

Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536808012567/lh2623sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536808012567/lh2623Isup2.hkl |
CCDC reference: 690917
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean
(C-C) = 0.004 Å
- R factor = 0.034
- wR factor = 0.101
- Data-to-parameter ratio = 9.1
checkCIF/PLATON results
No syntax errors found
Alert level B ABSTM02_ALERT_3_B The ratio of expected to reported Tmax/Tmin(RR') is < 0.75 Tmin and Tmax reported: 0.550 0.990 Tmin(prime) and Tmax expected: 0.930 0.991 RR(prime) = 0.592 Please check that your absorption correction is appropriate. PLAT061_ALERT_3_B Tmax/Tmin Range Test RR' too Large ............. 0.59
Alert level C PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size ....... 0.80 mm PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 22
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 27.46 From the CIF: _reflns_number_total 4938 Count of symmetry unique reflns 4985 Completeness (_total/calc) 99.06% 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 PLAT791_ALERT_1_G Confirm the Absolute Configuration of C2 ... R PLAT791_ALERT_1_G Confirm the Absolute Configuration of C3 ... R PLAT791_ALERT_1_G Confirm the Absolute Configuration of C21 ... R PLAT791_ALERT_1_G Confirm the Absolute Configuration of C24 ... S PLAT791_ALERT_1_G Confirm the Absolute Configuration of C102 ... R PLAT791_ALERT_1_G Confirm the Absolute Configuration of C103 ... R PLAT791_ALERT_1_G Confirm the Absolute Configuration of C121 ... R PLAT791_ALERT_1_G Confirm the Absolute Configuration of C124 ... S PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 1
0 ALERT level A = In general: serious problem 2 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 10 ALERT level G = General alerts; check 8 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 4 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
checkCIF publication errors
Alert level A PUBL024_ALERT_1_A The number of authors is greater than 5. Please specify the role of each of the co-authors for your paper.
Author Response: Jenkinson, Sarah F. - Post Doc chemist and crystallographer; Rule, Sebastian D. - preparative chemist; Booth, Kathrine V. - trainee crystallographer; Watkin, David J. - senior crystallographer; Fleet, George W. J. - Preparative Group Leader (Oxford); Petursson, Sigthor - Preparative Group Leader (Akureyi);. |
1 ALERT level A = Data missing that is essential or data in wrong format 0 ALERT level G = General alerts. Data that may be required is missing
The title lactone was recrystallized from a 1:1 mixture of ethyl acetate and cyclohexane: m.p. 395–397 K; [α]D23 +129.1 (c, 1.02 in CHCl3).
In the absence of significant anomalous scattering, Friedel pairs were merged and the absolute configuration was assigned from the starting material.
The relatively large ratio of minimum to maximum corrections applied in the multiscan process (1:1.80) reflect changes in the illuminated volume of the crystal. Changes in illuminated volume were kept to a minimum, and were taken into account (Görbitz, 1999) by the multi-scan inter-frame scaling (DENZO/SCALEPACK, Otwinowski & Minor, 1997).
The H atoms were all located in a difference map, but those attached to carbon atoms were repositioned geometrically. The H atoms were initially refined with soft restraints on the bond lengths and angles to regularize their geometry (C—H in the range 0.93–0.98, O—H = 0.82 Å) and Uiso(H) (in the range 1.2–1.5 times Ueq of the parent atom), after which the positions were refined with riding constraints.
Data collection: COLLECT (Nonius, 2001).; cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: CAMERON (Watkin et al., 1996); software used to prepare material for publication: CRYSTALS (Betteridge et al., 2003).
C25H22O5 | F(000) = 848 |
Mr = 402.45 | Dx = 1.304 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 4834 reflections |
a = 14.8159 (3) Å | θ = 5–27° |
b = 9.1959 (2) Å | µ = 0.09 mm−1 |
c = 15.0797 (2) Å | T = 150 K |
β = 93.7245 (12)° | Plate, colourless |
V = 2050.20 (7) Å3 | 0.80 × 0.30 × 0.10 mm |
Z = 4 |
Nonius KappaCCD area-detector diffractometer | 3950 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.047 |
ω scans | θmax = 27.5°, θmin = 5.2° |
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997) | h = −19→19 |
Tmin = 0.55, Tmax = 0.99 | k = −11→11 |
25081 measured reflections | l = −19→19 |
4938 independent reflections |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.034 | Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982)
[weight] = 1.0/[A0*T0(x) + A1*T1(x) ··· + An-1]*Tn-1(x)]
where Ai are the Chebychev coefficients listed below and x = F /Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)2]2 Ai are: 16.9 24.9 12.6 3.46 |
wR(F2) = 0.101 | (Δ/σ)max = 0.000289 |
S = 0.89 | Δρmax = 0.25 e Å−3 |
4938 reflections | Δρmin = −0.27 e Å−3 |
542 parameters | Extinction correction: Larson (1970), Equation 22 |
1 restraint | Extinction coefficient: 600 (50) |
Primary atom site location: structure-invariant direct methods |
C25H22O5 | V = 2050.20 (7) Å3 |
Mr = 402.45 | Z = 4 |
Monoclinic, P21 | Mo Kα radiation |
a = 14.8159 (3) Å | µ = 0.09 mm−1 |
b = 9.1959 (2) Å | T = 150 K |
c = 15.0797 (2) Å | 0.80 × 0.30 × 0.10 mm |
β = 93.7245 (12)° |
Nonius KappaCCD area-detector diffractometer | 4938 independent reflections |
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997) | 3950 reflections with I > 2σ(I) |
Tmin = 0.55, Tmax = 0.99 | Rint = 0.047 |
25081 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 1 restraint |
wR(F2) = 0.101 | H-atom parameters constrained |
S = 0.89 | Δρmax = 0.25 e Å−3 |
4938 reflections | Δρmin = −0.27 e Å−3 |
542 parameters |
x | y | z | Uiso*/Ueq | ||
O1 | 0.44166 (10) | 0.5327 (2) | 0.31715 (10) | 0.0244 | |
C2 | 0.40499 (15) | 0.5336 (3) | 0.22694 (15) | 0.0242 | |
C3 | 0.30725 (16) | 0.4866 (3) | 0.23203 (15) | 0.0254 | |
O4 | 0.25857 (10) | 0.5219 (2) | 0.15093 (10) | 0.0265 | |
C5 | 0.16129 (15) | 0.5192 (3) | 0.15751 (16) | 0.0257 | |
C6 | 0.13142 (16) | 0.6490 (3) | 0.21052 (15) | 0.0252 | |
C7 | 0.17991 (18) | 0.7781 (3) | 0.21395 (18) | 0.0330 | |
C8 | 0.1517 (2) | 0.8947 (3) | 0.26476 (19) | 0.0403 | |
C9 | 0.0760 (2) | 0.8806 (3) | 0.31222 (18) | 0.0432 | |
C10 | 0.0264 (2) | 0.7539 (4) | 0.30826 (19) | 0.0437 | |
C11 | 0.05367 (19) | 0.6375 (3) | 0.25762 (17) | 0.0335 | |
C12 | 0.12135 (15) | 0.5140 (3) | 0.06274 (15) | 0.0255 | |
C13 | 0.15139 (19) | 0.6107 (3) | 0.00038 (17) | 0.0339 | |
C14 | 0.1185 (2) | 0.6028 (4) | −0.08784 (18) | 0.0429 | |
C15 | 0.0551 (2) | 0.4987 (4) | −0.11333 (19) | 0.0486 | |
C16 | 0.02472 (19) | 0.4030 (4) | −0.0519 (2) | 0.0479 | |
C17 | 0.05739 (17) | 0.4106 (4) | 0.03651 (19) | 0.0368 | |
C18 | 0.31556 (18) | 0.3212 (3) | 0.23435 (18) | 0.0323 | |
O19 | 0.26098 (14) | 0.2338 (2) | 0.25627 (16) | 0.0478 | |
O20 | 0.39494 (13) | 0.2813 (2) | 0.20131 (13) | 0.0344 | |
C21 | 0.44429 (17) | 0.4094 (3) | 0.17435 (16) | 0.0296 | |
C22 | 0.54422 (17) | 0.3886 (3) | 0.19447 (16) | 0.0335 | |
O23 | 0.56825 (11) | 0.3965 (2) | 0.28758 (11) | 0.0301 | |
C24 | 0.53776 (15) | 0.5268 (3) | 0.32352 (15) | 0.0255 | |
C25 | 0.56837 (16) | 0.5320 (3) | 0.42104 (16) | 0.0277 | |
C26 | 0.53029 (17) | 0.6335 (3) | 0.47592 (17) | 0.0318 | |
C27 | 0.5559 (2) | 0.6362 (4) | 0.56635 (19) | 0.0417 | |
C28 | 0.6204 (2) | 0.5396 (4) | 0.6014 (2) | 0.0479 | |
C29 | 0.6607 (2) | 0.4425 (4) | 0.5464 (2) | 0.0479 | |
C30 | 0.63432 (19) | 0.4375 (3) | 0.45597 (19) | 0.0359 | |
O101 | 0.17514 (11) | 0.3628 (2) | 0.56763 (10) | 0.0280 | |
C102 | 0.26545 (16) | 0.3497 (3) | 0.60615 (15) | 0.0265 | |
C103 | 0.26225 (16) | 0.3956 (3) | 0.70212 (16) | 0.0266 | |
O104 | 0.34196 (11) | 0.3412 (2) | 0.74916 (10) | 0.0274 | |
C105 | 0.33862 (16) | 0.3463 (3) | 0.84483 (15) | 0.0254 | |
C106 | 0.27885 (16) | 0.2264 (3) | 0.87746 (17) | 0.0275 | |
C107 | 0.25628 (19) | 0.1047 (3) | 0.82618 (19) | 0.0368 | |
C108 | 0.2043 (2) | −0.0056 (4) | 0.8592 (2) | 0.0473 | |
C109 | 0.17436 (19) | 0.0054 (4) | 0.9435 (3) | 0.0506 | |
C110 | 0.1966 (2) | 0.1261 (4) | 0.9956 (2) | 0.0512 | |
C111 | 0.2483 (2) | 0.2372 (4) | 0.9627 (2) | 0.0394 | |
C112 | 0.43660 (16) | 0.3392 (3) | 0.88150 (15) | 0.0254 | |
C113 | 0.49799 (18) | 0.4396 (3) | 0.85136 (18) | 0.0320 | |
C114 | 0.58750 (19) | 0.4422 (3) | 0.8863 (2) | 0.0383 | |
C115 | 0.61626 (18) | 0.3427 (3) | 0.95059 (18) | 0.0348 | |
C116 | 0.55682 (18) | 0.2406 (3) | 0.97998 (16) | 0.0318 | |
C117 | 0.46694 (17) | 0.2387 (3) | 0.94582 (15) | 0.0276 | |
C118 | 0.27224 (17) | 0.5609 (3) | 0.69587 (17) | 0.0307 | |
O119 | 0.25584 (16) | 0.6510 (3) | 0.75019 (14) | 0.0446 | |
O120 | 0.30885 (13) | 0.5960 (2) | 0.61933 (12) | 0.0333 | |
C121 | 0.32735 (16) | 0.4648 (3) | 0.56966 (16) | 0.0299 | |
C122 | 0.30971 (17) | 0.4926 (4) | 0.47132 (17) | 0.0357 | |
O123 | 0.21497 (11) | 0.4979 (2) | 0.44632 (11) | 0.0315 | |
C124 | 0.17243 (16) | 0.3695 (3) | 0.47308 (15) | 0.0280 | |
C125 | 0.07503 (16) | 0.3717 (3) | 0.43830 (16) | 0.0286 | |
C126 | 0.01418 (18) | 0.4674 (3) | 0.47230 (17) | 0.0354 | |
C127 | −0.07582 (19) | 0.4661 (4) | 0.44074 (19) | 0.0426 | |
C128 | −0.10512 (19) | 0.3684 (4) | 0.3750 (2) | 0.0417 | |
C129 | −0.0444 (2) | 0.2749 (4) | 0.3393 (2) | 0.0412 | |
C130 | 0.0462 (2) | 0.2761 (3) | 0.37099 (18) | 0.0344 | |
H21 | 0.4102 | 0.6308 | 0.1980 | 0.0310* | |
H31 | 0.2815 | 0.5292 | 0.2838 | 0.0300* | |
H51 | 0.1461 | 0.4285 | 0.1912 | 0.0293* | |
H71 | 0.2332 | 0.7897 | 0.1793 | 0.0378* | |
H81 | 0.1854 | 0.9828 | 0.2657 | 0.0498* | |
H91 | 0.0574 | 0.9586 | 0.3462 | 0.0522* | |
H101 | −0.0270 | 0.7456 | 0.3417 | 0.0499* | |
H111 | 0.0193 | 0.5507 | 0.2559 | 0.0398* | |
H131 | 0.1944 | 0.6831 | 0.0155 | 0.0428* | |
H141 | 0.1417 | 0.6660 | −0.1305 | 0.0511* | |
H151 | 0.0293 | 0.4918 | −0.1722 | 0.0598* | |
H161 | −0.0195 | 0.3290 | −0.0668 | 0.0570* | |
H171 | 0.0384 | 0.3446 | 0.0768 | 0.0465* | |
H211 | 0.4312 | 0.4257 | 0.1074 | 0.0355* | |
H221 | 0.5780 | 0.4629 | 0.1587 | 0.0427* | |
H222 | 0.5617 | 0.2896 | 0.1766 | 0.0439* | |
H241 | 0.5627 | 0.6105 | 0.2909 | 0.0328* | |
H261 | 0.4846 | 0.7013 | 0.4543 | 0.0393* | |
H271 | 0.5298 | 0.7065 | 0.6043 | 0.0510* | |
H281 | 0.6372 | 0.5419 | 0.6640 | 0.0566* | |
H291 | 0.7087 | 0.3765 | 0.5704 | 0.0512* | |
H301 | 0.6622 | 0.3686 | 0.4199 | 0.0430* | |
H1021 | 0.2909 | 0.2513 | 0.5939 | 0.0322* | |
H1031 | 0.2066 | 0.3671 | 0.7308 | 0.0308* | |
H1051 | 0.3131 | 0.4449 | 0.8589 | 0.0297* | |
H1071 | 0.2755 | 0.0977 | 0.7683 | 0.0447* | |
H1081 | 0.1886 | −0.0904 | 0.8241 | 0.0582* | |
H1091 | 0.1414 | −0.0692 | 0.9676 | 0.0609* | |
H1101 | 0.1777 | 0.1334 | 1.0531 | 0.0637* | |
H1111 | 0.2619 | 0.3211 | 0.9967 | 0.0452* | |
H1131 | 0.4790 | 0.5064 | 0.8020 | 0.0373* | |
H1141 | 0.6288 | 0.5114 | 0.8631 | 0.0459* | |
H1151 | 0.6769 | 0.3437 | 0.9745 | 0.0399* | |
H1161 | 0.5788 | 0.1694 | 1.0226 | 0.0391* | |
H1171 | 0.4223 | 0.1678 | 0.9652 | 0.0343* | |
H1211 | 0.3914 | 0.4381 | 0.5851 | 0.0389* | |
H1221 | 0.3378 | 0.5873 | 0.4563 | 0.0426* | |
H1222 | 0.3394 | 0.4138 | 0.4383 | 0.0433* | |
H1241 | 0.2031 | 0.2834 | 0.4506 | 0.0363* | |
H1261 | 0.0340 | 0.5326 | 0.5187 | 0.0406* | |
H1271 | −0.1184 | 0.5305 | 0.4660 | 0.0513* | |
H1281 | −0.1677 | 0.3670 | 0.3552 | 0.0470* | |
H1291 | −0.0649 | 0.2101 | 0.2929 | 0.0471* | |
H1301 | 0.0895 | 0.2105 | 0.3457 | 0.0399* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0232 (7) | 0.0288 (9) | 0.0210 (7) | −0.0002 (7) | 0.0005 (6) | −0.0019 (7) |
C2 | 0.0265 (11) | 0.0255 (12) | 0.0202 (10) | 0.0009 (9) | −0.0007 (8) | 0.0009 (9) |
C3 | 0.0275 (11) | 0.0277 (13) | 0.0209 (10) | −0.0006 (10) | −0.0001 (8) | 0.0048 (10) |
O4 | 0.0243 (8) | 0.0340 (10) | 0.0209 (7) | 0.0030 (7) | −0.0011 (6) | 0.0044 (7) |
C5 | 0.0245 (11) | 0.0251 (12) | 0.0276 (11) | −0.0001 (10) | 0.0017 (8) | 0.0027 (10) |
C6 | 0.0300 (11) | 0.0240 (11) | 0.0211 (10) | 0.0031 (10) | −0.0022 (8) | 0.0024 (9) |
C7 | 0.0352 (13) | 0.0288 (13) | 0.0346 (13) | −0.0016 (11) | −0.0004 (10) | −0.0027 (11) |
C8 | 0.0518 (16) | 0.0289 (14) | 0.0387 (14) | −0.0017 (13) | −0.0081 (12) | −0.0037 (12) |
C9 | 0.0659 (19) | 0.0334 (16) | 0.0298 (13) | 0.0140 (15) | 0.0001 (12) | −0.0040 (12) |
C10 | 0.0570 (18) | 0.0398 (17) | 0.0361 (15) | 0.0146 (14) | 0.0169 (13) | 0.0055 (13) |
C11 | 0.0390 (13) | 0.0283 (13) | 0.0341 (13) | 0.0044 (11) | 0.0094 (10) | 0.0046 (11) |
C12 | 0.0239 (10) | 0.0255 (12) | 0.0269 (11) | 0.0055 (9) | −0.0005 (8) | −0.0051 (10) |
C13 | 0.0413 (14) | 0.0298 (14) | 0.0296 (12) | −0.0048 (11) | −0.0048 (10) | −0.0012 (11) |
C14 | 0.0528 (17) | 0.0505 (18) | 0.0244 (13) | 0.0027 (15) | −0.0041 (11) | 0.0001 (13) |
C15 | 0.0420 (15) | 0.072 (2) | 0.0303 (13) | 0.0034 (16) | −0.0085 (11) | −0.0144 (16) |
C16 | 0.0305 (13) | 0.066 (2) | 0.0468 (16) | −0.0103 (15) | −0.0029 (11) | −0.0195 (17) |
C17 | 0.0269 (12) | 0.0416 (16) | 0.0422 (14) | −0.0072 (12) | 0.0034 (10) | −0.0072 (13) |
C18 | 0.0321 (13) | 0.0315 (14) | 0.0318 (13) | −0.0024 (11) | −0.0098 (10) | 0.0067 (11) |
O19 | 0.0394 (11) | 0.0384 (12) | 0.0638 (14) | −0.0101 (10) | −0.0106 (10) | 0.0201 (11) |
O20 | 0.0399 (10) | 0.0248 (9) | 0.0376 (10) | 0.0003 (8) | −0.0035 (8) | −0.0012 (8) |
C21 | 0.0357 (12) | 0.0308 (13) | 0.0223 (10) | 0.0026 (11) | 0.0027 (9) | −0.0005 (10) |
C22 | 0.0373 (13) | 0.0370 (14) | 0.0267 (12) | 0.0071 (12) | 0.0052 (10) | −0.0038 (11) |
O23 | 0.0300 (8) | 0.0340 (10) | 0.0264 (8) | 0.0074 (8) | 0.0021 (6) | −0.0025 (8) |
C24 | 0.0224 (10) | 0.0262 (12) | 0.0282 (11) | 0.0001 (10) | 0.0032 (8) | −0.0014 (10) |
C25 | 0.0245 (11) | 0.0280 (12) | 0.0303 (12) | −0.0073 (10) | −0.0004 (9) | −0.0015 (10) |
C26 | 0.0289 (12) | 0.0327 (14) | 0.0336 (13) | −0.0030 (11) | 0.0009 (9) | −0.0074 (11) |
C27 | 0.0428 (15) | 0.0469 (18) | 0.0350 (14) | −0.0127 (14) | −0.0017 (11) | −0.0100 (14) |
C28 | 0.0585 (19) | 0.0486 (18) | 0.0344 (14) | −0.0137 (16) | −0.0135 (13) | −0.0068 (14) |
C29 | 0.0542 (18) | 0.0407 (18) | 0.0456 (17) | 0.0004 (15) | −0.0219 (14) | −0.0023 (14) |
C30 | 0.0372 (13) | 0.0318 (14) | 0.0373 (14) | 0.0023 (11) | −0.0080 (11) | −0.0043 (12) |
O101 | 0.0258 (8) | 0.0354 (10) | 0.0223 (8) | −0.0028 (7) | −0.0020 (6) | 0.0045 (7) |
C102 | 0.0243 (11) | 0.0282 (12) | 0.0268 (11) | 0.0022 (10) | −0.0011 (8) | 0.0006 (10) |
C103 | 0.0230 (10) | 0.0315 (13) | 0.0249 (11) | 0.0045 (10) | 0.0002 (8) | 0.0039 (10) |
O104 | 0.0251 (8) | 0.0349 (10) | 0.0219 (8) | 0.0045 (7) | −0.0009 (6) | 0.0021 (7) |
C105 | 0.0276 (11) | 0.0253 (12) | 0.0234 (10) | 0.0012 (10) | 0.0017 (8) | 0.0004 (10) |
C106 | 0.0224 (11) | 0.0293 (13) | 0.0309 (12) | 0.0040 (10) | 0.0017 (9) | 0.0040 (10) |
C107 | 0.0379 (14) | 0.0348 (15) | 0.0367 (14) | −0.0038 (12) | −0.0050 (11) | 0.0054 (12) |
C108 | 0.0436 (16) | 0.0373 (17) | 0.0591 (19) | −0.0105 (14) | −0.0108 (13) | 0.0091 (15) |
C109 | 0.0315 (14) | 0.0453 (19) | 0.075 (2) | 0.0004 (13) | 0.0064 (14) | 0.0245 (18) |
C110 | 0.0442 (17) | 0.052 (2) | 0.060 (2) | 0.0125 (16) | 0.0272 (15) | 0.0164 (17) |
C111 | 0.0377 (14) | 0.0385 (16) | 0.0435 (15) | 0.0096 (13) | 0.0152 (12) | 0.0036 (13) |
C112 | 0.0268 (11) | 0.0262 (12) | 0.0230 (10) | 0.0003 (10) | 0.0003 (8) | −0.0033 (9) |
C113 | 0.0333 (12) | 0.0267 (13) | 0.0356 (13) | −0.0018 (10) | −0.0012 (10) | 0.0016 (11) |
C114 | 0.0342 (14) | 0.0329 (15) | 0.0473 (15) | −0.0060 (12) | −0.0002 (11) | −0.0029 (13) |
C115 | 0.0284 (12) | 0.0387 (15) | 0.0363 (13) | 0.0009 (11) | −0.0051 (10) | −0.0111 (12) |
C116 | 0.0329 (13) | 0.0377 (15) | 0.0239 (11) | 0.0081 (11) | −0.0051 (9) | −0.0038 (11) |
C117 | 0.0307 (12) | 0.0303 (13) | 0.0215 (10) | 0.0026 (10) | 0.0008 (9) | −0.0010 (10) |
C118 | 0.0294 (12) | 0.0332 (14) | 0.0291 (12) | 0.0039 (10) | −0.0005 (9) | 0.0015 (11) |
O119 | 0.0597 (13) | 0.0362 (11) | 0.0382 (10) | 0.0110 (10) | 0.0052 (9) | −0.0041 (10) |
O120 | 0.0381 (10) | 0.0317 (10) | 0.0304 (9) | −0.0055 (8) | 0.0030 (7) | 0.0035 (8) |
C121 | 0.0255 (11) | 0.0375 (14) | 0.0268 (11) | −0.0026 (11) | 0.0028 (9) | −0.0006 (11) |
C122 | 0.0268 (12) | 0.0527 (18) | 0.0278 (12) | −0.0056 (12) | 0.0041 (9) | 0.0032 (13) |
O123 | 0.0274 (8) | 0.0407 (11) | 0.0264 (8) | −0.0048 (8) | 0.0019 (6) | 0.0068 (8) |
C124 | 0.0308 (11) | 0.0300 (13) | 0.0231 (11) | −0.0002 (10) | 0.0019 (9) | 0.0024 (10) |
C125 | 0.0297 (12) | 0.0313 (13) | 0.0247 (11) | −0.0025 (10) | 0.0010 (9) | 0.0040 (10) |
C126 | 0.0334 (13) | 0.0430 (16) | 0.0294 (12) | 0.0014 (12) | −0.0004 (10) | −0.0060 (12) |
C127 | 0.0342 (13) | 0.0577 (19) | 0.0359 (14) | 0.0035 (14) | 0.0024 (11) | 0.0010 (14) |
C128 | 0.0325 (13) | 0.0510 (19) | 0.0407 (14) | −0.0064 (13) | −0.0058 (11) | 0.0092 (14) |
C129 | 0.0456 (16) | 0.0385 (16) | 0.0380 (14) | −0.0092 (13) | −0.0091 (12) | −0.0012 (13) |
C130 | 0.0420 (14) | 0.0284 (13) | 0.0319 (13) | −0.0018 (12) | −0.0050 (11) | −0.0005 (11) |
O1—C2 | 1.432 (3) | O101—C102 | 1.429 (3) |
O1—C24 | 1.422 (3) | O101—C124 | 1.425 (3) |
C2—C3 | 1.518 (3) | C102—C103 | 1.511 (3) |
C2—C21 | 1.527 (4) | C102—C121 | 1.526 (4) |
C2—H21 | 1.000 | C102—H1021 | 1.002 |
C3—O4 | 1.416 (3) | C103—O104 | 1.428 (3) |
C3—C18 | 1.526 (4) | C103—C118 | 1.531 (4) |
C3—H31 | 0.973 | C103—H1031 | 0.991 |
O4—C5 | 1.451 (3) | O104—C105 | 1.448 (3) |
C5—C6 | 1.518 (3) | C105—C106 | 1.516 (3) |
C5—C12 | 1.512 (3) | C105—C112 | 1.521 (3) |
C5—H51 | 1.009 | C105—H1051 | 1.011 |
C6—C7 | 1.387 (4) | C106—C107 | 1.388 (4) |
C6—C11 | 1.396 (3) | C106—C111 | 1.393 (4) |
C7—C8 | 1.398 (4) | C107—C108 | 1.385 (4) |
C7—H71 | 0.980 | C107—H1071 | 0.938 |
C8—C9 | 1.374 (4) | C108—C109 | 1.377 (5) |
C8—H81 | 0.952 | C108—H1081 | 0.963 |
C9—C10 | 1.377 (5) | C109—C110 | 1.387 (5) |
C9—H91 | 0.933 | C109—H1091 | 0.930 |
C10—C11 | 1.390 (4) | C110—C111 | 1.388 (5) |
C10—H101 | 0.969 | C110—H1101 | 0.932 |
C11—H111 | 0.947 | C111—H1111 | 0.941 |
C12—C13 | 1.388 (4) | C112—C113 | 1.393 (4) |
C12—C17 | 1.382 (4) | C112—C117 | 1.393 (3) |
C13—C14 | 1.389 (4) | C113—C114 | 1.395 (4) |
C13—H131 | 0.939 | C113—H1131 | 0.991 |
C14—C15 | 1.378 (5) | C114—C115 | 1.381 (4) |
C14—H141 | 0.948 | C114—H1141 | 0.964 |
C15—C16 | 1.374 (5) | C115—C116 | 1.380 (4) |
C15—H151 | 0.946 | C115—H1151 | 0.946 |
C16—C17 | 1.390 (4) | C116—C117 | 1.396 (3) |
C16—H161 | 0.961 | C116—H1161 | 0.960 |
C17—H171 | 0.916 | C117—H1171 | 0.986 |
C18—O19 | 1.202 (3) | C118—O119 | 1.201 (3) |
C18—O20 | 1.357 (3) | C118—O120 | 1.346 (3) |
O20—C21 | 1.458 (3) | O120—C121 | 1.456 (3) |
C21—C22 | 1.504 (4) | C121—C122 | 1.511 (3) |
C21—H211 | 1.026 | C121—H1211 | 0.994 |
C22—O23 | 1.428 (3) | C122—O123 | 1.430 (3) |
C22—H221 | 1.021 | C122—H1221 | 0.998 |
C22—H222 | 0.989 | C122—H1222 | 0.998 |
O23—C24 | 1.402 (3) | O123—C124 | 1.409 (3) |
C24—C25 | 1.511 (3) | C124—C125 | 1.503 (3) |
C24—H241 | 0.997 | C124—H1241 | 0.984 |
C25—C26 | 1.392 (4) | C125—C126 | 1.382 (4) |
C25—C30 | 1.385 (4) | C125—C130 | 1.389 (4) |
C26—C27 | 1.392 (4) | C126—C127 | 1.387 (4) |
C26—H261 | 0.961 | C126—H1261 | 0.953 |
C27—C28 | 1.385 (5) | C127—C128 | 1.386 (5) |
C27—H271 | 0.961 | C127—H1271 | 0.962 |
C28—C29 | 1.380 (5) | C128—C129 | 1.379 (5) |
C28—H281 | 0.962 | C128—H1281 | 0.955 |
C29—C30 | 1.394 (4) | C129—C130 | 1.394 (4) |
C29—H291 | 0.986 | C129—H1291 | 0.954 |
C30—H301 | 0.948 | C130—H1301 | 0.977 |
C2—O1—C24 | 112.39 (17) | C102—O101—C124 | 112.03 (17) |
O1—C2—C3 | 104.75 (18) | O101—C102—C103 | 106.20 (18) |
O1—C2—C21 | 110.80 (19) | O101—C102—C121 | 111.3 (2) |
C3—C2—C21 | 102.2 (2) | C103—C102—C121 | 102.0 (2) |
O1—C2—H21 | 112.6 | O101—C102—H1021 | 110.8 |
C3—C2—H21 | 112.2 | C103—C102—H1021 | 117.7 |
C21—C2—H21 | 113.5 | C121—C102—H1021 | 108.5 |
C2—C3—O4 | 108.98 (18) | C102—C103—O104 | 107.53 (19) |
C2—C3—C18 | 102.1 (2) | C102—C103—C118 | 102.1 (2) |
O4—C3—C18 | 106.5 (2) | O104—C103—C118 | 107.4 (2) |
C2—C3—H31 | 110.6 | C102—C103—H1031 | 115.0 |
O4—C3—H31 | 113.3 | O104—C103—H1031 | 112.1 |
C18—C3—H31 | 114.7 | C118—C103—H1031 | 112.1 |
C3—O4—C5 | 112.91 (17) | C103—O104—C105 | 113.76 (17) |
O4—C5—C6 | 110.32 (19) | O104—C105—C106 | 111.0 (2) |
O4—C5—C12 | 105.39 (18) | O104—C105—C112 | 105.51 (17) |
C6—C5—C12 | 114.4 (2) | C106—C105—C112 | 114.5 (2) |
O4—C5—H51 | 107.6 | O104—C105—H1051 | 106.0 |
C6—C5—H51 | 107.6 | C106—C105—H1051 | 110.5 |
C12—C5—H51 | 111.3 | C112—C105—H1051 | 108.9 |
C5—C6—C7 | 121.7 (2) | C105—C106—C107 | 122.0 (2) |
C5—C6—C11 | 119.1 (2) | C105—C106—C111 | 118.6 (2) |
C7—C6—C11 | 119.2 (2) | C107—C106—C111 | 119.4 (3) |
C6—C7—C8 | 120.3 (3) | C106—C107—C108 | 120.6 (3) |
C6—C7—H71 | 120.5 | C106—C107—H1071 | 119.8 |
C8—C7—H71 | 119.2 | C108—C107—H1071 | 119.6 |
C7—C8—C9 | 119.7 (3) | C107—C108—C109 | 119.9 (3) |
C7—C8—H81 | 119.1 | C107—C108—H1081 | 121.1 |
C9—C8—H81 | 121.2 | C109—C108—H1081 | 119.0 |
C8—C9—C10 | 120.6 (3) | C108—C109—C110 | 120.1 (3) |
C8—C9—H91 | 119.5 | C108—C109—H1091 | 121.1 |
C10—C9—H91 | 119.9 | C110—C109—H1091 | 118.7 |
C9—C10—C11 | 120.1 (3) | C109—C110—C111 | 120.2 (3) |
C9—C10—H101 | 119.7 | C109—C110—H1101 | 120.7 |
C11—C10—H101 | 120.1 | C111—C110—H1101 | 119.1 |
C6—C11—C10 | 120.0 (3) | C106—C111—C110 | 119.8 (3) |
C6—C11—H111 | 120.7 | C106—C111—H1111 | 119.4 |
C10—C11—H111 | 119.3 | C110—C111—H1111 | 120.8 |
C5—C12—C13 | 119.8 (2) | C105—C112—C113 | 118.8 (2) |
C5—C12—C17 | 120.8 (2) | C105—C112—C117 | 122.6 (2) |
C13—C12—C17 | 119.4 (2) | C113—C112—C117 | 118.6 (2) |
C12—C13—C14 | 120.5 (3) | C112—C113—C114 | 120.9 (3) |
C12—C13—H131 | 122.2 | C112—C113—H1131 | 119.8 |
C14—C13—H131 | 117.3 | C114—C113—H1131 | 119.2 |
C13—C14—C15 | 119.6 (3) | C113—C114—C115 | 119.7 (3) |
C13—C14—H141 | 119.9 | C113—C114—H1141 | 119.0 |
C15—C14—H141 | 120.5 | C115—C114—H1141 | 121.2 |
C14—C15—C16 | 120.3 (3) | C114—C115—C116 | 120.1 (2) |
C14—C15—H151 | 122.4 | C114—C115—H1151 | 120.3 |
C16—C15—H151 | 117.4 | C116—C115—H1151 | 119.6 |
C15—C16—C17 | 120.4 (3) | C115—C116—C117 | 120.2 (2) |
C15—C16—H161 | 122.9 | C115—C116—H1161 | 118.9 |
C17—C16—H161 | 116.7 | C117—C116—H1161 | 120.8 |
C16—C17—C12 | 119.9 (3) | C116—C117—C112 | 120.3 (2) |
C16—C17—H171 | 120.0 | C116—C117—H1171 | 122.7 |
C12—C17—H171 | 120.0 | C112—C117—H1171 | 116.9 |
C3—C18—O19 | 128.2 (3) | C103—C118—O119 | 128.2 (3) |
C3—C18—O20 | 109.4 (2) | C103—C118—O120 | 109.7 (2) |
O19—C18—O20 | 122.3 (3) | O119—C118—O120 | 122.0 (3) |
C18—O20—C21 | 110.2 (2) | C118—O120—C121 | 110.0 (2) |
C2—C21—O20 | 104.14 (18) | C102—C121—O120 | 104.57 (19) |
C2—C21—C22 | 113.2 (2) | C102—C121—C122 | 113.7 (2) |
O20—C21—C22 | 110.3 (2) | O120—C121—C122 | 109.8 (2) |
C2—C21—H211 | 110.3 | C102—C121—H1211 | 109.4 |
O20—C21—H211 | 109.0 | O120—C121—H1211 | 107.1 |
C22—C21—H211 | 109.7 | C122—C121—H1211 | 111.9 |
C21—C22—O23 | 111.80 (19) | C121—C122—O123 | 111.63 (19) |
C21—C22—H221 | 108.5 | C121—C122—H1221 | 108.8 |
O23—C22—H221 | 112.7 | O123—C122—H1221 | 109.1 |
C21—C22—H222 | 109.5 | C121—C122—H1222 | 108.2 |
O23—C22—H222 | 105.2 | O123—C122—H1222 | 110.5 |
H221—C22—H222 | 109.0 | H1221—C122—H1222 | 108.5 |
C22—O23—C24 | 110.9 (2) | C122—O123—C124 | 110.2 (2) |
O1—C24—O23 | 110.67 (19) | O101—C124—O123 | 109.8 (2) |
O1—C24—C25 | 107.49 (18) | O101—C124—C125 | 108.28 (18) |
O23—C24—C25 | 108.6 (2) | O123—C124—C125 | 109.0 (2) |
O1—C24—H241 | 109.8 | O101—C124—H1241 | 109.1 |
O23—C24—H241 | 109.3 | O123—C124—H1241 | 110.5 |
C25—C24—H241 | 111.0 | C125—C124—H1241 | 110.2 |
C24—C25—C26 | 119.5 (2) | C124—C125—C126 | 120.9 (2) |
C24—C25—C30 | 120.7 (2) | C124—C125—C130 | 119.3 (2) |
C26—C25—C30 | 119.9 (2) | C126—C125—C130 | 119.8 (2) |
C25—C26—C27 | 120.0 (3) | C125—C126—C127 | 120.2 (3) |
C25—C26—H261 | 122.5 | C125—C126—H1261 | 119.7 |
C27—C26—H261 | 117.5 | C127—C126—H1261 | 120.0 |
C26—C27—C28 | 120.0 (3) | C126—C127—C128 | 120.0 (3) |
C26—C27—H271 | 120.1 | C126—C127—H1271 | 119.9 |
C28—C27—H271 | 119.9 | C128—C127—H1271 | 120.0 |
C27—C28—C29 | 120.0 (3) | C127—C128—C129 | 120.1 (3) |
C27—C28—H281 | 119.3 | C127—C128—H1281 | 119.0 |
C29—C28—H281 | 120.7 | C129—C128—H1281 | 121.0 |
C28—C29—C30 | 120.3 (3) | C128—C129—C130 | 120.0 (3) |
C28—C29—H291 | 120.5 | C128—C129—H1291 | 119.4 |
C30—C29—H291 | 119.2 | C130—C129—H1291 | 120.7 |
C29—C30—C25 | 119.8 (3) | C129—C130—C125 | 119.9 (3) |
C29—C30—H301 | 118.6 | C129—C130—H1301 | 120.3 |
C25—C30—H301 | 121.6 | C125—C130—H1301 | 119.8 |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H81···O19i | 0.95 | 2.57 | 3.520 (4) | 173 |
C14—H141···O119ii | 0.95 | 2.55 | 3.309 (4) | 137 |
C28—H281···O19iii | 0.96 | 2.57 | 3.225 (4) | 126 |
Symmetry codes: (i) x, y+1, z; (ii) x, y, z−1; (iii) −x+1, y+1/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C25H22O5 |
Mr | 402.45 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 150 |
a, b, c (Å) | 14.8159 (3), 9.1959 (2), 15.0797 (2) |
β (°) | 93.7245 (12) |
V (Å3) | 2050.20 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.80 × 0.30 × 0.10 |
Data collection | |
Diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.55, 0.99 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 25081, 4938, 3950 |
Rint | 0.047 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.101, 0.89 |
No. of reflections | 4938 |
No. of parameters | 542 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.25, −0.27 |
Computer programs: COLLECT (Nonius, 2001)., DENZO/SCALEPACK (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1994), CRYSTALS (Betteridge et al., 2003), CAMERON (Watkin et al., 1996).
Carbohydrates provide excellent starting materials for the synthesis of small chiral molecules (Collins & Ferrier, 1995). They are relatively inexpensive and provide an almost boundless pool of chiral building blocks (Draths et al., 1992). Much of their synthetic utility is however dependent on developing successful protecting group strategies.
Diazodiphenylmethane has been found to be a useful protecting group in the synthesis of methyl 2,3,6-tri-O-methyl-α-D-glucopyranoside and kojibiose octa-acetate (Jackson et al., 1982); monoalkylations of vicinal diols have been achieved with this reagent and other diaryldiazoalkanes with high regioselectivities (Petursson & Webber, 1982; Petursson et al., 2007; Petursson, 2003; Petursson, 2001). This is of particular interest for the protection of base sensitive sugar lactones as the reaction is carried out under neutral conditions (Best et al. 2008; Jenkinson et al. 2008).
The utility of the benzhydryl group as a protecting group in carbohydrate chemistry has here been demonstrated with the reaction of 3,5-O-benzylidene-D-xylono-1,4-lactone 1 with diphenyldiazomethane (Fig. 1). No epimerization at C2 was observed (Fig. 2).
Unlike the analogously protected lyxono lactone (Jenkinson et al., 2008), the asymmetric unit of the isomeric xylono lactone contains two crystallographically distinct molecules which are related by a pseudo 2-fold axis of symmetry. These are similar in geometry with the exception of two of the phenyl rings which sit at approximately 90° to each other (Fig. 3). When the core 20 atoms, of the carbohydrate backbone and 1 phenyl group, are mapped there is good overlap- r.m.s. deviations: posn 0.1139 Å, bond 0.0104 Å, torsion 2.5205°.
The crystal packing shows alternating layers of molecules in the ac plane (Fig. 4). The 5-ring lactones adopt envelope conformations with C2 or C102 out of the plane. The 6-ring ketals adopt chair conformations. There is no classic hydrogen-bonding.