Hydrogen-bonded chains of rings in 3-tert-butyl-1-phenyl-7-(4-trifluoro­methyl­benz­yl)-4,5,6,7-tetra­hydro-1H-pyrazolo[3,4-b]pyridine-5-spiro-1'-cyclo­hexane-2',6'-dione and 3-tert-butyl-7-(4-methoxy­benz­yl)-1-phenyl-4,5,6,7-tetra­hydro-1H-pyrazolo[3,4-b]pyridine-5-spiro-1'-cyclo­hexane-2',6'-dione

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

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; Trilleras et al., 2008), itself part of a programme exploring the use of multicomponent condensation reactions, especially those induced by microwave irradiation under solvent-free conditions, for the synthesis of novel heterocycles, we now report the molecular and supramolecular structures of the two title N⁷-benzyl derivatives (Figs. 1 and 2). Compounds (I) and (II) are related to the analogues (III) (Cruz et al., 2008) and (IV) (Trilleras et al., 2008) reported earlier, but they differ from these earlier examples in carrying no methyl substituents on the spirocyclohexane ring. Compounds (I) and (II) were synthesized using a straightforward modification of the synthetic method employed earlier (Cruz et al., 2008; Trilleras et al., 2008), using cyclohexane-1,3-dione in place of the 5,5-dimethylcyclohexane-1,3-dione used previously.

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

The molecules of compound (I) are linked into a chain of rings by two independent C—H···O hydrogen bonds (Table 2). Atoms C6 and C53 in the molecule at (x, y, z) both act as hydrogen-bond donors to the carbonyl atom O55 in the molecule at (1/2 - x, -1/2 + y, 3/2 - z); in this manner, molecules related by the 2₁ screw axis along (1/4, y, 3/4) are linked into a C(5) C(5)[R¹₂(8)] (Bernstein et al., 1995) chain of rings running parallel to the [010] direction (Fig. 3). Two chains of this type, related to one another by inversion, pass through each unit cell, but there are no direction-specific interactions between adjacent chains.

In the structure of compound (II) the molecules are again linked into a chain of rings, but now three hydrogen bonds are involved (Table 2), and the chain of rings is thus more complex than that observed in the structure of compound (I). Two of the hydrogen bonds are of the C—H···O type, utilizing both of the carbonyl O atoms as acceptors, in contrast to the hydrogen bonding in compound (I); these interactions link molecules related by the 2₁ screw axis along (1/2, y, 1/4) into a C(6) C(7)[R²₂(11)] chain of rings. The third hydrogen bond is of the C—H···π type, and this reinforces the chain generated by the C—H···O hydrogen bonds. As in compound (I), two inversion-related chains pass through each unit cell, but there are no direction-specific interactions between adjacent chains.

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

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

Related literature

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

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), cyclohexane-1,3-dione (2 mmol) and an excess of paraformaldehyde (80–100 mg) was exposed to microwave radiation at 473 K with a maximum power of 300 W for 25 min. The reaction mixtures were dissolved in hot ethanol. After cooling, the solid products were collected by filtration and washed with ethanol and then with hexane (2 × 5 cm³) to afford the pure products. Colourless crystals suitable for single-crystal X-ray diffraction were grown from solutions in ethanol. (I) Yield 75%, m. p. 488–490 K, HRMS found 509.2295, C₂₉H₃₀F₃N₃O₂ requires 509.2290; (II) yield 75%, m. p. 466–468 K, HRMS found 471.2524, C₂₉H₃₃N₃O₃ requires 471.2522.

S3. Refinement

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

Computing details

For both compounds, data collection: COLLECT (Nonius, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: Sir2004 (Burla et al., 2005); program(s) used to refine structure: OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PRPKAPPA (Ferguson, 1999).

Figures

	Fig. 1. The molecular structure of compound (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The molecular structure of compound (II) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 3. A stereoview of part of the crystal structure of compound (I) showing the formation of a C(5) C(5)[R^12(8)] chain of rings along [010]. For the sake of clarity, the H atoms bonded to C atoms not involved in the motifs shown have been omitted.
	Fig. 4. A stereoview of part of the crystal structure of compound (II) showing the formation of a complex chain of rings along [010]. For the sake of clarity, the H atoms bonded to C atoms not involved in the motifs shown have been omitted.

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

Crystal data

C29H30F3N3O2	F(000) = 1072
Mr = 509.56	Dx = 1.378 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5621 reflections
a = 11.9298 (18) Å	θ = 2.8–27.5°
b = 10.5678 (10) Å	µ = 0.10 mm^−1
c = 19.614 (2) Å	T = 120 K
β = 96.627 (10)°	Block, colourless
V = 2456.2 (5) Å^3	0.33 × 0.32 × 0.18 mm
Z = 4

Data collection

Bruker Nonius KappaCCD diffractometer	5621 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	3742 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.055
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 2.8°
ϕ & ω scans	h = −15→15
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −13→13
Tmin = 0.975, Tmax = 0.982	l = −25→24
31891 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) = 0.151	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0441P)^2 + 3.3381P] where P = (Fo^2 + 2Fc^2)/3
5621 reflections	(Δ/σ)max < 0.001
337 parameters	Δρmax = 0.43 e Å^−3
0 restraints	Δρmin = −0.38 e Å^−3

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

	x	y	z	Uiso*/Ueq
F71	0.63921 (14)	0.26114 (17)	0.51426 (10)	0.0492 (5)
F72	0.5838 (2)	0.1422 (2)	0.58851 (12)	0.0970 (10)
F73	0.50355 (16)	0.1401 (2)	0.48731 (14)	0.0810 (8)
O51	0.05228 (16)	0.32637 (19)	0.79945 (11)	0.0409 (5)
O55	0.17591 (16)	0.73348 (17)	0.76969 (9)	0.0336 (4)
N1	0.00441 (16)	0.69828 (18)	0.57055 (10)	0.0203 (4)
N2	−0.08783 (16)	0.76746 (19)	0.58430 (10)	0.0224 (4)
N7	0.13371 (16)	0.54283 (18)	0.62895 (10)	0.0206 (4)
C3	−0.10633 (18)	0.7332 (2)	0.64682 (11)	0.0193 (5)
C3A	−0.02656 (19)	0.6443 (2)	0.67493 (11)	0.0193 (5)
C4	−0.00999 (19)	0.5786 (2)	0.74262 (12)	0.0231 (5)
C5	0.10913 (19)	0.5223 (2)	0.75492 (12)	0.0234 (5)
C6	0.1356 (2)	0.4578 (2)	0.68737 (12)	0.0243 (5)
C7A	0.04295 (18)	0.6253 (2)	0.62549 (11)	0.0190 (5)
C11	0.04279 (19)	0.7137 (2)	0.50553 (11)	0.0213 (5)
C12	0.09258 (19)	0.6153 (2)	0.47397 (12)	0.0241 (5)
C13	0.1305 (2)	0.6358 (3)	0.41083 (13)	0.0318 (6)
C14	0.1177 (2)	0.7515 (3)	0.37961 (13)	0.0355 (7)
C15	0.0659 (2)	0.8482 (3)	0.41078 (13)	0.0336 (6)
C16	0.0277 (2)	0.8296 (3)	0.47388 (12)	0.0268 (5)
C31	−0.20476 (19)	0.7889 (2)	0.67846 (12)	0.0219 (5)
C32	−0.1617 (3)	0.8595 (3)	0.74348 (15)	0.0470 (8)
C33	−0.2711 (2)	0.8807 (3)	0.63053 (15)	0.0423 (8)
C34	−0.2811 (3)	0.6821 (3)	0.6958 (2)	0.0489 (8)
C51	0.1118 (2)	0.4178 (2)	0.80879 (13)	0.0275 (5)
C52	0.1915 (2)	0.4366 (3)	0.87194 (13)	0.0343 (6)
C53	0.3081 (2)	0.4644 (3)	0.85300 (15)	0.0391 (7)
C54	0.3107 (2)	0.5784 (3)	0.80783 (17)	0.0502 (9)
C55	0.1968 (2)	0.6228 (3)	0.77661 (12)	0.0279 (6)
C71	0.32137 (19)	0.4936 (2)	0.59577 (11)	0.0202 (5)
C72	0.43645 (19)	0.5138 (2)	0.60611 (12)	0.0242 (5)
C73	0.5100 (2)	0.4243 (2)	0.58585 (13)	0.0262 (5)
C74	0.4685 (2)	0.3136 (2)	0.55590 (12)	0.0242 (5)
C75	0.3539 (2)	0.2929 (2)	0.54549 (13)	0.0260 (5)
C76	0.28084 (19)	0.3825 (2)	0.56526 (12)	0.0240 (5)
C77	0.24373 (19)	0.5946 (2)	0.61712 (12)	0.0214 (5)
C741	0.5472 (2)	0.2150 (3)	0.53669 (14)	0.0310 (6)
H4A	−0.0666	0.5104	0.7436	0.028*
H4B	−0.0210	0.6395	0.7796	0.028*
H6A	0.2111	0.4180	0.6955	0.029*
H6B	0.0798	0.3895	0.6757	0.029*
H12	0.1008	0.5346	0.4953	0.029*
H13	0.1657	0.5689	0.3889	0.038*
H14	0.1445	0.7650	0.3364	0.043*
H15	0.0564	0.9283	0.3889	0.040*
H16	−0.0087	0.8963	0.4952	0.032*
H32A	−0.1195	0.8012	0.7758	0.071*
H32B	−0.2257	0.8944	0.7644	0.071*
H32C	−0.1121	0.9285	0.7323	0.071*
H33A	−0.2215	0.9495	0.6189	0.063*
H33B	−0.3334	0.9159	0.6530	0.063*
H33C	−0.3015	0.8365	0.5885	0.063*
H34A	−0.3060	0.6339	0.6541	0.073*
H34B	−0.3470	0.7171	0.7147	0.073*
H34C	−0.2397	0.6262	0.7297	0.073*
H52A	0.1936	0.3594	0.9007	0.041*
H52B	0.1655	0.5078	0.8989	0.041*
H53A	0.3601	0.4781	0.8955	0.047*
H53B	0.3355	0.3901	0.8290	0.047*
H54A	0.3570	0.5586	0.7704	0.060*
H54B	0.3483	0.6484	0.8351	0.060*
H72	0.4652	0.5898	0.6273	0.029*
H73	0.5890	0.4391	0.5926	0.031*
H75	0.3253	0.2166	0.5246	0.031*
H76	0.2018	0.3679	0.5579	0.029*
H77A	0.2789	0.6354	0.6597	0.026*
H77B	0.2329	0.6601	0.5809	0.026*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
F71	0.0314 (9)	0.0464 (10)	0.0748 (13)	0.0031 (8)	0.0279 (9)	−0.0098 (9)
F72	0.133 (2)	0.0944 (18)	0.0756 (15)	0.0901 (17)	0.0615 (15)	0.0502 (14)
F73	0.0324 (10)	0.0764 (15)	0.133 (2)	0.0111 (10)	0.0038 (11)	−0.0678 (15)
O51	0.0299 (10)	0.0407 (11)	0.0506 (12)	−0.0116 (9)	−0.0016 (9)	0.0204 (10)
O55	0.0382 (11)	0.0305 (10)	0.0310 (10)	−0.0079 (8)	−0.0009 (8)	−0.0009 (8)
N1	0.0172 (9)	0.0241 (10)	0.0203 (9)	0.0044 (8)	0.0048 (7)	0.0003 (8)
N2	0.0188 (10)	0.0249 (10)	0.0241 (10)	0.0053 (8)	0.0050 (8)	0.0000 (8)
N7	0.0152 (9)	0.0204 (10)	0.0269 (10)	0.0014 (8)	0.0059 (8)	0.0036 (8)
C3	0.0159 (11)	0.0217 (11)	0.0206 (11)	−0.0002 (9)	0.0036 (8)	−0.0026 (9)
C3A	0.0168 (11)	0.0209 (11)	0.0205 (11)	−0.0002 (9)	0.0034 (8)	−0.0008 (9)
C4	0.0198 (12)	0.0275 (12)	0.0226 (11)	0.0030 (10)	0.0052 (9)	0.0025 (10)
C5	0.0184 (12)	0.0258 (12)	0.0260 (12)	0.0013 (9)	0.0024 (9)	0.0067 (10)
C6	0.0193 (12)	0.0226 (12)	0.0318 (13)	0.0026 (9)	0.0059 (10)	0.0044 (10)
C7A	0.0168 (11)	0.0177 (11)	0.0226 (11)	0.0016 (9)	0.0023 (9)	−0.0006 (9)
C11	0.0167 (11)	0.0292 (12)	0.0177 (11)	−0.0033 (9)	0.0013 (9)	−0.0012 (10)
C12	0.0171 (11)	0.0284 (13)	0.0275 (12)	−0.0048 (10)	0.0046 (9)	−0.0054 (10)
C13	0.0220 (13)	0.0476 (16)	0.0273 (13)	−0.0077 (12)	0.0093 (10)	−0.0124 (12)
C14	0.0257 (14)	0.0610 (19)	0.0209 (12)	−0.0094 (13)	0.0071 (10)	0.0021 (13)
C15	0.0295 (14)	0.0444 (16)	0.0268 (13)	−0.0027 (12)	0.0028 (11)	0.0104 (12)
C16	0.0221 (12)	0.0332 (14)	0.0252 (12)	0.0015 (10)	0.0023 (10)	0.0021 (11)
C31	0.0190 (11)	0.0225 (12)	0.0250 (12)	0.0027 (9)	0.0059 (9)	−0.0010 (10)
C32	0.0448 (18)	0.0538 (19)	0.0410 (17)	0.0211 (15)	−0.0013 (13)	−0.0216 (15)
C33	0.0313 (15)	0.0593 (19)	0.0389 (16)	0.0260 (14)	0.0149 (12)	0.0156 (15)
C34	0.0342 (16)	0.0339 (16)	0.084 (2)	0.0004 (13)	0.0306 (16)	−0.0019 (16)
C51	0.0229 (12)	0.0285 (13)	0.0323 (13)	0.0043 (11)	0.0082 (10)	0.0085 (11)
C52	0.0528 (18)	0.0257 (13)	0.0243 (13)	0.0018 (12)	0.0039 (12)	0.0047 (11)
C53	0.0331 (15)	0.0370 (15)	0.0431 (16)	0.0001 (12)	−0.0130 (12)	0.0038 (13)
C54	0.0256 (15)	0.071 (2)	0.0508 (18)	−0.0102 (15)	−0.0094 (13)	0.0296 (17)
C55	0.0272 (13)	0.0353 (14)	0.0205 (12)	−0.0040 (11)	−0.0003 (10)	0.0060 (11)
C71	0.0183 (11)	0.0219 (11)	0.0210 (11)	0.0015 (9)	0.0052 (9)	0.0017 (9)
C72	0.0172 (11)	0.0292 (13)	0.0258 (12)	0.0006 (10)	0.0015 (9)	−0.0022 (10)
C73	0.0157 (11)	0.0311 (13)	0.0316 (13)	0.0018 (10)	0.0022 (9)	0.0004 (11)
C74	0.0218 (12)	0.0271 (12)	0.0245 (12)	0.0045 (10)	0.0063 (9)	0.0032 (10)
C75	0.0242 (12)	0.0247 (12)	0.0298 (13)	−0.0006 (10)	0.0063 (10)	−0.0020 (10)
C76	0.0159 (11)	0.0260 (12)	0.0304 (13)	−0.0007 (9)	0.0035 (9)	−0.0015 (10)
C77	0.0167 (11)	0.0226 (12)	0.0254 (12)	−0.0014 (9)	0.0048 (9)	−0.0004 (10)
C741	0.0253 (13)	0.0307 (14)	0.0378 (15)	0.0038 (11)	0.0067 (11)	−0.0005 (12)

Geometric parameters (Å, º)

F71—C741	1.321 (3)	C31—C34	1.513 (4)
F72—C741	1.309 (3)	C31—C32	1.515 (4)
F73—C741	1.311 (3)	C32—H32A	0.98
O51—C51	1.200 (3)	C32—H32B	0.98
O55—C55	1.200 (3)	C32—H32C	0.98
N1—C7A	1.361 (3)	C33—H33A	0.98
N1—N2	1.374 (3)	C33—H33B	0.98
N1—C11	1.413 (3)	C33—H33C	0.98
N2—C3	1.321 (3)	C34—H34A	0.98
N7—C7A	1.386 (3)	C34—H34B	0.98
N7—C6	1.455 (3)	C34—H34C	0.98
N7—C77	1.465 (3)	C51—C52	1.485 (4)
C3—C3A	1.404 (3)	C52—C53	1.510 (4)
C3—C31	1.510 (3)	C52—H52A	0.99
C3A—C7A	1.362 (3)	C52—H52B	0.99
C3A—C4	1.491 (3)	C53—C54	1.498 (4)
C4—C5	1.534 (3)	C53—H53A	0.99
C4—H4A	0.99	C53—H53B	0.99
C4—H4B	0.99	C54—C55	1.500 (4)
C5—C55	1.517 (3)	C54—H54A	0.99
C5—C51	1.526 (3)	C54—H54B	0.99
C5—C6	1.554 (3)	C71—C76	1.380 (3)
C6—H6A	0.99	C71—C72	1.381 (3)
C6—H6B	0.99	C71—C77	1.504 (3)
C11—C16	1.376 (3)	C72—C73	1.379 (3)
C11—C12	1.379 (3)	C72—H72	0.95
C12—C13	1.383 (3)	C73—C74	1.376 (3)
C12—H12	0.95	C73—H73	0.95
C13—C14	1.369 (4)	C74—C75	1.376 (3)
C13—H13	0.95	C74—C741	1.480 (3)
C14—C15	1.373 (4)	C75—C76	1.372 (3)
C14—H14	0.95	C75—H75	0.95
C15—C16	1.382 (4)	C76—H76	0.95
C15—H15	0.95	C77—H77A	0.99
C16—H16	0.95	C77—H77B	0.99
C31—C33	1.510 (3)
C7A—N1—N2	110.56 (18)	C31—C33—H33B	109.5
C7A—N1—C11	131.65 (19)	H33A—C33—H33B	109.5
N2—N1—C11	117.79 (18)	C31—C33—H33C	109.5
C3—N2—N1	105.07 (18)	H33A—C33—H33C	109.5
C7A—N7—C6	111.60 (18)	H33B—C33—H33C	109.5
C7A—N7—C77	117.83 (19)	C31—C34—H34A	109.5
C6—N7—C77	115.01 (18)	C31—C34—H34B	109.5
N2—C3—C3A	111.7 (2)	H34A—C34—H34B	109.5
N2—C3—C31	119.7 (2)	C31—C34—H34C	109.5
C3A—C3—C31	128.6 (2)	H34A—C34—H34C	109.5
C7A—C3A—C3	105.0 (2)	H34B—C34—H34C	109.5
C7A—C3A—C4	122.5 (2)	O51—C51—C52	123.0 (2)
C3—C3A—C4	132.5 (2)	O51—C51—C5	120.8 (2)
C3A—C4—C5	110.23 (19)	C52—C51—C5	116.2 (2)
C3A—C4—H4A	109.6	C51—C52—C53	109.9 (2)
C5—C4—H4A	109.6	C51—C52—H52A	109.7
C3A—C4—H4B	109.6	C53—C52—H52A	109.7
C5—C4—H4B	109.6	C51—C52—H52B	109.7
H4A—C4—H4B	108.1	C53—C52—H52B	109.7
C55—C5—C51	110.7 (2)	H52A—C52—H52B	108.2
C55—C5—C4	111.6 (2)	C54—C53—C52	112.7 (2)
C51—C5—C4	109.55 (19)	C54—C53—H53A	109.1
C55—C5—C6	110.2 (2)	C52—C53—H53A	109.1
C51—C5—C6	106.4 (2)	C54—C53—H53B	109.1
C4—C5—C6	108.17 (19)	C52—C53—H53B	109.1
N7—C6—C5	114.47 (19)	H53A—C53—H53B	107.8
N7—C6—H6A	108.6	C53—C54—C55	114.4 (2)
C5—C6—H6A	108.6	C53—C54—H54A	108.7
N7—C6—H6B	108.6	C55—C54—H54A	108.7
C5—C6—H6B	108.6	C53—C54—H54B	108.7
H6A—C6—H6B	107.6	C55—C54—H54B	108.7
N1—C7A—C3A	107.62 (19)	H54A—C54—H54B	107.6
N1—C7A—N7	125.9 (2)	O55—C55—C54	121.2 (3)
C3A—C7A—N7	126.5 (2)	O55—C55—C5	121.5 (2)
C16—C11—C12	120.6 (2)	C54—C55—C5	117.3 (2)
C16—C11—N1	118.1 (2)	C76—C71—C72	119.2 (2)
C12—C11—N1	121.3 (2)	C76—C71—C77	121.9 (2)
C11—C12—C13	119.1 (2)	C72—C71—C77	118.9 (2)
C11—C12—H12	120.5	C73—C72—C71	120.4 (2)
C13—C12—H12	120.5	C73—C72—H72	119.8
C14—C13—C12	120.6 (3)	C71—C72—H72	119.8
C14—C13—H13	119.7	C74—C73—C72	119.8 (2)
C12—C13—H13	119.7	C74—C73—H73	120.1
C13—C14—C15	119.9 (2)	C72—C73—H73	120.1
C13—C14—H14	120.1	C73—C74—C75	120.0 (2)
C15—C14—H14	120.1	C73—C74—C741	120.0 (2)
C14—C15—C16	120.3 (3)	C75—C74—C741	120.0 (2)
C14—C15—H15	119.8	C76—C75—C74	120.1 (2)
C16—C15—H15	119.8	C76—C75—H75	120.0
C11—C16—C15	119.4 (2)	C74—C75—H75	120.0
C11—C16—H16	120.3	C75—C76—C71	120.5 (2)
C15—C16—H16	120.3	C75—C76—H76	119.8
C3—C31—C33	111.8 (2)	C71—C76—H76	119.8
C3—C31—C34	108.5 (2)	N7—C77—C71	111.80 (19)
C33—C31—C34	109.5 (2)	N7—C77—H77A	109.3
C3—C31—C32	109.5 (2)	C71—C77—H77A	109.3
C33—C31—C32	108.1 (2)	N7—C77—H77B	109.3
C34—C31—C32	109.4 (2)	C71—C77—H77B	109.3
C31—C32—H32A	109.5	H77A—C77—H77B	107.9
C31—C32—H32B	109.5	F72—C741—F73	106.7 (3)
H32A—C32—H32B	109.5	F72—C741—F71	105.1 (2)
C31—C32—H32C	109.5	F73—C741—F71	104.6 (2)
H32A—C32—H32C	109.5	F72—C741—C74	112.4 (2)
H32B—C32—H32C	109.5	F73—C741—C74	113.7 (2)
C31—C33—H33A	109.5	F71—C741—C74	113.6 (2)
C7A—N1—N2—C3	−1.7 (2)	C3A—C3—C31—C33	−179.3 (2)
C11—N1—N2—C3	178.7 (2)	N2—C3—C31—C34	121.0 (3)
N1—N2—C3—C3A	1.0 (3)	C3A—C3—C31—C34	−58.4 (3)
N1—N2—C3—C31	−178.49 (19)	N2—C3—C31—C32	−119.6 (3)
N2—C3—C3A—C7A	−0.1 (3)	C3A—C3—C31—C32	61.0 (3)
C31—C3—C3A—C7A	179.4 (2)	C55—C5—C51—O51	−176.4 (2)
N2—C3—C3A—C4	179.2 (2)	C4—C5—C51—O51	60.1 (3)
C31—C3—C3A—C4	−1.3 (4)	C6—C5—C51—O51	−56.6 (3)
C7A—C3A—C4—C5	16.2 (3)	C55—C5—C51—C52	3.5 (3)
C3—C3A—C4—C5	−162.9 (2)	C4—C5—C51—C52	−120.1 (2)
C3A—C4—C5—C55	77.6 (2)	C6—C5—C51—C52	123.2 (2)
C3A—C4—C5—C51	−159.4 (2)	O51—C51—C52—C53	127.5 (3)
C3A—C4—C5—C6	−43.8 (3)	C5—C51—C52—C53	−52.4 (3)
C7A—N7—C6—C5	−42.8 (3)	C51—C52—C53—C54	57.8 (3)
C77—N7—C6—C5	94.9 (2)	C52—C53—C54—C55	−14.1 (4)
C55—C5—C6—N7	−61.5 (3)	C53—C54—C55—O55	142.5 (3)
C51—C5—C6—N7	178.38 (19)	C53—C54—C55—C5	−36.9 (4)
C4—C5—C6—N7	60.7 (3)	C51—C5—C55—O55	−137.3 (2)
N2—N1—C7A—C3A	1.7 (3)	C4—C5—C55—O55	−15.0 (3)
C11—N1—C7A—C3A	−178.8 (2)	C6—C5—C55—O55	105.2 (3)
N2—N1—C7A—N7	179.2 (2)	C51—C5—C55—C54	42.1 (3)
C11—N1—C7A—N7	−1.3 (4)	C4—C5—C55—C54	164.4 (2)
C3—C3A—C7A—N1	−1.0 (3)	C6—C5—C55—C54	−75.4 (3)
C4—C3A—C7A—N1	179.7 (2)	C76—C71—C72—C73	0.4 (4)
C3—C3A—C7A—N7	−178.4 (2)	C77—C71—C72—C73	−178.7 (2)
C4—C3A—C7A—N7	2.2 (4)	C71—C72—C73—C74	−0.8 (4)
C6—N7—C7A—N1	−166.0 (2)	C72—C73—C74—C75	0.8 (4)
C77—N7—C7A—N1	57.7 (3)	C72—C73—C74—C741	−177.5 (2)
C6—N7—C7A—C3A	11.0 (3)	C73—C74—C75—C76	−0.3 (4)
C77—N7—C7A—C3A	−125.3 (2)	C741—C74—C75—C76	177.9 (2)
C7A—N1—C11—C16	−148.7 (2)	C74—C75—C76—C71	−0.1 (4)
N2—N1—C11—C16	30.8 (3)	C72—C71—C76—C75	0.1 (4)
C7A—N1—C11—C12	32.1 (4)	C77—C71—C76—C75	179.1 (2)
N2—N1—C11—C12	−148.4 (2)	C7A—N7—C77—C71	−158.19 (19)
C16—C11—C12—C13	2.0 (3)	C6—N7—C77—C71	66.9 (3)
N1—C11—C12—C13	−178.9 (2)	C76—C71—C77—N7	23.9 (3)
C11—C12—C13—C14	−0.7 (4)	C72—C71—C77—N7	−157.1 (2)
C12—C13—C14—C15	−0.6 (4)	C73—C74—C741—F72	83.3 (3)
C13—C14—C15—C16	0.6 (4)	C75—C74—C741—F72	−94.9 (3)
C12—C11—C16—C15	−1.9 (4)	C73—C74—C741—F73	−155.3 (3)
N1—C11—C16—C15	179.0 (2)	C75—C74—C741—F73	26.5 (4)
C14—C15—C16—C11	0.6 (4)	C73—C74—C741—F71	−35.8 (3)
N2—C3—C31—C33	0.2 (3)	C75—C74—C741—F71	145.9 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6A···O55^i	0.99	2.42	3.309 (3)	149
C53—H53B···O55^i	0.99	2.54	3.448 (4)	153

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

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

Crystal data

C29H33N3O3	F(000) = 1008
Mr = 471.58	Dx = 1.291 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5566 reflections
a = 9.1904 (10) Å	θ = 2.9–27.5°
b = 11.9402 (14) Å	µ = 0.08 mm^−1
c = 22.2888 (16) Å	T = 120 K
β = 97.287 (9)°	Block, colourless
V = 2426.1 (4) Å^3	0.39 × 0.38 × 0.16 mm
Z = 4

Data collection

Bruker Nonius KappaCCD diffractometer	5566 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	3161 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.084
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 2.9°
ϕ & ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −15→15
Tmin = 0.977, Tmax = 0.987	l = −28→26
37788 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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.143	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.055P)^2 + 1.2855P] where P = (Fo^2 + 2Fc^2)/3
5566 reflections	(Δ/σ)max < 0.001
320 parameters	Δρmax = 0.26 e Å^−3
0 restraints	Δρmin = −0.32 e Å^−3

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

	x	y	z	Uiso*/Ueq
O51	0.47933 (18)	0.13490 (14)	0.15587 (7)	0.0376 (4)
O55	0.45927 (17)	0.47217 (13)	0.21851 (7)	0.0317 (4)
O741	0.45277 (18)	0.12686 (15)	0.54516 (7)	0.0416 (4)
N1	0.93029 (18)	0.43752 (15)	0.29610 (7)	0.0226 (4)
N2	0.97707 (18)	0.48699 (15)	0.24648 (8)	0.0240 (4)
N7	0.73001 (18)	0.31459 (15)	0.31852 (7)	0.0227 (4)
C3	0.8866 (2)	0.45035 (17)	0.19963 (9)	0.0232 (5)
C3A	0.7789 (2)	0.37823 (18)	0.21793 (9)	0.0233 (5)
C4	0.6530 (2)	0.31823 (19)	0.18358 (9)	0.0254 (5)
C5	0.5439 (2)	0.28334 (17)	0.22571 (9)	0.0230 (5)
C6	0.6305 (2)	0.23525 (18)	0.28461 (9)	0.0240 (5)
C7A	0.8089 (2)	0.37321 (17)	0.27925 (9)	0.0228 (5)
C11	1.0108 (2)	0.45717 (18)	0.35358 (9)	0.0247 (5)
C12	1.0135 (2)	0.37872 (19)	0.39882 (10)	0.0285 (5)
C13	1.0906 (3)	0.4010 (2)	0.45460 (10)	0.0345 (6)
C14	1.1684 (3)	0.4983 (2)	0.46461 (11)	0.0351 (6)
C15	1.1689 (3)	0.5753 (2)	0.41889 (11)	0.0354 (6)
C16	1.0886 (2)	0.5562 (2)	0.36325 (10)	0.0304 (5)
C31	0.9053 (2)	0.48938 (19)	0.13697 (10)	0.0273 (5)
C32	0.7766 (3)	0.5651 (2)	0.11281 (11)	0.0356 (6)
C33	1.0474 (3)	0.5555 (2)	0.13770 (10)	0.0338 (6)
C34	0.9101 (3)	0.3885 (2)	0.09521 (10)	0.0339 (6)
C51	0.4457 (2)	0.18749 (18)	0.19828 (10)	0.0260 (5)
C52	0.3096 (2)	0.16125 (19)	0.22596 (11)	0.0322 (5)
C53	0.2228 (2)	0.26539 (19)	0.23808 (11)	0.0315 (5)
C54	0.3187 (2)	0.35237 (19)	0.27360 (10)	0.0294 (5)
C55	0.4439 (2)	0.37999 (19)	0.23897 (9)	0.0255 (5)
C71	0.6093 (2)	0.31707 (18)	0.41168 (9)	0.0241 (5)
C72	0.4999 (2)	0.3592 (2)	0.44194 (10)	0.0302 (5)
C73	0.4473 (2)	0.2997 (2)	0.48779 (10)	0.0339 (6)
C74	0.5015 (3)	0.1950 (2)	0.50248 (10)	0.0308 (5)
C75	0.6116 (3)	0.1520 (2)	0.47332 (10)	0.0339 (6)
C76	0.6657 (2)	0.21226 (19)	0.42872 (10)	0.0297 (5)
C77	0.6643 (2)	0.38431 (18)	0.36249 (9)	0.0239 (5)
C741	0.3187 (3)	0.1552 (2)	0.56615 (11)	0.0454 (7)
H4A	0.6890	0.2511	0.1639	0.030*
H4B	0.6041	0.3678	0.1515	0.030*
H6A	0.5594	0.2083	0.3112	0.029*
H6B	0.6880	0.1698	0.2739	0.029*
H12	0.9626	0.3098	0.3917	0.034*
H13	1.0899	0.3483	0.4865	0.041*
H14	1.2220	0.5126	0.5032	0.042*
H15	1.2248	0.6421	0.4256	0.043*
H16	1.0867	0.6104	0.3319	0.036*
H32A	0.7763	0.6317	0.1385	0.053*
H32B	0.6843	0.5241	0.1132	0.053*
H32C	0.7869	0.5879	0.0713	0.053*
H33A	1.1306	0.5081	0.1536	0.051*
H33B	1.0441	0.6216	0.1635	0.051*
H33C	1.0588	0.5792	0.0965	0.051*
H34A	0.8164	0.3484	0.0923	0.051*
H34B	0.9896	0.3383	0.1116	0.051*
H34C	0.9272	0.4141	0.0549	0.051*
H52A	0.3370	0.1208	0.2645	0.039*
H52B	0.2466	0.1110	0.1985	0.039*
H53A	0.1793	0.2982	0.1991	0.038*
H53B	0.1416	0.2442	0.2611	0.038*
H29A	0.2608	0.4206	0.2791	0.035*
H54B	0.3566	0.3225	0.3140	0.035*
H72	0.4596	0.4307	0.4311	0.036*
H73	0.3739	0.3313	0.5090	0.041*
H75	0.6506	0.0800	0.4841	0.041*
H76	0.7429	0.1819	0.4092	0.036*
H77A	0.5818	0.4276	0.3410	0.029*
H77B	0.7386	0.4384	0.3809	0.029*
H74A	0.2409	0.1594	0.5318	0.068*
H74B	0.3285	0.2280	0.5866	0.068*
H74C	0.2936	0.0979	0.5946	0.068*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O51	0.0440 (10)	0.0315 (9)	0.0391 (9)	−0.0109 (8)	0.0126 (8)	−0.0081 (8)
O55	0.0336 (9)	0.0216 (9)	0.0398 (9)	−0.0001 (7)	0.0038 (7)	0.0040 (7)
O741	0.0433 (10)	0.0518 (11)	0.0309 (9)	−0.0091 (9)	0.0095 (7)	0.0105 (8)
N1	0.0202 (9)	0.0231 (10)	0.0246 (9)	−0.0023 (7)	0.0034 (7)	0.0019 (8)
N2	0.0205 (9)	0.0236 (10)	0.0286 (9)	−0.0013 (8)	0.0063 (7)	0.0013 (8)
N7	0.0237 (9)	0.0214 (9)	0.0237 (9)	−0.0031 (8)	0.0055 (7)	−0.0008 (8)
C3	0.0204 (11)	0.0203 (11)	0.0295 (11)	0.0008 (9)	0.0061 (9)	0.0002 (9)
C3A	0.0206 (10)	0.0225 (11)	0.0272 (11)	0.0016 (9)	0.0043 (8)	−0.0006 (9)
C4	0.0239 (11)	0.0260 (12)	0.0266 (11)	−0.0049 (9)	0.0041 (9)	−0.0011 (10)
C5	0.0224 (11)	0.0189 (11)	0.0278 (11)	−0.0001 (9)	0.0038 (9)	0.0003 (9)
C6	0.0227 (11)	0.0210 (11)	0.0285 (11)	−0.0011 (9)	0.0042 (9)	−0.0007 (9)
C7A	0.0209 (11)	0.0188 (11)	0.0293 (12)	0.0015 (9)	0.0061 (9)	0.0006 (9)
C11	0.0207 (11)	0.0264 (12)	0.0273 (11)	0.0014 (9)	0.0042 (9)	−0.0038 (10)
C12	0.0265 (12)	0.0268 (12)	0.0322 (12)	−0.0005 (10)	0.0030 (9)	−0.0004 (10)
C13	0.0326 (13)	0.0393 (14)	0.0309 (13)	0.0004 (11)	0.0009 (10)	0.0042 (11)
C14	0.0314 (13)	0.0416 (15)	0.0310 (13)	−0.0004 (11)	−0.0010 (10)	−0.0072 (11)
C15	0.0332 (13)	0.0318 (14)	0.0404 (14)	−0.0048 (11)	0.0015 (11)	−0.0077 (11)
C16	0.0297 (12)	0.0278 (13)	0.0333 (13)	−0.0026 (10)	0.0028 (10)	0.0010 (10)
C31	0.0266 (11)	0.0260 (12)	0.0302 (12)	−0.0041 (10)	0.0067 (9)	0.0009 (10)
C32	0.0341 (13)	0.0379 (14)	0.0351 (13)	0.0013 (11)	0.0053 (10)	0.0097 (11)
C33	0.0326 (13)	0.0361 (14)	0.0340 (13)	−0.0078 (11)	0.0091 (10)	−0.0003 (11)
C34	0.0364 (13)	0.0367 (14)	0.0299 (12)	−0.0033 (11)	0.0093 (10)	−0.0036 (11)
C51	0.0272 (12)	0.0199 (11)	0.0301 (12)	−0.0005 (9)	0.0011 (9)	0.0036 (10)
C52	0.0256 (12)	0.0278 (13)	0.0430 (14)	−0.0045 (10)	0.0032 (10)	0.0006 (11)
C53	0.0219 (11)	0.0297 (13)	0.0430 (14)	−0.0001 (10)	0.0049 (10)	0.0049 (11)
C54	0.0232 (11)	0.0294 (12)	0.0361 (13)	0.0009 (10)	0.0058 (9)	−0.0007 (10)
C55	0.0233 (11)	0.0247 (12)	0.0272 (11)	−0.0016 (9)	−0.0018 (9)	−0.0009 (10)
C71	0.0222 (11)	0.0243 (12)	0.0256 (11)	−0.0020 (9)	0.0021 (9)	0.0008 (9)
C72	0.0276 (12)	0.0286 (13)	0.0356 (13)	0.0041 (10)	0.0087 (10)	0.0031 (10)
C73	0.0293 (12)	0.0410 (15)	0.0332 (13)	−0.0015 (11)	0.0112 (10)	−0.0010 (11)
C74	0.0316 (12)	0.0368 (14)	0.0240 (11)	−0.0080 (11)	0.0031 (9)	0.0061 (10)
C75	0.0363 (14)	0.0329 (14)	0.0323 (13)	0.0027 (11)	0.0034 (10)	0.0082 (11)
C76	0.0267 (12)	0.0312 (13)	0.0322 (12)	0.0061 (10)	0.0080 (9)	0.0049 (10)
C77	0.0226 (11)	0.0222 (11)	0.0276 (11)	0.0008 (9)	0.0058 (9)	0.0008 (9)
C741	0.0463 (16)	0.0595 (19)	0.0329 (13)	−0.0152 (13)	0.0146 (12)	−0.0010 (13)

Geometric parameters (Å, º)

O51—C51	1.207 (3)	C31—C32	1.531 (3)
O55—C55	1.207 (3)	C32—H32A	0.98
O741—C74	1.370 (3)	C32—H32B	0.98
O741—C741	1.414 (3)	C32—H32C	0.98
N1—C7A	1.367 (3)	C33—H33A	0.98
N1—N2	1.370 (2)	C33—H33B	0.98
N1—C11	1.415 (3)	C33—H33C	0.98
N2—C3	1.324 (3)	C34—H34A	0.98
N7—C7A	1.394 (3)	C34—H34B	0.98
N7—C6	1.459 (3)	C34—H34C	0.98
N7—C77	1.472 (3)	C51—C52	1.496 (3)
C3—C3A	1.411 (3)	C52—C53	1.520 (3)
C3—C31	1.503 (3)	C52—H52A	0.99
C3A—C7A	1.361 (3)	C52—H52B	0.99
C3A—C4	1.488 (3)	C53—C54	1.518 (3)
C4—C5	1.517 (3)	C53—H53A	0.99
C4—H4A	0.99	C53—H53B	0.99
C4—H4B	0.99	C54—C55	1.501 (3)
C5—C55	1.527 (3)	C54—H29A	0.99
C5—C51	1.535 (3)	C54—H54B	0.99
C5—C6	1.556 (3)	C71—C72	1.375 (3)
C6—H6A	0.99	C71—C76	1.389 (3)
C6—H6B	0.99	C71—C77	1.498 (3)
C11—C12	1.374 (3)	C72—C73	1.381 (3)
C11—C16	1.385 (3)	C72—H72	0.95
C12—C13	1.377 (3)	C73—C74	1.371 (3)
C12—H12	0.95	C73—H73	0.95
C13—C14	1.367 (3)	C74—C75	1.369 (3)
C13—H13	0.95	C75—C76	1.371 (3)
C14—C15	1.373 (3)	C75—H75	0.95
C14—H14	0.95	C76—H76	0.95
C15—C16	1.379 (3)	C77—H77A	0.99
C15—H15	0.95	C77—H77B	0.99
C16—H16	0.95	C741—H74A	0.98
C31—C33	1.524 (3)	C741—H74B	0.98
C31—C34	1.526 (3)	C741—H74C	0.98
C74—O741—C741	117.6 (2)	C31—C33—H33B	109.5
C7A—N1—N2	110.42 (16)	H33A—C33—H33B	109.5
C7A—N1—C11	131.03 (17)	C31—C33—H33C	109.5
N2—N1—C11	118.54 (16)	H33A—C33—H33C	109.5
C3—N2—N1	105.32 (16)	H33B—C33—H33C	109.5
C7A—N7—C6	110.03 (16)	C31—C34—H34A	109.5
C7A—N7—C77	115.08 (16)	C31—C34—H34B	109.5
C6—N7—C77	115.40 (16)	H34A—C34—H34B	109.5
N2—C3—C3A	111.54 (18)	C31—C34—H34C	109.5
N2—C3—C31	119.73 (18)	H34A—C34—H34C	109.5
C3A—C3—C31	128.70 (19)	H34B—C34—H34C	109.5
C7A—C3A—C3	104.89 (18)	O51—C51—C52	121.6 (2)
C7A—C3A—C4	122.75 (19)	O51—C51—C5	120.25 (19)
C3—C3A—C4	132.35 (19)	C52—C51—C5	118.14 (19)
C3A—C4—C5	110.24 (17)	C51—C52—C53	112.77 (19)
C3A—C4—H4A	109.6	C51—C52—H52A	109.0
C5—C4—H4A	109.6	C53—C52—H52A	109.0
C3A—C4—H4B	109.6	C51—C52—H52B	109.0
C5—C4—H4B	109.6	C53—C52—H52B	109.0
H4A—C4—H4B	108.1	H52A—C52—H52B	107.8
C4—C5—C55	111.94 (17)	C54—C53—C52	111.67 (18)
C4—C5—C51	111.07 (17)	C54—C53—H53A	109.3
C55—C5—C51	107.62 (17)	C52—C53—H53A	109.3
C4—C5—C6	108.42 (17)	C54—C53—H53B	109.3
C55—C5—C6	111.81 (17)	C52—C53—H53B	109.3
C51—C5—C6	105.82 (16)	H53A—C53—H53B	107.9
N7—C6—C5	114.66 (17)	C55—C54—C53	108.32 (18)
N7—C6—H6A	108.6	C55—C54—H29A	110.0
C5—C6—H6A	108.6	C53—C54—H29A	110.0
N7—C6—H6B	108.6	C55—C54—H54B	110.0
C5—C6—H6B	108.6	C53—C54—H54B	110.0
H6A—C6—H6B	107.6	H29A—C54—H54B	108.4
C12—C11—C16	120.5 (2)	O55—C55—C54	121.9 (2)
C12—C11—N1	120.66 (19)	O55—C55—C5	120.93 (19)
C16—C11—N1	118.87 (19)	C54—C55—C5	116.92 (19)
C11—C12—C13	119.3 (2)	C72—C71—C76	117.8 (2)
C11—C12—H12	120.3	C72—C71—C77	119.9 (2)
C13—C12—H12	120.3	C76—C71—C77	122.29 (19)
C14—C13—C12	120.7 (2)	C71—C72—C73	121.4 (2)
C14—C13—H13	119.7	C71—C72—H72	119.3
C12—C13—H13	119.7	C73—C72—H72	119.3
C13—C14—C15	119.9 (2)	C74—C73—C72	119.7 (2)
C13—C14—H14	120.0	C74—C73—H73	120.2
C15—C14—H14	120.0	C72—C73—H73	120.2
C14—C15—C16	120.3 (2)	C75—C74—O741	115.7 (2)
C14—C15—H15	119.8	C75—C74—C73	119.8 (2)
C16—C15—H15	119.8	O741—C74—C73	124.5 (2)
C15—C16—C11	119.2 (2)	C74—C75—C76	120.4 (2)
C15—C16—H16	120.4	C74—C75—H75	119.8
C11—C16—H16	120.4	C76—C75—H75	119.8
C3A—C7A—N1	107.79 (18)	C75—C76—C71	120.9 (2)
C3A—C7A—N7	126.69 (19)	C75—C76—H76	119.5
N1—C7A—N7	125.51 (18)	C71—C76—H76	119.5
C3—C31—C33	110.47 (18)	N7—C77—C71	112.91 (17)
C3—C31—C34	109.73 (18)	N7—C77—H77A	109.0
C33—C31—C34	108.93 (18)	C71—C77—H77A	109.0
C3—C31—C32	109.60 (17)	N7—C77—H77B	109.0
C33—C31—C32	108.71 (19)	C71—C77—H77B	109.0
C34—C31—C32	109.37 (19)	H77A—C77—H77B	107.8
C31—C32—H32A	109.5	O741—C741—H74A	109.5
C31—C32—H32B	109.5	O741—C741—H74B	109.5
H32A—C32—H32B	109.5	H74A—C741—H74B	109.5
C31—C32—H32C	109.5	O741—C741—H74C	109.5
H32A—C32—H32C	109.5	H74A—C741—H74C	109.5
H32B—C32—H32C	109.5	H74B—C741—H74C	109.5
C31—C33—H33A	109.5
C7A—N1—N2—C3	−1.6 (2)	C77—N7—C7A—N1	61.0 (3)
C11—N1—N2—C3	177.26 (17)	N2—C3—C31—C33	8.6 (3)
N1—N2—C3—C3A	0.9 (2)	C3A—C3—C31—C33	−173.2 (2)
N1—N2—C3—C31	179.37 (17)	N2—C3—C31—C34	128.7 (2)
N2—C3—C3A—C7A	0.2 (2)	C3A—C3—C31—C34	−53.1 (3)
C31—C3—C3A—C7A	−178.2 (2)	N2—C3—C31—C32	−111.2 (2)
N2—C3—C3A—C4	178.6 (2)	C3A—C3—C31—C32	67.0 (3)
C31—C3—C3A—C4	0.3 (4)	C4—C5—C51—O51	15.2 (3)
C7A—C3A—C4—C5	16.8 (3)	C55—C5—C51—O51	138.0 (2)
C3—C3A—C4—C5	−161.4 (2)	C6—C5—C51—O51	−102.3 (2)
C3A—C4—C5—C55	80.4 (2)	C4—C5—C51—C52	−165.39 (19)
C3A—C4—C5—C51	−159.26 (18)	C55—C5—C51—C52	−42.5 (2)
C3A—C4—C5—C6	−43.4 (2)	C6—C5—C51—C52	77.1 (2)
C7A—N7—C6—C5	−44.7 (2)	O51—C51—C52—C53	−134.9 (2)
C77—N7—C6—C5	87.6 (2)	C5—C51—C52—C53	45.7 (3)
C4—C5—C6—N7	61.6 (2)	C51—C52—C53—C54	−51.7 (3)
C55—C5—C6—N7	−62.3 (2)	C52—C53—C54—C55	56.9 (2)
C51—C5—C6—N7	−179.15 (17)	C53—C54—C55—O55	115.6 (2)
C7A—N1—C11—C12	27.1 (3)	C53—C54—C55—C5	−59.0 (2)
N2—N1—C11—C12	−151.52 (19)	C4—C5—C55—O55	−2.3 (3)
C7A—N1—C11—C16	−153.8 (2)	C51—C5—C55—O55	−124.7 (2)
N2—N1—C11—C16	27.6 (3)	C6—C5—C55—O55	119.5 (2)
C16—C11—C12—C13	2.0 (3)	C4—C5—C55—C54	172.34 (18)
N1—C11—C12—C13	−178.86 (19)	C51—C5—C55—C54	50.0 (2)
C11—C12—C13—C14	−2.3 (3)	C6—C5—C55—C54	−65.8 (2)
C12—C13—C14—C15	0.6 (4)	C76—C71—C72—C73	0.0 (3)
C13—C14—C15—C16	1.5 (4)	C77—C71—C72—C73	−179.6 (2)
C14—C15—C16—C11	−1.8 (3)	C71—C72—C73—C74	−2.1 (4)
C12—C11—C16—C15	0.0 (3)	C741—O741—C74—C75	−165.5 (2)
N1—C11—C16—C15	−179.1 (2)	C741—O741—C74—C73	14.1 (3)
C3—C3A—C7A—N1	−1.2 (2)	C72—C73—C74—C75	2.7 (4)
C4—C3A—C7A—N1	−179.77 (19)	C72—C73—C74—O741	−176.9 (2)
C3—C3A—C7A—N7	178.09 (19)	O741—C74—C75—C76	178.4 (2)
C4—C3A—C7A—N7	−0.5 (3)	C73—C74—C75—C76	−1.3 (4)
N2—N1—C7A—C3A	1.8 (2)	C74—C75—C76—C71	−0.8 (4)
C11—N1—C7A—C3A	−176.9 (2)	C72—C71—C76—C75	1.4 (3)
N2—N1—C7A—N7	−177.49 (18)	C77—C71—C76—C75	−179.0 (2)
C11—N1—C7A—N7	3.8 (3)	C7A—N7—C77—C71	−167.58 (17)
C6—N7—C7A—C3A	14.3 (3)	C6—N7—C77—C71	62.6 (2)
C77—N7—C7A—C3A	−118.1 (2)	C72—C71—C77—N7	−155.42 (19)
C6—N7—C7A—N1	−166.59 (19)	C76—C71—C77—N7	25.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C52—H52A···O55^i	0.99	2.57	3.236 (3)	124
C77—H77A···O51^ii	0.99	2.54	3.275 (3)	131
C52—H52B···Cg1^i	0.99	2.82	3.384 (2)	117

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