Effect of substitution on the dimensionality of supramolecular aggregation in dihydro­benzo­pyrazolo­quinolines

Portilla, J.; Quiroga, J.; Cobo, J.; Low, J.N.; Glidewell, C.

doi:10.1107/S0108270105020093

organic compounds

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 61| Part 8| August 2005| Pages o483-o489

doi:10.1107/S0108270105020093

Effect of substitution on the dimensionality of supramolecular aggregation in dihydrobenzopyrazoloquinolines

Jaime Portilla,^a Jairo Quiroga,^a Justo Cobo,^b John N. Low ^c and Christopher Glidewell ^d ^*

^aGrupo de Investigación de Compuestos Heterocíclicos, Departamento de Química, Universidad de Valle, AA 25360 Cali, Colombia, ^bDepartamento de Química Inorgánica y Orgánica, Universidad de Jaén, 23071 Jaén, Spain, ^cDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, and ^dSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland
^*Correspondence e-mail: cg@st-andrews.ac.uk

(Received 21 June 2005; accepted 24 June 2005; online 23 July 2005)

Molecules of 8-methyl-10-phenyl-6,10-dihydro-5H-benzo[h]pyrazolo[3,4-b]quinoline, C₂₁H₁₇N₃, (I), are linked into cyclic centrosymmetric dimers by means of paired C—H⋯N hydrogen bonds. In each of 8-methyl-7,10-diphenyl-6,10-dihydro-5H-benzo[h]pyrazolo[3,4-b]quinoline, C₂₇H₂₁N₃, (II), and 8-methyl-7-(4-methylphenyl)-10-phenyl-6,10-dihydro-5H-benzo[h]pyrazolo[3,4-b]quinoline, C₂₈H₂₃N₃, (III), the molecules are linked by C—H⋯π(arene) hydrogen bonds into sheets, although the detailed construction of the sheets is entirely different in (II) and (III). The molecules of 7-(4-methoxyphenyl)-8-methyl-10-phenyl-6,10-dihydro-5H-benzo[h]pyrazolo[3,4-b]quinoline, C₂₈H₂₃N₃O, (IV), are linked into a complex three-dimensional framework structure by a combination of C—H⋯N, C—H⋯O and three independent C—H⋯π(arene) hydrogen bonds.

Comment

Pyrazolo[3,4-b]quinolines are of interest as possible antiviral and antimalarial agents, and because of their other biological properties, such as parasiticidic, bactericidal, vasodilator, and enzyme-inhibitory activity (Quiroga et al., 2001 ). We report here the structures of four dihydrobenzopyrazoloquinolines, (I)–(IV) (Figs. 1–4 ), synthesized by a simple solvent-free cyclocondensation, under microwave irradiation, of 5-amino-3-methyl-1-phenylpyrazole and the condensation products derived from 2-tetralone and a range of simple aldehydes. One objective of these structure determinations was the investigation of how the introduction of different simple aryl substituents at position 7 in compounds (II)–(IV) influences the supramolecular aggregation compared with that in the unsubstituted compound, (I). We have recently reported the structures of the isomorphous and isostructural chlorophenyl and bromophenyl analogues, compounds (V) and (VI) (Serrano et al., 2005a ,b ).

In each of compounds (I)–(IV), the bond distances within the fused heterocyclic components are consistent with aromatic delocalization within the pyridine ring, but with strong double-bond fixation in the C8—N9 bond of the pyrazole ring. The other distances and angles present no exceptional features. The non-aromatic carbocyclic ring adopts a nearly ideal screw-boat conformation (Evans & Boeyens, 1989 ) in each compound, as shown by the ring-puckering parameters (Cremer & Pople, 1975 ), given for the atom sequence C4a—C5—C6—C6a—C11a—C11b in Table 1. For a six-membered ring with equal bond lengths throughout, the screw-boat conformation is characterized by θ = 67.5 or 112.5°, and φ = (60k + 30)° (k = integer).

Associated with the screw-boat conformation of the non-aromatic carbocyclic ring, the two aromatic rings linked by the bond C11a—C11b (Figs. 1–4 ) are not parallel, and they make dihedral angles ranging from 11.11 (7)° in compound (III) to 15.78 (7)° in compound (II) (Table 1). The dihedral angles between the pyridine ring and the pendent C71–C76 aryl ring are likewise very similar for compounds (II)–(IV). On the other hand, the dihedral angles between the pyrazole ring and the pendent C101–C106 aryl ring show a rather larger variation. It may be noted here that rings C71–C76 and C101–C106 participate in the hydrogen bonding in each of (II)–(IV), and that the hydrogen bonding may be an important factor in controlling these dihedral angles.

The supramolecular aggregation in compound (I) is extremely simple and involves just one hydrogen bond (Table 2). Atom C5 in the molecule at (x, y, z) acts as hydrogen-bond donor, via the axial atom H5A, to pyrazole atom N9 in the molecule at (1 − x, 1 − y, 1 − z), so forming a centrosymmetric R₂²(16) dimer centred at ( $[{1\over 2}]$ , $[{1\over 2}]$ , $[{1\over 2}]$ ) (Fig. 5). The formation of this dimer is reinforced by a π–π stacking interaction involving the pyridine rings of the two component molecules. These rings are strictly parallel, with an interplanar spacing of 3.450 (2) Å. The ring-centroid separation is 3.729 (2) Å, corresponding to a nearly ideal ring offset of 1.415 (2) Å. There are no other direction-specific interactions between the molecules; in particular, C—H⋯π(arene) hydrogen bonds are absent. Hence, the structure of compound (I) simply consists of isolated centrosymmetric dimers.

By contrast with the structure of (I), there are no C—H⋯N hydrogen bonds in the structures of either (II) or (III). Instead, the molecules of (II) and (III) are linked into sheets by C—H⋯π(arene) hydrogen bonds, a type of interaction absent from the structure of (I). Despite crystallizing in the same space group, namely P2₁/c, the formation of the hydrogen-bonded sheets differs considerably between (II) and (III).

In compound (II), the pyridine ring and the pendent C101–C106 phenyl ring act as hydrogen-bond acceptors. In the shorter of the two hydrogen bonds (Table 2), atom C73 in the molecule at (x, y, z) acts as donor to the C101–C106 aryl ring in the molecule at (1 − x, 1 − y, −z), so generating a cyclic and centrosymmetric dimeric motif centred at ( $[{1\over 2}]$ , $[{1\over 2}]$ , 0). The second of the two hydrogen bonds then links this dimer at ( $[{1\over 2}]$ , $[{1\over 2}]$ , 0) to four adjacent dimers. Atoms C4 in the molecules at (x, y, z) and (1 − x, 1 − y, −z) act as hydrogen-bond donors to the pyridine rings in the molecules at (x, $[{1\over 2}]$ − y, $[{1\over 2}]$ + z) and (1 − x, $[{1\over 2}]$ + y, − $[{1\over 2}]$ − z), respectively, which themselves form parts of the dimers centred at ( $[{1\over 2}]$ , 0, $[{1\over 2}]$ ) and ( $[{1\over 2}]$ , 1, − $[{1\over 2}]$ ), respectively. Similarly, the pyridine rings at (x, y, z) and (1 − x, 1 − y, −z) accept hydrogen bonds from the C4 atoms in the molecules at (x, $[{1\over 2}]$ − y, z − $[{1\over 2}]$ ) and (1 − x, $[{1\over 2}]$ + y, $[{1\over 2}]$ − z), which are themselves components of dimers centred at ( $[{1\over 2}]$ , 0, − $[{1\over 2}]$ ) and ( $[{1\over 2}]$ , 1, $[{1\over 2}]$ ). Propagation by the space group of these two hydrogen bonds, associated with an inversion and a c-glide plane, respectively, then generates a (100) sheet in which large and small rings alternate (Fig. 6).

As in (II), the two-dimensional supramolecular structure of (III) is built from two C—H⋯π(arene) hydrogen bonds (Table 2), but now both are associated with translational symmetry operations and there are no directly connected pairs of molecules which are related by inversion. Again, unlike the hydrogen bonds in (II), for those in (III) the two donors form parts of the same aryl ring, while the acceptors are the two aryl rings pendent from the fused ring system.

Aryl atom C73 in the molecule at (x, y, z) acts as hydrogen-bond donor to the C101–C106 ring in the molecule at (1 − x, y − $[{1\over 2}]$ , $[{3\over 2}]$ − z), thereby forming a chain running parallel to the [010] direction and generated by the 2₁ screw axis along ( $[{1\over 2}]$ , y, $[{3\over 4}]$ ) (Fig. 7). In addition, atom C76 at (x, y, z) acts as hydrogen-bond donor to the C1/C2/C3/C4/C4a/C11b ring in the molecule at (x, $[{3\over 2}]$ − y, $[{1\over 2}]$ + z), thus producing a chain parallel to the [001] direction and generated by the c-glide plane at y = $[{3\over 4}]$ (Fig. 8). The combination of these two chains generates a (100) sheet in the form of a (4,4)-net (Fig. 9).

The constitution of compound (IV) differs from those of (I)–(III) in that it provides an additional acceptor of hydrogen bonds in the O atom of the methoxy substituent (Fig. 4). In fact, the molecules of (IV) are linked by a combination of C—H⋯N, C—H⋯O and C—H⋯π(arene) hydrogen bonds (Table 2) into a rather complex three-dimensional framework. The formation of this framework can be analysed very straightforwardly in terms of the component one-dimensional substructures.

In the first such substructure, the C—H⋯N and C—H⋯O hydrogen bonds combine to generate a chain of edge-fused rings. Aryl atom C72 in the molecule at (x, y, z) acts as hydrogen-bond donor to pyridine atom N11 in the molecule at (1 − x, 1 − y, 1 − z), thereby generating a centrosymmetric R₂²(14) ring centred at ( $[{1\over 2}]$ , $[{1\over 2}]$ , $[{1\over 2}]$ ). In addition, atom C2 at (x, y, z) acts as donor to atom O7 in the molecule at (1 + x, y, 1 + z), so generating by translation a C(12) chain running parallel to the [101] direction. The combination of these two hydrogen bonds then generates a chain of edge-fused rings, with R₂²(14) rings centred at (n + $[{1\over 2}]$ , $[{1\over 2}]$ , n + $[{1\over 2}]$ ) (n = zero or integer) and R₄⁴(22) rings centred at (n, $[{1\over 2}]$ , n) (n = zero or integer) (Fig. 10).

The second one-dimensional substructure also takes the form of a chain of edge-fused rings. Aryl atoms C75 in the molecules at (x, y, z) and (1 − x, 1 − y, 1 − z), which form the R₂²(14) dimer centred at ( $[{1\over 2}]$ , $[{1\over 2}]$ , $[{1\over 2}]$ ), act as hydrogen-bond donors to the C101–C106 rings in the molecules at (1 − x, 1 − y, −z) and (x, y, 1 + z), respectively, which themselves form part of the R₂²(14) dimers centred at ( $[{1\over 2}]$ , $[{1\over 2}]$ , − $[{1\over 2}]$ ) and ( $[{1\over 2}]$ , $[{1\over 2}]$ , $[{3\over 2}]$ ), respectively, so forming a chain of edge-fused centrosymmetric rings running parallel to the [001] direction (Fig. 11).

In addition to this [001] chain of edge-fused rings generated by inversion, there is a second substructure running parallel to [001] in the form of a simple chain generated by a c-glide plane. Aryl atom C4 in the molecule at (x, y, z) acts as hydrogen-bond donor to the pyridine ring in the molecule at (x, $[{3\over 2}]$ − y, $[{1\over 2}]$ + z), producing an [001] chain generated by the c-glide plane at y = $[{3\over 4}]$ (Fig. 12).

In the final substructure, atom C103 in the molecule at (x, y, z) acts as hydrogen-bond donor to the pendent C71–C76 aryl ring in the molecule at (1 − x, y − $[{1\over 2}]$ , $[{1\over 2}]$ − z), so forming a chain running parallel to the [010] direction and generated by the 2₁ screw axis along ( $[{1\over 2}]$ , y, $[{1\over 4}]$ ) (Fig. 13).

The combination of the chains along [010], [001] and [101] suffices to link all of the molecules into a single three-dimensional framework, the complexity of which arises largely from the occurrence in the structure of five independent hydrogen bonds (Table 2).

We briefly compare the supramolecular structures of compounds (I)–(IV) reported here with those of the pair of compounds, (V) and (VI) (see scheme), containing 4-halogenophenyl substituents, where the molecular skeleton is a simple positional isomer of the skeleton in compounds (I)–(IV), and which are themseleves strictly isostructural in space group P $[\overline{1}]$ , as reported recently (Serrano et al., 2005a,b). In these analogues, the molecules are linked by C—H⋯π(arene) hydrogen bonds into chains of edge-fused rings. Hence, within this rather compact group of compounds, viz. (I)–(VI), the supramolecular aggregation ranges from finite (zero-dimensional) in compound (I), via one-dimensional in compounds (V) and (VI) and two-dimensional in compounds (II) and (III), to three-dimensional in compound (IV).

The differences between the 4-methylphenyl compound, (III), and the 4-chlorophenyl compound, (V), in terms of both their space groups, namely P2₁/c for (III) as opposed to P $[\overline{1}]$ for (V), and their supramolecular dimensionality, namely two-dimensional for (III) as opposed to one-dimensional for (V), is unexpected, as methyl and chloro substituents on aryl rings are generally effectively isosteric. This is well illustrated, for example, by the related series of fused heterocycles (VII)–(IX) (see scheme) containing, respectively, 4-methylphenyl, 4-chlorophenyl and 4-bromophenyl substituents, which are all isomorphous and strictly isostructural (Portilla et al., 2005 ).

Figure 1
The molecule of (I)

, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

Figure 2
The molecule of (II)

, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

Figure 3
The molecule of (III)

, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

Figure 4
The molecule of (IV)

, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

Figure 5
Part of the crystal structure of (I)

, showing the formation of a centrosymmetric hydrogen-bonded dimer. For the sake of clarity, H atoms bonded to those C atoms which are not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) are at the symmetry position (1 − x, 1 − y, 1 − z).

Figure 6
A stereoview of part of the crystal structure of (II)

, showing the formation of a hydrogen-bonded (100) sheet generated by the combination of an inversion and a glide plane. For the sake of clarity, H atoms not involved in the motifs shown have been omitted.

Figure 7
A stereoview of part of the crystal structure of (III)

, showing the formation of a hydrogen-bonded chain along [010] generated by a 2₁ screw axis. For the sake of clarity, H atoms not involved in the motif shown have been omitted.

Figure 8
A stereoview of part of the crystal structure of (III)

, showing the formation of a hydrogen-bonded chain along [001] generated by a glide plane. For the sake of clarity, H atoms not involved in the motif shown have been omitted.

Figure 9
A stereoview of part of the crystal structure of (III)

, showing the formation of a hydrogen-bonded (100) sheet generated by the combination of the [010] and [001] chains. For the sake of clarity, H atoms not involved in the motifs shown have been omitted.

Figure 10
A stereoview of part of the crystal structure of (IV)

, showing the formation of a chain of edge-fused rings along [101] built from C—H⋯N and C—H⋯O hydrogen bonds. For the sake of clarity, H atoms not involved in the motif shown have been omitted.

Figure 11
A stereoview of part of the crystal structure of (IV)

, showing the formation of a chain of edge-fused rings along [001] built from C—H⋯N and C—H⋯π(arene) hydrogen bonds. For the sake of clarity, H atoms not involved in the motif shown have been omitted.

Figure 12
Part of the crystal structure of (IV)

, showing the formation of a simple [001] chain built from C—H⋯π(arene) hydrogen bonds. For the sake of clarity, H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (x, $[{3\over 2}]$ − y, $[{1\over 2}]$ + z) and (x, $[{3\over 2}]$ − y, z − $[{1\over 2}]$ ), respectively.

Figure 13
Part of the crystal structure of (IV)

, showing the formation of a simple [010] chain built from C—H⋯π(arene) hydrogen bonds. For the sake of clarity, H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (1 − x, y − $[{1\over 2}]$ , $[{1\over 2}]$ − z) and (1 − x, $[{1\over 2}]$ + y, $[{1\over 2}]$ − z), respectively.

Experimental

For the preparation of the title compounds, equimolar quantities of 5-amino-3-methyl-1-phenylpyrazole (1.0 mmol) and the corresponding methylene derivative (from 2-tetralone and the appropriate aldehyde) (1.0 mmol) were placed in open Pyrex glass vessels and irradiated in a domestic microwave oven for 3–5 min at 600 W. The reaction mixture was extracted with ethanol and the extract was evaporated. The solid residues were recrystallized from dimethylformamide to give crystals suitable for single-crystal X-ray diffraction. Analysis for (I): yellow crystals (m.p. 439–440 K, yield 60%), MS (30 eV) m/z (%) = 311 (100, M⁺), 296 (7); for (II): yellow crystals (m.p. 494–495 K, yield 78%), MS (30 eV) m/z (%) = 388 (36), 387 (100, M⁺), 372 (6); for (III): yellow crystals (m.p. 484–485 K, yield 75%), MS (30 eV) m/z (%) = 402 (36), 401 (100, M⁺), 386 (6); for (IV): pale-brown crystals (m.p. 484–485 K, yield 60%), MS (30 eV) m/z (%) = 418 (33), 417 (100, M⁺), 402 (6).

Compound (I)

Crystal data

C₂₁H₁₇N₃
M_r = 311.38
Triclinic, $[P \overline 1]$
a = 7.0870 (2) Å
b = 10.1321 (4) Å
c = 11.7977 (5) Å
α = 87.501 (2)°
β = 73.171 (3)°
γ = 74.828 (2)°
V = 782.13 (5) Å³
Z = 2
D_x = 1.322 Mg m⁻³
Mo Kα radiation
Cell parameters from 3576 reflections
θ = 3.1–27.6°
μ = 0.08 mm⁻¹
T = 120 (2) K
Rod, yellow
0.50 × 0.10 × 0.10 mm

Data collection

Bruker–Nonius KappaCCD area-detector diffractometer
φ and ω scans
Absorption correction: multi-scan(SADABS; Sheldrick, 2003 )T_min = 0.954, T_max = 0.992
15116 measured reflections
3576 independent reflections
2810 reflections with I > 2σ(I)
R_int = 0.039
θ_max = 27.6°
h = −8 → 9
k = −12 → 13
l = −15 → 15

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.114
S = 1.04
3576 reflections
218 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0601P)² + 0.1501P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Compound (II)

Crystal data

C₂₇H₂₁N₃
M_r = 387.47
Monoclinic, P 2₁ /c
a = 11.5561 (4) Å
b = 17.6751 (7) Å
c = 9.8469 (3) Å
β = 98.599 (2)°
V = 1988.67 (12) Å³
Z = 4
D_x = 1.294 Mg m⁻³
Mo Kα radiation
Cell parameters from 4539 reflections
θ = 2.9–27.5°
μ = 0.08 mm⁻¹
T = 120 (2) K
Block, yellow
0.40 × 0.20 × 0.20 mm

Data collection

Bruker–Nonius KappaCCD area-detector diffractometer
φ and ω scans
Absorption correction: multi-scan(SADABS; Sheldrick, 2003)T_min = 0.973, T_max = 0.985
26788 measured reflections
4539 independent reflections
3236 reflections with I > 2σ(I)
R_int = 0.053
θ_max = 27.5°
h = −15 → 13
k = −22 → 22
l = −12 → 12

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.126
S = 1.08
4539 reflections
272 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0639P)² + 0.3388P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Compound (III)

Crystal data

C₂₈H₂₃N₃
M_r = 401.49
Monoclinic, P 2₁ /c
a = 12.0313 (3) Å
b = 14.3347 (4) Å
c = 12.7956 (3) Å
β = 109.3092 (14)°
V = 2082.66 (9) Å³
Z = 4
D_x = 1.280 Mg m⁻³
Mo Kα radiation
Cell parameters from 4778 reflections
θ = 3.2–27.5°
μ = 0.08 mm⁻¹
T = 120 (2) K
Lath, yellow
0.66 × 0.42 × 0.14 mm

Data collection

Bruker–Nonius KappaCCD area-detector diffractometer
φ and ω scans
Absorption correction: multi-scan(SADABS; Sheldrick, 2003)T_min = 0.956, T_max = 0.989
38247 measured reflections
4778 independent reflections
3416 reflections with I > 2σ(I)
R_int = 0.059
θ_max = 27.5°
h = −15 → 15
k = −18 → 18
l = −16 → 16

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.129
S = 1.04
4778 reflections
282 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.066P)² + 0.5056P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Compound (IV)

Crystal data

C₂₈H₂₃N₃O
M_r = 417.49
Monoclinic, P 2₁ /c
a = 12.9148 (3) Å
b = 17.5938 (5) Å
c = 9.8192 (2) Å
β = 104.3370 (17)°
V = 2161.64 (9) Å³
Z = 4
D_x = 1.283 Mg m⁻³
Mo Kα radiation
Cell parameters from 4963 reflections
θ = 3.3–27.5°
μ = 0.08 mm⁻¹
T = 120 (2) K
Plate, pale brown
0.50 × 0.20 × 0.05 mm

Data collection

Bruker–Nonius KappaCCD area-detector diffractometer
φ and ω scans
Absorption correction: multi-scan(SADABS; Sheldrick, 2003)T_min = 0.974, T_max = 0.996
35681 measured reflections
4963 independent reflections
3449 reflections with I > 2σ(I)
R_int = 0.062
θ_max = 27.5°
h = −16 → 16
k = −22 → 22
l = −12 → 11

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.112
S = 1.04
4963 reflections
291 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0534P)² + 0.4296P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Ring-puckering parameters and selected dihedral angles (Å, °) for compounds (I)–(IV)

The ring-puckering parameters for the non-aromatic carbocyclic ring are calculated for the atom sequence C4a—C5—C6—C6a—C11a—C11b.

Parameter	(I)	(II)	(III)	(IV)
Q	0.423 (2)	0.461 (2)	0.460 (2)	0.450 (2)
θ	63.9 (2)	115.4 (2)	61.5 (2)	115.5 (2)
φ	89.6 (2)	274.1 (2)	96.6 (2)	271.6 (2)
(C1–C4/C4a/C11b)/pyridine	13.84 (7)	15.78 (7)	11.11 (7)	14.79 (7)
(C71–C76)/pyridine		63.45 (7)	65.27 (7)	60.88 (7)
(C101–C106)/pyrazole	26.21 (7)	33.16 (8)	18.56 (8)	30.30 (4)

Table 2
Hydrogen-bond geometry (Å, °) for compounds (I)–(IV)

Cg1–Cg4 are the centroids of rings N11/C10a/C7a/C7/C6a/C11a, C101–C106, C1–C4/C4a/C11a and C71–C76, respectively.

	D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
(I)	C5—H5A⋯N9ⁱ	0.99	2.60	3.4070 (18)	139
(II)	C4—H4⋯Cg1ⁱⁱ	0.95	2.82	3.7461 (17)	164
	C73—H73⋯Cg2ⁱⁱⁱ	0.95	2.62	3.4852 (17)	152
(III)	C73—H73⋯Cg2^iv	0.95	2.96	3.8991 (18)	168
	C76—H76⋯Cg3^v	0.95	2.90	3.8349 (17)	168
(IV)	C2—H2⋯O7^vi	0.95	2.53	3.3422 (18)	144
	C72—H72⋯N11ⁱ	0.95	2.60	3.3952 (17)	142
	C4—H4⋯Cg1^v	0.95	2.84	3.7766 (17)	168
	C75—H75⋯Cg2ⁱⁱⁱ	0.95	2.67	3.5605 (15)	157
	C103—H103⋯Cg4^vii	0.95	2.85	3.7417 (19)	157
Symmetry codes: (i) 1-x, 1-y, 1-z; (ii) $[x, \script{1 \over 2}-y, \script{1 \over 2}+z]$ ; (iii) 1-x, 1-y, -z; (iv) $[1-x, y-\script{1 \over 2}, \script{3 \over 2}-z]$ ; (v) $[x, \script{3 \over 2}-y, \script{1 \over 2}+z]$ ; (vi) 1+x, y, 1+z; (vii) $[1-x, y-\script{1 \over 2}, \script{1 \over 2}-z]$ .

Crystals of compound (I) are triclinic; space group P $[\overline{1}]$ was selected and then confirmed by the successful structure analysis. For each of compounds (II)–(IV), the space group P2₁/c was uniquely assigned from the systematic absences. All H atoms were located from difference maps and then treated as riding atoms, with C—H distances of 0.95 (aromatic), 0.98 (CH₃) or 0.99 Å (CH₂), and with U_iso(H) = 1.2U_eq(C), or 1.5U_eq(C) for the methyl groups. The crystals of compound (III) were very fragile, and attempts to cut small fragments from larger crystals resulted in shattering.

For all compounds, data collection: COLLECT (Hooft, 1999 ); cell refinement: DENZO (Otwinowski & Minor, 1997 ) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle, 2003 ) and SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I, II, III, IV. DOI: 10.1107/S0108270105020093/sk1854sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270105020093/sk1854Isup2.hkl

Structure factors: contains datablock II. DOI: 10.1107/S0108270105020093/sk1854IIsup3.hkl

Structure factors: contains datablock III. DOI: 10.1107/S0108270105020093/sk1854IIIsup4.hkl

Structure factors: contains datablock IV. DOI: 10.1107/S0108270105020093/sk1854IVsup5.hkl

Comment top

Pyrazolo[3,4-b]quinolines are of interest as possible antiviral and antimalarial agents, and because of their other biological properties, such as parasiticidic, bactericidal, vasodilator, and enzyme-inhibitory activity (Quiroga et al., 2001). Here, we report the structures of four dihydrobenzopyrazoloquinolines, (I)–(IV) (Figs. 1–4), synthesized by a simple solvent-free cyclocondensation, under microwave irradiation, of 5-amino-3-methyl-1-phenylpyrazole and the condensation products derived from 2-tetralone and a range of simple aldehydes. One objective of these structure determinations was the investigation of how the introduction of different simple aryl substituents at position 7 in compounds (II)–(IV) influences the supramolecular aggregation compared with that in the unsubstituted compound, (I). We have recently reported the structures of the isomorphous and isostructural chlorophenyl and bromophenyl analogues, compounds (V) and (VI) (Serrano et al., 2005a,b).

In each of compounds (I)–(IV), the bond distances within the fused heterocyclic components are consistent with aromatic delocalization within the pyridine ring, but with strong double-bond fixation in the C8—N9 bond of the pyrazole ring. The other distances and angles present no exceptional features. The non-aromatic carbocyclic ring adopts a nearly ideal screw-boat conformation (Evans & Boeyens, 1989) in each compound, as shown by the ring-puckering parameters (Cremer & Pople, 1975), given for the atom sequence C4a/C5/C6/C6a/C11a/C11b in Table 1. For a six-membered ring with equal bond lengths throughout, the screw-boat conformation is characterized by θ = 67.5° or 112.5°, and ϕ = (60k + 30)° (k = integer).

Associated with the screw-boat conformation of the non-aromatic carbocyclic ring, the two aromatic rings linked by the bond C11a—C11b (Figs. 1–4) are not parallel, and they make dihedral angles ranging from 11.11 (7)° in compound (III) to 15.78 (7)° in compound (II) (Table 1). The dihedral angles between the pyridine ring and the pendent aryl ring C71–C76 are likewise very similar for compounds (II)–(IV). On the other hand, the dihedral angles between the pyrazole ring and the pendent aryl ring C101–C106 show a rather larger variation. It may be noted here that the rings C71–C76 and C101–C106 participate in the hydrogen bonding in each of (II)–(IV), and that the hydrogen bonding may be an important factor in controlling these dihedral angles.

The supramolecular aggregation in compound (I) is extremely simple and involves just one hydrogen bond (Table 2). Atom C5 in the molecule at (x, y, z) acts as hydrogen-bond donor, via the axial atom H5A, to pyrazole atom N9 in the molecule at (1 − x, 1 − y, 1 − z), so forming a centrosymmetric R₂²(16) dimer centred at (1/2, 1/2, 1/2) (Fig. 5). The formation of this dimer is reinforced by a π–π stacking interaction involving the pyridine rings of the two component molecules. These rings are strictly parallel, with an interplanar spacing of 3.450 (2) Å. The ring-centroid separation is 3.729 (2) Å, corresponding to a nearly ideal ring offset of 1.415 (2) Å. There are no other direction-specific interactions between the molecules; in particular, C—H···π(arene) hydrogen bonds are absent. Hence, the structure of compound (I) simply consists of isolated centrosymmetric dimers.

By contrast with the structure of (I), there are no C—H···N hydrogen bonds in the structures of either (II) or (III). Instead, the molecules of (II) and (III) are linked into sheets by C—H···π(arene) hydrogen bonds, a type of interaction absent from the structure of (I). Despite crystallizing in the same space group, P2₁/c, the formation of the hydrogen-bonded sheets differs considerably between (II) and (III).

In compound (II), the pyridine ring and the pendent phenyl ring C101–C106 act as hydrogen-bond acceptors. In the shorter of the two hydrogen bonds (Table 2), atom C73 in the molecule at (x, y, z) acts as donor to the aryl ring C101–C106 in the molecule at (1 − x, 1 − y, −z), so generating a cyclic and centrosymmetric dimeric motif centred at (1/2, 1/2, 0). The second of the two hydrogen bonds then links this dimer at (1/2, 1/2, 0) to four adjacent dimers. The atoms C4 in the molecules at (x, y, z) and (1 − x, 1 − y, −z) act as hydrogen-bond donors to the pyridine rings in the molecules at (x, 1/2 − y, 1/2 + z) and (1 − x, 1/2 + y, −1/2 − z), respectively, which themselves form parts of the dimers centred at (1/2, 0, 1/2) and (1/2, 1, −1/2), respectively. Similarly, the pyridine rings at (x, y, z) and (1 − x, 1 − y, −z) accept hydrogen bonds from the atoms C4 in the molecules at (x, 1/2 − y, z − 1/2) and (1 − x, 1/2 + y, 1/2 − z), which are themselves components of dimers centred at (1/2, 0, −1/2) and (1/2, 1, 1/2). Propagation by the space group of these two hydrogen bonds, associated with an inversion and a c-glide plane, respectively, then generates a (100) sheet in which large and small rings alternate (Fig. 6).

As in (II), the two-dimensional supramolecular structure of (III) is built from two C—H···π(arene) hydrogen bonds (Table 2), but now both are associated with translational symmetry operations and there are no directly connected pairs of molecules which are related by inversion. Again, unlike the hydrogen bonds in (II), for those in (III), the two donors form parts of the same aryl ring, while the acceptors are the two aryl rings pendent from the fused ring system.

Aryl atom C73 in the molecule at (x, y, z) acts as hydrogen-bond donor to the ring C101–C106 in the molecule at (1 − x, y − 1/2, 3/2 − z), thereby forming a chain running parallel to the [010] direction and generated by the 2₁ screw axis along (1/2, y, 3/4) (Fig. 7). In addition, atom C76 at (x, y, z) acts as hydrogen-bond donor to the C1/C2/C3/C4/C4a/C11b ring in the molecule at (x, 3/2 − y, 1/2 + z), thus producing a chain parallel to the [001] direction and generated by the c-glide plane at y = 3/4 (Fig. 8). The combination of these two chains generates a (100) sheet in the form of a (4,4) net (Fig. 9).

The constitution of compound (IV) differs from those of (I)–(III) in that it provides an additional acceptor of hydrogen bonds in the O atom of the methoxy substituent (Fig. 4). In fact, the molecules of (IV) are linked by a combination of C—H···N, C—H···O and C—H···π(arene) hydrogen bonds (Table 2) into a rather complex three-dimensional framework. The formation of this framework can be analysed very straightforwardly in terms of the component one-dimensional substructures.

In the first such substructure, the C—H···N and C—H···O hydrogen bonds combine to generate a chain of edge-fused rings. Aryl atom C72 in the molecule at (x, y, z) acts as hydrogen-bond donor to pyridine atom N11 in the molecule at (1 − x, 1 − y, 1 − z), thereby generating a centrosymmetric R₂²(14) ring centred at (1/2, 1/2, 1/2). In addition, atom C2 at (x, y, z) acts as donor to atom O7 in the molecule at (1 + x, y, 1 + z), so generating by translation a C(12) chain running parallel to the [101] direction. The combination of these two hydrogen bonds then generates a chain of edge-fused rings, with R₂²(14) rings centred at (n + 1/2, 1/2, n + 1/2) (n = zero or integer) and R₄⁴(22) rings centred at (n, 1/2, n) (n = zero or integer) (Fig. 10).

The second one-dimensional substructure also takes the form of a chain of edge-fused rings. Aryl atoms C75 in the molecules at (x, y, z) and (1 − x, 1 − y, 1 − z), which form the R₂²(14) dimer centred at (1/2, 1/2, 1/2), act as hydrogen-bond donors to the C101–C106 rings in the molecules at (1 − x, 1 − y, −z) and (x, y, 1 + z), respectively, which themselves form part of the R₂²(14) dimers centred at (1/2, 1/2, −1/2) and (1/2, 1/2, 3/2), respectively, so forming a chain of edge-fused centrosymmetric rings running parallel to the [001] direction (Fig. 11).

In addition to this [001] chain of edge-fused rings generated by inversion, there is a second substructure running parallel to [001] in the form of a simple chain generated by a c-glide plane. Aryl atom C4 in the molecule at (x, y, z) acts as hydrogen-bond donor to the pyridine ring in the molecule at (x, 3/2 − y, 1/2 + z), producing an [001] chain generated by the c-glide plane at y = 3/4 (Fig. 12).

In the final substructure, atom C103 in the molecule at (x, y, z) acts as hydrogen-bond donor to the pendent aryl ring C71–C76 in the molecule at (1 − x, y − 1/2, 1/2 − z), so forming a chain running parallel to the [010] direction and generated by the 2₁ screw axis along (1/2, y, 1/4) (Fig. 13).

We briefly compare the supramolecular structures of compounds (I)–(IV) reported here with those of the pair of compounds, (V) and (VI), containing 4-halogenophenyl substituents, where the molecular skeleton is a simple positional isomer of the skeleton in compounds (I)–(IV), and which are themseleves strictly isostructural in space group P1, as reported recently (Serrano et al., 2005a,b). In these analogues, the molecules are linked by C—H···π(arene) hydrogen bonds into chains of edge-fused rings. Hence, within this rather compact group of compounds, (I)–(VI), the supramolecular aggregation ranges from finite (zero-dimensional) in compound (I), via one-dimensional in compounds (V) and (VI) and two-dimensional in compounds (II) and (III), to three-dimensional in compound (IV).

The differences between the 4-methylphenyl compound, (III), and the 4-chlorophenyl compound, (V), in terms of both their space groups, namely P2₁/c for (III) as opposed to P1 for (V), and their supramolecular dimensionality, namely two-dimensional for (III) as opposed to one-dimensional for (V), is unexpected, as methyl and chloro substituents on aryl rings are generally effectively isosteric. This is well illustrated, for example by the related series of fused heterocycles (VII)–(IX) (see scheme) containing, respectively, 4-methylphenyl, 4-chlorophenyl and 4-bromophenyl substituents, which are all isomorphous and strictly isostructural (Portilla et al., 2005).

Experimental top

Equimolar quantities of 5-amino-3-methyl-1-phenylpyrazole (1.0 mmol) and the corresponding methylene derivative (from 2-tetralone and the appropriate aldehyde) (1.0 mmol) were placed in open Pyrex glass vessels and irradiated in a domestic microwave oven for 3–5 min at 600 W. The reaction mixture was extracted with ethanol and the extract was evaporated. The solid residues were recrystallized from dimethylformamide to give crystals suitable for single-crystal X-ray diffraction. Analysis, for (I): yellow crystals (m.p. 439–440 K, yield 60%), MS (30 eV) m/z (%) = 311 (100, M+), 296 (7); for (II), yellow crystals (m.p. 494–495 K, yield 78%), MS (30 eV) m/z (%) = 388 (36), 387 (100, M+), 372 (6); for (III), yellow crystals (m.p. 484–485 K, yield 75%), MS (30 eV) m/z (%) = 402 (36), 401 (100, M+), 386 (6); for (IV), pale-brown crystals (m.p. 484–485 K, yield 60%), MS (30 eV) m/z (%) = 418 (33), 417 (100, M+), 402 (6).

Computing details top

For all compounds, data collection: COLLECT (Hooft, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures top

	Fig. 1. The molecule of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The molecule of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 3. The molecule of (III), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 4. The molecule of (IV), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 5. Part of the crystal structure of (I), showing the formation of a centrosymmetric hydrogen-bonded dimer. For the sake of clarity, the H atoms bonded to those C atoms which are not involved in the motif shown have been omitted. The atoms marked with an asterisk (*) are at the symmetry position (1 − x, 1 − y, 1 − z).
	Fig. 6. A stereoview of part of the crystal structure of (II), showing the formation of a hydrogen-bonded (100) sheet generated by a combination of an inversion and a glide plane. For the sake of clarity, the H atoms not involved in the motifs shown have been omitted.
	Fig. 7. A stereoview of part of the crystal structure of (III), showing the formation of a hydrogen-bonded chain along [010] generated by a 2₁ screw axis. For the sake of clarity, the H atoms not involved in the motif shown have been omitted.
	Fig. 8. A stereoview of part of the crystal structure of (III), showing the formation of a hydrogen-bonded chain along [001] generated by a glide plane. For the sake of clarity, the H atoms not involved in the motif shown have been omitted.
	Fig. 9. A tereoview of part of the crystal structure of (III), showing the formation of a hydrogen-bonded (100) sheet generated by the combination of the [010] and [001] chains. For the sake of clarity, the H atoms not involved in the motifs shown have been omitted.
	Fig. 10. A stereoview of part of the crystal structure of (IV), showing the formation of a chain of edge-fused rings along [101] built from C—H···N and C—H···O hydrogen bonds. For the sake of clarity, the H atoms not involved in the motif shown have been omitted.
	Fig. 11. A stereoview of part of the crystal structure of (IV), showing the formation of a chain of edge-fused rings along [001] built from C—H···N and C—H···π(arene) hydrogen bonds. For the sake of clarity, the H atoms not involved in the motif shown have been omitted.
	Fig. 12. Part of the crystal structure of (IV), showing the formation of a simple [001] chain built from C—H···π(arene) hydrogen bonds. For the sake of clarity, the H atoms not involved in the motif shown have been omitted. The atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (x, 3/2 − y, 1/2 + z) and (x, 3/2 − y, z − 1/2), respectively.
	Fig. 13. Part of the crystal structure of (IV), showing the formation of a simple [010] chain built from C—H···π(arene) hydrogen bonds. For the sake of clarity, the H atoms not involved in the motif shown have been omitted. The atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (1 − x, y − 1/2, 1/2 − z) and (1 − x, 1/2 + y, 1/2 − z), respectively.

(I) 8-methyl-10-phenyl-6,10-dihydro-5H-benzo[h]pyrazolo[3,4-b]quinoline top

Crystal data top

C₂₁H₁₇N₃	Z = 2
M_r = 311.38	F(000) = 328
Triclinic, P1	D_x = 1.322 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.0870 (2) Å	Cell parameters from 3576 reflections
b = 10.1321 (4) Å	θ = 3.1–27.6°
c = 11.7977 (5) Å	µ = 0.08 mm⁻¹
α = 87.501 (2)°	T = 120 K
β = 73.171 (3)°	Rod, yellow
γ = 74.828 (2)°	0.50 × 0.10 × 0.10 mm
V = 782.13 (5) Å³

Data collection top

Bruker Nonius KappaCCD area-detector diffractometer	3576 independent reflections
Radiation source: Bruker Nonius FR91 rotating anode	2810 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.6°, θ_min = 3.1°
ϕ and ω scans	h = −8→9
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −12→13
T_min = 0.954, T_max = 0.992	l = −15→15
15116 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.114	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0601P)² + 0.1501P] where P = (F_o² + 2F_c²)/3
3576 reflections	(Δ/σ)_max < 0.001
218 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₂₁H₁₇N₃	γ = 74.828 (2)°
M_r = 311.38	V = 782.13 (5) Å³
Triclinic, P1	Z = 2
a = 7.0870 (2) Å	Mo Kα radiation
b = 10.1321 (4) Å	µ = 0.08 mm⁻¹
c = 11.7977 (5) Å	T = 120 K
α = 87.501 (2)°	0.50 × 0.10 × 0.10 mm
β = 73.171 (3)°

Data collection top

Bruker Nonius KappaCCD area-detector diffractometer	3576 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	2810 reflections with I > 2σ(I)
T_min = 0.954, T_max = 0.992	R_int = 0.039
15116 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.114	H-atom parameters constrained
S = 1.04	Δρ_max = 0.23 e Å⁻³
3576 reflections	Δρ_min = −0.28 e Å⁻³
218 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N9	0.83108 (15)	0.57987 (10)	0.28704 (9)	0.0217 (2)
N10	0.83152 (15)	0.44571 (10)	0.31468 (9)	0.0200 (2)
N11	0.76537 (15)	0.31767 (10)	0.49337 (9)	0.0197 (2)
C1	0.77407 (18)	0.07787 (13)	0.62078 (11)	0.0231 (3)
C2	0.7677 (2)	−0.04040 (14)	0.68381 (12)	0.0272 (3)
C3	0.6828 (2)	−0.03104 (14)	0.80610 (12)	0.0295 (3)
C4	0.6037 (2)	0.09613 (14)	0.86384 (12)	0.0280 (3)
C4a	0.61181 (19)	0.21609 (14)	0.80260 (11)	0.0234 (3)
C5	0.5240 (2)	0.35489 (14)	0.86468 (11)	0.0260 (3)
C6	0.6455 (2)	0.45575 (14)	0.80616 (11)	0.0252 (3)
C6a	0.68421 (18)	0.45661 (13)	0.67356 (11)	0.0210 (3)
C7	0.70232 (18)	0.57262 (13)	0.60931 (11)	0.0213 (3)
C7a	0.75017 (17)	0.56198 (12)	0.48612 (11)	0.0202 (3)
C8	0.78261 (18)	0.64947 (13)	0.38828 (11)	0.0210 (3)
C10a	0.78021 (17)	0.43267 (13)	0.43543 (11)	0.0190 (3)
C11a	0.71542 (17)	0.33172 (13)	0.61172 (11)	0.0194 (3)
C11b	0.69941 (17)	0.20645 (13)	0.67939 (11)	0.0206 (3)
C81	0.7624 (2)	0.79962 (13)	0.38979 (13)	0.0275 (3)
C101	0.86390 (18)	0.34987 (12)	0.22219 (11)	0.0198 (3)
C102	0.78040 (18)	0.23804 (13)	0.24400 (11)	0.0229 (3)
C103	0.8042 (2)	0.15150 (13)	0.15000 (12)	0.0264 (3)
C104	0.9089 (2)	0.17522 (14)	0.03539 (12)	0.0271 (3)
C105	0.9963 (2)	0.28495 (13)	0.01468 (12)	0.0260 (3)
C106	0.97496 (19)	0.37182 (13)	0.10797 (11)	0.0232 (3)
H1	0.8296	0.0716	0.5370	0.028*
H2	0.8210	−0.1274	0.6436	0.033*
H3	0.6791	−0.1117	0.8499	0.035*
H4	0.5425	0.1017	0.9472	0.034*
H5E	0.5243	0.3461	0.9485	0.031*
H5A	0.3806	0.3905	0.8633	0.031*
H6E	0.5700	0.5488	0.8400	0.030*
H6A	0.7780	0.4318	0.8244	0.030*
H7	0.6826	0.6574	0.6482	0.026*
H81A	0.7887	0.8315	0.3085	0.041*
H81B	0.8614	0.8186	0.4258	0.041*
H81C	0.6239	0.8474	0.4361	0.041*
H103	0.7479	0.0749	0.1644	0.032*
H102	0.7080	0.2212	0.3223	0.027*
H104	0.9208	0.1168	−0.0286	0.033*
H105	1.0708	0.3006	−0.0634	0.031*
H106	1.0362	0.4462	0.0938	0.028*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N9	0.0234 (5)	0.0204 (6)	0.0224 (6)	−0.0077 (4)	−0.0070 (4)	0.0028 (4)
N10	0.0236 (5)	0.0187 (5)	0.0174 (5)	−0.0069 (4)	−0.0046 (4)	0.0022 (4)
N11	0.0193 (5)	0.0223 (5)	0.0167 (5)	−0.0051 (4)	−0.0043 (4)	0.0016 (4)
C1	0.0216 (6)	0.0269 (7)	0.0199 (6)	−0.0071 (5)	−0.0042 (5)	0.0022 (5)
C2	0.0278 (7)	0.0250 (7)	0.0285 (7)	−0.0072 (5)	−0.0077 (5)	0.0026 (6)
C3	0.0315 (7)	0.0307 (8)	0.0270 (7)	−0.0109 (6)	−0.0082 (6)	0.0098 (6)
C4	0.0290 (7)	0.0364 (8)	0.0190 (7)	−0.0116 (6)	−0.0058 (5)	0.0059 (6)
C4a	0.0197 (6)	0.0309 (7)	0.0202 (7)	−0.0077 (5)	−0.0059 (5)	0.0017 (5)
C5	0.0262 (7)	0.0320 (7)	0.0191 (7)	−0.0072 (5)	−0.0058 (5)	0.0008 (5)
C6	0.0264 (7)	0.0295 (7)	0.0196 (7)	−0.0079 (5)	−0.0052 (5)	−0.0028 (5)
C6a	0.0165 (6)	0.0264 (7)	0.0190 (6)	−0.0056 (5)	−0.0032 (5)	−0.0019 (5)
C7	0.0176 (6)	0.0231 (6)	0.0224 (7)	−0.0052 (5)	−0.0038 (5)	−0.0036 (5)
C7a	0.0150 (6)	0.0221 (6)	0.0227 (7)	−0.0045 (5)	−0.0043 (5)	−0.0008 (5)
C8	0.0175 (6)	0.0227 (6)	0.0234 (7)	−0.0061 (5)	−0.0061 (5)	0.0002 (5)
C10a	0.0146 (6)	0.0237 (6)	0.0179 (6)	−0.0046 (5)	−0.0036 (5)	0.0005 (5)
C11a	0.0147 (6)	0.0251 (7)	0.0176 (6)	−0.0043 (5)	−0.0041 (5)	0.0009 (5)
C11b	0.0162 (6)	0.0272 (7)	0.0190 (6)	−0.0068 (5)	−0.0055 (5)	0.0030 (5)
C81	0.0302 (7)	0.0234 (7)	0.0305 (8)	−0.0086 (5)	−0.0099 (6)	0.0014 (6)
C101	0.0201 (6)	0.0209 (6)	0.0181 (6)	−0.0034 (5)	−0.0067 (5)	0.0001 (5)
C102	0.0221 (6)	0.0247 (7)	0.0208 (7)	−0.0065 (5)	−0.0043 (5)	0.0018 (5)
C103	0.0299 (7)	0.0233 (7)	0.0282 (7)	−0.0091 (5)	−0.0097 (6)	0.0008 (5)
C104	0.0335 (7)	0.0253 (7)	0.0236 (7)	−0.0054 (6)	−0.0112 (6)	−0.0028 (5)
C105	0.0316 (7)	0.0262 (7)	0.0185 (7)	−0.0060 (5)	−0.0060 (5)	0.0020 (5)
C106	0.0271 (7)	0.0235 (7)	0.0196 (7)	−0.0080 (5)	−0.0068 (5)	0.0028 (5)

Geometric parameters (Å, º) top

C1—C2	1.3864 (18)	C8—N9	1.3233 (17)
C1—C11b	1.4004 (18)	C8—C81	1.4907 (18)
C1—H1	0.95	C81—H81A	0.98
C2—C3	1.3900 (19)	C81—H81B	0.98
C2—H2	0.95	C81—H81C	0.98
C3—C4	1.384 (2)	N9—N10	1.3834 (14)
C3—H3	0.95	N10—C10a	1.3741 (16)
C4—C4a	1.3923 (18)	N10—C101	1.4202 (16)
C4—H4	0.95	C101—C106	1.3915 (17)
C4a—C11b	1.4022 (17)	C101—C102	1.3920 (17)
C4a—C5	1.5064 (19)	C103—C104	1.3859 (19)
C5—C6	1.5224 (18)	C103—C102	1.3879 (18)
C5—H5E	0.99	C103—H103	0.95
C5—H5A	0.99	C102—H102	0.95
C6—C6a	1.5080 (17)	C104—C105	1.3887 (18)
C6—H6E	0.99	C104—H104	0.95
C6—H6A	0.99	C105—C106	1.3884 (18)
C6a—C7	1.3848 (17)	C105—H105	0.95
C6a—C11a	1.4223 (18)	C106—H106	0.95
C7—C7a	1.3957 (17)	C10a—N11	1.3376 (16)
C7—H7	0.95	N11—C11a	1.3415 (16)
C7a—C10a	1.4028 (17)	C11a—C11b	1.4819 (17)
C7a—C8	1.4266 (17)

C2—C1—C11b	120.64 (12)	C8—C81—H81A	109.5
C2—C1—H1	119.7	C8—C81—H81B	109.5
C11b—C1—H1	119.7	H81A—C81—H81B	109.5
C1—C2—C3	119.65 (12)	C8—C81—H81C	109.5
C1—C2—H2	120.2	H81A—C81—H81C	109.5
C3—C2—H2	120.2	H81B—C81—H81C	109.5
C4—C3—C2	119.81 (12)	C8—N9—N10	107.14 (10)
C4—C3—H3	120.1	C10a—N10—N9	110.09 (10)
C2—C3—H3	120.1	C10a—N10—C101	130.59 (10)
C3—C4—C4a	121.50 (12)	N9—N10—C101	119.05 (10)
C3—C4—H4	119.2	C106—C101—C102	120.18 (11)
C4a—C4—H4	119.2	C106—C101—N10	118.95 (11)
C4—C4a—C11b	118.62 (12)	C102—C101—N10	120.83 (11)
C4—C4a—C5	121.78 (11)	C104—C103—C102	120.99 (12)
C11b—C4a—C5	119.58 (11)	C104—C103—H103	119.5
C4a—C5—C6	111.57 (11)	C102—C103—H103	119.5
C4a—C5—H5E	109.3	C103—C102—C101	119.17 (12)
C6—C5—H5E	109.3	C103—C102—H102	120.4
C4a—C5—H5A	109.3	C101—C102—H102	120.4
C6—C5—H5A	109.3	C103—C104—C105	119.54 (12)
H5E—C5—H5A	108.0	C103—C104—H104	120.2
C6a—C6—C5	112.69 (10)	C105—C104—H104	120.2
C6a—C6—H6E	109.1	C106—C105—C104	120.10 (12)
C5—C6—H6E	109.1	C106—C105—H105	120.0
C6a—C6—H6A	109.1	C104—C105—H105	120.0
C5—C6—H6A	109.1	C105—C106—C101	119.97 (12)
H6E—C6—H6A	107.8	C105—C106—H106	120.0
C7—C6a—C11a	118.89 (11)	C101—C106—H106	120.0
C7—C6a—C6	122.34 (11)	N11—C10a—N10	126.33 (11)
C11a—C6a—C6	118.66 (11)	N11—C10a—C7a	126.58 (11)
C6a—C7—C7a	118.42 (11)	N10—C10a—C7a	107.08 (11)
C6a—C7—H7	120.8	C10a—N11—C11a	114.72 (10)
C7a—C7—H7	120.8	N11—C11a—C6a	124.08 (11)
C7—C7a—C10a	117.29 (11)	N11—C11a—C11b	116.51 (11)
C7—C7a—C8	137.65 (12)	C6a—C11a—C11b	119.38 (11)
C10a—C7a—C8	105.05 (11)	C1—C11b—C4a	119.74 (11)
N9—C8—C7a	110.62 (11)	C1—C11b—C11a	120.15 (11)
N9—C8—C81	120.75 (11)	C4a—C11b—C11a	120.10 (11)
C7a—C8—C81	128.60 (12)

C11b—C1—C2—C3	1.23 (18)	C103—C104—C105—C106	−1.4 (2)
C1—C2—C3—C4	0.58 (19)	C104—C105—C106—C101	−0.73 (19)
C2—C3—C4—C4a	−1.8 (2)	C102—C101—C106—C105	2.40 (18)
C3—C4—C4a—C11b	1.08 (19)	N10—C101—C106—C105	−175.44 (11)
C3—C4—C4a—C5	179.30 (12)	N9—N10—C10a—N11	179.88 (10)
C4—C4a—C5—C6	147.22 (12)	C101—N10—C10a—N11	6.07 (19)
C11b—C4a—C5—C6	−34.57 (15)	N9—N10—C10a—C7a	−1.19 (13)
C4a—C5—C6—C6a	48.85 (14)	C101—N10—C10a—C7a	−175.00 (11)
C5—C6—C6a—C7	149.47 (12)	C7—C7a—C10a—N11	0.84 (17)
C5—C6—C6a—C11a	−34.42 (15)	C8—C7a—C10a—N11	−179.85 (11)
C11a—C6a—C7—C7a	0.15 (17)	C7—C7a—C10a—N10	−178.08 (10)
C6—C6a—C7—C7a	176.25 (11)	C8—C7a—C10a—N10	1.23 (12)
C6a—C7—C7a—C10a	−1.05 (16)	N10—C10a—N11—C11a	179.10 (10)
C6a—C7—C7a—C8	179.93 (13)	C7a—C10a—N11—C11a	0.38 (17)
C7—C7a—C8—N9	178.21 (13)	C10a—N11—C11a—C6a	−1.40 (16)
C10a—C7a—C8—N9	−0.88 (13)	C10a—N11—C11a—C11b	−179.39 (9)
C7—C7a—C8—C81	−3.7 (2)	C7—C6a—C11a—N11	1.18 (17)
C10a—C7a—C8—C81	177.22 (11)	C6—C6a—C11a—N11	−175.07 (11)
C7a—C8—N9—N10	0.17 (13)	C7—C6a—C11a—C11b	179.12 (10)
C81—C8—N9—N10	−178.10 (10)	C6—C6a—C11a—C11b	2.87 (16)
C8—N9—N10—C10a	0.64 (12)	C2—C1—C11b—C4a	−1.90 (18)
C8—N9—N10—C101	175.27 (10)	C2—C1—C11b—C11a	177.28 (11)
C10a—N10—C101—C106	−159.94 (12)	C4—C4a—C11b—C1	0.74 (17)
N9—N10—C101—C106	26.70 (16)	C5—C4a—C11b—C1	−177.53 (11)
C10a—N10—C101—C102	22.24 (18)	C4—C4a—C11b—C11a	−178.43 (10)
N9—N10—C101—C102	−151.12 (11)	C5—C4a—C11b—C11a	3.30 (17)
C104—C103—C102—C101	−0.20 (19)	N11—C11a—C11b—C1	12.73 (16)
C106—C101—C102—C103	−1.92 (18)	C6a—C11a—C11b—C1	−165.36 (11)
N10—C101—C102—C103	175.87 (11)	N11—C11a—C11b—C4a	−168.10 (10)
C102—C103—C104—C105	1.8 (2)	C6a—C11a—C11b—C4a	13.81 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5A···N9ⁱ	0.99	2.60	3.407 (2)	139

Symmetry code: (i) −x+1, −y+1, −z+1.

(II) 8-methyl-7,10-diphenyl-6,10-dihydro-5H-benzo[h]pyrazolo[3,4-b]quinoline top

Crystal data top

C₂₇H₂₁N₃	F(000) = 816
M_r = 387.47	D_x = 1.294 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4539 reflections
a = 11.5561 (4) Å	θ = 2.9–27.5°
b = 17.6751 (7) Å	µ = 0.08 mm⁻¹
c = 9.8469 (3) Å	T = 120 K
β = 98.599 (2)°	Block, yellow
V = 1988.67 (12) Å³	0.40 × 0.20 × 0.20 mm
Z = 4

Data collection top

Bruker Nonius KappaCCD area-detector diffractometer	4539 independent reflections
Radiation source: Bruker Nonius FR91 rotating anode	3236 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.053
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.5°, θ_min = 2.9°
ϕ and ω scans	h = −15→13
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −22→22
T_min = 0.973, T_max = 0.985	l = −12→12
26788 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.126	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0639P)² + 0.3388P] where P = (F_o² + 2F_c²)/3
4539 reflections	(Δ/σ)_max < 0.001
272 parameters	Δρ_max = 0.28 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₂₇H₂₁N₃	V = 1988.67 (12) Å³
M_r = 387.47	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.5561 (4) Å	µ = 0.08 mm⁻¹
b = 17.6751 (7) Å	T = 120 K
c = 9.8469 (3) Å	0.40 × 0.20 × 0.20 mm
β = 98.599 (2)°

Data collection top

Bruker Nonius KappaCCD area-detector diffractometer	4539 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	3236 reflections with I > 2σ(I)
T_min = 0.973, T_max = 0.985	R_int = 0.053
26788 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.126	H-atom parameters constrained
S = 1.08	Δρ_max = 0.28 e Å⁻³
4539 reflections	Δρ_min = −0.29 e Å⁻³
272 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N9	0.43577 (11)	0.58317 (7)	0.12922 (12)	0.0246 (3)
N10	0.34752 (10)	0.54838 (7)	0.18563 (12)	0.0226 (3)
N11	0.33013 (10)	0.44465 (7)	0.34202 (11)	0.0203 (3)
C1	0.21854 (13)	0.35978 (9)	0.52740 (15)	0.0253 (3)
C2	0.15848 (14)	0.31124 (9)	0.60241 (16)	0.0304 (4)
C3	0.21065 (15)	0.24434 (10)	0.65426 (16)	0.0316 (4)
C4	0.32201 (14)	0.22656 (9)	0.62946 (16)	0.0305 (4)
C4a	0.38337 (13)	0.27438 (8)	0.55394 (15)	0.0257 (3)
C5	0.50310 (15)	0.25435 (9)	0.52218 (19)	0.0355 (4)
C6	0.57792 (13)	0.32386 (9)	0.51646 (16)	0.0292 (4)
C6a	0.51771 (13)	0.38214 (8)	0.41929 (14)	0.0227 (3)
C7	0.57744 (13)	0.42877 (9)	0.33974 (16)	0.0285 (4)
C7a	0.51099 (12)	0.48429 (8)	0.25861 (14)	0.0218 (3)
C8	0.53342 (13)	0.54537 (8)	0.17123 (14)	0.0236 (3)
C10a	0.39155 (12)	0.48847 (8)	0.26655 (13)	0.0203 (3)
C11a	0.39426 (12)	0.39257 (8)	0.41779 (13)	0.0198 (3)
C11b	0.33103 (12)	0.34207 (8)	0.50193 (13)	0.0209 (3)
C71	0.70476 (13)	0.41902 (8)	0.33270 (15)	0.0228 (3)
C72	0.74131 (13)	0.39804 (9)	0.20979 (15)	0.0252 (3)
C73	0.85936 (13)	0.38897 (9)	0.20265 (16)	0.0286 (4)
C74	0.94184 (13)	0.40076 (9)	0.31732 (16)	0.0289 (4)
C75	0.90609 (13)	0.42152 (9)	0.43990 (16)	0.0287 (4)
C76	0.78855 (13)	0.43018 (8)	0.44813 (15)	0.0268 (3)
C81	0.64537 (13)	0.57005 (9)	0.12594 (16)	0.0302 (4)
C101	0.23436 (12)	0.58166 (8)	0.16747 (14)	0.0233 (3)
C102	0.22464 (14)	0.66001 (9)	0.15294 (15)	0.0296 (4)
C103	0.11490 (15)	0.69317 (10)	0.13306 (16)	0.0353 (4)
C104	0.01560 (15)	0.64928 (10)	0.12814 (16)	0.0355 (4)
C105	0.02594 (14)	0.57183 (11)	0.14374 (17)	0.0351 (4)
C106	0.13507 (13)	0.53746 (9)	0.16269 (15)	0.0285 (4)
H1	0.1828	0.4057	0.4929	0.030*
H2	0.0817	0.3237	0.6184	0.036*
H3	0.1700	0.2110	0.7064	0.038*
H4	0.3573	0.1807	0.6648	0.037*
H5A	0.4952	0.2277	0.4328	0.043*
H5E	0.5419	0.2196	0.5937	0.043*
H6A	0.5959	0.3461	0.6095	0.035*
H6E	0.6528	0.3093	0.4864	0.035*
H72	0.6851	0.3899	0.1304	0.030*
H73	0.8837	0.3745	0.1184	0.034*
H74	1.0227	0.3946	0.3120	0.035*
H75	0.9627	0.4299	0.5189	0.034*
H76	0.7647	0.4438	0.5331	0.032*
H81A	0.6669	0.5341	0.0581	0.045*
H81B	0.7075	0.5717	0.2054	0.045*
H81C	0.6351	0.6205	0.0846	0.045*
H102	0.2929	0.6904	0.1567	0.036*
H103	0.1079	0.7465	0.1227	0.042*
H104	−0.0596	0.6723	0.1141	0.043*
H105	−0.0424	0.5418	0.1415	0.042*
H106	0.1415	0.4841	0.1723	0.034*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N9	0.0258 (7)	0.0241 (7)	0.0243 (6)	−0.0023 (5)	0.0052 (5)	0.0026 (5)
N10	0.0231 (6)	0.0214 (6)	0.0237 (6)	0.0003 (5)	0.0044 (5)	0.0035 (5)
N11	0.0225 (6)	0.0198 (6)	0.0189 (6)	0.0024 (5)	0.0046 (5)	0.0007 (5)
C1	0.0253 (8)	0.0266 (8)	0.0245 (7)	0.0029 (6)	0.0045 (6)	0.0030 (6)
C2	0.0267 (8)	0.0352 (9)	0.0309 (8)	0.0013 (7)	0.0094 (7)	0.0033 (7)
C3	0.0353 (9)	0.0325 (9)	0.0283 (8)	−0.0046 (7)	0.0094 (7)	0.0055 (7)
C4	0.0343 (9)	0.0248 (8)	0.0330 (9)	0.0015 (7)	0.0065 (7)	0.0085 (7)
C4a	0.0279 (8)	0.0231 (8)	0.0264 (8)	0.0019 (6)	0.0052 (6)	0.0016 (6)
C5	0.0318 (9)	0.0262 (9)	0.0510 (11)	0.0064 (7)	0.0141 (8)	0.0098 (7)
C6	0.0267 (8)	0.0287 (8)	0.0328 (8)	0.0064 (7)	0.0063 (6)	0.0059 (7)
C6a	0.0219 (7)	0.0227 (8)	0.0233 (7)	0.0004 (6)	0.0021 (6)	0.0014 (6)
C7	0.0252 (8)	0.0289 (8)	0.0328 (8)	0.0042 (7)	0.0086 (6)	0.0051 (7)
C7a	0.0229 (7)	0.0232 (8)	0.0194 (7)	0.0017 (6)	0.0038 (6)	−0.0001 (6)
C8	0.0267 (8)	0.0238 (8)	0.0204 (7)	0.0001 (6)	0.0036 (6)	0.0007 (6)
C10a	0.0250 (8)	0.0192 (7)	0.0164 (7)	0.0020 (6)	0.0024 (6)	−0.0001 (5)
C11a	0.0221 (7)	0.0193 (7)	0.0182 (7)	0.0015 (6)	0.0037 (6)	−0.0024 (5)
C11b	0.0234 (8)	0.0226 (7)	0.0168 (7)	−0.0008 (6)	0.0032 (6)	−0.0014 (6)
C71	0.0225 (7)	0.0200 (7)	0.0264 (8)	0.0022 (6)	0.0051 (6)	0.0037 (6)
C72	0.0245 (8)	0.0279 (8)	0.0224 (7)	−0.0012 (6)	0.0012 (6)	0.0014 (6)
C73	0.0299 (9)	0.0321 (9)	0.0260 (8)	0.0014 (7)	0.0114 (6)	0.0015 (7)
C74	0.0185 (7)	0.0314 (9)	0.0373 (9)	−0.0001 (6)	0.0057 (6)	0.0058 (7)
C75	0.0281 (8)	0.0257 (8)	0.0297 (8)	−0.0026 (7)	−0.0042 (6)	−0.0004 (6)
C76	0.0329 (9)	0.0239 (8)	0.0235 (8)	0.0044 (7)	0.0042 (6)	−0.0014 (6)
C81	0.0280 (9)	0.0320 (9)	0.0312 (8)	−0.0029 (7)	0.0067 (7)	0.0057 (7)
C101	0.0247 (8)	0.0266 (8)	0.0182 (7)	0.0049 (6)	0.0021 (6)	0.0011 (6)
C102	0.0340 (9)	0.0268 (8)	0.0268 (8)	0.0037 (7)	0.0008 (6)	−0.0002 (6)
C103	0.0451 (10)	0.0311 (9)	0.0287 (8)	0.0144 (8)	0.0022 (7)	−0.0012 (7)
C104	0.0328 (9)	0.0480 (11)	0.0266 (8)	0.0179 (8)	0.0079 (7)	0.0060 (7)
C105	0.0267 (9)	0.0466 (11)	0.0328 (9)	0.0033 (8)	0.0066 (7)	0.0095 (8)
C106	0.0288 (8)	0.0290 (9)	0.0280 (8)	0.0028 (7)	0.0050 (6)	0.0073 (6)

Geometric parameters (Å, º) top

C1—C2	1.384 (2)	C10a—N11	1.3467 (18)
C1—C11b	1.396 (2)	N11—C11a	1.3370 (18)
C1—H1	0.95	C11a—C11b	1.483 (2)
C2—C3	1.389 (2)	C71—C72	1.391 (2)
C2—H2	0.95	C71—C76	1.393 (2)
C3—C4	1.381 (2)	C72—C73	1.386 (2)
C3—H3	0.95	C72—H72	0.95
C4—C4a	1.389 (2)	C73—C74	1.380 (2)
C4—H4	0.95	C73—H73	0.95
C4a—C11b	1.402 (2)	C74—C75	1.383 (2)
C4a—C5	1.506 (2)	C74—H74	0.95
C5—C6	1.508 (2)	C75—C76	1.381 (2)
C5—H5A	0.99	C75—H75	0.95
C5—H5E	0.99	C76—H76	0.95
C6—C6a	1.504 (2)	C81—H81A	0.98
C6—H6A	0.99	C81—H81B	0.98
C6—H6E	0.99	C81—H81C	0.98
C6a—C7	1.390 (2)	C101—C106	1.383 (2)
C6a—C11a	1.436 (2)	C101—C102	1.395 (2)
C7—C7a	1.417 (2)	C102—C103	1.384 (2)
C7—C71	1.493 (2)	C102—H102	0.95
C7a—C10a	1.396 (2)	C103—C104	1.380 (3)
C7a—C8	1.428 (2)	C103—H103	0.95
C8—N9	1.3234 (19)	C104—C105	1.381 (3)
C8—C81	1.495 (2)	C104—H104	0.95
N9—N10	1.3769 (17)	C105—C106	1.387 (2)
N10—C10a	1.3762 (18)	C105—H105	0.95
N10—C101	1.4206 (18)	C106—H106	0.95

C2—C1—C11b	120.77 (14)	N11—C11a—C11b	116.61 (12)
C2—C1—H1	119.6	C6a—C11a—C11b	119.25 (12)
C11b—C1—H1	119.6	C1—C11b—C4a	119.22 (13)
C1—C2—C3	119.92 (15)	C1—C11b—C11a	121.02 (13)
C1—C2—H2	120.0	C4a—C11b—C11a	119.73 (13)
C3—C2—H2	120.0	C72—C71—C76	118.92 (14)
C4—C3—C2	119.55 (15)	C72—C71—C7	120.05 (13)
C4—C3—H3	120.2	C76—C71—C7	121.03 (13)
C2—C3—H3	120.2	C73—C72—C71	120.30 (14)
C3—C4—C4a	121.33 (15)	C73—C72—H72	119.9
C3—C4—H4	119.3	C71—C72—H72	119.9
C4a—C4—H4	119.3	C74—C73—C72	120.37 (14)
C4—C4a—C11b	119.20 (14)	C74—C73—H73	119.8
C4—C4a—C5	121.79 (14)	C72—C73—H73	119.8
C11b—C4a—C5	118.97 (13)	C73—C74—C75	119.63 (14)
C4a—C5—C6	111.46 (13)	C73—C74—H74	120.2
C4a—C5—H5A	109.3	C75—C74—H74	120.2
C6—C5—H5A	109.3	C76—C75—C74	120.36 (14)
C4a—C5—H5E	109.3	C76—C75—H75	119.8
C6—C5—H5E	109.3	C74—C75—H75	119.8
H5A—C5—H5E	108.0	C75—C76—C71	120.41 (14)
C6a—C6—C5	111.62 (13)	C75—C76—H76	119.8
C6a—C6—H6A	109.3	C71—C76—H76	119.8
C5—C6—H6A	109.3	C8—C81—H81A	109.5
C6a—C6—H6E	109.3	C8—C81—H81B	109.5
C5—C6—H6E	109.3	H81A—C81—H81B	109.5
H6A—C6—H6E	108.0	C8—C81—H81C	109.5
C7—C6a—C11a	119.63 (13)	H81A—C81—H81C	109.5
C7—C6a—C6	122.91 (13)	H81B—C81—H81C	109.5
C11a—C6a—C6	117.31 (13)	C106—C101—C102	120.23 (14)
C6a—C7—C7a	117.10 (14)	C106—C101—N10	120.92 (14)
C6a—C7—C71	122.26 (13)	C102—C101—N10	118.85 (14)
C7a—C7—C71	120.56 (13)	C103—C102—C101	119.54 (15)
C10a—C7a—C7	117.52 (13)	C103—C102—H102	120.2
C10a—C7a—C8	105.29 (12)	C101—C102—H102	120.2
C7—C7a—C8	137.00 (14)	C104—C103—C102	120.42 (16)
N9—C8—C7a	110.29 (13)	C104—C103—H103	119.8
N9—C8—C81	119.67 (13)	C102—C103—H103	119.8
C7a—C8—C81	130.04 (13)	C103—C104—C105	119.72 (15)
C8—N9—N10	107.27 (12)	C103—C104—H104	120.1
C10a—N10—N9	110.19 (11)	C105—C104—H104	120.1
C10a—N10—C101	130.18 (12)	C104—C105—C106	120.74 (16)
N9—N10—C101	119.19 (12)	C104—C105—H105	119.6
N11—C10a—N10	125.61 (13)	C106—C105—H105	119.6
N11—C10a—C7a	127.41 (13)	C101—C106—C105	119.35 (15)
N10—C10a—C7a	106.94 (12)	C101—C106—H106	120.3
C11a—N11—C10a	114.20 (12)	C105—C106—H106	120.3
N11—C11a—C6a	124.12 (13)

C11b—C1—C2—C3	0.6 (2)	C7—C6a—C11a—N11	1.0 (2)
C1—C2—C3—C4	−0.5 (2)	C6—C6a—C11a—N11	176.62 (13)
C2—C3—C4—C4a	0.2 (2)	C7—C6a—C11a—C11b	179.40 (13)
C3—C4—C4a—C11b	0.0 (2)	C6—C6a—C11a—C11b	−4.9 (2)
C3—C4—C4a—C5	−177.88 (15)	C2—C1—C11b—C4a	−0.3 (2)
C4—C4a—C5—C6	−147.16 (15)	C2—C1—C11b—C11a	177.95 (13)
C11b—C4a—C5—C6	34.9 (2)	C4—C4a—C11b—C1	0.1 (2)
C4a—C5—C6—C6a	−53.40 (19)	C5—C4a—C11b—C1	178.00 (14)
C5—C6—C6a—C7	−145.07 (15)	C4—C4a—C11b—C11a	−178.27 (13)
C5—C6—C6a—C11a	39.42 (19)	C5—C4a—C11b—C11a	−0.3 (2)
C11a—C6a—C7—C7a	−0.9 (2)	N11—C11a—C11b—C1	−15.48 (19)
C6—C6a—C7—C7a	−176.34 (14)	C6a—C11a—C11b—C1	165.96 (13)
C11a—C6a—C7—C71	−177.67 (13)	N11—C11a—C11b—C4a	162.81 (13)
C6—C6a—C7—C71	6.9 (2)	C6a—C11a—C11b—C4a	−15.75 (19)
C6a—C7—C7a—C10a	0.9 (2)	C6a—C7—C71—C72	114.74 (17)
C71—C7—C7a—C10a	177.72 (13)	C7a—C7—C71—C72	−61.9 (2)
C6a—C7—C7a—C8	175.16 (16)	C6a—C7—C71—C76	−64.9 (2)
C71—C7—C7a—C8	−8.0 (3)	C7a—C7—C71—C76	118.49 (17)
C10a—C7a—C8—N9	−0.27 (16)	C76—C71—C72—C73	−0.4 (2)
C7—C7a—C8—N9	−174.97 (17)	C7—C71—C72—C73	179.95 (14)
C10a—C7a—C8—C81	179.29 (14)	C71—C72—C73—C74	−0.1 (2)
C7—C7a—C8—C81	4.6 (3)	C72—C73—C74—C75	0.2 (2)
C7a—C8—N9—N10	−0.51 (16)	C73—C74—C75—C76	0.3 (2)
C81—C8—N9—N10	179.88 (12)	C74—C75—C76—C71	−0.8 (2)
C8—N9—N10—C10a	1.13 (15)	C72—C71—C76—C75	0.9 (2)
C8—N9—N10—C101	174.26 (12)	C7—C71—C76—C75	−179.51 (14)
N9—N10—C10a—N11	176.60 (13)	C10a—N10—C101—C106	−38.4 (2)
C101—N10—C10a—N11	4.4 (2)	N9—N10—C101—C106	150.00 (13)
N9—N10—C10a—C7a	−1.29 (15)	C10a—N10—C101—C102	142.24 (15)
C101—N10—C10a—C7a	−173.44 (13)	N9—N10—C101—C102	−29.31 (19)
C7—C7a—C10a—N11	−1.0 (2)	C106—C101—C102—C103	−0.3 (2)
C8—C7a—C10a—N11	−176.91 (13)	N10—C101—C102—C103	179.02 (13)
C7—C7a—C10a—N10	176.86 (13)	C101—C102—C103—C104	0.3 (2)
C8—C7a—C10a—N10	0.93 (15)	C102—C103—C104—C105	0.3 (2)
N10—C10a—N11—C11a	−176.54 (13)	C103—C104—C105—C106	−0.8 (2)
C7a—C10a—N11—C11a	0.9 (2)	C102—C101—C106—C105	−0.2 (2)
C10a—N11—C11a—C6a	−0.87 (19)	N10—C101—C106—C105	−179.49 (13)
C10a—N11—C11a—C11b	−179.35 (12)	C104—C105—C106—C101	0.7 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···Cg1ⁱ	0.95	2.82	3.7461 (17)	164
C73—H73···Cg2ⁱⁱ	0.95	2.62	3.4852 (17)	152

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

(III) 8-methyl-7-(4-methylphenyl)-10-phenyl-6,10-dihydro-5H- benzo[h]pyrazolo[3,4-b]quinoline top

Crystal data top

C₂₈H₂₃N₃	F(000) = 848
M_r = 401.49	D_x = 1.280 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4778 reflections
a = 12.0313 (3) Å	θ = 3.2–27.5°
b = 14.3347 (4) Å	µ = 0.08 mm⁻¹
c = 12.7956 (3) Å	T = 120 K
β = 109.3092 (14)°	Lath, yellow
V = 2082.66 (9) Å³	0.66 × 0.42 × 0.14 mm
Z = 4

Data collection top

Bruker Nonius KappaCCD area-detector diffractometer	4778 independent reflections
Radiation source: Bruker Nonius FR91 rotating anode	3416 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.059
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.5°, θ_min = 3.2°
ϕ and ω scans	h = −15→15
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −18→18
T_min = 0.956, T_max = 0.989	l = −16→16
38247 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.129	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.066P)² + 0.5056P] where P = (F_o² + 2F_c²)/3
4778 reflections	(Δ/σ)_max < 0.001
282 parameters	Δρ_max = 0.41 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₂₈H₂₃N₃	V = 2082.66 (9) Å³
M_r = 401.49	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.0313 (3) Å	µ = 0.08 mm⁻¹
b = 14.3347 (4) Å	T = 120 K
c = 12.7956 (3) Å	0.66 × 0.42 × 0.14 mm
β = 109.3092 (14)°

Data collection top

Bruker Nonius KappaCCD area-detector diffractometer	4778 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	3416 reflections with I > 2σ(I)
T_min = 0.956, T_max = 0.989	R_int = 0.059
38247 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.129	H-atom parameters constrained
S = 1.04	Δρ_max = 0.41 e Å⁻³
4778 reflections	Δρ_min = −0.31 e Å⁻³
282 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N9	0.30634 (11)	0.65547 (9)	0.73214 (10)	0.0258 (3)
N10	0.30409 (10)	0.66474 (9)	0.62375 (9)	0.0240 (3)
N11	0.43992 (10)	0.64102 (9)	0.52311 (9)	0.0226 (3)
C1	0.50934 (13)	0.64311 (11)	0.33420 (12)	0.0267 (3)
C2	0.54058 (15)	0.63637 (11)	0.23984 (13)	0.0304 (4)
C3	0.64913 (15)	0.59966 (12)	0.24608 (13)	0.0322 (4)
C4	0.72493 (14)	0.56801 (12)	0.34689 (13)	0.0317 (4)
C4a	0.69491 (13)	0.57393 (11)	0.44258 (12)	0.0264 (3)
C5	0.77415 (14)	0.53670 (12)	0.55198 (12)	0.0314 (4)
C6	0.76520 (13)	0.59487 (12)	0.64686 (13)	0.0315 (4)
C6a	0.63895 (12)	0.60365 (11)	0.64328 (12)	0.0244 (3)
C7	0.60599 (13)	0.60251 (11)	0.73788 (12)	0.0243 (3)
C7a	0.48778 (12)	0.62315 (10)	0.72366 (11)	0.0219 (3)
C8	0.41448 (13)	0.63049 (10)	0.79173 (12)	0.0239 (3)
C10a	0.41290 (12)	0.64386 (10)	0.61634 (11)	0.0217 (3)
C11a	0.55248 (12)	0.61967 (10)	0.53789 (12)	0.0217 (3)
C11b	0.58595 (12)	0.61283 (10)	0.43662 (12)	0.0226 (3)
C71	0.69221 (12)	0.57974 (11)	0.84904 (12)	0.0247 (3)
C72	0.74078 (13)	0.49082 (12)	0.87080 (12)	0.0294 (4)
C73	0.82076 (14)	0.46872 (12)	0.97366 (13)	0.0315 (4)
C74	0.85460 (13)	0.53490 (12)	1.05790 (12)	0.0297 (4)
C75	0.80652 (14)	0.62366 (12)	1.03547 (12)	0.0302 (4)
C76	0.72639 (13)	0.64641 (11)	0.93260 (12)	0.0274 (3)
C77	0.94094 (16)	0.50995 (15)	1.17000 (14)	0.0450 (5)
C81	0.44431 (14)	0.61437 (12)	0.91309 (12)	0.0296 (4)
C101	0.19686 (12)	0.68698 (10)	0.53990 (11)	0.0235 (3)
C102	0.09135 (13)	0.67465 (12)	0.56059 (12)	0.0285 (4)
C103	−0.01409 (14)	0.69713 (12)	0.47966 (13)	0.0328 (4)
C104	−0.01591 (14)	0.73023 (12)	0.37762 (13)	0.0343 (4)
C105	0.08906 (14)	0.74071 (12)	0.35707 (13)	0.0329 (4)
C106	0.19587 (13)	0.72066 (12)	0.43766 (12)	0.0289 (4)
H1	0.4349	0.6686	0.3295	0.032*
H2	0.4876	0.6569	0.1707	0.036*
H3	0.6715	0.5962	0.1816	0.039*
H4	0.7987	0.5418	0.3506	0.038*
H5A	0.7519	0.4715	0.5612	0.038*
H5E	0.8567	0.5367	0.5526	0.038*
H6A	0.7978	0.6578	0.6433	0.038*
H6E	0.8126	0.5658	0.7178	0.038*
H72	0.7188	0.4446	0.8144	0.035*
H73	0.8529	0.4076	0.9868	0.038*
H75	0.8289	0.6699	1.0918	0.036*
H76	0.6948	0.7077	0.9193	0.033*
H77A	0.9695	0.5671	1.2124	0.068*
H77B	1.0076	0.4759	1.1604	0.068*
H77C	0.9018	0.4706	1.2099	0.068*
H81A	0.4839	0.6696	0.9536	0.044*
H81B	0.4967	0.5603	0.9352	0.044*
H81C	0.3719	0.6026	0.9302	0.044*
H102	0.0916	0.6509	0.6300	0.034*
H103	−0.0860	0.6897	0.4944	0.039*
H104	−0.0885	0.7456	0.3223	0.041*
H105	0.0881	0.7620	0.2865	0.039*
H106	0.2676	0.7298	0.4232	0.035*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N9	0.0268 (7)	0.0306 (8)	0.0208 (6)	0.0015 (5)	0.0086 (5)	0.0010 (5)
N10	0.0213 (6)	0.0305 (7)	0.0201 (6)	0.0029 (5)	0.0067 (5)	0.0015 (5)
N11	0.0222 (6)	0.0230 (7)	0.0226 (6)	0.0002 (5)	0.0075 (5)	0.0001 (5)
C1	0.0291 (8)	0.0245 (8)	0.0263 (8)	0.0012 (6)	0.0091 (6)	0.0000 (6)
C2	0.0393 (9)	0.0288 (9)	0.0233 (8)	−0.0015 (7)	0.0107 (7)	0.0000 (6)
C3	0.0385 (9)	0.0350 (10)	0.0276 (8)	−0.0067 (7)	0.0169 (7)	−0.0057 (7)
C4	0.0286 (8)	0.0360 (10)	0.0343 (9)	−0.0020 (7)	0.0157 (7)	−0.0052 (7)
C4a	0.0271 (8)	0.0252 (8)	0.0276 (8)	−0.0030 (6)	0.0101 (6)	−0.0024 (6)
C5	0.0246 (8)	0.0380 (10)	0.0325 (8)	0.0053 (7)	0.0107 (6)	0.0006 (7)
C6	0.0244 (8)	0.0404 (10)	0.0287 (8)	0.0021 (7)	0.0075 (6)	0.0025 (7)
C6a	0.0216 (7)	0.0260 (8)	0.0246 (7)	0.0010 (6)	0.0063 (6)	0.0007 (6)
C7	0.0241 (7)	0.0241 (8)	0.0235 (7)	0.0007 (6)	0.0063 (6)	0.0002 (6)
C7a	0.0227 (7)	0.0213 (8)	0.0210 (7)	0.0004 (6)	0.0061 (6)	−0.0006 (6)
C8	0.0245 (7)	0.0236 (8)	0.0231 (7)	0.0011 (6)	0.0070 (6)	0.0007 (6)
C10a	0.0212 (7)	0.0216 (8)	0.0226 (7)	0.0008 (6)	0.0075 (6)	0.0001 (6)
C11a	0.0218 (7)	0.0182 (8)	0.0247 (7)	−0.0013 (6)	0.0075 (6)	−0.0002 (6)
C11b	0.0246 (7)	0.0191 (8)	0.0246 (7)	−0.0035 (6)	0.0087 (6)	−0.0011 (6)
C71	0.0196 (7)	0.0317 (9)	0.0225 (7)	0.0010 (6)	0.0067 (6)	0.0020 (6)
C72	0.0288 (8)	0.0306 (9)	0.0265 (8)	0.0012 (7)	0.0060 (6)	−0.0018 (6)
C73	0.0311 (8)	0.0310 (9)	0.0313 (8)	0.0069 (7)	0.0090 (7)	0.0082 (7)
C74	0.0243 (8)	0.0404 (10)	0.0232 (7)	0.0013 (7)	0.0062 (6)	0.0052 (7)
C75	0.0290 (8)	0.0352 (10)	0.0236 (8)	−0.0017 (7)	0.0052 (6)	−0.0023 (7)
C76	0.0268 (8)	0.0272 (9)	0.0271 (8)	0.0028 (6)	0.0074 (6)	0.0015 (6)
C77	0.0407 (10)	0.0597 (13)	0.0278 (9)	0.0106 (9)	0.0022 (7)	0.0075 (8)
C81	0.0291 (8)	0.0373 (10)	0.0230 (7)	0.0040 (7)	0.0095 (6)	0.0033 (6)
C101	0.0212 (7)	0.0236 (8)	0.0232 (7)	0.0025 (6)	0.0043 (6)	−0.0012 (6)
C102	0.0264 (8)	0.0351 (9)	0.0243 (8)	0.0027 (7)	0.0089 (6)	−0.0013 (6)
C103	0.0229 (8)	0.0421 (10)	0.0325 (9)	0.0019 (7)	0.0079 (7)	−0.0029 (7)
C104	0.0265 (8)	0.0408 (10)	0.0300 (8)	0.0065 (7)	0.0017 (6)	0.0012 (7)
C105	0.0337 (9)	0.0358 (10)	0.0264 (8)	0.0054 (7)	0.0062 (7)	0.0064 (7)
C106	0.0271 (8)	0.0302 (9)	0.0300 (8)	0.0027 (7)	0.0100 (6)	0.0047 (6)

Geometric parameters (Å, º) top

C1—C2	1.381 (2)	C75—H75	0.95
C1—C11b	1.399 (2)	C76—H76	0.95
C1—H1	0.95	C77—H77A	0.98
C2—C3	1.386 (2)	C77—H77B	0.98
C2—H2	0.95	C77—H77C	0.98
C3—C4	1.387 (2)	C7a—C10a	1.4026 (19)
C3—H3	0.95	C7a—C8	1.434 (2)
C4—C4a	1.389 (2)	C8—N9	1.3214 (19)
C4—H4	0.95	C8—C81	1.492 (2)
C4a—C11b	1.403 (2)	C81—H81A	0.98
C4a—C5	1.507 (2)	C81—H81B	0.98
C5—C6	1.506 (2)	C81—H81C	0.98
C5—H5A	0.99	N9—N10	1.3845 (16)
C5—H5E	0.99	N10—C10a	1.3764 (18)
C6—C6a	1.510 (2)	N10—C101	1.4148 (18)
C6—H6A	0.99	C101—C106	1.391 (2)
C6—H6E	0.99	C101—C102	1.391 (2)
C6a—C7	1.393 (2)	C102—C103	1.385 (2)
C6a—C11a	1.423 (2)	C102—H102	0.95
C7—C7a	1.404 (2)	C103—C104	1.383 (2)
C7—C71	1.4933 (19)	C103—H103	0.95
C71—C76	1.391 (2)	C104—C105	1.381 (2)
C71—C72	1.391 (2)	C104—H104	0.95
C72—C73	1.386 (2)	C105—C106	1.386 (2)
C72—H72	0.95	C105—H105	0.95
C73—C74	1.392 (2)	C106—H106	0.95
C73—H73	0.95	C10a—N11	1.3367 (18)
C74—C75	1.388 (2)	N11—C11a	1.3394 (18)
C74—C77	1.510 (2)	C11a—C11b	1.482 (2)
C75—C76	1.389 (2)

C2—C1—C11b	120.78 (14)	C74—C77—H77A	109.5
C2—C1—H1	119.6	C74—C77—H77B	109.5
C11b—C1—H1	119.6	H77A—C77—H77B	109.5
C1—C2—C3	119.99 (15)	C74—C77—H77C	109.5
C1—C2—H2	120.0	H77A—C77—H77C	109.5
C3—C2—H2	120.0	H77B—C77—H77C	109.5
C2—C3—C4	119.69 (14)	C10a—C7a—C7	117.81 (13)
C2—C3—H3	120.2	C10a—C7a—C8	104.73 (12)
C4—C3—H3	120.2	C7—C7a—C8	137.46 (13)
C3—C4—C4a	121.14 (15)	N9—C8—C7a	110.82 (12)
C3—C4—H4	119.4	N9—C8—C81	119.65 (13)
C4a—C4—H4	119.4	C7a—C8—C81	129.53 (13)
C4—C4a—C11b	119.14 (14)	C8—C81—H81A	109.5
C4—C4a—C5	121.88 (14)	C8—C81—H81B	109.5
C11b—C4a—C5	118.95 (13)	H81A—C81—H81B	109.5
C6—C5—C4a	111.16 (13)	C8—C81—H81C	109.5
C6—C5—H5A	109.4	H81A—C81—H81C	109.5
C4a—C5—H5A	109.4	H81B—C81—H81C	109.5
C6—C5—H5E	109.4	C8—N9—N10	107.06 (12)
C4a—C5—H5E	109.4	C10a—N10—N9	110.13 (11)
H5A—C5—H5E	108.0	C10a—N10—C101	130.26 (12)
C5—C6—C6a	111.17 (13)	N9—N10—C101	119.49 (11)
C5—C6—H6A	109.4	C106—C101—C102	119.91 (14)
C6a—C6—H6A	109.4	C106—C101—N10	120.91 (13)
C5—C6—H6E	109.4	C102—C101—N10	119.19 (13)
C6a—C6—H6E	109.4	C103—C102—C101	119.75 (14)
H6A—C6—H6E	108.0	C103—C102—H102	120.1
C7—C6a—C11a	119.75 (13)	C101—C102—H102	120.1
C7—C6a—C6	123.05 (13)	C104—C103—C102	120.72 (15)
C11a—C6a—C6	117.08 (13)	C104—C103—H103	119.6
C6a—C7—C7a	116.88 (13)	C102—C103—H103	119.6
C6a—C7—C71	121.50 (13)	C105—C104—C103	119.16 (14)
C7a—C7—C71	121.62 (13)	C105—C104—H104	120.4
C76—C71—C72	118.54 (14)	C103—C104—H104	120.4
C76—C71—C7	121.17 (14)	C104—C105—C106	121.14 (15)
C72—C71—C7	120.29 (13)	C104—C105—H105	119.4
C73—C72—C71	120.87 (15)	C106—C105—H105	119.4
C73—C72—H72	119.6	C105—C106—C101	119.30 (14)
C71—C72—H72	119.6	C105—C106—H106	120.4
C72—C73—C74	120.87 (15)	C101—C106—H106	120.4
C72—C73—H73	119.6	N11—C10a—N10	125.85 (13)
C74—C73—H73	119.6	N11—C10a—C7a	126.89 (13)
C75—C74—C73	118.00 (14)	N10—C10a—C7a	107.23 (12)
C75—C74—C77	121.50 (15)	C10a—N11—C11a	114.45 (12)
C73—C74—C77	120.50 (16)	N11—C11a—C6a	123.97 (13)
C74—C75—C76	121.50 (15)	N11—C11a—C11b	116.49 (12)
C74—C75—H75	119.2	C6a—C11a—C11b	119.54 (13)
C76—C75—H75	119.2	C1—C11b—C4a	119.25 (13)
C75—C76—C71	120.22 (15)	C1—C11b—C11a	120.89 (13)
C75—C76—H76	119.9	C4a—C11b—C11a	119.85 (13)
C71—C76—H76	119.9

C11b—C1—C2—C3	−0.3 (2)	C8—N9—N10—C101	177.07 (13)
C1—C2—C3—C4	1.4 (2)	C10a—N10—C101—C106	−21.6 (2)
C2—C3—C4—C4a	−1.2 (3)	N9—N10—C101—C106	162.93 (14)
C3—C4—C4a—C11b	−0.1 (2)	C10a—N10—C101—C102	158.27 (15)
C3—C4—C4a—C5	177.70 (15)	N9—N10—C101—C102	−17.2 (2)
C4—C4a—C5—C6	146.82 (15)	C106—C101—C102—C103	−0.8 (2)
C11b—C4a—C5—C6	−35.4 (2)	N10—C101—C102—C103	179.28 (14)
C4a—C5—C6—C6a	54.16 (18)	C101—C102—C103—C104	1.1 (3)
C5—C6—C6a—C7	141.78 (16)	C102—C103—C104—C105	0.0 (3)
C5—C6—C6a—C11a	−42.3 (2)	C103—C104—C105—C106	−1.5 (3)
C11a—C6a—C7—C7a	−3.7 (2)	C104—C105—C106—C101	1.8 (3)
C6—C6a—C7—C7a	172.13 (14)	C102—C101—C106—C105	−0.6 (2)
C11a—C6a—C7—C71	175.89 (14)	N10—C101—C106—C105	179.29 (14)
C6—C6a—C7—C71	−8.3 (2)	N9—N10—C10a—N11	176.29 (14)
C6a—C7—C71—C76	113.66 (17)	C101—N10—C10a—N11	0.5 (2)
C7a—C7—C71—C76	−66.8 (2)	N9—N10—C10a—C7a	−1.67 (16)
C6a—C7—C71—C72	−65.9 (2)	C101—N10—C10a—C7a	−177.45 (14)
C7a—C7—C71—C72	113.63 (17)	C7—C7a—C10a—N11	4.2 (2)
C76—C71—C72—C73	0.5 (2)	C8—C7a—C10a—N11	−176.11 (14)
C7—C71—C72—C73	−179.90 (14)	C7—C7a—C10a—N10	−177.89 (13)
C71—C72—C73—C74	0.0 (2)	C8—C7a—C10a—N10	1.82 (16)
C72—C73—C74—C75	−0.5 (2)	N10—C10a—N11—C11a	179.46 (14)
C72—C73—C74—C77	179.44 (15)	C7a—C10a—N11—C11a	−3.0 (2)
C73—C74—C75—C76	0.4 (2)	C10a—N11—C11a—C6a	−1.8 (2)
C77—C74—C75—C76	−179.49 (15)	C10a—N11—C11a—C11b	178.21 (13)
C74—C75—C76—C71	0.1 (2)	C7—C6a—C11a—N11	5.2 (2)
C72—C71—C76—C75	−0.6 (2)	C6—C6a—C11a—N11	−170.92 (14)
C7—C71—C76—C75	179.86 (14)	C7—C6a—C11a—C11b	−174.82 (14)
C6a—C7—C7a—C10a	−0.5 (2)	C6—C6a—C11a—C11b	9.1 (2)
C71—C7—C7a—C10a	179.94 (14)	C2—C1—C11b—C4a	−1.0 (2)
C6a—C7—C7a—C8	179.93 (17)	C2—C1—C11b—C11a	−179.77 (14)
C71—C7—C7a—C8	0.4 (3)	C4—C4a—C11b—C1	1.2 (2)
C10a—C7a—C8—N9	−1.42 (17)	C5—C4a—C11b—C1	−176.71 (14)
C7—C7a—C8—N9	178.20 (17)	C4—C4a—C11b—C11a	179.97 (14)
C10a—C7a—C8—C81	178.61 (15)	C5—C4a—C11b—C11a	2.1 (2)
C7—C7a—C8—C81	−1.8 (3)	N11—C11a—C11b—C1	10.8 (2)
C7a—C8—N9—N10	0.43 (17)	C6a—C11a—C11b—C1	−169.21 (14)
C81—C8—N9—N10	−179.60 (13)	N11—C11a—C11b—C4a	−167.97 (14)
C8—N9—N10—C10a	0.77 (16)	C6a—C11a—C11b—C4a	12.0 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C73—H73···Cg2ⁱ	0.95	2.96	3.8991 (18)	168
C76—H76···Cg3ⁱⁱ	0.95	2.90	3.8349 (17)	168

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

(IV) 7-(4-methoxyphenyl)-8-methyl-10-phenyl-6,10-dihydro-5H- benzo[h]pyrazolo[3,4-b]quinoline top

Crystal data top

C₂₈H₂₃N₃O	F(000) = 880
M_r = 417.49	D_x = 1.283 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4963 reflections
a = 12.9148 (3) Å	θ = 3.3–27.5°
b = 17.5938 (5) Å	µ = 0.08 mm⁻¹
c = 9.8192 (2) Å	T = 120 K
β = 104.3370 (17)°	Plate, pale brown
V = 2161.64 (9) Å³	0.50 × 0.20 × 0.05 mm
Z = 4

Data collection top

Bruker Nonius KappaCCD area-detector diffractometer	4963 independent reflections
Radiation source: Bruker Nonius FR91 rotating anode	3449 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.062
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.5°, θ_min = 3.3°
ϕ and ω scans	h = −16→16
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −22→22
T_min = 0.974, T_max = 0.996	l = −12→11
35681 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.112	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0534P)² + 0.4296P] where P = (F_o² + 2F_c²)/3
4963 reflections	(Δ/σ)_max = 0.001
291 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₂₈H₂₃N₃O	V = 2161.64 (9) Å³
M_r = 417.49	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.9148 (3) Å	µ = 0.08 mm⁻¹
b = 17.5938 (5) Å	T = 120 K
c = 9.8192 (2) Å	0.50 × 0.20 × 0.05 mm
β = 104.3370 (17)°

Data collection top

Bruker Nonius KappaCCD area-detector diffractometer	4963 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	3449 reflections with I > 2σ(I)
T_min = 0.974, T_max = 0.996	R_int = 0.062
35681 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.112	H-atom parameters constrained
S = 1.04	Δρ_max = 0.21 e Å⁻³
4963 reflections	Δρ_min = −0.27 e Å⁻³
291 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O7	−0.00309 (8)	0.60663 (7)	0.03830 (11)	0.0377 (3)
N9	0.56190 (9)	0.41506 (7)	0.15846 (12)	0.0237 (3)
N10	0.64399 (9)	0.44956 (7)	0.25661 (11)	0.0209 (3)
N11	0.66123 (9)	0.55376 (6)	0.42113 (11)	0.0198 (3)
C1	0.76553 (11)	0.63739 (9)	0.66044 (14)	0.0250 (3)
C2	0.82021 (12)	0.68454 (9)	0.76705 (15)	0.0298 (4)
C3	0.77204 (12)	0.75040 (10)	0.79858 (15)	0.0322 (4)
C4	0.67023 (12)	0.76916 (9)	0.72270 (15)	0.0300 (4)
C4a	0.61388 (11)	0.72238 (8)	0.61543 (14)	0.0244 (3)
C5	0.50473 (12)	0.74353 (9)	0.52858 (16)	0.0308 (4)
C6	0.43597 (11)	0.67437 (9)	0.48495 (15)	0.0261 (3)
C6a	0.49047 (11)	0.61550 (8)	0.41528 (13)	0.0203 (3)
C7	0.43553 (11)	0.57136 (8)	0.30262 (13)	0.0202 (3)
C7a	0.49543 (11)	0.51598 (8)	0.25225 (13)	0.0198 (3)
C8	0.47405 (11)	0.45416 (8)	0.15370 (14)	0.0221 (3)
C10a	0.60502 (11)	0.51027 (8)	0.31725 (13)	0.0192 (3)
C11a	0.60280 (10)	0.60557 (8)	0.46939 (13)	0.0189 (3)
C11b	0.66193 (11)	0.65542 (8)	0.58432 (13)	0.0208 (3)
C71	0.31912 (11)	0.58090 (8)	0.23634 (14)	0.0206 (3)
C72	0.24315 (11)	0.57061 (8)	0.31310 (14)	0.0233 (3)
C73	0.13443 (11)	0.57765 (9)	0.25071 (15)	0.0254 (3)
C74	0.10111 (11)	0.59604 (8)	0.10945 (15)	0.0245 (3)
C75	0.17600 (11)	0.60728 (9)	0.03142 (14)	0.0255 (3)
C76	0.28378 (11)	0.59988 (8)	0.09389 (14)	0.0236 (3)
C77	−0.08224 (13)	0.59641 (15)	0.1150 (2)	0.0576 (6)
C81	0.37100 (11)	0.42962 (9)	0.05751 (15)	0.0273 (3)
C101	0.74468 (11)	0.41267 (8)	0.29682 (14)	0.0217 (3)
C102	0.74869 (12)	0.33419 (9)	0.28130 (15)	0.0285 (3)
C103	0.84610 (13)	0.29716 (10)	0.31932 (17)	0.0365 (4)
C104	0.93899 (13)	0.33738 (10)	0.37330 (16)	0.0357 (4)
C105	0.93435 (12)	0.41570 (10)	0.38817 (16)	0.0330 (4)
C106	0.83735 (11)	0.45363 (9)	0.35031 (14)	0.0258 (3)
H1	0.7987	0.5923	0.6388	0.030*
H2	0.8905	0.6718	0.8184	0.036*
H3	0.8090	0.7826	0.8723	0.039*
H4	0.6381	0.8148	0.7441	0.036*
H5A	0.5118	0.7713	0.4437	0.037*
H5E	0.4698	0.7778	0.5837	0.037*
H6A	0.3681	0.6898	0.4190	0.031*
H6E	0.4185	0.6517	0.5688	0.031*
H72	0.2659	0.5585	0.4102	0.028*
H73	0.0835	0.5699	0.3045	0.030*
H75	0.1530	0.6201	−0.0654	0.031*
H76	0.3344	0.6077	0.0397	0.028*
H77A	−0.0808	0.5437	0.1474	0.086*
H77B	−0.1529	0.6079	0.0541	0.086*
H77C	−0.0675	0.6306	0.1962	0.086*
H81A	0.3492	0.4667	−0.0187	0.041*
H81B	0.3159	0.4264	0.1102	0.041*
H81C	0.3802	0.3797	0.0179	0.041*
H102	0.6849	0.3062	0.2448	0.034*
H103	0.8491	0.2436	0.3082	0.044*
H104	1.0056	0.3117	0.4001	0.043*
H105	0.9982	0.4435	0.4246	0.040*
H106	0.8345	0.5072	0.3610	0.031*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O7	0.0183 (5)	0.0595 (8)	0.0324 (6)	0.0006 (5)	0.0009 (4)	0.0116 (5)
N9	0.0242 (7)	0.0253 (7)	0.0209 (6)	−0.0027 (5)	0.0042 (5)	−0.0026 (5)
N10	0.0208 (6)	0.0215 (6)	0.0202 (6)	0.0007 (5)	0.0045 (5)	−0.0027 (5)
N11	0.0215 (6)	0.0196 (6)	0.0181 (6)	0.0010 (5)	0.0048 (4)	0.0019 (4)
C1	0.0242 (8)	0.0270 (8)	0.0230 (7)	0.0017 (6)	0.0044 (6)	−0.0003 (6)
C2	0.0255 (8)	0.0369 (9)	0.0244 (8)	−0.0017 (7)	0.0013 (6)	0.0002 (6)
C3	0.0330 (9)	0.0367 (10)	0.0249 (8)	−0.0050 (7)	0.0035 (6)	−0.0091 (6)
C4	0.0328 (9)	0.0282 (9)	0.0284 (8)	0.0018 (7)	0.0065 (6)	−0.0073 (6)
C4a	0.0255 (8)	0.0249 (8)	0.0227 (7)	0.0010 (6)	0.0059 (6)	−0.0016 (6)
C5	0.0282 (8)	0.0265 (9)	0.0349 (8)	0.0064 (7)	0.0025 (6)	−0.0059 (7)
C6	0.0233 (8)	0.0271 (9)	0.0272 (8)	0.0047 (6)	0.0051 (6)	−0.0024 (6)
C6a	0.0216 (7)	0.0201 (8)	0.0186 (7)	0.0020 (6)	0.0041 (5)	0.0027 (5)
C7	0.0215 (7)	0.0207 (7)	0.0187 (7)	0.0021 (6)	0.0057 (5)	0.0044 (5)
C7a	0.0206 (7)	0.0213 (8)	0.0174 (6)	−0.0003 (6)	0.0045 (5)	0.0024 (5)
C10a	0.0216 (7)	0.0190 (7)	0.0174 (6)	0.0009 (6)	0.0055 (5)	0.0023 (5)
C11a	0.0219 (7)	0.0184 (7)	0.0167 (6)	0.0015 (6)	0.0052 (5)	0.0038 (5)
C11b	0.0231 (7)	0.0222 (8)	0.0171 (6)	−0.0008 (6)	0.0052 (5)	0.0019 (5)
C71	0.0208 (7)	0.0194 (7)	0.0209 (7)	0.0005 (6)	0.0040 (5)	−0.0007 (5)
C72	0.0235 (7)	0.0262 (8)	0.0193 (7)	0.0021 (6)	0.0034 (6)	0.0037 (6)
C73	0.0216 (7)	0.0295 (8)	0.0259 (7)	−0.0014 (6)	0.0076 (6)	0.0036 (6)
C74	0.0175 (7)	0.0267 (8)	0.0262 (8)	0.0006 (6)	−0.0005 (6)	0.0022 (6)
C75	0.0267 (8)	0.0308 (9)	0.0171 (7)	0.0013 (6)	0.0017 (6)	0.0020 (6)
C76	0.0232 (7)	0.0269 (8)	0.0210 (7)	0.0001 (6)	0.0060 (5)	0.0000 (6)
C77	0.0208 (9)	0.1029 (18)	0.0480 (11)	−0.0027 (10)	0.0062 (8)	0.0209 (11)
C8	0.0243 (7)	0.0227 (8)	0.0190 (7)	−0.0006 (6)	0.0051 (5)	0.0015 (5)
C81	0.0260 (8)	0.0281 (8)	0.0263 (8)	−0.0015 (7)	0.0033 (6)	−0.0037 (6)
C101	0.0235 (7)	0.0243 (8)	0.0189 (7)	0.0052 (6)	0.0081 (5)	0.0022 (5)
C102	0.0301 (8)	0.0259 (9)	0.0321 (8)	0.0015 (7)	0.0124 (6)	0.0017 (6)
C103	0.0416 (10)	0.0286 (9)	0.0438 (9)	0.0122 (8)	0.0193 (8)	0.0083 (7)
C104	0.0322 (9)	0.0428 (11)	0.0330 (9)	0.0161 (8)	0.0093 (7)	0.0075 (7)
C105	0.0243 (8)	0.0443 (11)	0.0297 (8)	0.0050 (7)	0.0050 (6)	−0.0025 (7)
C106	0.0263 (8)	0.0274 (8)	0.0245 (7)	0.0031 (6)	0.0080 (6)	−0.0023 (6)

Geometric parameters (Å, º) top

C1—C2	1.384 (2)	C75—H75	0.95
C1—C11b	1.3980 (19)	C76—H76	0.95
C1—H1	0.95	O7—C77	1.423 (2)
C2—C3	1.386 (2)	C77—H77A	0.98
C2—H2	0.95	C77—H77B	0.98
C3—C4	1.381 (2)	C77—H77C	0.98
C3—H3	0.95	C7a—C10a	1.4047 (18)
C4—C4a	1.392 (2)	C7a—C8	1.4365 (19)
C4—H4	0.95	C8—N9	1.3177 (18)
C4a—C11b	1.400 (2)	C8—C81	1.4923 (19)
C4a—C5	1.503 (2)	C81—H81A	0.98
C5—C6	1.505 (2)	C81—H81B	0.98
C5—H5A	0.99	C81—H81C	0.98
C5—H5E	0.99	N9—N10	1.3840 (15)
C6—C6a	1.5082 (19)	N10—C10a	1.3774 (17)
C6—H6A	0.99	N10—C101	1.4191 (17)
C6—H6E	0.99	C101—C106	1.384 (2)
C6a—C7	1.3934 (19)	C101—C102	1.392 (2)
C6a—C11a	1.4268 (19)	C102—C103	1.383 (2)
C7—C7a	1.408 (2)	C102—H102	0.95
C7—C71	1.4925 (19)	C103—C104	1.381 (2)
C71—C72	1.3892 (19)	C103—H103	0.95
C71—C76	1.4001 (19)	C104—C105	1.389 (2)
C72—C73	1.3914 (19)	C104—H104	0.95
C72—H72	0.95	C105—C106	1.387 (2)
C73—C74	1.3850 (19)	C105—H105	0.95
C73—H73	0.95	C106—H106	0.95
C74—O7	1.3668 (16)	C10a—N11	1.3365 (17)
C74—C75	1.389 (2)	N11—C11a	1.3423 (18)
C75—C76	1.3812 (19)	C11a—C11b	1.4830 (19)

C2—C1—C11b	120.64 (14)	C74—O7—C77	117.24 (12)
C2—C1—H1	119.7	O7—C77—H77A	109.5
C11b—C1—H1	119.7	O7—C77—H77B	109.5
C1—C2—C3	119.79 (14)	H77A—C77—H77B	109.5
C1—C2—H2	120.1	O7—C77—H77C	109.5
C3—C2—H2	120.1	H77A—C77—H77C	109.5
C4—C3—C2	119.95 (14)	H77B—C77—H77C	109.5
C4—C3—H3	120.0	C10a—C7a—C7	117.99 (12)
C2—C3—H3	120.0	C10a—C7a—C8	104.83 (12)
C3—C4—C4a	121.09 (14)	C7—C7a—C8	136.89 (13)
C3—C4—H4	119.5	N9—C8—C7a	110.56 (12)
C4a—C4—H4	119.5	N9—C8—C81	119.77 (13)
C4—C4a—C11b	119.07 (13)	C7a—C8—C81	129.64 (13)
C4—C4a—C5	121.62 (13)	C8—C81—H81A	109.5
C11b—C4a—C5	119.26 (12)	C8—C81—H81B	109.5
C4a—C5—C6	111.46 (12)	H81A—C81—H81B	109.5
C4a—C5—H5A	109.3	C8—C81—H81C	109.5
C6—C5—H5A	109.3	H81A—C81—H81C	109.5
C4a—C5—H5E	109.3	H81B—C81—H81C	109.5
C6—C5—H5E	109.3	C8—N9—N10	107.46 (11)
H5A—C5—H5E	108.0	C10a—N10—N9	110.01 (11)
C5—C6—C6a	112.06 (12)	C10a—N10—C101	129.95 (11)
C5—C6—H6A	109.2	N9—N10—C101	118.97 (11)
C6a—C6—H6A	109.2	C106—C101—C102	120.40 (13)
C5—C6—H6E	109.2	C106—C101—N10	120.93 (13)
C6a—C6—H6E	109.2	C102—C101—N10	118.67 (13)
H6A—C6—H6E	107.9	C103—C102—C101	119.59 (15)
C7—C6a—C11a	119.88 (12)	C103—C102—H102	120.2
C7—C6a—C6	122.67 (12)	C101—C102—H102	120.2
C11a—C6a—C6	117.45 (12)	C104—C103—C102	120.53 (16)
C6a—C7—C7a	116.65 (12)	C104—C103—H103	119.7
C6a—C7—C71	122.92 (12)	C102—C103—H103	119.7
C7a—C7—C71	120.43 (12)	C103—C104—C105	119.54 (15)
C72—C71—C76	118.28 (12)	C103—C104—H104	120.2
C72—C71—C7	121.29 (12)	C105—C104—H104	120.2
C76—C71—C7	120.43 (12)	C106—C105—C104	120.61 (15)
C71—C72—C73	121.39 (13)	C106—C105—H105	119.7
C71—C72—H72	119.3	C104—C105—H105	119.7
C73—C72—H72	119.3	C101—C106—C105	119.34 (15)
C74—C73—C72	119.42 (13)	C101—C106—H106	120.3
C74—C73—H73	120.3	C105—C106—H106	120.3
C72—C73—H73	120.3	N11—C10a—N10	125.90 (12)
O7—C74—C73	124.48 (13)	N11—C10a—C7a	126.98 (12)
O7—C74—C75	115.51 (12)	N10—C10a—C7a	107.10 (11)
C73—C74—C75	119.98 (13)	C10a—N11—C11a	114.30 (11)
C76—C75—C74	120.30 (13)	N11—C11a—C6a	124.08 (12)
C76—C75—H75	119.9	N11—C11a—C11b	116.21 (12)
C74—C75—H75	119.9	C6a—C11a—C11b	119.70 (12)
C75—C76—C71	120.63 (13)	C1—C11b—C4a	119.44 (13)
C75—C76—H76	119.7	C1—C11b—C11a	121.13 (12)
C71—C76—H76	119.7	C4a—C11b—C11a	119.42 (12)

C11b—C1—C2—C3	−0.2 (2)	C8—N9—N10—C10a	1.90 (15)
C1—C2—C3—C4	−0.7 (2)	C8—N9—N10—C101	171.27 (11)
C2—C3—C4—C4a	0.9 (2)	C10a—N10—C101—C106	−37.2 (2)
C3—C4—C4a—C11b	−0.2 (2)	N9—N10—C101—C106	155.87 (12)
C3—C4—C4a—C5	−177.71 (14)	C10a—N10—C101—C102	142.88 (14)
C4—C4a—C5—C6	−146.79 (14)	N9—N10—C101—C102	−24.06 (18)
C11b—C4a—C5—C6	35.72 (19)	C106—C101—C102—C103	−0.2 (2)
C4a—C5—C6—C6a	−52.28 (17)	N10—C101—C102—C103	179.74 (12)
C5—C6—C6a—C7	−142.94 (13)	C101—C102—C103—C104	0.4 (2)
C5—C6—C6a—C11a	37.32 (17)	C102—C103—C104—C105	−0.6 (2)
C11a—C6a—C7—C7a	2.78 (19)	C103—C104—C105—C106	0.5 (2)
C6—C6a—C7—C7a	−176.95 (13)	C102—C101—C106—C105	0.1 (2)
C11a—C6a—C7—C71	−177.20 (12)	N10—C101—C106—C105	−179.84 (13)
C6—C6a—C7—C71	3.1 (2)	C104—C105—C106—C101	−0.2 (2)
C6a—C7—C71—C72	−60.70 (19)	N9—N10—C10a—N11	176.34 (12)
C7a—C7—C71—C72	119.32 (15)	C101—N10—C10a—N11	8.5 (2)
C6a—C7—C71—C76	119.91 (15)	N9—N10—C10a—C7a	−1.95 (14)
C7a—C7—C71—C76	−60.08 (19)	C101—N10—C10a—C7a	−169.80 (13)
C76—C71—C72—C73	1.0 (2)	C7—C7a—C10a—N11	−2.2 (2)
C7—C71—C72—C73	−178.41 (13)	C8—C7a—C10a—N11	−177.04 (13)
C71—C72—C73—C74	−0.7 (2)	C7—C7a—C10a—N10	176.07 (12)
C72—C73—C74—O7	−177.97 (14)	C8—C7a—C10a—N10	1.23 (14)
C72—C73—C74—C75	0.0 (2)	N10—C10a—N11—C11a	−174.93 (12)
O7—C74—C75—C76	178.42 (13)	C7a—C10a—N11—C11a	3.02 (19)
C73—C74—C75—C76	0.3 (2)	C10a—N11—C11a—C6a	−0.86 (19)
C74—C75—C76—C71	0.1 (2)	C10a—N11—C11a—C11b	−179.70 (11)
C72—C71—C76—C75	−0.7 (2)	C7—C6a—C11a—N11	−2.0 (2)
C7—C71—C76—C75	178.70 (13)	C6—C6a—C11a—N11	177.74 (13)
C73—C74—O7—C77	−1.3 (2)	C7—C6a—C11a—C11b	176.79 (12)
C75—C74—O7—C77	−179.38 (16)	C6—C6a—C11a—C11b	−3.46 (18)
C6a—C7—C7a—C10a	−0.91 (18)	C2—C1—C11b—C4a	0.8 (2)
C71—C7—C7a—C10a	179.07 (12)	C2—C1—C11b—C11a	179.66 (13)
C6a—C7—C7a—C8	171.79 (15)	C4—C4a—C11b—C1	−0.6 (2)
C71—C7—C7a—C8	−8.2 (2)	C5—C4a—C11b—C1	176.93 (13)
C10a—C7a—C8—N9	−0.09 (15)	C4—C4a—C11b—C11a	−179.49 (13)
C7—C7a—C8—N9	−173.42 (15)	C5—C4a—C11b—C11a	−1.9 (2)
C10a—C7a—C8—C81	177.82 (13)	N11—C11a—C11b—C1	−15.23 (19)
C7—C7a—C8—C81	4.5 (3)	C6a—C11a—C11b—C1	165.87 (13)
C7a—C8—N9—N10	−1.09 (15)	N11—C11a—C11b—C4a	163.62 (12)
C81—C8—N9—N10	−179.22 (12)	C6a—C11a—C11b—C4a	−15.28 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O7ⁱ	0.95	2.53	3.3422 (18)	144
C72—H72···N11ⁱⁱ	0.95	2.60	3.3952 (17)	142
C4—H4···Cg1ⁱⁱⁱ	0.95	2.84	3.7766 (17)	168
C75—H75···Cg2^iv	0.95	2.67	3.5605 (15)	157
C103—H103···Cg4^v	0.95	2.85	3.7417 (19)	157

Symmetry codes: (i) x+1, y, z+1; (ii) −x+1, −y+1, −z+1; (iii) x, −y+3/2, z+1/2; (iv) −x+1, −y+1, −z; (v) −x+1, y−1/2, −z+1/2.

Experimental details

	(I)	(II)	(III)	(IV)
Crystal data
Chemical formula	C₂₁H₁₇N₃	C₂₇H₂₁N₃	C₂₈H₂₃N₃	C₂₈H₂₃N₃O
M_r	311.38	387.47	401.49	417.49
Crystal system, space group	Triclinic, P1	Monoclinic, P2₁/c	Monoclinic, P2₁/c	Monoclinic, P2₁/c
Temperature (K)	120	120	120	120
a, b, c (Å)	7.0870 (2), 10.1321 (4), 11.7977 (5)	11.5561 (4), 17.6751 (7), 9.8469 (3)	12.0313 (3), 14.3347 (4), 12.7956 (3)	12.9148 (3), 17.5938 (5), 9.8192 (2)
α, β, γ (°)	87.501 (2), 73.171 (3), 74.828 (2)	90, 98.599 (2), 90	90, 109.3092 (14), 90	90, 104.3370 (17), 90
V (Å³)	782.13 (5)	1988.67 (12)	2082.66 (9)	2161.64 (9)
Z	2	4	4	4
Radiation type	Mo Kα	Mo Kα	Mo Kα	Mo Kα
µ (mm⁻¹)	0.08	0.08	0.08	0.08
Crystal size (mm)	0.50 × 0.10 × 0.10	0.40 × 0.20 × 0.20	0.66 × 0.42 × 0.14	0.50 × 0.20 × 0.05

Data collection
Diffractometer	Bruker Nonius KappaCCD area-detector diffractometer	Bruker Nonius KappaCCD area-detector diffractometer	Bruker Nonius KappaCCD area-detector diffractometer	Bruker Nonius KappaCCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)	Multi-scan (SADABS; Sheldrick, 2003)	Multi-scan (SADABS; Sheldrick, 2003)	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.954, 0.992	0.973, 0.985	0.956, 0.989	0.974, 0.996
No. of measured, independent and observed [I > 2σ(I)] reflections	15116, 3576, 2810	26788, 4539, 3236	38247, 4778, 3416	35681, 4963, 3449
R_int	0.039	0.053	0.059	0.062
(sin θ/λ)_max (Å⁻¹)	0.651	0.650	0.650	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.114, 1.04	0.048, 0.126, 1.08	0.050, 0.129, 1.04	0.044, 0.112, 1.04
No. of reflections	3576	4539	4778	4963
No. of parameters	218	272	282	291
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.28	0.28, −0.29	0.41, −0.31	0.21, −0.27

Computer programs: COLLECT (Hooft, 1999), DENZO (Otwinowski & Minor, 1997) and COLLECT, DENZO and COLLECT, OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997), OSCAIL and SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97 and PRPKAPPA (Ferguson, 1999).

Ring-puckering parameters and selected dihedral angles (Å, °) for compounds (I)–(IV) top

Parameter	(I)	(II)	(III)	(IV)
Q	0.423 (2)	0.461 (2)	0.460 (2)	0.450 (2)
θ	63.9 (2)	115.4 (2)	61.5 (2)	115.5 (2)
ϕ	89.6 (2)	274.1 (2)	96.6 (2)	271.6 (2)
(C1–C4,C4a,C11b)/pyridine	13.84 (7)	15.78 (7)	11.11 (7)	14.79 (7)
(C71–C76)/pyridine		63.45 (7)	65.27 (7)	60.88 (7)
(C101–C106)/pyrazole	26.21 (7)	33.16 (8)	18.56 (8)	30.30 (4)

The ring-puckering parameters for the non-aromatic carbocyclic ring are calculated for the atom sequence C4a/C5/C6/C6a/C11a/C11b.

Hydrogen-bond geometry (Å, °) for compounds (I)–(IV) top

Compound	D—H···A	D—H	H···A	D···A	D—H···A
(I)	C5—H5A···N9ⁱ	0.99	2.60	3.4070 (18)	139
(II)	C4—H4···Cg1ⁱⁱ	0.95	2.82	3.7461 (17)	164
	C73—H73···Cg2ⁱⁱⁱ	0.95	2.62	3.4852 (17)	152
(III)	C73—H73···Cg2^iv	0.95	2.96	3.8991 (18)	168
	C76—H76···Cg3^v	0.95	2.90	3.8349 (17)	168
(IV)	C2—H2···O7^vi	0.95	2.53	3.3422 (18)	144
	C72—H72···N11ⁱ	0.95	2.60	3.3952 (17)	142
	C4—H4···Cg1^v	0.95	2.84	3.7766 (17)	168
	C75—H75···Cg2ⁱⁱⁱ	0.95	2.67	3.5605 (15)	157
	C103—H103···Cg4^vii	0.95	2.85	3.7417 (19)	157

Cg1–Cg4 are the centroids of the rings N11/C10a/C7a/C7/C6a/C11a, C101–C106, C1–C4/C4a/C11a and C71–C76, respectively. Symmetry codes: (i) 1 − x, 1 − y, 1 − z; (ii) x, 1/2 − y, 1/2 + z; (iii) 1 − x, 1 − y, −z; (iv) 1 − x, y − 1/2, 3/2 − z; (v) x, 3/2 − y, 1/2 + z; (vi) 1 + x, y, 1 + z; (vii) 1 − x, y − 1/2, 1/2 − z.

Acknowledgements

The X-ray data were collected at the EPSRC X-ray Crystallographic Service, University of Southampton. JC thanks the Consejería de Innovación, Ciencia y Empresa (Junta de Andalucía, Spain) and the Universidad de Jaén for financial support. JQ and JP thank COLCIENCIAS and UNIVALLE (Universidad del Valle, Colombia) for financial support.

References

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Evans, D. G. & Boeyens, J. C. A. (1989). Acta Cryst. B45, 581–590. CrossRef CAS Web of Science IUCr Journals Google Scholar
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Hooft, R. W. W. (1999). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
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Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
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ISSN: 2053-2296

Volume 61| Part 8| August 2005| Pages o483-o489

doi:10.1107/S0108270105020093

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Effect of substitution on the dimensionality of supramolecular aggregation in di­hydro­benzo­pyrazolo­quinolines

Comment

Experimental

Compound (I)

Crystal data

Data collection

Refinement

Compound (II)

Crystal data

Data collection

Refinement

Compound (III)

Crystal data

Data collection

Refinement

Compound (IV)

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

Effect of substitution on the dimensionality of supramolecular aggregation in dihydrobenzopyrazoloquinolines