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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\overline{1}. 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).

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108036937/ga3109sup1.cif
Contains datablocks global, I, II, III, IV

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108036937/ga3109Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108036937/ga3109IIsup3.hkl
Contains datablock II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108036937/ga3109IIIsup4.hkl
Contains datablock III

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108036937/ga3109IVsup5.hkl
Contains datablock IV

CCDC references: 718141; 718142; 718143; 718144

Comment top

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 Å3 per void in (I) to 66 Å3 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 CH3E 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 top

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).

Experimental top

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.

Refinement top

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 Uiso(H) = kUeq(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 top

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 top
[Figure 1] 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.
[Figure 2] 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).
[Figure 3] 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 top
Crystal data top
C30H34ClN3O2·0.5C2H6OF(000) = 2248
Mr = 527.09Dx = 1.327 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 6021 reflections
a = 27.419 (4) Åθ = 3.0–27.5°
b = 10.5860 (13) ŵ = 0.18 mm1
c = 21.580 (3) ÅT = 120 K
β = 122.625 (11)°Block, colourless
V = 5275.5 (14) Å30.32 × 0.23 × 0.22 mm
Z = 8
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
6021 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode4812 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.059
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.0°
ϕ and ω scansh = 3534
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 1312
Tmin = 0.954, Tmax = 0.961l = 2827
36250 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)] = 0.051Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.132H-atom parameters constrained
S = 1.08 w = 1/[σ2(Fo2) + (0.0455P)2 + 11.7674P]
where P = (Fo2 + 2Fc2)/3
6021 reflections(Δ/σ)max = 0.001
352 parametersΔρmax = 0.55 e Å3
3 restraintsΔρmin = 0.52 e Å3
Crystal data top
C30H34ClN3O2·0.5C2H6OV = 5275.5 (14) Å3
Mr = 527.09Z = 8
Monoclinic, C2/cMo Kα radiation
a = 27.419 (4) ŵ = 0.18 mm1
b = 10.5860 (13) ÅT = 120 K
c = 21.580 (3) Å0.32 × 0.23 × 0.22 mm
β = 122.625 (11)°
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
6021 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
4812 reflections with I > 2σ(I)
Tmin = 0.954, Tmax = 0.961Rint = 0.059
36250 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0513 restraints
wR(F2) = 0.132H-atom parameters constrained
S = 1.08 w = 1/[σ2(Fo2) + (0.0455P)2 + 11.7674P]
where P = (Fo2 + 2Fc2)/3
6021 reflectionsΔρmax = 0.55 e Å3
352 parametersΔρmin = 0.52 e Å3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Cl70.39945 (2)0.66283 (6)0.82597 (3)0.03174 (14)
O510.40061 (6)0.58895 (14)0.42829 (8)0.0264 (3)
O550.30684 (6)0.25346 (13)0.44006 (8)0.0238 (3)
N10.15935 (7)0.50792 (15)0.35775 (8)0.0177 (3)
N20.13499 (7)0.48364 (15)0.28439 (8)0.0186 (3)
N70.25720 (7)0.53389 (15)0.46815 (8)0.0170 (3)
C30.17881 (8)0.46948 (17)0.27577 (10)0.0166 (4)
C3a0.23249 (8)0.48169 (17)0.34329 (10)0.0165 (4)
C40.29354 (8)0.47093 (18)0.36278 (10)0.0178 (4)
C50.33590 (8)0.46673 (18)0.44583 (10)0.0170 (4)
C60.31421 (8)0.56170 (17)0.48149 (10)0.0173 (4)
C7a0.21836 (8)0.50633 (17)0.39381 (10)0.0166 (4)
C110.12152 (8)0.53981 (18)0.38086 (10)0.0181 (4)
C120.13925 (8)0.61559 (19)0.44154 (11)0.0208 (4)
C130.10057 (9)0.64580 (19)0.46185 (11)0.0227 (4)
C140.04414 (9)0.6043 (2)0.42067 (11)0.0263 (4)
C150.02626 (9)0.5310 (2)0.35919 (12)0.0276 (5)
C160.06499 (8)0.4972 (2)0.33976 (11)0.0231 (4)
C310.16806 (8)0.44614 (18)0.20036 (10)0.0184 (4)
C320.19267 (10)0.3180 (2)0.19862 (12)0.0275 (4)
C330.10337 (9)0.4489 (2)0.14238 (11)0.0286 (5)
C340.19749 (9)0.5491 (2)0.18266 (11)0.0250 (4)
C510.39576 (8)0.51656 (18)0.46782 (10)0.0188 (4)
C520.44676 (8)0.4808 (2)0.54177 (11)0.0247 (4)
C530.44807 (8)0.3432 (2)0.56348 (11)0.0242 (4)
C540.38994 (8)0.31258 (19)0.55459 (11)0.0219 (4)
C550.34075 (8)0.33525 (18)0.47695 (10)0.0177 (4)
C710.28942 (8)0.50512 (18)0.59765 (10)0.0178 (4)
C720.31876 (8)0.42535 (19)0.65770 (11)0.0217 (4)
C730.35147 (9)0.4728 (2)0.72834 (11)0.0246 (4)
C740.35477 (8)0.6013 (2)0.73848 (10)0.0228 (4)
C750.32467 (8)0.68332 (19)0.68035 (11)0.0227 (4)
C760.29208 (8)0.63392 (19)0.61013 (10)0.0205 (4)
C770.25595 (8)0.45028 (18)0.52146 (10)0.0186 (4)
C5310.45796 (9)0.2566 (2)0.51527 (12)0.0294 (5)
C5320.49705 (10)0.3262 (2)0.64343 (12)0.0354 (5)
C810.4735 (2)0.6812 (4)0.7091 (4)0.0511 (10)0.50
C820.5250 (2)0.6483 (6)0.7867 (3)0.0511 (10)0.50
O810.43843 (16)0.5723 (5)0.6765 (2)0.0685 (14)0.50
H4A0.30280.54410.34230.021*
H4B0.29770.39320.34050.021*
H5A0.34270.56300.53530.021*
H5B0.31330.64740.46250.021*
H120.17780.64690.46920.025*
H130.11310.69560.50450.027*
H140.01770.62590.43450.032*
H150.01290.50370.33000.033*
H160.05270.44460.29820.028*
H12A0.17400.25150.21030.041*
H12B0.23450.31680.23500.041*
H12C0.18540.30320.14950.041*
H33A0.08400.38170.15250.043*
H33B0.09700.43590.09360.043*
H33C0.08740.53100.14380.043*
H34A0.23940.54610.21850.037*
H34B0.18250.63180.18500.037*
H34C0.18950.53570.13310.037*
H52A0.44720.53540.57930.030*
H52B0.48250.49860.54250.030*
H54A0.38970.22310.56780.026*
H54B0.38500.36610.58840.026*
H720.31640.33660.65020.026*
H730.37140.41750.76930.029*
H750.32630.77190.68830.027*
H760.27100.68960.56950.025*
H77A0.27270.36730.52160.022*
H77B0.21530.43650.50640.022*
H53A0.49450.27900.51990.044*
H53B0.42600.26590.46390.044*
H53C0.45980.16880.53090.044*
H53D0.53400.34670.64890.053*
H53E0.49780.23840.65830.053*
H53F0.49090.38260.67460.053*
H81A0.48770.70350.67700.061*0.50
H81B0.45020.75280.70900.061*0.50
H82A0.54020.56310.78990.077*0.50
H82B0.55540.71060.79910.077*0.50
H82C0.51240.65600.82110.077*0.50
H810.41310.57480.68700.103*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl70.0323 (3)0.0386 (3)0.0181 (2)0.0064 (2)0.0095 (2)0.0038 (2)
O510.0238 (7)0.0277 (8)0.0290 (8)0.0045 (6)0.0151 (6)0.0048 (6)
O550.0245 (7)0.0189 (7)0.0279 (7)0.0038 (6)0.0142 (6)0.0020 (6)
N10.0180 (7)0.0217 (8)0.0153 (7)0.0022 (6)0.0102 (6)0.0016 (6)
N20.0205 (8)0.0214 (8)0.0149 (7)0.0019 (6)0.0102 (6)0.0018 (6)
N70.0181 (7)0.0201 (8)0.0143 (7)0.0031 (6)0.0097 (6)0.0001 (6)
C30.0190 (8)0.0148 (8)0.0179 (8)0.0011 (7)0.0113 (7)0.0001 (7)
C3a0.0190 (9)0.0149 (8)0.0179 (8)0.0009 (7)0.0114 (7)0.0007 (7)
C40.0168 (8)0.0210 (9)0.0175 (8)0.0011 (7)0.0105 (7)0.0010 (7)
C50.0168 (8)0.0185 (9)0.0168 (8)0.0008 (7)0.0098 (7)0.0000 (7)
C60.0177 (8)0.0157 (9)0.0206 (9)0.0011 (7)0.0117 (7)0.0007 (7)
C7a0.0185 (8)0.0163 (8)0.0167 (8)0.0015 (7)0.0106 (7)0.0003 (7)
C110.0184 (8)0.0208 (9)0.0188 (9)0.0005 (7)0.0126 (7)0.0026 (7)
C120.0197 (9)0.0229 (10)0.0221 (9)0.0028 (7)0.0127 (8)0.0018 (7)
C130.0261 (10)0.0247 (10)0.0223 (9)0.0017 (8)0.0163 (8)0.0025 (8)
C140.0247 (10)0.0344 (11)0.0278 (10)0.0010 (8)0.0195 (9)0.0012 (9)
C150.0195 (9)0.0388 (12)0.0273 (10)0.0055 (9)0.0144 (8)0.0059 (9)
C160.0214 (9)0.0302 (11)0.0194 (9)0.0036 (8)0.0122 (8)0.0042 (8)
C310.0183 (9)0.0220 (9)0.0166 (8)0.0013 (7)0.0106 (7)0.0021 (7)
C320.0359 (11)0.0236 (10)0.0266 (10)0.0008 (9)0.0191 (9)0.0053 (8)
C330.0211 (10)0.0470 (13)0.0182 (9)0.0033 (9)0.0109 (8)0.0068 (9)
C340.0297 (10)0.0277 (11)0.0223 (9)0.0032 (8)0.0171 (8)0.0012 (8)
C510.0193 (9)0.0169 (9)0.0217 (9)0.0019 (7)0.0121 (8)0.0030 (7)
C520.0190 (9)0.0283 (11)0.0238 (10)0.0069 (8)0.0096 (8)0.0007 (8)
C530.0181 (9)0.0288 (11)0.0215 (9)0.0006 (8)0.0079 (8)0.0037 (8)
C540.0221 (9)0.0229 (10)0.0217 (9)0.0003 (8)0.0125 (8)0.0048 (8)
C550.0174 (8)0.0185 (9)0.0217 (9)0.0002 (7)0.0135 (7)0.0003 (7)
C710.0170 (8)0.0222 (9)0.0169 (8)0.0007 (7)0.0109 (7)0.0007 (7)
C720.0230 (9)0.0196 (9)0.0231 (9)0.0005 (7)0.0127 (8)0.0029 (7)
C730.0225 (9)0.0294 (11)0.0174 (9)0.0001 (8)0.0079 (8)0.0062 (8)
C740.0207 (9)0.0310 (11)0.0155 (9)0.0042 (8)0.0088 (7)0.0030 (8)
C750.0259 (10)0.0217 (10)0.0222 (9)0.0006 (8)0.0139 (8)0.0001 (8)
C760.0229 (9)0.0216 (9)0.0184 (9)0.0015 (7)0.0120 (8)0.0014 (7)
C770.0215 (9)0.0192 (9)0.0172 (8)0.0014 (7)0.0119 (7)0.0010 (7)
C5310.0264 (10)0.0330 (12)0.0304 (11)0.0081 (9)0.0164 (9)0.0060 (9)
C5320.0258 (11)0.0417 (13)0.0248 (11)0.0006 (10)0.0044 (9)0.0067 (10)
C810.0499 (18)0.020 (3)0.069 (2)0.0012 (17)0.0229 (16)0.0054 (18)
C820.0499 (18)0.020 (3)0.069 (2)0.0012 (17)0.0229 (16)0.0054 (18)
O810.039 (2)0.111 (4)0.061 (3)0.018 (2)0.031 (2)0.036 (3)
Geometric parameters (Å, º) top
Cl7—C741.731 (2)C33—H33C0.98
O51—C511.206 (2)C34—H34A0.98
O55—C551.204 (2)C34—H34B0.98
N1—C7a1.366 (2)C34—H34C0.98
N1—N21.371 (2)C51—C521.496 (3)
N1—C111.413 (2)C52—C531.525 (3)
N2—C31.320 (2)C52—H52A0.99
N7—C7a1.397 (2)C52—H52B0.99
N7—C61.459 (2)C53—C5311.517 (3)
N7—C771.467 (2)C53—C5321.521 (3)
C3—C3a1.412 (3)C53—C541.534 (3)
C3—C311.510 (2)C54—C551.499 (3)
C3a—C7a1.365 (2)C54—H54A0.99
C3a—C41.494 (2)C54—H54B0.99
C4—C51.523 (2)C71—C721.384 (3)
C4—H4A0.99C71—C761.384 (3)
C4—H4B0.99C71—C771.502 (3)
C5—C551.520 (3)C72—C731.381 (3)
C5—C511.535 (2)C72—H720.95
C5—C61.565 (2)C73—C741.372 (3)
C6—H5A0.99C73—H730.95
C6—H5B0.99C74—C751.376 (3)
C11—C121.381 (3)C75—C761.381 (3)
C11—C161.382 (3)C75—H750.95
C12—C131.386 (3)C76—H760.95
C12—H120.95C77—H77A0.99
C13—C141.376 (3)C77—H77B0.99
C13—H130.95C531—H53A0.98
C14—C151.378 (3)C531—H53B0.98
C14—H140.95C531—H53C0.98
C15—C161.383 (3)C532—H53D0.98
C15—H150.95C532—H53E0.98
C16—H160.95C532—H53F0.98
C31—C341.522 (3)C81—O811.4202 (10)
C31—C331.523 (3)C81—C821.5388 (11)
C31—C321.525 (3)C81—H81A0.99
C32—H12A0.98C81—H81B0.99
C32—H12B0.98C82—H82A0.98
C32—H12C0.98C82—H82B0.98
C33—H33A0.98C82—H82C0.98
C33—H33B0.98O81—H810.84
C7a—N1—N2110.22 (14)H34B—C34—H34C109.5
C7a—N1—C11132.17 (16)O51—C51—C52121.25 (17)
N2—N1—C11117.33 (15)O51—C51—C5120.44 (17)
C3—N2—N1105.68 (15)C52—C51—C5118.13 (16)
C7a—N7—C6109.96 (14)C51—C52—C53115.02 (16)
C7a—N7—C77116.69 (15)C51—C52—H52A108.5
C6—N7—C77116.28 (15)C53—C52—H52A108.5
N2—C3—C3a111.46 (16)C51—C52—H52B108.5
N2—C3—C31120.47 (16)C53—C52—H52B108.5
C3a—C3—C31128.06 (16)H52A—C52—H52B107.5
C7a—C3a—C3104.77 (16)C531—C53—C532109.36 (18)
C7a—C3a—C4123.17 (16)C531—C53—C52110.50 (17)
C3—C3a—C4132.05 (16)C532—C53—C52108.77 (18)
C3a—C4—C5111.19 (15)C531—C53—C54110.13 (17)
C3a—C4—H4A109.4C532—C53—C54109.83 (17)
C5—C4—H4A109.4C52—C53—C54108.24 (16)
C3a—C4—H4B109.4C55—C54—C53110.74 (15)
C5—C4—H4B109.4C55—C54—H54A109.5
H4A—C4—H4B108.0C53—C54—H54A109.5
C55—C5—C4112.11 (15)C55—C54—H54B109.5
C55—C5—C51110.71 (15)C53—C54—H54B109.5
C4—C5—C51111.34 (15)H54A—C54—H54B108.1
C55—C5—C6109.68 (14)O55—C55—C54122.18 (17)
C4—C5—C6108.00 (15)O55—C55—C5120.92 (17)
C51—C5—C6104.69 (14)C54—C55—C5116.89 (16)
N7—C6—C5115.09 (15)C72—C71—C76118.41 (18)
N7—C6—H5A108.5C72—C71—C77119.53 (17)
C5—C6—H5A108.5C76—C71—C77122.06 (17)
N7—C6—H5B108.5C73—C72—C71121.01 (19)
C5—C6—H5B108.5C73—C72—H72119.5
H5A—C6—H5B107.5C71—C72—H72119.5
C3a—C7a—N1107.85 (16)C74—C73—C72118.98 (18)
C3a—C7a—N7126.05 (17)C74—C73—H73120.5
N1—C7a—N7125.97 (16)C72—C73—H73120.5
C12—C11—C16119.83 (17)C73—C74—C75121.63 (18)
C12—C11—N1121.55 (17)C73—C74—Cl7119.60 (16)
C16—C11—N1118.58 (17)C75—C74—Cl7118.74 (16)
C11—C12—C13119.72 (18)C74—C75—C76118.46 (19)
C11—C12—H12120.1C74—C75—H75120.8
C13—C12—H12120.1C76—C75—H75120.8
C14—C13—C12120.51 (19)C75—C76—C71121.43 (18)
C14—C13—H13119.7C75—C76—H76119.3
C12—C13—H13119.7C71—C76—H76119.3
C13—C14—C15119.58 (18)N7—C77—C71111.51 (15)
C13—C14—H14120.2N7—C77—H77A109.3
C15—C14—H14120.2C71—C77—H77A109.3
C14—C15—C16120.32 (19)N7—C77—H77B109.3
C14—C15—H15119.8C71—C77—H77B109.3
C16—C15—H15119.8H77A—C77—H77B108.0
C11—C16—C15119.98 (18)C53—C531—H53A109.5
C11—C16—H16120.0C53—C531—H53B109.5
C15—C16—H16120.0H53A—C531—H53B109.5
C3—C31—C34109.36 (15)C53—C531—H53C109.5
C3—C31—C33110.27 (15)H53A—C531—H53C109.5
C34—C31—C33108.67 (17)H53B—C531—H53C109.5
C3—C31—C32109.90 (16)C53—C532—H53D109.5
C34—C31—C32109.24 (16)C53—C532—H53E109.5
C33—C31—C32109.39 (17)H53D—C532—H53E109.5
C31—C32—H12A109.5C53—C532—H53F109.5
C31—C32—H12B109.5H53D—C532—H53F109.5
H12A—C32—H12B109.5H53E—C532—H53F109.5
C31—C32—H12C109.5O81—C81—C82109.60 (16)
H12A—C32—H12C109.5O81—C81—H81A105.3
H12B—C32—H12C109.5C82—C81—H81A109.7
C31—C33—H33A109.5O81—C81—H81B110.9
C31—C33—H33B109.5C82—C81—H81B112.9
H33A—C33—H33B109.5H81A—C81—H81B108.2
C31—C33—H33C109.5C81—C82—H82A113.1
H33A—C33—H33C109.5C81—C82—H82B107.1
H33B—C33—H33C109.5H82A—C82—H82B109.5
C31—C34—H34A109.5C81—C82—H82C108.2
C31—C34—H34B109.5H82A—C82—H82C109.5
H34A—C34—H34B109.5H82B—C82—H82C109.5
C31—C34—H34C109.5C81—O81—H81106.1
H34A—C34—H34C109.5
C7a—N1—N2—C31.0 (2)N2—C3—C31—C34122.09 (19)
C11—N1—N2—C3173.73 (16)C3a—C3—C31—C3456.5 (3)
N1—N2—C3—C3a1.2 (2)N2—C3—C31—C332.7 (3)
N1—N2—C3—C31177.67 (16)C3a—C3—C31—C33175.97 (19)
N2—C3—C3a—C7a0.9 (2)N2—C3—C31—C32118.00 (19)
C31—C3—C3a—C7a177.82 (18)C3a—C3—C31—C3263.4 (2)
N2—C3—C3a—C4178.41 (19)C55—C5—C51—O51150.01 (18)
C31—C3—C3a—C42.9 (3)C4—C5—C51—O5124.6 (2)
C7a—C3a—C4—C510.4 (3)C6—C5—C51—O5191.9 (2)
C3—C3a—C4—C5168.80 (19)C55—C5—C51—C5234.7 (2)
C3a—C4—C5—C5581.75 (19)C4—C5—C51—C52160.10 (17)
C3a—C4—C5—C51153.60 (16)C6—C5—C51—C5283.5 (2)
C3a—C4—C5—C639.2 (2)O51—C51—C52—C53142.14 (19)
C7a—N7—C6—C546.4 (2)C5—C51—C52—C5342.6 (2)
C77—N7—C6—C589.02 (19)C51—C52—C53—C53168.1 (2)
C55—C5—C6—N761.2 (2)C51—C52—C53—C532171.87 (18)
C4—C5—C6—N761.29 (19)C51—C52—C53—C5452.6 (2)
C51—C5—C6—N7179.99 (15)C531—C53—C54—C5562.5 (2)
C3—C3a—C7a—N10.3 (2)C532—C53—C54—C55177.03 (18)
C4—C3a—C7a—N1179.14 (17)C52—C53—C54—C5558.4 (2)
C3—C3a—C7a—N7175.60 (17)C53—C54—C55—O55122.6 (2)
C4—C3a—C7a—N75.0 (3)C53—C54—C55—C556.4 (2)
N2—N1—C7a—C3a0.4 (2)C4—C5—C55—O5511.8 (2)
C11—N1—C7a—C3a173.22 (19)C51—C5—C55—O55136.84 (18)
N2—N1—C7a—N7176.31 (17)C6—C5—C55—O55108.13 (19)
C11—N1—C7a—N72.6 (3)C4—C5—C55—C54167.18 (15)
C6—N7—C7a—C3a13.1 (3)C51—C5—C55—C5442.2 (2)
C77—N7—C7a—C3a122.1 (2)C6—C5—C55—C5472.85 (19)
C6—N7—C7a—N1162.01 (17)C76—C71—C72—C732.0 (3)
C77—N7—C7a—N162.8 (2)C77—C71—C72—C73177.88 (18)
C7a—N1—C11—C1221.5 (3)C71—C72—C73—C740.2 (3)
N2—N1—C11—C12151.77 (18)C72—C73—C74—C752.4 (3)
C7a—N1—C11—C16160.8 (2)C72—C73—C74—Cl7175.63 (15)
N2—N1—C11—C1625.9 (3)C73—C74—C75—C762.2 (3)
C16—C11—C12—C131.6 (3)Cl7—C74—C75—C76175.80 (15)
N1—C11—C12—C13179.26 (18)C74—C75—C76—C710.1 (3)
C11—C12—C13—C142.1 (3)C72—C71—C76—C752.2 (3)
C12—C13—C14—C150.6 (3)C77—C71—C76—C75177.72 (17)
C13—C14—C15—C161.4 (3)C7a—N7—C77—C71167.33 (15)
C12—C11—C16—C150.4 (3)C6—N7—C77—C7160.3 (2)
N1—C11—C16—C15177.36 (19)C72—C71—C77—N7146.42 (17)
C14—C15—C16—C111.9 (3)C76—C71—C77—N733.5 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O81—H81···Cg10.842.323.316 (5)157
C52—H52A···O810.992.273.188 (5)154
C75—H75···Cg2i0.952.553.469 (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 top
Crystal data top
C30H34BrN3O2·0.5C2H6OF(000) = 2392
Mr = 571.55Dx = 1.431 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 6083 reflections
a = 27.4453 (7) Åθ = 3.0–27.5°
b = 10.5519 (8) ŵ = 1.59 mm1
c = 21.715 (2) ÅT = 120 K
β = 122.484 (7)°Block, colourless
V = 5304.8 (8) Å30.45 × 0.35 × 0.25 mm
Z = 8
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
6083 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode3856 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.091
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.0°
ϕ and ω scansh = 3535
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 1313
Tmin = 0.499, Tmax = 0.673l = 2828
46446 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)] = 0.069Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.206H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0974P)2 + 44.0587P]
where P = (Fo2 + 2Fc2)/3
6083 reflections(Δ/σ)max = 0.001
351 parametersΔρmax = 0.87 e Å3
3 restraintsΔρmin = 1.30 e Å3
Crystal data top
C30H34BrN3O2·0.5C2H6OV = 5304.8 (8) Å3
Mr = 571.55Z = 8
Monoclinic, C2/cMo Kα radiation
a = 27.4453 (7) ŵ = 1.59 mm1
b = 10.5519 (8) ÅT = 120 K
c = 21.715 (2) Å0.45 × 0.35 × 0.25 mm
β = 122.484 (7)°
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
6083 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
3856 reflections with I > 2σ(I)
Tmin = 0.499, Tmax = 0.673Rint = 0.091
46446 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0693 restraints
wR(F2) = 0.206H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0974P)2 + 44.0587P]
where P = (Fo2 + 2Fc2)/3
6083 reflectionsΔρmax = 0.87 e Å3
351 parametersΔρmin = 1.30 e Å3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Br770.40465 (2)0.66538 (6)0.82875 (3)0.0332 (2)
O510.40003 (14)0.5905 (3)0.42828 (19)0.0228 (8)
O550.30756 (13)0.2518 (3)0.44048 (17)0.0151 (7)
N10.15891 (15)0.5070 (4)0.35692 (18)0.0090 (7)
N20.13518 (15)0.4820 (4)0.28451 (19)0.0109 (7)
N70.25612 (14)0.5333 (3)0.46678 (19)0.0085 (7)
C30.17891 (18)0.4673 (4)0.2761 (2)0.0105 (9)
C3a0.23227 (18)0.4803 (4)0.3433 (2)0.0098 (8)
C40.29344 (18)0.4690 (4)0.3629 (2)0.0120 (9)
C50.33537 (18)0.4665 (4)0.4457 (2)0.0117 (9)
C60.31333 (17)0.5621 (4)0.4803 (2)0.0099 (8)
C7a0.21786 (18)0.5055 (4)0.3928 (2)0.0085 (8)
C110.12120 (18)0.5392 (4)0.3798 (2)0.0098 (8)
C120.13888 (19)0.6151 (4)0.4404 (2)0.0128 (9)
C130.10012 (19)0.6455 (4)0.4604 (2)0.0149 (9)
C140.0443 (2)0.6030 (5)0.4199 (3)0.0187 (10)
C150.0264 (2)0.5297 (5)0.3590 (3)0.0214 (11)
C160.06469 (19)0.4958 (5)0.3392 (2)0.0154 (10)
C310.16845 (19)0.4434 (4)0.2009 (2)0.0120 (9)
C320.1941 (2)0.3161 (5)0.2002 (3)0.0209 (10)
C330.1045 (2)0.4433 (5)0.1435 (2)0.0208 (11)
C340.1973 (2)0.5477 (5)0.1830 (3)0.0190 (10)
C510.39478 (19)0.5182 (4)0.4672 (3)0.0143 (9)
C520.4457 (2)0.4839 (5)0.5416 (3)0.0197 (10)
C530.44772 (19)0.3453 (5)0.5640 (3)0.0189 (10)
C540.3893 (2)0.3142 (5)0.5543 (3)0.0165 (10)
C550.34054 (17)0.3348 (4)0.4767 (2)0.0098 (8)
C710.28833 (18)0.5036 (4)0.5955 (2)0.0100 (9)
C720.31802 (19)0.4226 (5)0.6547 (2)0.0152 (9)
C730.3507 (2)0.4697 (5)0.7247 (2)0.0186 (10)
C740.3534 (2)0.5987 (5)0.7349 (3)0.0187 (10)
C750.3233 (2)0.6806 (5)0.6783 (2)0.0174 (10)
C760.2907 (2)0.6318 (5)0.6082 (2)0.0151 (9)
C770.25481 (19)0.4487 (4)0.5196 (2)0.0106 (9)
C5310.4583 (2)0.2591 (5)0.5169 (3)0.0267 (12)
C5320.4957 (2)0.3308 (6)0.6436 (3)0.0316 (13)
C810.4699 (6)0.6839 (8)0.7106 (9)0.052 (3)0.50
C820.5234 (6)0.6483 (14)0.7853 (8)0.052 (3)0.50
O810.4362 (4)0.5738 (11)0.6767 (5)0.059 (3)0.50
H4A0.30280.54170.34220.014*
H4B0.29780.39040.34140.014*
H5A0.34150.56430.53370.012*
H5B0.31220.64780.46110.012*
H120.17740.64600.46820.015*
H130.11230.69620.50240.018*
H140.01790.62420.43390.022*
H150.01270.50220.33030.026*
H160.05240.44290.29800.018*
H12A0.17600.24870.21220.031*
H12B0.23580.31680.23640.031*
H12C0.18710.30070.15160.031*
H33A0.08550.37610.15440.031*
H33B0.09850.42810.09540.031*
H33C0.08790.52550.14360.031*
H34A0.23900.54650.21880.028*
H34B0.18150.63010.18460.028*
H34C0.18980.53370.13400.028*
H52A0.44520.53870.57830.024*
H52B0.48160.50280.54300.024*
H54A0.38930.22480.56810.020*
H54B0.38370.36860.58710.020*
H720.31580.33370.64690.018*
H730.37090.41410.76520.022*
H750.32470.76930.68660.021*
H760.26950.68790.56810.018*
H77A0.27150.36560.51950.013*
H77B0.21420.43480.50480.013*
H53A0.49510.28150.52240.040*
H53B0.42700.26890.46570.040*
H53C0.45980.17090.53200.040*
H53D0.53280.35200.64960.047*
H53E0.49670.24300.65900.047*
H53F0.48860.38790.67350.047*
H81A0.48220.71950.67880.062*0.50
H81B0.44620.74820.71590.062*0.50
H82A0.52980.55650.78930.078*0.50
H82B0.55740.69120.79110.078*0.50
H82C0.51720.67690.82350.078*0.50
H810.40870.57180.68310.088*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br770.0305 (3)0.0400 (4)0.0194 (3)0.0051 (3)0.0071 (2)0.0028 (2)
O510.0124 (16)0.0253 (19)0.0300 (19)0.0031 (14)0.0109 (15)0.0098 (16)
O550.0147 (16)0.0105 (15)0.0205 (17)0.0023 (13)0.0098 (14)0.0015 (13)
N10.0061 (17)0.0152 (19)0.0053 (16)0.0009 (14)0.0028 (14)0.0011 (14)
N20.0082 (17)0.0178 (19)0.0069 (16)0.0016 (15)0.0042 (14)0.0018 (15)
N70.0051 (17)0.0133 (18)0.0084 (16)0.0013 (14)0.0044 (14)0.0006 (14)
C30.010 (2)0.013 (2)0.010 (2)0.0037 (17)0.0065 (17)0.0008 (17)
C3a0.009 (2)0.011 (2)0.011 (2)0.0014 (17)0.0067 (17)0.0009 (17)
C40.012 (2)0.014 (2)0.013 (2)0.0006 (18)0.0085 (18)0.0027 (18)
C50.008 (2)0.015 (2)0.013 (2)0.0015 (17)0.0058 (17)0.0001 (18)
C60.0044 (19)0.012 (2)0.014 (2)0.0023 (16)0.0056 (17)0.0000 (17)
C7a0.0066 (19)0.008 (2)0.0093 (19)0.0012 (16)0.0034 (17)0.0014 (16)
C110.010 (2)0.010 (2)0.012 (2)0.0023 (17)0.0081 (17)0.0030 (17)
C120.010 (2)0.016 (2)0.013 (2)0.0009 (18)0.0069 (18)0.0007 (18)
C130.013 (2)0.017 (2)0.015 (2)0.0009 (18)0.0085 (18)0.0036 (18)
C140.019 (2)0.027 (3)0.018 (2)0.001 (2)0.015 (2)0.001 (2)
C150.010 (2)0.033 (3)0.021 (2)0.000 (2)0.009 (2)0.002 (2)
C160.011 (2)0.024 (3)0.013 (2)0.0025 (19)0.0074 (18)0.0042 (19)
C310.012 (2)0.017 (2)0.010 (2)0.0035 (18)0.0071 (18)0.0017 (17)
C320.025 (3)0.020 (3)0.019 (2)0.000 (2)0.012 (2)0.004 (2)
C330.016 (2)0.036 (3)0.011 (2)0.003 (2)0.0077 (19)0.007 (2)
C340.024 (3)0.023 (3)0.017 (2)0.004 (2)0.015 (2)0.001 (2)
C510.010 (2)0.014 (2)0.019 (2)0.0031 (18)0.0079 (19)0.0036 (19)
C520.011 (2)0.025 (3)0.019 (2)0.007 (2)0.006 (2)0.000 (2)
C530.008 (2)0.024 (3)0.020 (2)0.0020 (19)0.0045 (19)0.007 (2)
C540.017 (2)0.016 (2)0.019 (2)0.0023 (19)0.011 (2)0.0027 (19)
C550.0063 (19)0.012 (2)0.015 (2)0.0019 (17)0.0080 (17)0.0019 (18)
C710.0057 (19)0.013 (2)0.013 (2)0.0003 (17)0.0059 (17)0.0019 (17)
C720.013 (2)0.015 (2)0.016 (2)0.0017 (18)0.0066 (19)0.0038 (18)
C730.012 (2)0.021 (3)0.013 (2)0.0029 (19)0.0006 (18)0.0060 (19)
C740.012 (2)0.023 (3)0.015 (2)0.005 (2)0.0028 (19)0.004 (2)
C750.019 (2)0.016 (2)0.015 (2)0.0013 (19)0.0078 (19)0.0009 (19)
C760.014 (2)0.020 (2)0.011 (2)0.0018 (18)0.0061 (18)0.0018 (18)
C770.012 (2)0.011 (2)0.012 (2)0.0022 (17)0.0085 (18)0.0009 (17)
C5310.014 (2)0.031 (3)0.033 (3)0.006 (2)0.011 (2)0.006 (2)
C5320.020 (3)0.033 (3)0.025 (3)0.003 (2)0.000 (2)0.010 (2)
C810.044 (5)0.032 (7)0.068 (6)0.008 (5)0.022 (4)0.002 (5)
C820.044 (5)0.032 (7)0.068 (6)0.008 (5)0.022 (4)0.002 (5)
O810.037 (5)0.083 (8)0.066 (7)0.012 (5)0.034 (5)0.007 (6)
Geometric parameters (Å, º) top
Br77—C741.883 (5)C33—H33C0.98
O51—C511.203 (6)C34—H34A0.98
O55—C551.200 (5)C34—H34B0.98
N1—N21.366 (5)C34—H34C0.98
N1—C7a1.368 (5)C51—C521.507 (6)
N1—C111.409 (5)C52—C531.532 (7)
N2—C31.317 (6)C52—H52A0.99
N7—C7a1.398 (5)C52—H52B0.99
N7—C61.466 (5)C53—C5311.511 (7)
N7—C771.469 (5)C53—C5321.516 (7)
C3—C3a1.413 (6)C53—C541.535 (6)
C3—C311.519 (6)C54—C551.502 (6)
C3a—C7a1.358 (6)C54—H54A0.99
C3a—C41.499 (6)C54—H54B0.99
C4—C51.529 (6)C71—C761.375 (7)
C4—H4A0.99C71—C721.386 (6)
C4—H4B0.99C71—C771.507 (6)
C5—C551.516 (6)C72—C731.377 (6)
C5—C511.536 (6)C72—H720.95
C5—C61.562 (6)C73—C741.374 (7)
C6—H5A0.99C73—H730.95
C6—H5B0.99C74—C751.361 (7)
C11—C161.387 (6)C75—C761.386 (6)
C11—C121.387 (6)C75—H750.95
C12—C131.385 (6)C76—H760.95
C12—H120.95C77—H77A0.99
C13—C141.369 (7)C77—H77B0.99
C13—H130.95C531—H53A0.98
C14—C151.375 (7)C531—H53B0.98
C14—H140.95C531—H53C0.98
C15—C161.379 (6)C532—H53D0.98
C15—H150.95C532—H53E0.98
C16—H160.95C532—H53F0.98
C31—C331.512 (6)C81—O811.4201 (10)
C31—C321.521 (6)C81—C821.5398 (11)
C31—C341.523 (6)C81—H81A0.99
C32—H12A0.98C81—H81B0.99
C32—H12B0.98C82—H82A0.98
C32—H12C0.98C82—H82B0.98
C33—H33A0.98C82—H82C0.98
C33—H33B0.98O81—H810.84
N2—N1—C7a109.9 (3)H34B—C34—H34C109.5
N2—N1—C11117.8 (3)O51—C51—C52121.0 (4)
C7a—N1—C11132.0 (4)O51—C51—C5121.4 (4)
C3—N2—N1106.0 (3)C52—C51—C5117.4 (4)
C7a—N7—C6109.7 (3)C51—C52—C53115.2 (4)
C7a—N7—C77116.8 (3)C51—C52—H52A108.5
C6—N7—C77116.2 (3)C53—C52—H52A108.5
N2—C3—C3a111.2 (4)C51—C52—H52B108.5
N2—C3—C31120.6 (4)C53—C52—H52B108.5
C3a—C3—C31128.2 (4)H52A—C52—H52B107.5
C7a—C3a—C3104.8 (4)C531—C53—C532110.2 (4)
C7a—C3a—C4123.3 (4)C531—C53—C52110.3 (4)
C3—C3a—C4131.8 (4)C532—C53—C52108.6 (4)
C3a—C4—C5110.8 (3)C531—C53—C54110.2 (4)
C3a—C4—H4A109.5C532—C53—C54109.8 (4)
C5—C4—H4A109.5C52—C53—C54107.6 (4)
C3a—C4—H4B109.5C55—C54—C53111.0 (4)
C5—C4—H4B109.5C55—C54—H54A109.4
H4A—C4—H4B108.1C53—C54—H54A109.4
C55—C5—C4111.7 (4)C55—C54—H54B109.4
C55—C5—C51111.1 (4)C53—C54—H54B109.4
C4—C5—C51110.9 (3)H54A—C54—H54B108.0
C55—C5—C6110.3 (3)O55—C55—C54122.2 (4)
C4—C5—C6108.3 (3)O55—C55—C5121.3 (4)
C51—C5—C6104.3 (3)C54—C55—C5116.4 (4)
N7—C6—C5114.8 (3)C76—C71—C72118.7 (4)
N7—C6—H5A108.6C76—C71—C77122.1 (4)
C5—C6—H5A108.6C72—C71—C77119.2 (4)
N7—C6—H5B108.6C73—C72—C71120.7 (4)
C5—C6—H5B108.6C73—C72—H72119.6
H5A—C6—H5B107.5C71—C72—H72119.6
C3a—C7a—N1108.0 (4)C74—C73—C72118.8 (4)
C3a—C7a—N7126.4 (4)C74—C73—H73120.6
N1—C7a—N7125.5 (4)C72—C73—H73120.6
C16—C11—C12119.7 (4)C75—C74—C73122.0 (4)
C16—C11—N1118.6 (4)C75—C74—Br77118.6 (4)
C12—C11—N1121.7 (4)C73—C74—Br77119.3 (4)
C13—C12—C11119.7 (4)C74—C75—C76118.5 (5)
C13—C12—H12120.2C74—C75—H75120.8
C11—C12—H12120.2C76—C75—H75120.8
C14—C13—C12120.4 (4)C71—C76—C75121.2 (4)
C14—C13—H13119.8C71—C76—H76119.4
C12—C13—H13119.8C75—C76—H76119.4
C13—C14—C15120.1 (4)N7—C77—C71111.4 (3)
C13—C14—H14120.0N7—C77—H77A109.3
C15—C14—H14120.0C71—C77—H77A109.3
C14—C15—C16120.4 (4)N7—C77—H77B109.3
C14—C15—H15119.8C71—C77—H77B109.3
C16—C15—H15119.8H77A—C77—H77B108.0
C15—C16—C11119.7 (4)C53—C531—H53A109.5
C15—C16—H16120.1C53—C531—H53B109.5
C11—C16—H16120.1H53A—C531—H53B109.5
C33—C31—C3110.6 (4)C53—C531—H53C109.5
C33—C31—C32109.3 (4)H53A—C531—H53C109.5
C3—C31—C32109.7 (4)H53B—C531—H53C109.5
C33—C31—C34108.8 (4)C53—C532—H53D109.5
C3—C31—C34109.2 (4)C53—C532—H53E109.5
C32—C31—C34109.2 (4)H53D—C532—H53E109.5
C31—C32—H12A109.5C53—C532—H53F109.5
C31—C32—H12B109.5H53D—C532—H53F109.5
H12A—C32—H12B109.5H53E—C532—H53F109.5
C31—C32—H12C109.5O81—C81—C82109.50 (16)
H12A—C32—H12C109.5O81—C81—H81A108.7
H12B—C32—H12C109.5C82—C81—H81A109.8
C31—C33—H33A109.5O81—C81—H81B109.5
C31—C33—H33B109.5C82—C81—H81B111.1
H33A—C33—H33B109.5H81A—C81—H81B108.2
C31—C33—H33C109.5C81—C82—H82A110.9
H33A—C33—H33C109.5C81—C82—H82B109.0
H33B—C33—H33C109.5H82A—C82—H82B109.5
C31—C34—H34A109.5C81—C82—H82C108.4
C31—C34—H34B109.5H82A—C82—H82C109.5
H34A—C34—H34B109.5H82B—C82—H82C109.5
C31—C34—H34C109.5C81—O81—H81109.2
H34A—C34—H34C109.5
C7a—N1—N2—C30.9 (5)N2—C3—C31—C331.4 (6)
C11—N1—N2—C3173.8 (4)C3a—C3—C31—C33176.8 (4)
N1—N2—C3—C3a1.0 (5)N2—C3—C31—C32119.2 (5)
N1—N2—C3—C31177.5 (4)C3a—C3—C31—C3262.5 (6)
N2—C3—C3a—C7a0.8 (5)N2—C3—C31—C34121.1 (5)
C31—C3—C3a—C7a177.6 (4)C3a—C3—C31—C3457.1 (6)
N2—C3—C3a—C4178.3 (4)C55—C5—C51—O51149.6 (4)
C31—C3—C3a—C43.4 (8)C4—C5—C51—O5124.7 (6)
C7a—C3a—C4—C59.9 (6)C6—C5—C51—O5191.6 (5)
C3—C3a—C4—C5169.0 (4)C55—C5—C51—C5235.5 (5)
C3a—C4—C5—C5582.8 (4)C4—C5—C51—C52160.3 (4)
C3a—C4—C5—C51152.7 (4)C6—C5—C51—C5283.3 (5)
C3a—C4—C5—C638.9 (5)O51—C51—C52—C53142.0 (5)
C7a—N7—C6—C546.9 (5)C5—C51—C52—C5343.1 (6)
C77—N7—C6—C588.3 (4)C51—C52—C53—C53167.5 (5)
C55—C5—C6—N761.1 (5)C51—C52—C53—C532171.6 (4)
C4—C5—C6—N761.4 (5)C51—C52—C53—C5452.8 (5)
C51—C5—C6—N7179.5 (3)C531—C53—C54—C5561.6 (5)
C3—C3a—C7a—N10.2 (5)C532—C53—C54—C55176.8 (4)
C4—C3a—C7a—N1178.9 (4)C52—C53—C54—C5558.7 (5)
C3—C3a—C7a—N7176.0 (4)C53—C54—C55—O55122.1 (5)
C4—C3a—C7a—N74.8 (7)C53—C54—C55—C557.2 (5)
N2—N1—C7a—C3a0.4 (5)C4—C5—C55—O5511.8 (6)
C11—N1—C7a—C3a173.3 (4)C51—C5—C55—O55136.2 (4)
N2—N1—C7a—N7176.7 (4)C6—C5—C55—O55108.7 (4)
C11—N1—C7a—N73.0 (7)C4—C5—C55—C54167.4 (4)
C6—N7—C7a—C3a13.8 (6)C51—C5—C55—C5443.0 (5)
C77—N7—C7a—C3a121.2 (5)C6—C5—C55—C5472.1 (4)
C6—N7—C7a—N1161.8 (4)C76—C71—C72—C731.9 (7)
C77—N7—C7a—N163.2 (6)C77—C71—C72—C73177.8 (4)
N2—N1—C11—C1626.2 (6)C71—C72—C73—C740.2 (7)
C7a—N1—C11—C16160.5 (5)C72—C73—C74—C752.4 (7)
N2—N1—C11—C12152.4 (4)C72—C73—C74—Br77172.8 (3)
C7a—N1—C11—C1221.0 (7)C73—C74—C75—C762.3 (7)
C16—C11—C12—C130.7 (7)Br77—C74—C75—C76172.9 (3)
N1—C11—C12—C13179.3 (4)C72—C71—C76—C752.0 (7)
C11—C12—C13—C141.1 (7)C77—C71—C76—C75177.7 (4)
C12—C13—C14—C150.0 (7)C74—C75—C76—C710.1 (7)
C13—C14—C15—C161.6 (8)C7a—N7—C77—C71168.1 (4)
C14—C15—C16—C112.0 (8)C6—N7—C77—C7159.9 (5)
C12—C11—C16—C150.8 (7)C76—C71—C77—N734.0 (6)
N1—C11—C16—C15177.8 (4)C72—C71—C77—N7145.7 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O81—H81···Cg10.842.253.060 (13)163
C52—H52A···O810.992.313.224 (12)153
C75—H75···Cg2i0.952.583.498 (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 top
Crystal data top
C31H37N3O2·0.5C2H6OF(000) = 2184
Mr = 506.67Dx = 1.268 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 6079 reflections
a = 27.281 (5) Åθ = 3.0–27.5°
b = 10.6438 (15) ŵ = 0.08 mm1
c = 21.567 (3) ÅT = 120 K
β = 122.082 (12)°Plate, colourless
V = 5306.1 (16) Å30.51 × 0.30 × 0.07 mm
Z = 8
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
6079 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode3421 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.118
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.0°
ϕ and ω scansh = 3535
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 1313
Tmin = 0.966, Tmax = 0.994l = 2828
48672 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.064H-atom parameters constrained
wR(F2) = 0.178 w = 1/[σ2(Fo2) + (0.0798P)2 + 5.3581P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
6079 reflectionsΔρmax = 0.33 e Å3
353 parametersΔρmin = 0.42 e Å3
3 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0013 (3)
Crystal data top
C31H37N3O2·0.5C2H6OV = 5306.1 (16) Å3
Mr = 506.67Z = 8
Monoclinic, C2/cMo Kα radiation
a = 27.281 (5) ŵ = 0.08 mm1
b = 10.6438 (15) ÅT = 120 K
c = 21.567 (3) Å0.51 × 0.30 × 0.07 mm
β = 122.082 (12)°
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
6079 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
3421 reflections with I > 2σ(I)
Tmin = 0.966, Tmax = 0.994Rint = 0.118
48672 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0643 restraints
wR(F2) = 0.178H-atom parameters constrained
S = 1.03Δρmax = 0.33 e Å3
6079 reflectionsΔρmin = 0.42 e Å3
353 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
O510.40116 (8)0.57688 (18)0.42391 (10)0.0338 (5)
O550.30648 (7)0.25161 (16)0.43702 (10)0.0310 (4)
N10.15866 (8)0.5062 (2)0.35618 (10)0.0231 (5)
N20.13449 (9)0.4803 (2)0.28306 (11)0.0255 (5)
N70.25593 (8)0.53193 (19)0.46551 (11)0.0231 (5)
C30.17842 (10)0.4655 (2)0.27438 (13)0.0228 (5)
C3a0.23187 (10)0.4787 (2)0.34157 (13)0.0225 (5)
C40.29293 (10)0.4681 (2)0.36048 (13)0.0239 (6)
C50.33488 (10)0.4648 (2)0.44311 (13)0.0231 (5)
C60.31297 (10)0.5592 (2)0.47861 (14)0.0244 (6)
C7a0.21749 (10)0.5043 (2)0.39186 (13)0.0231 (5)
C110.12056 (11)0.5395 (2)0.37907 (13)0.0238 (5)
C120.13788 (11)0.6173 (2)0.43854 (14)0.0277 (6)
C130.09940 (11)0.6477 (3)0.45937 (14)0.0306 (6)
C140.04337 (12)0.6045 (3)0.41959 (15)0.0337 (7)
C150.02575 (11)0.5303 (3)0.35935 (15)0.0341 (7)
C160.06436 (11)0.4959 (3)0.33921 (14)0.0298 (6)
C310.16826 (11)0.4382 (2)0.19967 (13)0.0262 (6)
C320.19113 (12)0.3083 (3)0.19900 (15)0.0346 (7)
C330.10375 (11)0.4429 (3)0.14166 (14)0.0358 (7)
C340.19923 (12)0.5361 (3)0.18114 (15)0.0326 (6)
C510.39511 (10)0.5122 (2)0.46521 (14)0.0249 (6)
C520.44470 (11)0.4807 (3)0.54006 (14)0.0299 (6)
C530.44664 (11)0.3431 (3)0.56176 (14)0.0296 (6)
C540.38808 (11)0.3108 (3)0.55163 (14)0.0291 (6)
C550.33985 (10)0.3333 (2)0.47468 (14)0.0246 (6)
C710.28853 (10)0.5055 (2)0.59495 (13)0.0227 (5)
C720.31999 (10)0.4286 (2)0.65533 (14)0.0272 (6)
C730.35308 (11)0.4790 (3)0.72453 (14)0.0298 (6)
C740.35590 (11)0.6068 (3)0.73634 (14)0.0273 (6)
C7410.39465 (12)0.6627 (3)0.81042 (14)0.0387 (7)
C750.32280 (11)0.6827 (3)0.67639 (13)0.0280 (6)
C760.28970 (11)0.6338 (2)0.60699 (13)0.0263 (6)
C770.25438 (11)0.4507 (2)0.51933 (13)0.0243 (6)
C5310.45835 (12)0.2583 (3)0.51433 (15)0.0359 (7)
C5320.49461 (13)0.3270 (3)0.64164 (15)0.0429 (8)
C810.4701 (3)0.6818 (4)0.7065 (4)0.0559 (12)0.50
C820.5207 (3)0.6490 (7)0.7840 (4)0.0559 (12)0.50
O810.4364 (2)0.5726 (5)0.6728 (3)0.0729 (16)0.50
H4A0.30220.54070.33970.029*
H4B0.29730.39050.33850.029*
H5A0.34110.56040.53210.029*
H5B0.31230.64440.45980.029*
H120.17610.64980.46510.033*
H130.11170.69860.50130.037*
H140.01690.62600.43380.040*
H150.01320.50220.33120.041*
H160.05220.44260.29820.036*
H12A0.17050.24500.20960.052*
H12B0.23260.30420.23630.052*
H12C0.18510.29200.15070.052*
H33A0.08340.38030.15310.054*
H33B0.09770.42470.09350.054*
H33C0.08870.52680.14110.054*
H34A0.24110.52960.21600.049*
H34B0.18600.62020.18410.049*
H34C0.19060.52140.13140.049*
H52A0.44260.53450.57600.036*
H52B0.48120.50100.54280.036*
H54A0.38800.22150.56440.035*
H54B0.38210.36290.58510.035*
H720.31880.34010.64900.033*
H730.37450.42430.76510.036*
H74A0.41910.72730.80770.058*
H74B0.41920.59680.84470.058*
H74C0.37110.70070.82750.058*
H750.32290.77090.68320.034*
H760.26730.68850.56680.032*
H77A0.27030.36720.51930.029*
H77B0.21370.43900.50520.029*
H53A0.49570.28040.52100.054*
H53B0.42770.26930.46280.054*
H53C0.45920.17050.52860.054*
H53D0.53180.35040.64800.064*
H53E0.49610.23920.65610.064*
H53F0.48690.38120.67220.064*
H81A0.48580.71160.67700.067*0.50
H81B0.44670.75030.70910.067*0.50
H82A0.55260.61260.78150.084*0.50
H82B0.53420.72500.81430.084*0.50
H82C0.50720.58780.80570.084*0.50
H810.40810.57450.67830.109*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O510.0262 (10)0.0413 (12)0.0347 (11)0.0041 (8)0.0167 (9)0.0063 (9)
O550.0281 (10)0.0274 (10)0.0360 (11)0.0039 (8)0.0159 (9)0.0039 (9)
N10.0191 (10)0.0315 (12)0.0200 (11)0.0025 (9)0.0114 (9)0.0024 (9)
N20.0235 (11)0.0320 (12)0.0226 (11)0.0018 (9)0.0134 (10)0.0013 (9)
N70.0219 (11)0.0286 (12)0.0201 (11)0.0024 (9)0.0121 (9)0.0001 (9)
C30.0203 (13)0.0242 (13)0.0238 (13)0.0001 (10)0.0115 (11)0.0002 (10)
C3a0.0212 (12)0.0231 (13)0.0237 (13)0.0002 (10)0.0122 (11)0.0020 (10)
C40.0188 (12)0.0299 (14)0.0225 (13)0.0019 (11)0.0106 (11)0.0006 (11)
C50.0232 (13)0.0253 (13)0.0218 (13)0.0006 (11)0.0126 (11)0.0006 (10)
C60.0223 (13)0.0276 (13)0.0242 (13)0.0020 (11)0.0130 (11)0.0001 (11)
C7a0.0214 (13)0.0263 (13)0.0216 (13)0.0020 (10)0.0115 (11)0.0009 (11)
C110.0234 (13)0.0280 (14)0.0230 (13)0.0002 (11)0.0143 (11)0.0010 (11)
C120.0251 (14)0.0308 (14)0.0290 (14)0.0033 (11)0.0157 (12)0.0008 (12)
C130.0354 (15)0.0341 (15)0.0285 (14)0.0002 (12)0.0211 (13)0.0018 (12)
C140.0281 (15)0.0446 (17)0.0359 (16)0.0022 (13)0.0221 (13)0.0045 (13)
C150.0238 (14)0.0487 (18)0.0329 (15)0.0056 (12)0.0173 (13)0.0068 (13)
C160.0247 (14)0.0399 (16)0.0265 (14)0.0041 (12)0.0148 (12)0.0040 (12)
C310.0238 (13)0.0330 (15)0.0234 (13)0.0033 (11)0.0135 (11)0.0038 (11)
C320.0402 (16)0.0351 (16)0.0304 (15)0.0008 (13)0.0199 (14)0.0050 (12)
C330.0250 (14)0.060 (2)0.0227 (14)0.0023 (13)0.0126 (12)0.0077 (13)
C340.0337 (15)0.0401 (17)0.0286 (15)0.0030 (13)0.0196 (13)0.0007 (12)
C510.0236 (13)0.0257 (13)0.0289 (14)0.0012 (11)0.0164 (12)0.0025 (11)
C520.0234 (13)0.0366 (15)0.0257 (14)0.0054 (12)0.0103 (12)0.0010 (12)
C530.0228 (13)0.0356 (15)0.0252 (14)0.0026 (11)0.0092 (12)0.0024 (12)
C540.0293 (14)0.0303 (14)0.0262 (14)0.0006 (11)0.0137 (12)0.0035 (11)
C550.0218 (13)0.0262 (14)0.0292 (14)0.0000 (11)0.0159 (12)0.0004 (11)
C710.0196 (12)0.0295 (14)0.0218 (13)0.0002 (11)0.0128 (11)0.0007 (11)
C720.0237 (13)0.0297 (14)0.0295 (15)0.0003 (11)0.0150 (12)0.0031 (12)
C730.0224 (13)0.0375 (16)0.0243 (14)0.0005 (12)0.0089 (12)0.0068 (12)
C740.0240 (13)0.0350 (15)0.0248 (14)0.0066 (11)0.0142 (12)0.0015 (11)
C7410.0356 (16)0.0496 (18)0.0248 (15)0.0087 (14)0.0118 (13)0.0019 (13)
C750.0286 (14)0.0300 (15)0.0268 (14)0.0020 (11)0.0156 (12)0.0003 (11)
C760.0246 (13)0.0302 (14)0.0232 (14)0.0002 (11)0.0121 (11)0.0023 (11)
C770.0273 (13)0.0249 (13)0.0247 (14)0.0013 (11)0.0166 (12)0.0015 (10)
C5310.0276 (15)0.0440 (17)0.0352 (16)0.0050 (13)0.0161 (13)0.0049 (13)
C5320.0344 (16)0.0487 (19)0.0307 (16)0.0000 (14)0.0071 (14)0.0039 (14)
C810.054 (3)0.053 (3)0.057 (3)0.008 (3)0.027 (2)0.002 (3)
C820.054 (3)0.053 (3)0.057 (3)0.008 (3)0.027 (2)0.002 (3)
O810.058 (3)0.092 (4)0.082 (4)0.025 (3)0.046 (3)0.039 (3)
Geometric parameters (Å, º) top
O51—C511.205 (3)C34—H34C0.98
O55—C551.208 (3)C51—C521.493 (4)
N1—C7a1.362 (3)C52—C531.530 (4)
N1—N21.376 (3)C52—H52A0.99
N1—C111.413 (3)C52—H52B0.99
N2—C31.317 (3)C53—C5311.520 (4)
N7—C7a1.393 (3)C53—C5321.521 (4)
N7—C61.456 (3)C53—C541.532 (4)
N7—C771.466 (3)C54—C551.491 (3)
C3—C3a1.415 (3)C54—H54A0.99
C3—C311.511 (3)C54—H54B0.99
C3a—C7a1.362 (3)C71—C721.384 (3)
C3a—C41.494 (3)C71—C761.387 (4)
C4—C51.523 (3)C71—C771.501 (3)
C4—H4A0.99C72—C731.378 (4)
C4—H4B0.99C72—H720.95
C5—C551.530 (3)C73—C741.378 (4)
C5—C511.533 (3)C73—H730.95
C5—C61.562 (3)C74—C751.378 (4)
C6—H5A0.99C74—C7411.494 (4)
C6—H5B0.99C741—H74A0.98
C11—C161.380 (4)C741—H74B0.98
C11—C121.382 (4)C741—H74C0.98
C12—C131.382 (3)C75—C761.375 (3)
C12—H120.95C75—H750.95
C13—C141.375 (4)C76—H760.95
C13—H130.95C77—H77A0.99
C14—C151.371 (4)C77—H77B0.99
C14—H140.95C531—H53A0.98
C15—C161.385 (4)C531—H53B0.98
C15—H150.95C531—H53C0.98
C16—H160.95C532—H53D0.98
C31—C321.520 (4)C532—H53E0.98
C31—C341.522 (4)C532—H53F0.98
C31—C331.525 (4)C81—O811.4201 (10)
C32—H12A0.98C81—C821.5393 (11)
C32—H12B0.98C81—H81A0.99
C32—H12C0.98C81—H81B0.99
C33—H33A0.98C82—H82A0.98
C33—H33B0.98C82—H82B0.98
C33—H33C0.98C82—H82C0.98
C34—H34A0.98O81—H810.84
C34—H34B0.98
C7a—N1—N2110.37 (18)C52—C51—C5117.9 (2)
C7a—N1—C11132.1 (2)C51—C52—C53114.2 (2)
N2—N1—C11117.21 (19)C51—C52—H52A108.7
C3—N2—N1105.58 (19)C53—C52—H52A108.7
C7a—N7—C6110.08 (19)C51—C52—H52B108.7
C7a—N7—C77117.2 (2)C53—C52—H52B108.7
C6—N7—C77116.2 (2)H52A—C52—H52B107.6
N2—C3—C3a111.3 (2)C531—C53—C532109.5 (2)
N2—C3—C31120.6 (2)C531—C53—C52110.4 (2)
C3a—C3—C31128.1 (2)C532—C53—C52108.8 (2)
C7a—C3a—C3105.0 (2)C531—C53—C54110.3 (2)
C7a—C3a—C4123.3 (2)C532—C53—C54109.9 (2)
C3—C3a—C4131.7 (2)C52—C53—C54107.9 (2)
C3a—C4—C5110.9 (2)C55—C54—C53111.1 (2)
C3a—C4—H4A109.5C55—C54—H54A109.4
C5—C4—H4A109.5C53—C54—H54A109.4
C3a—C4—H4B109.5C55—C54—H54B109.4
C5—C4—H4B109.5C53—C54—H54B109.4
H4A—C4—H4B108.0H54A—C54—H54B108.0
C4—C5—C55112.1 (2)O55—C55—C54122.5 (2)
C4—C5—C51111.8 (2)O55—C55—C5120.1 (2)
C55—C5—C51109.6 (2)C54—C55—C5117.3 (2)
C4—C5—C6108.3 (2)C72—C71—C76117.7 (2)
C55—C5—C6109.67 (19)C72—C71—C77120.6 (2)
C51—C5—C6105.19 (19)C76—C71—C77121.7 (2)
N7—C6—C5115.1 (2)C73—C72—C71120.8 (2)
N7—C6—H5A108.5C73—C72—H72119.6
C5—C6—H5A108.5C71—C72—H72119.6
N7—C6—H5B108.5C72—C73—C74121.6 (2)
C5—C6—H5B108.5C72—C73—H73119.2
H5A—C6—H5B107.5C74—C73—H73119.2
N1—C7a—C3a107.7 (2)C73—C74—C75117.4 (2)
N1—C7a—N7126.1 (2)C73—C74—C741122.0 (2)
C3a—C7a—N7126.1 (2)C75—C74—C741120.6 (2)
C16—C11—C12119.9 (2)C74—C741—H74A109.5
C16—C11—N1118.5 (2)C74—C741—H74B109.5
C12—C11—N1121.5 (2)H74A—C741—H74B109.5
C13—C12—C11119.8 (2)C74—C741—H74C109.5
C13—C12—H12120.1H74A—C741—H74C109.5
C11—C12—H12120.1H74B—C741—H74C109.5
C14—C13—C12120.2 (2)C76—C75—C74121.6 (2)
C14—C13—H13119.9C76—C75—H75119.2
C12—C13—H13119.9C74—C75—H75119.2
C15—C14—C13119.9 (2)C75—C76—C71120.9 (2)
C15—C14—H14120.1C75—C76—H76119.6
C13—C14—H14120.1C71—C76—H76119.6
C14—C15—C16120.5 (2)N7—C77—C71111.7 (2)
C14—C15—H15119.8N7—C77—H77A109.3
C16—C15—H15119.8C71—C77—H77A109.3
C11—C16—C15119.6 (2)N7—C77—H77B109.3
C11—C16—H16120.2C71—C77—H77B109.3
C15—C16—H16120.2H77A—C77—H77B108.0
C3—C31—C32110.0 (2)C53—C531—H53A109.5
C3—C31—C34109.6 (2)C53—C531—H53B109.5
C32—C31—C34109.4 (2)H53A—C531—H53B109.5
C3—C31—C33110.3 (2)C53—C531—H53C109.5
C32—C31—C33108.8 (2)H53A—C531—H53C109.5
C34—C31—C33108.8 (2)H53B—C531—H53C109.5
C31—C32—H12A109.5C53—C532—H53D109.5
C31—C32—H12B109.5C53—C532—H53E109.5
H12A—C32—H12B109.5H53D—C532—H53E109.5
C31—C32—H12C109.5C53—C532—H53F109.5
H12A—C32—H12C109.5H53D—C532—H53F109.5
H12B—C32—H12C109.5H53E—C532—H53F109.5
C31—C33—H33A109.5O81—C81—C82109.50 (16)
C31—C33—H33B109.5O81—C81—H81A108.4
H33A—C33—H33B109.5C82—C81—H81A109.1
C31—C33—H33C109.5O81—C81—H81B111.7
H33A—C33—H33C109.5C82—C81—H81B109.9
H33B—C33—H33C109.5H81A—C81—H81B108.2
C31—C34—H34A109.5C81—C82—H82A109.9
C31—C34—H34B109.5C81—C82—H82B109.8
H34A—C34—H34B109.5H82A—C82—H82B109.5
C31—C34—H34C109.5C81—C82—H82C108.7
H34A—C34—H34C109.5H82A—C82—H82C109.5
H34B—C34—H34C109.5H82B—C82—H82C109.5
O51—C51—C52121.8 (2)C81—O81—H81107.5
O51—C51—C5120.2 (2)
C7a—N1—N2—C31.2 (3)N2—C3—C31—C32115.3 (3)
C11—N1—N2—C3173.4 (2)C3a—C3—C31—C3264.7 (3)
N1—N2—C3—C3a1.2 (3)N2—C3—C31—C34124.5 (3)
N1—N2—C3—C31178.8 (2)C3a—C3—C31—C3455.6 (3)
N2—C3—C3a—C7a0.8 (3)N2—C3—C31—C334.8 (3)
C31—C3—C3a—C7a179.2 (2)C3a—C3—C31—C33175.3 (3)
N2—C3—C3a—C4178.7 (2)C4—C5—C51—O5120.3 (3)
C31—C3—C3a—C41.3 (4)C55—C5—C51—O51145.2 (2)
C7a—C3a—C4—C510.8 (3)C6—C5—C51—O5197.0 (3)
C3—C3a—C4—C5168.7 (3)C4—C5—C51—C52162.6 (2)
C3a—C4—C5—C5581.9 (2)C55—C5—C51—C5237.7 (3)
C3a—C4—C5—C51154.5 (2)C6—C5—C51—C5280.2 (3)
C3a—C4—C5—C639.1 (3)O51—C51—C52—C53136.4 (3)
C7a—N7—C6—C546.2 (3)C5—C51—C52—C5346.5 (3)
C77—N7—C6—C590.1 (3)C51—C52—C53—C53166.3 (3)
C4—C5—C6—N761.0 (3)C51—C52—C53—C532173.5 (2)
C55—C5—C6—N761.6 (3)C51—C52—C53—C5454.3 (3)
C51—C5—C6—N7179.4 (2)C531—C53—C54—C5562.7 (3)
N2—N1—C7a—C3a0.8 (3)C532—C53—C54—C55176.5 (2)
C11—N1—C7a—C3a172.8 (2)C52—C53—C54—C5557.9 (3)
N2—N1—C7a—N7176.9 (2)C53—C54—C55—O55122.3 (3)
C11—N1—C7a—N73.3 (4)C53—C54—C55—C555.7 (3)
C3—C3a—C7a—N10.0 (3)C4—C5—C55—O5510.5 (3)
C4—C3a—C7a—N1179.6 (2)C51—C5—C55—O55135.2 (2)
C3—C3a—C7a—N7176.1 (2)C6—C5—C55—O55109.8 (3)
C4—C3a—C7a—N74.3 (4)C4—C5—C55—C54167.5 (2)
C6—N7—C7a—N1161.9 (2)C51—C5—C55—C5442.8 (3)
C77—N7—C7a—N162.3 (3)C6—C5—C55—C5472.2 (3)
C6—N7—C7a—C3a13.5 (3)C76—C71—C72—C732.6 (4)
C77—N7—C7a—C3a122.3 (3)C77—C71—C72—C73177.6 (2)
C7a—N1—C11—C16159.9 (3)C71—C72—C73—C740.4 (4)
N2—N1—C11—C1626.8 (3)C72—C73—C74—C752.0 (4)
C7a—N1—C11—C1222.1 (4)C72—C73—C74—C741175.9 (2)
N2—N1—C11—C12151.1 (2)C73—C74—C75—C762.2 (4)
C16—C11—C12—C132.2 (4)C741—C74—C75—C76175.7 (2)
N1—C11—C12—C13179.9 (2)C74—C75—C76—C710.0 (4)
C11—C12—C13—C142.3 (4)C72—C71—C76—C752.4 (4)
C12—C13—C14—C150.4 (4)C77—C71—C76—C75177.8 (2)
C13—C14—C15—C161.6 (4)C7a—N7—C77—C71168.2 (2)
C12—C11—C16—C150.2 (4)C6—N7—C77—C7158.6 (3)
N1—C11—C16—C15178.2 (2)C72—C71—C77—N7143.4 (2)
C14—C15—C16—C111.7 (4)C76—C71—C77—N736.8 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O81—H81···Cg10.842.233.057 (7)166
C52—H52A···O810.992.223.145 (6)155
C75—H75···Cg2i0.952.593.519 (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 top
Crystal data top
C31H34F3N3O2·0.5C2H6OZ = 2
Mr = 560.65F(000) = 594
Triclinic, P1Dx = 1.332 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 10.3270 (12) ÅCell parameters from 6424 reflections
b = 11.9970 (14) Åθ = 2.8–27.5°
c = 12.427 (3) ŵ = 0.10 mm1
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) Å3
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
6424 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode3353 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.092
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 2.8°
ϕ and ω scansh = 1313
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 1515
Tmin = 0.963, Tmax = 0.973l = 1616
39346 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)] = 0.069Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.224H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.1175P)2 + 0.5775P]
where P = (Fo2 + 2Fc2)/3
6424 reflections(Δ/σ)max < 0.001
378 parametersΔρmax = 0.46 e Å3
3 restraintsΔρmin = 0.53 e Å3
Crystal data top
C31H34F3N3O2·0.5C2H6Oγ = 84.481 (9)°
Mr = 560.65V = 1398.0 (4) Å3
Triclinic, P1Z = 2
a = 10.3270 (12) ÅMo Kα radiation
b = 11.9970 (14) ŵ = 0.10 mm1
c = 12.427 (3) ÅT = 120 K
α = 75.016 (13)°0.47 × 0.35 × 0.28 mm
β = 70.059 (11)°
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
6424 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
3353 reflections with I > 2σ(I)
Tmin = 0.963, Tmax = 0.973Rint = 0.092
39346 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0693 restraints
wR(F2) = 0.224H-atom parameters constrained
S = 1.05Δρmax = 0.46 e Å3
6424 reflectionsΔρmin = 0.53 e Å3
378 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
F710.9210 (2)0.50091 (17)0.82642 (18)0.0489 (6)
F720.8580 (3)0.35315 (18)0.7966 (2)0.0722 (8)
F731.0380 (2)0.4394 (3)0.6759 (2)0.0861 (10)
O510.0749 (2)0.72548 (19)0.78300 (19)0.0356 (5)
O550.3465 (2)0.98307 (17)0.54177 (18)0.0320 (5)
N10.4623 (2)0.7687 (2)0.2764 (2)0.0243 (5)
N20.3737 (2)0.83214 (19)0.2231 (2)0.0261 (6)
N70.4747 (2)0.6969 (2)0.4773 (2)0.0230 (5)
C30.2657 (3)0.8551 (2)0.3107 (3)0.0245 (6)
C3a0.2838 (3)0.8083 (2)0.4213 (3)0.0240 (6)
C40.1960 (3)0.8104 (2)0.5440 (2)0.0242 (6)
C50.2818 (3)0.7866 (2)0.6245 (2)0.0246 (6)
C60.3788 (3)0.6813 (2)0.5971 (2)0.0242 (6)
C7a0.4101 (3)0.7554 (2)0.3956 (2)0.0241 (6)
C110.5825 (3)0.7238 (2)0.2036 (3)0.0238 (6)
C120.6402 (3)0.6208 (2)0.2452 (3)0.0258 (7)
C130.7574 (3)0.5799 (2)0.1722 (3)0.0272 (7)
C140.8173 (3)0.6400 (3)0.0576 (3)0.0312 (7)
C150.7579 (3)0.7421 (3)0.0161 (3)0.0341 (7)
C160.6412 (3)0.7846 (3)0.0876 (3)0.0302 (7)
C310.1506 (3)0.9300 (2)0.2837 (2)0.0258 (7)
C320.1608 (3)1.0480 (2)0.3074 (3)0.0312 (7)
C330.1606 (3)0.9469 (3)0.1559 (3)0.0314 (7)
C340.0125 (3)0.8757 (3)0.3629 (3)0.0316 (7)
C510.1943 (3)0.7508 (2)0.7547 (3)0.0263 (7)
C520.2628 (3)0.7479 (3)0.8443 (3)0.0322 (7)
C530.3392 (3)0.8598 (3)0.8215 (3)0.0308 (7)
C5310.2357 (3)0.9581 (3)0.8406 (3)0.0390 (8)
C5320.4231 (3)0.8435 (3)0.9038 (3)0.0357 (8)
C540.4368 (3)0.8862 (3)0.6943 (3)0.0282 (7)
C550.3596 (3)0.8942 (2)0.6105 (3)0.0263 (7)
C710.6832 (3)0.6674 (2)0.5354 (3)0.0251 (6)
C720.7550 (3)0.7156 (3)0.5877 (3)0.0274 (7)
C730.8279 (3)0.6481 (3)0.6560 (3)0.0304 (7)
C740.8290 (3)0.5299 (3)0.6729 (3)0.0302 (7)
C7410.9113 (3)0.4574 (3)0.7431 (3)0.0358 (8)
C750.7573 (3)0.4797 (3)0.6223 (3)0.0300 (7)
C760.6850 (3)0.5484 (2)0.5542 (3)0.0272 (7)
C770.6092 (3)0.7435 (2)0.4591 (3)0.0252 (6)
C810.5602 (16)0.4842 (18)0.9407 (8)0.077 (3)0.50
C820.457 (2)0.4830 (18)1.0643 (6)0.077 (3)0.50
O810.5048 (6)0.5504 (6)0.8537 (5)0.0702 (17)0.50
H14A0.12320.75150.57300.029*
H14B0.15060.88700.54450.029*
H6A0.43260.66240.65200.029*
H6B0.32050.61390.61410.029*
H120.59940.57800.32410.031*
H130.79740.50890.20160.033*
H140.89840.61150.00780.037*
H150.79810.78390.06330.041*
H160.60100.85520.05780.036*
H32A0.15051.03780.39070.047*
H32B0.08771.09930.28860.047*
H32C0.25081.08190.25810.047*
H33A0.25080.97900.10440.047*
H33B0.08791.00020.13940.047*
H33C0.14970.87240.14140.047*
H34A0.00730.79940.34980.047*
H34B0.06220.92500.34440.047*
H34C0.00360.86780.44570.047*
H52A0.32910.68250.84380.039*
H52B0.19220.73400.92360.039*
H53A0.28501.02980.82390.058*
H53B0.17410.94050.92260.058*
H53C0.18150.96730.78770.058*
H53D0.47010.91560.89000.054*
H53E0.49150.78200.88870.054*
H53F0.36180.82240.98580.054*
H54A0.48410.96000.67640.034*
H54B0.50770.82450.68430.034*
H720.75410.79700.57640.033*
H730.87690.68280.69110.037*
H750.75770.39820.63430.036*
H760.63570.51340.51970.033*
H77A0.59540.82060.47640.030*
H77B0.66680.75290.37540.030*
H81A0.65390.50270.93520.092*0.50
H81B0.56120.40380.93330.092*0.50
H82A0.43160.56431.06070.115*0.50
H82B0.49940.45381.12590.115*0.50
H82C0.37470.43811.08240.115*0.50
H810.54560.53110.79010.105*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
F710.0642 (13)0.0491 (12)0.0497 (13)0.0115 (10)0.0380 (11)0.0178 (10)
F720.1021 (19)0.0376 (12)0.102 (2)0.0008 (12)0.0780 (17)0.0004 (12)
F730.0510 (15)0.148 (3)0.0562 (16)0.0490 (16)0.0258 (13)0.0267 (16)
O510.0273 (12)0.0465 (14)0.0274 (12)0.0026 (10)0.0039 (10)0.0053 (10)
O550.0383 (12)0.0260 (11)0.0297 (12)0.0031 (9)0.0109 (10)0.0026 (9)
N10.0243 (13)0.0271 (13)0.0201 (13)0.0035 (10)0.0068 (11)0.0054 (10)
N20.0307 (13)0.0247 (13)0.0233 (13)0.0052 (10)0.0105 (11)0.0063 (10)
N70.0217 (12)0.0257 (12)0.0192 (13)0.0005 (10)0.0041 (10)0.0049 (10)
C30.0294 (15)0.0227 (15)0.0228 (15)0.0024 (12)0.0104 (13)0.0064 (12)
C3a0.0236 (14)0.0224 (14)0.0251 (16)0.0004 (12)0.0061 (13)0.0069 (12)
C40.0244 (14)0.0242 (15)0.0216 (15)0.0011 (12)0.0056 (12)0.0046 (12)
C50.0252 (15)0.0263 (15)0.0217 (15)0.0031 (12)0.0078 (13)0.0060 (12)
C60.0255 (15)0.0223 (14)0.0229 (15)0.0005 (12)0.0084 (13)0.0017 (12)
C7a0.0288 (15)0.0232 (15)0.0198 (15)0.0029 (12)0.0087 (13)0.0023 (11)
C110.0223 (14)0.0253 (15)0.0246 (16)0.0016 (12)0.0082 (12)0.0075 (12)
C120.0262 (15)0.0262 (15)0.0229 (16)0.0010 (12)0.0065 (13)0.0043 (12)
C130.0272 (15)0.0228 (15)0.0289 (17)0.0027 (12)0.0075 (14)0.0050 (12)
C140.0259 (16)0.0355 (17)0.0298 (18)0.0045 (13)0.0050 (14)0.0110 (14)
C150.0320 (17)0.0388 (18)0.0240 (17)0.0021 (14)0.0029 (14)0.0025 (14)
C160.0309 (16)0.0296 (16)0.0250 (17)0.0023 (13)0.0059 (14)0.0034 (13)
C310.0253 (15)0.0298 (16)0.0219 (16)0.0054 (12)0.0081 (13)0.0073 (12)
C320.0375 (17)0.0283 (16)0.0280 (17)0.0073 (13)0.0130 (15)0.0069 (13)
C330.0318 (17)0.0371 (18)0.0273 (17)0.0063 (13)0.0149 (14)0.0067 (14)
C340.0297 (16)0.0362 (17)0.0286 (17)0.0017 (13)0.0112 (14)0.0059 (13)
C510.0303 (17)0.0236 (15)0.0224 (16)0.0018 (12)0.0061 (13)0.0054 (12)
C520.0342 (17)0.0368 (18)0.0222 (16)0.0028 (14)0.0074 (14)0.0051 (13)
C530.0287 (16)0.0392 (18)0.0267 (17)0.0046 (13)0.0098 (14)0.0127 (14)
C5310.0392 (18)0.047 (2)0.038 (2)0.0140 (16)0.0171 (16)0.0202 (16)
C5320.0352 (17)0.0455 (19)0.0340 (19)0.0086 (15)0.0182 (15)0.0166 (15)
C540.0287 (16)0.0311 (16)0.0261 (16)0.0014 (13)0.0082 (13)0.0098 (13)
C550.0271 (15)0.0272 (16)0.0228 (16)0.0011 (12)0.0036 (13)0.0097 (13)
C710.0213 (14)0.0277 (15)0.0249 (16)0.0007 (12)0.0041 (13)0.0084 (12)
C720.0255 (15)0.0260 (15)0.0305 (17)0.0019 (12)0.0077 (13)0.0077 (13)
C730.0280 (16)0.0360 (18)0.0314 (18)0.0012 (13)0.0130 (14)0.0104 (14)
C740.0257 (15)0.0324 (17)0.0332 (18)0.0050 (13)0.0114 (14)0.0087 (14)
C7410.0378 (19)0.0371 (19)0.0380 (19)0.0031 (14)0.0187 (16)0.0113 (15)
C750.0314 (16)0.0262 (16)0.0337 (18)0.0012 (13)0.0131 (14)0.0068 (13)
C760.0249 (15)0.0292 (16)0.0295 (17)0.0022 (12)0.0086 (13)0.0100 (13)
C770.0242 (15)0.0241 (15)0.0258 (16)0.0039 (12)0.0079 (13)0.0026 (12)
C810.091 (5)0.058 (11)0.062 (3)0.058 (5)0.025 (3)0.002 (4)
C820.091 (5)0.058 (11)0.062 (3)0.058 (5)0.025 (3)0.002 (4)
O810.066 (4)0.094 (5)0.053 (4)0.029 (3)0.023 (3)0.027 (3)
Geometric parameters (Å, º) top
F71—C7411.310 (4)C33—H33C0.98
F72—C7411.328 (4)C34—H34A0.98
F73—C7411.323 (4)C34—H34B0.98
O51—C511.207 (4)C34—H34C0.98
O55—C551.210 (3)C51—C521.502 (4)
N1—C7a1.363 (4)C52—C531.536 (4)
N1—N21.369 (3)C52—H52A0.99
N1—C111.417 (3)C52—H52B0.99
N2—C31.332 (4)C53—C5321.518 (4)
N7—C7a1.405 (4)C53—C5311.523 (4)
N7—C61.455 (4)C53—C541.527 (4)
N7—C771.470 (3)C531—H53A0.98
C3—C3a1.413 (4)C531—H53B0.98
C3—C311.498 (4)C531—H53C0.98
C3a—C7a1.366 (4)C532—H53D0.98
C3a—C41.490 (4)C532—H53E0.98
C4—C51.509 (4)C532—H53F0.98
C4—H14A0.99C54—C551.493 (4)
C4—H14B0.99C54—H54A0.99
C5—C551.526 (4)C54—H54B0.99
C5—C511.528 (4)C71—C721.383 (4)
C5—C61.569 (4)C71—C761.385 (4)
C6—H6A0.99C71—C771.493 (4)
C6—H6B0.99C72—C731.381 (4)
C11—C121.374 (4)C72—H720.95
C11—C161.387 (4)C73—C741.378 (4)
C12—C131.377 (4)C73—H730.95
C12—H120.95C74—C751.380 (4)
C13—C141.373 (4)C74—C7411.486 (4)
C13—H130.95C75—C761.380 (4)
C14—C151.373 (4)C75—H750.95
C14—H140.95C76—H760.95
C15—C161.374 (4)C77—H77A0.99
C15—H150.95C77—H77B0.99
C16—H160.95C81—O811.4200 (11)
C31—C331.516 (4)C81—C821.5388 (11)
C31—C341.522 (4)C81—H81A0.99
C31—C321.538 (4)C81—H81B0.99
C32—H32A0.98C82—H82A0.98
C32—H32B0.98C82—H82B0.98
C32—H32C0.98C82—H82C0.98
C33—H33A0.98O81—H810.84
C33—H33B0.98
C7a—N1—N2110.6 (2)C52—C51—C5117.5 (3)
C7a—N1—C11131.9 (2)C51—C52—C53113.1 (2)
N2—N1—C11117.4 (2)C51—C52—H52A109.0
C3—N2—N1105.3 (2)C53—C52—H52A109.0
C7a—N7—C6110.4 (2)C51—C52—H52B109.0
C7a—N7—C77114.7 (2)C53—C52—H52B109.0
C6—N7—C77114.5 (2)H52A—C52—H52B107.8
N2—C3—C3a111.4 (2)C532—C53—C531110.2 (3)
N2—C3—C31119.9 (2)C532—C53—C54108.9 (2)
C3a—C3—C31128.5 (3)C531—C53—C54110.2 (3)
C7a—C3a—C3104.7 (2)C532—C53—C52109.8 (3)
C7a—C3a—C4122.8 (3)C531—C53—C52109.7 (3)
C3—C3a—C4132.4 (2)C54—C53—C52108.1 (2)
C3a—C4—C5110.5 (2)C53—C531—H53A109.5
C3a—C4—H14A109.6C53—C531—H53B109.5
C5—C4—H14A109.6H53A—C531—H53B109.5
C3a—C4—H14B109.6C53—C531—H53C109.5
C5—C4—H14B109.6H53A—C531—H53C109.5
H14A—C4—H14B108.1H53B—C531—H53C109.5
C4—C5—C55111.0 (2)C53—C532—H53D109.5
C4—C5—C51112.4 (2)C53—C532—H53E109.5
C55—C5—C51106.2 (2)H53D—C532—H53E109.5
C4—C5—C6107.5 (2)C53—C532—H53F109.5
C55—C5—C6113.3 (2)H53D—C532—H53F109.5
C51—C5—C6106.4 (2)H53E—C532—H53F109.5
N7—C6—C5116.2 (2)C55—C54—C53110.7 (2)
N7—C6—H6A108.2C55—C54—H54A109.5
C5—C6—H6A108.2C53—C54—H54A109.5
N7—C6—H6B108.2C55—C54—H54B109.5
C5—C6—H6B108.2C53—C54—H54B109.5
H6A—C6—H6B107.4H54A—C54—H54B108.1
N1—C7a—C3a108.0 (2)O55—C55—C54123.2 (3)
N1—C7a—N7125.9 (2)O55—C55—C5120.0 (3)
C3a—C7a—N7126.1 (3)C54—C55—C5116.5 (2)
C12—C11—C16119.7 (3)C72—C71—C76118.1 (3)
C12—C11—N1121.3 (3)C72—C71—C77120.0 (3)
C16—C11—N1119.0 (2)C76—C71—C77122.0 (3)
C11—C12—C13119.8 (3)C73—C72—C71121.5 (3)
C11—C12—H12120.1C73—C72—H72119.2
C13—C12—H12120.1C71—C72—H72119.2
C14—C13—C12121.0 (3)C74—C73—C72119.4 (3)
C14—C13—H13119.5C74—C73—H73120.3
C12—C13—H13119.5C72—C73—H73120.3
C13—C14—C15118.9 (3)C73—C74—C75120.2 (3)
C13—C14—H14120.6C73—C74—C741119.4 (3)
C15—C14—H14120.6C75—C74—C741120.4 (3)
C14—C15—C16121.0 (3)F71—C741—F73107.4 (3)
C14—C15—H15119.5F71—C741—F72105.8 (3)
C16—C15—H15119.5F73—C741—F72105.3 (3)
C15—C16—C11119.6 (3)F71—C741—C74113.7 (3)
C15—C16—H16120.2F73—C741—C74111.9 (3)
C11—C16—H16120.2F72—C741—C74112.1 (3)
C3—C31—C33111.2 (2)C76—C75—C74119.8 (3)
C3—C31—C34110.0 (2)C76—C75—H75120.1
C33—C31—C34109.0 (2)C74—C75—H75120.1
C3—C31—C32107.9 (2)C75—C76—C71121.1 (3)
C33—C31—C32109.2 (2)C75—C76—H76119.5
C34—C31—C32109.4 (2)C71—C76—H76119.5
C31—C32—H32A109.5N7—C77—C71112.4 (2)
C31—C32—H32B109.5N7—C77—H77A109.1
H32A—C32—H32B109.5C71—C77—H77A109.1
C31—C32—H32C109.5N7—C77—H77B109.1
H32A—C32—H32C109.5C71—C77—H77B109.1
H32B—C32—H32C109.5H77A—C77—H77B107.9
C31—C33—H33A109.5O81—C81—C82109.53 (16)
C31—C33—H33B109.5O81—C81—H81A118.1
H33A—C33—H33B109.5C82—C81—H81A110.8
C31—C33—H33C109.5O81—C81—H81B104.6
H33A—C33—H33C109.5C82—C81—H81B104.5
H33B—C33—H33C109.5H81A—C81—H81B108.2
C31—C34—H34A109.5C81—C82—H82A104.0
C31—C34—H34B109.5C81—C82—H82B111.9
H34A—C34—H34B109.5H82A—C82—H82B109.5
C31—C34—H34C109.5C81—C82—H82C112.4
H34A—C34—H34C109.5H82A—C82—H82C109.5
H34B—C34—H34C109.5H82B—C82—H82C109.5
O51—C51—C52122.0 (3)C81—O81—H81108.3
O51—C51—C5120.5 (3)
C7a—N1—N2—C31.5 (3)C3a—C3—C31—C3450.9 (4)
C11—N1—N2—C3174.9 (2)N2—C3—C31—C32106.4 (3)
N1—N2—C3—C3a0.8 (3)C3a—C3—C31—C3268.4 (4)
N1—N2—C3—C31176.4 (2)C4—C5—C51—O5112.4 (4)
N2—C3—C3a—C7a0.2 (3)C55—C5—C51—O51134.0 (3)
C31—C3—C3a—C7a175.0 (3)C6—C5—C51—O51104.9 (3)
N2—C3—C3a—C4179.4 (3)C4—C5—C51—C52168.0 (2)
C31—C3—C3a—C44.2 (5)C55—C5—C51—C5246.4 (3)
C7a—C3a—C4—C519.9 (4)C6—C5—C51—C5274.7 (3)
C3—C3a—C4—C5159.2 (3)O51—C51—C52—C53129.4 (3)
C3a—C4—C5—C5579.0 (3)C5—C51—C52—C5351.0 (3)
C3a—C4—C5—C51162.1 (2)C51—C52—C53—C532171.4 (2)
C3a—C4—C5—C645.4 (3)C51—C52—C53—C53167.4 (3)
C7a—N7—C6—C541.0 (3)C51—C52—C53—C5452.8 (3)
C77—N7—C6—C590.3 (3)C532—C53—C54—C55175.8 (2)
C4—C5—C6—N760.7 (3)C531—C53—C54—C5563.3 (3)
C55—C5—C6—N762.3 (3)C52—C53—C54—C5556.6 (3)
C51—C5—C6—N7178.7 (2)C53—C54—C55—O55113.0 (3)
N2—N1—C7a—C3a1.6 (3)C53—C54—C55—C560.0 (3)
C11—N1—C7a—C3a174.0 (3)C4—C5—C55—O550.4 (4)
N2—N1—C7a—N7178.9 (2)C51—C5—C55—O55122.0 (3)
C11—N1—C7a—N75.5 (5)C6—C5—C55—O55121.5 (3)
C3—C3a—C7a—N11.1 (3)C4—C5—C55—C54173.7 (2)
C4—C3a—C7a—N1179.6 (2)C51—C5—C55—C5451.2 (3)
C3—C3a—C7a—N7179.4 (3)C6—C5—C55—C5465.3 (3)
C4—C3a—C7a—N70.1 (4)C76—C71—C72—C730.6 (4)
C6—N7—C7a—N1169.2 (3)C77—C71—C72—C73178.1 (3)
C77—N7—C7a—N159.6 (4)C71—C72—C73—C740.2 (5)
C6—N7—C7a—C3a10.2 (4)C72—C73—C74—C750.3 (5)
C77—N7—C7a—C3a121.0 (3)C72—C73—C74—C741177.9 (3)
C7a—N1—C11—C1227.5 (4)C73—C74—C741—F7131.2 (4)
N2—N1—C11—C12147.9 (3)C75—C74—C741—F71150.6 (3)
C7a—N1—C11—C16153.6 (3)C73—C74—C741—F7390.7 (4)
N2—N1—C11—C1631.0 (4)C75—C74—C741—F7387.5 (4)
C16—C11—C12—C131.3 (4)C73—C74—C741—F72151.2 (3)
N1—C11—C12—C13179.8 (3)C75—C74—C741—F7230.6 (4)
C11—C12—C13—C140.6 (4)C73—C74—C75—C760.3 (5)
C12—C13—C14—C150.4 (5)C741—C74—C75—C76177.9 (3)
C13—C14—C15—C160.6 (5)C74—C75—C76—C710.1 (5)
C14—C15—C16—C110.1 (5)C72—C71—C76—C750.6 (4)
C12—C11—C16—C151.1 (4)C77—C71—C76—C75178.2 (3)
N1—C11—C16—C15179.9 (3)C7a—N7—C77—C71170.7 (2)
N2—C3—C31—C3313.4 (4)C6—N7—C77—C7160.1 (3)
C3a—C3—C31—C33171.8 (3)C72—C71—C77—N7139.9 (3)
N2—C3—C31—C34134.3 (3)C76—C71—C77—N741.3 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O81—H81···Cg10.842.583.245 (6)137
C52—H52A···O810.992.313.285 (8)170
C75—H75···Cg2i0.952.673.544 (4)154
C77—H77A···O55ii0.992.423.352 (3)157
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1, y+2, z+1.

Experimental details

(I)(II)(III)(IV)
Crystal data
Chemical formulaC30H34ClN3O2·0.5C2H6OC30H34BrN3O2·0.5C2H6OC31H37N3O2·0.5C2H6OC31H34F3N3O2·0.5C2H6O
Mr527.09571.55506.67560.65
Crystal system, space groupMonoclinic, C2/cMonoclinic, C2/cMonoclinic, C2/cTriclinic, P1
Temperature (K)120120120120
a, b, c (Å)27.419 (4), 10.5860 (13), 21.580 (3)27.4453 (7), 10.5519 (8), 21.715 (2)27.281 (5), 10.6438 (15), 21.567 (3)10.3270 (12), 11.9970 (14), 12.427 (3)
α, β, γ (°)90, 122.625 (11), 9090, 122.484 (7), 9090, 122.082 (12), 9075.016 (13), 70.059 (11), 84.481 (9)
V3)5275.5 (14)5304.8 (8)5306.1 (16)1398.0 (4)
Z8882
Radiation typeMo KαMo KαMo KαMo Kα
µ (mm1)0.181.590.080.10
Crystal size (mm)0.32 × 0.23 × 0.220.45 × 0.35 × 0.250.51 × 0.30 × 0.070.47 × 0.35 × 0.28
Data collection
DiffractometerBruker Nonius KappaCCD area-detector
diffractometer
Bruker Nonius KappaCCD area-detector
diffractometer
Bruker Nonius KappaCCD area-detector
diffractometer
Bruker Nonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Multi-scan
(SADABS; Sheldrick, 2003)
Multi-scan
(SADABS; Sheldrick, 2003)
Multi-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.954, 0.9610.499, 0.6730.966, 0.9940.963, 0.973
No. of measured, independent and
observed [I > 2σ(I)] reflections
36250, 6021, 4812 46446, 6083, 3856 48672, 6079, 3421 39346, 6424, 3353
Rint0.0590.0910.1180.092
(sin θ/λ)max1)0.6500.6500.6500.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.051, 0.132, 1.08 0.069, 0.206, 1.04 0.064, 0.178, 1.03 0.069, 0.224, 1.05
No. of reflections6021608360796424
No. of parameters352351353378
No. of restraints3333
H-atom treatmentH-atom parameters constrainedH-atom parameters constrainedH-atom parameters constrainedH-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0455P)2 + 11.7674P]
where P = (Fo2 + 2Fc2)/3
w = 1/[σ2(Fo2) + (0.0974P)2 + 44.0587P]
where P = (Fo2 + 2Fc2)/3
w = 1/[σ2(Fo2) + (0.0798P)2 + 5.3581P]
where P = (Fo2 + 2Fc2)/3
w = 1/[σ2(Fo2) + (0.1175P)2 + 0.5775P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)0.55, 0.520.87, 1.300.33, 0.420.46, 0.53

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)–(IV) top
Ring-puckering parameters
(I)(II)(III)(IV)
Q0.482 (2)0.483 (5)0.477 (3)0.475 (5)
θ53.6 (2)53.3 (6)53.1 (4)50.2 (4)
ϕ87.9 (3)86.7 (7)88.0 (4)100.9 (4)
Torsion angles
(I)(II)(III)(IV)
N2-C3-C31-C32-118.00 (19)-119.2 (5)-115.3 (3)-106.4 (3)
N2-C3-C31-C332.7 (3)1.4 (6)4.8 (3)13.4 (4)
N2-C3-C31-C34122.09 (19)121.1 (5)124.5 (3)134.3 (3)
N2-N1-C11-C12-151.77 (18)-152.4 (4)-151.1 (2)-147.9 (3)
C6-N7-C77-C7160.3 (2)59.9 (5)58.6 (3)60.1 (3)
N7-C77-C71-C72-146.42 (17)-145.7 (4)-143.4 (2)-139.9 (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)–(IV)a top
CompoundD-H···AD-HH···AD···AD-H···A
(I)O81-H81···Cg10.842.323.116 (5)157
C52-H52A···O810.992.273.188 (5)154
C75-H75···Cg2i0.952.553.469 (2)163
(II)O81-H81···Cg10.842.253.060 (13)163
C52-H52A···O810.992.313.224 (12)153
C75-H75···Cg2i0.952.583.498 (6)164
(III)O81-H81···Cg10.842.233.057 (7)166
C52-H52A···O810.992.223.145 (6)155
C75-H75···Cg2i0.952.593.519 (3)167
(IV)O81-H81···Cg10.842.583.245 (6)137
C52-H52A···O810.992.313.285 (8)170
C75-H75···Cg2ii0.952.673.544 (4)154
C77-H77A···O55iii0.992.423.352 (3)157
(a) Because of the ethanol disorder, only half of the heterocyclic molecules in each compound form hydrogen bonds to an ethanol molecule (see text). Cg1 represents the centroid of the ring C71–C76. Cg2 represents the centroid of the ring N1/N2/C3/C3a/C7a.

Symmetry codes: (i) 1/2 - x, 3/2 - y, 1 - z; (ii) 1 - x, 1 - y, 1 - z; (iii) 1 - x, 2 - y, 1 - z.
 

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