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Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296

A monoclinic polymorph of 3,7,7-trimeth­yl-1-phen­yl-5,6,7,8-tetra­hydro-1H-pyrazolo[3,4-b]quinolin-5-one

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 20 May 2005; accepted 23 May 2005; online 22 June 2005)

A second, monoclinic, polymorph of the title compound, C19H19N3O, is reported. In this polymorph, the mol­ecules are linked into chains by paired C—H⋯π hydrogen bonds and the chains are linked into sheets by π stacking inter­actions.

Comment

The structure of a triclinic form (space group P[\overline{1}], Z′ = 2) of the title compound, (I)[link], has been reported recently (Low et al., 2003[Low, J. N., Mera, J., Quiroga, J. & Cobo, J. (2003). Acta Cryst. E59, o1804-o1806.]); the crystals were grown from an ethanol solution. We now report the structure of a monoclinic polymorph of (I)[link] (space group P21/n, Z′ = 1; Fig. 1[link]), for which the crystals were

[Scheme 1]
grown from a dimethyl­formamide solution. In this polymorph, the supramolecular aggregation shows some inter­esting differences from both that of the triclinic form and that of the analogous compound 3-tert-but­yl-7,7-dimeth­yl-1-phen­yl-5,6,7,8-tetra­hydro­pyrazolo[3,4-b]quinolin-5-one, (II) (Low et al., 2004[Low, J. N., Cobo, J., Mera, J., Quiroga, J. & Glidewell, C. (2004). Acta Cryst. C60, o479-o482.]). For convenience, we denote the monoclinic polymorph reported here as (Ia) and the previously reported triclinic polymorph as (Ib).

The bond lengths in monoclinic polymorph (Ia) are very similar to those in both the triclinic polymorph (Ib) and (II), and thus require no further discussion here. The ring-puckering parameters (Cremer & Pople, 1975[Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354-1358.]) for the carbocyclic ring in monoclinic (Ia) are θ = 52.1 (2)° and φ = 167.4 (4)° for the atom sequence C4a—C5—C6—C7—C8—C8a, with a total puckering amplitude Q = 0.489 (2) Å; these parameters indicate an envelope conformation for this ring (Evans & Boeyens, 1989[Evans, D. G. & Boeyens, J. C. A. (1989). Acta Cryst. B45, 581-590.]), with the ring folded across the vector C6⋯C8. In this respect, (Ia) is very similar both to (Ib) and to (II). However, the patterns of supramolecular aggregation in (Ia), (Ib) and (II) are entirely different.

In monoclinic (Ia), the mol­ecules are linked into chains by two independent C—H⋯π hydrogen bonds acting in concert, and the resulting chains are linked into sheets by π stacking inter­actions; however, C—H⋯O and C—H⋯N hydrogen bonds are absent from the structure of (I)[link]. By contrast, the mol­ecules in triclinic (Ib) are linked into ribbons by a combination of C—H⋯O, C—H⋯N and C—H⋯π hydrogen bonds, while the mol­ecules of (II) are linked into chains by a single C—H⋯N hydrogen bond; however, C—H⋯π hydrogen bonds and π stacking inter­actions are both absent from the structure of (II).

Atoms C6 and C8 in the mol­ecule of (Ia) at (x, y, z) act as hydrogen-bond donors, via the axial atoms H6A and H8A, respectively, to the pyrazole and ar­yl rings of the mol­ecule at (−[{1\over 2}] + x, [3 \over 2] − y, −[{1\over 2}] + z), thereby forming a [101] chain generated by the n-glide plane at y = 0.75 (Fig. 2[link]). We may note here that the exactly corresponding pair of C—H bonds act as donors to ar­yl and pyrazole rings in the analogous chloro-substituted compound 3-tert-but­yl-1-(4-chloro­phen­yl)-7,7-dimeth­yl-5,6,7,8-tetra­hydro­pyrazolo[3,4-b]quinolin-5-one, (III), but such that H6A is donor to the ar­yl ring and H8A is donor to the pyrazole ring in a cyclic centrosymmetric dimer (Low et al., 2005[Low, J. N., Cobo, J., Mera, J., Quiroga, J. & Glidewell, C. (2005). Acta Cryst. E61, o49-o51.]).

The hydrogen-bonded chains in polymorph (Ia) are linked into sheets by π stacking inter­actions. The pyrazole rings in the mol­ecules at (x, y, z) and (1 − x, 1 − y, 1 − z) are strictly parallel, with an inter­planar spacing of 3.311 (2) Å, a ring centroid separation of 3.416 (2) Å and a centroid offset of 0.841 (2) Å; at the same time, the pyrazole ring at (x, y, z) and the pyridine ring containing N9 at (1 − x, 1 − y, 1 − z) make an inter­planar angle of only 1.1 (2)°; the inter­planar spacing is ca 3.30 Å, the corresponding ring centroid separation is 3.547 (2) Å and the centroid offset is 1.300 (2) Å (Fig. 3[link]). The mol­ecules at (x, y, z) and (1 − x, 1 − y, 1 − z) form parts of the hydrogen-bonded chains generated by the n-glide planes at y = 0.75 and y = 0.25, respectively; hence, propagation by the space group of these π stacking inter­actions links all of the [101] chains into a (10[\overline{1}]) sheet (Fig. 4[link]); however, there are no direction-specific inter­actions between adjacent sheets.

[Figure 1]
Figure 1
The mol­ecule of compound (I)[link] in the monoclinic polymorph (Ia), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2]
Figure 2
Stereoview of part of the crystal structure of polymorph (Ia), showing the formation of a hydrogen-bonded chain along [101]. For the sake of clarity, H atoms bonded to those C atoms not involved in the motifs shown have been omitted.
[Figure 3]
Figure 3
Part of the crystal structure of polymorph (Ia), showing a centrosymmetric π-stacked dimer. For the sake of clarity, H atoms have all been omitted. Atoms marked with an asterisk (*) are at the symmetry position (1 − x, 1 − y, 1 − z).
[Figure 4]
Figure 4
Stereoview of part of the crystal structure of polymorph (Ia), showing a (10[\overline 1]) sheet of π stacked [101] chains. For the sake of clarity, H atoms bonded to those C atoms not involved in the motifs shown have been omitted.

Experimental

The title compound was prepared as described previously (Low et al., 2003[Low, J. N., Mera, J., Quiroga, J. & Cobo, J. (2003). Acta Cryst. E59, o1804-o1806.]). Crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation of a dimethyl­formamide solution.

Crystal data
  • C19H19N3O

  • Mr = 305.37

  • Monoclinic, P 21 /n

  • a = 11.1485 (12) Å

  • b = 12.3739 (15) Å

  • c = 11.7412 (12) Å

  • β = 108.894 (6)°

  • V = 1532.4 (3) Å3

  • Z = 4

  • Dx = 1.324 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 3503 reflections

  • θ = 3.8–27.6°

  • μ = 0.08 mm−1

  • T = 120 (2) K

  • Block, colourless

  • 0.34 × 0.23 × 0.13 mm

Data collection
  • Bruker–Nonius 95mm CCD camera on a κ-goniostat 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 = 0.967, Tmax = 0.989

  • 17074 measured reflections

  • 3503 independent reflections

  • 2030 reflections with I > 2σ(I)

  • Rint = 0.090

  • θmax = 27.6°

  • h = −14 → 14

  • k = −15 → 16

  • l = −15 → 15

Refinement
  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.065

  • wR(F2) = 0.179

  • S = 1.03

  • 3503 reflections

  • 211 parameters

  • H-atom parameters constrained

  • w = 1/[σ2(Fo2) + (0.0933P)2 + 0.13P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max < 0.001

  • Δρmax = 0.28 e Å−3

  • Δρmin = −0.30 e Å−3

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

Cg1 and Cg2 are the centroids of rings N1/N2/C3/C3a/C9a and C11–C16, respectively.

D—H⋯A D—H H⋯A DA D—H⋯A
C6—H6ACg1i 0.99 2.97 3.716 (3) 133
C8—H8ACg2i 0.99 2.80 3.708 (3) 153
Symmetry code: (i) [x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}].

The space group P21/n was uniquely assigned from the systematic absences. All H atoms were located from difference maps and then treated as riding atoms, with C—H distances of 0.95 (aromatic), 0.98 (methyl) or 0.99 Å (CH2), and with Uiso(H) = 1.2Ueq(C), or 1.5Ueq(C) for the meth­yl groups.

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

The structure of a triclinic form (space group P1, Z' = 2) of the title compound, (I), has been reported recently (Low et al., 2003); the crystals were grown from an ethanol solution. We now report the structure of a monoclinic polymorph of (I) (space group P21/n, Z' = 1; Fig. 1), for which the crystals were grown from a dimethylformamide solution. In this polymorph, the supramolecular aggregation shows some interesting differences from both that of the triclinic form and that of the analogous compound 3-tert-butyl-7,7-dimethyl-1-phenyl-5,6,7,8-tetrahydropyrazolo[3,4-b]quinolin-5-one, (II) (Low et al., 2004). For convenience, we denote the monoclinic polymorph reported here as (Ia) and the previously reported triclinic polymorph as (Ib).

The bond lengths in monoclinic polymorph (Ia) are very similar to those in both the triclinic polymorph (Ib) and (II), and thus require no further discussion here. The ring-puckering parameters (Cremer & Pople, 1975) for the carbocyclic ring in monoclinic (Ia) are θ = 52.1 (2)° and ϕ = 167.4 (4)° for the atom sequence C4a—C5—C6—C7—C8—C8a, with a total puckering amplitude Q = 0.489 (2) Å; these parameters indicate an envelope conformation for this ring (Evans & Boeyens, 1989), with the ring folded across the vector C6···C8. In this respect, (Ia) is very similar both to (Ib) and to (II). However, the patterns of supramolecular aggregation in (Ia), (Ib) and (II) are entirely different.

In monoclinic (Ia), the molecules are linked into chains by two independent C—H···π hydrogen bonds acting in concert, and the resulting chains are linked into sheets by π-stacking interactions; however, C—H···O and C—H···N hydrogen bonds are absent from the structure of (I). By contrast, the molecules in triclinic (Ib) are linked into ribbons by a combination of C—H···O, C—H···N and C—H···π hydrogen bonds, while the molecules of (II) are linked into chains by a single C—H···N hydrogen bond; however, C—H···π hydrogen bonds and π stacking interactions are both absent from the structure of (II).

Atoms C6 and C8 in the molecule of (Ia) at (x, y, z) act as hydrogen-bond donors, via the axial atoms H6A and H8A, respectively, to the pyrazole and aryl rings of the molecule at (−1/2 + x, 1.5 − y, −1/2 + z), thereby forming a [101] chain generated by the n-glide plane at y = 0.75 (Fig. 2). We may note here that the exactly corresponding pair of C—H bonds act as donors to aryl and pyrazole rings in the analogous chloro-substituted compound 3-tert-butyl-7,7-dimethyl-1-(4-chlorophenyl)-5,6,7,8-tetrahydropyrazolo[3,4-b]quinolin-5-one, (III), but such that H6A is donor to the aryl ring and H8A is donor to the pyrazole ring in a cyclic centrosymmetric dimer (Low et al., 2005).

The hydrogen-bonded chains in polymorph (Ia) are linked into sheets by π stacking interactions. The pyrazole rings in the molecules at (x, y, z) and (1 − x, 1 − y, 1 − z) are strictly parallel with an interplanar spacing of 3.311 (2) Å, and a ring centroid separation of 3.416 (2) Å, giving a centroid offset of 0.841 (2) Å; at the same time, the pyrazole ring at (x, y, z) and the pyridine ring containing N9 at (1 − x, 1 − y, 1 − z) make an interplanar angle of only 1.1 (2)°; the interplanar spacing is ca 3.30 Å, with a corresponding ring centroid separation of 3.547 (2) ° and a centroid offset of 1.300 (2) Å (Fig. 3). The molecules at (x, y, z) and (1 − x, 1 − y, 1 − z) form parts of the hydrogen -bonded chains generated by the n-glide panes at y = 0.75 and y = 1/4, respectively; hence, propagation by the space group of these π stacking interactions links all of the [101] chains into a (101) sheet (Fig. 4); however, there are no direction-specific interactions between adjacent sheets.

Experimental top

The title compound was prepared as previously described (Low et al., 2003). Crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation of a dimethylformamide solution.

Refinement top

The space group P21/n was uniquely assigned from the systematic absences. All H atoms were located from difference maps, and then treated as riding atoms with C—H distances of 0.95 Å (aromatic), 0.98 Å (methyl) or 0.99 Å (CH2), and with Uiso(H) = 1.2Ueq(C), or 1.5Ueq(C) for the methyl groups.

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. The molecule of compound (I) in the monoclinic polymorph (Ia), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. Stereoview of part of the crystal structure of polymorph (Ia), showing the formation of a hydrogen-bonded chain along [101]. For the sake of clarity, H atoms bonded to those C atoms not involved in the motifs shown have been omitted.
[Figure 3] Fig. 3. Part of the crystal structure of polymorph (Ia), showing a centrosymmetric π-stacked dimer. For the sake of clarity, H atoms have all been omitted. Atoms marked with an asterisk (*) are at the symmetry position (1 − x, 1 − y, 1 − z).
[Figure 4] Fig. 4. Stereoview of part of the crystal structure of polymorph (Ia), showing a (10<img height=18 src=/home/ >sc/Desktop/publCIF/symbols/bar1.png >) sheet of π-stacked [101] chains. For the sake of clarity, H atoms bonded to those C atoms not involved in the motifs shown have been omitted.
3,7,7-Trimethyl-1-phenyl-5,6,7,8-tetrahydropyrazolo[3,4-b]quinolin-5-one top
Crystal data top
C19H19N3OF(000) = 648
Mr = 305.37Dx = 1.324 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 3503 reflections
a = 11.1485 (12) Åθ = 3.8–27.6°
b = 12.3739 (15) ŵ = 0.08 mm1
c = 11.7412 (12) ÅT = 120 K
β = 108.894 (6)°Block, colourless
V = 1532.4 (3) Å30.34 × 0.23 × 0.13 mm
Z = 4
Data collection top
Bruker-Nonius 95mm CCD camera on κ goniostat
diffractometer
3503 independent reflections
Radiation source: Bruker–Nonius FR91 rotating anode2030 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.090
Detector resolution: 9.091 pixels mm-1θmax = 27.6°, θmin = 3.8°
ϕ and ω scansh = 1414
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 1516
Tmin = 0.967, Tmax = 0.989l = 1515
17074 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)] = 0.065Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.179H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0933P)2 + 0.13P]
where P = (Fo2 + 2Fc2)/3
3503 reflections(Δ/σ)max < 0.001
211 parametersΔρmax = 0.28 e Å3
0 restraintsΔρmin = 0.30 e Å3
Crystal data top
C19H19N3OV = 1532.4 (3) Å3
Mr = 305.37Z = 4
Monoclinic, P21/nMo Kα radiation
a = 11.1485 (12) ŵ = 0.08 mm1
b = 12.3739 (15) ÅT = 120 K
c = 11.7412 (12) Å0.34 × 0.23 × 0.13 mm
β = 108.894 (6)°
Data collection top
Bruker-Nonius 95mm CCD camera on κ goniostat
diffractometer
3503 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
2030 reflections with I > 2σ(I)
Tmin = 0.967, Tmax = 0.989Rint = 0.090
17074 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0650 restraints
wR(F2) = 0.179H-atom parameters constrained
S = 1.03Δρmax = 0.28 e Å3
3503 reflectionsΔρmin = 0.30 e Å3
211 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O50.06313 (14)0.59447 (13)0.18537 (14)0.0376 (4)
N10.63008 (16)0.63171 (15)0.50347 (16)0.0293 (5)
N20.59896 (17)0.64830 (15)0.60774 (16)0.0325 (5)
N90.51581 (16)0.60051 (15)0.29234 (16)0.0305 (5)
C30.4742 (2)0.64810 (18)0.5768 (2)0.0308 (5)
C3A0.4188 (2)0.63089 (17)0.4500 (2)0.0293 (5)
C40.2983 (2)0.62201 (17)0.3674 (2)0.0296 (5)
C4A0.2870 (2)0.60329 (18)0.24814 (19)0.0281 (5)
C50.1589 (2)0.59384 (18)0.1562 (2)0.0296 (5)
C60.1544 (2)0.58424 (19)0.0276 (2)0.0315 (6)
C70.26272 (19)0.51538 (19)0.01188 (19)0.0321 (6)
C80.38796 (19)0.56800 (19)0.08644 (19)0.0325 (6)
C8A0.39794 (19)0.59121 (17)0.2146 (2)0.0288 (5)
C9A0.5219 (2)0.62022 (17)0.4062 (2)0.0278 (5)
C110.7611 (2)0.63359 (17)0.5127 (2)0.0292 (5)
C120.8519 (2)0.63701 (19)0.6265 (2)0.0341 (6)
C130.9787 (2)0.6423 (2)0.6372 (2)0.0386 (6)
C141.0161 (2)0.64317 (19)0.5358 (2)0.0371 (6)
C150.9259 (2)0.63880 (19)0.4233 (2)0.0371 (6)
C160.7982 (2)0.63443 (19)0.4109 (2)0.0349 (6)
C310.4094 (2)0.6631 (2)0.6683 (2)0.0362 (6)
C710.2541 (2)0.39993 (19)0.0545 (2)0.0387 (6)
C720.2529 (2)0.5139 (2)0.12062 (19)0.0383 (6)
H40.22530.62860.39190.036*
H6A0.15850.65750.00490.038*
H6B0.07240.55170.02010.038*
H8A0.39830.63660.04720.039*
H8B0.45860.51980.08600.039*
H120.82680.63570.69650.041*
H131.04080.64550.71480.046*
H141.10360.64670.54370.044*
H150.95160.63880.35360.045*
H160.73630.63200.33300.042*
H31A0.47300.66990.74830.054*
H31B0.35510.60060.66700.054*
H31C0.35750.72880.64970.054*
H71A0.17040.37000.01090.058*
H71B0.26640.40020.14100.058*
H71C0.31980.35550.03890.058*
H72A0.17140.48250.16820.057*
H72B0.32210.47040.13090.057*
H72C0.25890.58790.14800.057*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O50.0209 (8)0.0547 (11)0.0411 (10)0.0001 (7)0.0152 (7)0.0003 (8)
N10.0198 (10)0.0410 (12)0.0284 (10)0.0010 (8)0.0096 (8)0.0008 (8)
N20.0288 (11)0.0409 (12)0.0299 (11)0.0013 (8)0.0127 (9)0.0015 (8)
N90.0214 (10)0.0403 (11)0.0303 (11)0.0033 (8)0.0093 (8)0.0028 (8)
C30.0252 (12)0.0348 (13)0.0330 (13)0.0009 (10)0.0106 (10)0.0015 (10)
C3A0.0253 (12)0.0323 (13)0.0332 (13)0.0014 (9)0.0135 (10)0.0003 (10)
C40.0220 (12)0.0356 (13)0.0345 (13)0.0004 (9)0.0135 (10)0.0005 (10)
C4A0.0215 (11)0.0340 (13)0.0302 (13)0.0005 (9)0.0105 (10)0.0000 (9)
C50.0220 (11)0.0329 (13)0.0352 (13)0.0004 (9)0.0113 (10)0.0000 (10)
C60.0212 (11)0.0406 (14)0.0339 (13)0.0008 (10)0.0104 (10)0.0001 (10)
C70.0191 (11)0.0448 (14)0.0331 (13)0.0004 (10)0.0092 (9)0.0015 (11)
C80.0205 (11)0.0461 (15)0.0327 (13)0.0008 (10)0.0112 (10)0.0014 (11)
C8A0.0206 (11)0.0327 (13)0.0337 (13)0.0015 (9)0.0095 (10)0.0014 (10)
C9A0.0201 (11)0.0324 (13)0.0312 (13)0.0002 (9)0.0088 (10)0.0003 (9)
C110.0214 (11)0.0304 (13)0.0370 (13)0.0008 (9)0.0109 (10)0.0000 (10)
C120.0261 (12)0.0462 (15)0.0306 (13)0.0008 (10)0.0099 (11)0.0011 (10)
C130.0230 (12)0.0508 (15)0.0380 (14)0.0023 (11)0.0045 (11)0.0030 (11)
C140.0194 (12)0.0498 (16)0.0426 (15)0.0021 (10)0.0109 (11)0.0006 (11)
C150.0276 (12)0.0486 (15)0.0384 (14)0.0006 (11)0.0152 (11)0.0002 (11)
C160.0244 (12)0.0473 (15)0.0334 (13)0.0010 (10)0.0096 (10)0.0023 (11)
C310.0284 (12)0.0489 (15)0.0334 (13)0.0001 (11)0.0131 (11)0.0000 (11)
C710.0294 (13)0.0467 (16)0.0404 (14)0.0018 (11)0.0117 (11)0.0046 (11)
C720.0213 (11)0.0581 (17)0.0361 (14)0.0006 (11)0.0103 (10)0.0040 (11)
Geometric parameters (Å, º) top
N1—C9A1.373 (3)C4—H40.95
N1—N21.392 (3)C4A—C8A1.422 (3)
N1—C111.429 (3)C4A—C51.491 (3)
C11—C161.386 (3)C5—O51.222 (2)
C11—C121.392 (3)C5—C61.499 (3)
C12—C131.380 (3)C6—C71.537 (3)
C12—H120.95C6—H6A0.99
C13—C141.383 (3)C6—H6B0.99
C13—H130.95C7—C721.524 (3)
C14—C151.378 (3)C7—C711.527 (3)
C14—H140.95C7—C81.532 (3)
C15—C161.385 (3)C71—H71A0.98
C15—H150.95C71—H71B0.98
C16—H160.95C71—H71C0.98
N2—C31.319 (3)C72—H72A0.98
C3—C3A1.431 (3)C72—H72B0.98
C3—C311.487 (3)C72—H72C0.98
C31—H31A0.98C8—C8A1.500 (3)
C31—H31B0.98C8—H8A0.99
C31—H31C0.98C8—H8B0.99
C3A—C41.383 (3)C8A—N91.340 (3)
C3A—C9A1.409 (3)N9—C9A1.339 (3)
C4—C4A1.384 (3)
C9A—N1—N2110.19 (16)O5—C5—C4A121.0 (2)
C9A—N1—C11131.70 (19)O5—C5—C6122.4 (2)
N2—N1—C11118.06 (18)C4A—C5—C6116.58 (18)
C16—C11—C12120.0 (2)C5—C6—C7113.16 (18)
C16—C11—N1121.2 (2)C5—C6—H6A108.9
C12—C11—N1118.8 (2)C7—C6—H6A108.9
C13—C12—C11119.6 (2)C5—C6—H6B108.9
C13—C12—H12120.2C7—C6—H6B108.9
C11—C12—H12120.2H6A—C6—H6B107.8
C12—C13—C14120.6 (2)C72—C7—C71109.39 (19)
C12—C13—H13119.7C72—C7—C8109.84 (18)
C14—C13—H13119.7C71—C7—C8110.67 (18)
C15—C14—C13119.7 (2)C72—C7—C6109.22 (18)
C15—C14—H14120.2C71—C7—C6110.11 (18)
C13—C14—H14120.2C8—C7—C6107.57 (18)
C14—C15—C16120.6 (2)C7—C71—H71A109.5
C14—C15—H15119.7C7—C71—H71B109.5
C16—C15—H15119.7H71A—C71—H71B109.5
C15—C16—C11119.6 (2)C7—C71—H71C109.5
C15—C16—H16120.2H71A—C71—H71C109.5
C11—C16—H16120.2H71B—C71—H71C109.5
C3—N2—N1107.38 (18)C7—C72—H72A109.5
N2—C3—C3A110.4 (2)C7—C72—H72B109.5
N2—C3—C31121.1 (2)H72A—C72—H72B109.5
C3A—C3—C31128.6 (2)C7—C72—H72C109.5
C3—C31—H31A109.5H72A—C72—H72C109.5
C3—C31—H31B109.5H72B—C72—H72C109.5
H31A—C31—H31B109.5C8A—C8—C7114.35 (18)
C3—C31—H31C109.5C8A—C8—H8B108.7
H31A—C31—H31C109.5C7—C8—H8A108.7
H31B—C31—H31C109.5C8A—C8—H8B108.7
C4—C3A—C9A117.3 (2)C7—C8—H8A108.7
C4—C3A—C3137.3 (2)H8A—C8—H8B107.6
C9A—C3A—C3105.40 (19)N9—C8A—C4A123.45 (19)
C3A—C4—C4A118.1 (2)N9—C8A—C8115.93 (18)
C3A—C4—H4120.9C4A—C8A—C8120.61 (19)
C4A—C4—H4120.9C9A—N9—C8A114.67 (18)
C4—C4A—C8A119.7 (2)N9—C9A—N1126.62 (19)
C4—C4A—C5119.85 (19)N9—C9A—C3A126.7 (2)
C8A—C4A—C5120.44 (19)N1—C9A—C3A106.68 (19)
C9A—N1—C11—C167.1 (4)C8A—C4A—C5—C66.9 (3)
N2—N1—C11—C16169.93 (19)O5—C5—C6—C7142.7 (2)
C9A—N1—C11—C12174.3 (2)C4A—C5—C6—C737.6 (3)
N2—N1—C11—C128.7 (3)C5—C6—C7—C72177.91 (19)
C16—C11—C12—C130.7 (3)C5—C6—C7—C7162.0 (2)
N1—C11—C12—C13177.9 (2)C5—C6—C7—C858.7 (2)
C11—C12—C13—C140.7 (3)C72—C7—C8—C8A169.93 (18)
C12—C13—C14—C150.1 (4)C71—C7—C8—C8A69.2 (2)
C13—C14—C15—C160.5 (4)C6—C7—C8—C8A51.2 (3)
C14—C15—C16—C110.5 (4)C4—C4A—C8A—N92.3 (3)
C12—C11—C16—C150.1 (3)C5—C4A—C8A—N9178.9 (2)
N1—C11—C16—C15178.5 (2)C4—C4A—C8A—C8178.4 (2)
C9A—N1—N2—C30.5 (2)C5—C4A—C8A—C80.4 (3)
C11—N1—N2—C3177.16 (18)C7—C8—C8A—N9157.37 (19)
N1—N2—C3—C3A0.2 (2)C7—C8—C8A—C4A23.3 (3)
N1—N2—C3—C31179.55 (19)C4A—C8A—N9—C9A1.3 (3)
N2—C3—C3A—C4179.5 (3)C8—C8A—N9—C9A179.42 (19)
C31—C3—C3A—C40.1 (4)C8A—N9—C9A—N1179.0 (2)
N2—C3—C3A—C9A0.2 (2)C8A—N9—C9A—C3A0.5 (3)
C31—C3—C3A—C9A179.2 (2)N2—N1—C9A—N9178.2 (2)
C9A—C3A—C4—C4A0.0 (3)C11—N1—C9A—N94.6 (4)
C3—C3A—C4—C4A179.2 (2)N2—N1—C9A—C3A0.6 (2)
C3A—C4—C4A—C8A1.5 (3)C11—N1—C9A—C3A176.6 (2)
C3A—C4—C4A—C5179.6 (2)C4—C3A—C9A—N91.1 (3)
C4—C4A—C5—O55.4 (3)C3—C3A—C9A—N9178.3 (2)
C8A—C4A—C5—O5173.4 (2)C4—C3A—C9A—N1179.90 (19)
C4—C4A—C5—C6174.3 (2)C3—C3A—C9A—N10.4 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C6—H6A···Cg1i0.992.973.716 (3)133
C8—H8A···Cg2i0.992.803.708 (3)153
Symmetry code: (i) x1/2, y+3/2, z1/2.

Experimental details

Crystal data
Chemical formulaC19H19N3O
Mr305.37
Crystal system, space groupMonoclinic, P21/n
Temperature (K)120
a, b, c (Å)11.1485 (12), 12.3739 (15), 11.7412 (12)
β (°) 108.894 (6)
V3)1532.4 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.08
Crystal size (mm)0.34 × 0.23 × 0.13
Data collection
DiffractometerBruker-Nonius 95mm CCD camera on κ goniostat
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.967, 0.989
No. of measured, independent and
observed [I > 2σ(I)] reflections
17074, 3503, 2030
Rint0.090
(sin θ/λ)max1)0.653
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.065, 0.179, 1.03
No. of reflections3503
No. of parameters211
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.28, 0.30

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).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C6—H6A···Cg1i0.992.973.716 (3)133
C8—H8A···Cg2i0.992.803.708 (3)153
Symmetry code: (i) x1/2, y+3/2, z1/2.
 

Acknowledgements

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

References

First citationCremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358.  CrossRef CAS Web of Science Google Scholar
First citationEvans, D. G. & Boeyens, J. C. A. (1989). Acta Cryst. B45, 581–590.  CrossRef CAS Web of Science IUCr Journals 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 citationLow, J. N., Cobo, J., Mera, J., Quiroga, J. & Glidewell, C. (2004). Acta Cryst. C60, o479–o482.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
First citationLow, J. N., Cobo, J., Mera, J., Quiroga, J. & Glidewell, C. (2005). Acta Cryst. E61, o49–o51.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationLow, J. N., Mera, J., Quiroga, J. & Cobo, J. (2003). Acta Cryst. E59, o1804–o1806.  Web of Science CSD CrossRef IUCr Journals 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 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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