Synthesis and crystallographic, spectroscopic and computational characterization of 3,3′,4,4′-substituted biphenyls: effects of OR substituents on the intra-ring torsion angle

Presented here are the synthesis, characterization and study (using single crystal X-ray diffraction, Raman scattering, quantum mechanics calculations) of the structures of a series of bi­phenyls substituted in positions 3, 3′, 4 and 4′ with a variety of R (R = methyl, acetyl, hexyl) groups connected to the bi­phenyl core through oxygen atoms. The molecular conformation, particularly the torsion angle between aromatic rings has been extensively studied both in the solid as well as in the liquid state. The results show that the compounds appearing as rigorously planar in the solid present instead a twisted conformation in the melt. The solid versus melt issue strongly suggests that the reasons for planarity are to be found in the packing restraints. A `rule of thumb' is suggested for the design of biphenyls with different molecular conformations, based on the selection of the OR substituent.

Computing details

Data collection: Bruker APEX2 for (I), (IV); CrysAlis PRO (Oxford Diffraction, 2009) for (II), (Vb). Cell refinement: Bruker SAINT for (I), (IV); CrysAlis PRO for (II), (Vb). Data reduction: Bruker SAINT for (I), (IV); CrysAlis PRO for (II), (Vb). For all structures, program(s) used to solve structure: SHELXS97 (Sheldrick 2008). Program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015) for (I), (IV); SHELXL2018/1 (Sheldrick, 2015) for (II), (Vb). For all structures, molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL2018, PLATON (Spek, 2009).

(I)

Crystal data

C36H58O4	F(000) = 612
Mr = 554.82	Dx = 1.109 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 22.486 (2) Å	Cell parameters from 8395 reflections
b = 8.8585 (9) Å	θ = 2.5–30.2°
c = 8.3874 (8) Å	µ = 0.07 mm^−1
β = 96.221 (3)°	T = 150 K
V = 1660.8 (3) Å^3	Fragment, colourless
Z = 2	0.22 × 0.16 × 0.12 mm

Data collection

Bruker APEX-II CCD diffractometer	3347 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.084
Absorption correction: multi-scan Bruker SAINT	θmax = 31.6°, θmin = 2.5°
Tmin = 0.90, Tmax = 0.96	h = −32→31
26569 measured reflections	k = −13→12
4907 independent reflections	l = −11→11

Refinement

Refinement on F^2	Primary atom site location: direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.069	H-atom parameters constrained
wR(F^2) = 0.143	w = 1/[σ^2(Fo^2) + (0.0362P)^2 + 0.4066P] where P = (Fo^2 + 2Fc^2)/3
S = 1.25	(Δ/σ)max < 0.001
4907 reflections	Δρmax = 0.34 e Å^−3
183 parameters	Δρmin = −0.25 e Å^−3
0 restraints

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.62808 (4)	0.53454 (12)	0.56014 (11)	0.0255 (3)
O2	0.66405 (4)	0.37790 (12)	0.81108 (11)	0.0271 (3)
C1	0.50070 (6)	0.59344 (17)	0.79638 (16)	0.0235 (3)
H1A	0.463691	0.646004	0.790133	0.028*
C2	0.53584 (6)	0.60466 (17)	0.66974 (16)	0.0233 (3)
H2A	0.522363	0.663905	0.578510	0.028*
C3	0.58986 (6)	0.53073 (16)	0.67563 (15)	0.0202 (3)
C4	0.60933 (6)	0.44426 (16)	0.81256 (16)	0.0206 (3)
C5	0.57385 (6)	0.43294 (16)	0.93620 (16)	0.0214 (3)
H5A	0.587275	0.373179	1.027070	0.026*
C6	0.51860 (6)	0.50686 (16)	0.93197 (15)	0.0191 (3)
C7	0.61685 (6)	0.64258 (17)	0.43261 (16)	0.0240 (3)
H7A	0.612290	0.745040	0.476845	0.029*
H7B	0.579765	0.616410	0.363526	0.029*
C8	0.67018 (7)	0.63693 (19)	0.33730 (16)	0.0268 (3)
H8A	0.664135	0.710594	0.248258	0.032*
H8B	0.672609	0.535146	0.289684	0.032*
C9	0.72899 (7)	0.67160 (19)	0.43771 (17)	0.0286 (3)
H9A	0.733554	0.602253	0.530794	0.034*
H9B	0.727322	0.775802	0.479661	0.034*
C10	0.78390 (7)	0.6569 (2)	0.34676 (18)	0.0305 (4)
H10A	0.780598	0.562808	0.282761	0.037*
H10B	0.784702	0.742704	0.271369	0.037*
C11	0.84186 (7)	0.6543 (2)	0.4562 (2)	0.0417 (4)
H11A	0.839488	0.573880	0.537245	0.050*
H11B	0.846450	0.751823	0.513919	0.050*
C12	0.89717 (8)	0.6275 (3)	0.3699 (2)	0.0491 (5)
H12A	0.932599	0.621468	0.448711	0.074*
H12B	0.901868	0.711043	0.295708	0.074*
H12C	0.892598	0.532577	0.309666	0.074*
C13	0.68889 (7)	0.30644 (19)	0.95673 (17)	0.0271 (3)
H13A	0.663522	0.220440	0.982681	0.032*
H13B	0.691264	0.379189	1.046794	0.032*
C14	0.75054 (7)	0.25185 (19)	0.93039 (18)	0.0297 (4)
H14A	0.747335	0.188915	0.832296	0.036*
H14B	0.765587	0.186434	1.021653	0.036*
C15	0.79601 (7)	0.3752 (2)	0.91342 (19)	0.0323 (4)
H15A	0.801348	0.435073	1.013610	0.039*
H15B	0.780646	0.443657	0.825147	0.039*
C16	0.85627 (7)	0.3125 (2)	0.8791 (2)	0.0383 (4)
H16A	0.869997	0.238658	0.963735	0.046*
H16B	0.850988	0.257684	0.775665	0.046*
C17	0.90438 (8)	0.4308 (3)	0.8712 (2)	0.0518 (5)
H17A	0.911482	0.481910	0.976531	0.062*
H17B	0.890033	0.507698	0.790418	0.062*
C18	0.96299 (9)	0.3659 (4)	0.8282 (3)	0.0780 (8)
H18A	0.991880	0.447818	0.820919	0.117*
H18B	0.956223	0.313838	0.724760	0.117*
H18C	0.978748	0.294190	0.911253	0.117*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0282 (6)	0.0292 (6)	0.0209 (5)	0.0066 (4)	0.0110 (4)	0.0056 (4)
O2	0.0227 (5)	0.0386 (7)	0.0214 (5)	0.0095 (5)	0.0079 (4)	0.0075 (4)
C1	0.0195 (7)	0.0287 (8)	0.0227 (7)	0.0030 (6)	0.0039 (5)	0.0013 (6)
C2	0.0237 (7)	0.0274 (8)	0.0188 (6)	0.0032 (6)	0.0025 (5)	0.0041 (6)
C3	0.0216 (7)	0.0217 (7)	0.0180 (6)	−0.0019 (6)	0.0055 (5)	−0.0015 (5)
C4	0.0188 (7)	0.0221 (7)	0.0212 (6)	0.0012 (5)	0.0034 (5)	−0.0011 (5)
C5	0.0225 (7)	0.0232 (7)	0.0187 (6)	−0.0002 (6)	0.0026 (5)	0.0024 (5)
C6	0.0186 (7)	0.0196 (7)	0.0193 (6)	−0.0026 (5)	0.0035 (5)	−0.0015 (5)
C7	0.0263 (7)	0.0289 (8)	0.0173 (6)	0.0037 (6)	0.0047 (5)	0.0035 (6)
C8	0.0281 (8)	0.0361 (9)	0.0171 (6)	0.0040 (7)	0.0065 (5)	0.0040 (6)
C9	0.0289 (8)	0.0361 (9)	0.0221 (7)	−0.0008 (7)	0.0082 (6)	0.0009 (6)
C10	0.0285 (8)	0.0401 (10)	0.0243 (7)	−0.0021 (7)	0.0097 (6)	0.0031 (7)
C11	0.0286 (9)	0.0635 (13)	0.0338 (9)	−0.0032 (8)	0.0078 (7)	0.0019 (8)
C12	0.0275 (9)	0.0708 (15)	0.0503 (11)	−0.0006 (9)	0.0104 (8)	0.0022 (10)
C13	0.0259 (8)	0.0332 (9)	0.0228 (7)	0.0056 (6)	0.0059 (6)	0.0078 (6)
C14	0.0270 (8)	0.0347 (9)	0.0278 (7)	0.0077 (7)	0.0043 (6)	0.0044 (6)
C15	0.0247 (8)	0.0411 (10)	0.0309 (8)	0.0030 (7)	0.0025 (6)	−0.0017 (7)
C16	0.0257 (8)	0.0562 (12)	0.0332 (8)	0.0049 (8)	0.0041 (7)	−0.0015 (8)
C17	0.0291 (9)	0.0788 (16)	0.0473 (11)	−0.0053 (10)	0.0032 (8)	0.0021 (10)
C18	0.0297 (11)	0.136 (3)	0.0700 (15)	−0.0082 (14)	0.0141 (10)	−0.0142 (16)

Geometric parameters (Å, º)

O1—C3	1.3633 (16)	C10—H10B	0.9900
O1—C7	1.4371 (16)	C11—C12	1.524 (2)
O2—C4	1.3649 (17)	C11—H11A	0.9900
O2—C13	1.4342 (17)	C11—H11B	0.9900
C1—C2	1.3945 (19)	C12—H12A	0.9801
C1—C6	1.3944 (19)	C12—H12B	0.9801
C1—H1A	0.9500	C12—H12C	0.9801
C2—C3	1.376 (2)	C13—C14	1.507 (2)
C2—H2A	0.9500	C13—H13A	0.9900
C3—C4	1.4101 (19)	C13—H13B	0.9900
C4—C5	1.3788 (19)	C14—C15	1.514 (2)
C5—C6	1.4013 (19)	C14—H14A	0.9900
C5—H5A	0.9500	C14—H14B	0.9900
C6—C6^i	1.491 (3)	C15—C16	1.520 (2)
C7—C8	1.5125 (19)	C15—H15A	0.9900
C7—H7A	0.9900	C15—H15B	0.9900
C7—H7B	0.9900	C16—C17	1.512 (3)
C8—C9	1.520 (2)	C16—H16A	0.9900
C8—H8A	0.9900	C16—H16B	0.9900
C8—H8B	0.9900	C17—C18	1.517 (3)
C9—C10	1.526 (2)	C17—H17A	0.9900
C9—H9A	0.9900	C17—H17B	0.9900
C9—H9B	0.9900	C18—H18A	0.9801
C10—C11	1.511 (2)	C18—H18B	0.9801
C10—H10A	0.9900	C18—H18C	0.9801
C3—O1—C7	118.15 (11)	C12—C11—H11A	108.7
C4—O2—C13	116.79 (10)	C10—C11—H11B	108.7
C2—C1—C6	121.54 (13)	C12—C11—H11B	108.7
C2—C1—H1A	119.2	H11A—C11—H11B	107.6
C6—C1—H1A	119.2	C11—C12—H12A	109.5
C3—C2—C1	120.64 (13)	C11—C12—H12B	109.5
C3—C2—H2A	119.7	H12A—C12—H12B	109.5
C1—C2—H2A	119.7	C11—C12—H12C	109.5
O1—C3—C2	125.78 (12)	H12A—C12—H12C	109.5
O1—C3—C4	115.36 (12)	H12B—C12—H12C	109.5
C2—C3—C4	118.86 (12)	O2—C13—C14	107.24 (11)
O2—C4—C5	124.83 (12)	O2—C13—H13A	110.3
O2—C4—C3	115.28 (11)	C14—C13—H13A	110.3
C5—C4—C3	119.88 (13)	O2—C13—H13B	110.3
C4—C5—C6	122.04 (13)	C14—C13—H13B	110.3
C4—C5—H5A	119.0	H13A—C13—H13B	108.5
C6—C5—H5A	119.0	C13—C14—C15	115.07 (14)
C1—C6—C5	117.03 (12)	C13—C14—H14A	108.5
C1—C6—C6^i	122.18 (15)	C15—C14—H14A	108.5
C5—C6—C6^i	120.79 (15)	C13—C14—H14B	108.5
O1—C7—C8	106.61 (11)	C15—C14—H14B	108.5
O1—C7—H7A	110.4	H14A—C14—H14B	107.5
C8—C7—H7A	110.4	C14—C15—C16	112.29 (15)
O1—C7—H7B	110.4	C14—C15—H15A	109.1
C8—C7—H7B	110.4	C16—C15—H15A	109.1
H7A—C7—H7B	108.6	C14—C15—H15B	109.1
C7—C8—C9	113.11 (11)	C16—C15—H15B	109.1
C7—C8—H8A	109.0	H15A—C15—H15B	107.9
C9—C8—H8A	109.0	C17—C16—C15	114.31 (17)
C7—C8—H8B	109.0	C17—C16—H16A	108.7
C9—C8—H8B	109.0	C15—C16—H16A	108.7
H8A—C8—H8B	107.8	C17—C16—H16B	108.7
C8—C9—C10	114.10 (12)	C15—C16—H16B	108.7
C8—C9—H9A	108.7	H16A—C16—H16B	107.6
C10—C9—H9A	108.7	C16—C17—C18	113.1 (2)
C8—C9—H9B	108.7	C16—C17—H17A	109.0
C10—C9—H9B	108.7	C18—C17—H17A	109.0
H9A—C9—H9B	107.6	C16—C17—H17B	109.0
C11—C10—C9	112.89 (12)	C18—C17—H17B	109.0
C11—C10—H10A	109.0	H17A—C17—H17B	107.8
C9—C10—H10A	109.0	C17—C18—H18A	109.5
C11—C10—H10B	109.0	C17—C18—H18B	109.5
C9—C10—H10B	109.0	H18A—C18—H18B	109.5
H10A—C10—H10B	107.8	C17—C18—H18C	109.5
C10—C11—C12	114.09 (14)	H18A—C18—H18C	109.5
C10—C11—H11A	108.7	H18B—C18—H18C	109.5

Symmetry code: (i) −x+1, −y+1, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13A···O1^ii	0.99	2.50	3.4645 (19)	163

Symmetry code: (ii) x, −y+1/2, z+1/2.

(II)

Crystal data

C28H38O6	Z = 1
Mr = 470.58	F(000) = 254
Triclinic, P1	Dx = 1.194 Mg m^−3
a = 8.554 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.6844 (17) Å	Cell parameters from 706 reflections
c = 9.810 (3) Å	θ = 3.7–26.2°
α = 100.26 (2)°	µ = 0.08 mm^−1
β = 109.10 (3)°	T = 294 K
γ = 100.53 (2)°	Fragment, colourless
V = 654.4 (3) Å^3	0.28 × 0.18 × 0.14 mm

Data collection

Oxford Diffraction Gemini CCD S Ultra diffractometer	1554 reflections with I > 2σ(I)
ω scans, thick slices	Rint = 0.146
Absorption correction: multi-scan CrysAlisPro, Oxford Diffraction (2009)	θmax = 29.0°, θmin = 3.6°
Tmin = 0.96, Tmax = 0.99	h = −11→11
4799 measured reflections	k = −8→11
2919 independent reflections	l = −13→11

Refinement

Refinement on F^2	Primary atom site location: direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.069	H-atom parameters constrained
wR(F^2) = 0.183	w = 1/[σ^2(Fo^2) + (0.0729P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.99	(Δ/σ)max < 0.001
2919 reflections	Δρmax = 0.28 e Å^−3
154 parameters	Δρmin = −0.30 e Å^−3
0 restraints

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.70994 (19)	0.57970 (17)	0.73363 (17)	0.0500 (5)
O2	0.5616 (2)	0.78025 (17)	0.86529 (17)	0.0519 (5)
O3	0.3331 (2)	0.5636 (2)	0.7495 (2)	0.0625 (5)
C1	0.6055 (3)	0.8298 (2)	0.4675 (3)	0.0493 (6)
H1A	0.615786	0.839868	0.375759	0.059*
C2	0.6652 (3)	0.7110 (3)	0.5291 (3)	0.0500 (6)
H2A	0.716344	0.643038	0.480093	0.060*
C3	0.6512 (3)	0.6900 (3)	0.6611 (3)	0.0441 (6)
C4	0.5718 (3)	0.7916 (3)	0.7265 (3)	0.0428 (6)
C5	0.5139 (3)	0.9086 (3)	0.6652 (3)	0.0453 (6)
H5A	0.459982	0.974163	0.713264	0.054*
C6	0.5308 (3)	0.9361 (2)	0.5333 (3)	0.0415 (5)
C7	0.7953 (3)	0.4775 (3)	0.6664 (3)	0.0479 (6)
H7A	0.895059	0.545241	0.655960	0.058*
H7B	0.715571	0.411779	0.565905	0.058*
C8	0.8530 (3)	0.3692 (3)	0.7643 (3)	0.0496 (6)
H8A	0.752030	0.303283	0.774489	0.060*
H8B	0.930365	0.436713	0.864875	0.060*
C9	0.9458 (3)	0.2565 (3)	0.7048 (3)	0.0489 (6)
H9A	0.870233	0.192240	0.602490	0.059*
H9B	1.049443	0.322470	0.698516	0.059*
C10	0.9983 (3)	0.1416 (3)	0.8006 (3)	0.0497 (6)
H10A	1.079320	0.206224	0.901028	0.060*
H10B	0.895489	0.081116	0.812170	0.060*
C11	1.0812 (3)	0.0213 (3)	0.7385 (3)	0.0601 (7)
H11A	1.002203	−0.040478	0.636505	0.072*
H11B	1.186836	0.081545	0.730988	0.072*
C12	1.1264 (3)	−0.0968 (3)	0.8322 (3)	0.0668 (8)
H12A	1.179948	−0.171670	0.785776	0.100*
H12B	1.207678	−0.036300	0.933906	0.100*
H12C	1.021008	−0.159660	0.838196	0.100*
C13	0.4325 (4)	0.6594 (3)	0.8625 (3)	0.0539 (7)
C14	0.4350 (4)	0.6716 (3)	1.0175 (3)	0.0681 (8)
H14A	0.342355	0.584833	1.015274	0.102*
H14B	0.545305	0.660803	1.081744	0.102*
H14C	0.418795	0.776913	1.056754	0.102*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0578 (10)	0.0510 (9)	0.0627 (12)	0.0233 (8)	0.0431 (9)	0.0178 (8)
O2	0.0647 (10)	0.0506 (9)	0.0563 (12)	0.0177 (8)	0.0406 (9)	0.0152 (8)
O3	0.0712 (12)	0.0572 (10)	0.0725 (14)	0.0099 (9)	0.0505 (11)	0.0109 (10)
C1	0.0570 (14)	0.0469 (12)	0.0641 (17)	0.0159 (11)	0.0450 (14)	0.0179 (12)
C2	0.0504 (13)	0.0472 (13)	0.0692 (18)	0.0149 (11)	0.0427 (13)	0.0142 (12)
C3	0.0494 (13)	0.0412 (11)	0.0546 (16)	0.0144 (10)	0.0324 (12)	0.0159 (11)
C4	0.0507 (13)	0.0440 (11)	0.0437 (15)	0.0134 (10)	0.0298 (12)	0.0111 (11)
C5	0.0471 (13)	0.0415 (11)	0.0593 (17)	0.0150 (10)	0.0351 (13)	0.0096 (11)
C6	0.0423 (12)	0.0414 (11)	0.0487 (15)	0.0074 (10)	0.0292 (12)	0.0106 (10)
C7	0.0472 (13)	0.0480 (12)	0.0640 (17)	0.0182 (11)	0.0385 (13)	0.0118 (12)
C8	0.0532 (14)	0.0512 (13)	0.0587 (17)	0.0202 (11)	0.0346 (13)	0.0153 (12)
C9	0.0481 (13)	0.0520 (13)	0.0633 (17)	0.0162 (11)	0.0386 (13)	0.0181 (12)
C10	0.0458 (12)	0.0564 (13)	0.0628 (17)	0.0201 (11)	0.0343 (13)	0.0199 (13)
C11	0.0578 (15)	0.0585 (14)	0.089 (2)	0.0257 (12)	0.0508 (15)	0.0255 (14)
C12	0.0590 (15)	0.0601 (15)	0.094 (2)	0.0286 (13)	0.0374 (16)	0.0203 (15)
C13	0.0710 (17)	0.0515 (14)	0.067 (2)	0.0322 (13)	0.0492 (16)	0.0218 (14)
C14	0.103 (2)	0.0689 (16)	0.071 (2)	0.0439 (16)	0.0617 (18)	0.0336 (15)

Geometric parameters (Å, º)

O1—C3	1.364 (3)	C8—H8A	0.9900
O1—C7	1.448 (2)	C8—H8B	0.9900
O2—C13	1.367 (3)	C9—C10	1.517 (3)
O2—C4	1.412 (2)	C9—H9A	0.9900
O3—C13	1.200 (3)	C9—H9B	0.9900
C1—C2	1.379 (3)	C10—C11	1.514 (3)
C1—C6	1.397 (3)	C10—H10A	0.9900
C1—H1A	0.9500	C10—H10B	0.9900
C2—C3	1.379 (3)	C11—C12	1.515 (3)
C2—H2A	0.9500	C11—H11A	0.9900
C3—C4	1.398 (3)	C11—H11B	0.9900
C4—C5	1.359 (3)	C12—H12A	0.9901
C5—C6	1.404 (3)	C12—H12B	0.9900
C5—H5A	0.9500	C12—H12C	0.9900
C6—C6^i	1.477 (4)	C13—C14	1.498 (3)
C7—C8	1.494 (3)	C14—H14A	0.9800
C7—H7A	0.9900	C14—H14B	0.9800
C7—H7B	0.9900	C14—H14C	0.9800
C8—C9	1.520 (3)
C3—O1—C7	116.94 (17)	C10—C9—H9A	108.9
C13—O2—C4	116.82 (19)	C8—C9—H9A	108.9
C2—C1—C6	123.3 (2)	C10—C9—H9B	108.9
C2—C1—H1A	118.4	C8—C9—H9B	108.9
C6—C1—H1A	118.4	H9A—C9—H9B	107.7
C3—C2—C1	120.6 (2)	C11—C10—C9	114.2 (2)
C3—C2—H2A	119.7	C11—C10—H10A	108.7
C1—C2—H2A	119.7	C9—C10—H10A	108.7
O1—C3—C2	125.46 (19)	C11—C10—H10B	108.7
O1—C3—C4	117.5 (2)	C9—C10—H10B	108.7
C2—C3—C4	117.1 (2)	H10A—C10—H10B	107.6
C5—C4—C3	121.8 (2)	C12—C11—C10	113.6 (2)
C5—C4—O2	118.71 (19)	C12—C11—H11A	108.9
C3—C4—O2	119.31 (19)	C10—C11—H11A	108.9
C4—C5—C6	122.4 (2)	C12—C11—H11B	108.9
C4—C5—H5A	118.8	C10—C11—H11B	108.9
C6—C5—H5A	118.8	H11A—C11—H11B	107.7
C1—C6—C5	114.7 (2)	C11—C12—H12A	109.5
C1—C6—C6^i	122.6 (3)	C11—C12—H12B	109.5
C5—C6—C6^i	122.7 (2)	H12A—C12—H12B	109.5
O1—C7—C8	108.50 (18)	C11—C12—H12C	109.4
O1—C7—H7A	110.0	H12A—C12—H12C	109.5
C8—C7—H7A	110.0	H12B—C12—H12C	109.5
O1—C7—H7B	110.0	O3—C13—O2	122.9 (2)
C8—C7—H7B	110.0	O3—C13—C14	127.5 (2)
H7A—C7—H7B	108.4	O2—C13—C14	109.5 (2)
C7—C8—C9	113.11 (19)	C13—C14—H14A	109.4
C7—C8—H8A	109.0	C13—C14—H14B	109.5
C9—C8—H8A	109.0	H14A—C14—H14B	109.5
C7—C8—H8B	109.0	C13—C14—H14C	109.5
C9—C8—H8B	109.0	H14A—C14—H14C	109.5
H8A—C8—H8B	107.8	H14B—C14—H14C	109.5
C10—C9—C8	113.2 (2)

Symmetry code: (i) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O3^ii	0.95	2.48	3.298 (3)	145

Symmetry code: (ii) −x+1, −y+1, −z+1.

(IV)

Crystal data

C18H18O6	F(000) = 696
Mr = 330.32	Dx = 1.398 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 11.304 (2) Å	Cell parameters from 6780 reflections
b = 10.064 (2) Å	θ = 3.1–29.8°
c = 14.496 (3) Å	µ = 0.11 mm^−1
β = 107.822 (10)°	T = 150 K
V = 1570.0 (6) Å^3	Fragment, colourless
Z = 4	0.28 × 0.18 × 0.10 mm

Data collection

Bruker APEX-II CCD diffractometer	7986 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.030
Absorption correction: multi-scan Bruker SAINT	θmax = 32.8°, θmin = 2.7°
Tmin = 0.90, Tmax = 0.96	h = −16→16
25745 measured reflections	k = −15→14
9921 independent reflections	l = −22→20

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.063	w = 1/[σ^2(Fo^2) + (0.0853P)^2 + 1.1735P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.179	(Δ/σ)max < 0.001
S = 1.03	Δρmax = 0.65 e Å^−3
9921 reflections	Δρmin = −0.40 e Å^−3
440 parameters	Absolute structure: Flack x determined using 3206 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
355 restraints	Absolute structure parameter: 0.0 (2)
Primary atom site location: direct methods

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1A	1.0052 (2)	0.8249 (3)	0.45851 (17)	0.0385 (7)
O2A	0.8332 (4)	0.9299 (4)	0.3706 (2)	0.0522 (8)
O3A	0.8249 (2)	0.6430 (2)	0.44977 (16)	0.0244 (5)
C1A	0.9678 (3)	0.8630 (5)	0.6991 (2)	0.0375 (9)
H1AA	1.003185	0.913795	0.756159	0.045*
C2A	1.0025 (4)	0.8909 (5)	0.6161 (3)	0.0391 (9)
H2AA	1.054370	0.964414	0.614062	0.047*
C3A	0.9582 (3)	0.8075 (4)	0.5375 (2)	0.0257 (6)
C4A	0.8692 (3)	0.7097 (3)	0.53479 (19)	0.0158 (5)
C5A	0.8277 (3)	0.6915 (3)	0.6143 (2)	0.0156 (5)
H5AA	0.761967	0.630856	0.610492	0.019*
C6A	0.8816 (2)	0.7615 (3)	0.70047 (18)	0.0148 (5)
C7A	0.9328 (4)	0.8848 (4)	0.3781 (3)	0.0379 (7)
C8A	0.9925 (5)	0.8791 (6)	0.2989 (3)	0.0566 (14)
H8AA	0.996457	0.968838	0.273608	0.085*
H8AB	0.943345	0.821753	0.246488	0.085*
H8AC	1.076818	0.843175	0.324737	0.085*
C9A	0.7317 (4)	0.5446 (4)	0.4460 (3)	0.0330 (8)
H9AA	0.696987	0.512521	0.379271	0.049*
H9AB	0.665366	0.584041	0.467508	0.049*
H9AC	0.769065	0.470164	0.488469	0.049*
O1A'	0.71824 (19)	0.6785 (2)	1.02983 (14)	0.0172 (4)
O2A'	0.9005 (2)	0.5937 (3)	1.12222 (15)	0.0271 (5)
O3A'	0.8857 (2)	0.8711 (2)	1.03354 (14)	0.0214 (4)
C1A'	0.7579 (2)	0.6341 (3)	0.78943 (18)	0.0143 (5)
H1AB	0.728312	0.577401	0.734787	0.017*
C2A'	0.7192 (3)	0.6138 (3)	0.87088 (19)	0.0166 (5)
H2AB	0.661205	0.545525	0.870872	0.020*
C3A'	0.7653 (2)	0.6930 (3)	0.95128 (18)	0.0129 (4)
C4A'	0.8476 (2)	0.7969 (2)	0.95118 (18)	0.0115 (4)
C5A'	0.8852 (2)	0.8172 (2)	0.86969 (17)	0.0116 (4)
H5AB	0.942452	0.886383	0.869869	0.014*
C6A'	0.8405 (2)	0.7377 (2)	0.78759 (16)	0.0103 (4)
C7A'	0.7966 (3)	0.6300 (3)	1.1138 (2)	0.0190 (5)
C8A'	0.7327 (4)	0.6280 (4)	1.1897 (2)	0.0312 (7)
H8AD	0.783324	0.578332	1.246133	0.047*
H8AE	0.651454	0.585084	1.163808	0.047*
H8AF	0.721435	0.719299	1.208961	0.047*
C9A'	0.9809 (3)	0.9653 (3)	1.03937 (19)	0.0213 (5)
H9AD	1.009331	1.002815	1.104861	0.032*
H9AE	0.948578	1.036560	0.992340	0.032*
H9AF	1.050701	0.921545	1.024932	0.032*
O1B	0.4505 (4)	0.3141 (5)	0.5243 (2)	0.0737 (14)
O2B	0.6190 (2)	0.4214 (3)	0.61168 (17)	0.0299 (5)
O3B	0.6257 (4)	0.1488 (4)	0.5262 (3)	0.0656 (10)
C1B	0.4834 (3)	0.3818 (4)	0.2824 (3)	0.0344 (7)
H1BA	0.451078	0.439087	0.228446	0.041*
C2B	0.4429 (4)	0.3932 (6)	0.3643 (3)	0.0458 (10)
H2BA	0.380953	0.456329	0.365516	0.055*
C3B	0.4939 (4)	0.3117 (5)	0.4432 (3)	0.0447 (8)
C4B	0.5827 (5)	0.2226 (5)	0.4456 (3)	0.0468 (9)
C5B	0.6210 (5)	0.2085 (4)	0.3616 (3)	0.0414 (9)
H5BA	0.682291	0.144253	0.360996	0.050*
C6B	0.5707 (3)	0.2865 (3)	0.2807 (2)	0.0273 (6)
C7B	0.5261 (4)	0.3632 (5)	0.6074 (3)	0.0409 (9)
C8B	0.4681 (4)	0.3427 (7)	0.6864 (3)	0.0566 (15)
H8BA	0.510761	0.398194	0.742247	0.085*
H8BB	0.475491	0.249044	0.705851	0.085*
H8BC	0.380085	0.367509	0.662822	0.085*
C9B	0.7420 (8)	0.0805 (8)	0.5416 (6)	0.094 (2)
H9BA	0.788160	0.079461	0.610928	0.141*
H9BB	0.728376	−0.010946	0.517456	0.141*
H9BC	0.789922	0.128967	0.506470	0.141*
O1B'	0.7652 (2)	0.2704 (2)	−0.03688 (16)	0.0282 (5)
O2B'	0.6418 (4)	0.1059 (3)	−0.1127 (2)	0.0526 (9)
O3B'	0.5377 (2)	0.3698 (2)	−0.06364 (14)	0.0222 (4)
C1B'	0.7365 (3)	0.2234 (4)	0.2059 (2)	0.0307 (6)
H1BB	0.785264	0.191667	0.267520	0.037*
C2B'	0.7831 (3)	0.2164 (4)	0.1278 (2)	0.0317 (7)
H2BB	0.862009	0.177582	0.134938	0.038*
C3B'	0.7121 (3)	0.2672 (3)	0.0391 (2)	0.0225 (5)
C4B'	0.5955 (3)	0.3233 (3)	0.0264 (2)	0.0181 (5)
C5B'	0.5499 (3)	0.3284 (3)	0.1049 (2)	0.0191 (5)
H5BB	0.471035	0.367615	0.097367	0.023*
C6B'	0.6184 (3)	0.2766 (3)	0.1950 (2)	0.0222 (5)
C7B'	0.7195 (4)	0.1861 (4)	−0.1104 (3)	0.0320 (6)
C8B'	0.7793 (5)	0.2072 (5)	−0.1882 (3)	0.0483 (11)
H8BD	0.742120	0.146784	−0.242384	0.072*
H8BE	0.868631	0.189263	−0.162179	0.072*
H8BF	0.766436	0.299305	−0.211040	0.072*
C9B'	0.4328 (3)	0.4554 (3)	−0.0724 (2)	0.0289 (7)
H9BD	0.403254	0.491418	−0.138302	0.043*
H9BE	0.457756	0.528543	−0.025847	0.043*
H9BF	0.366000	0.404431	−0.058993	0.043*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1A	0.0292 (12)	0.073 (2)	0.0197 (10)	−0.0189 (12)	0.0173 (9)	−0.0055 (11)
O2A	0.0733 (19)	0.0501 (17)	0.0391 (16)	−0.0001 (16)	0.0258 (15)	0.0126 (14)
O3A	0.0380 (12)	0.0247 (10)	0.0166 (9)	−0.0080 (9)	0.0172 (9)	−0.0063 (8)
C1A	0.0357 (17)	0.058 (2)	0.0219 (14)	−0.0286 (17)	0.0134 (13)	−0.0123 (15)
C2A	0.0377 (18)	0.059 (2)	0.0251 (14)	−0.0262 (17)	0.0162 (14)	−0.0102 (14)
C3A	0.0218 (13)	0.0430 (17)	0.0167 (12)	−0.0097 (12)	0.0126 (10)	−0.0026 (11)
C4A	0.0166 (11)	0.0203 (12)	0.0113 (10)	0.0018 (9)	0.0053 (8)	−0.0007 (8)
C5A	0.0187 (11)	0.0150 (11)	0.0146 (10)	−0.0023 (9)	0.0073 (9)	0.0009 (8)
C6A	0.0108 (10)	0.0253 (12)	0.0085 (9)	−0.0003 (9)	0.0033 (8)	0.0005 (8)
C7A	0.0536 (17)	0.0408 (19)	0.0225 (13)	−0.0267 (14)	0.0162 (13)	−0.0038 (13)
C8A	0.069 (3)	0.082 (4)	0.0286 (18)	−0.040 (3)	0.0292 (19)	−0.009 (2)
C9A	0.050 (2)	0.0270 (15)	0.0301 (16)	−0.0158 (14)	0.0240 (16)	−0.0157 (13)
O1A'	0.0200 (9)	0.0238 (9)	0.0105 (8)	−0.0015 (7)	0.0085 (7)	0.0006 (7)
O2A'	0.0317 (11)	0.0374 (12)	0.0122 (9)	0.0088 (10)	0.0068 (8)	0.0058 (9)
O3A'	0.0347 (11)	0.0225 (9)	0.0122 (8)	−0.0063 (8)	0.0151 (8)	−0.0060 (7)
C1A'	0.0149 (11)	0.0184 (11)	0.0096 (10)	−0.0011 (9)	0.0039 (8)	0.0016 (9)
C2A'	0.0162 (11)	0.0230 (12)	0.0113 (10)	−0.0038 (10)	0.0054 (8)	0.0016 (9)
C3A'	0.0140 (10)	0.0166 (10)	0.0089 (9)	0.0010 (8)	0.0050 (8)	0.0028 (8)
C4A'	0.0149 (10)	0.0110 (9)	0.0096 (9)	0.0034 (8)	0.0050 (8)	0.0006 (7)
C5A'	0.0155 (10)	0.0119 (9)	0.0084 (9)	0.0015 (8)	0.0053 (8)	0.0013 (7)
C6A'	0.0099 (9)	0.0129 (9)	0.0078 (9)	0.0021 (7)	0.0020 (7)	0.0017 (7)
C7A'	0.0292 (12)	0.0203 (12)	0.0095 (10)	−0.0009 (10)	0.0086 (9)	0.0030 (9)
C8A'	0.0448 (19)	0.0382 (18)	0.0170 (13)	−0.0014 (15)	0.0190 (13)	0.0025 (12)
C9A'	0.0295 (14)	0.0263 (13)	0.0102 (10)	−0.0053 (11)	0.0094 (10)	−0.0034 (10)
O1B	0.064 (2)	0.129 (4)	0.0337 (15)	−0.053 (2)	0.0245 (14)	−0.0229 (19)
O2B	0.0371 (12)	0.0355 (12)	0.0205 (11)	−0.0113 (10)	0.0137 (10)	−0.0084 (9)
O3B	0.104 (3)	0.051 (2)	0.0499 (19)	−0.0019 (19)	0.036 (2)	0.0040 (15)
C1B	0.0298 (16)	0.052 (2)	0.0228 (14)	−0.0043 (14)	0.0107 (12)	−0.0032 (14)
C2B	0.0358 (19)	0.077 (3)	0.0292 (16)	−0.0054 (18)	0.0172 (14)	−0.0074 (16)
C3B	0.047 (2)	0.061 (2)	0.0283 (15)	−0.0242 (15)	0.0162 (14)	−0.0101 (15)
C4B	0.061 (2)	0.044 (2)	0.0372 (17)	−0.0223 (16)	0.0186 (17)	−0.0050 (15)
C5B	0.062 (2)	0.0302 (17)	0.0354 (17)	−0.0059 (16)	0.0199 (17)	−0.0009 (13)
C6B	0.0358 (15)	0.0262 (14)	0.0217 (12)	−0.0141 (11)	0.0117 (11)	−0.0100 (10)
C7B	0.0372 (16)	0.062 (2)	0.0286 (15)	−0.0162 (17)	0.0173 (13)	−0.0120 (16)
C8B	0.037 (2)	0.111 (5)	0.0258 (17)	−0.024 (3)	0.0158 (15)	−0.014 (2)
C9B	0.136 (5)	0.079 (5)	0.080 (5)	0.036 (4)	0.053 (4)	0.034 (4)
O1B'	0.0371 (12)	0.0339 (11)	0.0223 (10)	0.0046 (10)	0.0220 (9)	0.0027 (8)
O2B'	0.082 (2)	0.0435 (15)	0.0485 (18)	−0.0115 (15)	0.0439 (17)	−0.0187 (14)
O3B'	0.0364 (11)	0.0215 (9)	0.0144 (8)	0.0028 (8)	0.0161 (8)	−0.0008 (7)
C1B'	0.0396 (16)	0.0359 (16)	0.0190 (12)	0.0035 (13)	0.0125 (12)	−0.0006 (12)
C2B'	0.0353 (16)	0.0416 (18)	0.0224 (13)	0.0079 (14)	0.0152 (12)	0.0010 (12)
C3B'	0.0329 (13)	0.0211 (12)	0.0203 (11)	0.0012 (10)	0.0183 (10)	−0.0001 (10)
C4B'	0.0289 (12)	0.0145 (10)	0.0163 (10)	−0.0039 (9)	0.0149 (9)	−0.0016 (8)
C5B'	0.0298 (13)	0.0168 (11)	0.0150 (11)	−0.0057 (10)	0.0132 (10)	−0.0029 (9)
C6B'	0.0342 (13)	0.0170 (11)	0.0190 (11)	−0.0081 (10)	0.0133 (10)	−0.0033 (9)
C7B'	0.0481 (18)	0.0303 (14)	0.0242 (13)	0.0133 (12)	0.0209 (13)	0.0037 (11)
C8B'	0.067 (3)	0.063 (3)	0.0269 (17)	0.028 (2)	0.0314 (18)	0.0138 (17)
C9B'	0.0425 (17)	0.0292 (15)	0.0236 (14)	0.0067 (12)	0.0228 (13)	0.0005 (11)

Geometric parameters (Å, º)

O1A—C7A	1.345 (5)	O1B—C7B	1.340 (5)
O1A—C3A	1.412 (3)	O1B—C3B	1.405 (5)
O2A—C7A	1.187 (6)	O2B—C7B	1.188 (5)
O3A—C4A	1.357 (3)	O3B—C4B	1.344 (6)
O3A—C9A	1.434 (4)	O3B—C9B	1.440 (9)
C1A—C2A	1.404 (5)	C1B—C6B	1.381 (5)
C1A—C6A	1.415 (4)	C1B—C2B	1.402 (5)
C1A—H1AA	0.9500	C1B—H1BA	0.9500
C2A—C3A	1.380 (5)	C2B—C3B	1.382 (7)
C2A—H2AA	0.9500	C2B—H2BA	0.9500
C3A—C4A	1.400 (4)	C3B—C4B	1.338 (7)
C4A—C5A	1.384 (4)	C4B—C5B	1.418 (6)
C5A—C6A	1.400 (4)	C5B—C6B	1.381 (5)
C5A—H5AA	0.9500	C5B—H5BA	0.9500
C6A—C6A'	1.493 (3)	C6B—C6B'	1.502 (4)
C7A—C8A	1.502 (5)	C7B—C8B	1.497 (5)
C8A—H8AA	0.9801	C8B—H8BA	0.9801
C8A—H8AB	0.9801	C8B—H8BB	0.9801
C8A—H8AC	0.9801	C8B—H8BC	0.9801
C9A—H9AA	0.9801	C9B—H9BA	0.9800
C9A—H9AB	0.9801	C9B—H9BB	0.9800
C9A—H9AC	0.9801	C9B—H9BC	0.9800
O1A'—C7A'	1.358 (3)	O1B'—C7B'	1.337 (4)
O1A'—C3A'	1.404 (3)	O1B'—C3B'	1.407 (3)
O2A'—C7A'	1.200 (4)	O2B'—C7B'	1.186 (5)
O3A'—C4A'	1.362 (3)	O3B'—C4B'	1.351 (3)
O3A'—C9A'	1.417 (4)	O3B'—C9B'	1.439 (4)
C1A'—C2A'	1.394 (4)	C1B'—C2B'	1.389 (4)
C1A'—C6A'	1.406 (4)	C1B'—C6B'	1.401 (5)
C1A'—H1AB	0.9500	C1B'—H1BB	0.9500
C2A'—C3A'	1.376 (4)	C2B'—C3B'	1.388 (4)
C2A'—H2AB	0.9500	C2B'—H2BB	0.9500
C3A'—C4A'	1.400 (4)	C3B'—C4B'	1.393 (4)
C4A'—C5A'	1.388 (3)	C4B'—C5B'	1.387 (3)
C5A'—C6A'	1.394 (3)	C5B'—C6B'	1.400 (4)
C5A'—H5AB	0.9500	C5B'—H5BB	0.9500
C7A'—C8A'	1.489 (4)	C7B'—C8B'	1.497 (5)
C8A'—H8AD	0.9801	C8B'—H8BD	0.9801
C8A'—H8AE	0.9801	C8B'—H8BE	0.9801
C8A'—H8AF	0.9801	C8B'—H8BF	0.9801
C9A'—H9AD	0.9801	C9B'—H9BD	0.9801
C9A'—H9AE	0.9801	C9B'—H9BE	0.9801
C9A'—H9AF	0.9801	C9B'—H9BF	0.9801
C7A—O1A—C3A	118.5 (3)	C7B—O1B—C3B	118.0 (3)
C4A—O3A—C9A	116.0 (2)	C4B—O3B—C9B	118.0 (4)
C2A—C1A—C6A	122.0 (3)	C6B—C1B—C2B	119.5 (4)
C2A—C1A—H1AA	119.0	C6B—C1B—H1BA	120.3
C6A—C1A—H1AA	119.0	C2B—C1B—H1BA	120.3
C3A—C2A—C1A	117.4 (3)	C3B—C2B—C1B	119.4 (4)
C3A—C2A—H2AA	121.3	C3B—C2B—H2BA	120.3
C1A—C2A—H2AA	121.3	C1B—C2B—H2BA	120.3
C2A—C3A—C4A	121.8 (3)	C4B—C3B—C2B	122.5 (4)
C2A—C3A—O1A	117.6 (3)	C4B—C3B—O1B	116.2 (5)
C4A—C3A—O1A	120.7 (3)	C2B—C3B—O1B	121.2 (5)
O3A—C4A—C5A	124.5 (3)	C3B—C4B—O3B	117.5 (4)
O3A—C4A—C3A	115.8 (2)	C3B—C4B—C5B	117.9 (4)
C5A—C4A—C3A	119.6 (3)	O3B—C4B—C5B	124.5 (5)
C4A—C5A—C6A	120.7 (2)	C6B—C5B—C4B	121.1 (4)
C4A—C5A—H5AA	119.7	C6B—C5B—H5BA	119.4
C6A—C5A—H5AA	119.7	C4B—C5B—H5BA	119.4
C5A—C6A—C1A	117.7 (2)	C1B—C6B—C5B	119.4 (3)
C5A—C6A—C6A'	120.7 (2)	C1B—C6B—C6B'	120.0 (3)
C1A—C6A—C6A'	121.4 (2)	C5B—C6B—C6B'	120.4 (3)
O2A—C7A—O1A	124.1 (3)	O2B—C7B—O1B	122.6 (3)
O2A—C7A—C8A	125.4 (4)	O2B—C7B—C8B	128.0 (4)
O1A—C7A—C8A	110.4 (4)	O1B—C7B—C8B	109.3 (3)
C7A—C8A—H8AA	109.5	C7B—C8B—H8BA	109.5
C7A—C8A—H8AB	109.5	C7B—C8B—H8BB	109.5
H8AA—C8A—H8AB	109.5	H8BA—C8B—H8BB	109.5
C7A—C8A—H8AC	109.5	C7B—C8B—H8BC	109.5
H8AA—C8A—H8AC	109.5	H8BA—C8B—H8BC	109.5
H8AB—C8A—H8AC	109.5	H8BB—C8B—H8BC	109.5
O3A—C9A—H9AA	109.5	O3B—C9B—H9BA	109.8
O3A—C9A—H9AB	109.5	O3B—C9B—H9BB	110.9
H9AA—C9A—H9AB	109.5	H9BA—C9B—H9BB	109.4
O3A—C9A—H9AC	109.5	O3B—C9B—H9BC	107.8
H9AA—C9A—H9AC	109.5	H9BA—C9B—H9BC	109.4
H9AB—C9A—H9AC	109.5	H9BB—C9B—H9BC	109.4
C7A'—O1A'—C3A'	117.3 (2)	C7B'—O1B'—C3B'	117.2 (3)
C4A'—O3A'—C9A'	116.7 (2)	C4B'—O3B'—C9B'	115.7 (2)
C2A'—C1A'—C6A'	120.5 (2)	C2B'—C1B'—C6B'	120.9 (3)
C2A'—C1A'—H1AB	119.8	C2B'—C1B'—H1BB	119.6
C6A'—C1A'—H1AB	119.8	C6B'—C1B'—H1BB	119.6
C3A'—C2A'—C1A'	119.8 (2)	C3B'—C2B'—C1B'	118.7 (3)
C3A'—C2A'—H2AB	120.1	C3B'—C2B'—H2BB	120.7
C1A'—C2A'—H2AB	120.1	C1B'—C2B'—H2BB	120.7
C2A'—C3A'—C4A'	120.8 (2)	C2B'—C3B'—C4B'	121.8 (3)
C2A'—C3A'—O1A'	119.2 (2)	C2B'—C3B'—O1B'	118.0 (3)
C4A'—C3A'—O1A'	119.7 (2)	C4B'—C3B'—O1B'	120.0 (3)
O3A'—C4A'—C5A'	124.6 (2)	O3B'—C4B'—C5B'	126.0 (3)
O3A'—C4A'—C3A'	116.2 (2)	O3B'—C4B'—C3B'	115.3 (2)
C5A'—C4A'—C3A'	119.2 (2)	C5B'—C4B'—C3B'	118.7 (3)
C4A'—C5A'—C6A'	121.1 (2)	C4B'—C5B'—C6B'	120.9 (3)
C4A'—C5A'—H5AB	119.4	C4B'—C5B'—H5BB	119.6
C6A'—C5A'—H5AB	119.4	C6B'—C5B'—H5BB	119.6
C5A'—C6A'—C1A'	118.6 (2)	C5B'—C6B'—C1B'	118.9 (3)
C5A'—C6A'—C6A	120.3 (2)	C5B'—C6B'—C6B	120.7 (3)
C1A'—C6A'—C6A	121.0 (2)	C1B'—C6B'—C6B	120.2 (3)
O2A'—C7A'—O1A'	123.4 (3)	O2B'—C7B'—O1B'	123.8 (3)
O2A'—C7A'—C8A'	126.9 (3)	O2B'—C7B'—C8B'	125.2 (4)
O1A'—C7A'—C8A'	109.6 (3)	O1B'—C7B'—C8B'	110.9 (4)
C7A'—C8A'—H8AD	109.5	C7B'—C8B'—H8BD	109.5
C7A'—C8A'—H8AE	109.5	C7B'—C8B'—H8BE	109.5
H8AD—C8A'—H8AE	109.5	H8BD—C8B'—H8BE	109.5
C7A'—C8A'—H8AF	109.5	C7B'—C8B'—H8BF	109.5
H8AD—C8A'—H8AF	109.5	H8BD—C8B'—H8BF	109.5
H8AE—C8A'—H8AF	109.5	H8BE—C8B'—H8BF	109.5
O3A'—C9A'—H9AD	109.5	O3B'—C9B'—H9BD	109.5
O3A'—C9A'—H9AE	109.5	O3B'—C9B'—H9BE	109.5
H9AD—C9A'—H9AE	109.5	H9BD—C9B'—H9BE	109.5
O3A'—C9A'—H9AF	109.5	O3B'—C9B'—H9BF	109.5
H9AD—C9A'—H9AF	109.5	H9BD—C9B'—H9BF	109.5
H9AE—C9A'—H9AF	109.5	H9BE—C9B'—H9BF	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2A—H2AA···O3A^i	0.95	2.59	3.506 (5)	162
C5A—H5AA···O2B	0.95	2.66	3.592 (4)	167
C2A′—H2AB···O3B′^ii	0.95	2.61	3.512 (4)	160
C9A′—H9AF···O1B′^i	0.98	2.54	3.485 (4)	162
C2B—H2BA···O3B^iii	0.95	2.51	3.240 (6)	134
C8B—H8BC···O2A^iv	0.98	2.39	3.366 (6)	172
C9B—H9BB···O1B^iv	0.98	2.61	3.401 (11)	138
C9B′—H9BF···O1A′^iv	0.98	2.55	3.421 (4)	148

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

(Vb)

Crystal data

C16H18O4	F(000) = 584
Mr = 274.30	Dx = 1.264 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.1000 (7) Å	Cell parameters from 2116 reflections
b = 7.6709 (3) Å	θ = 4.1–26.7°
c = 15.2881 (7) Å	µ = 0.09 mm^−1
β = 110.181 (5)°	T = 294 K
V = 1441.97 (12) Å^3	Fragment, colourless
Z = 4	0.48 × 0.18 × 0.14 mm

Data collection

Oxford Diffraction Gemini CCD S Ultra diffractometer	2334 reflections with I > 2σ(I)
ω scans, thick slices	Rint = 0.055
Absorption correction: multi-scan CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	θmax = 29.5°, θmin = 3.8°
Tmin = 0.92, Tmax = 0.99	h = −17→17
42671 measured reflections	k = −10→10
3773 independent reflections	l = −20→19

Refinement

Refinement on F^2	Primary atom site location: direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.050	H-atom parameters constrained
wR(F^2) = 0.132	w = 1/[σ^2(Fo^2) + (0.0543P)^2 + 0.2499P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.001
3773 reflections	Δρmax = 0.17 e Å^−3
185 parameters	Δρmin = −0.17 e Å^−3
0 restraints

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	1.08189 (8)	0.39901 (16)	0.36020 (8)	0.0599 (3)
O2	0.96587 (9)	0.26155 (18)	0.44747 (8)	0.0683 (4)
O1'	0.28686 (8)	0.38500 (17)	0.07344 (9)	0.0679 (4)
O2'	0.38943 (9)	0.65661 (15)	0.05161 (8)	0.0582 (3)
C1	0.80803 (12)	0.4743 (2)	0.18792 (10)	0.0483 (4)
H1A	0.774002	0.524808	0.128166	0.058*
C2	0.92069 (12)	0.4789 (2)	0.22853 (11)	0.0495 (4)
H2A	0.962711	0.532951	0.196415	0.059*
C3	0.97181 (11)	0.40596 (19)	0.31468 (10)	0.0460 (4)
C4	0.90877 (12)	0.3293 (2)	0.36221 (10)	0.0469 (4)
C5	0.79721 (11)	0.3254 (2)	0.32164 (10)	0.0444 (3)
H5A	0.755064	0.273051	0.354161	0.053*
C6	0.74482 (11)	0.39729 (19)	0.23318 (9)	0.0421 (3)
C7	1.14949 (14)	0.4649 (3)	0.31293 (15)	0.0749 (6)
H7A	1.225908	0.446381	0.351206	0.112*
H7B	1.135931	0.589989	0.301545	0.112*
H7C	1.133435	0.404089	0.253308	0.112*
C8	0.90805 (15)	0.2138 (3)	0.50611 (12)	0.0756 (6)
H8A	0.959412	0.179015	0.567120	0.113*
H8B	0.859641	0.115859	0.478316	0.113*
H8C	0.864814	0.313100	0.513742	0.113*
C1'	0.56716 (12)	0.24702 (19)	0.20493 (10)	0.0471 (4)
H1A'	0.605421	0.151710	0.241286	0.057*
C2'	0.45432 (12)	0.2410 (2)	0.16667 (10)	0.0498 (4)
H2A'	0.416481	0.141748	0.176797	0.060*
C3'	0.39705 (12)	0.3781 (2)	0.11418 (10)	0.0472 (4)
C4'	0.45376 (12)	0.52447 (19)	0.10073 (9)	0.0440 (3)
C5'	0.56553 (12)	0.52812 (19)	0.13789 (9)	0.0432 (3)
H5A'	0.603399	0.626952	0.127304	0.052*
C6'	0.62470 (11)	0.38892 (18)	0.19108 (9)	0.0415 (3)
C7'	0.22693 (15)	0.2363 (3)	0.08319 (17)	0.0845 (7)
H7A'	0.149758	0.253081	0.046717	0.127*
H7B'	0.235743	0.220460	0.149015	0.127*
H7C'	0.253983	0.132739	0.060555	0.127*
C8'	0.44236 (15)	0.8102 (2)	0.03905 (14)	0.0682 (5)
H8A'	0.388087	0.894378	0.002435	0.102*
H8B'	0.492443	0.782116	0.006013	0.102*
H8C'	0.483249	0.860776	0.099983	0.102*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0405 (6)	0.0703 (8)	0.0650 (7)	−0.0062 (5)	0.0133 (5)	0.0046 (6)
O2	0.0438 (6)	0.1016 (10)	0.0524 (6)	0.0013 (6)	0.0074 (5)	0.0265 (6)
O1'	0.0390 (6)	0.0774 (8)	0.0770 (8)	0.0020 (6)	0.0071 (6)	0.0186 (6)
O2'	0.0542 (7)	0.0550 (7)	0.0608 (7)	0.0140 (5)	0.0140 (5)	0.0149 (5)
C1	0.0518 (9)	0.0499 (9)	0.0414 (8)	0.0026 (7)	0.0137 (7)	0.0053 (6)
C2	0.0506 (9)	0.0503 (9)	0.0504 (8)	−0.0057 (7)	0.0208 (7)	0.0015 (7)
C3	0.0384 (8)	0.0467 (8)	0.0507 (8)	−0.0019 (6)	0.0125 (6)	−0.0029 (6)
C4	0.0427 (8)	0.0522 (9)	0.0417 (8)	0.0023 (6)	0.0094 (6)	0.0034 (6)
C5	0.0413 (8)	0.0514 (8)	0.0411 (8)	0.0015 (6)	0.0149 (6)	0.0030 (6)
C6	0.0417 (8)	0.0435 (8)	0.0386 (7)	0.0031 (6)	0.0107 (6)	−0.0011 (6)
C7	0.0509 (10)	0.0881 (14)	0.0892 (14)	−0.0103 (9)	0.0288 (10)	0.0068 (11)
C8	0.0613 (11)	0.1097 (16)	0.0494 (10)	−0.0029 (11)	0.0111 (9)	0.0236 (10)
C1'	0.0476 (9)	0.0471 (8)	0.0418 (7)	0.0052 (6)	0.0093 (7)	0.0083 (6)
C2'	0.0485 (9)	0.0522 (9)	0.0464 (8)	−0.0028 (7)	0.0136 (7)	0.0067 (7)
C3'	0.0403 (8)	0.0576 (9)	0.0403 (7)	0.0037 (7)	0.0096 (6)	0.0021 (7)
C4'	0.0458 (8)	0.0474 (8)	0.0365 (7)	0.0090 (6)	0.0115 (6)	0.0031 (6)
C5'	0.0470 (8)	0.0423 (7)	0.0398 (7)	0.0017 (6)	0.0144 (6)	0.0009 (6)
C6'	0.0421 (8)	0.0461 (8)	0.0344 (7)	0.0035 (6)	0.0109 (6)	−0.0008 (6)
C7'	0.0482 (10)	0.0937 (16)	0.1006 (16)	−0.0128 (10)	0.0118 (10)	0.0129 (12)
C8'	0.0758 (12)	0.0496 (10)	0.0760 (12)	0.0140 (9)	0.0223 (10)	0.0168 (9)

Geometric parameters (Å, º)

O1—C3	1.3689 (17)	C7—H7C	0.9801
O1—C7	1.416 (2)	C8—H8A	0.9801
O2—C4	1.3625 (17)	C8—H8B	0.9801
O2—C8	1.407 (2)	C8—H8C	0.9801
O1'—C3'	1.3616 (17)	C1'—C6'	1.381 (2)
O1'—C7'	1.422 (2)	C1'—C2'	1.390 (2)
O2'—C4'	1.3656 (17)	C1'—H1A'	0.9500
O2'—C8'	1.414 (2)	C2'—C3'	1.377 (2)
C1—C6	1.381 (2)	C2'—H2A'	0.9500
C1—C2	1.390 (2)	C3'—C4'	1.400 (2)
C1—H1A	0.9500	C4'—C5'	1.376 (2)
C2—C3	1.374 (2)	C5'—C6'	1.4026 (19)
C2—H2A	0.9500	C5'—H5A'	0.9500
C3—C4	1.403 (2)	C7'—H7A'	0.9801
C4—C5	1.3770 (19)	C7'—H7B'	0.9801
C5—C6	1.4014 (19)	C7'—H7C'	0.9801
C5—H5A	0.9500	C8'—H8A'	0.9801
C6—C6'	1.4818 (19)	C8'—H8B'	0.9801
C7—H7A	0.9801	C8'—H8C'	0.9801
C7—H7B	0.9801
C3—O1—C7	117.48 (13)	H8A—C8—H8C	109.5
C4—O2—C8	118.06 (12)	H8B—C8—H8C	109.5
C3'—O1'—C7'	117.22 (13)	C6'—C1'—C2'	121.26 (13)
C4'—O2'—C8'	117.06 (12)	C6'—C1'—H1A'	119.4
C6—C1—C2	120.97 (13)	C2'—C1'—H1A'	119.4
C6—C1—H1A	119.5	C3'—C2'—C1'	120.41 (14)
C2—C1—H1A	119.5	C3'—C2'—H2A'	119.8
C3—C2—C1	120.60 (14)	C1'—C2'—H2A'	119.8
C3—C2—H2A	119.7	O1'—C3'—C2'	125.07 (14)
C1—C2—H2A	119.7	O1'—C3'—C4'	115.73 (13)
O1—C3—C2	125.64 (14)	C2'—C3'—C4'	119.20 (13)
O1—C3—C4	115.17 (13)	O2'—C4'—C5'	125.37 (14)
C2—C3—C4	119.18 (13)	O2'—C4'—C3'	114.71 (13)
O2—C4—C5	124.71 (14)	C5'—C4'—C3'	119.91 (13)
O2—C4—C3	115.36 (13)	C4'—C5'—C6'	121.36 (14)
C5—C4—C3	119.92 (13)	C4'—C5'—H5A'	119.3
C4—C5—C6	121.08 (14)	C6'—C5'—H5A'	119.3
C4—C5—H5A	119.5	C1'—C6'—C5'	117.85 (13)
C6—C5—H5A	119.5	C1'—C6'—C6	121.43 (12)
C1—C6—C5	118.23 (13)	C5'—C6'—C6	120.70 (13)
C1—C6—C6'	122.08 (12)	O1'—C7'—H7A'	109.5
C5—C6—C6'	119.69 (13)	O1'—C7'—H7B'	109.5
O1—C7—H7A	109.5	H7A'—C7'—H7B'	109.5
O1—C7—H7B	109.5	O1'—C7'—H7C'	109.5
H7A—C7—H7B	109.5	H7A'—C7'—H7C'	109.5
O1—C7—H7C	109.5	H7B'—C7'—H7C'	109.5
H7A—C7—H7C	109.5	O2'—C8'—H8A'	109.5
H7B—C7—H7C	109.5	O2'—C8'—H8B'	109.5
O2—C8—H8A	109.5	H8A'—C8'—H8B'	109.5
O2—C8—H8B	109.5	O2'—C8'—H8C'	109.5
H8A—C8—H8B	109.5	H8A'—C8'—H8C'	109.5
O2—C8—H8C	109.5	H8B'—C8'—H8C'	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8B···O1′^i	0.98	2.53	3.495 (2)	168
C7′—H7A′···O2^ii	0.98	2.37	3.332 (2)	169

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