Buy article online - an online subscription or single-article purchase is required to access this article.
Download citation
Download citation
link to html
The crystal structures of acetonitrile solvates of two related lithium calixarene complexes have been determined by low-temperature single-crystal X-ray diffraction using synchrotron radiation. Bis(μ-5,11,17,23-tetra-tert-butyl-26,28-dihydr­oxy-25-meth­oxy-27-oxido­calix[4]arene)dilithium(I) acetonitrile tetra­­solvate, [Li2(C45H57O4)2]·4C2H3N or [p-tert-butyl­calix[4]arene­(OMe)(OH)2(OLi)]2·4MeCN, (I), crystallizes with the complex across a centre of symmetry and with four mol­ecules of unbound aceto­nitrile of crystallization per com­plex. Tetra­acetonitrile­bis(μ-5,11,17,23-tetra-tert-butyl-26,28-dihydr­oxy-25,27-dioxidocalix[4]arene)tetra­lithium(I) acetonitrile octa­solvate, [Li4(C44H54O4)2(C2H3N)4]·8C2H3N or {p-tert-butyl­calix[4]arene(OH)2(OLi)[OLi(NCMe)2]}2·8MeCN, (II), also crystallizes with the complex lying across a centre of symmetry and contains eight mol­ecules of unbound acetonitrile per complex plus four more directly bound to two of the lithium ions, two on each ion. The cores of both complexes are partially supported by O—H...O hydrogen bonds. The meth­oxy methyl groups in (I) prevent the binding of any more than two Li+ ions, while the corresponding two O-atom sites in (II) bind an extra Li+ ion each, making four in total. The calixarene cone adopts an undistorted cone conformation in (I), but an elliptical one in (II).

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109025311/eg3021sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270109025311/eg3021Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270109025311/eg3021IIsup3.hkl
Contains datablock II

CCDC references: 746040; 746041

Comment top

Lithiated calixarenes are useful synthons and continue to attract interest for a number of reasons, most recently because of their hydrogen storage potential (Venkataramanan et al., 2008). A number of lithium-containing calixarenes have now been structurally characterized and some intruiging structures/reactivity have been highlighted (Dubberley et al., 1997; Gueneau et al., 2003), most notably the C—H activation in the chromium complex C92H111CrLi2N2O8.4CH3CN (Gibson et al., 1997).

A Cambridge Structural Database (CSD; Version 5.30 of November 2008 plus two updates; Allen, 2002) search yielded only a few results for lithium-containing calixarenes, some of which have lithium present as a secondary metal cation while the rest contain lithium as the primary metal of the complex.

We report here the structures of two new lithiated calixarenes which were isolated as by-products of attempted syntheses of boron or manganese-containing calixarene complexes. In each case the lithium originates from the butyl lithium reagent (see Experimental section).

The new lithium calixarene dimer (I) is located on a centre of symmetry (Fig 1). The molecule consists of two p-tert-butyl-calix[4]arene(OMe) ligands, each of which adopt a cone conformation with neglible distortion (Δ = 0.045 Å; Δ is the difference in length between vectors linking centroids of opposite rings). The molecule contains two lithium ions, both with tetrahedral geometry, which are four-coordinate. The lithium ions are bound to four O atoms, three from one calixarene and one from the other, which forms a bridge between the ligands. One of the O atoms of each calixarene (O2) retains its methyl group, having only lost one from the p-tert-butyl-calix[4]arene(OMe)2 starting material during the course of the reaction. As a result, these methyl groups are positioned pointing `up' and `down' when viewed from a side-on perspective. It is highly likely that the presence of these methyl groups is preventing further lithium ions from binding. A comparison can be made with compound (II), which has no methoxy groups in its starting calixarene but forms a very similar dimer, except with four lithium ions present. The dimeric structure, (I).4MeCN, has four acetonitrile molecules of crystallization present, two of which reside inside the cavities of the calixarenes, one in each, and two that are exo to the cavities.

An interesting feature of (I) is that there are four intramolecular hydrogen bonds supporting the metal–oxygen core of the molecule. Two O atoms (O1 and O3) of each calixarene remain protonated. Both of these H atoms point to, and hydrogen bond with, a neighboring O atom of the same calixarene ligand (O4), which acts as an acceptor to both (see Table 2).

Compound (II) also lies on a centre of symmetry. This time the calixarene adopts a distorted cone, or elliptical, conformation (Δ = 0.671 Å; Fig. 2). The molecule contains a total of four lithium ions, each of which is tetrahedral and four-coordinate. Two of the lithium ions [Li1 and Li1i; symmetry code: (i) -x + 2, -y + 1, -z + 2] are bound to four O atoms, two from each calixarene ligand. The other two lithium ions are only bound to two O atoms, one from each calixarene, but the coordination environment is completed by two molecules of acetonitrile per lithium ion. Lithium calixarenes containing these Li—NCMe moities have been seen before (Liu et al., 2006; Redshaw et al., 2008), with another example being the chromium calix[4]arene complex synthesized by Gibson et al. (1997). These acetonitrile ligands sit `above' and `below' the molecule, when viewed from a side-on perspective, and they appear in a `wing' shape relative to each other. The structure also contains eight more molecules of unbound acetonitrile per molecule of dimer. One acetonitrile sits in the cavity of each calixarene ligand, one MeCN sits just exo to each of the caivities, and the remaining four sit at regular intervals around the `waist' of the molecule. As seen in (I), there are four protonated O atoms, two on each calixarene (O2 and O4). The H atoms (H2 and H4) are pointing to, and hydrogen bonding with, a single neighboring O atom (O1; see Table 4).

The Li—O bond lengths for (I) and (II) are close to the mean when compared with the reported calix[4]arene O—Li bond lengths found in the CSD, the mean of these being 1.96 Å (range 1.83–2.35 Å). The Li—O lengths are shorter for bonds to the deprotonated phenoxy O atoms, as expected. The O—Li—O bond angles seen in (I) are larger, while those in (II) are mostly close to the average when compared to those reported in the CSD; the mean of these being 96.5° (range 86.3–105.4°). The exception is O4i—Li1—O2, which is much larger than any reported and in this case bridges the two calixarene molecules, giving rise to a significantly distorted tetrahedral environment at Li1 (see Tables 1 and 3 [no geometric parameters were selected for (I); please check that the correct ones have been added to Table 1]. The Li—N bond lengths are about average when compared with the reported values in the CSD (mean 2.02 Å, range 1.91–2.20 Å). The mean of the reported angles for O—Li—N is 125.1° (range 105.5–168.6°); the angles seen in (II) are rather less than those reported. The three hits from the CSD containing a lithium ion bound to two acetonitrile ligands and two O atoms, yielded an average N—Li—N bond angle of 102.0° (range 91.2–119.6°). The corresponding angles in (II) are only slightly higher than this average value.

The major differences in the two structures reported here are the fact that they contain different core motifs and that the calixarene ligands for (II) are noticably distorted compared with those of (I), which have neglible distortion. Other than these major differences, bond lengths and angles are similar and show nothing too unusual. There is a significant link between these structures and although they were obtained using different synthetic methods, they are quite similar. It would appear that (I) represents a partially reacted version of (II), with one O—Me per calixarene still present, blocking further reaction with more lithium.

Related literature top

For related literature, see: Allen (2002); Dubberley et al. (1997); Gibson et al. (1997); Gueneau et al. (2003); Liu et al. (2006); Redshaw et al. (2007, 2008); Venkataramanan et al. (2008).

Experimental top

For the synthesis of (I), calix[4]arene(OMe)2 (1.00 g, 1.48 mmol) in diethylether (30 ml) was cooled to 195 K and then n-BuLi was added (2.03 ml, 3.25 mmol, 1.6 M). The solution was allowed to warm to ambient temperature and was stirred for 3 h, and then MnCl2 (0.18 g, 1.43 mmol) in tetrahydrofuran (10 ml) was added. The solution was stirred for 12 h, the volatiles were removed in vacuo and the residue extracted into MeCN (30 ml). On cooling the brown/purple solution to 273 K, small colourless prisms of (I) formed (yield 0.39 g, 35%).

For the synthesis of (II), to 1,3-bis(trifluoromethyl)benzene (1.00, 4.67 mmol) was added n-BuLi (2.91 ml, 4.66 mmol, 1.6M) in diethyl ether (30 ml) at 195 K. After stirring for 2 h at room temp, {[ClB]2tert-butylcalix[4]arene} (1.71 g, 2.32 mmol) was added and stirring was continued for a further 12 h. Volatile components were removed in vacuo, and the residue was taken up in MeCN (30 ml). Prolonged standing (2–3 d) at 273 K afforded small colourless prisms of (II) (yield 0.33 g, 16%).

Refinement top

Aromatic (C—H = 0.95 Å), methyl (C—H = 0.98 Å) and methine (C—H = 0.99 Å) H atoms were placed in geometric positions using a riding model. Methyl H atoms, including those on MeCN, were refined allowing rotational freedom in all ordered groups. The coordinates of OH atoms were freely refined. Uiso values were set to 1.2Ueq of the carrier atom [1.5Ueq for OH in (I) and for all methyl H atoms]. Geometric and displacement parameter restraints were applied to two tBu groups, which were modelled as disordered with two sets of positions for the methyl groups [at C7 and C18 in (I)]. The major occupancies were 70.3 (17) and 86.4 (7)%, respectively. The N2/C48/C49 acetonitrile group in (I) has fairly large U values, but these were left unrestrained as applying the restraints had little effect on the displacement parameters and the observed values are a true reflection of reality in the crystal lattice. This behaviour is common for unbound solvent molecules in calixarene complexes (Redshaw et al., 2007).

Computing details top

Data collection: APEX2 (Bruker 2006) for (I); APEX2 (Bruker, 2006) for (II). Cell refinement: SAINT (Bruker, 2006) for (I); SAINT (Bruker 2006) for (II). For both compounds, data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Version 6.10; Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Version 6.10; Sheldrick, 2008) and local programs.

Figures top
[Figure 1] Fig. 1. A view of (I), showing part of the atom-labelling scheme. The calixarene numbering scheme starts at the ipso C atom, goes around the C6 ring, then the tBu group and finally the bridging CH2 unit. Displacement ellipsoids are drawn at the 30% probability level, H atoms are represented by circles of arbitrary radii and hydrogen bonding is shown by dashed lines. [Symmetry code: (i) -x, -y + 1, -z + 1.]
[Figure 2] Fig. 2. A view of (II), showing part of the atom-labelling scheme. The calixarene numbering scheme starts at the ipso C atom, goes around the C6 ring, then the tBu group and finally the bridging CH2 unit. Displacement ellipsoids are drawn at the 30% probability level, H atoms are represented by circles of arbitrary radii and hydrogen bonding is shown by dashed lines. [Symmetry code: (i) -x + 2, -y + 1, -z + 2.]
[Figure 3] Fig. 3. A view of the core for (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level, H atoms are represented by circles of arbitrary radii and hydrogen bonding is shown by dashed lines.
(I) bis(µ-5,11,17,23-tetra-tert-butyl-26,28-dihydroxy-25-methoxy-27- oxidocalix[4]arene)dilithium(I) acetonitrile tetrasolvate top
Crystal data top
[Li2(C45H57O4)2]·4C2H3NF(000) = 1624
Mr = 1501.91Dx = 1.109 Mg m3
Monoclinic, P21/nSynchrotron radiation, λ = 0.6911 Å
Hall symbol: -P 2ynCell parameters from 5608 reflections
a = 12.8368 (11) Åθ = 2.3–26.4°
b = 17.8044 (15) ŵ = 0.07 mm1
c = 19.6735 (16) ÅT = 150 K
β = 90.2746 (12)°Rod, colourless
V = 4496.4 (7) Å30.24 × 0.06 × 0.05 mm
Z = 2
Data collection top
Bruker APEX II CCD
diffractometer
8536 independent reflections
Radiation source: Daresbury SRS station 9.85918 reflections with I > 2σ(I)
Silicon 111 monochromatorRint = 0.063
ω rotation with narrow frames scansθmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Version 2004/1; Sheldrick, 2004)
h = 1515
Tmin = 0.984, Tmax = 0.997k = 2121
29080 measured reflectionsl = 2124
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.074Hydrogen site location: geom except OH coords freely refined
wR(F2) = 0.226H atoms treated by a mixture of independent and constrained refinement
S = 1.03 w = 1/[σ2(Fo2) + (0.1085P)2 + 3.2181P]
where P = (Fo2 + 2Fc2)/3
8536 reflections(Δ/σ)max = 0.002
561 parametersΔρmax = 0.75 e Å3
172 restraintsΔρmin = 0.37 e Å3
Crystal data top
[Li2(C45H57O4)2]·4C2H3NV = 4496.4 (7) Å3
Mr = 1501.91Z = 2
Monoclinic, P21/nSynchrotron radiation, λ = 0.6911 Å
a = 12.8368 (11) ŵ = 0.07 mm1
b = 17.8044 (15) ÅT = 150 K
c = 19.6735 (16) Å0.24 × 0.06 × 0.05 mm
β = 90.2746 (12)°
Data collection top
Bruker APEX II CCD
diffractometer
8536 independent reflections
Absorption correction: multi-scan
(SADABS; Version 2004/1; Sheldrick, 2004)
5918 reflections with I > 2σ(I)
Tmin = 0.984, Tmax = 0.997Rint = 0.063
29080 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.074172 restraints
wR(F2) = 0.226H atoms treated by a mixture of independent and constrained refinement
S = 1.03Δρmax = 0.75 e Å3
8536 reflectionsΔρmin = 0.37 e Å3
561 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.

Refinement. Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > σ(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ 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
xyzUiso*/UeqOcc. (<1)
Li10.0214 (3)0.4768 (3)0.4108 (2)0.0402 (10)
O10.16381 (14)0.49566 (11)0.44703 (10)0.0404 (5)
H10.125 (3)0.5273 (19)0.4802 (18)0.061*
O20.03983 (13)0.44608 (9)0.32171 (9)0.0343 (4)
O30.06579 (14)0.56860 (10)0.40956 (10)0.0381 (4)
H30.041 (3)0.5730 (19)0.4516 (18)0.057*
O40.04054 (14)0.57684 (10)0.51858 (9)0.0381 (4)
C10.26194 (19)0.52451 (15)0.43569 (13)0.0356 (6)
C20.3089 (2)0.57114 (15)0.48418 (14)0.0385 (6)
C30.4046 (2)0.60298 (16)0.46888 (15)0.0431 (7)
H3A0.43600.63580.50110.052*
C40.4564 (2)0.58896 (16)0.40853 (15)0.0423 (7)
C50.41016 (19)0.53838 (15)0.36412 (15)0.0404 (6)
H50.44610.52560.32360.049*
C60.31326 (19)0.50531 (14)0.37604 (14)0.0367 (6)
C70.5586 (2)0.62964 (18)0.39155 (18)0.0553 (8)
C80.5319 (6)0.7116 (4)0.3781 (8)0.099 (3)0.703 (17)
H8A0.59560.73920.36710.149*0.703 (17)
H8B0.50010.73340.41880.149*0.703 (17)
H8C0.48290.71490.33990.149*0.703 (17)
C90.6169 (7)0.5945 (6)0.3333 (4)0.079 (2)0.703 (17)
H9A0.68100.62290.32500.119*0.703 (17)
H9B0.57310.59520.29240.119*0.703 (17)
H9C0.63460.54240.34480.119*0.703 (17)
C100.6327 (5)0.6276 (5)0.4541 (3)0.067 (2)0.703 (17)
H10A0.69770.65360.44310.100*0.703 (17)
H10B0.64790.57530.46610.100*0.703 (17)
H10C0.59930.65260.49260.100*0.703 (17)
C8X0.5354 (14)0.6858 (15)0.3319 (14)0.102 (7)0.297 (17)
H8D0.59950.71260.32010.153*0.297 (17)
H8E0.48230.72190.34620.153*0.297 (17)
H8F0.51010.65780.29220.153*0.297 (17)
C9X0.6330 (16)0.5727 (12)0.3645 (18)0.107 (9)0.297 (17)
H9D0.69880.59740.35300.161*0.297 (17)
H9E0.60330.54930.32370.161*0.297 (17)
H9F0.64570.53420.39910.161*0.297 (17)
C10X0.6046 (17)0.677 (2)0.4485 (11)0.119 (9)0.297 (17)
H10D0.66920.70010.43290.178*0.297 (17)
H10E0.61960.64420.48770.178*0.297 (17)
H10F0.55470.71550.46170.178*0.297 (17)
C110.26415 (19)0.45412 (14)0.32329 (14)0.0375 (6)
H11A0.31930.42830.29720.045*
H11B0.22140.41540.34610.045*
C120.08800 (19)0.49991 (13)0.28061 (12)0.0311 (5)
C130.1965 (2)0.49980 (14)0.27562 (13)0.0347 (6)
C140.2409 (2)0.54884 (16)0.22944 (14)0.0422 (7)
H140.31430.54770.22360.051*
C150.1832 (2)0.59947 (16)0.19136 (14)0.0453 (7)
C160.0765 (2)0.60231 (16)0.20323 (14)0.0423 (6)
H160.03580.63880.17990.051*
C170.02708 (19)0.55343 (14)0.24823 (12)0.0336 (6)
C180.2364 (3)0.65003 (19)0.13841 (16)0.0579 (8)
C190.3268 (4)0.6920 (3)0.1709 (2)0.0823 (17)0.864 (7)
H19A0.37220.65620.19460.123*0.864 (7)
H19B0.29990.72870.20350.123*0.864 (7)
H19C0.36650.71800.13560.123*0.864 (7)
C200.1643 (4)0.7057 (4)0.1077 (4)0.112 (3)0.864 (7)
H20A0.10560.67950.08630.169*0.864 (7)
H20B0.20150.73510.07330.169*0.864 (7)
H20C0.13830.73940.14320.169*0.864 (7)
C210.2831 (4)0.5994 (3)0.0832 (2)0.0767 (16)0.864 (7)
H21A0.22800.56840.06300.115*0.864 (7)
H21B0.33650.56690.10340.115*0.864 (7)
H21C0.31470.63070.04780.115*0.864 (7)
C19X0.3538 (13)0.637 (2)0.135 (2)0.128 (14)*0.136 (7)
H19D0.38740.66170.17410.192*0.136 (7)
H19E0.38090.65910.09290.192*0.136 (7)
H19F0.36850.58350.13600.192*0.136 (7)
C20X0.209 (3)0.7282 (13)0.149 (2)0.116 (13)*0.136 (7)
H20D0.20960.73900.19820.174*0.136 (7)
H20E0.13960.73800.13070.174*0.136 (7)
H20F0.26010.76050.12660.174*0.136 (7)
C21X0.191 (2)0.6278 (16)0.0682 (10)0.073 (8)*0.136 (7)
H21D0.22560.58180.05230.109*0.136 (7)
H21E0.20380.66840.03570.109*0.136 (7)
H21F0.11630.61900.07220.109*0.136 (7)
C220.08684 (19)0.56515 (15)0.26564 (13)0.0359 (6)
H22A0.12850.56930.22330.043*
H22B0.11290.52160.29180.043*
C230.08764 (18)0.63548 (14)0.37778 (13)0.0337 (6)
C240.09855 (18)0.63590 (14)0.30719 (13)0.0340 (6)
C250.1139 (2)0.70451 (16)0.27513 (15)0.0461 (7)
H250.12220.70510.22710.055*
C260.1177 (3)0.77211 (17)0.30988 (17)0.0536 (8)
C270.1130 (2)0.76839 (16)0.38071 (16)0.0473 (7)
H270.11930.81360.40610.057*
C280.09938 (19)0.70132 (15)0.41544 (14)0.0376 (6)
C290.1266 (4)0.8470 (2)0.2705 (2)0.0736 (11)
C300.2345 (4)0.8537 (3)0.2413 (3)0.1007 (16)
H30A0.25040.80890.21420.151*
H30B0.23850.89840.21230.151*
H30C0.28490.85810.27830.151*
C310.0876 (6)0.9110 (2)0.3121 (3)0.122 (2)
H31A0.08380.95620.28380.183*
H31B0.01800.89910.32980.183*
H31C0.13510.91990.35010.183*
C320.0523 (3)0.8462 (2)0.2070 (2)0.0760 (11)
H32A0.07510.80710.17510.114*
H32B0.01920.83570.22190.114*
H32C0.05480.89520.18440.114*
C330.0936 (2)0.70126 (16)0.49264 (14)0.0426 (7)
H33A0.13690.74290.51030.051*
H33B0.12320.65360.50990.051*
C340.0796 (2)0.64663 (14)0.52886 (12)0.0358 (6)
C350.0169 (2)0.70987 (16)0.51952 (13)0.0386 (6)
C360.0586 (2)0.78038 (16)0.53160 (14)0.0442 (7)
H360.01500.82310.52620.053*
C370.1619 (2)0.79135 (16)0.55130 (14)0.0459 (7)
C380.2230 (2)0.72755 (16)0.55800 (14)0.0448 (7)
H380.29410.73320.57050.054*
C390.1844 (2)0.65577 (15)0.54722 (13)0.0385 (6)
C400.2031 (3)0.86959 (18)0.56844 (18)0.0584 (8)
C410.1657 (4)0.9264 (2)0.5184 (3)0.1048 (18)
H41A0.17930.90850.47220.157*
H41B0.20240.97390.52590.157*
H41C0.09060.93410.52420.157*
C420.1670 (3)0.8896 (2)0.6399 (2)0.0773 (11)
H42A0.19900.93710.65400.116*
H42B0.18790.84980.67160.116*
H42C0.09100.89480.64020.116*
C430.3239 (3)0.8695 (2)0.5725 (2)0.0757 (11)
H43A0.35250.85370.52870.114*
H43B0.34680.83450.60810.114*
H43C0.34870.92010.58340.114*
C440.2568 (2)0.58892 (16)0.55131 (14)0.0431 (7)
H44A0.21670.54450.56630.052*
H44B0.31120.59900.58600.052*
C450.0196 (2)0.37615 (16)0.28740 (16)0.0480 (7)
H45A0.02820.38490.24920.072*
H45B0.01190.34060.31930.072*
H45C0.08520.35540.27030.072*
N10.2374 (5)0.8298 (3)0.3158 (3)0.144 (2)
C460.2126 (3)0.7736 (2)0.33681 (18)0.0647 (9)
C470.1816 (3)0.70323 (19)0.36270 (16)0.0561 (8)
H47A0.23850.66700.35720.084*
H47B0.12000.68560.33780.084*
H47C0.16490.70820.41100.084*
N20.6234 (10)0.9253 (5)0.4142 (7)0.296 (7)
C480.5342 (8)0.9287 (3)0.4088 (4)0.136 (3)
C490.4287 (5)0.9297 (4)0.3997 (3)0.120 (2)
H49A0.41130.96100.36020.181*
H49B0.39550.95050.44030.181*
H49C0.40350.87840.39200.181*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Li10.040 (2)0.041 (2)0.040 (2)0.0083 (19)0.0106 (19)0.0056 (19)
O10.0335 (10)0.0496 (11)0.0380 (10)0.0119 (8)0.0052 (8)0.0018 (8)
O20.0337 (9)0.0343 (9)0.0350 (9)0.0055 (7)0.0065 (7)0.0007 (7)
O30.0434 (11)0.0390 (10)0.0320 (10)0.0011 (8)0.0065 (8)0.0015 (8)
O40.0403 (10)0.0405 (10)0.0335 (9)0.0116 (8)0.0081 (8)0.0018 (8)
C10.0280 (13)0.0396 (14)0.0394 (14)0.0027 (10)0.0009 (11)0.0073 (11)
C20.0334 (14)0.0420 (14)0.0401 (15)0.0007 (11)0.0037 (11)0.0034 (12)
C30.0329 (14)0.0434 (15)0.0528 (17)0.0036 (11)0.0101 (12)0.0007 (13)
C40.0242 (13)0.0459 (15)0.0569 (18)0.0009 (11)0.0014 (12)0.0015 (13)
C50.0260 (13)0.0436 (15)0.0518 (17)0.0027 (11)0.0050 (11)0.0032 (13)
C60.0277 (13)0.0370 (13)0.0454 (15)0.0032 (10)0.0007 (11)0.0001 (12)
C70.0286 (14)0.0570 (18)0.080 (2)0.0090 (13)0.0009 (14)0.0000 (16)
C80.056 (4)0.064 (4)0.178 (10)0.014 (3)0.006 (5)0.048 (5)
C90.047 (4)0.121 (6)0.070 (4)0.038 (4)0.018 (3)0.012 (4)
C100.032 (3)0.085 (5)0.083 (4)0.016 (3)0.005 (2)0.008 (3)
C8X0.053 (8)0.099 (13)0.154 (16)0.033 (8)0.018 (11)0.047 (12)
C9X0.028 (7)0.097 (11)0.20 (3)0.004 (7)0.031 (14)0.023 (12)
C10X0.054 (11)0.16 (2)0.138 (13)0.053 (13)0.017 (9)0.054 (14)
C110.0300 (13)0.0372 (13)0.0453 (15)0.0007 (10)0.0059 (11)0.0047 (12)
C120.0330 (13)0.0347 (13)0.0258 (12)0.0050 (10)0.0063 (10)0.0043 (10)
C130.0339 (13)0.0368 (13)0.0334 (13)0.0030 (10)0.0062 (10)0.0091 (11)
C140.0348 (14)0.0518 (16)0.0399 (15)0.0077 (12)0.0121 (12)0.0056 (13)
C150.0501 (17)0.0497 (16)0.0361 (15)0.0103 (13)0.0128 (13)0.0004 (12)
C160.0499 (17)0.0446 (15)0.0325 (14)0.0025 (12)0.0042 (12)0.0049 (12)
C170.0351 (13)0.0391 (13)0.0266 (12)0.0044 (11)0.0000 (10)0.0022 (10)
C180.066 (2)0.063 (2)0.0454 (18)0.0121 (16)0.0183 (15)0.0101 (15)
C190.106 (4)0.075 (3)0.066 (3)0.053 (3)0.030 (2)0.005 (2)
C200.086 (4)0.119 (5)0.133 (6)0.013 (3)0.048 (3)0.089 (4)
C210.108 (4)0.074 (3)0.048 (2)0.028 (3)0.037 (2)0.003 (2)
C220.0318 (13)0.0421 (14)0.0336 (14)0.0045 (11)0.0035 (10)0.0014 (11)
C230.0225 (12)0.0361 (13)0.0427 (15)0.0011 (10)0.0046 (10)0.0014 (11)
C240.0226 (12)0.0394 (14)0.0401 (14)0.0007 (10)0.0021 (10)0.0013 (11)
C250.0483 (17)0.0464 (16)0.0436 (16)0.0017 (13)0.0132 (13)0.0025 (13)
C260.0571 (19)0.0425 (16)0.061 (2)0.0052 (14)0.0197 (16)0.0011 (14)
C270.0398 (15)0.0402 (15)0.062 (2)0.0063 (12)0.0051 (14)0.0082 (14)
C280.0222 (12)0.0426 (14)0.0479 (16)0.0006 (10)0.0055 (11)0.0074 (12)
C290.102 (3)0.0473 (19)0.072 (2)0.0144 (19)0.021 (2)0.0056 (17)
C300.092 (3)0.107 (4)0.103 (4)0.042 (3)0.007 (3)0.048 (3)
C310.240 (7)0.046 (2)0.080 (3)0.006 (3)0.016 (4)0.007 (2)
C320.081 (3)0.062 (2)0.084 (3)0.0062 (19)0.002 (2)0.020 (2)
C330.0368 (15)0.0429 (15)0.0481 (16)0.0013 (11)0.0147 (12)0.0107 (12)
C340.0440 (15)0.0401 (14)0.0235 (12)0.0117 (11)0.0092 (11)0.0003 (10)
C350.0390 (14)0.0486 (15)0.0283 (13)0.0070 (12)0.0126 (11)0.0060 (11)
C360.0531 (18)0.0437 (15)0.0359 (15)0.0038 (13)0.0111 (13)0.0085 (12)
C370.0551 (18)0.0484 (16)0.0343 (15)0.0137 (14)0.0037 (13)0.0068 (12)
C380.0473 (16)0.0533 (17)0.0339 (15)0.0153 (13)0.0002 (12)0.0050 (12)
C390.0413 (15)0.0482 (15)0.0260 (13)0.0087 (12)0.0019 (11)0.0010 (11)
C400.064 (2)0.0531 (19)0.058 (2)0.0155 (16)0.0010 (16)0.0089 (15)
C410.141 (4)0.064 (2)0.109 (4)0.049 (3)0.055 (3)0.024 (2)
C420.090 (3)0.064 (2)0.079 (3)0.005 (2)0.001 (2)0.029 (2)
C430.075 (3)0.068 (2)0.084 (3)0.0276 (19)0.002 (2)0.004 (2)
C440.0442 (16)0.0498 (16)0.0354 (15)0.0083 (12)0.0064 (12)0.0022 (12)
C450.0529 (17)0.0395 (15)0.0516 (18)0.0121 (13)0.0074 (14)0.0075 (13)
N10.215 (6)0.092 (3)0.124 (4)0.036 (3)0.038 (4)0.033 (3)
C460.077 (2)0.066 (2)0.052 (2)0.0108 (18)0.0094 (17)0.0087 (17)
C470.058 (2)0.062 (2)0.0476 (18)0.0082 (16)0.0095 (15)0.0026 (15)
N20.263 (11)0.191 (8)0.433 (17)0.072 (8)0.203 (12)0.023 (9)
C480.182 (7)0.077 (3)0.150 (6)0.024 (4)0.069 (6)0.003 (3)
C490.135 (5)0.141 (5)0.086 (4)0.020 (4)0.026 (3)0.046 (3)
Geometric parameters (Å, º) top
Li1—O11.987 (5)C21—H21C0.9800
Li1—O21.853 (5)C19X—H19D0.9800
Li1—O31.981 (5)C19X—H19E0.9800
Li1—O4i1.866 (5)C19X—H19F0.9800
Li1—H12.10 (3)C20X—H20D0.9800
Li1—H32.06 (3)C20X—H20E0.9800
O1—C11.379 (3)C20X—H20F0.9800
O1—H11.00 (4)C21X—H21D0.9800
O2—C121.400 (3)C21X—H21E0.9800
O2—C451.439 (3)C21X—H21F0.9800
O3—C231.373 (3)C22—C241.509 (4)
O3—H30.89 (4)C22—H22A0.9900
O4—C341.355 (3)C22—H22B0.9900
O4—Li1i1.866 (5)C23—C241.395 (4)
C1—C61.391 (4)C23—C281.395 (4)
C1—C21.399 (4)C24—C251.388 (4)
C2—C31.387 (4)C25—C261.385 (4)
C2—C441.517 (4)C25—H250.9500
C3—C41.386 (4)C26—C271.396 (5)
C3—H3A0.9500C26—C291.546 (5)
C4—C51.386 (4)C27—C281.387 (4)
C4—C71.537 (4)C27—H270.9500
C5—C61.397 (4)C28—C331.520 (4)
C5—H50.9500C29—C311.490 (6)
C6—C111.516 (4)C29—C301.501 (6)
C7—C9X1.492 (13)C29—C321.576 (6)
C7—C91.508 (8)C30—H30A0.9800
C7—C10X1.514 (12)C30—H30B0.9800
C7—C81.521 (7)C30—H30C0.9800
C7—C101.552 (6)C31—H31A0.9800
C7—C8X1.568 (12)C31—H31B0.9800
C8—H8A0.9800C31—H31C0.9800
C8—H8B0.9800C32—H32A0.9800
C8—H8C0.9800C32—H32B0.9800
C9—H9A0.9800C32—H32C0.9800
C9—H9B0.9800C33—C351.520 (4)
C9—H9C0.9800C33—H33A0.9900
C10—H10A0.9800C33—H33B0.9900
C10—H10B0.9800C34—C351.396 (4)
C10—H10C0.9800C34—C391.401 (4)
C8X—H8D0.9800C35—C361.385 (4)
C8X—H8E0.9800C36—C371.393 (4)
C8X—H8F0.9800C36—H360.9500
C9X—H9D0.9800C37—C381.386 (4)
C9X—H9E0.9800C37—C401.527 (4)
C9X—H9F0.9800C38—C391.386 (4)
C10X—H10D0.9800C38—H380.9500
C10X—H10E0.9800C39—C441.512 (4)
C10X—H10F0.9800C40—C411.489 (5)
C11—C131.512 (4)C40—C421.525 (5)
C11—H11A0.9900C40—C431.552 (5)
C11—H11B0.9900C41—H41A0.9800
C12—C171.386 (4)C41—H41B0.9800
C12—C131.397 (3)C41—H41C0.9800
C13—C141.384 (4)C42—H42A0.9800
C14—C151.384 (4)C42—H42B0.9800
C14—H140.9500C42—H42C0.9800
C15—C161.392 (4)C43—H43A0.9800
C15—C181.539 (4)C43—H43B0.9800
C16—C171.396 (4)C43—H43C0.9800
C16—H160.9500C44—H44A0.9900
C17—C221.518 (4)C44—H44B0.9900
C18—C20X1.452 (18)C45—H45A0.9800
C18—C201.483 (6)C45—H45B0.9800
C18—C191.518 (5)C45—H45C0.9800
C18—C19X1.525 (16)N1—C461.128 (5)
C18—C211.536 (5)C46—C471.411 (5)
C18—C21X1.546 (14)C47—H47A0.9800
C19—H19A0.9800C47—H47B0.9800
C19—H19B0.9800C47—H47C0.9800
C19—H19C0.9800N2—C481.151 (12)
C20—H20A0.9800C48—C491.366 (10)
C20—H20B0.9800C49—H49A0.9800
C20—H20C0.9800C49—H49B0.9800
C21—H21A0.9800C49—H49C0.9800
C21—H21B0.9800
O1—Li1—O2105.5 (2)H21A—C21—H21B109.5
O1—Li1—O3112.6 (2)C18—C21—H21C109.5
O1—Li1—O4i102.4 (2)H21A—C21—H21C109.5
O2—Li1—O3107.8 (2)H21B—C21—H21C109.5
O2—Li1—O4i127.6 (3)C18—C19X—H19D109.5
O3—Li1—O4i100.9 (2)C18—C19X—H19E109.5
O2—Li1—H1131.1 (10)H19D—C19X—H19E109.5
O4i—Li1—H190.3 (9)C18—C19X—H19F109.5
O3—Li1—H190.6 (10)H19D—C19X—H19F109.5
O1—Li1—H128.1 (10)H19E—C19X—H19F109.5
O2—Li1—H3131.8 (10)C18—C20X—H20D109.5
O4i—Li1—H388.1 (10)C18—C20X—H20E109.5
O3—Li1—H325.3 (10)H20D—C20X—H20E109.5
O1—Li1—H394.6 (10)C18—C20X—H20F109.5
H1—Li1—H368.8 (14)H20D—C20X—H20F109.5
C1—O1—Li1147.6 (2)H20E—C20X—H20F109.5
C1—O1—H1110.8 (19)C18—C21X—H21D109.5
Li1—O1—H182.4 (19)C18—C21X—H21E109.5
C12—O2—C45113.61 (19)H21D—C21X—H21E109.5
C12—O2—Li1113.79 (19)C18—C21X—H21F109.5
C45—O2—Li1132.5 (2)H21D—C21X—H21F109.5
C23—O3—Li1146.7 (2)H21E—C21X—H21F109.5
C23—O3—H3115 (2)C24—C22—C17109.6 (2)
Li1—O3—H382 (2)C24—C22—H22A109.8
C34—O4—Li1i121.1 (2)C17—C22—H22A109.8
O1—C1—C6118.8 (2)C24—C22—H22B109.8
O1—C1—C2120.1 (2)C17—C22—H22B109.8
C6—C1—C2121.1 (2)H22A—C22—H22B108.2
C3—C2—C1118.3 (3)O3—C23—C24118.5 (2)
C3—C2—C44119.9 (2)O3—C23—C28120.6 (2)
C1—C2—C44121.8 (2)C24—C23—C28120.9 (2)
C4—C3—C2122.7 (3)C25—C24—C23118.1 (2)
C4—C3—H3A118.6C25—C24—C22120.2 (2)
C2—C3—H3A118.6C23—C24—C22121.7 (2)
C3—C4—C5116.9 (2)C26—C25—C24123.1 (3)
C3—C4—C7121.0 (3)C26—C25—H25118.5
C5—C4—C7122.2 (3)C24—C25—H25118.5
C4—C5—C6123.1 (3)C25—C26—C27116.8 (3)
C4—C5—H5118.4C25—C26—C29120.3 (3)
C6—C5—H5118.4C27—C26—C29123.0 (3)
C1—C6—C5117.6 (2)C28—C27—C26122.5 (3)
C1—C6—C11121.9 (2)C28—C27—H27118.7
C5—C6—C11120.4 (2)C26—C27—H27118.7
C9X—C7—C10X112.9 (12)C27—C28—C23118.4 (3)
C9—C7—C10X126.7 (9)C27—C28—C33119.9 (2)
C9—C7—C8112.2 (5)C23—C28—C33121.7 (2)
C9X—C7—C4107.8 (10)C31—C29—C30117.2 (4)
C9—C7—C4113.4 (4)C31—C29—C26111.2 (3)
C10X—C7—C4115.4 (8)C30—C29—C26109.0 (3)
C8—C7—C4107.4 (4)C31—C29—C32103.8 (4)
C9—C7—C10106.7 (4)C30—C29—C32105.0 (3)
C8—C7—C10107.2 (5)C26—C29—C32110.3 (3)
C4—C7—C10109.7 (3)C29—C30—H30A109.5
C9X—C7—C8X106.6 (11)C29—C30—H30B109.5
C10X—C7—C8X105.9 (12)H30A—C30—H30B109.5
C4—C7—C8X107.7 (7)C29—C30—H30C109.5
C7—C8—H8A109.5H30A—C30—H30C109.5
C7—C8—H8B109.5H30B—C30—H30C109.5
H8A—C8—H8B109.5C29—C31—H31A109.5
C7—C8—H8C109.5C29—C31—H31B109.5
H8A—C8—H8C109.5H31A—C31—H31B109.5
H8B—C8—H8C109.5C29—C31—H31C109.5
C7—C9—H9A109.5H31A—C31—H31C109.5
C7—C9—H9B109.5H31B—C31—H31C109.5
H9A—C9—H9B109.5C29—C32—H32A109.5
C7—C9—H9C109.5C29—C32—H32B109.5
H9A—C9—H9C109.5H32A—C32—H32B109.5
H9B—C9—H9C109.5C29—C32—H32C109.5
C7—C10—H10A109.5H32A—C32—H32C109.5
C7—C10—H10B109.5H32B—C32—H32C109.5
H10A—C10—H10B109.5C35—C33—C28112.8 (2)
C7—C10—H10C109.5C35—C33—H33A109.0
H10A—C10—H10C109.5C28—C33—H33A109.0
H10B—C10—H10C109.5C35—C33—H33B109.0
C7—C8X—H8D109.5C28—C33—H33B109.0
C7—C8X—H8E109.5H33A—C33—H33B107.8
H8D—C8X—H8E109.5O4—C34—C35120.5 (2)
C7—C8X—H8F109.5O4—C34—C39120.0 (2)
H8D—C8X—H8F109.5C35—C34—C39119.5 (2)
H8E—C8X—H8F109.5C36—C35—C34119.1 (3)
C7—C9X—H9D109.5C36—C35—C33120.7 (3)
C7—C9X—H9E109.5C34—C35—C33120.1 (2)
H9D—C9X—H9E109.5C35—C36—C37122.8 (3)
C7—C9X—H9F109.5C35—C36—H36118.6
H9D—C9X—H9F109.5C37—C36—H36118.6
H9E—C9X—H9F109.5C38—C37—C36116.7 (3)
C7—C10X—H10D109.5C38—C37—C40122.1 (3)
C7—C10X—H10E109.5C36—C37—C40121.2 (3)
H10D—C10X—H10E109.5C39—C38—C37122.6 (3)
C7—C10X—H10F109.5C39—C38—H38118.7
H10D—C10X—H10F109.5C37—C38—H38118.7
H10E—C10X—H10F109.5C38—C39—C34119.2 (3)
C13—C11—C6109.7 (2)C38—C39—C44119.9 (3)
C13—C11—H11A109.7C34—C39—C44120.7 (2)
C6—C11—H11A109.7C41—C40—C42110.6 (4)
C13—C11—H11B109.7C41—C40—C37111.3 (3)
C6—C11—H11B109.7C42—C40—C37108.1 (3)
H11A—C11—H11B108.2C41—C40—C43110.8 (3)
C17—C12—C13122.0 (2)C42—C40—C43105.1 (3)
C17—C12—O2119.1 (2)C37—C40—C43110.8 (3)
C13—C12—O2118.9 (2)C40—C41—H41A109.5
C17—C12—Li1110.84 (19)C40—C41—H41B109.5
C13—C12—Li1112.45 (19)H41A—C41—H41B109.5
C14—C13—C12117.3 (2)C40—C41—H41C109.5
C14—C13—C11120.7 (2)H41A—C41—H41C109.5
C12—C13—C11121.8 (2)H41B—C41—H41C109.5
C15—C14—C13123.1 (3)C40—C42—H42A109.5
C15—C14—H14118.5C40—C42—H42B109.5
C13—C14—H14118.5H42A—C42—H42B109.5
C14—C15—C16117.2 (2)C40—C42—H42C109.5
C14—C15—C18120.6 (3)H42A—C42—H42C109.5
C16—C15—C18122.2 (3)H42B—C42—H42C109.5
C15—C16—C17122.3 (3)C40—C43—H43A109.5
C15—C16—H16118.9C40—C43—H43B109.5
C17—C16—H16118.9H43A—C43—H43B109.5
C12—C17—C16117.6 (2)C40—C43—H43C109.5
C12—C17—C22122.2 (2)H43A—C43—H43C109.5
C16—C17—C22119.9 (2)H43B—C43—H43C109.5
C20—C18—C19108.5 (4)C39—C44—C2113.0 (2)
C20X—C18—C19X112.6 (18)C39—C44—H44A109.0
C20—C18—C21110.4 (4)C2—C44—H44A109.0
C19—C18—C21106.6 (4)C39—C44—H44B109.0
C20X—C18—C15110.7 (19)C2—C44—H44B109.0
C20—C18—C15112.9 (3)H44A—C44—H44B107.8
C19—C18—C15110.1 (3)O2—C45—H45A109.5
C19X—C18—C15112.6 (18)O2—C45—H45B109.5
C21—C18—C15108.2 (3)H45A—C45—H45B109.5
C20X—C18—C21X106.9 (16)O2—C45—H45C109.5
C19X—C18—C21X106.8 (18)H45A—C45—H45C109.5
C15—C18—C21X106.8 (11)H45B—C45—H45C109.5
C18—C19—H19A109.5N1—C46—C47179.7 (5)
C18—C19—H19B109.5C46—C47—H47A109.5
H19A—C19—H19B109.5C46—C47—H47B109.5
C18—C19—H19C109.5H47A—C47—H47B109.5
H19A—C19—H19C109.5C46—C47—H47C109.5
H19B—C19—H19C109.5H47A—C47—H47C109.5
C18—C20—H20A109.5H47B—C47—H47C109.5
C18—C20—H20B109.5N2—C48—C49176.8 (10)
H20A—C20—H20B109.5C48—C49—H49A109.5
C18—C20—H20C109.5C48—C49—H49B109.5
H20A—C20—H20C109.5H49A—C49—H49B109.5
H20B—C20—H20C109.5C48—C49—H49C109.5
C18—C21—H21A109.5H49A—C49—H49C109.5
C18—C21—H21B109.5H49B—C49—H49C109.5
O2—Li1—O1—C141.0 (5)C13—C12—C17—C22165.8 (2)
O4i—Li1—O1—C1176.2 (3)O2—C12—C17—C2211.6 (3)
O3—Li1—O1—C176.3 (5)Li1—C12—C17—C2229.9 (3)
O4i—Li1—O2—C12179.2 (3)C15—C16—C17—C121.2 (4)
O3—Li1—O2—C1259.3 (3)C15—C16—C17—C22172.6 (2)
O1—Li1—O2—C1261.2 (3)C14—C15—C18—C20X127.7 (17)
O4i—Li1—O2—C455.0 (5)C16—C15—C18—C20X52.3 (17)
O3—Li1—O2—C45124.8 (3)C14—C15—C18—C20174.2 (4)
O1—Li1—O2—C45114.7 (3)C16—C15—C18—C205.7 (5)
O2—Li1—O3—C2339.5 (5)C14—C15—C18—C1952.9 (4)
O4i—Li1—O3—C23175.1 (3)C16—C15—C18—C19127.1 (4)
O1—Li1—O3—C2376.5 (4)C14—C15—C18—C19X0.6 (18)
Li1—O1—C1—C648.5 (5)C16—C15—C18—C19X179.4 (18)
Li1—O1—C1—C2132.6 (4)C14—C15—C18—C2163.3 (4)
O1—C1—C2—C3175.8 (2)C16—C15—C18—C21116.7 (4)
C6—C1—C2—C35.3 (4)C14—C15—C18—C21X116.3 (12)
O1—C1—C2—C442.6 (4)C16—C15—C18—C21X63.7 (12)
C6—C1—C2—C44176.3 (2)C12—C17—C22—C24104.8 (3)
C1—C2—C3—C41.7 (4)C16—C17—C22—C2468.7 (3)
C44—C2—C3—C4179.9 (3)Li1—O3—C23—C2447.3 (5)
C2—C3—C4—C52.7 (4)Li1—O3—C23—C28133.1 (4)
C2—C3—C4—C7175.8 (3)O3—C23—C24—C25175.9 (2)
C3—C4—C5—C63.7 (4)C28—C23—C24—C254.6 (4)
C7—C4—C5—C6174.7 (3)O3—C23—C24—C220.1 (3)
O1—C1—C6—C5176.7 (2)C28—C23—C24—C22179.6 (2)
C2—C1—C6—C54.4 (4)C17—C22—C24—C2588.9 (3)
O1—C1—C6—C110.3 (4)C17—C22—C24—C2386.8 (3)
C2—C1—C6—C11179.3 (2)C23—C24—C25—C260.7 (4)
C4—C5—C6—C10.2 (4)C22—C24—C25—C26175.2 (3)
C4—C5—C6—C11176.2 (2)C24—C25—C26—C274.6 (5)
C3—C4—C7—C9X135.3 (15)C24—C25—C26—C29175.3 (3)
C5—C4—C7—C9X46.4 (16)C25—C26—C27—C283.4 (5)
C3—C4—C7—C9165.9 (5)C29—C26—C27—C28176.4 (3)
C5—C4—C7—C915.8 (6)C26—C27—C28—C231.5 (4)
C3—C4—C7—C10X8.0 (18)C26—C27—C28—C33179.3 (3)
C5—C4—C7—C10X173.7 (17)O3—C23—C28—C27174.8 (2)
C3—C4—C7—C869.6 (7)C24—C23—C28—C275.6 (4)
C5—C4—C7—C8108.8 (7)O3—C23—C28—C332.9 (4)
C3—C4—C7—C1046.7 (5)C24—C23—C28—C33176.6 (2)
C5—C4—C7—C10135.0 (5)C25—C26—C29—C31157.1 (4)
C3—C4—C7—C8X110.0 (15)C27—C26—C29—C3122.7 (6)
C5—C4—C7—C8X68.3 (15)C25—C26—C29—C3072.2 (5)
C1—C6—C11—C1385.7 (3)C27—C26—C29—C30107.9 (4)
C5—C6—C11—C1390.5 (3)C25—C26—C29—C3242.5 (5)
C45—O2—C12—C1796.1 (3)C27—C26—C29—C32137.3 (3)
Li1—O2—C12—C1787.2 (3)C27—C28—C33—C3590.4 (3)
C45—O2—C12—C1386.4 (3)C23—C28—C33—C3587.3 (3)
Li1—O2—C12—C1390.3 (3)Li1i—O4—C34—C3590.1 (3)
C45—O2—C12—Li1176.7 (3)Li1i—O4—C34—C3991.7 (3)
O2—Li1—C12—C17111.0 (3)O4—C34—C35—C36178.9 (2)
O4i—Li1—C12—C17109.4 (6)C39—C34—C35—C362.9 (4)
O3—Li1—C12—C1714.0 (2)O4—C34—C35—C334.5 (4)
O1—Li1—C12—C17126.6 (2)C39—C34—C35—C33173.7 (2)
O2—Li1—C12—C13108.7 (3)C28—C33—C35—C3689.2 (3)
O4i—Li1—C12—C13110.3 (6)C28—C33—C35—C3487.3 (3)
O3—Li1—C12—C13126.3 (2)C34—C35—C36—C371.5 (4)
O1—Li1—C12—C1313.7 (2)C33—C35—C36—C37175.0 (2)
O4i—Li1—C12—O21.6 (5)C35—C36—C37—C380.5 (4)
O3—Li1—C12—O2125.0 (3)C35—C36—C37—C40176.1 (3)
O1—Li1—C12—O2122.4 (3)C36—C37—C38—C391.3 (4)
C17—C12—C13—C148.8 (4)C40—C37—C38—C39175.4 (3)
O2—C12—C13—C14173.8 (2)C37—C38—C39—C340.1 (4)
Li1—C12—C13—C14144.1 (2)C37—C38—C39—C44176.4 (3)
C17—C12—C13—C11165.1 (2)O4—C34—C39—C38179.6 (2)
O2—C12—C13—C1112.3 (3)C35—C34—C39—C382.2 (4)
Li1—C12—C13—C1129.8 (3)O4—C34—C39—C444.0 (4)
C6—C11—C13—C1470.3 (3)C35—C34—C39—C44174.3 (2)
C6—C11—C13—C12103.4 (3)C38—C37—C40—C41140.3 (4)
C12—C13—C14—C153.3 (4)C36—C37—C40—C4143.3 (5)
C11—C13—C14—C15170.7 (2)C38—C37—C40—C4298.1 (4)
C13—C14—C15—C162.9 (4)C36—C37—C40—C4278.4 (4)
C13—C14—C15—C18177.1 (3)C38—C37—C40—C4316.6 (4)
C14—C15—C16—C174.0 (4)C36—C37—C40—C43167.0 (3)
C18—C15—C16—C17176.0 (3)C38—C39—C44—C288.0 (3)
C13—C12—C17—C167.8 (4)C34—C39—C44—C288.4 (3)
O2—C12—C17—C16174.8 (2)C3—C2—C44—C3991.1 (3)
Li1—C12—C17—C16143.7 (2)C1—C2—C44—C3987.2 (3)
Symmetry code: (i) x, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O41.00 (4)1.59 (4)2.568 (3)165 (3)
O3—H3···O40.89 (4)1.68 (4)2.541 (3)162 (3)
(II) Tetraacetonitrilebis(µ-5,11,17,23-tetra-tert-butyl-26,28-dihydroxy- 25,27-dioxidocalix[4]arene)tetralithium(I) acetonitrile octasolvate top
Crystal data top
[Li4(C44H54O4)2(C2H3N)4]·8C2H3NZ = 1
Mr = 1814.16F(000) = 976
Triclinic, P1Dx = 1.121 Mg m3
Hall symbol: -P 1Synchrotron radiation, λ = 0.8466 Å
a = 12.8190 (12) ÅCell parameters from 1271 reflections
b = 13.5649 (13) Åθ = 3.7–24.0°
c = 18.223 (3) ŵ = 0.07 mm1
α = 106.035 (2)°T = 150 K
β = 94.097 (2)°Tablet, colourless
γ = 115.286 (2)°0.15 × 0.14 × 0.07 mm
V = 2687.4 (5) Å3
Data collection top
Bruker APEX II CCD
diffractometer
7870 independent reflections
Radiation source: Daresbury SRS station 16.2SMX4532 reflections with I > 2σ(I)
Silicon 111 monochromatorRint = 0.052
ω rotation with narrow frames scansθmax = 28.4°, θmin = 3.7°
Absorption correction: multi-scan
(SADABS; Version 2.10; Sheldrick, 2003)
h = 1414
Tmin = 0.990, Tmax = 0.995k = 1515
15630 measured reflectionsl = 2020
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: geom except H2 and H4 coords freely refined
R[F2 > 2σ(F2)] = 0.065H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.172 w = 1/[σ^2^(Fo^2^) + (0.0771P)^2^]
where P = (Fo^2^ + 2Fc^2^)/3
S = 1.00(Δ/σ)max = 0.001
7870 reflectionsΔρmax = 0.25 e Å3
638 parametersΔρmin = 0.24 e Å3
0 restraintsExtinction correction: SHELXL97, Fc^*^=kFc[1+0.001xFc^2^λ^3^/sin(2θ)]^-1/4^
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0042 (8)
Crystal data top
[Li4(C44H54O4)2(C2H3N)4]·8C2H3Nγ = 115.286 (2)°
Mr = 1814.16V = 2687.4 (5) Å3
Triclinic, P1Z = 1
a = 12.8190 (12) ÅSynchrotron radiation, λ = 0.8466 Å
b = 13.5649 (13) ŵ = 0.07 mm1
c = 18.223 (3) ÅT = 150 K
α = 106.035 (2)°0.15 × 0.14 × 0.07 mm
β = 94.097 (2)°
Data collection top
Bruker APEX II CCD
diffractometer
7870 independent reflections
Absorption correction: multi-scan
(SADABS; Version 2.10; Sheldrick, 2003)
4532 reflections with I > 2σ(I)
Tmin = 0.990, Tmax = 0.995Rint = 0.052
15630 measured reflectionsθmax = 28.4°
Refinement top
R[F2 > 2σ(F2)] = 0.0650 restraints
wR(F2) = 0.172H atoms treated by a mixture of independent and constrained refinement
S = 1.00Δρmax = 0.25 e Å3
7870 reflectionsΔρmin = 0.24 e Å3
638 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.

Refinement. Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > σ(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ 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
xyzUiso*/Ueq
Li10.9268 (6)0.4028 (5)0.9851 (4)0.0430 (17)
Li20.8047 (5)0.5768 (5)0.9635 (3)0.0320 (14)
O10.83884 (18)0.52342 (18)0.86567 (13)0.0267 (6)
O20.8311 (2)0.3393 (2)0.88146 (14)0.0309 (6)
H20.841 (3)0.401 (3)0.877 (2)0.037*
O31.09210 (19)0.45547 (18)0.96967 (13)0.0315 (6)
O41.0586 (2)0.6357 (2)0.92266 (14)0.0363 (7)
H40.979 (3)0.599 (3)0.899 (2)0.044*
C10.8069 (3)0.5172 (3)0.79141 (19)0.0240 (8)
C20.8662 (3)0.6128 (3)0.7670 (2)0.0248 (8)
C30.8365 (3)0.6024 (3)0.6898 (2)0.0280 (9)
H30.87770.66750.67420.034*
C40.7481 (3)0.5000 (3)0.6335 (2)0.0283 (9)
C50.6892 (3)0.4076 (3)0.6601 (2)0.0271 (8)
H50.62780.33730.62390.033*
C60.7159 (3)0.4137 (3)0.7369 (2)0.0237 (8)
C70.7195 (3)0.4942 (3)0.5486 (2)0.0342 (9)
C80.6208 (4)0.3759 (3)0.4971 (2)0.0523 (12)
H8A0.64530.31630.49600.078*
H8B0.60420.37620.44390.078*
H8C0.54940.35890.51830.078*
C90.6790 (4)0.5857 (3)0.5482 (2)0.0546 (12)
H9A0.60630.56750.56800.082*
H9B0.66390.58540.49460.082*
H9C0.74090.66250.58160.082*
C100.8299 (3)0.5184 (3)0.5137 (2)0.0496 (11)
H10A0.89420.59490.54550.074*
H10B0.81170.51690.46010.074*
H10C0.85430.45890.51310.074*
C110.6510 (3)0.3078 (3)0.75983 (19)0.0258 (8)
H11A0.57000.26130.72670.031*
H11B0.64410.33330.81490.031*
C120.7993 (3)0.2520 (3)0.81150 (19)0.0237 (8)
C130.7115 (3)0.2318 (3)0.75150 (19)0.0210 (8)
C140.6822 (3)0.1413 (3)0.68119 (19)0.0249 (8)
H140.62230.12750.64010.030*
C150.7370 (3)0.0708 (3)0.66898 (19)0.0256 (8)
C160.8237 (3)0.0943 (3)0.73170 (19)0.0259 (8)
H160.86050.04580.72600.031*
C170.8586 (3)0.1849 (3)0.80184 (19)0.0253 (8)
C180.7101 (3)0.0252 (3)0.5913 (2)0.0297 (9)
C190.6051 (4)0.0457 (3)0.5328 (2)0.0514 (12)
H19A0.53470.06760.55520.077*
H19B0.59070.10810.48440.077*
H19C0.62260.02560.52140.077*
C200.8200 (4)0.0117 (3)0.5562 (2)0.0484 (11)
H20A0.83890.08560.54840.073*
H20B0.80450.04770.50580.073*
H20C0.88690.02070.59190.073*
C210.6835 (3)0.1397 (3)0.6045 (2)0.0418 (10)
H21A0.75140.12890.64020.063*
H21B0.66850.19940.55430.063*
H21C0.61360.16410.62720.063*
C220.9638 (3)0.2136 (3)0.8629 (2)0.0285 (9)
H22A0.97300.14320.85700.034*
H22B0.95020.24050.91590.034*
C231.1284 (3)0.4244 (3)0.9037 (2)0.0299 (9)
C241.0759 (3)0.3078 (3)0.8533 (2)0.0287 (9)
C251.1249 (3)0.2755 (3)0.7902 (2)0.0311 (9)
H251.08930.19600.75830.037*
C261.2233 (3)0.3542 (3)0.7720 (2)0.0302 (9)
C271.2690 (3)0.4699 (3)0.8199 (2)0.0338 (9)
H271.33450.52680.80850.041*
C281.2241 (3)0.5066 (3)0.8833 (2)0.0285 (9)
C291.2720 (3)0.3138 (3)0.7018 (2)0.0381 (10)
C301.1804 (4)0.2656 (4)0.6255 (2)0.0574 (12)
H30A1.10710.20220.62790.086*
H30B1.21120.23640.58140.086*
H30C1.16450.32730.61850.086*
C311.3012 (4)0.2162 (4)0.7077 (3)0.0635 (13)
H31A1.36510.24690.75360.095*
H31B1.32630.18750.66040.095*
H31C1.23080.15260.71290.095*
C321.3850 (4)0.4115 (4)0.6952 (3)0.0714 (15)
H32A1.36790.47200.68700.107*
H32B1.41420.38050.65080.107*
H32C1.44520.44460.74340.107*
C331.2789 (3)0.6362 (3)0.9268 (2)0.0299 (9)
H33A1.25540.64990.97770.036*
H33B1.36610.67000.93710.036*
C341.1271 (3)0.6887 (3)0.87651 (19)0.0267 (8)
C351.2397 (3)0.6954 (3)0.87983 (19)0.0267 (8)
C361.3122 (3)0.7556 (3)0.83702 (19)0.0280 (9)
H361.38910.76170.83940.034*
C371.2770 (3)0.8073 (3)0.79095 (19)0.0266 (8)
C381.1630 (3)0.7953 (3)0.78839 (19)0.0276 (8)
H381.13620.82900.75700.033*
C391.0870 (3)0.7363 (3)0.82971 (19)0.0252 (8)
C401.3590 (3)0.8791 (3)0.7469 (2)0.0357 (9)
C411.4726 (3)0.8697 (4)0.7480 (3)0.0522 (12)
H41A1.51470.89620.80230.078*
H41B1.52240.91810.72050.078*
H41C1.45410.78880.72200.078*
C421.3897 (4)1.0063 (3)0.7870 (3)0.0651 (14)
H42A1.31701.01390.78510.098*
H42B1.44171.05390.75990.098*
H42C1.43011.03240.84170.098*
C431.2962 (4)0.8395 (4)0.6620 (2)0.0710 (15)
H43A1.27230.75700.63670.106*
H43B1.34990.88460.63440.106*
H43C1.22600.85160.66030.106*
C440.9643 (3)0.7274 (3)0.8249 (2)0.0292 (9)
H44A0.96450.79200.80940.035*
H44B0.94610.73700.87750.035*
N10.6236 (3)0.4761 (3)0.94941 (18)0.0401 (8)
C450.5308 (3)0.4044 (3)0.9400 (2)0.0345 (9)
C460.4125 (3)0.3102 (3)0.9282 (2)0.0529 (12)
H46A0.40540.23850.89120.079*
H46B0.35380.32930.90710.079*
H46C0.39880.29940.97830.079*
N20.8329 (2)0.7478 (3)0.99599 (17)0.0325 (8)
C470.8544 (3)0.8414 (3)1.0269 (2)0.0319 (9)
C480.8829 (4)0.9616 (3)1.0682 (2)0.0517 (12)
H48A0.88491.00111.03030.078*
H48B0.96031.00111.10410.078*
H48C0.82260.96331.09790.078*
N30.9044 (4)0.2981 (4)0.5485 (3)0.0752 (13)
C490.9445 (4)0.3536 (4)0.6127 (3)0.0493 (11)
C500.9966 (4)0.4246 (4)0.6948 (2)0.0556 (12)
H50A0.94100.44890.71780.083*
H50B1.06990.49330.69890.083*
H50C1.01400.37950.72290.083*
N40.5849 (4)0.1088 (4)0.9839 (3)0.0847 (14)
C510.6295 (4)0.0267 (5)0.9687 (3)0.0566 (13)
C520.6872 (4)0.0780 (4)0.9494 (3)0.0705 (14)
H52A0.70340.05840.89700.106*
H52B0.76180.13190.98770.106*
H52C0.63560.11450.95040.106*
N50.8126 (4)0.9105 (4)0.8610 (2)0.0691 (12)
C530.7386 (4)0.8179 (5)0.8343 (3)0.0586 (13)
C540.6436 (4)0.7001 (4)0.8025 (3)0.0882 (18)
H54A0.58070.69200.83160.132*
H54B0.67390.64640.80720.132*
H54C0.61190.68230.74730.132*
N60.9783 (4)0.0484 (3)0.2773 (2)0.0683 (12)
C550.9821 (4)0.0852 (4)0.3414 (3)0.0466 (11)
C560.9881 (4)0.1325 (4)0.4243 (3)0.0714 (14)
H56A0.94940.06890.44440.107*
H56B0.94800.18080.43230.107*
H56C1.07110.17970.45220.107*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Li10.040 (4)0.039 (4)0.043 (4)0.014 (3)0.005 (3)0.013 (3)
Li20.029 (3)0.028 (3)0.039 (4)0.016 (3)0.008 (3)0.009 (3)
O10.0228 (13)0.0225 (13)0.0315 (14)0.0082 (11)0.0080 (11)0.0078 (11)
O20.0382 (15)0.0182 (14)0.0296 (14)0.0097 (12)0.0048 (11)0.0048 (13)
O30.0328 (15)0.0242 (14)0.0282 (14)0.0065 (12)0.0036 (11)0.0076 (12)
O40.0233 (14)0.0398 (16)0.0355 (15)0.0022 (12)0.0055 (12)0.0189 (13)
C10.023 (2)0.025 (2)0.026 (2)0.0144 (17)0.0093 (16)0.0066 (17)
C20.0173 (19)0.0196 (19)0.038 (2)0.0107 (16)0.0077 (16)0.0064 (17)
C30.028 (2)0.020 (2)0.041 (2)0.0135 (17)0.0111 (17)0.0142 (18)
C40.025 (2)0.024 (2)0.038 (2)0.0149 (17)0.0070 (17)0.0081 (18)
C50.024 (2)0.019 (2)0.035 (2)0.0116 (16)0.0015 (16)0.0024 (17)
C60.0190 (19)0.0161 (19)0.037 (2)0.0102 (16)0.0086 (16)0.0063 (17)
C70.038 (2)0.029 (2)0.033 (2)0.0152 (19)0.0006 (18)0.0083 (18)
C80.059 (3)0.043 (3)0.042 (3)0.015 (2)0.000 (2)0.014 (2)
C90.071 (3)0.050 (3)0.048 (3)0.036 (2)0.004 (2)0.014 (2)
C100.057 (3)0.053 (3)0.043 (3)0.025 (2)0.017 (2)0.022 (2)
C110.0198 (19)0.023 (2)0.031 (2)0.0098 (16)0.0063 (15)0.0048 (17)
C120.026 (2)0.0109 (18)0.029 (2)0.0055 (16)0.0092 (16)0.0035 (16)
C130.0222 (19)0.0135 (18)0.026 (2)0.0085 (15)0.0063 (16)0.0049 (16)
C140.021 (2)0.0201 (19)0.030 (2)0.0076 (16)0.0025 (15)0.0075 (17)
C150.024 (2)0.022 (2)0.031 (2)0.0112 (17)0.0055 (16)0.0103 (17)
C160.024 (2)0.019 (2)0.038 (2)0.0122 (16)0.0082 (17)0.0099 (18)
C170.022 (2)0.020 (2)0.029 (2)0.0056 (16)0.0055 (16)0.0093 (17)
C180.030 (2)0.022 (2)0.034 (2)0.0133 (17)0.0015 (17)0.0049 (17)
C190.064 (3)0.045 (3)0.039 (3)0.036 (2)0.006 (2)0.006 (2)
C200.057 (3)0.033 (2)0.047 (3)0.019 (2)0.021 (2)0.001 (2)
C210.041 (2)0.025 (2)0.045 (2)0.0124 (19)0.0013 (19)0.0012 (19)
C220.028 (2)0.0185 (19)0.035 (2)0.0083 (16)0.0032 (16)0.0082 (17)
C230.025 (2)0.023 (2)0.034 (2)0.0062 (17)0.0035 (17)0.0103 (18)
C240.024 (2)0.028 (2)0.033 (2)0.0110 (17)0.0002 (17)0.0117 (18)
C250.024 (2)0.024 (2)0.038 (2)0.0074 (17)0.0026 (17)0.0080 (18)
C260.025 (2)0.033 (2)0.032 (2)0.0129 (18)0.0039 (17)0.0107 (19)
C270.021 (2)0.029 (2)0.042 (2)0.0045 (17)0.0047 (17)0.014 (2)
C280.028 (2)0.026 (2)0.026 (2)0.0102 (18)0.0020 (17)0.0069 (17)
C290.030 (2)0.033 (2)0.047 (3)0.0118 (19)0.0081 (19)0.013 (2)
C300.060 (3)0.077 (3)0.041 (3)0.041 (3)0.011 (2)0.013 (2)
C310.069 (3)0.081 (4)0.070 (3)0.057 (3)0.028 (3)0.029 (3)
C320.052 (3)0.060 (3)0.078 (3)0.010 (3)0.034 (3)0.010 (3)
C330.021 (2)0.028 (2)0.034 (2)0.0060 (17)0.0016 (16)0.0101 (18)
C340.021 (2)0.024 (2)0.022 (2)0.0006 (16)0.0037 (15)0.0069 (17)
C350.026 (2)0.0149 (19)0.027 (2)0.0010 (16)0.0000 (16)0.0055 (16)
C360.023 (2)0.023 (2)0.032 (2)0.0062 (17)0.0070 (16)0.0076 (17)
C370.028 (2)0.020 (2)0.028 (2)0.0077 (17)0.0079 (16)0.0087 (17)
C380.028 (2)0.0190 (19)0.033 (2)0.0092 (17)0.0040 (17)0.0089 (17)
C390.025 (2)0.0166 (19)0.025 (2)0.0053 (16)0.0034 (16)0.0012 (16)
C400.034 (2)0.037 (2)0.047 (2)0.0189 (19)0.0198 (19)0.023 (2)
C410.039 (3)0.065 (3)0.071 (3)0.027 (2)0.031 (2)0.042 (3)
C420.064 (3)0.043 (3)0.110 (4)0.026 (2)0.054 (3)0.047 (3)
C430.064 (3)0.111 (4)0.055 (3)0.040 (3)0.029 (3)0.050 (3)
C440.025 (2)0.020 (2)0.035 (2)0.0062 (16)0.0058 (16)0.0052 (17)
N10.033 (2)0.043 (2)0.047 (2)0.0202 (18)0.0136 (16)0.0128 (17)
C450.027 (2)0.040 (3)0.038 (2)0.018 (2)0.0120 (19)0.010 (2)
C460.042 (3)0.039 (3)0.062 (3)0.010 (2)0.013 (2)0.009 (2)
N20.0335 (19)0.0299 (19)0.0376 (19)0.0171 (16)0.0095 (14)0.0123 (16)
C470.026 (2)0.034 (2)0.037 (2)0.0165 (19)0.0043 (17)0.011 (2)
C480.050 (3)0.029 (2)0.061 (3)0.017 (2)0.002 (2)0.000 (2)
N30.108 (4)0.067 (3)0.063 (3)0.057 (3)0.017 (3)0.014 (2)
C490.056 (3)0.047 (3)0.067 (3)0.039 (2)0.027 (3)0.025 (3)
C500.053 (3)0.070 (3)0.055 (3)0.041 (3)0.016 (2)0.016 (3)
N40.053 (3)0.102 (4)0.092 (3)0.020 (3)0.012 (2)0.051 (3)
C510.039 (3)0.073 (4)0.047 (3)0.022 (3)0.003 (2)0.014 (3)
C520.075 (4)0.044 (3)0.070 (3)0.021 (3)0.006 (3)0.000 (3)
N50.057 (3)0.070 (3)0.094 (3)0.035 (2)0.020 (2)0.037 (3)
C530.047 (3)0.065 (4)0.082 (4)0.039 (3)0.018 (3)0.029 (3)
C540.052 (3)0.056 (3)0.138 (5)0.026 (3)0.011 (3)0.008 (3)
N60.095 (3)0.070 (3)0.063 (3)0.055 (3)0.020 (2)0.026 (2)
C550.050 (3)0.042 (3)0.058 (3)0.028 (2)0.015 (2)0.019 (2)
C560.091 (4)0.077 (4)0.059 (3)0.050 (3)0.028 (3)0.019 (3)
Geometric parameters (Å, º) top
Li1—O21.919 (7)C26—C271.397 (5)
Li1—O31.996 (7)C26—C291.531 (5)
Li1—O3i1.996 (7)C27—C281.392 (5)
Li1—O4i1.912 (7)C27—H270.9500
Li1—H22.18 (4)C28—C331.519 (4)
Li2—O11.888 (6)C29—C321.531 (5)
Li2—O3i1.996 (6)C29—C301.532 (5)
Li2—N12.082 (7)C29—C311.549 (5)
Li2—N22.087 (6)C30—H30A0.9800
O1—C11.354 (4)C30—H30B0.9800
O2—C121.369 (4)C30—H30C0.9800
O2—H20.82 (3)C31—H31A0.9800
O3—C231.344 (4)C31—H31B0.9800
O3—Li2i1.996 (6)C31—H31C0.9800
O3—Li1i1.996 (7)C32—H32A0.9800
O4—C341.377 (4)C32—H32B0.9800
O4—Li1i1.912 (7)C32—H32C0.9800
O4—H40.93 (4)C33—C351.514 (4)
C1—C21.408 (4)C33—H33A0.9900
C1—C61.409 (4)C33—H33B0.9900
C2—C31.382 (4)C34—C391.391 (4)
C2—C441.531 (4)C34—C351.403 (5)
C3—C41.403 (5)C35—C361.395 (4)
C3—H30.9500C36—C371.393 (4)
C4—C51.398 (4)C36—H360.9500
C4—C71.537 (5)C37—C381.396 (4)
C5—C61.387 (4)C37—C401.540 (5)
C5—H50.9500C38—C391.389 (4)
C6—C111.514 (4)C38—H380.9500
C7—C81.524 (5)C39—C441.519 (4)
C7—C101.538 (5)C40—C411.514 (5)
C7—C91.538 (5)C40—C431.525 (5)
C8—H8A0.9800C40—C421.532 (5)
C8—H8B0.9800C41—H41A0.9800
C8—H8C0.9800C41—H41B0.9800
C9—H9A0.9800C41—H41C0.9800
C9—H9B0.9800C42—H42A0.9800
C9—H9C0.9800C42—H42B0.9800
C10—H10A0.9800C42—H42C0.9800
C10—H10B0.9800C43—H43A0.9800
C10—H10C0.9800C43—H43B0.9800
C11—C131.517 (4)C43—H43C0.9800
C11—H11A0.9900C44—H44A0.9900
C11—H11B0.9900C44—H44B0.9900
C12—C131.390 (4)N1—C451.131 (4)
C12—C171.399 (4)C45—C461.458 (5)
C13—C141.399 (4)C46—H46A0.9800
C14—C151.392 (4)C46—H46B0.9800
C14—H140.9500C46—H46C0.9800
C15—C161.399 (4)N2—C471.136 (4)
C15—C181.531 (4)C47—C481.460 (5)
C16—C171.387 (4)C48—H48A0.9800
C16—H160.9500C48—H48B0.9800
C17—C221.518 (4)C48—H48C0.9800
C18—C191.529 (5)N3—C491.139 (5)
C18—C201.532 (5)C49—C501.458 (6)
C18—C211.534 (5)C50—H50A0.9800
C19—H19A0.9800C50—H50B0.9800
C19—H19B0.9800C50—H50C0.9800
C19—H19C0.9800N4—C511.137 (6)
C20—H20A0.9800C51—C521.451 (6)
C20—H20B0.9800C52—H52A0.9800
C20—H20C0.9800C52—H52B0.9800
C21—H21A0.9800C52—H52C0.9800
C21—H21B0.9800N5—C531.137 (5)
C21—H21C0.9800C53—C541.449 (6)
C22—C241.523 (4)C54—H54A0.9800
C22—H22A0.9900C54—H54B0.9800
C22—H22B0.9900C54—H54C0.9800
C23—C241.413 (5)N6—C551.125 (5)
C23—C281.419 (5)C55—C561.450 (6)
C23—Li2i2.515 (7)C56—H56A0.9800
C24—C251.403 (5)C56—H56B0.9800
C25—C261.396 (5)C56—H56C0.9800
C25—H250.9500
O1—Li2—O3i99.6 (3)C26—C25—C24123.2 (3)
O2—Li1—O3104.6 (3)C26—C25—H25118.4
O2—Li1—O3i101.4 (3)C24—C25—H25118.4
O2—Li1—O4i141.2 (4)C25—C26—C27115.3 (3)
O3—Li1—O3i107.3 (3)C25—C26—C29120.8 (3)
O3—Li1—O4i99.9 (3)C27—C26—C29123.8 (3)
O3i—Li1—O4i99.4 (3)C28—C27—C26123.7 (3)
N1—Li2—O1105.4 (3)C28—C27—H27118.1
N1—Li2—O3i115.6 (3)C26—C27—H27118.1
N2—Li2—O1114.1 (3)C27—C28—C23120.1 (3)
N2—Li2—O3i116.5 (3)C27—C28—C33117.4 (3)
N1—Li2—N2105.4 (3)C23—C28—C33122.5 (3)
O4i—Li1—H2158.3 (10)C32—C29—C26112.7 (3)
O2—Li1—H222.1 (9)C32—C29—C30107.6 (3)
O3—Li1—H2100.2 (9)C26—C29—C30110.4 (3)
O3i—Li1—H282.3 (10)C32—C29—C31107.4 (3)
C1—O1—Li2136.7 (3)C26—C29—C31110.8 (3)
C12—O2—Li1142.0 (3)C30—C29—C31107.8 (3)
C12—O2—H2114 (3)C29—C30—H30A109.5
Li1—O2—H297 (3)C29—C30—H30B109.5
C23—O3—Li2i95.8 (3)H30A—C30—H30B109.5
C23—O3—Li1128.2 (3)C29—C30—H30C109.5
Li2i—O3—Li1115.4 (3)H30A—C30—H30C109.5
C23—O3—Li1i128.1 (3)H30B—C30—H30C109.5
Li2i—O3—Li1i118.4 (3)C29—C31—H31A109.5
Li1—O3—Li1i72.7 (3)C29—C31—H31B109.5
C34—O4—Li1i140.7 (3)H31A—C31—H31B109.5
C34—O4—H4110 (2)C29—C31—H31C109.5
Li1i—O4—H4108 (2)H31A—C31—H31C109.5
O1—C1—C2120.6 (3)H31B—C31—H31C109.5
O1—C1—C6120.3 (3)C29—C32—H32A109.5
C2—C1—C6119.1 (3)C29—C32—H32B109.5
C3—C2—C1119.5 (3)H32A—C32—H32B109.5
C3—C2—C44119.9 (3)C29—C32—H32C109.5
C1—C2—C44120.6 (3)H32A—C32—H32C109.5
C2—C3—C4123.0 (3)H32B—C32—H32C109.5
C2—C3—H3118.5C35—C33—C28111.2 (3)
C4—C3—H3118.5C35—C33—H33A109.4
C5—C4—C3115.9 (3)C28—C33—H33A109.4
C5—C4—C7123.7 (3)C35—C33—H33B109.4
C3—C4—C7120.3 (3)C28—C33—H33B109.4
C6—C5—C4123.2 (3)H33A—C33—H33B108.0
C6—C5—H5118.4O4—C34—C39121.0 (3)
C4—C5—H5118.4O4—C34—C35117.6 (3)
C5—C6—C1119.2 (3)C39—C34—C35121.3 (3)
C5—C6—C11119.7 (3)C36—C35—C34117.7 (3)
C1—C6—C11121.1 (3)C36—C35—C33121.7 (3)
C8—C7—C4112.0 (3)C34—C35—C33120.6 (3)
C8—C7—C10108.2 (3)C37—C36—C35123.0 (3)
C4—C7—C10109.9 (3)C37—C36—H36118.5
C8—C7—C9108.1 (3)C35—C36—H36118.5
C4—C7—C9108.7 (3)C36—C37—C38116.7 (3)
C10—C7—C9109.9 (3)C36—C37—C40123.1 (3)
C7—C8—H8A109.5C38—C37—C40120.1 (3)
C7—C8—H8B109.5C39—C38—C37122.8 (3)
H8A—C8—H8B109.5C39—C38—H38118.6
C7—C8—H8C109.5C37—C38—H38118.6
H8A—C8—H8C109.5C38—C39—C34118.4 (3)
H8B—C8—H8C109.5C38—C39—C44120.1 (3)
C7—C9—H9A109.5C34—C39—C44121.4 (3)
C7—C9—H9B109.5C41—C40—C43108.5 (3)
H9A—C9—H9B109.5C41—C40—C42108.7 (3)
C7—C9—H9C109.5C43—C40—C42108.9 (3)
H9A—C9—H9C109.5C41—C40—C37112.5 (3)
H9B—C9—H9C109.5C43—C40—C37110.3 (3)
C7—C10—H10A109.5C42—C40—C37107.9 (3)
C7—C10—H10B109.5C40—C41—H41A109.5
H10A—C10—H10B109.5C40—C41—H41B109.5
C7—C10—H10C109.5H41A—C41—H41B109.5
H10A—C10—H10C109.5C40—C41—H41C109.5
H10B—C10—H10C109.5H41A—C41—H41C109.5
C6—C11—C13113.3 (3)H41B—C41—H41C109.5
C6—C11—H11A108.9C40—C42—H42A109.5
C13—C11—H11A108.9C40—C42—H42B109.5
C6—C11—H11B108.9H42A—C42—H42B109.5
C13—C11—H11B108.9C40—C42—H42C109.5
H11A—C11—H11B107.7H42A—C42—H42C109.5
O2—C12—C13120.7 (3)H42B—C42—H42C109.5
O2—C12—C17118.2 (3)C40—C43—H43A109.5
C13—C12—C17121.1 (3)C40—C43—H43B109.5
C12—C13—C14118.5 (3)H43A—C43—H43B109.5
C12—C13—C11121.6 (3)C40—C43—H43C109.5
C14—C13—C11119.9 (3)H43A—C43—H43C109.5
C15—C14—C13122.8 (3)H43B—C43—H43C109.5
C15—C14—H14118.6C39—C44—C2114.1 (3)
C13—C14—H14118.6C39—C44—H44A108.7
C14—C15—C16116.3 (3)C2—C44—H44A108.7
C14—C15—C18123.6 (3)C39—C44—H44B108.7
C16—C15—C18120.1 (3)C2—C44—H44B108.7
C17—C16—C15123.4 (3)H44A—C44—H44B107.6
C17—C16—H16118.3C45—N1—Li2166.6 (3)
C15—C16—H16118.3N1—C45—C46178.5 (4)
C16—C17—C12118.0 (3)C45—C46—H46A109.5
C16—C17—C22119.8 (3)C45—C46—H46B109.5
C12—C17—C22122.0 (3)H46A—C46—H46B109.5
C19—C18—C15112.3 (3)C45—C46—H46C109.5
C19—C18—C20108.8 (3)H46A—C46—H46C109.5
C15—C18—C20107.8 (3)H46B—C46—H46C109.5
C19—C18—C21108.4 (3)C47—N2—Li2167.6 (3)
C15—C18—C21110.8 (3)N2—C47—C48178.7 (4)
C20—C18—C21108.6 (3)C47—C48—H48A109.5
C18—C19—H19A109.5C47—C48—H48B109.5
C18—C19—H19B109.5H48A—C48—H48B109.5
H19A—C19—H19B109.5C47—C48—H48C109.5
C18—C19—H19C109.5H48A—C48—H48C109.5
H19A—C19—H19C109.5H48B—C48—H48C109.5
H19B—C19—H19C109.5N3—C49—C50179.6 (5)
C18—C20—H20A109.5C49—C50—H50A109.5
C18—C20—H20B109.5C49—C50—H50B109.5
H20A—C20—H20B109.5H50A—C50—H50B109.5
C18—C20—H20C109.5C49—C50—H50C109.5
H20A—C20—H20C109.5H50A—C50—H50C109.5
H20B—C20—H20C109.5H50B—C50—H50C109.5
C18—C21—H21A109.5N4—C51—C52179.5 (5)
C18—C21—H21B109.5C51—C52—H52A109.5
H21A—C21—H21B109.5C51—C52—H52B109.5
C18—C21—H21C109.5H52A—C52—H52B109.5
H21A—C21—H21C109.5C51—C52—H52C109.5
H21B—C21—H21C109.5H52A—C52—H52C109.5
C17—C22—C24110.1 (3)H52B—C52—H52C109.5
C17—C22—H22A109.6N5—C53—C54178.2 (6)
C24—C22—H22A109.6C53—C54—H54A109.5
C17—C22—H22B109.6C53—C54—H54B109.5
C24—C22—H22B109.6H54A—C54—H54B109.5
H22A—C22—H22B108.2C53—C54—H54C109.5
O3—C23—C24121.5 (3)H54A—C54—H54C109.5
O3—C23—C28121.3 (3)H54B—C54—H54C109.5
C24—C23—C28117.1 (3)N6—C55—C56179.3 (5)
O3—C23—Li2i52.1 (2)C55—C56—H56A109.5
C24—C23—Li2i106.0 (2)C55—C56—H56B109.5
C28—C23—Li2i109.7 (3)H56A—C56—H56B109.5
C25—C24—C23120.3 (3)C55—C56—H56C109.5
C25—C24—C22117.3 (3)H56A—C56—H56C109.5
C23—C24—C22122.4 (3)H56B—C56—H56C109.5
O3i—Li2—O1—C1178.4 (3)Li2i—O3—C23—C2891.5 (3)
N1—Li2—O1—C161.6 (5)Li1—O3—C23—C28139.7 (3)
N2—Li2—O1—C153.6 (5)Li1i—O3—C23—C2841.8 (5)
O4i—Li1—O2—C1264.1 (8)Li1—O3—C23—Li2i128.9 (4)
O3—Li1—O2—C1263.2 (5)Li1i—O3—C23—Li2i133.3 (4)
O3i—Li1—O2—C12174.7 (3)O3—C23—C24—C25172.0 (3)
O4i—Li1—O3—C23131.5 (3)C28—C23—C24—C255.6 (5)
O2—Li1—O3—C2318.1 (5)Li2i—C23—C24—C25117.0 (3)
O3i—Li1—O3—C23125.2 (3)O3—C23—C24—C229.7 (5)
O4i—Li1—O3—Li2i10.6 (4)C28—C23—C24—C22172.6 (3)
O2—Li1—O3—Li2i139.0 (3)Li2i—C23—C24—C2264.7 (4)
O3i—Li1—O3—Li2i113.8 (3)C17—C22—C24—C2574.7 (4)
O4i—Li1—O3—Li1i103.2 (4)C17—C22—C24—C23103.7 (4)
O2—Li1—O3—Li1i107.2 (4)C23—C24—C25—C262.2 (5)
O3i—Li1—O3—Li1i0.000 (2)C22—C24—C25—C26176.2 (3)
Li2—O1—C1—C284.7 (4)C24—C25—C26—C271.7 (5)
Li2—O1—C1—C697.1 (4)C24—C25—C26—C29179.4 (3)
O1—C1—C2—C3176.4 (3)C25—C26—C27—C282.0 (5)
C6—C1—C2—C31.8 (5)C29—C26—C27—C28179.6 (3)
O1—C1—C2—C442.7 (5)C26—C27—C28—C231.6 (5)
C6—C1—C2—C44179.0 (3)C26—C27—C28—C33176.4 (3)
C1—C2—C3—C40.5 (5)O3—C23—C28—C27172.3 (3)
C44—C2—C3—C4179.6 (3)C24—C23—C28—C275.4 (5)
C2—C3—C4—C51.0 (5)Li2i—C23—C28—C27115.3 (3)
C2—C3—C4—C7180.0 (3)O3—C23—C28—C339.8 (5)
C3—C4—C5—C61.1 (5)C24—C23—C28—C33172.5 (3)
C7—C4—C5—C6179.9 (3)Li2i—C23—C28—C3366.7 (4)
C4—C5—C6—C10.2 (5)C25—C26—C29—C32176.0 (3)
C4—C5—C6—C11177.4 (3)C27—C26—C29—C326.5 (5)
O1—C1—C6—C5176.6 (3)C25—C26—C29—C3063.7 (4)
C2—C1—C6—C51.7 (5)C27—C26—C29—C30113.8 (4)
O1—C1—C6—C110.6 (5)C25—C26—C29—C3155.6 (4)
C2—C1—C6—C11178.9 (3)C27—C26—C29—C31126.9 (4)
C5—C4—C7—C80.7 (5)C27—C28—C33—C3574.1 (4)
C3—C4—C7—C8179.7 (3)C23—C28—C33—C35103.9 (4)
C5—C4—C7—C10121.1 (3)Li1i—O4—C34—C39156.2 (4)
C3—C4—C7—C1060.0 (4)Li1i—O4—C34—C3522.3 (6)
C5—C4—C7—C9118.7 (4)O4—C34—C35—C36176.0 (3)
C3—C4—C7—C960.3 (4)C39—C34—C35—C362.5 (5)
C5—C6—C11—C1390.3 (4)O4—C34—C35—C335.6 (5)
C1—C6—C11—C1386.9 (4)C39—C34—C35—C33175.9 (3)
Li1—O2—C12—C13172.6 (4)C28—C33—C35—C36100.8 (4)
Li1—O2—C12—C178.1 (6)C28—C33—C35—C3477.6 (4)
O2—C12—C13—C14179.9 (3)C34—C35—C36—C370.9 (5)
C17—C12—C13—C140.9 (5)C33—C35—C36—C37177.5 (3)
O2—C12—C13—C112.4 (5)C35—C36—C37—C380.7 (5)
C17—C12—C13—C11176.9 (3)C35—C36—C37—C40176.8 (3)
C6—C11—C13—C1286.9 (4)C36—C37—C38—C390.6 (5)
C6—C11—C13—C1490.8 (4)C40—C37—C38—C39176.9 (3)
C12—C13—C14—C150.2 (5)C37—C38—C39—C341.0 (5)
C11—C13—C14—C15178.0 (3)C37—C38—C39—C44179.5 (3)
C13—C14—C15—C160.6 (5)O4—C34—C39—C38175.8 (3)
C13—C14—C15—C18177.2 (3)C35—C34—C39—C382.6 (5)
C14—C15—C16—C172.5 (5)O4—C34—C39—C442.6 (5)
C18—C15—C16—C17175.4 (3)C35—C34—C39—C44178.9 (3)
C15—C16—C17—C123.5 (5)C36—C37—C40—C419.8 (5)
C15—C16—C17—C22172.3 (3)C38—C37—C40—C41172.8 (3)
O2—C12—C17—C16178.1 (3)C36—C37—C40—C43131.1 (4)
C13—C12—C17—C162.6 (5)C38—C37—C40—C4351.4 (4)
O2—C12—C17—C226.2 (5)C36—C37—C40—C42110.0 (4)
C13—C12—C17—C22173.0 (3)C38—C37—C40—C4267.4 (4)
C14—C15—C18—C197.8 (5)C38—C39—C44—C298.5 (4)
C16—C15—C18—C19174.5 (3)C34—C39—C44—C283.1 (4)
C14—C15—C18—C20112.0 (4)C3—C2—C44—C3989.6 (4)
C16—C15—C18—C2065.7 (4)C1—C2—C44—C3989.5 (4)
C14—C15—C18—C21129.2 (3)O1—Li2—N1—C4565.7 (16)
C16—C15—C18—C2153.1 (4)O3i—Li2—N1—C4543.1 (16)
C16—C17—C22—C2493.7 (4)N2—Li2—N1—C45173.3 (14)
C12—C17—C22—C2481.8 (4)O1—Li2—N2—C47144.7 (14)
Li2i—O3—C23—C2486.1 (3)O3i—Li2—N2—C4729.4 (17)
Li1—O3—C23—C2442.8 (5)N1—Li2—N2—C47100.2 (15)
Li1i—O3—C23—C24140.6 (3)
Symmetry code: (i) x+2, y+1, z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O10.82 (3)1.74 (3)2.554 (3)171 (4)
O4—H4···O10.93 (4)1.61 (4)2.525 (3)171 (3)

Experimental details

(I)(II)
Crystal data
Chemical formula[Li2(C45H57O4)2]·4C2H3N[Li4(C44H54O4)2(C2H3N)4]·8C2H3N
Mr1501.911814.16
Crystal system, space groupMonoclinic, P21/nTriclinic, P1
Temperature (K)150150
a, b, c (Å)12.8368 (11), 17.8044 (15), 19.6735 (16)12.8190 (12), 13.5649 (13), 18.223 (3)
α, β, γ (°)90, 90.2746 (12), 90106.035 (2), 94.097 (2), 115.286 (2)
V3)4496.4 (7)2687.4 (5)
Z21
Radiation typeSynchrotron, λ = 0.6911 ÅSynchrotron, λ = 0.8466 Å
µ (mm1)0.070.07
Crystal size (mm)0.24 × 0.06 × 0.050.15 × 0.14 × 0.07
Data collection
DiffractometerBruker APEX II CCD
diffractometer
Bruker APEX II CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Version 2004/1; Sheldrick, 2004)
Multi-scan
(SADABS; Version 2.10; Sheldrick, 2003)
Tmin, Tmax0.984, 0.9970.990, 0.995
No. of measured, independent and
observed [I > 2σ(I)] reflections
29080, 8536, 5918 15630, 7870, 4532
Rint0.0630.052
θmax (°)25.028.4
(sin θ/λ)max1)0.6120.562
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.074, 0.226, 1.03 0.065, 0.172, 1.00
No. of reflections85367870
No. of parameters561638
No. of restraints1720
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.75, 0.370.25, 0.24

Computer programs: APEX2 (Bruker 2006), APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SAINT (Bruker 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Version 6.10; Sheldrick, 2008) and local programs.

Selected geometric parameters (Å, º) for (I) top
Li1—O11.987 (5)Li1—O31.981 (5)
Li1—O21.853 (5)Li1—O4i1.866 (5)
O1—Li1—O2105.5 (2)O2—Li1—O3107.8 (2)
O1—Li1—O3112.6 (2)O2—Li1—O4i127.6 (3)
O1—Li1—O4i102.4 (2)O3—Li1—O4i100.9 (2)
Symmetry code: (i) x, y+1, z+1.
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O41.00 (4)1.59 (4)2.568 (3)165 (3)
O3—H3···O40.89 (4)1.68 (4)2.541 (3)162 (3)
Selected geometric parameters (Å, º) for (II) top
Li1—O21.919 (7)Li2—O11.888 (6)
Li1—O31.996 (7)Li2—O3i1.996 (6)
Li1—O3i1.996 (7)Li2—N12.082 (7)
Li1—O4i1.912 (7)Li2—N22.087 (6)
O1—Li2—O3i99.6 (3)O3i—Li1—O4i99.4 (3)
O2—Li1—O3104.6 (3)N1—Li2—O1105.4 (3)
O2—Li1—O3i101.4 (3)N1—Li2—O3i115.6 (3)
O2—Li1—O4i141.2 (4)N2—Li2—O1114.1 (3)
O3—Li1—O3i107.3 (3)N2—Li2—O3i116.5 (3)
O3—Li1—O4i99.9 (3)N1—Li2—N2105.4 (3)
Symmetry code: (i) x+2, y+1, z+2.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O10.82 (3)1.74 (3)2.554 (3)171 (4)
O4—H4···O10.93 (4)1.61 (4)2.525 (3)171 (3)
 

Subscribe to Acta Crystallographica Section C: Structural Chemistry

The full text of this article is available to subscribers to the journal.

If you have already registered and are using a computer listed in your registration details, please email support@iucr.org for assistance.

Buy online

You may purchase this article in PDF and/or HTML formats. For purchasers in the European Community who do not have a VAT number, VAT will be added at the local rate. Payments to the IUCr are handled by WorldPay, who will accept payment by credit card in several currencies. To purchase the article, please complete the form below (fields marked * are required), and then click on `Continue'.
E-mail address* 
Repeat e-mail address* 
(for error checking) 

Format*   PDF (US $40)
   HTML (US $40)
   PDF+HTML (US $50)
In order for VAT to be shown for your country javascript needs to be enabled.

VAT number 
(non-UK EC countries only) 
Country* 
 

Terms and conditions of use
Contact us

Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds