PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2010 March 1; 66(Pt 3): o667.
Published online 2010 February 20. doi:  10.1107/S1600536810005362
PMCID: PMC2983508

3,5-Dicarboxyanilinium nitrate dihydrate

Abstract

In the crystal of the title compound, C8H8NO4 +·NO3 ·2H2O, the 5-ammonio­isophthalic acid cations, the nitrate anions and the water mol­ecules are linked by N—H(...)O, O—H(...)O and C—H (...)O hydrogen bonds into a three-dimensional network. The structure is further stabilized by aromatic π–π stacking inter­actions, with centroid–centroid separations of 3.827 (2) Å.

Related literature

For the crystal structure of 5-amino­isophthalic acid hemihydrate, see: Dobson et al. (1998 [triangle]). For the use of 5-amino­isophthalic acid as a ligand, see: Liao et al. (2004 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0o667-scheme1.jpg

Experimental

Crystal data

  • C8H8NO4 +·NO3 ·2H2O
  • M r = 280.20
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0o667-efi1.jpg
  • a = 8.3436 (17) Å
  • b = 8.6234 (17) Å
  • c = 16.862 (3) Å
  • β = 97.31 (3)°
  • V = 1203.4 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.14 mm−1
  • T = 293 K
  • 0.35 × 0.25 × 0.10 mm

Data collection

  • Rigaku SCXmini diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 [triangle]) T min = 0.960, T max = 0.986
  • 12169 measured reflections
  • 2753 independent reflections
  • 1905 reflections with I > 2σ(I)
  • R int = 0.055

Refinement

  • R[F 2 > 2σ(F 2)] = 0.054
  • wR(F 2) = 0.129
  • S = 1.07
  • 2753 reflections
  • 190 parameters
  • ?
  • Δρmax = 0.28 e Å−3
  • Δρmin = −0.24 e Å−3

Data collection: CrystalClear (Rigaku 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: PRPKAPPA (Ferguson, 1999 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810005362/rz2414sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810005362/rz2414Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This work was supported by the Technical Fund Financing Projects (grant Nos. 9207042464 and 9207041482) from Southeast University to Zhi-Rong Qu.

supplementary crystallographic information

Comment

5-Aminobenzene-1,3-dioic acid (5-aminoisophthalic acid) is an important molecule due to its amphoteric property. The report on 5-aminobenzene-1,3-dioic acid hemihydrate (Dobson et al. 1998) is one of a series on hydrogen bonding in aminosubstituted carboxylic acids, and follows reports on a novel tetragonal phase of aminobutyric acid, on 8-aminocaprylic acid and on 3-aminoisobutyric acid monohydrate. In addition, 5-aminobenzene-1,3-dioic acid is an attractive ligand for use in the generation of polar coordination polymers (Liao et al., 2004).

The asymmetric unit of the title compound comprises two water molecules, a 5-ammonioisophthalic acid cation and one nitrate anion (Fig. 1). The crystal packing is stabilized by hydrogen bonds of N—H···O, O—H···O, C—H···O (Table 1) connecting neighbouring water molecules, cations and anions into a three-dimensional network (Fig. 2). The structure is further stabiized by aromatic π···π stacking interactions, with centroid-to-centroid separations of 3.827 (2) Å.

Experimental

5-Aminoisophthalic acid (1.81 g, 10 mmol) was dissolved in water (5 ml), ethanol (20 ml) and nitric acid (0.57 g, 10 mmol) and the solution was filtered. After slowly evaporating over a period of 3 d, colourless prismatic crystals of the title compound suitable for X-ray diffraction analysis were isolated.

Refinement

All the H atoms were calculated geometrically and were allowed to ride on their parent atomsd, with C—H = 0.93–0.97 Å, N—H = 0.89 Å, and with Uiso(H) = 1.2Ueq(C) and 1.5Ueq(N).

Figures

Fig. 1.
The asymmetric unit of the title compound, with displacement ellipsoids drawn at the 30% probability level. Intermolecular hydrogen bonds are shown as dashed lines.
Fig. 2.
Packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

Crystal data

C8H8NO4+·NO3·2H2OF(000) = 584
Mr = 280.20Dx = 1.547 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1753 reflections
a = 8.3436 (17) Åθ = 3.1–27.5°
b = 8.6234 (17) ŵ = 0.14 mm1
c = 16.862 (3) ÅT = 293 K
β = 97.31 (3)°Prism, colourless
V = 1203.4 (4) Å30.35 × 0.25 × 0.10 mm
Z = 4

Data collection

Rigaku SCXmini diffractometer2753 independent reflections
Radiation source: fine-focus sealed tube1905 reflections with I > 2σ(I)
graphiteRint = 0.055
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.2°
CCD profile fitting scansh = −10→10
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)k = −11→11
Tmin = 0.960, Tmax = 0.986l = −21→21
12169 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.054w = 1/[σ2(Fo2) + (0.0423P)2 + 0.7735P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.129(Δ/σ)max < 0.001
S = 1.07Δρmax = 0.28 e Å3
2753 reflectionsΔρmin = −0.24 e Å3
190 parametersExtinction correction: SHELXL97 (Sheldrick, 2008)
0 restraintsExtinction coefficient: 0.0014 (1)
Primary atom site location: structure-invariant direct methods

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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)

xyzUiso*/Ueq
O40.4952 (2)0.14675 (19)0.42859 (10)0.0442 (5)
H40.52750.06030.44320.066*
N10.3108 (2)0.6452 (2)0.29415 (11)0.0328 (5)
H1A0.36510.58130.26580.049*
H1B0.36320.73500.30100.049*
H1C0.21260.66140.26820.049*
C20.3575 (3)0.4279 (2)0.38793 (13)0.0280 (5)
H20.40700.37440.34980.034*
O10.1136 (3)0.6025 (2)0.62566 (11)0.0545 (6)
H10.06690.65590.65580.082*
O30.3885 (3)0.1368 (2)0.54276 (11)0.0513 (5)
C40.2667 (3)0.4405 (2)0.51780 (13)0.0296 (5)
H4A0.25560.39460.56670.036*
C10.2969 (3)0.5756 (2)0.37216 (13)0.0264 (5)
C50.2069 (3)0.5891 (3)0.50071 (14)0.0299 (5)
C60.2225 (3)0.6570 (2)0.42699 (13)0.0300 (5)
H60.18300.75630.41520.036*
O20.0772 (3)0.8101 (2)0.54705 (12)0.0605 (6)
C30.3432 (3)0.3610 (2)0.46132 (13)0.0275 (5)
C70.1260 (3)0.6799 (3)0.55994 (14)0.0356 (6)
O50.2218 (2)−0.0029 (2)0.30373 (12)0.0461 (5)
O60.4607 (2)−0.06093 (19)0.27628 (11)0.0441 (5)
O70.3495 (2)0.15470 (19)0.23390 (12)0.0460 (5)
N20.3433 (2)0.0312 (2)0.27105 (12)0.0333 (5)
C80.4106 (3)0.2034 (3)0.47971 (13)0.0304 (5)
O90.9920 (2)0.7569 (2)0.73715 (12)0.0422 (5)
O80.8512 (3)0.5594 (3)0.84014 (16)0.0667 (7)
H9A0.916 (5)0.828 (5)0.729 (2)0.091 (13)*
H8A0.904 (4)0.500 (5)0.885 (2)0.089 (13)*
H8B0.781 (6)0.612 (5)0.861 (3)0.111 (16)*
H9B0.949 (6)0.706 (6)0.771 (3)0.14 (2)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O40.0653 (12)0.0295 (9)0.0394 (10)0.0196 (9)0.0133 (9)0.0042 (7)
N10.0348 (11)0.0289 (10)0.0359 (11)0.0043 (8)0.0092 (9)0.0069 (8)
C20.0321 (12)0.0225 (11)0.0299 (12)0.0021 (9)0.0057 (10)−0.0010 (9)
O10.0824 (15)0.0496 (11)0.0354 (10)0.0243 (10)0.0225 (10)0.0014 (9)
O30.0760 (14)0.0357 (10)0.0470 (11)0.0214 (10)0.0261 (10)0.0177 (8)
C40.0365 (13)0.0251 (11)0.0269 (12)0.0028 (9)0.0025 (10)0.0010 (9)
C10.0283 (11)0.0236 (11)0.0275 (11)−0.0002 (9)0.0038 (9)0.0026 (9)
C50.0323 (12)0.0258 (11)0.0313 (12)0.0017 (9)0.0029 (10)−0.0025 (9)
C60.0345 (12)0.0204 (10)0.0348 (12)0.0054 (9)0.0027 (10)0.0003 (9)
O20.0920 (16)0.0371 (11)0.0573 (13)0.0270 (11)0.0282 (12)0.0011 (9)
C30.0317 (12)0.0209 (10)0.0293 (12)0.0016 (9)0.0021 (9)0.0008 (9)
C70.0421 (14)0.0308 (13)0.0343 (13)0.0059 (11)0.0063 (11)−0.0055 (10)
O50.0385 (10)0.0427 (10)0.0604 (12)−0.0026 (8)0.0199 (9)0.0066 (9)
O60.0436 (10)0.0346 (9)0.0562 (12)0.0130 (8)0.0149 (9)0.0030 (8)
O70.0483 (11)0.0269 (9)0.0643 (12)−0.0019 (8)0.0128 (9)0.0126 (8)
N20.0363 (11)0.0263 (10)0.0377 (11)−0.0009 (9)0.0063 (9)−0.0016 (8)
C80.0379 (13)0.0246 (11)0.0290 (12)0.0042 (10)0.0049 (10)−0.0001 (9)
O90.0356 (10)0.0465 (11)0.0460 (11)0.0073 (9)0.0106 (9)−0.0011 (9)
O80.0748 (16)0.0582 (14)0.0742 (17)0.0179 (12)0.0371 (14)0.0138 (12)

Geometric parameters (Å, °)

O4—C81.279 (3)C4—H4A0.9300
O4—H40.8200C1—C61.371 (3)
N1—C11.464 (3)C5—C61.395 (3)
N1—H1A0.8900C5—C71.496 (3)
N1—H1B0.8900C6—H60.9300
N1—H1C0.8900O2—C71.205 (3)
C2—C11.383 (3)C3—C81.488 (3)
C2—C31.384 (3)O5—N21.249 (2)
C2—H20.9300O6—N21.256 (2)
O1—C71.309 (3)O7—N21.240 (2)
O1—H10.8200O9—H9A0.88 (4)
O3—C81.243 (3)O9—H9B0.84 (5)
C4—C51.392 (3)O8—H8A0.97 (4)
C4—C31.393 (3)O8—H8B0.85 (5)
C8—O4—H4109.5C6—C5—C7118.5 (2)
C1—N1—H1A109.5C1—C6—C5119.2 (2)
C1—N1—H1B109.5C1—C6—H6120.4
H1A—N1—H1B109.5C5—C6—H6120.4
C1—N1—H1C109.5C2—C3—C4120.3 (2)
H1A—N1—H1C109.5C2—C3—C8119.59 (19)
H1B—N1—H1C109.5C4—C3—C8120.1 (2)
C1—C2—C3119.0 (2)O2—C7—O1124.5 (2)
C1—C2—H2120.5O2—C7—C5122.6 (2)
C3—C2—H2120.5O1—C7—C5112.9 (2)
C7—O1—H1109.5O7—N2—O5120.9 (2)
C5—C4—C3119.7 (2)O7—N2—O6119.8 (2)
C5—C4—H4A120.2O5—N2—O6119.32 (19)
C3—C4—H4A120.2O3—C8—O4123.7 (2)
C6—C1—C2121.8 (2)O3—C8—C3120.5 (2)
C6—C1—N1119.39 (19)O4—C8—C3115.8 (2)
C2—C1—N1118.78 (19)H9A—O9—H9B96 (4)
C4—C5—C6119.9 (2)H8A—O8—H8B103 (4)
C4—C5—C7121.6 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C2—H2···O6i0.932.583.324 (3)138
O9—H9A···O7ii0.88 (4)2.39 (4)3.048 (3)133 (3)
O9—H9A···O5ii0.88 (4)1.94 (4)2.801 (3)168 (4)
O8—H8B···O3iii0.85 (5)2.29 (5)3.057 (3)149 (4)
O8—H8A···O2iv0.97 (4)2.00 (4)2.882 (3)151 (3)
O4—H4···O3v0.821.842.652 (2)169
N1—H1C···O9vi0.891.982.839 (3)163
N1—H1B···O6vii0.892.002.859 (3)161
N1—H1B···O5vii0.892.553.134 (3)124
O9—H9B···O80.84 (5)1.96 (5)2.796 (3)171 (5)
N1—H1A···O7i0.892.462.933 (3)114
N1—H1A···O6i0.892.092.963 (3)165
O1—H1···O9viii0.821.802.611 (3)169

Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+1, −y+1, −z+1; (iii) −x+1, y+1/2, −z+3/2; (iv) −x+1, y−1/2, −z+3/2; (v) −x+1, −y, −z+1; (vi) x−1, −y+3/2, z−1/2; (vii) x, y+1, z; (viii) x−1, y, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RZ2414).

References

  • Dobson, A. J. & Gerkin, R. E. (1998). Acta Cryst. C54, 1503–1505. [PubMed]
  • Ferguson, G. (1999). PRPKAPPA University of Guelph, Canada.
  • Liao, Q.-X., Li, Z.-J., Zhang, J., Kang, Y., Dai, Y.-M. & Yao, Y.-G. (2004). Acta Cryst. C60, m509–m511. [PubMed]
  • Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography