Cyclo­dec-2'-ynyl (1S,1'R)-(-)-4,7,7-tri­methyl-3-oxo-2-oxabi­cyclo­[2.2.1]­heptane-1-carboxyl­ate

The synthesis and the crystal structure analysis via X-ray diffraction of the title compound, C₂₀H₂₈O₄, (I), are described. The title compound is a camphanic acid cyclo­decynyl ester. This compound contains a ten-membered ring including a triple bond and is prepared by condensation of (1S)-(-)-camphanic acid chloride with (R)-(+)-cyclo­dec-2-yn-1-ol [(II), 90% ee]. This alcohol [Hanack & Wächter (1987). Chem. Ber. 120, 727-734] has been isolated by kinetic deracemization of the corresponding acetate [Zelder (2001). PhD Thesis. In preparation] with the lipase from mucor miehei. With this structure analysis, the configuration of (II) was determined.

Key indicators

• Single-crystal X-ray study
• T = 291 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.040
• wR factor = 0.085
• Data-to-parameter ratio = 10.9

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



PLAT_320  Alert C Check Hybridisation of  C1'    in main residue          ?

PLAT_320  Alert C Check Hybridisation of  C2'    in main residue          ?

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           27.50
         From the CIF: _reflns_number_total               2407
         Count of symmetry unique reflns         2425
         Completeness (_total/calc)             99.26%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured         0
         Fraction of Friedel pairs measured     0.000
         Are heavy atom types Z>Si present           no
          Please check that the estimate of the number of Friedel pairs is
          correct. If it is not, please give the correct count in the
          _publ_section_exptl_refinement section of the submitted CIF.


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 2 Alert Level C = Please check

---

S1. Comment

No comment

S2. Experimental

The alcohol (II) was dissolved in pure pyridine·The (1S)-(-)-camphanic acid chloride was added in one portion and the mixture was stirred for 1 h at 313 K. After this process, the title compound was obtained in 85% yield. A small amount was dissolved in 1 ml of cyclohexane/diethyl ether (1:1) and crystals were obtained by vapor diffusion at room temperature.

S3. Refinement

H atoms were placed in calculated positions with U_iso constrained to be 1.5U_eq of the carrier atom for the methyl groups and with U_iso constrained to be 1.2U_eq of the carrier atom for the remaining positions. The absolute structure could not be determined reliably and the Friedel reflections were merged before final refinement.

Computing details

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1991); software used to prepare material for publication: SHELXL97 and PARST95 (Nardelli, 1995).

Figures

Fig. 1. The structure of (I) showing 30% probability displacement ellipsoids and the atom-numbering scheme.

(I)

Crystal data

C20H28O4	Dx = 1.214 Mg m^−3 Dm = not determined Mg m^−3 Dm measured by not measured
Mr = 332.42	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 11414 reflections
a = 6.5640 (3) Å	θ = 3.0–27.5°
b = 9.7316 (5) Å	µ = 0.08 mm^−1
c = 28.4686 (14) Å	T = 291 K
V = 1818.52 (15) Å^3	Plate, colourless
Z = 4	0.5 × 0.5 × 0.08 mm
F(000) = 720

Data collection

Nonius KappaCCD diffractometer	1036 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.062
Graphite monochromator	θmax = 27.5°, θmin = 3.0°
Detector resolution: 10 vertical, 18 horizontal pixels mm^-1	h = −8→8
109 frames via ω–rotation (Δω = 1°) with two sets at different κ–angles and two times 20 s per frame scans	k = −12→12
2407 measured reflections	l = −36→36
2407 independent reflections

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)] = 0.040	H-atom parameters constrained
wR(F^2) = 0.085	w = 1/[σ^2(Fo^2) + (0.025P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.96	(Δ/σ)max < 0.001
2407 reflections	Δρmax = 0.15 e Å^−3
221 parameters	Δρmin = −0.13 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.018 (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
O1	0.8919 (3)	0.69183 (19)	0.90156 (6)	0.0553 (6)
O2	0.9064 (3)	0.9255 (2)	0.94932 (6)	0.0571 (6)
O3	0.5836 (4)	0.6372 (2)	0.93045 (8)	0.0819 (8)
O4	1.0102 (4)	1.1446 (2)	0.95491 (9)	0.0827 (8)
C1	0.7061 (5)	0.8631 (3)	0.94319 (10)	0.0470 (8)
C3	0.8734 (6)	1.0658 (3)	0.94989 (10)	0.0555 (8)
C4	0.6468 (4)	1.0881 (3)	0.94386 (10)	0.0489 (8)
C5	0.5580 (5)	1.0389 (3)	0.99100 (9)	0.0638 (10)
H5A	0.6270	1.0820	1.0173	0.077*
H5B	0.4133	1.0585	0.9930	0.077*
C6	0.5975 (6)	0.8831 (3)	0.99009 (10)	0.0681 (10)
H6A	0.6832	0.8550	1.0161	0.082*
H6B	0.4709	0.8318	0.9912	0.082*
C7	0.6009 (5)	0.9658 (3)	0.91015 (9)	0.0498 (8)
C8	0.7212 (6)	0.7180 (3)	0.92567 (10)	0.0549 (9)
C9	0.7080 (6)	0.9766 (3)	0.86229 (9)	0.0720 (10)
H9A	0.8496	0.9972	0.8670	0.108*
H9B	0.6461	1.0485	0.8441	0.108*
H9C	0.6953	0.8909	0.8458	0.108*
C10	0.3750 (5)	0.9368 (4)	0.90170 (12)	0.0853 (11)
H10A	0.3597	0.8469	0.8883	0.128*
H10B	0.3206	1.0042	0.8805	0.128*
H10C	0.3030	0.9410	0.9310	0.128*
C11	0.5898 (6)	1.2321 (3)	0.93084 (11)	0.0765 (11)
H11A	0.6429	1.2532	0.9003	0.115*
H11B	0.6458	1.2948	0.9534	0.115*
H11C	0.4441	1.2407	0.9305	0.115*
C1'	0.6888 (5)	0.5408 (3)	0.80101 (12)	0.0573 (9)
C2'	0.7664 (5)	0.5567 (3)	0.83747 (12)	0.0554 (9)
C3'	0.8969 (5)	0.5565 (3)	0.87930 (10)	0.0551 (8)
H3'	0.8488	0.4868	0.9015	0.066*
C4'	1.1170 (5)	0.5284 (3)	0.86658 (10)	0.0570 (9)
H4'1	1.2032	0.5573	0.8924	0.068*
H4'2	1.1529	0.5834	0.8394	0.068*
C5'	1.1607 (5)	0.3772 (3)	0.85570 (11)	0.0710 (10)
H5'1	1.1459	0.3259	0.8847	0.085*
H5'2	1.3024	0.3701	0.8463	0.085*
C6'	1.0314 (6)	0.3049 (3)	0.81791 (11)	0.0682 (10)
H6'1	1.0715	0.2091	0.8167	0.082*
H6'2	0.8899	0.3079	0.8277	0.082*
C7'	1.0461 (5)	0.3640 (3)	0.76858 (11)	0.0732 (10)
H7'1	1.1792	0.3415	0.7560	0.088*
H7'2	1.0378	0.4633	0.7708	0.088*
C8'	0.8845 (6)	0.3149 (4)	0.73377 (11)	0.0819 (12)
H8'1	0.9148	0.3552	0.7034	0.098*
H8'2	0.8981	0.2161	0.7305	0.098*
C9'	0.6627 (6)	0.3466 (3)	0.74556 (11)	0.0752 (11)
H9'1	0.5783	0.3148	0.7198	0.090*
H9'2	0.6251	0.2941	0.7732	0.090*
C10'	0.6137 (6)	0.4972 (3)	0.75466 (10)	0.0677 (10)
H0'1	0.6760	0.5534	0.7305	0.081*
H0'2	0.4674	0.5108	0.7532	0.081*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0554 (16)	0.0531 (14)	0.0575 (13)	0.0024 (12)	0.0075 (12)	−0.0126 (11)
O2	0.0459 (14)	0.0596 (15)	0.0658 (13)	0.0033 (12)	−0.0086 (11)	−0.0114 (11)
O3	0.0750 (18)	0.0707 (15)	0.0999 (18)	−0.0231 (15)	0.0314 (15)	−0.0182 (13)
O4	0.0612 (17)	0.0713 (17)	0.1154 (19)	−0.0206 (14)	−0.0018 (14)	−0.0278 (14)
C1	0.044 (2)	0.050 (2)	0.0479 (19)	−0.0042 (16)	0.0048 (16)	−0.0057 (16)
C3	0.062 (3)	0.050 (2)	0.0546 (19)	0.004 (2)	0.0041 (18)	−0.0129 (17)
C4	0.049 (2)	0.049 (2)	0.0493 (19)	0.0094 (17)	0.0033 (16)	−0.0026 (16)
C5	0.072 (2)	0.061 (2)	0.059 (2)	0.005 (2)	0.0183 (18)	−0.0115 (17)
C6	0.086 (3)	0.068 (2)	0.0508 (19)	0.000 (2)	0.0192 (19)	−0.0038 (16)
C7	0.041 (2)	0.062 (2)	0.0457 (17)	−0.0013 (18)	−0.0016 (15)	−0.0008 (16)
C8	0.059 (3)	0.058 (2)	0.047 (2)	−0.003 (2)	0.005 (2)	−0.0050 (17)
C9	0.089 (3)	0.078 (2)	0.0494 (17)	−0.005 (2)	0.0003 (19)	0.0038 (17)
C10	0.055 (3)	0.103 (3)	0.098 (3)	−0.004 (2)	−0.012 (2)	−0.011 (2)
C11	0.082 (3)	0.063 (2)	0.085 (2)	0.008 (2)	−0.004 (2)	0.0025 (18)
C1'	0.054 (2)	0.052 (2)	0.067 (2)	0.0032 (17)	−0.0050 (19)	−0.0098 (19)
C2'	0.053 (2)	0.050 (2)	0.063 (2)	0.0066 (19)	0.0006 (19)	−0.0138 (18)
C3'	0.061 (2)	0.050 (2)	0.0544 (18)	0.0018 (19)	0.0028 (18)	−0.0090 (16)
C4'	0.054 (2)	0.058 (2)	0.0585 (19)	0.0076 (19)	−0.0048 (16)	−0.0062 (16)
C5'	0.062 (3)	0.079 (2)	0.072 (2)	0.019 (2)	0.000 (2)	0.005 (2)
C6'	0.073 (3)	0.053 (2)	0.079 (2)	0.013 (2)	0.009 (2)	−0.0061 (19)
C7'	0.067 (3)	0.082 (2)	0.070 (2)	0.002 (2)	0.020 (2)	−0.005 (2)
C8'	0.083 (3)	0.090 (3)	0.073 (2)	−0.006 (3)	0.003 (2)	−0.028 (2)
C9'	0.080 (3)	0.075 (3)	0.071 (2)	−0.015 (2)	−0.013 (2)	−0.0146 (19)
C10'	0.070 (3)	0.065 (2)	0.068 (2)	−0.0047 (19)	−0.0167 (19)	−0.0018 (17)

Geometric parameters (Å, º)

O1—C8	1.338 (4)	C11—H11B	0.9600
O1—C3'	1.462 (3)	C11—H11C	0.9600
O2—C3	1.383 (3)	C1'—C2'	1.167 (4)
O2—C1	1.459 (3)	C1'—C10'	1.471 (4)
O3—C8	1.205 (4)	C2'—C3'	1.467 (4)
O4—C3	1.189 (3)	C3'—C4'	1.514 (4)
C1—C8	1.501 (4)	C3'—H3'	0.9800
C1—C6	1.526 (4)	C4'—C5'	1.531 (4)
C1—C7	1.536 (4)	C4'—H4'1	0.9700
C3—C4	1.512 (4)	C4'—H4'2	0.9700
C4—C11	1.497 (4)	C5'—C6'	1.540 (4)
C4—C5	1.540 (4)	C5'—H5'1	0.9700
C4—C7	1.558 (4)	C5'—H5'2	0.9700
C5—C6	1.539 (4)	C6'—C7'	1.521 (4)
C5—H5A	0.9700	C6'—H6'1	0.9700
C5—H5B	0.9700	C6'—H6'2	0.9700
C6—H6A	0.9700	C7'—C8'	1.528 (4)
C6—H6B	0.9700	C7'—H7'1	0.9700
C7—C10	1.529 (4)	C7'—H7'2	0.9700
C7—C9	1.537 (4)	C8'—C9'	1.526 (5)
C9—H9A	0.9600	C8'—H8'1	0.9700
C9—H9B	0.9600	C8'—H8'2	0.9700
C9—H9C	0.9600	C9'—C10'	1.523 (4)
C10—H10A	0.9600	C9'—H9'1	0.9700
C10—H10B	0.9600	C9'—H9'2	0.9700
C10—H10C	0.9600	C10'—H0'1	0.9700
C11—H11A	0.9600	C10'—H0'2	0.9700
C8—O1—C3'	114.4 (2)	C4—C11—H11C	109.5
C3—O2—C1	105.7 (2)	H11A—C11—H11C	109.5
O2—C1—C8	111.8 (3)	H11B—C11—H11C	109.5
O2—C1—C6	105.3 (2)	C2'—C1'—C10'	169.4 (3)
C8—C1—C6	116.2 (3)	C1'—C2'—C3'	167.7 (3)
O2—C1—C7	102.0 (2)	O1—C3'—C2'	109.7 (2)
C8—C1—C7	116.0 (2)	O1—C3'—C4'	106.7 (2)
C6—C1—C7	104.1 (2)	C2'—C3'—C4'	111.3 (2)
O4—C3—O2	121.3 (3)	O1—C3'—H3'	109.7
O4—C3—C4	131.6 (3)	C2'—C3'—H3'	109.7
O2—C3—C4	107.1 (3)	C4'—C3'—H3'	109.7
C11—C4—C3	114.1 (3)	C3'—C4'—C5'	113.6 (3)
C11—C4—C5	114.3 (2)	C3'—C4'—H4'1	108.8
C3—C4—C5	103.2 (3)	C5'—C4'—H4'1	108.8
C11—C4—C7	120.9 (2)	C3'—C4'—H4'2	108.8
C3—C4—C7	98.7 (2)	C5'—C4'—H4'2	108.8
C5—C4—C7	103.1 (2)	H4'1—C4'—H4'2	107.7
C6—C5—C4	103.2 (2)	C4'—C5'—C6'	118.5 (3)
C6—C5—H5A	111.1	C4'—C5'—H5'1	107.7
C4—C5—H5A	111.1	C6'—C5'—H5'1	107.7
C6—C5—H5B	111.1	C4'—C5'—H5'2	107.7
C4—C5—H5B	111.1	C6'—C5'—H5'2	107.7
H5A—C5—H5B	109.1	H5'1—C5'—H5'2	107.1
C1—C6—C5	102.6 (2)	C7'—C6'—C5'	115.9 (3)
C1—C6—H6A	111.2	C7'—C6'—H6'1	108.3
C5—C6—H6A	111.2	C5'—C6'—H6'1	108.3
C1—C6—H6B	111.2	C7'—C6'—H6'2	108.3
C5—C6—H6B	111.2	C5'—C6'—H6'2	108.3
H6A—C6—H6B	109.2	H6'1—C6'—H6'2	107.4
C10—C7—C1	114.3 (3)	C6'—C7'—C8'	115.9 (3)
C10—C7—C9	108.5 (3)	C6'—C7'—H7'1	108.3
C1—C7—C9	112.4 (3)	C8'—C7'—H7'1	108.3
C10—C7—C4	115.2 (3)	C6'—C7'—H7'2	108.3
C1—C7—C4	91.9 (2)	C8'—C7'—H7'2	108.3
C9—C7—C4	113.9 (2)	H7'1—C7'—H7'2	107.4
O3—C8—O1	124.2 (3)	C9'—C8'—C7'	117.1 (3)
O3—C8—C1	121.8 (3)	C9'—C8'—H8'1	108.0
O1—C8—C1	113.8 (3)	C7'—C8'—H8'1	108.0
C7—C9—H9A	109.5	C9'—C8'—H8'2	108.0
C7—C9—H9B	109.5	C7'—C8'—H8'2	108.0
H9A—C9—H9B	109.5	H8'1—C8'—H8'2	107.3
C7—C9—H9C	109.5	C10'—C9'—C8'	115.7 (3)
H9A—C9—H9C	109.5	C10'—C9'—H9'1	108.4
H9B—C9—H9C	109.5	C8'—C9'—H9'1	108.4
C7—C10—H10A	109.5	C10'—C9'—H9'2	108.4
C7—C10—H10B	109.5	C8'—C9'—H9'2	108.4
H10A—C10—H10B	109.5	H9'1—C9'—H9'2	107.4
C7—C10—H10C	109.5	C1'—C10'—C9'	111.0 (3)
H10A—C10—H10C	109.5	C1'—C10'—H0'1	109.4
H10B—C10—H10C	109.5	C9'—C10'—H0'1	109.4
C4—C11—H11A	109.5	C1'—C10'—H0'2	109.4
C4—C11—H11B	109.5	C9'—C10'—H0'2	109.4
H11A—C11—H11B	109.5	H0'1—C10'—H0'2	108.0
C3—O2—C1—C8	160.6 (2)	C5—C4—C7—C10	64.2 (3)
C3—O2—C1—C6	−72.4 (3)	C11—C4—C7—C1	176.8 (3)
C3—O2—C1—C7	36.0 (3)	C3—C4—C7—C1	51.9 (2)
C1—O2—C3—O4	179.3 (3)	C5—C4—C7—C1	−53.9 (3)
C1—O2—C3—C4	−0.1 (3)	C11—C4—C7—C9	61.2 (4)
O4—C3—C4—C11	16.3 (5)	C3—C4—C7—C9	−63.7 (3)
O2—C3—C4—C11	−164.5 (2)	C5—C4—C7—C9	−169.6 (3)
O4—C3—C4—C5	−108.4 (4)	C3'—O1—C8—O3	2.2 (4)
O2—C3—C4—C5	70.9 (3)	C3'—O1—C8—C1	−172.7 (2)
O4—C3—C4—C7	145.9 (3)	O2—C1—C8—O3	159.2 (3)
O2—C3—C4—C7	−34.9 (3)	C6—C1—C8—O3	38.3 (4)
C11—C4—C5—C6	167.6 (3)	C7—C1—C8—O3	−84.4 (4)
C3—C4—C5—C6	−67.9 (3)	O2—C1—C8—O1	−25.8 (3)
C7—C4—C5—C6	34.5 (3)	C6—C1—C8—O1	−146.6 (3)
O2—C1—C6—C5	70.3 (3)	C7—C1—C8—O1	90.6 (3)
C8—C1—C6—C5	−165.4 (3)	C10'—C1'—C2'—C3'	21 (3)
C7—C1—C6—C5	−36.6 (3)	C8—O1—C3'—C2'	75.7 (3)
C4—C5—C6—C1	0.8 (3)	C8—O1—C3'—C4'	−163.6 (2)
O2—C1—C7—C10	−173.0 (2)	C1'—C2'—C3'—O1	145.8 (15)
C8—C1—C7—C10	65.2 (4)	C1'—C2'—C3'—C4'	27.9 (17)
C6—C1—C7—C10	−63.7 (3)	O1—C3'—C4'—C5'	163.8 (2)
O2—C1—C7—C9	62.8 (3)	C2'—C3'—C4'—C5'	−76.5 (3)
C8—C1—C7—C9	−59.0 (4)	C3'—C4'—C5'—C6'	54.5 (4)
C6—C1—C7—C9	172.1 (2)	C4'—C5'—C6'—C7'	61.8 (4)
O2—C1—C7—C4	−54.1 (2)	C5'—C6'—C7'—C8'	−166.7 (3)
C8—C1—C7—C4	−175.9 (3)	C6'—C7'—C8'—C9'	61.1 (4)
C6—C1—C7—C4	55.2 (3)	C7'—C8'—C9'—C10'	54.7 (4)
C11—C4—C7—C10	−65.1 (4)	C2'—C1'—C10'—C9'	16 (2)
C3—C4—C7—C10	170.0 (3)	C8'—C9'—C10'—C1'	−74.8 (4)