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The structure of the title compound, C9H18N2O2, has been determined. The morpholine ring exists in an almost ideal chair conformation. The central part of the mol­ecule is almost ideally planar. The mol­ecule is stabilized by weak C—H...N and C—H...O hydrogen bonds. Molecules of the title compound associate via N—H...O and C—H...O interactions to form a linear hydrogen-bonded chain along the z axis.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801003282/na6051sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801003282/na6051Isup2.hkl
Contains datablock I

CCDC reference: 159870

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.065
  • wR factor = 0.172
  • Data-to-parameter ratio = 10.6

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
PLAT_030 Alert C Refined Extinction parameter within range .... 2.60 Sigma
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check

Comment top

The transparent colourless crystals of the title compound, (I), become brown during the data collection. A reference crystal standing in the diffractometer box, but not in the X-ray beam, did not change colour.

A perspective view of the structure together with the atom-numbering scheme is shown in Fig. 1. A l l interatomic distances are normal. The morpholine ring exists in an almost ideal chair conformation, supported by the asymmetry parameters (Duax & Norton, 1975). The central part of the molecule consisting of atoms N1, C5, N2, C6 and O2 is almost ideally planar. For the least-squares plane calculated through atoms N1, C5, N2 and C6, the maximum deviation of 0.0316 (12) Å occurs for N1 and for the least-squares plane calculated through atoms N1, C5, N2, C6 and O2, the maximum deviation of 0.0413 (15) Å occurs for the same atom. The molecule has additional stabilization provided by intramolecular weak hydrogen bonds, viz. C1—H1A···N2 and C4—H4B···O2. These hydrogen bonds also explain the orientation of the morpholinyl substituent in relation to the urea chain, as shown by the torsion angles (Table 1).

Molecules of the title compound associate via N—H···O and C—H···O interactions to form a linear hydrogen-bonded chain along the z axis (Fig. 2).

Experimental top

Morpholine (2 mmol, 0.174 g) and tert-butyl isocyanate (2.4 mmol, 0.24 g) were dissolved in 20 ml of dry benzene (distilled over CaH2) and stirred at room temperature for 24 h. Benzene was distilled off under reduced pressure leaving 0.369 g (99.2% theoretical yield) of colorless crystalline solid. Recrystallization from benzene yielded C(CH3)3NHC(O)[N(CH2CH2)2O] in the form of colourless well shaped crystals (m.p. 448.7 K) (acc. to the Differential Scanning Calorimetry curve). 1H NMR (in CDCl3, chemical shifts in p.p..m): δ[NH(CO)] 7.26 (s, 2H), δ(OCH2CH2N) 3.68–3.71, δ[NH(CO)NCH2CH2O] 3.27–3.30 (t, 4H), δ(C—CH3) 1.35 (s, 9H). IR (in KBr pellet, wavenumber in cm-1): 2858, 2973 (CH3); 1622, 1535, 3358 [NHC(O)]; 1359, 1402 [C(CH3)3]; 1002, 1027, 1109, 1220, 1270 (NCH2 and OCH2). UV (in CH3OH solution): λmax = 226 nm

Refinement top

All H atoms were found on difference Fourier syntheses, calculated after four cycles of anistropic refinement. Their positionals parameters were free to refine.

Computing details top

Data collection: Kuma KM-4-CCD software; cell refinement: Kuma KM-4-CCD software; data reduction: Kuma KM-4-CCD software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL/PC (Sheldrick, 1990) and ORTEP-3 (Farrugia 1997); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. Asymmetry parameters (Duax & Norton, 1975) for (I).
[Figure 3] Fig. 3. A view along the z axis of part of the crystal structure of the title compound showing intermolecular hydrogen bonds creating the chain structure. Hydrogen bonds are indicated by dashed lines.
N-tert-Butylmorpholine-4-carboxamide top
Crystal data top
C9H18N2O2Dx = 1.189 Mg m3
Mr = 186.25Melting point: 448.7 K
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 16.909 (3) ÅCell parameters from 2228 reflections
b = 6.525 (1) Åθ = 5–22°
c = 9.622 (2) ŵ = 0.08 mm1
β = 101.46 (3)°T = 293 K
V = 1040.4 (3) Å3Rectangular prism, colourless
Z = 40.30 × 0.11 × 0.11 mm
F(000) = 408
Data collection top
Kuma KM-4-CCD
diffractometer
1838 independent reflections
Radiation source: fine-focus sealed tube1711 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.090
ω scansθmax = 25.1°, θmin = 3.7°
Absorption correction: numerical
(X-RED; Stoe & Cie, 1999)
h = 2020
Tmin = 0.975, Tmax = 0.991k = 77
10532 measured reflectionsl = 911
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.065H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.172 w = 1/[σ2(Fo2) + (0.1123P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.13(Δ/σ)max = 0.003
1838 reflectionsΔρmax = 0.19 e Å3
173 parametersΔρmin = 0.20 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.013 (5)
Crystal data top
C9H18N2O2V = 1040.4 (3) Å3
Mr = 186.25Z = 4
Monoclinic, P21/cMo Kα radiation
a = 16.909 (3) ŵ = 0.08 mm1
b = 6.525 (1) ÅT = 293 K
c = 9.622 (2) Å0.30 × 0.11 × 0.11 mm
β = 101.46 (3)°
Data collection top
Kuma KM-4-CCD
diffractometer
1838 independent reflections
Absorption correction: numerical
(X-RED; Stoe & Cie, 1999)
1711 reflections with I > 2σ(I)
Tmin = 0.975, Tmax = 0.991Rint = 0.090
10532 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0650 restraints
wR(F2) = 0.172H atoms treated by a mixture of independent and constrained refinement
S = 1.13Δρmax = 0.19 e Å3
1838 reflectionsΔρmin = 0.20 e Å3
173 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
xyzUiso*/Ueq
O20.23545 (9)0.6092 (2)0.38492 (15)0.0490 (5)
N20.22035 (10)0.8360 (3)0.20140 (19)0.0411 (5)
O10.44097 (10)0.3817 (3)0.1267 (2)0.0569 (5)
C50.25852 (12)0.6802 (3)0.2810 (2)0.0373 (5)
N10.32550 (11)0.6030 (3)0.2399 (2)0.0474 (5)
C10.37265 (14)0.7038 (4)0.1476 (3)0.0436 (6)
C20.39739 (15)0.5465 (4)0.0497 (3)0.0506 (6)
C60.14334 (12)0.9269 (4)0.2230 (2)0.0437 (6)
C30.39354 (17)0.2855 (4)0.2145 (3)0.0574 (7)
C40.36887 (18)0.4325 (4)0.3175 (3)0.0577 (7)
C70.12335 (19)1.0936 (5)0.1111 (3)0.0659 (8)
C80.15412 (18)1.0263 (5)0.3677 (3)0.0607 (7)
C90.07685 (17)0.7684 (5)0.2032 (4)0.0676 (8)
H2A0.3476 (15)0.495 (4)0.014 (2)0.050*
H4A0.4193 (15)0.485 (4)0.375 (3)0.050*
H2B0.4344 (15)0.603 (4)0.007 (3)0.050*
H1A0.3406 (15)0.809 (4)0.088 (3)0.050*
H8A0.1715 (15)0.941 (4)0.438 (3)0.050*
H2N0.2309 (15)0.853 (4)0.120 (3)0.050*
H8B0.1070 (16)1.086 (4)0.382 (3)0.050*
H3A0.4269 (16)0.184 (4)0.262 (3)0.050*
H3B0.3432 (16)0.230 (4)0.159 (3)0.050*
H1B0.4206 (16)0.761 (4)0.210 (3)0.050*
H7A0.1678 (16)1.199 (4)0.123 (3)0.050*
H4B0.3339 (15)0.363 (4)0.372 (3)0.050*
H7B0.1195 (15)1.033 (4)0.022 (3)0.050*
H7C0.0707 (16)1.151 (4)0.113 (3)0.050*
H9A0.0249 (16)0.830 (4)0.218 (3)0.050*
H8C0.2011 (16)1.133 (4)0.378 (3)0.050*
H9B0.0890 (15)0.654 (4)0.274 (3)0.050*
H9C0.0701 (15)0.719 (4)0.112 (3)0.050*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O20.0553 (10)0.0573 (10)0.0389 (8)0.0073 (7)0.0204 (7)0.0076 (7)
N20.0420 (10)0.0494 (11)0.0349 (9)0.0102 (8)0.0150 (7)0.0051 (8)
O10.0535 (10)0.0514 (10)0.0711 (11)0.0139 (8)0.0255 (8)0.0026 (8)
C50.0410 (11)0.0397 (11)0.0330 (10)0.0012 (9)0.0115 (8)0.0045 (8)
N10.0515 (11)0.0460 (11)0.0510 (11)0.0172 (8)0.0251 (9)0.0138 (8)
C10.0402 (11)0.0432 (12)0.0503 (13)0.0045 (10)0.0163 (10)0.0066 (10)
C20.0485 (13)0.0564 (14)0.0500 (13)0.0096 (11)0.0175 (11)0.0038 (11)
C60.0373 (11)0.0532 (13)0.0424 (11)0.0092 (9)0.0123 (9)0.0022 (10)
C30.0539 (14)0.0426 (13)0.0797 (18)0.0100 (11)0.0232 (13)0.0082 (12)
C40.0639 (16)0.0554 (16)0.0581 (15)0.0196 (12)0.0225 (13)0.0178 (12)
C70.0641 (17)0.078 (2)0.0596 (16)0.0289 (15)0.0225 (14)0.0191 (14)
C80.0603 (16)0.0746 (19)0.0490 (14)0.0231 (15)0.0154 (12)0.0050 (13)
C90.0454 (14)0.084 (2)0.0735 (19)0.0027 (14)0.0120 (13)0.0036 (17)
Geometric parameters (Å, º) top
O2—C51.233 (2)N1—C11.462 (3)
N2—C51.357 (3)C1—C21.507 (3)
N2—C61.483 (3)C6—C91.511 (4)
O1—C31.421 (3)C6—C81.513 (3)
O1—C21.425 (3)C6—C71.521 (3)
C5—N11.368 (3)C3—C41.497 (4)
N1—C41.455 (3)
C5—N2—C6123.56 (17)O1—C2—C1111.61 (19)
C3—O1—C2110.33 (18)N2—C6—C9111.1 (2)
O2—C5—N2123.19 (18)N2—C6—C8110.60 (19)
O2—C5—N1120.66 (19)C9—C6—C8111.1 (2)
N2—C5—N1116.15 (17)N2—C6—C7105.33 (18)
C5—N1—C4119.66 (19)C9—C6—C7110.2 (2)
C5—N1—C1126.37 (18)C8—C6—C7108.3 (2)
C4—N1—C1112.08 (19)O1—C3—C4112.0 (2)
N1—C1—C2109.0 (2)N1—C4—C3109.2 (2)
N1—C1—C2—O156.4 (3)N2—C5—N1—C118.4 (3)
C1—C2—O1—C358.3 (3)N2—C5—N1—C4178.6 (2)
C2—O1—C3—C458.6 (3)N1—C5—N2—C6174.9 (2)
O1—C3—C4—N156.8 (3)O2—C5—N2—C65.1 (3)
C3—C4—N1—C155.6 (3)C5—N2—C6—C7179.8 (2)
C4—N1—C1—C255.5 (3)C5—N2—C6—C863.4 (3)
O2—C5—N1—C41.4 (3)C5—N2—C6—C960.5 (3)
O2—C5—N1—C1161.6 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2N···O2i0.84 (3)2.29 (3)3.126 (2)170 (2)
C1—H1A···O2i0.98 (3)2.43 (3)3.306 (3)149 (2)
C2—H2B···O1ii0.98 (3)2.59 (3)3.523 (3)157.4 (18)
C1—H1A···N20.98 (3)2.50 (2)2.859 (3)101.6 (17)
C4—H4B···O20.98 (3)2.33 (2)2.724 (3)102.9 (17)
C8—H8A···O20.88 (3)2.52 (3)3.039 (3)119 (2)
C9—H9B···O21.01 (3)2.51 (3)3.077 (4)115.1 (17)
Symmetry codes: (i) x, y+3/2, z1/2; (ii) x+1, y+1, z.

Experimental details

Crystal data
Chemical formulaC9H18N2O2
Mr186.25
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)16.909 (3), 6.525 (1), 9.622 (2)
β (°) 101.46 (3)
V3)1040.4 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.08
Crystal size (mm)0.30 × 0.11 × 0.11
Data collection
DiffractometerKuma KM-4-CCD
diffractometer
Absorption correctionNumerical
(X-RED; Stoe & Cie, 1999)
Tmin, Tmax0.975, 0.991
No. of measured, independent and
observed [I > 2σ(I)] reflections
10532, 1838, 1711
Rint0.090
(sin θ/λ)max1)0.596
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.065, 0.172, 1.13
No. of reflections1838
No. of parameters173
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.19, 0.20

Computer programs: Kuma KM-4-CCD software, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP in SHELXTL/PC (Sheldrick, 1990) and ORTEP-3 (Farrugia 1997), SHELXL97.

Selected torsion angles (º) top
N1—C1—C2—O156.4 (3)N2—C5—N1—C118.4 (3)
C1—C2—O1—C358.3 (3)N2—C5—N1—C4178.6 (2)
C2—O1—C3—C458.6 (3)N1—C5—N2—C6174.9 (2)
O1—C3—C4—N156.8 (3)O2—C5—N2—C65.1 (3)
C3—C4—N1—C155.6 (3)C5—N2—C6—C7179.8 (2)
C4—N1—C1—C255.5 (3)C5—N2—C6—C863.4 (3)
O2—C5—N1—C41.4 (3)C5—N2—C6—C960.5 (3)
O2—C5—N1—C1161.6 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2N···O2i0.84 (3)2.29 (3)3.126 (2)170 (2)
C1—H1A···O2i0.98 (3)2.43 (3)3.306 (3)149 (2)
C2—H2B···O1ii0.98 (3)2.59 (3)3.523 (3)157.4 (18)
C1—H1A···N20.98 (3)2.50 (2)2.859 (3)101.6 (17)
C4—H4B···O20.98 (3)2.33 (2)2.724 (3)102.9 (17)
C8—H8A···O20.88 (3)2.52 (3)3.039 (3)119 (2)
C9—H9B···O21.01 (3)2.51 (3)3.077 (4)115.1 (17)
Symmetry codes: (i) x, y+3/2, z1/2; (ii) x+1, y+1, z.
 

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