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In the crystal structure of the title compound, C8H6N2O6·H2O, intra­molecular N—H...O and inter­molecular O—H...O, O—H...N, N—H...N and N—H...O hydrogen bonds result in the formation of a supra­molecular network structure.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807048477/at2415sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807048477/at2415Isup2.hkl
Contains datablock I

CCDC reference: 1168236

Key indicators

  • Single-crystal X-ray study
  • T = 273 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.051
  • wR factor = 0.180
  • Data-to-parameter ratio = 11.4

checkCIF/PLATON results

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Alert level B PLAT230_ALERT_2_B Hirshfeld Test Diff for O3 - C8 .. 19.58 su PLAT230_ALERT_2_B Hirshfeld Test Diff for O4 - C8 .. 8.91 su PLAT230_ALERT_2_B Hirshfeld Test Diff for N1 - C2 .. 7.95 su PLAT417_ALERT_2_B Short Inter D-H..H-D H1A .. H7B .. 1.96 Ang. PLAT417_ALERT_2_B Short Inter D-H..H-D H1C .. H7B .. 1.66 Ang. PLAT430_ALERT_2_B Short Inter D...A Contact O2 .. O2 .. 2.58 Ang.
Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.97 PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT230_ALERT_2_C Hirshfeld Test Diff for C3 - C8 .. 6.24 su PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C8 PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.25 PLAT480_ALERT_4_C Long H...A H-Bond Reported H1C .. O6 .. 2.62 Ang.
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 3
0 ALERT level A = In general: serious problem 6 ALERT level B = Potentially serious problem 6 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 9 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 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 La metal chains by reaction of the lanthanum(III) ion with 2-amino-5-nitro-1,3-benzenedicarboxylic 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). In the crystal structure, intramolecular N—H···O and N—H···N and intermolecular O—H···O, O—H···N and N—H···O 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. (1995, 1996); 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. Lanthanum (III) nitrate hexahydrate (432.8 mg, 1 mmol), 2-amino-5-nitro-1,3-benzenedicarboxylic acid (452.3 mg, 2 mmol), ammonia (0.5 mol/l, 8 ml) and distilled water (10 g) were placed into the bomb and sealed. The bomb was then heated under autogenous pressure up to 453 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.

Refinement top

H7A and H7B (for H2O) were located in difference syntheses and refined isotropically [O—H = 0.845 (19) and 0.859 (19) Å, Uiso(H) = 0.105 (18) and 0.101 (18) Å2, respectively]. The remaining H atoms were positioned geometrically, with O—H = 0.82 Å (for OH), N—H = 0.89 Å (for NH) and C—H = 0.93 Å for aromatic H, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C,N,O), where x = 1.2 for aromatic H atoms and x = 1.5 for all other H atoms.

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 La metal chains by reaction of the lanthanum(III) ion with 2-amino-5-nitro-1,3-benzenedicarboxylic 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). In the crystal structure, intramolecular N—H···O and N—H···N and intermolecular O—H···O, O—H···N and N—H···O 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. (1995, 1996); 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 molecular 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.
2-Ammonio-3-carboxy-5-nitrobenzoate monohydrate top
Crystal data top
C8H6N2O6·H2OF(000) = 1008
Mr = 244.16Dx = 1.734 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1493 reflections
a = 25.11 (2) Åθ = 2.8–26.8°
b = 6.5742 (16) ŵ = 0.16 mm1
c = 12.221 (2) ÅT = 273 K
β = 112.002 (1)°Prism, colourless
V = 1870.6 (17) Å30.24 × 0.15 × 0.15 mm
Z = 8
Data collection top
Bruker APEXII area-detector
diffractometer
1881 independent reflections
Radiation source: fine-focus sealed tube965 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.032
φ and ω scansθmax = 26.5°, θmin = 3.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 3131
Tmin = 0.964, Tmax = 0.978k = 88
6078 measured reflectionsl = 1515
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)] = 0.051H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.180 w = 1/[σ2(Fo2) + (0.095P)2 + 0.002P]
where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max < 0.001
1881 reflectionsΔρmax = 0.29 e Å3
165 parametersΔρmin = 0.34 e Å3
3 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.008 (2)
Crystal data top
C8H6N2O6·H2OV = 1870.6 (17) Å3
Mr = 244.16Z = 8
Monoclinic, C2/cMo Kα radiation
a = 25.11 (2) ŵ = 0.16 mm1
b = 6.5742 (16) ÅT = 273 K
c = 12.221 (2) Å0.24 × 0.15 × 0.15 mm
β = 112.002 (1)°
Data collection top
Bruker APEXII area-detector
diffractometer
1881 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
965 reflections with I > 2σ(I)
Tmin = 0.964, Tmax = 0.978Rint = 0.032
6078 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0513 restraints
wR(F2) = 0.180H atoms treated by a mixture of independent and constrained refinement
S = 1.08Δρmax = 0.29 e Å3
1881 reflectionsΔρmin = 0.34 e Å3
165 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
O10.53257 (9)0.2530 (4)1.04684 (18)0.0733 (7)
H10.56460.24491.04390.110*
O20.50729 (11)0.2165 (5)0.8602 (2)0.1059 (10)
O30.29265 (9)0.1319 (4)0.63238 (19)0.0811 (8)
O40.24250 (9)0.3056 (4)0.70420 (19)0.0803 (8)
O50.30586 (10)0.3713 (4)1.11162 (19)0.0856 (8)
O60.39304 (11)0.3002 (4)1.2188 (2)0.0978 (9)
O70.63154 (10)0.2295 (4)0.0267 (2)0.0743 (7)
N10.40250 (8)0.2104 (4)0.72988 (17)0.0512 (6)
H1A0.39020.08930.69780.077*
H1B0.44020.22000.74800.077*
H1C0.38460.30780.67870.077*
N20.35434 (12)0.3203 (4)1.1256 (2)0.0671 (8)
C10.43519 (11)0.2456 (4)0.9352 (2)0.0526 (7)
C20.39154 (13)0.2310 (4)0.8246 (3)0.0579 (8)
C30.33520 (12)0.2444 (4)0.8198 (2)0.0548 (8)
C40.32250 (12)0.2752 (4)0.9165 (2)0.0570 (8)
H4A0.28470.29000.91100.068*
C50.36690 (13)0.2835 (4)1.0216 (2)0.0543 (7)
C60.42259 (12)0.2684 (4)1.0317 (3)0.0549 (7)
H60.45200.27391.10580.066*
C70.49491 (12)0.2382 (5)0.9441 (3)0.0617 (8)
C80.28710 (11)0.2269 (4)0.7107 (2)0.0442 (7)
H7A0.6655 (11)0.222 (7)0.077 (3)0.105 (18)*
H7B0.6325 (18)0.218 (7)0.0425 (19)0.101 (18)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0405 (13)0.1081 (18)0.0635 (14)0.0010 (11)0.0108 (11)0.0007 (10)
O20.0443 (13)0.214 (3)0.0611 (15)0.0020 (14)0.0221 (12)0.0004 (15)
O30.0511 (13)0.119 (2)0.0651 (14)0.0077 (12)0.0123 (11)0.0048 (13)
O40.0402 (13)0.126 (2)0.0684 (14)0.0065 (11)0.0126 (11)0.0054 (12)
O50.0617 (16)0.128 (2)0.0783 (15)0.0096 (13)0.0387 (13)0.0036 (13)
O60.0690 (18)0.171 (3)0.0483 (14)0.0109 (15)0.0165 (13)0.0057 (14)
O70.0417 (13)0.1032 (19)0.0696 (16)0.0009 (11)0.0112 (12)0.0034 (13)
N10.0270 (11)0.0904 (17)0.0363 (12)0.0005 (10)0.0119 (9)0.0018 (10)
N20.0597 (18)0.0849 (19)0.0620 (17)0.0006 (14)0.0288 (15)0.0031 (13)
C10.0363 (15)0.0686 (19)0.0512 (17)0.0007 (12)0.0142 (13)0.0003 (12)
C20.0461 (17)0.074 (2)0.0523 (17)0.0027 (13)0.0175 (14)0.0012 (13)
C30.0401 (16)0.073 (2)0.0498 (16)0.0001 (12)0.0150 (13)0.0044 (13)
C40.0448 (17)0.0675 (19)0.0594 (18)0.0024 (12)0.0204 (15)0.0051 (13)
C50.0513 (17)0.0668 (18)0.0483 (16)0.0012 (13)0.0228 (14)0.0009 (12)
C60.0382 (15)0.0675 (19)0.0538 (17)0.0005 (12)0.0113 (13)0.0022 (13)
C70.0409 (16)0.090 (2)0.0520 (17)0.0022 (14)0.0144 (15)0.0026 (14)
C80.0284 (13)0.0701 (18)0.0332 (13)0.0006 (11)0.0105 (10)0.0007 (12)
Geometric parameters (Å, º) top
O1—C71.261 (3)N1—H1C0.8900
O1—H10.8200N2—C51.440 (4)
O2—C71.186 (3)C1—C61.340 (4)
O3—C81.194 (3)C1—C21.388 (4)
O4—C81.209 (3)C1—C71.463 (4)
O5—N21.211 (3)C2—C31.397 (4)
O6—N21.196 (3)C3—C41.351 (4)
O7—H7A0.845 (19)C3—C81.430 (4)
O7—H7B0.859 (19)C4—C51.350 (4)
N1—C21.293 (3)C4—H4A0.9300
N1—H1A0.8900C5—C61.361 (4)
N1—H1B0.8900C6—H60.9300
C7—O1—H1109.5C4—C3—C8115.8 (3)
H7A—O7—H7B108 (3)C2—C3—C8121.5 (3)
C2—N1—H1A109.5C5—C4—C3117.2 (3)
C2—N1—H1B109.5C5—C4—H4A121.4
H1A—N1—H1B109.5C3—C4—H4A121.4
C2—N1—H1C109.5C4—C5—C6122.5 (3)
H1A—N1—H1C109.5C4—C5—N2118.1 (3)
H1B—N1—H1C109.5C6—C5—N2119.3 (3)
O6—N2—O5125.5 (3)C1—C6—C5120.2 (3)
O6—N2—C5116.9 (3)C1—C6—H6119.9
O5—N2—C5117.6 (3)C5—C6—H6119.9
C6—C1—C2120.3 (3)O2—C7—O1121.9 (3)
C6—C1—C7120.8 (3)O2—C7—C1122.2 (3)
C2—C1—C7118.9 (3)O1—C7—C1115.9 (3)
N1—C2—C1121.6 (3)O3—C8—O4123.7 (3)
N1—C2—C3121.4 (3)O3—C8—C3118.6 (3)
C1—C2—C3117.0 (3)O4—C8—C3117.7 (3)
C4—C3—C2122.7 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1B···O20.891.732.514 (3)146
O7—H7B···O3i0.86 (2)2.57 (3)3.254 (4)137 (3)
O7—H7B···N1i0.86 (2)2.12 (2)2.927 (4)156 (4)
N1—H1C···O6ii0.892.623.225 (3)126
N1—H1C···N2ii0.892.573.384 (3)152
N1—H1C···O7i0.892.442.927 (4)115
N1—H1B···O2iii0.892.192.866 (4)132
N1—H1A···O6iv0.892.573.365 (3)149
O1—H1···O7v0.821.772.592 (4)176
Symmetry codes: (i) x+1, y, z+1/2; (ii) x, y+1, z1/2; (iii) x+1, y, z+3/2; (iv) x, y, z1/2; (v) x, y, z+1.

Experimental details

Crystal data
Chemical formulaC8H6N2O6·H2O
Mr244.16
Crystal system, space groupMonoclinic, C2/c
Temperature (K)273
a, b, c (Å)25.11 (2), 6.5742 (16), 12.221 (2)
β (°) 112.002 (1)
V3)1870.6 (17)
Z8
Radiation typeMo Kα
µ (mm1)0.16
Crystal size (mm)0.24 × 0.15 × 0.15
Data collection
DiffractometerBruker APEXII area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.964, 0.978
No. of measured, independent and
observed [I > 2σ(I)] reflections
6078, 1881, 965
Rint0.032
(sin θ/λ)max1)0.627
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.051, 0.180, 1.08
No. of reflections1881
No. of parameters165
No. of restraints3
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.29, 0.34

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
N1—H1B···O20.891.732.514 (3)146
O7—H7B···O3i0.859 (19)2.57 (3)3.254 (4)137 (3)
O7—H7B···N1i0.859 (19)2.12 (2)2.927 (4)156 (4)
N1—H1C···O6ii0.892.623.225 (3)126
N1—H1C···N2ii0.892.573.384 (3)152
N1—H1C···O7i0.892.442.927 (4)115
N1—H1B···O2iii0.892.192.866 (4)132
N1—H1A···O6iv0.892.573.365 (3)149
O1—H1···O7v0.821.772.592 (4)176
Symmetry codes: (i) x+1, y, z+1/2; (ii) x, y+1, z1/2; (iii) x+1, y, z+3/2; (iv) x, y, z1/2; (v) x, y, z+1.
 

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