Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807038676/hk2307sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807038676/hk2307Isup2.hkl |
CCDC reference: 1283870
Crystals of the title compound were synthesized using hydrothermal method in a 23 ml Teflon-lined Parr bomb. Praseodymium (III) nitrate hexahydrate (217.5 mg, 0.5 mmol), 3,5-dinitro-2-fluorobenzamide (229.1 mg, 1 mmol) 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 colorless solution was decanted from small colorless crystals. These crystals were washed with distilled water followed by ethanol, and allowed to air-dry at room temperature.
H1A, H1B (for OH2) and H3A, H3B (for NH2) were located in difference syntheses and refined isotropically [O—H = 0.85 (2) and 0.850 (17) Å, Uiso(H) = 0.097 (16) and 0.090 (14) Å2; N—H = 0.81 (3) and 0.83 (3) Å, Uiso(H) = 0.076 (12) and 0.09 (3) Å2]. 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 hydrogen-bonding interactions are of critical importance in biological systems, organic materials and coordination chemistry, hydrogen-bonding is currently the best tool in achieving this goal (Zaworotko, 1997; Braga & Grepioni, 2000). Supramolecular architectures are of considerable contemporary interest by virtue of their potential applications in various fields (Moulton & Zaworotko, 2001; Pan et al., 2001; Ma et al., 2001; Prior & Rosseinsky, 2001). We originally attempted to synthesize complexes featuring Pr metal chains by reaction of the praseodymium(III) ion with 3,5-dinitro-2-fluoro- benzamide ligand. Unfortunately, we obtained only the title compound, (I), and we report herein its crystal structure.
In the molecule of (I) (Fig. 1), the ligand bond lengths and angles are within normal ranges (Allen et al., 1987). It contains one (C7H4FN3O5) molecule and one uncoordinated water molecule.
In the crystal structure, O—H···O, O—H···F and N—H···O hydrogen bonds (Table 1) seem to be effective in the stabilization of the structure, resulting in the formation of a supramolecular network structure.
For general background, see: Desiraju (1995, 1997); Braga et al. (1998); Zaworotko (1997); Braga & Grepioni (2000); Moulton & Zaworotko (2001); Pan et al. (2001); Ma et al. (2001); Prior & Rosseinsky (2001). For bond-length data, see: Allen et al. (1987).
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; 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.
C7H4FN3O5·H2O | F(000) = 1008 |
Mr = 247.15 | Dx = 1.763 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 1503 reflections |
a = 25.529 (2) Å | θ = 3.2–26.9° |
b = 6.357 (4) Å | µ = 0.17 mm−1 |
c = 12.353 (5) Å | T = 273 K |
β = 111.749 (2)° | Prism, colourless |
V = 1862.1 (15) Å3 | 0.24 × 0.15 × 0.15 mm |
Z = 8 |
Bruker SMART CCD area-detector diffractometer | 1816 independent reflections |
Radiation source: fine-focus sealed tube | 978 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
φ and ω scans | θmax = 26.2°, θmin = 3.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −31→31 |
Tmin = 0.961, Tmax = 0.976 | k = −7→7 |
5928 measured reflections | l = −15→15 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.063 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.204 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.99 | w = 1/[σ2(Fo2) + (0.1305P)2 + 0.002P] where P = (Fo2 + 2Fc2)/3 |
1816 reflections | (Δ/σ)max < 0.001 |
170 parameters | Δρmax = 0.37 e Å−3 |
9 restraints | Δρmin = −0.42 e Å−3 |
C7H4FN3O5·H2O | V = 1862.1 (15) Å3 |
Mr = 247.15 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 25.529 (2) Å | µ = 0.17 mm−1 |
b = 6.357 (4) Å | T = 273 K |
c = 12.353 (5) Å | 0.24 × 0.15 × 0.15 mm |
β = 111.749 (2)° |
Bruker SMART CCD area-detector diffractometer | 1816 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 978 reflections with I > 2σ(I) |
Tmin = 0.961, Tmax = 0.976 | Rint = 0.029 |
5928 measured reflections |
R[F2 > 2σ(F2)] = 0.063 | 9 restraints |
wR(F2) = 0.204 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.99 | Δρmax = 0.37 e Å−3 |
1816 reflections | Δρmin = −0.42 e Å−3 |
170 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 | 0.40250 (9) | 0.2100 (4) | 0.7293 (2) | 0.0892 (8) | |
O1 | 0.63158 (10) | 0.2285 (4) | 0.0276 (2) | 0.0700 (7) | |
H1A | 0.6362 (14) | 0.212 (7) | −0.0365 (14) | 0.097 (16)* | |
H1B | 0.6666 (3) | 0.230 (6) | 0.069 (2) | 0.090 (14)* | |
O2 | 0.50775 (11) | 0.2156 (5) | 0.8601 (2) | 0.0965 (11) | |
O3 | 0.29274 (10) | 0.1317 (4) | 0.63040 (19) | 0.0760 (8) | |
O4 | 0.24203 (9) | 0.3063 (4) | 0.7042 (2) | 0.0756 (8) | |
O5 | 0.30600 (10) | 0.3717 (4) | 1.1127 (2) | 0.0805 (8) | |
O6 | 0.39278 (12) | 0.2999 (5) | 1.2189 (2) | 0.0907 (9) | |
N1 | 0.28703 (11) | 0.2254 (4) | 0.7090 (2) | 0.0583 (7) | |
N2 | 0.35445 (13) | 0.3192 (4) | 1.1254 (2) | 0.0629 (8) | |
N3 | 0.53272 (10) | 0.2546 (4) | 1.0473 (2) | 0.0491 (7) | |
H3A | 0.5631 (9) | 0.237 (5) | 1.042 (3) | 0.076 (12)* | |
H3B | 0.5194 (19) | 0.140 (4) | 1.056 (5) | 0.09 (3)* | |
C1 | 0.43548 (12) | 0.2448 (5) | 0.9348 (3) | 0.0523 (8) | |
C2 | 0.39099 (13) | 0.2303 (5) | 0.8241 (3) | 0.0498 (7) | |
C3 | 0.33520 (13) | 0.2443 (5) | 0.8193 (3) | 0.0502 (8) | |
C4 | 0.32298 (13) | 0.2750 (5) | 0.9164 (3) | 0.0520 (8) | |
H5 | 0.2859 | 0.2894 | 0.9113 | 0.062* | |
C5 | 0.36662 (13) | 0.2839 (5) | 1.0211 (3) | 0.0511 (8) | |
C6 | 0.42304 (13) | 0.2689 (5) | 1.0327 (3) | 0.0530 (8) | |
H7 | 0.4517 | 0.2752 | 1.1059 | 0.064* | |
C7 | 0.49530 (14) | 0.2381 (5) | 0.9437 (3) | 0.0625 (9) |
U11 | U22 | U33 | U12 | U13 | U23 | |
F1 | 0.0610 (14) | 0.134 (2) | 0.0738 (15) | 0.0015 (11) | 0.0260 (12) | −0.0017 (12) |
O1 | 0.0406 (14) | 0.0910 (19) | 0.0716 (17) | 0.0023 (12) | 0.0129 (12) | 0.0041 (13) |
O2 | 0.0419 (15) | 0.195 (3) | 0.0562 (16) | 0.0037 (15) | 0.0225 (12) | 0.0020 (15) |
O3 | 0.0557 (15) | 0.112 (2) | 0.0562 (14) | −0.0072 (13) | 0.0161 (12) | −0.0168 (13) |
O4 | 0.0399 (14) | 0.114 (2) | 0.0692 (16) | 0.0105 (12) | 0.0152 (12) | 0.0075 (13) |
O5 | 0.0601 (17) | 0.112 (2) | 0.0797 (17) | 0.0049 (14) | 0.0375 (14) | −0.0085 (14) |
O6 | 0.074 (2) | 0.143 (3) | 0.0487 (15) | 0.0138 (16) | 0.0154 (14) | −0.0041 (14) |
N1 | 0.0373 (15) | 0.0792 (19) | 0.0563 (17) | −0.0029 (12) | 0.0148 (13) | 0.0075 (14) |
N2 | 0.059 (2) | 0.0713 (18) | 0.0636 (18) | −0.0019 (14) | 0.0295 (16) | −0.0052 (13) |
N3 | 0.0235 (13) | 0.0753 (18) | 0.0417 (14) | −0.0018 (12) | 0.0041 (11) | −0.0009 (11) |
C1 | 0.0354 (17) | 0.0652 (19) | 0.0558 (19) | 0.0002 (13) | 0.0162 (15) | 0.0027 (14) |
C2 | 0.0397 (17) | 0.0690 (19) | 0.0432 (16) | 0.0009 (13) | 0.0183 (14) | −0.0011 (13) |
C3 | 0.0437 (18) | 0.0575 (18) | 0.0449 (16) | −0.0004 (13) | 0.0112 (14) | 0.0043 (13) |
C4 | 0.0423 (18) | 0.0555 (18) | 0.061 (2) | −0.0003 (13) | 0.0227 (16) | 0.0045 (13) |
C5 | 0.0470 (19) | 0.0602 (18) | 0.0486 (17) | 0.0026 (13) | 0.0207 (15) | 0.0002 (13) |
C6 | 0.0425 (17) | 0.065 (2) | 0.0455 (17) | −0.0019 (14) | 0.0097 (14) | −0.0010 (13) |
C7 | 0.0441 (19) | 0.078 (2) | 0.065 (2) | 0.0009 (15) | 0.0199 (18) | 0.0076 (16) |
F1—C2 | 1.315 (4) | O1—H1B | 0.850 (17) |
O2—C7 | 1.196 (4) | N3—H3A | 0.81 (3) |
O3—N1 | 1.193 (3) | N3—H3B | 0.83 (3) |
O4—N1 | 1.240 (4) | C1—C6 | 1.367 (4) |
O5—N2 | 1.233 (3) | C1—C2 | 1.420 (4) |
O6—N2 | 1.212 (4) | C2—C3 | 1.406 (4) |
N1—C3 | 1.464 (4) | C3—C4 | 1.361 (4) |
N2—C5 | 1.450 (4) | C4—C5 | 1.360 (4) |
N3—C7 | 1.287 (4) | C4—H5 | 0.9300 |
C1—C7 | 1.491 (4) | C5—C6 | 1.397 (4) |
O1—H1A | 0.85 (2) | C6—H7 | 0.9300 |
F1—C2—C1 | 120.1 (3) | C2—C1—C7 | 120.0 (3) |
F1—C2—C3 | 121.7 (3) | C3—C2—C1 | 118.2 (3) |
O2—C7—C1 | 122.2 (3) | C4—C3—C2 | 122.1 (3) |
O2—C7—N3 | 122.1 (3) | C4—C3—N1 | 116.4 (3) |
N3—C7—C1 | 115.7 (3) | C2—C3—N1 | 121.5 (3) |
O3—N1—O4 | 124.0 (3) | C5—C4—C3 | 118.0 (3) |
O3—N1—C3 | 119.0 (3) | C5—C4—H5 | 121.0 |
O4—N1—C3 | 117.0 (3) | C3—C4—H5 | 121.0 |
O5—N2—O6 | 124.5 (3) | C4—C5—C6 | 123.0 (3) |
O5—N2—C5 | 117.6 (3) | C4—C5—N2 | 118.8 (3) |
O6—N2—C5 | 117.9 (3) | C6—C5—N2 | 118.2 (3) |
H1A—O1—H1B | 95 (3) | C1—C6—C5 | 119.1 (3) |
C7—N3—H3A | 107 (3) | C1—C6—H7 | 120.5 |
C7—N3—H3B | 82 (4) | C5—C6—H7 | 120.5 |
H3A—N3—H3B | 110 (2) | O2—C7—H3B | 128.8 (19) |
C6—C1—C2 | 119.6 (3) | C1—C7—H3B | 98.3 (15) |
C6—C1—C7 | 120.4 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1B···O4i | 0.85 (2) | 2.04 (1) | 2.863 (3) | 162 (3) |
O1—H1A···O3ii | 0.85 (2) | 2.54 (2) | 3.273 (4) | 145 (3) |
O1—H1A···F1ii | 0.85 (2) | 2.21 (2) | 2.966 (4) | 147 (3) |
N3—H3A···O1iii | 0.81 (3) | 1.82 (2) | 2.629 (3) | 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 | C7H4FN3O5·H2O |
Mr | 247.15 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 273 |
a, b, c (Å) | 25.529 (2), 6.357 (4), 12.353 (5) |
β (°) | 111.749 (2) |
V (Å3) | 1862.1 (15) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.17 |
Crystal size (mm) | 0.24 × 0.15 × 0.15 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.961, 0.976 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5928, 1816, 978 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.620 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.063, 0.204, 0.99 |
No. of reflections | 1816 |
No. of parameters | 170 |
No. of restraints | 9 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.37, −0.42 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Siemens, 1996), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1B···O4i | 0.850 (17) | 2.041 (11) | 2.863 (3) | 162 (3) |
O1—H1A···O3ii | 0.85 (2) | 2.54 (2) | 3.273 (4) | 145 (3) |
O1—H1A···F1ii | 0.85 (2) | 2.214 (18) | 2.966 (4) | 147 (3) |
N3—H3A···O1iii | 0.81 (3) | 1.820 (15) | 2.629 (3) | 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 hydrogen-bonding interactions are of critical importance in biological systems, organic materials and coordination chemistry, hydrogen-bonding is currently the best tool in achieving this goal (Zaworotko, 1997; Braga & Grepioni, 2000). Supramolecular architectures are of considerable contemporary interest by virtue of their potential applications in various fields (Moulton & Zaworotko, 2001; Pan et al., 2001; Ma et al., 2001; Prior & Rosseinsky, 2001). We originally attempted to synthesize complexes featuring Pr metal chains by reaction of the praseodymium(III) ion with 3,5-dinitro-2-fluoro- benzamide ligand. Unfortunately, we obtained only the title compound, (I), and we report herein its crystal structure.
In the molecule of (I) (Fig. 1), the ligand bond lengths and angles are within normal ranges (Allen et al., 1987). It contains one (C7H4FN3O5) molecule and one uncoordinated water molecule.
In the crystal structure, O—H···O, O—H···F and N—H···O hydrogen bonds (Table 1) seem to be effective in the stabilization of the structure, resulting in the formation of a supramolecular network structure.