Hydrogen-bonded chains in isostructural 5-meth­yl-2-(4-methyl­phen­yl)-7,8-dihydro-6H-cyclo­penta­[g]­pyra­zolo­[1,5-a]pyrimidine, 2-(4-chloro­phen­yl)-5-meth­yl-7,8-dihydro-6H-cyclo­penta­[g]pyrazolo[1,5-a]pyrimidine and 2-(4-bromo­phen­yl)-5-meth­yl-7,8-dihydro-6H-cyclo­penta­[g]pyrazolo[1,5-a]pyrimidine, and sheets of π-stacked hydrogen-bonded chains in 2-(4-methoxy­phen­yl)-5-meth­yl-7,8-dihydro-6H-cyclo­penta­[g]­pyrazolo[1,5-a]pyrimidine

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

doi:10.1107/S0108270105016720

organic compounds

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 61| Part 7| July 2005| Pages o452-o456

doi:10.1107/S0108270105016720

Hydrogen-bonded chains in isostructural 5-methyl-2-(4-methylphenyl)-7,8-dihydro-6H-cyclopenta[g]pyrazolo[1,5-a]pyrimidine, 2-(4-chlorophenyl)-5-methyl-7,8-dihydro-6H-cyclopenta[g]pyrazolo[1,5-a]pyrimidine and 2-(4-bromophenyl)-5-methyl-7,8-dihydro-6H-cyclopenta[g]pyrazolo[1,5-a]pyrimidine, and sheets of π-stacked hydrogen-bonded chains in 2-(4-methoxyphenyl)-5-methyl-7,8-dihydro-6H-cyclopenta[g]pyrazolo[1,5-a]pyrimidine

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 24 May 2005; accepted 25 May 2005; online 22 June 2005)

5-Methyl-2-(4-methylphenyl)-7,8-dihydro-6H-cyclopenta[g]pyrazolo[1,5-a]pyrimidine, C₁₇H₁₇N₃, 2-(4-chlorophenyl)-5-methyl-7,8-dihydro-6H-cyclopenta[g]pyrazolo[1,5-a]pyrimidine, C₁₆H₁₄ClN₃, and 2-(4-bromophenyl)-5-methyl-7,8-dihydro-6H-cyclopenta[g]pyrazolo[1,5-a]pyrimidine, C₁₆H₁₄BrN₃, are isostructural; in each compound, the molecules are linked into chains by a single C—H⋯π(arene) hydrogen bond. Molecules of 2-(4-methoxyphenyl)-5-methyl-7,8-dihydro-6H-cyclopenta[g]pyrazolo[1,5-a]pyrimidine, C₁₇H₁₇N₃O, are linked by a single C—H⋯N hydrogen bond into chains, which are themselves linked into sheets by a π–π stacking interaction.

Comment

Pyrazolo[1,5-a]pyrimidines are purine analogues which have shown useful properties as antimetabolites, and which have been of pharmaceutical interest because of their antitrypanosomal activity (Novinson et al., 1976 ) and their antischistosomal activity (Senga et al., 1981 ). These interesting biological properties have prompted the search for new and efficient procedures of wide generality for the synthesis of pyrazolo[1,5-a]pyrimidine derivatives (Al-Shiekh et al., 2004 ; Makarov et al., 2005 ). We report here the structures of four cyclopenta[g]pyrazolo[1,5-a]pyrimidines, namely 5-methyl-2-(4-methylphenyl)-7,8-dihydro-6H-cyclopenta[g]pyrazolo[1,5-a]pyrimidine, (I), 2-(4-chlorophenyl)-5-methyl-7,8-dihydro-6H-cyclopenta[g]pyrazolo[1,5-a]pyrimidine, (II), 2-(4-bromophenyl)-5-methyl-7,8-dihydro-6H-cyclopenta[g]pyrazolo[1,5-a]pyrimidine, (III), and 2-(4-methoxyphenyl)-5-methyl-7,8-dihydro-6H-cyclopenta[g]pyrazolo[1,5-a]pyrimidine, (IV), prepared by solvent-free cyclocondensation reactions between 5-amino-1H-pyrazole derivatives and 2-acetylcyclopentanone, induced by microwave irradiation.

Compounds (I)–(III) form isomorphous crystals, and the compounds are isostructural. This fact is consistent with the similar steric requirements of methyl, chloro and bromo substituents, as reflected, for example, in the similar unit-cell dimensions of (I)–(III).

The corresponding bond lengths within the heterobicyclic fragments in compounds (I)–(IV) (Figs. 1–4 ) are very similar (Table 1), but the patterns of these bond distances show some interesting properties. In each of (I)–(IV), the N1—C2 bond, which is formally a double bond, is not significantly shorter than the C3A—N4 and C8A—N8B bonds, both of which are formally single bonds; at the same time, the cross-ring bonds C3A—N8B are by far the longest C—N bond in any molecule. These observations, together with the clear bond fixation in the pyrimidine ring, suggest that the ten π electrons of the pyrazolopyrimidine units are not fully delocalized around the periphery, but instead adopt a more characteristic arrangement, reminiscent of that in naphthalene.

In all of these compounds, the five-membered carbocyclic ring has an envelope conformation, with the fold across the line C6⋯C8; the total puckering amplitude Q (Cremer & Pople, 1975 ) is larger in (III) [0.231 (4) Å] than in any of (I) [0.111 (3) Å], (II) [0.159 (3) Å] or (IV) [0.095 (2) Å], but in each case the ring-puckering parameter φ₂ [257.1 (14)° in (I), 255.0 (10)° in (II), 73.3 (8)° in (III) and 73.6 (8)° in (IV) for the atom sequence C5A—C6—C7—C8—C8A] is very close to the ideal value of 36n° (Evans & Boeyens, 1989 ), with n = 7 in (I) and (II), and n = 2 in (III) and (IV). The 4-substituted C21–C26 aryl ring is nearly coplanar with the heterobicyclic ring system in each of (I)–(IV); thus, the dihedral angles between the aryl ring and the mean plane of the pyrazolopyrimidine ring system are 12.0 (2)° in (I), 14.5 (2)° in (II), 14.2 (2)° in (III) and 3.6 (2)° in (IV). In compound (IV), methoxy atom C241 is nearly coplanar with the aryl ring and, consistent with this, the exocyclic C—C—O angles at atom C24 show the usual deviations from 120° (Table 1).

Despite the strong similarities between compounds (I)–(IV) in terms both of their overall constitutions and of their intramolecular geometries and conformations, the pattern of supramolecular aggregation in compound (IV) is very different from that in the isostructural trio (I)–(III), both from the point of view of the direction-specific interactions present and in terms of their overall supramolecular structures.

In each of compounds (I)–(III), the molecules are linked into chains by a single C—H⋯π(arene) hydrogen bond (Table 2); atom C6 in the molecule at (x, y, z) acts as a donor, via atom H6A, to the pyrazole ring in the molecule at (x, −1 + y, z), so generating by translation a chain running parallel to the [010] direction (Fig. 5). It should be noted that C—H⋯N and, in (II) and (III), C—H⋯halogen hydrogen bonds, as well as aromatic π–π stacking interactions, are all absent from the structures of (I)–(III).

By contrast, in compound (IV), the molecules are linked into chains by a C—H⋯N hydrogen bond (Table 2), and these chains are themselves linked into sheets by a π–π stacking interaction. Aryl atom C22 in the molecule at (x, y, z) acts as a hydrogen-bond donor to pyrimidine atom N4 in the molecule at (1 − x, − $[{1\over 2}]$ + y, $[{1\over 2}]$ − z), so forming a C(7) chain running parallel to the [010] direction and generated by the 2₁ screw axis along ( $[{1\over 2}]$ , y, $[{1\over 4}]$ ) (Fig. 6). The π–π stacking interaction involves the fused heterocyclic rings of the molecules at (x, y, z) and (1 − x, 2 − y, −z), where the interplanar spacing is 3.504 (2) Å; the ring-centroid separation of the pyrazole and pyrimidine rings, respectively, is 3.577 (2) Å, corresponding to a ring-centroid offset of 0.719 (2) Å; the corresponding separation of the pyrimidine centroids is 3.799 (2) Å, with a centroid offset of 1.489 (2) Å. These two molecules lie in the C(7) chains along ( $[{1\over 2}]$ , y, $[1\over4]$ ) and ( $[{1\over 2}]$ , y, − $[1\over4]$ ), respectively, and propagation by the space group of this stacking interaction generates a sheet lying parallel to (100) (Fig. 7).

It is striking that, although the substituents in the aryl rings, viz. 4-methyl in (I), 4-chloro in (II), 4-bromo in (III) and 4-methoxy in (IV), play no direct role whatever in the supramolecular aggregation, nonetheless the types of direction-specific intermolecular interaction apparent in the crystal structures of (I)–(III) are entirely different from those apparent in the structure of (IV). The influence of these remote substituents on the supramolecular structures thus appears to be indirect and rather subtle, but real nonetheless; such subtle influences necessarily hinder the effective prediction of such structures.

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. For clarity, only the major orientation of the disordered CH₂ group is shown. 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 via C—H⋯π(arene) hydrogen bonds (dashed lines) of a chain along [010]. For clarity, H atoms bonded to those C atoms that are not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (x, −1 + y, z) and (x, 1 + y, z), respectively. The [010] chains in (II)

and (III)

are essentially identical to that in (I)

Figure 6
Part of the crystal structure of (IV)

, showing the formation via C—H⋯N hydrogen bonds (dashed lines) of a C(7) chain along [010]. 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 compound (IV)

, showing the formation of a (100) sheet of π-stacked [010] chains. For clarity, H atoms not involved in the motif shown have been omitted.

Experimental

Equimolar mixtures of the appropriate 5-amino-3-aryl-1H-pyrazole (2.6 mmol) [where aryl is 4-methylphenyl for (I), 4-chlorophenyl for (II), 4-bromophenyl for (III) and 4-methoxyphenyl for (IV)] and 2-acetylcyclopentanone (2.6 mmol) were placed in open Pyrex glass vessels and irradiated in a domestic microwave oven for 1.5–2 min at 600 W. The product mixtures were extracted with ethanol and, after removal of the solvent, the resulting solids were recrystallized from dimethylformamide to give crystals of (I)–(IV) suitable for single-crystal X-ray diffraction. For (I), m.p. 512–513 K, yield 80%; MS (30 eV) m/z (%): 263 (100, M⁺), 248 (4). For (II), m.p. 496–497 K, yield 83%; MS (30 eV) m/z (%): 285/283 (35/100, M⁺), 268 (3), 241 (2). For (III), m.p. 496–497 K, yield 83%; MS (30 eV) m/z (%): 329/327 (97/100, M⁺), 312 (3). For (IV), m.p. 497–498 K, yield 85%; MS (30 eV) m/z (%): 279 (100, M⁺), 264 (27), 236 (7).

Compound (I)

Crystal data

C₁₇H₁₇N₃
M_r = 263.34
Monoclinic, P 2₁ /c
a = 13.2882 (7) Å
b = 6.8383 (4) Å
c = 15.1947 (8) Å
β = 104.018 (3)°
V = 1339.60 (13) Å³
Z = 4
D_x = 1.306 Mg m⁻³
Mo Kα radiation
Cell parameters from 3076 reflections
θ = 3.2–27.5°
μ = 0.08 mm⁻¹
T = 120 (2) K
Needle, colourless
0.52 × 0.08 × 0.04 mm

Data collection

Nonius KappaCCD diffractometer
φ and ω scans
Absorption correction: multi-scan(SADABS; Sheldrick, 2003 )T_min = 0.955, T_max = 0.997
13947 measured reflections
3076 independent reflections
1640 reflections with I > 2σ(I)
R_int = 0.085
θ_max = 27.5°
h = −17 → 16
k = −8 → 8
l = −19 → 19

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.064
wR(F²) = 0.175
S = 1.01
3076 reflections
183 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0891P)² + 0.0582P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Compound (II)

Crystal data

C₁₆H₁₄ClN₃
M_r = 283.75
Monoclinic, P 2₁ /c
a = 13.6800 (11) Å
b = 6.6669 (6) Å
c = 15.2010 (16) Å
β = 106.980 (6)°
V = 1325.9 (2) Å³
Z = 4
D_x = 1.421 Mg m⁻³
Mo Kα radiation
Cell parameters from 3040 reflections
θ = 3.4–27.6°
μ = 0.28 mm⁻¹
T = 120 (2) K
Plate, colourless
0.34 × 0.18 × 0.03 mm

Data collection

Nonius KappaCCD diffractometer
φ and ω scans
Absorption correction: multi-scan(SADABS; Sheldrick, 2003)T_min = 0.922, T_max = 0.992
14750 measured reflections
3040 independent reflections
2060 reflections with I > 2σ(I)
R_int = 0.072
θ_max = 27.6°
h = −16 → 17
k = −8 → 8
l = −17 → 19

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.141
S = 1.03
3040 reflections
182 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0726P)² + 0.3419P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.49 e Å⁻³

Compound (III)

Crystal data

C₁₆H₁₄BrN₃
M_r = 328.21
Monoclinic, P 2₁ /c
a = 13.5387 (6) Å
b = 6.8551 (2) Å
c = 15.2767 (7) Å
β = 105.708 (2)°
V = 1364.87 (10) Å³
Z = 4
D_x = 1.597 Mg m⁻³
Mo Kα radiation
Cell parameters from 3125 reflections
θ = 3.3–27.5°
μ = 3.00 mm⁻¹
T = 120 (2) K
Plate, colourless
0.66 × 0.20 × 0.02 mm

Data collection

Nonius KappaCCD diffractometer
φ and ω scans
Absorption correction: multi-scan(SADABS; Sheldrick, 2003)T_min = 0.242, T_max = 0.942
18357 measured reflections
3125 independent reflections
2438 reflections with I > 2σ(I)
R_int = 0.069
θ_max = 27.5°
h = −17 → 17
k = −8 → 8
l = −19 → 19

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.096
S = 1.05
3125 reflections
186 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0473P)² + 0.618P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.68 e Å⁻³

Compound (IV)

Crystal data

C₁₇H₁₇N₃O
M_r = 279.34
Monoclinic, P 2₁ /c
a = 9.4691 (3) Å
b = 8.1711 (2) Å
c = 18.0278 (6) Å
β = 95.3430 (14)°
V = 1388.80 (7) Å³
Z = 4
D_x = 1.336 Mg m⁻³
Mo Kα radiation
Cell parameters from 3192 reflections
θ = 3.0–27.5°
μ = 0.09 mm⁻¹
T = 120 (2) K
Block, colourless
0.40 × 0.38 × 0.30 mm

Data collection

Nonius KappaCCD diffractometer
φ and ω scans
Absorption correction: multi-scan(SADABS; Sheldrick, 2003)T_min = 0.956, T_max = 0.975
16180 measured reflections
3192 independent reflections
2520 reflections with I > 2σ(I)
R_int = 0.033
θ_max = 27.5°
h = −12 → 12
k = −9 → 10
l = −18 → 23

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.126
S = 1.06
3192 reflections
193 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0744P)² + 0.2357P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.25 e Å⁻³
Extinction correction: SHELXL97
Extinction coefficient: 0.028 (5)

Table 1
Selected geometric parameters (Å, °) for compounds (I)–(IV)

	(I)	(II)	(III)	(IV)
N1—C2	1.348 (3)	1.349 (2)	1.351 (3)	1.3522 (16)
C2—C3	1.400 (3)	1.407 (3)	1.408 (4)	1.4047 (18)
C3—C3A	1.380 (3)	1.380 (3)	1.381 (4)	1.3858 (18)
C3A—N4	1.356 (3)	1.358 (3)	1.361 (3)	1.3622 (16)
N4—C5	1.333 (3)	1.328 (3)	1.335 (3)	1.3255 (17)
C5—C5A	1.418 (3)	1.419 (3)	1.417 (4)	1.4202 (18)
C5A—C8A	1.358 (3)	1.360 (3)	1.362 (4)	1.3614 (18)
C8A—N8B	1.354 (3)	1.345 (3)	1.353 (3)	1.3587 (16)
N8B—N1	1.357 (3)	1.355 (3)	1.355 (3)	1.3592 (14)
C3A—N8B	1.403 (3)	1.401 (3)	1.395 (3)	1.3928 (15)
C23—C24—O24				124.80 (12)
C25—C24—O24				115.26 (11)
C24—O24—C241				117.88 (10)
N1—C2—C21—C22	−168.1 (2)	−166.2 (2)	−166.4 (2)	176.30 (11)
C23—C24—O24—C241				3.40 (18)

Table 2
Hydrogen bonds and short intramolecular contacts (Å, °) for compounds (I)–(IV)

Cg is the centroid of the N1/C2/C3/C3A/N8B ring.

Compound	D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
(I)	C6—H6A⋯Cgⁱ	0.99	2.94	3.902 (3)	163
(II)	C6—H6A⋯Cgⁱ	0.99	2.87	3.820 (3)	160
(III)	C6—H6A⋯Cgⁱ	0.99	2.99	3.942 (3)	161
(IV)	C22—H22⋯N4ⁱⁱ	0.95	2.54	3.436 (2)	156
Symmetry codes: (i) x, -1 + y, z; (ii) $[1 - x, -{1\over2} + y, {1\over2} - z]$ .

For each of (I)–(IV), the space group P2₁/c was uniquely assigned from the systematic absences. All H atoms were located from difference maps in fully ordered sites; they were then treated as riding atoms, with C—H distances of 0.95 (aromatic), 0.98 (methyl) or 0.99 Å (CH₂), and with U_iso(H) values of 1.2U_eq(C), or 1.5U_eq(C) for the methyl groups. For compounds (I) and (II), although not for (IV), the displacement parameters for atom C7 were somewhat higher than those of neighbouring C atoms, and were consistent with an enhanced vibrational amplitude approximately normal to the C6–C8 plane and tangential to the envelope fold. For compound (III), it was necessary to model this atom and its associated H atoms over two sets of sites, with refined occupancies of 0.853 (17) and 0.147 (17). The crystals of compound (III) are very fragile, and attempts to cut small fragments from larger crystals always 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: WinGX (Farrugia, 1999 ) and SIR92 (Altomare et al., 1993 ) for (I), (II) and (III), and OSCAIL (McArdle, 2003 ) and SHELXS97 (Sheldrick, 1997 ) for (IV); 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/S0108270105016720/sk1849sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270105016720/sk1849Isup2.hkl

Structure factors: contains datablock II. DOI: 10.1107/S0108270105016720/sk1849IIsup3.hkl

Structure factors: contains datablock III. DOI: 10.1107/S0108270105016720/sk1849IIIsup4.hkl

Structure factors: contains datablock IV. DOI: 10.1107/S0108270105016720/sk1849IVsup5.hkl

Comment top

Pyrazolo[1,5-a]pyrimidines are purine analogues which have shown useful properties as antimetabolites, and which have been of pharmaceutical interest because of their antitrypanosomal activity (Novinson et al., 1976) and their antischistosomal activity (Senga et al., 1981). These interesting biological properties have prompted the search for new and efficient procedures of wide generality for the synthesis of pyrazolo[1,5-a]pyrimidine derivatives (Al-Shiekh et al., 2004; Makarov et al., 2005). We report here the structures of four cyclopenta[e]pyrazolo[1,5-a]pyrimidines, namely 5-methyl-2-(4-methylphenyl)-7,8-dihydro-6H- cyclopenta[g]pyrazolo[1,5-a]pyrimidine, (I), 2-(4-chlorophenyl)-5-methyl-7,8-dihydro-6H- cyclopenta[g]pyrazolo[1,5-a]pyrimidine, (II), 2-(4-bromophenyl)-5-methyl-7,8-dihydro-6H- cyclopenta[g]pyrazolo[1,5-a]pyrimidine, (III), and 2-(4-methoxyphenyl)-5-methyl-7,8-dihydro-6H- cyclopenta[g]pyrazolo[1,5-a]pyrimidine, (IV), prepared by solvent-free cyclocondensation reactions between 5-amino-1H-pyrazole derivatives and 2-acetylcyclopentanone, induced by microwave irradiation.

Compounds (I)–(III) form isomorphous crystals, and the compounds are isostructural, consistent with the similar steric requirements of methyl, chloro and bromo substituents, as reflected for example in the similar unit-cell dimensions of (I)–(III).

The corresponding bond lengths within the heterobicyclic fragments in compounds (I)–(IV) (Figs. 1–4) are very similar (Table 1), but the patterns of these bond distances show some interesting properties. In each of (I)–(IV), the N1—C2 bond, which is formally a double bond, is not significantly shorter than the C3A—N4 and C8A—N8B bonds, both of which are formally single bonds; at the same time the cross-ring bonds C3A—N8B are by far the longest C—N bond in either molecule. These observations, together with the clear bond-fixation in the pyrimidine ring, suggest that the ten π electrons of the pyrazolopyrimidine units are not fully delocalized around the periphery, but instead adopt a more characteristic arrangement, reminiscent of that in naphthalene.

In all of these compounds, the five-membered carbocyclic ring has an envelope conformation, with the fold across the line C6···C8; the total puckering amplitude Q (Cremer & Pople, 1975) is rather larger in (III) [0.231 (4) Å] than in any of (I) [0.111 (3) Å], (II) [0.159 (3) Å] or (IV) [0.095 (2) Å], but in each case the ring-puckering parameter ϕ₂ [257.1 (14)° in (I), 255.0 (10)° in (II), 73.3 (8)° in (III) and 73.6 (8)° in (IV) for the atom sequence C5A, C6, C7, C8, C8A] is very close to the ideal value of 36n° (Evans & Boeyens, 1989), with n = 7 in (I) and (II), and n = 2 in (III) and (IV). The 4-substituted C21–C26 aryl ring is nearly coplanar with the heterobicyclic ring in each of (I)–(IV); thus the dihedral angles between the aryl ring and the mean plane of the pyrazolopyrimidine ring are 12.0 (2)° in (I), 14.5 (2)° in (II), 14.2 (2)° in (III) and 3.6 (2)° in (III). In compound (IV) the methoxy atom C241 is nearly coplanar with the aryl ring and, consistent with this, the exocyclic C—C—O angles at C24 show the usual deviations from 120° (Table 1).

In each of compounds (I)–(III), the molecules are linked into chains by a single C—H···π(arene) hydrogen bond (Table 2): atom C6 in the molecule at (x, y, z) acts as a donor, via atom H6A, to the pyrazole ring in the molecule at (x, −1 + y, z), so generating by translation a chain running parallel to the [010] direction (Fig. 5). It should be noted that C—H···N and, in (II) and (III), C—H···halogen hydrogen bonds, and aromatic π–π stacking interactions, are all absent from the structures of (I)–(III).

By contrast, in compound (IV), the molecules are linked into chains by a C—H···N hydrogen bond (Table 2), and these chains are themselves linked into sheets by a π–π stacking interaction. Aryl atom C22 in the molecule at (x, y, z) acts as a hydrogen-bond donor to pyrimidine atom N4 in the molecule at (1 − x, −1/2 + y, 1/2 − z), so forming a C(7) chain running parallel to the [010] direction and generated by the 2₁ screw axis along (1/2, y, 1/4) (Fig. 6). The π–π stacking interaction involves the fused heterocyclic rings of the molecules at (x, y, z) and (1 − x, 2 − y, −z), where the interplanar spacing is 3.504 (2) Å; the ring-centroid separation of the pyrazole and pyrimidine rings, respectively, is 3.577 (2) Å, corresponding to a ring-centroid offset of 0.719 (2) Å; the corresponding separation of the pyrimidine centroids is 3.799 (2) Å, with a centroid offset of 1.489 (2) Å. These two molecules lie in the C(7) chains along (1/2, y,1/4) and (1/2, y, −0.25), respectively, and propagation by the space group of this stacking interaction generates a sheet lying parallel to (100) (Fig. 7).

It is striking to that, although the substituents in the aryl rings, viz. 4-methyl in (I), 4-chloro in (II), 4-bromo in (III) and 4-methoxy in (IV), play no direct role whatever in the supramolecular aggregation, nonetheless the types of direction-specific intermolecular interaction apparent in the crystal structures of (I)–(III) are entirely different from those apparent in the structure of (IV). The influence of these remote substituents on the supramolecular structures thus appears to be indirect and rather subtle, but real nonetheless; such subtle influences necessarily hinder the effective prediction of such structures.

Experimental top

Equimolar mixtures of the appropriate 5-amino-3-aryl-1H-pyrazole (2.6 mmol) [where aryl is 4-methylphenyl for (I), 4-chlorophenyl for (II), 4-bromophenyl for (III) and 4-methoxyphenyl for (IV)] and 2-acetylcyclopentanone (2.6 mmol) were placed in open Pyrex-glass vessels and irradiated in a domestic microwave oven for 1.5–2 min at 600 W. The product mixtures were extracted with ethanol, and after removal of the solvent the resulting solids were recrystallized from dimethylformamide to give crystals of (I)–(IV) suitable for single-crystal X-ray diffraction. For (I), m.p. 512–513 K, yield 80%; MS (30 eV) m/z (%): 263 (100, M+), 248 (4). For (II), m.p. 496–497 K, yield 83%; MS: (30 eV) m/z (%): 285/283 (35/100, M+), 268 (3), 241 (2). For (III), m.p. 496–497 K, yield 83%; MS: (30 eV) m/z (%): 329/327 (97/100, M+), 312 (3). For (IV), m.p. 497–498 K, yield 85%; MS: (30 eV) m/z (%): 279 (100, M+), 264 (27), 236 (7).

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: WinGX (Farrugia, 1999) and SIR92 (Altomare et al., 1993) for (I), (II), (III); OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997) for (IV). Program(s) used to refine structure: OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick, 1997) for (I), (II), (III); OSCAIL and SHELXL97 (Sheldrick, 1997) for (IV). For all 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. The molecule of (III), showing the atom-labelling scheme. For clarity, only the major orientation of the disordered CH₂ group is shown. 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 by the C—H···π(arene) hydrogen bond of a chain along [010]. For clarity, H atoms bonded to those C atoms that are not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (x, −1 + y, z) and (x, 1 + y, z), respectively. The [010] chains in (II) and (III) are essentially identical to that in (I).
	Fig. 6. Part of the crystal structure of (IV), showing the formation by the C—H···N hydrogen bond of a C(7) chain along [010]. 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, −1/2 + y, 1/2 − z) and (1 − x, 1/2 + y, 1/2 − z), respectively.
	Fig. 7. A stereoview of part of the crystal structure of compound (IV), showing the formation of a (100) sheet of π-stacked [010] chains. For clarity, H atoms not involved in the motif shown have been omitted.

(I) 5-methyl-2-(4-methylphenyl)-7,8-dihydro-6H- cyclopenta[g]pyrazolo[1,5-a]pyrimidine top

Crystal data top

C₁₇H₁₇N₃	F(000) = 560
M_r = 263.34	D_x = 1.306 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3076 reflections
a = 13.2882 (7) Å	θ = 3.2–27.5°
b = 6.8383 (4) Å	µ = 0.08 mm⁻¹
c = 15.1947 (8) Å	T = 120 K
β = 104.018 (3)°	Needle, colourless
V = 1339.60 (13) Å³	0.52 × 0.08 × 0.04 mm
Z = 4

Data collection top

Nonius KappaCCD diffractometer	3076 independent reflections
Radiation source: Bruker-Nonius FR91 rotating anode	1640 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.085
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.5°, θ_min = 3.2°
ϕ and ω scans	h = −17→16
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −8→8
T_min = 0.955, T_max = 0.997	l = −19→19
13947 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)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.175	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0891P)² + 0.0582P] where P = (F_o² + 2F_c²)/3
3076 reflections	(Δ/σ)_max < 0.001
183 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₁₇H₁₇N₃	V = 1339.60 (13) Å³
M_r = 263.34	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.2882 (7) Å	µ = 0.08 mm⁻¹
b = 6.8383 (4) Å	T = 120 K
c = 15.1947 (8) Å	0.52 × 0.08 × 0.04 mm
β = 104.018 (3)°

Data collection top

Nonius KappaCCD diffractometer	3076 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	1640 reflections with I > 2σ(I)
T_min = 0.955, T_max = 0.997	R_int = 0.085
13947 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.064	0 restraints
wR(F²) = 0.175	H-atom parameters constrained
S = 1.01	Δρ_max = 0.35 e Å⁻³
3076 reflections	Δρ_min = −0.29 e Å⁻³
183 parameters

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

	x	y	z	U_iso*/U_eq
N1	0.28324 (14)	0.4477 (3)	0.19324 (13)	0.0258 (5)
N4	0.04482 (14)	0.1982 (3)	0.10167 (13)	0.0279 (5)
N8B	0.21206 (14)	0.3036 (3)	0.18910 (12)	0.0240 (5)
C2	0.23925 (17)	0.5664 (3)	0.12375 (15)	0.0238 (6)
C3	0.14141 (18)	0.5009 (4)	0.07606 (16)	0.0265 (6)
C3A	0.12370 (17)	0.3295 (3)	0.11783 (16)	0.0258 (6)
C5	0.05294 (17)	0.0436 (4)	0.15636 (16)	0.0270 (6)
C5A	0.14031 (18)	0.0171 (4)	0.23026 (15)	0.0255 (6)
C6	0.16504 (19)	−0.1433 (4)	0.30027 (17)	0.0329 (6)
C7	0.2658 (2)	−0.0766 (5)	0.3649 (2)	0.0763 (13)
C8	0.30840 (19)	0.0996 (4)	0.32186 (17)	0.0333 (6)
C8A	0.21968 (17)	0.1475 (3)	0.24522 (15)	0.0249 (6)
C21	0.29531 (17)	0.7434 (3)	0.10803 (14)	0.0233 (6)
C22	0.24563 (18)	0.8880 (3)	0.04843 (16)	0.0265 (6)
C23	0.29724 (18)	1.0569 (3)	0.03507 (16)	0.0284 (6)
C24	0.40046 (18)	1.0871 (3)	0.07952 (16)	0.0265 (6)
C25	0.45066 (18)	0.9414 (4)	0.13829 (16)	0.0285 (6)
C26	0.39874 (18)	0.7730 (4)	0.15188 (15)	0.0277 (6)
C51	−0.03292 (19)	−0.1036 (4)	0.13818 (18)	0.0364 (7)
C241	0.4567 (2)	1.2719 (4)	0.06545 (17)	0.0352 (7)
H3	0.0964	0.5619	0.0253	0.032*
H6A	0.1746	−0.2700	0.2718	0.040*
H6B	0.1090	−0.1571	0.3325	0.040*
H7A	0.3170	−0.1845	0.3754	0.092*
H7B	0.2527	−0.0385	0.4240	0.092*
H8A	0.3257	0.2100	0.3650	0.040*
H8B	0.3705	0.0634	0.3004	0.040*
H22	0.1753	0.8703	0.0165	0.032*
H23	0.2614	1.1542	−0.0053	0.034*
H24A	0.4995	1.3169	0.1238	0.053*
H24B	0.4060	1.3733	0.0395	0.053*
H24C	0.5011	1.2455	0.0239	0.053*
H25	0.5213	0.9580	0.1693	0.034*
H26	0.4346	0.6755	0.1920	0.033*
H51A	−0.0903	−0.0558	0.1624	0.055*
H51B	−0.0073	−0.2276	0.1676	0.055*
H51C	−0.0574	−0.1240	0.0726	0.055*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0264 (11)	0.0235 (11)	0.0275 (11)	−0.0008 (9)	0.0069 (9)	0.0004 (9)
C2	0.0257 (13)	0.0254 (13)	0.0223 (12)	0.0035 (11)	0.0093 (11)	−0.0003 (11)
C21	0.0263 (13)	0.0223 (13)	0.0220 (12)	0.0010 (10)	0.0073 (10)	−0.0025 (10)
C26	0.0275 (14)	0.0282 (14)	0.0251 (13)	0.0014 (11)	0.0018 (11)	−0.0009 (11)
C25	0.0233 (13)	0.0321 (15)	0.0296 (13)	0.0003 (11)	0.0053 (11)	−0.0072 (12)
C24	0.0288 (14)	0.0258 (13)	0.0267 (13)	−0.0022 (11)	0.0100 (11)	−0.0080 (11)
C241	0.0365 (15)	0.0335 (15)	0.0366 (15)	−0.0075 (13)	0.0110 (12)	−0.0068 (13)
C23	0.0305 (14)	0.0264 (14)	0.0283 (13)	0.0005 (11)	0.0073 (11)	0.0012 (11)
C22	0.0235 (13)	0.0270 (13)	0.0292 (13)	0.0014 (11)	0.0066 (11)	−0.0023 (11)
C3	0.0251 (13)	0.0272 (13)	0.0254 (12)	0.0011 (11)	0.0024 (11)	0.0029 (11)
C3A	0.0241 (13)	0.0272 (14)	0.0264 (13)	0.0026 (11)	0.0065 (11)	0.0005 (11)
N4	0.0242 (11)	0.0271 (12)	0.0312 (11)	−0.0019 (9)	0.0046 (9)	0.0030 (10)
C5	0.0248 (14)	0.0273 (14)	0.0304 (14)	0.0026 (11)	0.0097 (11)	0.0002 (12)
C51	0.0356 (15)	0.0325 (15)	0.0410 (16)	−0.0017 (12)	0.0089 (12)	0.0063 (13)
C5A	0.0263 (13)	0.0261 (13)	0.0268 (13)	0.0068 (11)	0.0114 (11)	0.0026 (11)
C6	0.0375 (15)	0.0294 (14)	0.0355 (15)	0.0033 (12)	0.0159 (12)	0.0057 (12)
C7	0.0433 (19)	0.094 (3)	0.079 (3)	−0.0200 (19)	−0.0105 (18)	0.055 (2)
C8	0.0299 (14)	0.0386 (16)	0.0306 (14)	0.0023 (12)	0.0055 (11)	0.0052 (12)
C8A	0.0252 (13)	0.0280 (13)	0.0236 (12)	0.0053 (11)	0.0098 (10)	0.0029 (11)
N8B	0.0232 (11)	0.0237 (11)	0.0246 (10)	0.0001 (9)	0.0046 (9)	0.0015 (9)

Geometric parameters (Å, º) top

N1—C2	1.348 (3)	C3A—N4	1.356 (3)
N1—N8B	1.357 (3)	C3A—N8B	1.403 (3)
C2—C3	1.400 (3)	N4—C5	1.333 (3)
C2—C21	1.471 (3)	C5—C5A	1.418 (3)
C21—C26	1.389 (3)	C5—C51	1.497 (3)
C21—C22	1.395 (3)	C51—H51A	0.98
C26—C25	1.383 (3)	C51—H51B	0.98
C26—H26	0.95	C51—H51C	0.98
C25—C24	1.395 (3)	C5A—C8A	1.358 (3)
C25—H25	0.95	C5A—C6	1.508 (3)
C24—C23	1.390 (3)	C6—C7	1.526 (4)
C24—C241	1.509 (3)	C6—H6A	0.99
C241—H24A	0.98	C6—H6B	0.99
C241—H24B	0.98	C7—C8	1.542 (4)
C241—H24C	0.98	C7—H7A	0.99
C23—C22	1.383 (3)	C7—H7B	0.99
C23—H23	0.95	C8—C8A	1.479 (3)
C22—H22	0.95	C8—H8A	0.99
C3—C3A	1.380 (3)	C8—H8B	0.99
C3—H3	0.95	C8A—N8B	1.354 (3)

C2—N1—N8B	103.65 (18)	N4—C5—C51	118.4 (2)
N1—C2—C3	112.6 (2)	C5A—C5—C51	120.1 (2)
N1—C2—C21	118.8 (2)	C5—C51—H51A	109.5
C3—C2—C21	128.5 (2)	C5—C51—H51B	109.5
C26—C21—C22	117.8 (2)	H51A—C51—H51B	109.5
C26—C21—C2	121.5 (2)	C5—C51—H51C	109.5
C22—C21—C2	120.7 (2)	H51A—C51—H51C	109.5
C25—C26—C21	121.4 (2)	H51B—C51—H51C	109.5
C25—C26—H26	119.3	C8A—C5A—C5	120.2 (2)
C21—C26—H26	119.3	C8A—C5A—C6	109.4 (2)
C26—C25—C24	120.8 (2)	C5—C5A—C6	130.4 (2)
C26—C25—H25	119.6	C5A—C6—C7	104.1 (2)
C24—C25—H25	119.6	C5A—C6—H6A	110.9
C23—C24—C25	117.9 (2)	C7—C6—H6A	110.9
C23—C24—C241	121.3 (2)	C5A—C6—H6B	110.9
C25—C24—C241	120.8 (2)	C7—C6—H6B	110.9
C24—C241—H24A	109.5	H6A—C6—H6B	109.0
C24—C241—H24B	109.5	C6—C7—C8	108.4 (2)
H24A—C241—H24B	109.5	C6—C7—H7A	110.0
C24—C241—H24C	109.5	C8—C7—H7A	110.0
H24A—C241—H24C	109.5	C6—C7—H7B	110.0
H24B—C241—H24C	109.5	C8—C7—H7B	110.0
C22—C23—C24	121.3 (2)	H7A—C7—H7B	108.4
C22—C23—H23	119.4	C8A—C8—C7	101.7 (2)
C24—C23—H23	119.4	C8A—C8—H8A	111.4
C23—C22—C21	120.9 (2)	C7—C8—H8A	111.4
C23—C22—H22	119.5	C8A—C8—H8B	111.4
C21—C22—H22	119.5	C7—C8—H8B	111.4
C3A—C3—C2	105.9 (2)	H8A—C8—H8B	109.3
C3A—C3—H3	127.0	N8B—C8A—C5A	118.4 (2)
C2—C3—H3	127.0	N8B—C8A—C8	126.4 (2)
N4—C3A—C3	133.6 (2)	C5A—C8A—C8	115.1 (2)
N4—C3A—N8B	121.5 (2)	C8A—N8B—N1	126.75 (19)
C3—C3A—N8B	105.0 (2)	C8A—N8B—C3A	120.4 (2)
C5—N4—C3A	118.0 (2)	N1—N8B—C3A	112.81 (18)
N4—C5—C5A	121.5 (2)

N8B—N1—C2—C3	0.4 (2)	N4—C5—C5A—C8A	−1.9 (3)
N8B—N1—C2—C21	179.27 (18)	C51—C5—C5A—C8A	178.0 (2)
N1—C2—C21—C26	11.7 (3)	N4—C5—C5A—C6	179.4 (2)
C3—C2—C21—C26	−169.6 (2)	C51—C5—C5A—C6	−0.6 (4)
N1—C2—C21—C22	−168.1 (2)	C8A—C5A—C6—C7	5.8 (3)
C3—C2—C21—C22	10.6 (3)	C5—C5A—C6—C7	−175.5 (3)
C22—C21—C26—C25	1.0 (3)	C5A—C6—C7—C8	−10.6 (3)
C2—C21—C26—C25	−178.7 (2)	C6—C7—C8—C8A	11.0 (3)
C21—C26—C25—C24	−0.2 (3)	C5—C5A—C8A—N8B	1.2 (3)
C26—C25—C24—C23	−0.3 (3)	C6—C5A—C8A—N8B	−179.95 (19)
C26—C25—C24—C241	179.3 (2)	C5—C5A—C8A—C8	−177.4 (2)
C25—C24—C23—C22	0.0 (3)	C6—C5A—C8A—C8	1.4 (3)
C241—C24—C23—C22	−179.6 (2)	C7—C8—C8A—N8B	173.7 (3)
C24—C23—C22—C21	0.8 (3)	C7—C8—C8A—C5A	−7.9 (3)
C26—C21—C22—C23	−1.3 (3)	C5A—C8A—N8B—N1	−179.7 (2)
C2—C21—C22—C23	178.4 (2)	C8—C8A—N8B—N1	−1.3 (4)
N1—C2—C3—C3A	−0.7 (3)	C5A—C8A—N8B—C3A	0.5 (3)
C21—C2—C3—C3A	−179.4 (2)	C8—C8A—N8B—C3A	178.9 (2)
C2—C3—C3A—N4	−178.3 (2)	C2—N1—N8B—C8A	−179.7 (2)
C2—C3—C3A—N8B	0.6 (2)	C2—N1—N8B—C3A	0.1 (2)
C3—C3A—N4—C5	179.6 (2)	N4—C3A—N8B—C8A	−1.5 (3)
N8B—C3A—N4—C5	0.8 (3)	C3—C3A—N8B—C8A	179.37 (19)
C3A—N4—C5—C5A	0.9 (3)	N4—C3A—N8B—N1	178.68 (19)
C3A—N4—C5—C51	−179.0 (2)	C3—C3A—N8B—N1	−0.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6A···Cgⁱ	0.99	2.94	3.902 (3)	163

Symmetry code: (i) x, y−1, z.

(II) 2-(4-chlorophenyl)-5-methyl-7,8-dihydro-6H- cyclopenta[g]pyrazolo[1,5-a]pyrimidine top

Crystal data top

C₁₆H₁₄ClN₃	F(000) = 592
M_r = 283.75	D_x = 1.421 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3040 reflections
a = 13.6800 (11) Å	θ = 3.4–27.6°
b = 6.6669 (6) Å	µ = 0.28 mm⁻¹
c = 15.2010 (16) Å	T = 120 K
β = 106.980 (6)°	Plate, colourless
V = 1325.9 (2) Å³	0.34 × 0.18 × 0.03 mm
Z = 4

Data collection top

Nonius KappaCCD diffractometer	3040 independent reflections
Radiation source: Bruker-Nonius FR91 rotating anode	2060 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.072
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.6°, θ_min = 3.4°
ϕ & ω scans	h = −16→17
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −8→8
T_min = 0.922, T_max = 0.992	l = −17→19
14750 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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.141	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0726P)² + 0.3419P] where P = (F_o² + 2F_c²)/3
3040 reflections	(Δ/σ)_max < 0.001
182 parameters	Δρ_max = 0.38 e Å⁻³
0 restraints	Δρ_min = −0.49 e Å⁻³

Crystal data top

C₁₆H₁₄ClN₃	V = 1325.9 (2) Å³
M_r = 283.75	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.6800 (11) Å	µ = 0.28 mm⁻¹
b = 6.6669 (6) Å	T = 120 K
c = 15.2010 (16) Å	0.34 × 0.18 × 0.03 mm
β = 106.980 (6)°

Data collection top

Nonius KappaCCD diffractometer	3040 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	2060 reflections with I > 2σ(I)
T_min = 0.922, T_max = 0.992	R_int = 0.072
14750 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	0 restraints
wR(F²) = 0.141	H-atom parameters constrained
S = 1.03	Δρ_max = 0.38 e Å⁻³
3040 reflections	Δρ_min = −0.49 e Å⁻³
182 parameters

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

	x	y	z	U_iso*/U_eq
Cl24	0.46187 (4)	1.29423 (9)	0.06360 (4)	0.0324 (2)
N1	0.28435 (13)	0.4384 (3)	0.19754 (13)	0.0230 (4)
N4	0.04453 (13)	0.1925 (3)	0.10474 (13)	0.0253 (5)
N8B	0.21315 (13)	0.2947 (3)	0.19358 (13)	0.0213 (4)
C2	0.23879 (16)	0.5622 (3)	0.12731 (15)	0.0218 (5)
C3	0.13983 (16)	0.4982 (4)	0.07837 (16)	0.0252 (5)
C3A	0.12360 (16)	0.3240 (3)	0.12111 (15)	0.0226 (5)
C5	0.05428 (17)	0.0352 (3)	0.16026 (17)	0.0256 (5)
C5A	0.14297 (16)	0.0047 (3)	0.23560 (16)	0.0236 (5)
C6	0.16917 (17)	−0.1605 (4)	0.30626 (17)	0.0278 (6)
C7	0.2702 (2)	−0.0880 (5)	0.3741 (2)	0.0533 (9)
C8	0.31289 (17)	0.0810 (4)	0.32808 (17)	0.0284 (6)
C8A	0.22232 (16)	0.1356 (4)	0.24982 (16)	0.0236 (5)
C21	0.29402 (16)	0.7402 (3)	0.11099 (15)	0.0222 (5)
C22	0.24311 (16)	0.8927 (3)	0.05310 (16)	0.0237 (5)
C23	0.29389 (16)	1.0622 (4)	0.03824 (16)	0.0258 (5)
C24	0.39768 (17)	1.0795 (3)	0.08118 (16)	0.0244 (5)
C25	0.45133 (17)	0.9302 (4)	0.13841 (16)	0.0267 (5)
C26	0.39875 (17)	0.7617 (4)	0.15286 (16)	0.0255 (5)
C51	−0.03146 (18)	−0.1142 (4)	0.14149 (18)	0.0320 (6)
H3	0.0938	0.5616	0.0267	0.030*
H22	0.1720	0.8798	0.0232	0.028*
H23	0.2580	1.1658	−0.0010	0.031*
H25	0.5227	0.9428	0.1672	0.032*
H26	0.4348	0.6585	0.1922	0.031*
H6A	0.1786	−0.2900	0.2779	0.033*
H6B	0.1153	−0.1760	0.3373	0.033*
H7A	0.2578	−0.0385	0.4314	0.064*
H7B	0.3197	−0.2001	0.3902	0.064*
H8A	0.3362	0.1957	0.3704	0.034*
H8B	0.3702	0.0335	0.3061	0.034*
H51A	−0.0815	−0.0717	0.1726	0.048*
H51B	−0.0042	−0.2462	0.1646	0.048*
H51C	−0.0647	−0.1222	0.0751	0.048*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl24	0.0293 (3)	0.0289 (4)	0.0364 (4)	−0.0089 (3)	0.0054 (3)	0.0011 (3)
N1	0.0214 (9)	0.0211 (10)	0.0248 (10)	−0.0003 (8)	0.0040 (8)	0.0008 (8)
N4	0.0190 (9)	0.0258 (11)	0.0295 (11)	−0.0006 (8)	0.0046 (8)	0.0033 (9)
N8B	0.0190 (9)	0.0224 (10)	0.0213 (10)	−0.0008 (8)	0.0040 (7)	0.0002 (8)
C2	0.0219 (11)	0.0220 (12)	0.0205 (12)	0.0020 (9)	0.0049 (9)	−0.0019 (10)
C3	0.0215 (12)	0.0268 (13)	0.0253 (13)	0.0020 (10)	0.0037 (9)	0.0033 (11)
C3A	0.0184 (11)	0.0230 (13)	0.0249 (12)	0.0017 (9)	0.0040 (9)	−0.0010 (10)
C5	0.0233 (12)	0.0247 (13)	0.0293 (13)	0.0031 (10)	0.0085 (10)	−0.0003 (11)
C5A	0.0240 (12)	0.0216 (12)	0.0266 (13)	0.0025 (10)	0.0095 (10)	0.0016 (10)
C6	0.0273 (12)	0.0268 (13)	0.0310 (14)	0.0031 (10)	0.0114 (10)	0.0065 (11)
C7	0.0346 (15)	0.060 (2)	0.055 (2)	−0.0107 (14)	−0.0031 (13)	0.0317 (17)
C8	0.0226 (11)	0.0326 (14)	0.0272 (13)	0.0009 (10)	0.0029 (9)	0.0073 (11)
C8A	0.0219 (11)	0.0250 (12)	0.0242 (13)	0.0042 (9)	0.0074 (9)	0.0007 (10)
C21	0.0217 (11)	0.0237 (12)	0.0206 (12)	0.0003 (9)	0.0053 (9)	−0.0018 (9)
C22	0.0191 (11)	0.0264 (13)	0.0243 (12)	−0.0007 (9)	0.0044 (9)	−0.0016 (10)
C23	0.0259 (12)	0.0226 (13)	0.0275 (13)	0.0030 (10)	0.0057 (10)	0.0016 (10)
C24	0.0250 (12)	0.0222 (12)	0.0271 (13)	−0.0048 (10)	0.0095 (10)	−0.0046 (10)
C25	0.0229 (12)	0.0281 (13)	0.0254 (13)	−0.0014 (10)	0.0013 (9)	−0.0037 (10)
C26	0.0231 (12)	0.0261 (13)	0.0251 (13)	0.0027 (9)	0.0033 (9)	0.0000 (10)
C51	0.0250 (12)	0.0286 (14)	0.0389 (15)	−0.0041 (10)	0.0038 (10)	0.0057 (12)

Geometric parameters (Å, º) top

N1—C2	1.349 (3)	N4—C5	1.328 (3)
N1—N8B	1.355 (3)	C5—C5A	1.419 (3)
C2—C3	1.407 (3)	C5—C51	1.501 (3)
C2—C21	1.466 (3)	C51—H51A	0.98
C21—C22	1.391 (3)	C51—H51B	0.98
C21—C26	1.395 (3)	C51—H51C	0.98
C26—C25	1.385 (3)	C5A—C8A	1.360 (3)
C26—H26	0.95	C5A—C6	1.507 (3)
C25—C24	1.384 (3)	C6—C7	1.541 (4)
C25—H25	0.95	C6—H6A	0.99
C24—C23	1.383 (3)	C6—H6B	0.99
C24—Cl24	1.740 (2)	C7—C8	1.530 (4)
C23—C22	1.379 (3)	C7—H7A	0.99
C23—H23	0.95	C7—H7B	0.99
C22—H22	0.95	C8—C8A	1.491 (3)
C3—C3A	1.380 (3)	C8—H8A	0.99
C3—H3	0.95	C8—H8B	0.99
C3A—N4	1.358 (3)	C8A—N8B	1.345 (3)
C3A—N8B	1.401 (3)

C2—N1—N8B	103.73 (17)	C5—C51—H51B	109.5
N1—C2—C3	112.5 (2)	H51A—C51—H51B	109.5
N1—C2—C21	119.15 (18)	C5—C51—H51C	109.5
C3—C2—C21	128.3 (2)	H51A—C51—H51C	109.5
C22—C21—C26	118.1 (2)	H51B—C51—H51C	109.5
C22—C21—C2	120.72 (19)	C8A—C5A—C5	119.4 (2)
C26—C21—C2	121.2 (2)	C8A—C5A—C6	110.07 (19)
C25—C26—C21	121.5 (2)	C5—C5A—C6	130.5 (2)
C25—C26—H26	119.2	C5A—C6—C7	103.2 (2)
C21—C26—H26	119.2	C5A—C6—H6A	111.1
C24—C25—C26	118.6 (2)	C7—C6—H6A	111.1
C24—C25—H25	120.7	C5A—C6—H6B	111.1
C26—C25—H25	120.7	C7—C6—H6B	111.1
C23—C24—C25	121.3 (2)	H6A—C6—H6B	109.1
C23—C24—Cl24	119.37 (18)	C8—C7—C6	108.2 (2)
C25—C24—Cl24	119.33 (17)	C8—C7—H7A	110.1
C22—C23—C24	119.2 (2)	C6—C7—H7A	110.1
C22—C23—H23	120.4	C8—C7—H7B	110.1
C24—C23—H23	120.4	C6—C7—H7B	110.1
C23—C22—C21	121.3 (2)	H7A—C7—H7B	108.4
C23—C22—H22	119.4	C8A—C8—C7	101.85 (19)
C21—C22—H22	119.4	C8A—C8—H8A	111.4
C3A—C3—C2	105.58 (19)	C7—C8—H8A	111.4
C3A—C3—H3	127.2	C8A—C8—H8B	111.4
C2—C3—H3	127.2	C7—C8—H8B	111.4
N4—C3A—C3	133.3 (2)	H8A—C8—H8B	109.3
N4—C3A—N8B	121.4 (2)	N8B—C8A—C5A	118.9 (2)
C3—C3A—N8B	105.28 (19)	N8B—C8A—C8	127.0 (2)
C5—N4—C3A	117.82 (19)	C5A—C8A—C8	114.1 (2)
N4—C5—C5A	122.0 (2)	C8A—N8B—N1	126.65 (18)
N4—C5—C51	118.4 (2)	C8A—N8B—C3A	120.49 (19)
C5A—C5—C51	119.7 (2)	N1—N8B—C3A	112.85 (18)
C5—C51—H51A	109.5

N8B—N1—C2—C3	−0.4 (2)	N4—C5—C5A—C8A	−2.6 (4)
N8B—N1—C2—C21	179.24 (19)	C51—C5—C5A—C8A	177.0 (2)
N1—C2—C21—C22	−166.2 (2)	N4—C5—C5A—C6	179.7 (2)
C3—C2—C21—C22	13.5 (4)	C51—C5—C5A—C6	−0.7 (4)
N1—C2—C21—C26	13.8 (3)	C8A—C5A—C6—C7	8.7 (3)
C3—C2—C21—C26	−166.5 (2)	C5—C5A—C6—C7	−173.4 (3)
C22—C21—C26—C25	0.5 (4)	C5A—C6—C7—C8	−15.2 (3)
C2—C21—C26—C25	−179.5 (2)	C6—C7—C8—C8A	15.6 (3)
C21—C26—C25—C24	0.2 (4)	C5—C5A—C8A—N8B	2.2 (3)
C26—C25—C24—C23	−0.6 (4)	C6—C5A—C8A—N8B	−179.7 (2)
C26—C25—C24—Cl24	178.95 (18)	C5—C5A—C8A—C8	−176.9 (2)
C25—C24—C23—C22	0.1 (4)	C6—C5A—C8A—C8	1.2 (3)
Cl24—C24—C23—C22	−179.35 (18)	C7—C8—C8A—N8B	170.4 (3)
C24—C23—C22—C21	0.6 (4)	C7—C8—C8A—C5A	−10.6 (3)
C26—C21—C22—C23	−1.0 (4)	C5A—C8A—N8B—N1	−179.6 (2)
C2—C21—C22—C23	179.0 (2)	C8—C8A—N8B—N1	−0.7 (4)
N1—C2—C3—C3A	−0.1 (3)	C5A—C8A—N8B—C3A	−0.5 (3)
C21—C2—C3—C3A	−179.7 (2)	C8—C8A—N8B—C3A	178.4 (2)
C2—C3—C3A—N4	−178.6 (2)	C2—N1—N8B—C8A	180.0 (2)
C2—C3—C3A—N8B	0.5 (2)	C2—N1—N8B—C3A	0.8 (2)
C3—C3A—N4—C5	179.5 (3)	N4—C3A—N8B—C8A	−0.9 (3)
N8B—C3A—N4—C5	0.5 (3)	C3—C3A—N8B—C8A	179.9 (2)
C3A—N4—C5—C5A	1.2 (3)	N4—C3A—N8B—N1	178.3 (2)
C3A—N4—C5—C51	−178.5 (2)	C3—C3A—N8B—N1	−0.9 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6A···Cgⁱ	0.99	2.87	3.820 (3)	160

Symmetry code: (i) x, y−1, z.

(III) 2-(4-bromophenyl)-5-methyl-7,8-dihydro-6H- cyclopenta[g]pyrazolo[1,5-a]pyrimidine top

Crystal data top

C₁₆H₁₄BrN₃	F(000) = 664
M_r = 328.21	D_x = 1.597 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3125 reflections
a = 13.5387 (6) Å	θ = 3.3–27.5°
b = 6.8551 (2) Å	µ = 3.00 mm⁻¹
c = 15.2767 (7) Å	T = 120 K
β = 105.708 (2)°	Plate, colourless
V = 1364.87 (10) Å³	0.66 × 0.20 × 0.02 mm
Z = 4

Data collection top

Nonius KappaCCD diffractometer	3125 independent reflections
Radiation source: Bruker-Nonius FR91 rotating anode	2438 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.069
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.5°, θ_min = 3.3°
ϕ and ω scans	h = −17→17
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −8→8
T_min = 0.242, T_max = 0.942	l = −19→19
18357 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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.096	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0473P)² + 0.618P] where P = (F_o² + 2F_c²)/3
3125 reflections	(Δ/σ)_max = 0.001
186 parameters	Δρ_max = 0.41 e Å⁻³
2 restraints	Δρ_min = −0.68 e Å⁻³

Crystal data top

C₁₆H₁₄BrN₃	V = 1364.87 (10) Å³
M_r = 328.21	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.5387 (6) Å	µ = 3.00 mm⁻¹
b = 6.8551 (2) Å	T = 120 K
c = 15.2767 (7) Å	0.66 × 0.20 × 0.02 mm
β = 105.708 (2)°

Data collection top

Nonius KappaCCD diffractometer	3125 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	2438 reflections with I > 2σ(I)
T_min = 0.242, T_max = 0.942	R_int = 0.069
18357 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	2 restraints
wR(F²) = 0.096	H-atom parameters constrained
S = 1.05	Δρ_max = 0.41 e Å⁻³
3125 reflections	Δρ_min = −0.68 e Å⁻³
186 parameters

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Br24	0.46697 (2)	1.29662 (4)	0.06561 (2)	0.02998 (12)
N1	0.28031 (16)	0.4414 (3)	0.19783 (15)	0.0206 (5)
N4	0.04328 (17)	0.1944 (3)	0.10205 (16)	0.0242 (5)
N8B	0.20942 (16)	0.2989 (3)	0.19183 (15)	0.0199 (5)
C2	0.23623 (19)	0.5604 (4)	0.12763 (18)	0.0210 (6)
C3	0.13854 (19)	0.4957 (4)	0.07760 (18)	0.0219 (6)
C3A	0.12190 (19)	0.3252 (4)	0.11961 (18)	0.0206 (6)
C5	0.0517 (2)	0.0409 (4)	0.15732 (19)	0.0234 (6)
C5A	0.13850 (19)	0.0146 (4)	0.23266 (18)	0.0213 (6)
C6	0.1635 (2)	−0.1454 (4)	0.3035 (2)	0.0280 (6)
C7	0.2581 (3)	−0.0600 (9)	0.3765 (4)	0.0328 (14)	0.853 (17)
C7A	0.2785 (9)	−0.114 (2)	0.351 (2)	0.030*	0.147 (17)
C8	0.3055 (2)	0.0958 (4)	0.32725 (19)	0.0276 (6)
C8A	0.2175 (2)	0.1445 (4)	0.24852 (18)	0.0210 (5)
C21	0.2917 (2)	0.7362 (4)	0.11228 (19)	0.0206 (5)
C22	0.2412 (2)	0.8831 (4)	0.05358 (18)	0.0220 (6)
C23	0.2926 (2)	1.0497 (4)	0.03934 (19)	0.0237 (6)
C24	0.3960 (2)	1.0683 (4)	0.08394 (18)	0.0213 (6)
C25	0.4487 (2)	0.9254 (4)	0.14247 (19)	0.0233 (6)
C26	0.3959 (2)	0.7598 (4)	0.15640 (19)	0.0234 (6)
C51	−0.0339 (2)	−0.1050 (4)	0.1373 (2)	0.0315 (7)
H3	0.0937	0.5564	0.0260	0.026*
H6A	0.1814	−0.2684	0.2775	0.034*
H6B	0.1053	−0.1695	0.3297	0.034*
H7A	0.2361	−0.0006	0.4272	0.039*	0.853 (17)
H7B	0.3086	−0.1642	0.4013	0.039*	0.853 (17)
H7C	0.3207	−0.2113	0.3296	0.036*	0.147 (17)
H7D	0.2915	−0.1289	0.4180	0.036*	0.147 (17)
H8A	0.3289	0.2111	0.3664	0.033*
H8B	0.3638	0.0423	0.3073	0.033*
H22	0.1705	0.8685	0.0230	0.026*
H23	0.2577	1.1495	−0.0003	0.028*
H25	0.5195	0.9405	0.1724	0.028*
H26	0.4310	0.6610	0.1965	0.028*
H51A	−0.0629	−0.1157	0.0714	0.047*
H51B	−0.0873	−0.0623	0.1653	0.047*
H51C	−0.0073	−0.2322	0.1621	0.047*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br24	0.02841 (17)	0.02698 (18)	0.03312 (19)	−0.00983 (12)	0.00588 (13)	0.00026 (12)
N1	0.0178 (11)	0.0214 (11)	0.0224 (12)	−0.0014 (9)	0.0052 (9)	0.0008 (9)
N4	0.0172 (11)	0.0244 (12)	0.0295 (13)	−0.0022 (9)	0.0039 (10)	0.0016 (10)
N8B	0.0171 (10)	0.0209 (11)	0.0209 (12)	0.0012 (9)	0.0040 (9)	0.0015 (9)
C2	0.0181 (13)	0.0233 (13)	0.0221 (14)	0.0022 (10)	0.0061 (11)	−0.0019 (11)
C3	0.0178 (13)	0.0236 (13)	0.0223 (14)	0.0012 (11)	0.0020 (11)	0.0039 (11)
C3A	0.0158 (12)	0.0223 (13)	0.0231 (14)	0.0027 (10)	0.0041 (11)	0.0006 (10)
C5	0.0206 (13)	0.0207 (13)	0.0307 (16)	0.0015 (11)	0.0097 (12)	0.0009 (11)
C5A	0.0205 (13)	0.0214 (13)	0.0244 (14)	0.0037 (11)	0.0106 (11)	−0.0001 (11)
C6	0.0308 (15)	0.0256 (14)	0.0319 (17)	0.0028 (12)	0.0157 (13)	0.0068 (12)
C7	0.0281 (19)	0.039 (2)	0.032 (2)	0.0042 (18)	0.0098 (17)	0.0157 (18)
C8	0.0233 (14)	0.0323 (15)	0.0255 (15)	0.0034 (12)	0.0036 (12)	0.0073 (12)
C8A	0.0197 (13)	0.0212 (12)	0.0232 (15)	0.0041 (11)	0.0078 (11)	0.0027 (11)
C21	0.0190 (13)	0.0204 (12)	0.0227 (14)	−0.0003 (10)	0.0064 (11)	−0.0021 (10)
C22	0.0156 (12)	0.0256 (13)	0.0233 (15)	0.0032 (11)	0.0029 (11)	0.0003 (11)
C23	0.0224 (14)	0.0209 (13)	0.0269 (15)	0.0024 (11)	0.0050 (12)	0.0016 (11)
C24	0.0221 (13)	0.0195 (12)	0.0237 (15)	−0.0037 (10)	0.0084 (11)	−0.0029 (10)
C25	0.0185 (13)	0.0252 (14)	0.0234 (15)	−0.0014 (11)	0.0010 (11)	−0.0047 (11)
C26	0.0220 (13)	0.0228 (13)	0.0226 (14)	0.0029 (11)	0.0012 (11)	−0.0011 (11)
C51	0.0246 (14)	0.0266 (15)	0.0407 (18)	−0.0034 (12)	0.0043 (13)	0.0052 (13)

Geometric parameters (Å, º) top

N1—C2	1.351 (3)	C5—C51	1.498 (4)
N1—N8B	1.355 (3)	C51—H51A	0.98
C2—C3	1.408 (4)	C51—H51B	0.98
C2—C21	1.472 (4)	C51—H51C	0.98
C21—C26	1.398 (4)	C5A—C8A	1.362 (4)
C21—C22	1.398 (4)	C5A—C6	1.513 (4)
C22—C23	1.385 (4)	C6—C7A	1.545 (5)
C22—H22	0.95	C6—C7	1.566 (5)
C23—C24	1.386 (4)	C6—H6A	0.99
C23—H23	0.95	C6—H6B	0.99
C24—C25	1.387 (4)	C7—C8	1.543 (4)
C24—Br24	1.897 (3)	C7—H7A	0.99
C25—C26	1.389 (4)	C7—H7B	0.99
C25—H25	0.95	C7A—C8	1.555 (5)
C26—H26	0.95	C7A—H7C	0.99
C3—C3A	1.381 (4)	C7A—H7D	0.99
C3—H3	0.95	C8—C8A	1.484 (4)
C3A—N4	1.361 (3)	C8—H8A	0.99
C3A—N8B	1.395 (3)	C8—H8B	0.99
N4—C5	1.335 (3)	C8A—N8B	1.353 (3)
C5—C5A	1.417 (4)

C2—N1—N8B	103.2 (2)	C8A—C5A—C6	109.5 (2)
N1—C2—C3	112.9 (2)	C5—C5A—C6	130.5 (2)
N1—C2—C21	119.1 (2)	C5A—C6—C7A	103.9 (5)
C3—C2—C21	128.0 (2)	C5A—C6—C7	102.7 (2)
C26—C21—C22	118.7 (2)	C5A—C6—H6A	111.2
C26—C21—C2	120.6 (2)	C7A—C6—H6A	89.0
C22—C21—C2	120.6 (2)	C7—C6—H6A	111.2
C23—C22—C21	121.0 (2)	C5A—C6—H6B	111.2
C23—C22—H22	119.5	C7A—C6—H6B	130.0
C21—C22—H22	119.5	C7—C6—H6B	111.2
C22—C23—C24	118.8 (2)	H6A—C6—H6B	109.1
C22—C23—H23	120.6	C8—C7—C6	106.2 (3)
C24—C23—H23	120.6	C8—C7—H7A	110.5
C23—C24—C25	121.8 (2)	C6—C7—H7A	110.5
C23—C24—Br24	119.2 (2)	C8—C7—H7B	110.5
C25—C24—Br24	119.02 (19)	C6—C7—H7B	110.5
C24—C25—C26	118.7 (2)	H7A—C7—H7B	108.7
C24—C25—H25	120.7	C6—C7A—C8	106.6 (4)
C26—C25—H25	120.7	C6—C7A—H7C	110.4
C25—C26—C21	121.0 (3)	C8—C7A—H7C	110.4
C25—C26—H26	119.5	C6—C7A—H7D	110.4
C21—C26—H26	119.5	C8—C7A—H7D	110.4
C3A—C3—C2	105.2 (2)	H7C—C7A—H7D	108.6
C3A—C3—H3	127.4	C8A—C8—C7	101.7 (2)
C2—C3—H3	127.4	C8A—C8—C7A	102.2 (5)
N4—C3A—C3	133.1 (3)	C8A—C8—H8A	111.4
N4—C3A—N8B	121.5 (2)	C7—C8—H8A	111.4
C3—C3A—N8B	105.4 (2)	C7A—C8—H8A	130.8
C5—N4—C3A	117.8 (2)	C8A—C8—H8B	111.4
N4—C5—C5A	121.6 (2)	C7—C8—H8B	111.4
N4—C5—C51	117.9 (2)	C7A—C8—H8B	89.3
C5A—C5—C51	120.4 (2)	H8A—C8—H8B	109.3
C5—C51—H51A	109.5	N8B—C8A—C5A	118.3 (2)
C5—C51—H51B	109.5	N8B—C8A—C8	127.1 (2)
H51A—C51—H51B	109.5	C5A—C8A—C8	114.6 (2)
C5—C51—H51C	109.5	C8A—N8B—N1	126.0 (2)
H51A—C51—H51C	109.5	C8A—N8B—C3A	120.8 (2)
H51B—C51—H51C	109.5	N1—N8B—C3A	113.3 (2)
C8A—C5A—C5	120.0 (2)

N8B—N1—C2—C3	0.2 (3)	C5—C5A—C6—C7A	166.9 (15)
N8B—N1—C2—C21	179.7 (2)	C8A—C5A—C6—C7	13.1 (4)
N1—C2—C21—C26	13.4 (4)	C5—C5A—C6—C7	−168.4 (4)
C3—C2—C21—C26	−167.2 (3)	C5A—C6—C7—C8	−21.8 (5)
N1—C2—C21—C22	−166.4 (2)	C7A—C6—C7—C8	74.0 (10)
C3—C2—C21—C22	13.1 (4)	C5A—C6—C7A—C8	17 (2)
C26—C21—C22—C23	−0.3 (4)	C7—C6—C7A—C8	−72.8 (11)
C2—C21—C22—C23	179.5 (2)	C6—C7—C8—C8A	22.0 (5)
C21—C22—C23—C24	0.5 (4)	C6—C7—C8—C7A	−71.9 (9)
C22—C23—C24—C25	−0.3 (4)	C6—C7A—C8—C8A	−16 (2)
C22—C23—C24—Br24	−179.6 (2)	C6—C7A—C8—C7	74.9 (13)
C23—C24—C25—C26	0.0 (4)	C5—C5A—C8A—N8B	1.3 (4)
Br24—C24—C25—C26	179.2 (2)	C6—C5A—C8A—N8B	179.9 (2)
C24—C25—C26—C21	0.2 (4)	C5—C5A—C8A—C8	−177.6 (2)
C22—C21—C26—C25	−0.1 (4)	C6—C5A—C8A—C8	1.0 (3)
C2—C21—C26—C25	−179.8 (3)	C7—C8—C8A—N8B	166.4 (4)
N1—C2—C3—C3A	−0.4 (3)	C7A—C8—C8A—N8B	−168.9 (15)
C21—C2—C3—C3A	−179.9 (3)	C7—C8—C8A—C5A	−14.8 (4)
C2—C3—C3A—N4	−178.6 (3)	C7A—C8—C8A—C5A	9.9 (15)
C2—C3—C3A—N8B	0.4 (3)	C5A—C8A—N8B—N1	179.8 (2)
C3—C3A—N4—C5	179.9 (3)	C8—C8A—N8B—N1	−1.4 (4)
N8B—C3A—N4—C5	1.1 (4)	C5A—C8A—N8B—C3A	0.6 (4)
C3A—N4—C5—C5A	0.8 (4)	C8—C8A—N8B—C3A	179.3 (3)
C3A—N4—C5—C51	−179.0 (2)	C2—N1—N8B—C8A	−179.2 (2)
N4—C5—C5A—C8A	−2.0 (4)	C2—N1—N8B—C3A	0.1 (3)
C51—C5—C5A—C8A	177.7 (3)	N4—C3A—N8B—C8A	−1.9 (4)
N4—C5—C5A—C6	179.6 (3)	C3—C3A—N8B—C8A	179.0 (2)
C51—C5—C5A—C6	−0.6 (4)	N4—C3A—N8B—N1	178.8 (2)
C8A—C5A—C6—C7A	−11.6 (15)	C3—C3A—N8B—N1	−0.3 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6A···Cgⁱ	0.99	2.99	3.942 (3)	161

Symmetry code: (i) x, y−1, z.

(IV) (4-methoxyphenyl)-5-methyl- 7,8-dihydro-6H-cyclopenta[g]pyrazolo[1,5-a]pyrimidine top

Crystal data top

C₁₇H₁₇N₃O	F(000) = 592
M_r = 279.34	D_x = 1.336 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3192 reflections
a = 9.4691 (3) Å	θ = 3.0–27.5°
b = 8.1711 (2) Å	µ = 0.09 mm⁻¹
c = 18.0278 (6) Å	T = 120 K
β = 95.3430 (14)°	Block, colourless
V = 1388.80 (7) Å³	0.40 × 0.38 × 0.30 mm
Z = 4

Data collection top

Nonius KappaCCD diffractometer	3192 independent reflections
Radiation source: Bruker-Nonius FR91 rotating anode	2520 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.5°, θ_min = 3.0°
ϕ and ω scans	h = −12→12
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −9→10
T_min = 0.956, T_max = 0.975	l = −18→23
16180 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.042	H-atom parameters constrained
wR(F²) = 0.126	w = 1/[σ²(F_o²) + (0.0744P)² + 0.2357P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
3192 reflections	Δρ_max = 0.28 e Å⁻³
193 parameters	Δρ_min = −0.25 e Å⁻³
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.028 (5)

Crystal data top

C₁₇H₁₇N₃O	V = 1388.80 (7) Å³
M_r = 279.34	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.4691 (3) Å	µ = 0.09 mm⁻¹
b = 8.1711 (2) Å	T = 120 K
c = 18.0278 (6) Å	0.40 × 0.38 × 0.30 mm
β = 95.3430 (14)°

Data collection top

Nonius KappaCCD diffractometer	3192 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	2520 reflections with I > 2σ(I)
T_min = 0.956, T_max = 0.975	R_int = 0.033
16180 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.126	H-atom parameters constrained
S = 1.06	Δρ_max = 0.28 e Å⁻³
3192 reflections	Δρ_min = −0.25 e Å⁻³
193 parameters

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

	x	y	z	U_iso*/U_eq
O24	0.02704 (11)	0.07954 (12)	0.15877 (5)	0.0299 (3)
N1	0.23322 (11)	0.78754 (13)	0.06768 (6)	0.0204 (3)
N4	0.51632 (11)	1.03723 (14)	0.14924 (6)	0.0216 (3)
N8B	0.31726 (11)	0.92262 (13)	0.07384 (6)	0.0189 (3)
C2	0.28422 (13)	0.69345 (15)	0.12582 (7)	0.0190 (3)
C3	0.39961 (13)	0.76585 (16)	0.16825 (7)	0.0202 (3)
C3A	0.42028 (13)	0.91482 (16)	0.13414 (7)	0.0194 (3)
C5	0.51003 (13)	1.16535 (16)	0.10395 (7)	0.0205 (3)
C5A	0.40583 (13)	1.17745 (15)	0.04224 (7)	0.0198 (3)
C6	0.37829 (14)	1.31336 (16)	−0.01357 (7)	0.0231 (3)
C7	0.25751 (14)	1.24589 (17)	−0.06941 (7)	0.0256 (3)
C8	0.20303 (14)	1.08492 (16)	−0.03653 (7)	0.0235 (3)
C8A	0.30944 (13)	1.05514 (16)	0.02812 (7)	0.0191 (3)
C21	0.21810 (13)	0.53367 (16)	0.13736 (6)	0.0185 (3)
C22	0.27118 (13)	0.42800 (16)	0.19362 (7)	0.0215 (3)
C23	0.21110 (13)	0.27504 (16)	0.20273 (7)	0.0215 (3)
C24	0.09482 (13)	0.22649 (16)	0.15516 (7)	0.0209 (3)
C25	0.03881 (14)	0.33155 (16)	0.09878 (7)	0.0233 (3)
C26	0.09968 (13)	0.48305 (16)	0.09039 (7)	0.0214 (3)
C51	0.61754 (15)	1.29849 (17)	0.11988 (8)	0.0277 (3)
C241	0.07396 (16)	−0.02903 (17)	0.21789 (8)	0.0296 (3)
H3	0.4522	0.7221	0.2112	0.024*
H6A	0.4642	1.3374	−0.0390	0.028*
H6B	0.3480	1.4143	0.0108	0.028*
H7A	0.1795	1.3266	−0.0767	0.031*
H7B	0.2937	1.2244	−0.1183	0.031*
H8A	0.1067	1.0989	−0.0203	0.028*
H8B	0.2019	0.9943	−0.0731	0.028*
H22	0.3502	0.4611	0.2265	0.026*
H23	0.2493	0.2041	0.2412	0.026*
H24A	0.1751	−0.0524	0.2161	0.044*
H24B	0.0200	−0.1313	0.2125	0.044*
H24C	0.0591	0.0219	0.2657	0.044*
H25	−0.0410	0.2988	0.0663	0.028*
H26	0.0607	0.5543	0.0522	0.026*
H51A	0.5695	1.3991	0.1332	0.041*
H51B	0.6675	1.3182	0.0755	0.041*
H51C	0.6859	1.2653	0.1613	0.041*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O24	0.0327 (6)	0.0260 (6)	0.0297 (5)	−0.0103 (4)	−0.0039 (4)	0.0064 (4)
N1	0.0200 (5)	0.0212 (6)	0.0196 (6)	−0.0038 (4)	−0.0004 (4)	−0.0001 (4)
N4	0.0192 (6)	0.0250 (6)	0.0203 (6)	−0.0035 (4)	−0.0002 (4)	−0.0012 (4)
N8B	0.0174 (5)	0.0217 (6)	0.0173 (5)	−0.0027 (4)	0.0000 (4)	−0.0007 (4)
C2	0.0182 (6)	0.0225 (7)	0.0163 (6)	0.0001 (5)	0.0025 (5)	−0.0012 (5)
C3	0.0190 (6)	0.0240 (7)	0.0172 (6)	−0.0006 (5)	−0.0003 (5)	0.0002 (5)
C3A	0.0170 (6)	0.0253 (7)	0.0156 (6)	−0.0011 (5)	0.0000 (5)	−0.0020 (5)
C5	0.0186 (6)	0.0240 (7)	0.0192 (6)	−0.0010 (5)	0.0028 (5)	−0.0021 (5)
C5A	0.0192 (6)	0.0223 (7)	0.0186 (6)	−0.0003 (5)	0.0047 (5)	−0.0015 (5)
C6	0.0245 (7)	0.0229 (7)	0.0223 (7)	−0.0001 (5)	0.0041 (5)	0.0009 (5)
C7	0.0247 (7)	0.0274 (7)	0.0241 (7)	0.0016 (6)	−0.0008 (5)	0.0046 (5)
C8	0.0236 (7)	0.0262 (7)	0.0200 (6)	−0.0012 (5)	−0.0019 (5)	0.0012 (5)
C8A	0.0192 (6)	0.0217 (7)	0.0167 (6)	0.0005 (5)	0.0031 (5)	−0.0009 (5)
C21	0.0172 (6)	0.0221 (7)	0.0165 (6)	−0.0004 (5)	0.0025 (5)	−0.0018 (5)
C22	0.0186 (6)	0.0264 (7)	0.0190 (6)	−0.0011 (5)	−0.0013 (5)	−0.0019 (5)
C23	0.0219 (6)	0.0246 (7)	0.0177 (6)	0.0015 (5)	0.0004 (5)	0.0021 (5)
C24	0.0215 (6)	0.0220 (7)	0.0197 (6)	−0.0026 (5)	0.0046 (5)	−0.0008 (5)
C25	0.0205 (7)	0.0280 (7)	0.0205 (6)	−0.0046 (5)	−0.0019 (5)	0.0002 (5)
C26	0.0212 (6)	0.0256 (7)	0.0171 (6)	−0.0013 (5)	−0.0005 (5)	0.0027 (5)
C51	0.0267 (7)	0.0288 (7)	0.0270 (7)	−0.0075 (6)	−0.0005 (6)	−0.0003 (6)
C241	0.0329 (8)	0.0259 (7)	0.0303 (8)	−0.0022 (6)	0.0054 (6)	0.0073 (6)

Geometric parameters (Å, º) top

N1—C2	1.3522 (16)	C3A—N4	1.3622 (16)
N1—N8B	1.3592 (14)	C3A—N8B	1.3928 (15)
C2—C3	1.4047 (17)	N4—C5	1.3255 (17)
C2—C21	1.4710 (18)	C5—C5A	1.4202 (18)
C21—C22	1.3900 (18)	C5—C51	1.4993 (18)
C21—C26	1.4031 (18)	C51—H51A	0.98
C22—C23	1.3893 (18)	C51—H51B	0.98
C22—H22	0.95	C51—H51C	0.98
C23—C24	1.3890 (18)	C5A—C8A	1.3614 (18)
C23—H23	0.95	C5A—C6	1.5049 (18)
C24—O24	1.3659 (16)	C6—C7	1.5528 (18)
C24—C25	1.3968 (18)	C6—H6A	0.99
O24—C241	1.4255 (16)	C6—H6B	0.99
C241—H24A	0.98	C7—C8	1.5507 (18)
C241—H24B	0.98	C7—H7A	0.99
C241—H24C	0.98	C7—H7B	0.99
C25—C26	1.3798 (18)	C8—C8A	1.4880 (18)
C25—H25	0.95	C8—H8A	0.99
C26—H26	0.95	C8—H8B	0.99
C3—C3A	1.3858 (18)	C8A—N8B	1.3587 (16)
C3—H3	0.95

C2—N1—N8B	103.55 (10)	N4—C5—C5A	121.71 (12)
N1—C2—C3	112.71 (11)	N4—C5—C51	117.67 (11)
N1—C2—C21	119.22 (11)	C5A—C5—C51	120.62 (11)
C3—C2—C21	128.06 (11)	C5—C51—H51A	109.5
C22—C21—C26	118.14 (12)	C5—C51—H51B	109.5
C22—C21—C2	121.65 (11)	H51A—C51—H51B	109.5
C26—C21—C2	120.20 (11)	C5—C51—H51C	109.5
C23—C22—C21	121.39 (12)	H51A—C51—H51C	109.5
C23—C22—H22	119.3	H51B—C51—H51C	109.5
C21—C22—H22	119.3	C8A—C5A—C5	120.01 (12)
C24—C23—C22	119.59 (12)	C8A—C5A—C6	110.20 (11)
C24—C23—H23	120.2	C5—C5A—C6	129.77 (12)
C22—C23—H23	120.2	C5A—C6—C7	104.05 (10)
O24—C24—C23	124.80 (12)	C5A—C6—H6A	110.9
O24—C24—C25	115.26 (11)	C7—C6—H6A	110.9
C23—C24—C25	119.94 (12)	C5A—C6—H6B	110.9
C24—O24—C241	117.88 (10)	C7—C6—H6B	110.9
O24—C241—H24A	109.5	H6A—C6—H6B	109.0
O24—C241—H24B	109.5	C8—C7—C6	107.73 (10)
H24A—C241—H24B	109.5	C8—C7—H7A	110.2
O24—C241—H24C	109.5	C6—C7—H7A	110.2
H24A—C241—H24C	109.5	C8—C7—H7B	110.2
H24B—C241—H24C	109.5	C6—C7—H7B	110.2
C26—C25—C24	119.80 (12)	H7A—C7—H7B	108.5
C26—C25—H25	120.1	C8A—C8—C7	102.30 (10)
C24—C25—H25	120.1	C8A—C8—H8A	111.3
C25—C26—C21	121.12 (12)	C7—C8—H8A	111.3
C25—C26—H26	119.4	C8A—C8—H8B	111.3
C21—C26—H26	119.4	C7—C8—H8B	111.3
C3A—C3—C2	105.25 (11)	H8A—C8—H8B	109.2
C3A—C3—H3	127.4	N8B—C8A—C5A	118.29 (12)
C2—C3—H3	127.4	N8B—C8A—C8	126.88 (11)
N4—C3A—C3	132.49 (12)	C5A—C8A—C8	114.82 (11)
N4—C3A—N8B	121.90 (11)	C8A—N8B—N1	126.82 (11)
C3—C3A—N8B	105.60 (11)	C8A—N8B—C3A	120.31 (11)
C5—N4—C3A	117.77 (11)	N1—N8B—C3A	112.87 (10)

N8B—N1—C2—C3	−0.48 (13)	C3A—N4—C5—C51	−178.90 (11)
N8B—N1—C2—C21	−179.92 (10)	N4—C5—C5A—C8A	−0.33 (19)
N1—C2—C21—C22	176.30 (11)	C51—C5—C5A—C8A	179.55 (12)
C3—C2—C21—C22	−3.0 (2)	N4—C5—C5A—C6	177.83 (12)
N1—C2—C21—C26	−2.73 (18)	C51—C5—C5A—C6	−2.3 (2)
C3—C2—C21—C26	177.93 (12)	C8A—C5A—C6—C7	−5.51 (14)
C26—C21—C22—C23	1.18 (18)	C5—C5A—C6—C7	176.19 (12)
C2—C21—C22—C23	−177.88 (11)	C5A—C6—C7—C8	9.12 (14)
C21—C22—C23—C24	−0.52 (19)	C6—C7—C8—C8A	−9.16 (13)
C22—C23—C24—O24	−179.95 (11)	C5—C5A—C8A—N8B	−0.70 (18)
C22—C23—C24—C25	−0.21 (18)	C6—C5A—C8A—N8B	−179.20 (10)
C23—C24—O24—C241	3.40 (18)	C5—C5A—C8A—C8	178.05 (11)
C25—C24—O24—C241	−176.35 (11)	C6—C5A—C8A—C8	−0.44 (15)
O24—C24—C25—C26	−179.98 (11)	C7—C8—C8A—N8B	−175.22 (12)
C23—C24—C25—C26	0.25 (19)	C7—C8—C8A—C5A	6.15 (14)
C24—C25—C26—C21	0.43 (19)	C5A—C8A—N8B—N1	−178.31 (11)
C22—C21—C26—C25	−1.13 (18)	C8—C8A—N8B—N1	3.1 (2)
C2—C21—C26—C25	177.94 (11)	C5A—C8A—N8B—C3A	1.05 (17)
N1—C2—C3—C3A	0.38 (14)	C8—C8A—N8B—C3A	−177.54 (12)
C21—C2—C3—C3A	179.75 (12)	C2—N1—N8B—C8A	179.81 (11)
C2—C3—C3A—N4	−179.23 (13)	C2—N1—N8B—C3A	0.42 (13)
C2—C3—C3A—N8B	−0.10 (13)	N4—C3A—N8B—C8A	−0.39 (18)
C3—C3A—N4—C5	178.38 (13)	C3—C3A—N8B—C8A	−179.64 (10)
N8B—C3A—N4—C5	−0.64 (17)	N4—C3A—N8B—N1	179.05 (11)
C3A—N4—C5—C5A	0.99 (18)	C3—C3A—N8B—N1	−0.20 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C22—H22···N4ⁱ	0.95	2.54	3.436 (2)	156

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

Experimental details

	(I)	(II)	(III)	(IV)
Crystal data
Chemical formula	C₁₇H₁₇N₃	C₁₆H₁₄ClN₃	C₁₆H₁₄BrN₃	C₁₇H₁₇N₃O
M_r	263.34	283.75	328.21	279.34
Crystal system, space group	Monoclinic, P2₁/c	Monoclinic, P2₁/c	Monoclinic, P2₁/c	Monoclinic, P2₁/c
Temperature (K)	120	120	120	120
a, b, c (Å)	13.2882 (7), 6.8383 (4), 15.1947 (8)	13.6800 (11), 6.6669 (6), 15.2010 (16)	13.5387 (6), 6.8551 (2), 15.2767 (7)	9.4691 (3), 8.1711 (2), 18.0278 (6)
β (°)	104.018 (3)	106.980 (6)	105.708 (2)	95.3430 (14)
V (Å³)	1339.60 (13)	1325.9 (2)	1364.87 (10)	1388.80 (7)
Z	4	4	4	4
Radiation type	Mo Kα	Mo Kα	Mo Kα	Mo Kα
µ (mm⁻¹)	0.08	0.28	3.00	0.09
Crystal size (mm)	0.52 × 0.08 × 0.04	0.34 × 0.18 × 0.03	0.66 × 0.20 × 0.02	0.40 × 0.38 × 0.30

Data collection
Diffractometer	Nonius KappaCCD diffractometer	Nonius KappaCCD diffractometer	Nonius KappaCCD diffractometer	Nonius KappaCCD 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	0.955, 0.997	0.922, 0.992	0.242, 0.942	0.956, 0.975
No. of measured, independent and observed [I > 2σ(I)] reflections	13947, 3076, 1640	14750, 3040, 2060	18357, 3125, 2438	16180, 3192, 2520
R_int	0.085	0.072	0.069	0.033
(sin θ/λ)_max (Å⁻¹)	0.650	0.652	0.650	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.064, 0.175, 1.01	0.056, 0.141, 1.03	0.037, 0.096, 1.05	0.042, 0.126, 1.06
No. of reflections	3076	3040	3125	3192
No. of parameters	183	182	186	193
No. of restraints	0	0	2	0
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)	0.35, −0.29	0.38, −0.49	0.41, −0.68	0.28, −0.25

Computer programs: COLLECT (Hooft, 1999), DENZO (Otwinowski & Minor, 1997) and COLLECT, DENZO and COLLECT, WinGX (Farrugia, 1999) and SIR92 (Altomare et al., 1993), OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997), OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick, 1997), OSCAIL and SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97 and PRPKAPPA (Ferguson, 1999).

Selected geometric parameters (Å, °) for compounds (I)–(IV) top

Parameter	(I)	(II)	(III)	(IV)
N1-C2	1.348 (3)	1.349 (2)	1.351 (3)	1.3522 (16)
C2-C3	1.400 (3)	1.407 (3)	1.408 (4)	1.4047 (18)
C3-C3A	1.380 (3)	1.380 (3)	1.381 (4)	1.3858 (18)
C3A-N4	1.356 (3)	1.358 (3)	1.361 (3)	1.3622 (16)
N4-C5	1.333 (3)	1.328 (3)	1.335 (3)	1.3255 (17)
C5-C5A	1.418 (3)	1.419 (3)	1.417 (4)	1.4202 (18)
C5A-C8A	1.358 (3)	1.360 (3)	1.362 (4)	1.3614 (18)
C8A-N8B	1.354 (3)	1.345 (3)	1.353 (3)	1.3587 (16)
N8B-N1	1.357 (3)	1.355 (3)	1.355 (3)	1.3592 (14)
C3A-N8B	1.403 (3)	1.401 (3)	1.395 (3)	1.3928 (15)
C23-C24-O24				124.80 (12)
C25-C24-O24				115.26 (11)
C24-O24-C241				117.88 (10)
N1-C2-C21-C22	-168.1 (2)	-166.2 (2)	-166.4 (2)	176.30 (11)
C23-C24-O24-C241				3.40 (18)

Hydrogen bonds and short intramolecular contacts (Å, °) for compounds (I)–(IV) top

Compound	D-H···A	D-H	H···A	D···A	D-H···A
(I)	C6-H6A···Cgⁱ	0.99	2.94	3.902 (3)	163
(II)	C6-H6A···Cgⁱ	0.99	2.87	3.820 (3)	160
(III)	C6-H6A···Cgⁱ	0.99	2.99	3.942 (3)	161
(IV)	C22-H22···N4ⁱⁱ	0.95	2.54	3.436 (2)	156

Symmetry codes: (i) x, −1 + y, z; (ii) 1 − x, −0.5 + y, 0.5 − z.

Cg is the centroid of ring N1, C2, C3, C3A, N8B

Acknowledgements

X-ray data were collected at the EPSRC X-ray Crystallographic Service, University of Southampton, England. 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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ISSN: 2053-2296

Volume 61| Part 7| July 2005| Pages o452-o456

doi:10.1107/S0108270105016720