3-Eth­oxy­methyl-1,4-dihydro­quinolin-4-one

Zaghary, W.A.; Al-Wabli, R.I.; Ng, S.W.

doi:10.1107/S1600536812028383

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 7| July 2012| Page o2234

https://doi.org/10.1107/S1600536812028383

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3-Ethoxymethyl-1,4-dihydroquinolin-4-one

Wafaa A. Zaghary,^a Reem I. Al-Wabli ^a and Seik Weng Ng ^b,^c ^*

^aDepartment of Pharmaceutical Chemistry, College of Pharmacy, King Saud University, Riyadh 11451, Saudi Arabia, ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and ^cChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 21 June 2012; accepted 22 June 2012; online 27 June 2012)

In the title molecule, C₁₂H₁₃NO₂, the dihydroquinolinone fused-ring system is nearly planar [maximum deviation = 0.012 (3) Å], and the mean plane passing through the extended ethoxymethyl substituent is aligned at 86.9 (2)° with respect to the fused-ring system. In the crystal, adjacent molecules are linked by an N—H⋯O_carbonyl hydrogen bond to generate a chain running along the b-axis direction.

Related literature

For the crystal structure of 1,4-dihydroquinolin-4-one, see: Nasiri et al. (2006 ).

Experimental

Crystal data

C₁₂H₁₃NO₂
M_r = 203.23
Orthorhombic, P n a 2₁
a = 18.179 (3) Å
b = 12.4052 (16) Å
c = 4.4529 (5) Å
V = 1004.2 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 100 K
0.35 × 0.05 × 0.03 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012 ) T_min = 0.969, T_max = 0.997
3157 measured reflections
1306 independent reflections
913 reflections with I > 2σ(I)
R_int = 0.068

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.116
S = 1.01
1306 reflections
140 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.98 (4)	1.78 (4)	2.707 (3)	157 (4)
Symmetry code: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812028383/xu5578sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812028383/xu5578Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812028383/xu5578Isup3.cml

checkCIF report

Comment top

The title compound was the unexpected product of the Mannich reaction involving 4-hydroxyquinoline, morpholine and paraformaldehyde in ethanol medium in an attempt to place the O(CH₂CH₂)N–CH₂– unit at the 3-position of 4-hydroxyquinoline. The compound was to have been radiolabeled with ⁹⁹^mTc for an imaging study. The ethyl group in the unexpected product (Scheme I) probably come from the ethanol solvent. The mean plane passing through the extended ethoxymethyl substituent is aligned at 86.9 (2) ° with respect to the mean plane passing through the dihydroquinoline fused-ring (Fig. 1). Adjacent molecules are linked by an N—H···O_carbonyl hydrogen bond to generate a chain running along the b-axis of the orthorhombic unit cell (Table 1).

Related literature top

For the crystal structure of 1,4-dihydroquinolin-4-one, see: Nasiri et al. (2006).

Experimental top

A mixture of paraformaldehyde (0.18 g, 0.002 mole) and morpholine (0.174 g, 0.002 mole) in alcohol (15 ml) was heated for 30 min. A solution of 4-quinolinol (0.29 g, 0.002 mole) in ethanol (5 ml) was added and the mixture was heated for 24 h. The solid that formed collected and purified by coloumn chromatography. Colorless crystals were obtained upon recrystallization from toluene/ethanol (9:1).

Structure description top

For the crystal structure of 1,4-dihydroquinolin-4-one, see: Nasiri et al. (2006).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of C₁₂H₁₃NO₂ at the 70% probability level; H atoms are drawn as spheres of arbitrary radius.
	Fig. 2. Hydrogen-bonded chain structure.

3-Ethoxymethyl-1,4-dihydroquinolin-4-one top

Crystal data top

C₁₂H₁₃NO₂	F(000) = 432
M_r = 203.23	D_x = 1.344 Mg m⁻³
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 568 reflections
a = 18.179 (3) Å	θ = 2.8–27.5°
b = 12.4052 (16) Å	µ = 0.09 mm⁻¹
c = 4.4529 (5) Å	T = 100 K
V = 1004.2 (2) Å³	Prism, colourless
Z = 4	0.35 × 0.05 × 0.03 mm

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	1306 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	913 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.068
Detector resolution: 10.4041 pixels mm^-1	θ_max = 27.5°, θ_min = 2.8°
ω scans	h = −23→19
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	k = −9→16
T_min = 0.969, T_max = 0.997	l = −5→4
3157 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.116	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ²(F_o²) + (0.0411P)²] where P = (F_o² + 2F_c²)/3
1306 reflections	(Δ/σ)_max = 0.001
140 parameters	Δρ_max = 0.24 e Å⁻³
1 restraint	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₁₂H₁₃NO₂	V = 1004.2 (2) Å³
M_r = 203.23	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 18.179 (3) Å	µ = 0.09 mm⁻¹
b = 12.4052 (16) Å	T = 100 K
c = 4.4529 (5) Å	0.35 × 0.05 × 0.03 mm

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	1306 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	913 reflections with I > 2σ(I)
T_min = 0.969, T_max = 0.997	R_int = 0.068
3157 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	1 restraint
wR(F²) = 0.116	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.24 e Å⁻³
1306 reflections	Δρ_min = −0.24 e Å⁻³
140 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.27733 (13)	0.81501 (17)	0.7508 (6)	0.0265 (6)
O2	0.09593 (14)	0.90044 (19)	0.8715 (5)	0.0280 (6)
N1	0.25633 (17)	1.1355 (2)	0.5678 (7)	0.0225 (7)
C1	0.3120 (2)	1.0792 (3)	0.4303 (7)	0.0197 (8)
C2	0.3589 (2)	1.1317 (3)	0.2279 (8)	0.0225 (8)
H2	0.3530	1.2064	0.1877	0.027*
C3	0.4137 (2)	1.0741 (3)	0.0880 (8)	0.0247 (9)
H3	0.4458	1.1096	−0.0481	0.030*
C4	0.4227 (2)	0.9630 (3)	0.1440 (7)	0.0242 (9)
H4	0.4602	0.9235	0.0441	0.029*
C5	0.3768 (2)	0.9127 (3)	0.3447 (8)	0.0237 (8)
H5	0.3836	0.8382	0.3852	0.028*
C6	0.3200 (2)	0.9685 (3)	0.4915 (7)	0.0197 (8)
C7	0.2704 (2)	0.9143 (2)	0.6992 (8)	0.0206 (8)
C8	0.2146 (2)	0.9797 (3)	0.8361 (7)	0.0216 (8)
C9	0.2103 (2)	1.0867 (3)	0.7638 (8)	0.0224 (8)
H9	0.1731	1.1290	0.8562	0.027*
C10	0.1592 (2)	0.9320 (3)	1.0447 (8)	0.0241 (8)
H10A	0.1803	0.8685	1.1481	0.029*
H10B	0.1448	0.9856	1.1986	0.029*
C11	0.0402 (2)	0.8545 (3)	1.0569 (10)	0.0352 (10)
H11A	0.0247	0.9072	1.2113	0.042*
H11B	0.0596	0.7898	1.1601	0.042*
C12	−0.0242 (2)	0.8243 (3)	0.8626 (10)	0.0373 (11)
H12A	−0.0630	0.7929	0.9877	0.056*
H12B	−0.0085	0.7715	0.7120	0.056*
H12C	−0.0431	0.8888	0.7616	0.056*
H1	0.245 (2)	1.209 (3)	0.503 (10)	0.055 (13)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0336 (16)	0.0153 (11)	0.0306 (13)	−0.0011 (11)	0.0012 (14)	0.0050 (12)
O2	0.0230 (15)	0.0297 (13)	0.0313 (14)	−0.0058 (11)	0.0033 (13)	0.0058 (12)
N1	0.0239 (18)	0.0165 (13)	0.0271 (16)	−0.0001 (13)	−0.0047 (15)	0.0019 (14)
C1	0.021 (2)	0.0180 (16)	0.0205 (17)	−0.0020 (16)	−0.0043 (15)	−0.0005 (15)
C2	0.025 (2)	0.0178 (15)	0.0246 (17)	−0.0028 (15)	−0.0051 (19)	0.0070 (17)
C3	0.024 (2)	0.0262 (18)	0.0240 (17)	−0.0048 (17)	−0.0032 (18)	0.0027 (17)
C4	0.021 (2)	0.0256 (19)	0.026 (2)	0.0002 (16)	−0.0016 (17)	−0.0012 (16)
C5	0.030 (2)	0.0197 (16)	0.0212 (17)	0.0015 (16)	−0.0048 (18)	0.0027 (17)
C6	0.024 (2)	0.0180 (16)	0.0174 (17)	−0.0051 (15)	−0.0062 (15)	0.0007 (15)
C7	0.020 (2)	0.0183 (15)	0.0230 (18)	−0.0038 (15)	−0.0057 (16)	0.0024 (17)
C8	0.025 (2)	0.0195 (16)	0.0206 (17)	−0.0024 (15)	−0.0062 (17)	0.0022 (16)
C9	0.024 (2)	0.0202 (16)	0.0225 (17)	0.0029 (15)	−0.0022 (18)	−0.0017 (17)
C10	0.027 (2)	0.0228 (17)	0.0222 (17)	0.0001 (16)	−0.0001 (18)	0.0001 (17)
C11	0.039 (3)	0.028 (2)	0.038 (2)	−0.0043 (19)	0.016 (2)	0.002 (2)
C12	0.025 (2)	0.033 (2)	0.054 (3)	−0.0017 (17)	0.013 (2)	0.006 (2)

Geometric parameters (Å, º) top

O1—C7	1.260 (4)	C5—H5	0.9500
O2—C11	1.425 (4)	C6—C7	1.456 (5)
O2—C10	1.439 (4)	C7—C8	1.434 (5)
N1—C9	1.352 (4)	C8—C9	1.369 (4)
N1—C1	1.373 (5)	C8—C10	1.494 (5)
N1—H1	0.98 (4)	C9—H9	0.9500
C1—C2	1.402 (5)	C10—H10A	0.9900
C1—C6	1.408 (4)	C10—H10B	0.9900
C2—C3	1.374 (5)	C11—C12	1.504 (6)
C2—H2	0.9500	C11—H11A	0.9900
C3—C4	1.410 (5)	C11—H11B	0.9900
C3—H3	0.9500	C12—H12A	0.9800
C4—C5	1.373 (5)	C12—H12B	0.9800
C4—H4	0.9500	C12—H12C	0.9800
C5—C6	1.404 (5)

C11—O2—C10	111.4 (3)	C9—C8—C7	119.3 (3)
C9—N1—C1	121.1 (3)	C9—C8—C10	119.5 (3)
C9—N1—H1	119 (3)	C7—C8—C10	121.2 (3)
C1—N1—H1	120 (3)	N1—C9—C8	123.4 (3)
N1—C1—C2	119.9 (3)	N1—C9—H9	118.3
N1—C1—C6	119.1 (3)	C8—C9—H9	118.3
C2—C1—C6	120.9 (3)	O2—C10—C8	108.3 (3)
C3—C2—C1	119.4 (3)	O2—C10—H10A	110.0
C3—C2—H2	120.3	C8—C10—H10A	110.0
C1—C2—H2	120.3	O2—C10—H10B	110.0
C2—C3—C4	120.8 (3)	C8—C10—H10B	110.0
C2—C3—H3	119.6	H10A—C10—H10B	108.4
C4—C3—H3	119.6	O2—C11—C12	108.6 (3)
C5—C4—C3	119.2 (3)	O2—C11—H11A	110.0
C5—C4—H4	120.4	C12—C11—H11A	110.0
C3—C4—H4	120.4	O2—C11—H11B	110.0
C4—C5—C6	121.7 (3)	C12—C11—H11B	110.0
C4—C5—H5	119.1	H11A—C11—H11B	108.3
C6—C5—H5	119.1	C11—C12—H12A	109.5
C5—C6—C1	117.9 (3)	C11—C12—H12B	109.5
C5—C6—C7	121.6 (3)	H12A—C12—H12B	109.5
C1—C6—C7	120.6 (3)	C11—C12—H12C	109.5
O1—C7—C8	123.1 (3)	H12A—C12—H12C	109.5
O1—C7—C6	120.4 (3)	H12B—C12—H12C	109.5
C8—C7—C6	116.5 (3)

C9—N1—C1—C2	180.0 (3)	C1—C6—C7—O1	179.2 (3)
C9—N1—C1—C6	1.2 (5)	C5—C6—C7—C8	179.9 (3)
N1—C1—C2—C3	−178.9 (3)	C1—C6—C7—C8	−0.6 (5)
C6—C1—C2—C3	−0.2 (5)	O1—C7—C8—C9	−179.0 (3)
C1—C2—C3—C4	0.5 (5)	C6—C7—C8—C9	0.8 (5)
C2—C3—C4—C5	−1.0 (5)	O1—C7—C8—C10	−1.9 (5)
C3—C4—C5—C6	1.3 (5)	C6—C7—C8—C10	177.9 (3)
C4—C5—C6—C1	−0.9 (5)	C1—N1—C9—C8	−1.0 (5)
C4—C5—C6—C7	178.6 (3)	C7—C8—C9—N1	−0.1 (5)
N1—C1—C6—C5	179.2 (3)	C10—C8—C9—N1	−177.2 (3)
C2—C1—C6—C5	0.4 (5)	C11—O2—C10—C8	−179.7 (3)
N1—C1—C6—C7	−0.4 (5)	C9—C8—C10—O2	85.7 (4)
C2—C1—C6—C7	−179.2 (3)	C7—C8—C10—O2	−91.5 (4)
C5—C6—C7—O1	−0.3 (5)	C10—O2—C11—C12	179.6 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.98 (4)	1.78 (4)	2.707 (3)	157 (4)

Symmetry code: (i) −x+1/2, y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₃NO₂
M_r	203.23
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	100
a, b, c (Å)	18.179 (3), 12.4052 (16), 4.4529 (5)
V (Å³)	1004.2 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.35 × 0.05 × 0.03

Data collection
Diffractometer	Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2012)
T_min, T_max	0.969, 0.997
No. of measured, independent and observed [I > 2σ(I)] reflections	3157, 1306, 913
R_int	0.068
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.116, 1.01
No. of reflections	1306
No. of parameters	140
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.24

Computer programs: CrysAlis PRO (Agilent, 2012), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.98 (4)	1.78 (4)	2.707 (3)	157 (4)

Symmetry code: (i) −x+1/2, y+1/2, z−1/2.

Acknowledgements

The authors thank the Research Center for Female Scientific and Medical Colleges, the Deanship of Scientific Research of King Saud University, and the Ministry of Higher Education of Malaysia (grant No. UM.C/HIR/MOHE/SC/12) for supporting this study.

References

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