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Crystal structures of (±)-(1SR,5SR,6SR,7SR,10SR,11SR,13RS,14SR)-13-hy­dr­oxy-7-meth­­oxy­meth­­oxy-11,15,18,18-tetra­methyl-3-oxo-2,4-dioxa­tetra­cyclo­[12.3.1.01,5.06,11]octa­dec-15-en-10-yl benzoate, its 13-epimer and 13-one derivative

aSchool of Medicine, Keio University, Hiyoshi 4-1-1, Kohoku-ku, Yokohama 223-8521, Japan, and bDepartment of Applied Chemistry, Faculty of Science and Technology, Keio University, Hiyoshi 3-14-1, Kohoku-ku, Yokohama 223-8522, Japan
*Correspondence e-mail: oec@keio.jp

Edited by H. Ishida, Okayama University, Japan (Received 24 March 2015; accepted 6 April 2015; online 9 April 2015)

The title compounds, C29H38O8·0.25C5H12, (A), C29H38O8, (B), and C29H36O8, (C), are tetra­cyclic benzoates possessing a taxane skeleton with a fused dioxolane ring as the core structure. In the asymmetric unit of (A), there are two independent benzoate mol­ecules (A and A′) and a half mol­ecule of solvent pentane disordered about an inversion center. The mol­ecular conformations of (A), (B) and (C) are similar except for the flexible meth­oxy­meth­oxy group. The cyclo­hexane, cyclo­hexene and central cyclo­octane rings adopt chair, half-chair and chair–chair (extended crown) forms, respectively. The dioxolane rings are essentially planar, while the dioxolane ring of A′ is slightly twisted from the mean plane. In the crystal of (A), inter­molecular O—H⋯O, C—H⋯O and C—H⋯π inter­actions link the independent benzoates alternately, forming a chain structure. In the crystals of (B) and (C), mol­ecules are linked through O—H⋯O and C—H⋯π inter­actions, and C—H⋯O hydrogen bonds, respectively, into similar chains. Further, weak inter­molecular C—H⋯O inter­actions connect the chains into a three-dimensional network in (A) and a sheet in (B), whereas no other interactions are observed for (C).

1. Chemical context

Paclitaxel is a well-known natural diterpenoid containing a taxane framework (tri­cyclo­[9.3.1.03,8]penta­decane; Fig. 1[link]), with potent anti­tumor activity (Wall & Wani, 1995[Wall, M. E. & Wani, M. C. (1995). ACS Symp. Ser. 583, 18-30.]). The complicated structure and significant bioactivity have attracted chemical and medicinal inter­est. Recently, we reported the crystal structure of the precursor for cyclization to build the taxane skeleton (Oishi et al., 2015[Oishi, T., Yamaguchi, Y., Fukaya, K., Sugai, T., Watanabe, A., Sato, T. & Chida, N. (2015). Acta Cryst. E71, 8-11.]; §4), which was obtained in a synthetic study of paclitaxel. The cyclization reaction was accomplished (Fukaya et al., 2015[Fukaya, K., Sugai, T., Yamaguchi, Y., Watanabe, A., Sato, T. & Chida, N. (2015). In preparation.]) to afford strained tetra­cyclic benzoates (A) and its 13-epimer (B), then further oxidation gave a ketone (C).

[Scheme 1]
[Figure 1]
Figure 1
Left: Structure of the tri­cyclo­[9.3.1.03,8]penta­decane (taxane) skeleton; Right: Core structure of the title compounds. Red lines indicate the taxane skeleton. R1 = OC(=O)Ph, R2 = OCH2OCH3.

2. Structural commentary

The asymmetric units of the title compounds, (A), (B) and (C), are shown in Figs. 2[link], 3[link] and 4[link], respectively. Their mol­ecular conformations are similar except for the flexible meth­oxy­meth­oxy group (Fig. 5[link]).

[Figure 2]
Figure 2
The asymmetric unit of compound (A) with the atom labelling. Displacement ellipsoids are drawn at the 30% probability level. The left benzoate mol­ecule has been moved by a symmetry operation of (−x + 1, −y + 1, −z + 1) from its original position. The pentane solvent mol­ecule is disordered by symmetry over two sites with occupancy 0.50. Only H atoms connected to O and chiral C atoms are shown for clarity.
[Figure 3]
Figure 3
The asymmetric unit of compound (B) with the atom labelling. Displacement ellipsoids are drawn at the 30% probability level. Only H atoms connected to O and chiral C atoms are shown for clarity.
[Figure 4]
Figure 4
The asymmetric unit of compound (C) with the atom labelling. Displacement ellipsoids are drawn at the 30% probability level. Only H atoms connected to O and chiral C atoms are shown for clarity.
[Figure 5]
Figure 5
The mol­ecular conformations of compounds, (A), (B) and (C). In (A), there are two independent benzoates indicated as A (C1–C37) and A′ (C1′–C37′). Black dashed lines indicate the intra­molecular C—H⋯O inter­actions. Purple dotted lines indicate intra­molecular H⋯H short contacts. For clarity, only H atoms involved in these inter­actions are shown.

2.1. (±)-(1SR,5SR,6SR,7SR,10SR,11SR,13RS,14SR)-13-Hy­droxy-7-meth­oxy­meth­oxy-3-oxo-11,15,18,18-tetra­methyl-2,4-dioxa­tetra­cyclo­[12.3.1.01,5.06,11]octa­dec-15-en-10-yl benzoate, (A)

The two independent mol­ecules, A (C1–C37) and A′ (C1′–C37′), adopt slightly different conformations. The pentane solvent mol­ecule is disordered around the center of symmetry. The dioxolane ring in A (C1/C2/O20/C21/O22) is essentially planar with a maximum deviation of 0.0434 (18) Å for atom C1, while the dioxolane ring in A′ (C1′/C2′/O20′/C21′/O22′) shows a flattened twisted form with puckering parameters of Q(2) = 0.0713 (17) Å and φ(2) = 47.8 (14)°. Atoms C1′ and C2′ deviate from the mean plane of the other atoms by 0.104 (4) and −0.019 (4) Å, respectively.

The cyclo­hexane rings (C3–C8 in A and C3′–C8′ in A′) adopt chair forms with puckering parameters of Q = 0.5728 (19) Å, θ = 174.96 (19)°, φ = 352 (2)°, Q(2) = 0.0508 (19) Å and Q(3) = – 0.5705 (19) Å for the C3–C8 ring, and Q = 0.570 (2) Å, θ = 6.68 (19)°, φ = 181.2 (16)°, Q(2) = 0.0691 (19) Å and Q(3) = 0.5656 (19) Å for the C3′–C8′ ring. The larger substituents (C3—C2 and C3′—C2′; C4—O34 and C4′—C34′; C7—O24 and C7′—C24′) are in the equatorial positions, but substituents on quaternary carbons (C8—C9 and C8′—C9′) are slightly tilted from the equatorial positions with angles to the Cremer & Pople plane of 59.74 (13) and 59.59 (13)°, respectively.

The cyclo­hexene ring in A (C1/C14/C13/C12/C11/C15) adopts a half-chair form with puckering parameters of Q = 0.5419 (18) Å, θ = 50.2 (2)°, φ = 318.9 (3)°, Q(2) = 0.4162 (19) Å and Q(3) = −0.3470 (19) Å. Atoms C1 and C15 deviate from the mean plane of the other four atoms by 0.272 (3) and −0.547 (3) Å, respectively. The cyclo­hexene ring in A′ (C1′/C14′/C13′/C12′/C11′/C15′) also adopts a half-chair form with puckering parameters of Q = 0.5364 (19) Å, θ = 129.8 (2)°, φ = 138.8 (3)°, Q(2) = 0.4124 (19) Å and Q(3) = −0.3431 (19) Å. Atoms C1′ and C15′ deviate from the mean plane of other atoms by −0.268 (3) and 0.543 (3) Å, respectively.

The central cyclo­octane ring in A (C1–C3/C8–C11/C15) adopts a chair–chair (an extended crown) form with puckering parameters of Q = 0.8995 (18) Å, Q(2) = 0.3441 (18) Å, φ(2) = 305.1 (3)°, Q(3) = 0.0632 (18) Å, φ(3) = 180.8 (16)° and Q(4) = −0.8286 (18) Å. The cyclo­octane ring in A′ (C1′–C3′/C8′–C11′) also adopts a similar form with puckering parameters of Q = 0.8940 (18) Å, Q(2) = 0.3432 (18) Å, φ(2) = 130.3 (3)°, Q(3) = 0.0866 (19) Å, φ(3) = 11.1 (12)° and Q(4) = 0.8209 (18) Å. There is a short intra­molecular contact of 1.93 Å between atoms H2 and H10 in A, while the distance between H2′ and H10′ in A′ is 2.05 Å. The meth­oxy­meth­oxy groups (O34/C35/O36/C37 in A and O34′/C35′/O36′/C37′ in A′) show helical forms with weak intra­molecular C—H⋯O inter­actions (Fig. 5[link], Table 1[link]).

Table 1
Hydrogen-bond geometry (Å, °) for A[link]

Cg1 is the centroid of the C27–C32 benzene ring.

D—H⋯A D—H H⋯A DA D—H⋯A
C14—H14A⋯O34 0.99 2.47 3.320 (2) 143
C14′—H14D⋯O34′ 0.99 2.36 3.221 (2) 145
O33—H33⋯O22′i 0.84 2.05 2.8563 (17) 160
O33′—H33′⋯O22ii 0.84 2.05 2.8839 (16) 169
C7—H7⋯O26iii 1.00 2.28 3.236 (2) 159
C4′—H4′⋯O36iv 1.00 2.40 3.311 (2) 151
C17′—H17F⋯O33i 0.98 2.48 3.431 (2) 164
C30′—H30′⋯O23′v 0.95 2.53 3.453 (2) 163
C3P—H3PB⋯O33 0.99 2.49 3.369 (9) 149
C4P—H4PA⋯O33i 0.99 2.41 3.291 (12) 148
C16′—H16DCg1i 0.98 2.85 3.5315 (19) 127
Symmetry codes: (i) -x+1, -y+2, -z+1; (ii) -x+1, -y+1, -z+1; (iii) -x+1, -y+2, -z+2; (iv) x+1, y, z-1; (v) x, y-1, z.

2.2. (±)-(1SR,5SR,6SR,7SR,10SR,11SR,13SR,14SR)-13-Hy­droxy-7-meth­oxy­meth­oxy-3-oxo-11,15,18,18-tetra­methyl-2,4-dioxa­tetra­cyclo­[12.3.1.01,5.06,11]octa­dec-15-en-10-yl benzoate, (B)

Compound (B) is the C10-epimer of (A). The dioxolane ring in (B) (C1/C2/O20/C21/O22) is essentially planar with a maximum deviation of 0.0124 (11) Å for atom O22. The cyclo­hexane ring (C3–C8) adopts a chair form with puckering parameters of Q = 0.564 (2) Å, θ = 4.1 (2)°, φ = 124 (3)°, Q(2) = 0.039 (2) Å and Q(3) = 0.562 (2) Å. The larger substituents (C3—C2, C4—O34 and C7—O24) are in the equatorial positions, while the substituents on quaternary carbon (C8—C9) is slightly tilted from the equatorial position with an angle to the Cremer & Pople plane of 57.89 (13)°.

The cyclo­hexene ring (C1/C14/C13/C12/C11/C15) adopts a half-chair form with puckering parameters of Q = 0.540 (2) Å, θ = 130.1 (2)°, φ = 136.3 (3)°, Q(2) = 0.413 (2) Å and Q(3) = −0.348 (2) Å. Atoms C1 and C15 deviate from the mean plane of the other four atoms by 0.237 (4) and −0.575 (4) Å, respectively. The central cyclo­octane ring (C1–C3/C8–C11/C15) adopts a chair-chair form with puckering parameters of Q = 0.863 (2) Å, Q(2) = 0.283 (2) Å, φ(2) = 126.7 (4)°, Q(3) = 0.113 (2) Å, φ(3) = 23.1 (10)° and Q(4) = 0.807 (2) Å. The elongated bond lengths of 1.584 (3) Å for C10—C11 and 1.571 (3) Å for C11—C15, and the extraordinary sp3 angle of 126.80 (17)° for C8—C9—C10 suggest strain in the fused ring system. There are intra­molecular C—H⋯O inter­actions (C2—H2⋯O33 and C14—H14A⋯O34; Table 2[link]).

Table 2
Hydrogen-bond geometry (Å, °) for B[link]

Cg2 is the centroid of the C27–C32 benzene ring.

D—H⋯A D—H H⋯A DA D—H⋯A
C2—H2⋯O33 0.98 2.27 3.200 (2) 157
C14—H14A⋯O34 0.97 2.47 3.293 (2) 142
O33—H33⋯O23i 0.82 1.96 2.7823 (19) 179
C7—H7⋯O26ii 0.98 2.50 3.353 (2) 145
C16—H16ACg2iii 0.98 2.93 3.594 (2) 128
Symmetry codes: (i) [x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]; (ii) -x+2, -y, -z+2; (iii) [x-{\script{3\over 2}}, -y-{\script{1\over 2}}, z-{\script{3\over 2}}].

2.3. (±)-(1SR,5SR,6SR,7SR,10SR,11SR,14SR)-3,13-Dioxo-7-meth­oxy­meth­oxy-11,15,18,18-tetra­methyl-2,4-dioxa­tetra­cyclo­[12.3.1.01,5.06,11]octa­dec-15-en-10-yl benzoate, (C)

Compound (C) is the C10-oxo derivative of (A) and (B). The dioxolane ring in (C) (C1/C2/O20/C21/O22) is essentially planar with a maximum deviation of 0.0280 (12) Å for atom O22. The cyclo­hexane ring (C3–C8) adopts a chair form with puckering parameters of Q = 0.563 (2) Å, θ = 5.9 (2)°, φ = 227 (2)°, Q(2) = 0.056 (2) Å and Q(3) = 0.560 (2) Å. The substituents including that on the quaternary carbon (C3—C2, C4—O34, C7—O24 and C8—C9) are in the equatorial positions.

The cyclo­hexene ring (C1/C14/C13/C12/C11/C15) adopts a half-chair form with puckering parameters of Q = 0.533 (2) Å, θ = 131.7 (2)°, φ = 135.3 (3)°, Q(2) = 0.398 (2) Å and Q(3) = −0.354 (2) Å. Atoms C1 and C15 deviate from the mean plane of the other four atoms by 0.222 (4) and −0.577 (4) Å, respectively. The central cyclo­octane ring (C1–C3/C8–C11/C15) adopts a chair-chair form with puckering parameters of Q = 0.898 (2) Å, Q(2) = 0.311 (2) Å, φ(2) = 113.2 (4)°, Q(3) = 0.066 (2) Å, φ(3) = 353 (2)° and Q(4) = 0.839 (2) Å. There is a short intra­molecular contact of 1.88 Å between the atoms H2 and H16A.

3. Supra­molecular features

3.1. Compound (A)

The crystal packing is stabilized by inter­molecular O—H⋯O hydrogen bonds (O33—H33⋯O22′i and O33′—H33′⋯O22ii; Table 1[link]) connecting the A and A′ mol­ecules alternately to form a chain with a C(7) motif running along the b axis (Fig. 6[link]). Further inter­molecular weak C—H⋯O and C—H⋯π inter­actions (C17′—C17F⋯O33i, C30′—H30′⋯O23′v and C16′—H16DCg1i; Table 1[link]) support the chain structure. Inter­estingly, the geometric data for the corresponding inter­actions (C17—H17C⋯O33′ii, C30—H30⋯O23vi and C16—H16ACg1′) are 2.76 Å for H17C⋯O33′ii, 2.80 Å for H30⋯O23vi and 2.95 Å for H16—Cg1′, and 118.8° for C30—H30⋯O23vi and 119° for C16—H16ACg1′, which are out of the range for proper values of a hydrogen bond [symmetry code: (vi) x, y + 1, z; Cg1′ is the centroid of the C27′–C32′ benzene ring.]

[Figure 6]
Figure 6
A partial packing view of (A) showing the chain structure. Yellow lines indicate the inter­molecular O—H⋯O hydrogen bonds, generating C(7) chains. Black dashed lines indicate the weak inter­molecular C—H⋯O and C—H⋯π inter­actions. Cg1 is the centroid of the C27–C32 benzene ring. Only H atoms involved in hydrogen bonds are shown for clarity. The pentane solvent mol­ecules have been omitted. [Symmetry codes: (i) −x + 1, −y + 2, −z + 1; (ii) −x + 1, −y + 1, −z + 1; (v) x, y − 1, z.]

The chains are inter­locked by a pair of inter­molecular C—H⋯O hydrogen bonds (C7—H7⋯O26iii; Table 1[link]) with an R22(10) graph-set motif, forming a tape parallel to ([\overline{1}]01) and along the b axis (Fig. 7[link]). The adjacent tapes are connected by inter­molecular C—H⋯O inter­actions (C4′—H4′⋯O36iv; Table 1[link]), forming a layer parallel to (001). Among the layers, disordered solvent pentane mol­ecules are held by weak inter­molecular C—H⋯O inter­actions (C3P—H3PB⋯O33 and C4P—H4PA⋯O33i; Table 1[link]), constructing a three-dimensional architecture.

[Figure 7]
Figure 7
A packing diagram of (A) viewed down to b axis showing a three-dimensional network. The chains (projected as butterfly-like shapes) are connected by the inter­molecular C—H⋯O inter­actions (black dashed lines). Only H atoms involved in hydrogen bonds are shown for clarity. [Symmetry codes: (iii) −x + 1, −y + 2, −z + 2; (iv) x + 1, y, z − 1.]

3.2. Compound (B)

The crystal packing is stabilized by an inter­molecular O—H⋯O hydrogen bond (O33—H33⋯O23i; Table 2[link]) connecting the enanti­omers alternately to form a chain with a C(9) motif along [101] (Fig. 8[link]). Further, an inter­molecular weak C—H⋯π inter­action (C16—H16ACg2iii; Table 2[link]) supports the chain formation. The chains are connected by a pair of inter­molecular C—H⋯O hydrogen bonds (C7—H7⋯O26ii; Fig. 9[link], Table 2[link]) with an R22(10) graph-set motif, forming a sheet parallel to (10[\overline{1}]).

[Figure 8]
Figure 8
A partial packing view of (B) showing a chain structure. The inter­molecular O—H⋯O hydrogen bonds (yellow lines) link the enanti­omers alternately, generating C(9) chains. In the chain, further inter­molecular weak C—H⋯π inter­actions (black dashed lines) are also observed. Cg2 is the centroid of the C27–C32 phenyl ring. Only H atoms involved in hydrogen bonds are shown for clarity. [Symmetry codes: (i) x + [{1\over 2}], −y + [{1\over 2}], −z + [{1\over 2}]; (iii) x − [{1\over 2}], −y + [{1\over 2}], z − [{1\over 2}].]
[Figure 9]
Figure 9
A packing diagram of (B) viewed along [[\overline{1}]0[\overline{1}]], showing parallel sheets. The chains (projected as fly-like shapes) are connected by pairs of inter­molecular C—H⋯O inter­actions (black dashed lines), forming sheets parallel to (10[\overline{1}]). Only H atoms involved in hydrogen bonds are shown for clarity. [Symmetry codes: (ii) −x + 2, −y, −z + 2.]

3.3. Compound (C)

The crystal packing is stabilized by a pair of inter­molecular C—H⋯O inter­actions (C31—H31⋯O33i; Table 3[link]) with an R22(22) graph-set motif, forming an inversion dimer (Figs. 10[link] and 11[link]). The dimers are further linked into a chain along the c axis by inter­molecular C—H⋯O inter­actions (C19—H19C⋯O23ii and C16—H16A⋯O23ii; Table 3[link]) with R22(16) and R22(14) graph-set motifs, respectively. There is an inter­molecular O36⋯C25iii short contact of 3.012 (3) Å involving the carbonyl group of the benzoyl moiety [symmetry code: (iii) x, −y + [{3\over 2}], z − [{1\over 2}]].

Table 3
Hydrogen-bond geometry (Å, °) for C[link]

D—H⋯A D—H H⋯A DA D—H⋯A
C31—H31⋯O33i 0.95 2.35 3.147 (3) 141
C19—H19C⋯O23ii 0.98 2.43 3.310 (3) 149
C16—H16A⋯O23ii 0.98 2.56 3.491 (3) 158
Symmetry codes: (i) -x+2, -y+1, -z+2; (ii) -x+2, -y+1, -z+1.
[Figure 10]
Figure 10
A partial packing view of (C) showing the chain structure. Inter­molecular C—H⋯O inter­actions (blacked dashed lines) link the enanti­omers. Only H atoms involved in hydrogen bonds are shown for clarity. [Symmetry codes: (i) −x + 2, −y + 1, −z + 2; (ii) −x + 2, −y + 1, −z + 1.]
[Figure 11]
Figure 11
A packing diagram of (C) viewed down the c axis. Black dashed lines indicate the inter­molecular C—H⋯O inter­actions. Overlapped mol­ecules (projection as a spider-like shape) do not constitute the same chain. A half body of the spider is only linked to the adjacent inverted one.

4. Database survey

In the Cambridge Structural Database (CSD, Version 5.36, November 2014; Groom & Allen, 2014[Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662-671.]), 85 structures containing a tri­cyclo­[9.3.1.03,8]penta­dec-11-ene skeleton, (a), are found (Fig. 12[link]). These include a large number of paclitaxels and its analogues, and one compound (NEGBOQ; Poujol et al., 1997[Poujol, H., Ahond, A., Al Mourabit, A., Chiaroni, A., Poupat, C., Riche, C. & Potier, P. (1997). Tetrahedron, 53, 5169-5184.]) containing a 2,4-dioxa­tetra­cyclo[12.3.1.01,5.06,11]octa­dec-14-ene skeleton, (e), which is an olefin regioisomer for the tetra­cyclic core of the title compound, (d). On the other hand, there are two related structures (PAHTEZ; Mendoza et al., 2011[Mendoza, A., Ishihara, Y. & Baran, P. S. (2011). Nat. Chem. 4, 21-25.], and RIYTAW; Wilde et al., 2014[Wilde, M. C., Isomura, M., Mendoza, A. & Baran, P. S. (2014). J. Am. Chem. Soc. 136, 4909-4912.]) containing a tri­cyclo­[9.3.1.03,8]penta­dec-12-ene skeleton, (b), and one related structure (SOJWOD; Paquette & Zhao, 1998[Paquette, L. A. & Zhao, M. (1998). J. Am. Chem. Soc. 120, 5203-5212.]) for a tri­cyclo­[9.3.1.03,8]penta­dec-13-ene skeleton, (c).

[Figure 12]
Figure 12
Core structures for database survey; tri­cyclo­[9.3.1.03,8]penta­decane (taxane) and its (a) 11-ene, (b) 12-ene and (c) 13-ene derivatives, (d) tetra­cyclic core of the title compounds and (e) its regioisomer of olefin and (f) de­hydro derivative of regioisomer.

Another tetra­cyclic taxoid (ILIQUP; Ohba et al., 2003[Ohba, S., Chinen, A., Matsumoto, Y. & Chida, N. (2003). Acta Cryst. E59, o1476-o1477.]), which was unexpectedly generated by a cyclization reaction in our previous study, is closely related to the title compound. Additionally, a precursor of cyclization obtained in our previous study is also available (NOTROF; Oishi et al., 2015[Oishi, T., Yamaguchi, Y., Fukaya, K., Sugai, T., Watanabe, A., Sato, T. & Chida, N. (2015). Acta Cryst. E71, 8-11.]). Another compound, closely related to the title compounds with a 2,4-dioxa­tetra­cyclo­[12.3.1.01,5.06,11]octa­deca-8,14-diene skeleton, (f), was reported in the literature (Nicolaou et al., 1995[Nicolaou, K. C., Yang, Z., Liu, J., Nantermet, P. G., Claiborne, C. F., Renaud, J., Guy, R. K. & Shibayama, K. (1995). J. Am. Chem. Soc. 117, 645-652.]), but was not deposited in the CSD.

5. Synthesis and crystallization

The title compounds were obtained in a synthetic study on paclitaxel (Fukaya et al., 2015[Fukaya, K., Sugai, T., Yamaguchi, Y., Watanabe, A., Sato, T. & Chida, N. (2015). In preparation.]). The cyclo­hexene unit (C1/C14/C13/C12/C11/C15) was synthesized according to a reported procedure (Nicolaou et al., 1995[Nicolaou, K. C., Yang, Z., Liu, J., Nantermet, P. G., Claiborne, C. F., Renaud, J., Guy, R. K. & Shibayama, K. (1995). J. Am. Chem. Soc. 117, 645-652.]), and coupled with the substituted cyclo­hexane unit (C3–C8) prepared from 3-methyl­anisole by a Shapiro reaction (Nicolaou et al., 1995[Nicolaou, K. C., Yang, Z., Liu, J., Nantermet, P. G., Claiborne, C. F., Renaud, J., Guy, R. K. & Shibayama, K. (1995). J. Am. Chem. Soc. 117, 645-652.]). Further manipulation of the functional groups and cyclization reaction afforded the tetra­cyclic benzoates (A) and its C10-epimer (B), which were oxidized into ketone (C). Each compound was purified by silica gel chromatography. Colorless crystals of (A) were grown from a benzene solution under a pentane-saturated atmosphere by slow evaporation at ambient temperature. Similarly, colorless crystals of (B) and (C) were obtained in the same manner.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4[link]. C-bound H atoms were positioned geometrically with C—H = 0.95–1.00 Å, and constrained to ride on their parent atoms with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C). The H atom of hy­droxy group was placed guided by difference maps, with O—H = 0.84 Å and with Uiso(H) = 1.5Ueq(O).

Table 4
Experimental details

  A B C
Crystal data
Chemical formula C29H38O8·0.25C5H12 C29H38O8 C29H36O8
Mr 532.64 514.59 512.59
Crystal system, space group Triclinic, P[\overline{1}] Monoclinic, P21/n Monoclinic, P21/c
Temperature (K) 90 90 90
a, b, c (Å) 11.3343 (5), 15.4666 (7), 16.4870 (8) 9.3612 (6), 19.6336 (15), 14.1965 (9) 13.2416 (8), 13.1779 (8), 15.2428 (8)
α, β, γ (°) 85.1124 (14), 78.3773 (14), 78.5231 (15) 90, 101.762 (2), 90 90, 109.387 (2), 90
V3) 2771.3 (2) 2554.4 (3) 2509.0 (3)
Z 4 4 4
Radiation type Mo Kα Mo Kα Mo Kα
μ (mm−1) 0.09 0.10 0.10
Crystal size (mm) 0.32 × 0.21 × 0.17 0.23 × 0.23 × 0.14 0.22 × 0.14 × 0.09
 
Data collection
Diffractometer Bruker D8 Venture Bruker D8 Venture Bruker D8 Venture
Absorption correction Multi-scan (SADABS; Bruker, 2014[Bruker (2014). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Multi-scan (SADABS; Bruker, 2014[Bruker (2014). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Multi-scan (SADABS; Bruker, 2014[Bruker (2014). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.])
Tmin, Tmax 0.97, 0.98 0.98, 0.99 0.92, 0.99
No. of measured, independent and observed [I > 2σ(I)] reflections 50997, 9735, 7339 23252, 4480, 3212 22512, 4395, 3050
Rint 0.041 0.058 0.063
(sin θ/λ)max−1) 0.595 0.595 0.595
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.040, 0.099, 1.02 0.043, 0.111, 1.02 0.044, 0.105, 0.96
No. of reflections 9735 4480 4395
No. of parameters 726 340 339
H-atom treatment H-atom parameters constrained H-atom parameters constrained H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 0.27, −0.24 0.51, −0.21 0.29, −0.25
Computer programs: APEX2 and SAINT (Bruker, 2014[Bruker (2014). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]), SHELXS2013 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), SHELXL2014 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]), Mercury (Macrae et al., 2006[Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453-457.]), publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]) and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Supporting information


Computing details top

For all compounds, data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: publCIF (Westrip, 2010) and PLATON (Spek, 2009).

(A) (±)-(1SR,5SR,6SR,7SR,10SR,11SR,13RS,14SR)-13-Hydroxy-7-methoxymethoxy-11,15,18,18-tetramethyl-3-oxo-2,4-dioxatetracyclo[12.3.1.01,5.06,11]octadec-15-en-10-yl benzoate pentane 0.25-solvate top
Crystal data top
C29H38O8·0.25C5H12F(000) = 1146
Mr = 532.64Dx = 1.277 Mg m3
Triclinic, P1Melting point: 509.2 K
a = 11.3343 (5) ÅMo Kα radiation, λ = 0.71073 Å
b = 15.4666 (7) ÅCell parameters from 9428 reflections
c = 16.4870 (8) Åθ = 2.4–25.0°
α = 85.1124 (14)°µ = 0.09 mm1
β = 78.3773 (14)°T = 90 K
γ = 78.5231 (15)°Prism, colorless
V = 2771.3 (2) Å30.32 × 0.21 × 0.17 mm
Z = 4
Data collection top
Bruker D8 Venture
diffractometer
9735 independent reflections
Radiation source: fine-focus sealed tube7339 reflections with I > 2σ(I)
Multilayered confocal mirror monochromatorRint = 0.041
Detector resolution: 8.333 pixels mm-1θmax = 25.0°, θmin = 2.2°
φ and ω scansh = 1313
Absorption correction: multi-scan
(SADABS; Bruker, 2014)
k = 1818
Tmin = 0.97, Tmax = 0.98l = 1919
50997 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.039P)2 + 1.4256P]
where P = (Fo2 + 2Fc2)/3
9735 reflections(Δ/σ)max = 0.008
726 parametersΔρmax = 0.27 e Å3
0 restraintsΔρmin = 0.24 e Å3
Special details top

Experimental. M.p. 507.2–509.2 K (not corrected); IR (film) 3502, 2950, 1799, 1717, 1451, 1272, 1098, 1055, 713 cm-1; 1H NMR (500 MHz, CDCl3) δ (p.p.m.) 8.03–8.00 (m, 2H), 7.60–7.55 (m, 1H), 7.48–7.43 (m, 2H), 5.50 (bs, 1H), 4.78 (d, J = 7.2 Hz, 1H), 4.71 (dd, J = 11.3, 4.3 Hz, 1H), 4.58 (d, J = 7.2 Hz, 1H), 4.50 (d, J = 3.7 Hz, 1H), 4.31 (dd, J = 9.0, 2.0 Hz, 1H), 3.56 (ddd, J = 10.7, 10.7, 5.2 Hz, 1H), 3.35 (s, 3H), 2.87 (bd, J = 18.3 Hz, 1H), 2.41–2.30 (m, 2H), 2.11 (s, 1H), 2.08 (dd, J = 10.7, 3.7 Hz, 1H), 1.89 (dddd, J = 12.7, 4.3, 4.0, 4.0 Hz, 1H), 1.77 (s, 3H), 1.72–1.50 (m, 4H), 1.29 (s, 3H), 1.25 (s, 3H), 1.17 (s, 3H); 13C NMR (125 MHz, CDCl3) δ (p.p.m.) 165.9 (C), 154.1 (C), 136.7 (C), 133.4 (CH), 130.3 (C), 129.7 (CH), 128.6 (CH), 120.9 (CH), 97.8 (CH2), 87.1 (C), 80.0 (CH), 78.1 (CH), 75.0 (CH), 67.1 (CH), 60.6 (CH), 55.9 (CH3), 47.8 (CH2), 46.2 (CH), 42.6 (C), 40.2 (C), 31.9 (CH2), 31.2 (CH2), 25.9 (CH3), 25.1 (CH3), 24.7 (CH2), 19.8 (CH3), 13.6 (CH3); LRMS (EI) m/z 514 (M+, 4%), 483 (1), 469 (1), 453 (1), 409 (4), 393 (12), 348 (1), 332 (1), 121 (83), 105 (100), 77 (67); HRMS (EI) m/z calcd for C29H38O8+ [M]+ 514.2567, found 514.2545.

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.

Problematic three reflections with |I(obs)-I(calc)|/σW(I) greater than 10 (1 1 0, 9 9 11 and 5 3 11) have been omitted in the final refinement.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
C10.39192 (15)0.71883 (11)0.80546 (10)0.0182 (4)
C20.29323 (15)0.76771 (11)0.87419 (10)0.0178 (4)
H20.23660.81230.84550.021*
C30.33237 (15)0.81694 (11)0.93856 (10)0.0167 (4)
H30.42270.81460.92120.02*
C40.31165 (16)0.77206 (11)1.02534 (11)0.0199 (4)
H40.22340.7671.04280.024*
C50.34803 (17)0.82311 (11)1.08803 (11)0.0228 (4)
H5A0.43730.82251.07390.027*
H5B0.32970.79431.14390.027*
C60.27850 (17)0.91845 (11)1.08866 (11)0.0231 (4)
H6A0.18930.91961.10490.028*
H6B0.30350.95131.12930.028*
C70.30713 (16)0.96120 (11)1.00303 (10)0.0192 (4)
H70.39730.96040.98850.023*
C80.27009 (15)0.91625 (11)0.93435 (10)0.0169 (4)
C90.32337 (16)0.96195 (11)0.85154 (10)0.0196 (4)
H9B0.2851.02530.85420.024*
H9A0.41160.95850.85110.024*
C100.31409 (16)0.93271 (11)0.76616 (10)0.0196 (4)
H100.23260.91530.77030.024*
C110.41687 (15)0.85809 (11)0.72360 (10)0.0184 (4)
H110.43450.87950.66420.022*
C120.53785 (16)0.85012 (11)0.75254 (10)0.0201 (4)
C130.58295 (16)0.77927 (11)0.79574 (11)0.0211 (4)
H130.6590.77820.8120.025*
C140.52260 (15)0.70092 (11)0.82067 (11)0.0201 (4)
H14A0.5220.68540.88020.024*
H14B0.57060.64990.78880.024*
C150.38464 (15)0.76528 (11)0.72002 (10)0.0191 (4)
C160.25946 (16)0.77064 (12)0.69574 (11)0.0225 (4)
H16A0.19410.79160.74230.034*
H16B0.25150.7120.68190.034*
H16C0.25290.81180.64760.034*
C170.47951 (17)0.71477 (12)0.65165 (11)0.0237 (4)
H17B0.46750.7420.59730.036*
H17C0.46920.65310.65470.036*
H17A0.56230.71710.65940.036*
C180.60684 (17)0.92447 (12)0.72667 (12)0.0278 (4)
H18A0.63970.92330.6670.042*
H18B0.67450.91770.75690.042*
H18C0.55130.98090.73920.042*
C190.13055 (15)0.92911 (11)0.94717 (11)0.0214 (4)
H19C0.10760.90050.90340.032*
H19A0.09580.99240.9450.032*
H19B0.09880.90271.00130.032*
O200.22400 (11)0.70057 (8)0.91336 (7)0.0214 (3)
C210.26240 (16)0.62580 (12)0.87360 (11)0.0216 (4)
O220.35432 (11)0.63298 (7)0.80929 (7)0.0215 (3)
O230.22106 (12)0.56013 (8)0.89208 (8)0.0298 (3)
O240.24272 (10)1.05356 (7)1.00196 (7)0.0201 (3)
C250.30152 (16)1.11360 (11)1.02153 (10)0.0197 (4)
O260.39773 (11)1.09511 (8)1.04546 (8)0.0283 (3)
C270.23598 (16)1.20589 (11)1.01040 (10)0.0194 (4)
C280.29728 (17)1.27379 (12)1.01677 (11)0.0231 (4)
H280.37821.26021.02780.028*
C290.24120 (18)1.36072 (12)1.00719 (11)0.0272 (4)
H290.28371.40681.01130.033*
C300.12343 (18)1.38076 (12)0.99168 (11)0.0275 (4)
H300.08471.44070.98550.033*
C310.06173 (17)1.31401 (12)0.98513 (12)0.0276 (4)
H310.01951.32810.97480.033*
C320.11788 (16)1.22643 (12)0.99364 (11)0.0226 (4)
H320.07581.18060.9880.027*
O330.32219 (12)1.00634 (8)0.70805 (8)0.0276 (3)
H330.26641.0490.72460.041*
O340.38701 (11)0.68492 (7)1.01813 (7)0.0218 (3)
C350.33439 (17)0.61646 (12)1.06299 (11)0.0248 (4)
H35A0.24770.6251.05680.03*
H35B0.37740.55971.03870.03*
O360.33867 (12)0.61094 (8)1.14683 (7)0.0288 (3)
C370.4588 (2)0.58010 (15)1.16272 (15)0.0452 (6)
H37B0.51320.61931.13350.068*
H37C0.4890.52011.14320.068*
H37A0.4570.57951.22240.068*
C1'0.80525 (16)0.74195 (11)0.31038 (11)0.0190 (4)
C2'0.90913 (15)0.67289 (11)0.26359 (10)0.0185 (4)
H2'0.87110.64230.22740.022*
C3'0.98195 (15)0.60049 (11)0.31378 (10)0.0182 (4)
H3'0.93970.60520.37310.022*
C4'1.11310 (16)0.61437 (11)0.30982 (11)0.0225 (4)
H4'1.15510.61920.25060.027*
C5'1.18605 (17)0.53955 (12)0.35504 (12)0.0274 (4)
H5'A1.15050.53970.4150.033*
H5'B1.27180.54830.34780.033*
C6'1.18424 (17)0.45122 (12)0.32163 (12)0.0265 (4)
H6'A1.22180.45010.2620.032*
H6'B1.23210.40280.35140.032*
C7'1.05332 (16)0.43877 (11)0.33368 (11)0.0216 (4)
H7'1.01720.44050.39420.026*
C8'0.97153 (15)0.50882 (11)0.28678 (10)0.0188 (4)
C9'0.83902 (16)0.49154 (11)0.31629 (11)0.0205 (4)
H9'A0.82450.48860.37760.025*
H9'B0.840.43140.29950.025*
C10'0.72291 (15)0.55088 (11)0.29171 (11)0.0193 (4)
H10'0.74010.56670.23090.023*
C11'0.66133 (16)0.63631 (11)0.33978 (10)0.0189 (4)
H11'0.57150.63770.34540.023*
C12'0.68111 (15)0.62936 (11)0.42879 (11)0.0191 (4)
C13'0.74589 (16)0.68057 (11)0.45440 (11)0.0211 (4)
H13'0.75480.67320.51080.025*
C14'0.80599 (16)0.74896 (12)0.40147 (11)0.0220 (4)
H14D0.89170.74180.40940.026*
H14E0.76250.80840.41910.026*
C15'0.67950 (16)0.72807 (11)0.29790 (11)0.0199 (4)
C16'0.66754 (17)0.73683 (12)0.20653 (11)0.0237 (4)
H16D0.73620.69740.17430.036*
H16E0.66860.7980.18570.036*
H16F0.59020.72070.20120.036*
C17'0.57506 (16)0.79806 (11)0.34144 (12)0.0237 (4)
H17D0.57140.79110.40150.036*
H17E0.4970.79040.32880.036*
H17F0.59030.85720.32180.036*
C18'0.61846 (17)0.56509 (12)0.48620 (11)0.0264 (4)
H18D0.52940.58380.49210.04*
H18E0.64170.56310.54060.04*
H18F0.64330.50630.46350.04*
C19'1.01302 (17)0.49893 (12)0.19299 (11)0.0237 (4)
H19D1.02530.43660.18060.035*
H19E1.09020.52050.17420.035*
H19F0.95010.53350.16420.035*
O20'0.98878 (11)0.72516 (7)0.20899 (7)0.0218 (3)
C21'0.93856 (16)0.81059 (12)0.21184 (11)0.0219 (4)
O22'0.83303 (11)0.82463 (7)0.26720 (7)0.0230 (3)
O23'0.98135 (12)0.86793 (8)0.17053 (8)0.0291 (3)
O24'1.05092 (11)0.35259 (7)0.30544 (7)0.0232 (3)
C25'1.05285 (16)0.28473 (12)0.36162 (11)0.0230 (4)
O26'1.05309 (14)0.29155 (9)0.43359 (8)0.0366 (4)
C27'1.05285 (16)0.20029 (11)0.32452 (11)0.0226 (4)
C28'1.03407 (19)0.12820 (13)0.37777 (13)0.0328 (5)
H28'1.02360.13320.43590.039*
C29'1.0305 (2)0.04866 (13)0.34638 (14)0.0403 (5)
H29'1.01670.00060.38310.048*
C30'1.04693 (18)0.04084 (13)0.26221 (13)0.0343 (5)
H30'1.0440.01370.24090.041*
C31'1.06757 (16)0.11189 (12)0.20896 (12)0.0270 (4)
H31'1.08040.10590.15080.032*
C32'1.06975 (15)0.19203 (12)0.23947 (11)0.0231 (4)
H32'1.08280.24120.20240.028*
O33'0.62847 (11)0.49828 (8)0.30885 (8)0.0254 (3)
H33'0.64350.45950.27360.038*
O34'1.09963 (11)0.69699 (8)0.34778 (8)0.0255 (3)
C35'1.1978 (2)0.74151 (14)0.32338 (13)0.0370 (5)
H35D1.22640.73750.26280.044*
H35F1.16850.80470.3350.044*
O36'1.29654 (12)0.70912 (10)0.36255 (10)0.0446 (4)
C37'1.2687 (2)0.72296 (17)0.44817 (15)0.0529 (7)
H37D1.34150.69980.47250.079*
H37E1.20210.69230.47470.079*
H37F1.24320.78640.45690.079*
C1P0.2437 (5)0.9991 (4)0.5096 (4)0.0466 (14)0.5
H1PA0.21921.00950.5690.07*0.5
H1PB0.19430.95990.49450.07*0.5
H1PC0.23071.05550.47770.07*0.5
C2P0.3778 (6)0.9566 (6)0.4905 (6)0.0345 (17)0.5
H2PA0.40020.9420.43140.041*0.5
H2PB0.39060.90070.52420.041*0.5
C3P0.4624 (5)1.0156 (5)0.5077 (5)0.036 (3)0.5
H3PA0.45361.06960.4710.043*0.5
H3PB0.43571.03380.56560.043*0.5
C4P0.5962 (7)0.9719 (8)0.4947 (7)0.044 (2)0.5
H4PA0.62280.95280.4370.053*0.5
H4PB0.60550.91840.53220.053*0.5
C5P0.6788 (7)1.0321 (6)0.5108 (6)0.047 (2)0.5
H5PA0.67411.08340.47150.07*0.5
H5PB0.76360.99980.50380.07*0.5
H5PC0.65211.05220.56750.07*0.5
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0196 (9)0.0124 (9)0.0231 (9)0.0029 (7)0.0042 (7)0.0035 (7)
C20.0196 (9)0.0145 (9)0.0193 (9)0.0040 (7)0.0026 (7)0.0005 (7)
C30.0138 (9)0.0148 (9)0.0206 (9)0.0020 (7)0.0009 (7)0.0039 (7)
C40.0203 (10)0.0151 (9)0.0226 (10)0.0024 (7)0.0008 (8)0.0021 (7)
C50.0287 (11)0.0216 (10)0.0192 (9)0.0069 (8)0.0045 (8)0.0011 (8)
C60.0247 (10)0.0228 (10)0.0223 (10)0.0053 (8)0.0021 (8)0.0077 (8)
C70.0174 (9)0.0146 (9)0.0248 (10)0.0008 (7)0.0030 (8)0.0042 (7)
C80.0149 (9)0.0166 (9)0.0186 (9)0.0031 (7)0.0010 (7)0.0029 (7)
C90.0190 (9)0.0154 (9)0.0241 (10)0.0014 (7)0.0038 (8)0.0037 (7)
C100.0195 (9)0.0159 (9)0.0219 (9)0.0012 (7)0.0034 (7)0.0019 (7)
C110.0189 (9)0.0188 (9)0.0163 (9)0.0027 (7)0.0013 (7)0.0010 (7)
C120.0188 (9)0.0220 (10)0.0183 (9)0.0031 (7)0.0001 (7)0.0049 (8)
C130.0153 (9)0.0255 (10)0.0219 (9)0.0019 (7)0.0030 (7)0.0048 (8)
C140.0200 (10)0.0172 (9)0.0211 (9)0.0022 (7)0.0035 (8)0.0035 (7)
C150.0185 (9)0.0194 (9)0.0188 (9)0.0027 (7)0.0025 (7)0.0033 (7)
C160.0255 (10)0.0225 (10)0.0209 (9)0.0042 (8)0.0070 (8)0.0026 (8)
C170.0263 (10)0.0220 (10)0.0220 (10)0.0020 (8)0.0038 (8)0.0044 (8)
C180.0232 (10)0.0267 (11)0.0327 (11)0.0050 (8)0.0034 (8)0.0006 (9)
C190.0178 (9)0.0188 (9)0.0269 (10)0.0013 (7)0.0025 (8)0.0071 (8)
O200.0205 (7)0.0192 (7)0.0249 (7)0.0077 (5)0.0003 (5)0.0052 (5)
C210.0230 (10)0.0206 (10)0.0225 (10)0.0041 (8)0.0071 (8)0.0023 (8)
O220.0245 (7)0.0153 (6)0.0241 (7)0.0046 (5)0.0015 (6)0.0038 (5)
O230.0360 (8)0.0211 (7)0.0353 (8)0.0141 (6)0.0050 (6)0.0013 (6)
O240.0193 (6)0.0147 (6)0.0271 (7)0.0027 (5)0.0042 (5)0.0065 (5)
C250.0187 (10)0.0205 (10)0.0204 (9)0.0044 (8)0.0021 (8)0.0051 (7)
O260.0252 (8)0.0221 (7)0.0403 (8)0.0016 (6)0.0127 (6)0.0069 (6)
C270.0233 (10)0.0180 (9)0.0158 (9)0.0026 (7)0.0012 (7)0.0033 (7)
C280.0240 (10)0.0229 (10)0.0236 (10)0.0040 (8)0.0059 (8)0.0054 (8)
C290.0372 (12)0.0194 (10)0.0271 (10)0.0077 (8)0.0070 (9)0.0044 (8)
C300.0347 (12)0.0173 (10)0.0254 (10)0.0029 (8)0.0011 (9)0.0009 (8)
C310.0184 (10)0.0287 (11)0.0314 (11)0.0018 (8)0.0019 (8)0.0013 (9)
C320.0212 (10)0.0233 (10)0.0233 (10)0.0071 (8)0.0011 (8)0.0018 (8)
O330.0342 (8)0.0182 (7)0.0259 (7)0.0014 (6)0.0026 (6)0.0019 (6)
O340.0255 (7)0.0151 (6)0.0237 (7)0.0036 (5)0.0030 (5)0.0006 (5)
C350.0298 (11)0.0187 (10)0.0274 (10)0.0073 (8)0.0076 (8)0.0029 (8)
O360.0321 (8)0.0298 (7)0.0229 (7)0.0051 (6)0.0048 (6)0.0051 (6)
C370.0452 (14)0.0441 (14)0.0534 (15)0.0124 (11)0.0287 (12)0.0146 (11)
C1'0.0211 (10)0.0112 (9)0.0243 (10)0.0038 (7)0.0033 (8)0.0000 (7)
C2'0.0175 (9)0.0180 (9)0.0209 (9)0.0068 (7)0.0034 (7)0.0008 (7)
C3'0.0185 (9)0.0171 (9)0.0181 (9)0.0020 (7)0.0031 (7)0.0003 (7)
C4'0.0204 (10)0.0221 (10)0.0261 (10)0.0044 (8)0.0056 (8)0.0031 (8)
C5'0.0193 (10)0.0299 (11)0.0341 (11)0.0042 (8)0.0097 (8)0.0017 (9)
C6'0.0237 (10)0.0219 (10)0.0318 (11)0.0030 (8)0.0085 (8)0.0011 (8)
C7'0.0242 (10)0.0176 (9)0.0224 (10)0.0009 (7)0.0048 (8)0.0031 (7)
C8'0.0189 (9)0.0175 (9)0.0199 (9)0.0019 (7)0.0043 (7)0.0022 (7)
C9'0.0240 (10)0.0144 (9)0.0238 (10)0.0033 (7)0.0053 (8)0.0034 (7)
C10'0.0207 (10)0.0168 (9)0.0221 (9)0.0063 (7)0.0045 (8)0.0030 (7)
C11'0.0170 (9)0.0172 (9)0.0231 (9)0.0039 (7)0.0032 (7)0.0038 (7)
C12'0.0179 (9)0.0163 (9)0.0214 (9)0.0003 (7)0.0010 (7)0.0039 (7)
C13'0.0213 (10)0.0232 (10)0.0181 (9)0.0021 (8)0.0031 (8)0.0043 (8)
C14'0.0216 (10)0.0195 (10)0.0260 (10)0.0042 (7)0.0041 (8)0.0067 (8)
C15'0.0202 (10)0.0153 (9)0.0245 (10)0.0023 (7)0.0047 (8)0.0042 (7)
C16'0.0235 (10)0.0203 (10)0.0271 (10)0.0014 (8)0.0074 (8)0.0002 (8)
C17'0.0211 (10)0.0181 (10)0.0319 (11)0.0022 (7)0.0052 (8)0.0039 (8)
C18'0.0265 (11)0.0252 (10)0.0263 (10)0.0050 (8)0.0014 (8)0.0033 (8)
C19'0.0258 (10)0.0194 (10)0.0243 (10)0.0001 (8)0.0046 (8)0.0029 (8)
O20'0.0205 (7)0.0184 (7)0.0248 (7)0.0039 (5)0.0021 (5)0.0033 (5)
C21'0.0204 (10)0.0216 (10)0.0260 (10)0.0064 (8)0.0079 (8)0.0007 (8)
O22'0.0226 (7)0.0148 (6)0.0303 (7)0.0043 (5)0.0021 (6)0.0009 (5)
O23'0.0298 (8)0.0242 (7)0.0345 (8)0.0115 (6)0.0059 (6)0.0067 (6)
O24'0.0294 (7)0.0154 (6)0.0235 (7)0.0007 (5)0.0069 (5)0.0016 (5)
C25'0.0204 (10)0.0235 (10)0.0255 (11)0.0023 (8)0.0077 (8)0.0011 (8)
O26'0.0626 (10)0.0264 (8)0.0268 (8)0.0135 (7)0.0178 (7)0.0013 (6)
C27'0.0184 (10)0.0195 (10)0.0301 (11)0.0006 (7)0.0075 (8)0.0021 (8)
C28'0.0420 (13)0.0270 (11)0.0291 (11)0.0067 (9)0.0059 (9)0.0012 (9)
C29'0.0523 (14)0.0217 (11)0.0457 (14)0.0112 (10)0.0027 (11)0.0000 (10)
C30'0.0337 (12)0.0260 (11)0.0440 (13)0.0073 (9)0.0034 (10)0.0121 (10)
C31'0.0191 (10)0.0304 (11)0.0315 (11)0.0022 (8)0.0030 (8)0.0115 (9)
C32'0.0141 (9)0.0242 (10)0.0305 (11)0.0008 (7)0.0048 (8)0.0029 (8)
O33'0.0259 (7)0.0194 (7)0.0340 (8)0.0078 (5)0.0057 (6)0.0095 (6)
O34'0.0230 (7)0.0230 (7)0.0334 (7)0.0082 (5)0.0084 (6)0.0017 (6)
C35'0.0419 (13)0.0394 (13)0.0365 (12)0.0245 (10)0.0065 (10)0.0009 (10)
O36'0.0221 (8)0.0521 (10)0.0644 (11)0.0103 (7)0.0081 (7)0.0220 (8)
C37'0.0500 (15)0.0592 (16)0.0602 (17)0.0112 (12)0.0312 (13)0.0112 (13)
C1P0.040 (3)0.054 (4)0.045 (3)0.006 (3)0.007 (3)0.007 (3)
C2P0.047 (5)0.029 (3)0.026 (3)0.002 (4)0.006 (4)0.005 (2)
C3P0.057 (9)0.022 (5)0.021 (3)0.000 (6)0.008 (6)0.008 (3)
C4P0.054 (7)0.042 (4)0.031 (3)0.003 (5)0.002 (4)0.004 (3)
C5P0.047 (6)0.051 (5)0.040 (3)0.011 (5)0.003 (5)0.008 (3)
Geometric parameters (Å, º) top
C1—O221.466 (2)C3'—C8'1.555 (2)
C1—C141.519 (2)C3'—H3'1.0
C1—C151.536 (2)C4'—O34'1.438 (2)
C1—C21.551 (2)C4'—C5'1.516 (2)
C2—O201.455 (2)C4'—H4'1.0
C2—C31.538 (2)C5'—C6'1.521 (3)
C2—H21.0C5'—H5'A0.99
C3—C41.531 (2)C5'—H5'B0.99
C3—C81.560 (2)C6'—C7'1.506 (3)
C3—H31.0C6'—H6'A0.99
C4—O341.445 (2)C6'—H6'B0.99
C4—C51.517 (2)C7'—O24'1.456 (2)
C4—H41.0C7'—C8'1.542 (2)
C5—C61.527 (2)C7'—H7'1.0
C5—H5A0.99C8'—C19'1.534 (2)
C5—H5B0.99C8'—C9'1.552 (2)
C6—C71.509 (2)C9'—C10'1.552 (2)
C6—H6A0.99C9'—H9'A0.99
C6—H6B0.99C9'—H9'B0.99
C7—O241.470 (2)C10'—O33'1.440 (2)
C7—C81.544 (2)C10'—C11'1.565 (2)
C7—H71.0C10'—H10'1.0
C8—C191.527 (2)C11'—C12'1.520 (2)
C8—C91.550 (2)C11'—C15'1.557 (2)
C9—C101.544 (2)C11'—H11'1.0
C9—H9B0.99C12'—C13'1.326 (2)
C9—H9A0.99C12'—C18'1.496 (2)
C10—O331.429 (2)C13'—C14'1.495 (2)
C10—C111.567 (2)C13'—H13'0.95
C10—H101.0C14'—H14D0.99
C11—C121.520 (2)C14'—H14E0.99
C11—C151.559 (2)C15'—C16'1.532 (2)
C11—H111.0C15'—C17'1.539 (2)
C12—C131.327 (2)C16'—H16D0.98
C12—C181.502 (2)C16'—H16E0.98
C13—C141.496 (2)C16'—H16F0.98
C13—H130.95C17'—H17D0.98
C14—H14A0.99C17'—H17E0.98
C14—H14B0.99C17'—H17F0.98
C15—C161.535 (2)C18'—H18D0.98
C15—C171.538 (2)C18'—H18E0.98
C16—H16A0.98C18'—H18F0.98
C16—H16B0.98C19'—H19D0.98
C16—H16C0.98C19'—H19E0.98
C17—H17B0.98C19'—H19F0.98
C17—H17C0.98O20'—C21'1.331 (2)
C17—H17A0.98C21'—O23'1.192 (2)
C18—H18A0.98C21'—O22'1.342 (2)
C18—H18B0.98O24'—C25'1.339 (2)
C18—H18C0.98C25'—O26'1.201 (2)
C19—H19C0.98C25'—C27'1.489 (3)
C19—H19A0.98C27'—C28'1.383 (3)
C19—H19B0.98C27'—C32'1.390 (3)
O20—C211.330 (2)C28'—C29'1.385 (3)
C21—O231.193 (2)C28'—H28'0.95
C21—O221.343 (2)C29'—C30'1.375 (3)
O24—C251.340 (2)C29'—H29'0.95
C25—O261.207 (2)C30'—C31'1.374 (3)
C25—C271.487 (2)C30'—H30'0.95
C27—C321.391 (2)C31'—C32'1.383 (3)
C27—C281.391 (2)C31'—H31'0.95
C28—C291.379 (3)C32'—H32'0.95
C28—H280.95O33'—H33'0.84
C29—C301.379 (3)O34'—C35'1.397 (2)
C29—H290.95C35'—O36'1.390 (3)
C30—C311.380 (3)C35'—H35D0.99
C30—H300.95C35'—H35F0.99
C31—C321.386 (3)O36'—C37'1.408 (3)
C31—H310.95C37'—H37D0.98
C32—H320.95C37'—H37E0.98
O33—H330.84C37'—H37F0.98
O34—C351.401 (2)C1P—C2P1.512 (7)
C35—O361.388 (2)C1P—H1PA0.98
C35—H35A0.99C1P—H1PB0.98
C35—H35B0.99C1P—H1PC0.98
O36—C371.419 (2)C2P—C3P1.527 (12)
C37—H37B0.98C2P—H2PA0.99
C37—H37C0.98C2P—H2PB0.99
C37—H37A0.98C3P—C4P1.513 (9)
C1'—O22'1.468 (2)C3P—H3PA0.99
C1'—C14'1.517 (2)C3P—H3PB0.99
C1'—C15'1.539 (2)C4P—C5P1.519 (13)
C1'—C2'1.548 (2)C4P—H4PA0.99
C2'—O20'1.455 (2)C4P—H4PB0.99
C2'—C3'1.539 (2)C5P—H5PA0.98
C2'—H2'1.0C5P—H5PB0.98
C3'—C4'1.531 (2)C5P—H5PC0.98
O22—C1—C14106.92 (13)C4'—C3'—H3'106.8
O22—C1—C15109.83 (13)C2'—C3'—H3'106.8
C14—C1—C15110.95 (14)C8'—C3'—H3'106.8
O22—C1—C2101.66 (13)O34'—C4'—C5'111.30 (14)
C14—C1—C2115.83 (14)O34'—C4'—C3'105.04 (13)
C15—C1—C2111.06 (13)C5'—C4'—C3'111.67 (15)
O20—C2—C3111.66 (13)O34'—C4'—H4'109.6
O20—C2—C1104.22 (12)C5'—C4'—H4'109.6
C3—C2—C1119.74 (14)C3'—C4'—H4'109.6
O20—C2—H2106.8C4'—C5'—C6'110.44 (15)
C3—C2—H2106.8C4'—C5'—H5'A109.6
C1—C2—H2106.8C6'—C5'—H5'A109.6
C4—C3—C2112.38 (14)C4'—C5'—H5'B109.6
C4—C3—C8114.30 (13)C6'—C5'—H5'B109.6
C2—C3—C8109.19 (13)H5'A—C5'—H5'B108.1
C4—C3—H3106.8C7'—C6'—C5'108.79 (15)
C2—C3—H3106.8C7'—C6'—H6'A109.9
C8—C3—H3106.8C5'—C6'—H6'A109.9
O34—C4—C5110.55 (14)C7'—C6'—H6'B109.9
O34—C4—C3105.85 (13)C5'—C6'—H6'B109.9
C5—C4—C3111.33 (14)H6'A—C6'—H6'B108.3
O34—C4—H4109.7O24'—C7'—C6'109.24 (14)
C5—C4—H4109.7O24'—C7'—C8'107.71 (13)
C3—C4—H4109.7C6'—C7'—C8'114.27 (15)
C4—C5—C6110.58 (14)O24'—C7'—H7'108.5
C4—C5—H5A109.5C6'—C7'—H7'108.5
C6—C5—H5A109.5C8'—C7'—H7'108.5
C4—C5—H5B109.5C19'—C8'—C7'109.93 (14)
C6—C5—H5B109.5C19'—C8'—C9'111.03 (14)
H5A—C5—H5B108.1C7'—C8'—C9'105.96 (14)
C7—C6—C5108.84 (14)C19'—C8'—C3'112.37 (14)
C7—C6—H6A109.9C7'—C8'—C3'106.79 (13)
C5—C6—H6A109.9C9'—C8'—C3'110.48 (14)
C7—C6—H6B109.9C8'—C9'—C10'124.69 (14)
C5—C6—H6B109.9C8'—C9'—H9'A106.2
H6A—C6—H6B108.3C10'—C9'—H9'A106.2
O24—C7—C6110.10 (13)C8'—C9'—H9'B106.2
O24—C7—C8106.75 (13)C10'—C9'—H9'B106.2
C6—C7—C8114.54 (14)H9'A—C9'—H9'B106.3
O24—C7—H7108.4O33'—C10'—C9'106.31 (13)
C6—C7—H7108.4O33'—C10'—C11'102.98 (13)
C8—C7—H7108.4C9'—C10'—C11'119.59 (14)
C19—C8—C7109.82 (14)O33'—C10'—H10'109.1
C19—C8—C9111.08 (14)C9'—C10'—H10'109.1
C7—C8—C9105.73 (13)C11'—C10'—H10'109.1
C19—C8—C3112.58 (14)C12'—C11'—C15'110.97 (14)
C7—C8—C3106.92 (13)C12'—C11'—C10'112.90 (14)
C9—C8—C3110.40 (13)C15'—C11'—C10'119.20 (14)
C10—C9—C8122.76 (14)C12'—C11'—H11'104.0
C10—C9—H9B106.6C15'—C11'—H11'104.0
C8—C9—H9B106.6C10'—C11'—H11'104.0
C10—C9—H9A106.6C13'—C12'—C18'122.25 (16)
C8—C9—H9A106.6C13'—C12'—C11'121.39 (16)
H9B—C9—H9A106.6C18'—C12'—C11'116.29 (15)
O33—C10—C9108.12 (14)C12'—C13'—C14'125.10 (16)
O33—C10—C11103.00 (13)C12'—C13'—H13'117.4
C9—C10—C11118.56 (14)C14'—C13'—H13'117.4
O33—C10—H10108.9C13'—C14'—C1'111.79 (14)
C9—C10—H10108.9C13'—C14'—H14D109.3
C11—C10—H10108.9C1'—C14'—H14D109.3
C12—C11—C15110.87 (14)C13'—C14'—H14E109.3
C12—C11—C10113.25 (14)C1'—C14'—H14E109.3
C15—C11—C10118.18 (14)H14D—C14'—H14E107.9
C12—C11—H11104.3C16'—C15'—C1'112.57 (14)
C15—C11—H11104.3C16'—C15'—C17'105.41 (14)
C10—C11—H11104.3C1'—C15'—C17'111.34 (14)
C13—C12—C18121.45 (16)C16'—C15'—C11'113.16 (14)
C13—C12—C11121.67 (16)C1'—C15'—C11'106.73 (13)
C18—C12—C11116.82 (15)C17'—C15'—C11'107.59 (14)
C12—C13—C14124.68 (16)C15'—C16'—H16D109.5
C12—C13—H13117.7C15'—C16'—H16E109.5
C14—C13—H13117.7H16D—C16'—H16E109.5
C13—C14—C1111.73 (14)C15'—C16'—H16F109.5
C13—C14—H14A109.3H16D—C16'—H16F109.5
C1—C14—H14A109.3H16E—C16'—H16F109.5
C13—C14—H14B109.3C15'—C17'—H17D109.5
C1—C14—H14B109.3C15'—C17'—H17E109.5
H14A—C14—H14B107.9H17D—C17'—H17E109.5
C16—C15—C1112.74 (14)C15'—C17'—H17F109.5
C16—C15—C17105.90 (14)H17D—C17'—H17F109.5
C1—C15—C17110.91 (14)H17E—C17'—H17F109.5
C16—C15—C11112.53 (14)C12'—C18'—H18D109.5
C1—C15—C11106.34 (13)C12'—C18'—H18E109.5
C17—C15—C11108.40 (14)H18D—C18'—H18E109.5
C15—C16—H16A109.5C12'—C18'—H18F109.5
C15—C16—H16B109.5H18D—C18'—H18F109.5
H16A—C16—H16B109.5H18E—C18'—H18F109.5
C15—C16—H16C109.5C8'—C19'—H19D109.5
H16A—C16—H16C109.5C8'—C19'—H19E109.5
H16B—C16—H16C109.5H19D—C19'—H19E109.5
C15—C17—H17B109.5C8'—C19'—H19F109.5
C15—C17—H17C109.5H19D—C19'—H19F109.5
H17B—C17—H17C109.5H19E—C19'—H19F109.5
C15—C17—H17A109.5C21'—O20'—C2'110.28 (13)
H17B—C17—H17A109.5O23'—C21'—O20'124.57 (17)
H17C—C17—H17A109.5O23'—C21'—O22'123.78 (16)
C12—C18—H18A109.5O20'—C21'—O22'111.64 (15)
C12—C18—H18B109.5C21'—O22'—C1'111.54 (13)
H18A—C18—H18B109.5C25'—O24'—C7'117.38 (13)
C12—C18—H18C109.5O26'—C25'—O24'123.87 (17)
H18A—C18—H18C109.5O26'—C25'—C27'124.10 (17)
H18B—C18—H18C109.5O24'—C25'—C27'112.03 (15)
C8—C19—H19C109.5C28'—C27'—C32'119.59 (17)
C8—C19—H19A109.5C28'—C27'—C25'117.84 (17)
H19C—C19—H19A109.5C32'—C27'—C25'122.57 (16)
C8—C19—H19B109.5C27'—C28'—C29'120.05 (19)
H19C—C19—H19B109.5C27'—C28'—H28'120.0
H19A—C19—H19B109.5C29'—C28'—H28'120.0
C21—O20—C2110.60 (13)C30'—C29'—C28'120.18 (19)
O23—C21—O20124.81 (17)C30'—C29'—H29'119.9
O23—C21—O22123.59 (16)C28'—C29'—H29'119.9
O20—C21—O22111.60 (15)C31'—C30'—C29'120.00 (19)
C21—O22—C1111.40 (13)C31'—C30'—H30'120.0
C25—O24—C7116.45 (13)C29'—C30'—H30'120.0
O26—C25—O24123.80 (16)C30'—C31'—C32'120.44 (18)
O26—C25—C27123.31 (16)C30'—C31'—H31'119.8
O24—C25—C27112.90 (15)C32'—C31'—H31'119.8
C32—C27—C28119.41 (16)C31'—C32'—C27'119.73 (17)
C32—C27—C25122.92 (16)C31'—C32'—H32'120.1
C28—C27—C25117.67 (16)C27'—C32'—H32'120.1
C29—C28—C27120.35 (17)C10'—O33'—H33'109.5
C29—C28—H28119.8C35'—O34'—C4'115.53 (14)
C27—C28—H28119.8O36'—C35'—O34'114.07 (17)
C28—C29—C30120.01 (18)O36'—C35'—H35D108.7
C28—C29—H29120.0O34'—C35'—H35D108.7
C30—C29—H29120.0O36'—C35'—H35F108.7
C29—C30—C31120.18 (17)O34'—C35'—H35F108.7
C29—C30—H30119.9H35D—C35'—H35F107.6
C31—C30—H30119.9C35'—O36'—C37'112.82 (17)
C30—C31—C32120.23 (17)O36'—C37'—H37D109.5
C30—C31—H31119.9O36'—C37'—H37E109.5
C32—C31—H31119.9H37D—C37'—H37E109.5
C31—C32—C27119.80 (17)O36'—C37'—H37F109.5
C31—C32—H32120.1H37D—C37'—H37F109.5
C27—C32—H32120.1H37E—C37'—H37F109.5
C10—O33—H33109.5C2P—C1P—H1PA109.5
C35—O34—C4115.66 (13)C2P—C1P—H1PB109.5
O36—C35—O34114.13 (14)H1PA—C1P—H1PB109.5
O36—C35—H35A108.7C2P—C1P—H1PC109.5
O34—C35—H35A108.7H1PA—C1P—H1PC109.5
O36—C35—H35B108.7H1PB—C1P—H1PC109.5
O34—C35—H35B108.7C1P—C2P—C3P113.0 (6)
H35A—C35—H35B107.6C1P—C2P—H2PA109.0
C35—O36—C37112.85 (15)C3P—C2P—H2PA109.0
O36—C37—H37B109.5C1P—C2P—H2PB109.0
O36—C37—H37C109.5C3P—C2P—H2PB109.0
H37B—C37—H37C109.5H2PA—C2P—H2PB107.8
O36—C37—H37A109.5C4P—C3P—C2P113.9 (5)
H37B—C37—H37A109.5C4P—C3P—H3PA108.8
H37C—C37—H37A109.5C2P—C3P—H3PA108.8
O22'—C1'—C14'107.45 (13)C4P—C3P—H3PB108.8
O22'—C1'—C15'109.95 (13)C2P—C3P—H3PB108.8
C14'—C1'—C15'111.00 (14)H3PA—C3P—H3PB107.7
O22'—C1'—C2'101.43 (13)C3P—C4P—C5P113.0 (6)
C14'—C1'—C2'116.01 (14)C3P—C4P—H4PA109.0
C15'—C1'—C2'110.45 (13)C5P—C4P—H4PA109.0
O20'—C2'—C3'111.74 (13)C3P—C4P—H4PB109.0
O20'—C2'—C1'104.56 (13)C5P—C4P—H4PB109.0
C3'—C2'—C1'119.08 (14)H4PA—C4P—H4PB107.8
O20'—C2'—H2'106.9C4P—C5P—H5PA109.5
C3'—C2'—H2'106.9C4P—C5P—H5PB109.5
C1'—C2'—H2'106.9H5PA—C5P—H5PB109.5
C4'—C3'—C2'112.31 (14)C4P—C5P—H5PC109.5
C4'—C3'—C8'115.02 (14)H5PA—C5P—H5PC109.5
C2'—C3'—C8'108.62 (13)H5PB—C5P—H5PC109.5
O22—C1—C2—O206.62 (15)C14'—C1'—C2'—O20'109.03 (15)
C14—C1—C2—O20108.85 (15)C15'—C1'—C2'—O20'123.57 (14)
C15—C1—C2—O20123.41 (14)O22'—C1'—C2'—C3'132.64 (15)
O22—C1—C2—C3132.30 (14)C14'—C1'—C2'—C3'16.6 (2)
C14—C1—C2—C316.8 (2)C15'—C1'—C2'—C3'110.81 (17)
C15—C1—C2—C3110.91 (17)O20'—C2'—C3'—C4'13.44 (19)
O20—C2—C3—C411.23 (19)C1'—C2'—C3'—C4'108.67 (17)
C1—C2—C3—C4110.86 (16)O20'—C2'—C3'—C8'114.93 (15)
O20—C2—C3—C8116.69 (14)C1'—C2'—C3'—C8'122.97 (16)
C1—C2—C3—C8121.21 (16)C2'—C3'—C4'—O34'62.79 (17)
C2—C3—C4—O3461.23 (17)C8'—C3'—C4'—O34'172.30 (13)
C8—C3—C4—O34173.60 (13)C2'—C3'—C4'—C5'176.44 (15)
C2—C3—C4—C5178.60 (14)C8'—C3'—C4'—C5'51.5 (2)
C8—C3—C4—C553.42 (19)O34'—C4'—C5'—C6'172.16 (14)
O34—C4—C5—C6173.67 (14)C3'—C4'—C5'—C6'55.1 (2)
C3—C4—C5—C656.31 (19)C4'—C5'—C6'—C7'59.6 (2)
C4—C5—C6—C759.01 (19)C5'—C6'—C7'—O24'177.36 (14)
C5—C6—C7—O24179.24 (13)C5'—C6'—C7'—C8'61.9 (2)
C5—C6—C7—C860.47 (19)O24'—C7'—C8'—C19'54.39 (18)
O24—C7—C8—C1954.43 (17)C6'—C7'—C8'—C19'67.17 (19)
C6—C7—C8—C1967.71 (18)O24'—C7'—C8'—C9'65.65 (16)
O24—C7—C8—C965.48 (16)C6'—C7'—C8'—C9'172.78 (14)
C6—C7—C8—C9172.38 (14)O24'—C7'—C8'—C3'176.55 (13)
O24—C7—C8—C3176.86 (13)C6'—C7'—C8'—C3'54.99 (19)
C6—C7—C8—C354.72 (18)C4'—C3'—C8'—C19'71.54 (18)
C4—C3—C8—C1970.39 (18)C2'—C3'—C8'—C19'55.28 (18)
C2—C3—C8—C1956.45 (18)C4'—C3'—C8'—C7'49.07 (19)
C4—C3—C8—C750.29 (18)C2'—C3'—C8'—C7'175.89 (14)
C2—C3—C8—C7177.14 (13)C4'—C3'—C8'—C9'163.86 (14)
C4—C3—C8—C9164.85 (14)C2'—C3'—C8'—C9'69.33 (17)
C2—C3—C8—C968.31 (17)C19'—C8'—C9'—C10'66.3 (2)
C19—C8—C9—C1064.8 (2)C7'—C8'—C9'—C10'174.41 (15)
C7—C8—C9—C10176.12 (14)C3'—C8'—C9'—C10'59.1 (2)
C3—C8—C9—C1060.8 (2)C8'—C9'—C10'—O33'161.84 (15)
C8—C9—C10—O33155.68 (15)C8'—C9'—C10'—C11'82.4 (2)
C8—C9—C10—C1187.7 (2)O33'—C10'—C11'—C12'89.06 (16)
O33—C10—C11—C1295.01 (16)C9'—C10'—C11'—C12'28.5 (2)
C9—C10—C11—C1224.3 (2)O33'—C10'—C11'—C15'138.00 (15)
O33—C10—C11—C15132.92 (15)C9'—C10'—C11'—C15'104.46 (18)
C9—C10—C11—C15107.80 (18)C15'—C11'—C12'—C13'21.8 (2)
C15—C11—C12—C1322.0 (2)C10'—C11'—C12'—C13'115.02 (18)
C10—C11—C12—C13113.52 (18)C15'—C11'—C12'—C18'155.27 (15)
C15—C11—C12—C18155.30 (15)C10'—C11'—C12'—C18'67.92 (19)
C10—C11—C12—C1869.16 (19)C18'—C12'—C13'—C14'177.07 (16)
C18—C12—C13—C14177.24 (16)C11'—C12'—C13'—C14'0.2 (3)
C11—C12—C13—C140.0 (3)C12'—C13'—C14'—C1'10.8 (2)
C12—C13—C14—C111.1 (2)O22'—C1'—C14'—C13'164.26 (14)
O22—C1—C14—C13164.41 (13)C15'—C1'—C14'—C13'44.01 (19)
C15—C1—C14—C1344.66 (19)C2'—C1'—C14'—C13'83.12 (18)
C2—C1—C14—C1383.13 (18)O22'—C1'—C15'—C16'51.20 (18)
O22—C1—C15—C1652.28 (18)C14'—C1'—C15'—C16'169.96 (14)
C14—C1—C15—C16170.27 (14)C2'—C1'—C15'—C16'59.92 (18)
C2—C1—C15—C1659.38 (18)O22'—C1'—C15'—C17'66.92 (18)
O22—C1—C15—C1766.29 (17)C14'—C1'—C15'—C17'51.83 (18)
C14—C1—C15—C1751.70 (18)C2'—C1'—C15'—C17'178.04 (14)
C2—C1—C15—C17177.95 (14)O22'—C1'—C15'—C11'175.93 (13)
O22—C1—C15—C11176.05 (12)C14'—C1'—C15'—C11'65.31 (17)
C14—C1—C15—C1165.96 (17)C2'—C1'—C15'—C11'64.81 (17)
C2—C1—C15—C1164.39 (17)C12'—C11'—C15'—C16'176.85 (14)
C12—C11—C15—C16176.78 (14)C10'—C11'—C15'—C16'43.1 (2)
C10—C11—C15—C1643.7 (2)C12'—C11'—C15'—C1'52.47 (17)
C12—C11—C15—C152.87 (17)C10'—C11'—C15'—C1'81.28 (18)
C10—C11—C15—C180.24 (17)C12'—C11'—C15'—C17'67.12 (17)
C12—C11—C15—C1766.44 (17)C10'—C11'—C15'—C17'159.12 (14)
C10—C11—C15—C17160.45 (14)C3'—C2'—O20'—C21'136.82 (14)
C3—C2—O20—C21135.34 (14)C1'—C2'—O20'—C21'6.71 (17)
C1—C2—O20—C214.71 (17)C2'—O20'—C21'—O23'176.50 (16)
C2—O20—C21—O23179.45 (17)C2'—O20'—C21'—O22'3.45 (19)
C2—O20—C21—O220.49 (18)O23'—C21'—O22'—C1'178.39 (16)
O23—C21—O22—C1175.69 (16)O20'—C21'—O22'—C1'1.65 (19)
O20—C21—O22—C14.37 (19)C14'—C1'—O22'—C21'116.66 (15)
C14—C1—O22—C21115.03 (15)C15'—C1'—O22'—C21'122.43 (15)
C15—C1—O22—C21124.50 (14)C2'—C1'—O22'—C21'5.52 (17)
C2—C1—O22—C216.83 (17)C6'—C7'—O24'—C25'91.63 (18)
C6—C7—O24—C2588.35 (17)C8'—C7'—O24'—C25'143.73 (15)
C8—C7—O24—C25146.75 (14)C7'—O24'—C25'—O26'2.1 (3)
C7—O24—C25—O265.8 (2)C7'—O24'—C25'—C27'178.74 (14)
C7—O24—C25—C27173.98 (13)O26'—C25'—C27'—C28'9.8 (3)
O26—C25—C27—C32171.09 (17)O24'—C25'—C27'—C28'169.38 (16)
O24—C25—C27—C329.1 (2)O26'—C25'—C27'—C32'170.79 (18)
O26—C25—C27—C289.3 (3)O24'—C25'—C27'—C32'10.0 (2)
O24—C25—C27—C28170.50 (15)C32'—C27'—C28'—C29'0.9 (3)
C32—C27—C28—C290.5 (3)C25'—C27'—C28'—C29'178.55 (18)
C25—C27—C28—C29179.89 (16)C27'—C28'—C29'—C30'0.7 (3)
C27—C28—C29—C300.4 (3)C28'—C29'—C30'—C31'0.3 (3)
C28—C29—C30—C310.5 (3)C29'—C30'—C31'—C32'1.2 (3)
C29—C30—C31—C320.4 (3)C30'—C31'—C32'—C27'1.0 (3)
C30—C31—C32—C271.2 (3)C28'—C27'—C32'—C31'0.0 (3)
C28—C27—C32—C311.3 (3)C25'—C27'—C32'—C31'179.37 (16)
C25—C27—C32—C31179.11 (16)C5'—C4'—O34'—C35'83.68 (19)
C5—C4—O34—C3599.01 (17)C3'—C4'—O34'—C35'155.31 (15)
C3—C4—O34—C35140.30 (14)C4'—O34'—C35'—O36'79.7 (2)
C4—O34—C35—O3679.12 (18)O34'—C35'—O36'—C37'66.5 (2)
O34—C35—O36—C3771.1 (2)C1P—C2P—C3P—C4P175.9 (6)
O22'—C1'—C2'—O20'7.02 (15)C2P—C3P—C4P—C5P179.1 (10)
Hydrogen-bond geometry (Å, º) top
Cg1 is the centroid of the C27–C32 benzene ring.
D—H···AD—HH···AD···AD—H···A
C14—H14A···O340.992.473.320 (2)143
C14—H14D···O340.992.363.221 (2)145
O33—H33···O22i0.842.052.8563 (17)160
O33—H33···O22ii0.842.052.8839 (16)169
C7—H7···O26iii1.002.283.236 (2)159
C4—H4···O36iv1.002.403.311 (2)151
C17—H17F···O33i0.982.483.431 (2)164
C30—H30···O23v0.952.533.453 (2)163
C3P—H3PB···O330.992.493.369 (9)149
C4P—H4PA···O33i0.992.413.291 (12)148
C16—H16D···Cg1i0.982.853.5315 (19)127
Symmetry codes: (i) x+1, y+2, z+1; (ii) x+1, y+1, z+1; (iii) x+1, y+2, z+2; (iv) x+1, y, z1; (v) x, y1, z.
(B) (±)-(1SR,5SR,6SR,7SR,10SR,11SR,13SR,14SR)-13-Hydroxy-7-methoxymethoxy-11,15,18,18-tetramethyl-3-oxo-2,4-dioxatetracyclo[12.3.1.01,5.06,11]octadec-15-en-10-yl benzoate top
Crystal data top
C29H38O8Dx = 1.338 Mg m3
Mr = 514.59Melting point: 489.2 K
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 9.3612 (6) ÅCell parameters from 4716 reflections
b = 19.6336 (15) Åθ = 2.4–23.9°
c = 14.1965 (9) ŵ = 0.10 mm1
β = 101.762 (2)°T = 90 K
V = 2554.4 (3) Å3Prism, colorless
Z = 40.23 × 0.23 × 0.14 mm
F(000) = 1104
Data collection top
Bruker D8 Venture
diffractometer
4480 independent reflections
Radiation source: fine-focus sealed tube3212 reflections with I > 2σ(I)
Multilayered confocal mirror monochromatorRint = 0.058
Detector resolution: 8.333 pixels mm-1θmax = 25.0°, θmin = 2.5°
φ and ω scansh = 1111
Absorption correction: multi-scan
(SADABS; Bruker, 2014)
k = 2321
Tmin = 0.98, Tmax = 0.99l = 1616
23252 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.111H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.054P)2 + 1.0752P]
where P = (Fo2 + 2Fc2)/3
4480 reflections(Δ/σ)max = 0.001
340 parametersΔρmax = 0.51 e Å3
0 restraintsΔρmin = 0.21 e Å3
Special details top

Experimental. M.p. 488.2–489.2 K (not corrected); IR (film) 3483, 2940, 1799, 1717, 1274, 1099, 1042, 773 cm-1; 1H NMR (500 MHz, CDCl3, at 333 K) δ (p.p.m.) 8.02 (d, J = 7.7 Hz, 2H), 7.58 (t, J = 7.5 Hz, 1H), 7.46 (t, J = 7.7 Hz, 2H), 5.50 (s, 1H), 4.92 (d, J = 4.3 Hz, 1H), 4.91 (dd J = 11.7, 4.9 Hz, 1H), 4.80 (d, J = 6.9 Hz, 1H), 4.64 (d, J = 6.9 Hz, 1H), 4.31 (d, J = 10.9 Hz, 1H), 3.68 (ddd, J = 10.9, 10.6, 4.9 Hz, 1H), 3.39 (s, 3H), 3.19 (d, J = 16.9 Hz, 1H), 2.42 (dd, J = 10.9, 4.3 Hz, 1H), 2.33 (s, 1H), 2.33–2.27 (m, 1H), 2.26 (d, J = 16.9 Hz, 1H), 2.02 (dd, J = 16.0, 10.9 Hz, 1H), 1.95–1.87 (m, 1H), 1.88 (s, 3H), 1.82 (dddd, J = 13.6, 13.6, 13.6, 4.6 Hz, 1H), 1.72 (d, J = 16.0 Hz, 1H), 1.49–1.40 (m, 1H), 1.46 (s, 1H), 1.41 (s, 3H), 1.20 (s, 3H), 1.18 (s, 3H); 13C NMR (125 MHz, CDCl3, at 333 K) δ (p.p.m.) 166.3 (C), 154.4 (C), 136.3 (C), 133.4 (CH), 130.4 (C), 129.8 (CH), 128.7 (CH), 122.3 (CH), 97.7 (CH2), 88.5 (C), 79.5 (CH), 75.2 (CH), 74.3 (CH), 70.3 (CH), 60.0 (CH), 56.1 (CH3), 44.8 (CH2), 44.2 (CH), 42.0 (C), 39.0 (C), 32.0 (CH2), 30.7 (CH2), 28.6 (CH3), 25.6 (CH2), 22.9 (CH3), 20.8 (CH3), 16.1 (CH3); LRMS (EI) m/z 514 (M+, 3%), 483 (1), 469 (1), 453 (1), 409 (2), 393 (6), 348 (1), 332 (2), 121 (78), 105 (100), 77 (59); HRMS (EI) m/z calcd for C29H38O8+ [M]+ 514.2567, found 514.2560.

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.

Problematic one reflection with |I(obs)-I(calc)|/σW(I) greater than 10 (-1 0 1) has been omitted in the final refinement.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.7169 (2)0.18654 (10)0.68618 (13)0.0143 (4)
C20.6544 (2)0.17259 (10)0.77738 (14)0.0136 (4)
H20.67820.21230.81950.016*
C30.7047 (2)0.10935 (10)0.83870 (13)0.0131 (4)
H30.78840.09050.81580.016*
C40.5888 (2)0.05350 (10)0.82692 (14)0.0157 (5)
H40.50050.07110.84540.019*
C50.6453 (2)0.00784 (10)0.88896 (14)0.0181 (5)
H5A0.72790.02750.86710.022*
H5B0.56950.04220.88270.022*
C60.6915 (2)0.01330 (11)0.99391 (14)0.0192 (5)
H6A0.60730.03011.01690.023*
H6B0.72950.0261.03250.023*
C70.8069 (2)0.06816 (10)1.00523 (13)0.0155 (4)
H70.89520.04910.98840.019*
C80.7615 (2)0.13268 (10)0.94372 (14)0.0135 (4)
C90.9051 (2)0.17425 (10)0.94939 (14)0.0164 (5)
H9B0.93930.18481.0170.02*
H9A0.97520.14240.93260.02*
C100.9238 (2)0.24112 (10)0.89436 (14)0.0166 (5)
H101.01810.2590.92810.02*
C110.9370 (2)0.24049 (10)0.78491 (14)0.0172 (5)
H111.00360.27820.78010.021*
C121.0208 (2)0.17776 (11)0.76571 (14)0.0174 (5)
C130.9588 (2)0.12865 (10)0.70699 (14)0.0167 (5)
H131.01560.09110.69890.02*
C140.8037 (2)0.12964 (10)0.65293 (14)0.0154 (4)
H14A0.75810.08640.66170.018*
H14B0.80210.13510.58480.018*
C150.8037 (2)0.25338 (10)0.69973 (14)0.0154 (5)
C160.7084 (2)0.31455 (10)0.71360 (14)0.0191 (5)
H16B0.64470.32550.65350.029*
H16C0.76950.3530.73550.029*
H16A0.65120.30350.76040.029*
C170.8650 (2)0.27030 (11)0.60997 (15)0.0209 (5)
H17A0.93770.23730.60290.031*
H17B0.9080.31490.61680.031*
H17C0.78740.26930.55410.031*
C181.1796 (2)0.17407 (12)0.81421 (16)0.0242 (5)
H18B1.21930.13110.79980.036*
H18C1.18870.17830.88250.036*
H18A1.2320.21040.79120.036*
C190.6461 (2)0.17224 (11)0.98432 (14)0.0176 (5)
H19C0.61490.21110.94440.026*
H19A0.68730.18711.04850.026*
H19B0.56390.14320.98540.026*
O200.49732 (15)0.17278 (7)0.74303 (9)0.0176 (3)
C210.4646 (2)0.18489 (10)0.64927 (15)0.0178 (5)
O220.58327 (14)0.19463 (7)0.61213 (9)0.0170 (3)
O230.34190 (16)0.18696 (8)0.60281 (10)0.0247 (4)
O240.84116 (15)0.09012 (7)1.10583 (9)0.0168 (3)
C250.9381 (2)0.05274 (10)1.16731 (14)0.0154 (4)
O261.00007 (16)0.00371 (7)1.14311 (10)0.0237 (4)
C270.9612 (2)0.07873 (10)1.26731 (14)0.0153 (4)
C280.8754 (2)0.13006 (11)1.29508 (14)0.0194 (5)
H280.79790.14841.25080.023*
C290.9062 (2)0.15358 (12)1.38896 (15)0.0252 (5)
H290.84910.18781.40770.03*
C301.0214 (2)0.12650 (11)1.45491 (15)0.0231 (5)
H301.04170.14281.51780.028*
C311.1063 (2)0.07552 (11)1.42812 (15)0.0227 (5)
H311.18320.05711.47280.027*
C321.0765 (2)0.05194 (10)1.33430 (14)0.0187 (5)
H321.13420.01791.3160.022*
O330.82270 (15)0.29278 (7)0.90665 (10)0.0200 (3)
H330.82710.29930.96420.03*
O340.55698 (14)0.03544 (7)0.72690 (9)0.0188 (3)
C350.4129 (2)0.01081 (12)0.69395 (15)0.0232 (5)
H35A0.39570.02810.73220.028*
H35B0.3430.0460.70070.028*
O360.39527 (17)0.00779 (8)0.59939 (11)0.0289 (4)
C370.4715 (3)0.06965 (12)0.58715 (17)0.0315 (6)
H37C0.57390.06370.61260.047*
H37A0.45660.08050.51990.047*
H37B0.43490.10610.62070.047*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0139 (11)0.0176 (11)0.0096 (10)0.0000 (9)0.0017 (8)0.0003 (8)
C20.0092 (10)0.0182 (11)0.0126 (10)0.0005 (8)0.0003 (8)0.0006 (8)
C30.0116 (11)0.0156 (10)0.0126 (11)0.0014 (8)0.0039 (8)0.0003 (8)
C40.0154 (11)0.0203 (11)0.0114 (11)0.0014 (9)0.0026 (9)0.0038 (8)
C50.0187 (11)0.0147 (11)0.0216 (12)0.0040 (9)0.0060 (9)0.0018 (9)
C60.0218 (12)0.0190 (11)0.0174 (11)0.0008 (9)0.0052 (9)0.0041 (9)
C70.0192 (11)0.0184 (11)0.0091 (10)0.0018 (9)0.0030 (9)0.0003 (8)
C80.0132 (11)0.0142 (11)0.0129 (11)0.0003 (8)0.0025 (8)0.0007 (8)
C90.0167 (11)0.0174 (11)0.0133 (11)0.0010 (9)0.0009 (9)0.0013 (8)
C100.0154 (11)0.0171 (11)0.0162 (11)0.0002 (9)0.0010 (9)0.0025 (8)
C110.0153 (11)0.0185 (11)0.0179 (11)0.0039 (9)0.0039 (9)0.0010 (9)
C120.0160 (11)0.0205 (11)0.0170 (11)0.0006 (9)0.0067 (9)0.0004 (9)
C130.0176 (11)0.0178 (11)0.0162 (11)0.0030 (9)0.0071 (9)0.0015 (9)
C140.0200 (11)0.0156 (11)0.0118 (11)0.0001 (9)0.0059 (9)0.0001 (8)
C150.0170 (11)0.0153 (11)0.0141 (11)0.0000 (9)0.0040 (9)0.0005 (8)
C160.0217 (12)0.0188 (11)0.0152 (11)0.0028 (9)0.0003 (9)0.0027 (8)
C170.0248 (12)0.0187 (11)0.0207 (12)0.0029 (9)0.0079 (10)0.0009 (9)
C180.0184 (12)0.0282 (13)0.0263 (13)0.0004 (10)0.0052 (10)0.0049 (10)
C190.0199 (12)0.0188 (11)0.0140 (11)0.0016 (9)0.0032 (9)0.0003 (8)
O200.0137 (8)0.0265 (8)0.0119 (8)0.0036 (6)0.0011 (6)0.0032 (6)
C210.0195 (13)0.0173 (11)0.0167 (12)0.0003 (9)0.0041 (10)0.0018 (9)
O220.0152 (8)0.0225 (8)0.0124 (7)0.0000 (6)0.0007 (6)0.0024 (6)
O230.0157 (9)0.0375 (10)0.0189 (8)0.0007 (7)0.0014 (7)0.0077 (7)
O240.0197 (8)0.0197 (8)0.0101 (7)0.0043 (6)0.0011 (6)0.0004 (6)
C250.0159 (11)0.0149 (11)0.0154 (11)0.0005 (9)0.0033 (9)0.0034 (8)
O260.0295 (9)0.0225 (8)0.0179 (8)0.0102 (7)0.0023 (7)0.0004 (6)
C270.0173 (11)0.0139 (10)0.0152 (11)0.0024 (9)0.0042 (9)0.0024 (8)
C280.0175 (12)0.0242 (12)0.0158 (12)0.0022 (9)0.0021 (9)0.0018 (9)
C290.0241 (13)0.0317 (13)0.0203 (13)0.0071 (10)0.0060 (10)0.0027 (10)
C300.0268 (13)0.0293 (13)0.0135 (11)0.0049 (10)0.0045 (10)0.0027 (9)
C310.0227 (12)0.0235 (12)0.0195 (12)0.0011 (10)0.0010 (10)0.0050 (9)
C320.0221 (12)0.0155 (11)0.0181 (11)0.0006 (9)0.0031 (9)0.0010 (9)
O330.0251 (8)0.0187 (8)0.0162 (8)0.0041 (6)0.0046 (7)0.0028 (6)
O340.0166 (8)0.0248 (8)0.0140 (8)0.0046 (6)0.0004 (6)0.0050 (6)
C350.0183 (12)0.0304 (13)0.0196 (12)0.0042 (10)0.0007 (9)0.0070 (9)
O360.0293 (9)0.0288 (9)0.0249 (9)0.0012 (7)0.0031 (7)0.0049 (7)
C370.0328 (14)0.0255 (13)0.0355 (14)0.0026 (11)0.0056 (11)0.0103 (11)
Geometric parameters (Å, º) top
C1—O221.469 (2)C15—C171.536 (3)
C1—C141.512 (3)C16—H16B0.96
C1—C151.535 (3)C16—H16C0.96
C1—C21.550 (3)C16—H16A0.96
C2—O201.452 (2)C17—H17A0.96
C2—C31.534 (3)C17—H17B0.96
C2—H20.98C17—H17C0.96
C3—C41.528 (3)C18—H18B0.96
C3—C81.547 (3)C18—H18C0.96
C3—H30.98C18—H18A0.96
C4—O341.435 (2)C19—H19C0.96
C4—C51.522 (3)C19—H19A0.96
C4—H40.98C19—H19B0.96
C5—C61.522 (3)O20—C211.325 (2)
C5—H5A0.97C21—O231.203 (2)
C5—H5B0.97C21—O221.337 (2)
C6—C71.511 (3)O24—C251.342 (2)
C6—H6A0.97C25—O261.210 (2)
C6—H6B0.97C25—C271.482 (3)
C7—O241.464 (2)C27—C321.389 (3)
C7—C81.548 (3)C27—C281.395 (3)
C7—H70.98C28—C291.384 (3)
C8—C191.535 (3)C28—H280.93
C8—C91.561 (3)C29—C301.382 (3)
C9—C101.556 (3)C29—H290.93
C9—H9B0.97C30—C311.379 (3)
C9—H9A0.97C30—H300.93
C10—O331.422 (2)C31—C321.384 (3)
C10—C111.584 (3)C31—H310.93
C10—H100.98C32—H320.93
C11—C121.515 (3)O33—H330.82
C11—C151.571 (3)O34—C351.419 (2)
C11—H110.98C35—O361.368 (2)
C12—C131.328 (3)C35—H35A0.97
C12—C181.507 (3)C35—H35B0.97
C13—C141.498 (3)O36—C371.437 (3)
C13—H130.93C37—H37C0.96
C14—H14A0.97C37—H37A0.96
C14—H14B0.97C37—H37B0.96
C15—C161.533 (3)
O22—C1—C14106.84 (15)C13—C14—H14B109.2
O22—C1—C15110.43 (15)C1—C14—H14B109.2
C14—C1—C15111.48 (16)H14A—C14—H14B107.9
O22—C1—C2101.84 (15)C16—C15—C1112.24 (16)
C14—C1—C2116.66 (16)C16—C15—C17105.23 (16)
C15—C1—C2109.08 (15)C1—C15—C17111.01 (16)
O20—C2—C3111.43 (15)C16—C15—C11114.78 (16)
O20—C2—C1104.36 (14)C1—C15—C11106.00 (16)
C3—C2—C1119.49 (16)C17—C15—C11107.56 (16)
O20—C2—H2107.0C15—C16—H16B109.5
C3—C2—H2107.0C15—C16—H16C109.5
C1—C2—H2107.0H16B—C16—H16C109.5
C4—C3—C2112.93 (16)C15—C16—H16A109.5
C4—C3—C8114.52 (15)H16B—C16—H16A109.5
C2—C3—C8108.22 (16)H16C—C16—H16A109.5
C4—C3—H3106.9C15—C17—H17A109.5
C2—C3—H3106.9C15—C17—H17B109.5
C8—C3—H3106.9H17A—C17—H17B109.5
O34—C4—C5110.78 (16)C15—C17—H17C109.5
O34—C4—C3106.57 (15)H17A—C17—H17C109.5
C5—C4—C3110.44 (16)H17B—C17—H17C109.5
O34—C4—H4109.7C12—C18—H18B109.5
C5—C4—H4109.7C12—C18—H18C109.5
C3—C4—H4109.7H18B—C18—H18C109.5
C4—C5—C6110.28 (17)C12—C18—H18A109.5
C4—C5—H5A109.6H18B—C18—H18A109.5
C6—C5—H5A109.6H18C—C18—H18A109.5
C4—C5—H5B109.6C8—C19—H19C109.5
C6—C5—H5B109.6C8—C19—H19A109.5
H5A—C5—H5B108.1H19C—C19—H19A109.5
C7—C6—C5110.65 (16)C8—C19—H19B109.5
C7—C6—H6A109.5H19C—C19—H19B109.5
C5—C6—H6A109.5H19A—C19—H19B109.5
C7—C6—H6B109.5C21—O20—C2110.43 (15)
C5—C6—H6B109.5O23—C21—O20123.82 (19)
H6A—C6—H6B108.1O23—C21—O22123.79 (18)
O24—C7—C6108.86 (15)O20—C21—O22112.39 (18)
O24—C7—C8106.83 (15)C21—O22—C1110.93 (15)
C6—C7—C8114.51 (17)C25—O24—C7117.26 (15)
O24—C7—H7108.8O26—C25—O24123.40 (18)
C6—C7—H7108.8O26—C25—C27124.13 (18)
C8—C7—H7108.8O24—C25—C27112.46 (17)
C19—C8—C3112.46 (16)C32—C27—C28119.50 (18)
C19—C8—C7109.62 (16)C32—C27—C25117.84 (18)
C3—C8—C7107.59 (15)C28—C27—C25122.63 (18)
C19—C8—C9112.39 (16)C29—C28—C27119.61 (19)
C3—C8—C9109.13 (15)C29—C28—H28120.2
C7—C8—C9105.30 (16)C27—C28—H28120.2
C10—C9—C8126.80 (17)C30—C29—C28120.3 (2)
C10—C9—H9B105.6C30—C29—H29119.8
C8—C9—H9B105.6C28—C29—H29119.8
C10—C9—H9A105.6C31—C30—C29120.4 (2)
C8—C9—H9A105.6C31—C30—H30119.8
H9B—C9—H9A106.1C29—C30—H30119.8
O33—C10—C9113.25 (16)C30—C31—C32119.6 (2)
O33—C10—C11108.23 (15)C30—C31—H31120.2
C9—C10—C11121.68 (16)C32—C31—H31120.2
O33—C10—H10103.9C31—C32—C27120.6 (2)
C9—C10—H10103.9C31—C32—H32119.7
C11—C10—H10103.9C27—C32—H32119.7
C12—C11—C15110.59 (16)C10—O33—H33109.5
C12—C11—C10109.26 (16)C35—O34—C4113.70 (14)
C15—C11—C10123.08 (16)O36—C35—O34109.31 (16)
C12—C11—H11104.0O36—C35—H35A109.8
C15—C11—H11104.0O34—C35—H35A109.8
C10—C11—H11104.0O36—C35—H35B109.8
C13—C12—C18121.05 (19)O34—C35—H35B109.8
C13—C12—C11121.81 (19)H35A—C35—H35B108.3
C18—C12—C11117.12 (18)C35—O36—C37112.38 (17)
C12—C13—C14124.47 (19)O36—C37—H37C109.5
C12—C13—H13117.8O36—C37—H37A109.5
C14—C13—H13117.8H37C—C37—H37A109.5
C13—C14—C1112.09 (16)O36—C37—H37B109.5
C13—C14—H14A109.2H37C—C37—H37B109.5
C1—C14—H14A109.2H37A—C37—H37B109.5
O22—C1—C2—O201.49 (18)O22—C1—C14—C13164.37 (15)
C14—C1—C2—O20114.39 (18)C15—C1—C14—C1343.6 (2)
C15—C1—C2—O20118.23 (16)C2—C1—C14—C1382.6 (2)
O22—C1—C2—C3126.81 (17)O22—C1—C15—C1650.0 (2)
C14—C1—C2—C310.9 (3)C14—C1—C15—C16168.56 (16)
C15—C1—C2—C3116.45 (19)C2—C1—C15—C1661.2 (2)
O20—C2—C3—C415.6 (2)O22—C1—C15—C1767.5 (2)
C1—C2—C3—C4106.25 (19)C14—C1—C15—C1751.1 (2)
O20—C2—C3—C8112.22 (17)C2—C1—C15—C17178.64 (16)
C1—C2—C3—C8125.90 (18)O22—C1—C15—C11176.00 (14)
C2—C3—C4—O3459.3 (2)C14—C1—C15—C1165.40 (19)
C8—C3—C4—O34176.20 (15)C2—C1—C15—C1164.86 (19)
C2—C3—C4—C5179.71 (16)C12—C11—C15—C16178.07 (16)
C8—C3—C4—C555.8 (2)C10—C11—C15—C1646.4 (3)
O34—C4—C5—C6174.93 (15)C12—C11—C15—C153.6 (2)
C3—C4—C5—C657.1 (2)C10—C11—C15—C178.1 (2)
C4—C5—C6—C757.8 (2)C12—C11—C15—C1765.2 (2)
C5—C6—C7—O24176.31 (15)C10—C11—C15—C17163.09 (17)
C5—C6—C7—C856.8 (2)C3—C2—O20—C21130.71 (17)
C4—C3—C8—C1969.6 (2)C1—C2—O20—C210.4 (2)
C2—C3—C8—C1957.3 (2)C2—O20—C21—O23179.11 (19)
C4—C3—C8—C751.2 (2)C2—O20—C21—O221.0 (2)
C2—C3—C8—C7178.13 (15)O23—C21—O22—C1178.01 (19)
C4—C3—C8—C9164.96 (16)O20—C21—O22—C12.1 (2)
C2—C3—C8—C968.11 (19)C14—C1—O22—C21120.70 (17)
O24—C7—C8—C1949.8 (2)C15—C1—O22—C21117.90 (17)
C6—C7—C8—C1970.8 (2)C2—C1—O22—C212.14 (19)
O24—C7—C8—C3172.37 (14)C6—C7—O24—C2583.5 (2)
C6—C7—C8—C351.8 (2)C8—C7—O24—C25152.31 (16)
O24—C7—C8—C971.32 (18)C7—O24—C25—O262.0 (3)
C6—C7—C8—C9168.07 (16)C7—O24—C25—C27178.54 (15)
C19—C8—C9—C1065.5 (2)O26—C25—C27—C3210.3 (3)
C3—C8—C9—C1060.0 (2)O24—C25—C27—C32169.09 (17)
C7—C8—C9—C10175.21 (18)O26—C25—C27—C28171.9 (2)
C8—C9—C10—O3352.8 (3)O24—C25—C27—C288.7 (3)
C8—C9—C10—C1178.9 (3)C32—C27—C28—C290.0 (3)
O33—C10—C11—C12169.30 (16)C25—C27—C28—C29177.76 (19)
C9—C10—C11—C1235.5 (2)C27—C28—C29—C300.1 (3)
O33—C10—C11—C1537.1 (2)C28—C29—C30—C310.4 (3)
C9—C10—C11—C1596.7 (2)C29—C30—C31—C320.6 (3)
C15—C11—C12—C1323.7 (3)C30—C31—C32—C270.6 (3)
C10—C11—C12—C13114.8 (2)C28—C27—C32—C310.3 (3)
C15—C11—C12—C18154.73 (17)C25—C27—C32—C31178.12 (18)
C10—C11—C12—C1866.8 (2)C5—C4—O34—C3588.2 (2)
C18—C12—C13—C14177.43 (18)C3—C4—O34—C35151.61 (17)
C11—C12—C13—C141.0 (3)C4—O34—C35—O36177.35 (16)
C12—C13—C14—C110.5 (3)O34—C35—O36—C3772.7 (2)
Hydrogen-bond geometry (Å, º) top
Cg2 is the centroid of the C27–C32 benzene ring.
D—H···AD—HH···AD···AD—H···A
C2—H2···O330.982.273.200 (2)157
C14—H14A···O340.972.473.293 (2)142
O33—H33···O23i0.821.962.7823 (19)179
C7—H7···O26ii0.982.503.353 (2)145
C16—H16A···Cg2iii0.982.933.594 (2)128
Symmetry codes: (i) x+1/2, y+1/2, z+1/2; (ii) x+2, y, z+2; (iii) x3/2, y1/2, z3/2.
(C) (±)-(1SR,5SR,6SR,7SR,10SR,11SR,14SR)-7-Methoxymethoxy-11,15,18,18-tetramethyl-3,13-dioxo-2,4-dioxatetracyclo[12.3.1.01,5.06,11]octadec-15-en-10-yl benzoate top
Crystal data top
C29H36O8Dx = 1.357 Mg m3
Mr = 512.59Melting point: 512.2 K
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 13.2416 (8) ÅCell parameters from 6186 reflections
b = 13.1779 (8) Åθ = 2.8–24.9°
c = 15.2428 (8) ŵ = 0.10 mm1
β = 109.387 (2)°T = 90 K
V = 2509.0 (3) Å3Plate, colorless
Z = 40.22 × 0.14 × 0.09 mm
F(000) = 1096
Data collection top
Bruker D8 Venture
diffractometer
4395 independent reflections
Radiation source: fine-focus sealed tube3050 reflections with I > 2σ(I)
Multilayered confocal mirror monochromatorRint = 0.063
Detector resolution: 8.333 pixels mm-1θmax = 25.0°, θmin = 2.4°
φ and ω scansh = 1514
Absorption correction: multi-scan
(SADABS; Bruker, 2014)
k = 1515
Tmin = 0.92, Tmax = 0.99l = 1618
22512 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.105H-atom parameters constrained
S = 0.96 w = 1/[σ2(Fo2) + (0.0391P)2 + 2.2049P]
where P = (Fo2 + 2Fc2)/3
4395 reflections(Δ/σ)max = 0.001
339 parametersΔρmax = 0.29 e Å3
0 restraintsΔρmin = 0.25 e Å3
Special details top

Experimental. M.p. 510.7–512.2 K (not corrected); IR (film) 2934, 1804, 1718, 1689, 1668, 1272, 1230, 1108, 1058, 732, 713 cm-1; 1H NMR (500 MHz, CDCl3) δ (p.p.m.) 8.05–8.98 (m, 2H), 7.62–7.56 (m, 1H), 7.49–7.43 (m, 2H), 5.73 (bs, 1H), 4.79 (d, J = 6.9 Hz, 1H), 4.76 (dd, J = 11.0, 4.0 Hz, 1H), 4.60 (d, J = 6.9 Hz, 1H), 4.22 (d, J = 3.4 Hz, 1H), 3.62 (ddd, J = 10.6, 10.3, 5.2 Hz, 1H), 3.37 (s, 3H), 3.00 (bd, J = 17.0 Hz, 1H), 2.61 (d, J = 10.9 Hz, 1H), 2.51 (d, J = 17.0 Hz, 1H), 2.47 (s, 1H), 2.42–2.35 (m, 1H), 2.33 (dd, J = 10.6, 3.4 Hz, 1H), 2.13 (d, J = 10.9 Hz, 1H), 1.95–1.88 (m, 1H), 1.71 (s, 3H), 1.71–1.52 (m, 2H), 1.27 (s, 3H), 1.17 (s, 3H), 1.16 (s, 3H); 13C NMR (125 MHz, CDCl3) δ (p.p.m.) 211.2 (C), 165.9 (C), 153.7 (C), 135.8 (C), 133.5 (CH), 129.8 (C), 129.7 (CH), 128.7 (CH), 122.6 (CH), 97.8 (CH2), 87.0 (C), 79.3 (CH), 79.0 (CH), 74.7 (CH), 65.7 (CH), 56.0 (CH3), 51.2 (CH2), 48.0 (CH), 47.1 (C), 44.1 (C), 31.9 (CH2), 31.2 (CH2), 25.1 (CH3), 24.6 (CH3), 24.6 (CH2), 19.3 (CH3), 12.3 (CH3); LRMS (EI) m/z 512 (M+, 5%), 346 (9), 302 (7), 121 (28), 105 (100), 77 (55); HRMS (EI) m/z calcd for C29H36O8+ [M]+ 512.2410, found 514.2408.

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.

Problematic two reflections with |I(obs)-I(calc)|/σW(I) greater than 10 (1 1 0 and 11 4 3) have been omitted in the final refinement.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.81842 (17)0.32712 (17)0.49210 (14)0.0156 (5)
C20.83265 (18)0.43504 (17)0.53612 (14)0.0157 (5)
H20.89390.43120.59590.019*
C30.73832 (17)0.48566 (16)0.55835 (14)0.0141 (5)
H30.67870.4350.54220.017*
C40.69530 (17)0.58009 (17)0.49830 (14)0.0151 (5)
H40.75510.6290.50480.018*
C50.60735 (18)0.63170 (17)0.52421 (14)0.0186 (5)
H5A0.5430.58790.50550.022*
H5B0.58840.69620.48940.022*
C60.63941 (18)0.65384 (17)0.62826 (14)0.0191 (5)
H6A0.6990.70340.64660.023*
H6B0.5780.68340.64270.023*
C70.67390 (18)0.55614 (17)0.68165 (13)0.0152 (5)
H70.61220.50780.66410.018*
C80.77033 (17)0.50500 (16)0.66456 (14)0.0144 (5)
C90.78727 (18)0.40213 (17)0.71791 (14)0.0170 (5)
H9B0.80220.41760.78460.02*
H9A0.71850.36480.69630.02*
C100.87422 (19)0.33035 (17)0.71100 (14)0.0176 (5)
C110.84777 (17)0.23989 (17)0.64233 (14)0.0169 (5)
H110.88530.17990.67910.02*
C120.72983 (18)0.21357 (17)0.60918 (15)0.0170 (5)
C130.66633 (18)0.23789 (17)0.52443 (15)0.0179 (5)
H130.59220.22280.50840.021*
C140.70379 (17)0.28774 (17)0.45229 (14)0.0175 (5)
H14A0.65550.34510.42430.021*
H14B0.69940.23830.40230.021*
C150.89166 (17)0.24989 (17)0.55936 (14)0.0177 (5)
C161.00975 (18)0.28215 (18)0.59015 (16)0.0209 (5)
H16A1.01710.35070.61650.031*
H16B1.03460.28160.53630.031*
H16C1.05280.23470.63730.031*
C170.88509 (19)0.14530 (17)0.51289 (16)0.0221 (6)
H17C0.90390.1520.45620.033*
H17A0.81210.11880.4970.033*
H17B0.93510.09850.55590.033*
C180.69208 (19)0.15857 (18)0.67848 (15)0.0222 (6)
H18B0.61440.14880.65280.033*
H18C0.70960.19850.73580.033*
H18A0.72750.09240.69220.033*
C190.87058 (18)0.57156 (17)0.70192 (15)0.0186 (5)
H19A0.88090.59050.76650.028*
H19B0.86170.6330.66390.028*
H19C0.93320.53370.69920.028*
O200.86805 (11)0.49630 (11)0.47260 (9)0.0165 (4)
C210.87791 (17)0.43902 (18)0.40303 (15)0.0169 (5)
O220.85523 (12)0.34137 (12)0.41269 (10)0.0187 (4)
O230.90357 (12)0.47131 (12)0.34036 (10)0.0224 (4)
O240.70651 (11)0.57550 (11)0.78110 (9)0.0170 (4)
C250.63110 (18)0.57567 (16)0.82216 (15)0.0146 (5)
O260.53686 (12)0.56418 (12)0.78106 (10)0.0203 (4)
C270.67949 (18)0.58868 (16)0.92408 (14)0.0150 (5)
C280.61586 (19)0.57355 (17)0.97941 (15)0.0212 (5)
H280.54220.55740.95150.025*
C290.6597 (2)0.58201 (18)1.07519 (15)0.0237 (6)
H290.61610.57121.11280.028*
C300.7661 (2)0.60592 (18)1.11608 (16)0.0255 (6)
H300.7960.61091.18180.031*
C310.8296 (2)0.62271 (18)1.06145 (16)0.0250 (6)
H310.90280.64031.08960.03*
C320.78646 (19)0.61393 (18)0.96603 (15)0.0215 (5)
H320.83040.62530.92880.026*
O330.96560 (13)0.34029 (12)0.76362 (10)0.0236 (4)
O340.65380 (12)0.54447 (11)0.40409 (9)0.0182 (4)
C350.67590 (19)0.60542 (18)0.33721 (15)0.0214 (6)
H35A0.75320.62180.35920.026*
H35B0.66030.5660.27890.026*
O360.61766 (12)0.69614 (11)0.31770 (10)0.0200 (4)
C370.50654 (18)0.68122 (18)0.27053 (16)0.0243 (6)
H37B0.47460.6470.3120.036*
H37C0.49670.63930.21520.036*
H37A0.47170.74710.25180.036*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0189 (13)0.0175 (13)0.0133 (11)0.0015 (10)0.0092 (10)0.0016 (9)
C20.0189 (13)0.0148 (13)0.0149 (11)0.0009 (10)0.0079 (10)0.0026 (9)
C30.0149 (12)0.0126 (12)0.0152 (11)0.0002 (10)0.0056 (9)0.0016 (9)
C40.0166 (12)0.0147 (13)0.0130 (11)0.0004 (10)0.0037 (10)0.0012 (9)
C50.0216 (13)0.0163 (13)0.0183 (11)0.0057 (10)0.0071 (10)0.0028 (10)
C60.0228 (13)0.0159 (13)0.0212 (12)0.0041 (10)0.0109 (10)0.0006 (10)
C70.0192 (12)0.0160 (13)0.0112 (11)0.0035 (10)0.0061 (10)0.0036 (9)
C80.0154 (12)0.0156 (13)0.0129 (11)0.0015 (10)0.0058 (9)0.0010 (9)
C90.0199 (13)0.0170 (13)0.0150 (11)0.0001 (10)0.0070 (10)0.0003 (9)
C100.0209 (14)0.0182 (13)0.0137 (11)0.0007 (11)0.0055 (11)0.0052 (10)
C110.0187 (13)0.0134 (13)0.0178 (11)0.0010 (10)0.0049 (10)0.0024 (9)
C120.0197 (13)0.0128 (13)0.0201 (12)0.0010 (10)0.0089 (10)0.0034 (10)
C130.0180 (13)0.0132 (13)0.0226 (12)0.0012 (10)0.0070 (10)0.0040 (10)
C140.0192 (13)0.0151 (13)0.0154 (11)0.0009 (10)0.0021 (10)0.0013 (9)
C150.0191 (13)0.0144 (13)0.0197 (12)0.0023 (10)0.0066 (10)0.0003 (10)
C160.0204 (13)0.0179 (14)0.0257 (12)0.0051 (10)0.0094 (10)0.0026 (10)
C170.0260 (14)0.0167 (14)0.0252 (12)0.0024 (11)0.0106 (11)0.0014 (10)
C180.0242 (14)0.0209 (14)0.0229 (12)0.0011 (11)0.0096 (11)0.0002 (10)
C190.0205 (13)0.0180 (13)0.0181 (11)0.0001 (10)0.0074 (10)0.0028 (10)
O200.0199 (9)0.0152 (9)0.0177 (8)0.0015 (7)0.0109 (7)0.0013 (7)
C210.0127 (12)0.0184 (14)0.0175 (12)0.0024 (10)0.0022 (10)0.0007 (10)
O220.0258 (9)0.0165 (9)0.0177 (8)0.0001 (7)0.0122 (7)0.0014 (7)
O230.0254 (9)0.0267 (10)0.0201 (8)0.0039 (8)0.0139 (7)0.0004 (7)
O240.0194 (9)0.0194 (9)0.0139 (7)0.0010 (7)0.0079 (7)0.0032 (6)
C250.0171 (13)0.0079 (12)0.0222 (12)0.0014 (10)0.0109 (11)0.0004 (9)
O260.0175 (10)0.0225 (10)0.0211 (8)0.0019 (7)0.0066 (7)0.0029 (7)
C270.0199 (13)0.0108 (12)0.0146 (11)0.0022 (10)0.0061 (10)0.0003 (9)
C280.0256 (14)0.0157 (13)0.0235 (12)0.0022 (11)0.0098 (11)0.0009 (10)
C290.0333 (16)0.0241 (15)0.0172 (12)0.0041 (12)0.0129 (12)0.0027 (10)
C300.0390 (16)0.0196 (14)0.0150 (12)0.0049 (12)0.0052 (12)0.0012 (10)
C310.0263 (14)0.0230 (15)0.0220 (13)0.0033 (11)0.0029 (11)0.0035 (10)
C320.0243 (14)0.0214 (14)0.0212 (12)0.0008 (11)0.0106 (11)0.0026 (10)
O330.0205 (10)0.0264 (10)0.0200 (8)0.0017 (8)0.0016 (8)0.0005 (7)
O340.0248 (9)0.0179 (9)0.0124 (7)0.0017 (7)0.0068 (7)0.0018 (6)
C350.0241 (14)0.0254 (15)0.0162 (12)0.0067 (11)0.0087 (11)0.0051 (10)
O360.0203 (9)0.0162 (9)0.0221 (8)0.0005 (7)0.0052 (7)0.0047 (7)
C370.0200 (14)0.0243 (15)0.0275 (13)0.0014 (11)0.0065 (11)0.0056 (11)
Geometric parameters (Å, º) top
C1—O221.459 (2)C15—C171.539 (3)
C1—C141.526 (3)C16—H16A0.98
C1—C151.539 (3)C16—H16B0.98
C1—C21.557 (3)C16—H16C0.98
C2—O201.453 (2)C17—H17C0.98
C2—C31.550 (3)C17—H17A0.98
C2—H21.0C17—H17B0.98
C3—C41.538 (3)C18—H18B0.98
C3—C81.552 (3)C18—H18C0.98
C3—H31.0C18—H18A0.98
C4—O341.435 (2)C19—H19A0.98
C4—C51.510 (3)C19—H19B0.98
C4—H41.0C19—H19C0.98
C5—C61.528 (3)O20—C211.343 (3)
C5—H5A0.99C21—O231.193 (2)
C5—H5B0.99C21—O221.341 (3)
C6—C71.510 (3)O24—C251.343 (2)
C6—H6A0.99C25—O261.206 (3)
C6—H6B0.99C25—C271.481 (3)
C7—O241.454 (2)C27—C321.387 (3)
C7—C81.540 (3)C27—C281.390 (3)
C7—H71.0C28—C291.385 (3)
C8—C191.534 (3)C28—H280.95
C8—C91.558 (3)C29—C301.374 (3)
C9—C101.521 (3)C29—H290.95
C9—H9B0.99C30—C311.384 (3)
C9—H9A0.99C30—H300.95
C10—O331.217 (3)C31—C321.380 (3)
C10—C111.548 (3)C31—H310.95
C11—C121.514 (3)C32—H320.95
C11—C151.563 (3)O34—C351.403 (3)
C11—H111.0C35—O361.400 (3)
C12—C131.326 (3)C35—H35A0.99
C12—C181.497 (3)C35—H35B0.99
C13—C141.500 (3)O36—C371.421 (3)
C13—H130.95C37—H37B0.98
C14—H14A0.99C37—H37C0.98
C14—H14B0.99C37—H37A0.98
C15—C161.536 (3)
O22—C1—C14106.01 (16)C1—C14—H14B109.1
O22—C1—C15109.12 (17)H14A—C14—H14B107.8
C14—C1—C15111.33 (18)C16—C15—C1111.91 (18)
O22—C1—C2102.36 (16)C16—C15—C17106.55 (18)
C14—C1—C2116.36 (18)C1—C15—C17111.04 (18)
C15—C1—C2110.96 (17)C16—C15—C11112.98 (17)
O20—C2—C3111.62 (17)C1—C15—C11105.87 (17)
O20—C2—C1103.89 (15)C17—C15—C11108.51 (18)
C3—C2—C1119.76 (18)C15—C16—H16A109.5
O20—C2—H2107.0C15—C16—H16B109.5
C3—C2—H2107.0H16A—C16—H16B109.5
C1—C2—H2107.0C15—C16—H16C109.5
C4—C3—C2112.61 (17)H16A—C16—H16C109.5
C4—C3—C8114.01 (17)H16B—C16—H16C109.5
C2—C3—C8109.74 (17)C15—C17—H17C109.5
C4—C3—H3106.7C15—C17—H17A109.5
C2—C3—H3106.7H17C—C17—H17A109.5
C8—C3—H3106.7C15—C17—H17B109.5
O34—C4—C5109.67 (17)H17C—C17—H17B109.5
O34—C4—C3105.90 (17)H17A—C17—H17B109.5
C5—C4—C3111.98 (17)C12—C18—H18B109.5
O34—C4—H4109.7C12—C18—H18C109.5
C5—C4—H4109.7H18B—C18—H18C109.5
C3—C4—H4109.7C12—C18—H18A109.5
C4—C5—C6112.64 (18)H18B—C18—H18A109.5
C4—C5—H5A109.1H18C—C18—H18A109.5
C6—C5—H5A109.1C8—C19—H19A109.5
C4—C5—H5B109.1C8—C19—H19B109.5
C6—C5—H5B109.1H19A—C19—H19B109.5
H5A—C5—H5B107.8C8—C19—H19C109.5
C7—C6—C5109.07 (18)H19A—C19—H19C109.5
C7—C6—H6A109.9H19B—C19—H19C109.5
C5—C6—H6A109.9C21—O20—C2110.57 (17)
C7—C6—H6B109.9O23—C21—O22124.3 (2)
C5—C6—H6B109.9O23—C21—O20124.0 (2)
H6A—C6—H6B108.3O22—C21—O20111.64 (18)
O24—C7—C6110.13 (17)C21—O22—C1111.30 (16)
O24—C7—C8106.08 (16)C25—O24—C7118.46 (17)
C6—C7—C8113.65 (17)O26—C25—O24123.99 (19)
O24—C7—H7109.0O26—C25—C27124.93 (19)
C6—C7—H7109.0O24—C25—C27111.07 (19)
C8—C7—H7109.0C32—C27—C28119.1 (2)
C19—C8—C7110.53 (18)C32—C27—C25122.10 (19)
C19—C8—C3112.58 (17)C28—C27—C25118.8 (2)
C7—C8—C3107.06 (16)C29—C28—C27120.1 (2)
C19—C8—C9110.29 (17)C29—C28—H28120.0
C7—C8—C9106.03 (17)C27—C28—H28120.0
C3—C8—C9110.09 (17)C30—C29—C28120.3 (2)
C10—C9—C8119.09 (18)C30—C29—H29119.8
C10—C9—H9B107.5C28—C29—H29119.8
C8—C9—H9B107.5C29—C30—C31120.0 (2)
C10—C9—H9A107.5C29—C30—H30120.0
C8—C9—H9A107.5C31—C30—H30120.0
H9B—C9—H9A107.0C32—C31—C30120.0 (2)
O33—C10—C9119.8 (2)C32—C31—H31120.0
O33—C10—C11118.8 (2)C30—C31—H31120.0
C9—C10—C11121.29 (19)C31—C32—C27120.5 (2)
C12—C11—C10112.27 (18)C31—C32—H32119.7
C12—C11—C15111.64 (17)C27—C32—H32119.7
C10—C11—C15114.89 (18)C35—O34—C4115.90 (17)
C12—C11—H11105.7O36—C35—O34114.22 (17)
C10—C11—H11105.7O36—C35—H35A108.7
C15—C11—H11105.7O34—C35—H35A108.7
C13—C12—C18123.5 (2)O36—C35—H35B108.7
C13—C12—C11121.4 (2)O34—C35—H35B108.7
C18—C12—C11115.12 (18)H35A—C35—H35B107.6
C12—C13—C14124.3 (2)C35—O36—C37113.22 (18)
C12—C13—H13117.9O36—C37—H37B109.5
C14—C13—H13117.9O36—C37—H37C109.5
C13—C14—C1112.63 (17)H37B—C37—H37C109.5
C13—C14—H14A109.1O36—C37—H37A109.5
C1—C14—H14A109.1H37B—C37—H37A109.5
C13—C14—H14B109.1H37C—C37—H37A109.5
O22—C1—C2—O203.79 (19)O22—C1—C14—C13161.48 (17)
C14—C1—C2—O20111.28 (19)C15—C1—C14—C1342.9 (2)
C15—C1—C2—O20120.08 (18)C2—C1—C14—C1385.5 (2)
O22—C1—C2—C3129.13 (18)O22—C1—C15—C1655.9 (2)
C14—C1—C2—C314.1 (3)C14—C1—C15—C16172.61 (17)
C15—C1—C2—C3114.6 (2)C2—C1—C15—C1656.1 (2)
O20—C2—C3—C47.8 (2)O22—C1—C15—C1763.0 (2)
C1—C2—C3—C4113.8 (2)C14—C1—C15—C1753.7 (2)
O20—C2—C3—C8120.39 (18)C2—C1—C15—C17175.02 (17)
C1—C2—C3—C8118.0 (2)O22—C1—C15—C11179.44 (16)
C2—C3—C4—O3463.5 (2)C14—C1—C15—C1163.9 (2)
C8—C3—C4—O34170.62 (16)C2—C1—C15—C1167.4 (2)
C2—C3—C4—C5177.00 (18)C12—C11—C15—C16176.93 (18)
C8—C3—C4—C551.1 (2)C10—C11—C15—C1647.6 (3)
O34—C4—C5—C6169.18 (18)C12—C11—C15—C154.1 (2)
C3—C4—C5—C651.9 (3)C10—C11—C15—C175.2 (2)
C4—C5—C6—C755.8 (2)C12—C11—C15—C1765.1 (2)
C5—C6—C7—O24179.09 (17)C10—C11—C15—C17165.54 (18)
C5—C6—C7—C860.2 (2)C3—C2—O20—C21131.96 (18)
O24—C7—C8—C1955.8 (2)C1—C2—O20—C211.6 (2)
C6—C7—C8—C1965.3 (2)C2—O20—C21—O23178.3 (2)
O24—C7—C8—C3178.79 (16)C2—O20—C21—O221.6 (2)
C6—C7—C8—C357.6 (2)O23—C21—O22—C1175.5 (2)
O24—C7—C8—C963.7 (2)O20—C21—O22—C14.4 (2)
C6—C7—C8—C9175.17 (17)C14—C1—O22—C21117.38 (19)
C4—C3—C8—C1969.6 (2)C15—C1—O22—C21122.62 (19)
C2—C3—C8—C1957.8 (2)C2—C1—O22—C215.0 (2)
C4—C3—C8—C752.1 (2)C6—C7—O24—C2586.3 (2)
C2—C3—C8—C7179.44 (17)C8—C7—O24—C25150.29 (18)
C4—C3—C8—C9166.90 (18)C7—O24—C25—O262.7 (3)
C2—C3—C8—C965.7 (2)C7—O24—C25—C27175.64 (17)
C19—C8—C9—C1063.2 (2)O26—C25—C27—C32171.9 (2)
C7—C8—C9—C10177.06 (18)O24—C25—C27—C329.8 (3)
C3—C8—C9—C1061.6 (2)O26—C25—C27—C289.1 (3)
C8—C9—C10—O3386.1 (2)O24—C25—C27—C28169.24 (19)
C8—C9—C10—C1198.0 (2)C32—C27—C28—C291.1 (3)
O33—C10—C11—C12158.08 (19)C25—C27—C28—C29177.9 (2)
C9—C10—C11—C1217.9 (3)C27—C28—C29—C300.4 (3)
O33—C10—C11—C1572.9 (3)C28—C29—C30—C310.7 (4)
C9—C10—C11—C15111.1 (2)C29—C30—C31—C321.0 (4)
C10—C11—C12—C13104.9 (2)C30—C31—C32—C270.2 (4)
C15—C11—C12—C1325.8 (3)C28—C27—C32—C310.8 (3)
C10—C11—C12—C1875.4 (2)C25—C27—C32—C31178.2 (2)
C15—C11—C12—C18153.96 (19)C5—C4—O34—C35100.2 (2)
C18—C12—C13—C14176.4 (2)C3—C4—O34—C35138.79 (18)
C11—C12—C13—C143.3 (3)C4—O34—C35—O3672.6 (2)
C12—C13—C14—C111.5 (3)O34—C35—O36—C3768.7 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C14—H14A···O340.992.653.479 (3)142
C31—H31···O33i0.952.353.147 (3)141
C19—H19C···O23ii0.982.433.310 (3)149
C16—H16A···O23ii0.982.563.491 (3)158
Symmetry codes: (i) x+2, y+1, z+2; (ii) x+2, y+1, z+1.
 

Acknowledgements

This research was partially supported by the Keio Gijuku Fukuzawa Memorial Fund for the Advancement of Education and Research. We also thank Professor S. Ohba (Keio University, Japan) for providing valuable advice.

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