The asymmetric unit of the title compound consists of an Li ion, half of the diphenyl-4,4-disulfonate ligand, and a water molecule. The Li ion exhibits a four-coordinate tetrahedral geometry with three oxygen atoms of the Bph(SO3 −)2 ligands and a water molecule. The tetrahedral LiO4 units, which are interconnected by biphenyl moieties, form a layer structure parallel to (100). These layers are further connected by hydrogen-bonding interactions to yield a three-dimensional network.
Keywords: crystal structure, hydrogen bonding, Li ion
Abstract
The asymmetric unit of the title compound, μ-biphenyl-4,4′-disulfonato-bis(aqualithium), [Li2(C12H8O6S2)(H2O)2] or Li2[Bph(SO3)2](H2O)2, consists of an Li ion, half of the diphenyl-4,4′-disulfonate [Bph(SO3 −)2] ligand, and a water molecule. The Li ion exhibits a four-coordinate tetrahedral geometry with three oxygen atoms of the Bph(SO3 −)2 ligands and a water molecule. The tetrahedral LiO4 units, which are interconnected by biphenyl moieties, form a layer structure parallel to (100). These layers are further connected by hydrogen-bonding interactions to yield a three-dimensional network.
1. Chemical context
Coordination networks (CNs) are crystalline materials composed of infinite arrays of s-block metal ions, connected by organic linkers, forming chain, layer or 3-D networks. These materials offer several advantages such as being non-toxic, abundant on the planet, and cheap and provide good results when gravimetric methods are used (Banerjee & Parise 2011 ▸). Li–dicarboxylates may be good candidates as electrode materials for eco-friendly alternatives to other inorganic materials, and have been reported for use in battery applications (Armand et al., 2009 ▸; Ogihara et al., 2014 ▸, 2023 ▸; Yasuda & Ogihara, 2014 ▸; Mikita et al., 2020 ▸). To improve our chemistry and electrode applications, we investigated CNs using disulfonate ligands. While the structures of dicarboxylate salts of alkali metals have been reported (Banerjee & Parise, 2011 ▸), the CNs of the disulfonates of alkali metals are still scarcely reported. Our present investigation focuses on the use of diphenyl-4,4′-disulfonic acid [Bph(SO3H)2] as a structural building block in the synthesis of CNs. Here, we report a rare example of a crystal structure of a Li–disulfonate CN material.
2. Structural commentary
The title compound [Li2(Bph(SO3)2)(H2O)2] (Fig. 1 ▸) consists of two Li cations, two water molecules, and a diphenyl-4,4′-disulfonate [Bph(SO3 −)2] ligand. Its asymmetric unit consists of an Li ion, half of the Bph(SO3 −)2 ligand, and a water molecule. The key feature of the structure is a di-periodic layer structure in which the layers are built up by LiO4 units bridged by Bph(SO3 −)2 ligands (Fig. 2 ▸). The biphenyl groups of the ligands exhibit a planar and herringbone-type arrangement in the layer (Fig. 3 ▸). Two parallel biphenyl groups are stacked not in a face-to-face but rather in a parallel-displaced fashion. The slippage of the layers is 4.43 Å and the nearest intermolecular centroid-to-centroid distance between adjacent parallel phenyl groups is 5.47 Å. The angle formed by the two centroids of the phenyl rings and the ring plane is 34.5°. Intermolecular distances between the carbon atoms of the planar biphenyl moieties of 3.66 Å are indicative of some degree of π–π stacking interaction along the crystallographic b-axis direction. Similar herringbone-type stacking of aromatic organic moieties are found in Li–dicarboxylate CN materials in which herringbone-type stacking structures play an important role in electron mobilities and electrode performance (Ogihara et al., 2017 ▸; Ozawa et al., 2018 ▸). The Li cation exhibits a four-coordinate tetrahedral geometry formed by an oxygen atom of a coordinated water molecule and three oxygen atoms coming from three different Bph(SO3 −)2 ligands. The tetrahedrons are connected to one another by O–S–O bridges of the disulfonate group, and the shortest Li⋯Li distance is 4.80 Å. All the oxygen atoms of a sulfonate group coordinate to different Li cations. Thus, each sulfonate group coordinates to three Li cations to obtain a di-periodic layer. The bond distances between the Li cation and the oxygen atoms lie in the range 1.901 (5)–1.944 (5) Å at angles of 103.7 (2)–114.8 (2) °, which are shorter than those of reported Na2-disulfonate [2.313 (3)–2.560 (3) Å] and K2-disulfonate [2.657 (3)–3.079 (4) Å] complexes (Albat & Stock 2016 ▸; Smith et al., 2007 ▸). Similar trends of bond distances are observed in alkali metal–carboxylate network materials (Banerjee & Parise, 2011 ▸).
Figure 1.
Part of the crystal structure of the title compound with labeling scheme and 50% probability displacement ellipsoids. [Symmetry code: (iii) −x + 2, −y + 1, −z + 1.]
Figure 2.
View of the layer structure of the title compound along the crystallographic b-axis. The layer is built up by LiO4 tetrahedra connected by the organic ligands. The dashed lines represent hydrogen bonds between the oxygen atoms of the Bph(SO3 −)2 ligands and the coordinated water molecules.
Figure 3.
View of the herringbone-type stacking structure in the layer along the crystallographic a-axis.
3. Supramolecular features
The hydrogen atoms of the coordinated water molecules are oriented in such a direction exiting the di-periodic layers to form hydrogen-bonding interactions (Table 1 ▸). A hydrogen atom of the water molecule (H4) and an oxygen atom of the Bph(SO3 −)2 ligand acts as a hydrogen-bond donor and a hydrogen-bond acceptor, respectively, resulting in a three-dimensional hydrogen-bonding network (Fig. 2 ▸). Because of the hydrogen-bonding interaction, another hydrogen atom of the coordinated water molecule (H1) is directed towards the oxygen atom of the Bph(SO3 −)2 ligand, where the distance between the oxygen atoms of 3.204 (3) Å is indicative of some degree of interaction. Li2–dicarboxylates where the dicarboxylate is terephthalate, biphenyl dicarboxylate or naphthalene dicarboxylate, also consist of LiO4 layers (Banerjee & Parise 2011 ▸; Kaduk et al., 2000 ▸; Armand et al., 2009 ▸; Banerjee et al., 2009a ▸,b ▸; Ogihara et al., 2014 ▸). In contrast to the sulfonate compound, four oxygen atoms come from the carboxylate group and LiO4 units share the edges and corners of the tetrahedrons, forming a coordination-bonded three-dimensional structure in these Li2–dicarboxylates.
Table 1. Hydrogen-bond geometry (Å, °).
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| O4—H4⋯O2i | 0.89 (5) | 2.17 (5) | 3.016 (3) | 157 (5) |
| O4—H1⋯O3ii | 2.41 (5) | 3.21 (1) | 0.89 (5) | 149 (4) |
| O4—H1⋯O4iii | 2.50 (5) | 3.14 (1) | 0.89 (5) | 129 (4) |
Symmetry codes: (i)
; (ii)
; (iii)
.
4. Database survey
A survey of the Cambridge Structural Database (CSD, v5.44, April 2023; Groom et al., 2016 ▸) for structures with biphenyl and sulfonate and alkali metals resulted in seven hits. Of these, the alkali metal-coordinated compounds are a potassium complex (HIQKEY; Smith et al., 2007 ▸), which is related to this work, and a sodium complex (SIWVUP; Anderson et al., 1998 ▸). No coordination bonds are found in other alkali-metal salts. Our structure is a rare example of the crystal structure of an Li–disulfonate CN material.
5. Synthesis and crystallization
An aqueous solution (5 mL) of LiOH (0.28 g, 1 mmol L−1) was added to an aqueous solution of Bph(SO3H)2 (1.8 g, 2 mmol L−1). Colorless crystals began to form at ambient temperature in one month. One of these crystals was used for X-ray crystallography.
6. Refinement
Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. Hydrogen-atom parameters were fully refined. The final cycle of the full-matrix least-squares refinement on F 2 was based on 1666 observed reflections and 133 variable parameters.
Table 2. Experimental details.
| Crystal data | |
| Chemical formula | [Li2(C12H8O6S2)(H2O)2] |
| M r | 362.22 |
| Crystal system, space group | Monoclinic, P21/c |
| Temperature (K) | 286 |
| a, b, c (Å) | 15.8584 (11), 5.3693 (4), 8.8636 (6) |
| β (°) | 99.994 (7) |
| V (Å3) | 743.27 (9) |
| Z | 2 |
| Radiation type | Mo Kα |
| μ (mm−1) | 0.40 |
| Crystal size (mm) | 0.50 × 0.40 × 0.20 |
| Data collection | |
| Diffractometer | Rigaku R-AXIS RAPID |
| Absorption correction | Multi-scan (ABSCOR; Rigaku, 1995 ▸) |
| T min, T max | 0.213, 0.924 |
| No. of measured, independent and observed [F 2 > 2.0σ(F 2)] reflections | 9858, 1666, 1490 |
| R int | 0.067 |
| (sin θ/λ)max (Å−1) | 0.649 |
| Refinement | |
| R[F 2 > 2σ(F 2)], wR(F 2), S | 0.061, 0.159, 1.12 |
| No. of reflections | 1666 |
| No. of parameters | 133 |
| No. of restraints | 3 |
| H-atom treatment | All H-atom parameters refined |
| Δρmax, Δρmin (e Å−3) | 0.74, −0.28 |
Supplementary Material
Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989023010411/jp2001sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989023010411/jp2001Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989023010411/jp2001Isup3.cdx
CCDC reference: 2295223
Additional supporting information: crystallographic information; 3D view; checkCIF report
Acknowledgments
We would like to thank Dr Mitsutaro Umehara for the help with the database survey.
supplementary crystallographic information
Crystal data
| [Li2(C12H8O6S2)(H2O)2] | F(000) = 372.00 |
| Mr = 362.22 | Dx = 1.618 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71075 Å |
| a = 15.8584 (11) Å | Cell parameters from 17604 reflections |
| b = 5.3693 (4) Å | θ = 3.2–27.6° |
| c = 8.8636 (6) Å | µ = 0.40 mm−1 |
| β = 99.994 (7)° | T = 286 K |
| V = 743.27 (9) Å3 | Block, colorless |
| Z = 2 | 0.50 × 0.40 × 0.20 mm |
Data collection
| Rigaku R-AXIS RAPID diffractometer | 1490 reflections with F2 > 2.0σ(F2) |
| Detector resolution: 10.000 pixels mm-1 | Rint = 0.067 |
| ω scans | θmax = 27.5°, θmin = 3.9° |
| Absorption correction: multi-scan (ABSCOR; Rigaku, 1995) | h = −20→20 |
| Tmin = 0.213, Tmax = 0.924 | k = −6→6 |
| 9858 measured reflections | l = −11→11 |
| 1666 independent reflections |
Refinement
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.061 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.159 | All H-atom parameters refined |
| S = 1.12 | w = 1/[σ2(Fo2) + (0.0948P)2 + 0.3642P] where P = (Fo2 + 2Fc2)/3 |
| 1666 reflections | (Δ/σ)max < 0.001 |
| 133 parameters | Δρmax = 0.74 e Å−3 |
| 3 restraints | Δρmin = −0.28 e Å−3 |
| Primary atom site location: structure-invariant direct methods |
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. |
| Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 sigma(F2) is used only for calculating R-factor (gt). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | ||
| S1 | 0.67846 (4) | 0.56370 (10) | 0.59448 (6) | 0.0341 (3) | |
| O1 | 0.66681 (15) | 0.8238 (3) | 0.6295 (3) | 0.0550 (6) | |
| O2 | 0.62416 (15) | 0.4887 (5) | 0.4532 (2) | 0.0566 (6) | |
| O3 | 0.67041 (13) | 0.4012 (4) | 0.7215 (2) | 0.0451 (5) | |
| O4 | 0.49748 (14) | 1.0921 (5) | 0.6579 (3) | 0.0587 (6) | |
| C1 | 0.78551 (17) | 0.5384 (4) | 0.5648 (3) | 0.0346 (5) | |
| C2 | 0.81715 (19) | 0.7143 (6) | 0.4756 (4) | 0.0566 (8) | |
| C3 | 0.90075 (19) | 0.6964 (6) | 0.4499 (4) | 0.0588 (9) | |
| C4 | 0.95484 (15) | 0.5075 (4) | 0.5137 (3) | 0.0354 (5) | |
| C5 | 0.9221 (2) | 0.3349 (6) | 0.6046 (5) | 0.0628 (9) | |
| C6 | 0.8381 (2) | 0.3489 (6) | 0.6297 (5) | 0.0608 (9) | |
| Li1 | 0.6195 (3) | 1.0777 (8) | 0.7388 (5) | 0.0413 (9) | |
| H1 | 0.464 (3) | 0.986 (9) | 0.696 (7) | 0.13 (2)* | |
| H2 | 0.778 (3) | 0.874 (10) | 0.441 (5) | 0.083 (13)* | |
| H3 | 0.916 (3) | 0.789 (10) | 0.375 (6) | 0.099 (16)* | |
| H4 | 0.462 (3) | 1.197 (9) | 0.600 (6) | 0.12 (2)* | |
| H5 | 0.954 (3) | 0.196 (9) | 0.644 (5) | 0.078 (13)* | |
| H6 | 0.823 (3) | 0.262 (9) | 0.695 (6) | 0.096 (16)* |
Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S1 | 0.0333 (4) | 0.0345 (4) | 0.0359 (4) | 0.0043 (2) | 0.0093 (2) | −0.0016 (2) |
| O1 | 0.0641 (13) | 0.0359 (11) | 0.0724 (13) | 0.0116 (9) | 0.0324 (11) | 0.0000 (9) |
| O2 | 0.0377 (11) | 0.0905 (17) | 0.0413 (10) | 0.0008 (10) | 0.0057 (9) | −0.0115 (10) |
| O3 | 0.0481 (11) | 0.0404 (9) | 0.0485 (10) | −0.0001 (8) | 0.0131 (8) | 0.0050 (8) |
| O4 | 0.0396 (12) | 0.0691 (14) | 0.0666 (14) | 0.0048 (10) | 0.0073 (10) | 0.0160 (11) |
| C1 | 0.0334 (12) | 0.0316 (11) | 0.0386 (11) | 0.0022 (8) | 0.0060 (9) | −0.0036 (8) |
| C2 | 0.0352 (13) | 0.0581 (17) | 0.077 (2) | 0.0112 (12) | 0.0120 (13) | 0.0322 (15) |
| C3 | 0.0356 (14) | 0.0630 (19) | 0.079 (2) | 0.0077 (12) | 0.0137 (14) | 0.0355 (16) |
| C4 | 0.0302 (13) | 0.0337 (11) | 0.0414 (12) | 0.0007 (8) | 0.0042 (10) | −0.0033 (9) |
| C5 | 0.0479 (17) | 0.0465 (15) | 0.100 (3) | 0.0186 (13) | 0.0298 (17) | 0.0301 (17) |
| C6 | 0.0489 (16) | 0.0460 (15) | 0.095 (2) | 0.0149 (13) | 0.0333 (17) | 0.0300 (17) |
| Li1 | 0.041 (2) | 0.041 (2) | 0.043 (2) | 0.0029 (17) | 0.0106 (18) | 0.0036 (16) |
Geometric parameters (Å, º)
| S1—O3 | 1.4472 (19) | C1—C2 | 1.381 (4) |
| S1—O2 | 1.448 (2) | C2—C3 | 1.387 (4) |
| S1—O1 | 1.4492 (19) | C2—H2 | 1.07 (5) |
| S1—C1 | 1.768 (3) | C3—C4 | 1.384 (4) |
| O1—Li1 | 1.901 (5) | C3—H3 | 0.90 (5) |
| O2—Li1i | 1.922 (5) | C4—C5 | 1.387 (4) |
| O3—Li1ii | 1.933 (5) | C4—C4iii | 1.496 (5) |
| O4—Li1 | 1.944 (5) | C5—C6 | 1.390 (4) |
| O4—H1 | 0.88 (2) | C5—H5 | 0.94 (5) |
| O4—H4 | 0.89 (2) | C6—H6 | 0.81 (5) |
| C1—C6 | 1.377 (4) | ||
| O3—S1—O2 | 112.66 (14) | C4—C3—C2 | 121.8 (3) |
| O3—S1—O1 | 112.48 (12) | C4—C3—H3 | 119 (3) |
| O2—S1—O1 | 112.00 (15) | C2—C3—H3 | 118 (3) |
| O3—S1—C1 | 106.61 (11) | C3—C4—C5 | 117.3 (2) |
| O2—S1—C1 | 107.01 (12) | C3—C4—C4iii | 121.1 (3) |
| O1—S1—C1 | 105.51 (12) | C5—C4—C4iii | 121.6 (3) |
| S1—O1—Li1 | 151.24 (19) | C4—C5—C6 | 121.5 (3) |
| S1—O2—Li1i | 145.2 (2) | C4—C5—H5 | 121 (3) |
| S1—O3—Li1ii | 134.28 (19) | C6—C5—H5 | 118 (3) |
| Li1—O4—H1 | 117 (4) | C1—C6—C5 | 120.1 (3) |
| Li1—O4—H4 | 136 (4) | C1—C6—H6 | 119 (4) |
| H1—O4—H4 | 106 (4) | C5—C6—H6 | 120 (4) |
| C6—C1—C2 | 119.4 (3) | O1—Li1—O2iv | 114.8 (2) |
| C6—C1—S1 | 121.5 (2) | O1—Li1—O3v | 113.3 (2) |
| C2—C1—S1 | 119.09 (19) | O2iv—Li1—O3v | 107.5 (2) |
| C1—C2—C3 | 119.9 (3) | O1—Li1—O4 | 107.2 (3) |
| C1—C2—H2 | 117 (2) | O2iv—Li1—O4 | 103.7 (2) |
| C3—C2—H2 | 122 (2) | O3v—Li1—O4 | 109.8 (2) |
| O3—S1—O1—Li1 | −27.3 (5) | O2—S1—C1—C2 | 74.3 (3) |
| O2—S1—O1—Li1 | 100.8 (5) | O1—S1—C1—C2 | −45.2 (3) |
| C1—S1—O1—Li1 | −143.1 (4) | C6—C1—C2—C3 | 1.1 (5) |
| O3—S1—O2—Li1i | −131.3 (4) | S1—C1—C2—C3 | −179.5 (3) |
| O1—S1—O2—Li1i | 100.7 (4) | C1—C2—C3—C4 | −1.1 (6) |
| C1—S1—O2—Li1i | −14.4 (4) | C2—C3—C4—C5 | 0.2 (5) |
| O2—S1—O3—Li1ii | 12.8 (3) | C2—C3—C4—C4iii | −179.3 (3) |
| O1—S1—O3—Li1ii | 140.6 (3) | C3—C4—C5—C6 | 0.6 (6) |
| C1—S1—O3—Li1ii | −104.2 (3) | C4iii—C4—C5—C6 | −179.8 (4) |
| O3—S1—C1—C6 | 14.5 (3) | C2—C1—C6—C5 | −0.3 (6) |
| O2—S1—C1—C6 | −106.3 (3) | S1—C1—C6—C5 | −179.7 (3) |
| O1—S1—C1—C6 | 134.3 (3) | C4—C5—C6—C1 | −0.6 (6) |
| O3—S1—C1—C2 | −165.0 (2) |
Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) x, y−1, z; (iii) −x+2, −y+1, −z+1; (iv) x, −y+3/2, z+1/2; (v) x, y+1, z.
Hydrogen-bond geometry (Å, º)
| D—H···A | D—H | H···A | D···A | D—H···A |
| O4—H4···O2vi | 0.89 (5) | 2.17 (5) | 3.016 (3) | 157 (5) |
| O4—H1···O3vii | 2.41 (5) | 3.21 (1) | 0.89 (5) | 149 (4) |
| O4—H1···O4viii | 2.50 (5) | 3.14 (1) | 0.89 (5) | 129 (4) |
Symmetry codes: (vi) −x+1, −y+2, −z+1; (vii) −x+1, y+1/2, −z+3/2; (viii) −x+1, y−1/2, −z+3/2.
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Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989023010411/jp2001sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989023010411/jp2001Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989023010411/jp2001Isup3.cdx
CCDC reference: 2295223
Additional supporting information: crystallographic information; 3D view; checkCIF report