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In each of 3-tert-butyl-1-phenyl-7-(4-trifluoro­methyl­benz­yl)-4,5,6,7-tetra­hydro-1H-pyrazolo[3,4-b]pyridine-5-spiro-1'-cyclo­hexane-2',6'-dione, C29H30F3N3O2, (I), and 3-tert-butyl-7-(4-methoxy­benz­yl)-1-phenyl-4,5,6,7-tetra­hydro-1H-pyrazolo[3,4-b]pyridine-5-spiro-1'-cyclo­hexane-2',6'-dione, C29H33N3O3, (II), the reduced pyridine ring adopts a half-chair conformation. The mol­ecules of compound (I) are linked by two C-H...O hydrogen bonds to form a C(5)C(5)[R12(8)] chain of rings, while in compound (II), two C-H...O hydrogen bonds link the mol­ecules into a C(6)C(7)[R22(11)] chain of rings, which is further reinforced by a C-H...[pi] hydrogen bond. The significance of this study lies in its observation of significant differences in hydrogen-bonded structures consequent upon very minor changes in remote substituents.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108038808/sk3277sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108038808/sk3277Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108038808/sk3277IIsup3.hkl
Contains datablock II

CCDC references: 718159; 718160

Comment top

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; Trilleras 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 the two title N7-benzyl derivatives (Figs. 1 and 2). Compounds (I) and (II) are related to the analogues (III) (Cruz et al., 2008) and (IV) (Trilleras et al., 2008) reported earlier, but they differ from these earlier examples in carrying no methyl substituents on the spirocyclohexane ring. Compounds (I) and (II) were synthesized using a straightforward modification of the synthetic method employed earlier (Cruz et al., 2008; Trilleras et al., 2008), using cyclohexane-1,3-dione in place of the 5,5-dimethylcyclohexane-1,3-dione used previously.

Despite their different molecular constitutions, different space groups, and different patterns of supramolecular aggregation, described below, the conformations of compounds (I) and (II) are fairly similar (Table 1). The reduced pyridine rings both adopt half-chair conformations, for which the idealized ring-puckering angles (Cremer & Pople, 1975), assuming equal bond distances throughout the rings, are θ = 50.8° and ϕ = (60n + 30)°, where n represents an integer. Similarly, the orientation of the three peripheral substituents relative to the heterocyclic core of the molecule is very similar in compounds (I) and (II), as shown by the relevant torsional angles. The overall molecular conformations, together with the pyramidal coordination at N7, mean that the molecules have no internal symmetry, and hence that they are chiral. However, the centrosymmetric space group in each case accommodates a racemic mixture of the two enantiomers.

The molecules of compound (I) are linked into a chain of rings by two independent C—H···O hydrogen bonds (Table 2). Atoms C6 and C53 in the molecule at (x, y, z) both act as hydrogen-bond donors to the carbonyl atom O55 in the molecule at (1/2 - x, -1/2 + y, 3/2 - z); in this manner, molecules related by the 21 screw axis along (1/4, y, 3/4) are linked into a C(5) C(5)[R12(8)] (Bernstein et al., 1995) chain of rings running parallel to the [010] direction (Fig. 3). 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 the structure of compound (II) the molecules are again linked into a chain of rings, but now three hydrogen bonds are involved (Table 2), and the chain of rings is thus more complex than that observed in the structure of compound (I). Two of the hydrogen bonds are of the C—H···O type, utilizing both of the carbonyl O atoms as acceptors, in contrast to the hydrogen bonding in compound (I); these interactions link molecules related by the 21 screw axis along (1/2, y, 1/4) into a C(6) C(7)[R22(11)] chain of rings. The third hydrogen bond is of the C—H···π type, and this reinforces the chain generated by the C—H···O hydrogen bonds. As in compound (I), two inversion-related chains pass through each unit cell, but there are no direction-specific interactions between adjacent chains.

Thus, the overall molecular shapes for compounds (I) and (II) are rather similar, while their molecular constitutions vary only in the identity of the 4-substituent in the pendent benzyl ring; nonetheless, the intermolecular hydrogen bonding in compounds (I) and (II) is significantly different. It is thus interesting to note not only that these substituents, CF3 in (I) and OCH3 in (II), play no direct role in the hydrogen bonding, but also that they are located well away from the atoms which do participate in hydrogen-bond formation, most of which in fact are components of the spirocyclohexane ring.

It is also of interest briefly to compare the crystal structures of compounds (I) and (II) with those of the analogous 4',4'-dimethyl compounds (III) (Cruz et al., 2008) and (IV) (Trilleras et al., 2008). Firstly, both (III) and (IV) crystallize in the triclinic system, where (III) forms an ethanol hemisolvate, while compounds (I) and (II) both form monoclinic crystals. Secondly, the heterocyclic molecules in compounds (III) and (IV) are both linked by a combination of one C—H···O hydrogen bond and one C—H···π hydrogen bond. However, the resulting structures differ not only from those of compounds (I) and (II) but also from each other. In (III) the hydrogen bonds generate a chain of edge-fused centrosymmetric rings, while in (IV) a centrosymmetric dimer is formed. Thus, the presence or absence of two peripheral methyl groups has a marked influence, albeit indirect, on the range of hydrogen bonds displayed and thence on the overall supramolecular structures.

Related literature top

For related literature, see: Bernstein et al. (1995); Cremer & Pople (1975); Cruz et al. (2008); Trilleras et al. (2008).

Experimental top

Microwave-induced syntheses were carried out using a focused microwave reactor (CEM Discover TM). A mixture of the appropriately substituted N-benzylaminopyrazole (2 mmol), cyclohexane-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, the solid products were collected by filtration and washed with ethanol and then with hexane (2 × 5 cm3) to afford the pure products. Colourless crystals suitable for single-crystal X-ray diffraction were grown from solutions in ethanol. (I) Yield 75%, m. p. 488–490 K, HRMS found 509.2295, C29H30F3N3O2 requires 509.2290; (II) yield 75%, m. p. 466–468 K, HRMS found 471.2524, C29H33N3O3 requires 471.2522.

Refinement top

For compounds (I) and (II), the space groups P21/n and P21/c, respectively, were uniquely assigned from the systematic absences. All H atoms were located in difference maps and then treated as riding atoms in geometrically idealized positions with distances C—H 0.95 Å (aromatic), 0.98 Å (CH3) or 0.99 Å (CH2) and O—H 0.84 Å, and with Uiso(H) = kUeq(carrier), where k = 1.5 for the methyl and hydroxyl H atoms, and 1.2 for all other H atoms. The conformationally chiral reference molecules for the two compounds were chosen to have the same hand.

Computing details top

For both compounds, data collection: COLLECT (Nonius, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: Sir2004 (Burla et al., 2005); program(s) used to refine structure: 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).

Figures top
[Figure 1] Fig. 1. The molecular structure of compound (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. The molecular structure of compound (II) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 3] Fig. 3. A stereoview of part of the crystal structure of compound (I) showing the formation of a C(5) C(5)[R12(8)] chain of rings along [010]. For the sake of clarity, the H atoms bonded to C atoms not involved in the motifs shown have been omitted.
[Figure 4] Fig. 4. A stereoview of part of the crystal structure of compound (II) showing the formation of a complex chain of rings along [010]. For the sake of clarity, the H atoms bonded to C atoms not involved in the motifs shown have been omitted.
(I) 3-tert-butyl-1-phenyl-7-(4-trifluoromethylbenzyl)-4,5,6,7-tetrahydro- 1H-pyrazolo[3,4-b]pyridine-5-spiro-1'-cyclohexane-2',6'-dione top
Crystal data top
C29H30F3N3O2F(000) = 1072
Mr = 509.56Dx = 1.378 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 5621 reflections
a = 11.9298 (18) Åθ = 2.8–27.5°
b = 10.5678 (10) ŵ = 0.10 mm1
c = 19.614 (2) ÅT = 120 K
β = 96.627 (10)°Block, colourless
V = 2456.2 (5) Å30.33 × 0.32 × 0.18 mm
Z = 4
Data collection top
Bruker Nonius KappaCCD
diffractometer
5621 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode3742 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.055
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 2.8°
ϕ & ω scansh = 1515
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 1313
Tmin = 0.975, Tmax = 0.982l = 2524
31891 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.061Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.151H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0441P)2 + 3.3381P]
where P = (Fo2 + 2Fc2)/3
5621 reflections(Δ/σ)max < 0.001
337 parametersΔρmax = 0.43 e Å3
0 restraintsΔρmin = 0.38 e Å3
Crystal data top
C29H30F3N3O2V = 2456.2 (5) Å3
Mr = 509.56Z = 4
Monoclinic, P21/nMo Kα radiation
a = 11.9298 (18) ŵ = 0.10 mm1
b = 10.5678 (10) ÅT = 120 K
c = 19.614 (2) Å0.33 × 0.32 × 0.18 mm
β = 96.627 (10)°
Data collection top
Bruker Nonius KappaCCD
diffractometer
5621 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
3742 reflections with I > 2σ(I)
Tmin = 0.975, Tmax = 0.982Rint = 0.055
31891 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0610 restraints
wR(F2) = 0.151H-atom parameters constrained
S = 1.07Δρmax = 0.43 e Å3
5621 reflectionsΔρmin = 0.38 e Å3
337 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
F710.63921 (14)0.26114 (17)0.51426 (10)0.0492 (5)
F720.5838 (2)0.1422 (2)0.58851 (12)0.0970 (10)
F730.50355 (16)0.1401 (2)0.48731 (14)0.0810 (8)
O510.05228 (16)0.32637 (19)0.79945 (11)0.0409 (5)
O550.17591 (16)0.73348 (17)0.76969 (9)0.0336 (4)
N10.00441 (16)0.69828 (18)0.57055 (10)0.0203 (4)
N20.08783 (16)0.76746 (19)0.58430 (10)0.0224 (4)
N70.13371 (16)0.54283 (18)0.62895 (10)0.0206 (4)
C30.10633 (18)0.7332 (2)0.64682 (11)0.0193 (5)
C3A0.02656 (19)0.6443 (2)0.67493 (11)0.0193 (5)
C40.00999 (19)0.5786 (2)0.74262 (12)0.0231 (5)
C50.10913 (19)0.5223 (2)0.75492 (12)0.0234 (5)
C60.1356 (2)0.4578 (2)0.68737 (12)0.0243 (5)
C7A0.04295 (18)0.6253 (2)0.62549 (11)0.0190 (5)
C110.04279 (19)0.7137 (2)0.50553 (11)0.0213 (5)
C120.09258 (19)0.6153 (2)0.47397 (12)0.0241 (5)
C130.1305 (2)0.6358 (3)0.41083 (13)0.0318 (6)
C140.1177 (2)0.7515 (3)0.37961 (13)0.0355 (7)
C150.0659 (2)0.8482 (3)0.41078 (13)0.0336 (6)
C160.0277 (2)0.8296 (3)0.47388 (12)0.0268 (5)
C310.20476 (19)0.7889 (2)0.67846 (12)0.0219 (5)
C320.1617 (3)0.8595 (3)0.74348 (15)0.0470 (8)
C330.2711 (2)0.8807 (3)0.63053 (15)0.0423 (8)
C340.2811 (3)0.6821 (3)0.6958 (2)0.0489 (8)
C510.1118 (2)0.4178 (2)0.80879 (13)0.0275 (5)
C520.1915 (2)0.4366 (3)0.87194 (13)0.0343 (6)
C530.3081 (2)0.4644 (3)0.85300 (15)0.0391 (7)
C540.3107 (2)0.5784 (3)0.80783 (17)0.0502 (9)
C550.1968 (2)0.6228 (3)0.77661 (12)0.0279 (6)
C710.32137 (19)0.4936 (2)0.59577 (11)0.0202 (5)
C720.43645 (19)0.5138 (2)0.60611 (12)0.0242 (5)
C730.5100 (2)0.4243 (2)0.58585 (13)0.0262 (5)
C740.4685 (2)0.3136 (2)0.55590 (12)0.0242 (5)
C750.3539 (2)0.2929 (2)0.54549 (13)0.0260 (5)
C760.28084 (19)0.3825 (2)0.56526 (12)0.0240 (5)
C770.24373 (19)0.5946 (2)0.61712 (12)0.0214 (5)
C7410.5472 (2)0.2150 (3)0.53669 (14)0.0310 (6)
H4A0.06660.51040.74360.028*
H4B0.02100.63950.77960.028*
H6A0.21110.41800.69550.029*
H6B0.07980.38950.67570.029*
H120.10080.53460.49530.029*
H130.16570.56890.38890.038*
H140.14450.76500.33640.043*
H150.05640.92830.38890.040*
H160.00870.89630.49520.032*
H32A0.11950.80120.77580.071*
H32B0.22570.89440.76440.071*
H32C0.11210.92850.73230.071*
H33A0.22150.94950.61890.063*
H33B0.33340.91590.65300.063*
H33C0.30150.83650.58850.063*
H34A0.30600.63390.65410.073*
H34B0.34700.71710.71470.073*
H34C0.23970.62620.72970.073*
H52A0.19360.35940.90070.041*
H52B0.16550.50780.89890.041*
H53A0.36010.47810.89550.047*
H53B0.33550.39010.82900.047*
H54A0.35700.55860.77040.060*
H54B0.34830.64840.83510.060*
H720.46520.58980.62730.029*
H730.58900.43910.59260.031*
H750.32530.21660.52460.031*
H760.20180.36790.55790.029*
H77A0.27890.63540.65970.026*
H77B0.23290.66010.58090.026*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
F710.0314 (9)0.0464 (10)0.0748 (13)0.0031 (8)0.0279 (9)0.0098 (9)
F720.133 (2)0.0944 (18)0.0756 (15)0.0901 (17)0.0615 (15)0.0502 (14)
F730.0324 (10)0.0764 (15)0.133 (2)0.0111 (10)0.0038 (11)0.0678 (15)
O510.0299 (10)0.0407 (11)0.0506 (12)0.0116 (9)0.0016 (9)0.0204 (10)
O550.0382 (11)0.0305 (10)0.0310 (10)0.0079 (8)0.0009 (8)0.0009 (8)
N10.0172 (9)0.0241 (10)0.0203 (9)0.0044 (8)0.0048 (7)0.0003 (8)
N20.0188 (10)0.0249 (10)0.0241 (10)0.0053 (8)0.0050 (8)0.0000 (8)
N70.0152 (9)0.0204 (10)0.0269 (10)0.0014 (8)0.0059 (8)0.0036 (8)
C30.0159 (11)0.0217 (11)0.0206 (11)0.0002 (9)0.0036 (8)0.0026 (9)
C3A0.0168 (11)0.0209 (11)0.0205 (11)0.0002 (9)0.0034 (8)0.0008 (9)
C40.0198 (12)0.0275 (12)0.0226 (11)0.0030 (10)0.0052 (9)0.0025 (10)
C50.0184 (12)0.0258 (12)0.0260 (12)0.0013 (9)0.0024 (9)0.0067 (10)
C60.0193 (12)0.0226 (12)0.0318 (13)0.0026 (9)0.0059 (10)0.0044 (10)
C7A0.0168 (11)0.0177 (11)0.0226 (11)0.0016 (9)0.0023 (9)0.0006 (9)
C110.0167 (11)0.0292 (12)0.0177 (11)0.0033 (9)0.0013 (9)0.0012 (10)
C120.0171 (11)0.0284 (13)0.0275 (12)0.0048 (10)0.0046 (9)0.0054 (10)
C130.0220 (13)0.0476 (16)0.0273 (13)0.0077 (12)0.0093 (10)0.0124 (12)
C140.0257 (14)0.0610 (19)0.0209 (12)0.0094 (13)0.0071 (10)0.0021 (13)
C150.0295 (14)0.0444 (16)0.0268 (13)0.0027 (12)0.0028 (11)0.0104 (12)
C160.0221 (12)0.0332 (14)0.0252 (12)0.0015 (10)0.0023 (10)0.0021 (11)
C310.0190 (11)0.0225 (12)0.0250 (12)0.0027 (9)0.0059 (9)0.0010 (10)
C320.0448 (18)0.0538 (19)0.0410 (17)0.0211 (15)0.0013 (13)0.0216 (15)
C330.0313 (15)0.0593 (19)0.0389 (16)0.0260 (14)0.0149 (12)0.0156 (15)
C340.0342 (16)0.0339 (16)0.084 (2)0.0004 (13)0.0306 (16)0.0019 (16)
C510.0229 (12)0.0285 (13)0.0323 (13)0.0043 (11)0.0082 (10)0.0085 (11)
C520.0528 (18)0.0257 (13)0.0243 (13)0.0018 (12)0.0039 (12)0.0047 (11)
C530.0331 (15)0.0370 (15)0.0431 (16)0.0001 (12)0.0130 (12)0.0038 (13)
C540.0256 (15)0.071 (2)0.0508 (18)0.0102 (15)0.0094 (13)0.0296 (17)
C550.0272 (13)0.0353 (14)0.0205 (12)0.0040 (11)0.0003 (10)0.0060 (11)
C710.0183 (11)0.0219 (11)0.0210 (11)0.0015 (9)0.0052 (9)0.0017 (9)
C720.0172 (11)0.0292 (13)0.0258 (12)0.0006 (10)0.0015 (9)0.0022 (10)
C730.0157 (11)0.0311 (13)0.0316 (13)0.0018 (10)0.0022 (9)0.0004 (11)
C740.0218 (12)0.0271 (12)0.0245 (12)0.0045 (10)0.0063 (9)0.0032 (10)
C750.0242 (12)0.0247 (12)0.0298 (13)0.0006 (10)0.0063 (10)0.0020 (10)
C760.0159 (11)0.0260 (12)0.0304 (13)0.0007 (9)0.0035 (9)0.0015 (10)
C770.0167 (11)0.0226 (12)0.0254 (12)0.0014 (9)0.0048 (9)0.0004 (10)
C7410.0253 (13)0.0307 (14)0.0378 (15)0.0038 (11)0.0067 (11)0.0005 (12)
Geometric parameters (Å, º) top
F71—C7411.321 (3)C31—C341.513 (4)
F72—C7411.309 (3)C31—C321.515 (4)
F73—C7411.311 (3)C32—H32A0.98
O51—C511.200 (3)C32—H32B0.98
O55—C551.200 (3)C32—H32C0.98
N1—C7A1.361 (3)C33—H33A0.98
N1—N21.374 (3)C33—H33B0.98
N1—C111.413 (3)C33—H33C0.98
N2—C31.321 (3)C34—H34A0.98
N7—C7A1.386 (3)C34—H34B0.98
N7—C61.455 (3)C34—H34C0.98
N7—C771.465 (3)C51—C521.485 (4)
C3—C3A1.404 (3)C52—C531.510 (4)
C3—C311.510 (3)C52—H52A0.99
C3A—C7A1.362 (3)C52—H52B0.99
C3A—C41.491 (3)C53—C541.498 (4)
C4—C51.534 (3)C53—H53A0.99
C4—H4A0.99C53—H53B0.99
C4—H4B0.99C54—C551.500 (4)
C5—C551.517 (3)C54—H54A0.99
C5—C511.526 (3)C54—H54B0.99
C5—C61.554 (3)C71—C761.380 (3)
C6—H6A0.99C71—C721.381 (3)
C6—H6B0.99C71—C771.504 (3)
C11—C161.376 (3)C72—C731.379 (3)
C11—C121.379 (3)C72—H720.95
C12—C131.383 (3)C73—C741.376 (3)
C12—H120.95C73—H730.95
C13—C141.369 (4)C74—C751.376 (3)
C13—H130.95C74—C7411.480 (3)
C14—C151.373 (4)C75—C761.372 (3)
C14—H140.95C75—H750.95
C15—C161.382 (4)C76—H760.95
C15—H150.95C77—H77A0.99
C16—H160.95C77—H77B0.99
C31—C331.510 (3)
C7A—N1—N2110.56 (18)C31—C33—H33B109.5
C7A—N1—C11131.65 (19)H33A—C33—H33B109.5
N2—N1—C11117.79 (18)C31—C33—H33C109.5
C3—N2—N1105.07 (18)H33A—C33—H33C109.5
C7A—N7—C6111.60 (18)H33B—C33—H33C109.5
C7A—N7—C77117.83 (19)C31—C34—H34A109.5
C6—N7—C77115.01 (18)C31—C34—H34B109.5
N2—C3—C3A111.7 (2)H34A—C34—H34B109.5
N2—C3—C31119.7 (2)C31—C34—H34C109.5
C3A—C3—C31128.6 (2)H34A—C34—H34C109.5
C7A—C3A—C3105.0 (2)H34B—C34—H34C109.5
C7A—C3A—C4122.5 (2)O51—C51—C52123.0 (2)
C3—C3A—C4132.5 (2)O51—C51—C5120.8 (2)
C3A—C4—C5110.23 (19)C52—C51—C5116.2 (2)
C3A—C4—H4A109.6C51—C52—C53109.9 (2)
C5—C4—H4A109.6C51—C52—H52A109.7
C3A—C4—H4B109.6C53—C52—H52A109.7
C5—C4—H4B109.6C51—C52—H52B109.7
H4A—C4—H4B108.1C53—C52—H52B109.7
C55—C5—C51110.7 (2)H52A—C52—H52B108.2
C55—C5—C4111.6 (2)C54—C53—C52112.7 (2)
C51—C5—C4109.55 (19)C54—C53—H53A109.1
C55—C5—C6110.2 (2)C52—C53—H53A109.1
C51—C5—C6106.4 (2)C54—C53—H53B109.1
C4—C5—C6108.17 (19)C52—C53—H53B109.1
N7—C6—C5114.47 (19)H53A—C53—H53B107.8
N7—C6—H6A108.6C53—C54—C55114.4 (2)
C5—C6—H6A108.6C53—C54—H54A108.7
N7—C6—H6B108.6C55—C54—H54A108.7
C5—C6—H6B108.6C53—C54—H54B108.7
H6A—C6—H6B107.6C55—C54—H54B108.7
N1—C7A—C3A107.62 (19)H54A—C54—H54B107.6
N1—C7A—N7125.9 (2)O55—C55—C54121.2 (3)
C3A—C7A—N7126.5 (2)O55—C55—C5121.5 (2)
C16—C11—C12120.6 (2)C54—C55—C5117.3 (2)
C16—C11—N1118.1 (2)C76—C71—C72119.2 (2)
C12—C11—N1121.3 (2)C76—C71—C77121.9 (2)
C11—C12—C13119.1 (2)C72—C71—C77118.9 (2)
C11—C12—H12120.5C73—C72—C71120.4 (2)
C13—C12—H12120.5C73—C72—H72119.8
C14—C13—C12120.6 (3)C71—C72—H72119.8
C14—C13—H13119.7C74—C73—C72119.8 (2)
C12—C13—H13119.7C74—C73—H73120.1
C13—C14—C15119.9 (2)C72—C73—H73120.1
C13—C14—H14120.1C73—C74—C75120.0 (2)
C15—C14—H14120.1C73—C74—C741120.0 (2)
C14—C15—C16120.3 (3)C75—C74—C741120.0 (2)
C14—C15—H15119.8C76—C75—C74120.1 (2)
C16—C15—H15119.8C76—C75—H75120.0
C11—C16—C15119.4 (2)C74—C75—H75120.0
C11—C16—H16120.3C75—C76—C71120.5 (2)
C15—C16—H16120.3C75—C76—H76119.8
C3—C31—C33111.8 (2)C71—C76—H76119.8
C3—C31—C34108.5 (2)N7—C77—C71111.80 (19)
C33—C31—C34109.5 (2)N7—C77—H77A109.3
C3—C31—C32109.5 (2)C71—C77—H77A109.3
C33—C31—C32108.1 (2)N7—C77—H77B109.3
C34—C31—C32109.4 (2)C71—C77—H77B109.3
C31—C32—H32A109.5H77A—C77—H77B107.9
C31—C32—H32B109.5F72—C741—F73106.7 (3)
H32A—C32—H32B109.5F72—C741—F71105.1 (2)
C31—C32—H32C109.5F73—C741—F71104.6 (2)
H32A—C32—H32C109.5F72—C741—C74112.4 (2)
H32B—C32—H32C109.5F73—C741—C74113.7 (2)
C31—C33—H33A109.5F71—C741—C74113.6 (2)
C7A—N1—N2—C31.7 (2)C3A—C3—C31—C33179.3 (2)
C11—N1—N2—C3178.7 (2)N2—C3—C31—C34121.0 (3)
N1—N2—C3—C3A1.0 (3)C3A—C3—C31—C3458.4 (3)
N1—N2—C3—C31178.49 (19)N2—C3—C31—C32119.6 (3)
N2—C3—C3A—C7A0.1 (3)C3A—C3—C31—C3261.0 (3)
C31—C3—C3A—C7A179.4 (2)C55—C5—C51—O51176.4 (2)
N2—C3—C3A—C4179.2 (2)C4—C5—C51—O5160.1 (3)
C31—C3—C3A—C41.3 (4)C6—C5—C51—O5156.6 (3)
C7A—C3A—C4—C516.2 (3)C55—C5—C51—C523.5 (3)
C3—C3A—C4—C5162.9 (2)C4—C5—C51—C52120.1 (2)
C3A—C4—C5—C5577.6 (2)C6—C5—C51—C52123.2 (2)
C3A—C4—C5—C51159.4 (2)O51—C51—C52—C53127.5 (3)
C3A—C4—C5—C643.8 (3)C5—C51—C52—C5352.4 (3)
C7A—N7—C6—C542.8 (3)C51—C52—C53—C5457.8 (3)
C77—N7—C6—C594.9 (2)C52—C53—C54—C5514.1 (4)
C55—C5—C6—N761.5 (3)C53—C54—C55—O55142.5 (3)
C51—C5—C6—N7178.38 (19)C53—C54—C55—C536.9 (4)
C4—C5—C6—N760.7 (3)C51—C5—C55—O55137.3 (2)
N2—N1—C7A—C3A1.7 (3)C4—C5—C55—O5515.0 (3)
C11—N1—C7A—C3A178.8 (2)C6—C5—C55—O55105.2 (3)
N2—N1—C7A—N7179.2 (2)C51—C5—C55—C5442.1 (3)
C11—N1—C7A—N71.3 (4)C4—C5—C55—C54164.4 (2)
C3—C3A—C7A—N11.0 (3)C6—C5—C55—C5475.4 (3)
C4—C3A—C7A—N1179.7 (2)C76—C71—C72—C730.4 (4)
C3—C3A—C7A—N7178.4 (2)C77—C71—C72—C73178.7 (2)
C4—C3A—C7A—N72.2 (4)C71—C72—C73—C740.8 (4)
C6—N7—C7A—N1166.0 (2)C72—C73—C74—C750.8 (4)
C77—N7—C7A—N157.7 (3)C72—C73—C74—C741177.5 (2)
C6—N7—C7A—C3A11.0 (3)C73—C74—C75—C760.3 (4)
C77—N7—C7A—C3A125.3 (2)C741—C74—C75—C76177.9 (2)
C7A—N1—C11—C16148.7 (2)C74—C75—C76—C710.1 (4)
N2—N1—C11—C1630.8 (3)C72—C71—C76—C750.1 (4)
C7A—N1—C11—C1232.1 (4)C77—C71—C76—C75179.1 (2)
N2—N1—C11—C12148.4 (2)C7A—N7—C77—C71158.19 (19)
C16—C11—C12—C132.0 (3)C6—N7—C77—C7166.9 (3)
N1—C11—C12—C13178.9 (2)C76—C71—C77—N723.9 (3)
C11—C12—C13—C140.7 (4)C72—C71—C77—N7157.1 (2)
C12—C13—C14—C150.6 (4)C73—C74—C741—F7283.3 (3)
C13—C14—C15—C160.6 (4)C75—C74—C741—F7294.9 (3)
C12—C11—C16—C151.9 (4)C73—C74—C741—F73155.3 (3)
N1—C11—C16—C15179.0 (2)C75—C74—C741—F7326.5 (4)
C14—C15—C16—C110.6 (4)C73—C74—C741—F7135.8 (3)
N2—C3—C31—C330.2 (3)C75—C74—C741—F71145.9 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C6—H6A···O55i0.992.423.309 (3)149
C53—H53B···O55i0.992.543.448 (4)153
Symmetry code: (i) x+1/2, y1/2, z+3/2.
(II) 3-tert-butyl-7-(4-methoxybenzyl)-1-phenyl-4,5,6,7-tetrahydro- 1H-pyrazolo[3,4-b]pyridine-5-spiro-1'-cyclohexane-2',6'-dione top
Crystal data top
C29H33N3O3F(000) = 1008
Mr = 471.58Dx = 1.291 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5566 reflections
a = 9.1904 (10) Åθ = 2.9–27.5°
b = 11.9402 (14) ŵ = 0.08 mm1
c = 22.2888 (16) ÅT = 120 K
β = 97.287 (9)°Block, colourless
V = 2426.1 (4) Å30.39 × 0.38 × 0.16 mm
Z = 4
Data collection top
Bruker Nonius KappaCCD
diffractometer
5566 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode3161 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.084
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 2.9°
ϕ & ω scansh = 1111
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 1515
Tmin = 0.977, Tmax = 0.987l = 2826
37788 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.054Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.143H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.055P)2 + 1.2855P]
where P = (Fo2 + 2Fc2)/3
5566 reflections(Δ/σ)max < 0.001
320 parametersΔρmax = 0.26 e Å3
0 restraintsΔρmin = 0.32 e Å3
Crystal data top
C29H33N3O3V = 2426.1 (4) Å3
Mr = 471.58Z = 4
Monoclinic, P21/cMo Kα radiation
a = 9.1904 (10) ŵ = 0.08 mm1
b = 11.9402 (14) ÅT = 120 K
c = 22.2888 (16) Å0.39 × 0.38 × 0.16 mm
β = 97.287 (9)°
Data collection top
Bruker Nonius KappaCCD
diffractometer
5566 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
3161 reflections with I > 2σ(I)
Tmin = 0.977, Tmax = 0.987Rint = 0.084
37788 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0540 restraints
wR(F2) = 0.143H-atom parameters constrained
S = 1.04Δρmax = 0.26 e Å3
5566 reflectionsΔρmin = 0.32 e Å3
320 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O510.47933 (18)0.13490 (14)0.15587 (7)0.0376 (4)
O550.45927 (17)0.47217 (13)0.21851 (7)0.0317 (4)
O7410.45277 (18)0.12686 (15)0.54516 (7)0.0416 (4)
N10.93029 (18)0.43752 (15)0.29610 (7)0.0226 (4)
N20.97707 (18)0.48699 (15)0.24648 (8)0.0240 (4)
N70.73001 (18)0.31459 (15)0.31852 (7)0.0227 (4)
C30.8866 (2)0.45035 (17)0.19963 (9)0.0232 (5)
C3A0.7789 (2)0.37823 (18)0.21793 (9)0.0233 (5)
C40.6530 (2)0.31823 (19)0.18358 (9)0.0254 (5)
C50.5439 (2)0.28334 (17)0.22571 (9)0.0230 (5)
C60.6305 (2)0.23525 (18)0.28461 (9)0.0240 (5)
C7A0.8089 (2)0.37321 (17)0.27925 (9)0.0228 (5)
C111.0108 (2)0.45717 (18)0.35358 (9)0.0247 (5)
C121.0135 (2)0.37872 (19)0.39882 (10)0.0285 (5)
C131.0906 (3)0.4010 (2)0.45460 (10)0.0345 (6)
C141.1684 (3)0.4983 (2)0.46461 (11)0.0351 (6)
C151.1689 (3)0.5753 (2)0.41889 (11)0.0354 (6)
C161.0886 (2)0.5562 (2)0.36325 (10)0.0304 (5)
C310.9053 (2)0.48938 (19)0.13697 (10)0.0273 (5)
C320.7766 (3)0.5651 (2)0.11281 (11)0.0356 (6)
C331.0474 (3)0.5555 (2)0.13770 (10)0.0338 (6)
C340.9101 (3)0.3885 (2)0.09521 (10)0.0339 (6)
C510.4457 (2)0.18749 (18)0.19828 (10)0.0260 (5)
C520.3096 (2)0.16125 (19)0.22596 (11)0.0322 (5)
C530.2228 (2)0.26539 (19)0.23808 (11)0.0315 (5)
C540.3187 (2)0.35237 (19)0.27360 (10)0.0294 (5)
C550.4439 (2)0.37999 (19)0.23897 (9)0.0255 (5)
C710.6093 (2)0.31707 (18)0.41168 (9)0.0241 (5)
C720.4999 (2)0.3592 (2)0.44194 (10)0.0302 (5)
C730.4473 (2)0.2997 (2)0.48779 (10)0.0339 (6)
C740.5015 (3)0.1950 (2)0.50248 (10)0.0308 (5)
C750.6116 (3)0.1520 (2)0.47332 (10)0.0339 (6)
C760.6657 (2)0.21226 (19)0.42872 (10)0.0297 (5)
C770.6643 (2)0.38431 (18)0.36249 (9)0.0239 (5)
C7410.3187 (3)0.1552 (2)0.56615 (11)0.0454 (7)
H4A0.68900.25110.16390.030*
H4B0.60410.36780.15150.030*
H6A0.55940.20830.31120.029*
H6B0.68800.16980.27390.029*
H120.96260.30980.39170.034*
H131.08990.34830.48650.041*
H141.22200.51260.50320.042*
H151.22480.64210.42560.043*
H161.08670.61040.33190.036*
H32A0.77630.63170.13850.053*
H32B0.68430.52410.11320.053*
H32C0.78690.58790.07130.053*
H33A1.13060.50810.15360.051*
H33B1.04410.62160.16350.051*
H33C1.05880.57920.09650.051*
H34A0.81640.34840.09230.051*
H34B0.98960.33830.11160.051*
H34C0.92720.41410.05490.051*
H52A0.33700.12080.26450.039*
H52B0.24660.11100.19850.039*
H53A0.17930.29820.19910.038*
H53B0.14160.24420.26110.038*
H29A0.26080.42060.27910.035*
H54B0.35660.32250.31400.035*
H720.45960.43070.43110.036*
H730.37390.33130.50900.041*
H750.65060.08000.48410.041*
H760.74290.18190.40920.036*
H77A0.58180.42760.34100.029*
H77B0.73860.43840.38090.029*
H74A0.24090.15940.53180.068*
H74B0.32850.22800.58660.068*
H74C0.29360.09790.59460.068*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O510.0440 (10)0.0315 (9)0.0391 (9)0.0109 (8)0.0126 (8)0.0081 (8)
O550.0336 (9)0.0216 (9)0.0398 (9)0.0001 (7)0.0038 (7)0.0040 (7)
O7410.0433 (10)0.0518 (11)0.0309 (9)0.0091 (9)0.0095 (7)0.0105 (8)
N10.0202 (9)0.0231 (10)0.0246 (9)0.0023 (7)0.0034 (7)0.0019 (8)
N20.0205 (9)0.0236 (10)0.0286 (9)0.0013 (8)0.0063 (7)0.0013 (8)
N70.0237 (9)0.0214 (9)0.0237 (9)0.0031 (8)0.0055 (7)0.0008 (8)
C30.0204 (11)0.0203 (11)0.0295 (11)0.0008 (9)0.0061 (9)0.0002 (9)
C3A0.0206 (10)0.0225 (11)0.0272 (11)0.0016 (9)0.0043 (8)0.0006 (9)
C40.0239 (11)0.0260 (12)0.0266 (11)0.0049 (9)0.0041 (9)0.0011 (10)
C50.0224 (11)0.0189 (11)0.0278 (11)0.0001 (9)0.0038 (9)0.0003 (9)
C60.0227 (11)0.0210 (11)0.0285 (11)0.0011 (9)0.0042 (9)0.0007 (9)
C7A0.0209 (11)0.0188 (11)0.0293 (12)0.0015 (9)0.0061 (9)0.0006 (9)
C110.0207 (11)0.0264 (12)0.0273 (11)0.0014 (9)0.0042 (9)0.0038 (10)
C120.0265 (12)0.0268 (12)0.0322 (12)0.0005 (10)0.0030 (9)0.0004 (10)
C130.0326 (13)0.0393 (14)0.0309 (13)0.0004 (11)0.0009 (10)0.0042 (11)
C140.0314 (13)0.0416 (15)0.0310 (13)0.0004 (11)0.0010 (10)0.0072 (11)
C150.0332 (13)0.0318 (14)0.0404 (14)0.0048 (11)0.0015 (11)0.0077 (11)
C160.0297 (12)0.0278 (13)0.0333 (13)0.0026 (10)0.0028 (10)0.0010 (10)
C310.0266 (11)0.0260 (12)0.0302 (12)0.0041 (10)0.0067 (9)0.0009 (10)
C320.0341 (13)0.0379 (14)0.0351 (13)0.0013 (11)0.0053 (10)0.0097 (11)
C330.0326 (13)0.0361 (14)0.0340 (13)0.0078 (11)0.0091 (10)0.0003 (11)
C340.0364 (13)0.0367 (14)0.0299 (12)0.0033 (11)0.0093 (10)0.0036 (11)
C510.0272 (12)0.0199 (11)0.0301 (12)0.0005 (9)0.0011 (9)0.0036 (10)
C520.0256 (12)0.0278 (13)0.0430 (14)0.0045 (10)0.0032 (10)0.0006 (11)
C530.0219 (11)0.0297 (13)0.0430 (14)0.0001 (10)0.0049 (10)0.0049 (11)
C540.0232 (11)0.0294 (12)0.0361 (13)0.0009 (10)0.0058 (9)0.0007 (10)
C550.0233 (11)0.0247 (12)0.0272 (11)0.0016 (9)0.0018 (9)0.0009 (10)
C710.0222 (11)0.0243 (12)0.0256 (11)0.0020 (9)0.0021 (9)0.0008 (9)
C720.0276 (12)0.0286 (13)0.0356 (13)0.0041 (10)0.0087 (10)0.0031 (10)
C730.0293 (12)0.0410 (15)0.0332 (13)0.0015 (11)0.0112 (10)0.0010 (11)
C740.0316 (12)0.0368 (14)0.0240 (11)0.0080 (11)0.0031 (9)0.0061 (10)
C750.0363 (14)0.0329 (14)0.0323 (13)0.0027 (11)0.0034 (10)0.0082 (11)
C760.0267 (12)0.0312 (13)0.0322 (12)0.0061 (10)0.0080 (9)0.0049 (10)
C770.0226 (11)0.0222 (11)0.0276 (11)0.0008 (9)0.0058 (9)0.0008 (9)
C7410.0463 (16)0.0595 (19)0.0329 (13)0.0152 (13)0.0146 (12)0.0010 (13)
Geometric parameters (Å, º) top
O51—C511.207 (3)C31—C321.531 (3)
O55—C551.207 (3)C32—H32A0.98
O741—C741.370 (3)C32—H32B0.98
O741—C7411.414 (3)C32—H32C0.98
N1—C7A1.367 (3)C33—H33A0.98
N1—N21.370 (2)C33—H33B0.98
N1—C111.415 (3)C33—H33C0.98
N2—C31.324 (3)C34—H34A0.98
N7—C7A1.394 (3)C34—H34B0.98
N7—C61.459 (3)C34—H34C0.98
N7—C771.472 (3)C51—C521.496 (3)
C3—C3A1.411 (3)C52—C531.520 (3)
C3—C311.503 (3)C52—H52A0.99
C3A—C7A1.361 (3)C52—H52B0.99
C3A—C41.488 (3)C53—C541.518 (3)
C4—C51.517 (3)C53—H53A0.99
C4—H4A0.99C53—H53B0.99
C4—H4B0.99C54—C551.501 (3)
C5—C551.527 (3)C54—H29A0.99
C5—C511.535 (3)C54—H54B0.99
C5—C61.556 (3)C71—C721.375 (3)
C6—H6A0.99C71—C761.389 (3)
C6—H6B0.99C71—C771.498 (3)
C11—C121.374 (3)C72—C731.381 (3)
C11—C161.385 (3)C72—H720.95
C12—C131.377 (3)C73—C741.371 (3)
C12—H120.95C73—H730.95
C13—C141.367 (3)C74—C751.369 (3)
C13—H130.95C75—C761.371 (3)
C14—C151.373 (3)C75—H750.95
C14—H140.95C76—H760.95
C15—C161.379 (3)C77—H77A0.99
C15—H150.95C77—H77B0.99
C16—H160.95C741—H74A0.98
C31—C331.524 (3)C741—H74B0.98
C31—C341.526 (3)C741—H74C0.98
C74—O741—C741117.6 (2)C31—C33—H33B109.5
C7A—N1—N2110.42 (16)H33A—C33—H33B109.5
C7A—N1—C11131.03 (17)C31—C33—H33C109.5
N2—N1—C11118.54 (16)H33A—C33—H33C109.5
C3—N2—N1105.32 (16)H33B—C33—H33C109.5
C7A—N7—C6110.03 (16)C31—C34—H34A109.5
C7A—N7—C77115.08 (16)C31—C34—H34B109.5
C6—N7—C77115.40 (16)H34A—C34—H34B109.5
N2—C3—C3A111.54 (18)C31—C34—H34C109.5
N2—C3—C31119.73 (18)H34A—C34—H34C109.5
C3A—C3—C31128.70 (19)H34B—C34—H34C109.5
C7A—C3A—C3104.89 (18)O51—C51—C52121.6 (2)
C7A—C3A—C4122.75 (19)O51—C51—C5120.25 (19)
C3—C3A—C4132.35 (19)C52—C51—C5118.14 (19)
C3A—C4—C5110.24 (17)C51—C52—C53112.77 (19)
C3A—C4—H4A109.6C51—C52—H52A109.0
C5—C4—H4A109.6C53—C52—H52A109.0
C3A—C4—H4B109.6C51—C52—H52B109.0
C5—C4—H4B109.6C53—C52—H52B109.0
H4A—C4—H4B108.1H52A—C52—H52B107.8
C4—C5—C55111.94 (17)C54—C53—C52111.67 (18)
C4—C5—C51111.07 (17)C54—C53—H53A109.3
C55—C5—C51107.62 (17)C52—C53—H53A109.3
C4—C5—C6108.42 (17)C54—C53—H53B109.3
C55—C5—C6111.81 (17)C52—C53—H53B109.3
C51—C5—C6105.82 (16)H53A—C53—H53B107.9
N7—C6—C5114.66 (17)C55—C54—C53108.32 (18)
N7—C6—H6A108.6C55—C54—H29A110.0
C5—C6—H6A108.6C53—C54—H29A110.0
N7—C6—H6B108.6C55—C54—H54B110.0
C5—C6—H6B108.6C53—C54—H54B110.0
H6A—C6—H6B107.6H29A—C54—H54B108.4
C12—C11—C16120.5 (2)O55—C55—C54121.9 (2)
C12—C11—N1120.66 (19)O55—C55—C5120.93 (19)
C16—C11—N1118.87 (19)C54—C55—C5116.92 (19)
C11—C12—C13119.3 (2)C72—C71—C76117.8 (2)
C11—C12—H12120.3C72—C71—C77119.9 (2)
C13—C12—H12120.3C76—C71—C77122.29 (19)
C14—C13—C12120.7 (2)C71—C72—C73121.4 (2)
C14—C13—H13119.7C71—C72—H72119.3
C12—C13—H13119.7C73—C72—H72119.3
C13—C14—C15119.9 (2)C74—C73—C72119.7 (2)
C13—C14—H14120.0C74—C73—H73120.2
C15—C14—H14120.0C72—C73—H73120.2
C14—C15—C16120.3 (2)C75—C74—O741115.7 (2)
C14—C15—H15119.8C75—C74—C73119.8 (2)
C16—C15—H15119.8O741—C74—C73124.5 (2)
C15—C16—C11119.2 (2)C74—C75—C76120.4 (2)
C15—C16—H16120.4C74—C75—H75119.8
C11—C16—H16120.4C76—C75—H75119.8
C3A—C7A—N1107.79 (18)C75—C76—C71120.9 (2)
C3A—C7A—N7126.69 (19)C75—C76—H76119.5
N1—C7A—N7125.51 (18)C71—C76—H76119.5
C3—C31—C33110.47 (18)N7—C77—C71112.91 (17)
C3—C31—C34109.73 (18)N7—C77—H77A109.0
C33—C31—C34108.93 (18)C71—C77—H77A109.0
C3—C31—C32109.60 (17)N7—C77—H77B109.0
C33—C31—C32108.71 (19)C71—C77—H77B109.0
C34—C31—C32109.37 (19)H77A—C77—H77B107.8
C31—C32—H32A109.5O741—C741—H74A109.5
C31—C32—H32B109.5O741—C741—H74B109.5
H32A—C32—H32B109.5H74A—C741—H74B109.5
C31—C32—H32C109.5O741—C741—H74C109.5
H32A—C32—H32C109.5H74A—C741—H74C109.5
H32B—C32—H32C109.5H74B—C741—H74C109.5
C31—C33—H33A109.5
C7A—N1—N2—C31.6 (2)C77—N7—C7A—N161.0 (3)
C11—N1—N2—C3177.26 (17)N2—C3—C31—C338.6 (3)
N1—N2—C3—C3A0.9 (2)C3A—C3—C31—C33173.2 (2)
N1—N2—C3—C31179.37 (17)N2—C3—C31—C34128.7 (2)
N2—C3—C3A—C7A0.2 (2)C3A—C3—C31—C3453.1 (3)
C31—C3—C3A—C7A178.2 (2)N2—C3—C31—C32111.2 (2)
N2—C3—C3A—C4178.6 (2)C3A—C3—C31—C3267.0 (3)
C31—C3—C3A—C40.3 (4)C4—C5—C51—O5115.2 (3)
C7A—C3A—C4—C516.8 (3)C55—C5—C51—O51138.0 (2)
C3—C3A—C4—C5161.4 (2)C6—C5—C51—O51102.3 (2)
C3A—C4—C5—C5580.4 (2)C4—C5—C51—C52165.39 (19)
C3A—C4—C5—C51159.26 (18)C55—C5—C51—C5242.5 (2)
C3A—C4—C5—C643.4 (2)C6—C5—C51—C5277.1 (2)
C7A—N7—C6—C544.7 (2)O51—C51—C52—C53134.9 (2)
C77—N7—C6—C587.6 (2)C5—C51—C52—C5345.7 (3)
C4—C5—C6—N761.6 (2)C51—C52—C53—C5451.7 (3)
C55—C5—C6—N762.3 (2)C52—C53—C54—C5556.9 (2)
C51—C5—C6—N7179.15 (17)C53—C54—C55—O55115.6 (2)
C7A—N1—C11—C1227.1 (3)C53—C54—C55—C559.0 (2)
N2—N1—C11—C12151.52 (19)C4—C5—C55—O552.3 (3)
C7A—N1—C11—C16153.8 (2)C51—C5—C55—O55124.7 (2)
N2—N1—C11—C1627.6 (3)C6—C5—C55—O55119.5 (2)
C16—C11—C12—C132.0 (3)C4—C5—C55—C54172.34 (18)
N1—C11—C12—C13178.86 (19)C51—C5—C55—C5450.0 (2)
C11—C12—C13—C142.3 (3)C6—C5—C55—C5465.8 (2)
C12—C13—C14—C150.6 (4)C76—C71—C72—C730.0 (3)
C13—C14—C15—C161.5 (4)C77—C71—C72—C73179.6 (2)
C14—C15—C16—C111.8 (3)C71—C72—C73—C742.1 (4)
C12—C11—C16—C150.0 (3)C741—O741—C74—C75165.5 (2)
N1—C11—C16—C15179.1 (2)C741—O741—C74—C7314.1 (3)
C3—C3A—C7A—N11.2 (2)C72—C73—C74—C752.7 (4)
C4—C3A—C7A—N1179.77 (19)C72—C73—C74—O741176.9 (2)
C3—C3A—C7A—N7178.09 (19)O741—C74—C75—C76178.4 (2)
C4—C3A—C7A—N70.5 (3)C73—C74—C75—C761.3 (4)
N2—N1—C7A—C3A1.8 (2)C74—C75—C76—C710.8 (4)
C11—N1—C7A—C3A176.9 (2)C72—C71—C76—C751.4 (3)
N2—N1—C7A—N7177.49 (18)C77—C71—C76—C75179.0 (2)
C11—N1—C7A—N73.8 (3)C7A—N7—C77—C71167.58 (17)
C6—N7—C7A—C3A14.3 (3)C6—N7—C77—C7162.6 (2)
C77—N7—C7A—C3A118.1 (2)C72—C71—C77—N7155.42 (19)
C6—N7—C7A—N1166.59 (19)C76—C71—C77—N725.0 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C52—H52A···O55i0.992.573.236 (3)124
C77—H77A···O51ii0.992.543.275 (3)131
C52—H52B···Cg1i0.992.823.384 (2)117
Symmetry codes: (i) x+1, y1/2, z+1/2; (ii) x+1, y+1/2, z+1/2.

Experimental details

(I)(II)
Crystal data
Chemical formulaC29H30F3N3O2C29H33N3O3
Mr509.56471.58
Crystal system, space groupMonoclinic, P21/nMonoclinic, P21/c
Temperature (K)120120
a, b, c (Å)11.9298 (18), 10.5678 (10), 19.614 (2)9.1904 (10), 11.9402 (14), 22.2888 (16)
β (°) 96.627 (10) 97.287 (9)
V3)2456.2 (5)2426.1 (4)
Z44
Radiation typeMo KαMo Kα
µ (mm1)0.100.08
Crystal size (mm)0.33 × 0.32 × 0.180.39 × 0.38 × 0.16
Data collection
DiffractometerBruker Nonius KappaCCD
diffractometer
Bruker Nonius KappaCCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Multi-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.975, 0.9820.977, 0.987
No. of measured, independent and
observed [I > 2σ(I)] reflections
31891, 5621, 3742 37788, 5566, 3161
Rint0.0550.084
(sin θ/λ)max1)0.6500.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.061, 0.151, 1.07 0.054, 0.143, 1.04
No. of reflections56215566
No. of parameters337320
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.43, 0.380.26, 0.32

Computer programs: COLLECT (Nonius, 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).

Selected geometric parameters (Å, °) for compounds (I) and (II) top
(a)Ring-puckering parameters
Parameter(I)(II)
Q0.480 (2)0.477 (2)
θ51.5 (2)49.5 (2)
ϕ96.6 (4)93.6 (3)
(b)Torsional angles
Parameter(I)(II)
N2-C3-C31-C32-119.6 (3)-111.2 (2)
N2-C3-C31-C330.2 (3)8.6 (3)
N2-C3-C31-C34121.0 (3)128.7 (2)
N2-N1-C11-C12-148.4 (2)-151.52 (19)
C6-N7-C77-C7166.9 (3)62.6 (2)
N7-C77-C71-C72-157.1 (2)-155.42 (19)
C73-C74-O74-C74114.1 (3)
Ring-puckering parameters are specified for the atom sequence (N7,C6,C5,C4,C3A,C7A)
Hydrogen bonds and short intermolecular contacts (Å, °) for compounds (I) and (II) top
CompoundD-H···AD-HH···AD···AD-H···A
(I)C6-H6A···O55i0.992.423.309 (3)149
C53-H53B···O55i0.992.543.448 (4)153
(II)C52-H52A···O55ii0.992.573.236 (3)124
C77-H77A···O51iii0.992.543.275 (3)131
C52-H52B···Cg1a,ii0.992.823.384 (2)117
a Cg1 represents the centroid of the ring (N1,N2,C3,C3A,C7A). Symmetry codes: i (0.5 - x, -0.5 + y, 1.5 - z), ii (1 - x, -0.5 + y, 0.5 - z), iii (1 - x, 0.5 + y, 0.5 - z)
 

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