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Acta Cryst. (2007). E63, o3831    [ doi:10.1107/S1600536807039724 ]

2-Fluoro-3,5-dinitrobenzoic acid-ammonia (1/1)

H. Zhong, X.-M. Yang, H.-L. Xie and C.-J. Luo

Abstract top

In the crystal structure of the title complex, C7H3FN2O6·NH3, the uncoordinated ammonia molecule interacts with nearby nitro and carboxyl groups and the F atom of the 3,5-dinitro-2-fluorobenzoic acid by way of N-H...O, N-H...F and O-H...N hydrogen bonds. These hydrogen bonds lead to a supramolecular network structure.

Comment top

In the synthesis of crystal structures by design, the assembly of molecular units in predefined arrangements is a key goal (Desiraju, 1995, 1997; Braga et al., 1998). Due to carboxyl groups are one of the most important classes of biological ligands, the coordination of metal-carboxyl groups complexes are of critical importance in biological systems, organic materials and coordination chemistry. Recently, carboxyl groups with variable coordination modes have been used to construct metal-organic supramolecular structure (McCann et al., 1996; McCann et al., 1995; Wai et al., 1990; Yaghi et al., 1996; Min & Lee 2002; Maira et al., 2001). We originally attempted to synthesize complexes featuring Pr metal chains by reaction of the praseodymium(III) ion with 3,5-dinitro-2-fluorobenzoic acid ligand. Unfortunately, we obtained only the title compound, (I).

In the molecule of (I) (Fig. 1), the ligand bond lengths and angles are within normal ranges (Allen et al., 1987). In the title complex (I), contains one 3,5-dinitro-2-fluorobenzoic acid molecule and one uncoordinated ammonia molecule. The uncoordinated ammonia molecule interacts with nearby nitro and carboxyl groups and F atom of the 3,5-dinitro-2-fluorobenzoic acid ligands by way of N—H···O, N—H···F and O—H···N hydrogen bonds, with the N···O, N···F and O···N distances of 2.813 (4), 2.940 (4) and 2.579 (4) Å, respectively (Fig. 2 and Table 1). These hydrogen bonds lead to a supramolecular network structure.

Related literature top

For related literature, see: Allen et al. (1987); Braga et al. (1998); Desiraju (1995, 1997); Maira et al. (2001); McCann et al. (1995, 1996); Min & Lee (2002); Wai et al. (1990); Yaghi et al. (1996).

Experimental top

Crystals of the title compound (I) were synthesized using hydrothermal method in a 23 ml Teflon-lined Parr bomb, which was then sealed. Praseodymium (III) nitrate hexahydrate (217.5 mg, 0.5 mmol), 3,5-dinitro-2-fluorobenzoic acid (230.1 mg, 1 mmol), ammonia (0.5 mol/l, 2 ml) and distilled water (5 g) were placed into the bomb and sealed. The bomb was then heated under autogenous pressure up to 443 K over the course of 7 d and allowed to cool at room temperature for 24 h. Upon opening the bomb, a clear colourless solution was decanted from small colourless crystals. These crystals were washed with distilled water, followed by ethanol, and allowed to air-dry at room temperature.

Refinement top

H atoms of ammonia and hydroxyl group were located from difference Fourier syntheses and refined with restraints to the O—H distances and the H—O—H angles. The remaining H atoms were positioned geometrically, with C—H = 0.93 Å for aromatic H, and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1996); software used to prepare material for publication: SHELXTL (Siemens, 1996).

Figures top
[Figure 1] Fig. 1. The structure of the title molecule (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. A packing diagram of (I). Hydrogen bonds are shown as dashed lines.
3,5-Dinitro-2-fluorobenzoic acid–ammonia (1/1) top
Crystal data top
C7H3FN2O6·NH3F(000) = 1008
Mr = 247.15Dx = 1.857 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1499 reflections
a = 25.08 (2) Åθ = 3.0–26.9°
b = 6.214 (3) ŵ = 0.18 mm−1
c = 12.237 (4) ÅT = 273 K
β = 112.004 (1)°Prism, colourless
V = 1768.0 (19) Å30.24 × 0.15 × 0.14 mm
Z = 8
Data collection top
Bruker APEXII area-detector
diffractometer		1876 independent reflections
Radiation source: fine-focus sealed tube977 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.032
φ and ω scansθmax = 27.0°, θmin = 3.4°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −31→31
Tmin = 0.959, Tmax = 0.975k = −7→7
6068 measured reflectionsl = −15→15
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.049H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.172 w = 1/[σ2(Fo2) + (0.1059P)2 + 0.02P]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max < 0.001
1876 reflectionsΔρmax = 0.27 e Å−3
171 parametersΔρmin = −0.30 e Å−3
6 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.014 (3)
Crystal data top
C7H3FN2O6·NH3V = 1768.0 (19) Å3
Mr = 247.15Z = 8
Monoclinic, C2/cMo Kα radiation
a = 25.08 (2) ŵ = 0.18 mm−1
b = 6.214 (3) ÅT = 273 K
c = 12.237 (4) Å0.24 × 0.15 × 0.14 mm
β = 112.004 (1)°
Data collection top
Bruker APEXII area-detector
diffractometer		1876 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		977 reflections with I > 2σ(I)
Tmin = 0.959, Tmax = 0.975Rint = 0.032
6068 measured reflectionsθmax = 27.0°
Refinement top
R[F2 > 2σ(F2)] = 0.049H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.172Δρmax = 0.27 e Å−3
S = 1.01Δρmin = −0.30 e Å−3
1876 reflectionsAbsolute structure: ?
171 parametersFlack parameter: ?
6 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
F10.40241 (8)0.2109 (4)0.72936 (17)0.0874 (7)
O10.53280 (10)0.2528 (3)1.04732 (19)0.0660 (7)
O20.50766 (10)0.2179 (5)0.85991 (19)0.0934 (9)
O30.29277 (9)0.1317 (4)0.63059 (17)0.0747 (7)
O40.24215 (9)0.3061 (4)0.70445 (19)0.0743 (7)
O50.30610 (9)0.3713 (4)1.11276 (19)0.0799 (7)
O60.39272 (12)0.3013 (4)1.2183 (2)0.0915 (9)
N30.63157 (10)0.2284 (4)0.0279 (2)0.0512 (6)
N10.35425 (12)0.3194 (4)1.1251 (2)0.0618 (7)
N20.28703 (10)0.2260 (4)0.7096 (2)0.0571 (7)
C10.43546 (11)0.2452 (4)0.9348 (2)0.0510 (7)
C20.39091 (11)0.2306 (4)0.8240 (2)0.0495 (7)
C30.33530 (12)0.2445 (4)0.8196 (2)0.0505 (7)
C40.32304 (12)0.2745 (4)0.9169 (2)0.0521 (7)
H40.28520.28820.91140.063*
C50.36643 (12)0.2841 (4)1.0208 (2)0.0506 (7)
C60.42307 (12)0.2693 (4)1.0325 (2)0.0531 (7)
H60.45240.27581.10660.064*
C70.49529 (12)0.2386 (5)0.9436 (3)0.0606 (8)
H10.5630 (14)0.246 (4)1.036 (2)0.064 (9)*
H3A0.6302 (10)0.217 (4)−0.0331 (15)0.050 (7)*
H3B0.6656 (9)0.231 (5)0.074 (2)0.085 (12)*
H3C0.620 (3)0.110 (9)0.048 (4)0.060 (2)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
F10.0594 (13)0.1295 (18)0.0730 (13)−0.0004 (10)0.0243 (10)−0.0022 (10)
O10.0385 (13)0.0933 (17)0.0601 (14)−0.0008 (10)0.0113 (11)−0.0013 (10)
O20.0407 (13)0.188 (3)0.0543 (14)0.0040 (13)0.0208 (11)0.0013 (13)
O30.0542 (13)0.1070 (18)0.0586 (13)−0.0069 (12)0.0162 (11)−0.0154 (12)
O40.0406 (13)0.1082 (18)0.0699 (14)0.0103 (11)0.0159 (10)0.0071 (11)
O50.0591 (15)0.1091 (18)0.0814 (15)0.0028 (12)0.0376 (12)−0.0094 (13)
O60.0797 (19)0.140 (2)0.0500 (14)0.0146 (14)0.0186 (13)−0.0040 (13)
N30.0286 (12)0.0725 (16)0.0467 (15)0.0015 (10)0.0074 (11)0.0027 (12)
N10.0571 (17)0.0696 (16)0.0631 (16)0.0001 (12)0.0274 (14)−0.0040 (12)
N20.0371 (14)0.0770 (17)0.0542 (15)−0.0022 (11)0.0137 (11)0.0071 (12)
C10.0377 (15)0.0616 (17)0.0546 (17)0.0004 (12)0.0181 (13)0.0025 (12)
C20.0387 (15)0.0663 (17)0.0455 (15)0.0006 (12)0.0180 (13)−0.0012 (11)
C30.0434 (16)0.0561 (16)0.0477 (15)−0.0001 (11)0.0119 (13)0.0041 (11)
C40.0424 (16)0.0555 (16)0.0608 (17)0.0006 (11)0.0222 (14)0.0044 (12)
C50.0468 (17)0.0589 (16)0.0470 (15)0.0031 (12)0.0185 (13)0.0011 (11)
C60.0439 (16)0.0623 (17)0.0486 (16)−0.0009 (12)0.0119 (13)−0.0004 (12)
C70.0413 (16)0.076 (2)0.0585 (18)−0.0003 (13)0.0123 (15)0.0044 (14)
Geometric parameters (Å, º) top
F1—C21.300 (3)N3—H3C0.86 (6)
O1—C71.268 (4)C1—C61.352 (4)
O2—C71.183 (4)C1—C21.400 (4)
O3—N21.184 (3)C1—C71.464 (4)
O4—N21.211 (3)C2—C31.378 (4)
O5—N11.203 (3)C3—C41.350 (4)
O6—N11.191 (3)C4—C51.330 (4)
N1—C51.436 (4)C4—H40.9300
N2—C31.438 (4)C5—C61.376 (4)
N3—H3A0.739 (15)C6—H60.9300
N3—H3B0.830 (18)O1—H10.82 (3)
F1—C2—C1120.4 (2)C6—C1—C2120.0 (3)
F1—C2—C3122.0 (3)C6—C1—C7120.4 (3)
O1—C7—O2122.5 (3)C2—C1—C7119.6 (3)
O1—C7—C1115.3 (3)C3—C2—C1117.6 (2)
O2—C7—C1122.2 (3)C4—C3—C2122.4 (3)
O3—N2—O4123.8 (3)C4—C3—N2116.5 (3)
O3—N2—C3119.1 (2)C2—C3—N2121.1 (3)
O4—N2—C3117.1 (3)C5—C4—C3118.3 (3)
O5—N1—O6124.1 (3)C5—C4—H4120.8
O5—N1—C5117.8 (3)C3—C4—H4120.8
O6—N1—C5118.1 (3)C4—C5—C6122.7 (3)
C7—O1—H1102 (2)C4—C5—N1119.1 (3)
H3C—N3—H3A108 (4)C6—C5—N1118.2 (2)
H3C—N3—H3B101 (3)C1—C6—C5119.1 (3)
H3A—N3—H3B110 (2)C1—C6—H6120.5
H3A—N3—H3C108 (4)C5—C6—H6120.5
H3B—N3—H3C101 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3B···O4i0.83 (2)2.00 (2)2.813 (4)168 (3)
N3—H3A···F1ii0.74 (2)2.23 (2)2.940 (4)162 (2)
O1—H1···N3iii0.82 (3)1.76 (4)2.579 (4)174 (3)
Symmetry codes: (i) x+1/2, −y+1/2, z−1/2; (ii) −x+1, y, −z+1/2; (iii) x, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3B···O4i0.830 (18)1.996 (18)2.813 (4)168 (3)
N3—H3A···F1ii0.739 (15)2.228 (17)2.940 (4)162 (2)
O1—H1···N3iii0.82 (3)1.76 (4)2.579 (4)174 (3)
Symmetry codes: (i) x+1/2, −y+1/2, z−1/2; (ii) −x+1, y, −z+1/2; (iii) x, y, z+1.
Acknowledgements top

This work was supported by the Science and Technology Bureau of Jian, Jiangxi Province of China (grant No. 20052817).

references
References top

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