Bis(2-carboxy­anilinium) sulfate monohydrate

The title compound, 2C₇H₈NO₂⁺·SO₄^2-·H₂O, (I), exhibits a complex three-dimensional network of hydrogen bonds, involving all hydrogen donor atoms. A total of ten hydrogen bonds are present in the asymmetric unit, five of which are three-centre hydrogen bonds with one hydrogen donor and two acceptors. The suitability of the compound for possiblecharge-density study was investigated. As the quality of crystals did not seem sufficient for this purpose, no further experiments were carried out.

S1. Comment

NO COMMENT

S2. Experimental

Crystals of the title compound were grown by very slow evaporation of an ethanol solution of anthranilic acid and sulfuric acid (95% water solution) in an equimolar ratio.

S3. Refinement

During the refinement in SHELXL (Sheldrick, 1997), all the H atoms were located and refined, with the exception of the carboxyl H atom. The structure was transferred to the JANA (Petricek & Dusek, 2000) crystallographic computing system and the section of the difference Fourier map through the carboxylic acid group was drawn, on which the remaining H22 atom was located. Having experimental evidence that the H22 atom was present in the crystal, the atom was set to a calculated positionand and refined in SHELXL using two constraints: (i) the O22—H22 distance was kept at 0.9 Å, within an s.u. of 0.02 Å; (ii) the carboxylic acid group C27—O21—O22—H22 was kept planar within an s.u. of 0.1 Å. During the refinement, some H atoms of the –NH₃⁺ groups were moving slowly towards the parent N18 and N28 atoms. These groups were constrained to idealized geometry with tetrahedral angles, fixed N—H distances, free rotation around the C—N bond and refined isotropic displacement parameters for H atoms.

Computing details

Data collection: COLLECT (Nonius, 1999); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO and SCALEPACK (Otwinowski & Minor 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1990); software used to prepare material for publication: SHELXL97.

bis(anthranilium) sulfate monohydrate

Crystal data

2C7H8O2N^+·SO4^2^−·H2O	F(000) = 816
Mr = 390.36	Dx = 1.496 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71070 Å
a = 11.0632 (5) Å	Cell parameters from 7879 reflections
b = 15.8711 (9) Å	θ = 1.0–25.0°
c = 9.9597 (4) Å	µ = 0.24 mm^−1
β = 97.559 (3)°	T = 293 K
V = 1733.58 (14) Å^3	Plate, translucent, colourless
Z = 4	0.4 × 0.3 × 0.1 mm

Data collection

Nonius KappaCCD diffractometer	3050 independent reflections
Radiation source: fine-focus sealed tube	2164 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.070
Detector resolution: 0.110 pixels mm^-1	θmax = 25.1°, θmin = 3.2°
CCD (rotation scans, rotation per image 2°, 118 images collected using ω scans, total scan length 242.0° ω, which corresponds to the half of Ewald sphere)	h = 0→13
Absorption correction: multi-scan (Blessing, 1995)	k = −18→18
Tmin = 0.882, Tmax = 0.931	l = −11→11
14306 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.053	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.140	w = 1/[σ^2(Fo^2) + (0.0551P)^2 + 1.3544P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
3050 reflections	Δρmax = 0.35 e Å^−3
292 parameters	Δρmin = −0.33 e Å^−3
2 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0053 (14)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
S1	0.61258 (7)	0.12301 (5)	0.13576 (8)	0.0508 (3)
O2	0.4935 (2)	0.13613 (16)	0.1788 (3)	0.0727 (7)
O3	0.6336 (3)	0.03399 (16)	0.1147 (3)	0.0832 (8)
O4	0.6195 (3)	0.16539 (18)	0.0079 (3)	0.0827 (8)
O5	0.7048 (3)	0.1531 (3)	0.2391 (4)	0.1482 (18)
O6	0.8219 (2)	0.24805 (19)	−0.0659 (3)	0.0612 (6)
C11	0.1430 (2)	−0.0294 (2)	0.2431 (3)	0.0463 (7)
C12	0.2197 (3)	0.0148 (2)	0.1677 (3)	0.0465 (7)
C13	0.1764 (3)	0.0813 (2)	0.0864 (4)	0.0581 (9)
C14	0.0557 (3)	0.1055 (3)	0.0798 (4)	0.0663 (10)
C15	−0.0217 (3)	0.0627 (3)	0.1534 (4)	0.0656 (10)
C16	0.0216 (3)	−0.0041 (2)	0.2336 (4)	0.0573 (9)
C17	0.1887 (3)	−0.0993 (2)	0.3360 (3)	0.0525 (8)
O11	0.1025 (2)	−0.14037 (19)	0.3863 (3)	0.0725 (8)
O12	0.2955 (2)	−0.11612 (18)	0.3630 (3)	0.0747 (8)
N18	0.3481 (2)	−0.00793 (18)	0.1702 (3)	0.0506 (7)
H18A	0.3585	−0.0332	0.0928	0.095 (14)*
H18B	0.3702	−0.0428	0.2391	0.084 (13)*
H18C	0.3937	0.0384	0.1801	0.094 (15)*
C21	0.7094 (3)	−0.1406 (2)	0.5066 (3)	0.0480 (7)
C22	0.6331 (2)	−0.1936 (2)	0.5688 (3)	0.0470 (7)
C23	0.6796 (3)	−0.2570 (3)	0.6547 (3)	0.0625 (9)
C24	0.8038 (3)	−0.2680 (3)	0.6814 (4)	0.0682 (10)
C25	0.8818 (3)	−0.2160 (3)	0.6244 (3)	0.0627 (10)
C26	0.8351 (3)	−0.1527 (2)	0.5372 (3)	0.0562 (8)
C27	0.6605 (3)	−0.0753 (2)	0.4079 (4)	0.0631 (9)
O21	0.5535 (2)	−0.0589 (2)	0.3818 (3)	0.0887 (9)
O22	0.7432 (3)	−0.0378 (2)	0.3496 (4)	0.1182 (14)
N28	0.5005 (2)	−0.1836 (2)	0.5471 (3)	0.0537 (7)
H28A	0.4660	−0.2323	0.5197	0.080 (13)*
H28B	0.4804	−0.1445	0.4840	0.082 (13)*
H28C	0.4746	−0.1678	0.6241	0.084 (13)*
H13	0.228 (3)	0.110 (2)	0.036 (3)	0.056 (9)*
H14	0.022 (4)	0.151 (3)	0.021 (4)	0.093 (13)*
H15	−0.104 (3)	0.078 (2)	0.148 (3)	0.068 (10)*
H16	−0.032 (3)	−0.034 (2)	0.286 (3)	0.066 (10)*
H23	0.623 (3)	−0.291 (3)	0.692 (4)	0.081 (12)*
H24	0.839 (4)	−0.309 (3)	0.739 (4)	0.084 (12)*
H25	0.971 (3)	−0.223 (2)	0.642 (3)	0.067 (10)*
H26	0.889 (3)	−0.116 (2)	0.493 (4)	0.071 (10)*
H61	0.787 (4)	0.275 (3)	−0.132 (5)	0.090 (16)*
H62	0.767 (4)	0.218 (3)	−0.037 (4)	0.094 (16)*
H11	0.138 (5)	−0.178 (4)	0.452 (6)	0.13 (2)*
H22	0.702 (6)	−0.008 (3)	0.282 (4)	0.19 (3)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0481 (5)	0.0607 (5)	0.0458 (4)	0.0003 (4)	0.0142 (3)	−0.0025 (4)
O2	0.0680 (16)	0.0726 (17)	0.0866 (17)	0.0057 (12)	0.0442 (13)	−0.0027 (13)
O3	0.109 (2)	0.0586 (16)	0.0912 (19)	0.0204 (15)	0.0488 (16)	0.0033 (14)
O4	0.0908 (19)	0.088 (2)	0.0784 (17)	0.0126 (15)	0.0433 (14)	0.0290 (15)
O5	0.091 (2)	0.224 (5)	0.116 (3)	0.012 (3)	−0.034 (2)	−0.087 (3)
O6	0.0485 (14)	0.0712 (17)	0.0652 (16)	0.0010 (13)	0.0125 (12)	0.0033 (13)
C11	0.0341 (15)	0.057 (2)	0.0484 (16)	−0.0035 (13)	0.0064 (12)	−0.0053 (14)
C12	0.0366 (15)	0.057 (2)	0.0464 (16)	0.0000 (13)	0.0084 (12)	−0.0067 (14)
C13	0.051 (2)	0.063 (2)	0.061 (2)	−0.0042 (16)	0.0120 (16)	0.0022 (17)
C14	0.051 (2)	0.069 (3)	0.078 (2)	0.0075 (17)	0.0048 (17)	0.010 (2)
C15	0.0387 (19)	0.075 (3)	0.083 (3)	0.0073 (17)	0.0077 (17)	0.001 (2)
C16	0.0358 (17)	0.073 (2)	0.064 (2)	−0.0035 (16)	0.0102 (15)	−0.0029 (18)
C17	0.0386 (17)	0.064 (2)	0.0555 (18)	−0.0034 (14)	0.0078 (13)	−0.0003 (15)
O11	0.0421 (13)	0.092 (2)	0.0850 (18)	−0.0050 (12)	0.0149 (12)	0.0282 (15)
O12	0.0386 (13)	0.091 (2)	0.0938 (19)	0.0009 (12)	0.0067 (11)	0.0306 (15)
N18	0.0391 (14)	0.0629 (18)	0.0517 (16)	0.0002 (13)	0.0129 (11)	−0.0070 (14)
C21	0.0403 (16)	0.062 (2)	0.0432 (15)	0.0032 (14)	0.0110 (12)	−0.0059 (14)
C22	0.0386 (16)	0.064 (2)	0.0394 (15)	0.0012 (14)	0.0086 (12)	−0.0053 (14)
C23	0.058 (2)	0.078 (3)	0.053 (2)	0.0054 (19)	0.0149 (16)	0.0129 (18)
C24	0.063 (2)	0.084 (3)	0.057 (2)	0.021 (2)	0.0078 (17)	0.011 (2)
C25	0.0440 (19)	0.089 (3)	0.0545 (19)	0.0125 (18)	0.0042 (15)	−0.0063 (19)
C26	0.0440 (18)	0.071 (2)	0.0555 (19)	0.0005 (16)	0.0137 (15)	−0.0061 (17)
C27	0.046 (2)	0.080 (3)	0.068 (2)	0.0088 (17)	0.0208 (16)	0.0173 (18)
O21	0.0474 (15)	0.124 (3)	0.096 (2)	0.0121 (14)	0.0157 (13)	0.0491 (18)
O22	0.0615 (18)	0.127 (3)	0.177 (3)	0.0306 (18)	0.058 (2)	0.095 (3)
N28	0.0423 (14)	0.074 (2)	0.0470 (15)	0.0002 (14)	0.0140 (11)	0.0002 (15)

Geometric parameters (Å, º)

S1—O5	1.432 (3)	N18—H18A	0.8900
S1—O4	1.451 (2)	N18—H18B	0.8900
S1—O3	1.451 (3)	N18—H18C	0.8900
S1—O2	1.453 (2)	C21—C22	1.393 (4)
O6—H61	0.84 (5)	C21—C26	1.398 (4)
O6—H62	0.85 (5)	C21—C27	1.481 (5)
C11—C16	1.393 (4)	C22—C23	1.376 (5)
C11—C12	1.394 (4)	C22—N28	1.462 (4)
C11—C17	1.490 (4)	C23—C24	1.377 (5)
C12—C13	1.378 (5)	C23—H23	0.94 (4)
C12—N18	1.462 (4)	C24—C25	1.370 (5)
C13—C14	1.382 (5)	C24—H24	0.92 (4)
C13—H13	0.93 (3)	C25—C26	1.383 (5)
C14—C15	1.378 (5)	C25—H25	0.98 (3)
C14—H14	0.97 (4)	C26—H26	0.98 (4)
C15—C16	1.374 (5)	C27—O21	1.206 (4)
C15—H15	0.93 (4)	C27—O22	1.292 (4)
C16—H16	0.97 (4)	O22—H22	0.90 (2)
C17—O12	1.207 (4)	N28—H28A	0.8900
C17—O11	1.308 (4)	N28—H28B	0.8900
O11—H11	0.93 (6)	N28—H28C	0.8900
O5—S1—O4	111.2 (3)	C12—N18—H18C	109.5
O5—S1—O3	108.4 (2)	H18A—N18—H18C	109.5
O4—S1—O3	107.24 (16)	H18B—N18—H18C	109.5
O5—S1—O2	109.2 (2)	C22—C21—C26	117.6 (3)
O4—S1—O2	110.31 (16)	C22—C21—C27	121.9 (3)
O3—S1—O2	110.53 (15)	C26—C21—C27	120.5 (3)
H61—O6—H62	106 (4)	C23—C22—C21	121.3 (3)
C16—C11—C12	117.9 (3)	C23—C22—N28	117.2 (3)
C16—C11—C17	120.2 (3)	C21—C22—N28	121.5 (3)
C12—C11—C17	121.9 (3)	C22—C23—C24	119.6 (4)
C13—C12—C11	120.8 (3)	C22—C23—H23	117 (2)
C13—C12—N18	117.4 (3)	C24—C23—H23	123 (2)
C11—C12—N18	121.7 (3)	C25—C24—C23	120.7 (4)
C12—C13—C14	120.0 (3)	C25—C24—H24	117 (3)
C12—C13—H13	120 (2)	C23—C24—H24	123 (3)
C14—C13—H13	120 (2)	C24—C25—C26	119.7 (3)
C15—C14—C13	120.1 (4)	C24—C25—H25	122 (2)
C15—C14—H14	118 (2)	C26—C25—H25	118 (2)
C13—C14—H14	122 (2)	C25—C26—C21	121.0 (3)
C16—C15—C14	119.8 (3)	C25—C26—H26	121 (2)
C16—C15—H15	120 (2)	C21—C26—H26	118 (2)
C14—C15—H15	120 (2)	O21—C27—O22	122.4 (3)
C15—C16—C11	121.4 (3)	O21—C27—C21	123.8 (3)
C15—C16—H16	120 (2)	O22—C27—C21	113.7 (3)
C11—C16—H16	118 (2)	C27—O22—H22	105 (5)
O12—C17—O11	123.1 (3)	C22—N28—H28A	109.5
O12—C17—C11	123.0 (3)	C22—N28—H28B	109.5
O11—C17—C11	113.8 (3)	H28A—N28—H28B	109.5
C17—O11—H11	109 (3)	C22—N28—H28C	109.5
C12—N18—H18A	109.5	H28A—N28—H28C	109.5
C12—N18—H18B	109.5	H28B—N28—H28C	109.5
H18A—N18—H18B	109.5
C16—C11—C12—C13	−0.1 (5)	C26—C21—C22—C23	−1.6 (5)
C17—C11—C12—C13	−177.5 (3)	C27—C21—C22—C23	176.4 (3)
C16—C11—C12—N18	−179.3 (3)	C26—C21—C22—N28	177.6 (3)
C17—C11—C12—N18	3.3 (4)	C27—C21—C22—N28	−4.4 (5)
C11—C12—C13—C14	0.6 (5)	C21—C22—C23—C24	0.8 (5)
N18—C12—C13—C14	179.9 (3)	N28—C22—C23—C24	−178.4 (3)
C12—C13—C14—C15	−0.6 (6)	C22—C23—C24—C25	0.6 (6)
C13—C14—C15—C16	0.1 (6)	C23—C24—C25—C26	−1.1 (6)
C14—C15—C16—C11	0.4 (6)	C24—C25—C26—C21	0.2 (5)
C12—C11—C16—C15	−0.4 (5)	C22—C21—C26—C25	1.1 (5)
C17—C11—C16—C15	177.0 (3)	C27—C21—C26—C25	−177.0 (3)
C16—C11—C17—O12	−169.2 (3)	C22—C21—C27—O21	5.7 (6)
C12—C11—C17—O12	8.2 (5)	C26—C21—C27—O21	−176.3 (4)
C16—C11—C17—O11	10.3 (4)	C22—C21—C27—O22	−173.2 (4)
C12—C11—C17—O11	−172.3 (3)	C26—C21—C27—O22	4.8 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N18—H18A···O3^i	0.89	2.08	2.901 (4)	153
N18—H18A···O4^i	0.89	2.35	3.112 (4)	144
N18—H18B···O12	0.89	1.96	2.696 (4)	140
N18—H18B···O21	0.89	2.33	3.000 (4)	132
N18—H18C···O2	0.89	1.91	2.791 (4)	173
N28—H28A···O4^ii	0.89	1.88	2.760 (4)	170
N28—H28B···O21	0.89	1.94	2.687 (4)	141
N28—H28B···O12	0.89	2.28	2.926 (4)	129
N28—H28C···O2^iii	0.89	2.01	2.825 (4)	151
N28—H28C···O5^iii	0.89	2.56	3.348 (5)	148
O6—H61···O5^iv	0.84 (5)	1.86 (5)	2.693 (4)	171 (4)
O6—H62···O4	0.85 (5)	1.94 (5)	2.776 (4)	169 (4)
O11—H11···O6^ii	0.93 (6)	1.66 (6)	2.577 (4)	170 (5)
O22—H22···O3	0.90 (2)	1.86 (2)	2.737 (4)	165 (6)
O22—H22···O5	0.90 (2)	2.59 (5)	3.231 (6)	129 (5)

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