Crystal engineering with short-chained amphiphiles: deca­sodium octa-n-butane­sulfonate di-μ-chlorido-bis­[di­chlorido­palladate(II)] tetra­hydrate, a layered inorganic–organic hybrid material

Thoelen, F.; Frank, W.

doi:10.1107/S2056989019004201

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ISSN: 2056-9890

Volume 75| Part 5| May 2019| Pages 557-561

https://doi.org/10.1107/S2056989019004201

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Crystal engineering with short-chained amphiphiles: decasodium octa-n-butanesulfonate di-μ-chlorido-bis[dichloridopalladate(II)] tetrahydrate, a layered inorganic–organic hybrid material

Felix Thoelen ^a and Walter Frank ^a ^*

^aInstitut für Anorganische Chemie und Strukturchemie, Lehrstuhl II: Material- und Strukturforschung, Heinrich-Heine-Universität Düsseldorf, D-40225 Düsseldorf, Germany
^*Correspondence e-mail: wfrank@hhu.de

Edited by M. Weil, Vienna University of Technology, Austria (Received 25 February 2019; accepted 28 March 2019; online 2 April 2019)

In the course of crystal-engineering experiments, crystals of the hydrated title salt, Na₁₀[Pd₂Cl₆](C₄H₉SO₃)₈·4H₂O, were obtained from a water/2-propanol solution of sodium n-butanesulfonate and sodium tetrachloridopalladate(II). In the crystal, sodium n-butanesulfonate anions and water molecules are arranged in an amphiphilic inverse bilayered cationic array represented by the formula {[Na₁₀(C₄H₉SO₃)₈(H₂O)₄]²⁺}_n. Within this lamellar array: (i) a hydrophilic layer region parallel to the bc plane is established by the Na⁺ cations, the H₂O molecules (as aqua ligands in κNa,κNa′-bridging coordination mode) and the O₃S– groups of the sulfonate ions, and (ii) hydrophobic regions are present containing all the n-butyl groups in an almost parallel orientation, with the chain direction approximately perpendicular to the aforementioned hydrophilic layer. Unexpectedly, the flat centrosymmetric [Pd₂Cl₆]²⁻ anion in the structure is placed between the butyl groups, within the hydrophobic regions, but due to its appropriate length primarily bonded to the hydrophilic `inorganic' layer regions above and below the hydrophobic area via Pd—Cl_t⋯Na- and Pd—Cl_t⋯H—O(H)—Na-type (Cl_t is terminal chloride) interactions. In addition to these hydrogen-bonding interactions, both aqua ligands are engaged in charge-supported S—O⋯H—O hydrogen bonds of a motif characterized by the D₄³(9) graph-set descriptor within the hydrophilic region. The crystal structure of the title compound is the first reported for a metal n-butanesulfonate.

Keywords: crystal structure; sodium n-butanesulfonate; hexachloridodipalladate(II); amphiphile; bilayered structure; inorganic–organic hybrid material.

CCDC reference: 1906335

1. Chemical context

Sodium alkanesulfonates are artificial soaps (anionic tensides) with a widespread use (Schramm et al., 2003 ). They are known to have a bilayered structure like `natural' soaps, with an extreme tendency for disorder in the crystalline state (Buerger, 1942 ; Buerger et al., 1942 ). Compounds containing alkanesulfonate ions of the general formula C_nH_2n+1SO₃⁻ with n = 1–4 may be defined as short-chained alkanesulfonates (SCAS). In contrast to methanesulfonates (n = 1) and ethanesulfonates (n = 2), there is only rare structure information for the next higher homologues (n = 3, 4) (Frank & Jablonka, 2008 ; Russell et al., 1994 ). Solid sodium methanesulfonate is described as an inorganic–organic three-dimensional network (Wei & Hingerty, 1981 ). However, closer inspection shows the compound to have a bilayered soap-like structure with only one of five CH₃SO₃⁻ anions connecting in the third dimension. In crystal-engineering experiments, we successfully exchanged this connecting anion by selected other ionic moieties and were able to retain the lamellar structure (Thoelen & Frank, 2017 , 2018 ; Verheyen & Frank, 2009 ). An aim of subsequent attempts was to include chloridopalladate(II) anions Pd_nCl_2n+2²⁻ that are known to be catalytically active (Bouquillion et al., 1999 ; Jimeno et al., 2012 ; Lassahn et al., 2003 ; Mu et al., 2012 ), by using [PdCl₄]²⁻ in the form of its sodium salt as a typical precursor in aqueous palladium(II) chemistry.

In the investigation described herein, the incorporation of hexachloridodipalladate(II) anions into the sodium n-butanesulfonate layered system was realized, resulting in the title compound (1) having the typical brown colour of palladium complexes with a square-planar coordination environment. According to the results of elemental analysis and vibrational spectroscopic investigations, hydrated sodium cations, n-butanesulfonate and hexachloridodipalladate(II) anions are present in the solid. The crystal structure determination of this compound is the first of a metal n-butanesulfonate and eventually confirmed the composition Na₁₀(C₄H₉SO₃)₈[Pd₂Cl₆]·4H₂O and a lamellar amphiphilic structure.

2. Structural commentary

Fig. 1 shows the asymmetric unit of the crystal structure that contains (all in general positions) five sodium cations, two water molecules, four n-butanesulfonate anions and, close to a center of inversion, one half of a hexachloridodipalladate anion. The five Na⁺ cations are in quite different coordination environments (Fig. 2), defined by five sulfonato ligands (Na4, Na5), four sulfonato ligands and one aqua ligand (Na3), four sulfonato ligands and two aqua ligands (Na2) and four sulfonato ligands, one aqua ligand and one terminal chlorido ligand of the [Pd₂Cl₆]²⁻ anion (Na1). Bond lengths and angles of the n-butanesulfonate anions are as expected (see supplementary Tables). All these anions are found with an entirely anti-periplanar conformation of the alkyl groups, without any disorder. Altogether, n-butanesulfonate anions, Na⁺ cations and water molecules form a tenside-like inverse bilayered cationic array, which can be described by the formula {[Na₁₀(H₂O)₄(C₄H₉SO₃)₈]²⁺}_n. In this arrangement, the layer-like regions are oriented parallel to the bc plane of the unit cell. As visualized by the blue and the red sections of the transparent background of Fig. 3, hydrophilic and hydrophobic regions are given, reminiscent of sections of the structures of `pure' short-chained sodium alkanesulfonates (Frank & Jablonka, 2008; Wei & Hingerty, 1981). The hydrophilic areas contain the Na⁺ cations, the H₂O molecules serving as aqua ligands in μ(κNa,κNa′) bridging mode coordination, and the O₃S– groups of the sulfonate ions. With all the C₄-chains in an approximately parallel orientation, the butyl groups are arranged on both sides of the hydrophilic region to complete the amphiphilic double layer with an inverse bilayer thickness according to unit-cell parameter a. The centrosymmetric [Pd₂Cl₆]²⁻ anions in the structure of 1 are placed between the n-butyl groups within the hydrophobic regions. In a first view, this position seems to be unexpected; however, the length of the dipalladate(II) anion is appropriate to allow for pronounced bonding to the hydrophilic `inorganic' layered regions above and below the hydrophobic area (Fig. 3). To interact with the inorganic areas above and below the hydrophobic region, a building block is needed that fits to the thickness of the hydrophobic double layer. In the concrete case of 1, the thickness is determined by the lengths of two `end-facing' n-butyl groups.

Figure 1
The asymmetric unit of 1, chosen to give a compact segment with all n-butyl groups of the hydrophobic layer region oriented in one direction. In addition, the symmetry-related second half of the hexachloridodipallate(II) anion is shown in transparent mode [symmetry code: (i) −x, 1 − y, 1 − z.]. The direction of coordinative bonding to atoms of neighbouring moieties is given by sharpened sticks, and hydrogen bonds are shown as segmented solid bonds. Displacement ellipsoids are drawn at the 50% probability level, hydrogen atoms are drawn with an arbitrary radius. Note the coordination of the hexachloridodipalladate(II) ion to hydrophilic moieties by hydrogen bonding and `local' ionic interactions.

Figure 2
Coordination environments of sodium cations. For clarity, n-butylgroups of the n-butanesulfonate anions are not shown. [Symmetry codes: (i) x, $[{1\over 2}]$ − y, $[{1\over 2}]$ + z; (ii) 1 − x, 1 − y, 1 − z; (iii) x, 1 + y, z; (iv) x, −1 + y, z; (v) 1 − x, − $[{1\over 2}]$ + y, $[{1\over 2}]$ − z; (vi) 1 − x, $[{1\over 2}]$ + y, $[{1\over 2}]$ − z]. The Na—O distances [Na1—O = 2.284 (3)–2.540 (3) Å; Na2—O = 2.283 (3)–2.700 (3) Å; Na3—O = 2.212 (2)–2.649 (3) Å; Na4—O = 2.308 (5)–2.479 (3) Å; Na5—O = 2.391 (3)–3.000 (4) Å] are within the reported range for short-chained sodium alkanesulfonates (Wei & Hingerty, 1981

Figure 3
Diagram displaying hydrophilic (blue) and hydrophobic sections (red) of the bilayered amphiphile packing of 1; layers are parallel to the bc plane of the unit cell. Note the inverse bilayer thickness corresponding to the unit-cell dimension along [100]. The hexachloridodipalladate(II) anions are placed within the hydrophobic region but are primarily bonded to the hydrophilic.

As expected, the Pd—Cl bonds to the terminal chlorido ligands [2.2776 (12) and 2.2800 (10) Å] are slightly shorter than the Pd—μ-Cl bonds [2.3159 (11) and 2.3212 (12) Å]. These geometric parameters, as well as the Cl—Pd—Cl bond angles of 86.20 (4) to 92.45 (4)° and the Pd—μ-Cl—Pd angle of 93.80 (4)°, are in good agreement with those found in Cs₂[Pd₂Cl₆] (Schüpp & Keller, 1999 ) or in several hexachloridodipalladates with large organic cations (e.g. Chitanda et al., 2008 ; Gerisch et al., 1997 ; Makitova et al., 2007 ). Alternatively to the formula given above, compound 1 might be formulated as a hydrated double salt of sodium n-butanesulfonate and sodium hexachloridodipalladate(II): Na₈(C₄H₉SO₃)₈·Na₂Pd₂Cl₆·4H₂O. This choice takes into account that the Na—Cl distance from the terminal chlorido ligand Cl2 of the hexachloridodipalladate(II) anion to the sodium cation Na1 [2.8560 (18) Å] is close to the distances of 2.809 (3) to 2.821 (2) Å in Na₂PdCl₄ (Schröder & Keller, 1989 ). However, this is a singular similarity, and because all the sodium cations of 1 clearly are components of the layer-like hydrophilic region, there is a much closer structural relationship of 1 to sodium methanesulfonate (Wei & Hingerty, 1981) and sodium 1-propanesulfonate monohydrate (Frank & Jablonka, 2008). As in the structures of these compounds, the asymmetric unit in 1 contains five Na⁺ cations, establishing a closely related Na—O coordination network, and the separation of hydrophilic layers and hydrophobic areas is similar to the most prominent structural feature of crystallized amphiphiles where the neighbouring hydrophobic areas in the layer-like structures are connected by van der Waals forces only.

3. Supramolecular features

As emphasized in Fig.1, in addition to the coordinative bonding to two Na⁺ cations [O1—Na1 = 2.326 (3) Å, O1—Na2 = 2.407 (4) Å; O2—Na3 = 2.311 (4) Å, O2—Na2′ = 2.488 (4) Å], the two crystallographically independent water molecules O1 and O2 in 1 are engaged in non-covalent bonding within the hydrophilic region (Table 1). The water molecule containing O1 serves as donor for both a charge-supported O—H⋯Cl-type hydrogen bond of medium strength to one of the terminal chlorido ligands of the [Pd₂Cl₆]²⁻ anion [D⋯A distance = 3.127 (3) Å] and a charge-supported weak O—H⋯O type hydrogen bond to an O atom of a sulfonate anion containing S4 [D⋯A = 2.879 (4) Å]. In contrast, the water molecule containing O2 is engaged in two O—H⋯O type hydrogen bonds to sulfonate ions, one of moderate strength to an O atom of the sulfonate ion containing S4 [D⋯A = 2.723 (4) Å] and a weak one to an O atom of the sulfonate ion containing S3 [D⋯A = 2.884 (4) Å]. Pd—Cl_term⋯H—O(Na₂)—H⋯O14(S4)⋯H—O(Na₂)—H⋯O—S is the entire path of hydrogen bonding described by the D³₄(9) graph-set descriptor (Russell et al., 1994; Grell et al., 1999 ), with the sulfonate oxygen atom O14 as the central double acceptor.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O14ⁱ	0.80 (3)	2.10 (4)	2.879 (4)	164 (5)
O1—H2⋯Cl1	0.82 (3)	2.32 (4)	3.127 (3)	172 (6)
O2—H3⋯O10ⁱⁱ	0.81 (3)	1.95 (4)	2.723 (4)	159 (5)
O2—H4⋯O14ⁱⁱ	0.80 (3)	2.10 (4)	2.884 (4)	164 (6)
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

4. Database survey

A search in the Cambridge Structural Database (Version 5.40, update November 2018; Groom et al., 2016 ) for short-chained sodium alkanesulfonates Na(C_nH_2n+1SO₃) with n = 1–4 gave three hits, viz. the structures of sodium methanesulfonate (BAKLAA; Wei & Hingerty, 1981), sodium 1-propanesulfonate monohydrate (GOKHIY; Frank & Jablonka, 2008) and α-cyclodextrin sodium 1-propanesulfonate nonahydrate (ACDPRS; Harata, 1977 ). For crystal structures with n-butanesulfonate anions, only one entry was found (WETNUE; Russell et al., 1994), describing the lamellar structure of guanidinium n-butanesulfonate. Searching for the hexachloridodipalladate(II) anion results in 46 entries. However, from a structural point of view, the role of the [Pd₂Cl₆]²⁻ ion in 1 is completely different from the role of this species in all the other compounds. In addition to the reports on these compounds having organic components, there is one report on an inorganic ternary chloride containing the [Pd₂Cl₆]²⁻ ion (CsPdCl₃; Schüpp & Keller, 1999).

5. Synthesis and Crystallization

Thin brown platelets of 1 were obtained by slow isothermal evaporation of the solvent from a solution of 5 ml of distilled water and 5 ml of isopropanol containing 3.203 g (20 mmol) of sodium n-butanesulfonate and 1.177 g (4 mmol) of sodium tetrachloridopalladate(II). The evaporation temperature of the solution was adjusted to 288 K with a thermostat. After three days, crystals suitable for X-ray crystal structure determination could be harvested (5.985 g; 81.6% based on PdCl₄^2–). A single crystal was selected directly from the mother liquor. Raman spectroscopy was done with a Bruker MultiRAM spectrometer, equipped with a Nd:YAG laser (1064 nm) and an InGaAs detector (4000–70 cm⁻¹): ν(C—H): 2969 (m), 2920 (s), 2872 (m); δ_s(C—H): 1445 (w), 1412 (w); δ_as(C—H): 1306 (w); ν_as(S—O): 1071 (s); ν_s(C—S): 800 (m); δ(S—O): 551 (m), 536 (m); ν(Pd—Cl_term): 343 (m), ν(Pd—μ-Cl): 305 (s); ν(Pd—μ-Cl): 273 (m). Band assignments were made according to Fujimori (1959 ) and Gerisch et al. (1997). An IR spectrum was recorded by using a Spektrum Two FT–IR spectrometer (Perkin Elmer company) with an LiTaO₃ detector (4000–350 cm⁻¹) and an universal ATR equipment: ν(O—H): 3503 (s), 3462 (sh), 3436 (s), 3367 (s); ν(C—H): 2967 (s), 2936 (s), 2872 (m); δ(O—H): 1662 (m), 1602 (m); δ_s(C—H) 1465 (m), 1412 (w), 1378 (w), δ_as(C—H): 1314 (w), 1286 (w); ν_as(C—H): 1241 (w); ν_s(S—O): 1190 (s), 1166 (s); ν_as(S—O): 1057 (s), 1044 (s); ν_s(C—S): 794 (m); δ(S—O): 555 (m), 534 (m); band assignment according to Fujimori (1959). A CHS analysis was performed with a vario micro cube (Elementar Analysensysteme GmbH). Analysis calculated for C₃₂H₈₀Cl₆Na₁₀O₂₈Pd₂S₈ (1824.84 g mol⁻¹): C 21.06, H 4.42, S 14.06; found: C 20.78, H 4.49, S 12.98.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The positions of all hydrogen atoms were identified in difference-Fourier syntheses. In the course of the converging refinement, a riding model was applied using idealized C—H bond lengths (0.97–0.98 Å) as well as H—C—H and C—C—H angles. In addition, H atoms of CH₃ groups were allowed to rotate around the neighboring C—C bonds. The U_iso(H) values were set to 1.5U_eq(C_methyl) and 1.2U_eq(C_methylene), respectively. H—O distances of the water molecules were restrained to 0.83 (3) Å.

Table 2
Experimental details

Crystal data
Chemical formula	Na₁₀[Pd₂Cl₆](C₄H₉O₃S)₈·4H₂O
M_r	1824.84
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	213
a, b, c (Å)	15.9049 (4), 9.9047 (2), 22.6734 (7)
β (°)	94.315 (2)
V (Å³)	3561.69 (16)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	1.10
Crystal size (mm)	0.43 × 0.13 × 0.06

Data collection
Diffractometer	Stoe IPDS_2T
Absorption correction	Multi-scan (PLATON; Spek, 2009 )
T_min, T_max	0.650, 0.937
No. of measured, independent and observed [I > 2σ(I)] reflections	48866, 8183, 7116
R_int	0.072
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.062, 0.099, 1.54
No. of reflections	8183
No. of parameters	408
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.73, −0.43
Computer programs: X-AREA (Stoe & Cie, 2009 ), SHELXT (Sheldrick, 2015a ), SHELXL2018 (Sheldrick, 2015b ), DIAMOND (Brandenburg, 2016 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1906335

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989019004201/wm5491sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019004201/wm5491Isup2.hkl

checkCIF report

Computing details top

Data collection: X-AREA (Stoe & Cie, 2009); cell refinement: X-AREA (Stoe & Cie, 2009); data reduction: X-AREA (Stoe & Cie, 2009); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg, 2016); software used to prepare material for publication: publCIF (Westrip, 2010).

Decasodium octa-n-butanesulfonate di-µ-chlorido-bis[dichloridopalladate(II)] tetrahydrate top

Crystal data top

Na₁₀[Pd₂Cl₆](C₄H₉O₃S)₈·4H₂O	F(000) = 1856
M_r = 1824.84	D_x = 1.702 Mg m⁻³ D_m = 1.712 Mg m⁻³ D_m measured by flotation in chloroform/bromoform
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 15.9049 (4) Å	Cell parameters from 49957 reflections
b = 9.9047 (2) Å	θ = 4.1–59.3°
c = 22.6734 (7) Å	µ = 1.10 mm⁻¹
β = 94.315 (2)°	T = 213 K
V = 3561.69 (16) Å³	Thin platelets, brown
Z = 2	0.43 × 0.13 × 0.06 mm

Data collection top

Stoe IPDS_2T diffractometer	7116 reflections with I > 2σ(I)
ω scan	R_int = 0.072
Absorption correction: multi-scan (PLATON; Spek, 2009)	θ_max = 27.5°, θ_min = 2.1°
T_min = 0.650, T_max = 0.937	h = −20→20
48866 measured reflections	k = −11→12
8183 independent reflections	l = −29→29

Refinement top

Refinement on F²	4 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.062	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.099	w = 1/[σ²(F_o²) + (0.0215P)² + 3.8152P] where P = (F_o² + 2F_c²)/3
S = 1.54	(Δ/σ)_max < 0.001
8183 reflections	Δρ_max = 0.73 e Å⁻³
408 parameters	Δρ_min = −0.43 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	U_iso*/U_eq
Pd1	0.10273 (2)	0.51478 (3)	0.52464 (2)	0.02493 (8)
Cl1	0.18814 (7)	0.69241 (11)	0.55153 (7)	0.0452 (3)
Cl2	0.20910 (6)	0.36261 (11)	0.54280 (6)	0.0361 (3)
Cl3	0.01032 (7)	0.34122 (11)	0.49624 (7)	0.0465 (3)
S1	0.37572 (5)	0.04330 (8)	0.48827 (4)	0.01605 (17)
S2	0.40803 (5)	0.51616 (8)	0.41684 (4)	0.01565 (17)
S3	0.37879 (6)	0.32626 (9)	0.19446 (4)	0.01684 (17)
S4	0.35920 (5)	0.87006 (9)	0.26546 (4)	0.01710 (17)
Na1	0.38885 (9)	0.35553 (15)	0.55924 (7)	0.0216 (3)
Na2	0.46690 (10)	0.73138 (16)	0.54410 (7)	0.0283 (4)
Na3	0.38987 (10)	0.20007 (16)	0.34308 (7)	0.0274 (3)
Na4	0.48859 (9)	0.56786 (15)	0.28553 (7)	0.0230 (3)
Na5	0.46642 (10)	0.86689 (15)	0.39298 (7)	0.0245 (3)
O1	0.36894 (19)	0.5796 (3)	0.58556 (14)	0.0283 (6)
H1	0.367 (3)	0.583 (5)	0.6209 (15)	0.037 (15)*
H2	0.322 (2)	0.604 (6)	0.574 (3)	0.054 (18)*
O2	0.5354 (2)	0.1883 (3)	0.35206 (15)	0.0329 (7)
H3	0.556 (3)	0.116 (4)	0.344 (2)	0.040 (15)*
H4	0.552 (4)	0.240 (5)	0.328 (2)	0.053 (18)*
O3	0.40321 (17)	0.1195 (3)	0.54127 (12)	0.0241 (6)
O4	0.40499 (17)	−0.0958 (3)	0.49020 (14)	0.0291 (6)
O5	0.40033 (19)	0.1094 (3)	0.43503 (13)	0.0334 (7)
O6	0.41514 (16)	0.4210 (3)	0.46581 (12)	0.0250 (6)
O7	0.43673 (17)	0.4534 (3)	0.36366 (12)	0.0248 (6)
O8	0.45103 (16)	0.6439 (3)	0.43105 (12)	0.0232 (6)
O9	0.3628 (2)	0.2671 (3)	0.25054 (13)	0.0351 (7)
O10	0.42717 (18)	0.4508 (3)	0.20055 (14)	0.0317 (7)
O11	0.41987 (17)	0.2306 (3)	0.15672 (12)	0.0268 (6)
O12	0.38437 (18)	0.7351 (3)	0.28429 (14)	0.0318 (7)
O13	0.37292 (17)	0.9671 (3)	0.31322 (12)	0.0282 (6)
O14	0.39915 (16)	0.9112 (3)	0.21230 (11)	0.0227 (6)
C1	0.2645 (2)	0.0366 (4)	0.48516 (18)	0.0263 (8)
H1A	0.247524	−0.006022	0.521426	0.032*
H1B	0.242490	0.129115	0.484160	0.032*
C2	0.2242 (3)	−0.0399 (5)	0.4324 (2)	0.0322 (9)
H2A	0.237766	0.005670	0.395932	0.039*
H2B	0.247891	−0.131170	0.431978	0.039*
C3	0.1293 (3)	−0.0491 (5)	0.4338 (2)	0.0397 (11)
H3A	0.115781	−0.088804	0.471540	0.048*
H3B	0.105327	0.042000	0.431444	0.048*
C4	0.0894 (4)	−0.1334 (8)	0.3836 (3)	0.0677 (19)
H4A	0.101675	−0.093553	0.346175	0.102*
H4B	0.028870	−0.136552	0.386313	0.102*
H4C	0.112114	−0.224331	0.386268	0.102*
C5	0.2997 (2)	0.5537 (4)	0.40159 (18)	0.0218 (8)
H5A	0.276788	0.588722	0.437482	0.026*
H5B	0.293682	0.624250	0.371248	0.026*
C6	0.2495 (2)	0.4298 (4)	0.3802 (2)	0.0280 (9)
H6A	0.272963	0.394351	0.344612	0.034*
H6B	0.255302	0.359666	0.410749	0.034*
C7	0.1563 (3)	0.4605 (5)	0.3663 (2)	0.0372 (10)
H7A	0.149960	0.526981	0.334304	0.045*
H7B	0.133087	0.499702	0.401316	0.045*
C8	0.1075 (3)	0.3334 (6)	0.3481 (3)	0.0614 (17)
H8A	0.048969	0.356374	0.337654	0.092*
H8B	0.110742	0.269793	0.380703	0.092*
H8C	0.131600	0.292931	0.314234	0.092*
C9	0.2808 (2)	0.3675 (4)	0.15778 (17)	0.0248 (8)
H9A	0.290621	0.413088	0.120555	0.030*
H9B	0.250007	0.283805	0.147917	0.030*
C10	0.2260 (3)	0.4574 (5)	0.1931 (2)	0.0374 (11)
H10A	0.210258	0.408265	0.228162	0.045*
H10B	0.258374	0.537204	0.206608	0.045*
C11	0.1472 (3)	0.5017 (6)	0.1572 (3)	0.0472 (13)
H11A	0.119599	0.421943	0.138975	0.057*
H11B	0.163221	0.560869	0.125302	0.057*
C12	0.0847 (3)	0.5754 (6)	0.1927 (4)	0.070 (2)
H12A	0.040022	0.612826	0.166142	0.105*
H12B	0.113199	0.647803	0.215028	0.105*
H12C	0.060712	0.512844	0.219803	0.105*
C13	0.2498 (2)	0.8633 (4)	0.2452 (2)	0.0265 (8)
H13A	0.239772	0.797174	0.213276	0.032*
H13B	0.220841	0.831048	0.279147	0.032*
C14	0.2112 (2)	0.9972 (4)	0.2249 (2)	0.0315 (9)
H14A	0.242041	1.032898	0.192421	0.038*
H14B	0.217053	1.062014	0.257575	0.038*
C15	0.1180 (3)	0.9829 (5)	0.2040 (2)	0.0379 (10)
H15A	0.112726	0.920407	0.170397	0.045*
H15B	0.087968	0.943249	0.235982	0.045*
C16	0.0765 (3)	1.1155 (5)	0.1856 (2)	0.0432 (12)
H16A	0.106069	1.155756	0.154136	0.065*
H16B	0.078677	1.176286	0.219272	0.065*
H16C	0.018177	1.099456	0.171769	0.065*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pd1	0.01842 (13)	0.02374 (15)	0.03245 (17)	0.00385 (12)	0.00072 (11)	0.00322 (13)
Cl1	0.0311 (5)	0.0272 (5)	0.0747 (9)	0.0030 (4)	−0.0117 (5)	−0.0018 (6)
Cl2	0.0231 (5)	0.0286 (5)	0.0551 (7)	0.0068 (4)	−0.0055 (5)	0.0019 (5)
Cl3	0.0225 (5)	0.0257 (5)	0.0895 (10)	0.0045 (4)	−0.0078 (6)	0.0017 (6)
S1	0.0189 (4)	0.0142 (4)	0.0150 (4)	−0.0004 (3)	0.0011 (3)	−0.0014 (3)
S2	0.0176 (4)	0.0146 (4)	0.0147 (4)	0.0009 (3)	0.0008 (3)	0.0012 (3)
S3	0.0225 (4)	0.0154 (4)	0.0123 (4)	−0.0003 (3)	−0.0002 (3)	0.0009 (3)
S4	0.0165 (4)	0.0174 (4)	0.0174 (4)	0.0015 (3)	0.0016 (3)	0.0020 (3)
Na1	0.0265 (8)	0.0197 (7)	0.0185 (7)	0.0001 (6)	0.0012 (6)	0.0020 (6)
Na2	0.0318 (8)	0.0238 (8)	0.0295 (9)	0.0042 (7)	0.0027 (7)	0.0019 (7)
Na3	0.0344 (9)	0.0290 (8)	0.0187 (8)	0.0055 (7)	0.0024 (6)	0.0036 (7)
Na4	0.0250 (7)	0.0195 (7)	0.0245 (8)	0.0035 (6)	0.0015 (6)	−0.0007 (6)
Na5	0.0280 (8)	0.0232 (7)	0.0219 (8)	0.0031 (6)	−0.0008 (6)	0.0017 (6)
O1	0.0271 (15)	0.0317 (16)	0.0252 (16)	0.0021 (13)	−0.0040 (13)	−0.0052 (13)
O2	0.0381 (17)	0.0225 (15)	0.0397 (19)	−0.0021 (13)	0.0135 (14)	−0.0004 (14)
O3	0.0264 (14)	0.0263 (14)	0.0193 (13)	0.0004 (11)	−0.0005 (11)	−0.0071 (11)
O4	0.0261 (14)	0.0174 (13)	0.0431 (18)	0.0043 (11)	−0.0029 (13)	−0.0030 (12)
O5	0.0380 (16)	0.0452 (18)	0.0170 (14)	−0.0123 (14)	0.0007 (12)	0.0077 (13)
O6	0.0236 (13)	0.0268 (14)	0.0242 (15)	0.0010 (11)	−0.0007 (11)	0.0086 (12)
O7	0.0265 (14)	0.0274 (14)	0.0209 (14)	0.0038 (11)	0.0048 (11)	−0.0024 (11)
O8	0.0241 (13)	0.0175 (12)	0.0273 (15)	−0.0027 (10)	−0.0028 (11)	0.0005 (11)
O9	0.0493 (19)	0.0403 (17)	0.0161 (14)	−0.0015 (15)	0.0045 (13)	0.0069 (13)
O10	0.0278 (15)	0.0198 (13)	0.0465 (19)	−0.0052 (12)	−0.0046 (13)	0.0022 (13)
O11	0.0306 (15)	0.0288 (14)	0.0205 (14)	0.0124 (12)	−0.0017 (11)	−0.0062 (12)
O12	0.0288 (15)	0.0237 (14)	0.0432 (19)	0.0058 (12)	0.0055 (13)	0.0122 (13)
O13	0.0287 (14)	0.0345 (16)	0.0207 (14)	0.0046 (12)	−0.0021 (11)	−0.0062 (12)
O14	0.0222 (13)	0.0282 (14)	0.0177 (13)	−0.0032 (11)	0.0024 (10)	0.0017 (11)
C1	0.0175 (17)	0.031 (2)	0.030 (2)	0.0028 (15)	0.0008 (15)	−0.0085 (17)
C2	0.030 (2)	0.035 (2)	0.032 (2)	−0.0031 (18)	−0.0025 (17)	−0.0074 (19)
C3	0.023 (2)	0.044 (3)	0.050 (3)	−0.0036 (19)	−0.0059 (19)	0.005 (2)
C4	0.040 (3)	0.091 (5)	0.069 (4)	−0.017 (3)	−0.016 (3)	−0.008 (4)
C5	0.0198 (17)	0.0196 (17)	0.026 (2)	0.0039 (14)	0.0010 (15)	0.0023 (15)
C6	0.025 (2)	0.0258 (19)	0.032 (2)	−0.0028 (16)	−0.0032 (16)	−0.0009 (17)
C7	0.0211 (19)	0.044 (3)	0.046 (3)	−0.0001 (19)	−0.0029 (18)	−0.004 (2)
C8	0.031 (3)	0.065 (4)	0.086 (5)	−0.014 (3)	−0.012 (3)	−0.004 (3)
C9	0.0201 (18)	0.034 (2)	0.0195 (19)	0.0016 (16)	−0.0022 (14)	−0.0025 (17)
C10	0.027 (2)	0.036 (2)	0.050 (3)	0.0024 (18)	0.0039 (19)	−0.010 (2)
C11	0.033 (2)	0.046 (3)	0.062 (3)	0.013 (2)	0.007 (2)	0.010 (3)
C12	0.032 (3)	0.058 (4)	0.120 (6)	0.013 (3)	0.005 (3)	−0.020 (4)
C13	0.0148 (17)	0.029 (2)	0.036 (2)	−0.0021 (15)	0.0011 (15)	0.0046 (18)
C14	0.0227 (19)	0.028 (2)	0.043 (3)	0.0036 (16)	−0.0029 (17)	0.0034 (19)
C15	0.023 (2)	0.045 (3)	0.045 (3)	0.0004 (19)	−0.0025 (18)	0.007 (2)
C16	0.027 (2)	0.051 (3)	0.051 (3)	0.010 (2)	−0.003 (2)	0.009 (2)

Geometric parameters (Å, º) top

Pd1—Cl1	2.2776 (12)	O1—H2	0.82 (3)
Pd1—Cl2	2.2800 (10)	O2—H3	0.81 (3)
Pd1—Cl3ⁱ	2.3159 (11)	O2—H4	0.80 (3)
Pd1—Cl3	2.3212 (12)	C1—C2	1.517 (6)
Cl2—Na1	2.8560 (18)	C1—H1A	0.9800
S1—O5	1.453 (3)	C1—H1B	0.9800
S1—O4	1.453 (3)	C2—C3	1.514 (6)
S1—O3	1.458 (3)	C2—H2A	0.9800
S1—C1	1.767 (4)	C2—H2B	0.9800
S2—O6	1.454 (3)	C3—C4	1.512 (8)
S2—O7	1.460 (3)	C3—H3A	0.9800
S2—O8	1.462 (3)	C3—H3B	0.9800
S2—C5	1.771 (4)	C4—H4A	0.9700
S3—O9	1.440 (3)	C4—H4B	0.9700
S3—O10	1.455 (3)	C4—H4C	0.9700
S3—O11	1.463 (3)	C5—C6	1.524 (5)
S3—C9	1.759 (4)	C5—H5A	0.9800
S4—O12	1.451 (3)	C5—H5B	0.9800
S4—O13	1.452 (3)	C6—C7	1.522 (6)
S4—O14	1.462 (3)	C6—H6A	0.9800
S4—C13	1.767 (4)	C6—H6B	0.9800
Na1—O6	2.284 (3)	C7—C8	1.520 (7)
Na1—O1	2.326 (3)	C7—H7A	0.9800
Na1—O11ⁱⁱ	2.386 (3)	C7—H7B	0.9800
Na1—O3	2.387 (3)	C8—H8A	0.9700
Na1—O8ⁱⁱⁱ	2.540 (3)	C8—H8B	0.9700
Na2—O4^iv	2.283 (3)	C8—H8C	0.9700
Na2—O1	2.407 (4)	C9—C10	1.516 (6)
Na2—O6ⁱⁱⁱ	2.431 (3)	C9—H9A	0.9800
Na2—O2ⁱⁱⁱ	2.488 (4)	C9—H9B	0.9800
Na2—O5ⁱⁱⁱ	2.649 (3)	C10—C11	1.507 (7)
Na2—O8	2.700 (3)	C10—H10A	0.9800
Na3—O9	2.212 (3)	C10—H10B	0.9800
Na3—O5	2.264 (3)	C11—C12	1.514 (7)
Na3—O2	2.311 (4)	C11—H11A	0.9800
Na3—O13^v	2.414 (3)	C11—H11B	0.9800
Na3—O7	2.649 (3)	C12—H12A	0.9700
Na4—O7	2.308 (3)	C12—H12B	0.9700
Na4—O12	2.342 (3)	C12—H12C	0.9700
Na4—O14^vi	2.363 (3)	C13—C14	1.519 (6)
Na4—O10	2.393 (3)	C13—H13A	0.9800
Na4—O11^vii	2.479 (3)	C13—H13B	0.9800
Na5—O8	2.391 (3)	C14—C15	1.529 (6)
Na5—O13	2.462 (3)	C14—H14A	0.9800
Na5—O3ⁱⁱⁱ	2.465 (3)	C14—H14B	0.9800
Na5—O4^iv	2.505 (3)	C15—C16	1.515 (6)
Na5—O11^vii	2.582 (3)	C15—H15A	0.9800
Na5—O5^iv	2.817 (4)	C15—H15B	0.9800
Na5—O10^vii	2.931 (4)	C16—H16A	0.9700
Na5—O12	3.000 (4)	C16—H16B	0.9700
O1—H1	0.80 (3)	C16—H16C	0.9700

Cl1—Pd1—Cl2	92.45 (4)	O5^iv—Na5—O12	119.93 (10)
Cl1—Pd1—Cl3ⁱ	90.99 (4)	O10^vii—Na5—O12	76.60 (9)
Cl2—Pd1—Cl3ⁱ	176.53 (4)	Na1—O1—H1	108 (4)
Cl1—Pd1—Cl3	177.19 (4)	Na2—O1—H1	116 (4)
Cl2—Pd1—Cl3	90.36 (4)	Na1—O1—H2	109 (4)
Cl3ⁱ—Pd1—Cl3	86.20 (4)	Na2—O1—H2	107 (4)
Pd1—Cl2—Na1	139.61 (5)	H1—O1—H2	102 (5)
Pd1ⁱ—Cl3—Pd1	93.80 (4)	Na3—O2—Na2ⁱⁱⁱ	88.93 (12)
O5—S1—O4	110.28 (19)	Na3—O2—H3	116 (4)
O5—S1—O3	111.62 (17)	Na2ⁱⁱⁱ—O2—H3	122 (4)
O4—S1—O3	112.98 (17)	Na3—O2—H4	107 (4)
O5—S1—C1	108.38 (19)	Na2ⁱⁱⁱ—O2—H4	117 (4)
O4—S1—C1	106.46 (18)	H3—O2—H4	104 (5)
O3—S1—C1	106.83 (17)	C2—C1—S1	114.3 (3)
O5—S1—Na5^v	61.48 (14)	C2—C1—H1A	108.7
O6—S2—O7	110.06 (17)	S1—C1—H1A	108.7
O6—S2—O8	112.61 (17)	C2—C1—H1B	108.7
O7—S2—O8	112.35 (16)	S1—C1—H1B	108.7
O6—S2—C5	107.70 (17)	H1A—C1—H1B	107.6
O7—S2—C5	106.74 (17)	C3—C2—C1	112.1 (4)
O8—S2—C5	107.05 (17)	C3—C2—H2A	109.2
O9—S3—O10	112.86 (19)	C1—C2—H2A	109.2
O9—S3—O11	111.67 (18)	C3—C2—H2B	109.2
O10—S3—O11	110.37 (18)	C1—C2—H2B	109.2
O9—S3—C9	107.65 (19)	H2A—C2—H2B	107.9
O10—S3—C9	106.94 (19)	C4—C3—C2	112.3 (4)
O11—S3—C9	107.02 (18)	C4—C3—H3A	109.1
O12—S4—O13	111.59 (18)	C2—C3—H3A	109.1
O12—S4—O14	111.84 (17)	C4—C3—H3B	109.1
O13—S4—O14	112.33 (17)	C2—C3—H3B	109.1
O12—S4—C13	106.62 (18)	H3A—C3—H3B	107.9
O13—S4—C13	107.99 (19)	C3—C4—H4A	109.5
O14—S4—C13	106.06 (18)	C3—C4—H4B	109.5
O6—Na1—O1	90.30 (12)	H4A—C4—H4B	109.5
O6—Na1—O11ⁱⁱ	157.10 (12)	C3—C4—H4C	109.5
O1—Na1—O11ⁱⁱ	97.25 (12)	H4A—C4—H4C	109.5
O6—Na1—O3	95.34 (11)	H4B—C4—H4C	109.5
O1—Na1—O3	174.22 (12)	C6—C5—S2	111.9 (3)
O11ⁱⁱ—Na1—O3	78.00 (10)	C6—C5—H5A	109.2
O6—Na1—O8ⁱⁱⁱ	80.06 (10)	S2—C5—H5A	109.2
O1—Na1—O8ⁱⁱⁱ	97.50 (11)	C6—C5—H5B	109.2
O11ⁱⁱ—Na1—O8ⁱⁱⁱ	77.54 (10)	S2—C5—H5B	109.2
O3—Na1—O8ⁱⁱⁱ	84.77 (10)	H5A—C5—H5B	107.9
O6—Na1—Cl2	97.08 (9)	C7—C6—C5	112.6 (3)
O1—Na1—Cl2	81.71 (9)	C7—C6—H6A	109.1
O11ⁱⁱ—Na1—Cl2	105.37 (9)	C5—C6—H6A	109.1
O3—Na1—Cl2	96.29 (8)	C7—C6—H6B	109.1
O8ⁱⁱⁱ—Na1—Cl2	177.04 (9)	C5—C6—H6B	109.1
O4^iv—Na2—O1	114.31 (12)	H6A—C6—H6B	107.8
O4^iv—Na2—O6ⁱⁱⁱ	136.11 (12)	C6—C7—C8	111.1 (4)
O1—Na2—O6ⁱⁱⁱ	100.08 (11)	C6—C7—H7A	109.4
O4^iv—Na2—O2ⁱⁱⁱ	103.31 (12)	C8—C7—H7A	109.4
O1—Na2—O2ⁱⁱⁱ	76.94 (11)	C6—C7—H7B	109.4
O6ⁱⁱⁱ—Na2—O2ⁱⁱⁱ	110.63 (12)	C8—C7—H7B	109.4
O4^iv—Na2—O5ⁱⁱⁱ	87.44 (11)	H7A—C7—H7B	108.0
O1—Na2—O5ⁱⁱⁱ	146.38 (12)	C7—C8—H8A	109.5
O6ⁱⁱⁱ—Na2—O5ⁱⁱⁱ	77.03 (11)	C7—C8—H8B	109.5
O2ⁱⁱⁱ—Na2—O5ⁱⁱⁱ	73.07 (11)	H8A—C8—H8B	109.5
O4^iv—Na2—O8	74.15 (10)	C7—C8—H8C	109.5
O1—Na2—O8	98.82 (11)	H8A—C8—H8C	109.5
O6ⁱⁱⁱ—Na2—O8	74.38 (10)	H8B—C8—H8C	109.5
O2ⁱⁱⁱ—Na2—O8	173.81 (12)	C10—C9—S3	114.2 (3)
O5ⁱⁱⁱ—Na2—O8	112.15 (10)	C10—C9—H9A	108.7
O9—Na3—O5	171.09 (14)	S3—C9—H9A	108.7
O9—Na3—O2	102.75 (13)	C10—C9—H9B	108.7
O5—Na3—O2	83.98 (13)	S3—C9—H9B	108.7
O9—Na3—O13^v	90.64 (12)	H9A—C9—H9B	107.6
O5—Na3—O13^v	83.01 (12)	C11—C10—C9	111.9 (4)
O2—Na3—O13^v	93.81 (12)	C11—C10—H10A	109.2
O9—Na3—O7	85.12 (11)	C9—C10—H10A	109.2
O5—Na3—O7	102.30 (12)	C11—C10—H10B	109.2
O2—Na3—O7	76.45 (11)	C9—C10—H10B	109.2
O13^v—Na3—O7	168.18 (11)	H10A—C10—H10B	107.9
O7—Na4—O12	93.62 (11)	C10—C11—C12	114.0 (5)
O7—Na4—O14^vi	88.54 (10)	C10—C11—H11A	108.8
O12—Na4—O14^vi	176.01 (12)	C12—C11—H11A	108.8
O7—Na4—O10	103.43 (11)	C10—C11—H11B	108.8
O12—Na4—O10	95.00 (12)	C12—C11—H11B	108.8
O14^vi—Na4—O10	87.75 (11)	H11A—C11—H11B	107.7
O7—Na4—O11^vii	98.26 (11)	C11—C12—H12A	109.5
O12—Na4—O11^vii	86.19 (12)	C11—C12—H12B	109.5
O14^vi—Na4—O11^vii	90.18 (11)	H12A—C12—H12B	109.5
O10—Na4—O11^vii	158.15 (12)	C11—C12—H12C	109.5
O8—Na5—O13	124.40 (12)	H12A—C12—H12C	109.5
O8—Na5—O3ⁱⁱⁱ	86.35 (10)	H12B—C12—H12C	109.5
O13—Na5—O3ⁱⁱⁱ	148.92 (12)	C14—C13—S4	114.4 (3)
O8—Na5—O4^iv	76.20 (10)	C14—C13—H13A	108.7
O13—Na5—O4^iv	109.44 (11)	S4—C13—H13A	108.7
O3ⁱⁱⁱ—Na5—O4^iv	79.97 (10)	C14—C13—H13B	108.7
O8—Na5—O11^vii	76.62 (10)	S4—C13—H13B	108.7
O13—Na5—O11^vii	107.11 (10)	H13A—C13—H13B	107.6
O3ⁱⁱⁱ—Na5—O11^vii	72.99 (9)	C13—C14—C15	111.9 (4)
O4^iv—Na5—O11^vii	142.52 (11)	C13—C14—H14A	109.2
O8—Na5—O5^iv	127.94 (10)	C15—C14—H14A	109.2
O13—Na5—O5^iv	71.62 (10)	C13—C14—H14B	109.2
O3ⁱⁱⁱ—Na5—O5^iv	93.85 (10)	C15—C14—H14B	109.2
O4^iv—Na5—O5^iv	52.85 (9)	H14A—C14—H14B	107.9
O11^vii—Na5—O5^iv	152.22 (10)	C16—C15—C14	113.4 (4)
O8—Na5—O10^vii	127.13 (10)	C16—C15—H15A	108.9
O13—Na5—O10^vii	72.78 (9)	C14—C15—H15A	108.9
O3ⁱⁱⁱ—Na5—O10^vii	85.23 (10)	C16—C15—H15B	108.9
O4^iv—Na5—O10^vii	151.57 (11)	C14—C15—H15B	108.9
O11^vii—Na5—O10^vii	51.04 (8)	H15A—C15—H15B	107.7
O5^iv—Na5—O10^vii	104.68 (9)	C15—C16—H16A	109.5
O8—Na5—O12	81.05 (10)	C15—C16—H16B	109.5
O13—Na5—O12	51.00 (9)	H16A—C16—H16B	109.5
O3ⁱⁱⁱ—Na5—O12	144.57 (10)	C15—C16—H16C	109.5
O4^iv—Na5—O12	127.80 (10)	H16A—C16—H16C	109.5
O11^vii—Na5—O12	71.92 (9)	H16B—C16—H16C	109.5

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O14^viii	0.80 (3)	2.10 (4)	2.879 (4)	164 (5)
O1—H2···Cl1	0.82 (3)	2.32 (4)	3.127 (3)	172 (6)
O2—H3···O10^vi	0.81 (3)	1.95 (4)	2.723 (4)	159 (5)
O2—H4···O14^vi	0.80 (3)	2.10 (4)	2.884 (4)	164 (6)

Symmetry codes: (vi) −x+1, y−1/2, −z+1/2; (viii) x, −y+3/2, z+1/2.

Acknowledgements

We thank E. Hammes and P. Roloff for technical support and Dr G. Reiss for discussions.

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