Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807039724/at2369sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807039724/at2369Isup2.hkl |
CCDC reference: 1196947
Key indicators
- Single-crystal X-ray study
- T = 273 K
- Mean (C-C) = 0.004 Å
- R factor = 0.049
- wR factor = 0.171
- Data-to-parameter ratio = 11.0
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT230_ALERT_2_B Hirshfeld Test Diff for F1 - C2 .. 14.44 su PLAT417_ALERT_2_B Short Inter D-H..H-D H1 .. H3C .. 1.62 Ang. PLAT430_ALERT_2_B Short Inter D...A Contact O2 .. O2 .. 2.57 Ang.
Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.98 PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ..... ? PLAT230_ALERT_2_C Hirshfeld Test Diff for O2 - C7 .. 6.13 su PLAT352_ALERT_3_C Short N-H Bond (0.87A) N3 - H3A ... 0.74 Ang. PLAT430_ALERT_2_C Short Inter D...A Contact O5 .. N2 .. 2.88 Ang. PLAT431_ALERT_2_C Short Inter HL..A Contact F1 .. O2 .. 2.85 Ang.
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 6
0 ALERT level A = In general: serious problem 3 ALERT level B = Potentially serious problem 7 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 6 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
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.
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).
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.
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).
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).
C7H3FN2O6·NH3 | F(000) = 1008 |
Mr = 247.15 | Dx = 1.857 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 1499 reflections |
a = 25.08 (2) Å | θ = 3.0–26.9° |
b = 6.214 (3) Å | µ = 0.18 mm−1 |
c = 12.237 (4) Å | T = 273 K |
β = 112.004 (1)° | Prism, colourless |
V = 1768.0 (19) Å3 | 0.24 × 0.15 × 0.14 mm |
Z = 8 |
Bruker APEXII area-detector diffractometer | 1876 independent reflections |
Radiation source: fine-focus sealed tube | 977 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
φ and ω scans | θmax = 27.0°, θmin = 3.4° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −31→31 |
Tmin = 0.959, Tmax = 0.975 | k = −7→7 |
6068 measured reflections | l = −15→15 |
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)] = 0.049 | H 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 reflections | Δρmax = 0.27 e Å−3 |
171 parameters | Δρmin = −0.30 e Å−3 |
6 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.014 (3) |
C7H3FN2O6·NH3 | V = 1768.0 (19) Å3 |
Mr = 247.15 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 25.08 (2) Å | µ = 0.18 mm−1 |
b = 6.214 (3) Å | T = 273 K |
c = 12.237 (4) Å | 0.24 × 0.15 × 0.14 mm |
β = 112.004 (1)° |
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 = 0.975 | Rint = 0.032 |
6068 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 6 restraints |
wR(F2) = 0.172 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.27 e Å−3 |
1876 reflections | Δρmin = −0.30 e Å−3 |
171 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 | ||
F1 | 0.40241 (8) | 0.2109 (4) | 0.72936 (17) | 0.0874 (7) | |
O1 | 0.53280 (10) | 0.2528 (3) | 1.04732 (19) | 0.0660 (7) | |
O2 | 0.50766 (10) | 0.2179 (5) | 0.85991 (19) | 0.0934 (9) | |
O3 | 0.29277 (9) | 0.1317 (4) | 0.63059 (17) | 0.0747 (7) | |
O4 | 0.24215 (9) | 0.3061 (4) | 0.70445 (19) | 0.0743 (7) | |
O5 | 0.30610 (9) | 0.3713 (4) | 1.11276 (19) | 0.0799 (7) | |
O6 | 0.39272 (12) | 0.3013 (4) | 1.2183 (2) | 0.0915 (9) | |
N3 | 0.63157 (10) | 0.2284 (4) | 0.0279 (2) | 0.0512 (6) | |
N1 | 0.35425 (12) | 0.3194 (4) | 1.1251 (2) | 0.0618 (7) | |
N2 | 0.28703 (10) | 0.2260 (4) | 0.7096 (2) | 0.0571 (7) | |
C1 | 0.43546 (11) | 0.2452 (4) | 0.9348 (2) | 0.0510 (7) | |
C2 | 0.39091 (11) | 0.2306 (4) | 0.8240 (2) | 0.0495 (7) | |
C3 | 0.33530 (12) | 0.2445 (4) | 0.8196 (2) | 0.0505 (7) | |
C4 | 0.32304 (12) | 0.2745 (4) | 0.9169 (2) | 0.0521 (7) | |
H4 | 0.2852 | 0.2882 | 0.9114 | 0.063* | |
C5 | 0.36643 (12) | 0.2841 (4) | 1.0208 (2) | 0.0506 (7) | |
C6 | 0.42307 (12) | 0.2693 (4) | 1.0325 (2) | 0.0531 (7) | |
H6 | 0.4524 | 0.2758 | 1.1066 | 0.064* | |
C7 | 0.49529 (12) | 0.2386 (5) | 0.9436 (3) | 0.0606 (8) | |
H1 | 0.5630 (14) | 0.246 (4) | 1.036 (2) | 0.064 (9)* | |
H3A | 0.6302 (10) | 0.217 (4) | −0.0331 (15) | 0.050 (7)* | |
H3B | 0.6656 (9) | 0.231 (5) | 0.074 (2) | 0.085 (12)* | |
H3C | 0.620 (3) | 0.110 (9) | 0.048 (4) | 0.060 (2)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
F1 | 0.0594 (13) | 0.1295 (18) | 0.0730 (13) | −0.0004 (10) | 0.0243 (10) | −0.0022 (10) |
O1 | 0.0385 (13) | 0.0933 (17) | 0.0601 (14) | −0.0008 (10) | 0.0113 (11) | −0.0013 (10) |
O2 | 0.0407 (13) | 0.188 (3) | 0.0543 (14) | 0.0040 (13) | 0.0208 (11) | 0.0013 (13) |
O3 | 0.0542 (13) | 0.1070 (18) | 0.0586 (13) | −0.0069 (12) | 0.0162 (11) | −0.0154 (12) |
O4 | 0.0406 (13) | 0.1082 (18) | 0.0699 (14) | 0.0103 (11) | 0.0159 (10) | 0.0071 (11) |
O5 | 0.0591 (15) | 0.1091 (18) | 0.0814 (15) | 0.0028 (12) | 0.0376 (12) | −0.0094 (13) |
O6 | 0.0797 (19) | 0.140 (2) | 0.0500 (14) | 0.0146 (14) | 0.0186 (13) | −0.0040 (13) |
N3 | 0.0286 (12) | 0.0725 (16) | 0.0467 (15) | 0.0015 (10) | 0.0074 (11) | 0.0027 (12) |
N1 | 0.0571 (17) | 0.0696 (16) | 0.0631 (16) | 0.0001 (12) | 0.0274 (14) | −0.0040 (12) |
N2 | 0.0371 (14) | 0.0770 (17) | 0.0542 (15) | −0.0022 (11) | 0.0137 (11) | 0.0071 (12) |
C1 | 0.0377 (15) | 0.0616 (17) | 0.0546 (17) | 0.0004 (12) | 0.0181 (13) | 0.0025 (12) |
C2 | 0.0387 (15) | 0.0663 (17) | 0.0455 (15) | 0.0006 (12) | 0.0180 (13) | −0.0012 (11) |
C3 | 0.0434 (16) | 0.0561 (16) | 0.0477 (15) | −0.0001 (11) | 0.0119 (13) | 0.0041 (11) |
C4 | 0.0424 (16) | 0.0555 (16) | 0.0608 (17) | 0.0006 (11) | 0.0222 (14) | 0.0044 (12) |
C5 | 0.0468 (17) | 0.0589 (16) | 0.0470 (15) | 0.0031 (12) | 0.0185 (13) | 0.0011 (11) |
C6 | 0.0439 (16) | 0.0623 (17) | 0.0486 (16) | −0.0009 (12) | 0.0119 (13) | −0.0004 (12) |
C7 | 0.0413 (16) | 0.076 (2) | 0.0585 (18) | −0.0003 (13) | 0.0123 (15) | 0.0044 (14) |
F1—C2 | 1.300 (3) | N3—H3C | 0.86 (6) |
O1—C7 | 1.268 (4) | C1—C6 | 1.352 (4) |
O2—C7 | 1.183 (4) | C1—C2 | 1.400 (4) |
O3—N2 | 1.184 (3) | C1—C7 | 1.464 (4) |
O4—N2 | 1.211 (3) | C2—C3 | 1.378 (4) |
O5—N1 | 1.203 (3) | C3—C4 | 1.350 (4) |
O6—N1 | 1.191 (3) | C4—C5 | 1.330 (4) |
N1—C5 | 1.436 (4) | C4—H4 | 0.9300 |
N2—C3 | 1.438 (4) | C5—C6 | 1.376 (4) |
N3—H3A | 0.739 (15) | C6—H6 | 0.9300 |
N3—H3B | 0.830 (18) | O1—H1 | 0.82 (3) |
F1—C2—C1 | 120.4 (2) | C6—C1—C2 | 120.0 (3) |
F1—C2—C3 | 122.0 (3) | C6—C1—C7 | 120.4 (3) |
O1—C7—O2 | 122.5 (3) | C2—C1—C7 | 119.6 (3) |
O1—C7—C1 | 115.3 (3) | C3—C2—C1 | 117.6 (2) |
O2—C7—C1 | 122.2 (3) | C4—C3—C2 | 122.4 (3) |
O3—N2—O4 | 123.8 (3) | C4—C3—N2 | 116.5 (3) |
O3—N2—C3 | 119.1 (2) | C2—C3—N2 | 121.1 (3) |
O4—N2—C3 | 117.1 (3) | C5—C4—C3 | 118.3 (3) |
O5—N1—O6 | 124.1 (3) | C5—C4—H4 | 120.8 |
O5—N1—C5 | 117.8 (3) | C3—C4—H4 | 120.8 |
O6—N1—C5 | 118.1 (3) | C4—C5—C6 | 122.7 (3) |
C7—O1—H1 | 102 (2) | C4—C5—N1 | 119.1 (3) |
H3C—N3—H3A | 108 (4) | C6—C5—N1 | 118.2 (2) |
H3C—N3—H3B | 101 (3) | C1—C6—C5 | 119.1 (3) |
H3A—N3—H3B | 110 (2) | C1—C6—H6 | 120.5 |
H3A—N3—H3C | 108 (4) | C5—C6—H6 | 120.5 |
H3B—N3—H3C | 101 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3B···O4i | 0.83 (2) | 2.00 (2) | 2.813 (4) | 168 (3) |
N3—H3A···F1ii | 0.74 (2) | 2.23 (2) | 2.940 (4) | 162 (2) |
O1—H1···N3iii | 0.82 (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. |
Experimental details
Crystal data | |
Chemical formula | C7H3FN2O6·NH3 |
Mr | 247.15 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 273 |
a, b, c (Å) | 25.08 (2), 6.214 (3), 12.237 (4) |
β (°) | 112.004 (1) |
V (Å3) | 1768.0 (19) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.18 |
Crystal size (mm) | 0.24 × 0.15 × 0.14 |
Data collection | |
Diffractometer | Bruker APEXII area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.959, 0.975 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6068, 1876, 977 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.638 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.172, 1.01 |
No. of reflections | 1876 |
No. of parameters | 171 |
No. of restraints | 6 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.27, −0.30 |
Computer programs: APEX2 (Bruker, 2005), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Siemens, 1996).
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3B···O4i | 0.830 (18) | 1.996 (18) | 2.813 (4) | 168 (3) |
N3—H3A···F1ii | 0.739 (15) | 2.228 (17) | 2.940 (4) | 162 (2) |
O1—H1···N3iii | 0.82 (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. |
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.