Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100012531/sx1110sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100012531/sx1110IIsup2.hkl |
CCDC reference: 162564
For related literature, see: Adrian & Wilcox (1992); Allen et al. (1991); Cowart et al. (1988); Cremer & Pople (1975); Crossley et al. (1995); Cudero et al. (1997); Goldberg & Alper (1995); Larsen et al. (1970); Quiroga et al. (1999); Sheldrick (1997); Wilcox (1985); Wilcox et al. (1987).
5-Amino-3-methyl-1-phenyl-pyrazole, (I) (2.89 mmol), formaldehyde 37% (4.5 mmol) and acetic acid (0.2 ml) in ethanol (10 ml) were heated at 323 K for 5 min and monitored by thin-layer chromatography. After cooling, crystals were obtained, filtered off and recrystalized from ethanol [yield 53%; m.p. 551 (1) K]. Spectroscopic analysis: 1H and 13C NMR, MS and elemental analysis. 1H NMR (300 MHz, DMSO -d6), (δ, p.p.m.): 1.92 (6H, s), 3.56 [2H, d, J = 15.7 Hz], 4.26 [2H, d, J = 15.7 Hz], 4.31 (2H, s), 7.29 [2H, t, J = 7.4 Hz], 7.50 [4H, br.t, J = 7.9 Hz], 7.96 [4H, d, J = 8.7 Hz]; 13C NMR (75 MHz, DMSO -d6), (δ, p.p.m.): 12.1 (C-16, C-17), 47.4 (C-4, C-9), 67.5 (C-15), 104.3, 119.7, 125.5, 129.3, 139.2, 144.7, 144.9; MS (70 eV), m/e (%): 382 (100), 354 (23), 198 (53), 77 (30); C23H22N6 (382.46): calcd. C 72.19, H 5.81, N 22.01; found C 72.13, H 5.82, N 22.05.
The aryl, methyl and methylenic H atoms were added at calculated positions. The H atoms treated with a riding model with SHELXL97 (Sheldrick, 1997) defaults (C—H 0.93–0.97 Å) were not refined.
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1993); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: MSC/AFC Diffractometer Control Software; program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ZORTEP (Zsolnai, 1995); software used to prepare material for publication: SHELXL97.
C23H22N6 | F(000) = 808 |
Mr = 382.46 | Dx = 1.290 Mg m−3 |
Triclinic, P1 | Melting point: 393 K |
a = 11.224 (1) Å | Mo Kα radiation, λ = 0.71069 Å |
b = 13.650 (1) Å | Cell parameters from 17 reflections |
c = 14.110 (1) Å | θ = 20.5–22.5° |
α = 75.270 (2)° | µ = 0.08 mm−1 |
β = 73.070 (2)° | T = 293 K |
γ = 76.270 (2)° | Transparent prisms, colourless |
V = 1968.7 (3) Å3 | 0.20 × 0.15 × 0.12 mm |
Z = 4 |
Rigaku AFC7S diffractometer | Rint = 0.091 |
Radiation source: fine-focus sealed tube | θmax = 25.5°, θmin = 2.2° |
Graphite monochromator | h = −13→13 |
ω/2θ scans | k = −16→0 |
7664 measured reflections | l = −17→16 |
7332 independent reflections | 3 standard reflections every 150 reflections |
4249 reflections with I > 2σ(I) | intensity decay: 3.6% |
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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.141 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Calculated w = 1/[σ2(Fo2) + (0.0738P)2 + 0.0251P] where P = (Fo2 + 2Fc2)/3 |
7332 reflections | (Δ/σ)max < 0.001 |
570 parameters | Δρmax = 0.17 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
C23H22N6 | γ = 76.270 (2)° |
Mr = 382.46 | V = 1968.7 (3) Å3 |
Triclinic, P1 | Z = 4 |
a = 11.224 (1) Å | Mo Kα radiation |
b = 13.650 (1) Å | µ = 0.08 mm−1 |
c = 14.110 (1) Å | T = 293 K |
α = 75.270 (2)° | 0.20 × 0.15 × 0.12 mm |
β = 73.070 (2)° |
Rigaku AFC7S diffractometer | Rint = 0.091 |
7664 measured reflections | 3 standard reflections every 150 reflections |
7332 independent reflections | intensity decay: 3.6% |
4249 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.141 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.17 e Å−3 |
7332 reflections | Δρmin = −0.23 e Å−3 |
570 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
N1 | 0.16530 (16) | 0.88309 (13) | 0.43637 (13) | 0.0482 (4) | |
N2 | 0.22728 (17) | 0.95533 (15) | 0.44375 (14) | 0.0565 (5) | |
C3 | 0.2711 (2) | 1.00200 (18) | 0.34865 (18) | 0.0532 (5) | |
C3A | 0.23639 (18) | 0.96234 (16) | 0.27955 (16) | 0.0456 (5) | |
C4 | 0.25174 (19) | 0.98986 (17) | 0.16708 (16) | 0.0489 (5) | |
H41 | 0.2332 | 1.0640 | 0.1455 | 0.053 (6)* | |
H42 | 0.3384 | 0.9658 | 0.1330 | 0.057 (6)* | |
N5 | 0.16390 (15) | 0.94134 (13) | 0.13979 (12) | 0.0469 (4) | |
C5A | 0.03748 (18) | 0.99199 (15) | 0.16578 (14) | 0.0421 (5) | |
N6 | −0.01459 (15) | 1.08203 (13) | 0.11151 (12) | 0.0459 (4) | |
N7 | −0.13973 (16) | 1.11021 (14) | 0.15972 (13) | 0.0496 (4) | |
C8 | −0.16285 (18) | 1.03730 (16) | 0.24076 (15) | 0.0456 (5) | |
C8A | −0.05489 (18) | 0.96013 (15) | 0.24827 (15) | 0.0429 (5) | |
C9 | −0.02889 (18) | 0.86386 (16) | 0.32385 (16) | 0.0469 (5) | |
H91 | −0.0623 | 0.8776 | 0.3917 | 0.045 (5)* | |
H92 | −0.0702 | 0.8116 | 0.3179 | 0.048 (5)* | |
N10 | 0.11016 (15) | 0.82642 (12) | 0.30538 (12) | 0.0452 (4) | |
C10A | 0.16926 (18) | 0.88772 (15) | 0.33821 (15) | 0.0425 (5) | |
C15 | 0.1670 (2) | 0.83437 (16) | 0.19604 (16) | 0.0504 (5) | |
H151 | 0.2542 | 0.7990 | 0.1859 | 0.043 (5)* | |
H152 | 0.1221 | 0.7999 | 0.1688 | 0.059 (6)* | |
C16 | 0.3433 (3) | 1.0882 (2) | 0.3274 (2) | 0.0784 (8) | |
H161 | 0.3632 | 1.0913 | 0.3881 | 0.144 (14)* | |
H162 | 0.2926 | 1.1522 | 0.3041 | 0.168 (18)* | |
H163 | 0.4202 | 1.0760 | 0.2763 | 0.152 (16)* | |
C17 | −0.2905 (2) | 1.04182 (18) | 0.31298 (18) | 0.0572 (6) | |
H171 | −0.3441 | 1.1053 | 0.2925 | 0.064 (7)* | |
H172 | −0.2823 | 1.0381 | 0.3797 | 0.091 (9)* | |
H173 | −0.3272 | 0.9850 | 0.3131 | 0.076 (8)* | |
C18 | 0.10585 (19) | 0.81778 (17) | 0.52437 (15) | 0.0475 (5) | |
C19 | 0.0415 (2) | 0.8563 (2) | 0.61018 (18) | 0.0630 (6) | |
H19 | 0.0376 | 0.9248 | 0.6114 | 0.084 (9)* | |
C20 | −0.0168 (3) | 0.7921 (3) | 0.6940 (2) | 0.0784 (8) | |
H20 | −0.0584 | 0.8169 | 0.7528 | 0.083 (8)* | |
C21 | −0.0143 (3) | 0.6921 (3) | 0.6917 (2) | 0.0791 (8) | |
H21 | −0.0568 | 0.6500 | 0.7479 | 0.095 (9)* | |
C22 | 0.0515 (2) | 0.6539 (2) | 0.60580 (19) | 0.0719 (7) | |
H22 | 0.0539 | 0.5856 | 0.6045 | 0.070 (8)* | |
C23 | 0.1133 (2) | 0.71577 (18) | 0.52235 (17) | 0.0583 (6) | |
H23 | 0.1597 | 0.6895 | 0.4652 | 0.085 (8)* | |
C24 | 0.03833 (19) | 1.14399 (17) | 0.01828 (15) | 0.0465 (5) | |
C25 | 0.1455 (2) | 1.1038 (2) | −0.04826 (16) | 0.0593 (6) | |
H25 | 0.1846 | 1.0357 | −0.0322 | 0.073 (8)* | |
C26 | 0.1936 (3) | 1.1663 (2) | −0.13895 (17) | 0.0676 (7) | |
H26 | 0.2663 | 1.1401 | −0.1834 | 0.089 (9)* | |
C27 | 0.1353 (3) | 1.2667 (2) | −0.16430 (19) | 0.0696 (7) | |
H27 | 0.1687 | 1.3083 | −0.2251 | 0.084 (8)* | |
C28 | 0.0271 (3) | 1.3048 (2) | −0.09863 (19) | 0.0717 (7) | |
H28 | −0.0138 | 1.3720 | −0.1162 | 0.103 (10)* | |
C29 | −0.0216 (2) | 1.24479 (18) | −0.00716 (18) | 0.0602 (6) | |
H29 | −0.0940 | 1.2717 | 0.0371 | 0.076* | |
N31 | 0.64128 (16) | 0.37172 (13) | 0.04055 (12) | 0.0490 (4) | |
N32 | 0.70257 (18) | 0.44389 (14) | −0.03196 (13) | 0.0570 (5) | |
C33 | 0.7494 (2) | 0.48927 (17) | 0.01786 (16) | 0.0546 (6) | |
C33A | 0.71959 (19) | 0.44904 (15) | 0.12253 (15) | 0.0473 (5) | |
C34 | 0.7416 (2) | 0.47491 (17) | 0.21237 (16) | 0.0500 (5) | |
H341 | 0.8290 | 0.4492 | 0.2154 | 0.051 (6)* | |
H342 | 0.7255 | 0.5490 | 0.2061 | 0.058 (6)* | |
N35 | 0.65622 (16) | 0.42776 (12) | 0.30635 (12) | 0.0456 (4) | |
C35A | 0.53044 (19) | 0.48049 (15) | 0.31739 (14) | 0.0430 (5) | |
N36 | 0.48362 (16) | 0.57113 (13) | 0.35117 (12) | 0.0464 (4) | |
N37 | 0.35803 (16) | 0.60266 (14) | 0.34987 (14) | 0.0528 (5) | |
C38 | 0.3283 (2) | 0.53033 (17) | 0.31812 (15) | 0.0492 (5) | |
C38A | 0.43365 (19) | 0.45174 (15) | 0.29628 (14) | 0.0452 (5) | |
C39 | 0.4540 (2) | 0.35577 (16) | 0.25608 (16) | 0.0493 (5) | |
H391 | 0.4123 | 0.3043 | 0.3078 | 0.055 (6)* | |
H392 | 0.4175 | 0.3709 | 0.1984 | 0.045 (5)* | |
N40 | 0.59152 (16) | 0.31553 (12) | 0.22529 (12) | 0.0462 (4) | |
C40A | 0.65002 (18) | 0.37518 (15) | 0.13366 (14) | 0.0429 (5) | |
C45 | 0.6547 (2) | 0.32114 (15) | 0.30189 (16) | 0.0510 (5) | |
H451 | 0.6115 | 0.2870 | 0.3678 | 0.053 (6)* | |
H452 | 0.7411 | 0.2844 | 0.2866 | 0.046 (6)* | |
C46 | 0.8210 (3) | 0.5756 (2) | −0.0379 (2) | 0.0776 (8) | |
H461 | 0.9102 | 0.5493 | −0.0511 | 0.129 (13)* | |
H462 | 0.8007 | 0.6270 | 0.0025 | 0.140 (14)* | |
H463 | 0.7977 | 0.6057 | −0.1008 | 0.126 (13)* | |
C47 | 0.1978 (2) | 0.5399 (2) | 0.3060 (2) | 0.0674 (7) | |
H471 | 0.1445 | 0.5989 | 0.3309 | 0.116 (11)* | |
H472 | 0.1641 | 0.4791 | 0.3435 | 0.109 (11)* | |
H473 | 0.2009 | 0.5480 | 0.2357 | 0.115 (11)* | |
C48 | 0.58348 (19) | 0.30512 (16) | 0.01262 (14) | 0.0450 (5) | |
C49 | 0.5254 (2) | 0.34092 (19) | −0.06645 (17) | 0.0588 (6) | |
H49 | 0.5252 | 0.4083 | −0.1024 | 0.081 (8)* | |
C50 | 0.4674 (2) | 0.2755 (2) | −0.0917 (2) | 0.0692 (7) | |
H50 | 0.4289 | 0.2989 | −0.1454 | 0.106 (10)* | |
C51 | 0.4664 (2) | 0.1768 (2) | −0.03826 (19) | 0.0641 (6) | |
H51 | 0.4246 | 0.1341 | −0.0540 | 0.077 (8)* | |
C52 | 0.5268 (2) | 0.14081 (19) | 0.03842 (19) | 0.0628 (6) | |
H52 | 0.5273 | 0.0732 | 0.0738 | 0.072 (8)* | |
C53 | 0.5872 (2) | 0.20394 (17) | 0.06376 (17) | 0.0571 (6) | |
H53 | 0.6300 | 0.1787 | 0.1148 | 0.063 (7)* | |
C54 | 0.5431 (2) | 0.63194 (16) | 0.38489 (15) | 0.0461 (5) | |
C55 | 0.6505 (2) | 0.58929 (18) | 0.42038 (16) | 0.0557 (6) | |
H55 | 0.6849 | 0.5199 | 0.4230 | 0.056 (6)* | |
C56 | 0.7061 (2) | 0.6517 (2) | 0.45198 (17) | 0.0647 (6) | |
H56 | 0.7797 | 0.6241 | 0.4741 | 0.057 (7)* | |
C57 | 0.6541 (3) | 0.7537 (2) | 0.45109 (18) | 0.0691 (7) | |
H57 | 0.6921 | 0.7947 | 0.4728 | 0.081 (8)* | |
C58 | 0.5465 (3) | 0.7943 (2) | 0.4182 (2) | 0.0715 (7) | |
H58 | 0.5107 | 0.8631 | 0.4183 | 0.081 (8)* | |
C59 | 0.4902 (2) | 0.73471 (18) | 0.38497 (19) | 0.0621 (6) | |
H59 | 0.4169 | 0.7632 | 0.3626 | 0.089 (9)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0530 (10) | 0.0521 (10) | 0.0455 (10) | −0.0106 (8) | −0.0158 (8) | −0.0148 (8) |
N2 | 0.0589 (11) | 0.0630 (12) | 0.0592 (12) | −0.0159 (9) | −0.0196 (9) | −0.0220 (10) |
C3 | 0.0492 (13) | 0.0587 (13) | 0.0584 (14) | −0.0119 (11) | −0.0169 (11) | −0.0167 (11) |
C3A | 0.0371 (11) | 0.0516 (12) | 0.0507 (12) | −0.0068 (9) | −0.0098 (9) | −0.0167 (10) |
C4 | 0.0391 (11) | 0.0570 (14) | 0.0492 (12) | −0.0087 (10) | −0.0041 (9) | −0.0157 (10) |
N5 | 0.0458 (10) | 0.0520 (10) | 0.0436 (10) | −0.0057 (8) | −0.0090 (8) | −0.0161 (8) |
C5A | 0.0417 (11) | 0.0499 (12) | 0.0386 (10) | −0.0078 (9) | −0.0119 (9) | −0.0134 (9) |
N6 | 0.0417 (10) | 0.0555 (11) | 0.0388 (9) | −0.0092 (8) | −0.0093 (7) | −0.0067 (8) |
N7 | 0.0420 (10) | 0.0586 (11) | 0.0452 (10) | −0.0089 (8) | −0.0092 (8) | −0.0070 (9) |
C8 | 0.0409 (11) | 0.0528 (12) | 0.0454 (12) | −0.0102 (10) | −0.0106 (9) | −0.0120 (10) |
C8A | 0.0426 (11) | 0.0486 (11) | 0.0415 (11) | −0.0109 (9) | −0.0132 (9) | −0.0096 (9) |
C9 | 0.0445 (11) | 0.0533 (12) | 0.0483 (12) | −0.0148 (10) | −0.0135 (9) | −0.0115 (10) |
N10 | 0.0483 (10) | 0.0434 (9) | 0.0475 (10) | −0.0057 (8) | −0.0143 (8) | −0.0148 (8) |
C10A | 0.0394 (11) | 0.0451 (11) | 0.0444 (11) | −0.0031 (9) | −0.0114 (9) | −0.0143 (9) |
C15 | 0.0558 (13) | 0.0502 (12) | 0.0507 (12) | −0.0021 (10) | −0.0166 (10) | −0.0225 (10) |
C16 | 0.0801 (19) | 0.091 (2) | 0.083 (2) | −0.0428 (17) | −0.0240 (17) | −0.0212 (17) |
C17 | 0.0461 (12) | 0.0605 (15) | 0.0586 (15) | −0.0086 (11) | −0.0086 (11) | −0.0064 (11) |
C18 | 0.0427 (11) | 0.0566 (13) | 0.0429 (11) | −0.0033 (10) | −0.0128 (9) | −0.0122 (10) |
C19 | 0.0638 (15) | 0.0714 (17) | 0.0538 (14) | 0.0002 (13) | −0.0118 (12) | −0.0268 (12) |
C20 | 0.0710 (18) | 0.105 (2) | 0.0486 (15) | 0.0000 (16) | −0.0019 (13) | −0.0263 (16) |
C21 | 0.0676 (17) | 0.101 (2) | 0.0522 (16) | −0.0178 (16) | −0.0018 (13) | 0.0003 (16) |
C22 | 0.0769 (18) | 0.0659 (17) | 0.0634 (17) | −0.0144 (14) | −0.0076 (14) | −0.0058 (13) |
C23 | 0.0643 (15) | 0.0568 (14) | 0.0474 (13) | −0.0069 (11) | −0.0040 (11) | −0.0135 (11) |
C24 | 0.0506 (12) | 0.0576 (13) | 0.0371 (11) | −0.0209 (10) | −0.0115 (9) | −0.0084 (10) |
C25 | 0.0600 (14) | 0.0760 (17) | 0.0417 (12) | −0.0167 (13) | −0.0060 (11) | −0.0145 (12) |
C26 | 0.0684 (16) | 0.099 (2) | 0.0412 (13) | −0.0339 (15) | −0.0041 (12) | −0.0170 (14) |
C27 | 0.0890 (19) | 0.0847 (19) | 0.0454 (14) | −0.0509 (16) | −0.0131 (14) | −0.0018 (14) |
C28 | 0.092 (2) | 0.0659 (17) | 0.0580 (16) | −0.0326 (15) | −0.0165 (15) | 0.0013 (13) |
C29 | 0.0660 (15) | 0.0606 (15) | 0.0542 (14) | −0.0193 (12) | −0.0118 (12) | −0.0079 (11) |
N31 | 0.0597 (11) | 0.0488 (10) | 0.0369 (9) | −0.0153 (9) | −0.0059 (8) | −0.0071 (8) |
N32 | 0.0692 (12) | 0.0582 (11) | 0.0385 (10) | −0.0214 (10) | −0.0015 (9) | −0.0050 (9) |
C33 | 0.0591 (14) | 0.0548 (13) | 0.0444 (12) | −0.0171 (11) | 0.0002 (10) | −0.0088 (10) |
C33A | 0.0516 (12) | 0.0437 (11) | 0.0425 (12) | −0.0081 (10) | −0.0050 (9) | −0.0095 (9) |
C34 | 0.0488 (13) | 0.0488 (13) | 0.0508 (12) | −0.0102 (10) | −0.0073 (10) | −0.0115 (10) |
N35 | 0.0535 (10) | 0.0428 (9) | 0.0403 (9) | −0.0069 (8) | −0.0118 (8) | −0.0091 (7) |
C35A | 0.0524 (12) | 0.0386 (10) | 0.0349 (10) | −0.0087 (9) | −0.0054 (9) | −0.0074 (8) |
N36 | 0.0484 (10) | 0.0462 (10) | 0.0445 (10) | −0.0069 (8) | −0.0077 (8) | −0.0145 (8) |
N37 | 0.0501 (11) | 0.0530 (11) | 0.0556 (11) | −0.0057 (9) | −0.0099 (9) | −0.0182 (9) |
C38 | 0.0519 (13) | 0.0528 (12) | 0.0405 (11) | −0.0128 (10) | −0.0035 (9) | −0.0108 (10) |
C38A | 0.0521 (12) | 0.0448 (11) | 0.0371 (11) | −0.0143 (10) | −0.0033 (9) | −0.0085 (9) |
C39 | 0.0561 (13) | 0.0492 (12) | 0.0425 (11) | −0.0179 (10) | −0.0040 (10) | −0.0104 (10) |
N40 | 0.0592 (11) | 0.0389 (9) | 0.0378 (9) | −0.0096 (8) | −0.0080 (8) | −0.0068 (7) |
C40A | 0.0488 (12) | 0.0393 (10) | 0.0366 (11) | −0.0040 (9) | −0.0065 (9) | −0.0087 (9) |
C45 | 0.0660 (14) | 0.0404 (11) | 0.0414 (12) | −0.0046 (10) | −0.0125 (10) | −0.0044 (9) |
C46 | 0.094 (2) | 0.0782 (18) | 0.0554 (16) | −0.0438 (16) | 0.0040 (14) | −0.0025 (15) |
C47 | 0.0526 (14) | 0.0811 (18) | 0.0730 (18) | −0.0118 (14) | −0.0129 (12) | −0.0262 (15) |
C48 | 0.0474 (12) | 0.0473 (12) | 0.0374 (11) | −0.0040 (9) | −0.0069 (9) | −0.0113 (9) |
C49 | 0.0626 (15) | 0.0556 (14) | 0.0546 (14) | −0.0038 (11) | −0.0193 (12) | −0.0054 (11) |
C50 | 0.0687 (16) | 0.0806 (19) | 0.0640 (16) | −0.0003 (14) | −0.0317 (14) | −0.0188 (14) |
C51 | 0.0580 (14) | 0.0746 (17) | 0.0673 (16) | −0.0109 (13) | −0.0164 (12) | −0.0270 (14) |
C52 | 0.0806 (17) | 0.0509 (14) | 0.0613 (15) | −0.0137 (12) | −0.0188 (13) | −0.0155 (12) |
C53 | 0.0769 (16) | 0.0488 (13) | 0.0490 (13) | −0.0074 (11) | −0.0244 (12) | −0.0086 (10) |
C54 | 0.0542 (13) | 0.0467 (12) | 0.0360 (11) | −0.0155 (10) | −0.0033 (9) | −0.0087 (9) |
C55 | 0.0727 (16) | 0.0537 (14) | 0.0449 (12) | −0.0158 (12) | −0.0170 (11) | −0.0094 (10) |
C56 | 0.0716 (17) | 0.0797 (18) | 0.0497 (14) | −0.0219 (14) | −0.0187 (12) | −0.0124 (12) |
C57 | 0.0846 (19) | 0.0738 (18) | 0.0574 (15) | −0.0386 (15) | −0.0015 (13) | −0.0236 (13) |
C58 | 0.0798 (19) | 0.0551 (15) | 0.0827 (19) | −0.0213 (14) | −0.0073 (15) | −0.0251 (14) |
C59 | 0.0645 (15) | 0.0510 (14) | 0.0719 (16) | −0.0137 (12) | −0.0100 (13) | −0.0190 (12) |
N1—C10A | 1.358 (3) | N31—C40A | 1.359 (2) |
N1—N2 | 1.374 (2) | N31—N32 | 1.375 (2) |
N1—C18 | 1.421 (3) | N31—C48 | 1.419 (3) |
N2—C3 | 1.333 (3) | N32—C33 | 1.321 (3) |
C3—C3A | 1.409 (3) | C33—C33A | 1.408 (3) |
C3—C16 | 1.504 (3) | C33—C46 | 1.504 (3) |
C3A—C10A | 1.365 (3) | C33A—C40A | 1.368 (3) |
C3A—C4 | 1.503 (3) | C33A—C34 | 1.498 (3) |
C4—N5 | 1.490 (3) | C34—N35 | 1.487 (3) |
C4—H41 | 0.9700 | C34—H341 | 0.9700 |
C4—H42 | 0.9700 | C34—H342 | 0.9700 |
N5—C5A | 1.409 (2) | N35—C35A | 1.408 (3) |
N5—C15 | 1.472 (3) | N35—C45 | 1.477 (3) |
C5A—C8A | 1.368 (3) | C35A—C38A | 1.369 (3) |
C5A—N6 | 1.371 (3) | C35A—N36 | 1.371 (2) |
N6—N7 | 1.380 (2) | N36—N37 | 1.377 (2) |
N6—C24 | 1.420 (2) | N36—C54 | 1.418 (3) |
N7—C8 | 1.318 (3) | N37—C38 | 1.325 (3) |
C8—C8A | 1.415 (3) | C38—C38A | 1.414 (3) |
C8—C17 | 1.495 (3) | C38—C47 | 1.495 (3) |
C8A—C9 | 1.495 (3) | C38A—C39 | 1.500 (3) |
C9—N10 | 1.489 (2) | C39—N40 | 1.484 (3) |
C9—H91 | 0.9700 | C39—H391 | 0.9700 |
C9—H92 | 0.9700 | C39—H392 | 0.9700 |
N10—C10A | 1.412 (2) | N40—C40A | 1.410 (2) |
N10—C15 | 1.474 (3) | N40—C45 | 1.480 (3) |
C15—H151 | 0.9700 | C45—H451 | 0.9700 |
C15—H152 | 0.9700 | C45—H452 | 0.9700 |
C16—H161 | 0.9600 | C46—H461 | 0.9600 |
C16—H162 | 0.9600 | C46—H462 | 0.9600 |
C16—H163 | 0.9600 | C46—H463 | 0.9600 |
C17—H171 | 0.9600 | C47—H471 | 0.9600 |
C17—H172 | 0.9600 | C47—H472 | 0.9600 |
C17—H173 | 0.9600 | C47—H473 | 0.9600 |
C18—C19 | 1.378 (3) | C48—C49 | 1.379 (3) |
C18—C23 | 1.382 (3) | C48—C53 | 1.383 (3) |
C19—C20 | 1.374 (4) | C49—C50 | 1.386 (3) |
C19—H19 | 0.9300 | C49—H49 | 0.9300 |
C20—C21 | 1.366 (4) | C50—C51 | 1.367 (4) |
C20—H20 | 0.9300 | C50—H50 | 0.9300 |
C21—C22 | 1.380 (4) | C51—C52 | 1.368 (3) |
C21—H21 | 0.9300 | C51—H51 | 0.9300 |
C22—C23 | 1.371 (3) | C52—C53 | 1.380 (3) |
C22—H22 | 0.9300 | C52—H52 | 0.9300 |
C23—H23 | 0.9300 | C53—H53 | 0.9300 |
C24—C25 | 1.385 (3) | C54—C55 | 1.384 (3) |
C24—C29 | 1.387 (3) | C54—C59 | 1.387 (3) |
C25—C26 | 1.385 (3) | C55—C56 | 1.386 (3) |
C25—H25 | 0.9300 | C55—H55 | 0.9300 |
C26—C27 | 1.376 (4) | C56—C57 | 1.374 (4) |
C26—H26 | 0.9300 | C56—H56 | 0.9300 |
C27—C28 | 1.376 (4) | C57—C58 | 1.364 (4) |
C27—H27 | 0.9300 | C57—H57 | 0.9300 |
C28—C29 | 1.378 (3) | C58—C59 | 1.375 (3) |
C28—H28 | 0.9300 | C58—H58 | 0.9300 |
C29—H29 | 0.9300 | C59—H59 | 0.9300 |
C10A—N1—N2 | 110.55 (17) | C40A—N31—N32 | 110.32 (16) |
C10A—N1—C18 | 128.67 (17) | C40A—N31—C48 | 129.27 (17) |
N2—N1—C18 | 120.76 (16) | N32—N31—C48 | 120.39 (16) |
C3—N2—N1 | 105.01 (16) | C33—N32—N31 | 105.19 (17) |
N2—C3—C3A | 111.51 (19) | N32—C33—C33A | 111.99 (19) |
N2—C3—C16 | 119.9 (2) | N32—C33—C46 | 120.0 (2) |
C3A—C3—C16 | 128.5 (2) | C33A—C33—C46 | 128.0 (2) |
C10A—C3A—C3 | 104.69 (19) | C40A—C33A—C33 | 104.34 (18) |
C10A—C3A—C4 | 120.96 (18) | C40A—C33A—C34 | 121.21 (18) |
C3—C3A—C4 | 134.2 (2) | C33—C33A—C34 | 134.33 (19) |
N5—C4—C3A | 109.42 (16) | N35—C34—C33A | 109.73 (16) |
N5—C4—H41 | 109.8 | N35—C34—H341 | 109.7 |
C3A—C4—H41 | 109.8 | C33A—C34—H341 | 109.7 |
N5—C4—H42 | 109.8 | N35—C34—H342 | 109.7 |
C3A—C4—H42 | 109.8 | C33A—C34—H342 | 109.7 |
H41—C4—H42 | 108.2 | H341—C34—H342 | 108.2 |
C5A—N5—C15 | 106.57 (16) | C35A—N35—C45 | 106.56 (16) |
C5A—N5—C4 | 111.97 (15) | C35A—N35—C34 | 111.79 (16) |
C15—N5—C4 | 109.74 (16) | C45—N35—C34 | 109.53 (16) |
C8A—C5A—N6 | 108.02 (17) | C38A—C35A—N36 | 107.79 (18) |
C8A—C5A—N5 | 126.46 (19) | C38A—C35A—N35 | 126.79 (18) |
N6—C5A—N5 | 125.52 (18) | N36—C35A—N35 | 125.43 (18) |
C5A—N6—N7 | 109.93 (16) | C35A—N36—N37 | 110.16 (16) |
C5A—N6—C24 | 130.77 (17) | C35A—N36—C54 | 130.64 (18) |
N7—N6—C24 | 119.28 (16) | N37—N36—C54 | 119.20 (16) |
C8—N7—N6 | 105.58 (16) | C38—N37—N36 | 105.63 (16) |
N7—C8—C8A | 111.92 (17) | N37—C38—C38A | 111.46 (19) |
N7—C8—C17 | 121.06 (19) | N37—C38—C47 | 120.5 (2) |
C8A—C8—C17 | 127.02 (19) | C38A—C38—C47 | 128.0 (2) |
C5A—C8A—C8 | 104.53 (18) | C35A—C38A—C38 | 104.94 (18) |
C5A—C8A—C9 | 121.65 (18) | C35A—C38A—C39 | 121.32 (19) |
C8—C8A—C9 | 133.80 (18) | C38—C38A—C39 | 133.71 (19) |
N10—C9—C8A | 109.36 (16) | N40—C39—C38A | 109.64 (16) |
N10—C9—H91 | 109.8 | N40—C39—H391 | 109.7 |
C8A—C9—H91 | 109.8 | C38A—C39—H391 | 109.7 |
N10—C9—H92 | 109.8 | N40—C39—H392 | 109.7 |
C8A—C9—H92 | 109.8 | C38A—C39—H392 | 109.7 |
H91—C9—H92 | 108.3 | H391—C39—H392 | 108.2 |
C10A—N10—C15 | 106.30 (16) | C40A—N40—C45 | 106.19 (16) |
C10A—N10—C9 | 111.22 (15) | C40A—N40—C39 | 111.50 (15) |
C15—N10—C9 | 109.95 (16) | C45—N40—C39 | 110.11 (16) |
N1—C10A—C3A | 108.22 (17) | N31—C40A—C33A | 108.15 (17) |
N1—C10A—N10 | 124.60 (18) | N31—C40A—N40 | 124.97 (18) |
C3A—C10A—N10 | 127.16 (18) | C33A—C40A—N40 | 126.82 (18) |
N5—C15—N10 | 113.19 (16) | N35—C45—N40 | 113.06 (16) |
N5—C15—H151 | 108.9 | N35—C45—H451 | 109.0 |
N10—C15—H151 | 108.9 | N40—C45—H451 | 109.0 |
N5—C15—H152 | 108.9 | N35—C45—H452 | 109.0 |
N10—C15—H152 | 108.9 | N40—C45—H452 | 109.0 |
H151—C15—H152 | 107.8 | H451—C45—H452 | 107.8 |
C3—C16—H161 | 109.5 | C33—C46—H461 | 109.5 |
C3—C16—H162 | 109.5 | C33—C46—H462 | 109.5 |
H161—C16—H162 | 109.5 | H461—C46—H462 | 109.5 |
C3—C16—H163 | 109.5 | C33—C46—H463 | 109.5 |
H161—C16—H163 | 109.5 | H461—C46—H463 | 109.5 |
H162—C16—H163 | 109.5 | H462—C46—H463 | 109.5 |
C8—C17—H171 | 109.5 | C38—C47—H471 | 109.5 |
C8—C17—H172 | 109.5 | C38—C47—H472 | 109.5 |
H171—C17—H172 | 109.5 | H471—C47—H472 | 109.5 |
C8—C17—H173 | 109.5 | C38—C47—H473 | 109.5 |
H171—C17—H173 | 109.5 | H471—C47—H473 | 109.5 |
H172—C17—H173 | 109.5 | H472—C47—H473 | 109.5 |
C19—C18—C23 | 120.8 (2) | C49—C48—C53 | 120.1 (2) |
C19—C18—N1 | 120.1 (2) | C49—C48—N31 | 119.96 (19) |
C23—C18—N1 | 119.11 (19) | C53—C48—N31 | 119.90 (19) |
C20—C19—C18 | 119.1 (2) | C48—C49—C50 | 119.3 (2) |
C20—C19—H19 | 120.5 | C48—C49—H49 | 120.3 |
C18—C19—H19 | 120.5 | C50—C49—H49 | 120.3 |
C21—C20—C19 | 120.7 (2) | C51—C50—C49 | 120.5 (2) |
C21—C20—H20 | 119.6 | C51—C50—H50 | 119.8 |
C19—C20—H20 | 119.6 | C49—C50—H50 | 119.8 |
C20—C21—C22 | 119.8 (3) | C50—C51—C52 | 120.0 (2) |
C20—C21—H21 | 120.1 | C50—C51—H51 | 120.0 |
C22—C21—H21 | 120.1 | C52—C51—H51 | 120.0 |
C23—C22—C21 | 120.4 (3) | C51—C52—C53 | 120.6 (2) |
C23—C22—H22 | 119.8 | C51—C52—H52 | 119.7 |
C21—C22—H22 | 119.8 | C53—C52—H52 | 119.7 |
C22—C23—C18 | 119.1 (2) | C52—C53—C48 | 119.4 (2) |
C22—C23—H23 | 120.5 | C52—C53—H53 | 120.3 |
C18—C23—H23 | 120.5 | C48—C53—H53 | 120.3 |
C25—C24—C29 | 120.2 (2) | C55—C54—C59 | 119.9 (2) |
C25—C24—N6 | 120.8 (2) | C55—C54—N36 | 120.81 (19) |
C29—C24—N6 | 118.96 (19) | C59—C54—N36 | 119.3 (2) |
C26—C25—C24 | 119.2 (2) | C54—C55—C56 | 118.9 (2) |
C26—C25—H25 | 120.4 | C54—C55—H55 | 120.5 |
C24—C25—H25 | 120.4 | C56—C55—H55 | 120.5 |
C27—C26—C25 | 121.0 (3) | C57—C56—C55 | 121.0 (2) |
C27—C26—H26 | 119.5 | C57—C56—H56 | 119.5 |
C25—C26—H26 | 119.5 | C55—C56—H56 | 119.5 |
C28—C27—C26 | 119.2 (2) | C58—C57—C56 | 119.5 (2) |
C28—C27—H27 | 120.4 | C58—C57—H57 | 120.2 |
C26—C27—H27 | 120.4 | C56—C57—H57 | 120.2 |
C27—C28—C29 | 121.0 (3) | C57—C58—C59 | 120.8 (3) |
C27—C28—H28 | 119.5 | C57—C58—H58 | 119.6 |
C29—C28—H28 | 119.5 | C59—C58—H58 | 119.6 |
C28—C29—C24 | 119.4 (2) | C58—C59—C54 | 119.8 (3) |
C28—C29—H29 | 120.3 | C58—C59—H59 | 120.1 |
C24—C29—H29 | 120.3 | C54—C59—H59 | 120.1 |
C10A—N1—N2—C3 | −1.4 (2) | C40A—N31—N32—C33 | 0.9 (2) |
C18—N1—N2—C3 | 179.93 (18) | C48—N31—N32—C33 | −177.46 (19) |
N1—N2—C3—C3A | 1.1 (2) | N31—N32—C33—C33A | −0.4 (2) |
N1—N2—C3—C16 | 179.0 (2) | N31—N32—C33—C46 | −178.5 (2) |
N2—C3—C3A—C10A | −0.5 (2) | N32—C33—C33A—C40A | −0.2 (3) |
C16—C3—C3A—C10A | −178.1 (2) | C46—C33—C33A—C40A | 177.7 (2) |
N2—C3—C3A—C4 | 175.2 (2) | N32—C33—C33A—C34 | −176.1 (2) |
C16—C3—C3A—C4 | −2.5 (4) | C46—C33—C33A—C34 | 1.8 (4) |
C10A—C3A—C4—N5 | 11.7 (3) | C40A—C33A—C34—N35 | −12.5 (3) |
C3—C3A—C4—N5 | −163.4 (2) | C33—C33A—C34—N35 | 162.9 (2) |
C3A—C4—N5—C5A | 74.4 (2) | C33A—C34—N35—C35A | −74.2 (2) |
C3A—C4—N5—C15 | −43.7 (2) | C33A—C34—N35—C45 | 43.7 (2) |
C15—N5—C5A—C8A | 18.5 (3) | C45—N35—C35A—C38A | −18.9 (3) |
C4—N5—C5A—C8A | −101.5 (2) | C34—N35—C35A—C38A | 100.7 (2) |
C15—N5—C5A—N6 | −160.79 (18) | C45—N35—C35A—N36 | 161.47 (18) |
C4—N5—C5A—N6 | 79.2 (2) | C34—N35—C35A—N36 | −78.9 (2) |
C8A—C5A—N6—N7 | 1.5 (2) | C38A—C35A—N36—N37 | −1.4 (2) |
N5—C5A—N6—N7 | −179.10 (17) | N35—C35A—N36—N37 | 178.27 (17) |
C8A—C5A—N6—C24 | −176.95 (18) | C38A—C35A—N36—C54 | 178.46 (19) |
N5—C5A—N6—C24 | 2.5 (3) | N35—C35A—N36—C54 | −1.8 (3) |
C5A—N6—N7—C8 | −1.0 (2) | C35A—N36—N37—C38 | 1.6 (2) |
C24—N6—N7—C8 | 177.65 (17) | C54—N36—N37—C38 | −178.30 (17) |
N6—N7—C8—C8A | 0.1 (2) | N36—N37—C38—C38A | −1.2 (2) |
N6—N7—C8—C17 | 179.67 (18) | N36—N37—C38—C47 | −179.16 (19) |
N6—C5A—C8A—C8 | −1.3 (2) | N36—C35A—C38A—C38 | 0.7 (2) |
N5—C5A—C8A—C8 | 179.27 (18) | N35—C35A—C38A—C38 | −179.02 (19) |
N6—C5A—C8A—C9 | −179.69 (17) | N36—C35A—C38A—C39 | 179.15 (17) |
N5—C5A—C8A—C9 | 0.9 (3) | N35—C35A—C38A—C39 | −0.5 (3) |
N7—C8—C8A—C5A | 0.7 (2) | N37—C38—C38A—C35A | 0.3 (2) |
C17—C8—C8A—C5A | −178.8 (2) | C47—C38—C38A—C35A | 178.1 (2) |
N7—C8—C8A—C9 | 178.8 (2) | N37—C38—C38A—C39 | −177.9 (2) |
C17—C8—C8A—C9 | −0.7 (4) | C47—C38—C38A—C39 | −0.1 (4) |
C5A—C8A—C9—N10 | 11.5 (3) | C35A—C38A—C39—N40 | −11.6 (3) |
C8—C8A—C9—N10 | −166.3 (2) | C38—C38A—C39—N40 | 166.4 (2) |
C8A—C9—N10—C10A | 74.5 (2) | C38A—C39—N40—C40A | −74.8 (2) |
C8A—C9—N10—C15 | −43.0 (2) | C38A—C39—N40—C45 | 42.8 (2) |
N2—N1—C10A—C3A | 1.1 (2) | N32—N31—C40A—C33A | −1.1 (2) |
C18—N1—C10A—C3A | 179.69 (18) | C48—N31—C40A—C33A | 177.12 (19) |
N2—N1—C10A—N10 | −177.42 (17) | N32—N31—C40A—N40 | 176.21 (18) |
C18—N1—C10A—N10 | 1.2 (3) | C48—N31—C40A—N40 | −5.6 (3) |
C3—C3A—C10A—N1 | −0.4 (2) | C33—C33A—C40A—N31 | 0.7 (2) |
C4—C3A—C10A—N1 | −176.77 (17) | C34—C33A—C40A—N31 | 177.30 (18) |
C3—C3A—C10A—N10 | 178.09 (19) | C33—C33A—C40A—N40 | −176.46 (19) |
C4—C3A—C10A—N10 | 1.7 (3) | C34—C33A—C40A—N40 | 0.1 (3) |
C15—N10—C10A—N1 | −164.31 (18) | C45—N40—C40A—N31 | 164.07 (19) |
C9—N10—C10A—N1 | 76.0 (2) | C39—N40—C40A—N31 | −76.0 (2) |
C15—N10—C10A—C3A | 17.4 (3) | C45—N40—C40A—C33A | −19.2 (3) |
C9—N10—C10A—C3A | −102.2 (2) | C39—N40—C40A—C33A | 100.8 (2) |
C5A—N5—C15—N10 | −52.4 (2) | C35A—N35—C45—N40 | 52.2 (2) |
C4—N5—C15—N10 | 69.0 (2) | C34—N35—C45—N40 | −68.9 (2) |
C10A—N10—C15—N5 | −52.0 (2) | C40A—N40—C45—N35 | 52.8 (2) |
C9—N10—C15—N5 | 68.5 (2) | C39—N40—C45—N35 | −68.0 (2) |
C10A—N1—C18—C19 | −139.0 (2) | C40A—N31—C48—C49 | 145.9 (2) |
N2—N1—C18—C19 | 39.5 (3) | N32—N31—C48—C49 | −36.1 (3) |
C10A—N1—C18—C23 | 40.9 (3) | C40A—N31—C48—C53 | −35.1 (3) |
N2—N1—C18—C23 | −140.7 (2) | N32—N31—C48—C53 | 142.9 (2) |
C23—C18—C19—C20 | −0.7 (4) | C53—C48—C49—C50 | 2.1 (3) |
N1—C18—C19—C20 | 179.1 (2) | N31—C48—C49—C50 | −178.9 (2) |
C18—C19—C20—C21 | −1.8 (4) | C48—C49—C50—C51 | 0.7 (4) |
C19—C20—C21—C22 | 2.5 (4) | C49—C50—C51—C52 | −2.4 (4) |
C20—C21—C22—C23 | −0.7 (4) | C50—C51—C52—C53 | 1.2 (4) |
C21—C22—C23—C18 | −1.9 (4) | C51—C52—C53—C48 | 1.6 (4) |
C19—C18—C23—C22 | 2.6 (3) | C49—C48—C53—C52 | −3.3 (3) |
N1—C18—C23—C22 | −177.3 (2) | N31—C48—C53—C52 | 177.7 (2) |
C5A—N6—C24—C25 | 19.9 (3) | C35A—N36—C54—C55 | −22.3 (3) |
N7—N6—C24—C25 | −158.41 (19) | N37—N36—C54—C55 | 157.59 (19) |
C5A—N6—C24—C29 | −162.5 (2) | C35A—N36—C54—C59 | 159.7 (2) |
N7—N6—C24—C29 | 19.3 (3) | N37—N36—C54—C59 | −20.5 (3) |
C29—C24—C25—C26 | 1.7 (3) | C59—C54—C55—C56 | −2.4 (3) |
N6—C24—C25—C26 | 179.34 (19) | N36—C54—C55—C56 | 179.57 (19) |
C24—C25—C26—C27 | −1.1 (3) | C54—C55—C56—C57 | 1.8 (3) |
C25—C26—C27—C28 | −0.5 (4) | C55—C56—C57—C58 | −0.3 (4) |
C26—C27—C28—C29 | 1.6 (4) | C56—C57—C58—C59 | −0.7 (4) |
C27—C28—C29—C24 | −1.1 (4) | C57—C58—C59—C54 | 0.1 (4) |
C25—C24—C29—C28 | −0.6 (3) | C55—C54—C59—C58 | 1.5 (3) |
N6—C24—C29—C28 | −178.32 (19) | N36—C54—C59—C58 | 179.5 (2) |
Experimental details
Crystal data | |
Chemical formula | C23H22N6 |
Mr | 382.46 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 11.224 (1), 13.650 (1), 14.110 (1) |
α, β, γ (°) | 75.270 (2), 73.070 (2), 76.270 (2) |
V (Å3) | 1968.7 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.20 × 0.15 × 0.12 |
Data collection | |
Diffractometer | Rigaku AFC7S diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7664, 7332, 4249 |
Rint | 0.091 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.141, 1.02 |
No. of reflections | 7332 |
No. of parameters | 570 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.17, −0.23 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1993), MSC/AFC Diffractometer Control Software, SHELXS86 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ZORTEP (Zsolnai, 1995), SHELXL97.
C4—N5 | 1.490 (3) | C34—N35 | 1.487 (3) |
N5—C5A | 1.409 (2) | N35—C35A | 1.408 (3) |
N5—C15 | 1.472 (3) | N35—C45 | 1.477 (3) |
C9—N10 | 1.489 (2) | C39—N40 | 1.484 (3) |
N10—C10A | 1.412 (2) | N40—C40A | 1.410 (2) |
N10—C15 | 1.474 (3) | N40—C45 | 1.480 (3) |
C5A—N5—C4 | 111.97 (15) | C35A—N35—C34 | 111.79 (16) |
C10A—N10—C9 | 111.22 (15) | C40A—N40—C39 | 111.50 (15) |
N5—C15—N10 | 113.19 (16) | N35—C45—N40 | 113.06 (16) |
C4—N5—C5A—N6 | 79.2 (2) | C34—N35—C35A—N36 | −78.9 (2) |
C9—N10—C10A—N1 | 76.0 (2) | C39—N40—C40A—N31 | −76.0 (2) |
N2—N1—C18—C19 | 39.5 (3) | N32—N31—C48—C49 | −36.1 (3) |
N7—N6—C24—C29 | 19.3 (3) | N37—N36—C54—C59 | −20.5 (3) |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- Purchase subscription
- Reduced-price subscriptions
- If you have already subscribed, you may need to register
As part of an ongoing study of the reactivity of pyrazole derivatives as activated aromatic precursors (Quiroga et al., 1999), the synthesis of fused amino-heterocycle systems was undertaken to obtain a compound with a five-membered aromatic ring: a new Tröger's base. The molecular structure of 3,4,7,8-bis(1-phenylpyrazol)-1,5-methylene-1,5-diazacyclooctane, the first pyrazolic Tröger's base, has been reported in the literature (Cudero et al., 1997). In the Cambridge Structural Database (Allen et al., 1991), this compound has the refcode NIMHIA. Tröger's bases are concave chiral molecules with interesting structural properties. Several Tröger's base analogues with potential applications in the design of synthetic enzymes, artificial receptor systems, selective organic catalysts and reagents (Cowart et al., 1988; Adrian, Jr. & Wilcox, 1992), chelating and biomimetic systems (Wilcox, 1985; Crossley et al., 1995) and metal complexes with catalytic activity (Goldberg et al., 1995) have been reported. The title Tröger's base, (II), was synthesized from 5-amino-3-methyl-1-phenyl pyrazole, (I), by reaction with formaldehyde. \sch
Compound (II) has a folded structure wherein the two N atoms and the three methylene carbons form a hingelike bridge between the two pyrazole rings. Comparing the bond lengths of the free molecule of pyrazole (Larsen et al., 1970) with the pyrazole moiety in the title compound, it was found that the N—N bond length changes from 1.334 and 1.338 Å in the free molecule to 1.374 (2) Å for N1—N2, 1.380 (2) Å, for N6—N7, 1.375 (2) Å for N31—N32 and 1.377 (2) Å for N36—N37 in the title compound. The C—N bond length in the free molecule of pyrazole changes from 1.325 and 1.339 Å to 1.358 (3) Å for N1—C10a, 1.371 (3) for N6—C5a, 1.359 (2) for N31—C40a and 1.371 (2) Å for N36—C35a in the title structure. Values of the bond angles of the pyrazole ring of the free molecule and values of the bond angles of the pyrazole moiety of compound (II) are similar. When bond lengths and bond angles of the eight-membered ring in the structure NIMHIA are compared to bond lengths and bond angles of same ring in the title structure, minor differences in these values were found. The other bond lengths values of phenyl and pyrazole rings of the NIMHIA structure are very close to those values in the title structure. The tetrahydropyrimidin backbone adopts a half chair conformation (Cremer & Pople, 1975). This conformation is similar to that in NIMHIA. In Tröger's bases, the dihedral angle, formed by the least-squares planes containing aryl substituent rings, varies from 92° to 104° (Wilcox et al., 1987). This same dihedral angle in the NIMHIA structure containing pyrazole rings has a value of 96.4 (4)° while in compound (II) are 85.95 (7) and 86.82 (9)°. There are two molecules o fopposite chirality in the asymmetric unit and the packing in the lattice is characterized by a non-crystallographic n-glide plane relating these molecules. These molecules also exhibit dyad symmetry. The equation found for the glide plane is 0.0178x + 0.0006y + 0.9998z - 5.1954 = 0 and the translations are approximately (a+b)/2. Fig. 2 shows the packing with the two independent enantiomers related by the pseudo n glide plane.