Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229615014308/dt3032sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615014308/dt3032Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615014308/dt3032IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615014308/dt3032IIIsup4.hkl | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229615014308/dt3032Isup5.cml | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229615014308/dt3032IIsup6.cml | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229615014308/dt3032IIIsup7.cml |
CCDC references: 1415729; 1415728; 1415727
C-Alkyl (including C-arylmethyl) derivatives of Meldrum's acids are attractive building blocks in organic synthesis (Mierina, 2013) that is mainly due to the unusually high acidity of the resulting compounds (Nakamura et al., 2004; Byun et al., 2001). Arylmethyl Meldrum's acids show good and excellent antiradical and antioxidant properties (Mierina et al., 2014) also. Despite the wide-ranging applications of these compounds, the crystal structure of this type of Meldrum's acids derivatives is poorly studied. A search of the Cambridge Structural Database (Groom & Allen, 2014) revealed only one arylmethyl Meldrum's acid, namely 5-(2,3-dimethoxybenzyl)-2,2-dimethyl-1,3-dioxane-4,6-dione (CSD refcode FONZOY; reference?), studied by a single-crystal X-ray diffraction. Only a few studies have been devoted to the determination of intramolecular interactions into arylmethyl Meldrum's acids. Anomalous deshielding in 1H NMR spectra were observed for the α-H atom in the dicarbonyl fragment for compounds containing different hydrogen-bond acceptors in the ortho-position of the benzene ring in comparison with derivatives of Meldrum's acids without a hydrogen-bond acceptor at the same position. The effect was even more pronounced when an additional substituent was introduced at the benzylic position. Moreover, in the crystalline state, strong intramolecular hydrogen bonding was observed also (Fillion et al., 2009). The aim of this work was to gain more knowledge on the conformations, the intra- and mainly intermolecular contacts (hydrogen bonds, van der Waals and π–π interactions) in 5-arylmethyl-2,2-dimethyl-1,3-dioxane-4,6-diones in the crystalline state depending on different substituents. In order to find out whether these interactions in crystals of Meldrum's acid derivatives are general or unique, three structures of arylmethyl Meldrum's acids were analyzed, namely 5-[4-(diethylamino)benzyl]-2,2-dimethyl-1,3-dioxane-4,6-dione, (I), 2,2-dimethyl-5-(2,4,6-trimethoxybenzyl)-1,3-dioxane-4,6-dione, (II), 5-(4-hydroxy-3,5-dimethoxybenzyl)-2,2-dimethyl-1,3-dioxane-4,6-dione, (III).
1H (300 MHz) and 13C (75.5 MHz) NMR spectra were recorded on Bruker Avance 300 spectrometer; the samples were dissolved in CDCl3-d and the spectra were calibrated to the residue of CHCl3. IR spectra were recorded on Perkin–Elmer spectrometer (model: Spectrum BX, FT—IR system) for solid sample in KBr disc. Melting points were measured with a STUART melting point SMP10 apparatus and are uncorrected. Microanalysis was done with Carlo–Erba Instruments element analyzer (model: EA1108). High resolution mass spectra were recorded on Agilent 1290 Infinity series UPLC chromatograph equipped with Agilent 6230 TOF LC/MS mass spectrometer. Meldrum's acid, aromatic aldehydes, NaBH4, acetic acid and solvents were commercially available and were used without further purification.
\ Arylmethyl Meldrum's acids (I)–(III) were synthesized according to a known method (Frost et al., 2009) with some modifications from Meldrum's acid (IV) and aromatic aldehyde, followed by reduction of the obtained 5-arylidene-1,3-dioxane-4,6-dione, (V)–(VII), with NaBH4 (see Scheme 1).
5-[(4-Hydroxy-3,5-dimethoxyphenyl)methylene]-2,2-dimethyl-1,3-dioxane-4,6-\ dione, (VII), is a known compound (Le et al., 2013) and was used without further purification.
The syntheses were carried out according to a modification of the method of Frost et al. (2009). Arylidene Meldrum's acids (V)–(VII) (12 mmol) were dissolved in chloroform (50 ml) and the solutions cooled to 270–273 K (ice bath), followed by addition of glacial acetic acid (5.7 ml). NaBH4 (0.53 g) was added portionwise after 5 min and the mixtures were further mixed for approximately 45 min until the colour of the solutions disappeared. The reactions were quenched with water (50 ml). The organic layers were separated and the water solutions extracted with chloroform (50 ml). For each preparation, all chloroform extracts were combined and washed with brine (2 × 75 ml) and water (2 × 75 ml). The chloroform extracts were dried over Na2SO4, evaporated and recrystallized from ethanol. Single crystals of (I)–(III) suitable for X-ray analysis were obtained from solutions in methanol.
The syntheses were carried out according to the previously described method of Bigi et al. (2001). In brief, 2,2-dimethyl-1,3-dioxane-4,6-dione, (IV) (1 g, 6.9 mmol), an aromatic aldehyde (6.9 mmol) and water (50 ml) were heated at 348 K for 2 h, followed with cooling to room temperature and filtration of the resulted precipitates. The solid material was air-dried in each case and recrystalized from ethanol.
The compound appeared as white solid (yield 35%, m.p. 411-412 K). IR (KBr) ν (cm-1): 3690, 2995, 2940, 2900, 2450, 2360, 2340, 1675, 1605, 1565, 1515, 1475, 1385, 1365, 1345, 1295, 1255, 1210, 1195, 1110, 1100, 1035, 1020, 990, 960, 925, 825, 810, 795, 745, 730, 690, 645, 620, 550, 525, 520, 425; 1H NMR (300 MHz, CDCl3): δ 1.14 [6H, t, J = 7.1 Hz, N(CH2CH3)2], 1.45 (3H, s, Me), 1.73 (3H, s, Me), 3.3 [4H, q, J = 7.1 Hz, N(CH2CH3)2], 3.41 (2H, d, J = 4.7 Hz, CH2), 3.72 (1H, t, J = 4.7 Hz, CH), 6.61 (2H, d, J = 8.5 Hz, 2 × CArH), 7.17 (2H, d, J = 8.5 Hz, 2 × CArH); 13C NMR (75.5 MHz, CDCl3): δ 12.6 [N(CH2CH3)2], 27.5 (Me), 28.5 (Me), 31.7 (CH2), 44.4 [N(CH2CH3)2], 48.6 (CH), 105.2 (CMe2), 112.0 (2 × CArH), 123.6 (CArCH2), 130.9 (2 × CArH), 146.9 (CArNEt2), 165.8 (COOR). Analysis calculated for C17H23NO4: C 66.86, H 7.59, N 4.59%; found: C 66.53, H 7.70, N 4.38%.
The compound appeared as white solid (yield 55%, m.p. 416–417 K). IR (KBr) ν (cm-1): 3680, 3010, 2980, 2950, 2910, 2865, 2840, 1780, 1750, 1610, 1600, 1505, 1465, 1420, 1395, 1390, 1375, 1335, 1265, 1235, 1215, 1205, 1155, 1120, 1085, 1075, 1035, 1025, 990, 955, 945, 925, 865, 835, 795, 750, 740, 705, 630, 545, 490, 420; 1H NMR (300 MHz, CDCl3): δ 1.75 (3H, s, Me), 1.82 (3H, s, Me), 3.37 (2H, d, J = 7.3 Hz, CH2), 3.79 (9H, s, 3 × OMe), 3.92 (1H, t, J = 7.3 Hz, CH), 6.12 (2H, s, 2 × CArH); 13C NMR (75.5 MHz, CDCl3): δ 22.8 (CH2), 27.7 (Me), 28.7 (Me), 45.0 (CH), 55.4 (OMe), 55.7 (2 × OMe), 90.7 (2 × CArH), 105.1 (CMe2/CArCH2), 105.2 (CMe2/CArCH2), 159.0 (2 × CArOMe), 160.4 (CArOMe), 165.8 (COOR). Analysis calculated for C16H20O7: C 59.22, H 6.22%; found: C 59.20, H 6.20%.
The compound appeared as white solid (yield 36%, m.p. 398 K). IR (KBr) ν (cm-1): 3560, 3500, 2995, 2955, 2940, 2875, 2840, 1785, 1750, 1615, 1520, 1460, 1420, 1995, 1385, 1350, 1310, 1265, 1245, 1215, 1195, 1115, 1055, 1020, 1000, 970, 950, 905, 885, 865, 850, 835, 810, 690, 670, 645, 635, 620, 585, 490, 455; 1H NMR (300 MHz, CDCl3): δ 1.47 (3H, s, Me), 1.72 (3H, s, Me), 3.42 (2H, d, J = 4.6 Hz, CH2), 3.72 (1H, t, J = 4.6 Hz, CH), 3.85 (6H, s, 2 × OMe), 5.48 (1H, brs, OH), 6.55 (2H, s, 2 × CArH); 13C NMR (75.5 MHz, CDCl3): δ 27.6 (Me), 28.7 (Me), 32.6 (CH2), 48.6 (CH), 56.5 (OMe), 105.4 (CMe2), 106.7 (2 × CArH), 128.2 (CArCH2), 133.9 (CArOH), 147.0 (2 × CArOMe), 165.7 (COOR). Analysis calculated for [M + Na]+ m/z: 333.0950; found m/z: 333.0942.
This compound is known [m.p. 398 K; literature 397–398 K (Strods et al., 1978)]. Nevertheless, NMR spectral data have not been provided previously. 1H NMR (300 MHz, CDCl3): δ 1.21 [6H, t, J = 7.1 Hz, N(CH2CH3)2], 1.75 (6H, s, 2 × Me), 3.46 [4H, q, J = 7.1 Hz, N(CH2CH3)2], 6.65 (2H, d, J = 9.3 Hz, 2 × CArH), 8.21 (2H, d, J = 9.3 Hz, 2 × CArH), 8.24 (1H, s, CH); 13C NMR (75.5 MHz, CDCl3): δ 12.7 [N(CH2CH3)2], 27.3 (2 × Me), 45.0 [N(CH2CH3)2], 103.4 (CMe2), 104.2 (C═CH), 111.1 (2 × CArH), 119.8 (CArCH), 139.4 (2 × CArH), 152.8 (CArNEt2), 157.8 (CH), 161.6 (COOR), 165.4 (COOR).
The compound appeared as bright-yellow solid (yield 78%; m.p. 487 K). IR (KBr) ν (cm-1): 1750, 1725, 1595, 1570, 1495, 1470, 1450, 1395, 1385, 1365, 1335, 1285, 1230, 1205, 1190, 1155, 1140, 1110, 1030, 1005, 940, 905, 825, 785, 725, 490, 430; 1H NMR (300 MHz, CDCl3): δ 1.84 (6H, s, 2 × Me), 3.85 (6H, s, 2 × OMe), 3.88 (3H, s, OMe), 6.11 (2H, s, 2 × CArH), 8.49 (1H, s, CH); 13C NMR (75.5 MHz, CDCl3): δ 27.4 (2 × Me), 55.7 (OMe), 55.8 (2 × OMe), 90.8 (2 × CArH), 104.2 (CMe2), 106.1 (CArCH), 114.6 (C═CH), 147.8 (CH), 161.1 (2 × CArOMe), 161.2 (CArOMe), 163.7 (COOR), 165.9 (COOR). Analysis calculated for [M + Na]+ m/z: 345.0945; found m/z: 345.0945.
Crystal data, data collection and structure refinement details are summarized in Table 1.
In (I), the position of the transferred H atom was located from a difference electron-density map and was refined in a least-squares full-matrix isotropic approximation.
The molecular structure of (I)–(III), with the atom-numbering schemes, are shown in Figs. 1, 2 and 3, respectively. The packing diagrams showing supramolecular features of the structures are presented in Figs. 4, 5 and 6, respectively. In the crystal, 5-[4-(diethylamino)benzyl]-2,2-dimethyl-1,3-dioxane-4,6-dione, (I), exists in the zwitterionic form. The sum of the valence angles at the C5 atom is 359.1 (3)°; thus it is in the sp2 hybridization state. An analysis of the bond lengths in the dicarbonyl fragment shows differentiation of single [C5—C6 = 1.411 (2) Å and C4—O2 = 1.252 (2) Å] and double bonds [C4—C5 = 1.384 (2) Å and C6—O19 = 1.229 (2) Å], suggesting the formation of the enolate structure. The absorption band in the IR spectrum at 1675 cm-1 is consistent with the existence of the enolate form. The H atom on O20 is transferred to atom N16 forming the zwitterionic structure of the residue. The heterocycle assumes a distorted boat conformation. Atoms C2 and C5 deviate from the least-squares plane [±0.006 (1) Å] calculated for the other four atoms in the heterocycle by 0.517 (2) and 0.074 (2) Å, respectively. The corresponding dihedral angles between the plane bottom of the boat and the triangles formed by atoms C2/O1/O3 and C4–C6 are 39.4 (2) and 6.1 (2)°, respectively. The total puckering amplitude for the heterocycle is 0.389 (2) Å. This is the first example where an anilinium-type zwitterionic form of Meldrum's acid is described and the inner ions are linked with the arylmethyl moiety. Whereas, until now, the crystal structures of inner salts have been established only for dimethylaminomethyl Meldrum's acid (Li et al., 2005) and a pyridin-1-yl derivative of Meldrum's acid (Zia-Ebrahimi et al., 1994), where the distance between the ammonium ion and the deprotonated enalizated malonate moiety is remarkably shorter – just CH2 functionality. In the crystal, the residues are assembled by means of strong N—H···O hydrogen bonds into infinite chains with the graph set C(10) along the unit-cell a axis (Fig. 2).
As we have already mentioned in the Introduction, the ability of the acidic C—H bond to form an intramolecular C—H···X (X = O, S, F) bonds in benzyl Meldrum's acids has been investigated by Fillion et al. (2009), and it was concluded that an intramolecular C5—H···O hydrogen bond is able to drive the conformational properties of arylmethyl Meldrum's acids in the solid state. In this respect, it was interesting to find out whether 2,2-dimethyl-5-(2,4,6-trimethoxybenzyl)-1,3-dioxane-4,6-dione, (II), which contains methoxy groups in both ortho-positions of the benzyl fragment, assumes the conformation with an intramolecular C5—H···O hydrogen bond. It turned out that this kind of hydrogen bond is not present in the crystal structure of (II). In the molecule, the arylmethyl fragment is rotated in the opposite direction to the acidic C5—H bond. The conformation of this type of Meldrum's acids is well described by the torsion angles H—C5—C7—C8 and C5—C7—C8—C9 (Table 2). The planar 2,4,6-trimethoxyphenyl fragment is almost perpendicular to the average plane of the six-membered heterocycle of the Meldrum's acid. The 1,3-dioxane moiety adopts a boat conformation. Atoms C2 and C5 deviate from the mean plane [±0.008 (1) Å] formed by the other four atoms in the heterocycle by 0.502 (2) and 0.383 (2) Å. The corresponding dihedral angles between the bottom of the boat and the triangles formed by atoms C2/O1/O3 and C4–C6 are 37.3 (1) and 27.2 (2)°, respectively. The puckering amplitude Q for the heterocycle is 0.515 (2) Å. Compound (II) has no classical hydrogen-bond donors and acceptors. Its packing in the crystal is governed, mainly, by van der Waals interactions. Two short contacts (Table 3) can be attributed to C—H···O type hydrogen bonds. Fig. 4 shows a fragment of the crystal packing for the structure of (II). Thus, one can conclude that the presence of a hydrogen-bond acceptor in the ortho-position of the arylmethyl fragment does not guarantee the formation of a C5—H···O intramolecular bond and the molecular conformation is dependent on the overall balance of the free energy of the crystal lattice.
The crystal structure of 5-(4-hydroxy-3,5-dimethoxybenzyl)-2,2-dimethyl-1,3-dioxane-4,6-dione, (III), contains two independent molecules (A and B) in the asymmetric unit. The molecules differ in their conformations defined, mainly, by the torsion angles along the C5—C7 and C7—C8 bonds (Table 2). The dihedral angles between the least-squares mean planes of the heterocycle and benzene rings in the molecules A and B are 41.8 (1) and 55.1 (1)°, respectively. In both molecules, the Meldrum's acid heterocycles assume the boat conformation. Atoms C2 and C5 deviate from the mean planes formed by the other four atoms of the rings in molecules A and B by 0.441 (2)/0.477 (2) and 0.476 (3)/0.469 (2) Å, respectively. The corresponding dihedral angles between the bottom of the boat and the triangles formed by atoms C2/O1/O3 and C4–C6 for molecules A and B are 32.3 (2)/33.4 (2) and 35.0 (2)/33.5 (2)°, respectively. The corresponding values of the puckering amplitude Q for the heterocycle in molecules A and B are 0.533 (2) and 0.546 (2) Å, respectively. Molecules A and B form dimers by means of hydrogen bonds of the O—H···O type (Table 3). The dimers are associated into a tetrameric synthon through π–π interactions of the partially overlapping aryl rings of molecules A and B (Fig. 6). The distance between the centroids is 3.678 Å. The hydroxy groups are also involved in intramolecular hydrogen bonds with the O atoms of adjacent methoxy groups. There are also intramolecular C—H···O interactions in the structure. Their geometrical parameters are given in the Table 3.
Despite the high structural similarity of studied arylmethyl Meldrum's acids, the nature of different substituents resulted in remarkable differences in both the molecular conformations and the crystal packing arrangements. The presence of a substituent with a basic centre in compound (I) leads to the formation of an inner salt accompanied by drastic changes in the conformation of the 1,3-dioxane-4,6-dione fragment. By virtue of strong hydrogen bonds of the N—H···O type, the residues are assembled into infinite chains with the graph-set C(10). Compound (II) contains methoxy groups in both the ortho- and para-positions of the arylmethyl fragment. Hypothetically, one could expect the formation of an intramolecular C5—H···O hydrogen bond. However, in the crystal, this hydrogen bond was not observed. Because of the absence of classical hydrogen-bond donors in this structure, the crystal packing is controled by the van der Waals forces and weak C—H···O interactions. Compound (III) contains methoxy groups in both meta-positions and a hydroxy group in the para-position. The substituted aryl moiety forms an extensive conjugated π-electron system that can give rise to the emergence of π–π interactions in the crystal packing. Indeed, in the structure of (III), we observed the formation of supramolecular tetrameric synthons which comprise hydrogen-bonded dimers associated into tetramers through π–π interactions of overlapping benzene rings.
For all compounds, data collection: COLLECT (Bruker, 2004); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
C17H23NO4 | F(000) = 1312 |
Mr = 305.36 | Dx = 1.224 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 41560 reflections |
a = 15.0721 (4) Å | θ = 1.0–27.1° |
b = 11.3109 (3) Å | µ = 0.09 mm−1 |
c = 19.4443 (4) Å | T = 190 K |
V = 3314.85 (14) Å3 | Block, colourless |
Z = 8 | 0.42 × 0.25 × 0.18 mm |
Nonius KappaCCD diffractometer | 2532 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.036 |
Graphite monochromator | θmax = 27.0°, θmin = 2.5° |
CCD scans | h = −19→19 |
6647 measured reflections | k = −14→14 |
3586 independent reflections | l = −24→24 |
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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.135 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0749P)2 + 0.3201P] where P = (Fo2 + 2Fc2)/3 |
3586 reflections | (Δ/σ)max = 0.004 |
207 parameters | Δρmax = 0.42 e Å−3 |
0 restraints | Δρmin = −0.32 e Å−3 |
C17H23NO4 | V = 3314.85 (14) Å3 |
Mr = 305.36 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 15.0721 (4) Å | µ = 0.09 mm−1 |
b = 11.3109 (3) Å | T = 190 K |
c = 19.4443 (4) Å | 0.42 × 0.25 × 0.18 mm |
Nonius KappaCCD diffractometer | 2532 reflections with I > 2σ(I) |
6647 measured reflections | Rint = 0.036 |
3586 independent reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.135 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.42 e Å−3 |
3586 reflections | Δρmin = −0.32 e Å−3 |
207 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
O19 | −0.39182 (8) | 0.89445 (11) | 0.25622 (6) | 0.0368 (3) | |
O3 | −0.22071 (7) | 0.89290 (11) | 0.10008 (6) | 0.0304 (3) | |
N16 | −0.70440 (9) | 0.52977 (13) | 0.07922 (7) | 0.0298 (3) | |
O1 | −0.25444 (7) | 0.87494 (11) | 0.21756 (5) | 0.0326 (3) | |
O20 | −0.32271 (7) | 0.93560 (12) | 0.02228 (6) | 0.0342 (3) | |
C8 | −0.52464 (9) | 0.81687 (14) | 0.10696 (8) | 0.0235 (4) | |
C10 | −0.63975 (10) | 0.71860 (15) | 0.04146 (8) | 0.0283 (4) | |
H2 | −0.6781 | 0.7176 | 0.0040 | 0.034* | |
C9 | −0.58260 (10) | 0.81321 (15) | 0.05149 (8) | 0.0271 (4) | |
H3 | −0.5831 | 0.8756 | 0.0203 | 0.033* | |
C13 | −0.52375 (10) | 0.71987 (15) | 0.15134 (8) | 0.0275 (4) | |
H4 | −0.4839 | 0.7192 | 0.1879 | 0.033* | |
C6 | −0.34447 (11) | 0.88844 (14) | 0.20485 (8) | 0.0265 (4) | |
C4 | −0.30898 (10) | 0.90911 (14) | 0.08390 (8) | 0.0254 (4) | |
C17 | −0.76788 (11) | 0.52129 (17) | 0.13946 (9) | 0.0370 (4) | |
H7A | −0.8090 | 0.4569 | 0.1313 | 0.044* | |
H7B | −0.7345 | 0.5027 | 0.1807 | 0.044* | |
C7 | −0.46781 (10) | 0.92404 (15) | 0.12018 (8) | 0.0269 (4) | |
H8A | −0.4930 | 0.9673 | 0.1586 | 0.032* | |
H8B | −0.4709 | 0.9750 | 0.0801 | 0.032* | |
C5 | −0.37157 (10) | 0.89992 (13) | 0.13570 (7) | 0.0233 (3) | |
C12 | −0.58020 (10) | 0.62493 (15) | 0.14266 (8) | 0.0285 (4) | |
H10 | −0.5788 | 0.5614 | 0.1730 | 0.034* | |
C11 | −0.63914 (10) | 0.62607 (14) | 0.08772 (8) | 0.0263 (4) | |
C2 | −0.20050 (11) | 0.83192 (17) | 0.16270 (9) | 0.0345 (4) | |
C15 | −0.66273 (13) | 0.41035 (17) | 0.06799 (11) | 0.0439 (5) | |
H13A | −0.6246 | 0.3919 | 0.1068 | 0.053* | |
H13B | −0.7091 | 0.3509 | 0.0661 | 0.053* | |
C18 | −0.81919 (13) | 0.63211 (19) | 0.15121 (10) | 0.0455 (5) | |
H14A | −0.7792 | 0.6949 | 0.1631 | 0.068* | |
H14B | −0.8607 | 0.6201 | 0.1880 | 0.068* | |
H14C | −0.8508 | 0.6527 | 0.1100 | 0.068* | |
C21 | −0.21448 (15) | 0.70056 (19) | 0.15389 (10) | 0.0498 (5) | |
H15A | −0.1985 | 0.6605 | 0.1956 | 0.075* | |
H15B | −0.1781 | 0.6723 | 0.1169 | 0.075* | |
H15C | −0.2757 | 0.6854 | 0.1436 | 0.075* | |
C22 | −0.10625 (12) | 0.8645 (2) | 0.18035 (11) | 0.0553 (6) | |
H16A | −0.1014 | 0.9488 | 0.1844 | 0.083* | |
H16B | −0.0673 | 0.8371 | 0.1447 | 0.083* | |
H16C | −0.0900 | 0.8283 | 0.2232 | 0.083* | |
C14 | −0.60972 (16) | 0.4049 (2) | 0.00370 (14) | 0.0656 (7) | |
H17A | −0.6458 | 0.4293 | −0.0344 | 0.098* | |
H17B | −0.5897 | 0.3253 | −0.0036 | 0.098* | |
H17C | −0.5594 | 0.4565 | 0.0076 | 0.098* | |
HN16 | −0.7422 (14) | 0.548 (2) | 0.0384 (10) | 0.051 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O19 | 0.0388 (7) | 0.0469 (8) | 0.0247 (6) | −0.0034 (6) | 0.0066 (5) | −0.0072 (5) |
O3 | 0.0221 (6) | 0.0414 (7) | 0.0277 (6) | 0.0028 (5) | 0.0011 (5) | 0.0019 (5) |
N16 | 0.0285 (7) | 0.0276 (8) | 0.0332 (8) | −0.0021 (6) | −0.0092 (6) | 0.0010 (6) |
O1 | 0.0293 (6) | 0.0439 (8) | 0.0248 (6) | 0.0008 (5) | −0.0034 (5) | −0.0052 (5) |
O20 | 0.0293 (6) | 0.0499 (8) | 0.0235 (6) | 0.0060 (6) | 0.0032 (5) | 0.0070 (5) |
C8 | 0.0190 (7) | 0.0263 (9) | 0.0250 (8) | 0.0029 (6) | 0.0038 (6) | −0.0016 (6) |
C10 | 0.0272 (8) | 0.0332 (10) | 0.0244 (8) | 0.0030 (7) | −0.0047 (6) | −0.0014 (7) |
C9 | 0.0267 (8) | 0.0292 (9) | 0.0253 (8) | 0.0044 (7) | 0.0020 (7) | 0.0026 (7) |
C13 | 0.0231 (8) | 0.0348 (10) | 0.0247 (8) | −0.0015 (7) | −0.0040 (6) | 0.0005 (7) |
C6 | 0.0302 (8) | 0.0230 (9) | 0.0264 (8) | −0.0034 (7) | 0.0004 (7) | −0.0044 (7) |
C4 | 0.0226 (8) | 0.0256 (9) | 0.0280 (8) | 0.0011 (7) | 0.0009 (6) | −0.0013 (7) |
C17 | 0.0364 (10) | 0.0431 (11) | 0.0316 (9) | −0.0167 (8) | −0.0078 (8) | 0.0109 (8) |
C7 | 0.0250 (8) | 0.0266 (9) | 0.0292 (8) | 0.0017 (7) | 0.0043 (7) | −0.0003 (7) |
C5 | 0.0239 (8) | 0.0206 (8) | 0.0253 (8) | −0.0021 (6) | 0.0007 (6) | −0.0016 (6) |
C12 | 0.0270 (8) | 0.0299 (9) | 0.0288 (8) | −0.0026 (7) | −0.0027 (7) | 0.0054 (7) |
C11 | 0.0231 (8) | 0.0275 (9) | 0.0283 (8) | −0.0014 (7) | −0.0011 (6) | −0.0019 (7) |
C2 | 0.0313 (9) | 0.0445 (11) | 0.0278 (9) | 0.0078 (8) | −0.0018 (7) | −0.0002 (8) |
C15 | 0.0406 (10) | 0.0325 (11) | 0.0585 (12) | 0.0018 (8) | −0.0150 (9) | −0.0060 (9) |
C18 | 0.0428 (11) | 0.0549 (13) | 0.0389 (10) | −0.0079 (10) | 0.0086 (9) | −0.0006 (9) |
C21 | 0.0640 (13) | 0.0414 (12) | 0.0441 (11) | 0.0172 (10) | 0.0016 (10) | 0.0007 (9) |
C22 | 0.0313 (10) | 0.0883 (19) | 0.0465 (12) | 0.0063 (11) | −0.0073 (9) | 0.0032 (11) |
C14 | 0.0586 (13) | 0.0534 (15) | 0.0848 (17) | 0.0049 (11) | 0.0067 (13) | −0.0183 (13) |
O19—C6 | 1.229 (2) | C17—H7B | 0.9700 |
O3—C4 | 1.3794 (18) | C7—C5 | 1.506 (2) |
O3—C2 | 1.432 (2) | C7—H8A | 0.9700 |
N16—C11 | 1.477 (2) | C7—H8B | 0.9700 |
N16—C15 | 1.505 (2) | C12—C11 | 1.389 (2) |
N16—C17 | 1.515 (2) | C12—H10 | 0.9300 |
N16—HN16 | 1.00 (2) | C2—C22 | 1.507 (3) |
O1—C6 | 1.388 (2) | C2—C21 | 1.510 (3) |
O1—C2 | 1.427 (2) | C15—C14 | 1.485 (3) |
O20—C4 | 1.252 (2) | C15—H13A | 0.9700 |
C8—C9 | 1.388 (2) | C15—H13B | 0.9700 |
C8—C13 | 1.396 (2) | C18—H14A | 0.9600 |
C8—C7 | 1.506 (2) | C18—H14B | 0.9600 |
C10—C11 | 1.380 (2) | C18—H14C | 0.9600 |
C10—C9 | 1.387 (2) | C21—H15A | 0.9600 |
C10—H2 | 0.9300 | C21—H15B | 0.9600 |
C9—H3 | 0.9300 | C21—H15C | 0.9600 |
C13—C12 | 1.380 (2) | C22—H16A | 0.9600 |
C13—H4 | 0.9300 | C22—H16B | 0.9600 |
C6—C5 | 1.411 (2) | C22—H16C | 0.9600 |
C4—C5 | 1.384 (2) | C14—H17A | 0.9600 |
C17—C18 | 1.491 (3) | C14—H17B | 0.9600 |
C17—H7A | 0.9700 | C14—H17C | 0.9600 |
C4—O3—C2 | 117.59 (12) | C13—C12—H10 | 120.6 |
C11—N16—C15 | 113.58 (13) | C11—C12—H10 | 120.6 |
C11—N16—C17 | 112.37 (13) | C10—C11—C12 | 120.82 (15) |
C15—N16—C17 | 108.58 (14) | C10—C11—N16 | 118.81 (14) |
C11—N16—HN16 | 108.2 (13) | C12—C11—N16 | 120.34 (14) |
C15—N16—HN16 | 108.2 (13) | O1—C2—O3 | 110.50 (13) |
C17—N16—HN16 | 105.5 (12) | O1—C2—C22 | 106.47 (15) |
C6—O1—C2 | 117.49 (12) | O3—C2—C22 | 106.04 (15) |
C9—C8—C13 | 117.57 (15) | O1—C2—C21 | 109.92 (15) |
C9—C8—C7 | 120.95 (14) | O3—C2—C21 | 110.34 (14) |
C13—C8—C7 | 121.43 (14) | C22—C2—C21 | 113.44 (17) |
C11—C10—C9 | 119.29 (14) | C14—C15—N16 | 112.59 (17) |
C11—C10—H2 | 120.4 | C14—C15—H13A | 109.1 |
C9—C10—H2 | 120.4 | N16—C15—H13A | 109.1 |
C10—C9—C8 | 121.52 (15) | C14—C15—H13B | 109.1 |
C10—C9—H3 | 119.2 | N16—C15—H13B | 109.1 |
C8—C9—H3 | 119.2 | H13A—C15—H13B | 107.8 |
C12—C13—C8 | 122.00 (14) | C17—C18—H14A | 109.5 |
C12—C13—H4 | 119.0 | C17—C18—H14B | 109.5 |
C8—C13—H4 | 119.0 | H14A—C18—H14B | 109.5 |
O19—C6—O1 | 115.41 (14) | C17—C18—H14C | 109.5 |
O19—C6—C5 | 126.94 (15) | H14A—C18—H14C | 109.5 |
O1—C6—C5 | 117.56 (14) | H14B—C18—H14C | 109.5 |
O20—C4—O3 | 114.16 (13) | C2—C21—H15A | 109.5 |
O20—C4—C5 | 127.00 (14) | C2—C21—H15B | 109.5 |
O3—C4—C5 | 118.78 (14) | H15A—C21—H15B | 109.5 |
C18—C17—N16 | 113.13 (14) | C2—C21—H15C | 109.5 |
C18—C17—H7A | 109.0 | H15A—C21—H15C | 109.5 |
N16—C17—H7A | 109.0 | H15B—C21—H15C | 109.5 |
C18—C17—H7B | 109.0 | C2—C22—H16A | 109.5 |
N16—C17—H7B | 109.0 | C2—C22—H16B | 109.5 |
H7A—C17—H7B | 107.8 | H16A—C22—H16B | 109.5 |
C8—C7—C5 | 115.84 (13) | C2—C22—H16C | 109.5 |
C8—C7—H8A | 108.3 | H16A—C22—H16C | 109.5 |
C5—C7—H8A | 108.3 | H16B—C22—H16C | 109.5 |
C8—C7—H8B | 108.3 | C15—C14—H17A | 109.5 |
C5—C7—H8B | 108.3 | C15—C14—H17B | 109.5 |
H8A—C7—H8B | 107.4 | H17A—C14—H17B | 109.5 |
C4—C5—C6 | 120.20 (14) | C15—C14—H17C | 109.5 |
C4—C5—C7 | 119.80 (14) | H17A—C14—H17C | 109.5 |
C6—C5—C7 | 119.09 (13) | H17B—C14—H17C | 109.5 |
C13—C12—C11 | 118.75 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H8A···O19 | 0.97 | 2.57 | 2.9019 | 100 |
C7—H8B···O20 | 0.97 | 2.54 | 2.9023 | 102 |
N16—HN16···O20i | 1.00 (2) | 1.70 (2) | 2.688 (2) | 169 (2) |
C10—H2···O3i | 0.93 | 2.46 | 3.264 (2) | 144 |
C17—H7B···O1ii | 0.97 | 2.46 | 3.253 (2) | 139 |
C17—H7B···O19ii | 0.97 | 2.57 | 3.459 (2) | 152 |
C12—H10···O19ii | 0.93 | 2.38 | 3.292 (2) | 168 |
Symmetry codes: (i) x−1/2, −y+3/2, −z; (ii) −x−1, y−1/2, −z+1/2. |
C16H20O7 | F(000) = 1376 |
Mr = 324.32 | Dx = 1.438 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 15283 reflections |
a = 9.8128 (2) Å | θ = 1.0–27.5° |
b = 10.0235 (2) Å | µ = 0.11 mm−1 |
c = 30.4669 (6) Å | T = 190 K |
V = 2996.68 (10) Å3 | Plate, colourless |
Z = 8 | 0.26 × 0.24 × 0.10 mm |
Nonius KappaCCD diffractometer | 2421 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.040 |
Graphite monochromator | θmax = 27.4°, θmin = 2.5° |
CCD scans | h = −12→12 |
6059 measured reflections | k = −12→12 |
3374 independent reflections | l = −39→39 |
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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.105 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0465P)2 + 0.7724P] where P = (Fo2 + 2Fc2)/3 |
3374 reflections | (Δ/σ)max = 0.009 |
213 parameters | Δρmax = 0.27 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
C16H20O7 | V = 2996.68 (10) Å3 |
Mr = 324.32 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 9.8128 (2) Å | µ = 0.11 mm−1 |
b = 10.0235 (2) Å | T = 190 K |
c = 30.4669 (6) Å | 0.26 × 0.24 × 0.10 mm |
Nonius KappaCCD diffractometer | 2421 reflections with I > 2σ(I) |
6059 measured reflections | Rint = 0.040 |
3374 independent reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.105 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.27 e Å−3 |
3374 reflections | Δρmin = −0.24 e Å−3 |
213 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
O3 | 0.70620 (11) | −0.09851 (11) | 0.07913 (4) | 0.0200 (3) | |
O1 | 0.63264 (10) | 0.08643 (11) | 0.03698 (3) | 0.0208 (3) | |
O15 | 0.36539 (11) | 0.25988 (11) | 0.21152 (4) | 0.0219 (3) | |
O20 | 0.50007 (11) | 0.23932 (11) | 0.06669 (4) | 0.0230 (3) | |
O21 | 0.65142 (12) | −0.11714 (12) | 0.14892 (4) | 0.0264 (3) | |
O17 | −0.03063 (10) | 0.01509 (12) | 0.16158 (4) | 0.0246 (3) | |
O19 | 0.40355 (10) | −0.04681 (11) | 0.09580 (4) | 0.0223 (3) | |
C5 | 0.62662 (15) | 0.10193 (16) | 0.11675 (5) | 0.0178 (3) | |
H1 | 0.7135 | 0.1476 | 0.1219 | 0.021* | |
C14 | 0.28290 (17) | 0.34188 (17) | 0.23906 (6) | 0.0248 (4) | |
H2A | 0.2214 | 0.3932 | 0.2213 | 0.037* | |
H2B | 0.3401 | 0.4010 | 0.2556 | 0.037* | |
H2C | 0.2316 | 0.2866 | 0.2588 | 0.037* | |
C9 | 0.32122 (15) | 0.01330 (15) | 0.12661 (5) | 0.0181 (3) | |
C11 | 0.10456 (15) | 0.05114 (16) | 0.16010 (5) | 0.0196 (4) | |
C6 | 0.57935 (15) | 0.14942 (16) | 0.07239 (5) | 0.0181 (3) | |
C12 | 0.16063 (16) | 0.14689 (16) | 0.18732 (5) | 0.0202 (4) | |
H6 | 0.1068 | 0.1932 | 0.2073 | 0.024* | |
C10 | 0.18333 (15) | −0.01686 (15) | 0.12965 (5) | 0.0190 (4) | |
H7 | 0.1446 | −0.0814 | 0.1116 | 0.023* | |
C22 | 0.87603 (16) | 0.05431 (17) | 0.04927 (6) | 0.0247 (4) | |
H8A | 0.8727 | 0.1099 | 0.0749 | 0.037* | |
H8B | 0.8973 | 0.1079 | 0.0241 | 0.037* | |
H8C | 0.9450 | −0.0127 | 0.0530 | 0.037* | |
C4 | 0.66056 (15) | −0.04586 (16) | 0.11732 (5) | 0.0187 (3) | |
C7 | 0.53346 (15) | 0.14686 (17) | 0.15413 (5) | 0.0207 (4) | |
H10A | 0.5723 | 0.1135 | 0.1813 | 0.025* | |
H10B | 0.5378 | 0.2434 | 0.1555 | 0.025* | |
C23 | 0.73435 (18) | −0.09981 (17) | 0.00263 (5) | 0.0265 (4) | |
H11A | 0.7991 | −0.1710 | 0.0058 | 0.040* | |
H11B | 0.7566 | −0.0479 | −0.0229 | 0.040* | |
H11C | 0.6445 | −0.1365 | −0.0006 | 0.040* | |
C18 | 0.35868 (17) | −0.16978 (16) | 0.07704 (6) | 0.0236 (4) | |
H12A | 0.3385 | −0.2322 | 0.1001 | 0.035* | |
H12B | 0.4292 | −0.2054 | 0.0586 | 0.035* | |
H12C | 0.2782 | −0.1544 | 0.0599 | 0.035* | |
C2 | 0.73884 (15) | −0.01231 (16) | 0.04268 (5) | 0.0199 (4) | |
C8 | 0.38392 (15) | 0.10803 (16) | 0.15365 (5) | 0.0175 (3) | |
C16 | −0.10763 (16) | 0.06787 (18) | 0.19715 (6) | 0.0267 (4) | |
H15A | −0.0627 | 0.0474 | 0.2243 | 0.040* | |
H15B | −0.1970 | 0.0289 | 0.1971 | 0.040* | |
H15C | −0.1152 | 0.1629 | 0.1940 | 0.040* | |
C13 | 0.29995 (15) | 0.17235 (15) | 0.18408 (5) | 0.0184 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O3 | 0.0245 (6) | 0.0159 (6) | 0.0196 (6) | 0.0020 (5) | 0.0024 (5) | 0.0005 (5) |
O1 | 0.0229 (6) | 0.0206 (6) | 0.0189 (6) | 0.0049 (4) | −0.0004 (5) | 0.0003 (5) |
O15 | 0.0239 (6) | 0.0207 (6) | 0.0212 (6) | −0.0012 (5) | 0.0019 (5) | −0.0073 (5) |
O20 | 0.0212 (6) | 0.0181 (6) | 0.0298 (7) | 0.0038 (5) | −0.0009 (5) | 0.0007 (5) |
O21 | 0.0319 (7) | 0.0243 (7) | 0.0228 (7) | −0.0006 (5) | 0.0010 (5) | 0.0057 (5) |
O17 | 0.0175 (6) | 0.0285 (7) | 0.0277 (7) | −0.0019 (5) | 0.0049 (5) | −0.0045 (5) |
O19 | 0.0204 (6) | 0.0215 (6) | 0.0251 (7) | −0.0034 (5) | 0.0041 (5) | −0.0102 (5) |
C5 | 0.0152 (7) | 0.0184 (8) | 0.0199 (8) | −0.0018 (6) | 0.0006 (6) | −0.0026 (7) |
C14 | 0.0315 (9) | 0.0210 (9) | 0.0220 (9) | 0.0001 (8) | 0.0039 (7) | −0.0059 (7) |
C9 | 0.0210 (8) | 0.0161 (8) | 0.0173 (9) | 0.0015 (6) | 0.0025 (6) | 0.0003 (7) |
C11 | 0.0171 (8) | 0.0186 (8) | 0.0231 (9) | −0.0011 (6) | 0.0004 (6) | 0.0032 (7) |
C6 | 0.0167 (7) | 0.0160 (8) | 0.0216 (9) | −0.0043 (6) | 0.0020 (6) | −0.0012 (7) |
C12 | 0.0221 (8) | 0.0183 (8) | 0.0202 (9) | 0.0016 (7) | 0.0051 (7) | −0.0013 (7) |
C10 | 0.0206 (8) | 0.0165 (8) | 0.0199 (9) | −0.0008 (6) | −0.0010 (6) | −0.0014 (7) |
C22 | 0.0230 (8) | 0.0223 (9) | 0.0287 (10) | 0.0020 (7) | 0.0057 (7) | 0.0013 (8) |
C4 | 0.0158 (7) | 0.0217 (8) | 0.0185 (8) | −0.0017 (7) | −0.0015 (6) | 0.0000 (7) |
C7 | 0.0190 (8) | 0.0221 (9) | 0.0210 (9) | −0.0015 (7) | −0.0003 (6) | −0.0048 (7) |
C23 | 0.0346 (9) | 0.0222 (9) | 0.0226 (9) | 0.0047 (7) | 0.0014 (7) | −0.0014 (8) |
C18 | 0.0294 (9) | 0.0169 (8) | 0.0244 (9) | −0.0024 (7) | 0.0028 (7) | −0.0045 (7) |
C2 | 0.0224 (8) | 0.0167 (8) | 0.0206 (9) | 0.0044 (6) | 0.0037 (7) | 0.0034 (7) |
C8 | 0.0190 (8) | 0.0164 (8) | 0.0171 (8) | −0.0004 (6) | 0.0012 (6) | 0.0010 (7) |
C16 | 0.0207 (8) | 0.0340 (10) | 0.0256 (10) | −0.0002 (7) | 0.0057 (7) | −0.0006 (8) |
C13 | 0.0231 (8) | 0.0140 (8) | 0.0180 (8) | 0.0001 (6) | −0.0020 (6) | −0.0005 (7) |
O3—C4 | 1.3539 (19) | C11—C10 | 1.386 (2) |
O3—C2 | 1.4430 (18) | C12—C13 | 1.394 (2) |
O1—C6 | 1.3551 (18) | C12—H6 | 0.9300 |
O1—C2 | 1.4477 (18) | C10—H7 | 0.9300 |
O15—C13 | 1.3714 (18) | C22—C2 | 1.516 (2) |
O15—C14 | 1.4265 (18) | C22—H8A | 0.9600 |
O20—C6 | 1.2032 (18) | C22—H8B | 0.9600 |
O21—C4 | 1.2022 (18) | C22—H8C | 0.9600 |
O17—C11 | 1.3757 (19) | C7—C8 | 1.518 (2) |
O17—C16 | 1.4231 (19) | C7—H10A | 0.9700 |
O19—C9 | 1.3773 (18) | C7—H10B | 0.9700 |
O19—C18 | 1.4282 (18) | C23—C2 | 1.503 (2) |
C5—C6 | 1.506 (2) | C23—H11A | 0.9600 |
C5—C4 | 1.518 (2) | C23—H11B | 0.9600 |
C5—C7 | 1.528 (2) | C23—H11C | 0.9600 |
C5—H1 | 0.9800 | C18—H12A | 0.9600 |
C14—H2A | 0.9600 | C18—H12B | 0.9600 |
C14—H2B | 0.9600 | C18—H12C | 0.9600 |
C14—H2C | 0.9600 | C8—C13 | 1.398 (2) |
C9—C10 | 1.390 (2) | C16—H15A | 0.9600 |
C9—C8 | 1.400 (2) | C16—H15B | 0.9600 |
C11—C12 | 1.383 (2) | C16—H15C | 0.9600 |
C4—O3—C2 | 120.09 (12) | O21—C4—C5 | 124.94 (15) |
C6—O1—C2 | 120.05 (12) | O3—C4—C5 | 116.29 (13) |
C13—O15—C14 | 117.48 (12) | C8—C7—C5 | 119.70 (13) |
C11—O17—C16 | 116.07 (12) | C8—C7—H10A | 107.4 |
C9—O19—C18 | 118.00 (12) | C5—C7—H10A | 107.4 |
C6—C5—C4 | 112.72 (13) | C8—C7—H10B | 107.4 |
C6—C5—C7 | 113.04 (13) | C5—C7—H10B | 107.4 |
C4—C5—C7 | 114.21 (13) | H10A—C7—H10B | 106.9 |
C6—C5—H1 | 105.3 | C2—C23—H11A | 109.5 |
C4—C5—H1 | 105.3 | C2—C23—H11B | 109.5 |
C7—C5—H1 | 105.3 | H11A—C23—H11B | 109.5 |
O15—C14—H2A | 109.5 | C2—C23—H11C | 109.5 |
O15—C14—H2B | 109.5 | H11A—C23—H11C | 109.5 |
H2A—C14—H2B | 109.5 | H11B—C23—H11C | 109.5 |
O15—C14—H2C | 109.5 | O19—C18—H12A | 109.5 |
H2A—C14—H2C | 109.5 | O19—C18—H12B | 109.5 |
H2B—C14—H2C | 109.5 | H12A—C18—H12B | 109.5 |
O19—C9—C10 | 121.43 (14) | O19—C18—H12C | 109.5 |
O19—C9—C8 | 116.11 (13) | H12A—C18—H12C | 109.5 |
C10—C9—C8 | 122.43 (14) | H12B—C18—H12C | 109.5 |
O17—C11—C12 | 123.12 (14) | O3—C2—O1 | 110.00 (11) |
O17—C11—C10 | 115.50 (14) | O3—C2—C23 | 105.59 (13) |
C12—C11—C10 | 121.38 (14) | O1—C2—C23 | 106.28 (12) |
O20—C6—O1 | 118.91 (14) | O3—C2—C22 | 111.04 (13) |
O20—C6—C5 | 124.44 (14) | O1—C2—C22 | 110.73 (13) |
O1—C6—C5 | 116.64 (13) | C23—C2—C22 | 112.98 (13) |
C11—C12—C13 | 118.34 (15) | C13—C8—C9 | 116.37 (14) |
C11—C12—H6 | 120.8 | C13—C8—C7 | 116.43 (14) |
C13—C12—H6 | 120.8 | C9—C8—C7 | 127.18 (14) |
C11—C10—C9 | 118.72 (15) | O17—C16—H15A | 109.5 |
C11—C10—H7 | 120.6 | O17—C16—H15B | 109.5 |
C9—C10—H7 | 120.6 | H15A—C16—H15B | 109.5 |
C2—C22—H8A | 109.5 | O17—C16—H15C | 109.5 |
C2—C22—H8B | 109.5 | H15A—C16—H15C | 109.5 |
H8A—C22—H8B | 109.5 | H15B—C16—H15C | 109.5 |
C2—C22—H8C | 109.5 | O15—C13—C12 | 122.21 (14) |
H8A—C22—H8C | 109.5 | O15—C13—C8 | 115.04 (13) |
H8B—C22—H8C | 109.5 | C12—C13—C8 | 122.72 (15) |
O21—C4—O3 | 118.76 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
C22—H8C···O20i | 0.96 | 2.58 | 3.425 (2) | 147 |
C16—H15B···O21ii | 0.96 | 2.55 | 3.345 (2) | 140 |
Symmetry codes: (i) −x+3/2, y−1/2, z; (ii) x−1, y, z. |
C15H18O7 | F(000) = 2624 |
Mr = 310.29 | Dx = 1.408 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 22.9942 (5) Å | Cell parameters from 14754 reflections |
b = 10.1840 (2) Å | θ = 1.0–27.5° |
c = 26.9904 (7) Å | µ = 0.11 mm−1 |
β = 112.125 (1)° | T = 190 K |
V = 5855.0 (2) Å3 | Block, colourless |
Z = 16 | 0.32 × 0.14 × 0.10 mm |
Nonius KappaCCD diffractometer | 3333 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.071 |
Graphite monochromator | θmax = 27.5°, θmin = 4.1° |
CCD scans | h = −29→29 |
11293 measured reflections | k = −13→12 |
6610 independent reflections | l = −35→34 |
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)] = 0.056 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.128 | H-atom parameters constrained |
S = 0.96 | w = 1/[σ2(Fo2) + (0.0491P)2] where P = (Fo2 + 2Fc2)/3 |
6610 reflections | (Δ/σ)max < 0.001 |
407 parameters | Δρmax = 0.26 e Å−3 |
1 restraint | Δρmin = −0.28 e Å−3 |
C15H18O7 | V = 5855.0 (2) Å3 |
Mr = 310.29 | Z = 16 |
Monoclinic, C2/c | Mo Kα radiation |
a = 22.9942 (5) Å | µ = 0.11 mm−1 |
b = 10.1840 (2) Å | T = 190 K |
c = 26.9904 (7) Å | 0.32 × 0.14 × 0.10 mm |
β = 112.125 (1)° |
Nonius KappaCCD diffractometer | 3333 reflections with I > 2σ(I) |
11293 measured reflections | Rint = 0.071 |
6610 independent reflections |
R[F2 > 2σ(F2)] = 0.056 | 1 restraint |
wR(F2) = 0.128 | H-atom parameters constrained |
S = 0.96 | Δρmax = 0.26 e Å−3 |
6610 reflections | Δρmin = −0.28 e Å−3 |
407 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
O19A | 0.68746 (7) | 0.22214 (15) | 0.00532 (6) | 0.0288 (4) | |
O3A | 0.75965 (7) | 0.57215 (14) | 0.01900 (6) | 0.0285 (4) | |
O16A | 0.64076 (8) | 0.02557 (15) | 0.22066 (7) | 0.0310 (4) | |
H16A | 0.6485 | 0.0576 | 0.2503 | 0.046* | |
O1B | 0.44928 (7) | −0.16261 (16) | 0.18401 (7) | 0.0315 (4) | |
O16B | 0.65988 (7) | 0.51559 (16) | 0.13938 (7) | 0.0313 (4) | |
H16B | 0.6829 | 0.5362 | 0.1698 | 0.047* | |
O17A | 0.73529 (7) | 0.18461 (15) | 0.27644 (7) | 0.0335 (4) | |
O15B | 0.58398 (7) | 0.40497 (15) | 0.04951 (6) | 0.0313 (4) | |
O3B | 0.47010 (7) | −0.16576 (16) | 0.10492 (6) | 0.0323 (4) | |
O15A | 0.61118 (7) | −0.02194 (15) | 0.11918 (6) | 0.0302 (4) | |
O17B | 0.64798 (8) | 0.47330 (16) | 0.23247 (7) | 0.0347 (4) | |
O1A | 0.67768 (7) | 0.42422 (15) | −0.02468 (6) | 0.0284 (4) | |
O20B | 0.45815 (8) | 0.01801 (16) | 0.05925 (7) | 0.0372 (5) | |
C11A | 0.67329 (10) | 0.0924 (2) | 0.19515 (10) | 0.0231 (6) | |
O19B | 0.42579 (8) | 0.02352 (18) | 0.21338 (7) | 0.0398 (5) | |
C9A | 0.75431 (10) | 0.2423 (2) | 0.19489 (10) | 0.0247 (6) | |
H2 | 0.7864 | 0.3007 | 0.2130 | 0.030* | |
O20A | 0.83454 (8) | 0.51768 (17) | 0.09498 (7) | 0.0448 (5) | |
C8A | 0.73847 (10) | 0.2205 (2) | 0.14057 (10) | 0.0229 (6) | |
C10B | 0.60468 (10) | 0.4106 (2) | 0.18890 (10) | 0.0246 (6) | |
C12A | 0.65821 (10) | 0.0684 (2) | 0.14124 (10) | 0.0222 (6) | |
C6B | 0.44930 (11) | −0.0293 (3) | 0.18611 (10) | 0.0284 (6) | |
C7B | 0.46316 (10) | 0.1855 (2) | 0.14484 (10) | 0.0304 (6) | |
H7A | 0.4273 | 0.1955 | 0.1115 | 0.037* | |
H7B | 0.4506 | 0.2148 | 0.1735 | 0.037* | |
C4B | 0.46868 (10) | −0.0324 (2) | 0.10159 (10) | 0.0271 (6) | |
C7A | 0.77508 (10) | 0.2871 (2) | 0.11156 (10) | 0.0279 (6) | |
H9A | 0.7902 | 0.2201 | 0.0938 | 0.033* | |
H9B | 0.8116 | 0.3287 | 0.1380 | 0.033* | |
C18A | 0.77638 (11) | 0.2876 (2) | 0.30543 (10) | 0.0355 (7) | |
H10A | 0.8174 | 0.2737 | 0.3048 | 0.053* | |
H10B | 0.7790 | 0.2875 | 0.3418 | 0.053* | |
H10C | 0.7603 | 0.3705 | 0.2892 | 0.053* | |
C11B | 0.61265 (10) | 0.4346 (2) | 0.14147 (10) | 0.0250 (6) | |
C13B | 0.52368 (10) | 0.2968 (2) | 0.09572 (10) | 0.0268 (6) | |
H12 | 0.4964 | 0.2583 | 0.0643 | 0.032* | |
C13A | 0.69063 (10) | 0.1314 (2) | 0.11425 (10) | 0.0233 (6) | |
H13 | 0.6805 | 0.1144 | 0.0781 | 0.028* | |
C6A | 0.70026 (10) | 0.3358 (2) | 0.01592 (10) | 0.0236 (6) | |
C10A | 0.72232 (10) | 0.1770 (2) | 0.22221 (9) | 0.0237 (6) | |
C12B | 0.57198 (10) | 0.3768 (2) | 0.09423 (10) | 0.0245 (6) | |
C5A | 0.73943 (10) | 0.3910 (2) | 0.06974 (9) | 0.0223 (6) | |
H17 | 0.7104 | 0.4346 | 0.0833 | 0.027* | |
C9B | 0.55630 (10) | 0.3305 (2) | 0.19025 (10) | 0.0291 (6) | |
H18 | 0.5513 | 0.3152 | 0.2224 | 0.035* | |
C22A | 0.69361 (12) | 0.6065 (2) | −0.07065 (10) | 0.0370 (7) | |
H19A | 0.7044 | 0.6979 | −0.0686 | 0.055* | |
H19B | 0.6521 | 0.5941 | −0.0970 | 0.055* | |
H19C | 0.7231 | 0.5567 | −0.0805 | 0.055* | |
C2B | 0.48196 (11) | −0.2303 (2) | 0.15522 (10) | 0.0288 (6) | |
C14B | 0.54495 (11) | 0.3423 (3) | 0.00071 (10) | 0.0386 (7) | |
H21A | 0.5481 | 0.2487 | 0.0053 | 0.058* | |
H21B | 0.5585 | 0.3672 | −0.0275 | 0.058* | |
H21C | 0.5021 | 0.3690 | −0.0083 | 0.058* | |
C8B | 0.51559 (10) | 0.2736 (2) | 0.14324 (10) | 0.0255 (6) | |
C22B | 0.45127 (12) | −0.3631 (2) | 0.14144 (11) | 0.0409 (7) | |
H23A | 0.4076 | −0.3524 | 0.1198 | 0.061* | |
H23B | 0.4555 | −0.4088 | 0.1737 | 0.061* | |
H23C | 0.4712 | −0.4129 | 0.1220 | 0.061* | |
C21B | 0.55136 (10) | −0.2401 (2) | 0.18788 (11) | 0.0357 (7) | |
H24A | 0.5712 | −0.2906 | 0.1686 | 0.054* | |
H24B | 0.5578 | −0.2823 | 0.2213 | 0.054* | |
H24C | 0.5693 | −0.1537 | 0.1945 | 0.054* | |
C2A | 0.69550 (10) | 0.5607 (2) | −0.01715 (10) | 0.0259 (6) | |
C5B | 0.48038 (10) | 0.0394 (2) | 0.15315 (9) | 0.0230 (6) | |
H26 | 0.5257 | 0.0353 | 0.1737 | 0.028* | |
C4A | 0.78254 (11) | 0.4965 (2) | 0.06355 (10) | 0.0276 (6) | |
C21A | 0.65274 (11) | 0.6377 (2) | 0.00289 (11) | 0.0376 (7) | |
H28A | 0.6565 | 0.6049 | 0.0373 | 0.056* | |
H28B | 0.6101 | 0.6285 | −0.0218 | 0.056* | |
H28C | 0.6644 | 0.7287 | 0.0059 | 0.056* | |
C14A | 0.59698 (12) | −0.0571 (3) | 0.06491 (11) | 0.0434 (7) | |
H29A | 0.5824 | 0.0189 | 0.0426 | 0.065* | |
H29B | 0.5649 | −0.1233 | 0.0544 | 0.065* | |
H29C | 0.6340 | −0.0908 | 0.0610 | 0.065* | |
C18B | 0.64126 (13) | 0.4580 (3) | 0.28239 (11) | 0.0458 (8) | |
H30A | 0.6010 | 0.4906 | 0.2796 | 0.069* | |
H30B | 0.6737 | 0.5063 | 0.3094 | 0.069* | |
H30C | 0.6446 | 0.3667 | 0.2919 | 0.069* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O19A | 0.0338 (10) | 0.0249 (10) | 0.0303 (11) | −0.0059 (8) | 0.0152 (8) | −0.0009 (8) |
O3A | 0.0253 (9) | 0.0283 (9) | 0.0279 (10) | −0.0059 (7) | 0.0055 (8) | 0.0058 (8) |
O16A | 0.0363 (10) | 0.0367 (10) | 0.0249 (10) | −0.0101 (8) | 0.0172 (9) | −0.0030 (8) |
O1B | 0.0302 (9) | 0.0383 (11) | 0.0291 (11) | −0.0053 (8) | 0.0149 (8) | 0.0068 (8) |
O16B | 0.0340 (10) | 0.0326 (10) | 0.0283 (10) | −0.0091 (8) | 0.0127 (8) | −0.0054 (9) |
O17A | 0.0412 (10) | 0.0353 (10) | 0.0233 (10) | −0.0132 (8) | 0.0115 (8) | −0.0067 (8) |
O15B | 0.0323 (9) | 0.0390 (10) | 0.0229 (10) | −0.0101 (8) | 0.0109 (8) | −0.0028 (8) |
O3B | 0.0408 (10) | 0.0340 (11) | 0.0218 (10) | −0.0076 (8) | 0.0113 (8) | −0.0026 (8) |
O15A | 0.0330 (9) | 0.0346 (10) | 0.0226 (10) | −0.0142 (8) | 0.0101 (8) | −0.0043 (8) |
O17B | 0.0403 (10) | 0.0402 (10) | 0.0245 (11) | −0.0089 (8) | 0.0133 (9) | −0.0066 (8) |
O1A | 0.0295 (9) | 0.0235 (9) | 0.0277 (10) | −0.0032 (7) | 0.0056 (8) | 0.0019 (8) |
O20B | 0.0458 (11) | 0.0442 (11) | 0.0221 (11) | −0.0051 (9) | 0.0134 (9) | 0.0038 (9) |
C11A | 0.0231 (13) | 0.0219 (13) | 0.0279 (15) | −0.0012 (10) | 0.0138 (11) | 0.0044 (11) |
O19B | 0.0414 (11) | 0.0568 (12) | 0.0301 (11) | 0.0046 (9) | 0.0234 (9) | 0.0034 (9) |
C9A | 0.0221 (12) | 0.0220 (14) | 0.0279 (16) | −0.0034 (10) | 0.0069 (12) | −0.0010 (11) |
O20A | 0.0315 (10) | 0.0488 (12) | 0.0400 (12) | −0.0185 (9) | −0.0029 (9) | 0.0093 (9) |
C8A | 0.0183 (12) | 0.0232 (13) | 0.0252 (15) | 0.0019 (10) | 0.0060 (11) | 0.0065 (11) |
C10B | 0.0261 (13) | 0.0238 (14) | 0.0232 (15) | 0.0018 (11) | 0.0084 (11) | −0.0057 (12) |
C12A | 0.0218 (12) | 0.0226 (13) | 0.0213 (14) | 0.0016 (10) | 0.0071 (11) | 0.0022 (11) |
C6B | 0.0214 (13) | 0.0446 (18) | 0.0181 (15) | −0.0027 (12) | 0.0062 (11) | 0.0035 (13) |
C7B | 0.0258 (13) | 0.0386 (16) | 0.0304 (16) | 0.0003 (12) | 0.0147 (12) | −0.0010 (13) |
C4B | 0.0241 (13) | 0.0328 (16) | 0.0253 (16) | −0.0036 (11) | 0.0104 (12) | 0.0005 (12) |
C7A | 0.0203 (12) | 0.0324 (14) | 0.0297 (15) | 0.0004 (11) | 0.0080 (11) | 0.0060 (12) |
C18A | 0.0402 (15) | 0.0340 (15) | 0.0276 (16) | −0.0069 (12) | 0.0073 (13) | −0.0088 (12) |
C11B | 0.0229 (13) | 0.0230 (13) | 0.0307 (16) | −0.0006 (11) | 0.0118 (12) | −0.0013 (12) |
C13B | 0.0252 (13) | 0.0271 (14) | 0.0262 (15) | −0.0014 (11) | 0.0077 (11) | −0.0037 (11) |
C13A | 0.0266 (13) | 0.0265 (13) | 0.0192 (14) | 0.0033 (11) | 0.0113 (11) | 0.0028 (11) |
C6A | 0.0193 (12) | 0.0285 (15) | 0.0269 (15) | −0.0009 (11) | 0.0132 (11) | 0.0016 (12) |
C10A | 0.0257 (13) | 0.0254 (14) | 0.0192 (14) | 0.0020 (11) | 0.0075 (11) | 0.0011 (11) |
C12B | 0.0285 (13) | 0.0242 (13) | 0.0215 (14) | 0.0016 (11) | 0.0102 (12) | 0.0011 (11) |
C5A | 0.0224 (12) | 0.0231 (13) | 0.0228 (14) | −0.0020 (10) | 0.0100 (11) | −0.0010 (11) |
C9B | 0.0312 (14) | 0.0315 (15) | 0.0269 (16) | 0.0014 (12) | 0.0134 (12) | 0.0007 (12) |
C22A | 0.0450 (16) | 0.0326 (15) | 0.0311 (17) | −0.0031 (12) | 0.0119 (13) | 0.0061 (13) |
C2B | 0.0289 (13) | 0.0363 (15) | 0.0219 (15) | −0.0051 (12) | 0.0105 (12) | 0.0011 (12) |
C14B | 0.0383 (15) | 0.0497 (18) | 0.0258 (16) | −0.0107 (13) | 0.0097 (13) | −0.0068 (13) |
C8B | 0.0243 (13) | 0.0228 (13) | 0.0307 (16) | 0.0023 (11) | 0.0119 (12) | 0.0008 (11) |
C22B | 0.0399 (16) | 0.0406 (16) | 0.0386 (18) | −0.0147 (13) | 0.0107 (13) | 0.0014 (14) |
C21B | 0.0270 (14) | 0.0346 (15) | 0.0424 (18) | −0.0033 (11) | 0.0096 (13) | −0.0022 (13) |
C2A | 0.0228 (13) | 0.0233 (14) | 0.0290 (15) | −0.0028 (10) | 0.0067 (11) | 0.0029 (11) |
C5B | 0.0174 (12) | 0.0307 (14) | 0.0200 (14) | −0.0026 (10) | 0.0061 (10) | −0.0025 (11) |
C4A | 0.0253 (13) | 0.0299 (15) | 0.0266 (15) | −0.0017 (11) | 0.0087 (12) | 0.0000 (12) |
C21A | 0.0360 (15) | 0.0322 (15) | 0.0452 (19) | 0.0025 (12) | 0.0159 (14) | 0.0006 (13) |
C14A | 0.0422 (16) | 0.0555 (18) | 0.0331 (17) | −0.0186 (14) | 0.0147 (14) | −0.0190 (14) |
C18B | 0.0538 (18) | 0.0559 (19) | 0.0313 (18) | −0.0101 (15) | 0.0202 (15) | −0.0117 (14) |
O19A—C6A | 1.202 (3) | C7A—H9A | 0.9700 |
O3A—C4A | 1.357 (3) | C7A—H9B | 0.9700 |
O3A—C2A | 1.434 (3) | C18A—H10A | 0.9600 |
O16A—C11A | 1.373 (3) | C18A—H10B | 0.9600 |
O16A—H16A | 0.8200 | C18A—H10C | 0.9600 |
O1B—C6B | 1.358 (3) | C11B—C12B | 1.396 (3) |
O1B—C2B | 1.444 (3) | C13B—C8B | 1.384 (3) |
O16B—C11B | 1.382 (3) | C13B—C12B | 1.391 (3) |
O16B—H16B | 0.8200 | C13B—H12 | 0.9300 |
O17A—C10A | 1.382 (3) | C13A—H13 | 0.9300 |
O17A—C18A | 1.431 (3) | C6A—C5A | 1.500 (3) |
O15B—C12B | 1.366 (3) | C5A—C4A | 1.513 (3) |
O15B—C14B | 1.434 (3) | C5A—H17 | 0.9800 |
O3B—C4B | 1.360 (3) | C9B—C8B | 1.388 (3) |
O3B—C2B | 1.439 (3) | C9B—H18 | 0.9300 |
O15A—C12A | 1.373 (3) | C22A—C2A | 1.503 (3) |
O15A—C14A | 1.421 (3) | C22A—H19A | 0.9600 |
O17B—C10B | 1.379 (3) | C22A—H19B | 0.9600 |
O17B—C18B | 1.421 (3) | C22A—H19C | 0.9600 |
O1A—C6A | 1.361 (3) | C2B—C22B | 1.506 (3) |
O1A—C2A | 1.441 (3) | C2B—C21B | 1.508 (3) |
O20B—C4B | 1.192 (3) | C14B—H21A | 0.9600 |
C11A—C12A | 1.385 (3) | C14B—H21B | 0.9600 |
C11A—C10A | 1.388 (3) | C14B—H21C | 0.9600 |
O19B—C6B | 1.193 (3) | C22B—H23A | 0.9600 |
C9A—C8A | 1.389 (3) | C22B—H23B | 0.9600 |
C9A—C10A | 1.391 (3) | C22B—H23C | 0.9600 |
C9A—H2 | 0.9300 | C21B—H24A | 0.9600 |
O20A—C4A | 1.197 (3) | C21B—H24B | 0.9600 |
C8A—C13A | 1.396 (3) | C21B—H24C | 0.9600 |
C8A—C7A | 1.509 (3) | C2A—C21A | 1.508 (3) |
C10B—C11B | 1.382 (3) | C5B—H26 | 0.9800 |
C10B—C9B | 1.391 (3) | C21A—H28A | 0.9600 |
C12A—C13A | 1.381 (3) | C21A—H28B | 0.9600 |
C6B—C5B | 1.507 (3) | C21A—H28C | 0.9600 |
C7B—C8B | 1.516 (3) | C14A—H29A | 0.9600 |
C7B—C5B | 1.534 (3) | C14A—H29B | 0.9600 |
C7B—H7A | 0.9700 | C14A—H29C | 0.9600 |
C7B—H7B | 0.9700 | C18B—H30A | 0.9600 |
C4B—C5B | 1.504 (3) | C18B—H30B | 0.9600 |
C7A—C5A | 1.539 (3) | C18B—H30C | 0.9600 |
C4A—O3A—C2A | 120.85 (17) | C4A—C5A—H17 | 106.7 |
C11A—O16A—H16A | 109.5 | C7A—C5A—H17 | 106.7 |
C6B—O1B—C2B | 120.49 (19) | C8B—C9B—C10B | 119.4 (2) |
C11B—O16B—H16B | 109.5 | C8B—C9B—H18 | 120.3 |
C10A—O17A—C18A | 117.06 (19) | C10B—C9B—H18 | 120.3 |
C12B—O15B—C14B | 116.95 (18) | C2A—C22A—H19A | 109.5 |
C4B—O3B—C2B | 120.63 (19) | C2A—C22A—H19B | 109.5 |
C12A—O15A—C14A | 116.99 (19) | H19A—C22A—H19B | 109.5 |
C10B—O17B—C18B | 117.16 (19) | C2A—C22A—H19C | 109.5 |
C6A—O1A—C2A | 121.48 (18) | H19A—C22A—H19C | 109.5 |
O16A—C11A—C12A | 118.1 (2) | H19B—C22A—H19C | 109.5 |
O16A—C11A—C10A | 122.1 (2) | O3B—C2B—O1B | 109.75 (18) |
C12A—C11A—C10A | 119.6 (2) | O3B—C2B—C22B | 105.82 (19) |
C8A—C9A—C10A | 120.1 (2) | O1B—C2B—C22B | 105.7 (2) |
C8A—C9A—H2 | 119.9 | O3B—C2B—C21B | 111.4 (2) |
C10A—C9A—H2 | 119.9 | O1B—C2B—C21B | 111.6 (2) |
C9A—C8A—C13A | 119.0 (2) | C22B—C2B—C21B | 112.3 (2) |
C9A—C8A—C7A | 120.0 (2) | O15B—C14B—H21A | 109.5 |
C13A—C8A—C7A | 121.0 (2) | O15B—C14B—H21B | 109.5 |
O17B—C10B—C11B | 113.8 (2) | H21A—C14B—H21B | 109.5 |
O17B—C10B—C9B | 125.2 (2) | O15B—C14B—H21C | 109.5 |
C11B—C10B—C9B | 121.0 (2) | H21A—C14B—H21C | 109.5 |
O15A—C12A—C13A | 125.2 (2) | H21B—C14B—H21C | 109.5 |
O15A—C12A—C11A | 114.8 (2) | C13B—C8B—C9B | 119.7 (2) |
C13A—C12A—C11A | 120.1 (2) | C13B—C8B—C7B | 120.9 (2) |
O19B—C6B—O1B | 118.9 (2) | C9B—C8B—C7B | 119.4 (2) |
O19B—C6B—C5B | 125.5 (2) | C2B—C22B—H23A | 109.5 |
O1B—C6B—C5B | 115.6 (2) | C2B—C22B—H23B | 109.5 |
C8B—C7B—C5B | 114.44 (19) | H23A—C22B—H23B | 109.5 |
C8B—C7B—H7A | 108.7 | C2B—C22B—H23C | 109.5 |
C5B—C7B—H7A | 108.7 | H23A—C22B—H23C | 109.5 |
C8B—C7B—H7B | 108.7 | H23B—C22B—H23C | 109.5 |
C5B—C7B—H7B | 108.7 | C2B—C21B—H24A | 109.5 |
H7A—C7B—H7B | 107.6 | C2B—C21B—H24B | 109.5 |
O20B—C4B—O3B | 119.0 (2) | H24A—C21B—H24B | 109.5 |
O20B—C4B—C5B | 125.3 (2) | C2B—C21B—H24C | 109.5 |
O3B—C4B—C5B | 115.6 (2) | H24A—C21B—H24C | 109.5 |
C8A—C7A—C5A | 116.26 (19) | H24B—C21B—H24C | 109.5 |
C8A—C7A—H9A | 108.2 | O3A—C2A—O1A | 109.85 (16) |
C5A—C7A—H9A | 108.2 | O3A—C2A—C22A | 106.17 (19) |
C8A—C7A—H9B | 108.2 | O1A—C2A—C22A | 105.08 (19) |
C5A—C7A—H9B | 108.2 | O3A—C2A—C21A | 110.85 (19) |
H9A—C7A—H9B | 107.4 | O1A—C2A—C21A | 111.27 (19) |
O17A—C18A—H10A | 109.5 | C22A—C2A—C21A | 113.3 (2) |
O17A—C18A—H10B | 109.5 | C4B—C5B—C6B | 111.15 (19) |
H10A—C18A—H10B | 109.5 | C4B—C5B—C7B | 112.9 (2) |
O17A—C18A—H10C | 109.5 | C6B—C5B—C7B | 112.5 (2) |
H10A—C18A—H10C | 109.5 | C4B—C5B—H26 | 106.6 |
H10B—C18A—H10C | 109.5 | C6B—C5B—H26 | 106.6 |
C10B—C11B—O16B | 121.6 (2) | C7B—C5B—H26 | 106.6 |
C10B—C11B—C12B | 119.7 (2) | O20A—C4A—O3A | 118.4 (2) |
O16B—C11B—C12B | 118.7 (2) | O20A—C4A—C5A | 124.8 (2) |
C8B—C13B—C12B | 121.0 (2) | O3A—C4A—C5A | 116.72 (19) |
C8B—C13B—H12 | 119.5 | C2A—C21A—H28A | 109.5 |
C12B—C13B—H12 | 119.5 | C2A—C21A—H28B | 109.5 |
C12A—C13A—C8A | 120.8 (2) | H28A—C21A—H28B | 109.5 |
C12A—C13A—H13 | 119.6 | C2A—C21A—H28C | 109.5 |
C8A—C13A—H13 | 119.6 | H28A—C21A—H28C | 109.5 |
O19A—C6A—O1A | 117.4 (2) | H28B—C21A—H28C | 109.5 |
O19A—C6A—C5A | 126.5 (2) | O15A—C14A—H29A | 109.5 |
O1A—C6A—C5A | 116.1 (2) | O15A—C14A—H29B | 109.5 |
O17A—C10A—C11A | 113.6 (2) | H29A—C14A—H29B | 109.5 |
O17A—C10A—C9A | 126.1 (2) | O15A—C14A—H29C | 109.5 |
C11A—C10A—C9A | 120.3 (2) | H29A—C14A—H29C | 109.5 |
O15B—C12B—C13B | 125.3 (2) | H29B—C14A—H29C | 109.5 |
O15B—C12B—C11B | 115.5 (2) | O17B—C18B—H30A | 109.5 |
C13B—C12B—C11B | 119.2 (2) | O17B—C18B—H30B | 109.5 |
C6A—C5A—C4A | 109.77 (19) | H30A—C18B—H30B | 109.5 |
C6A—C5A—C7A | 114.36 (19) | O17B—C18B—H30C | 109.5 |
C4A—C5A—C7A | 112.26 (18) | H30A—C18B—H30C | 109.5 |
C6A—C5A—H17 | 106.7 | H30B—C18B—H30C | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
O16A—H16A···O17A | 0.82 | 2.26 | 2.674 (2) | 112 |
O16B—H16B···O17B | 0.82 | 2.22 | 2.663 (3) | 114 |
C13B—H12···O20B | 0.93 | 2.59 | 3.191 (3) | 123 |
C13A—H13···O19A | 0.93 | 2.31 | 3.056 (3) | 137 |
O16A—H16A···O19Bi | 0.82 | 2.29 | 2.750 (3) | 116 |
O16B—H16B···O17Aii | 0.82 | 2.42 | 3.132 (2) | 145 |
C5A—H17···O16B | 0.98 | 2.38 | 3.329 (3) | 164 |
C21B—H24C···O16A | 0.96 | 2.38 | 3.310 (3) | 164 |
C5B—H26···O16A | 0.98 | 2.47 | 3.447 (3) | 177 |
Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x+3/2, y+1/2, −z+1/2. |
Experimental details
(I) | (II) | (III) | |
Crystal data | |||
Chemical formula | C17H23NO4 | C16H20O7 | C15H18O7 |
Mr | 305.36 | 324.32 | 310.29 |
Crystal system, space group | Orthorhombic, Pbca | Orthorhombic, Pbca | Monoclinic, C2/c |
Temperature (K) | 190 | 190 | 190 |
a, b, c (Å) | 15.0721 (4), 11.3109 (3), 19.4443 (4) | 9.8128 (2), 10.0235 (2), 30.4669 (6) | 22.9942 (5), 10.1840 (2), 26.9904 (7) |
α, β, γ (°) | 90, 90, 90 | 90, 90, 90 | 90, 112.125 (1), 90 |
V (Å3) | 3314.85 (14) | 2996.68 (10) | 5855.0 (2) |
Z | 8 | 8 | 16 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.09 | 0.11 | 0.11 |
Crystal size (mm) | 0.42 × 0.25 × 0.18 | 0.26 × 0.24 × 0.10 | 0.32 × 0.14 × 0.10 |
Data collection | |||
Diffractometer | Nonius KappaCCD diffractometer | Nonius KappaCCD diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | – | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6647, 3586, 2532 | 6059, 3374, 2421 | 11293, 6610, 3333 |
Rint | 0.036 | 0.040 | 0.071 |
(sin θ/λ)max (Å−1) | 0.639 | 0.648 | 0.650 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.135, 1.05 | 0.042, 0.105, 1.00 | 0.056, 0.128, 0.96 |
No. of reflections | 3586 | 3374 | 6610 |
No. of parameters | 207 | 213 | 407 |
No. of restraints | 0 | 0 | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.42, −0.32 | 0.27, −0.24 | 0.26, −0.28 |
Computer programs: COLLECT (Bruker, 2004), SCALEPACK (Otwinowski & Minor, 1997), DENZO (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012).
(I) | (II) | (III) | (VIII) | |
H—C5—C7—C8 | 172.75 | 28.94/34.45 | 35.25 | |
C5—C7—C8—C9 | 49.11 | 12.67 | 70.70/87.89 | 113.29 |
D—H···A | D—H | H···A | D···A | D—H···A |
Compound (I) | ||||
N16—HN16···O20i | 1.00 (2) | 1.70 (2) | 2.688 (2) | 169 (2) |
C10—H2···O3i | 0.93 | 2.46 | 3.264 (2) | 144 |
C12—H10···O19ii | 0.93 | 2.38 | 3.292 (2) | 168 |
Compound (II) | ||||
C22—H8C···O20iii | 0.96 | 2.58 | 3.425 (2) | 147 |
C16—H15B···O20iv | 0.96 | 2.55 | 3.345 (2) | 140 |
Compound (III) | ||||
O16A—H16A···O17A | 0.82 | 2.26 | 2.674 (2) | 112 |
O16B—H16B···O17B | 0.82 | 2.22 | 2.663 (3) | 114 |
C13B—H12···O20B | 0.93 | 2.59 | 3.191 (3) | 123 |
C13A—H13···O19A | 0.93 | 2.31 | 3.056 (3) | 137 |
O16A—H16A···O19Bv | 0.82 | 2.29 | 2.750 (3) | 116 |
O16B—H16B···O17Avi | 0.82 | 2.42 | 3.132 (2) | 145 |
Symmetry codes: (i) x-1/2, -y+3/2, -z; (ii) -x-1, y-1/2, -z+1/2, (iii) -x+3/2, y-1/2, z; (iv) x-1, y, z, (v) -x+1, y, -z+1/2; (vi) -x+3/2, y+1/2, -z+1/2. |