(1S,2S)-1-{2-[(4-Methoxy­benzyl)­oxy]­ethyl}-2-methyl-3-butenyl (1S,4R)-4,7,7-tri­methyl-3-oxo-2-oxabi­cyclo­[2.2.1]­heptane-1-carboxyl­ate

The title compound, C₂₅H₃₄O₆, crystallizes in the ortho­rhombic space group P2₁2₁2₁. The crystal structure has been determined to establish the absolute configuration of the parent compound by introducing a chiral auxiliary of known structure.

Key indicators

• Single-crystal X-ray study
• T = 83 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.041
• wR factor = 0.092
• Data-to-parameter ratio = 9.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?

Alert level G
REFLT03_ALERT_4_G 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.
           From the CIF: _diffrn_reflns_theta_max           25.65
           From the CIF: _reflns_number_total               2511
           Count of symmetry unique reflns         2516
           Completeness (_total/calc)             99.80%
           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

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion

---

Computing details

Data collection: SMART (Siemens, 1995); cell refinement: SMART; data reduction: SAINT (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1994); software used to prepare material for publication: SHELXL97.

(1S,2S)-1-{2-[(4-methoxybenzyl)oxy]ethyl}-2-methyl-3-butenyl (1S,4R)-4,7,7-trimethyl-3-oxo-2-oxabicyclo[2.2.1]heptane-1-carboxylate

Crystal data

C25H34O6	Dx = 1.242 Mg m^−3
Mr = 430.52	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 7013 reflections
a = 6.8297 (1) Å	θ = 2.2–25.7°
b = 12.0970 (2) Å	µ = 0.09 mm^−1
c = 27.8762 (4) Å	T = 83 K
V = 2303.10 (6) Å^3	Needle, colourless
Z = 4	0.42 × 0.16 × 0.10 mm
F(000) = 928

Data collection

Siemens SMART CCD diffractometer	2511 independent reflections
Radiation source: fine-focus sealed tube	2171 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.057
ω scans	θmax = 25.7°, θmin = 2.2°
Absorption correction: multi-scan (Blessing, 1995)	h = −8→8
Tmin = 0.964, Tmax = 0.992	k = −14→14
4366 measured reflections	l = −33→33

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.092	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0387P)^2 + 0.8019P] where P = (Fo^2 + 2Fc^2)/3
2511 reflections	(Δ/σ)max = 0.001
280 parameters	Δρmax = 0.22 e Å^−3
0 restraints	Δρmin = −0.21 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
O1	1.2001 (3)	0.43484 (18)	0.72906 (7)	0.0253 (5)
C1	0.8047 (4)	0.4469 (2)	0.80452 (9)	0.0165 (6)
O2	1.0006 (2)	0.48323 (16)	0.78955 (6)	0.0183 (4)
C2	0.6623 (4)	0.4948 (2)	0.76731 (9)	0.0199 (6)
H2A	0.6859	0.5729	0.7620	0.024*
H2B	0.5272	0.4842	0.7770	0.024*
O3	0.9090 (3)	0.51367 (18)	0.88198 (6)	0.0273 (5)
C3	0.7129 (4)	0.4256 (3)	0.72205 (10)	0.0221 (6)
H3A	0.7603	0.4725	0.6963	0.026*
H3B	0.5995	0.3849	0.7108	0.026*
O4	0.5907 (3)	0.46863 (16)	0.86920 (6)	0.0185 (4)
C4	0.8767 (4)	0.3454 (2)	0.73982 (9)	0.0183 (6)
O5	0.6013 (3)	0.74096 (15)	0.90856 (6)	0.0193 (4)
C5	1.0478 (4)	0.4220 (2)	0.74986 (9)	0.0187 (6)
O6	1.3802 (3)	1.01032 (15)	0.95605 (6)	0.0214 (4)
C6	0.8121 (4)	0.3206 (2)	0.79262 (9)	0.0180 (6)
C7	0.6161 (4)	0.2606 (2)	0.79684 (10)	0.0244 (7)
H7A	0.5864	0.2482	0.8301	0.037*
H7B	0.6237	0.1909	0.7805	0.037*
H7C	0.5150	0.3049	0.7826	0.037*
C8	0.9677 (4)	0.2583 (2)	0.82148 (10)	0.0233 (6)
H8A	0.9202	0.2453	0.8534	0.035*
H8B	1.0852	0.3017	0.8229	0.035*
H8C	0.9952	0.1889	0.8062	0.035*
C9	0.9259 (4)	0.2490 (2)	0.70727 (10)	0.0236 (6)
H9A	0.9630	0.2764	0.6762	0.035*
H9B	0.8134	0.2020	0.7041	0.035*
H9C	1.0324	0.2077	0.7208	0.035*
C10	0.7788 (4)	0.4808 (2)	0.85646 (9)	0.0170 (6)
C11	0.6826 (5)	0.2251 (2)	0.94362 (10)	0.0276 (7)
H11A	0.5807	0.1861	0.9294	0.033*
H11B	0.8009	0.1899	0.9500	0.033*
C12	0.6595 (5)	0.3305 (2)	0.95472 (9)	0.0236 (7)
H12A	0.7662	0.3654	0.9689	0.028*
C13	0.4795 (4)	0.4004 (2)	0.94701 (10)	0.0210 (6)
H13A	0.4385	0.4262	0.9788	0.025*
C14	0.3052 (4)	0.3373 (3)	0.92592 (10)	0.0247 (7)
H14A	0.2778	0.2737	0.9454	0.037*
H14B	0.3360	0.3139	0.8939	0.037*
H14C	0.1924	0.3846	0.9252	0.037*
C15	0.5343 (4)	0.5045 (2)	0.91805 (9)	0.0191 (6)
H15A	0.6477	0.5396	0.9333	0.023*
C16	0.3743 (4)	0.5901 (2)	0.91227 (10)	0.0196 (6)
H16A	0.2642	0.5567	0.8958	0.024*
H16B	0.3297	0.6128	0.9438	0.024*
C17	0.4390 (4)	0.6912 (2)	0.88472 (9)	0.0199 (6)
H17A	0.4764	0.6703	0.8524	0.024*
H17B	0.3319	0.7435	0.8826	0.024*
C18	0.6690 (4)	0.8353 (2)	0.88272 (9)	0.0205 (6)
H18A	0.5694	0.8925	0.8832	0.025*
H18B	0.6930	0.8152	0.8496	0.025*
C19	0.8548 (4)	0.8790 (2)	0.90481 (9)	0.0171 (6)
C20	0.9610 (4)	0.8208 (2)	0.93880 (9)	0.0208 (6)
H20A	0.9144	0.7528	0.9493	0.025*
C21	1.1364 (4)	0.8615 (2)	0.95779 (10)	0.0206 (6)
H21A	1.2044	0.8216	0.9809	0.025*
C22	1.2075 (4)	0.9626 (2)	0.94149 (9)	0.0183 (6)
C23	1.1017 (4)	1.0223 (2)	0.90755 (9)	0.0226 (6)
H23A	1.1488	1.0900	0.8967	0.027*
C24	0.9276 (4)	0.9816 (2)	0.88991 (9)	0.0221 (6)
H24A	0.8572	1.0230	0.8677	0.027*
C25	1.4987 (4)	0.9515 (2)	0.98972 (9)	0.0217 (6)
H25A	1.6139	0.9940	0.9968	0.033*
H25B	1.5361	0.8816	0.9763	0.033*
H25C	1.4256	0.9396	1.0187	0.033*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0195 (11)	0.0339 (12)	0.0224 (10)	−0.0018 (10)	0.0046 (9)	−0.0016 (10)
C1	0.0146 (13)	0.0171 (14)	0.0177 (13)	−0.0020 (11)	−0.0002 (11)	0.0014 (11)
O2	0.0163 (9)	0.0182 (10)	0.0203 (9)	−0.0026 (9)	0.0018 (8)	−0.0024 (8)
C2	0.0188 (14)	0.0203 (14)	0.0206 (13)	0.0035 (13)	−0.0004 (11)	0.0011 (12)
O3	0.0195 (10)	0.0399 (12)	0.0224 (10)	−0.0028 (10)	−0.0019 (9)	−0.0093 (10)
C3	0.0209 (15)	0.0249 (16)	0.0203 (14)	0.0029 (13)	−0.0015 (12)	0.0008 (13)
O4	0.0175 (9)	0.0226 (10)	0.0154 (9)	−0.0029 (8)	0.0008 (8)	−0.0031 (8)
C4	0.0192 (14)	0.0198 (14)	0.0160 (13)	−0.0001 (12)	−0.0023 (11)	0.0017 (11)
O5	0.0197 (10)	0.0193 (10)	0.0188 (9)	−0.0031 (9)	−0.0022 (8)	0.0022 (8)
C5	0.0196 (15)	0.0193 (14)	0.0172 (13)	0.0063 (12)	−0.0024 (13)	0.0018 (12)
O6	0.0224 (10)	0.0192 (10)	0.0226 (10)	−0.0028 (9)	−0.0039 (8)	0.0029 (8)
C6	0.0203 (14)	0.0185 (14)	0.0152 (13)	−0.0033 (12)	0.0006 (11)	0.0005 (11)
C7	0.0282 (16)	0.0221 (15)	0.0230 (14)	−0.0084 (14)	−0.0015 (13)	0.0018 (13)
C8	0.0310 (16)	0.0184 (14)	0.0206 (14)	0.0012 (14)	−0.0007 (13)	0.0044 (12)
C9	0.0257 (16)	0.0236 (15)	0.0214 (14)	0.0006 (14)	−0.0009 (12)	−0.0063 (13)
C10	0.0165 (13)	0.0159 (14)	0.0185 (13)	0.0005 (12)	−0.0009 (11)	0.0005 (12)
C11	0.0313 (17)	0.0242 (16)	0.0274 (16)	−0.0032 (15)	−0.0028 (14)	0.0054 (14)
C12	0.0270 (16)	0.0255 (16)	0.0183 (14)	−0.0069 (13)	−0.0039 (12)	0.0015 (13)
C13	0.0248 (15)	0.0221 (14)	0.0161 (13)	−0.0041 (13)	0.0002 (12)	−0.0028 (12)
C14	0.0243 (16)	0.0276 (16)	0.0222 (14)	−0.0075 (14)	0.0008 (12)	−0.0005 (13)
C15	0.0194 (13)	0.0224 (14)	0.0155 (13)	−0.0049 (12)	0.0004 (11)	−0.0051 (11)
C16	0.0177 (14)	0.0195 (14)	0.0217 (14)	−0.0025 (12)	0.0009 (12)	−0.0023 (12)
C17	0.0177 (14)	0.0234 (15)	0.0187 (13)	−0.0005 (12)	−0.0012 (12)	−0.0011 (12)
C18	0.0232 (15)	0.0195 (14)	0.0187 (13)	−0.0004 (13)	0.0011 (12)	0.0044 (12)
C19	0.0165 (15)	0.0201 (14)	0.0146 (13)	0.0033 (12)	0.0028 (11)	−0.0004 (11)
C20	0.0231 (15)	0.0187 (14)	0.0207 (14)	−0.0005 (12)	0.0035 (12)	0.0024 (12)
C21	0.0226 (16)	0.0175 (14)	0.0218 (14)	0.0039 (12)	0.0011 (12)	0.0039 (12)
C22	0.0202 (14)	0.0184 (14)	0.0164 (13)	0.0008 (12)	0.0026 (11)	−0.0047 (12)
C23	0.0289 (16)	0.0167 (14)	0.0221 (14)	−0.0035 (13)	−0.0008 (12)	0.0035 (12)
C24	0.0285 (16)	0.0186 (14)	0.0192 (13)	0.0008 (13)	−0.0019 (12)	0.0047 (12)
C25	0.0214 (16)	0.0240 (15)	0.0195 (14)	−0.0002 (13)	0.0001 (11)	−0.0015 (12)

Geometric parameters (Å, º)

O1—C5	1.201 (3)	C11—H11A	0.9300
C1—O2	1.469 (3)	C11—H11B	0.9300
C1—C10	1.516 (4)	C12—C13	1.508 (4)
C1—C2	1.536 (4)	C12—H12A	0.9300
C1—C6	1.564 (4)	C13—C14	1.532 (4)
O2—C5	1.370 (3)	C13—C15	1.541 (4)
C2—C3	1.553 (4)	C13—H13A	0.9800
C2—H2A	0.9700	C14—H14A	0.9600
C2—H2B	0.9700	C14—H14B	0.9600
O3—C10	1.206 (3)	C14—H14C	0.9600
C3—C4	1.562 (4)	C15—C16	1.515 (4)
C3—H3A	0.9700	C15—H15A	0.9800
C3—H3B	0.9700	C16—C17	1.509 (4)
O4—C10	1.341 (3)	C16—H16A	0.9700
O4—C15	1.480 (3)	C16—H16B	0.9700
C4—C9	1.514 (4)	C17—H17A	0.9700
C4—C5	1.518 (4)	C17—H17B	0.9700
C4—C6	1.566 (4)	C18—C19	1.506 (4)
O5—C17	1.425 (3)	C18—H18A	0.9700
O5—C18	1.427 (3)	C18—H18B	0.9700
O6—C22	1.375 (3)	C19—C20	1.385 (4)
O6—C25	1.429 (3)	C19—C24	1.401 (4)
C6—C7	1.527 (4)	C20—C21	1.399 (4)
C6—C8	1.531 (4)	C20—H20A	0.9300
C7—H7A	0.9600	C21—C22	1.393 (4)
C7—H7B	0.9600	C21—H21A	0.9300
C7—H7C	0.9600	C22—C23	1.392 (4)
C8—H8A	0.9600	C23—C24	1.378 (4)
C8—H8B	0.9600	C23—H23A	0.9300
C8—H8C	0.9600	C24—H24A	0.9300
C9—H9A	0.9600	C25—H25A	0.9600
C9—H9B	0.9600	C25—H25B	0.9600
C9—H9C	0.9600	C25—H25C	0.9600
C11—C12	1.322 (4)
O2—C1—C10	107.3 (2)	C11—C12—H12A	116.4
O2—C1—C2	105.8 (2)	C13—C12—H12A	116.4
C10—C1—C2	118.0 (2)	C12—C13—C14	114.1 (2)
O2—C1—C6	101.7 (2)	C12—C13—C15	109.6 (2)
C10—C1—C6	118.1 (2)	C14—C13—C15	113.3 (2)
C2—C1—C6	104.3 (2)	C12—C13—H13A	106.4
C5—O2—C1	106.4 (2)	C14—C13—H13A	106.4
C1—C2—C3	101.8 (2)	C15—C13—H13A	106.4
C1—C2—H2A	111.4	C13—C14—H14A	109.5
C3—C2—H2A	111.4	C13—C14—H14B	109.5
C1—C2—H2B	111.4	H14A—C14—H14B	109.5
C3—C2—H2B	111.4	C13—C14—H14C	109.5
H2A—C2—H2B	109.3	H14A—C14—H14C	109.5
C2—C3—C4	103.7 (2)	H14B—C14—H14C	109.5
C2—C3—H3A	111.0	O4—C15—C16	106.9 (2)
C4—C3—H3A	111.0	O4—C15—C13	107.8 (2)
C2—C3—H3B	111.0	C16—C15—C13	116.1 (2)
C4—C3—H3B	111.0	O4—C15—H15A	108.6
H3A—C3—H3B	109.0	C16—C15—H15A	108.6
C10—O4—C15	117.4 (2)	C13—C15—H15A	108.6
C9—C4—C5	114.2 (2)	C17—C16—C15	113.4 (2)
C9—C4—C3	116.6 (2)	C17—C16—H16A	108.9
C5—C4—C3	103.3 (2)	C15—C16—H16A	108.9
C9—C4—C6	118.6 (2)	C17—C16—H16B	108.9
C5—C4—C6	99.2 (2)	C15—C16—H16B	108.9
C3—C4—C6	102.4 (2)	H16A—C16—H16B	107.7
C17—O5—C18	110.79 (19)	O5—C17—C16	109.4 (2)
O1—C5—O2	121.6 (3)	O5—C17—H17A	109.8
O1—C5—C4	131.1 (3)	C16—C17—H17A	109.8
O2—C5—C4	107.3 (2)	O5—C17—H17B	109.8
C22—O6—C25	118.1 (2)	C16—C17—H17B	109.8
C7—C6—C8	109.5 (2)	H17A—C17—H17B	108.2
C7—C6—C1	114.8 (2)	O5—C18—C19	110.3 (2)
C8—C6—C1	113.1 (2)	O5—C18—H18A	109.6
C7—C6—C4	114.2 (2)	C19—C18—H18A	109.6
C8—C6—C4	113.1 (2)	O5—C18—H18B	109.6
C1—C6—C4	91.2 (2)	C19—C18—H18B	109.6
C6—C7—H7A	109.5	H18A—C18—H18B	108.1
C6—C7—H7B	109.5	C20—C19—C24	117.9 (3)
H7A—C7—H7B	109.5	C20—C19—C18	122.9 (2)
C6—C7—H7C	109.5	C24—C19—C18	119.2 (2)
H7A—C7—H7C	109.5	C19—C20—C21	121.9 (3)
H7B—C7—H7C	109.5	C19—C20—H20A	119.0
C6—C8—H8A	109.5	C21—C20—H20A	119.0
C6—C8—H8B	109.5	C22—C21—C20	118.9 (3)
H8A—C8—H8B	109.5	C22—C21—H21A	120.5
C6—C8—H8C	109.5	C20—C21—H21A	120.5
H8A—C8—H8C	109.5	O6—C22—C23	115.4 (2)
H8B—C8—H8C	109.5	O6—C22—C21	124.9 (3)
C4—C9—H9A	109.5	C23—C22—C21	119.8 (3)
C4—C9—H9B	109.5	C24—C23—C22	120.3 (3)
H9A—C9—H9B	109.5	C24—C23—H23A	119.8
C4—C9—H9C	109.5	C22—C23—H23A	119.8
H9A—C9—H9C	109.5	C23—C24—C19	121.2 (3)
H9B—C9—H9C	109.5	C23—C24—H24A	119.4
O3—C10—O4	125.9 (2)	C19—C24—H24A	119.4
O3—C10—C1	124.5 (2)	O6—C25—H25A	109.5
O4—C10—C1	109.6 (2)	O6—C25—H25B	109.5
C12—C11—H11A	120.0	H25A—C25—H25B	109.5
C12—C11—H11B	120.0	O6—C25—H25C	109.5
H11A—C11—H11B	120.0	H25A—C25—H25C	109.5
C11—C12—C13	127.3 (3)	H25B—C25—H25C	109.5