1-[(3-Chloro­phen­yl)(morpholin-4-yl)­meth­yl]naphthalen-2-ol

Shu, L.-J.

doi:10.1107/S1600536811021726

organic compounds

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Volume 67| Part 7| July 2011| Page o1681

doi:10.1107/S1600536811021726

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1-[(3-Chlorophenyl)(morpholin-4-yl)methyl]naphthalen-2-ol

Li-Jin Shu ^a ^*

^aKey Laboratory of Organosilicon Chemistry and Material Technology of the Ministry of Education, Hangzhou Normal University, Hangzhou 310012, People's Republic of China
^*Correspondence e-mail: sljchem@yahoo.com.cn

(Received 5 June 2011; accepted 6 June 2011; online 18 June 2011)

In the title compound, C₂₁H₂₀ClNO₂, the dihedral angle between the naphthylene ring system and the phenyl ring is 77.86 (15)°. The morpholine ring adopts a chair conformation. The hydroxyl group is involved in intramolecular O—H⋯N hydrogen bonding. A weak intermolecular C—H⋯π interaction is present in the crystal structure.

Related literature

For related structures, see: Devi & Bhuyan (2004 ); Domling & Ugi (2000 ); Fu et al. (2009 ). For multi-component reactions, see: Hulme & Gore (2003 ); Ugi (1962 ).

Experimental

Crystal data

C₂₁H₂₀ClNO₂
M_r = 353.83
Monoclinic, C c
a = 14.1896 (18) Å
b = 15.881 (2) Å
c = 10.3998 (10) Å
β = 132.13 (2)°
V = 1738.0 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 298 K
0.40 × 0.30 × 0.20 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.89, T_max = 1.00
7216 measured reflections
3127 independent reflections
2050 reflections with I > 2σ(I)
R_int = 0.105

Refinement

R[F² > 2σ(F²)] = 0.085
wR(F²) = 0.240
S = 0.99
3127 reflections
226 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.29 e Å⁻³
Absolute structure: Flack (1983 ), 1551 Friedel pairs
Flack parameter: 0.07 (16)

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C3–C8 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯N1	0.82	1.97	2.649 (6)	139
C21—H21A⋯Cgⁱ	0.93	2.87	3.770 (7)	164
Symmetry code: (i) $[x, -y+1, z-{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811021726/xu5238sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811021726/xu5238Isup2.hkl

checkCIF report

Comment top

Multi-component reactions (MCRs) (Hulme & Gore, 2003; Ugi, 1962) involving at least three starting materials in a one-pot reaction have attracted considerable attention in terms of saving both energy and raw materials (Devi & Bhuyan, 2004; Fu, et al. 2009). Compared to conventional multi-step organic syntheses, MCRs have merits over multi-step reactions that include the simplicity of a one-pot procedure and the buildup of complex molecules (Domling & Ugi, 2000). We report here the synthesis and crystal structure of the title compound, 1-((3-chlorophenyl)(morpholino)methyl)naphthalen-2-ol.

In the title compound (Fig. 1) bond lengths and angles have normal values. The dihedral angle between the naphthylene ring system and the benzene ring is 77.86 (15)°. The H atom of hydroxyl is involved in strong intramolecular O—H···N hydrogen bonds (Table 1). Weak intermolecular C—H···π interaction is present in the crystal structure.

Related literature top

For related structures, see: Devi & Bhuyan (2004); Domling & Ugi (2000); Fu et al. (2009). For multi-component reactions, see: Hulme & Gore (2003); Ugi (1962).

Experimental top

A dry 50 ml flask was charged with 3-chlorobenzaldehyde (10 mmol), naphthalen-2-ol (10 mmol) and morpholine (10 mmol). The mixture was stirred at 373 K for 12 h and then added ethanol (15 ml), after heated under reflux for 1 h, the precipitate was filtered out and washed with ethanol for 3 times to give the title compound. Colourless crystals suitable for X-ray diffraction were obtained by slow evaporation of a dichloromethane solution.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. A view of the asymmetric unit with the atomic numbering scheme. The displacement ellipsoids were drawn at the 30% probability level.

1-[(3-Chlorophenyl)(morpholin-4-yl)methyl]naphthalen-2-ol top

Crystal data top

C₂₁H₂₀ClNO₂	F(000) = 744
M_r = 353.83	D_x = 1.352 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 3951 reflections
a = 14.1896 (18) Å	θ = 3.7–27.5°
b = 15.881 (2) Å	µ = 0.23 mm⁻¹
c = 10.3998 (10) Å	T = 298 K
β = 132.13 (2)°	Block, colourless
V = 1738.0 (7) Å³	0.40 × 0.30 × 0.20 mm
Z = 4

Data collection top

Rigaku Mercury2 diffractometer	3127 independent reflections
Radiation source: fine-focus sealed tube	2050 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.105
Detector resolution: 13.6612 pixels mm^-1	θ_max = 25.2°, θ_min = 3.7°
CCD profile fitting scans	h = −16→16
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −18→18
T_min = 0.89, T_max = 1.00	l = −12→12
7216 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.085	H-atom parameters constrained
wR(F²) = 0.240	w = 1/[σ²(F_o²) + (0.116P)² + 0.730P] where P = (F_o² + 2F_c²)/3
S = 0.99	(Δ/σ)_max < 0.001
3127 reflections	Δρ_max = 0.33 e Å⁻³
226 parameters	Δρ_min = −0.29 e Å⁻³
2 restraints	Absolute structure: Flack (1983), 1551 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.07 (16)

Crystal data top

C₂₁H₂₀ClNO₂	V = 1738.0 (7) Å³
M_r = 353.83	Z = 4
Monoclinic, Cc	Mo Kα radiation
a = 14.1896 (18) Å	µ = 0.23 mm⁻¹
b = 15.881 (2) Å	T = 298 K
c = 10.3998 (10) Å	0.40 × 0.30 × 0.20 mm
β = 132.13 (2)°

Data collection top

Rigaku Mercury2 diffractometer	3127 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2050 reflections with I > 2σ(I)
T_min = 0.89, T_max = 1.00	R_int = 0.105
7216 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.085	H-atom parameters constrained
wR(F²) = 0.240	Δρ_max = 0.33 e Å⁻³
S = 0.99	Δρ_min = −0.29 e Å⁻³
3127 reflections	Absolute structure: Flack (1983), 1551 Friedel pairs
226 parameters	Absolute structure parameter: 0.07 (16)
2 restraints

Special details top

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) top

	x	y	z	U_iso*/U_eq
Cl1	0.84978 (14)	0.53891 (11)	0.59226 (19)	0.0747 (5)
N1	0.4387 (4)	0.6957 (3)	−0.0609 (6)	0.0481 (11)
C4	0.2270 (5)	0.5435 (4)	0.0113 (7)	0.0554 (15)
H4A	0.2462	0.5206	−0.0511	0.066*
C2	0.3791 (4)	0.6606 (3)	0.1069 (6)	0.0433 (13)
C3	0.2871 (4)	0.6169 (4)	0.1035 (7)	0.0458 (12)
O1	0.5267 (4)	0.7746 (2)	0.2256 (5)	0.0681 (12)
H1A	0.5381	0.7522	0.1660	0.102*
C10	0.4042 (6)	0.7604 (4)	0.3021 (8)	0.0615 (17)
H10A	0.4455	0.8085	0.3690	0.074*
C11	0.4105 (4)	0.6255 (4)	0.0053 (6)	0.0441 (13)
H11A	0.3346	0.5962	−0.0957	0.053*
C18	0.7153 (5)	0.5175 (4)	0.3731 (7)	0.0506 (13)
C1	0.4344 (5)	0.7309 (4)	0.2081 (7)	0.0530 (15)
C17	0.6232 (4)	0.5757 (4)	0.2811 (7)	0.0496 (14)
H17A	0.6314	0.6259	0.3337	0.060*
O2	0.3993 (4)	0.7915 (3)	−0.3232 (6)	0.0786 (13)
C16	0.5163 (5)	0.5618 (4)	0.1089 (6)	0.0474 (13)
C21	0.5104 (5)	0.4884 (3)	0.0364 (8)	0.0536 (15)
H21A	0.4409	0.4773	−0.0798	0.064*
C6	0.1102 (6)	0.5319 (5)	0.0997 (8)	0.071 (2)
H6A	0.0540	0.5025	0.1006	0.085*
C15	0.3269 (5)	0.7510 (4)	−0.1813 (8)	0.0530 (14)
H15A	0.2571	0.7192	−0.2820	0.064*
H15B	0.2997	0.7736	−0.1241	0.064*
C12	0.4812 (5)	0.6659 (4)	−0.1490 (7)	0.0529 (14)
H12A	0.5596	0.6343	−0.0681	0.063*
H12B	0.4175	0.6288	−0.2439	0.063*
C8	0.2555 (5)	0.6503 (4)	0.1990 (7)	0.0578 (16)
C19	0.7135 (6)	0.4438 (4)	0.3062 (8)	0.0629 (16)
H19A	0.7796	0.4051	0.3719	0.075*
C20	0.6086 (7)	0.4297 (4)	0.1365 (9)	0.0699 (17)
H20A	0.6023	0.3794	0.0856	0.084*
C9	0.3224 (6)	0.7255 (4)	0.3030 (8)	0.0646 (16)
H9A	0.3065	0.7482	0.3693	0.077*
C7	0.1665 (6)	0.6075 (6)	0.1928 (9)	0.080 (2)
H7A	0.1439	0.6296	0.2518	0.096*
C14	0.3634 (7)	0.8196 (5)	−0.2346 (9)	0.083 (2)
H14A	0.2923	0.8581	−0.3084	0.099*
H14B	0.4334	0.8506	−0.1325	0.099*
C13	0.5017 (6)	0.7377 (5)	−0.2158 (9)	0.074 (2)
H13A	0.5733	0.7699	−0.1181	0.089*
H13B	0.5247	0.7165	−0.2790	0.089*
C5	0.1409 (6)	0.5033 (5)	0.0082 (8)	0.0641 (17)
H5A	0.1017	0.4548	−0.0583	0.077*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0583 (8)	0.0818 (10)	0.0641 (8)	0.0128 (8)	0.0329 (7)	−0.0010 (8)
N1	0.0500 (19)	0.057 (3)	0.050 (2)	−0.0125 (19)	0.0387 (17)	−0.007 (2)
C4	0.046 (2)	0.075 (4)	0.051 (3)	−0.003 (3)	0.035 (2)	0.002 (3)
C2	0.040 (2)	0.053 (3)	0.035 (2)	0.005 (2)	0.025 (2)	0.008 (2)
C3	0.045 (2)	0.056 (3)	0.043 (2)	0.011 (2)	0.033 (2)	0.012 (2)
O1	0.066 (2)	0.058 (2)	0.070 (2)	−0.005 (2)	0.042 (2)	−0.010 (2)
C10	0.073 (3)	0.047 (3)	0.056 (3)	0.013 (3)	0.040 (3)	−0.008 (3)
C11	0.035 (2)	0.055 (3)	0.041 (2)	0.002 (2)	0.0247 (19)	0.001 (2)
C18	0.058 (3)	0.047 (3)	0.066 (3)	0.008 (2)	0.050 (2)	0.000 (2)
C1	0.048 (3)	0.052 (3)	0.051 (3)	−0.003 (3)	0.030 (2)	−0.013 (3)
C17	0.042 (2)	0.066 (4)	0.053 (3)	0.005 (2)	0.036 (2)	0.008 (3)
O2	0.105 (3)	0.081 (3)	0.077 (2)	0.036 (2)	0.072 (2)	0.033 (2)
C16	0.052 (2)	0.053 (3)	0.050 (3)	−0.016 (2)	0.039 (2)	−0.009 (2)
C21	0.064 (3)	0.044 (3)	0.058 (3)	−0.005 (3)	0.043 (3)	−0.013 (3)
C6	0.061 (3)	0.090 (5)	0.074 (4)	0.009 (3)	0.050 (3)	0.026 (4)
C15	0.046 (3)	0.052 (3)	0.055 (3)	0.010 (2)	0.031 (2)	0.009 (3)
C12	0.059 (3)	0.062 (3)	0.052 (3)	0.000 (3)	0.043 (2)	0.000 (3)
C8	0.064 (3)	0.077 (4)	0.049 (3)	0.018 (3)	0.045 (2)	0.024 (3)
C19	0.085 (3)	0.043 (3)	0.075 (3)	−0.001 (3)	0.059 (3)	−0.007 (3)
C20	0.108 (4)	0.040 (3)	0.096 (4)	−0.002 (3)	0.083 (3)	−0.004 (3)
C9	0.094 (3)	0.057 (4)	0.062 (3)	0.024 (3)	0.060 (3)	0.006 (3)
C7	0.083 (3)	0.122 (6)	0.078 (3)	0.031 (4)	0.071 (3)	0.037 (4)
C14	0.095 (4)	0.097 (5)	0.090 (4)	0.033 (4)	0.075 (3)	0.045 (4)
C13	0.084 (3)	0.096 (5)	0.077 (4)	−0.004 (4)	0.068 (3)	−0.001 (4)
C5	0.061 (3)	0.074 (4)	0.070 (4)	−0.003 (3)	0.050 (3)	0.007 (3)

Geometric parameters (Å, º) top

Cl1—C18	1.765 (6)	C16—C21	1.360 (8)
N1—C12	1.472 (7)	C21—C20	1.395 (9)
N1—C15	1.480 (7)	C21—H21A	0.9300
N1—C11	1.499 (7)	C6—C5	1.362 (10)
C4—C5	1.359 (9)	C6—C7	1.407 (11)
C4—C3	1.382 (8)	C6—H6A	0.9300
C4—H4A	0.9300	C15—C14	1.465 (10)
C2—C1	1.364 (7)	C15—H15A	0.9700
C2—C3	1.459 (7)	C15—H15B	0.9700
C2—C11	1.502 (8)	C12—C13	1.462 (10)
C3—C8	1.437 (8)	C12—H12A	0.9700
O1—C1	1.381 (7)	C12—H12B	0.9700
O1—H1A	0.8200	C8—C7	1.396 (9)
C10—C9	1.290 (9)	C8—C9	1.457 (9)
C10—C1	1.387 (9)	C19—C20	1.362 (9)
C10—H10A	0.9300	C19—H19A	0.9300
C11—C16	1.506 (7)	C20—H20A	0.9300
C11—H11A	0.9800	C9—H9A	0.9300
C18—C17	1.342 (7)	C7—H7A	0.9300
C18—C19	1.353 (8)	C14—H14A	0.9700
C17—C16	1.383 (7)	C14—H14B	0.9700
C17—H17A	0.9300	C13—H13A	0.9700
O2—C13	1.383 (8)	C13—H13B	0.9700
O2—C14	1.393 (9)	C5—H5A	0.9300

C12—N1—C15	108.6 (5)	C14—C15—H15A	110.1
C12—N1—C11	113.2 (4)	N1—C15—H15A	110.1
C15—N1—C11	111.4 (4)	C14—C15—H15B	110.1
C5—C4—C3	122.7 (7)	N1—C15—H15B	110.1
C5—C4—H4A	118.7	H15A—C15—H15B	108.4
C3—C4—H4A	118.7	C13—C12—N1	109.9 (5)
C1—C2—C3	116.8 (5)	C13—C12—H12A	109.7
C1—C2—C11	124.0 (5)	N1—C12—H12A	109.7
C3—C2—C11	119.2 (5)	C13—C12—H12B	109.7
C4—C3—C8	117.2 (5)	N1—C12—H12B	109.7
C4—C3—C2	123.0 (5)	H12A—C12—H12B	108.2
C8—C3—C2	119.8 (5)	C7—C8—C3	118.7 (6)
C1—O1—H1A	109.5	C7—C8—C9	123.5 (6)
C9—C10—C1	124.4 (6)	C3—C8—C9	117.7 (5)
C9—C10—H10A	117.8	C18—C19—C20	115.8 (6)
C1—C10—H10A	117.8	C18—C19—H19A	122.1
N1—C11—C2	110.0 (4)	C20—C19—H19A	122.1
N1—C11—C16	112.5 (4)	C19—C20—C21	122.3 (6)
C2—C11—C16	111.7 (4)	C19—C20—H20A	118.9
N1—C11—H11A	107.4	C21—C20—H20A	118.9
C2—C11—H11A	107.4	C10—C9—C8	119.2 (6)
C16—C11—H11A	107.4	C10—C9—H9A	120.4
C17—C18—C19	123.7 (6)	C8—C9—H9A	120.4
C17—C18—Cl1	118.7 (5)	C8—C7—C6	121.7 (7)
C19—C18—Cl1	117.5 (4)	C8—C7—H7A	119.2
C2—C1—O1	121.1 (6)	C6—C7—H7A	119.2
C2—C1—C10	122.0 (6)	O2—C14—C15	113.0 (7)
O1—C1—C10	116.8 (5)	O2—C14—H14A	109.0
C18—C17—C16	120.8 (6)	C15—C14—H14A	109.0
C18—C17—H17A	119.6	O2—C14—H14B	109.0
C16—C17—H17A	119.6	C15—C14—H14B	109.0
C13—O2—C14	108.4 (5)	H14A—C14—H14B	107.8
C21—C16—C17	117.4 (5)	O2—C13—C12	115.5 (5)
C21—C16—C11	121.2 (5)	O2—C13—H13A	108.4
C17—C16—C11	121.4 (5)	C12—C13—H13A	108.4
C16—C21—C20	119.9 (5)	O2—C13—H13B	108.4
C16—C21—H21A	120.0	C12—C13—H13B	108.4
C20—C21—H21A	120.0	H13A—C13—H13B	107.5
C5—C6—C7	117.7 (6)	C4—C5—C6	122.0 (7)
C5—C6—H6A	121.1	C4—C5—H5A	119.0
C7—C6—H6A	121.1	C6—C5—H5A	119.0
C14—C15—N1	108.2 (5)

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C3–C8 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N1	0.82	1.97	2.649 (6)	139
C21—H21A···Cgⁱ	0.93	2.87	3.770 (7)	164

Symmetry code: (i) x, −y+1, z−1/2.

Experimental details

Crystal data
Chemical formula	C₂₁H₂₀ClNO₂
M_r	353.83
Crystal system, space group	Monoclinic, Cc
Temperature (K)	298
a, b, c (Å)	14.1896 (18), 15.881 (2), 10.3998 (10)
β (°)	132.13 (2)
V (Å³)	1738.0 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.23
Crystal size (mm)	0.40 × 0.30 × 0.20

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.89, 1.00
No. of measured, independent and observed [I > 2σ(I)] reflections	7216, 3127, 2050
R_int	0.105
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.085, 0.240, 0.99
No. of reflections	3127
No. of parameters	226
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.29
Absolute structure	Flack (1983), 1551 Friedel pairs
Absolute structure parameter	0.07 (16)

Computer programs: CrystalClear (Rigaku, 2005), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C3–C8 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N1	0.82	1.97	2.649 (6)	139
C21—H21A···Cgⁱ	0.93	2.87	3.770 (7)	164

Symmetry code: (i) x, −y+1, z−1/2.

Acknowledgements

This work was supported by a start-up grant from Hangzhou Normal University, China.

References

Devi, I. & Bhuyan, P. J. (2004). Tetrahedron Lett. 45, 8625–8627. Web of Science CrossRef CAS Google Scholar
Domling, A. & Ugi, I. (2000). Angew. Chem. Int. Ed. 39, 3168–3210. CrossRef CAS Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Fu, D.-W., Ge, J.-Z., Dai, J., Ye, H.-Y. & Qu, Z.-R. (2009). Inorg. Chem. Commun. 12, 994-997. Web of Science CSD CrossRef CAS Google Scholar
Hulme, C. & Gore, V. (2003). Curr. Med. Chem. 10, 51–8. Web of Science CrossRef PubMed CAS Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Ugi, I. (1962). Angew. Chem. Int. Ed. Engl. 1, 8–21. CrossRef Google Scholar

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Volume 67| Part 7| July 2011| Page o1681

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