1-[5-(4,5-Dimethyl-1,3,2-dioxaboro­lan-2-yl)thio­phen-2-yl]ethanone and 4-(4,4,5,5-tetra­methyl-1,3,2-dioxa­borolan-2-yl)benzaldehyde

In both title compounds, C₁₀H₁₃BO₃S, (I), and C₁₃H₁₇BO₃, (II), the mol­ecules adopt nearly planar conformations. The crystal packing of (I) consists of a supra­molecular two-dimensional network with a herringbone-like topology formed by self assembly of centrosymmetric pairs of mol­ecules linked via dipole–dipole inter­actions. The crystal structure of (II) consists of a supra­molecular two-dimensional network built up from centrosymmetric pairs of mol­ecules via π–π inter­actions. These pairs of mol­ecules are self-organized in an offset fashion related by a symmetry centre, generating supra­molecular ribbons running along the [101] direction. Neighbouring ribbons are stacked via complementary van der Waals and hydro­phobic methyl–methyl inter­actions.

S1. Comment

Compounds containing boronate esters [RB(OR)₂] represent valuable intermediates in organic synthesis, particularly in the Suzuki–Miyaura coupling reaction (Miyaura & Suzuki, 1995). They are also well established compounds for the detection of carbohydrates (Striegler, 2003), as a result of their ability to form cyclic esters with appropriate diols (Schnürch et al., 2007). It has been found that some imines containing boronate ester groups display antifungal behaviour against both Aspergillus niger and A. flavus (Vogels et al., 2001). Crystallographic studies related to the structure–property relationship of boronate esters remains largely unexplored and only a few crystal structures have been reported so far. In particular, there is a crystallograhic report on the space group revision of 4-formylphenylboronic acid (Fronczek et al., 2001), where both the formyl and B(OH)₂ groups were found ordered, in contrast with the previous, disordered, report (Feulner et al., 1990). In this contribution, as part of our ongoing investigation of the synthesis and solid-state reactivity of unsaturated pyridyl compounds (Linares & Briceño, 2010; Hill et al., 2012), we describe the molecular structures of the title compounds, (I) and (II), which are interesting precursors for the preparation of asymmetric olefins via a condensation process.

The molecule of (I) (Fig. 1) adopts a nearly planar conformation, The acetyl and boronate ester substituents make dihedral angles of 3.35 (6) and 2.96 (2)° with respect to the mean plane of the thiophene ring. The methyl groups are oriented in a trans configuration on the five-membered ring formed by atoms B1/O2/C1/C2/O1. The B—O distances are statistically similar, with B1—O1 = 1.363 (4) Å and B1—O2 = 1.347 (5) Å. Likewise, the C—S [1.711 (3) and 1.712 (3) Å] and C═C [C3—C4 = 1.373 (4) Å and C5—C6 = 1.362 (4) Å] distances from the thiophene ring are also similar, displaying bond lengths typical for C—S single and C═C double bonds, respectively [average C—S 1.69 (8) Å and average C═C = 1.34 (3) Å (Cambridge structural Database, Version 5.32; Allen, 2002)]. The B—O distances are significantly different, with B1—O1 [1.363 (4) Å] slightly longer than B1—O2 [1.347 (5) Å]. In contrast, the C—S [1.711 (3) and 1.712 (3) Å] and C═C [C3—C4 = 1.373 (4) and C5—C6 = 1.362 (4) Å] distances from the thiophene ring are statistically similar, displaying lengths typical for C—S single bonds and C═C double bonds, respectively [Standard reference?]. The carbonyl group is oriented cis to the S atom of the thiophene ring, forming an S1—C6—C7—O3 torsion angle of -1.569 (3)°.

The crystal structure of (I) consists of supramolecular layers built up from centrosymmetric pairs of molecules linked by dipole–dipole interactions between carbonyl and B—O groups [B1ⁱ···O3 = 3.545 (5) Å and O1ⁱ···C7 = 3.699 (5) Å; symmetry code: (i) -x, -y, -z + 1] (Fig. 2b), generating a herringbone-like supramolecular two-dimensional network parallel to the bc plane (Fig. 2a). The three-dimensional array is accomplished by the stacking of the layers through van der Waals and hydrophobic methyl–methyl interactions.

The molecule of (II) (Fig. 3) deviates from planarity, with the boronate ester group forming a dihedral angle of 7.53 (2)° with respect to the mean plane of the benzaldehyde group. The B—O [B1—O1 = 1.348 (3) Å and B1—O2 = 1.349 (3) Å] distances found for (II) are similar, in contrast with what is observed for (I).

The crystal structure of (II) also consists of supramolecular layers built up from centrosymmetric pairs of molecules via π–π interactions [Cg1···Cg1ⁱⁱ = 3.811 (3) Å; Cg1 is the centroid of the C3–C8 aromatic ring; symmetry code: (ii) -x + 2, -y, -z + 1]. These pairs are self-organized in an offset fashion related by a symmetry centre, generating supramolecular ribbons running along the [101] direction. Neighbouring ribbons are stacked via complementary van der Waals and hydrophobic methyl–methyl interactions, generating a two-dimensional network (Fig. 4). The final three-dimensional array is stabilized via van der Waals interactions.

Related literature

For related literature, see: Allen (2002); Feulner et al. (1990); Fronczek et al. (2001); Hill et al. (2012); Linares & Briceño (2010); Miyaura & Suzuki (1995); Schnürch et al. (2007); Striegler (2003); Vogels et al. (2001).

S2. Experimental

Compounds (I) and (II) were synthesized from commercially available 5-acetylthiophen-2-ylboronic acid and 4-formylphenylboronic acid (Sigma–Aldrich Co.) by reaction with the corresponding diols (Schnürch et al., 2007). Colourless crystals of both compounds were grown from a petroleum ether–tetrahydrofuran [Solvent ratio?] solution kept at 277 K.

S3. Refinement

C-bound H atoms were placed in idealized positions, with C—H = 0.93 and 0.98 Å for aromatic and methine groups, respectively, and 0.96 Å for methyl groups, and refined as riding, with U_iso(H) = 1.2U_eq(C) for for aromatic and methine groups and 1.5U_eq(C) for methyl groups.

Computing details

For both compounds, data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: CrystalStructure (Rigaku/MSC, 2005) and SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures

	Fig. 1. The molecular structure of (I), showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 35% probability level.
	Fig. 2. (a) A view of the herringbone array in the structure of (I). Dashed lines indicate dipole–dipole interactions? (b) Pairs of molecules of (I) linked by dipole–dipole interactions (dashed lines) between carbonyl and B—O groups. [Symmetry code: (i) -x, -y, -z + 1.]
	Fig. 3. The molecular structure of (II), showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 35% probability level.
	Fig. 4. A view of the two-dimensional network in (II), built-up from centrosymmetric pairs of molecules via π–π^ii interactions (dashed lines). [Symmetry code: (ii) -x + 2, -y, -z + 1.]

(I) 1-[5-(4,5-Dimethyl-1,3,2-dioxaborolan-2-yl)thiophen-2-yl]ethanone

Crystal data

C10H13BO3S	F(000) = 472
Mr = 224.07	Dx = 1.226 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 836 reflections
a = 6.038 (3) Å	θ = 2.0–27.5°
b = 10.286 (4) Å	µ = 0.25 mm^−1
c = 20.096 (8) Å	T = 293 K
β = 103.390 (16)°	Block, colourless
V = 1214.2 (9) Å^3	0.42 × 0.33 × 0.22 mm
Z = 4

Data collection

Rigaku AFC-7S Mercury diffractometer	2365 independent reflections
Radiation source: Normal-focus sealed tube	1479 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.060
ω scans	θmax = 27.7°, θmin = 2.1°
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	h = −6→6
Tmin = 0.962, Tmax = 0.980	k = −12→13
13808 measured reflections	l = −25→25

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)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.167	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0619P)^2 + 0.3633P] where P = (Fo^2 + 2Fc^2)/3
2365 reflections	(Δ/σ)max < 0.001
139 parameters	Δρmax = 0.18 e Å^−3
0 restraints	Δρmin = −0.27 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
S1	−0.08116 (13)	−0.06102 (8)	0.41076 (4)	0.0722 (3)
O1	−0.2449 (4)	0.2032 (3)	0.33680 (13)	0.0985 (9)
O2	0.1025 (4)	0.2696 (2)	0.32444 (14)	0.0980 (8)
O3	−0.0798 (5)	−0.3107 (3)	0.48410 (19)	0.1243 (11)
B1	−0.0174 (7)	0.1781 (4)	0.3488 (2)	0.0738 (10)
C1	−0.0545 (8)	0.3691 (4)	0.2914 (2)	0.1065 (14)
H1	−0.0580	0.3696	0.2424	0.128*
C2	−0.2886 (8)	0.3259 (5)	0.3013 (2)	0.1107 (15)
H2	−0.3437	0.3890	0.3303	0.133*
C3	0.0868 (5)	0.0540 (3)	0.38535 (15)	0.0630 (8)
C4	0.3103 (5)	0.0150 (3)	0.40285 (16)	0.0702 (9)
H4	0.4287	0.0644	0.3936	0.084*
C5	0.3439 (5)	−0.1055 (3)	0.43578 (16)	0.0675 (8)
H5	0.4856	−0.1448	0.4502	0.081*
C6	0.1463 (5)	−0.1590 (3)	0.44453 (15)	0.0625 (8)
C7	0.1096 (7)	−0.2809 (3)	0.4785 (2)	0.0847 (11)
C8	0.3125 (7)	−0.3645 (4)	0.5073 (2)	0.1080 (14)
H8A	0.2626	−0.4502	0.5158	0.162*
H8B	0.3975	−0.3274	0.5493	0.162*
H8C	0.4074	−0.3695	0.4751	0.162*
C9	−0.4652 (8)	0.3080 (7)	0.2357 (3)	0.170 (3)
H9A	−0.5990	0.2692	0.2453	0.255*
H9B	−0.4059	0.2523	0.2056	0.255*
H9C	−0.5035	0.3909	0.2142	0.255*
C10	0.0263 (12)	0.4987 (5)	0.3210 (4)	0.187 (3)
H10A	0.1768	0.5148	0.3147	0.280*
H10B	0.0290	0.4994	0.3689	0.280*
H10C	−0.0750	0.5652	0.2983	0.280*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0442 (5)	0.0841 (6)	0.0895 (6)	−0.0001 (4)	0.0179 (4)	0.0033 (5)
O1	0.0650 (16)	0.122 (2)	0.1110 (19)	0.0254 (14)	0.0258 (13)	0.0537 (16)
O2	0.0786 (18)	0.1005 (18)	0.120 (2)	0.0116 (14)	0.0334 (15)	0.0405 (16)
O3	0.099 (2)	0.0847 (18)	0.210 (3)	−0.0057 (15)	0.077 (2)	0.0258 (19)
B1	0.059 (2)	0.093 (3)	0.072 (2)	0.010 (2)	0.0217 (19)	0.012 (2)
C1	0.110 (3)	0.110 (3)	0.105 (3)	0.026 (3)	0.036 (3)	0.049 (3)
C2	0.102 (3)	0.135 (3)	0.106 (3)	0.048 (3)	0.046 (3)	0.056 (3)
C3	0.0529 (18)	0.0754 (19)	0.0611 (17)	−0.0002 (15)	0.0140 (14)	0.0021 (16)
C4	0.0474 (19)	0.086 (2)	0.079 (2)	−0.0043 (16)	0.0180 (15)	0.0076 (18)
C5	0.0469 (19)	0.076 (2)	0.081 (2)	0.0058 (15)	0.0175 (16)	0.0074 (17)
C6	0.0569 (19)	0.0630 (17)	0.0701 (19)	0.0010 (14)	0.0196 (15)	−0.0017 (15)
C7	0.087 (3)	0.067 (2)	0.111 (3)	0.0005 (19)	0.046 (2)	0.001 (2)
C8	0.099 (3)	0.089 (3)	0.144 (4)	0.024 (2)	0.046 (3)	0.037 (3)
C9	0.080 (3)	0.276 (8)	0.149 (5)	0.029 (4)	0.018 (3)	0.104 (5)
C10	0.217 (7)	0.098 (4)	0.242 (7)	0.013 (4)	0.043 (6)	0.013 (4)

Geometric parameters (Å, º)

S1—C3	1.711 (3)	C4—H4	0.9300
S1—C6	1.712 (3)	C5—C6	1.362 (4)
O1—B1	1.363 (4)	C5—H5	0.9300
O1—C2	1.443 (4)	C6—C7	1.469 (5)
O2—B1	1.347 (5)	C7—C8	1.499 (5)
O2—C1	1.447 (4)	C8—H8A	0.9600
O3—C7	1.214 (4)	C8—H8B	0.9600
B1—C3	1.533 (5)	C8—H8C	0.9600
C1—C10	1.495 (7)	C9—H9A	0.9600
C1—C2	1.538 (6)	C9—H9B	0.9600
C1—H1	0.9800	C9—H9C	0.9600
C2—C9	1.503 (6)	C10—H10A	0.9600
C2—H2	0.9800	C10—H10B	0.9600
C3—C4	1.373 (4)	C10—H10C	0.9600
C4—C5	1.397 (4)
C3—S1—C6	92.80 (15)	C4—C5—H5	123.7
B1—O1—C2	108.4 (3)	C5—C6—C7	129.5 (3)
B1—O2—C1	108.1 (3)	C5—C6—S1	110.9 (2)
O2—B1—O1	114.0 (3)	C7—C6—S1	119.6 (2)
O2—B1—C3	124.1 (3)	O3—C7—C6	120.3 (4)
O1—B1—C3	121.9 (3)	O3—C7—C8	121.5 (3)
O2—C1—C10	109.3 (4)	C6—C7—C8	118.1 (3)
O2—C1—C2	105.1 (3)	C7—C8—H8A	109.5
C10—C1—C2	115.6 (5)	C7—C8—H8B	109.5
O2—C1—H1	108.9	H8A—C8—H8B	109.5
C10—C1—H1	108.9	C7—C8—H8C	109.5
C2—C1—H1	108.9	H8A—C8—H8C	109.5
O1—C2—C9	109.8 (4)	H8B—C8—H8C	109.5
O1—C2—C1	104.3 (3)	C2—C9—H9A	109.5
C9—C2—C1	114.1 (4)	C2—C9—H9B	109.5
O1—C2—H2	109.5	H9A—C9—H9B	109.5
C9—C2—H2	109.5	C2—C9—H9C	109.5
C1—C2—H2	109.5	H9A—C9—H9C	109.5
C4—C3—B1	129.5 (3)	H9B—C9—H9C	109.5
C4—C3—S1	109.7 (2)	C1—C10—H10A	109.5
B1—C3—S1	120.8 (2)	C1—C10—H10B	109.5
C3—C4—C5	114.0 (3)	H10A—C10—H10B	109.5
C3—C4—H4	123.0	C1—C10—H10C	109.5
C5—C4—H4	123.0	H10A—C10—H10C	109.5
C6—C5—C4	112.6 (3)	H10B—C10—H10C	109.5
C6—C5—H5	123.7
C1—O2—B1—O1	−0.5 (5)	O1—B1—C3—S1	1.7 (5)
C1—O2—B1—C3	178.0 (3)	C6—S1—C3—C4	0.2 (2)
C2—O1—B1—O2	−1.0 (5)	C6—S1—C3—B1	−179.8 (3)
C2—O1—B1—C3	−179.5 (3)	B1—C3—C4—C5	−179.7 (3)
B1—O2—C1—C10	126.2 (4)	S1—C3—C4—C5	0.2 (4)
B1—O2—C1—C2	1.6 (5)	C3—C4—C5—C6	−0.8 (4)
B1—O1—C2—C9	124.6 (4)	C4—C5—C6—C7	−177.6 (3)
B1—O1—C2—C1	1.9 (5)	C4—C5—C6—S1	0.9 (4)
O2—C1—C2—O1	−2.1 (5)	C3—S1—C6—C5	−0.7 (3)
C10—C1—C2—O1	−122.6 (5)	C3—S1—C6—C7	178.0 (3)
O2—C1—C2—C9	−121.9 (4)	C5—C6—C7—O3	176.8 (4)
C10—C1—C2—C9	117.6 (5)	S1—C6—C7—O3	−1.7 (5)
O2—B1—C3—C4	3.3 (6)	C5—C6—C7—C8	−1.8 (6)
O1—B1—C3—C4	−178.3 (3)	S1—C6—C7—C8	179.8 (3)
O2—B1—C3—S1	−176.6 (3)

(II) 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzaldehyde

Crystal data

C13H17BO3	Z = 2
Mr = 232.08	F(000) = 248
Triclinic, P1	Dx = 1.158 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71070 Å
a = 6.664 (5) Å	Cell parameters from 836 reflections
b = 9.537 (8) Å	θ = 2.0–27.5°
c = 10.771 (9) Å	µ = 0.08 mm^−1
α = 102.252 (19)°	T = 293 K
β = 93.24 (3)°	Block, colourless
γ = 94.07 (3)°	0.48 × 0.37 × 0.22 mm
V = 665.5 (9) Å^3

Data collection

Rigaku AFC-7S Mercury diffractometer	2388 independent reflections
Radiation source: Normal-focus sealed tube	1639 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
ω scans	θmax = 27.6°, θmin = 1.9°
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	h = −8→6
Tmin = 0.962, Tmax = 0.980	k = −11→11
7390 measured reflections	l = −12→12

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.064	H-atom parameters constrained
wR(F^2) = 0.203	w = 1/[σ^2(Fo^2) + (0.104P)^2 + 0.0631P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max < 0.001
2388 reflections	Δρmax = 0.18 e Å^−3
155 parameters	Δρmin = −0.17 e Å^−3
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.07 (2)

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
O3	1.1747 (3)	−0.3505 (2)	0.4710 (2)	0.1084 (7)
O2	0.4989 (2)	0.1506 (2)	0.22127 (18)	0.0902 (7)
O1	0.8126 (2)	0.20802 (17)	0.17153 (17)	0.0795 (6)
B1	0.6941 (3)	0.1217 (3)	0.2263 (2)	0.0566 (6)
C1	0.6909 (3)	0.3024 (2)	0.1174 (2)	0.0629 (6)
C2	0.4752 (3)	0.2699 (3)	0.1615 (2)	0.0695 (7)
C3	0.7750 (3)	0.0026 (2)	0.28926 (18)	0.0547 (6)
C4	0.9722 (3)	−0.0348 (2)	0.2788 (2)	0.0664 (6)
H4	1.0572	0.0117	0.2318	0.080*
C5	1.0452 (3)	−0.1389 (2)	0.3359 (2)	0.0660 (6)
H5	1.1771	−0.1628	0.3257	0.079*
C6	0.9245 (3)	−0.2079 (2)	0.40811 (19)	0.0604 (6)
C7	0.7271 (3)	−0.1734 (3)	0.4189 (2)	0.0732 (7)
H7	0.6428	−0.2206	0.4658	0.088*
C8	0.6542 (3)	−0.0697 (2)	0.3607 (2)	0.0658 (6)
H8	0.5213	−0.0477	0.3694	0.079*
C9	1.0048 (4)	−0.3154 (3)	0.4735 (2)	0.0840 (8)
H9	0.9171	−0.3596	0.5205	0.101*
C10	0.7845 (5)	0.4531 (3)	0.1694 (5)	0.1437 (16)
H10A	0.9154	0.4636	0.1378	0.216*
H10B	0.7976	0.4714	0.2607	0.216*
H10C	0.7003	0.5205	0.1427	0.216*
C11	0.7053 (5)	0.2615 (5)	−0.0236 (3)	0.1370 (15)
H11A	0.8409	0.2844	−0.0432	0.206*
H11B	0.6145	0.3138	−0.0650	0.206*
H11C	0.6699	0.1600	−0.0530	0.206*
C12	0.4097 (7)	0.3872 (4)	0.2619 (4)	0.171 (2)
H12A	0.2771	0.3599	0.2840	0.257*
H12B	0.4072	0.4740	0.2304	0.257*
H12C	0.5024	0.4032	0.3360	0.257*
C13	0.3148 (4)	0.2223 (5)	0.0534 (3)	0.1282 (14)
H13A	0.1874	0.2044	0.0870	0.192*
H13B	0.3494	0.1357	−0.0017	0.192*
H13C	0.3055	0.2965	0.0060	0.192*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O3	0.1236 (17)	0.0989 (15)	0.1151 (17)	0.0498 (12)	0.0004 (12)	0.0399 (13)
O2	0.0573 (10)	0.1166 (14)	0.1230 (15)	0.0164 (8)	0.0113 (8)	0.0808 (12)
O1	0.0631 (9)	0.0861 (11)	0.1092 (13)	0.0235 (7)	0.0220 (8)	0.0563 (10)
B1	0.0565 (13)	0.0616 (14)	0.0538 (13)	0.0075 (10)	0.0045 (9)	0.0164 (11)
C1	0.0620 (13)	0.0651 (13)	0.0695 (14)	0.0144 (9)	0.0056 (9)	0.0291 (11)
C2	0.0642 (13)	0.0795 (15)	0.0780 (15)	0.0235 (10)	0.0147 (10)	0.0383 (12)
C3	0.0575 (12)	0.0563 (12)	0.0505 (11)	0.0057 (9)	0.0018 (8)	0.0123 (9)
C4	0.0628 (13)	0.0691 (14)	0.0753 (15)	0.0116 (10)	0.0144 (10)	0.0292 (12)
C5	0.0601 (12)	0.0650 (14)	0.0773 (15)	0.0166 (10)	0.0071 (10)	0.0212 (12)
C6	0.0776 (14)	0.0523 (12)	0.0511 (12)	0.0129 (10)	0.0023 (9)	0.0094 (9)
C7	0.0801 (15)	0.0748 (15)	0.0749 (16)	0.0106 (11)	0.0180 (11)	0.0345 (12)
C8	0.0590 (12)	0.0737 (14)	0.0713 (14)	0.0111 (10)	0.0102 (9)	0.0271 (12)
C9	0.115 (2)	0.0703 (16)	0.0744 (17)	0.0280 (14)	0.0103 (13)	0.0242 (13)
C10	0.103 (2)	0.0728 (19)	0.249 (5)	−0.0027 (16)	−0.003 (3)	0.029 (2)
C11	0.101 (2)	0.248 (5)	0.076 (2)	0.026 (2)	0.0237 (16)	0.058 (3)
C12	0.219 (4)	0.126 (3)	0.188 (4)	0.060 (3)	0.138 (4)	0.033 (3)
C13	0.0748 (18)	0.201 (4)	0.128 (3)	−0.010 (2)	−0.0174 (16)	0.092 (3)

Geometric parameters (Å, º)

O3—C9	1.203 (3)	C6—C9	1.475 (3)
O2—B1	1.349 (3)	C7—C8	1.380 (3)
O2—C2	1.435 (3)	C7—H7	0.9300
O1—B1	1.348 (3)	C8—H8	0.9300
O1—C1	1.442 (3)	C9—H9	0.9300
B1—C3	1.553 (3)	C10—H10A	0.9600
C1—C11	1.496 (4)	C10—H10B	0.9600
C1—C10	1.504 (4)	C10—H10C	0.9600
C1—C2	1.570 (3)	C11—H11A	0.9600
C2—C12	1.490 (4)	C11—H11B	0.9600
C2—C13	1.507 (4)	C11—H11C	0.9600
C3—C8	1.390 (3)	C12—H12A	0.9600
C3—C4	1.391 (3)	C12—H12B	0.9600
C4—C5	1.376 (3)	C12—H12C	0.9600
C4—H4	0.9300	C13—H13A	0.9600
C5—C6	1.377 (3)	C13—H13B	0.9600
C5—H5	0.9300	C13—H13C	0.9600
C6—C7	1.383 (3)
B1—O2—C2	110.10 (17)	C6—C7—H7	119.7
B1—O1—C1	109.69 (17)	C7—C8—C3	121.5 (2)
O1—B1—O2	112.8 (2)	C7—C8—H8	119.3
O1—B1—C3	123.31 (19)	C3—C8—H8	119.3
O2—B1—C3	123.89 (19)	O3—C9—C6	125.3 (3)
O1—C1—C11	106.2 (2)	O3—C9—H9	117.4
O1—C1—C10	106.6 (2)	C6—C9—H9	117.4
C11—C1—C10	110.4 (3)	C1—C10—H10A	109.5
O1—C1—C2	103.52 (16)	C1—C10—H10B	109.5
C11—C1—C2	114.2 (2)	H10A—C10—H10B	109.5
C10—C1—C2	114.9 (2)	C1—C10—H10C	109.5
O2—C2—C12	105.7 (2)	H10A—C10—H10C	109.5
O2—C2—C13	107.6 (2)	H10B—C10—H10C	109.5
C12—C2—C13	111.2 (3)	C1—C11—H11A	109.5
O2—C2—C1	103.43 (15)	C1—C11—H11B	109.5
C12—C2—C1	114.2 (2)	H11A—C11—H11B	109.5
C13—C2—C1	113.9 (2)	C1—C11—H11C	109.5
C8—C3—C4	116.9 (2)	H11A—C11—H11C	109.5
C8—C3—B1	121.37 (19)	H11B—C11—H11C	109.5
C4—C3—B1	121.71 (18)	C2—C12—H12A	109.5
C5—C4—C3	121.8 (2)	C2—C12—H12B	109.5
C5—C4—H4	119.1	H12A—C12—H12B	109.5
C3—C4—H4	119.1	C2—C12—H12C	109.5
C4—C5—C6	120.5 (2)	H12A—C12—H12C	109.5
C4—C5—H5	119.7	H12B—C12—H12C	109.5
C6—C5—H5	119.7	C2—C13—H13A	109.5
C5—C6—C7	118.7 (2)	C2—C13—H13B	109.5
C5—C6—C9	120.6 (2)	H13A—C13—H13B	109.5
C7—C6—C9	120.7 (2)	C2—C13—H13C	109.5
C8—C7—C6	120.6 (2)	H13A—C13—H13C	109.5
C8—C7—H7	119.7	H13B—C13—H13C	109.5