Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807047988/zl2065sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807047988/zl2065Isup2.hkl |
CCDC reference: 669131
1. Preparation of cinnamoyl chloride: Cinnamoyl chloride was prepared according to the reported method (Adams & Ulich, 1920).
2. Preparation of (R,E)-3-carboxy-2-(cinnamoyloxy) -N,N,N-trimethylpropan-1-ammonium chloride:
L-carnitine hydrochloride (30.06 g, 0.125 mol) was dissolved in anhydrous trifluoroacetic acid (100 ml), followed by the addition of excess cinnamoyl chloride in an ice bath. The resulting mixture was stirred at 318–323 K until the starting material disappeared as evidenced by TLC (about 20 h). After the reaction was completed, the solvent was removed in vacuo and 400 ml acetone were added. The mixture was stirred for another 2 h, the white precipitate was removed, and then 800 ml diethyl ether were added to the filtrate. The resultant mixture was cooled to room temperature and filtered, the white precipitate obtained was then collected and recrystallized from ethanol-diethyl ether (V:V=1:4) to afford the target compound as colourless needles (36.30 g, 76.0% yield).
3. Preparation of (R,E)-4-chloro-2-(cinnamoyloxy)- N,N,N-trimethyl-4-oxobutan-1-ammonium chloride:
(R,E)-3-carboxy-2-(cinnamoyloxy)-N,N,N-trimethylpropan -1-ammonium chloride (26.4 g, 0.09 mol) was dissolved in 100 ml of dichlormethane at 273 K, to which freshly distilled oxalyl chloride (15 ml, 0.12 mol) was added dropwise. The resulting mixture was reacted at 318–323 K for 4 h. The solvent was removed in vacuo and the white residue obtained was directly used in the following reaction without further purification.
4. Synthesis of the title compound
The above intermediate was dissolved in 100 ml of anhydrous dimethyl sulfoxide (DMSO) followed by the addition of phenylmethanol (20 ml, 0.18 mol) at room temperature. The resulting mixture was reacted at 323 K for 5 h. After adding 80 ml of diethyl ether and stirring for another 2 h, a white precipitate was collected and dried in vacuo at 313 K. The crude product was recrystallized from a mixture of acetic ether/diethyl ether (V:V=1:2, 75 ml) to give the title compound as colourless crystals (21.80 g, 58.0% yield).
m.p. 363–365 K; IR (KBr, ν cm-1): 3067, 3027(CH), 1729, 1695(C=O), 1669, 1628(C=C), 1504, 1588(Ar—C), 1486, 1431(CH2, CH3), 1208(C—N) 681, 695, 723, 758, 917(Ar); 1H NMR (MeOD, p.p.m.): 2.71–2.76(m, 2H, –CH2), 2.98(s, 9H, –CH3), 3.58, 3.60 (d, 2H, N—CH2), 3.71–3.76 (dd, 1H, J=5.7; 13.2 Hz, N—CH2), 4.79(d, 2H, O—CH2), 5.60–5.64(m, 1H, –CH—O), 6.05, 6.10 (1H, d, J=4.8 Hz, CH=), 6.34, 6.40 (1H, d, J=4.8 Hz, =CH), 6.84–7.00 (m, 5H, CH2C6H5), 7.10–7.40 (m, 5H, CH—C6H5); 13C NMR (MeOD, p.p.m.): 26.45(C7), 129.0(C1), 127.7(C2,C4,C6), 129.0(C3), 141.2(C5), 68.4(C7), 167.1(C8), 37.2(C9), 63.6(C10), 70.2(C11), 54.7(C12,C13,C14), 158.5(C15), 128.2(C16), 136.2(C17), 135.2(C18), 126.4(C19, C23), 128.7(C20, C21, C22); ESI-MS (m/z): 436.2 [M+H]+; Analysis found: C 61.28, H 6.83, N 3.01%; calculated for C23H29O4Cl2N: C 60.74, H 6.38, N 3.08%.
20 mg of the title compound were dissolved in 5 ml of 95% methanol, then a mixture of acetic acid and diethyl ether (V:V=1:2, 15 ml) was added slowly, the resulting slightly cloudy solution was kept at 263 K for 24 h. Slow evaporation gave colourless single crystals, which were suitable for X-Ray analysis.
All H atoms except H1A bound to the Cl atoms were placed in geometrically calculated positions and refined using a riding model with C—H = 0.97 Å (for CH2 groups) and 0.96 Å (for CH3 groups). Their isotropic displacement parameters Uiso were set to 1.2 times (1.5 times for CH3 groups) the equivalent displacement parameter Ueq of their parent atoms.
In the refinement, the H atom attached to Cl atom was obtained from a difference density map as the highest peak after assignement of all other hydrogen atoms. The peak (0.32 e Å-3 at 0.2314 0.4121 0.2017) was localized 0.68 Å from Cl(2) and 1.32 Å from Cl(1), respectively. Considering the charge equilibrium, the H atom attached to the Cl atom could be suitable for the peak. Upon refinement the R factor dropped from 0.0511 to 0.0489, and the equivalent dispalcement parameter of the H atom refined to 0.091. In the final model the Uiso value was set to be 1.5 times Ueq of that of the closest Cl atom.
L-carnitine and cinnamic acid are reported to have some pharmaceutical applications (Crill & Helms, 2007; Christov et al., 2006; Kim et al., 2006). In order to study the biological activities of novel synthetic L-carnitine derivatives, a cinnamoyl L-carnitine benzoate was prepared and its crystal structure (Fig. 1) is reported here.
The title compound is a quaternary ammonium salt with a scaffold similar to that of acetyl-L-carnitine hydrochloride (Destro & Heyda, 1977; Weber et al., 1995). C16—C17 (1.332 Å) and C15—C16 and C17—C18 (1.467 and 1.466 Å) have bond lengths typical for partially delocalized C—C single and C=C double bonds, thus pointing towards the existence of a conjugated system along the chain O3—C15—C16—C17—C18. All other bond distances and angles are well within the expected ranges.
The compound is a hydrochloride solvate and the two chlorine atoms in the structure are tightly bonded by a strong Cl—H···Cl hydrogen bond as is evident from the small separation of the two chlorine atoms (3.068 (2) Å), which is very close to the standard value of 3.11 Å in hydrogen dichloride ions (Atwood et al., 1990). Cl···Cl nonbonding contacts other than Cl—H···Cl hydrogen bonds exhibit values usually larger than 3.36 Å (Stoyanov et al., 2006). The hydrogen atom was tentatively localized in a difference density map, and the values are in agreement with previously reported data when taking the accuracy of the X-ray experiment for the determination of hydrogen atoms into account. The refined H—Cl distance of 1.37 Å is slightly longer than that reported for the covalent HCl molecule in the gaseous state without a Cl—H···Cl bond (1.28 Å, Luo et al., 2002), and the H···Cl separation of 1.70 Å is slightly longer than the previously reported values (1.65 Å, Atwood et al., 1990).
The molecules are held together partly by a range of two C—H···O and, owing to the existence of two benzene rings, two C—H···π interactions. (see the Hydrogen-bond geometry table), which contribute to the stabilization of the molecular geometry and the crystal strucuture.
Adams & Ulich (1920) report the synthesis of cinnamoyl chloride. Pharmaceutical applications of L-carnitine and cinnamic acid are described by Christov et al. (2006), Crill & Helms (2007) and Kim et al. (2006). Acetyl-L-carnitine hydrochloride is described by Destro & Heyda (1977) and Weber et al. (1995). Background information related to Cl—H···Cl hydrogen bonds is given by Stoyanov et al. (2006), Atwood et al. (1990) and Luo et al. (2002).
Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: APEX2 (Bruker, 2005); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
C23H28NO4+·Cl−·HCl | Dx = 1.236 Mg m−3 |
Mr = 454.37 | Melting point: 363-365K K |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.1670 (4) Å | Cell parameters from 3797 reflections |
b = 10.4488 (4) Å | θ = 2.6–21.0° |
c = 22.9795 (11) Å | µ = 0.29 mm−1 |
V = 2441.18 (18) Å3 | T = 293 K |
Z = 4 | Prism, colourless |
F(000) = 960 | 0.41 × 0.26 × 0.23 mm |
Bruker APEXII CCD area-detector diffractometer | 5648 independent reflections |
Radiation source: fine-focus sealed tube | 3350 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.040 |
φ and ω scans | θmax = 27.6°, θmin = 2.1° |
Absorption correction: multi-scan (APEX2; Bruker, 2005) | h = −13→10 |
Tmin = 0.889, Tmax = 0.935 | k = −13→13 |
19537 measured reflections | l = −29→29 |
Refinement on F2 | H-atom parameters constrained |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.1668P)2 + 0.001P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.049 | (Δ/σ)max < 0.001 |
wR(F2) = 0.206 | Δρmax = 0.24 e Å−3 |
S = 0.81 | Δρmin = −0.25 e Å−3 |
5648 reflections | Absolute structure: Flack (1983), 2454 Friedel pairs |
279 parameters | Absolute structure parameter: −0.01 (11) |
0 restraints |
C23H28NO4+·Cl−·HCl | V = 2441.18 (18) Å3 |
Mr = 454.37 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 10.1670 (4) Å | µ = 0.29 mm−1 |
b = 10.4488 (4) Å | T = 293 K |
c = 22.9795 (11) Å | 0.41 × 0.26 × 0.23 mm |
Bruker APEXII CCD area-detector diffractometer | 5648 independent reflections |
Absorption correction: multi-scan (APEX2; Bruker, 2005) | 3350 reflections with I > 2σ(I) |
Tmin = 0.889, Tmax = 0.935 | Rint = 0.040 |
19537 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | H-atom parameters constrained |
wR(F2) = 0.206 | Δρmax = 0.24 e Å−3 |
S = 0.81 | Δρmin = −0.25 e Å−3 |
5648 reflections | Absolute structure: Flack (1983), 2454 Friedel pairs |
279 parameters | Absolute structure parameter: −0.01 (11) |
0 restraints |
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 | 1.5794 (5) | 0.6771 (5) | 0.3970 (3) | 0.0975 (15) | |
H1 | 1.6264 | 0.7037 | 0.3645 | 0.117* | |
C2 | 1.6308 (5) | 0.6890 (5) | 0.4490 (3) | 0.108 (2) | |
H2 | 1.7145 | 0.7239 | 0.4527 | 0.130* | |
C3 | 1.5644 (7) | 0.6513 (5) | 0.4982 (3) | 0.109 (2) | |
H3 | 1.6028 | 0.6603 | 0.5347 | 0.131* | |
C4 | 1.4367 (5) | 0.5985 (4) | 0.49251 (19) | 0.0781 (11) | |
H4 | 1.3891 | 0.5742 | 0.5252 | 0.094* | |
C5 | 1.3849 (3) | 0.5841 (4) | 0.43810 (15) | 0.0598 (8) | |
C6 | 1.4565 (5) | 0.6255 (4) | 0.39051 (19) | 0.0771 (11) | |
H6 | 1.4205 | 0.6182 | 0.3535 | 0.093* | |
C7 | 1.2561 (5) | 0.5165 (5) | 0.4303 (2) | 0.0883 (14) | |
H7A | 1.2715 | 0.4291 | 0.4179 | 0.106* | |
H7B | 1.2092 | 0.5142 | 0.4671 | 0.106* | |
C8 | 1.0922 (3) | 0.5120 (3) | 0.35739 (15) | 0.0540 (7) | |
C9 | 1.0245 (3) | 0.5897 (3) | 0.31191 (15) | 0.0551 (7) | |
H9A | 1.0902 | 0.6249 | 0.2859 | 0.066* | |
H9B | 0.9803 | 0.6609 | 0.3306 | 0.066* | |
C10 | 0.9248 (3) | 0.5160 (3) | 0.27626 (13) | 0.0484 (7) | |
H10 | 0.9662 | 0.4409 | 0.2585 | 0.058* | |
C11 | 0.8743 (3) | 0.6043 (3) | 0.23001 (14) | 0.0594 (8) | |
H11A | 0.9495 | 0.6339 | 0.2078 | 0.071* | |
H11B | 0.8372 | 0.6785 | 0.2493 | 0.071* | |
C12 | 0.7716 (6) | 0.6435 (6) | 0.1363 (2) | 0.113 (2) | |
H12A | 0.7571 | 0.7297 | 0.1494 | 0.170* | |
H12B | 0.7022 | 0.6189 | 0.1103 | 0.170* | |
H12C | 0.8544 | 0.6387 | 0.1164 | 0.170* | |
C13 | 0.8013 (5) | 0.4216 (5) | 0.1668 (2) | 0.0918 (13) | |
H13A | 0.7359 | 0.3963 | 0.1390 | 0.138* | |
H13B | 0.7994 | 0.3642 | 0.1994 | 0.138* | |
H13C | 0.8866 | 0.4189 | 0.1489 | 0.138* | |
C14 | 0.6389 (4) | 0.5535 (6) | 0.2142 (2) | 0.0973 (15) | |
H14A | 0.6177 | 0.6371 | 0.2287 | 0.146* | |
H14B | 0.6376 | 0.4931 | 0.2457 | 0.146* | |
H14C | 0.5754 | 0.5288 | 0.1854 | 0.146* | |
C15 | 0.7964 (3) | 0.3504 (3) | 0.32137 (13) | 0.0478 (7) | |
C16 | 0.6979 (3) | 0.3258 (3) | 0.36670 (13) | 0.0460 (6) | |
H16 | 0.6558 | 0.3936 | 0.3852 | 0.055* | |
C17 | 0.6692 (3) | 0.2054 (3) | 0.38118 (13) | 0.0472 (7) | |
H17 | 0.7132 | 0.1416 | 0.3608 | 0.057* | |
C18 | 0.5758 (3) | 0.1630 (3) | 0.42578 (13) | 0.0482 (7) | |
C19 | 0.5485 (3) | 0.0341 (3) | 0.43073 (15) | 0.0553 (8) | |
H19 | 0.5914 | −0.0241 | 0.4067 | 0.066* | |
C20 | 0.4571 (4) | −0.0096 (4) | 0.47148 (17) | 0.0682 (10) | |
H20 | 0.4374 | −0.0964 | 0.4737 | 0.082* | |
C21 | 0.3967 (4) | 0.0752 (4) | 0.50804 (17) | 0.0734 (11) | |
H21 | 0.3367 | 0.0459 | 0.5355 | 0.088* | |
C22 | 0.4246 (4) | 0.2045 (4) | 0.50423 (18) | 0.0758 (11) | |
H22 | 0.3829 | 0.2619 | 0.5291 | 0.091* | |
C23 | 0.5146 (4) | 0.2490 (4) | 0.46349 (15) | 0.0634 (9) | |
H23 | 0.5340 | 0.3359 | 0.4614 | 0.076* | |
Cl2 | 0.34728 (19) | 0.4253 (2) | 0.25740 (8) | 0.1340 (6) | |
N1 | 0.7733 (3) | 0.5557 (3) | 0.18732 (12) | 0.0619 (7) | |
O1 | 1.1776 (3) | 0.5832 (2) | 0.38699 (11) | 0.0688 (7) | |
O2 | 1.0754 (3) | 0.4004 (2) | 0.36643 (13) | 0.0726 (7) | |
O3 | 0.81958 (19) | 0.47657 (18) | 0.31532 (9) | 0.0479 (5) | |
O4 | 0.8494 (3) | 0.2695 (2) | 0.29206 (11) | 0.0683 (7) | |
Cl1 | 0.15256 (13) | 0.39911 (12) | 0.15612 (6) | 0.0978 (4) | |
H1A | 0.2369 | 0.4149 | 0.2018 | 0.147* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.070 (3) | 0.079 (3) | 0.144 (5) | −0.001 (2) | 0.023 (3) | −0.009 (3) |
C2 | 0.071 (3) | 0.066 (3) | 0.187 (7) | 0.001 (2) | −0.032 (4) | 0.007 (4) |
C3 | 0.124 (4) | 0.074 (3) | 0.130 (5) | 0.010 (3) | −0.081 (4) | −0.003 (3) |
C4 | 0.095 (3) | 0.065 (2) | 0.075 (2) | 0.016 (2) | −0.020 (2) | 0.0058 (19) |
C5 | 0.0508 (18) | 0.064 (2) | 0.064 (2) | 0.0027 (16) | −0.0048 (15) | −0.0002 (16) |
C6 | 0.077 (3) | 0.074 (2) | 0.081 (3) | −0.006 (2) | 0.006 (2) | −0.017 (2) |
C7 | 0.066 (2) | 0.111 (3) | 0.088 (3) | −0.018 (2) | −0.023 (2) | 0.038 (3) |
C8 | 0.0402 (15) | 0.0566 (18) | 0.0652 (19) | −0.0015 (13) | 0.0066 (14) | 0.0054 (15) |
C9 | 0.0482 (16) | 0.0491 (15) | 0.0681 (19) | −0.0052 (14) | −0.0019 (15) | 0.0114 (15) |
C10 | 0.0399 (14) | 0.0460 (15) | 0.0593 (17) | −0.0063 (13) | 0.0092 (13) | 0.0046 (13) |
C11 | 0.0593 (19) | 0.0567 (18) | 0.0623 (19) | −0.0174 (16) | −0.0050 (15) | 0.0104 (16) |
C12 | 0.129 (4) | 0.124 (4) | 0.086 (3) | −0.052 (4) | −0.041 (3) | 0.049 (3) |
C13 | 0.097 (3) | 0.088 (3) | 0.091 (3) | −0.004 (3) | −0.017 (3) | −0.018 (2) |
C14 | 0.053 (2) | 0.140 (5) | 0.100 (3) | 0.003 (3) | −0.006 (2) | 0.014 (3) |
C15 | 0.0490 (17) | 0.0421 (14) | 0.0524 (16) | −0.0023 (13) | 0.0060 (13) | −0.0033 (13) |
C16 | 0.0440 (15) | 0.0473 (15) | 0.0466 (14) | −0.0017 (12) | 0.0046 (12) | 0.0005 (12) |
C17 | 0.0445 (15) | 0.0454 (15) | 0.0517 (15) | −0.0005 (13) | 0.0039 (13) | −0.0024 (12) |
C18 | 0.0408 (14) | 0.0533 (16) | 0.0505 (15) | 0.0009 (13) | −0.0002 (13) | 0.0099 (13) |
C19 | 0.0486 (17) | 0.0518 (16) | 0.0654 (19) | 0.0045 (15) | 0.0097 (15) | 0.0088 (15) |
C20 | 0.063 (2) | 0.059 (2) | 0.082 (2) | −0.0047 (18) | 0.0094 (19) | 0.0221 (18) |
C21 | 0.066 (2) | 0.085 (3) | 0.069 (2) | −0.010 (2) | 0.0172 (19) | 0.019 (2) |
C22 | 0.076 (2) | 0.084 (3) | 0.068 (2) | −0.004 (2) | 0.028 (2) | −0.0030 (19) |
C23 | 0.068 (2) | 0.057 (2) | 0.065 (2) | −0.0015 (17) | 0.0157 (18) | −0.0021 (16) |
Cl2 | 0.1186 (12) | 0.1575 (15) | 0.1259 (11) | −0.0422 (12) | 0.0160 (10) | −0.0017 (11) |
N1 | 0.0561 (16) | 0.0646 (17) | 0.0651 (17) | −0.0086 (13) | −0.0024 (13) | 0.0080 (14) |
O1 | 0.0624 (14) | 0.0648 (14) | 0.0792 (16) | −0.0067 (12) | −0.0189 (12) | 0.0145 (12) |
O2 | 0.0708 (16) | 0.0542 (14) | 0.0927 (17) | −0.0047 (13) | −0.0099 (14) | 0.0186 (13) |
O3 | 0.0420 (11) | 0.0416 (10) | 0.0601 (11) | −0.0014 (8) | 0.0139 (9) | 0.0014 (9) |
O4 | 0.0802 (16) | 0.0450 (11) | 0.0795 (15) | −0.0014 (12) | 0.0327 (14) | −0.0070 (11) |
Cl1 | 0.0803 (7) | 0.0913 (8) | 0.1218 (9) | −0.0201 (6) | 0.0286 (7) | −0.0118 (7) |
C1—C2 | 1.310 (8) | C12—H12C | 0.9600 |
C1—C6 | 1.368 (7) | C13—N1 | 1.506 (6) |
C1—H1 | 0.9300 | C13—H13A | 0.9600 |
C2—C3 | 1.374 (9) | C13—H13B | 0.9600 |
C2—H2 | 0.9300 | C13—H13C | 0.9600 |
C3—C4 | 1.416 (9) | C14—N1 | 1.499 (6) |
C3—H3 | 0.9300 | C14—H14A | 0.9600 |
C4—C5 | 1.365 (5) | C14—H14B | 0.9600 |
C4—H4 | 0.9300 | C14—H14C | 0.9600 |
C5—C6 | 1.383 (6) | C15—O4 | 1.208 (4) |
C5—C7 | 1.499 (6) | C15—O3 | 1.347 (3) |
C6—H6 | 0.9300 | C15—C16 | 1.468 (4) |
C7—O1 | 1.454 (5) | C16—C17 | 1.333 (4) |
C7—H7A | 0.9700 | C16—H16 | 0.9300 |
C7—H7B | 0.9700 | C17—C18 | 1.466 (4) |
C8—O2 | 1.197 (4) | C17—H17 | 0.9300 |
C8—O1 | 1.330 (4) | C18—C19 | 1.379 (5) |
C8—C9 | 1.492 (5) | C18—C23 | 1.395 (5) |
C9—C10 | 1.514 (4) | C19—C20 | 1.396 (5) |
C9—H9A | 0.9700 | C19—H19 | 0.9300 |
C9—H9B | 0.9700 | C20—C21 | 1.367 (6) |
C10—O3 | 1.456 (3) | C20—H20 | 0.9300 |
C10—C11 | 1.497 (4) | C21—C22 | 1.383 (7) |
C10—H10 | 0.9800 | C21—H21 | 0.9300 |
C11—N1 | 1.508 (4) | C22—C23 | 1.390 (5) |
C11—H11A | 0.9700 | C22—H22 | 0.9300 |
C11—H11B | 0.9700 | C23—H23 | 0.9300 |
C12—N1 | 1.488 (5) | Cl2—H1A | 1.7033 |
C12—H12A | 0.9600 | Cl1—H1A | 1.3661 |
C12—H12B | 0.9600 | ||
C2—C1—C6 | 120.1 (6) | H12A—C12—H12C | 109.5 |
C2—C1—H1 | 119.9 | H12B—C12—H12C | 109.5 |
C6—C1—H1 | 119.9 | N1—C13—H13A | 109.5 |
C1—C2—C3 | 121.8 (5) | N1—C13—H13B | 109.5 |
C1—C2—H2 | 119.1 | H13A—C13—H13B | 109.5 |
C3—C2—H2 | 119.1 | N1—C13—H13C | 109.5 |
C2—C3—C4 | 119.0 (5) | H13A—C13—H13C | 109.5 |
C2—C3—H3 | 120.5 | H13B—C13—H13C | 109.5 |
C4—C3—H3 | 120.5 | N1—C14—H14A | 109.5 |
C5—C4—C3 | 118.8 (5) | N1—C14—H14B | 109.5 |
C5—C4—H4 | 120.6 | H14A—C14—H14B | 109.5 |
C3—C4—H4 | 120.6 | N1—C14—H14C | 109.5 |
C4—C5—C6 | 119.1 (4) | H14A—C14—H14C | 109.5 |
C4—C5—C7 | 119.9 (4) | H14B—C14—H14C | 109.5 |
C6—C5—C7 | 120.9 (4) | O4—C15—O3 | 123.3 (3) |
C1—C6—C5 | 121.1 (5) | O4—C15—C16 | 125.3 (3) |
C1—C6—H6 | 119.4 | O3—C15—C16 | 111.4 (2) |
C5—C6—H6 | 119.4 | C17—C16—C15 | 119.4 (3) |
O1—C7—C5 | 109.6 (3) | C17—C16—H16 | 120.3 |
O1—C7—H7A | 109.8 | C15—C16—H16 | 120.3 |
C5—C7—H7A | 109.8 | C16—C17—C18 | 127.0 (3) |
O1—C7—H7B | 109.8 | C16—C17—H17 | 116.5 |
C5—C7—H7B | 109.8 | C18—C17—H17 | 116.5 |
H7A—C7—H7B | 108.2 | C19—C18—C23 | 119.2 (3) |
O2—C8—O1 | 123.3 (3) | C19—C18—C17 | 118.9 (3) |
O2—C8—C9 | 125.9 (3) | C23—C18—C17 | 121.9 (3) |
O1—C8—C9 | 110.8 (3) | C18—C19—C20 | 120.6 (3) |
C8—C9—C10 | 114.3 (3) | C18—C19—H19 | 119.7 |
C8—C9—H9A | 108.7 | C20—C19—H19 | 119.7 |
C10—C9—H9A | 108.7 | C21—C20—C19 | 120.0 (3) |
C8—C9—H9B | 108.7 | C21—C20—H20 | 120.0 |
C10—C9—H9B | 108.7 | C19—C20—H20 | 120.0 |
H9A—C9—H9B | 107.6 | C20—C21—C22 | 120.1 (3) |
O3—C10—C11 | 111.1 (3) | C20—C21—H21 | 119.9 |
O3—C10—C9 | 107.6 (2) | C22—C21—H21 | 119.9 |
C11—C10—C9 | 107.5 (2) | C21—C22—C23 | 120.3 (4) |
O3—C10—H10 | 110.2 | C21—C22—H22 | 119.8 |
C11—C10—H10 | 110.2 | C23—C22—H22 | 119.8 |
C9—C10—H10 | 110.2 | C22—C23—C18 | 119.8 (3) |
C10—C11—N1 | 119.2 (3) | C22—C23—H23 | 120.1 |
C10—C11—H11A | 107.5 | C18—C23—H23 | 120.1 |
N1—C11—H11A | 107.5 | C12—N1—C14 | 108.9 (4) |
C10—C11—H11B | 107.5 | C12—N1—C13 | 109.2 (4) |
N1—C11—H11B | 107.5 | C14—N1—C13 | 106.7 (4) |
H11A—C11—H11B | 107.0 | C12—N1—C11 | 108.2 (3) |
N1—C12—H12A | 109.5 | C14—N1—C11 | 111.0 (3) |
N1—C12—H12B | 109.5 | C13—N1—C11 | 112.8 (3) |
H12A—C12—H12B | 109.5 | C8—O1—C7 | 116.1 (3) |
N1—C12—H12C | 109.5 | C15—O3—C10 | 118.0 (2) |
C6—C1—C2—C3 | −0.2 (8) | C16—C17—C18—C23 | −7.1 (5) |
C1—C2—C3—C4 | −0.2 (8) | C23—C18—C19—C20 | 2.4 (5) |
C2—C3—C4—C5 | 1.5 (7) | C17—C18—C19—C20 | −178.0 (3) |
C3—C4—C5—C6 | −2.3 (6) | C18—C19—C20—C21 | −1.9 (6) |
C3—C4—C5—C7 | 173.8 (4) | C19—C20—C21—C22 | 0.9 (6) |
C2—C1—C6—C5 | −0.6 (7) | C20—C21—C22—C23 | −0.3 (7) |
C4—C5—C6—C1 | 1.9 (6) | C21—C22—C23—C18 | 0.8 (6) |
C7—C5—C6—C1 | −174.1 (4) | C19—C18—C23—C22 | −1.8 (5) |
C4—C5—C7—O1 | 139.3 (4) | C17—C18—C23—C22 | 178.6 (3) |
C6—C5—C7—O1 | −44.7 (6) | C10—C11—N1—C12 | −162.3 (4) |
O2—C8—C9—C10 | 1.3 (5) | C10—C11—N1—C14 | 78.3 (4) |
O1—C8—C9—C10 | −179.7 (3) | C10—C11—N1—C13 | −41.3 (4) |
C8—C9—C10—O3 | 64.7 (3) | O2—C8—O1—C7 | 2.7 (5) |
C8—C9—C10—C11 | −175.5 (3) | C9—C8—O1—C7 | −176.3 (3) |
O3—C10—C11—N1 | −62.9 (4) | C5—C7—O1—C8 | 152.0 (3) |
C9—C10—C11—N1 | 179.6 (3) | O4—C15—O3—C10 | −7.4 (5) |
O4—C15—C16—C17 | 5.6 (5) | C16—C15—O3—C10 | 173.8 (2) |
O3—C15—C16—C17 | −175.6 (3) | C11—C10—O3—C15 | 122.9 (3) |
C15—C16—C17—C18 | 178.9 (3) | C9—C10—O3—C15 | −119.7 (3) |
C16—C17—C18—C19 | 173.3 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C9—H9A···O4i | 0.97 | 2.42 | 3.299 (4) | 150 |
C11—H11A···O4i | 0.97 | 2.49 | 3.336 (4) | 146 |
C12—H12A···O2i | 0.96 | 2.49 | 3.103 (6) | 121 |
C13—H13C···Cl1ii | 0.96 | 2.72 | 3.587 (6) | 151 |
C12—H12B···Cg2iii | 0.96 | 2.62 | 3.551 (5) | 164 |
C20—H20···Cg1iv | 0.93 | 2.95 | 3.776 (4) | 148 |
Cl1—H1A···Cl2 | 1.37 | 1.70 | 3.068 (2) | 176 |
C10—H10···O4 | 0.98 | 2.28 | 2.712 (4) | 105 |
C13—H13B···O4 | 0.96 | 2.40 | 3.324 (6) | 161 |
C14—H14B···O3 | 0.96 | 2.45 | 3.069 (5) | 122 |
C17—H17···O4 | 0.93 | 2.49 | 2.828 (4) | 102 |
Symmetry codes: (i) −x+2, y+1/2, −z+1/2; (ii) x+1, y, z; (iii) −x+1, y+1/2, −z+1/2; (iv) x−1, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | C23H28NO4+·Cl−·HCl |
Mr | 454.37 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 293 |
a, b, c (Å) | 10.1670 (4), 10.4488 (4), 22.9795 (11) |
V (Å3) | 2441.18 (18) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.29 |
Crystal size (mm) | 0.41 × 0.26 × 0.23 |
Data collection | |
Diffractometer | Bruker APEXII CCD area-detector |
Absorption correction | Multi-scan (APEX2; Bruker, 2005) |
Tmin, Tmax | 0.889, 0.935 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19537, 5648, 3350 |
Rint | 0.040 |
(sin θ/λ)max (Å−1) | 0.652 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.206, 0.81 |
No. of reflections | 5648 |
No. of parameters | 279 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.24, −0.25 |
Absolute structure | Flack (1983), 2454 Friedel pairs |
Absolute structure parameter | −0.01 (11) |
Computer programs: APEX2 (Bruker, 2005), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), WinGX (Farrugia, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
C9—H9A···O4i | 0.97 | 2.42 | 3.299 (4) | 150.2 |
C11—H11A···O4i | 0.97 | 2.49 | 3.336 (4) | 145.9 |
C12—H12A···O2i | 0.96 | 2.49 | 3.103 (6) | 121.3 |
C13—H13C···Cl1ii | 0.96 | 2.72 | 3.587 (6) | 151.1 |
C12—H12B···Cg2iii | 0.96 | 2.62 | 3.551 (5) | 164.1 |
C20—H20···Cg1iv | 0.93 | 2.95 | 3.776 (4) | 148.4 |
Cl1—H1A···Cl2 | 1.37 | 1.70 | 3.068 (2) | 176.1 |
C10—H10···O4 | 0.98 | 2.28 | 2.712 (4) | 105.4 |
C13—H13B···O4 | 0.96 | 2.40 | 3.324 (6) | 160.9 |
C14—H14B···O3 | 0.96 | 2.45 | 3.069 (5) | 121.8 |
C17—H17···O4 | 0.93 | 2.49 | 2.828 (4) | 101.6 |
Symmetry codes: (i) −x+2, y+1/2, −z+1/2; (ii) x+1, y, z; (iii) −x+1, y+1/2, −z+1/2; (iv) x−1, y−1, z. |
L-carnitine and cinnamic acid are reported to have some pharmaceutical applications (Crill & Helms, 2007; Christov et al., 2006; Kim et al., 2006). In order to study the biological activities of novel synthetic L-carnitine derivatives, a cinnamoyl L-carnitine benzoate was prepared and its crystal structure (Fig. 1) is reported here.
The title compound is a quaternary ammonium salt with a scaffold similar to that of acetyl-L-carnitine hydrochloride (Destro & Heyda, 1977; Weber et al., 1995). C16—C17 (1.332 Å) and C15—C16 and C17—C18 (1.467 and 1.466 Å) have bond lengths typical for partially delocalized C—C single and C=C double bonds, thus pointing towards the existence of a conjugated system along the chain O3—C15—C16—C17—C18. All other bond distances and angles are well within the expected ranges.
The compound is a hydrochloride solvate and the two chlorine atoms in the structure are tightly bonded by a strong Cl—H···Cl hydrogen bond as is evident from the small separation of the two chlorine atoms (3.068 (2) Å), which is very close to the standard value of 3.11 Å in hydrogen dichloride ions (Atwood et al., 1990). Cl···Cl nonbonding contacts other than Cl—H···Cl hydrogen bonds exhibit values usually larger than 3.36 Å (Stoyanov et al., 2006). The hydrogen atom was tentatively localized in a difference density map, and the values are in agreement with previously reported data when taking the accuracy of the X-ray experiment for the determination of hydrogen atoms into account. The refined H—Cl distance of 1.37 Å is slightly longer than that reported for the covalent HCl molecule in the gaseous state without a Cl—H···Cl bond (1.28 Å, Luo et al., 2002), and the H···Cl separation of 1.70 Å is slightly longer than the previously reported values (1.65 Å, Atwood et al., 1990).
The molecules are held together partly by a range of two C—H···O and, owing to the existence of two benzene rings, two C—H···π interactions. (see the Hydrogen-bond geometry table), which contribute to the stabilization of the molecular geometry and the crystal strucuture.