Bis[μ-2-(phenyl­sulfan­yl)anilido-κ2N:N]bis­[bis­(tetra­hydro­furan-κO)lithium]

Mdluli, V.; Golen, J.A.; Manke, D.R.

doi:10.1107/S2414314616001309

metal-organic compounds

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ISSN: 2414-3146

Volume 1| Part 1| January 2016| x160130

doi:10.1107/S2414314616001309

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Bis[μ-2-(phenylsulfanyl)anilido-κ²N:N]bis[bis(tetrahydrofuran-κO)lithium]

Velabo Mdluli,^a James A. Golen ^a and David R. Manke ^a ^*

^aDepartment of Chemistry and Biochemistry, University of Massachusetts Dartmouth, 285 Old Westport Road, North Dartmouth, MA 02747, USA
^*Correspondence e-mail: dmanke@umassd.edu

Edited by M. Weil, Vienna University of Technology, Austria (Received 19 January 2016; accepted 20 January 2016; online 26 January 2016)

The title compound, [Li₂(C₁₂H₁₀NS)₂(C₄H₈O)₄], exists as a dimer in the solid state, with a central four-membered Li₂N₂ ring that is planar by crystallographic inversion symmetry. The Li atoms are bridged by the N atoms of two anilide ligands, and each Li atom is coordinated by two O atoms from tetrahydrofuran ligands, resulting in a distorted tetrahedral N₂O₂ environment. One of the tetrahydrofuran rings is disordered over two sets of sites in a 0.665 (16):0.335 (6) ratio.

Keywords: crystal structure; lithium anilide; thioaniline.

CCDC reference: 1448763

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Chemical scheme

Structure description

Lithium amide complexes can lead to ladder-shaped conformations with solvation of the lithium atom often controlling the oligimerization/polymerization of the lithium complex (Clegg et al., 1995 ). Herein, we report the crystal structure of the lithium 2-(phenylthio)aniline bis(tetrahydrofuran) dimer. In the crystal, the dimerization results in a centrosymmetric Li₂N₂ ring (Fig. 1), with Li—N—Liⁱ and N—Li—Nⁱ [symmetry code: (i) −x, −y + 1, −z + 1] angles of 75.65 (10) and 104.35 (13)°, respectively, that are consistent with similar dimers (von Bülow et al., 1996 , 2004 ; Cole et al., 2002 ). The dihedral angle between the least-squares planes of the Li₂N₂ ring and the aniline aromatic ring is 84.14 (12)°, and the dihedral angle between the two aromatic ring planes in the 2-(phenylthio)anilide is 79.52 (7)°, similar to that observed in the parent 2-(phenylthio)aniline (Mdluli et al., 2016 ). No π–π interactions are noted between the aromatic rings. The packing of the molecules in the title compound is shown in Fig. 2.

Figure 1
The molecular structure of the title compound, showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 30% probability level; H atoms are drawn as spheres of arbitrary radius. Non-labelled atoms are generated by symmetry code (−x, −y + 1, −z + 1). Bonds in the minor disorder components of the disordered tetrahydrofuran molecules are drawn as dashed lines.

Figure 2
View of the molecular packing of the title compound along the b axis. Only the major component of the disordered tetrahydrofuran molecule is shown.

Synthesis and crystallization

A solution of 2-phenylthioaniline (668 mg, 3.34 mmol) in 3 ml of dry tetrahydrofuran was frozen. Upon melting, 1.41 ml of a 2.5 M n-butyllithium solution in hexanes (3.53 mmol) was added dropwise. After stirring for 30 minutes at room temperature, 7 ml of dry pentane was added and the solution was stirred for additional 1.5 h. The resulting precipitate was isolated via vacuum filtration as a white powder (589 mg, 84% yield). ¹H NMR (400 MHz, C₆D₆): δ 7.60 (d, J = 7.2 Hz, 1 H, Ar-H), 7.24 (d, J = 7.6 Hz, 2 H, Ar-H), 7.17 (dt, J = 7.6 Hz, 1.6 Hz, 1 H, Ar-H), 7.14 (t, J = 7.6 Hz, 2 H, Ar-H), 6.77 (m, 2H, Ar-H), 6.38 (t, J = 7.2 Hz, 1 H, Ar-H), 3.68 (br s, 1 H, NH), 3.33 (m, 8 H, OCH₂), 1.25 (m, 8 H, CH₂); ¹³C NMR (100 MHz, C₆D₆): δ 165.8, 139.9, 138.2, 131.1, 128.9, 127.9, 125.3, 123.9, 117.7, 110.1, 67.5, 24.9. A sample suitable for single-crystal X-ray analysis was grown from pentane/tetrahydrofuran layering.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. One of the tetrahydrofuran ligands (C17–C20) is disordered over two sets of sites with a refined occupancy ratio of 0.665 (6):0.335 (6).

Table 1
Experimental details

Crystal data
Chemical formula	[Li₂(C₁₂H₁₀NS)₂(C₄H₈O)₄]
M_r	702.83
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	200
a, b, c (Å)	9.6540 (7), 9.9211 (6), 11.2854 (8)
α, β, γ (°)	73.537 (3), 88.138 (3), 72.420 (3)
V (Å³)	986.50 (12)
Z	1
Radiation type	Mo Kα
μ (mm⁻¹)	0.18
Crystal size (mm)	0.5 × 0.4 × 0.3

Data collection
Diffractometer	Bruker D8 Venture CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.717, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	28827, 3607, 3140
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.604

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.111, 1.06
No. of reflections	3607
No. of parameters	249
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.29
Computer programs: APEX2 (Bruker, 2014), SAINT (Bruker, 2014), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), OLEX2 (Dolomanov et al., 2009 ), publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1448763

Crystal structure: contains datablock I. DOI: 10.1107/S2414314616001309/wm4006sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616001309/wm4006Isup2.hkl

checkCIF report

Experimental top

Structure description top

Lithium amide complexes can lead to ladder-shaped conformations with solvation of the lithium atom often controlling the oligimerization/polymerization of the lithium complex (Clegg et al., 1995). Herein, we report the crystal structure of the lithium 2-(phenylthio)aniline bis(tetrahydrofuran) dimer. In the crystal, the dimerization results in a centrosymmetric Li₂N₂ ring (Fig. 1), with Li—N—Liⁱ and N—Li—Nⁱ [symmetry code: (i) −x, −y + 1, −z + 1] angles of 75.65 (10) and 104.35 (13)°, respectively, that are consistent with similar dimers (von Bülow et al., 1996, 2004; Cole et al., 2002). The dihedral angle between the least-squares planes of the Li₂N₂ ring and the aniline aromatic ring is 84.14 (12)°, and the dihedral angle between the two aromatic ring planes in the 2-(phenylthio)anilide is 79.52 (7)°, similar to that observed in the parent 2-(phenylthio)aniline (Mdluli et al., 2016). No π–π interactions are noted between the aromatic rings. The packing of the molecules in the title compound is shown in Fig. 2.

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of the title compound, showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 30% probability level; H atoms are drawn as spheres of arbitrary radius. Non-labelled atoms are generated by symmetry code (−x, −y + 1, −z + 1).
	Fig. 2. View of the molecular packing of the title compound along the b axis. Only the major component of the disordered tetrahydrofuran molecule is shown.

Bis[µ-2-(phenylsulfanyl)anilido-κ²N:N]bis[bis(tetrahydrofuran-κO)lithium] top

Crystal data top

[Li₂(C₁₂H₁₀NS)₂(C₄H₈O)₄]	Z = 1
M_r = 702.83	F(000) = 376
Triclinic, P1	D_x = 1.183 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.6540 (7) Å	Cell parameters from 9896 reflections
b = 9.9211 (6) Å	θ = 2.8–25.4°
c = 11.2854 (8) Å	µ = 0.18 mm⁻¹
α = 73.537 (3)°	T = 200 K
β = 88.138 (3)°	Block, colourless
γ = 72.420 (3)°	0.5 × 0.4 × 0.3 mm
V = 986.50 (12) Å³

Data collection top

Bruker D8 Venture CMOS diffractometer	3607 independent reflections
Radiation source: Mo	3140 reflections with I > 2σ(I)
TRIUMPH monochromator	R_int = 0.028
φ and ω scans	θ_max = 25.4°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2014)	h = −11→11
T_min = 0.717, T_max = 0.745	k = −11→11
28827 measured reflections	l = −13→13

Refinement top

Refinement on F²	2 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.042	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.111	w = 1/[σ²(F_o²) + (0.0453P)² + 0.5014P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
3607 reflections	Δρ_max = 0.31 e Å⁻³
249 parameters	Δρ_min = −0.29 e Å⁻³

Crystal data top

[Li₂(C₁₂H₁₀NS)₂(C₄H₈O)₄]	γ = 72.420 (3)°
M_r = 702.83	V = 986.50 (12) Å³
Triclinic, P1	Z = 1
a = 9.6540 (7) Å	Mo Kα radiation
b = 9.9211 (6) Å	µ = 0.18 mm⁻¹
c = 11.2854 (8) Å	T = 200 K
α = 73.537 (3)°	0.5 × 0.4 × 0.3 mm
β = 88.138 (3)°

Data collection top

Bruker D8 Venture CMOS diffractometer	3607 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2014)	3140 reflections with I > 2σ(I)
T_min = 0.717, T_max = 0.745	R_int = 0.028
28827 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	2 restraints
wR(F²) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.31 e Å⁻³
3607 reflections	Δρ_min = −0.29 e Å⁻³
249 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
S1	−0.30805 (5)	0.81860 (5)	0.70119 (4)	0.04242 (15)
O2	0.20072 (17)	0.30404 (15)	0.70998 (12)	0.0599 (4)
O1	0.19444 (14)	0.62852 (15)	0.58373 (13)	0.0495 (3)
N1	−0.11758 (15)	0.57436 (16)	0.58744 (13)	0.0363 (3)
C5	−0.2987 (2)	0.3401 (2)	0.80627 (15)	0.0417 (4)
H5	−0.2982	0.2402	0.8287	0.050*
C4	−0.3909 (2)	0.4374 (2)	0.86382 (16)	0.0475 (5)
H4	−0.4536	0.4053	0.9244	0.057*
C3	−0.38852 (19)	0.5810 (2)	0.83053 (15)	0.0428 (4)
H3	−0.4499	0.6482	0.8697	0.051*
C2	−0.29859 (17)	0.63076 (18)	0.74082 (14)	0.0343 (4)
C7	−0.15499 (19)	0.81895 (18)	0.78363 (14)	0.0364 (4)
C8	−0.1379 (2)	0.9553 (2)	0.77518 (17)	0.0486 (5)
H8	−0.2073	1.0430	0.7273	0.058*
C9	−0.0207 (3)	0.9644 (2)	0.83585 (19)	0.0584 (5)
H9	−0.0101	1.0583	0.8296	0.070*
C10	0.0814 (3)	0.8377 (2)	0.90577 (18)	0.0559 (5)
H10	0.1620	0.8442	0.9474	0.067*
C6	−0.20865 (18)	0.38618 (18)	0.71778 (14)	0.0358 (4)
H6	−0.1463	0.3161	0.6818	0.043*
C1	−0.20482 (16)	0.53452 (17)	0.67779 (13)	0.0305 (3)
C11	0.0650 (2)	0.7019 (2)	0.91449 (17)	0.0496 (5)
H11	0.1351	0.6147	0.9622	0.060*
C12	−0.0523 (2)	0.69133 (19)	0.85455 (15)	0.0409 (4)
H12	−0.0630	0.5973	0.8617	0.049*
C13	0.3512 (2)	0.5869 (3)	0.5733 (2)	0.0645 (6)
H13A	0.3806	0.5253	0.5159	0.077*
H13B	0.4024	0.5306	0.6552	0.077*
C16	0.1363 (3)	0.7835 (2)	0.5654 (2)	0.0651 (6)
H16A	0.0683	0.8051	0.6299	0.078*
H16B	0.0841	0.8331	0.4831	0.078*
C15	0.2689 (4)	0.8345 (3)	0.5745 (2)	0.0821 (8)
H15A	0.2522	0.9379	0.5237	0.098*
H15B	0.2940	0.8255	0.6613	0.098*
C14	0.3859 (3)	0.7291 (3)	0.5241 (2)	0.0685 (7)
H14A	0.3803	0.7608	0.4325	0.082*
H14B	0.4840	0.7204	0.5548	0.082*
C19A	0.339 (2)	0.1959 (19)	0.8969 (15)	0.072 (4)	0.335 (16)
H19A	0.4223	0.2352	0.8796	0.086*	0.335 (16)
H19B	0.3322	0.1589	0.9874	0.086*	0.335 (16)
C19	0.2946 (10)	0.1622 (9)	0.9113 (7)	0.0678 (19)	0.665 (16)
H19C	0.2378	0.0942	0.9484	0.081*	0.665 (16)
H19D	0.3514	0.1730	0.9776	0.081*	0.665 (16)
C18A	0.3465 (19)	0.0797 (15)	0.8334 (7)	0.085 (5)	0.335 (16)
H18A	0.4470	0.0124	0.8387	0.102*	0.335 (16)
H18B	0.2806	0.0212	0.8692	0.102*	0.335 (16)
C18	0.3925 (10)	0.1098 (14)	0.8142 (6)	0.106 (4)	0.665 (16)
H18C	0.4769	0.1483	0.8042	0.128*	0.665 (16)
H18D	0.4282	0.0007	0.8367	0.128*	0.665 (16)
C17	0.2979 (3)	0.1703 (3)	0.7028 (2)	0.0780 (8)
H17A	0.3555	0.1867	0.6289	0.094*	0.665 (16)
H17B	0.2443	0.1015	0.6969	0.094*	0.665 (16)
H17C	0.3821	0.1873	0.6553	0.094*	0.335 (16)
H17D	0.2493	0.1196	0.6616	0.094*	0.335 (16)
C20	0.1985 (3)	0.3084 (3)	0.83512 (19)	0.0763 (8)
H20A	0.0981	0.3262	0.8631	0.092*	0.665 (16)
H20B	0.2351	0.3888	0.8430	0.092*	0.665 (16)
H20C	0.1136	0.2826	0.8751	0.092*	0.335 (16)
H20D	0.1941	0.4079	0.8394	0.092*	0.335 (16)
Li1	0.1010 (3)	0.4805 (3)	0.5771 (3)	0.0373 (6)
H1	−0.127 (2)	0.666 (2)	0.5744 (18)	0.046 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0422 (3)	0.0367 (2)	0.0421 (3)	0.00113 (18)	−0.00049 (18)	−0.01541 (18)
O2	0.0736 (10)	0.0496 (8)	0.0369 (7)	0.0096 (7)	0.0010 (6)	−0.0123 (6)
O1	0.0451 (7)	0.0522 (8)	0.0577 (8)	−0.0190 (6)	0.0086 (6)	−0.0220 (6)
N1	0.0379 (8)	0.0371 (8)	0.0343 (7)	−0.0095 (6)	0.0115 (6)	−0.0136 (6)
C5	0.0497 (10)	0.0467 (10)	0.0314 (8)	−0.0207 (8)	0.0013 (7)	−0.0087 (7)
C4	0.0455 (10)	0.0687 (13)	0.0324 (9)	−0.0245 (9)	0.0137 (8)	−0.0148 (8)
C3	0.0375 (9)	0.0577 (11)	0.0330 (9)	−0.0083 (8)	0.0100 (7)	−0.0201 (8)
C2	0.0317 (8)	0.0409 (9)	0.0294 (8)	−0.0058 (7)	0.0028 (6)	−0.0143 (7)
C7	0.0462 (9)	0.0362 (8)	0.0245 (7)	−0.0061 (7)	0.0070 (7)	−0.0127 (6)
C8	0.0678 (13)	0.0328 (9)	0.0402 (10)	−0.0062 (8)	−0.0025 (9)	−0.0119 (7)
C9	0.0858 (16)	0.0410 (10)	0.0524 (12)	−0.0225 (10)	−0.0062 (11)	−0.0153 (9)
C10	0.0712 (14)	0.0565 (12)	0.0444 (11)	−0.0254 (10)	−0.0089 (10)	−0.0134 (9)
C6	0.0387 (9)	0.0396 (9)	0.0300 (8)	−0.0090 (7)	0.0026 (7)	−0.0142 (7)
C1	0.0270 (7)	0.0389 (8)	0.0243 (7)	−0.0054 (6)	0.0004 (6)	−0.0119 (6)
C11	0.0600 (12)	0.0427 (10)	0.0393 (10)	−0.0115 (9)	−0.0085 (8)	−0.0045 (8)
C12	0.0525 (10)	0.0334 (8)	0.0340 (9)	−0.0107 (8)	0.0007 (7)	−0.0080 (7)
C13	0.0451 (11)	0.0752 (15)	0.0701 (14)	−0.0195 (11)	−0.0112 (10)	−0.0131 (12)
C16	0.0808 (16)	0.0516 (12)	0.0715 (14)	−0.0256 (11)	0.0367 (12)	−0.0287 (11)
C15	0.139 (3)	0.0798 (17)	0.0572 (14)	−0.0705 (18)	0.0168 (15)	−0.0269 (13)
C14	0.0582 (13)	0.0924 (18)	0.0600 (13)	−0.0404 (13)	−0.0098 (11)	−0.0094 (12)
C19A	0.081 (9)	0.084 (8)	0.042 (5)	−0.026 (5)	0.002 (5)	−0.003 (5)
C19	0.073 (4)	0.066 (4)	0.040 (3)	0.004 (3)	0.000 (2)	−0.006 (3)
C18A	0.076 (9)	0.047 (5)	0.091 (8)	0.011 (5)	0.016 (6)	0.009 (5)
C18	0.074 (5)	0.126 (7)	0.068 (3)	0.043 (4)	0.000 (3)	−0.028 (3)
C17	0.105 (2)	0.0522 (13)	0.0573 (14)	0.0086 (13)	0.0074 (13)	−0.0215 (11)
C20	0.102 (2)	0.0644 (14)	0.0389 (11)	0.0107 (13)	0.0029 (12)	−0.0180 (10)
Li1	0.0353 (14)	0.0407 (15)	0.0350 (14)	−0.0082 (12)	0.0055 (11)	−0.0136 (11)

Geometric parameters (Å, º) top

S1—C2	1.7631 (17)	C13—H13B	0.9900
S1—C7	1.7730 (18)	C13—C14	1.497 (3)
O2—C17	1.396 (2)	C16—H16A	0.9900
O2—C20	1.424 (2)	C16—H16B	0.9900
O2—Li1	1.957 (3)	C16—C15	1.527 (4)
O1—C13	1.453 (2)	C15—H15A	0.9900
O1—C16	1.424 (2)	C15—H15B	0.9900
O1—Li1	1.960 (3)	C15—C14	1.508 (4)
N1—C1	1.350 (2)	C14—H14A	0.9900
N1—Li1	2.047 (3)	C14—H14B	0.9900
N1—Li1ⁱ	2.067 (3)	C19A—H19A	0.9900
N1—H1	0.85 (2)	C19A—H19B	0.9900
C5—H5	0.9500	C19A—C18A	1.503 (5)
C5—C4	1.394 (3)	C19A—C20	1.506 (18)
C5—C6	1.374 (2)	C19—H19C	0.9900
C4—H4	0.9500	C19—H19D	0.9900
C4—C3	1.373 (3)	C19—C18	1.523 (9)
C3—H3	0.9500	C19—C20	1.495 (8)
C3—C2	1.393 (2)	C18A—H18A	0.9900
C2—C1	1.435 (2)	C18A—H18B	0.9900
C7—C8	1.389 (2)	C18A—C17	1.496 (5)
C7—C12	1.395 (2)	C18—H18C	0.9900
C8—H8	0.9500	C18—H18D	0.9900
C8—C9	1.379 (3)	C18—C17	1.446 (7)
C9—H9	0.9500	C17—H17A	0.9900
C9—C10	1.383 (3)	C17—H17B	0.9900
C10—H10	0.9500	C17—H17C	0.9900
C10—C11	1.379 (3)	C17—H17D	0.9900
C6—H6	0.9500	C20—H20A	0.9900
C6—C1	1.423 (2)	C20—H20B	0.9900
C11—H11	0.9500	C20—H20C	0.9900
C11—C12	1.384 (3)	C20—H20D	0.9900
C12—H12	0.9500	Li1—N1ⁱ	2.067 (3)
C13—H13A	0.9900	Li1—Li1ⁱ	2.523 (6)

C2—S1—C7	103.95 (8)	C14—C15—H15B	111.3
C17—O2—C20	109.36 (16)	C13—C14—C15	102.65 (19)
C17—O2—Li1	129.63 (15)	C13—C14—H14A	111.2
C20—O2—Li1	120.28 (14)	C13—C14—H14B	111.2
C13—O1—Li1	116.03 (15)	C15—C14—H14A	111.2
C16—O1—C13	110.43 (16)	C15—C14—H14B	111.2
C16—O1—Li1	131.38 (16)	H14A—C14—H14B	109.1
C1—N1—Li1ⁱ	124.66 (14)	H19A—C19A—H19B	109.6
C1—N1—Li1	128.65 (14)	C18A—C19A—H19A	111.9
C1—N1—H1	108.9 (14)	C18A—C19A—H19B	111.9
Li1—N1—Li1ⁱ	75.65 (13)	C18A—C19A—C20	99.3 (12)
Li1ⁱ—N1—H1	110.8 (14)	C20—C19A—H19A	111.9
Li1—N1—H1	103.8 (14)	C20—C19A—H19B	111.9
C4—C5—H5	119.4	H19C—C19—H19D	109.3
C6—C5—H5	119.4	C18—C19—H19C	111.5
C6—C5—C4	121.22 (17)	C18—C19—H19D	111.5
C5—C4—H4	120.9	C20—C19—H19C	111.5
C3—C4—C5	118.21 (16)	C20—C19—H19D	111.5
C3—C4—H4	120.9	C20—C19—C18	101.3 (6)
C4—C3—H3	119.1	C19A—C18A—H18A	111.3
C4—C3—C2	121.79 (16)	C19A—C18A—H18B	111.3
C2—C3—H3	119.1	H18A—C18A—H18B	109.2
C3—C2—S1	118.23 (13)	C17—C18A—C19A	102.2 (10)
C3—C2—C1	121.48 (16)	C17—C18A—H18A	111.3
C1—C2—S1	120.23 (12)	C17—C18A—H18B	111.3
C8—C7—S1	117.10 (13)	C19—C18—H18C	111.1
C8—C7—C12	119.08 (17)	C19—C18—H18D	111.1
C12—C7—S1	123.82 (13)	H18C—C18—H18D	109.1
C7—C8—H8	119.8	C17—C18—C19	103.4 (6)
C9—C8—C7	120.44 (17)	C17—C18—H18C	111.1
C9—C8—H8	119.8	C17—C18—H18D	111.1
C8—C9—H9	119.8	O2—C17—C18A	106.2 (7)
C8—C9—C10	120.43 (18)	O2—C17—C18	107.1 (4)
C10—C9—H9	119.8	O2—C17—H17A	110.3
C9—C10—H10	120.3	O2—C17—H17B	110.3
C11—C10—C9	119.42 (19)	O2—C17—H17C	110.5
C11—C10—H10	120.3	O2—C17—H17D	110.5
C5—C6—H6	118.6	C18A—C17—H17C	110.5
C5—C6—C1	122.75 (15)	C18A—C17—H17D	110.5
C1—C6—H6	118.6	C18—C17—H17A	110.3
N1—C1—C2	125.42 (15)	C18—C17—H17B	110.3
N1—C1—C6	120.06 (14)	H17A—C17—H17B	108.6
C6—C1—C2	114.52 (14)	H17C—C17—H17D	108.7
C10—C11—H11	119.6	O2—C20—C19A	105.0 (6)
C10—C11—C12	120.72 (18)	O2—C20—C19	107.0 (3)
C12—C11—H11	119.6	O2—C20—H20A	110.3
C7—C12—H12	120.1	O2—C20—H20B	110.3
C11—C12—C7	119.90 (16)	O2—C20—H20C	110.7
C11—C12—H12	120.1	O2—C20—H20D	110.7
O1—C13—H13A	110.6	C19A—C20—H20C	110.7
O1—C13—H13B	110.6	C19A—C20—H20D	110.7
O1—C13—C14	105.51 (18)	C19—C20—H20A	110.3
H13A—C13—H13B	108.8	C19—C20—H20B	110.3
C14—C13—H13A	110.6	H20A—C20—H20B	108.6
C14—C13—H13B	110.6	H20C—C20—H20D	108.8
O1—C16—H16A	110.8	O2—Li1—O1	105.23 (14)
O1—C16—H16B	110.8	O2—Li1—N1	117.69 (14)
O1—C16—C15	104.7 (2)	O2—Li1—N1ⁱ	108.46 (14)
H16A—C16—H16B	108.9	O2—Li1—Li1ⁱ	129.5 (2)
C15—C16—H16A	110.8	O1—Li1—N1ⁱ	114.96 (14)
C15—C16—H16B	110.8	O1—Li1—N1	106.56 (14)
C16—C15—H15A	111.3	O1—Li1—Li1ⁱ	125.23 (19)
C16—C15—H15B	111.3	N1—Li1—N1ⁱ	104.35 (13)
H15A—C15—H15B	109.2	N1—Li1—Li1ⁱ	52.53 (10)
C14—C15—C16	102.42 (17)	N1ⁱ—Li1—Li1ⁱ	51.82 (10)
C14—C15—H15A	111.3

S1—C2—C1—N1	0.7 (2)	C12—C7—C8—C9	0.2 (3)
S1—C2—C1—C6	−179.37 (11)	C13—O1—C16—C15	−13.8 (2)
S1—C7—C8—C9	−179.42 (16)	C16—O1—C13—C14	−10.1 (2)
S1—C7—C12—C11	179.10 (14)	C16—C15—C14—C13	−37.5 (2)
O1—C13—C14—C15	29.9 (2)	C19A—C18A—C17—O2	−30.5 (14)
O1—C16—C15—C14	31.9 (2)	C19—C18—C17—O2	32.4 (12)
C5—C4—C3—C2	0.8 (3)	C18A—C19A—C20—O2	−37.9 (13)
C5—C6—C1—N1	−177.75 (15)	C18—C19—C20—O2	22.8 (11)
C5—C6—C1—C2	2.3 (2)	C17—O2—C20—C19A	20.4 (7)
C4—C5—C6—C1	−1.0 (3)	C17—O2—C20—C19	−3.8 (5)
C4—C3—C2—S1	177.98 (14)	C20—O2—C17—C18A	6.4 (7)
C4—C3—C2—C1	0.6 (3)	C20—O2—C17—C18	−18.4 (7)
C3—C2—C1—N1	177.97 (15)	C20—C19A—C18A—C17	40.7 (16)
C3—C2—C1—C6	−2.1 (2)	C20—C19—C18—C17	−33.1 (13)
C2—S1—C7—C8	−176.80 (13)	Li1—O2—C17—C18A	176.5 (7)
C2—S1—C7—C12	3.65 (16)	Li1—O2—C17—C18	151.6 (6)
C7—S1—C2—C3	100.61 (14)	Li1—O2—C20—C19A	−150.7 (7)
C7—S1—C2—C1	−82.00 (14)	Li1—O2—C20—C19	−175.0 (5)
C7—C8—C9—C10	0.1 (3)	Li1—O1—C13—C14	155.11 (17)
C8—C7—C12—C11	−0.4 (3)	Li1—O1—C16—C15	−176.02 (17)
C8—C9—C10—C11	−0.1 (3)	Li1ⁱ—N1—C1—C2	−133.47 (17)
C9—C10—C11—C12	−0.2 (3)	Li1—N1—C1—C2	126.91 (18)
C10—C11—C12—C7	0.5 (3)	Li1ⁱ—N1—C1—C6	46.6 (2)
C6—C5—C4—C3	−0.6 (3)	Li1—N1—C1—C6	−53.1 (2)

Symmetry code: (i) −x, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	[Li₂(C₁₂H₁₀NS)₂(C₄H₈O)₄]
M_r	702.83
Crystal system, space group	Triclinic, P1
Temperature (K)	200
a, b, c (Å)	9.6540 (7), 9.9211 (6), 11.2854 (8)
α, β, γ (°)	73.537 (3), 88.138 (3), 72.420 (3)
V (Å³)	986.50 (12)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.18
Crystal size (mm)	0.5 × 0.4 × 0.3

Data collection
Diffractometer	Bruker D8 Venture CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2014)
T_min, T_max	0.717, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	28827, 3607, 3140
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.604

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.111, 1.06
No. of reflections	3607
No. of parameters	249
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.29

Computer programs: APEX2 (Bruker, 2014), SAINT (Bruker, 2014), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), OLEX2 (Dolomanov et al., 2009) and publCIF (Westrip, 2010).

Acknowledgements

We greatly acknowledge support from the National Science Foundation (CHE-1429086).

References

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