Four N⁷-benzyl-substituted 4,5,6,7-tetra­hydro-1H-pyrazolo[3,4-b]pyri­dine-5-spiro-1′-cyclo­hexane-2′,6′-di­ones as ethanol hemisolvates: similar mol­ecular constitutions but different crystal structures

3-tert-Butyl-7-(4-chloro­benzyl)-4′,4′-dimethyl-1-phenyl-4,5,6,7-tetra­hydro-1H-pyrazolo[3,4-b]pyridine-5-spiro-1′-cyclo­hexane-2′,6′-dione ethanol hemisolvate, C₃₀H₃₄ClN₃O₂·0.5C₂H₆O, (I), its 7-(4-bromo­benzyl)- analogue, C₃₀H₃₄BrN₃O₂·0.5C₂H₆O, (II), and its 7-(4-methyl­benzyl)- analogue, C₃₁H₃₇N₃O₂·0.5C₂H₆O, (III), are isomorphous, with the ethanol component disordered across a twofold rotation axis in the space group C2/c. In the corresponding 7-[4-(trifluoro­methyl)benzyl]- compound, C₃₁H₃₄F₃N₃O₂·0.5C₂H₆O, (IV), the ethanol component is disordered across a centre of inversion in the space group P. In each of (I)–(IV), the reduced pyridine ring adopts a half-chair conformation. The heterocyclic components in (I)–(III) are linked into centrosymmetric dimers by a single C—H...π inter­action, with the half-occupancy ethanol component linked to the dimer by a combination of C—H...O and O—H...π(arene) hydrogen bonds. The heterocyclic mol­ecules in (IV) are linked into chains of centrosymmetric rings by C—H...O and C—H...π hydrogen bonds, again with the half-occupancy ethanol component pendent from the chain. The significance of this study lies in the isomorphism of the related derivatives (I)–(III), in the stoichiometric hemisolvation by ethanol, where the disordered solvent mol­ecule is linked to the heterocyclic component by a two-point linkage, and in the differences between the crystal structures of (I)–(III) and that of (IV).

S1. Comment

Spiranes are rather rigid structures which are useful as frameworks for the attachment of functional groups incorporating pharmacophoric or metal-coordinating moieties. Spiro skeletons are not only present in numerous naturally occurring alkaloids, but have also been used in drug discovery and in the development of combinatorial libraries (Bazgir et al., 2008). The development of new routes for the synthesis of these frameworks has attracted considerable attention and several distinct approaches have been reported for the preparation of heterocyclic spiranes. These include palladium-promoted spiroannulations onto carbocyclic or heterocyclic substrates (Møller & Undheim, 2003), spirocyclizations mediated by BF₃–Et₂O (Caputo et al., 2003), spiroannulation of carboxylic acids (Rahimizadeh et al., 2007), and oxidative rearrangement sequences and intramolecular Mannich reactions (Marti & Carreira, 2003).

We report here the structures of four closely related compounds, (I)–(IV), all obtained using three-component cyclocondensations induced by microwave irradiation, and all crystallizing as ethanol hemisolvates. We have been investigating such cyclocondensations as part of a programme for the synthesis of fused pyrazolo derivatives (Quiroga et al., 1999), and we have recently reported (Low et al., 2004) the structure of compound (V), obtained from the condensation reaction between 5-amino-3-tert-butyl-1-phenylpyrazole, 5,5-dimethylcyclohexane-1,3-dione (dimedone) and formaldehyde. The constitution of the heterocyclic component in (I)–(IV) differs from that in (V) in having a substituted benzyl group at position N7, rather than an H atom. Compounds (I)–(IV) were synthesized using a straightforward modification of the synthetic method employed earlier, but employing in each case an appropriately-substituted 5-(benzylamino)-3-tert-butyl-1-phenylpyrazole as the amino component (see scheme).

Compounds (I)–(IV) (Fig. 1) all crystallize as stoichiometric ethanol hemisolvates, with the ethanol disordered across a twofold rotation axis in (I)–(III) and across a centre of inversion in (IV). Compounds (I)–(III) are isomorphous in space group C2/c, while (IV) crystallizes in space group P1 with very different unit-cell dimensions. Examination of the refined structures using PLATON (Spek, 2003) showed that artificial removal of the ethanol component from the structures gave rise to four voids per unit cell in (I)–(III), with volumes ranging from 72 ų per void in (I) to 66 ų per void in (II) and (III), amounting in total to ca 5% of the unit-cell volume, and located near (1/2, 2/3, 3/4) and the symmetry-related equivalent positions. In (IV), a similar investigation found a single void centred at (1/2, 1/2, 1.0) and accounting for ca 6.3% of the unit-cell volume. It is possible that the structural role of the ethanol is simply to occupy otherwise void space; this is certainly consistent with its very limited participation in the supramolecular aggregation in the structures of (I)–(IV).

Thus, in each of the two distinct structures, the half-occupancy ethanol component is linked to the heterocyclic component by a combination of a C—H···O hydrogen bond and an O—H···π(arene) hydrogen bond in which the aryl ring of the benzyl substituent acts as the acceptor (Table 2). Statistically, the pairs of heterocyclic molecules related by a twofold axis in (I)–(III) or by inversion in (IV) are each associated with a disordered ethanol molecule lying across the symmetry element in question. However, at the local level, each ethanol site is occupied by a single molecule with a definite orientation, although the two alternative orientations occur with equal probability. Thus, for each ethanol location, one set of atomic sites is fully occupied while the other is vacant. Hence, a specific ethanol molecule is either linked to the heterocycle at (x, y, z) or to its symmetry-relayed companion, but it cannot be linked to two such heterocycles. Thus, the ethanol component plays no further role in the supramolecular aggregation.

The isomorphism of (I)–(III) may be compared with the isomorphous series (VI)–(VIII) (Portilla et al., 2005). On the other hand, in the closely-related 7-aryl-benzo[h]pyrazolo[3,4-b]quinolines, the 4-chlorophenyl and 4-methylphenyl derivatives are isomorphous, while in the isomeric 11-aryl-benzo[f]pyrazolo[3,4-b]quinolines, the corresponding derivatives are not isomorphous (Portilla et al., 2008), although the 4-chlorophenyl compound is isomorphous with the 4-bromophenyl derivative (Serrano et al., 2005a,b).

In each of (I)–(IV), the reduced pyridine ring adopts a half-chair conformation, as shown by the ring-puckering parameters (Table 1; Cremer & Pople, 1975). For an idealized half-chair ring with equal bond lengths throughout, the ring-puckering angles are θ = 50.8° and ϕ = (60k + 30)°, where k represents an integer. The similarity between the corresponding parameters is very high for the isomorphous compounds (I)–(III), while the parameters for (IV) differ slightly.

The rest of the molecular conformation is determined by the orientation of the three pendent substituents relative to the heterocyclic molecular core, and these orientations can be defined in terms of just six torsion angles (Table 1). The tert-butyl substituent is always slightly rotated about the C3—C31 bond so that atom C33 lies just out of the plane of the pyrazole ring. As with the ring-puckering angles for the pyridine ring, the corresponding torsion angles in the isomorphous compounds (I)–(III) are all very similar, while the out-of-plane rotation of the tert-butyl group is significantly larger in (IV). The observed conformations, together with the pyramidal coordination at atom N7, mean that the molecules have no internal symmetry and hence that they are chiral, although the space group in all cases accommodates a racemic mixture of enantiomers.

The supramolecular aggregation depends upon hydrogen-bond formation between the heterocyclic molecules, and the ethanol components are simply pendent from the resulting hydrogen-bonded aggregates. The aggregation is dominated by hydrogen bonds of C—H···π type, augmented in the case of (IV) by a C—H···O hydrogen bond (Table 2). Of the short intermolecular contacts indicated by PLATON (Spek, 2003) as possible hydrogen bonds, we have discounted all those involving methyl C—H bonds as potential donors. Not only are methyl C—H bonds expected to be of rather low acidity but, in general, methyl groups CH₃—E undergo extremely fast rotation about the C—E bond even in the solid state, as shown by solid-state NMR spectroscopy (Riddell & Rogerson, 1996, 1997). Such contacts of C—H···O type occur in (I)–(III). In each case, however, the fast rotation of the methyl groups about the C—C bonds will render such contacts structurally insignificant. In addition, we have discarded intermolecular C—H···O contacts in which the H···O distance exceeds 2.50 Å, and all contacts where the D—H···A angle is less than 125°. Finally, we have excluded from consideration the intermolecular C—H···Cl and C—H···Br contacts in (I) and (II), as it has been concluded that such contacts involving covalently bound Cl or Br are probably no more than van der Waals contacts, and that geometrically they are certainly at the outer limit of what could conceivably be described as a hydrogen bond (Aakeröy et al., 1999; Brammer et al., 2001; Thallapally & Nangia, 2001).

In compounds (I)–(III) a single C—H···π interaction (Table 2) links pairs of pyrazolopyridine units into a centrosymmetric dimer (Fig. 2), but there are no direction-specific interactions between these dimers, so that the supramolecular structure can be regarded as finite or zero-dimensional.

By contrast, in compound (IV), where an entirely equivalent dimer is formed by paired C—H···π interactions, these dimeric units are further linked by a C—H..O hydrogen bond (Table 2) into a chain of centrosymmetric rings running parallel to the [010] direction (Fig. 3). Rings of R²₂(14) type (Bernstein et al., 1995) formed by pairs of C—H···O hydrogen bonds are centred at (1/2, n, 1/2), where n represents an integer, while the rings formed by pairs of C—H···π interactions are centred at (1/2, 0.5 + n, 1/2), where n represents an integer. There are no direction-specific interactions between these chains of rings, so that the supramolecular structure is one-dimensional.

Compounds (I)–(IV) are thus similar in constitution and their heterocyclic components are very similar in both configuration and conformation. Despite these close resemblances, the range of direction-specific intermolecular interactions and the crystal structures differ between those of the isomorphous compounds (I)–(III) on the one hand and compound (IV) on the other. The contrast between compounds (III) and (IV) is particularly striking, as their compositions differ only in the formal replacement of a CH₃ group in (III) by a CF₃ group in (IV), and as neither of these substituents plays any direct role in the supramolecular aggregation. The prediction of the crystal structures of molecular compounds remains an extremely difficult undertaking which has so far met with very limited success (Day et al., 2005). Any attempts at the present time to explain the structural differences found here between compounds (III) and (IV) are thus likely to be largely speculative.

Related literature

For related literature, see: Aakeröy et al. (1999); Bazgir et al. (2008); Bernstein et al. (1995); Brammer et al. (2001); Caputo et al. (2003); Cremer & Pople (1975); Day et al. (2005); Low et al. (2004); Møller & Undheim (2003); Marti & Carreira (2003); Portilla et al. (2005, 2008); Quiroga et al. (1999); Rahimizadeh et al. (2007); Riddell & Rogerson (1996, 1997); Serrano et al. (2005a, 2005b); Spek (2003); Thallapally & Nangia (2001).

S2. Experimental

Microwave-induced syntheses were carried out using a focused microwave reactor (CEM Discover). A mixture of the appropriately substituted aminopyrazole (see scheme) (2 mmol), 5,5-dimethylcyclohexane-1,3-dione (2 mmol) and an excess of paraformaldehyde (80–100 mg) was exposed to microwave radiation at 473 K with a maximum power of 300 W for 25 min. The reaction mixtures were then dissolved in hot ethanol. After cooling, the solid products were collected by filtration and washed with ethanol and then hexane (2 × 5 ml) to afford the pure products, (I)–(IV), as colourless crystals. For (I), yield 85%, m.p. 453–455 K; HRMS found 503.2336; C₃₀H₃₄ClN₃O₂ requires 503.2340. For (II), yield 77%, m.p. 439–441 K; HRMS found 547.1828, C₃₀H₃₄BrN₃O₂ requires 547.1834. For (III), yield 75%, m.p. 472–474 K; HRMS found 483.2894, C₃₁H₃₇N₃O₂ requires 483.2886. For (IV), yield 85%, m.p. 418–420 K; HRMS found 537.2610, C₃₁H₃₄F₃N₃O₂ requires 537.2603.

S3. Refinement

For compounds (I)–(III), the systematic absences permitted Cc or C2/c as possible space groups; C2/c was selected, and confirmed by the structure analysis. Crystals of compound (IV) are triclinic; space group P1 was selected, and confirmed by the structure analysis. All H atoms were located in difference maps and then treated as riding atoms in geometrically idealized positions, with C—H = 0.95 (aromatic), 0.98 (CH₃) or 0.99 Å (CH₂) and O—H = 0.84 Å, and with U_iso(H) = kU_eq(carrier), where k = 1.5 for the methyl and hydroxyl H atoms, and 1.2 for all other H atoms. In (I)–(III), the ethanol component was disordered across a twofold axis, selected as that along (1/2, y, 3/4), while in (IV) this component was disordered across a centre of inversion, selected as that at (1/2, 1/2, 1). For each compound, it proved necessary to apply restraints to the C—C and C—O distances of 1.540 (1) and 1.420 (1) Å respectively, and to the non-bonded C···O distance of 2.418 (2) Å, in the disordered ethanol component. The reference heterocyclic molecule in (IV) was selected to be of the same hand as those in (I)–(III).

Computing details

For all 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

	Fig. 1. The independent molecular components in (I)–(IV). (a) Compound (I), (b) (II), (c) (III) and (d) (IV) [The labels for C13 and C14 have been swapped to match the bonds in the CIF data tables for (IV). Please check]. The ethanol components all have 0.5 occupancy, so that only half of the heterocyclic molecules are linked to ethanol molecules via hydrogen bonds (see text). Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The centrosymmetric hydrogen-bonded dimer formed in each of the isomorphous compounds (I)–(III). For the sake of clarity, the half-occupancy ethanol molecules, H atoms not involved in the hydrogen-bonded motif shown, and the unit-cell outline have all been omitted. The atom marked with an asterisk (*) is at the symmetry position (1/2 - x, 3/2 - y, 1 - z).
	Fig. 3. A stereoview of part of the crystal structure of (IV), showing the formation of a chain of centrosymmetric hydrogen-bonded rings along [010] built from C—H···O and C—H···π hydrogen bonds. For the sake of clarity, the half-occupancy ethanol molecules and H atoms not involved in the motifs shown have been omitted.

(I) 3-tert-Butyl-7-(4-chlorobenzyl)-4',4'-dimethyl-1-phenyl-4,5,6,7- tetrahydro-1H-pyrazolo[3,4-b]pyridine-5-spiro-1'-cyclohexane- 2',6'-dione ethanol hemisolvate

Crystal data

C30H34ClN3O2·0.5C2H6O	F(000) = 2248
Mr = 527.09	Dx = 1.327 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 6021 reflections
a = 27.419 (4) Å	θ = 3.0–27.5°
b = 10.5860 (13) Å	µ = 0.18 mm^−1
c = 21.580 (3) Å	T = 120 K
β = 122.625 (11)°	Block, colourless
V = 5275.5 (14) Å^3	0.32 × 0.23 × 0.22 mm
Z = 8

Data collection

Bruker Nonius KappaCCD area-detector diffractometer	6021 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	4812 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.059
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.0°
ϕ and ω scans	h = −35→34
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −13→12
Tmin = 0.954, Tmax = 0.961	l = −28→27
36250 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.132	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0455P)^2 + 11.7674P] where P = (Fo^2 + 2Fc^2)/3
6021 reflections	(Δ/σ)max = 0.001
352 parameters	Δρmax = 0.55 e Å^−3
3 restraints	Δρmin = −0.52 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cl7	0.39945 (2)	0.66283 (6)	0.82597 (3)	0.03174 (14)
O51	0.40061 (6)	0.58895 (14)	0.42829 (8)	0.0264 (3)
O55	0.30684 (6)	0.25346 (13)	0.44006 (8)	0.0238 (3)
N1	0.15935 (7)	0.50792 (15)	0.35775 (8)	0.0177 (3)
N2	0.13499 (7)	0.48364 (15)	0.28439 (8)	0.0186 (3)
N7	0.25720 (7)	0.53389 (15)	0.46815 (8)	0.0170 (3)
C3	0.17881 (8)	0.46948 (17)	0.27577 (10)	0.0166 (4)
C3a	0.23249 (8)	0.48169 (17)	0.34329 (10)	0.0165 (4)
C4	0.29354 (8)	0.47093 (18)	0.36278 (10)	0.0178 (4)
C5	0.33590 (8)	0.46673 (18)	0.44583 (10)	0.0170 (4)
C6	0.31421 (8)	0.56170 (17)	0.48149 (10)	0.0173 (4)
C7a	0.21836 (8)	0.50633 (17)	0.39381 (10)	0.0166 (4)
C11	0.12152 (8)	0.53981 (18)	0.38086 (10)	0.0181 (4)
C12	0.13925 (8)	0.61559 (19)	0.44154 (11)	0.0208 (4)
C13	0.10057 (9)	0.64580 (19)	0.46185 (11)	0.0227 (4)
C14	0.04414 (9)	0.6043 (2)	0.42067 (11)	0.0263 (4)
C15	0.02626 (9)	0.5310 (2)	0.35919 (12)	0.0276 (5)
C16	0.06499 (8)	0.4972 (2)	0.33976 (11)	0.0231 (4)
C31	0.16806 (8)	0.44614 (18)	0.20036 (10)	0.0184 (4)
C32	0.19267 (10)	0.3180 (2)	0.19862 (12)	0.0275 (4)
C33	0.10337 (9)	0.4489 (2)	0.14238 (11)	0.0286 (5)
C34	0.19749 (9)	0.5491 (2)	0.18266 (11)	0.0250 (4)
C51	0.39576 (8)	0.51656 (18)	0.46782 (10)	0.0188 (4)
C52	0.44676 (8)	0.4808 (2)	0.54177 (11)	0.0247 (4)
C53	0.44807 (8)	0.3432 (2)	0.56348 (11)	0.0242 (4)
C54	0.38994 (8)	0.31258 (19)	0.55459 (11)	0.0219 (4)
C55	0.34075 (8)	0.33525 (18)	0.47695 (10)	0.0177 (4)
C71	0.28942 (8)	0.50512 (18)	0.59765 (10)	0.0178 (4)
C72	0.31876 (8)	0.42535 (19)	0.65770 (11)	0.0217 (4)
C73	0.35147 (9)	0.4728 (2)	0.72834 (11)	0.0246 (4)
C74	0.35477 (8)	0.6013 (2)	0.73848 (10)	0.0228 (4)
C75	0.32467 (8)	0.68332 (19)	0.68035 (11)	0.0227 (4)
C76	0.29208 (8)	0.63392 (19)	0.61013 (10)	0.0205 (4)
C77	0.25595 (8)	0.45028 (18)	0.52146 (10)	0.0186 (4)
C531	0.45796 (9)	0.2566 (2)	0.51527 (12)	0.0294 (5)
C532	0.49705 (10)	0.3262 (2)	0.64343 (12)	0.0354 (5)
C81	0.4735 (2)	0.6812 (4)	0.7091 (4)	0.0511 (10)	0.50
C82	0.5250 (2)	0.6483 (6)	0.7867 (3)	0.0511 (10)	0.50
O81	0.43843 (16)	0.5723 (5)	0.6765 (2)	0.0685 (14)	0.50
H4A	0.3028	0.5441	0.3423	0.021*
H4B	0.2977	0.3932	0.3405	0.021*
H5A	0.3427	0.5630	0.5353	0.021*
H5B	0.3133	0.6474	0.4625	0.021*
H12	0.1778	0.6469	0.4692	0.025*
H13	0.1131	0.6956	0.5045	0.027*
H14	0.0177	0.6259	0.4345	0.032*
H15	−0.0129	0.5037	0.3300	0.033*
H16	0.0527	0.4446	0.2982	0.028*
H12A	0.1740	0.2515	0.2103	0.041*
H12B	0.2345	0.3168	0.2350	0.041*
H12C	0.1854	0.3032	0.1495	0.041*
H33A	0.0840	0.3817	0.1525	0.043*
H33B	0.0970	0.4359	0.0936	0.043*
H33C	0.0874	0.5310	0.1438	0.043*
H34A	0.2394	0.5461	0.2185	0.037*
H34B	0.1825	0.6318	0.1850	0.037*
H34C	0.1895	0.5357	0.1331	0.037*
H52A	0.4472	0.5354	0.5793	0.030*
H52B	0.4825	0.4986	0.5425	0.030*
H54A	0.3897	0.2231	0.5678	0.026*
H54B	0.3850	0.3661	0.5884	0.026*
H72	0.3164	0.3366	0.6502	0.026*
H73	0.3714	0.4175	0.7693	0.029*
H75	0.3263	0.7719	0.6883	0.027*
H76	0.2710	0.6896	0.5695	0.025*
H77A	0.2727	0.3673	0.5216	0.022*
H77B	0.2153	0.4365	0.5064	0.022*
H53A	0.4945	0.2790	0.5199	0.044*
H53B	0.4260	0.2659	0.4639	0.044*
H53C	0.4598	0.1688	0.5309	0.044*
H53D	0.5340	0.3467	0.6489	0.053*
H53E	0.4978	0.2384	0.6583	0.053*
H53F	0.4909	0.3826	0.6746	0.053*
H81A	0.4877	0.7035	0.6770	0.061*	0.50
H81B	0.4502	0.7528	0.7090	0.061*	0.50
H82A	0.5402	0.5631	0.7899	0.077*	0.50
H82B	0.5554	0.7106	0.7991	0.077*	0.50
H82C	0.5124	0.6560	0.8211	0.077*	0.50
H81	0.4131	0.5748	0.6870	0.103*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl7	0.0323 (3)	0.0386 (3)	0.0181 (2)	−0.0064 (2)	0.0095 (2)	−0.0038 (2)
O51	0.0238 (7)	0.0277 (8)	0.0290 (8)	−0.0045 (6)	0.0151 (6)	0.0048 (6)
O55	0.0245 (7)	0.0189 (7)	0.0279 (7)	−0.0038 (6)	0.0142 (6)	−0.0020 (6)
N1	0.0180 (7)	0.0217 (8)	0.0153 (7)	−0.0022 (6)	0.0102 (6)	−0.0016 (6)
N2	0.0205 (8)	0.0214 (8)	0.0149 (7)	−0.0019 (6)	0.0102 (6)	−0.0018 (6)
N7	0.0181 (7)	0.0201 (8)	0.0143 (7)	−0.0031 (6)	0.0097 (6)	0.0001 (6)
C3	0.0190 (8)	0.0148 (8)	0.0179 (8)	−0.0011 (7)	0.0113 (7)	−0.0001 (7)
C3a	0.0190 (9)	0.0149 (8)	0.0179 (8)	−0.0009 (7)	0.0114 (7)	0.0007 (7)
C4	0.0168 (8)	0.0210 (9)	0.0175 (8)	−0.0011 (7)	0.0105 (7)	−0.0010 (7)
C5	0.0168 (8)	0.0185 (9)	0.0168 (8)	−0.0008 (7)	0.0098 (7)	0.0000 (7)
C6	0.0177 (8)	0.0157 (9)	0.0206 (9)	−0.0011 (7)	0.0117 (7)	−0.0007 (7)
C7a	0.0185 (8)	0.0163 (8)	0.0167 (8)	−0.0015 (7)	0.0106 (7)	0.0003 (7)
C11	0.0184 (8)	0.0208 (9)	0.0188 (9)	0.0005 (7)	0.0126 (7)	0.0026 (7)
C12	0.0197 (9)	0.0229 (10)	0.0221 (9)	−0.0028 (7)	0.0127 (8)	−0.0018 (7)
C13	0.0261 (10)	0.0247 (10)	0.0223 (9)	−0.0017 (8)	0.0163 (8)	−0.0025 (8)
C14	0.0247 (10)	0.0344 (11)	0.0278 (10)	0.0010 (8)	0.0195 (9)	−0.0012 (9)
C15	0.0195 (9)	0.0388 (12)	0.0273 (10)	−0.0055 (9)	0.0144 (8)	−0.0059 (9)
C16	0.0214 (9)	0.0302 (11)	0.0194 (9)	−0.0036 (8)	0.0122 (8)	−0.0042 (8)
C31	0.0183 (9)	0.0220 (9)	0.0166 (8)	−0.0013 (7)	0.0106 (7)	−0.0021 (7)
C32	0.0359 (11)	0.0236 (10)	0.0266 (10)	0.0008 (9)	0.0191 (9)	−0.0053 (8)
C33	0.0211 (10)	0.0470 (13)	0.0182 (9)	−0.0033 (9)	0.0109 (8)	−0.0068 (9)
C34	0.0297 (10)	0.0277 (11)	0.0223 (9)	−0.0032 (8)	0.0171 (8)	0.0012 (8)
C51	0.0193 (9)	0.0169 (9)	0.0217 (9)	−0.0019 (7)	0.0121 (8)	−0.0030 (7)
C52	0.0190 (9)	0.0283 (11)	0.0238 (10)	−0.0069 (8)	0.0096 (8)	0.0007 (8)
C53	0.0181 (9)	0.0288 (11)	0.0215 (9)	−0.0006 (8)	0.0079 (8)	0.0037 (8)
C54	0.0221 (9)	0.0229 (10)	0.0217 (9)	0.0003 (8)	0.0125 (8)	0.0048 (8)
C55	0.0174 (8)	0.0185 (9)	0.0217 (9)	0.0002 (7)	0.0135 (7)	0.0003 (7)
C71	0.0170 (8)	0.0222 (9)	0.0169 (8)	−0.0007 (7)	0.0109 (7)	0.0007 (7)
C72	0.0230 (9)	0.0196 (9)	0.0231 (9)	−0.0005 (7)	0.0127 (8)	0.0029 (7)
C73	0.0225 (9)	0.0294 (11)	0.0174 (9)	−0.0001 (8)	0.0079 (8)	0.0062 (8)
C74	0.0207 (9)	0.0310 (11)	0.0155 (9)	−0.0042 (8)	0.0088 (7)	−0.0030 (8)
C75	0.0259 (10)	0.0217 (10)	0.0222 (9)	−0.0006 (8)	0.0139 (8)	0.0001 (8)
C76	0.0229 (9)	0.0216 (9)	0.0184 (9)	0.0015 (7)	0.0120 (8)	0.0014 (7)
C77	0.0215 (9)	0.0192 (9)	0.0172 (8)	−0.0014 (7)	0.0119 (7)	0.0010 (7)
C531	0.0264 (10)	0.0330 (12)	0.0304 (11)	0.0081 (9)	0.0164 (9)	0.0060 (9)
C532	0.0258 (11)	0.0417 (13)	0.0248 (11)	−0.0006 (10)	0.0044 (9)	0.0067 (10)
C81	0.0499 (18)	0.020 (3)	0.069 (2)	−0.0012 (17)	0.0229 (16)	−0.0054 (18)
C82	0.0499 (18)	0.020 (3)	0.069 (2)	−0.0012 (17)	0.0229 (16)	−0.0054 (18)
O81	0.039 (2)	0.111 (4)	0.061 (3)	−0.018 (2)	0.031 (2)	−0.036 (3)

Geometric parameters (Å, º)

Cl7—C74	1.731 (2)	C33—H33C	0.98
O51—C51	1.206 (2)	C34—H34A	0.98
O55—C55	1.204 (2)	C34—H34B	0.98
N1—C7a	1.366 (2)	C34—H34C	0.98
N1—N2	1.371 (2)	C51—C52	1.496 (3)
N1—C11	1.413 (2)	C52—C53	1.525 (3)
N2—C3	1.320 (2)	C52—H52A	0.99
N7—C7a	1.397 (2)	C52—H52B	0.99
N7—C6	1.459 (2)	C53—C531	1.517 (3)
N7—C77	1.467 (2)	C53—C532	1.521 (3)
C3—C3a	1.412 (3)	C53—C54	1.534 (3)
C3—C31	1.510 (2)	C54—C55	1.499 (3)
C3a—C7a	1.365 (2)	C54—H54A	0.99
C3a—C4	1.494 (2)	C54—H54B	0.99
C4—C5	1.523 (2)	C71—C72	1.384 (3)
C4—H4A	0.99	C71—C76	1.384 (3)
C4—H4B	0.99	C71—C77	1.502 (3)
C5—C55	1.520 (3)	C72—C73	1.381 (3)
C5—C51	1.535 (2)	C72—H72	0.95
C5—C6	1.565 (2)	C73—C74	1.372 (3)
C6—H5A	0.99	C73—H73	0.95
C6—H5B	0.99	C74—C75	1.376 (3)
C11—C12	1.381 (3)	C75—C76	1.381 (3)
C11—C16	1.382 (3)	C75—H75	0.95
C12—C13	1.386 (3)	C76—H76	0.95
C12—H12	0.95	C77—H77A	0.99
C13—C14	1.376 (3)	C77—H77B	0.99
C13—H13	0.95	C531—H53A	0.98
C14—C15	1.378 (3)	C531—H53B	0.98
C14—H14	0.95	C531—H53C	0.98
C15—C16	1.383 (3)	C532—H53D	0.98
C15—H15	0.95	C532—H53E	0.98
C16—H16	0.95	C532—H53F	0.98
C31—C34	1.522 (3)	C81—O81	1.4202 (10)
C31—C33	1.523 (3)	C81—C82	1.5388 (11)
C31—C32	1.525 (3)	C81—H81A	0.99
C32—H12A	0.98	C81—H81B	0.99
C32—H12B	0.98	C82—H82A	0.98
C32—H12C	0.98	C82—H82B	0.98
C33—H33A	0.98	C82—H82C	0.98
C33—H33B	0.98	O81—H81	0.84
C7a—N1—N2	110.22 (14)	H34B—C34—H34C	109.5
C7a—N1—C11	132.17 (16)	O51—C51—C52	121.25 (17)
N2—N1—C11	117.33 (15)	O51—C51—C5	120.44 (17)
C3—N2—N1	105.68 (15)	C52—C51—C5	118.13 (16)
C7a—N7—C6	109.96 (14)	C51—C52—C53	115.02 (16)
C7a—N7—C77	116.69 (15)	C51—C52—H52A	108.5
C6—N7—C77	116.28 (15)	C53—C52—H52A	108.5
N2—C3—C3a	111.46 (16)	C51—C52—H52B	108.5
N2—C3—C31	120.47 (16)	C53—C52—H52B	108.5
C3a—C3—C31	128.06 (16)	H52A—C52—H52B	107.5
C7a—C3a—C3	104.77 (16)	C531—C53—C532	109.36 (18)
C7a—C3a—C4	123.17 (16)	C531—C53—C52	110.50 (17)
C3—C3a—C4	132.05 (16)	C532—C53—C52	108.77 (18)
C3a—C4—C5	111.19 (15)	C531—C53—C54	110.13 (17)
C3a—C4—H4A	109.4	C532—C53—C54	109.83 (17)
C5—C4—H4A	109.4	C52—C53—C54	108.24 (16)
C3a—C4—H4B	109.4	C55—C54—C53	110.74 (15)
C5—C4—H4B	109.4	C55—C54—H54A	109.5
H4A—C4—H4B	108.0	C53—C54—H54A	109.5
C55—C5—C4	112.11 (15)	C55—C54—H54B	109.5
C55—C5—C51	110.71 (15)	C53—C54—H54B	109.5
C4—C5—C51	111.34 (15)	H54A—C54—H54B	108.1
C55—C5—C6	109.68 (14)	O55—C55—C54	122.18 (17)
C4—C5—C6	108.00 (15)	O55—C55—C5	120.92 (17)
C51—C5—C6	104.69 (14)	C54—C55—C5	116.89 (16)
N7—C6—C5	115.09 (15)	C72—C71—C76	118.41 (18)
N7—C6—H5A	108.5	C72—C71—C77	119.53 (17)
C5—C6—H5A	108.5	C76—C71—C77	122.06 (17)
N7—C6—H5B	108.5	C73—C72—C71	121.01 (19)
C5—C6—H5B	108.5	C73—C72—H72	119.5
H5A—C6—H5B	107.5	C71—C72—H72	119.5
C3a—C7a—N1	107.85 (16)	C74—C73—C72	118.98 (18)
C3a—C7a—N7	126.05 (17)	C74—C73—H73	120.5
N1—C7a—N7	125.97 (16)	C72—C73—H73	120.5
C12—C11—C16	119.83 (17)	C73—C74—C75	121.63 (18)
C12—C11—N1	121.55 (17)	C73—C74—Cl7	119.60 (16)
C16—C11—N1	118.58 (17)	C75—C74—Cl7	118.74 (16)
C11—C12—C13	119.72 (18)	C74—C75—C76	118.46 (19)
C11—C12—H12	120.1	C74—C75—H75	120.8
C13—C12—H12	120.1	C76—C75—H75	120.8
C14—C13—C12	120.51 (19)	C75—C76—C71	121.43 (18)
C14—C13—H13	119.7	C75—C76—H76	119.3
C12—C13—H13	119.7	C71—C76—H76	119.3
C13—C14—C15	119.58 (18)	N7—C77—C71	111.51 (15)
C13—C14—H14	120.2	N7—C77—H77A	109.3
C15—C14—H14	120.2	C71—C77—H77A	109.3
C14—C15—C16	120.32 (19)	N7—C77—H77B	109.3
C14—C15—H15	119.8	C71—C77—H77B	109.3
C16—C15—H15	119.8	H77A—C77—H77B	108.0
C11—C16—C15	119.98 (18)	C53—C531—H53A	109.5
C11—C16—H16	120.0	C53—C531—H53B	109.5
C15—C16—H16	120.0	H53A—C531—H53B	109.5
C3—C31—C34	109.36 (15)	C53—C531—H53C	109.5
C3—C31—C33	110.27 (15)	H53A—C531—H53C	109.5
C34—C31—C33	108.67 (17)	H53B—C531—H53C	109.5
C3—C31—C32	109.90 (16)	C53—C532—H53D	109.5
C34—C31—C32	109.24 (16)	C53—C532—H53E	109.5
C33—C31—C32	109.39 (17)	H53D—C532—H53E	109.5
C31—C32—H12A	109.5	C53—C532—H53F	109.5
C31—C32—H12B	109.5	H53D—C532—H53F	109.5
H12A—C32—H12B	109.5	H53E—C532—H53F	109.5
C31—C32—H12C	109.5	O81—C81—C82	109.60 (16)
H12A—C32—H12C	109.5	O81—C81—H81A	105.3
H12B—C32—H12C	109.5	C82—C81—H81A	109.7
C31—C33—H33A	109.5	O81—C81—H81B	110.9
C31—C33—H33B	109.5	C82—C81—H81B	112.9
H33A—C33—H33B	109.5	H81A—C81—H81B	108.2
C31—C33—H33C	109.5	C81—C82—H82A	113.1
H33A—C33—H33C	109.5	C81—C82—H82B	107.1
H33B—C33—H33C	109.5	H82A—C82—H82B	109.5
C31—C34—H34A	109.5	C81—C82—H82C	108.2
C31—C34—H34B	109.5	H82A—C82—H82C	109.5
H34A—C34—H34B	109.5	H82B—C82—H82C	109.5
C31—C34—H34C	109.5	C81—O81—H81	106.1
H34A—C34—H34C	109.5
C7a—N1—N2—C3	−1.0 (2)	N2—C3—C31—C34	122.09 (19)
C11—N1—N2—C3	173.73 (16)	C3a—C3—C31—C34	−56.5 (3)
N1—N2—C3—C3a	1.2 (2)	N2—C3—C31—C33	2.7 (3)
N1—N2—C3—C31	−177.67 (16)	C3a—C3—C31—C33	−175.97 (19)
N2—C3—C3a—C7a	−0.9 (2)	N2—C3—C31—C32	−118.00 (19)
C31—C3—C3a—C7a	177.82 (18)	C3a—C3—C31—C32	63.4 (2)
N2—C3—C3a—C4	178.41 (19)	C55—C5—C51—O51	150.01 (18)
C31—C3—C3a—C4	−2.9 (3)	C4—C5—C51—O51	24.6 (2)
C7a—C3a—C4—C5	10.4 (3)	C6—C5—C51—O51	−91.9 (2)
C3—C3a—C4—C5	−168.80 (19)	C55—C5—C51—C52	−34.7 (2)
C3a—C4—C5—C55	81.75 (19)	C4—C5—C51—C52	−160.10 (17)
C3a—C4—C5—C51	−153.60 (16)	C6—C5—C51—C52	83.5 (2)
C3a—C4—C5—C6	−39.2 (2)	O51—C51—C52—C53	−142.14 (19)
C7a—N7—C6—C5	−46.4 (2)	C5—C51—C52—C53	42.6 (2)
C77—N7—C6—C5	89.02 (19)	C51—C52—C53—C531	68.1 (2)
C55—C5—C6—N7	−61.2 (2)	C51—C52—C53—C532	−171.87 (18)
C4—C5—C6—N7	61.29 (19)	C51—C52—C53—C54	−52.6 (2)
C51—C5—C6—N7	−179.99 (15)	C531—C53—C54—C55	−62.5 (2)
C3—C3a—C7a—N1	0.3 (2)	C532—C53—C54—C55	177.03 (18)
C4—C3a—C7a—N1	−179.14 (17)	C52—C53—C54—C55	58.4 (2)
C3—C3a—C7a—N7	−175.60 (17)	C53—C54—C55—O55	122.6 (2)
C4—C3a—C7a—N7	5.0 (3)	C53—C54—C55—C5	−56.4 (2)
N2—N1—C7a—C3a	0.4 (2)	C4—C5—C55—O55	−11.8 (2)
C11—N1—C7a—C3a	−173.22 (19)	C51—C5—C55—O55	−136.84 (18)
N2—N1—C7a—N7	176.31 (17)	C6—C5—C55—O55	108.13 (19)
C11—N1—C7a—N7	2.6 (3)	C4—C5—C55—C54	167.18 (15)
C6—N7—C7a—C3a	13.1 (3)	C51—C5—C55—C54	42.2 (2)
C77—N7—C7a—C3a	−122.1 (2)	C6—C5—C55—C54	−72.85 (19)
C6—N7—C7a—N1	−162.01 (17)	C76—C71—C72—C73	−2.0 (3)
C77—N7—C7a—N1	62.8 (2)	C77—C71—C72—C73	177.88 (18)
C7a—N1—C11—C12	21.5 (3)	C71—C72—C73—C74	−0.2 (3)
N2—N1—C11—C12	−151.77 (18)	C72—C73—C74—C75	2.4 (3)
C7a—N1—C11—C16	−160.8 (2)	C72—C73—C74—Cl7	−175.63 (15)
N2—N1—C11—C16	25.9 (3)	C73—C74—C75—C76	−2.2 (3)
C16—C11—C12—C13	1.6 (3)	Cl7—C74—C75—C76	175.80 (15)
N1—C11—C12—C13	179.26 (18)	C74—C75—C76—C71	−0.1 (3)
C11—C12—C13—C14	−2.1 (3)	C72—C71—C76—C75	2.2 (3)
C12—C13—C14—C15	0.6 (3)	C77—C71—C76—C75	−177.72 (17)
C13—C14—C15—C16	1.4 (3)	C7a—N7—C77—C71	−167.33 (15)
C12—C11—C16—C15	0.4 (3)	C6—N7—C77—C71	60.3 (2)
N1—C11—C16—C15	−177.36 (19)	C72—C71—C77—N7	−146.42 (17)
C14—C15—C16—C11	−1.9 (3)	C76—C71—C77—N7	33.5 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O81—H81···Cg1	0.84	2.32	3.316 (5)	157
C52—H52A···O81	0.99	2.27	3.188 (5)	154
C75—H75···Cg2^i	0.95	2.55	3.469 (2)	163

Symmetry code: (i) −x+1/2, −y+3/2, −z+1.

(II) 3-tert-Butyl-7-(4-bromobenzyl)-4',4'-dimethyl-1-phenyl-4,5,6,7- tetrahydro-1H-pyrazolo[3,4-b]pyridine-5-spiro-1'-cyclohexane- 2',6'-dione ethanol hemisolvate

Crystal data

C30H34BrN3O2·0.5C2H6O	F(000) = 2392
Mr = 571.55	Dx = 1.431 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 6083 reflections
a = 27.4453 (7) Å	θ = 3.0–27.5°
b = 10.5519 (8) Å	µ = 1.59 mm^−1
c = 21.715 (2) Å	T = 120 K
β = 122.484 (7)°	Block, colourless
V = 5304.8 (8) Å^3	0.45 × 0.35 × 0.25 mm
Z = 8

Data collection

Bruker Nonius KappaCCD area-detector diffractometer	6083 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	3856 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.091
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.0°
ϕ and ω scans	h = −35→35
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −13→13
Tmin = 0.499, Tmax = 0.673	l = −28→28
46446 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.069	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.206	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0974P)^2 + 44.0587P] where P = (Fo^2 + 2Fc^2)/3
6083 reflections	(Δ/σ)max = 0.001
351 parameters	Δρmax = 0.87 e Å^−3
3 restraints	Δρmin = −1.30 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Br77	0.40465 (2)	0.66538 (6)	0.82875 (3)	0.0332 (2)
O51	0.40003 (14)	0.5905 (3)	0.42828 (19)	0.0228 (8)
O55	0.30756 (13)	0.2518 (3)	0.44048 (17)	0.0151 (7)
N1	0.15891 (15)	0.5070 (4)	0.35692 (18)	0.0090 (7)
N2	0.13518 (15)	0.4820 (4)	0.28451 (19)	0.0109 (7)
N7	0.25612 (14)	0.5333 (3)	0.46678 (19)	0.0085 (7)
C3	0.17891 (18)	0.4673 (4)	0.2761 (2)	0.0105 (9)
C3a	0.23227 (18)	0.4803 (4)	0.3433 (2)	0.0098 (8)
C4	0.29344 (18)	0.4690 (4)	0.3629 (2)	0.0120 (9)
C5	0.33537 (18)	0.4665 (4)	0.4457 (2)	0.0117 (9)
C6	0.31333 (17)	0.5621 (4)	0.4803 (2)	0.0099 (8)
C7a	0.21786 (18)	0.5055 (4)	0.3928 (2)	0.0085 (8)
C11	0.12120 (18)	0.5392 (4)	0.3798 (2)	0.0098 (8)
C12	0.13888 (19)	0.6151 (4)	0.4404 (2)	0.0128 (9)
C13	0.10012 (19)	0.6455 (4)	0.4604 (2)	0.0149 (9)
C14	0.0443 (2)	0.6030 (5)	0.4199 (3)	0.0187 (10)
C15	0.0264 (2)	0.5297 (5)	0.3590 (3)	0.0214 (11)
C16	0.06469 (19)	0.4958 (5)	0.3392 (2)	0.0154 (10)
C31	0.16845 (19)	0.4434 (4)	0.2009 (2)	0.0120 (9)
C32	0.1941 (2)	0.3161 (5)	0.2002 (3)	0.0209 (10)
C33	0.1045 (2)	0.4433 (5)	0.1435 (2)	0.0208 (11)
C34	0.1973 (2)	0.5477 (5)	0.1830 (3)	0.0190 (10)
C51	0.39478 (19)	0.5182 (4)	0.4672 (3)	0.0143 (9)
C52	0.4457 (2)	0.4839 (5)	0.5416 (3)	0.0197 (10)
C53	0.44772 (19)	0.3453 (5)	0.5640 (3)	0.0189 (10)
C54	0.3893 (2)	0.3142 (5)	0.5543 (3)	0.0165 (10)
C55	0.34054 (17)	0.3348 (4)	0.4767 (2)	0.0098 (8)
C71	0.28833 (18)	0.5036 (4)	0.5955 (2)	0.0100 (9)
C72	0.31802 (19)	0.4226 (5)	0.6547 (2)	0.0152 (9)
C73	0.3507 (2)	0.4697 (5)	0.7247 (2)	0.0186 (10)
C74	0.3534 (2)	0.5987 (5)	0.7349 (3)	0.0187 (10)
C75	0.3233 (2)	0.6806 (5)	0.6783 (2)	0.0174 (10)
C76	0.2907 (2)	0.6318 (5)	0.6082 (2)	0.0151 (9)
C77	0.25481 (19)	0.4487 (4)	0.5196 (2)	0.0106 (9)
C531	0.4583 (2)	0.2591 (5)	0.5169 (3)	0.0267 (12)
C532	0.4957 (2)	0.3308 (6)	0.6436 (3)	0.0316 (13)
C81	0.4699 (6)	0.6839 (8)	0.7106 (9)	0.052 (3)	0.50
C82	0.5234 (6)	0.6483 (14)	0.7853 (8)	0.052 (3)	0.50
O81	0.4362 (4)	0.5738 (11)	0.6767 (5)	0.059 (3)	0.50
H4A	0.3028	0.5417	0.3422	0.014*
H4B	0.2978	0.3904	0.3414	0.014*
H5A	0.3415	0.5643	0.5337	0.012*
H5B	0.3122	0.6478	0.4611	0.012*
H12	0.1774	0.6460	0.4682	0.015*
H13	0.1123	0.6962	0.5024	0.018*
H14	0.0179	0.6242	0.4339	0.022*
H15	−0.0127	0.5022	0.3303	0.026*
H16	0.0524	0.4429	0.2980	0.018*
H12A	0.1760	0.2487	0.2122	0.031*
H12B	0.2358	0.3168	0.2364	0.031*
H12C	0.1871	0.3007	0.1516	0.031*
H33A	0.0855	0.3761	0.1544	0.031*
H33B	0.0985	0.4281	0.0954	0.031*
H33C	0.0879	0.5255	0.1436	0.031*
H34A	0.2390	0.5465	0.2188	0.028*
H34B	0.1815	0.6301	0.1846	0.028*
H34C	0.1898	0.5337	0.1340	0.028*
H52A	0.4452	0.5387	0.5783	0.024*
H52B	0.4816	0.5028	0.5430	0.024*
H54A	0.3893	0.2248	0.5681	0.020*
H54B	0.3837	0.3686	0.5871	0.020*
H72	0.3158	0.3337	0.6469	0.018*
H73	0.3709	0.4141	0.7652	0.022*
H75	0.3247	0.7693	0.6866	0.021*
H76	0.2695	0.6879	0.5681	0.018*
H77A	0.2715	0.3656	0.5195	0.013*
H77B	0.2142	0.4348	0.5048	0.013*
H53A	0.4951	0.2815	0.5224	0.040*
H53B	0.4270	0.2689	0.4657	0.040*
H53C	0.4598	0.1709	0.5320	0.040*
H53D	0.5328	0.3520	0.6496	0.047*
H53E	0.4967	0.2430	0.6590	0.047*
H53F	0.4886	0.3879	0.6735	0.047*
H81A	0.4822	0.7195	0.6788	0.062*	0.50
H81B	0.4462	0.7482	0.7159	0.062*	0.50
H82A	0.5298	0.5565	0.7893	0.078*	0.50
H82B	0.5574	0.6912	0.7911	0.078*	0.50
H82C	0.5172	0.6769	0.8235	0.078*	0.50
H81	0.4087	0.5718	0.6831	0.088*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br77	0.0305 (3)	0.0400 (4)	0.0194 (3)	−0.0051 (3)	0.0071 (2)	−0.0028 (2)
O51	0.0124 (16)	0.0253 (19)	0.0300 (19)	−0.0031 (14)	0.0109 (15)	0.0098 (16)
O55	0.0147 (16)	0.0105 (15)	0.0205 (17)	−0.0023 (13)	0.0098 (14)	−0.0015 (13)
N1	0.0061 (17)	0.0152 (19)	0.0053 (16)	−0.0009 (14)	0.0028 (14)	−0.0011 (14)
N2	0.0082 (17)	0.0178 (19)	0.0069 (16)	−0.0016 (15)	0.0042 (14)	−0.0018 (15)
N7	0.0051 (17)	0.0133 (18)	0.0084 (16)	−0.0013 (14)	0.0044 (14)	0.0006 (14)
C3	0.010 (2)	0.013 (2)	0.010 (2)	−0.0037 (17)	0.0065 (17)	−0.0008 (17)
C3a	0.009 (2)	0.011 (2)	0.011 (2)	−0.0014 (17)	0.0067 (17)	0.0009 (17)
C4	0.012 (2)	0.014 (2)	0.013 (2)	0.0006 (18)	0.0085 (18)	0.0027 (18)
C5	0.008 (2)	0.015 (2)	0.013 (2)	−0.0015 (17)	0.0058 (17)	0.0001 (18)
C6	0.0044 (19)	0.012 (2)	0.014 (2)	−0.0023 (16)	0.0056 (17)	0.0000 (17)
C7a	0.0066 (19)	0.008 (2)	0.0093 (19)	−0.0012 (16)	0.0034 (17)	0.0014 (16)
C11	0.010 (2)	0.010 (2)	0.012 (2)	0.0023 (17)	0.0081 (17)	0.0030 (17)
C12	0.010 (2)	0.016 (2)	0.013 (2)	−0.0009 (18)	0.0069 (18)	−0.0007 (18)
C13	0.013 (2)	0.017 (2)	0.015 (2)	−0.0009 (18)	0.0085 (18)	−0.0036 (18)
C14	0.019 (2)	0.027 (3)	0.018 (2)	0.001 (2)	0.015 (2)	−0.001 (2)
C15	0.010 (2)	0.033 (3)	0.021 (2)	0.000 (2)	0.009 (2)	−0.002 (2)
C16	0.011 (2)	0.024 (3)	0.013 (2)	−0.0025 (19)	0.0074 (18)	−0.0042 (19)
C31	0.012 (2)	0.017 (2)	0.010 (2)	−0.0035 (18)	0.0071 (18)	−0.0017 (17)
C32	0.025 (3)	0.020 (3)	0.019 (2)	0.000 (2)	0.012 (2)	−0.004 (2)
C33	0.016 (2)	0.036 (3)	0.011 (2)	−0.003 (2)	0.0077 (19)	−0.007 (2)
C34	0.024 (3)	0.023 (3)	0.017 (2)	−0.004 (2)	0.015 (2)	−0.001 (2)
C51	0.010 (2)	0.014 (2)	0.019 (2)	−0.0031 (18)	0.0079 (19)	−0.0036 (19)
C52	0.011 (2)	0.025 (3)	0.019 (2)	−0.007 (2)	0.006 (2)	0.000 (2)
C53	0.008 (2)	0.024 (3)	0.020 (2)	0.0020 (19)	0.0045 (19)	0.007 (2)
C54	0.017 (2)	0.016 (2)	0.019 (2)	−0.0023 (19)	0.011 (2)	0.0027 (19)
C55	0.0063 (19)	0.012 (2)	0.015 (2)	0.0019 (17)	0.0080 (17)	0.0019 (18)
C71	0.0057 (19)	0.013 (2)	0.013 (2)	0.0003 (17)	0.0059 (17)	0.0019 (17)
C72	0.013 (2)	0.015 (2)	0.016 (2)	0.0017 (18)	0.0066 (19)	0.0038 (18)
C73	0.012 (2)	0.021 (3)	0.013 (2)	−0.0029 (19)	0.0006 (18)	0.0060 (19)
C74	0.012 (2)	0.023 (3)	0.015 (2)	−0.005 (2)	0.0028 (19)	−0.004 (2)
C75	0.019 (2)	0.016 (2)	0.015 (2)	0.0013 (19)	0.0078 (19)	−0.0009 (19)
C76	0.014 (2)	0.020 (2)	0.011 (2)	0.0018 (18)	0.0061 (18)	0.0018 (18)
C77	0.012 (2)	0.011 (2)	0.012 (2)	−0.0022 (17)	0.0085 (18)	0.0009 (17)
C531	0.014 (2)	0.031 (3)	0.033 (3)	0.006 (2)	0.011 (2)	0.006 (2)
C532	0.020 (3)	0.033 (3)	0.025 (3)	−0.003 (2)	0.000 (2)	0.010 (2)
C81	0.044 (5)	0.032 (7)	0.068 (6)	−0.008 (5)	0.022 (4)	−0.002 (5)
C82	0.044 (5)	0.032 (7)	0.068 (6)	−0.008 (5)	0.022 (4)	−0.002 (5)
O81	0.037 (5)	0.083 (8)	0.066 (7)	−0.012 (5)	0.034 (5)	−0.007 (6)

Geometric parameters (Å, º)

Br77—C74	1.883 (5)	C33—H33C	0.98
O51—C51	1.203 (6)	C34—H34A	0.98
O55—C55	1.200 (5)	C34—H34B	0.98
N1—N2	1.366 (5)	C34—H34C	0.98
N1—C7a	1.368 (5)	C51—C52	1.507 (6)
N1—C11	1.409 (5)	C52—C53	1.532 (7)
N2—C3	1.317 (6)	C52—H52A	0.99
N7—C7a	1.398 (5)	C52—H52B	0.99
N7—C6	1.466 (5)	C53—C531	1.511 (7)
N7—C77	1.469 (5)	C53—C532	1.516 (7)
C3—C3a	1.413 (6)	C53—C54	1.535 (6)
C3—C31	1.519 (6)	C54—C55	1.502 (6)
C3a—C7a	1.358 (6)	C54—H54A	0.99
C3a—C4	1.499 (6)	C54—H54B	0.99
C4—C5	1.529 (6)	C71—C76	1.375 (7)
C4—H4A	0.99	C71—C72	1.386 (6)
C4—H4B	0.99	C71—C77	1.507 (6)
C5—C55	1.516 (6)	C72—C73	1.377 (6)
C5—C51	1.536 (6)	C72—H72	0.95
C5—C6	1.562 (6)	C73—C74	1.374 (7)
C6—H5A	0.99	C73—H73	0.95
C6—H5B	0.99	C74—C75	1.361 (7)
C11—C16	1.387 (6)	C75—C76	1.386 (6)
C11—C12	1.387 (6)	C75—H75	0.95
C12—C13	1.385 (6)	C76—H76	0.95
C12—H12	0.95	C77—H77A	0.99
C13—C14	1.369 (7)	C77—H77B	0.99
C13—H13	0.95	C531—H53A	0.98
C14—C15	1.375 (7)	C531—H53B	0.98
C14—H14	0.95	C531—H53C	0.98
C15—C16	1.379 (6)	C532—H53D	0.98
C15—H15	0.95	C532—H53E	0.98
C16—H16	0.95	C532—H53F	0.98
C31—C33	1.512 (6)	C81—O81	1.4201 (10)
C31—C32	1.521 (6)	C81—C82	1.5398 (11)
C31—C34	1.523 (6)	C81—H81A	0.99
C32—H12A	0.98	C81—H81B	0.99
C32—H12B	0.98	C82—H82A	0.98
C32—H12C	0.98	C82—H82B	0.98
C33—H33A	0.98	C82—H82C	0.98
C33—H33B	0.98	O81—H81	0.84
N2—N1—C7a	109.9 (3)	H34B—C34—H34C	109.5
N2—N1—C11	117.8 (3)	O51—C51—C52	121.0 (4)
C7a—N1—C11	132.0 (4)	O51—C51—C5	121.4 (4)
C3—N2—N1	106.0 (3)	C52—C51—C5	117.4 (4)
C7a—N7—C6	109.7 (3)	C51—C52—C53	115.2 (4)
C7a—N7—C77	116.8 (3)	C51—C52—H52A	108.5
C6—N7—C77	116.2 (3)	C53—C52—H52A	108.5
N2—C3—C3a	111.2 (4)	C51—C52—H52B	108.5
N2—C3—C31	120.6 (4)	C53—C52—H52B	108.5
C3a—C3—C31	128.2 (4)	H52A—C52—H52B	107.5
C7a—C3a—C3	104.8 (4)	C531—C53—C532	110.2 (4)
C7a—C3a—C4	123.3 (4)	C531—C53—C52	110.3 (4)
C3—C3a—C4	131.8 (4)	C532—C53—C52	108.6 (4)
C3a—C4—C5	110.8 (3)	C531—C53—C54	110.2 (4)
C3a—C4—H4A	109.5	C532—C53—C54	109.8 (4)
C5—C4—H4A	109.5	C52—C53—C54	107.6 (4)
C3a—C4—H4B	109.5	C55—C54—C53	111.0 (4)
C5—C4—H4B	109.5	C55—C54—H54A	109.4
H4A—C4—H4B	108.1	C53—C54—H54A	109.4
C55—C5—C4	111.7 (4)	C55—C54—H54B	109.4
C55—C5—C51	111.1 (4)	C53—C54—H54B	109.4
C4—C5—C51	110.9 (3)	H54A—C54—H54B	108.0
C55—C5—C6	110.3 (3)	O55—C55—C54	122.2 (4)
C4—C5—C6	108.3 (3)	O55—C55—C5	121.3 (4)
C51—C5—C6	104.3 (3)	C54—C55—C5	116.4 (4)
N7—C6—C5	114.8 (3)	C76—C71—C72	118.7 (4)
N7—C6—H5A	108.6	C76—C71—C77	122.1 (4)
C5—C6—H5A	108.6	C72—C71—C77	119.2 (4)
N7—C6—H5B	108.6	C73—C72—C71	120.7 (4)
C5—C6—H5B	108.6	C73—C72—H72	119.6
H5A—C6—H5B	107.5	C71—C72—H72	119.6
C3a—C7a—N1	108.0 (4)	C74—C73—C72	118.8 (4)
C3a—C7a—N7	126.4 (4)	C74—C73—H73	120.6
N1—C7a—N7	125.5 (4)	C72—C73—H73	120.6
C16—C11—C12	119.7 (4)	C75—C74—C73	122.0 (4)
C16—C11—N1	118.6 (4)	C75—C74—Br77	118.6 (4)
C12—C11—N1	121.7 (4)	C73—C74—Br77	119.3 (4)
C13—C12—C11	119.7 (4)	C74—C75—C76	118.5 (5)
C13—C12—H12	120.2	C74—C75—H75	120.8
C11—C12—H12	120.2	C76—C75—H75	120.8
C14—C13—C12	120.4 (4)	C71—C76—C75	121.2 (4)
C14—C13—H13	119.8	C71—C76—H76	119.4
C12—C13—H13	119.8	C75—C76—H76	119.4
C13—C14—C15	120.1 (4)	N7—C77—C71	111.4 (3)
C13—C14—H14	120.0	N7—C77—H77A	109.3
C15—C14—H14	120.0	C71—C77—H77A	109.3
C14—C15—C16	120.4 (4)	N7—C77—H77B	109.3
C14—C15—H15	119.8	C71—C77—H77B	109.3
C16—C15—H15	119.8	H77A—C77—H77B	108.0
C15—C16—C11	119.7 (4)	C53—C531—H53A	109.5
C15—C16—H16	120.1	C53—C531—H53B	109.5
C11—C16—H16	120.1	H53A—C531—H53B	109.5
C33—C31—C3	110.6 (4)	C53—C531—H53C	109.5
C33—C31—C32	109.3 (4)	H53A—C531—H53C	109.5
C3—C31—C32	109.7 (4)	H53B—C531—H53C	109.5
C33—C31—C34	108.8 (4)	C53—C532—H53D	109.5
C3—C31—C34	109.2 (4)	C53—C532—H53E	109.5
C32—C31—C34	109.2 (4)	H53D—C532—H53E	109.5
C31—C32—H12A	109.5	C53—C532—H53F	109.5
C31—C32—H12B	109.5	H53D—C532—H53F	109.5
H12A—C32—H12B	109.5	H53E—C532—H53F	109.5
C31—C32—H12C	109.5	O81—C81—C82	109.50 (16)
H12A—C32—H12C	109.5	O81—C81—H81A	108.7
H12B—C32—H12C	109.5	C82—C81—H81A	109.8
C31—C33—H33A	109.5	O81—C81—H81B	109.5
C31—C33—H33B	109.5	C82—C81—H81B	111.1
H33A—C33—H33B	109.5	H81A—C81—H81B	108.2
C31—C33—H33C	109.5	C81—C82—H82A	110.9
H33A—C33—H33C	109.5	C81—C82—H82B	109.0
H33B—C33—H33C	109.5	H82A—C82—H82B	109.5
C31—C34—H34A	109.5	C81—C82—H82C	108.4
C31—C34—H34B	109.5	H82A—C82—H82C	109.5
H34A—C34—H34B	109.5	H82B—C82—H82C	109.5
C31—C34—H34C	109.5	C81—O81—H81	109.2
H34A—C34—H34C	109.5
C7a—N1—N2—C3	−0.9 (5)	N2—C3—C31—C33	1.4 (6)
C11—N1—N2—C3	173.8 (4)	C3a—C3—C31—C33	−176.8 (4)
N1—N2—C3—C3a	1.0 (5)	N2—C3—C31—C32	−119.2 (5)
N1—N2—C3—C31	−177.5 (4)	C3a—C3—C31—C32	62.5 (6)
N2—C3—C3a—C7a	−0.8 (5)	N2—C3—C31—C34	121.1 (5)
C31—C3—C3a—C7a	177.6 (4)	C3a—C3—C31—C34	−57.1 (6)
N2—C3—C3a—C4	178.3 (4)	C55—C5—C51—O51	149.6 (4)
C31—C3—C3a—C4	−3.4 (8)	C4—C5—C51—O51	24.7 (6)
C7a—C3a—C4—C5	9.9 (6)	C6—C5—C51—O51	−91.6 (5)
C3—C3a—C4—C5	−169.0 (4)	C55—C5—C51—C52	−35.5 (5)
C3a—C4—C5—C55	82.8 (4)	C4—C5—C51—C52	−160.3 (4)
C3a—C4—C5—C51	−152.7 (4)	C6—C5—C51—C52	83.3 (5)
C3a—C4—C5—C6	−38.9 (5)	O51—C51—C52—C53	−142.0 (5)
C7a—N7—C6—C5	−46.9 (5)	C5—C51—C52—C53	43.1 (6)
C77—N7—C6—C5	88.3 (4)	C51—C52—C53—C531	67.5 (5)
C55—C5—C6—N7	−61.1 (5)	C51—C52—C53—C532	−171.6 (4)
C4—C5—C6—N7	61.4 (5)	C51—C52—C53—C54	−52.8 (5)
C51—C5—C6—N7	179.5 (3)	C531—C53—C54—C55	−61.6 (5)
C3—C3a—C7a—N1	0.2 (5)	C532—C53—C54—C55	176.8 (4)
C4—C3a—C7a—N1	−178.9 (4)	C52—C53—C54—C55	58.7 (5)
C3—C3a—C7a—N7	−176.0 (4)	C53—C54—C55—O55	122.1 (5)
C4—C3a—C7a—N7	4.8 (7)	C53—C54—C55—C5	−57.2 (5)
N2—N1—C7a—C3a	0.4 (5)	C4—C5—C55—O55	−11.8 (6)
C11—N1—C7a—C3a	−173.3 (4)	C51—C5—C55—O55	−136.2 (4)
N2—N1—C7a—N7	176.7 (4)	C6—C5—C55—O55	108.7 (4)
C11—N1—C7a—N7	3.0 (7)	C4—C5—C55—C54	167.4 (4)
C6—N7—C7a—C3a	13.8 (6)	C51—C5—C55—C54	43.0 (5)
C77—N7—C7a—C3a	−121.2 (5)	C6—C5—C55—C54	−72.1 (4)
C6—N7—C7a—N1	−161.8 (4)	C76—C71—C72—C73	−1.9 (7)
C77—N7—C7a—N1	63.2 (6)	C77—C71—C72—C73	177.8 (4)
N2—N1—C11—C16	26.2 (6)	C71—C72—C73—C74	−0.2 (7)
C7a—N1—C11—C16	−160.5 (5)	C72—C73—C74—C75	2.4 (7)
N2—N1—C11—C12	−152.4 (4)	C72—C73—C74—Br77	−172.8 (3)
C7a—N1—C11—C12	21.0 (7)	C73—C74—C75—C76	−2.3 (7)
C16—C11—C12—C13	0.7 (7)	Br77—C74—C75—C76	172.9 (3)
N1—C11—C12—C13	179.3 (4)	C72—C71—C76—C75	2.0 (7)
C11—C12—C13—C14	−1.1 (7)	C77—C71—C76—C75	−177.7 (4)
C12—C13—C14—C15	0.0 (7)	C74—C75—C76—C71	0.1 (7)
C13—C14—C15—C16	1.6 (8)	C7a—N7—C77—C71	−168.1 (4)
C14—C15—C16—C11	−2.0 (8)	C6—N7—C77—C71	59.9 (5)
C12—C11—C16—C15	0.8 (7)	C76—C71—C77—N7	34.0 (6)
N1—C11—C16—C15	−177.8 (4)	C72—C71—C77—N7	−145.7 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O81—H81···Cg1	0.84	2.25	3.060 (13)	163
C52—H52A···O81	0.99	2.31	3.224 (12)	153
C75—H75···Cg2^i	0.95	2.58	3.498 (6)	164

Symmetry code: (i) −x+1/2, −y+3/2, −z+1.

(III) 3-tert-Butyl-4',4'-dimethyl-7-(4-methylbenzyl)-1-phenyl-4,5,6,7- tetrahydro-1H-pyrazolo[3,4-b]pyridine-5-spiro-1'-cyclohexane- 2',6'-dione ethanol hemisolvate

Crystal data

C31H37N3O2·0.5C2H6O	F(000) = 2184
Mr = 506.67	Dx = 1.268 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 6079 reflections
a = 27.281 (5) Å	θ = 3.0–27.5°
b = 10.6438 (15) Å	µ = 0.08 mm^−1
c = 21.567 (3) Å	T = 120 K
β = 122.082 (12)°	Plate, colourless
V = 5306.1 (16) Å^3	0.51 × 0.30 × 0.07 mm
Z = 8

Data collection

Bruker Nonius KappaCCD area-detector diffractometer	6079 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	3421 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.118
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.0°
ϕ and ω scans	h = −35→35
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −13→13
Tmin = 0.966, Tmax = 0.994	l = −28→28
48672 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.064	H-atom parameters constrained
wR(F^2) = 0.178	w = 1/[σ^2(Fo^2) + (0.0798P)^2 + 5.3581P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
6079 reflections	Δρmax = 0.33 e Å^−3
353 parameters	Δρmin = −0.42 e Å^−3
3 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0013 (3)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
O51	0.40116 (8)	0.57688 (18)	0.42391 (10)	0.0338 (5)
O55	0.30648 (7)	0.25161 (16)	0.43702 (10)	0.0310 (4)
N1	0.15866 (8)	0.5062 (2)	0.35618 (10)	0.0231 (5)
N2	0.13449 (9)	0.4803 (2)	0.28306 (11)	0.0255 (5)
N7	0.25593 (8)	0.53193 (19)	0.46551 (11)	0.0231 (5)
C3	0.17842 (10)	0.4655 (2)	0.27438 (13)	0.0228 (5)
C3a	0.23187 (10)	0.4787 (2)	0.34157 (13)	0.0225 (5)
C4	0.29293 (10)	0.4681 (2)	0.36048 (13)	0.0239 (6)
C5	0.33488 (10)	0.4648 (2)	0.44311 (13)	0.0231 (5)
C6	0.31297 (10)	0.5592 (2)	0.47861 (14)	0.0244 (6)
C7a	0.21749 (10)	0.5043 (2)	0.39186 (13)	0.0231 (5)
C11	0.12056 (11)	0.5395 (2)	0.37907 (13)	0.0238 (5)
C12	0.13788 (11)	0.6173 (2)	0.43854 (14)	0.0277 (6)
C13	0.09940 (11)	0.6477 (3)	0.45937 (14)	0.0306 (6)
C14	0.04337 (12)	0.6045 (3)	0.41959 (15)	0.0337 (7)
C15	0.02575 (11)	0.5303 (3)	0.35935 (15)	0.0341 (7)
C16	0.06436 (11)	0.4959 (3)	0.33921 (14)	0.0298 (6)
C31	0.16826 (11)	0.4382 (2)	0.19967 (13)	0.0262 (6)
C32	0.19113 (12)	0.3083 (3)	0.19900 (15)	0.0346 (7)
C33	0.10375 (11)	0.4429 (3)	0.14166 (14)	0.0358 (7)
C34	0.19923 (12)	0.5361 (3)	0.18114 (15)	0.0326 (6)
C51	0.39511 (10)	0.5122 (2)	0.46521 (14)	0.0249 (6)
C52	0.44470 (11)	0.4807 (3)	0.54006 (14)	0.0299 (6)
C53	0.44664 (11)	0.3431 (3)	0.56176 (14)	0.0296 (6)
C54	0.38808 (11)	0.3108 (3)	0.55163 (14)	0.0291 (6)
C55	0.33985 (10)	0.3333 (2)	0.47468 (14)	0.0246 (6)
C71	0.28853 (10)	0.5055 (2)	0.59495 (13)	0.0227 (5)
C72	0.31999 (10)	0.4286 (2)	0.65533 (14)	0.0272 (6)
C73	0.35308 (11)	0.4790 (3)	0.72453 (14)	0.0298 (6)
C74	0.35590 (11)	0.6068 (3)	0.73634 (14)	0.0273 (6)
C741	0.39465 (12)	0.6627 (3)	0.81042 (14)	0.0387 (7)
C75	0.32280 (11)	0.6827 (3)	0.67639 (13)	0.0280 (6)
C76	0.28970 (11)	0.6338 (2)	0.60699 (13)	0.0263 (6)
C77	0.25438 (11)	0.4507 (2)	0.51933 (13)	0.0243 (6)
C531	0.45835 (12)	0.2583 (3)	0.51433 (15)	0.0359 (7)
C532	0.49461 (13)	0.3270 (3)	0.64164 (15)	0.0429 (8)
C81	0.4701 (3)	0.6818 (4)	0.7065 (4)	0.0559 (12)	0.50
C82	0.5207 (3)	0.6490 (7)	0.7840 (4)	0.0559 (12)	0.50
O81	0.4364 (2)	0.5726 (5)	0.6728 (3)	0.0729 (16)	0.50
H4A	0.3022	0.5407	0.3397	0.029*
H4B	0.2973	0.3905	0.3385	0.029*
H5A	0.3411	0.5604	0.5321	0.029*
H5B	0.3123	0.6444	0.4598	0.029*
H12	0.1761	0.6498	0.4651	0.033*
H13	0.1117	0.6986	0.5013	0.037*
H14	0.0169	0.6260	0.4338	0.040*
H15	−0.0132	0.5022	0.3312	0.041*
H16	0.0522	0.4426	0.2982	0.036*
H12A	0.1705	0.2450	0.2096	0.052*
H12B	0.2326	0.3042	0.2363	0.052*
H12C	0.1851	0.2920	0.1507	0.052*
H33A	0.0834	0.3803	0.1531	0.054*
H33B	0.0977	0.4247	0.0935	0.054*
H33C	0.0887	0.5268	0.1411	0.054*
H34A	0.2411	0.5296	0.2160	0.049*
H34B	0.1860	0.6202	0.1841	0.049*
H34C	0.1906	0.5214	0.1314	0.049*
H52A	0.4426	0.5345	0.5760	0.036*
H52B	0.4812	0.5010	0.5428	0.036*
H54A	0.3880	0.2215	0.5644	0.035*
H54B	0.3821	0.3629	0.5851	0.035*
H72	0.3188	0.3401	0.6490	0.033*
H73	0.3745	0.4243	0.7651	0.036*
H74A	0.4191	0.7273	0.8077	0.058*
H74B	0.4192	0.5968	0.8447	0.058*
H74C	0.3711	0.7007	0.8275	0.058*
H75	0.3229	0.7709	0.6832	0.034*
H76	0.2673	0.6885	0.5668	0.032*
H77A	0.2703	0.3672	0.5193	0.029*
H77B	0.2137	0.4390	0.5052	0.029*
H53A	0.4957	0.2804	0.5210	0.054*
H53B	0.4277	0.2693	0.4628	0.054*
H53C	0.4592	0.1705	0.5286	0.054*
H53D	0.5318	0.3504	0.6480	0.064*
H53E	0.4961	0.2392	0.6561	0.064*
H53F	0.4869	0.3812	0.6722	0.064*
H81A	0.4858	0.7116	0.6770	0.067*	0.50
H81B	0.4467	0.7503	0.7091	0.067*	0.50
H82A	0.5526	0.6126	0.7815	0.084*	0.50
H82B	0.5342	0.7250	0.8143	0.084*	0.50
H82C	0.5072	0.5878	0.8057	0.084*	0.50
H81	0.4081	0.5745	0.6783	0.109*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O51	0.0262 (10)	0.0413 (12)	0.0347 (11)	−0.0041 (8)	0.0167 (9)	0.0063 (9)
O55	0.0281 (10)	0.0274 (10)	0.0360 (11)	−0.0039 (8)	0.0159 (9)	−0.0039 (9)
N1	0.0191 (10)	0.0315 (12)	0.0200 (11)	−0.0025 (9)	0.0114 (9)	−0.0024 (9)
N2	0.0235 (11)	0.0320 (12)	0.0226 (11)	−0.0018 (9)	0.0134 (10)	−0.0013 (9)
N7	0.0219 (11)	0.0286 (12)	0.0201 (11)	−0.0024 (9)	0.0121 (9)	0.0001 (9)
C3	0.0203 (13)	0.0242 (13)	0.0238 (13)	−0.0001 (10)	0.0115 (11)	−0.0002 (10)
C3a	0.0212 (12)	0.0231 (13)	0.0237 (13)	−0.0002 (10)	0.0122 (11)	0.0020 (10)
C4	0.0188 (12)	0.0299 (14)	0.0225 (13)	−0.0019 (11)	0.0106 (11)	−0.0006 (11)
C5	0.0232 (13)	0.0253 (13)	0.0218 (13)	−0.0006 (11)	0.0126 (11)	0.0006 (10)
C6	0.0223 (13)	0.0276 (13)	0.0242 (13)	−0.0020 (11)	0.0130 (11)	−0.0001 (11)
C7a	0.0214 (13)	0.0263 (13)	0.0216 (13)	−0.0020 (10)	0.0115 (11)	−0.0009 (11)
C11	0.0234 (13)	0.0280 (14)	0.0230 (13)	−0.0002 (11)	0.0143 (11)	0.0010 (11)
C12	0.0251 (14)	0.0308 (14)	0.0290 (14)	−0.0033 (11)	0.0157 (12)	−0.0008 (12)
C13	0.0354 (15)	0.0341 (15)	0.0285 (14)	−0.0002 (12)	0.0211 (13)	−0.0018 (12)
C14	0.0281 (15)	0.0446 (17)	0.0359 (16)	−0.0022 (13)	0.0221 (13)	−0.0045 (13)
C15	0.0238 (14)	0.0487 (18)	0.0329 (15)	−0.0056 (12)	0.0173 (13)	−0.0068 (13)
C16	0.0247 (14)	0.0399 (16)	0.0265 (14)	−0.0041 (12)	0.0148 (12)	−0.0040 (12)
C31	0.0238 (13)	0.0330 (15)	0.0234 (13)	−0.0033 (11)	0.0135 (11)	−0.0038 (11)
C32	0.0402 (16)	0.0351 (16)	0.0304 (15)	−0.0008 (13)	0.0199 (14)	−0.0050 (12)
C33	0.0250 (14)	0.060 (2)	0.0227 (14)	−0.0023 (13)	0.0126 (12)	−0.0077 (13)
C34	0.0337 (15)	0.0401 (17)	0.0286 (15)	−0.0030 (13)	0.0196 (13)	0.0007 (12)
C51	0.0236 (13)	0.0257 (13)	0.0289 (14)	−0.0012 (11)	0.0164 (12)	−0.0025 (11)
C52	0.0234 (13)	0.0366 (15)	0.0257 (14)	−0.0054 (12)	0.0103 (12)	−0.0010 (12)
C53	0.0228 (13)	0.0356 (15)	0.0252 (14)	−0.0026 (11)	0.0092 (12)	0.0024 (12)
C54	0.0293 (14)	0.0303 (14)	0.0262 (14)	0.0006 (11)	0.0137 (12)	0.0035 (11)
C55	0.0218 (13)	0.0262 (14)	0.0292 (14)	0.0000 (11)	0.0159 (12)	0.0004 (11)
C71	0.0196 (12)	0.0295 (14)	0.0218 (13)	−0.0002 (11)	0.0128 (11)	−0.0007 (11)
C72	0.0237 (13)	0.0297 (14)	0.0295 (15)	0.0003 (11)	0.0150 (12)	0.0031 (12)
C73	0.0224 (13)	0.0375 (16)	0.0243 (14)	−0.0005 (12)	0.0089 (12)	0.0068 (12)
C74	0.0240 (13)	0.0350 (15)	0.0248 (14)	−0.0066 (11)	0.0142 (12)	−0.0015 (11)
C741	0.0356 (16)	0.0496 (18)	0.0248 (15)	−0.0087 (14)	0.0118 (13)	−0.0019 (13)
C75	0.0286 (14)	0.0300 (15)	0.0268 (14)	−0.0020 (11)	0.0156 (12)	0.0003 (11)
C76	0.0246 (13)	0.0302 (14)	0.0232 (14)	0.0002 (11)	0.0121 (11)	0.0023 (11)
C77	0.0273 (13)	0.0249 (13)	0.0247 (14)	−0.0013 (11)	0.0166 (12)	0.0015 (10)
C531	0.0276 (15)	0.0440 (17)	0.0352 (16)	0.0050 (13)	0.0161 (13)	0.0049 (13)
C532	0.0344 (16)	0.0487 (19)	0.0307 (16)	0.0000 (14)	0.0071 (14)	0.0039 (14)
C81	0.054 (3)	0.053 (3)	0.057 (3)	−0.008 (3)	0.027 (2)	−0.002 (3)
C82	0.054 (3)	0.053 (3)	0.057 (3)	−0.008 (3)	0.027 (2)	−0.002 (3)
O81	0.058 (3)	0.092 (4)	0.082 (4)	−0.025 (3)	0.046 (3)	−0.039 (3)

Geometric parameters (Å, º)

O51—C51	1.205 (3)	C34—H34C	0.98
O55—C55	1.208 (3)	C51—C52	1.493 (4)
N1—C7a	1.362 (3)	C52—C53	1.530 (4)
N1—N2	1.376 (3)	C52—H52A	0.99
N1—C11	1.413 (3)	C52—H52B	0.99
N2—C3	1.317 (3)	C53—C531	1.520 (4)
N7—C7a	1.393 (3)	C53—C532	1.521 (4)
N7—C6	1.456 (3)	C53—C54	1.532 (4)
N7—C77	1.466 (3)	C54—C55	1.491 (3)
C3—C3a	1.415 (3)	C54—H54A	0.99
C3—C31	1.511 (3)	C54—H54B	0.99
C3a—C7a	1.362 (3)	C71—C72	1.384 (3)
C3a—C4	1.494 (3)	C71—C76	1.387 (4)
C4—C5	1.523 (3)	C71—C77	1.501 (3)
C4—H4A	0.99	C72—C73	1.378 (4)
C4—H4B	0.99	C72—H72	0.95
C5—C55	1.530 (3)	C73—C74	1.378 (4)
C5—C51	1.533 (3)	C73—H73	0.95
C5—C6	1.562 (3)	C74—C75	1.378 (4)
C6—H5A	0.99	C74—C741	1.494 (4)
C6—H5B	0.99	C741—H74A	0.98
C11—C16	1.380 (4)	C741—H74B	0.98
C11—C12	1.382 (4)	C741—H74C	0.98
C12—C13	1.382 (3)	C75—C76	1.375 (3)
C12—H12	0.95	C75—H75	0.95
C13—C14	1.375 (4)	C76—H76	0.95
C13—H13	0.95	C77—H77A	0.99
C14—C15	1.371 (4)	C77—H77B	0.99
C14—H14	0.95	C531—H53A	0.98
C15—C16	1.385 (4)	C531—H53B	0.98
C15—H15	0.95	C531—H53C	0.98
C16—H16	0.95	C532—H53D	0.98
C31—C32	1.520 (4)	C532—H53E	0.98
C31—C34	1.522 (4)	C532—H53F	0.98
C31—C33	1.525 (4)	C81—O81	1.4201 (10)
C32—H12A	0.98	C81—C82	1.5393 (11)
C32—H12B	0.98	C81—H81A	0.99
C32—H12C	0.98	C81—H81B	0.99
C33—H33A	0.98	C82—H82A	0.98
C33—H33B	0.98	C82—H82B	0.98
C33—H33C	0.98	C82—H82C	0.98
C34—H34A	0.98	O81—H81	0.84
C34—H34B	0.98
C7a—N1—N2	110.37 (18)	C52—C51—C5	117.9 (2)
C7a—N1—C11	132.1 (2)	C51—C52—C53	114.2 (2)
N2—N1—C11	117.21 (19)	C51—C52—H52A	108.7
C3—N2—N1	105.58 (19)	C53—C52—H52A	108.7
C7a—N7—C6	110.08 (19)	C51—C52—H52B	108.7
C7a—N7—C77	117.2 (2)	C53—C52—H52B	108.7
C6—N7—C77	116.2 (2)	H52A—C52—H52B	107.6
N2—C3—C3a	111.3 (2)	C531—C53—C532	109.5 (2)
N2—C3—C31	120.6 (2)	C531—C53—C52	110.4 (2)
C3a—C3—C31	128.1 (2)	C532—C53—C52	108.8 (2)
C7a—C3a—C3	105.0 (2)	C531—C53—C54	110.3 (2)
C7a—C3a—C4	123.3 (2)	C532—C53—C54	109.9 (2)
C3—C3a—C4	131.7 (2)	C52—C53—C54	107.9 (2)
C3a—C4—C5	110.9 (2)	C55—C54—C53	111.1 (2)
C3a—C4—H4A	109.5	C55—C54—H54A	109.4
C5—C4—H4A	109.5	C53—C54—H54A	109.4
C3a—C4—H4B	109.5	C55—C54—H54B	109.4
C5—C4—H4B	109.5	C53—C54—H54B	109.4
H4A—C4—H4B	108.0	H54A—C54—H54B	108.0
C4—C5—C55	112.1 (2)	O55—C55—C54	122.5 (2)
C4—C5—C51	111.8 (2)	O55—C55—C5	120.1 (2)
C55—C5—C51	109.6 (2)	C54—C55—C5	117.3 (2)
C4—C5—C6	108.3 (2)	C72—C71—C76	117.7 (2)
C55—C5—C6	109.67 (19)	C72—C71—C77	120.6 (2)
C51—C5—C6	105.19 (19)	C76—C71—C77	121.7 (2)
N7—C6—C5	115.1 (2)	C73—C72—C71	120.8 (2)
N7—C6—H5A	108.5	C73—C72—H72	119.6
C5—C6—H5A	108.5	C71—C72—H72	119.6
N7—C6—H5B	108.5	C72—C73—C74	121.6 (2)
C5—C6—H5B	108.5	C72—C73—H73	119.2
H5A—C6—H5B	107.5	C74—C73—H73	119.2
N1—C7a—C3a	107.7 (2)	C73—C74—C75	117.4 (2)
N1—C7a—N7	126.1 (2)	C73—C74—C741	122.0 (2)
C3a—C7a—N7	126.1 (2)	C75—C74—C741	120.6 (2)
C16—C11—C12	119.9 (2)	C74—C741—H74A	109.5
C16—C11—N1	118.5 (2)	C74—C741—H74B	109.5
C12—C11—N1	121.5 (2)	H74A—C741—H74B	109.5
C13—C12—C11	119.8 (2)	C74—C741—H74C	109.5
C13—C12—H12	120.1	H74A—C741—H74C	109.5
C11—C12—H12	120.1	H74B—C741—H74C	109.5
C14—C13—C12	120.2 (2)	C76—C75—C74	121.6 (2)
C14—C13—H13	119.9	C76—C75—H75	119.2
C12—C13—H13	119.9	C74—C75—H75	119.2
C15—C14—C13	119.9 (2)	C75—C76—C71	120.9 (2)
C15—C14—H14	120.1	C75—C76—H76	119.6
C13—C14—H14	120.1	C71—C76—H76	119.6
C14—C15—C16	120.5 (2)	N7—C77—C71	111.7 (2)
C14—C15—H15	119.8	N7—C77—H77A	109.3
C16—C15—H15	119.8	C71—C77—H77A	109.3
C11—C16—C15	119.6 (2)	N7—C77—H77B	109.3
C11—C16—H16	120.2	C71—C77—H77B	109.3
C15—C16—H16	120.2	H77A—C77—H77B	108.0
C3—C31—C32	110.0 (2)	C53—C531—H53A	109.5
C3—C31—C34	109.6 (2)	C53—C531—H53B	109.5
C32—C31—C34	109.4 (2)	H53A—C531—H53B	109.5
C3—C31—C33	110.3 (2)	C53—C531—H53C	109.5
C32—C31—C33	108.8 (2)	H53A—C531—H53C	109.5
C34—C31—C33	108.8 (2)	H53B—C531—H53C	109.5
C31—C32—H12A	109.5	C53—C532—H53D	109.5
C31—C32—H12B	109.5	C53—C532—H53E	109.5
H12A—C32—H12B	109.5	H53D—C532—H53E	109.5
C31—C32—H12C	109.5	C53—C532—H53F	109.5
H12A—C32—H12C	109.5	H53D—C532—H53F	109.5
H12B—C32—H12C	109.5	H53E—C532—H53F	109.5
C31—C33—H33A	109.5	O81—C81—C82	109.50 (16)
C31—C33—H33B	109.5	O81—C81—H81A	108.4
H33A—C33—H33B	109.5	C82—C81—H81A	109.1
C31—C33—H33C	109.5	O81—C81—H81B	111.7
H33A—C33—H33C	109.5	C82—C81—H81B	109.9
H33B—C33—H33C	109.5	H81A—C81—H81B	108.2
C31—C34—H34A	109.5	C81—C82—H82A	109.9
C31—C34—H34B	109.5	C81—C82—H82B	109.8
H34A—C34—H34B	109.5	H82A—C82—H82B	109.5
C31—C34—H34C	109.5	C81—C82—H82C	108.7
H34A—C34—H34C	109.5	H82A—C82—H82C	109.5
H34B—C34—H34C	109.5	H82B—C82—H82C	109.5
O51—C51—C52	121.8 (2)	C81—O81—H81	107.5
O51—C51—C5	120.2 (2)
C7a—N1—N2—C3	−1.2 (3)	N2—C3—C31—C32	−115.3 (3)
C11—N1—N2—C3	173.4 (2)	C3a—C3—C31—C32	64.7 (3)
N1—N2—C3—C3a	1.2 (3)	N2—C3—C31—C34	124.5 (3)
N1—N2—C3—C31	−178.8 (2)	C3a—C3—C31—C34	−55.6 (3)
N2—C3—C3a—C7a	−0.8 (3)	N2—C3—C31—C33	4.8 (3)
C31—C3—C3a—C7a	179.2 (2)	C3a—C3—C31—C33	−175.3 (3)
N2—C3—C3a—C4	178.7 (2)	C4—C5—C51—O51	20.3 (3)
C31—C3—C3a—C4	−1.3 (4)	C55—C5—C51—O51	145.2 (2)
C7a—C3a—C4—C5	10.8 (3)	C6—C5—C51—O51	−97.0 (3)
C3—C3a—C4—C5	−168.7 (3)	C4—C5—C51—C52	−162.6 (2)
C3a—C4—C5—C55	81.9 (2)	C55—C5—C51—C52	−37.7 (3)
C3a—C4—C5—C51	−154.5 (2)	C6—C5—C51—C52	80.2 (3)
C3a—C4—C5—C6	−39.1 (3)	O51—C51—C52—C53	−136.4 (3)
C7a—N7—C6—C5	−46.2 (3)	C5—C51—C52—C53	46.5 (3)
C77—N7—C6—C5	90.1 (3)	C51—C52—C53—C531	66.3 (3)
C4—C5—C6—N7	61.0 (3)	C51—C52—C53—C532	−173.5 (2)
C55—C5—C6—N7	−61.6 (3)	C51—C52—C53—C54	−54.3 (3)
C51—C5—C6—N7	−179.4 (2)	C531—C53—C54—C55	−62.7 (3)
N2—N1—C7a—C3a	0.8 (3)	C532—C53—C54—C55	176.5 (2)
C11—N1—C7a—C3a	−172.8 (2)	C52—C53—C54—C55	57.9 (3)
N2—N1—C7a—N7	176.9 (2)	C53—C54—C55—O55	122.3 (3)
C11—N1—C7a—N7	3.3 (4)	C53—C54—C55—C5	−55.7 (3)
C3—C3a—C7a—N1	0.0 (3)	C4—C5—C55—O55	−10.5 (3)
C4—C3a—C7a—N1	−179.6 (2)	C51—C5—C55—O55	−135.2 (2)
C3—C3a—C7a—N7	−176.1 (2)	C6—C5—C55—O55	109.8 (3)
C4—C3a—C7a—N7	4.3 (4)	C4—C5—C55—C54	167.5 (2)
C6—N7—C7a—N1	−161.9 (2)	C51—C5—C55—C54	42.8 (3)
C77—N7—C7a—N1	62.3 (3)	C6—C5—C55—C54	−72.2 (3)
C6—N7—C7a—C3a	13.5 (3)	C76—C71—C72—C73	−2.6 (4)
C77—N7—C7a—C3a	−122.3 (3)	C77—C71—C72—C73	177.6 (2)
C7a—N1—C11—C16	−159.9 (3)	C71—C72—C73—C74	0.4 (4)
N2—N1—C11—C16	26.8 (3)	C72—C73—C74—C75	2.0 (4)
C7a—N1—C11—C12	22.1 (4)	C72—C73—C74—C741	−175.9 (2)
N2—N1—C11—C12	−151.1 (2)	C73—C74—C75—C76	−2.2 (4)
C16—C11—C12—C13	2.2 (4)	C741—C74—C75—C76	175.7 (2)
N1—C11—C12—C13	−179.9 (2)	C74—C75—C76—C71	0.0 (4)
C11—C12—C13—C14	−2.3 (4)	C72—C71—C76—C75	2.4 (4)
C12—C13—C14—C15	0.4 (4)	C77—C71—C76—C75	−177.8 (2)
C13—C14—C15—C16	1.6 (4)	C7a—N7—C77—C71	−168.2 (2)
C12—C11—C16—C15	−0.2 (4)	C6—N7—C77—C71	58.6 (3)
N1—C11—C16—C15	−178.2 (2)	C72—C71—C77—N7	−143.4 (2)
C14—C15—C16—C11	−1.7 (4)	C76—C71—C77—N7	36.8 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O81—H81···Cg1	0.84	2.23	3.057 (7)	166
C52—H52A···O81	0.99	2.22	3.145 (6)	155
C75—H75···Cg2^i	0.95	2.59	3.519 (3)	167

Symmetry code: (i) −x+1/2, −y+3/2, −z+1.

(IV) 3-tert-Butyl-4',4'-dimethyl-1-phenyl-7-[4-(trifluoromethyl)benzyl]- 4,5,6,7-tetrahydro-1H-pyrazolo[3,4-b]pyridine-5-spiro-1'- cyclohexane-2',6'-dione ethanol hemisolvate

Crystal data

C31H34F3N3O2·0.5C2H6O	Z = 2
Mr = 560.65	F(000) = 594
Triclinic, P1	Dx = 1.332 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.3270 (12) Å	Cell parameters from 6424 reflections
b = 11.9970 (14) Å	θ = 2.8–27.5°
c = 12.427 (3) Å	µ = 0.10 mm^−1
α = 75.016 (13)°	T = 120 K
β = 70.059 (11)°	Block, colourless
γ = 84.481 (9)°	0.47 × 0.35 × 0.28 mm
V = 1398.0 (4) Å^3

Data collection

Bruker Nonius KappaCCD area-detector diffractometer	6424 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	3353 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.092
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 2.8°
ϕ and ω scans	h = −13→13
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −15→15
Tmin = 0.963, Tmax = 0.973	l = −16→16
39346 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.069	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.224	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.1175P)^2 + 0.5775P] where P = (Fo^2 + 2Fc^2)/3
6424 reflections	(Δ/σ)max < 0.001
378 parameters	Δρmax = 0.46 e Å^−3
3 restraints	Δρmin = −0.53 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
F71	0.9210 (2)	0.50091 (17)	0.82642 (18)	0.0489 (6)
F72	0.8580 (3)	0.35315 (18)	0.7966 (2)	0.0722 (8)
F73	1.0380 (2)	0.4394 (3)	0.6759 (2)	0.0861 (10)
O51	0.0749 (2)	0.72548 (19)	0.78300 (19)	0.0356 (5)
O55	0.3465 (2)	0.98307 (17)	0.54177 (18)	0.0320 (5)
N1	0.4623 (2)	0.7687 (2)	0.2764 (2)	0.0243 (5)
N2	0.3737 (2)	0.83214 (19)	0.2231 (2)	0.0261 (6)
N7	0.4747 (2)	0.6969 (2)	0.4773 (2)	0.0230 (5)
C3	0.2657 (3)	0.8551 (2)	0.3107 (3)	0.0245 (6)
C3a	0.2838 (3)	0.8083 (2)	0.4213 (3)	0.0240 (6)
C4	0.1960 (3)	0.8104 (2)	0.5440 (2)	0.0242 (6)
C5	0.2818 (3)	0.7866 (2)	0.6245 (2)	0.0246 (6)
C6	0.3788 (3)	0.6813 (2)	0.5971 (2)	0.0242 (6)
C7a	0.4101 (3)	0.7554 (2)	0.3956 (2)	0.0241 (6)
C11	0.5825 (3)	0.7238 (2)	0.2036 (3)	0.0238 (6)
C12	0.6402 (3)	0.6208 (2)	0.2452 (3)	0.0258 (7)
C13	0.7574 (3)	0.5799 (2)	0.1722 (3)	0.0272 (7)
C14	0.8173 (3)	0.6400 (3)	0.0576 (3)	0.0312 (7)
C15	0.7579 (3)	0.7421 (3)	0.0161 (3)	0.0341 (7)
C16	0.6412 (3)	0.7846 (3)	0.0876 (3)	0.0302 (7)
C31	0.1506 (3)	0.9300 (2)	0.2837 (2)	0.0258 (7)
C32	0.1608 (3)	1.0480 (2)	0.3074 (3)	0.0312 (7)
C33	0.1606 (3)	0.9469 (3)	0.1559 (3)	0.0314 (7)
C34	0.0125 (3)	0.8757 (3)	0.3629 (3)	0.0316 (7)
C51	0.1943 (3)	0.7508 (2)	0.7547 (3)	0.0263 (7)
C52	0.2628 (3)	0.7479 (3)	0.8443 (3)	0.0322 (7)
C53	0.3392 (3)	0.8598 (3)	0.8215 (3)	0.0308 (7)
C531	0.2357 (3)	0.9581 (3)	0.8406 (3)	0.0390 (8)
C532	0.4231 (3)	0.8435 (3)	0.9038 (3)	0.0357 (8)
C54	0.4368 (3)	0.8862 (3)	0.6943 (3)	0.0282 (7)
C55	0.3596 (3)	0.8942 (2)	0.6105 (3)	0.0263 (7)
C71	0.6832 (3)	0.6674 (2)	0.5354 (3)	0.0251 (6)
C72	0.7550 (3)	0.7156 (3)	0.5877 (3)	0.0274 (7)
C73	0.8279 (3)	0.6481 (3)	0.6560 (3)	0.0304 (7)
C74	0.8290 (3)	0.5299 (3)	0.6729 (3)	0.0302 (7)
C741	0.9113 (3)	0.4574 (3)	0.7431 (3)	0.0358 (8)
C75	0.7573 (3)	0.4797 (3)	0.6223 (3)	0.0300 (7)
C76	0.6850 (3)	0.5484 (2)	0.5542 (3)	0.0272 (7)
C77	0.6092 (3)	0.7435 (2)	0.4591 (3)	0.0252 (6)
C81	0.5602 (16)	0.4842 (18)	0.9407 (8)	0.077 (3)	0.50
C82	0.457 (2)	0.4830 (18)	1.0643 (6)	0.077 (3)	0.50
O81	0.5048 (6)	0.5504 (6)	0.8537 (5)	0.0702 (17)	0.50
H14A	0.1232	0.7515	0.5730	0.029*
H14B	0.1506	0.8870	0.5445	0.029*
H6A	0.4326	0.6624	0.6520	0.029*
H6B	0.3205	0.6139	0.6141	0.029*
H12	0.5994	0.5780	0.3241	0.031*
H13	0.7974	0.5089	0.2016	0.033*
H14	0.8984	0.6115	0.0078	0.037*
H15	0.7981	0.7839	−0.0633	0.041*
H16	0.6010	0.8552	0.0578	0.036*
H32A	0.1505	1.0378	0.3907	0.047*
H32B	0.0877	1.0993	0.2886	0.047*
H32C	0.2508	1.0819	0.2581	0.047*
H33A	0.2508	0.9790	0.1044	0.047*
H33B	0.0879	1.0002	0.1394	0.047*
H33C	0.1497	0.8724	0.1414	0.047*
H34A	0.0073	0.7994	0.3498	0.047*
H34B	−0.0622	0.9250	0.3444	0.047*
H34C	0.0036	0.8678	0.4457	0.047*
H52A	0.3291	0.6825	0.8438	0.039*
H52B	0.1922	0.7340	0.9236	0.039*
H53A	0.2850	1.0298	0.8239	0.058*
H53B	0.1741	0.9405	0.9226	0.058*
H53C	0.1815	0.9673	0.7877	0.058*
H53D	0.4701	0.9156	0.8900	0.054*
H53E	0.4915	0.7820	0.8887	0.054*
H53F	0.3618	0.8224	0.9858	0.054*
H54A	0.4841	0.9600	0.6764	0.034*
H54B	0.5077	0.8245	0.6843	0.034*
H72	0.7541	0.7970	0.5764	0.033*
H73	0.8769	0.6828	0.6911	0.037*
H75	0.7577	0.3982	0.6343	0.036*
H76	0.6357	0.5134	0.5197	0.033*
H77A	0.5954	0.8206	0.4764	0.030*
H77B	0.6668	0.7529	0.3754	0.030*
H81A	0.6539	0.5027	0.9352	0.092*	0.50
H81B	0.5612	0.4038	0.9333	0.092*	0.50
H82A	0.4316	0.5643	1.0607	0.115*	0.50
H82B	0.4994	0.4538	1.1259	0.115*	0.50
H82C	0.3747	0.4381	1.0824	0.115*	0.50
H81	0.5456	0.5311	0.7901	0.105*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
F71	0.0642 (13)	0.0491 (12)	0.0497 (13)	0.0115 (10)	−0.0380 (11)	−0.0178 (10)
F72	0.1021 (19)	0.0376 (12)	0.102 (2)	0.0008 (12)	−0.0780 (17)	0.0004 (12)
F73	0.0510 (15)	0.148 (3)	0.0562 (16)	0.0490 (16)	−0.0258 (13)	−0.0267 (16)
O51	0.0273 (12)	0.0465 (14)	0.0274 (12)	−0.0026 (10)	−0.0039 (10)	−0.0053 (10)
O55	0.0383 (12)	0.0260 (11)	0.0297 (12)	−0.0031 (9)	−0.0109 (10)	−0.0026 (9)
N1	0.0243 (13)	0.0271 (13)	0.0201 (13)	0.0035 (10)	−0.0068 (11)	−0.0054 (10)
N2	0.0307 (13)	0.0247 (13)	0.0233 (13)	0.0052 (10)	−0.0105 (11)	−0.0063 (10)
N7	0.0217 (12)	0.0257 (12)	0.0192 (13)	0.0005 (10)	−0.0041 (10)	−0.0049 (10)
C3	0.0294 (15)	0.0227 (15)	0.0228 (15)	0.0024 (12)	−0.0104 (13)	−0.0064 (12)
C3a	0.0236 (14)	0.0224 (14)	0.0251 (16)	0.0004 (12)	−0.0061 (13)	−0.0069 (12)
C4	0.0244 (14)	0.0242 (15)	0.0216 (15)	0.0011 (12)	−0.0056 (12)	−0.0046 (12)
C5	0.0252 (15)	0.0263 (15)	0.0217 (15)	0.0031 (12)	−0.0078 (13)	−0.0060 (12)
C6	0.0255 (15)	0.0223 (14)	0.0229 (15)	−0.0005 (12)	−0.0084 (13)	−0.0017 (12)
C7a	0.0288 (15)	0.0232 (15)	0.0198 (15)	−0.0029 (12)	−0.0087 (13)	−0.0023 (11)
C11	0.0223 (14)	0.0253 (15)	0.0246 (16)	0.0016 (12)	−0.0082 (12)	−0.0075 (12)
C12	0.0262 (15)	0.0262 (15)	0.0229 (16)	−0.0010 (12)	−0.0065 (13)	−0.0043 (12)
C13	0.0272 (15)	0.0228 (15)	0.0289 (17)	0.0027 (12)	−0.0075 (14)	−0.0050 (12)
C14	0.0259 (16)	0.0355 (17)	0.0298 (18)	0.0045 (13)	−0.0050 (14)	−0.0110 (14)
C15	0.0320 (17)	0.0388 (18)	0.0240 (17)	−0.0021 (14)	−0.0029 (14)	−0.0025 (14)
C16	0.0309 (16)	0.0296 (16)	0.0250 (17)	0.0023 (13)	−0.0059 (14)	−0.0034 (13)
C31	0.0253 (15)	0.0298 (16)	0.0219 (16)	0.0054 (12)	−0.0081 (13)	−0.0073 (12)
C32	0.0375 (17)	0.0283 (16)	0.0280 (17)	0.0073 (13)	−0.0130 (15)	−0.0069 (13)
C33	0.0318 (17)	0.0371 (18)	0.0273 (17)	0.0063 (13)	−0.0149 (14)	−0.0067 (14)
C34	0.0297 (16)	0.0362 (17)	0.0286 (17)	0.0017 (13)	−0.0112 (14)	−0.0059 (13)
C51	0.0303 (17)	0.0236 (15)	0.0224 (16)	0.0018 (12)	−0.0061 (13)	−0.0054 (12)
C52	0.0342 (17)	0.0368 (18)	0.0222 (16)	0.0028 (14)	−0.0074 (14)	−0.0051 (13)
C53	0.0287 (16)	0.0392 (18)	0.0267 (17)	0.0046 (13)	−0.0098 (14)	−0.0127 (14)
C531	0.0392 (18)	0.047 (2)	0.038 (2)	0.0140 (16)	−0.0171 (16)	−0.0202 (16)
C532	0.0352 (17)	0.0455 (19)	0.0340 (19)	0.0086 (15)	−0.0182 (15)	−0.0166 (15)
C54	0.0287 (16)	0.0311 (16)	0.0261 (16)	−0.0014 (13)	−0.0082 (13)	−0.0098 (13)
C55	0.0271 (15)	0.0272 (16)	0.0228 (16)	0.0011 (12)	−0.0036 (13)	−0.0097 (13)
C71	0.0213 (14)	0.0277 (15)	0.0249 (16)	−0.0007 (12)	−0.0041 (13)	−0.0084 (12)
C72	0.0255 (15)	0.0260 (15)	0.0305 (17)	−0.0019 (12)	−0.0077 (13)	−0.0077 (13)
C73	0.0280 (16)	0.0360 (18)	0.0314 (18)	−0.0012 (13)	−0.0130 (14)	−0.0104 (14)
C74	0.0257 (15)	0.0324 (17)	0.0332 (18)	0.0050 (13)	−0.0114 (14)	−0.0087 (14)
C741	0.0378 (19)	0.0371 (19)	0.0380 (19)	0.0031 (14)	−0.0187 (16)	−0.0113 (15)
C75	0.0314 (16)	0.0262 (16)	0.0337 (18)	0.0012 (13)	−0.0131 (14)	−0.0068 (13)
C76	0.0249 (15)	0.0292 (16)	0.0295 (17)	−0.0022 (12)	−0.0086 (13)	−0.0100 (13)
C77	0.0242 (15)	0.0241 (15)	0.0258 (16)	−0.0039 (12)	−0.0079 (13)	−0.0026 (12)
C81	0.091 (5)	0.058 (11)	0.062 (3)	0.058 (5)	−0.025 (3)	−0.002 (4)
C82	0.091 (5)	0.058 (11)	0.062 (3)	0.058 (5)	−0.025 (3)	−0.002 (4)
O81	0.066 (4)	0.094 (5)	0.053 (4)	0.029 (3)	−0.023 (3)	−0.027 (3)

Geometric parameters (Å, º)

F71—C741	1.310 (4)	C33—H33C	0.98
F72—C741	1.328 (4)	C34—H34A	0.98
F73—C741	1.323 (4)	C34—H34B	0.98
O51—C51	1.207 (4)	C34—H34C	0.98
O55—C55	1.210 (3)	C51—C52	1.502 (4)
N1—C7a	1.363 (4)	C52—C53	1.536 (4)
N1—N2	1.369 (3)	C52—H52A	0.99
N1—C11	1.417 (3)	C52—H52B	0.99
N2—C3	1.332 (4)	C53—C532	1.518 (4)
N7—C7a	1.405 (4)	C53—C531	1.523 (4)
N7—C6	1.455 (4)	C53—C54	1.527 (4)
N7—C77	1.470 (3)	C531—H53A	0.98
C3—C3a	1.413 (4)	C531—H53B	0.98
C3—C31	1.498 (4)	C531—H53C	0.98
C3a—C7a	1.366 (4)	C532—H53D	0.98
C3a—C4	1.490 (4)	C532—H53E	0.98
C4—C5	1.509 (4)	C532—H53F	0.98
C4—H14A	0.99	C54—C55	1.493 (4)
C4—H14B	0.99	C54—H54A	0.99
C5—C55	1.526 (4)	C54—H54B	0.99
C5—C51	1.528 (4)	C71—C72	1.383 (4)
C5—C6	1.569 (4)	C71—C76	1.385 (4)
C6—H6A	0.99	C71—C77	1.493 (4)
C6—H6B	0.99	C72—C73	1.381 (4)
C11—C12	1.374 (4)	C72—H72	0.95
C11—C16	1.387 (4)	C73—C74	1.378 (4)
C12—C13	1.377 (4)	C73—H73	0.95
C12—H12	0.95	C74—C75	1.380 (4)
C13—C14	1.373 (4)	C74—C741	1.486 (4)
C13—H13	0.95	C75—C76	1.380 (4)
C14—C15	1.373 (4)	C75—H75	0.95
C14—H14	0.95	C76—H76	0.95
C15—C16	1.374 (4)	C77—H77A	0.99
C15—H15	0.95	C77—H77B	0.99
C16—H16	0.95	C81—O81	1.4200 (11)
C31—C33	1.516 (4)	C81—C82	1.5388 (11)
C31—C34	1.522 (4)	C81—H81A	0.99
C31—C32	1.538 (4)	C81—H81B	0.99
C32—H32A	0.98	C82—H82A	0.98
C32—H32B	0.98	C82—H82B	0.98
C32—H32C	0.98	C82—H82C	0.98
C33—H33A	0.98	O81—H81	0.84
C33—H33B	0.98
C7a—N1—N2	110.6 (2)	C52—C51—C5	117.5 (3)
C7a—N1—C11	131.9 (2)	C51—C52—C53	113.1 (2)
N2—N1—C11	117.4 (2)	C51—C52—H52A	109.0
C3—N2—N1	105.3 (2)	C53—C52—H52A	109.0
C7a—N7—C6	110.4 (2)	C51—C52—H52B	109.0
C7a—N7—C77	114.7 (2)	C53—C52—H52B	109.0
C6—N7—C77	114.5 (2)	H52A—C52—H52B	107.8
N2—C3—C3a	111.4 (2)	C532—C53—C531	110.2 (3)
N2—C3—C31	119.9 (2)	C532—C53—C54	108.9 (2)
C3a—C3—C31	128.5 (3)	C531—C53—C54	110.2 (3)
C7a—C3a—C3	104.7 (2)	C532—C53—C52	109.8 (3)
C7a—C3a—C4	122.8 (3)	C531—C53—C52	109.7 (3)
C3—C3a—C4	132.4 (2)	C54—C53—C52	108.1 (2)
C3a—C4—C5	110.5 (2)	C53—C531—H53A	109.5
C3a—C4—H14A	109.6	C53—C531—H53B	109.5
C5—C4—H14A	109.6	H53A—C531—H53B	109.5
C3a—C4—H14B	109.6	C53—C531—H53C	109.5
C5—C4—H14B	109.6	H53A—C531—H53C	109.5
H14A—C4—H14B	108.1	H53B—C531—H53C	109.5
C4—C5—C55	111.0 (2)	C53—C532—H53D	109.5
C4—C5—C51	112.4 (2)	C53—C532—H53E	109.5
C55—C5—C51	106.2 (2)	H53D—C532—H53E	109.5
C4—C5—C6	107.5 (2)	C53—C532—H53F	109.5
C55—C5—C6	113.3 (2)	H53D—C532—H53F	109.5
C51—C5—C6	106.4 (2)	H53E—C532—H53F	109.5
N7—C6—C5	116.2 (2)	C55—C54—C53	110.7 (2)
N7—C6—H6A	108.2	C55—C54—H54A	109.5
C5—C6—H6A	108.2	C53—C54—H54A	109.5
N7—C6—H6B	108.2	C55—C54—H54B	109.5
C5—C6—H6B	108.2	C53—C54—H54B	109.5
H6A—C6—H6B	107.4	H54A—C54—H54B	108.1
N1—C7a—C3a	108.0 (2)	O55—C55—C54	123.2 (3)
N1—C7a—N7	125.9 (2)	O55—C55—C5	120.0 (3)
C3a—C7a—N7	126.1 (3)	C54—C55—C5	116.5 (2)
C12—C11—C16	119.7 (3)	C72—C71—C76	118.1 (3)
C12—C11—N1	121.3 (3)	C72—C71—C77	120.0 (3)
C16—C11—N1	119.0 (2)	C76—C71—C77	122.0 (3)
C11—C12—C13	119.8 (3)	C73—C72—C71	121.5 (3)
C11—C12—H12	120.1	C73—C72—H72	119.2
C13—C12—H12	120.1	C71—C72—H72	119.2
C14—C13—C12	121.0 (3)	C74—C73—C72	119.4 (3)
C14—C13—H13	119.5	C74—C73—H73	120.3
C12—C13—H13	119.5	C72—C73—H73	120.3
C13—C14—C15	118.9 (3)	C73—C74—C75	120.2 (3)
C13—C14—H14	120.6	C73—C74—C741	119.4 (3)
C15—C14—H14	120.6	C75—C74—C741	120.4 (3)
C14—C15—C16	121.0 (3)	F71—C741—F73	107.4 (3)
C14—C15—H15	119.5	F71—C741—F72	105.8 (3)
C16—C15—H15	119.5	F73—C741—F72	105.3 (3)
C15—C16—C11	119.6 (3)	F71—C741—C74	113.7 (3)
C15—C16—H16	120.2	F73—C741—C74	111.9 (3)
C11—C16—H16	120.2	F72—C741—C74	112.1 (3)
C3—C31—C33	111.2 (2)	C76—C75—C74	119.8 (3)
C3—C31—C34	110.0 (2)	C76—C75—H75	120.1
C33—C31—C34	109.0 (2)	C74—C75—H75	120.1
C3—C31—C32	107.9 (2)	C75—C76—C71	121.1 (3)
C33—C31—C32	109.2 (2)	C75—C76—H76	119.5
C34—C31—C32	109.4 (2)	C71—C76—H76	119.5
C31—C32—H32A	109.5	N7—C77—C71	112.4 (2)
C31—C32—H32B	109.5	N7—C77—H77A	109.1
H32A—C32—H32B	109.5	C71—C77—H77A	109.1
C31—C32—H32C	109.5	N7—C77—H77B	109.1
H32A—C32—H32C	109.5	C71—C77—H77B	109.1
H32B—C32—H32C	109.5	H77A—C77—H77B	107.9
C31—C33—H33A	109.5	O81—C81—C82	109.53 (16)
C31—C33—H33B	109.5	O81—C81—H81A	118.1
H33A—C33—H33B	109.5	C82—C81—H81A	110.8
C31—C33—H33C	109.5	O81—C81—H81B	104.6
H33A—C33—H33C	109.5	C82—C81—H81B	104.5
H33B—C33—H33C	109.5	H81A—C81—H81B	108.2
C31—C34—H34A	109.5	C81—C82—H82A	104.0
C31—C34—H34B	109.5	C81—C82—H82B	111.9
H34A—C34—H34B	109.5	H82A—C82—H82B	109.5
C31—C34—H34C	109.5	C81—C82—H82C	112.4
H34A—C34—H34C	109.5	H82A—C82—H82C	109.5
H34B—C34—H34C	109.5	H82B—C82—H82C	109.5
O51—C51—C52	122.0 (3)	C81—O81—H81	108.3
O51—C51—C5	120.5 (3)
C7a—N1—N2—C3	−1.5 (3)	C3a—C3—C31—C34	−50.9 (4)
C11—N1—N2—C3	174.9 (2)	N2—C3—C31—C32	−106.4 (3)
N1—N2—C3—C3a	0.8 (3)	C3a—C3—C31—C32	68.4 (4)
N1—N2—C3—C31	176.4 (2)	C4—C5—C51—O51	12.4 (4)
N2—C3—C3a—C7a	0.2 (3)	C55—C5—C51—O51	134.0 (3)
C31—C3—C3a—C7a	−175.0 (3)	C6—C5—C51—O51	−104.9 (3)
N2—C3—C3a—C4	179.4 (3)	C4—C5—C51—C52	−168.0 (2)
C31—C3—C3a—C4	4.2 (5)	C55—C5—C51—C52	−46.4 (3)
C7a—C3a—C4—C5	19.9 (4)	C6—C5—C51—C52	74.7 (3)
C3—C3a—C4—C5	−159.2 (3)	O51—C51—C52—C53	−129.4 (3)
C3a—C4—C5—C55	79.0 (3)	C5—C51—C52—C53	51.0 (3)
C3a—C4—C5—C51	−162.1 (2)	C51—C52—C53—C532	−171.4 (2)
C3a—C4—C5—C6	−45.4 (3)	C51—C52—C53—C531	67.4 (3)
C7a—N7—C6—C5	−41.0 (3)	C51—C52—C53—C54	−52.8 (3)
C77—N7—C6—C5	90.3 (3)	C532—C53—C54—C55	175.8 (2)
C4—C5—C6—N7	60.7 (3)	C531—C53—C54—C55	−63.3 (3)
C55—C5—C6—N7	−62.3 (3)	C52—C53—C54—C55	56.6 (3)
C51—C5—C6—N7	−178.7 (2)	C53—C54—C55—O55	113.0 (3)
N2—N1—C7a—C3a	1.6 (3)	C53—C54—C55—C5	−60.0 (3)
C11—N1—C7a—C3a	−174.0 (3)	C4—C5—C55—O55	0.4 (4)
N2—N1—C7a—N7	−178.9 (2)	C51—C5—C55—O55	−122.0 (3)
C11—N1—C7a—N7	5.5 (5)	C6—C5—C55—O55	121.5 (3)
C3—C3a—C7a—N1	−1.1 (3)	C4—C5—C55—C54	173.7 (2)
C4—C3a—C7a—N1	179.6 (2)	C51—C5—C55—C54	51.2 (3)
C3—C3a—C7a—N7	179.4 (3)	C6—C5—C55—C54	−65.3 (3)
C4—C3a—C7a—N7	0.1 (4)	C76—C71—C72—C73	0.6 (4)
C6—N7—C7a—N1	−169.2 (3)	C77—C71—C72—C73	−178.1 (3)
C77—N7—C7a—N1	59.6 (4)	C71—C72—C73—C74	−0.2 (5)
C6—N7—C7a—C3a	10.2 (4)	C72—C73—C74—C75	−0.3 (5)
C77—N7—C7a—C3a	−121.0 (3)	C72—C73—C74—C741	177.9 (3)
C7a—N1—C11—C12	27.5 (4)	C73—C74—C741—F71	31.2 (4)
N2—N1—C11—C12	−147.9 (3)	C75—C74—C741—F71	−150.6 (3)
C7a—N1—C11—C16	−153.6 (3)	C73—C74—C741—F73	−90.7 (4)
N2—N1—C11—C16	31.0 (4)	C75—C74—C741—F73	87.5 (4)
C16—C11—C12—C13	1.3 (4)	C73—C74—C741—F72	151.2 (3)
N1—C11—C12—C13	−179.8 (3)	C75—C74—C741—F72	−30.6 (4)
C11—C12—C13—C14	−0.6 (4)	C73—C74—C75—C76	0.3 (5)
C12—C13—C14—C15	−0.4 (5)	C741—C74—C75—C76	−177.9 (3)
C13—C14—C15—C16	0.6 (5)	C74—C75—C76—C71	0.1 (5)
C14—C15—C16—C11	0.1 (5)	C72—C71—C76—C75	−0.6 (4)
C12—C11—C16—C15	−1.1 (4)	C77—C71—C76—C75	178.2 (3)
N1—C11—C16—C15	179.9 (3)	C7a—N7—C77—C71	−170.7 (2)
N2—C3—C31—C33	13.4 (4)	C6—N7—C77—C71	60.1 (3)
C3a—C3—C31—C33	−171.8 (3)	C72—C71—C77—N7	−139.9 (3)
N2—C3—C31—C34	134.3 (3)	C76—C71—C77—N7	41.3 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O81—H81···Cg1	0.84	2.58	3.245 (6)	137
C52—H52A···O81	0.99	2.31	3.285 (8)	170
C75—H75···Cg2^i	0.95	2.67	3.544 (4)	154
C77—H77A···O55^ii	0.99	2.42	3.352 (3)	157

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+2, −z+1.