Di-tert-butyl 2,2′-(biphenyl-2,2′-diyl­dioxy)diacetate

Ali, Q.; Ibad, F.; Shah, M.R.; VanDerveer, D.

doi:10.1107/S1600536808019764

organic compounds

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ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page o1408

doi:10.1107/S1600536808019764

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Di-tert-butyl 2,2′-(biphenyl-2,2′-diyldioxy)diacetate

Qamar Ali,^a Farooq Ibad,^a Muhammad Raza Shah ^a ^* and Donald VanDerveer ^b

^aHEJ Research Institute of Chemistry, International Center for Chemical and Biological Sciences, University of Karachi, Karachi 75270, Pakistan, and ^bChemistry Department, Clemson University, Clemson, SC 29634-0973, USA
^*Correspondence e-mail: raza_shahm@yahoo.com

(Received 23 April 2008; accepted 28 June 2008; online 5 July 2008)

The title compound, C₂₄H₃₀O₆, does not exhibit π–π interactions due to the steric effect of the bulky tert-butyl groups present in the molecule. The presence of these groups at the 2 and 2′ positions hinders the free motion of the benzene rings relative to each other, causing them to adopt an antiperiplanar arrangement. The benzene rings are twisted by just under 50.96 (17)° with respect to each other. The carbonyl groups within the molecule are directed in different directions, one towards the biphenyl group and the other away from it. The molecules are linked together by C=O⋯H—C hydrogen bonds.

Related literature

For general background on chemical and biological studies of biphenyl compounds, see: Toshiaki et al. (2007 ); Kamoda et al. (2006 ); Makarov et al. (2005 ); Weisburger et al. (1967 ); Spivey et al. (1999 ); Sisson et al. (2006 ); Litvinchuk et al. (2004 ); Baudry et al. (2006 ). For the crystal structures of related compounds, see: Ali et al. (2008 ); Ibad et al. (2008 ).

Experimental

Crystal data

C₂₄H₃₀O₆
M_r = 414.48
Triclinic, $[P \overline 1]$
a = 7.7458 (15) Å
b = 12.112 (2) Å
c = 13.480 (3) Å
α = 67.36 (3)°
β = 82.11 (3)°
γ = 82.68 (3)°
V = 1152.3 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 153 (2) K
0.48 × 0.38 × 0.19 mm

Data collection

Rigaku Mercury CCD diffractometer
Absorption correction: multi-scan (REQAB; Jacobson, 1998 ) T_min = 0.960, T_max = 0.984
8742 measured reflections
4191 independent reflections
3687 reflections with I > 2σ(I)
R_int = 0.012

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.113
S = 1.06
4191 reflections
271 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯O2ⁱ	0.99	2.51	3.482 (2)	166
C20—H20C⋯O5ⁱⁱ	0.98	2.47	3.414 (2)	162
Symmetry codes: (i) -x+1, -y+1, -z+2; (ii) -x+1, -y+1, -z+1.

Data collection: CrystalClear (Rigaku/MSC, 2006 ); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808019764/ez2127sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808019764/ez2127Isup2.hkl

checkCIF report

Comment top

Biphenyl moieties have been found to act as pharmacophores in many biological studies such as antimycobacterial testing (Kamoda et al., 2006). Several derivatives of biphenyl are reported to be potential inhibitors of HRV-2 (Makarov et al., 2005). However, they also show carcinogenic activity (Weisburger et al., 1967). Furthermore, they occupy a unique place in various classes of organic compounds not only due to their prevalence as the core framework of numerous natural products, but also for their use as chiral reagents, as chiral phases for chromatography, and as chiral nucleophilic catalysts (Spivey et al., 1999). Biphenyl derivatives are also used as precursors for the synthesis of oligo(p-phenylene)s (Sisson et al., 2006). Oligo(p-phenylene)s have been extensively studied in the domain of artificial ion channels (Litvinchuk et al., 2004). Our interest in the synthesis of biphenyl derivatives stems from the fact that we wish to attach macrocycles like porphyrins and calix[4]arenes to oligo(p-phenylene)s to obtain functionalized pores (Baudry et al., 2006). In order to achieve these goals the synthesis of a number of biphenyl derivatives has been accomplished (Ali et al., 2008; Ibad et al., 2008). In this paper we report the synthesis and crystal structure of the title compound (I).

The OCH₂C(═O)OC(CH₃)₃ residues are twisted away fom the biphenyl, as seen in the value of the C14—O4—C15—C16 torsion angle of 67.83 (14). The crystal packing diagram (Fig. 2) shows that there are fairly strong C—H···O interactions that are 0.2 Å less than the sum of the van der Waals radii, which results in the molecules forming chains in the c-direction.

Related literature top

For general background on chemical and biological studies of biphenyl compounds, see: Toshiaki et al. (1994); Kamoda et al. (2006); Makarov et al. (2005); Weisburger et al. (1967); Spivey et al. (1999); Sisson et al. (2006); Litvinchuk et al. (2004); Baudry et al., 2006). For the crystal structures of related compounds, see: Ali et al. (2008); Ibad et al. (2008).

Experimental top

K₂CO₃ (414 mg, 3 mmol) and 2,2'-dihydroxybiphenyl (186 mg, 1 mmol) in 15 ml of acetone were stirred for 10 minutes, followed by addition of tertiary butyl bromoacetate (371 mg, 3 mmol). The reaction mixture was stirred at room temperature for three hours. Solvent was evaporated under reduced pressure and the residue was dissolved in a mixture of water (50 ml) and dichloromethane (50 ml). The aqueous layer was extracted three times with dichloromethane.The combined organic phases were evaporated under reduced pressure and the solid residue was dissolved in hot hexane. Slow evaporation of hot hexane gave colorless crystals (736 mg) in 80% yield.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2006); cell refinement: CrystalClear (Rigaku/MSC, 2006); data reduction: CrystalClear (Rigaku/MSC, 2006); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Crystal Structure of (I) showing the atom labelling scheme (50% ellipsoids).
	Fig. 2. Partial packing diagram viewed along the a axis.

Di-tert-butyl 2,2'-(biphenyl-2,2'-diyldioxy)diacetate top

Crystal data top

C₂₄H₃₀O₆	Z = 2
M_r = 414.48	F(000) = 444
Triclinic, P1	D_x = 1.195 Mg m⁻³
a = 7.7458 (15) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.112 (2) Å	Cell parameters from 3800 reflections
c = 13.480 (3) Å	θ = 3.0–26.4°
α = 67.36 (3)°	µ = 0.09 mm⁻¹
β = 82.11 (3)°	T = 153 K
γ = 82.68 (3)°	Chip, colorless
V = 1152.3 (4) Å³	0.48 × 0.38 × 0.19 mm

Data collection top

Rigaku Mercury CCD (2x2 bin mode) diffractometer	4191 independent reflections
Radiation source: Sealed Tube	3687 reflections with I > 2σ(I)
Graphite Monochromator monochromator	R_int = 0.012
Detector resolution: 14.6306 pixels mm^-1	θ_max = 25.4°, θ_min = 2.9°
ω scans	h = −9→9
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	k = −14→14
T_min = 0.960, T_max = 0.984	l = −13→16
8742 measured reflections

Refinement top

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.113	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0624P)² + 0.3008P] where P = (F_o² + 2F_c²)/3
4191 reflections	(Δ/σ)_max < 0.001
271 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₂₄H₃₀O₆	γ = 82.68 (3)°
M_r = 414.48	V = 1152.3 (4) Å³
Triclinic, P1	Z = 2
a = 7.7458 (15) Å	Mo Kα radiation
b = 12.112 (2) Å	µ = 0.09 mm⁻¹
c = 13.480 (3) Å	T = 153 K
α = 67.36 (3)°	0.48 × 0.38 × 0.19 mm
β = 82.11 (3)°

Data collection top

Rigaku Mercury CCD (2x2 bin mode) diffractometer	4191 independent reflections
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	3687 reflections with I > 2σ(I)
T_min = 0.960, T_max = 0.984	R_int = 0.012
8742 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.113	H-atom parameters constrained
S = 1.06	Δρ_max = 0.20 e Å⁻³
4191 reflections	Δρ_min = −0.21 e Å⁻³
271 parameters

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
O1	0.63964 (12)	0.48792 (8)	0.74773 (7)	0.0256 (2)
O2	0.67544 (15)	0.42265 (9)	0.92572 (8)	0.0407 (3)
O3	0.51537 (11)	0.70530 (8)	0.73639 (7)	0.0242 (2)
O4	0.22493 (12)	0.95936 (8)	0.46008 (7)	0.0279 (2)
O5	0.13650 (14)	0.94540 (8)	0.27408 (8)	0.0351 (2)
O6	0.14967 (12)	1.14648 (8)	0.18911 (7)	0.0285 (2)
C1	0.63803 (16)	0.49982 (12)	0.84152 (10)	0.0240 (3)
C2	0.58898 (17)	0.62861 (11)	0.83262 (10)	0.0249 (3)
H2A	0.5043	0.6279	0.8949	0.030*
H2B	0.6951	0.6628	0.8381	0.030*
C3	0.35750 (16)	0.67899 (11)	0.71761 (10)	0.0217 (3)
C4	0.24448 (17)	0.60667 (11)	0.79977 (11)	0.0264 (3)
H4A	0.2749	0.5724	0.8720	0.032*
C5	0.08664 (17)	0.58520 (12)	0.77493 (12)	0.0307 (3)
H5A	0.0099	0.5348	0.8302	0.037*
C6	0.04097 (17)	0.63678 (12)	0.67037 (12)	0.0306 (3)
H6A	−0.0676	0.6228	0.6539	0.037*
C7	0.15448 (16)	0.70935 (11)	0.58920 (11)	0.0258 (3)
H7A	0.1216	0.7451	0.5175	0.031*
C8	0.31533 (15)	0.73087 (10)	0.61059 (10)	0.0211 (3)
C9	0.44218 (16)	0.80053 (11)	0.52109 (10)	0.0219 (3)
C10	0.61274 (17)	0.75052 (13)	0.50921 (11)	0.0285 (3)
H10A	0.6473	0.6736	0.5598	0.034*
C11	0.73297 (18)	0.81058 (15)	0.42515 (12)	0.0372 (4)
H11A	0.8482	0.7749	0.4181	0.045*
C12	0.68340 (19)	0.92246 (16)	0.35221 (12)	0.0403 (4)
H12A	0.7657	0.9645	0.2952	0.048*
C13	0.51479 (18)	0.97446 (14)	0.36101 (11)	0.0335 (3)
H13A	0.4815	1.0514	0.3100	0.040*
C14	0.39452 (16)	0.91327 (12)	0.44496 (10)	0.0245 (3)
C15	0.16606 (19)	1.06562 (11)	0.37635 (11)	0.0284 (3)
H15A	0.2491	1.1275	0.3596	0.034*
H15B	0.0507	1.0966	0.4011	0.034*
C16	0.15050 (16)	1.04284 (11)	0.27501 (11)	0.0255 (3)
C17	0.67465 (19)	0.36897 (12)	0.73667 (12)	0.0309 (3)
C18	0.6458 (3)	0.40082 (18)	0.61993 (16)	0.0636 (6)
H18A	0.5237	0.4314	0.6089	0.095*
H18B	0.6720	0.3291	0.6017	0.095*
H18C	0.7230	0.4626	0.5734	0.095*
C19	0.5431 (3)	0.28453 (16)	0.81140 (19)	0.0589 (5)
H19A	0.5651	0.2644	0.8865	0.088*
H19B	0.5544	0.2110	0.7960	0.088*
H19C	0.4247	0.3235	0.8001	0.088*
C20	0.8607 (2)	0.32095 (15)	0.75818 (16)	0.0461 (4)
H20A	0.8746	0.3010	0.8345	0.069*
H20B	0.9400	0.3820	0.7131	0.069*
H20C	0.8886	0.2487	0.7410	0.069*
C21	0.12658 (19)	1.15005 (13)	0.08041 (11)	0.0313 (3)
C22	0.2762 (2)	1.07515 (15)	0.04516 (14)	0.0449 (4)
H22A	0.3876	1.1053	0.0455	0.067*
H22B	0.2633	1.0805	−0.0279	0.067*
H22C	0.2744	0.9913	0.0951	0.067*
C23	0.1343 (2)	1.28210 (13)	0.01004 (12)	0.0386 (4)
H23A	0.2499	1.3070	0.0098	0.058*
H23B	0.0444	1.3296	0.0387	0.058*
H23C	0.1136	1.2950	−0.0639	0.058*
C24	−0.0517 (2)	1.10931 (17)	0.08184 (13)	0.0458 (4)
H24A	−0.1431	1.1605	0.1051	0.069*
H24B	−0.0581	1.0258	0.1321	0.069*
H24C	−0.0689	1.1153	0.0092	0.069*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0307 (5)	0.0248 (5)	0.0223 (5)	−0.0003 (4)	−0.0047 (4)	−0.0096 (4)
O2	0.0582 (7)	0.0344 (6)	0.0223 (5)	0.0101 (5)	−0.0090 (5)	−0.0052 (5)
O3	0.0245 (4)	0.0238 (4)	0.0226 (5)	−0.0039 (3)	−0.0061 (4)	−0.0049 (4)
O4	0.0285 (5)	0.0244 (5)	0.0218 (5)	0.0031 (4)	−0.0014 (4)	−0.0005 (4)
O5	0.0451 (6)	0.0234 (5)	0.0360 (6)	−0.0064 (4)	−0.0066 (4)	−0.0080 (4)
O6	0.0397 (5)	0.0235 (5)	0.0207 (5)	−0.0042 (4)	−0.0067 (4)	−0.0047 (4)
C1	0.0232 (6)	0.0285 (7)	0.0181 (6)	−0.0020 (5)	−0.0023 (5)	−0.0064 (5)
C2	0.0276 (6)	0.0280 (7)	0.0189 (6)	−0.0018 (5)	−0.0060 (5)	−0.0075 (5)
C3	0.0206 (6)	0.0192 (6)	0.0246 (6)	0.0003 (5)	−0.0034 (5)	−0.0077 (5)
C4	0.0255 (6)	0.0241 (6)	0.0239 (7)	0.0006 (5)	−0.0018 (5)	−0.0036 (5)
C5	0.0238 (6)	0.0252 (7)	0.0341 (8)	−0.0028 (5)	0.0012 (5)	−0.0024 (6)
C6	0.0214 (6)	0.0272 (7)	0.0407 (8)	−0.0036 (5)	−0.0055 (6)	−0.0088 (6)
C7	0.0248 (6)	0.0235 (6)	0.0281 (7)	0.0001 (5)	−0.0068 (5)	−0.0078 (5)
C8	0.0212 (6)	0.0173 (6)	0.0236 (6)	0.0008 (4)	−0.0023 (5)	−0.0071 (5)
C9	0.0229 (6)	0.0245 (6)	0.0196 (6)	−0.0039 (5)	−0.0037 (5)	−0.0085 (5)
C10	0.0243 (6)	0.0354 (7)	0.0244 (7)	0.0010 (5)	−0.0050 (5)	−0.0097 (6)
C11	0.0215 (6)	0.0561 (9)	0.0304 (7)	−0.0012 (6)	−0.0013 (5)	−0.0131 (7)
C12	0.0288 (7)	0.0581 (10)	0.0264 (7)	−0.0125 (7)	0.0020 (6)	−0.0061 (7)
C13	0.0331 (7)	0.0362 (8)	0.0245 (7)	−0.0080 (6)	−0.0037 (6)	−0.0021 (6)
C14	0.0250 (6)	0.0270 (6)	0.0215 (6)	−0.0027 (5)	−0.0040 (5)	−0.0082 (5)
C15	0.0355 (7)	0.0203 (6)	0.0234 (7)	0.0032 (5)	−0.0056 (5)	−0.0024 (5)
C16	0.0244 (6)	0.0211 (6)	0.0268 (7)	−0.0015 (5)	−0.0040 (5)	−0.0040 (5)
C17	0.0370 (7)	0.0250 (7)	0.0348 (8)	−0.0033 (6)	−0.0037 (6)	−0.0155 (6)
C18	0.1049 (17)	0.0525 (11)	0.0492 (11)	0.0072 (11)	−0.0259 (11)	−0.0343 (10)
C19	0.0529 (10)	0.0426 (9)	0.0859 (15)	−0.0215 (8)	0.0172 (10)	−0.0317 (10)
C20	0.0403 (9)	0.0373 (8)	0.0676 (12)	0.0044 (7)	−0.0056 (8)	−0.0292 (8)
C21	0.0412 (8)	0.0321 (7)	0.0215 (7)	−0.0085 (6)	−0.0057 (6)	−0.0083 (6)
C22	0.0565 (10)	0.0422 (9)	0.0359 (9)	−0.0074 (7)	0.0058 (7)	−0.0166 (7)
C23	0.0557 (9)	0.0333 (8)	0.0239 (7)	−0.0079 (7)	−0.0098 (6)	−0.0041 (6)
C24	0.0480 (9)	0.0551 (10)	0.0339 (8)	−0.0188 (8)	−0.0107 (7)	−0.0095 (8)

Geometric parameters (Å, º) top

O1—C1	1.3247 (16)	C12—H12A	0.9500
O1—C17	1.4921 (16)	C13—C14	1.3924 (19)
O2—C1	1.2044 (17)	C13—H13A	0.9500
O3—C3	1.3811 (15)	C15—C16	1.5168 (19)
O3—C2	1.4180 (16)	C15—H15A	0.9900
O4—C14	1.3805 (16)	C15—H15B	0.9900
O4—C15	1.4183 (16)	C17—C20	1.507 (2)
O5—C16	1.2038 (16)	C17—C18	1.511 (2)
O6—C16	1.3407 (17)	C17—C19	1.513 (2)
O6—C21	1.4839 (16)	C18—H18A	0.9800
C1—C2	1.5196 (18)	C18—H18B	0.9800
C2—H2A	0.9900	C18—H18C	0.9800
C2—H2B	0.9900	C19—H19A	0.9800
C3—C4	1.3939 (19)	C19—H19B	0.9800
C3—C8	1.4006 (18)	C19—H19C	0.9800
C4—C5	1.3910 (19)	C20—H20A	0.9800
C4—H4A	0.9500	C20—H20B	0.9800
C5—C6	1.380 (2)	C20—H20C	0.9800
C5—H5A	0.9500	C21—C23	1.517 (2)
C6—C7	1.391 (2)	C21—C22	1.518 (2)
C6—H6A	0.9500	C21—C24	1.520 (2)
C7—C8	1.3938 (17)	C22—H22A	0.9800
C7—H7A	0.9500	C22—H22B	0.9800
C8—C9	1.4950 (18)	C22—H22C	0.9800
C9—C10	1.3966 (19)	C23—H23A	0.9800
C9—C14	1.3967 (19)	C23—H23B	0.9800
C10—C11	1.389 (2)	C23—H23C	0.9800
C10—H10A	0.9500	C24—H24A	0.9800
C11—C12	1.377 (2)	C24—H24B	0.9800
C11—H11A	0.9500	C24—H24C	0.9800
C12—C13	1.386 (2)

C1—O1—C17	122.25 (11)	C16—C15—H15B	109.3
C3—O3—C2	117.83 (10)	H15A—C15—H15B	108.0
C14—O4—C15	116.99 (11)	O5—C16—O6	125.86 (13)
C16—O6—C21	121.03 (10)	O5—C16—C15	123.97 (12)
O2—C1—O1	126.99 (13)	O6—C16—C15	110.14 (11)
O2—C1—C2	120.93 (12)	O1—C17—C20	109.60 (11)
O1—C1—C2	112.04 (11)	O1—C17—C18	102.02 (12)
O3—C2—C1	115.22 (10)	C20—C17—C18	111.65 (15)
O3—C2—H2A	108.5	O1—C17—C19	109.59 (12)
C1—C2—H2A	108.5	C20—C17—C19	112.56 (14)
O3—C2—H2B	108.5	C18—C17—C19	110.90 (16)
C1—C2—H2B	108.5	C17—C18—H18A	109.5
H2A—C2—H2B	107.5	C17—C18—H18B	109.5
O3—C3—C4	122.53 (11)	H18A—C18—H18B	109.5
O3—C3—C8	116.03 (11)	C17—C18—H18C	109.5
C4—C3—C8	121.43 (11)	H18A—C18—H18C	109.5
C5—C4—C3	119.31 (12)	H18B—C18—H18C	109.5
C5—C4—H4A	120.3	C17—C19—H19A	109.5
C3—C4—H4A	120.3	C17—C19—H19B	109.5
C6—C5—C4	120.34 (12)	H19A—C19—H19B	109.5
C6—C5—H5A	119.8	C17—C19—H19C	109.5
C4—C5—H5A	119.8	H19A—C19—H19C	109.5
C5—C6—C7	119.79 (12)	H19B—C19—H19C	109.5
C5—C6—H6A	120.1	C17—C20—H20A	109.5
C7—C6—H6A	120.1	C17—C20—H20B	109.5
C6—C7—C8	121.50 (12)	H20A—C20—H20B	109.5
C6—C7—H7A	119.2	C17—C20—H20C	109.5
C8—C7—H7A	119.2	H20A—C20—H20C	109.5
C7—C8—C3	117.62 (12)	H20B—C20—H20C	109.5
C7—C8—C9	120.83 (11)	O6—C21—C23	102.98 (11)
C3—C8—C9	121.45 (11)	O6—C21—C22	109.69 (12)
C10—C9—C14	117.97 (12)	C23—C21—C22	110.79 (13)
C10—C9—C8	119.72 (11)	O6—C21—C24	109.62 (12)
C14—C9—C8	122.25 (11)	C23—C21—C24	110.38 (13)
C11—C10—C9	121.56 (13)	C22—C21—C24	112.92 (13)
C11—C10—H10A	119.2	C21—C22—H22A	109.5
C9—C10—H10A	119.2	C21—C22—H22B	109.5
C12—C11—C10	119.28 (14)	H22A—C22—H22B	109.5
C12—C11—H11A	120.4	C21—C22—H22C	109.5
C10—C11—H11A	120.4	H22A—C22—H22C	109.5
C11—C12—C13	120.73 (13)	H22B—C22—H22C	109.5
C11—C12—H12A	119.6	C21—C23—H23A	109.5
C13—C12—H12A	119.6	C21—C23—H23B	109.5
C12—C13—C14	119.66 (13)	H23A—C23—H23B	109.5
C12—C13—H13A	120.2	C21—C23—H23C	109.5
C14—C13—H13A	120.2	H23A—C23—H23C	109.5
O4—C14—C13	123.23 (12)	H23B—C23—H23C	109.5
O4—C14—C9	115.98 (11)	C21—C24—H24A	109.5
C13—C14—C9	120.78 (12)	C21—C24—H24B	109.5
O4—C15—C16	111.40 (11)	H24A—C24—H24B	109.5
O4—C15—H15A	109.3	C21—C24—H24C	109.5
C16—C15—H15A	109.3	H24A—C24—H24C	109.5
O4—C15—H15B	109.3	H24B—C24—H24C	109.5

C17—O1—C1—O2	5.8 (2)	C8—C9—C10—C11	177.90 (12)
C17—O1—C1—C2	−176.69 (10)	C9—C10—C11—C12	0.5 (2)
C3—O3—C2—C1	63.42 (14)	C10—C11—C12—C13	−1.0 (2)
O2—C1—C2—O3	−168.21 (12)	C11—C12—C13—C14	0.4 (2)
O1—C1—C2—O3	14.12 (15)	C15—O4—C14—C13	9.65 (18)
C2—O3—C3—C4	20.01 (17)	C15—O4—C14—C9	−171.68 (11)
C2—O3—C3—C8	−160.90 (11)	C12—C13—C14—O4	179.23 (13)
O3—C3—C4—C5	179.27 (12)	C12—C13—C14—C9	0.6 (2)
C8—C3—C4—C5	0.22 (19)	C10—C9—C14—O4	−179.80 (11)
C3—C4—C5—C6	−1.2 (2)	C8—C9—C14—O4	2.91 (17)
C4—C5—C6—C7	0.8 (2)	C10—C9—C14—C13	−1.10 (19)
C5—C6—C7—C8	0.5 (2)	C8—C9—C14—C13	−178.39 (12)
C6—C7—C8—C3	−1.45 (19)	C14—O4—C15—C16	67.83 (14)
C6—C7—C8—C9	174.84 (12)	C21—O6—C16—O5	1.3 (2)
O3—C3—C8—C7	−178.03 (11)	C21—O6—C16—C15	−176.87 (11)
C4—C3—C8—C7	1.08 (18)	O4—C15—C16—O5	21.25 (18)
O3—C3—C8—C9	5.71 (17)	O4—C15—C16—O6	−160.51 (11)
C4—C3—C8—C9	−175.19 (11)	C1—O1—C17—C20	−66.57 (16)
C7—C8—C9—C10	−125.19 (13)	C1—O1—C17—C18	174.98 (14)
C3—C8—C9—C10	50.96 (17)	C1—O1—C17—C19	57.41 (17)
C7—C8—C9—C14	52.05 (17)	C16—O6—C21—C23	−179.93 (12)
C3—C8—C9—C14	−131.80 (13)	C16—O6—C21—C22	−61.94 (16)
C14—C9—C10—C11	0.54 (19)	C16—O6—C21—C24	62.58 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O2ⁱ	0.99	2.51	3.482 (2)	166
C20—H20C···O5ⁱⁱ	0.98	2.47	3.414 (2)	162

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

Experimental details

Crystal data
Chemical formula	C₂₄H₃₀O₆
M_r	414.48
Crystal system, space group	Triclinic, P1
Temperature (K)	153
a, b, c (Å)	7.7458 (15), 12.112 (2), 13.480 (3)
α, β, γ (°)	67.36 (3), 82.11 (3), 82.68 (3)
V (Å³)	1152.3 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.48 × 0.38 × 0.19

Data collection
Diffractometer	Rigaku Mercury CCD (2x2 bin mode) diffractometer
Absorption correction	Multi-scan (REQAB; Jacobson, 1998)
T_min, T_max	0.960, 0.984
No. of measured, independent and observed [I > 2σ(I)] reflections	8742, 4191, 3687
R_int	0.012
(sin θ/λ)_max (Å⁻¹)	0.604

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.113, 1.06
No. of reflections	4191
No. of parameters	271
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.21

Computer programs: CrystalClear (Rigaku/MSC, 2006), SHELXTL (Sheldrick, 2008).

Selected torsion angles (º) top

C3—C8—C9—C10

50.96 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O2ⁱ	0.99	2.513	3.482 (2)	166.4
C20—H20C···O5ⁱⁱ	0.98	2.470	3.414 (2)	161.7

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

Acknowledgements

The authors thank the Organization for the Prohibition of Chemical Weapons for financial support.

References

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