Lithium borodilactate

metal-organic papers

m212

Structure Reports

Online ISSN 1600-5368

Lithium borodilactate

S. Dhanuskodi, P. A. Angeli Mary, S. Thamotharan and V. Parthasarathi*

Department of Physics, Bharathidasan University, Tiruchirappalli 620 024, India

Correspondence e-mail: [email protected]

Key indicators

Single-crystal X-ray study T= 293 K

Mean(C±C) = 0.004 AÊ Rfactor = 0.028 wRfactor = 0.079 Data-to-parameter ratio = 6.4

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2002 International Union of Crystallography Printed in Great Britain ± all rights reserved

The asymmetric unit of the title compound, Li+_C

6H8BO6ÿ,

consists of two lithium borodilactate moieties. Li+_{cations are}

tetracoordinated by O atoms of the borodilactate anions. The LiÐO distances range from 1.907 (5) to 2.050 (5) AÊ. The trivalent boron is tetrahedrally coordinated by four O atoms of the borodilactate moieties. Boron makes two short and two long covalent bonds with O atoms, and the distances range from 1.430 (3) to 1.507 (3) AÊ. This compound exhibits non-linear optical properties, combined with good chemical stability.

Comment

The present work is part of a study aimed at developing potential semiorganic NLO (non-linear optical) materials for optoelectronic applications, such as optical computing, optical data storage and optical communication. In a previous communication (Angeli Maryet al., 2002), the crystal structure of ammonium borodilactate, an NLO material, has been reported.

The title compound, (I), crystallizes in the noncentrosym-metric space group P21 with Z = 4. The asymmetric unit

consists of two borodilactate moieties linked through two Li+

cations. The LiÐO distances range from 1.907 (5) to 2.050 (5) AÊ. In this structure, both lithium cations are tetra-coordinated by four O atoms of the borodilactate anions. The Li+ _{cations and borodilactate anions form a polymeric}

network. Similar arrangements have been reported in the literature (He et al., 2001). The lithium tetrahedra are distorted, with the bond angles ranging from 100 to 124_{. In} both anions, boron forms two short and two long covalent bonds with O atoms. The bond angles around boron range from 104 to 114_{, indicating a distorted tetrahedral} environ-ment. Similar bond lengths and deviations from tetrahedral values of bond angles around boron have been reported (Stibrany & Brant, 2001; Hill et al., 1997) in related boron

derivatives. A short intermolecular CÐH O contact is observed between C16 and O12, with an H16B O12 distance of 2.45 AÊ. The crystal structure is additionally stabilized by van der Waals interactions.

Experimental

The title compound was prepared by mixing 1.847 g (0.025M) of lithium carbonate, 3.09 g (0.05M) of boric acid and 9.08 g (0.1M) of racemic lactic acid. The components were thoroughly dissolved in 100 ml of distilled water and the solution was evaporated to dryness by heating at 323 K for 8 h. The yield was around 60%. Single crystals were obtained by slow evaporation of a saturated aqueous solution at 298 K. Crystals of size up to 543 mm were obtained in 15±20 d. The UV±Vis spectrum of a crystal was recorded using a Varian Cary 5E UV±Vis±NIR spectrophotometer. The crystal has a transmittance window in the range 240±1250 nm. The optical second harmonic generation of this crystal has been tested with the Kurtz powder technique, using a Q-switched Nd±YAG laser (1064 nm, pulse width 8 ns). Green radiation (532 nm) was observed, which con®rms the second-order NLO activity.

Crystal data

Li+_C 6H8BO6ÿ

Mr= 193.88

Monoclinic,P21

a= 6.7089 (16) AÊ

b= 12.0650 (15) AÊ

c= 11.0782 (16) AÊ

= 97.472 (17)

V= 889.1 (3) AÊ3

Z= 4

Dx= 1.448 Mg mÿ3 Dm= 1.40 Mg mÿ3

Dmmeasured by ¯otation in

bromoform and glacial acetic acid MoKradiation

Cell parameters from 25 re¯ections

= 20±30 = 0.13 mmÿ1

T= 293 (2) K Prism, white

0.230.150.10 mm

Data collection

Enraf±Nonius CAD-4 diffractometer

!±2scans

Absorption correction: scan (Northet al., 1968)

Tmin= 0.972,Tmax= 0.988 1801 measured re¯ections 1655 independent re¯ections 1496 re¯ections withI> 2(I)

Rint= 0.020

max= 25.0

h= 0!7

k=ÿ14!14

l=ÿ13!13 2 standard re¯ections

frequency: 100 min intensity decay: none

Re®nement

Re®nement onF2

R[F2_{> 2(F}2_{)] = 0.028}

wR(F2_{) = 0.079}

S= 0.99 1655 re¯ections 258 parameters

H-atom parameters constrained

w= 1/[2_(F

o2) + (0.0558P)2

+ 0.114P]

whereP= (Fo2+ 2Fc2)/3

(/)max< 0.001

max= 0.18 e AÊÿ3

min=ÿ0.19 e AÊÿ3

Extinction correction:SHELXL97 Extinction coef®cient: 0.021 (4)

Table 1

Selected geometric parameters (AÊ,_).

Li1ÐO16 1.907 (5) Li1ÐO15i _{1.979 (5)} Li1ÐO13ii _{1.997 (4)} Li1ÐO25 2.050 (5) B1ÐO11 1.430 (3) B1ÐO15 1.443 (4) B1ÐO12 1.495 (4) B1ÐO14 1.507 (3)

Li2ÐO26 1.910 (5) Li2ÐO23iii _{1.948 (5)} Li2ÐO11iii _{1.960 (5)} Li2ÐO21iv _{1.969 (5)} B2ÐO21 1.443 (4) B2ÐO25 1.450 (3) B2ÐO22 1.486 (3) B2ÐO24 1.506 (3)

O16ÐLi1ÐO13ii _{105.3 (2)} O15i_ÐLi1ÐO13ii _{100.4 (2)} O16ÐLi1ÐO25 105.9 (2) O13ii_{ÐLi1ÐO25 123.9 (2)} O11ÐB1ÐO12 104.7 (2) O15ÐB1ÐO12 112.7 (2) O11ÐB1ÐO14 113.0 (2) O15ÐB1ÐO14 104.0 (2)

O26ÐLi2ÐO23iii _{112.3 (2)} O23iii_ÐLi2ÐO11iii _{107.4 (2)} O26ÐLi2ÐO21iv _{104.9 (2)} O11iii_ÐLi2ÐO21iv _{111.7 (2)} O21ÐB2ÐO22 104.8 (2) O25ÐB2ÐO22 113.6 (2) O21ÐB2ÐO24 111.9 (2) O25ÐB2ÐO24 104.7 (2)

Symmetry codes: (i) xÿ1;y;z; (ii) ÿx;1

2‡y;ÿz; (iii) ÿx;12‡y;1ÿz; (iv)

ÿ1ÿx;1 2‡y;1ÿz.

All H atoms were ®xed geometrically and made to ride on their parent atoms. There are four chiral C atoms (C12, C15, C22 and C25) in the two dilactate moieties. The absolute con®guration of the lactate anions could not be established unambiguously in the present study, because the structure contains only light atoms (Flack, 1983). However, the reported coordinates correspond, arbitrarily, to anR con®guration in every case.

Data collection: CAD-4 EXPRESS (Enraf±Nonius, 1994); cell re®nement:CAD-4EXPRESS; data reduction:MolEN(Fair, 1990);

Acta Cryst.(2002). E58, m212±m214 S. Dhanuskodiet al. Li+C₆H₈BO₆ÿ

m213

metal-organic papers

Figure 1

The molecular structure of (I), showing 50% probability displacement

metal-organic papers

m214

program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to re®ne structure:SHELXL97 (Sheldrick, 1997); molecular graphics:PLATON(Spek, 2001); software used to prepare material for publication:SHELXL97.

The authors thank Professors R. Jeyaraman and K. Panchanatheeswaran, Department of Chemistry, Bhar-athidasan University, Tiruchirapalli, for fruitful discussions, and also Professor V. Balasubramaniyan, MGV's Pharmacy College, Nashik, for his kind help in the synthesis of the title compound. One of the authors (PAAM) is grateful to the University Grants Commission, New Delhi, for the award of a Teacher Fellowship during the IX plan period.

References

Angeli Mary, P. A., Dhanuskodi, S., Thamotharan, S. & Parthasarathi, V. (2002).Acta Cryst.E58, o45±o47.

Enraf±Nonius (1994). CAD-4 EXPRESS. Version 5.1/1.2. Enraf±Nonius, Delft, The Netherlands.

Fair, C. K. (1990).MolEN.Enraf±Nonius, Delft, The Netherlands. Flack, H. D. (1983).Acta Cryst.A39, 876±881.

He, M., Li, H., Chen, X.-L., Xu, Y.-P. & Xu, T. (2001),Acta Cryst.C57, 1010± 1011.

Hill, G. S., Manojlovic Muir, L., Muir, K. W. & Puddephatt, R. J. (1997).

Organometallics,16, 525±530.

North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968).Acta Cryst.A24, 351± 359.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of GoÈttingen, Germany.

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Acta Cryst. (2002). E58, m212–m214

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Acta Cryst. (2002). E58, m212–m214 [doi:10.1107/S1600536802006773]

Lithium borodilactate

S. Dhanuskodi, P. A. Angeli Mary, S. Thamotharan and V. Parthasarathi

S1. Comment

The present work is part of a study aimed at developing potential semiorganic NLO (non-linear optical) materials for

optoelectronic applications, such as optical computing, optical data storage and optical communication. In a previous

communication (Angeli Mary et al., 2002), the crystal structure of ammonium borodilactate, an NLO material, has been

reported. The title compound, (I), crystallizes in the noncentrosymmetric space group P21 with Z = 4. The asymmetric

unit consists of two borodilactate moieties linked through two Li+ _{cations. The Li—O distances range from 1.907 (5) to}

2.049 (5) Å. In this structure, both lithium cations are tetracoordinated by four O atoms of the borodilactate anions. The

Li+ _{cations and borodilactate anions form a ploymeric network. Similar arrangements have been reported in the literature}

(He et al., 2001). The lithium tetrahedra are slightly distorted, with the bond angles ranging from 105 to 112°. In both

anions, boron forms two short and two long covalent bonds with O atoms. The bond angles around boron range from 104

to 115°, indicating a distorted tetrahedral environment. Similar bond lengths and deviations from tetrahedral values of

bond angles around boron have been reported (Stibrany & Brant, 2001; Hill et al., 1997) in related boron derivatives. A

short intermolecular C—H···O contact is observed between C16 and O12, with an H16B···O12 distance of 2.45 Å. The

crystal structure is additionally stabilized by van der Waals interactions.

S2. Experimental

The title compound was prepared by mixing 1.847 g (0.025 M) of lithium carbonate, 3.09 g (0.05 M) of boric acid and

9.08 g (0.1 M) of racemic lactic acid. The components were thoroughly dissolved in 100 ml of distilled water and the

solution was evaporated to dryness by heating at 323 K for 8 h. The yield was around 60%. Single crystals were obtained

by slow evaporation of a saturated aqueous solution at 298 K. Crystals of size up to 5 × 4 × 3 mm were obtained in 15–20

d. The UV–Vis spectrum of a crystal was recorded using a Varian Cary 5E UV-Vis-NIR spectrophotometer. The crystal

has a transmittance window in the range 240–1250 nm. The optical second harmonic generation of this crystal has been

tested with the Kurtz powder technique, using a Q-switched Nd–YAG laser (1064 nm, pulse width 8 ns). Green radiation

(532 nm) was observed, which confirms the second-order NLO activity.

S3. Refinement

All H atoms were fixed geometrically and made to ride on their parent atoms. There are four chiral C atoms (C12, C15,

C22 and C25) in the two dilactate moieties. The absolute configuration of the lactate anions could not be established

unambiguously in the present study, because the structure contains only light atoms (Flack, 1983). However, the reported

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Acta Cryst. (2002). E58, m212–m214

Figure 1

The molecular structure of (I), showing 50% probability displacement ellipsoids and the atom-numbering scheme.

Figure 2

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Acta Cryst. (2002). E58, m212–m214

Lithium Borodilactate

Crystal data Li+_·C

6H8BO6− Mr = 193.88 Monoclinic, P21 a = 6.7089 (16) Å b = 12.0650 (15) Å c = 11.0782 (16) Å β = 97.472 (17)° V = 889.1 (3) Å3 Z = 4

F(000) = 400

Dx = 1.448 Mg m−3 Dm = 1.40 Mg m−3

Dm measured by flotation in bromoform and

glacial acetic acid

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 25 reflections θ = 20–30°

µ = 0.13 mm−1 T = 293 K Prisma, white

0.23 × 0.15 × 0.10 mm

Data collection Enraf-Nonius CAD-4

diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

ω–2θ scans

Absorption correction: ψ scan (North et al., 1968)

Tmin = 0.972, Tmax = 0.988

1801 measured reflections

1655 independent reflections 1496 reflections with I > 2σ(I) Rint = 0.020

θmax = 25.0°, θmin = 2.5° h = 0→7

k = −14→14 l = −13→13

2 standard reflections every 100 min intensity decay: none

Refinement Refinement on F2

Least-squares matrix: full R[F2 _{> 2σ(F}2_{)] = 0.028} wR(F2_{) = 0.079} S = 0.99 1655 reflections 258 parameters 1 restraint

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrained Calculated w = 1/[σ2_(F

o2) + (0.0558P)2 +

0.114P]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001

Δρmax = 0.18 e Å−3

Δρmin = −0.19 e Å−3

Extinction correction: SHELXL97, Fc*_{=kFc[1+0.001xFc}2_λ3_/sin(2θ)]-1/4

Extinction coefficient: 0.021 (4)

Special details

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 F2 _{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 F2_{. 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 F2

are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

x y z Uiso*/Ueq

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Acta Cryst. (2002). E58, m212–m214

B1 0.2839 (4) −0.1164 (3) 0.1516 (3) 0.0297 (6) O11 0.4128 (3) −0.14247 (15) 0.26104 (15) 0.0316 (4) O12 0.3199 (3) −0.20686 (18) 0.06477 (15) 0.0357 (4) O13 0.4807 (3) −0.36792 (18) 0.07402 (18) 0.0458 (5) O14 0.0641 (3) −0.12026 (17) 0.16668 (16) 0.0362 (5) O15 0.3107 (2) −0.00737 (17) 0.10269 (16) 0.0331 (4) O16 −0.2081 (3) −0.0230 (2) 0.0997 (2) 0.0501 (6) C11 0.4271 (4) −0.2840 (2) 0.1223 (2) 0.0320 (6) C12 0.4737 (4) −0.2559 (2) 0.2562 (2) 0.0334 (6) H12 0.3896 −0.3014 0.3026 0.040* C13 0.6905 (5) −0.2732 (3) 0.3053 (3) 0.0486 (8) H13A 0.7736 −0.2291 0.2597 0.073* H13B 0.7243 −0.3501 0.2982 0.073* H13C 0.7125 −0.2516 0.3894 0.073* C14 −0.0292 (4) −0.0386 (2) 0.1048 (2) 0.0342 (6) C15 0.1189 (4) 0.0293 (2) 0.0436 (2) 0.0369 (6) H15 0.1068 0.0082 −0.0425 0.044* C16 0.0907 (5) 0.1521 (3) 0.0517 (3) 0.0561 (9) H16A 0.1099 0.1744 0.1355 0.084* H16B −0.0428 0.1714 0.0158 0.084* H16C 0.1869 0.1892 0.0088 0.084* Li2 −0.4752 (6) 0.4567 (4) 0.5990 (4) 0.0312 (9) B2 −0.2459 (4) 0.1439 (3) 0.3577 (3) 0.0298 (6) O21 −0.2642 (3) 0.03134 (15) 0.39894 (16) 0.0334 (4) O22 −0.0291 (3) 0.15737 (16) 0.34584 (17) 0.0355 (4) O23 0.2542 (3) 0.06181 (18) 0.39764 (18) 0.0421 (5) O24 −0.2973 (3) 0.22676 (16) 0.45056 (15) 0.0349 (4) O25 −0.3783 (3) 0.17125 (15) 0.24773 (14) 0.0327 (4) O26 −0.5079 (3) 0.36935 (19) 0.45402 (17) 0.0465 (5) C21 0.0722 (4) 0.0708 (2) 0.3926 (2) 0.0296 (6) C22 −0.0696 (4) −0.0112 (2) 0.4400 (2) 0.0353 (6) H22 −0.0539 −0.0839 0.4030 0.042* C23 −0.0298 (5) −0.0215 (3) 0.5771 (3) 0.0544 (9) H23A −0.0554 0.0484 0.6137 0.082* H23B 0.1079 −0.0423 0.6008 0.082* H23C −0.1165 −0.0770 0.6040 0.082* C24 −0.4384 (4) 0.2931 (2) 0.4016 (2) 0.0318 (6) C25 −0.5032 (4) 0.2633 (2) 0.2708 (2) 0.0348 (6) H25 −0.6437 0.2390 0.2616 0.042* C26 −0.4840 (7) 0.3598 (3) 0.1873 (3) 0.0669 (11) H26A −0.3458 0.3825 0.1938 0.100* H26B −0.5644 0.4204 0.2098 0.100* H26C −0.5295 0.3383 0.1049 0.100*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

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Acta Cryst. (2002). E58, m212–m214

B1 0.0263 (14) 0.0320 (15) 0.0315 (13) −0.0004 (12) 0.0061 (11) −0.0013 (12) O11 0.0368 (10) 0.0277 (9) 0.0298 (8) 0.0036 (8) 0.0026 (7) −0.0025 (8) O12 0.0370 (10) 0.0415 (11) 0.0286 (9) 0.0014 (9) 0.0039 (7) −0.0042 (9) O13 0.0520 (13) 0.0405 (12) 0.0457 (11) 0.0052 (10) 0.0091 (9) −0.0127 (10) O14 0.0286 (9) 0.0386 (11) 0.0430 (10) −0.0006 (8) 0.0108 (7) 0.0039 (9) O15 0.0224 (8) 0.0371 (10) 0.0399 (9) 0.0025 (7) 0.0046 (7) 0.0082 (8) O16 0.0254 (10) 0.0550 (14) 0.0700 (13) 0.0051 (9) 0.0070 (9) −0.0088 (11) C11 0.0294 (13) 0.0313 (14) 0.0367 (12) −0.0012 (11) 0.0098 (11) −0.0014 (12) C12 0.0393 (15) 0.0291 (13) 0.0328 (13) 0.0009 (11) 0.0082 (11) 0.0002 (11) C13 0.0518 (19) 0.0457 (17) 0.0456 (15) 0.0113 (15) −0.0039 (13) −0.0028 (14) C14 0.0247 (13) 0.0403 (16) 0.0376 (14) 0.0041 (11) 0.0041 (10) −0.0088 (12) C15 0.0310 (13) 0.0421 (16) 0.0366 (13) 0.0051 (12) 0.0001 (10) 0.0058 (12) C16 0.0425 (17) 0.052 (2) 0.074 (2) 0.0076 (15) 0.0091 (15) 0.0143 (17) Li2 0.028 (2) 0.030 (2) 0.037 (2) −0.0002 (17) 0.0100 (17) −0.0007 (17) B2 0.0266 (14) 0.0316 (16) 0.0324 (14) −0.0042 (11) 0.0082 (11) −0.0019 (12) O21 0.0252 (9) 0.0311 (10) 0.0436 (10) −0.0030 (7) 0.0036 (7) 0.0053 (8) O22 0.0289 (9) 0.0328 (10) 0.0465 (10) −0.0010 (8) 0.0107 (7) 0.0052 (8) O23 0.0259 (10) 0.0436 (12) 0.0587 (12) 0.0031 (8) 0.0127 (8) −0.0029 (10) O24 0.0349 (10) 0.0380 (11) 0.0316 (9) 0.0061 (9) 0.0030 (7) −0.0052 (8) O25 0.0368 (10) 0.0305 (9) 0.0309 (9) 0.0065 (8) 0.0053 (7) −0.0053 (8) O26 0.0548 (12) 0.0463 (13) 0.0395 (10) 0.0139 (10) 0.0109 (9) −0.0126 (10) C21 0.0292 (14) 0.0299 (13) 0.0305 (12) 0.0017 (11) 0.0074 (10) −0.0063 (11) C22 0.0267 (12) 0.0296 (13) 0.0489 (15) −0.0004 (11) 0.0027 (11) 0.0000 (13) C23 0.0351 (15) 0.076 (2) 0.0506 (17) −0.0070 (16) 0.0001 (13) 0.0212 (17) C24 0.0309 (13) 0.0334 (13) 0.0326 (12) 0.0004 (11) 0.0105 (10) −0.0029 (12) C25 0.0366 (14) 0.0357 (15) 0.0321 (13) 0.0085 (12) 0.0047 (11) −0.0028 (11) C26 0.120 (3) 0.0429 (18) 0.0413 (16) 0.025 (2) 0.0232 (18) 0.0075 (15)

Geometric parameters (Å, º)

Li1—O16 1.907 (5) Li2—O26 1.910 (5) Li1—O15i _{1.979 (5) Li2—O23}vi _{1.948 (5)}

Li1—O13ii _{1.997 (4) Li2—O11}vi _{1.960 (5)}

Li1—O25 2.050 (5) Li2—O21vii _{1.969 (5)}

B1—O11 1.430 (3) B2—O21 1.443 (4) B1—O15 1.443 (4) B2—O25 1.450 (3) B1—O12 1.495 (4) B2—O22 1.486 (3) B1—O14 1.507 (3) B2—O24 1.506 (3) O11—C12 1.431 (3) O21—C22 1.421 (3) O11—Li2iii _{1.960 (5) O21—Li2}viii _{1.969 (5)}

O12—C11 1.292 (3) O22—C21 1.315 (3) O13—C11 1.220 (3) O23—C21 1.220 (3) O13—Li1iv _{1.997 (4) O23—Li2}iii _{1.948 (5)}

O14—C14 1.311 (3) O24—C24 1.303 (3) O15—C15 1.436 (3) O25—C25 1.434 (3) O15—Li1v _{1.979 (5) O26—C24 1.213 (3)}

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Acta Cryst. (2002). E58, m212–m214

C12—C13 1.500 (4) C24—C25 1.502 (3) C14—C15 1.514 (4) C25—C26 1.503 (4) C15—C16 1.498 (5)

O16—Li1—O15i _{112.9 (2) O26—Li2—O23}vi _{112.3 (2)}

O16—Li1—O13ii _{105.3 (2) O26—Li2—O11}vi _{108.5 (2)}

O15i_—Li1—O13ii _{100.4 (2) O23}vi_—Li2—O11vi _{107.4 (2)}

O16—Li1—O25 105.9 (2) O26—Li2—O21vii _{104.9 (2)}

O15i_{—Li1—O25 108.6 (2) O23}vi_—Li2—O21vii _{112.1 (2)}

O13ii_{—Li1—O25 123.9 (2) O11}vi_—Li2—O21vii _{111.7 (2)}

O11—B1—O15 115.3 (2) O21—B2—O25 114.4 (2) O11—B1—O12 104.7 (2) O21—B2—O22 104.8 (2) O15—B1—O12 112.7 (2) O25—B2—O22 113.6 (2) O11—B1—O14 113.0 (2) O21—B2—O24 111.9 (2) O15—B1—O14 104.0 (2) O25—B2—O24 104.7 (2) O12—B1—O14 106.9 (2) O22—B2—O24 107.5 (2) B1—O11—C12 108.8 (2) C22—O21—B2 109.2 (2) B1—O11—Li2iii _{125.5 (2) C22—O21—Li2}viii _{127.6 (2)}

C12—O11—Li2iii _{125.5 (2) B2—O21—Li2}viii _{123.1 (2)}

C11—O12—B1 109.58 (19) C21—O22—B2 109.9 (2) C11—O13—Li1iv _{133.5 (2) C21—O23—Li2}iii _{144.5 (2)}

C14—O14—B1 109.0 (2) C24—O24—B2 110.02 (19) C15—O15—B1 107.7 (2) C25—O25—B2 109.57 (19) C15—O15—Li1v _{124.0 (2) C25—O25—Li1 122.95 (19)}

B1—O15—Li1v _{127.8 (2) B2—O25—Li1 125.8 (2)}

C14—O16—Li1 151.4 (3) C24—O26—Li2 144.3 (2) O13—C11—O12 123.9 (2) O23—C21—O22 123.5 (2) O13—C11—C12 125.5 (2) O23—C21—C22 126.6 (2) O12—C11—C12 110.6 (2) O22—C21—C22 109.9 (2) O11—C12—C13 112.8 (2) O21—C22—C23 112.7 (2) O11—C12—C11 103.2 (2) O21—C22—C21 104.2 (2) C13—C12—C11 113.0 (2) C23—C22—C21 111.4 (2) O16—C14—O14 123.0 (3) O26—C24—O24 124.8 (2) O16—C14—C15 126.8 (3) O26—C24—C25 124.2 (2) O14—C14—C15 110.1 (2) O24—C24—C25 111.0 (2) O15—C15—C16 112.9 (3) O25—C25—C24 104.8 (2) O15—C15—C14 103.3 (2) O25—C25—C26 113.0 (2) C16—C15—C14 114.4 (3) C24—C25—C26 111.8 (3)

O15—B1—O11—C12 −141.5 (2) O25—B2—O21—Li2viii _{−42.9 (3)}

O12—B1—O11—C12 −17.0 (3) O22—B2—O21—Li2viii _{−167.9 (2)}

O14—B1—O11—C12 99.1 (2) O24—B2—O21—Li2viii _{75.9 (3)}

O15—B1—O11—Li2iii _{43.7 (3) O21—B2—O22—C21 −9.1 (3)}

O12—B1—O11—Li2iii _{168.2 (2) O25—B2—O22—C21 −134.6 (2)}

O14—B1—O11—Li2iii _{−75.8 (3) O24—B2—O22—C21 110.1 (2)}

supporting information

sup-7

Acta Cryst. (2002). E58, m212–m214

O11—B1—O14—C14 140.9 (2) O21—B2—O25—C25 122.3 (2) O15—B1—O14—C14 15.1 (3) O22—B2—O25—C25 −117.5 (2) O12—B1—O14—C14 −104.3 (2) O24—B2—O25—C25 −0.5 (3) O11—B1—O15—C15 −148.2 (2) O21—B2—O25—Li1 −43.3 (3) O12—B1—O15—C15 91.6 (2) O22—B2—O25—Li1 77.0 (3) O14—B1—O15—C15 −23.8 (2) O24—B2—O25—Li1 −166.0 (2) O11—B1—O15—Li1v _{39.3 (3) O16—Li1—O25—C25 172.9 (2)}

O12—B1—O15—Li1v _{−80.9 (3) O15}i_{—Li1—O25—C25 −65.7 (3)}

O14—B1—O15—Li1v _{163.6 (2) O13}ii_{—Li1—O25—C25 51.5 (3)}

O15i_{—Li1—O16—C14 −173.8 (4) O16—Li1—O25—B2 −23.4 (3)}

O13ii_{—Li1—O16—C14 77.7 (5) O15}i_{—Li1—O25—B2 98.1 (3)}

O25—Li1—O16—C14 −55.1 (6) O13ii_{—Li1—O25—B2 −144.8 (2)}

Li1iv_{—O13—C11—O12 −1.6 (4) O23}vi_{—Li2—O26—C24 74.6 (5)}

Li1iv_{—O13—C11—C12 177.9 (3) O11}vi_{—Li2—O26—C24 −43.9 (5)}

B1—O12—C11—O13 −179.5 (2) O21vii_{—Li2—O26—C24 −163.4 (3)}

B1—O12—C11—C12 1.0 (3) Li2iii_{—O23—C21—O22 −152.2 (3)}

B1—O11—C12—C13 139.6 (2) Li2iii_{—O23—C21—C22 29.3 (5)}

Li2iii_{—O11—C12—C13 −45.6 (3) B2—O22—C21—O23 −178.1 (2)}

B1—O11—C12—C11 17.2 (2) B2—O22—C21—C22 0.6 (3) Li2iii_{—O11—C12—C11 −167.9 (2) B2—O21—C22—C23 107.1 (3)}

O13—C11—C12—O11 169.2 (2) Li2viii_{—O21—C22—C23 −70.5 (3)}

O12—C11—C12—O11 −11.3 (3) B2—O21—C22—C21 −13.8 (3) O13—C11—C12—C13 47.0 (4) Li2viii_{—O21—C22—C21 168.5 (2)}

O12—C11—C12—C13 −133.5 (3) O23—C21—C22—O21 −173.2 (2) Li1—O16—C14—O14 141.6 (4) O22—C21—C22—O21 8.2 (3) Li1—O16—C14—C15 −38.6 (6) O23—C21—C22—C23 65.0 (3) B1—O14—C14—O16 178.9 (3) O22—C21—C22—C23 −113.7 (3) B1—O14—C14—C15 −0.9 (3) Li2—O26—C24—O24 10.0 (6) B1—O15—C15—C16 147.3 (3) Li2—O26—C24—C25 −169.4 (3) Li1v_{—O15—C15—C16 −39.8 (4) B2—O24—C24—O26 −178.7 (3)}

B1—O15—C15—C14 23.2 (3) B2—O24—C24—C25 0.8 (3) Li1v_{—O15—C15—C14 −164.0 (2) B2—O25—C25—C24 0.9 (3)}

O16—C14—C15—O15 166.4 (3) Li1—O25—C25—C24 166.9 (2) O14—C14—C15—O15 −13.8 (3) B2—O25—C25—C26 122.9 (3) O16—C14—C15—C16 43.2 (4) Li1—O25—C25—C26 −71.1 (3) O14—C14—C15—C16 −137.0 (3) O26—C24—C25—O25 178.4 (3) O25—B2—O21—C22 139.4 (2) O24—C24—C25—O25 −1.1 (3) O22—B2—O21—C22 14.3 (2) O26—C24—C25—C26 55.6 (4) O24—B2—O21—C22 −101.9 (2) O24—C24—C25—C26 −123.9 (3)