In the crystal structure of the title compound, cinnamoyl dimethyldopamine, C19H21NO3, the shortest distance between the centers of the C=C double bonds in neighboring cinnamoyl moieties is 5.483 (4) Å. Such a long center-to-center distance and the criss-crossed arrangement of the C=C bond axes, with a torsion angle of 83.8 (2)°, contribute to the photostability of the title compound in the solid state.
Supporting information
CCDC reference: 185781
Key indicators
- Single-crystal X-ray study
- T = 250 K
- Mean (C-C) = 0.004 Å
- R factor = 0.056
- wR factor = 0.156
- Data-to-parameter ratio = 15.2
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level C:
REFLT_03
From the CIF: _diffrn_reflns_theta_max 75.00
From the CIF: _reflns_number_total 3176
TEST2: Reflns within _diffrn_reflns_theta_max
Count of symmetry unique reflns 3360
Completeness (_total/calc) 94.52%
Alert C: < 95% complete
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
The title compound was prepared from dimethyldopamine and trans-cinnamoyl
chloride through solvent-free reaction (Ito et al., 2001). Crystals of
(I) were grown from an acetone solution.
The relatively low completeness (0.945 for θmax=75°) is a result of the
blind region of the low-temperature apparatus. All H-atom positional
parameters were calculated geometrically and fixed with Uiso(H) =
1.2Ueq(parent atom).
Data collection: WinAFC Diffractometer Control Software (Rigaku, 1999); cell refinement: WinAFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1999); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: TEXSAN.
Crystal data top
C19H21NO3 | F(000) = 664 |
Mr = 311.38 | Dx = 1.275 Mg m−3 |
Monoclinic, P21/a | Cu Kα radiation, λ = 1.5418 Å |
a = 24.449 (2) Å | Cell parameters from 25 reflections |
b = 5.2431 (5) Å | θ = 25.0–30.0° |
c = 12.6633 (9) Å | µ = 0.69 mm−1 |
β = 91.714 (6)° | T = 250 K |
V = 1622.6 (2) Å3 | Needle, colourless |
Z = 4 | 0.75 × 0.15 × 0.05 mm |
Data collection top
Rigaku AFC-7R diffractometer | Rint = 0.025 |
θ–2θ scans | θmax = 75°, θmin = 2.5° |
Absorption correction: integration (Coppens et al., 1965) | h = 0→30 |
Tmin = 0.842, Tmax = 0.965 | k = −6→0 |
4079 measured reflections | l = −15→15 |
3176 independent reflections | 3 standard reflections every 150 reflections |
2641 reflections with I > 2σ(I) | intensity decay: 8.1% |
Refinement top
Refinement on F2 | w = 1/[σ2(Fo2) + (0.0408P)2 + 1.4606P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.056 | (Δ/σ)max = 0.001 |
wR(F2) = 0.156 | Δρmax = 0.28 e Å−3 |
S = 1.26 | Δρmin = −0.25 e Å−3 |
3176 reflections | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
209 parameters | Extinction coefficient: 0.0028 (3) |
H-atom parameters constrained | |
Crystal data top
C19H21NO3 | V = 1622.6 (2) Å3 |
Mr = 311.38 | Z = 4 |
Monoclinic, P21/a | Cu Kα radiation |
a = 24.449 (2) Å | µ = 0.69 mm−1 |
b = 5.2431 (5) Å | T = 250 K |
c = 12.6633 (9) Å | 0.75 × 0.15 × 0.05 mm |
β = 91.714 (6)° | |
Data collection top
Rigaku AFC-7R diffractometer | 2641 reflections with I > 2σ(I) |
Absorption correction: integration (Coppens et al., 1965) | Rint = 0.025 |
Tmin = 0.842, Tmax = 0.965 | 3 standard reflections every 150 reflections |
4079 measured reflections | intensity decay: 8.1% |
3176 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.056 | 209 parameters |
wR(F2) = 0.156 | H-atom parameters constrained |
S = 1.26 | Δρmax = 0.28 e Å−3 |
3176 reflections | Δρmin = −0.25 e Å−3 |
Special details top
Refinement. Refinement was based on F2 against all reflections. The weighted
R-factor (wR) and goodness of fit (S) were based on
F2, and conventional R-factor (R) was calculated on
F, with F set to zero for negative F2. The threshold
expression of I > 2σ(I) was used only for calculating
R-factor(gt). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.42822 (8) | 0.6551 (4) | 0.0621 (2) | 0.0519 (5) | |
O2 | 0.67592 (7) | −0.1566 (4) | 0.4609 (1) | 0.0500 (5) | |
O3 | 0.61383 (7) | 0.1929 (4) | 0.5347 (1) | 0.0539 (5) | |
N4 | 0.43206 (8) | 0.2244 (4) | 0.0733 (2) | 0.0456 (5) | |
C5 | 0.1854 (1) | 0.6130 (6) | −0.2582 (2) | 0.0469 (6) | |
C6 | 0.1942 (1) | 0.4245 (6) | −0.1840 (2) | 0.0459 (6) | |
C7 | 0.2423 (1) | 0.4186 (5) | −0.1235 (2) | 0.0404 (6) | |
C8 | 0.28253 (9) | 0.6035 (5) | −0.1365 (2) | 0.0349 (5) | |
C9 | 0.2724 (1) | 0.7964 (5) | −0.2101 (2) | 0.0440 (6) | |
C10 | 0.2243 (1) | 0.7998 (5) | −0.2711 (2) | 0.0489 (6) | |
C11 | 0.3344 (1) | 0.6020 (5) | −0.0747 (2) | 0.0375 (5) | |
C12 | 0.3553 (1) | 0.4147 (5) | −0.0169 (2) | 0.0385 (5) | |
C13 | 0.4084 (1) | 0.4435 (5) | 0.0432 (2) | 0.0374 (5) | |
C14 | 0.4841 (1) | 0.2087 (6) | 0.1330 (2) | 0.0525 (7) | |
C15 | 0.4771 (1) | 0.0830 (6) | 0.2386 (2) | 0.0516 (7) | |
C16 | 0.53078 (9) | 0.0195 (5) | 0.2959 (2) | 0.0409 (6) | |
C17 | 0.5645 (1) | −0.1684 (6) | 0.2576 (2) | 0.0446 (6) | |
C18 | 0.6133 (1) | −0.2338 (5) | 0.3106 (2) | 0.0422 (6) | |
C19 | 0.62896 (9) | −0.1088 (5) | 0.4026 (2) | 0.0377 (5) | |
C20 | 0.59536 (9) | 0.0827 (5) | 0.4425 (2) | 0.0374 (5) | |
C21 | 0.5469 (1) | 0.1451 (5) | 0.3887 (2) | 0.0408 (6) | |
C22 | 0.7096 (1) | −0.3586 (6) | 0.4246 (2) | 0.0495 (7) | |
C23 | 0.5813 (1) | 0.3872 (6) | 0.5787 (2) | 0.0523 (7) | |
H4 | 0.4140 | 0.0695 | 0.0549 | 0.0547* | |
H5 | 0.1526 | 0.6142 | −0.3005 | 0.0562* | |
H6 | 0.1670 | 0.2978 | −0.1742 | 0.0551* | |
H7 | 0.2479 | 0.2873 | −0.0726 | 0.0485* | |
H9 | 0.2987 | 0.9275 | −0.2186 | 0.0527* | |
H10 | 0.2182 | 0.9311 | −0.3218 | 0.0587* | |
H11 | 0.3554 | 0.7544 | −0.0767 | 0.0450* | |
H12 | 0.3361 | 0.2575 | −0.0135 | 0.0462* | |
H14A | 0.4980 | 0.3760 | 0.1438 | 0.0629* | |
H14B | 0.5092 | 0.1120 | 0.0936 | 0.0629* | |
H15A | 0.4569 | 0.1949 | 0.2818 | 0.0619* | |
H15B | 0.4571 | −0.0708 | 0.2279 | 0.0619* | |
H17 | 0.5542 | −0.2546 | 0.1941 | 0.0534* | |
H18 | 0.6358 | −0.3644 | 0.2833 | 0.0506* | |
H21 | 0.5243 | 0.2759 | 0.4156 | 0.0490* | |
H22A | 0.6895 | −0.5136 | 0.4242 | 0.0593* | |
H22B | 0.7409 | −0.3748 | 0.4703 | 0.0593* | |
H22C | 0.7209 | −0.3216 | 0.3550 | 0.0593* | |
H23A | 0.5462 | 0.3202 | 0.5937 | 0.0627* | |
H23B | 0.5985 | 0.4477 | 0.6421 | 0.0627* | |
H23C | 0.5773 | 0.5238 | 0.5298 | 0.0627* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.051 (1) | 0.040 (1) | 0.064 (1) | −0.0040 (8) | −0.0139 (9) | −0.0034 (9) |
O2 | 0.0405 (9) | 0.062 (1) | 0.0468 (10) | 0.0141 (9) | −0.0136 (8) | −0.0122 (9) |
O3 | 0.051 (1) | 0.065 (1) | 0.0446 (10) | 0.0138 (9) | −0.0140 (8) | −0.0208 (9) |
N4 | 0.039 (1) | 0.040 (1) | 0.057 (1) | −0.0034 (9) | −0.0161 (10) | 0.005 (1) |
C5 | 0.041 (1) | 0.056 (2) | 0.044 (1) | 0.010 (1) | −0.007 (1) | −0.005 (1) |
C6 | 0.038 (1) | 0.053 (2) | 0.046 (1) | −0.001 (1) | −0.001 (1) | −0.001 (1) |
C7 | 0.042 (1) | 0.043 (1) | 0.036 (1) | 0.002 (1) | 0.0010 (10) | 0.005 (1) |
C8 | 0.040 (1) | 0.035 (1) | 0.029 (1) | 0.0042 (10) | 0.0002 (9) | −0.0034 (9) |
C9 | 0.048 (1) | 0.039 (1) | 0.045 (1) | 0.000 (1) | −0.003 (1) | 0.003 (1) |
C10 | 0.055 (2) | 0.048 (2) | 0.043 (1) | 0.007 (1) | −0.009 (1) | 0.008 (1) |
C11 | 0.040 (1) | 0.037 (1) | 0.036 (1) | −0.001 (1) | −0.0021 (10) | −0.0034 (10) |
C12 | 0.038 (1) | 0.037 (1) | 0.040 (1) | −0.003 (1) | −0.0032 (10) | −0.001 (1) |
C13 | 0.039 (1) | 0.039 (1) | 0.034 (1) | −0.002 (1) | −0.0012 (10) | −0.0018 (10) |
C14 | 0.036 (1) | 0.055 (2) | 0.066 (2) | −0.005 (1) | −0.014 (1) | 0.012 (1) |
C15 | 0.034 (1) | 0.077 (2) | 0.043 (1) | 0.005 (1) | −0.007 (1) | −0.007 (1) |
C16 | 0.033 (1) | 0.054 (2) | 0.035 (1) | −0.002 (1) | −0.0030 (10) | 0.001 (1) |
C17 | 0.041 (1) | 0.056 (2) | 0.037 (1) | −0.004 (1) | −0.006 (1) | −0.009 (1) |
C18 | 0.039 (1) | 0.047 (1) | 0.040 (1) | 0.002 (1) | −0.001 (1) | −0.007 (1) |
C19 | 0.032 (1) | 0.044 (1) | 0.037 (1) | −0.0012 (10) | −0.0042 (9) | 0.001 (1) |
C20 | 0.038 (1) | 0.041 (1) | 0.033 (1) | −0.001 (1) | −0.0038 (9) | −0.0037 (10) |
C21 | 0.036 (1) | 0.049 (1) | 0.037 (1) | 0.007 (1) | −0.0008 (10) | −0.002 (1) |
C22 | 0.040 (1) | 0.055 (2) | 0.053 (2) | 0.011 (1) | −0.006 (1) | −0.002 (1) |
C23 | 0.058 (2) | 0.052 (2) | 0.046 (1) | 0.004 (1) | −0.002 (1) | −0.014 (1) |
Geometric parameters (Å, º) top
O1—C13 | 1.231 (3) | C12—H12 | 0.950 |
O2—C19 | 1.369 (3) | C14—C15 | 1.505 (4) |
O2—C22 | 1.426 (3) | C14—H14A | 0.950 |
O3—C20 | 1.367 (3) | C14—H14B | 0.950 |
O3—C23 | 1.417 (4) | C15—C16 | 1.518 (3) |
N4—C13 | 1.337 (3) | C15—H15A | 0.950 |
N4—C14 | 1.461 (3) | C15—H15B | 0.950 |
N4—H4 | 0.950 | C16—C17 | 1.382 (4) |
C5—C6 | 1.376 (4) | C16—C21 | 1.394 (3) |
C5—C10 | 1.378 (4) | C17—C18 | 1.393 (3) |
C5—H5 | 0.950 | C17—H17 | 0.950 |
C6—C7 | 1.385 (3) | C18—C19 | 1.382 (3) |
C6—H6 | 0.950 | C18—H18 | 0.950 |
C7—C8 | 1.395 (3) | C19—C20 | 1.401 (3) |
C7—H7 | 0.950 | C20—C21 | 1.388 (3) |
C8—C9 | 1.392 (3) | C21—H21 | 0.950 |
C8—C11 | 1.470 (3) | C22—H22A | 0.950 |
C9—C10 | 1.388 (4) | C22—H22B | 0.950 |
C9—H9 | 0.950 | C22—H22C | 0.950 |
C10—H10 | 0.950 | C23—H23A | 0.950 |
C11—C12 | 1.319 (3) | C23—H23B | 0.950 |
C11—H11 | 0.950 | C23—H23C | 0.950 |
C12—C13 | 1.492 (3) | | |
| | | |
C19—O2—C22 | 116.5 (2) | H14A—C14—H14B | 109.5 |
C20—O3—C23 | 117.7 (2) | C14—C15—C16 | 113.6 (2) |
C13—N4—C14 | 123.9 (2) | C14—C15—H15A | 108.4 |
C13—N4—H4 | 118.0 | C14—C15—H15B | 108.4 |
C14—N4—H4 | 118.0 | C16—C15—H15A | 108.4 |
C6—C5—C10 | 119.8 (2) | C16—C15—H15B | 108.4 |
C6—C5—H5 | 120.1 | H15A—C15—H15B | 109.5 |
C10—C5—H5 | 120.1 | C15—C16—C17 | 120.4 (2) |
C5—C6—C7 | 120.4 (2) | C15—C16—C21 | 121.2 (2) |
C5—C6—H6 | 119.8 | C17—C16—C21 | 118.4 (2) |
C7—C6—H6 | 119.8 | C16—C17—C18 | 121.2 (2) |
C6—C7—C8 | 120.6 (2) | C16—C17—H17 | 119.4 |
C6—C7—H7 | 119.7 | C18—C17—H17 | 119.4 |
C8—C7—H7 | 119.7 | C17—C18—C19 | 120.1 (2) |
C7—C8—C9 | 118.1 (2) | C17—C18—H18 | 120.0 |
C7—C8—C11 | 122.3 (2) | C19—C18—H18 | 119.9 |
C9—C8—C11 | 119.6 (2) | O2—C19—C18 | 125.1 (2) |
C8—C9—C10 | 120.9 (2) | O2—C19—C20 | 115.4 (2) |
C8—C9—H9 | 119.6 | C18—C19—C20 | 119.5 (2) |
C10—C9—H9 | 119.5 | O3—C20—C19 | 115.3 (2) |
C5—C10—C9 | 120.0 (2) | O3—C20—C21 | 125.1 (2) |
C5—C10—H10 | 120.0 | C19—C20—C21 | 119.6 (2) |
C9—C10—H10 | 120.0 | C16—C21—C20 | 121.2 (2) |
C8—C11—C12 | 127.8 (2) | C16—C21—H21 | 119.4 |
C8—C11—H11 | 116.1 | C20—C21—H21 | 119.4 |
C12—C11—H11 | 116.1 | O2—C22—H22A | 109.5 |
C11—C12—C13 | 121.7 (2) | O2—C22—H22B | 109.5 |
C11—C12—H12 | 119.2 | O2—C22—H22C | 109.5 |
C13—C12—H12 | 119.2 | H22A—C22—H22B | 109.5 |
O1—C13—N4 | 123.7 (2) | H22A—C22—H22C | 109.5 |
O1—C13—C12 | 121.4 (2) | H22B—C22—H22C | 109.5 |
N4—C13—C12 | 114.9 (2) | O3—C23—H23A | 109.5 |
N4—C14—C15 | 111.3 (2) | O3—C23—H23B | 109.5 |
N4—C14—H14A | 109.0 | O3—C23—H23C | 109.5 |
N4—C14—H14B | 109.0 | H23A—C23—H23B | 109.5 |
C15—C14—H14A | 109.0 | H23A—C23—H23C | 109.5 |
C15—C14—H14B | 109.0 | H23B—C23—H23C | 109.5 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4···O1i | 0.95 | 2.20 | 2.990 (3) | 140 |
Symmetry code: (i) x, y−1, z. |
Experimental details
Crystal data |
Chemical formula | C19H21NO3 |
Mr | 311.38 |
Crystal system, space group | Monoclinic, P21/a |
Temperature (K) | 250 |
a, b, c (Å) | 24.449 (2), 5.2431 (5), 12.6633 (9) |
β (°) | 91.714 (6) |
V (Å3) | 1622.6 (2) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 0.69 |
Crystal size (mm) | 0.75 × 0.15 × 0.05 |
|
Data collection |
Diffractometer | Rigaku AFC-7R diffractometer |
Absorption correction | Integration (Coppens et al., 1965) |
Tmin, Tmax | 0.842, 0.965 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4079, 3176, 2641 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.626 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.056, 0.156, 1.26 |
No. of reflections | 3176 |
No. of parameters | 209 |
No. of restraints | ? |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.28, −0.25 |
Selected bond lengths (Å) topO1—C13 | 1.231 (3) | C11—C12 | 1.319 (3) |
N4—C13 | 1.337 (3) | C12—C13 | 1.492 (3) |
N4—C14 | 1.461 (3) | C14—C15 | 1.505 (4) |
C8—C11 | 1.470 (3) | C15—C16 | 1.518 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4···O1i | 0.95 | 2.20 | 2.990 (3) | 140 |
Symmetry code: (i) x, y−1, z. |
Solid-state photochemistry of some dopamine derivatives was investigated by Ito et al. (2001). The crystal structure of the photostable title compound, (I), has been determined to investigate the geometrical factors which prevent the [2 + 2] photodimerization.
The shortest intermolecular distance between the C═C double bonds of the cinnamoyl moieties is 5.087 (4) Å for C12···C11(1/2 - x, 1/2 + y, -z), and the center-to-center distance of the C═C double bonds is 5.483 (4) Å for this pair. These molecules are related by 21 screw axis parallel to b, and the C═C bond axes are criss-crossed with each other, making a torsion angle of 83.8 (2)° (Fig. 2). Intermolecular N—H···O hydrogen bonds form a linear chain along b (Table 2).