.5 - z), viii (0.5 - x, -0.5 + y, z) |
In continuation of our structural study of N7-benzyl-substituted pyrazolo[3,4-b]pyridine-5-spiro-1'-cyclohexane-2',6'-diones (Cruz et al., 2008) – itself part of a programme exploring the use of multicomponent condensation reactions, especially those induced by microwave irradiation under solvent-free conditions, for the synthesis of novel heterocycles – we now report the molecular and supramolecular structures of four N7-(alkoxybenzyl) derivatives, (I)–(IV) (Figs. 1–4). Compounds (I)–(IV) were synthesized using the reaction between a substituted N-benzylaminopyrazole, 5,5-dimethylcyclohexane-1,3-dione (dimedone) and excess paraformaldehyde, under solvent-free conditions, in a straightforward modification of the synthetic method employed by Cruz et al. (2008).
Compounds (I)–(III) crystallized in solvent-free form, but compound (IV) was found to be a partial ethanol solvate, with 0.67 molecules of ethanol per molecule of the pyrazolopyridine in the crystal selected for data collection. We have not investigated systematically the stoichiometry of this solvate or related solvates, but it is entirely possible that the ethanol content may vary somewhat from one crystal to another. Examination using PLATON (Spek, 2003) of the refined structure of (IV), but with the ethanol component omitted, found eight voids, each of volume ca 96 Å3 and together accounting for some 12.2% of the unit-cell volume. It is possible that the ethanol of solvation is present in this strucutre merely as a placeholder component, occupying what would otherwise be empty space.
In each compound the reduced pyridine ring adopts a half-chair conformation, as shown (Table 1) by the ring-puckering parameters (Cremer & Pople, 1975), defined here for the atom-sequence (N7, C6, C5, C4, C3A, C7A). For an idealized half-chair ring with equal bond lengths throughout, the ring-puckering angles are θ = 50.8° and ϕ = (60k + 30)°, where k represents an integer.
The rest of the molecular conformation is determined by the orientation of the three pendent substituents relative to the heterocyclic molecular core, and by the orientation of the alkoxy substituents relative to the adjacent aryl ring (Table 1). As indicated by the relevant torsion angles (Table 1), while the orientation of the phenyl and benzyl units relative to the molecular core is fairly similar in each compound, there is considerable variation in the degree to which the tert-butyl group has been rotated about the C3—C31 bond. Since the rotational barrier about this bond approximates to a sixfold barrier, as found when a fragment of local C3 symmetry, such as a tert-butyl group, is bonded to a fragment with effective local C2 symmetry, such as a planar ring, it can be expected that the barrier is exceptionally low, no more than a few tens of joules per mole (Tannenbaum et al., 1956; Naylor & Wilson, 1957), so accounting for the variation in the relative orientation of the tert-butyl group.
The orientations of the methoxy substituents in (I), (II) and (IV) show some interesting variations. As shown by the relevant torsion angles (Table 1), the single methoxy group in (I), that at C73 in (II), and those at C73 and C75 in (IV) are all almost coplanar with the adjacent aryl rings. The deviations from the mean planes of these rings are 0.235 (3) Å for atom C741 in (I), 0.006 (3) Å for atom C731 in (II), and 0.147 (5) Å and 0.164 (5) Å for atoms C731 and C751, respectively, in (IV). Associated with each of these effectively in-plane methoxy groups is a marked difference between the two exocyclic C—C—O angles, typically almost 10°. By contrast, the C74/O74/C741 plane in compound (IV) is almost orthogonal to the adjacent ring, with atom C741 displaced by 1.058 (5) Å from the ring plane, while atom C721 in compound (II) is displaced from the adjacent ring plane by 0.944 (3) Å. At the same time, in compound (IV) the exocyclic C—C—O angles at atom C74 are identical within experimental uncertainty, and those at atom C72 in compound (II) differ by less than 3°. Although the in-plane conformation appears to be the most favoured and of lowest energy, maximizing the orbital overlap between the π orbitals of the ring and formally non-bonding 2p orbital on the O atom, this orientation is nonetheless rather easily disrupted by non-bonded (steric) interactions between adjacent substituents. In (III), the five-membered ring formed by the methylenedioxo unit adopts an envelope conformation, folded across the line O71···O72.
Although compounds (I)–(IV) all contain potential hydrogen-bond acceptors – in the methoxy groups in (I), (II) and (IV), and in the methylenedioxo unit in (III) – in no case do these O atoms play any significant role in the supramolecular aggregation. There is a rather long C—H···O contact involving such an O atom in (III) (Table 2), although this is possibly only of marginal structural significance, at best, while the methoxy O atoms in the other three compounds do not form even weak contacts of this type. The principal intermolecular interactions in this series are of C—H···π type and of C—H···O type utilizing carbonyl O atoms as the hydrogen-bond acceptors. There are no π–π stacking interactions in any of (I)–(IV). The partial-occupancy ethanol component in (IV) is connected to the heterocyclic component by a three-point linkage (Table 2), but it plays no role in the supramolecular aggregation, acting simply as a pendent group.
In compound (I), pairs of molecules are linked by the cooperative action of C—H···O and C—H···π hydrogen bonds into centrosymmetric dimers, within which the paired C—H···O hydrogen bonds define an R22(22) (Bernstein et al., 1995) motif (Fig. 5), but there are no direction-specific interactions between these dimers; hence the supramolecular aggregation in compound (I) can be regarded as finite, or zero-dimensional.
A single C—H···O hydrogen bond links molecules of (II), which are related by the 21 screw axis along (1/2, y, 3/4), into a simple C(11) chain running parallel to the [010] direction (Fig. 6). Two chains of this type related to one another by inversion pass through each unit cell, but there are no direction-specific interactions between adjacent chains.
In (III), a combination of a C—H···O hydrogen bond, with C15 as the donor, and a C—H···π hydrogen bond link the molecules into a chain of centrosymmetric edge-fused rings running parallel to the [100] direction (Fig. 7). Within this chain, R22(22) rings exactly analogous to those observed in compound (I) are centred at (n, 1/2, 1/2), where n represents an integer, and these alternate with rings formed by pairs of C—H···π hydrogen bonds, centred at (n + 1/2, 1/2, 1/2), where n represents zero or an integer. Within the structure of (III) there are two further C—H···O contacts, both rather long, and it is of interest to examine their possible structural effects. The interaction involving C13 as the donor links the chains of rings, which are related by translation along [010], while that involving C72 as the donor links the R22(22) rings into a chain along [001]. Thus, if these two interactions are regarded as structurally significant, the supramolecular structure based on the one-dimensional chains of rings along [100] (Fig. 7) become successively linked into two-dimensional and three-dimensional arrays.
The heterocyclic components in (IV) are linked into a sheet by two C—H···O hydrogen bonds, both utilizing the same carbonyl acceptor atom, and the formation of the sheet is readily analysed in terms of the individual actions of the two hydrogen bonds. The aryl atom C13 at (x, y, z) acts as a hydrogen-bond donor to the carbonyl atom O51 at (-x, -1/2 + y, 1/2 - z), so linking molecules related by the 21 screw axis along (0, y, 1/4), and so forming a C(11) chain running parallel to the [010] direction. In the second substructure, the methylene atom C77 at (x, y, z) acts as a hydrogen-bond donor to atom O51 at (1/2 - x, -1/2 + y, z), thus linking molecules related by the b-glide plane at x = 1/4 into a C(7) chain, again running parallel to the [010] direction. The combination of these two chain motifs generates a sheet of R34(28) rings lying parallel to (001) (Fig. 8) and occupying the domain 0 < z < 0.5. A second sheet, related to the first by inversion, occupies the domain 0.5 < z < 1.0, but there are no direction-specific interactions between adjacent sheets. As noted above, the partial-occupancy ethanol molecules are pendent from this sheet, but they play no role in its formation.
Although the methoxy substituents in compounds (I), (II) and (IV) play no direct role in the supramolecular aggregation, it is striking that, as the degree of methoxy substitution increases, so too does the dimensionality of the hydrogen-bonded structure, from zero-dimensional in the monomethoxy compound (I), to one-dimensional in the dimethoxy compound (II) to two-dimensional in the trimethoxy compound (IV). It is interesting to note that the variations in the molecular constitution occur solely in the substituted benzyl ring, which is, of course, remote from the main hydrogen-bond acceptor sites, the carbonyl O atoms and the main hydrogen-bond donor sites, most of which are provided by the unsubstituted phenyl ring.