1-Ethyl 2,2-dimethyl 3-(1,3-benzodioxol-5-yl)propane-1,2,2-tricarboxyl­ate

The mol­ecular structure of the title triester compound, C₁₇H₂₀O₈, consists of a benzodioxole fused-ring system, an ethoxy­carbon­ylmethyl group and two methoxy­carbonyl groups arranged around a tetra­hedral carbon center. Unlike similar triesters, which are oils, the title compound crystallizes at room temperature as inter­digitated bilayers of triester mol­ecules, with short O...H contacts from the methyl­ene H atoms of benzodioxole to the carbonyl O atom of the ethoxy­carbon­ylmethyl group and to a ring O atom of the benzodioxole group of a neighboring mol­ecule within the bilayer. The persistence of these short C—H...O interactions from the activated H atoms of the benzodioxole ring at both 100 and 300 K indicate that they help provide the stabilization necessary for crystallization from the oil.

S1. Comment

The title compound, (I), was prepared in the course of preparation of analogs of 1,2-dihydronaphthalen-2-amine (Hathaway et al., 1982). Unlike similar triesters, which are oils, the title compound crystallized at room temperature. It was prepared from dimethyl (1,3-benzodioxol-5-ylmethyl)malonate, (II), by alkylation with ethyl chloroacetate. The starting compound (II) was prepared from piperonal as shown in the scheme.

While the following details, as well as the figures and table, are derived from the structure at 100 K, similar geometry is found for the room temperature structure except where otherwise noted.

The benzodioxole fused ring, two methoxycarbonyl groups, and an (ethoxycarbonyl)methyl group are arranged around the tetrahedral C2. Bond lengths and angles within the six-membered ring are consistent with its aromatic character, although significant bond length alternation is found. The C33—C34 bond length of 1.3848 (17) Å for the two ring C atoms that are also part of the five-membered ring is close in value to the average C—C bond length in the six-membered ring (1.390 Å). The two neighboring bonds (C32—C33, C34—C35) have the shortest lengths in the ring (Table 1), while the next two neighboring bonds (C31—C32, C35—C36) are the longest; and the opposite bond in the ring (C31—C36) is again close to the average.

The gross shape of the molecule is flattened with respect to the tetrahedron about C2 and, in the projection of Fig. 1, can be viewed as being formed by intersecting diester and monoester chains, both with an anti conformation, which cross at approximately a right angle [87.84 (4)° between their mean planes] and share C2. The diester chain, which extends from the ethoxy group (C112) to the methoxy group at C221, exhibits a significant twist, with the ethoxy-group plane forming an angle of 28.40 (6)° relative to the plane of the remaining atoms in this chain. The monoester chain runs from the fused-ring system to the methoxy group C211. The fused-ring system is almost coplanar with the mean plane of the molecule [dihedral 13.34 (3)°] and forms an angle of 76.72 (3)° with the plane of the monoester chain.

The extended structure consists of interdigitated bilayers of the title molecule parallel to the crystallographic bc plane (Fig. 2). The ethoxy chain and benzodioxole ring of each molecule are directed into the bilayer such that the ethoxy chain of one molecule lies between benzodioxole rings of two neighbors and vice versa. Shortest O—H contact distances between neighboring molecules are 2.48 Å [O112···H37Aⁱ; (i) 1 - x, 1 - y, 1 - z], linking the carbonyl O atom of the ethoxy group to a methylene H atom of the benzodioxole group, and 2.52 Å [O34···H37Bⁱⁱ; (ii) 1 - x, -y, 1 - z] linking an O atom of the benzodioxole group to the other methylene H atom within the bilayer in the 300 K structure. These contacts decrease in length to 2.355 (15) Å and 2.406 (15) Å at 100 K. Since C37 is bound to two O atoms, it is not surprising that the H atoms attached to it would be activated.

One methoxy group (C211) is approximately parallel with and on the outer edges of the bilayer. The other methoxy group (C221) is approximately perpendicular to the bilayer and partially extends into the neighboring bilayer. The short C—H···O hydrogen bonds that link neighboring molecules within the layer and the enhanced dispersion forces arising from partial extension of ethoxy groups into neighboring layers likely provide the stabilization needed for the compound to crystallize from the oil.

Related literature

For related literature, see: Hathaway et al. (1982).

S2. Experimental

To a solution of (II) (10.6 g, 0.040 mol) in 30 ml of DMF under nitrogen was added sodium hydride (50% in mineral oil, 1.92 g, 0.040 mol). The resulting red solution was stirred for 45 min, after which a solution of ethyl chloroacetate (4.9 g, 0.040 mol) in 10 ml of DMF was added dropwise over 10 min. The resulting solution was heated at 333 K overnight. The reaction mixture was poured into 100 ml of water, and extracted three times with ether. The combined ether layers were dried with magnesium sulfate, and the solvent removed under reduced pressure. The residual yellow oil was dissolved in acetonitrile, and the acetonitrile was washed twice with hexane. The acetonitrile was removed under reduced pressure to produce the title compound as a yellow oil, which crystallized upon standing (9.11 g, 65%). 1H-NMR (CDCl₃, 300 MHz): δ 1.27 (t, 3H, J = 7.1 Hz, H112), 2.86 (s, 2H, H11), 3.30 (s, 2H, H3), 3.76 (s, 6H, OCH₃'s), 4.16 (q, 2H, J = 7.1 Hz, H111), 5.93 (s, 2H, H37), 6.52 (dd, 1H, J = 7.9 Hz and 2.7 Hz, H36), 6.56 (d, 1H, J = 2.7 Hz, H32) and 6.71 (d, 1H, J = 7.9 Hz, H35). 13 C-NMR (CDCl₃, 75.5 MHz): δ 14.1 (C112), 36.8 (C3), 38.5 (C1), 52.8 (OCH₃'s), 56.8 (C2), 60.8 (C111), 101.0 (C37), 108.2 (C32 or C35), 110.2 (C32 or C35), 123.2 (C36), 129.0 (C31), 146.8 (C33 or C34), 147.6 (C33 or C34), 170.4 (C21 and C22) and 170.6 (C11).

S3. Refinement

All non-H atoms were refined with anisotropic displacement parameters in both structures. For T = 100 K, all H atoms were found in difference maps and freely refined. Refined C—H bond lengths range from 0.953 to 1.07 Å. All of the H atoms in the 300 K structure were visible in difference maps except for two of the methyl groups (C112, C211), for which only some of the H atoms were visible. All H-atom positions were calculated to give an idealized geometry about their parent atoms in the 300 K structure. Multiple difference map peaks around the methyl groups C112 and C211 implied disorder and H-atom positions were calculated to give twofold disorder. The torsion angle of the methyl group at C221 was refined to match the electron density. Calculated C—H bond lengths in the 300 K structure are assigned in the range 0.96–0.97 Å for methyl and methylene H atoms and 0.93 Å for aromatic H atoms.

Computing details

Data collection: KappaCCD software for I_100K. Cell refinement: SCALEPACK (Otwinowski & Minor, 1997) for I_100K; HKL SCALEPACK (Otwinowski & Minor, 1997) for I_300K. Data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997) for I_100K. Program(s) used to solve structure: maXus (Mackay et al., 1999) and SIR97 (Altomare et al., 1999)' for I_100K; 'maXus (Mackay et al., 1999)and SIR97 (Altomare et al., 1999)' for I_300K. For both compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 2008). Molecular graphics: ORTEP (Johnson, 1976) for I_100K. For both compounds, software used to prepare material for publication: PARST (Nardelli, 1995).

Figures

	Fig. 1. The title compound with the atom-labeling scheme, T = 100 K. Displacement ellipsoids are drawn at the 50% level.
	Fig. 2. The packing at 100 K. The bilayer structure is shown within the unit cell boundaries, with molecules from neighboring layers shown to the left and right.

(I_100K) 1-Ethyl 2,2-dimethyl 3-(1,3-benzodioxol-5-yl)propane-1,2,2-tricarboxylate

Crystal data

C17H20O8	F(000) = 744
Mr = 352.33	Dx = 1.399 Mg m^−3
Monoclinic, P21/c	Melting point = 340–341 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 10.3799 (2) Å	Cell parameters from 5085 reflections
b = 11.7642 (2) Å	θ = 1.0–30.0°
c = 14.5275 (3) Å	µ = 0.11 mm^−1
β = 109.4783 (8)°	T = 100 K
V = 1672.49 (6) Å^3	Irregular, colourless
Z = 4	0.30 × 0.30 × 0.25 mm

Data collection

Nonius KappaCCD diffractometer	3573 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.051
Graphite monochromator	θmax = 30.0°, θmin = 3.4°
CCD scans	h = 0→14
4861 measured reflections	k = 0→16
4861 independent reflections	l = −20→19

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)] = 0.042	Hydrogen site location: difference Fourier map
wR(F^2) = 0.108	All H-atom parameters refined
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0733P)^2 + 0.1393P] where P = (Fo^2 + 2Fc^2)/3
4861 reflections	(Δ/σ)max < 0.001
306 parameters	Δρmax = 0.29 e Å^−3
0 restraints	Δρmin = −0.25 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
C1	0.37676 (12)	0.53491 (11)	0.20482 (9)	0.0203 (2)
H1A	0.4104 (14)	0.4604 (13)	0.2317 (10)	0.024 (4)*
H1B	0.3614 (14)	0.5319 (12)	0.1352 (11)	0.024 (3)*
C2	0.24179 (11)	0.56349 (10)	0.22145 (8)	0.0185 (2)
C3	0.25195 (13)	0.55367 (11)	0.33026 (9)	0.0206 (2)
H3A	0.3258 (14)	0.6056 (12)	0.3677 (10)	0.021 (3)*
H3B	0.1652 (14)	0.5814 (12)	0.3345 (10)	0.022 (3)*
C31	0.28393 (12)	0.43606 (10)	0.37383 (8)	0.0195 (2)
C32	0.42093 (12)	0.40029 (11)	0.41452 (8)	0.0209 (2)
H32	0.4938 (14)	0.4493 (12)	0.4139 (10)	0.025 (4)*
C33	0.44457 (11)	0.29421 (11)	0.45633 (8)	0.0203 (2)
C34	0.33948 (12)	0.22335 (10)	0.45930 (9)	0.0210 (2)
C35	0.20479 (13)	0.25490 (11)	0.41948 (10)	0.0246 (3)
H35	0.1306 (15)	0.2057 (13)	0.4221 (11)	0.031 (4)*
C36	0.17930 (12)	0.36327 (11)	0.37656 (9)	0.0219 (2)
H36	0.0855 (15)	0.3880 (12)	0.3485 (10)	0.024 (4)*
O33	0.56824 (8)	0.24104 (8)	0.49873 (7)	0.0269 (2)
O34	0.39303 (9)	0.12216 (8)	0.50364 (7)	0.0269 (2)
C37	0.53777 (13)	0.14246 (11)	0.54577 (10)	0.0261 (3)
H37A	0.5603 (14)	0.1598 (13)	0.6150 (11)	0.026 (4)*
H37B	0.5863 (15)	0.0754 (13)	0.5320 (10)	0.028 (4)*
C11	0.48473 (12)	0.62470 (11)	0.24745 (9)	0.0223 (2)
O111	0.61081 (9)	0.58373 (8)	0.26863 (7)	0.0273 (2)
O112	0.46014 (10)	0.72261 (8)	0.25945 (8)	0.0347 (2)
C111	0.71926 (13)	0.66928 (13)	0.30554 (11)	0.0295 (3)
H11A	0.7112 (16)	0.7257 (14)	0.2535 (12)	0.038 (4)*
H11B	0.7014 (16)	0.7109 (14)	0.3603 (12)	0.034 (4)*
C112	0.85335 (17)	0.61144 (17)	0.33654 (18)	0.0524 (5)
H12A	0.934 (2)	0.6701 (18)	0.3583 (15)	0.066 (6)*
H12B	0.859 (2)	0.568 (2)	0.2796 (18)	0.079 (7)*
H12C	0.861 (3)	0.555 (3)	0.396 (2)	0.114 (10)*
C21	0.19455 (12)	0.68495 (10)	0.18709 (9)	0.0212 (2)
O211	0.19863 (9)	0.70123 (7)	0.09667 (6)	0.0255 (2)
O212	0.15514 (9)	0.75435 (8)	0.23209 (7)	0.0282 (2)
C211	0.17092 (16)	0.81621 (13)	0.06056 (12)	0.0339 (3)
H21A	0.1817 (18)	0.8156 (15)	−0.0046 (14)	0.050 (5)*
H21B	0.2396 (17)	0.8727 (15)	0.1062 (12)	0.041 (4)*
H21C	0.0786 (18)	0.8389 (14)	0.0534 (12)	0.041 (4)*
C22	0.13020 (12)	0.48291 (10)	0.15953 (8)	0.0204 (2)
O221	0.00934 (8)	0.51196 (8)	0.16648 (6)	0.0265 (2)
O222	0.14782 (9)	0.40523 (8)	0.11153 (7)	0.0290 (2)
C221	−0.10594 (14)	0.44128 (14)	0.11268 (11)	0.0325 (3)
H22A	−0.186 (2)	0.4784 (18)	0.1212 (15)	0.070 (6)*
H22B	−0.0990 (17)	0.3649 (15)	0.1375 (12)	0.041 (4)*
H22C	−0.1164 (18)	0.4436 (15)	0.0442 (14)	0.049 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0207 (6)	0.0209 (6)	0.0203 (6)	0.0003 (5)	0.0081 (5)	−0.0025 (5)
C2	0.0192 (5)	0.0171 (5)	0.0196 (5)	0.0001 (4)	0.0069 (4)	−0.0019 (4)
C3	0.0216 (6)	0.0211 (6)	0.0198 (5)	−0.0005 (5)	0.0077 (5)	−0.0035 (5)
C31	0.0207 (6)	0.0206 (6)	0.0173 (5)	−0.0007 (4)	0.0067 (4)	−0.0035 (4)
C32	0.0189 (6)	0.0235 (6)	0.0195 (6)	−0.0042 (5)	0.0055 (5)	−0.0032 (5)
C33	0.0162 (5)	0.0252 (6)	0.0188 (5)	−0.0002 (4)	0.0047 (4)	−0.0031 (5)
C34	0.0229 (6)	0.0202 (6)	0.0209 (6)	0.0013 (5)	0.0085 (5)	−0.0001 (5)
C35	0.0203 (6)	0.0249 (6)	0.0304 (6)	−0.0026 (5)	0.0110 (5)	0.0010 (5)
C36	0.0182 (6)	0.0252 (6)	0.0233 (6)	0.0010 (5)	0.0080 (5)	−0.0003 (5)
O33	0.0177 (4)	0.0294 (5)	0.0311 (5)	0.0016 (4)	0.0048 (4)	0.0048 (4)
O34	0.0229 (4)	0.0231 (5)	0.0338 (5)	0.0016 (3)	0.0085 (4)	0.0046 (4)
C37	0.0247 (6)	0.0233 (7)	0.0274 (7)	0.0016 (5)	0.0046 (5)	−0.0007 (5)
C11	0.0207 (6)	0.0265 (6)	0.0211 (6)	−0.0008 (5)	0.0089 (5)	−0.0010 (5)
O111	0.0190 (4)	0.0273 (5)	0.0351 (5)	−0.0017 (3)	0.0086 (4)	−0.0008 (4)
O112	0.0268 (5)	0.0264 (5)	0.0507 (6)	−0.0040 (4)	0.0125 (4)	−0.0121 (5)
C111	0.0222 (6)	0.0340 (7)	0.0315 (7)	−0.0073 (5)	0.0079 (5)	−0.0003 (6)
C112	0.0262 (8)	0.0437 (10)	0.0803 (14)	−0.0019 (7)	0.0083 (8)	−0.0111 (10)
C21	0.0179 (6)	0.0211 (6)	0.0250 (6)	−0.0019 (5)	0.0078 (5)	−0.0016 (5)
O211	0.0320 (5)	0.0212 (5)	0.0257 (4)	0.0036 (4)	0.0128 (4)	0.0045 (4)
O212	0.0330 (5)	0.0221 (5)	0.0334 (5)	0.0053 (4)	0.0163 (4)	−0.0014 (4)
C211	0.0373 (8)	0.0271 (7)	0.0433 (9)	0.0097 (6)	0.0216 (7)	0.0139 (6)
C22	0.0211 (6)	0.0198 (6)	0.0191 (5)	−0.0008 (4)	0.0052 (5)	0.0025 (5)
O221	0.0180 (4)	0.0281 (5)	0.0309 (5)	−0.0027 (3)	0.0047 (4)	−0.0037 (4)
O222	0.0315 (5)	0.0241 (5)	0.0316 (5)	−0.0038 (4)	0.0106 (4)	−0.0091 (4)
C221	0.0218 (7)	0.0362 (8)	0.0336 (8)	−0.0086 (6)	0.0016 (6)	0.0007 (6)

Geometric parameters (Å, º)

C1—C11	1.5141 (17)	C37—H37A	0.975 (15)
C1—C2	1.5361 (16)	C37—H37B	0.992 (15)
C1—H1A	0.976 (15)	C11—O112	1.2050 (15)
C1—H1B	0.971 (14)	C11—O111	1.3309 (15)
C2—C22	1.5345 (16)	O111—C111	1.4714 (16)
C2—C21	1.5388 (17)	C111—C112	1.478 (2)
C2—C3	1.5531 (16)	C111—H11A	0.988 (17)
C3—C31	1.5116 (17)	C111—H11B	1.003 (16)
C3—H3A	0.989 (14)	C112—H12A	1.05 (2)
C3—H3B	0.979 (14)	C112—H12B	0.99 (2)
C31—C36	1.3940 (17)	C112—H12C	1.07 (3)
C31—C32	1.4101 (17)	C21—O212	1.1999 (14)
C32—C33	1.3737 (18)	C21—O211	1.3419 (14)
C32—H32	0.953 (14)	O211—C211	1.4446 (16)
C33—O33	1.3752 (14)	C211—H21A	0.990 (19)
C33—C34	1.3848 (17)	C211—H21B	1.036 (17)
C34—C35	1.3739 (17)	C211—H21C	0.966 (17)
C34—O34	1.3792 (15)	C22—O222	1.1999 (15)
C35—C36	1.4050 (18)	C22—O221	1.3362 (14)
C35—H35	0.974 (15)	O221—C221	1.4527 (16)
C36—H36	0.967 (14)	C221—H22A	0.98 (2)
O33—C37	1.4339 (16)	C221—H22B	0.961 (18)
O34—C37	1.4407 (16)	C221—H22C	0.964 (18)
C11—C1—C2	111.87 (10)	O34—C37—H37A	109.3 (8)
C11—C1—H1A	110.2 (8)	O33—C37—H37B	109.9 (8)
C2—C1—H1A	111.0 (8)	O34—C37—H37B	108.1 (9)
C11—C1—H1B	107.1 (8)	H37A—C37—H37B	114.3 (12)
C2—C1—H1B	109.3 (8)	O112—C11—O111	123.52 (11)
H1A—C1—H1B	107.2 (11)	O112—C11—C1	124.23 (11)
C22—C2—C1	108.80 (9)	O111—C11—C1	112.25 (10)
C22—C2—C21	106.67 (9)	C11—O111—C111	114.23 (10)
C1—C2—C21	111.16 (10)	O111—C111—C112	108.93 (13)
C22—C2—C3	109.42 (9)	O111—C111—H11A	108.7 (9)
C1—C2—C3	112.81 (10)	C112—C111—H11A	111.9 (9)
C21—C2—C3	107.78 (9)	O111—C111—H11B	107.6 (9)
C31—C3—C2	115.16 (10)	C112—C111—H11B	112.8 (9)
C31—C3—H3A	108.3 (8)	H11A—C111—H11B	106.8 (13)
C2—C3—H3A	106.9 (8)	C111—C112—H12A	111.5 (11)
C31—C3—H3B	110.9 (8)	C111—C112—H12B	107.1 (14)
C2—C3—H3B	106.7 (8)	H12A—C112—H12B	109.2 (17)
H3A—C3—H3B	108.7 (11)	C111—C112—H12C	110.0 (15)
C36—C31—C32	119.41 (11)	H12A—C112—H12C	108.9 (18)
C36—C31—C3	120.65 (11)	H12B—C112—H12C	110 (2)
C32—C31—C3	119.91 (11)	O212—C21—O211	124.33 (11)
C33—C32—C31	117.58 (11)	O212—C21—C2	125.78 (11)
C33—C32—H32	121.9 (9)	O211—C21—C2	109.84 (10)
C31—C32—H32	120.5 (9)	C21—O211—C211	114.94 (10)
C32—C33—O33	127.85 (11)	O211—C211—H21A	105.5 (11)
C32—C33—C34	122.29 (11)	O211—C211—H21B	110.9 (9)
O33—C33—C34	109.86 (11)	H21A—C211—H21B	110.2 (14)
C35—C34—O34	128.67 (11)	O211—C211—H21C	111.6 (10)
C35—C34—C33	121.72 (12)	H21A—C211—H21C	108.8 (14)
O34—C34—C33	109.58 (10)	H21B—C211—H21C	109.7 (14)
C34—C35—C36	116.52 (11)	O222—C22—O221	124.58 (11)
C34—C35—H35	122.0 (9)	O222—C22—C2	125.43 (11)
C36—C35—H35	121.4 (9)	O221—C22—C2	109.99 (10)
C31—C36—C35	122.47 (11)	C22—O221—C221	116.02 (10)
C31—C36—H36	119.2 (8)	O221—C221—H22A	105.0 (12)
C35—C36—H36	118.3 (8)	O221—C221—H22B	112.8 (10)
C33—O33—C37	105.07 (9)	H22A—C221—H22B	109.2 (16)
C34—O34—C37	104.84 (9)	O221—C221—H22C	109.1 (11)
O33—C37—O34	107.23 (10)	H22A—C221—H22C	108.0 (16)
O33—C37—H37A	107.9 (9)	H22B—C221—H22C	112.4 (15)

(I_300K)

Crystal data

C17H20O8	F(000) = 744
Mr = 352.34	Dx = 1.349 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3333 reflections
a = 10.4985 (2) Å	θ = 1.0–25.4°
b = 11.8828 (2) Å	µ = 0.11 mm^−1
c = 14.7540 (3) Å	T = 300 K
β = 109.5329 (9)°	Irregular, colourless
V = 1734.66 (6) Å^3	0.30 × 0.30 × 0.25 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer	Rint = 0.047
Radiation source: fine-focus sealed tube	θmax = 25.3°, θmin = 1.5°
CCD scans	h = −12→12
6310 measured reflections	k = −14→14
3157 independent reflections	l = −17→17
1879 reflections with I > 2σ(I)

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.047	H-atom parameters constrained
wR(F^2) = 0.144	w = 1/[σ^2(Fo^2) + (0.0715P)^2 + 0.1953P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
3157 reflections	Δρmax = 0.29 e Å^−3
228 parameters	Δρmin = −0.18 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.024 (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	Occ. (<1)
C1	0.3751 (2)	0.53110 (18)	0.20770 (15)	0.0579 (6)
H1A	0.4063	0.4582	0.2361	0.07*
H1B	0.3599	0.5257	0.1393	0.07*
C2	0.2413 (2)	0.55942 (17)	0.22284 (14)	0.0515 (5)
C3	0.2501 (2)	0.54881 (19)	0.32990 (15)	0.0591 (6)
H3A	0.3183	0.601	0.3677	0.071*
H3B	0.1642	0.5721	0.335	0.071*
C31	0.2833 (2)	0.43345 (18)	0.37376 (14)	0.0546 (6)
C32	0.4184 (2)	0.3995 (2)	0.41591 (15)	0.0595 (6)
H32	0.4891	0.4466	0.4159	0.071*
C33	0.4428 (2)	0.2955 (2)	0.45678 (15)	0.0573 (6)
C34	0.3409 (2)	0.22425 (19)	0.45871 (16)	0.0601 (6)
C35	0.2086 (2)	0.2537 (2)	0.41820 (19)	0.0713 (7)
H35	0.1392	0.2054	0.4189	0.086*
C36	0.1821 (2)	0.3597 (2)	0.37569 (17)	0.0652 (6)
H36	0.0925	0.3819	0.3474	0.078*
O33	0.56622 (15)	0.24473 (15)	0.50155 (13)	0.0787 (5)
O34	0.39486 (16)	0.12507 (14)	0.50430 (13)	0.0786 (5)
C37	0.5368 (2)	0.1444 (2)	0.54286 (19)	0.0748 (7)
H37A	0.5647	0.1519	0.6122	0.09*
H37B	0.5852	0.0815	0.5278	0.09*
C11	0.4836 (2)	0.6176 (2)	0.25127 (17)	0.0644 (6)
O111	0.60554 (16)	0.57736 (14)	0.26771 (14)	0.0862 (6)
O112	0.46276 (18)	0.71285 (17)	0.26786 (17)	0.1014 (7)
C111	0.7161 (3)	0.6577 (3)	0.3058 (2)	0.0994 (9)
H11A	0.7107	0.715	0.2578	0.119*
H11B	0.7074	0.6944	0.3621	0.119*
C112	0.8423 (4)	0.6031 (3)	0.3307 (4)	0.1549 (17)
H12A	0.9133	0.6573	0.3556	0.232*	0.5
H12B	0.8516	0.5679	0.2747	0.232*	0.5
H12C	0.8481	0.547	0.3787	0.232*	0.5
H12D	0.8287	0.5242	0.317	0.232*	0.5
H12E	0.8904	0.6136	0.398	0.232*	0.5
H12F	0.8939	0.6344	0.2939	0.232*	0.5
C21	0.1957 (2)	0.67913 (19)	0.18941 (17)	0.0601 (6)
O211	0.20030 (17)	0.69597 (13)	0.10097 (12)	0.0721 (5)
O212	0.15593 (18)	0.74784 (14)	0.23263 (13)	0.0827 (6)
C211	0.1710 (3)	0.8084 (2)	0.0634 (2)	0.1000 (10)
H21A	0.1775	0.8114	0.0001	0.15*	0.5
H21B	0.2347	0.8599	0.1048	0.15*	0.5
H21C	0.0811	0.8288	0.0604	0.15*	0.5
H21D	0.1514	0.8553	0.1101	0.15*	0.5
H21E	0.0942	0.8069	0.0054	0.15*	0.5
H21F	0.2478	0.8379	0.0498	0.15*	0.5
C22	0.1321 (2)	0.47983 (19)	0.16182 (16)	0.0571 (6)
O221	0.01192 (15)	0.50771 (13)	0.16555 (11)	0.0732 (5)
O222	0.15100 (18)	0.40274 (15)	0.11606 (13)	0.0845 (6)
C221	−0.1020 (3)	0.4376 (2)	0.1122 (2)	0.0921 (9)
H22A	−0.1838	0.4686	0.1173	0.138*
H22B	−0.0891	0.3628	0.1383	0.138*
H22C	−0.1083	0.4352	0.0458	0.138*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0613 (13)	0.0559 (13)	0.0594 (13)	0.0012 (11)	0.0240 (11)	−0.0091 (11)
C2	0.0536 (12)	0.0463 (12)	0.0567 (13)	−0.0009 (10)	0.0209 (10)	−0.0077 (10)
C3	0.0609 (13)	0.0612 (14)	0.0577 (13)	−0.0028 (11)	0.0229 (11)	−0.0120 (11)
C31	0.0556 (13)	0.0597 (14)	0.0498 (12)	−0.0060 (11)	0.0193 (10)	−0.0082 (10)
C32	0.0536 (14)	0.0673 (16)	0.0559 (13)	−0.0152 (11)	0.0162 (11)	−0.0086 (12)
C33	0.0487 (13)	0.0668 (16)	0.0549 (13)	−0.0044 (11)	0.0152 (11)	−0.0083 (12)
C34	0.0593 (14)	0.0567 (14)	0.0668 (15)	−0.0021 (11)	0.0247 (12)	−0.0015 (12)
C35	0.0574 (15)	0.0674 (17)	0.0946 (18)	−0.0103 (12)	0.0326 (13)	0.0054 (14)
C36	0.0499 (13)	0.0732 (17)	0.0754 (15)	−0.0010 (12)	0.0247 (12)	0.0001 (13)
O33	0.0528 (10)	0.0856 (13)	0.0905 (12)	−0.0008 (9)	0.0143 (9)	0.0086 (10)
O34	0.0677 (11)	0.0676 (11)	0.0998 (13)	0.0008 (9)	0.0270 (9)	0.0103 (10)
C37	0.0710 (17)	0.0665 (17)	0.0810 (17)	0.0040 (13)	0.0176 (14)	−0.0050 (14)
C11	0.0593 (15)	0.0673 (17)	0.0722 (15)	−0.0009 (12)	0.0294 (12)	−0.0075 (13)
O111	0.0572 (11)	0.0765 (12)	0.1274 (16)	−0.0041 (9)	0.0342 (10)	−0.0060 (11)
O112	0.0754 (12)	0.0759 (13)	0.154 (2)	−0.0126 (10)	0.0406 (13)	−0.0421 (13)
C111	0.0597 (17)	0.108 (2)	0.130 (3)	−0.0179 (16)	0.0300 (17)	−0.0066 (19)
C112	0.080 (2)	0.118 (3)	0.244 (5)	−0.004 (2)	0.024 (3)	−0.003 (3)
C21	0.0582 (14)	0.0550 (14)	0.0715 (16)	−0.0027 (11)	0.0275 (12)	−0.0090 (12)
O211	0.0898 (12)	0.0560 (10)	0.0776 (11)	0.0088 (8)	0.0373 (9)	0.0074 (8)
O212	0.0991 (13)	0.0602 (11)	0.1021 (14)	0.0164 (9)	0.0513 (12)	−0.0076 (9)
C211	0.121 (2)	0.0699 (18)	0.128 (2)	0.0295 (16)	0.067 (2)	0.0349 (18)
C22	0.0633 (15)	0.0504 (14)	0.0558 (13)	−0.0001 (11)	0.0176 (11)	−0.0012 (11)
O221	0.0524 (10)	0.0760 (11)	0.0862 (11)	−0.0073 (8)	0.0163 (8)	−0.0127 (9)
O222	0.0853 (12)	0.0691 (12)	0.0970 (13)	−0.0074 (9)	0.0275 (10)	−0.0306 (10)
C221	0.0673 (16)	0.097 (2)	0.098 (2)	−0.0237 (15)	0.0090 (15)	−0.0050 (17)

Geometric parameters (Å, º)

C1—C11	1.509 (3)	C11—O111	1.311 (3)
C1—C2	1.532 (3)	O111—C111	1.462 (3)
C1—H1A	0.97	C111—C112	1.409 (4)
C1—H1B	0.97	C111—H11A	0.97
C2—C22	1.526 (3)	C111—H11B	0.97
C2—C21	1.529 (3)	C112—H12A	0.96
C2—C3	1.556 (3)	C112—H12B	0.96
C3—C31	1.506 (3)	C112—H12C	0.96
C3—H3A	0.97	C112—H12D	0.96
C3—H3B	0.97	C112—H12E	0.96
C31—C36	1.385 (3)	C112—H12F	0.96
C31—C32	1.404 (3)	C21—O212	1.194 (2)
C32—C33	1.361 (3)	C21—O211	1.337 (3)
C32—H32	0.93	O211—C211	1.439 (3)
C33—C34	1.372 (3)	C211—H21A	0.96
C33—O33	1.381 (3)	C211—H21B	0.96
C34—C35	1.362 (3)	C211—H21C	0.96
C34—O34	1.381 (3)	C211—H21D	0.96
C35—C36	1.392 (3)	C211—H21E	0.96
C35—H35	0.93	C211—H21F	0.96
C36—H36	0.93	C22—O222	1.193 (3)
O33—C37	1.419 (3)	C22—O221	1.323 (3)
O34—C37	1.425 (3)	O221—C221	1.454 (3)
C37—H37A	0.97	C221—H22A	0.96
C37—H37B	0.97	C221—H22B	0.96
C11—O112	1.193 (3)	C221—H22C	0.96
C11—C1—C2	112.73 (17)	O111—C11—C1	112.4 (2)
C11—C1—H1A	109	C11—O111—C111	115.7 (2)
C2—C1—H1A	109	C112—C111—O111	110.9 (3)
C11—C1—H1B	109	C112—C111—H11A	109.5
C2—C1—H1B	109	O111—C111—H11A	109.5
H1A—C1—H1B	107.8	C112—C111—H11B	109.5
C22—C2—C21	107.06 (17)	O111—C111—H11B	109.5
C22—C2—C1	108.83 (17)	H11A—C111—H11B	108.1
C21—C2—C1	111.19 (17)	C111—C112—H12A	109.5
C22—C2—C3	109.05 (16)	C111—C112—H12B	109.5
C21—C2—C3	107.97 (17)	H12A—C112—H12B	109.5
C1—C2—C3	112.59 (17)	C111—C112—H12C	109.5
C31—C3—C2	115.88 (17)	H12A—C112—H12C	109.5
C31—C3—H3A	108.3	H12B—C112—H12C	109.5
C2—C3—H3A	108.3	C111—C112—H12D	109.5
C31—C3—H3B	108.3	C111—C112—H12E	109.5
C2—C3—H3B	108.3	H12D—C112—H12E	109.5
H3A—C3—H3B	107.4	C111—C112—H12F	109.5
C36—C31—C32	118.5 (2)	H12D—C112—H12F	109.5
C36—C31—C3	121.1 (2)	H12E—C112—H12F	109.5
C32—C31—C3	120.40 (19)	O212—C21—O211	123.5 (2)
C33—C32—C31	118.0 (2)	O212—C21—C2	126.3 (2)
C33—C32—H32	121	O211—C21—C2	110.13 (18)
C31—C32—H32	121	C21—O211—C211	116.19 (19)
C32—C33—C34	122.5 (2)	O211—C211—H21A	109.5
C32—C33—O33	128.0 (2)	O211—C211—H21B	109.5
C34—C33—O33	109.5 (2)	H21A—C211—H21B	109.5
C35—C34—C33	121.3 (2)	O211—C211—H21C	109.5
C35—C34—O34	128.7 (2)	H21A—C211—H21C	109.5
C33—C34—O34	110.0 (2)	H21B—C211—H21C	109.5
C34—C35—C36	116.8 (2)	O211—C211—H21D	109.5
C34—C35—H35	121.6	O211—C211—H21E	109.5
C36—C35—H35	121.6	H21D—C211—H21E	109.5
C31—C36—C35	122.8 (2)	O211—C211—H21F	109.5
C31—C36—H36	118.6	H21D—C211—H21F	109.5
C35—C36—H36	118.6	H21E—C211—H21F	109.5
C33—O33—C37	105.58 (17)	O222—C22—O221	123.8 (2)
C34—O34—C37	105.11 (17)	O222—C22—C2	125.1 (2)
O33—C37—O34	108.22 (19)	O221—C22—C2	111.05 (19)
O33—C37—H37A	110.1	C22—O221—C221	117.20 (19)
O34—C37—H37A	110.1	O221—C221—H22A	109.5
O33—C37—H37B	110.1	O221—C221—H22B	109.5
O34—C37—H37B	110.1	H22A—C221—H22B	109.5
H37A—C37—H37B	108.4	O221—C221—H22C	109.5
O112—C11—O111	122.9 (2)	H22A—C221—H22C	109.5
O112—C11—C1	124.7 (2)	H22B—C221—H22C	109.5