N-(4-Chloro­phen­yl)morpholine-4-carboxamide

Li, Y.-F.

doi:10.1107/S1600536811034611

organic compounds

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Volume 67| Part 9| September 2011| Page o2492

doi:10.1107/S1600536811034611

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N-(4-Chlorophenyl)morpholine-4-carboxamide

Yu-Feng Li ^a ^*

^aMicroscale Science Institute, Department of Chemistry and Chemical Engineering, Weifang University, Weifang 261061, People's Republic of China
^*Correspondence e-mail: liyufeng8111@163.com

(Received 7 August 2011; accepted 23 August 2011; online 27 August 2011)

In the title molecule, C₁₁H₁₃ClN₂O₂, the morpholine ring has a chair conformation. In the crystal, molecules are linked into chains along [100] by N—H⋯O hydrogen bonds.

Related literature

For the applications of morpholine compounds, see: Arrieta et al. (2007 ). For related structures, see: Li (2011a ,b ).

Experimental

Crystal data

C₁₁H₁₃ClN₂O₂
M_r = 240.68
Orthorhombic, P b c a
a = 9.3359 (19) Å
b = 11.105 (2) Å
c = 22.426 (5) Å
V = 2325.0 (8) Å³
Z = 8
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 293 K
0.26 × 0.19 × 0.18 mm

Data collection

Bruker SMART CCD diffractometer
20865 measured reflections
2660 independent reflections
2081 reflections with I > 2σ(I)
R_int = 0.059

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.124
S = 1.07
2660 reflections
149 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N⋯O2ⁱ	0.838 (19)	2.114 (19)	2.9226 (19)	162.2 (19)
Symmetry code: (i) $[x+{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811034611/lh5309sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811034611/lh5309Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811034611/lh5309Isup3.cml

checkCIF report

Comment top

Morpholine compounds are an important intermediate reagent in organic synthesis (Arrieta et al., 2007). As part of our search for new carboxamide compounds (Li, 2011a,b) we have determined the crystal structure of the title compound containing a morpholine ring. The molecular structure of the title compound is shown in Fig. 1. The morpholine ring (N1/C1/C2/C3/C4/O1) is in a chair conformation. In the crystal, molecules are linked into chains along [100] by N—H···O hydrogen bonds.

Related literature top

For the applications of morpholine compounds, see: Arrieta et al. (2007). For related structures, see: Li (2011a,b).

Experimental top

A mixture of morpholine (0.1 mol), and (4-chlorophenyl)carbamic chloride (0.1 mol) was stirred in refluxing ethanol (20 ml) for 4 h to afford the title compound (0.065 mol, yield 65%). Colourless blocks of the title compound were obtained by recrystallization from ethanol at room temperature.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound showing 30% probability displacement ellipsoids.

N-(4-Chlorophenyl)morpholine-4-carboxamide top

Crystal data top

C₁₁H₁₃ClN₂O₂	F(000) = 1008
M_r = 240.68	D_x = 1.375 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2081 reflections
a = 9.3359 (19) Å	θ = 2.6–27.4°
b = 11.105 (2) Å	µ = 0.32 mm⁻¹
c = 22.426 (5) Å	T = 293 K
V = 2325.0 (8) Å³	Block, colorless
Z = 8	0.26 × 0.19 × 0.18 mm

Data collection top

Bruker SMART CCD diffractometer	2081 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.059
Graphite monochromator	θ_max = 27.5°, θ_min = 3.0°
ϕ and ω scans	h = −11→12
20865 measured reflections	k = −14→14
2660 independent reflections	l = −29→29

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.124	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0583P)² + 0.5192P] where P = (F_o² + 2F_c²)/3
2660 reflections	(Δ/σ)_max < 0.001
149 parameters	Δρ_max = 0.40 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₁₁H₁₃ClN₂O₂	V = 2325.0 (8) Å³
M_r = 240.68	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 9.3359 (19) Å	µ = 0.32 mm⁻¹
b = 11.105 (2) Å	T = 293 K
c = 22.426 (5) Å	0.26 × 0.19 × 0.18 mm

Data collection top

Bruker SMART CCD diffractometer	2081 reflections with I > 2σ(I)
20865 measured reflections	R_int = 0.059
2660 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.124	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.40 e Å⁻³
2660 reflections	Δρ_min = −0.29 e Å⁻³
149 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
Cl1	0.12457 (6)	0.60377 (5)	0.44436 (2)	0.0656 (2)
O1	0.41840 (19)	0.16232 (19)	0.04233 (6)	0.0854 (6)
O2	0.14298 (12)	0.24548 (12)	0.21323 (5)	0.0505 (3)
N1	0.34301 (15)	0.19345 (14)	0.16222 (6)	0.0473 (4)
N2	0.35998 (15)	0.31812 (13)	0.24422 (6)	0.0407 (3)
C1	0.2740 (3)	0.1513 (3)	0.06064 (9)	0.0782 (7)
H1A	0.2252	0.0940	0.0351	0.094*
H1B	0.2264	0.2285	0.0567	0.094*
C2	0.2651 (2)	0.1097 (2)	0.12415 (8)	0.0598 (5)
H2B	0.1657	0.1058	0.1365	0.072*
H2C	0.3061	0.0298	0.1277	0.072*
C3	0.48960 (18)	0.21365 (17)	0.14282 (7)	0.0477 (4)
H3A	0.5456	0.1411	0.1489	0.057*
H3B	0.5322	0.2777	0.1663	0.057*
C4	0.4918 (2)	0.2472 (2)	0.07824 (9)	0.0695 (6)
H4A	0.4477	0.3257	0.0733	0.083*
H4B	0.5903	0.2531	0.0649	0.083*
C5	0.27454 (16)	0.25192 (14)	0.20668 (7)	0.0377 (3)
C6	0.30274 (16)	0.38724 (13)	0.29171 (7)	0.0370 (3)
C7	0.36139 (17)	0.37550 (15)	0.34817 (7)	0.0416 (4)
H7A	0.4372	0.3226	0.3545	0.050*
C8	0.30729 (19)	0.44249 (15)	0.39539 (7)	0.0452 (4)
H8A	0.3465	0.4350	0.4333	0.054*
C9	0.19474 (19)	0.52025 (14)	0.38526 (7)	0.0450 (4)
C10	0.13723 (18)	0.53487 (15)	0.32897 (8)	0.0459 (4)
H10A	0.0626	0.5888	0.3226	0.055*
C11	0.19215 (18)	0.46827 (14)	0.28228 (7)	0.0426 (4)
H11A	0.1546	0.4779	0.2442	0.051*
H1N	0.445 (2)	0.2955 (18)	0.2483 (9)	0.052 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0811 (4)	0.0609 (3)	0.0549 (3)	0.0125 (2)	0.0184 (2)	−0.0133 (2)
O1	0.0807 (11)	0.1309 (16)	0.0446 (7)	−0.0306 (11)	0.0110 (8)	−0.0221 (8)
O2	0.0341 (6)	0.0664 (8)	0.0511 (7)	−0.0016 (5)	0.0026 (5)	−0.0106 (5)
N1	0.0405 (7)	0.0582 (9)	0.0432 (7)	−0.0077 (6)	0.0057 (6)	−0.0150 (6)
N2	0.0347 (7)	0.0469 (8)	0.0404 (7)	0.0043 (6)	0.0000 (6)	−0.0087 (6)
C1	0.0687 (14)	0.115 (2)	0.0509 (12)	−0.0185 (14)	−0.0091 (11)	−0.0168 (12)
C2	0.0559 (11)	0.0712 (13)	0.0522 (10)	−0.0190 (9)	0.0065 (9)	−0.0229 (9)
C3	0.0364 (8)	0.0592 (10)	0.0475 (9)	0.0008 (7)	0.0050 (7)	−0.0114 (8)
C4	0.0668 (13)	0.0873 (16)	0.0543 (11)	−0.0210 (12)	0.0089 (11)	−0.0037 (10)
C5	0.0346 (8)	0.0410 (8)	0.0375 (8)	0.0013 (6)	0.0002 (6)	0.0008 (6)
C6	0.0376 (8)	0.0342 (8)	0.0391 (8)	−0.0014 (6)	0.0045 (6)	−0.0013 (6)
C7	0.0441 (9)	0.0378 (8)	0.0429 (9)	0.0044 (6)	−0.0011 (7)	−0.0006 (6)
C8	0.0537 (10)	0.0437 (9)	0.0383 (8)	−0.0004 (7)	0.0031 (7)	0.0000 (7)
C9	0.0537 (9)	0.0356 (8)	0.0457 (9)	−0.0019 (7)	0.0134 (8)	−0.0036 (6)
C10	0.0488 (9)	0.0354 (8)	0.0534 (10)	0.0062 (7)	0.0072 (8)	0.0019 (7)
C11	0.0475 (9)	0.0380 (8)	0.0422 (8)	0.0033 (7)	0.0007 (7)	0.0035 (6)

Geometric parameters (Å, º) top

Cl1—C9	1.7452 (16)	C3—C4	1.496 (3)
O1—C1	1.415 (3)	C3—H3A	0.9700
O1—C4	1.417 (3)	C3—H3B	0.9700
O2—C5	1.2390 (19)	C4—H4A	0.9700
N1—C5	1.351 (2)	C4—H4B	0.9700
N1—C3	1.453 (2)	C6—C7	1.385 (2)
N1—C2	1.457 (2)	C6—C11	1.386 (2)
N2—C5	1.373 (2)	C7—C8	1.389 (2)
N2—C6	1.4175 (19)	C7—H7A	0.9300
N2—H1N	0.84 (2)	C8—C9	1.379 (2)
C1—C2	1.499 (3)	C8—H8A	0.9300
C1—H1A	0.9700	C9—C10	1.381 (3)
C1—H1B	0.9700	C10—C11	1.381 (2)
C2—H2B	0.9700	C10—H10A	0.9300
C2—H2C	0.9700	C11—H11A	0.9300

C1—O1—C4	110.71 (16)	O1—C4—H4A	109.2
C5—N1—C3	126.33 (14)	C3—C4—H4A	109.2
C5—N1—C2	120.22 (14)	O1—C4—H4B	109.2
C3—N1—C2	113.14 (13)	C3—C4—H4B	109.2
C5—N2—C6	122.11 (14)	H4A—C4—H4B	107.9
C5—N2—H1N	117.2 (13)	O2—C5—N1	121.93 (14)
C6—N2—H1N	116.0 (13)	O2—C5—N2	122.28 (14)
O1—C1—C2	110.80 (19)	N1—C5—N2	115.78 (13)
O1—C1—H1A	109.5	C7—C6—C11	119.67 (15)
C2—C1—H1A	109.5	C7—C6—N2	119.12 (14)
O1—C1—H1B	109.5	C11—C6—N2	121.19 (14)
C2—C1—H1B	109.5	C6—C7—C8	120.16 (15)
H1A—C1—H1B	108.1	C6—C7—H7A	119.9
N1—C2—C1	109.42 (17)	C8—C7—H7A	119.9
N1—C2—H2B	109.8	C9—C8—C7	119.14 (16)
C1—C2—H2B	109.8	C9—C8—H8A	120.4
N1—C2—H2C	109.8	C7—C8—H8A	120.4
C1—C2—H2C	109.8	C8—C9—C10	121.34 (15)
H2B—C2—H2C	108.2	C8—C9—Cl1	119.59 (14)
N1—C3—C4	109.94 (15)	C10—C9—Cl1	119.06 (14)
N1—C3—H3A	109.7	C11—C10—C9	119.06 (16)
C4—C3—H3A	109.7	C11—C10—H10A	120.5
N1—C3—H3B	109.7	C9—C10—H10A	120.5
C4—C3—H3B	109.7	C10—C11—C6	120.59 (16)
H3A—C3—H3B	108.2	C10—C11—H11A	119.7
O1—C4—C3	112.21 (18)	C6—C11—H11A	119.7

C4—O1—C1—C2	−60.2 (3)	C6—N2—C5—N1	177.97 (15)
C5—N1—C2—C1	120.4 (2)	C5—N2—C6—C7	130.52 (17)
C3—N1—C2—C1	−53.6 (2)	C5—N2—C6—C11	−51.2 (2)
O1—C1—C2—N1	57.1 (3)	C11—C6—C7—C8	1.6 (2)
C5—N1—C3—C4	−121.82 (19)	N2—C6—C7—C8	179.86 (15)
C2—N1—C3—C4	51.7 (2)	C6—C7—C8—C9	0.1 (2)
C1—O1—C4—C3	58.8 (3)	C7—C8—C9—C10	−1.6 (3)
N1—C3—C4—O1	−53.6 (2)	C7—C8—C9—Cl1	179.34 (13)
C3—N1—C5—O2	166.36 (17)	C8—C9—C10—C11	1.3 (3)
C2—N1—C5—O2	−6.8 (3)	Cl1—C9—C10—C11	−179.61 (13)
C3—N1—C5—N2	−14.0 (2)	C9—C10—C11—C6	0.4 (3)
C2—N1—C5—N2	172.86 (16)	C7—C6—C11—C10	−1.8 (2)
C6—N2—C5—O2	−2.4 (2)	N2—C6—C11—C10	179.88 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N···O2ⁱ	0.838 (19)	2.114 (19)	2.9226 (19)	162.2 (19)

Symmetry code: (i) x+1/2, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₃ClN₂O₂
M_r	240.68
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	293
a, b, c (Å)	9.3359 (19), 11.105 (2), 22.426 (5)
V (Å³)	2325.0 (8)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.32
Crystal size (mm)	0.26 × 0.19 × 0.18

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	20865, 2660, 2081
R_int	0.059
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.124, 1.07
No. of reflections	2660
No. of parameters	149
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.29

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N···O2ⁱ	0.838 (19)	2.114 (19)	2.9226 (19)	162.2 (19)

Symmetry code: (i) x+1/2, y, −z+1/2.

References

Arrieta, A., Otaegui, D., Zubia, A., Cossío, F. P., Díaz-Ortiz, A., Hoz, A., Herrero, A., Prieto, P., Foces-Foces, C., Pizarro, J. L. & Arriortua, M. I. (2007). J. Org. Chem. 72, 4313–4322. Web of Science CSD CrossRef PubMed CAS Google Scholar
Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Li, Y.-F. (2011a). Acta Cryst. E67, o1796. Web of Science CSD CrossRef IUCr Journals Google Scholar
Li, Y.-F. (2011b). Acta Cryst. E67, o1792. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 9| September 2011| Page o2492

doi:10.1107/S1600536811034611

Open

access