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Acta Crystallogr Sect E Struct Rep Online. 2010 January 1; 66(Pt 1): o66.
Published online 2009 December 9. doi:  10.1107/S1600536809051848
PMCID: PMC2979996

(7-Dimethylamino-1-hydroxy-3-naphthyl)(morpholino)methanone

Abstract

In the title compound, C17H20N2O3, the morpholine ring is in a slightly distorted chair form. The crystal structure is stabilized by an inter­molecular O—H(...)O hydrogen bond between the H atom of the hydroxyl group and the O atom of a neighbouring carbonyl group. A weak inter­molecular C—H(...)π inter­action is also present.

Related literature

For the synthesis and applications of organic photochromic dyes, see: Gabbutt et al. (2003 [triangle], 2004 [triangle]); Kumar et al. (1995 [triangle]); Gemert & Selvig (2000 [triangle]); Nelson et al. (2002 [triangle]). For their potential use as variable optical transmission materials and in optical storage, see; Crano & Guglielmetti (1999 [triangle]).

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Object name is e-66-00o66-scheme1.jpg

Experimental

Crystal data

  • C17H20N2O3
  • M r = 300.35
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-00o66-efi7.jpg
  • a = 12.6250 (5) Å
  • b = 13.9634 (6) Å
  • c = 8.8369 (3) Å
  • V = 1557.84 (11) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 296 K
  • 0.41 × 0.18 × 0.08 mm

Data collection

  • Bruker APEXII CCD diffractometer
  • 8069 measured reflections
  • 2044 independent reflections
  • 1475 reflections with I > 2σ(I)
  • R int = 0.025

Refinement

  • R[F 2 > 2σ(F 2)] = 0.044
  • wR(F 2) = 0.115
  • S = 1.04
  • 2044 reflections
  • 200 parameters
  • 1 restraint
  • H-atom parameters constrained
  • Δρmax = 0.19 e Å−3
  • Δρmin = −0.15 e Å−3

Data collection: APEX2 (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809051848/lx2129sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809051848/lx2129Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

The synthesis of organic photochromic dyes and their application has become of great interest recently (Gabbutt et al., 2003, 2004; Kumar et al., 1995; Gemert & Selvig, 2000; Nelson et al., 2002. Because they may be useful such as variable optical transmission materials (ophthalmic glasses and lenses) or in potential use such as optical storage (optical disks or memories) (Crano & Guglielmetti, 1999). Here we report the crystal structure of the title compound (Fig. 1). In the title compound, the conformation of the morpholine ring is in a slightly distorted chair form. The crystal packing (Fig. 2) is stabilized by an intermolecular O—H···O hydrogen bond between the H atom of the hydroxyl group and the O atom of a neighbouring C═O unit, with a O1—H1···O2i (Table 1). The molecular packing (Fig. 2) is further stabilized by a intermolecular C—H···π interaction between a methyl H atom of the dimethylamino group and the N-bonded benzene ring, with a C17—H17C···Cgii (Table 1; Cg is the centroid of the C5–C10 benzene ring).

Experimental

The title compound was synthesized from the reaction of 1-hydroxy-7-dimethylamino-3-naphthonic acid (116 g, 0.5 mol) and morpholine (48 g, 1.2 mol) in anhydrous CH2Cl2 for 24 h at room temperature. The reaction was quenched by the addition of water and the organic layer separated, dried over anhydrous MgSO4, filtered and concentrated to give the title compound (120 g, yield 81%). Single crystals suitable for X-ray diffraction were prepared by evaporation of a solution of the title compound in ethyl acetate at room temperature.

Refinement

All the Friedel pairs were merged. All hydrogen atoms were placed in calculated positions using a riding model, with C—H = 0.93–0.97 Å, O—H = 0.82 Å, and with Uiso(H) = 1.2–1.5 Ueq(C, O).

Figures

Fig. 1.
The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are presented as a small spheres of arbitrary radius.
Fig. 2.
O—H···O and C—H···π interactions (dotted lines) in the crystal structure of the title compound. Cg denotes the ring centroid. [Symmetry codes: (i) - x + 3/2, y, z -1/2; (ii) - x + ...

Crystal data

C17H20N2O3F(000) = 640
Mr = 300.35Dx = 1.281 Mg m3
Orthorhombic, Pca21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2acCell parameters from 2694 reflections
a = 12.6250 (5) Åθ = 2.9–22.0°
b = 13.9634 (6) ŵ = 0.09 mm1
c = 8.8369 (3) ÅT = 296 K
V = 1557.84 (11) Å3Block, silver
Z = 40.41 × 0.18 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer1475 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.025
graphiteθmax = 28.3°, θmin = 1.5°
Detector resolution: 10 pixels mm-1h = −16→11
[var phi] and ω scansk = −9→18
8069 measured reflectionsl = −9→11
2044 independent reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.044H-atom parameters constrained
wR(F2) = 0.115w = 1/[σ2(Fo2) + (0.0628P)2 + 0.0129P] where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
2044 reflectionsΔρmax = 0.19 e Å3
200 parametersΔρmin = −0.15 e Å3
1 restraintExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.009 (2)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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)

xyzUiso*/Ueq
O10.67137 (15)0.76538 (16)0.3748 (2)0.0597 (6)
H10.72570.79210.40330.090*
O20.64658 (15)0.84718 (18)0.9402 (3)0.0682 (6)
O30.31381 (16)0.94813 (16)1.1678 (2)0.0583 (6)
N10.38830 (19)0.55244 (19)0.1665 (3)0.0600 (8)
N20.47850 (17)0.89337 (17)0.9690 (3)0.0475 (6)
C10.4410 (2)0.76093 (18)0.7082 (3)0.0432 (6)
H1A0.38860.75950.78210.052*
C20.53284 (19)0.81050 (16)0.7348 (3)0.0387 (6)
C30.6131 (2)0.81177 (19)0.6231 (3)0.0397 (6)
H3A0.67620.84390.64220.048*
C40.59920 (19)0.76642 (18)0.4873 (3)0.0389 (6)
C50.50466 (19)0.71367 (16)0.4583 (3)0.0362 (5)
C60.4919 (2)0.66117 (17)0.3236 (3)0.0412 (6)
H6A0.54460.66340.25010.049*
C70.4022 (2)0.60611 (19)0.2982 (3)0.0465 (7)
C80.3216 (2)0.6086 (2)0.4082 (4)0.0514 (8)
H8A0.25930.57460.39110.062*
C90.3321 (2)0.65914 (19)0.5389 (4)0.0483 (7)
H9A0.27720.65890.60900.058*
C100.4249 (2)0.71200 (17)0.5702 (3)0.0383 (6)
C110.5567 (2)0.8524 (2)0.8856 (3)0.0448 (6)
C120.38259 (19)0.94019 (19)0.9127 (3)0.0429 (6)
H12A0.36630.91650.81210.051*
H12B0.39441.00870.90580.051*
C130.2917 (2)0.9210 (2)1.0154 (4)0.0552 (8)
H13A0.23030.95610.97990.066*
H13B0.27480.85331.01240.066*
C140.4045 (2)0.8996 (2)1.2216 (4)0.0616 (8)
H14A0.39100.83121.22150.074*
H14B0.41840.91901.32510.074*
C150.5006 (2)0.9204 (2)1.1257 (3)0.0595 (9)
H15A0.51770.98801.13100.071*
H15B0.56080.88441.16310.071*
C160.3346 (3)0.4603 (2)0.1784 (5)0.0888 (13)
H16A0.28100.46390.25520.133*
H16B0.38500.41160.20470.133*
H16C0.30240.44480.08310.133*
C170.4705 (3)0.5571 (3)0.0525 (5)0.0855 (13)
H17A0.50210.61960.05330.128*
H17B0.44020.5449−0.04530.128*
H17C0.52360.50980.07380.128*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0421 (11)0.0899 (15)0.0471 (12)−0.0209 (10)0.0090 (10)−0.0154 (11)
O20.0366 (11)0.1086 (17)0.0593 (13)0.0192 (11)−0.0110 (11)−0.0273 (12)
O30.0509 (12)0.0789 (14)0.0452 (11)0.0120 (11)0.0080 (9)0.0015 (10)
N10.0498 (16)0.0608 (15)0.0693 (18)0.0048 (12)−0.0095 (14)−0.0306 (13)
N20.0353 (12)0.0696 (15)0.0375 (12)0.0122 (11)−0.0063 (11)−0.0107 (11)
C10.0382 (15)0.0469 (14)0.0443 (16)0.0039 (12)0.0031 (13)−0.0048 (12)
C20.0342 (14)0.0419 (13)0.0400 (14)0.0046 (11)0.0011 (12)−0.0038 (11)
C30.0314 (15)0.0431 (14)0.0446 (15)−0.0028 (11)−0.0034 (12)−0.0046 (11)
C40.0312 (14)0.0436 (13)0.0419 (14)−0.0025 (11)0.0033 (12)−0.0003 (12)
C50.0332 (13)0.0360 (12)0.0394 (14)0.0048 (10)−0.0043 (11)0.0004 (11)
C60.0359 (15)0.0431 (13)0.0446 (14)0.0041 (12)0.0002 (12)−0.0042 (11)
C70.0443 (17)0.0410 (14)0.0542 (17)0.0081 (12)−0.0123 (14)−0.0087 (12)
C80.0376 (16)0.0493 (15)0.067 (2)−0.0063 (12)−0.0098 (15)−0.0082 (14)
C90.0379 (16)0.0511 (15)0.0557 (17)−0.0018 (13)0.0043 (13)−0.0048 (14)
C100.0350 (14)0.0370 (12)0.0428 (14)−0.0022 (11)−0.0006 (12)−0.0015 (10)
C110.0350 (16)0.0535 (15)0.0460 (15)0.0050 (12)−0.0005 (13)−0.0093 (13)
C120.0377 (15)0.0492 (14)0.0417 (14)0.0086 (12)0.0018 (12)−0.0014 (12)
C130.0396 (17)0.071 (2)0.0551 (19)0.0011 (14)−0.0013 (14)0.0017 (15)
C140.064 (2)0.077 (2)0.0447 (16)0.0134 (17)−0.0017 (16)−0.0045 (16)
C150.0465 (18)0.086 (2)0.0455 (17)0.0145 (17)−0.0083 (14)−0.0217 (17)
C160.099 (3)0.0587 (18)0.109 (3)−0.0026 (19)−0.028 (3)−0.032 (2)
C170.077 (2)0.106 (3)0.073 (2)0.011 (2)−0.002 (2)−0.053 (2)

Geometric parameters (Å, °)

O1—C41.349 (3)C6—H6A0.9300
O1—H10.8200C7—C81.409 (4)
O2—C111.235 (3)C8—C91.360 (4)
O3—C141.413 (4)C8—H8A0.9300
O3—C131.426 (4)C9—C101.411 (4)
N1—C71.395 (4)C9—H9A0.9300
N1—C171.448 (4)C12—C131.487 (4)
N1—C161.458 (4)C12—H12A0.9700
N2—C111.359 (3)C12—H12B0.9700
N2—C151.461 (4)C13—H13A0.9700
N2—C121.463 (3)C13—H13B0.9700
C1—C21.370 (3)C14—C151.508 (4)
C1—C101.413 (4)C14—H14A0.9700
C1—H1A0.9300C14—H14B0.9700
C2—C31.414 (4)C15—H15A0.9700
C2—C111.487 (4)C15—H15B0.9700
C3—C41.368 (4)C16—H16A0.9600
C3—H3A0.9300C16—H16B0.9600
C4—C51.426 (3)C16—H16C0.9600
C5—C61.407 (4)C17—H17A0.9600
C5—C101.412 (4)C17—H17B0.9600
C6—C71.387 (4)C17—H17C0.9600
C4—O1—H1109.5O2—C11—C2120.9 (2)
C14—O3—C13110.4 (2)N2—C11—C2120.3 (2)
C7—N1—C17117.8 (2)N2—C12—C13110.5 (2)
C7—N1—C16118.2 (3)N2—C12—H12A109.5
C17—N1—C16115.0 (3)C13—C12—H12A109.5
C11—N2—C15118.9 (2)N2—C12—H12B109.5
C11—N2—C12127.2 (2)C13—C12—H12B109.5
C15—N2—C12111.4 (2)H12A—C12—H12B108.1
C2—C1—C10120.9 (3)O3—C13—C12112.2 (2)
C2—C1—H1A119.5O3—C13—H13A109.2
C10—C1—H1A119.5C12—C13—H13A109.2
C1—C2—C3119.5 (2)O3—C13—H13B109.2
C1—C2—C11121.6 (2)C12—C13—H13B109.2
C3—C2—C11118.4 (2)H13A—C13—H13B107.9
C4—C3—C2121.0 (2)O3—C14—C15111.7 (3)
C4—C3—H3A119.5O3—C14—H14A109.3
C2—C3—H3A119.5C15—C14—H14A109.3
O1—C4—C3124.4 (2)O3—C14—H14B109.3
O1—C4—C5115.3 (2)C15—C14—H14B109.3
C3—C4—C5120.3 (2)H14A—C14—H14B107.9
C6—C5—C10120.2 (2)N2—C15—C14109.2 (2)
C6—C5—C4121.1 (2)N2—C15—H15A109.8
C10—C5—C4118.7 (2)C14—C15—H15A109.8
C7—C6—C5121.3 (2)N2—C15—H15B109.8
C7—C6—H6A119.4C14—C15—H15B109.8
C5—C6—H6A119.4H15A—C15—H15B108.3
C6—C7—N1122.4 (3)N1—C16—H16A109.5
C6—C7—C8117.7 (2)N1—C16—H16B109.5
N1—C7—C8119.9 (2)H16A—C16—H16B109.5
C9—C8—C7121.9 (3)N1—C16—H16C109.5
C9—C8—H8A119.1H16A—C16—H16C109.5
C7—C8—H8A119.1H16B—C16—H16C109.5
C8—C9—C10121.3 (3)N1—C17—H17A109.5
C8—C9—H9A119.4N1—C17—H17B109.5
C10—C9—H9A119.4H17A—C17—H17B109.5
C9—C10—C5117.6 (2)N1—C17—H17C109.5
C9—C10—C1122.8 (3)H17A—C17—H17C109.5
C5—C10—C1119.6 (2)H17B—C17—H17C109.5
O2—C11—N2118.7 (3)
C10—C1—C2—C3−0.7 (4)C6—C5—C10—C9−2.2 (3)
C10—C1—C2—C11−172.5 (2)C4—C5—C10—C9−179.9 (2)
C1—C2—C3—C41.8 (4)C6—C5—C10—C1176.7 (2)
C11—C2—C3—C4173.8 (2)C4—C5—C10—C1−1.0 (3)
C2—C3—C4—O1179.2 (2)C2—C1—C10—C9179.2 (2)
C2—C3—C4—C5−2.4 (4)C2—C1—C10—C50.4 (4)
O1—C4—C5—C62.9 (4)C15—N2—C11—O2−6.4 (4)
C3—C4—C5—C6−175.7 (2)C12—N2—C11—O2154.2 (3)
O1—C4—C5—C10−179.5 (2)C15—N2—C11—C2170.5 (3)
C3—C4—C5—C102.0 (4)C12—N2—C11—C2−28.8 (4)
C10—C5—C6—C7−0.8 (3)C1—C2—C11—O2138.2 (3)
C4—C5—C6—C7176.9 (2)C3—C2—C11—O2−33.7 (4)
C5—C6—C7—N1−179.1 (2)C1—C2—C11—N2−38.7 (4)
C5—C6—C7—C83.4 (4)C3—C2—C11—N2149.4 (3)
C17—N1—C7—C6−1.3 (4)C11—N2—C12—C13144.1 (3)
C16—N1—C7—C6144.3 (3)C15—N2—C12—C13−54.0 (3)
C17—N1—C7—C8176.1 (3)C14—O3—C13—C12−57.6 (3)
C16—N1—C7—C8−38.3 (4)N2—C12—C13—O355.1 (3)
C6—C7—C8—C9−3.1 (4)C13—O3—C14—C1558.8 (3)
N1—C7—C8—C9179.3 (3)C11—N2—C15—C14−141.8 (3)
C7—C8—C9—C100.2 (4)C12—N2—C15—C1454.6 (3)
C8—C9—C10—C52.5 (4)O3—C14—C15—N2−57.5 (3)
C8—C9—C10—C1−176.4 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1···O2i0.821.822.631 (3)172
C17—H17C···Cgii0.962.803.533 (2)134

Symmetry codes: (i) −x+3/2, y, z−1/2; (ii) −x+1, −y+1, z−1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: LX2129).

References

  • Bruker (2007). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Crano, J. C. & Guglielmetti, R. J. (1999). Editors. Organic Photochromic and Thermochromic Compounds, Vol 1. New York: Plenum Press.
  • Gabbutt, C. D., Hepworth, J. D., Heron, B. M., Thomas, D. A., Kilner, C. & Partington, S. M. (2004). Heterocycles, 63, 567–582.
  • Gabbutt, C. D., Heron, B. M., Instone, A. C., Thomas, D. A., Partington, S. M., Hursthouse, M. B. & Gelbrich, T. (2003). Eur. J. Org. Chem. pp. 1220–1230.
  • Gemert, B. V. & Selvig, C. D. (2000). US Patent 6106744.
  • Kumar, A., Gemert, B. V. & Knowles, D. B. (1995). US Patent 5458814.
  • Nelson, C. M., Chopra, A., Knowles, D. B., Gemert, B. V. & Kumar, A. (2002). US Patent 6348604 B1.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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