2-Hydr­oxy-4,6-dimeth­oxy-3-(3-methylbutano­yl)benzaldehyde

The structure of the title compound, C₁₄H₁₈O₅, has two independent mol­ecules related by a local noncrystallographic a-glide plane perpendicular to the b axis. The pseudo-glide plane shows a discontinuity at z = 0. Both mol­ecules have an intra­molecular hydrogen bond between the hydr­oxy and aldehyde groups. There are stacks of mol­ecules along the a-­axis direction. Neighboring mol­ecules in the stack have an inter­planar angle of 1.6 (1)°, inter­planar distances ranging between 3.399 (3) and 3.417 (3) Å, and a ring offset of 1.38 (1) Å.

S1. Comment

The title compound, (I), was obtained by a Friedel–Crafts acylation reaction of 4,6-dimethoxysalicylaldehyde with 3-methylbutyric acid chloride (Reggelin et al., 1999). Only one of two possible regioisomers was obtained. The constitution of (I) could not be determined by HMBC correlations (Bax & Summers, 1986). Only after the application of 1,n-ADEQUATE experiments (Reif et al., 1996) was pit ossible to ascertain the substitution pattern (Köck et al., 1996). To corroborate the results from the NMR studies, a crystal structure analysis of (I) was performed.

The structure contains two independent molecules (A and B). They are illustrated in Fig. 1. The dimensions of the two molecules are very similar. The r.m.s. deviation of a least-squares fit of the non-H atoms is 0.011 Å. In each of the molecules, there is an intramolecular O—H···O hydrogen bond between the hydroxyl group and the aldehyde group (Table 1). The aldehyde and the two methoxy groups are almost coplanar with the benzene plane. The angle between the plane of the benzene ring and the plane of the keto group attached to C1 (or C15) is 43.6 (1)° for both molecules. This nonplanar orientation is required to avoid a short repulsive contact between atoms O1 and O2 (or between O6 and O7).

The crystal structure shows stacks of molecules along the crystallographic a-axis direction. The order of the molecules in the stack is ABAB etc., as shown in Fig. 2. The interplanar angle between the benzene rings of molecules A and B is 1.6 (1)°. The perpendicular distance between the planes, defined as the shortest distance of a ring centroid to the plane of the adjacent ring, ranges from 3.399 to 3.417 Å. There is an offset of 1.38 Å [are s.u. values available (also in abstract)?] between the centroids of neighboring rings. There are intermolecular π–π contacts between neighboring benzaldehyde groups. The shortest intermolecular C(π)···C(π) distances are between 3.335 (3) and 3.428 (3) Å and are illustrated in Fig. 2 as broken lines. Those involving the aldehyde C atoms are slightly shorter than the perpendicular distances between the benzene planes. The molecules in the stack are also connected by four intermolecular C—H···O interactions (Table 1, entries 3 to 6) with H···O distances between 2.52 and 2.57 Å (also shown in Fig. 2). The stacks are connected by additional intermolecular C—H···O contacts (Table 1, entries 7 and 8), with H···O distances of 2.47 and 2.52 Å, to bilayers parallel to the [001] plane, as shown in Fig. 3. There are also four intermolecular O_keto···C_methoxy interactions, with O···C distances of 2.910 (2), 2.929 (2), 3.015 (2) and 3.019 (2) Å, which connect the stacks in the b-axis direction. These O···C distances are significantly shorter than the van der Waals contact distance of 3.22 Å (Bondi, 1964), and the C═O···C and O···C—O angles are almost linear. No significant interactions are observed between neighboring bilayers in the c-axis direction.

The two molecules are related by pseudo-symmetry. Inspection of the fractional coordinates shows the two molecules to be related by the pseudo-relationship x_A=x_B + 1/2, y_A = 1.257 - y_B + 0.539z_B and z_A = z_B. This is a local noncrystallographic a-glide plane perpendicular to the b axis, intersecting the b axis at positions y = 0.128 and y = 0.628, as shown in Fig. 3. The pseudo-glide plane is continuous in the crystallographic a-axis direction, resulting in a value of the unit-cell angle γ of approximately 90°. In the c-axis direction, the pseudo-glide plane acts only in one unit cell and shows discontinuities at z = 0 and z = 1. Similar pseudo-symmetry has been observed by us in other crystal structures (Bats, Hoyer & Mulzer, 1999; Bats, Öhlinger & Mulzer, 1999).

Related literature

For related literature, see: Bats, Hoyer & Mulzer (1999); Bats, Öhlinger & Mulzer (1999); Bax & Summers (1986); Bondi (1964); Köck et al. (1996); Reggelin et al. (1999); Reif et al. (1996).

S2. Experimental

The preparation of (I) has been reported by Köck et al. (1996). Single crystals were obtained by slow evaporation of a solution of (I) in CDCl₃ at about 280 K.

S3. Refinement

H atoms were positioned geometrically and tretaed as riding [Csp²—H = 0.95 Å, C_primary—H = 1.00 Å, C_secondary—H = 0.99 Å, C_methyl—H = 0.98 Å, O—H = 0.84 Å, and U_iso(H) = 1.2U_eq(C) and 1.5U_eq(C_methyl,O)]. The torsion angle about the C—C axis was refined for the methyl groups and the torsion angle about the C—O axis was refined for the hydroxy groups. The triclinic unit cell can be transformed to a C-centered cell with monoclinic shape. The Laue symmetry, however, showed the structure to be triclinic (R_int = 0.067) rather than monoclinic (R_int = 0.56). The present unit cell can be reduced by the transformation a_red = −a, b_red = b and c_red = −a − c. The choice of the reduced cell was found to depend on the exact value of the cell angle β and changed during the final refinement of the unit-cell parameters. The original setting was retained in this work.

Computing details

Data collection: SMART (Siemens, 1995); cell refinement: SMART (Siemens, 1995); 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 (Sheldrick, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

	Fig. 1. The two independent molecules, A and B, of (I), with the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are drawn as small spheres of arbitrary radii.
	Fig. 2. The stacking of the molecules. The shortest intermolecular Cπ···Cπ interactions are shown as broken lines; dotted lines represent intermolecular C—H···O interactions. [Symmetry code (i): x + 1, y, z.
	Fig. 3. A projection of the crystal packing of (I) down a. Dashed lines represent C—H···O interactions between stacks. The local pseudo-a-glide planes are shown as dotted lines. A and B represent the positions of molecules A and B.

2-Hydroxy-4,6-dimethoxy-3-(3-methylbutanoyl)benzaldehyde

Crystal data

C14H18O5	Z = 4
Mr = 266.28	F(000) = 568
Triclinic, P1	Dx = 1.333 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.2946 (10) Å	Cell parameters from 164 reflections
b = 8.2775 (13) Å	θ = 3–23°
c = 22.400 (3) Å	µ = 0.10 mm^−1
α = 95.949 (6)°	T = 160 K
β = 99.410 (8)°	Rod, colorless
γ = 90.099 (6)°	0.50 × 0.22 × 0.16 mm
V = 1326.9 (3) Å^3

Data collection

Siemens SMART 1K CCD diffractometer	3128 reflections with I > 2σ(I)
Radiation source: normal-focus sealed tube	Rint = 0.067
Graphite monochromator	θmax = 27.5°, θmin = 1.9°
ω scans	h = −9→9
19412 measured reflections	k = −10→10
5830 independent reflections	l = −28→28

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.131	H-atom parameters constrained
S = 0.97	w = 1/[σ^2(Fo^2) + (0.06P)^2] where P = (Fo^2 + 2Fc^2)/3
5830 reflections	(Δ/σ)max = 0.001
353 parameters	Δρmax = 0.23 e Å^−3
0 restraints	Δρmin = −0.24 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	0.4421 (2)	0.99181 (17)	0.27024 (7)	0.0303 (4)
O2	0.5985 (2)	0.97494 (16)	0.16837 (6)	0.0286 (4)
H2	0.6286	0.9947	0.1352	0.043*
O3	0.6770 (2)	0.92291 (18)	0.06135 (7)	0.0339 (4)
O4	0.6531 (2)	0.44873 (16)	0.07131 (6)	0.0294 (4)
O5	0.5163 (2)	0.52705 (17)	0.27523 (6)	0.0280 (4)
C1	0.5566 (3)	0.7526 (2)	0.22359 (9)	0.0215 (5)
C2	0.5903 (3)	0.8130 (2)	0.17034 (9)	0.0220 (5)
C3	0.6223 (3)	0.7097 (2)	0.11897 (9)	0.0219 (5)
C4	0.6179 (3)	0.5405 (2)	0.12210 (9)	0.0233 (5)
C5	0.5806 (3)	0.4767 (2)	0.17310 (9)	0.0229 (5)
H5	0.5741	0.3624	0.1741	0.028*
C6	0.5522 (3)	0.5824 (2)	0.22355 (9)	0.0229 (5)
C7	0.5322 (3)	0.8695 (3)	0.27780 (9)	0.0232 (5)
C8	0.6337 (3)	0.8413 (2)	0.34006 (9)	0.0280 (5)
H8A	0.7627	0.8098	0.3365	0.034*
H8B	0.5727	0.7491	0.3544	0.034*
C9	0.6400 (3)	0.9884 (3)	0.38773 (10)	0.0348 (6)
H9	0.6683	1.0873	0.3685	0.042*
C10	0.4555 (4)	1.0129 (3)	0.41024 (11)	0.0520 (8)
H10A	0.4273	0.9189	0.4306	0.078*
H10B	0.3570	1.0244	0.3756	0.078*
H10C	0.4633	1.1113	0.4390	0.078*
C11	0.7954 (4)	0.9700 (3)	0.44102 (11)	0.0518 (8)
H11A	0.8010	1.0661	0.4708	0.078*
H11B	0.9143	0.9588	0.4261	0.078*
H11C	0.7708	0.8731	0.4604	0.078*
C12	0.6669 (3)	0.7753 (3)	0.06646 (10)	0.0278 (5)
H12	0.6903	0.7013	0.0333	0.033*
C13	0.6574 (3)	0.2756 (2)	0.07226 (10)	0.0306 (6)
H13A	0.7485	0.2486	0.1069	0.046*
H13B	0.6925	0.2250	0.0343	0.046*
H13C	0.5341	0.2351	0.0762	0.046*
C14	0.5009 (3)	0.3543 (2)	0.27716 (10)	0.0312 (6)
H14A	0.4012	0.3091	0.2450	0.047*
H14B	0.4723	0.3324	0.3168	0.047*
H14C	0.6187	0.3037	0.2710	0.047*
O6	−0.0592 (2)	0.41049 (17)	0.26941 (6)	0.0299 (4)
O7	0.0955 (2)	0.37158 (16)	0.16711 (6)	0.0292 (4)
H7	0.1224	0.3340	0.1334	0.044*
O8	0.1716 (2)	0.36713 (18)	0.05945 (7)	0.0349 (4)
O9	0.1570 (2)	0.84623 (16)	0.07265 (6)	0.0291 (4)
O10	0.0167 (2)	0.87816 (16)	0.27580 (6)	0.0285 (4)
C15	0.0568 (3)	0.6244 (2)	0.22362 (9)	0.0219 (5)
C16	0.0888 (3)	0.5355 (2)	0.16986 (9)	0.0227 (5)
C17	0.1224 (3)	0.6109 (2)	0.11911 (9)	0.0228 (5)
C18	0.1197 (3)	0.7824 (2)	0.12264 (9)	0.0245 (5)
C19	0.0820 (3)	0.8738 (2)	0.17419 (9)	0.0239 (5)
H19	0.0760	0.9887	0.1757	0.029*
C20	0.0528 (3)	0.7950 (2)	0.22393 (9)	0.0224 (5)
C21	0.0327 (3)	0.5366 (3)	0.27717 (10)	0.0249 (5)
C22	0.1337 (3)	0.5978 (3)	0.33969 (9)	0.0279 (5)
H22A	0.0732	0.6979	0.3543	0.033*
H22B	0.2629	0.6275	0.3364	0.033*
C23	0.1395 (3)	0.4778 (3)	0.38708 (10)	0.0340 (6)
H23	0.1667	0.3682	0.3676	0.041*
C24	−0.0463 (4)	0.4659 (3)	0.40937 (12)	0.0535 (7)
H24A	−0.0732	0.5708	0.4304	0.080*
H24B	−0.0401	0.3821	0.4375	0.080*
H24C	−0.1449	0.4371	0.3745	0.080*
C25	0.2947 (4)	0.5237 (3)	0.44056 (11)	0.0510 (7)
H25A	0.4144	0.5229	0.4260	0.076*
H25B	0.2963	0.4451	0.4705	0.076*
H25C	0.2734	0.6325	0.4596	0.076*
C26	0.1641 (3)	0.5172 (3)	0.06555 (10)	0.0280 (5)
H26	0.1874	0.5740	0.0327	0.034*
C27	0.1609 (3)	1.0195 (2)	0.07336 (10)	0.0301 (5)
H27A	0.0369	1.0615	0.0763	0.045*
H27B	0.1988	1.0486	0.0358	0.045*
H27C	0.2498	1.0668	0.1085	0.045*
C28	0.0027 (3)	1.0527 (2)	0.27838 (10)	0.0311 (6)
H28A	0.1202	1.0995	0.2717	0.047*
H28B	−0.0235	1.0961	0.3184	0.047*
H28C	−0.0981	1.0807	0.2468	0.047*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0326 (9)	0.0250 (9)	0.0319 (9)	0.0064 (7)	0.0037 (7)	−0.0005 (7)
O2	0.0392 (10)	0.0197 (9)	0.0281 (9)	−0.0013 (7)	0.0082 (8)	0.0037 (6)
O3	0.0480 (11)	0.0242 (9)	0.0316 (9)	0.0013 (7)	0.0113 (8)	0.0058 (7)
O4	0.0426 (10)	0.0214 (9)	0.0248 (8)	0.0007 (7)	0.0099 (7)	−0.0015 (6)
O5	0.0352 (9)	0.0233 (9)	0.0273 (9)	−0.0003 (7)	0.0088 (7)	0.0047 (6)
C1	0.0190 (11)	0.0206 (12)	0.0238 (12)	0.0011 (9)	0.0016 (9)	0.0000 (9)
C2	0.0207 (11)	0.0173 (12)	0.0270 (12)	0.0009 (9)	0.0005 (9)	0.0030 (9)
C3	0.0223 (11)	0.0202 (12)	0.0220 (11)	0.0003 (9)	0.0014 (9)	0.0010 (9)
C4	0.0204 (11)	0.0231 (12)	0.0250 (12)	−0.0009 (9)	0.0023 (9)	−0.0017 (9)
C5	0.0227 (12)	0.0175 (12)	0.0279 (13)	0.0000 (9)	0.0028 (10)	0.0016 (9)
C6	0.0191 (11)	0.0244 (13)	0.0250 (12)	−0.0001 (9)	0.0020 (9)	0.0042 (9)
C7	0.0214 (12)	0.0235 (12)	0.0246 (12)	−0.0045 (9)	0.0052 (9)	0.0001 (9)
C8	0.0263 (12)	0.0314 (13)	0.0260 (12)	0.0016 (10)	0.0043 (10)	0.0011 (10)
C9	0.0391 (14)	0.0365 (14)	0.0261 (13)	−0.0011 (11)	0.0004 (11)	−0.0027 (10)
C10	0.0528 (18)	0.066 (2)	0.0356 (15)	0.0157 (14)	0.0124 (13)	−0.0090 (13)
C11	0.0515 (18)	0.0629 (19)	0.0326 (15)	0.0018 (14)	−0.0070 (13)	−0.0120 (13)
C12	0.0316 (13)	0.0255 (14)	0.0248 (13)	0.0026 (10)	0.0027 (10)	−0.0009 (10)
C13	0.0419 (15)	0.0160 (12)	0.0336 (13)	0.0014 (10)	0.0079 (11)	−0.0019 (9)
C14	0.0357 (14)	0.0234 (13)	0.0361 (14)	−0.0012 (10)	0.0064 (11)	0.0097 (10)
O6	0.0325 (9)	0.0272 (9)	0.0297 (9)	−0.0046 (7)	0.0040 (7)	0.0033 (7)
O7	0.0391 (10)	0.0204 (9)	0.0287 (9)	0.0002 (7)	0.0083 (8)	0.0003 (6)
O8	0.0484 (11)	0.0233 (9)	0.0338 (9)	0.0002 (7)	0.0120 (8)	−0.0011 (7)
O9	0.0410 (10)	0.0211 (9)	0.0266 (9)	−0.0007 (7)	0.0093 (7)	0.0036 (6)
O10	0.0366 (9)	0.0221 (9)	0.0275 (9)	0.0024 (7)	0.0092 (7)	−0.0009 (6)
C15	0.0199 (11)	0.0218 (12)	0.0232 (12)	−0.0026 (9)	0.0016 (9)	0.0014 (9)
C16	0.0227 (12)	0.0173 (12)	0.0259 (12)	−0.0013 (9)	−0.0022 (9)	0.0017 (9)
C17	0.0209 (11)	0.0225 (12)	0.0241 (12)	−0.0008 (9)	0.0026 (9)	0.0007 (9)
C18	0.0230 (12)	0.0236 (13)	0.0263 (12)	0.0004 (9)	0.0014 (9)	0.0040 (9)
C19	0.0251 (12)	0.0173 (12)	0.0279 (13)	−0.0002 (9)	0.0018 (10)	−0.0007 (9)
C20	0.0198 (11)	0.0238 (12)	0.0229 (12)	−0.0011 (9)	0.0037 (9)	−0.0013 (9)
C21	0.0207 (12)	0.0240 (13)	0.0300 (13)	0.0028 (9)	0.0058 (10)	0.0002 (9)
C22	0.0264 (12)	0.0306 (13)	0.0254 (12)	−0.0011 (10)	0.0026 (10)	−0.0004 (10)
C23	0.0402 (14)	0.0365 (14)	0.0244 (12)	−0.0002 (11)	0.0018 (10)	0.0045 (10)
C24	0.0565 (19)	0.070 (2)	0.0360 (16)	−0.0119 (15)	0.0125 (14)	0.0098 (13)
C25	0.0523 (18)	0.0616 (19)	0.0359 (15)	−0.0029 (14)	−0.0058 (13)	0.0113 (13)
C26	0.0324 (13)	0.0240 (13)	0.0268 (13)	−0.0011 (10)	0.0031 (10)	0.0010 (10)
C27	0.0393 (14)	0.0184 (12)	0.0342 (13)	0.0001 (10)	0.0083 (11)	0.0058 (10)
C28	0.0369 (14)	0.0220 (13)	0.0347 (14)	0.0020 (10)	0.0101 (11)	−0.0028 (10)

Geometric parameters (Å, º)

O1—C7	1.219 (2)	O6—C21	1.221 (2)
O2—C2	1.347 (2)	O7—C16	1.353 (2)
O2—H2	0.8400	O7—H7	0.8400
O3—C12	1.242 (2)	O8—C26	1.238 (2)
O4—C4	1.362 (2)	O9—C18	1.352 (2)
O4—C13	1.436 (2)	O9—C27	1.433 (2)
O5—C6	1.352 (2)	O10—C20	1.352 (2)
O5—C14	1.440 (2)	O10—C28	1.444 (2)
C1—C2	1.397 (3)	C15—C16	1.398 (3)
C1—C6	1.409 (3)	C15—C20	1.412 (3)
C1—C7	1.507 (3)	C15—C21	1.499 (3)
C2—C3	1.412 (3)	C16—C17	1.407 (3)
C3—C4	1.410 (3)	C17—C18	1.414 (3)
C3—C12	1.428 (3)	C17—C26	1.435 (3)
C4—C5	1.373 (3)	C18—C19	1.380 (3)
C5—C6	1.399 (3)	C19—C20	1.393 (3)
C5—H5	0.9500	C19—H19	0.9500
C7—C8	1.509 (3)	C21—C22	1.509 (3)
C8—C9	1.529 (3)	C22—C23	1.523 (3)
C8—H8A	0.9900	C22—H22A	0.9900
C8—H8B	0.9900	C22—H22B	0.9900
C9—C10	1.519 (3)	C23—C25	1.524 (3)
C9—C11	1.526 (3)	C23—C24	1.525 (3)
C9—H9	1.0000	C23—H23	1.0000
C10—H10A	0.9800	C24—H24A	0.9800
C10—H10B	0.9800	C24—H24B	0.9800
C10—H10C	0.9800	C24—H24C	0.9800
C11—H11A	0.9800	C25—H25A	0.9800
C11—H11B	0.9800	C25—H25B	0.9800
C11—H11C	0.9800	C25—H25C	0.9800
C12—H12	0.9500	C26—H26	0.9500
C13—H13A	0.9800	C27—H27A	0.9800
C13—H13B	0.9800	C27—H27B	0.9800
C13—H13C	0.9800	C27—H27C	0.9800
C14—H14A	0.9800	C28—H28A	0.9800
C14—H14B	0.9800	C28—H28B	0.9800
C14—H14C	0.9800	C28—H28C	0.9800
C2—O2—H2	109.5	C16—O7—H7	109.5
C4—O4—C13	117.78 (16)	C18—O9—C27	118.26 (16)
C6—O5—C14	118.57 (15)	C20—O10—C28	118.54 (16)
C2—C1—C6	116.88 (18)	C16—C15—C20	116.57 (18)
C2—C1—C7	119.48 (18)	C16—C15—C21	119.46 (18)
C6—C1—C7	123.62 (18)	C20—C15—C21	123.95 (18)
O2—C2—C1	119.19 (17)	O7—C16—C15	119.16 (18)
O2—C2—C3	118.66 (18)	O7—C16—C17	118.51 (17)
C1—C2—C3	122.11 (18)	C15—C16—C17	122.28 (18)
C4—C3—C2	118.16 (19)	C16—C17—C18	118.39 (18)
C4—C3—C12	120.97 (18)	C16—C17—C26	121.18 (19)
C2—C3—C12	120.80 (19)	C18—C17—C26	120.40 (19)
O4—C4—C5	123.76 (18)	O9—C18—C19	124.06 (19)
O4—C4—C3	114.89 (18)	O9—C18—C17	115.03 (17)
C5—C4—C3	121.35 (19)	C19—C18—C17	120.9 (2)
C4—C5—C6	119.02 (19)	C18—C19—C20	119.02 (19)
C4—C5—H5	120.5	C18—C19—H19	120.5
C6—C5—H5	120.5	C20—C19—H19	120.5
O5—C6—C5	121.83 (18)	O10—C20—C19	121.68 (18)
O5—C6—C1	115.73 (17)	O10—C20—C15	115.55 (18)
C5—C6—C1	122.43 (19)	C19—C20—C15	122.76 (18)
O1—C7—C1	119.59 (18)	O6—C21—C15	119.81 (19)
O1—C7—C8	120.74 (18)	O6—C21—C22	120.3 (2)
C1—C7—C8	119.44 (17)	C15—C21—C22	119.72 (19)
C7—C8—C9	114.24 (17)	C21—C22—C23	114.87 (18)
C7—C8—H8A	108.7	C21—C22—H22A	108.6
C9—C8—H8A	108.7	C23—C22—H22A	108.5
C7—C8—H8B	108.7	C21—C22—H22B	108.6
C9—C8—H8B	108.7	C23—C22—H22B	108.5
H8A—C8—H8B	107.6	H22A—C22—H22B	107.5
C10—C9—C11	110.3 (2)	C22—C23—C25	110.70 (19)
C10—C9—C8	112.0 (2)	C22—C23—C24	111.8 (2)
C11—C9—C8	109.98 (19)	C25—C23—C24	110.3 (2)
C10—C9—H9	108.1	C22—C23—H23	108.0
C11—C9—H9	108.1	C25—C23—H23	108.0
C8—C9—H9	108.1	C24—C23—H23	108.0
C9—C10—H10A	109.5	C23—C24—H24A	109.5
C9—C10—H10B	109.5	C23—C24—H24B	109.5
H10A—C10—H10B	109.5	H24A—C24—H24B	109.5
C9—C10—H10C	109.5	C23—C24—H24C	109.5
H10A—C10—H10C	109.5	H24A—C24—H24C	109.5
H10B—C10—H10C	109.5	H24B—C24—H24C	109.5
C9—C11—H11A	109.5	C23—C25—H25A	109.5
C9—C11—H11B	109.5	C23—C25—H25B	109.5
H11A—C11—H11B	109.5	H25A—C25—H25B	109.5
C9—C11—H11C	109.5	C23—C25—H25C	109.5
H11A—C11—H11C	109.5	H25A—C25—H25C	109.5
H11B—C11—H11C	109.5	H25B—C25—H25C	109.5
O3—C12—C3	124.16 (19)	O8—C26—C17	124.1 (2)
O3—C12—H12	117.9	O8—C26—H26	117.9
C3—C12—H12	117.9	C17—C26—H26	117.9
O4—C13—H13A	109.5	O9—C27—H27A	109.5
O4—C13—H13B	109.5	O9—C27—H27B	109.5
H13A—C13—H13B	109.5	H27A—C27—H27B	109.5
O4—C13—H13C	109.5	O9—C27—H27C	109.5
H13A—C13—H13C	109.5	H27A—C27—H27C	109.5
H13B—C13—H13C	109.5	H27B—C27—H27C	109.5
O5—C14—H14A	109.5	O10—C28—H28A	109.5
O5—C14—H14B	109.5	O10—C28—H28B	109.5
H14A—C14—H14B	109.5	H28A—C28—H28B	109.5
O5—C14—H14C	109.5	O10—C28—H28C	109.5
H14A—C14—H14C	109.5	H28A—C28—H28C	109.5
H14B—C14—H14C	109.5	H28B—C28—H28C	109.5
C6—C1—C2—O2	−179.03 (17)	C20—C15—C16—O7	179.48 (17)
C7—C1—C2—O2	−0.6 (3)	C21—C15—C16—O7	0.7 (3)
C6—C1—C2—C3	−1.2 (3)	C20—C15—C16—C17	2.3 (3)
C7—C1—C2—C3	177.19 (18)	C21—C15—C16—C17	−176.54 (19)
O2—C2—C3—C4	178.45 (17)	O7—C16—C17—C18	−178.50 (17)
C1—C2—C3—C4	0.6 (3)	C15—C16—C17—C18	−1.3 (3)
O2—C2—C3—C12	1.4 (3)	O7—C16—C17—C26	−0.4 (3)
C1—C2—C3—C12	−176.38 (19)	C15—C16—C17—C26	176.9 (2)
C13—O4—C4—C5	−2.2 (3)	C27—O9—C18—C19	1.1 (3)
C13—O4—C4—C3	177.79 (17)	C27—O9—C18—C17	−178.63 (17)
C2—C3—C4—O4	−178.95 (18)	C16—C17—C18—O9	178.69 (18)
C12—C3—C4—O4	−2.0 (3)	C26—C17—C18—O9	0.5 (3)
C2—C3—C4—C5	1.1 (3)	C16—C17—C18—C19	−1.1 (3)
C12—C3—C4—C5	178.1 (2)	C26—C17—C18—C19	−179.2 (2)
O4—C4—C5—C6	177.98 (18)	O9—C18—C19—C20	−177.46 (18)
C3—C4—C5—C6	−2.0 (3)	C17—C18—C19—C20	2.3 (3)
C14—O5—C6—C5	−2.1 (3)	C28—O10—C20—C19	1.9 (3)
C14—O5—C6—C1	177.01 (17)	C28—O10—C20—C15	−177.38 (17)
C4—C5—C6—O5	−179.51 (18)	C18—C19—C20—O10	179.49 (18)
C4—C5—C6—C1	1.4 (3)	C18—C19—C20—C15	−1.2 (3)
C2—C1—C6—O5	−178.94 (18)	C16—C15—C20—O10	178.30 (18)
C7—C1—C6—O5	2.7 (3)	C21—C15—C20—O10	−2.9 (3)
C2—C1—C6—C5	0.2 (3)	C16—C15—C20—C19	−1.0 (3)
C7—C1—C6—C5	−178.13 (19)	C21—C15—C20—C19	177.7 (2)
C2—C1—C7—O1	41.0 (3)	C16—C15—C21—O6	−41.3 (3)
C6—C1—C7—O1	−140.7 (2)	C20—C15—C21—O6	139.9 (2)
C2—C1—C7—C8	−133.5 (2)	C16—C15—C21—C22	134.1 (2)
C6—C1—C7—C8	44.7 (3)	C20—C15—C21—C22	−44.6 (3)
O1—C7—C8—C9	−10.0 (3)	O6—C21—C22—C23	10.5 (3)
C1—C7—C8—C9	164.52 (19)	C15—C21—C22—C23	−164.97 (18)
C7—C8—C9—C10	76.1 (3)	C21—C22—C23—C25	160.6 (2)
C7—C8—C9—C11	−160.9 (2)	C21—C22—C23—C24	−76.0 (3)
C4—C3—C12—O3	−178.41 (19)	C16—C17—C26—O8	0.9 (3)
C2—C3—C12—O3	−1.5 (3)	C18—C17—C26—O8	178.94 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3	0.84	1.79	2.549 (2)	149
O7—H7···O8	0.84	1.80	2.558 (2)	149
C8—H8A···O10^i	0.99	2.57	3.372 (3)	139
C14—H14C···O6^i	0.98	2.52	3.277 (3)	134
C22—H22B···O5	0.99	2.57	3.371 (3)	138
C28—H28A···O1	0.98	2.52	3.277 (3)	134
C12—H12···O8^ii	0.95	2.47	3.337 (3)	152
C27—H27B···O3^iii	0.98	2.52	3.492 (3)	170

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