Contributions of secondary alcohol–ketone O—H...O=C and furan–acetate Csp²—H...OOC synthons to the supra­molecular packings of two bioactive mol­ecules

The crystal structures of rubescin D (1, C₂₆H₃₀O₅) and monadelphin A (2, C₃₀H₃₆O₁₁), bioactive mol­ecules of the vilasinin and gedunin classes of limonoids, respectively, are reported for the first time and the synthons affecting their crystal packings are analyzed on the basis of their occurrences in mol­ecules in the Cambridge Structural Database that share the same moieties. Rubescin D, 1, crystallizes in the space group P2₁ and its mol­ecular structure consists of three six-membered rings A, C and D having, respectively, envelope, twist-boat and half-chair conformations, and three five-membered rings with half-chair (B and E) and planar conformations (F). Many synthons found in the crystal packing of 1 are in agreement with expectations derived from mol­ecules displaying the same moieties. However, the secondary alcohol–ketone O—H...O=C synthon, which has a low occurrence (2.9%), con­tributes much to the layered packing, while the furan–ketone Csp²—H...O=C and secondary alcohol–epoxide O—H...OC₂ synthons usually found in these com­pounds (occurrences of 20.6 and 17.6%, respectively) are missing. The packing of 1 is close to that of ceramicine B (3), but is com­pletely different from that of TS3 (4), suggesting that the absence of the epoxide group in 3 would have favoured the furan–secondary alcohol Csp²—H...OH synthon and that the missing hy­droxy group in 4, a strong hydrogen-bond donor, would have favoured the involvement of water mol­ecules in the crystal packing. The mol­ecular structure of monadelphin A, 2, consists of four six-membered fused rings (A, B, C and D) and one five-membered ring (E); they have twist-boat (A and C), chair (B), screw-boat (D) and planar (E) conformations. The mol­ecule crystallizes in the space group P2₁2₁2₁ with the con­tribution of many synthons usually found in com­pounds having the same moieties. However, the secondary alcohol–acetate O—H...OOC and secondary alcohol–ketone O—H...O=C synthons (occurrences of 16.7% each in these com­pounds) are missing. The furan–acetate Csp²—H...OOC synthon not observed in these com­pounds greatly con­tributes to the layered packing of 2. The layered packing is very close to those of 7-oxogedunin (5) and 6-de­hydro-7-deacet­oxy-7-oxogedunin (6), which both crystallize in the space group P2₁.

Computing details

For both structures, data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: DIAMOND for Windows (Brandenburg & Putz, 2018).

7-(Furan-3-yl)-12-hydroxy-1,6,11,16-tetramethyl-3,14-dioxahexacyclo[11.6.1.0^2,4.0^2,11.0^6,10.0^16,20]icosa-9,17-dien-19-one (1)

Crystal data

C26H30O5	F(000) = 452
Mr = 422.50	Dx = 1.321 Mg m^−3
Monoclinic, P21	Cu Kα radiation, λ = 1.54184 Å
a = 7.1783 (3) Å	Cell parameters from 3518 reflections
b = 11.6806 (5) Å	θ = 5.1–76.2°
c = 13.0308 (6) Å	µ = 0.73 mm^−1
β = 103.545 (5)°	T = 100 K
V = 1062.20 (8) Å^3	Needle, colorless
Z = 2	0.11 × 0.10 × 0.06 mm

Data collection

Rigaku OD SuperNova Dual source diffractometer with an Atlas detector	4410 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Cu) X-ray Source	3885 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.087
Detector resolution: 10.4508 pixels mm^-1	θmax = 76.6°, θmin = 5.2°
ω scans	h = −9→9
Absorption correction: gaussian (CrysAlis PRO; Rigaku OD, 2015)	k = −14→14
Tmin = 0.935, Tmax = 0.963	l = −16→16
11588 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.063	w = 1/[σ^2(Fo^2) + (0.0915P)^2 + 0.3275P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.172	(Δ/σ)max < 0.001
S = 1.03	Δρmax = 0.43 e Å^−3
4410 reflections	Δρmin = −0.37 e Å^−3
288 parameters	Absolute structure: Refined as an inversion twin
1 restraint	Absolute structure parameter: 0.0 (4)

Special details

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

Refinement. Refined as a 2-component inversion twin.

A low-temperature (100 K) with Supernova, Dual, Cu at zero, Atlas, X-ray apparatus equipped with a micro-focus sealed X-ray tube (λ = 1.54184 Å) and a CCD plate detector were used. Measurements were performed via ω-scans and numerical absorption corrections based on Gaussian integration over a multifaceted crystal model by using CrysAlisPro 1.171.38.43 software (Rigaku Oxford Diffraction, 2015) were done. The structures were solved by direct methods using SHELXT(Sheldrick, 2015a) and refined on F² by full matrix least-squares procedures within the independent atom model (IAM) by using SHELXL-2018 program (Sheldrick, 2015b).

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

	x	y	z	Uiso*/Ueq
O3	0.6956 (4)	0.6099 (3)	0.6959 (2)	0.0203 (6)
O1	0.7383 (4)	0.6364 (3)	0.4770 (2)	0.0209 (6)
O2	0.0282 (4)	0.3880 (3)	0.4804 (2)	0.0221 (6)
O4	0.3157 (4)	0.3368 (3)	0.6583 (2)	0.0215 (6)
O5	1.2276 (5)	0.3258 (4)	1.0660 (3)	0.0338 (8)
C9	0.5202 (6)	0.5558 (3)	0.6410 (3)	0.0166 (7)
C8	0.3689 (6)	0.5378 (4)	0.7087 (3)	0.0189 (8)
C18	0.6983 (6)	0.4887 (4)	0.6676 (3)	0.0199 (8)
H18	0.7565	0.4727	0.6065	0.024*
C6	0.1363 (6)	0.4796 (4)	0.5410 (3)	0.0199 (8)
H6	0.0557	0.5499	0.5381	0.024*
C1	0.5869 (6)	0.5843 (4)	0.4550 (3)	0.0183 (8)
C12	0.4829 (6)	0.5087 (4)	0.8204 (3)	0.0205 (8)
C7	0.2238 (6)	0.4445 (4)	0.6561 (3)	0.0184 (8)
H7	0.1195	0.4386	0.6951	0.022*
C16	0.6435 (6)	0.4202 (4)	0.8452 (3)	0.0187 (8)
C15	0.7815 (6)	0.4808 (4)	0.9409 (3)	0.0206 (8)
H15	0.8453	0.5446	0.9110	0.025*
C4	0.1984 (6)	0.4872 (4)	0.3689 (3)	0.0198 (8)
C17	0.7400 (6)	0.3991 (4)	0.7536 (3)	0.0210 (8)
H17A	0.8803	0.3952	0.7822	0.025*
H17B	0.6978	0.3237	0.7218	0.025*
C11	0.2938 (5)	0.4986 (4)	0.4848 (3)	0.0179 (7)
H11	0.3711	0.4268	0.5001	0.021*
C19	0.9388 (6)	0.4078 (4)	1.0055 (3)	0.0220 (8)
C14	0.6436 (7)	0.5363 (4)	0.9995 (3)	0.0258 (9)
H14B	0.6025	0.4815	1.0478	0.031*
H14A	0.7009	0.6046	1.0397	0.031*
C5	0.0791 (6)	0.3786 (4)	0.3784 (3)	0.0222 (8)
H5A	−0.0376	0.3756	0.3202	0.027*
H5B	0.1556	0.3086	0.3758	0.027*
C3	0.3563 (6)	0.4775 (4)	0.3111 (3)	0.0231 (8)
H3	0.3324	0.4401	0.2446	0.028*
C10	0.4408 (5)	0.5920 (4)	0.5246 (3)	0.0167 (7)
C2	0.5318 (6)	0.5215 (4)	0.3530 (4)	0.0241 (9)
H2	0.6275	0.5114	0.3143	0.029*
C22	0.9287 (7)	0.3285 (4)	1.0889 (3)	0.0264 (9)
H22	0.8194	0.3122	1.1157	0.032*
C23	0.0639 (6)	0.5856 (4)	0.3194 (3)	0.0249 (9)
H23A	−0.0376	0.5945	0.3577	0.030*
H23B	0.0064	0.5680	0.2452	0.030*
H23C	0.1373	0.6569	0.3238	0.030*
C21	1.1054 (8)	0.2818 (4)	1.1216 (4)	0.0289 (10)
H21	1.1394	0.2260	1.1758	0.035*
C26	0.5734 (6)	0.3051 (4)	0.8803 (3)	0.0223 (8)
H26A	0.5199	0.3173	0.9420	0.027*
H26C	0.6814	0.2516	0.8985	0.027*
H26B	0.4745	0.2731	0.8225	0.027*
C20	1.1217 (7)	0.4017 (5)	0.9964 (4)	0.0302 (10)
H20	1.1712	0.4452	0.9472	0.036*
C24	0.3705 (6)	0.7186 (4)	0.5115 (3)	0.0205 (8)
H24A	0.2353	0.7221	0.5142	0.025*
H24B	0.3849	0.7482	0.4434	0.025*
H24C	0.4470	0.7651	0.5686	0.025*
C13	0.4797 (7)	0.5683 (4)	0.9082 (4)	0.0253 (9)
H13	0.3855	0.6241	0.9124	0.030*
C25	0.2539 (6)	0.6475 (4)	0.7161 (3)	0.0220 (8)
H25A	0.3424	0.7106	0.7421	0.026*
H25B	0.1707	0.6350	0.7649	0.026*
H25C	0.1753	0.6669	0.6461	0.026*
H1	0.256 (10)	0.302 (6)	0.606 (5)	0.026*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O3	0.0156 (13)	0.0214 (15)	0.0239 (13)	−0.0025 (11)	0.0044 (11)	−0.0014 (11)
O1	0.0146 (13)	0.0230 (15)	0.0266 (14)	−0.0015 (11)	0.0080 (11)	0.0038 (11)
O2	0.0154 (13)	0.0275 (16)	0.0250 (14)	−0.0056 (12)	0.0079 (11)	−0.0002 (12)
O4	0.0213 (14)	0.0180 (14)	0.0254 (14)	0.0015 (12)	0.0061 (11)	0.0017 (12)
O5	0.0296 (18)	0.038 (2)	0.0325 (17)	0.0088 (15)	0.0043 (13)	0.0014 (14)
C9	0.0134 (17)	0.0148 (17)	0.0233 (18)	0.0008 (14)	0.0079 (14)	−0.0022 (14)
C8	0.0163 (18)	0.020 (2)	0.0225 (19)	0.0014 (15)	0.0092 (15)	0.0010 (14)
C18	0.0130 (17)	0.026 (2)	0.0221 (17)	0.0013 (16)	0.0065 (14)	0.0010 (16)
C6	0.0140 (17)	0.024 (2)	0.0245 (18)	0.0011 (16)	0.0096 (14)	0.0012 (16)
C1	0.0126 (17)	0.0205 (19)	0.0232 (18)	0.0004 (14)	0.0071 (14)	0.0045 (15)
C12	0.0197 (19)	0.0210 (19)	0.0242 (19)	0.0000 (15)	0.0117 (15)	0.0009 (15)
C7	0.0127 (17)	0.0209 (19)	0.0246 (18)	0.0008 (15)	0.0103 (14)	0.0026 (14)
C16	0.0203 (19)	0.020 (2)	0.0178 (17)	−0.0010 (15)	0.0081 (14)	−0.0011 (14)
C15	0.0218 (19)	0.021 (2)	0.0198 (17)	0.0009 (17)	0.0058 (15)	0.0020 (15)
C4	0.0149 (17)	0.023 (2)	0.0236 (18)	−0.0033 (16)	0.0078 (15)	−0.0025 (15)
C17	0.0171 (19)	0.025 (2)	0.0234 (19)	0.0062 (16)	0.0099 (15)	0.0036 (15)
C11	0.0133 (16)	0.0202 (19)	0.0222 (18)	−0.0040 (15)	0.0083 (14)	−0.0008 (14)
C19	0.024 (2)	0.023 (2)	0.0186 (17)	0.0024 (17)	0.0042 (15)	−0.0005 (15)
C14	0.031 (2)	0.025 (2)	0.0228 (19)	0.0045 (17)	0.0083 (17)	−0.0021 (16)
C5	0.020 (2)	0.024 (2)	0.0244 (19)	−0.0018 (16)	0.0092 (16)	0.0004 (15)
C3	0.0215 (19)	0.028 (2)	0.0220 (18)	−0.0052 (17)	0.0103 (15)	−0.0066 (16)
C10	0.0134 (17)	0.0171 (18)	0.0216 (18)	−0.0008 (15)	0.0077 (14)	0.0008 (14)
C2	0.0183 (19)	0.034 (2)	0.0245 (19)	−0.0032 (17)	0.0142 (16)	−0.0012 (16)
C22	0.030 (2)	0.025 (2)	0.0241 (19)	−0.0011 (18)	0.0051 (16)	0.0014 (17)
C23	0.019 (2)	0.029 (2)	0.026 (2)	0.0002 (16)	0.0041 (16)	0.0023 (17)
C21	0.039 (3)	0.023 (2)	0.0215 (19)	0.0022 (19)	0.0022 (18)	−0.0013 (16)
C26	0.021 (2)	0.024 (2)	0.0235 (18)	−0.0020 (16)	0.0087 (16)	0.0023 (15)
C20	0.028 (2)	0.037 (3)	0.026 (2)	0.002 (2)	0.0083 (18)	0.0054 (19)
C24	0.0181 (18)	0.020 (2)	0.0248 (19)	0.0002 (15)	0.0086 (15)	0.0011 (15)
C13	0.027 (2)	0.027 (2)	0.025 (2)	0.0056 (17)	0.0109 (17)	0.0004 (16)
C25	0.021 (2)	0.023 (2)	0.0248 (18)	0.0059 (16)	0.0103 (15)	−0.0013 (16)

Geometric parameters (Å, º)

O3—C9	1.441 (5)	C4—C5	1.552 (6)
O3—C18	1.465 (5)	C17—H17A	0.9900
O1—C1	1.219 (5)	C17—H17B	0.9900
O2—C6	1.443 (5)	C11—C10	1.521 (5)
O2—C5	1.463 (5)	C11—H11	1.0000
O4—C7	1.417 (5)	C19—C20	1.348 (7)
O4—H1	0.82 (7)	C19—C22	1.442 (6)
O5—C21	1.362 (7)	C14—C13	1.511 (6)
O5—C20	1.366 (6)	C14—H14B	0.9900
C9—C18	1.470 (5)	C14—H14A	0.9900
C9—C10	1.549 (5)	C5—H5A	0.9900
C9—C8	1.565 (5)	C5—H5B	0.9900
C8—C12	1.532 (6)	C3—C2	1.352 (6)
C8—C25	1.540 (6)	C3—H3	0.9500
C8—C7	1.552 (6)	C10—C24	1.559 (6)
C18—C17	1.510 (6)	C2—H2	0.9500
C18—H18	1.0000	C22—C21	1.355 (7)
C6—C11	1.500 (5)	C22—H22	0.9500
C6—C7	1.540 (5)	C23—H23A	0.9800
C6—H6	1.0000	C23—H23B	0.9800
C1—C2	1.488 (6)	C23—H23C	0.9800
C1—C10	1.542 (5)	C21—H21	0.9500
C12—C13	1.344 (6)	C26—H26A	0.9800
C12—C16	1.526 (6)	C26—H26C	0.9800
C7—H7	1.0000	C26—H26B	0.9800
C16—C17	1.534 (5)	C20—H20	0.9500
C16—C26	1.542 (6)	C24—H24A	0.9800
C16—C15	1.568 (6)	C24—H24B	0.9800
C15—C19	1.505 (6)	C24—H24C	0.9800
C15—C14	1.528 (6)	C13—H13	0.9500
C15—H15	1.0000	C25—H25A	0.9800
C4—C3	1.504 (5)	C25—H25B	0.9800
C4—C11	1.512 (5)	C25—H25C	0.9800
C4—C23	1.542 (6)
C9—O3—C18	60.8 (2)	C6—C11—H11	103.0
C6—O2—C5	109.6 (3)	C4—C11—H11	103.0
C7—O4—H1	106 (5)	C10—C11—H11	103.0
C21—O5—C20	105.7 (4)	C20—C19—C22	104.7 (4)
O3—C9—C18	60.4 (3)	C20—C19—C15	126.8 (4)
O3—C9—C10	116.4 (3)	C22—C19—C15	128.4 (4)
C18—C9—C10	118.5 (3)	C13—C14—C15	100.8 (3)
O3—C9—C8	114.8 (3)	C13—C14—H14B	111.6
C18—C9—C8	118.4 (3)	C15—C14—H14B	111.6
C10—C9—C8	116.3 (3)	C13—C14—H14A	111.6
C12—C8—C25	107.4 (3)	C15—C14—H14A	111.6
C12—C8—C7	114.7 (3)	H14B—C14—H14A	109.4
C25—C8—C7	107.3 (3)	O2—C5—C4	105.7 (3)
C12—C8—C9	106.2 (3)	O2—C5—H5A	110.6
C25—C8—C9	112.2 (3)	C4—C5—H5A	110.6
C7—C8—C9	109.2 (3)	O2—C5—H5B	110.6
O3—C18—C9	58.8 (3)	C4—C5—H5B	110.6
O3—C18—C17	119.7 (3)	H5A—C5—H5B	108.7
C9—C18—C17	123.7 (3)	C2—C3—C4	120.6 (4)
O3—C18—H18	114.5	C2—C3—H3	119.7
C9—C18—H18	114.5	C4—C3—H3	119.7
C17—C18—H18	114.5	C11—C10—C1	105.7 (3)
O2—C6—C11	102.3 (3)	C11—C10—C9	101.8 (3)
O2—C6—C7	112.3 (3)	C1—C10—C9	114.5 (3)
C11—C6—C7	109.4 (3)	C11—C10—C24	117.5 (3)
O2—C6—H6	110.8	C1—C10—C24	103.8 (3)
C11—C6—H6	110.8	C9—C10—C24	113.7 (3)
C7—C6—H6	110.8	C3—C2—C1	125.2 (4)
O1—C1—C2	119.5 (4)	C3—C2—H2	117.4
O1—C1—C10	121.6 (4)	C1—C2—H2	117.4
C2—C1—C10	118.6 (3)	C21—C22—C19	106.7 (4)
C13—C12—C16	109.5 (4)	C21—C22—H22	126.7
C13—C12—C8	125.6 (4)	C19—C22—H22	126.7
C16—C12—C8	124.1 (4)	C4—C23—H23A	109.5
O4—C7—C6	109.7 (3)	C4—C23—H23B	109.5
O4—C7—C8	110.7 (3)	H23A—C23—H23B	109.5
C6—C7—C8	108.7 (3)	C4—C23—H23C	109.5
O4—C7—H7	109.2	H23A—C23—H23C	109.5
C6—C7—H7	109.2	H23B—C23—H23C	109.5
C8—C7—H7	109.2	C22—C21—O5	110.7 (4)
C12—C16—C17	113.6 (3)	C22—C21—H21	124.7
C12—C16—C26	111.8 (4)	O5—C21—H21	124.7
C17—C16—C26	109.2 (3)	C16—C26—H26A	109.5
C12—C16—C15	99.7 (3)	C16—C26—H26C	109.5
C17—C16—C15	112.1 (3)	H26A—C26—H26C	109.5
C26—C16—C15	110.3 (3)	C16—C26—H26B	109.5
C19—C15—C14	116.8 (4)	H26A—C26—H26B	109.5
C19—C15—C16	116.1 (4)	H26C—C26—H26B	109.5
C14—C15—C16	103.0 (3)	C19—C20—O5	112.2 (4)
C19—C15—H15	106.7	C19—C20—H20	123.9
C14—C15—H15	106.7	O5—C20—H20	123.9
C16—C15—H15	106.7	C10—C24—H24A	109.5
C3—C4—C11	106.8 (3)	C10—C24—H24B	109.5
C3—C4—C23	108.6 (4)	H24A—C24—H24B	109.5
C11—C4—C23	116.4 (4)	C10—C24—H24C	109.5
C3—C4—C5	118.2 (4)	H24A—C24—H24C	109.5
C11—C4—C5	96.9 (3)	H24B—C24—H24C	109.5
C23—C4—C5	109.8 (3)	C12—C13—C14	112.1 (4)
C18—C17—C16	114.8 (3)	C12—C13—H13	123.9
C18—C17—H17A	108.6	C14—C13—H13	123.9
C16—C17—H17A	108.6	C8—C25—H25A	109.5
C18—C17—H17B	108.6	C8—C25—H25B	109.5
C16—C17—H17B	108.6	H25A—C25—H25B	109.5
H17A—C17—H17B	107.6	C8—C25—H25C	109.5
C6—C11—C4	105.0 (3)	H25A—C25—H25C	109.5
C6—C11—C10	118.8 (3)	H25B—C25—H25C	109.5
C4—C11—C10	121.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C18—H18···O1	1.00	2.53	3.093 (5)	115
O4—H1···O2	0.82 (7)	2.26 (7)	2.784 (4)	122 (6)
C6—H6···O1^i	1.00	2.45	3.332 (5)	147
C21—H21···O3^ii	0.95	2.26	3.183 (5)	164
O4—H1···O1^iii	0.82 (7)	2.22 (7)	2.902 (4)	140 (6)

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

13-(Acetyloxy)-7-(furan-3-yl)-18-hydroxy-1,8,12,16,16-pentamethyl-5,15,19-trioxo-3,6-dioxapentacyclo[9.8.0.0^2,4.0^2,8.0^12,17]nonadecan-9-yl acetate (2)

Crystal data

C30H36O11	Dx = 1.342 Mg m^−3
Mr = 572.59	Cu Kα radiation, λ = 1.54184 Å
Orthorhombic, P212121	Cell parameters from 3267 reflections
a = 11.2394 (8) Å	θ = 3.9–75.2°
b = 11.9259 (11) Å	µ = 0.86 mm^−1
c = 21.1432 (17) Å	T = 100 K
V = 2834.0 (4) Å^3	Block, colorless
Z = 4	0.39 × 0.19 × 0.03 mm
F(000) = 1216

Data collection

Rigaku OD SuperNova Dual source diffractometer with an Atlas detector	5897 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Cu) X-ray Source	4413 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.084
Detector resolution: 10.4508 pixels mm^-1	θmax = 78.7°, θmin = 4.2°
ω scans	h = −12→14
Absorption correction: gaussian (CrysAlis PRO; Rigaku OD, 2015)	k = −14→15
Tmin = 0.832, Tmax = 0.971	l = −26→26
23725 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.051	w = 1/[σ^2(Fo^2) + (0.0622P)^2 + 0.3498P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.149	(Δ/σ)max < 0.001
S = 1.05	Δρmax = 0.22 e Å^−3
5897 reflections	Δρmin = −0.20 e Å^−3
381 parameters	Absolute structure: Refined as an inversion twin
0 restraints	Absolute structure parameter: 0.3 (3)

Special details

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

Refinement. Refined as a 2-component inversion twin.

A low-temperature (100 K) with Supernova, Dual, Cu at zero, Atlas, X-ray apparatus equipped with a micro-focus sealed X-ray tube (λ = 1.54184 Å) and a CCD plate detector were used. Measurements were performed via ω-scans and numerical absorption corrections based on Gaussian integration over a multifaceted crystal model by using CrysAlisPro 1.171.38.43 software (Rigaku Oxford Diffraction, 2015) were done. The structures were solved by direct methods using SHELXT(Sheldrick, 2015a) and refined on F² by full matrix least squares procedures within the independent atom model (IAM) by using SHELXL-2018 program (Sheldrick, 2015b).

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

	x	y	z	Uiso*/Ueq
O10	0.6975 (3)	0.2275 (3)	0.18082 (13)	0.0366 (6)
O2	0.9552 (3)	0.1427 (3)	0.45240 (15)	0.0428 (7)
O8	0.4604 (2)	0.2177 (3)	0.33525 (15)	0.0424 (7)
O3	1.0200 (3)	0.2463 (3)	0.34797 (15)	0.0451 (7)
O4	1.0278 (3)	0.4545 (3)	0.15875 (15)	0.0442 (7)
O5	1.1874 (3)	0.4869 (3)	0.21654 (18)	0.0506 (8)
O11	0.5260 (3)	0.2873 (3)	0.13801 (18)	0.0593 (10)
O9	0.4130 (3)	0.1033 (4)	0.2551 (2)	0.0649 (11)
O1	0.4942 (3)	0.0626 (4)	0.49729 (19)	0.0614 (10)
O7	0.7961 (4)	0.3606 (4)	−0.00568 (16)	0.0665 (11)
C9	0.7309 (3)	0.2876 (3)	0.31879 (16)	0.0301 (8)
H9	0.7638	0.2219	0.2951	0.036*
C12	0.7221 (3)	0.3388 (4)	0.20501 (18)	0.0335 (8)
H12	0.6907	0.3958	0.1746	0.040*
C5	0.7535 (4)	0.1575 (4)	0.41050 (18)	0.0349 (8)
H5	0.7752	0.0974	0.3796	0.042*
C7	0.9240 (3)	0.2752 (4)	0.36778 (18)	0.0357 (9)
C11	0.6601 (3)	0.3537 (4)	0.26869 (18)	0.0337 (8)
H11A	0.5774	0.3253	0.2663	0.040*
H11B	0.6573	0.4342	0.2802	0.040*
C14	0.8936 (4)	0.4058 (3)	0.27223 (19)	0.0340 (8)
C6	0.8712 (4)	0.2181 (4)	0.42640 (18)	0.0368 (9)
H6	0.8539	0.2773	0.4586	0.044*
C8	0.8426 (3)	0.3596 (4)	0.33577 (19)	0.0335 (8)
C10	0.6626 (3)	0.2345 (4)	0.37529 (18)	0.0335 (8)
C15	1.0066 (4)	0.4682 (4)	0.2728 (2)	0.0404 (9)
H15	1.0493	0.4729	0.3143	0.048*
C1	0.5690 (3)	0.1541 (4)	0.3459 (2)	0.0372 (9)
H1	0.5996	0.1278	0.3040	0.045*
C13	0.8607 (4)	0.3506 (4)	0.20943 (19)	0.0356 (8)
C24	0.3904 (4)	0.1831 (4)	0.2877 (2)	0.0452 (10)
C26	0.5988 (4)	0.3187 (4)	0.4190 (2)	0.0393 (9)
H26B	0.6560	0.3499	0.4493	0.047*
H26A	0.5350	0.2803	0.4420	0.047*
H26C	0.5649	0.3795	0.3935	0.047*
C29	0.5948 (4)	0.2123 (4)	0.1494 (2)	0.0467 (10)
C28	0.9276 (4)	0.2383 (4)	0.20345 (19)	0.0383 (9)
H28A	0.9008	0.1870	0.2368	0.046*
H28C	1.0133	0.2514	0.2078	0.046*
H28B	0.9112	0.2051	0.1620	0.046*
C16	1.0817 (4)	0.4704 (4)	0.2147 (2)	0.0433 (10)
C3	0.5683 (5)	0.0709 (4)	0.4559 (2)	0.0483 (11)
C17	0.8996 (4)	0.4308 (4)	0.1554 (2)	0.0407 (9)
H17	0.8555	0.5031	0.1603	0.049*
C18	0.8788 (4)	0.3875 (4)	0.0897 (2)	0.0441 (10)
C27	0.8195 (4)	0.4601 (4)	0.37986 (19)	0.0392 (9)
H27C	0.7501	0.5021	0.3647	0.047*
H27B	0.8893	0.5093	0.3801	0.047*
H27A	0.8042	0.4329	0.4228	0.047*
C4	0.6999 (4)	0.0948 (4)	0.4693 (2)	0.0433 (10)
C2	0.5406 (4)	0.0510 (5)	0.3864 (3)	0.0519 (12)
H2B	0.4552	0.0321	0.3818	0.062*
H2A	0.5876	−0.0137	0.3710	0.062*
C19	0.7883 (6)	0.4154 (6)	0.0510 (2)	0.0615 (15)
H19	0.7268	0.4666	0.0617	0.074*
C22	0.7563 (5)	−0.0244 (4)	0.4747 (2)	0.0506 (12)
H22C	0.7411	−0.0664	0.4357	0.061*
H22A	0.7209	−0.0643	0.5106	0.061*
H22B	0.8423	−0.0174	0.4812	0.061*
C20	0.8974 (5)	0.2972 (5)	−0.0020 (2)	0.0571 (13)
H20	0.9257	0.2499	−0.0349	0.068*
C21	0.9513 (5)	0.3106 (5)	0.0540 (2)	0.0501 (12)
H21	1.0231	0.2761	0.0676	0.060*
C30	0.5796 (5)	0.0926 (5)	0.1307 (3)	0.0569 (13)
H30A	0.6576	0.0560	0.1290	0.068*
H30C	0.5417	0.0887	0.0891	0.068*
H30B	0.5295	0.0544	0.1619	0.068*
C23	0.7148 (5)	0.1544 (5)	0.5327 (2)	0.0508 (12)
H23C	0.7994	0.1578	0.5437	0.061*
H23B	0.6717	0.1129	0.5656	0.061*
H23A	0.6827	0.2306	0.5297	0.061*
C25	0.2848 (4)	0.2573 (5)	0.2798 (3)	0.0600 (14)
H25C	0.2561	0.2810	0.3215	0.072*
H25B	0.2216	0.2163	0.2578	0.072*
H25A	0.3071	0.3235	0.2551	0.072*
O6	0.8954 (3)	0.5267 (3)	0.26821 (14)	0.0391 (6)
H31	1.001 (5)	0.122 (5)	0.425 (3)	0.047*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O10	0.0379 (14)	0.0395 (15)	0.0324 (13)	−0.0015 (13)	−0.0020 (12)	−0.0048 (12)
O2	0.0369 (15)	0.057 (2)	0.0343 (14)	0.0057 (15)	−0.0077 (13)	0.0035 (14)
O8	0.0266 (13)	0.0531 (19)	0.0475 (16)	0.0021 (13)	0.0021 (12)	−0.0016 (14)
O3	0.0308 (13)	0.062 (2)	0.0428 (15)	0.0029 (14)	0.0020 (12)	0.0044 (15)
O4	0.0414 (16)	0.0498 (18)	0.0415 (15)	−0.0050 (15)	0.0108 (13)	0.0046 (14)
O5	0.0377 (16)	0.0523 (19)	0.062 (2)	−0.0059 (15)	0.0091 (15)	0.0093 (16)
O11	0.059 (2)	0.058 (2)	0.061 (2)	0.0028 (19)	−0.0274 (18)	−0.0016 (17)
O9	0.0454 (19)	0.060 (2)	0.089 (3)	−0.0004 (18)	−0.021 (2)	−0.023 (2)
O1	0.0489 (19)	0.065 (2)	0.070 (2)	0.0008 (18)	0.0254 (19)	0.0166 (19)
O7	0.072 (3)	0.096 (3)	0.0316 (16)	0.008 (2)	0.0011 (17)	0.0027 (18)
C9	0.0282 (16)	0.039 (2)	0.0234 (15)	−0.0007 (16)	−0.0005 (14)	−0.0002 (14)
C12	0.0324 (18)	0.039 (2)	0.0294 (17)	0.0003 (16)	−0.0023 (15)	−0.0028 (16)
C5	0.0312 (18)	0.045 (2)	0.0286 (17)	0.0014 (18)	0.0035 (15)	−0.0007 (16)
C7	0.0294 (17)	0.046 (2)	0.0317 (18)	−0.0046 (18)	−0.0042 (15)	−0.0042 (16)
C11	0.0298 (17)	0.040 (2)	0.0313 (18)	0.0019 (17)	−0.0013 (15)	−0.0007 (16)
C14	0.0325 (19)	0.032 (2)	0.0373 (19)	0.0015 (16)	0.0017 (17)	0.0023 (16)
C6	0.0340 (19)	0.047 (2)	0.0292 (18)	0.0044 (19)	−0.0022 (15)	−0.0020 (17)
C8	0.0302 (18)	0.040 (2)	0.0303 (18)	−0.0004 (16)	0.0015 (15)	−0.0046 (16)
C10	0.0291 (17)	0.042 (2)	0.0294 (18)	0.0011 (17)	0.0036 (14)	0.0011 (16)
C15	0.0339 (19)	0.043 (2)	0.044 (2)	−0.0029 (18)	0.0024 (18)	−0.0004 (18)
C1	0.0264 (17)	0.043 (2)	0.042 (2)	−0.0021 (17)	0.0018 (16)	0.0018 (18)
C13	0.0354 (19)	0.040 (2)	0.0310 (18)	0.0010 (17)	0.0035 (16)	0.0003 (17)
C24	0.0283 (18)	0.051 (3)	0.057 (3)	−0.0072 (19)	−0.007 (2)	−0.001 (2)
C26	0.0343 (19)	0.048 (2)	0.036 (2)	0.0056 (19)	0.0050 (17)	−0.0025 (17)
C29	0.048 (2)	0.055 (3)	0.037 (2)	−0.001 (2)	−0.011 (2)	−0.005 (2)
C28	0.0352 (19)	0.045 (2)	0.0349 (19)	0.0030 (18)	0.0041 (16)	−0.0001 (17)
C16	0.045 (2)	0.037 (2)	0.048 (2)	−0.0039 (19)	0.004 (2)	0.0059 (19)
C3	0.045 (2)	0.044 (3)	0.057 (3)	0.004 (2)	0.015 (2)	0.012 (2)
C17	0.040 (2)	0.043 (2)	0.038 (2)	−0.0018 (19)	0.0066 (18)	0.0077 (18)
C18	0.048 (2)	0.047 (3)	0.037 (2)	0.002 (2)	0.009 (2)	0.0067 (18)
C27	0.041 (2)	0.045 (2)	0.0310 (19)	−0.002 (2)	0.0021 (16)	−0.0053 (17)
C4	0.044 (2)	0.051 (3)	0.035 (2)	0.006 (2)	0.011 (2)	0.0102 (19)
C2	0.042 (2)	0.052 (3)	0.062 (3)	−0.010 (2)	−0.002 (2)	0.010 (2)
C19	0.064 (3)	0.085 (4)	0.036 (2)	0.009 (3)	0.004 (2)	0.007 (2)
C22	0.048 (2)	0.057 (3)	0.046 (2)	0.008 (2)	0.009 (2)	0.012 (2)
C20	0.067 (3)	0.068 (3)	0.036 (2)	−0.008 (3)	0.016 (2)	−0.002 (2)
C21	0.054 (3)	0.060 (3)	0.036 (2)	−0.005 (2)	0.011 (2)	0.000 (2)
C30	0.061 (3)	0.059 (3)	0.050 (3)	−0.008 (3)	−0.009 (3)	−0.013 (2)
C23	0.058 (3)	0.064 (3)	0.030 (2)	0.010 (3)	0.010 (2)	0.006 (2)
C25	0.036 (2)	0.069 (4)	0.075 (3)	0.002 (2)	−0.015 (2)	−0.002 (3)
O6	0.0393 (15)	0.0340 (15)	0.0441 (15)	−0.0023 (13)	0.0046 (13)	0.0013 (12)

Geometric parameters (Å, º)

O10—C29	1.344 (5)	C1—C2	1.533 (6)
O10—C12	1.449 (5)	C1—H1	1.0000
O2—C6	1.416 (5)	C13—C28	1.541 (6)
O2—H31	0.81 (6)	C13—C17	1.553 (6)
O8—C24	1.342 (6)	C24—C25	1.490 (7)
O8—C1	1.454 (5)	C26—H26B	0.9800
O3—C7	1.208 (5)	C26—H26A	0.9800
O4—C16	1.343 (6)	C26—H26C	0.9800
O4—C17	1.470 (5)	C29—C30	1.491 (7)
O5—C16	1.205 (6)	C28—H28A	0.9800
O11—C29	1.206 (6)	C28—H28C	0.9800
O9—C24	1.201 (7)	C28—H28B	0.9800
O1—C3	1.213 (6)	C3—C2	1.520 (7)
O7—C19	1.367 (7)	C3—C4	1.533 (7)
O7—C20	1.369 (8)	C17—C18	1.502 (6)
C9—C11	1.543 (5)	C17—H17	1.0000
C9—C10	1.554 (5)	C18—C19	1.348 (8)
C9—C8	1.564 (5)	C18—C21	1.439 (7)
C9—H9	1.0000	C27—H27C	0.9800
C12—C11	1.526 (5)	C27—H27B	0.9800
C12—C13	1.568 (5)	C27—H27A	0.9800
C12—H12	1.0000	C4—C23	1.527 (7)
C5—C6	1.544 (6)	C4—C22	1.561 (7)
C5—C10	1.562 (6)	C2—H2B	0.9900
C5—C4	1.571 (6)	C2—H2A	0.9900
C5—H5	1.0000	C19—H19	0.9500
C7—C8	1.519 (6)	C22—H22C	0.9800
C7—C6	1.534 (6)	C22—H22A	0.9800
C11—H11A	0.9900	C22—H22B	0.9800
C11—H11B	0.9900	C20—C21	1.341 (8)
C14—O6	1.445 (5)	C20—H20	0.9500
C14—C15	1.472 (6)	C21—H21	0.9500
C14—C13	1.527 (6)	C30—H30A	0.9800
C14—C8	1.561 (5)	C30—H30C	0.9800
C6—H6	1.0000	C30—H30B	0.9800
C8—C27	1.541 (6)	C23—H23C	0.9800
C10—C26	1.542 (6)	C23—H23B	0.9800
C10—C1	1.553 (6)	C23—H23A	0.9800
C15—O6	1.435 (5)	C25—H25C	0.9800
C15—C16	1.490 (6)	C25—H25B	0.9800
C15—H15	1.0000	C25—H25A	0.9800
C29—O10—C12	117.5 (3)	C10—C26—H26C	109.5
C6—O2—H31	110 (4)	H26B—C26—H26C	109.5
C24—O8—C1	116.6 (4)	H26A—C26—H26C	109.5
C16—O4—C17	120.7 (3)	O11—C29—O10	123.3 (5)
C19—O7—C20	105.5 (4)	O11—C29—C30	125.7 (5)
C11—C9—C10	118.8 (3)	O10—C29—C30	111.0 (4)
C11—C9—C8	106.9 (3)	C13—C28—H28A	109.5
C10—C9—C8	116.4 (3)	C13—C28—H28C	109.5
C11—C9—H9	104.4	H28A—C28—H28C	109.5
C10—C9—H9	104.4	C13—C28—H28B	109.5
C8—C9—H9	104.4	H28A—C28—H28B	109.5
O10—C12—C11	109.3 (3)	H28C—C28—H28B	109.5
O10—C12—C13	107.0 (3)	O5—C16—O4	119.7 (4)
C11—C12—C13	113.0 (3)	O5—C16—C15	122.3 (4)
O10—C12—H12	109.1	O4—C16—C15	118.0 (4)
C11—C12—H12	109.1	O1—C3—C2	122.9 (5)
C13—C12—H12	109.1	O1—C3—C4	123.0 (5)
C6—C5—C10	112.9 (4)	C2—C3—C4	114.0 (4)
C6—C5—C4	112.3 (3)	O4—C17—C18	105.2 (4)
C10—C5—C4	113.9 (3)	O4—C17—C13	111.0 (4)
C6—C5—H5	105.6	C18—C17—C13	115.1 (4)
C10—C5—H5	105.6	O4—C17—H17	108.4
C4—C5—H5	105.6	C18—C17—H17	108.4
O3—C7—C8	124.9 (4)	C13—C17—H17	108.4
O3—C7—C6	119.9 (4)	C19—C18—C21	105.5 (5)
C8—C7—C6	114.9 (3)	C19—C18—C17	126.5 (5)
C12—C11—C9	108.1 (3)	C21—C18—C17	128.0 (4)
C12—C11—H11A	110.1	C8—C27—H27C	109.5
C9—C11—H11A	110.1	C8—C27—H27B	109.5
C12—C11—H11B	110.1	H27C—C27—H27B	109.5
C9—C11—H11B	110.1	C8—C27—H27A	109.5
H11A—C11—H11B	108.4	H27C—C27—H27A	109.5
O6—C14—C15	58.9 (3)	H27B—C27—H27A	109.5
O6—C14—C13	112.5 (3)	C23—C4—C3	110.8 (4)
C15—C14—C13	115.7 (4)	C23—C4—C22	108.4 (4)
O6—C14—C8	114.1 (3)	C3—C4—C22	103.6 (4)
C15—C14—C8	119.2 (4)	C23—C4—C5	115.6 (4)
C13—C14—C8	120.5 (3)	C3—C4—C5	108.2 (4)
O2—C6—C7	109.7 (3)	C22—C4—C5	109.6 (4)
O2—C6—C5	111.0 (4)	C3—C2—C1	111.9 (4)
C7—C6—C5	111.3 (3)	C3—C2—H2B	109.2
O2—C6—H6	108.2	C1—C2—H2B	109.2
C7—C6—H6	108.2	C3—C2—H2A	109.2
C5—C6—H6	108.2	C1—C2—H2A	109.2
C7—C8—C27	110.3 (3)	H2B—C2—H2A	107.9
C7—C8—C14	113.4 (3)	C18—C19—O7	111.4 (5)
C27—C8—C14	108.0 (3)	C18—C19—H19	124.3
C7—C8—C9	102.8 (3)	O7—C19—H19	124.3
C27—C8—C9	115.5 (3)	C4—C22—H22C	109.5
C14—C8—C9	106.9 (3)	C4—C22—H22A	109.5
C26—C10—C1	109.1 (3)	H22C—C22—H22A	109.5
C26—C10—C9	115.2 (4)	C4—C22—H22B	109.5
C1—C10—C9	106.1 (3)	H22C—C22—H22B	109.5
C26—C10—C5	113.6 (3)	H22A—C22—H22B	109.5
C1—C10—C5	105.7 (3)	C21—C20—O7	111.1 (5)
C9—C10—C5	106.4 (3)	C21—C20—H20	124.4
O6—C15—C14	59.6 (3)	O7—C20—H20	124.4
O6—C15—C16	115.3 (4)	C20—C21—C18	106.4 (5)
C14—C15—C16	119.3 (4)	C20—C21—H21	126.8
O6—C15—H15	116.7	C18—C21—H21	126.8
C14—C15—H15	116.7	C29—C30—H30A	109.5
C16—C15—H15	116.7	C29—C30—H30C	109.5
O8—C1—C2	109.2 (3)	H30A—C30—H30C	109.5
O8—C1—C10	108.0 (4)	C29—C30—H30B	109.5
C2—C1—C10	114.3 (4)	H30A—C30—H30B	109.5
O8—C1—H1	108.4	H30C—C30—H30B	109.5
C2—C1—H1	108.4	C4—C23—H23C	109.5
C10—C1—H1	108.4	C4—C23—H23B	109.5
C14—C13—C28	109.1 (3)	H23C—C23—H23B	109.5
C14—C13—C17	107.8 (4)	C4—C23—H23A	109.5
C28—C13—C17	109.8 (3)	H23C—C23—H23A	109.5
C14—C13—C12	109.3 (3)	H23B—C23—H23A	109.5
C28—C13—C12	113.7 (4)	C24—C25—H25C	109.5
C17—C13—C12	106.9 (3)	C24—C25—H25B	109.5
O9—C24—O8	123.3 (4)	H25C—C25—H25B	109.5
O9—C24—C25	125.1 (5)	C24—C25—H25A	109.5
O8—C24—C25	111.6 (4)	H25C—C25—H25A	109.5
C10—C26—H26B	109.5	H25B—C25—H25A	109.5
C10—C26—H26A	109.5	C15—O6—C14	61.5 (3)
H26B—C26—H26A	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11A···O8	0.99	2.35	3.106 (5)	133
C30—H30B···O9	0.98	2.44	3.231 (7)	138
O2—H31···O3	0.81 (6)	2.21 (6)	2.633 (5)	113 (5)
C5—H5···O5^i	1.00	2.46	3.435 (5)	165
C11—H11B···O9^ii	0.99	2.29	3.128 (6)	142
C25—H25A···O5^iii	0.98	2.50	3.238 (7)	132
C20—H20···O11^iv	0.95	2.49	3.372 (6)	154

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