3,5-Dicarboxyanilinium nitrate dihydrate

Liang, W.-X.; Zhu, Y.-T.

doi:10.1107/S1600536810005362

organic compounds

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ISSN: 2056-9890

Volume 66| Part 3| March 2010| Page o667

doi:10.1107/S1600536810005362

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3,5-Dicarboxyanilinium nitrate dihydrate

Wen-Xian Liang ^a ^* and Yun-Ti Zhu ^a

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: lwx927lh@163.com

(Received 28 January 2010; accepted 9 February 2010; online 20 February 2010)

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 ). For the use of 5-aminoisophthalic acid as a ligand, see: Liao et al. (2004 ).

Experimental

Crystal data

C₈H₈NO₄⁺·NO₃⁻·2H₂O
M_r = 280.20
Monoclinic, P 2₁ /c
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 ) 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[F² > 2σ(F²)] = 0.054
wR(F²) = 0.129
S = 1.07
2753 reflections
190 parameters
?
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O6ⁱ	0.93	2.58	3.324 (3)	138
O9—H9A⋯O7ⁱⁱ	0.88 (4)	2.39 (4)	3.048 (3)	133 (3)
O9—H9A⋯O5ⁱⁱ	0.88 (4)	1.94 (4)	2.801 (3)	168 (4)
O8—H8B⋯O3ⁱⁱⁱ	0.85 (5)	2.29 (5)	3.057 (3)	149 (4)
O8—H8A⋯O2^iv	0.97 (4)	2.00 (4)	2.882 (3)	151 (3)
O4—H4⋯O3^v	0.82	1.84	2.652 (2)	169
N1—H1C⋯O9^vi	0.89	1.98	2.839 (3)	163
N1—H1B⋯O6^vii	0.89	2.00	2.859 (3)	161
N1—H1B⋯O5^vii	0.89	2.55	3.134 (3)	124
O9—H9B⋯O8	0.84 (5)	1.96 (5)	2.796 (3)	171 (5)
N1—H1A⋯O7ⁱ	0.89	2.46	2.933 (3)	114
N1—H1A⋯O6ⁱ	0.89	2.09	2.963 (3)	165
O1—H1⋯O9^viii	0.82	1.80	2.611 (3)	169
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z+1; (iii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (v) -x+1, -y, -z+1; (vi) $[x-1, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (vii) x, y+1, z; (viii) x-1, y, z.

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

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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.

Computing details top

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

Figures top

	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.

3,5-Dicarboxyanilinium nitrate dihydrate top

Crystal data top

C₈H₈NO₄⁺·NO₃⁻·2H₂O	F(000) = 584
M_r = 280.20	D_x = 1.547 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1753 reflections
a = 8.3436 (17) Å	θ = 3.1–27.5°
b = 8.6234 (17) Å	µ = 0.14 mm⁻¹
c = 16.862 (3) Å	T = 293 K
β = 97.31 (3)°	Prism, colourless
V = 1203.4 (4) Å³	0.35 × 0.25 × 0.10 mm
Z = 4

Data collection top

Rigaku SCXmini diffractometer	2753 independent reflections
Radiation source: fine-focus sealed tube	1905 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.055
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.2°
CCD profile fitting scans	h = −10→10
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −11→11
T_min = 0.960, T_max = 0.986	l = −21→21
12169 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.054	w = 1/[σ²(F_o²) + (0.0423P)² + 0.7735P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.129	(Δ/σ)_max < 0.001
S = 1.07	Δρ_max = 0.28 e Å⁻³
2753 reflections	Δρ_min = −0.24 e Å⁻³
190 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008)
0 restraints	Extinction coefficient: 0.0014 (1)
Primary atom site location: structure-invariant direct methods

Crystal data top

C₈H₈NO₄⁺·NO₃⁻·2H₂O	V = 1203.4 (4) Å³
M_r = 280.20	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.3436 (17) Å	µ = 0.14 mm⁻¹
b = 8.6234 (17) Å	T = 293 K
c = 16.862 (3) Å	0.35 × 0.25 × 0.10 mm
β = 97.31 (3)°

Data collection top

Rigaku SCXmini diffractometer	2753 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1905 reflections with I > 2σ(I)
T_min = 0.960, T_max = 0.986	R_int = 0.055
12169 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	190 parameters
wR(F²) = 0.129	0 restraints
S = 1.07	Δρ_max = 0.28 e Å⁻³
2753 reflections	Δρ_min = −0.24 e Å⁻³

Special details top

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) top

	x	y	z	U_iso*/U_eq
O4	0.4952 (2)	0.14675 (19)	0.42859 (10)	0.0442 (5)
H4	0.5275	0.0603	0.4432	0.066*
N1	0.3108 (2)	0.6452 (2)	0.29415 (11)	0.0328 (5)
H1A	0.3651	0.5813	0.2658	0.049*
H1B	0.3632	0.7350	0.3010	0.049*
H1C	0.2126	0.6614	0.2682	0.049*
C2	0.3575 (3)	0.4279 (2)	0.38793 (13)	0.0280 (5)
H2	0.4070	0.3744	0.3498	0.034*
O1	0.1136 (3)	0.6025 (2)	0.62566 (11)	0.0545 (6)
H1	0.0669	0.6559	0.6558	0.082*
O3	0.3885 (3)	0.1368 (2)	0.54276 (11)	0.0513 (5)
C4	0.2667 (3)	0.4405 (2)	0.51780 (13)	0.0296 (5)
H4A	0.2556	0.3946	0.5667	0.036*
C1	0.2969 (3)	0.5756 (2)	0.37216 (13)	0.0264 (5)
C5	0.2069 (3)	0.5891 (3)	0.50071 (14)	0.0299 (5)
C6	0.2225 (3)	0.6570 (2)	0.42699 (13)	0.0300 (5)
H6	0.1830	0.7563	0.4152	0.036*
O2	0.0772 (3)	0.8101 (2)	0.54705 (12)	0.0605 (6)
C3	0.3432 (3)	0.3610 (2)	0.46132 (13)	0.0275 (5)
C7	0.1260 (3)	0.6799 (3)	0.55994 (14)	0.0356 (6)
O5	0.2218 (2)	−0.0029 (2)	0.30373 (12)	0.0461 (5)
O6	0.4607 (2)	−0.06093 (19)	0.27628 (11)	0.0441 (5)
O7	0.3495 (2)	0.15470 (19)	0.23390 (12)	0.0460 (5)
N2	0.3433 (2)	0.0312 (2)	0.27105 (12)	0.0333 (5)
C8	0.4106 (3)	0.2034 (3)	0.47971 (13)	0.0304 (5)
O9	0.9920 (2)	0.7569 (2)	0.73715 (12)	0.0422 (5)
O8	0.8512 (3)	0.5594 (3)	0.84014 (16)	0.0667 (7)
H9A	0.916 (5)	0.828 (5)	0.729 (2)	0.091 (13)*
H8A	0.904 (4)	0.500 (5)	0.885 (2)	0.089 (13)*
H8B	0.781 (6)	0.612 (5)	0.861 (3)	0.111 (16)*
H9B	0.949 (6)	0.706 (6)	0.771 (3)	0.14 (2)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O4	0.0653 (12)	0.0295 (9)	0.0394 (10)	0.0196 (9)	0.0133 (9)	0.0042 (7)
N1	0.0348 (11)	0.0289 (10)	0.0359 (11)	0.0043 (8)	0.0092 (9)	0.0069 (8)
C2	0.0321 (12)	0.0225 (11)	0.0299 (12)	0.0021 (9)	0.0057 (10)	−0.0010 (9)
O1	0.0824 (15)	0.0496 (11)	0.0354 (10)	0.0243 (10)	0.0225 (10)	0.0014 (9)
O3	0.0760 (14)	0.0357 (10)	0.0470 (11)	0.0214 (10)	0.0261 (10)	0.0177 (8)
C4	0.0365 (13)	0.0251 (11)	0.0269 (12)	0.0028 (9)	0.0025 (10)	0.0010 (9)
C1	0.0283 (11)	0.0236 (11)	0.0275 (11)	−0.0002 (9)	0.0038 (9)	0.0026 (9)
C5	0.0323 (12)	0.0258 (11)	0.0313 (12)	0.0017 (9)	0.0029 (10)	−0.0025 (9)
C6	0.0345 (12)	0.0204 (10)	0.0348 (12)	0.0054 (9)	0.0027 (10)	0.0003 (9)
O2	0.0920 (16)	0.0371 (11)	0.0573 (13)	0.0270 (11)	0.0282 (12)	0.0011 (9)
C3	0.0317 (12)	0.0209 (10)	0.0293 (12)	0.0016 (9)	0.0021 (9)	0.0008 (9)
C7	0.0421 (14)	0.0308 (13)	0.0343 (13)	0.0059 (11)	0.0063 (11)	−0.0055 (10)
O5	0.0385 (10)	0.0427 (10)	0.0604 (12)	−0.0026 (8)	0.0199 (9)	0.0066 (9)
O6	0.0436 (10)	0.0346 (9)	0.0562 (12)	0.0130 (8)	0.0149 (9)	0.0030 (8)
O7	0.0483 (11)	0.0269 (9)	0.0643 (12)	−0.0019 (8)	0.0128 (9)	0.0126 (8)
N2	0.0363 (11)	0.0263 (10)	0.0377 (11)	−0.0009 (9)	0.0063 (9)	−0.0016 (8)
C8	0.0379 (13)	0.0246 (11)	0.0290 (12)	0.0042 (10)	0.0049 (10)	−0.0001 (9)
O9	0.0356 (10)	0.0465 (11)	0.0460 (11)	0.0073 (9)	0.0106 (9)	−0.0011 (9)
O8	0.0748 (16)	0.0582 (14)	0.0742 (17)	0.0179 (12)	0.0371 (14)	0.0138 (12)

Geometric parameters (Å, º) top

O4—C8	1.279 (3)	C4—H4A	0.9300
O4—H4	0.8200	C1—C6	1.371 (3)
N1—C1	1.464 (3)	C5—C6	1.395 (3)
N1—H1A	0.8900	C5—C7	1.496 (3)
N1—H1B	0.8900	C6—H6	0.9300
N1—H1C	0.8900	O2—C7	1.205 (3)
C2—C1	1.383 (3)	C3—C8	1.488 (3)
C2—C3	1.384 (3)	O5—N2	1.249 (2)
C2—H2	0.9300	O6—N2	1.256 (2)
O1—C7	1.309 (3)	O7—N2	1.240 (2)
O1—H1	0.8200	O9—H9A	0.88 (4)
O3—C8	1.243 (3)	O9—H9B	0.84 (5)
C4—C5	1.392 (3)	O8—H8A	0.97 (4)
C4—C3	1.393 (3)	O8—H8B	0.85 (5)

C8—O4—H4	109.5	C6—C5—C7	118.5 (2)
C1—N1—H1A	109.5	C1—C6—C5	119.2 (2)
C1—N1—H1B	109.5	C1—C6—H6	120.4
H1A—N1—H1B	109.5	C5—C6—H6	120.4
C1—N1—H1C	109.5	C2—C3—C4	120.3 (2)
H1A—N1—H1C	109.5	C2—C3—C8	119.59 (19)
H1B—N1—H1C	109.5	C4—C3—C8	120.1 (2)
C1—C2—C3	119.0 (2)	O2—C7—O1	124.5 (2)
C1—C2—H2	120.5	O2—C7—C5	122.6 (2)
C3—C2—H2	120.5	O1—C7—C5	112.9 (2)
C7—O1—H1	109.5	O7—N2—O5	120.9 (2)
C5—C4—C3	119.7 (2)	O7—N2—O6	119.8 (2)
C5—C4—H4A	120.2	O5—N2—O6	119.32 (19)
C3—C4—H4A	120.2	O3—C8—O4	123.7 (2)
C6—C1—C2	121.8 (2)	O3—C8—C3	120.5 (2)
C6—C1—N1	119.39 (19)	O4—C8—C3	115.8 (2)
C2—C1—N1	118.78 (19)	H9A—O9—H9B	96 (4)
C4—C5—C6	119.9 (2)	H8A—O8—H8B	103 (4)
C4—C5—C7	121.6 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O6ⁱ	0.93	2.58	3.324 (3)	138
O9—H9A···O7ⁱⁱ	0.88 (4)	2.39 (4)	3.048 (3)	133 (3)
O9—H9A···O5ⁱⁱ	0.88 (4)	1.94 (4)	2.801 (3)	168 (4)
O8—H8B···O3ⁱⁱⁱ	0.85 (5)	2.29 (5)	3.057 (3)	149 (4)
O8—H8A···O2^iv	0.97 (4)	2.00 (4)	2.882 (3)	151 (3)
O4—H4···O3^v	0.82	1.84	2.652 (2)	169
N1—H1C···O9^vi	0.89	1.98	2.839 (3)	163
N1—H1B···O6^vii	0.89	2.00	2.859 (3)	161
N1—H1B···O5^vii	0.89	2.55	3.134 (3)	124
O9—H9B···O8	0.84 (5)	1.96 (5)	2.796 (3)	171 (5)
N1—H1A···O7ⁱ	0.89	2.46	2.933 (3)	114
N1—H1A···O6ⁱ	0.89	2.09	2.963 (3)	165
O1—H1···O9^viii	0.82	1.80	2.611 (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.

Experimental details

Crystal data
Chemical formula	C₈H₈NO₄⁺·NO₃⁻·2H₂O
M_r	280.20
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	8.3436 (17), 8.6234 (17), 16.862 (3)
β (°)	97.31 (3)
V (Å³)	1203.4 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.14
Crystal size (mm)	0.35 × 0.25 × 0.10

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.960, 0.986
No. of measured, independent and observed [I > 2σ(I)] reflections	12169, 2753, 1905
R_int	0.055
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.129, 1.07
No. of reflections	2753
No. of parameters	190
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.24

Computer programs: CrystalClear (Rigaku 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PRPKAPPA (Ferguson, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O6ⁱ	0.93	2.58	3.324 (3)	137.5
O9—H9A···O7ⁱⁱ	0.88 (4)	2.39 (4)	3.048 (3)	133 (3)
O9—H9A···O5ⁱⁱ	0.88 (4)	1.94 (4)	2.801 (3)	168 (4)
O8—H8B···O3ⁱⁱⁱ	0.85 (5)	2.29 (5)	3.057 (3)	149 (4)
O8—H8A···O2^iv	0.97 (4)	2.00 (4)	2.882 (3)	151 (3)
O4—H4···O3^v	0.82	1.84	2.652 (2)	169.3
N1—H1C···O9^vi	0.89	1.98	2.839 (3)	162.6
N1—H1B···O6^vii	0.89	2.00	2.859 (3)	160.5
N1—H1B···O5^vii	0.89	2.55	3.134 (3)	123.6
O9—H9B···O8	0.84 (5)	1.96 (5)	2.796 (3)	171 (5)
N1—H1A···O7ⁱ	0.89	2.46	2.933 (3)	113.5
N1—H1A···O6ⁱ	0.89	2.09	2.963 (3)	165.3
O1—H1···O9^viii	0.82	1.80	2.611 (3)	168.8

Acknowledgements

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

References

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