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Evaporation of an aqueous solution of sulfanilic acid (systematic name: 4-aminobenzene-1-sulfonic acid) at 273 K affords a crystalline dihydrate, C
6H
7NO
3S·2H
2O. The organic molecule exists as a zwitterion; two zwitterions are aligned in an antiparallel fashion about a crystallographic centre of inversion. They interact directly
via two N—H
O hydrogen bonds between the ammonium group of one zwitterion and the sulfonate group of its symmetry-related counterpart, and their aromatic rings are π-stacked, with an interplanar distance of 3.533 (3) Å. One of the cocrystallized water molecules connects the resulting pairs into layers and the second crosslinks the layers into a three-dimensional network. All H atoms connected to N or O atoms find acceptors in suitable geometries. In the resulting crystal, polar and hydrogen-bond-dominated slabs alternate with stacks of organic arene rings. Although the new dihydrate shows efficient space filling, with a packing coefficient of 75.7%, it is unstable and undergoes fast desolvation at room temperature. In this process, the orthorhombic ansolvate forms as a pure phase.
Supporting information
CCDC reference: 1587239
Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2009); data reduction: SAINT-Plus (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2017 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2017 (Sheldrick, 2015).
4-Aminobenzene-1-sulfonic acid dihydrate
top
Crystal data top
C6H7NO3S·2H2O | F(000) = 440 |
Mr = 209.22 | Dx = 1.632 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 11.3338 (6) Å | Cell parameters from 5814 reflections |
b = 5.7650 (3) Å | θ = 5.7–62.7° |
c = 13.9048 (8) Å | µ = 0.37 mm−1 |
β = 110.3710 (11)° | T = 100 K |
V = 851.71 (8) Å3 | Transparent platelet, colourless |
Z = 4 | 0.20 × 0.12 × 0.02 mm |
Data collection top
Bruker D8 gonimeter with an APEX CCD detector diffractometer | 3264 independent reflections |
Radiation source: Incoatec microsource | 2834 reflections with I > 2σ(I) |
Multilayer optics monochromator | Rint = 0.060 |
ω scans | θmax = 33.3°, θmin = 2.9° |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −17→17 |
Tmin = 0.898, Tmax = 1.000 | k = −8→8 |
28058 measured reflections | l = −21→21 |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.036 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.093 | w = 1/[σ2(Fo2) + (0.040P)2 + 0.670P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.004 |
3264 reflections | Δρmax = 0.64 e Å−3 |
146 parameters | Δρmin = −0.47 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | 0.44658 (2) | 1.06435 (5) | 0.21108 (2) | 0.00910 (8) | |
O1 | 0.50583 (8) | 1.03106 (16) | 0.32230 (6) | 0.01236 (16) | |
O2 | 0.34514 (8) | 0.89939 (16) | 0.16541 (7) | 0.01307 (17) | |
O3 | 0.41028 (8) | 1.30458 (15) | 0.18416 (7) | 0.01308 (17) | |
N1 | 0.82843 (9) | 0.86847 (18) | 0.01350 (8) | 0.01115 (18) | |
H1A | 0.8316 (17) | 0.716 (3) | −0.0011 (13) | 0.018 (4)* | |
H1B | 0.904 (2) | 0.922 (4) | 0.0529 (17) | 0.031 (5)* | |
H1C | 0.8032 (18) | 0.945 (3) | −0.0484 (15) | 0.020 (5)* | |
C1 | 0.56405 (10) | 0.9992 (2) | 0.15760 (8) | 0.00969 (19) | |
C2 | 0.56254 (11) | 0.7856 (2) | 0.11052 (9) | 0.0112 (2) | |
H2 | 0.501644 | 0.671824 | 0.109839 | 0.013* | |
C3 | 0.65147 (11) | 0.7406 (2) | 0.06433 (9) | 0.0113 (2) | |
H3 | 0.651525 | 0.595896 | 0.031647 | 0.014* | |
C4 | 0.73980 (10) | 0.9090 (2) | 0.06655 (8) | 0.00986 (19) | |
C5 | 0.74390 (11) | 1.1202 (2) | 0.11611 (9) | 0.0114 (2) | |
H5 | 0.806388 | 1.232035 | 0.118439 | 0.014* | |
C6 | 0.65530 (11) | 1.1652 (2) | 0.16215 (9) | 0.0113 (2) | |
H6 | 0.656920 | 1.308275 | 0.196510 | 0.014* | |
O4 | 0.15086 (9) | 0.58774 (16) | 0.05400 (7) | 0.01464 (17) | |
H4A | 0.104 (2) | 0.580 (4) | 0.0877 (18) | 0.039 (6)* | |
H4B | 0.216 (2) | 0.643 (4) | 0.0974 (18) | 0.039 (6)* | |
O5 | 0.44760 (9) | 1.56610 (16) | 0.36443 (7) | 0.01373 (17) | |
H5A | 0.426 (2) | 1.499 (4) | 0.3081 (18) | 0.031 (5)* | |
H5B | 0.458 (2) | 1.706 (4) | 0.3501 (16) | 0.034 (6)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.00924 (12) | 0.00977 (13) | 0.00848 (12) | 0.00031 (9) | 0.00332 (9) | 0.00032 (9) |
O1 | 0.0131 (4) | 0.0148 (4) | 0.0090 (3) | 0.0007 (3) | 0.0036 (3) | 0.0010 (3) |
O2 | 0.0101 (3) | 0.0150 (4) | 0.0139 (4) | −0.0025 (3) | 0.0038 (3) | −0.0015 (3) |
O3 | 0.0154 (4) | 0.0114 (4) | 0.0134 (4) | 0.0031 (3) | 0.0064 (3) | 0.0017 (3) |
N1 | 0.0113 (4) | 0.0115 (4) | 0.0116 (4) | 0.0007 (3) | 0.0052 (3) | −0.0001 (3) |
C1 | 0.0096 (4) | 0.0106 (5) | 0.0088 (4) | 0.0006 (4) | 0.0032 (3) | 0.0007 (4) |
C2 | 0.0118 (4) | 0.0102 (5) | 0.0117 (5) | −0.0013 (4) | 0.0042 (4) | −0.0007 (4) |
C3 | 0.0131 (5) | 0.0097 (5) | 0.0115 (5) | −0.0005 (4) | 0.0049 (4) | −0.0012 (4) |
C4 | 0.0096 (4) | 0.0115 (5) | 0.0090 (4) | 0.0010 (4) | 0.0038 (4) | 0.0008 (4) |
C5 | 0.0116 (4) | 0.0109 (5) | 0.0120 (5) | −0.0012 (4) | 0.0043 (4) | −0.0006 (4) |
C6 | 0.0118 (4) | 0.0099 (5) | 0.0119 (5) | −0.0006 (4) | 0.0038 (4) | −0.0011 (4) |
O4 | 0.0150 (4) | 0.0155 (4) | 0.0141 (4) | −0.0021 (3) | 0.0060 (3) | −0.0027 (3) |
O5 | 0.0166 (4) | 0.0122 (4) | 0.0128 (4) | 0.0004 (3) | 0.0057 (3) | 0.0011 (3) |
Geometric parameters (Å, º) top
S1—O3 | 1.4560 (9) | C2—H2 | 0.9500 |
S1—O2 | 1.4564 (9) | C3—C4 | 1.3870 (16) |
S1—O1 | 1.4685 (9) | C3—H3 | 0.9500 |
S1—C1 | 1.7765 (11) | C4—C5 | 1.3919 (16) |
N1—C4 | 1.4572 (14) | C5—C6 | 1.3905 (16) |
N1—H1A | 0.90 (2) | C5—H5 | 0.9500 |
N1—H1B | 0.90 (2) | C6—H6 | 0.9500 |
N1—H1C | 0.92 (2) | O4—H4A | 0.83 (2) |
C1—C2 | 1.3916 (16) | O4—H4B | 0.84 (2) |
C1—C6 | 1.3943 (16) | O5—H5A | 0.83 (2) |
C2—C3 | 1.3952 (15) | O5—H5B | 0.85 (2) |
| | | |
O3—S1—O2 | 113.54 (5) | C1—C2—H2 | 120.4 |
O3—S1—O1 | 112.32 (5) | C3—C2—H2 | 120.4 |
O2—S1—O1 | 112.09 (5) | C4—C3—C2 | 119.40 (11) |
O3—S1—C1 | 106.22 (5) | C4—C3—H3 | 120.3 |
O2—S1—C1 | 105.80 (5) | C2—C3—H3 | 120.3 |
O1—S1—C1 | 106.18 (5) | C3—C4—C5 | 121.51 (10) |
C4—N1—H1A | 110.9 (11) | C3—C4—N1 | 119.74 (10) |
C4—N1—H1B | 108.5 (14) | C5—C4—N1 | 118.73 (10) |
H1A—N1—H1B | 111.4 (18) | C6—C5—C4 | 119.10 (11) |
C4—N1—H1C | 110.6 (12) | C6—C5—H5 | 120.4 |
H1A—N1—H1C | 106.3 (16) | C4—C5—H5 | 120.4 |
H1B—N1—H1C | 109.0 (18) | C5—C6—C1 | 119.60 (11) |
C2—C1—C6 | 121.07 (10) | C5—C6—H6 | 120.2 |
C2—C1—S1 | 119.71 (9) | C1—C6—H6 | 120.2 |
C6—C1—S1 | 119.20 (9) | H4A—O4—H4B | 101 (2) |
C1—C2—C3 | 119.25 (10) | H5A—O5—H5B | 104 (2) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O4i | 0.90 (2) | 1.94 (2) | 2.8296 (14) | 168.6 (16) |
N1—H1B···O5ii | 0.90 (2) | 1.87 (2) | 2.7610 (14) | 173 (2) |
N1—H1C···S1iii | 0.92 (2) | 2.945 (19) | 3.5833 (11) | 127.7 (14) |
N1—H1C···O2iii | 0.92 (2) | 2.09 (2) | 2.9056 (14) | 146.8 (16) |
N1—H1C···O5iv | 0.92 (2) | 2.352 (19) | 2.8657 (13) | 115.0 (14) |
C5—H5···O1v | 0.95 | 2.64 | 3.5636 (15) | 165 |
O4—H4A···O1vi | 0.83 (2) | 2.06 (2) | 2.8888 (13) | 174 (2) |
O4—H4B···O2 | 0.84 (2) | 2.06 (2) | 2.8463 (13) | 156 (2) |
O5—H5A···S1 | 0.83 (2) | 2.89 (2) | 3.5912 (10) | 143.0 (19) |
O5—H5A···O3 | 0.83 (2) | 2.01 (2) | 2.8279 (13) | 168 (2) |
O5—H5B···S1vii | 0.85 (2) | 2.80 (2) | 3.5750 (10) | 152.4 (19) |
O5—H5B···O1vii | 0.85 (2) | 2.02 (2) | 2.8693 (13) | 173 (2) |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+3/2, y−1/2, −z+1/2; (iii) −x+1, −y+2, −z; (iv) x+1/2, −y+5/2, z−1/2; (v) −x+3/2, y+1/2, −z+1/2; (vi) −x+1/2, y−1/2, −z+1/2; (vii) x, y+1, z. |
Packing descriptors for the crystal forms of sulfanilic acid topCSD refcode | Space group | Temperature (K) | Composition | Density (Mg m-3) | Volume/formula (Å3) | Volume/non-H atom (Å3) | Packing coefficient (%) |
AFAZEM | Pca21 | 120 | Anhydrous C6H7NO3S | 1.514 | 190.0 | 17.3 | 67.1 |
AFAZEM01 | P21/c | 120 | Anhydrous C6H7NO3S | 1.688 | 170.4 | 15.5 | 75.3 |
SANACM | P21/c | 293 | C6H7NO3S.H2O | 1.568 | 201.4 | 16.8 | 72.7 |
SANACM01 | P212121 | 150 | C6H7NO3S.H2O | 1.615 | 196.5 | 16.4 | 73.7 |
This work | P21/n | 100 | C6H7NO3S.2H2O | 1.632 | 212.9 | 16.4 | 75.7 |
References for CSD refcodes: AFAZEM (Low & Glidewell, 2002);
AFAZEM01 (Callear & Hursthouse, 2008);
SANACM [Rae & Maslen (1962), redetermined by Nazarenko
(2017a,b)];
SANACM01 (Banu & Golzar Hossain, 2006). |
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