Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805040390/ob6602sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805040390/ob6602Isup2.hkl |
CCDC reference: 296627
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (C-C)= 0.004 Å
- R factor = 0.053
- wR factor = 0.190
- Data-to-parameter ratio = 15.0
checkCIF/PLATON results
No syntax errors found No errors found in this datablock
An ethanol solution of benzoylacetone and 2-(hydroxymethyl)aniline (1:1) was refluxed for 28 h. After removal of the solvent, the residue was recrystallized from CH2Cl2 and diethyl ether (1:1, v/v) at 278 K to afford the yellow compound (I) (yield, 52%; m.p., 391.2–392.6 K).
All H atoms were placed at geometrically idealized positions, and treated as riding atoms, with C–H = 0.93 Å, N–H = 0.86 Å and O–H = 0.82 Å, and with Uiso(H) = 1.2Ueq(C,N) or 1.5Ueq(O).
Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON.
Fig. 1. Molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level. The intramolecular hydrogen bond is shown as a dashed line. |
C17H17NO2 | F(000) = 568 |
Mr = 267.32 | Dx = 1.260 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 8.5030 (17) Å | Cell parameters from 25 reflections |
b = 11.543 (2) Å | θ = 9–14° |
c = 14.717 (3) Å | µ = 0.08 mm−1 |
β = 102.74 (3)° | T = 295 K |
V = 1408.9 (5) Å3 | Block, yellow |
Z = 4 | 0.40 × 0.30 × 0.20 mm |
Enraf–Nonius CAD-4 diffractometer | 1867 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.028 |
Graphite monochromator | θmax = 26.0°, θmin = 2.3° |
ω/2θ scans | h = 0→10 |
Absorption correction: empirical (using intensity measurements) via ψ scan (North et al., 1968) | k = 0→14 |
Tmin = 0.953, Tmax = 0.984 | l = −18→17 |
2957 measured reflections | 3 standard reflections every 200 reflections |
2766 independent reflections | intensity decay: none |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.053 | H-atom parameters constrained |
wR(F2) = 0.190 | w = 1/[σ2(Fo2) + (0.1005P)2 + 0.3124P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max < 0.001 |
2766 reflections | Δρmax = 0.21 e Å−3 |
184 parameters | Δρmin = −0.19 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: 0.023 (6) |
C17H17NO2 | V = 1408.9 (5) Å3 |
Mr = 267.32 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.5030 (17) Å | µ = 0.08 mm−1 |
b = 11.543 (2) Å | T = 295 K |
c = 14.717 (3) Å | 0.40 × 0.30 × 0.20 mm |
β = 102.74 (3)° |
Enraf–Nonius CAD-4 diffractometer | 1867 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) via ψ scan (North et al., 1968) | Rint = 0.028 |
Tmin = 0.953, Tmax = 0.984 | 3 standard reflections every 200 reflections |
2957 measured reflections | intensity decay: none |
2766 independent reflections |
R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
wR(F2) = 0.190 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.21 e Å−3 |
2766 reflections | Δρmin = −0.19 e Å−3 |
184 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 | ||
O1 | 0.76595 (19) | 0.87795 (17) | 0.09528 (11) | 0.0626 (5) | |
O2 | 0.3700 (2) | 1.19095 (16) | 0.07980 (12) | 0.0619 (5) | |
H2O | 0.3197 | 1.1717 | 0.0278 | 0.093* | |
N | 0.6549 (2) | 0.93678 (18) | 0.24276 (13) | 0.0521 (5) | |
H1N | 0.6363 | 0.9135 | 0.1859 | 0.062* | |
C2 | 1.1606 (4) | 0.8183 (3) | −0.0244 (2) | 0.0846 (10) | |
H2 | 1.1521 | 0.8278 | −0.0880 | 0.101* | |
C3 | 1.3003 (3) | 0.7753 (3) | 0.0299 (3) | 0.0741 (8) | |
H3 | 1.3862 | 0.7558 | 0.0032 | 0.089* | |
C4 | 1.3125 (3) | 0.7613 (3) | 0.1234 (2) | 0.0735 (8) | |
H4 | 1.4071 | 0.7325 | 0.1607 | 0.088* | |
C5 | 1.1841 (3) | 0.7901 (2) | 0.1627 (2) | 0.0648 (7) | |
H5 | 1.1940 | 0.7807 | 0.2264 | 0.078* | |
C6 | 1.0425 (3) | 0.8323 (2) | 0.10951 (17) | 0.0504 (6) | |
C1 | 1.0315 (3) | 0.8479 (3) | 0.0146 (2) | 0.0713 (8) | |
H1 | 0.9378 | 0.8782 | −0.0227 | 0.086* | |
C7 | 0.9015 (3) | 0.8667 (2) | 0.14939 (16) | 0.0489 (6) | |
C8 | 0.9250 (3) | 0.8873 (2) | 0.24581 (16) | 0.0526 (6) | |
H8 | 1.0279 | 0.8755 | 0.2823 | 0.063* | |
C9 | 0.8063 (3) | 0.9237 (2) | 0.29023 (16) | 0.0484 (6) | |
C10 | 0.8505 (3) | 0.9501 (3) | 0.39235 (17) | 0.0656 (7) | |
H10A | 0.8009 | 1.0216 | 0.4042 | 0.098* | |
H10B | 0.9655 | 0.9569 | 0.4121 | 0.098* | |
H10C | 0.8133 | 0.8886 | 0.4263 | 0.098* | |
C11 | 0.5193 (3) | 0.9835 (2) | 0.27196 (15) | 0.0475 (6) | |
C12 | 0.4797 (3) | 0.9486 (2) | 0.35449 (17) | 0.0575 (7) | |
H12 | 0.5401 | 0.8919 | 0.3914 | 0.069* | |
C13 | 0.3493 (3) | 0.9993 (3) | 0.38118 (19) | 0.0645 (7) | |
H13 | 0.3246 | 0.9782 | 0.4374 | 0.077* | |
C14 | 0.2570 (3) | 1.0794 (2) | 0.32608 (19) | 0.0610 (7) | |
H14 | 0.1708 | 1.1138 | 0.3452 | 0.073* | |
C15 | 0.2912 (3) | 1.1099 (2) | 0.24152 (18) | 0.0533 (6) | |
H15 | 0.2255 | 1.1628 | 0.2032 | 0.064* | |
C16 | 0.4222 (2) | 1.0624 (2) | 0.21339 (15) | 0.0460 (6) | |
C17 | 0.4632 (3) | 1.0968 (3) | 0.12242 (17) | 0.0599 (7) | |
H17A | 0.5765 | 1.1174 | 0.1337 | 0.072* | |
H17B | 0.4458 | 1.0311 | 0.0804 | 0.072* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0447 (9) | 0.0947 (14) | 0.0461 (9) | 0.0126 (9) | 0.0051 (7) | −0.0076 (9) |
O2 | 0.0664 (11) | 0.0649 (11) | 0.0480 (10) | 0.0052 (9) | −0.0014 (8) | 0.0000 (8) |
N | 0.0437 (10) | 0.0698 (13) | 0.0416 (10) | 0.0099 (9) | 0.0069 (8) | −0.0044 (9) |
C2 | 0.0677 (18) | 0.121 (3) | 0.0729 (19) | −0.0076 (19) | 0.0329 (16) | −0.0120 (19) |
C3 | 0.0580 (16) | 0.0708 (18) | 0.104 (2) | −0.0023 (14) | 0.0407 (16) | −0.0122 (17) |
C4 | 0.0538 (15) | 0.0663 (18) | 0.104 (2) | 0.0141 (13) | 0.0262 (16) | 0.0087 (16) |
C5 | 0.0541 (14) | 0.0674 (17) | 0.0741 (18) | 0.0144 (13) | 0.0167 (13) | 0.0079 (14) |
C6 | 0.0447 (12) | 0.0517 (14) | 0.0565 (14) | −0.0029 (10) | 0.0148 (10) | −0.0068 (11) |
C1 | 0.0502 (15) | 0.104 (2) | 0.0616 (17) | 0.0003 (15) | 0.0170 (12) | −0.0090 (16) |
C7 | 0.0403 (11) | 0.0537 (14) | 0.0514 (13) | 0.0027 (10) | 0.0075 (10) | −0.0016 (11) |
C8 | 0.0394 (11) | 0.0676 (16) | 0.0482 (13) | 0.0035 (11) | 0.0039 (10) | −0.0031 (11) |
C9 | 0.0456 (12) | 0.0543 (14) | 0.0443 (12) | 0.0003 (10) | 0.0076 (10) | −0.0010 (10) |
C10 | 0.0553 (15) | 0.092 (2) | 0.0465 (14) | 0.0000 (14) | 0.0050 (11) | −0.0082 (13) |
C11 | 0.0414 (11) | 0.0565 (14) | 0.0449 (12) | −0.0006 (10) | 0.0101 (10) | −0.0074 (10) |
C12 | 0.0573 (14) | 0.0657 (16) | 0.0505 (13) | 0.0052 (12) | 0.0139 (11) | 0.0065 (12) |
C13 | 0.0629 (16) | 0.0794 (19) | 0.0574 (15) | 0.0011 (14) | 0.0267 (13) | 0.0002 (14) |
C14 | 0.0517 (14) | 0.0677 (17) | 0.0697 (17) | 0.0009 (12) | 0.0264 (13) | −0.0107 (14) |
C15 | 0.0447 (12) | 0.0551 (14) | 0.0603 (15) | 0.0022 (11) | 0.0120 (11) | −0.0041 (11) |
C16 | 0.0408 (11) | 0.0508 (13) | 0.0452 (12) | −0.0033 (10) | 0.0072 (10) | −0.0065 (10) |
C17 | 0.0508 (14) | 0.0792 (18) | 0.0489 (14) | 0.0095 (12) | 0.0093 (11) | 0.0047 (13) |
O1—C7 | 1.255 (3) | C8—C9 | 1.383 (3) |
O2—C17 | 1.408 (3) | C8—H8 | 0.9300 |
O2—H2O | 0.8200 | C9—C10 | 1.498 (3) |
N—C9 | 1.331 (3) | C10—H10A | 0.9600 |
N—C11 | 1.423 (3) | C10—H10B | 0.9600 |
N—H1N | 0.8600 | C10—H10C | 0.9600 |
C2—C3 | 1.370 (4) | C11—C12 | 1.390 (3) |
C2—C1 | 1.388 (4) | C11—C16 | 1.393 (3) |
C2—H2 | 0.9300 | C12—C13 | 1.384 (3) |
C3—C4 | 1.367 (4) | C12—H12 | 0.9300 |
C3—H3 | 0.9300 | C13—C14 | 1.360 (4) |
C4—C5 | 1.384 (4) | C13—H13 | 0.9300 |
C4—H4 | 0.9300 | C14—C15 | 1.385 (4) |
C5—C6 | 1.372 (3) | C14—H14 | 0.9300 |
C5—H5 | 0.9300 | C15—C16 | 1.383 (3) |
C6—C1 | 1.391 (4) | C15—H15 | 0.9300 |
C6—C7 | 1.501 (3) | C16—C17 | 1.509 (3) |
C1—H1 | 0.9300 | C17—H17A | 0.9700 |
C7—C8 | 1.409 (3) | C17—H17B | 0.9700 |
C17—O2—H2O | 109.5 | C9—C10—H10A | 109.5 |
C9—N—C11 | 129.7 (2) | C9—C10—H10B | 109.5 |
C9—N—H1N | 115.1 | H10A—C10—H10B | 109.5 |
C11—N—H1N | 115.1 | C9—C10—H10C | 109.5 |
C3—C2—C1 | 120.8 (3) | H10A—C10—H10C | 109.5 |
C3—C2—H2 | 119.6 | H10B—C10—H10C | 109.5 |
C1—C2—H2 | 119.6 | C12—C11—C16 | 120.4 (2) |
C4—C3—C2 | 119.6 (3) | C12—C11—N | 121.5 (2) |
C4—C3—H3 | 120.2 | C16—C11—N | 118.1 (2) |
C2—C3—H3 | 120.2 | C13—C12—C11 | 119.3 (2) |
C3—C4—C5 | 120.0 (3) | C13—C12—H12 | 120.4 |
C3—C4—H4 | 120.0 | C11—C12—H12 | 120.4 |
C5—C4—H4 | 120.0 | C14—C13—C12 | 120.8 (2) |
C6—C5—C4 | 121.4 (3) | C14—C13—H13 | 119.6 |
C6—C5—H5 | 119.3 | C12—C13—H13 | 119.6 |
C4—C5—H5 | 119.3 | C13—C14—C15 | 120.0 (2) |
C5—C6—C1 | 118.4 (2) | C13—C14—H14 | 120.0 |
C5—C6—C7 | 123.2 (2) | C15—C14—H14 | 120.0 |
C1—C6—C7 | 118.4 (2) | C16—C15—C14 | 120.8 (2) |
C2—C1—C6 | 119.9 (3) | C16—C15—H15 | 119.6 |
C2—C1—H1 | 120.0 | C14—C15—H15 | 119.6 |
C6—C1—H1 | 120.0 | C15—C16—C11 | 118.7 (2) |
O1—C7—C6 | 118.7 (2) | C15—C16—C17 | 121.3 (2) |
O1—C7—C8 | 121.9 (2) | C11—C16—C17 | 120.0 (2) |
C6—C7—C8 | 119.4 (2) | O2—C17—C16 | 112.4 (2) |
C9—C8—C7 | 124.8 (2) | O2—C17—H17A | 109.1 |
C9—C8—H8 | 117.6 | C16—C17—H17A | 109.1 |
C7—C8—H8 | 117.6 | O2—C17—H17B | 109.1 |
N—C9—C8 | 120.6 (2) | C16—C17—H17B | 109.1 |
N—C9—C10 | 120.2 (2) | H17A—C17—H17B | 107.9 |
C8—C9—C10 | 119.2 (2) | ||
C1—C2—C3—C4 | 0.1 (5) | C7—C8—C9—C10 | −175.9 (2) |
C2—C3—C4—C5 | 0.2 (5) | C9—N—C11—C12 | −48.7 (4) |
C3—C4—C5—C6 | 0.4 (5) | C9—N—C11—C16 | 134.0 (3) |
C4—C5—C6—C1 | −1.3 (4) | C16—C11—C12—C13 | −4.6 (4) |
C4—C5—C6—C7 | −178.8 (2) | N—C11—C12—C13 | 178.1 (2) |
C3—C2—C1—C6 | −1.0 (5) | C11—C12—C13—C14 | 2.3 (4) |
C5—C6—C1—C2 | 1.6 (4) | C12—C13—C14—C15 | 1.1 (4) |
C7—C6—C1—C2 | 179.2 (3) | C13—C14—C15—C16 | −2.2 (4) |
C5—C6—C7—O1 | −163.3 (3) | C14—C15—C16—C11 | −0.1 (4) |
C1—C6—C7—O1 | 19.2 (4) | C14—C15—C16—C17 | −178.6 (2) |
C5—C6—C7—C8 | 17.7 (4) | C12—C11—C16—C15 | 3.5 (3) |
C1—C6—C7—C8 | −159.8 (2) | N—C11—C16—C15 | −179.1 (2) |
O1—C7—C8—C9 | −1.6 (4) | C12—C11—C16—C17 | −178.0 (2) |
C6—C7—C8—C9 | 177.4 (2) | N—C11—C16—C17 | −0.6 (3) |
C11—N—C9—C8 | −173.1 (2) | C15—C16—C17—O2 | 8.6 (3) |
C11—N—C9—C10 | 6.0 (4) | C11—C16—C17—O2 | −169.9 (2) |
C7—C8—C9—N | 3.3 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N—H1N···O1 | 0.86 | 1.95 | 2.640 (3) | 136 |
O2—H2O···O1i | 0.82 | 1.89 | 2.701 (2) | 172 |
C12—H12···O2ii | 0.93 | 2.45 | 3.297 (3) | 152 |
Symmetry codes: (i) −x+1, −y+2, −z; (ii) −x+1, y−1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C17H17NO2 |
Mr | 267.32 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 295 |
a, b, c (Å) | 8.5030 (17), 11.543 (2), 14.717 (3) |
β (°) | 102.74 (3) |
V (Å3) | 1408.9 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.40 × 0.30 × 0.20 |
Data collection | |
Diffractometer | Enraf–Nonius CAD-4 diffractometer |
Absorption correction | Empirical (using intensity measurements) via ψ scan (North et al., 1968) |
Tmin, Tmax | 0.953, 0.984 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2957, 2766, 1867 |
Rint | 0.028 |
(sin θ/λ)max (Å−1) | 0.616 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.190, 1.08 |
No. of reflections | 2766 |
No. of parameters | 184 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.21, −0.19 |
Computer programs: CAD-4 Software (Enraf–Nonius, 1989), CAD-4 Software, XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), PLATON.
O1—C7 | 1.255 (3) | C6—C7 | 1.501 (3) |
O2—C17 | 1.408 (3) | C7—C8 | 1.409 (3) |
N—C9 | 1.331 (3) | C8—C9 | 1.383 (3) |
N—C11 | 1.423 (3) | C9—C10 | 1.498 (3) |
C9—N—C11 | 129.7 (2) | N—C9—C8 | 120.6 (2) |
O1—C7—C6 | 118.7 (2) | N—C9—C10 | 120.2 (2) |
O1—C7—C8 | 121.9 (2) | C8—C9—C10 | 119.2 (2) |
C6—C7—C8 | 119.4 (2) | ||
C5—C6—C7—C8 | 17.7 (4) | C9—N—C11—C12 | −48.7 (4) |
C7—C8—C9—N | 3.3 (4) | C15—C16—C17—O2 | 8.6 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N—H1N···O1 | 0.86 | 1.95 | 2.640 (3) | 136 |
O2—H2O···O1i | 0.82 | 1.89 | 2.701 (2) | 172 |
C12—H12···O2ii | 0.93 | 2.45 | 3.297 (3) | 152 |
Symmetry codes: (i) −x+1, −y+2, −z; (ii) −x+1, y−1/2, −z+1/2. |
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Enaminones have been studied extensively, not only because of plentiful reaction chemistry (Christoffers et al., 2003; Tietze et al., 1989), but also owing to their applications in coordination chemistry (Kim et al., 2001; Doherty et al., 1999) as well as chiral auxiliaries in organic synthesis (Christoffers, 2003). As part of an ongoing investigation of the chemistry of enaminones, compound (I) has been synthesized by the condensation of benzoylacetone and 2-hydroxymethylaniline (Shi et al., 2004, 2005) and its crystal structure has been determined (Fig. 1). An organometallic analog of (I), hereafter (II), has already been studied (Shi, 2005).
The bond lengths and angles of the O═C–C═C–N system in (I) are similar to the corresponding values in (II) (Table 1). For (I) and (II), the bond lengths in the O═C–C═C–N system indicate electron delocalization (Gilli et al., 2000). The dihedral angles between the O═C–C═C–N system and the planes of the C1—C6 and C11—C16 rings in (I) are 18.94 (14) and 41.06 (12)°, repsectively. The corresponding angles in (II) are 5.4 (3) and 67.8 (3)°, respectively. The bonds linking the O═ C–C═C–N system and the aromatic ring in (I) and (II) are typical single bonds (Csp2–Csp2), suggesting that the C1–C6 benzene ring in (I) and the substituted cyclopentadienyl ring in (II) are not involved in the conjugation of the O═C–C═C–N system.
As in (II), the strong intramolecular hydrogen bond between the enamine N atom and the carbonyl O atom in (I) stabilizes the enaminone. Furthermore, intermolecular O–H···O═C hydrogen bonds form centrosymmetric R22(16) dimers. Unlike in (II), C—H···O hydrogen bonds (Table 2) are also observed in (I).