organic papers
o1370
Maet al. C15H17NO2 doi:10.1107/S1600536805011384 Acta Cryst.(2005). E61, o1370–o1371
Acta Crystallographica Section E Structure Reports
Online
ISSN 1600-5368
1-Morpholinomethyl-2-naphthol
Shan-Shan Ma, Ming-Jie Zhang,* Dong-Yan Yuan and Zhao-Bin Qi
Department of Chemistry, Tianjin University, Tianjin 300072, People’s Republic of China
Correspondence e-mail: [email protected]
Key indicators
Single-crystal X-ray study
T= 293 K
Mean(C–C) = 0.002 A˚
Rfactor = 0.046
wRfactor = 0.132
Data-to-parameter ratio = 18.3
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2005 International Union of Crystallography Printed in Great Britain – all rights reserved
The title compound, C15H17NO2, is a product of a Mannich
reaction involving 2-naphthol, formaldehyde and morpholine. The morpholine ring has a chair conformation and the crystal
structure is stabilized by an intramolecular O—H N
hydrogen bond linking the naphthol OH group and the morpholine N atom.
Comment
The Mannich reaction (Arendet al., 1998; Bur & Martin, 2001) is an important C—C bond formation reaction widely used in the synthesis of secondary and tertiary amine derivatives, and is a key step in the synthesis of many bioactive molecules and complex natural products (Itoet al., 2001; Liras et al., 2001). We have prepared the title compound, (I), by the Mannich reaction (Shrineret al., 1946) and the crystal structure of (I) is reported in this paper.
The molecular structure of (I) is shown in Fig. 1. In the structure, the morpholine ring has the usual chair conforma-tion. The naphthol ring system is almost planar, with atoms C5 and C6 deviating by 0.0200 (2) and 0.0174 (2) A˚ , respectively, from the mean plane. An intramolecular hydrogen bond between the hydroxy group and the N atom stabilizes the crystal structure.
[image:1.610.207.460.602.716.2]Received 7 March 2005 Accepted 12 April 2005 Online 16 April 2005
Figure 1
Experimental
A sample of 2-naphthol (68 g) was dissolved in 95% alcohol (450 ml) and cooled at 278 K. Morpholine (49 g) was added very slowly to formalin (38 g) cooled to 278 K. The 2-naphthol solution was added in three portions with stirring. A flaky crystalline precipitate was obtained. This was filtered, dried and recrystallized from 95% alcohol. Colorless plates were formed in 75% yield. M.p. 388–389 K. IR (KBr, cm1):
3433, 2974, 2851, 1458, 1116;1H NMR (CDCl 3,
p.p.m.):7.095–8.367 (m, 6H), 4.181 (s, 2H), 3.713–3.821 (m, 4H), 2.685–2.722 (m, 4H).
Crystal data
C15H17NO2
Mr= 243.30 Monoclinic,P21=c
a= 22.162 (6) A˚
b= 5.8941 (17) A˚
c= 9.743 (3) A˚
= 91.120 (4)
V= 1272.5 (6) A˚3
Z= 4
Dx= 1.270 Mg m
3
MoKradiation Cell parameters from 1509
reflections
= 2.8–22.9
= 0.08 mm1
T= 293 (2) K Block, colourless 0.260.240.22 mm
Data collection
Bruker SMART CCD area-detector diffractometer
’and!scans
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)
Tmin= 0.978,Tmax= 0.982 7978 measured reflections
3052 independent reflections 1908 reflections withI> 2(I)
Rint= 0.026
max= 28.0
h=24!29
k=7!7
l=9!12
Refinement
Refinement onF2
R[F2> 2(F2)] = 0.046
wR(F2) = 0.132
S= 1.08 3052 reflections 167 parameters
H atoms treated by a mixture of independent and constrained refinement
w= 1/[2(F
o2) + (0.047P)2 + 0.1845P]
whereP= (Fo2+ 2Fc2)/3 (/)max= 0.001
max= 0.19 e A˚
3
min=0.15 e A˚
3
Table 1
Selected bond lengths (A˚ ).
N1—C15 1.462 (2)
N1—C12 1.465 (2)
N1—C11 1.472 (2)
O1—C2 1.364 (2)
Table 2
Hydrogen-bond geometry (A˚ ,).
D—H A D—H H A D A D—H A
O1—H1 N1 0.87 (1) 1.80 (1) 2.597 (2) 153 (2)
The H atom of the hydroxy group was located in a difference Fourier map and was refined isotropically. The remaining H atoms were positioned geometrically (C—H = 0.93–0.97 A˚ ) and refined as riding on their parent atom, with Uiso(H) values equal to
1.2Ueq(carrier atom).
Data collection:SMART(Bruker, 1997); cell refinement:SAINT
(Bruker, 1997); data reduction:SAINT; program(s) used to solve structure:SHELXS97(Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics:
SHELXTL (Bruker, 1997); software used to prepare material for publication:SHELXTL.
References
Arend, M., Westermann, B. & Risch, N. (1998).Angew. Chem. Int. Ed.37, 1044–1070.
Bruker (1997).SMART,SAINTandSHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.
Bur, S. K. & Martin, S. F. (2001).Tetrahedron,57, 3221–3242.
Ito, M., Clark, C. W., Mortimore, M., Goh, J. B. & Martin, S. F. (2001).J. Am. Chem. Soc.123, 8003–8010.
Liras, S., Davoren, J. E. & Bordner, J. (2001).Org. Lett.3, 703–706. Sheldrick, G. M. (1996).SADABS. University of Go¨ttingen, Germany. Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of
Go¨ttingen, Germany.
supporting information
sup-1 Acta Cryst. (2005). E61, o1370–o1371
supporting information
Acta Cryst. (2005). E61, o1370–o1371 [https://doi.org/10.1107/S1600536805011384]
1-Morpholinomethyl-2-naphthol
Shan-Shan Ma, Ming-Jie Zhang, Dong-Yan Yuan and Zhao-Bin Qi
1-Morpholinomethyl-2-naphthol
Crystal data
C15H17NO2 Mr = 243.30
Monoclinic, P21/c Hall symbol: -P 2ybc a = 22.162 (6) Å b = 5.8941 (17) Å c = 9.743 (3) Å β = 91.120 (4)° V = 1272.5 (6) Å3 Z = 4
F(000) = 520 Dx = 1.270 Mg m−3 Melting point: 388 K
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 1509 reflections θ = 2.8–22.9°
µ = 0.08 mm−1 T = 293 K Block, colourless 0.26 × 0.24 × 0.22 mm
Data collection
Bruker SMART CCD area-detector diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
φ and ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) Tmin = 0.978, Tmax = 0.982
7978 measured reflections 3052 independent reflections 1908 reflections with I > 2σ(I) Rint = 0.026
θmax = 28.0°, θmin = 2.8° h = −24→29
k = −7→7 l = −9→12
Refinement
Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.046 wR(F2) = 0.132 S = 1.08 3052 reflections 167 parameters 1 restraint
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ2(Fo2) + (0.047P)2 + 0.1845P] where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.001 Δρmax = 0.19 e Å−3 Δρmin = −0.15 e Å−3
Special details
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)
x y z Uiso*/Ueq
N1 0.34428 (5) 0.6766 (2) 0.41978 (12) 0.0390 (3)
O1 0.31060 (5) 0.3988 (2) 0.61056 (12) 0.0588 (3)
H1 0.3316 (8) 0.496 (3) 0.5649 (18) 0.079 (7)*
O2 0.45996 (5) 0.6207 (2) 0.30210 (14) 0.0690 (4)
C1 0.23684 (7) 0.5785 (2) 0.46180 (15) 0.0414 (3)
C2 0.25363 (7) 0.4140 (3) 0.55596 (15) 0.0456 (4)
C3 0.21193 (8) 0.2517 (3) 0.60067 (18) 0.0575 (4)
H3 0.2241 0.1422 0.6641 0.069*
C4 0.15450 (8) 0.2530 (3) 0.55275 (19) 0.0613 (5)
H4 0.1277 0.1434 0.5832 0.074*
C5 0.13429 (7) 0.4173 (3) 0.45740 (17) 0.0523 (4)
C6 0.17602 (7) 0.5838 (3) 0.41225 (15) 0.0441 (4)
C7 0.15384 (7) 0.7494 (3) 0.31923 (18) 0.0570 (4)
H7 0.1798 0.8611 0.2878 0.068*
C8 0.09514 (8) 0.7486 (4) 0.2746 (2) 0.0716 (6)
H8 0.0818 0.8597 0.2134 0.086*
C9 0.05502 (9) 0.5846 (4) 0.3191 (2) 0.0789 (6)
H9 0.0151 0.5860 0.2880 0.095*
C10 0.07437 (8) 0.4229 (4) 0.4078 (2) 0.0701 (6)
H10 0.0474 0.3127 0.4367 0.084*
C11 0.28129 (7) 0.7560 (3) 0.41663 (17) 0.0477 (4)
H11A 0.2707 0.8034 0.3239 0.057*
H11B 0.2780 0.8875 0.4759 0.057*
C12 0.35504 (7) 0.5130 (3) 0.30967 (16) 0.0480 (4)
H12A 0.3464 0.5831 0.2214 0.058*
H12B 0.3284 0.3837 0.3194 0.058*
C13 0.41922 (8) 0.4359 (3) 0.3161 (2) 0.0622 (5)
H13A 0.4271 0.3607 0.4032 0.075*
H13B 0.4259 0.3269 0.2434 0.075*
C14 0.45005 (7) 0.7817 (3) 0.40741 (19) 0.0590 (5)
H14A 0.4772 0.9090 0.3960 0.071*
H14B 0.4591 0.7126 0.4958 0.071*
C15 0.38623 (7) 0.8662 (3) 0.40550 (16) 0.0458 (4)
H15A 0.3809 0.9727 0.4802 0.055*
H15B 0.3778 0.9450 0.3198 0.055*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
supporting information
sup-3 Acta Cryst. (2005). E61, o1370–o1371
O1 0.0617 (8) 0.0656 (8) 0.0490 (7) −0.0017 (6) −0.0039 (5) 0.0176 (6)
O2 0.0572 (8) 0.0531 (7) 0.0978 (10) −0.0103 (6) 0.0292 (7) −0.0125 (7)
C1 0.0467 (8) 0.0386 (8) 0.0394 (8) 0.0009 (6) 0.0093 (6) −0.0007 (6)
C2 0.0529 (9) 0.0448 (9) 0.0393 (8) 0.0009 (7) 0.0064 (7) 0.0009 (7)
C3 0.0688 (12) 0.0498 (10) 0.0543 (10) 0.0005 (8) 0.0155 (8) 0.0134 (8)
C4 0.0639 (11) 0.0529 (10) 0.0678 (11) −0.0109 (8) 0.0222 (9) 0.0068 (9)
C5 0.0489 (10) 0.0523 (10) 0.0562 (10) −0.0036 (7) 0.0151 (7) −0.0041 (8)
C6 0.0439 (8) 0.0441 (8) 0.0448 (8) 0.0026 (7) 0.0114 (6) −0.0026 (7)
C7 0.0464 (9) 0.0605 (11) 0.0643 (11) 0.0059 (8) 0.0083 (8) 0.0100 (9)
C8 0.0507 (11) 0.0848 (14) 0.0795 (13) 0.0115 (10) 0.0017 (9) 0.0154 (11)
C9 0.0434 (10) 0.1024 (17) 0.0909 (15) 0.0004 (11) 0.0009 (10) 0.0040 (14)
C10 0.0510 (11) 0.0769 (14) 0.0829 (14) −0.0123 (9) 0.0140 (10) −0.0021 (11)
C11 0.0466 (9) 0.0406 (8) 0.0561 (9) 0.0018 (7) 0.0057 (7) 0.0051 (7)
C12 0.0542 (10) 0.0435 (8) 0.0464 (9) −0.0072 (7) 0.0051 (7) −0.0091 (7)
C13 0.0544 (10) 0.0449 (9) 0.0881 (14) −0.0060 (8) 0.0209 (9) −0.0114 (9)
C14 0.0504 (10) 0.0559 (10) 0.0707 (12) −0.0141 (8) 0.0026 (8) −0.0018 (9)
C15 0.0537 (9) 0.0387 (8) 0.0451 (9) −0.0069 (7) 0.0034 (7) −0.0031 (7)
Geometric parameters (Å, º)
N1—C15 1.462 (2) C7—H7 0.93
N1—C12 1.465 (2) C8—C9 1.389 (3)
N1—C11 1.472 (2) C8—H8 0.93
O1—C2 1.364 (2) C9—C10 1.351 (3)
O1—H1 0.867 (9) C9—H9 0.93
O2—C14 1.418 (2) C10—H10 0.93
O2—C13 1.4231 (19) C11—H11A 0.97
C1—C2 1.381 (2) C11—H11B 0.97
C1—C6 1.423 (2) C12—C13 1.493 (2)
C1—C11 1.509 (2) C12—H12A 0.97
C2—C3 1.405 (2) C12—H12B 0.97
C3—C4 1.347 (2) C13—H13A 0.97
C3—H3 0.9300 C13—H13B 0.97
C4—C5 1.409 (2) C14—C15 1.499 (2)
C4—H4 0.9300 C14—H14A 0.97
C5—C10 1.404 (2) C14—H14B 0.97
C5—C6 1.424 (2) C15—H15A 0.97
C6—C7 1.414 (2) C15—H15B 0.97
C7—C8 1.363 (2)
C15—N1—C12 108.67 (12) C9—C10—H10 119.2
C15—N1—C11 111.07 (12) C5—C10—H10 119.2
C12—N1—C11 111.21 (11) N1—C11—C1 113.45 (12)
C2—O1—H1 105.0 (14) N1—C11—H11A 108.9
C14—O2—C13 109.58 (13) C1—C11—H11A 108.9
C2—C1—C6 118.82 (14) N1—C11—H11B 108.9
C2—C1—C11 120.77 (14) C1—C11—H11B 108.9
O1—C2—C1 122.74 (14) N1—C12—C13 109.75 (13)
O1—C2—C3 116.36 (14) N1—C12—H12A 109.7
C1—C2—C3 120.90 (15) C13—C12—H12A 109.7
C4—C3—C2 120.76 (16) N1—C12—H12B 109.7
C4—C3—H3 119.6 C13—C12—H12B 109.7
C2—C3—H3 119.6 H12A—C12—H12B 108.2
C3—C4—C5 121.22 (15) O2—C13—C12 111.62 (14)
C3—C4—H4 119.4 O2—C13—H13A 109.3
C5—C4—H4 119.4 C12—C13—H13A 109.3
C10—C5—C4 121.95 (16) O2—C13—H13B 109.3
C10—C5—C6 119.54 (16) C12—C13—H13B 109.3
C4—C5—C6 118.50 (15) H13A—C13—H13B 108.0
C7—C6—C1 123.22 (14) O2—C14—C15 111.89 (13)
C7—C6—C5 117.00 (15) O2—C14—H14A 109.2
C1—C6—C5 119.78 (14) C15—C14—H14A 109.2
C8—C7—C6 121.32 (17) O2—C14—H14B 109.2
C8—C7—H7 119.3 C15—C14—H14B 109.2
C6—C7—H7 119.3 H14A—C14—H14B 107.9
C7—C8—C9 121.05 (18) N1—C15—C14 110.26 (13)
C7—C8—H8 119.5 N1—C15—H15A 109.6
C9—C8—H8 119.5 C14—C15—H15A 109.6
C10—C9—C8 119.57 (18) N1—C15—H15B 109.6
C10—C9—H9 120.2 C14—C15—H15B 109.6
C8—C9—H9 120.2 H15A—C15—H15B 108.1
C9—C10—C5 121.53 (18)
C6—C1—C2—O1 −178.85 (13) C5—C6—C7—C8 −0.2 (2)
C11—C1—C2—O1 −1.5 (2) C6—C7—C8—C9 0.0 (3)
C6—C1—C2—C3 1.1 (2) C7—C8—C9—C10 −0.1 (3)
C11—C1—C2—C3 178.48 (14) C8—C9—C10—C5 0.5 (3)
O1—C2—C3—C4 179.90 (15) C4—C5—C10—C9 178.28 (18)
C1—C2—C3—C4 −0.1 (3) C6—C5—C10—C9 −0.8 (3)
C2—C3—C4—C5 −0.5 (3) C15—N1—C11—C1 −167.23 (12)
C3—C4—C5—C10 −179.13 (17) C12—N1—C11—C1 71.60 (16)
C3—C4—C5—C6 −0.1 (3) C2—C1—C11—N1 29.8 (2)
C2—C1—C6—C7 177.92 (14) C6—C1—C11—N1 −152.85 (13)
C11—C1—C6—C7 0.6 (2) C15—N1—C12—C13 57.55 (16)
C2—C1—C6—C5 −1.6 (2) C11—N1—C12—C13 −179.89 (13)
C11—C1—C6—C5 −179.01 (13) C14—O2—C13—C12 58.5 (2)
C10—C5—C6—C7 0.6 (2) N1—C12—C13—O2 −59.43 (19)
C4—C5—C6—C7 −178.46 (15) C13—O2—C14—C15 −57.53 (19)
C10—C5—C6—C1 −179.79 (15) C12—N1—C15—C14 −56.74 (16)
C4—C5—C6—C1 1.1 (2) C11—N1—C15—C14 −179.39 (12)
supporting information
sup-5 Acta Cryst. (2005). E61, o1370–o1371
Hydrogen-bond geometry (Å, º)
D—H···A D—H H···A D···A D—H···A
