Diethyl 9,10-endo-ethano-9,10-di­hydro­anthracene-11,11-di­carboxyl­ate

Simpson, M.; Storey, J.M.D.; Harrison, W.T.A.

doi:10.1107/S1600536804012279

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 60| Part 6| June 2004| Pages o1081-o1083

https://doi.org/10.1107/S1600536804012279

Diethyl 9,10-endo-ethano-9,10-dihydroanthracene-11,11-dicarboxylate

Michael Simpson,^a John M. D. Storey ^a and William T. A. Harrison ^a ^*

^aDepartment of Chemistry, University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, Scotland
^*Correspondence e-mail: w.harrison@abdn.ac.uk

(Received 14 May 2004; accepted 20 May 2004; online 29 May 2004)

The title compound, C₂₂H₂₂O₄, possesses normal geometrical parameters and the dihedral angle between the two benzene ring planes is 57.62 (5)°. The crystal packing is controlled by van der Waals forces and a possible C—H⋯O interaction, the latter resulting in a supramolecular C(6) motif.

Comment

The title compound, (I) (Fig. 1), was created as an intermediate in the synthesis of 2-methylene malonic acid diethyl ester, (II). The alkene produced in the absence of anthracene is very unstable and polymerizes easily. The presence of the anthracene acts to trap the monomer in a Diels–Alder reaction and purification of (I) prior to thermolysis allows the generation of (II) (by a retro-Diels–Alder reaction) in a much more stable form. The presence of excess maleic anhydride in this reaction ensures that the released anthracene is consumed by the formation of an anthracene-maleic anhydride adduct and is not free to regenerate (I). Thus, this type of reaction may be useful in the trapping of alkenes and allow for easier purification.

The geometrical parameters for (I) are broadly similar to those of related 9,10-bridged anthracene derivatives (Table 1) (Gable et al., 1996 ; Karolak-Wojciechowska et al., 1998 ; Burrows et al., 1999 ). The two benzene rings in (I) (atoms C2–C7 and C9–C14) are both essentially planar (r.m.s. deviations from the least-squares planes are 0.010 and 0.001 Å, respectively). The dihedral angle between these rings is 57.62 (5)°, which is typical for these 9,10-bridged anthracene systems, e.g. the corresponding dihedral angle in 11,12-bis(N,N-dimethylaminomethyl)-9,10-dihydro-9,10-ethanoanthracene (Karolak-Wojciechowska et al., 1998) is 58.8 (2)°. The three six-membered rings of the bicyclic core of (I) (C1/C2/C7/C8/C9/C14, C1/C2/C7/C8/C15/C16 and C1/C14/C9/C8/C15/C16; see Fig. 1) are all forced into boat forms. The ester substituents show no unusual features.

The only significant intermolecular interaction in (I), as identified in a PLATON (Spek, 2003 ) analysis of the structure, is a C8—H8⋯O3ⁱ bond (Table 2). This bridgehead H8 atom attached to an sp³-hybridized C atom may be slightly activated due to ring strain (Desiraju & Steiner, 1999 ). This connectivity results in C(6) chains (Bernstein et al., 1995 ), generated by n-glide symmetry (Fig. 2). Otherwise, the crystal packing is controlled by van der Waals forces.

Figure 1
View of (I

) (50% displacement ellipsoids). H atoms are drawn as small spheres of arbitrary radius.

Figure 2
Detail of a chain of molecules of (I

) linked by C—H⋯O interactions. [Symmetry codes: (i) as in Table 2

; (ii) x + 1, y, z + 1.]

Experimental

A round-bottomed flask was fitted with a still head and condenser and diethyl malonate (9.70 g, 9.2 ml, 61 mmol), anthracene (12.00 g, 67 mmol), paraformaldehyde (3.64 g, 0.12 mol), copper(II) acetate monohydrate (0.60 g, 3.0 mmol), acetic acid (50 ml) and xylene (50 ml) were quickly added. The reaction mixture was heated at 383 K for 15 h and a clear dark-green solution resulted. The temperature was increased in order to distil off the acetic acid, then the reaction mixture was cooled to room temperature and filtered under suction. The filtrate was retained and the xylene evaporated on a rotary evaporator to yield a green oil which was left to crystallize. Purification was carried out by recrystallization from hot hexane. Filtration and washing with ice-cold hexane (25 ml) resulted in the pure anthracene adduct (I) (14.72 g, 69%) as colourless plates [m.p. 404.5–405 K; literature (De Keyser et al., 1988 ) 403–404 K from EtOH]; R_F(hexane–propan-2-ol 50:1) 0.13; ν_max (KBr disc)/cm⁻¹: 2974 (C—H), 1732 (C=O), 1460–1446 (aromatic C=C) and 757 (4 adjacent Ar-H); δH (250 MHz; CDCl₃): 1.15 (6H, t, J = 7.0 Hz, 2 × CH₃), 2.47 [2H, d, J = 2.4 Hz, (EtO₂C)₂CCH₂], 3.95–4.09 (4H, m, 2 × OCH₂), 4.33 (1H, poorly resolved t, J = 2.4 Hz, Ar₂CHCH₂), 4.97 [1H, s, Ar₂CHC(CO₂Et)₂] and 7.07–7.33 (8H, m, Ar-H); δC (CDCl₃): 14.0, 36.4, 43.9, 49.6, 60.0, 61.7, 123.3, 125.7, [De Keyser et al. (1988) give 125.68 and 125.74], 126.4, 139.8, 144.0 and 170.2.

Crystal data

C₂₂H₂₂O₄
M_r = 350.40
Monoclinic, P2₁/n
a = 9.2424 (2) Å
b = 16.5210 (5) Å
c = 11.9154 (4) Å
β = 98.631 (2)°
V = 1798.80 (9) Å³
Z = 4
D_x = 1.294 Mg m⁻³
Mo Kα radiation
Cell parameters from 21 198 reflections
θ = 2.9–27.5°
μ = 0.09 mm⁻¹
T = 120 (2) K
Plate, colourless
0.28 × 0.20 × 0.03 mm

Data collection

Enraf–Nonius KappaCCD diffractometer
ω and φ scans
Absorption correction: multi-scan (SORTAV; Blessing, 1995 ) T_min = 0.976, T_max = 0.999
21 237 measured reflections
3538 independent reflections
2750 reflections with I > 2σ(I)
R_int = 0.120
θ_max = 26.0°
h = −11 → 11
k = −20 → 20
l = −14 → 14

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.143
S = 1.06
3538 reflections
238 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0607P)² + 0.8446P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.25 e Å⁻³
Extinction correction: SHELXL97
Extinction coefficient: 0.012 (3)

Table 1
Selected geometrical parameters (Å °)

C1—C16	1.576 (3)
C8—C15	1.550 (3)
C15—C16	1.559 (3)

C20—C16—C17—O2	−131.2 (2)
C17—C16—C20—O3	−109.9 (2)

Table 2
Hydrogen-bonding geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8⋯O3ⁱ	1.00	2.56	3.380 (2)	139
Symmetry code: (i) $[{\script{1\over 2}}+x,{\script{1\over 2}}-y,{\script{1\over 2}}+z]$ .

All H atoms were geometrically placed in idealized locations and refined as riding on their carrier C atoms with C—H distances set to 0.95, 0.98, 0.99 and 1.00 Å for aromatic, sp², terminal sp³ and bridgehead sp³ hybrid C atoms, respectively. The constraint U_iso(H) = 1.2U_eq(C) or U_iso(H) = 1.5U_eq(methyl C) was applied as appropriate.

Data collection: COLLECT (Nonius, 1998 ); cell refinement: COLLECT and DENZO (Otwinowski & Minor, 1997 ); data reduction: COLLECT and DENZO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, ms01. DOI: https://doi.org/10.1107/S1600536804012279/hg6050sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536804012279/hg6050Isup2.hkl

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: COLLECT and DENZO (Otwinowski & Minor, 1997); data reduction: COLLECT and DENZO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

(I) top

Crystal data top

C₂₂H₂₂O₄	F(000) = 744
M_r = 350.40	D_x = 1.294 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 21198 reflections
a = 9.2424 (2) Å	θ = 2.9–27.5°
b = 16.5210 (5) Å	µ = 0.09 mm⁻¹
c = 11.9154 (4) Å	T = 120 K
β = 98.631 (2)°	Plate, colourless
V = 1798.80 (9) Å³	0.28 × 0.20 × 0.03 mm
Z = 4

Data collection top

Enraf–Nonius KappaCCD diffractometer	3538 independent reflections
Radiation source: fine-focus sealed tube	2750 reflections with I > 2σ(I)'
Graphite monochromator	R_int = 0.120
ω and φ scans	θ_max = 26.0°, θ_min = 3.0°
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	h = −11→11
T_min = 0.976, T_max = 0.999	k = −20→20
21237 measured reflections	l = −14→14

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.055	H-atom parameters constrained
wR(F²) = 0.143	w = 1/[σ²(F_o²) + (0.0607P)² + 0.8446P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
3538 reflections	Δρ_max = 0.30 e Å⁻³
238 parameters	Δρ_min = −0.25 e Å⁻³
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.012 (3)

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.0216 (2)	0.24941 (11)	0.79618 (16)	0.0207 (4)
H1	0.0063	0.2266	0.7176	0.025*
C2	0.1800 (2)	0.27254 (11)	0.83512 (16)	0.0221 (4)
C3	0.2947 (2)	0.26234 (12)	0.77362 (17)	0.0267 (5)
H3	0.2785	0.2375	0.7009	0.032*
C4	0.4342 (2)	0.28899 (13)	0.81988 (18)	0.0303 (5)
H4	0.5134	0.2828	0.7782	0.036*
C5	0.4574 (2)	0.32439 (13)	0.92616 (18)	0.0306 (5)
H5	0.5526	0.3426	0.9568	0.037*
C6	0.3427 (2)	0.33370 (12)	0.98894 (17)	0.0272 (5)
H6	0.3596	0.3572	1.0625	0.033*
C7	0.2032 (2)	0.30808 (12)	0.94241 (16)	0.0237 (4)
C8	0.0657 (2)	0.31482 (12)	0.99611 (16)	0.0234 (4)
H8	0.0844	0.3424	1.0716	0.028*
C9	−0.0462 (2)	0.35975 (12)	0.91330 (16)	0.0233 (4)
C10	−0.1241 (2)	0.42843 (12)	0.93459 (18)	0.0279 (5)
H10	−0.1088	0.4528	1.0076	0.033*
C11	−0.2248 (2)	0.46132 (13)	0.84820 (19)	0.0314 (5)
H11	−0.2782	0.5084	0.8622	0.038*
C12	−0.2475 (2)	0.42579 (13)	0.74195 (18)	0.0305 (5)
H12	−0.3166	0.4487	0.6835	0.037*
C13	−0.1706 (2)	0.35706 (12)	0.71985 (17)	0.0247 (4)
H13	−0.1866	0.3328	0.6467	0.030*
C14	−0.0703 (2)	0.32413 (11)	0.80559 (16)	0.0217 (4)
C15	0.0035 (2)	0.22833 (12)	1.00520 (16)	0.0238 (4)
H15A	−0.0908	0.2312	1.0349	0.029*
H15B	0.0725	0.1958	1.0587	0.029*
C16	−0.0199 (2)	0.18699 (11)	0.88621 (15)	0.0210 (4)
C17	0.0766 (2)	0.11174 (12)	0.88462 (15)	0.0220 (4)
C18	0.1230 (2)	−0.00151 (13)	0.77158 (19)	0.0327 (5)
H18A	0.0615	−0.0390	0.7201	0.039*
H18B	0.1501	−0.0290	0.8456	0.039*
C19	0.2581 (3)	0.01865 (16)	0.7228 (2)	0.0473 (6)
H19A	0.3088	−0.0314	0.7079	0.071*
H19B	0.3227	0.0521	0.7767	0.071*
H19C	0.2314	0.0485	0.6516	0.071*
C20	−0.1775 (2)	0.15905 (12)	0.85190 (16)	0.0219 (4)
C21	−0.3694 (2)	0.08520 (17)	0.9188 (2)	0.0441 (6)
H21A	−0.3710	0.0253	0.9166	0.053*
H21B	−0.4223	0.1056	0.8458	0.053*
C22	−0.4421 (3)	0.11405 (15)	1.0129 (2)	0.0402 (6)
H22A	−0.5432	0.0944	1.0026	0.060*
H22B	−0.4419	0.1734	1.0139	0.060*
H22C	−0.3895	0.0937	1.0849	0.060*
O1	0.03986 (15)	0.07194 (8)	0.78719 (12)	0.0287 (4)
O2	0.17203 (16)	0.09130 (9)	0.95894 (12)	0.0321 (4)
O3	−0.25370 (15)	0.17464 (9)	0.76424 (12)	0.0333 (4)
O4	−0.21870 (16)	0.11370 (10)	0.93410 (12)	0.0366 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0227 (9)	0.0208 (10)	0.0182 (9)	−0.0013 (8)	0.0025 (7)	−0.0005 (7)
C2	0.0247 (10)	0.0175 (10)	0.0242 (10)	−0.0001 (8)	0.0043 (8)	0.0042 (8)
C3	0.0307 (11)	0.0228 (11)	0.0270 (11)	0.0004 (8)	0.0062 (8)	0.0043 (8)
C4	0.0245 (10)	0.0291 (12)	0.0387 (12)	0.0025 (9)	0.0092 (9)	0.0099 (9)
C5	0.0236 (10)	0.0271 (12)	0.0396 (12)	−0.0024 (8)	0.0000 (9)	0.0078 (9)
C6	0.0293 (11)	0.0217 (10)	0.0284 (11)	−0.0013 (8)	−0.0032 (8)	0.0022 (8)
C7	0.0245 (10)	0.0199 (10)	0.0258 (10)	0.0004 (8)	0.0014 (8)	0.0019 (8)
C8	0.0244 (10)	0.0248 (10)	0.0205 (10)	−0.0030 (8)	0.0020 (8)	−0.0038 (8)
C9	0.0230 (10)	0.0233 (10)	0.0239 (10)	−0.0035 (8)	0.0047 (7)	−0.0001 (8)
C10	0.0272 (11)	0.0248 (11)	0.0325 (11)	−0.0048 (8)	0.0068 (8)	−0.0069 (9)
C11	0.0277 (11)	0.0226 (11)	0.0446 (13)	0.0022 (9)	0.0078 (9)	−0.0013 (9)
C12	0.0275 (11)	0.0268 (12)	0.0368 (12)	0.0011 (9)	0.0034 (9)	0.0064 (9)
C13	0.0244 (10)	0.0236 (11)	0.0257 (10)	−0.0036 (8)	0.0020 (8)	0.0014 (8)
C14	0.0214 (10)	0.0193 (10)	0.0248 (10)	−0.0044 (8)	0.0049 (8)	−0.0007 (8)
C15	0.0257 (10)	0.0266 (11)	0.0193 (10)	−0.0003 (8)	0.0036 (8)	0.0001 (8)
C16	0.0221 (10)	0.0209 (10)	0.0196 (9)	−0.0001 (7)	0.0022 (7)	−0.0006 (7)
C17	0.0213 (9)	0.0221 (10)	0.0229 (10)	−0.0035 (8)	0.0044 (8)	0.0012 (8)
C18	0.0334 (12)	0.0214 (11)	0.0428 (13)	0.0066 (9)	0.0039 (10)	−0.0087 (9)
C19	0.0495 (15)	0.0438 (15)	0.0524 (15)	0.0110 (12)	0.0203 (12)	0.0001 (12)
C20	0.0232 (10)	0.0199 (10)	0.0232 (10)	0.0018 (8)	0.0053 (8)	−0.0031 (8)
C21	0.0316 (13)	0.0571 (16)	0.0457 (14)	−0.0259 (11)	0.0128 (10)	−0.0100 (12)
C22	0.0332 (12)	0.0418 (14)	0.0464 (14)	0.0044 (10)	0.0083 (10)	0.0025 (11)
O1	0.0286 (8)	0.0245 (8)	0.0319 (8)	0.0049 (6)	0.0005 (6)	−0.0079 (6)
O2	0.0312 (8)	0.0340 (9)	0.0294 (8)	0.0072 (6)	−0.0010 (6)	0.0024 (6)
O3	0.0283 (8)	0.0345 (9)	0.0339 (8)	−0.0054 (6)	−0.0065 (6)	0.0042 (6)
O4	0.0305 (8)	0.0487 (10)	0.0306 (8)	−0.0174 (7)	0.0043 (6)	0.0057 (7)

Geometric parameters (Å, º) top

C1—C14	1.512 (3)	C13—C14	1.384 (3)
C1—C2	1.516 (3)	C13—H13	0.9500
C1—C16	1.576 (3)	C15—C16	1.559 (3)
C1—H1	1.0000	C15—H15A	0.9900
C2—C3	1.387 (3)	C15—H15B	0.9900
C2—C7	1.394 (3)	C16—C20	1.524 (3)
C3—C4	1.395 (3)	C16—C17	1.532 (3)
C3—H3	0.9500	C17—O2	1.201 (2)
C4—C5	1.382 (3)	C17—O1	1.333 (2)
C4—H4	0.9500	C18—O1	1.463 (2)
C5—C6	1.395 (3)	C18—C19	1.492 (3)
C5—H5	0.9500	C18—H18A	0.9900
C6—C7	1.391 (3)	C18—H18B	0.9900
C6—H6	0.9500	C19—H19A	0.9800
C7—C8	1.510 (3)	C19—H19B	0.9800
C8—C9	1.513 (3)	C19—H19C	0.9800
C8—C15	1.550 (3)	C20—O3	1.197 (2)
C8—H8	1.0000	C20—O4	1.333 (2)
C9—C10	1.387 (3)	C21—O4	1.455 (2)
C9—C14	1.399 (3)	C21—C22	1.470 (3)
C10—C11	1.390 (3)	C21—H21A	0.9900
C10—H10	0.9500	C21—H21B	0.9900
C11—C12	1.383 (3)	C22—H22A	0.9800
C11—H11	0.9500	C22—H22B	0.9800
C12—C13	1.386 (3)	C22—H22C	0.9800
C12—H12	0.9500

C14—C1—C2	107.37 (15)	C13—C14—C1	126.00 (17)
C14—C1—C16	106.66 (15)	C9—C14—C1	113.45 (16)
C2—C1—C16	106.21 (14)	C8—C15—C16	110.04 (15)
C14—C1—H1	112.1	C8—C15—H15A	109.7
C2—C1—H1	112.1	C16—C15—H15A	109.7
C16—C1—H1	112.1	C8—C15—H15B	109.7
C3—C2—C7	120.74 (18)	C16—C15—H15B	109.7
C3—C2—C1	125.96 (18)	H15A—C15—H15B	108.2
C7—C2—C1	113.29 (16)	C20—C16—C17	106.61 (15)
C2—C3—C4	119.17 (19)	C20—C16—C15	111.94 (15)
C2—C3—H3	120.4	C17—C16—C15	111.39 (15)
C4—C3—H3	120.4	C20—C16—C1	109.64 (15)
C5—C4—C3	120.18 (19)	C17—C16—C1	108.70 (15)
C5—C4—H4	119.9	C15—C16—C1	108.50 (15)
C3—C4—H4	119.9	O2—C17—O1	124.51 (18)
C4—C5—C6	120.81 (19)	O2—C17—C16	125.72 (17)
C4—C5—H5	119.6	O1—C17—C16	109.77 (15)
C6—C5—H5	119.6	O1—C18—C19	110.52 (18)
C7—C6—C5	119.10 (19)	O1—C18—H18A	109.5
C7—C6—H6	120.4	C19—C18—H18A	109.5
C5—C6—H6	120.4	O1—C18—H18B	109.5
C6—C7—C2	119.98 (18)	C19—C18—H18B	109.5
C6—C7—C8	126.67 (18)	H18A—C18—H18B	108.1
C2—C7—C8	113.34 (16)	C18—C19—H19A	109.5
C7—C8—C9	107.23 (15)	C18—C19—H19B	109.5
C7—C8—C15	107.81 (16)	H19A—C19—H19B	109.5
C9—C8—C15	105.88 (15)	C18—C19—H19C	109.5
C7—C8—H8	111.9	H19A—C19—H19C	109.5
C9—C8—H8	111.9	H19B—C19—H19C	109.5
C15—C8—H8	111.9	O3—C20—O4	124.48 (18)
C10—C9—C14	119.77 (18)	O3—C20—C16	125.63 (18)
C10—C9—C8	127.21 (18)	O4—C20—C16	109.88 (16)
C14—C9—C8	113.00 (17)	O4—C21—C22	109.74 (19)
C9—C10—C11	119.48 (19)	O4—C21—H21A	109.7
C9—C10—H10	120.3	C22—C21—H21A	109.7
C11—C10—H10	120.3	O4—C21—H21B	109.7
C12—C11—C10	120.33 (19)	C22—C21—H21B	109.7
C12—C11—H11	119.8	H21A—C21—H21B	108.2
C10—C11—H11	119.8	C21—C22—H22A	109.5
C11—C12—C13	120.67 (19)	C21—C22—H22B	109.5
C11—C12—H12	119.7	H22A—C22—H22B	109.5
C13—C12—H12	119.7	C21—C22—H22C	109.5
C14—C13—C12	119.20 (18)	H22A—C22—H22C	109.5
C14—C13—H13	120.4	H22B—C22—H22C	109.5
C12—C13—H13	120.4	C17—O1—C18	116.73 (15)
C13—C14—C9	120.55 (18)	C20—O4—C21	117.59 (17)

C14—C1—C2—C3	−125.2 (2)	C2—C1—C14—C13	126.6 (2)
C16—C1—C2—C3	121.0 (2)	C16—C1—C14—C13	−119.9 (2)
C14—C1—C2—C7	53.7 (2)	C2—C1—C14—C9	−53.7 (2)
C16—C1—C2—C7	−60.1 (2)	C16—C1—C14—C9	59.8 (2)
C7—C2—C3—C4	−0.7 (3)	C7—C8—C15—C16	−55.1 (2)
C1—C2—C3—C4	178.10 (18)	C9—C8—C15—C16	59.4 (2)
C2—C3—C4—C5	0.6 (3)	C8—C15—C16—C20	−123.56 (17)
C3—C4—C5—C6	0.3 (3)	C8—C15—C16—C17	117.18 (17)
C4—C5—C6—C7	−1.1 (3)	C8—C15—C16—C1	−2.4 (2)
C5—C6—C7—C2	1.0 (3)	C14—C1—C16—C20	66.91 (18)
C5—C6—C7—C8	−178.54 (18)	C2—C1—C16—C20	−178.79 (15)
C3—C2—C7—C6	−0.1 (3)	C14—C1—C16—C17	−176.91 (14)
C1—C2—C7—C6	−179.02 (17)	C2—C1—C16—C17	−62.61 (18)
C3—C2—C7—C8	179.51 (17)	C14—C1—C16—C15	−55.63 (19)
C1—C2—C7—C8	0.5 (2)	C2—C1—C16—C15	58.68 (19)
C6—C7—C8—C9	124.7 (2)	C20—C16—C17—O2	−131.2 (2)
C2—C7—C8—C9	−54.8 (2)	C15—C16—C17—O2	−8.8 (3)
C6—C7—C8—C15	−121.7 (2)	C1—C16—C17—O2	110.7 (2)
C2—C7—C8—C15	58.8 (2)	C20—C16—C17—O1	49.30 (19)
C7—C8—C9—C10	−126.4 (2)	C15—C16—C17—O1	171.68 (15)
C15—C8—C9—C10	118.7 (2)	C1—C16—C17—O1	−68.82 (19)
C7—C8—C9—C14	54.7 (2)	C17—C16—C20—O3	−109.9 (2)
C15—C8—C9—C14	−60.2 (2)	C15—C16—C20—O3	128.1 (2)
C14—C9—C10—C11	−0.3 (3)	C1—C16—C20—O3	7.6 (3)
C8—C9—C10—C11	−179.15 (19)	C17—C16—C20—O4	69.68 (19)
C9—C10—C11—C12	0.2 (3)	C15—C16—C20—O4	−52.4 (2)
C10—C11—C12—C13	0.0 (3)	C1—C16—C20—O4	−172.83 (15)
C11—C12—C13—C14	0.0 (3)	O2—C17—O1—C18	0.0 (3)
C12—C13—C14—C9	−0.2 (3)	C16—C17—O1—C18	179.50 (16)
C12—C13—C14—C1	179.54 (18)	C19—C18—O1—C17	−86.8 (2)
C10—C9—C14—C13	0.3 (3)	O3—C20—O4—C21	−3.8 (3)
C8—C9—C14—C13	179.30 (17)	C16—C20—O4—C21	176.68 (17)
C10—C9—C14—C1	−179.41 (17)	C22—C21—O4—C20	−121.4 (2)
C8—C9—C14—C1	−0.4 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···O3ⁱ	1.00	2.56	3.380 (2)	139

Symmetry code: (i) x+1/2, −y+1/2, z+1/2.

Acknowledgements

We thank the EPSRC UK National Crystallography Service (University of Southampton) for the data collection.

References

Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Blessing, R. H. (1995). Acta Cryst. A51, 33–38. CrossRef CAS Web of Science IUCr Journals Google Scholar
Burrows, L., Masnovi, J. & Baker, R. J. (1999). Acta Cryst. C55, 236–239. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
De Keyser, J.-L., De Cock, C. J. C., Poupaert, J. H. & Dumont, P. (1988). J. Org. Chem. 53, 4859–4862. CrossRef CAS Web of Science Google Scholar
Desiraju, G. R. & Steiner, T. (1999). The Weak Hydrogen Bond. Oxford: IUCr/OUP. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Gable, R. W., Qureshi, A. & Schiesser, C. H. (1996). Acta Cryst. C52, 674–675. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Karolak-Wojciechowska, J., Trzeźwińska, H. B., Alibert-Franco, S., Santelli-Rouvier, C. & Barbe, J. (1998). J. Chem. Crystallogr. 28, 905–911. Web of Science CSD CrossRef CAS Google Scholar
Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr andR. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Sheldrick, G. M. (1997). SHELXL97. University of Göttingen, Germany. Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar

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