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Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296

7-Amino-2-tert-butyl-5-methyl­pyrazolo[1,5-a]pyrimidine: a three-dimensional framework structure built from two N—H⋯N hydrogen bonds

CROSSMARK_Color_square_no_text.svg

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 26 October 2006; accepted 27 October 2006; online 12 December 2006)

The bond distances in the title compound, C11H16N4, provide evidence for peripheral delocalization of π electrons. The mol­ecules are linked by two independent N—H⋯N hydrogen bonds into a three-dimensional framework structure.

Comment

We are inter­ested in the synthesis of fused pyrazole systems, in particular pyrazolo[1,5-a]pyrimidine, because of their potential biological activity. We report here the structure of 7-amino-2-tert-butyl-5-methyl­pyrazolo[1,5-a]pyrimidine, (I)[link] (Fig. 1[link]), and we compare this with the structure of the isomeric compound 7-amino-5-tert-butyl-2-methyl­pyrazolo[1,5-a]pyrimidine, (II)[link] (Portilla, Quiroga, de la Torre et al., 2006[Portilla, J., Quiroga, J., de la Torre, J. M., Cobo, J., Low, J. N. & Glidewell, C. (2006). Acta Cryst. C62, o521-o524.]) and with that of the simpler analogue 7-amino-2,5-dimethyl­pyrazolo[1,5-a]pyrimidine, which crystallizes as a hemihydrate, (III)[link] (Portilla, Quiroga, Cobo et al., 2006[Portilla, J., Quiroga, J., Cobo, J., Low, J. N. & Glidewell, C. (2006). Acta Cryst. C62, o186-o189.]).

[Scheme 1]

The bond distances within the fused heterocyclic system (Table 1[link]) show evidence for electronic delocalization. Thus, within the periphery of the classically localized form (I)[link], the N1=C2 and N4=C5 bonds are both formally double bonds, while C3A—N4 and C7—N7A are both single bonds; however, N1=C2 is not significantly shorter than C3A—N4. Similarly, the C3=C3A and C6=C7 bonds are both formally double bonds, while C2—C3 and C5—C6 are both formally single bonds; however, the C—C distances in the periphery span an overall range of less than 0.02 Å, with no clear distinction between those which are formally single bonds and those which are formally double bonds. These observations, taken all together, point to a significant contribution to the overall mol­ecular–electronic structure from a peripherally delocalized ten-π-electron form.

The mol­ecules of compound (I)[link] are linked by two independent N—H⋯N hydrogen bonds (Table 2[link]) into a three-dimensional framework structure, whose formation is rather easily analysed in terms of two simple substructures, one of which is one-dimensional and the other of which is finite and zero-dimensional.

In the one-dimensional substructure, amino atom N7 in the mol­ecule at (x, y, z) acts as a hydrogen-bond donor, via H7A, to the pyrimidine ring atom N4 in the mol­ecule at (−y + [{1\over 2}], x − [{1\over 2}] + x, z + [{1\over 4}]), while atom N7 at (−y + [{1\over 2}], x − [{1\over 2}], z + [{1\over 4}]) in turn acts as a donor to atom N4 at (−x + 1, −y, z + [{1\over 2}]), so forming a C(6) (Bernstein et al., 1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]) helical chain running along the [001] direction and generated by the 41 screw axis along ([1\over2], 0, z) (Fig. 2[link]). The finite substructure serves to link the C(6) chains; atom N7 in the mol­ecule at (x, y, z) acts as a hydrogen-bond donor, via H7B, to the pyrazole ring atom N1 in the mol­ecule at (y, x, −z + 1), so forming an R22(10) motif generated by the twofold rotation axis along x = y at z = [1\over 2] (Fig. 3[link]). This motif directly links the C(6) chain along ([1\over 2], 0, z) with the four similar chains along (0, [1\over2], z), (0, −[1\over2], z), (1, −[1\over2], z) and (1, [1\over2], z), and by propagation of this inter­action, all of the C(6) chains, and hence all of the mol­ecules, are linked into a single three-dimensional framework structure, built from only two hydrogen bonds.

In the isomeric compound (II), which crystallizes with Z′ = 2 in the space group P[\overline{1}] (Portilla, Quiroga, de la Torre et al., 2006[Portilla, J., Quiroga, J., de la Torre, J. M., Cobo, J., Low, J. N. & Glidewell, C. (2006). Acta Cryst. C62, o521-o524.]), the supra­molecular structure is only one-dimensional, in contrast to the three-dimensional structure of (I)[link]; four independent N—H⋯N hydrogen bonds link the mol­ecules of (II) into chains containing three different types of centrosymmetric ring, one of R22(10) type and two of R44(14) type. In the hemihydrate (III), which crystallizes in the space group C2 (Portilla, Quiroga, Cobo et al., 2006[Portilla, J., Quiroga, J., Cobo, J., Low, J. N. & Glidewell, C. (2006). Acta Cryst. C62, o186-o189.]), the components are linked by a combination of O—H⋯N, N—H⋯N and N—H⋯O hydrogen bonds into a complex three-dimensional framework. Hence, minor changes in the simple hydro­carbyl substituents in compounds (I)–(III) provoke significant changes both in crystallization behaviour, as manifested in the space groups and Z′ values, and in the supra­molecular structures.

[Figure 1]
Figure 1
A mol­ecule of (I)[link], showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2]
Figure 2
A stereoview of part of the crystal structure of (I)[link], showing the formation of a hydrogen-bonded C(6) helical chain generated by the 41 screw axis along ([1\over2], 0, z). For the sake of clarity, H atoms bonded to C atoms have been omitted.
[Figure 3]
Figure 3
Part of the crystal structure of (I)[link], showing the formation of the R22(10) motif which links the C(6) helical chains. For the sake of clarity, H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*) are at the symmetry position (y, x, −z + 1).

Experimental

An intimate mixture of 5-amino-3-tert-butyl-1H-pyrazole (139 mg, 1 mmol) and 3-amino­crotononitrile (82 mg, 1 mmol) was 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 then extracted with ethanol and, after removal of the solvent, the product was crystallized from ethanol, providing colourless crystals of (I)[link] suitable for single-crystal X-ray diffraction (yield 92%; m.p. 489–490 K). MS m/z (%): 204 (100, M+), 189 (18).

Crystal data
  • C11H16N4

  • Mr = 204.28

  • Tetragonal, P 41 21 2

  • a = 10.8271 (2) Å

  • c = 19.9208 (3) Å

  • V = 2335.24 (7) Å3

  • Z = 8

  • Dx = 1.162 Mg m−3

  • Mo Kα radiation

  • μ = 0.07 mm−1

  • T = 120 (2) K

  • Block, colourless

  • 0.50 × 0.50 × 0.20 mm

Data collection
  • Bruker–Nonius KappaCCD 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 = 0.941, Tmax = 0.985

  • 16594 measured reflections

  • 1605 independent reflections

  • 1418 reflections with I > 2σ(I)

  • Rint = 0.038

  • θmax = 27.5°

Refinement
  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.035

  • wR(F2) = 0.091

  • S = 1.05

  • 1605 reflections

  • 140 parameters

  • H-atom parameters constrained

  • w = 1/[σ2(Fo2) + (0.0594P)2 + 0.2575P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max < 0.001

  • Δρmax = 0.14 e Å−3

  • Δρmin = −0.20 e Å−3

Table 1
Selected bond lengths (Å)

N1—C2 1.3491 (19)
C2—C3 1.401 (2)
C3—C3A 1.384 (2)
C3A—N4 1.353 (2)
N4—C5 1.332 (2)
C5—C6 1.398 (2)
C6—C7 1.389 (2)
C7—N7A 1.3705 (19)
N7A—N1 1.3683 (17)
C3A—N7A 1.3906 (18)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N7—H7A⋯N4i 0.95 1.97 2.9034 (18) 168
N7—H7B⋯N1ii 0.95 2.27 3.1202 (19) 149
Symmetry codes: (i) [-y+{\script{1\over 2}}, x-{\script{1\over 2}}, z+{\script{1\over 4}}]; (ii) y, x, -z+1.

The systematic absences permitted P41212 and P43212 as possible space groups, but in the absence of significant resonant scattering, it was not possible to distinguish between these enantiomeric space groups. P41212 was selected, although this choice has no chemical significance, and the Friedel-equivalent reflections were merged. All H atoms were located in difference maps and then treated as riding atoms, with C—H distances of 0.95 (CH) or 0.98 Å (CH3) and N—H distances of 0.95 Å, and with Uiso(H) values of kUeq(C,N), where k = 1.5 for the methyl groups and 1.2 otherwise.

Data collection: COLLECT (Hooft, 1999[Hooft, R. W. W. (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: OSCAIL (McArdle, 2003[McArdle, P. (2003). OSCAIL for Windows. Version 10. Crystallography Centre, Chemistry Department, NUI Galway, Ireland.]) and SHELXS97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); program(s) used to refine structure: OSCAIL 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


Comment top

We are interested in the synthesis of fused pyrazolo systems, in particular pyrazolo[1,5-a]pyrimidine, because of their potential biological activity. We report here the structure of 7-amino-2-tert-butyl-5-methylpyrazolo[1,5-a]pyrimidine, (I) (Fig. 1), and we compare this with the structure of the isomeric compound 7-amino-5-tert-butyl-2-methylpyrazolo[1,5-a]pyrimidine, (II) (Portilla, Quiroga, de la Torre et al., 2006), and with that of the simpler analogue 7-amino-2,5-dimethylpyrazolo[1,5-a]pyrimidine, which crystallizes as a hemihydrate, (III) (Portilla, Quiroga, Cobo et al., 2006).

The bond distances within the fused heterocyclic system (Table 1) show evidence for electronic delocalization. Thus, within the periphery of the classically localized form (I), the N1C2 and N4C5 bonds are both formally double bonds, while C3A—N4 and C7—N7A are both single bonds; however, N1C2 is not significantly shorter than C3A—N4. Similarly, the C3C3A and C6C7 bonds are both formally double bonds, while C2—C3 and C5—C6 are both formally single bonds; however, the C—C distances in the periphery span an overall range of less than 0.02 Å, with no clear distinction between those which are formally single bonds and those which are formally double bonds. These observations, taken all together, point to a significant contribution to the overall molecular–electronic structure from a peripherally delocalized ten-π-electron form.

The molecules of compound (I) are linked by two independent N—H···N hydrogen bonds (Table 2) into a three-dimensional framework structure, whose formation is rather easily analysed in terms of two simple sub-structures, one of which is one-dimensional and the other of which is finite and zero-dimensional.

In the one-dimensional sub-structure, amino atom N7 in the molecule at (x, y, z) acts as a hydrogen-bond donor, via H7A, to the pyrimidine ring atom N4 in the molecule at (−y + 1/2, x − 1/2 + x, z + 1/4), while N7 at (−y + 1/2, x − 1/2, z + 1/4) in turns acts as a donor to N4 at (−x + 1, −y, z + 1/2), so forming a C(6) (Bernstein et al., 1995) helical chain running along the [001] direction and generated by the 41 screw axis along (1/2, 0, z) (Fig. 2). The finite sub-structure serves to link the C(6) chains; atom N7 in the molecule at (x, y, z) acts as a hydrogen-bond donor, via H7B, to the pyrazole ring atom N1 in the molecule at (y, x, −z + 1), so forming an R22(10) motif generated by the twofold rotation axis along x = y at z = 1/2 (Fig. 3). This motif directly links the C(6) chain along (1/2, 0, z) with the four similar chains along (0, 1/2, z), (0, −1/2, z), (1, −1/2, z) and (1, 1/2, z), and by propagation of this interaction, all of the C(6) chains, and hence all of the molecules, are linked into a single three-dimensional framework structure, built from only two hydrogen bonds.

In the isomeric compound (II), which crystallizes with Z' = 2 in space group P1 (Portilla, Quiroga, de la Torre et al., 2006), the supramolecular structure is only one-dimensional, in contrast to the three-dimensional structure of (I); four independent N—H···N hydrogen bonds link the molecules of (II) into chains containing three different types of centrosymmetric ring, one of R22(10) type and two of R44(14) type. In the hemihydrate (III), which crystallizes in space group C2 (Portilla, Quiroga, Cobo et al., 2006), the components are linked by a combination of O—H···N, N—H···N and N—H···O hydrogen bonds into a complex three-dimensional framework. Hence minor changes in the simple hydrocarbyl substituents in compounds (I)–(III) provoke significant changes both in crystallization behaviour, as manifested in the space groups and Z' values, and in the supramolecular structures.

Experimental top

An intimate mixture of 5-amino-3-tert-butyl-1H-pyrazole (139 mg, 1 mmol) and 3-aminocrotononitrile (82 mg, 1 mmol) was placed in a open Pyrex-glass vessel and irradiated in a domestic microwave oven for 2.5 min at 600 W. The reaction mixture was then extracted with ethanol, and after removal of the solvent, the product (I) was crystallized from ethanol, providing colourless crystals suitable for single-crystal X-ray diffraction (yield 92%, m.p. 489–490 K). MS m/z (%) 204 (100, M+), 189 (18).

Refinement top

The systematic absences permitted P41212 and P43212 as possible space groups, but in the absence of significant resonant scattering it was not possible to distinguish between these enantiomeric space groups. P41212 was selected, although this choice has no chemical significance, and the Friedel-equivalent reflections were merged. All H atoms were located in difference maps and then treated as riding atoms with C—H distances of 0.95 (CH) or 0.98 Å (CH3) and N—H distances of 0.95 Å, and with Uiso(H) = kUeq(C,N), where k = 1.5 for the methyl groups and 1.2 otherwise.

Computing details top

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

Figures top
[Figure 1] Fig. 1. A molecule of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. A stereoview of part of the crystal structure of (I), showing the formation of a hydrogen-bonded C(6) helical chain generated by the 41 screw axis along (1/2, 0, z). For the sake of clarity, H atoms bonded to C atoms have been omitted.
[Figure 3] Fig. 3. Part of the crystal structure of (I), showing the formation of the R22(10) motif which links the C(6) helical chains. For the sake of clarity, H atoms bonded to C atoms have been omitted. The atoms marked with an asterisk (*) are at the symmetry position (y, x, −z + 1).
7-Amino-2-tert-butyl-5-methylpyrazolo[1,5-a]pyrimidine top
Crystal data top
C11H16N4Dx = 1.162 Mg m3
Mr = 204.28Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P41212Cell parameters from 1605 reflections
Hall symbol: P 4abw 2nwθ = 2.9–27.5°
a = 10.8271 (2) ŵ = 0.07 mm1
c = 19.9208 (3) ÅT = 120 K
V = 2335.24 (7) Å3Block, yellow
Z = 80.50 × 0.50 × 0.20 mm
F(000) = 880
Data collection top
Bruker–Nonius KappaCCD
diffractometer
1605 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode1418 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.038
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 2.9°
ϕ and ω scansh = 1414
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 1314
Tmin = 0.941, Tmax = 0.985l = 2525
16594 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.035Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.091H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0594P)2 + 0.2575P]
where P = (Fo2 + 2Fc2)/3
1605 reflections(Δ/σ)max < 0.001
140 parametersΔρmax = 0.14 e Å3
0 restraintsΔρmin = 0.20 e Å3
Crystal data top
C11H16N4Z = 8
Mr = 204.28Mo Kα radiation
Tetragonal, P41212µ = 0.07 mm1
a = 10.8271 (2) ÅT = 120 K
c = 19.9208 (3) Å0.50 × 0.50 × 0.20 mm
V = 2335.24 (7) Å3
Data collection top
Bruker–Nonius KappaCCD
diffractometer
1605 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
1418 reflections with I > 2σ(I)
Tmin = 0.941, Tmax = 0.985Rint = 0.038
16594 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0350 restraints
wR(F2) = 0.091H-atom parameters constrained
S = 1.05Δρmax = 0.14 e Å3
1605 reflectionsΔρmin = 0.20 e Å3
140 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.60373 (12)0.43466 (12)0.43204 (6)0.0186 (3)
C20.66623 (15)0.44506 (14)0.37372 (7)0.0183 (3)
C210.68144 (16)0.57105 (14)0.34169 (8)0.0211 (3)
C220.55745 (17)0.63853 (16)0.34185 (9)0.0306 (4)
C230.77559 (18)0.64512 (17)0.38191 (9)0.0323 (4)
C240.7271 (2)0.55723 (18)0.26920 (8)0.0355 (5)
C30.70917 (15)0.33092 (14)0.35020 (7)0.0211 (3)
C3A0.66825 (15)0.24374 (15)0.39590 (7)0.0188 (3)
N40.67679 (13)0.11919 (12)0.39836 (6)0.0218 (3)
C50.61991 (16)0.06367 (15)0.44939 (7)0.0211 (3)
C510.62832 (19)0.07485 (15)0.45159 (8)0.0303 (4)
C60.55759 (15)0.12722 (15)0.50022 (7)0.0202 (3)
C70.55272 (14)0.25538 (15)0.49971 (7)0.0178 (3)
N70.50241 (13)0.32629 (13)0.54701 (6)0.0228 (3)
H22A0.49600.58890.31790.046*
H22B0.56660.71870.31950.046*
H22C0.53030.65130.38830.046*
H23A0.74630.65470.42820.049*
H23B0.78610.72670.36140.049*
H23C0.85490.60150.38200.049*
H24A0.80650.51370.26900.053*
H24B0.73750.63920.24910.053*
H24C0.66660.50990.24320.053*
H30.75670.31630.31090.025*
H51A0.61990.10810.40610.045*
H51B0.56210.10760.48000.045*
H51C0.70850.09920.47020.045*
H60.51840.08250.53530.024*
N7A0.60580 (12)0.31054 (12)0.44492 (6)0.0169 (3)
H7A0.46400.28680.58410.027*
H7B0.50650.41330.54130.027*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0226 (7)0.0143 (6)0.0189 (6)0.0013 (5)0.0023 (5)0.0014 (5)
C20.0185 (8)0.0196 (8)0.0169 (6)0.0001 (6)0.0009 (5)0.0008 (6)
C210.0242 (8)0.0196 (8)0.0193 (7)0.0016 (6)0.0017 (6)0.0025 (6)
C220.0291 (9)0.0230 (9)0.0398 (9)0.0010 (7)0.0032 (8)0.0112 (8)
C230.0344 (10)0.0267 (9)0.0359 (9)0.0069 (8)0.0048 (8)0.0027 (7)
C240.0563 (12)0.0263 (9)0.0240 (8)0.0017 (9)0.0122 (8)0.0039 (7)
C30.0238 (8)0.0230 (8)0.0165 (6)0.0028 (7)0.0037 (6)0.0010 (6)
C3A0.0204 (8)0.0212 (8)0.0147 (6)0.0035 (6)0.0013 (6)0.0024 (6)
N40.0297 (8)0.0178 (6)0.0179 (6)0.0052 (6)0.0003 (5)0.0010 (5)
C50.0275 (8)0.0180 (8)0.0176 (7)0.0024 (7)0.0044 (6)0.0008 (6)
C510.0489 (11)0.0187 (8)0.0232 (7)0.0035 (8)0.0007 (8)0.0017 (7)
C60.0234 (8)0.0198 (8)0.0174 (6)0.0004 (6)0.0000 (7)0.0015 (6)
C70.0170 (7)0.0209 (7)0.0154 (6)0.0005 (6)0.0005 (6)0.0018 (6)
N70.0289 (7)0.0189 (7)0.0205 (6)0.0015 (6)0.0082 (6)0.0001 (5)
N7A0.0201 (7)0.0147 (6)0.0159 (5)0.0020 (5)0.0018 (5)0.0001 (5)
Geometric parameters (Å, º) top
N1—C21.3491 (19)C22—H22C0.98
C2—C31.401 (2)C23—H23A0.98
C3—C3A1.384 (2)C23—H23B0.98
C3A—N41.353 (2)C23—H23C0.98
N4—C51.332 (2)C24—H24A0.98
C5—C61.398 (2)C24—H24B0.98
C6—C71.389 (2)C24—H24C0.98
C7—N7A1.3705 (19)C3—H30.95
N7A—N11.3683 (17)C5—C511.503 (2)
C3A—N7A1.3906 (18)C51—H51A0.98
C2—C211.515 (2)C51—H51B0.98
C21—C231.525 (2)C51—H51C0.98
C21—C221.528 (2)C6—H60.95
C21—C241.534 (2)C7—N71.332 (2)
C22—H22A0.98N7—H7A0.95
C22—H22B0.98N7—H7B0.95
C2—N1—N7A103.61 (12)C3A—C3—C2105.98 (13)
N1—C2—C3112.38 (13)C3A—C3—H3127.0
N1—C2—C21119.50 (13)C2—C3—H3127.0
C3—C2—C21128.12 (13)N4—C3A—C3132.99 (15)
C2—C21—C23108.96 (13)N4—C3A—N7A121.76 (14)
C2—C21—C22109.51 (13)C3—C3A—N7A105.24 (13)
C23—C21—C22109.55 (14)C5—N4—C3A116.49 (14)
C2—C21—C24110.11 (14)N4—C5—C6123.64 (14)
C23—C21—C24109.30 (15)N4—C5—C51116.40 (14)
C22—C21—C24109.39 (14)C6—C5—C51119.95 (14)
C21—C22—H22A109.5C5—C51—H51A109.5
C21—C22—H22B109.5C5—C51—H51B109.5
H22A—C22—H22B109.5H51A—C51—H51B109.5
C21—C22—H22C109.5C5—C51—H51C109.5
H22A—C22—H22C109.5H51A—C51—H51C109.5
H22B—C22—H22C109.5H51B—C51—H51C109.5
C21—C23—H23A109.5C7—C6—C5120.33 (14)
C21—C23—H23B109.5C7—C6—H6119.8
H23A—C23—H23B109.5C5—C6—H6119.8
C21—C23—H23C109.5N7—C7—N7A118.93 (14)
H23A—C23—H23C109.5N7—C7—C6125.90 (14)
H23B—C23—H23C109.5N7A—C7—C6115.17 (14)
C21—C24—H24A109.5C7—N7—H7A118.0
C21—C24—H24B109.5C7—N7—H7B117.9
H24A—C24—H24B109.5H7A—N7—H7B124.1
C21—C24—H24C109.5N1—N7A—C7124.79 (12)
H24A—C24—H24C109.5N1—N7A—C3A112.77 (12)
H24B—C24—H24C109.5C7—N7A—C3A122.45 (13)
N7A—N1—C2—C30.94 (17)C3A—N4—C5—C51179.33 (15)
N7A—N1—C2—C21178.62 (14)N4—C5—C6—C70.3 (2)
N1—C2—C21—C2373.54 (18)C51—C5—C6—C7177.96 (16)
C3—C2—C21—C23106.99 (19)C5—C6—C7—N7176.03 (15)
N1—C2—C21—C2246.3 (2)C5—C6—C7—N7A3.7 (2)
C3—C2—C21—C22133.20 (17)C2—N1—N7A—C7179.87 (14)
N1—C2—C21—C24166.60 (15)C2—N1—N7A—C3A0.02 (17)
C3—C2—C21—C2412.9 (2)N7—C7—N7A—N15.0 (2)
N1—C2—C3—C3A1.50 (18)C6—C7—N7A—N1175.21 (14)
C21—C2—C3—C3A178.01 (16)N7—C7—N7A—C3A175.10 (14)
C2—C3—C3A—N4176.97 (18)C6—C7—N7A—C3A4.7 (2)
C2—C3—C3A—N7A1.36 (17)N4—C3A—N7A—N1177.69 (14)
C3—C3A—N4—C5176.66 (17)C3—C3A—N7A—N10.88 (17)
N7A—C3A—N4—C51.5 (2)N4—C3A—N7A—C72.2 (2)
C3A—N4—C5—C62.4 (2)C3—C3A—N7A—C7179.23 (14)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N7—H7A···N4i0.951.972.9034 (18)168
N7—H7B···N1ii0.952.273.1202 (19)149
Symmetry codes: (i) y+1/2, x1/2, z+1/4; (ii) y, x, z+1.

Experimental details

Crystal data
Chemical formulaC11H16N4
Mr204.28
Crystal system, space groupTetragonal, P41212
Temperature (K)120
a, c (Å)10.8271 (2), 19.9208 (3)
V3)2335.24 (7)
Z8
Radiation typeMo Kα
µ (mm1)0.07
Crystal size (mm)0.50 × 0.50 × 0.20
Data collection
DiffractometerBruker–Nonius KappaCCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.941, 0.985
No. of measured, independent and
observed [I > 2σ(I)] reflections
16594, 1605, 1418
Rint0.038
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.035, 0.091, 1.05
No. of reflections1605
No. of parameters140
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.14, 0.20

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

Selected bond lengths (Å) top
N1—C21.3491 (19)C5—C61.398 (2)
C2—C31.401 (2)C6—C71.389 (2)
C3—C3A1.384 (2)C7—N7A1.3705 (19)
C3A—N41.353 (2)N7A—N11.3683 (17)
N4—C51.332 (2)C3A—N7A1.3906 (18)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N7—H7A···N4i0.951.972.9034 (18)168
N7—H7B···N1ii0.952.273.1202 (19)149
Symmetry codes: (i) y+1/2, x1/2, z+1/4; (ii) y, x, z+1.
 

Acknowledgements

X-ray data were collected at the EPSRC National Crystallography 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. JP and JQ thank COLCIENCIAS and UNIVALLE (Universidad del Valle, Colombia) for financial support.

References

First citationBernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573.  CrossRef CAS Web of Science Google Scholar
First citationFerguson, G. (1999). PRPKAPPA. University of Guelph, Canada.  Google Scholar
First citationHooft, R. W. W. (1999). COLLECT. Nonius BV, Delft, The Netherlands.  Google Scholar
First citationMcArdle, P. (2003). OSCAIL for Windows. Version 10. Crystallography Centre, Chemistry Department, NUI Galway, Ireland.  Google Scholar
First citationOtwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.  Google Scholar
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 citationPortilla, J., Quiroga, J., de la Torre, J. M., Cobo, J., Low, J. N. & Glidewell, C. (2006). Acta Cryst. C62, o521–o524.  Web of Science 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
First citationSpek, A. L. (2003). J. Appl. Cryst. 36, 7–13.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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