A new (monohydrate) form of 3,5-di­carb­oxy­anilinium nitrate: crystal structure and Hirshfeld surface analysis

The title compound crystallizes in the same space group (P2₁/c) as the previously reported dihydrate form, but with two formula units per asymmetric unit instead of one. In the crystal, the components are linked into a three-dimensional network by classical inter­molecular O—H...O and N—H...O hydrogen bonds and π–π stacking inter­actions.

Computing details

Data collection: BIS (Bruker, 2014), APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

3,5-Dicarboxyanilinium nitrate monohydrate

Crystal data

C8H8NO4^+·NO3^−·H2O	F(000) = 1088
Mr = 262.18	Dx = 1.633 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.7026 (4) Å	Cell parameters from 5578 reflections
b = 8.5449 (2) Å	θ = 2.4–28.9°
c = 16.9929 (4) Å	µ = 0.15 mm^−1
β = 92.800 (2)°	T = 298 K
V = 2132.31 (9) Å^3	Plate, colorless
Z = 8	0.14 × 0.12 × 0.1 mm

Data collection

Bruker APEXII CCD diffractometer	3653 reflections with I > 2σ(I)
Mirror optics monochromator	Rint = 0.069
φ and ω scans	θmax = 27.5°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2014)	h = −18→19
Tmin = 0.627, Tmax = 0.746	k = −11→10
20897 measured reflections	l = −22→20
4881 independent reflections

Refinement

Refinement on F^2	Primary atom site location: heavy-atom method
Least-squares matrix: full	Secondary atom site location: other
R[F^2 > 2σ(F^2)] = 0.048	Hydrogen site location: mixed
wR(F^2) = 0.142	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0742P)^2 + 0.5757P] where P = (Fo^2 + 2Fc^2)/3
4881 reflections	(Δ/σ)max = 0.001
368 parameters	Δρmax = 0.38 e Å^−3
0 restraints	Δρmin = −0.36 e Å^−3

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1B	0.67893 (13)	0.3682 (2)	0.28611 (10)	0.0301 (4)
O1A	0.82519 (13)	1.17198 (18)	0.43486 (9)	0.0423 (4)
O2W	0.58027 (15)	−0.0690 (2)	0.65998 (12)	0.0603 (5)
H2WA	0.546 (3)	−0.012 (5)	0.622 (2)	0.090*
H2WB	0.615 (3)	−0.127 (4)	0.631 (2)	0.090*
O3A	0.97439 (10)	1.86406 (16)	0.43414 (8)	0.0346 (3)
H3A	0.9913 (18)	1.922 (3)	0.3898 (16)	0.052*
O2A	0.78909 (12)	1.14271 (17)	0.56010 (9)	0.0452 (4)
O4A	0.92628 (11)	1.69085 (17)	0.34332 (8)	0.0396 (4)
O3B	0.56209 (12)	0.38877 (19)	0.62141 (9)	0.0465 (4)
H3B	0.539 (2)	0.324 (4)	0.6536 (18)	0.070*
O1B	0.70854 (12)	0.86590 (18)	0.53880 (9)	0.0418 (4)
O4B	0.55015 (15)	0.17909 (18)	0.54420 (10)	0.0574 (5)
O2B	0.75437 (11)	0.88596 (16)	0.41625 (8)	0.0362 (3)
O6A	1.10763 (13)	1.85507 (18)	0.24130 (10)	0.0503 (4)
O5A	1.03844 (10)	2.02758 (17)	0.30967 (9)	0.0380 (4)
O7A	1.18270 (10)	2.05003 (17)	0.29317 (9)	0.0389 (4)
O1W	0.49992 (10)	0.22720 (19)	0.73709 (9)	0.0357 (3)
H1WA	0.4800 (19)	0.284 (3)	0.7699 (16)	0.053*
H1WB	0.4622 (19)	0.147 (3)	0.7312 (15)	0.053*
O7B	0.70536 (11)	−0.14901 (17)	0.22552 (10)	0.0450 (4)
O5B	0.76172 (10)	0.07156 (17)	0.26536 (9)	0.0403 (4)
O6B	0.62322 (10)	0.01340 (18)	0.28938 (9)	0.0410 (4)
N2A	1.11052 (12)	1.97532 (18)	0.28112 (9)	0.0295 (4)
N2B	0.69618 (11)	−0.02251 (18)	0.25969 (10)	0.0299 (4)
C1A	0.82076 (13)	1.2200 (2)	0.50630 (11)	0.0254 (4)
C2A	0.85560 (12)	1.3807 (2)	0.52255 (10)	0.0225 (4)
C3A	0.88063 (11)	1.4777 (2)	0.46159 (10)	0.0218 (4)
H3AA	0.876949	1.441662	0.409886	0.026*
C4A	0.91116 (11)	1.62859 (19)	0.47816 (10)	0.0206 (3)
C8A	0.93717 (12)	1.7299 (2)	0.41105 (10)	0.0244 (4)
C5A	0.91825 (12)	1.68168 (19)	0.55568 (10)	0.0219 (3)
H5A	0.939205	1.782250	0.567040	0.026*
C6A	0.89382 (11)	1.5833 (2)	0.61539 (10)	0.0212 (3)
N1A	0.90040 (13)	1.6379 (2)	0.69669 (9)	0.0267 (3)
C7A	0.86173 (12)	1.4334 (2)	0.59991 (10)	0.0230 (4)
H7A	0.844537	1.369037	0.640745	0.028*
C8B	0.57193 (14)	0.3132 (2)	0.55560 (12)	0.0321 (4)
C4B	0.61297 (13)	0.4121 (2)	0.49363 (11)	0.0268 (4)
C3B	0.64094 (13)	0.5653 (2)	0.51020 (11)	0.0261 (4)
H3BA	0.633618	0.607888	0.559853	0.031*
C2B	0.67981 (12)	0.6536 (2)	0.45190 (11)	0.0236 (4)
C1B	0.71606 (12)	0.8134 (2)	0.46854 (11)	0.0254 (4)
C7B	0.69130 (12)	0.5897 (2)	0.37756 (10)	0.0244 (4)
H7B	0.716729	0.648905	0.338290	0.029*
C6B	0.66436 (12)	0.4375 (2)	0.36321 (10)	0.0240 (4)
C5B	0.62522 (13)	0.3476 (2)	0.42002 (11)	0.0271 (4)
H5B	0.607314	0.245226	0.409039	0.033*
H1B	0.7317 (17)	0.954 (3)	0.5397 (14)	0.041*
H1BA	0.7200 (16)	0.426 (3)	0.2570 (13)	0.033*
H1BB	0.7054 (15)	0.273 (3)	0.2872 (13)	0.033*
H1BC	0.6263 (18)	0.350 (3)	0.2638 (13)	0.033*
H1AA	0.9473 (17)	1.618 (3)	0.7214 (13)	0.033*
H1AB	0.8549 (16)	1.593 (3)	0.7224 (13)	0.033*
H1AC	0.8850 (15)	1.734 (3)	0.7023 (13)	0.033*
H1A	0.804 (3)	1.090 (5)	0.433 (2)	0.087 (12)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1B	0.0342 (9)	0.0260 (9)	0.0305 (9)	−0.0018 (7)	0.0048 (7)	−0.0073 (7)
O1A	0.0685 (11)	0.0235 (8)	0.0348 (8)	−0.0118 (7)	0.0009 (7)	−0.0098 (6)
O2W	0.0750 (14)	0.0476 (11)	0.0614 (12)	0.0152 (9)	0.0353 (10)	0.0080 (9)
O3A	0.0509 (9)	0.0253 (7)	0.0279 (7)	−0.0142 (6)	0.0051 (6)	0.0020 (6)
O2A	0.0679 (11)	0.0298 (8)	0.0381 (8)	−0.0217 (7)	0.0046 (7)	0.0034 (6)
O4A	0.0628 (10)	0.0343 (8)	0.0219 (7)	−0.0123 (7)	0.0033 (6)	0.0008 (6)
O3B	0.0690 (11)	0.0400 (9)	0.0318 (8)	−0.0176 (8)	0.0154 (7)	0.0013 (7)
O1B	0.0616 (10)	0.0277 (8)	0.0375 (8)	−0.0182 (7)	0.0179 (7)	−0.0130 (6)
O4B	0.0931 (14)	0.0302 (9)	0.0507 (10)	−0.0227 (8)	0.0230 (9)	0.0021 (7)
O2B	0.0534 (9)	0.0237 (7)	0.0320 (7)	−0.0118 (6)	0.0081 (6)	−0.0002 (5)
O6A	0.0677 (12)	0.0278 (8)	0.0560 (10)	0.0005 (7)	0.0081 (8)	−0.0119 (7)
O5A	0.0419 (8)	0.0315 (8)	0.0419 (8)	0.0004 (6)	0.0170 (6)	0.0065 (6)
O7A	0.0353 (8)	0.0388 (8)	0.0425 (9)	−0.0050 (6)	0.0013 (6)	0.0046 (6)
O1W	0.0359 (8)	0.0355 (8)	0.0365 (8)	−0.0048 (6)	0.0102 (6)	−0.0007 (6)
O7B	0.0558 (10)	0.0263 (8)	0.0541 (10)	0.0004 (7)	0.0153 (8)	−0.0108 (7)
O5B	0.0417 (9)	0.0335 (8)	0.0467 (9)	−0.0101 (6)	0.0127 (7)	−0.0036 (6)
O6B	0.0338 (8)	0.0393 (8)	0.0508 (9)	0.0046 (6)	0.0117 (7)	−0.0038 (7)
N2A	0.0394 (9)	0.0220 (8)	0.0273 (8)	−0.0009 (7)	0.0050 (6)	0.0059 (6)
N2B	0.0354 (9)	0.0247 (8)	0.0298 (8)	0.0019 (7)	0.0050 (6)	0.0011 (6)
C1A	0.0306 (9)	0.0202 (9)	0.0254 (9)	−0.0024 (7)	0.0009 (7)	−0.0008 (7)
C2A	0.0251 (9)	0.0176 (8)	0.0248 (9)	−0.0016 (6)	0.0005 (6)	0.0004 (6)
C3A	0.0233 (8)	0.0218 (8)	0.0202 (8)	−0.0007 (6)	−0.0006 (6)	−0.0023 (6)
C4A	0.0219 (8)	0.0199 (8)	0.0202 (8)	0.0008 (6)	0.0012 (6)	0.0019 (6)
C8A	0.0286 (9)	0.0210 (9)	0.0236 (9)	−0.0010 (7)	0.0022 (7)	0.0024 (7)
C5A	0.0253 (9)	0.0166 (8)	0.0236 (8)	−0.0017 (6)	0.0007 (6)	−0.0017 (6)
C6A	0.0229 (8)	0.0219 (8)	0.0188 (8)	0.0020 (6)	0.0013 (6)	−0.0025 (6)
N1A	0.0345 (9)	0.0258 (8)	0.0200 (8)	−0.0003 (7)	0.0030 (6)	−0.0031 (6)
C7A	0.0267 (9)	0.0198 (8)	0.0227 (8)	−0.0010 (7)	0.0032 (7)	0.0011 (6)
C8B	0.0361 (11)	0.0265 (10)	0.0339 (10)	−0.0055 (8)	0.0040 (8)	0.0051 (8)
C4B	0.0291 (9)	0.0212 (9)	0.0303 (9)	−0.0025 (7)	0.0017 (7)	0.0032 (7)
C3B	0.0282 (9)	0.0232 (9)	0.0273 (9)	−0.0019 (7)	0.0038 (7)	−0.0018 (7)
C2B	0.0230 (9)	0.0189 (8)	0.0288 (9)	−0.0012 (7)	0.0010 (7)	−0.0017 (7)
C1B	0.0281 (9)	0.0206 (8)	0.0277 (9)	0.0000 (7)	0.0027 (7)	−0.0018 (7)
C7B	0.0280 (9)	0.0189 (9)	0.0264 (9)	−0.0001 (7)	0.0034 (7)	0.0010 (7)
C6B	0.0247 (9)	0.0219 (9)	0.0254 (9)	−0.0004 (7)	0.0003 (7)	−0.0033 (7)
C5B	0.0300 (9)	0.0187 (8)	0.0324 (10)	−0.0045 (7)	0.0005 (7)	−0.0009 (7)

Geometric parameters (Å, º)

C6A—N1A	1.457 (2)	O6B—N2B	1.246 (2)
N1B—H1BA	0.94 (2)	C1A—C2A	1.486 (2)
N1B—H1BB	0.90 (2)	C2A—C3A	1.390 (2)
N1B—H1BC	0.86 (3)	C2A—C7A	1.388 (2)
O1A—C1A	1.286 (2)	C3A—H3AA	0.9300
O2A—C1A	1.237 (2)	C3A—C4A	1.390 (2)
O1A—H1A	0.77 (4)	C4A—C8A	1.496 (2)
O2W—H2WA	0.93 (4)	C4A—C5A	1.392 (2)
O2W—H2WB	0.88 (4)	C5A—H5A	0.9300
O3A—H3A	0.94 (3)	C5A—C6A	1.379 (2)
O3A—C8A	1.322 (2)	C6A—C7A	1.386 (2)
O4A—C8A	1.202 (2)	N1A—H1AA	0.81 (3)
N1B—C6B	1.463 (2)	N1A—H1AB	0.90 (2)
O1B—C1B	1.285 (2)	N1A—H1AC	0.86 (2)
O2B—C1B	1.241 (2)	C7A—H7A	0.9300
O3B—H3B	0.86 (3)	C8B—C4B	1.499 (2)
O3B—C8B	1.305 (2)	C4B—C3B	1.397 (3)
O1B—H1B	0.82 (3)	C4B—C5B	1.386 (3)
O4B—C8B	1.203 (2)	C3B—H3BA	0.9300
O6A—N2A	1.230 (2)	C3B—C2B	1.390 (2)
O5A—N2A	1.268 (2)	C2B—C1B	1.488 (2)
O7A—N2A	1.247 (2)	C2B—C7B	1.394 (2)
O1W—H1WA	0.81 (3)	C7B—H7B	0.9300
O1W—H1WB	0.88 (3)	C7B—C6B	1.378 (2)
O7B—N2B	1.237 (2)	C6B—C5B	1.381 (2)
O5B—N2B	1.255 (2)	C5B—H5B	0.9300
C6B—N1B—H1BA	112.8 (13)	C5A—C6A—N1A	119.66 (15)
C6B—N1B—H1BB	115.3 (14)	C5A—C6A—C7A	121.50 (15)
C6B—N1B—H1BC	107.5 (15)	C7A—C6A—N1A	118.84 (15)
H1BA—N1B—H1BB	101.1 (19)	C6A—N1A—H1AA	116.1 (16)
H1BA—N1B—H1BC	117 (2)	C6A—N1A—H1AB	107.9 (14)
H1BB—N1B—H1BC	103 (2)	C6A—N1A—H1AC	114.0 (15)
C1A—O1A—H1A	107 (3)	H1AA—N1A—H1AB	107 (2)
H2WA—O2W—H2WB	103 (3)	H1AA—N1A—H1AC	112 (2)
C8A—O3A—H3A	109.6 (16)	H1AB—N1A—H1AC	98 (2)
C8B—O3B—H3B	107 (2)	C2A—C7A—H7A	120.5
C1B—O1B—H1B	106.3 (17)	C6A—C7A—C2A	119.04 (16)
H1WA—O1W—H1WB	107 (3)	C6A—C7A—H7A	120.5
O6A—N2A—O5A	119.84 (18)	O3B—C8B—C4B	112.86 (16)
O6A—N2A—O7A	121.63 (17)	O2B—C1B—O1B	123.59 (17)
O7A—N2A—O5A	118.51 (16)	O4B—C8B—O3B	124.69 (18)
O7B—N2B—O5B	119.63 (16)	O4B—C8B—C4B	122.45 (18)
O7B—N2B—O6B	121.39 (17)	C3B—C4B—C8B	120.73 (17)
O6B—N2B—O5B	118.97 (16)	C5B—C4B—C8B	118.98 (16)
O1A—C1A—C2A	115.93 (16)	C5B—C4B—C3B	120.27 (16)
O2A—C1A—O1A	124.42 (17)	C4B—C3B—H3BA	120.3
O2A—C1A—C2A	119.64 (16)	C2B—C3B—C4B	119.49 (17)
C3A—C2A—C1A	120.90 (16)	C2B—C3B—H3BA	120.3
C7A—C2A—C1A	118.78 (15)	C3B—C2B—C1B	121.24 (16)
C7A—C2A—C3A	120.32 (16)	C3B—C2B—C7B	120.38 (16)
C2A—C3A—H3AA	120.1	C7B—C2B—C1B	118.24 (16)
C4A—C3A—C2A	119.79 (15)	O1B—C1B—C2B	116.78 (16)
C4A—C3A—H3AA	120.1	O2B—C1B—C2B	119.57 (16)
C3A—C4A—C8A	118.33 (15)	C2B—C7B—H7B	120.6
C3A—C4A—C5A	120.17 (15)	C6B—C7B—C2B	118.89 (16)
C5A—C4A—C8A	121.49 (15)	C6B—C7B—H7B	120.6
O3A—C8A—C4A	113.16 (15)	C7B—C6B—N1B	119.14 (16)
O4A—C8A—O3A	124.00 (16)	C7B—C6B—C5B	121.83 (16)
O4A—C8A—C4A	122.84 (16)	C5B—C6B—N1B	119.03 (16)
C4A—C5A—H5A	120.4	C4B—C5B—H5B	120.4
C6A—C5A—C4A	119.17 (15)	C6B—C5B—C4B	119.13 (16)
C6A—C5A—H5A	120.4	C6B—C5B—H5B	120.4
N1B—C6B—C5B—C4B	178.76 (17)	C5A—C4A—C8A—O3A	6.0 (2)
O1A—C1A—C2A—C3A	7.5 (3)	C5A—C4A—C8A—O4A	−175.09 (18)
O1A—C1A—C2A—C7A	−173.26 (17)	C5A—C6A—C7A—C2A	1.1 (3)
O2A—C1A—C2A—C3A	−171.65 (18)	N1A—C6A—C7A—C2A	−179.81 (16)
O2A—C1A—C2A—C7A	7.6 (3)	C7A—C2A—C3A—C4A	−0.6 (3)
O3B—C8B—C4B—C3B	3.4 (3)	C8B—C4B—C3B—C2B	179.20 (17)
O3B—C8B—C4B—C5B	−178.43 (18)	C8B—C4B—C5B—C6B	−178.95 (17)
O4B—C8B—C4B—C3B	−177.3 (2)	C4B—C3B—C2B—C1B	−175.94 (17)
O4B—C8B—C4B—C5B	0.9 (3)	C4B—C3B—C2B—C7B	−0.3 (3)
C1A—C2A—C3A—C4A	178.62 (16)	C3B—C4B—C5B—C6B	−0.8 (3)
C1A—C2A—C7A—C6A	−179.75 (16)	C3B—C2B—C1B—O1B	−0.9 (3)
C2A—C3A—C4A—C8A	−179.76 (16)	C3B—C2B—C1B—O2B	176.44 (18)
C2A—C3A—C4A—C5A	1.2 (3)	C3B—C2B—C7B—C6B	−0.6 (3)
C3A—C2A—C7A—C6A	−0.5 (3)	C2B—C7B—C6B—N1B	−178.06 (17)
C3A—C4A—C8A—O3A	−173.07 (16)	C2B—C7B—C6B—C5B	0.9 (3)
C3A—C4A—C8A—O4A	5.8 (3)	C1B—C2B—C7B—C6B	175.10 (16)
C3A—C4A—C5A—C6A	−0.6 (3)	C7B—C2B—C1B—O1B	−176.57 (17)
C4A—C5A—C6A—N1A	−179.61 (16)	C7B—C2B—C1B—O2B	0.7 (3)
C4A—C5A—C6A—C7A	−0.5 (3)	C7B—C6B—C5B—C4B	−0.2 (3)
C8A—C4A—C5A—C6A	−179.67 (16)	C5B—C4B—C3B—C2B	1.1 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2W—H2WA···O4B	0.93 (4)	2.11 (4)	2.911 (3)	143 (3)
O2W—H2WB···O1B^i	0.88 (4)	2.14 (4)	2.913 (2)	147 (3)
O2W—H2WB···O7B^ii	0.88 (4)	2.79 (4)	3.198 (3)	110 (3)
O3A—H3A···O5A	0.94 (3)	1.80 (3)	2.7399 (19)	173 (2)
O3B—H3B···O1W	0.86 (3)	1.76 (3)	2.604 (2)	165 (3)
O1W—H1WA···O2W^iii	0.81 (3)	1.97 (3)	2.772 (2)	173 (3)
O1W—H1WB···O7B^iv	0.88 (3)	2.60 (3)	3.185 (2)	124 (2)
O1W—H1WB···O6B^iv	0.88 (3)	1.88 (3)	2.762 (2)	175 (3)
C7A—H7A···O5B^v	0.93	2.54	3.236 (2)	131
N1B—H1BA···O6A^vi	0.94 (2)	2.60 (2)	3.197 (3)	121.7 (17)
N1B—H1BA···O7A^vi	0.94 (2)	2.01 (2)	2.938 (2)	173 (2)
N1B—H1BB···O5B	0.90 (2)	1.96 (2)	2.842 (2)	168 (2)
N1B—H1BB···O6B	0.90 (2)	2.53 (2)	3.142 (2)	125.9 (18)
N1B—H1BC···O2W^vii	0.86 (3)	2.64 (2)	3.056 (3)	111.2 (17)
N1B—H1BC···O1W^vii	0.86 (3)	2.00 (3)	2.841 (2)	165 (2)
N1A—H1AA···O6A^viii	0.81 (3)	2.38 (3)	3.104 (3)	150 (2)
N1A—H1AA···O5A^viii	0.81 (3)	2.32 (3)	3.070 (2)	154 (2)
N1A—H1AB···O7B^v	0.90 (2)	2.25 (2)	2.934 (2)	132.1 (18)
N1A—H1AB···O5B^v	0.90 (2)	2.12 (2)	2.992 (2)	162.9 (19)
N1A—H1AC···O4A^viii	0.86 (2)	2.53 (2)	2.899 (2)	107.3 (17)
N1A—H1AC···O5A^ix	0.86 (2)	2.34 (2)	3.000 (2)	133.8 (19)
N1A—H1AC···O7A^ix	0.86 (2)	2.10 (3)	2.942 (2)	167 (2)
O1A—H1A···O2B	0.77 (4)	1.91 (4)	2.669 (2)	174 (4)
O1B—H1B···O2A	0.82 (3)	1.85 (3)	2.662 (2)	170 (3)

Symmetry codes: (i) x, y−1, z; (ii) x, −y−1/2, z+1/2; (iii) −x+1, y+1/2, −z+3/2; (iv) −x+1, −y, −z+1; (v) x, −y+3/2, z+1/2; (vi) −x+2, y−3/2, −z+1/2; (vii) x, −y+1/2, z−1/2; (viii) x, −y+7/2, z+1/2; (ix) −x+2, −y+4, −z+1.