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organic compounds
Two isomeric 10-methyl-8-phenyl-11-pyridyl-6,8-dihydro-5H-benzo[f]pyrazolo[3,4-b]quinolines: cyclic hydrogen-bonded tetramers versus isolated molecules
aGrupo de Investigación de Compuestos Heterocíclicos, Departamento de Química, Universidad de Valle, AA 25360 Cali, Colombia, bDepartamento de Química Inorgánica y Orgánica, Universidad de Jaén, 23071 Jaén, Spain, cDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, and dSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland
*Correspondence e-mail: cg@st-andrews.ac.uk
The molecules of 10-methyl-8-phenyl-11-(3-pyridyl)-6,8-dihydro-5H-benzo[f]pyrazolo[3,4-b]quinoline, C26H20N4, (I), are linked by a single C—H⋯N hydrogen bond into cyclic R
(12) tetramers generated by a
axis. In isomeric 10-methyl-8-phenyl-11-(4-pyridyl)-6,8-dihydro-5H-benzo[f]pyrazolo[3,4-b]quinoline, (II)
, which crystallizes with Z′ = 2 in P21212, the two independent molecules are nearly enantiomeric but there are no direction-specific interactions between them.
Comment
We report here the structures of two isomeric 11-pyridyl-10-methyl-8-phenyl-6,8-dihydro-5H-benzo[f]pyrazolo[3,4-b]quinolines, (I) and (II)
. Compound (I)
is a pyridyl analogue of the isostructural pair 11-(4-chlorophenyl)-10-methyl-8-phenyl-6,8-dihydro-5H-benzo[f]pyrazolo[3,4-b]quinoline, (III) (Serrano et al., 2005a
), and 11-(4-bromophenyl)-10-methyl-8-phenyl-6,8-dihydro-5H-benzo[f]pyrazolo[3,4-b]quinoline, (IV) (Serrano et al., 2005b
), while compound (II)
is a simple positional isomer of (I)
.
The non-aromatic carbocyclic rings in both compounds adopt screw-boat conformations, as shown by the ring-puckering parameters (Cremer & Pople, 1975; Evans & Boeyens, 1989
). For (I)
, these are θ = 71.0 (2)° and φ = 94.3 (33)° for the atom sequence C4a/C5/C6/C6a/C11a/C11b (Fig. 1
), as compared with the idealized values, for an ring with equal bond distances throughout, of θ = 67.5° and φ = (60k + 30)°. In (II)
, for the atom sequences C11a—C11b—C14a—C15—C16—C16a in molecule 1 and C21a—C21b—C24a—C25—C26—C26a in molecule 2 (Fig. 2
), the corresponding values are 69.9 (5) and 214.9 (5)°, respectively, in molecule 1, and 108.8 (4) and 33.1 (5)°, respectively, in molecule 2. In compounds (I)
and (II)
, the molecules have no internal symmetry and they are chiral. For (I)
, the P
21c accommodates equal numbers of the two enantiomers, but for (II)
, in P21212, each crystal will, in the absence of inversion contain just a single However, the ring-puckering parameters for compound (II)
show that the two independent molecules are very close to being enantiomers (Fig. 2
), although no possible additional symmetry was detected.
The overall conformations in (I) and (II)
are very similar. For example, the dihedral angles between the pyrazole ring and its pendent aryl ring are 18.3 (2)° in (I)
, and 10.7 (2) and 16.7 (2)° in (II)
, the dihedral angles between the two pyridine rings are 66.6 (2)° in (I)
, and 75.4 (2) and 72.4 (2)° in (II)
, and the dihedral angles between the fused pyridine ring and the fused aryl ring are 27.3 (2)° in (I)
and 24.4 (2) and 26.4 (2)° in (II)
. The difference in the orientation of the two pendent rings, viz. one aryl and one pyridyl, is striking. The near coplanarity of the pyrazole and pendent aryl rings may be associated with the short intramolecular C—H⋯N contacts involving these rings (Tables 1
and 2
). The modest differences between the corresponding values for the two molecules in compound (II)
are sufficient to preclude the possibility of additional symmetry. The bond distances and angles show no unusual values.
The molecules in compound (I) are linked by a single C—H⋯N hydrogen bond (Table 1
). Aryl atom C114 in the molecule at (x, y, z) acts as hydrogen-bond donor to the pyridyl atom N113 in the molecule at (y, 1 − x, 2 − z), while atom C114 at (y, 1 − x, 2 − z) in turn acts as donor to atom N113 at (1 − x, 1 − y, z). Propagation of this hydrogen bond thus produces a puckered R
(12) tetramer generated by the
axis along (
,
, z) (Fig. 3
). A second such tetramer, related to the first by the action of the c-glide planes, is generated by the
axis along (0, 0, z), but there are no direction-specific interactions between adjacent tetramers. By contrast, there are no direction-specific interactions of any kind between molecules of compound (II)
. In particular, the pyridyl N atoms N114 and N224 have no potential hydrogen-bond donors with N⋯H distances less than 2.65 Å.
The very different space groups and patterns of supramolecular aggregation manifested by isomers (I) and (II)
may be contrasted with their 4-haloaryl analogues (III) and (IV), which are strictly isomorphous and isostructural in P
, and where the molecules are linked by C—H⋯π(arene) hydrogen bonds, although C—H⋯N hydrogen bonds, as found here for (I)
, are absent from both (III)
and (IV).
![]() | Figure 1 The molecule of (I) ![]() |
![]() | Figure 2 The two independent molecules of (II) ![]() |
![]() | Figure 3 A stereoview of part of the crystal structure of (I) ![]() ![]() ![]() |
Experimental
Equimolar amounts of 5-amino-3-methyl-1-phenylpyrazole (173 mg, 1.0 mmol), 2-tetralone (146 mg, 1.0 mmol) and the appropriate pyridinecarbaldehyde [pyridine-3-carbaldehyde for (I) and pyridine-4-carbaldehyde for (II)] (107.0 mg, 1.0 mmol) were placed in open Pyrex glass vessels and irradiated in a domestic microwave oven for 4.5 min at 600 W. The reaction mixtures were then extracted with ethanol and, after removal of the solvent, the products were recrystallized from ethanol–dimethylformamide (1:1 v/v) to give crystals suitable for single-crystal X-ray diffraction. Compound (I)
, yellow crystals, 55% yield, m.p. 445–446 K; MS (30 eV) m/z (%): 389 (30), 388 (100, M+), 387 (58), 373 (4). Compound (II)
, yellow crystals, 40% yield, m.p. 493 K; MS (30 eV) m/z (%): 388 (100, M+), 373 (5).
Compound (I)![[link]](../../../../../../logos/arrows/c_arr.gif)
Crystal data
|
Data collection
Refinement
|
|
Compound (II)![[link]](../../../../../../logos/arrows/c_arr.gif)
Crystal data
|
Data collection
Refinement
|
|
P21c for (I)
and P21212 for (II)
were both assigned uniquely from the All H atoms were located from difference maps and then treated as riding atoms, with C—H distances of 0.95 (aromatic), 0.98 (CH3) or 0.99 Å (CH2), and with Uiso(H) = 1.2Ueq(C), or 1.5Ueq(C) for the methyl groups. In the absence of significant the Flack (1983
) parameter was indeterminate for both compounds (Flack & Bernardinelli, 2000
). Hence, Friedel-equivalent reflections were merged prior to the final refinements. Accordingly, it was not possible to establish the absolute axis assignment in (I)
or the absolute configurations of the molecules in the crystal of (II)
selected for data collection (Jones, 1986
).
For both compounds, data collection: COLLECT (Hooft, 1999); cell DENZO (Otwinowski & Minor, 1997
) and COLLECT; data reduction: DENZO and COLLECT; structure solution: OSCAIL (McArdle, 2003
) and SHELXS97 (Sheldrick, 1997
); structure OSCAIL and SHELXL97 (Sheldrick, 1997
); molecular graphics: PLATON (Spek, 2003
); publication software: SHELXL97 and PRPKAPPA (Ferguson, 1999
).
Supporting information
10.1107/S0108270105021876/gg1280sup1.cif
contains datablocks global, I, II. DOI:Structure factors: contains datablock I. DOI: 10.1107/S0108270105021876/gg1280Isup2.hkl
Structure factors: contains datablock II. DOI: 10.1107/S0108270105021876/gg1280IIsup3.hkl
Equimolar amounts of 5-amino-3-methyl-1-phenylpyrazole (173 mg, 1.0 mmol), 2-tetralone (146 mg, 1.0 mmol) and the appropriate pyridylcarboxaldehyde [3-pyridylcarboxaldehyde for (I) and 4-pyridylcarboxaldehyde for (II)] (107.0 mg, 1.0 mmol) were placed in open Pyrex glass vessels and irradiated in a domestic microwave oven for 4.5 min at 600 W. The reaction mixture was then extracted with ethanol and, after removal of the solvent, the product was recrystallized from ethanol–dimethylformamide (1:1 v/v) to give crystals suitable for single-crystal X-ray diffraction. Compound (I), yellow crystals, 55% yield, m.p. 445–446 K, MS (30 eV) m/z (%): 389 (30), 388 (100, M+), 387 (58), 373 (4). Compound (II), yellow crystals, 40% yield, m.p. 493 K, MS (30 eV) m/z (%): 388 (100, M+), 373 (5).
The space groups P421c for (I) and P21212 for (II) were both assigned uniquely from the All H atoms were located from difference maps and then treated as riding atoms with C—H distances of 0.95 (aromatic), 0.98 (CH3) or 0.99 Å (CH2), and with Uiso(H) = 1.2Ueq(C), or 1.5Ueq(C) for the methyl groups. In the absence of significant the (Flack, 1983) was indeterminate for both compounds (Flack & Bernardinelli, 2000). Hence, Friedel-equivalent reflections were merged prior to the final refinements. Accordingly, it was not possible to establish the absolute axis assignment in (I) or the absolute configurations of the molecules in the crystal of (II) selected for data collection (Jones, 1986).
For both compounds, data collection: COLLECT (Hooft, 1999); cell
DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).C26H20N4 | Dx = 1.290 Mg m−3 |
Mr = 388.46 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, P421c | Cell parameters from 2537 reflections |
Hall symbol: P -4 2n | θ = 3.7–27.5° |
a = 19.2181 (6) Å | µ = 0.08 mm−1 |
c = 10.8347 (2) Å | T = 120 K |
V = 4001.64 (19) Å3 | Lath, yellow |
Z = 8 | 0.44 × 0.35 × 0.10 mm |
F(000) = 1632 |
Bruker Nonius KappaCCD area-detector diffractometer | 2537 independent reflections |
Radiation source: Bruker Nonius FR91 rotating anode | 2004 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.070 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.7° |
ϕ and ω scans | h = −21→24 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −24→20 |
Tmin = 0.955, Tmax = 0.992 | l = −11→13 |
28744 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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.089 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0472P)2 + 0.2954P] where P = (Fo2 + 2Fc2)/3 |
2537 reflections | (Δ/σ)max < 0.001 |
272 parameters | Δρmax = 0.16 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
C26H20N4 | Z = 8 |
Mr = 388.46 | Mo Kα radiation |
Tetragonal, P421c | µ = 0.08 mm−1 |
a = 19.2181 (6) Å | T = 120 K |
c = 10.8347 (2) Å | 0.44 × 0.35 × 0.10 mm |
V = 4001.64 (19) Å3 |
Bruker Nonius KappaCCD area-detector diffractometer | 2537 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2004 reflections with I > 2σ(I) |
Tmin = 0.955, Tmax = 0.992 | Rint = 0.070 |
28744 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.089 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.16 e Å−3 |
2537 reflections | Δρmin = −0.20 e Å−3 |
272 parameters |
x | y | z | Uiso*/Ueq | ||
N7 | 0.24290 (9) | 0.78531 (9) | 0.60646 (15) | 0.0238 (4) | |
N8 | 0.24404 (9) | 0.67359 (9) | 0.50319 (17) | 0.0250 (4) | |
N9 | 0.28393 (9) | 0.61370 (9) | 0.50806 (17) | 0.0269 (4) | |
N113 | 0.47725 (11) | 0.65085 (11) | 0.97103 (19) | 0.0369 (5) | |
C1 | 0.43867 (12) | 0.84834 (12) | 0.8828 (2) | 0.0282 (5) | |
C2 | 0.46357 (13) | 0.89273 (13) | 0.9739 (2) | 0.0336 (6) | |
C3 | 0.41896 (13) | 0.93873 (12) | 1.0321 (2) | 0.0316 (6) | |
C4 | 0.34984 (12) | 0.94151 (12) | 0.9962 (2) | 0.0295 (5) | |
C4a | 0.32421 (12) | 0.89771 (11) | 0.90475 (19) | 0.0249 (5) | |
C5 | 0.25044 (12) | 0.90444 (12) | 0.85856 (19) | 0.0285 (5) | |
C6 | 0.24859 (13) | 0.89273 (11) | 0.7200 (2) | 0.0285 (5) | |
C6a | 0.27731 (11) | 0.82191 (12) | 0.69152 (19) | 0.0235 (5) | |
C7a | 0.26967 (11) | 0.72187 (11) | 0.58485 (18) | 0.0228 (5) | |
C10 | 0.33329 (11) | 0.62421 (11) | 0.59064 (19) | 0.0250 (5) | |
C10a | 0.32778 (11) | 0.69279 (11) | 0.64186 (19) | 0.0227 (5) | |
C11 | 0.36385 (11) | 0.73278 (11) | 0.73043 (19) | 0.0220 (5) | |
C11a | 0.33775 (11) | 0.79896 (11) | 0.75649 (19) | 0.0224 (5) | |
C11b | 0.36840 (12) | 0.84806 (11) | 0.8488 (2) | 0.0248 (5) | |
C81 | 0.18668 (11) | 0.67654 (11) | 0.42073 (19) | 0.0241 (5) | |
C82 | 0.18300 (13) | 0.62958 (14) | 0.3241 (2) | 0.0350 (6) | |
C83 | 0.12723 (13) | 0.63231 (14) | 0.2439 (2) | 0.0391 (6) | |
C84 | 0.07553 (12) | 0.68086 (13) | 0.2580 (2) | 0.0338 (6) | |
C85 | 0.07955 (12) | 0.72783 (13) | 0.3542 (2) | 0.0335 (6) | |
C86 | 0.13455 (12) | 0.72579 (13) | 0.4364 (2) | 0.0299 (5) | |
C101 | 0.38295 (13) | 0.56611 (12) | 0.6182 (2) | 0.0324 (6) | |
C111 | 0.42608 (11) | 0.70082 (11) | 0.78941 (19) | 0.0235 (5) | |
C112 | 0.42481 (12) | 0.68291 (12) | 0.9138 (2) | 0.0283 (5) | |
C114 | 0.53347 (13) | 0.63575 (14) | 0.9027 (2) | 0.0384 (6) | |
C115 | 0.53983 (12) | 0.65233 (12) | 0.7799 (2) | 0.0346 (6) | |
C116 | 0.48531 (11) | 0.68560 (11) | 0.7219 (2) | 0.0269 (5) | |
H1 | 0.4700 | 0.8175 | 0.8427 | 0.034* | |
H2 | 0.5113 | 0.8915 | 0.9962 | 0.040* | |
H3 | 0.4356 | 0.9682 | 1.0960 | 0.038* | |
H4 | 0.3194 | 0.9739 | 1.0348 | 0.035* | |
H5A | 0.2323 | 0.9514 | 0.8780 | 0.034* | |
H5B | 0.2205 | 0.8697 | 0.9002 | 0.034* | |
H6A | 0.2001 | 0.8962 | 0.6897 | 0.034* | |
H6B | 0.2767 | 0.9288 | 0.6779 | 0.034* | |
H10A | 0.3688 | 0.5244 | 0.5728 | 0.049* | |
H10B | 0.3825 | 0.5563 | 0.7070 | 0.049* | |
H10C | 0.4300 | 0.5797 | 0.5929 | 0.049* | |
H82 | 0.2185 | 0.5958 | 0.3131 | 0.042* | |
H83 | 0.1246 | 0.6000 | 0.1777 | 0.047* | |
H84 | 0.0374 | 0.6822 | 0.2023 | 0.041* | |
H85 | 0.0442 | 0.7619 | 0.3640 | 0.040* | |
H86 | 0.1367 | 0.7578 | 0.5030 | 0.036* | |
H112 | 0.3845 | 0.6941 | 0.9605 | 0.034* | |
H114 | 0.5711 | 0.6122 | 0.9415 | 0.046* | |
H115 | 0.5810 | 0.6411 | 0.7357 | 0.041* | |
H116 | 0.4883 | 0.6979 | 0.6371 | 0.032* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N7 | 0.0231 (10) | 0.0231 (10) | 0.0253 (9) | 0.0003 (8) | 0.0008 (8) | 0.0006 (8) |
N8 | 0.0241 (10) | 0.0227 (10) | 0.0284 (9) | 0.0039 (8) | −0.0037 (8) | −0.0030 (8) |
N9 | 0.0245 (10) | 0.0251 (11) | 0.0312 (10) | 0.0028 (8) | −0.0006 (9) | −0.0012 (8) |
N113 | 0.0338 (13) | 0.0362 (13) | 0.0408 (11) | −0.0016 (10) | −0.0085 (10) | 0.0089 (10) |
C1 | 0.0273 (14) | 0.0247 (13) | 0.0327 (12) | −0.0024 (10) | 0.0003 (10) | −0.0016 (10) |
C2 | 0.0309 (14) | 0.0362 (15) | 0.0338 (13) | −0.0047 (11) | −0.0048 (11) | −0.0017 (11) |
C3 | 0.0392 (15) | 0.0295 (14) | 0.0263 (12) | −0.0064 (11) | −0.0003 (10) | −0.0044 (10) |
C4 | 0.0375 (15) | 0.0255 (13) | 0.0257 (12) | 0.0000 (11) | 0.0050 (11) | −0.0004 (10) |
C4a | 0.0315 (13) | 0.0218 (12) | 0.0213 (10) | −0.0029 (10) | 0.0037 (10) | 0.0041 (9) |
C5 | 0.0321 (14) | 0.0263 (13) | 0.0272 (12) | 0.0032 (10) | 0.0040 (10) | 0.0010 (10) |
C6 | 0.0295 (12) | 0.0250 (13) | 0.0309 (13) | 0.0030 (10) | −0.0024 (10) | 0.0003 (10) |
C6a | 0.0230 (11) | 0.0221 (12) | 0.0254 (11) | −0.0023 (10) | 0.0033 (9) | 0.0015 (9) |
C7a | 0.0242 (12) | 0.0225 (12) | 0.0218 (10) | −0.0020 (9) | 0.0006 (9) | 0.0003 (9) |
C10 | 0.0238 (12) | 0.0249 (12) | 0.0265 (11) | −0.0007 (10) | 0.0006 (10) | 0.0008 (10) |
C10a | 0.0218 (12) | 0.0237 (12) | 0.0227 (10) | −0.0006 (9) | 0.0018 (9) | 0.0016 (9) |
C11 | 0.0220 (12) | 0.0231 (12) | 0.0210 (11) | −0.0013 (9) | 0.0013 (9) | 0.0037 (9) |
C11a | 0.0215 (11) | 0.0226 (11) | 0.0230 (11) | −0.0022 (9) | 0.0042 (9) | 0.0018 (9) |
C11b | 0.0299 (13) | 0.0213 (12) | 0.0231 (10) | −0.0050 (10) | 0.0027 (10) | 0.0047 (9) |
C81 | 0.0223 (12) | 0.0267 (12) | 0.0234 (11) | −0.0032 (10) | −0.0014 (9) | 0.0014 (9) |
C82 | 0.0321 (14) | 0.0395 (15) | 0.0333 (13) | 0.0088 (12) | −0.0048 (11) | −0.0076 (11) |
C83 | 0.0363 (15) | 0.0497 (17) | 0.0314 (13) | 0.0048 (12) | −0.0056 (11) | −0.0112 (12) |
C84 | 0.0270 (13) | 0.0451 (15) | 0.0293 (12) | −0.0013 (12) | −0.0052 (10) | −0.0011 (11) |
C85 | 0.0237 (13) | 0.0363 (14) | 0.0405 (13) | 0.0015 (11) | −0.0031 (11) | −0.0020 (12) |
C86 | 0.0265 (13) | 0.0308 (13) | 0.0323 (12) | −0.0015 (11) | −0.0010 (10) | −0.0056 (11) |
C101 | 0.0308 (14) | 0.0237 (12) | 0.0427 (14) | 0.0034 (11) | −0.0054 (11) | −0.0041 (11) |
C111 | 0.0228 (12) | 0.0194 (11) | 0.0281 (11) | −0.0033 (9) | −0.0022 (10) | 0.0011 (9) |
C112 | 0.0258 (12) | 0.0278 (12) | 0.0312 (12) | −0.0036 (11) | −0.0014 (10) | 0.0034 (10) |
C114 | 0.0250 (14) | 0.0360 (15) | 0.0542 (16) | −0.0004 (11) | −0.0113 (13) | 0.0104 (13) |
C115 | 0.0254 (13) | 0.0304 (14) | 0.0479 (15) | 0.0032 (11) | −0.0038 (11) | 0.0014 (12) |
C116 | 0.0254 (12) | 0.0255 (12) | 0.0298 (11) | −0.0018 (10) | −0.0002 (10) | 0.0013 (10) |
C1—C2 | 1.390 (3) | C83—H83 | 0.95 |
C1—C11b | 1.400 (3) | C84—C85 | 1.381 (3) |
C1—H1 | 0.95 | C84—H84 | 0.95 |
C2—C3 | 1.384 (3) | C85—C86 | 1.383 (3) |
C2—H2 | 0.95 | C85—H85 | 0.95 |
C3—C4 | 1.385 (3) | C86—H86 | 0.95 |
C3—H3 | 0.95 | C7a—C10a | 1.393 (3) |
C4—C4a | 1.390 (3) | N9—C10 | 1.320 (3) |
C4—H4 | 0.95 | C10—C10a | 1.434 (3) |
C4a—C11b | 1.414 (3) | C10—C101 | 1.499 (3) |
C4a—C5 | 1.509 (3) | C101—H10A | 0.98 |
C5—C6 | 1.518 (3) | C101—H10B | 0.98 |
C5—H5A | 0.99 | C101—H10C | 0.98 |
C5—H5B | 0.99 | C10a—C11 | 1.411 (3) |
C6—C6a | 1.501 (3) | C11—C11a | 1.396 (3) |
C6—H6A | 0.99 | C11—C111 | 1.489 (3) |
C6—H6B | 0.99 | C11a—C11b | 1.496 (3) |
C6a—N7 | 1.335 (3) | C111—C116 | 1.384 (3) |
C6a—C11a | 1.428 (3) | C111—C112 | 1.392 (3) |
N7—C7a | 1.344 (3) | C112—N113 | 1.334 (3) |
N8—C7a | 1.373 (3) | C112—H112 | 0.95 |
N8—N9 | 1.384 (2) | N113—C114 | 1.341 (3) |
N8—C81 | 1.420 (3) | C114—C115 | 1.374 (3) |
C81—C82 | 1.384 (3) | C114—H114 | 0.95 |
C81—C86 | 1.389 (3) | C115—C116 | 1.379 (3) |
C82—C83 | 1.381 (3) | C115—H115 | 0.95 |
C82—H82 | 0.95 | C116—H116 | 0.95 |
C83—C84 | 1.372 (4) | ||
C2—C1—C11b | 121.4 (2) | C84—C85—H85 | 119.7 |
C2—C1—H1 | 119.3 | C86—C85—H85 | 119.7 |
C11b—C1—H1 | 119.3 | C85—C86—C81 | 119.5 (2) |
C3—C2—C1 | 120.2 (2) | C85—C86—H86 | 120.3 |
C3—C2—H2 | 119.9 | C81—C86—H86 | 120.3 |
C1—C2—H2 | 119.9 | N7—C7a—N8 | 126.01 (19) |
C2—C3—C4 | 119.4 (2) | N7—C7a—C10a | 126.41 (19) |
C2—C3—H3 | 120.3 | N8—C7a—C10a | 107.58 (18) |
C4—C3—H3 | 120.3 | C10—N9—N8 | 107.26 (18) |
C3—C4—C4a | 121.1 (2) | N9—C10—C10a | 110.49 (19) |
C3—C4—H4 | 119.5 | N9—C10—C101 | 118.61 (19) |
C4a—C4—H4 | 119.5 | C10a—C10—C101 | 130.89 (19) |
C4—C4a—C11b | 120.1 (2) | C10—C101—H10A | 109.5 |
C4—C4a—C5 | 121.2 (2) | C10—C101—H10B | 109.5 |
C11b—C4a—C5 | 118.67 (19) | H10A—C101—H10B | 109.5 |
C4a—C5—C6 | 109.71 (19) | C10—C101—H10C | 109.5 |
C4a—C5—H5A | 109.7 | H10A—C101—H10C | 109.5 |
C6—C5—H5A | 109.7 | H10B—C101—H10C | 109.5 |
C4a—C5—H5B | 109.7 | C7a—C10a—C11 | 118.47 (19) |
C6—C5—H5B | 109.7 | C7a—C10a—C10 | 104.85 (19) |
H5A—C5—H5B | 108.2 | C11—C10a—C10 | 136.7 (2) |
C6a—C6—C5 | 109.21 (19) | C11a—C11—C10a | 117.2 (2) |
C6a—C6—H6A | 109.8 | C11a—C11—C111 | 125.29 (19) |
C5—C6—H6A | 109.8 | C10a—C11—C111 | 117.51 (18) |
C6a—C6—H6B | 109.8 | C11—C11a—C6a | 118.3 (2) |
C5—C6—H6B | 109.8 | C11—C11a—C11b | 124.6 (2) |
H6A—C6—H6B | 108.3 | C6a—C11a—C11b | 117.07 (18) |
N7—C6a—C11a | 125.5 (2) | C1—C11b—C4a | 117.7 (2) |
N7—C6a—C6 | 115.95 (19) | C1—C11b—C11a | 123.9 (2) |
C11a—C6a—C6 | 118.55 (19) | C4a—C11b—C11a | 118.4 (2) |
C6a—N7—C7a | 114.12 (18) | C116—C111—C112 | 118.3 (2) |
C7a—N8—N9 | 109.80 (17) | C116—C111—C11 | 121.39 (18) |
C7a—N8—C81 | 131.05 (18) | C112—C111—C11 | 120.3 (2) |
N9—N8—C81 | 119.15 (17) | N113—C112—C111 | 123.4 (2) |
C82—C81—C86 | 120.0 (2) | N113—C112—H112 | 118.3 |
C82—C81—N8 | 119.3 (2) | C111—C112—H112 | 118.3 |
C86—C81—N8 | 120.69 (19) | C112—N113—C114 | 116.9 (2) |
C83—C82—C81 | 119.4 (2) | N113—C114—C115 | 123.8 (2) |
C83—C82—H82 | 120.3 | N113—C114—H114 | 118.1 |
C81—C82—H82 | 120.3 | C115—C114—H114 | 118.1 |
C84—C83—C82 | 121.2 (2) | C114—C115—C116 | 118.8 (2) |
C84—C83—H83 | 119.4 | C114—C115—H115 | 120.6 |
C82—C83—H83 | 119.4 | C116—C115—H115 | 120.6 |
C83—C84—C85 | 119.3 (2) | C115—C116—C111 | 118.8 (2) |
C83—C84—H84 | 120.4 | C115—C116—H116 | 120.6 |
C85—C84—H84 | 120.4 | C111—C116—H116 | 120.6 |
C84—C85—C86 | 120.7 (2) | ||
C11b—C1—C2—C3 | −1.0 (3) | N9—C10—C10a—C7a | 1.4 (2) |
C1—C2—C3—C4 | −1.9 (4) | C101—C10—C10a—C7a | −177.0 (2) |
C2—C3—C4—C4a | 1.5 (4) | N9—C10—C10a—C11 | 179.9 (2) |
C3—C4—C4a—C11b | 1.6 (3) | C101—C10—C10a—C11 | 1.5 (4) |
C3—C4—C4a—C5 | −175.2 (2) | C7a—C10a—C11—C11a | 1.1 (3) |
C4—C4a—C5—C6 | 141.2 (2) | C10—C10a—C11—C11a | −177.2 (2) |
C11b—C4a—C5—C6 | −35.6 (3) | C7a—C10a—C11—C111 | −179.55 (18) |
C4a—C5—C6—C6a | 58.4 (3) | C10—C10a—C11—C111 | 2.1 (4) |
C5—C6—C6a—N7 | 137.7 (2) | C10a—C11—C11a—C6a | −0.7 (3) |
C5—C6—C6a—C11a | −41.9 (3) | C111—C11—C11a—C6a | −179.96 (19) |
C11a—C6a—N7—C7a | 0.4 (3) | C10a—C11—C11a—C11b | 179.01 (19) |
C6—C6a—N7—C7a | −179.13 (18) | C111—C11—C11a—C11b | −0.3 (3) |
C7a—N8—C81—C82 | 161.8 (2) | N7—C6a—C11a—C11 | −0.1 (3) |
N9—N8—C81—C82 | −18.1 (3) | C6—C6a—C11a—C11 | 179.4 (2) |
C7a—N8—C81—C86 | −18.3 (3) | N7—C6a—C11a—C11b | −179.82 (19) |
N9—N8—C81—C86 | 161.8 (2) | C6—C6a—C11a—C11b | −0.3 (3) |
C86—C81—C82—C83 | 0.1 (4) | C2—C1—C11b—C4a | 4.0 (3) |
N8—C81—C82—C83 | 179.9 (2) | C2—C1—C11b—C11a | −176.6 (2) |
C81—C82—C83—C84 | 0.2 (4) | C4—C4a—C11b—C1 | −4.3 (3) |
C82—C83—C84—C85 | 0.1 (4) | C5—C4a—C11b—C1 | 172.6 (2) |
C83—C84—C85—C86 | −0.7 (4) | C4—C4a—C11b—C11a | 176.23 (19) |
C84—C85—C86—C81 | 0.9 (4) | C5—C4a—C11b—C11a | −6.9 (3) |
C82—C81—C86—C85 | −0.6 (3) | C11—C11a—C11b—C1 | 27.2 (3) |
N8—C81—C86—C85 | 179.5 (2) | C6a—C11a—C11b—C1 | −153.2 (2) |
C6a—N7—C7a—N8 | 179.3 (2) | C11—C11a—C11b—C4a | −153.4 (2) |
C6a—N7—C7a—C10a | 0.1 (3) | C6a—C11a—C11b—C4a | 26.3 (3) |
N9—N8—C7a—N7 | −178.43 (19) | C11a—C11—C111—C116 | −115.0 (2) |
C81—N8—C7a—N7 | 1.6 (4) | C10a—C11—C111—C116 | 65.7 (3) |
N9—N8—C7a—C10a | 0.9 (2) | C11a—C11—C111—C112 | 67.7 (3) |
C81—N8—C7a—C10a | −179.0 (2) | C10a—C11—C111—C112 | −111.6 (2) |
C7a—N8—N9—C10 | 0.0 (2) | C116—C111—C112—N113 | −1.1 (3) |
C81—N8—N9—C10 | 179.92 (18) | C11—C111—C112—N113 | 176.4 (2) |
N8—N9—C10—C10a | −0.9 (2) | C111—C112—N113—C114 | 0.0 (4) |
N8—N9—C10—C101 | 177.77 (19) | C112—N113—C114—C115 | 1.0 (4) |
N7—C7a—C10a—C11 | −0.8 (3) | N113—C114—C115—C116 | −0.9 (4) |
N8—C7a—C10a—C11 | 179.81 (18) | C114—C115—C116—C111 | −0.2 (3) |
N7—C7a—C10a—C10 | 178.0 (2) | C112—C111—C116—C115 | 1.2 (3) |
N8—C7a—C10a—C10 | −1.4 (2) | C11—C111—C116—C115 | −176.3 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C86—H86···N7 | 0.95 | 2.39 | 3.007 (3) | 123 |
C114—H114···N113i | 0.95 | 2.49 | 3.417 (3) | 165 |
Symmetry code: (i) y, −x+1, −z+2. |
C26H20N4 | F(000) = 1632 |
Mr = 388.46 | Dx = 1.325 Mg m−3 |
Orthorhombic, P21212 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2 2ab | Cell parameters from 4952 reflections |
a = 18.6288 (8) Å | θ = 3.6–27.5° |
b = 19.1956 (8) Å | µ = 0.08 mm−1 |
c = 10.8885 (3) Å | T = 120 K |
V = 3893.6 (3) Å3 | Lath, yellow |
Z = 8 | 0.42 × 0.18 × 0.10 mm |
Bruker Nonius KappaCCD area-detector diffractometer | 4952 independent reflections |
Radiation source: Bruker Nonius FR91 rotating anode | 3590 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.075 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.6° |
ϕ and ω scans | h = −24→23 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −18→24 |
Tmin = 0.976, Tmax = 0.992 | l = −14→14 |
25232 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)] = 0.065 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.152 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0545P)2 + 3.0251P] where P = (Fo2 + 2Fc2)/3 |
4952 reflections | (Δ/σ)max < 0.001 |
543 parameters | Δρmax = 0.26 e Å−3 |
0 restraints | Δρmin = −0.31 e Å−3 |
C26H20N4 | V = 3893.6 (3) Å3 |
Mr = 388.46 | Z = 8 |
Orthorhombic, P21212 | Mo Kα radiation |
a = 18.6288 (8) Å | µ = 0.08 mm−1 |
b = 19.1956 (8) Å | T = 120 K |
c = 10.8885 (3) Å | 0.42 × 0.18 × 0.10 mm |
Bruker Nonius KappaCCD area-detector diffractometer | 4952 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 3590 reflections with I > 2σ(I) |
Tmin = 0.976, Tmax = 0.992 | Rint = 0.075 |
25232 measured reflections |
R[F2 > 2σ(F2)] = 0.065 | 0 restraints |
wR(F2) = 0.152 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.26 e Å−3 |
4952 reflections | Δρmin = −0.31 e Å−3 |
543 parameters |
x | y | z | Uiso*/Ueq | ||
N17 | 0.24040 (19) | 0.77900 (18) | 0.3666 (3) | 0.0244 (8) | |
N18 | 0.23840 (18) | 0.66625 (18) | 0.2655 (3) | 0.0243 (8) | |
N19 | 0.27873 (19) | 0.60594 (19) | 0.2693 (3) | 0.0257 (8) | |
N124 | 0.5501 (2) | 0.6209 (2) | 0.6319 (3) | 0.0345 (9) | |
C10a | 0.3246 (2) | 0.6837 (2) | 0.4041 (4) | 0.0227 (9) | |
C11 | 0.4417 (2) | 0.8361 (2) | 0.6466 (4) | 0.0269 (10) | |
C11a | 0.3382 (2) | 0.7901 (2) | 0.5171 (4) | 0.0235 (9) | |
C11b | 0.3702 (2) | 0.8398 (2) | 0.6088 (4) | 0.0241 (9) | |
C12 | 0.4682 (2) | 0.8818 (2) | 0.7354 (4) | 0.0316 (11) | |
C13 | 0.4243 (3) | 0.9317 (3) | 0.7864 (4) | 0.0325 (11) | |
C14 | 0.3543 (3) | 0.9378 (2) | 0.7463 (4) | 0.0309 (11) | |
C14a | 0.3266 (2) | 0.8925 (2) | 0.6574 (4) | 0.0254 (9) | |
C15 | 0.2524 (3) | 0.9024 (2) | 0.6097 (4) | 0.0302 (10) | |
C16 | 0.2503 (3) | 0.8877 (2) | 0.4732 (4) | 0.0291 (10) | |
C16a | 0.2767 (2) | 0.8150 (2) | 0.4505 (4) | 0.0242 (9) | |
C17a | 0.2653 (2) | 0.7142 (2) | 0.3472 (3) | 0.0237 (9) | |
C101 | 0.3804 (2) | 0.5576 (2) | 0.3777 (5) | 0.0338 (11) | |
C110 | 0.3296 (2) | 0.6153 (2) | 0.3519 (4) | 0.0244 (9) | |
C111 | 0.3625 (2) | 0.7230 (2) | 0.4923 (4) | 0.0240 (9) | |
C121 | 0.4275 (2) | 0.6897 (2) | 0.5459 (4) | 0.0232 (9) | |
C122 | 0.4294 (2) | 0.6607 (2) | 0.6633 (4) | 0.0290 (10) | |
C123 | 0.4914 (3) | 0.6271 (2) | 0.7008 (4) | 0.0324 (11) | |
C125 | 0.5478 (2) | 0.6490 (2) | 0.5195 (4) | 0.0309 (11) | |
C126 | 0.4886 (2) | 0.6829 (2) | 0.4734 (4) | 0.0254 (9) | |
C181 | 0.1812 (2) | 0.6721 (2) | 0.1794 (3) | 0.0230 (9) | |
C182 | 0.1736 (3) | 0.6213 (2) | 0.0893 (4) | 0.0319 (11) | |
C183 | 0.1187 (3) | 0.6268 (3) | 0.0048 (4) | 0.0350 (11) | |
C184 | 0.0729 (2) | 0.6826 (3) | 0.0063 (4) | 0.0327 (11) | |
C185 | 0.0812 (3) | 0.7332 (3) | 0.0958 (4) | 0.0371 (12) | |
C186 | 0.1341 (2) | 0.7283 (2) | 0.1826 (4) | 0.0292 (10) | |
N27 | 0.22061 (19) | 0.23995 (18) | 0.1360 (3) | 0.0245 (8) | |
N28 | 0.33362 (19) | 0.24184 (18) | 0.2434 (3) | 0.0246 (8) | |
N29 | 0.39404 (19) | 0.28351 (18) | 0.2435 (3) | 0.0265 (8) | |
N224 | 0.3758 (2) | 0.5496 (2) | −0.1165 (4) | 0.0383 (10) | |
C20A | 0.3137 (2) | 0.3276 (2) | 0.1086 (4) | 0.0236 (9) | |
C21 | 0.1554 (2) | 0.4384 (2) | −0.1343 (4) | 0.0299 (10) | |
C21a | 0.2072 (2) | 0.3368 (2) | −0.0115 (4) | 0.0233 (9) | |
C21b | 0.1563 (2) | 0.3674 (2) | −0.1041 (4) | 0.0232 (9) | |
C22 | 0.1091 (3) | 0.4639 (2) | −0.2239 (4) | 0.0341 (11) | |
C23 | 0.0617 (3) | 0.4189 (3) | −0.2828 (4) | 0.0332 (11) | |
C24 | 0.0608 (2) | 0.3497 (2) | −0.2515 (4) | 0.0310 (10) | |
C24a | 0.1066 (2) | 0.3228 (2) | −0.1602 (4) | 0.0243 (9) | |
C25 | 0.1003 (3) | 0.2484 (2) | −0.1187 (4) | 0.0286 (10) | |
C26 | 0.1113 (2) | 0.2450 (2) | 0.0192 (4) | 0.0288 (10) | |
C26a | 0.1832 (2) | 0.2752 (2) | 0.0507 (4) | 0.0241 (9) | |
C27a | 0.2842 (2) | 0.2678 (2) | 0.1605 (4) | 0.0233 (9) | |
C201 | 0.4418 (2) | 0.3862 (2) | 0.1431 (4) | 0.0325 (11) | |
C210 | 0.3833 (2) | 0.3342 (2) | 0.1632 (4) | 0.0257 (9) | |
C211 | 0.2733 (2) | 0.3640 (2) | 0.0188 (4) | 0.0236 (9) | |
C221 | 0.3062 (2) | 0.4283 (2) | −0.0320 (4) | 0.0227 (9) | |
C222 | 0.3354 (2) | 0.4315 (2) | −0.1502 (4) | 0.0279 (10) | |
C223 | 0.3698 (3) | 0.4922 (2) | −0.1862 (4) | 0.0331 (11) | |
C225 | 0.3472 (3) | 0.5456 (2) | −0.0034 (4) | 0.0318 (11) | |
C226 | 0.3135 (2) | 0.4873 (2) | 0.0405 (4) | 0.0264 (10) | |
C281 | 0.3289 (2) | 0.1829 (2) | 0.3225 (4) | 0.0234 (9) | |
C282 | 0.3770 (3) | 0.1783 (2) | 0.4203 (4) | 0.0315 (11) | |
C283 | 0.3738 (3) | 0.1213 (3) | 0.4972 (4) | 0.0342 (11) | |
C284 | 0.3239 (3) | 0.0694 (2) | 0.4800 (4) | 0.0329 (11) | |
C285 | 0.2760 (3) | 0.0749 (2) | 0.3829 (4) | 0.0362 (11) | |
C286 | 0.2785 (2) | 0.1314 (2) | 0.3042 (4) | 0.0284 (10) | |
H10A | 0.3702 | 0.5184 | 0.3226 | 0.051* | |
H10B | 0.3748 | 0.5424 | 0.4631 | 0.051* | |
H10C | 0.4297 | 0.5737 | 0.3643 | 0.051* | |
H11 | 0.4727 | 0.8022 | 0.6115 | 0.032* | |
H12 | 0.5169 | 0.8784 | 0.7608 | 0.038* | |
H13 | 0.4421 | 0.9617 | 0.8488 | 0.039* | |
H14 | 0.3245 | 0.9733 | 0.7795 | 0.037* | |
H15A | 0.2365 | 0.9508 | 0.6254 | 0.036* | |
H15B | 0.2192 | 0.8705 | 0.6529 | 0.036* | |
H16A | 0.2006 | 0.8927 | 0.4423 | 0.035* | |
H16B | 0.2811 | 0.9215 | 0.4291 | 0.035* | |
H122 | 0.3891 | 0.6639 | 0.7164 | 0.035* | |
H123 | 0.4921 | 0.6073 | 0.7807 | 0.039* | |
H125 | 0.5892 | 0.6453 | 0.4689 | 0.037* | |
H126 | 0.4894 | 0.7016 | 0.3927 | 0.030* | |
H182 | 0.2060 | 0.5832 | 0.0859 | 0.038* | |
H183 | 0.1126 | 0.5914 | −0.0552 | 0.042* | |
H184 | 0.0360 | 0.6866 | −0.0534 | 0.039* | |
H185 | 0.0496 | 0.7720 | 0.0970 | 0.045* | |
H186 | 0.1386 | 0.7629 | 0.2444 | 0.035* | |
H20A | 0.4845 | 0.3723 | 0.1894 | 0.049* | |
H20B | 0.4257 | 0.4321 | 0.1713 | 0.049* | |
H20C | 0.4534 | 0.3885 | 0.0554 | 0.049* | |
H21 | 0.1868 | 0.4696 | −0.0930 | 0.036* | |
H22 | 0.1098 | 0.5119 | −0.2449 | 0.041* | |
H23 | 0.0301 | 0.4360 | −0.3443 | 0.040* | |
H24 | 0.0285 | 0.3193 | −0.2923 | 0.037* | |
H25A | 0.1369 | 0.2195 | −0.1606 | 0.034* | |
H25B | 0.0523 | 0.2300 | −0.1400 | 0.034* | |
H26A | 0.0730 | 0.2716 | 0.0614 | 0.035* | |
H26B | 0.1088 | 0.1960 | 0.0472 | 0.035* | |
H222 | 0.3318 | 0.3930 | −0.2046 | 0.034* | |
H223 | 0.3907 | 0.4932 | −0.2658 | 0.040* | |
H225 | 0.3506 | 0.5851 | 0.0487 | 0.038* | |
H226 | 0.2949 | 0.4873 | 0.1217 | 0.032* | |
H282 | 0.4116 | 0.2139 | 0.4337 | 0.038* | |
H283 | 0.4068 | 0.1178 | 0.5635 | 0.041* | |
H284 | 0.3223 | 0.0304 | 0.5338 | 0.039* | |
H285 | 0.2411 | 0.0395 | 0.3704 | 0.043* | |
H286 | 0.2456 | 0.1346 | 0.2377 | 0.034* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C11 | 0.029 (2) | 0.029 (2) | 0.023 (2) | −0.001 (2) | 0.0010 (18) | −0.0027 (18) |
C12 | 0.028 (2) | 0.036 (3) | 0.031 (2) | −0.005 (2) | −0.002 (2) | 0.000 (2) |
C13 | 0.036 (3) | 0.038 (3) | 0.023 (2) | −0.010 (2) | −0.002 (2) | −0.003 (2) |
C14 | 0.039 (3) | 0.035 (3) | 0.018 (2) | 0.000 (2) | 0.006 (2) | −0.0040 (19) |
C14a | 0.028 (2) | 0.027 (2) | 0.021 (2) | −0.004 (2) | 0.0049 (18) | 0.0020 (17) |
C15 | 0.036 (3) | 0.032 (3) | 0.023 (2) | 0.005 (2) | 0.0027 (19) | 0.0020 (18) |
C16 | 0.028 (2) | 0.031 (3) | 0.028 (2) | 0.001 (2) | 0.001 (2) | 0.0015 (19) |
C16a | 0.025 (2) | 0.028 (2) | 0.020 (2) | −0.0077 (19) | 0.0022 (18) | 0.0038 (17) |
N17 | 0.026 (2) | 0.0255 (19) | 0.0215 (17) | 0.0000 (16) | 0.0017 (15) | 0.0013 (15) |
C17a | 0.026 (2) | 0.027 (2) | 0.018 (2) | −0.001 (2) | 0.0052 (18) | 0.0029 (17) |
N18 | 0.0231 (19) | 0.0294 (19) | 0.0204 (17) | 0.0029 (16) | −0.0049 (15) | −0.0024 (15) |
C181 | 0.023 (2) | 0.031 (2) | 0.0145 (18) | −0.007 (2) | −0.0010 (16) | −0.0002 (17) |
C182 | 0.033 (3) | 0.035 (3) | 0.027 (2) | 0.005 (2) | −0.004 (2) | −0.0052 (19) |
C183 | 0.034 (3) | 0.050 (3) | 0.022 (2) | −0.003 (2) | −0.0017 (19) | −0.007 (2) |
C184 | 0.027 (2) | 0.047 (3) | 0.024 (2) | −0.004 (2) | −0.0060 (19) | 0.003 (2) |
C185 | 0.034 (3) | 0.037 (3) | 0.040 (3) | 0.003 (2) | −0.009 (2) | 0.003 (2) |
C186 | 0.025 (2) | 0.032 (3) | 0.031 (2) | −0.005 (2) | −0.0036 (19) | −0.001 (2) |
N19 | 0.0257 (19) | 0.029 (2) | 0.0221 (18) | 0.0021 (17) | 0.0000 (16) | 0.0001 (15) |
C110 | 0.024 (2) | 0.026 (2) | 0.023 (2) | −0.0020 (19) | 0.0029 (18) | 0.0019 (17) |
C101 | 0.029 (3) | 0.028 (2) | 0.044 (3) | 0.000 (2) | −0.003 (2) | −0.001 (2) |
C10a | 0.025 (2) | 0.022 (2) | 0.0212 (19) | −0.0014 (19) | 0.0026 (17) | 0.0020 (16) |
C111 | 0.023 (2) | 0.030 (2) | 0.019 (2) | −0.0012 (19) | 0.0031 (17) | 0.0044 (18) |
C121 | 0.024 (2) | 0.024 (2) | 0.021 (2) | −0.0019 (18) | −0.0009 (18) | −0.0001 (17) |
C122 | 0.028 (2) | 0.034 (3) | 0.025 (2) | −0.004 (2) | −0.0004 (19) | 0.0041 (19) |
C123 | 0.029 (2) | 0.037 (3) | 0.031 (2) | −0.003 (2) | −0.004 (2) | 0.015 (2) |
N124 | 0.028 (2) | 0.043 (2) | 0.033 (2) | 0.0027 (19) | −0.0035 (17) | 0.0095 (19) |
C125 | 0.026 (2) | 0.040 (3) | 0.026 (2) | 0.002 (2) | 0.0003 (19) | 0.005 (2) |
C126 | 0.025 (2) | 0.025 (2) | 0.026 (2) | −0.0036 (19) | −0.0008 (18) | 0.0028 (18) |
C11a | 0.024 (2) | 0.028 (2) | 0.0184 (19) | −0.0013 (19) | 0.0044 (17) | 0.0036 (17) |
C11b | 0.027 (2) | 0.027 (2) | 0.0183 (19) | −0.0040 (19) | 0.0026 (17) | 0.0026 (17) |
C21 | 0.028 (2) | 0.032 (3) | 0.029 (2) | 0.001 (2) | −0.005 (2) | −0.004 (2) |
C22 | 0.037 (3) | 0.034 (3) | 0.032 (2) | 0.008 (2) | 0.000 (2) | 0.004 (2) |
C23 | 0.035 (3) | 0.039 (3) | 0.026 (2) | 0.006 (2) | −0.003 (2) | −0.001 (2) |
C24 | 0.033 (3) | 0.041 (3) | 0.019 (2) | 0.000 (2) | −0.0006 (19) | −0.007 (2) |
C24a | 0.023 (2) | 0.032 (2) | 0.0187 (19) | −0.001 (2) | 0.0051 (17) | −0.0035 (18) |
C25 | 0.032 (2) | 0.027 (2) | 0.027 (2) | −0.003 (2) | 0.0037 (19) | −0.0066 (19) |
C26 | 0.030 (2) | 0.028 (2) | 0.028 (2) | −0.006 (2) | −0.0051 (19) | −0.0009 (19) |
C26a | 0.022 (2) | 0.024 (2) | 0.026 (2) | −0.0023 (19) | 0.0042 (18) | −0.0064 (17) |
N27 | 0.0250 (19) | 0.026 (2) | 0.0226 (17) | 0.0005 (16) | 0.0008 (15) | −0.0033 (15) |
C27a | 0.026 (2) | 0.025 (2) | 0.019 (2) | −0.0010 (19) | 0.0022 (17) | −0.0028 (17) |
N28 | 0.0250 (19) | 0.0257 (19) | 0.0230 (17) | 0.0000 (16) | −0.0032 (15) | 0.0051 (15) |
C281 | 0.027 (2) | 0.023 (2) | 0.020 (2) | 0.005 (2) | 0.0035 (18) | 0.0019 (17) |
C282 | 0.035 (3) | 0.031 (3) | 0.029 (2) | −0.006 (2) | −0.004 (2) | 0.0043 (19) |
C283 | 0.042 (3) | 0.040 (3) | 0.020 (2) | 0.002 (2) | −0.007 (2) | 0.003 (2) |
C284 | 0.042 (3) | 0.033 (3) | 0.024 (2) | 0.004 (2) | 0.006 (2) | 0.0041 (19) |
C285 | 0.037 (3) | 0.029 (3) | 0.044 (3) | −0.006 (2) | −0.005 (2) | 0.001 (2) |
C286 | 0.030 (2) | 0.027 (2) | 0.028 (2) | 0.004 (2) | −0.0048 (19) | 0.0006 (19) |
N29 | 0.028 (2) | 0.0260 (19) | 0.0250 (18) | −0.0006 (17) | −0.0015 (16) | 0.0007 (15) |
C210 | 0.029 (2) | 0.025 (2) | 0.023 (2) | 0.002 (2) | 0.0011 (18) | −0.0001 (18) |
C201 | 0.027 (2) | 0.036 (3) | 0.034 (2) | 0.000 (2) | −0.002 (2) | 0.004 (2) |
C20A | 0.026 (2) | 0.024 (2) | 0.0208 (19) | −0.0032 (19) | 0.0015 (17) | −0.0020 (17) |
C211 | 0.029 (2) | 0.022 (2) | 0.020 (2) | 0.0009 (19) | 0.0036 (18) | −0.0040 (17) |
C221 | 0.022 (2) | 0.023 (2) | 0.023 (2) | 0.0025 (18) | 0.0004 (17) | 0.0036 (17) |
C222 | 0.030 (2) | 0.029 (2) | 0.025 (2) | 0.005 (2) | −0.0012 (19) | 0.0009 (18) |
C223 | 0.042 (3) | 0.032 (3) | 0.025 (2) | 0.003 (2) | 0.011 (2) | 0.004 (2) |
N224 | 0.042 (2) | 0.029 (2) | 0.044 (2) | 0.001 (2) | 0.009 (2) | 0.0025 (19) |
C225 | 0.035 (3) | 0.029 (3) | 0.031 (2) | −0.001 (2) | 0.010 (2) | −0.0023 (19) |
C226 | 0.031 (2) | 0.029 (2) | 0.019 (2) | 0.002 (2) | 0.0032 (18) | −0.0006 (17) |
C21a | 0.025 (2) | 0.023 (2) | 0.023 (2) | 0.0012 (19) | 0.0024 (17) | −0.0049 (17) |
C21b | 0.020 (2) | 0.030 (2) | 0.0199 (19) | 0.0057 (19) | 0.0056 (17) | 0.0003 (17) |
C11—C12 | 1.395 (6) | C21—C22 | 1.391 (6) |
C11—C11b | 1.397 (6) | C21—C21b | 1.402 (6) |
C11—H11 | 0.95 | C21—H21 | 0.95 |
C12—C13 | 1.377 (6) | C22—C23 | 1.391 (7) |
C12—H12 | 0.95 | C22—H22 | 0.95 |
C13—C14 | 1.381 (6) | C23—C24 | 1.371 (6) |
C13—H13 | 0.95 | C23—H23 | 0.95 |
C14—C14a | 1.400 (6) | C24—C24a | 1.409 (6) |
C14—H14 | 0.95 | C24—H24 | 0.95 |
C14a—C11b | 1.401 (6) | C24a—C21b | 1.402 (6) |
C14a—C15 | 1.488 (6) | C24a—C25 | 1.501 (6) |
C15—C16 | 1.513 (6) | C25—C26 | 1.517 (6) |
C15—H15A | 0.99 | C25—H25A | 0.99 |
C15—H15B | 0.99 | C25—H25B | 0.99 |
C16—C16a | 1.500 (6) | C26—C26a | 1.498 (6) |
C16—H16A | 0.99 | C26—H26A | 0.99 |
C16—H16B | 0.99 | C26—H26B | 0.99 |
C16a—N17 | 1.330 (5) | C26a—N27 | 1.344 (5) |
C16a—C11a | 1.438 (6) | C26a—C21a | 1.434 (6) |
N17—C17a | 1.343 (5) | N27—C27a | 1.327 (5) |
C17a—N18 | 1.375 (5) | C27a—N28 | 1.382 (5) |
C17a—C10a | 1.396 (6) | C27a—C20A | 1.392 (6) |
N18—N19 | 1.381 (5) | N28—N29 | 1.381 (5) |
N18—C181 | 1.424 (5) | N28—C281 | 1.425 (5) |
C181—C182 | 1.390 (6) | C281—C286 | 1.378 (6) |
C181—C186 | 1.390 (6) | C281—C282 | 1.395 (6) |
C182—C183 | 1.380 (6) | C282—C283 | 1.380 (6) |
C182—H182 | 0.95 | C282—H282 | 0.95 |
C183—C184 | 1.369 (7) | C283—C284 | 1.375 (7) |
C183—H183 | 0.95 | C283—H283 | 0.95 |
C184—C185 | 1.384 (6) | C284—C285 | 1.389 (6) |
C184—H184 | 0.95 | C284—H284 | 0.95 |
C185—C186 | 1.369 (6) | C285—C286 | 1.383 (6) |
C185—H185 | 0.95 | C285—H285 | 0.95 |
C186—H186 | 0.95 | C286—H286 | 0.95 |
N19—C110 | 1.319 (5) | N29—C210 | 1.322 (5) |
C110—C10a | 1.433 (6) | C210—C20A | 1.432 (6) |
C110—C101 | 1.484 (6) | C210—C201 | 1.494 (6) |
C101—H10A | 0.98 | C201—H20A | 0.98 |
C101—H10B | 0.98 | C201—H20B | 0.98 |
C101—H10C | 0.98 | C201—H20C | 0.98 |
C10a—C111 | 1.410 (6) | C20A—C211 | 1.419 (6) |
C111—C11a | 1.392 (6) | C211—C21a | 1.377 (6) |
C111—C121 | 1.488 (6) | C211—C221 | 1.485 (6) |
C121—C126 | 1.391 (6) | C221—C226 | 1.387 (6) |
C121—C122 | 1.395 (6) | C221—C222 | 1.399 (6) |
C122—C123 | 1.383 (6) | C222—C223 | 1.385 (6) |
C122—H122 | 0.95 | C222—H222 | 0.95 |
C123—N124 | 1.331 (6) | C223—N224 | 1.343 (6) |
C123—H123 | 0.95 | C223—H223 | 0.95 |
N124—C125 | 1.338 (5) | N224—C225 | 1.344 (6) |
C125—C126 | 1.376 (6) | C225—C226 | 1.368 (6) |
C125—H125 | 0.95 | C225—H225 | 0.95 |
C126—H126 | 0.95 | C226—H226 | 0.95 |
C11a—C11b | 1.505 (6) | C21a—C21b | 1.504 (6) |
C12—C11—C11b | 120.7 (4) | C22—C21—C21b | 120.9 (4) |
C12—C11—H11 | 119.7 | C22—C21—H21 | 119.5 |
C11b—C11—H11 | 119.7 | C21b—C21—H21 | 119.5 |
C13—C12—C11 | 120.5 (4) | C21—C22—C23 | 119.9 (4) |
C13—C12—H12 | 119.8 | C21—C22—H22 | 120.1 |
C11—C12—H12 | 119.8 | C23—C22—H22 | 120.1 |
C12—C13—C14 | 119.5 (4) | C24—C23—C22 | 119.6 (4) |
C12—C13—H13 | 120.2 | C24—C23—H23 | 120.2 |
C14—C13—H13 | 120.2 | C22—C23—H23 | 120.2 |
C13—C14—C14a | 121.0 (4) | C23—C24—C24a | 121.6 (4) |
C13—C14—H14 | 119.5 | C23—C24—H24 | 119.2 |
C14a—C14—H14 | 119.5 | C24a—C24—H24 | 119.2 |
C14—C14a—C11b | 119.7 (4) | C21b—C24a—C24 | 118.9 (4) |
C14—C14a—C15 | 120.3 (4) | C21b—C24a—C25 | 120.1 (4) |
C11b—C14a—C15 | 119.9 (4) | C24—C24a—C25 | 120.9 (4) |
C14a—C15—C16 | 110.1 (4) | C24a—C25—C26 | 109.2 (4) |
C14a—C15—H15A | 109.6 | C24a—C25—H25A | 109.8 |
C16—C15—H15A | 109.6 | C26—C25—H25A | 109.8 |
C14a—C15—H15B | 109.6 | C24a—C25—H25B | 109.8 |
C16—C15—H15B | 109.6 | C26—C25—H25B | 109.8 |
H15A—C15—H15B | 108.2 | H25A—C25—H25B | 108.3 |
C16a—C16—C15 | 109.1 (4) | C26a—C26—C25 | 109.3 (4) |
C16a—C16—H16A | 109.9 | C26a—C26—H26A | 109.8 |
C15—C16—H16A | 109.9 | C25—C26—H26A | 109.8 |
C16a—C16—H16B | 109.9 | C26a—C26—H26B | 109.8 |
C15—C16—H16B | 109.9 | C25—C26—H26B | 109.8 |
H16A—C16—H16B | 108.3 | H26A—C26—H26B | 108.3 |
N17—C16a—C11a | 125.3 (4) | N27—C26a—C21a | 125.4 (4) |
N17—C16a—C16 | 115.5 (4) | N27—C26a—C26 | 115.3 (4) |
C11a—C16a—C16 | 119.2 (4) | C21a—C26a—C26 | 119.3 (4) |
C16a—N17—C17a | 114.4 (4) | C27a—N27—C26a | 113.5 (4) |
N17—C17a—N18 | 126.6 (4) | N27—C27a—N28 | 125.5 (4) |
N17—C17a—C10a | 126.3 (4) | N27—C27a—C20A | 127.1 (4) |
N18—C17a—C10a | 107.1 (4) | N28—C27a—C20A | 107.4 (4) |
C17a—N18—N19 | 110.1 (3) | N29—N28—C27a | 109.6 (3) |
C17a—N18—C181 | 130.2 (4) | N29—N28—C281 | 120.6 (3) |
N19—N18—C181 | 119.5 (3) | C27a—N28—C281 | 129.8 (4) |
C182—C181—C186 | 119.9 (4) | C286—C281—C282 | 120.2 (4) |
C182—C181—N18 | 119.0 (4) | C286—C281—N28 | 121.6 (4) |
C186—C181—N18 | 121.1 (4) | C282—C281—N28 | 118.1 (4) |
C183—C182—C181 | 119.5 (4) | C283—C282—C281 | 119.0 (4) |
C183—C182—H182 | 120.3 | C283—C282—H282 | 120.5 |
C181—C182—H182 | 120.3 | C281—C282—H282 | 120.5 |
C184—C183—C182 | 120.9 (4) | C284—C283—C282 | 121.4 (4) |
C184—C183—H183 | 119.5 | C284—C283—H283 | 119.3 |
C182—C183—H183 | 119.5 | C282—C283—H283 | 119.3 |
C183—C184—C185 | 119.1 (4) | C283—C284—C285 | 118.9 (4) |
C183—C184—H184 | 120.4 | C283—C284—H284 | 120.5 |
C185—C184—H184 | 120.4 | C285—C284—H284 | 120.5 |
C186—C185—C184 | 121.3 (5) | C286—C285—C284 | 120.6 (4) |
C186—C185—H185 | 119.4 | C286—C285—H285 | 119.7 |
C184—C185—H185 | 119.4 | C284—C285—H285 | 119.7 |
C185—C186—C181 | 119.3 (4) | C281—C286—C285 | 119.7 (4) |
C185—C186—H186 | 120.3 | C281—C286—H286 | 120.1 |
C181—C186—H186 | 120.3 | C285—C286—H286 | 120.1 |
C110—N19—N18 | 107.3 (3) | C210—N29—N28 | 107.6 (3) |
N19—C110—C10a | 110.4 (4) | N29—C210—C20A | 110.3 (4) |
N19—C110—C101 | 119.0 (4) | N29—C210—C201 | 118.6 (4) |
C10a—C110—C101 | 130.6 (4) | C20A—C210—C201 | 131.1 (4) |
C110—C101—H10A | 109.5 | C210—C201—H20A | 109.5 |
C110—C101—H10B | 109.5 | C210—C201—H20B | 109.5 |
H10A—C101—H10B | 109.5 | H20A—C201—H20B | 109.5 |
C110—C101—H10C | 109.5 | C210—C201—H20C | 109.5 |
H10A—C101—H10C | 109.5 | H20A—C201—H20C | 109.5 |
H10B—C101—H10C | 109.5 | H20B—C201—H20C | 109.5 |
C17a—C10a—C111 | 118.3 (4) | C27a—C20A—C211 | 118.4 (4) |
C17a—C10a—C110 | 105.1 (4) | C27a—C20A—C210 | 105.2 (4) |
C111—C10a—C110 | 136.6 (4) | C211—C20A—C210 | 136.4 (4) |
C11a—C111—C10a | 117.6 (4) | C21a—C211—C20A | 116.9 (4) |
C11a—C111—C121 | 125.9 (4) | C21a—C211—C221 | 126.6 (4) |
C10a—C111—C121 | 116.4 (4) | C20A—C211—C221 | 116.5 (4) |
C126—C121—C122 | 117.4 (4) | C226—C221—C222 | 116.7 (4) |
C126—C121—C111 | 118.9 (4) | C226—C221—C211 | 120.5 (4) |
C122—C121—C111 | 123.5 (4) | C222—C221—C211 | 122.7 (4) |
C123—C122—C121 | 118.6 (4) | C223—C222—C221 | 118.5 (4) |
C123—C122—H122 | 120.7 | C223—C222—H222 | 120.7 |
C121—C122—H122 | 120.7 | C221—C222—H222 | 120.7 |
N124—C123—C122 | 124.1 (4) | N224—C223—C222 | 124.6 (4) |
N124—C123—H123 | 117.9 | N224—C223—H223 | 117.7 |
C122—C123—H123 | 117.9 | C222—C223—H223 | 117.7 |
C123—N124—C125 | 117.0 (4) | C223—N224—C225 | 116.0 (4) |
N124—C125—C126 | 123.3 (4) | N224—C225—C226 | 123.3 (4) |
N124—C125—H125 | 118.4 | N224—C225—H225 | 118.4 |
C126—C125—H125 | 118.4 | C226—C225—H225 | 118.4 |
C125—C126—C121 | 119.6 (4) | C225—C226—C221 | 120.9 (4) |
C125—C126—H126 | 120.2 | C225—C226—H226 | 119.6 |
C121—C126—H126 | 120.2 | C221—C226—H226 | 119.6 |
C111—C11a—C16a | 118.0 (4) | C211—C21a—C26a | 118.6 (4) |
C111—C11a—C11b | 125.9 (4) | C211—C21a—C21b | 125.1 (4) |
C16a—C11a—C11b | 116.0 (4) | C26a—C21a—C21b | 116.2 (4) |
C11—C11b—C14a | 118.6 (4) | C24a—C21b—C21 | 118.9 (4) |
C11—C11b—C11a | 122.8 (4) | C24a—C21b—C21a | 118.0 (4) |
C14a—C11b—C11a | 118.6 (4) | C21—C21b—C21a | 123.1 (4) |
C11b—C11—C12—C13 | −0.6 (7) | C21b—C21—C22—C23 | 1.6 (7) |
C11—C12—C13—C14 | −2.1 (7) | C21—C22—C23—C24 | 0.3 (7) |
C12—C13—C14—C14a | 2.2 (7) | C22—C23—C24—C24a | 0.3 (7) |
C13—C14—C14a—C11b | 0.4 (6) | C23—C24—C24a—C21b | −2.7 (6) |
C13—C14—C14a—C15 | −176.4 (4) | C23—C24—C24a—C25 | 174.3 (4) |
C14—C14a—C15—C16 | 141.1 (4) | C21b—C24a—C25—C26 | 36.2 (5) |
C11b—C14a—C15—C16 | −35.7 (6) | C24—C24a—C25—C26 | −140.7 (4) |
C14a—C15—C16—C16a | 57.5 (5) | C24a—C25—C26—C26a | −57.7 (5) |
C15—C16—C16a—N17 | 139.0 (4) | C25—C26—C26a—N27 | −138.1 (4) |
C15—C16—C16a—C11a | −42.0 (5) | C25—C26—C26a—C21a | 40.9 (5) |
C11a—C16a—N17—C17a | 0.6 (6) | C21a—C26a—N27—C27a | 0.5 (6) |
C16—C16a—N17—C17a | 179.6 (3) | C26—C26a—N27—C27a | 179.4 (4) |
C16a—N17—C17a—N18 | −179.5 (4) | C26a—N27—C27a—N28 | −179.3 (4) |
C16a—N17—C17a—C10a | −1.3 (6) | C26a—N27—C27a—C20A | 0.4 (6) |
N17—C17a—N18—N19 | 178.8 (4) | N27—C27a—N28—N29 | 179.0 (4) |
C10a—C17a—N18—N19 | 0.3 (4) | C20A—C27a—N28—N29 | −0.8 (4) |
N17—C17a—N18—C181 | 2.6 (7) | N27—C27a—N28—C281 | −2.0 (7) |
C10a—C17a—N18—C181 | −175.9 (4) | C20A—C27a—N28—C281 | 178.2 (4) |
C17a—N18—C181—C182 | 166.7 (4) | N29—N28—C281—C286 | −163.9 (4) |
N19—N18—C181—C182 | −9.2 (5) | C27a—N28—C281—C286 | 17.2 (6) |
C17a—N18—C181—C186 | −11.9 (6) | N29—N28—C281—C282 | 16.1 (5) |
N19—N18—C181—C186 | 172.2 (4) | C27a—N28—C281—C282 | −162.8 (4) |
C186—C181—C182—C183 | −0.9 (6) | C286—C281—C282—C283 | 0.6 (7) |
N18—C181—C182—C183 | −179.5 (4) | N28—C281—C282—C283 | −179.4 (4) |
C181—C182—C183—C184 | 2.0 (7) | C281—C282—C283—C284 | −0.5 (7) |
C182—C183—C184—C185 | −1.5 (7) | C282—C283—C284—C285 | 0.0 (7) |
C183—C184—C185—C186 | −0.1 (7) | C283—C284—C285—C286 | 0.4 (7) |
C184—C185—C186—C181 | 1.1 (7) | C282—C281—C286—C285 | −0.2 (6) |
C182—C181—C186—C185 | −0.7 (6) | N28—C281—C286—C285 | 179.7 (4) |
N18—C181—C186—C185 | 177.9 (4) | C284—C285—C286—C281 | −0.2 (7) |
C17a—N18—N19—C110 | 0.4 (4) | C27a—N28—N29—C210 | −0.1 (4) |
C181—N18—N19—C110 | 177.1 (3) | C281—N28—N29—C210 | −179.2 (3) |
N18—N19—C110—C10a | −0.9 (4) | N28—N29—C210—C20A | 1.0 (4) |
N18—N19—C110—C101 | 178.5 (4) | N28—N29—C210—C201 | −178.6 (3) |
N17—C17a—C10a—C111 | 1.1 (6) | N27—C27a—C20A—C211 | −0.4 (6) |
N18—C17a—C10a—C111 | 179.6 (4) | N28—C27a—C20A—C211 | 179.4 (3) |
N17—C17a—C10a—C110 | −179.3 (4) | N27—C27a—C20A—C210 | −178.5 (4) |
N18—C17a—C10a—C110 | −0.8 (4) | N28—C27a—C20A—C210 | 1.3 (4) |
N19—C110—C10a—C17a | 1.1 (4) | N29—C210—C20A—C27a | −1.4 (5) |
C101—C110—C10a—C17a | −178.2 (4) | C201—C210—C20A—C27a | 178.1 (4) |
N19—C110—C10a—C111 | −179.4 (5) | N29—C210—C20A—C211 | −179.0 (5) |
C101—C110—C10a—C111 | 1.3 (8) | C201—C210—C20A—C211 | 0.5 (8) |
C17a—C10a—C111—C11a | 0.0 (6) | C27a—C20A—C211—C21a | −0.6 (6) |
C110—C10a—C111—C11a | −179.5 (4) | C210—C20A—C211—C21a | 176.8 (4) |
C17a—C10a—C111—C121 | −177.0 (3) | C27a—C20A—C211—C221 | 178.7 (4) |
C110—C10a—C111—C121 | 3.5 (7) | C210—C20A—C211—C221 | −4.0 (7) |
C11a—C111—C121—C126 | −104.7 (5) | C21a—C211—C221—C226 | 109.5 (5) |
C10a—C111—C121—C126 | 72.0 (5) | C20A—C211—C221—C226 | −69.6 (5) |
C11a—C111—C121—C122 | 79.5 (6) | C21a—C211—C221—C222 | −74.8 (6) |
C10a—C111—C121—C122 | −103.8 (5) | C20A—C211—C221—C222 | 106.1 (5) |
C126—C121—C122—C123 | 0.0 (6) | C226—C221—C222—C223 | 0.7 (6) |
C111—C121—C122—C123 | 175.9 (4) | C211—C221—C222—C223 | −175.2 (4) |
C121—C122—C123—N124 | 0.4 (7) | C221—C222—C223—N224 | −1.9 (7) |
C122—C123—N124—C125 | −0.3 (7) | C222—C223—N224—C225 | 1.7 (7) |
C123—N124—C125—C126 | −0.3 (7) | C223—N224—C225—C226 | −0.3 (7) |
N124—C125—C126—C121 | 0.7 (7) | N224—C225—C226—C221 | −0.8 (7) |
C122—C121—C126—C125 | −0.5 (6) | C222—C221—C226—C225 | 0.6 (6) |
C111—C121—C126—C125 | −176.6 (4) | C211—C221—C226—C225 | 176.5 (4) |
C10a—C111—C11a—C16a | −0.6 (5) | C20A—C211—C21a—C26a | 1.4 (5) |
C121—C111—C11a—C16a | 176.1 (4) | C221—C211—C21a—C26a | −177.8 (4) |
C10a—C111—C11a—C11b | 179.1 (4) | C20A—C211—C21a—C21b | 179.9 (4) |
C121—C111—C11a—C11b | −4.3 (6) | C221—C211—C21a—C21b | 0.8 (6) |
N17—C16a—C11a—C111 | 0.3 (6) | N27—C26a—C21a—C211 | −1.5 (6) |
C16—C16a—C11a—C111 | −178.6 (4) | C26—C26a—C21a—C211 | 179.7 (4) |
N17—C16a—C11a—C11b | −179.4 (4) | N27—C26a—C21a—C21b | 179.9 (4) |
C16—C16a—C11a—C11b | 1.7 (5) | C26—C26a—C21a—C21b | 1.1 (5) |
C12—C11—C11b—C14a | 3.1 (6) | C24—C24a—C21b—C21 | 4.4 (6) |
C12—C11—C11b—C11a | −177.6 (4) | C25—C24a—C21b—C21 | −172.6 (4) |
C14—C14a—C11b—C11 | −3.0 (6) | C24—C24a—C21b—C21a | −176.9 (4) |
C15—C14a—C11b—C11 | 173.8 (4) | C25—C24a—C21b—C21a | 6.1 (6) |
C14—C14a—C11b—C11a | 177.6 (4) | C22—C21—C21b—C24a | −3.9 (6) |
C15—C14a—C11b—C11a | −5.6 (6) | C22—C21—C21b—C21a | 177.5 (4) |
C111—C11a—C11b—C11 | 24.8 (6) | C211—C21a—C21b—C24a | 155.4 (4) |
C16a—C11a—C11b—C11 | −155.6 (4) | C26a—C21a—C21b—C24a | −26.0 (5) |
C111—C11a—C11b—C14a | −155.9 (4) | C211—C21a—C21b—C21 | −26.0 (6) |
C16a—C11a—C11b—C14a | 23.7 (5) | C26a—C21a—C21b—C21 | 152.5 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C182—H182···N19 | 0.95 | 2.45 | 2.786 (6) | 101 |
C186—H186···N17 | 0.95 | 2.34 | 2.980 (5) | 125 |
C282—H282···N29 | 0.95 | 2.49 | 2.808 (5) | 100 |
C286—H286···N27 | 0.95 | 2.35 | 2.976 (5) | 123 |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C26H20N4 | C26H20N4 |
Mr | 388.46 | 388.46 |
Crystal system, space group | Tetragonal, P421c | Orthorhombic, P21212 |
Temperature (K) | 120 | 120 |
a, b, c (Å) | 19.2181 (6), 19.2181 (6), 10.8347 (2) | 18.6288 (8), 19.1956 (8), 10.8885 (3) |
α, β, γ (°) | 90, 90, 90 | 90, 90, 90 |
V (Å3) | 4001.64 (19) | 3893.6 (3) |
Z | 8 | 8 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.08 | 0.08 |
Crystal size (mm) | 0.44 × 0.35 × 0.10 | 0.42 × 0.18 × 0.10 |
Data collection | ||
Diffractometer | Bruker Nonius KappaCCD area-detector diffractometer | Bruker Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.955, 0.992 | 0.976, 0.992 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 28744, 2537, 2004 | 25232, 4952, 3590 |
Rint | 0.070 | 0.075 |
(sin θ/λ)max (Å−1) | 0.650 | 0.650 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.089, 1.05 | 0.065, 0.152, 1.06 |
No. of reflections | 2537 | 4952 |
No. of parameters | 272 | 543 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.16, −0.20 | 0.26, −0.31 |
Computer programs: COLLECT (Hooft, 1999), DENZO (Otwinowski & Minor, 1997) and COLLECT, DENZO and COLLECT, OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997), OSCAIL and SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97 and PRPKAPPA (Ferguson, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
C86—H86···N7 | 0.95 | 2.39 | 3.007 (3) | 123 |
C114—H114···N113i | 0.95 | 2.49 | 3.417 (3) | 165 |
Symmetry code: (i) y, −x+1, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C182—H182···N19 | 0.95 | 2.45 | 2.786 (6) | 101 |
C186—H186···N17 | 0.95 | 2.34 | 2.980 (5) | 125 |
C282—H282···N29 | 0.95 | 2.49 | 2.808 (5) | 100 |
C286—H286···N27 | 0.95 | 2.35 | 2.976 (5) | 123 |
Acknowledgements
The X-ray data were collected at the EPSRC X-ray Crystallographic Service, University of Southampton. JC thanks the Consejería de Innovación, Ciencia y Empresa (Junta de Andalucía, Spain) and the Universidad de Jaén for financial support. JP and HS thank COLCIENCIAS and UNIVALLE (Universidad del Valle, Colombia) for financial support.
References
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We report here the structures of two isomeric 11-(pyridyl)-10-methyl-8-phenyl-6,8-dihydro-5H-benzo[f]pyrazolo[3,4-b]quinolines, (I) and (II). Compound (I) is a pyridyl analogue of the isostructural pair 11-(4-chlorophenyl)-10-methyl-8-phenyl-6,8-dihydro-5H-benzo[f]pyrazolo[3,4-b]quinoline, (III) (Serrano et al., 2005a), and 11-(4-bromophenyl)-10-methyl-8-phenyl-6,8-dihydro-5H-benzo[f]pyrazolo[3,4-b]quinoline, (IV) (Serrano et al., 2005b), while compound (II) is a simple positional isomer of (I).
The non-aromatic carbocyclic rings in both compounds adopt the screw-boat conformation, as shown by the ring-puckering parameters (Cremer & Pople, 1975; Evans & Boeyens, 1989). For (I), these are θ = 71.0 (2)° and ϕ = 94.3 (33)° for the atom sequence C4a/C5/C6/C6a/C11a/C11b (Fig. 1), as compared with the idealized values, for an ring with equal bond distances throughout, of θ = 67.5° and ϕ = (60k + 30)°. In (II), for the atom sequences C11a/C11b/C14a/C15/C16/C16a in molecule 1 and C21a/C21b/C24a/C25/C26/C26a in molecule 2 (Fig 2), the corresponding values are 69.9 (5) and 214.9 (5)°, respectively, in molecule 1, and 108.8 (4) and 33.1 (5)°, respectively, in molecule 2. In compounds (I) and (II), the molecules have no internal symmetry and they are chiral. For (I), the space group P421c accommodates equal numbers of the two enantiomers, but for (II), in space group P21212, each crystal will, in the absence of inversion twinning, contain just a single enantiomer. However, the ring-puckering parameters for compound (II) show that the two independent molecules are very close to being enantiomers (Fig. 2), although no possible additional symmetry was detected.
The overall conformations in (I) and (II) are very similar. For example, the dihedral angles between the pyrazole ring and its pendent aryl ring are 18.3 (2)° in (I), and 10.7 (2) and 16.7 (2)° in (II), the dihedral angles between the two pyridine rings are 66.6 (2)° in (I), and 75.4 (2) and 72.4 (2)° in (II), and the dihedral angles between the fused pyridine ring and the fused aryl ring are 27.3 (2)° in (I) and 24.4 (2) and 26.4 (2)° in (II). The difference in the orientation of the two pendent rings, one aryl and one pyridyl, is striking. The near coplanarity of the pyrazole and pendent aryl rings may be associated with the short intramolecular C—H···N contacts involving these rings (Tables 1 and 2). The modest differences between the corresponding values for the two molecules in compound (II) are sufficient to preclude the possibility of additional symmetry. The bond distances and angles show no unusual values.
The molecules in compound (I) are linked by a single C—H···N hydrogen bond (Table 1). Aryl atom C114 in the molecule at (x, y, z) acts as hydrogen-bond donor to the pyridyl atom N113 in the molecule at (y, 1 − x, 2 − z), while atom C114 at (y, 1 − x, 2 − z) in turn acts as donor to atom N113 at (1 − x, 1 − y, z). Propagation of this hydrogen bond thus produces a puckered R44(12) tetramer generated by the 4 axis along (1/2, 1/2, z) (Fig. 3). A second such tetramer, related to the first by the action of the c-glide planes, is generated by the 4 axis along (0, 0, z), but there are no direction-specific interactions between adjacent tetramers. By contrast, there are no direction-specific interactions of any kind between molecules of compound (II). In particular, the pyridyl N atoms N114 and N224 have no potential hydrogen-bond donors with N···H distances less than 2.65 Å.
The very different space groups and patterns of supramolecular aggregation manifested by isomers (I) and (II) may be contrasted with their 4-haloaryl analogues, (III) and (IV), which are strictly isomorphous and isostructural in space group P1, and where the molecules are linked by C—H···π(arene) hydrogen bonds, although C—H···N hydrogen bonds, as found here for (I), are absent from both (II) [(III)?] and (IV).