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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 61| Part 6| June 2005| Pages o404-o407
doi:10.1107/S010827010501379X

1-Benz­yl-4-(4-nitro­phen­yl)-2,3-di­hydro-1H-1,5-benzodiazepine: a three-dimensional framework structure generated by two C—H⋯O hydrogen bonds and one C—H⋯π(arene) hydrogen bond

CROSSMARK_Color_square_no_text.svg
Harlen Torres,a Braulio Insuasty,a 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 28 April 2005; accepted 29 April 2005; online 20 May 2005)

In the title compound, C22H19N3O2, the seven-membered ring adopts a boat conformation. The mol­ecules are linked by a combination of two C—H⋯O hydrogen bonds and one C—H⋯π(arene) hydrogen bond into a complex three-dimensional framework structure; each individual hydrogen bond generates a one-dimensional substructure, and pairwise combinations of two hydrogen bonds generate a further set of three one-dimensional substructures.

Comment

Benzodiazepines are an important class of psychotherapeutic compounds. We describe here the mol­ecular and supramol­ecular structures of a benzodiazepine resulting from the cyclo­condensation of a substituted 1,2-diamino­benzene with the Mannich adduct precursor of a vin­yl ketone.

[Scheme 1]

The seven-membered ring in the title compound, (I)[link], adopts a boat conformation, with an approximate local mirror plane through atom C3 and the mid-point of the C5A—C9A bond (Table 1[link] and Fig. 1[link]); it is of inter­est that atoms N1 and N5 are not coplanar with the adjacent ar­yl ring, as shown both by the N5—C5A—C9A—N1 torsion angle (Table 1[link]) and by the deviations of the two N atoms, viz. 0.242 (5) Å for N1 and −0.092 (2) Å for N5, from the plane of the ar­yl ring. Although the configuration of atom N1 is pyramidal, neither this atom nor atom N5 acts as an acceptor of hydrogen bonds. The remaining bond lengths and angles present no unusual values.

The mol­ecules of (I)[link] are linked into a three-dimensional framework of some complexity by a combination of two C—H⋯O hydrogen bonds and one C—H⋯π(arene) hydrogen bond (Table 2[link]). It is convenient to consider firstly the substructures generated by each of these three hydrogen bonds acting individually, and then the substructures generated by each of the three pairwise combinations of the hydrogen bonds.

In the shorter of the two C—H⋯O hydrogen bonds, ar­yl atom C43 in the mol­ecule at (x, y, z) acts as a hydrogen-bond donor to nitro atom O41 in the mol­ecule at ([{1\over 2}] + x, [{1\over 2}] − y, −z), so producing a C(5) chain running parallel to the [100] direction and generated by the 21 screw axis along (x, [{1\over 4}], 0) (Fig. 2[link]). In the second C—H⋯O hydrogen bond, ar­yl atom C14 in the mol­ecule at (x, y, z) acts as a hydrogen-bond donor to nitro atom O42 in the mol­ecule at (−[{1\over 2}] − x, −y, [{1\over 2}] + z), so producing a C(16) chain running parallel to the [001] direction and generated by the 21 screw axis along (−[{1\over 4}], 0, z) (Fig. 3[link]). The third hydrogen bond is of the C—H⋯π(arene) type, and ar­yl atom C46 in the mol­ecule at (x, y, z) acts as a donor to the C5A/C6–C9/C9A ar­yl ring in the mol­ecule at (1 − x, −[{1\over 2}] + y, [{1\over 2}] − z), so forming a chain running parallel to the [010] direction and generated by the 21 screw axis along ([{1\over 2}], y, [{1\over 4}]) (Fig. 4[link]). Hence, each of the three individual hydrogen bonds generates a chain, and these chains run in mutually orthogonal directions.

In addition, each pairwise combination of hydrogen bonds generates a further chain motif, in a direction orthogonal to the chain directions generated by each of the two components acting individually. Thus, for example, atom C43 in the mol­ecule at (−[{1\over 2}] − x, −y, [{1\over 2}] + z) acts as a donor to atom O41 at (−1 − x, −[{1\over 2}] + y, [{1\over 2}] − z), while atom C14 at (−1 − x, −[{1\over 2}] + y, [{1\over 2}] − z) acts as a donor to atom O42 at (−[{1\over 2}] + x, −[{1\over 2}] − y, −z); atom C43 at (−[{1\over 2}] + x, −[{1\over 2}] − y, −z) in turn acts as a donor to atom O41 at (x, −1 + y, z), so completing a C22(21) chain running parallel to the [010] direction (Fig. 5[link]). By contrast, the two individual hydrogen bonds generate homogeneous C(5) and C(16) chains along [100] and [001], respectively (Figs. 2[link] and 3[link]). In a similar way, the two hydrogen bonds involving C14 and C46 as donors (Figs. 3[link] and 4[link]) combine to form a chain along [100], whose repeat unit spans three unit cells and hence which generates a triple-helical substructure (Fig. 6[link]); the bonds involving atoms C43 and C46 as donors (Figs. 2[link] and 4[link]) combine to form a chain along [001] (Fig. 7[link]). The combination of all three hydrogen bonds, and all of the resulting one-dimensional substructures, then generates a single but rather elaborate three-dimensional framework.

[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
Part of the crystal structure of (I)[link], showing the formation of a C(5) chain along [100]. For clarity, H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*), a hash (#) or a dollar sign ($) are at the symmetry positions ([{1\over 2}] + x, [{1\over 2}] − y, −z), (1 + x, y, z) and (−[{1\over 2}] + x, [{1\over 2}] − y, −z), respectively.
[Figure 3]
Figure 3
Part of the crystal structure of (I)[link], showing the formation of a C(16) chain along [001]. For clarity, H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (−[{1\over 2}] − x, −y, [{1\over 2}] + z) and (x, y, 1 + z), respectively.
[Figure 4]
Figure 4
Part of the crystal structure of (I)[link], showing the formation of a chain along [010] generated by the C—H⋯π(arene) hydrogen bond. For clarity, H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*), a hash (#) or a dollar sign ($) are at the symmetry positions (1 − x, −[{1\over 2}] + y, [{1\over 2}] − z), (1 − x, [{1\over 2}] + y, [{1\over 2}] − z) and (x, 1 + y, z), respectively.
[Figure 5]
Figure 5
A stereoview of part of the crystal structure of (I)[link], showing the formation of a C22(21) chain along [010] generated by the combination of the two C—H⋯O hydrogen bonds. For clarity, H atoms not involved in the motif shown have been omitted.
[Figure 6]
Figure 6
A stereoview of part of the crystal structure of (I)[link], showing the formation of a triple helix along [100] generated by the combination of one C—H⋯O hydrogen bond and one C—H⋯π(arene) hydrogen bond. For clarity, H atoms not involved in the motif shown have been omitted.
[Figure 7]
Figure 7
A stereoview of part of the crystal structure of (I)[link], showing the formation of a chain along [001] generated by the combination of one C—H⋯O hydrogen bond and one C—H⋯π(arene) hydrogen bond. For clarity, H atoms not involved in the motif shown have been omitted.

Experimental

A solution in ethanol (50 ml) of N-benz­yl-o-phenyl­enediamine (0.5 mmol), 2-(dimethyl­amino)­eth­yl 4-nitro­phen­yl ketone hydro­chloride (0.5 mmol) and glacial acetic acid (1 ml) was heated under reflux for 12 h. The solvent was then removed under reduced pressure and the resulting solid residue was purified by column chromatog­raphy on silica using hexane/eth­yl acetate (4:1 v/v) as eluant (yield 53%, m.p. 392 K). MS (70 eV) m/z (%): 357 (63, M+), 266 (35, [M − PhCH2]+), 119 (56), 91 (100, [C7H7]+). Crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation of a solution in ethanol.

Crystal data

  • C22H19N3O2

  • Mr = 357.40

  • Orthorhombic, P 21 21 21

  • a = 7.3810 (2) Å

  • b = 10.8016 (3) Å

  • c = 22.1319 (5) Å

  • V = 1764.50 (8) Å3

  • Z = 4

  • Dx = 1.345 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 2314 reflections

  • θ = 2.9–27.5°

  • μ = 0.09 mm−1

  • T = 120 (2) K

  • Block, red

  • 0.38 × 0.36 × 0.34 mm
Data collection

  • 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 = 0.963, Tmax = 0.971

  • 12 216 measured reflections

  • 2314 independent reflections

  • 2127 reflections with I > 2σ(I)

  • Rint = 0.031

  • θmax = 27.5°

  • h = −9 → 9

  • k = −13 → 13

  • l = −28 → 27
Refinement

  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.044

  • wR(F2) = 0.107

  • S = 1.16

  • 2314 reflections

  • 245 parameters

  • H-atom parameters constrained

  • w = 1/[σ2(Fo2) + (0.0676P)2 + 0.1595P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max < 0.001

  • Δρmax = 0.43 e Å−3

  • Δρmin = −0.44 e Å−3

  • Extinction correction: SHELXL97 (Sheldrick, 1997[Spek, A. L. (2003). J. Appl. Cryst. 36, 7-13.])

  • Extinction coefficient: 0.097 (7)

Table 1
Selected torsion angles (°)[link]

N1—C2—C3—C4 −55.9 (2)
C2—C3—C4—N5 73.7 (2)
C3—C4—N5—C5A −0.8 (2)
C4—N5—C5A—C9A −41.8 (2)
N5—C5A—C9A—N1 −9.1 (3)
C5A—C9A—N1—C2 66.3 (2)
C9A—N1—C2—C3 −24.8 (2)
C43—C44—N44—O41 2.6 (3)

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

Cg is the centroid of the C5A/C6–C9/C9A benzene ring.
D—H⋯A D—H H⋯A D⋯A D—H⋯A
C14—H14⋯O42i 0.95 2.55 3.378 (3) 146
C43—H43⋯O41ii 0.95 2.42 3.153 (3) 134
C46—H46⋯Cgiii 0.95 2.74 3.578 (2) 147
Symmetry codes: (i) [-x-{\script{1\over 2}}, -y, z+{\script{1\over 2}}]; (ii) [x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]; (iii) -x+1, [y-{\script{1\over 2}}], [-z+{\script{1\over 2}}].

The space group P212121 was uniquely assigned from the systematic absences. All H atoms were located from difference maps in fully ordered sites; these atoms were then treated as riding, with C—H distances of 0.95 (aromatic) or 0.99 Å (CH2), and with Uiso(H) values of 1.2Ueq(C). In the absence of significant anomalous scattering, the Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]) parameter was indeterminate (Flack & Bernardinelli, 2000[Flack, H. D. & Bernardinelli, G. (2000). J. Appl. Cryst. 33, 1143-1148.]). Accordingly, the Friedel equivalent reflections were merged prior to the final refinements.

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

Crystal structure: contains datablocks global, I. DOI: 10.1107/S010827010501379X/sk1842sup1.cif

Structure factors: contains datablock s0234. DOI: 10.1107/S010827010501379X/sk1842Isup2.hkl


Comment top

Benzodiazepines are an important class of psychotherapeutic compounds. Here we describe the molecular and supramolecular structure of a benzodiazepine resulting from the cyclocondensation of a substituted 1,2-diaminobenzene with the Mannich adduct precursor of a vinyl ketone.

The seven-membered ring in the title compound, (I), adopts a boat conformation, with an approximate local mirror plane through atom C3 and the mid-point of the C5A—C9A bond (Table 1 and Fig. 1); it is of interest that atoms N1 and N5 are not coplanar with the adjacent aryl ring, as shown both by the N5—C5A—C9A—N1 torsional angle (Table 1) and by the deviations of the two N atoms, viz. 0.242 (5) Å for N1 and −0.092 (2) Å for N5, from the plane of the aryl ring. Although the configuration of atom N1 is pyramidal, neither this atom nor atom N5 acts as an acceptor of hydrogen bonds. The remaining bond lengths and angles present no unusual values.

The molecules of (I) are linked into a three-dimensional framework of some complexity by a combination of two C—H···O hydrogen bonds and one C—H···π(arene) hydrogen bond (Table 2). It is convenient to consider firstly the substructures generated by each of these three hydrogen bonds acting individually, and then the substructures generated by each of the three pairwise combinations of the hydrogen bonds.

In the shorter of the two C—H···O hydrogen bonds, aryl atom C43 in the molecule at (x, y, z) acts as a hydrogen-bond donor to nitro atom O41 in the molecule at (1/2 + x, 1/2 − y, −z), so producing a C(5) chain running parallel to the [100] direction, and generated by the 21 screw axis along (x, 1/4, 0) (Fig. 2). In the second C—H···O hydrogen bond, aryl atom C14 in the molecule at (x, y, z) acts as a hydrogen-bond donor to nitro atom O42 in the molecule at (−1/2 − x, −y, 1/2 + z), so producing a C(16) chain running parallel to the [001] direction and generated by the 21 screw axis along (−1/4, 0, z) (Fig. 3). The third hydrogen bond is of the C—H···π(arene) type, and aryl atom C46 in the molecule at (x, y, z) acts as a donor to the aryl ring (C5A/C6/C7/C8/C9/C9A) in the molecule at (1 − x, −1/2 + y, 1/2 − z), so forming a chain running parallel to the [010] direction and generated by the 21 screw axis along (1/2, y, 1/4) (Fig. 4). Hence each of the three individual hydrogen bonds generates a chain, and these chain run in mutually orthogonal directions.

In addition, each pairwise combination of hydrogen bonds generates a further chain motif, in a direction orthogonal to the chain directions generated by each of the two components acting individually. Thus, for example, atom C43 in the molecule at (−1/2 − x, −y, 1/2 + z) acts as a donor to atom O41 at (−1 − x, −1/2 + y, 1/2 − z), while atom C14 at (−1 − x, −1/2 + y, 1/2 − z) acts as a donor to atom O42 at (−1/2 + x, −1/2 − y, −z); atom C43 at (−1/2 + x, −1/2 − y, −z) in turn acts as a donor to atom O41 at (x, −1 + y, z), so completing a C22(21) chain running parallel to the [010] direction (Fig. 5). By contrast, the two individual hydrogen bonds generate homogeneous C(5) and C(16) chains along [100] and [001], respectively (Figs. 2 and 3). In a similar way, the two hydrogen bonds involving C14 and C46 as donors (Figs. 3 and 4) combine to form a chain along [100], whose repeat unit spans three unit cells and hence which generates a triple-helical substructure (Fig. 6); the bonds involving atoms C43 and C46 as donors (Figs. 2 and 4) combine to form a chain along [001] (Fig. 7). The combination of all three hydrogen bonds, and all of the resulting one-dimensional substructures, then generates a single but rather elaborate three-dimensional framework.

Experimental top

A solution in ethanol (50 ml) of N-benzyl-o-phenylenediamine (0.5 mmol), 2-dimethylaminoethyl(4-nitrophenyl)ketone hydrochloride (0.5 mmol) and glacial acetic acid (1 ml) was heated under reflux for 12 h. The solvent was then removed under reduced pressure and the resulting solid residue was purified by column chromatography on silica using hexane/ethyl acetate (4:1, v/v) as eluant. Yield 53%, m.p. 392 K. MS (70 eV) m/z (%): 357 (63, M+), 266 (35, [M-PhCH2]+), 119 (56), 91 (100, [C7H7]+). Crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation of a solution in ethanol.

Refinement top

The space group P212121 was uniquely assigned from the systematic absences. All H atoms were located from difference maps in fully ordered sites; these atoms were then treated as riding, with C—H distances of 0.95 Å (aromatic) or 0.99 Å (CH2), and with Uiso(H) values of 1.2Ueq(C). In the absence of significant anomalous scattering, the Flack (1983) parameter was indeterminate (Flack & Bernardinelli, 2000). Accordingly, the Friedel equivalent reflections were merged prior to the final refinements.

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. Part of the crystal structure of (I), showing the formation of a C(5) chain along [100]. For clarity the H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*), a hash (#) or a dollar sign ($) are at the symmetry positions (1/2 + x, 1/2 − y, −z), (1 + x, y, z) and (−1/2 + x, 1/2 − y, −z), respectively.
[Figure 3] Fig. 3. Part of the crystal structure of (I), showing the formation of a C(16) chain along [001]. For clarity, H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (−1/2 − x, −y, 1/2 + z) and (x, y, 1 + z), respectively.
[Figure 4] Fig. 4. Part of the crystal structure of (I), showing the formation of a chain along [010] generated by the C—H···π(arene) hydrogen bond. For clarity, H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*), a hash (#) or a dollar sign ($) are at the symmetry positions (1 − x, −1/2 + y, 1/2 − z), (1 − x, 1/2 + y, 1/2 − z) and (x, 1 + y, z), respectively.
[Figure 5] Fig. 5. A stereoview of part of the crystal structure of (I), showing the formation of a C22(21) chain along [010] generated by the combination of the two C—H···O hydrogen bonds. For clarity, H atoms not involved in the motif shown have been omitted.
[Figure 6] Fig. 6. SA stereoview of part of the crystal structure of (I), showing the formation of a triple helix along [100] generated by the combination of one C—H···O hydrogen bond and one C—H···π(arene) hydrogen bond. For clarity, H atoms not involved in the motif shown have been omitted.
[Figure 7] Fig. 7. A stereoview of part of the crystal structure of (I), showing the formation of a chain along [001] generated by the combination of one C—H···O hydrogen bond and one C—H···π(arene) hydrogen bond. For clarity, H atoms not involved in the motif shown have been omitted.
1-Benzyl-4-(4-nitrophenyl)-2,3-dihydro-1H-1,5-benzodiazepine top
Crystal data top
C22H19N3O2F(000) = 752
Mr = 357.40Dx = 1.345 Mg m−3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 2314 reflections
a = 7.3810 (2) Åθ = 2.9–27.5°
b = 10.8016 (3) ŵ = 0.09 mm−1
c = 22.1319 (5) ÅT = 120 K
V = 1764.50 (8) Å3Block, red
Z = 40.38 × 0.36 × 0.34 mm
Data collection top
Nonius KappaCCD
diffractometer		2314 independent reflections
Radiation source: Bruker-Nonius FR91 rotating anode2127 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.031
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 2.9°
ϕ and ω scansh = −9→9
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		k = −13→13
Tmin = 0.963, Tmax = 0.971l = −28→27
12216 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)] = 0.044H-atom parameters constrained
wR(F2) = 0.107 w = 1/[σ2(Fo2) + (0.0676P)2 + 0.1595P]
where P = (Fo2 + 2Fc2)/3
S = 1.16(Δ/σ)max < 0.001
2314 reflectionsΔρmax = 0.43 e Å−3
245 parametersΔρmin = −0.44 e Å−3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.097 (7)
Crystal data top
C22H19N3O2V = 1764.50 (8) Å3
Mr = 357.40Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 7.3810 (2) ŵ = 0.09 mm−1
b = 10.8016 (3) ÅT = 120 K
c = 22.1319 (5) Å0.38 × 0.36 × 0.34 mm
Data collection top
Nonius KappaCCD
diffractometer		2314 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		2127 reflections with I > 2σ(I)
Tmin = 0.963, Tmax = 0.971Rint = 0.031
12216 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0440 restraints
wR(F2) = 0.107H-atom parameters constrained
S = 1.16Δρmax = 0.43 e Å−3
2314 reflectionsΔρmin = −0.44 e Å−3
245 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O41−0.1912 (2)0.15148 (16)0.01598 (8)0.0436 (5)
O42−0.2876 (2)−0.00225 (14)0.06924 (7)0.0329 (4)
N10.6100 (2)0.08669 (14)0.31442 (7)0.0210 (4)
N50.5770 (2)0.17704 (14)0.18991 (7)0.0194 (3)
N44−0.1706 (2)0.07260 (15)0.05545 (8)0.0244 (4)
C10.6251 (3)0.0814 (2)0.38081 (8)0.0253 (4)
C20.5229 (3)−0.02509 (16)0.29030 (8)0.0207 (4)
C30.5539 (3)−0.03925 (16)0.22264 (8)0.0198 (4)
C40.4901 (3)0.07385 (16)0.18898 (8)0.0182 (4)
C5A0.7381 (3)0.18672 (17)0.22433 (8)0.0196 (4)
C60.8767 (3)0.25633 (17)0.19874 (8)0.0228 (4)
C71.0438 (3)0.26822 (18)0.22697 (9)0.0248 (4)
C81.0716 (3)0.21083 (18)0.28233 (9)0.0238 (4)
C90.9322 (3)0.14745 (18)0.31009 (9)0.0232 (4)
C9A0.7605 (2)0.13598 (17)0.28313 (8)0.0193 (4)
C110.4412 (3)0.08352 (19)0.41082 (8)0.0233 (4)
C120.3610 (3)0.19673 (19)0.42456 (8)0.0270 (5)
C130.1934 (3)0.2011 (2)0.45328 (9)0.0311 (5)
C140.1037 (3)0.09308 (19)0.46813 (9)0.0291 (5)
C150.1815 (3)−0.0202 (2)0.45434 (9)0.0290 (5)
C160.3499 (3)−0.02467 (19)0.42624 (9)0.0278 (5)
C410.3222 (3)0.06828 (16)0.15215 (8)0.0176 (4)
C420.2926 (3)0.15603 (17)0.10663 (8)0.0204 (4)
C430.1333 (3)0.15706 (17)0.07421 (8)0.0215 (4)
C440.0029 (3)0.06916 (17)0.08755 (8)0.0198 (4)
C450.0287 (3)−0.02115 (17)0.13111 (8)0.0211 (4)
C460.1900 (3)−0.02151 (17)0.16321 (8)0.0209 (4)
H1A0.69730.15290.39520.030*
H1B0.68980.00480.39260.030*
H2A0.3911−0.02110.29840.025*
H2B0.5718−0.09870.31140.025*
H3A0.6845−0.05230.21480.024*
H3B0.4875−0.11290.20780.024*
H60.85670.29660.16120.027*
H71.13790.31500.20860.030*
H81.18710.21520.30120.029*
H90.95280.11060.34850.028*
H120.42120.27160.41420.032*
H130.14040.27890.46270.037*
H14−0.01080.09640.48770.035*
H150.1198−0.09480.46410.035*
H160.4033−0.10260.41740.033*
H420.38360.21570.09800.025*
H430.11340.21680.04340.026*
H45−0.0620−0.08150.13880.025*
H460.2108−0.08330.19300.025*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O410.0370 (9)0.0441 (9)0.0498 (10)−0.0031 (8)−0.0184 (8)0.0248 (8)
O420.0248 (8)0.0301 (8)0.0437 (9)−0.0072 (7)−0.0092 (7)0.0042 (7)
N10.0205 (8)0.0239 (8)0.0186 (7)−0.0037 (7)0.0006 (6)−0.0014 (6)
N50.0205 (8)0.0183 (7)0.0196 (7)−0.0002 (7)−0.0004 (6)−0.0001 (6)
N440.0235 (9)0.0221 (8)0.0275 (8)0.0024 (7)−0.0056 (7)0.0020 (7)
C10.0242 (10)0.0316 (10)0.0201 (9)−0.0029 (9)−0.0013 (8)0.0009 (8)
C20.0206 (9)0.0179 (8)0.0235 (9)−0.0019 (7)−0.0028 (7)0.0028 (7)
C30.0203 (9)0.0166 (8)0.0226 (8)−0.0003 (7)−0.0024 (7)−0.0007 (7)
C40.0196 (9)0.0179 (8)0.0170 (8)0.0013 (7)0.0017 (7)−0.0018 (7)
C5A0.0195 (9)0.0162 (8)0.0231 (9)0.0006 (7)0.0012 (7)−0.0027 (7)
C60.0261 (10)0.0190 (9)0.0233 (9)−0.0015 (8)0.0028 (8)−0.0033 (7)
C70.0215 (10)0.0235 (9)0.0294 (10)−0.0052 (8)0.0059 (8)−0.0068 (8)
C80.0177 (9)0.0245 (9)0.0293 (9)−0.0009 (8)−0.0021 (8)−0.0088 (8)
C90.0221 (10)0.0229 (9)0.0247 (9)0.0001 (8)−0.0023 (8)−0.0023 (8)
C9A0.0196 (9)0.0167 (8)0.0216 (8)0.0006 (7)−0.0003 (7)−0.0029 (7)
C110.0253 (10)0.0295 (10)0.0151 (8)−0.0015 (9)−0.0009 (7)0.0014 (7)
C120.0348 (11)0.0238 (10)0.0223 (9)−0.0059 (9)0.0029 (9)−0.0016 (8)
C130.0380 (12)0.0287 (10)0.0265 (10)0.0032 (10)0.0063 (9)−0.0023 (8)
C140.0282 (11)0.0375 (11)0.0216 (9)−0.0026 (10)0.0037 (8)0.0018 (8)
C150.0322 (11)0.0296 (10)0.0252 (9)−0.0069 (9)0.0021 (9)0.0057 (8)
C160.0338 (12)0.0231 (10)0.0264 (10)0.0005 (9)0.0010 (9)0.0032 (8)
C410.0182 (9)0.0179 (8)0.0167 (8)0.0002 (7)0.0001 (7)−0.0005 (7)
C420.0210 (9)0.0195 (9)0.0208 (9)−0.0035 (8)0.0021 (7)0.0018 (7)
C430.0253 (10)0.0204 (9)0.0189 (8)0.0007 (8)0.0000 (7)0.0040 (7)
C440.0192 (9)0.0205 (9)0.0196 (8)0.0019 (8)−0.0030 (7)−0.0007 (7)
C450.0211 (9)0.0184 (8)0.0236 (9)−0.0024 (8)−0.0001 (7)0.0031 (7)
C460.0241 (9)0.0183 (8)0.0201 (8)−0.0007 (8)−0.0019 (7)0.0034 (7)
Geometric parameters (Å, º) top
N1—C9A1.413 (2)C41—C461.398 (2)
N1—C21.468 (2)C41—C421.400 (2)
N1—C11.475 (2)C42—C431.378 (2)
C1—C111.512 (3)C42—H420.95
C1—H1A0.99C43—C441.384 (3)
C1—H1B0.99C43—H430.95
C11—C161.392 (3)C44—C451.385 (2)
C11—C121.392 (3)C44—N441.465 (2)
C12—C131.392 (3)N44—O421.222 (2)
C12—H120.95N44—O411.230 (2)
C13—C141.382 (3)C45—C461.386 (3)
C13—H130.95C45—H450.95
C14—C151.386 (3)C46—H460.95
C14—H140.95N5—C5A1.416 (2)
C15—C161.391 (3)C5A—C61.390 (3)
C15—H150.95C5A—C9A1.422 (3)
C16—H160.95C6—C71.388 (3)
C2—C31.522 (2)C6—H60.95
C2—H2A0.99C7—C81.388 (3)
C2—H2B0.99C7—H70.95
C3—C41.506 (2)C8—C91.380 (3)
C3—H3A0.99C8—H80.95
C3—H3B0.99C9—C9A1.406 (3)
C4—N51.286 (2)C9—H90.95
C4—C411.484 (2)
C9A—N1—C2118.40 (15)C41—C4—C3119.96 (15)
C9A—N1—C1116.30 (15)C46—C41—C42119.12 (17)
C2—N1—C1111.34 (15)C46—C41—C4121.00 (16)
N1—C1—C11111.66 (15)C42—C41—C4119.86 (16)
N1—C1—H1A109.3C43—C42—C41120.89 (17)
C11—C1—H1A109.3C43—C42—H42119.6
N1—C1—H1B109.3C41—C42—H42119.6
C11—C1—H1B109.3C42—C43—C44118.50 (16)
H1A—C1—H1B107.9C42—C43—H43120.8
C16—C11—C12118.58 (18)C44—C43—H43120.8
C16—C11—C1122.02 (18)C43—C44—C45122.43 (17)
C12—C11—C1119.40 (18)C43—C44—N44119.16 (16)
C13—C12—C11120.51 (18)C45—C44—N44118.40 (16)
C13—C12—H12119.7O42—N44—O41123.27 (17)
C11—C12—H12119.7O42—N44—C44118.70 (15)
C14—C13—C12120.39 (19)O41—N44—C44118.04 (16)
C14—C13—H13119.8C44—C45—C46118.49 (17)
C12—C13—H13119.8C44—C45—H45120.8
C13—C14—C15119.66 (19)C46—C45—H45120.8
C13—C14—H14120.2C45—C46—C41120.53 (16)
C15—C14—H14120.2C45—C46—H46119.7
C14—C15—C16119.98 (19)C41—C46—H46119.7
C14—C15—H15120.0C4—N5—C5A119.43 (15)
C16—C15—H15120.0C6—C5A—N5116.02 (16)
C15—C16—C11120.88 (19)C6—C5A—C9A119.72 (17)
C15—C16—H16119.6N5—C5A—C9A124.17 (16)
C11—C16—H16119.6C7—C6—C5A121.35 (18)
N1—C2—C3112.01 (14)C7—C6—H6119.3
N1—C2—H2A109.2C5A—C6—H6119.3
C3—C2—H2A109.2C8—C7—C6119.16 (18)
N1—C2—H2B109.2C8—C7—H7120.4
C3—C2—H2B109.2C6—C7—H7120.4
H2A—C2—H2B107.9C9—C8—C7120.27 (18)
C4—C3—C2110.99 (14)C9—C8—H8119.9
C4—C3—H3A109.4C7—C8—H8119.9
C2—C3—H3A109.4C8—C9—C9A121.78 (17)
C4—C3—H3B109.4C8—C9—H9119.1
C2—C3—H3B109.4C9A—C9—H9119.1
H3A—C3—H3B108.0C9—C9A—N1122.26 (16)
N5—C4—C41117.40 (16)C9—C9A—C5A117.34 (17)
N5—C4—C3122.63 (16)N1—C9A—C5A120.15 (16)
C9A—N1—C1—C11154.54 (16)C41—C42—C43—C44−0.1 (3)
C2—N1—C1—C11−65.8 (2)C42—C43—C44—C45−1.6 (3)
N1—C1—C11—C1693.2 (2)C42—C43—C44—N44177.16 (16)
N1—C1—C11—C12−87.9 (2)C43—C44—N44—O42−177.07 (18)
C16—C11—C12—C130.2 (3)C45—C44—N44—O421.7 (3)
C1—C11—C12—C13−178.71 (17)C43—C44—N44—O412.6 (3)
C11—C12—C13—C14−0.5 (3)C45—C44—N44—O41−178.56 (19)
C12—C13—C14—C150.1 (3)C43—C44—C45—C461.3 (3)
C13—C14—C15—C160.6 (3)N44—C44—C45—C46−177.46 (16)
C14—C15—C16—C11−0.9 (3)C44—C45—C46—C410.7 (3)
C12—C11—C16—C150.5 (3)C42—C41—C46—C45−2.3 (3)
C1—C11—C16—C15179.39 (17)C4—C41—C46—C45175.94 (16)
C1—N1—C2—C3−163.59 (16)C41—C4—N5—C5A−179.90 (15)
N1—C2—C3—C4−55.9 (2)C4—N5—C5A—C6141.63 (18)
C2—C3—C4—N573.7 (2)N5—C5A—C6—C7−177.24 (15)
C3—C4—N5—C5A−0.8 (2)C9A—C5A—C6—C76.0 (3)
C4—N5—C5A—C9A−41.8 (2)C5A—C6—C7—C8−1.0 (3)
N5—C5A—C9A—N1−9.1 (3)C6—C7—C8—C9−2.9 (3)
C5A—C9A—N1—C266.3 (2)C7—C8—C9—C9A1.6 (3)
C9A—N1—C2—C3−24.8 (2)C8—C9—C9A—N1−170.97 (17)
C2—C3—C4—C41−107.26 (17)C8—C9—C9A—C5A3.3 (3)
N5—C4—C41—C46−158.87 (18)C2—N1—C9A—C9−119.59 (19)
C3—C4—C41—C4622.0 (2)C1—N1—C9A—C917.2 (3)
N5—C4—C41—C4219.4 (2)C1—N1—C9A—C5A−156.92 (17)
C3—C4—C41—C42−159.75 (17)C6—C5A—C9A—C9−7.0 (3)
C46—C41—C42—C432.0 (3)N5—C5A—C9A—C9176.53 (16)
C4—C41—C42—C43−176.25 (16)C6—C5A—C9A—N1167.38 (17)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C14—H14···O42i0.952.553.378 (3)146
C43—H43···O41ii0.952.423.153 (3)134
C46—H46···Cgiii0.952.743.578 (2)147
Symmetry codes: (i) −x−1/2, −y, z+1/2; (ii) x+1/2, −y+1/2, −z; (iii) −x+1, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formulaC22H19N3O2
Mr357.40
Crystal system, space groupOrthorhombic, P212121
Temperature (K)120
a, b, c (Å)7.3810 (2), 10.8016 (3), 22.1319 (5)
V (Å3)1764.50 (8)
Z4
Radiation typeMo Kα
µ (mm−1)0.09
Crystal size (mm)0.38 × 0.36 × 0.34
Data collection
DiffractometerNonius KappaCCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.963, 0.971
No. of measured, independent and
observed [I > 2σ(I)] reflections		12216, 2314, 2127
Rint0.031
(sin θ/λ)max (Å−1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.044, 0.107, 1.16
No. of reflections2314
No. of parameters245
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.43, −0.44

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 torsion angles (º) top
N1—C2—C3—C4−55.9 (2)N5—C5A—C9A—N1−9.1 (3)
C2—C3—C4—N573.7 (2)C5A—C9A—N1—C266.3 (2)
C3—C4—N5—C5A−0.8 (2)C9A—N1—C2—C3−24.8 (2)
C4—N5—C5A—C9A−41.8 (2)C43—C44—N44—O412.6 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C14—H14···O42i0.952.553.378 (3)146
C43—H43···O41ii0.952.423.153 (3)134
C46—H46···Cgiii0.952.743.578 (2)147
Symmetry codes: (i) −x−1/2, −y, z+1/2; (ii) x+1/2, −y+1/2, −z; (iii) −x+1, y−1/2, −z+1/2.
 

Acknowledgements

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

References

First citationFerguson, G. (1999). PRPKAPPA. University of Guelph, Canada.  Google Scholar
 First citationFlack, H. D. (1983). Acta Cryst. A39, 876–881.  CrossRef CAS Web of Science IUCr Journals Google Scholar
 First citationFlack, H. D. & Bernardinelli, G. (2000). J. Appl. Cryst. 33, 1143–1148.  Web of Science CrossRef CAS IUCr Journals 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 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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Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296
Volume 61| Part 6| June 2005| Pages o404-o407
doi:10.1107/S010827010501379X
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