Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680704086X/at2378sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680704086X/at2378Isup2.hkl |
CCDC reference: 1101558
Crystals of the title compound were synthesized using hydrothermal method in a 23 ml Teflon-lined Parr bomb, which was then sealed. Neodymium (III) nitrate hexahydrate (219.1 mg, 0.5 mmol), 2-hydroxy-anilinoformic acid (153.1 mg, 1 mmol), ammonia (0.5 mol/l, 2 ml) and distilled water (3 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 colourless crystals. These crystals were washed with distilled water followed by ethanol, and allowed to air-dry at room temperature.
H atoms of ammonia 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 O—H = 0.82 Å (for OH), N—H = 0.86 Å (for NH) and C—H = 0.93 Å for aromatic H, and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C, N) or Uiso(H) = 1.5Ueq(O).
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 structures (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 Nd metal chains by reaction of the neodymium(III) ion with 2-hydroxy-anilinoformic acid 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 (C7H7NO3) molecule and one ammonia molecule.
In the crystal structure, intramolecular O—H···O and intermolecular N—H···O, N—H···N and O—H···N hydrogen bonds (Table 1, Fig. 2) result in the formation of a supramolecular network structure.
For general background, see: Desiraju (1995, 1997); Braga et al. (1998); Mccann et al. (1996, 1995); Wai et al. (1990); Yaghi et al. (1996); Min & Lee (2002); Maira et al. (2001). For bond-length data, see: Allen et al. (1987).
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).
C7H7NO3·NH3 | F(000) = 360 |
Mr = 170.17 | Dx = 1.553 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 1897 reflections |
a = 13.0017 (14) Å | θ = 2.7–27.9° |
b = 3.988 (2) Å | µ = 0.12 mm−1 |
c = 15.358 (2) Å | T = 273 K |
β = 113.927 (4)° | Prism, colourless |
V = 727.9 (5) Å3 | 0.64 × 0.13 × 0.10 mm |
Z = 4 |
Bruker APEXII area-detector diffractometer | 1432 independent reflections |
Radiation source: fine-focus sealed tube | 852 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.050 |
φ and ω scans | θmax = 26.5°, θmin = 2.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −16→15 |
Tmin = 0.926, Tmax = 0.988 | k = −4→4 |
4379 measured reflections | l = −19→19 |
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)] = 0.055 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.194 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | w = 1/[σ2(Fo2) + (0.1557P)2 + 0.02P] where P = (Fo2 + 2Fc2)/3 |
1432 reflections | (Δ/σ)max < 0.001 |
123 parameters | Δρmax = 0.34 e Å−3 |
6 restraints | Δρmin = −0.40 e Å−3 |
C7H7NO3·NH3 | V = 727.9 (5) Å3 |
Mr = 170.17 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 13.0017 (14) Å | µ = 0.12 mm−1 |
b = 3.988 (2) Å | T = 273 K |
c = 15.358 (2) Å | 0.64 × 0.13 × 0.10 mm |
β = 113.927 (4)° |
Bruker APEXII area-detector diffractometer | 1432 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 852 reflections with I > 2σ(I) |
Tmin = 0.926, Tmax = 0.988 | Rint = 0.050 |
4379 measured reflections |
R[F2 > 2σ(F2)] = 0.055 | 6 restraints |
wR(F2) = 0.194 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | Δρmax = 0.34 e Å−3 |
1432 reflections | Δρmin = −0.40 e Å−3 |
123 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 | 0.6556 (3) | 1.3946 (8) | −0.1911 (2) | 0.0849 (10) | |
H1AA | 0.6752 | 1.4601 | −0.2326 | 0.127* | |
O2 | 0.8205 (2) | 1.1177 (7) | −0.13776 (16) | 0.0666 (9) | |
O3 | 0.6313 (2) | 0.9654 (7) | 0.0654 (2) | 0.0746 (9) | |
H3A | 0.6366 | 1.1483 | 0.0912 | 0.112* | |
N1 | 0.7137 (2) | 1.1124 (7) | −0.05209 (18) | 0.0501 (8) | |
H1A | 0.6521 | 1.1847 | −0.0508 | 0.060* | |
N2 | 0.5039 (2) | 0.5292 (8) | 0.1088 (2) | 0.0521 (8) | |
C1 | 0.7879 (3) | 0.6672 (9) | 0.1621 (3) | 0.0668 (11) | |
H1 | 0.7539 | 0.6265 | 0.2039 | 0.080* | |
C2 | 0.8910 (3) | 0.5422 (10) | 0.1823 (3) | 0.0640 (10) | |
H2 | 0.9279 | 0.4156 | 0.2370 | 0.077* | |
C3 | 0.9404 (3) | 0.6048 (9) | 0.1209 (3) | 0.0612 (10) | |
H3 | 1.0117 | 0.5204 | 0.1335 | 0.073* | |
C4 | 0.8853 (3) | 0.7912 (9) | 0.0409 (3) | 0.0571 (9) | |
H4 | 0.9193 | 0.8330 | −0.0009 | 0.069* | |
C5 | 0.7794 (3) | 0.9184 (8) | 0.0215 (2) | 0.0479 (8) | |
C6 | 0.7326 (2) | 0.8485 (7) | 0.0835 (2) | 0.0398 (7) | |
C7 | 0.7361 (3) | 1.2060 (9) | −0.1293 (2) | 0.0497 (8) | |
H2A | 0.496 (3) | 0.353 (6) | 0.078 (3) | 0.092 (16)* | |
H2B | 0.546 (2) | 0.635 (7) | 0.093 (2) | 0.080 (10)* | |
H2C | 0.547 (4) | 0.456 (11) | 0.1634 (17) | 0.101 (3)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.097 (2) | 0.098 (2) | 0.0700 (18) | −0.0120 (17) | 0.0455 (16) | 0.0082 (15) |
O2 | 0.0646 (15) | 0.092 (2) | 0.0615 (16) | −0.0094 (12) | 0.0442 (13) | −0.0098 (12) |
O3 | 0.0825 (18) | 0.0757 (19) | 0.095 (2) | 0.0218 (13) | 0.0663 (16) | 0.0250 (15) |
N1 | 0.0523 (15) | 0.0578 (17) | 0.0517 (16) | −0.0046 (12) | 0.0329 (13) | 0.0013 (12) |
N2 | 0.0649 (18) | 0.0522 (18) | 0.0545 (17) | 0.0054 (14) | 0.0400 (14) | 0.0048 (14) |
C1 | 0.091 (3) | 0.061 (2) | 0.067 (2) | 0.0063 (19) | 0.051 (2) | 0.0075 (18) |
C2 | 0.069 (2) | 0.066 (2) | 0.057 (2) | 0.0021 (18) | 0.0256 (18) | −0.0003 (17) |
C3 | 0.0501 (18) | 0.064 (2) | 0.070 (2) | −0.0046 (16) | 0.0253 (17) | −0.0072 (18) |
C4 | 0.0523 (18) | 0.061 (2) | 0.066 (2) | −0.0081 (15) | 0.0322 (17) | −0.0043 (17) |
C5 | 0.0543 (18) | 0.0482 (18) | 0.0501 (17) | −0.0115 (14) | 0.0304 (15) | −0.0099 (14) |
C6 | 0.0452 (15) | 0.0375 (15) | 0.0471 (16) | 0.0042 (12) | 0.0294 (13) | 0.0043 (12) |
C7 | 0.0523 (18) | 0.058 (2) | 0.0438 (16) | −0.0147 (15) | 0.0245 (14) | −0.0080 (15) |
O1—C7 | 1.325 (4) | C1—C6 | 1.338 (5) |
O1—H1AA | 0.8200 | C1—C2 | 1.343 (5) |
O2—C7 | 1.209 (4) | C1—H1 | 0.9300 |
O3—C6 | 1.315 (3) | C2—C3 | 1.362 (5) |
O3—H3A | 0.8200 | C2—H2 | 0.9300 |
N1—C5 | 1.350 (4) | C3—C4 | 1.364 (5) |
N1—C7 | 1.382 (4) | C3—H3 | 0.9300 |
N1—H1A | 0.8600 | C4—C5 | 1.382 (5) |
N2—H2A | 0.829 (18) | C4—H4 | 0.9300 |
N2—H2B | 0.803 (17) | C5—C6 | 1.351 (4) |
N2—H2C | 0.850 (18) | ||
C7—O1—H1AA | 109.5 | C2—C3—C4 | 120.0 (3) |
C6—O3—H3A | 109.5 | C2—C3—H3 | 120.0 |
C5—N1—C7 | 126.3 (3) | C4—C3—H3 | 120.0 |
C5—N1—H1A | 116.8 | C3—C4—C5 | 120.5 (3) |
C7—N1—H1A | 116.8 | C3—C4—H4 | 119.7 |
H2C—N2—H2A | 99 (3) | C5—C4—H4 | 119.7 |
H2C—N2—H2B | 103 (3) | N1—C5—C6 | 113.3 (3) |
H2A—N2—H2B | 103 (3) | N1—C5—C4 | 128.9 (3) |
H2A—N2—H2C | 99 (3) | C6—C5—C4 | 117.8 (3) |
H2B—N2—H2C | 103 (3) | O3—C6—C1 | 120.5 (3) |
C6—C1—C2 | 122.0 (3) | O3—C6—C5 | 118.4 (3) |
C6—C1—H1 | 119.0 | C1—C6—C5 | 121.1 (3) |
C2—C1—H1 | 119.0 | O2—C7—O1 | 125.2 (3) |
C1—C2—C3 | 118.6 (4) | O2—C7—N1 | 122.0 (3) |
C1—C2—H2 | 120.7 | O1—C7—N1 | 112.8 (3) |
C3—C2—H2 | 120.7 |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O3i | 0.83 (2) | 2.50 (3) | 3.213 (4) | 145 (4) |
N2—H2A···O3ii | 0.83 (2) | 2.41 (4) | 3.023 (4) | 131 (3) |
N1—H1A···N2iii | 0.86 | 2.18 | 2.968 (4) | 153 |
O3—H3A···N2iv | 0.82 | 2.39 | 3.023 (4) | 134 |
O1—H1AA···O2v | 0.82 | 2.11 | 2.909 (4) | 165 |
N2—H2B···O3 | 0.80 (2) | 1.88 (2) | 2.667 (4) | 167 (3) |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) x, y−1, z; (iii) −x+1, −y+2, −z; (iv) x, y+1, z; (v) −x+3/2, y+1/2, −z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C7H7NO3·NH3 |
Mr | 170.17 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 273 |
a, b, c (Å) | 13.0017 (14), 3.988 (2), 15.358 (2) |
β (°) | 113.927 (4) |
V (Å3) | 727.9 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.12 |
Crystal size (mm) | 0.64 × 0.13 × 0.10 |
Data collection | |
Diffractometer | Bruker APEXII area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.926, 0.988 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4379, 1432, 852 |
Rint | 0.050 |
(sin θ/λ)max (Å−1) | 0.628 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.194, 1.00 |
No. of reflections | 1432 |
No. of parameters | 123 |
No. of restraints | 6 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.34, −0.40 |
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 |
N2—H2A···O3i | 0.829 (18) | 2.50 (3) | 3.213 (4) | 145 (4) |
N2—H2A···O3ii | 0.829 (18) | 2.41 (4) | 3.023 (4) | 131 (3) |
N1—H1A···N2iii | 0.86 | 2.18 | 2.968 (4) | 153 |
O3—H3A···N2iv | 0.82 | 2.39 | 3.023 (4) | 134 |
O1—H1AA···O2v | 0.82 | 2.11 | 2.909 (4) | 165 |
N2—H2B···O3 | 0.803 (17) | 1.879 (18) | 2.667 (4) | 167 (3) |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) x, y−1, z; (iii) −x+1, −y+2, −z; (iv) x, y+1, z; (v) −x+3/2, y+1/2, −z−1/2. |
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 structures (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 Nd metal chains by reaction of the neodymium(III) ion with 2-hydroxy-anilinoformic acid 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 (C7H7NO3) molecule and one ammonia molecule.
In the crystal structure, intramolecular O—H···O and intermolecular N—H···O, N—H···N and O—H···N hydrogen bonds (Table 1, Fig. 2) result in the formation of a supramolecular network structure.