(4S,5S)-2-(2-Fluoro­phen­yl)-1,3-dioxolane-4,5-dicarboxamide

Li, X.-H.; Wang, D.-C.; Liu, B.-N.; Xu, W.

doi:10.1107/S1600536808039470

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 64| Part 12| December 2008| Page o2499

doi:10.1107/S1600536808039470

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(4S,5S)-2-(2-Fluorophenyl)-1,3-dioxolane-4,5-dicarboxamide

Xin-Hua Li,^a De-Cai Wang,^a ^* Bo-Nian Liu ^b and Wei Xu ^a

^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

(Received 21 November 2008; accepted 24 November 2008; online 29 November 2008)

In the molecule of the title compound, C₁₁H₁₁FN₂O₄, the five-membered ring adopts an envelope conformation. An intramolecular N—H⋯F hydrogen bond occurs. In the crystal structure, 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

C₁₁H₁₁FN₂O₄
M_r = 254.22
Orthorhombic, P 2₁ 2₁ 2₁
a = 4.8760 (5) Å
b = 9.1290 (7) Å
c = 24.8160 (9) Å
V = 1104.63 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 294 (2) K
0.40 × 0.10 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.978, T_max = 0.987
2157 measured reflections
1301 independent reflections
898 reflections with I > 2σ(I)
R_int = 0.072
3 standard reflections frequency: 120 min intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.060
wR(F²) = 0.125
S = 1.00
1301 reflections
164 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (ii) x-1, y, z; (iii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ .

Data collection: CAD-4 Software (Enraf–Nonius, 1985 ); cell refinement: 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

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808039470/hk2584sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808039470/hk2584Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

For general background, see: Kim et al. (1994); Pandey et al. (1997). For bond-length data, see: Allen et al. (1987).

Experimental top

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.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell refinement: 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).

Figures top

Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

(4S,5S)-2-(2-Fluorophenyl)-1,3-dioxolane-4,5-dicarboxamide top

Crystal data top

C₁₁H₁₁FN₂O₄	F(000) = 528
M_r = 254.22	D_x = 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

Data collection top

Enraf–Nonius CAD-4 diffractometer	898 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.072
Graphite monochromator	θ_max = 26.0°, θ_min = 1.6°
ω/2θ scans	h = −5→5
Absorption correction: ψ scan (North et al., 1968)	k = 0→11
T_min = 0.978, T_max = 0.987	l = 0→30
2157 measured reflections	3 standard reflections every 120 min
1301 independent reflections	intensity decay: none

Refinement top

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(F_o²) + (0.002P)² + 1.775P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
1301 reflections	Δρ_max = 0.27 e Å⁻³
164 parameters	Δρ_min = −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)

Crystal data top

C₁₁H₁₁FN₂O₄	V = 1104.63 (15) Å³
M_r = 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

Data collection top

Enraf–Nonius CAD-4 diffractometer	898 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.072
T_min = 0.978, T_max = 0.987	3 standard reflections every 120 min
2157 measured reflections	intensity decay: none
1301 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.060	0 restraints
wR(F²) = 0.125	H-atom parameters constrained
S = 1.00	Δρ_max = 0.27 e Å⁻³
1301 reflections	Δρ_min = −0.23 e Å⁻³
164 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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
M_r	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)
T_min, T_max	0.978, 0.987
No. of measured, independent and observed [I > 2σ(I)] reflections	2157, 1301, 898
R_int	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
Δρ_max, Δρ_min (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).

Hydrogen-bond geometry (Å, º) top

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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