Crystal structures of polymerized lithium chloride and dimethyl sulfoxide in the form of {2LiCl·3DMSO}n and {LiCl·DMSO}n

Valdez, N.R.; Herman, D.J.; Nemer, M.B.; Rodriguez, M.A.; Allcorn, E.

doi:10.1107/S2056989022011896

research communications

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ISSN: 2056-9890

Volume 79| Part 1| January 2023| Pages 33-37

https://doi.org/10.1107/S2056989022011896

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Crystal structures of polymerized lithium chloride and dimethyl sulfoxide in the form of {2LiCl·3DMSO}_n and {LiCl·DMSO}_n

Nichole R. Valdez,^a ^*‡ David J. Herman,^a § Martin B. Nemer,^a ¶ Mark A. Rodriguez ^a ‡ and Eric Allcorn ^a §

^aSandia National Laboratories, 1515 Eubank Blvd. SE, Albuquerque, NM 87123, USA
^*Correspondence e-mail: nrvalde@sandia.gov

Edited by B. Therrien, University of Neuchâtel, Switzerland (Received 25 October 2022; accepted 13 December 2022; online 1 January 2023)

Two novel LiCl·DMSO polymer structures were created by combining dry LiCl salt with dimethyl sulfoxide (DMSO), namely, catena-poly[[chloridolithium(I)]-μ-(dimethyl sulfoxide)-κ²O:O-[chloridolithium(I)]-di-μ-(dimethyl sulfoxide)-κ⁴O:O], [Li₂Cl₂(C₂H₆OS)₃]_n, and catena-poly[lithium(I)-μ-chlorido-μ-(dimethyl sulfoxide)-κ²O:O], [LiCl(C₂H₆OS)]_n. The initial synthesized phase had very small block-shaped crystals (<0.08 mm) with monoclinic symmetry and a 2 LiCl: 3 DMSO ratio. As the solution evaporated, a second phase formed with a plate-shaped crystal morphology. After about 20 minutes, large (>0.20 mm) octahedron-shaped crystals formed. The plate crystals and the octahedron crystals are the same tetragonal structure with a 1 LiCl: 1 DMSO ratio. These structures are reported and compared to other known LiCl·solvent compounds.

Keywords: crystal structure; LiCl; DMSO; polymer.

CCDC references: 2226319; 2226318

1. Chemical context

Lithium salts are soluble in a wide range of solvents and are widely used in lithium-metal and lithium-ion battery applications (Bushkova et al., 2017 ; Mauger et al., 2018 ; Younesi et al. 2015 ). While typically implemented as liquid electrolyte solutions, the lithium salt and solvent systems can also form complex molecular phases, including intercalating compounds (Yamada et al., 2010 ), crystalline solvates (Ugata et al., 2021 ), and polymeric structures (Rao et al., 1984 ; Chivers et al., 2001 ).

Dimethyl sulfoxide (DMSO) and lithium chloride (LiCl) are very common materials in many industries, and have each been used in novel battery systems, including solid-polymer (Voigt & van Wüllen, 2012 ), dual-ion (Wang et al., 2022 ), lithium–oxygen (Togasaki et al., 2016 ; Reddy et al., 2018 ; Zhang et al., 2021 ) and molten-salt electrolyte batteries (Allcorn et al., 2020 ). Given that DMSO and water both exhibit a coordination number of four solvent molecules per cation (Megyes et al., 2006 ; Bouazizi & Nasr, 2007 ), it is reasonable to hypothesize that the two solvents solvate lithium ions similarly. For Li⁺ cations in binary solvent solutions of DMSO and water, the solvent molecules are analogous; there is effectively no selective solvation of Li⁺ cations for either DMSO or water (Pasgreta et al., 2007 ). Thus it is not surprising that lithium salts would form similar crystalline phases when comparing phase diagrams in pure DMSO (Kirillov et al., 2015 ) and pure water (Perron et al., 1997 ). Since LiCl is hydrated with 1–2 water molecules per Li⁺ cation in ambient conditions (Conde, 2004 ; Pátek & Klomfar, 2006 ), it is reasonable to expect that LiCl would form similar if not analogous solvate phases in DMSO (1–2 DMSO molecules per Li⁺ cation).

2. Synthesis and crystallization

Material samples were prepared using lithium chloride (Acros Organics, LiCl 99% anhydrous) and dimethyl sulfoxide (Sigma-Aldrich, C₂H₆OS ≥99.9% anhydrous). Before use, the LiCl was heated to 423.15 K (150°C) under vacuum to remove any trace moisture, and the sample preparation was carried out in a humidity-controlled dry room, dew point below 223.15 K (−50°C).

Dry LiCl was added to a jar of DMSO at a ratio of 5 g LiCl per 25 g DMSO, approximately twice the limit at 298.15 K (25°C) before saturation is initially observed (Xin et al., 2018 ). As the salt tends to agglomerate quickly upon being added to the DMSO, the initial larger agglomerates were manually broken up. The jar was then sealed and the entire solution was stirred vigorously with a magnetic stir bar for 3 days. An aliquot of the sample (solids and saturated DMSO combined) was removed for analysis. During sample preparation for single crystal X-ray diffraction analysis, DMSO evaporated from the sample aliquot, resulting in a second, likely metastable, phase with different crystal morphology.

3. Structural Commentary

Monoclinic Crystals

The initial crystals synthesized as described in the previous section are small (<0.08 mm), block-shaped, and have monoclinic symmetry C2/c. The polymer has a 2 LiCl: 3 DMSO ratio, and the repeating unit is composed of four LiCl, and six DMSO, see Fig. 1 and Scheme.

Figure 1
Monoclinic structure: asymmetric unit (a) and polymeric chain view (b). The repeating unit of the polymer has four LiCl and six DMSO. The sulfur atom of the DMSO is disordered across two positions. Only one position is shown.

The polymers appear to be held together by hydrogen bonding, see Table 1 and packing diagram Fig. 2. The most notable bond is between Cl1 and H2B (2.730 Å), where the Cl atom on one polymer chain is connected to one of the hydrogen atoms on one of the methyl groups of the non-disordered DMSO molecule of another polymer chain. There is likely some hydrogen bond contribution from the adjacent H3B, which is located on the other methyl group of the same DMSO molecule (hydrogen-bond length 2.88 Å). If the disordered DMSO molecule contributes to hydrogen bonding between polymer chains, it would be through hydrogen H1A and Cl1, however this bond is very long [2.98 (3) Å]. The other values in the table represent hydrogen bonding between a DMSO molecule and a Cl atom along the same polymer chain.

Table 1
Hydrogen-bond geometry (Å, °) for the monoclinic structure

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯Cl1ⁱ	0.97 (1)	2.98 (4)	3.569 (3)	120 (3)
C1—H1B⋯Cl1ⁱⁱ	0.97 (1)	2.79 (2)	3.690 (3)	156 (3)
C2—H2A⋯Cl1ⁱⁱⁱ	0.98	2.71	3.680 (3)	169
C2—H2B⋯Cl1^iv	0.98	2.73	3.632 (3)	153
C3—H3B⋯Cl1^iv	0.98	2.88	3.752 (3)	149
Symmetry codes: (i) $[-x+1, y-1, -z+{\script{1\over 2}}]$ ; (ii) $[x, -y+1, z-{\script{1\over 2}}]$ ; (iii) $[-x+1, y, -z+{\script{1\over 2}}]$ ; (iv) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Figure 2
Monoclinic structure: packing diagram. The structure is held together by hydrogen bonding. The hydrogen bonds between Cl1 and H2B as well as Cl1 and H3B are shown.

Tetragonal Crystals

The second crystal phase formed during sample preparation as DMSO evaporated. At first, plate-shaped crystals appeared among the smaller block-shaped crystals. As more time passed (∼20 minutes), much larger (0.2–0.4 mm) octahedron-shaped crystals formed. The plate crystals and the octahedron crystals are the same tetragonal I4₁/a structure with a 1 LiCl: 1 DMSO ratio. The repeating unit has four LiCl, and four DMSO. The DMSO molecules are not disordered in this structure, see Fig. 3 and Scheme.

Figure 3
Tetragonal structure: asymmetric unit (a) and polymeric chain view (b). The repeating unit of the polymer has four LiCl and four DMSO. The DMSO molecules in this structure are not disordered.

As with the monoclinic structure, the tetragonal structure is composed of polymer chains held together by hydrogen bonding, see Table 2 and the packing diagram Fig. 4. The Cl1 of one chain is linked to the DMSO of another chain through H2A [2.84 (2) Å] and H2C [2.83 (2) Å]. There may be some contribution from H1B, though the bond is much longer [2.95 (2) Å].

Table 2
Hydrogen-bond geometry (Å, °) for the tetragonal structure

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1B⋯Cl1ⁱ	0.98 (2)	2.95 (2)	3.821 (2)	148 (2)
C2—H2A⋯Cl1ⁱⁱ	0.95 (2)	2.84 (2)	3.768 (2)	165 (2)
C2—H2C⋯Cl1ⁱ	0.96 (2)	2.83 (2)	3.716 (2)	153 (2)
Symmetry codes: (i) $[x-{\script{1\over 2}}, y, -z+{\script{3\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, -y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 4
Tetragonal structure: packing diagram. The structure is held together by hydrogen bonding. The hydrogen bonds between Cl1 and H2A and Cl1 and H2C are shown. The atoms involved in hydrogen bonding are darkened for clarity.

4. Database Survey

After the structures were solved, a search was performed on the Cambridge Structural Database (CSD, version 5.43, November 2021; Groom et al., 2016 ). There were only two results with the relevant chemistry, and neither had DMSO. One was a LiCl sulfolane adduct (SIWFOT; Harvey et al., 1991 ), and the other was a crown ether complex (XEGBIX; Reuter et al., 2017 ). These two LiCl·DMSO structures are novel, and other phases likely exist in the LiCl–DMSO system as a function of temperature, analogous to the LiCl–H₂O system (Perron et al., 1997). An extensive list of LiCl structures with various other ligands can be found in Chivers et al. (2001).

5. Refinement

Crystal data, data collection, and structure refinement details are summarized in Table 3. One of the DMSO molecules on the monoclinic structure is disordered. The two positions of the sulfur atom show a C₂ symmetry-related disorder about the oxygen atom in the b-axis direction of the unit cell. An attempt was made to model the disorder using a lower space group (Cc); however, the refinement was unstable. Without the ability to use a PART instruction, the DMSO molecule was fixed to an occupancy of 0.5. The hydrogen atoms on the disordered DMSO molecule were placed manually. For the monclinic structure, all H atoms were refined with U_iso(H) = 1.5U_eq(C). Bond-length restraints of 0.98 ± 0.02 Å were applied to the H atoms on C2 and C3.

Table 3
Experimental details

	Monoclinic	Tetragonal
Crystal data
Chemical formula	[Li₂Cl₂(C₂H₆OS)₃]	[LiCl(C₂H₆OS)]
M_r	319.16	120.52
Crystal system, space group	Monoclinic, C2/c	Tetragonal, I4₁/a
Temperature (K)	100	100
a, b, c (Å)	19.2841 (17), 7.6436 (7), 11.5335 (10)	14.2411 (14), 14.2411 (14), 10.8809 (16)
α, β, γ (°)	90, 118.315 (5), 90	90, 90, 90
V (Å³)	1496.6 (2)	2206.7 (5)
Z	4	16
Radiation type	Cu Kα	Cu Kα
μ (mm⁻¹)	7.72	8.49
Crystal size (mm)	0.07 × 0.07 × 0.05	0.4 × 0.4 × 0.4

Data collection
Diffractometer	Bruker APEXII CCD	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )	Multi-scan (SADABS; Krause et al., 2015)
T_min, T_max	0.639, 0.754	0.513, 0.754
No. of measured, independent and observed [I > 2σ(I)] reflections	10606, 1417, 1166	8174, 1072, 1030
R_int	0.064	0.047
(sin θ/λ)_max (Å⁻¹)	0.610	0.618

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.081, 1.09	0.028, 0.073, 1.07
No. of reflections	1417	1072
No. of parameters	92	79
No. of restraints	68	0
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.39	0.32, −0.37
Computer programs: APEX2 and SAINT (Bruker, 2016 ), SHELXT2014/5 (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC references: 2226319; 2226318

Crystal structure: contains datablocks Monoclinic, Tetragonal. DOI: https://doi.org/10.1107/S2056989022011896/tx2060sup1.cif

checkCIF report

Computing details top

For both structures, data collection: APEX2 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT2014/5 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: Olex2 (Dolomanov et al., 2009); software used to prepare material for publication: Olex2 (Dolomanov et al., 2009).

catena-Poly[[chloridolithium(I)]-µ-(dimethyl sulfoxide)-κ²O:O-[chloridolithium(I)]-di-µ-(dimethyl sulfoxide)-κ⁴O:O] (Monoclinic) top

Crystal data top

[Li₂Cl₂(C₂H₆OS)₃]	F(000) = 664
M_r = 319.16	D_x = 1.416 Mg m⁻³
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54178 Å
a = 19.2841 (17) Å	Cell parameters from 4022 reflections
b = 7.6436 (7) Å	θ = 5.2–71.2°
c = 11.5335 (10) Å	µ = 7.72 mm⁻¹
β = 118.315 (5)°	T = 100 K
V = 1496.6 (2) Å³	Block, colourless
Z = 4	0.07 × 0.07 × 0.05 mm

Data collection top

Bruker APEXII CCD diffractometer	1166 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.064
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 70.0°, θ_min = 5.2°
T_min = 0.639, T_max = 0.754	h = −22→23
10606 measured reflections	k = −9→9
1417 independent reflections	l = −14→14

Refinement top

Refinement on F²	68 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.035	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.081	w = 1/[σ²(F_o²) + (0.0023P)² + 6.8363P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max = 0.001
1417 reflections	Δρ_max = 0.46 e Å⁻³
92 parameters	Δρ_min = −0.39 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)
Li1	0.4831 (3)	0.5661 (7)	0.3715 (4)	0.0215 (10)
Cl1	0.39011 (4)	0.78167 (9)	0.26503 (6)	0.02346 (19)
O1	0.500000	0.4171 (4)	0.250000	0.0231 (6)
S1	0.46168 (7)	0.23074 (17)	0.24491 (12)	0.0150 (3)	0.5
C1	0.46522 (18)	0.1205 (4)	0.1177 (3)	0.0227 (6)
H1A	0.463 (2)	−0.006 (2)	0.125 (4)	0.052 (12)*
H1B	0.439 (2)	0.178 (5)	0.033 (2)	0.052 (12)*
H1C	0.519 (2)	0.121 (12)	0.129 (9)	0.21 (4)*
O2	0.57073 (10)	0.5856 (3)	0.55161 (17)	0.0184 (4)
S2	0.65940 (4)	0.60785 (9)	0.63468 (6)	0.01629 (18)
C2	0.68091 (16)	0.8173 (4)	0.5918 (3)	0.0207 (6)
H2A	0.659005	0.824918	0.496007	0.031*
H2B	0.738110	0.833830	0.633975	0.031*
H2C	0.657431	0.908521	0.621951	0.031*
C3	0.70219 (17)	0.4751 (4)	0.5580 (3)	0.0229 (6)
H3A	0.694545	0.351352	0.571155	0.034*
H3B	0.758674	0.500205	0.597297	0.034*
H3C	0.676854	0.500799	0.463501	0.034*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Li1	0.017 (2)	0.032 (3)	0.014 (2)	−0.001 (2)	0.0064 (18)	−0.0028 (19)
Cl1	0.0195 (3)	0.0272 (4)	0.0174 (3)	−0.0028 (3)	0.0037 (3)	0.0043 (3)
O1	0.0408 (17)	0.0139 (13)	0.0175 (14)	0.000	0.0162 (13)	0.000
S1	0.0136 (6)	0.0169 (6)	0.0141 (6)	−0.0003 (5)	0.0063 (5)	−0.0001 (5)
C1	0.0275 (16)	0.0185 (15)	0.0152 (14)	−0.0019 (13)	0.0045 (13)	−0.0008 (11)
O2	0.0111 (9)	0.0284 (11)	0.0139 (9)	−0.0011 (8)	0.0046 (7)	0.0003 (8)
S2	0.0125 (3)	0.0213 (4)	0.0138 (3)	−0.0014 (3)	0.0052 (3)	0.0013 (3)
C2	0.0189 (14)	0.0214 (15)	0.0198 (14)	−0.0024 (11)	0.0074 (12)	0.0001 (11)
C3	0.0202 (14)	0.0260 (16)	0.0238 (15)	−0.0008 (12)	0.0114 (12)	−0.0019 (12)

Geometric parameters (Å, º) top

Li1—Li1ⁱ	3.162 (9)	C1—H1A	0.972 (14)
Li1—Li1ⁱⁱ	2.899 (9)	C1—H1B	0.967 (14)
Li1—Cl1	2.313 (5)	C1—H1C	0.974 (15)
Li1—O1	1.949 (5)	O2—S2	1.5219 (18)
Li1—S1	2.881 (5)	S2—C2	1.782 (3)
Li1—O2ⁱⁱ	2.021 (5)	S2—C3	1.785 (3)
Li1—O2	1.966 (5)	C2—H2A	0.9800
Li1—S2ⁱⁱ	3.024 (5)	C2—H2B	0.9800
O1—S1	1.593 (3)	C2—H2C	0.9800
O1—S1ⁱ	1.593 (3)	C3—H3A	0.9800
S1—S1ⁱ	1.426 (2)	C3—H3B	0.9800
S1—C1	1.721 (3)	C3—H3C	0.9800
S1—C1ⁱ	1.758 (3)

Li1ⁱⁱ—Li1—Li1ⁱ	149.9 (3)	S1ⁱ—S1—O1	63.41 (6)
Li1ⁱⁱ—Li1—S2ⁱⁱ	68.36 (17)	S1ⁱ—S1—C1ⁱ	64.48 (13)
Cl1—Li1—Li1ⁱⁱ	122.2 (3)	S1ⁱ—S1—C1	67.14 (13)
Cl1—Li1—Li1ⁱ	87.91 (16)	C1ⁱ—S1—Li1	96.24 (14)
Cl1—Li1—S1	118.43 (18)	C1—S1—Li1	144.41 (15)
Cl1—Li1—S2ⁱⁱ	80.40 (13)	C1—S1—C1ⁱ	101.25 (18)
O1—Li1—Li1ⁱⁱ	119.9 (3)	S1—C1—S1ⁱ	48.38 (11)
O1—Li1—Li1ⁱ	35.76 (16)	S1ⁱ—C1—H1A	117 (2)
O1—Li1—Cl1	112.8 (2)	S1—C1—H1A	113 (2)
O1—Li1—S1	31.64 (11)	S1—C1—H1B	115 (2)
O1—Li1—O2	116.8 (2)	S1ⁱ—C1—H1B	120 (2)
O1—Li1—O2ⁱⁱ	106.0 (3)	S1—C1—H1C	111 (5)
O1—Li1—S2ⁱⁱ	100.72 (19)	S1ⁱ—C1—H1C	62 (5)
S1—Li1—Li1ⁱ	65.90 (10)	H1A—C1—H1B	121 (3)
S1—Li1—Li1ⁱⁱ	96.7 (2)	H1A—C1—H1C	95 (5)
S1—Li1—S2ⁱⁱ	71.72 (12)	H1B—C1—H1C	98 (5)
O2ⁱⁱ—Li1—Li1ⁱⁱ	42.59 (14)	Li1—O2—Li1ⁱⁱ	93.3 (2)
O2—Li1—Li1ⁱ	120.1 (3)	S2—O2—Li1ⁱⁱ	116.46 (16)
O2—Li1—Li1ⁱⁱ	44.10 (13)	S2—O2—Li1	145.04 (17)
O2ⁱⁱ—Li1—Li1ⁱ	138.89 (18)	O2—S2—Li1ⁱⁱ	36.75 (11)
O2ⁱⁱ—Li1—Cl1	102.2 (2)	O2—S2—C2	105.41 (12)
O2—Li1—Cl1	124.6 (2)	O2—S2—C3	105.66 (12)
O2ⁱⁱ—Li1—S1	74.44 (17)	C2—S2—Li1ⁱⁱ	135.83 (14)
O2—Li1—S1	116.6 (2)	C2—S2—C3	98.65 (14)
O2—Li1—O2ⁱⁱ	86.7 (2)	C3—S2—Li1ⁱⁱ	111.54 (14)
O2ⁱⁱ—Li1—S2ⁱⁱ	26.78 (8)	S2—C2—H2A	109.5
O2—Li1—S2ⁱⁱ	111.96 (19)	S2—C2—H2B	109.5
S2ⁱⁱ—Li1—Li1ⁱ	123.1 (2)	S2—C2—H2C	109.5
Li1ⁱ—O1—Li1	108.5 (3)	H2A—C2—H2B	109.5
S1—O1—Li1ⁱ	136.79 (16)	H2A—C2—H2C	109.5
S1ⁱ—O1—Li1ⁱ	108.45 (16)	H2B—C2—H2C	109.5
S1—O1—Li1	108.45 (16)	S2—C3—H3A	109.5
S1ⁱ—O1—Li1	136.79 (16)	S2—C3—H3B	109.5
S1—O1—S1ⁱ	53.18 (13)	S2—C3—H3C	109.5
O1—S1—Li1	39.92 (10)	H3A—C3—H3B	109.5
O1—S1—C1ⁱ	103.64 (12)	H3A—C3—H3C	109.5
O1—S1—C1	105.29 (13)	H3B—C3—H3C	109.5
S1ⁱ—S1—Li1	93.68 (11)

Li1ⁱ—O1—S1—Li1	−147.5 (2)	Li1—O2—S2—C2	63.5 (4)
Li1ⁱ—O1—S1—S1ⁱ	77.3 (2)	Li1ⁱⁱ—O2—S2—C2	−151.0 (2)
Li1—O1—S1—S1ⁱ	−135.24 (17)	Li1ⁱⁱ—O2—S2—C3	105.2 (2)
Li1ⁱ—O1—S1—C1ⁱ	129.2 (2)	Li1—O2—S2—C3	−40.4 (4)
Li1—O1—S1—C1	170.72 (19)	O1—S1—C1—S1ⁱ	51.77 (9)
Li1ⁱ—O1—S1—C1	23.3 (3)	S1ⁱ—O1—S1—Li1	135.24 (17)
Li1—O1—S1—C1ⁱ	−83.35 (19)	S1ⁱ—O1—S1—C1ⁱ	51.89 (13)
Li1—S1—C1—S1ⁱ	62.0 (2)	S1ⁱ—O1—S1—C1	−54.04 (13)
Li1—O2—S2—Li1ⁱⁱ	−145.5 (3)	C1ⁱ—S1—C1—S1ⁱ	−55.91 (15)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···Cl1ⁱⁱⁱ	0.97 (1)	2.98 (4)	3.569 (3)	120 (3)
C1—H1B···Cl1^iv	0.97 (1)	2.79 (2)	3.690 (3)	156 (3)
C2—H2A···Cl1ⁱ	0.98	2.71	3.680 (3)	169
C2—H2B···Cl1^v	0.98	2.73	3.632 (3)	153
C3—H3B···Cl1^v	0.98	2.88	3.752 (3)	149

Symmetry codes: (i) −x+1, y, −z+1/2; (iii) −x+1, y−1, −z+1/2; (iv) x, −y+1, z−1/2; (v) x+1/2, −y+3/2, z+1/2.

catena-Poly[lithium(I)-µ-chlorido-µ-(dimethyl sulfoxide)-κ²O:O] (Tetragonal) top

Crystal data top

[LiCl(C₂H₆OS)]	D_x = 1.451 Mg m⁻³
M_r = 120.52	Cu Kα radiation, λ = 1.54178 Å
Tetragonal, I4₁/a	Cell parameters from 6535 reflections
a = 14.2411 (14) Å	θ = 4.4–72.3°
c = 10.8809 (16) Å	µ = 8.49 mm⁻¹
V = 2206.7 (5) Å³	T = 100 K
Z = 16	Octahedron, clear colourless
F(000) = 992	0.4 × 0.4 × 0.4 mm

Data collection top

Bruker APEXII CCD diffractometer	1030 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.047
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 72.3°, θ_min = 5.1°
T_min = 0.513, T_max = 0.754	h = −17→16
8174 measured reflections	k = −16→17
1072 independent reflections	l = −13→13

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.028	All H-atom parameters refined
wR(F²) = 0.073	w = 1/[σ²(F_o²) + (0.0416P)² + 1.762P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
1072 reflections	Δρ_max = 0.32 e Å⁻³
79 parameters	Δρ_min = −0.37 e Å⁻³

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.81811 (3)	0.36163 (2)	0.89755 (3)	0.02090 (17)
S1	0.58855 (3)	0.44534 (2)	0.62126 (3)	0.01513 (16)
O1	0.69499 (7)	0.45632 (8)	0.62414 (8)	0.0182 (3)
C1	0.56163 (11)	0.37206 (12)	0.74923 (14)	0.0238 (3)
H1A	0.6017 (15)	0.3177 (14)	0.7468 (19)	0.035 (5)*
H1B	0.4949 (14)	0.3561 (14)	0.7438 (18)	0.032 (5)*
H1C	0.5707 (14)	0.4087 (14)	0.822 (2)	0.030 (5)*
C2	0.56716 (10)	0.36370 (11)	0.50047 (14)	0.0194 (3)
H2A	0.6049 (14)	0.3099 (14)	0.5150 (18)	0.030 (5)*
H2B	0.5842 (13)	0.3952 (14)	0.425 (2)	0.029 (5)*
H2C	0.5011 (14)	0.3503 (14)	0.5012 (18)	0.030 (5)*
Li1	0.77950 (17)	0.48024 (16)	0.7596 (2)	0.0185 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0232 (2)	0.0197 (2)	0.0198 (2)	0.00734 (14)	0.00006 (13)	0.00281 (13)
S1	0.0163 (2)	0.0145 (2)	0.0145 (2)	−0.00053 (13)	0.00054 (12)	0.00014 (11)
O1	0.0173 (6)	0.0243 (6)	0.0128 (5)	−0.0070 (4)	−0.0005 (3)	0.0004 (4)
C1	0.0222 (8)	0.0307 (9)	0.0184 (8)	−0.0065 (7)	0.0026 (6)	0.0052 (6)
C2	0.0176 (7)	0.0212 (7)	0.0193 (7)	−0.0011 (6)	−0.0023 (5)	−0.0025 (6)
Li1	0.0216 (12)	0.0206 (12)	0.0133 (10)	0.0025 (10)	−0.0006 (9)	−0.0006 (9)

Geometric parameters (Å, º) top

Cl1—Li1	2.326 (2)	C1—H1B	0.98 (2)
Cl1—Li1ⁱ	2.336 (2)	C1—H1C	0.96 (2)
S1—O1	1.5241 (11)	C2—H2A	0.95 (2)
S1—C1	1.7819 (15)	C2—H2B	0.97 (2)
S1—C2	1.7810 (15)	C2—H2C	0.96 (2)
O1—Li1ⁱⁱ	1.943 (3)	Li1—Li1ⁱ	2.8126 (10)
O1—Li1	1.933 (3)	Li1—Li1ⁱⁱ	2.8127 (10)
C1—H1A	0.96 (2)

Li1—Cl1—Li1ⁱ	74.22 (7)	H2A—C2—H2C	113.1 (18)
O1—S1—C1	104.95 (7)	H2B—C2—H2C	110.1 (16)
O1—S1—C2	104.61 (6)	Cl1—Li1—Cl1ⁱⁱ	124.69 (11)
C2—S1—C1	99.06 (8)	Cl1ⁱⁱ—Li1—Li1ⁱ	134.17 (10)
S1—O1—Li1	130.77 (9)	Cl1—Li1—Li1ⁱⁱ	144.79 (11)
S1—O1—Li1ⁱⁱ	125.94 (9)	Cl1ⁱⁱ—Li1—Li1ⁱⁱ	52.72 (8)
Li1—O1—Li1ⁱⁱ	93.06 (8)	Cl1—Li1—Li1ⁱ	53.05 (7)
S1—C1—H1A	108.8 (12)	O1ⁱ—Li1—Cl1	96.36 (10)
S1—C1—H1B	107.3 (12)	O1ⁱ—Li1—Cl1ⁱⁱ	113.41 (11)
S1—C1—H1C	107.3 (12)	O1—Li1—Cl1ⁱⁱ	96.30 (10)
H1A—C1—H1B	112.8 (18)	O1—Li1—Cl1	120.75 (12)
H1A—C1—H1C	112.5 (17)	O1—Li1—O1ⁱ	104.58 (12)
H1B—C1—H1C	107.9 (16)	O1—Li1—Li1ⁱ	124.99 (13)
S1—C2—H2A	107.9 (12)	O1ⁱ—Li1—Li1ⁱ	43.34 (7)
S1—C2—H2B	106.4 (12)	O1ⁱ—Li1—Li1ⁱⁱ	117.22 (12)
S1—C2—H2C	107.0 (12)	O1—Li1—Li1ⁱⁱ	43.60 (6)
H2A—C2—H2B	111.9 (16)	Li1ⁱ—Li1—Li1ⁱⁱ	159.29 (10)

C1—S1—O1—Li1ⁱⁱ	−179.33 (12)	C2—S1—O1—Li1ⁱⁱ	76.90 (13)
C1—S1—O1—Li1	−43.92 (15)	C2—S1—O1—Li1	−147.69 (13)

Symmetry codes: (i) y+1/4, −x+5/4, z+1/4; (ii) −y+5/4, x−1/4, z−1/4.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1B···Cl1ⁱⁱⁱ	0.98 (2)	2.95 (2)	3.821 (2)	148 (2)
C2—H2A···Cl1^iv	0.95 (2)	2.84 (2)	3.768 (2)	165 (2)
C2—H2C···Cl1ⁱⁱⁱ	0.96 (2)	2.83 (2)	3.716 (2)	153 (2)

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

Footnotes

‡1819 Materials Characterization & Performance.

§7546 Power Sources R&D.

¶1512 Diagnostic Science & Engineering.

Acknowledgements

The authors wish to thank Bertha Montoya and Claudina Cammack for aiding the synthesis. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology & Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International Inc., for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-NA0003525. This paper describes objective technical results and analysis. Any subjective views or opinions that might be expressed in the paper do not necessarily represent the views of the U.S. Department of Energy or the United States Government.

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