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

Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296
Volume 62| Part 8| August 2006| Pages o521-o524
doi:10.1107/S0108270106025893

A hydrogen-bonded chain of rings in 7-amino-5-tert-butyl-2-methyl­pyrazolo[1,5-a]pyrimidine, and a hydrogen-bonded framework structure in 3,7-di­amino-2,5-di­methyl­pyrazolo[1,5-a]pyrimidine mono­hydrate

CROSSMARK_Color_square_no_text.svg
Jaime Portilla,a Jairo Quiroga,a José M. de la Torre,b Justo Cobo,b John N. Lowc and Christopher Glidewelld*

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 4 July 2006; accepted 5 July 2006; online 29 July 2006)

In 7-amino-5-tert-butyl-2-methyl­pyrazolo[1,5-a]pyrimidine, C11H16N4, which crystallizes with Z′ = 2 in the space group P[\overline{1}], the independent mol­ecules are linked by four N—H⋯N hydrogen bonds into chains containing three types of ring. In 3,7-diamino-2,5-dimethyl­pyrazolo[1,5-a]pyrimidine monohydrate, C8H11N5·H2O, the mol­ecular components are linked into a three-dimensional framework structure by a combination of O—H⋯N, N—H⋯N and N—H⋯O hydrogen bonds.

Comment

We report here the structures of 7-amino-5-tert-butyl-2-methyl­pyrazolo[1,5-a]pyrimidine, (I)[link] (Fig. 1[link]), and 3,7-di­amino-2,5-dimethyl­pyrazolo[1,5-a]pyrimidine monohydrate, (II)[link] (Fig. 2[link]), which we compare with the structure of 7-amino-2,5-dimethyl­pyrazolo[1,5-a]pyrimidine hemihydrate, (III). The structure of (III) was determined many years ago using diffraction data collected at ambient temperature (Mornon et al., 1975[Mornon, J.-P., Delettré, J. & Bally, R. (1975). Acta Cryst. B31, 2119-2121.]) and it was recently redetermined using diffraction data collected at 120 K (Portilla et al., 2006[Portilla, J., Quiroga, J., Cobo, J., Low, J. N. & Glidewell, C. (2006). Acta Cryst. C62, o186-o189.]). The heterocyclic system in (I)[link] differs from that in (III) only in the replacement of the methyl substituent on the pyrimidine ring by a tert-butyl substituent, while the heterocyclic system in (II)[link] differs from that in (III) only by the incorporation of a second amino group, and this provides an opportunity to observe the effects of simple changes of substituent upon the supra­molecular aggregation. Compound (I)[link] was prepared in a similar fashion to compound (III) (Portilla et al., 2006[Portilla, J., Quiroga, J., Cobo, J., Low, J. N. & Glidewell, C. (2006). Acta Cryst. C62, o186-o189.]), here using a solvent-free cyclo­condensation between 5-amino-3-methyl-1H-pyrazole and 4,4-dimethyl-3-oxopenta­nenitrile induced by microwave irradiation. Compound (II)[link] was prepared by nitro­sation of (III) to yield (IV), followed by palladium-catalyzed reduction with hydrazine.

[Scheme 1]

The pattern of the bond lengths in both (I)[link] and (II)[link] closely mimics the pattern found for (III), and it is not necessary to discuss this in detail again. Following the earlier discussion (Portilla et al., 2006[Portilla, J., Quiroga, J., Cobo, J., Low, J. N. & Glidewell, C. (2006). Acta Cryst. C62, o186-o189.]), it can be concluded that in all three of these compounds there is a considerable degree of aromatic 10-π-electron delocalization around the periphery of the heterocyclic components.

Compound (I)[link] crystallizes with Z′ = 2, and within the selected asymmetric unit (Fig. 1[link]) the two independent mol­ecules are linked by two N—H⋯N hydrogen bonds (Table 1[link]), forming an R22(10) (Bernstein et al., 1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]) dimer. Dimers of this type are then linked by two further N—H⋯N hydrogen bonds to form a complex chain of rings. Atoms N17 and N27 in the dimeric unit at (x, y, z) act as hydrogen-bond donors via atoms H17B and H27B, respectively, to the ring atoms N24 at (−x, 1 − y, 2 − z) and N14 at (1 − x, 1 − y, 1 − z), so generating by inversion two distinct R44(14) motifs centred at (0, [{1 \over 2}], 1) and ([{1 \over 2}], [{1 \over 2}], [{1 \over 2}]), respectively. Propagation by inversion of these two inter­actions then generates a chain of edge-fused rings running parallel to the [10[\overline{1}]] direction, with R44(14) rings containing pairs of N17 atoms centred at (n, [{1 \over 2}], 1 − n) (n = zero or integer), R44(14) rings containing pairs of N27 atoms centred at ([{1 \over 2}] + n, [{1 \over 2}], [{1 \over 2}] − n) (n = zero or integer) and R22(10) rings occupying the inter­mediate locations in the chain (Fig. 3[link]).

Within the selected asymmetric unit of compound (II)[link] (Fig. 2[link]), the components are linked by an N—H⋯O hydrogen bond (Table 2[link]). The amino group bonded to atom C3 exhibits orientational disorder, and this was modelled in terms of one H-atom site with full occupancy and two H-atom sites each with 0.5 occupancy. While such disorder undoubtedly complicates the analysis and the full description of the overall supra­molecular aggregation, it is possible in this case to demonstrate the occurrence of a three-dimensional hydrogen-bonded structure without reference to this disordered amino group. It may be noted here that the only two possible hydrogen-bond acceptors adjacent to atom N3 in the mol­ecule at (x, y, z), viz. atoms O1 and N3 in the mol­ecules are (2 − x, [{1\over 2}] + y, [{3\over 2}] − z) and (2 − x, 2 − y, 1 − z), respectively, are both distant from the reference N3 atom by more than 3.2 Å (Table 2[link]), and the corresponding D⋯A and H⋯A distances are probably too long for significant hydrogen bonding to occur. Hence, without effective tethering via hydrogen bonds, the amino group based on N3 is more or less free to rotate about the N3—C3 bond and this possibly accounts for the observed disorder. Therefore, we analyse the supra­molecular aggregation of compound (II)[link] without reference to the amino group based on N3.

Two O—H⋯N hydrogen bonds link the bimolecular aggregates into a sheet, and adjacent sheets are linked by paired N—H⋯N hydrogen bonds to form a single three-dimensional framework structure. The water mol­ecule at (x, y, z) acts as hydrogen-bond donor, via atoms H1A and H1B, to atoms N1 at (1 − x, −[{1\over 2}] + y, [{3\over 2}] − z) and N4 at (2 − x, −[{1\over 2}] + y, [{3\over 2}] − z), so forming a sheet parallel to (001) built from a single type of R66(22) ring (Fig. 4[link]). Two sheets of this type pass through each unit cell, generated by the 21 screw axes at y = [{1 \over 4}] and y = [{3 \over 4}], and lying in the domains −0.04 < z < 0.54 and 0.46 < z < 1.04, respectively. The (001) sheets are linked by a centrosymmetric R22(10) motif, in which paired N—H⋯N hydrogen bonds link the heterocyclic mol­ecules at (x, y, z) and (1 − x, 1 − y, 1 − z) (Fig. 5[link]). Propagation of this motif links each (001) sheet to the two adjacent sheets, so forming a continuous framework.

In compound (III), where the water mol­ecules lie across twofold rotation axes in the space group C2, the mol­ecular components are linked by a combination of O—H⋯N, N—H⋯N and N—H⋯O hydrogen bonds into a three-dimensional framework structure (Portilla et al., 2006[Portilla, J., Quiroga, J., Cobo, J., Low, J. N. & Glidewell, C. (2006). Acta Cryst. C62, o186-o189.]). Within that structure, it is possible to identify a centrosymmetric R22(10) motif, precisely similar to that found here in compound (II)[link] (Fig. 5[link]), but there are no further similarities between the supra­molecular structures of (I)[link], (II)[link] and (III).

[Figure 1]
Figure 1
The two independent mol­ecules of compound (I)[link], showing the atom-labelling scheme and the N—H⋯N hydrogen bonds (dashed lines) within the selected asymmetric unit. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2]
Figure 2
The independent components of compound (II)[link], showing the atom-labelling scheme and the N—H⋯O hydrogen bond (dashed line) within the selected asymmetric unit. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. The atoms bonded to atom N3 are disordered; see Comment for discussion.
[Figure 3]
Figure 3
A stereoview of part of the crystal structure of compound (I)[link], showing the formation of a chain along [10[\overline{1}]] built from R22(10) rings and two types of R44(14) ring. For the sake of clarity, H atoms bonded to C or N atoms which are not involved in the motifs shown have been omitted.
[Figure 4]
Figure 4
A stereoview of part of the crystal structure of compound (II)[link], showing the formation of a sheet of R66(22) rings parallel to (001). For the sake of clarity, H atoms bonded to C or N atoms which are not involved in the motif shown have been omitted.
[Figure 5]
Figure 5
A part of the crystal structure of compound (II)[link], showing the formation of the R22(10) motif linking the (001) sheets. For the sake of clarity, the water mol­ecules and H atoms bonded to C or N atoms which are not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) are at the symmetry position (1 − x, 1 − y, 1 − z).

Experimental

For the synthesis of compound (I)[link], equimolar quanti­ties (2 mmol of each component) of 5-amino-3-methyl-1H-pyrazole and 4,4-di­methyl-3-oxopenta­nenitrile were placed in an open Pyrex glass vessel and irradiated in a domestic microwave oven for 2.5 min at 600 W. The reaction mixture was extracted with ethanol. After removal of the solvent, the resulting product, (I)[link], was crystallized from a solution in ethanol to give colourless crystals suitable for single-crystal X-ray diffraction (m.p. 490–491 K, yield 90%). MS (30 eV) m/z (%): 204 (100, M+), 189 (12). For the synthesis of compound (II)[link], a solution of sodium nitrite (30 mmol) in water (10 ml) was added to a solution of 7-amino-2,5-dimethyl­pyrazolo[1,5-a]pyrimidine (Portilla et al., 2006[Portilla, J., Quiroga, J., Cobo, J., Low, J. N. & Glidewell, C. (2006). Acta Cryst. C62, o186-o189.]) (10 mmol) in ethanol (20 ml). To this solution was then added, dropwise at 273–283 K with magnetic stirring, a mixture of concentrated sulfuric acid (5 ml), water (10 ml) and ethanol (10 ml). The resulting solid was collected by filtration and crystallized from a solution in ethanol to yield 7-amino-2,5-dimethyl-3-nitroso­pyra­zolo[1,5-a]pyrimidine as green crystals (m.p. 501–502 K, yield 95%). MS (30 eV) m/z (%): 191 (100, M+), 150 (27), 135 (42). To a solution of this nitroso compound (2 mmol) in methanol (20 ml) was added hydrazine hydrate (6 mmol) and a catalytic amount (50 mg) of palladium on activated carbon. This mixture was then heated under reflux with magnetic stirring for 3 h. After removal of the catalyst from the hot solution by filtration, the filtrate was cooled and the resulting solid product, (II)[link], was collected by filtration and crystallized from a solution in ethanol to yield yellow crystals suitable for single-crystal X-ray diffraction (m.p. 484–486 K, yield 80%). MS (30 eV) m/z (%): 177 (57, M+), 136 (31), 109 (100).

Compound (I)[link]

Crystal data

  • C11H16N4

  • Mr = 204.28

  • Triclinic, [P \overline 1]

  • a = 9.8216 (5) Å

  • b = 11.3582 (7) Å

  • c = 12.2783 (8) Å

  • α = 70.429 (3)°

  • β = 69.895 (4)°

  • γ = 66.454 (4)°

  • V = 1147.66 (12) Å3

  • Z = 4

  • Dx = 1.182 Mg m−3

  • Mo Kα radiation

  • μ = 0.08 mm−1

  • T = 120 (2) K

  • Plate, colourless

  • 0.15 × 0.10 × 0.04 mm
Data collection

  • Bruker–Nonius KappaCCD area-detector diffractometer

  • φ and ω scans

  • Absorption correction: multi-scan (SADABS; Sheldrick, 2003[Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany.]) Tmin = 0.982, Tmax = 0.997

  • 22882 measured reflections

  • 4863 independent reflections

  • 2931 reflections with I > 2σ(I)

  • Rint = 0.066

  • θmax = 26.8°
Refinement

  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.056

  • wR(F2) = 0.150

  • S = 1.04

  • 4863 reflections

  • 280 parameters

  • H-atom parameters constrained

  • w = 1/[σ2(Fo2) + (0.0716P)2 + 0.1822P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max < 0.001

  • Δρmax = 0.22 e Å−3

  • Δρmin = −0.23 e Å−3

  • Extinction correction: SHELXL97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.])

  • Extinction coefficient: 0.015 (3)

Table 1
Hydrogen-bond geometry (Å, °) for (I)[link]

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N17—H17A⋯N21 0.88 2.20 3.017 (3) 155
N17—H17B⋯N24i 0.88 2.20 3.054 (2) 165
N27—H27A⋯N11 0.88 2.23 3.021 (3) 150
N27—H27B⋯N14ii 0.88 2.10 2.951 (2) 162
Symmetry codes: (i) -x, -y+1, -z+2; (ii) -x+1, -y+1, -z+1.

Compound (II)[link]

Crystal data

  • C8H11N5·H2O

  • Mr = 195.23

  • Monoclinic, P 21 /c

  • a = 8.0970 (2) Å

  • b = 9.8881 (3) Å

  • c = 11.9661 (3) Å

  • β = 96.230 (5)°

  • V = 952.40 (5) Å3

  • Z = 4

  • Dx = 1.362 Mg m−3

  • Mo Kα radiation

  • μ = 0.10 mm−1

  • T = 120 (2) K

  • Plate, yellow

  • 0.50 × 0.36 × 0.10 mm
Data collection

  • Bruker–Nonius KappaCCD area-detector diffractometer

  • φ and ω scans

  • Absorption correction: multi-scan (SADABS; Sheldrick, 2003[Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany.]) Tmin = 0.938, Tmax = 0.990

  • 12664 measured reflections

  • 2188 independent reflections

  • 1631 reflections with I > 2σ(I)

  • Rint = 0.034

  • θmax = 27.5°
Refinement

  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.048

  • wR(F2) = 0.151

  • S = 1.06

  • 2188 reflections

  • 129 parameters

  • H-atom parameters constrained

  • w = 1/[σ2(Fo2) + (0.0821P)2 + 0.2832P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max < 0.001

  • Δρmax = 0.26 e Å−3

  • Δρmin = −0.20 e Å−3

  • Extinction correction: SHELXL97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.])

  • Extinction coefficient: 0.034 (7)

Table 2
Hydrogen-bond geometry (Å, °) for (II)[link]

D—H⋯A D—H H⋯A D⋯A D—H⋯A
O1—H1A⋯N1i 0.90 2.17 3.059 (2) 168
O1—H1B⋯N4ii 0.90 1.94 2.817 (2) 166
N3—H3A⋯O1iii 0.86 2.57 3.386 (2) 158
N3—H3C⋯N3iv 0.86 2.43 3.279 (2) 171
N7—H7A⋯O1 0.86 2.10 2.933 (2) 163
N7—H7B⋯N1v 0.86 2.45 3.205 (2) 147
Symmetry codes: (i) [-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]; (ii) [-x+2, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]; (iii) -x+2, [y+{\script{1\over 2}}, -z+{\script{3\over 2}}]; (iv) -x+2, -y+2, -z+1; (v) -x+1, -y+1, -z+1.

Compound (I)[link] crystallized in the triclinic system; space group P[\overline{1}] was assumed and confirmed by the analysis. For compound (II), the space group P21/c was uniquely assigned from the systematic absences. All H atoms were located in difference maps, and then treated as riding atoms. For compound (I), the distances were C—H = 0.95 (aromatic) or 0.98 Å (methyl) and N—H = 0.88 Å, and for compound (II), the distances were C—H = 0.93 (aromatic) or 0.96 Å (methyl), N—H = 0.86–0.87 Å and O—H = 0.90 Å, with Uiso(H) = kUeq(C, N,O), where k = 1.5 for O—H or methyl groups and 1.2 for all other H atoms. In compound (II), the amino group containing N3 was modelled using three sites, with one, labelled H3A, of unit occupancy and two others, labelled H3B and H3C, each with 0.5 occupancy.

For both compounds, data collection: COLLECT (Nonius, 1999[Nonius (1999). COLLECT. Nonius BV, Delft, The Netherlands.]); cell refinement: DENZO (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SIR2004 (Burla et al., 2005[Burla, M. C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G. L., De Caro, L., Giacovazzo, C., Polidori, G. & Spagna, R. (2005). J. Appl. Cryst. 38, 381-388.]); program(s) used to refine structure: OSCAIL (McArdle, 2003[McArdle, P. (2003). OSCAIL for Windows. Version 10. Crystallography Centre, Chemistry Department, NUI Galway, Ireland.]) and SHELXL97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); molecular graphics: PLATON (Spek, 2003[Spek, A. L. (2003). J. Appl. Cryst. 36, 7-13.]); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999[Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada.]).

Supporting information

Crystal structure: contains datablocks global, I, II. DOI: 10.1107/S0108270106025893/sk3040sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270106025893/sk3040Isup2.hkl

Structure factors: contains datablock II. DOI: 10.1107/S0108270106025893/sk3040IIsup3.hkl


Comment top

We report here the structures of 7-amino-5-tert-butyl-2-methylpyrazolo[1,5-a]pyrimidine, (I) (Fig. 1), and 3,7-diamino-2,5-dimethylpyrazolo[1,5-a]pyrimidine monohydrate, (II) (Fig. 2), which we compare with the structure of 7-amino-2,5-dimethylpyrazolo[1,5-a]pyrimidine hemihydrate, (III). The structure of (III) was determined many years ago using diffraction data collected at ambient temperature (Mornon et al., 1975), and it was recently redetermined using diffraction data collected at 120 K (Portilla et al., 2006). The heterocyclic system in (I) differs from that in (III) only in the replacement of the methyl substituent on the pyrimidine ring by a tert-butyl substituent, while the heterocyclic system in (II) differs from that in (III) only by the incorporation of a second amino group, and this provides an opportunity to observe the effects of simple changes of substituent upon the supramolecular aggregation. Compound (I) was prepared in a similar fashion to compound (III) (Portilla et al., 2006), here using a solvent-free cyclocondensation between 5-amino-3-methyl-1H-pyrazole and 4,4-dimethyl-3-oxopentanenitrile induced by microwave irradiation. Compound (II) was prepared by nitrosation of (III) to yield (IV), followed by palladium-catalysed reduction with hydrazine.

The pattern of the bond lengths in both (I) and (II) closely mimics the pattern found for (III), and it is not necessary to discuss this in detail again. Following the earlier discussion (Portilla et al., 2006), it can be concluded that in all three of these compounds there is a considerable degree of aromatic 10-π-electron delocalization around the periphery of the heterocyclic components.

Compound (I) crystallizes with Z' = 2 and within the selected asymmetric unit (Fig. 1) the two independent molecules are linked by two N—H···N hydrogen bonds (Table 1), forming an R22(10) (Bernstein et al., 1995) dimer. Dimers of this type are then linked by two further N—H···N hydrogen bonds to form a complex chain of rings. Atoms N17 and N27 in the dimeric unit at (x, y, z) act as hydrogen-bond donors via atoms H17B and H27B, respectively, to the ring atoms N24 at (−x, 1 − y, 2 − z) and N14 at (1 − x, 1 − y, 1 − z), so generating by inversion two distinct R44(14) motifs centred at (0, 1/2, 1) and (1/2, 1/2, 1/2), respectively. Propagation by inversion of these two interactions then generates a chain of edge-fused rings running parallel to the [101] direction, with R44(14) rings containing pairs of N17 atoms centred at (n, 1/2, 1 − n) (n = zero or integer), R44(14) rings containing pairs of N27 atoms centred at (1/2 + n, 1/2, 1/2 − n) (n = zero or integer) and R22(10) rings occupying the intermediate locations in the chain (Fig. 3).

Within the selected asymmetric unit of compound (II) (Fig. 2), the components are linked by an N—H···O hydrogen bond (Table 2). The amino group bonded to atom C3 exhibits orientational disorder, and this was modelled in terms of one H-atom site with full occupancy and two H-atom sites each with 0.5 occupancy. While such disorder undoubtedly complicates the analysis and the full description of the overall supramolecular aggregation, it is possible in this case to demonstrate the occurrence of a three-dimensional hydrogen-bonded structure without reference to this disordered amino group. It may be noted here that the only two possible hydrogen-bond acceptors adjacent to atom N3 in the molecule at (x, y, z), atoms O1 and N3 in the molecules are (2 − x, 1/2 + y, 3/2 − z) and (2 − x, 2 − y, 1 − z), respectively, are both distant from the reference atom N3 by more than 3.2 Å (Table 2), and the corresponding D···A and H···A distances are probably too long for significant hydrogen bonding to occur. Hence, without effective tethering via hydrogen bonds, the amino group based on N3 is more or less free to rotate about the N3—C3 bond and this possibly accounts for the observed disorder. Therefore, we analyse the supramolecular aggregation of compound (II) without reference to the amino group based on N3.

Two O—H···N hydrogen bonds link the bimolecular aggregates into a sheet, and adjacent sheets are linked by paired N—H···N hydrogen bonds to form a single three-dimensional framework structure. The water molecule at (x, y, z) acts as hydrogen-bond donor, via atoms H1A and H1B, to atoms N1 at (1 − x, −1/2 + y, 3/2 − z) and N4 at (2 − x, −1/2 + y, 3/2 − z), so forming a sheet parallel to (001) built from a single type of R66(22) ring (Fig. 4). Two sheets of this type pass through each unit cell, generated by the 21 screw axes at y = 1/4 and y = 3/4, and lying in the domains −0.04 < z < 0.54 and 0.46 < z < 1.04, respectively. The (001) sheets are linked by a centrosymmetric R22(10) motif, in which paired N—H···N hydrogen bonds link the heterocyclic molecules at (x, y, z) and (1 − x, 1 − y, 1 − z) (Fig. 5). Propagation of this motif links each (001) sheet to the two adjacent sheets, so forming a continuous framework.

In compound (III), where the water molecules lie across twofold rotation axes in space group C2, the molecular components are linked by a combination of O—H···N, N—H···N and N—H···O hydrogen bonds into a three-dimensional framework structure (Portilla et al., 2006). Within that structure, it is possible to identify a centrosymmetric R22(10) motif, precisely similar to that found here in compound (II) (Fig. 5), but there are no further similarities between the supramolecular structures of (I), (II) and (III).

Experimental top

For the synthesis of compound (I), equimolar quantities (2 mmol of each component) of 5-amino-3-methyl-1H-pyrazole and 4,4-dimethyl-3-oxopentanenitrile were placed in an open Pyrex glass vessel and irradiated in a domestic microwave oven for 2.5 min at 600 W. The reaction mixture was extracted with ethanol. After removal of the solvent, the resulting product, (I), was crystallized from a solution in ethanol to give colourless crystals suitable for single-crystal X-ray diffraction (m.p. 490–491 K, yield 90%). MS (30 eV) m/z (%) 204 (100, M+), 189?(12). For the synthesis of compound (II), a solution of sodium nitrite (30 mmol) in water (10 ml) was added to a solution of 7-amino-2,5-dimethylpyrazolo[1,5-a]pyrimidine (Portilla et al., 2006) (10 mmol) in ethanol (20 ml). To this solution was then added, dropwise at 273–283 K with magnetic stirring, a mixture of concentrated sulfuric acid (5 ml), water (10 ml) and ethanol (10 ml). The resulting solid was collected by filtration and crystallized from a solution in ethanol to yield 7-amino-2,5-dimethyl-3-nitrosopyrazolo[1,5-a]pyrimidine as green crystals (m.p. 501–502 K, yield 95%). MS (30 eV) m/z (%) 191 (100, M+), 150?(27), 135?(42). To a solution of this nitroso compound (2 mmol) in methanol (20 ml) was added hydrazine hydrate (6 mmol) and a catalytic amount (50 mg) of palladium on activated carbon. This mixture was then heated under reflux with magnetic stirring for 3 h. After removal of the catalyst from the hot solution by filtration, the filtrate was cooled and the resulting solid product, (II), was collected by filtration and crystallized from a solution in ethanol to yield yellow crystals suitable for single-crystal X-ray diffraction (m.p. 484–486 K, yield 80%). MS (30 eV) m/z (%) 177 (57, M+), 136?(31), 109?(100).

Refinement top

Compound (I) crystallized in the triclinic system; space group P1 was assumed and confirmed by the analysis. H atoms were treated as riding atoms, with C—H(aromatic) = 0.95 Å and Uiso(H) = 1.2Ueq(C), C—H(methyl) = 0.98 Å and Uiso(H) = 1.5Ueq(C), and N—H 0.88 Å and Uiso = 1.2Ueq(N).

Computing details top

For both compounds, data collection: COLLECT (Nonius, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures top
[Figure 1] Fig. 1. The two independent molecules of compound (I), showing the atom-labelling scheme and the N—H···N hydrogen bonds (dashed lines) within the selected asymmetric unit. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. The independent components of compound (II), showing the atom-labelling scheme and the N—H···O hydrogen bond (dashed line) within the selected asymmetric unit. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. The atoms bonded to atom N3 are disordered; see text for discussion.
[Figure 3] Fig. 3. A stereoview of part of the crystal structure of compound (I), showing the formation of a chain along [101] built from R22(10) rings and two types of R44(14) ring. For the sake of clarity, H atoms bonded to C or N atoms which are not involved in the motifs shown have been omitted.
[Figure 4] Fig. 4. A stereoview of part of the crystal structure of compound (II), showing the formation of a sheet of R66(22) rings parallel to (001). For the sake of clarity, H atoms bonded to C or N atoms which are not involved in the motif shown have been omitted.
[Figure 5] Fig. 5. A part of the crystal structure of compound (II), showing the formation of the R22(10) motif linking the (001) sheets. For the sake of clarity, the water molecules and H atoms bonded to C or N atoms which are not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) are at the symmetry position (1 − x, 1 − y, 1 − z).
(I) 7-amino-5-tert-butyl-2-methylpyrazolo[1,5-a]pyrimidine top
Crystal data top
C11H16N4Z = 4
Mr = 204.28F(000) = 440
Triclinic, P1Dx = 1.182 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 9.8216 (5) ÅCell parameters from 4863 reflections
b = 11.3582 (7) Åθ = 1.8–26.8°
c = 12.2783 (8) ŵ = 0.08 mm−1
α = 70.429 (3)°T = 120 K
β = 69.895 (4)°Plate, colourless
γ = 66.454 (4)°0.15 × 0.10 × 0.04 mm
V = 1147.66 (12) Å3
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer		4863 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode2931 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.066
Detector resolution: 9.091 pixels mm-1θmax = 26.8°, θmin = 1.8°
ϕ and ω scansh = −12→12
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		k = −14→14
Tmin = 0.982, Tmax = 0.997l = −15→15
22882 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.056H-atom parameters constrained
wR(F2) = 0.150 w = 1/[σ2(Fo2) + (0.0716P)2 + 0.1822P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
4863 reflectionsΔρmax = 0.22 e Å−3
280 parametersΔρmin = −0.23 e Å−3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.015 (3)
Crystal data top
C11H16N4γ = 66.454 (4)°
Mr = 204.28V = 1147.66 (12) Å3
Triclinic, P1Z = 4
a = 9.8216 (5) ÅMo Kα radiation
b = 11.3582 (7) ŵ = 0.08 mm−1
c = 12.2783 (8) ÅT = 120 K
α = 70.429 (3)°0.15 × 0.10 × 0.04 mm
β = 69.895 (4)°
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer		4863 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		2931 reflections with I > 2σ(I)
Tmin = 0.982, Tmax = 0.997Rint = 0.066
22882 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0560 restraints
wR(F2) = 0.150H-atom parameters constrained
S = 1.04Δρmax = 0.22 e Å−3
4863 reflectionsΔρmin = −0.23 e Å−3
280 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N110.37049 (17)0.36806 (16)0.61371 (14)0.0282 (4)
C120.4201 (2)0.36923 (19)0.49663 (17)0.0280 (5)
C1210.3062 (2)0.4204 (2)0.42243 (18)0.0330 (5)
C130.5786 (2)0.32068 (19)0.45904 (17)0.0287 (5)
C13a0.6333 (2)0.28735 (18)0.55905 (16)0.0255 (5)
N140.77577 (17)0.23631 (16)0.57755 (13)0.0276 (4)
C150.7861 (2)0.21580 (18)0.68892 (16)0.0262 (5)
C1510.9485 (2)0.1559 (2)0.70726 (17)0.0304 (5)
C1521.0307 (2)0.0311 (2)0.65728 (19)0.0427 (6)
C1530.9487 (2)0.1201 (2)0.83874 (18)0.0367 (5)
C1541.0342 (2)0.2564 (2)0.6401 (2)0.0434 (6)
C160.6581 (2)0.24704 (19)0.78210 (17)0.0275 (5)
C170.5117 (2)0.29950 (19)0.76373 (16)0.0272 (5)
N170.38121 (19)0.33238 (17)0.84558 (14)0.0383 (5)
N17a0.50345 (17)0.31734 (15)0.65074 (13)0.0254 (4)
N210.04316 (18)0.42094 (15)0.86094 (14)0.0291 (4)
C22−0.0314 (2)0.3620 (2)0.96560 (17)0.0302 (5)
C2210.0523 (3)0.2316 (2)1.03234 (19)0.0389 (6)
C23−0.1849 (2)0.4373 (2)0.99916 (17)0.0316 (5)
C23a−0.2078 (2)0.55158 (19)0.91046 (16)0.0266 (5)
N24−0.32966 (18)0.66167 (16)0.89615 (14)0.0296 (4)
C25−0.3102 (2)0.75522 (19)0.79646 (16)0.0268 (5)
C251−0.4501 (2)0.8775 (2)0.78242 (17)0.0319 (5)
C252−0.4790 (3)0.9545 (2)0.8740 (2)0.0423 (6)
C253−0.4296 (3)0.9684 (2)0.65822 (19)0.0498 (7)
C254−0.5900 (2)0.8350 (2)0.8085 (2)0.0490 (6)
C26−0.1701 (2)0.74355 (19)0.71148 (16)0.0268 (5)
C27−0.0442 (2)0.63184 (19)0.72674 (16)0.0259 (5)
N270.09465 (18)0.60902 (17)0.65322 (14)0.0353 (5)
N27a−0.06730 (17)0.53745 (15)0.82785 (13)0.0257 (4)
H12A0.20540.46600.46750.049*
H12B0.30020.34660.40200.049*
H12C0.33850.48220.34920.049*
H130.63750.31210.38080.034*
H15A0.9757−0.03300.70020.064*
H15B1.1357−0.00760.66730.064*
H15C1.03310.05440.57240.064*
H15D0.89920.20000.87000.055*
H15E1.05450.08020.84700.055*
H15F0.89260.05720.88350.055*
H15G1.03690.27950.55520.065*
H15H1.13900.21810.65040.065*
H15J0.98130.33600.67190.065*
H16A0.67140.23220.85920.033*
H17a0.29310.36460.82580.046*
H17B0.38320.32190.91940.046*
H22A0.14040.18570.97660.058*
H22B−0.01650.17851.07290.058*
H22C0.08790.24481.09140.058*
H23−0.25870.41441.06900.038*
H25A−0.49550.89810.95440.064*
H25B−0.56981.03270.86740.064*
H25C−0.39000.98180.85870.064*
H25D−0.34220.99810.64220.075*
H25E−0.52251.04510.65410.075*
H25F−0.41100.92040.59870.075*
H25G−0.57440.78760.74930.073*
H25H−0.68140.91320.80470.073*
H25J−0.60390.77690.88830.073*
H26−0.16120.81300.64260.032*
H27a0.16790.53480.67070.042*
H27B0.11330.66810.58710.042*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N110.0254 (9)0.0316 (10)0.0264 (10)−0.0094 (7)−0.0078 (7)−0.0034 (7)
C120.0336 (12)0.0251 (11)0.0268 (11)−0.0134 (9)−0.0078 (9)−0.0026 (8)
C1210.0337 (12)0.0360 (12)0.0311 (12)−0.0120 (10)−0.0121 (9)−0.0045 (9)
C130.0286 (11)0.0332 (12)0.0231 (11)−0.0110 (9)−0.0041 (9)−0.0058 (9)
C13a0.0255 (11)0.0255 (11)0.0234 (11)−0.0106 (8)−0.0027 (9)−0.0033 (8)
N140.0261 (9)0.0324 (10)0.0228 (9)−0.0105 (7)−0.0056 (7)−0.0033 (7)
C150.0296 (11)0.0270 (11)0.0233 (11)−0.0129 (9)−0.0073 (9)−0.0019 (8)
C1510.0269 (11)0.0349 (12)0.0264 (11)−0.0086 (9)−0.0069 (9)−0.0045 (9)
C1520.0348 (13)0.0498 (15)0.0388 (13)−0.0019 (11)−0.0125 (10)−0.0153 (11)
C1530.0344 (12)0.0401 (13)0.0347 (12)−0.0077 (10)−0.0145 (10)−0.0066 (10)
C1540.0354 (13)0.0528 (15)0.0420 (14)−0.0190 (11)−0.0157 (10)0.0015 (11)
C160.0289 (11)0.0303 (11)0.0216 (10)−0.0091 (9)−0.0077 (9)−0.0029 (8)
C170.0311 (12)0.0266 (11)0.0209 (11)−0.0096 (9)−0.0039 (9)−0.0038 (8)
N170.0287 (10)0.0536 (12)0.0229 (9)−0.0040 (9)−0.0055 (8)−0.0090 (8)
N17a0.0245 (9)0.0288 (9)0.0213 (9)−0.0096 (7)−0.0057 (7)−0.0023 (7)
N210.0301 (9)0.0271 (9)0.0276 (10)−0.0061 (8)−0.0104 (8)−0.0035 (7)
C220.0401 (13)0.0311 (12)0.0242 (11)−0.0150 (10)−0.0101 (9)−0.0054 (9)
C2210.0484 (14)0.0344 (13)0.0342 (12)−0.0143 (10)−0.0152 (10)−0.0015 (10)
C230.0338 (12)0.0343 (12)0.0238 (11)−0.0147 (10)−0.0016 (9)−0.0043 (9)
C23a0.0267 (11)0.0307 (12)0.0218 (10)−0.0106 (9)−0.0015 (9)−0.0081 (9)
N240.0281 (9)0.0314 (10)0.0250 (9)−0.0090 (8)−0.0028 (7)−0.0057 (8)
C250.0286 (11)0.0302 (11)0.0232 (11)−0.0099 (9)−0.0064 (9)−0.0076 (9)
C2510.0306 (11)0.0346 (12)0.0281 (11)−0.0072 (9)−0.0076 (9)−0.0080 (9)
C2520.0450 (14)0.0340 (13)0.0442 (14)−0.0060 (11)−0.0104 (11)−0.0131 (10)
C2530.0442 (14)0.0439 (14)0.0379 (14)0.0043 (11)−0.0104 (11)−0.0034 (11)
C2540.0341 (13)0.0500 (15)0.0645 (17)−0.0063 (11)−0.0171 (12)−0.0189 (13)
C260.0299 (11)0.0282 (11)0.0216 (10)−0.0114 (9)−0.0069 (9)−0.0018 (8)
C270.0255 (11)0.0308 (11)0.0213 (10)−0.0112 (9)−0.0034 (9)−0.0055 (9)
N270.0270 (10)0.0376 (10)0.0258 (9)−0.0067 (8)−0.0030 (8)0.0036 (8)
N27a0.0267 (9)0.0274 (9)0.0208 (9)−0.0088 (7)−0.0053 (7)−0.0032 (7)
Geometric parameters (Å, º) top
N11—C121.347 (2)N21—C221.343 (2)
N11—N17a1.370 (2)N21—N27a1.374 (2)
C12—C131.390 (3)C22—C231.397 (3)
C12—C1211.499 (3)C22—C2211.490 (3)
C121—H12A0.98C221—H22A0.98
C121—H12B0.98C221—H22B0.98
C121—H12C0.98C221—H22C0.98
C13—C13a1.385 (3)C23—C23a1.382 (3)
C13—H130.95C23—H230.95
C13a—N141.352 (2)C23a—N241.352 (2)
C13a—N17a1.390 (2)C23a—N27a1.389 (2)
N14—C151.341 (2)N24—C251.339 (2)
C15—C161.393 (3)C25—C261.400 (3)
C15—C1511.528 (3)C25—C2511.525 (3)
C151—C1531.527 (3)C251—C2531.527 (3)
C151—C1541.534 (3)C251—C2541.532 (3)
C151—C1521.538 (3)C251—C2521.533 (3)
C152—H15A0.98C252—H25A0.98
C152—H15B0.98C252—H25B0.98
C152—H15C0.98C252—H25C0.98
C153—H15D0.98C253—H25D0.98
C153—H15E0.98C253—H25E0.98
C153—H15F0.98C253—H25F0.98
C154—H15G0.98C254—H25G0.98
C154—H15H0.98C254—H25H0.98
C154—H15J0.98C254—H25J0.98
C16—C171.386 (3)C26—C271.386 (3)
C16—H16A0.95C26—H260.95
C17—N171.333 (2)C27—N271.330 (2)
C17—N17a1.360 (2)C27—N27a1.361 (2)
N17—H17a0.88N27—H27a0.88
N17—H17B0.88N27—H27B0.88
C12—N11—N17a103.14 (14)C22—N21—N27a103.35 (15)
N11—C12—C13113.05 (17)N21—C22—C23112.59 (17)
N11—C12—C121119.53 (17)N21—C22—C221119.71 (18)
C13—C12—C121127.42 (18)C23—C22—C221127.69 (19)
C12—C121—H12A109.5C22—C221—H22A109.5
C12—C121—H12B109.5C22—C221—H22B109.5
H12A—C121—H12B109.5H22A—C221—H22B109.5
C12—C121—H12C109.5C22—C221—H22C109.5
H12A—C121—H12C109.5H22A—C221—H22C109.5
H12B—C121—H12C109.5H22B—C221—H22C109.5
C13a—C13—C12105.90 (17)C23a—C23—C22106.28 (17)
C13a—C13—H13127.0C23a—C23—H23126.9
C12—C13—H13127.0C22—C23—H23126.9
N14—C13a—C13133.06 (18)N24—C23a—C23133.25 (18)
N14—C13a—N17a121.82 (17)N24—C23a—N27a121.79 (16)
C13—C13a—N17a105.11 (16)C23—C23a—N27a104.93 (17)
C15—N14—C13a116.77 (16)C25—N24—C23a116.89 (16)
N14—C15—C16122.64 (17)N24—C25—C26122.56 (18)
N14—C15—C151115.46 (16)N24—C25—C251115.60 (16)
C16—C15—C151121.90 (17)C26—C25—C251121.82 (17)
C153—C151—C15111.88 (16)C25—C251—C253112.87 (17)
C153—C151—C154108.22 (17)C25—C251—C254109.31 (17)
C15—C151—C154109.05 (16)C253—C251—C254109.20 (18)
C153—C151—C152109.42 (17)C25—C251—C252108.22 (16)
C15—C151—C152108.62 (17)C253—C251—C252108.59 (19)
C154—C151—C152109.62 (18)C254—C251—C252108.57 (17)
C151—C152—H15A109.5C251—C252—H25A109.5
C151—C152—H15B109.5C251—C252—H25B109.5
H15A—C152—H15B109.5H25A—C252—H25B109.5
C151—C152—H15C109.5C251—C252—H25C109.5
H15A—C152—H15C109.5H25A—C252—H25C109.5
H15B—C152—H15C109.5H25B—C252—H25C109.5
C151—C153—H15D109.5C251—C253—H25D109.5
C151—C153—H15E109.5C251—C253—H25E109.5
H15D—C153—H15E109.5H25D—C253—H25E109.5
C151—C153—H15F109.5C251—C253—H25F109.5
H15D—C153—H15F109.5H25D—C253—H25F109.5
H15E—C153—H15F109.5H25E—C253—H25F109.5
C151—C154—H15G109.5C251—C254—H25G109.5
C151—C154—H15H109.5C251—C254—H25H109.5
H15G—C154—H15H109.5H25G—C254—H25H109.5
C151—C154—H15J109.5C251—C254—H25J109.5
H15G—C154—H15J109.5H25G—C254—H25J109.5
H15H—C154—H15J109.5H25H—C254—H25J109.5
C17—C16—C15120.87 (18)C27—C26—C25120.74 (17)
C17—C16—H16A119.6C27—C26—H26119.6
C15—C16—H16A119.6C25—C26—H26119.6
N17—C17—N17a118.06 (17)N27—C27—N27a117.81 (17)
N17—C17—C16126.33 (18)N27—C27—C26126.57 (17)
N17a—C17—C16115.61 (17)N27a—C27—C26115.62 (16)
C17—N17—H17a120.0C27—N27—H27a120.0
C17—N17—H17B120.0C27—N27—H27B120.0
H17a—N17—H17B120.0H27a—N27—H27B120.0
C17—N17a—N11124.94 (15)C27—N27a—N21124.79 (15)
C17—N17a—C13a122.26 (16)C27—N27a—C23a122.37 (16)
N11—N17a—C13a112.79 (15)N21—N27a—C23a112.83 (15)
N17a—N11—C12—C130.3 (2)N27a—N21—C22—C230.2 (2)
N17a—N11—C12—C121−179.40 (16)N27a—N21—C22—C221−178.84 (17)
N11—C12—C13—C13a−0.5 (2)N21—C22—C23—C23a−0.7 (2)
C121—C12—C13—C13a179.23 (19)C221—C22—C23—C23a178.2 (2)
C12—C13—C13a—N14−179.8 (2)C22—C23—C23a—N24−177.2 (2)
C12—C13—C13a—N17a0.4 (2)C22—C23—C23a—N27a0.9 (2)
C13—C13a—N14—C15−179.7 (2)C23—C23a—N24—C25179.9 (2)
N17a—C13a—N14—C150.0 (3)N27a—C23a—N24—C252.1 (3)
C13a—N14—C15—C16−1.2 (3)C23a—N24—C25—C26−1.9 (3)
C13a—N14—C15—C151178.99 (17)C23a—N24—C25—C251179.42 (16)
N14—C15—C151—C153−172.90 (17)N24—C25—C251—C253−169.65 (19)
C16—C15—C151—C1537.3 (3)C26—C25—C251—C25311.6 (3)
N14—C15—C151—C15467.4 (2)N24—C25—C251—C254−47.9 (2)
C16—C15—C151—C154−112.4 (2)C26—C25—C251—C254133.4 (2)
N14—C15—C151—C152−52.0 (2)N24—C25—C251—C25270.2 (2)
C16—C15—C151—C152128.2 (2)C26—C25—C251—C252−108.6 (2)
N14—C15—C16—C171.2 (3)N24—C25—C26—C270.8 (3)
C151—C15—C16—C17−179.01 (18)C251—C25—C26—C27179.47 (17)
C15—C16—C17—N17179.56 (19)C25—C26—C27—N27−179.74 (19)
C15—C16—C17—N17a0.0 (3)C25—C26—C27—N27a0.1 (3)
N17—C17—N17a—N110.7 (3)N27—C27—N27a—N211.3 (3)
C16—C17—N17a—N11−179.79 (17)C26—C27—N27a—N21−178.53 (16)
N17—C17—N17a—C13a179.28 (17)N27—C27—N27a—C23a179.97 (17)
C16—C17—N17a—C13a−1.2 (3)C26—C27—N27a—C23a0.1 (3)
C12—N11—N17a—C17178.67 (17)C22—N21—N27a—C27179.17 (17)
C12—N11—N17a—C13a−0.1 (2)C22—N21—N27a—C23a0.4 (2)
N14—C13a—N17a—C171.2 (3)N24—C23a—N27a—C27−1.3 (3)
C13—C13a—N17a—C17−178.99 (17)C23—C23a—N27a—C27−179.64 (17)
N14—C13a—N17a—N11179.96 (17)N24—C23a—N27a—N21177.56 (16)
C13—C13a—N17a—N11−0.2 (2)C23—C23a—N27a—N21−0.8 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N17—H17A···N210.882.203.017 (3)155
N17—H17B···N24i0.882.203.054 (2)165
N27—H27A···N110.882.233.021 (3)150
N27—H27B···N14ii0.882.102.951 (2)162
Symmetry codes: (i) −x, −y+1, −z+2; (ii) −x+1, −y+1, −z+1.
(II) 3,7-diamino-2,5-dimethylpyrazolo[1,5-a]pyrimidine monohydrate top
Crystal data top
C8H11N5·H2OF(000) = 416
Mr = 195.23Dx = 1.362 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2188 reflections
a = 8.0970 (2) Åθ = 3.4–27.5°
b = 9.8881 (3) ŵ = 0.10 mm−1
c = 11.9661 (3) ÅT = 120 K
β = 96.230 (5)°Plate, colourless
V = 952.40 (5) Å30.50 × 0.36 × 0.10 mm
Z = 4
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer		2188 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode1631 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.034
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.4°
ϕ and ω scansh = −10→10
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		k = −12→12
Tmin = 0.938, Tmax = 0.990l = −15→13
12664 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.048H-atom parameters constrained
wR(F2) = 0.151 w = 1/[σ2(Fo2) + (0.0821P)2 + 0.2832P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max < 0.001
2188 reflectionsΔρmax = 0.26 e Å−3
129 parametersΔρmin = −0.20 e Å−3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.034 (7)
Crystal data top
C8H11N5·H2OV = 952.40 (5) Å3
Mr = 195.23Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.0970 (2) ŵ = 0.10 mm−1
b = 9.8881 (3) ÅT = 120 K
c = 11.9661 (3) Å0.50 × 0.36 × 0.10 mm
β = 96.230 (5)°
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer		2188 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		1631 reflections with I > 2σ(I)
Tmin = 0.938, Tmax = 0.990Rint = 0.034
12664 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0480 restraints
wR(F2) = 0.151H-atom parameters constrained
S = 1.06Δρmax = 0.26 e Å−3
2188 reflectionsΔρmin = −0.20 e Å−3
129 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
N10.67420 (16)0.64475 (14)0.52283 (11)0.0341 (4)
C20.7499 (2)0.74788 (16)0.47362 (14)0.0342 (4)
C210.6493 (3)0.8480 (2)0.40191 (17)0.0500 (5)
C30.9216 (2)0.74919 (16)0.50283 (14)0.0323 (4)
N31.0371 (2)0.84245 (16)0.46815 (14)0.0461 (4)
C3a0.95449 (19)0.64217 (16)0.57677 (13)0.0287 (4)
N41.09631 (16)0.59980 (14)0.63648 (11)0.0319 (3)
C51.0820 (2)0.49713 (17)0.70698 (13)0.0321 (4)
C511.2371 (2)0.4522 (2)0.77640 (16)0.0455 (5)
C60.9308 (2)0.43295 (17)0.71830 (13)0.0330 (4)
C70.7865 (2)0.47443 (16)0.65583 (13)0.0305 (4)
N70.63538 (18)0.42136 (16)0.65922 (13)0.0432 (4)
N7a0.80186 (16)0.58154 (13)0.58556 (11)0.0295 (3)
O10.61519 (17)0.25918 (14)0.86251 (13)0.0529 (4)
H21B0.53450.82190.39510.075*
H21A0.68740.85060.32870.075*
H21C0.66150.93590.43580.075*
H3A1.13680.81940.49310.055*
H3B1.02080.85830.39720.055*0.50
H3C1.01750.92710.47680.055*0.50
H51A1.32880.50670.75860.068*
H52B1.25860.35910.76040.068*
H52C1.22350.46190.85470.068*
H60.92750.36150.76850.040*
H7A0.62680.35970.70900.052*
H7B0.55380.44120.60980.052*
H1A0.53500.21360.89310.079*
H1B0.69630.19660.86570.079*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0309 (7)0.0360 (8)0.0344 (7)0.0007 (6)−0.0015 (5)0.0043 (6)
C20.0384 (9)0.0316 (9)0.0321 (8)−0.0005 (7)0.0018 (7)0.0005 (7)
C210.0533 (12)0.0417 (11)0.0522 (11)−0.0002 (9)−0.0075 (9)0.0129 (9)
C30.0375 (9)0.0282 (8)0.0317 (8)−0.0043 (6)0.0059 (6)0.0003 (6)
N30.0451 (9)0.0396 (9)0.0539 (10)−0.0092 (7)0.0070 (7)0.0118 (7)
C3a0.0280 (8)0.0283 (8)0.0302 (8)−0.0032 (6)0.0060 (6)−0.0038 (6)
N40.0284 (7)0.0336 (7)0.0339 (7)−0.0021 (6)0.0047 (5)−0.0016 (6)
C50.0322 (8)0.0343 (9)0.0301 (8)0.0038 (7)0.0043 (6)−0.0027 (7)
C510.0318 (9)0.0570 (12)0.0470 (10)0.0056 (8)0.0017 (7)0.0063 (9)
C60.0341 (9)0.0333 (9)0.0318 (8)0.0005 (7)0.0049 (6)0.0055 (6)
C70.0317 (8)0.0310 (8)0.0293 (8)−0.0026 (6)0.0055 (6)−0.0003 (6)
N70.0328 (8)0.0502 (9)0.0452 (9)−0.0118 (7)−0.0016 (6)0.0159 (7)
N7a0.0280 (7)0.0303 (7)0.0299 (7)−0.0014 (5)0.0020 (5)0.0033 (5)
O10.0400 (7)0.0518 (9)0.0689 (9)0.0086 (6)0.0143 (7)0.0168 (7)
Geometric parameters (Å, º) top
N1—C21.357 (2)N4—C51.333 (2)
N1—N7a1.3616 (18)C5—C61.399 (2)
C2—C31.397 (3)C5—C511.496 (2)
C2—C211.492 (2)C51—H51A0.96
C21—H21B0.96C51—H52B0.96
C21—H21A0.96C51—H52C0.96
C21—H21C0.96C6—C71.379 (2)
C3—C3a1.387 (2)C6—H60.93
C3—N31.408 (2)C7—N71.336 (2)
N3—H3A0.86C7—N7a1.366 (2)
N3—H3B0.86N7—H7A0.866
N3—H3C0.86N7—H7B0.86
C3a—N41.351 (2)O1—H1A0.90
C3a—N7a1.388 (2)O1—H1B0.90
C2—N1—N7a103.45 (12)N4—C5—C6122.96 (15)
N1—C2—C3112.51 (14)N4—C5—C51116.86 (15)
N1—C2—C21120.26 (15)C6—C5—C51120.18 (15)
C3—C2—C21127.16 (16)C5—C51—H51A109.5
C2—C21—H21B109.5C5—C51—H52B109.5
C2—C21—H21A109.5H51A—C51—H52B109.5
H21B—C21—H21A109.5C5—C51—H52C109.5
C2—C21—H21C109.5H51A—C51—H52C109.5
H21B—C21—H21C109.5H52B—C51—H52C109.5
H21A—C21—H21C109.5C7—C6—C5120.77 (15)
C3a—C3—C2105.63 (14)C7—C6—H6119.6
C3a—C3—N3126.91 (16)C5—C6—H6119.6
C2—C3—N3127.42 (15)N7—C7—N7a117.92 (15)
C3—N3—H3A110.6N7—C7—C6126.26 (15)
C3—N3—H3B112.0N7a—C7—C6115.82 (14)
H3A—N3—H3B115.4C7—N7—H7A116.2
C3—N3—H3C117.7C7—N7—H7B121.8
H3A—N3—H3C113.3H7A—N7—H7B121.6
H3B—N3—H3C86.0N1—N7a—C7125.48 (13)
N4—C3a—C3131.84 (15)N1—N7a—C3a112.89 (13)
N4—C3a—N7a122.59 (14)C7—N7a—C3a121.53 (14)
C3—C3a—N7a105.50 (14)H1A—O1—H1B101.2
C5—N4—C3a116.31 (13)
N7a—N1—C2—C30.89 (18)N4—C5—C6—C7−0.2 (3)
N7a—N1—C2—C21−176.35 (15)C51—C5—C6—C7179.20 (16)
N1—C2—C3—C3a−1.40 (19)C5—C6—C7—N7179.98 (15)
C21—C2—C3—C3a175.61 (17)C5—C6—C7—N7a−1.1 (2)
N1—C2—C3—N3−179.21 (16)C2—N1—N7a—C7176.40 (14)
C21—C2—C3—N3−2.2 (3)C2—N1—N7a—C3a−0.04 (17)
C2—C3—C3a—N4−175.77 (16)N7—C7—N7a—N14.1 (2)
N3—C3—C3a—N42.1 (3)C6—C7—N7a—N1−174.94 (14)
C2—C3—C3a—N7a1.27 (17)N7—C7—N7a—C3a−179.76 (15)
N3—C3—C3a—N7a179.09 (15)C6—C7—N7a—C3a1.2 (2)
C3—C3a—N4—C5175.31 (16)N4—C3a—N7a—N1176.58 (13)
N7a—C3a—N4—C5−1.3 (2)C3—C3a—N7a—N1−0.81 (18)
C3a—N4—C5—C61.4 (2)N4—C3a—N7a—C70.0 (2)
C3a—N4—C5—C51−178.03 (14)C3—C3a—N7a—C7−177.41 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···N1i0.902.173.059 (2)168
O1—H1B···N4ii0.901.942.817 (2)166
N3—H3A···O1iii0.862.573.386 (2)158
N3—H3C···N3iv0.862.433.279 (2)171
N7—H7A···O10.862.102.933 (2)163
N7—H7B···N1v0.862.453.205 (2)147
Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x+2, y−1/2, −z+3/2; (iii) −x+2, y+1/2, −z+3/2; (iv) −x+2, −y+2, −z+1; (v) −x+1, −y+1, −z+1.

Experimental details

(I)(II)
Crystal data
Chemical formulaC11H16N4C8H11N5·H2O
Mr204.28195.23
Crystal system, space groupTriclinic, P1Monoclinic, P21/c
Temperature (K)120120
a, b, c (Å)9.8216 (5), 11.3582 (7), 12.2783 (8)8.0970 (2), 9.8881 (3), 11.9661 (3)
α, β, γ (°)70.429 (3), 69.895 (4), 66.454 (4)90, 96.230 (5), 90
V (Å3)1147.66 (12)952.40 (5)
Z44
Radiation typeMo KαMo Kα
µ (mm−1)0.080.10
Crystal size (mm)0.15 × 0.10 × 0.040.50 × 0.36 × 0.10
Data collection
DiffractometerBruker Nonius KappaCCD area-detector
diffractometer		Bruker Nonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)		Multi-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.982, 0.9970.938, 0.990
No. of measured, independent and
observed [I > 2σ(I)] reflections		22882, 4863, 2931 12664, 2188, 1631
Rint0.0660.034
(sin θ/λ)max (Å−1)0.6340.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.056, 0.150, 1.04 0.048, 0.151, 1.06
No. of reflections48632188
No. of parameters280129
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.22, −0.230.26, −0.20

Computer programs: COLLECT (Nonius, 1999), DENZO (Otwinowski & Minor, 1997) and COLLECT, DENZO and COLLECT, SIR2004 (Burla et al., 2005), OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97 and PRPKAPPA (Ferguson, 1999).

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N17—H17A···N210.882.203.017 (3)155
N17—H17B···N24i0.882.203.054 (2)165
N27—H27A···N110.882.233.021 (3)150
N27—H27B···N14ii0.882.102.951 (2)162
Symmetry codes: (i) −x, −y+1, −z+2; (ii) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···N1i0.902.173.059 (2)168
O1—H1B···N4ii0.901.942.817 (2)166
N3—H3A···O1iii0.862.573.386 (2)158
N3—H3C···N3iv0.862.433.279 (2)171
N7—H7A···O10.862.102.933 (2)163
N7—H7B···N1v0.862.453.205 (2)147
Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x+2, y−1/2, −z+3/2; (iii) −x+2, y+1/2, −z+3/2; (iv) −x+2, −y+2, −z+1; (v) −x+1, −y+1, −z+1.
 

Acknowledgements

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

References

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 First citationPortilla, J., Quiroga, J., Cobo, J., Low, J. N. & Glidewell, C. (2006). Acta Cryst. C62, o186–o189.  CSD CrossRef CAS IUCr Journals Google Scholar
 First citationSheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.  Google Scholar
 First citationSheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany.  Google Scholar
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Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296
Volume 62| Part 8| August 2006| Pages o521-o524
doi:10.1107/S0108270106025893
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