(μ-1,4,7,10-Tetra­oxacyclo­dodeca­ne)bis­[(1,4,7,10-tetra­oxacyclo­dodeca­ne)lithium] bis­(perchlorate)

Guzei, I.A.; Spencer, L.C.; Xiao, L.; Burnette, R.R.

doi:10.1107/S1600536810009542

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 4| April 2010| Pages m438-m439

doi:10.1107/S1600536810009542

Open

access

(μ-1,4,7,10-Tetraoxacyclododecane)bis[(1,4,7,10-tetraoxacyclododecane)lithium] bis(perchlorate)

Ilia A. Guzei,^a ^* Lara C. Spencer,^a Lingyun Xiao ^b and Ronald R. Burnette ^c

^aDepartment of Chemistry, University of Wisconsin-Madison, 1101 University Ave, Madison, WI 53706, USA, ^bSmall Molecule Process & Product Development, AMGEN, One Amgen Center Drive, Thousand Oaks, CA 91320, USA, and ^cSchool of Pharmacy, University of Wisconsin-Madison, 777 Highland Ave, Madison, WI 53705, USA
^*Correspondence e-mail: iguzei@chem.wisc.edu

(Received 4 March 2010; accepted 12 March 2010; online 24 March 2010)

12-Crown-4 ether (12C4) and LiClO₄ combine to form the ionic title compound, [Li₂(C₈H₁₆O₄)₃](ClO₄)₂, which is composed of discrete Li/12C4 cations and perchlorate anions. In the [Li₂(12C4)₃]²⁺ cation there are two peripheral 12C4 ligands, which each form four Li—O bonds with only one Li⁺ atom. Additionally there is a central 12C4 in which diagonal O atoms form one Li—O bond each with both Li⁺ atoms. Therefore each Li⁺ atom is pentacoordinated in a distorted square-pyramidal geometry, forming four longer bonds to the O atoms on the peripheral 12C4 and one shorter bond to an O atom of the central 12C4. The cation occupies a crystallographic inversion centre located at the center of the ring of the central 12C4 ligand. The Li⁺ atom lies above the cavity of the peripheral 12C4 by 0.815 (2) Å because it is too large to fit in the cavity.

Related literature

For applications of crown ethers, see: Jagannadh & Sarma (1999 ); Lehn (1973 , 1995 ); Doyle & McCord (1998 ); Blasius et al. (1982 ); Blasius & Janzen (1982 ); Hayashita et al. (1992 ); Frühauf & Zeller (1991 ). For 12-crown-4 ether geometry, see: Raithby et al. (1997 ); Jones et al. (1997 ). For the size of the crown ether cavity and lithium ion, see: Shoham et al. (1983 ); Dalley (1978 ); Shannon (1976 ). For tris(1,4,7,10-tetraoxacyclododecane)dilithium bis[tetrahydridoaluminate(III)], see: Bollmann & Olbrich (2004 ). Bond distances and angles were confirmed to be typical by a Mogul structural check (Bruno et al., 2002 ). For a description of 1,4,7,10-tetraoxacyclododecane-trideuteroacetonitrile-lithium perchlorate, synthesized simultaneously with the title compound, see: Guzei et al. (2010 ). The outlier reflections were omitted based on the statistics test described by Prince & Nicholson (1983 ); Rollett (1988 ).

Experimental

Crystal data

[Li₂(C₈H₁₆O₄)₃](ClO₄)₂
M_r = 741.40
Monoclinic, P 2₁ /c
a = 7.7395 (7) Å
b = 14.1924 (13) Å
c = 15.2801 (14) Å
β = 95.962 (2)°
V = 1669.3 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 100 K
0.40 × 0.30 × 0.20 mm

Data collection

Bruker CCD-1000 area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2003 ) T_min = 0.897, T_max = 0.947
13593 measured reflections
3412 independent reflections
3139 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.092
S = 1.04
3412 reflections
217 parameters
H-atom parameters constrained
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Table 1
Selected bond lengths (Å)

O1—Li1	2.094 (3)
O2—Li1	2.079 (3)
O3—Li1	2.074 (3)
O4—Li1	2.061 (3)
O5—Li1	1.936 (3)

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL and FCF_filter (Guzei, 2007 ); molecular graphics: SHELXTL and DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: SHELXTL, publCIF (Westrip, 2010 ) and modiCIFer (Guzei, 2007).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810009542/si2246sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810009542/si2246Isup2.hkl

checkCIF report

Comment top

Crown ethers complex with metal ions through the oxygen atoms with remarkable selectivity. They have high conformational flexibility, act as host molecules for various guests (Jagannadh et al., 1999), and have a broad range of applications. Their importance has been studied in numerous fields such as molecular design (Lehn, 1973), supramolecular chemistry (Lehn, 1995), analytical chemistry (Doyle & McCord, 1998; Blasius et al., 1982; Blasius & Janzen, 1982; Hayashita et al., 1992) and medicine (Fruhauf & Zeller, 1991). In this study, the goal was to understand the nature of crown ether/Li⁺ complexes, and to extend its application to facilitate the characterization of host-guest type drug delivery systems. Thus, we are developing a systematic methodology based on experimental X-ray crystallography. As a result several novel complexes including the title compound (I) were synthesized.

12-crown-4 ether (12C4) and LiClO₄ combine to form an ionic compound composed of discrete cations and anions. The cation is formed by two Li⁺ metals and three 12C4 ligands interacting to form a complex while the anion is uncomplexed perchlorate. In the cation, two of the 12C4 ligands are peripheral, each interacting with only one Li⁺. The third 12C4 lies between the two Li⁺ atoms and two opposite oxygen atoms each interact with one of the Li⁺ atoms. The cation occupies an inversion center located at the center of the ring of the central 12C4. Each Li⁺ is pentacoordinate with a distorted square pyramidal geometry forming four bonds to the oxygen atoms of a peripheral 12C4 and one bond to an oxygen atom belonging to the center 12C4. The Li—O bond to the central 12C4 is significantly shorter (1.936 (3) Å) than those to the oxygen atoms on the peripheral 12C4 (av. 2.077 (14) Å). The peripheral 12C4 has approximate C4 symmetry and is in the common [3333] conformation (Raithby et al., 1997; Jones et al., 1997) with the oxygen atoms being coplanar within of 0.013 Å . The central 12C4 is in the [66] conformation (Raithby et al., 1997). The Li⁺ atom resides above the cavity of the peripheral 12C4 by 0.815 (2) Å. The average diagonal length measured between atom pairs O1/O3 and O2/O4 of the peripheral 12C4 is 3.8211 (15) Å resulting in an adjusted diameter of the cavity of 1.0211 Å (Shoham et al., 1983; Dalley, 1978) . The Li⁺ has an ionic diameter between 1.18 Å and 1.52 Å; thus it is to large to fit in the cavity (Shannon, 1976).

The angles and distances involving the lithium atoms are similar to those in tris(1,4,7,10-tetraoxacyclododecane)-di-lithium bis(tetrahydridoaluminate(III)) (Bollmann & Olbrich, 2004) which contains the same cationic lithium complex as (I) with a different anion . A Mogul structural check confirmed that (I) exhibits typical geometrical parameters (Bruno et al., 2002).

The Li⁺ cation complexes form sheets in the ac plane which stack along the b axis. The anions are positioned between adjacent sheets of cations.

Related literature top

For applications of crown ethers, see: Jagannadh et al. (1999); Lehn (1973, (1995); Doyle & McCord (1998); Blasius et al. (1982); Blasius & Janzen (1982); Hayashita et al. (1992); Frühauf & Zeller (1991). For 12-crown-4 ether geometry, see: Raithby et al. (1997); Jones et al. (1997). For the size of the crown ether cavity and lithium ion, see: Shoham et al. (1983); Dalley (1978); Shannon (1976). For the related compund tris(1,4,7,10-tetraoxacyclododecane)-di-lithium bis[tetrahydridoaluminate(III)], see: Bollmann & Olbrich (2004). Bond distances and angles were confirmed to be typical by a Mogul structural check (Bruno et al., 2002). For a description of 1,4,7,10-tetraoxacyclododecane-trideuteroacetonitrile-lithium perchlorate synthesized simultaneously with the title compound, see: Guzei et al. (2010). The outlier reflections were omitted based on the statistics test described by Prince & Nicholson (1983); Rollett (1988).

Experimental top

All chemicals were purchased from the Aldrich Chemical Co. Inc. and were used as received. 12-crown-4 (12C4, C₈H₁₆O₄, 98% pure) and lithium perchlorate (LiClO₄, 99% pure) were separately dissolved in acetonitrile-d₃ (CD₃CN, 99% pure). These two solutions were then mixed together according to a 1:1 molar ratio of 12C4/LiClO₄.The final solution was kept in a desiccator and the solvent was allowed to evaporate gradually in order to produce a supersaturated solution. The supersaturated solution was stored at –20 °C refrigerator, until crystals formed after 48 hours. Two types of colorless crystals suitable for X-ray diffraction were obtained and separated from the solution, one of which was compound (I) the other being 1,4,7,10-tetraoxacyclododecane-trideuteroacetonitrile-lithium perchlorate (Guzei et al., 2010).

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL and FCF_filter (Guzei, 2007); molecular graphics: SHELXTL and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL, publCIF (Westrip, 2010) and modiCIFer (Guzei, 2007).

Figures top

Fig. 1. Molecular structure of (I). The thermal ellipsoids are shown at 50% probability level. All hydrogen atoms were omitted for clarity. Symmetry transformations used to generate equivalent atoms: i -x, -y, -z+2.

(µ-1,4,7,10-Tetraoxacyclododecane)bis[(1,4,7,10-tetraoxacyclododecane)lithium] bis(perchlorate) top

Crystal data top

[Li₂(C₈H₁₆O₄)₃](ClO₄)₂	F(000) = 784
M_r = 741.40	D_x = 1.475 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 999 reflections
a = 7.7395 (7) Å	θ = 2.7–26.4°
b = 14.1924 (13) Å	µ = 0.28 mm⁻¹
c = 15.2801 (14) Å	T = 100 K
β = 95.962 (2)°	Block, colourless
V = 1669.3 (3) Å³	0.40 × 0.30 × 0.20 mm
Z = 2

Data collection top

Bruker CCD-1000 area-detector diffractometer	3412 independent reflections
Radiation source: fine-focus sealed tube	3139 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
0.30° ω and 0.4 ° ϕ scans	θ_max = 26.4°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −9→9
T_min = 0.897, T_max = 0.947	k = −17→17
13593 measured reflections	l = −19→19

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.092	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0467P)² + 1.027P] where P = (F_o² + 2F_c²)/3
3412 reflections	(Δ/σ)_max < 0.001
217 parameters	Δρ_max = 0.51 e Å⁻³
0 restraints	Δρ_min = −0.36 e Å⁻³

Crystal data top

[Li₂(C₈H₁₆O₄)₃](ClO₄)₂	V = 1669.3 (3) Å³
M_r = 741.40	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.7395 (7) Å	µ = 0.28 mm⁻¹
b = 14.1924 (13) Å	T = 100 K
c = 15.2801 (14) Å	0.40 × 0.30 × 0.20 mm
β = 95.962 (2)°

Data collection top

Bruker CCD-1000 area-detector diffractometer	3412 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2003)	3139 reflections with I > 2σ(I)
T_min = 0.897, T_max = 0.947	R_int = 0.027
13593 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.092	H-atom parameters constrained
S = 1.04	Δρ_max = 0.51 e Å⁻³
3412 reflections	Δρ_min = −0.36 e Å⁻³
217 parameters

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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
O1	0.37224 (13)	−0.00939 (8)	0.79331 (7)	0.0253 (2)
O2	0.14456 (14)	−0.11875 (7)	0.68986 (7)	0.0228 (2)
O3	−0.10708 (13)	0.00835 (7)	0.70392 (6)	0.0206 (2)
O4	0.11574 (14)	0.11599 (7)	0.80927 (7)	0.0223 (2)
O5	0.01430 (12)	−0.10039 (7)	0.88536 (6)	0.0188 (2)
O6	−0.20229 (14)	0.05033 (7)	0.94017 (7)	0.0233 (2)
Li1	0.1036 (3)	−0.02805 (17)	0.79255 (15)	0.0201 (5)
C1	0.4243 (2)	−0.04051 (12)	0.71080 (10)	0.0279 (3)
H1A	0.5516	−0.0498	0.7151	0.033*
H1B	0.3909	0.0063	0.6641	0.033*
C2	0.3315 (2)	−0.13188 (12)	0.69088 (11)	0.0303 (4)
H2A	0.3585	−0.1557	0.6329	0.036*
H2B	0.3719	−0.1792	0.7360	0.036*
C3	0.0620 (2)	−0.08202 (11)	0.60923 (10)	0.0261 (3)
H3A	0.0564	−0.1304	0.5624	0.031*
H3B	0.1261	−0.0267	0.5900	0.031*
C4	−0.1181 (2)	−0.05422 (12)	0.62882 (10)	0.0261 (3)
H4A	−0.1794	−0.0223	0.5770	0.031*
H4B	−0.1849	−0.1112	0.6414	0.031*
C5	−0.0971 (2)	0.10586 (11)	0.68153 (10)	0.0243 (3)
H5A	−0.2113	0.1291	0.6550	0.029*
H5B	−0.0103	0.1158	0.6392	0.029*
C6	−0.0433 (2)	0.15582 (11)	0.76647 (10)	0.0255 (3)
H6A	−0.0256	0.2236	0.7548	0.031*
H6B	−0.1366	0.1503	0.8058	0.031*
C7	0.2697 (2)	0.15160 (11)	0.77685 (10)	0.0251 (3)
H7A	0.2919	0.2173	0.7966	0.030*
H7B	0.2586	0.1501	0.7117	0.030*
C8	0.4132 (2)	0.08828 (12)	0.81403 (10)	0.0277 (3)
H8A	0.5222	0.1058	0.7895	0.033*
H8B	0.4315	0.0963	0.8787	0.033*
C9	0.1074 (2)	−0.16375 (11)	0.94693 (10)	0.0236 (3)
H9A	0.1499	−0.2182	0.9148	0.028*
H9B	0.0280	−0.1878	0.9886	0.028*
C10	−0.17131 (18)	−0.10405 (11)	0.88613 (9)	0.0211 (3)
H10A	−0.2075	−0.1703	0.8930	0.025*
H10B	−0.2275	−0.0808	0.8290	0.025*
C11	−0.23197 (18)	−0.04594 (11)	0.95912 (10)	0.0219 (3)
H11A	−0.3572	−0.0569	0.9632	0.026*
H11B	−0.1670	−0.0636	1.0160	0.026*
C12	−0.2582 (2)	0.11475 (11)	1.00296 (10)	0.0248 (3)
H12A	−0.3248	0.0802	1.0447	0.030*
H12B	−0.3363	0.1622	0.9723	0.030*
Cl1	0.42590 (4)	0.18127 (2)	0.53628 (2)	0.01772 (11)
O7	0.49851 (14)	0.23355 (8)	0.61216 (7)	0.0266 (3)
O8	0.38979 (16)	0.24318 (8)	0.46246 (8)	0.0325 (3)
O9	0.26490 (16)	0.13825 (9)	0.55554 (7)	0.0334 (3)
O10	0.54620 (18)	0.11021 (10)	0.51571 (9)	0.0421 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0200 (5)	0.0360 (6)	0.0202 (5)	−0.0012 (4)	0.0035 (4)	0.0050 (4)
O2	0.0284 (6)	0.0210 (5)	0.0197 (5)	−0.0002 (4)	0.0064 (4)	0.0007 (4)
O3	0.0213 (5)	0.0225 (5)	0.0179 (5)	−0.0017 (4)	0.0012 (4)	0.0025 (4)
O4	0.0266 (5)	0.0227 (5)	0.0177 (5)	−0.0050 (4)	0.0026 (4)	−0.0001 (4)
O5	0.0162 (5)	0.0221 (5)	0.0183 (5)	0.0005 (4)	0.0026 (4)	0.0035 (4)
O6	0.0276 (5)	0.0241 (5)	0.0191 (5)	0.0013 (4)	0.0060 (4)	−0.0004 (4)
Li1	0.0201 (11)	0.0215 (12)	0.0188 (11)	−0.0005 (9)	0.0028 (9)	0.0021 (9)
C1	0.0204 (7)	0.0401 (9)	0.0240 (8)	0.0036 (6)	0.0065 (6)	0.0031 (7)
C2	0.0344 (9)	0.0293 (8)	0.0295 (8)	0.0115 (7)	0.0138 (7)	0.0026 (7)
C3	0.0332 (8)	0.0269 (8)	0.0181 (7)	−0.0032 (6)	0.0033 (6)	−0.0031 (6)
C4	0.0287 (8)	0.0304 (8)	0.0183 (7)	−0.0091 (6)	−0.0015 (6)	−0.0031 (6)
C5	0.0217 (7)	0.0234 (7)	0.0273 (8)	0.0013 (6)	0.0001 (6)	0.0063 (6)
C6	0.0266 (8)	0.0219 (7)	0.0290 (8)	0.0054 (6)	0.0075 (6)	0.0020 (6)
C7	0.0283 (8)	0.0264 (8)	0.0211 (7)	−0.0099 (6)	0.0043 (6)	−0.0009 (6)
C8	0.0229 (7)	0.0377 (9)	0.0220 (7)	−0.0124 (6)	−0.0006 (6)	−0.0002 (6)
C9	0.0288 (8)	0.0193 (7)	0.0226 (7)	0.0045 (6)	0.0020 (6)	0.0022 (6)
C10	0.0167 (7)	0.0260 (7)	0.0207 (7)	−0.0057 (5)	0.0019 (5)	−0.0007 (6)
C11	0.0186 (7)	0.0269 (8)	0.0206 (7)	−0.0004 (6)	0.0050 (5)	0.0031 (6)
C12	0.0228 (7)	0.0292 (8)	0.0223 (7)	0.0086 (6)	0.0012 (6)	−0.0023 (6)
Cl1	0.01952 (18)	0.01895 (18)	0.01472 (18)	−0.00176 (12)	0.00186 (12)	0.00107 (11)
O7	0.0229 (5)	0.0326 (6)	0.0233 (5)	−0.0044 (4)	−0.0018 (4)	−0.0071 (5)
O8	0.0369 (6)	0.0321 (6)	0.0267 (6)	−0.0082 (5)	−0.0056 (5)	0.0132 (5)
O9	0.0339 (6)	0.0468 (7)	0.0197 (5)	−0.0226 (5)	0.0043 (5)	−0.0008 (5)
O10	0.0496 (8)	0.0424 (8)	0.0346 (7)	0.0217 (6)	0.0055 (6)	−0.0075 (6)

Geometric parameters (Å, º) top

O1—C1	1.4326 (18)	C4—H4B	0.9900
O1—C8	1.450 (2)	C5—C6	1.499 (2)
O1—Li1	2.094 (3)	C5—H5A	0.9900
O2—C3	1.4264 (18)	C5—H5B	0.9900
O2—C2	1.4573 (19)	C6—H6A	0.9900
O2—Li1	2.079 (3)	C6—H6B	0.9900
O3—C5	1.4296 (18)	C7—C8	1.494 (2)
O3—C4	1.4466 (18)	C7—H7A	0.9900
O3—Li1	2.074 (3)	C7—H7B	0.9900
O4—C7	1.4295 (18)	C8—H8A	0.9900
O4—C6	1.4473 (18)	C8—H8B	0.9900
O4—Li1	2.061 (3)	C9—C12ⁱ	1.499 (2)
O5—C10	1.4388 (16)	C9—H9A	0.9900
O5—C9	1.4394 (17)	C9—H9B	0.9900
O5—Li1	1.936 (3)	C10—C11	1.501 (2)
O6—C11	1.4203 (18)	C10—H10A	0.9900
O6—C12	1.4247 (18)	C10—H10B	0.9900
C1—C2	1.498 (2)	C11—H11A	0.9900
C1—H1A	0.9900	C11—H11B	0.9900
C1—H1B	0.9900	C12—C9ⁱ	1.499 (2)
C2—H2A	0.9900	C12—H12A	0.9900
C2—H2B	0.9900	C12—H12B	0.9900
C3—C4	1.508 (2)	Cl1—O10	1.4294 (12)
C3—H3A	0.9900	Cl1—O8	1.4343 (11)
C3—H3B	0.9900	Cl1—O7	1.4407 (11)
C4—H4A	0.9900	Cl1—O9	1.4451 (11)

C1—O1—C8	114.32 (12)	C6—C5—H5A	110.6
C1—O1—Li1	109.00 (11)	O3—C5—H5B	110.6
C8—O1—Li1	108.46 (11)	C6—C5—H5B	110.6
C3—O2—C2	114.29 (11)	H5A—C5—H5B	108.8
C3—O2—Li1	109.63 (11)	O4—C6—C5	110.67 (12)
C2—O2—Li1	107.45 (11)	O4—C6—H6A	109.5
C5—O3—C4	113.86 (11)	C5—C6—H6A	109.5
C5—O3—Li1	109.81 (11)	O4—C6—H6B	109.5
C4—O3—Li1	110.02 (11)	C5—C6—H6B	109.5
C7—O4—C6	113.93 (11)	H6A—C6—H6B	108.1
C7—O4—Li1	109.66 (11)	O4—C7—C8	105.61 (12)
C6—O4—Li1	107.81 (11)	O4—C7—H7A	110.6
C10—O5—C9	113.85 (11)	C8—C7—H7A	110.6
C10—O5—Li1	117.26 (11)	O4—C7—H7B	110.6
C9—O5—Li1	128.14 (11)	C8—C7—H7B	110.6
C11—O6—C12	114.41 (11)	H7A—C7—H7B	108.7
O5—Li1—O4	116.76 (12)	O1—C8—C7	110.79 (12)
O5—Li1—O3	107.10 (12)	O1—C8—H8A	109.5
O4—Li1—O3	81.74 (10)	C7—C8—H8A	109.5
O5—Li1—O2	108.58 (12)	O1—C8—H8B	109.5
O4—Li1—O2	134.35 (13)	C7—C8—H8B	109.5
O3—Li1—O2	80.36 (9)	H8A—C8—H8B	108.1
O5—Li1—O1	119.53 (12)	O5—C9—C12ⁱ	110.75 (12)
O4—Li1—O1	80.89 (10)	O5—C9—H9A	109.5
O3—Li1—O1	133.22 (12)	C12ⁱ—C9—H9A	109.5
O2—Li1—O1	81.58 (10)	O5—C9—H9B	109.5
O1—C1—C2	105.85 (12)	C12ⁱ—C9—H9B	109.5
O1—C1—H1A	110.6	H9A—C9—H9B	108.1
C2—C1—H1A	110.6	O5—C10—C11	112.07 (11)
O1—C1—H1B	110.6	O5—C10—H10A	109.2
C2—C1—H1B	110.6	C11—C10—H10A	109.2
H1A—C1—H1B	108.7	O5—C10—H10B	109.2
O2—C2—C1	110.23 (12)	C11—C10—H10B	109.2
O2—C2—H2A	109.6	H10A—C10—H10B	107.9
C1—C2—H2A	109.6	O6—C11—C10	107.90 (11)
O2—C2—H2B	109.6	O6—C11—H11A	110.1
C1—C2—H2B	109.6	C10—C11—H11A	110.1
H2A—C2—H2B	108.1	O6—C11—H11B	110.1
O2—C3—C4	105.34 (12)	C10—C11—H11B	110.1
O2—C3—H3A	110.7	H11A—C11—H11B	108.4
C4—C3—H3A	110.7	O6—C12—C9ⁱ	111.52 (12)
O2—C3—H3B	110.7	O6—C12—H12A	109.3
C4—C3—H3B	110.7	C9ⁱ—C12—H12A	109.3
H3A—C3—H3B	108.8	O6—C12—H12B	109.3
O3—C4—C3	109.81 (12)	C9ⁱ—C12—H12B	109.3
O3—C4—H4A	109.7	H12A—C12—H12B	108.0
C3—C4—H4A	109.7	O10—Cl1—O8	109.72 (8)
O3—C4—H4B	109.7	O10—Cl1—O7	109.37 (7)
C3—C4—H4B	109.7	O8—Cl1—O7	110.20 (7)
H4A—C4—H4B	108.2	O10—Cl1—O9	109.99 (9)
O3—C5—C6	105.53 (12)	O8—Cl1—O9	108.50 (7)
O3—C5—H5A	110.6	O7—Cl1—O9	109.04 (7)

C10—O5—Li1—O4	79.93 (16)	C1—O1—Li1—O4	−119.04 (11)
C9—O5—Li1—O4	−110.63 (15)	C8—O1—Li1—O4	6.01 (12)
C10—O5—Li1—O3	−9.32 (17)	C1—O1—Li1—O3	−49.5 (2)
C9—O5—Li1—O3	160.13 (11)	C8—O1—Li1—O3	75.50 (19)
C10—O5—Li1—O2	−94.65 (14)	C1—O1—Li1—O2	18.65 (12)
C9—O5—Li1—O2	74.80 (17)	C8—O1—Li1—O2	143.69 (10)
C10—O5—Li1—O1	174.62 (12)	C8—O1—C1—C2	−165.58 (12)
C9—O5—Li1—O1	−15.9 (2)	Li1—O1—C1—C2	−44.04 (15)
C7—O4—Li1—O5	142.15 (13)	C3—O2—C2—C1	81.88 (16)
C6—O4—Li1—O5	−93.29 (15)	Li1—O2—C2—C1	−40.01 (16)
C7—O4—Li1—O3	−112.81 (10)	O1—C1—C2—O2	56.83 (16)
C6—O4—Li1—O3	11.75 (11)	C2—O2—C3—C4	−167.89 (12)
C7—O4—Li1—O2	−45.1 (2)	Li1—O2—C3—C4	−47.21 (15)
C6—O4—Li1—O2	79.51 (19)	C5—O3—C4—C3	89.63 (15)
C7—O4—Li1—O1	23.59 (12)	Li1—O3—C4—C3	−34.13 (15)
C6—O4—Li1—O1	148.15 (10)	O2—C3—C4—O3	53.90 (15)
C5—O3—Li1—O5	133.72 (12)	C4—O3—C5—C6	−166.51 (12)
C4—O3—Li1—O5	−100.20 (13)	Li1—O3—C5—C6	−42.64 (14)
C5—O3—Li1—O4	18.16 (12)	C7—O4—C6—C5	82.64 (15)
C4—O3—Li1—O4	144.25 (10)	Li1—O4—C6—C5	−39.31 (15)
C5—O3—Li1—O2	−119.67 (11)	O3—C5—C6—O4	55.08 (15)
C4—O3—Li1—O2	6.42 (12)	C6—O4—C7—C8	−168.01 (12)
C5—O3—Li1—O1	−51.0 (2)	Li1—O4—C7—C8	−47.09 (14)
C4—O3—Li1—O1	75.10 (19)	C1—O1—C8—C7	88.01 (15)
C3—O2—Li1—O5	128.64 (12)	Li1—O1—C8—C7	−33.84 (15)
C2—O2—Li1—O5	−106.61 (13)	O4—C7—C8—O1	54.00 (15)
C3—O2—Li1—O4	−44.6 (2)	C10—O5—C9—C12ⁱ	−134.05 (13)
C2—O2—Li1—O4	80.17 (19)	Li1—O5—C9—C12ⁱ	56.20 (18)
C3—O2—Li1—O3	23.72 (12)	C9—O5—C10—C11	81.83 (15)
C2—O2—Li1—O3	148.47 (10)	Li1—O5—C10—C11	−107.23 (14)
C3—O2—Li1—O1	−112.94 (11)	C12—O6—C11—C10	178.36 (11)
C2—O2—Li1—O1	11.80 (12)	O5—C10—C11—O6	67.70 (15)
C1—O1—Li1—O5	125.29 (14)	C11—O6—C12—C9ⁱ	112.52 (14)
C8—O1—Li1—O5	−109.67 (15)

Symmetry code: (i) −x, −y, −z+2.

Experimental details

Crystal data
Chemical formula	[Li₂(C₈H₁₆O₄)₃](ClO₄)₂
M_r	741.40
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	7.7395 (7), 14.1924 (13), 15.2801 (14)
β (°)	95.962 (2)
V (Å³)	1669.3 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.28
Crystal size (mm)	0.40 × 0.30 × 0.20

Data collection
Diffractometer	Bruker CCD-1000 area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2003)
T_min, T_max	0.897, 0.947
No. of measured, independent and observed [I > 2σ(I)] reflections	13593, 3412, 3139
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.626

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.092, 1.04
No. of reflections	3412
No. of parameters	217
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.51, −0.36

Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXTL (Sheldrick, 2008), SHELXTL and FCF_filter (Guzei, 2007), SHELXTL and DIAMOND (Brandenburg, 1999), SHELXTL, publCIF (Westrip, 2010) and modiCIFer (Guzei, 2007).

Selected bond lengths (Å) top

O1—Li1	2.094 (3)	O4—Li1	2.061 (3)
O2—Li1	2.079 (3)	O5—Li1	1.936 (3)
O3—Li1	2.074 (3)

References

Blasius, E. & Janzen, K. P. (1982). Pure Appl. Chem. 54, 2115–2128. CrossRef CAS Web of Science Google Scholar
Blasius, E., Janzen, K. P., Klotz, H. & Toussaint, A. (1982). Makromol. Chem. 183, 1401–1411. CrossRef CAS Google Scholar
Bollmann, M. & Olbrich, F. (2004). Private communication. Google Scholar
Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2003). SMART, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruno, I. J., Cole, J. C., Edgington, P. R., Kessler, M., Macrae, C. F., McCabe, P., Pearson, J. & Taylor, R. (2002). Acta Cryst. B58, 389–397. Web of Science CrossRef CAS IUCr Journals Google Scholar
Dalley, N. D. (1978). Synthetic Multidentate Macrocyclic Compounds, edited by R. M. Izatt & J. J. Christensen, pp. 207–243. New York: Academic Press. Google Scholar
Doyle, J. M. & McCord, B. R. (1998). J. Chromatogr. B, 714, 105–111. CrossRef CAS Google Scholar
Frühauf, S. & Zeller, W. J. (1991). Cancer Res. 51, 2943–2948. PubMed Web of Science Google Scholar
Guzei, I. A. (2007). FCF_filter and modiCIFer. Molecular Structure Laboratory, University of Wisconsin-Madison, Madison, Wisconsin, USA. Google Scholar
Guzei, I. A., Spencer, L. C., Xiao, L. & Burnette, R. R. (2010). Acta Cryst. E66, m440–m441. Web of Science CrossRef IUCr Journals Google Scholar
Hayashita, T., Lee, J. H., Hankins, M. G., Lee, J. C., Kim, J. S., Knobeloch, J. M. & Bartsch, R. A. (1992). Anal. Chem. 64, 815–819. CrossRef CAS Web of Science Google Scholar
Jagannadh, B. & Sarma, J. A. R. P. (1999). J. Phys. Chem. A, 103, 10993–10997. Web of Science CrossRef CAS Google Scholar
Jones, P. G., Moers, O. & Blaschette, A. (1997). Acta Cryst. C53, 1809–1811. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Lehn, J. M. (1973). Structure Bonding, 16, 1–69. CrossRef CAS Google Scholar
Lehn, J. M. (1995). Supramolecular Chemistry: Concepts and Perspectives. Weinheim: VCH. Google Scholar
Prince, E. & Nicholson, W. L. (1983). Acta Cryst. A39, 407–410. CrossRef CAS IUCr Journals Google Scholar
Raithby, P. R., Shields, G. P. & Allen, F. H. (1997). Acta Cryst. B53, 241–251. CrossRef CAS Web of Science IUCr Journals Google Scholar
Rollett, J. S. (1988). Crystallographic Computing, Vol. 4, pp. 149–166. Oxford University Press. Google Scholar
Shannon, R. D. (1976). Acta Cryst. A32, 751–767. CrossRef CAS IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shoham, G., Lipscomb, W. N. & Olsher, U. (1983). J. Chem. Soc. Chem. Commun. pp. 208–209. CrossRef Web of Science Google Scholar
Westrip, S. P. (2010). publCIF. In preparation. Google Scholar

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