N-Phenyl­morpholine-4-carboxamide

Meng, S.-M.; Wang, K.-W.; Xie, H.; Fan, Y.-Q.; Guo, Y.

doi:10.1107/S1600536810052207

organic compounds

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ISSN: 2056-9890

Volume 67| Part 1| January 2011| Page o225

https://doi.org/10.1107/S1600536810052207

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N-Phenylmorpholine-4-carboxamide

Shuang-Ming Meng,^a Ke-Wei Wang,^a Hai Xie,^a Yue-Qin Fan ^a and Yong Guo ^a ^*

^aCollege of Chemistry and Chemical Engineering, Shanxi Datong University, Datong 037009, People's Republic of China
^*Correspondence e-mail: ybsymsm@126.com

(Received 7 December 2010; accepted 13 December 2010; online 24 December 2010)

In the title compound, C₁₁H₁₄N₂O₂, the urea-type NC=ON moiety [planar to within 0.0002 (13) Å] is inclined to the phenyl ring by 42.88 (8) Å, and the morpholine ring has a chair conformation. In the crystal, intermolecular N—H⋯O hydrogen bonds link the molecules into infinite chains in [001].

Related literature

For amides as functional groups in biologically relevant molecules, see: Allen et al. (2010 ). For the synthesis of this and similar compounds, see: Montalbetti et al. (2005 ).

Experimental

Crystal data

C₁₁H₁₄N₂O₂
M_r = 206.24
Monoclinic, P 2₁ /c
a = 8.0907 (10) Å
b = 15.754 (2) Å
c = 8.4529 (11) Å
β = 104.205 (2)°
V = 1044.5 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.29 × 0.21 × 0.19 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.976, T_max = 0.981
5309 measured reflections
2056 independent reflections
1633 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.105
S = 1.04
2056 reflections
139 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1ⁱ	0.844 (17)	2.130 (18)	2.9543 (16)	165.3 (16)
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

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

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810052207/su2236sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810052207/su2236Isup2.hkl

checkCIF report

Comment top

Amides are one of the most important and prolific functional groups found in biologically relevant molecules (Allen et al., 2010), which lead to the synthesis of N-phenylmorpholine-4-carboxamide. In this study, this new acetamide derivative was prepared and its structure is presented herein.

In the title compound all the bond lengths and angles are within normal ranges. The molecule of the title compound is markedly non-planar (Fig. 1). The urea-type moiety [atoms N1,C7,O1,N2 - planar to within 0.0002 (13) Å] is inclined to the phenyl ring by 42.88 (8) Å. The morpholine ring has a chair conformation.

In the crystal, intermolecular N—H···O hydrogen bonds link the molecules into infinite one-dimensional chains propagagting in [001] (see Fig. 2 and Table 1).

Related literature top

For amides as functional groups in biologically relevant molecules, see: Allen et al. (2010). For the synthesis of this and similar compounds, see: Montalbetti et al. (2005).

Experimental top

The title compound was synthesized according to the literature procedure (Montalbetti et al., 2005). To a solution of isocyanatobenzene (1.19 g, 10 mmol) and morpholine (0.87 ml, 10 mmol) in CH₂Cl₂ (25 ml) was added triethylamine (1.20 ml, 10 mmol) in one portion. The reaction mixture was stirred at room temperature for 3 h, and then poured into ice-water (100 ml) under stirring. The combined organic phase was washed with water (3 × 20 ml), dried over MgSO₄, and filtered. Colourless single crystals were obtained by slow evaporation of the filtrate at room temperature.

Structure description top

In the crystal, intermolecular N—H···O hydrogen bonds link the molecules into infinite one-dimensional chains propagagting in [001] (see Fig. 2 and Table 1).

For amides as functional groups in biologically relevant molecules, see: Allen et al. (2010). For the synthesis of this and similar compounds, see: Montalbetti et al. (2005).

Computing details top

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

Figures top

	Fig. 1. Molecular structure of the title molecule. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. View along the b-axis of the one-dimensional polymeric chain of the title compound formed by hydrogen bonding (green dashed lines). H-atoms not involved in hydrogen bonding have been omitted for clarity.

N-Phenylmorpholine-4-carboxamide top

Crystal data top

C₁₁H₁₄N₂O₂	F(000) = 440
M_r = 206.24	D_x = 1.312 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5309 reflections
a = 8.0907 (10) Å	θ = 2.6–26.1°
b = 15.754 (2) Å	µ = 0.09 mm⁻¹
c = 8.4529 (11) Å	T = 293 K
β = 104.205 (2)°	Block, colourless
V = 1044.5 (2) Å³	0.29 × 0.21 × 0.19 mm
Z = 4

Data collection top

Bruker SMART APEX CCD diffractometer	2056 independent reflections
Radiation source: fine-focus sealed tube	1633 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
ω scans	θ_max = 26.1°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −8→9
T_min = 0.976, T_max = 0.981	k = −12→19
5309 measured reflections	l = −10→9

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.105	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.051P)² + 0.1766P] where P = (F_o² + 2F_c²)/3
2056 reflections	(Δ/σ)_max < 0.001
139 parameters	Δρ_max = 0.13 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₁₁H₁₄N₂O₂	V = 1044.5 (2) Å³
M_r = 206.24	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.0907 (10) Å	µ = 0.09 mm⁻¹
b = 15.754 (2) Å	T = 293 K
c = 8.4529 (11) Å	0.29 × 0.21 × 0.19 mm
β = 104.205 (2)°

Data collection top

Bruker SMART APEX CCD diffractometer	2056 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1633 reflections with I > 2σ(I)
T_min = 0.976, T_max = 0.981	R_int = 0.016
5309 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.105	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.13 e Å⁻³
2056 reflections	Δρ_min = −0.18 e Å⁻³
139 parameters

Special details top

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

	x	y	z	U_iso*/U_eq
C1	0.32831 (18)	0.27851 (9)	0.53510 (15)	0.0363 (3)
C6	0.21670 (19)	0.23577 (9)	0.60820 (17)	0.0423 (4)
H006	0.2379	0.1796	0.6410	0.051*
C2	0.2934 (2)	0.36162 (9)	0.48415 (18)	0.0446 (4)
H007	0.3679	0.3909	0.4358	0.054*
C7	0.56729 (17)	0.17667 (8)	0.59477 (16)	0.0354 (3)
C11	0.79490 (19)	0.07168 (10)	0.61799 (19)	0.0466 (4)
H00A	0.7747	0.0651	0.7258	0.056*
H00B	0.9098	0.0932	0.6306	0.056*
C5	0.0740 (2)	0.27684 (11)	0.6320 (2)	0.0533 (4)
H010	0.0011	0.2486	0.6838	0.064*
C9	0.6653 (2)	0.04917 (11)	0.2800 (2)	0.0532 (4)
H01A	0.5540	0.0256	0.2783	0.064*
H01B	0.6755	0.0528	0.1683	0.064*
C8	0.6786 (2)	0.13675 (10)	0.35298 (18)	0.0515 (4)
H01C	0.7849	0.1629	0.3450	0.062*
H01D	0.5854	0.1716	0.2929	0.062*
C10	0.7776 (2)	−0.01294 (10)	0.5331 (2)	0.0535 (4)
H01E	0.8650	−0.0511	0.5929	0.064*
H01F	0.6674	−0.0373	0.5327	0.064*
C4	0.0387 (2)	0.35911 (12)	0.5799 (2)	0.0633 (5)
H014	−0.0584	0.3862	0.5951	0.076*
C3	0.1479 (2)	0.40080 (11)	0.5054 (2)	0.0587 (5)
H015	0.1236	0.4561	0.4687	0.070*
N2	0.67253 (16)	0.13193 (8)	0.52338 (14)	0.0450 (3)
O1	0.55772 (13)	0.16176 (6)	0.73527 (11)	0.0438 (3)
O2	0.79327 (14)	−0.00542 (7)	0.36958 (15)	0.0565 (3)
N1	0.47270 (16)	0.23906 (8)	0.50123 (15)	0.0425 (3)
H1N	0.505 (2)	0.2590 (11)	0.421 (2)	0.051*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0432 (8)	0.0365 (7)	0.0307 (6)	0.0074 (6)	0.0117 (6)	−0.0014 (5)
C6	0.0503 (9)	0.0360 (7)	0.0430 (8)	0.0046 (6)	0.0162 (7)	0.0020 (6)
C2	0.0550 (9)	0.0384 (8)	0.0453 (8)	0.0065 (7)	0.0213 (7)	0.0050 (6)
C7	0.0396 (7)	0.0314 (7)	0.0375 (7)	0.0000 (6)	0.0135 (6)	−0.0023 (6)
C11	0.0415 (8)	0.0472 (9)	0.0516 (9)	0.0114 (7)	0.0123 (7)	0.0019 (7)
C5	0.0504 (9)	0.0546 (10)	0.0616 (10)	0.0050 (8)	0.0265 (8)	0.0052 (8)
C9	0.0503 (9)	0.0595 (10)	0.0538 (9)	0.0068 (8)	0.0202 (7)	−0.0086 (8)
C8	0.0658 (11)	0.0506 (9)	0.0463 (8)	0.0153 (8)	0.0293 (8)	0.0033 (7)
C10	0.0486 (9)	0.0437 (9)	0.0701 (11)	0.0086 (7)	0.0185 (8)	0.0023 (8)
C4	0.0603 (11)	0.0606 (11)	0.0781 (12)	0.0253 (9)	0.0347 (9)	0.0106 (9)
C3	0.0698 (11)	0.0421 (9)	0.0711 (11)	0.0222 (8)	0.0306 (9)	0.0134 (8)
N2	0.0531 (8)	0.0446 (7)	0.0417 (7)	0.0159 (6)	0.0199 (6)	0.0024 (5)
O1	0.0544 (6)	0.0438 (6)	0.0369 (5)	0.0098 (5)	0.0182 (5)	0.0034 (4)
O2	0.0538 (7)	0.0500 (7)	0.0693 (8)	0.0108 (5)	0.0220 (6)	−0.0118 (6)
N1	0.0525 (8)	0.0407 (7)	0.0411 (7)	0.0138 (6)	0.0245 (6)	0.0091 (5)

Geometric parameters (Å, º) top

C1—C2	1.386 (2)	C5—H010	0.9300
C1—C6	1.387 (2)	C9—O2	1.414 (2)
C1—N1	1.4132 (18)	C9—C8	1.504 (2)
C6—C5	1.380 (2)	C9—H01A	0.9700
C6—H006	0.9300	C9—H01B	0.9700
C2—C3	1.379 (2)	C8—N2	1.4553 (18)
C2—H007	0.9300	C8—H01C	0.9700
C7—O1	1.2315 (16)	C8—H01D	0.9700
C7—N2	1.3559 (18)	C10—O2	1.424 (2)
C7—N1	1.3711 (18)	C10—H01E	0.9700
C11—N2	1.4601 (18)	C10—H01F	0.9700
C11—C10	1.504 (2)	C4—C3	1.372 (2)
C11—H00A	0.9700	C4—H014	0.9300
C11—H00B	0.9700	C3—H015	0.9300
C5—C4	1.376 (2)	N1—H1N	0.844 (17)

C2—C1—C6	119.46 (13)	H01A—C9—H01B	108.0
C2—C1—N1	117.91 (13)	N2—C8—C9	109.95 (13)
C6—C1—N1	122.52 (12)	N2—C8—H01C	109.7
C5—C6—C1	119.76 (14)	C9—C8—H01C	109.7
C5—C6—H006	120.1	N2—C8—H01D	109.7
C1—C6—H006	120.1	C9—C8—H01D	109.7
C3—C2—C1	119.86 (15)	H01C—C8—H01D	108.2
C3—C2—H007	120.1	O2—C10—C11	111.67 (13)
C1—C2—H007	120.1	O2—C10—H01E	109.3
O1—C7—N2	121.67 (13)	C11—C10—H01E	109.3
O1—C7—N1	122.31 (12)	O2—C10—H01F	109.3
N2—C7—N1	116.02 (12)	C11—C10—H01F	109.3
N2—C11—C10	110.11 (13)	H01E—C10—H01F	107.9
N2—C11—H00A	109.6	C3—C4—C5	119.41 (15)
C10—C11—H00A	109.6	C3—C4—H014	120.3
N2—C11—H00B	109.6	C5—C4—H014	120.3
C10—C11—H00B	109.6	C4—C3—C2	120.78 (15)
H00A—C11—H00B	108.2	C4—C3—H015	119.6
C4—C5—C6	120.69 (15)	C2—C3—H015	119.6
C4—C5—H010	119.7	C7—N2—C8	126.22 (12)
C6—C5—H010	119.7	C7—N2—C11	120.64 (12)
O2—C9—C8	111.64 (14)	C8—N2—C11	113.14 (12)
O2—C9—H01A	109.3	C9—O2—C10	110.01 (11)
C8—C9—H01A	109.3	C7—N1—C1	124.79 (12)
O2—C9—H01B	109.3	C7—N1—H1N	119.4 (12)
C8—C9—H01B	109.3	C1—N1—H1N	115.7 (12)

C2—C1—C6—C5	−1.2 (2)	O1—C7—N2—C11	−8.0 (2)
N1—C1—C6—C5	−177.35 (13)	N1—C7—N2—C11	172.05 (13)
C6—C1—C2—C3	−0.5 (2)	C9—C8—N2—C7	−128.09 (16)
N1—C1—C2—C3	175.89 (14)	C9—C8—N2—C11	51.77 (18)
C1—C6—C5—C4	1.8 (2)	C10—C11—N2—C7	128.49 (15)
O2—C9—C8—N2	−55.97 (18)	C10—C11—N2—C8	−51.38 (18)
N2—C11—C10—O2	54.81 (17)	C8—C9—O2—C10	60.27 (17)
C6—C5—C4—C3	−0.8 (3)	C11—C10—O2—C9	−59.74 (17)
C5—C4—C3—C2	−0.9 (3)	O1—C7—N1—C1	−16.0 (2)
C1—C2—C3—C4	1.5 (3)	N2—C7—N1—C1	163.93 (13)
O1—C7—N2—C8	171.82 (14)	C2—C1—N1—C7	150.53 (14)
N1—C7—N2—C8	−8.1 (2)	C6—C1—N1—C7	−33.2 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱ	0.844 (17)	2.130 (18)	2.9543 (16)	165.3 (16)

Symmetry code: (i) x, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₄N₂O₂
M_r	206.24
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	8.0907 (10), 15.754 (2), 8.4529 (11)
β (°)	104.205 (2)
V (Å³)	1044.5 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.29 × 0.21 × 0.19

Data collection
Diffractometer	Bruker SMART APEX CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.976, 0.981
No. of measured, independent and observed [I > 2σ(I)] reflections	5309, 2056, 1633
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.618

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.105, 1.04
No. of reflections	2056
No. of parameters	139
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.13, −0.18

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL-Plus (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱ	0.844 (17)	2.130 (18)	2.9543 (16)	165.3 (16)

Symmetry code: (i) x, −y+1/2, z−1/2.

Acknowledgements

We thank the Natural Science Foundation of Shanxi (No. 2010011018) for support.

References

Allen, C. L., Burel, C. & Williams, J. M. J. (2010). Tetrahedron Lett. 20, 2724–2726. Web of Science CrossRef Google Scholar
Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Montalbetti, C. & Falque, V. (2005). Tetrahedron Lett. 61, 10827–10852. CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar