Crystal engineering with heteroboranes. I. 1-Carboxy-1,2-dicarba-closo-dodecaborane(11)

The title compound, C₃H₁₂B₁₀O₂ or 1-COOH-1,2-closo-C₂B₁₀H₁₁, forms centrosymmetric dimers through intermolecular hydrogen bonding between the carboxylic acid groups, resulting in the formation of an eight-membered ring [R(8)]. The C=O bond of the carboxylic acid group almost eclipses the unsubstituted cage C atom, with a C-C-C-O torsion angle of 2.6 (2)°.

S1. Comment

The usefulness of heteroboranes in studies of crystal engineering has only recently begun to be exploited (Centore et al., 1994; Davidson et al., 1996; Hosmane et al., 1998; Lee et al., 2000), yet such compounds have a number of potential advantages in this respect. Heteroboranes are generally thermally and chemically stable compounds. They exist as polyhedra or fragments of polyhedra of differing size and shape, but have architectures that are well understood (Wade, 1976). Isomeric possibilities mean that C-substituted (hetero)carboranes have the potential to function as supramolecular building blocks with differing directionalities. Significant variation is also possible in the number and nature of the substituents that can be attached to the B atoms of heteroboranes, affording these species the potential to act as supramolecular building blocks in three dimensions. Finally, heteroboranes are usually neutral or anionic, but can also be cationic (see e.g. Douek & Welch, 1993).

Within the field of crystal engineering, the carboxylic acid group is frequently used to afford supramolecular assemblies through intermolecular H···O bonding (Leiserowitz, 1976). Accordingly, we have begun a systematic study of the crystal chemistry of carboxylic acid carboranes and their derivatives. Herein, we describe the structure of the simplest carboxylic acid carborane, 1,2-dicarba-closo-dodecaborane(12)–1-carboxylic acid, (I). \sch

Compound (I) crystallizes as a dimer, linked by two O—H···O hydrogen bonds about a centre of inversion (Fig. 1), typical of the packing of carboxylic acid units (Leiserowitz, 1976). In graph-set terminology (Etter, 1990; Etter & MacDonald, 1990), this motif is denoted R₂²(8). The only other carboxylic acid carborane to be structurally characterized so far is 1,12-closo-C₂B₁₀H₁₀-1,12-(COOH)₂, (II) (Centore et al., 1994). In (II), the molecules pack as linear hydrogen-bonded chains. The dimensions of the hydrogen bond in (I) (Table 2) identify it as `strong' (Desiraju & Steiner, 1999) and bear good comparison with the corresponding O···O distance in (II) (2.639 Å).

In carboxylic acid derivatives of 1,2-dicarbaborane, we may define the orientation of the carboxylic acid group by θ, the C2—C1—C3—O2 dihedral angle. In compound (I), θ = 2.6 (2)°. This is complemented by a C1—C2 connectivity of length 1.632 (2) Å, in excellent agreement with that in the parent compound 1,2-closo-C₂B₁₀H₁₂ [1.630 (6) Å; Davidson et al., 1996], and by a C1—C3 bond of 1.507 (2) Å.

The C—B distances span the range 1.690 (2)–1.729 (2) Å and the B—B distances 1.759 (2)–1.795 (3) Å. There is no evidence for disorder of the C2 vertex, identified on the twin bases of refined (as B) isotropic displacement parameters and intra-cage distances.

Related literature

For related literature, see: Centore et al. (1994); Davidson et al. (1996); Desiraju & Steiner (1999); Douek & Welch (1993); Etter (1990); Etter & MacDonald (1990); Hosmane et al. (1998); Lee et al. (2000); Leiserowitz (1976); Wade (1976); Zakharkin & Grebennikov (1967).

S2. Experimental

Compound (I) was prepared based on the literature method of Zakharkin & Grebennikov (1967) in 73% yield and crystals were grown by evaporation of an acetonitrile solution. Analysis: calculated for C₃H₁₂B₁₀O₂: C 19.1, H 6.4%; found: C 18.3, H 6.90%; ¹H FT-NMR (400.1 MHz, TMS, δ, p.p.m.): 10.40 (1H, br, O—H), 4.00 (1H, s, C—H); ¹¹B-{1H} FT-NMR (128.4 MHz, BF₃·OEt₂, δ, p.p.m.): 0.77 (2B), -5.97 (2B), -8.79 (2B), -10.52(2B), -11.65(2B). NMR spectra were recorded from solution in CDCl₃ at 293 K on a Bruker DPX400 spectrometer.

S3. Refinement

All H atoms (both cage H atoms and COOH) were located from the difference Fourier map and refined, but cage H atoms were restrained, with B—H = 1.10 (2) Å.

Computing details

Data collection: XSCANS (Bruker, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. A perspective view of the dimer of (I) with displacement ellipsoids shown at the 50% probability level. H atoms are drawn as small spheres of arbitrary radii and hydrogen bonds are shown as dotted lines.

1,2-Dicarba-closo-dodecaborane(12)–1-carboxylic acid

Crystal data

C3H12B10O2	F(000) = 384
Mr = 188.23	Dx = 1.188 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 6.988 (2) Å	Cell parameters from 46 reflections
b = 12.031 (3) Å	θ = 3.2–12.5°
c = 12.869 (4) Å	µ = 0.07 mm^−1
β = 103.33 (2)°	T = 160 K
V = 1052.8 (5) Å^3	Needle, colourless
Z = 4	0.82 × 0.24 × 0.20 mm

Data collection

Bruker P4 diffractometer	Rint = 0.041
Radiation source: fine-focus sealed tube	θmax = 25.0°, θmin = 2.4°
Graphite monochromator	h = −1→8
ω scans	k = −14→1
2577 measured reflections	l = −15→15
1849 independent reflections	3 standard reflections every 97 reflections
1557 reflections with I > 2σ(I)	intensity decay: none

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.119	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0612P)^2 + 0.3182P] where P = (Fo^2 + 2Fc^2)/3
1849 reflections	(Δ/σ)max = 0.013
184 parameters	Δρmax = 0.21 e Å^−3
10 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
C1	0.2990 (2)	0.09740 (12)	0.19910 (11)	0.0205 (3)
C2	0.1608 (2)	0.00725 (13)	0.24206 (13)	0.0258 (4)
H2	0.156 (3)	−0.0617 (16)	0.2103 (15)	0.030 (5)*
B3	0.3853 (3)	0.04007 (16)	0.32434 (14)	0.0281 (4)
H3	0.503 (2)	−0.0211 (14)	0.3317 (15)	0.036 (5)*
B4	0.4129 (3)	0.18515 (15)	0.29881 (14)	0.0252 (4)
H4	0.561 (2)	0.2158 (15)	0.2983 (15)	0.035 (5)*
B5	0.2059 (3)	0.22885 (14)	0.19796 (13)	0.0224 (4)
H5	0.227 (3)	0.2857 (14)	0.1351 (13)	0.032 (5)*
B6	0.0466 (3)	0.11200 (15)	0.15923 (14)	0.0243 (4)
H6	−0.021 (3)	0.0895 (15)	0.0762 (11)	0.031 (5)*
B7	0.1689 (3)	0.02422 (16)	0.37368 (16)	0.0328 (5)
H7	0.151 (3)	−0.0493 (14)	0.4200 (15)	0.046 (6)*
B8	0.3270 (3)	0.14071 (17)	0.41208 (14)	0.0293 (4)
H8	0.419 (3)	0.1497 (16)	0.4917 (12)	0.037 (5)*
B9	0.2149 (3)	0.25692 (15)	0.33484 (14)	0.0247 (4)
H9	0.234 (3)	0.3438 (12)	0.3654 (14)	0.033 (5)*
B10	−0.0095 (3)	0.21156 (15)	0.24783 (14)	0.0253 (4)
H10	−0.135 (2)	0.2662 (14)	0.2222 (14)	0.038 (5)*
B11	−0.0369 (3)	0.06777 (16)	0.27325 (16)	0.0298 (4)
H11	−0.172 (3)	0.0199 (16)	0.2630 (18)	0.050 (6)*
B12	0.0656 (3)	0.15804 (16)	0.38111 (15)	0.0291 (4)
H12	−0.016 (2)	0.1772 (15)	0.4428 (13)	0.031 (5)*
O1	0.50751 (17)	0.12697 (9)	0.08288 (9)	0.0296 (3)
O2	0.35818 (18)	−0.03929 (9)	0.07678 (9)	0.0316 (3)
C3	0.3924 (2)	0.05412 (13)	0.11255 (11)	0.0222 (3)
H1	0.552 (4)	0.094 (2)	0.026 (2)	0.072 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0248 (8)	0.0207 (7)	0.0175 (7)	0.0011 (6)	0.0078 (6)	0.0017 (6)
C2	0.0351 (9)	0.0188 (8)	0.0280 (8)	−0.0008 (7)	0.0167 (7)	0.0015 (6)
B3	0.0360 (10)	0.0300 (10)	0.0197 (8)	0.0100 (8)	0.0095 (7)	0.0052 (7)
B4	0.0270 (9)	0.0294 (9)	0.0190 (8)	−0.0002 (7)	0.0048 (7)	−0.0025 (7)
B5	0.0278 (9)	0.0193 (8)	0.0214 (8)	0.0013 (7)	0.0083 (7)	−0.0001 (7)
B6	0.0229 (9)	0.0247 (9)	0.0254 (9)	0.0011 (7)	0.0059 (7)	−0.0027 (7)
B7	0.0505 (12)	0.0262 (9)	0.0286 (10)	0.0053 (9)	0.0235 (9)	0.0058 (7)
B8	0.0370 (11)	0.0342 (10)	0.0179 (8)	0.0066 (8)	0.0086 (8)	0.0014 (7)
B9	0.0307 (10)	0.0233 (9)	0.0215 (8)	0.0004 (7)	0.0092 (7)	−0.0023 (7)
B10	0.0267 (9)	0.0220 (8)	0.0290 (9)	0.0015 (7)	0.0098 (7)	−0.0029 (7)
B11	0.0332 (10)	0.0244 (9)	0.0375 (10)	−0.0043 (8)	0.0198 (8)	−0.0054 (8)
B12	0.0375 (10)	0.0283 (9)	0.0267 (9)	0.0017 (8)	0.0180 (8)	−0.0012 (7)
O1	0.0377 (7)	0.0303 (6)	0.0260 (6)	−0.0037 (5)	0.0178 (5)	−0.0032 (5)
O2	0.0412 (7)	0.0282 (6)	0.0313 (6)	−0.0028 (5)	0.0205 (5)	−0.0067 (5)
C3	0.0249 (8)	0.0251 (8)	0.0175 (7)	0.0035 (6)	0.0065 (6)	0.0016 (6)

Geometric parameters (Å, º)

C1—C2	1.631 (2)	B6—B10	1.759 (2)
C1—C3	1.507 (2)	B6—B11	1.781 (3)
C1—B3	1.729 (2)	B6—H6	1.099 (14)
C1—B4	1.710 (2)	B7—B8	1.782 (3)
C1—B5	1.709 (2)	B7—B11	1.777 (3)
C1—B6	1.728 (2)	B7—B12	1.776 (3)
C2—B3	1.724 (3)	B7—H7	1.091 (15)
C2—B6	1.723 (2)	B8—B9	1.788 (3)
C2—B7	1.694 (2)	B8—B12	1.790 (3)
C2—B11	1.690 (2)	B8—H8	1.083 (14)
C2—H2	0.922 (19)	B9—B10	1.789 (3)
B3—B4	1.795 (3)	B9—B12	1.774 (3)
B3—B7	1.780 (3)	B9—H9	1.114 (14)
B3—B8	1.766 (3)	B10—B11	1.779 (3)
B3—H3	1.093 (14)	B10—B12	1.794 (3)
B4—B5	1.785 (2)	B10—H10	1.087 (14)
B4—B8	1.782 (2)	B11—B12	1.778 (3)
B4—B9	1.780 (3)	B11—H11	1.090 (15)
B4—H4	1.102 (14)	B12—H12	1.103 (14)
B5—B6	1.791 (2)	O1—C3	1.3051 (19)
B5—B9	1.780 (2)	O1—H1	0.95 (3)
B5—B10	1.779 (3)	O2—C3	1.2170 (19)
B5—H5	1.097 (14)
C3—C1—C2	114.31 (12)	B12—B7—B11	60.06 (11)
C3—C1—B5	122.84 (12)	C2—B7—B3	59.43 (10)
C2—C1—B5	111.34 (12)	B12—B7—B3	108.15 (13)
C3—C1—B4	124.21 (13)	B11—B7—B3	108.71 (13)
C2—C1—B4	111.44 (11)	C2—B7—B8	104.34 (12)
B5—C1—B4	62.96 (10)	B12—B7—B8	60.40 (11)
C3—C1—B6	113.67 (12)	B11—B7—B8	108.42 (13)
C2—C1—B6	61.63 (10)	B3—B7—B8	59.44 (11)
B5—C1—B6	62.78 (10)	C2—B7—H7	117.9 (11)
B4—C1—B6	115.23 (12)	B12—B7—H7	127.4 (11)
C3—C1—B3	115.72 (12)	B11—B7—H7	117.5 (11)
C2—C1—B3	61.64 (10)	B3—B7—H7	119.7 (11)
B5—C1—B3	115.30 (11)	B8—B7—H7	128.9 (11)
B4—C1—B3	62.93 (10)	B3—B8—B4	60.78 (10)
B6—C1—B3	115.45 (12)	B3—B8—B7	60.21 (11)
C1—C2—B11	111.99 (12)	B4—B8—B7	108.26 (12)
C1—C2—B7	111.89 (13)	B3—B8—B9	108.46 (12)
B11—C2—B7	63.33 (11)	B4—B8—B9	59.83 (10)
C1—C2—B6	61.96 (10)	B7—B8—B9	107.26 (13)
B11—C2—B6	62.90 (11)	B3—B8—B12	108.15 (14)
B7—C2—B6	115.74 (13)	B4—B8—B12	107.58 (12)
C1—C2—B3	61.96 (10)	B7—B8—B12	59.63 (11)
B11—C2—B3	115.69 (13)	B9—B8—B12	59.44 (10)
B7—C2—B3	62.76 (11)	B3—B8—H8	119.9 (10)
B6—C2—B3	116.01 (12)	B4—B8—H8	120.3 (10)
C1—C2—H2	114.3 (12)	B7—B8—H8	122.4 (10)
B11—C2—H2	123.0 (12)	B9—B8—H8	122.5 (10)
B7—C2—H2	122.8 (12)	B12—B8—H8	123.6 (10)
B6—C2—H2	114.8 (12)	B12—B9—B5	108.39 (12)
B3—C2—H2	114.4 (12)	B12—B9—B4	108.35 (13)
C2—B3—C1	56.39 (9)	B5—B9—B4	60.19 (10)
C2—B3—B8	103.80 (13)	B12—B9—B8	60.33 (11)
C1—B3—B8	103.91 (12)	B5—B9—B8	108.23 (12)
C2—B3—B7	57.81 (11)	B4—B9—B8	59.91 (10)
C1—B3—B7	103.49 (13)	B12—B9—B10	60.45 (11)
B8—B3—B7	60.35 (11)	B5—B9—B10	59.79 (10)
C2—B3—B4	103.38 (12)	B4—B9—B10	108.10 (12)
C1—B3—B4	58.02 (9)	B8—B9—B10	108.52 (13)
B8—B3—B4	60.04 (10)	B12—B9—H9	122.9 (9)
B7—B3—B4	107.79 (13)	B5—B9—H9	120.1 (9)
C2—B3—H3	117.4 (10)	B4—B9—H9	120.6 (10)
C1—B3—H3	116.2 (10)	B8—B9—H9	122.4 (9)
B8—B3—H3	133.5 (10)	B10—B9—H9	121.6 (10)
B7—B3—H3	125.7 (10)	B6—B10—B5	60.80 (10)
B4—B3—H3	124.0 (10)	B6—B10—B11	60.44 (10)
C1—B4—B9	103.88 (12)	B5—B10—B11	108.41 (12)
C1—B4—B8	104.03 (13)	B6—B10—B9	108.60 (13)
B9—B4—B8	60.26 (10)	B5—B10—B9	59.86 (10)
C1—B4—B5	58.50 (9)	B11—B10—B9	107.31 (13)
B9—B4—B5	59.90 (10)	B6—B10—B12	108.39 (13)
B8—B4—B5	108.28 (13)	B5—B10—B12	107.56 (13)
C1—B4—B3	59.05 (9)	B11—B10—B12	59.68 (10)
B9—B4—B3	107.53 (13)	B9—B10—B12	59.34 (10)
B8—B4—B3	59.18 (10)	B6—B10—H10	120.1 (10)
B5—B4—B3	108.43 (13)	B5—B10—H10	120.9 (10)
C1—B4—H4	118.5 (10)	B11—B10—H10	122.0 (10)
B9—B4—H4	128.9 (10)	B9—B10—H10	122.5 (10)
B8—B4—H4	126.9 (10)	B12—B10—H10	123.0 (10)
B5—B4—H4	120.2 (10)	C2—B11—B7	58.44 (10)
B3—B4—H4	117.9 (10)	C2—B11—B12	104.13 (14)
C1—B5—B10	103.95 (12)	B7—B11—B12	59.95 (11)
C1—B5—B9	103.91 (11)	C2—B11—B10	104.28 (13)
B10—B5—B9	60.36 (10)	B7—B11—B10	108.48 (14)
C1—B5—B4	58.54 (9)	B12—B11—B10	60.56 (10)
B10—B5—B4	108.32 (12)	C2—B11—B6	59.45 (10)
B9—B5—B4	59.90 (10)	B7—B11—B6	108.85 (13)
C1—B5—B6	59.14 (9)	B12—B11—B6	108.12 (13)
B10—B5—B6	59.05 (10)	B10—B11—B6	59.23 (10)
B9—B5—B6	107.61 (12)	C2—B11—H11	118.5 (11)
B4—B5—B6	108.57 (12)	B7—B11—H11	117.8 (12)
C1—B5—H5	117.8 (10)	B12—B11—H11	126.9 (12)
B10—B5—H5	127.7 (9)	B10—B11—H11	128.3 (11)
B9—B5—H5	129.3 (9)	B6—B11—H11	119.9 (12)
B4—B5—H5	119.6 (9)	B9—B12—B7	108.17 (13)
B6—B5—H5	117.8 (9)	B9—B12—B11	108.06 (12)
C2—B6—C1	56.41 (9)	B7—B12—B11	59.99 (11)
C2—B6—B10	103.75 (12)	B9—B12—B8	60.23 (11)
C1—B6—B10	103.98 (12)	B7—B12—B8	59.98 (11)
C2—B6—B11	57.65 (10)	B11—B12—B8	108.03 (13)
C1—B6—B11	103.36 (12)	B9—B12—B10	60.21 (10)
B10—B6—B11	60.33 (10)	B7—B12—B10	107.87 (12)
C2—B6—B5	103.45 (12)	B11—B12—B10	59.76 (10)
C1—B6—B5	58.08 (9)	B8—B12—B10	108.25 (13)
B10—B6—B5	60.14 (10)	B9—B12—H12	122.9 (9)
B11—B6—B5	107.82 (12)	B7—B12—H12	120.7 (9)
C2—B6—H6	117.1 (10)	B11—B12—H12	120.5 (9)
C1—B6—H6	116.4 (9)	B8—B12—H12	122.2 (9)
B10—B6—H6	133.5 (9)	B10—B12—H12	121.9 (9)
B11—B6—H6	125.4 (9)	C3—O1—H1	106.0 (16)
B5—B6—H6	124.4 (9)	O2—C3—O1	126.15 (14)
C2—B7—B12	104.06 (13)	O2—C3—C1	121.19 (14)
C2—B7—B11	58.23 (11)	O1—C3—C1	112.66 (13)
C3—C1—C2—B11	−144.37 (13)	B11—B7—B8—B9	0.49 (16)
B5—C1—C2—B11	0.24 (17)	B3—B7—B8—B9	101.79 (13)
B4—C1—C2—B11	68.47 (16)	C2—B7—B8—B12	98.23 (14)
B6—C1—C2—B11	−39.49 (12)	B11—B7—B8—B12	37.42 (12)
B3—C1—C2—B11	108.33 (14)	B3—B7—B8—B12	138.72 (13)
C3—C1—C2—B7	146.69 (13)	C1—B5—B9—B12	−60.98 (15)
B5—C1—C2—B7	−68.70 (16)	B10—B5—B9—B12	37.35 (12)
B4—C1—C2—B7	−0.47 (17)	B4—B5—B9—B12	−101.06 (14)
B6—C1—C2—B7	−108.43 (14)	B6—B5—B9—B12	0.61 (17)
B3—C1—C2—B7	39.39 (13)	C1—B5—B9—B4	40.08 (11)
C3—C1—C2—B6	−104.88 (13)	B10—B5—B9—B4	138.41 (13)
B5—C1—C2—B6	39.73 (12)	B6—B5—B9—B4	101.67 (13)
B4—C1—C2—B6	107.97 (13)	C1—B5—B9—B8	2.93 (16)
B3—C1—C2—B6	147.82 (12)	B10—B5—B9—B8	101.26 (14)
C3—C1—C2—B3	107.30 (14)	B4—B5—B9—B8	−37.15 (12)
B5—C1—C2—B3	−108.09 (13)	B6—B5—B9—B8	64.52 (15)
B4—C1—C2—B3	−39.86 (12)	C1—B5—B9—B10	−98.33 (12)
B6—C1—C2—B3	−147.82 (12)	B4—B5—B9—B10	−138.41 (13)
B11—C2—B3—C1	−102.40 (14)	B6—B5—B9—B10	−36.74 (11)
B7—C2—B3—C1	−138.53 (13)	C1—B4—B9—B12	61.07 (15)
B6—C2—B3—C1	−31.53 (12)	B8—B4—B9—B12	−37.35 (12)
C1—C2—B3—B8	97.70 (13)	B5—B4—B9—B12	101.13 (14)
B11—C2—B3—B8	−4.70 (17)	B3—B4—B9—B12	−0.41 (16)
B7—C2—B3—B8	−40.83 (12)	C1—B4—B9—B5	−40.06 (11)
B6—C2—B3—B8	66.16 (16)	B8—B4—B9—B5	−138.48 (13)
C1—C2—B3—B7	138.53 (13)	B3—B4—B9—B5	−101.54 (13)
B11—C2—B3—B7	36.13 (13)	C1—B4—B9—B8	98.42 (13)
B6—C2—B3—B7	106.99 (14)	B5—B4—B9—B8	138.48 (13)
C1—C2—B3—B4	35.74 (11)	B3—B4—B9—B8	36.94 (12)
B11—C2—B3—B4	−66.66 (16)	C1—B4—B9—B10	−2.94 (15)
B7—C2—B3—B4	−102.79 (13)	B8—B4—B9—B10	−101.36 (14)
B6—C2—B3—B4	4.21 (17)	B5—B4—B9—B10	37.12 (12)
C3—C1—B3—C2	−105.02 (14)	B3—B4—B9—B10	−64.42 (15)
B5—C1—B3—C2	101.67 (14)	B3—B8—B9—B12	100.61 (15)
B4—C1—B3—C2	137.94 (13)	B4—B8—B9—B12	138.49 (13)
B6—C1—B3—C2	31.26 (12)	B7—B8—B9—B12	37.02 (12)
C3—C1—B3—B8	157.48 (13)	B3—B8—B9—B5	−0.60 (17)
C2—C1—B3—B8	−97.50 (14)	B4—B8—B9—B5	37.27 (12)
B5—C1—B3—B8	4.17 (17)	B7—B8—B9—B5	−64.20 (15)
B4—C1—B3—B8	40.44 (12)	B12—B8—B9—B5	−101.22 (14)
B6—C1—B3—B8	−66.24 (16)	B3—B8—B9—B4	−37.88 (13)
C3—C1—B3—B7	−140.22 (13)	B7—B8—B9—B4	−101.47 (13)
C2—C1—B3—B7	−35.19 (12)	B12—B8—B9—B4	−138.49 (13)
B5—C1—B3—B7	66.47 (16)	B3—B8—B9—B10	62.75 (16)
B4—C1—B3—B7	102.74 (13)	B4—B8—B9—B10	100.63 (13)
B6—C1—B3—B7	−3.93 (17)	B7—B8—B9—B10	−0.84 (16)
C3—C1—B3—B4	117.04 (14)	B12—B8—B9—B10	−37.86 (12)
C2—C1—B3—B4	−137.94 (13)	C2—B6—B10—B5	97.80 (13)
B5—C1—B3—B4	−36.27 (13)	C1—B6—B10—B5	39.54 (11)
B6—C1—B3—B4	−106.68 (14)	B11—B6—B10—B5	137.13 (13)
C3—C1—B4—B9	153.68 (13)	C2—B6—B10—B11	−39.34 (12)
C2—C1—B4—B9	−63.03 (15)	C1—B6—B10—B11	−97.60 (13)
B5—C1—B4—B9	40.77 (11)	B5—B6—B10—B11	−137.13 (13)
B6—C1—B4—B9	4.68 (16)	C2—B6—B10—B9	60.45 (15)
B3—C1—B4—B9	−102.33 (13)	C1—B6—B10—B9	2.19 (15)
C3—C1—B4—B8	−144.03 (14)	B11—B6—B10—B9	99.79 (14)
C2—C1—B4—B8	−0.74 (15)	B5—B6—B10—B9	−37.34 (12)
B5—C1—B4—B8	103.06 (13)	C2—B6—B10—B12	−2.48 (16)
B6—C1—B4—B8	66.98 (15)	C1—B6—B10—B12	−60.74 (15)
B3—C1—B4—B8	−40.04 (11)	B11—B6—B10—B12	36.86 (13)
C3—C1—B4—B5	112.91 (15)	B5—B6—B10—B12	−100.28 (14)
C2—C1—B4—B5	−103.80 (13)	C1—B5—B10—B6	−40.07 (11)
B6—C1—B4—B5	−36.09 (12)	B9—B5—B10—B6	−138.33 (13)
B3—C1—B4—B5	−143.10 (13)	B4—B5—B10—B6	−101.10 (13)
C3—C1—B4—B3	−104.00 (15)	C1—B5—B10—B11	−1.48 (16)
C2—C1—B4—B3	39.30 (12)	B9—B5—B10—B11	−99.75 (14)
B5—C1—B4—B3	143.10 (13)	B4—B5—B10—B11	−62.52 (16)
B6—C1—B4—B3	107.01 (13)	B6—B5—B10—B11	38.59 (12)
C2—B3—B4—C1	−35.00 (10)	C1—B5—B10—B9	98.26 (12)
B8—B3—B4—C1	−133.39 (13)	B4—B5—B10—B9	37.23 (12)
B7—B3—B4—C1	−95.07 (14)	B6—B5—B10—B9	138.33 (13)
C2—B3—B4—B9	60.98 (14)	C1—B5—B10—B12	61.60 (14)
C1—B3—B4—B9	95.97 (13)	B9—B5—B10—B12	−36.66 (11)
B8—B3—B4—B9	−37.41 (12)	B4—B5—B10—B12	0.57 (16)
B7—B3—B4—B9	0.90 (16)	B6—B5—B10—B12	101.67 (13)
C2—B3—B4—B8	98.39 (13)	B12—B9—B10—B6	−100.81 (13)
C1—B3—B4—B8	133.39 (13)	B5—B9—B10—B6	37.76 (12)
B7—B3—B4—B8	38.31 (12)	B4—B9—B10—B6	0.46 (17)
C2—B3—B4—B5	−2.34 (15)	B8—B9—B10—B6	−63.00 (15)
C1—B3—B4—B5	32.66 (11)	B12—B9—B10—B5	−138.57 (13)
B8—B3—B4—B5	−100.73 (14)	B4—B9—B10—B5	−37.30 (12)
B7—B3—B4—B5	−62.42 (15)	B8—B9—B10—B5	−100.76 (13)
C3—C1—B5—B10	141.88 (14)	B12—B9—B10—B11	−36.93 (12)
C2—C1—B5—B10	0.79 (15)	B5—B9—B10—B11	101.63 (13)
B4—C1—B5—B10	−103.17 (13)	B4—B9—B10—B11	64.34 (15)
B6—C1—B5—B10	40.03 (11)	B8—B9—B10—B11	0.87 (16)
B3—C1—B5—B10	−66.91 (15)	B5—B9—B10—B12	138.57 (13)
C3—C1—B5—B9	−155.73 (13)	B4—B9—B10—B12	101.27 (14)
C2—C1—B5—B9	63.18 (15)	B8—B9—B10—B12	37.81 (12)
B4—C1—B5—B9	−40.78 (11)	C1—C2—B11—B7	−104.31 (14)
B6—C1—B5—B9	102.41 (13)	B6—C2—B11—B7	−143.40 (13)
B3—C1—B5—B9	−4.52 (17)	B3—C2—B11—B7	−35.92 (13)
C3—C1—B5—B4	−114.96 (16)	C1—C2—B11—B12	−63.84 (15)
C2—C1—B5—B4	103.96 (13)	B7—C2—B11—B12	40.47 (12)
B6—C1—B5—B4	143.19 (12)	B6—C2—B11—B12	−102.94 (13)
B3—C1—B5—B4	36.25 (13)	B3—C2—B11—B12	4.55 (17)
C3—C1—B5—B6	101.85 (15)	C1—C2—B11—B10	−1.16 (17)
C2—C1—B5—B6	−39.23 (12)	B7—C2—B11—B10	103.15 (14)
B4—C1—B5—B6	−143.19 (12)	B6—C2—B11—B10	−40.25 (12)
B3—C1—B5—B6	−106.94 (14)	B3—C2—B11—B10	67.23 (16)
B9—B4—B5—C1	−132.88 (12)	C1—C2—B11—B6	39.09 (12)
B8—B4—B5—C1	−95.57 (13)	B7—C2—B11—B6	143.40 (13)
B3—B4—B5—C1	−32.87 (11)	B3—C2—B11—B6	107.49 (14)
C1—B4—B5—B10	95.46 (12)	B12—B7—B11—C2	133.35 (13)
B9—B4—B5—B10	−37.43 (12)	B3—B7—B11—C2	32.72 (12)
B8—B4—B5—B10	−0.11 (16)	B8—B7—B11—C2	95.78 (14)
B3—B4—B5—B10	62.58 (15)	C2—B7—B11—B12	−133.35 (13)
C1—B4—B5—B9	132.88 (12)	B3—B7—B11—B12	−100.64 (14)
B8—B4—B5—B9	37.31 (12)	B8—B7—B11—B12	−37.57 (12)
B3—B4—B5—B9	100.01 (13)	C2—B7—B11—B10	−95.73 (13)
C1—B4—B5—B6	32.86 (11)	B12—B7—B11—B10	37.62 (12)
B9—B4—B5—B6	−100.03 (13)	B3—B7—B11—B10	−63.01 (16)
B8—B4—B5—B6	−62.71 (15)	B8—B7—B11—B10	0.05 (17)
B3—B4—B5—B6	−0.02 (16)	C2—B7—B11—B6	−32.86 (12)
B11—C2—B6—C1	138.52 (12)	B12—B7—B11—B6	100.50 (13)
B7—C2—B6—C1	102.26 (15)	B3—B7—B11—B6	−0.14 (17)
B3—C2—B6—C1	31.53 (12)	B8—B7—B11—B6	62.93 (16)
C1—C2—B6—B10	−97.82 (12)	B6—B10—B11—C2	40.37 (12)
B11—C2—B6—B10	40.69 (12)	B5—B10—B11—C2	1.62 (17)
B7—C2—B6—B10	4.43 (18)	B9—B10—B11—C2	−61.60 (15)
B3—C2—B6—B10	−66.29 (16)	B12—B10—B11—C2	−98.38 (14)
C1—C2—B6—B11	−138.52 (12)	B6—B10—B11—B7	101.40 (14)
B7—C2—B6—B11	−36.26 (14)	B5—B10—B11—B7	62.65 (16)
B3—C2—B6—B11	−106.98 (15)	B9—B10—B11—B7	−0.57 (16)
C1—C2—B6—B5	−35.75 (10)	B12—B10—B11—B7	−37.35 (12)
B11—C2—B6—B5	102.76 (13)	B6—B10—B11—B12	138.75 (13)
B7—C2—B6—B5	66.50 (16)	B5—B10—B11—B12	100.00 (14)
B3—C2—B6—B5	−4.22 (17)	B9—B10—B11—B12	36.78 (12)
C3—C1—B6—C2	105.91 (14)	B5—B10—B11—B6	−38.75 (12)
B5—C1—B6—C2	−137.97 (12)	B9—B10—B11—B6	−101.97 (14)
B4—C1—B6—C2	−101.82 (13)	B12—B10—B11—B6	−138.75 (13)
B3—C1—B6—C2	−31.26 (12)	C1—B6—B11—C2	−34.55 (11)
C3—C1—B6—B10	−156.70 (12)	B10—B6—B11—C2	−133.21 (14)
C2—C1—B6—B10	97.39 (13)	B5—B6—B11—C2	−94.91 (13)
B5—C1—B6—B10	−40.58 (11)	C2—B6—B11—B7	32.47 (12)
B4—C1—B6—B10	−4.42 (16)	C1—B6—B11—B7	−2.08 (15)
B3—C1—B6—B10	66.13 (16)	B10—B6—B11—B7	−100.74 (14)
C3—C1—B6—B11	141.02 (13)	B5—B6—B11—B7	−62.45 (15)
C2—C1—B6—B11	35.11 (11)	C2—B6—B11—B12	96.04 (15)
B5—C1—B6—B11	−102.86 (12)	C1—B6—B11—B12	61.49 (15)
B4—C1—B6—B11	−66.71 (15)	B10—B6—B11—B12	−37.17 (12)
B3—C1—B6—B11	3.85 (16)	B5—B6—B11—B12	1.13 (17)
C3—C1—B6—B5	−116.13 (13)	C2—B6—B11—B10	133.21 (14)
C2—C1—B6—B5	137.97 (12)	C1—B6—B11—B10	98.66 (13)
B4—C1—B6—B5	36.15 (12)	B5—B6—B11—B10	38.30 (12)
B3—C1—B6—B5	106.71 (13)	B5—B9—B12—B7	63.56 (17)
C1—B5—B6—C2	34.99 (10)	B4—B9—B12—B7	−0.23 (17)
B10—B5—B6—C2	−98.31 (13)	B8—B9—B12—B7	−37.39 (13)
B9—B5—B6—C2	−61.00 (14)	B10—B9—B12—B7	100.62 (14)
B4—B5—B6—C2	2.37 (15)	B5—B9—B12—B11	0.09 (17)
B10—B5—B6—C1	−133.30 (12)	B4—B9—B12—B11	−63.70 (16)
B9—B5—B6—C1	−95.99 (12)	B8—B9—B12—B11	−100.87 (14)
B4—B5—B6—C1	−32.62 (11)	B10—B9—B12—B11	37.15 (12)
C1—B5—B6—B10	133.30 (12)	B5—B9—B12—B8	100.96 (14)
B9—B5—B6—B10	37.32 (12)	B4—B9—B12—B8	37.17 (12)
B4—B5—B6—B10	100.68 (13)	B10—B9—B12—B8	138.01 (13)
C1—B5—B6—B11	94.92 (13)	B5—B9—B12—B10	−37.06 (12)
B10—B5—B6—B11	−38.38 (12)	B4—B9—B12—B10	−100.85 (13)
B9—B5—B6—B11	−1.07 (16)	B8—B9—B12—B10	−138.01 (13)
B4—B5—B6—B11	62.29 (15)	C2—B7—B12—B9	−61.20 (17)
C1—C2—B7—B12	63.96 (17)	B11—B7—B12—B9	−100.79 (14)
B11—C2—B7—B12	−40.51 (12)	B3—B7—B12—B9	0.79 (18)
B6—C2—B7—B12	−4.41 (19)	B8—B7—B12—B9	37.51 (12)
B3—C2—B7—B12	103.01 (14)	C2—B7—B12—B11	39.59 (12)
C1—C2—B7—B11	104.47 (14)	B3—B7—B12—B11	101.58 (14)
B6—C2—B7—B11	36.10 (13)	B8—B7—B12—B11	138.29 (13)
B3—C2—B7—B11	143.52 (13)	C2—B7—B12—B8	−98.71 (14)
C1—C2—B7—B3	−39.05 (12)	B11—B7—B12—B8	−138.29 (13)
B11—C2—B7—B3	−143.52 (13)	B3—B7—B12—B8	−36.72 (12)
B6—C2—B7—B3	−107.42 (15)	C2—B7—B12—B10	2.47 (18)
C1—C2—B7—B8	1.45 (17)	B11—B7—B12—B10	−37.12 (13)
B11—C2—B7—B8	−103.02 (14)	B3—B7—B12—B10	64.46 (17)
B6—C2—B7—B8	−66.92 (17)	B8—B7—B12—B10	101.17 (14)
B3—C2—B7—B8	40.50 (12)	C2—B11—B12—B9	61.28 (16)
C1—B3—B7—C2	34.56 (11)	B7—B11—B12—B9	100.99 (14)
B8—B3—B7—C2	133.06 (13)	B10—B11—B12—B9	−37.34 (12)
B4—B3—B7—C2	94.88 (13)	B6—B11—B12—B9	−0.75 (17)
C2—B3—B7—B12	−95.93 (14)	C2—B11—B12—B7	−39.71 (12)
C1—B3—B7—B12	−61.37 (16)	B10—B11—B12—B7	−138.33 (14)
B8—B3—B7—B12	37.13 (13)	B6—B11—B12—B7	−101.74 (14)
B4—B3—B7—B12	−1.04 (17)	C2—B11—B12—B8	−2.42 (16)
C2—B3—B7—B11	−32.25 (12)	B7—B11—B12—B8	37.29 (12)
C1—B3—B7—B11	2.30 (17)	B10—B11—B12—B8	−101.04 (14)
B8—B3—B7—B11	100.80 (14)	B6—B11—B12—B8	−64.45 (16)
B4—B3—B7—B11	62.63 (16)	C2—B11—B12—B10	98.62 (13)
C2—B3—B7—B8	−133.06 (13)	B7—B11—B12—B10	138.33 (14)
C1—B3—B7—B8	−98.50 (13)	B6—B11—B12—B10	36.59 (12)
B4—B3—B7—B8	−38.18 (12)	B3—B8—B12—B9	−101.16 (13)
C2—B3—B8—B4	−97.67 (13)	B4—B8—B12—B9	−36.94 (12)
C1—B3—B8—B4	−39.42 (11)	B7—B8—B12—B9	−138.21 (13)
B7—B3—B8—B4	−137.21 (13)	B3—B8—B12—B7	37.05 (12)
C2—B3—B8—B7	39.55 (12)	B4—B8—B12—B7	101.26 (14)
C1—B3—B8—B7	97.79 (14)	B9—B8—B12—B7	138.21 (13)
B4—B3—B8—B7	137.21 (13)	B3—B8—B12—B11	−0.24 (17)
C2—B3—B8—B9	−60.21 (16)	B4—B8—B12—B11	63.97 (16)
C1—B3—B8—B9	−1.96 (17)	B7—B8—B12—B11	−37.29 (12)
B7—B3—B8—B9	−99.75 (15)	B9—B8—B12—B11	100.91 (14)
B4—B3—B8—B9	37.46 (12)	B3—B8—B12—B10	−63.48 (16)
C2—B3—B8—B12	2.75 (16)	B4—B8—B12—B10	0.74 (17)
C1—B3—B8—B12	60.99 (16)	B7—B8—B12—B10	−100.53 (13)
B7—B3—B8—B12	−36.80 (13)	B9—B8—B12—B10	37.68 (12)
B4—B3—B8—B12	100.42 (14)	B6—B10—B12—B9	101.17 (14)
C1—B4—B8—B3	39.97 (11)	B5—B10—B12—B9	36.89 (11)
B9—B4—B8—B3	138.14 (14)	B11—B10—B12—B9	138.35 (13)
B5—B4—B8—B3	100.98 (14)	B6—B10—B12—B7	0.04 (18)
C1—B4—B8—B7	1.60 (16)	B5—B10—B12—B7	−64.24 (16)
B9—B4—B8—B7	99.77 (14)	B11—B10—B12—B7	37.22 (13)
B5—B4—B8—B7	62.61 (16)	B9—B10—B12—B7	−101.13 (15)
B3—B4—B8—B7	−38.37 (13)	B6—B10—B12—B11	−37.19 (12)
C1—B4—B8—B9	−98.17 (13)	B5—B10—B12—B11	−101.47 (13)
B5—B4—B8—B9	−37.16 (12)	B9—B10—B12—B11	−138.35 (13)
B3—B4—B8—B9	−138.14 (14)	B6—B10—B12—B8	63.47 (16)
C1—B4—B8—B12	−61.40 (15)	B5—B10—B12—B8	−0.81 (17)
B9—B4—B8—B12	36.77 (12)	B11—B10—B12—B8	100.66 (14)
B5—B4—B8—B12	−0.39 (17)	B9—B10—B12—B8	−37.69 (12)
B3—B4—B8—B12	−101.37 (14)	C2—C1—C3—O2	2.6 (2)
C2—B7—B8—B3	−40.49 (12)	B5—C1—C3—O2	−137.41 (15)
B12—B7—B8—B3	−138.72 (13)	B4—C1—C3—O2	145.03 (15)
B11—B7—B8—B3	−101.30 (14)	B6—C1—C3—O2	−65.56 (18)
C2—B7—B8—B4	−1.86 (17)	B3—C1—C3—O2	71.49 (19)
B12—B7—B8—B4	−100.09 (14)	C2—C1—C3—O1	−177.63 (12)
B11—B7—B8—B4	−62.67 (16)	B5—C1—C3—O1	42.31 (19)
B3—B7—B8—B4	38.63 (12)	B4—C1—C3—O1	−35.25 (19)
C2—B7—B8—B9	61.29 (16)	B6—C1—C3—O1	114.16 (14)
B12—B7—B8—B9	−36.94 (12)	B3—C1—C3—O1	−108.79 (15)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2^i	0.95 (3)	1.72 (3)	2.6655 (16)	177 (2)

Symmetry code: (i) −x+1, −y, −z.