Hexamethyl 13,14-dioxapenta-cyclo-[8.2.1.1(4,7).0(2,9).0(3,8)]tetra-deca-5,11-diene-1,4,5,6,11,12-hexa-carboxyl-ate.

In the title compound, C(24)H(24)O(14), the stereochemistry at the cyclo-butane ring is cis-anti-cis and the -COOMe groups in the bicyclic rings are syn to each other. The mol-ecule lies on a twofold rotation axis. In the crystal, weak C-H⋯O hydrogen bonds connect mol-ecules into chains along [001], forming R(2) (2)(10) rings.

Related literature

For related structures, see: Lough et al. (2012a ▶,b ▶). For the synthetic background, see: Ballantine et al. (2009 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C24H24O14

M = 536.43

Monoclinic,

a = 25.1309 (18) Å

b = 10.0840 (7) Å

c = 9.5922 (7) Å

β = 95.430 (2)°

V = 2419.9 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.12 mm−1

T = 147 K

0.15 × 0.10 × 0.07 mm

Data collection

Bruker Kappa APEX DUO CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T min = 0.711, T max = 0.746

11038 measured reflections

2787 independent reflections

2366 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.098

S = 1.04

2787 reflections

175 parameters

H-atom parameters constrained

Δρmax = 0.42 e Å−3

Δρmin = −0.25 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT (Bruker, 2007 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812039232/hb6954sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812039232/hb6954Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812039232/hb6954Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C24H24O14	F(000) = 1120
Mr = 536.43	Dx = 1.472 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 6078 reflections
a = 25.1309 (18) Å	θ = 3.0–27.5°
b = 10.0840 (7) Å	µ = 0.12 mm−1
c = 9.5922 (7) Å	T = 147 K
β = 95.430 (2)°	Needle, colourless
V = 2419.9 (3) Å3	0.15 × 0.10 × 0.07 mm
Z = 4

Bruker Kappa APEX DUO CCD diffractometer	2787 independent reflections
Radiation source: fine-focus sealed tube	2366 reflections with I > 2σ(I)
Bruker Triumph monochromator	Rint = 0.028
φ and ω scans	θmax = 27.5°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −32→32
Tmin = 0.711, Tmax = 0.746	k = −13→12
11038 measured reflections	l = −11→12

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.098	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0518P)2 + 1.6228P] where P = (Fo2 + 2Fc2)/3
2787 reflections	(Δ/σ)max = 0.001
175 parameters	Δρmax = 0.42 e Å−3
0 restraints	Δρmin = −0.25 e Å−3

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.

	x	y	z	Uiso*/Ueq
O1	0.92545 (3)	0.44122 (8)	0.38295 (8)	0.01527 (19)
O2	0.91010 (5)	0.09784 (10)	0.30367 (10)	0.0322 (3)
O3	0.94389 (4)	0.20695 (9)	0.49626 (9)	0.0237 (2)
O4	0.80179 (4)	0.21560 (10)	0.15093 (10)	0.0272 (2)
O5	0.85951 (3)	0.23192 (9)	−0.01412 (9)	0.0206 (2)
O6	0.84027 (4)	0.69996 (9)	0.08929 (10)	0.0250 (2)
O7	0.80331 (4)	0.50766 (9)	0.00853 (10)	0.0227 (2)
C1	0.97293 (4)	0.35610 (11)	0.20451 (11)	0.0133 (2)
H1	0.9723	0.3106	0.1117	0.016*
C2	0.92422 (4)	0.33021 (12)	0.28941 (11)	0.0141 (2)
C3	0.87579 (4)	0.36255 (12)	0.18620 (11)	0.0149 (2)
C4	0.87513 (5)	0.49467 (12)	0.17852 (12)	0.0157 (2)
C5	0.92285 (4)	0.54296 (12)	0.27571 (11)	0.0149 (2)
H5A	0.9202	0.6361	0.3103	0.018*
C6	0.97323 (4)	0.51140 (11)	0.20141 (11)	0.0134 (2)
H6	0.9748	0.5528	0.1071	0.016*
C7	0.92448 (5)	0.19809 (12)	0.36304 (12)	0.0171 (3)
C8	0.93932 (6)	0.08885 (15)	0.58051 (15)	0.0322 (3)
H8A	0.9590	0.1018	0.6726	0.048*
H8B	0.9543	0.0129	0.5338	0.048*
H8C	0.9016	0.0721	0.5920	0.048*
C9	0.84091 (5)	0.26211 (12)	0.10758 (12)	0.0165 (2)
C10	0.82628 (5)	0.14106 (15)	−0.10214 (14)	0.0263 (3)
H10A	0.8400	0.1345	−0.1942	0.039*
H10B	0.7895	0.1742	−0.1134	0.039*
H10C	0.8270	0.0533	−0.0582	0.039*
C11	0.83860 (4)	0.58061 (13)	0.08826 (12)	0.0170 (2)
C12	0.76407 (5)	0.58064 (14)	−0.08202 (15)	0.0266 (3)
H12A	0.7429	0.5185	−0.1433	0.040*
H12B	0.7824	0.6433	−0.1392	0.040*
H12C	0.7404	0.6294	−0.0247	0.040*

	U11	U22	U33	U12	U13	U23
O1	0.0186 (4)	0.0149 (4)	0.0123 (4)	0.0003 (3)	0.0013 (3)	−0.0014 (3)
O2	0.0547 (7)	0.0168 (5)	0.0246 (5)	−0.0047 (4)	0.0011 (4)	−0.0007 (4)
O3	0.0295 (5)	0.0222 (5)	0.0183 (4)	−0.0033 (4)	−0.0035 (4)	0.0069 (4)
O4	0.0228 (5)	0.0311 (6)	0.0287 (5)	−0.0110 (4)	0.0078 (4)	−0.0079 (4)
O5	0.0188 (4)	0.0252 (5)	0.0177 (4)	−0.0039 (3)	0.0015 (3)	−0.0053 (4)
O6	0.0227 (5)	0.0180 (5)	0.0329 (5)	0.0026 (3)	−0.0045 (4)	−0.0004 (4)
O7	0.0180 (4)	0.0207 (5)	0.0274 (5)	−0.0002 (3)	−0.0091 (4)	0.0033 (4)
C1	0.0127 (5)	0.0146 (6)	0.0120 (5)	−0.0002 (4)	−0.0012 (4)	−0.0003 (4)
C2	0.0143 (5)	0.0150 (6)	0.0127 (5)	−0.0004 (4)	−0.0001 (4)	−0.0018 (4)
C3	0.0116 (5)	0.0190 (6)	0.0142 (5)	−0.0004 (4)	0.0009 (4)	0.0002 (4)
C4	0.0121 (5)	0.0188 (6)	0.0160 (5)	0.0002 (4)	0.0002 (4)	−0.0011 (4)
C5	0.0154 (5)	0.0138 (6)	0.0153 (5)	0.0013 (4)	−0.0004 (4)	−0.0001 (4)
C6	0.0133 (5)	0.0138 (6)	0.0126 (5)	−0.0004 (4)	−0.0019 (4)	−0.0001 (4)
C7	0.0166 (6)	0.0179 (6)	0.0174 (6)	0.0007 (4)	0.0038 (4)	0.0013 (5)
C8	0.0412 (8)	0.0286 (8)	0.0263 (7)	0.0004 (6)	0.0011 (6)	0.0140 (6)
C9	0.0139 (5)	0.0180 (6)	0.0172 (5)	0.0004 (4)	−0.0007 (4)	0.0001 (5)
C10	0.0243 (7)	0.0316 (8)	0.0223 (6)	−0.0046 (5)	−0.0013 (5)	−0.0102 (6)
C11	0.0125 (5)	0.0196 (6)	0.0188 (5)	0.0009 (4)	0.0013 (4)	0.0003 (5)
C12	0.0193 (6)	0.0274 (7)	0.0306 (7)	0.0005 (5)	−0.0106 (5)	0.0074 (6)

O1—C2	1.4331 (14)	C3—C4	1.3343 (17)
O1—C5	1.4500 (14)	C3—C9	1.4960 (16)
O2—C7	1.1991 (16)	C4—C11	1.4808 (16)
O3—C7	1.3271 (15)	C4—C5	1.5275 (15)
O3—C8	1.4499 (16)	C5—C6	1.5435 (16)
O4—C9	1.1987 (15)	C5—H5A	1.0000
O5—C9	1.3331 (15)	C6—C6i	1.563 (2)
O5—C10	1.4547 (15)	C6—H6	1.0000
O6—C11	1.2043 (16)	C8—H8A	0.9800
O7—C11	1.3358 (15)	C8—H8B	0.9800
O7—C12	1.4514 (14)	C8—H8C	0.9800
C1—C1i	1.545 (2)	C10—H10A	0.9800
C1—C2	1.5553 (15)	C10—H10B	0.9800
C1—C6	1.5663 (16)	C10—H10C	0.9800
C1—H1	1.0000	C12—H12A	0.9800
C2—C7	1.5076 (16)	C12—H12B	0.9800
C2—C3	1.5295 (15)	C12—H12C	0.9800
C2—O1—C5	96.42 (8)	C5—C6—H6	115.8
C7—O3—C8	116.11 (11)	C6i—C6—H6	115.8
C9—O5—C10	114.99 (10)	C1—C6—H6	115.8
C11—O7—C12	116.12 (10)	O2—C7—O3	125.51 (12)
C1i—C1—C2	113.51 (11)	O2—C7—C2	122.33 (11)
C1i—C1—C6	90.30 (5)	O3—C7—C2	112.12 (10)
C2—C1—C6	100.56 (9)	O3—C8—H8A	109.5
C1i—C1—H1	116.2	O3—C8—H8B	109.5
C2—C1—H1	116.2	H8A—C8—H8B	109.5
C6—C1—H1	116.2	O3—C8—H8C	109.5
O1—C2—C7	113.46 (9)	H8A—C8—H8C	109.5
O1—C2—C3	101.97 (9)	H8B—C8—H8C	109.5
C7—C2—C3	117.36 (10)	O4—C9—O5	125.55 (11)
O1—C2—C1	103.01 (9)	O4—C9—C3	123.42 (11)
C7—C2—C1	115.14 (9)	O5—C9—C3	111.03 (10)
C3—C2—C1	104.05 (9)	O5—C10—H10A	109.5
C4—C3—C9	130.13 (11)	O5—C10—H10B	109.5
C4—C3—C2	104.70 (10)	H10A—C10—H10B	109.5
C9—C3—C2	125.05 (10)	O5—C10—H10C	109.5
C3—C4—C11	128.35 (11)	H10A—C10—H10C	109.5
C3—C4—C5	106.24 (10)	H10B—C10—H10C	109.5
C11—C4—C5	125.29 (11)	O6—C11—O7	125.15 (11)
O1—C5—C4	100.80 (9)	O6—C11—C4	124.12 (11)
O1—C5—C6	101.41 (9)	O7—C11—C4	110.72 (11)
C4—C5—C6	106.46 (9)	O7—C12—H12A	109.5
O1—C5—H5A	115.4	O7—C12—H12B	109.5
C4—C5—H5A	115.4	H12A—C12—H12B	109.5
C6—C5—H5A	115.4	O7—C12—H12C	109.5
C5—C6—C6i	114.97 (11)	H12A—C12—H12C	109.5
C5—C6—C1	101.06 (9)	H12B—C12—H12C	109.5
C6i—C6—C1	89.66 (5)
C5—O1—C2—C7	−178.09 (9)	O1—C5—C6—C1	37.92 (10)
C5—O1—C2—C3	−50.92 (9)	C4—C5—C6—C1	−67.09 (10)
C5—O1—C2—C1	56.76 (9)	C1i—C1—C6—C5	−117.62 (10)
C1i—C1—C2—O1	62.75 (8)	C2—C1—C6—C5	−3.62 (10)
C6—C1—C2—O1	−32.23 (10)	C1i—C1—C6—C6i	−2.22 (12)
C1i—C1—C2—C7	−61.30 (10)	C2—C1—C6—C6i	111.78 (10)
C6—C1—C2—C7	−156.28 (9)	C8—O3—C7—O2	−10.06 (19)
C1i—C1—C2—C3	168.84 (6)	C8—O3—C7—C2	172.22 (11)
C6—C1—C2—C3	73.86 (10)	O1—C2—C7—O2	160.49 (12)
O1—C2—C3—C4	32.45 (11)	C3—C2—C7—O2	41.86 (17)
C7—C2—C3—C4	157.06 (10)	C1—C2—C7—O2	−81.16 (15)
C1—C2—C3—C4	−74.43 (11)	O1—C2—C7—O3	−21.71 (14)
O1—C2—C3—C9	−151.28 (10)	C3—C2—C7—O3	−140.34 (10)
C7—C2—C3—C9	−26.67 (16)	C1—C2—C7—O3	96.65 (12)
C1—C2—C3—C9	101.85 (12)	C10—O5—C9—O4	4.24 (18)
C9—C3—C4—C11	0.3 (2)	C10—O5—C9—C3	−176.27 (10)
C2—C3—C4—C11	176.35 (11)	C4—C3—C9—O4	−94.36 (17)
C9—C3—C4—C5	−175.80 (11)	C2—C3—C9—O4	90.36 (16)
C2—C3—C4—C5	0.21 (12)	C4—C3—C9—O5	86.14 (16)
C2—O1—C5—C4	50.47 (9)	C2—C3—C9—O5	−89.15 (13)
C2—O1—C5—C6	−58.97 (9)	C12—O7—C11—O6	−0.57 (18)
C3—C4—C5—O1	−32.25 (12)	C12—O7—C11—C4	178.21 (10)
C11—C4—C5—O1	151.47 (11)	C3—C4—C11—O6	178.87 (13)
C3—C4—C5—C6	73.20 (12)	C5—C4—C11—O6	−5.68 (19)
C11—C4—C5—C6	−103.08 (12)	C3—C4—C11—O7	0.08 (18)
O1—C5—C6—C6i	−56.92 (8)	C5—C4—C11—O7	175.53 (11)
C4—C5—C6—C6i	−161.93 (7)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O1ii	1.00	2.38	3.2105 (13)	140

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯O1i	1.00	2.38	3.2105 (13)	140

Symmetry code: (i) .