Molecular conformation and supramolecular aggregation in two fused pyrazoles: π-stacked R_{\bf 2}^{\bf 2}(6) dimers in 2,8,8-tri­methyl-6,7,8,9-tetra­hydro­pyrazolo­[2,3-a]­quinazolin-6-one, and sheets of alternating R_2^2(12) and R_6^6(48) rings in 3-tert-butyl-4′,4′-di­methyl-1-phenyl-4,5,6,7-tetra­hydro-1H-pyrazolo­[3,4-b]­pyridine-5-spiro-1′-cyclo­hexane-2′,6′-dione

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

doi:10.1107/S0108270104004159

organic compounds

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 60| Part 4| April 2004| Pages o265-o269

doi:10.1107/S0108270104004159

Molecular conformation and supramolecular aggregation in two fused pyrazoles: π-stacked R $[_{\bf 2}^{\bf 2}]$ (6) dimers in 2,8,8-trimethyl-6,7,8,9-tetrahydropyrazolo[2,3-a]quinazolin-6-one, and sheets of alternating R(12) and R(48) rings in 3-tert-butyl-4′,4′-dimethyl-1-phenyl-4,5,6,7-tetrahydro-1H-pyrazolo[3,4-b]pyridine-5-spiro-1′-cyclohexane-2′,6′-dione

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

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

(Received 18 February 2004; accepted 20 February 2004; online 20 March 2004)

In 2,8,8-trimethyl-6,7,8,9-tetrahydropyrazolo[2,3-a]quinazolin-6-one, C₁₃H₁₅N₃O, (I), the heterobicyclic system is planar and exhibits peripheral ten π-electron delocalization. In 3-tert-butyl-4′,4′-dimethyl-1-phenyl-4,5,6,7-tetrahydro-1H- pyrazolo[3,4-b]pyridine-5-spiro-1′-cyclohexane-2′,6′-dione, C₂₃H₂₅N₃O₂, (II), the pyrazole ring exhibits marked bond fixation, while the reduced pyridine ring adopts a half-chair conformation. Molecules of (I) are linked into centrosymmetric [R_2^2] (6) dimers by a single C—H⋯N hydrogen bond [H⋯N = 2.50 Å, C⋯N = 3.3397 (17) Å and C—H⋯N = 148°], and these dimers are linked into chains by a single π–π stacking interaction. In (II), the combined action of one N—H⋯O hydrogen bond [H⋯O = 2.40 Å, N⋯O = 3.2248 (15) Å and N—H⋯O = 157°] and one C—H⋯O hydrogen bond [H⋯O = 2.48 Å, C⋯O = 3.407 (2) Å and C—H⋯O = 164°] links the molecules into sheets built from alternating centrosymmetric [R_2^2] (12) and [R_6^6] (48) rings; there is a weak C—H⋯N interaction [H⋯N = 2.60 Å, C⋯N = 3.5149 (18) Å and C—H⋯N = 154°] between molecules in adjacent sheets.

Comment

As part of a program aimed at the synthesis of fused pyrazolo derivatives (Quiroga et al., 1999 ), we have been investigating three-component cyclocondensations induced by microwave irradiation. From the reactions between formaldehyde, 5,5-dimethylcyclohexane-1,3-dione (dimedone) and either 5-amino-3-methyl-1H-pyrazole or 5-amino-3-tert-butyl-1-phenylpyrazole (which differ primarily in terms of the absence or presence of the substituent at atom N1), we have isolated two very different products, whose molecular and supramolecular structures are presented here. Using 5-amino-3-methyl-1H-pyrazole, which has only an H atom at N1, we obtained 2,8,8-trimethyl-6,7,8,9-tetrahydropyrazolo[2,3-a]quinazolin-6-one, (I), while with the N-phenyl-substituted 5-amino-3-tert-butyl-1-phenylpyrazole, the product was 3-tert-butyl-4′,4′-dimethyl-1-phenyl-4,5,6,7-tetrahydro-1H-pyrazolo[3,4-b]pyridine-5-spiro-1′-cyclohexane-2′,6′-dione, (II).

The presence or otherwise of a substituent at atom N1 in the precursor pyrazole appears to determine which two nucleophilic atoms participate in the cyclocondensation. Ring atom N1 and amine atom N5 are involved in the formation of (I), while ring atom C3 along with atom N5 are involved in the formation of (II). In the formation of (II), two molecules of formaldehyde give a double Mannich-type reaction between the activated methylene group in the dimedone component and the two nucleophilic residues of the pyrazole ring, resulting in an interesting spiro-pyrazolopyridine derivative.

In (I) (Fig. 1), the two fused heterocyclic rings (N1/N2/C3/C4/C4a/N5/C6/C6a/C10a) are completely planar, with the bond angles at each of atoms N1, C3, C4a, C6a and C10a independently summing to 360.0° within experimental uncertainty. For the carbocyclic ring (C6a/C7–C10/C10a), the ring-puckering parameters (Cremer & Pople, 1975 ) for the atom sequence C6a—C7⋯C10—C10a [θ = 54.3 (2)° and φ = 163.8 (2)°] indicate an envelope conformation (Evans & Boeyens, 1989 ), consistent with the enforced coplanarity of atoms C6a, C7, C10a and C10. This ring thus exhibits a pseudo-mirror plane passing through atoms C6a, C9, C91 and C92 (Fig. 1).

The bond lengths in the fused heterocyclic rings in (I) show some unusual values (Table 1). Thus, for example, the formally single C4a—N5 and C10a—N1 bonds are only slightly longer than the formally double C3=N2 bond, although each of these single bonds is significantly shorter than the formally single C4a—N1 bond. Similarly, the lengths of the C3—C4 and C4=C4a bonds, formally single and double bonds, respectively, differ by less than 0.03 Å. These observations, together with the planarity at atom N1, suggest that this heterocyclic system exhibits a degree of naphthalene-type delocalization, involving a peripheral system of ten π electrons with only modest participation by the cross-ring bond (Glidewell & Lloyd, 1984 ).

The conformation of (II) (Fig. 2) is more complex than that of (I). Although the pyrazole ring in (I) is planar, with the bond angles at each of atoms N1, C3, C3a and C7a summing independently to 360.0° within experimental uncertainty, the six-membered heterocyclic ring is not planar, in contrast to the heterocyclic ring in (I), and includes a markedly non-planar N atom (N7). For the atom sequence N7—C6—C5—C4—C3a—C7a, the ring-puckering parameters [θ = 130.7 (2)° and φ = 269.7 (2)°] indicate a half-chair conformation. As expected, the spiro-fused carbocyclic C5/C51–C55 ring adopts a nearly perfect chair conformation [θ = 5.6 (2)°; this angle is zero for the ideal chair conformation]. Finally, the dihedral angle between the pendent phenyl ring and the pyrazole ring is 11.8 (2)°, while the orientation of the tert-butyl group is such that atom C34 is nearly coplanar with the pyrazole ring (Table 3). The bond lengths in the heterocyclic portion of the molecule (Table 3) are consistent with complete bond fixation in the pyrazole ring according to the classical representation shown in the scheme above. The remaining geometric parameters show no unusual values.

The one-dimensional supramolecular structure of (I) is readily analysed in terms of a single C—H⋯N hydrogen bond (Table 2) and a single aromatic π–π stacking interaction. Atom C6 in the molecule at (x, y, z) acts as a hydrogen-bond donor to atom N5 in the molecule at (1 − x, 1 − y, 1 − z), thereby forming a centrosymmetric dimer centred at ( $[1 \over 2]$ , $[1 \over 2]$ , $[1 \over 2]$ ) and characterized by an [R_2^2] (6) motif (Bernstein et al., 1995 ; Fig. 3). The six-membered heterocyclic rings (N1/C4a/N5/C6/C6a/C10a) in the molecules at (x, y, z) and (−x, 1 − y, 1 − z) are parallel, with an interplanar spacing of 3.293 (2) Å. The ring-centroid separation is 3.557 (2) Å, corresponding to a centroid offset of 1.345 (2) Å. The effect of the π–π stacking interaction is to link adjacent [R_2^2] (6) dimers into a chain running parallel to the [100] direction (Fig. 4). Two chains of this type pass through each unit cell but there are no direction-specific interactions between adjacent chains.

The two-dimensional supramolecular aggregation in (II) involves two hydrogen bonds, one each of the N—H⋯O and C—H⋯O types; there is also a long and rather weak C—H⋯N contact, which may just be significant (Table 4). However, C—H⋯π(arene) hydrogen bonds and aromatic π–π stacking interactions are absent from the structure of (II). Atom N7 in the molecule at (x, y, z) acts as a hydrogen-bond donor to carbonyl atom O51 in the molecule at (1 − x, 1 − y, 1 − z), so forming a centrosymmetric [R_2^2] (12) dimer centred at ( $[1 \over 2]$ , $[1 \over 2]$ , $[1 \over 2]$ ) (Fig. 5). Dimers of this type are linked into sheets by the C—H⋯O hydrogen bond.

Aryl atom C15 in the molecule at (x, y, z) acts as a hydrogen-bond donor to the second carbonyl O atom, O55, in the molecule at (−1 + x, $[1 \over 2]$ − y, − $[1 \over 2]$ + z), while atom C15 at (−1 + x, $[1 \over 2]$ − y, − $[1 \over 2]$ + z) in turn acts as a donor to atom O55 at (−2 + x, y, −1 + z). In this manner, a C(11) chain is formed, running parallel to the [201] direction and generated by the c-glide plane at y = $[1 \over 4]$ (Fig. 6). In the reference [201] chain, the molecules at (x, y, z) and (−1 + x, $[1 \over 2]$ − y, − $[1 \over 2]$ + z) form [R_2^2] (12) dimers with the molecules at (1 − x, 1 − y, 1 − z) and (−x, − $[1 \over 2]$ + y, $[1 \over 2]$ − z), respectively. These latter two molecules lie in [201] chains generated by the c-glide planes at y = $[3 \over 4]$ and y = − $[1 \over 4]$ , respectively. Hence, propagation by the space group of these two hydrogen-bond motifs generates a (20 $[\overline 1]$ ) sheet built from [R_2^2] (12) and [R_6^6] (48) rings, both of which are centrosymmetric and alternating in a chessboard fashion (Fig. 7). The resulting net is of (6,3)-type if the isolated molecules of (II) are regarded as the nodes of the net and of (4,4)-type if the [R_2^2] (12) dimers are taken as the nodes (Batten & Robson, 1998 ).

Finally, there is a weak C—H⋯N interaction (Table 4), in which atom C54 at (x, y, z) acts as a hydrogen-bond donor, via H54B, to ring atom N1 in the molecule at (x, $[1 \over 2]$ − y, $[1 \over 2]$ + z). The coplanarity of atom N1 means that it is unlikely to be very basic, and hence it is likely to be a poor hydrogen-bond acceptor; accordingly, the H⋯N and C⋯N distances in this interaction are significantly longer than those in the C—H⋯N hydrogen bond of (I) (Table 2). On the other hand, if this interaction is indeed significant, its presence generates a C(8) chain running parallel to the [001] direction (Fig. 8), which serves to link adjacent (20 $[\overline 1]$ ) sheets into a three-dimensional array.

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
Part of the crystal structure of (I

), showing the formation of an [R_2^2]

(6) dimer. For clarity, H atoms 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 4
A stereoview of part of the crystal structure of (I

), showing the formation of a π-stacked chain of [R_2^2]

(6) dimers. For clarity, H atoms not involved in the motif shown have been omitted.

Figure 5
Part of the crystal structure of (II

), showing the formation of an [R_2^2]

(12) dimer. For clarity, H atoms 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
Part of the crystal structure of (II

), showing the formation of a C(11) chain along [201]. For 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, $[1 \over 2]$ − y, − $[1 \over 2]$ + z) and (1 + x, $[1 \over 2]$ − y, $[1 \over 2]$ + z), respectively.

Figure 7
A stereoview of part of the crystal structure of (II

), showing the formation of a (20 $[\overline 1]$ ) sheet of alternating [R_2^2]

(12) and

(48) rings.

Figure 8
Part of the crystal structure of (II

), showing the formation of a C(8) chain along [001]. For 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, $[1\over2]$ − y, $[1\over2]$ + z) and (x, $[1\over2]$ − y, − $[1\over2]$ + z), respectively.

Experimental

For the synthesis of (I), a mixture of 5-amino-3-methyl-1H-pyrazole (1.16 mmol), dimedone (1.16 mmol) and formaldehyde (1.20 mmol) was placed in an open Pyrex glass vessel and irradiated in a domestic microwave oven for 2 min (at 600 W). The resulting solid was washed with ethanol, dried and recrystallized from ethanol (m.p. 398 K, yield 54%). The mass spectrum (EI, 70 eV) shows the following peaks: m/z (%) 229 (83, M⁺), 173 (100), 145 (20), 77 (19), 51 (22), 39 (22). For the synthesis of (II), a mixture of 5-amino-3-tert-butyl-1-phenylpyrazole (1.1 mmol), dimedone (1.1 mmol) and formaldehyde (4.0 mmol) was placed in an open Pyrex glass vessel and irradiated in a domestic microwave oven for 3 min (at 600 W). The product of the reaction was recrystallized from absolute ethanol (m.p. 487 K, yield 58%). The mass spectrum (EI, 70 eV) shows the following peaks: m/z (%) 379 (60, M⁺), 295 (50), 294 (100), 77 (31), 57 (25), 55 (27), 41 (43).

Compound (I)

Crystal data

C₁₃H₁₅N₃O
M_r = 229.28
Monoclinic, P2₁/n
a = 5.9856 (3) Å
b = 18.1464 (9) Å
c = 10.7139 (4) Å
β = 98.457 (3)°
V = 1151.06 (9) Å³
Z = 4
D_x = 1.323 Mg m⁻³
Mo Kα radiation
Cell parameters from 2592 reflections
θ = 3.0–27.5°
μ = 0.09 mm⁻¹
T = 120 (2) K
Block, yellow
0.36 × 0.30 × 0.20 mm

Data collection

Nonius KappaCCD diffractometer
φ scans, and ω scans with κ offsets
Absorption correction: multi-scan (SORTAV; Blessing, 1995 , 1997 ) T_min = 0.931, T_max = 0.983
12 603 measured reflections
2592 independent reflections
2068 reflections with I > 2σ(I)
R_int = 0.060
θ_max = 27.5°
h = −7 → 7
k = −23 → 23
l = −13 → 13

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.114
S = 1.04
2592 reflections
157 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0624P)² + 0.2121P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Selected interatomic distances (Å) for (I)

N1—N2	1.3646 (14)
N2—C3	1.3398 (16)
C3—C4	1.3997 (15)
C4—C4a	1.3733 (11)
C4a—N1	1.3996 (12)
C4a—N5	1.3581 (13)
N5—C6	1.3120 (17)
C6—C6a	1.4203 (18)
C6a—C10a	1.3730 (18)
C10a—N1	1.3556 (16)

Table 2
Hydrogen-bonding geometry (Å, °) for (I)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯N5ⁱ	0.95	2.50	3.3397 (17)	148
Symmetry code: (i) 1-x,1-y,1-z.

Compound (II)

Crystal data

C₂₃H₂₉N₃O₂
M_r = 379.49
Monoclinic, P2₁/c
a = 10.0469 (2) Å
b = 16.4547 (4) Å
c = 12.7983 (2) Å
β = 108.4950 (12)°
V = 2006.52 (7) Å³
Z = 4
D_x = 1.256 Mg m⁻³
Mo Kα radiation
Cell parameters from 4595 reflections
θ = 3.0–27.5°
μ = 0.08 mm⁻¹
T = 120 (2) K
Plate, colourless
0.20 × 0.10 × 0.03 mm

Data collection

Nonius KappaCCD diffractometer
φ scans, and ω scans with κ offsets
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997) T_min = 0.927, T_max = 0.994
27 838 measured reflections
4595 independent reflections
3298 reflections with I > 2σ(I)
R_int = 0.051
θ_max = 27.5°
h = −12 → 13
k = −21 → 21
l = −16 → 16

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.124
S = 1.03
4595 reflections
258 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0749P)²] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 3
Selected geometric parameters (Å, °) for (II)

N1—N2	1.3784 (15)
N2—C3	1.3318 (17)
C3—C3a	1.4210 (17)
C3a—C7a	1.3628 (19)
C7a—N1	1.3739 (16)

N2—C3—C31—C32	−135.69 (13)
N2—C3—C31—C33	103.95 (14)
N2—C3—C31—C34	−14.90 (18)

Table 4
Hydrogen-bonding geometry (Å, °) for (II)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N7—H7⋯O51ⁱ	0.88	2.40	3.2248 (15)	157
C15—H15⋯O55ⁱⁱ	0.95	2.48	3.407 (2)	164
C54—H54B⋯N1ⁱⁱⁱ	0.99	2.60	3.5149 (18)	154
Symmetry codes: (i) 1-x,1-y,1-z; (ii) $[x-1,{\script{1\over 2}}-y,z-{\script{1\over 2}}]$ ; (iii) $[x,{\script{1\over 2}}-y,{\script{1\over 2}}+z]$ .

For (I) and (II), space groups P2₁/n and P2₁/c, respectively, were uniquely assigned from the systematic absences. All H atoms were located from difference maps and subsequently treated as riding atoms, with C—H distances of 0.95 (aromatic and heteroaromatic CH groups), 0.98 (CH₃) and 0.99 Å (CH₂), and N—H distances of 0.88 Å.

For both compounds, data collection: KappaCCD Server Software (Nonius, 1997 ); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997 ); data reduction: DENZO–SMN; program(s) used to solve structure: OSCAIL (McArdle, 2003 ) and SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: OSCAIL [for (I) only] 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. DOI: 10.1107/S0108270104004159/sk1707sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270104004159/sk1707Isup2.hkl

Structure factors: contains datablock 849. DOI: 10.1107/S0108270104004159/sk1707IIsup3.hkl

Comment top

As part of a program for the synthesis of fused pyrazolo derivatives (Quiroga et al., 1999), we have been investigating three-component cyclocondensations induced by microwave irradiation. From the reactions between formaldehyde, 5,5-dimethylcyclohexane-1,3-dione (dimedone) and either 5-amino-3-methyl-1H-pyrazole or 5-amino-3-tert-butyl-1-phenylpyrazole (which differ primarily in terms of the absence or presence of the substituent at atom N1), we have isolated two very different products, whose molecular and supramolecular structures are presented here. Using 5-amino-3-methyl-1H-pyrazole, which has only an H atom at N1, we obtained 2,8,8-trimethyl-6,7,8,9-tetrahydropyrazolo[2,3-a]quinazolin-6-one, (I), while with the N-phenyl-substituted 5-amino-3-tert-butyl-1-phenylpyrazole, the product was 3-tert-butyl-4',4'-dimethyl-1-phenyl-4,5,6,7-tetrahydro-1H- pyrazolo[3,4-b]pyridine-5-spiro-1'-cyclohexane-2',6'-dione, (II)

In (I) (Fig. 1), the two fused heterocyclic rings (atoms N1–C10A) are completely planar, with the bond angles at each of atoms N1, C3, C4A, C6A and C10A independently summing to 360.0° within experimental uncertainty. For the carbocyclic ring (C6A/C7–C10/C10A), the ring-puckering parameters (Cremer & Pople, 1975) for the atom sequence C6A–C10A [θ = 54.3 (2)° and ϕ = 163.8 (2)°] indicate an envelope conformation (Evans & Boeyens, 1989), consistent with the enforced coplanarity of atoms C6A, C7, C10A and C10. This ring thus exhibits a pseudo-mirror plane passing through atoms C6A, C9, C91 and C92 (Fig. 1).

The bond lengths in the fused heterocyclic rings in (I) show some unusual values (Table 1). Thus, for example, the formally single C4A—N5 and C10A—N1 bonds are only slightly longer than the formally double C3—N2 bond, although each of these single bonds is significantly shorter than the formally single C4A—N1 bond. Similarly, the lengths of the C3—C4 and C4—C4A bonds, formally single and double bonds, respectively, differ by less than 0.03 Å. These observations, together with the planarity at atom N1, suggest that this heterocyclic system exhibits a degree of naphthalene-type delocalization, involving a peripheral system of ten π-electrons with only modest participation by the cross-ring bond (Glidewell & Lloyd, 1984).

The conformation of (II) (Fig. 3) is more complex than that of (I). Although the pyrazole ring in (I) is planar, with the bond angles at each of atoms N1, C3, C3A and C7A summing independently to 360.0° within experimental uncertainty, the six-membered heterocyclic ring is not planar, in contrast to the heterocyclic ring in (I), and includes a markedly non-planar N atom (N7). For the atom sequence N7—C6—C5—C4—C3A—C7A, the ring-puckering parameters [θ = 130.7 (2)° and ϕ = 269.7 (2)°] indicate a half-chair conformation. As expected, the spiro-fused carbocyclic C5/C51–C55 ring adopts a nearly perfect chair conformation [θ = 5.6 (2)°; this angle is zero for the ideal chair conformation]. Finally, the dihedral angle between the pendent phenyl ring and the pyrazole ring is 11.8 (2)°, while the orientation of the tert-butyl group is such that atom C34 is nearly coplanar with the pyrazole ring (Table 3). The bond lengths in the heterocyclic portion of the molecule (Table 3) are consistent with complete bond fixation in the pyrazole ring according to the classical representation, (II). The remaining geometric parameters show no unusual values.

The one-dimensional supramolecular structure of (I) is readily analysed in terms of a single C—H···N hydrogen bond (Table 2) and a single aromatic π–π stacking interaction. Atom C6 in the molecule at (x, y, z) acts as a hydrogen-bond donor to atom N5 in the molecule at (1 − x, 1 − y, 1 − z), thereby forming a centrosymmetric dimer, centred at (1/2, 1/2, 1/2) and characterized by an R²₂(6) motif (Bernstein et al., 1995; Fig. 3). The six-membered heterocyclic rings (N1/C4A/N5/C6/C6A/C10A) in the molecules at (x, y, z) and (-x, 1 − y, 1 − z) are parallel, with an interplanar spacing of 3.293 (2) Å. The ring-centroid separation is 3.557 (2) Å, corresponding to a centroid offset of 1.345 (2) Å. The effect of the π–π stacking interaction is to link adjacent R²₂(6) dimers into a chain running parallel to the [100] direction (Fig. 4). Two chains of this type pass through each unit cell but there are no direction-specific interactions between adjacent chains.

The two-dimensional supramolecular aggregation in (II) involves two hydrogen bonds, one each of N—H···O and C—H···O types; there is also a long and rather weak C—H···N contact, which may just be significant (Table 4). However, C—H···π(arene) hydrogen bonds and aromatic π–π stacking interactions are absent from the structure of (II). Atom N7 in the molecule at (x, y, z) acts as a hydrogen-bond donor to carbonyl atom O51 in the molecule at (1 − x, 1 − y, 1 − z), so forming a centrosymmetric R²₂(12) dimer centred at (1/2, 1/2, 1/2) (Fig. 5). Dimers of this type are linked into sheets by the C—H···O hydrogen bond.

Aryl atom C15 in the molecule at (x, y, z) acts as a hydrogen-bond donor to the second carbonyl O atom, O55, in the molecule at (−1 + x, 0.5 − y, −0.5 + z), while atom C15 at (−1 + x, 0.5 − y, −0.5 + z) in turns acts as a donor to atom O55 at (−2 + x, y, −1 + z). In this manner, a C(11) chain is formed, running parallel to the [201] direction and generated by the c-glide plane at y = 0.25 (Fig. 6). In the reference [201] chain, the molecules at (x, y, z) and (−1 + x, 0.5 − y, −0.5 + z) form R²₂(12) dimers with the molecules at (1 − x, 1 − y, 1 − z) and (-x, −0.5 + y, 0.5 − z), respectively. These latter two molecules lie in [201] chains generated by the c-glide planes at y = 0.75 and y = −0.25, respectively. Hence propagation by the space group of these two hydrogen-bond motifs generates a (20–1) sheet built from R²₂(12) and R⁶₆(48) rings, both centrosymmetric, alternating in a chessboard fashion (Fig. 7). The resulting net is of (6,3) type if the isolated molecules of (II) are regarded as the nodes of the net and of (4,4) type if the R²₂(12) dimers are taken as the nodes (Batten & Robson, 1998).

Finally, there is a weak C—H···N interaction (Table 4), in which atom C54 at (x, y, z) acts as a hydrogen-bond donor, via H54B, to ring atom N1 in the molecule at (x, 0.5 − y, 0.5 + z). The coplanarity of atom N1 means that it is unlikely to be very basic, and hence it is likely to be a rather poor hydrogen-bond acceptor; accordingly, the H···N and C···N distances in this interaction are significantly longer than those in the C—H···N hydrogen bond of (I) (Table 2). On the other hand, if this interaction is indeed significant, its presence generates a C(8) chain running parallel to the [001] direction (Fig. 8), which serves to link together adjacent (20–1) sheets into a three-dimensional array.

Experimental top

For the synthesis of (I), a mixture of 5-amino-3-methyl-1H-pyrazole (1.16 mmol), dimedone (1.16 mmol) and formaldehyde (1.20 mmol) was placed in an open Pyrex glass vessel and irradiated in a domestic microwave oven for 2 min (at 600 W). The resulting solid was washed with ethanol, dried and recrystalized from ethanol (m.p. 398 K, yield 54%). The mass spectrum (EI, 70 eV) shows the following peaks: m/z (%), 229 (83, M+),173 (100), 145 (20), 77 (19), 51 (22), 39 (22). For the synthesis of (II), a mixture of 5-amino-3-tert-butyl-1-phenylpyrazole (1.1 mmol), dimedone (1.1 mmol) and formaldehyde (4.0 mmol) was placed in an open Pyrex glass vessel and irradiated in a domestic microwave oven for 3 min (at 600 W). The product of the reaction was recrystallized from absolute ethanol (m. p. 487 K, yield 58%). The mass spectrum (EI, 70 eV) shows the following peaks: m/z (%), 379 (60, M+), 295 (50), 294 (100), 77 (31), 57 (25), 55 (27), 41 (43).

Computing details top

For both compounds, data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997); data reduction: DENZO–SMN. Program(s) used to solve structure: OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997) for (I); OSCAIL (McArdle, 1995, 2003) and SHELXS97 (Sheldrick, 1997) for (II). Program(s) used to refine structure: OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick, 1997) for (I); SHELXL97 (Sheldrick, 1997) for (II). For both compounds, 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. Part of the crystal structure of (I), showing the formation of an R²₂(6) dimer. For clarity, H atoms 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).
	Fig. 4. A stereoview of part of the crystal structure of (I), showing the formation of a π-stacked chain of R²₂(6) dimers. For clarity, H atoms not involved in the motif shown have been omitted.
	Fig. 5. Part of the crystal structure of (II), showing the formation of an R²₂(12) dimer. For clarity, H atoms 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).
	Fig. 6. Part of the crystal structure of (II), showing the formation of a C(11) chain along [201]. For 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, 0.5 − y, −0.5 + z) and (1 + x, 0.5 − y, 0.5 + z), respectively.
	Fig. 7. A stereoview of part of the crystal structure of (II), showing the formation of a (20–1) sheet of alternating R²₂(12) and R⁶₆(48) rings.
	Fig. 8. Part of the crystal structure of (II), showing the formation of a C(8) chain along [001]. For 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, 0.5 − y, 0.5 + z)and (x, 0.5 − y, −0.5 + z), respectively.

(I) 2,8,8-Trimethyl-6,7,8,9-tetrahydropyrazolo[2,3-a]quinazolin-6-one top

Crystal data top

C₁₃H₁₅N₃O	F(000) = 488
M_r = 229.28	D_x = 1.323 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2592 reflections
a = 5.9856 (3) Å	θ = 3.0–27.5°
b = 18.1464 (9) Å	µ = 0.09 mm⁻¹
c = 10.7139 (4) Å	T = 120 K
β = 98.457 (3)°	Block, yellow
V = 1151.06 (9) Å³	0.36 × 0.30 × 0.20 mm
Z = 4

Data collection top

Nonius KappaCCD diffractometer	2592 independent reflections
Radiation source: rotating anode	2068 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.060
ϕ scans, and ω scans with κ offsets	θ_max = 27.5°, θ_min = 3.0°
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997)	h = −7→7
T_min = 0.931, T_max = 0.983	k = −23→23
12603 measured reflections	l = −13→13

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) + (0.0624P)² + 0.2121P] where P = (F_o² + 2F_c²)/3
2592 reflections	(Δ/σ)_max = 0.001
157 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

C₁₃H₁₅N₃O	V = 1151.06 (9) Å³
M_r = 229.28	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 5.9856 (3) Å	µ = 0.09 mm⁻¹
b = 18.1464 (9) Å	T = 120 K
c = 10.7139 (4) Å	0.36 × 0.30 × 0.20 mm
β = 98.457 (3)°

Data collection top

Nonius KappaCCD diffractometer	2592 independent reflections
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997)	2068 reflections with I > 2σ(I)
T_min = 0.931, T_max = 0.983	R_int = 0.060
12603 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 = 0.21 e Å⁻³
2592 reflections	Δρ_min = −0.34 e Å⁻³
157 parameters

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

	x	y	z	U_iso*/U_eq
N1	−0.03710 (17)	0.58920 (5)	0.64734 (10)	0.0183 (2)
N2	−0.20258 (18)	0.58786 (5)	0.72237 (10)	0.0200 (2)
C3	−0.1624 (2)	0.52522 (7)	0.78804 (12)	0.0214 (3)
C4	0.02664 (13)	0.48719 (4)	0.75877 (7)	0.0220 (3)
C4A	0.10583 (14)	0.52792 (4)	0.66651 (8)	0.0197 (3)
N5	0.27588 (18)	0.51740 (6)	0.59730 (10)	0.0239 (3)
C6	0.2967 (2)	0.56750 (7)	0.51147 (12)	0.0234 (3)
C6A	0.1541 (2)	0.63003 (7)	0.48777 (12)	0.0201 (3)
C7	0.1761 (2)	0.68044 (7)	0.38261 (12)	0.0223 (3)
O7	0.33053 (17)	0.67425 (5)	0.32005 (9)	0.0322 (3)
C8	−0.0062 (2)	0.73760 (7)	0.35273 (12)	0.0249 (3)
C9	−0.0915 (2)	0.76828 (7)	0.47044 (12)	0.0211 (3)
C10	−0.1768 (2)	0.70417 (7)	0.54389 (12)	0.0222 (3)
C10A	−0.0160 (2)	0.64114 (6)	0.55888 (11)	0.0186 (3)
C31	−0.31810 (18)	0.50231 (5)	0.87717 (11)	0.0277 (3)
C91	−0.2872 (2)	0.82158 (7)	0.43113 (14)	0.0288 (3)
C92	0.1017 (2)	0.80865 (7)	0.55239 (13)	0.0243 (3)
H31A	−0.4400	0.5385	0.8752	0.042*
H31B	−0.2344	0.4994	0.9628	0.042*
H31C	−0.3824	0.4539	0.8522	0.042*
H4	0.0876	0.4425	0.7952	0.026*
H6	0.4148	0.5616	0.4620	0.028*
H8A	−0.1348	0.7155	0.2965	0.030*
H8B	0.0530	0.7788	0.3065	0.030*
H92A	0.2276	0.7745	0.5762	0.036*
H92B	0.0486	0.8273	0.6287	0.036*
H92C	0.1526	0.8499	0.5048	0.036*
H91A	−0.3435	0.8402	0.5065	0.043*
H91B	−0.4090	0.7958	0.3773	0.043*
H91C	−0.2343	0.8629	0.3844	0.043*
H10A	−0.2007	0.7218	0.6284	0.027*
H10B	−0.3241	0.6871	0.4990	0.027*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0186 (5)	0.0174 (5)	0.0197 (5)	0.0003 (4)	0.0052 (4)	−0.0008 (4)
N2	0.0201 (5)	0.0200 (5)	0.0212 (6)	−0.0019 (4)	0.0078 (4)	0.0006 (4)
C3	0.0249 (7)	0.0198 (6)	0.0196 (6)	−0.0044 (5)	0.0035 (5)	−0.0015 (5)
C4	0.0254 (7)	0.0185 (6)	0.0215 (6)	−0.0002 (5)	0.0016 (5)	0.0000 (5)
C4A	0.0197 (6)	0.0177 (6)	0.0212 (6)	0.0012 (5)	0.0013 (5)	−0.0026 (4)
N5	0.0232 (6)	0.0228 (6)	0.0262 (6)	0.0024 (4)	0.0055 (5)	−0.0023 (4)
C6	0.0216 (6)	0.0237 (6)	0.0258 (7)	−0.0009 (5)	0.0067 (5)	−0.0046 (5)
C6A	0.0208 (6)	0.0203 (6)	0.0199 (6)	−0.0022 (5)	0.0050 (5)	−0.0028 (5)
C7	0.0245 (7)	0.0247 (6)	0.0184 (6)	−0.0057 (5)	0.0055 (5)	−0.0044 (5)
O7	0.0361 (6)	0.0347 (6)	0.0296 (6)	−0.0022 (4)	0.0177 (5)	0.0001 (4)
C8	0.0279 (7)	0.0283 (7)	0.0180 (6)	−0.0021 (5)	0.0025 (5)	0.0028 (5)
C9	0.0217 (6)	0.0209 (6)	0.0210 (6)	−0.0011 (5)	0.0040 (5)	0.0032 (5)
C10	0.0206 (6)	0.0218 (6)	0.0251 (7)	0.0021 (5)	0.0066 (5)	0.0036 (5)
C10A	0.0190 (6)	0.0181 (6)	0.0186 (6)	−0.0026 (5)	0.0023 (5)	−0.0015 (4)
C31	0.0326 (7)	0.0242 (6)	0.0282 (7)	−0.0029 (6)	0.0108 (6)	0.0029 (5)
C91	0.0254 (7)	0.0248 (7)	0.0354 (8)	0.0013 (5)	0.0023 (6)	0.0090 (5)
C92	0.0254 (7)	0.0224 (6)	0.0246 (7)	−0.0007 (5)	0.0028 (5)	0.0005 (5)

Geometric parameters (Å, º) top

N1—N2	1.3646 (14)	C7—O7	1.2240 (16)
N2—C3	1.3398 (16)	C7—C8	1.5056 (19)
C3—C4	1.3997 (15)	C8—C9	1.5330 (18)
C4—C4A	1.3733 (11)	C8—H8A	0.99
C4A—N1	1.3996 (12)	C8—H8B	0.99
C4A—N5	1.3581 (13)	C9—C91	1.5296 (17)
N5—C6	1.3120 (17)	C9—C92	1.5319 (17)
C6—C6A	1.4203 (18)	C9—C10	1.5334 (17)
C6A—C10A	1.3730 (18)	C92—H92A	0.98
C10A—N1	1.3556 (16)	C92—H92B	0.98
C3—C31	1.4883 (15)	C92—H92C	0.98
C31—H31A	0.98	C91—H91A	0.98
C31—H31B	0.98	C91—H91B	0.98
C31—H31C	0.98	C91—H91C	0.98
C4—H4	0.95	C10—C10A	1.4884 (17)
C6—H6	0.95	C10—H10A	0.99
C6A—C7	1.4722 (18)	C10—H10B	0.99

C10A—N1—N2	125.07 (10)	C9—C8—H8A	108.9
C10A—N1—C4A	122.49 (10)	C7—C8—H8B	108.9
N2—N1—C4A	112.36 (8)	C9—C8—H8B	108.9
C3—N2—N1	103.57 (10)	H8A—C8—H8B	107.8
N2—C3—C4	112.91 (11)	C91—C9—C92	109.78 (10)
N2—C3—C31	119.53 (10)	C91—C9—C8	109.71 (11)
C4—C3—C31	127.53 (10)	C92—C9—C8	109.30 (11)
C3—C31—H31A	109.5	C91—C9—C10	108.77 (10)
C3—C31—H31B	109.5	C92—C9—C10	110.42 (10)
H31A—C31—H31B	109.5	C8—C9—C10	108.84 (10)
C3—C31—H31C	109.5	C9—C92—H92A	109.5
H31A—C31—H31C	109.5	C9—C92—H92B	109.5
H31B—C31—H31C	109.5	H92A—C92—H92B	109.5
C4A—C4—C3	105.78 (6)	C9—C92—H92C	109.5
C4A—C4—H4	127.1	H92A—C92—H92C	109.5
C3—C4—H4	127.1	H92B—C92—H92C	109.5
N5—C4A—C4	133.09 (6)	C9—C91—H91A	109.5
N5—C4A—N1	121.50 (8)	C9—C91—H91B	109.5
C4—C4A—N1	105.37 (5)	H91A—C91—H91B	109.5
C6—N5—C4A	116.19 (10)	C9—C91—H91C	109.5
N5—C6—C6A	124.22 (12)	H91A—C91—H91C	109.5
N5—C6—H6	117.9	H91B—C91—H91C	109.5
C6A—C6—H6	117.9	C10A—C10—C9	112.31 (10)
C10A—C6A—C6	119.55 (11)	C10A—C10—H10A	109.1
C10A—C6A—C7	119.39 (11)	C9—C10—H10A	109.1
C6—C6A—C7	120.93 (11)	C10A—C10—H10B	109.1
O7—C7—C6A	121.47 (12)	C9—C10—H10B	109.1
O7—C7—C8	121.93 (12)	H10A—C10—H10B	107.9
C6A—C7—C8	116.54 (11)	N1—C10A—C6A	116.03 (11)
C7—C8—C9	113.20 (10)	N1—C10A—C10	118.98 (11)
C7—C8—H8A	108.9	C6A—C10A—C10	124.98 (11)

C10A—N1—N2—C3	176.55 (11)	C6—C6A—C7—C8	170.40 (11)
C4A—N1—N2—C3	−0.24 (12)	O7—C7—C8—C9	−145.78 (12)
N1—N2—C3—C4	1.12 (13)	C6A—C7—C8—C9	36.82 (15)
N1—N2—C3—C31	−176.92 (10)	C7—C8—C9—C91	−175.95 (10)
N2—C3—C4—C4A	−1.59 (11)	C7—C8—C9—C92	63.63 (13)
C31—C3—C4—C4A	176.26 (11)	C7—C8—C9—C10	−57.03 (14)
C3—C4—C4A—N5	−176.37 (11)	C91—C9—C10—C10A	166.13 (11)
C3—C4—C4A—N1	1.31 (6)	C92—C9—C10—C10A	−73.34 (13)
C10A—N1—C4A—N5	0.42 (15)	C8—C9—C10—C10A	46.63 (14)
N2—N1—C4A—N5	177.30 (9)	N2—N1—C10A—C6A	−176.06 (10)
C10A—N1—C4A—C4	−177.59 (9)	C4A—N1—C10A—C6A	0.42 (16)
N2—N1—C4A—C4	−0.71 (9)	N2—N1—C10A—C10	2.90 (17)
C4—C4A—N5—C6	176.89 (7)	C4A—N1—C10A—C10	179.38 (10)
N1—C4A—N5—C6	−0.48 (15)	C6—C6A—C10A—N1	−1.13 (17)
C4A—N5—C6—C6A	−0.28 (18)	C7—C6A—C10A—N1	174.84 (10)
N5—C6—C6A—C10A	1.1 (2)	C6—C6A—C10A—C10	179.98 (11)
N5—C6—C6A—C7	−174.76 (12)	C7—C6A—C10A—C10	−4.06 (19)
C10A—C6A—C7—O7	177.08 (11)	C9—C10—C10A—N1	163.17 (10)
C6—C6A—C7—O7	−7.01 (19)	C9—C10—C10A—C6A	−17.97 (17)
C10A—C6A—C7—C8	−5.50 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···N5ⁱ	0.95	2.50	3.3397 (17)	148

Symmetry code: (i) −x+1, −y+1, −z+1.

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

Crystal data top

C₂₃H₂₉N₃O₂	F(000) = 816
M_r = 379.49	D_x = 1.256 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4595 reflections
a = 10.0469 (2) Å	θ = 3.0–27.5°
b = 16.4547 (4) Å	µ = 0.08 mm⁻¹
c = 12.7983 (2) Å	T = 120 K
β = 108.4950 (12)°	Plate, colourless
V = 2006.52 (7) Å³	0.20 × 0.10 × 0.03 mm
Z = 4

Data collection top

Nonius KappaCCD diffractometer	4595 independent reflections
Radiation source: rotating anode	3298 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.051
ϕ scans, and ω scans with κ offsets	θ_max = 27.5°, θ_min = 3.0°
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997)	h = −12→13
T_min = 0.927, T_max = 0.994	k = −21→21
27838 measured reflections	l = −16→16

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.124	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0749P)²] where P = (F_o² + 2F_c²)/3
4595 reflections	(Δ/σ)_max < 0.001
258 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

C₂₃H₂₉N₃O₂	V = 2006.52 (7) Å³
M_r = 379.49	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.0469 (2) Å	µ = 0.08 mm⁻¹
b = 16.4547 (4) Å	T = 120 K
c = 12.7983 (2) Å	0.20 × 0.10 × 0.03 mm
β = 108.4950 (12)°

Data collection top

Nonius KappaCCD diffractometer	4595 independent reflections
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997)	3298 reflections with I > 2σ(I)
T_min = 0.927, T_max = 0.994	R_int = 0.051
27838 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.124	H-atom parameters constrained
S = 1.03	Δρ_max = 0.26 e Å⁻³
4595 reflections	Δρ_min = −0.34 e Å⁻³
258 parameters

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

	x	y	z	U_iso*/U_eq
N1	0.51417 (11)	0.35382 (7)	0.23582 (8)	0.0188 (3)
N2	0.61700 (11)	0.38397 (7)	0.19635 (8)	0.0202 (3)
C3	0.72904 (14)	0.39597 (8)	0.28453 (10)	0.0195 (3)
C3A	0.70101 (14)	0.37403 (8)	0.38289 (10)	0.0183 (3)
C4	0.78931 (14)	0.37412 (8)	0.50203 (10)	0.0208 (3)
C5	0.69795 (14)	0.36451 (8)	0.57720 (10)	0.0188 (3)
C6	0.57761 (14)	0.30174 (8)	0.52534 (10)	0.0217 (3)
N7	0.48636 (12)	0.32235 (7)	0.41519 (8)	0.0209 (3)
C7A	0.56441 (14)	0.34946 (8)	0.34879 (10)	0.0181 (3)
C11	0.38297 (14)	0.33163 (8)	0.15884 (10)	0.0189 (3)
C12	0.35341 (15)	0.35533 (8)	0.04973 (10)	0.0226 (3)
C13	0.22594 (16)	0.33500 (9)	−0.02672 (11)	0.0271 (3)
C14	0.12748 (16)	0.29159 (10)	0.00452 (12)	0.0332 (4)
C15	0.15777 (16)	0.26726 (11)	0.11293 (12)	0.0365 (4)
C16	0.28489 (16)	0.28704 (9)	0.19028 (11)	0.0292 (4)
C31	0.85797 (14)	0.43659 (9)	0.27134 (11)	0.0237 (3)
C32	0.99143 (14)	0.39206 (10)	0.33790 (11)	0.0286 (3)
C33	0.86070 (16)	0.52447 (9)	0.31246 (12)	0.0313 (4)
C34	0.84992 (16)	0.43752 (10)	0.14989 (11)	0.0326 (4)
C51	0.63690 (14)	0.44582 (8)	0.59829 (10)	0.0192 (3)
O51	0.65929 (10)	0.50821 (6)	0.55571 (7)	0.0238 (2)
C52	0.55781 (14)	0.44448 (8)	0.67999 (10)	0.0213 (3)
C53	0.65276 (14)	0.41225 (8)	0.79241 (10)	0.0208 (3)
C531	0.56547 (15)	0.40639 (9)	0.87041 (11)	0.0261 (3)
C532	0.77781 (15)	0.46879 (9)	0.83934 (11)	0.0252 (3)
C54	0.70789 (15)	0.32786 (8)	0.77600 (10)	0.0213 (3)
C55	0.78206 (15)	0.32938 (8)	0.69047 (10)	0.0208 (3)
O55	0.90072 (11)	0.30508 (7)	0.70890 (8)	0.0311 (3)
H4A	0.8423	0.4258	0.5195	0.025*
H4B	0.8579	0.3290	0.5157	0.025*
H6A	0.6205	0.2480	0.5223	0.026*
H6B	0.5194	0.2966	0.5746	0.026*
H7	0.4240	0.3594	0.4171	0.025*
H12	0.4206	0.3854	0.0276	0.027*
H13	0.2061	0.3511	−0.1014	0.033*
H14	0.0395	0.2785	−0.0480	0.040*
H15	0.0907	0.2367	0.1346	0.044*
H16	0.3049	0.2701	0.2647	0.035*
H32A	1.0736	0.4205	0.3303	0.043*
H32B	0.9894	0.3364	0.3103	0.043*
H32C	0.9969	0.3908	0.4157	0.043*
H33A	0.7748	0.5525	0.2693	0.047*
H33B	0.9425	0.5528	0.3039	0.047*
H33C	0.8666	0.5242	0.3904	0.047*
H34A	0.9323	0.4656	0.1421	0.049*
H34B	0.7646	0.4660	0.1066	0.049*
H34C	0.8477	0.3816	0.1231	0.049*
H52A	0.4742	0.4092	0.6522	0.026*
H52B	0.5254	0.5001	0.6892	0.026*
H53A	0.6252	0.3882	0.9430	0.039*
H53B	0.4890	0.3674	0.8410	0.039*
H53C	0.5261	0.4599	0.8772	0.039*
H53D	0.7442	0.5228	0.8516	0.038*
H53E	0.8308	0.4731	0.7872	0.038*
H53F	0.8387	0.4469	0.9094	0.038*
H54A	0.7736	0.3085	0.8469	0.026*
H54B	0.6284	0.2892	0.7528	0.026*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0177 (6)	0.0212 (6)	0.0181 (6)	−0.0029 (5)	0.0067 (5)	−0.0011 (4)
N2	0.0192 (6)	0.0227 (6)	0.0198 (6)	−0.0043 (5)	0.0075 (5)	−0.0010 (5)
C3	0.0200 (7)	0.0194 (7)	0.0198 (7)	−0.0004 (6)	0.0072 (5)	−0.0015 (5)
C3A	0.0204 (7)	0.0181 (7)	0.0176 (7)	−0.0007 (5)	0.0078 (5)	−0.0012 (5)
C4	0.0210 (7)	0.0232 (7)	0.0186 (7)	−0.0008 (6)	0.0068 (5)	−0.0007 (5)
C5	0.0196 (7)	0.0207 (7)	0.0163 (6)	−0.0006 (6)	0.0060 (5)	0.0002 (5)
C6	0.0256 (8)	0.0218 (7)	0.0178 (7)	−0.0039 (6)	0.0071 (6)	−0.0009 (5)
N7	0.0203 (6)	0.0256 (6)	0.0184 (6)	−0.0025 (5)	0.0084 (5)	−0.0005 (5)
C7A	0.0214 (7)	0.0167 (7)	0.0175 (6)	−0.0002 (5)	0.0080 (5)	−0.0014 (5)
C11	0.0182 (7)	0.0187 (7)	0.0192 (7)	0.0008 (5)	0.0051 (5)	−0.0037 (5)
C12	0.0238 (8)	0.0242 (7)	0.0209 (7)	−0.0006 (6)	0.0088 (6)	−0.0014 (6)
C13	0.0277 (8)	0.0313 (8)	0.0200 (7)	0.0000 (7)	0.0042 (6)	−0.0018 (6)
C14	0.0236 (8)	0.0421 (10)	0.0286 (8)	−0.0054 (7)	0.0009 (6)	−0.0049 (7)
C15	0.0280 (9)	0.0478 (10)	0.0318 (8)	−0.0146 (8)	0.0068 (7)	0.0020 (7)
C16	0.0283 (8)	0.0367 (9)	0.0218 (7)	−0.0081 (7)	0.0068 (6)	0.0016 (6)
C31	0.0216 (8)	0.0302 (8)	0.0197 (7)	−0.0068 (6)	0.0071 (6)	−0.0016 (6)
C32	0.0210 (8)	0.0392 (9)	0.0260 (8)	−0.0045 (7)	0.0081 (6)	0.0001 (6)
C33	0.0320 (9)	0.0309 (9)	0.0290 (8)	−0.0090 (7)	0.0068 (7)	0.0002 (6)
C34	0.0281 (9)	0.0502 (10)	0.0211 (7)	−0.0133 (7)	0.0099 (6)	0.0008 (7)
C51	0.0177 (7)	0.0221 (7)	0.0150 (6)	−0.0004 (6)	0.0011 (5)	0.0013 (5)
O51	0.0262 (6)	0.0218 (5)	0.0231 (5)	−0.0012 (4)	0.0072 (4)	0.0038 (4)
C52	0.0235 (8)	0.0212 (7)	0.0202 (7)	0.0026 (6)	0.0082 (6)	0.0009 (5)
C53	0.0228 (7)	0.0229 (7)	0.0172 (7)	−0.0010 (6)	0.0072 (5)	−0.0003 (5)
C531	0.0279 (8)	0.0303 (8)	0.0221 (7)	−0.0003 (6)	0.0110 (6)	0.0021 (6)
C532	0.0275 (8)	0.0258 (8)	0.0225 (7)	−0.0018 (6)	0.0082 (6)	−0.0024 (6)
C54	0.0238 (8)	0.0219 (7)	0.0181 (6)	0.0002 (6)	0.0064 (5)	0.0039 (5)
C55	0.0255 (8)	0.0159 (7)	0.0204 (7)	0.0004 (6)	0.0064 (6)	−0.0007 (5)
O55	0.0284 (6)	0.0392 (6)	0.0262 (5)	0.0119 (5)	0.0095 (4)	0.0059 (4)
C6	0.0256 (8)	0.0218 (7)	0.0178 (7)	−0.0039 (6)	0.0071 (6)	−0.0009 (5)
N7	0.0203 (6)	0.0256 (6)	0.0184 (6)	−0.0025 (5)	0.0084 (5)	−0.0005 (5)
C7A	0.0214 (7)	0.0167 (7)	0.0175 (6)	−0.0002 (5)	0.0080 (5)	−0.0014 (5)

Geometric parameters (Å, º) top

N1—N2	1.3784 (15)	C3A—C4	1.5012 (17)
N2—C3	1.3318 (17)	C4—C5	1.5341 (18)
C3—C3A	1.4210 (17)	C4—H4A	0.99
C3A—C7A	1.3628 (19)	C4—H4B	0.99
C7A—N1	1.3739 (16)	C5—C51	1.5312 (19)
N1—C11	1.4204 (17)	C5—C55	1.5404 (18)
C11—C16	1.3866 (19)	C5—C6	1.5684 (19)
C11—C12	1.3882 (18)	C51—O51	1.2163 (15)
C12—C13	1.3836 (19)	C51—C52	1.5007 (17)
C12—H12	0.95	C52—C53	1.5462 (18)
C13—C14	1.378 (2)	C52—H52A	0.99
C13—H13	0.95	C52—H52B	0.99
C14—C15	1.382 (2)	C53—C532	1.5251 (19)
C14—H14	0.95	C53—C531	1.5266 (18)
C15—C16	1.384 (2)	C53—C54	1.5340 (19)
C15—H15	0.95	C531—H53A	0.98
C16—H16	0.95	C531—H53B	0.98
C3—C31	1.5139 (19)	C531—H53C	0.98
C31—C32	1.528 (2)	C532—H53D	0.98
C31—C34	1.5307 (18)	C532—H53E	0.98
C31—C33	1.536 (2)	C532—H53F	0.98
C32—H32A	0.98	C54—C55	1.5072 (18)
C32—H32B	0.98	C54—H54A	0.99
C32—H32C	0.98	C54—H54B	0.99
C33—H33A	0.98	C55—O55	1.2076 (17)
C33—H33B	0.98	C6—N7	1.4569 (16)
C33—H33C	0.98	C6—H6A	0.99
C34—H34A	0.98	C6—H6B	0.99
C34—H34B	0.98	N7—C7A	1.3996 (16)
C34—H34C	0.98	N7—H7	0.88

C7A—N1—N2	109.67 (10)	C5—C4—H4B	109.4
C7A—N1—C11	131.83 (11)	H4A—C4—H4B	108.0
N2—N1—C11	118.48 (10)	C51—C5—C4	111.92 (11)
C16—C11—C12	119.71 (12)	C51—C5—C55	107.03 (10)
C16—C11—N1	121.55 (12)	C4—C5—C55	111.73 (11)
C12—C11—N1	118.74 (12)	C51—C5—C6	110.60 (11)
C13—C12—C11	119.88 (13)	C4—C5—C6	109.68 (10)
C13—C12—H12	120.1	C55—C5—C6	105.68 (10)
C11—C12—H12	120.1	O51—C51—C52	122.59 (12)
C14—C13—C12	120.58 (13)	O51—C51—C5	121.14 (12)
C14—C13—H13	119.7	C52—C51—C5	116.12 (11)
C12—C13—H13	119.7	C51—C52—C53	110.28 (11)
C13—C14—C15	119.45 (14)	C51—C52—H52A	109.6
C13—C14—H14	120.3	C53—C52—H52A	109.6
C15—C14—H14	120.3	C51—C52—H52B	109.6
C14—C15—C16	120.62 (15)	C53—C52—H52B	109.6
C14—C15—H15	119.7	H52A—C52—H52B	108.1
C16—C15—H15	119.7	C532—C53—C531	110.69 (11)
C15—C16—C11	119.77 (13)	C532—C53—C54	108.54 (11)
C15—C16—H16	120.1	C531—C53—C54	109.86 (11)
C11—C16—H16	120.1	C532—C53—C52	110.20 (11)
C3—N2—N1	105.85 (10)	C531—C53—C52	108.50 (11)
N2—C3—C3A	111.18 (12)	C54—C53—C52	109.03 (10)
N2—C3—C31	119.61 (11)	C53—C531—H53A	109.5
C3A—C3—C31	128.90 (12)	C53—C531—H53B	109.5
C3—C31—C32	110.89 (11)	H53A—C531—H53B	109.5
C3—C31—C34	110.25 (11)	C53—C531—H53C	109.5
C32—C31—C34	108.98 (12)	H53A—C531—H53C	109.5
C3—C31—C33	107.47 (11)	H53B—C531—H53C	109.5
C32—C31—C33	110.08 (12)	C53—C532—H53D	109.5
C34—C31—C33	109.14 (11)	C53—C532—H53E	109.5
C31—C32—H32A	109.5	H53D—C532—H53E	109.5
C31—C32—H32B	109.5	C53—C532—H53F	109.5
H32A—C32—H32B	109.5	H53D—C532—H53F	109.5
C31—C32—H32C	109.5	H53E—C532—H53F	109.5
H32A—C32—H32C	109.5	C55—C54—C53	111.57 (11)
H32B—C32—H32C	109.5	C55—C54—H54A	109.3
C31—C33—H33A	109.5	C53—C54—H54A	109.3
C31—C33—H33B	109.5	C55—C54—H54B	109.3
H33A—C33—H33B	109.5	C53—C54—H54B	109.3
C31—C33—H33C	109.5	H54A—C54—H54B	108.0
H33A—C33—H33C	109.5	O55—C55—C54	122.52 (12)
H33B—C33—H33C	109.5	O55—C55—C5	121.40 (12)
C31—C34—H34A	109.5	C54—C55—C5	116.08 (12)
C31—C34—H34B	109.5	N7—C6—C5	114.85 (11)
H34A—C34—H34B	109.5	N7—C6—H6A	108.6
C31—C34—H34C	109.5	C5—C6—H6A	108.6
H34A—C34—H34C	109.5	N7—C6—H6B	108.6
H34B—C34—H34C	109.5	C5—C6—H6B	108.6
C7A—C3A—C3	104.72 (11)	H6A—C6—H6B	107.5
C7A—C3A—C4	122.42 (11)	C7A—N7—C6	111.09 (11)
C3—C3A—C4	132.86 (12)	C7A—N7—H7	109.7
C3A—C4—C5	111.01 (11)	C6—N7—H7	111.7
C3A—C4—H4A	109.4	C3A—C7A—N1	108.54 (11)
C5—C4—H4A	109.4	C3A—C7A—N7	126.97 (12)
C3A—C4—H4B	109.4	N1—C7A—N7	124.47 (12)

C7A—N1—C11—C16	−10.6 (2)	C4—C5—C51—C52	−174.05 (10)
N2—N1—C11—C16	167.59 (12)	C55—C5—C51—C52	−51.32 (15)
C7A—N1—C11—C12	169.58 (13)	C6—C5—C51—C52	63.33 (14)
N2—N1—C11—C12	−12.28 (18)	O51—C51—C52—C53	−118.13 (14)
C16—C11—C12—C13	0.6 (2)	C5—C51—C52—C53	57.57 (15)
N1—C11—C12—C13	−179.53 (12)	C51—C52—C53—C532	62.51 (14)
C11—C12—C13—C14	0.2 (2)	C51—C52—C53—C531	−176.15 (11)
C12—C13—C14—C15	−1.0 (2)	C51—C52—C53—C54	−56.53 (14)
C13—C14—C15—C16	0.9 (3)	C532—C53—C54—C55	−64.73 (13)
C14—C15—C16—C11	−0.1 (3)	C531—C53—C54—C55	174.11 (11)
C12—C11—C16—C15	−0.7 (2)	C52—C53—C54—C55	55.33 (14)
N1—C11—C16—C15	179.44 (14)	C53—C54—C55—O55	125.23 (14)
C7A—N1—N2—C3	1.31 (14)	C53—C54—C55—C5	−54.37 (15)
C11—N1—N2—C3	−177.22 (11)	C51—C5—C55—O55	−130.33 (13)
N1—N2—C3—C3A	−0.13 (14)	C4—C5—C55—O55	−7.49 (18)
N1—N2—C3—C31	−174.27 (11)	C6—C5—C55—O55	111.75 (14)
N2—C3—C31—C32	−135.69 (13)	C51—C5—C55—C54	49.27 (15)
N2—C3—C31—C33	103.95 (14)	C4—C5—C55—C54	172.11 (11)
N2—C3—C31—C34	−14.90 (18)	C6—C5—C55—C54	−68.65 (14)
C3A—C3—C31—C32	51.34 (19)	C51—C5—C6—N7	66.04 (14)
C3A—C3—C31—C34	172.13 (13)	C4—C5—C6—N7	−57.88 (15)
C3A—C3—C31—C33	−69.02 (17)	C55—C5—C6—N7	−178.46 (11)
N2—C3—C3A—C7A	−1.08 (15)	C5—C6—N7—C7A	43.97 (15)
C31—C3—C3A—C7A	172.37 (13)	C3—C3A—C7A—N1	1.85 (15)
N2—C3—C3A—C4	178.76 (13)	C4—C3A—C7A—N1	−178.01 (11)
C31—C3—C3A—C4	−7.8 (2)	C3—C3A—C7A—N7	−179.44 (12)
C7A—C3A—C4—C5	−14.17 (18)	C4—C3A—C7A—N7	0.7 (2)
C3—C3A—C4—C5	166.02 (14)	N2—N1—C7A—C3A	−2.04 (15)
C3A—C4—C5—C51	−83.73 (13)	C11—N1—C7A—C3A	176.23 (13)
C3A—C4—C5—C55	156.26 (11)	N2—N1—C7A—N7	179.22 (11)
C3A—C4—C5—C6	39.42 (14)	C11—N1—C7A—N7	−2.5 (2)
C4—C5—C51—O51	1.72 (17)	C6—N7—C7A—C3A	−15.63 (19)
C55—C5—C51—O51	124.44 (13)	C6—N7—C7A—N1	162.88 (12)
C6—C5—C51—O51	−120.91 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N7—H7···O51ⁱ	0.88	2.40	3.2248 (15)	157
C15—H15···O55ⁱⁱ	0.95	2.48	3.407 (2)	164
C54—H54B···N1ⁱⁱⁱ	0.99	2.60	3.5149 (18)	154

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

Experimental details

	(I)	(II)
Crystal data
Chemical formula	C₁₃H₁₅N₃O	C₂₃H₂₉N₃O₂
M_r	229.28	379.49
Crystal system, space group	Monoclinic, P2₁/n	Monoclinic, P2₁/c
Temperature (K)	120	120
a, b, c (Å)	5.9856 (3), 18.1464 (9), 10.7139 (4)	10.0469 (2), 16.4547 (4), 12.7983 (2)
β (°)	98.457 (3)	108.4950 (12)
V (Å³)	1151.06 (9)	2006.52 (7)
Z	4	4
Radiation type	Mo Kα	Mo Kα
µ (mm⁻¹)	0.09	0.08
Crystal size (mm)	0.36 × 0.30 × 0.20	0.20 × 0.10 × 0.03

Data collection
Diffractometer	Nonius KappaCCD diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (SORTAV; Blessing, 1995, 1997)	Multi-scan (SORTAV; Blessing, 1995, 1997)
T_min, T_max	0.931, 0.983	0.927, 0.994
No. of measured, independent and observed [I > 2σ(I)] reflections	12603, 2592, 2068	27838, 4595, 3298
R_int	0.060	0.051
(sin θ/λ)_max (Å⁻¹)	0.650	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.114, 1.04	0.042, 0.124, 1.03
No. of reflections	2592	4595
No. of parameters	157	258
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.34	0.26, −0.34

Computer programs: KappaCCD Server Software (Nonius, 1997), DENZO–SMN (Otwinowski & Minor, 1997), DENZO–SMN, OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997), OSCAIL (McArdle, 1995, 2003) and SHELXS97 (Sheldrick, 1997), OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97 and PRPKAPPA (Ferguson, 1999).

Selected bond lengths (Å) for (I) top

N1—N2	1.3646 (14)	C4A—N5	1.3581 (13)
N2—C3	1.3398 (16)	N5—C6	1.3120 (17)
C3—C4	1.3997 (15)	C6—C6A	1.4203 (18)
C4—C4A	1.3733 (11)	C6A—C10A	1.3730 (18)
C4A—N1	1.3996 (12)	C10A—N1	1.3556 (16)

Hydrogen-bond geometry (Å, º) for (I) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···N5ⁱ	0.95	2.50	3.3397 (17)	148

Symmetry code: (i) −x+1, −y+1, −z+1.

Selected geometric parameters (Å, º) for (II) top

N1—N2	1.3784 (15)	C3A—C7A	1.3628 (19)
N2—C3	1.3318 (17)	C7A—N1	1.3739 (16)
C3—C3A	1.4210 (17)

N2—C3—C31—C32	−135.69 (13)	N2—C3—C31—C34	−14.90 (18)
N2—C3—C31—C33	103.95 (14)

Hydrogen-bond geometry (Å, º) for (II) top

D—H···A	D—H	H···A	D···A	D—H···A
N7—H7···O51ⁱ	0.88	2.40	3.2248 (15)	157
C15—H15···O55ⁱⁱ	0.95	2.48	3.407 (2)	164
C54—H54B···N1ⁱⁱⁱ	0.99	2.60	3.5149 (18)	154

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

Footnotes

‡Postal address: Department of Electrical Engineering and Physics, University of Dundee, Dundee DD1 4HN, Scotland.

Acknowledgements

X-ray data were collected at the EPSRC X-ray Crystallographic Service, University of Southampton, England; the authors thank the staff for all their help and advice. JNL thanks NCR Self-Service, Dundee, for grants that have provided computing facilities for this work. JQ and JM thank COLCIENCIAS and Universidad del Valle, and JC thanks Consejería de Educación y Ciencia (Junta de Andalucía, Spain) for financial support.

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Volume 60| Part 4| April 2004| Pages o265-o269

doi:10.1107/S0108270104004159