Synthesis and crystal structure of sodium (ethane-1,2-di­yl)bis­[(3-meth­oxy­prop­yl)phosphinodi­thiol­ate] octa­hydrate

Nell, B.P.; Tyler, D.R.; Zakharov, L.N.; Johnston, D.H.

doi:10.1107/S2056989024009642

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ISSN: 2056-9890

Volume 80| Part 11| November 2024| Pages 1138-1141

https://doi.org/10.1107/S2056989024009642

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Synthesis and crystal structure of sodium (ethane-1,2-diyl)bis[(3-methoxypropyl)phosphinodithiolate] octahydrate

Bryan P. Nell,^a ^* David R. Tyler,^b Lev N. Zakharov ^b and Dean H. Johnston ^c ^*

^aDepartment of Chemistry, Ripon College, Ripon, WI 54971, USA, ^bDepartment of Chemistry and Biochemistry, University of Oregon, Eugene, OR 97403, USA, and ^cDepartment of Chemistry, Otterbein University, Westerville, OH 43081, USA
^*Correspondence e-mail: nellb@ripon.edu, djohnston@otterbein.edu

Edited by S. P. Kelley, University of Missouri-Columbia, USA (Received 5 August 2024; accepted 30 September 2024; online 8 October 2024)

The title compound, catena-poly[[triaquasodium]-di-μ-aqua-[triaquasodium]-μ-(ethane-1,2-diyl)bis[(3-methoxypropyl)phosphinodithiolato]], [Na₂(C₁₀H₂₂O₂P₂S₄)(H₂O)₈]_n, crystallizes in the triclinic space group P1. The dianionic [CH₃O(CH₂)₃P(=S)(S—)CH₂CH₂P(=S)(S—)(CH₂)₃OCH₃]²⁻ ligand fragments are joined by a dicationic [Na₂(H₂O)₈]²⁺ cluster that includes the oxygen of the methoxypropyl unit of the ligand to form infinite chains.

Keywords: dithiophosphinate; phosphinodithiolate; crystal structure.

CCDC reference: 2388007

1. Chemical context

Complexes of the type Fe(P₂)₂X₂ have been shown to react with dinitrogen at high pressure to form [Fe(P₂)₂(N₂)X]⁺ (Miller et al., 2002 ). This reaction can potentially be used to scrub dinitrogen-contaminated natural gas. Unfortunately, the phosphine ligands in these dinitrogen-scrubbing complexes slowly dissociate in aqueous solution leading to degradation of the complexes, preventing a practical pressure-swing process from being developed. One potential method to develop complexes that are more robust is to use a phosphine macrocycle in place of the two bidentate ligands. For background on phosphine macrocycles, see: Caminade & Majoral (1994 ); Swor & Tyler (2011 ). The ‘macrocycle effect’ predicts that the binding constant for a macrocyclic ligand is orders of magnitude higher than the binding constant for two bidentate ligands (Melson, 1979 ).

In addition to their usefulness in the N₂-scrubbing scheme described above, macrocyclic phosphine compounds are sought after in general as ligands for transition-metal complexes because of their strong binding properties. However, the synthesis of phosphine macrocycles is a relatively underdeveloped area. One approach to macrocyclic phosphines is a template synthesis in which two secondary bidentate phosphines are coordinated to a common metal center and then covalently linked (Lambert & Desreux, 2000 ; Nell & Tyler, 2014 ). Previously, we showed that complexes of the [Cu(P₂)₂]⁺ type (where P₂ is a bidentate secondary phosphine) can react under basic conditions with various dihalides to form macrocyclic tetraphosphine Cu complexes (Nell et al., 2016 ). The title molecule is an unexpected side-product of the process of removing the Cu metal center using aqueous NaSH to react with the Cu metal (Costantino et al., 2008 ). Interestingly in this case, the P₂ ligand was 1,2-bis(methoxypropyl)phosphinoethane (MeOPrPE), which has been oxidized to the dithiophosphinate species, a reaction commonly encountered between secondary phosphines and elemental sulfur.

2. Structural commentary

The title compound is a P,S,Na-complex in which there are two P(=S)(—S) groups consisting of two terminal sulfur atoms bonded to each phosphorus atom, providing a −2 charge. Two sodium cations and eight water molecules form [Na₂(H₂O)₈]²⁺ bridges between the anions. The oxygen of the methoxypropyl unit of the ligand is also bonded to the [Na₂(H₂O)₈]²⁺ cluster, completing a pseudo-octahedral coordination environment around each sodium cation and linking the cations and anions to form an infinite chain. The asymmetric unit (see Fig. 1) contains half of one dianionic bis(phosphinodithiolate) chain, one sodium cation, and four water molecules, one of which is disordered over two positions with 50:50 occupancy.

Figure 1
Displacement ellipsoid (50%) diagram and atom-numbering scheme for the asymmetric unit of the title compound.

Interestingly the lengths of the two P—S bonds for the phosphorus atom P1 differ by 0.0206 (6) Å. While the structure can formally be described as having one phosphorus–sulfur single bond and one double bond, clearly these should be equivalent by resonance. Indeed, comparison to seven similar dialkylphosphinodithiolate structures (Pinkerton, 1990 ; Ebels et al., 1997 ; Klevtsova et al., 2003 ; Kokina et al., 2008 , 2010 ; Marc et al., 2012 ; Guo et al., 2022 ) shows that the average difference in phosphorus–sulfur bonds in these compounds is only 0.006 Å. A closer look at the hydrogen bonding in the structure shows that the asymmetry is likely due to the fact that sulfur S1 has two hydrogen-bonding contacts (see Fig. 2, Table 1) compared to the three contacts for S2. A similar asymmetry in phosphorus–sulfur bond lengths is observed in the structure of sodium diethyldithiophosphinate dihydrate (Svensson & Albertsson, 1989 ), though the hydrogen-bonding network is quite symmetrical in that structure.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2C⋯S1ⁱ	0.78 (1)	2.52 (1)	3.2920 (13)	167 (2)
O52—H52⋯S1ⁱ	0.79 (2)	2.42 (2)	3.193 (3)	167 (4)
O3—H3AA⋯S2ⁱⁱ	0.79 (1)	2.50 (1)	3.2840 (13)	177 (2)
O4—H4C⋯S2ⁱⁱⁱ	0.78 (1)	2.49 (2)	3.2535 (14)	169 (2)
O51—H51⋯S2^iv	0.78 (1)	2.52 (1)	3.117 (2)	134 (2)
O52—H51⋯S2^iv	0.83 (1)	2.52 (1)	3.314 (2)	162 (2)
O2—H2D⋯O4^v	0.77 (1)	2.05 (1)	2.8069 (19)	170 (2)
O3—H3BB⋯O3ⁱⁱ	0.79 (2)	2.02 (2)	2.801 (2)	171 (4)
O3—H3C⋯O52^vi	0.71 (4)	2.04 (4)	2.748 (3)	174 (5)
O4—H4D⋯O51^vii	0.75 (1)	2.07 (2)	2.731 (3)	147 (3)
O51—H51A⋯O3^vi	0.79 (2)	2.05 (2)	2.825 (3)	173 (5)
Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .

Figure 2
Displacement ellipsoid (50%) diagram showing O—H⋯S contacts in orange with selected atom labels. Only one position of the disordered water molecule is shown for clarity. See Table 1

for donor–acceptor distances and angles.

The sodium ion and water molecules form [Na₂(H₂O)₈]²⁺ dimers around an inversion center. The coordination sphere of the sodium ion is filled by two bridging water molecules (O2), three terminal water molecules (O3, O4, and O51/O52), and one ether oxygen of the ligand molecule (O1). As shown in Fig. 3, there is one intra-dimer hydrogen bond (O3—H3C⋯O52). A similar contact, O51—H51A⋯O3, is present in the second component of the disorder but is not shown in Fig. 3. The dimers are linked by additional hydrogen-bond contacts between atoms O2 and O4 of neighboring dimers (O2—H2D⋯O4). An additional intradimer contact, O4—H4D⋯O51, is present but not shown in Fig. 3.

Figure 3
Displacement ellipsoid (50%) diagram showing O—H⋯O contacts in orange with selected atom labels. Only one position of the disordered water molecule is shown for clarity. See Table 1

for donor–acceptor distances and angles.

3. Supramolecular features

The sodium ion–water dimers can be visualized as edge-sharing octahedra (see Fig. 4) with two of the outer oxygen positions occupied by equivalent ether oxygen atoms from one end of the bis(phosphinodithiolate) ligand. The ligands then link successive sodium ion dimers, forming infinite zigzag chains running parallel to the (0 $[\overline{1}]$ 1) plane. The hydrogen-bonding interactions between the water molecules and the sulfur atoms (Table 1) create additional interactions linking the chains in all directions.

Figure 4
Polyhedral representation showing [Na₂(H₂O)₈]²⁺ dimers (purple) linked by bis(phosphinodithiolate) chains. The O—H⋯S contacts are shown in orange. Only one position of the disordered water molecule is shown and hydrogen atoms omitted for clarity.

4. Database survey

A search of the CSD (version 2024.2.0; Groom et al., 2016 ) demonstrates that there are relatively few structurally characterized dialkyldithiophosphinates and no existing examples of structures with dithiophosphinate groups linked by an alkyl chain.

A number of structures contain diphenyldithiophosphinates as bidentate ligands coordinated to late transition metals such as platinum and palladium (Alison & Stephenson, 1971 ; Fackler et al., 1982 ; Landtiser et al., 1995 ). In some cases, the dialkyldithiophosphinate ends up serving as a counter-ion instead of coordinating to the metal center (Kokina et al., 2008). Diethyldithiophosphinates have also been used to form molybdenum(IV)sulfur clusters, Mo₃S₄(Et₂PS₂)₄ (Keck et al., 1981 ).

The structure most closely related to the title compound is that of sodium diethyldithiophosphinate dihydrate (CSD refcode SAGWUS; Svensson & Albertsson, 1989). Each sulfur atom is hydrogen bonded to two water molecules, forming an extended network in the ab plane, with successive layers separated by sodium cations. The sodium ions are found in a similar distorted octahedral environment, but with two of the six coordination sites occupied by sulfur instead of water. The octahedra are linked by edge sharing within the layer with every third octahedron missing.

5. Synthesis and crystallization

The title molecule was prepared serendipitously while attempting to remove the Cu^I template of a [Cu(P₂)₂]⁺ complex. 1,2-Bis(methoxypropyl)phosphinoethane (MeOPrPE) (2 eq.) was reacted with Cu(MeCN)₄PF₆ (1 eq.) in acetonitrile to yield the corresponding Cu(MeOPrPE)₂PF₆ complex. As a proof-of-concept, an attempt to remove the copper and yield the free phosphine back was performed. The copper complex was dissolved in 10 mL of THF and added to a solution of 10 eq. NaSH-hydrate in 30 mL of absolute EtOH. The mixture was refluxed for 24 h, forming Cu₂S as a black precipitate. The reaction mixture was cooled to RT, filtered through a celite plug, then the solvent was allowed to slowly evaporate at RT in air, yielding crystals of the title molecule.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All hydrogen atoms were located in the difference maps. Carbon-bonded hydrogen atoms were freely refined. For the water molecules the O—H distances were restrained (SADI) to have similar distances. The displacement parameters for the water hydrogen atoms were constrained to be U_iso(H) = 1.5U_eq(O). The occupancy of the disordered water molecule (O51/O52) was fixed at 0.50 since free refinement gave an occupancy of 0.486 (8).

Table 2
Experimental details

Crystal data
Chemical formula	[Na₂(C₁₀H₂₂O₂P₂S₄)(H₂O)₈]
M_r	277.28
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	173
a, b, c (Å)	6.7412 (8), 8.2961 (8), 11.8621 (17)
α, β, γ (°)	79.608 (2), 89.207 (2), 87.030 (1)
V (Å³)	651.63 (14)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.56
Crystal size (mm)	0.19 × 0.12 × 0.06

Data collection
Diffractometer	Bruker SMART APEX CCD area detector
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.838, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	7596, 3007, 2736
R_int	0.014
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.068, 1.02
No. of reflections	3007
No. of parameters	210
No. of restraints	45
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.20
Computer programs: SMART and SAINT (Bruker, 2003 ), SHELXTL (Sheldrick, 2008 ), SHELXL2018/3 (Sheldrick, 2015 ), Mercury (Macrae et al., 2020 ), OLEX2 (Dolomanov et al., 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 2388007

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2056989024009642/ev2010sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989024009642/ev2010Isup2.hkl

checkCIF report

Computing details top

catena-Poly[[triaquasodium]-di-µ-aqua-[triaquasodium]-µ-(ethane-1,2-diyl)bis[(3-methoxypropyl)phosphinodithiolato]] top

Crystal data top

[Na₂(C₁₀H₂₂O₂P₂S₄)(H₂O)₈]	Z = 2
M_r = 277.28	F(000) = 294
Triclinic, P1	D_x = 1.413 Mg m⁻³
a = 6.7412 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.2961 (8) Å	Cell parameters from 4713 reflections
c = 11.8621 (17) Å	θ = 2.5–28.3°
α = 79.608 (2)°	µ = 0.56 mm⁻¹
β = 89.207 (2)°	T = 173 K
γ = 87.030 (1)°	Block, colorless
V = 651.63 (14) Å³	0.19 × 0.12 × 0.06 mm

Data collection top

Bruker SMART APEX CCD area detector diffractometer	3007 independent reflections
Radiation source: sealed tube	2736 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.014
phi and ω scans	θ_max = 28.3°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −8→8
T_min = 0.838, T_max = 1.000	k = −10→10
7596 measured reflections	l = −15→15

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.026	Hydrogen site location: difference Fourier map
wR(F²) = 0.068	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0357P)² + 0.2159P] where P = (F_o² + 2F_c²)/3
3007 reflections	(Δ/σ)_max = 0.001
210 parameters	Δρ_max = 0.43 e Å⁻³
45 restraints	Δρ_min = −0.20 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	Occ. (<1)
S1	0.65743 (5)	0.71747 (4)	0.84910 (3)	0.02676 (10)
S2	0.95943 (5)	0.52147 (4)	0.67995 (3)	0.02722 (10)
P1	0.83354 (5)	0.52284 (4)	0.83414 (3)	0.01867 (9)
C1	0.1587 (3)	−0.0034 (2)	0.84426 (17)	0.0374 (4)
H1A	0.050 (3)	−0.019 (2)	0.7965 (17)	0.045 (5)*
H1B	0.234 (3)	−0.108 (3)	0.8699 (17)	0.050 (6)*
H1C	0.101 (3)	0.035 (3)	0.906 (2)	0.060 (7)*
C2	0.4380 (2)	0.15096 (17)	0.85447 (12)	0.0257 (3)
H2A	0.529 (3)	0.058 (2)	0.8688 (15)	0.032 (4)*
H2B	0.381 (3)	0.164 (2)	0.9249 (16)	0.032 (4)*
C3	0.5383 (2)	0.30505 (17)	0.79961 (12)	0.0254 (3)
H3A	0.589 (3)	0.293 (2)	0.7283 (16)	0.034 (5)*
H3B	0.443 (3)	0.396 (2)	0.7870 (15)	0.032 (4)*
C4	0.7036 (2)	0.33531 (17)	0.87807 (12)	0.0258 (3)
H4A	0.650 (3)	0.341 (2)	0.9483 (16)	0.035 (5)*
H4B	0.801 (3)	0.250 (2)	0.8855 (16)	0.041 (5)*
C5	1.0347 (2)	0.50194 (19)	0.93811 (11)	0.0243 (3)
H5A	1.110 (3)	0.409 (2)	0.9306 (15)	0.035 (5)*
H5B	1.112 (3)	0.591 (2)	0.9135 (15)	0.033 (5)*
Na1	0.33236 (8)	0.08688 (6)	0.58806 (5)	0.02448 (13)
O1	0.28216 (15)	0.11749 (12)	0.78382 (8)	0.0281 (2)
O2	0.66857 (17)	−0.02101 (15)	0.60507 (10)	0.0331 (3)
H2C	0.683 (3)	−0.089 (2)	0.6599 (14)	0.050*
H2D	0.754 (3)	0.037 (2)	0.6050 (18)	0.050*
O3	0.42969 (18)	0.35106 (14)	0.48142 (10)	0.0309 (2)
H3AA	0.339 (3)	0.382 (2)	0.4406 (16)	0.046*
H3BB	0.480 (6)	0.432 (3)	0.488 (4)	0.046*	0.5
H3C	0.501 (7)	0.313 (5)	0.448 (4)	0.046*	0.5
O4	−0.00709 (18)	0.18169 (19)	0.57874 (12)	0.0445 (3)
H4C	−0.020 (4)	0.255 (2)	0.6113 (19)	0.067*
H4D	−0.047 (4)	0.215 (3)	0.5202 (15)	0.067*
O51	0.2410 (4)	−0.1906 (3)	0.6086 (2)	0.0316 (5)	0.5
H51	0.209 (3)	−0.259 (2)	0.6588 (15)	0.047*
H51A	0.332 (5)	−0.242 (5)	0.589 (4)	0.047*	0.5
O52	0.3145 (4)	−0.2131 (3)	0.6610 (2)	0.0279 (5)	0.5
H52	0.391 (5)	−0.245 (5)	0.711 (3)	0.042*	0.5

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0338 (2)	0.02347 (17)	0.02226 (18)	0.00774 (14)	−0.00349 (14)	−0.00436 (13)
S2	0.03110 (19)	0.02942 (19)	0.01979 (17)	0.00183 (14)	0.00272 (13)	−0.00193 (13)
P1	0.02118 (17)	0.01825 (16)	0.01566 (16)	−0.00006 (12)	−0.00169 (12)	−0.00069 (12)
C1	0.0294 (8)	0.0350 (9)	0.0437 (10)	−0.0088 (7)	0.0076 (7)	0.0057 (7)
C2	0.0362 (8)	0.0205 (7)	0.0205 (7)	−0.0040 (6)	0.0011 (6)	−0.0036 (5)
C3	0.0343 (8)	0.0221 (7)	0.0195 (7)	−0.0055 (6)	−0.0003 (6)	−0.0017 (5)
C4	0.0368 (8)	0.0207 (7)	0.0194 (7)	−0.0054 (6)	−0.0027 (6)	−0.0007 (5)
C5	0.0223 (7)	0.0291 (7)	0.0199 (7)	0.0009 (6)	−0.0020 (5)	−0.0009 (5)
Na1	0.0237 (3)	0.0255 (3)	0.0249 (3)	−0.0031 (2)	−0.0013 (2)	−0.0055 (2)
O1	0.0341 (6)	0.0263 (5)	0.0237 (5)	−0.0114 (4)	0.0028 (4)	−0.0017 (4)
O2	0.0330 (6)	0.0364 (6)	0.0307 (6)	0.0025 (5)	−0.0107 (5)	−0.0089 (5)
O3	0.0313 (6)	0.0240 (5)	0.0379 (7)	−0.0031 (4)	−0.0060 (5)	−0.0061 (5)
O4	0.0266 (6)	0.0632 (9)	0.0524 (8)	0.0012 (6)	−0.0069 (5)	−0.0341 (7)
O51	0.0327 (13)	0.0287 (12)	0.0326 (13)	−0.0039 (10)	0.0035 (11)	−0.0027 (10)
O52	0.0267 (12)	0.0293 (12)	0.0274 (13)	−0.0076 (9)	−0.0047 (10)	−0.0017 (10)

Geometric parameters (Å, º) top

S1—P1	1.9867 (5)	Na1—Na1ⁱⁱ	3.4885 (11)
S2—P1	2.0073 (5)	Na1—O1	2.3986 (12)
P1—C4	1.8155 (14)	Na1—O2ⁱⁱ	2.4494 (13)
P1—C5	1.8262 (14)	Na1—O2	2.3908 (13)
C1—H1A	0.96 (2)	Na1—O3	2.4413 (13)
C1—H1B	0.99 (2)	Na1—H3C	2.57 (4)
C1—H1C	0.93 (2)	Na1—O4	2.3783 (13)
C1—O1	1.4219 (18)	Na1—O51	2.383 (2)
C2—H2A	0.951 (18)	Na1—O52	2.491 (2)
C2—H2B	0.937 (18)	O2—H2C	0.783 (13)
C2—C3	1.5141 (19)	O2—H2D	0.768 (14)
C2—O1	1.4218 (18)	O3—H3AA	0.788 (14)
C3—H3A	0.929 (19)	O3—H3BB	0.786 (16)
C3—H3B	0.959 (18)	O3—H3C	0.71 (4)
C3—C4	1.521 (2)	O4—H4C	0.775 (14)
C4—H4A	0.911 (19)	O4—H4D	0.748 (14)
C4—H4B	0.93 (2)	O51—H51	0.782 (14)
C5—C5ⁱ	1.530 (3)	O51—H51A	0.785 (16)
C5—H5A	0.918 (19)	O52—H51	0.826 (14)
C5—H5B	0.928 (18)	O52—H52	0.789 (16)

S1—P1—S2	116.51 (2)	O2—Na1—O3	92.52 (4)
C4—P1—S1	110.54 (6)	O2—Na1—H3C	80.5 (10)
C4—P1—S2	109.33 (5)	O2ⁱⁱ—Na1—H3C	70.7 (10)
C4—P1—C5	102.98 (7)	O2—Na1—O52	74.03 (7)
C5—P1—S1	109.49 (5)	O2ⁱⁱ—Na1—O52	86.90 (7)
C5—P1—S2	107.08 (5)	O3—Na1—Na1ⁱⁱ	85.84 (4)
H1A—C1—H1B	110.3 (16)	O3—Na1—O2ⁱⁱ	81.58 (4)
H1A—C1—H1C	105.4 (18)	O3—Na1—H3C	16.1 (10)
H1B—C1—H1C	110.3 (18)	O3—Na1—O52	162.66 (7)
O1—C1—H1A	109.7 (12)	O4—Na1—Na1ⁱⁱ	136.49 (4)
O1—C1—H1B	111.5 (12)	O4—Na1—O1	80.67 (4)
O1—C1—H1C	109.5 (14)	O4—Na1—O2ⁱⁱ	93.34 (5)
H2A—C2—H2B	107.4 (14)	O4—Na1—O2	176.86 (6)
C3—C2—H2A	111.9 (11)	O4—Na1—O3	90.54 (5)
C3—C2—H2B	110.5 (10)	O4—Na1—H3C	102.6 (10)
O1—C2—H2A	109.2 (10)	O4—Na1—O51	91.08 (8)
O1—C2—H2B	107.1 (11)	O4—Na1—O52	103.10 (7)
O1—C2—C3	110.62 (11)	O51—Na1—Na1ⁱⁱ	75.92 (6)
C2—C3—H3A	109.8 (11)	O51—Na1—O1	97.55 (7)
C2—C3—H3B	109.9 (10)	O51—Na1—O2ⁱⁱ	73.40 (7)
C2—C3—C4	108.62 (12)	O51—Na1—O2	86.43 (7)
H3A—C3—H3B	107.0 (14)	O51—Na1—O3	154.98 (8)
C4—C3—H3A	110.6 (11)	O52—Na1—H3C	146.6 (10)
C4—C3—H3B	110.9 (10)	C1—O1—Na1	112.06 (10)
P1—C4—H4A	106.5 (11)	C2—O1—C1	111.26 (12)
P1—C4—H4B	105.7 (12)	C2—O1—Na1	122.95 (9)
C3—C4—P1	116.31 (10)	Na1—O2—Na1ⁱⁱ	92.22 (4)
C3—C4—H4A	108.2 (11)	Na1—O2—H2C	111.4 (16)
C3—C4—H4B	110.7 (12)	Na1ⁱⁱ—O2—H2C	122.1 (16)
H4A—C4—H4B	109.2 (16)	Na1—O2—H2D	120.1 (16)
P1—C5—H5A	107.2 (11)	Na1ⁱⁱ—O2—H2D	105.4 (16)
P1—C5—H5B	105.3 (11)	H2C—O2—H2D	106 (2)
C5ⁱ—C5—P1	114.30 (13)	Na1—O3—H3AA	104.3 (15)
C5ⁱ—C5—H5A	111.7 (11)	Na1—O3—H3BB	143 (3)
C5ⁱ—C5—H5B	110.9 (11)	Na1—O3—H3C	92 (4)
H5A—C5—H5B	107.1 (15)	H3AA—O3—H3BB	104 (3)
Na1ⁱⁱ—Na1—H3C	69.8 (10)	H3AA—O3—H3C	106 (4)
O1—Na1—Na1ⁱⁱ	141.45 (4)	Na1—O4—H4C	108.4 (19)
O1—Na1—O2ⁱⁱ	169.16 (4)	Na1—O4—H4D	116 (2)
O1—Na1—O3	107.34 (4)	H4C—O4—H4D	104 (3)
O1—Na1—H3C	119.4 (10)	Na1—O51—H51	136.6 (15)
O1—Na1—O52	85.69 (6)	Na1—O51—H51A	108 (3)
O2ⁱⁱ—Na1—Na1ⁱⁱ	43.22 (3)	H51—O51—H51A	95 (3)
O2—Na1—Na1ⁱⁱ	44.56 (3)	Na1—O52—H51	120.9 (13)
O2—Na1—O1	97.76 (4)	Na1—O52—H52	112 (3)
O2—Na1—O2ⁱⁱ	87.78 (4)	H51—O52—H52	120 (3)

S1—P1—C4—C3	69.75 (12)	C3—C2—O1—C1	−166.90 (13)
S1—P1—C5—C5ⁱ	53.71 (16)	C3—C2—O1—Na1	56.02 (14)
S2—P1—C4—C3	−59.78 (13)	C4—P1—C5—C5ⁱ	−63.91 (16)
S2—P1—C5—C5ⁱ	−179.14 (13)	C5—P1—C4—C3	−173.38 (12)
C2—C3—C4—P1	−175.75 (10)	O1—C2—C3—C4	−179.89 (12)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2C···S1ⁱⁱⁱ	0.78 (1)	2.52 (1)	3.2920 (13)	167 (2)
O52—H52···S1ⁱⁱⁱ	0.79 (2)	2.42 (2)	3.193 (3)	167 (4)
O3—H3AA···S2^iv	0.79 (1)	2.50 (1)	3.2840 (13)	177 (2)
O4—H4C···S2^v	0.78 (1)	2.49 (2)	3.2535 (14)	169 (2)
O51—H51···S2^vi	0.78 (1)	2.52 (1)	3.117 (2)	134 (2)
O52—H51···S2^vi	0.83 (1)	2.52 (1)	3.314 (2)	162 (2)
O2—H2D···O4^vii	0.77 (1)	2.05 (1)	2.8069 (19)	170 (2)
O3—H3BB···O3^iv	0.79 (2)	2.02 (2)	2.801 (2)	171 (4)
O3—H3C···O52ⁱⁱ	0.71 (4)	2.04 (4)	2.748 (3)	174 (5)
O4—H4D···O51^viii	0.75 (1)	2.07 (2)	2.731 (3)	147 (3)
O51—H51A···O3ⁱⁱ	0.79 (2)	2.05 (2)	2.825 (3)	173 (5)

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

Acknowledgements

DHJ thanks the National Science Foundation for funding to support the diffraction facilities at Otterbein University and BPN thanks Ripon College for funding.

Funding information

Funding for this research was provided by: National Science Foundation, Directorate for Mathematical and Physical Sciences; Ripon College.

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