Engineering crystals that facilitate the acyl-transfer reaction: insight from a comparison of the crystal structures of myo-inositol-1,3,5-orthoformate-derived benzoates and carbonates

Minor variations in the mol­ecular structure of constituent mol­ecules of reactive crystals often yield crystals with significantly different properties due to altered modes of mol­ecular association in the solid state. Hence, these studies could provide a better understanding of the complex chemical processes occurring in the crystalline state. However, reactions that proceed efficiently in mol­ecular crystals are only a small fraction of the reactions that are known to proceed (with comparable efficiency) in the solution state. Hence, for consistent progress in this area of research, investigation of newer reactive mol­ecular crystals which support different kinds of reactions and their related systems is essential. The crystal structures and acyl-transfer reactivity of a myo-inositol-1,3,5-orthoformate-derived dibenzoate and its carbonate (4-O-benzoyl-2-O-phen­oxy­carbonyl-myo-inositol 1,3,5-orthoformate, C₂₁H₁₈O₉) and thio­carbonate (4-O-benzoyl-2-O-phen­oxy­thio­carbonyl-myo-inositol 1,3,5-orthoformate, C₂₁H₁₈O₈S) analogs are compared with the aim of understanding the relationship between crystal structure and acyl-transfer reactivity. Insertion of an O atom in the acyl (or thioac­yl) group of an ester gives the corresponding carbonate (or thio­carbonate). This seemingly minor change in mol­ecular structure results in a considerable change in the packing of the mol­ecules in the crystals of myo-inositol-1,3,5-orthoformate-derived benzoates and the corresponding carbonates. These differences result in a lack of inter­molecular acyl-transfer reactivity in crystals of myo-inositol-1,3,5-orthoformate-derived carbonates. Hence, this study illustrates the sensitivity of the relative orientation of mol­ecules, their packing and ensuing changes in the reactivity of resulting crystals to minor changes in mol­ecular structure.

Computing details

For both compounds, data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXS97 (Sheldrick 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: APEX3 (Bruker, 2016), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

(2) 4-O-Benzoyl-2-O-phenoxycarbonyl-myo-inositol 1,3,5-orthoformate

Crystal data

C21H18O9	F(000) = 864
Mr = 414.35	Dx = 1.522 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.7254 (3) Å	Cell parameters from 9903 reflections
b = 5.8819 (1) Å	θ = 3.2–30.1°
c = 21.1510 (5) Å	µ = 0.12 mm^−1
β = 99.321 (1)°	T = 100 K
V = 1807.77 (6) Å^3	Plate, colourless
Z = 4	0.32 × 0.09 × 0.04 mm

Data collection

Bruker D8 VENTURE Kappa Duo PHOTON II CPAD diffractometer	5276 independent reflections
Radiation source: micro-focus sealed tube, Incoatech IµS HB	4753 reflections with I > 2σ(I)
Multilayer mirrors monochromator	Rint = 0.025
φ and ω scans	θmax = 30.1°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2016)	h = −20→20
Tmin = 0.962, Tmax = 0.995	k = −8→8
33549 measured reflections	l = −29→29

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.102	w = 1/[σ^2(Fo^2) + (0.0461P)^2 + 1.0428P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
5276 reflections	Δρmax = 0.46 e Å^−3
275 parameters	Δρmin = −0.34 e Å^−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.

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

	x	y	z	Uiso*/Ueq
O1	0.13854 (5)	0.64559 (13)	0.66334 (4)	0.01530 (15)
O2	0.15708 (5)	0.46235 (15)	0.54207 (4)	0.02106 (18)
O3	0.17425 (5)	0.91648 (13)	0.59153 (3)	0.01429 (15)
O4	0.41106 (5)	0.73391 (13)	0.60497 (4)	0.01546 (15)
O5	0.23649 (5)	0.94413 (13)	0.69908 (3)	0.01446 (15)
O6	0.37149 (5)	0.41873 (14)	0.69649 (4)	0.01990 (17)
O7	0.51452 (5)	0.87270 (15)	0.68537 (4)	0.02058 (17)
O8	0.08992 (5)	0.25039 (15)	0.46675 (4)	0.02285 (19)
O9	0.24558 (5)	0.23199 (14)	0.49075 (4)	0.01731 (16)
C1	0.21432 (7)	0.50025 (18)	0.65412 (5)	0.01559 (19)
H1	0.1977	0.3376	0.6600	0.019*
C2	0.23607 (7)	0.53578 (18)	0.58689 (5)	0.01505 (19)
H2	0.2918	0.4465	0.5808	0.018*
C3	0.25189 (7)	0.78912 (18)	0.57739 (5)	0.01371 (18)
H3	0.2611	0.8187	0.5323	0.016*
C4	0.33713 (7)	0.86469 (18)	0.62430 (5)	0.01375 (18)
H4	0.3483	1.0308	0.6191	0.016*
C5	0.31853 (7)	0.81586 (18)	0.69239 (5)	0.01355 (18)
H5	0.3716	0.8683	0.7247	0.016*
C6	0.29765 (7)	0.56518 (18)	0.70377 (5)	0.01540 (19)
H6	0.2820	0.5468	0.7478	0.018*
C7	0.15991 (7)	0.87391 (17)	0.65461 (5)	0.01318 (18)
H7	0.1059	0.9670	0.6623	0.016*
C8	0.17312 (7)	0.30724 (18)	0.49909 (5)	0.01411 (19)
C9	0.08649 (7)	0.09062 (18)	0.41716 (5)	0.01427 (19)
C10	0.05095 (7)	−0.1206 (2)	0.42686 (6)	0.0203 (2)
H10	0.0369	−0.1626	0.4675	0.024*
C11	0.03618 (8)	−0.2713 (2)	0.37526 (8)	0.0320 (3)
H11	0.0105	−0.4170	0.3803	0.038*
C12	0.05894 (8)	−0.2087 (3)	0.31676 (7)	0.0354 (4)
H12	0.0485	−0.3116	0.2817	0.042*
C13	0.09678 (9)	0.0024 (3)	0.30889 (5)	0.0309 (3)
H13	0.1135	0.0426	0.2688	0.037*
C14	0.11030 (8)	0.1552 (2)	0.35925 (6)	0.0217 (2)
H14	0.1354	0.3015	0.3541	0.026*
C15	0.49428 (7)	0.73871 (18)	0.64185 (5)	0.01532 (19)
C16	0.55608 (7)	0.56019 (19)	0.62296 (5)	0.0161 (2)
C17	0.64682 (7)	0.5533 (2)	0.65440 (5)	0.0200 (2)
H17	0.6688	0.6664	0.6851	0.024*
C18	0.70509 (8)	0.3810 (2)	0.64077 (6)	0.0236 (2)
H18	0.7668	0.3760	0.6625	0.028*
C19	0.67390 (8)	0.2163 (2)	0.59565 (6)	0.0247 (2)
H19	0.7141	0.0987	0.5865	0.030*
C20	0.58366 (9)	0.2237 (2)	0.56373 (6)	0.0269 (3)
H20	0.5624	0.1117	0.5325	0.032*
C21	0.52442 (8)	0.3946 (2)	0.57744 (6)	0.0226 (2)
H21	0.4626	0.3985	0.5559	0.027*
H6A	0.4080 (13)	0.404 (3)	0.7353 (10)	0.046 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0137 (3)	0.0128 (3)	0.0192 (4)	−0.0001 (3)	0.0021 (3)	0.0016 (3)
O2	0.0141 (3)	0.0233 (4)	0.0231 (4)	0.0051 (3)	−0.0050 (3)	−0.0141 (3)
O3	0.0151 (3)	0.0146 (3)	0.0131 (3)	0.0061 (3)	0.0021 (2)	0.0024 (3)
O4	0.0120 (3)	0.0197 (4)	0.0143 (3)	0.0036 (3)	0.0011 (3)	−0.0012 (3)
O5	0.0131 (3)	0.0150 (3)	0.0149 (3)	0.0013 (3)	0.0011 (3)	−0.0044 (3)
O6	0.0183 (4)	0.0194 (4)	0.0203 (4)	0.0075 (3)	−0.0020 (3)	0.0034 (3)
O7	0.0168 (3)	0.0229 (4)	0.0211 (4)	−0.0013 (3)	0.0002 (3)	−0.0051 (3)
O8	0.0132 (3)	0.0298 (5)	0.0243 (4)	0.0015 (3)	−0.0008 (3)	−0.0174 (3)
O9	0.0139 (3)	0.0218 (4)	0.0162 (3)	0.0019 (3)	0.0023 (3)	−0.0046 (3)
C1	0.0147 (4)	0.0104 (4)	0.0204 (5)	0.0018 (3)	−0.0008 (4)	0.0009 (4)
C2	0.0125 (4)	0.0146 (4)	0.0160 (4)	0.0033 (3)	−0.0036 (3)	−0.0056 (4)
C3	0.0133 (4)	0.0157 (5)	0.0118 (4)	0.0041 (3)	0.0010 (3)	−0.0003 (3)
C4	0.0131 (4)	0.0136 (4)	0.0146 (4)	0.0015 (3)	0.0024 (3)	−0.0004 (3)
C5	0.0127 (4)	0.0148 (4)	0.0127 (4)	0.0011 (3)	0.0007 (3)	−0.0021 (3)
C6	0.0153 (4)	0.0156 (5)	0.0144 (4)	0.0026 (4)	0.0000 (3)	0.0032 (4)
C7	0.0138 (4)	0.0125 (4)	0.0130 (4)	0.0011 (3)	0.0014 (3)	−0.0004 (3)
C8	0.0147 (4)	0.0134 (4)	0.0136 (4)	0.0003 (3)	0.0003 (3)	−0.0024 (3)
C9	0.0117 (4)	0.0167 (5)	0.0137 (4)	0.0019 (3)	−0.0001 (3)	−0.0059 (4)
C10	0.0150 (4)	0.0191 (5)	0.0276 (6)	0.0035 (4)	0.0055 (4)	0.0017 (4)
C11	0.0128 (5)	0.0185 (5)	0.0632 (9)	0.0011 (4)	0.0011 (5)	−0.0159 (6)
C12	0.0180 (5)	0.0477 (8)	0.0352 (7)	0.0154 (5)	−0.0113 (5)	−0.0299 (6)
C13	0.0296 (6)	0.0492 (8)	0.0130 (5)	0.0236 (6)	0.0008 (4)	−0.0034 (5)
C14	0.0231 (5)	0.0218 (5)	0.0221 (5)	0.0079 (4)	0.0088 (4)	0.0033 (4)
C15	0.0134 (4)	0.0176 (5)	0.0147 (4)	0.0005 (4)	0.0018 (3)	0.0023 (4)
C16	0.0145 (4)	0.0202 (5)	0.0140 (4)	0.0031 (4)	0.0032 (3)	0.0021 (4)
C17	0.0151 (5)	0.0250 (5)	0.0194 (5)	0.0018 (4)	0.0017 (4)	0.0023 (4)
C18	0.0153 (5)	0.0309 (6)	0.0249 (5)	0.0071 (4)	0.0037 (4)	0.0067 (5)
C19	0.0246 (5)	0.0287 (6)	0.0227 (5)	0.0118 (5)	0.0096 (4)	0.0052 (5)
C20	0.0284 (6)	0.0295 (6)	0.0227 (6)	0.0087 (5)	0.0043 (4)	−0.0059 (5)
C21	0.0194 (5)	0.0275 (6)	0.0201 (5)	0.0059 (4)	0.0006 (4)	−0.0041 (4)

Geometric parameters (Å, º)

O1—C7	1.3984 (12)	C5—H5	1.0000
O1—C1	1.4438 (12)	C6—H6	1.0000
O2—C8	1.3356 (12)	C7—H7	1.0000
O2—C2	1.4427 (12)	C9—C10	1.3762 (15)
O3—C7	1.4067 (12)	C9—C14	1.3808 (15)
O3—C3	1.4382 (12)	C10—C11	1.3955 (18)
O4—C15	1.3421 (12)	C10—H10	0.9500
O4—C4	1.4451 (12)	C11—C12	1.383 (2)
O5—C7	1.4083 (12)	C11—H11	0.9500
O5—C5	1.4505 (12)	C12—C13	1.382 (2)
O6—C6	1.4150 (12)	C12—H12	0.9500
O6—H6A	0.91 (2)	C13—C14	1.3830 (18)
O7—C15	1.2117 (13)	C13—H13	0.9500
O8—C8	1.3450 (12)	C14—H14	0.9500
O8—C9	1.4031 (12)	C15—C16	1.4861 (15)
O9—C8	1.1944 (12)	C16—C17	1.3933 (14)
C1—C2	1.5218 (15)	C16—C21	1.3956 (16)
C1—C6	1.5286 (14)	C17—C18	1.3879 (16)
C1—H1	1.0000	C17—H17	0.9500
C2—C3	1.5265 (15)	C18—C19	1.3848 (19)
C2—H2	1.0000	C18—H18	0.9500
C3—C4	1.5342 (14)	C19—C20	1.3902 (17)
C3—H3	1.0000	C19—H19	0.9500
C4—C5	1.5360 (14)	C20—C21	1.3920 (16)
C4—H4	1.0000	C20—H20	0.9500
C5—C6	1.5332 (15)	C21—H21	0.9500
C7—O1—C1	110.81 (8)	O1—C7—H7	107.6
C8—O2—C2	116.06 (8)	O3—C7—H7	107.6
C7—O3—C3	110.54 (7)	O5—C7—H7	107.6
C15—O4—C4	118.89 (8)	O9—C8—O2	127.90 (9)
C7—O5—C5	111.82 (7)	O9—C8—O8	126.49 (9)
C6—O6—H6A	108.2 (12)	O2—C8—O8	105.61 (8)
C8—O8—C9	117.79 (8)	C10—C9—C14	122.53 (10)
O1—C1—C2	109.22 (8)	C10—C9—O8	117.49 (10)
O1—C1—C6	108.14 (8)	C14—C9—O8	119.70 (10)
C2—C1—C6	109.91 (8)	C9—C10—C11	118.14 (11)
O1—C1—H1	109.9	C9—C10—H10	120.9
C2—C1—H1	109.8	C11—C10—H10	120.9
C6—C1—H1	109.9	C12—C11—C10	120.06 (12)
O2—C2—C1	107.68 (9)	C12—C11—H11	120.0
O2—C2—C3	109.25 (8)	C10—C11—H11	120.0
C1—C2—C3	108.47 (8)	C13—C12—C11	120.52 (11)
O2—C2—H2	110.5	C13—C12—H12	119.7
C1—C2—H2	110.5	C11—C12—H12	119.7
C3—C2—H2	110.5	C12—C13—C14	120.11 (12)
O3—C3—C2	109.74 (8)	C12—C13—H13	119.9
O3—C3—C4	108.02 (8)	C14—C13—H13	119.9
C2—C3—C4	108.90 (8)	C9—C14—C13	118.61 (12)
O3—C3—H3	110.0	C9—C14—H14	120.7
C2—C3—H3	110.0	C13—C14—H14	120.7
C4—C3—H3	110.0	O7—C15—O4	122.98 (10)
O4—C4—C3	103.76 (8)	O7—C15—C16	125.30 (10)
O4—C4—C5	115.00 (8)	O4—C15—C16	111.72 (9)
C3—C4—C5	107.50 (8)	C17—C16—C21	119.75 (10)
O4—C4—H4	110.1	C17—C16—C15	118.30 (10)
C3—C4—H4	110.1	C21—C16—C15	121.87 (10)
C5—C4—H4	110.1	C18—C17—C16	119.97 (11)
O5—C5—C6	107.07 (8)	C18—C17—H17	120.0
O5—C5—C4	105.79 (8)	C16—C17—H17	120.0
C6—C5—C4	113.44 (8)	C19—C18—C17	120.43 (11)
O5—C5—H5	110.1	C19—C18—H18	119.8
C6—C5—H5	110.1	C17—C18—H18	119.8
C4—C5—H5	110.1	C18—C19—C20	119.81 (11)
O6—C6—C1	108.59 (9)	C18—C19—H19	120.1
O6—C6—C5	113.03 (8)	C20—C19—H19	120.1
C1—C6—C5	106.95 (8)	C19—C20—C21	120.22 (12)
O6—C6—H6	109.4	C19—C20—H20	119.9
C1—C6—H6	109.4	C21—C20—H20	119.9
C5—C6—H6	109.4	C20—C21—C16	119.81 (11)
O1—C7—O3	111.58 (8)	C20—C21—H21	120.1
O1—C7—O5	111.50 (8)	C16—C21—H21	120.1
O3—C7—O5	110.75 (8)
C7—O1—C1—C2	−58.73 (10)	C1—O1—C7—O3	63.24 (10)
C7—O1—C1—C6	60.85 (10)	C1—O1—C7—O5	−61.18 (10)
C8—O2—C2—C1	−125.41 (10)	C3—O3—C7—O1	−62.78 (10)
C8—O2—C2—C3	116.98 (10)	C3—O3—C7—O5	62.06 (10)
O1—C1—C2—O2	−64.14 (10)	C5—O5—C7—O1	61.36 (10)
C6—C1—C2—O2	177.38 (8)	C5—O5—C7—O3	−63.53 (10)
O1—C1—C2—C3	53.98 (10)	C2—O2—C8—O9	−4.93 (17)
C6—C1—C2—C3	−64.50 (10)	C2—O2—C8—O8	174.66 (9)
C7—O3—C3—C2	58.03 (10)	C9—O8—C8—O9	−1.47 (17)
C7—O3—C3—C4	−60.57 (10)	C9—O8—C8—O2	178.93 (9)
O2—C2—C3—O3	63.09 (10)	C8—O8—C9—C10	110.16 (11)
C1—C2—C3—O3	−54.03 (10)	C8—O8—C9—C14	−75.73 (13)
O2—C2—C3—C4	−178.87 (8)	C14—C9—C10—C11	−1.94 (16)
C1—C2—C3—C4	64.02 (10)	O8—C9—C10—C11	171.99 (9)
C15—O4—C4—C3	−171.63 (8)	C9—C10—C11—C12	1.35 (16)
C15—O4—C4—C5	−54.52 (12)	C10—C11—C12—C13	0.31 (18)
O3—C3—C4—O4	−178.17 (7)	C11—C12—C13—C14	−1.47 (18)
C2—C3—C4—O4	62.71 (10)	C10—C9—C14—C13	0.81 (16)
O3—C3—C4—C5	59.60 (10)	O8—C9—C14—C13	−172.98 (10)
C2—C3—C4—C5	−59.53 (10)	C12—C13—C14—C9	0.92 (17)
C7—O5—C5—C6	−59.86 (10)	C4—O4—C15—O7	−11.34 (15)
C7—O5—C5—C4	61.42 (10)	C4—O4—C15—C16	168.02 (8)
O4—C4—C5—O5	−173.80 (8)	O7—C15—C16—C17	−4.59 (17)
C3—C4—C5—O5	−58.83 (10)	O4—C15—C16—C17	176.07 (9)
O4—C4—C5—C6	−56.73 (11)	O7—C15—C16—C21	172.07 (11)
C3—C4—C5—C6	58.24 (10)	O4—C15—C16—C21	−7.27 (15)
O1—C1—C6—O6	178.12 (8)	C21—C16—C17—C18	−0.55 (17)
C2—C1—C6—O6	−62.73 (11)	C15—C16—C17—C18	176.19 (10)
O1—C1—C6—C5	−59.61 (10)	C16—C17—C18—C19	0.52 (18)
C2—C1—C6—C5	59.54 (10)	C17—C18—C19—C20	0.06 (18)
O5—C5—C6—O6	177.99 (8)	C18—C19—C20—C21	−0.61 (19)
C4—C5—C6—O6	61.68 (11)	C19—C20—C21—C16	0.6 (2)
O5—C5—C6—C1	58.55 (10)	C17—C16—C21—C20	−0.01 (18)
C4—C5—C6—C1	−57.77 (10)	C15—C16—C21—C20	−176.62 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O6—H6A···O7^i	0.91 (2)	1.88 (2)	2.7885 (11)	178.8 (18)
C1—H1···O5^ii	1.00	2.49	3.4073 (13)	152
C11—H11···O1^iii	0.95	2.61	3.3842 (14)	139
C10—H10···O8^iii	0.95	2.55	3.3855 (15)	146
C7—H7···π^iv	1.00	2.67	3.5596 (12)	149
C13—H13···O1^v	0.95	2.57	3.3506 (14)	140
C19—H19···O9^vi	0.95	2.67	3.5216 (15)	150

Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) x, y−1, z; (iii) −x, −y, −z+1; (iv) −x, −y+1, −z+1; (v) x, −y+1/2, z−1/2; (vi) −x+1, −y, −z+1.

(3) 4-O-Benzoyl-2-O-phenoxythiocarbonyl-myo-inositol 1,3,5-orthoformate

Crystal data

C21H18O8S	F(000) = 896
Mr = 430.41	Dx = 1.530 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.5888 (7) Å	Cell parameters from 5599 reflections
b = 6.0440 (3) Å	θ = 2.6–27.9°
c = 21.5364 (12) Å	µ = 0.22 mm^−1
β = 100.216 (2)°	T = 100 K
V = 1868.86 (17) Å^3	Needle, colourless
Z = 4	0.33 × 0.02 × 0.02 mm

Data collection

Bruker D8 VENTURE Kappa Duo PHOTON II CPAD diffractometer	4628 independent reflections
Radiation source: micro-focus sealed tube, Incoatech IµS HB	3279 reflections with I > 2σ(I)
Multilayer mirrors monochromator	Rint = 0.090
φ and ω scans	θmax = 28.3°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2016)	h = −19→19
Tmin = 0.930, Tmax = 0.996	k = −7→8
37126 measured reflections	l = −28→28

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.056	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.116	w = 1/[σ^2(Fo^2) + (0.0375P)^2 + 2.1958P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
4628 reflections	Δρmax = 0.50 e Å^−3
275 parameters	Δρmin = −0.44 e Å^−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.

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

	x	y	z	Uiso*/Ueq
S1	0.27761 (4)	0.24367 (10)	0.48531 (3)	0.01741 (14)
O1	0.13153 (11)	0.6454 (3)	0.66367 (8)	0.0156 (4)
O2	0.15598 (11)	0.4315 (3)	0.54815 (8)	0.0166 (4)
O3	0.16495 (11)	0.8894 (3)	0.58781 (8)	0.0154 (4)
O4	0.40715 (10)	0.7296 (3)	0.60686 (8)	0.0171 (4)
O5	0.22794 (10)	0.9475 (3)	0.69317 (8)	0.0147 (4)
O6	0.36910 (12)	0.4395 (3)	0.70203 (9)	0.0226 (4)
O7	0.50933 (11)	0.8925 (3)	0.68337 (9)	0.0225 (4)
O8	0.09258 (10)	0.2388 (3)	0.47020 (8)	0.0168 (4)
C1	0.20965 (16)	0.5047 (4)	0.65828 (12)	0.0160 (5)
H1	0.1946	0.3477	0.6672	0.019*
C2	0.23269 (16)	0.5229 (4)	0.59242 (11)	0.0155 (5)
H2	0.2912	0.4393	0.5901	0.019*
C3	0.24521 (15)	0.7658 (4)	0.57749 (11)	0.0142 (5)
H3	0.2543	0.7830	0.5328	0.017*
C4	0.33025 (15)	0.8552 (4)	0.62278 (11)	0.0159 (5)
H4	0.3388	1.0160	0.6144	0.019*
C5	0.31250 (15)	0.8235 (4)	0.69014 (12)	0.0150 (5)
H5	0.3658	0.8838	0.7212	0.018*
C6	0.29348 (16)	0.5827 (4)	0.70606 (12)	0.0169 (5)
H6	0.2783	0.5750	0.7495	0.020*
C7	0.15127 (15)	0.8666 (4)	0.65048 (11)	0.0137 (5)
H7	0.0958	0.9578	0.6554	0.016*
C8	0.17562 (16)	0.3044 (4)	0.50182 (11)	0.0143 (5)
C9	0.08834 (15)	0.0857 (4)	0.42039 (11)	0.0134 (5)
C10	0.05671 (15)	−0.1245 (4)	0.43089 (12)	0.0153 (5)
H10	0.0460	−0.1669	0.4715	0.018*
C11	0.04107 (16)	−0.2717 (4)	0.38082 (13)	0.0230 (6)
H11	0.0180	−0.4158	0.3866	0.028*
C12	0.05913 (17)	−0.2085 (4)	0.32239 (13)	0.0249 (6)
H12	0.0488	−0.3100	0.2882	0.030*
C13	0.09218 (17)	0.0019 (5)	0.31354 (13)	0.0234 (6)
H13	0.1051	0.0433	0.2734	0.028*
C14	0.10641 (16)	0.1518 (4)	0.36257 (12)	0.0178 (5)
H14	0.1281	0.2971	0.3566	0.021*
C15	0.49149 (15)	0.7509 (4)	0.64318 (11)	0.0166 (5)
C16	0.55778 (16)	0.5808 (4)	0.62811 (12)	0.0184 (5)
C17	0.64762 (16)	0.5778 (4)	0.66313 (12)	0.0185 (5)
H17	0.6665	0.6878	0.6943	0.022*
C18	0.70941 (16)	0.4140 (4)	0.65246 (12)	0.0196 (5)
H18	0.7707	0.4117	0.6765	0.024*
C19	0.68264 (17)	0.2544 (4)	0.60729 (12)	0.0227 (5)
H19	0.7253	0.1424	0.6002	0.027*
C20	0.59330 (17)	0.2574 (5)	0.57209 (13)	0.0259 (6)
H20	0.5751	0.1476	0.5408	0.031*
C21	0.53049 (17)	0.4188 (4)	0.58228 (13)	0.0223 (6)
H21	0.4692	0.4196	0.5583	0.027*
H6A	0.407 (2)	0.434 (5)	0.7417 (16)	0.039 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0135 (3)	0.0216 (3)	0.0175 (3)	−0.0010 (2)	0.0039 (2)	−0.0046 (3)
O1	0.0143 (8)	0.0140 (8)	0.0189 (9)	−0.0014 (6)	0.0042 (7)	−0.0003 (7)
O2	0.0125 (8)	0.0162 (8)	0.0203 (9)	−0.0001 (6)	0.0005 (7)	−0.0095 (7)
O3	0.0152 (8)	0.0147 (8)	0.0158 (9)	0.0051 (6)	0.0012 (7)	0.0014 (7)
O4	0.0111 (7)	0.0215 (9)	0.0186 (9)	0.0012 (7)	0.0022 (6)	−0.0028 (7)
O5	0.0127 (8)	0.0144 (8)	0.0164 (9)	0.0029 (6)	0.0012 (7)	−0.0034 (7)
O6	0.0210 (9)	0.0213 (9)	0.0241 (11)	0.0096 (7)	0.0001 (8)	0.0019 (8)
O7	0.0168 (9)	0.0237 (9)	0.0255 (10)	0.0004 (7)	0.0000 (7)	−0.0061 (8)
O8	0.0111 (7)	0.0203 (8)	0.0187 (9)	−0.0010 (7)	0.0016 (6)	−0.0081 (7)
C1	0.0179 (12)	0.0099 (10)	0.0195 (13)	0.0018 (9)	0.0017 (10)	0.0012 (10)
C2	0.0130 (11)	0.0148 (11)	0.0172 (13)	0.0018 (9)	−0.0020 (9)	−0.0042 (10)
C3	0.0118 (10)	0.0177 (11)	0.0130 (12)	0.0008 (9)	0.0017 (8)	0.0002 (10)
C4	0.0127 (11)	0.0160 (11)	0.0184 (13)	−0.0010 (9)	0.0013 (9)	−0.0016 (10)
C5	0.0106 (11)	0.0163 (11)	0.0175 (13)	0.0031 (9)	0.0009 (9)	−0.0030 (9)
C6	0.0163 (12)	0.0167 (11)	0.0169 (13)	0.0054 (9)	0.0011 (9)	0.0012 (10)
C7	0.0116 (11)	0.0130 (11)	0.0165 (13)	0.0014 (9)	0.0022 (9)	−0.0017 (9)
C8	0.0164 (11)	0.0100 (11)	0.0160 (12)	−0.0026 (8)	0.0014 (9)	0.0005 (9)
C9	0.0097 (10)	0.0139 (11)	0.0157 (12)	0.0019 (9)	−0.0001 (9)	−0.0055 (9)
C10	0.0101 (10)	0.0154 (11)	0.0202 (13)	0.0021 (9)	0.0026 (9)	−0.0006 (10)
C11	0.0110 (10)	0.0179 (12)	0.0388 (17)	0.0016 (10)	0.0012 (10)	−0.0095 (12)
C12	0.0156 (12)	0.0312 (15)	0.0250 (15)	0.0101 (10)	−0.0047 (10)	−0.0191 (12)
C13	0.0165 (12)	0.0368 (15)	0.0162 (13)	0.0119 (11)	0.0011 (10)	0.0002 (11)
C14	0.0161 (11)	0.0185 (12)	0.0189 (14)	0.0042 (9)	0.0035 (10)	0.0006 (10)
C15	0.0147 (11)	0.0172 (11)	0.0173 (12)	−0.0010 (10)	0.0013 (9)	0.0026 (11)
C16	0.0158 (12)	0.0226 (12)	0.0176 (13)	0.0006 (10)	0.0051 (10)	−0.0001 (10)
C17	0.0157 (12)	0.0230 (12)	0.0166 (13)	0.0001 (10)	0.0025 (10)	0.0001 (10)
C18	0.0140 (11)	0.0249 (13)	0.0199 (14)	0.0037 (10)	0.0033 (10)	0.0049 (11)
C19	0.0248 (13)	0.0211 (12)	0.0238 (14)	0.0084 (11)	0.0084 (10)	0.0014 (12)
C20	0.0243 (13)	0.0257 (13)	0.0274 (15)	0.0034 (11)	0.0033 (11)	−0.0097 (12)
C21	0.0173 (12)	0.0267 (14)	0.0225 (14)	−0.0004 (10)	0.0024 (10)	−0.0049 (11)

Geometric parameters (Å, º)

S1—C8	1.632 (2)	C5—H5	1.0000
O1—C7	1.407 (3)	C6—H6	1.0000
O1—C1	1.443 (3)	C7—H7	1.0000
O2—C8	1.330 (3)	C9—C14	1.377 (3)
O2—C2	1.445 (3)	C9—C10	1.384 (3)
O3—C7	1.406 (3)	C10—C11	1.385 (3)
O3—C3	1.439 (3)	C10—H10	0.9500
O4—C15	1.342 (3)	C11—C12	1.384 (4)
O4—C4	1.445 (3)	C11—H11	0.9500
O5—C7	1.404 (3)	C12—C13	1.385 (4)
O5—C5	1.455 (3)	C12—H12	0.9500
O6—C6	1.417 (3)	C13—C14	1.378 (4)
O6—H6A	0.93 (3)	C13—H13	0.9500
O7—C15	1.212 (3)	C14—H14	0.9500
O8—C8	1.340 (3)	C15—C16	1.486 (3)
O8—C9	1.410 (3)	C16—C17	1.392 (3)
C1—C2	1.519 (3)	C16—C21	1.397 (4)
C1—C6	1.527 (3)	C17—C18	1.385 (3)
C1—H1	1.0000	C17—H17	0.9500
C2—C3	1.521 (3)	C18—C19	1.376 (4)
C2—H2	1.0000	C18—H18	0.9500
C3—C4	1.534 (3)	C19—C20	1.387 (3)
C3—H3	1.0000	C19—H19	0.9500
C4—C5	1.530 (3)	C20—C21	1.382 (4)
C4—H4	1.0000	C20—H20	0.9500
C5—C6	1.532 (3)	C21—H21	0.9500
C7—O1—C1	110.54 (17)	O5—C7—H7	107.7
C8—O2—C2	118.11 (17)	O3—C7—H7	107.7
C7—O3—C3	110.82 (17)	O1—C7—H7	107.7
C15—O4—C4	118.78 (18)	O2—C8—O8	104.86 (18)
C7—O5—C5	111.99 (17)	O2—C8—S1	128.27 (17)
C6—O6—H6A	108 (2)	O8—C8—S1	126.85 (18)
C8—O8—C9	119.64 (17)	C14—C9—C10	122.5 (2)
O1—C1—C2	109.94 (18)	C14—C9—O8	120.5 (2)
O1—C1—C6	108.27 (18)	C10—C9—O8	116.7 (2)
C2—C1—C6	108.88 (19)	C9—C10—C11	118.4 (2)
O1—C1—H1	109.9	C9—C10—H10	120.8
C2—C1—H1	109.9	C11—C10—H10	120.8
C6—C1—H1	109.9	C12—C11—C10	119.9 (2)
O2—C2—C1	108.33 (18)	C12—C11—H11	120.0
O2—C2—C3	109.74 (19)	C10—C11—H11	120.0
C1—C2—C3	108.80 (19)	C11—C12—C13	120.4 (2)
O2—C2—H2	110.0	C11—C12—H12	119.8
C1—C2—H2	110.0	C13—C12—H12	119.8
C3—C2—H2	110.0	C14—C13—C12	120.4 (3)
O3—C3—C2	109.70 (18)	C14—C13—H13	119.8
O3—C3—C4	107.89 (18)	C12—C13—H13	119.8
C2—C3—C4	108.63 (19)	C9—C14—C13	118.4 (2)
O3—C3—H3	110.2	C9—C14—H14	120.8
C2—C3—H3	110.2	C13—C14—H14	120.8
C4—C3—H3	110.2	O7—C15—O4	122.8 (2)
O4—C4—C5	115.35 (19)	O7—C15—C16	125.4 (2)
O4—C4—C3	103.79 (18)	O4—C15—C16	111.8 (2)
C5—C4—C3	107.75 (19)	C17—C16—C21	119.8 (2)
O4—C4—H4	109.9	C17—C16—C15	118.5 (2)
C5—C4—H4	109.9	C21—C16—C15	121.6 (2)
C3—C4—H4	109.9	C18—C17—C16	119.8 (2)
O5—C5—C4	105.38 (18)	C18—C17—H17	120.1
O5—C5—C6	106.91 (18)	C16—C17—H17	120.1
C4—C5—C6	113.53 (19)	C19—C18—C17	120.4 (2)
O5—C5—H5	110.3	C19—C18—H18	119.8
C4—C5—H5	110.3	C17—C18—H18	119.8
C6—C5—H5	110.3	C18—C19—C20	119.9 (2)
O6—C6—C1	108.03 (19)	C18—C19—H19	120.0
O6—C6—C5	113.12 (19)	C20—C19—H19	120.0
C1—C6—C5	107.33 (19)	C21—C20—C19	120.5 (2)
O6—C6—H6	109.4	C21—C20—H20	119.8
C1—C6—H6	109.4	C19—C20—H20	119.8
C5—C6—H6	109.4	C20—C21—C16	119.5 (2)
O5—C7—O3	111.24 (18)	C20—C21—H21	120.2
O5—C7—O1	111.51 (18)	C16—C21—H21	120.2
O3—C7—O1	110.85 (18)
C7—O1—C1—C2	−58.2 (2)	C5—O5—C7—O3	−62.9 (2)
C7—O1—C1—C6	60.7 (2)	C5—O5—C7—O1	61.4 (2)
C8—O2—C2—C1	−138.1 (2)	C3—O3—C7—O5	61.0 (2)
C8—O2—C2—C3	103.2 (2)	C3—O3—C7—O1	−63.7 (2)
O1—C1—C2—O2	−66.3 (2)	C1—O1—C7—O5	−61.2 (2)
C6—C1—C2—O2	175.27 (17)	C1—O1—C7—O3	63.3 (2)
O1—C1—C2—C3	53.0 (2)	C2—O2—C8—O8	178.04 (18)
C6—C1—C2—C3	−65.5 (2)	C2—O2—C8—S1	−3.1 (3)
C7—O3—C3—C2	58.5 (2)	C9—O8—C8—O2	−174.99 (19)
C7—O3—C3—C4	−59.7 (2)	C9—O8—C8—S1	6.2 (3)
O2—C2—C3—O3	65.4 (2)	C8—O8—C9—C14	−76.2 (3)
C1—C2—C3—O3	−53.0 (2)	C8—O8—C9—C10	109.9 (2)
O2—C2—C3—C4	−176.92 (18)	C14—C9—C10—C11	−1.3 (3)
C1—C2—C3—C4	64.7 (2)	O8—C9—C10—C11	172.49 (19)
C15—O4—C4—C5	−55.0 (3)	C9—C10—C11—C12	1.5 (3)
C15—O4—C4—C3	−172.58 (19)	C10—C11—C12—C13	−0.5 (4)
O3—C3—C4—O4	−177.29 (17)	C11—C12—C13—C14	−0.8 (4)
C2—C3—C4—O4	63.8 (2)	C10—C9—C14—C13	0.1 (3)
O3—C3—C4—C5	59.9 (2)	O8—C9—C14—C13	−173.5 (2)
C2—C3—C4—C5	−58.9 (2)	C12—C13—C14—C9	1.0 (3)
C7—O5—C5—C4	61.4 (2)	C4—O4—C15—O7	−10.6 (3)
C7—O5—C5—C6	−59.6 (2)	C4—O4—C15—C16	169.01 (19)
O4—C4—C5—O5	−174.79 (17)	O7—C15—C16—C17	1.3 (4)
C3—C4—C5—O5	−59.4 (2)	O4—C15—C16—C17	−178.3 (2)
O4—C4—C5—C6	−58.1 (3)	O7—C15—C16—C21	177.9 (2)
C3—C4—C5—C6	57.3 (2)	O4—C15—C16—C21	−1.6 (3)
O1—C1—C6—O6	178.09 (18)	C21—C16—C17—C18	−0.2 (4)
C2—C1—C6—O6	−62.4 (2)	C15—C16—C17—C18	176.5 (2)
O1—C1—C6—C5	−59.6 (2)	C16—C17—C18—C19	0.2 (4)
C2—C1—C6—C5	59.9 (2)	C17—C18—C19—C20	0.1 (4)
O5—C5—C6—O6	177.24 (18)	C18—C19—C20—C21	−0.4 (4)
C4—C5—C6—O6	61.5 (3)	C19—C20—C21—C16	0.5 (4)
O5—C5—C6—C1	58.2 (2)	C17—C16—C21—C20	−0.2 (4)
C4—C5—C6—C1	−57.6 (2)	C15—C16—C21—C20	−176.8 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O6—H6A···O7^i	0.93 (3)	1.86 (3)	2.786 (3)	172 (3)
C1—H1···O5^ii	1.00	2.51	3.450 (3)	156
C10—H10···O8^iii	0.95	2.60	3.377 (3)	139
C11—H11···O1^iii	0.95	2.65	3.392 (3)	135
C7—H7···π^iv	1.00	2.52	3.442 (2)	153
C13—H13···O1^v	0.95	2.71	3.493 (3)	140
C19—H19···S1^vi	0.95	2.97	3.713 (3)	136

Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) x, y−1, z; (iii) −x, −y, −z+1; (iv) −x, −y+1, −z+1; (v) x, −y+1/2, z−1/2; (vi) −x+1, −y, −z+1.