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Four derivatives of 2,6-bis­(hydroxy­methyl)­phenol, with various para substituents, have been investigated; these are 2,6-bis­(hydroxy­methyl)-4-methyl­phenol, C9H12O3, (I), 2,6-bis­(hydroxy­methyl)-4-methoxy­phenol, C9H12O4, (II), 2,6-bis­(hydroxy­methyl)-4-phenoxy­phenol, C14H14O4, (III), and 2,6-bis­(hydroxy­methyl)-4-[1-(4-methoxy­phenyl)-1-methyl­ethyl]­phenol, C18H22O4, (IV). All four structures display hydrogen-bonding networks resulting in sheets, with possible weak inter-sheet π–π interactions in one case. In all the structures but one, the mol­ecules form centrosymmetric dimeric subunits held together by two hydrogen bonds between the hydroxy­methyl groups and, in two cases, by probable π–π interactions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102013239/gd1213sup1.cif
Contains datablocks I, II, III, IV, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102013239/gd1213Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102013239/gd1213IIsup3.hkl
Contains datablock II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102013239/gd1213IIIsup4.hkl
Contains datablock III

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102013239/gd1213IVsup5.hkl
Contains datablock IV

CCDC references: 195629; 195630; 195631; 195632

Comment top

Para derivatives of 2,6-bis(hydroxymethyl)phenol are intermediates in the synthesis of calixarenes (Gutsche, 1989) and homooxacalixarenes (Masci, 2001). A search of the Cambridge Structural Database (Version 5.22; Allen & Kennard, 1993) gives few structural determinations of such compounds, those reported being for 2,6-bis(hydroxymethyl)-4-isopropylphenol (Oehler et al., 1985), 2,6-bis(hydroxymethyl)-4-phenylphenol (Perrin & Cherared, 1986), 2,4,6-tris(hydroxymethyl)phenol and 3,5,3',5'-tetrahydroxymethyl-4,4'-dihydroxydiphenylmethane (Perrin et al., 1986), and 4-bromo-2,6-bis(hydroxymethyl)phenol (Crisp et al., 2000). These compounds have been shown to crystallize as extensively hydrogen-bonded two- or three-dimensional assemblages. We report herein the crystal structure of four new compounds in this series, i.e (I)–(IV) in the Scheme below.

The molecule of (I), with a 4-methyl substituent, can be viewed as part of 4-methylhexahomotrioxacalix[3]arene (Masci, 2001). The O atom of one of the hydroxymethyl groups (O1) is close to the mean plane of the aromatic ring, at a distance of 0.106 (3) Å. The second hydroxymethyl O atom (O3) is more strongly displaced, by 1.386 (3) Å, on the same side of this plane. The three OH groups of the molecule are involved in hydrogen bonds, as both donors and acceptors, which results in six hydrogen bonds linking each molecule to four neighbours. Sheets are formed parallel to the bc plane, most likely held together by van der Waals interactions. The molecules, with phenol groups alternately up and down, have their aromatic rings roughly perpendicular to the sheets. Inside the sheets, the molecules are tightly associated in dimeric subunits around symmetry centers, by two hydrogen bonds between complementary hydroxymethyl groups and by probabe ππ interactions between the parallel aromatic rings [distance between the centroids = 3.835 (3) Å, interplanar spacing = 3.481 (3) Å and centroid offset = 1.609 (3) Å; rings related by the inversion centre at (1/2, 0, 1/2)]. The shortest interatomic contact [C2···C6i 3.479 (3) Å; symmetry code: (i) 1 - x, -y, 1 - z] is only slightly longer than twice the van der Waals radius of C (1.7 Å), which, together with the other geometric parameters, is indicative of ππ interactions. Such dimers were also present in 2,6-bis(hydroxymethyl)-4-isopropylphenol, 2,4,6-trihydroxymethylphenol (with four hydrogen bonds in this case) and 4-bromo-2,6-bis(hydroxymethyl)phenol. As in some previous cases, no intramolecular hydrogen bonding is present, which has been considered an indication that such bonds cannot be invoked to explain the stability of these compounds (Perrin et al., 1986).

With a 4-methoxy substituent in place of the methyl group, compound (II) presents additional possibilities for hydrogen-bonding interactions. As in (I), one of the hydroxymethyl O atoms (O3) is located near the aromatic mean plane, at a distance of 0.153 (3) Å, whereas the other hydroxymethyl O atom (O1) is more displaced [0.966 (3) Å], on the other side of the plane. The C atom of the methoxy substituent is close to the plane [0.107 (4) Å], on the same side as atom O1. Each molecule is involved in six hydrogen bonds with four neighbours, the phenolic atom O2 being donor only, whereas atoms O1 and O3 are both donors and acceptors. Sheets are formed parallel to the bc plane, as in (I), but there is no dimerization in this case and the molecules are not perpendicular to the sheet plane.

The situation is somewhat different in compound (III), which differs from (II) by the presence of a phenoxy group in place of the methoxy substituent. Atom O3 is close to the mean aromatic plane [0.272 (6) Å], whereas atoms O1 and C9 are more distant, at distances of 1.110 (6) and 1.184 (6) Å, atom O1 being on the same side as O3, and atom C9 on the other side. Six hydrogen bonds link each molecule to four of its neighbours, atoms O1, O2 and O3 being donors as well as acceptors. Atom O4 is not involved in hydrogen bonding, probably due to the bulkiness of the benzene-ring substituent. As in (I), centrosymmetric dimers are formed, which are held together by two complementary hydrogen bonds between hydroxymethyl groups and probable ππ interactions [distance between the centroids = 3.953 (3) Å, interplanar spacing = 3.602 (3) Å and centroid offset = 1.629 (3) Å; rings related by the inversion centre at (0, 1, 1/2)]. This interaction is weaker than in compound (I), as indicated also by the shortest interatomic contact between the two rings [C2···C4ii 3.683 (3) Å; symmetry code: (ii) -x, 2 - y, 1 - z]. Sheets are formed parallel to the bc plane, but the phenolic aromatic rings are nearly parallel to this plane, whereas the benzene rings, roughly perpendicular to the former, with a dihedral angle of 81.9 (1)°, project on either side of the planes. The sheets can thus be viewed as hydrophilic at the centre and hydrophobic at the borders. In addition to van der Waals interactions, some weak ππ interactions are possibly involved to ensure the cohesion between sheets [distance between the centroids = 4.208 (3) Å, interplanar spacing = 4.014 (3) Å, centroid offset = 1.263 (3) Å and shortest interatomic contact C10···C14iii = 3.727 (3) Å; rings related by the inversion centre at (1/2, 1, 1); symmetry code: (iii) 1 - x, 2 - y, 2 - z].

In compound (IV), the para substituent is 1-(4-methoxyphenyl)-1-methylethyl, which results in two aromatic rings bound by a C atom, as in the previously reported compound 3,5,3',5'-tetrahydroxymethyl-4,4'-dihydroxydiphenylmethane (Perrin et al., 1986). Atoms O1, O3 and C12 are located on the same side of the mean plane defined by the phenol ring, at distances of 0.302 (3), 0.828 (3) and 0.821 (3) Å, respectively. In contrast to (I)–(III), compound (IV) presents an intramolecular hydrogen bond, between the phenolic H atom and atom O3. As a result, each molecule is linked to three neighbours by four intermolecular hydrogen bonds only, atoms O1 and O3 being both donors and acceptors. As in (I) and (III), centrosymmetric dimers are formed, but there is no evidence, in this case, of significant ππ interactions due to the large offset between the two rings [distance betweenthe centroids = 4.881 (3) Å, interplanar spacing = 3.584 (3) Å and centroid offset = 3.313 (3) Å; rings related by an inversion centre at (1, 1/2, 0)]. The hydrogen-bonding network in (IV) gives rise to sheets parallel to the ab plane, with the phenol rings roughly perpendicular to it and the methoxyphenyl groups located on each side of the sheets.

Experimental top

Bishydroxymethylation of suitable 4-substituted phenols was carried out in alkaline solution by adapting the literature method of Hanus & Fuchs (1939). Pure samples were obtained by recrystallization from acetone in the case of compounds (I), (II) and (IV), and by recrystallization from chloroform in the case of compound (III).

Refinement top

The hydroxy H atoms were found in the difference Fourier map for all four title compounds and were treated as riding atoms with an isotropic displacement parameter equal to 1.2 times that of the parent atom. All other H atoms were introduced at calculated positions and were refined as riding, with C—H bond lengths of 0.93 (CH), 0.97 (CH2) and 0.96 Å (CH3), and an isotropic displacement parameter 1.2 (CH and CH2) or 1.5 (CH3) times that of the parent atom.

Computing details top

For all compounds, data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997); data reduction: DENZO–SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL (Bruker, 1999) and PLATON (Spek, 2000).

Figures top
[Figure 1] Fig. 1. View of the molecule of (I) with the atom-numbering scheme. H atoms are drawn as small spheres of arbitrary radii. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. View of the packing in (I). H atoms have been omitted for clarity, except for those involved in hydrogen bonding. The hydrogen bonds are shown as dashed lines. [Symmetry codes: (i) x, 0.5 - y, 0.5 + z; (ii) 1 - x, -y, -z; (iii) 1 - x, -y, 1 - z.]
[Figure 3] Fig. 3. View of the molecule of (II) with the atom-numbering scheme. H atoms are drawn as small spheres of arbitrary radii. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 4] Fig. 4. View of the packing in (II). H atoms have been omitted for clarity, except for those involved in hydrogen bonding. The hydrogen bonds are shown as dashed lines. [Symmetry codes: (i) x, 0.5 - y, 0.5 + z; (ii) 2 - x, 1 - y, 1 - z; (iii) 2 - x, -y, 1 - z.]
[Figure 5] Fig. 5. View of the molecule of (III) with the atom-numbering scheme. H atoms are drawn as small spheres of arbitrary radii. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 6] Fig. 6. View of the packing in (III), with the bc plane horizontal. H atoms have been omitted for clarity, except for those involved in hydrogen bonding. The hydrogen bonds are shown as dashed lines. [Symmetry codes: (i) -x, 2 - y, 1 - z; (ii) -x, 2 - y, -z; (iii) x, 2.5 - y, 0.5 + z.]
[Figure 7] Fig. 7. View of the molecule of (IV) with the atom-numbering scheme. H atoms are drawn as small spheres of arbitrary radii. The intramolecular hydrogen bond is represented as a dashed line. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 8] Fig. 8. View of the packing in (IV). H atoms have been omitted for clarity, except for those involved in hydrogen bonding. The hydrogen bonds are shown as dashed lines. [Symmetry codes: (i) 1.5 - x, 0.5 + y, z; (ii) 2 - x, -y, 1 - z.]
(I) 2,6-bis(hydroxymethyl)-4-methylphenol top
Crystal data top
C9H12O3F(000) = 360
Mr = 168.19Dx = 1.382 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4701 reflections
a = 8.4545 (5) Åθ = 3.1–25.7°
b = 12.5846 (8) ŵ = 0.10 mm1
c = 8.4726 (5) ÅT = 100 K
β = 116.269 (3)°Irregular, colourless
V = 808.36 (9) Å30.20 × 0.20 × 0.05 mm
Z = 4
Data collection top
Nonius KappaCCD
diffractometer
1151 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.047
Graphite monochromatorθmax = 25.7°, θmin = 3.1°
ϕ scansh = 1010
4701 measured reflectionsk = 1515
1524 independent reflectionsl = 1010
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.111H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0494P)2 + 0.1964P]
where P = (Fo2 + 2Fc2)/3
1524 reflections(Δ/σ)max < 0.001
110 parametersΔρmax = 0.14 e Å3
0 restraintsΔρmin = 0.25 e Å3
Crystal data top
C9H12O3V = 808.36 (9) Å3
Mr = 168.19Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.4545 (5) ŵ = 0.10 mm1
b = 12.5846 (8) ÅT = 100 K
c = 8.4726 (5) Å0.20 × 0.20 × 0.05 mm
β = 116.269 (3)°
Data collection top
Nonius KappaCCD
diffractometer
1151 reflections with I > 2σ(I)
4701 measured reflectionsRint = 0.047
1524 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0430 restraints
wR(F2) = 0.111H-atom parameters constrained
S = 1.03Δρmax = 0.14 e Å3
1524 reflectionsΔρmin = 0.25 e Å3
110 parameters
Special details top

Experimental. crystal-to-detector distance 28 mm

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. Structure solved by direct methods and subsequent Fourier-difference synthesis. All non-hydrogen atoms were refined with anisotropic displacement parameters. The hydroxyl protons were found on the Fourier-difference map and introduced as riding atoms with an isotropic displacement parameter equal to 1.2 times that of the parent atom. All other H atoms were introduced at calculated positions as riding atoms with an isotropic displacement parameter equal to 1.2 (CH, CH2) or 1.5 (CH3) times that of the parent atom. 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.

A 180° range in ϕ was scanned during data collections, with 2° ϕ steps. The crystal-to-detector distance was fixed at 28 mm.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.22982 (16)0.17630 (10)0.56654 (15)0.0215 (3)
H10.27490.23480.61050.026*
O20.35083 (16)0.11455 (10)0.15260 (16)0.0216 (3)
H20.38080.08440.06660.026*
O30.66096 (17)0.03892 (10)0.14721 (16)0.0243 (3)
H30.69810.07860.25770.029*
C10.4502 (2)0.14288 (13)0.4561 (2)0.0191 (4)
C20.4919 (2)0.11785 (13)0.3180 (2)0.0189 (4)
C30.6659 (2)0.10044 (13)0.3483 (2)0.0206 (4)
C40.7975 (2)0.10758 (14)0.5211 (2)0.0214 (4)
H40.91410.09660.54270.026*
C50.7611 (2)0.13041 (13)0.6622 (2)0.0211 (4)
C60.5848 (2)0.14787 (13)0.6259 (2)0.0202 (4)
H60.55730.16330.71820.024*
C70.2582 (2)0.15875 (14)0.4143 (2)0.0202 (4)
H7A0.21270.21910.33580.024*
H7B0.19200.09650.35270.024*
C80.7118 (3)0.06917 (14)0.2026 (2)0.0230 (4)
H8A0.65240.11640.10310.028*
H8B0.83780.07690.24250.028*
C90.9037 (3)0.13202 (15)0.8491 (2)0.0272 (5)
H9A1.01530.11610.85030.041*
H9B0.87800.07980.91720.041*
H9C0.90870.20120.89900.041*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0244 (7)0.0217 (6)0.0214 (7)0.0005 (5)0.0129 (6)0.0010 (5)
O20.0221 (7)0.0247 (7)0.0172 (7)0.0025 (5)0.0079 (6)0.0012 (5)
O30.0325 (8)0.0215 (6)0.0199 (7)0.0033 (5)0.0125 (6)0.0002 (5)
C10.0211 (10)0.0155 (8)0.0212 (9)0.0003 (7)0.0097 (8)0.0003 (7)
C20.0207 (10)0.0162 (8)0.0179 (9)0.0004 (7)0.0069 (8)0.0002 (7)
C30.0243 (10)0.0174 (8)0.0225 (10)0.0002 (7)0.0125 (8)0.0018 (7)
C40.0192 (10)0.0191 (8)0.0249 (10)0.0004 (7)0.0087 (8)0.0008 (7)
C50.0228 (10)0.0167 (8)0.0227 (10)0.0004 (7)0.0090 (8)0.0016 (7)
C60.0243 (10)0.0173 (8)0.0200 (9)0.0004 (7)0.0107 (8)0.0001 (7)
C70.0222 (10)0.0218 (9)0.0166 (9)0.0002 (7)0.0086 (8)0.0011 (7)
C80.0231 (10)0.0230 (9)0.0254 (10)0.0015 (7)0.0130 (8)0.0009 (8)
C90.0236 (11)0.0313 (10)0.0238 (10)0.0015 (8)0.0079 (9)0.0023 (8)
Geometric parameters (Å, º) top
O1—C71.4297 (19)C4—C51.390 (3)
O1—H10.8369C4—H40.9300
O2—C21.381 (2)C5—C61.399 (3)
O2—H20.9503C5—C91.507 (2)
O3—C81.441 (2)C6—H60.9300
O3—H30.9817C7—H7A0.9700
C1—C61.385 (3)C7—H7B0.9700
C1—C21.400 (3)C8—H8A0.9700
C1—C71.514 (2)C8—H8B0.9700
C2—C31.394 (3)C9—H9A0.9600
C3—C41.396 (3)C9—H9B0.9600
C3—C81.501 (2)C9—H9C0.9600
C7—O1—H1108.2C5—C6—H6119.1
C2—O2—H2112.7O1—C7—C1113.58 (13)
C8—O3—H3104.2O1—C7—H7A108.8
C6—C1—C2118.89 (17)C1—C7—H7A108.8
C6—C1—C7122.69 (15)O1—C7—H7B108.8
C2—C1—C7118.36 (16)C1—C7—H7B108.8
O2—C2—C3123.33 (16)H7A—C7—H7B107.7
O2—C2—C1115.52 (16)O3—C8—C3111.53 (14)
C3—C2—C1121.13 (16)O3—C8—H8A109.3
C2—C3—C4118.02 (17)C3—C8—H8A109.3
C2—C3—C8121.68 (17)O3—C8—H8B109.3
C4—C3—C8120.23 (17)C3—C8—H8B109.3
C5—C4—C3122.57 (17)H8A—C8—H8B108.0
C5—C4—H4118.7C5—C9—H9A109.5
C3—C4—H4118.7C5—C9—H9B109.5
C4—C5—C6117.57 (17)H9A—C9—H9B109.5
C4—C5—C9121.85 (16)C5—C9—H9C109.5
C6—C5—C9120.54 (16)H9A—C9—H9C109.5
C1—C6—C5121.81 (16)H9B—C9—H9C109.5
C1—C6—H6119.1
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O2i0.841.982.8010 (17)166
O2—H2···O3ii0.951.782.6728 (17)155
O3—H3···O1iii0.981.822.7824 (17)167
Symmetry codes: (i) x, y+1/2, z+1/2; (ii) x+1, y, z; (iii) x+1, y, z+1.
(II) 2,6-bis(hydroxymethyl)-4-methoxyphenol top
Crystal data top
C9H12O4F(000) = 392
Mr = 184.19Dx = 1.455 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4917 reflections
a = 4.6556 (5) Åθ = 2.8–25.7°
b = 14.5930 (15) ŵ = 0.12 mm1
c = 12.4616 (9) ÅT = 100 K
β = 96.658 (4)°Irregular, colourless
V = 840.92 (14) Å30.30 × 0.20 × 0.08 mm
Z = 4
Data collection top
Nonius KappaCCD
diffractometer
1185 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.053
Graphite monochromatorθmax = 25.7°, θmin = 2.8°
ϕ scansh = 55
4917 measured reflectionsk = 1717
1528 independent reflectionsl = 1515
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.109H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0457P)2 + 0.2874P]
where P = (Fo2 + 2Fc2)/3
1528 reflections(Δ/σ)max < 0.001
119 parametersΔρmax = 0.17 e Å3
0 restraintsΔρmin = 0.24 e Å3
Crystal data top
C9H12O4V = 840.92 (14) Å3
Mr = 184.19Z = 4
Monoclinic, P21/cMo Kα radiation
a = 4.6556 (5) ŵ = 0.12 mm1
b = 14.5930 (15) ÅT = 100 K
c = 12.4616 (9) Å0.30 × 0.20 × 0.08 mm
β = 96.658 (4)°
Data collection top
Nonius KappaCCD
diffractometer
1185 reflections with I > 2σ(I)
4917 measured reflectionsRint = 0.053
1528 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0420 restraints
wR(F2) = 0.109H-atom parameters constrained
S = 1.04Δρmax = 0.17 e Å3
1528 reflectionsΔρmin = 0.24 e Å3
119 parameters
Special details top

Experimental. crystal-to-detector distance 28 mm

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. Structure solved by direct methods and subsequent Fourier-difference synthesis. All non-hydrogen atoms were refined with anisotropic displacement parameters. The hydroxyl protons were found on the Fourier-difference map and introduced as riding atoms with an isotropic displacement parameter equal to 1.2 times that of the parent atom. All other H atoms were introduced at calculated positions as riding atoms with an isotropic displacement parameter equal to 1.2 (CH, CH2) or 1.5 (CH3) times that of the parent atom. 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.9721 (3)0.46012 (9)0.60068 (10)0.0254 (3)
H11.03600.44190.66810.030*
O21.0713 (3)0.35196 (9)0.40032 (10)0.0240 (3)
H21.03940.41560.42510.029*
O31.1581 (3)0.08398 (9)0.30709 (11)0.0276 (4)
H31.27660.05340.36130.033*
O40.5570 (3)0.07497 (9)0.61347 (10)0.0243 (3)
C10.7737 (4)0.30994 (13)0.54130 (15)0.0212 (4)
C20.9414 (4)0.28799 (13)0.45892 (15)0.0208 (4)
C30.9789 (4)0.19647 (13)0.42988 (14)0.0198 (4)
C40.8456 (4)0.12738 (13)0.48285 (15)0.0208 (4)
H40.86630.06660.46270.025*
C50.6809 (4)0.14876 (13)0.56609 (15)0.0210 (4)
C60.6460 (4)0.23931 (13)0.59494 (15)0.0217 (4)
H60.53640.25330.65060.026*
C70.7160 (4)0.40828 (13)0.56661 (17)0.0253 (4)
H7A0.61510.43700.50290.030*
H7B0.58950.41040.62310.030*
C81.1611 (4)0.17773 (13)0.33988 (15)0.0221 (4)
H8A1.09160.21530.27810.026*
H8B1.35900.19570.36340.026*
C90.4065 (4)0.09498 (14)0.70529 (16)0.0275 (5)
H9A0.53690.12370.76060.041*
H9B0.33440.03910.73270.041*
H9C0.24780.13550.68380.041*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0342 (8)0.0186 (7)0.0234 (7)0.0036 (6)0.0038 (6)0.0008 (5)
O20.0302 (7)0.0169 (7)0.0261 (7)0.0015 (5)0.0082 (6)0.0007 (5)
O30.0390 (8)0.0214 (7)0.0223 (7)0.0073 (6)0.0024 (6)0.0019 (6)
O40.0292 (7)0.0194 (7)0.0258 (7)0.0005 (5)0.0095 (6)0.0012 (5)
C10.0209 (9)0.0200 (10)0.0222 (9)0.0014 (7)0.0004 (8)0.0014 (8)
C20.0192 (9)0.0209 (10)0.0216 (9)0.0014 (7)0.0002 (8)0.0000 (8)
C30.0187 (9)0.0201 (10)0.0201 (9)0.0023 (7)0.0005 (8)0.0005 (7)
C40.0227 (10)0.0172 (9)0.0219 (9)0.0021 (7)0.0000 (8)0.0014 (7)
C50.0203 (9)0.0204 (10)0.0218 (9)0.0005 (7)0.0009 (8)0.0029 (7)
C60.0223 (9)0.0225 (10)0.0204 (9)0.0024 (8)0.0030 (8)0.0005 (8)
C70.0243 (10)0.0218 (10)0.0299 (10)0.0012 (8)0.0039 (9)0.0013 (8)
C80.0249 (10)0.0206 (10)0.0210 (9)0.0026 (8)0.0037 (8)0.0005 (7)
C90.0304 (11)0.0277 (11)0.0260 (10)0.0007 (8)0.0102 (9)0.0024 (8)
Geometric parameters (Å, º) top
O1—C71.434 (2)C3—C81.508 (2)
O1—H10.8983C4—C51.395 (3)
O2—C21.369 (2)C4—H40.9300
O2—H20.9946C5—C61.384 (3)
O3—C81.427 (2)C6—H60.9300
O3—H30.9341C7—H7A0.9700
O4—C51.386 (2)C7—H7B0.9700
O4—C91.439 (2)C8—H8A0.9700
C1—C21.397 (3)C8—H8B0.9700
C1—C61.398 (3)C9—H9A0.9600
C1—C71.500 (3)C9—H9B0.9600
C2—C31.400 (3)C9—H9C0.9600
C3—C41.390 (3)
C7—O1—H1107.1C5—C6—H6119.7
C2—O2—H2112.3C1—C6—H6119.7
C8—O3—H3105.4O1—C7—C1113.83 (15)
C5—O4—C9116.50 (15)O1—C7—H7A108.8
C2—C1—C6119.15 (17)C1—C7—H7A108.8
C2—C1—C7120.17 (17)O1—C7—H7B108.8
C6—C1—C7120.55 (16)C1—C7—H7B108.8
O2—C2—C1123.70 (17)H7A—C7—H7B107.7
O2—C2—C3115.89 (16)O3—C8—C3113.52 (15)
C1—C2—C3120.39 (17)O3—C8—H8A108.9
C4—C3—C2119.55 (17)C3—C8—H8A108.9
C4—C3—C8122.85 (17)O3—C8—H8B108.9
C2—C3—C8117.60 (16)C3—C8—H8B108.9
C3—C4—C5120.34 (17)H8A—C8—H8B107.7
C3—C4—H4119.8O4—C9—H9A109.5
C5—C4—H4119.8O4—C9—H9B109.5
C6—C5—O4124.34 (17)H9A—C9—H9B109.5
C6—C5—C4119.87 (17)O4—C9—H9C109.5
O4—C5—C4115.78 (16)H9A—C9—H9C109.5
C5—C6—C1120.69 (17)H9B—C9—H9C109.5
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O3i0.901.802.6951 (19)175
O2—H2···O1ii0.991.842.7496 (18)150
O3—H3···O4iii0.932.042.7956 (19)137
Symmetry codes: (i) x, y+1/2, z+1/2; (ii) x+2, y+1, z+1; (iii) x+2, y, z+1.
(III) 2,6-bis(hydroxymethyl)-4-phenoxyphenol top
Crystal data top
C14H14O4F(000) = 520
Mr = 246.25Dx = 1.333 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 9055 reflections
a = 11.1451 (11) Åθ = 3.0–25.7°
b = 13.5515 (12) ŵ = 0.10 mm1
c = 8.1935 (9) ÅT = 100 K
β = 97.486 (6)°Platelet, colourless
V = 1226.9 (2) Å30.25 × 0.20 × 0.08 mm
Z = 4
Data collection top
Nonius KappaCCD
diffractometer
1350 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.083
Graphite monochromatorθmax = 25.7°, θmin = 3.0°
ϕ scansh = 1313
9055 measured reflectionsk = 160
2314 independent reflectionsl = 09
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.069H-atom parameters constrained
wR(F2) = 0.171 w = 1/[σ2(Fo2) + (0.0508P)2 + 1.3956P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
2314 reflectionsΔρmax = 0.27 e Å3
164 parametersΔρmin = 0.26 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.016 (3)
Crystal data top
C14H14O4V = 1226.9 (2) Å3
Mr = 246.25Z = 4
Monoclinic, P21/cMo Kα radiation
a = 11.1451 (11) ŵ = 0.10 mm1
b = 13.5515 (12) ÅT = 100 K
c = 8.1935 (9) Å0.25 × 0.20 × 0.08 mm
β = 97.486 (6)°
Data collection top
Nonius KappaCCD
diffractometer
1350 reflections with I > 2σ(I)
9055 measured reflectionsRint = 0.083
2314 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0690 restraints
wR(F2) = 0.171H-atom parameters constrained
S = 1.03Δρmax = 0.27 e Å3
2314 reflectionsΔρmin = 0.26 e Å3
164 parameters
Special details top

Experimental. crystal-to-detector distance 28 mm

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. Structure solved by direct methods and subsequent Fourier-difference synthesis. All non-hydrogen atoms were refined with anisotropic displacement parameters. The H atoms bound to O atoms have been found on the Fourier-difference map and introduced as riding atoms with an isotropic displacement parameter equal to 1.2 times tat of the parent atom. All other hydrogen atoms were introduced at calculated positions as riding atoms with an isotropic displacement parameter equal to 1.2 times that of the parent atom. 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.0185 (2)0.91081 (18)0.0823 (3)0.0296 (6)
H10.05180.88330.15860.035*
O20.0828 (2)1.10527 (16)0.2397 (3)0.0286 (6)
H20.06051.08340.13470.034*
O30.1490 (2)1.19638 (17)0.7209 (3)0.0290 (6)
H30.10811.25760.73640.035*
O40.2683 (2)0.84138 (17)0.7230 (3)0.0298 (6)
C10.1386 (3)0.9358 (3)0.3159 (4)0.0257 (8)
C20.1236 (3)1.0346 (2)0.3543 (4)0.0233 (8)
C30.1542 (3)1.0699 (3)0.5157 (4)0.0249 (8)
C40.2024 (3)1.0048 (3)0.6364 (4)0.0257 (8)
H40.22401.02700.74360.031*
C50.2188 (3)0.9064 (3)0.5987 (4)0.0266 (8)
C60.1865 (3)0.8715 (3)0.4418 (4)0.0268 (8)
H60.19640.80500.41900.032*
C70.1076 (3)0.8986 (3)0.1424 (4)0.0292 (9)
H7A0.15560.93390.07090.035*
H7B0.12840.82920.13870.035*
C80.1385 (3)1.1774 (3)0.5484 (4)0.0286 (9)
H8A0.19951.21480.50070.034*
H8B0.05961.19880.49650.034*
C90.3891 (3)0.8594 (3)0.7865 (4)0.0266 (9)
C100.4704 (3)0.9005 (3)0.6931 (5)0.0339 (9)
H100.44590.91850.58440.041*
C110.5888 (4)0.9146 (3)0.7625 (5)0.0417 (11)
H110.64340.94390.70080.050*
C120.6273 (4)0.8857 (3)0.9235 (5)0.0401 (11)
H120.70760.89410.96850.048*
C130.5459 (4)0.8446 (3)1.0152 (5)0.0426 (11)
H130.57120.82531.12310.051*
C140.4249 (3)0.8313 (3)0.9479 (5)0.0359 (10)
H140.36950.80401.01060.043*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0282 (15)0.0342 (14)0.0251 (13)0.0040 (11)0.0012 (11)0.0045 (11)
O20.0371 (16)0.0270 (14)0.0194 (12)0.0013 (11)0.0045 (11)0.0028 (11)
O30.0412 (16)0.0254 (13)0.0200 (13)0.0020 (11)0.0025 (11)0.0026 (11)
O40.0242 (14)0.0293 (14)0.0330 (14)0.0001 (11)0.0069 (11)0.0077 (11)
C10.023 (2)0.031 (2)0.0234 (18)0.0039 (15)0.0016 (15)0.0021 (16)
C20.021 (2)0.0243 (18)0.0236 (19)0.0023 (14)0.0004 (15)0.0038 (16)
C30.025 (2)0.0260 (19)0.0240 (19)0.0033 (15)0.0032 (15)0.0024 (15)
C40.027 (2)0.0273 (19)0.0218 (19)0.0029 (15)0.0001 (15)0.0020 (16)
C50.0221 (19)0.0279 (19)0.0276 (19)0.0034 (15)0.0052 (15)0.0040 (17)
C60.024 (2)0.0250 (19)0.030 (2)0.0012 (15)0.0009 (16)0.0022 (16)
C70.030 (2)0.029 (2)0.028 (2)0.0019 (16)0.0029 (17)0.0025 (17)
C80.037 (2)0.029 (2)0.0189 (18)0.0011 (16)0.0003 (16)0.0008 (16)
C90.021 (2)0.0264 (19)0.031 (2)0.0021 (15)0.0019 (16)0.0002 (16)
C100.026 (2)0.038 (2)0.035 (2)0.0012 (17)0.0009 (17)0.0007 (18)
C110.028 (2)0.051 (3)0.047 (3)0.0023 (19)0.007 (2)0.003 (2)
C120.026 (2)0.041 (2)0.050 (3)0.0033 (18)0.0068 (19)0.007 (2)
C130.041 (3)0.043 (2)0.040 (2)0.002 (2)0.010 (2)0.004 (2)
C140.031 (2)0.037 (2)0.037 (2)0.0056 (17)0.0068 (18)0.0064 (19)
Geometric parameters (Å, º) top
O1—C71.437 (4)C6—H60.9300
O1—H10.8528C7—H7A0.9700
O2—C21.375 (4)C7—H7B0.9700
O2—H20.9139C8—H8A0.9700
O3—C81.427 (4)C8—H8B0.9700
O3—H30.9632C9—C101.378 (5)
O4—C91.400 (4)C9—C141.384 (5)
O4—C51.404 (4)C10—C111.380 (5)
C1—C21.391 (5)C10—H100.9300
C1—C61.402 (5)C11—C121.389 (5)
C1—C71.506 (5)C11—H110.9300
C2—C31.405 (5)C12—C131.370 (6)
C3—C41.381 (5)C12—H120.9300
C3—C81.496 (5)C13—C141.401 (5)
C4—C51.385 (5)C13—H130.9300
C4—H40.9300C14—H140.9300
C5—C61.373 (5)
C7—O1—H1101.4C1—C7—H7B109.1
C2—O2—H2116.2H7A—C7—H7B107.9
C8—O3—H3107.9O3—C8—C3110.9 (3)
C9—O4—C5115.3 (3)O3—C8—H8A109.5
C2—C1—C6118.6 (3)C3—C8—H8A109.5
C2—C1—C7121.1 (3)O3—C8—H8B109.5
C6—C1—C7120.3 (3)C3—C8—H8B109.5
O2—C2—C1123.7 (3)H8A—C8—H8B108.0
O2—C2—C3115.1 (3)C10—C9—C14120.9 (3)
C1—C2—C3121.2 (3)C10—C9—O4122.3 (3)
C4—C3—C2118.8 (3)C14—C9—O4116.8 (3)
C4—C3—C8122.5 (3)C9—C10—C11119.4 (4)
C2—C3—C8118.6 (3)C9—C10—H10120.3
C3—C4—C5120.3 (3)C11—C10—H10120.3
C3—C4—H4119.8C10—C11—C12120.8 (4)
C5—C4—H4119.8C10—C11—H11119.6
C6—C5—C4121.0 (3)C12—C11—H11119.6
C6—C5—O4119.5 (3)C13—C12—C11119.4 (4)
C4—C5—O4119.5 (3)C13—C12—H12120.3
C5—C6—C1120.2 (3)C11—C12—H12120.3
C5—C6—H6119.9C12—C13—C14120.6 (4)
C1—C6—H6119.9C12—C13—H13119.7
O1—C7—C1112.3 (3)C14—C13—H13119.7
O1—C7—H7A109.1C9—C14—C13118.9 (4)
C1—C7—H7A109.1C9—C14—H14120.5
O1—C7—H7B109.2C13—C14—H14120.5
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O3i0.851.902.727 (3)164
O2—H2···O1ii0.911.782.651 (3)158
O3—H3···O2iii0.961.882.797 (3)158
Symmetry codes: (i) x, y+2, z+1; (ii) x, y+2, z; (iii) x, y+5/2, z+1/2.
(IV) 2,6-bis(hydroxymethyl)-4-[1-(4-methoxyphenyl)-1-methylethyl]phenol top
Crystal data top
C18H22O4F(000) = 1296
Mr = 302.36Dx = 1.343 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 16226 reflections
a = 7.0604 (4) Åθ = 2.6–25.7°
b = 16.4995 (11) ŵ = 0.09 mm1
c = 25.6678 (17) ÅT = 100 K
V = 2990.1 (3) Å3Irregular, colourless
Z = 80.35 × 0.20 × 0.08 mm
Data collection top
Nonius KappaCCD
diffractometer
2188 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.064
Graphite monochromatorθmax = 25.7°, θmin = 2.6°
ϕ scansh = 88
16226 measured reflectionsk = 2020
2824 independent reflectionsl = 3131
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.119H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0611P)2 + 0.9384P]
where P = (Fo2 + 2Fc2)/3
2824 reflections(Δ/σ)max < 0.001
202 parametersΔρmax = 0.25 e Å3
0 restraintsΔρmin = 0.25 e Å3
Crystal data top
C18H22O4V = 2990.1 (3) Å3
Mr = 302.36Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 7.0604 (4) ŵ = 0.09 mm1
b = 16.4995 (11) ÅT = 100 K
c = 25.6678 (17) Å0.35 × 0.20 × 0.08 mm
Data collection top
Nonius KappaCCD
diffractometer
2188 reflections with I > 2σ(I)
16226 measured reflectionsRint = 0.064
2824 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0450 restraints
wR(F2) = 0.119H-atom parameters constrained
S = 1.04Δρmax = 0.25 e Å3
2824 reflectionsΔρmin = 0.25 e Å3
202 parameters
Special details top

Experimental. crystal-to-detector distance 28 mm

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. Structure solved by direct methods and subsequent Fourier-difference synthesis. All non-hydrogen atoms were refined with anisotropic displacement parameters. The protons bound to O atoms were found on the difference Fourier map and introduced as riding atoms with a displacement parameter equal to 1.2 times that of the parent atom. All other H atoms were introduced at calculated positions as riding atoms with an isotropic displacement parameter equal to 1.2 (CH, CH2) or 1.5 (CH3) times that of the parent atom. 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.74357 (17)0.14395 (7)0.46826 (5)0.0220 (3)
H10.62780.16150.48260.026*
O20.77232 (17)0.10769 (7)0.46688 (5)0.0234 (3)
H20.81810.15920.47140.028*
O30.93433 (18)0.23197 (7)0.52217 (5)0.0245 (3)
H31.05790.20400.52950.029*
O41.12084 (17)0.34651 (7)0.68990 (5)0.0256 (3)
C10.7401 (2)0.01371 (10)0.51532 (6)0.0191 (4)
C20.7632 (2)0.07076 (10)0.51498 (6)0.0193 (4)
C30.7756 (2)0.11425 (10)0.56131 (7)0.0188 (4)
C40.7599 (2)0.07237 (10)0.60860 (6)0.0197 (4)
H40.76980.10110.63960.024*
C50.7300 (2)0.01072 (10)0.61056 (6)0.0195 (4)
C60.7220 (2)0.05245 (10)0.56288 (7)0.0198 (4)
H60.70380.10830.56330.024*
C70.7341 (2)0.05734 (10)0.46371 (7)0.0204 (4)
H7A0.83930.03890.44250.024*
H7B0.61790.04290.44580.024*
C80.8006 (3)0.20532 (10)0.56110 (7)0.0220 (4)
H8A0.84390.22270.59520.026*
H8B0.67900.23080.55460.026*
C90.6871 (2)0.05623 (10)0.66146 (6)0.0209 (4)
C100.4733 (2)0.07601 (11)0.65992 (7)0.0258 (4)
H10A0.43650.10090.69220.039*
H10B0.40260.02690.65500.039*
H10C0.44810.11250.63160.039*
C110.7253 (3)0.00394 (11)0.71011 (7)0.0241 (4)
H11A0.85570.01250.71040.036*
H11B0.64560.04320.70930.036*
H11C0.69840.03500.74090.036*
C120.8054 (2)0.13376 (10)0.66671 (7)0.0209 (4)
C130.9807 (3)0.14340 (10)0.64250 (7)0.0228 (4)
H131.02650.10180.62150.027*
C141.0898 (3)0.21319 (10)0.64861 (7)0.0236 (4)
H141.20510.21820.63140.028*
C151.0253 (3)0.27532 (10)0.68061 (7)0.0219 (4)
C160.8525 (3)0.26638 (10)0.70612 (7)0.0238 (4)
H160.80880.30740.72790.029*
C170.7454 (3)0.19701 (10)0.69939 (7)0.0221 (4)
H170.63080.19210.71700.027*
C181.3019 (3)0.35616 (11)0.66596 (8)0.0288 (4)
H18A1.38650.31500.67860.043*
H18B1.35190.40870.67440.043*
H18C1.28910.35130.62890.043*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0243 (6)0.0182 (6)0.0234 (7)0.0003 (5)0.0028 (5)0.0008 (5)
O20.0315 (7)0.0202 (6)0.0186 (6)0.0010 (5)0.0004 (5)0.0035 (5)
O30.0243 (7)0.0212 (6)0.0280 (7)0.0000 (5)0.0030 (5)0.0056 (5)
O40.0256 (7)0.0211 (6)0.0301 (7)0.0020 (5)0.0013 (5)0.0033 (5)
C10.0164 (8)0.0218 (8)0.0190 (9)0.0017 (7)0.0001 (6)0.0002 (7)
C20.0172 (8)0.0223 (9)0.0183 (9)0.0016 (7)0.0006 (6)0.0030 (7)
C30.0164 (8)0.0194 (8)0.0206 (9)0.0005 (7)0.0000 (7)0.0002 (7)
C40.0184 (8)0.0226 (9)0.0179 (9)0.0006 (7)0.0002 (7)0.0008 (7)
C50.0175 (8)0.0218 (9)0.0194 (9)0.0002 (7)0.0000 (6)0.0013 (7)
C60.0204 (9)0.0175 (8)0.0215 (9)0.0000 (7)0.0005 (7)0.0004 (7)
C70.0214 (9)0.0188 (8)0.0210 (9)0.0005 (7)0.0001 (7)0.0014 (7)
C80.0245 (9)0.0196 (9)0.0218 (9)0.0014 (7)0.0019 (7)0.0012 (7)
C90.0231 (9)0.0212 (9)0.0182 (9)0.0021 (7)0.0016 (7)0.0006 (7)
C100.0235 (9)0.0291 (10)0.0249 (10)0.0012 (8)0.0016 (7)0.0042 (7)
C110.0304 (10)0.0226 (9)0.0193 (9)0.0021 (8)0.0005 (7)0.0011 (7)
C120.0246 (9)0.0218 (9)0.0163 (8)0.0013 (7)0.0027 (7)0.0000 (7)
C130.0248 (9)0.0213 (9)0.0223 (9)0.0034 (8)0.0001 (7)0.0033 (7)
C140.0219 (9)0.0254 (9)0.0235 (9)0.0016 (8)0.0011 (7)0.0004 (7)
C150.0268 (9)0.0188 (8)0.0200 (9)0.0010 (7)0.0052 (7)0.0001 (7)
C160.0300 (10)0.0215 (9)0.0199 (9)0.0039 (8)0.0010 (7)0.0014 (7)
C170.0251 (9)0.0213 (9)0.0199 (9)0.0024 (7)0.0030 (7)0.0002 (7)
C180.0300 (10)0.0286 (10)0.0278 (10)0.0065 (8)0.0016 (8)0.0009 (8)
Geometric parameters (Å, º) top
O1—C71.4353 (19)C9—C121.534 (2)
O1—H10.9420C9—C111.541 (2)
O2—C21.378 (2)C9—C101.545 (2)
O2—H20.9166C10—H10A0.9600
O3—C81.444 (2)C10—H10B0.9600
O3—H31.0049C10—H10C0.9600
O4—C151.375 (2)C11—H11A0.9600
O4—C181.427 (2)C11—H11B0.9600
C1—C61.384 (2)C11—H11C0.9600
C1—C21.403 (2)C12—C131.394 (3)
C1—C71.508 (2)C12—C171.404 (2)
C2—C31.392 (2)C13—C141.394 (2)
C3—C41.401 (2)C13—H130.9300
C3—C81.513 (2)C14—C151.390 (2)
C4—C51.388 (2)C14—H140.9300
C4—H40.9300C15—C161.393 (3)
C5—C61.405 (2)C16—C171.383 (2)
C5—C91.537 (2)C16—H160.9300
C6—H60.9300C17—H170.9300
C7—H7A0.9700C18—H18A0.9600
C7—H7B0.9700C18—H18B0.9600
C8—H8A0.9700C18—H18C0.9600
C8—H8B0.9700
C7—O1—H1107.3C5—C9—C10105.91 (14)
C2—O2—H2108.3C11—C9—C10108.07 (14)
C8—O3—H3107.4C9—C10—H10A109.5
C15—O4—C18117.38 (14)C9—C10—H10B109.5
C6—C1—C2118.36 (15)H10A—C10—H10B109.5
C6—C1—C7123.48 (15)C9—C10—H10C109.5
C2—C1—C7118.16 (14)H10A—C10—H10C109.5
O2—C2—C3122.32 (15)H10B—C10—H10C109.5
O2—C2—C1116.74 (14)C9—C11—H11A109.5
C3—C2—C1120.94 (15)C9—C11—H11B109.5
C2—C3—C4118.76 (15)H11A—C11—H11B109.5
C2—C3—C8121.09 (15)C9—C11—H11C109.5
C4—C3—C8120.13 (15)H11A—C11—H11C109.5
C5—C4—C3122.04 (16)H11B—C11—H11C109.5
C5—C4—H4119.0C13—C12—C17116.69 (16)
C3—C4—H4119.0C13—C12—C9122.66 (15)
C4—C5—C6117.28 (15)C17—C12—C9120.53 (16)
C4—C5—C9122.91 (15)C12—C13—C14122.31 (16)
C6—C5—C9119.54 (15)C12—C13—H13118.8
C1—C6—C5122.56 (16)C14—C13—H13118.8
C1—C6—H6118.7C15—C14—C13119.64 (17)
C5—C6—H6118.7C15—C14—H14120.2
O1—C7—C1113.73 (14)C13—C14—H14120.2
O1—C7—H7A108.8O4—C15—C14124.87 (16)
C1—C7—H7A108.8O4—C15—C16116.01 (15)
O1—C7—H7B108.8C14—C15—C16119.12 (16)
C1—C7—H7B108.8C17—C16—C15120.53 (16)
H7A—C7—H7B107.7C17—C16—H16119.7
O3—C8—C3112.40 (14)C15—C16—H16119.7
O3—C8—H8A109.1C16—C17—C12121.67 (17)
C3—C8—H8A109.1C16—C17—H17119.2
O3—C8—H8B109.1C12—C17—H17119.2
C3—C8—H8B109.1O4—C18—H18A109.5
H8A—C8—H8B107.9O4—C18—H18B109.5
C12—C9—C5112.01 (14)H18A—C18—H18B109.5
C12—C9—C11107.47 (14)O4—C18—H18C109.5
C5—C9—C11112.37 (14)H18A—C18—H18C109.5
C12—C9—C10110.99 (14)H18B—C18—H18C109.5
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O3i0.942.082.7720 (16)129
O2—H2···O30.921.952.7436 (17)143
O3—H3···O1ii1.001.722.7095 (17)169
Symmetry codes: (i) x+3/2, y+1/2, z; (ii) x+2, y, z+1.

Experimental details

(I)(II)(III)(IV)
Crystal data
Chemical formulaC9H12O3C9H12O4C14H14O4C18H22O4
Mr168.19184.19246.25302.36
Crystal system, space groupMonoclinic, P21/cMonoclinic, P21/cMonoclinic, P21/cOrthorhombic, Pbca
Temperature (K)100100100100
a, b, c (Å)8.4545 (5), 12.5846 (8), 8.4726 (5)4.6556 (5), 14.5930 (15), 12.4616 (9)11.1451 (11), 13.5515 (12), 8.1935 (9)7.0604 (4), 16.4995 (11), 25.6678 (17)
α, β, γ (°)90, 116.269 (3), 9090, 96.658 (4), 9090, 97.486 (6), 9090, 90, 90
V3)808.36 (9)840.92 (14)1226.9 (2)2990.1 (3)
Z4448
Radiation typeMo KαMo KαMo KαMo Kα
µ (mm1)0.100.120.100.09
Crystal size (mm)0.20 × 0.20 × 0.050.30 × 0.20 × 0.080.25 × 0.20 × 0.080.35 × 0.20 × 0.08
Data collection
DiffractometerNonius KappaCCD
diffractometer
Nonius KappaCCD
diffractometer
Nonius KappaCCD
diffractometer
Nonius KappaCCD
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
4701, 1524, 1151 4917, 1528, 1185 9055, 2314, 1350 16226, 2824, 2188
Rint0.0470.0530.0830.064
(sin θ/λ)max1)0.6100.6090.6100.609
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.111, 1.03 0.042, 0.109, 1.04 0.069, 0.171, 1.03 0.045, 0.119, 1.04
No. of reflections1524152823142824
No. of parameters110119164202
H-atom treatmentH-atom parameters constrainedH-atom parameters constrainedH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.14, 0.250.17, 0.240.27, 0.260.25, 0.25

Computer programs: KappaCCD Server Software (Nonius, 1997), DENZO–SMN (Otwinowski & Minor, 1997), DENZO–SMN, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1999) and PLATON (Spek, 2000).

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O2i0.841.982.8010 (17)165.6
O2—H2···O3ii0.951.782.6728 (17)155.3
O3—H3···O1iii0.981.822.7824 (17)167.4
Symmetry codes: (i) x, y+1/2, z+1/2; (ii) x+1, y, z; (iii) x+1, y, z+1.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O3i0.901.802.6951 (19)174.7
O2—H2···O1ii0.991.842.7496 (18)150.1
O3—H3···O4iii0.932.042.7956 (19)137.1
Symmetry codes: (i) x, y+1/2, z+1/2; (ii) x+2, y+1, z+1; (iii) x+2, y, z+1.
Hydrogen-bond geometry (Å, º) for (III) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O3i0.851.902.727 (3)164.4
O2—H2···O1ii0.911.782.651 (3)158.4
O3—H3···O2iii0.961.882.797 (3)158.1
Symmetry codes: (i) x, y+2, z+1; (ii) x, y+2, z; (iii) x, y+5/2, z+1/2.
Hydrogen-bond geometry (Å, º) for (IV) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O3i0.942.082.7720 (16)129
O2—H2···O30.921.952.7436 (17)143
O3—H3···O1ii1.001.722.7095 (17)169
Symmetry codes: (i) x+3/2, y+1/2, z; (ii) x+2, y, z+1.
 

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