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, [Li
2(C
45H
57O
4)
2]·4C
2H
3N 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, [Li
4(C
44H
54O
4)
2(C
2H
3N)
4]·8C
2H
3N 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
CCDC references: 746040; 746041
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%).
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).
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.
(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]·4C2H3N | F(000) = 1624 |
Mr = 1501.91 | Dx = 1.109 Mg m−3 |
Monoclinic, P21/n | Synchrotron radiation, λ = 0.6911 Å |
Hall symbol: -P 2yn | Cell parameters from 5608 reflections |
a = 12.8368 (11) Å | θ = 2.3–26.4° |
b = 17.8044 (15) Å | µ = 0.07 mm−1 |
c = 19.6735 (16) Å | T = 150 K |
β = 90.2746 (12)° | Rod, colourless |
V = 4496.4 (7) Å3 | 0.24 × 0.06 × 0.05 mm |
Z = 2 | |
Data collection top
Bruker APEX II CCD diffractometer | 8536 independent reflections |
Radiation source: Daresbury SRS station 9.8 | 5918 reflections with I > 2σ(I) |
Silicon 111 monochromator | Rint = 0.063 |
ω rotation with narrow frames scans | θmax = 25.0°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Version 2004/1; Sheldrick, 2004) | h = −15→15 |
Tmin = 0.984, Tmax = 0.997 | k = −21→21 |
29080 measured reflections | l = −21→24 |
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)] = 0.074 | Hydrogen site location: geom except OH coords freely refined |
wR(F2) = 0.226 | H 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 parameters | Δρmax = 0.75 e Å−3 |
172 restraints | Δρmin = −0.37 e Å−3 |
Crystal data top
[Li2(C45H57O4)2]·4C2H3N | V = 4496.4 (7) Å3 |
Mr = 1501.91 | Z = 2 |
Monoclinic, P21/n | Synchrotron radiation, λ = 0.6911 Å |
a = 12.8368 (11) Å | µ = 0.07 mm−1 |
b = 17.8044 (15) Å | T = 150 K |
c = 19.6735 (16) Å | 0.24 × 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 = 0.997 | Rint = 0.063 |
29080 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.074 | 172 restraints |
wR(F2) = 0.226 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.75 e Å−3 |
8536 reflections | Δρmin = −0.37 e Å−3 |
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 | x | y | z | Uiso*/Ueq | Occ. (<1) |
Li1 | 0.0214 (3) | 0.4768 (3) | 0.4108 (2) | 0.0402 (10) | |
O1 | 0.16381 (14) | 0.49566 (11) | 0.44703 (10) | 0.0404 (5) | |
H1 | 0.125 (3) | 0.5273 (19) | 0.4802 (18) | 0.061* | |
O2 | 0.03983 (13) | 0.44608 (9) | 0.32171 (9) | 0.0343 (4) | |
O3 | −0.06579 (14) | 0.56860 (10) | 0.40956 (10) | 0.0381 (4) | |
H3 | −0.041 (3) | 0.5730 (19) | 0.4516 (18) | 0.057* | |
O4 | 0.04054 (14) | 0.57684 (10) | 0.51858 (9) | 0.0381 (4) | |
C1 | 0.26194 (19) | 0.52451 (15) | 0.43569 (13) | 0.0356 (6) | |
C2 | 0.3089 (2) | 0.57114 (15) | 0.48418 (14) | 0.0385 (6) | |
C3 | 0.4046 (2) | 0.60298 (16) | 0.46888 (15) | 0.0431 (7) | |
H3A | 0.4360 | 0.6358 | 0.5011 | 0.052* | |
C4 | 0.4564 (2) | 0.58896 (16) | 0.40853 (15) | 0.0423 (7) | |
C5 | 0.41016 (19) | 0.53838 (15) | 0.36412 (15) | 0.0404 (6) | |
H5 | 0.4461 | 0.5256 | 0.3236 | 0.049* | |
C6 | 0.31326 (19) | 0.50531 (14) | 0.37604 (14) | 0.0367 (6) | |
C7 | 0.5586 (2) | 0.62964 (18) | 0.39155 (18) | 0.0553 (8) | |
C8 | 0.5319 (6) | 0.7116 (4) | 0.3781 (8) | 0.099 (3) | 0.703 (17) |
H8A | 0.5956 | 0.7392 | 0.3671 | 0.149* | 0.703 (17) |
H8B | 0.5001 | 0.7334 | 0.4188 | 0.149* | 0.703 (17) |
H8C | 0.4829 | 0.7149 | 0.3399 | 0.149* | 0.703 (17) |
C9 | 0.6169 (7) | 0.5945 (6) | 0.3333 (4) | 0.079 (2) | 0.703 (17) |
H9A | 0.6810 | 0.6229 | 0.3250 | 0.119* | 0.703 (17) |
H9B | 0.5731 | 0.5952 | 0.2924 | 0.119* | 0.703 (17) |
H9C | 0.6346 | 0.5424 | 0.3448 | 0.119* | 0.703 (17) |
C10 | 0.6327 (5) | 0.6276 (5) | 0.4541 (3) | 0.067 (2) | 0.703 (17) |
H10A | 0.6977 | 0.6536 | 0.4431 | 0.100* | 0.703 (17) |
H10B | 0.6479 | 0.5753 | 0.4661 | 0.100* | 0.703 (17) |
H10C | 0.5993 | 0.6526 | 0.4926 | 0.100* | 0.703 (17) |
C8X | 0.5354 (14) | 0.6858 (15) | 0.3319 (14) | 0.102 (7) | 0.297 (17) |
H8D | 0.5995 | 0.7126 | 0.3201 | 0.153* | 0.297 (17) |
H8E | 0.4823 | 0.7219 | 0.3462 | 0.153* | 0.297 (17) |
H8F | 0.5101 | 0.6578 | 0.2922 | 0.153* | 0.297 (17) |
C9X | 0.6330 (16) | 0.5727 (12) | 0.3645 (18) | 0.107 (9) | 0.297 (17) |
H9D | 0.6988 | 0.5974 | 0.3530 | 0.161* | 0.297 (17) |
H9E | 0.6033 | 0.5493 | 0.3237 | 0.161* | 0.297 (17) |
H9F | 0.6457 | 0.5342 | 0.3991 | 0.161* | 0.297 (17) |
C10X | 0.6046 (17) | 0.677 (2) | 0.4485 (11) | 0.119 (9) | 0.297 (17) |
H10D | 0.6692 | 0.7001 | 0.4329 | 0.178* | 0.297 (17) |
H10E | 0.6196 | 0.6442 | 0.4877 | 0.178* | 0.297 (17) |
H10F | 0.5547 | 0.7155 | 0.4617 | 0.178* | 0.297 (17) |
C11 | 0.26415 (19) | 0.45412 (14) | 0.32329 (14) | 0.0375 (6) | |
H11A | 0.3193 | 0.4283 | 0.2972 | 0.045* | |
H11B | 0.2214 | 0.4154 | 0.3461 | 0.045* | |
C12 | 0.08800 (19) | 0.49991 (13) | 0.28061 (12) | 0.0311 (5) | |
C13 | 0.1965 (2) | 0.49980 (14) | 0.27562 (13) | 0.0347 (6) | |
C14 | 0.2409 (2) | 0.54884 (16) | 0.22944 (14) | 0.0422 (7) | |
H14 | 0.3143 | 0.5477 | 0.2236 | 0.051* | |
C15 | 0.1832 (2) | 0.59947 (16) | 0.19136 (14) | 0.0453 (7) | |
C16 | 0.0765 (2) | 0.60231 (16) | 0.20323 (14) | 0.0423 (6) | |
H16 | 0.0358 | 0.6388 | 0.1799 | 0.051* | |
C17 | 0.02708 (19) | 0.55343 (14) | 0.24823 (12) | 0.0336 (6) | |
C18 | 0.2364 (3) | 0.65003 (19) | 0.13841 (16) | 0.0579 (8) | |
C19 | 0.3268 (4) | 0.6920 (3) | 0.1709 (2) | 0.0823 (17) | 0.864 (7) |
H19A | 0.3722 | 0.6562 | 0.1946 | 0.123* | 0.864 (7) |
H19B | 0.2999 | 0.7287 | 0.2035 | 0.123* | 0.864 (7) |
H19C | 0.3665 | 0.7180 | 0.1356 | 0.123* | 0.864 (7) |
C20 | 0.1643 (4) | 0.7057 (4) | 0.1077 (4) | 0.112 (3) | 0.864 (7) |
H20A | 0.1056 | 0.6795 | 0.0863 | 0.169* | 0.864 (7) |
H20B | 0.2015 | 0.7351 | 0.0733 | 0.169* | 0.864 (7) |
H20C | 0.1383 | 0.7394 | 0.1432 | 0.169* | 0.864 (7) |
C21 | 0.2831 (4) | 0.5994 (3) | 0.0832 (2) | 0.0767 (16) | 0.864 (7) |
H21A | 0.2280 | 0.5684 | 0.0630 | 0.115* | 0.864 (7) |
H21B | 0.3365 | 0.5669 | 0.1034 | 0.115* | 0.864 (7) |
H21C | 0.3147 | 0.6307 | 0.0478 | 0.115* | 0.864 (7) |
C19X | 0.3538 (13) | 0.637 (2) | 0.135 (2) | 0.128 (14)* | 0.136 (7) |
H19D | 0.3874 | 0.6617 | 0.1741 | 0.192* | 0.136 (7) |
H19E | 0.3809 | 0.6591 | 0.0929 | 0.192* | 0.136 (7) |
H19F | 0.3685 | 0.5835 | 0.1360 | 0.192* | 0.136 (7) |
C20X | 0.209 (3) | 0.7282 (13) | 0.149 (2) | 0.116 (13)* | 0.136 (7) |
H20D | 0.2096 | 0.7390 | 0.1982 | 0.174* | 0.136 (7) |
H20E | 0.1396 | 0.7380 | 0.1307 | 0.174* | 0.136 (7) |
H20F | 0.2601 | 0.7605 | 0.1266 | 0.174* | 0.136 (7) |
C21X | 0.191 (2) | 0.6278 (16) | 0.0682 (10) | 0.073 (8)* | 0.136 (7) |
H21D | 0.2256 | 0.5818 | 0.0523 | 0.109* | 0.136 (7) |
H21E | 0.2038 | 0.6684 | 0.0357 | 0.109* | 0.136 (7) |
H21F | 0.1163 | 0.6190 | 0.0722 | 0.109* | 0.136 (7) |
C22 | −0.08684 (19) | 0.56515 (15) | 0.26564 (13) | 0.0359 (6) | |
H22A | −0.1285 | 0.5693 | 0.2233 | 0.043* | |
H22B | −0.1129 | 0.5216 | 0.2918 | 0.043* | |
C23 | −0.08764 (18) | 0.63548 (14) | 0.37778 (13) | 0.0337 (6) | |
C24 | −0.09855 (18) | 0.63590 (14) | 0.30719 (13) | 0.0340 (6) | |
C25 | −0.1139 (2) | 0.70451 (16) | 0.27513 (15) | 0.0461 (7) | |
H25 | −0.1222 | 0.7051 | 0.2271 | 0.055* | |
C26 | −0.1177 (3) | 0.77211 (17) | 0.30988 (17) | 0.0536 (8) | |
C27 | −0.1130 (2) | 0.76839 (16) | 0.38071 (16) | 0.0473 (7) | |
H27 | −0.1193 | 0.8136 | 0.4061 | 0.057* | |
C28 | −0.09938 (19) | 0.70132 (15) | 0.41544 (14) | 0.0376 (6) | |
C29 | −0.1266 (4) | 0.8470 (2) | 0.2705 (2) | 0.0736 (11) | |
C30 | −0.2345 (4) | 0.8537 (3) | 0.2413 (3) | 0.1007 (16) | |
H30A | −0.2504 | 0.8089 | 0.2142 | 0.151* | |
H30B | −0.2385 | 0.8984 | 0.2123 | 0.151* | |
H30C | −0.2849 | 0.8581 | 0.2783 | 0.151* | |
C31 | −0.0876 (6) | 0.9110 (2) | 0.3121 (3) | 0.122 (2) | |
H31A | −0.0838 | 0.9562 | 0.2838 | 0.183* | |
H31B | −0.0180 | 0.8991 | 0.3298 | 0.183* | |
H31C | −0.1351 | 0.9199 | 0.3501 | 0.183* | |
C32 | −0.0523 (3) | 0.8462 (2) | 0.2070 (2) | 0.0760 (11) | |
H32A | −0.0751 | 0.8071 | 0.1751 | 0.114* | |
H32B | 0.0192 | 0.8357 | 0.2219 | 0.114* | |
H32C | −0.0548 | 0.8952 | 0.1844 | 0.114* | |
C33 | −0.0936 (2) | 0.70126 (16) | 0.49264 (14) | 0.0426 (7) | |
H33A | −0.1369 | 0.7429 | 0.5103 | 0.051* | |
H33B | −0.1232 | 0.6536 | 0.5099 | 0.051* | |
C34 | 0.0796 (2) | 0.64663 (14) | 0.52886 (12) | 0.0358 (6) | |
C35 | 0.0169 (2) | 0.70987 (16) | 0.51952 (13) | 0.0386 (6) | |
C36 | 0.0586 (2) | 0.78038 (16) | 0.53160 (14) | 0.0442 (7) | |
H36 | 0.0150 | 0.8231 | 0.5262 | 0.053* | |
C37 | 0.1619 (2) | 0.79135 (16) | 0.55130 (14) | 0.0459 (7) | |
C38 | 0.2230 (2) | 0.72755 (16) | 0.55800 (14) | 0.0448 (7) | |
H38 | 0.2941 | 0.7332 | 0.5705 | 0.054* | |
C39 | 0.1844 (2) | 0.65577 (15) | 0.54722 (13) | 0.0385 (6) | |
C40 | 0.2031 (3) | 0.86959 (18) | 0.56844 (18) | 0.0584 (8) | |
C41 | 0.1657 (4) | 0.9264 (2) | 0.5184 (3) | 0.1048 (18) | |
H41A | 0.1793 | 0.9085 | 0.4722 | 0.157* | |
H41B | 0.2024 | 0.9739 | 0.5259 | 0.157* | |
H41C | 0.0906 | 0.9341 | 0.5242 | 0.157* | |
C42 | 0.1670 (3) | 0.8896 (2) | 0.6399 (2) | 0.0773 (11) | |
H42A | 0.1990 | 0.9371 | 0.6540 | 0.116* | |
H42B | 0.1879 | 0.8498 | 0.6716 | 0.116* | |
H42C | 0.0910 | 0.8948 | 0.6402 | 0.116* | |
C43 | 0.3239 (3) | 0.8695 (2) | 0.5725 (2) | 0.0757 (11) | |
H43A | 0.3525 | 0.8537 | 0.5287 | 0.114* | |
H43B | 0.3468 | 0.8345 | 0.6081 | 0.114* | |
H43C | 0.3487 | 0.9201 | 0.5834 | 0.114* | |
C44 | 0.2568 (2) | 0.58892 (16) | 0.55131 (14) | 0.0431 (7) | |
H44A | 0.2167 | 0.5445 | 0.5663 | 0.052* | |
H44B | 0.3112 | 0.5990 | 0.5860 | 0.052* | |
C45 | 0.0196 (2) | 0.37615 (16) | 0.28740 (16) | 0.0480 (7) | |
H45A | −0.0282 | 0.3849 | 0.2492 | 0.072* | |
H45B | −0.0119 | 0.3406 | 0.3193 | 0.072* | |
H45C | 0.0852 | 0.3554 | 0.2703 | 0.072* | |
N1 | 0.2374 (5) | 0.8298 (3) | 0.3158 (3) | 0.144 (2) | |
C46 | 0.2126 (3) | 0.7736 (2) | 0.33681 (18) | 0.0647 (9) | |
C47 | 0.1816 (3) | 0.70323 (19) | 0.36270 (16) | 0.0561 (8) | |
H47A | 0.2385 | 0.6670 | 0.3572 | 0.084* | |
H47B | 0.1200 | 0.6856 | 0.3378 | 0.084* | |
H47C | 0.1649 | 0.7082 | 0.4110 | 0.084* | |
N2 | 0.6234 (10) | 0.9253 (5) | 0.4142 (7) | 0.296 (7) | |
C48 | 0.5342 (8) | 0.9287 (3) | 0.4088 (4) | 0.136 (3) | |
C49 | 0.4287 (5) | 0.9297 (4) | 0.3997 (3) | 0.120 (2) | |
H49A | 0.4113 | 0.9610 | 0.3602 | 0.181* | |
H49B | 0.3955 | 0.9505 | 0.4403 | 0.181* | |
H49C | 0.4035 | 0.8784 | 0.3920 | 0.181* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Li1 | 0.040 (2) | 0.041 (2) | 0.040 (2) | −0.0083 (19) | 0.0106 (19) | 0.0056 (19) |
O1 | 0.0335 (10) | 0.0496 (11) | 0.0380 (10) | −0.0119 (8) | 0.0052 (8) | −0.0018 (8) |
O2 | 0.0337 (9) | 0.0343 (9) | 0.0350 (9) | −0.0055 (7) | 0.0065 (7) | 0.0007 (7) |
O3 | 0.0434 (11) | 0.0390 (10) | 0.0320 (10) | −0.0011 (8) | 0.0065 (8) | 0.0015 (8) |
O4 | 0.0403 (10) | 0.0405 (10) | 0.0335 (9) | −0.0116 (8) | 0.0081 (8) | 0.0018 (8) |
C1 | 0.0280 (13) | 0.0396 (14) | 0.0394 (14) | −0.0027 (10) | −0.0009 (11) | 0.0073 (11) |
C2 | 0.0334 (14) | 0.0420 (14) | 0.0401 (15) | −0.0007 (11) | −0.0037 (11) | 0.0034 (12) |
C3 | 0.0329 (14) | 0.0434 (15) | 0.0528 (17) | −0.0036 (11) | −0.0101 (12) | −0.0007 (13) |
C4 | 0.0242 (13) | 0.0459 (15) | 0.0569 (18) | 0.0009 (11) | −0.0014 (12) | 0.0015 (13) |
C5 | 0.0260 (13) | 0.0436 (15) | 0.0518 (17) | 0.0027 (11) | 0.0050 (11) | −0.0032 (13) |
C6 | 0.0277 (13) | 0.0370 (13) | 0.0454 (15) | 0.0032 (10) | 0.0007 (11) | −0.0001 (12) |
C7 | 0.0286 (14) | 0.0570 (18) | 0.080 (2) | −0.0090 (13) | 0.0009 (14) | 0.0000 (16) |
C8 | 0.056 (4) | 0.064 (4) | 0.178 (10) | −0.014 (3) | 0.006 (5) | 0.048 (5) |
C9 | 0.047 (4) | 0.121 (6) | 0.070 (4) | −0.038 (4) | 0.018 (3) | −0.012 (4) |
C10 | 0.032 (3) | 0.085 (5) | 0.083 (4) | −0.016 (3) | −0.005 (2) | −0.008 (3) |
C8X | 0.053 (8) | 0.099 (13) | 0.154 (16) | −0.033 (8) | 0.018 (11) | 0.047 (12) |
C9X | 0.028 (7) | 0.097 (11) | 0.20 (3) | −0.004 (7) | 0.031 (14) | −0.023 (12) |
C10X | 0.054 (11) | 0.16 (2) | 0.138 (13) | −0.053 (13) | 0.017 (9) | −0.054 (14) |
C11 | 0.0300 (13) | 0.0372 (13) | 0.0453 (15) | 0.0007 (10) | 0.0059 (11) | −0.0047 (12) |
C12 | 0.0330 (13) | 0.0347 (13) | 0.0258 (12) | −0.0050 (10) | 0.0063 (10) | −0.0043 (10) |
C13 | 0.0339 (13) | 0.0368 (13) | 0.0334 (13) | −0.0030 (10) | 0.0062 (10) | −0.0091 (11) |
C14 | 0.0348 (14) | 0.0518 (16) | 0.0399 (15) | −0.0077 (12) | 0.0121 (12) | −0.0056 (13) |
C15 | 0.0501 (17) | 0.0497 (16) | 0.0361 (15) | −0.0103 (13) | 0.0128 (13) | 0.0004 (12) |
C16 | 0.0499 (17) | 0.0446 (15) | 0.0325 (14) | −0.0025 (12) | 0.0042 (12) | 0.0049 (12) |
C17 | 0.0351 (13) | 0.0391 (13) | 0.0266 (12) | −0.0044 (11) | 0.0000 (10) | −0.0022 (10) |
C18 | 0.066 (2) | 0.063 (2) | 0.0454 (18) | −0.0121 (16) | 0.0183 (15) | 0.0101 (15) |
C19 | 0.106 (4) | 0.075 (3) | 0.066 (3) | −0.053 (3) | 0.030 (2) | 0.005 (2) |
C20 | 0.086 (4) | 0.119 (5) | 0.133 (6) | 0.013 (3) | 0.048 (3) | 0.089 (4) |
C21 | 0.108 (4) | 0.074 (3) | 0.048 (2) | −0.028 (3) | 0.037 (2) | −0.003 (2) |
C22 | 0.0318 (13) | 0.0421 (14) | 0.0336 (14) | −0.0045 (11) | −0.0035 (10) | 0.0014 (11) |
C23 | 0.0225 (12) | 0.0361 (13) | 0.0427 (15) | −0.0011 (10) | 0.0046 (10) | 0.0014 (11) |
C24 | 0.0226 (12) | 0.0394 (14) | 0.0401 (14) | −0.0007 (10) | −0.0021 (10) | −0.0013 (11) |
C25 | 0.0483 (17) | 0.0464 (16) | 0.0436 (16) | 0.0017 (13) | −0.0132 (13) | 0.0025 (13) |
C26 | 0.0571 (19) | 0.0425 (16) | 0.061 (2) | 0.0052 (14) | −0.0197 (16) | −0.0011 (14) |
C27 | 0.0398 (15) | 0.0402 (15) | 0.062 (2) | 0.0063 (12) | −0.0051 (14) | −0.0082 (14) |
C28 | 0.0222 (12) | 0.0426 (14) | 0.0479 (16) | 0.0006 (10) | 0.0055 (11) | −0.0074 (12) |
C29 | 0.102 (3) | 0.0473 (19) | 0.072 (2) | 0.0144 (19) | −0.021 (2) | 0.0056 (17) |
C30 | 0.092 (3) | 0.107 (4) | 0.103 (4) | 0.042 (3) | 0.007 (3) | 0.048 (3) |
C31 | 0.240 (7) | 0.046 (2) | 0.080 (3) | −0.006 (3) | −0.016 (4) | 0.007 (2) |
C32 | 0.081 (3) | 0.062 (2) | 0.084 (3) | −0.0062 (19) | −0.002 (2) | 0.020 (2) |
C33 | 0.0368 (15) | 0.0429 (15) | 0.0481 (16) | −0.0013 (11) | 0.0147 (12) | −0.0107 (12) |
C34 | 0.0440 (15) | 0.0401 (14) | 0.0235 (12) | −0.0117 (11) | 0.0092 (11) | −0.0003 (10) |
C35 | 0.0390 (14) | 0.0486 (15) | 0.0283 (13) | −0.0070 (12) | 0.0126 (11) | −0.0060 (11) |
C36 | 0.0531 (18) | 0.0437 (15) | 0.0359 (15) | −0.0038 (13) | 0.0111 (13) | −0.0085 (12) |
C37 | 0.0551 (18) | 0.0484 (16) | 0.0343 (15) | −0.0137 (14) | 0.0037 (13) | −0.0068 (12) |
C38 | 0.0473 (16) | 0.0533 (17) | 0.0339 (15) | −0.0153 (13) | 0.0002 (12) | −0.0050 (12) |
C39 | 0.0413 (15) | 0.0482 (15) | 0.0260 (13) | −0.0087 (12) | 0.0019 (11) | −0.0010 (11) |
C40 | 0.064 (2) | 0.0531 (19) | 0.058 (2) | −0.0155 (16) | −0.0010 (16) | −0.0089 (15) |
C41 | 0.141 (4) | 0.064 (2) | 0.109 (4) | −0.049 (3) | −0.055 (3) | 0.024 (2) |
C42 | 0.090 (3) | 0.064 (2) | 0.079 (3) | −0.005 (2) | −0.001 (2) | −0.029 (2) |
C43 | 0.075 (3) | 0.068 (2) | 0.084 (3) | −0.0276 (19) | −0.002 (2) | −0.004 (2) |
C44 | 0.0442 (16) | 0.0498 (16) | 0.0354 (15) | −0.0083 (12) | −0.0064 (12) | 0.0022 (12) |
C45 | 0.0529 (17) | 0.0395 (15) | 0.0516 (18) | −0.0121 (13) | 0.0074 (14) | −0.0075 (13) |
N1 | 0.215 (6) | 0.092 (3) | 0.124 (4) | −0.036 (3) | 0.038 (4) | 0.033 (3) |
C46 | 0.077 (2) | 0.066 (2) | 0.052 (2) | −0.0108 (18) | 0.0094 (17) | 0.0087 (17) |
C47 | 0.058 (2) | 0.062 (2) | 0.0476 (18) | −0.0082 (16) | 0.0095 (15) | 0.0026 (15) |
N2 | 0.263 (11) | 0.191 (8) | 0.433 (17) | −0.072 (8) | −0.203 (12) | 0.023 (9) |
C48 | 0.182 (7) | 0.077 (3) | 0.150 (6) | −0.024 (4) | −0.069 (6) | 0.003 (3) |
C49 | 0.135 (5) | 0.141 (5) | 0.086 (4) | 0.020 (4) | 0.026 (3) | 0.046 (3) |
Geometric parameters (Å, º) top
Li1—O1 | 1.987 (5) | C21—H21C | 0.9800 |
Li1—O2 | 1.853 (5) | C19X—H19D | 0.9800 |
Li1—O3 | 1.981 (5) | C19X—H19E | 0.9800 |
Li1—O4i | 1.866 (5) | C19X—H19F | 0.9800 |
Li1—H1 | 2.10 (3) | C20X—H20D | 0.9800 |
Li1—H3 | 2.06 (3) | C20X—H20E | 0.9800 |
O1—C1 | 1.379 (3) | C20X—H20F | 0.9800 |
O1—H1 | 1.00 (4) | C21X—H21D | 0.9800 |
O2—C12 | 1.400 (3) | C21X—H21E | 0.9800 |
O2—C45 | 1.439 (3) | C21X—H21F | 0.9800 |
O3—C23 | 1.373 (3) | C22—C24 | 1.509 (4) |
O3—H3 | 0.89 (4) | C22—H22A | 0.9900 |
O4—C34 | 1.355 (3) | C22—H22B | 0.9900 |
O4—Li1i | 1.866 (5) | C23—C24 | 1.395 (4) |
C1—C6 | 1.391 (4) | C23—C28 | 1.395 (4) |
C1—C2 | 1.399 (4) | C24—C25 | 1.388 (4) |
C2—C3 | 1.387 (4) | C25—C26 | 1.385 (4) |
C2—C44 | 1.517 (4) | C25—H25 | 0.9500 |
C3—C4 | 1.386 (4) | C26—C27 | 1.396 (5) |
C3—H3A | 0.9500 | C26—C29 | 1.546 (5) |
C4—C5 | 1.386 (4) | C27—C28 | 1.387 (4) |
C4—C7 | 1.537 (4) | C27—H27 | 0.9500 |
C5—C6 | 1.397 (4) | C28—C33 | 1.520 (4) |
C5—H5 | 0.9500 | C29—C31 | 1.490 (6) |
C6—C11 | 1.516 (4) | C29—C30 | 1.501 (6) |
C7—C9X | 1.492 (13) | C29—C32 | 1.576 (6) |
C7—C9 | 1.508 (8) | C30—H30A | 0.9800 |
C7—C10X | 1.514 (12) | C30—H30B | 0.9800 |
C7—C8 | 1.521 (7) | C30—H30C | 0.9800 |
C7—C10 | 1.552 (6) | C31—H31A | 0.9800 |
C7—C8X | 1.568 (12) | C31—H31B | 0.9800 |
C8—H8A | 0.9800 | C31—H31C | 0.9800 |
C8—H8B | 0.9800 | C32—H32A | 0.9800 |
C8—H8C | 0.9800 | C32—H32B | 0.9800 |
C9—H9A | 0.9800 | C32—H32C | 0.9800 |
C9—H9B | 0.9800 | C33—C35 | 1.520 (4) |
C9—H9C | 0.9800 | C33—H33A | 0.9900 |
C10—H10A | 0.9800 | C33—H33B | 0.9900 |
C10—H10B | 0.9800 | C34—C35 | 1.396 (4) |
C10—H10C | 0.9800 | C34—C39 | 1.401 (4) |
C8X—H8D | 0.9800 | C35—C36 | 1.385 (4) |
C8X—H8E | 0.9800 | C36—C37 | 1.393 (4) |
C8X—H8F | 0.9800 | C36—H36 | 0.9500 |
C9X—H9D | 0.9800 | C37—C38 | 1.386 (4) |
C9X—H9E | 0.9800 | C37—C40 | 1.527 (4) |
C9X—H9F | 0.9800 | C38—C39 | 1.386 (4) |
C10X—H10D | 0.9800 | C38—H38 | 0.9500 |
C10X—H10E | 0.9800 | C39—C44 | 1.512 (4) |
C10X—H10F | 0.9800 | C40—C41 | 1.489 (5) |
C11—C13 | 1.512 (4) | C40—C42 | 1.525 (5) |
C11—H11A | 0.9900 | C40—C43 | 1.552 (5) |
C11—H11B | 0.9900 | C41—H41A | 0.9800 |
C12—C17 | 1.386 (4) | C41—H41B | 0.9800 |
C12—C13 | 1.397 (3) | C41—H41C | 0.9800 |
C13—C14 | 1.384 (4) | C42—H42A | 0.9800 |
C14—C15 | 1.384 (4) | C42—H42B | 0.9800 |
C14—H14 | 0.9500 | C42—H42C | 0.9800 |
C15—C16 | 1.392 (4) | C43—H43A | 0.9800 |
C15—C18 | 1.539 (4) | C43—H43B | 0.9800 |
C16—C17 | 1.396 (4) | C43—H43C | 0.9800 |
C16—H16 | 0.9500 | C44—H44A | 0.9900 |
C17—C22 | 1.518 (4) | C44—H44B | 0.9900 |
C18—C20X | 1.452 (18) | C45—H45A | 0.9800 |
C18—C20 | 1.483 (6) | C45—H45B | 0.9800 |
C18—C19 | 1.518 (5) | C45—H45C | 0.9800 |
C18—C19X | 1.525 (16) | N1—C46 | 1.128 (5) |
C18—C21 | 1.536 (5) | C46—C47 | 1.411 (5) |
C18—C21X | 1.546 (14) | C47—H47A | 0.9800 |
C19—H19A | 0.9800 | C47—H47B | 0.9800 |
C19—H19B | 0.9800 | C47—H47C | 0.9800 |
C19—H19C | 0.9800 | N2—C48 | 1.151 (12) |
C20—H20A | 0.9800 | C48—C49 | 1.366 (10) |
C20—H20B | 0.9800 | C49—H49A | 0.9800 |
C20—H20C | 0.9800 | C49—H49B | 0.9800 |
C21—H21A | 0.9800 | C49—H49C | 0.9800 |
C21—H21B | 0.9800 | | |
| | | |
O1—Li1—O2 | 105.5 (2) | H21A—C21—H21B | 109.5 |
O1—Li1—O3 | 112.6 (2) | C18—C21—H21C | 109.5 |
O1—Li1—O4i | 102.4 (2) | H21A—C21—H21C | 109.5 |
O2—Li1—O3 | 107.8 (2) | H21B—C21—H21C | 109.5 |
O2—Li1—O4i | 127.6 (3) | C18—C19X—H19D | 109.5 |
O3—Li1—O4i | 100.9 (2) | C18—C19X—H19E | 109.5 |
O2—Li1—H1 | 131.1 (10) | H19D—C19X—H19E | 109.5 |
O4i—Li1—H1 | 90.3 (9) | C18—C19X—H19F | 109.5 |
O3—Li1—H1 | 90.6 (10) | H19D—C19X—H19F | 109.5 |
O1—Li1—H1 | 28.1 (10) | H19E—C19X—H19F | 109.5 |
O2—Li1—H3 | 131.8 (10) | C18—C20X—H20D | 109.5 |
O4i—Li1—H3 | 88.1 (10) | C18—C20X—H20E | 109.5 |
O3—Li1—H3 | 25.3 (10) | H20D—C20X—H20E | 109.5 |
O1—Li1—H3 | 94.6 (10) | C18—C20X—H20F | 109.5 |
H1—Li1—H3 | 68.8 (14) | H20D—C20X—H20F | 109.5 |
C1—O1—Li1 | 147.6 (2) | H20E—C20X—H20F | 109.5 |
C1—O1—H1 | 110.8 (19) | C18—C21X—H21D | 109.5 |
Li1—O1—H1 | 82.4 (19) | C18—C21X—H21E | 109.5 |
C12—O2—C45 | 113.61 (19) | H21D—C21X—H21E | 109.5 |
C12—O2—Li1 | 113.79 (19) | C18—C21X—H21F | 109.5 |
C45—O2—Li1 | 132.5 (2) | H21D—C21X—H21F | 109.5 |
C23—O3—Li1 | 146.7 (2) | H21E—C21X—H21F | 109.5 |
C23—O3—H3 | 115 (2) | C24—C22—C17 | 109.6 (2) |
Li1—O3—H3 | 82 (2) | C24—C22—H22A | 109.8 |
C34—O4—Li1i | 121.1 (2) | C17—C22—H22A | 109.8 |
O1—C1—C6 | 118.8 (2) | C24—C22—H22B | 109.8 |
O1—C1—C2 | 120.1 (2) | C17—C22—H22B | 109.8 |
C6—C1—C2 | 121.1 (2) | H22A—C22—H22B | 108.2 |
C3—C2—C1 | 118.3 (3) | O3—C23—C24 | 118.5 (2) |
C3—C2—C44 | 119.9 (2) | O3—C23—C28 | 120.6 (2) |
C1—C2—C44 | 121.8 (2) | C24—C23—C28 | 120.9 (2) |
C4—C3—C2 | 122.7 (3) | C25—C24—C23 | 118.1 (2) |
C4—C3—H3A | 118.6 | C25—C24—C22 | 120.2 (2) |
C2—C3—H3A | 118.6 | C23—C24—C22 | 121.7 (2) |
C3—C4—C5 | 116.9 (2) | C26—C25—C24 | 123.1 (3) |
C3—C4—C7 | 121.0 (3) | C26—C25—H25 | 118.5 |
C5—C4—C7 | 122.2 (3) | C24—C25—H25 | 118.5 |
C4—C5—C6 | 123.1 (3) | C25—C26—C27 | 116.8 (3) |
C4—C5—H5 | 118.4 | C25—C26—C29 | 120.3 (3) |
C6—C5—H5 | 118.4 | C27—C26—C29 | 123.0 (3) |
C1—C6—C5 | 117.6 (2) | C28—C27—C26 | 122.5 (3) |
C1—C6—C11 | 121.9 (2) | C28—C27—H27 | 118.7 |
C5—C6—C11 | 120.4 (2) | C26—C27—H27 | 118.7 |
C9X—C7—C10X | 112.9 (12) | C27—C28—C23 | 118.4 (3) |
C9—C7—C10X | 126.7 (9) | C27—C28—C33 | 119.9 (2) |
C9—C7—C8 | 112.2 (5) | C23—C28—C33 | 121.7 (2) |
C9X—C7—C4 | 107.8 (10) | C31—C29—C30 | 117.2 (4) |
C9—C7—C4 | 113.4 (4) | C31—C29—C26 | 111.2 (3) |
C10X—C7—C4 | 115.4 (8) | C30—C29—C26 | 109.0 (3) |
C8—C7—C4 | 107.4 (4) | C31—C29—C32 | 103.8 (4) |
C9—C7—C10 | 106.7 (4) | C30—C29—C32 | 105.0 (3) |
C8—C7—C10 | 107.2 (5) | C26—C29—C32 | 110.3 (3) |
C4—C7—C10 | 109.7 (3) | C29—C30—H30A | 109.5 |
C9X—C7—C8X | 106.6 (11) | C29—C30—H30B | 109.5 |
C10X—C7—C8X | 105.9 (12) | H30A—C30—H30B | 109.5 |
C4—C7—C8X | 107.7 (7) | C29—C30—H30C | 109.5 |
C7—C8—H8A | 109.5 | H30A—C30—H30C | 109.5 |
C7—C8—H8B | 109.5 | H30B—C30—H30C | 109.5 |
H8A—C8—H8B | 109.5 | C29—C31—H31A | 109.5 |
C7—C8—H8C | 109.5 | C29—C31—H31B | 109.5 |
H8A—C8—H8C | 109.5 | H31A—C31—H31B | 109.5 |
H8B—C8—H8C | 109.5 | C29—C31—H31C | 109.5 |
C7—C9—H9A | 109.5 | H31A—C31—H31C | 109.5 |
C7—C9—H9B | 109.5 | H31B—C31—H31C | 109.5 |
H9A—C9—H9B | 109.5 | C29—C32—H32A | 109.5 |
C7—C9—H9C | 109.5 | C29—C32—H32B | 109.5 |
H9A—C9—H9C | 109.5 | H32A—C32—H32B | 109.5 |
H9B—C9—H9C | 109.5 | C29—C32—H32C | 109.5 |
C7—C10—H10A | 109.5 | H32A—C32—H32C | 109.5 |
C7—C10—H10B | 109.5 | H32B—C32—H32C | 109.5 |
H10A—C10—H10B | 109.5 | C35—C33—C28 | 112.8 (2) |
C7—C10—H10C | 109.5 | C35—C33—H33A | 109.0 |
H10A—C10—H10C | 109.5 | C28—C33—H33A | 109.0 |
H10B—C10—H10C | 109.5 | C35—C33—H33B | 109.0 |
C7—C8X—H8D | 109.5 | C28—C33—H33B | 109.0 |
C7—C8X—H8E | 109.5 | H33A—C33—H33B | 107.8 |
H8D—C8X—H8E | 109.5 | O4—C34—C35 | 120.5 (2) |
C7—C8X—H8F | 109.5 | O4—C34—C39 | 120.0 (2) |
H8D—C8X—H8F | 109.5 | C35—C34—C39 | 119.5 (2) |
H8E—C8X—H8F | 109.5 | C36—C35—C34 | 119.1 (3) |
C7—C9X—H9D | 109.5 | C36—C35—C33 | 120.7 (3) |
C7—C9X—H9E | 109.5 | C34—C35—C33 | 120.1 (2) |
H9D—C9X—H9E | 109.5 | C35—C36—C37 | 122.8 (3) |
C7—C9X—H9F | 109.5 | C35—C36—H36 | 118.6 |
H9D—C9X—H9F | 109.5 | C37—C36—H36 | 118.6 |
H9E—C9X—H9F | 109.5 | C38—C37—C36 | 116.7 (3) |
C7—C10X—H10D | 109.5 | C38—C37—C40 | 122.1 (3) |
C7—C10X—H10E | 109.5 | C36—C37—C40 | 121.2 (3) |
H10D—C10X—H10E | 109.5 | C39—C38—C37 | 122.6 (3) |
C7—C10X—H10F | 109.5 | C39—C38—H38 | 118.7 |
H10D—C10X—H10F | 109.5 | C37—C38—H38 | 118.7 |
H10E—C10X—H10F | 109.5 | C38—C39—C34 | 119.2 (3) |
C13—C11—C6 | 109.7 (2) | C38—C39—C44 | 119.9 (3) |
C13—C11—H11A | 109.7 | C34—C39—C44 | 120.7 (2) |
C6—C11—H11A | 109.7 | C41—C40—C42 | 110.6 (4) |
C13—C11—H11B | 109.7 | C41—C40—C37 | 111.3 (3) |
C6—C11—H11B | 109.7 | C42—C40—C37 | 108.1 (3) |
H11A—C11—H11B | 108.2 | C41—C40—C43 | 110.8 (3) |
C17—C12—C13 | 122.0 (2) | C42—C40—C43 | 105.1 (3) |
C17—C12—O2 | 119.1 (2) | C37—C40—C43 | 110.8 (3) |
C13—C12—O2 | 118.9 (2) | C40—C41—H41A | 109.5 |
C17—C12—Li1 | 110.84 (19) | C40—C41—H41B | 109.5 |
C13—C12—Li1 | 112.45 (19) | H41A—C41—H41B | 109.5 |
C14—C13—C12 | 117.3 (2) | C40—C41—H41C | 109.5 |
C14—C13—C11 | 120.7 (2) | H41A—C41—H41C | 109.5 |
C12—C13—C11 | 121.8 (2) | H41B—C41—H41C | 109.5 |
C15—C14—C13 | 123.1 (3) | C40—C42—H42A | 109.5 |
C15—C14—H14 | 118.5 | C40—C42—H42B | 109.5 |
C13—C14—H14 | 118.5 | H42A—C42—H42B | 109.5 |
C14—C15—C16 | 117.2 (2) | C40—C42—H42C | 109.5 |
C14—C15—C18 | 120.6 (3) | H42A—C42—H42C | 109.5 |
C16—C15—C18 | 122.2 (3) | H42B—C42—H42C | 109.5 |
C15—C16—C17 | 122.3 (3) | C40—C43—H43A | 109.5 |
C15—C16—H16 | 118.9 | C40—C43—H43B | 109.5 |
C17—C16—H16 | 118.9 | H43A—C43—H43B | 109.5 |
C12—C17—C16 | 117.6 (2) | C40—C43—H43C | 109.5 |
C12—C17—C22 | 122.2 (2) | H43A—C43—H43C | 109.5 |
C16—C17—C22 | 119.9 (2) | H43B—C43—H43C | 109.5 |
C20—C18—C19 | 108.5 (4) | C39—C44—C2 | 113.0 (2) |
C20X—C18—C19X | 112.6 (18) | C39—C44—H44A | 109.0 |
C20—C18—C21 | 110.4 (4) | C2—C44—H44A | 109.0 |
C19—C18—C21 | 106.6 (4) | C39—C44—H44B | 109.0 |
C20X—C18—C15 | 110.7 (19) | C2—C44—H44B | 109.0 |
C20—C18—C15 | 112.9 (3) | H44A—C44—H44B | 107.8 |
C19—C18—C15 | 110.1 (3) | O2—C45—H45A | 109.5 |
C19X—C18—C15 | 112.6 (18) | O2—C45—H45B | 109.5 |
C21—C18—C15 | 108.2 (3) | H45A—C45—H45B | 109.5 |
C20X—C18—C21X | 106.9 (16) | O2—C45—H45C | 109.5 |
C19X—C18—C21X | 106.8 (18) | H45A—C45—H45C | 109.5 |
C15—C18—C21X | 106.8 (11) | H45B—C45—H45C | 109.5 |
C18—C19—H19A | 109.5 | N1—C46—C47 | 179.7 (5) |
C18—C19—H19B | 109.5 | C46—C47—H47A | 109.5 |
H19A—C19—H19B | 109.5 | C46—C47—H47B | 109.5 |
C18—C19—H19C | 109.5 | H47A—C47—H47B | 109.5 |
H19A—C19—H19C | 109.5 | C46—C47—H47C | 109.5 |
H19B—C19—H19C | 109.5 | H47A—C47—H47C | 109.5 |
C18—C20—H20A | 109.5 | H47B—C47—H47C | 109.5 |
C18—C20—H20B | 109.5 | N2—C48—C49 | 176.8 (10) |
H20A—C20—H20B | 109.5 | C48—C49—H49A | 109.5 |
C18—C20—H20C | 109.5 | C48—C49—H49B | 109.5 |
H20A—C20—H20C | 109.5 | H49A—C49—H49B | 109.5 |
H20B—C20—H20C | 109.5 | C48—C49—H49C | 109.5 |
C18—C21—H21A | 109.5 | H49A—C49—H49C | 109.5 |
C18—C21—H21B | 109.5 | H49B—C49—H49C | 109.5 |
| | | |
O2—Li1—O1—C1 | 41.0 (5) | C13—C12—C17—C22 | −165.8 (2) |
O4i—Li1—O1—C1 | 176.2 (3) | O2—C12—C17—C22 | 11.6 (3) |
O3—Li1—O1—C1 | −76.3 (5) | Li1—C12—C17—C22 | −29.9 (3) |
O4i—Li1—O2—C12 | 179.2 (3) | C15—C16—C17—C12 | −1.2 (4) |
O3—Li1—O2—C12 | 59.3 (3) | C15—C16—C17—C22 | 172.6 (2) |
O1—Li1—O2—C12 | −61.2 (3) | C14—C15—C18—C20X | −127.7 (17) |
O4i—Li1—O2—C45 | −5.0 (5) | C16—C15—C18—C20X | 52.3 (17) |
O3—Li1—O2—C45 | −124.8 (3) | C14—C15—C18—C20 | −174.2 (4) |
O1—Li1—O2—C45 | 114.7 (3) | C16—C15—C18—C20 | 5.7 (5) |
O2—Li1—O3—C23 | −39.5 (5) | C14—C15—C18—C19 | −52.9 (4) |
O4i—Li1—O3—C23 | −175.1 (3) | C16—C15—C18—C19 | 127.1 (4) |
O1—Li1—O3—C23 | 76.5 (4) | C14—C15—C18—C19X | −0.6 (18) |
Li1—O1—C1—C6 | −48.5 (5) | C16—C15—C18—C19X | 179.4 (18) |
Li1—O1—C1—C2 | 132.6 (4) | C14—C15—C18—C21 | 63.3 (4) |
O1—C1—C2—C3 | −175.8 (2) | C16—C15—C18—C21 | −116.7 (4) |
C6—C1—C2—C3 | 5.3 (4) | C14—C15—C18—C21X | 116.3 (12) |
O1—C1—C2—C44 | 2.6 (4) | C16—C15—C18—C21X | −63.7 (12) |
C6—C1—C2—C44 | −176.3 (2) | C12—C17—C22—C24 | 104.8 (3) |
C1—C2—C3—C4 | −1.7 (4) | C16—C17—C22—C24 | −68.7 (3) |
C44—C2—C3—C4 | 179.9 (3) | Li1—O3—C23—C24 | 47.3 (5) |
C2—C3—C4—C5 | −2.7 (4) | Li1—O3—C23—C28 | −133.1 (4) |
C2—C3—C4—C7 | 175.8 (3) | O3—C23—C24—C25 | −175.9 (2) |
C3—C4—C5—C6 | 3.7 (4) | C28—C23—C24—C25 | 4.6 (4) |
C7—C4—C5—C6 | −174.7 (3) | O3—C23—C24—C22 | −0.1 (3) |
O1—C1—C6—C5 | 176.7 (2) | C28—C23—C24—C22 | −179.6 (2) |
C2—C1—C6—C5 | −4.4 (4) | C17—C22—C24—C25 | 88.9 (3) |
O1—C1—C6—C11 | 0.3 (4) | C17—C22—C24—C23 | −86.8 (3) |
C2—C1—C6—C11 | 179.3 (2) | C23—C24—C25—C26 | 0.7 (4) |
C4—C5—C6—C1 | −0.2 (4) | C22—C24—C25—C26 | −175.2 (3) |
C4—C5—C6—C11 | 176.2 (2) | C24—C25—C26—C27 | −4.6 (5) |
C3—C4—C7—C9X | 135.3 (15) | C24—C25—C26—C29 | 175.3 (3) |
C5—C4—C7—C9X | −46.4 (16) | C25—C26—C27—C28 | 3.4 (5) |
C3—C4—C7—C9 | 165.9 (5) | C29—C26—C27—C28 | −176.4 (3) |
C5—C4—C7—C9 | −15.8 (6) | C26—C27—C28—C23 | 1.5 (4) |
C3—C4—C7—C10X | 8.0 (18) | C26—C27—C28—C33 | 179.3 (3) |
C5—C4—C7—C10X | −173.7 (17) | O3—C23—C28—C27 | 174.8 (2) |
C3—C4—C7—C8 | −69.6 (7) | C24—C23—C28—C27 | −5.6 (4) |
C5—C4—C7—C8 | 108.8 (7) | O3—C23—C28—C33 | −2.9 (4) |
C3—C4—C7—C10 | 46.7 (5) | C24—C23—C28—C33 | 176.6 (2) |
C5—C4—C7—C10 | −135.0 (5) | C25—C26—C29—C31 | −157.1 (4) |
C3—C4—C7—C8X | −110.0 (15) | C27—C26—C29—C31 | 22.7 (6) |
C5—C4—C7—C8X | 68.3 (15) | C25—C26—C29—C30 | 72.2 (5) |
C1—C6—C11—C13 | 85.7 (3) | C27—C26—C29—C30 | −107.9 (4) |
C5—C6—C11—C13 | −90.5 (3) | C25—C26—C29—C32 | −42.5 (5) |
C45—O2—C12—C17 | 96.1 (3) | C27—C26—C29—C32 | 137.3 (3) |
Li1—O2—C12—C17 | −87.2 (3) | C27—C28—C33—C35 | −90.4 (3) |
C45—O2—C12—C13 | −86.4 (3) | C23—C28—C33—C35 | 87.3 (3) |
Li1—O2—C12—C13 | 90.3 (3) | Li1i—O4—C34—C35 | −90.1 (3) |
C45—O2—C12—Li1 | −176.7 (3) | Li1i—O4—C34—C39 | 91.7 (3) |
O2—Li1—C12—C17 | 111.0 (3) | O4—C34—C35—C36 | 178.9 (2) |
O4i—Li1—C12—C17 | 109.4 (6) | C39—C34—C35—C36 | −2.9 (4) |
O3—Li1—C12—C17 | −14.0 (2) | O4—C34—C35—C33 | −4.5 (4) |
O1—Li1—C12—C17 | −126.6 (2) | C39—C34—C35—C33 | 173.7 (2) |
O2—Li1—C12—C13 | −108.7 (3) | C28—C33—C35—C36 | 89.2 (3) |
O4i—Li1—C12—C13 | −110.3 (6) | C28—C33—C35—C34 | −87.3 (3) |
O3—Li1—C12—C13 | 126.3 (2) | C34—C35—C36—C37 | 1.5 (4) |
O1—Li1—C12—C13 | 13.7 (2) | C33—C35—C36—C37 | −175.0 (2) |
O4i—Li1—C12—O2 | −1.6 (5) | C35—C36—C37—C38 | 0.5 (4) |
O3—Li1—C12—O2 | −125.0 (3) | C35—C36—C37—C40 | −176.1 (3) |
O1—Li1—C12—O2 | 122.4 (3) | C36—C37—C38—C39 | −1.3 (4) |
C17—C12—C13—C14 | −8.8 (4) | C40—C37—C38—C39 | 175.4 (3) |
O2—C12—C13—C14 | 173.8 (2) | C37—C38—C39—C34 | −0.1 (4) |
Li1—C12—C13—C14 | −144.1 (2) | C37—C38—C39—C44 | 176.4 (3) |
C17—C12—C13—C11 | 165.1 (2) | O4—C34—C39—C38 | −179.6 (2) |
O2—C12—C13—C11 | −12.3 (3) | C35—C34—C39—C38 | 2.2 (4) |
Li1—C12—C13—C11 | 29.8 (3) | O4—C34—C39—C44 | 4.0 (4) |
C6—C11—C13—C14 | 70.3 (3) | C35—C34—C39—C44 | −174.3 (2) |
C6—C11—C13—C12 | −103.4 (3) | C38—C37—C40—C41 | 140.3 (4) |
C12—C13—C14—C15 | 3.3 (4) | C36—C37—C40—C41 | −43.3 (5) |
C11—C13—C14—C15 | −170.7 (2) | C38—C37—C40—C42 | −98.1 (4) |
C13—C14—C15—C16 | 2.9 (4) | C36—C37—C40—C42 | 78.4 (4) |
C13—C14—C15—C18 | −177.1 (3) | C38—C37—C40—C43 | 16.6 (4) |
C14—C15—C16—C17 | −4.0 (4) | C36—C37—C40—C43 | −167.0 (3) |
C18—C15—C16—C17 | 176.0 (3) | C38—C39—C44—C2 | −88.0 (3) |
C13—C12—C17—C16 | 7.8 (4) | C34—C39—C44—C2 | 88.4 (3) |
O2—C12—C17—C16 | −174.8 (2) | C3—C2—C44—C39 | 91.1 (3) |
Li1—C12—C17—C16 | 143.7 (2) | C1—C2—C44—C39 | −87.2 (3) |
Symmetry code: (i) −x, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O4 | 1.00 (4) | 1.59 (4) | 2.568 (3) | 165 (3) |
O3—H3···O4 | 0.89 (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]·8C2H3N | Z = 1 |
Mr = 1814.16 | F(000) = 976 |
Triclinic, P1 | Dx = 1.121 Mg m−3 |
Hall symbol: -P 1 | Synchrotron radiation, λ = 0.8466 Å |
a = 12.8190 (12) Å | Cell parameters from 1271 reflections |
b = 13.5649 (13) Å | θ = 3.7–24.0° |
c = 18.223 (3) Å | µ = 0.07 mm−1 |
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 16.2SMX | 4532 reflections with I > 2σ(I) |
Silicon 111 monochromator | Rint = 0.052 |
ω rotation with narrow frames scans | θmax = 28.4°, θmin = 3.7° |
Absorption correction: multi-scan (SADABS; Version 2.10; Sheldrick, 2003) | h = −14→14 |
Tmin = 0.990, Tmax = 0.995 | k = −15→15 |
15630 measured reflections | l = −20→20 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: geom except H2 and H4 coords freely refined |
R[F2 > 2σ(F2)] = 0.065 | H 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 reflections | Δρmax = 0.25 e Å−3 |
638 parameters | Δρmin = −0.24 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc^*^=kFc[1+0.001xFc^2^λ^3^/sin(2θ)]^-1/4^ |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0042 (8) |
Crystal data top
[Li4(C44H54O4)2(C2H3N)4]·8C2H3N | γ = 115.286 (2)° |
Mr = 1814.16 | V = 2687.4 (5) Å3 |
Triclinic, P1 | Z = 1 |
a = 12.8190 (12) Å | Synchrotron radiation, λ = 0.8466 Å |
b = 13.5649 (13) Å | µ = 0.07 mm−1 |
c = 18.223 (3) Å | T = 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 = 0.995 | Rint = 0.052 |
15630 measured reflections | θmax = 28.4° |
Refinement top
R[F2 > 2σ(F2)] = 0.065 | 0 restraints |
wR(F2) = 0.172 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | Δρmax = 0.25 e Å−3 |
7870 reflections | Δρmin = −0.24 e Å−3 |
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 | x | y | z | Uiso*/Ueq | |
Li1 | 0.9268 (6) | 0.4028 (5) | 0.9851 (4) | 0.0430 (17) | |
Li2 | 0.8047 (5) | 0.5768 (5) | 0.9635 (3) | 0.0320 (14) | |
O1 | 0.83884 (18) | 0.52342 (18) | 0.86567 (13) | 0.0267 (6) | |
O2 | 0.8311 (2) | 0.3393 (2) | 0.88146 (14) | 0.0309 (6) | |
H2 | 0.841 (3) | 0.401 (3) | 0.877 (2) | 0.037* | |
O3 | 1.09210 (19) | 0.45547 (18) | 0.96967 (13) | 0.0315 (6) | |
O4 | 1.0586 (2) | 0.6357 (2) | 0.92266 (14) | 0.0363 (7) | |
H4 | 0.979 (3) | 0.599 (3) | 0.899 (2) | 0.044* | |
C1 | 0.8069 (3) | 0.5172 (3) | 0.79141 (19) | 0.0240 (8) | |
C2 | 0.8662 (3) | 0.6128 (3) | 0.7670 (2) | 0.0248 (8) | |
C3 | 0.8365 (3) | 0.6024 (3) | 0.6898 (2) | 0.0280 (9) | |
H3 | 0.8777 | 0.6675 | 0.6742 | 0.034* | |
C4 | 0.7481 (3) | 0.5000 (3) | 0.6335 (2) | 0.0283 (9) | |
C5 | 0.6892 (3) | 0.4076 (3) | 0.6601 (2) | 0.0271 (8) | |
H5 | 0.6278 | 0.3373 | 0.6239 | 0.033* | |
C6 | 0.7159 (3) | 0.4137 (3) | 0.7369 (2) | 0.0237 (8) | |
C7 | 0.7195 (3) | 0.4942 (3) | 0.5486 (2) | 0.0342 (9) | |
C8 | 0.6208 (4) | 0.3759 (3) | 0.4971 (2) | 0.0523 (12) | |
H8A | 0.6453 | 0.3163 | 0.4960 | 0.078* | |
H8B | 0.6042 | 0.3762 | 0.4439 | 0.078* | |
H8C | 0.5494 | 0.3589 | 0.5183 | 0.078* | |
C9 | 0.6790 (4) | 0.5857 (3) | 0.5482 (2) | 0.0546 (12) | |
H9A | 0.6063 | 0.5675 | 0.5680 | 0.082* | |
H9B | 0.6639 | 0.5854 | 0.4946 | 0.082* | |
H9C | 0.7409 | 0.6625 | 0.5816 | 0.082* | |
C10 | 0.8299 (3) | 0.5184 (3) | 0.5137 (2) | 0.0496 (11) | |
H10A | 0.8942 | 0.5949 | 0.5455 | 0.074* | |
H10B | 0.8117 | 0.5169 | 0.4601 | 0.074* | |
H10C | 0.8543 | 0.4589 | 0.5131 | 0.074* | |
C11 | 0.6510 (3) | 0.3078 (3) | 0.75983 (19) | 0.0258 (8) | |
H11A | 0.5700 | 0.2613 | 0.7267 | 0.031* | |
H11B | 0.6441 | 0.3333 | 0.8149 | 0.031* | |
C12 | 0.7993 (3) | 0.2520 (3) | 0.81150 (19) | 0.0237 (8) | |
C13 | 0.7115 (3) | 0.2318 (3) | 0.75150 (19) | 0.0210 (8) | |
C14 | 0.6822 (3) | 0.1413 (3) | 0.68119 (19) | 0.0249 (8) | |
H14 | 0.6223 | 0.1275 | 0.6401 | 0.030* | |
C15 | 0.7370 (3) | 0.0708 (3) | 0.66898 (19) | 0.0256 (8) | |
C16 | 0.8237 (3) | 0.0943 (3) | 0.73170 (19) | 0.0259 (8) | |
H16 | 0.8605 | 0.0458 | 0.7260 | 0.031* | |
C17 | 0.8586 (3) | 0.1849 (3) | 0.80184 (19) | 0.0253 (8) | |
C18 | 0.7101 (3) | −0.0252 (3) | 0.5913 (2) | 0.0297 (9) | |
C19 | 0.6051 (4) | −0.0457 (3) | 0.5328 (2) | 0.0514 (12) | |
H19A | 0.5347 | −0.0676 | 0.5552 | 0.077* | |
H19B | 0.5907 | −0.1081 | 0.4844 | 0.077* | |
H19C | 0.6226 | 0.0256 | 0.5214 | 0.077* | |
C20 | 0.8200 (4) | 0.0117 (3) | 0.5562 (2) | 0.0484 (11) | |
H20A | 0.8389 | 0.0856 | 0.5484 | 0.073* | |
H20B | 0.8045 | −0.0477 | 0.5058 | 0.073* | |
H20C | 0.8869 | 0.0207 | 0.5919 | 0.073* | |
C21 | 0.6835 (3) | −0.1397 (3) | 0.6045 (2) | 0.0418 (10) | |
H21A | 0.7514 | −0.1289 | 0.6402 | 0.063* | |
H21B | 0.6685 | −0.1994 | 0.5543 | 0.063* | |
H21C | 0.6136 | −0.1641 | 0.6272 | 0.063* | |
C22 | 0.9638 (3) | 0.2136 (3) | 0.8629 (2) | 0.0285 (9) | |
H22A | 0.9730 | 0.1432 | 0.8570 | 0.034* | |
H22B | 0.9502 | 0.2405 | 0.9159 | 0.034* | |
C23 | 1.1284 (3) | 0.4244 (3) | 0.9037 (2) | 0.0299 (9) | |
C24 | 1.0759 (3) | 0.3078 (3) | 0.8533 (2) | 0.0287 (9) | |
C25 | 1.1249 (3) | 0.2755 (3) | 0.7902 (2) | 0.0311 (9) | |
H25 | 1.0893 | 0.1960 | 0.7583 | 0.037* | |
C26 | 1.2233 (3) | 0.3542 (3) | 0.7720 (2) | 0.0302 (9) | |
C27 | 1.2690 (3) | 0.4699 (3) | 0.8199 (2) | 0.0338 (9) | |
H27 | 1.3345 | 0.5268 | 0.8085 | 0.041* | |
C28 | 1.2241 (3) | 0.5066 (3) | 0.8833 (2) | 0.0285 (9) | |
C29 | 1.2720 (3) | 0.3138 (3) | 0.7018 (2) | 0.0381 (10) | |
C30 | 1.1804 (4) | 0.2656 (4) | 0.6255 (2) | 0.0574 (12) | |
H30A | 1.1071 | 0.2022 | 0.6279 | 0.086* | |
H30B | 1.2112 | 0.2364 | 0.5814 | 0.086* | |
H30C | 1.1645 | 0.3273 | 0.6185 | 0.086* | |
C31 | 1.3012 (4) | 0.2162 (4) | 0.7077 (3) | 0.0635 (13) | |
H31A | 1.3651 | 0.2469 | 0.7536 | 0.095* | |
H31B | 1.3263 | 0.1875 | 0.6604 | 0.095* | |
H31C | 1.2308 | 0.1526 | 0.7129 | 0.095* | |
C32 | 1.3850 (4) | 0.4115 (4) | 0.6952 (3) | 0.0714 (15) | |
H32A | 1.3679 | 0.4720 | 0.6870 | 0.107* | |
H32B | 1.4142 | 0.3805 | 0.6508 | 0.107* | |
H32C | 1.4452 | 0.4446 | 0.7434 | 0.107* | |
C33 | 1.2789 (3) | 0.6362 (3) | 0.9268 (2) | 0.0299 (9) | |
H33A | 1.2554 | 0.6499 | 0.9777 | 0.036* | |
H33B | 1.3661 | 0.6700 | 0.9371 | 0.036* | |
C34 | 1.1271 (3) | 0.6887 (3) | 0.87651 (19) | 0.0267 (8) | |
C35 | 1.2397 (3) | 0.6954 (3) | 0.87983 (19) | 0.0267 (8) | |
C36 | 1.3122 (3) | 0.7556 (3) | 0.83702 (19) | 0.0280 (9) | |
H36 | 1.3891 | 0.7617 | 0.8394 | 0.034* | |
C37 | 1.2770 (3) | 0.8073 (3) | 0.79095 (19) | 0.0266 (8) | |
C38 | 1.1630 (3) | 0.7953 (3) | 0.78839 (19) | 0.0276 (8) | |
H38 | 1.1362 | 0.8290 | 0.7570 | 0.033* | |
C39 | 1.0870 (3) | 0.7363 (3) | 0.82971 (19) | 0.0252 (8) | |
C40 | 1.3590 (3) | 0.8791 (3) | 0.7469 (2) | 0.0357 (9) | |
C41 | 1.4726 (3) | 0.8697 (4) | 0.7480 (3) | 0.0522 (12) | |
H41A | 1.5147 | 0.8962 | 0.8023 | 0.078* | |
H41B | 1.5224 | 0.9181 | 0.7205 | 0.078* | |
H41C | 1.4541 | 0.7888 | 0.7220 | 0.078* | |
C42 | 1.3897 (4) | 1.0063 (3) | 0.7870 (3) | 0.0651 (14) | |
H42A | 1.3170 | 1.0139 | 0.7851 | 0.098* | |
H42B | 1.4417 | 1.0539 | 0.7599 | 0.098* | |
H42C | 1.4301 | 1.0324 | 0.8417 | 0.098* | |
C43 | 1.2962 (4) | 0.8395 (4) | 0.6620 (2) | 0.0710 (15) | |
H43A | 1.2723 | 0.7570 | 0.6367 | 0.106* | |
H43B | 1.3499 | 0.8846 | 0.6344 | 0.106* | |
H43C | 1.2260 | 0.8516 | 0.6603 | 0.106* | |
C44 | 0.9643 (3) | 0.7274 (3) | 0.8249 (2) | 0.0292 (9) | |
H44A | 0.9645 | 0.7920 | 0.8094 | 0.035* | |
H44B | 0.9461 | 0.7370 | 0.8775 | 0.035* | |
N1 | 0.6236 (3) | 0.4761 (3) | 0.94941 (18) | 0.0401 (8) | |
C45 | 0.5308 (3) | 0.4044 (3) | 0.9400 (2) | 0.0345 (9) | |
C46 | 0.4125 (3) | 0.3102 (3) | 0.9282 (2) | 0.0529 (12) | |
H46A | 0.4054 | 0.2385 | 0.8912 | 0.079* | |
H46B | 0.3538 | 0.3293 | 0.9071 | 0.079* | |
H46C | 0.3988 | 0.2994 | 0.9783 | 0.079* | |
N2 | 0.8329 (2) | 0.7478 (3) | 0.99599 (17) | 0.0325 (8) | |
C47 | 0.8544 (3) | 0.8414 (3) | 1.0269 (2) | 0.0319 (9) | |
C48 | 0.8829 (4) | 0.9616 (3) | 1.0682 (2) | 0.0517 (12) | |
H48A | 0.8849 | 1.0011 | 1.0303 | 0.078* | |
H48B | 0.9603 | 1.0011 | 1.1041 | 0.078* | |
H48C | 0.8226 | 0.9633 | 1.0979 | 0.078* | |
N3 | 0.9044 (4) | 0.2981 (4) | 0.5485 (3) | 0.0752 (13) | |
C49 | 0.9445 (4) | 0.3536 (4) | 0.6127 (3) | 0.0493 (11) | |
C50 | 0.9966 (4) | 0.4246 (4) | 0.6948 (2) | 0.0556 (12) | |
H50A | 0.9410 | 0.4489 | 0.7178 | 0.083* | |
H50B | 1.0699 | 0.4933 | 0.6989 | 0.083* | |
H50C | 1.0140 | 0.3795 | 0.7229 | 0.083* | |
N4 | 0.5849 (4) | −0.1088 (4) | 0.9839 (3) | 0.0847 (14) | |
C51 | 0.6295 (4) | −0.0267 (5) | 0.9687 (3) | 0.0566 (13) | |
C52 | 0.6872 (4) | 0.0780 (4) | 0.9494 (3) | 0.0705 (14) | |
H52A | 0.7034 | 0.0584 | 0.8970 | 0.106* | |
H52B | 0.7618 | 0.1319 | 0.9877 | 0.106* | |
H52C | 0.6356 | 0.1145 | 0.9504 | 0.106* | |
N5 | 0.8126 (4) | 0.9105 (4) | 0.8610 (2) | 0.0691 (12) | |
C53 | 0.7386 (4) | 0.8179 (5) | 0.8343 (3) | 0.0586 (13) | |
C54 | 0.6436 (4) | 0.7001 (4) | 0.8025 (3) | 0.0882 (18) | |
H54A | 0.5807 | 0.6920 | 0.8316 | 0.132* | |
H54B | 0.6739 | 0.6464 | 0.8072 | 0.132* | |
H54C | 0.6119 | 0.6823 | 0.7473 | 0.132* | |
N6 | 0.9783 (4) | 0.0484 (3) | 0.2773 (2) | 0.0683 (12) | |
C55 | 0.9821 (4) | 0.0852 (4) | 0.3414 (3) | 0.0466 (11) | |
C56 | 0.9881 (4) | 0.1325 (4) | 0.4243 (3) | 0.0714 (14) | |
H56A | 0.9494 | 0.0689 | 0.4444 | 0.107* | |
H56B | 0.9480 | 0.1808 | 0.4323 | 0.107* | |
H56C | 1.0711 | 0.1797 | 0.4522 | 0.107* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Li1 | 0.040 (4) | 0.039 (4) | 0.043 (4) | 0.014 (3) | 0.005 (3) | 0.013 (3) |
Li2 | 0.029 (3) | 0.028 (3) | 0.039 (4) | 0.016 (3) | 0.008 (3) | 0.009 (3) |
O1 | 0.0228 (13) | 0.0225 (13) | 0.0315 (14) | 0.0082 (11) | 0.0080 (11) | 0.0078 (11) |
O2 | 0.0382 (15) | 0.0182 (14) | 0.0296 (14) | 0.0097 (12) | 0.0048 (11) | 0.0048 (13) |
O3 | 0.0328 (15) | 0.0242 (14) | 0.0282 (14) | 0.0065 (12) | 0.0036 (11) | 0.0076 (12) |
O4 | 0.0233 (14) | 0.0398 (16) | 0.0355 (15) | 0.0022 (12) | 0.0055 (12) | 0.0189 (13) |
C1 | 0.023 (2) | 0.025 (2) | 0.026 (2) | 0.0144 (17) | 0.0093 (16) | 0.0066 (17) |
C2 | 0.0173 (19) | 0.0196 (19) | 0.038 (2) | 0.0107 (16) | 0.0077 (16) | 0.0064 (17) |
C3 | 0.028 (2) | 0.020 (2) | 0.041 (2) | 0.0135 (17) | 0.0111 (17) | 0.0142 (18) |
C4 | 0.025 (2) | 0.024 (2) | 0.038 (2) | 0.0149 (17) | 0.0070 (17) | 0.0081 (18) |
C5 | 0.024 (2) | 0.019 (2) | 0.035 (2) | 0.0116 (16) | 0.0015 (16) | 0.0024 (17) |
C6 | 0.0190 (19) | 0.0161 (19) | 0.037 (2) | 0.0102 (16) | 0.0086 (16) | 0.0063 (17) |
C7 | 0.038 (2) | 0.029 (2) | 0.033 (2) | 0.0152 (19) | 0.0006 (18) | 0.0083 (18) |
C8 | 0.059 (3) | 0.043 (3) | 0.042 (3) | 0.015 (2) | 0.000 (2) | 0.014 (2) |
C9 | 0.071 (3) | 0.050 (3) | 0.048 (3) | 0.036 (2) | −0.004 (2) | 0.014 (2) |
C10 | 0.057 (3) | 0.053 (3) | 0.043 (3) | 0.025 (2) | 0.017 (2) | 0.022 (2) |
C11 | 0.0198 (19) | 0.023 (2) | 0.031 (2) | 0.0098 (16) | 0.0063 (15) | 0.0048 (17) |
C12 | 0.026 (2) | 0.0109 (18) | 0.029 (2) | 0.0055 (16) | 0.0092 (16) | 0.0035 (16) |
C13 | 0.0222 (19) | 0.0135 (18) | 0.026 (2) | 0.0085 (15) | 0.0063 (16) | 0.0049 (16) |
C14 | 0.021 (2) | 0.0201 (19) | 0.030 (2) | 0.0076 (16) | 0.0025 (15) | 0.0075 (17) |
C15 | 0.024 (2) | 0.022 (2) | 0.031 (2) | 0.0112 (17) | 0.0055 (16) | 0.0103 (17) |
C16 | 0.024 (2) | 0.019 (2) | 0.038 (2) | 0.0122 (16) | 0.0082 (17) | 0.0099 (18) |
C17 | 0.022 (2) | 0.020 (2) | 0.029 (2) | 0.0056 (16) | 0.0055 (16) | 0.0093 (17) |
C18 | 0.030 (2) | 0.022 (2) | 0.034 (2) | 0.0133 (17) | 0.0015 (17) | 0.0049 (17) |
C19 | 0.064 (3) | 0.045 (3) | 0.039 (3) | 0.036 (2) | −0.006 (2) | −0.006 (2) |
C20 | 0.057 (3) | 0.033 (2) | 0.047 (3) | 0.019 (2) | 0.021 (2) | 0.001 (2) |
C21 | 0.041 (2) | 0.025 (2) | 0.045 (2) | 0.0124 (19) | −0.0013 (19) | −0.0012 (19) |
C22 | 0.028 (2) | 0.0185 (19) | 0.035 (2) | 0.0083 (16) | 0.0032 (16) | 0.0082 (17) |
C23 | 0.025 (2) | 0.023 (2) | 0.034 (2) | 0.0062 (17) | −0.0035 (17) | 0.0103 (18) |
C24 | 0.024 (2) | 0.028 (2) | 0.033 (2) | 0.0110 (17) | 0.0002 (17) | 0.0117 (18) |
C25 | 0.024 (2) | 0.024 (2) | 0.038 (2) | 0.0074 (17) | −0.0026 (17) | 0.0080 (18) |
C26 | 0.025 (2) | 0.033 (2) | 0.032 (2) | 0.0129 (18) | 0.0039 (17) | 0.0107 (19) |
C27 | 0.021 (2) | 0.029 (2) | 0.042 (2) | 0.0045 (17) | −0.0047 (17) | 0.014 (2) |
C28 | 0.028 (2) | 0.026 (2) | 0.026 (2) | 0.0102 (18) | −0.0020 (17) | 0.0069 (17) |
C29 | 0.030 (2) | 0.033 (2) | 0.047 (3) | 0.0118 (19) | 0.0081 (19) | 0.013 (2) |
C30 | 0.060 (3) | 0.077 (3) | 0.041 (3) | 0.041 (3) | 0.011 (2) | 0.013 (2) |
C31 | 0.069 (3) | 0.081 (4) | 0.070 (3) | 0.057 (3) | 0.028 (3) | 0.029 (3) |
C32 | 0.052 (3) | 0.060 (3) | 0.078 (3) | 0.010 (3) | 0.034 (3) | 0.010 (3) |
C33 | 0.021 (2) | 0.028 (2) | 0.034 (2) | 0.0060 (17) | 0.0016 (16) | 0.0101 (18) |
C34 | 0.021 (2) | 0.024 (2) | 0.022 (2) | −0.0006 (16) | 0.0037 (15) | 0.0069 (17) |
C35 | 0.026 (2) | 0.0149 (19) | 0.027 (2) | 0.0010 (16) | 0.0000 (16) | 0.0055 (16) |
C36 | 0.023 (2) | 0.023 (2) | 0.032 (2) | 0.0062 (17) | 0.0070 (16) | 0.0076 (17) |
C37 | 0.028 (2) | 0.020 (2) | 0.028 (2) | 0.0077 (17) | 0.0079 (16) | 0.0087 (17) |
C38 | 0.028 (2) | 0.0190 (19) | 0.033 (2) | 0.0092 (17) | 0.0040 (17) | 0.0089 (17) |
C39 | 0.025 (2) | 0.0166 (19) | 0.025 (2) | 0.0053 (16) | 0.0034 (16) | 0.0012 (16) |
C40 | 0.034 (2) | 0.037 (2) | 0.047 (2) | 0.0189 (19) | 0.0198 (19) | 0.023 (2) |
C41 | 0.039 (3) | 0.065 (3) | 0.071 (3) | 0.027 (2) | 0.031 (2) | 0.042 (3) |
C42 | 0.064 (3) | 0.043 (3) | 0.110 (4) | 0.026 (2) | 0.054 (3) | 0.047 (3) |
C43 | 0.064 (3) | 0.111 (4) | 0.055 (3) | 0.040 (3) | 0.029 (3) | 0.050 (3) |
C44 | 0.025 (2) | 0.020 (2) | 0.035 (2) | 0.0062 (16) | 0.0058 (16) | 0.0052 (17) |
N1 | 0.033 (2) | 0.043 (2) | 0.047 (2) | 0.0202 (18) | 0.0136 (16) | 0.0128 (17) |
C45 | 0.027 (2) | 0.040 (3) | 0.038 (2) | 0.018 (2) | 0.0120 (19) | 0.010 (2) |
C46 | 0.042 (3) | 0.039 (3) | 0.062 (3) | 0.010 (2) | 0.013 (2) | 0.009 (2) |
N2 | 0.0335 (19) | 0.0299 (19) | 0.0376 (19) | 0.0171 (16) | 0.0095 (14) | 0.0123 (16) |
C47 | 0.026 (2) | 0.034 (2) | 0.037 (2) | 0.0165 (19) | 0.0043 (17) | 0.011 (2) |
C48 | 0.050 (3) | 0.029 (2) | 0.061 (3) | 0.017 (2) | −0.002 (2) | 0.000 (2) |
N3 | 0.108 (4) | 0.067 (3) | 0.063 (3) | 0.057 (3) | 0.017 (3) | 0.014 (2) |
C49 | 0.056 (3) | 0.047 (3) | 0.067 (3) | 0.039 (2) | 0.027 (3) | 0.025 (3) |
C50 | 0.053 (3) | 0.070 (3) | 0.055 (3) | 0.041 (3) | 0.016 (2) | 0.016 (3) |
N4 | 0.053 (3) | 0.102 (4) | 0.092 (3) | 0.020 (3) | 0.012 (2) | 0.051 (3) |
C51 | 0.039 (3) | 0.073 (4) | 0.047 (3) | 0.022 (3) | 0.003 (2) | 0.014 (3) |
C52 | 0.075 (4) | 0.044 (3) | 0.070 (3) | 0.021 (3) | 0.006 (3) | 0.000 (3) |
N5 | 0.057 (3) | 0.070 (3) | 0.094 (3) | 0.035 (2) | 0.020 (2) | 0.037 (3) |
C53 | 0.047 (3) | 0.065 (4) | 0.082 (4) | 0.039 (3) | 0.018 (3) | 0.029 (3) |
C54 | 0.052 (3) | 0.056 (3) | 0.138 (5) | 0.026 (3) | 0.011 (3) | 0.008 (3) |
N6 | 0.095 (3) | 0.070 (3) | 0.063 (3) | 0.055 (3) | 0.020 (2) | 0.026 (2) |
C55 | 0.050 (3) | 0.042 (3) | 0.058 (3) | 0.028 (2) | 0.015 (2) | 0.019 (2) |
C56 | 0.091 (4) | 0.077 (4) | 0.059 (3) | 0.050 (3) | 0.028 (3) | 0.019 (3) |
Geometric parameters (Å, º) top
Li1—O2 | 1.919 (7) | C26—C27 | 1.397 (5) |
Li1—O3 | 1.996 (7) | C26—C29 | 1.531 (5) |
Li1—O3i | 1.996 (7) | C27—C28 | 1.392 (5) |
Li1—O4i | 1.912 (7) | C27—H27 | 0.9500 |
Li1—H2 | 2.18 (4) | C28—C33 | 1.519 (4) |
Li2—O1 | 1.888 (6) | C29—C32 | 1.531 (5) |
Li2—O3i | 1.996 (6) | C29—C30 | 1.532 (5) |
Li2—N1 | 2.082 (7) | C29—C31 | 1.549 (5) |
Li2—N2 | 2.087 (6) | C30—H30A | 0.9800 |
O1—C1 | 1.354 (4) | C30—H30B | 0.9800 |
O2—C12 | 1.369 (4) | C30—H30C | 0.9800 |
O2—H2 | 0.82 (3) | C31—H31A | 0.9800 |
O3—C23 | 1.344 (4) | C31—H31B | 0.9800 |
O3—Li2i | 1.996 (6) | C31—H31C | 0.9800 |
O3—Li1i | 1.996 (7) | C32—H32A | 0.9800 |
O4—C34 | 1.377 (4) | C32—H32B | 0.9800 |
O4—Li1i | 1.912 (7) | C32—H32C | 0.9800 |
O4—H4 | 0.93 (4) | C33—C35 | 1.514 (4) |
C1—C2 | 1.408 (4) | C33—H33A | 0.9900 |
C1—C6 | 1.409 (4) | C33—H33B | 0.9900 |
C2—C3 | 1.382 (4) | C34—C39 | 1.391 (4) |
C2—C44 | 1.531 (4) | C34—C35 | 1.403 (5) |
C3—C4 | 1.403 (5) | C35—C36 | 1.395 (4) |
C3—H3 | 0.9500 | C36—C37 | 1.393 (4) |
C4—C5 | 1.398 (4) | C36—H36 | 0.9500 |
C4—C7 | 1.537 (5) | C37—C38 | 1.396 (4) |
C5—C6 | 1.387 (4) | C37—C40 | 1.540 (5) |
C5—H5 | 0.9500 | C38—C39 | 1.389 (4) |
C6—C11 | 1.514 (4) | C38—H38 | 0.9500 |
C7—C8 | 1.524 (5) | C39—C44 | 1.519 (4) |
C7—C10 | 1.538 (5) | C40—C41 | 1.514 (5) |
C7—C9 | 1.538 (5) | C40—C43 | 1.525 (5) |
C8—H8A | 0.9800 | C40—C42 | 1.532 (5) |
C8—H8B | 0.9800 | C41—H41A | 0.9800 |
C8—H8C | 0.9800 | C41—H41B | 0.9800 |
C9—H9A | 0.9800 | C41—H41C | 0.9800 |
C9—H9B | 0.9800 | C42—H42A | 0.9800 |
C9—H9C | 0.9800 | C42—H42B | 0.9800 |
C10—H10A | 0.9800 | C42—H42C | 0.9800 |
C10—H10B | 0.9800 | C43—H43A | 0.9800 |
C10—H10C | 0.9800 | C43—H43B | 0.9800 |
C11—C13 | 1.517 (4) | C43—H43C | 0.9800 |
C11—H11A | 0.9900 | C44—H44A | 0.9900 |
C11—H11B | 0.9900 | C44—H44B | 0.9900 |
C12—C13 | 1.390 (4) | N1—C45 | 1.131 (4) |
C12—C17 | 1.399 (4) | C45—C46 | 1.458 (5) |
C13—C14 | 1.399 (4) | C46—H46A | 0.9800 |
C14—C15 | 1.392 (4) | C46—H46B | 0.9800 |
C14—H14 | 0.9500 | C46—H46C | 0.9800 |
C15—C16 | 1.399 (4) | N2—C47 | 1.136 (4) |
C15—C18 | 1.531 (4) | C47—C48 | 1.460 (5) |
C16—C17 | 1.387 (4) | C48—H48A | 0.9800 |
C16—H16 | 0.9500 | C48—H48B | 0.9800 |
C17—C22 | 1.518 (4) | C48—H48C | 0.9800 |
C18—C19 | 1.529 (5) | N3—C49 | 1.139 (5) |
C18—C20 | 1.532 (5) | C49—C50 | 1.458 (6) |
C18—C21 | 1.534 (5) | C50—H50A | 0.9800 |
C19—H19A | 0.9800 | C50—H50B | 0.9800 |
C19—H19B | 0.9800 | C50—H50C | 0.9800 |
C19—H19C | 0.9800 | N4—C51 | 1.137 (6) |
C20—H20A | 0.9800 | C51—C52 | 1.451 (6) |
C20—H20B | 0.9800 | C52—H52A | 0.9800 |
C20—H20C | 0.9800 | C52—H52B | 0.9800 |
C21—H21A | 0.9800 | C52—H52C | 0.9800 |
C21—H21B | 0.9800 | N5—C53 | 1.137 (5) |
C21—H21C | 0.9800 | C53—C54 | 1.449 (6) |
C22—C24 | 1.523 (4) | C54—H54A | 0.9800 |
C22—H22A | 0.9900 | C54—H54B | 0.9800 |
C22—H22B | 0.9900 | C54—H54C | 0.9800 |
C23—C24 | 1.413 (5) | N6—C55 | 1.125 (5) |
C23—C28 | 1.419 (5) | C55—C56 | 1.450 (6) |
C23—Li2i | 2.515 (7) | C56—H56A | 0.9800 |
C24—C25 | 1.403 (5) | C56—H56B | 0.9800 |
C25—C26 | 1.396 (5) | C56—H56C | 0.9800 |
C25—H25 | 0.9500 | | |
| | | |
O1—Li2—O3i | 99.6 (3) | C26—C25—C24 | 123.2 (3) |
O2—Li1—O3 | 104.6 (3) | C26—C25—H25 | 118.4 |
O2—Li1—O3i | 101.4 (3) | C24—C25—H25 | 118.4 |
O2—Li1—O4i | 141.2 (4) | C25—C26—C27 | 115.3 (3) |
O3—Li1—O3i | 107.3 (3) | C25—C26—C29 | 120.8 (3) |
O3—Li1—O4i | 99.9 (3) | C27—C26—C29 | 123.8 (3) |
O3i—Li1—O4i | 99.4 (3) | C28—C27—C26 | 123.7 (3) |
N1—Li2—O1 | 105.4 (3) | C28—C27—H27 | 118.1 |
N1—Li2—O3i | 115.6 (3) | C26—C27—H27 | 118.1 |
N2—Li2—O1 | 114.1 (3) | C27—C28—C23 | 120.1 (3) |
N2—Li2—O3i | 116.5 (3) | C27—C28—C33 | 117.4 (3) |
N1—Li2—N2 | 105.4 (3) | C23—C28—C33 | 122.5 (3) |
O4i—Li1—H2 | 158.3 (10) | C32—C29—C26 | 112.7 (3) |
O2—Li1—H2 | 22.1 (9) | C32—C29—C30 | 107.6 (3) |
O3—Li1—H2 | 100.2 (9) | C26—C29—C30 | 110.4 (3) |
O3i—Li1—H2 | 82.3 (10) | C32—C29—C31 | 107.4 (3) |
C1—O1—Li2 | 136.7 (3) | C26—C29—C31 | 110.8 (3) |
C12—O2—Li1 | 142.0 (3) | C30—C29—C31 | 107.8 (3) |
C12—O2—H2 | 114 (3) | C29—C30—H30A | 109.5 |
Li1—O2—H2 | 97 (3) | C29—C30—H30B | 109.5 |
C23—O3—Li2i | 95.8 (3) | H30A—C30—H30B | 109.5 |
C23—O3—Li1 | 128.2 (3) | C29—C30—H30C | 109.5 |
Li2i—O3—Li1 | 115.4 (3) | H30A—C30—H30C | 109.5 |
C23—O3—Li1i | 128.1 (3) | H30B—C30—H30C | 109.5 |
Li2i—O3—Li1i | 118.4 (3) | C29—C31—H31A | 109.5 |
Li1—O3—Li1i | 72.7 (3) | C29—C31—H31B | 109.5 |
C34—O4—Li1i | 140.7 (3) | H31A—C31—H31B | 109.5 |
C34—O4—H4 | 110 (2) | C29—C31—H31C | 109.5 |
Li1i—O4—H4 | 108 (2) | H31A—C31—H31C | 109.5 |
O1—C1—C2 | 120.6 (3) | H31B—C31—H31C | 109.5 |
O1—C1—C6 | 120.3 (3) | C29—C32—H32A | 109.5 |
C2—C1—C6 | 119.1 (3) | C29—C32—H32B | 109.5 |
C3—C2—C1 | 119.5 (3) | H32A—C32—H32B | 109.5 |
C3—C2—C44 | 119.9 (3) | C29—C32—H32C | 109.5 |
C1—C2—C44 | 120.6 (3) | H32A—C32—H32C | 109.5 |
C2—C3—C4 | 123.0 (3) | H32B—C32—H32C | 109.5 |
C2—C3—H3 | 118.5 | C35—C33—C28 | 111.2 (3) |
C4—C3—H3 | 118.5 | C35—C33—H33A | 109.4 |
C5—C4—C3 | 115.9 (3) | C28—C33—H33A | 109.4 |
C5—C4—C7 | 123.7 (3) | C35—C33—H33B | 109.4 |
C3—C4—C7 | 120.3 (3) | C28—C33—H33B | 109.4 |
C6—C5—C4 | 123.2 (3) | H33A—C33—H33B | 108.0 |
C6—C5—H5 | 118.4 | O4—C34—C39 | 121.0 (3) |
C4—C5—H5 | 118.4 | O4—C34—C35 | 117.6 (3) |
C5—C6—C1 | 119.2 (3) | C39—C34—C35 | 121.3 (3) |
C5—C6—C11 | 119.7 (3) | C36—C35—C34 | 117.7 (3) |
C1—C6—C11 | 121.1 (3) | C36—C35—C33 | 121.7 (3) |
C8—C7—C4 | 112.0 (3) | C34—C35—C33 | 120.6 (3) |
C8—C7—C10 | 108.2 (3) | C37—C36—C35 | 123.0 (3) |
C4—C7—C10 | 109.9 (3) | C37—C36—H36 | 118.5 |
C8—C7—C9 | 108.1 (3) | C35—C36—H36 | 118.5 |
C4—C7—C9 | 108.7 (3) | C36—C37—C38 | 116.7 (3) |
C10—C7—C9 | 109.9 (3) | C36—C37—C40 | 123.1 (3) |
C7—C8—H8A | 109.5 | C38—C37—C40 | 120.1 (3) |
C7—C8—H8B | 109.5 | C39—C38—C37 | 122.8 (3) |
H8A—C8—H8B | 109.5 | C39—C38—H38 | 118.6 |
C7—C8—H8C | 109.5 | C37—C38—H38 | 118.6 |
H8A—C8—H8C | 109.5 | C38—C39—C34 | 118.4 (3) |
H8B—C8—H8C | 109.5 | C38—C39—C44 | 120.1 (3) |
C7—C9—H9A | 109.5 | C34—C39—C44 | 121.4 (3) |
C7—C9—H9B | 109.5 | C41—C40—C43 | 108.5 (3) |
H9A—C9—H9B | 109.5 | C41—C40—C42 | 108.7 (3) |
C7—C9—H9C | 109.5 | C43—C40—C42 | 108.9 (3) |
H9A—C9—H9C | 109.5 | C41—C40—C37 | 112.5 (3) |
H9B—C9—H9C | 109.5 | C43—C40—C37 | 110.3 (3) |
C7—C10—H10A | 109.5 | C42—C40—C37 | 107.9 (3) |
C7—C10—H10B | 109.5 | C40—C41—H41A | 109.5 |
H10A—C10—H10B | 109.5 | C40—C41—H41B | 109.5 |
C7—C10—H10C | 109.5 | H41A—C41—H41B | 109.5 |
H10A—C10—H10C | 109.5 | C40—C41—H41C | 109.5 |
H10B—C10—H10C | 109.5 | H41A—C41—H41C | 109.5 |
C6—C11—C13 | 113.3 (3) | H41B—C41—H41C | 109.5 |
C6—C11—H11A | 108.9 | C40—C42—H42A | 109.5 |
C13—C11—H11A | 108.9 | C40—C42—H42B | 109.5 |
C6—C11—H11B | 108.9 | H42A—C42—H42B | 109.5 |
C13—C11—H11B | 108.9 | C40—C42—H42C | 109.5 |
H11A—C11—H11B | 107.7 | H42A—C42—H42C | 109.5 |
O2—C12—C13 | 120.7 (3) | H42B—C42—H42C | 109.5 |
O2—C12—C17 | 118.2 (3) | C40—C43—H43A | 109.5 |
C13—C12—C17 | 121.1 (3) | C40—C43—H43B | 109.5 |
C12—C13—C14 | 118.5 (3) | H43A—C43—H43B | 109.5 |
C12—C13—C11 | 121.6 (3) | C40—C43—H43C | 109.5 |
C14—C13—C11 | 119.9 (3) | H43A—C43—H43C | 109.5 |
C15—C14—C13 | 122.8 (3) | H43B—C43—H43C | 109.5 |
C15—C14—H14 | 118.6 | C39—C44—C2 | 114.1 (3) |
C13—C14—H14 | 118.6 | C39—C44—H44A | 108.7 |
C14—C15—C16 | 116.3 (3) | C2—C44—H44A | 108.7 |
C14—C15—C18 | 123.6 (3) | C39—C44—H44B | 108.7 |
C16—C15—C18 | 120.1 (3) | C2—C44—H44B | 108.7 |
C17—C16—C15 | 123.4 (3) | H44A—C44—H44B | 107.6 |
C17—C16—H16 | 118.3 | C45—N1—Li2 | 166.6 (3) |
C15—C16—H16 | 118.3 | N1—C45—C46 | 178.5 (4) |
C16—C17—C12 | 118.0 (3) | C45—C46—H46A | 109.5 |
C16—C17—C22 | 119.8 (3) | C45—C46—H46B | 109.5 |
C12—C17—C22 | 122.0 (3) | H46A—C46—H46B | 109.5 |
C19—C18—C15 | 112.3 (3) | C45—C46—H46C | 109.5 |
C19—C18—C20 | 108.8 (3) | H46A—C46—H46C | 109.5 |
C15—C18—C20 | 107.8 (3) | H46B—C46—H46C | 109.5 |
C19—C18—C21 | 108.4 (3) | C47—N2—Li2 | 167.6 (3) |
C15—C18—C21 | 110.8 (3) | N2—C47—C48 | 178.7 (4) |
C20—C18—C21 | 108.6 (3) | C47—C48—H48A | 109.5 |
C18—C19—H19A | 109.5 | C47—C48—H48B | 109.5 |
C18—C19—H19B | 109.5 | H48A—C48—H48B | 109.5 |
H19A—C19—H19B | 109.5 | C47—C48—H48C | 109.5 |
C18—C19—H19C | 109.5 | H48A—C48—H48C | 109.5 |
H19A—C19—H19C | 109.5 | H48B—C48—H48C | 109.5 |
H19B—C19—H19C | 109.5 | N3—C49—C50 | 179.6 (5) |
C18—C20—H20A | 109.5 | C49—C50—H50A | 109.5 |
C18—C20—H20B | 109.5 | C49—C50—H50B | 109.5 |
H20A—C20—H20B | 109.5 | H50A—C50—H50B | 109.5 |
C18—C20—H20C | 109.5 | C49—C50—H50C | 109.5 |
H20A—C20—H20C | 109.5 | H50A—C50—H50C | 109.5 |
H20B—C20—H20C | 109.5 | H50B—C50—H50C | 109.5 |
C18—C21—H21A | 109.5 | N4—C51—C52 | 179.5 (5) |
C18—C21—H21B | 109.5 | C51—C52—H52A | 109.5 |
H21A—C21—H21B | 109.5 | C51—C52—H52B | 109.5 |
C18—C21—H21C | 109.5 | H52A—C52—H52B | 109.5 |
H21A—C21—H21C | 109.5 | C51—C52—H52C | 109.5 |
H21B—C21—H21C | 109.5 | H52A—C52—H52C | 109.5 |
C17—C22—C24 | 110.1 (3) | H52B—C52—H52C | 109.5 |
C17—C22—H22A | 109.6 | N5—C53—C54 | 178.2 (6) |
C24—C22—H22A | 109.6 | C53—C54—H54A | 109.5 |
C17—C22—H22B | 109.6 | C53—C54—H54B | 109.5 |
C24—C22—H22B | 109.6 | H54A—C54—H54B | 109.5 |
H22A—C22—H22B | 108.2 | C53—C54—H54C | 109.5 |
O3—C23—C24 | 121.5 (3) | H54A—C54—H54C | 109.5 |
O3—C23—C28 | 121.3 (3) | H54B—C54—H54C | 109.5 |
C24—C23—C28 | 117.1 (3) | N6—C55—C56 | 179.3 (5) |
O3—C23—Li2i | 52.1 (2) | C55—C56—H56A | 109.5 |
C24—C23—Li2i | 106.0 (2) | C55—C56—H56B | 109.5 |
C28—C23—Li2i | 109.7 (3) | H56A—C56—H56B | 109.5 |
C25—C24—C23 | 120.3 (3) | C55—C56—H56C | 109.5 |
C25—C24—C22 | 117.3 (3) | H56A—C56—H56C | 109.5 |
C23—C24—C22 | 122.4 (3) | H56B—C56—H56C | 109.5 |
| | | |
O3i—Li2—O1—C1 | −178.4 (3) | Li2i—O3—C23—C28 | −91.5 (3) |
N1—Li2—O1—C1 | 61.6 (5) | Li1—O3—C23—C28 | 139.7 (3) |
N2—Li2—O1—C1 | −53.6 (5) | Li1i—O3—C23—C28 | 41.8 (5) |
O4i—Li1—O2—C12 | −64.1 (8) | Li1—O3—C23—Li2i | −128.9 (4) |
O3—Li1—O2—C12 | 63.2 (5) | Li1i—O3—C23—Li2i | 133.3 (4) |
O3i—Li1—O2—C12 | 174.7 (3) | O3—C23—C24—C25 | −172.0 (3) |
O4i—Li1—O3—C23 | 131.5 (3) | C28—C23—C24—C25 | 5.6 (5) |
O2—Li1—O3—C23 | −18.1 (5) | Li2i—C23—C24—C25 | −117.0 (3) |
O3i—Li1—O3—C23 | −125.2 (3) | O3—C23—C24—C22 | 9.7 (5) |
O4i—Li1—O3—Li2i | 10.6 (4) | C28—C23—C24—C22 | −172.6 (3) |
O2—Li1—O3—Li2i | −139.0 (3) | Li2i—C23—C24—C22 | 64.7 (4) |
O3i—Li1—O3—Li2i | 113.8 (3) | C17—C22—C24—C25 | −74.7 (4) |
O4i—Li1—O3—Li1i | −103.2 (4) | C17—C22—C24—C23 | 103.7 (4) |
O2—Li1—O3—Li1i | 107.2 (4) | C23—C24—C25—C26 | −2.2 (5) |
O3i—Li1—O3—Li1i | 0.000 (2) | C22—C24—C25—C26 | 176.2 (3) |
Li2—O1—C1—C2 | 84.7 (4) | C24—C25—C26—C27 | −1.7 (5) |
Li2—O1—C1—C6 | −97.1 (4) | C24—C25—C26—C29 | −179.4 (3) |
O1—C1—C2—C3 | 176.4 (3) | C25—C26—C27—C28 | 2.0 (5) |
C6—C1—C2—C3 | −1.8 (5) | C29—C26—C27—C28 | 179.6 (3) |
O1—C1—C2—C44 | −2.7 (5) | C26—C27—C28—C23 | 1.6 (5) |
C6—C1—C2—C44 | 179.0 (3) | C26—C27—C28—C33 | −176.4 (3) |
C1—C2—C3—C4 | 0.5 (5) | O3—C23—C28—C27 | 172.3 (3) |
C44—C2—C3—C4 | 179.6 (3) | C24—C23—C28—C27 | −5.4 (5) |
C2—C3—C4—C5 | 1.0 (5) | Li2i—C23—C28—C27 | 115.3 (3) |
C2—C3—C4—C7 | −180.0 (3) | O3—C23—C28—C33 | −9.8 (5) |
C3—C4—C5—C6 | −1.1 (5) | C24—C23—C28—C33 | 172.5 (3) |
C7—C4—C5—C6 | 179.9 (3) | Li2i—C23—C28—C33 | −66.7 (4) |
C4—C5—C6—C1 | −0.2 (5) | C25—C26—C29—C32 | −176.0 (3) |
C4—C5—C6—C11 | −177.4 (3) | C27—C26—C29—C32 | 6.5 (5) |
O1—C1—C6—C5 | −176.6 (3) | C25—C26—C29—C30 | 63.7 (4) |
C2—C1—C6—C5 | 1.7 (5) | C27—C26—C29—C30 | −113.8 (4) |
O1—C1—C6—C11 | 0.6 (5) | C25—C26—C29—C31 | −55.6 (4) |
C2—C1—C6—C11 | 178.9 (3) | C27—C26—C29—C31 | 126.9 (4) |
C5—C4—C7—C8 | −0.7 (5) | C27—C28—C33—C35 | 74.1 (4) |
C3—C4—C7—C8 | −179.7 (3) | C23—C28—C33—C35 | −103.9 (4) |
C5—C4—C7—C10 | −121.1 (3) | Li1i—O4—C34—C39 | −156.2 (4) |
C3—C4—C7—C10 | 60.0 (4) | Li1i—O4—C34—C35 | 22.3 (6) |
C5—C4—C7—C9 | 118.7 (4) | O4—C34—C35—C36 | −176.0 (3) |
C3—C4—C7—C9 | −60.3 (4) | C39—C34—C35—C36 | 2.5 (5) |
C5—C6—C11—C13 | 90.3 (4) | O4—C34—C35—C33 | 5.6 (5) |
C1—C6—C11—C13 | −86.9 (4) | C39—C34—C35—C33 | −175.9 (3) |
Li1—O2—C12—C13 | 172.6 (4) | C28—C33—C35—C36 | −100.8 (4) |
Li1—O2—C12—C17 | −8.1 (6) | C28—C33—C35—C34 | 77.6 (4) |
O2—C12—C13—C14 | −179.9 (3) | C34—C35—C36—C37 | −0.9 (5) |
C17—C12—C13—C14 | 0.9 (5) | C33—C35—C36—C37 | 177.5 (3) |
O2—C12—C13—C11 | 2.4 (5) | C35—C36—C37—C38 | −0.7 (5) |
C17—C12—C13—C11 | −176.9 (3) | C35—C36—C37—C40 | 176.8 (3) |
C6—C11—C13—C12 | 86.9 (4) | C36—C37—C38—C39 | 0.6 (5) |
C6—C11—C13—C14 | −90.8 (4) | C40—C37—C38—C39 | −176.9 (3) |
C12—C13—C14—C15 | 0.2 (5) | C37—C38—C39—C34 | 1.0 (5) |
C11—C13—C14—C15 | 178.0 (3) | C37—C38—C39—C44 | 179.5 (3) |
C13—C14—C15—C16 | 0.6 (5) | O4—C34—C39—C38 | 175.8 (3) |
C13—C14—C15—C18 | −177.2 (3) | C35—C34—C39—C38 | −2.6 (5) |
C14—C15—C16—C17 | −2.5 (5) | O4—C34—C39—C44 | −2.6 (5) |
C18—C15—C16—C17 | 175.4 (3) | C35—C34—C39—C44 | 178.9 (3) |
C15—C16—C17—C12 | 3.5 (5) | C36—C37—C40—C41 | 9.8 (5) |
C15—C16—C17—C22 | −172.3 (3) | C38—C37—C40—C41 | −172.8 (3) |
O2—C12—C17—C16 | 178.1 (3) | C36—C37—C40—C43 | 131.1 (4) |
C13—C12—C17—C16 | −2.6 (5) | C38—C37—C40—C43 | −51.4 (4) |
O2—C12—C17—C22 | −6.2 (5) | C36—C37—C40—C42 | −110.0 (4) |
C13—C12—C17—C22 | 173.0 (3) | C38—C37—C40—C42 | 67.4 (4) |
C14—C15—C18—C19 | −7.8 (5) | C38—C39—C44—C2 | 98.5 (4) |
C16—C15—C18—C19 | 174.5 (3) | C34—C39—C44—C2 | −83.1 (4) |
C14—C15—C18—C20 | 112.0 (4) | C3—C2—C44—C39 | −89.6 (4) |
C16—C15—C18—C20 | −65.7 (4) | C1—C2—C44—C39 | 89.5 (4) |
C14—C15—C18—C21 | −129.2 (3) | O1—Li2—N1—C45 | 65.7 (16) |
C16—C15—C18—C21 | 53.1 (4) | O3i—Li2—N1—C45 | −43.1 (16) |
C16—C17—C22—C24 | 93.7 (4) | N2—Li2—N1—C45 | −173.3 (14) |
C12—C17—C22—C24 | −81.8 (4) | O1—Li2—N2—C47 | −144.7 (14) |
Li2i—O3—C23—C24 | 86.1 (3) | O3i—Li2—N2—C47 | −29.4 (17) |
Li1—O3—C23—C24 | −42.8 (5) | N1—Li2—N2—C47 | 100.2 (15) |
Li1i—O3—C23—C24 | −140.6 (3) | | |
Symmetry code: (i) −x+2, −y+1, −z+2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1 | 0.82 (3) | 1.74 (3) | 2.554 (3) | 171 (4) |
O4—H4···O1 | 0.93 (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 |
Mr | 1501.91 | 1814.16 |
Crystal system, space group | Monoclinic, P21/n | Triclinic, P1 |
Temperature (K) | 150 | 150 |
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), 90 | 106.035 (2), 94.097 (2), 115.286 (2) |
V (Å3) | 4496.4 (7) | 2687.4 (5) |
Z | 2 | 1 |
Radiation type | Synchrotron, λ = 0.6911 Å | Synchrotron, λ = 0.8466 Å |
µ (mm−1) | 0.07 | 0.07 |
Crystal size (mm) | 0.24 × 0.06 × 0.05 | 0.15 × 0.14 × 0.07 |
|
Data collection |
Diffractometer | Bruker APEX II CCD diffractometer | Bruker APEX II CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Version 2004/1; Sheldrick, 2004) | Multi-scan (SADABS; Version 2.10; Sheldrick, 2003) |
Tmin, Tmax | 0.984, 0.997 | 0.990, 0.995 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 29080, 8536, 5918 | 15630, 7870, 4532 |
Rint | 0.063 | 0.052 |
θmax (°) | 25.0 | 28.4 |
(sin θ/λ)max (Å−1) | 0.612 | 0.562 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.074, 0.226, 1.03 | 0.065, 0.172, 1.00 |
No. of reflections | 8536 | 7870 |
No. of parameters | 561 | 638 |
No. of restraints | 172 | 0 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.75, −0.37 | 0.25, −0.24 |
Selected geometric parameters (Å, º) for (I) topLi1—O1 | 1.987 (5) | Li1—O3 | 1.981 (5) |
Li1—O2 | 1.853 (5) | Li1—O4i | 1.866 (5) |
| | | |
O1—Li1—O2 | 105.5 (2) | O2—Li1—O3 | 107.8 (2) |
O1—Li1—O3 | 112.6 (2) | O2—Li1—O4i | 127.6 (3) |
O1—Li1—O4i | 102.4 (2) | O3—Li1—O4i | 100.9 (2) |
Symmetry code: (i) −x, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O4 | 1.00 (4) | 1.59 (4) | 2.568 (3) | 165 (3) |
O3—H3···O4 | 0.89 (4) | 1.68 (4) | 2.541 (3) | 162 (3) |
Selected geometric parameters (Å, º) for (II) topLi1—O2 | 1.919 (7) | Li2—O1 | 1.888 (6) |
Li1—O3 | 1.996 (7) | Li2—O3i | 1.996 (6) |
Li1—O3i | 1.996 (7) | Li2—N1 | 2.082 (7) |
Li1—O4i | 1.912 (7) | Li2—N2 | 2.087 (6) |
| | | |
O1—Li2—O3i | 99.6 (3) | O3i—Li1—O4i | 99.4 (3) |
O2—Li1—O3 | 104.6 (3) | N1—Li2—O1 | 105.4 (3) |
O2—Li1—O3i | 101.4 (3) | N1—Li2—O3i | 115.6 (3) |
O2—Li1—O4i | 141.2 (4) | N2—Li2—O1 | 114.1 (3) |
O3—Li1—O3i | 107.3 (3) | N2—Li2—O3i | 116.5 (3) |
O3—Li1—O4i | 99.9 (3) | N1—Li2—N2 | 105.4 (3) |
Symmetry code: (i) −x+2, −y+1, −z+2. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1 | 0.82 (3) | 1.74 (3) | 2.554 (3) | 171 (4) |
O4—H4···O1 | 0.93 (4) | 1.61 (4) | 2.525 (3) | 171 (3) |
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.