Four N⁷-alkoxy­benzyl-substituted 4,5,6,7-tetra­hydro-1H-pyrazolo[3,4-b]pyridine-5-spiro-1'-cyclo­hexane-2',6'-diones: hydrogen-bonded supra­molecular structures in zero, one, two or three dimensions

3-tert-Butyl-7-(4-methoxy­benz­yl)-4',4'-dimethyl-1-phenyl-4,5,6,7-tetra­hydro-1H-pyrazolo[3,4-b]pyridine-5-spiro-1'-cyclohex­ane-2',6'-dione, C₃₁H₃₇N₃O₃, (I), 3-tert-butyl-7-(2,3-dimethoxy­benz­yl)-4',4'-dimethyl-1-phenyl-4,5,6,7-tetra­hydro-1H-pyrazolo[3,4-b]pyridine-5-spiro-1'-cyclo­hexane-2',6'-dione, C₃₂H₃₉N₃O₄, (II), 3-tert-butyl-4',4'-dimethyl-7-(3,4-methyl­ene­dioxy­benz­yl)-1-phenyl-4,5,6,7-tetra­hydro-1H-pyrazolo[3,4-b]pyridine-5-spiro-1'-cyclo­hexane-2',6'-dione, C₃₁H₃₅N₃O₄, (III), and 3-tert-butyl-4',4'-dimethyl-1-phenyl-7-(3,4,5-trimethoxy­benz­yl)-4,5,6,7-tetra­hydro-1H-pyrazolo[3,4-b]pyridine-5-spiro-1'-cyclo­hexane-2',6'-dione ethanol 0.67-solvate, C₃₃H₄₁N₃O₅·0.67C₂H₆O, (IV), all contain reduced pyridine rings having half-chair conformations. The mol­ecules of (I) and (II) are linked into centrosymmetric dimers and simple chains, respectively, by C-H...O hydrogen bonds, augmented only in (I) by a C-H...[pi] hydrogen bond. The mol­ecules of (III) are linked by a combination of C-H...O and C-H...[pi] hydrogen bonds into a chain of edge-fused centrosymmetric rings, further linked by weak hydrogen bonds into supra­molecular arrays in two or three dimensions. The heterocyclic mol­ecules in (IV) are linked by two independent C-H...O hydrogen bonds into sheets, from which the partial-occupancy ethanol mol­ecules are pendent. The significance of this study lies in its finding of a very wide range of supra­molecular aggregation modes dependent on rather modest changes in the peripheral substituents remote from the main hydrogen-bond acceptor sites.

S1. Comment

In continuation of our structural study of N⁷-benzyl-substituted pyrazolo[3,4-b]pyridine-5-spiro-1'-cyclohexane-2',6'-diones (Cruz et al., 2008) – itself part of a programme exploring the use of multicomponent condensation reactions, especially those induced by microwave irradiation under solvent-free conditions, for the synthesis of novel heterocycles – we now report the molecular and supramolecular structures of four N⁷-(alkoxybenzyl) derivatives, (I)–(IV) (Figs. 1–4). Compounds (I)–(IV) were synthesized using the reaction between a substituted N-benzylaminopyrazole, 5,5-dimethylcyclohexane-1,3-dione (dimedone) and excess paraformaldehyde, under solvent-free conditions, in a straightforward modification of the synthetic method employed by Cruz et al. (2008).

Compounds (I)–(III) crystallized in solvent-free form, but compound (IV) was found to be a partial ethanol solvate, with 0.67 molecules of ethanol per molecule of the pyrazolopyridine in the crystal selected for data collection. We have not investigated systematically the stoichiometry of this solvate or related solvates, but it is entirely possible that the ethanol content may vary somewhat from one crystal to another. Examination using PLATON (Spek, 2003) of the refined structure of (IV), but with the ethanol component omitted, found eight voids, each of volume ca 96 ų and together accounting for some 12.2% of the unit-cell volume. It is possible that the ethanol of solvation is present in this strucutre merely as a placeholder component, occupying what would otherwise be empty space.

In each compound the reduced pyridine ring adopts a half-chair conformation, as shown (Table 1) by the ring-puckering parameters (Cremer & Pople, 1975), defined here for the atom-sequence (N7, C6, C5, C4, C3A, C7A). 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 rest of the molecular conformation is determined by the orientation of the three pendent substituents relative to the heterocyclic molecular core, and by the orientation of the alkoxy substituents relative to the adjacent aryl ring (Table 1). As indicated by the relevant torsion angles (Table 1), while the orientation of the phenyl and benzyl units relative to the molecular core is fairly similar in each compound, there is considerable variation in the degree to which the tert-butyl group has been rotated about the C3—C31 bond. Since the rotational barrier about this bond approximates to a sixfold barrier, as found when a fragment of local C₃ symmetry, such as a tert-butyl group, is bonded to a fragment with effective local C₂ symmetry, such as a planar ring, it can be expected that the barrier is exceptionally low, no more than a few tens of joules per mole (Tannenbaum et al., 1956; Naylor & Wilson, 1957), so accounting for the variation in the relative orientation of the tert-butyl group.

The orientations of the methoxy substituents in (I), (II) and (IV) show some interesting variations. As shown by the relevant torsion angles (Table 1), the single methoxy group in (I), that at C73 in (II), and those at C73 and C75 in (IV) are all almost coplanar with the adjacent aryl rings. The deviations from the mean planes of these rings are 0.235 (3) Å for atom C741 in (I), 0.006 (3) Å for atom C731 in (II), and 0.147 (5) Å and 0.164 (5) Å for atoms C731 and C751, respectively, in (IV). Associated with each of these effectively in-plane methoxy groups is a marked difference between the two exocyclic C—C—O angles, typically almost 10°. By contrast, the C74/O74/C741 plane in compound (IV) is almost orthogonal to the adjacent ring, with atom C741 displaced by 1.058 (5) Å from the ring plane, while atom C721 in compound (II) is displaced from the adjacent ring plane by 0.944 (3) Å. At the same time, in compound (IV) the exocyclic C—C—O angles at atom C74 are identical within experimental uncertainty, and those at atom C72 in compound (II) differ by less than 3°. Although the in-plane conformation appears to be the most favoured and of lowest energy, maximizing the orbital overlap between the π orbitals of the ring and formally non-bonding 2p orbital on the O atom, this orientation is nonetheless rather easily disrupted by non-bonded (steric) interactions between adjacent substituents. In (III), the five-membered ring formed by the methylenedioxo unit adopts an envelope conformation, folded across the line O71···O72.

Although compounds (I)–(IV) all contain potential hydrogen-bond acceptors – in the methoxy groups in (I), (II) and (IV), and in the methylenedioxo unit in (III) – in no case do these O atoms play any significant role in the supramolecular aggregation. There is a rather long C—H···O contact involving such an O atom in (III) (Table 2), although this is possibly only of marginal structural significance, at best, while the methoxy O atoms in the other three compounds do not form even weak contacts of this type. The principal intermolecular interactions in this series are of C—H···π type and of C—H···O type utilizing carbonyl O atoms as the hydrogen-bond acceptors. There are no π–π stacking interactions in any of (I)–(IV). The partial-occupancy ethanol component in (IV) is connected to the heterocyclic component by a three-point linkage (Table 2), but it plays no role in the supramolecular aggregation, acting simply as a pendent group.

In compound (I), pairs of molecules are linked by the cooperative action of C—H···O and C—H···π hydrogen bonds into centrosymmetric dimers, within which the paired C—H···O hydrogen bonds define an R²₂(22) (Bernstein et al., 1995) motif (Fig. 5), but there are no direction-specific interactions between these dimers; hence the supramolecular aggregation in compound (I) can be regarded as finite, or zero-dimensional.

A single C—H···O hydrogen bond links molecules of (II), which are related by the 2₁ screw axis along (1/2, y, 3/4), into a simple C(11) chain running parallel to the [010] direction (Fig. 6). Two chains of this type related to one another by inversion pass through each unit cell, but there are no direction-specific interactions between adjacent chains.

In (III), a combination of a C—H···O hydrogen bond, with C15 as the donor, and a C—H···π hydrogen bond link the molecules into a chain of centrosymmetric edge-fused rings running parallel to the [100] direction (Fig. 7). Within this chain, R²₂(22) rings exactly analogous to those observed in compound (I) are centred at (n, 1/2, 1/2), where n represents an integer, and these alternate with rings formed by pairs of C—H···π hydrogen bonds, centred at (n + 1/2, 1/2, 1/2), where n represents zero or an integer. Within the structure of (III) there are two further C—H···O contacts, both rather long, and it is of interest to examine their possible structural effects. The interaction involving C13 as the donor links the chains of rings, which are related by translation along [010], while that involving C72 as the donor links the R²₂(22) rings into a chain along [001]. Thus, if these two interactions are regarded as structurally significant, the supramolecular structure based on the one-dimensional chains of rings along [100] (Fig. 7) become successively linked into two-dimensional and three-dimensional arrays.

The heterocyclic components in (IV) are linked into a sheet by two C—H···O hydrogen bonds, both utilizing the same carbonyl acceptor atom, and the formation of the sheet is readily analysed in terms of the individual actions of the two hydrogen bonds. The aryl atom C13 at (x, y, z) acts as a hydrogen-bond donor to the carbonyl atom O51 at (-x, -1/2 + y, 1/2 - z), so linking molecules related by the 2₁ screw axis along (0, y, 1/4), and so forming a C(11) chain running parallel to the [010] direction. In the second substructure, the methylene atom C77 at (x, y, z) acts as a hydrogen-bond donor to atom O51 at (1/2 - x, -1/2 + y, z), thus linking molecules related by the b-glide plane at x = 1/4 into a C(7) chain, again running parallel to the [010] direction. The combination of these two chain motifs generates a sheet of R³₄(28) rings lying parallel to (001) (Fig. 8) and occupying the domain 0 < z < 0.5. A second sheet, related to the first by inversion, occupies the domain 0.5 < z < 1.0, but there are no direction-specific interactions between adjacent sheets. As noted above, the partial-occupancy ethanol molecules are pendent from this sheet, but they play no role in its formation.

Although the methoxy substituents in compounds (I), (II) and (IV) play no direct role in the supramolecular aggregation, it is striking that, as the degree of methoxy substitution increases, so too does the dimensionality of the hydrogen-bonded structure, from zero-dimensional in the monomethoxy compound (I), to one-dimensional in the dimethoxy compound (II) to two-dimensional in the trimethoxy compound (IV). It is interesting to note that the variations in the molecular constitution occur solely in the substituted benzyl ring, which is, of course, remote from the main hydrogen-bond acceptor sites, the carbonyl O atoms and the main hydrogen-bond donor sites, most of which are provided by the unsubstituted phenyl ring.

Related literature

For related literature, see: Bernstein et al. (1995); Cremer & Pople (1975); Cruz et al. (2008); Naylor & Wilson (1957); Spek (2003); Tannenbaum et al. (1956).

S2. Experimental

Microwave-induced syntheses were carried out using a focused microwave reactor (CEM Discover TM). A mixture of the appropriately-substituted N-benzylaminopyrazole (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 dissolved in hot ethanol. After cooling these solutions, the solid products were collected by filtration and washed with ethanol, and then with hexane (2 × 5 ml) to afford the pure products. Colourless crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation of solutions in ethanol. For (I), yield 75%, m.p. 445–447 K; HRMS found 499.2835, C₃₁H₃₇N₃O₃ requires 499.2835. For (II), yield 85%, m.p. 503–505 K; HRMS found 529.2941, C₃₂H₃₉N₃O₄ requires 529.2941. For (III), yield 70%, m.p. 475–477 K; HRMS found 513.2635, C₃₁H₃₅N₃O₄ requires 513.2628. For (IV), yield 71%, m.p. 456–458 K; HRMS found 559.3032, C₃₃H₄₁N₃O₅ requires 559.3046.

S3. Refinement

For compounds (II) and (IV), the space groups P2₁/c and Pbca, respectively, were uniquely assigned from the systematic absences. Crystals of compounds (I) and (III) are triclinic; for each, the space group P1 was selected, and then 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 distances of 0.95 Å (aromatic), 0.98 Å (CH₃) or 0.99 Å (CH₂) and O—H of 0.84 Å, and with U_iso(H) = kU_eq(carrier), where k = 1.5 for the methyl and hydroxyl H atoms, and k = 1.2 for all other H atoms. In the crystal of compound (IV) selected for data collection, the site occupancy for the ethanol component refined to a value of 0.670 (7). Crystals of compound (III) diffracted rather weakly, even at 120 K, with only 49% of the data labelled `observed'; the merging R index was also fairly high at 0.129.

Computing details

For all compounds, data collection: COLLECT (Hooft, 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 molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The molecular structure of (II). Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 3. The molecular structure of (III). Displacement ellipsoids are drawn at the 30%3probability level.
	Fig. 4. The molecular structure of (IV). The ethanol component has occupancy 0.670 (7) (see text). Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 5. Part of the crystal structure of (I), showing the formation of a centrosymmetric dimer. For the sake of clarity, H atoms not involved in the motifs shown have been omitted. The atoms marked with an asterisk (*) are at the symmetry position (-x, 1 - y, 1 - z).
	Fig. 6. A stereoview of part of the crystal structure of (II), showing the formation of a C(11) chain along [010]. For the sake of clarity, H atoms not involved in the motif shown have been omitted.
	Fig. 7. A stereoview of part of the crystal structure of (III), showing the formation of a chain along [100] containing two types of centrosymmetric ring. For the sake of clarity, H atoms bonded to C atoms not involved in the motifs shown have been omitted.
	Fig. 8. A stereoview of part of the crystal structure of (IV), showing the formation of a sheet parallel to (001). For the sake of clarity, the partial-occupancy ethanol component and H atoms bonded to C atoms not involved in the motifs shown have been omitted.

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

Crystal data

C31H37N3O3	Z = 2
Mr = 499.64	F(000) = 536
Triclinic, P1	Dx = 1.272 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.5971 (8) Å	Cell parameters from 5986 reflections
b = 11.2549 (16) Å	θ = 2.9–27.5°
c = 12.1452 (14) Å	µ = 0.08 mm^−1
α = 86.979 (11)°	T = 120 K
β = 85.487 (10)°	Block, colourless
γ = 87.216 (7)°	0.51 × 0.36 × 0.18 mm
V = 1304.7 (3) Å^3

Data collection

Bruker–Nonius KappaCCD diffractometer	5986 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	3281 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.081
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 2.9°
ϕ & ω scans	h = −12→12
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −14→14
Tmin = 0.971, Tmax = 0.985	l = −15→15
36057 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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.199	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.097P)^2 + 0.8153P] where P = (Fo^2 + 2Fc^2)/3
5986 reflections	(Δ/σ)max < 0.001
340 parameters	Δρmax = 0.31 e Å^−3
0 restraints	Δρmin = −0.39 e Å^−3

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

	x	y	z	Uiso*/Ueq
O51	0.4779 (2)	0.00564 (17)	0.65960 (16)	0.0346 (5)
O55	0.04805 (18)	0.16760 (17)	0.72396 (16)	0.0332 (5)
O74	0.37110 (19)	0.67738 (17)	1.10638 (15)	0.0322 (5)
N1	0.2259 (2)	0.46482 (18)	0.49574 (17)	0.0254 (5)
N2	0.1859 (2)	0.42601 (18)	0.39927 (17)	0.0258 (5)
N7	0.3035 (2)	0.38248 (18)	0.67103 (17)	0.0247 (5)
C3	0.1963 (3)	0.3078 (2)	0.4093 (2)	0.0240 (6)
C3A	0.2418 (3)	0.2687 (2)	0.5139 (2)	0.0247 (6)
C4	0.2708 (3)	0.1492 (2)	0.5675 (2)	0.0243 (6)
C5	0.2964 (3)	0.1558 (2)	0.6900 (2)	0.0247 (6)
C6	0.3739 (3)	0.2723 (2)	0.7081 (2)	0.0254 (6)
C7A	0.2588 (3)	0.3713 (2)	0.5655 (2)	0.0240 (6)
C11	0.2435 (3)	0.5880 (2)	0.5041 (2)	0.0239 (6)
C12	0.3616 (3)	0.6248 (2)	0.5485 (2)	0.0277 (6)
C13	0.3805 (3)	0.7454 (2)	0.5533 (2)	0.0295 (6)
C14	0.2852 (3)	0.8269 (2)	0.5111 (2)	0.0285 (6)
C15	0.1693 (3)	0.7892 (2)	0.4656 (2)	0.0279 (6)
C16	0.1462 (3)	0.6693 (2)	0.4630 (2)	0.0263 (6)
C31	0.1705 (3)	0.2408 (2)	0.3091 (2)	0.0257 (6)
C32	0.1476 (3)	0.1094 (2)	0.3370 (2)	0.0324 (6)
C33	0.0434 (3)	0.2964 (2)	0.2550 (2)	0.0294 (6)
C34	0.2991 (3)	0.2532 (3)	0.2274 (2)	0.0327 (6)
C51	0.3974 (3)	0.0536 (2)	0.7266 (2)	0.0277 (6)
C52	0.3976 (3)	0.0201 (2)	0.8476 (2)	0.0293 (6)
C53	0.2509 (3)	0.0085 (2)	0.9040 (2)	0.0296 (6)
C54	0.1698 (3)	0.1276 (2)	0.8843 (2)	0.0281 (6)
C55	0.1601 (3)	0.1533 (2)	0.7628 (2)	0.0267 (6)
C71	0.2545 (3)	0.4873 (2)	0.8472 (2)	0.0252 (6)
C72	0.1807 (3)	0.4782 (2)	0.9484 (2)	0.0296 (6)
C73	0.2158 (3)	0.5396 (2)	1.0381 (2)	0.0301 (6)
C74	0.3292 (3)	0.6099 (2)	1.0259 (2)	0.0265 (6)
C75	0.4099 (3)	0.6151 (2)	0.9270 (2)	0.0309 (6)
C76	0.3719 (3)	0.5554 (2)	0.8384 (2)	0.0304 (6)
C77	0.1980 (3)	0.4363 (2)	0.7496 (2)	0.0272 (6)
C531	0.1782 (3)	−0.0920 (2)	0.8545 (2)	0.0336 (7)
C532	0.2587 (3)	−0.0193 (3)	1.0270 (2)	0.0354 (7)
C741	0.2828 (3)	0.6810 (3)	1.2059 (2)	0.0371 (7)
H4A	0.3541	0.1110	0.5283	0.029*
H4B	0.1904	0.0989	0.5609	0.029*
H6A	0.3867	0.2760	0.7879	0.031*
H6B	0.4681	0.2666	0.6687	0.031*
H12	0.4289	0.5679	0.5753	0.033*
H13	0.4596	0.7718	0.5858	0.035*
H14	0.2993	0.9096	0.5134	0.034*
H15	0.1045	0.8462	0.4357	0.033*
H16	0.0647	0.6434	0.4334	0.032*
H32A	0.2325	0.0714	0.3654	0.049*
H32B	0.1262	0.0707	0.2703	0.049*
H32C	0.0693	0.1015	0.3934	0.049*
H33A	−0.0407	0.2849	0.3049	0.044*
H33B	0.0335	0.2584	0.1855	0.044*
H33C	0.0557	0.3818	0.2400	0.044*
H34A	0.3145	0.3378	0.2101	0.049*
H34B	0.2839	0.2141	0.1594	0.049*
H34C	0.3812	0.2156	0.2604	0.049*
H52A	0.4459	0.0813	0.8841	0.035*
H52B	0.4512	−0.0566	0.8574	0.035*
H54A	0.0747	0.1241	0.9219	0.034*
H54B	0.2182	0.1923	0.9156	0.034*
H72	0.1030	0.4284	0.9577	0.036*
H73	0.1618	0.5329	1.1069	0.036*
H75	0.4918	0.6599	0.9198	0.037*
H76	0.4273	0.5610	0.7701	0.037*
H77A	0.1312	0.3750	0.7767	0.033*
H77B	0.1449	0.5004	0.7097	0.033*
H53A	0.1746	−0.0755	0.7747	0.050*
H53B	0.0829	−0.0972	0.8892	0.050*
H53C	0.2307	−0.1676	0.8678	0.050*
H53D	0.3042	0.0451	1.0595	0.053*
H53E	0.3130	−0.0944	1.0385	0.053*
H53F	0.1640	−0.0268	1.0624	0.053*
H74A	0.1873	0.7057	1.1886	0.056*
H74B	0.3174	0.7381	1.2543	0.056*
H74C	0.2828	0.6017	1.2433	0.056*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O51	0.0351 (11)	0.0319 (11)	0.0358 (11)	0.0085 (9)	−0.0014 (9)	−0.0031 (9)
O55	0.0246 (10)	0.0374 (11)	0.0377 (11)	0.0017 (8)	−0.0069 (8)	0.0006 (9)
O74	0.0314 (10)	0.0400 (11)	0.0260 (10)	−0.0053 (9)	0.0007 (8)	−0.0086 (8)
N1	0.0332 (12)	0.0199 (11)	0.0236 (11)	−0.0015 (9)	−0.0053 (9)	−0.0022 (9)
N2	0.0305 (12)	0.0226 (11)	0.0251 (11)	−0.0019 (9)	−0.0038 (9)	−0.0053 (9)
N7	0.0271 (11)	0.0209 (11)	0.0263 (11)	0.0014 (9)	−0.0037 (9)	−0.0040 (9)
C3	0.0244 (13)	0.0192 (13)	0.0281 (14)	−0.0031 (10)	0.0016 (10)	−0.0015 (10)
C3A	0.0250 (13)	0.0221 (13)	0.0271 (14)	−0.0010 (10)	0.0002 (10)	−0.0036 (11)
C4	0.0262 (13)	0.0185 (13)	0.0287 (14)	−0.0014 (10)	−0.0044 (11)	−0.0015 (10)
C5	0.0239 (13)	0.0227 (13)	0.0276 (14)	−0.0007 (10)	−0.0029 (10)	−0.0021 (11)
C6	0.0276 (14)	0.0215 (13)	0.0276 (14)	−0.0014 (10)	−0.0040 (11)	−0.0021 (11)
C7A	0.0246 (13)	0.0219 (13)	0.0255 (13)	−0.0008 (10)	−0.0016 (10)	−0.0030 (11)
C11	0.0280 (13)	0.0197 (13)	0.0239 (13)	−0.0016 (10)	0.0011 (10)	−0.0046 (10)
C12	0.0285 (14)	0.0255 (14)	0.0285 (14)	0.0012 (11)	−0.0014 (11)	−0.0005 (11)
C13	0.0316 (15)	0.0251 (14)	0.0323 (15)	−0.0071 (11)	−0.0009 (12)	−0.0041 (12)
C14	0.0367 (15)	0.0180 (13)	0.0308 (14)	−0.0029 (11)	−0.0003 (12)	−0.0016 (11)
C15	0.0345 (15)	0.0217 (13)	0.0269 (14)	0.0031 (11)	−0.0010 (11)	−0.0016 (11)
C16	0.0286 (14)	0.0257 (14)	0.0248 (13)	−0.0022 (11)	−0.0028 (11)	−0.0010 (11)
C31	0.0244 (13)	0.0247 (14)	0.0283 (14)	−0.0011 (10)	−0.0024 (11)	−0.0031 (11)
C32	0.0395 (16)	0.0263 (15)	0.0322 (15)	−0.0011 (12)	−0.0047 (12)	−0.0058 (12)
C33	0.0331 (15)	0.0255 (14)	0.0301 (14)	−0.0015 (11)	−0.0039 (12)	−0.0048 (11)
C34	0.0349 (16)	0.0317 (15)	0.0319 (15)	−0.0013 (12)	−0.0007 (12)	−0.0085 (12)
C51	0.0259 (14)	0.0201 (13)	0.0374 (15)	−0.0027 (11)	−0.0047 (12)	−0.0005 (11)
C52	0.0297 (14)	0.0254 (14)	0.0333 (15)	0.0013 (11)	−0.0070 (12)	−0.0004 (12)
C53	0.0308 (15)	0.0279 (15)	0.0306 (15)	−0.0024 (11)	−0.0071 (12)	0.0011 (12)
C54	0.0246 (14)	0.0278 (14)	0.0323 (15)	−0.0011 (11)	−0.0038 (11)	−0.0020 (11)
C55	0.0271 (14)	0.0199 (13)	0.0330 (15)	0.0008 (10)	−0.0037 (11)	−0.0013 (11)
C71	0.0292 (14)	0.0200 (13)	0.0262 (14)	0.0016 (10)	−0.0023 (11)	−0.0015 (10)
C72	0.0292 (14)	0.0308 (15)	0.0290 (14)	−0.0053 (11)	0.0001 (11)	−0.0018 (12)
C73	0.0338 (15)	0.0315 (15)	0.0245 (14)	−0.0020 (12)	0.0008 (11)	−0.0018 (12)
C74	0.0302 (14)	0.0262 (14)	0.0231 (13)	−0.0016 (11)	−0.0015 (11)	−0.0024 (11)
C75	0.0288 (14)	0.0341 (15)	0.0302 (15)	−0.0086 (12)	0.0033 (11)	−0.0059 (12)
C76	0.0350 (15)	0.0325 (15)	0.0235 (14)	−0.0034 (12)	0.0031 (11)	−0.0041 (12)
C77	0.0295 (14)	0.0247 (14)	0.0270 (14)	−0.0006 (11)	0.0001 (11)	−0.0021 (11)
C531	0.0376 (16)	0.0298 (15)	0.0346 (15)	−0.0072 (12)	−0.0070 (12)	−0.0004 (12)
C532	0.0369 (16)	0.0360 (16)	0.0337 (16)	−0.0021 (13)	−0.0068 (12)	0.0011 (13)
C741	0.0352 (16)	0.0508 (19)	0.0256 (14)	−0.0020 (14)	0.0010 (12)	−0.0106 (13)

Geometric parameters (Å, º)

O51—C51	1.208 (3)	C32—H32C	0.98
O55—C55	1.208 (3)	C33—H33A	0.98
O74—C74	1.365 (3)	C33—H33B	0.98
O74—C741	1.422 (3)	C33—H33C	0.98
N1—C7A	1.357 (3)	C34—H34A	0.98
N1—N2	1.361 (3)	C34—H34B	0.98
N1—C11	1.414 (3)	C34—H34C	0.98
N2—C3	1.329 (3)	C51—C52	1.498 (4)
N7—C7A	1.397 (3)	C52—C53	1.525 (4)
N7—C6	1.451 (3)	C52—H52A	0.99
N7—C77	1.467 (3)	C52—H52B	0.99
C3—C3A	1.418 (4)	C53—C532	1.516 (4)
C3—C31	1.508 (4)	C53—C531	1.530 (4)
C3A—C7A	1.364 (3)	C53—C54	1.535 (4)
C3A—C4	1.487 (3)	C54—C55	1.498 (4)
C4—C5	1.533 (3)	C54—H54A	0.99
C4—H4A	0.99	C54—H54B	0.99
C4—H4B	0.99	C71—C72	1.372 (4)
C5—C55	1.521 (4)	C71—C76	1.387 (4)
C5—C51	1.538 (4)	C71—C77	1.494 (4)
C5—C6	1.572 (4)	C72—C73	1.391 (4)
C6—H6A	0.99	C72—H72	0.95
C6—H6B	0.99	C73—C74	1.370 (4)
C11—C16	1.379 (4)	C73—H73	0.95
C11—C12	1.383 (4)	C74—C75	1.377 (4)
C12—C13	1.383 (4)	C75—C76	1.380 (4)
C12—H12	0.95	C75—H75	0.95
C13—C14	1.372 (4)	C76—H76	0.95
C13—H13	0.95	C77—H77A	0.99
C14—C15	1.375 (4)	C77—H77B	0.99
C14—H14	0.95	C531—H53A	0.98
C15—C16	1.380 (4)	C531—H53B	0.98
C15—H15	0.95	C531—H53C	0.98
C16—H16	0.95	C532—H53D	0.98
C31—C32	1.522 (4)	C532—H53E	0.98
C31—C33	1.523 (4)	C532—H53F	0.98
C31—C34	1.528 (4)	C741—H74A	0.98
C32—H32A	0.98	C741—H74B	0.98
C32—H32B	0.98	C741—H74C	0.98
C74—O74—C741	116.4 (2)	C31—C34—H34B	109.5
C7A—N1—N2	110.6 (2)	H34A—C34—H34B	109.5
C7A—N1—C11	130.2 (2)	C31—C34—H34C	109.5
N2—N1—C11	118.7 (2)	H34A—C34—H34C	109.5
C3—N2—N1	105.7 (2)	H34B—C34—H34C	109.5
C7A—N7—C6	109.9 (2)	O51—C51—C52	121.4 (2)
C7A—N7—C77	114.5 (2)	O51—C51—C5	120.4 (2)
C6—N7—C77	116.8 (2)	C52—C51—C5	118.1 (2)
N2—C3—C3A	111.0 (2)	C51—C52—C53	113.0 (2)
N2—C3—C31	117.1 (2)	C51—C52—H52A	109.0
C3A—C3—C31	131.7 (2)	C53—C52—H52A	109.0
C7A—C3A—C3	104.4 (2)	C51—C52—H52B	109.0
C7A—C3A—C4	122.1 (2)	C53—C52—H52B	109.0
C3—C3A—C4	133.5 (2)	H52A—C52—H52B	107.8
C3A—C4—C5	112.3 (2)	C532—C53—C52	110.2 (2)
C3A—C4—H4A	109.1	C532—C53—C531	109.0 (2)
C5—C4—H4A	109.1	C52—C53—C531	109.8 (2)
C3A—C4—H4B	109.1	C532—C53—C54	110.2 (2)
C5—C4—H4B	109.1	C52—C53—C54	107.5 (2)
H4A—C4—H4B	107.9	C531—C53—C54	110.2 (2)
C55—C5—C4	111.4 (2)	C55—C54—C53	109.9 (2)
C55—C5—C51	110.1 (2)	C55—C54—H54A	109.7
C4—C5—C51	110.8 (2)	C53—C54—H54A	109.7
C55—C5—C6	109.8 (2)	C55—C54—H54B	109.7
C4—C5—C6	109.9 (2)	C53—C54—H54B	109.7
C51—C5—C6	104.6 (2)	H54A—C54—H54B	108.2
N7—C6—C5	115.2 (2)	O55—C55—C54	121.2 (2)
N7—C6—H6A	108.5	O55—C55—C5	121.4 (2)
C5—C6—H6A	108.5	C54—C55—C5	117.4 (2)
N7—C6—H6B	108.5	C72—C71—C76	117.4 (2)
C5—C6—H6B	108.5	C72—C71—C77	119.5 (2)
H6A—C6—H6B	107.5	C76—C71—C77	122.8 (2)
C16—C11—C12	121.2 (2)	C71—C72—C73	122.1 (3)
C16—C11—N1	119.5 (2)	C71—C72—H72	119.0
C12—C11—N1	119.3 (2)	C73—C72—H72	119.0
C13—C12—C11	119.1 (2)	C74—C73—C72	119.3 (2)
C13—C12—H12	120.5	C74—C73—H73	120.4
C11—C12—H12	120.5	C72—C73—H73	120.4
C14—C13—C12	120.1 (3)	O74—C74—C73	124.7 (2)
C14—C13—H13	120.0	O74—C74—C75	115.6 (2)
C12—C13—H13	120.0	C73—C74—C75	119.8 (2)
C13—C14—C15	120.2 (2)	C74—C75—C76	120.1 (3)
C13—C14—H14	119.9	C74—C75—H75	119.9
C15—C14—H14	119.9	C76—C75—H75	119.9
C14—C15—C16	120.6 (2)	C75—C76—C71	121.2 (2)
C14—C15—H15	119.7	C75—C76—H76	119.4
C16—C15—H15	119.7	C71—C76—H76	119.4
C11—C16—C15	118.7 (2)	N7—C77—C71	115.1 (2)
C11—C16—H16	120.6	N7—C77—H77A	108.5
C15—C16—H16	120.6	C71—C77—H77A	108.5
N1—C7A—C3A	108.3 (2)	N7—C77—H77B	108.5
N1—C7A—N7	124.1 (2)	C71—C77—H77B	108.5
C3A—C7A—N7	127.6 (2)	H77A—C77—H77B	107.5
C3—C31—C32	112.5 (2)	C53—C531—H53A	109.5
C3—C31—C33	109.9 (2)	C53—C531—H53B	109.5
C32—C31—C33	109.1 (2)	H53A—C531—H53B	109.5
C3—C31—C34	107.2 (2)	C53—C531—H53C	109.5
C32—C31—C34	109.5 (2)	H53A—C531—H53C	109.5
C33—C31—C34	108.6 (2)	H53B—C531—H53C	109.5
C31—C32—H32A	109.5	C53—C532—H53D	109.5
C31—C32—H32B	109.5	C53—C532—H53E	109.5
H32A—C32—H32B	109.5	H53D—C532—H53E	109.5
C31—C32—H32C	109.5	C53—C532—H53F	109.5
H32A—C32—H32C	109.5	H53D—C532—H53F	109.5
H32B—C32—H32C	109.5	H53E—C532—H53F	109.5
C31—C33—H33A	109.5	O74—C741—H74A	109.5
C31—C33—H33B	109.5	O74—C741—H74B	109.5
H33A—C33—H33B	109.5	H74A—C741—H74B	109.5
C31—C33—H33C	109.5	O74—C741—H74C	109.5
H33A—C33—H33C	109.5	H74A—C741—H74C	109.5
H33B—C33—H33C	109.5	H74B—C741—H74C	109.5
C31—C34—H34A	109.5
C7A—N1—N2—C3	−0.9 (3)	C3A—C3—C31—C32	20.8 (4)
C11—N1—N2—C3	171.7 (2)	N2—C3—C31—C33	−43.4 (3)
N1—N2—C3—C3A	0.7 (3)	C3A—C3—C31—C33	142.5 (3)
N1—N2—C3—C31	−174.5 (2)	N2—C3—C31—C34	74.5 (3)
N2—C3—C3A—C7A	−0.3 (3)	C3A—C3—C31—C34	−99.6 (3)
C31—C3—C3A—C7A	174.0 (3)	C55—C5—C51—O51	147.2 (2)
N2—C3—C3A—C4	−179.8 (3)	C4—C5—C51—O51	23.4 (3)
C31—C3—C3A—C4	−5.4 (5)	C6—C5—C51—O51	−94.9 (3)
C7A—C3A—C4—C5	9.6 (3)	C55—C5—C51—C52	−35.9 (3)
C3—C3A—C4—C5	−171.1 (3)	C4—C5—C51—C52	−159.6 (2)
C3A—C4—C5—C55	87.3 (3)	C6—C5—C51—C52	82.0 (3)
C3A—C4—C5—C51	−149.7 (2)	O51—C51—C52—C53	−136.6 (3)
C3A—C4—C5—C6	−34.6 (3)	C5—C51—C52—C53	46.5 (3)
C7A—N7—C6—C5	−46.4 (3)	C51—C52—C53—C532	−177.2 (2)
C77—N7—C6—C5	86.2 (3)	C51—C52—C53—C531	62.8 (3)
C55—C5—C6—N7	−66.4 (3)	C51—C52—C53—C54	−57.1 (3)
C4—C5—C6—N7	56.5 (3)	C532—C53—C54—C55	−178.9 (2)
C51—C5—C6—N7	175.4 (2)	C52—C53—C54—C55	61.1 (3)
C7A—N1—C11—C16	−146.0 (3)	C531—C53—C54—C55	−58.6 (3)
N2—N1—C11—C16	43.1 (3)	C53—C54—C55—O55	121.4 (3)
C7A—N1—C11—C12	37.2 (4)	C53—C54—C55—C5	−56.2 (3)
N2—N1—C11—C12	−133.8 (2)	C4—C5—C55—O55	−12.9 (3)
C16—C11—C12—C13	1.2 (4)	C51—C5—C55—O55	−136.3 (3)
N1—C11—C12—C13	178.0 (2)	C6—C5—C55—O55	109.0 (3)
C11—C12—C13—C14	−2.1 (4)	C4—C5—C55—C54	164.6 (2)
C12—C13—C14—C15	1.1 (4)	C51—C5—C55—C54	41.3 (3)
C13—C14—C15—C16	0.9 (4)	C6—C5—C55—C54	−73.4 (3)
C12—C11—C16—C15	0.8 (4)	C76—C71—C72—C73	3.6 (4)
N1—C11—C16—C15	−176.1 (2)	C77—C71—C72—C73	−169.6 (2)
C14—C15—C16—C11	−1.8 (4)	C71—C72—C73—C74	−1.2 (4)
N2—N1—C7A—C3A	0.7 (3)	C741—O74—C74—C73	−5.3 (4)
C11—N1—C7A—C3A	−170.8 (2)	C741—O74—C74—C75	175.0 (2)
N2—N1—C7A—N7	−180.0 (2)	C72—C73—C74—O74	177.7 (2)
C11—N1—C7A—N7	8.5 (4)	C72—C73—C74—C75	−2.6 (4)
C3—C3A—C7A—N1	−0.2 (3)	O74—C74—C75—C76	−176.4 (2)
C4—C3A—C7A—N1	179.3 (2)	C73—C74—C75—C76	3.9 (4)
C3—C3A—C7A—N7	−179.5 (2)	C74—C75—C76—C71	−1.3 (4)
C4—C3A—C7A—N7	0.0 (4)	C72—C71—C76—C75	−2.3 (4)
C6—N7—C7A—N1	−160.7 (2)	C77—C71—C76—C75	170.7 (2)
C77—N7—C7A—N1	65.6 (3)	C7A—N7—C77—C71	−159.8 (2)
C6—N7—C7A—C3A	18.5 (4)	C6—N7—C77—C71	69.7 (3)
C77—N7—C7A—C3A	−115.2 (3)	C72—C71—C77—N7	−143.6 (2)
N2—C3—C31—C32	−165.1 (2)	C76—C71—C77—N7	43.6 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15···O55^i	0.95	2.54	3.229 (3)	130
C16—H16···Cg1^i	0.95	2.88	3.589 (3)	132

Symmetry code: (i) −x, −y+1, −z+1.

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

Crystal data

C32H39N3O4	F(000) = 1136
Mr = 529.66	Dx = 1.260 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6394 reflections
a = 12.4683 (15) Å	θ = 3.2–27.5°
b = 10.2892 (12) Å	µ = 0.08 mm^−1
c = 21.7635 (16) Å	T = 120 K
β = 90.843 (10)°	Block, colourless
V = 2791.7 (5) Å^3	0.32 × 0.25 × 0.12 mm
Z = 4

Data collection

Bruker–Nonius KappaCCD diffractometer	6394 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	4404 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.065
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.2°
ϕ & ω scans	h = −16→16
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −13→13
Tmin = 0.965, Tmax = 0.990	l = −28→28
45254 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)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.138	H-atom parameters constrained
S = 1.18	w = 1/[σ^2(Fo^2) + (0.0286P)^2 + 3.2694P] where P = (Fo^2 + 2Fc^2)/3
6394 reflections	(Δ/σ)max < 0.001
359 parameters	Δρmax = 0.28 e Å^−3
0 restraints	Δρmin = −0.31 e Å^−3

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

	x	y	z	Uiso*/Ueq
O51	0.87453 (14)	0.75668 (17)	0.61797 (8)	0.0285 (4)
O55	0.83207 (14)	0.37125 (17)	0.70208 (9)	0.0313 (4)
O72	0.48952 (13)	0.35748 (17)	0.79412 (7)	0.0247 (4)
O73	0.32584 (13)	0.47921 (18)	0.84955 (8)	0.0270 (4)
N1	0.60221 (14)	0.30765 (19)	0.54413 (9)	0.0179 (4)
N2	0.67439 (14)	0.25107 (19)	0.50560 (9)	0.0173 (4)
N7	0.59712 (14)	0.47487 (18)	0.62258 (9)	0.0175 (4)
C3	0.76637 (17)	0.3113 (2)	0.51733 (10)	0.0165 (5)
C3A	0.75543 (17)	0.4060 (2)	0.56364 (10)	0.0184 (5)
C4	0.83106 (18)	0.5005 (2)	0.59254 (11)	0.0215 (5)
C5	0.78300 (17)	0.5648 (2)	0.64916 (10)	0.0182 (5)
C6	0.65969 (17)	0.5904 (2)	0.63767 (11)	0.0188 (5)
C7A	0.65012 (17)	0.3997 (2)	0.57969 (10)	0.0174 (5)
C11	0.49320 (17)	0.2708 (2)	0.53941 (10)	0.0176 (5)
C12	0.41355 (18)	0.3633 (2)	0.53586 (11)	0.0208 (5)
C13	0.30822 (19)	0.3241 (2)	0.52898 (11)	0.0236 (5)
C14	0.28311 (19)	0.1946 (3)	0.52431 (11)	0.0239 (5)
C15	0.36305 (18)	0.1021 (2)	0.52861 (11)	0.0242 (5)
C16	0.46844 (18)	0.1409 (2)	0.53686 (11)	0.0196 (5)
C31	0.86410 (17)	0.2769 (2)	0.48063 (10)	0.0182 (5)
C32	0.95863 (19)	0.2431 (3)	0.52294 (12)	0.0270 (6)
C33	0.84272 (19)	0.1611 (2)	0.43891 (11)	0.0238 (5)
C34	0.89340 (19)	0.3941 (2)	0.44119 (11)	0.0237 (5)
C51	0.83268 (18)	0.6997 (2)	0.65931 (11)	0.0195 (5)
C52	0.8237 (2)	0.7586 (2)	0.72212 (11)	0.0270 (6)
C53	0.8540 (2)	0.6655 (3)	0.77381 (12)	0.0312 (6)
C54	0.7830 (2)	0.5442 (3)	0.76690 (12)	0.0298 (6)
C55	0.80049 (17)	0.4814 (2)	0.70631 (11)	0.0219 (5)
C71	0.45886 (17)	0.4772 (2)	0.70299 (10)	0.0177 (5)
C72	0.43340 (18)	0.4518 (2)	0.76333 (11)	0.0193 (5)
C73	0.34713 (18)	0.5151 (2)	0.79076 (11)	0.0205 (5)
C74	0.28774 (18)	0.6041 (2)	0.75745 (11)	0.0218 (5)
C75	0.31304 (19)	0.6284 (2)	0.69711 (12)	0.0244 (5)
C76	0.39746 (18)	0.5658 (2)	0.66993 (11)	0.0227 (5)
C77	0.55088 (18)	0.4043 (2)	0.67472 (11)	0.0198 (5)
C531	0.9715 (2)	0.6265 (3)	0.76954 (15)	0.0418 (7)
C532	0.8330 (3)	0.7304 (4)	0.83507 (14)	0.0574 (10)
C721	0.5395 (2)	0.3965 (3)	0.85102 (12)	0.0307 (6)
C731	0.2419 (2)	0.5468 (3)	0.87925 (12)	0.0294 (6)
H4A	0.8494	0.5684	0.5622	0.026*
H4B	0.8981	0.4550	0.6046	0.026*
H6A	0.6297	0.6306	0.6750	0.023*
H6B	0.6514	0.6537	0.6037	0.023*
H12	0.4309	0.4531	0.5381	0.025*
H13	0.2527	0.3872	0.5275	0.028*
H14	0.2106	0.1686	0.5181	0.029*
H15	0.3457	0.0123	0.5259	0.029*
H16	0.5237	0.0777	0.5408	0.024*
H32A	0.9391	0.1701	0.5494	0.040*
H32B	0.9771	0.3186	0.5484	0.040*
H32C	1.0205	0.2189	0.4982	0.040*
H33A	0.7807	0.1797	0.4121	0.036*
H33B	0.8278	0.0843	0.4640	0.036*
H33C	0.9058	0.1448	0.4137	0.036*
H34A	0.9108	0.4681	0.4679	0.036*
H34B	0.8325	0.4166	0.4142	0.036*
H34C	0.9557	0.3727	0.4162	0.036*
H52A	0.7490	0.7883	0.7279	0.032*
H52B	0.8709	0.8359	0.7247	0.032*
H54A	0.8003	0.4819	0.8002	0.036*
H54B	0.7067	0.5692	0.7704	0.036*
H74	0.2297	0.6485	0.7760	0.026*
H75	0.2716	0.6891	0.6740	0.029*
H76	0.4137	0.5834	0.6282	0.027*
H77A	0.6074	0.3899	0.7064	0.024*
H77B	0.5252	0.3182	0.6605	0.024*
H53A	1.0168	0.7036	0.7749	0.063*
H53B	0.9844	0.5876	0.7292	0.063*
H53C	0.9888	0.5631	0.8018	0.063*
H53D	0.7572	0.7549	0.8371	0.086*
H53E	0.8778	0.8083	0.8391	0.086*
H53F	0.8504	0.6698	0.8685	0.086*
H72A	0.4949	0.3689	0.8854	0.046*
H72B	0.5473	0.4912	0.8517	0.046*
H72C	0.6104	0.3559	0.8548	0.046*
H73A	0.1736	0.5285	0.8581	0.044*
H73B	0.2562	0.6404	0.8781	0.044*
H73C	0.2379	0.5181	0.9221	0.044*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O51	0.0304 (9)	0.0218 (9)	0.0335 (10)	−0.0044 (8)	0.0112 (8)	−0.0017 (8)
O55	0.0257 (9)	0.0200 (10)	0.0481 (12)	−0.0013 (8)	−0.0052 (8)	0.0060 (8)
O72	0.0298 (9)	0.0248 (9)	0.0193 (9)	0.0085 (8)	−0.0003 (7)	−0.0009 (7)
O73	0.0277 (9)	0.0325 (10)	0.0210 (9)	0.0082 (8)	0.0069 (7)	−0.0007 (8)
N1	0.0121 (9)	0.0190 (10)	0.0225 (10)	−0.0019 (8)	0.0024 (7)	−0.0029 (8)
N2	0.0137 (9)	0.0178 (10)	0.0204 (10)	0.0002 (8)	0.0033 (7)	−0.0012 (8)
N7	0.0145 (9)	0.0174 (10)	0.0209 (10)	−0.0019 (8)	0.0041 (7)	−0.0028 (8)
C3	0.0137 (10)	0.0152 (11)	0.0206 (12)	−0.0006 (9)	−0.0001 (9)	0.0024 (9)
C3A	0.0157 (11)	0.0186 (12)	0.0210 (12)	−0.0007 (9)	0.0021 (9)	−0.0007 (10)
C4	0.0154 (11)	0.0214 (12)	0.0278 (13)	−0.0030 (10)	0.0047 (9)	−0.0055 (10)
C5	0.0148 (10)	0.0181 (12)	0.0216 (12)	−0.0013 (9)	0.0013 (9)	−0.0019 (10)
C6	0.0168 (11)	0.0190 (12)	0.0207 (12)	0.0006 (9)	0.0017 (9)	−0.0018 (10)
C7A	0.0165 (11)	0.0160 (11)	0.0198 (11)	−0.0010 (9)	0.0014 (9)	0.0005 (9)
C11	0.0131 (10)	0.0230 (12)	0.0166 (11)	−0.0039 (9)	0.0014 (8)	−0.0008 (9)
C12	0.0205 (12)	0.0159 (11)	0.0261 (13)	−0.0005 (10)	0.0019 (9)	0.0012 (10)
C13	0.0173 (11)	0.0252 (13)	0.0284 (13)	0.0047 (10)	−0.0005 (10)	0.0015 (11)
C14	0.0143 (11)	0.0301 (14)	0.0274 (13)	−0.0039 (10)	0.0004 (9)	−0.0022 (11)
C15	0.0195 (12)	0.0209 (12)	0.0322 (14)	−0.0063 (10)	0.0020 (10)	−0.0043 (11)
C16	0.0172 (11)	0.0173 (11)	0.0244 (12)	0.0012 (9)	0.0025 (9)	−0.0018 (10)
C31	0.0153 (11)	0.0179 (12)	0.0215 (12)	−0.0009 (9)	0.0028 (9)	−0.0025 (10)
C32	0.0177 (12)	0.0326 (14)	0.0307 (14)	0.0059 (11)	0.0014 (10)	−0.0034 (12)
C33	0.0197 (12)	0.0225 (13)	0.0292 (13)	−0.0009 (10)	0.0066 (10)	−0.0066 (11)
C34	0.0188 (12)	0.0234 (13)	0.0290 (13)	−0.0045 (10)	0.0065 (10)	0.0000 (11)
C51	0.0149 (11)	0.0174 (12)	0.0262 (13)	0.0016 (9)	−0.0003 (9)	−0.0008 (10)
C52	0.0286 (13)	0.0228 (13)	0.0297 (14)	−0.0024 (11)	0.0000 (11)	−0.0085 (11)
C53	0.0351 (15)	0.0342 (15)	0.0241 (13)	−0.0009 (12)	−0.0055 (11)	−0.0049 (12)
C54	0.0247 (13)	0.0389 (16)	0.0257 (14)	−0.0011 (12)	0.0001 (10)	0.0076 (12)
C55	0.0132 (11)	0.0215 (13)	0.0310 (14)	−0.0046 (10)	−0.0019 (9)	0.0022 (11)
C71	0.0146 (11)	0.0173 (11)	0.0212 (12)	−0.0012 (9)	0.0012 (9)	−0.0035 (9)
C72	0.0181 (11)	0.0166 (12)	0.0231 (12)	−0.0006 (9)	−0.0011 (9)	−0.0019 (10)
C73	0.0205 (11)	0.0206 (12)	0.0205 (12)	−0.0022 (10)	0.0028 (9)	−0.0035 (10)
C74	0.0160 (11)	0.0209 (12)	0.0287 (13)	0.0016 (10)	0.0036 (9)	−0.0038 (10)
C75	0.0196 (12)	0.0245 (13)	0.0289 (13)	0.0036 (10)	−0.0005 (10)	0.0024 (11)
C76	0.0203 (12)	0.0262 (13)	0.0215 (12)	0.0000 (10)	0.0030 (9)	0.0020 (10)
C77	0.0163 (11)	0.0196 (12)	0.0236 (12)	−0.0004 (9)	0.0039 (9)	−0.0010 (10)
C531	0.0315 (15)	0.0434 (18)	0.0499 (19)	−0.0051 (14)	−0.0176 (13)	−0.0005 (15)
C532	0.076 (3)	0.068 (2)	0.0283 (17)	0.002 (2)	−0.0061 (16)	−0.0131 (16)
C721	0.0299 (14)	0.0379 (16)	0.0241 (13)	0.0075 (12)	−0.0052 (11)	−0.0014 (12)
C731	0.0327 (14)	0.0330 (15)	0.0227 (13)	0.0046 (12)	0.0093 (11)	−0.0048 (11)

Geometric parameters (Å, º)

O51—C51	1.200 (3)	C32—H32C	0.98
O55—C55	1.204 (3)	C33—H33A	0.98
O72—C72	1.366 (3)	C33—H33B	0.98
O72—C721	1.435 (3)	C33—H33C	0.98
O73—C73	1.361 (3)	C34—H34A	0.98
O73—C731	1.420 (3)	C34—H34B	0.98
N1—C7A	1.356 (3)	C34—H34C	0.98
N1—N2	1.369 (3)	C51—C52	1.501 (3)
N1—C11	1.413 (3)	C52—C53	1.521 (4)
N2—C3	1.325 (3)	C52—H52A	0.99
N7—C7A	1.387 (3)	C52—H52B	0.99
N7—C6	1.456 (3)	C53—C532	1.517 (4)
N7—C77	1.472 (3)	C53—C531	1.523 (4)
C3—C3A	1.410 (3)	C53—C54	1.536 (4)
C3—C31	1.509 (3)	C54—C55	1.487 (4)
C3A—C7A	1.365 (3)	C54—H54A	0.99
C3A—C4	1.488 (3)	C54—H54B	0.99
C4—C5	1.529 (3)	C71—C72	1.380 (3)
C4—H4A	0.99	C71—C76	1.385 (3)
C4—H4B	0.99	C71—C77	1.509 (3)
C5—C55	1.524 (3)	C72—C73	1.399 (3)
C5—C51	1.534 (3)	C73—C74	1.378 (3)
C5—C6	1.576 (3)	C74—C75	1.378 (3)
C6—H6A	0.99	C74—H74	0.95
C6—H6B	0.99	C75—C76	1.375 (3)
C11—C16	1.373 (3)	C75—H75	0.95
C11—C12	1.377 (3)	C76—H76	0.95
C12—C13	1.380 (3)	C77—H77A	0.99
C12—H12	0.95	C77—H77B	0.99
C13—C14	1.372 (4)	C531—H53A	0.98
C13—H13	0.95	C531—H53B	0.98
C14—C15	1.381 (3)	C531—H53C	0.98
C14—H14	0.95	C532—H53D	0.98
C15—C16	1.383 (3)	C532—H53E	0.98
C15—H15	0.95	C532—H53F	0.98
C16—H16	0.95	C721—H72A	0.98
C31—C33	1.519 (3)	C721—H72B	0.98
C31—C32	1.525 (3)	C721—H72C	0.98
C31—C34	1.527 (3)	C731—H73A	0.98
C32—H32A	0.98	C731—H73B	0.98
C32—H32B	0.98	C731—H73C	0.98
C72—O72—C721	115.93 (19)	C31—C34—H34C	109.5
C73—O73—C731	116.75 (19)	H34A—C34—H34C	109.5
C7A—N1—N2	111.01 (17)	H34B—C34—H34C	109.5
C7A—N1—C11	130.08 (19)	O51—C51—C52	121.6 (2)
N2—N1—C11	118.79 (18)	O51—C51—C5	120.9 (2)
C3—N2—N1	104.96 (18)	C52—C51—C5	117.5 (2)
C7A—N7—C6	110.35 (17)	C51—C52—C53	113.5 (2)
C7A—N7—C77	116.10 (18)	C51—C52—H52A	108.9
C6—N7—C77	116.30 (18)	C53—C52—H52A	108.9
N2—C3—C3A	111.61 (19)	C51—C52—H52B	108.9
N2—C3—C31	119.5 (2)	C53—C52—H52B	108.9
C3A—C3—C31	128.9 (2)	H52A—C52—H52B	107.7
C7A—C3A—C3	104.7 (2)	C532—C53—C52	109.2 (2)
C7A—C3A—C4	121.9 (2)	C532—C53—C531	110.4 (2)
C3—C3A—C4	133.4 (2)	C52—C53—C531	110.4 (2)
C3A—C4—C5	111.72 (18)	C532—C53—C54	109.7 (3)
C3A—C4—H4A	109.3	C52—C53—C54	107.6 (2)
C5—C4—H4A	109.3	C531—C53—C54	109.5 (2)
C3A—C4—H4B	109.3	C55—C54—C53	110.4 (2)
C5—C4—H4B	109.3	C55—C54—H54A	109.6
H4A—C4—H4B	107.9	C53—C54—H54A	109.6
C55—C5—C4	111.2 (2)	C55—C54—H54B	109.6
C55—C5—C51	109.83 (19)	C53—C54—H54B	109.6
C4—C5—C51	110.19 (19)	H54A—C54—H54B	108.1
C55—C5—C6	110.54 (18)	O55—C55—C54	121.9 (2)
C4—C5—C6	109.71 (18)	O55—C55—C5	120.7 (2)
C51—C5—C6	105.24 (18)	C54—C55—C5	117.2 (2)
N7—C6—C5	114.70 (18)	C72—C71—C76	119.1 (2)
N7—C6—H6A	108.6	C72—C71—C77	118.7 (2)
C5—C6—H6A	108.6	C76—C71—C77	122.2 (2)
N7—C6—H6B	108.6	O72—C72—C71	118.5 (2)
C5—C6—H6B	108.6	O72—C72—C73	120.9 (2)
H6A—C6—H6B	107.6	C71—C72—C73	120.5 (2)
N1—C7A—C3A	107.7 (2)	O73—C73—C74	124.3 (2)
N1—C7A—N7	124.28 (19)	O73—C73—C72	115.9 (2)
C3A—C7A—N7	128.0 (2)	C74—C73—C72	119.7 (2)
C16—C11—C12	120.6 (2)	C73—C74—C75	119.5 (2)
C16—C11—N1	118.7 (2)	C73—C74—H74	120.2
C12—C11—N1	120.7 (2)	C75—C74—H74	120.2
C11—C12—C13	119.3 (2)	C76—C75—C74	120.9 (2)
C11—C12—H12	120.4	C76—C75—H75	119.6
C13—C12—H12	120.4	C74—C75—H75	119.6
C14—C13—C12	120.5 (2)	C75—C76—C71	120.4 (2)
C14—C13—H13	119.7	C75—C76—H76	119.8
C12—C13—H13	119.7	C71—C76—H76	119.8
C13—C14—C15	120.1 (2)	N7—C77—C71	112.22 (19)
C13—C14—H14	120.0	N7—C77—H77A	109.2
C15—C14—H14	120.0	C71—C77—H77A	109.2
C14—C15—C16	119.6 (2)	N7—C77—H77B	109.2
C14—C15—H15	120.2	C71—C77—H77B	109.2
C16—C15—H15	120.2	H77A—C77—H77B	107.9
C11—C16—C15	119.9 (2)	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—C33	111.36 (18)	C53—C531—H53C	109.5
C3—C31—C32	110.90 (19)	H53A—C531—H53C	109.5
C33—C31—C32	108.0 (2)	H53B—C531—H53C	109.5
C3—C31—C34	108.31 (19)	C53—C532—H53D	109.5
C33—C31—C34	108.93 (19)	C53—C532—H53E	109.5
C32—C31—C34	109.28 (19)	H53D—C532—H53E	109.5
C31—C32—H32A	109.5	C53—C532—H53F	109.5
C31—C32—H32B	109.5	H53D—C532—H53F	109.5
H32A—C32—H32B	109.5	H53E—C532—H53F	109.5
C31—C32—H32C	109.5	O72—C721—H72A	109.5
H32A—C32—H32C	109.5	O72—C721—H72B	109.5
H32B—C32—H32C	109.5	H72A—C721—H72B	109.5
C31—C33—H33A	109.5	O72—C721—H72C	109.5
C31—C33—H33B	109.5	H72A—C721—H72C	109.5
H33A—C33—H33B	109.5	H72B—C721—H72C	109.5
C31—C33—H33C	109.5	O73—C731—H73A	109.5
H33A—C33—H33C	109.5	O73—C731—H73B	109.5
H33B—C33—H33C	109.5	H73A—C731—H73B	109.5
C31—C34—H34A	109.5	O73—C731—H73C	109.5
C31—C34—H34B	109.5	H73A—C731—H73C	109.5
H34A—C34—H34B	109.5	H73B—C731—H73C	109.5
C7A—N1—N2—C3	−1.1 (2)	N2—C3—C31—C34	112.8 (2)
C11—N1—N2—C3	175.3 (2)	C3A—C3—C31—C34	−64.8 (3)
N1—N2—C3—C3A	0.6 (2)	C55—C5—C51—O51	144.1 (2)
N1—N2—C3—C31	−177.38 (19)	C4—C5—C51—O51	21.3 (3)
N2—C3—C3A—C7A	0.1 (3)	C6—C5—C51—O51	−96.9 (2)
C31—C3—C3A—C7A	177.8 (2)	C55—C5—C51—C52	−37.7 (3)
N2—C3—C3A—C4	−178.5 (2)	C4—C5—C51—C52	−160.5 (2)
C31—C3—C3A—C4	−0.8 (4)	C6—C5—C51—C52	81.3 (2)
C7A—C3A—C4—C5	12.0 (3)	O51—C51—C52—C53	−134.5 (2)
C3—C3A—C4—C5	−169.6 (2)	C5—C51—C52—C53	47.3 (3)
C3A—C4—C5—C55	85.0 (2)	C51—C52—C53—C532	−175.1 (2)
C3A—C4—C5—C51	−152.9 (2)	C51—C52—C53—C531	63.4 (3)
C3A—C4—C5—C6	−37.5 (3)	C51—C52—C53—C54	−56.1 (3)
C7A—N7—C6—C5	−44.8 (3)	C532—C53—C54—C55	178.5 (2)
C77—N7—C6—C5	90.2 (2)	C52—C53—C54—C55	59.8 (3)
C55—C5—C6—N7	−65.5 (2)	C531—C53—C54—C55	−60.3 (3)
C4—C5—C6—N7	57.4 (3)	C53—C54—C55—O55	120.2 (3)
C51—C5—C6—N7	175.93 (19)	C53—C54—C55—C5	−56.4 (3)
N2—N1—C7A—C3A	1.1 (3)	C4—C5—C55—O55	−11.4 (3)
C11—N1—C7A—C3A	−174.7 (2)	C51—C5—C55—O55	−133.6 (2)
N2—N1—C7A—N7	179.1 (2)	C6—C5—C55—O55	110.7 (2)
C11—N1—C7A—N7	3.2 (4)	C4—C5—C55—C54	165.22 (19)
C3—C3A—C7A—N1	−0.7 (3)	C51—C5—C55—C54	43.0 (3)
C4—C3A—C7A—N1	178.1 (2)	C6—C5—C55—C54	−72.7 (2)
C3—C3A—C7A—N7	−178.5 (2)	C721—O72—C72—C71	125.3 (2)
C4—C3A—C7A—N7	0.3 (4)	C721—O72—C72—C73	−59.2 (3)
C6—N7—C7A—N1	−161.0 (2)	C76—C71—C72—O72	175.3 (2)
C77—N7—C7A—N1	63.9 (3)	C77—C71—C72—O72	−2.9 (3)
C6—N7—C7A—C3A	16.5 (3)	C76—C71—C72—C73	−0.3 (3)
C77—N7—C7A—C3A	−118.6 (3)	C77—C71—C72—C73	−178.5 (2)
C7A—N1—C11—C16	−137.0 (3)	C731—O73—C73—C74	−5.2 (3)
N2—N1—C11—C16	47.4 (3)	C731—O73—C73—C72	177.0 (2)
C7A—N1—C11—C12	44.6 (4)	O72—C72—C73—O73	1.8 (3)
N2—N1—C11—C12	−130.9 (2)	C71—C72—C73—O73	177.3 (2)
C16—C11—C12—C13	−0.7 (4)	O72—C72—C73—C74	−176.0 (2)
N1—C11—C12—C13	177.6 (2)	C71—C72—C73—C74	−0.5 (3)
C11—C12—C13—C14	−1.5 (4)	O73—C73—C74—C75	−176.6 (2)
C12—C13—C14—C15	2.2 (4)	C72—C73—C74—C75	1.0 (4)
C13—C14—C15—C16	−0.8 (4)	C73—C74—C75—C76	−0.7 (4)
C12—C11—C16—C15	2.2 (4)	C74—C75—C76—C71	−0.2 (4)
N1—C11—C16—C15	−176.2 (2)	C72—C71—C76—C75	0.6 (4)
C14—C15—C16—C11	−1.4 (4)	C77—C71—C76—C75	178.8 (2)
N2—C3—C31—C33	−7.0 (3)	C7A—N7—C77—C71	−155.66 (19)
C3A—C3—C31—C33	175.4 (2)	C6—N7—C77—C71	72.0 (2)
N2—C3—C31—C32	−127.3 (2)	C72—C71—C77—N7	−156.3 (2)
C3A—C3—C31—C32	55.1 (3)	C76—C71—C77—N7	25.6 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C74—H74···O55^i	0.95	2.47	3.256 (3)	140

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

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

Crystal data

C31H35N3O4	Z = 2
Mr = 513.62	F(000) = 548
Triclinic, P1	Dx = 1.304 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.2691 (14) Å	Cell parameters from 6010 reflections
b = 11.0898 (11) Å	θ = 2.8–27.5°
c = 12.802 (2) Å	µ = 0.09 mm^−1
α = 92.844 (10)°	T = 120 K
β = 95.185 (12)°	Block, colourless
γ = 91.070 (11)°	0.54 × 0.29 × 0.10 mm
V = 1308.6 (3) Å^3

Data collection

Bruker–Nonius KappaCCD diffractometer	6010 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	2954 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.129
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 2.8°
ϕ & ω scans	h = −12→12
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −14→14
Tmin = 0.964, Tmax = 0.991	l = −16→16
36798 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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.171	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0718P)^2 + 0.282P] where P = (Fo^2 + 2Fc^2)/3
6010 reflections	(Δ/σ)max < 0.001
348 parameters	Δρmax = 0.31 e Å^−3
0 restraints	Δρmin = −0.34 e Å^−3

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

	x	y	z	Uiso*/Ueq
O51	0.5728 (2)	0.99129 (17)	0.66461 (16)	0.0328 (5)
O55	0.9779 (2)	0.81602 (18)	0.74159 (16)	0.0346 (5)
O71	0.8475 (2)	0.3713 (2)	1.07939 (16)	0.0436 (6)
O72	0.6089 (2)	0.30962 (18)	1.07474 (16)	0.0369 (5)
N1	0.7543 (2)	0.52473 (19)	0.48136 (18)	0.0250 (5)
N2	0.7985 (2)	0.57304 (19)	0.39266 (18)	0.0256 (6)
N7	0.6924 (2)	0.59297 (19)	0.65551 (17)	0.0224 (5)
C3	0.8075 (3)	0.6912 (2)	0.4144 (2)	0.0228 (6)
C3A	0.7729 (3)	0.7204 (2)	0.5180 (2)	0.0228 (6)
C4	0.7617 (3)	0.8374 (2)	0.5794 (2)	0.0268 (7)
C5	0.7237 (3)	0.8208 (2)	0.6917 (2)	0.0230 (6)
C6	0.6305 (3)	0.7029 (2)	0.6978 (2)	0.0229 (6)
C7A	0.7397 (3)	0.6126 (2)	0.5571 (2)	0.0228 (6)
C11	0.7286 (3)	0.3986 (2)	0.4806 (2)	0.0234 (6)
C12	0.6249 (3)	0.3531 (2)	0.5399 (2)	0.0256 (6)
C13	0.6020 (3)	0.2299 (2)	0.5392 (2)	0.0266 (7)
C14	0.6760 (3)	0.1533 (2)	0.4764 (2)	0.0284 (7)
C15	0.7764 (3)	0.2001 (2)	0.4155 (2)	0.0281 (7)
C16	0.8056 (3)	0.3227 (2)	0.4184 (2)	0.0259 (7)
C31	0.8456 (3)	0.7739 (2)	0.3302 (2)	0.0243 (6)
C32	0.9729 (4)	0.8574 (3)	0.3709 (3)	0.0426 (8)
C33	0.8851 (3)	0.7015 (3)	0.2335 (2)	0.0313 (7)
C34	0.7141 (3)	0.8502 (3)	0.3003 (2)	0.0321 (7)
C51	0.6276 (3)	0.9241 (2)	0.7270 (2)	0.0244 (6)
C52	0.6040 (3)	0.9363 (2)	0.8408 (2)	0.0263 (7)
C53	0.7474 (3)	0.9441 (3)	0.9095 (2)	0.0286 (7)
C54	0.8336 (3)	0.8310 (3)	0.8842 (2)	0.0268 (7)
C55	0.8574 (3)	0.8201 (2)	0.7704 (2)	0.0238 (6)
C71	0.7327 (3)	0.4784 (2)	0.8180 (2)	0.0229 (6)
C72	0.8276 (3)	0.4598 (2)	0.9065 (2)	0.0270 (7)
C73	0.7732 (3)	0.4031 (3)	0.9874 (2)	0.0288 (7)
C74	0.6317 (3)	0.3668 (2)	0.9843 (2)	0.0269 (7)
C75	0.5366 (3)	0.3848 (3)	0.9000 (2)	0.0303 (7)
C76	0.5894 (3)	0.4416 (2)	0.8164 (2)	0.0287 (7)
C77	0.7970 (3)	0.5315 (2)	0.7263 (2)	0.0246 (6)
C78	0.7372 (3)	0.3345 (3)	1.1432 (2)	0.0389 (8)
C531	0.8311 (3)	1.0574 (3)	0.8871 (2)	0.0357 (8)
C532	0.7184 (4)	0.9491 (3)	1.0249 (2)	0.0398 (8)
H4A	0.6866	0.8865	0.5429	0.032*
H4B	0.8553	0.8825	0.5819	0.032*
H6A	0.6148	0.6921	0.7723	0.027*
H6B	0.5344	0.7137	0.6593	0.027*
H12	0.5701	0.4060	0.5806	0.031*
H13	0.5345	0.1976	0.5826	0.032*
H14	0.6579	0.0686	0.4751	0.034*
H15	0.8260	0.1474	0.3710	0.034*
H16	0.8774	0.3544	0.3783	0.031*
H32A	1.0584	0.8091	0.3885	0.064*
H32B	0.9486	0.9038	0.4338	0.064*
H32C	0.9936	0.9128	0.3166	0.064*
H33A	0.8031	0.6485	0.2061	0.047*
H33B	0.9695	0.6525	0.2523	0.047*
H33C	0.9082	0.7567	0.1796	0.047*
H34A	0.6875	0.8964	0.3627	0.048*
H34B	0.6325	0.7972	0.2721	0.048*
H34C	0.7378	0.9059	0.2470	0.048*
H52A	0.5463	0.8658	0.8595	0.032*
H52B	0.5482	1.0098	0.8542	0.032*
H54A	0.9284	0.8354	0.9267	0.032*
H54B	0.7800	0.7584	0.9032	0.032*
H72	0.9264	0.4855	0.9104	0.032*
H75	0.4379	0.3596	0.8981	0.036*
H76	0.5250	0.4555	0.7564	0.034*
H77A	0.8753	0.5899	0.7534	0.030*
H77B	0.8414	0.4660	0.6856	0.030*
H78A	0.7667	0.2615	1.1803	0.047*
H78B	0.7201	0.3996	1.1961	0.047*
H53A	0.7754	1.1286	0.9047	0.053*
H53B	0.8474	1.0558	0.8125	0.053*
H53C	0.9246	1.0609	0.9296	0.053*
H53D	0.6627	0.8768	1.0395	0.060*
H53E	0.6631	1.0212	1.0406	0.060*
H53F	0.8108	0.9525	1.0688	0.060*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O51	0.0397 (12)	0.0258 (11)	0.0334 (13)	0.0080 (9)	0.0014 (10)	0.0062 (9)
O55	0.0254 (11)	0.0421 (12)	0.0378 (13)	0.0024 (9)	0.0098 (9)	0.0025 (10)
O71	0.0342 (12)	0.0713 (16)	0.0265 (13)	−0.0062 (11)	−0.0019 (10)	0.0247 (11)
O72	0.0367 (12)	0.0467 (13)	0.0283 (12)	−0.0089 (10)	0.0023 (10)	0.0167 (10)
N1	0.0341 (14)	0.0201 (12)	0.0225 (13)	0.0002 (10)	0.0091 (11)	0.0045 (10)
N2	0.0305 (13)	0.0247 (13)	0.0229 (14)	0.0019 (10)	0.0067 (10)	0.0061 (10)
N7	0.0280 (13)	0.0210 (12)	0.0194 (13)	0.0052 (10)	0.0056 (10)	0.0054 (10)
C3	0.0215 (14)	0.0252 (15)	0.0224 (16)	0.0042 (11)	0.0034 (12)	0.0043 (12)
C3A	0.0213 (14)	0.0234 (14)	0.0244 (16)	0.0021 (11)	0.0027 (12)	0.0055 (12)
C4	0.0356 (17)	0.0198 (14)	0.0261 (16)	0.0014 (12)	0.0062 (13)	0.0053 (12)
C5	0.0258 (15)	0.0223 (14)	0.0218 (16)	0.0006 (12)	0.0057 (12)	0.0033 (12)
C6	0.0247 (15)	0.0218 (14)	0.0230 (16)	0.0023 (12)	0.0046 (12)	0.0039 (12)
C7A	0.0220 (14)	0.0237 (15)	0.0228 (16)	0.0012 (11)	0.0008 (12)	0.0051 (12)
C11	0.0268 (15)	0.0205 (14)	0.0225 (16)	0.0008 (12)	−0.0012 (12)	0.0043 (12)
C12	0.0266 (15)	0.0254 (15)	0.0256 (16)	0.0031 (12)	0.0067 (12)	−0.0004 (12)
C13	0.0273 (16)	0.0261 (15)	0.0271 (17)	−0.0021 (12)	0.0040 (13)	0.0051 (13)
C14	0.0326 (17)	0.0204 (14)	0.0327 (18)	0.0020 (12)	0.0032 (14)	0.0048 (13)
C15	0.0339 (17)	0.0227 (15)	0.0280 (17)	0.0045 (12)	0.0040 (13)	0.0022 (12)
C16	0.0285 (16)	0.0247 (15)	0.0257 (16)	0.0019 (12)	0.0071 (13)	0.0055 (12)
C31	0.0273 (15)	0.0238 (15)	0.0227 (16)	−0.0003 (12)	0.0049 (12)	0.0071 (12)
C32	0.044 (2)	0.055 (2)	0.0288 (19)	−0.0183 (16)	0.0055 (15)	0.0061 (16)
C33	0.0372 (17)	0.0332 (16)	0.0253 (17)	0.0090 (14)	0.0092 (13)	0.0069 (13)
C34	0.0420 (18)	0.0299 (16)	0.0268 (17)	0.0104 (14)	0.0098 (14)	0.0102 (13)
C51	0.0226 (15)	0.0186 (14)	0.0321 (17)	−0.0037 (11)	0.0022 (13)	0.0030 (13)
C52	0.0249 (15)	0.0249 (15)	0.0306 (17)	0.0033 (12)	0.0083 (13)	0.0032 (13)
C53	0.0309 (16)	0.0337 (16)	0.0221 (16)	−0.0013 (13)	0.0090 (13)	−0.0008 (13)
C54	0.0242 (15)	0.0347 (16)	0.0218 (16)	0.0011 (13)	0.0026 (12)	0.0047 (13)
C55	0.0238 (16)	0.0205 (14)	0.0281 (17)	0.0018 (11)	0.0046 (13)	0.0048 (12)
C71	0.0283 (16)	0.0197 (14)	0.0211 (16)	0.0023 (12)	0.0035 (12)	0.0030 (12)
C72	0.0252 (15)	0.0304 (16)	0.0256 (17)	−0.0025 (12)	0.0016 (13)	0.0059 (13)
C73	0.0310 (17)	0.0322 (16)	0.0236 (17)	0.0006 (13)	0.0013 (13)	0.0075 (13)
C74	0.0346 (17)	0.0265 (15)	0.0212 (16)	0.0002 (13)	0.0061 (13)	0.0110 (13)
C75	0.0274 (16)	0.0334 (17)	0.0308 (18)	−0.0027 (13)	0.0031 (13)	0.0082 (14)
C76	0.0290 (16)	0.0320 (16)	0.0253 (17)	0.0025 (13)	0.0013 (13)	0.0071 (13)
C77	0.0282 (16)	0.0226 (14)	0.0235 (16)	0.0057 (12)	0.0007 (12)	0.0062 (12)
C78	0.0367 (18)	0.055 (2)	0.0257 (18)	−0.0050 (16)	0.0020 (14)	0.0145 (15)
C531	0.0387 (18)	0.0342 (17)	0.0338 (19)	−0.0046 (14)	0.0072 (15)	−0.0068 (14)
C532	0.0412 (19)	0.051 (2)	0.0287 (18)	0.0032 (16)	0.0110 (15)	−0.0005 (15)

Geometric parameters (Å, º)

O51—C51	1.204 (3)	C32—H32A	0.98
O55—C55	1.208 (3)	C32—H32B	0.98
O71—C73	1.374 (3)	C32—H32C	0.98
O71—C78	1.431 (4)	C33—H33A	0.98
O72—C74	1.378 (3)	C33—H33B	0.98
O72—C78	1.425 (4)	C33—H33C	0.98
N1—C7A	1.357 (3)	C34—H34A	0.98
N1—N2	1.371 (3)	C34—H34B	0.98
N1—C11	1.414 (3)	C34—H34C	0.98
N2—C3	1.326 (3)	C51—C52	1.493 (4)
N7—C7A	1.397 (3)	C52—C53	1.525 (4)
N7—C6	1.458 (3)	C52—H52A	0.99
N7—C77	1.468 (3)	C52—H52B	0.99
C3—C3A	1.415 (4)	C53—C531	1.518 (4)
C3—C31	1.511 (4)	C53—C532	1.524 (4)
C3A—C7A	1.359 (4)	C53—C54	1.536 (4)
C3A—C4	1.495 (4)	C54—C55	1.493 (4)
C4—C5	1.530 (4)	C54—H54A	0.99
C4—H4A	0.99	C54—H54B	0.99
C4—H4B	0.99	C71—C76	1.380 (4)
C5—C55	1.525 (4)	C71—C72	1.396 (4)
C5—C51	1.539 (4)	C71—C77	1.504 (4)
C5—C6	1.562 (4)	C72—C73	1.367 (4)
C6—H6A	0.99	C72—H72	0.95
C6—H6B	0.99	C73—C74	1.362 (4)
C11—C12	1.380 (4)	C74—C75	1.356 (4)
C11—C16	1.382 (4)	C75—C76	1.389 (4)
C12—C13	1.378 (4)	C75—H75	0.95
C12—H12	0.95	C76—H76	0.95
C13—C14	1.376 (4)	C77—H77A	0.99
C13—H13	0.95	C77—H77B	0.99
C14—C15	1.377 (4)	C78—H78A	0.99
C14—H14	0.95	C78—H78B	0.99
C15—C16	1.379 (4)	C531—H53A	0.98
C15—H15	0.95	C531—H53B	0.98
C16—H16	0.95	C531—H53C	0.98
C31—C33	1.519 (4)	C532—H53D	0.98
C31—C32	1.523 (4)	C532—H53E	0.98
C31—C34	1.528 (4)	C532—H53F	0.98
C73—O71—C78	104.6 (2)	C31—C34—H34A	109.5
C74—O72—C78	105.0 (2)	C31—C34—H34B	109.5
C7A—N1—N2	110.8 (2)	H34A—C34—H34B	109.5
C7A—N1—C11	130.7 (2)	C31—C34—H34C	109.5
N2—N1—C11	118.5 (2)	H34A—C34—H34C	109.5
C3—N2—N1	105.1 (2)	H34B—C34—H34C	109.5
C7A—N7—C6	109.9 (2)	O51—C51—C52	121.7 (2)
C7A—N7—C77	114.2 (2)	O51—C51—C5	121.0 (3)
C6—N7—C77	116.7 (2)	C52—C51—C5	117.3 (2)
N2—C3—C3A	111.3 (2)	C51—C52—C53	111.4 (2)
N2—C3—C31	119.2 (2)	C51—C52—H52A	109.4
C3A—C3—C31	129.4 (2)	C53—C52—H52A	109.4
C7A—C3A—C3	104.8 (2)	C51—C52—H52B	109.4
C7A—C3A—C4	122.1 (2)	C53—C52—H52B	109.4
C3—C3A—C4	133.0 (2)	H52A—C52—H52B	108.0
C3A—C4—C5	112.9 (2)	C531—C53—C532	109.1 (3)
C3A—C4—H4A	109.0	C531—C53—C52	109.6 (2)
C5—C4—H4A	109.0	C532—C53—C52	109.7 (2)
C3A—C4—H4B	109.0	C531—C53—C54	110.5 (2)
C5—C4—H4B	109.0	C532—C53—C54	109.7 (2)
H4A—C4—H4B	107.8	C52—C53—C54	108.2 (2)
C55—C5—C4	112.6 (2)	C55—C54—C53	111.1 (2)
C55—C5—C51	107.7 (2)	C55—C54—H54A	109.4
C4—C5—C51	110.1 (2)	C53—C54—H54A	109.4
C55—C5—C6	110.0 (2)	C55—C54—H54B	109.4
C4—C5—C6	110.9 (2)	C53—C54—H54B	109.4
C51—C5—C6	105.2 (2)	H54A—C54—H54B	108.0
N7—C6—C5	115.3 (2)	O55—C55—C54	121.4 (3)
N7—C6—H6A	108.4	O55—C55—C5	121.3 (3)
C5—C6—H6A	108.4	C54—C55—C5	117.2 (2)
N7—C6—H6B	108.4	C76—C71—C72	119.4 (2)
C5—C6—H6B	108.4	C76—C71—C77	123.7 (2)
H6A—C6—H6B	107.5	C72—C71—C77	116.8 (2)
N1—C7A—C3A	108.0 (2)	C73—C72—C71	117.5 (3)
N1—C7A—N7	124.7 (2)	C73—C72—H72	121.2
C3A—C7A—N7	127.3 (3)	C71—C72—H72	121.2
C12—C11—C16	120.9 (2)	C74—C73—C72	122.3 (3)
C12—C11—N1	119.8 (2)	C74—C73—O71	110.2 (2)
C16—C11—N1	119.3 (2)	C72—C73—O71	127.5 (3)
C13—C12—C11	119.1 (3)	C75—C74—C73	121.5 (3)
C13—C12—H12	120.4	C75—C74—O72	128.9 (3)
C11—C12—H12	120.4	C73—C74—O72	109.5 (2)
C14—C13—C12	120.7 (3)	C74—C75—C76	117.4 (3)
C14—C13—H13	119.7	C74—C75—H75	121.3
C12—C13—H13	119.7	C76—C75—H75	121.3
C13—C14—C15	119.6 (3)	C71—C76—C75	121.9 (3)
C13—C14—H14	120.2	C71—C76—H76	119.1
C15—C14—H14	120.2	C75—C76—H76	119.0
C14—C15—C16	120.7 (3)	N7—C77—C71	114.1 (2)
C14—C15—H15	119.7	N7—C77—H77A	108.7
C16—C15—H15	119.7	C71—C77—H77A	108.7
C15—C16—C11	119.0 (3)	N7—C77—H77B	108.7
C15—C16—H16	120.5	C71—C77—H77B	108.7
C11—C16—H16	120.5	H77A—C77—H77B	107.6
C3—C31—C33	110.8 (2)	O72—C78—O71	107.1 (2)
C3—C31—C32	110.4 (2)	O72—C78—H78A	110.3
C33—C31—C32	109.0 (2)	O71—C78—H78A	110.3
C3—C31—C34	108.4 (2)	O72—C78—H78B	110.3
C33—C31—C34	109.2 (2)	O71—C78—H78B	110.3
C32—C31—C34	109.1 (2)	H78A—C78—H78B	108.6
C31—C32—H32A	109.5	C53—C531—H53A	109.5
C31—C32—H32B	109.5	C53—C531—H53B	109.5
H32A—C32—H32B	109.5	H53A—C531—H53B	109.5
C31—C32—H32C	109.5	C53—C531—H53C	109.5
H32A—C32—H32C	109.5	H53A—C531—H53C	109.5
H32B—C32—H32C	109.5	H53B—C531—H53C	109.5
C31—C33—H33A	109.5	C53—C532—H53D	109.5
C31—C33—H33B	109.5	C53—C532—H53E	109.5
H33A—C33—H33B	109.5	H53D—C532—H53E	109.5
C31—C33—H33C	109.5	C53—C532—H53F	109.5
H33A—C33—H33C	109.5	H53D—C532—H53F	109.5
H33B—C33—H33C	109.5	H53E—C532—H53F	109.5
C7A—N1—N2—C3	−1.3 (3)	C3A—C3—C31—C34	−64.2 (4)
C11—N1—N2—C3	177.3 (2)	C55—C5—C51—O51	135.6 (3)
N1—N2—C3—C3A	1.5 (3)	C4—C5—C51—O51	12.5 (3)
N1—N2—C3—C31	−176.5 (2)	C6—C5—C51—O51	−107.1 (3)
N2—C3—C3A—C7A	−1.1 (3)	C55—C5—C51—C52	−45.2 (3)
C31—C3—C3A—C7A	176.6 (3)	C4—C5—C51—C52	−168.3 (2)
N2—C3—C3A—C4	−177.7 (3)	C6—C5—C51—C52	72.2 (3)
C31—C3—C3A—C4	0.0 (5)	O51—C51—C52—C53	−126.8 (3)
C7A—C3A—C4—C5	5.3 (4)	C5—C51—C52—C53	54.0 (3)
C3—C3A—C4—C5	−178.6 (3)	C51—C52—C53—C531	63.5 (3)
C3A—C4—C5—C55	94.1 (3)	C51—C52—C53—C532	−176.8 (2)
C3A—C4—C5—C51	−145.7 (2)	C51—C52—C53—C54	−57.1 (3)
C3A—C4—C5—C6	−29.7 (3)	C531—C53—C54—C55	−62.4 (3)
C7A—N7—C6—C5	−47.7 (3)	C532—C53—C54—C55	177.2 (2)
C77—N7—C6—C5	84.4 (3)	C52—C53—C54—C55	57.6 (3)
C55—C5—C6—N7	−71.5 (3)	C53—C54—C55—O55	121.9 (3)
C4—C5—C6—N7	53.8 (3)	C53—C54—C55—C5	−54.9 (3)
C51—C5—C6—N7	172.8 (2)	C4—C5—C55—O55	−9.6 (4)
N2—N1—C7A—C3A	0.7 (3)	C51—C5—C55—O55	−131.2 (3)
C11—N1—C7A—C3A	−177.8 (3)	C6—C5—C55—O55	114.7 (3)
N2—N1—C7A—N7	178.1 (2)	C4—C5—C55—C54	167.3 (2)
C11—N1—C7A—N7	−0.3 (5)	C51—C5—C55—C54	45.7 (3)
C3—C3A—C7A—N1	0.2 (3)	C6—C5—C55—C54	−68.4 (3)
C4—C3A—C7A—N1	177.3 (2)	C76—C71—C72—C73	1.2 (4)
C3—C3A—C7A—N7	−177.1 (3)	C77—C71—C72—C73	−175.1 (2)
C4—C3A—C7A—N7	−0.1 (4)	C71—C72—C73—C74	−0.9 (4)
C6—N7—C7A—N1	−155.6 (3)	C71—C72—C73—O71	177.2 (3)
C77—N7—C7A—N1	71.0 (3)	C78—O71—C73—C74	−11.4 (3)
C6—N7—C7A—C3A	21.4 (4)	C78—O71—C73—C72	170.3 (3)
C77—N7—C7A—C3A	−112.1 (3)	C72—C73—C74—C75	0.2 (5)
C7A—N1—C11—C12	29.2 (4)	O71—C73—C74—C75	−178.2 (3)
N2—N1—C11—C12	−149.1 (3)	C72—C73—C74—O72	178.3 (3)
C7A—N1—C11—C16	−152.3 (3)	O71—C73—C74—O72	−0.1 (3)
N2—N1—C11—C16	29.4 (4)	C78—O72—C74—C75	−170.5 (3)
C16—C11—C12—C13	2.2 (4)	C78—O72—C74—C73	11.6 (3)
N1—C11—C12—C13	−179.4 (2)	C73—C74—C75—C76	0.2 (4)
C11—C12—C13—C14	−3.3 (4)	O72—C74—C75—C76	−177.5 (3)
C12—C13—C14—C15	1.5 (4)	C72—C71—C76—C75	−0.9 (4)
C13—C14—C15—C16	1.3 (4)	C77—C71—C76—C75	175.2 (3)
C14—C15—C16—C11	−2.4 (4)	C74—C75—C76—C71	0.2 (4)
C12—C11—C16—C15	0.6 (4)	C7A—N7—C77—C71	−163.1 (2)
N1—C11—C16—C15	−177.8 (3)	C6—N7—C77—C71	66.8 (3)
N2—C3—C31—C33	−6.5 (4)	C76—C71—C77—N7	27.1 (4)
C3A—C3—C31—C33	176.0 (3)	C72—C71—C77—N7	−156.8 (2)
N2—C3—C31—C32	−127.3 (3)	C74—O72—C78—O71	−18.5 (3)
C3A—C3—C31—C32	55.2 (4)	C73—O71—C78—O72	18.3 (3)
N2—C3—C31—C34	113.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···O51^i	0.95	2.58	3.182 (3)	121
C15—H15···O55^ii	0.95	2.46	3.173 (3)	132
C72—H72···O71^iii	0.95	2.60	3.503 (3)	160
C6—H6A···Cg2^iv	0.99	2.69	3.670 (3)	169

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

(IV) 3-tert-butyl-4',4'-dimethyl-1-phenyl-7-(3,4,5-trimethoxybenzyl)- 4,5,6,7-tetrahydro-1H-pyrazolo[3,4-b]pyridine-5-spiro-1'- cyclohexane-2',6'-dione ethanol 0.67-solvate

Crystal data

C33H41N3O5·0.67C2H6O	F(000) = 2539.4
Mr = 590.55	Dx = 1.240 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 7255 reflections
a = 13.5770 (17) Å	θ = 2.9–27.5°
b = 17.476 (3) Å	µ = 0.08 mm^−1
c = 26.670 (3) Å	T = 120 K
V = 6328.0 (15) Å^3	Block, colourless
Z = 8	0.32 × 0.32 × 0.28 mm

Data collection

Bruker–Nonius KappaCCD diffractometer	7255 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	4959 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.058
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 2.9°
ϕ & ω scans	h = −17→17
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −22→22
Tmin = 0.974, Tmax = 0.977	l = −34→33
53340 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)] = 0.087	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.206	H-atom parameters constrained
S = 1.17	w = 1/[σ^2(Fo^2) + (0.0324P)^2 + 20.6148P] where P = (Fo^2 + 2Fc^2)/3
7255 reflections	(Δ/σ)max = 0.001
407 parameters	Δρmax = 0.59 e Å^−3
0 restraints	Δρmin = −0.36 e Å^−3

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
O51	0.2505 (2)	0.69729 (13)	0.25657 (10)	0.0302 (6)
O55	0.41600 (19)	0.49173 (15)	0.22916 (10)	0.0312 (6)
O73	0.28600 (19)	0.33226 (16)	0.44498 (9)	0.0320 (6)
O74	0.0964 (2)	0.33718 (17)	0.46867 (10)	0.0365 (7)
O75	−0.04206 (19)	0.34512 (18)	0.39790 (10)	0.0374 (7)
N1	0.1328 (2)	0.40095 (16)	0.15897 (11)	0.0224 (6)
N2	0.1485 (2)	0.42596 (17)	0.11103 (11)	0.0257 (7)
N7	0.1632 (2)	0.44356 (15)	0.24469 (10)	0.0193 (6)
C3	0.1937 (3)	0.4931 (2)	0.11628 (13)	0.0253 (8)
C3A	0.2098 (3)	0.5104 (2)	0.16709 (13)	0.0228 (7)
C4	0.2593 (3)	0.5759 (2)	0.19249 (13)	0.0246 (8)
C5	0.2707 (2)	0.56254 (18)	0.24859 (13)	0.0214 (7)
C6	0.1793 (2)	0.51708 (19)	0.26848 (13)	0.0209 (7)
C7A	0.1702 (2)	0.45129 (19)	0.19283 (12)	0.0197 (7)
C11	0.0818 (2)	0.33133 (19)	0.16553 (13)	0.0213 (7)
C12	0.0119 (3)	0.32487 (19)	0.20278 (13)	0.0225 (7)
C13	−0.0392 (3)	0.2570 (2)	0.20820 (14)	0.0262 (8)
C14	−0.0215 (3)	0.1971 (2)	0.17613 (15)	0.0309 (9)
C15	0.0481 (3)	0.2042 (2)	0.13891 (14)	0.0284 (8)
C16	0.1005 (3)	0.2710 (2)	0.13373 (14)	0.0261 (8)
C31	0.2264 (3)	0.5363 (2)	0.07028 (14)	0.0313 (9)
C32	0.3375 (3)	0.5263 (3)	0.06520 (15)	0.0390 (10)
C33	0.1755 (4)	0.5050 (3)	0.02363 (15)	0.0426 (11)
C34	0.2027 (3)	0.6210 (2)	0.07521 (15)	0.0395 (10)
C51	0.2724 (2)	0.63847 (19)	0.27734 (13)	0.0230 (7)
C52	0.2993 (3)	0.6354 (2)	0.33161 (14)	0.0269 (8)
C53	0.3964 (3)	0.5938 (2)	0.34064 (13)	0.0248 (8)
C54	0.3917 (3)	0.51472 (19)	0.31575 (13)	0.0238 (7)
C55	0.3647 (2)	0.51939 (19)	0.26136 (13)	0.0223 (7)
C71	0.1797 (3)	0.36435 (18)	0.32065 (13)	0.0206 (7)
C72	0.2499 (3)	0.35259 (19)	0.35697 (12)	0.0219 (7)
C73	0.2215 (3)	0.3419 (2)	0.40610 (13)	0.0260 (8)
C74	0.1236 (3)	0.3411 (2)	0.41890 (13)	0.0285 (8)
C75	0.0529 (3)	0.3497 (2)	0.38184 (14)	0.0283 (8)
C76	0.0808 (3)	0.3628 (2)	0.33297 (13)	0.0244 (8)
C77	0.2115 (3)	0.37681 (18)	0.26748 (12)	0.0203 (7)
C531	0.4813 (3)	0.6393 (2)	0.31860 (16)	0.0320 (9)
C532	0.4122 (3)	0.5815 (2)	0.39656 (15)	0.0382 (10)
C731	0.3879 (3)	0.3404 (3)	0.43396 (15)	0.0380 (10)
C741	0.0871 (4)	0.2629 (3)	0.48607 (18)	0.0560 (14)
C751	−0.1170 (3)	0.3495 (3)	0.36077 (16)	0.0397 (10)
O81	0.1041 (4)	0.5421 (2)	0.38922 (17)	0.0512 (17)	0.670 (7)
C81	0.1075 (5)	0.5454 (4)	0.4395 (3)	0.0453 (19)	0.670 (7)
C82	0.1311 (6)	0.6240 (4)	0.4569 (3)	0.053 (2)	0.670 (7)
H4A	0.2202	0.6230	0.1869	0.030*
H4B	0.3251	0.5838	0.1774	0.030*
H6A	0.1874	0.5088	0.3050	0.025*
H6B	0.1197	0.5489	0.2636	0.025*
H12	−0.0010	0.3667	0.2246	0.027*
H13	−0.0867	0.2517	0.2341	0.031*
H14	−0.0574	0.1507	0.1796	0.037*
H15	0.0600	0.1627	0.1167	0.034*
H16	0.1493	0.2756	0.1084	0.031*
H32A	0.3529	0.4721	0.0599	0.059*
H32B	0.3699	0.5442	0.0959	0.059*
H32C	0.3613	0.5562	0.0365	0.059*
H33A	0.1041	0.5116	0.0269	0.064*
H33B	0.1908	0.4504	0.0200	0.064*
H33C	0.1988	0.5327	−0.0060	0.064*
H34A	0.2365	0.6419	0.1047	0.059*
H34B	0.1315	0.6276	0.0791	0.059*
H34C	0.2250	0.6480	0.0451	0.059*
H52A	0.2462	0.6090	0.3503	0.032*
H52B	0.3043	0.6882	0.3448	0.032*
H54A	0.4566	0.4894	0.3190	0.029*
H54B	0.3425	0.4829	0.3335	0.029*
H72	0.3177	0.3518	0.3483	0.026*
H76	0.0323	0.3707	0.3078	0.029*
H77A	0.2838	0.3842	0.2666	0.024*
H77B	0.1958	0.3306	0.2475	0.024*
H53A	0.4838	0.6900	0.3343	0.048*
H53B	0.4717	0.6450	0.2824	0.048*
H53C	0.5433	0.6122	0.3249	0.048*
H53D	0.4139	0.6312	0.4136	0.057*
H53E	0.4747	0.5548	0.4020	0.057*
H53F	0.3580	0.5507	0.4101	0.057*
H73A	0.3993	0.3900	0.4178	0.057*
H73B	0.4086	0.2992	0.4113	0.057*
H73C	0.4260	0.3375	0.4651	0.057*
H74A	0.1499	0.2361	0.4821	0.084*
H74B	0.0360	0.2364	0.4668	0.084*
H74C	0.0686	0.2638	0.5216	0.084*
H75A	−0.1058	0.3099	0.3354	0.060*
H75B	−0.1153	0.4000	0.3449	0.060*
H75C	−0.1814	0.3415	0.3765	0.060*
H81	0.0903	0.4973	0.3802	0.077*	0.670 (7)
H81A	0.1582	0.5094	0.4520	0.054*	0.670 (7)
H81B	0.0431	0.5295	0.4535	0.054*	0.670 (7)
H82A	0.1002	0.6330	0.4896	0.080*	0.670 (7)
H82B	0.1060	0.6613	0.4326	0.080*	0.670 (7)
H82C	0.2027	0.6297	0.4600	0.080*	0.670 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O51	0.0322 (14)	0.0175 (12)	0.0410 (15)	0.0040 (11)	−0.0003 (12)	0.0028 (11)
O55	0.0262 (13)	0.0316 (14)	0.0359 (15)	0.0051 (12)	0.0037 (11)	−0.0082 (12)
O73	0.0301 (14)	0.0416 (16)	0.0242 (13)	0.0055 (13)	−0.0036 (11)	−0.0016 (12)
O74	0.0401 (16)	0.0436 (17)	0.0258 (14)	−0.0033 (14)	0.0061 (12)	0.0020 (12)
O75	0.0238 (14)	0.0559 (19)	0.0326 (15)	−0.0014 (13)	0.0047 (11)	0.0107 (13)
N1	0.0234 (15)	0.0200 (14)	0.0239 (15)	−0.0041 (12)	0.0001 (12)	0.0033 (12)
N2	0.0317 (17)	0.0238 (15)	0.0217 (15)	−0.0063 (13)	0.0000 (13)	0.0057 (12)
N7	0.0204 (14)	0.0165 (13)	0.0210 (14)	−0.0017 (11)	−0.0011 (11)	0.0012 (11)
C3	0.0266 (19)	0.0219 (17)	0.0274 (19)	−0.0038 (15)	−0.0018 (15)	0.0031 (15)
C3A	0.0218 (17)	0.0229 (17)	0.0239 (18)	−0.0033 (14)	−0.0004 (14)	0.0033 (14)
C4	0.0260 (18)	0.0207 (17)	0.0273 (18)	−0.0063 (15)	−0.0010 (15)	0.0026 (14)
C5	0.0209 (17)	0.0183 (16)	0.0250 (17)	−0.0023 (14)	0.0021 (14)	0.0011 (14)
C6	0.0209 (16)	0.0179 (16)	0.0239 (17)	−0.0033 (14)	0.0018 (14)	−0.0020 (13)
C7A	0.0198 (16)	0.0184 (16)	0.0210 (17)	−0.0003 (14)	−0.0011 (13)	0.0008 (13)
C11	0.0197 (16)	0.0201 (17)	0.0241 (18)	−0.0027 (14)	−0.0044 (14)	0.0036 (14)
C12	0.0228 (17)	0.0181 (16)	0.0266 (18)	−0.0008 (14)	−0.0024 (14)	0.0018 (14)
C13	0.0229 (18)	0.0248 (18)	0.0307 (19)	−0.0047 (15)	−0.0016 (15)	0.0067 (15)
C14	0.032 (2)	0.0217 (18)	0.039 (2)	−0.0055 (16)	−0.0079 (17)	0.0049 (16)
C15	0.030 (2)	0.0197 (17)	0.035 (2)	0.0014 (15)	−0.0084 (17)	−0.0025 (15)
C16	0.0229 (18)	0.0274 (19)	0.0279 (19)	0.0005 (15)	−0.0031 (15)	−0.0007 (15)
C31	0.043 (2)	0.0285 (19)	0.0220 (19)	−0.0128 (18)	−0.0015 (17)	0.0086 (15)
C32	0.046 (3)	0.039 (2)	0.031 (2)	−0.014 (2)	0.0077 (19)	0.0063 (18)
C33	0.060 (3)	0.043 (2)	0.025 (2)	−0.019 (2)	−0.0049 (19)	0.0076 (18)
C34	0.053 (3)	0.034 (2)	0.031 (2)	−0.011 (2)	−0.0023 (19)	0.0159 (18)
C51	0.0173 (16)	0.0194 (17)	0.0322 (19)	−0.0006 (14)	0.0042 (14)	−0.0023 (14)
C52	0.0289 (19)	0.0186 (17)	0.033 (2)	−0.0017 (15)	0.0028 (16)	−0.0055 (15)
C53	0.0275 (19)	0.0202 (17)	0.0267 (19)	−0.0005 (15)	−0.0021 (15)	−0.0045 (14)
C54	0.0236 (18)	0.0178 (16)	0.0299 (19)	−0.0004 (14)	−0.0010 (15)	−0.0010 (14)
C55	0.0206 (17)	0.0150 (15)	0.031 (2)	−0.0010 (14)	0.0024 (15)	−0.0040 (14)
C71	0.0234 (17)	0.0141 (15)	0.0243 (17)	−0.0023 (13)	0.0000 (14)	−0.0003 (13)
C72	0.0224 (17)	0.0195 (16)	0.0239 (17)	0.0009 (14)	0.0016 (14)	−0.0015 (14)
C73	0.0281 (19)	0.0242 (18)	0.0256 (19)	0.0022 (15)	−0.0031 (15)	0.0002 (15)
C74	0.037 (2)	0.030 (2)	0.0184 (18)	0.0024 (17)	0.0058 (15)	0.0004 (15)
C75	0.0229 (18)	0.033 (2)	0.029 (2)	0.0009 (16)	0.0055 (15)	0.0046 (16)
C76	0.0221 (18)	0.0279 (18)	0.0231 (18)	−0.0020 (15)	−0.0016 (14)	0.0045 (15)
C77	0.0218 (17)	0.0160 (15)	0.0232 (17)	−0.0009 (13)	0.0004 (14)	0.0018 (13)
C531	0.0258 (19)	0.0240 (19)	0.046 (2)	−0.0056 (16)	−0.0030 (17)	−0.0014 (17)
C532	0.047 (3)	0.035 (2)	0.032 (2)	0.001 (2)	−0.0073 (19)	−0.0056 (18)
C731	0.028 (2)	0.053 (3)	0.032 (2)	0.011 (2)	−0.0049 (17)	−0.0032 (19)
C741	0.082 (4)	0.043 (3)	0.042 (3)	−0.015 (3)	0.017 (3)	0.000 (2)
C751	0.026 (2)	0.050 (3)	0.043 (2)	−0.0013 (19)	0.0014 (18)	0.008 (2)
O81	0.091 (4)	0.020 (2)	0.042 (3)	−0.010 (2)	0.025 (3)	−0.0026 (19)
C81	0.042 (4)	0.046 (4)	0.048 (4)	−0.009 (3)	−0.014 (3)	0.020 (3)
C82	0.065 (5)	0.052 (5)	0.044 (4)	0.015 (4)	−0.006 (4)	0.002 (3)

Geometric parameters (Å, º)

O51—C51	1.205 (4)	C34—H34A	0.98
O55—C55	1.207 (4)	C34—H34B	0.98
O73—C73	1.368 (4)	C34—H34C	0.98
O73—C731	1.421 (5)	C51—C52	1.493 (5)
O74—C74	1.379 (4)	C52—C53	1.525 (5)
O74—C741	1.384 (5)	C52—H52A	0.99
O75—C75	1.361 (4)	C52—H52B	0.99
O75—C751	1.422 (5)	C53—C531	1.519 (5)
N1—C7A	1.359 (4)	C53—C532	1.522 (5)
N1—N2	1.368 (4)	C53—C54	1.535 (5)
N1—C11	1.411 (4)	C54—C55	1.498 (5)
N2—C3	1.331 (4)	C54—H54A	0.99
N7—C7A	1.393 (4)	C54—H54B	0.99
N7—C6	1.449 (4)	C71—C72	1.374 (5)
N7—C77	1.470 (4)	C71—C76	1.383 (5)
C3—C3A	1.405 (5)	C71—C77	1.498 (5)
C3—C31	1.507 (5)	C72—C73	1.379 (5)
C3A—C7A	1.352 (5)	C72—H72	0.95
C3A—C4	1.490 (5)	C73—C74	1.372 (5)
C4—C5	1.522 (5)	C74—C75	1.386 (5)
C4—H4A	0.99	C75—C76	1.376 (5)
C4—H4B	0.99	C76—H76	0.95
C5—C55	1.521 (5)	C77—H77A	0.99
C5—C51	1.533 (5)	C77—H77B	0.99
C5—C6	1.566 (5)	C531—H53A	0.98
C6—H6A	0.99	C531—H53B	0.98
C6—H6B	0.99	C531—H53C	0.98
C11—C16	1.376 (5)	C532—H53D	0.98
C11—C12	1.378 (5)	C532—H53E	0.98
C12—C13	1.383 (5)	C532—H53F	0.98
C12—H12	0.95	C731—H73A	0.98
C13—C14	1.372 (5)	C731—H73B	0.98
C13—H13	0.95	C731—H73C	0.98
C14—C15	1.377 (6)	C741—H74A	0.98
C14—H14	0.95	C741—H74B	0.98
C15—C16	1.375 (5)	C741—H74C	0.98
C15—H15	0.95	C751—H75A	0.98
C16—H16	0.95	C751—H75B	0.98
C31—C34	1.521 (6)	C751—H75C	0.98
C31—C32	1.524 (6)	O81—C81	1.344 (8)
C31—C33	1.525 (5)	O81—H81	0.84
C32—H32A	0.98	C81—C82	1.485 (10)
C32—H32B	0.98	C81—H81A	0.99
C32—H32C	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
C73—O73—C731	117.0 (3)	C51—C52—H52B	109.1
C74—O74—C741	113.2 (3)	C53—C52—H52B	109.1
C75—O75—C751	117.1 (3)	H52A—C52—H52B	107.9
C7A—N1—N2	110.9 (3)	C531—C53—C532	110.3 (3)
C7A—N1—C11	131.2 (3)	C531—C53—C52	110.3 (3)
N2—N1—C11	117.9 (3)	C532—C53—C52	110.1 (3)
C3—N2—N1	104.8 (3)	C531—C53—C54	109.6 (3)
C7A—N7—C6	109.8 (3)	C532—C53—C54	107.6 (3)
C7A—N7—C77	117.2 (3)	C52—C53—C54	108.9 (3)
C6—N7—C77	117.1 (3)	C55—C54—C53	112.3 (3)
N2—C3—C3A	111.3 (3)	C55—C54—H54A	109.1
N2—C3—C31	119.5 (3)	C53—C54—H54A	109.1
C3A—C3—C31	129.1 (3)	C55—C54—H54B	109.1
C7A—C3A—C3	105.3 (3)	C53—C54—H54B	109.1
C7A—C3A—C4	122.4 (3)	H54A—C54—H54B	107.9
C3—C3A—C4	132.4 (3)	O55—C55—C54	121.7 (3)
C3A—C4—C5	112.0 (3)	O55—C55—C5	121.6 (3)
C3A—C4—H4A	109.2	C54—C55—C5	116.7 (3)
C5—C4—H4A	109.2	C72—C71—C76	120.2 (3)
C3A—C4—H4B	109.2	C72—C71—C77	119.3 (3)
C5—C4—H4B	109.2	C76—C71—C77	120.5 (3)
H4A—C4—H4B	107.9	C71—C72—C73	119.7 (3)
C55—C5—C4	112.4 (3)	C71—C72—H72	120.1
C55—C5—C51	107.7 (3)	C73—C72—H72	120.1
C4—C5—C51	111.1 (3)	O73—C73—C74	115.5 (3)
C55—C5—C6	109.7 (3)	O73—C73—C72	123.9 (3)
C4—C5—C6	109.3 (3)	C74—C73—C72	120.6 (3)
C51—C5—C6	106.4 (3)	C73—C74—O74	120.0 (3)
N7—C6—C5	114.9 (3)	C73—C74—C75	119.5 (3)
N7—C6—H6A	108.5	O74—C74—C75	120.4 (3)
C5—C6—H6A	108.5	O75—C75—C76	124.6 (3)
N7—C6—H6B	108.5	O75—C75—C74	115.2 (3)
C5—C6—H6B	108.5	C76—C75—C74	120.2 (3)
H6A—C6—H6B	107.5	C75—C76—C71	119.7 (3)
C3A—C7A—N1	107.8 (3)	C75—C76—H76	120.2
C3A—C7A—N7	127.3 (3)	C71—C76—H76	120.2
N1—C7A—N7	124.9 (3)	N7—C77—C71	112.2 (3)
C16—C11—C12	120.6 (3)	N7—C77—H77A	109.2
C16—C11—N1	119.5 (3)	C71—C77—H77A	109.2
C12—C11—N1	119.9 (3)	N7—C77—H77B	109.2
C11—C12—C13	119.4 (3)	C71—C77—H77B	109.2
C11—C12—H12	120.3	H77A—C77—H77B	107.9
C13—C12—H12	120.3	C53—C531—H53A	109.5
C14—C13—C12	120.1 (3)	C53—C531—H53B	109.5
C14—C13—H13	120.0	H53A—C531—H53B	109.5
C12—C13—H13	120.0	C53—C531—H53C	109.5
C13—C14—C15	120.1 (3)	H53A—C531—H53C	109.5
C13—C14—H14	120.0	H53B—C531—H53C	109.5
C15—C14—H14	120.0	C53—C532—H53D	109.5
C16—C15—C14	120.3 (4)	C53—C532—H53E	109.5
C16—C15—H15	119.9	H53D—C532—H53E	109.5
C14—C15—H15	119.9	C53—C532—H53F	109.5
C15—C16—C11	119.5 (3)	H53D—C532—H53F	109.5
C15—C16—H16	120.2	H53E—C532—H53F	109.5
C11—C16—H16	120.2	O73—C731—H73A	109.5
C3—C31—C34	110.8 (3)	O73—C731—H73B	109.5
C3—C31—C32	107.9 (3)	H73A—C731—H73B	109.5
C34—C31—C32	109.2 (3)	O73—C731—H73C	109.5
C3—C31—C33	110.5 (3)	H73A—C731—H73C	109.5
C34—C31—C33	108.9 (3)	H73B—C731—H73C	109.5
C32—C31—C33	109.6 (4)	O74—C741—H74A	109.5
C31—C32—H32A	109.5	O74—C741—H74B	109.5
C31—C32—H32B	109.5	H74A—C741—H74B	109.5
H32A—C32—H32B	109.5	O74—C741—H74C	109.5
C31—C32—H32C	109.5	H74A—C741—H74C	109.5
H32A—C32—H32C	109.5	H74B—C741—H74C	109.5
H32B—C32—H32C	109.5	O75—C751—H75A	109.5
C31—C33—H33A	109.5	O75—C751—H75B	109.5
C31—C33—H33B	109.5	H75A—C751—H75B	109.5
H33A—C33—H33B	109.5	O75—C751—H75C	109.5
C31—C33—H33C	109.5	H75A—C751—H75C	109.5
H33A—C33—H33C	109.5	H75B—C751—H75C	109.5
H33B—C33—H33C	109.5	C81—O81—H81	109.5
C31—C34—H34A	109.5	O81—C81—C82	111.0 (6)
C31—C34—H34B	109.5	O81—C81—H81A	109.4
H34A—C34—H34B	109.5	C82—C81—H81A	109.4
C31—C34—H34C	109.5	O81—C81—H81B	109.4
H34A—C34—H34C	109.5	C82—C81—H81B	109.4
H34B—C34—H34C	109.5	H81A—C81—H81B	108.0
O51—C51—C52	122.4 (3)	C81—C82—H82A	109.5
O51—C51—C5	120.3 (3)	C81—C82—H82B	109.5
C52—C51—C5	117.2 (3)	H82A—C82—H82B	109.5
C51—C52—C53	112.4 (3)	C81—C82—H82C	109.5
C51—C52—H52A	109.1	H82A—C82—H82C	109.5
C53—C52—H52A	109.1	H82B—C82—H82C	109.5
C7A—N1—N2—C3	−1.4 (4)	C55—C5—C51—O51	134.8 (3)
C11—N1—N2—C3	177.5 (3)	C4—C5—C51—O51	11.3 (5)
N1—N2—C3—C3A	1.7 (4)	C6—C5—C51—O51	−107.6 (4)
N1—N2—C3—C31	177.5 (3)	C55—C5—C51—C52	−46.9 (4)
N2—C3—C3A—C7A	−1.4 (4)	C4—C5—C51—C52	−170.5 (3)
C31—C3—C3A—C7A	−176.6 (4)	C6—C5—C51—C52	70.7 (4)
N2—C3—C3A—C4	177.8 (4)	O51—C51—C52—C53	−128.7 (4)
C31—C3—C3A—C4	2.6 (7)	C5—C51—C52—C53	53.1 (4)
C7A—C3A—C4—C5	7.4 (5)	C51—C52—C53—C531	66.8 (4)
C3—C3A—C4—C5	−171.7 (4)	C51—C52—C53—C532	−171.2 (3)
C3A—C4—C5—C55	87.1 (4)	C51—C52—C53—C54	−53.5 (4)
C3A—C4—C5—C51	−152.1 (3)	C531—C53—C54—C55	−66.7 (4)
C3A—C4—C5—C6	−35.0 (4)	C532—C53—C54—C55	173.4 (3)
C7A—N7—C6—C5	−47.0 (4)	C52—C53—C54—C55	54.0 (4)
C77—N7—C6—C5	89.8 (3)	C53—C54—C55—O55	124.4 (4)
C55—C5—C6—N7	−65.3 (4)	C53—C54—C55—C5	−54.0 (4)
C4—C5—C6—N7	58.4 (4)	C4—C5—C55—O55	−8.4 (4)
C51—C5—C6—N7	178.5 (3)	C51—C5—C55—O55	−131.2 (3)
C3—C3A—C7A—N1	0.4 (4)	C6—C5—C55—O55	113.4 (4)
C4—C3A—C7A—N1	−178.9 (3)	C4—C5—C55—C54	170.0 (3)
C3—C3A—C7A—N7	−176.6 (3)	C51—C5—C55—C54	47.3 (4)
C4—C3A—C7A—N7	4.1 (6)	C6—C5—C55—C54	−68.1 (4)
N2—N1—C7A—C3A	0.6 (4)	C76—C71—C72—C73	−2.3 (5)
C11—N1—C7A—C3A	−178.2 (3)	C77—C71—C72—C73	179.3 (3)
N2—N1—C7A—N7	177.7 (3)	C731—O73—C73—C74	−173.9 (3)
C11—N1—C7A—N7	−1.1 (6)	C731—O73—C73—C72	5.5 (5)
C6—N7—C7A—C3A	16.1 (5)	C71—C72—C73—O73	−177.8 (3)
C77—N7—C7A—C3A	−120.7 (4)	C71—C72—C73—C74	1.6 (5)
C6—N7—C7A—N1	−160.5 (3)	O73—C73—C74—O74	5.2 (5)
C77—N7—C7A—N1	62.8 (4)	C72—C73—C74—O74	−174.2 (3)
C7A—N1—C11—C16	−141.4 (4)	O73—C73—C74—C75	−179.4 (3)
N2—N1—C11—C16	39.9 (5)	C72—C73—C74—C75	1.1 (6)
C7A—N1—C11—C12	40.2 (5)	C741—O74—C74—C73	−88.9 (5)
N2—N1—C11—C12	−138.5 (3)	C741—O74—C74—C75	95.7 (5)
C16—C11—C12—C13	0.3 (5)	C751—O75—C75—C76	4.1 (6)
N1—C11—C12—C13	178.6 (3)	C751—O75—C75—C74	−176.6 (4)
C11—C12—C13—C14	−1.1 (5)	C73—C74—C75—O75	177.5 (3)
C12—C13—C14—C15	0.9 (6)	O74—C74—C75—O75	−7.1 (5)
C13—C14—C15—C16	0.2 (6)	C73—C74—C75—C76	−3.2 (6)
C14—C15—C16—C11	−1.0 (5)	O74—C74—C75—C76	172.2 (3)
C12—C11—C16—C15	0.8 (5)	O75—C75—C76—C71	−178.3 (4)
N1—C11—C16—C15	−177.6 (3)	C74—C75—C76—C71	2.5 (6)
N2—C3—C31—C34	136.9 (4)	C72—C71—C76—C75	0.3 (5)
C3A—C3—C31—C34	−48.2 (5)	C77—C71—C76—C75	178.7 (3)
N2—C3—C31—C32	−103.7 (4)	C7A—N7—C77—C71	−166.5 (3)
C3A—C3—C31—C32	71.3 (5)	C6—N7—C77—C71	59.8 (4)
N2—C3—C31—C33	16.1 (5)	C72—C71—C77—N7	−131.5 (3)
C3A—C3—C31—C33	−168.9 (4)	C76—C71—C77—N7	50.1 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O81—H81···Cg2	0.84	2.69	3.423 (4)	147
C6—H6A···O81	0.99	2.58	3.406 (6)	141
C52—H52A···O81	0.99	2.48	3.470 (6)	174
C13—H13···O51^i	0.95	2.43	3.194 (5)	137
C77—H77B···O51^ii	0.99	2.45	3.193 (4)	131

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