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In the crystal structure of the title complex, C7H7NO3·NH3, inter­molecular N—H...O, N—H...N and O—H...N hydrogen bonds result in the formation of a supra­molecular network structure.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680704086X/at2378sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S160053680704086X/at2378Isup2.hkl
Contains datablock I

CCDC reference: 1101558

Key indicators

  • Single-crystal X-ray study
  • T = 273 K
  • Mean [sigma](C-C) = 0.006 Å
  • R factor = 0.055
  • wR factor = 0.194
  • Data-to-parameter ratio = 11.6

checkCIF/PLATON results

No syntax errors found



Alert level B PLAT230_ALERT_2_B Hirshfeld Test Diff for O1 - C7 .. 12.09 su PLAT230_ALERT_2_B Hirshfeld Test Diff for O3 - C6 .. 8.02 su PLAT230_ALERT_2_B Hirshfeld Test Diff for C1 - C6 .. 8.09 su PLAT417_ALERT_2_B Short Inter D-H..H-D H2A .. H3A .. 1.94 Ang.
Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.96 PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size ....... 0.64 mm PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ..... ? PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C6 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C7 PLAT334_ALERT_2_C Small Average Benzene C-C Dist. C1 -C6 1.36 Ang. PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 6 PLAT420_ALERT_2_C D-H Without Acceptor N2 - H2C ... ? PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 1
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 6
0 ALERT level A = In general: serious problem 4 ALERT level B = Potentially serious problem 10 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 8 ALERT type 2 Indicator that the structure model may be wrong or deficient 4 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

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 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.

Related literature top

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).

Experimental top

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.

Refinement top

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).

Structure description 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 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).

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, 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.
N-(2-Hydroxyphenyl)carbamic acid–ammonia (1/1) top
Crystal data top
C7H7NO3·NH3F(000) = 360
Mr = 170.17Dx = 1.553 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1897 reflections
a = 13.0017 (14) Åθ = 2.7–27.9°
b = 3.988 (2) ŵ = 0.12 mm1
c = 15.358 (2) ÅT = 273 K
β = 113.927 (4)°Prism, colourless
V = 727.9 (5) Å30.64 × 0.13 × 0.10 mm
Z = 4
Data collection top
Bruker APEXII area-detector
diffractometer
1432 independent reflections
Radiation source: fine-focus sealed tube852 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.050
φ and ω scansθmax = 26.5°, θmin = 2.9°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1615
Tmin = 0.926, Tmax = 0.988k = 44
4379 measured reflectionsl = 1919
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.055Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.194H 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 parametersΔρmax = 0.34 e Å3
6 restraintsΔρmin = 0.40 e Å3
Crystal data top
C7H7NO3·NH3V = 727.9 (5) Å3
Mr = 170.17Z = 4
Monoclinic, P21/nMo Kα radiation
a = 13.0017 (14) ŵ = 0.12 mm1
b = 3.988 (2) ÅT = 273 K
c = 15.358 (2) Å0.64 × 0.13 × 0.10 mm
β = 113.927 (4)°
Data collection top
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 = 0.988Rint = 0.050
4379 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0556 restraints
wR(F2) = 0.194H atoms treated by a mixture of independent and constrained refinement
S = 1.00Δρmax = 0.34 e Å3
1432 reflectionsΔρmin = 0.40 e Å3
123 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
xyzUiso*/Ueq
O10.6556 (3)1.3946 (8)0.1911 (2)0.0849 (10)
H1AA0.67521.46010.23260.127*
O20.8205 (2)1.1177 (7)0.13776 (16)0.0666 (9)
O30.6313 (2)0.9654 (7)0.0654 (2)0.0746 (9)
H3A0.63661.14830.09120.112*
N10.7137 (2)1.1124 (7)0.05209 (18)0.0501 (8)
H1A0.65211.18470.05080.060*
N20.5039 (2)0.5292 (8)0.1088 (2)0.0521 (8)
C10.7879 (3)0.6672 (9)0.1621 (3)0.0668 (11)
H10.75390.62650.20390.080*
C20.8910 (3)0.5422 (10)0.1823 (3)0.0640 (10)
H20.92790.41560.23700.077*
C30.9404 (3)0.6048 (9)0.1209 (3)0.0612 (10)
H31.01170.52040.13350.073*
C40.8853 (3)0.7912 (9)0.0409 (3)0.0571 (9)
H40.91930.83300.00090.069*
C50.7794 (3)0.9184 (8)0.0215 (2)0.0479 (8)
C60.7326 (2)0.8485 (7)0.0835 (2)0.0398 (7)
C70.7361 (3)1.2060 (9)0.1293 (2)0.0497 (8)
H2A0.496 (3)0.353 (6)0.078 (3)0.092 (16)*
H2B0.546 (2)0.635 (7)0.093 (2)0.080 (10)*
H2C0.547 (4)0.456 (11)0.1634 (17)0.101 (3)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.097 (2)0.098 (2)0.0700 (18)0.0120 (17)0.0455 (16)0.0082 (15)
O20.0646 (15)0.092 (2)0.0615 (16)0.0094 (12)0.0442 (13)0.0098 (12)
O30.0825 (18)0.0757 (19)0.095 (2)0.0218 (13)0.0663 (16)0.0250 (15)
N10.0523 (15)0.0578 (17)0.0517 (16)0.0046 (12)0.0329 (13)0.0013 (12)
N20.0649 (18)0.0522 (18)0.0545 (17)0.0054 (14)0.0400 (14)0.0048 (14)
C10.091 (3)0.061 (2)0.067 (2)0.0063 (19)0.051 (2)0.0075 (18)
C20.069 (2)0.066 (2)0.057 (2)0.0021 (18)0.0256 (18)0.0003 (17)
C30.0501 (18)0.064 (2)0.070 (2)0.0046 (16)0.0253 (17)0.0072 (18)
C40.0523 (18)0.061 (2)0.066 (2)0.0081 (15)0.0322 (17)0.0043 (17)
C50.0543 (18)0.0482 (18)0.0501 (17)0.0115 (14)0.0304 (15)0.0099 (14)
C60.0452 (15)0.0375 (15)0.0471 (16)0.0042 (12)0.0294 (13)0.0043 (12)
C70.0523 (18)0.058 (2)0.0438 (16)0.0147 (15)0.0245 (14)0.0080 (15)
Geometric parameters (Å, º) top
O1—C71.325 (4)C1—C61.338 (5)
O1—H1AA0.8200C1—C21.343 (5)
O2—C71.209 (4)C1—H10.9300
O3—C61.315 (3)C2—C31.362 (5)
O3—H3A0.8200C2—H20.9300
N1—C51.350 (4)C3—C41.364 (5)
N1—C71.382 (4)C3—H30.9300
N1—H1A0.8600C4—C51.382 (5)
N2—H2A0.829 (18)C4—H40.9300
N2—H2B0.803 (17)C5—C61.351 (4)
N2—H2C0.850 (18)
C7—O1—H1AA109.5C2—C3—C4120.0 (3)
C6—O3—H3A109.5C2—C3—H3120.0
C5—N1—C7126.3 (3)C4—C3—H3120.0
C5—N1—H1A116.8C3—C4—C5120.5 (3)
C7—N1—H1A116.8C3—C4—H4119.7
H2C—N2—H2A99 (3)C5—C4—H4119.7
H2C—N2—H2B103 (3)N1—C5—C6113.3 (3)
H2A—N2—H2B103 (3)N1—C5—C4128.9 (3)
H2A—N2—H2C99 (3)C6—C5—C4117.8 (3)
H2B—N2—H2C103 (3)O3—C6—C1120.5 (3)
C6—C1—C2122.0 (3)O3—C6—C5118.4 (3)
C6—C1—H1119.0C1—C6—C5121.1 (3)
C2—C1—H1119.0O2—C7—O1125.2 (3)
C1—C2—C3118.6 (4)O2—C7—N1122.0 (3)
C1—C2—H2120.7O1—C7—N1112.8 (3)
C3—C2—H2120.7
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O3i0.83 (2)2.50 (3)3.213 (4)145 (4)
N2—H2A···O3ii0.83 (2)2.41 (4)3.023 (4)131 (3)
N1—H1A···N2iii0.862.182.968 (4)153
O3—H3A···N2iv0.822.393.023 (4)134
O1—H1AA···O2v0.822.112.909 (4)165
N2—H2B···O30.80 (2)1.88 (2)2.667 (4)167 (3)
Symmetry codes: (i) x+1, y+1, z; (ii) x, y1, z; (iii) x+1, y+2, z; (iv) x, y+1, z; (v) x+3/2, y+1/2, z1/2.

Experimental details

Crystal data
Chemical formulaC7H7NO3·NH3
Mr170.17
Crystal system, space groupMonoclinic, P21/n
Temperature (K)273
a, b, c (Å)13.0017 (14), 3.988 (2), 15.358 (2)
β (°) 113.927 (4)
V3)727.9 (5)
Z4
Radiation typeMo Kα
µ (mm1)0.12
Crystal size (mm)0.64 × 0.13 × 0.10
Data collection
DiffractometerBruker APEXII area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.926, 0.988
No. of measured, independent and
observed [I > 2σ(I)] reflections
4379, 1432, 852
Rint0.050
(sin θ/λ)max1)0.628
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.055, 0.194, 1.00
No. of reflections1432
No. of parameters123
No. of restraints6
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.34, 0.40

Computer programs: APEX2 (Bruker, 2005), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Siemens, 1996).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O3i0.829 (18)2.50 (3)3.213 (4)145 (4)
N2—H2A···O3ii0.829 (18)2.41 (4)3.023 (4)131 (3)
N1—H1A···N2iii0.862.182.968 (4)153
O3—H3A···N2iv0.822.393.023 (4)134
O1—H1AA···O2v0.822.112.909 (4)165
N2—H2B···O30.803 (17)1.879 (18)2.667 (4)167 (3)
Symmetry codes: (i) x+1, y+1, z; (ii) x, y1, z; (iii) x+1, y+2, z; (iv) x, y+1, z; (v) x+3/2, y+1/2, z1/2.
 

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