Absolute configuration of the p-nitro­benzoate ester of the cyclo­adduct of (S)-4-hydr­oxy-2-pentynoate and acetic acid 8-acet­oxy-1,4-dihydro-1,4-methanona­pththalen-5-yl ester

The regio- and absolute stereochemistry of the title compound, ethyl 3,6-diacet­oxy-11-[1-(4- nitro­benzo­yloxy)eth­yl]tetra­cyclo­[6.4.1.0^2,7.0^9,12]trideca-2,4,6,10-tetra­ene-10-carboxyl­ate, C₂₉H₂₇O₁₀, has been established. In the crystal structure, weak inter­molecular hydrogen bonds link mol­ecules into a three-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.045
• wR factor = 0.125
• Data-to-parameter ratio = 8.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT220_ALERT_2_C Large Non-Solvent    O     Ueq(max)/Ueq(min) ...       2.75 Ratio
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          6
PLAT432_ALERT_2_C Short Inter X...Y Contact  O8     ..  C16     ..       2.94 Ang.

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           27.50
           From the CIF: _reflns_number_total               3175
           Count of symmetry unique reflns         3203
           Completeness (_total/calc)             99.13%
           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
   3 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

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

---

Computing details

Data collection: COLLECT (Nonius, 2002); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXTL/PC (Sheldrick, 2001); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL/PC.

ethyl 3,6-diacetoxy-11-[1-(4- nitrobenzoyloxy)ethyl]tetracyclo[6.4.1.0^2,7.0^9,12]trideca-2,4,6,10- tetraene-10-carboxylate

Crystal data

C29H27NO10	F(000) = 576
Mr = 549.52	Dx = 1.412 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 8306 reflections
a = 13.5862 (6) Å	θ = 2.7–27.5°
b = 7.3020 (3) Å	µ = 0.11 mm^−1
c = 14.3462 (7) Å	T = 150 K
β = 114.709 (2)°	Block, colourless
V = 1292.93 (10) Å^3	0.40 × 0.40 × 0.34 mm
Z = 2

Data collection

Bruker–Nonius KappaCCD diffractometer	3175 independent reflections
Radiation source: fine-focus sealed tube	2230 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.055
Detector resolution: 9 pixels mm^-1	θmax = 27.5°, θmin = 2.7°
φ and ω scans with κ offsets	h = −17→16
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	k = −9→8
Tmin = 0.869, Tmax = 0.962	l = −16→18
8306 measured 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)] = 0.045	H-atom parameters constrained
wR(F^2) = 0.125	w = 1/[σ^2(Fo^2) + (0.0697P)^2 + 0.0871P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
3175 reflections	Δρmax = 0.30 e Å^−3
366 parameters	Δρmin = −0.26 e Å^−3
1 restraint	Extinction correction: SHELXTL/PC, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.037 (5)

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	0.31033 (18)	0.2413 (3)	0.68162 (17)	0.0279 (6)
O2	0.2145 (2)	0.4931 (4)	0.6048 (2)	0.0396 (7)
O3	−0.0721 (3)	−0.0817 (5)	0.1946 (2)	0.0629 (9)
O4	−0.0254 (3)	−0.3131 (5)	0.2987 (3)	0.0765 (12)
O5	0.6042 (2)	0.4978 (3)	0.98251 (18)	0.0320 (6)
O6	0.74865 (19)	0.3146 (4)	1.01677 (18)	0.0321 (6)
O7	0.44345 (19)	−0.3154 (3)	0.54348 (18)	0.0298 (6)
O8	0.4074 (2)	−0.6158 (4)	0.54355 (19)	0.0367 (6)
O9	0.83179 (19)	−0.3521 (3)	0.89647 (18)	0.0306 (6)
O10	0.9068 (2)	−0.1343 (4)	0.8371 (2)	0.0501 (8)
N1	−0.0239 (3)	−0.1495 (5)	0.2802 (3)	0.0467 (9)
C1	0.4953 (3)	0.2498 (5)	0.7910 (2)	0.0253 (7)
C2	0.5227 (3)	0.0931 (5)	0.7357 (2)	0.0243 (7)
H2A	0.5236	0.1256	0.6684	0.029*
C3	0.4779 (3)	−0.1004 (5)	0.7412 (3)	0.0261 (8)
H3A	0.3983	−0.1183	0.7001	0.031*
C4	0.5511 (3)	−0.2301 (5)	0.7181 (3)	0.0258 (8)
C5	0.5401 (3)	−0.3316 (5)	0.6334 (3)	0.0266 (8)
C6	0.6255 (3)	−0.4393 (5)	0.6345 (3)	0.0322 (8)
H6A	0.6173	−0.5087	0.5757	0.039*
C7	0.7221 (3)	−0.4445 (5)	0.7218 (3)	0.0317 (8)
H7A	0.7798	−0.5201	0.7236	0.038*
C8	0.7348 (3)	−0.3391 (5)	0.8070 (3)	0.0274 (8)
C9	0.6516 (3)	−0.2319 (5)	0.8055 (3)	0.0269 (8)
C10	0.6402 (3)	−0.0975 (5)	0.8809 (3)	0.0273 (8)
H10A	0.6933	−0.1113	0.9541	0.033*
C11	0.6379 (3)	0.0918 (5)	0.8312 (2)	0.0255 (7)
H11A	0.7011	0.1187	0.8149	0.031*
C12	0.5949 (3)	0.2542 (5)	0.8694 (2)	0.0239 (7)
C13	0.5200 (3)	−0.1300 (5)	0.8582 (2)	0.0269 (7)
H13A	0.4915	−0.0382	0.8915	0.032*
H13B	0.5061	−0.2553	0.8762	0.032*
C14	0.3906 (3)	0.3511 (5)	0.7633 (3)	0.0268 (8)
H14A	0.3959	0.4751	0.7362	0.032*
C15	0.3560 (3)	0.3702 (5)	0.8505 (3)	0.0325 (8)
H15A	0.2830	0.4227	0.8243	0.049*
H15B	0.4068	0.4508	0.9033	0.049*
H15C	0.3559	0.2493	0.8802	0.049*
C16	0.2296 (3)	0.3293 (5)	0.6068 (3)	0.0292 (8)
C17	0.1615 (3)	0.2002 (5)	0.5240 (3)	0.0287 (8)
C18	0.0930 (3)	0.2742 (6)	0.4296 (3)	0.0348 (9)
H18A	0.0871	0.4032	0.4205	0.042*
C19	0.0336 (3)	0.1582 (6)	0.3491 (3)	0.0366 (9)
H19A	−0.0103	0.2061	0.2831	0.044*
C20	0.0394 (3)	−0.0271 (6)	0.3666 (3)	0.0341 (9)
C21	0.1029 (3)	−0.1033 (6)	0.4602 (3)	0.0336 (8)
H21A	0.1034	−0.2318	0.4707	0.040*
C22	0.1658 (3)	0.0123 (5)	0.5383 (3)	0.0331 (9)
H22A	0.2128	−0.0375	0.6028	0.040*
C23	0.6464 (3)	0.3683 (5)	0.9604 (3)	0.0269 (8)
C24	0.8090 (3)	0.4245 (6)	1.1080 (2)	0.0322 (9)
H24A	0.7927	0.5558	1.0915	0.039*
H24B	0.8877	0.4062	1.1294	0.039*
C25	0.7800 (3)	0.3725 (6)	1.1948 (3)	0.0371 (9)
H25A	0.8258	0.4407	1.2566	0.056*
H25B	0.7915	0.2408	1.2081	0.056*
H25C	0.7038	0.4020	1.1762	0.056*
C26	0.3851 (3)	−0.4705 (5)	0.5018 (3)	0.0267 (8)
C27	0.2925 (3)	−0.4297 (6)	0.4017 (3)	0.0337 (9)
H27A	0.2637	−0.5444	0.3649	0.051*
H27B	0.3174	−0.3515	0.3604	0.051*
H27C	0.2354	−0.3663	0.4140	0.051*
C28	0.9143 (3)	−0.2401 (5)	0.9038 (3)	0.0319 (8)
C29	1.0117 (3)	−0.2690 (6)	1.0014 (3)	0.0444 (10)
H29A	1.0516	−0.1536	1.0231	0.067*
H29B	1.0584	−0.3616	0.9911	0.067*
H29C	0.9892	−0.3110	1.0545	0.067*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0259 (13)	0.0254 (13)	0.0262 (12)	0.0000 (11)	0.0049 (10)	−0.0001 (11)
O2	0.0393 (16)	0.0283 (14)	0.0405 (15)	0.0061 (12)	0.0063 (13)	−0.0003 (13)
O3	0.061 (2)	0.074 (2)	0.0334 (16)	−0.0017 (19)	−0.0001 (15)	−0.0067 (18)
O4	0.092 (3)	0.048 (2)	0.058 (2)	−0.023 (2)	0.000 (2)	−0.0122 (19)
O5	0.0372 (14)	0.0251 (13)	0.0290 (13)	0.0035 (11)	0.0092 (11)	−0.0032 (11)
O6	0.0268 (14)	0.0358 (15)	0.0284 (13)	0.0004 (11)	0.0062 (11)	−0.0086 (11)
O7	0.0326 (14)	0.0238 (12)	0.0266 (13)	−0.0003 (11)	0.0059 (11)	−0.0018 (11)
O8	0.0421 (15)	0.0277 (14)	0.0370 (14)	−0.0029 (12)	0.0132 (12)	0.0006 (13)
O9	0.0252 (13)	0.0297 (13)	0.0325 (13)	0.0006 (11)	0.0077 (11)	0.0027 (12)
O10	0.0481 (18)	0.0531 (19)	0.0386 (15)	−0.0156 (15)	0.0079 (13)	0.0061 (16)
N1	0.037 (2)	0.055 (3)	0.041 (2)	−0.0058 (18)	0.0086 (17)	−0.0063 (19)
C1	0.0296 (19)	0.0230 (16)	0.0224 (16)	0.0002 (15)	0.0099 (15)	0.0013 (16)
C2	0.0251 (17)	0.0254 (17)	0.0204 (15)	0.0018 (14)	0.0076 (14)	0.0017 (15)
C3	0.0236 (17)	0.0251 (18)	0.0278 (17)	0.0028 (15)	0.0090 (14)	0.0002 (16)
C4	0.0246 (18)	0.0231 (17)	0.0306 (18)	0.0014 (15)	0.0124 (15)	0.0034 (16)
C5	0.0255 (18)	0.0251 (18)	0.0264 (17)	−0.0038 (15)	0.0081 (15)	−0.0004 (16)
C6	0.039 (2)	0.0276 (19)	0.0314 (18)	0.0027 (17)	0.0158 (17)	−0.0029 (18)
C7	0.031 (2)	0.0271 (19)	0.039 (2)	0.0043 (16)	0.0158 (17)	−0.0007 (18)
C8	0.0234 (18)	0.0263 (18)	0.0293 (18)	0.0022 (15)	0.0080 (15)	0.0020 (16)
C9	0.0269 (18)	0.0252 (17)	0.0258 (17)	−0.0016 (15)	0.0081 (15)	−0.0002 (16)
C10	0.0289 (18)	0.0261 (18)	0.0231 (16)	0.0020 (15)	0.0072 (14)	−0.0028 (16)
C11	0.0243 (18)	0.0275 (18)	0.0245 (17)	0.0014 (15)	0.0100 (14)	0.0003 (16)
C12	0.0276 (18)	0.0185 (16)	0.0263 (17)	−0.0003 (15)	0.0121 (15)	0.0001 (16)
C13	0.0294 (18)	0.0231 (17)	0.0258 (17)	0.0019 (15)	0.0093 (15)	0.0029 (15)
C14	0.0264 (18)	0.0247 (18)	0.0261 (16)	−0.0025 (14)	0.0078 (15)	−0.0013 (15)
C15	0.0314 (19)	0.035 (2)	0.0320 (18)	0.0032 (17)	0.0139 (16)	0.0002 (18)
C16	0.0257 (19)	0.032 (2)	0.0282 (18)	0.0037 (15)	0.0094 (16)	0.0046 (17)
C17	0.0257 (18)	0.0300 (19)	0.0280 (18)	0.0017 (15)	0.0088 (15)	0.0023 (16)
C18	0.028 (2)	0.034 (2)	0.035 (2)	0.0047 (17)	0.0056 (17)	0.0055 (19)
C19	0.028 (2)	0.042 (2)	0.030 (2)	−0.0012 (18)	0.0025 (17)	0.0020 (19)
C20	0.0260 (19)	0.041 (2)	0.0315 (19)	−0.0053 (17)	0.0084 (16)	−0.0069 (18)
C21	0.035 (2)	0.0291 (19)	0.037 (2)	−0.0012 (17)	0.0152 (17)	0.0000 (18)
C22	0.033 (2)	0.035 (2)	0.0267 (18)	−0.0013 (17)	0.0085 (16)	0.0026 (17)
C23	0.0302 (19)	0.0227 (17)	0.0286 (17)	0.0008 (16)	0.0131 (15)	0.0010 (16)
C24	0.0257 (18)	0.041 (2)	0.0248 (17)	−0.0060 (16)	0.0050 (15)	−0.0113 (17)
C25	0.031 (2)	0.045 (2)	0.0286 (18)	−0.0022 (19)	0.0068 (16)	−0.0045 (19)
C26	0.0322 (19)	0.0230 (18)	0.0288 (18)	−0.0025 (15)	0.0165 (16)	−0.0029 (16)
C27	0.033 (2)	0.038 (2)	0.0269 (18)	−0.0052 (17)	0.0089 (16)	−0.0037 (18)
C28	0.032 (2)	0.0273 (18)	0.0339 (19)	−0.0006 (17)	0.0113 (16)	0.0018 (18)
C29	0.034 (2)	0.040 (2)	0.047 (2)	−0.0071 (19)	0.0053 (18)	0.005 (2)

Geometric parameters (Å, º)

O1—C16	1.335 (4)	C11—C12	1.520 (5)
O1—C14	1.462 (4)	C11—H11A	1.0000
O2—C16	1.212 (4)	C12—C23	1.458 (5)
O3—N1	1.229 (5)	C13—H13A	0.9900
O4—N1	1.226 (5)	C13—H13B	0.9900
O5—C23	1.215 (4)	C14—C15	1.515 (5)
O6—C23	1.341 (4)	C14—H14A	1.0000
O6—C24	1.460 (4)	C15—H15A	0.9800
O7—C26	1.368 (4)	C15—H15B	0.9800
O7—C5	1.409 (4)	C15—H15C	0.9800
O8—C26	1.193 (4)	C16—C17	1.496 (5)
O9—C28	1.356 (4)	C17—C22	1.385 (5)
O9—C8	1.406 (4)	C17—C18	1.392 (5)
O10—C28	1.202 (5)	C18—C19	1.388 (5)
N1—C20	1.478 (5)	C18—H18A	0.9500
C1—C12	1.351 (5)	C19—C20	1.372 (6)
C1—C14	1.501 (5)	C19—H19A	0.9500
C1—C2	1.525 (5)	C20—C21	1.374 (5)
C2—C3	1.554 (5)	C21—C22	1.378 (5)
C2—C11	1.592 (5)	C21—H21A	0.9500
C2—H2A	1.0000	C22—H22A	0.9500
C3—C4	1.507 (5)	C24—C25	1.503 (5)
C3—C13	1.546 (4)	C24—H24A	0.9900
C3—H3A	1.0000	C24—H24B	0.9900
C4—C5	1.378 (5)	C25—H25A	0.9800
C4—C9	1.417 (5)	C25—H25B	0.9800
C5—C6	1.395 (5)	C25—H25C	0.9800
C6—C7	1.386 (5)	C26—C27	1.492 (5)
C6—H6A	0.9500	C27—H27A	0.9800
C7—C8	1.392 (5)	C27—H27B	0.9800
C7—H7A	0.9500	C27—H27C	0.9800
C8—C9	1.369 (5)	C28—C29	1.485 (5)
C9—C10	1.515 (5)	C29—H29A	0.9800
C10—C13	1.545 (5)	C29—H29B	0.9800
C10—C11	1.550 (5)	C29—H29C	0.9800
C10—H10A	1.0000
C16—O1—C14	117.9 (3)	O1—C14—H14A	109.6
C23—O6—C24	115.6 (3)	C1—C14—H14A	109.6
C26—O7—C5	118.6 (3)	C15—C14—H14A	109.6
C28—O9—C8	117.3 (3)	C14—C15—H15A	109.5
O4—N1—O3	123.9 (4)	C14—C15—H15B	109.5
O4—N1—C20	117.7 (4)	H15A—C15—H15B	109.5
O3—N1—C20	118.4 (4)	C14—C15—H15C	109.5
C12—C1—C14	135.8 (3)	H15A—C15—H15C	109.5
C12—C1—C2	94.2 (3)	H15B—C15—H15C	109.5
C14—C1—C2	130.0 (3)	O2—C16—O1	124.6 (3)
C1—C2—C3	118.0 (3)	O2—C16—C17	124.1 (3)
C1—C2—C11	85.5 (2)	O1—C16—C17	111.3 (3)
C3—C2—C11	102.5 (3)	C22—C17—C18	119.9 (4)
C1—C2—H2A	115.4	C22—C17—C16	122.2 (3)
C3—C2—H2A	115.4	C18—C17—C16	117.9 (3)
C11—C2—H2A	115.4	C19—C18—C17	119.5 (4)
C4—C3—C13	99.9 (3)	C19—C18—H18A	120.2
C4—C3—C2	104.6 (3)	C17—C18—H18A	120.2
C13—C3—C2	101.9 (3)	C20—C19—C18	118.7 (4)
C4—C3—H3A	116.0	C20—C19—H19A	120.6
C13—C3—H3A	116.0	C18—C19—H19A	120.6
C2—C3—H3A	116.0	C19—C20—C21	122.9 (4)
C5—C4—C9	119.0 (3)	C19—C20—N1	118.3 (4)
C5—C4—C3	134.0 (3)	C21—C20—N1	118.8 (4)
C9—C4—C3	107.0 (3)	C20—C21—C22	118.0 (4)
C4—C5—C6	120.7 (3)	C20—C21—H21A	121.0
C4—C5—O7	118.5 (3)	C22—C21—H21A	121.0
C6—C5—O7	120.7 (3)	C21—C22—C17	120.9 (4)
C7—C6—C5	119.6 (3)	C21—C22—H22A	119.6
C7—C6—H6A	120.2	C17—C22—H22A	119.6
C5—C6—H6A	120.2	O5—C23—O6	123.6 (3)
C6—C7—C8	120.1 (3)	O5—C23—C12	125.2 (3)
C6—C7—H7A	120.0	O6—C23—C12	111.2 (3)
C8—C7—H7A	120.0	O6—C24—C25	111.1 (3)
C9—C8—C7	120.3 (3)	O6—C24—H24A	109.4
C9—C8—O9	120.3 (3)	C25—C24—H24A	109.4
C7—C8—O9	119.3 (3)	O6—C24—H24B	109.4
C8—C9—C4	120.2 (3)	C25—C24—H24B	109.4
C8—C9—C10	133.6 (3)	H24A—C24—H24B	108.0
C4—C9—C10	106.1 (3)	C24—C25—H25A	109.5
C9—C10—C13	99.5 (3)	C24—C25—H25B	109.5
C9—C10—C11	103.8 (3)	H25A—C25—H25B	109.5
C13—C10—C11	102.9 (3)	C24—C25—H25C	109.5
C9—C10—H10A	116.1	H25A—C25—H25C	109.5
C13—C10—H10A	116.1	H25B—C25—H25C	109.5
C11—C10—H10A	116.1	O8—C26—O7	122.5 (3)
C12—C11—C10	117.9 (3)	O8—C26—C27	126.6 (3)
C12—C11—C2	85.3 (2)	O7—C26—C27	110.9 (3)
C10—C11—C2	103.0 (3)	C26—C27—H27A	109.5
C12—C11—H11A	115.4	C26—C27—H27B	109.5
C10—C11—H11A	115.4	H27A—C27—H27B	109.5
C2—C11—H11A	115.4	C26—C27—H27C	109.5
C1—C12—C23	134.2 (3)	H27A—C27—H27C	109.5
C1—C12—C11	94.8 (3)	H27B—C27—H27C	109.5
C23—C12—C11	130.9 (3)	O10—C28—O9	122.3 (3)
C10—C13—C3	94.9 (3)	O10—C28—C29	126.0 (4)
C10—C13—H13A	112.8	O9—C28—C29	111.7 (3)
C3—C13—H13A	112.8	C28—C29—H29A	109.5
C10—C13—H13B	112.8	C28—C29—H29B	109.5
C3—C13—H13B	112.8	H29A—C29—H29B	109.5
H13A—C13—H13B	110.2	C28—C29—H29C	109.5
O1—C14—C1	104.4 (3)	H29A—C29—H29C	109.5
O1—C14—C15	109.1 (3)	H29B—C29—H29C	109.5
C1—C14—C15	114.4 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13B···O5^i	0.99	2.38	3.189 (4)	139
C15—H15C···O5^ii	0.98	2.58	3.513 (4)	159
C25—H25A···O4^iii	0.98	2.58	3.345 (6)	135

Symmetry codes: (i) x, y−1, z; (ii) −x+1, y−1/2, −z+2; (iii) x+1, y+1, z+1.