A vinyl­ic α-carbamoyl­oxyborane with a carbenoid-type bonding arrangement

In the crystal structure, the title compound, C₂₅H₅₂BNO₃Si, a vinyl­ic α-carbamoyl­oxyborane, forms the five-membered ring of an alkyl­idene oxoniaboratadi­hydro­furan as a result of the bonding interaction of the carbonyl group with the boron atom. The ring is almost planar, with the boron atom in a tetrahedral configuration. The mol­ecule exhibits a carbenoid-type bonding arrangement.

Key indicators

• Single-crystal X-ray study
• T = 193 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.059
• wR factor = 0.169
• Data-to-parameter ratio = 10.6

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level A:



THETM_01  Alert A The value of sine(theta_max)/wavelength is less than 0.550
          Calculated sin(theta_max)/wavelength =    0.5327

General Notes



ABSTM_02  When printed, the submitted absorption T values will be replaced
          by the scaled T values. Since the ratio of scaled T's is
          identical to the ratio of reported T values, the scaling does
          not imply a change to the absorption corrections used in the
          study.
          Ratio of Tmax expected/reported      1.372
          Tmax scaled      0.919 Tmin scaled      0.686


 1 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 0 Alert Level C = Please check

---

S1. Comment

Nucleophilic substitution at cyclopropane and especially vinyl-type carbon atoms occurs only if the respective carbon bears both a metal and a leaving group (carbenoid) (Boche & Lohrenz, 2001; Kocieński & Barber, 1990), or if a metallate rearrangement is involved. The latter requires a leaving group and an -ate complex of Al, B, Cu, Ni, Zn or Zr at the same carbon atom (Nelson & Matthews, 1994; Harada et al., 1993; Sidduri et al., 1993). Here we describe the solid-state structure of the vinylic α-carbamoyloxy boran, (I), which was formed from the corresponding lithium borate and acetic acid (Birkinshaw & Kocieński, 1991).

Owing to the bonding contact of the carbonyl group to boron, the structure has to be described as an oxoniaborata dihydrofuran. A comparable situation can be found in the crystal structure of 2,2-Diethyl-3,4-dimethoxy-5-((1-phenylethyl)amino)1-oxonia-2-borata -1(5),3-cyclopentadiene (Barua et al., 1987).

Most remarkably, the C1—O1 bond is lengthened to 1.460 (4) Å. In six non-metallated carbamoyloxy-substituted vinylic compounds, the mean C_sp2—O(carbamoyloxy) value is 1.396 Å (Boche et al. 1992). It thus turns out that a boron substituent together with a leaving group leads also to a carbenoid-type bonding situation, as is the case with lithium (Boche & Lohrenz, 2001; Boche et al., 1992).

S2. Experimental

Please give some details of the preparation of the title compound.

S3. Refinement

The disorder of the isopropyl group bonded to C5 was refined using restraints for distances and temperature factores.

Computing details

Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2001); software used to prepare material for publication: SHELXTL (Sheldrick, 1996).

Figures

Fig. 1. DIAMOND (Brandenburg, 2001) drawing of the title compound, showing the atomic numbering and disorder of the isopropyl group bonded to C5. Displacement ellipsoids are drawn here at the 30% probability level. Methyl and methylene H atoms are not shown.

3,3-diethyl-5-diisopropylamino-2- (2,4-dimethyl-3-(tert-butyl-dimethylsilyloxy)-pentyliden)- 4-oxonia-3-borata-2,3-dihydrofuran

Crystal data

C25H52BNO3Si	F(000) = 1008
Mr = 453.58	Dx = 0.995 Mg m^−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54178 Å
a = 14.684 (6) Å	Cell parameters from 25 reflections
b = 9.355 (1) Å	θ = 35–50°
c = 22.515 (9) Å	µ = 0.84 mm^−1
β = 101.68 (2)°	T = 193 K
V = 3028.8 (18) Å^3	Needle, colorless
Z = 4	0.4 × 0.2 × 0.1 mm

Data collection

Enraf Nonius CAD-4 diffractometer	2882 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.046
Graphite monochromator	θmax = 55.2°, θmin = 4.0°
ω scans	h = 0→15
Absorption correction: part of the refinement model (ΔF) (DIFABS; Walker & Stuart, 1983)	k = 0→9
Tmin = 0.50, Tmax = 0.67	l = −23→23
3959 measured reflections	2 standard reflections every 60 min
3786 independent reflections	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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.169	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0818P)^2 + 2.3718P] where P = (Fo^2 + 2Fc^2)/3
3786 reflections	(Δ/σ)max < 0.001
356 parameters	Δρmax = 0.55 e Å^−3
25 restraints	Δρmin = −0.18 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	Occ. (<1)
B1	−0.0863 (3)	0.3880 (4)	0.63219 (18)	0.0489 (10)
O1	−0.05233 (16)	0.6150 (2)	0.68841 (10)	0.0547 (6)
O2	−0.11881 (15)	0.5355 (2)	0.59696 (10)	0.0521 (6)
C1	−0.0441 (2)	0.4605 (4)	0.69673 (16)	0.0548 (9)
C2	−0.0079 (3)	0.4197 (5)	0.75204 (19)	0.0740 (13)
H2	−0.005 (3)	0.325 (5)	0.7562 (18)	0.085 (14)*
C3	0.0219 (4)	0.5076 (5)	0.8088 (2)	0.0938 (17)
H3	0.037 (3)	0.605 (5)	0.796 (2)	0.103 (15)*
C5	0.1097 (3)	0.4618 (5)	0.84798 (19)	0.0837 (13)
H5B	0.1166	0.5149	0.8872	0.100*	0.548 (18)
H5A	0.1184	0.5161	0.8870	0.100*	0.452 (18)
O3	0.10279 (16)	0.3106 (3)	0.86086 (10)	0.0606 (7)
Si1	0.13984 (6)	0.22269 (11)	0.92340 (4)	0.0539 (3)
C9	0.0881 (3)	0.2950 (5)	0.98653 (17)	0.0801 (12)
H9A	0.1091	0.2376	1.0231	0.120*
H9B	0.0201	0.2910	0.9750	0.120*
H9C	0.1078	0.3944	0.9946	0.120*
C10	0.2679 (3)	0.2308 (5)	0.9465 (2)	0.0824 (13)
H10A	0.2885	0.1681	0.9815	0.124*
H10B	0.2871	0.3292	0.9575	0.124*
H10C	0.2960	0.1993	0.9128	0.124*
C11	0.1014 (3)	0.0354 (5)	0.90311 (18)	0.0721 (11)
C12	0.1355 (5)	−0.0655 (6)	0.9554 (2)	0.120 (2)
H12A	0.1119	−0.0340	0.9910	0.181*
H12B	0.2036	−0.0655	0.9650	0.181*
H12C	0.1129	−0.1623	0.9441	0.181*
C13	0.1393 (4)	−0.0128 (5)	0.8480 (2)	0.0933 (14)
H13A	0.1167	0.0518	0.8139	0.140*
H13B	0.1180	−0.1103	0.8368	0.140*
H13C	0.2074	−0.0108	0.8578	0.140*
C14	−0.0064 (3)	0.0318 (6)	0.8857 (3)	0.1135 (18)
H14A	−0.0324	0.0619	0.9205	0.170*
H14B	−0.0272	−0.0656	0.8739	0.170*
H14C	−0.0278	0.0970	0.8516	0.170*
C15	−0.1772 (3)	0.2943 (4)	0.6325 (2)	0.0608 (10)
H15A	−0.200 (2)	0.252 (4)	0.5930 (18)	0.069 (11)*
H15B	−0.158 (3)	0.214 (5)	0.6611 (18)	0.082 (12)*
C16	−0.2568 (3)	0.3723 (5)	0.6520 (2)	0.0913 (14)
H16A	−0.3077	0.3051	0.6529	0.137*
H16B	−0.2789	0.4493	0.6232	0.137*
H16C	−0.2353	0.4129	0.6926	0.137*
C17	−0.0115 (3)	0.3166 (4)	0.5991 (2)	0.0629 (10)
H17A	0.012 (3)	0.240 (4)	0.6222 (17)	0.077 (13)*
H17B	−0.045 (3)	0.281 (4)	0.5574 (18)	0.076 (12)*
C18	0.0688 (3)	0.4131 (5)	0.5903 (2)	0.0814 (13)
H18A	0.1149	0.3563	0.5748	0.122*
H18B	0.0978	0.4560	0.6292	0.122*
H18C	0.0449	0.4889	0.5612	0.122*
C19	−0.0951 (2)	0.6402 (4)	0.63183 (15)	0.0471 (8)
N1	−0.10997 (19)	0.7748 (3)	0.61510 (12)	0.0511 (7)
C20	−0.1566 (3)	0.8062 (4)	0.55203 (16)	0.0622 (10)
H20	−0.166 (2)	0.717 (4)	0.5315 (13)	0.045 (9)*
C21	−0.2498 (3)	0.8737 (5)	0.5495 (2)	0.0946 (15)
H21A	−0.2818	0.8841	0.5071	0.142*
H21B	−0.2416	0.9680	0.5688	0.142*
H21C	−0.2869	0.8130	0.5710	0.142*
C22	−0.0932 (4)	0.8947 (5)	0.52033 (19)	0.0931 (15)
H22A	−0.1218	0.9041	0.4772	0.140*
H22B	−0.0329	0.8470	0.5245	0.140*
H22C	−0.0844	0.9897	0.5389	0.140*
C23	−0.0802 (3)	0.8962 (4)	0.65749 (18)	0.0663 (11)
H23	−0.102 (2)	0.975 (4)	0.6307 (16)	0.067 (11)*
C24	−0.1303 (4)	0.8964 (5)	0.71037 (19)	0.0964 (16)
H24A	−0.1206	0.9886	0.7314	0.145*
H24B	−0.1055	0.8196	0.7386	0.145*
H24C	−0.1969	0.8812	0.6952	0.145*
C25	0.0239 (3)	0.9069 (5)	0.6762 (2)	0.0925 (15)
H25A	0.0477	0.8253	0.7020	0.139*
H25B	0.0405	0.9959	0.6988	0.139*
H25C	0.0515	0.9066	0.6401	0.139*
C4	−0.0586 (4)	0.5000 (7)	0.8490 (2)	0.123 (2)
H4A	−0.0721	0.3998	0.8565	0.185*
H4B	−0.1151	0.5466	0.8268	0.185*
H4C	−0.0369	0.5489	0.8877	0.185*
C6	0.1766 (10)	0.526 (2)	0.8083 (5)	0.080 (4)	0.452 (18)
H6A	0.1437	0.5973	0.7786	0.096*	0.452 (18)
C7	0.2545 (10)	0.594 (3)	0.8533 (8)	0.119 (7)	0.452 (18)
H7A	0.2809	0.5244	0.8845	0.179*	0.452 (18)
H7B	0.2303	0.6761	0.8724	0.179*	0.452 (18)
H7C	0.3030	0.6267	0.8322	0.179*	0.452 (18)
C8	0.218 (2)	0.408 (4)	0.7768 (16)	0.175 (14)	0.452 (18)
H8A	0.2680	0.4472	0.7588	0.262*	0.452 (18)
H8B	0.1695	0.3674	0.7448	0.262*	0.452 (18)
H8C	0.2427	0.3337	0.8062	0.262*	0.452 (18)
C6A	0.2064 (7)	0.4703 (13)	0.8266 (6)	0.077 (4)	0.548 (18)
H6AA	0.2575	0.4361	0.8599	0.092*	0.548 (18)
C7A	0.2273 (15)	0.6199 (18)	0.8083 (13)	0.169 (10)	0.548 (18)
H7A1	0.2912	0.6243	0.8019	0.254*	0.548 (18)
H7A2	0.2200	0.6868	0.8405	0.254*	0.548 (18)
H7A3	0.1841	0.6458	0.7707	0.254*	0.548 (18)
C8A	0.2056 (12)	0.384 (2)	0.7704 (6)	0.103 (5)	0.548 (18)
H8A1	0.1903	0.2846	0.7777	0.155*	0.548 (18)
H8A2	0.2671	0.3885	0.7598	0.155*	0.548 (18)
H8A3	0.1589	0.4232	0.7370	0.155*	0.548 (18)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
B1	0.049 (2)	0.034 (2)	0.062 (2)	0.0032 (18)	0.0075 (19)	0.0079 (18)
O1	0.0689 (16)	0.0378 (13)	0.0550 (14)	0.0025 (11)	0.0068 (12)	0.0021 (11)
O2	0.0589 (14)	0.0396 (13)	0.0560 (13)	0.0006 (11)	0.0071 (11)	−0.0015 (11)
C1	0.060 (2)	0.037 (2)	0.065 (2)	0.0001 (17)	0.0058 (18)	0.0066 (17)
C2	0.104 (3)	0.040 (2)	0.068 (3)	−0.001 (2)	−0.008 (2)	0.006 (2)
C3	0.142 (5)	0.054 (3)	0.069 (3)	−0.008 (3)	−0.018 (3)	0.002 (2)
C5	0.102 (4)	0.082 (3)	0.065 (3)	−0.008 (3)	0.012 (2)	−0.005 (2)
O3	0.0621 (15)	0.0678 (17)	0.0513 (13)	0.0156 (13)	0.0102 (11)	0.0004 (12)
Si1	0.0439 (5)	0.0689 (7)	0.0486 (5)	0.0029 (5)	0.0092 (4)	−0.0005 (5)
C9	0.077 (3)	0.102 (3)	0.064 (2)	0.000 (3)	0.023 (2)	−0.011 (2)
C10	0.055 (2)	0.105 (4)	0.082 (3)	0.000 (2)	0.003 (2)	−0.009 (3)
C11	0.075 (3)	0.075 (3)	0.068 (2)	−0.008 (2)	0.020 (2)	−0.003 (2)
C12	0.177 (6)	0.087 (4)	0.098 (4)	−0.005 (4)	0.029 (4)	0.017 (3)
C13	0.108 (4)	0.083 (3)	0.092 (3)	−0.003 (3)	0.029 (3)	−0.021 (3)
C14	0.081 (3)	0.124 (5)	0.139 (5)	−0.036 (3)	0.031 (3)	−0.027 (4)
C15	0.060 (2)	0.055 (2)	0.067 (2)	−0.004 (2)	0.0119 (19)	0.000 (2)
C16	0.062 (3)	0.100 (4)	0.120 (4)	0.001 (3)	0.036 (3)	0.002 (3)
C17	0.051 (2)	0.058 (3)	0.079 (3)	0.005 (2)	0.011 (2)	−0.002 (2)
C18	0.061 (3)	0.096 (3)	0.092 (3)	−0.005 (2)	0.027 (2)	−0.007 (3)
C19	0.0448 (19)	0.046 (2)	0.052 (2)	0.0050 (16)	0.0129 (16)	0.0012 (18)
N1	0.0632 (18)	0.0371 (17)	0.0536 (17)	0.0079 (14)	0.0128 (14)	0.0013 (13)
C20	0.085 (3)	0.044 (2)	0.055 (2)	0.011 (2)	0.0075 (19)	−0.0003 (18)
C21	0.093 (3)	0.083 (3)	0.096 (3)	0.030 (3)	−0.007 (3)	0.002 (3)
C22	0.146 (5)	0.073 (3)	0.068 (3)	0.001 (3)	0.040 (3)	0.010 (2)
C23	0.095 (3)	0.039 (2)	0.063 (2)	0.008 (2)	0.011 (2)	−0.0024 (19)
C24	0.157 (5)	0.069 (3)	0.068 (3)	0.028 (3)	0.033 (3)	−0.005 (2)
C25	0.102 (4)	0.059 (3)	0.103 (3)	−0.016 (2)	−0.010 (3)	−0.003 (2)
C4	0.095 (4)	0.203 (7)	0.075 (3)	0.033 (4)	0.025 (3)	−0.036 (4)
C6	0.088 (9)	0.077 (11)	0.078 (8)	−0.015 (8)	0.027 (7)	0.045 (6)
C7	0.088 (10)	0.123 (15)	0.158 (14)	−0.059 (10)	0.052 (10)	−0.014 (11)
C8	0.11 (2)	0.25 (3)	0.15 (2)	−0.08 (2)	−0.001 (15)	−0.04 (2)
C6A	0.084 (7)	0.068 (7)	0.084 (8)	−0.012 (6)	0.027 (6)	0.027 (6)
C7A	0.156 (15)	0.102 (10)	0.26 (3)	−0.001 (10)	0.075 (17)	0.078 (15)
C8A	0.047 (6)	0.204 (15)	0.069 (8)	0.000 (9)	0.035 (6)	0.014 (9)

Geometric parameters (Å, º)

B1—C17	1.594 (6)	C17—H17A	0.91 (4)
B1—C15	1.599 (5)	C17—H17B	1.02 (4)
B1—C1	1.609 (5)	C18—H18A	0.9800
B1—O2	1.614 (4)	C18—H18B	0.9800
O1—C19	1.322 (4)	C18—H18C	0.9800
O1—C1	1.460 (4)	C19—N1	1.320 (4)
O2—C19	1.259 (4)	N1—C20	1.476 (4)
C1—C2	1.308 (5)	N1—C23	1.491 (4)
C2—C3	1.508 (6)	C20—C21	1.498 (6)
C2—H2	0.89 (4)	C20—C22	1.526 (6)
C3—C5	1.471 (6)	C20—H20	0.95 (3)
C3—C4	1.629 (7)	C21—H21A	0.9800
C3—H3	1.00 (5)	C21—H21B	0.9800
C5—O3	1.452 (5)	C21—H21C	0.9800
C5—C6	1.573 (9)	C22—H22A	0.9800
C5—C6A	1.591 (8)	C22—H22B	0.9800
C5—H5B	1.0000	C22—H22C	0.9800
C5—H5A	1.0000	C23—C25	1.505 (6)
O3—Si1	1.626 (2)	C23—C24	1.520 (6)
Si1—C10	1.848 (4)	C23—H23	0.96 (4)
Si1—C9	1.869 (4)	C24—H24A	0.9800
Si1—C11	1.869 (4)	C24—H24B	0.9800
C9—H9A	0.9800	C24—H24C	0.9800
C9—H9B	0.9800	C25—H25A	0.9800
C9—H9C	0.9800	C25—H25B	0.9800
C10—H10A	0.9800	C25—H25C	0.9800
C10—H10B	0.9800	C4—H4A	0.9800
C10—H10C	0.9800	C4—H4B	0.9800
C11—C12	1.513 (6)	C4—H4C	0.9800
C11—C13	1.527 (6)	C6—C8	1.499 (10)
C11—C14	1.553 (6)	C6—C7	1.510 (10)
C12—H12A	0.9800	C6—H6A	1.0000
C12—H12B	0.9800	C7—H7A	0.9800
C12—H12C	0.9800	C7—H7B	0.9800
C13—H13A	0.9800	C7—H7C	0.9800
C13—H13B	0.9800	C8—H8A	0.9800
C13—H13C	0.9800	C8—H8B	0.9800
C14—H14A	0.9800	C8—H8C	0.9800
C14—H14B	0.9800	C6A—C8A	1.497 (10)
C14—H14C	0.9800	C6A—C7A	1.507 (9)
C15—C16	1.516 (6)	C6A—H6AA	1.0000
C15—H15A	0.97 (4)	C7A—H7A1	0.9800
C15—H15B	0.99 (4)	C7A—H7A2	0.9800
C16—H16A	0.9800	C7A—H7A3	0.9800
C16—H16B	0.9800	C8A—H8A1	0.9800
C16—H16C	0.9800	C8A—H8A2	0.9800
C17—C18	1.529 (5)	C8A—H8A3	0.9800
C17—B1—C15	115.3 (3)	C15—C16—H16C	109.5
C17—B1—C1	115.1 (3)	H16A—C16—H16C	109.5
C15—B1—C1	113.3 (3)	H16B—C16—H16C	109.5
C17—B1—O2	106.9 (3)	C18—C17—B1	115.8 (3)
C15—B1—O2	107.9 (3)	C18—C17—H17A	109 (2)
C1—B1—O2	96.0 (2)	B1—C17—H17A	106 (3)
C19—O1—C1	108.1 (3)	C18—C17—H17B	108 (2)
C19—O2—B1	110.0 (2)	B1—C17—H17B	108 (2)
C2—C1—O1	114.7 (3)	H17A—C17—H17B	109 (3)
C2—C1—B1	138.1 (3)	C17—C18—H18A	109.5
O1—C1—B1	107.1 (3)	C17—C18—H18B	109.5
C1—C2—C3	129.8 (4)	H18A—C18—H18B	109.5
C1—C2—H2	113 (3)	C17—C18—H18C	109.5
C3—C2—H2	117 (3)	H18A—C18—H18C	109.5
C5—C3—C2	114.8 (4)	H18B—C18—H18C	109.5
C5—C3—C4	107.5 (4)	O2—C19—N1	123.7 (3)
C2—C3—C4	109.1 (4)	O2—C19—O1	118.6 (3)
C5—C3—H3	103 (3)	N1—C19—O1	117.6 (3)
C2—C3—H3	107 (3)	C19—N1—C20	118.8 (3)
C4—C3—H3	116 (3)	C19—N1—C23	122.3 (3)
O3—C5—C3	108.4 (4)	C20—N1—C23	118.9 (3)
O3—C5—C6	124.0 (9)	N1—C20—C21	111.2 (3)
C3—C5—C6	96.9 (7)	N1—C20—C22	110.5 (3)
O3—C5—C6A	102.2 (6)	C21—C20—C22	113.1 (4)
C3—C5—C6A	122.1 (7)	N1—C20—H20	106.7 (18)
C6—C5—C6A	27.2 (5)	C21—C20—H20	108.2 (19)
O3—C5—H5B	107.8	C22—C20—H20	106.8 (19)
C3—C5—H5B	107.8	C20—C21—H21A	109.5
C6—C5—H5B	110.5	C20—C21—H21B	109.5
C6A—C5—H5B	107.8	H21A—C21—H21B	109.5
O3—C5—H5A	108.7	C20—C21—H21C	109.5
C3—C5—H5A	108.7	H21A—C21—H21C	109.5
C6—C5—H5A	108.9	H21B—C21—H21C	109.5
C6A—C5—H5A	106.1	C20—C22—H22A	109.5
H5B—C5—H5A	1.7	C20—C22—H22B	109.5
C5—O3—Si1	129.9 (2)	H22A—C22—H22B	109.5
O3—Si1—C10	111.47 (18)	C20—C22—H22C	109.5
O3—Si1—C9	111.05 (17)	H22A—C22—H22C	109.5
C10—Si1—C9	108.6 (2)	H22B—C22—H22C	109.5
O3—Si1—C11	103.34 (16)	N1—C23—C25	112.3 (3)
C10—Si1—C11	110.3 (2)	N1—C23—C24	112.1 (4)
C9—Si1—C11	112.1 (2)	C25—C23—C24	113.9 (4)
Si1—C9—H9A	109.5	N1—C23—H23	99 (2)
Si1—C9—H9B	109.5	C25—C23—H23	108 (2)
H9A—C9—H9B	109.5	C24—C23—H23	110 (2)
Si1—C9—H9C	109.5	C23—C24—H24A	109.5
H9A—C9—H9C	109.5	C23—C24—H24B	109.5
H9B—C9—H9C	109.5	H24A—C24—H24B	109.5
Si1—C10—H10A	109.5	C23—C24—H24C	109.5
Si1—C10—H10B	109.5	H24A—C24—H24C	109.5
H10A—C10—H10B	109.5	H24B—C24—H24C	109.5
Si1—C10—H10C	109.5	C23—C25—H25A	109.5
H10A—C10—H10C	109.5	C23—C25—H25B	109.5
H10B—C10—H10C	109.5	H25A—C25—H25B	109.5
C12—C11—C13	109.4 (4)	C23—C25—H25C	109.5
C12—C11—C14	110.0 (4)	H25A—C25—H25C	109.5
C13—C11—C14	108.0 (4)	H25B—C25—H25C	109.5
C12—C11—Si1	111.0 (3)	C3—C4—H4A	109.5
C13—C11—Si1	109.5 (3)	C3—C4—H4B	109.5
C14—C11—Si1	108.9 (3)	H4A—C4—H4B	109.5
C11—C12—H12A	109.5	C3—C4—H4C	109.5
C11—C12—H12B	109.5	H4A—C4—H4C	109.5
H12A—C12—H12B	109.5	H4B—C4—H4C	109.5
C11—C12—H12C	109.5	C8—C6—C7	108 (2)
H12A—C12—H12C	109.5	C8—C6—C5	110.5 (18)
H12B—C12—H12C	109.5	C7—C6—C5	104.9 (10)
C11—C13—H13A	109.5	C8—C6—H6A	111.2
C11—C13—H13B	109.5	C7—C6—H6A	111.2
H13A—C13—H13B	109.5	C5—C6—H6A	111.2
C11—C13—H13C	109.5	C8A—C6A—C7A	103.7 (19)
H13A—C13—H13C	109.5	C8A—C6A—C5	112.0 (9)
H13B—C13—H13C	109.5	C7A—C6A—C5	111.8 (11)
C11—C14—H14A	109.5	C8A—C6A—H6AA	109.7
C11—C14—H14B	109.5	C7A—C6A—H6AA	109.7
H14A—C14—H14B	109.5	C5—C6A—H6AA	109.7
C11—C14—H14C	109.5	C6A—C7A—H7A1	109.5
H14A—C14—H14C	109.5	C6A—C7A—H7A2	109.5
H14B—C14—H14C	109.5	H7A1—C7A—H7A2	109.5
C16—C15—B1	115.5 (4)	C6A—C7A—H7A3	109.5
C16—C15—H15A	109 (2)	H7A1—C7A—H7A3	109.5
B1—C15—H15A	110 (2)	H7A2—C7A—H7A3	109.5
C16—C15—H15B	108 (2)	C6A—C8A—H8A1	109.5
B1—C15—H15B	107 (2)	C6A—C8A—H8A2	109.5
H15A—C15—H15B	107 (3)	H8A1—C8A—H8A2	109.5
C15—C16—H16A	109.5	C6A—C8A—H8A3	109.5
C15—C16—H16B	109.5	H8A1—C8A—H8A3	109.5
H16A—C16—H16B	109.5	H8A2—C8A—H8A3	109.5
C17—B1—O2—C19	−115.6 (3)	C9—Si1—C11—C14	57.4 (4)
C15—B1—O2—C19	119.8 (3)	C17—B1—C15—C16	−167.9 (4)
C1—B1—O2—C19	2.9 (3)	C1—B1—C15—C16	56.6 (5)
C19—O1—C1—C2	−176.1 (4)	O2—B1—C15—C16	−48.5 (5)
C19—O1—C1—B1	2.8 (4)	C15—B1—C17—C18	171.4 (4)
C17—B1—C1—C2	−72.9 (6)	C1—B1—C17—C18	−53.8 (5)
C15—B1—C1—C2	62.8 (6)	O2—B1—C17—C18	51.5 (4)
O2—B1—C1—C2	175.2 (5)	B1—O2—C19—N1	178.0 (3)
C17—B1—C1—O1	108.7 (3)	B1—O2—C19—O1	−1.6 (4)
C15—B1—C1—O1	−115.7 (3)	C1—O1—C19—O2	−0.8 (4)
O2—B1—C1—O1	−3.2 (3)	C1—O1—C19—N1	179.6 (3)
O1—C1—C2—C3	3.5 (7)	O2—C19—N1—C20	−0.3 (5)
B1—C1—C2—C3	−174.9 (5)	O1—C19—N1—C20	179.3 (3)
C1—C2—C3—C5	−139.0 (5)	O2—C19—N1—C23	−179.5 (3)
C1—C2—C3—C4	100.4 (6)	O1—C19—N1—C23	0.1 (5)
C2—C3—C5—O3	−53.3 (6)	C19—N1—C20—C21	114.2 (4)
C4—C3—C5—O3	68.2 (5)	C23—N1—C20—C21	−66.5 (5)
C2—C3—C5—C6	76.1 (9)	C19—N1—C20—C22	−119.3 (4)
C4—C3—C5—C6	−162.4 (8)	C23—N1—C20—C22	60.0 (4)
C2—C3—C5—C6A	64.8 (7)	C19—N1—C23—C25	65.9 (5)
C4—C3—C5—C6A	−173.7 (6)	C20—N1—C23—C25	−113.3 (4)
C3—C5—O3—Si1	−140.7 (3)	C19—N1—C23—C24	−63.9 (5)
C6—C5—O3—Si1	107.1 (7)	C20—N1—C23—C24	117.0 (4)
C6A—C5—O3—Si1	89.2 (6)	O3—C5—C6—C8	11 (2)
C5—O3—Si1—C10	−62.8 (4)	C3—C5—C6—C8	−107.2 (18)
C5—O3—Si1—C9	58.4 (4)	C6A—C5—C6—C8	52 (2)
C5—O3—Si1—C11	178.7 (3)	O3—C5—C6—C7	−105.3 (18)
O3—Si1—C11—C12	176.4 (3)	C3—C5—C6—C7	137.0 (18)
C10—Si1—C11—C12	57.2 (4)	C6A—C5—C6—C7	−64.3 (18)
C9—Si1—C11—C12	−63.9 (4)	O3—C5—C6A—C8A	62.2 (14)
O3—Si1—C11—C13	55.6 (3)	C3—C5—C6A—C8A	−58.9 (14)
C10—Si1—C11—C13	−63.7 (4)	C6—C5—C6A—C8A	−84 (3)
C9—Si1—C11—C13	175.2 (3)	O3—C5—C6A—C7A	178.0 (17)
O3—Si1—C11—C14	−62.3 (3)	C3—C5—C6A—C7A	56.9 (18)
C10—Si1—C11—C14	178.4 (3)	C6—C5—C6A—C7A	31.8 (16)