Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801003282/na6051sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801003282/na6051Isup2.hkl |
CCDC reference: 159870
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (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
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
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
All H atoms were found on difference Fourier syntheses, calculated after four cycles of anistropic refinement. Their positionals parameters were free to refine.
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.
C9H18N2O2 | Dx = 1.189 Mg m−3 |
Mr = 186.25 | Melting point: 448.7 K |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 16.909 (3) Å | Cell parameters from 2228 reflections |
b = 6.525 (1) Å | θ = 5–22° |
c = 9.622 (2) Å | µ = 0.08 mm−1 |
β = 101.46 (3)° | T = 293 K |
V = 1040.4 (3) Å3 | Rectangular prism, colourless |
Z = 4 | 0.30 × 0.11 × 0.11 mm |
F(000) = 408 |
Kuma KM-4-CCD diffractometer | 1838 independent reflections |
Radiation source: fine-focus sealed tube | 1711 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.090 |
ω scans | θmax = 25.1°, θmin = 3.7° |
Absorption correction: numerical (X-RED; Stoe & Cie, 1999) | h = −20→20 |
Tmin = 0.975, Tmax = 0.991 | k = −7→7 |
10532 measured reflections | l = −9→11 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.065 | H 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 reflections | Δρmax = 0.19 e Å−3 |
173 parameters | Δρmin = −0.20 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.013 (5) |
C9H18N2O2 | V = 1040.4 (3) Å3 |
Mr = 186.25 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 16.909 (3) Å | µ = 0.08 mm−1 |
b = 6.525 (1) Å | T = 293 K |
c = 9.622 (2) Å | 0.30 × 0.11 × 0.11 mm |
β = 101.46 (3)° |
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 = 0.991 | Rint = 0.090 |
10532 measured reflections |
R[F2 > 2σ(F2)] = 0.065 | 0 restraints |
wR(F2) = 0.172 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.13 | Δρmax = 0.19 e Å−3 |
1838 reflections | Δρmin = −0.20 e Å−3 |
173 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
O2 | 0.23545 (9) | 0.6092 (2) | 0.38492 (15) | 0.0490 (5) | |
N2 | 0.22035 (10) | 0.8360 (3) | 0.20140 (19) | 0.0411 (5) | |
O1 | 0.44097 (10) | 0.3817 (3) | 0.1267 (2) | 0.0569 (5) | |
C5 | 0.25852 (12) | 0.6802 (3) | 0.2810 (2) | 0.0373 (5) | |
N1 | 0.32550 (11) | 0.6030 (3) | 0.2399 (2) | 0.0474 (5) | |
C1 | 0.37265 (14) | 0.7038 (4) | 0.1476 (3) | 0.0436 (6) | |
C2 | 0.39739 (15) | 0.5465 (4) | 0.0497 (3) | 0.0506 (6) | |
C6 | 0.14334 (12) | 0.9269 (4) | 0.2230 (2) | 0.0437 (6) | |
C3 | 0.39354 (17) | 0.2855 (4) | 0.2145 (3) | 0.0574 (7) | |
C4 | 0.36887 (18) | 0.4325 (4) | 0.3175 (3) | 0.0577 (7) | |
C7 | 0.12335 (19) | 1.0936 (5) | 0.1111 (3) | 0.0659 (8) | |
C8 | 0.15412 (18) | 1.0263 (5) | 0.3677 (3) | 0.0607 (7) | |
C9 | 0.07685 (17) | 0.7684 (5) | 0.2032 (4) | 0.0676 (8) | |
H2A | 0.3476 (15) | 0.495 (4) | −0.014 (2) | 0.050* | |
H4A | 0.4193 (15) | 0.485 (4) | 0.375 (3) | 0.050* | |
H2B | 0.4344 (15) | 0.603 (4) | −0.007 (3) | 0.050* | |
H1A | 0.3406 (15) | 0.809 (4) | 0.088 (3) | 0.050* | |
H8A | 0.1715 (15) | 0.941 (4) | 0.438 (3) | 0.050* | |
H2N | 0.2309 (15) | 0.853 (4) | 0.120 (3) | 0.050* | |
H8B | 0.1070 (16) | 1.086 (4) | 0.382 (3) | 0.050* | |
H3A | 0.4269 (16) | 0.184 (4) | 0.262 (3) | 0.050* | |
H3B | 0.3432 (16) | 0.230 (4) | 0.159 (3) | 0.050* | |
H1B | 0.4206 (16) | 0.761 (4) | 0.210 (3) | 0.050* | |
H7A | 0.1678 (16) | 1.199 (4) | 0.123 (3) | 0.050* | |
H4B | 0.3339 (15) | 0.363 (4) | 0.372 (3) | 0.050* | |
H7B | 0.1195 (15) | 1.033 (4) | 0.022 (3) | 0.050* | |
H7C | 0.0707 (16) | 1.151 (4) | 0.113 (3) | 0.050* | |
H9A | 0.0249 (16) | 0.830 (4) | 0.218 (3) | 0.050* | |
H8C | 0.2011 (16) | 1.133 (4) | 0.378 (3) | 0.050* | |
H9B | 0.0890 (15) | 0.654 (4) | 0.274 (3) | 0.050* | |
H9C | 0.0701 (15) | 0.719 (4) | 0.112 (3) | 0.050* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O2 | 0.0553 (10) | 0.0573 (10) | 0.0389 (8) | 0.0073 (7) | 0.0204 (7) | 0.0076 (7) |
N2 | 0.0420 (10) | 0.0494 (11) | 0.0349 (9) | 0.0102 (8) | 0.0150 (7) | 0.0051 (8) |
O1 | 0.0535 (10) | 0.0514 (10) | 0.0711 (11) | 0.0139 (8) | 0.0255 (8) | 0.0026 (8) |
C5 | 0.0410 (11) | 0.0397 (11) | 0.0330 (10) | 0.0012 (9) | 0.0115 (8) | −0.0045 (8) |
N1 | 0.0515 (11) | 0.0460 (11) | 0.0510 (11) | 0.0172 (8) | 0.0251 (9) | 0.0138 (8) |
C1 | 0.0402 (11) | 0.0432 (12) | 0.0503 (13) | 0.0045 (10) | 0.0163 (10) | 0.0066 (10) |
C2 | 0.0485 (13) | 0.0564 (14) | 0.0500 (13) | 0.0096 (11) | 0.0175 (11) | 0.0038 (11) |
C6 | 0.0373 (11) | 0.0532 (13) | 0.0424 (11) | 0.0092 (9) | 0.0123 (9) | 0.0022 (10) |
C3 | 0.0539 (14) | 0.0426 (13) | 0.0797 (18) | 0.0100 (11) | 0.0232 (13) | 0.0082 (12) |
C4 | 0.0639 (16) | 0.0554 (16) | 0.0581 (15) | 0.0196 (12) | 0.0225 (13) | 0.0178 (12) |
C7 | 0.0641 (17) | 0.078 (2) | 0.0596 (16) | 0.0289 (15) | 0.0225 (14) | 0.0191 (14) |
C8 | 0.0603 (16) | 0.0746 (19) | 0.0490 (14) | 0.0231 (15) | 0.0154 (12) | −0.0050 (13) |
C9 | 0.0454 (14) | 0.084 (2) | 0.0735 (19) | −0.0027 (14) | 0.0120 (13) | −0.0036 (17) |
O2—C5 | 1.233 (2) | N1—C1 | 1.462 (3) |
N2—C5 | 1.357 (3) | C1—C2 | 1.507 (3) |
N2—C6 | 1.483 (3) | C6—C9 | 1.511 (4) |
O1—C3 | 1.421 (3) | C6—C8 | 1.513 (3) |
O1—C2 | 1.425 (3) | C6—C7 | 1.521 (3) |
C5—N1 | 1.368 (3) | C3—C4 | 1.497 (4) |
N1—C4 | 1.455 (3) | ||
C5—N2—C6 | 123.56 (17) | O1—C2—C1 | 111.61 (19) |
C3—O1—C2 | 110.33 (18) | N2—C6—C9 | 111.1 (2) |
O2—C5—N2 | 123.19 (18) | N2—C6—C8 | 110.60 (19) |
O2—C5—N1 | 120.66 (19) | C9—C6—C8 | 111.1 (2) |
N2—C5—N1 | 116.15 (17) | N2—C6—C7 | 105.33 (18) |
C5—N1—C4 | 119.66 (19) | C9—C6—C7 | 110.2 (2) |
C5—N1—C1 | 126.37 (18) | C8—C6—C7 | 108.3 (2) |
C4—N1—C1 | 112.08 (19) | O1—C3—C4 | 112.0 (2) |
N1—C1—C2 | 109.0 (2) | N1—C4—C3 | 109.2 (2) |
N1—C1—C2—O1 | −56.4 (3) | N2—C5—N1—C1 | 18.4 (3) |
C1—C2—O1—C3 | 58.3 (3) | N2—C5—N1—C4 | −178.6 (2) |
C2—O1—C3—C4 | −58.6 (3) | N1—C5—N2—C6 | 174.9 (2) |
O1—C3—C4—N1 | 56.8 (3) | O2—C5—N2—C6 | −5.1 (3) |
C3—C4—N1—C1 | −55.6 (3) | C5—N2—C6—C7 | −179.8 (2) |
C4—N1—C1—C2 | 55.5 (3) | C5—N2—C6—C8 | 63.4 (3) |
O2—C5—N1—C4 | 1.4 (3) | C5—N2—C6—C9 | −60.5 (3) |
O2—C5—N1—C1 | −161.6 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N···O2i | 0.84 (3) | 2.29 (3) | 3.126 (2) | 170 (2) |
C1—H1A···O2i | 0.98 (3) | 2.43 (3) | 3.306 (3) | 149 (2) |
C2—H2B···O1ii | 0.98 (3) | 2.59 (3) | 3.523 (3) | 157.4 (18) |
C1—H1A···N2 | 0.98 (3) | 2.50 (2) | 2.859 (3) | 101.6 (17) |
C4—H4B···O2 | 0.98 (3) | 2.33 (2) | 2.724 (3) | 102.9 (17) |
C8—H8A···O2 | 0.88 (3) | 2.52 (3) | 3.039 (3) | 119 (2) |
C9—H9B···O2 | 1.01 (3) | 2.51 (3) | 3.077 (4) | 115.1 (17) |
Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) −x+1, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | C9H18N2O2 |
Mr | 186.25 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 16.909 (3), 6.525 (1), 9.622 (2) |
β (°) | 101.46 (3) |
V (Å3) | 1040.4 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.30 × 0.11 × 0.11 |
Data collection | |
Diffractometer | Kuma KM-4-CCD diffractometer |
Absorption correction | Numerical (X-RED; Stoe & Cie, 1999) |
Tmin, Tmax | 0.975, 0.991 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10532, 1838, 1711 |
Rint | 0.090 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.065, 0.172, 1.13 |
No. of reflections | 1838 |
No. of parameters | 173 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 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.
N1—C1—C2—O1 | −56.4 (3) | N2—C5—N1—C1 | 18.4 (3) |
C1—C2—O1—C3 | 58.3 (3) | N2—C5—N1—C4 | −178.6 (2) |
C2—O1—C3—C4 | −58.6 (3) | N1—C5—N2—C6 | 174.9 (2) |
O1—C3—C4—N1 | 56.8 (3) | O2—C5—N2—C6 | −5.1 (3) |
C3—C4—N1—C1 | −55.6 (3) | C5—N2—C6—C7 | −179.8 (2) |
C4—N1—C1—C2 | 55.5 (3) | C5—N2—C6—C8 | 63.4 (3) |
O2—C5—N1—C4 | 1.4 (3) | C5—N2—C6—C9 | −60.5 (3) |
O2—C5—N1—C1 | −161.6 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N···O2i | 0.84 (3) | 2.29 (3) | 3.126 (2) | 170 (2) |
C1—H1A···O2i | 0.98 (3) | 2.43 (3) | 3.306 (3) | 149 (2) |
C2—H2B···O1ii | 0.98 (3) | 2.59 (3) | 3.523 (3) | 157.4 (18) |
C1—H1A···N2 | 0.98 (3) | 2.50 (2) | 2.859 (3) | 101.6 (17) |
C4—H4B···O2 | 0.98 (3) | 2.33 (2) | 2.724 (3) | 102.9 (17) |
C8—H8A···O2 | 0.88 (3) | 2.52 (3) | 3.039 (3) | 119 (2) |
C9—H9B···O2 | 1.01 (3) | 2.51 (3) | 3.077 (4) | 115.1 (17) |
Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) −x+1, −y+1, −z. |
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).