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

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 64| Part 10| October 2008| Page o1978
doi:10.1107/S1600536808029735

(Z)-tert-Butyl 2-(4-amino-9H-fluoren-9-yl­­idene)acetate

Marios Krokidis,a Dionissios Papaioannoua and Vassilios Nastopoulosa*

aDepartment of Chemistry, University of Patras, 265 04 Patras, Greece
*Correspondence e-mail: nastopoulos@chemistry.upatras.gr

(Received 4 September 2008; accepted 16 September 2008; online 20 September 2008)

The title compound, C19H19NO2, obtained as an almost equimolar mixture (as shown by 1H NMR) with the E isomer through a Wittig reaction between 4-amino-9H-fluoren-9-one and the stabilized ylide Ph3P=CHCO2C(CH3)3, was obtained pure in the Z configuration following crystallization from toluene. The mol­ecule shows a planar arrangement of the ring system and the new double bond, whereas the carbonyl O atom forms a 45.1 (3)° dihedral angle with it. The mol­ecules are linked by N—H⋯O hydrogen bonds, forming cyclic structures with R44(24) graph-set motifs. These motifs are connected to each other, giving rise to a sheet structure parallel to the ab plane. The linkage within the sheets is further enhanced by π–π stacking inter­actions between the fluorene units [centroid–centroid distance = 3.583 (2) Å].

Related literature

For general background on retinoids, see: Meyer et al. (1978[Meyer, H., Bollag, W., Hänni, R. & Rüegg, R. (1978). Experientia (Generalia), 34, 1105-1246.]); Sporn et al. (1994[Sporn, M. B., Roberts, A. B. & Goodman, D. S. (1994). Editors. The Retinoids - Biology, Chemistry and Medicine, 2nd ed. New York: Raven Press.]). For hydrogen-bond motifs, see: Bernstein et al. (1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]). For related literature, see: Magoulas & Papaioannou (2003[Magoulas, G. & Papaioannou, D. (2003). ARKIVOC, vi, 213-227.]).

[Scheme 1]

Experimental

Crystal data

  • C19H19NO2

  • Mr = 293.35

  • Orthorhombic, P b c a

  • a = 9.0820 (12) Å

  • b = 13.7330 (17) Å

  • c = 24.568 (3) Å

  • V = 3064.2 (7) Å3

  • Z = 8

  • Mo Kα radiation

  • μ = 0.08 mm−1

  • T = 100 (2) K

  • 0.32 × 0.26 × 0.16 mm
Data collection

  • Oxford Diffraction Xcalibur-3 with Sapphire CCD diffractometer

  • Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]) Tmin = 0.956, Tmax = 0.989

  • 18331 measured reflections

  • 2671 independent reflections

  • 1671 reflections with I > 2σ(I)

  • Rint = 0.119
Refinement

  • R[F2 > 2σ(F2)] = 0.063

  • wR(F2) = 0.143

  • S = 1.01

  • 2671 reflections

  • 211 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.30 e Å−3

  • Δρmin = −0.22 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N—H1N⋯O1i 0.85 (3) 2.62 (3) 3.295 (3) 137 (3)
N—H2N⋯O2ii 0.92 (3) 2.24 (3) 3.133 (3) 163 (3)
Symmetry codes: (i) [-x, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]; (ii) [x-{\script{1\over 2}}, y, -z+{\script{3\over 2}}].

Data collection: CrysAlis CCD (Oxford Diffraction, 2008[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]); cell refinement: CrysAlis RED (Oxford Diffraction, 2008[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]); data reduction: CrysAlis RED; program(s) used to solve structure: SIR92 (Altomare et al., 1994[Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: PLATON (Spek, 2003[Spek, A. L. (2003). J. Appl. Cryst. 36, 7-13.]), ORTEP-3 (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]) and DIAMOND (Brandenburg, 2008[Brandenburg, K. (2008). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: WinGX (Farrugia, 1999[Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837-838.]) and publCIF (Westrip, 2008[Westrip, S. P. (2008). publCIF. In preparation.]).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808029735/dn2370sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808029735/dn2370Isup2.hkl

checkCIF report


Comment top

Retinoids, a large family of natural and synthetic compounds structurally related to vitamin A play an important role in a variety of biological functions including vision, development, reproduction and cell differentiation and have been applied successfully to the management of severe skin disorders (Sporn et al., 1994; Meyer et al., 1978). For example, acitretin (1) is presently regarded as the drug of choice for the treatment of psoriasis. However, retinoids are toxic compounds in large doses as well as teratogenic. Therefore, a huge array of analogs have been synthesized aiming at improving the therapeutic efficacy to toxicity index as well as to secure better selectivities for various therapeutic applications. These analogs usually involve changes in the lipophilic part of the molecules and/or the tetraene chain. As concerns the latter, double bonds have been for example replaced by the isosteric amide bond and/or incorporated into aromatic rings to restrict conformational freedom of the chain (Sporn et al.., 1994). Along this line, we have recently reported the synthesis of analogs like compound 2 (Magoulas & Papaioannou, 2003). We thought that the tetraene chain might be mimicked by compounds of the general formula 3, which could be readily assembled by joining commercially available cinnamic acids and an 4-amino-9H-fluoren-9-one derived α,β-unsaturated carboxylic acid (Fig. 1).

The latter could be readily obtained by a Wittig reaction between 4-amino-9H-fluoeren-9-one (4) and the stabilized ylide tert-butoxycarbonylmethylenetriphenylphosphorane(BCMP). Indeed, condensation of 4 and BCMP, followed by routine flash column chromatography purification of the reaction mixture, provided tert-butyl 2-(4-amino-9H-fluoren-9-ylidene)acetate as an inseparable, by TLC, mixture of the E (5a) and Z (5 b) isomers (Fig. 2).

Examination of this reaction product by 1H-NMR revealed that the two isomers were present in the ratio 1:0.8. Crystallization of this mixture of isomers from toluene provided one of the two isomers almost free of the other isomer. On the other hand, evaporation of the mother liquor and crystallization of the residue provided the other isomer almost free of the first one as shown by 1H-NMR experiments and comparing the spectra of the two isomers with the one received from their mixture. In an attempt to identify which isomer is which, we decided to proceed with further recrystallizations of the almost pure isomers, obtained as described above. To our delight, the second recrystallization of the former isomer provided it in a suitable crystalline form to allow for an X-ray analysis. Unsuccessful were, however, our attempts to obtain the second isomer in an also suitable crystalline form for X-ray analysis.

We now wish to report the results of the X-ray crystallographic analysis of the former isomer which allowed us to determine unambiguously its configuration around the exocyclic double bond. As it can be seen from Figure 3, this compound actually has the Z configuration around the double bond (isomer 5 b) and therefore the other isomer should be the E isomer (5a).

The molecule shows an almost planar arrangement of the ring system and the new double bond (the maximum deviation from their mean plane being 0.091 (2) Å for atom C10), whereas the carbonyl O2 atom lies 0.602 (3) Å outside the plane and forms a 45.1 (3)° dihedral angle with it. The C9═ C10 (Csp2–Csp2) distance of 1.340 (4) Å confirms the localization of the double bond at this position. Each molecule is linked to four neighbouring molecules via intermolecular hydrogen bonds between the amide H atoms and the two O atoms (N—H1N···O1 and N—H2N···O2) to form cyclic structures with R44(24) graph-set motifs (Bernstein et al.., 1995). This bonding pattern results in a network of connected R44(24) rings lying on pleated layers parallel to the ab plane (Table 1 and Fig. 4). The tert-butyl moieties are packed between the layers.

The linkage inside each layer is further supported by weak π—π stacking interactions among the central five-membered ring and one of the attached six-membered rings of the fluorene moieties. Specifically, the C1'-C4'-C5'-C8'-C9 fulvene ring at (x, y, z) and the C1'-C1-C2-C3-C4-C4' aryl ring at (1/2+x, y, 3/2-z) are almost parallel forming between them a dihedral angle of 6.5 (2)°. The centroid separation of the two rings is 3.583 (2) Å and the perpendicular distance of the first centroid on the plane of the second ring is 3.421 (1) Å, corresponding to a centroid offset of 1.07 (2) Å.

Related literature top

For general background on retinoids, see: Meyer et al. (1978); Sporn et al. (1994). For hydrogen-bond motifs, see: Bernstein et al. (1995). For related literature, see: Magoulas & Papaioannou (2003).

Experimental top

A mixture of 4-amino-9H-fluoren-9-one (0.78 g, 4 mmol) and ylide BCMP (3.16 g, 8.4 mmol) in anhydrous DMF (4 ml) was stirred at 100 oC for 4 days under an atmosphere of argon. The resulting solution was diluted with 30 ml e thylacetate (EtOAc) and then washed with H2O (3 x 10 ml). The organic layer was dried (Na2SO4) and evaporated to dryness under reduced pressure. The residue was subjected to flash column chromatography using as eluant the solvent system PhMe/EtOAc (9.5:0.5).

The fractions with Rf 0.3 in the same solvent system were pooled and evaporated to leave 1.1 g (95% yield) of pure compound in the form of a reddish oil. 1H NMR of the product revealed the presence of the two geometrical isomers in the ratio 1:0.8 calculated on the basis of the integration of the two peaks at 8.839 and 8.329 p.p.m. where proton H-8 resonates for the isomers 5a and 5 b, respectively.The product was dissolved in the minimum volume of hot toluene. The resulting solution was then left to attain ambient temperature and then cooled at 5 oC for 2 days. The crystalline precipitate was collected, washed with ice-cold toluene and dried under reduced pressure. It weighed 60 mg. 1H NMR of the crystals thus obtained showed them to be almost the pure isomer (5a:5 b=1:10) with H-8 resonating at 8.329 p.p.m.. The mother liquor from the crystallization was evaporated to dryness and the residue was crystallized also from toluene to provide 70 mg of the almost pure alternative isomer with H-8 resonating at 8.839 p.p.m.. Recrystallization of the first crystalline isomer finally gave reddish crystals suitable for X-ray analysis. This isomer had m.p. 386–387 K.

Refinement top

The amine H atoms and that attached to C14 were located in difference Fourier maps and their positions were refined freely along with Uiso(H) equal to 1.5Ueq and 1.2Ueq of their parent atoms, respectively. The methyl H atoms were constrained to an ideal geometry [C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C)], but were allowed to rotate freely about the C—C bonds. The remaining phenyl group H atoms were placed in geometrically idealized positions and constrained to ride on their parent C atoms [C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C)]. Five low-angle reflections were omitted from the final cycles of refinement because their observed intensities were significantly lower than the calculated values, being apparently obscured by the beam stop.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis RED (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2008); software used to prepare material for publication: WinGX (Farrugia, 1999) and publCIF (Westrip, 2008).

Figures top
[Figure 1] Fig. 1. Synthetic scheme, part 1.
[Figure 2] Fig. 2. Synthetic scheme, part 2.
[Figure 3] Fig. 3. The molecular structure of the title compound (5 b) with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 4] Fig. 4. Part of the crystal structure of compound 5b, showing the network of the connected R44(24) cyclic structures parallel to the ab plane and the π—π stacking interactions among the fluorene moieties (green dotted lines). For the sake of clarity, only the H-atoms involved in the bonding pattern (dashed lines) are drawn. [Symmetry codes: (i) -x, y+1/2, -z+3/2, (ii) x-1/2, y, -z+3/2, (iii) -x, -0.5+y, 1.5-z and (iv) 0.5+x, y, 1.5-z]
(Z)-tert-butyl 2-(4-amino-9H-fluoren-9-ylidene)acetate top
Crystal data top
C19H19NO2F(000) = 1248
Mr = 293.35Dx = 1.272 Mg m−3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 3945 reflections
a = 9.0820 (12) Åθ = 3.1–30.2°
b = 13.7330 (17) ŵ = 0.08 mm−1
c = 24.568 (3) ÅT = 100 K
V = 3064.2 (7) Å3Prism, light yellow
Z = 80.32 × 0.26 × 0.16 mm
Data collection top
Oxford Diffraction Xcalibur-3 with Sapphire CCD
diffractometer		2671 independent reflections
Radiation source: Enhance (Mo) X-ray source1671 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.119
Detector resolution: 16.0288 pixels mm-1θmax = 25.0°, θmin = 3.2°
ω and ϕ scansh = −8→10
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2008)		k = −16→14
Tmin = 0.956, Tmax = 0.989l = −27→29
18331 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)] = 0.063Hydrogen site location: difference Fourier map
wR(F2) = 0.143H atoms treated by a mixture of independent and constrained refinement
S = 1.01 w = 1/[σ2(Fo2) + (0.069P)2]
where P = (Fo2 + 2Fc2)/3
2671 reflections(Δ/σ)max < 0.001
211 parametersΔρmax = 0.30 e Å−3
0 restraintsΔρmin = −0.22 e Å−3
Crystal data top
C19H19NO2V = 3064.2 (7) Å3
Mr = 293.35Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 9.0820 (12) ŵ = 0.08 mm−1
b = 13.7330 (17) ÅT = 100 K
c = 24.568 (3) Å0.32 × 0.26 × 0.16 mm
Data collection top
Oxford Diffraction Xcalibur-3 with Sapphire CCD
diffractometer		2671 independent reflections
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2008)		1671 reflections with I > 2σ(I)
Tmin = 0.956, Tmax = 0.989Rint = 0.119
18331 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0630 restraints
wR(F2) = 0.143H atoms treated by a mixture of independent and constrained refinement
S = 1.01Δρmax = 0.30 e Å−3
2671 reflectionsΔρmin = −0.22 e Å−3
211 parameters
Special details top

Experimental. IR (KBr, n, cm-1): 3404 and 3338 (w), 1700 (s), 1628 (m); 1H NMR (400 MHz, CDCl3): d 8.329 (d, J = 7.6 Hz, 1H, H-8), 7.623 (d, J = 7.6 Hz, 1H, H-5), 7.528 (d, J= 7.6 Hz, 1H, H-1), 7.319 (t, J = 6.8 Hz, 1H, H-7), 7.152 (t, J= 6.8 Hz, 1H, H-6), 7.089 (t, J = 8 Hz, 1H, H-2), 6.707 (d, J= 7.6 Hz, 1H, H-3), 6.628 (s, 1H, H-10), 3.959 (s, 2H, NH2),1.541 (s, 9H, H-13) p.p.m.; EI—MS m/z: 293 (M+, 9), 237 (100), 220 (11), 193 (13), 180 (17), 165 (12).

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C1'0.1196 (3)0.06224 (19)0.71979 (11)0.0225 (7)
C10.0627 (3)0.11302 (19)0.67557 (12)0.0268 (7)
H10.09060.09770.64020.032*
C2−0.0373 (3)0.18742 (19)0.68596 (12)0.0301 (7)
H2−0.07510.22320.65700.036*
C3−0.0816 (3)0.20922 (19)0.73829 (12)0.0275 (7)
H3−0.14960.25890.74370.033*
C4−0.0270 (3)0.15855 (19)0.78340 (12)0.0236 (7)
C4'0.0775 (3)0.08588 (18)0.77339 (11)0.0225 (7)
C5'0.1565 (3)0.02216 (19)0.81212 (12)0.0225 (7)
C50.1598 (3)0.0176 (2)0.86812 (12)0.0271 (7)
H50.10170.05920.88880.033*
C60.2509 (3)−0.0500 (2)0.89319 (12)0.0315 (8)
H60.2537−0.05340.93100.038*
C70.3378 (3)−0.1125 (2)0.86264 (12)0.0294 (7)
H70.3974−0.15790.88010.035*
C80.3365 (3)−0.1077 (2)0.80637 (11)0.0248 (7)
H80.3956−0.14920.78590.030*
C8'0.2461 (3)−0.04057 (18)0.78088 (11)0.0216 (7)
C90.2258 (3)−0.02063 (19)0.72239 (12)0.0224 (7)
C100.2879 (3)−0.0755 (2)0.68355 (12)0.0241 (7)
H100.350 (3)−0.129 (2)0.6933 (11)0.029*
C110.2785 (3)−0.0635 (2)0.62405 (12)0.0258 (7)
C120.2695 (3)−0.1621 (2)0.54059 (11)0.0268 (7)
C130.2656 (4)−0.2720 (2)0.53364 (13)0.0450 (9)
H13A0.3497−0.30030.55120.067*
H13B0.2675−0.28780.49560.067*
H13C0.1772−0.29740.54970.067*
C140.4087 (4)−0.1212 (3)0.51722 (13)0.0445 (9)
H14A0.4062−0.05140.51940.067*
H14B0.4175−0.14060.47980.067*
H14C0.4915−0.14530.53740.067*
C150.1325 (4)−0.1164 (2)0.51698 (13)0.0421 (9)
H15A0.0472−0.14250.53490.063*
H15B0.1272−0.13040.47870.063*
H15C0.1358−0.04720.52230.063*
N−0.0702 (3)0.18283 (18)0.83630 (11)0.0298 (6)
H1N−0.147 (4)0.218 (2)0.8360 (13)0.045*
H2N−0.095 (3)0.132 (2)0.8587 (13)0.045*
O10.2699 (2)−0.15191 (12)0.60048 (7)0.0262 (5)
O20.2815 (3)0.01219 (14)0.59924 (8)0.0384 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C1'0.0268 (16)0.0110 (14)0.0297 (17)−0.0066 (12)−0.0013 (13)−0.0008 (12)
C10.0332 (17)0.0165 (15)0.0306 (17)−0.0016 (13)−0.0030 (14)0.0037 (13)
C20.0370 (19)0.0179 (15)0.0353 (18)−0.0032 (14)−0.0047 (15)0.0060 (14)
C30.0291 (18)0.0108 (15)0.043 (2)0.0003 (13)−0.0027 (15)−0.0014 (13)
C40.0264 (16)0.0130 (14)0.0314 (18)−0.0047 (12)0.0012 (14)−0.0025 (12)
C4'0.0288 (16)0.0111 (14)0.0277 (17)−0.0044 (12)−0.0031 (13)0.0004 (12)
C5'0.0263 (16)0.0124 (14)0.0289 (17)−0.0047 (12)−0.0032 (14)−0.0029 (12)
C50.0349 (18)0.0194 (15)0.0270 (17)−0.0007 (13)0.0022 (14)−0.0055 (13)
C60.0423 (19)0.0264 (17)0.0259 (17)−0.0013 (15)−0.0006 (15)−0.0039 (13)
C70.0369 (18)0.0204 (16)0.0310 (18)0.0022 (14)−0.0043 (15)−0.0008 (14)
C80.0316 (17)0.0146 (14)0.0281 (17)−0.0009 (13)−0.0018 (14)−0.0051 (13)
C8'0.0296 (16)0.0109 (13)0.0243 (16)−0.0051 (12)−0.0001 (14)−0.0038 (12)
C90.0230 (16)0.0126 (14)0.0317 (17)−0.0043 (12)−0.0033 (14)−0.0004 (12)
C100.0329 (18)0.0107 (14)0.0287 (17)−0.0011 (12)−0.0011 (14)−0.0008 (13)
C110.0332 (18)0.0153 (15)0.0288 (16)−0.0029 (13)0.0013 (14)−0.0008 (13)
C120.0359 (18)0.0220 (16)0.0225 (16)−0.0015 (14)0.0017 (14)−0.0009 (12)
C130.083 (3)0.0263 (18)0.0259 (18)−0.0044 (18)0.0041 (18)−0.0059 (14)
C140.052 (2)0.053 (2)0.0285 (18)−0.0116 (18)0.0043 (17)0.0036 (16)
C150.049 (2)0.046 (2)0.0303 (18)0.0002 (17)−0.0025 (17)−0.0051 (16)
N0.0346 (16)0.0172 (14)0.0374 (16)0.0019 (12)0.0056 (13)−0.0018 (12)
O10.0446 (13)0.0125 (10)0.0214 (11)−0.0021 (9)0.0032 (10)−0.0001 (8)
O20.0723 (17)0.0127 (10)0.0303 (12)−0.0024 (10)−0.0025 (11)0.0043 (9)
Geometric parameters (Å, º) top
C1'—C11.391 (4)C8'—C91.475 (4)
C1'—C4'1.409 (4)C9—C101.340 (4)
C1'—C91.493 (4)C10—C111.474 (4)
C1—C21.391 (4)C10—H100.96 (3)
C1—H10.9300C11—O21.205 (3)
C2—C31.380 (4)C11—O11.347 (3)
C2—H20.9300C12—O11.478 (3)
C3—C41.399 (4)C12—C141.498 (4)
C3—H30.9300C12—C151.510 (4)
C4—N1.398 (4)C12—C131.519 (4)
C4—C4'1.400 (4)C13—H13A0.9600
C4'—C5'1.478 (4)C13—H13B0.9600
C5'—C51.377 (4)C13—H13C0.9600
C5'—C8'1.412 (4)C14—H14A0.9600
C5—C61.387 (4)C14—H14B0.9600
C5—H50.9300C14—H14C0.9600
C6—C71.387 (4)C15—H15A0.9600
C6—H60.9300C15—H15B0.9600
C7—C81.384 (4)C15—H15C0.9600
C7—H70.9300N—H1N0.85 (3)
C8—C8'1.384 (4)N—H2N0.92 (3)
C8—H80.9300
C1—C1'—C4'120.9 (3)C10—C9—C1'132.1 (3)
C1—C1'—C9131.0 (3)C8'—C9—C1'105.3 (2)
C4'—C1'—C9108.1 (2)C9—C10—C11128.3 (3)
C1'—C1—C2117.9 (3)C9—C10—H10120.2 (16)
C1'—C1—H1121.1C11—C10—H10111.5 (16)
C2—C1—H1121.1O2—C11—O1124.1 (3)
C3—C2—C1121.4 (3)O2—C11—C10126.6 (3)
C3—C2—H2119.3O1—C11—C10109.2 (2)
C1—C2—H2119.3O1—C12—C14110.1 (2)
C2—C3—C4121.8 (3)O1—C12—C15110.2 (2)
C2—C3—H3119.1C14—C12—C15113.1 (3)
C4—C3—H3119.1O1—C12—C13101.9 (2)
N—C4—C3121.2 (3)C14—C12—C13110.5 (3)
N—C4—C4'121.6 (3)C15—C12—C13110.6 (3)
C3—C4—C4'117.1 (3)C12—C13—H13A109.5
C4—C4'—C1'120.8 (3)C12—C13—H13B109.5
C4—C4'—C5'129.7 (3)H13A—C13—H13B109.5
C1'—C4'—C5'109.5 (2)C12—C13—H13C109.5
C5—C5'—C8'120.2 (3)H13A—C13—H13C109.5
C5—C5'—C4'132.9 (3)H13B—C13—H13C109.5
C8'—C5'—C4'106.9 (2)C12—C14—H14A109.5
C5'—C5—C6119.1 (3)C12—C14—H14B109.5
C5'—C5—H5120.4H14A—C14—H14B109.5
C6—C5—H5120.4C12—C14—H14C109.5
C5—C6—C7120.9 (3)H14A—C14—H14C109.5
C5—C6—H6119.6H14B—C14—H14C109.5
C7—C6—H6119.6C12—C15—H15A109.5
C8—C7—C6120.4 (3)C12—C15—H15B109.5
C8—C7—H7119.8H15A—C15—H15B109.5
C6—C7—H7119.8C12—C15—H15C109.5
C8'—C8—C7119.3 (3)H15A—C15—H15C109.5
C8'—C8—H8120.4H15B—C15—H15C109.5
C7—C8—H8120.4C4—N—H1N111 (2)
C8—C8'—C5'120.1 (3)C4—N—H2N116 (2)
C8—C8'—C9129.7 (2)H1N—N—H2N104 (3)
C5'—C8'—C9110.1 (2)C11—O1—C12120.9 (2)
C10—C9—C8'122.4 (3)
C4'—C1'—C1—C2−0.3 (4)C7—C8—C8'—C5'0.0 (4)
C9—C1'—C1—C2179.3 (3)C7—C8—C8'—C9179.4 (3)
C1'—C1—C2—C3−1.4 (4)C5—C5'—C8'—C80.8 (4)
C1—C2—C3—C40.8 (4)C4'—C5'—C8'—C8178.5 (2)
C2—C3—C4—N178.5 (3)C5—C5'—C8'—C9−178.8 (2)
C2—C3—C4—C4'1.4 (4)C4'—C5'—C8'—C9−1.0 (3)
N—C4—C4'—C1'179.9 (2)C8—C8'—C9—C106.5 (5)
C3—C4—C4'—C1'−3.1 (4)C5'—C8'—C9—C10−174.0 (3)
N—C4—C4'—C5'1.6 (4)C8—C8'—C9—C1'−177.6 (3)
C3—C4—C4'—C5'178.7 (3)C5'—C8'—C9—C1'1.9 (3)
C1—C1'—C4'—C42.6 (4)C1—C1'—C9—C10−6.4 (5)
C9—C1'—C4'—C4−177.1 (2)C4'—C1'—C9—C10173.2 (3)
C1—C1'—C4'—C5'−178.8 (2)C1—C1'—C9—C8'178.3 (3)
C9—C1'—C4'—C5'1.5 (3)C4'—C1'—C9—C8'−2.0 (3)
C4—C4'—C5'—C5−4.5 (5)C8'—C9—C10—C11−179.2 (3)
C1'—C4'—C5'—C5177.1 (3)C1'—C9—C10—C116.2 (5)
C4—C4'—C5'—C8'178.1 (3)C9—C10—C11—O239.7 (5)
C1'—C4'—C5'—C8'−0.3 (3)C9—C10—C11—O1−142.0 (3)
C8'—C5'—C5—C6−0.7 (4)O2—C11—O1—C122.5 (4)
C4'—C5'—C5—C6−177.8 (3)C10—C11—O1—C12−175.8 (2)
C5'—C5—C6—C7−0.1 (4)C14—C12—O1—C1160.3 (3)
C5—C6—C7—C80.8 (5)C15—C12—O1—C11−65.1 (3)
C6—C7—C8—C8'−0.7 (4)C13—C12—O1—C11177.6 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N—H1N···O1i0.85 (3)2.62 (3)3.295 (3)137 (3)
N—H2N···O2ii0.92 (3)2.24 (3)3.133 (3)163 (3)
Symmetry codes: (i) −x, y+1/2, −z+3/2; (ii) x−1/2, y, −z+3/2.

Experimental details

Crystal data
Chemical formulaC19H19NO2
Mr293.35
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)100
a, b, c (Å)9.0820 (12), 13.7330 (17), 24.568 (3)
V (Å3)3064.2 (7)
Z8
Radiation typeMo Kα
µ (mm−1)0.08
Crystal size (mm)0.32 × 0.26 × 0.16
Data collection
DiffractometerOxford Diffraction Xcalibur-3 with Sapphire CCD
diffractometer
Absorption correctionMulti-scan
(CrysAlis RED; Oxford Diffraction, 2008)
Tmin, Tmax0.956, 0.989
No. of measured, independent and
observed [I > 2σ(I)] reflections		18331, 2671, 1671
Rint0.119
(sin θ/λ)max (Å−1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.063, 0.143, 1.01
No. of reflections2671
No. of parameters211
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)0.30, −0.22

Computer programs: CrysAlis CCD (Oxford Diffraction, 2008), CrysAlis RED (Oxford Diffraction, 2008), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2008), WinGX (Farrugia, 1999) and publCIF (Westrip, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N—H1N···O1i0.85 (3)2.62 (3)3.295 (3)137 (3)
N—H2N···O2ii0.92 (3)2.24 (3)3.133 (3)163 (3)
Symmetry codes: (i) −x, y+1/2, −z+3/2; (ii) x−1/2, y, −z+3/2.
 

Acknowledgements

The authors thank Dr A. Tasiopoulos (Department of Chemistry, University of Cyprus) for help with the data collection.

References

First citationAltomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435.  CrossRef Web of Science IUCr Journals Google Scholar
 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 citationBrandenburg, K. (2008). DIAMOND. Crystal Impact GbR, Bonn, Germany.  Google Scholar
 First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
 First citationFarrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.  CrossRef CAS IUCr Journals Google Scholar
 First citationMagoulas, G. & Papaioannou, D. (2003). ARKIVOC, vi, 213–227.  CrossRef Google Scholar
 First citationMeyer, H., Bollag, W., Hänni, R. & Rüegg, R. (1978). Experientia (Generalia), 34, 1105–1246.  Google Scholar
 First citationOxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.  Google Scholar
 First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationSpek, A. L. (2003). J. Appl. Cryst. 36, 7–13.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationSporn, M. B., Roberts, A. B. & Goodman, D. S. (1994). Editors. The Retinoids – Biology, Chemistry and Medicine, 2nd ed. New York: Raven Press.  Google Scholar
 First citationWestrip, S. P. (2008). publCIF. In preparation.  Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

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ISSN: 2056-9890
Volume 64| Part 10| October 2008| Page o1978
doi:10.1107/S1600536808029735
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