Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107063342/gd3169sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107063342/gd3169Isup2.hkl |
CCDC reference: 677220
For related literature, see: Allen (2002); Allen et al. (1987); Cai et al. (2001); Frisch et al. (1998); Gillespie (1963, 1992); Oddershede & Larsen (2001); Pauling (1967).
Suitable crystals of (I) were obtained by slow evaporation of an aqueous solution of 1,5-naphthalenedisulfonic acid. MO calculations were performed using GAUSSIAN98 (Frisch et al., 1998).
H atoms bonded to C atom were treated as riding atom in geometrically idealized positions, with C—H distances of 0.93 Å and Uiso(H) = 1.2Ueq(C). H atoms bonded to O atoms were located in difference maps and their coordinates were refined with Uiso(H) = 1.5Ueq(O), giving a range of O—H distances of 0.80 (4)–0.86 (4) Å for the terminal H atoms and 1.02 (4) and 1.42 (4) Å for the bridging H atom.
Data collection: CrysAlis CCD (Oxford Diffraction, 2005); cell refinement: CrysAlis CCD (Oxford Diffraction, 2005); data reduction: CrysAlis RED (Oxford Diffraction, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1990b); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
2H5O2+·C10H6O6S22− | F(000) = 752 |
Mr = 360.37 | Dx = 1.616 Mg m−3 Dm = 1.61 Mg m−3 Dm measured by floatation |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 1082 reflections |
a = 9.1183 (18) Å | θ = 3.6–28.9° |
b = 7.1051 (14) Å | µ = 0.41 mm−1 |
c = 22.954 (4) Å | T = 295 K |
β = 95.08 (1)° | Plate, colourless |
V = 1481.3 (5) Å3 | 0.32 × 0.28 × 0.11 mm |
Z = 4 |
Kuma KM-4 diffractometer with CCD area detector | 1835 independent reflections |
Radiation source: fine-focus sealed tube | 1575 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.017 |
Detector resolution: 1024x1024 with blocks 2x2 pixels mm-1 | θmax = 28.9°, θmin = 3.6° |
ω–scan | h = −11→12 |
Absorption correction: analytical face-indexed, SHELXTL (Sheldrick, 1990b) | k = −9→9 |
Tmin = 0.884, Tmax = 0.961 | l = −31→28 |
9288 measured reflections |
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)] = 0.030 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.077 | w = 1/[σ2(Fo2) + (0.0381P)2 + 0.9846P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max = 0.001 |
1835 reflections | Δρmax = 0.28 e Å−3 |
116 parameters | Δρmin = −0.28 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0378 (15) |
2H5O2+·C10H6O6S22− | V = 1481.3 (5) Å3 |
Mr = 360.37 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 9.1183 (18) Å | µ = 0.41 mm−1 |
b = 7.1051 (14) Å | T = 295 K |
c = 22.954 (4) Å | 0.32 × 0.28 × 0.11 mm |
β = 95.08 (1)° |
Kuma KM-4 diffractometer with CCD area detector | 1835 independent reflections |
Absorption correction: analytical face-indexed, SHELXTL (Sheldrick, 1990b) | 1575 reflections with I > 2σ(I) |
Tmin = 0.884, Tmax = 0.961 | Rint = 0.017 |
9288 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.077 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.28 e Å−3 |
1835 reflections | Δρmin = −0.28 e Å−3 |
116 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.43372 (4) | 0.15337 (5) | 0.636456 (13) | 0.03117 (14) | |
O1 | 0.51167 (12) | 0.00295 (15) | 0.67039 (4) | 0.0380 (3) | |
O2 | 0.29174 (12) | 0.19037 (17) | 0.65773 (4) | 0.0417 (3) | |
O3 | 0.52443 (14) | 0.31903 (15) | 0.63376 (5) | 0.0460 (3) | |
C1 | 0.25634 (16) | 0.0434 (2) | 0.54291 (6) | 0.0339 (3) | |
H1 | 0.1809 | 0.0663 | 0.5667 | 0.041* | |
C2 | 0.39923 (15) | 0.06717 (19) | 0.56418 (5) | 0.0281 (3) | |
C3 | 0.51847 (15) | 0.03049 (18) | 0.52944 (5) | 0.0269 (3) | |
C4 | 0.66794 (16) | 0.0504 (2) | 0.55032 (6) | 0.0325 (3) | |
H4 | 0.6921 | 0.0876 | 0.5888 | 0.039* | |
C5 | 0.77700 (16) | 0.0160 (2) | 0.51518 (6) | 0.0363 (3) | |
H5 | 0.8747 | 0.0319 | 0.5297 | 0.044* | |
O4 | 0.75030 (15) | 0.0361 (2) | 0.74097 (5) | 0.0461 (3) | |
H41 | 0.664 (3) | 0.028 (3) | 0.7222 (11) | 0.069* | |
H42 | 0.736 (2) | 0.103 (4) | 0.7690 (11) | 0.069* | |
O5 | 0.9387 (2) | 0.1384 (2) | 0.68043 (10) | 0.0664 (7) | |
H51 | 0.962 (4) | 0.060 (6) | 0.6578 (15) | 0.099* | |
H52 | 0.960 (4) | 0.254 (6) | 0.6733 (16) | 0.099* | |
H2 | 0.836 (4) | 0.094 (4) | 0.7213 (13) | 0.069* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0441 (2) | 0.0285 (2) | 0.02254 (18) | 0.00090 (14) | 0.01200 (13) | −0.00211 (12) |
O1 | 0.0476 (6) | 0.0383 (6) | 0.0279 (5) | 0.0014 (5) | 0.0028 (4) | 0.0012 (4) |
O2 | 0.0488 (6) | 0.0502 (7) | 0.0285 (5) | 0.0094 (5) | 0.0162 (4) | −0.0016 (5) |
O3 | 0.0657 (7) | 0.0324 (6) | 0.0427 (6) | −0.0084 (5) | 0.0205 (5) | −0.0095 (5) |
C1 | 0.0356 (7) | 0.0376 (7) | 0.0304 (7) | 0.0026 (6) | 0.0128 (5) | 0.0006 (6) |
C2 | 0.0383 (7) | 0.0256 (6) | 0.0215 (6) | 0.0023 (5) | 0.0094 (5) | 0.0008 (5) |
C3 | 0.0360 (7) | 0.0230 (6) | 0.0228 (6) | 0.0019 (5) | 0.0083 (5) | 0.0015 (5) |
C4 | 0.0397 (7) | 0.0341 (7) | 0.0242 (6) | 0.0006 (6) | 0.0050 (5) | −0.0017 (5) |
C5 | 0.0340 (7) | 0.0414 (8) | 0.0338 (7) | −0.0011 (6) | 0.0055 (6) | −0.0003 (6) |
O4 | 0.0442 (6) | 0.0575 (8) | 0.0373 (6) | −0.0024 (6) | 0.0082 (5) | −0.0120 (5) |
O5 | 0.0756 (13) | 0.0470 (7) | 0.0898 (16) | −0.0114 (8) | 0.0442 (12) | −0.0162 (8) |
S1—O3 | 1.4431 (12) | C4—C5 | 1.357 (2) |
S1—O2 | 1.4475 (11) | C4—H4 | 0.9300 |
S1—O1 | 1.4683 (11) | C5—C1i | 1.406 (2) |
S1—C2 | 1.7703 (13) | C5—H5 | 0.9300 |
C1—C2 | 1.361 (2) | O4—H41 | 0.86 (3) |
C1—C5i | 1.406 (2) | O4—H42 | 0.82 (3) |
C1—H1 | 0.9300 | O4—H2 | 1.02 (4) |
C2—C3 | 1.4281 (18) | O5—H51 | 0.80 (4) |
C3—C4 | 1.411 (2) | O5—H52 | 0.86 (4) |
C3—C3i | 1.431 (2) | ||
O3—S1—O2 | 113.54 (7) | C4—C3—C3i | 119.38 (15) |
O3—S1—O1 | 111.35 (7) | C2—C3—C3i | 117.10 (15) |
O2—S1—O1 | 111.02 (7) | C5—C4—C3 | 121.11 (13) |
O3—S1—C2 | 107.27 (7) | C5—C4—H4 | 119.4 |
O2—S1—C2 | 106.80 (7) | C3—C4—H4 | 119.4 |
O1—S1—C2 | 106.42 (6) | C4—C5—C1i | 120.63 (14) |
C2—C1—C5i | 119.82 (13) | C4—C5—H5 | 119.7 |
C2—C1—H1 | 120.1 | C1i—C5—H5 | 119.7 |
C5i—C1—H1 | 120.1 | H41—O4—H42 | 103 (2) |
C1—C2—C3 | 121.94 (12) | H41—O4—H2 | 120 (2) |
C1—C2—S1 | 117.66 (10) | H42—O4—H2 | 107 (2) |
C3—C2—S1 | 120.37 (10) | H51—O5—H52 | 118 (4) |
C4—C3—C2 | 123.52 (12) |
Symmetry code: (i) −x+1, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H2···O5 | 1.02 (4) | 1.42 (4) | 2.416 (2) | 163 (3) |
O4—H41···O1 | 0.86 (3) | 1.76 (3) | 2.6059 (19) | 167 (2) |
O4—H42···O2ii | 0.82 (3) | 1.83 (3) | 2.6294 (17) | 164 (2) |
O5—H51···O3iii | 0.80 (4) | 1.90 (4) | 2.6562 (19) | 156 (4) |
O5—H52···O1iv | 0.86 (4) | 1.83 (4) | 2.6891 (19) | 171 (4) |
Symmetry codes: (ii) −x+1, y, −z+3/2; (iii) x+1/2, y−1/2, z; (iv) x+1/2, y+1/2, z. |
Experimental details
Crystal data | |
Chemical formula | 2H5O2+·C10H6O6S22− |
Mr | 360.37 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 295 |
a, b, c (Å) | 9.1183 (18), 7.1051 (14), 22.954 (4) |
β (°) | 95.08 (1) |
V (Å3) | 1481.3 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.41 |
Crystal size (mm) | 0.32 × 0.28 × 0.11 |
Data collection | |
Diffractometer | Kuma KM-4 diffractometer with CCD area detector |
Absorption correction | Analytical face-indexed, SHELXTL (Sheldrick, 1990b) |
Tmin, Tmax | 0.884, 0.961 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9288, 1835, 1575 |
Rint | 0.017 |
(sin θ/λ)max (Å−1) | 0.679 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.077, 1.06 |
No. of reflections | 1835 |
No. of parameters | 116 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.28, −0.28 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2005), CrysAlis RED (Oxford Diffraction, 2005), SHELXS97 (Sheldrick, 1990a), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 1990b).
S1—O3 | 1.4431 (12) | C1—C5i | 1.406 (2) |
S1—O2 | 1.4475 (11) | C2—C3 | 1.4281 (18) |
S1—O1 | 1.4683 (11) | C3—C4 | 1.411 (2) |
S1—C2 | 1.7703 (13) | C3—C3i | 1.431 (2) |
C1—C2 | 1.361 (2) | C4—C5 | 1.357 (2) |
O3—S1—O2 | 113.54 (7) | O3—S1—C2 | 107.27 (7) |
O3—S1—O1 | 111.35 (7) | O2—S1—C2 | 106.80 (7) |
O2—S1—O1 | 111.02 (7) | O1—S1—C2 | 106.42 (6) |
Symmetry code: (i) −x+1, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H2···O5 | 1.02 (4) | 1.42 (4) | 2.416 (2) | 163 (3) |
O4—H41···O1 | 0.86 (3) | 1.76 (3) | 2.6059 (19) | 167 (2) |
O4—H42···O2ii | 0.82 (3) | 1.83 (3) | 2.6294 (17) | 164 (2) |
O5—H51···O3iii | 0.80 (4) | 1.90 (4) | 2.6562 (19) | 156 (4) |
O5—H52···O1iv | 0.86 (4) | 1.83 (4) | 2.6891 (19) | 171 (4) |
Symmetry codes: (ii) −x+1, y, −z+3/2; (iii) x+1/2, y−1/2, z; (iv) x+1/2, y+1/2, z. |
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In solid hydrates of strong acids, the H atom has been found to be hydrated to form a series of cations which have been characterized as H3O+, H5O2+, H7O3+ and H9O4+ depending upon the degree of hydration. A search of the Cambridge Structural Database (Version 5.28; Allen, 2002) for structures containing the 1,5-naphthalenedisulfonate anion yielded only seven examples, all salts of the metals of groups 1 and 2 (Cai et al., 2001). The structure of 1,5-naphthalenedisulfonic acid itself is not known. We report here the crystal structure of 1,5-naphthalenedisulfonic acid tetrahydrate, in which the H atoms of the SO3H groups are transferred to the water molecules to form the salt 2H5O2+·C10H6(SO3)2]2-, (I).
The anion in (I) lies across a centre of inversion so that the asymmetric unit of (I) consists of one-half of a naphthalene-1,5-disulfonate(2-) anion and an H5O2+ cation (Fig. 1). The naphthalene ring of the anion is essentially planar [the greatest deviations of the C atoms from the weighted mean ring plane are smaller than 0.010 (2) Å], but its bond distances exhibit significant differences from those of naphthalene itself (Brock & Dunitz, 1982; Oddershede & Larsen, 2001). The C2—C3, C3—C4 and C3—C3i bonds [symmetry code: (i) -x + 1, -y, -z + 1; Table 1] are significantly longer than the other C—C bonds within the ring. The distortions are the result of the substitution effect of the SO3 groups joined to the ring at the 1,5-positions. The ab-initio gas-phase geometry calculated for an isolated anion shows quite good correlation between the C—C bonds and C—C—C angles within the ring (Fig. 2). Thus the distortions arise mainly from the electronic structure and to a lesser degree from the molecular interaction as well as from the crystal packing forces. The S—O bonds of the SO3- group are all intermediate in length between double S═O and single bonds (Allen et al., 1987), indicating charge delocalization onto all O atoms of this group.
The C—S bond length in the crystal structure is shorter than that calculated for the gas-phase structure (1.841 Å), owing to the interactions of negatively charged SO3- groups with the π-aromatic ring. In the crystal structure, this interaction decreases as a result of the hydrogen-bonding system, which reduces the charge on the SO3- groups. The small differences between the experimental S—O bond lengths result from the strengths of the hydrogen bonds in which the O atoms are involved (Table 2).
The acidic H atom is dihydrated such that pairs of water molecules are joined together via a short O—H···O hydrogen bond to form a discrete H5O2+ ion. However, the acidic H atom is not located at the centre between the O atoms, but closer to one of the two water molecules (Table 2). This is in contrast to the results of molecular orbital (MO) calculations performed for an isolated H5O2+ cation, which is predicted to be symmetric (O···O = 2.417 Å, O—H = 1.210 Å and O—H—O = 176.6°), although in the crystal structure the cation is nonsymmetrical. Ab initio MO calculations indicate that substantial energy is involved in the hydration of the hydronium ion (e.g. H3O+ + H2O = H5O2+, 37 kcal mol-1). The H5O2+ ion has a gauche conformation, with a dihedral angle of 99.5° as defined by the dihedral angle between the two planes defined by atoms O4, H41 and H42 and atoms O5, H51 and H52. Thus the bonding arrangement together with the lone-pair of electrons around each O atom in H5O2+ is tetrahedral. However, because of the hydrogen-bonding system and, especially, to the lone-pair of electrons on both O atoms, the tetrahedron is significantly distorted, since the lone-pair of electrons afford a wider region than the bonding pair, as predicted by the valence-shell electron pair repulsion model (Gillespie, 1963, 1992).
The molecular arrangement in the crystal structure of (I) is mainly determined by relatively strong and directional hydrogen bonds (Table 2), and to a lesser degree by a π–π interaction between the naphthalene ring systems, where the interplanar spacing is ca 3.53 Å (Fig. 3). This value is comparable to the sum of the C atom van der Waals radii of the π-ring system (Pauling, 1967). However, as a result of the mutual shift of the rings, the π–π interaction is not fully effective. The π–π overlaping between the rings takes place only via the outermost C—C bonds (C1—C5i and C5—C1i). The 1,5-naphthalenedisulfate anions are stacked in the crystal structure along the b axis at z = 0 and z = 1/2, and they make an angle of 17.7° with the (010) plane, so forming sheets parallel to (001). The H5O2+ cations are located between these sheets and join together via O—H···O hydrogen bonds into a three-dimensional network. Each H5O2+ cation links four anions. Atom O1 of the SO3_ group is involved in two hydrogen bonds while the other two O atoms of SO3_ are each involved in one hydrogen bond (Table 2).