Ethyl (O-B)-5-(di­fluoro­boryl­oxy)­tri­cyclo­[4.3.1.1^3,8]­un­decane-4-carboxyl­ate

The title compound, C₁₄H₁₉BF₂O₃, can be described as a resonance hybrid. The entering BF₂ moiety interacts with the C=O (oxo) groups of the parent compound, 5-(ethoxy­carbonyl)­adamantan-4-one, generating two conjugated double bonds in the six-membered di­fluoro­dioxoborane ring. In spite of the conjugation between the multiple bonds, the tetrahedral configuration of the B atom gives rise to a non-planar conformation of the six-membered ring, which assumes a state intermediate between the boat and sofa forms.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.049
• wR factor = 0.170
• Data-to-parameter ratio = 32.7

checkCIF/PLATON results

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Computing details

Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1992); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

ethyl 5-oxotricyclo[4.3.1.1^3,8]undecane-4-carboxylate difluoroborate

Crystal data

C14H19BF2O3	Z = 2
Mr = 284.10	F(000) = 300
Triclinic, P1	Dx = 1.390 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71070 Å
a = 7.169 (1) Å	Cell parameters from 25 reflections
b = 8.049 (1) Å	θ = 18.0–18.9°
c = 11.858 (1) Å	µ = 0.11 mm^−1
α = 89.06 (1)°	T = 293 K
β = 83.36 (1)°	Prism, colourless
γ = 87.22 (1)°	0.50 × 0.50 × 0.45 mm
V = 678.82 (14) Å^3

Data collection

Enraf-Nonius CAD-4 diffractometer	3332 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.011
Graphite monochromator	θmax = 35.0°, θmin = 2.5°
ω–θ scans	h = −11→11
Absorption correction: ψ scan (North et al., 1968)	k = −6→12
Tmin = 0.936, Tmax = 0.951	l = −19→19
6462 measured reflections	3 standard reflections every 60 min
5947 independent reflections	intensity decay: 2%

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.170	H-atom parameters constrained
S = 1.10	w = 1/[σ^2(Fo^2) + (0.0914P)^2] where P = (Fo^2 + 2Fc^2)/3
5947 reflections	(Δ/σ)max = 0.001
182 parameters	Δρmax = 0.30 e Å^−3
179 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	0.71014 (18)	0.36899 (15)	0.07444 (10)	0.0542 (3)
H1	0.7036	0.4513	0.0130	0.070*
C2	0.54699 (19)	0.25402 (17)	0.07187 (10)	0.0555 (3)
H2A	0.4298	0.3178	0.0914	0.072*
H2B	0.5473	0.2141	−0.0049	0.072*
C3	0.55396 (16)	0.10398 (13)	0.15272 (8)	0.0445 (2)
H3	0.4684	0.0239	0.1285	0.058*
C4	0.48439 (13)	0.14624 (12)	0.27490 (8)	0.0392 (2)
C5	0.56568 (14)	0.26194 (12)	0.33489 (8)	0.0399 (2)
C6	0.73827 (15)	0.34994 (14)	0.28805 (10)	0.0468 (2)
H6	0.7709	0.4217	0.3481	0.061*
C7	0.90558 (15)	0.22488 (16)	0.25932 (10)	0.0508 (3)
H7A	1.0212	0.2827	0.2593	0.066*
H7B	0.9034	0.1405	0.3187	0.066*
C8	0.90812 (16)	0.13906 (14)	0.14523 (10)	0.0497 (3)
H8	1.0286	0.0761	0.1298	0.065*
C9	0.89596 (18)	0.26922 (16)	0.05192 (10)	0.0556 (3)
H9A	0.9039	0.2155	−0.0212	0.072*
H9B	0.9997	0.3426	0.0505	0.072*
C10	0.70457 (18)	0.46273 (14)	0.18583 (12)	0.0558 (3)
H10A	0.5830	0.5211	0.2013	0.073*
H10B	0.7994	0.5454	0.1770	0.073*
C11	0.75014 (18)	0.01804 (13)	0.14085 (9)	0.0499 (3)
H11A	0.7702	−0.0404	0.0693	0.065*
H11B	0.7564	−0.0639	0.2014	0.065*
C12	0.35195 (14)	0.04821 (13)	0.33921 (9)	0.0413 (2)
C13	0.17288 (19)	−0.19549 (17)	0.36122 (11)	0.0588 (3)
H13A	0.0543	−0.1382	0.3881	0.076*
H13B	0.2328	−0.2351	0.4265	0.076*
C14	0.1412 (2)	−0.33506 (18)	0.28921 (14)	0.0743 (4)
H14A	0.0844	−0.2940	0.2241	0.112*
H14B	0.0593	−0.4104	0.3316	0.112*
H14C	0.2591	−0.3923	0.2647	0.112*
O1	0.50478 (11)	0.29875 (10)	0.44054 (6)	0.0504 (2)
O2	0.28850 (11)	0.07668 (10)	0.44265 (6)	0.0503 (2)
O3	0.29505 (11)	−0.08253 (10)	0.29158 (7)	0.0496 (2)
B1	0.32616 (18)	0.23966 (17)	0.49515 (10)	0.0470 (3)
F1	0.33825 (12)	0.21058 (11)	0.60759 (6)	0.0662 (2)
F2	0.18140 (10)	0.34935 (10)	0.47812 (7)	0.0663 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0600 (7)	0.0482 (6)	0.0526 (6)	−0.0072 (5)	0.0006 (5)	0.0160 (5)
C2	0.0583 (7)	0.0632 (7)	0.0458 (6)	−0.0079 (6)	−0.0088 (5)	0.0089 (5)
C3	0.0515 (5)	0.0464 (5)	0.0355 (4)	−0.0153 (4)	0.0007 (4)	−0.0035 (4)
C4	0.0374 (4)	0.0411 (5)	0.0384 (4)	−0.0091 (4)	0.0017 (3)	−0.0026 (4)
C5	0.0384 (4)	0.0396 (5)	0.0408 (5)	−0.0059 (4)	0.0022 (4)	−0.0046 (4)
C6	0.0422 (5)	0.0457 (5)	0.0520 (6)	−0.0140 (4)	0.0034 (4)	−0.0094 (4)
C7	0.0383 (5)	0.0618 (7)	0.0520 (6)	−0.0073 (5)	−0.0020 (4)	0.0018 (5)
C8	0.0442 (5)	0.0507 (6)	0.0505 (6)	0.0032 (4)	0.0085 (4)	0.0019 (5)
C9	0.0569 (6)	0.0583 (7)	0.0479 (6)	−0.0100 (5)	0.0119 (5)	0.0076 (5)
C10	0.0537 (6)	0.0393 (5)	0.0720 (8)	−0.0088 (5)	0.0054 (5)	0.0030 (5)
C11	0.0634 (7)	0.0408 (5)	0.0415 (5)	−0.0021 (5)	0.0106 (5)	−0.0022 (4)
C12	0.0357 (4)	0.0453 (5)	0.0426 (5)	−0.0090 (4)	−0.0001 (4)	−0.0030 (4)
C13	0.0581 (7)	0.0613 (7)	0.0572 (7)	−0.0305 (6)	0.0041 (5)	0.0026 (5)
C14	0.0890 (10)	0.0561 (7)	0.0762 (9)	−0.0328 (7)	0.0107 (8)	−0.0061 (6)
O1	0.0505 (4)	0.0546 (4)	0.0450 (4)	−0.0135 (3)	0.0062 (3)	−0.0144 (3)
O2	0.0483 (4)	0.0548 (4)	0.0454 (4)	−0.0154 (3)	0.0104 (3)	−0.0044 (3)
O3	0.0490 (4)	0.0518 (4)	0.0483 (4)	−0.0233 (3)	0.0020 (3)	−0.0046 (3)
B1	0.0470 (6)	0.0532 (6)	0.0383 (5)	−0.0047 (5)	0.0070 (4)	−0.0044 (5)
F1	0.0804 (5)	0.0777 (5)	0.0390 (3)	−0.0118 (4)	0.0024 (3)	−0.0004 (3)
F2	0.0560 (4)	0.0665 (5)	0.0725 (5)	0.0075 (4)	0.0047 (4)	−0.0010 (4)

Geometric parameters (Å, º)

C1—C9	1.5205 (18)	C8—C11	1.5351 (16)
C1—C10	1.5275 (19)	C8—H8	0.9800
C1—C2	1.5295 (18)	C9—H9A	0.9700
C1—H1	0.9800	C9—H9B	0.9700
C2—C3	1.5321 (16)	C10—H10A	0.9700
C2—H2A	0.9700	C10—H10B	0.9700
C2—H2B	0.9700	C11—H11A	0.9700
C3—C4	1.5154 (13)	C11—H11B	0.9700
C3—C11	1.5295 (17)	C12—O2	1.2784 (12)
C3—H3	0.9800	C12—O3	1.3065 (12)
C4—C5	1.3723 (13)	C13—O3	1.4701 (13)
C4—C12	1.4111 (13)	C13—C14	1.4643 (19)
C5—O1	1.3118 (12)	C13—H13A	0.9700
C5—C6	1.5014 (13)	C13—H13B	0.9700
C6—C10	1.5370 (18)	C14—H14A	0.9600
C6—C7	1.5387 (16)	C14—H14B	0.9600
C6—H6	0.9800	C14—H14C	0.9600
C7—C8	1.5270 (17)	O1—B1	1.4638 (14)
C7—H7A	0.9700	O2—B1	1.5104 (15)
C7—H7B	0.9700	B1—F2	1.3606 (16)
C8—C9	1.5181 (17)	B1—F1	1.3618 (15)
C9—C1—C10	109.56 (10)	C8—C9—C1	108.92 (9)
C9—C1—C2	109.73 (10)	C8—C9—H9A	109.9
C10—C1—C2	113.50 (10)	C1—C9—H9A	109.9
C9—C1—H1	108.0	C8—C9—H9B	109.9
C10—C1—H1	108.0	C1—C9—H9B	109.9
C2—C1—H1	108.0	H9A—C9—H9B	108.3
C3—C2—C1	113.98 (10)	C1—C10—C6	113.70 (9)
C3—C2—H2A	108.8	C1—C10—H10A	108.8
C1—C2—H2A	108.8	C6—C10—H10A	108.8
C3—C2—H2B	108.8	C1—C10—H10B	108.8
C1—C2—H2B	108.8	C6—C10—H10B	108.8
H2A—C2—H2B	107.7	H10A—C10—H10B	107.7
C4—C3—C2	113.16 (9)	C3—C11—C8	113.26 (9)
C4—C3—C11	112.16 (9)	C3—C11—H11A	108.9
C2—C3—C11	110.84 (9)	C8—C11—H11A	108.9
C4—C3—H3	106.7	C3—C11—H11B	108.9
C2—C3—H3	106.7	C8—C11—H11B	108.9
C11—C3—H3	106.7	H11A—C11—H11B	107.7
C5—C4—C12	115.55 (9)	O2—C12—O3	117.89 (9)
C5—C4—C3	122.80 (8)	O2—C12—C4	123.87 (9)
C12—C4—C3	120.83 (8)	O3—C12—C4	118.20 (9)
O1—C5—C4	122.69 (9)	O3—C13—C14	107.16 (10)
O1—C5—C6	114.10 (8)	O3—C13—H13A	110.3
C4—C5—C6	123.11 (9)	C14—C13—H13A	110.3
C5—C6—C10	112.51 (10)	O3—C13—H13B	110.3
C5—C6—C7	110.81 (9)	C14—C13—H13B	110.3
C10—C6—C7	111.58 (9)	H13A—C13—H13B	108.5
C5—C6—H6	107.2	C13—C14—H14A	109.5
C10—C6—H6	107.2	C13—C14—H14B	109.5
C7—C6—H6	107.2	H14A—C14—H14B	109.5
C8—C7—C6	114.51 (10)	C13—C14—H14C	109.5
C8—C7—H7A	108.6	H14A—C14—H14C	109.5
C6—C7—H7A	108.6	H14B—C14—H14C	109.5
C8—C7—H7B	108.6	C5—O1—B1	121.26 (8)
C6—C7—H7B	108.6	C12—O2—B1	119.47 (8)
H7A—C7—H7B	107.6	C12—O3—C13	118.71 (9)
C9—C8—C7	109.56 (10)	F2—B1—F1	111.94 (9)
C9—C8—C11	108.92 (10)	F2—B1—O1	110.90 (10)
C7—C8—C11	114.15 (9)	F1—B1—O1	109.72 (10)
C9—C8—H8	108.0	F2—B1—O2	107.60 (10)
C7—C8—H8	108.0	F1—B1—O2	107.63 (10)
C11—C8—H8	108.0	O1—B1—O2	108.93 (8)
C9—C1—C2—C3	54.66 (13)	C2—C1—C10—C6	67.50 (13)
C10—C1—C2—C3	−68.29 (14)	C5—C6—C10—C1	−79.66 (12)
C1—C2—C3—C4	79.37 (13)	C7—C6—C10—C1	45.60 (13)
C1—C2—C3—C11	−47.63 (13)	C4—C3—C11—C8	−78.53 (11)
C2—C3—C4—C5	−59.52 (14)	C2—C3—C11—C8	49.02 (12)
C11—C3—C4—C5	66.78 (13)	C9—C8—C11—C3	−57.55 (11)
C2—C3—C4—C12	131.28 (11)	C7—C8—C11—C3	65.23 (12)
C11—C3—C4—C12	−102.41 (11)	C5—C4—C12—O2	9.69 (16)
C12—C4—C5—O1	−10.53 (16)	C3—C4—C12—O2	179.63 (10)
C3—C4—C5—O1	179.75 (10)	C5—C4—C12—O3	−168.04 (10)
C12—C4—C5—C6	165.77 (10)	C3—C4—C12—O3	1.90 (16)
C3—C4—C5—C6	−3.95 (17)	C4—C5—O1—B1	−10.67 (16)
O1—C5—C6—C10	−118.55 (10)	C6—C5—O1—B1	172.72 (10)
C4—C5—C6—C10	64.86 (14)	O3—C12—O2—B1	−170.48 (10)
O1—C5—C6—C7	115.77 (10)	C4—C12—O2—B1	11.78 (16)
C4—C5—C6—C7	−60.83 (14)	O2—C12—O3—C13	−4.30 (16)
C5—C6—C7—C8	81.21 (12)	C4—C12—O3—C13	173.57 (10)
C10—C6—C7—C8	−45.00 (13)	C14—C13—O3—C12	−176.39 (12)
C6—C7—C8—C9	53.94 (12)	C5—O1—B1—F2	−88.99 (12)
C6—C7—C8—C11	−68.50 (13)	C5—O1—B1—F1	146.84 (10)
C7—C8—C9—C1	−62.40 (12)	C5—O1—B1—O2	29.25 (14)
C11—C8—C9—C1	63.10 (12)	C12—O2—B1—F2	90.69 (11)
C10—C1—C9—C8	63.46 (12)	C12—O2—B1—F1	−148.50 (10)
C2—C1—C9—C8	−61.79 (13)	C12—O2—B1—O1	−29.60 (14)
C9—C1—C10—C6	−55.54 (12)