Structure of salts of lithium chloride and lithium hexa­fluoro­phosphate as solvates with pyridine and vinyl­pyridine and structural comparisons: (C₅H₅N)LiPF₆, [p-(CH₂=CH)C₅H₄N]LiPF₆, [(C₅H₅N)LiCl]_n, and [p-(CH₂=CH)C₅H₄N]₂Li(μ-Cl)₂Li[p-(CH₂=CH)C₅H₄N]₂

Due to the flammability of liquid electrolytes used in lithium ion batteries, solid lithium ion conductors are of inter­est to reduce danger and increase safety. The two dominating general classes of electrolytes under exploration as alternatives are ceramic and polymer electrolytes. Our group has been exploring the preparation of mol­ecular solvates of lithium salts as alternatives. Dissolution of LiCl or LiPF₆ in pyridine (py) or vinyl­pyridine (VnPy) and slow vapor diffusion with diethyl ether gives solvates of the lithium salts coordinated by pyridine ligands. For LiPF₆, the solvates formed in pyridine and vinyl­pyridine, namely tetra­kis­(pyridine-κN)lithium(I) hexa­fluoro­phosphate, [Li(C₅H₅N)₄]PF₆, and tetra­kis­(4-ethenyl­pyridine-κN)lithium(I) hexa­fluoro­phosphate, [Li(C₇H₇N)₄]PF₆, exhibit analogous structures involving tetra­coordinated lithium ions with neighboring PF₆⁻ anions in the I and Aea2 space groups, respectively. For LiCl solvates, two very different structures form. catena-Poly[[(pyridine-κN)lithium]-μ₃-chlorido], [LiCl(C₅H₅N)]_n, crystalizes in the P2₁2₁2₁ space group and contains channels of edge-fused LiCl rhombs templated by rows of π-stacked pyridine ligands, while the structure of the LiCl–VnPy solvate, namely di-μ-chlorido-bis­[bis(4-ethenyl­pyridine-κN)lithium], [Li₂Cl₂(C₇H₇N)₄], is described in the P2₁/n space group as dinuclear (VnPy)₂Li(μ-Cl)₂Li(VnPy)₂ units packed with neighbors via a dense array of π–π inter­actions.

Computing details

Data collection: SAINT (Bruker, 2008) for LiCl.Py, PyLiPF6; COSMO (Bruker, 2008) for VnPyLiPF6, VnPyLiCl. Cell refinement: APEX2 (Bruker, 2008) for LiCl.Py, PyLiPF6; SAINT (Bruker, 2008) for VnPyLiPF6, VnPyLiCl. Data reduction: SAINT (Bruker, 2008) for LiCl.Py, PyLiPF6, VnPyLiCl; SADABS (Bruker, 2008) for VnPyLiPF6. For all compounds, 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).

(LiCl.Py) catena-Poly[[(pyridine-κN)lithium]-µ₃-chlorido]

Crystal data

[LiCl(C5H5N)]	Dx = 1.335 Mg m^−3
Mr = 121.49	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 1105 reflections
a = 3.9329 (17) Å	θ = 3.3–28.0°
b = 8.615 (4) Å	µ = 0.50 mm^−1
c = 17.836 (7) Å	T = 100 K
V = 604.3 (4) Å^3	Prism, colourless
Z = 4	0.25 × 0.09 × 0.05 mm
F(000) = 248

Data collection

Bruker APEXII CCD diffractometer	1220 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
φ and ω scans	θmax = 28.1°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −5→2
Tmin = 0.546, Tmax = 0.746	k = −11→7
2313 measured reflections	l = −23→19
1328 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.029	w = 1/[σ^2(Fo^2) + (0.0293P)^2 + 0.1143P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.067	(Δ/σ)max = 0.001
S = 1.06	Δρmax = 0.27 e Å^−3
1328 reflections	Δρmin = −0.22 e Å^−3
74 parameters	Absolute structure: Refined as an inversion twin
0 restraints	Absolute structure parameter: 0.68 (12)

Special details

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

Refinement. Refined as a 2-component inversion twin.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C2	0.7280 (7)	0.4721 (3)	0.32361 (15)	0.0215 (6)
H2	0.8063	0.5632	0.2990	0.026*
C3	0.7698 (6)	0.3315 (3)	0.28749 (14)	0.0265 (5)
H3	0.8699	0.3265	0.2391	0.032*
C4	0.6618 (7)	0.1984 (3)	0.32371 (16)	0.0273 (6)
H4	0.6911	0.0995	0.3010	0.033*
C5	0.5111 (7)	0.2114 (3)	0.39323 (14)	0.0245 (5)
H5	0.4319	0.1219	0.4190	0.029*
C6	0.4776 (6)	0.3574 (2)	0.42465 (13)	0.0218 (5)
H6	0.3737	0.3656	0.4726	0.026*
N1	0.5838 (5)	0.4877 (2)	0.39114 (11)	0.0189 (4)
Cl1	0.53512 (13)	0.66119 (6)	0.57635 (3)	0.01760 (14)
Li1	0.5376 (11)	0.6961 (4)	0.4424 (2)	0.0225 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C2	0.0237 (12)	0.0187 (13)	0.0221 (12)	−0.0007 (11)	0.0009 (10)	0.0037 (12)
C3	0.0288 (12)	0.0290 (14)	0.0217 (11)	0.0039 (14)	0.0005 (10)	−0.0031 (13)
C4	0.0307 (14)	0.0179 (12)	0.0334 (14)	0.0037 (11)	−0.0095 (12)	−0.0083 (12)
C5	0.0270 (13)	0.0158 (10)	0.0307 (11)	−0.0040 (11)	−0.0060 (12)	0.0024 (9)
C6	0.0253 (11)	0.0183 (10)	0.0217 (9)	−0.0021 (11)	0.0000 (12)	0.0012 (10)
N1	0.0207 (10)	0.0147 (9)	0.0214 (9)	−0.0005 (9)	−0.0020 (9)	0.0001 (8)
Cl1	0.0182 (2)	0.0137 (2)	0.0209 (2)	0.0003 (2)	0.0001 (2)	0.0020 (2)
Li1	0.025 (2)	0.0172 (18)	0.0248 (18)	0.0005 (17)	0.0013 (18)	−0.0013 (15)

Geometric parameters (Å, º)

C2—H2	0.9500	C6—N1	1.339 (3)
C2—C3	1.382 (4)	N1—Li1	2.022 (4)
C2—N1	1.338 (3)	Cl1—Li1^i	2.351 (4)
C3—H3	0.9500	Cl1—Li1^ii	2.335 (4)
C3—C4	1.384 (4)	Cl1—Li1	2.409 (4)
C4—H4	0.9500	Li1—Cl1^i	2.335 (4)
C4—C5	1.379 (4)	Li1—Cl1^ii	2.351 (4)
C5—H5	0.9500	Li1—Li1^i	2.993 (6)
C5—C6	1.383 (3)	Li1—Li1^ii	2.993 (6)
C6—H6	0.9500
C3—C2—H2	118.0	Li1^ii—Cl1—Li1^i	114.11 (16)
N1—C2—H2	118.0	Li1^ii—Cl1—Li1	78.22 (13)
N1—C2—C3	123.9 (2)	Li1^i—Cl1—Li1	77.91 (13)
C2—C3—H3	120.9	N1—Li1—Cl1^i	109.13 (19)
C2—C3—C4	118.2 (2)	N1—Li1—Cl1	109.74 (17)
C4—C3—H3	120.9	N1—Li1—Cl1^ii	118.4 (2)
C3—C4—H4	120.5	N1—Li1—Li1^ii	130.2 (2)
C5—C4—C3	119.0 (2)	N1—Li1—Li1^i	121.80 (19)
C5—C4—H4	120.5	Cl1^i—Li1—Cl1^ii	114.11 (16)
C4—C5—H5	120.7	Cl1^i—Li1—Cl1	102.17 (16)
C4—C5—C6	118.6 (2)	Cl1^ii—Li1—Cl1	101.69 (15)
C6—C5—H5	120.7	Cl1^ii—Li1—Li1^i	119.2 (2)
C5—C6—H6	118.2	Cl1—Li1—Li1^ii	49.79 (14)
N1—C6—C5	123.5 (2)	Cl1^ii—Li1—Li1^ii	51.90 (7)
N1—C6—H6	118.2	Cl1—Li1—Li1^i	50.19 (15)
C2—N1—C6	116.7 (2)	Cl1^i—Li1—Li1^i	51.98 (7)
C2—N1—Li1	122.3 (2)	Cl1^i—Li1—Li1^ii	119.0 (2)
C6—N1—Li1	120.98 (19)	Li1^i—Li1—Li1^ii	82.14 (19)
C2—C3—C4—C5	1.4 (4)	C4—C5—C6—N1	0.0 (4)
C3—C2—N1—C6	0.4 (4)	C5—C6—N1—C2	0.2 (4)
C3—C2—N1—Li1	178.7 (2)	C5—C6—N1—Li1	−178.2 (3)
C3—C4—C5—C6	−0.9 (4)	N1—C2—C3—C4	−1.2 (4)

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

(VnPyLiPF6) Tetrakis(4-ethenylpyridine-κN)lithium(I) hexafluoridophosphate

Crystal data

[Li(C7H7N)4]PF6	Dx = 1.321 Mg m^−3
Mr = 572.45	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Aea2	Cell parameters from 9047 reflections
a = 24.725 (3) Å	θ = 2.5–30.7°
b = 14.7026 (18) Å	µ = 0.16 mm^−1
c = 15.8325 (19) Å	T = 100 K
V = 5755.4 (12) Å^3	Plate, white
Z = 8	0.22 × 0.2 × 0.13 mm
F(000) = 2368

Data collection

Bruker Kappa APEXII DUO diffractometer	7552 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.024
φ and ω scans	θmax = 31.8°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −35→35
Tmin = 0.676, Tmax = 0.746	k = −21→21
47438 measured reflections	l = −23→18
8431 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.038	H-atom parameters constrained
wR(F^2) = 0.098	w = 1/[σ^2(Fo^2) + (0.0445P)^2 + 3.0263P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max < 0.001
8431 reflections	Δρmax = 0.35 e Å^−3
413 parameters	Δρmin = −0.18 e Å^−3
89 restraints	Absolute structure: Flack x determined using 2975 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.02 (2)

Special details

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Li1	0.14201 (16)	0.9130 (3)	0.1775 (3)	0.0342 (8)
P1	0.10028 (2)	0.33816 (3)	0.21537 (4)	0.02714 (10)
F1	0.12130 (7)	0.32007 (12)	0.30912 (11)	0.0521 (4)
F2	0.12089 (7)	0.23982 (10)	0.18679 (11)	0.0506 (4)
F3	0.07900 (7)	0.35560 (11)	0.12108 (10)	0.0472 (4)
F4	0.07900 (7)	0.43618 (10)	0.24373 (11)	0.0495 (4)
F5	0.15716 (7)	0.38102 (14)	0.19032 (14)	0.0720 (6)
F6	0.04304 (5)	0.29565 (10)	0.23922 (10)	0.0430 (3)
N1	0.07919 (7)	0.89967 (14)	0.09429 (13)	0.0346 (4)
N2	0.19757 (7)	0.99627 (13)	0.11855 (13)	0.0336 (4)
N3	0.17298 (7)	0.78979 (11)	0.21588 (13)	0.0323 (3)
C1A	0.22631 (15)	0.7930 (4)	0.2435 (6)	0.030 (3)	0.344 (10)
H1A	0.2464	0.8479	0.2389	0.037*	0.344 (10)
C2A	0.2503 (2)	0.7159 (6)	0.2779 (8)	0.033 (2)	0.344 (10)
H2A	0.2867	0.7182	0.2968	0.040*	0.344 (10)
C3A	0.2209 (3)	0.6356 (4)	0.2847 (6)	0.0290 (15)	0.344 (10)
C4A	0.1676 (4)	0.6324 (3)	0.2570 (8)	0.0346 (18)	0.344 (10)
H4A	0.1475	0.5775	0.2617	0.042*	0.344 (10)
C5A	0.1436 (2)	0.7095 (3)	0.2226 (6)	0.033 (2)	0.344 (10)
H5A	0.1072	0.7073	0.2037	0.039*	0.344 (10)
N4	0.10509 (8)	0.96988 (13)	0.28383 (13)	0.0339 (4)
C1	0.2214 (2)	0.7750 (4)	0.2498 (4)	0.0322 (10)	0.656 (10)
H1	0.2457	0.8249	0.2521	0.039*	0.656 (10)
C2	0.2391 (2)	0.6935 (4)	0.2817 (4)	0.0330 (10)	0.656 (10)
H2	0.2747	0.6879	0.3036	0.040*	0.656 (10)
C3	0.2039 (2)	0.6187 (3)	0.2817 (4)	0.0289 (9)	0.656 (10)
C4	0.1533 (2)	0.6327 (3)	0.2435 (5)	0.0342 (9)	0.656 (10)
H4	0.1278	0.5845	0.2395	0.041*	0.656 (10)
C5	0.1412 (2)	0.7187 (3)	0.2117 (5)	0.0367 (12)	0.656 (10)
H5	0.1071	0.7264	0.1849	0.044*	0.656 (10)
C6A	0.2455 (5)	0.5528 (6)	0.3308 (5)	0.038 (2)	0.344 (10)
H6A	0.2835	0.5537	0.3406	0.046*	0.344 (10)
C6	0.2183 (2)	0.5305 (3)	0.3166 (3)	0.0387 (12)	0.656 (10)
H6	0.1921	0.4833	0.3124	0.046*	0.656 (10)
C7A	0.2191 (5)	0.4815 (5)	0.3576 (6)	0.056 (3)	0.344 (10)
H7AA	0.1811	0.4775	0.3493	0.067*	0.344 (10)
H7AB	0.2378	0.4336	0.3855	0.067*	0.344 (10)
C7	0.2638 (2)	0.5108 (3)	0.3531 (3)	0.0495 (14)	0.656 (10)
H7A	0.2910	0.5560	0.3586	0.059*	0.656 (10)
H7B	0.2699	0.4513	0.3743	0.059*	0.656 (10)
C8	0.08223 (10)	0.91691 (17)	0.01165 (16)	0.0364 (5)
H8	0.1149	0.9417	−0.0100	0.044*
C9	0.04003 (10)	0.90054 (16)	−0.04454 (15)	0.0372 (5)
H9	0.0441	0.9141	−0.1029	0.045*
C10	−0.00820 (9)	0.86414 (15)	−0.01456 (14)	0.0316 (4)
C11	−0.01175 (9)	0.84603 (15)	0.07169 (14)	0.0322 (4)
H11	−0.0439	0.8211	0.0950	0.039*
C12	0.03237 (9)	0.86497 (17)	0.12304 (15)	0.0340 (4)
H12	0.0293	0.8527	0.1818	0.041*
C13	−0.05394 (12)	0.84616 (17)	−0.07238 (18)	0.0422 (6)
H13	−0.0516	0.8701	−0.1280	0.051*
C14	−0.09769 (12)	0.79964 (18)	−0.05298 (19)	0.0480 (6)
H14A	−0.1016	0.7745	0.0020	0.058*
H14B	−0.1253	0.7911	−0.0939	0.058*
C15	0.10539 (9)	0.93168 (15)	0.36077 (16)	0.0326 (4)
H15	0.1206	0.8726	0.3663	0.039*
C16	0.08502 (8)	0.97286 (14)	0.43260 (14)	0.0292 (4)
H16	0.0858	0.9418	0.4852	0.035*
C17	0.06338 (8)	1.06011 (14)	0.42741 (15)	0.0286 (4)
C18	0.06200 (11)	1.09908 (16)	0.34747 (17)	0.0408 (6)
H18	0.0468	1.1578	0.3399	0.049*
C19	0.08276 (11)	1.05246 (18)	0.27898 (18)	0.0444 (6)
H19	0.0810	1.0809	0.2252	0.053*
C20	0.04202 (9)	1.11046 (15)	0.50041 (17)	0.0352 (5)
H20	0.0246	1.1667	0.4892	0.042*
C21	0.04486 (9)	1.08451 (17)	0.58049 (16)	0.0361 (5)
H21A	0.0619	1.0287	0.5948	0.043*
H21B	0.0298	1.1217	0.6236	0.043*
C22	0.24872 (9)	0.97492 (17)	0.09983 (16)	0.0362 (5)
H22	0.2606	0.9145	0.1103	0.043*
C23	0.28526 (9)	1.03606 (19)	0.06597 (17)	0.0410 (5)
H23	0.3214	1.0176	0.0553	0.049*
C24	0.26935 (8)	1.12403 (17)	0.04759 (14)	0.0330 (4)
C25	0.21660 (10)	1.14679 (16)	0.06709 (19)	0.0414 (6)
H25	0.2037	1.2067	0.0571	0.050*
C26	0.18271 (10)	1.08169 (17)	0.1012 (2)	0.0468 (7)
H26	0.1465	1.0988	0.1132	0.056*
C27	0.30739 (10)	1.1894 (2)	0.00872 (18)	0.0469 (6)
H27	0.3445	1.1724	0.0077	0.056*
C28	0.29522 (14)	1.2675 (2)	−0.0241 (2)	0.0571 (8)
H28A	0.2587	1.2876	−0.0247	0.068*
H28B	0.3228	1.3047	−0.0476	0.068*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Li1	0.0343 (18)	0.0331 (18)	0.035 (2)	0.0036 (14)	0.0031 (15)	0.0067 (16)
P1	0.0258 (2)	0.0242 (2)	0.0315 (3)	−0.00090 (16)	0.0031 (2)	0.0018 (2)
F1	0.0568 (9)	0.0595 (10)	0.0401 (9)	0.0110 (8)	−0.0191 (7)	−0.0036 (8)
F2	0.0580 (9)	0.0369 (7)	0.0568 (10)	0.0200 (7)	−0.0059 (7)	−0.0082 (7)
F3	0.0678 (10)	0.0437 (8)	0.0299 (8)	0.0078 (7)	0.0038 (7)	0.0103 (6)
F4	0.0750 (11)	0.0257 (6)	0.0479 (9)	0.0074 (7)	0.0129 (8)	0.0004 (6)
F5	0.0433 (9)	0.0842 (13)	0.0885 (16)	−0.0298 (9)	0.0251 (9)	−0.0150 (11)
F6	0.0308 (6)	0.0489 (8)	0.0493 (9)	−0.0090 (6)	0.0041 (6)	0.0118 (7)
N1	0.0313 (8)	0.0413 (10)	0.0311 (10)	0.0071 (7)	0.0024 (7)	0.0056 (8)
N2	0.0322 (9)	0.0336 (9)	0.0351 (10)	0.0040 (7)	0.0070 (7)	0.0021 (8)
N3	0.0432 (9)	0.0259 (7)	0.0277 (9)	0.0009 (6)	−0.0031 (8)	−0.0002 (8)
C1A	0.049 (5)	0.011 (4)	0.031 (4)	−0.007 (3)	−0.007 (3)	0.008 (3)
C2A	0.050 (4)	0.018 (4)	0.031 (4)	−0.008 (3)	0.006 (4)	0.004 (3)
C3A	0.048 (4)	0.017 (3)	0.023 (3)	−0.004 (2)	0.012 (3)	0.001 (3)
C4A	0.054 (4)	0.024 (3)	0.026 (4)	−0.004 (3)	0.002 (4)	−0.002 (2)
C5A	0.044 (4)	0.022 (3)	0.032 (5)	−0.010 (3)	0.005 (3)	0.001 (3)
N4	0.0354 (9)	0.0364 (10)	0.0299 (10)	0.0062 (7)	0.0049 (7)	0.0076 (8)
C1	0.045 (2)	0.0168 (14)	0.034 (2)	−0.0065 (14)	−0.0074 (17)	0.0015 (15)
C2	0.045 (2)	0.0205 (19)	0.033 (2)	0.0005 (14)	−0.010 (2)	0.0020 (19)
C3	0.047 (2)	0.0170 (13)	0.0228 (16)	0.0003 (13)	0.0061 (19)	−0.0021 (13)
C4	0.0456 (19)	0.0282 (15)	0.029 (3)	−0.0038 (13)	0.0004 (17)	−0.0030 (13)
C5	0.049 (2)	0.0322 (19)	0.028 (2)	0.0022 (17)	−0.0008 (18)	0.0003 (18)
C6A	0.056 (5)	0.026 (4)	0.033 (4)	0.009 (4)	−0.011 (3)	0.004 (3)
C6	0.054 (3)	0.0269 (19)	0.035 (2)	0.0061 (17)	−0.0077 (17)	−0.0054 (16)
C7A	0.105 (9)	0.026 (4)	0.035 (4)	−0.002 (4)	−0.012 (4)	0.006 (3)
C7	0.066 (3)	0.034 (2)	0.048 (3)	0.011 (2)	−0.011 (2)	−0.0021 (19)
C8	0.0384 (11)	0.0387 (12)	0.0321 (12)	0.0104 (9)	0.0093 (9)	0.0062 (9)
C9	0.0511 (13)	0.0383 (12)	0.0222 (10)	0.0132 (10)	0.0058 (9)	0.0039 (9)
C10	0.0432 (11)	0.0262 (9)	0.0255 (10)	0.0102 (8)	−0.0023 (8)	−0.0022 (8)
C11	0.0371 (11)	0.0327 (10)	0.0268 (11)	0.0038 (8)	0.0005 (8)	0.0004 (8)
C12	0.0345 (10)	0.0432 (12)	0.0243 (10)	0.0052 (9)	0.0019 (8)	0.0050 (9)
C13	0.0616 (16)	0.0356 (12)	0.0294 (12)	0.0067 (11)	−0.0112 (10)	−0.0039 (10)
C14	0.0629 (17)	0.0406 (13)	0.0405 (15)	0.0017 (12)	−0.0187 (12)	−0.0048 (11)
C15	0.0389 (11)	0.0255 (9)	0.0334 (12)	0.0054 (8)	0.0043 (8)	0.0074 (8)
C16	0.0344 (10)	0.0265 (9)	0.0268 (10)	0.0023 (7)	0.0027 (7)	0.0074 (8)
C17	0.0283 (9)	0.0239 (9)	0.0336 (11)	−0.0011 (7)	0.0026 (7)	0.0053 (8)
C18	0.0489 (13)	0.0320 (11)	0.0414 (14)	0.0132 (10)	0.0101 (10)	0.0148 (10)
C19	0.0536 (14)	0.0448 (13)	0.0349 (13)	0.0154 (11)	0.0104 (11)	0.0203 (11)
C20	0.0351 (10)	0.0270 (10)	0.0435 (13)	0.0032 (8)	0.0044 (9)	−0.0001 (9)
C21	0.0319 (10)	0.0376 (12)	0.0387 (13)	−0.0035 (8)	0.0036 (9)	−0.0063 (10)
C22	0.0330 (10)	0.0412 (12)	0.0343 (12)	0.0093 (9)	−0.0001 (9)	0.0035 (9)
C23	0.0243 (9)	0.0585 (15)	0.0404 (14)	0.0079 (9)	0.0028 (8)	0.0027 (12)
C24	0.0288 (9)	0.0475 (13)	0.0227 (10)	−0.0058 (9)	−0.0001 (7)	−0.0043 (9)
C25	0.0389 (12)	0.0301 (11)	0.0551 (16)	0.0013 (9)	0.0163 (11)	0.0029 (10)
C26	0.0355 (11)	0.0331 (11)	0.072 (2)	0.0059 (9)	0.0241 (12)	0.0061 (12)
C27	0.0346 (11)	0.0668 (17)	0.0392 (14)	−0.0173 (11)	0.0035 (9)	−0.0003 (13)
C28	0.0641 (18)	0.0568 (18)	0.0503 (18)	−0.0281 (15)	0.0141 (14)	−0.0041 (14)

Geometric parameters (Å, º)

Li1—N1	2.046 (5)	C7A—H7AB	0.9500
Li1—N2	2.063 (4)	C7—H7A	0.9500
Li1—N3	2.058 (4)	C7—H7B	0.9500
Li1—N4	2.090 (5)	C8—H8	0.9500
P1—F1	1.5950 (17)	C8—C9	1.392 (4)
P1—F2	1.5985 (15)	C9—H9	0.9500
P1—F3	1.6035 (17)	C9—C10	1.391 (3)
P1—F4	1.5985 (15)	C10—C11	1.394 (3)
P1—F5	1.5912 (16)	C10—C13	1.479 (3)
P1—F6	1.5925 (14)	C11—H11	0.9500
N1—C8	1.335 (3)	C11—C12	1.389 (3)
N1—C12	1.344 (3)	C12—H12	0.9500
N2—C22	1.336 (3)	C13—H13	0.9500
N2—C26	1.337 (3)	C13—C14	1.316 (4)
N3—C1A	1.3900	C14—H14A	0.9500
N3—C5A	1.3900	C14—H14B	0.9500
N3—C1	1.330 (5)	C15—H15	0.9500
N3—C5	1.310 (5)	C15—C16	1.383 (3)
C1A—H1A	0.9500	C16—H16	0.9500
C1A—C2A	1.3900	C16—C17	1.392 (3)
C2A—H2A	0.9500	C17—C18	1.390 (3)
C2A—C3A	1.3900	C17—C20	1.471 (3)
C3A—C4A	1.3900	C18—H18	0.9500
C3A—C6A	1.546 (8)	C18—C19	1.382 (4)
C4A—H4A	0.9500	C19—H19	0.9500
C4A—C5A	1.3900	C20—H20	0.9500
C5A—H5A	0.9500	C20—C21	1.326 (4)
N4—C15	1.341 (3)	C21—H21A	0.9500
N4—C19	1.336 (3)	C21—H21B	0.9500
C1—H1	0.9500	C22—H22	0.9500
C1—C2	1.372 (6)	C22—C23	1.382 (4)
C2—H2	0.9500	C23—H23	0.9500
C2—C3	1.402 (5)	C23—C24	1.383 (4)
C3—C4	1.405 (6)	C24—C25	1.382 (3)
C3—C6	1.455 (6)	C24—C27	1.479 (3)
C4—H4	0.9500	C25—H25	0.9500
C4—C5	1.393 (6)	C25—C26	1.382 (3)
C5—H5	0.9500	C26—H26	0.9500
C6A—H6A	0.9500	C27—H27	0.9500
C6A—C7A	1.307 (14)	C27—C28	1.296 (5)
C6—H6	0.9500	C28—H28A	0.9500
C6—C7	1.298 (7)	C28—H28B	0.9500
C7A—H7AA	0.9500
N1—Li1—N2	105.7 (2)	C7—C6—H6	117.3
N1—Li1—N3	112.9 (2)	C6A—C7A—H7AA	120.0
N1—Li1—N4	103.02 (18)	C6A—C7A—H7AB	120.0
N2—Li1—N4	114.7 (2)	H7AA—C7A—H7AB	120.0
N3—Li1—N2	114.09 (19)	C6—C7—H7A	120.0
N3—Li1—N4	106.1 (2)	C6—C7—H7B	120.0
F1—P1—F2	90.50 (9)	H7A—C7—H7B	120.0
F1—P1—F3	179.58 (11)	N1—C8—H8	118.3
F1—P1—F4	89.78 (9)	N1—C8—C9	123.5 (2)
F2—P1—F3	89.18 (9)	C9—C8—H8	118.3
F2—P1—F4	179.37 (10)	C8—C9—H9	120.3
F4—P1—F3	90.53 (9)	C10—C9—C8	119.4 (2)
F5—P1—F1	90.57 (11)	C10—C9—H9	120.3
F5—P1—F2	90.34 (10)	C9—C10—C11	117.5 (2)
F5—P1—F3	89.70 (11)	C9—C10—C13	120.9 (2)
F5—P1—F4	90.23 (10)	C11—C10—C13	121.6 (2)
F5—P1—F6	179.22 (12)	C10—C11—H11	120.5
F6—P1—F1	90.20 (10)	C12—C11—C10	119.1 (2)
F6—P1—F2	89.74 (9)	C12—C11—H11	120.5
F6—P1—F3	89.53 (9)	N1—C12—C11	123.7 (2)
F6—P1—F4	89.70 (9)	N1—C12—H12	118.2
C8—N1—Li1	124.8 (2)	C11—C12—H12	118.2
C8—N1—C12	116.9 (2)	C10—C13—H13	117.4
C12—N1—Li1	118.2 (2)	C14—C13—C10	125.2 (3)
C22—N2—Li1	126.2 (2)	C14—C13—H13	117.4
C22—N2—C26	115.8 (2)	C13—C14—H14A	120.0
C26—N2—Li1	117.88 (18)	C13—C14—H14B	120.0
C1A—N3—Li1	114.6 (2)	H14A—C14—H14B	120.0
C1A—N3—C5A	120.0	N4—C15—H15	117.9
C5A—N3—Li1	125.2 (2)	N4—C15—C16	124.14 (19)
C1—N3—Li1	126.7 (3)	C16—C15—H15	117.9
C5—N3—Li1	117.6 (3)	C15—C16—H16	120.2
C5—N3—C1	115.5 (4)	C15—C16—C17	119.6 (2)
N3—C1A—H1A	120.0	C17—C16—H16	120.2
C2A—C1A—N3	120.0	C16—C17—C20	123.7 (2)
C2A—C1A—H1A	120.0	C18—C17—C16	116.3 (2)
C1A—C2A—H2A	120.0	C18—C17—C20	119.95 (19)
C1A—C2A—C3A	120.0	C17—C18—H18	120.0
C3A—C2A—H2A	120.0	C19—C18—C17	120.1 (2)
C2A—C3A—C6A	120.0 (6)	C19—C18—H18	120.0
C4A—C3A—C2A	120.0	N4—C19—C18	124.0 (2)
C4A—C3A—C6A	119.7 (6)	N4—C19—H19	118.0
C3A—C4A—H4A	120.0	C18—C19—H19	118.0
C3A—C4A—C5A	120.0	C17—C20—H20	117.0
C5A—C4A—H4A	120.0	C21—C20—C17	126.0 (2)
N3—C5A—H5A	120.0	C21—C20—H20	117.0
C4A—C5A—N3	120.0	C20—C21—H21A	120.0
C4A—C5A—H5A	120.0	C20—C21—H21B	120.0
C15—N4—Li1	124.16 (18)	H21A—C21—H21B	120.0
C19—N4—Li1	119.9 (2)	N2—C22—H22	118.3
C19—N4—C15	115.8 (2)	N2—C22—C23	123.5 (2)
N3—C1—H1	117.3	C23—C22—H22	118.3
N3—C1—C2	125.4 (5)	C22—C23—H23	119.9
C2—C1—H1	117.3	C22—C23—C24	120.3 (2)
C1—C2—H2	120.4	C24—C23—H23	119.9
C1—C2—C3	119.1 (4)	C23—C24—C27	121.0 (2)
C3—C2—H2	120.4	C25—C24—C23	116.6 (2)
C2—C3—C4	116.0 (4)	C25—C24—C27	122.4 (2)
C2—C3—C6	123.2 (4)	C24—C25—H25	120.3
C4—C3—C6	120.8 (4)	C24—C25—C26	119.5 (2)
C3—C4—H4	120.7	C26—C25—H25	120.3
C5—C4—C3	118.7 (4)	N2—C26—C25	124.4 (2)
C5—C4—H4	120.7	N2—C26—H26	117.8
N3—C5—C4	125.2 (4)	C25—C26—H26	117.8
N3—C5—H5	117.4	C24—C27—H27	116.7
C4—C5—H5	117.4	C28—C27—C24	126.5 (3)
C3A—C6A—H6A	117.0	C28—C27—H27	116.7
C7A—C6A—C3A	126.0 (10)	C27—C28—H28A	120.0
C7A—C6A—H6A	117.0	C27—C28—H28B	120.0
C3—C6—H6	117.3	H28A—C28—H28B	120.0
C7—C6—C3	125.4 (5)
Li1—N1—C8—C9	174.8 (2)	C5—N3—C1—C2	−1.8 (7)
Li1—N1—C12—C11	−174.8 (2)	C6A—C3A—C4A—C5A	174.0 (8)
Li1—N2—C22—C23	−175.0 (2)	C6—C3—C4—C5	179.3 (5)
Li1—N2—C26—C25	175.6 (3)	C8—N1—C12—C11	0.5 (4)
Li1—N3—C1A—C2A	174.4 (3)	C8—C9—C10—C11	0.2 (3)
Li1—N3—C5A—C4A	−173.8 (3)	C8—C9—C10—C13	179.8 (2)
Li1—N3—C1—C2	173.8 (4)	C9—C10—C11—C12	0.1 (3)
Li1—N3—C5—C4	−172.5 (4)	C9—C10—C13—C14	169.1 (3)
Li1—N4—C15—C16	174.2 (2)	C10—C11—C12—N1	−0.5 (4)
Li1—N4—C19—C18	−173.7 (3)	C11—C10—C13—C14	−11.4 (4)
N1—C8—C9—C10	−0.1 (4)	C12—N1—C8—C9	−0.2 (3)
N2—C22—C23—C24	−1.7 (4)	C13—C10—C11—C12	−179.5 (2)
N3—C1A—C2A—C3A	0.0	C15—N4—C19—C18	1.6 (4)
N3—C1—C2—C3	−1.7 (7)	C15—C16—C17—C18	2.4 (3)
C1A—N3—C5A—C4A	0.0	C15—C16—C17—C20	−178.4 (2)
C1A—C2A—C3A—C4A	0.0	C16—C17—C18—C19	−1.7 (4)
C1A—C2A—C3A—C6A	−174.0 (8)	C16—C17—C20—C21	6.7 (4)
C2A—C3A—C4A—C5A	0.0	C17—C18—C19—N4	−0.3 (5)
C2A—C3A—C6A—C7A	164.2 (9)	C18—C17—C20—C21	−174.1 (2)
C3A—C4A—C5A—N3	0.0	C19—N4—C15—C16	−0.8 (4)
C4A—C3A—C6A—C7A	−9.8 (13)	C20—C17—C18—C19	179.1 (2)
C5A—N3—C1A—C2A	0.0	C22—N2—C26—C25	−0.8 (4)
N4—C15—C16—C17	−1.2 (4)	C22—C23—C24—C25	1.8 (4)
C1—N3—C5—C4	3.5 (7)	C22—C23—C24—C27	−177.9 (2)
C1—C2—C3—C4	3.6 (6)	C23—C24—C25—C26	−1.5 (4)
C1—C2—C3—C6	−177.9 (5)	C23—C24—C27—C28	167.6 (3)
C2—C3—C4—C5	−2.1 (6)	C24—C25—C26—N2	1.1 (5)
C2—C3—C6—C7	1.6 (8)	C25—C24—C27—C28	−12.2 (4)
C3—C4—C5—N3	−1.6 (7)	C26—N2—C22—C23	1.1 (4)
C4—C3—C6—C7	−179.9 (5)	C27—C24—C25—C26	178.2 (3)

(PyLiPF6) Tetrakis(pyridine-κN)lithium(I) hexafluoridophosphate

Crystal data

[Li(C5H5N)4]PF6	Dx = 1.447 Mg m^−3
Mr = 468.31	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I4	Cell parameters from 2265 reflections
a = 12.3857 (12) Å	θ = 3.3–28.0°
c = 7.0065 (10) Å	µ = 0.19 mm^−1
V = 1074.8 (3) Å^3	T = 123 K
Z = 2	Block, colourless
F(000) = 480	0.14 × 0.1 × 0.1 mm

Data collection

Bruker APEXII CCD diffractometer	1193 independent reflections
Radiation source: sealed tube	1176 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.054
φ and ω scans	θmax = 28.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −16→16
Tmin = 0.676, Tmax = 0.746	k = −16→16
2460 measured reflections	l = −9→2

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.049	H-atom parameters constrained
wR(F^2) = 0.119	w = 1/[σ^2(Fo^2) + (0.1069P)^2 + 0.0419P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max < 0.001
1193 reflections	Δρmax = 1.48 e Å^−3
73 parameters	Δρmin = −0.39 e Å^−3
0 restraints	Absolute structure: Classical Flack method preferred over Parsons because s.u. lower.
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.02 (17)

Special details

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
P1	0.0000	0.0000	0.0000	0.0171 (3)
C5	0.21944 (16)	0.44485 (15)	0.0856 (3)	0.0202 (5)
H5	0.2473	0.4932	0.1787	0.024*
C3	0.25165 (18)	0.32443 (17)	−0.1747 (4)	0.0245 (5)
H3	0.2989	0.2908	−0.2634	0.029*
F1	−0.04041 (12)	0.12237 (11)	−0.0006 (4)	0.0364 (4)
F2	0.0000	0.0000	0.2291 (3)	0.0382 (6)
N1	0.11235 (13)	0.42544 (14)	0.0836 (3)	0.0185 (4)
C2	0.14176 (17)	0.30135 (17)	−0.1754 (4)	0.0254 (5)
H2	0.1126	0.2503	−0.2625	0.030*
C1	0.07569 (15)	0.35447 (15)	−0.0462 (3)	0.0219 (5)
H1	0.0004	0.3399	−0.0496	0.026*
C4	0.29072 (16)	0.39758 (15)	−0.0418 (3)	0.0232 (5)
H4	0.3654	0.4151	−0.0381	0.028*
Li1	0.0000	0.5000	0.2500	0.0197 (13)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.0154 (3)	0.0154 (3)	0.0204 (5)	0.000	0.000	0.000
C5	0.0179 (8)	0.0157 (9)	0.0271 (11)	−0.0031 (6)	0.0009 (9)	−0.0007 (8)
C3	0.0255 (10)	0.0216 (9)	0.0263 (10)	0.0059 (7)	0.0047 (9)	0.0002 (9)
F1	0.0408 (8)	0.0189 (6)	0.0496 (9)	0.0081 (5)	0.0020 (9)	−0.0050 (7)
F2	0.0385 (12)	0.0557 (14)	0.0203 (9)	−0.0094 (11)	0.000	0.000
N1	0.0152 (7)	0.0158 (7)	0.0245 (9)	0.0007 (5)	0.0017 (7)	−0.0001 (7)
C2	0.0276 (11)	0.0245 (9)	0.0241 (10)	0.0036 (8)	−0.0046 (9)	−0.0056 (9)
C1	0.0163 (8)	0.0220 (8)	0.0274 (11)	0.0005 (7)	−0.0039 (7)	−0.0014 (8)
C4	0.0164 (8)	0.0183 (8)	0.0349 (13)	−0.0003 (6)	0.0049 (8)	0.0024 (8)
Li1	0.0140 (16)	0.0140 (16)	0.031 (3)	0.000	0.000	0.000

Geometric parameters (Å, º)

P1—F1^i	1.5961 (13)	C3—C4	1.387 (3)
P1—F1	1.5961 (13)	N1—C1	1.344 (3)
P1—F1^ii	1.5961 (13)	N1—Li1	2.0366 (17)
P1—F1^iii	1.5961 (13)	C2—H2	0.9500
P1—F2	1.6050 (19)	C2—C1	1.386 (3)
P1—F2^ii	1.6050 (19)	C1—H1	0.9500
C5—H5	0.9500	C4—H4	0.9500
C5—N1	1.348 (2)	Li1—N1^iv	2.0366 (18)
C5—C4	1.385 (3)	Li1—N1^v	2.0366 (18)
C3—H3	0.9500	Li1—N1^vi	2.0366 (18)
C3—C2	1.391 (3)
F1^i—P1—F1^ii	179.68 (18)	C4—C3—C2	118.6 (2)
F1^ii—P1—F1	89.999 (1)	C5—N1—Li1	125.83 (16)
F1^i—P1—F1	90.002 (1)	C1—N1—C5	117.13 (18)
F1^i—P1—F1^iii	90.000 (1)	C1—N1—Li1	116.95 (13)
F1^ii—P1—F1^iii	90.000 (1)	C3—C2—H2	120.7
F1^iii—P1—F1	179.68 (18)	C1—C2—C3	118.5 (2)
F1—P1—F2	90.16 (9)	C1—C2—H2	120.7
F1^ii—P1—F2	89.84 (9)	N1—C1—C2	123.57 (18)
F1^i—P1—F2	89.84 (9)	N1—C1—H1	118.2
F1^ii—P1—F2^ii	90.16 (9)	C2—C1—H1	118.2
F1^iii—P1—F2	90.16 (9)	C5—C4—C3	119.12 (19)
F1^iii—P1—F2^ii	89.84 (9)	C5—C4—H4	120.4
F1^i—P1—F2^ii	90.16 (9)	C3—C4—H4	120.4
F1—P1—F2^ii	89.84 (9)	N1—Li1—N1^v	109.12 (5)
F2^ii—P1—F2	180.0	N1^iv—Li1—N1^vi	109.12 (5)
N1—C5—H5	118.5	N1^vi—Li1—N1^v	109.12 (5)
N1—C5—C4	123.0 (2)	N1^iv—Li1—N1^v	110.17 (11)
C4—C5—H5	118.5	N1—Li1—N1^iv	109.12 (5)
C2—C3—H3	120.7	N1—Li1—N1^vi	110.17 (11)
C4—C3—H3	120.7
C5—N1—C1—C2	0.1 (3)	C4—C5—N1—C1	1.8 (3)
C3—C2—C1—N1	−1.7 (3)	C4—C5—N1—Li1	−174.69 (15)
N1—C5—C4—C3	−1.9 (3)	C4—C3—C2—C1	1.5 (3)
C2—C3—C4—C5	0.1 (3)	Li1—N1—C1—C2	176.85 (17)

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

(VnPyLiCl) Di-µ-chlorido-bis[bis(4-ethenylpyridine-κN)lithium]

Crystal data

[Li2Cl2(C7H7N)4]	F(000) = 1056
Mr = 505.32	Dx = 1.191 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 12.240 (4) Å	Cell parameters from 1856 reflections
b = 18.880 (6) Å	θ = 2.3–23.8°
c = 12.675 (4) Å	µ = 0.25 mm^−1
β = 105.864 (6)°	T = 178 K
V = 2817.6 (15) Å^3	Needle, colorless
Z = 4	0.54 × 0.14 × 0.12 mm

Data collection

Bruker APEXII CCD diffractometer	3525 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.059
Absorption correction: multi-scan (SADABS; Bruker, 2008)	θmax = 27.9°, θmin = 2.0°
Tmin = 0.623, Tmax = 0.746	h = −15→16
14219 measured reflections	k = −21→24
6712 independent reflections	l = −16→16

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.117	H-atom parameters constrained
S = 0.97	w = 1/[σ^2(Fo^2) + (0.0409P)^2] where P = (Fo^2 + 2Fc^2)/3
6712 reflections	(Δ/σ)max = 0.001
398 parameters	Δρmax = 0.24 e Å^−3
262 restraints	Δρmin = −0.23 e Å^−3

Special details

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cl1	0.04098 (5)	0.18119 (3)	0.84320 (4)	0.04474 (17)
Cl2	0.01435 (5)	0.32396 (3)	1.02943 (4)	0.04049 (16)
N1	−0.0176 (18)	0.3539 (8)	0.7336 (18)	0.033 (2)	0.387 (7)
N1A	−0.0041 (11)	0.3686 (5)	0.7379 (11)	0.0320 (15)	0.613 (7)
N2	0.05742 (16)	0.14075 (10)	1.12737 (14)	0.0403 (5)
N3	−0.19376 (17)	0.18916 (11)	0.96066 (15)	0.0428 (5)
N4	0.24168 (16)	0.33486 (10)	0.90803 (14)	0.0387 (5)
C11	−0.1051 (13)	0.3242 (6)	0.6630 (14)	0.0312 (18)	0.387 (7)
H11	−0.1214	0.2761	0.6746	0.037*	0.387 (7)
C11A	−0.0911 (8)	0.3431 (4)	0.6593 (9)	0.0346 (14)	0.613 (7)
H11A	−0.1096	0.2944	0.6618	0.041*	0.613 (7)
C12	−0.1737 (9)	0.3580 (5)	0.5749 (9)	0.0317 (17)	0.387 (7)
H12	−0.2344	0.3329	0.5267	0.038*	0.387 (7)
C12A	−0.1565 (5)	0.3844 (3)	0.5734 (5)	0.0333 (12)	0.613 (7)
H12A	−0.2196	0.3644	0.5207	0.040*	0.613 (7)
C13	−0.1564 (7)	0.4278 (6)	0.5547 (7)	0.0294 (16)	0.387 (7)
C13A	−0.1284 (5)	0.4539 (3)	0.5666 (5)	0.0307 (11)	0.613 (7)
C14	−0.0684 (9)	0.4629 (5)	0.6232 (9)	0.0375 (17)	0.387 (7)
H14	−0.0515	0.5108	0.6114	0.045*	0.387 (7)
C14A	−0.0369 (5)	0.4790 (3)	0.6497 (5)	0.0404 (13)	0.613 (7)
H14A	−0.0154	0.5273	0.6494	0.048*	0.613 (7)
C15	−0.0006 (13)	0.4213 (8)	0.7174 (14)	0.040 (2)	0.387 (7)
H15	0.0591	0.4448	0.7696	0.048*	0.387 (7)
C15A	0.0209 (8)	0.4369 (4)	0.7290 (9)	0.0407 (15)	0.613 (7)
H15A	0.0837	0.4563	0.7827	0.049*	0.613 (7)
C16	−0.2375 (7)	0.4634 (5)	0.4572 (7)	0.0448 (18)	0.387 (7)
H16	−0.3003	0.4363	0.4165	0.054*	0.387 (7)
C16A	−0.1889 (5)	0.5011 (3)	0.4790 (4)	0.0410 (12)	0.613 (7)
H16A	−0.1609	0.5482	0.4814	0.049*	0.613 (7)
C17	−0.2287 (9)	0.5256 (5)	0.4255 (8)	0.056 (2)	0.387 (7)
H17A	−0.1671	0.5546	0.4638	0.067*	0.387 (7)
H17B	−0.2837	0.5438	0.3632	0.067*	0.387 (7)
C17A	−0.2769 (5)	0.4860 (3)	0.3978 (5)	0.0554 (15)	0.613 (7)
H17C	−0.3086	0.4397	0.3912	0.066*	0.613 (7)
H17D	−0.3095	0.5213	0.3451	0.066*	0.613 (7)
C21	0.1396 (2)	0.16278 (13)	1.21453 (19)	0.0432 (6)
H21	0.1509	0.2124	1.2247	0.052*
C22	0.20870 (19)	0.11834 (13)	1.29039 (17)	0.0390 (6)
H22	0.2655	0.1373	1.3506	0.047*
C23	0.19441 (19)	0.04563 (12)	1.27781 (17)	0.0366 (6)
C24	0.1084 (2)	0.02242 (13)	1.18896 (19)	0.0459 (6)
H24	0.0942	−0.0268	1.1773	0.055*
C25	0.0435 (2)	0.07105 (13)	1.11762 (18)	0.0449 (6)
H25	−0.0150	0.0536	1.0576	0.054*
C26	0.2663 (2)	−0.00623 (14)	1.3529 (2)	0.0461 (6)
H26	0.2514	−0.0549	1.3355	0.055*
C27	0.3475 (2)	0.00779 (16)	1.4400 (2)	0.0616 (8)
H27A	0.3658	0.0556	1.4610	0.074*
H27B	0.3888	−0.0297	1.4829	0.074*
C31	−0.2534 (2)	0.21440 (15)	1.0260 (2)	0.0543 (7)
H31	−0.2128	0.2325	1.0956	0.065*
C32	−0.3698 (2)	0.21591 (14)	0.9988 (2)	0.0525 (7)
H32	−0.4074	0.2347	1.0489	0.063*
C33	−0.4319 (2)	0.19017 (12)	0.89910 (19)	0.0411 (6)
C34	−0.3709 (2)	0.16274 (13)	0.83037 (18)	0.0419 (6)
H34	−0.4096	0.1437	0.7608	0.050*
C35	−0.2543 (2)	0.16344 (13)	0.86414 (18)	0.0411 (6)
H35	−0.2143	0.1445	0.8160	0.049*
C36	−0.5568 (2)	0.19276 (15)	0.8684 (2)	0.0543 (7)
H36	−0.5906	0.2126	0.9208	0.065*
C37	−0.6252 (3)	0.17103 (17)	0.7779 (2)	0.0694 (9)
H37A	−0.5958	0.1508	0.7226	0.083*
H37B	−0.7049	0.1752	0.7664	0.083*
C41	0.2996 (2)	0.33606 (13)	1.01455 (17)	0.0392 (6)
H41	0.2630	0.3185	1.0663	0.047*
C42	0.4086 (2)	0.36104 (13)	1.05325 (18)	0.0388 (6)
H42	0.4452	0.3603	1.1297	0.047*
C43	0.46518 (19)	0.38744 (12)	0.98053 (17)	0.0367 (6)
C44	0.4064 (2)	0.38527 (14)	0.86991 (18)	0.0449 (6)
H44	0.4413	0.4020	0.8164	0.054*
C45	0.2975 (2)	0.35886 (14)	0.83809 (18)	0.0435 (6)
H45	0.2598	0.3576	0.7619	0.052*
C46	0.5785 (2)	0.41851 (14)	1.0165 (2)	0.0489 (7)
H46	0.6100	0.4356	0.9607	0.059*
C47	0.6407 (2)	0.42523 (16)	1.1167 (2)	0.0670 (9)
H47A	0.6131	0.4090	1.1756	0.080*
H47B	0.7137	0.4464	1.1312	0.080*
Li1	0.0748 (3)	0.3033 (2)	0.8702 (3)	0.0425 (10)
Li2	−0.0223 (3)	0.2051 (2)	0.9992 (3)	0.0427 (10)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0565 (4)	0.0394 (4)	0.0356 (3)	0.0083 (3)	0.0078 (3)	−0.0059 (3)
Cl2	0.0497 (4)	0.0331 (3)	0.0401 (3)	−0.0005 (3)	0.0147 (3)	−0.0036 (3)
N1	0.035 (4)	0.024 (4)	0.038 (3)	−0.009 (4)	0.003 (3)	−0.004 (4)
N1A	0.035 (3)	0.024 (4)	0.035 (2)	−0.006 (3)	0.0060 (19)	−0.001 (3)
N2	0.0492 (13)	0.0321 (12)	0.0389 (11)	0.0030 (9)	0.0108 (10)	−0.0008 (9)
N3	0.0476 (13)	0.0382 (13)	0.0410 (11)	−0.0030 (10)	0.0096 (10)	−0.0022 (9)
N4	0.0379 (11)	0.0432 (13)	0.0338 (11)	0.0055 (9)	0.0077 (9)	0.0035 (9)
C11	0.031 (4)	0.020 (4)	0.040 (3)	−0.011 (3)	0.005 (3)	−0.001 (3)
C11A	0.039 (3)	0.020 (3)	0.044 (2)	−0.013 (2)	0.011 (2)	−0.001 (3)
C12	0.036 (4)	0.023 (4)	0.034 (3)	−0.009 (3)	0.005 (2)	−0.006 (3)
C12A	0.036 (2)	0.027 (3)	0.034 (2)	−0.012 (3)	0.0054 (17)	−0.003 (3)
C13	0.035 (3)	0.024 (4)	0.029 (3)	−0.006 (3)	0.010 (2)	−0.003 (3)
C13A	0.037 (3)	0.022 (2)	0.033 (2)	−0.001 (2)	0.0104 (18)	−0.001 (2)
C14	0.044 (4)	0.020 (3)	0.044 (4)	−0.010 (3)	0.004 (3)	−0.003 (3)
C14A	0.045 (3)	0.027 (3)	0.041 (3)	−0.010 (2)	−0.001 (2)	−0.005 (2)
C15	0.042 (4)	0.026 (4)	0.044 (3)	−0.016 (3)	−0.002 (3)	−0.012 (4)
C15A	0.043 (3)	0.025 (3)	0.048 (3)	−0.010 (2)	0.002 (2)	−0.006 (2)
C16	0.045 (4)	0.040 (4)	0.043 (3)	0.001 (3)	0.001 (3)	0.004 (3)
C16A	0.048 (3)	0.032 (3)	0.039 (2)	0.003 (2)	0.007 (2)	0.0075 (19)
C17	0.061 (6)	0.049 (5)	0.053 (5)	0.006 (4)	0.006 (4)	0.015 (4)
C17A	0.057 (3)	0.050 (4)	0.050 (3)	0.003 (3)	−0.001 (2)	0.014 (3)
C21	0.0573 (16)	0.0272 (14)	0.0445 (14)	−0.0026 (12)	0.0130 (12)	−0.0014 (11)
C22	0.0464 (15)	0.0341 (14)	0.0345 (13)	−0.0036 (12)	0.0077 (11)	−0.0007 (10)
C23	0.0456 (15)	0.0315 (14)	0.0361 (12)	0.0006 (11)	0.0168 (11)	0.0009 (10)
C24	0.0646 (18)	0.0271 (14)	0.0458 (15)	−0.0011 (12)	0.0147 (13)	−0.0031 (11)
C25	0.0550 (17)	0.0382 (16)	0.0377 (13)	−0.0030 (12)	0.0063 (12)	−0.0074 (11)
C26	0.0590 (18)	0.0318 (15)	0.0490 (15)	0.0060 (12)	0.0173 (14)	0.0052 (12)
C27	0.0498 (18)	0.0491 (19)	0.079 (2)	0.0082 (14)	0.0058 (16)	0.0174 (15)
C31	0.064 (2)	0.0515 (18)	0.0490 (15)	−0.0117 (14)	0.0180 (14)	−0.0149 (13)
C32	0.0615 (19)	0.0454 (17)	0.0560 (17)	−0.0040 (14)	0.0251 (14)	−0.0109 (13)
C33	0.0453 (15)	0.0303 (14)	0.0510 (14)	0.0052 (11)	0.0184 (12)	0.0138 (11)
C34	0.0484 (16)	0.0382 (15)	0.0345 (13)	−0.0009 (12)	0.0035 (11)	0.0042 (10)
C35	0.0480 (16)	0.0379 (15)	0.0371 (13)	0.0026 (11)	0.0110 (11)	0.0003 (11)
C36	0.0561 (19)	0.0497 (18)	0.0613 (18)	0.0037 (14)	0.0230 (15)	0.0115 (14)
C37	0.0523 (19)	0.079 (2)	0.075 (2)	−0.0007 (17)	0.0139 (16)	0.0111 (17)
C41	0.0399 (15)	0.0455 (16)	0.0329 (13)	0.0046 (11)	0.0110 (11)	0.0087 (10)
C42	0.0398 (15)	0.0445 (15)	0.0305 (12)	0.0050 (12)	0.0068 (10)	0.0036 (10)
C43	0.0382 (14)	0.0351 (14)	0.0363 (13)	0.0064 (11)	0.0094 (11)	0.0038 (10)
C44	0.0517 (17)	0.0507 (17)	0.0358 (13)	0.0041 (13)	0.0181 (12)	0.0088 (11)
C45	0.0464 (16)	0.0518 (17)	0.0290 (12)	0.0061 (13)	0.0048 (11)	0.0021 (11)
C46	0.0469 (16)	0.0540 (18)	0.0478 (15)	−0.0040 (13)	0.0167 (13)	0.0056 (12)
C47	0.0486 (18)	0.078 (2)	0.069 (2)	−0.0139 (16)	0.0071 (15)	0.0085 (16)
Li1	0.045 (2)	0.043 (3)	0.038 (2)	0.0041 (19)	0.0079 (18)	0.0032 (18)
Li2	0.052 (3)	0.034 (2)	0.039 (2)	0.0016 (19)	0.0054 (18)	0.0010 (18)

Geometric parameters (Å, º)

Cl1—Li1	2.350 (4)	C17A—H17C	0.9500
Cl1—Li2	2.355 (4)	C17A—H17D	0.9500
Cl2—Li1	2.364 (4)	C21—H21	0.9500
Cl2—Li2	2.300 (4)	C21—C22	1.378 (3)
N1—C11	1.318 (15)	C22—H22	0.9500
N1—C15	1.316 (14)	C22—C23	1.388 (3)
N1—Li1	2.030 (18)	C23—C24	1.386 (3)
N1A—C11A	1.333 (10)	C23—C26	1.477 (3)
N1A—C15A	1.338 (8)	C24—H24	0.9500
N1A—Li1	2.093 (11)	C24—C25	1.378 (3)
N2—C21	1.341 (3)	C25—H25	0.9500
N2—C25	1.328 (3)	C26—H26	0.9500
N2—Li2	2.050 (4)	C26—C27	1.295 (3)
N3—C31	1.332 (3)	C27—H27A	0.9500
N3—C35	1.337 (3)	C27—H27B	0.9500
N3—Li2	2.043 (5)	C31—H31	0.9500
N4—C41	1.343 (3)	C31—C32	1.372 (4)
N4—C45	1.338 (3)	C32—H32	0.9500
N4—Li1	2.054 (4)	C32—C33	1.373 (3)
C11—H11	0.9500	C33—C34	1.393 (3)
C11—C12	1.359 (15)	C33—C36	1.472 (4)
C11A—H11A	0.9500	C34—H34	0.9500
C11A—C12A	1.399 (9)	C34—C35	1.373 (3)
C12—H12	0.9500	C35—H35	0.9500
C12—C13	1.370 (10)	C36—H36	0.9500
C12A—H12A	0.9500	C36—C37	1.288 (3)
C12A—C13A	1.367 (6)	C37—H37A	0.9500
C13—C14	1.356 (10)	C37—H37B	0.9500
C13—C16	1.515 (12)	C41—H41	0.9500
C13A—C14A	1.394 (6)	C41—C42	1.372 (3)
C13A—C16A	1.458 (7)	C42—H42	0.9500
C14—H14	0.9500	C42—C43	1.388 (3)
C14—C15	1.480 (17)	C43—C44	1.391 (3)
C14A—H14A	0.9500	C43—C46	1.460 (3)
C14A—C15A	1.325 (10)	C44—H44	0.9500
C15—H15	0.9500	C44—C45	1.376 (3)
C15A—H15A	0.9500	C45—H45	0.9500
C16—H16	0.9500	C46—H46	0.9500
C16—C17	1.256 (16)	C46—C47	1.296 (3)
C16A—H16A	0.9500	C47—H47A	0.9500
C16A—C17A	1.302 (10)	C47—H47B	0.9500
C17—H17A	0.9500	Li1—Li2	2.929 (6)
C17—H17B	0.9500
Li1—Cl1—Li2	77.00 (14)	C24—C25—H25	117.9
Li2—Cl2—Li1	77.80 (14)	C23—C26—H26	116.7
C11—N1—Li1	122.6 (10)	C27—C26—C23	126.7 (3)
C15—N1—C11	116.1 (13)	C27—C26—H26	116.7
C15—N1—Li1	120.9 (11)	C26—C27—H27A	120.0
C11A—N1A—C15A	116.0 (7)	C26—C27—H27B	120.0
C11A—N1A—Li1	119.1 (6)	H27A—C27—H27B	120.0
C15A—N1A—Li1	124.7 (7)	N3—C31—H31	118.0
C21—N2—Li2	123.8 (2)	N3—C31—C32	124.0 (2)
C25—N2—C21	115.62 (19)	C32—C31—H31	118.0
C25—N2—Li2	119.48 (19)	C31—C32—H32	120.0
C31—N3—C35	116.0 (2)	C31—C32—C33	120.0 (2)
C31—N3—Li2	120.0 (2)	C33—C32—H32	120.0
C35—N3—Li2	123.28 (19)	C32—C33—C34	116.8 (2)
C41—N4—Li1	117.24 (18)	C32—C33—C36	120.4 (2)
C45—N4—C41	115.8 (2)	C34—C33—C36	122.9 (2)
C45—N4—Li1	126.81 (18)	C33—C34—H34	120.3
N1—C11—H11	117.9	C35—C34—C33	119.4 (2)
N1—C11—C12	124.3 (9)	C35—C34—H34	120.3
C12—C11—H11	117.9	N3—C35—C34	123.9 (2)
N1A—C11A—H11A	118.3	N3—C35—H35	118.0
N1A—C11A—C12A	123.5 (5)	C34—C35—H35	118.0
C12A—C11A—H11A	118.3	C33—C36—H36	116.6
C11—C12—H12	119.6	C37—C36—C33	126.8 (3)
C11—C12—C13	120.8 (8)	C37—C36—H36	116.6
C13—C12—H12	119.6	C36—C37—H37A	120.0
C11A—C12A—H12A	120.5	C36—C37—H37B	120.0
C13A—C12A—C11A	118.9 (5)	H37A—C37—H37B	120.0
C13A—C12A—H12A	120.5	N4—C41—H41	118.0
C12—C13—C16	118.6 (7)	N4—C41—C42	124.0 (2)
C14—C13—C12	119.1 (8)	C42—C41—H41	118.0
C14—C13—C16	122.2 (9)	C41—C42—H42	120.0
C12A—C13A—C14A	116.3 (5)	C41—C42—C43	119.9 (2)
C12A—C13A—C16A	123.5 (5)	C43—C42—H42	120.0
C14A—C13A—C16A	120.3 (4)	C42—C43—C44	116.4 (2)
C13—C14—H14	122.3	C42—C43—C46	122.8 (2)
C13—C14—C15	115.4 (8)	C44—C43—C46	120.8 (2)
C15—C14—H14	122.3	C43—C44—H44	120.0
C13A—C14A—H14A	119.3	C45—C44—C43	119.9 (2)
C15A—C14A—C13A	121.5 (5)	C45—C44—H44	120.0
C15A—C14A—H14A	119.3	N4—C45—C44	123.9 (2)
N1—C15—C14	124.1 (10)	N4—C45—H45	118.0
N1—C15—H15	118.0	C44—C45—H45	118.0
C14—C15—H15	118.0	C43—C46—H46	116.6
N1A—C15A—H15A	118.1	C47—C46—C43	126.8 (2)
C14A—C15A—N1A	123.8 (6)	C47—C46—H46	116.6
C14A—C15A—H15A	118.1	C46—C47—H47A	120.0
C13—C16—H16	117.2	C46—C47—H47B	120.0
C17—C16—C13	125.6 (10)	H47A—C47—H47B	120.0
C17—C16—H16	117.2	Cl1—Li1—Cl2	101.68 (15)
C13A—C16A—H16A	116.3	Cl1—Li1—Li2	51.58 (11)
C17A—C16A—C13A	127.3 (6)	Cl2—Li1—Li2	50.12 (11)
C17A—C16A—H16A	116.3	N1—Li1—Cl1	107.6 (5)
C16—C17—H17A	120.0	N1—Li1—Cl2	114.8 (8)
C16—C17—H17B	120.0	N1—Li1—N4	110.4 (6)
H17A—C17—H17B	120.0	N1—Li1—Li2	123.9 (6)
C16A—C17A—H17C	120.0	N1A—Li1—Cl1	115.9 (3)
C16A—C17A—H17D	120.0	N1A—Li1—Cl2	113.8 (5)
H17C—C17A—H17D	120.0	N1A—Li1—Li2	130.6 (4)
N2—C21—H21	117.8	N4—Li1—Cl1	116.30 (19)
N2—C21—C22	124.4 (2)	N4—Li1—Cl2	106.03 (16)
C22—C21—H21	117.8	N4—Li1—N1A	103.2 (4)
C21—C22—H22	120.4	N4—Li1—Li2	125.63 (17)
C21—C22—C23	119.2 (2)	Cl1—Li2—Li1	51.42 (11)
C23—C22—H22	120.4	Cl2—Li2—Cl1	103.49 (16)
C22—C23—C26	123.2 (2)	Cl2—Li2—Li1	52.08 (11)
C24—C23—C22	116.8 (2)	N2—Li2—Cl1	110.95 (19)
C24—C23—C26	120.0 (2)	N2—Li2—Cl2	114.67 (17)
C23—C24—H24	120.1	N2—Li2—Li1	129.8 (2)
C25—C24—C23	119.7 (2)	N3—Li2—Cl1	108.85 (16)
C25—C24—H24	120.1	N3—Li2—Cl2	108.91 (19)
N2—C25—C24	124.2 (2)	N3—Li2—N2	109.7 (2)
N2—C25—H25	117.9	N3—Li2—Li1	120.46 (17)
N1—C11—C12—C13	−1 (2)	C25—N2—C21—C22	1.1 (4)
N1A—C11A—C12A—C13A	2.3 (13)	C26—C23—C24—C25	−178.4 (2)
N2—C21—C22—C23	0.1 (4)	C31—N3—C35—C34	0.7 (3)
N3—C31—C32—C33	0.2 (4)	C31—C32—C33—C34	0.6 (4)
N4—C41—C42—C43	0.3 (4)	C31—C32—C33—C36	−178.9 (2)
C11—N1—C15—C14	−4 (3)	C32—C33—C34—C35	−0.7 (3)
C11—C12—C13—C14	1.0 (17)	C32—C33—C36—C37	179.6 (3)
C11—C12—C13—C16	−178.2 (11)	C33—C34—C35—N3	0.1 (4)
C11A—N1A—C15A—C14A	1.6 (17)	C34—C33—C36—C37	0.1 (4)
C11A—C12A—C13A—C14A	−2.0 (9)	C35—N3—C31—C32	−0.8 (4)
C11A—C12A—C13A—C16A	178.3 (7)	C36—C33—C34—C35	178.7 (2)
C12—C13—C14—C15	−2.0 (16)	C41—N4—C45—C44	−1.7 (4)
C12—C13—C16—C17	−176.1 (10)	C41—C42—C43—C44	−1.3 (3)
C12A—C13A—C14A—C15A	1.6 (10)	C41—C42—C43—C46	176.4 (2)
C12A—C13A—C16A—C17A	1.4 (9)	C42—C43—C44—C45	0.9 (3)
C13—C14—C15—N1	4 (2)	C42—C43—C46—C47	0.6 (4)
C13A—C14A—C15A—N1A	−1.5 (14)	C43—C44—C45—N4	0.6 (4)
C14—C13—C16—C17	4.7 (14)	C44—C43—C46—C47	178.2 (3)
C14A—C13A—C16A—C17A	−178.3 (6)	C45—N4—C41—C42	1.2 (3)
C15—N1—C11—C12	3 (3)	C46—C43—C44—C45	−176.9 (2)
C15A—N1A—C11A—C12A	−2.0 (16)	Li1—N1—C11—C12	175.3 (15)
C16—C13—C14—C15	177.2 (10)	Li1—N1—C15—C14	−176.6 (15)
C16A—C13A—C14A—C15A	−178.7 (7)	Li1—N1A—C11A—C12A	173.5 (9)
C21—N2—C25—C24	−1.2 (4)	Li1—N1A—C15A—C14A	−173.6 (10)
C21—C22—C23—C24	−1.1 (3)	Li1—N4—C41—C42	−174.7 (2)
C21—C22—C23—C26	178.2 (2)	Li1—N4—C45—C44	173.8 (2)
C22—C23—C24—C25	1.0 (3)	Li2—N2—C21—C22	−166.9 (2)
C22—C23—C26—C27	2.3 (4)	Li2—N2—C25—C24	167.4 (2)
C23—C24—C25—N2	0.2 (4)	Li2—N3—C31—C32	169.6 (2)
C24—C23—C26—C27	−178.3 (3)	Li2—N3—C35—C34	−169.4 (2)