[Et₄N][7-Me₂S-nido-B₁₁H₁₂]

Tetraethyl­ammonium 7-di­methyl­sulfanyl-nido-dodeca­hydro­undecaborate, [Et₄N][7-Me₂S-nido-B₁₁H₁₂] or C₈H₂₀N⁺·C₂H₁₈B₁₁S^-, is a product of the deprotonation of [7-Me₂S-nido-B₁₁H₁₃] with KHBEt₃ and precipitation with tetraethyl­ammonium chloride. The effect of removing one endo-terminal H atom is to cause a general contraction of the open-face B-B distances.

S1. Comment

There is currently some interest in the modification of the catalytic properties of transition metals held on dicarbaborane clusters by the introduction of cluster substituent groups at boron or carbon cluster vertices (Teixidor et al., 1996, 2000; Tutusaus et al., 2002). Thus, for example, addition of an R₂S group to an open-face boron vertex in [C₂B₉H₁₁]²⁻ leads to the monoanionic dicarbollide [10-R₂S-7,8-C₂B₉H₁₀]⁻ from which metallacarboranes such as [3-RuH(PPh₃)₂-8-R₂S-7,8-C₂B₉H₉] may be formed (Tutusaus et al., 2002).

It is of interest to extend this work to binary borane compounds with substituents such as Me₂S on the five-membered open face, as in [Me₂SB₁₁H₁₃], (I) (Scheme I and Keller et al., 1993). Double deprotonation of this cluster, together with simultaneous Me₂S loss, is known to give K₂[closo-B₁₁H₁₁] in high yield (Volkov, et al., 1999), from which a variety of substituted nido-undecaborate anions may be synthesized (Volkov et al., 2001). In the preparation of K₂[closo-B₁₁H₁₁], we obtained an occasional by-product, K[7-Me₂S-nido-B₁₁H₁₂], to which the addition of aqueous [Et₄N]Cl afforded the title compound, [Et₄N][7-Me₂S-nido-B₁₁H₁₂], (II) (Scheme 1 and Fig. 1). ¹¹B NMR spectra of (II) feature a 2:2:2:2:2:1 relative intensity pattern rather than the 2:2:2:2:1:1:1 pattern expected for a nido eleven-vertex cluster with C_s symmetry. This result is caused by? coincidental overlap of the resonances due to B7 and B5, which inhibited the complete characterization of (II), and we therefore carried out a single-crystal X-ray diffraction study.

Both the clusters in (I) and its conjugate anion, the anion of (II), contain pseudo-mirror planes through B1/B5/B7, such that interatomic distances B7—B2 and B7—B3, B7—B8 and B7—B11, and B8—B9 and B10—B11 are equal within experimental error. Therefore, in this discussion, for comparison purposes, average values are given. The Me₂S ligand, which is freely rotating in solution, lies off the pseudo-mirror plane.

The main effect of deprotonation on interatomic separations in (II) is in the upper-belt open-face B atoms, with the average B—B distance shrinking from 1.904 to 1.822 Å. The largest change is for distances associated with the B7 vertex, the site of the removed endo-terminal proton. Thus the B7—B8/B11 distances contract markedly by ca 0.19 Å, from 1.943 (4) in (I) to 1.754 (3) Å in (II). There is a smaller 0.018 Å contraction of the B7—B2/B3 distance in the lower-belt vertices [from 1.762 (4) to 1.744 (3) Å]. The B9—B10 vector also exhibits a contraction of 0.046 Å, whereas the H-atom-bridged B10—B11 and B8—B9 edges slightly increase by ca 0.04 Å, from 1.853 (3) to 1.892 (3) Å. The shortening of the B7 vertex may be ascribed to its more intimate intracluster bonding. On deprotonation, the electron pair and the associated orbital in the endo-terminal B7—H bond become involved in direct cluster bonding. A similar, albeit smaller, effect may be noted in the formally isoelectronic isostructural pair [B₁₁H₁₄]⁻ and [B₁₁H₁₃]²⁻ (Getman et al., 1988; Fitchie, 1967), viz. 1.89 to 1.80 Å for B7—B8/B11. This may also be reflected in the decrease of the S—B7 distance, 1.910 (3) to 1.8829 (19) Å, and in the upward tilt of the S—B7 vector towards the plane of the open-face atoms defined by the centroid of B7/B8/B9/B10/B11 [from 164.2° in (I) to 154.0° in (II)]. There may also be some additional steric relief as the Me₂S group rotates to allow a methyl group to fill the vacancy created by the loss of the proton.

Compound (II) may be directly compared with its isostructural analogue [NBzEt₃][7-(C₅H₄N)-nido-B₁₁H₁₂], (III) (Volkov et al., 2001), in which the ligand is a pyridine group. There are no significant difference in the cluster interatomic dimensions between the two molecules. The bridging-H-atom assymmetry that is often observed in boron hydrides (Beaudet, 1988) and has been noted for (I) and (III) is mirrored in (II), with the long B—H(bridge) distance [ca 1.32 (2) Å] being toward the B7 vertex.

Finally, we note that the N,N,N',N'-tetramethyl-1,8-diaminonapthalenide salt of (II) may be obtained more conveniently and in high yield by deprotonation of (I) with the mild non-nucleophilic base N,N,N',N'-tetramethyl-1,8-diaminonapthalene.

S2. Experimental

Compound (II) was obtained in an experiment to produce K₂[B₁₁H₁₁] according to the method of Volkov (1999), in which a reduced yield of the target compound was obtained. A pale-yellow residue, remaining after filtering off the solid K₂[B₁₁H₁₁] product and reducing the THF filtrate to dryness, was extracted with two aliquots of diethylether. ¹¹B NMR spectrometry of the first aliquot showed it to be predominantly one compound together with a small amount of K₂[B₁₁H₁₁]. After removal of ether, a white powder was obtained (19% based on K[Me₂SB₁₁H₁₂]), a portion of which was dissolved in water and added to a solution of [Et₄N]Cl:xH₂O to yield compound (II). Colourless single crystals were grown by hexane diffusion into a CD₂Cl₂ solution of the compound. The second aliquot was almost pure K₂[B₁₁H₁₁]. The N,N,N',N'-tetramethyl-1,8-diaminonaphthalenide salt of (II) may be produced directly by addition of N,N,N',N'-tetramethyl-1,8-diaminonaphthalene (Proton Sponge) to (I) dissolved in a minimum of CHCl₃. Crystals of the compound drop out of solution overnight. Analysis; ¹¹B NMR for (II) [p.p.m., 96.3 MHz, CD₂Cl₂, 298 K; assignments by comparison with (III) (Volkov et al., 2001), for which the chemical shift values are shown in square brackets]: B7/5 − 7.9 [+3.4, −11.5], B2/3 − 13.3 [−12.3], B8/11 − 17.7 [−18.7], B9/10 − 23.3 [−24.7], B1 − 29.1 [−29.1], B4/6 − 30.1 [−31.6]; δ(¹H) with relative intensities in parentheses: +1.76 (1), +1.32 (4), +0.83 (1), +0.69 (1) +0.39 (3), −4.90 (2) and +2.46 (6). The measured ¹¹B and ¹H NMR spectra for both compounds show very similar chemical shift values, except for the resonance due to the B7 vertex, which is shifted to higher field by −11.3 p.p.m. The resonance due to the antipodal B5 vertex also moves slightly to higher field (−2.6 p.p.m.).

S3. Refinement

Cluster H atoms were located via Fourier difference syntheses, with positional and isotropic displacement parameters freely refined and B—H_terminal distances in the range 1.084 (18)–1.140 (18) Å. H atoms attached to the C atoms of the cation were treated using the SHELXL97 (Sheldrick, 1997) defaults. Methyl groups in the dimethyl sulfide cluster substituent and ethyl groups in the cation were included in calculated positions, with a refined rotational parameter for each methyl or ethyl group and U_iso values of 1.5–1.2 times the U_eq value of the parent C atom.

Computing details

Data collection: COLLECT (Nonius, 1997–2000); cell refinement: HKL SCALEPACK (Otwinowski & Minor 1997); data reduction: HKL DENZO (Otwinowski & Minor 1997) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

Fig. 1. The anion in (II), with displacement ellipsoids shown at the 50% probability level.

[Tetraethylammonium][7-dimethylsulfide-nido-dodecahydroundecaborate]

Crystal data

C8H20N^+·C2H18B11S^−	F(000) = 704
Mr = 323.38	Dx = 1.041 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P2ybc	Cell parameters from 3666 reflections
a = 10.5939 (3) Å	θ = 1.0–25.0°
b = 11.7359 (3) Å	µ = 0.15 mm^−1
c = 16.9528 (4) Å	T = 173 K
β = 101.666 (1)°	Needle, colourless
V = 2064.18 (9) Å^3	0.32 × 0.22 × 0.12 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer	2821 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.033
Graphite monochromator	θmax = 25.0°, θmin = 2.6°
Detector resolution: 9 pixels mm^-1	h = −12→12
CCD scans	k = −13→12
6232 measured reflections	l = −20→20
3628 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.096	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0345P)^2 + 0.8016P] where P = (Fo^2 + 2Fc^2)/3
3628 reflections	(Δ/σ)max < 0.001
256 parameters	Δρmax = 0.18 e Å^−3
0 restraints	Δρmin = −0.23 e Å^−3

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

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

	x	y	z	Uiso*/Ueq
S	0.05411 (4)	0.03318 (4)	0.22159 (3)	0.02434 (14)
C12	−0.11657 (17)	0.02979 (18)	0.18459 (12)	0.0334 (5)
H12A	−0.1561	−0.0235	0.2170	0.050*
H12B	−0.1347	0.0048	0.1283	0.050*
H12C	−0.1523	0.1062	0.1883	0.050*
C13	0.0597 (2)	0.0993 (2)	0.31727 (11)	0.0396 (5)
H13A	0.0197	0.1748	0.3093	0.059*
H13B	0.1496	0.1070	0.3455	0.059*
H13C	0.0127	0.0522	0.3495	0.059*
B1	0.3201 (2)	0.27822 (18)	0.12985 (13)	0.0239 (5)
B2	0.21021 (19)	0.25461 (17)	0.19455 (12)	0.0223 (4)
B3	0.27632 (19)	0.13810 (17)	0.15197 (12)	0.0217 (4)
B4	0.2880 (2)	0.17349 (18)	0.05140 (13)	0.0253 (5)
B5	0.2305 (2)	0.31648 (17)	0.03487 (13)	0.0247 (5)
B6	0.1806 (2)	0.36743 (17)	0.12230 (12)	0.0236 (5)
B7	0.11244 (19)	0.14065 (17)	0.15462 (12)	0.0205 (4)
B8	0.1561 (2)	0.08697 (17)	0.06757 (12)	0.0228 (4)
B9	0.1351 (2)	0.20274 (18)	−0.01136 (13)	0.0281 (5)
B10	0.0651 (2)	0.32797 (18)	0.03453 (13)	0.0262 (5)
B11	0.05001 (19)	0.27941 (17)	0.13883 (12)	0.0220 (4)
H1	0.4152 (17)	0.3138 (15)	0.1518 (10)	0.023 (5)*
H2	0.2311 (17)	0.2749 (15)	0.2598 (11)	0.028 (5)*
H3	0.3457 (17)	0.0777 (15)	0.1895 (10)	0.025 (5)*
H4	0.3706 (18)	0.1396 (16)	0.0252 (11)	0.035 (5)*
H5	0.2668 (16)	0.3740 (15)	−0.0073 (10)	0.026 (5)*
H6	0.1911 (17)	0.4585 (16)	0.1424 (11)	0.032 (5)*
H8	0.1524 (17)	−0.0064 (16)	0.0486 (11)	0.027 (5)*
H9	0.1283 (19)	0.1857 (18)	−0.0755 (13)	0.045 (6)*
H9B	0.0631 (19)	0.1414 (18)	0.0153 (12)	0.043 (6)*
H10	0.0044 (19)	0.3951 (17)	0.0001 (11)	0.038 (5)*
H10B	−0.0014 (19)	0.2623 (17)	0.0636 (12)	0.042 (6)*
H11	−0.0251 (16)	0.3174 (15)	0.1695 (10)	0.024 (5)*
N	0.40988 (13)	0.74484 (12)	0.10833 (8)	0.0225 (3)
C14	0.29352 (18)	0.70354 (18)	0.04765 (12)	0.0340 (5)
H14A	0.2758	0.6236	0.0606	0.041*
H14B	0.2179	0.7497	0.0539	0.041*
C15	0.3068 (2)	0.7092 (2)	−0.03952 (12)	0.0474 (6)
H15A	0.3072	0.7891	−0.0564	0.071*
H15B	0.2341	0.6695	−0.0734	0.071*
H15C	0.3877	0.6727	−0.0453	0.071*
C16	0.3836 (2)	0.72729 (17)	0.19227 (11)	0.0332 (5)
H16A	0.3584	0.6468	0.1974	0.040*
H16B	0.4648	0.7403	0.2319	0.040*
C17	0.2801 (2)	0.80299 (19)	0.21416 (14)	0.0478 (6)
H17A	0.3088	0.8825	0.2162	0.072*
H17B	0.2642	0.7806	0.2670	0.072*
H17C	0.2005	0.7949	0.1735	0.072*
C18	0.53029 (17)	0.67862 (15)	0.10206 (12)	0.0270 (4)
H18A	0.5514	0.6943	0.0488	0.032*
H18B	0.6027	0.7074	0.1436	0.032*
C19	0.5212 (2)	0.55113 (16)	0.11194 (13)	0.0364 (5)
H19A	0.4988	0.5342	0.1640	0.055*
H19B	0.6043	0.5161	0.1097	0.055*
H19C	0.4545	0.5204	0.0685	0.055*
C20	0.43215 (17)	0.86994 (15)	0.09177 (11)	0.0254 (4)
H20A	0.4446	0.8772	0.0357	0.030*
H20B	0.3533	0.9130	0.0957	0.030*
C21	0.54558 (18)	0.92491 (16)	0.14709 (13)	0.0341 (5)
H21A	0.5384	0.9130	0.2032	0.051*
H21B	0.5462	1.0068	0.1359	0.051*
H21C	0.6258	0.8906	0.1381	0.051*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S	0.0259 (3)	0.0215 (2)	0.0276 (2)	−0.0010 (2)	0.01006 (18)	0.0029 (2)
C12	0.0274 (11)	0.0394 (11)	0.0337 (11)	−0.0126 (9)	0.0066 (8)	−0.0020 (9)
C13	0.0436 (13)	0.0525 (14)	0.0235 (10)	−0.0177 (11)	0.0090 (9)	−0.0027 (10)
B1	0.0200 (11)	0.0236 (11)	0.0285 (11)	−0.0015 (9)	0.0057 (9)	0.0030 (9)
B2	0.0222 (11)	0.0228 (11)	0.0225 (10)	−0.0026 (9)	0.0058 (8)	−0.0002 (9)
B3	0.0199 (10)	0.0206 (10)	0.0246 (10)	0.0012 (9)	0.0043 (8)	0.0011 (9)
B4	0.0289 (12)	0.0213 (11)	0.0285 (11)	0.0045 (9)	0.0123 (9)	0.0025 (9)
B5	0.0282 (12)	0.0212 (11)	0.0271 (11)	0.0023 (9)	0.0115 (9)	0.0045 (9)
B6	0.0265 (11)	0.0185 (10)	0.0271 (11)	0.0002 (9)	0.0082 (9)	−0.0001 (9)
B7	0.0199 (10)	0.0211 (10)	0.0210 (10)	−0.0014 (8)	0.0054 (8)	0.0012 (8)
B8	0.0271 (11)	0.0185 (10)	0.0233 (10)	0.0030 (9)	0.0065 (9)	0.0012 (9)
B9	0.0392 (13)	0.0229 (11)	0.0229 (11)	0.0015 (10)	0.0079 (10)	0.0022 (9)
B10	0.0272 (12)	0.0232 (11)	0.0284 (11)	0.0035 (9)	0.0058 (9)	0.0038 (9)
B11	0.0225 (11)	0.0200 (10)	0.0246 (11)	0.0011 (9)	0.0075 (9)	−0.0008 (8)
N	0.0184 (8)	0.0233 (8)	0.0256 (8)	0.0007 (6)	0.0041 (6)	0.0003 (6)
C14	0.0181 (10)	0.0415 (12)	0.0395 (12)	−0.0012 (9)	−0.0010 (8)	−0.0081 (10)
C15	0.0419 (13)	0.0606 (15)	0.0343 (12)	0.0058 (12)	−0.0048 (10)	−0.0122 (11)
C16	0.0449 (12)	0.0295 (10)	0.0275 (10)	−0.0039 (9)	0.0126 (9)	0.0025 (9)
C17	0.0648 (15)	0.0381 (12)	0.0522 (14)	−0.0050 (11)	0.0395 (12)	−0.0029 (11)
C18	0.0197 (10)	0.0234 (10)	0.0369 (11)	0.0037 (8)	0.0033 (8)	−0.0012 (8)
C19	0.0415 (12)	0.0252 (10)	0.0428 (12)	0.0041 (9)	0.0089 (10)	−0.0021 (9)
C20	0.0228 (10)	0.0217 (9)	0.0328 (10)	0.0046 (8)	0.0083 (8)	0.0058 (8)
C21	0.0298 (11)	0.0214 (10)	0.0508 (13)	−0.0008 (8)	0.0072 (9)	0.0009 (9)

Geometric parameters (Å, º)

S—C12	1.7904 (19)	B5—H5	1.108 (18)
S—C13	1.7881 (19)	B6—H6	1.120 (19)
S—B7	1.8829 (19)	B8—H8	1.140 (18)
B1—B2	1.776 (3)	B9—H9	1.09 (2)
B1—B3	1.769 (3)	B10—H10	1.11 (2)
B1—B4	1.792 (3)	B11—H11	1.127 (17)
B1—B5	1.754 (3)	B8—H9B	1.34 (2)
B1—B6	1.794 (3)	B9—H9B	1.20 (2)
B2—B3	1.757 (3)	B10—H10B	1.21 (2)
B2—B6	1.788 (3)	B11—H10B	1.30 (2)
B2—B7	1.743 (3)	N—C16	1.518 (2)
B2—B11	1.791 (3)	N—C14	1.517 (2)
B3—B4	1.783 (3)	N—C18	1.516 (2)
B3—B7	1.746 (3)	N—C20	1.522 (2)
B3—B8	1.815 (3)	C14—C15	1.514 (3)
B4—B5	1.788 (3)	C14—H14A	0.9900
B4—B8	1.793 (3)	C14—H14B	0.9900
B4—B9	1.782 (3)	C15—H15A	0.9800
B5—B9	1.760 (3)	C15—H15B	0.9800
B5—B6	1.775 (3)	C15—H15C	0.9800
B5—B10	1.757 (3)	C16—C17	1.514 (3)
B6—B10	1.786 (3)	C16—H16A	0.9900
B6—B11	1.794 (3)	C16—H16B	0.9900
B7—B8	1.750 (3)	C17—H17A	0.9800
B7—B11	1.758 (3)	C17—H17B	0.9800
B8—B9	1.888 (3)	C17—H17C	0.9800
B9—B10	1.884 (3)	C18—C19	1.511 (2)
B10—B11	1.895 (3)	C18—H18A	0.9900
C12—H12A	0.9800	C18—H18B	0.9900
C12—H12B	0.9800	C19—H19A	0.9800
C12—H12C	0.9800	C19—H19B	0.9800
C13—H13A	0.9800	C19—H19C	0.9800
C13—H13B	0.9800	C20—C21	1.511 (3)
C13—H13C	0.9800	C20—H20A	0.9900
B1—H1	1.084 (18)	C20—H20B	0.9900
B2—H2	1.110 (18)	C21—H21A	0.9800
B3—H3	1.122 (18)	C21—H21B	0.9800
B4—H4	1.130 (18)	C21—H21C	0.9800
C13—S—C12	99.97 (9)	B8—B7—S	116.24 (13)
C13—S—B7	107.57 (9)	B11—B7—S	123.58 (12)
C12—S—B7	103.59 (9)	B7—B8—B4	105.78 (14)
S—C12—H12A	109.5	B7—B8—B3	58.61 (11)
S—C12—H12B	109.5	B4—B8—B3	59.23 (11)
H12A—C12—H12B	109.5	B7—B8—B9	108.98 (14)
S—C12—H12C	109.5	B4—B8—B9	57.85 (11)
H12A—C12—H12C	109.5	B3—B8—B9	106.49 (14)
H12B—C12—H12C	109.5	B7—B8—H8	125.8 (9)
S—C13—H13A	109.5	B4—B8—H8	118.9 (9)
S—C13—H13B	109.5	B3—B8—H8	121.2 (9)
H13A—C13—H13B	109.5	B9—B8—H8	119.9 (9)
S—C13—H13C	109.5	B7—B8—H9B	95.8 (8)
H13A—C13—H13C	109.5	B4—B8—H9B	96.9 (9)
H13B—C13—H13C	109.5	B3—B8—H9B	131.8 (9)
B5—B1—B3	108.42 (15)	H8—B8—H9B	107.0 (13)
B5—B1—B2	107.83 (14)	B5—B9—B4	60.62 (12)
B3—B1—B2	59.41 (11)	B5—B9—B10	57.53 (11)
B5—B1—B4	60.54 (12)	B4—B9—B10	106.86 (15)
B3—B1—B4	60.09 (11)	B5—B9—B8	104.81 (14)
B2—B1—B4	107.55 (14)	B4—B9—B8	58.40 (11)
B5—B1—B6	60.01 (11)	B10—B9—B8	105.57 (14)
B3—B1—B6	108.05 (14)	B5—B9—H9	119.9 (11)
B2—B1—B6	60.10 (11)	B4—B9—H9	115.3 (11)
B4—B1—B6	108.49 (15)	B10—B9—H9	126.9 (11)
B5—B1—H1	120.6 (9)	B8—B9—H9	123.2 (11)
B3—B1—H1	123.4 (9)	B5—B9—H9B	129.6 (10)
B2—B1—H1	121.9 (9)	B4—B9—H9B	103.2 (10)
B4—B1—H1	122.8 (9)	B10—B9—H9B	88.8 (10)
B6—B1—H1	119.6 (9)	H9—B9—H9B	110.2 (14)
B7—B2—B3	59.87 (11)	B5—B10—B6	60.12 (12)
B7—B2—B1	107.00 (14)	B5—B10—B9	57.69 (12)
B3—B2—B1	60.12 (11)	B6—B10—B9	106.58 (14)
B7—B2—B6	107.11 (14)	B5—B10—B11	104.24 (14)
B3—B2—B6	108.91 (14)	B6—B10—B11	58.24 (11)
B1—B2—B6	60.47 (11)	B9—B10—B11	105.38 (14)
B7—B2—B11	59.64 (11)	B5—B10—H10	122.0 (10)
B3—B2—B11	108.89 (14)	B6—B10—H10	118.8 (10)
B1—B2—B11	108.58 (14)	B9—B10—H10	125.0 (10)
B6—B2—B11	60.15 (11)	B11—B10—H10	123.9 (10)
B7—B2—H2	122.4 (9)	B5—B10—H10B	127.6 (9)
B3—B2—H2	124.2 (9)	B6—B10—H10B	100.5 (10)
B1—B2—H2	124.0 (9)	B9—B10—H10B	88.9 (9)
B6—B2—H2	119.7 (9)	H10—B10—H10B	110.1 (14)
B11—B2—H2	117.9 (9)	B7—B11—B2	58.80 (11)
B7—B3—B2	59.67 (11)	B7—B11—B6	106.20 (14)
B7—B3—B1	107.12 (14)	B2—B11—B6	59.83 (11)
B2—B3—B1	60.47 (11)	B7—B11—B10	108.70 (14)
B7—B3—B4	106.40 (14)	B2—B11—B10	106.94 (13)
B2—B3—B4	108.80 (14)	B6—B11—B10	57.85 (11)
B1—B3—B4	60.60 (11)	B7—B11—H10B	94.4 (9)
B7—B3—B8	58.85 (11)	B2—B11—H10B	131.1 (9)
B2—B3—B8	107.86 (14)	B6—B11—H10B	96.8 (9)
B1—B3—B8	108.22 (14)	B7—B11—H11	125.1 (9)
B4—B3—B8	59.78 (11)	B2—B11—H11	120.2 (9)
B7—B3—H3	122.5 (9)	B6—B11—H11	118.9 (9)
B2—B3—H3	121.9 (9)	B10—B11—H11	120.8 (9)
B1—B3—H3	122.5 (9)	H10B—B11—H11	108.6 (12)
B4—B3—H3	121.7 (9)	C18—N—C14	111.64 (14)
B8—B3—H3	120.9 (9)	C18—N—C16	108.21 (14)
B9—B4—B3	112.65 (14)	C14—N—C16	108.33 (14)
B9—B4—B5	59.06 (12)	C18—N—C20	108.52 (13)
B3—B4—B5	106.32 (14)	C14—N—C20	108.56 (14)
B9—B4—B1	108.91 (14)	C16—N—C20	111.62 (13)
B3—B4—B1	59.32 (11)	C15—C14—N	115.14 (16)
B5—B4—B1	58.68 (12)	C15—C14—H14A	108.5
B9—B4—B8	63.75 (12)	N—C14—H14A	108.5
B3—B4—B8	60.99 (11)	C15—C14—H14B	108.5
B5—B4—B8	107.69 (14)	N—C14—H14B	108.5
B1—B4—B8	108.17 (14)	H14A—C14—H14B	107.5
B9—B4—H4	121.0 (10)	C14—C15—H15A	109.5
B3—B4—H4	120.2 (10)	C14—C15—H15B	109.5
B5—B4—H4	122.3 (10)	H15A—C15—H15B	109.5
B1—B4—H4	119.1 (10)	C14—C15—H15C	109.5
B8—B4—H4	123.4 (10)	H15A—C15—H15C	109.5
B1—B5—B10	112.15 (15)	H15B—C15—H15C	109.5
B1—B5—B9	111.72 (15)	C17—C16—N	115.40 (16)
B10—B5—B9	64.78 (13)	C17—C16—H16A	108.4
B1—B5—B6	61.12 (12)	N—C16—H16A	108.4
B10—B5—B6	60.76 (12)	C17—C16—H16B	108.4
B9—B5—B6	112.72 (15)	N—C16—H16B	108.4
B1—B5—B4	60.78 (12)	H16A—C16—H16B	107.5
B10—B5—B4	112.37 (15)	C16—C17—H17A	109.5
B9—B5—B4	60.31 (12)	C16—C17—H17B	109.5
B6—B5—B4	109.56 (14)	H17A—C17—H17B	109.5
B1—B5—H5	123.7 (9)	C16—C17—H17C	109.5
B10—B5—H5	115.3 (9)	H17A—C17—H17C	109.5
B9—B5—H5	114.7 (9)	H17B—C17—H17C	109.5
B6—B5—H5	122.3 (9)	C19—C18—N	115.24 (15)
B4—B5—H5	121.5 (9)	C19—C18—H18A	108.5
B5—B6—B10	59.12 (12)	N—C18—H18A	108.5
B5—B6—B2	106.38 (14)	C19—C18—H18B	108.5
B10—B6—B2	111.98 (15)	N—C18—H18B	108.5
B5—B6—B11	107.81 (14)	H18A—C18—H18B	107.5
B10—B6—B11	63.92 (12)	C18—C19—H19A	109.5
B2—B6—B11	60.02 (11)	C18—C19—H19B	109.5
B5—B6—B1	58.87 (11)	H19A—C19—H19B	109.5
B10—B6—B1	108.91 (14)	C18—C19—H19C	109.5
B2—B6—B1	59.42 (11)	H19A—C19—H19C	109.5
B11—B6—B1	107.64 (14)	H19B—C19—H19C	109.5
B5—B6—H6	123.2 (9)	C21—C20—N	115.51 (14)
B10—B6—H6	120.6 (10)	C21—C20—H20A	108.4
B2—B6—H6	120.4 (10)	N—C20—H20A	108.4
B11—B6—H6	122.3 (9)	C21—C20—H20B	108.4
B1—B6—H6	120.4 (10)	N—C20—H20B	108.4
B2—B7—B3	60.47 (11)	H20A—C20—H20B	107.5
B2—B7—B8	111.49 (14)	C20—C21—H21A	109.5
B3—B7—B8	62.53 (11)	C20—C21—H21B	109.5
B2—B7—B11	61.56 (11)	H21A—C21—H21B	109.5
B3—B7—B11	110.94 (14)	C20—C21—H21C	109.5
B8—B7—B11	111.13 (14)	H21A—C21—H21C	109.5
B2—B7—S	121.44 (13)	H21B—C21—H21C	109.5
B3—B7—S	116.96 (13)
B5—B1—B2—B7	62.63 (18)	B2—B3—B7—B8	140.25 (15)
B3—B1—B2—B7	−38.64 (13)	B1—B3—B7—B8	101.31 (15)
B4—B1—B2—B7	−1.25 (19)	B4—B3—B7—B8	37.73 (13)
B6—B1—B2—B7	100.40 (15)	B2—B3—B7—B11	36.60 (14)
B5—B1—B2—B3	101.27 (16)	B1—B3—B7—B11	−2.34 (19)
B4—B1—B2—B3	37.38 (14)	B4—B3—B7—B11	−65.92 (17)
B6—B1—B2—B3	139.03 (15)	B8—B3—B7—B11	−103.65 (15)
B5—B1—B2—B6	−37.76 (14)	B2—B3—B7—S	−112.61 (15)
B3—B1—B2—B6	−139.03 (15)	B1—B3—B7—S	−151.56 (12)
B4—B1—B2—B6	−101.65 (16)	B4—B3—B7—S	144.86 (13)
B5—B1—B2—B11	−0.31 (19)	B8—B3—B7—S	107.13 (15)
B3—B1—B2—B11	−101.58 (15)	C13—S—B7—B2	22.63 (17)
B4—B1—B2—B11	−64.20 (17)	C12—S—B7—B2	127.91 (15)
B6—B1—B2—B11	37.45 (13)	C13—S—B7—B3	92.93 (15)
B1—B2—B3—B7	−136.34 (15)	C12—S—B7—B3	−161.80 (13)
B6—B2—B3—B7	−99.25 (15)	C13—S—B7—B8	163.89 (14)
B11—B2—B3—B7	−35.28 (13)	C12—S—B7—B8	−90.84 (14)
B7—B2—B3—B1	136.34 (15)	C13—S—B7—B11	−52.06 (17)
B6—B2—B3—B1	37.09 (14)	C12—S—B7—B11	53.21 (17)
B11—B2—B3—B1	101.06 (15)	B2—B7—B8—B4	−0.62 (19)
B7—B2—B3—B4	98.42 (15)	B3—B7—B8—B4	−37.34 (13)
B1—B2—B3—B4	−37.92 (14)	B11—B7—B8—B4	66.01 (17)
B6—B2—B3—B4	−0.84 (19)	S—B7—B8—B4	−145.61 (13)
B11—B2—B3—B4	63.14 (17)	B2—B7—B8—B3	36.72 (14)
B7—B2—B3—B8	35.09 (13)	B11—B7—B8—B3	103.35 (15)
B1—B2—B3—B8	−101.25 (15)	S—B7—B8—B3	−108.27 (15)
B6—B2—B3—B8	−64.16 (17)	B2—B7—B8—B9	−61.44 (19)
B11—B2—B3—B8	−0.19 (18)	B3—B7—B8—B9	−98.16 (15)
B5—B1—B3—B7	−61.68 (17)	B11—B7—B8—B9	5.20 (19)
B2—B1—B3—B7	38.57 (13)	S—B7—B8—B9	153.58 (13)
B4—B1—B3—B7	−99.53 (15)	B9—B4—B8—B7	−102.80 (15)
B6—B1—B3—B7	1.86 (19)	B3—B4—B8—B7	37.06 (13)
B5—B1—B3—B2	−100.25 (15)	B5—B4—B8—B7	−62.17 (17)
B4—B1—B3—B2	−138.10 (15)	B1—B4—B8—B7	−0.18 (19)
B6—B1—B3—B2	−36.71 (13)	B9—B4—B8—B3	−139.86 (14)
B5—B1—B3—B4	37.85 (13)	B5—B4—B8—B3	−99.23 (15)
B2—B1—B3—B4	138.10 (15)	B1—B4—B8—B3	−37.24 (13)
B6—B1—B3—B4	101.38 (16)	B3—B4—B8—B9	139.86 (14)
B5—B1—B3—B8	0.39 (18)	B5—B4—B8—B9	40.63 (13)
B2—B1—B3—B8	100.64 (15)	B1—B4—B8—B9	102.62 (16)
B4—B1—B3—B8	−37.46 (13)	B2—B3—B8—B7	−35.44 (13)
B6—B1—B3—B8	63.92 (17)	B1—B3—B8—B7	−99.39 (15)
B7—B3—B4—B9	1.5 (2)	B4—B3—B8—B7	−137.21 (15)
B2—B3—B4—B9	−61.38 (19)	B7—B3—B8—B4	137.21 (15)
B1—B3—B4—B9	−99.25 (16)	B2—B3—B8—B4	101.77 (15)
B8—B3—B4—B9	38.79 (14)	B1—B3—B8—B4	37.82 (13)
B7—B3—B4—B5	64.22 (17)	B7—B3—B8—B9	102.51 (15)
B2—B3—B4—B5	1.34 (19)	B2—B3—B8—B9	67.08 (16)
B1—B3—B4—B5	−36.52 (14)	B1—B3—B8—B9	3.13 (17)
B8—B3—B4—B5	101.52 (15)	B4—B3—B8—B9	−34.70 (13)
B7—B3—B4—B1	100.74 (15)	B1—B5—B9—B4	−33.70 (14)
B2—B3—B4—B1	37.87 (14)	B10—B5—B9—B4	−138.83 (15)
B8—B3—B4—B1	138.04 (15)	B6—B5—B9—B4	−100.32 (16)
B7—B3—B4—B8	−37.30 (13)	B1—B5—B9—B10	105.13 (16)
B2—B3—B4—B8	−100.18 (15)	B6—B5—B9—B10	38.51 (14)
B1—B3—B4—B8	−138.04 (15)	B4—B5—B9—B10	138.83 (15)
B5—B1—B4—B9	−32.38 (14)	B1—B5—B9—B8	5.88 (19)
B3—B1—B4—B9	105.67 (16)	B10—B5—B9—B8	−99.25 (15)
B2—B1—B4—B9	68.58 (17)	B6—B5—B9—B8	−60.74 (18)
B6—B1—B4—B9	5.03 (19)	B4—B5—B9—B8	39.58 (13)
B5—B1—B4—B3	−138.04 (15)	B3—B4—B9—B5	96.03 (16)
B2—B1—B4—B3	−37.09 (13)	B1—B4—B9—B5	32.23 (14)
B6—B1—B4—B3	−100.63 (15)	B8—B4—B9—B5	133.68 (15)
B3—B1—B4—B5	138.04 (15)	B3—B4—B9—B10	60.56 (18)
B2—B1—B4—B5	100.96 (15)	B5—B4—B9—B10	−35.47 (13)
B6—B1—B4—B5	37.41 (13)	B1—B4—B9—B10	−3.24 (19)
B5—B1—B4—B8	−100.07 (15)	B8—B4—B9—B10	98.21 (15)
B3—B1—B4—B8	37.98 (13)	B3—B4—B9—B8	−37.65 (14)
B2—B1—B4—B8	0.89 (19)	B5—B4—B9—B8	−133.68 (15)
B6—B1—B4—B8	−62.66 (17)	B1—B4—B9—B8	−101.45 (15)
B3—B1—B5—B10	66.43 (18)	B7—B8—B9—B5	56.41 (18)
B2—B1—B5—B10	3.6 (2)	B4—B8—B9—B5	−40.68 (14)
B4—B1—B5—B10	104.08 (16)	B3—B8—B9—B5	−5.39 (18)
B6—B1—B5—B10	−34.23 (14)	B7—B8—B9—B4	97.09 (15)
B3—B1—B5—B9	−4.1 (2)	B3—B8—B9—B4	35.29 (13)
B2—B1—B5—B9	−66.98 (18)	B7—B8—B9—B10	−3.40 (19)
B4—B1—B5—B9	33.52 (14)	B4—B8—B9—B10	−100.49 (15)
B6—B1—B5—B9	−104.78 (16)	B3—B8—B9—B10	−65.20 (17)
B3—B1—B5—B6	100.66 (15)	B1—B5—B10—B6	34.36 (14)
B2—B1—B5—B6	37.81 (14)	B9—B5—B10—B6	138.84 (15)
B4—B1—B5—B6	138.30 (15)	B4—B5—B10—B6	100.64 (16)
B3—B1—B5—B4	−37.65 (13)	B1—B5—B10—B9	−104.48 (16)
B2—B1—B5—B4	−100.50 (15)	B6—B5—B10—B9	−138.84 (15)
B6—B1—B5—B4	−138.30 (15)	B4—B5—B10—B9	−38.20 (14)
B9—B4—B5—B1	143.80 (15)	B1—B5—B10—B11	−5.08 (19)
B3—B4—B5—B1	36.81 (13)	B9—B5—B10—B11	99.40 (15)
B8—B4—B5—B1	100.89 (15)	B6—B5—B10—B11	−39.44 (13)
B9—B4—B5—B10	40.09 (15)	B4—B5—B10—B11	61.20 (18)
B3—B4—B5—B10	−66.90 (19)	B2—B6—B10—B5	−96.49 (15)
B1—B4—B5—B10	−103.71 (16)	B11—B6—B10—B5	−133.59 (14)
B8—B4—B5—B10	−2.8 (2)	B1—B6—B10—B5	−32.70 (13)
B3—B4—B5—B9	−106.99 (16)	B5—B6—B10—B9	35.48 (13)
B1—B4—B5—B9	−143.80 (15)	B2—B6—B10—B9	−61.01 (18)
B8—B4—B5—B9	−42.91 (14)	B11—B6—B10—B9	−98.11 (15)
B9—B4—B5—B6	105.62 (16)	B1—B6—B10—B9	2.78 (18)
B3—B4—B5—B6	−1.4 (2)	B5—B6—B10—B11	133.59 (14)
B1—B4—B5—B6	−38.18 (14)	B2—B6—B10—B11	37.10 (13)
B8—B4—B5—B6	62.71 (18)	B1—B6—B10—B11	100.90 (15)
B1—B5—B6—B10	−143.34 (15)	B4—B9—B10—B5	36.83 (14)
B9—B5—B6—B10	−40.21 (15)	B8—B9—B10—B5	97.89 (16)
B4—B5—B6—B10	−105.31 (16)	B5—B9—B10—B6	−36.55 (13)
B1—B5—B6—B2	−37.16 (13)	B4—B9—B10—B6	0.28 (18)
B10—B5—B6—B2	106.18 (15)	B8—B9—B10—B6	61.34 (17)
B9—B5—B6—B2	65.97 (19)	B5—B9—B10—B11	−97.35 (15)
B4—B5—B6—B2	0.87 (19)	B4—B9—B10—B11	−60.53 (17)
B1—B5—B6—B11	−100.25 (15)	B8—B9—B10—B11	0.53 (18)
B10—B5—B6—B11	43.09 (14)	B3—B7—B11—B2	−36.16 (13)
B9—B5—B6—B11	2.9 (2)	B8—B7—B11—B2	−103.73 (15)
B4—B5—B6—B11	−62.21 (18)	S—B7—B11—B2	110.64 (16)
B10—B5—B6—B1	143.34 (15)	B2—B7—B11—B6	38.02 (13)
B9—B5—B6—B1	103.13 (16)	B3—B7—B11—B6	1.86 (19)
B4—B5—B6—B1	38.03 (14)	B8—B7—B11—B6	−65.71 (17)
B7—B2—B6—B5	−63.29 (17)	S—B7—B11—B6	148.66 (13)
B3—B2—B6—B5	−0.02 (19)	B2—B7—B11—B10	98.89 (15)
B1—B2—B6—B5	36.91 (14)	B3—B7—B11—B10	62.74 (18)
B11—B2—B6—B5	−101.44 (15)	B8—B7—B11—B10	−4.83 (19)
B7—B2—B6—B10	−0.57 (19)	S—B7—B11—B10	−150.46 (13)
B3—B2—B6—B10	62.70 (18)	B3—B2—B11—B7	35.37 (13)
B1—B2—B6—B10	99.64 (16)	B1—B2—B11—B7	99.24 (15)
B11—B2—B6—B10	−38.72 (14)	B6—B2—B11—B7	136.83 (14)
B7—B2—B6—B11	38.15 (13)	B7—B2—B11—B6	−136.83 (14)
B3—B2—B6—B11	101.42 (15)	B3—B2—B11—B6	−101.46 (15)
B1—B2—B6—B11	138.35 (15)	B1—B2—B11—B6	−37.59 (13)
B7—B2—B6—B1	−100.21 (15)	B7—B2—B11—B10	−101.97 (15)
B3—B2—B6—B1	−36.93 (14)	B3—B2—B11—B10	−66.60 (17)
B11—B2—B6—B1	−138.35 (15)	B1—B2—B11—B10	−2.73 (18)
B3—B1—B6—B5	−101.28 (16)	B6—B2—B11—B10	34.86 (13)
B2—B1—B6—B5	−137.69 (15)	B5—B6—B11—B7	61.47 (17)
B4—B1—B6—B5	−37.64 (13)	B10—B6—B11—B7	102.23 (15)
B5—B1—B6—B10	32.79 (14)	B2—B6—B11—B7	−37.55 (13)
B3—B1—B6—B10	−68.49 (17)	B1—B6—B11—B7	−0.65 (18)
B2—B1—B6—B10	−104.90 (16)	B5—B6—B11—B2	99.02 (15)
B4—B1—B6—B10	−4.85 (19)	B10—B6—B11—B2	139.77 (14)
B5—B1—B6—B2	137.69 (15)	B1—B6—B11—B2	36.90 (13)
B3—B1—B6—B2	36.41 (13)	B5—B6—B11—B10	−40.75 (13)
B4—B1—B6—B2	100.05 (15)	B2—B6—B11—B10	−139.77 (14)
B5—B1—B6—B11	100.53 (15)	B1—B6—B11—B10	−102.88 (15)
B3—B1—B6—B11	−0.74 (19)	B5—B10—B11—B7	−57.38 (17)
B2—B1—B6—B11	−37.16 (13)	B6—B10—B11—B7	−97.76 (15)
B4—B1—B6—B11	62.89 (17)	B9—B10—B11—B7	2.48 (18)
B1—B2—B7—B3	38.75 (13)	B5—B10—B11—B2	4.68 (18)
B6—B2—B7—B3	102.32 (15)	B6—B10—B11—B2	−35.71 (13)
B11—B2—B7—B3	140.71 (14)	B9—B10—B11—B2	64.54 (17)
B3—B2—B7—B8	−37.57 (14)	B5—B10—B11—B6	40.38 (13)
B1—B2—B7—B8	1.18 (19)	B9—B10—B11—B6	100.24 (15)
B6—B2—B7—B8	64.75 (18)	C18—N—C14—C15	−57.8 (2)
B11—B2—B7—B8	103.14 (15)	C16—N—C14—C15	−176.87 (17)
B3—B2—B7—B11	−140.71 (14)	C20—N—C14—C15	61.8 (2)
B1—B2—B7—B11	−101.95 (15)	C18—N—C16—C17	170.04 (17)
B6—B2—B7—B11	−38.38 (13)	C14—N—C16—C17	−68.8 (2)
B3—B2—B7—S	105.33 (16)	C20—N—C16—C17	50.7 (2)
B1—B2—B7—S	144.08 (13)	C14—N—C18—C19	−56.8 (2)
B6—B2—B7—S	−152.35 (13)	C16—N—C18—C19	62.3 (2)
B11—B2—B7—S	−113.97 (15)	C20—N—C18—C19	−176.42 (15)
B1—B3—B7—B2	−38.94 (13)	C18—N—C20—C21	−58.33 (19)
B4—B3—B7—B2	−102.53 (15)	C14—N—C20—C21	−179.84 (15)
B8—B3—B7—B2	−140.25 (15)	C16—N—C20—C21	60.82 (19)