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.
Supporting information
CCDC references: 1509169; 1509168
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
top
Crystal data top
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) Å3 | Plate, colourless |
Z = 4 | 0.32 × 0.09 × 0.04 mm |
Data collection top
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 top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.040 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.102 | w = 1/[σ2(Fo2) + (0.0461P)2 + 1.0428P] where P = (Fo2 + 2Fc2)/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 top
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 (Å2) top | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
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) top
D—H···A | D—H | H···A | D···A | D—H···A |
O6—H6A···O7i | 0.91 (2) | 1.88 (2) | 2.7885 (11) | 178.8 (18) |
C1—H1···O5ii | 1.00 | 2.49 | 3.4073 (13) | 152 |
C11—H11···O1iii | 0.95 | 2.61 | 3.3842 (14) | 139 |
C10—H10···O8iii | 0.95 | 2.55 | 3.3855 (15) | 146 |
C7—H7···πiv | 1.00 | 2.67 | 3.5596 (12) | 149 |
C13—H13···O1v | 0.95 | 2.57 | 3.3506 (14) | 140 |
C19—H19···O9vi | 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
top
Crystal data top
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) Å3 | Needle, colourless |
Z = 4 | 0.33 × 0.02 × 0.02 mm |
Data collection top
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 top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.056 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.116 | w = 1/[σ2(Fo2) + (0.0375P)2 + 2.1958P] where P = (Fo2 + 2Fc2)/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 top
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 (Å2) top | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
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) top
D—H···A | D—H | H···A | D···A | D—H···A |
O6—H6A···O7i | 0.93 (3) | 1.86 (3) | 2.786 (3) | 172 (3) |
C1—H1···O5ii | 1.00 | 2.51 | 3.450 (3) | 156 |
C10—H10···O8iii | 0.95 | 2.60 | 3.377 (3) | 139 |
C11—H11···O1iii | 0.95 | 2.65 | 3.392 (3) | 135 |
C7—H7···πiv | 1.00 | 2.52 | 3.442 (2) | 153 |
C13—H13···O1v | 0.95 | 2.71 | 3.493 (3) | 140 |
C19—H19···S1vi | 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. |