Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S205322961502015X/qs3050sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S205322961502015X/qs3050musa25sup2.hkl | |
Chemdraw file https://doi.org/10.1107/S205322961502015X/qs3050musa25sup4.cdx | |
Structure factor file (CIF format) https://doi.org/10.1107/S205322961502015X/qs3050musa26sup3.hkl | |
Chemdraw file https://doi.org/10.1107/S205322961502015X/qs3050musa26sup5.cdx |
CCDC references: 1433081; 1433080
Podand-type ligands are an interesting class of acyclic ligands (Fenton, 1987). They have potential donor atoms, such as oxygen, nitrogen and sulfur, which can form host–guest complexes with many transition metals and can undergo conformational changes due to high flexibility (Oepen et al., 1978; Vögtle et al., 1981; Kumar et al., 2013). These metal complexes can be stabilized by the presence of spheroidal cavities. Such compounds can catalyze reactions and have a high significance in materials science (Neogi & Bharadwaj, 2006). Furthermore, organic phosphates have special importance as they are components of many biological molecules, such as nucleic acids, vitamins and enzymes, which perform essential functions in key life processes (Timosheva et al. 2005).
Interestingly, from hydrolysis studies, Kumara Swamy has noted the formation of several phosphate esters of type I while investigating penta- and hexacoordinated cyclic phosphoranes with six- and higher-membered rings (Kumara Swamy et al., 1998). These reactions are helpful in determining the hydrolytic stability of phosphorane rings (Kumara Swamy et al., 2000). Compound (2) (literature yield 19%) and other similar compounds were synthesized previously by us through hydrolysis of spirophosphoranes with a saturated 1,3,2-dioxaphosphorine ring (see Scheme 1). An alternative route for the synthesis of similar compounds was explored by reacting ClP(O)(OCH2CMe2CH2O) with an equimolar amount of diol in the presence of Et3N (Kumara Swamy et al., 1998).
In this paper, we use a new method to synthesize 2,2'-[benzene-1,2-diylbis(oxy)]bis(5,5-dimethyl-1,3,2-dioxaphosphinane) 2,2'-dioxide, C6H4{O[cyclo-P(O)OCH2CMe2CH2O]}2, (1), 2-[(2'-hydroxybiphenyl-2-yl)oxy]-5,5-dimethyl-1,3,2-dioxaphosphinane 2-oxide, [cyclo-P(O)OCH2CMe2CH2O](2,2'-OC6H4–C6H4OH), (2), and oxybis(5,5-dimethyl-1,3,2-dioxaphosphinane) 2,2'-dioxide, O[cyclo-P(O)OCH2CMe2CH2O]2, (3). This involves the use of cyclo-[P(O)(H)OCH2CMe2CH2O] and the corresponding diol in the presence of N-chlorodiisopropylamine (NCDA). Using this novel approach and adjusting the ratios of reactants, one or both of the –OH groups of the diol could be reacted with thydrogen phosphite under fewer [less stringent?] air-restriction conditions.
Compounds (1), (2) and (3) are readily isolated in a pure crystalline state by reacting hydrogen phosphite and diol/ClN(iPr)2, and recrystallizing the product from dichloromethane and n-hexane. The side product [H2(iPr)2N]+.Cl- is easily removed by washing the precipitate with water. Our new synthetic route leading to compounds (1)–(3) in this study is illustrated in Scheme 2. A range of products can be prepared by reacting 5,5-dimethyl-1,3,2-dioxaphosphinane 2-oxide with either one mole or half a mole of the diol (as in Scheme 2).
The products were characterized by NMR and X-ray methods. The δ phosphorus NMR values [-13.89 p.p.m. for (1), -14.26 p.p.m. for (2) and -21.13 p.p.m. for (3)] are in the expected range for tetracoordinated phosphate esters. An interesting feature in the 1H NMR spectra for the OCH2 groups in all three compounds is illustrated in Fig. 1. A clear AX pattern is observed for compounds (1) and (3), whereas an AB pattern is observed for compound (2). This is due to hydrogen–hydrogen coupling and then 3J coupling to phosphorus, as shown in Fig. 1. Furthermore, two separate signals are observed for the CH3 group in 5,5-dimethyl-1,3,2-dioxaphosphinane.
Chemicals were procured from Aldrich or from local manufacturers and were purified when required. Solvents were purified according to standard procedures (Perrin et al., 1986). NMR spectra were recorded on a Bruker 400 MHz spectrometer. Chemical shifts (CDCl3, p.p.m.) are measured against tetramethylsilane (1H and 13C) or external 85% H3PO4.
N-Chlorodiisopropylamine was prepared as described in the literature (Antczak et al., 1977). Preparations of [cyclo-P(O)OCH2CMe2CH2O](2,2'-OC6H4—C6H4OH), (2) (Kumara Swamy et al., 1998), and O[cyclo-P(O)OCH2CMe2CH2O]2, (3) (Bukowska-Strzyzewska & Dobrowolska, 1978; Cook & White, 1976), have also been described.
To an ice-cold mixture of 5,5-dimethyl-1,3,2-dioxaphosphinane 2-oxide (0.38 g, 2.53 mmol) and 1,2-dihydroxybenzene (0.14 g, 1.27 mmol) in dry diethyl ether (30 ml) was added N-chlorodiisoproylamine (0.34 g, 2.53 mmol) dropwise using a syringe over a period of 5 min. The mixture was brought slowly to room temperature and stirred under nitrogen overnight. The solvent was reduced to 10 ml under vacuum and n-hexane (3 ml) was added to afford (1) and the diisopropylamine hydrochloride salt. The solid was collected, washed quickly with water (15 ml) and then dried in air. The solid was crystallized from dichloromethane and n-hexane (2:1 v/v) to produce a white crystalline solid (yield 0.26 g, 50%; m.p. 420–423 K). 1H NMR (CDCl3, 400 MHz): δ 7.36–7.06 (m, 4H, Ar—H), 4.36 (d, 4H, CH2), 3.91 (dd, 4H, CH2), 1.26 (s, 6H, CH3), 0.84 (s, 6H, CH3). 13C NMR (CDCl3, 400 MHz): δ 141.05, 125.91, 121.36 (aromatic carbons), 78.59 (2C, CMe2), 32.29 (4C, CH2), 21.94 (2C, CH3) 20.11 (2C, CH3). 31P NMR (CDCl3, 400 MHz): δ -13.89. Analysis calculated for C16H24O8P2: C 47.30, H 5.95%; found: C 47.43, H 6.16%.
The procedure was essentially the same as that for the preparation of (1) using 5,5-dimethyl-1,3,2-dioxaphosphinane 2-oxide (0.65 g, 4.33 mmol), 2,2'-biphenol (0.81 g, 4.33 mmol) and N-chlorodiisoproylamine (0.59 g, 4.33 mmol) [yield: 0.94 g, 65%; m.p. 451–454 K (literature 455 K)]. 1H NMR (CDCl3, 400 MHz): δ 6.94–7.66 (m, 8H, Ar—H), 5.35 (br, 1H, OH), 3.45–3.60 (m, 4H, CH2), 1.11 (s, 3H, CH3), 0.44 (s, 3H, CH3). 31P NMR (CDCl3, 400 MHz): δ -14.26 (literature value in DMSO + CDCl2 is -15.1). Analysis calculated for C17H19O5P: C 61.08, H 5.73%; found: C 61.19, H 5.95%.
The procedure was essentially the same as that for the preparation of (1) using 5,5-dimethyl-1,3,2-dioxaphosphinane 2-oxide (0.46 g, 3.06 mmol), H2O (0.03 g, 1.53 mmol) and N-chlorodiisoproylamine (0.41 g, 3.06 mmol) [yield 0.26 g, 58%; m.p. 441 K (literature 461–465 K)]. 1H NMR (CDCl3, 400 MHz): 4.41 (d, 4H, CH2), 3.93 (dd, 4H, CH2), 1.26 (s, 6H, CH3), 0.84 (s, 6H, CH3). 31P NMR (CDCl3, 400 MHz): δ -21.13. Analysis calculated for C10H20O7P2: C 38.23, H 6.24%; found: C 38.31, H 6.33%.
Crystal data, data collection and structure refinement details for compounds (1) and (3) are summarized in Table 1. Intensity data were measured for crystals of three compounds (1)–(3). Compound (1) is novel, where as the results for compounds (2) and (3) have been reported previously [for (2), see Kumara Swamy et al. (1998); for (3), see Cook & White (1976) and Bukowska-Strzyzewska & Dobrowolska (1978)], but we record here our results for compound (3) which we find are more precise and accurate than those currently reported in the literature. In both analyses, all H atoms were located in difference maps. In the refinements, the methyl-group H atoms were refined as rigid groups by rotation about the C—C bond to agree best with the electron density, while the remaining H atoms (coordinates and isotropic displacement parameters) were refined freely.
X-ray and NMR analyses of compounds (1) and (3) confirm that the six-membered phosphorinane ring is intact and always adopts the chair conformation. The molecular structure of compound (1) (Fig. 2) confirms that the two cyclo-P(O)OCH2CMe2CH2O groups are linked through a catechol group. The conformations about the two catechol O atoms are quite different, viz. the C2—C1—O1—P1 torsion angle is -169.11 (11)° and indicates a trans arrangement, whereas the C1—C2—O2—P2 angle is 92.48 (16)°, and indicates a gauche conformation. Both six-membered POCCCO rings have good chair shapes; in each, the catechol O atom is in an axial site, and the short P1—O16 and P2—O26 bonds are equatorially bound [the P═O distances are 1.4493 (13) and 1.4473 (13) Å, respectively, whereas the other P—O distances are in the range 1.5509 (13)–1.5894 (12) Å].
In compound (3), the two cyclo-P(O)OCH2CMe2CH2O groups are linked through a central O atom, and are related by a pseudo-twofold symmetry axis (Fig. 3). Both six-membered rings have chair conformations. At both P atoms, the linking O3 atom is in an axial position and a shorter P═O bond is equatorially bonded; the order of P—O bond lengths in both groups is P═ O (as P1—O1 ca 1.44 Å) < P—Oring (as P1—O11 ca 1.55 Å) < P—Olinking (as P1—O3 ca 1.60 Å).
These dimensions for (1) and (3) are very similar to those for compound (2) (Kumara Swamy et al., 1998). We also note that the angles about the P atoms are very similar, and, following the atom-numbering scheme for compound (1), find that the O16—P1—O1/O11/O15 angles in compound (1) and the corresponding angles in all three compounds are greater than the regular tetrahedral angle (109.5°), lying in the range 111.97 (9)–115.97 (7)°. The angles corresponding to O11—P1—O15 lie in the narrow range 106.03 (12)–107.24 (6)°. The angles involving a link atom, e.g. O1 in (1), fall into two groups, viz. 100.67 (6)–101.96 (13) and 104.11 (14)–106.92 (8)°, depending on the orientation of the atom beyond the link atom, e.g. C1 is trans to O11 about the O1—P1 bond and, typically, the O1—P1—O11 angle of 100.67 (6)° is in the first group, with the least obtuse angles, and C1 is cis to O15 about the same bond and the O1—P1—O15 angle of 106.28 (7)° is in the second group.
In the phosphorinane rings we note a consistency in the chair conformations through all the rings in compounds (1) and (3). In each ring, there are three distinct groupings of torsion angles, viz low (absolute) values in the angles about the P atom, medium values about the O—C bonds and higher values about the C—C bonds. In compound (3), the ranges of values in the two phosphorinane rings are, respectively, -39.6 (3) to -43.6 (3), 49.9 (4) to 54.5 (4), and -55.8 (4) to 57.9 (4)°. The values in the P1-containing ring in compound (1) are very similar, but the second ring in (1) shows more extreme values, viz. 34.44 (14) to -35.32 (14), -49.53 (18) to 51.53 (19) and 59.36 (19) to -60.63 (19)° for the three pairs; here the chair is slightly flatter around the P atoms and deeper at the opposite end.
There are few short intermolecular contacts in either of compounds (1) and (3). The shortest intermolecular distances are of C—H···O contacts with a minimum H···O distance of 2.58 Å [2.656 (16) and 2.34 (2) Å in CIF] in compound (1) and 2.64 (3) Å in compound (3).
For both compounds, data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEPII (Johnson, 1976) and ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and WinGX (Farrugia, 2012).
C16H24O8P2 | Z = 2 |
Mr = 406.29 | F(000) = 428 |
Triclinic, P1 | Dx = 1.389 Mg m−3 |
a = 9.5706 (5) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.2415 (5) Å | Cell parameters from 6760 reflections |
c = 11.6998 (5) Å | θ = 2.9–32.6° |
α = 94.507 (4)° | µ = 0.26 mm−1 |
β = 110.270 (4)° | T = 293 K |
γ = 111.616 (5)° | Polyhedron, colourless |
V = 971.75 (8) Å3 | 0.28 × 0.22 × 0.22 mm |
Oxford Diffraction Xcalibur 3/Sapphire3 CCD diffractometer | 3522 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 3111 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.018 |
Detector resolution: 16.0050 pixels mm-1 | θmax = 25.3°, θmin = 2.9° |
Thin slice φ and ω scans | h = −11→11 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010) | k = −12→12 |
Tmin = 0.970, Tmax = 1.000 | l = −14→14 |
13183 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.032 | Hydrogen site location: mixed |
wR(F2) = 0.090 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0467P)2 + 0.2387P] where P = (Fo2 + 2Fc2)/3 |
3522 reflections | (Δ/σ)max = 0.001 |
287 parameters | Δρmax = 0.17 e Å−3 |
0 restraints | Δρmin = −0.37 e Å−3 |
C16H24O8P2 | γ = 111.616 (5)° |
Mr = 406.29 | V = 971.75 (8) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.5706 (5) Å | Mo Kα radiation |
b = 10.2415 (5) Å | µ = 0.26 mm−1 |
c = 11.6998 (5) Å | T = 293 K |
α = 94.507 (4)° | 0.28 × 0.22 × 0.22 mm |
β = 110.270 (4)° |
Oxford Diffraction Xcalibur 3/Sapphire3 CCD diffractometer | 3522 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010) | 3111 reflections with I > 2σ(I) |
Tmin = 0.970, Tmax = 1.000 | Rint = 0.018 |
13183 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.090 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.17 e Å−3 |
3522 reflections | Δρmin = −0.37 e Å−3 |
287 parameters |
Experimental. CrysAlisPro, Agilent Technologies, Version 1.171.36.21 Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.63738 (18) | 0.36947 (17) | 0.56114 (14) | 0.0383 (3) | |
C2 | 0.7132 (2) | 0.50869 (18) | 0.54993 (15) | 0.0425 (4) | |
C3 | 0.7894 (3) | 0.5337 (3) | 0.46828 (19) | 0.0622 (5) | |
C4 | 0.7932 (3) | 0.4196 (3) | 0.3998 (2) | 0.0716 (6) | |
C5 | 0.7198 (3) | 0.2817 (3) | 0.41188 (19) | 0.0619 (5) | |
C6 | 0.6412 (2) | 0.2556 (2) | 0.49250 (17) | 0.0485 (4) | |
O1 | 0.55679 (14) | 0.35278 (11) | 0.64127 (10) | 0.0425 (3) | |
P1 | 0.48663 (5) | 0.21159 (4) | 0.68809 (4) | 0.04313 (14) | |
O11 | 0.41657 (13) | 0.26452 (13) | 0.77506 (11) | 0.0478 (3) | |
C12 | 0.5333 (2) | 0.3758 (2) | 0.88942 (17) | 0.0468 (4) | |
C13 | 0.6671 (2) | 0.33522 (18) | 0.96936 (16) | 0.0446 (4) | |
C131 | 0.7915 (3) | 0.4668 (2) | 1.07755 (18) | 0.0623 (5) | |
H13A | 0.7386 | 0.4884 | 1.1279 | 0.094* | |
H13B | 0.8337 | 0.5484 | 1.0444 | 0.094* | |
H13C | 0.8804 | 0.4462 | 1.1282 | 0.094* | |
C132 | 0.5956 (3) | 0.2043 (2) | 1.0188 (2) | 0.0687 (6) | |
H13D | 0.5183 | 0.1230 | 0.9496 | 0.103* | |
H13E | 0.5409 | 0.2253 | 1.0678 | 0.103* | |
H13F | 0.6826 | 0.1820 | 1.0702 | 0.103* | |
C14 | 0.7544 (2) | 0.3058 (2) | 0.89078 (17) | 0.0458 (4) | |
O15 | 0.63898 (15) | 0.19196 (12) | 0.77626 (11) | 0.0485 (3) | |
O16 | 0.36583 (18) | 0.08262 (14) | 0.59102 (13) | 0.0673 (4) | |
O2 | 0.70552 (14) | 0.62353 (12) | 0.61712 (11) | 0.0446 (3) | |
P2 | 0.84618 (5) | 0.71344 (4) | 0.75157 (4) | 0.04369 (14) | |
O21 | 0.78129 (14) | 0.82044 (12) | 0.78995 (11) | 0.0477 (3) | |
C22 | 0.7949 (2) | 0.94625 (19) | 0.73635 (19) | 0.0458 (4) | |
C23 | 0.96791 (19) | 1.02969 (16) | 0.74533 (15) | 0.0394 (4) | |
C231 | 0.9688 (3) | 1.1526 (2) | 0.67952 (19) | 0.0591 (5) | |
H23A | 1.0775 | 1.2074 | 0.6848 | 0.089* | |
H23B | 0.9356 | 1.2144 | 0.7193 | 0.089* | |
H23C | 0.8936 | 1.1133 | 0.5930 | 0.089* | |
C232 | 1.0925 (2) | 1.0900 (2) | 0.88173 (17) | 0.0561 (5) | |
H23D | 1.0916 | 1.0117 | 0.9220 | 0.084* | |
H23E | 1.0638 | 1.1533 | 0.9245 | 0.084* | |
H23F | 1.2003 | 1.1428 | 0.8844 | 0.084* | |
C24 | 1.0084 (2) | 0.92816 (19) | 0.67482 (19) | 0.0480 (4) | |
O25 | 1.00235 (14) | 0.80403 (12) | 0.72902 (12) | 0.0508 (3) | |
O26 | 0.87952 (18) | 0.62723 (14) | 0.84088 (13) | 0.0689 (4) | |
H3 | 0.842 (3) | 0.628 (3) | 0.465 (2) | 0.076 (7)* | |
H4 | 0.845 (3) | 0.440 (3) | 0.347 (2) | 0.084 (7)* | |
H5 | 0.717 (3) | 0.203 (2) | 0.364 (2) | 0.067 (6)* | |
H6 | 0.593 (2) | 0.164 (2) | 0.4979 (17) | 0.051 (5)* | |
H121 | 0.581 (2) | 0.464 (2) | 0.8678 (16) | 0.046 (5)* | |
H122 | 0.469 (2) | 0.383 (2) | 0.9349 (18) | 0.056 (5)* | |
H141 | 0.828 (2) | 0.267 (2) | 0.9339 (18) | 0.059 (5)* | |
H142 | 0.811 (2) | 0.390 (2) | 0.8635 (17) | 0.049 (5)* | |
H221 | 0.716 (2) | 0.911 (2) | 0.6498 (18) | 0.047 (5)* | |
H222 | 0.765 (2) | 0.999 (2) | 0.7866 (18) | 0.057 (5)* | |
H241 | 0.934 (2) | 0.894 (2) | 0.589 (2) | 0.054 (5)* | |
H242 | 1.117 (3) | 0.975 (2) | 0.6787 (18) | 0.060 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0345 (8) | 0.0408 (8) | 0.0341 (8) | 0.0151 (7) | 0.0087 (6) | 0.0084 (6) |
C2 | 0.0423 (9) | 0.0417 (9) | 0.0376 (8) | 0.0172 (7) | 0.0099 (7) | 0.0116 (7) |
C3 | 0.0714 (13) | 0.0601 (13) | 0.0551 (11) | 0.0210 (11) | 0.0305 (10) | 0.0247 (10) |
C4 | 0.0831 (16) | 0.0895 (17) | 0.0542 (12) | 0.0355 (13) | 0.0411 (12) | 0.0211 (12) |
C5 | 0.0695 (13) | 0.0698 (14) | 0.0483 (11) | 0.0337 (11) | 0.0233 (10) | 0.0043 (10) |
C6 | 0.0489 (10) | 0.0442 (10) | 0.0460 (9) | 0.0194 (8) | 0.0136 (8) | 0.0054 (8) |
O1 | 0.0457 (6) | 0.0333 (6) | 0.0473 (6) | 0.0137 (5) | 0.0208 (5) | 0.0086 (5) |
P1 | 0.0428 (2) | 0.0308 (2) | 0.0453 (3) | 0.00669 (18) | 0.0167 (2) | 0.00380 (18) |
O11 | 0.0353 (6) | 0.0501 (7) | 0.0505 (7) | 0.0114 (5) | 0.0171 (5) | 0.0072 (5) |
C12 | 0.0457 (10) | 0.0431 (10) | 0.0519 (10) | 0.0189 (8) | 0.0212 (8) | 0.0048 (8) |
C13 | 0.0453 (9) | 0.0389 (9) | 0.0446 (9) | 0.0141 (7) | 0.0168 (8) | 0.0086 (7) |
C131 | 0.0599 (12) | 0.0614 (12) | 0.0488 (10) | 0.0190 (10) | 0.0128 (9) | 0.0007 (9) |
C132 | 0.0756 (14) | 0.0655 (13) | 0.0651 (13) | 0.0229 (11) | 0.0328 (11) | 0.0297 (11) |
C14 | 0.0432 (9) | 0.0422 (9) | 0.0525 (10) | 0.0206 (8) | 0.0170 (8) | 0.0130 (8) |
O15 | 0.0583 (7) | 0.0366 (6) | 0.0542 (7) | 0.0240 (6) | 0.0230 (6) | 0.0081 (5) |
O16 | 0.0688 (9) | 0.0416 (7) | 0.0580 (8) | −0.0039 (6) | 0.0210 (7) | −0.0036 (6) |
O2 | 0.0442 (6) | 0.0352 (6) | 0.0466 (6) | 0.0160 (5) | 0.0103 (5) | 0.0114 (5) |
P2 | 0.0440 (3) | 0.0328 (2) | 0.0454 (3) | 0.01260 (19) | 0.0111 (2) | 0.01387 (18) |
O21 | 0.0504 (7) | 0.0383 (6) | 0.0548 (7) | 0.0120 (5) | 0.0285 (6) | 0.0129 (5) |
C22 | 0.0446 (10) | 0.0374 (9) | 0.0563 (11) | 0.0182 (8) | 0.0207 (9) | 0.0108 (8) |
C23 | 0.0402 (8) | 0.0313 (8) | 0.0413 (8) | 0.0107 (7) | 0.0151 (7) | 0.0095 (6) |
C231 | 0.0689 (12) | 0.0414 (10) | 0.0612 (12) | 0.0186 (9) | 0.0228 (10) | 0.0212 (9) |
C232 | 0.0534 (11) | 0.0474 (10) | 0.0461 (10) | 0.0063 (9) | 0.0129 (8) | 0.0080 (8) |
C24 | 0.0480 (10) | 0.0410 (9) | 0.0558 (11) | 0.0137 (8) | 0.0274 (9) | 0.0115 (8) |
O25 | 0.0420 (6) | 0.0405 (6) | 0.0704 (8) | 0.0191 (5) | 0.0213 (6) | 0.0143 (6) |
O26 | 0.0764 (9) | 0.0460 (7) | 0.0577 (8) | 0.0174 (7) | 0.0040 (7) | 0.0232 (6) |
C1—C6 | 1.382 (2) | C132—H13D | 0.9600 |
C1—C2 | 1.382 (2) | C132—H13E | 0.9600 |
C1—O1 | 1.3900 (19) | C132—H13F | 0.9600 |
C2—C3 | 1.376 (3) | C14—O15 | 1.468 (2) |
C2—O2 | 1.402 (2) | C14—H141 | 0.94 (2) |
C3—C4 | 1.383 (3) | C14—H142 | 0.98 (2) |
C3—H3 | 0.92 (2) | O2—P2 | 1.5894 (12) |
C4—C5 | 1.370 (3) | P2—O26 | 1.4473 (13) |
C4—H4 | 0.91 (3) | P2—O21 | 1.5509 (13) |
C5—C6 | 1.383 (3) | P2—O25 | 1.5667 (13) |
C5—H5 | 0.93 (2) | O21—C22 | 1.460 (2) |
C6—H6 | 0.90 (2) | C22—C23 | 1.518 (2) |
O1—P1 | 1.5830 (12) | C22—H221 | 0.969 (19) |
P1—O16 | 1.4493 (13) | C22—H222 | 0.95 (2) |
P1—O11 | 1.5597 (12) | C23—C24 | 1.515 (2) |
P1—O15 | 1.5611 (13) | C23—C231 | 1.525 (2) |
O11—C12 | 1.457 (2) | C23—C232 | 1.528 (2) |
C12—C13 | 1.520 (2) | C231—H23A | 0.9600 |
C12—H121 | 0.952 (19) | C231—H23B | 0.9600 |
C12—H122 | 0.96 (2) | C231—H23C | 0.9600 |
C13—C14 | 1.519 (2) | C232—H23D | 0.9600 |
C13—C132 | 1.524 (3) | C232—H23E | 0.9600 |
C13—C131 | 1.530 (2) | C232—H23F | 0.9600 |
C131—H13A | 0.9600 | C24—O25 | 1.456 (2) |
C131—H13B | 0.9600 | C24—H241 | 0.96 (2) |
C131—H13C | 0.9600 | C24—H242 | 0.95 (2) |
C6—C1—C2 | 120.07 (16) | H13D—C132—H13F | 109.5 |
C6—C1—O1 | 123.55 (15) | H13E—C132—H13F | 109.5 |
C2—C1—O1 | 116.36 (14) | O15—C14—C13 | 111.47 (14) |
C3—C2—C1 | 120.02 (17) | O15—C14—H141 | 103.7 (12) |
C3—C2—O2 | 119.93 (16) | C13—C14—H141 | 110.4 (12) |
C1—C2—O2 | 119.98 (15) | O15—C14—H142 | 106.2 (11) |
C2—C3—C4 | 119.8 (2) | C13—C14—H142 | 114.2 (11) |
C2—C3—H3 | 117.6 (15) | H141—C14—H142 | 110.4 (16) |
C4—C3—H3 | 122.5 (15) | C14—O15—P1 | 117.81 (10) |
C5—C4—C3 | 120.3 (2) | C2—O2—P2 | 120.58 (10) |
C5—C4—H4 | 121.9 (16) | O26—P2—O21 | 113.95 (8) |
C3—C4—H4 | 117.8 (16) | O26—P2—O25 | 111.94 (8) |
C4—C5—C6 | 120.2 (2) | O21—P2—O25 | 107.24 (6) |
C4—C5—H5 | 121.8 (13) | O26—P2—O2 | 114.73 (7) |
C6—C5—H5 | 117.9 (14) | O21—P2—O2 | 101.88 (7) |
C1—C6—C5 | 119.64 (19) | O25—P2—O2 | 106.26 (7) |
C1—C6—H6 | 121.9 (12) | C22—O21—P2 | 120.39 (10) |
C5—C6—H6 | 118.4 (12) | O21—C22—C23 | 111.45 (14) |
C1—O1—P1 | 126.34 (10) | O21—C22—H221 | 107.1 (11) |
O16—P1—O11 | 113.30 (8) | C23—C22—H221 | 111.1 (11) |
O16—P1—O15 | 113.22 (8) | O21—C22—H222 | 101.8 (12) |
O11—P1—O15 | 106.22 (7) | C23—C22—H222 | 112.7 (12) |
O16—P1—O1 | 115.97 (7) | H221—C22—H222 | 112.2 (16) |
O11—P1—O1 | 100.67 (6) | C24—C23—C22 | 107.77 (14) |
O15—P1—O1 | 106.28 (7) | C24—C23—C231 | 108.23 (14) |
C12—O11—P1 | 117.71 (10) | C22—C23—C231 | 108.12 (14) |
O11—C12—C13 | 112.49 (14) | C24—C23—C232 | 111.05 (15) |
O11—C12—H121 | 109.1 (11) | C22—C23—C232 | 111.39 (15) |
C13—C12—H121 | 110.0 (11) | C231—C23—C232 | 110.17 (14) |
O11—C12—H122 | 104.9 (12) | C23—C231—H23A | 109.5 |
C13—C12—H122 | 109.0 (12) | C23—C231—H23B | 109.5 |
H121—C12—H122 | 111.3 (16) | H23A—C231—H23B | 109.5 |
C14—C13—C12 | 108.54 (14) | C23—C231—H23C | 109.5 |
C14—C13—C132 | 111.04 (16) | H23A—C231—H23C | 109.5 |
C12—C13—C132 | 111.07 (16) | H23B—C231—H23C | 109.5 |
C14—C13—C131 | 107.97 (15) | C23—C232—H23D | 109.5 |
C12—C13—C131 | 107.27 (15) | C23—C232—H23E | 109.5 |
C132—C13—C131 | 110.81 (15) | H23D—C232—H23E | 109.5 |
C13—C131—H13A | 109.5 | C23—C232—H23F | 109.5 |
C13—C131—H13B | 109.5 | H23D—C232—H23F | 109.5 |
H13A—C131—H13B | 109.5 | H23E—C232—H23F | 109.5 |
C13—C131—H13C | 109.5 | O25—C24—C23 | 111.35 (14) |
H13A—C131—H13C | 109.5 | O25—C24—H241 | 108.6 (12) |
H13B—C131—H13C | 109.5 | C23—C24—H241 | 111.1 (11) |
C13—C132—H13D | 109.5 | O25—C24—H242 | 106.1 (12) |
C13—C132—H13E | 109.5 | C23—C24—H242 | 111.4 (13) |
H13D—C132—H13E | 109.5 | H241—C24—H242 | 108.2 (17) |
C13—C132—H13F | 109.5 | C24—O25—P2 | 119.42 (11) |
C6—C1—C2—C3 | 1.4 (2) | C131—C13—C14—O15 | −173.11 (14) |
O1—C1—C2—C3 | −177.12 (15) | C13—C14—O15—P1 | 54.46 (17) |
C6—C1—C2—O2 | 178.32 (14) | O16—P1—O15—C14 | −169.25 (12) |
O1—C1—C2—O2 | −0.2 (2) | O11—P1—O15—C14 | −44.30 (13) |
C1—C2—C3—C4 | −1.5 (3) | O1—P1—O15—C14 | 62.31 (13) |
O2—C2—C3—C4 | −178.38 (18) | C3—C2—O2—P2 | −90.64 (18) |
C2—C3—C4—C5 | 0.7 (3) | C1—C2—O2—P2 | 92.48 (16) |
C3—C4—C5—C6 | 0.2 (3) | C2—O2—P2—O26 | −53.81 (15) |
C2—C1—C6—C5 | −0.6 (3) | C2—O2—P2—O21 | −177.43 (11) |
O1—C1—C6—C5 | 177.88 (16) | C2—O2—P2—O25 | 70.43 (13) |
C4—C5—C6—C1 | −0.2 (3) | O26—P2—O21—C22 | 158.91 (12) |
C6—C1—O1—P1 | 12.4 (2) | O25—P2—O21—C22 | 34.44 (14) |
C2—C1—O1—P1 | −169.11 (11) | O2—P2—O21—C22 | −76.96 (13) |
C1—O1—P1—O16 | −58.42 (15) | P2—O21—C22—C23 | −49.53 (18) |
C1—O1—P1—O11 | 178.93 (12) | O21—C22—C23—C24 | 59.36 (19) |
C1—O1—P1—O15 | 68.38 (13) | O21—C22—C23—C231 | 176.13 (14) |
O16—P1—O11—C12 | 168.51 (12) | O21—C22—C23—C232 | −62.68 (19) |
O15—P1—O11—C12 | 43.60 (13) | C22—C23—C24—O25 | −60.63 (19) |
O1—P1—O11—C12 | −67.00 (13) | C231—C23—C24—O25 | −177.34 (15) |
P1—O11—C12—C13 | −53.54 (18) | C232—C23—C24—O25 | 61.62 (19) |
O11—C12—C13—C14 | 57.12 (19) | C23—C24—O25—P2 | 51.53 (19) |
O11—C12—C13—C132 | −65.2 (2) | O26—P2—O25—C24 | −161.00 (13) |
O11—C12—C13—C131 | 173.54 (15) | O21—P2—O25—C24 | −35.32 (14) |
C12—C13—C14—O15 | −57.14 (18) | O2—P2—O25—C24 | 73.05 (13) |
C132—C13—C14—O15 | 65.23 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···O16 | 0.90 (2) | 2.656 (19) | 3.224 (2) | 122.2 (15) |
C14—H142···O26 | 0.98 (2) | 2.34 (2) | 3.239 (2) | 152.9 (15) |
C22—H221···O16i | 0.969 (19) | 2.663 (19) | 3.540 (2) | 150.6 (14) |
C231—H23C···O16i | 0.96 | 2.60 | 3.489 (2) | 154 |
C22—H222···O15ii | 0.95 (2) | 2.66 (2) | 3.441 (2) | 140.4 (15) |
C131—H13C···O26iii | 0.96 | 2.59 | 3.471 (3) | 152 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y+1, z; (iii) −x+2, −y+1, −z+2. |
C10H20O7P2 | Dx = 1.398 Mg m−3 |
Mr = 314.20 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbca | Cell parameters from 7659 reflections |
a = 9.8434 (2) Å | θ = 2.9–32.5° |
b = 11.3589 (3) Å | µ = 0.32 mm−1 |
c = 26.6986 (8) Å | T = 293 K |
V = 2985.18 (13) Å3 | Prism, colourless |
Z = 8 | 0.40 × 0.18 × 0.14 mm |
F(000) = 1328 |
Oxford Diffraction Xcalibur 3/Sapphire3 CCD diffractometer | 2141 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 1920 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.038 |
Detector resolution: 16.0050 pixels mm-1 | θmax = 23.3°, θmin = 3.1° |
Thin slice φ and ω scans | h = −10→10 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010) | k = −12→12 |
Tmin = 0.847, Tmax = 1.000 | l = −29→29 |
33060 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.046 | Hydrogen site location: mixed |
wR(F2) = 0.094 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.14 | w = 1/[σ2(Fo2) + (0.0182P)2 + 4.2243P] where P = (Fo2 + 2Fc2)/3 |
2141 reflections | (Δ/σ)max = 0.001 |
208 parameters | Δρmax = 0.24 e Å−3 |
0 restraints | Δρmin = −0.29 e Å−3 |
C10H20O7P2 | V = 2985.18 (13) Å3 |
Mr = 314.20 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 9.8434 (2) Å | µ = 0.32 mm−1 |
b = 11.3589 (3) Å | T = 293 K |
c = 26.6986 (8) Å | 0.40 × 0.18 × 0.14 mm |
Oxford Diffraction Xcalibur 3/Sapphire3 CCD diffractometer | 2141 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010) | 1920 reflections with I > 2σ(I) |
Tmin = 0.847, Tmax = 1.000 | Rint = 0.038 |
33060 measured reflections | θmax = 23.3° |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.094 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.14 | Δρmax = 0.24 e Å−3 |
2141 reflections | Δρmin = −0.29 e Å−3 |
208 parameters |
Experimental. CrysAlisPro, Agilent Technologies, Version 1.171.36.21 Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. |
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. |
x | y | z | Uiso*/Ueq | ||
P1 | 0.45899 (9) | 0.53260 (8) | 0.61971 (3) | 0.0490 (3) | |
O1 | 0.4212 (3) | 0.4270 (2) | 0.64655 (11) | 0.0842 (9) | |
O11 | 0.4325 (2) | 0.52680 (18) | 0.56282 (8) | 0.0515 (6) | |
C12 | 0.4428 (4) | 0.6361 (4) | 0.53372 (15) | 0.0594 (10) | |
C13 | 0.3530 (3) | 0.7315 (3) | 0.55525 (12) | 0.0478 (8) | |
C131 | 0.2040 (3) | 0.6951 (3) | 0.55180 (14) | 0.0636 (10) | |
H13A | 0.1890 | 0.6265 | 0.5721 | 0.095* | |
H13B | 0.1817 | 0.6776 | 0.5176 | 0.095* | |
H13C | 0.1476 | 0.7583 | 0.5636 | 0.095* | |
C132 | 0.3768 (5) | 0.8453 (4) | 0.52559 (17) | 0.0938 (16) | |
H13D | 0.3179 | 0.9059 | 0.5381 | 0.141* | |
H13E | 0.3577 | 0.8316 | 0.4908 | 0.141* | |
H13F | 0.4697 | 0.8695 | 0.5293 | 0.141* | |
C14 | 0.3931 (4) | 0.7527 (3) | 0.60888 (15) | 0.0558 (9) | |
O15 | 0.3881 (2) | 0.6456 (2) | 0.63904 (8) | 0.0544 (6) | |
P2 | 0.75239 (9) | 0.49307 (8) | 0.61789 (3) | 0.0476 (2) | |
O2 | 0.7449 (3) | 0.4006 (2) | 0.58107 (9) | 0.0713 (7) | |
O21 | 0.7854 (2) | 0.44840 (18) | 0.67142 (8) | 0.0536 (6) | |
C22 | 0.8171 (4) | 0.5358 (4) | 0.70966 (14) | 0.0593 (10) | |
C23 | 0.9300 (3) | 0.6177 (3) | 0.69381 (11) | 0.0457 (8) | |
C231 | 1.0617 (4) | 0.5494 (4) | 0.68676 (15) | 0.0763 (12) | |
H23A | 1.0806 | 0.5044 | 0.7164 | 0.115* | |
H23B | 1.1349 | 0.6034 | 0.6807 | 0.115* | |
H23C | 1.0528 | 0.4971 | 0.6587 | 0.115* | |
C232 | 0.9474 (5) | 0.7134 (4) | 0.73355 (14) | 0.0826 (13) | |
H23D | 0.8632 | 0.7550 | 0.7377 | 0.124* | |
H23E | 1.0168 | 0.7675 | 0.7231 | 0.124* | |
H23F | 0.9731 | 0.6779 | 0.7648 | 0.124* | |
C24 | 0.8875 (4) | 0.6773 (3) | 0.64565 (13) | 0.0540 (9) | |
O25 | 0.8577 (2) | 0.5910 (2) | 0.60644 (8) | 0.0545 (6) | |
O3 | 0.6157 (2) | 0.5672 (2) | 0.62471 (10) | 0.0640 (7) | |
H121 | 0.541 (4) | 0.660 (3) | 0.5358 (12) | 0.066 (11)* | |
H122 | 0.412 (4) | 0.615 (3) | 0.5020 (14) | 0.075 (12)* | |
H141 | 0.482 (4) | 0.780 (3) | 0.6115 (13) | 0.064 (11)* | |
H142 | 0.335 (4) | 0.806 (3) | 0.6248 (12) | 0.065 (11)* | |
H221 | 0.846 (3) | 0.491 (3) | 0.7376 (13) | 0.063 (10)* | |
H222 | 0.734 (4) | 0.577 (4) | 0.7158 (14) | 0.089 (14)* | |
H241 | 0.959 (3) | 0.721 (3) | 0.6335 (11) | 0.052 (9)* | |
H242 | 0.808 (4) | 0.723 (3) | 0.6510 (12) | 0.063 (11)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.0390 (5) | 0.0484 (5) | 0.0597 (6) | 0.0035 (4) | −0.0082 (4) | 0.0031 (4) |
O1 | 0.0702 (18) | 0.0701 (17) | 0.112 (2) | 0.0042 (15) | 0.0012 (16) | 0.0369 (16) |
O11 | 0.0488 (13) | 0.0462 (13) | 0.0594 (14) | 0.0086 (11) | −0.0104 (11) | −0.0125 (11) |
C12 | 0.059 (3) | 0.070 (3) | 0.049 (2) | 0.019 (2) | 0.0053 (19) | −0.0011 (19) |
C13 | 0.0449 (18) | 0.0511 (19) | 0.0474 (19) | 0.0139 (16) | 0.0055 (15) | 0.0043 (15) |
C131 | 0.050 (2) | 0.075 (3) | 0.066 (2) | 0.0138 (19) | −0.0110 (18) | −0.005 (2) |
C132 | 0.089 (3) | 0.080 (3) | 0.113 (4) | 0.030 (3) | 0.034 (3) | 0.041 (3) |
C14 | 0.048 (2) | 0.046 (2) | 0.074 (3) | 0.0039 (18) | 0.000 (2) | −0.0137 (19) |
O15 | 0.0554 (15) | 0.0649 (15) | 0.0428 (12) | 0.0116 (12) | −0.0045 (11) | −0.0030 (11) |
P2 | 0.0389 (5) | 0.0475 (5) | 0.0563 (5) | −0.0013 (4) | −0.0077 (4) | 0.0025 (4) |
O2 | 0.0698 (17) | 0.0644 (16) | 0.0797 (17) | −0.0022 (13) | −0.0101 (15) | −0.0171 (14) |
O21 | 0.0502 (14) | 0.0472 (13) | 0.0634 (14) | −0.0076 (11) | −0.0058 (11) | 0.0150 (11) |
C22 | 0.058 (2) | 0.071 (3) | 0.049 (2) | 0.000 (2) | 0.0056 (19) | 0.015 (2) |
C23 | 0.048 (2) | 0.0509 (19) | 0.0383 (17) | −0.0042 (16) | 0.0008 (15) | 0.0003 (14) |
C231 | 0.046 (2) | 0.100 (3) | 0.083 (3) | 0.001 (2) | −0.015 (2) | −0.010 (2) |
C232 | 0.112 (4) | 0.079 (3) | 0.057 (2) | −0.015 (3) | −0.002 (2) | −0.013 (2) |
C24 | 0.057 (2) | 0.051 (2) | 0.054 (2) | −0.014 (2) | 0.0004 (19) | 0.0078 (17) |
O25 | 0.0576 (15) | 0.0648 (15) | 0.0412 (12) | −0.0149 (12) | −0.0023 (11) | 0.0074 (11) |
O3 | 0.0413 (13) | 0.0538 (14) | 0.0969 (19) | 0.0054 (11) | −0.0222 (13) | −0.0075 (13) |
P1—O1 | 1.446 (3) | P2—O2 | 1.440 (2) |
P1—O11 | 1.542 (2) | P2—O25 | 1.551 (2) |
P1—O15 | 1.549 (2) | P2—O21 | 1.551 (2) |
P1—O3 | 1.597 (2) | P2—O3 | 1.597 (2) |
O11—C12 | 1.468 (4) | O21—C22 | 1.458 (4) |
C12—C13 | 1.512 (5) | C22—C23 | 1.510 (5) |
C12—H121 | 1.00 (4) | C22—H221 | 0.95 (3) |
C12—H122 | 0.93 (4) | C22—H222 | 0.96 (4) |
C13—C14 | 1.505 (5) | C23—C24 | 1.512 (5) |
C13—C131 | 1.527 (5) | C23—C231 | 1.523 (5) |
C13—C132 | 1.534 (5) | C23—C232 | 1.529 (4) |
C131—H13A | 0.9600 | C231—H23A | 0.9600 |
C131—H13B | 0.9600 | C231—H23B | 0.9600 |
C131—H13C | 0.9600 | C231—H23C | 0.9600 |
C132—H13D | 0.9600 | C232—H23D | 0.9600 |
C132—H13E | 0.9600 | C232—H23E | 0.9600 |
C132—H13F | 0.9600 | C232—H23F | 0.9600 |
C14—O15 | 1.460 (4) | C24—O25 | 1.463 (4) |
C14—H141 | 0.93 (4) | C24—H241 | 0.92 (3) |
C14—H142 | 0.94 (3) | C24—H242 | 0.95 (3) |
O1—P1—O11 | 114.16 (16) | O2—P2—O21 | 113.65 (14) |
O1—P1—O15 | 113.95 (15) | O25—P2—O21 | 106.03 (12) |
O11—P1—O15 | 106.70 (12) | O2—P2—O3 | 114.75 (15) |
O1—P1—O3 | 114.26 (15) | O25—P2—O3 | 101.96 (13) |
O11—P1—O3 | 104.83 (14) | O21—P2—O3 | 104.11 (14) |
O15—P1—O3 | 101.76 (13) | C22—O21—P2 | 117.9 (2) |
C12—O11—P1 | 118.3 (2) | O21—C22—C23 | 112.4 (3) |
O11—C12—C13 | 111.4 (3) | O21—C22—H221 | 105 (2) |
O11—C12—H121 | 105 (2) | C23—C22—H221 | 109 (2) |
C13—C12—H121 | 110 (2) | O21—C22—H222 | 106 (2) |
O11—C12—H122 | 104 (2) | C23—C22—H222 | 112 (3) |
C13—C12—H122 | 110 (2) | H221—C22—H222 | 113 (3) |
H121—C12—H122 | 115 (3) | C22—C23—C24 | 108.1 (3) |
C14—C13—C12 | 108.8 (3) | C22—C23—C231 | 110.3 (3) |
C14—C13—C131 | 110.7 (3) | C24—C23—C231 | 111.0 (3) |
C12—C13—C131 | 110.2 (3) | C22—C23—C232 | 109.1 (3) |
C14—C13—C132 | 108.4 (3) | C24—C23—C232 | 107.6 (3) |
C12—C13—C132 | 108.6 (3) | C231—C23—C232 | 110.7 (3) |
C131—C13—C132 | 110.1 (3) | C23—C231—H23A | 109.5 |
C13—C131—H13A | 109.5 | C23—C231—H23B | 109.5 |
C13—C131—H13B | 109.5 | H23A—C231—H23B | 109.5 |
H13A—C131—H13B | 109.5 | C23—C231—H23C | 109.5 |
C13—C131—H13C | 109.5 | H23A—C231—H23C | 109.5 |
H13A—C131—H13C | 109.5 | H23B—C231—H23C | 109.5 |
H13B—C131—H13C | 109.5 | C23—C232—H23D | 109.5 |
C13—C132—H13D | 109.5 | C23—C232—H23E | 109.5 |
C13—C132—H13E | 109.5 | H23D—C232—H23E | 109.5 |
H13D—C132—H13E | 109.5 | C23—C232—H23F | 109.5 |
C13—C132—H13F | 109.5 | H23D—C232—H23F | 109.5 |
H13D—C132—H13F | 109.5 | H23E—C232—H23F | 109.5 |
H13E—C132—H13F | 109.5 | O25—C24—C23 | 111.4 (3) |
O15—C14—C13 | 112.5 (3) | O25—C24—H241 | 105.4 (19) |
O15—C14—H141 | 106 (2) | C23—C24—H241 | 109 (2) |
C13—C14—H141 | 112 (2) | O25—C24—H242 | 108 (2) |
O15—C14—H142 | 106 (2) | C23—C24—H242 | 110 (2) |
C13—C14—H142 | 112 (2) | H241—C24—H242 | 113 (3) |
H141—C14—H142 | 109 (3) | C24—O25—P2 | 118.3 (2) |
C14—O15—P1 | 119.4 (2) | P1—O3—P2 | 132.41 (15) |
O2—P2—O25 | 115.03 (15) | ||
O1—P1—O11—C12 | 168.6 (2) | P2—O21—C22—C23 | −53.7 (4) |
O15—P1—O11—C12 | 41.8 (3) | O21—C22—C23—C24 | 57.8 (4) |
O3—P1—O11—C12 | −65.6 (3) | O21—C22—C23—C231 | −63.7 (4) |
P1—O11—C12—C13 | −54.3 (4) | O21—C22—C23—C232 | 174.6 (3) |
O11—C12—C13—C14 | 57.9 (4) | C22—C23—C24—O25 | −57.7 (4) |
O11—C12—C13—C131 | −63.6 (4) | C231—C23—C24—O25 | 63.4 (4) |
O11—C12—C13—C132 | 175.8 (3) | C232—C23—C24—O25 | −175.4 (3) |
C12—C13—C14—O15 | −55.8 (4) | C23—C24—O25—P2 | 54.5 (4) |
C131—C13—C14—O15 | 65.4 (4) | O2—P2—O25—C24 | −170.1 (2) |
C132—C13—C14—O15 | −173.8 (3) | O21—P2—O25—C24 | −43.6 (3) |
C13—C14—O15—P1 | 49.8 (4) | O3—P2—O25—C24 | 65.1 (3) |
O1—P1—O15—C14 | −166.5 (2) | O1—P1—O3—P2 | 49.1 (3) |
O11—P1—O15—C14 | −39.6 (3) | O11—P1—O3—P2 | −76.6 (2) |
O3—P1—O15—C14 | 70.0 (3) | O15—P1—O3—P2 | 172.4 (2) |
O2—P2—O21—C22 | 170.2 (2) | O2—P2—O3—P1 | 32.1 (3) |
O25—P2—O21—C22 | 42.9 (3) | O25—P2—O3—P1 | 157.1 (2) |
O3—P2—O21—C22 | −64.2 (3) | O21—P2—O3—P1 | −92.8 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C24—H241···O1i | 0.92 (3) | 2.64 (3) | 3.405 (5) | 141 (2) |
Symmetry code: (i) −x+3/2, y+1/2, z. |
Experimental details
(musa25) | (musa26) | |
Crystal data | ||
Chemical formula | C16H24O8P2 | C10H20O7P2 |
Mr | 406.29 | 314.20 |
Crystal system, space group | Triclinic, P1 | Orthorhombic, Pbca |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 9.5706 (5), 10.2415 (5), 11.6998 (5) | 9.8434 (2), 11.3589 (3), 26.6986 (8) |
α, β, γ (°) | 94.507 (4), 110.270 (4), 111.616 (5) | 90, 90, 90 |
V (Å3) | 971.75 (8) | 2985.18 (13) |
Z | 2 | 8 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.26 | 0.32 |
Crystal size (mm) | 0.28 × 0.22 × 0.22 | 0.40 × 0.18 × 0.14 |
Data collection | ||
Diffractometer | Oxford Diffraction Xcalibur 3/Sapphire3 CCD diffractometer | Oxford Diffraction Xcalibur 3/Sapphire3 CCD diffractometer |
Absorption correction | Multi-scan (CrysAlis PRO; Agilent, 2010) | Multi-scan (CrysAlis PRO; Agilent, 2010) |
Tmin, Tmax | 0.970, 1.000 | 0.847, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13183, 3522, 3111 | 33060, 2141, 1920 |
Rint | 0.018 | 0.038 |
θmax (°) | 25.3 | 23.3 |
(sin θ/λ)max (Å−1) | 0.600 | 0.555 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.090, 1.05 | 0.046, 0.094, 1.14 |
No. of reflections | 3522 | 2141 |
No. of parameters | 287 | 208 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.17, −0.37 | 0.24, −0.29 |
Computer programs: CrysAlis PRO (Agilent, 2010), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), ORTEPII (Johnson, 1976) and ORTEP-3 for Windows (Farrugia, 2012), SHELXL97 (Sheldrick, 2008) and WinGX (Farrugia, 2012).