Bis{bis­[1-meth­oxy-2-(2-meth­oxy­eth­oxy)ethane-κ3O,O′,O′′]sodium} 1,1,2,2-tetra­phenyl­ethane-1,2-diide

Minyaev, M.E.; Ellis, J.E.

doi:10.1107/S1600536814012823

metal-organic compounds

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ISSN: 2056-9890

Volume 70| Part 7| July 2014| Pages m249-m250

https://doi.org/10.1107/S1600536814012823

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Bis{bis[1-methoxy-2-(2-methoxyethoxy)ethane-κ³O,O′,O′′]sodium} 1,1,2,2-tetraphenylethane-1,2-diide

Mikhail E. Minyaev ^a ^* and John E. Ellis ^b

^aA.V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, 29 Leninsky Prospect, 119991 Moscow, Russian Federation, and ^bUniversity of Minnesota, 207 Pleasant St. SE, Minneapolis, MN 55455, USA
^*Correspondence e-mail: mminyaev@mail.ru

(Received 23 May 2014; accepted 2 June 2014; online 7 June 2014)

Crystals of the title salt, [Na(C₆H₁₄O₃)₂]₂(C₂₆H₂₀), were grown from a tetrahydrofuran/diglyme/Et₂O solvent mixture [diglyme is 1-methoxy-2-(2-methoxyethoxy)ethane]. The cations and dianion are separated in the crystal structure, unlike in the other three structurally characterized dialkali metal tetraphenylethylene salts. The asymmetric unit contains one [Na(diglyme)₂]⁺ cation and one half of the [Ph₂CCPh₂]²⁻ dianion. The latter lies on a twofold rotation axis. C—C bond-length redistribution displays that excessive electron density of the dianion is predominantly located at the C atoms of a former double bond and at all eight ortho positions. The studied crystal was a twin, with the ratio of two major components being 0.2143 (9):0.7857 (9). The twin operation is a twofold rotation around the a axis.

CCDC reference: 1006312

Related literature

For the crystal structure of free tetraphenylethylenide, see: Hua et al. (2007 ). For the preparation and reactivity of disodiumtetraphenylethylene, see: Schlenk & Bergmann (1928 ). For UV–VIS data, see: Roberts & Szwarc (1965 ). For ¹H and ¹³C{¹H} NMR spectra, see: Roitershtein et al. (1998 ). For crystal structures of related alkali-metal tetraphenylethylene salts, see: Bock et al. (1989 , 1996 ); Minyaev et al. (2007 ). For crystal structures of hetero- and homoleptic d- and f-metal complexes with the tetraphenylethilene dianion, see: Roitershtein et al. (1998, 2004 , 2007 ); Minyaev et al. (2007).

Experimental

Crystal data

[Na(C₆H₁₄O₃)₂]₂(C₂₆H₂₀)
M_r = 915.08
Monoclinic, C 2/c
a = 10.048 (2) Å
b = 24.165 (5) Å
c = 20.978 (4) Å
β = 92.92 (3)°
V = 5087.0 (18) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 123 K
0.50 × 0.30 × 0.20 mm

Data collection

Siemens SMART Platform CCD diffractometer
Absorption correction: multi-scan (TWINABS; Bruker, 2003 ) T_min = 0.657, T_max = 0.746
6286 measured reflections
6286 independent reflections
5347 reflections with I > 2σ(I)

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.115
S = 1.06
6286 reflections
294 parameters
H-atom parameters constrained
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Selected bond lengths (Å)

C1—C1ⁱ	1.507 (3)
C1—C2	1.438 (2)
C1—C8	1.429 (2)
C2—C3	1.424 (3)
C2—C7	1.434 (3)
C3—C4	1.384 (3)
C4—C5	1.390 (3)
C5—C6	1.390 (3)
C6—C7	1.387 (3)
C8—C9	1.433 (3)
C8—C13	1.436 (3)
C9—C10	1.380 (3)
C10—C11	1.389 (3)
C11—C12	1.394 (3)
C12—C13	1.378 (3)
Symmetry code: (i) $[-x+1, y, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2003); cell refinement: CELL_NOW (Sheldrick, 2003 ) and SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS2012 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL2012 (Sheldrick, 2008) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1006312

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: https://doi.org/10.1107/S1600536814012823/pj2012sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536814012823/pj2012Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536814012823/pj2012Isup3.cdx

checkCIF report

Comment top

Detailed preparation and reactivity of disodiumtetraphenylethylene were described by Schlenk & Bergmann (1928). Since then, properties of the tetraphenylethylene dianion and radical-anion have been intensively studied, including electronic spectra, ¹H and ¹³C NMR spectral data, electrochemistry and etc. For example, ligand to metal charge transfer absorption band of the disodiumtetraphenylethylene in THF solution was reported by Roberts & Szwarc (1965); ¹H and ¹³C{¹H} NMR spectra of disodiumtetraphenylethylene in THF_d-8 have been reported by Roitershtein et al. (1998).

Synthetic applications of the tetraphenylethylene dianion are remarkably few. Reactivity of the tetraphenylethylene dianion towards formation either d- or f-element complexes is not well established so far. Only five crystal structures of hetero- and homoleptic complexes of lanthanides and yttrium with the tetraphenylethylene dianion have been reported: [Na(thf)₆]₂[Y(Ph₄C₂)₂](thf)₂, (Roitershtein et al., 1998), [Na(diglyme)₂][Lu(Ph₄C₂)₂](thf)_0.5 (Roitershtein et al., 2004), [Na(thf)₃][Na(thf)₄][Yb(Ph₄C₂)₂] (Minyaev et al., 2007), [(C₅H₅)Lu(Ph₄C₂)(dme)](dme) (Roitershtein et al., 2004) (dme is 1,2-dimethoxyethane), [(1,3–Ph₂C₅H₃)Lu(Ph₄C₂)(thf)] (Roitershtein et al., 2007).

As a part of our research project on synthesis and structural characterization of new tetraphenylethenide derivatives of rare-earth metals, we have explored reaction of disodiumtetraphenylethylene with anhydrous scandium(III) iodide (2:1 molar ratio), which was supposed to lead to formation of a homoleptic tetraphenylethenide ate-complex Na[Sc(Ph₄C₂)₂]. Anhydrous ScI₃ was activated by refluxing in THF in order to destroy its polymeric structure. According to ¹H NMR and UV-VIS spectral data, the final product after work-up contained expected Na[Sc(Ph₄C₂)₂] and some unreacted Na₂[Ph₄C₂]. Most likely, ScI₃ coordination polymer was not fully converted into the monomer or short oligomers, therefore, the tetraphenylethylene dianion was not fully consumed. Attempts to grow crystals of the reaction product in various solvents and conditions allowed us to obtain only crystals of the title compound when diglyme was used as σ-donating chelating ligand. Analogous reactions of M₂[Ph₄C₂] (M= Na, K) with LnCl₃(thf)₃ (Ln=Sc, Y, Lu), which have a molecular structure, go smoothly without any complications.

Crystal structure of free tetraphenylethylene is well known (see, for example, Hua et al., 2007). However, only three X-ray crystal structures of solvated dialkali metal tetraphenylethenides have been known up to date: {Na[Na(Ph₄C₂)(Et₂O)₂]}_n (Bock et al., 1989); {[Cs(diglyme)]₂[Ph₄C₂]} (Bock et al., 1996); {[K(dme)₂]₂[Ph₄C₂]} (Minyaev et al., 2007). There are interionic short contacts M⁺–Ph₄C₂^2- (M= Na, K, Cs) in all three crystal structures, which may have some impact on the C—C bond length redistribution inside the easily polarizable tetraphenylethylene dianion.

The title compound, [Na(diglyme)₂]⁺₂[Ph₂CCPh₂]^2-, is the only example with separated counterions in crystalline lattice. Consequently, one may suppose that the C—C bond distances of the dianion are relatively unperturbed. However, some non-covalent interionic bonding is present. A three-dimensional framework is formed by C—H_diglyme···C_Ph π-interactions (e.g., C14—H14A···C13, C15—H15A···C2, C17—H17B···C11, C22—H22A···η²-C10—C11, C23—H23A···η⁶-C2—C3—C4—C5—C6—C7) and by C—H_Ph···O_diglyme hydrogen bonds (C4—H4···O4). The asymmetric unit contains one cation [Na(diglyme)₂]⁺ and a half of the dianion [Ph₂CCPh₂]^2-. The center of the tetraphenylethylene former C–C double bond (C₌–C₌) lies on a 2-fold rotation axis. The dianion accommodates a twist conformation. The angle between two planes, formed by C_ipso, C₌ and C_ipso carbon atoms (C2—C1—C8 and C2ⁱ—C1ⁱ—C8ⁱ, respectively), equals to 82.4°. The C₌–C₌ bond (atoms C1–C1ⁱ) is elongated up to a single bond (1.507 (3) Å, see table 1). Based on table 1, the C₌–C_ipso bond lengths are shorter and C_ipso–C_ortho — longer than those in free tetraphenylethylene. Averaged C—C bond distances inside the dianion are 1.434 Å (C₌–C_ipso), 1.432 Å (C_ipso–C_ortho), 1.382 Å (C_ortho–C_meta), 1.391 Å (C_meta–C_para). For comparison, the same C—C bond distances in free tetraphenylethylene (Hua et al., 2007) are 1.356 (2) Å (C₌–C₌), 1.494 Å (C₌–C_ipso), 1.397 Å (C_ipso–C_ortho), 1.388 Å (C_ortho–C_meta), 1.384 Å (C_meta–C_para).

The observed C—C bond length redistribution inside the dianion could be rationalized by localization of excessive negative charge predominantly not only at C₌ carbon atoms but also at all eight C_ortho positions (see Fig.1).

Similar averaged C—C bond lengths in the Ph₄C₂^2- dianion can be found in {[Cs(diglyme)]₂[Ph₄C₂]} (Bock et al., 1996) — 1.51 (1) Å (C₌–C₌), 1.436 Å (C₌–C_ipso), 1.423 Å (C_ipso–C_ortho), 1.387 Å (C_ortho–C_meta), 1.385 Å (C_meta–C_para), and in {[K(dme)₂]₂[Ph₄C₂]} (Minyaev et al., 2007) — 1.496 (2) Å (C₌–C₌), 1.433 Å (C₌–C_ipso), 1.430 Å (C_ipso–C_ortho), 1.384 Å (C_ortho–C_meta), 1.392 Å (C_meta–C_para). Therefore, M—Ph₄C₂ (M=K, Cs) short contacts do not introduce much influence on the C—C bond length redistribution, compared to that of the title compound with separated counterions.

In coordination polymer {Na[Na(Ph₄C₂)(Et₂O)₂]}_n (Bock et al., 1989), the C₌–C₌ bond length is 1.487 Å, but some similar C—C distances vary essentially. Thus, phenyl rings coordinated with Na⁺ and Na(Et₂O)₂⁺ moieties display the following averaged bond lengths: 1.463 Å (C₌–C_ipso), 1.444 Å (C_ipso–C_ortho), 1.397 Å (C_ortho–C_meta), 1.396 Å (C_meta–C_para). For phenyl rings that almost do not interact with the Na⁺ cation, the averaged C—C bond distances are 1.436 Å (C₌–C_ipso), 1.416 Å (C_ipso–C_ortho. Actual bond lengths are 1.407 Å, 1.423 Å for a one phenyl ring and 1.405 Å, 1.427 Å for another one.), 1.392 Å (C_ortho–C_meta), 1.391 Å (C_meta–C_para). It is obvious that excessive electron density of the dianion is not equally localized at ortho-positions of coordinated and uncoordinated phenyl groups, and charge redistribution inside the dianion is quite different from such of three previous salts. Impact on C—C bond distances could be partly explained by stronger polarizing ability of Na⁺, compared to K⁺ and Cs⁺.

It is worth mentioning that the angle between two C_ipso—C₌—C_ipso planes decreases in the following order: [Na(diglyme)₂]₂[Ph₂CCPh₂] (82.4°), {[Cs(diglyme)]₂[Ph₄C₂]} (75.5°), {[K(dme)₂]₂[Ph₄C₂]} (68.7°), {Na[Na(Ph₄C₂)(Et₂O)₂]}_n (56.1°), which has a positive correlation with the M—Ph₄C₂ strength interaction (M=Na, K, Cs). The same angle is 8.8° in free Ph₂C=CPh₂.

The C—C bond length redistribution changes even more dramatically in crystalline lattice of rare-earth complexes due to higher polarizing ability of Ln³⁺ and Yb²⁺. The coordinated tetraphenylethelene dianion in rare-earth complexes exhibits bis-η³-allylic coordination mode, where the excessive negative charge of the dianion is localized at C₌ carbon atoms and only at two C_ortho positions coordinated with the metal cation (Roitershtein et al., 1998; Roitershtein et al., 2004; Minyaev et al., 2007; Roitershtein et al., 2007).

Related literature top

For the crystal structure of free tetraphenylethylenide, see: Hua et al. (2007). For the preparation and reactivity of disodiumtetraphenylethylene, see: Schlenk & Bergmann (1928). For UV–VIS data, see: Roberts & Szwarc (1965). For ¹H and ¹³C{¹H} NMR spectra, see: Roitershtein et al. (1998). For crystal structures of related alkali-metal tetraphenylethylene salts, see: Bock et al. (1989, 1996); Minyaev et al. (2007). For crystal structures of hetero- and homoleptic d- and f-metal complexes with the tetraphenylethilene dianion, see: Roitershtein et al. (1998, 2004, 2007); Minyaev et al. (2007).

Experimental top

All synthetic manipulations were carried out under vacuum or argon atmosphere, using Schlenk glassware, dry box techniques and absolute solvents. A 250 ml flask with freshly cut sodium metal (0.60 g, 26 mmol) was evacuated. Sodium mirror was formed on the flask's walls upon heating under dynamic vacuum. Tetraphenylethylene solution in THF (1.249 g, 3.76 mmol in 100 ml) was added into the flask. The solution was stirred for 1 day, the color changed to purple (λ_max= 485 nm). Simultaneously, anhydrous ScI₃ (0.784 g, 1.84 mmol) was stirred for 5 h in THF (50 ml) and then refluxed for 2 h while stirring to form a finely divided suspension. The Na₂[Ph₄C₂] solution was added dropwise into the ScI₃ suspension. The reaction mixture was stirred for 1 day. λ_max of the reaction mixture = 422 nm (very br.), which is a superposition of 2 ligand to metal charge transfer absorption bands: 485 nm for Na₂[Ph₄C₂] (Roberts & Szwarc, 1965) and 392 nm for Na[Sc(Ph₄C₂)₂]. λ_max did not change after 3 day of stirring. Then the reaction mixture was filtered, the filter cake and the flask were washed with THF (2x20 ml). Most THF was evaporated from the solution, leaving some solid and c.a. 20 ml of the solution. Pentane (c.a. 100 ml) was layered on a top of the solution. After 1 day, the mixture was stirred. Precipitate was filtered off, washed with pentane (2x20 ml) and with diethyl ether (2x20 ml), dried under vacuum for 4 h. The yield of crude product was 1.473 g.

To grow crystals of the title compound, the obtained crude product (150 mg) was dissolved in mixture of THF (20 ml) and diglyme (5 ml). Diethyl ether (35 ml) was layered on a top of the resulting solution. After 2 weeks, crystals formed on Schlenk tube's walls.

The ¹H NMR spectrum of the crude product consisted of two sets of proton signals. The first set belongs to Na₂[Ph₄C₂] (see Roitershtein et al., 1998). The second set corresponds to Na[Sc(Ph₄C₂)₂] – ¹H NMR (300 MHz, -30°C, THF_d-8, δ, p.p.m.): 4.65 (dd, 4H), 6.29 (t, 4H), 6.58 (t, 4H), 6.87 (br.t, 12H), 7.07 (t, 4H), 7.14 (d, 8H), 7.65 (dd, 4H).

Based on qualitative analysis with xylenol orange indicator, the filter cake contained significant amounts of scandium.

Structure description top

For the crystal structure of free tetraphenylethylenide, see: Hua et al. (2007). For the preparation and reactivity of disodiumtetraphenylethylene, see: Schlenk & Bergmann (1928). For UV–VIS data, see: Roberts & Szwarc (1965). For ¹H and ¹³C{¹H} NMR spectra, see: Roitershtein et al. (1998). For crystal structures of related alkali-metal tetraphenylethylene salts, see: Bock et al. (1989, 1996); Minyaev et al. (2007). For crystal structures of hetero- and homoleptic d- and f-metal complexes with the tetraphenylethilene dianion, see: Roitershtein et al. (1998, 2004, 2007); Minyaev et al. (2007).

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: CELL_NOW (Sheldrick, 2003) and SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS2012 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2008); molecular graphics: SHELXTL (Bruker, 2003); software used to prepare material for publication: SHELXTL2012 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. Some of possible resonance forms, showing charge redistribution among one C₌ and two C_ortho positions.
	Fig. 2. Molecular structure of [Na(diglyme)₂]⁺₂[Ph₂CCPh₂]^2- (50% atomic displacement parameters). One cation is shown. Hydrogen atoms are omitted for clarity. Symmetry code: (i) -x + 1, y, -z + 1/2.

Bis{bis[1-methoxy-2-(2-methoxyethoxy)ethane-κ³O,O',O'']sodium} 1,1,2,2-tetraphenylethane-1,2-diide top

Crystal data top

[Na(C₆H₁₄O₃)₂]₂(C₂₆H₂₀)	F(000) = 1976
M_r = 915.08	D_x = 1.195 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.048 (2) Å	Cell parameters from 4057 reflections
b = 24.165 (5) Å	θ = 2.2–28.2°
c = 20.978 (4) Å	µ = 0.10 mm⁻¹
β = 92.92 (3)°	T = 123 K
V = 5087.0 (18) Å³	Block, red
Z = 4	0.50 × 0.30 × 0.20 mm

Data collection top

Siemens SMART Platform CCD diffractometer	6286 independent reflections
Radiation source: normal-focus sealed tube	5347 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.0
area detector, ω scans per phi	θ_max = 28.3°, θ_min = 1.7°
Absorption correction: multi-scan (TWINABS; Bruker, 2003)	h = −13→13
T_min = 0.657, T_max = 0.746	k = 0→32
6286 measured reflections	l = 0→27

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.115	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0435P)² + 4.6083P] where P = (F_o² + 2F_c²)/3
6286 reflections	(Δ/σ)_max < 0.001
294 parameters	Δρ_max = 0.42 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

[Na(C₆H₁₄O₃)₂]₂(C₂₆H₂₀)	V = 5087.0 (18) Å³
M_r = 915.08	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 10.048 (2) Å	µ = 0.10 mm⁻¹
b = 24.165 (5) Å	T = 123 K
c = 20.978 (4) Å	0.50 × 0.30 × 0.20 mm
β = 92.92 (3)°

Data collection top

Siemens SMART Platform CCD diffractometer	6286 independent reflections
Absorption correction: multi-scan (TWINABS; Bruker, 2003)	5347 reflections with I > 2σ(I)
T_min = 0.657, T_max = 0.746	R_int = 0.0
6286 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.115	H-atom parameters constrained
S = 1.06	Δρ_max = 0.42 e Å⁻³
6286 reflections	Δρ_min = −0.23 e Å⁻³
294 parameters

Special details top

Experimental. moisture and air sensitive

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 F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. Refined as a 2-component twin. BASF=0.214

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

	x	y	z	U_iso*/U_eq
C1	0.42755 (17)	0.13927 (7)	0.25769 (8)	0.0214 (3)
C2	0.38922 (17)	0.17452 (7)	0.30886 (8)	0.0219 (3)
C3	0.47563 (19)	0.21800 (7)	0.33076 (8)	0.0251 (4)
H3	0.5576	0.2228	0.3108	0.030*
C4	0.4459 (2)	0.25360 (8)	0.37973 (9)	0.0326 (4)
H4	0.5062	0.2825	0.3915	0.039*
C5	0.3292 (2)	0.24769 (9)	0.41196 (9)	0.0379 (5)
H5	0.3084	0.2723	0.4453	0.045*
C6	0.2442 (2)	0.20449 (9)	0.39376 (9)	0.0346 (4)
H6	0.1654	0.1990	0.4162	0.042*
C7	0.27099 (19)	0.16925 (8)	0.34386 (8)	0.0273 (4)
H7	0.2091	0.1407	0.3325	0.033*
C8	0.33820 (18)	0.10525 (7)	0.21972 (8)	0.0221 (3)
C9	0.3903 (2)	0.06401 (7)	0.17867 (9)	0.0276 (4)
H9	0.4842	0.0598	0.1779	0.033*
C10	0.3100 (2)	0.03023 (8)	0.14016 (9)	0.0343 (4)
H10	0.3500	0.0033	0.1142	0.041*
C11	0.1720 (2)	0.03466 (9)	0.13839 (10)	0.0383 (5)
H11	0.1170	0.0109	0.1124	0.046*
C12	0.1172 (2)	0.07532 (9)	0.17626 (10)	0.0344 (5)
H12	0.0232	0.0797	0.1751	0.041*
C13	0.19548 (19)	0.10935 (8)	0.21528 (9)	0.0271 (4)
H13	0.1535	0.1365	0.2401	0.032*
Na1	0.19803 (8)	0.37669 (3)	0.10184 (3)	0.03106 (18)
C14	0.0899 (3)	0.25199 (9)	0.14723 (13)	0.0545 (7)
H14A	0.1255	0.2159	0.1610	0.082*
H14B	0.0679	0.2512	0.1012	0.082*
H14C	0.0093	0.2601	0.1700	0.082*
O1	0.18706 (16)	0.29378 (6)	0.16114 (6)	0.0393 (4)
C15	0.2176 (2)	0.29889 (11)	0.22790 (10)	0.0453 (6)
H15A	0.2590	0.2644	0.2448	0.054*
H15B	0.1352	0.3058	0.2506	0.054*
C16	0.3109 (2)	0.34577 (12)	0.23745 (10)	0.0499 (6)
H16A	0.3346	0.3508	0.2835	0.060*
H16B	0.3936	0.3387	0.2151	0.060*
O2	0.24528 (15)	0.39425 (7)	0.21202 (7)	0.0409 (4)
C17	0.3210 (3)	0.44350 (13)	0.21969 (12)	0.0576 (7)
H17A	0.4123	0.4375	0.2055	0.069*
H17B	0.3271	0.4546	0.2652	0.069*
C18	0.2538 (3)	0.48737 (10)	0.18068 (13)	0.0573 (7)
H18A	0.1606	0.4918	0.1930	0.069*
H18B	0.3006	0.5231	0.1876	0.069*
O3	0.25612 (17)	0.47153 (6)	0.11525 (8)	0.0458 (4)
C19	0.2039 (4)	0.51249 (11)	0.07319 (17)	0.0764 (9)
H19A	0.2505	0.5475	0.0817	0.115*
H19B	0.1086	0.5173	0.0796	0.115*
H19C	0.2161	0.5011	0.0290	0.115*
C20	0.4897 (3)	0.40361 (14)	0.03195 (17)	0.0767 (10)
H20A	0.5734	0.3834	0.0282	0.115*
H20B	0.4985	0.4292	0.0681	0.115*
H20C	0.4692	0.4245	−0.0074	0.115*
O4	0.38983 (16)	0.36721 (7)	0.04155 (8)	0.0476 (4)
C21	0.3632 (3)	0.32886 (12)	−0.00971 (13)	0.0573 (7)
H21A	0.3594	0.2908	0.0076	0.069*
H21B	0.4365	0.3303	−0.0395	0.069*
C22	0.2354 (2)	0.34211 (10)	−0.04470 (10)	0.0403 (5)
H22A	0.2401	0.3792	−0.0646	0.048*
H22B	0.2160	0.3145	−0.0788	0.048*
O5	0.13343 (14)	0.34110 (6)	0.00064 (6)	0.0321 (3)
C23	0.01609 (19)	0.36844 (9)	−0.02316 (9)	0.0316 (4)
H23A	−0.0179	0.3510	−0.0635	0.038*
H23B	0.0353	0.4079	−0.0317	0.038*
C24	−0.0849 (2)	0.36364 (10)	0.02655 (10)	0.0368 (5)
H24A	−0.1696	0.3812	0.0111	0.044*
H24B	−0.1026	0.3242	0.0355	0.044*
O6	−0.03470 (15)	0.39049 (6)	0.08320 (7)	0.0360 (3)
C25	−0.1223 (3)	0.38392 (10)	0.13393 (11)	0.0484 (6)
H25A	−0.2067	0.4028	0.1230	0.073*
H25B	−0.0813	0.4000	0.1731	0.073*
H25C	−0.1390	0.3444	0.1407	0.073*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0197 (8)	0.0234 (8)	0.0211 (8)	0.0002 (7)	0.0015 (6)	0.0031 (6)
C2	0.0211 (8)	0.0239 (8)	0.0205 (8)	0.0045 (7)	0.0005 (6)	0.0062 (6)
C3	0.0286 (9)	0.0264 (9)	0.0203 (8)	0.0018 (7)	0.0025 (7)	0.0014 (7)
C4	0.0408 (11)	0.0292 (10)	0.0277 (9)	0.0020 (8)	−0.0006 (8)	−0.0026 (8)
C5	0.0461 (13)	0.0394 (11)	0.0286 (10)	0.0145 (10)	0.0071 (9)	−0.0055 (8)
C6	0.0293 (10)	0.0475 (12)	0.0279 (9)	0.0123 (9)	0.0088 (8)	0.0050 (8)
C7	0.0239 (9)	0.0338 (9)	0.0242 (8)	0.0032 (7)	0.0025 (7)	0.0055 (7)
C8	0.0246 (9)	0.0210 (8)	0.0207 (8)	−0.0023 (7)	−0.0001 (7)	0.0072 (6)
C9	0.0327 (10)	0.0241 (9)	0.0257 (9)	−0.0016 (7)	−0.0008 (7)	0.0023 (7)
C10	0.0478 (12)	0.0259 (9)	0.0287 (9)	−0.0052 (9)	−0.0019 (9)	−0.0007 (7)
C11	0.0459 (13)	0.0334 (10)	0.0344 (10)	−0.0174 (9)	−0.0115 (9)	0.0032 (8)
C12	0.0259 (10)	0.0419 (11)	0.0346 (10)	−0.0100 (9)	−0.0060 (8)	0.0123 (9)
C13	0.0257 (9)	0.0286 (9)	0.0266 (9)	−0.0013 (7)	−0.0006 (7)	0.0073 (7)
Na1	0.0402 (4)	0.0287 (4)	0.0236 (3)	0.0006 (3)	−0.0053 (3)	−0.0037 (3)
C14	0.086 (2)	0.0275 (11)	0.0514 (14)	−0.0008 (12)	0.0215 (14)	−0.0041 (10)
O1	0.0509 (9)	0.0384 (8)	0.0292 (7)	0.0107 (7)	0.0063 (7)	0.0061 (6)
C15	0.0422 (13)	0.0667 (15)	0.0274 (10)	0.0218 (12)	0.0066 (9)	0.0130 (10)
C16	0.0314 (12)	0.0934 (19)	0.0245 (10)	0.0162 (12)	−0.0013 (8)	0.0027 (11)
O2	0.0330 (8)	0.0578 (9)	0.0316 (7)	0.0016 (7)	−0.0030 (6)	−0.0143 (7)
C17	0.0473 (14)	0.0851 (19)	0.0401 (12)	−0.0176 (14)	−0.0006 (11)	−0.0301 (13)
C18	0.0553 (15)	0.0454 (13)	0.0728 (17)	−0.0110 (12)	0.0181 (14)	−0.0372 (13)
O3	0.0510 (10)	0.0311 (7)	0.0546 (9)	0.0033 (7)	−0.0039 (8)	−0.0116 (7)
C19	0.093 (2)	0.0369 (14)	0.099 (2)	0.0093 (15)	0.008 (2)	0.0144 (15)
C20	0.075 (2)	0.0665 (19)	0.092 (2)	−0.0355 (16)	0.0292 (18)	−0.0306 (17)
O4	0.0354 (8)	0.0539 (10)	0.0535 (10)	−0.0069 (7)	0.0021 (7)	−0.0270 (8)
C21	0.0390 (13)	0.0708 (18)	0.0615 (16)	0.0057 (12)	−0.0025 (12)	−0.0355 (14)
C22	0.0356 (12)	0.0547 (13)	0.0308 (10)	0.0024 (10)	0.0043 (8)	−0.0084 (9)
O5	0.0291 (7)	0.0430 (8)	0.0240 (6)	0.0017 (6)	0.0002 (5)	−0.0018 (6)
C23	0.0302 (10)	0.0405 (11)	0.0237 (9)	−0.0031 (8)	−0.0026 (7)	0.0000 (8)
C24	0.0314 (11)	0.0467 (12)	0.0325 (10)	−0.0039 (9)	0.0025 (8)	−0.0009 (9)
O6	0.0396 (8)	0.0414 (8)	0.0277 (7)	0.0008 (6)	0.0075 (6)	−0.0005 (6)
C25	0.0632 (16)	0.0432 (12)	0.0411 (12)	0.0041 (11)	0.0258 (12)	0.0012 (10)

Geometric parameters (Å, º) top

C1—C1ⁱ	1.507 (3)	C15—H15A	0.9900
C1—C2	1.438 (2)	C15—H15B	0.9900
C1—C8	1.429 (2)	C16—O2	1.434 (3)
C2—C3	1.424 (3)	C16—H16A	0.9900
C2—C7	1.434 (3)	C16—H16B	0.9900
C3—C4	1.384 (3)	O2—C17	1.417 (3)
C3—H3	0.9500	C17—C18	1.481 (4)
C4—C5	1.390 (3)	C17—H17A	0.9900
C4—H4	0.9500	C17—H17B	0.9900
C5—C6	1.390 (3)	C18—O3	1.426 (3)
C5—H5	0.9500	C18—H18A	0.9900
C6—C7	1.387 (3)	C18—H18B	0.9900
C6—H6	0.9500	O3—C19	1.410 (3)
C7—H7	0.9500	C19—H19A	0.9800
C8—C9	1.433 (3)	C19—H19B	0.9800
C8—C13	1.436 (3)	C19—H19C	0.9800
C9—C10	1.380 (3)	C20—O4	1.357 (3)
C9—H9	0.9500	C20—H20A	0.9800
C10—C11	1.389 (3)	C20—H20B	0.9800
C10—H10	0.9500	C20—H20C	0.9800
C11—C12	1.394 (3)	O4—C21	1.434 (3)
C11—H11	0.9500	C21—C22	1.481 (3)
C12—C13	1.378 (3)	C21—H21A	0.9900
C12—H12	0.9500	C21—H21B	0.9900
C13—H13	0.9500	C22—O5	1.434 (2)
Na1—O5	2.3510 (16)	C22—H22A	0.9900
Na1—O1	2.3639 (16)	C22—H22B	0.9900
Na1—O4	2.3694 (19)	O5—C23	1.420 (2)
Na1—O2	2.3742 (16)	C23—C24	1.496 (3)
Na1—O6	2.3747 (18)	C23—H23A	0.9900
Na1—O3	2.3781 (17)	C23—H23B	0.9900
Na1—C16	3.100 (2)	C24—O6	1.424 (3)
Na1—C23	3.126 (2)	C24—H24A	0.9900
C14—O1	1.425 (3)	C24—H24B	0.9900
C14—H14A	0.9800	O6—C25	1.424 (3)
C14—H14B	0.9800	C25—H25A	0.9800
C14—H14C	0.9800	C25—H25B	0.9800
O1—C15	1.424 (3)	C25—H25C	0.9800
C15—C16	1.478 (4)

C8—C1—C2	124.90 (16)	O2—C16—Na1	47.30 (8)
C8—C1—C1ⁱ	117.83 (15)	C15—C16—Na1	81.98 (12)
C2—C1—C1ⁱ	117.26 (15)	O2—C16—H16A	110.2
C3—C2—C7	114.07 (16)	C15—C16—H16A	110.2
C3—C2—C1	119.72 (15)	Na1—C16—H16A	157.5
C7—C2—C1	126.15 (16)	O2—C16—H16B	110.2
C4—C3—C2	123.15 (17)	C15—C16—H16B	110.2
C4—C3—H3	118.4	Na1—C16—H16B	83.3
C2—C3—H3	118.4	H16A—C16—H16B	108.5
C3—C4—C5	121.09 (19)	C17—O2—C16	114.22 (19)
C3—C4—H4	119.5	C17—O2—Na1	109.88 (13)
C5—C4—H4	119.5	C16—O2—Na1	106.35 (12)
C4—C5—C6	117.74 (18)	O2—C17—C18	108.2 (2)
C4—C5—H5	121.1	O2—C17—H17A	110.1
C6—C5—H5	121.1	C18—C17—H17A	110.1
C7—C6—C5	121.88 (19)	O2—C17—H17B	110.1
C7—C6—H6	119.1	C18—C17—H17B	110.1
C5—C6—H6	119.1	H17A—C17—H17B	108.4
C6—C7—C2	122.00 (18)	O3—C18—C17	108.06 (19)
C6—C7—H7	119.0	O3—C18—H18A	110.1
C2—C7—H7	119.0	C17—C18—H18A	110.1
C1—C8—C9	119.78 (16)	O3—C18—H18B	110.1
C1—C8—C13	126.40 (17)	C17—C18—H18B	110.1
C9—C8—C13	113.75 (16)	H18A—C18—H18B	108.4
C10—C9—C8	122.88 (19)	C19—O3—C18	112.9 (2)
C10—C9—H9	118.6	C19—O3—Na1	121.42 (17)
C8—C9—H9	118.6	C18—O3—Na1	110.89 (14)
C9—C10—C11	121.5 (2)	O3—C19—H19A	109.5
C9—C10—H10	119.2	O3—C19—H19B	109.5
C11—C10—H10	119.2	H19A—C19—H19B	109.5
C10—C11—C12	117.48 (18)	O3—C19—H19C	109.5
C10—C11—H11	121.3	H19A—C19—H19C	109.5
C12—C11—H11	121.3	H19B—C19—H19C	109.5
C13—C12—C11	121.95 (19)	O4—C20—H20A	109.5
C13—C12—H12	119.0	O4—C20—H20B	109.5
C11—C12—H12	119.0	H20A—C20—H20B	109.5
C12—C13—C8	122.37 (19)	O4—C20—H20C	109.5
C12—C13—H13	118.8	H20A—C20—H20C	109.5
C8—C13—H13	118.8	H20B—C20—H20C	109.5
O5—Na1—O1	98.46 (6)	C20—O4—C21	114.7 (2)
O5—Na1—O4	71.18 (6)	C20—O4—Na1	130.10 (17)
O1—Na1—O4	105.07 (7)	C21—O4—Na1	109.70 (14)
O5—Na1—O2	167.64 (6)	O4—C21—C22	110.8 (2)
O1—Na1—O2	69.60 (6)	O4—C21—H21A	109.5
O4—Na1—O2	114.15 (7)	C22—C21—H21A	109.5
O5—Na1—O6	71.24 (6)	O4—C21—H21B	109.5
O1—Na1—O6	97.69 (6)	C22—C21—H21B	109.5
O4—Na1—O6	138.30 (6)	H21A—C21—H21B	108.1
O2—Na1—O6	106.35 (6)	O5—C22—C21	107.37 (18)
O5—Na1—O3	120.94 (6)	O5—C22—H22A	110.2
O1—Na1—O3	140.56 (6)	C21—C22—H22A	110.2
O4—Na1—O3	87.41 (6)	O5—C22—H22B	110.2
O2—Na1—O3	71.15 (6)	C21—C22—H22B	110.2
O6—Na1—O3	96.77 (6)	H22A—C22—H22B	108.5
O5—Na1—C16	144.27 (7)	C23—O5—C22	111.57 (15)
O1—Na1—C16	48.50 (7)	C23—O5—Na1	109.48 (11)
O4—Na1—C16	101.37 (7)	C22—O5—Na1	114.77 (12)
O2—Na1—C16	26.35 (6)	O5—C23—C24	107.43 (16)
O6—Na1—C16	119.74 (6)	O5—C23—Na1	45.17 (8)
O3—Na1—C16	92.73 (7)	C24—C23—Na1	78.98 (11)
O5—Na1—C23	25.36 (5)	O5—C23—H23A	110.2
O1—Na1—C23	110.27 (6)	C24—C23—H23A	110.2
O4—Na1—C23	90.17 (6)	Na1—C23—H23A	154.8
O2—Na1—C23	155.18 (6)	O5—C23—H23B	110.2
O6—Na1—C23	48.84 (5)	C24—C23—H23B	110.2
O3—Na1—C23	106.88 (6)	Na1—C23—H23B	88.8
C16—Na1—C23	157.75 (7)	H23A—C23—H23B	108.5
O1—C14—H14A	109.5	O6—C24—C23	108.80 (17)
O1—C14—H14B	109.5	O6—C24—H24A	109.9
H14A—C14—H14B	109.5	C23—C24—H24A	109.9
O1—C14—H14C	109.5	O6—C24—H24B	109.9
H14A—C14—H14C	109.5	C23—C24—H24B	109.9
H14B—C14—H14C	109.5	H24A—C24—H24B	108.3
C15—O1—C14	111.96 (18)	C24—O6—C25	111.52 (18)
C15—O1—Na1	115.51 (14)	C24—O6—Na1	112.19 (12)
C14—O1—Na1	122.87 (14)	C25—O6—Na1	120.14 (14)
O1—C15—C16	107.65 (18)	O6—C25—H25A	109.5
O1—C15—H15A	110.2	O6—C25—H25B	109.5
C16—C15—H15A	110.2	H25A—C25—H25B	109.5
O1—C15—H15B	110.2	O6—C25—H25C	109.5
C16—C15—H15B	110.2	H25A—C25—H25C	109.5
H15A—C15—H15B	108.5	H25B—C25—H25C	109.5
O2—C16—C15	107.43 (17)

C8—C1—C2—C3	−161.55 (16)	C14—O1—C15—C16	−175.81 (19)
C1ⁱ—C1—C2—C3	17.1 (2)	Na1—O1—C15—C16	−28.6 (2)
C8—C1—C2—C7	21.4 (3)	O1—C15—C16—O2	59.8 (2)
C1ⁱ—C1—C2—C7	−159.90 (15)	O1—C15—C16—Na1	19.41 (14)
C7—C2—C3—C4	−2.6 (2)	C15—C16—O2—C17	177.87 (18)
C1—C2—C3—C4	−179.96 (17)	Na1—C16—O2—C17	−121.37 (18)
C2—C3—C4—C5	1.8 (3)	C15—C16—O2—Na1	−60.75 (18)
C3—C4—C5—C6	0.6 (3)	C16—O2—C17—C18	169.02 (18)
C4—C5—C6—C7	−2.1 (3)	Na1—O2—C17—C18	49.6 (2)
C5—C6—C7—C2	1.3 (3)	O2—C17—C18—O3	−64.0 (3)
C3—C2—C7—C6	1.1 (2)	C17—C18—O3—C19	−175.3 (2)
C1—C2—C7—C6	178.24 (17)	C17—C18—O3—Na1	44.6 (2)
C2—C1—C8—C9	−167.86 (16)	C20—O4—C21—C22	−108.3 (3)
C1ⁱ—C1—C8—C9	13.5 (2)	Na1—O4—C21—C22	48.4 (3)
C2—C1—C8—C13	15.4 (3)	O4—C21—C22—O5	−57.4 (3)
C1ⁱ—C1—C8—C13	−163.26 (15)	C21—C22—O5—C23	162.93 (18)
C1—C8—C9—C10	−179.18 (17)	C21—C22—O5—Na1	37.7 (2)
C13—C8—C9—C10	−2.1 (2)	C22—O5—C23—C24	178.34 (17)
C8—C9—C10—C11	0.7 (3)	Na1—O5—C23—C24	−53.51 (18)
C9—C10—C11—C12	1.1 (3)	C22—O5—C23—Na1	−128.15 (18)
C10—C11—C12—C13	−1.4 (3)	O5—C23—C24—O6	61.5 (2)
C11—C12—C13—C8	−0.1 (3)	Na1—C23—C24—O6	26.01 (14)
C1—C8—C13—C12	178.66 (17)	C23—C24—O6—C25	−175.77 (18)
C9—C8—C13—C12	1.8 (2)	C23—C24—O6—Na1	−37.7 (2)

Symmetry code: (i) −x+1, y, −z+1/2.

Selected bond lengths (Å) top

C1—C1ⁱ	1.507 (3)	C6—C7	1.387 (3)
C1—C2	1.438 (2)	C8—C9	1.433 (3)
C1—C8	1.429 (2)	C8—C13	1.436 (3)
C2—C3	1.424 (3)	C9—C10	1.380 (3)
C2—C7	1.434 (3)	C10—C11	1.389 (3)
C3—C4	1.384 (3)	C11—C12	1.394 (3)
C4—C5	1.390 (3)	C12—C13	1.378 (3)
C5—C6	1.390 (3)

Symmetry code: (i) −x+1, y, −z+1/2.

Acknowledgements

The authors are grateful to the US National Science Foundation (grant CHE-0841014) for financial support and to Victor Young, Jr, Director of the X-ray Crystallographic Facility at the University of Minnesota.

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