Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807043656/wn2203sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807043656/wn2203Isup2.hkl |
CCDC reference: 663750
Key indicators
- Single-crystal X-ray study
- T = 183 K
- Mean (C-C)= 0.002 Å
- R factor = 0.044
- wR factor = 0.108
- Data-to-parameter ratio = 20.2
checkCIF/PLATON results
No syntax errors found No errors found in this datablock
1.96 g Dicyclohexylcarbodiimide (9.51 mmol) were stirred at room temperature for 5 h together with 5 ml glacial acetic acid and 1 mol% (110 mg) [Pd(PPh3)4] in 10 ml THF. On standing at -20° for three days, colorless crystals of the title compound were produced; these were identified by their melting point and 1H NMR spectrum (Ogawa et al. 1990, Smart et al. 1960). 13C NMR (CDCl3, 293 K) [p.p.m.]: 23.9 (CH3), 24.6 (CH2), 25.2 (CH2), 25.4 (CH2), 26.2 (CH2), 30.7 (CH2), 32.6 (CH2), 55.6 (CH), 56,4 (CH), 153.9 (C=O), 170.9 (C=O).
Hydrogen atoms were placed in idealized positions and refined using a riding model, with distances of N—H = 0.88 Å and C—H = 0.98–1.00 Å; Uiso(H) = 1.5Ueq(C,N).
Acylated N-aryl- and N-alkylurea derivatives have been investigated, e.g. as intermediates in the synthesis of amidines and heterocyclic compounds derived therefrom, as well as precursors for poly(amide-imide)s (Wei et al. 2006, Ramsden & Rose 1997, Khorana 1953, Smith et al. 1958, Detar & Silverstein 1966a,b, Ogawa et al. 1990, Smart et al. 1960). Although quite a number of acylated dicyclohexylurea derivatives have been structurally characterized (Ball et al. 1990, Banerjee et al. 2000, Bechtel et al. 1979, Behrens & Rehder 2006, Chérioux et al. 2002, Orea Flores et al. 2006, Gallagher et al. 1999, Goel et al. 2003, Ishida et al. 1983, Mazumdar et al. 2003, Perollier et al. 1999, Salas-Coronado et al. 2001, Toniolo et al. 1990), the structure of the most simple derivative, with an acetyl group, has not yet been reported.
The molecular structure of the title compound (Fig. 1) shows the two urea nitrogen atoms N1 and N2 having a planar geometry, with an angle of 69.00 (6)° between [C6, N1, H1N, C7] and [C7, N2, C8, C14]. The bond lengths and angles have expected values. The crystal structure is determined by hydrogen bonds. The strongest interactions are observed between the amide N1—H1N group and the acetyl oxygen atom (H···O 2.035 Å). Two of these hydrogen bonds link two molecules, forming a dimeric cyclic unit. These dimers are linked to produce infinite chains by additional C—H···O bonds from one of the cyclohexyl substituents to the carbonyl oxygen atom of the urea unit (Fig. 2, Table 1).
For related literature, see: Ball et al. (1990); Banerjee et al. (2000); Bechtel et al. (1979); Behrens & Rehder (2006); Chérioux et al. (2002); Orea Flores et al. (2006); Gallagher et al. (1999); Goel et al. (2003); Ishida et al. (1983); Mazumdar et al. (2003); Perollier et al. (1999); Salas-Coronado et al. (2001); Toniolo et al. (1990).
For related literature, see: Detar & Silverstein (1966a, 1966b); Khorana (1953); Ogawa et al. (1990); Ramsden & Rose (1997); Smart et al. (1960); Smith et al. (1958); Wei et al. (2006).
Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1990); software used to prepare material for publication: XP (Siemens, 1990).
C15H26N2O2 | F(000) = 584 |
Mr = 266.38 | Dx = 1.157 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P2yn | Cell parameters from 5982 reflections |
a = 10.6174 (4) Å | θ = 2.5–27.5° |
b = 14.2451 (9) Å | µ = 0.08 mm−1 |
c = 10.8862 (6) Å | T = 183 K |
β = 111.795 (3)° | Cuboid, colourless |
V = 1528.80 (14) Å3 | 0.3 × 0.2 × 0.2 mm |
Z = 4 |
Nonius KappaCCD diffractometer | 2103 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.030 |
Graphite monochromator | θmax = 27.5°, θmin = 2.5° |
phi–scan, ω–scan | h = −13→13 |
5982 measured reflections | k = −16→18 |
3494 independent reflections | l = −14→14 |
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) = 0.108 | H-atom parameters constrained |
S = 0.95 | w = 1/[σ2(Fo2) + (0.0565P)2] where P = (Fo2 + 2Fc2)/3 |
3494 reflections | (Δ/σ)max < 0.001 |
173 parameters | Δρmax = 0.17 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
C15H26N2O2 | V = 1528.80 (14) Å3 |
Mr = 266.38 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.6174 (4) Å | µ = 0.08 mm−1 |
b = 14.2451 (9) Å | T = 183 K |
c = 10.8862 (6) Å | 0.3 × 0.2 × 0.2 mm |
β = 111.795 (3)° |
Nonius KappaCCD diffractometer | 2103 reflections with I > 2σ(I) |
5982 measured reflections | Rint = 0.030 |
3494 independent reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.108 | H-atom parameters constrained |
S = 0.95 | Δρmax = 0.17 e Å−3 |
3494 reflections | Δρmin = −0.18 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 | ||
C1 | 0.06204 (15) | 0.63488 (12) | 0.96118 (14) | 0.0552 (4) | |
H1A | 0.1613 | 0.6441 | 0.9905 | 0.083* | |
H1B | 0.0443 | 0.5666 | 0.9597 | 0.083* | |
C2 | 0.01037 (16) | 0.68244 (14) | 1.05960 (14) | 0.0639 (5) | |
H2A | 0.0525 | 0.6522 | 1.1473 | 0.096* | |
H2B | 0.0376 | 0.7493 | 1.0690 | 0.096* | |
C3 | −0.14216 (16) | 0.67575 (12) | 1.01465 (16) | 0.0576 (4) | |
H3A | −0.1688 | 0.6092 | 1.0153 | 0.086* | |
H3B | −0.1730 | 0.7108 | 1.0769 | 0.086* | |
C4 | −0.20999 (14) | 0.71539 (13) | 0.87715 (14) | 0.0584 (4) | |
H4A | −0.1919 | 0.7837 | 0.8789 | 0.088* | |
H4B | −0.3093 | 0.7064 | 0.8478 | 0.088* | |
C5 | −0.15866 (13) | 0.66796 (12) | 0.77887 (14) | 0.0571 (4) | |
H5A | −0.1864 | 0.6012 | 0.7692 | 0.086* | |
H5B | −0.2006 | 0.6984 | 0.6913 | 0.086* | |
C6 | −0.00597 (12) | 0.67416 (9) | 0.82379 (12) | 0.0348 (3) | |
H6 | 0.0198 | 0.7418 | 0.8251 | 0.052* | |
N1 | 0.03787 (10) | 0.62479 (8) | 0.72894 (10) | 0.0384 (3) | |
H1N | −0.0132 | 0.5789 | 0.6825 | 0.058* | |
C7 | 0.15079 (12) | 0.64555 (9) | 0.70914 (12) | 0.0350 (3) | |
O1 | 0.23242 (9) | 0.70596 (7) | 0.76652 (9) | 0.0460 (3) | |
N2 | 0.17255 (10) | 0.58545 (7) | 0.61161 (10) | 0.0348 (3) | |
C8 | 0.28978 (12) | 0.52058 (9) | 0.65772 (12) | 0.0345 (3) | |
H8 | 0.2645 | 0.4638 | 0.5997 | 0.052* | |
C9 | 0.41480 (12) | 0.56302 (10) | 0.64319 (14) | 0.0420 (3) | |
H9A | 0.4454 | 0.6183 | 0.7020 | 0.063* | |
H9B | 0.3927 | 0.5840 | 0.5508 | 0.063* | |
C10 | 0.52742 (14) | 0.48970 (11) | 0.67961 (15) | 0.0526 (4) | |
H10A | 0.4983 | 0.4363 | 0.6173 | 0.079* | |
H10B | 0.6095 | 0.5176 | 0.6717 | 0.079* | |
C11 | 0.56119 (15) | 0.45453 (11) | 0.82013 (16) | 0.0591 (4) | |
H11A | 0.6302 | 0.4043 | 0.8395 | 0.089* | |
H11B | 0.6001 | 0.5066 | 0.8831 | 0.089* | |
C12 | 0.43630 (15) | 0.41690 (10) | 0.83923 (15) | 0.0526 (4) | |
H12A | 0.4601 | 0.4000 | 0.9334 | 0.079* | |
H12B | 0.4056 | 0.3591 | 0.7859 | 0.079* | |
C13 | 0.32072 (14) | 0.48780 (10) | 0.79900 (13) | 0.0434 (3) | |
H13A | 0.3463 | 0.5423 | 0.8597 | 0.065* | |
H13B | 0.2388 | 0.4586 | 0.8056 | 0.065* | |
C14 | 0.09682 (12) | 0.59270 (9) | 0.47971 (13) | 0.0363 (3) | |
O2 | 0.11724 (8) | 0.53978 (7) | 0.39946 (9) | 0.0435 (3) | |
C15 | −0.00869 (13) | 0.66818 (10) | 0.43522 (13) | 0.0449 (4) | |
H15A | −0.0302 | 0.6815 | 0.3413 | 0.067* | |
H15B | 0.0259 | 0.7252 | 0.4871 | 0.067* | |
H15C | −0.0908 | 0.6472 | 0.4481 | 0.067* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0564 (9) | 0.0703 (11) | 0.0422 (8) | 0.0220 (8) | 0.0222 (7) | 0.0044 (8) |
C2 | 0.0658 (10) | 0.0937 (14) | 0.0366 (8) | 0.0233 (9) | 0.0240 (7) | 0.0030 (9) |
C3 | 0.0711 (10) | 0.0585 (10) | 0.0630 (10) | −0.0031 (8) | 0.0478 (8) | −0.0074 (8) |
C4 | 0.0411 (8) | 0.0827 (12) | 0.0558 (10) | 0.0064 (8) | 0.0230 (7) | −0.0156 (9) |
C5 | 0.0386 (8) | 0.0856 (12) | 0.0474 (9) | 0.0047 (8) | 0.0163 (6) | −0.0181 (9) |
C6 | 0.0381 (7) | 0.0349 (7) | 0.0358 (7) | −0.0018 (5) | 0.0188 (5) | −0.0058 (6) |
N1 | 0.0375 (6) | 0.0437 (7) | 0.0386 (6) | −0.0075 (5) | 0.0193 (5) | −0.0128 (5) |
C7 | 0.0366 (7) | 0.0369 (7) | 0.0336 (7) | 0.0010 (6) | 0.0154 (6) | −0.0016 (6) |
O1 | 0.0426 (5) | 0.0449 (6) | 0.0549 (6) | −0.0092 (5) | 0.0233 (4) | −0.0152 (5) |
N2 | 0.0355 (6) | 0.0400 (6) | 0.0324 (6) | 0.0020 (5) | 0.0167 (5) | −0.0031 (5) |
C8 | 0.0382 (7) | 0.0341 (7) | 0.0349 (7) | −0.0003 (6) | 0.0176 (5) | −0.0028 (6) |
C9 | 0.0392 (7) | 0.0458 (8) | 0.0449 (8) | −0.0011 (6) | 0.0204 (6) | 0.0014 (7) |
C10 | 0.0389 (7) | 0.0638 (10) | 0.0564 (10) | 0.0041 (7) | 0.0193 (6) | −0.0021 (8) |
C11 | 0.0510 (9) | 0.0614 (10) | 0.0542 (10) | 0.0149 (8) | 0.0072 (7) | −0.0017 (8) |
C12 | 0.0707 (10) | 0.0418 (8) | 0.0416 (8) | 0.0095 (7) | 0.0165 (7) | 0.0044 (7) |
C13 | 0.0547 (8) | 0.0403 (8) | 0.0404 (8) | 0.0008 (7) | 0.0236 (6) | 0.0038 (7) |
C14 | 0.0356 (7) | 0.0400 (8) | 0.0365 (7) | −0.0093 (6) | 0.0170 (6) | −0.0052 (6) |
O2 | 0.0484 (6) | 0.0479 (6) | 0.0368 (5) | −0.0063 (4) | 0.0188 (4) | −0.0102 (4) |
C15 | 0.0392 (7) | 0.0521 (9) | 0.0402 (8) | 0.0009 (6) | 0.0111 (6) | −0.0006 (7) |
C1—C6 | 1.5065 (19) | N2—C8 | 1.4802 (15) |
C1—C2 | 1.5311 (19) | C8—C9 | 1.5194 (17) |
C1—H1A | 0.9900 | C8—C13 | 1.5219 (18) |
C1—H1B | 0.9900 | C8—H8 | 1.0000 |
C2—C3 | 1.511 (2) | C9—C10 | 1.5250 (19) |
C2—H2A | 0.9900 | C9—H9A | 0.9900 |
C2—H2B | 0.9900 | C9—H9B | 0.9900 |
C3—C4 | 1.509 (2) | C10—C11 | 1.521 (2) |
C3—H3A | 0.9900 | C10—H10A | 0.9900 |
C3—H3B | 0.9900 | C10—H10B | 0.9900 |
C4—C5 | 1.5268 (19) | C11—C12 | 1.514 (2) |
C4—H4A | 0.9900 | C11—H11A | 0.9900 |
C4—H4B | 0.9900 | C11—H11B | 0.9900 |
C5—C6 | 1.5121 (17) | C12—C13 | 1.5227 (18) |
C5—H5A | 0.9900 | C12—H12A | 0.9900 |
C5—H5B | 0.9900 | C12—H12B | 0.9900 |
C6—N1 | 1.4608 (15) | C13—H13A | 0.9900 |
C6—H6 | 1.0000 | C13—H13B | 0.9900 |
N1—C7 | 1.3278 (15) | C14—O2 | 1.2325 (15) |
N1—H1N | 0.8800 | C14—C15 | 1.4977 (18) |
C7—O1 | 1.2165 (15) | C15—H15A | 0.9800 |
C7—N2 | 1.4477 (15) | C15—H15B | 0.9800 |
N2—C14 | 1.3645 (16) | C15—H15C | 0.9800 |
C6—C1—C2 | 111.49 (12) | N2—C8—C9 | 111.93 (10) |
C6—C1—H1A | 109.3 | N2—C8—C13 | 111.91 (10) |
C2—C1—H1A | 109.3 | C9—C8—C13 | 110.99 (11) |
C6—C1—H1B | 109.3 | N2—C8—H8 | 107.2 |
C2—C1—H1B | 109.3 | C9—C8—H8 | 107.2 |
H1A—C1—H1B | 108.0 | C13—C8—H8 | 107.2 |
C3—C2—C1 | 111.40 (13) | C8—C9—C10 | 109.35 (12) |
C3—C2—H2A | 109.3 | C8—C9—H9A | 109.8 |
C1—C2—H2A | 109.3 | C10—C9—H9A | 109.8 |
C3—C2—H2B | 109.3 | C8—C9—H9B | 109.8 |
C1—C2—H2B | 109.3 | C10—C9—H9B | 109.8 |
H2A—C2—H2B | 108.0 | H9A—C9—H9B | 108.3 |
C4—C3—C2 | 110.92 (12) | C11—C10—C9 | 110.88 (12) |
C4—C3—H3A | 109.5 | C11—C10—H10A | 109.5 |
C2—C3—H3A | 109.5 | C9—C10—H10A | 109.5 |
C4—C3—H3B | 109.5 | C11—C10—H10B | 109.5 |
C2—C3—H3B | 109.5 | C9—C10—H10B | 109.5 |
H3A—C3—H3B | 108.0 | H10A—C10—H10B | 108.1 |
C3—C4—C5 | 111.49 (13) | C12—C11—C10 | 111.31 (12) |
C3—C4—H4A | 109.3 | C12—C11—H11A | 109.4 |
C5—C4—H4A | 109.3 | C10—C11—H11A | 109.4 |
C3—C4—H4B | 109.3 | C12—C11—H11B | 109.4 |
C5—C4—H4B | 109.3 | C10—C11—H11B | 109.4 |
H4A—C4—H4B | 108.0 | H11A—C11—H11B | 108.0 |
C6—C5—C4 | 111.49 (11) | C11—C12—C13 | 112.26 (12) |
C6—C5—H5A | 109.3 | C11—C12—H12A | 109.2 |
C4—C5—H5A | 109.3 | C13—C12—H12A | 109.2 |
C6—C5—H5B | 109.3 | C11—C12—H12B | 109.2 |
C4—C5—H5B | 109.3 | C13—C12—H12B | 109.2 |
H5A—C5—H5B | 108.0 | H12A—C12—H12B | 107.9 |
N1—C6—C1 | 111.22 (11) | C12—C13—C8 | 110.05 (11) |
N1—C6—C5 | 109.15 (10) | C12—C13—H13A | 109.7 |
C1—C6—C5 | 111.13 (11) | C8—C13—H13A | 109.7 |
N1—C6—H6 | 108.4 | C12—C13—H13B | 109.7 |
C1—C6—H6 | 108.4 | C8—C13—H13B | 109.7 |
C5—C6—H6 | 108.4 | H13A—C13—H13B | 108.2 |
C7—N1—C6 | 123.46 (10) | O2—C14—N2 | 120.64 (12) |
C7—N1—H1N | 118.3 | O2—C14—C15 | 121.14 (12) |
C6—N1—H1N | 118.3 | N2—C14—C15 | 118.19 (11) |
O1—C7—N1 | 126.04 (12) | C14—C15—H15A | 109.5 |
O1—C7—N2 | 121.17 (11) | C14—C15—H15B | 109.5 |
N1—C7—N2 | 112.76 (11) | H15A—C15—H15B | 109.5 |
C14—N2—C7 | 122.34 (11) | C14—C15—H15C | 109.5 |
C14—N2—C8 | 119.79 (10) | H15A—C15—H15C | 109.5 |
C7—N2—C8 | 117.62 (9) | H15B—C15—H15C | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O2i | 0.88 | 2.04 | 2.907 (3) | 171 |
C12—H12B···O1ii | 0.99 | 2.57 | 3.469 (3) | 151 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1/2, y−1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | C15H26N2O2 |
Mr | 266.38 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 183 |
a, b, c (Å) | 10.6174 (4), 14.2451 (9), 10.8862 (6) |
β (°) | 111.795 (3) |
V (Å3) | 1528.80 (14) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.3 × 0.2 × 0.2 |
Data collection | |
Diffractometer | Nonius KappaCCD |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5982, 3494, 2103 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.108, 0.95 |
No. of reflections | 3494 |
No. of parameters | 173 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.17, −0.18 |
Computer programs: COLLECT (Nonius, 1998), DENZO (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP (Siemens, 1990).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O2i | 0.880 | 2.035 | 2.907 (3) | 171 |
C12—H12B···O1ii | 0.990 | 2.571 | 3.469 (3) | 151 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1/2, y−1/2, −z+3/2. |
Acylated N-aryl- and N-alkylurea derivatives have been investigated, e.g. as intermediates in the synthesis of amidines and heterocyclic compounds derived therefrom, as well as precursors for poly(amide-imide)s (Wei et al. 2006, Ramsden & Rose 1997, Khorana 1953, Smith et al. 1958, Detar & Silverstein 1966a,b, Ogawa et al. 1990, Smart et al. 1960). Although quite a number of acylated dicyclohexylurea derivatives have been structurally characterized (Ball et al. 1990, Banerjee et al. 2000, Bechtel et al. 1979, Behrens & Rehder 2006, Chérioux et al. 2002, Orea Flores et al. 2006, Gallagher et al. 1999, Goel et al. 2003, Ishida et al. 1983, Mazumdar et al. 2003, Perollier et al. 1999, Salas-Coronado et al. 2001, Toniolo et al. 1990), the structure of the most simple derivative, with an acetyl group, has not yet been reported.
The molecular structure of the title compound (Fig. 1) shows the two urea nitrogen atoms N1 and N2 having a planar geometry, with an angle of 69.00 (6)° between [C6, N1, H1N, C7] and [C7, N2, C8, C14]. The bond lengths and angles have expected values. The crystal structure is determined by hydrogen bonds. The strongest interactions are observed between the amide N1—H1N group and the acetyl oxygen atom (H···O 2.035 Å). Two of these hydrogen bonds link two molecules, forming a dimeric cyclic unit. These dimers are linked to produce infinite chains by additional C—H···O bonds from one of the cyclohexyl substituents to the carbonyl oxygen atom of the urea unit (Fig. 2, Table 1).