organic compounds
(4S,5S)-2-(2-Fluorophenyl)-1,3-dioxolane-4,5-dicarboxamide
aSate Key Laboratory of Materials-Oriented Chemical Engineering, College of Life Science and Pharmaceutical Engineering, Nanjing University of Technology, Xinmofan Road No. 5 Nanjing, Nanjing 210009, People's Republic of China, and bCollege of Science, Nanjing University of Technolgy, Xinmofan Road No. 5 Nanjing, Nanjing 210009, People's Republic of China
*Correspondence e-mail: dcwang@njut.edu.cn
In the molecule of the title compound, C11H11FN2O4, the five-membered ring adopts an An intramolecular N—H⋯F hydrogen bond occurs. In the intermolecular N—H⋯O hydrogen bonds link the molecules.
Related literature
For general background, see: Kim et al. (1994); Pandey et al. (1997). For bond-length data, see: Allen et al. (1987).
Experimental
Crystal data
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Refinement
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Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
Supporting information
10.1107/S1600536808039470/hk2584sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808039470/hk2584Isup2.hkl
For the preparatrion of the title compound, a mixture of 2-fluorbenzaldehyde (302 mg, 2.43 mmol), (2S,3S)-diethyltartrate (500 mg, 2.43 mmol), anhydrous copper sulfate (776 mg, 2.86 mmol) and one drop of methanesulfonic acid in anhydrous toluen (8 ml) was stirred at room temperature for 12 h. Anhydrous potassium carbonate (40 mg) was added to the reaction mixture, which was then stirred for a further 20 min. The resulting colorless precipitate was obtained by evaporation and dried in vacuo (yield; 87%). The obtained colorless product (10 mmol) was dissolved in anhydrous ethanol (50 ml), then a current of dry ammonia, dried with calcium chloride passed into the reaction mixture at room temperature for about 6 h. The reaction mixture was evaporated to dryness. Pure compound was obtained by crystallization from dichloromethane. Crystals suitable for X-ray analysis were obatined by slow evaporation of an ethanol solution after one week.
H atoms were positioned geometrically, with N-H = 0.86 Å (for NH2) and C-H = 0.93 and 0.98 Å for aromatic and methine H, respectively, and constrained to ride on their parent atoms with Uiso(H) = 1.2Ueq(C,N).
Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell
CAD-4 Software (Enraf–Nonius, 1985); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. |
C11H11FN2O4 | F(000) = 528 |
Mr = 254.22 | Dx = 1.529 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 25 reflections |
a = 4.8760 (5) Å | θ = 9–12° |
b = 9.1290 (7) Å | µ = 0.13 mm−1 |
c = 24.8160 (9) Å | T = 294 K |
V = 1104.63 (15) Å3 | Block, colorless |
Z = 4 | 0.40 × 0.10 × 0.10 mm |
Enraf–Nonius CAD-4 diffractometer | 898 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.072 |
Graphite monochromator | θmax = 26.0°, θmin = 1.6° |
ω/2θ scans | h = −5→5 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→11 |
Tmin = 0.978, Tmax = 0.987 | l = 0→30 |
2157 measured reflections | 3 standard reflections every 120 min |
1301 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)] = 0.060 | H-atom parameters constrained |
wR(F2) = 0.125 | w = 1/[σ2(Fo2) + (0.002P)2 + 1.775P] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max < 0.001 |
1301 reflections | Δρmax = 0.27 e Å−3 |
164 parameters | Δρmin = −0.23 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.023 (4) |
C11H11FN2O4 | V = 1104.63 (15) Å3 |
Mr = 254.22 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 4.8760 (5) Å | µ = 0.13 mm−1 |
b = 9.1290 (7) Å | T = 294 K |
c = 24.8160 (9) Å | 0.40 × 0.10 × 0.10 mm |
Enraf–Nonius CAD-4 diffractometer | 898 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.072 |
Tmin = 0.978, Tmax = 0.987 | 3 standard reflections every 120 min |
2157 measured reflections | intensity decay: none |
1301 independent reflections |
R[F2 > 2σ(F2)] = 0.060 | 0 restraints |
wR(F2) = 0.125 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.27 e Å−3 |
1301 reflections | Δρmin = −0.23 e Å−3 |
164 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 | 0.6898 (8) | 0.3384 (4) | 0.36430 (13) | 0.0497 (10) | |
O2 | 0.9373 (9) | 0.5438 (3) | 0.37339 (12) | 0.0489 (10) | |
O3 | 1.1580 (8) | 0.2201 (5) | 0.44108 (17) | 0.0576 (11) | |
O4 | 0.7161 (10) | 0.6057 (4) | 0.50750 (13) | 0.0599 (12) | |
N1 | 0.7627 (11) | 0.0954 (4) | 0.44684 (15) | 0.0513 (12) | |
H1A | 0.8450 | 0.0144 | 0.4540 | 0.062* | |
H1B | 0.5866 | 0.0979 | 0.4449 | 0.062* | |
N2 | 0.5605 (12) | 0.6946 (5) | 0.42850 (18) | 0.0681 (16) | |
H2A | 0.4529 | 0.7561 | 0.4441 | 0.082* | |
H2B | 0.5674 | 0.6905 | 0.3939 | 0.082* | |
F1 | 0.4814 (11) | 0.6150 (5) | 0.30682 (15) | 0.1054 (16) | |
C1 | 0.6335 (15) | 0.5470 (7) | 0.2681 (2) | 0.0633 (18) | |
C2 | 0.572 (2) | 0.5797 (8) | 0.2158 (3) | 0.083 (2) | |
H2 | 0.4353 | 0.6472 | 0.2076 | 0.099* | |
C3 | 0.715 (2) | 0.5109 (8) | 0.1758 (3) | 0.088 (3) | |
H3 | 0.6700 | 0.5274 | 0.1399 | 0.105* | |
C4 | 0.9265 (19) | 0.4170 (9) | 0.1887 (2) | 0.095 (3) | |
H4 | 1.0286 | 0.3731 | 0.1615 | 0.114* | |
C5 | 0.9875 (19) | 0.3878 (8) | 0.2426 (2) | 0.076 (2) | |
H5 | 1.1281 | 0.3230 | 0.2511 | 0.092* | |
C6 | 0.8410 (14) | 0.4542 (6) | 0.2832 (2) | 0.0539 (16) | |
C7 | 0.9126 (13) | 0.4196 (6) | 0.34082 (18) | 0.0466 (13) | |
H7 | 1.0818 | 0.3617 | 0.3423 | 0.056* | |
C8 | 0.7392 (14) | 0.3487 (5) | 0.42137 (18) | 0.0461 (14) | |
H8 | 0.5644 | 0.3507 | 0.4409 | 0.055* | |
C9 | 0.8871 (13) | 0.4968 (5) | 0.42764 (19) | 0.0470 (14) | |
H9 | 1.0617 | 0.4826 | 0.4465 | 0.056* | |
C10 | 0.9067 (11) | 0.2163 (6) | 0.4389 (2) | 0.0407 (12) | |
C11 | 0.7142 (14) | 0.6068 (5) | 0.4576 (2) | 0.0492 (14) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.056 (2) | 0.0459 (19) | 0.0467 (19) | −0.007 (2) | −0.009 (2) | 0.0041 (16) |
O2 | 0.059 (2) | 0.0420 (18) | 0.0451 (19) | −0.007 (2) | 0.006 (2) | −0.0011 (15) |
O3 | 0.038 (2) | 0.059 (2) | 0.075 (3) | −0.006 (2) | −0.003 (2) | 0.007 (2) |
O4 | 0.079 (3) | 0.054 (2) | 0.046 (2) | −0.016 (3) | 0.003 (2) | −0.0063 (17) |
N1 | 0.055 (3) | 0.044 (2) | 0.055 (2) | −0.001 (3) | −0.009 (3) | 0.008 (2) |
N2 | 0.093 (4) | 0.060 (3) | 0.052 (3) | 0.020 (4) | 0.000 (3) | −0.004 (2) |
F1 | 0.106 (4) | 0.128 (4) | 0.082 (3) | 0.045 (4) | −0.016 (3) | 0.000 (3) |
C1 | 0.071 (5) | 0.066 (4) | 0.054 (3) | 0.003 (4) | −0.003 (3) | 0.005 (3) |
C2 | 0.106 (6) | 0.072 (4) | 0.070 (4) | −0.004 (5) | −0.022 (5) | 0.017 (4) |
C3 | 0.118 (7) | 0.091 (5) | 0.053 (4) | −0.021 (6) | −0.021 (5) | 0.021 (4) |
C4 | 0.108 (6) | 0.134 (7) | 0.043 (3) | −0.003 (7) | 0.000 (4) | −0.005 (4) |
C5 | 0.088 (5) | 0.087 (5) | 0.054 (4) | 0.010 (5) | 0.009 (4) | −0.010 (3) |
C6 | 0.068 (4) | 0.048 (3) | 0.046 (3) | −0.003 (3) | 0.000 (3) | 0.005 (2) |
C7 | 0.048 (3) | 0.047 (3) | 0.045 (3) | 0.002 (3) | 0.001 (3) | 0.000 (2) |
C8 | 0.063 (4) | 0.037 (2) | 0.038 (3) | 0.003 (3) | −0.002 (3) | 0.002 (2) |
C9 | 0.056 (4) | 0.042 (3) | 0.043 (3) | 0.001 (3) | 0.002 (3) | 0.003 (2) |
C10 | 0.045 (3) | 0.039 (3) | 0.038 (3) | 0.001 (3) | 0.001 (3) | −0.002 (2) |
C11 | 0.062 (4) | 0.039 (3) | 0.047 (3) | −0.009 (3) | 0.002 (3) | −0.006 (2) |
O1—C7 | 1.438 (6) | C3—C4 | 1.378 (11) |
O1—C8 | 1.440 (5) | C3—H3 | 0.9300 |
O2—C7 | 1.398 (5) | C4—H4 | 0.9300 |
O2—C9 | 1.434 (5) | C5—C4 | 1.396 (8) |
O3—C10 | 1.227 (6) | C5—H5 | 0.9300 |
O4—C11 | 1.240 (5) | C6—C1 | 1.372 (8) |
N1—C10 | 1.323 (6) | C6—C5 | 1.376 (8) |
N1—H1A | 0.8600 | C7—C6 | 1.505 (7) |
N1—H1B | 0.8600 | C7—H7 | 0.9800 |
N2—H2A | 0.8600 | C8—H8 | 0.9800 |
N2—H2B | 0.8600 | C9—C8 | 1.540 (7) |
F1—C1 | 1.363 (7) | C9—H9 | 0.9800 |
C2—C1 | 1.366 (7) | C10—C8 | 1.522 (7) |
C2—H2 | 0.9300 | C11—N2 | 1.313 (7) |
C3—C2 | 1.367 (10) | C11—C9 | 1.507 (7) |
C7—O1—C8 | 103.8 (4) | C5—C6—C7 | 118.9 (6) |
C7—O2—C9 | 106.6 (3) | O1—C7—C6 | 108.5 (5) |
C10—N1—H1A | 120.0 | O1—C7—H7 | 110.1 |
C10—N1—H1B | 120.0 | O2—C7—O1 | 104.4 (4) |
H1A—N1—H1B | 120.0 | O2—C7—C6 | 113.5 (4) |
C11—N2—H2A | 120.0 | O2—C7—H7 | 110.1 |
C11—N2—H2B | 120.0 | C6—C7—H7 | 110.1 |
H2A—N2—H2B | 120.0 | O1—C8—C10 | 108.6 (4) |
F1—C1—C2 | 116.8 (7) | O1—C8—C9 | 103.6 (4) |
F1—C1—C6 | 119.4 (5) | O1—C8—H8 | 109.9 |
C2—C1—C6 | 123.9 (7) | C9—C8—H8 | 109.9 |
C1—C2—C3 | 118.5 (7) | C10—C8—C9 | 114.6 (5) |
C1—C2—H2 | 120.8 | C10—C8—H8 | 109.9 |
C3—C2—H2 | 120.8 | O2—C9—C8 | 104.3 (4) |
C2—C3—C4 | 119.9 (6) | O2—C9—C11 | 111.0 (4) |
C2—C3—H3 | 120.0 | O2—C9—H9 | 109.8 |
C4—C3—H3 | 120.0 | C8—C9—H9 | 109.8 |
C3—C4—C5 | 120.1 (7) | C11—C9—C8 | 111.9 (5) |
C3—C4—H4 | 120.0 | C11—C9—H9 | 109.8 |
C5—C4—H4 | 120.0 | O3—C10—N1 | 123.2 (6) |
C6—C5—C4 | 120.5 (7) | O3—C10—C8 | 121.8 (5) |
C6—C5—H5 | 119.8 | O4—C11—N2 | 123.9 (6) |
C4—C5—H5 | 119.8 | O4—C11—C9 | 118.9 (5) |
C1—C6—C5 | 117.1 (6) | N1—C10—C8 | 114.8 (4) |
C1—C6—C7 | 124.1 (5) | N2—C11—C9 | 117.1 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O4i | 0.86 | 2.32 | 3.089 (4) | 149 |
N1—H1B···O3ii | 0.86 | 2.37 | 3.164 (4) | 153 |
N2—H2A···O4iii | 0.86 | 2.09 | 2.944 (5) | 172 |
N2—H2B···F1 | 0.86 | 2.31 | 3.130 (4) | 160 |
Symmetry codes: (i) x+1/2, −y+1/2, −z+1; (ii) x−1, y, z; (iii) x−1/2, −y+3/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C11H11FN2O4 |
Mr | 254.22 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 294 |
a, b, c (Å) | 4.8760 (5), 9.1290 (7), 24.8160 (9) |
V (Å3) | 1104.63 (15) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.13 |
Crystal size (mm) | 0.40 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Enraf–Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.978, 0.987 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2157, 1301, 898 |
Rint | 0.072 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.060, 0.125, 1.00 |
No. of reflections | 1301 |
No. of parameters | 164 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.27, −0.23 |
Computer programs: CAD-4 Software (Enraf–Nonius, 1985), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O4i | 0.86 | 2.32 | 3.089 (4) | 149 |
N1—H1B···O3ii | 0.86 | 2.37 | 3.164 (4) | 153 |
N2—H2A···O4iii | 0.86 | 2.09 | 2.944 (5) | 172 |
N2—H2B···F1 | 0.86 | 2.31 | 3.130 (4) | 160 |
Symmetry codes: (i) x+1/2, −y+1/2, −z+1; (ii) x−1, y, z; (iii) x−1/2, −y+3/2, −z+1. |
Acknowledgements
The authors thank the Center of Testing and Analysis, Nanjing University, for support.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Antitumor platinum drug is one kind of the most effective anticancer agents currently available. (2S,3S)-Diethyl 2,3-O-alkyltartrate analogues are starting materials for the syntheses of platinum complexes with antitumor activity (Kim et al., 1994), and are also important intermediates in organic syntheses (Pandey et al., 1997). As part of our studies on the syntheses and characterizations of these compounds, we report herein the crystal structure of the title compound.
In the molecule of the title compound (Fig. 1) the bond lengths (Allen et al., 1987) and angles are within normal ranges. The five-membered ring adopts envelope conformation with C7 atom displaced by 0.557 (3) Å from the plane of the other ring atoms. The intramolecular N-H···F hydrogen bond (Table 1) results in the formation of a nine-membered ring: (F1/C1/C6/C7/O2/C9/C11/N2/H2B) having twisted conformation.
In the crystal structure, intermolecular N-H···O hydrogen bonds (Table 1) link the molecules, in which they may be effective in the stabilization of the structure.