Buy article online - an online subscription or single-article purchase is required to access this article.
Download citation
Download citation
link to html
In the crystal structure of the title compound, C6H5N4O6·H2O, inter­molecular O—H...N and O—H...O hydrogen bonds result in the formation of a supra­molecular network structure; intra­molecular O—H...O and N—H...O hydrogen bonds are also present.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807040779/hk2313sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807040779/hk2313Isup2.hkl
Contains datablock I

CCDC reference: 1101500

Key indicators

  • Single-crystal X-ray study
  • T = 273 K
  • Mean [sigma](C-C) = 0.005 Å
  • R factor = 0.051
  • wR factor = 0.180
  • Data-to-parameter ratio = 10.5

checkCIF/PLATON results

No syntax errors found



Alert level B PLAT230_ALERT_2_B Hirshfeld Test Diff for O1 - N1 .. 7.21 su PLAT230_ALERT_2_B Hirshfeld Test Diff for N2 - C6 .. 8.98 su PLAT351_ALERT_3_B Long C-H Bond (0.96A) C6 - H2B ... 1.18 Ang. PLAT430_ALERT_2_B Short Inter D...A Contact O2 .. O2 .. 2.60 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 O6 - N4 .. 5.45 su PLAT230_ALERT_2_C Hirshfeld Test Diff for N1 - C1 .. 5.50 su PLAT230_ALERT_2_C Hirshfeld Test Diff for N1 - C5 .. 6.10 su PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.11 PLAT320_ALERT_2_C Check Hybridisation of C6 in Main Residue . ? PLAT322_ALERT_2_C Check Hybridisation of H2B in Main Residue . ? PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 5 PLAT417_ALERT_2_C Short Inter D-H..H-D H2A .. H2A .. 2.13 Ang.
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 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 10 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 0 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 amido groups are one of the most important classes of biological ligands, the coordination of metal-amido groups complexes are of critical importance in biological systems, organic materials and coordination chemistry. Recently, amido groups with variable coordination modes have been used to construct metal-organic supramolecular structures (Harrop et al., 2003; Qi, Ma et al., 2003; Qi, Qiu et al., 2003; Rauko et al., 2001; Foster et al., 1999; Zhou et al., 1999). We originally attempted to synthesize complexes featuring La metal chains by reaction of the lanthanum(III) ion with 1-hydroxy-2,4-dinitro-6-carboxamidopyridine ligand. Unfortunately, we obtained only the title compound, (I), and we report herein its crystal structure.

In the molecule of (I) (Fig. 1), the bond lengths and angles are within normal ranges (Allen et al., 1987). It contains one 1-hydroxy-2,4-dinitro-6-carbox- amidopyridine molecule and one water molecule.

In the crystal structure, intramolecular N—H···O and O—H···O and intermolecular O—H···N and O—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); Desiraju (1997); Braga et al. (1998); Harrop et al. (2003); Qi, Ma et al. (2003); Qi, Qiu et al. (2003); Rauko et al. (2001); Foster et al. (1999); Zhou et al. (1999). 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. Lanthanum (III) nitrate hexahydrate (216.4 mg, 0.5 mmol), 1-hydroxy-2,4-dinitro-6-carboxamidopyridine (229.2 mg, 1 mmol) and distilled water (4 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.

Refinement top

H7A, H7B (for OH2) and H2A, H2B (for NH2) were located in difference syntheses and refined isotropically [O—H = 0.85 (2) and 0.85 (3) Å, Uiso(H) = 0.084 (2) and 0.093 (13) Å2; N—H = 0.82 (5) and 0.85 (5) Å, Uiso(H) = 0.11 (4) and 0.12 (6) Å2]. The remaining H atoms were positioned geometrically, with O—H = 0.82 Å (for OH) and C—H = 0.93 Å for aromatic H, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C,O), where x = 1.2 for aromatic H, and x = 1.5 for OH 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 amido groups are one of the most important classes of biological ligands, the coordination of metal-amido groups complexes are of critical importance in biological systems, organic materials and coordination chemistry. Recently, amido groups with variable coordination modes have been used to construct metal-organic supramolecular structures (Harrop et al., 2003; Qi, Ma et al., 2003; Qi, Qiu et al., 2003; Rauko et al., 2001; Foster et al., 1999; Zhou et al., 1999). We originally attempted to synthesize complexes featuring La metal chains by reaction of the lanthanum(III) ion with 1-hydroxy-2,4-dinitro-6-carboxamidopyridine ligand. Unfortunately, we obtained only the title compound, (I), and we report herein its crystal structure.

In the molecule of (I) (Fig. 1), the bond lengths and angles are within normal ranges (Allen et al., 1987). It contains one 1-hydroxy-2,4-dinitro-6-carbox- amidopyridine molecule and one water molecule.

In the crystal structure, intramolecular N—H···O and O—H···O and intermolecular O—H···N and O—H···O hydrogen bonds (Table 1, Fig. 2) result in the formation of a supramolecular network structure.

For general background, see: Desiraju (1995); Desiraju (1997); Braga et al. (1998); Harrop et al. (2003); Qi, Ma et al. (2003); Qi, Qiu et al. (2003); Rauko et al. (2001); Foster et al. (1999); Zhou et al. (1999). For bond-length data, see: Allen et al. (1987).

Computing details top

Data collection: SMART (Siemens, 1996); 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.
1-Hydroxy-4,6-dinitropyridine-2-carboxamide monohydrate top
Crystal data top
C6H5N4O6·H2OF(000) = 1016
Mr = 247.16Dx = 1.798 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1477 reflections
a = 25.1116 (13) Åθ = 2.8–26.8°
b = 6.409 (3) ŵ = 0.17 mm1
c = 12.228 (2) ÅT = 273 K
β = 111.914 (3)°Prism, colorless
V = 1825.9 (9) Å30.24 × 0.15 × 0.14 mm
Z = 8
Data collection top
Bruker SMART CCD area-detector
diffractometer
1802 independent reflections
Radiation source: fine-focus sealed tube961 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.030
φ and ω scansθmax = 26.3°, θmin = 3.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 3131
Tmin = 0.961, Tmax = 0.976k = 78
5880 measured reflectionsl = 1415
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)] = 0.051Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.180H atoms treated by a mixture of independent and constrained refinement
S = 1.10 w = 1/[σ2(Fo2) + (0.0954P)2 + 0.002P]
where P = (Fo2 + 2Fc2)/3
1802 reflections(Δ/σ)max < 0.001
171 parametersΔρmax = 0.34 e Å3
6 restraintsΔρmin = 0.35 e Å3
Crystal data top
C6H5N4O6·H2OV = 1825.9 (9) Å3
Mr = 247.16Z = 8
Monoclinic, C2/cMo Kα radiation
a = 25.1116 (13) ŵ = 0.17 mm1
b = 6.409 (3) ÅT = 273 K
c = 12.228 (2) Å0.24 × 0.15 × 0.14 mm
β = 111.914 (3)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
1802 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
961 reflections with I > 2σ(I)
Tmin = 0.961, Tmax = 0.976Rint = 0.030
5880 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0516 restraints
wR(F2) = 0.180H atoms treated by a mixture of independent and constrained refinement
S = 1.10Δρmax = 0.34 e Å3
1802 reflectionsΔρmin = 0.35 e Å3
171 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
O10.40223 (9)0.2097 (4)0.72917 (18)0.0690 (7)
H10.43700.21400.74630.104*
O20.50781 (11)0.2161 (5)0.8613 (2)0.0991 (10)
O30.29276 (9)0.1316 (4)0.63107 (18)0.0767 (7)
O40.24231 (9)0.3054 (4)0.7040 (2)0.0754 (7)
O50.30587 (10)0.3718 (4)1.11209 (19)0.0812 (8)
O60.39283 (12)0.3006 (4)1.2182 (2)0.0920 (9)
O70.13173 (10)0.2718 (4)0.5262 (2)0.0702 (7)
H7A0.1131 (12)0.247 (8)0.570 (3)0.084 (2)*
H7B0.1644 (6)0.270 (5)0.582 (2)0.093 (13)*
N10.39102 (12)0.2308 (4)0.8248 (2)0.0688 (8)
N20.53304 (9)0.2532 (5)1.0472 (2)0.0500 (6)
H2A0.516 (3)0.155 (6)1.006 (5)0.11 (4)*
H2B0.526 (4)0.363 (6)1.006 (6)0.12 (6)*
N30.28695 (11)0.2261 (4)0.7096 (2)0.0568 (7)
N40.35437 (12)0.3200 (4)1.1256 (2)0.0640 (7)
C10.33551 (12)0.2440 (4)0.8194 (2)0.0495 (7)
C20.32299 (13)0.2744 (4)0.9176 (2)0.0517 (7)
H20.28530.28810.91240.062*
C30.36654 (13)0.2836 (4)1.0208 (3)0.0510 (7)
C40.42297 (13)0.2684 (4)1.0325 (3)0.0525 (7)
H40.45220.27441.10660.063*
C50.43531 (11)0.2447 (4)0.9346 (3)0.0518 (7)
C60.49504 (13)0.2384 (5)0.9435 (3)0.0592 (8)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0383 (12)0.1196 (19)0.0513 (12)0.0013 (11)0.0192 (10)0.0030 (11)
O20.0390 (13)0.201 (3)0.0591 (15)0.0051 (14)0.0201 (12)0.0031 (15)
O30.0529 (13)0.114 (2)0.0584 (13)0.0069 (13)0.0150 (11)0.0153 (13)
O40.0372 (13)0.115 (2)0.0687 (15)0.0086 (11)0.0142 (11)0.0072 (12)
O50.0588 (16)0.115 (2)0.0808 (16)0.0075 (13)0.0390 (13)0.0070 (14)
O60.0717 (18)0.151 (2)0.0477 (14)0.0125 (15)0.0155 (13)0.0017 (14)
O70.0379 (13)0.0927 (17)0.0711 (15)0.0018 (11)0.0102 (12)0.0045 (12)
N10.0546 (18)0.088 (2)0.0626 (17)0.0005 (13)0.0209 (15)0.0005 (13)
N20.0286 (13)0.0732 (16)0.0403 (13)0.0026 (11)0.0035 (11)0.0013 (11)
N30.0377 (15)0.0807 (18)0.0496 (15)0.0028 (12)0.0136 (12)0.0046 (12)
N40.0606 (19)0.0761 (18)0.0605 (17)0.0012 (14)0.0286 (16)0.0047 (13)
C10.0404 (16)0.0590 (18)0.0479 (16)0.0002 (12)0.0151 (13)0.0037 (12)
C20.0430 (17)0.0583 (18)0.0548 (17)0.0012 (12)0.0192 (14)0.0044 (12)
C30.0474 (17)0.0606 (18)0.0489 (16)0.0022 (13)0.0224 (14)0.0011 (12)
C40.0396 (16)0.0646 (19)0.0492 (17)0.0013 (13)0.0118 (13)0.0011 (12)
C50.0356 (16)0.0668 (18)0.0507 (17)0.0003 (12)0.0137 (14)0.0024 (13)
C60.0408 (17)0.082 (2)0.0548 (19)0.0005 (15)0.0178 (16)0.0057 (16)
Geometric parameters (Å, º) top
O1—N11.308 (3)N2—C61.275 (4)
O1—H10.8200N3—C11.442 (4)
O2—C61.172 (4)N4—C31.443 (4)
O3—N31.189 (3)C1—C21.364 (4)
O4—N31.209 (3)C2—C31.328 (4)
O5—N41.213 (3)C2—H20.9300
O6—N41.189 (4)C3—C41.373 (4)
O7—H7A0.85 (3)C4—C51.353 (4)
O7—H7B0.85 (2)C4—H40.9300
N1—C11.373 (4)C5—C61.463 (4)
N1—C51.390 (4)C6—H2A0.92 (6)
N2—H2A0.82 (5)C6—H2B1.17 (7)
N2—H2B0.85 (5)
N1—O1—H1109.5N1—C1—N3122.0 (3)
H7A—O7—H7B95 (3)C3—C2—C1117.7 (3)
O1—N1—C1121.1 (3)C3—C2—H2121.2
O1—N1—C5120.6 (3)C1—C2—H2121.2
C1—N1—C5118.3 (3)C2—C3—C4123.2 (3)
H2A—N2—H2B109 (3)C2—C3—N4118.6 (3)
H2A—N2—C646 (4)C4—C3—N4118.1 (3)
H2B—N2—C663 (5)C5—C4—C3118.9 (3)
H2B—N2—H2A109 (4)C5—C4—H4120.5
C6—N2—H2A46 (4)C3—C4—H4120.5
H2A—N2—H2B109 (3)C4—C5—N1119.8 (3)
C6—N2—H2B63 (5)C4—C5—C6120.3 (3)
H2A—N2—H2B109 (3)N1—C5—C6119.9 (3)
O3—N3—O4124.0 (3)O2—C6—N2121.3 (3)
O3—N3—C1118.4 (3)O2—C6—C5122.7 (3)
O4—N3—C1117.6 (3)N2—C6—C5116.0 (3)
O6—N4—O5125.2 (3)O2—C6—H2A113 (5)
O6—N4—C3117.6 (3)C5—C6—H2A109 (5)
O5—N4—C3117.3 (3)O2—C6—H2B109 (4)
C2—C1—N1122.0 (3)C5—C6—H2B116 (5)
C2—C1—N3116.0 (3)H2A—C6—H2B80 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O20.821.812.539 (3)148
N2—H2A···O20.82 (5)1.75 (7)2.133 (3)106 (5)
O7—H7B···O40.85 (2)1.98 (2)2.824 (3)172 (3)
O1—H1···O2i0.822.242.863 (3)133
O7—H7A···N2ii0.85 (3)1.92 (2)2.590 (3)135 (3)
Symmetry codes: (i) x+1, y, z+3/2; (ii) x1/2, y+1/2, z1/2.

Experimental details

Crystal data
Chemical formulaC6H5N4O6·H2O
Mr247.16
Crystal system, space groupMonoclinic, C2/c
Temperature (K)273
a, b, c (Å)25.1116 (13), 6.409 (3), 12.228 (2)
β (°) 111.914 (3)
V3)1825.9 (9)
Z8
Radiation typeMo Kα
µ (mm1)0.17
Crystal size (mm)0.24 × 0.15 × 0.14
Data collection
DiffractometerBruker SMART CCD area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.961, 0.976
No. of measured, independent and
observed [I > 2σ(I)] reflections
5880, 1802, 961
Rint0.030
(sin θ/λ)max1)0.624
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.051, 0.180, 1.10
No. of reflections1802
No. of parameters171
No. of restraints6
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.34, 0.35

Computer programs: SMART (Siemens, 1996), 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
O1—H1···O20.821.812.539 (3)148
N2—H2A···O20.82 (5)1.75 (7)2.133 (3)106 (5)
O7—H7B···O40.85 (2)1.98 (2)2.824 (3)172 (3)
O1—H1···O2i0.822.242.863 (3)133
O7—H7A···N2ii0.85 (3)1.92 (2)2.590 (3)135 (3)
Symmetry codes: (i) x+1, y, z+3/2; (ii) x1/2, y+1/2, z1/2.
 

Subscribe to Acta Crystallographica Section E: Crystallographic Communications

The full text of this article is available to subscribers to the journal.

If you have already registered and are using a computer listed in your registration details, please email support@iucr.org for assistance.

Buy online

You may purchase this article in PDF and/or HTML formats. For purchasers in the European Community who do not have a VAT number, VAT will be added at the local rate. Payments to the IUCr are handled by WorldPay, who will accept payment by credit card in several currencies. To purchase the article, please complete the form below (fields marked * are required), and then click on `Continue'.
E-mail address* 
Repeat e-mail address* 
(for error checking) 

Format*   PDF (US $40)
   HTML (US $40)
   PDF+HTML (US $50)
In order for VAT to be shown for your country javascript needs to be enabled.

VAT number 
(non-UK EC countries only) 
Country* 
 

Terms and conditions of use
Contact us

Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds