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
CCDC references: 195629; 195630; 195631; 195632
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).
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.
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).
(I) 2,6-bis(hydroxymethyl)-4-methylphenol
top
Crystal data top
C9H12O3 | F(000) = 360 |
Mr = 168.19 | Dx = 1.382 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4701 reflections |
a = 8.4545 (5) Å | θ = 3.1–25.7° |
b = 12.5846 (8) Å | µ = 0.10 mm−1 |
c = 8.4726 (5) Å | T = 100 K |
β = 116.269 (3)° | Irregular, colourless |
V = 808.36 (9) Å3 | 0.20 × 0.20 × 0.05 mm |
Z = 4 | |
Data collection top
Nonius KappaCCD diffractometer | 1151 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.047 |
Graphite monochromator | θmax = 25.7°, θmin = 3.1° |
ϕ scans | h = −10→10 |
4701 measured reflections | k = −15→15 |
1524 independent reflections | l = −10→10 |
Refinement top
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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.111 | H-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 parameters | Δρmax = 0.14 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
Crystal data top
C9H12O3 | V = 808.36 (9) Å3 |
Mr = 168.19 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.4545 (5) Å | µ = 0.10 mm−1 |
b = 12.5846 (8) Å | T = 100 K |
c = 8.4726 (5) Å | 0.20 × 0.20 × 0.05 mm |
β = 116.269 (3)° | |
Data collection top
Nonius KappaCCD diffractometer | 1151 reflections with I > 2σ(I) |
4701 measured reflections | Rint = 0.047 |
1524 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.111 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.14 e Å−3 |
1524 reflections | Δρmin = −0.25 e Å−3 |
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 | x | y | z | Uiso*/Ueq | |
O1 | 0.22982 (16) | 0.17630 (10) | 0.56654 (15) | 0.0215 (3) | |
H1 | 0.2749 | 0.2348 | 0.6105 | 0.026* | |
O2 | 0.35083 (16) | 0.11455 (10) | 0.15260 (16) | 0.0216 (3) | |
H2 | 0.3808 | 0.0844 | 0.0666 | 0.026* | |
O3 | 0.66096 (17) | −0.03892 (10) | 0.14721 (16) | 0.0243 (3) | |
H3 | 0.6981 | −0.0786 | 0.2577 | 0.029* | |
C1 | 0.4502 (2) | 0.14288 (13) | 0.4561 (2) | 0.0191 (4) | |
C2 | 0.4919 (2) | 0.11785 (13) | 0.3180 (2) | 0.0189 (4) | |
C3 | 0.6659 (2) | 0.10044 (13) | 0.3483 (2) | 0.0206 (4) | |
C4 | 0.7975 (2) | 0.10758 (14) | 0.5211 (2) | 0.0214 (4) | |
H4 | 0.9141 | 0.0966 | 0.5427 | 0.026* | |
C5 | 0.7611 (2) | 0.13041 (13) | 0.6622 (2) | 0.0211 (4) | |
C6 | 0.5848 (2) | 0.14787 (13) | 0.6259 (2) | 0.0202 (4) | |
H6 | 0.5573 | 0.1633 | 0.7182 | 0.024* | |
C7 | 0.2582 (2) | 0.15875 (14) | 0.4143 (2) | 0.0202 (4) | |
H7A | 0.2127 | 0.2191 | 0.3358 | 0.024* | |
H7B | 0.1920 | 0.0965 | 0.3527 | 0.024* | |
C8 | 0.7118 (3) | 0.06917 (14) | 0.2026 (2) | 0.0230 (4) | |
H8A | 0.6524 | 0.1164 | 0.1031 | 0.028* | |
H8B | 0.8378 | 0.0769 | 0.2425 | 0.028* | |
C9 | 0.9037 (3) | 0.13202 (15) | 0.8491 (2) | 0.0272 (5) | |
H9A | 1.0153 | 0.1161 | 0.8503 | 0.041* | |
H9B | 0.8780 | 0.0798 | 0.9172 | 0.041* | |
H9C | 0.9087 | 0.2012 | 0.8990 | 0.041* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0244 (7) | 0.0217 (6) | 0.0214 (7) | −0.0005 (5) | 0.0129 (6) | −0.0010 (5) |
O2 | 0.0221 (7) | 0.0247 (7) | 0.0172 (7) | 0.0025 (5) | 0.0079 (6) | −0.0012 (5) |
O3 | 0.0325 (8) | 0.0215 (6) | 0.0199 (7) | 0.0033 (5) | 0.0125 (6) | −0.0002 (5) |
C1 | 0.0211 (10) | 0.0155 (8) | 0.0212 (9) | −0.0003 (7) | 0.0097 (8) | 0.0003 (7) |
C2 | 0.0207 (10) | 0.0162 (8) | 0.0179 (9) | −0.0004 (7) | 0.0069 (8) | 0.0002 (7) |
C3 | 0.0243 (10) | 0.0174 (8) | 0.0225 (10) | 0.0002 (7) | 0.0125 (8) | 0.0018 (7) |
C4 | 0.0192 (10) | 0.0191 (8) | 0.0249 (10) | 0.0004 (7) | 0.0087 (8) | 0.0008 (7) |
C5 | 0.0228 (10) | 0.0167 (8) | 0.0227 (10) | 0.0004 (7) | 0.0090 (8) | 0.0016 (7) |
C6 | 0.0243 (10) | 0.0173 (8) | 0.0200 (9) | 0.0004 (7) | 0.0107 (8) | 0.0001 (7) |
C7 | 0.0222 (10) | 0.0218 (9) | 0.0166 (9) | 0.0002 (7) | 0.0086 (8) | −0.0011 (7) |
C8 | 0.0231 (10) | 0.0230 (9) | 0.0254 (10) | 0.0015 (7) | 0.0130 (8) | 0.0009 (8) |
C9 | 0.0236 (11) | 0.0313 (10) | 0.0238 (10) | 0.0015 (8) | 0.0079 (9) | −0.0023 (8) |
Geometric parameters (Å, º) top
O1—C7 | 1.4297 (19) | C4—C5 | 1.390 (3) |
O1—H1 | 0.8369 | C4—H4 | 0.9300 |
O2—C2 | 1.381 (2) | C5—C6 | 1.399 (3) |
O2—H2 | 0.9503 | C5—C9 | 1.507 (2) |
O3—C8 | 1.441 (2) | C6—H6 | 0.9300 |
O3—H3 | 0.9817 | C7—H7A | 0.9700 |
C1—C6 | 1.385 (3) | C7—H7B | 0.9700 |
C1—C2 | 1.400 (3) | C8—H8A | 0.9700 |
C1—C7 | 1.514 (2) | C8—H8B | 0.9700 |
C2—C3 | 1.394 (3) | C9—H9A | 0.9600 |
C3—C4 | 1.396 (3) | C9—H9B | 0.9600 |
C3—C8 | 1.501 (2) | C9—H9C | 0.9600 |
| | | |
C7—O1—H1 | 108.2 | C5—C6—H6 | 119.1 |
C2—O2—H2 | 112.7 | O1—C7—C1 | 113.58 (13) |
C8—O3—H3 | 104.2 | O1—C7—H7A | 108.8 |
C6—C1—C2 | 118.89 (17) | C1—C7—H7A | 108.8 |
C6—C1—C7 | 122.69 (15) | O1—C7—H7B | 108.8 |
C2—C1—C7 | 118.36 (16) | C1—C7—H7B | 108.8 |
O2—C2—C3 | 123.33 (16) | H7A—C7—H7B | 107.7 |
O2—C2—C1 | 115.52 (16) | O3—C8—C3 | 111.53 (14) |
C3—C2—C1 | 121.13 (16) | O3—C8—H8A | 109.3 |
C2—C3—C4 | 118.02 (17) | C3—C8—H8A | 109.3 |
C2—C3—C8 | 121.68 (17) | O3—C8—H8B | 109.3 |
C4—C3—C8 | 120.23 (17) | C3—C8—H8B | 109.3 |
C5—C4—C3 | 122.57 (17) | H8A—C8—H8B | 108.0 |
C5—C4—H4 | 118.7 | C5—C9—H9A | 109.5 |
C3—C4—H4 | 118.7 | C5—C9—H9B | 109.5 |
C4—C5—C6 | 117.57 (17) | H9A—C9—H9B | 109.5 |
C4—C5—C9 | 121.85 (16) | C5—C9—H9C | 109.5 |
C6—C5—C9 | 120.54 (16) | H9A—C9—H9C | 109.5 |
C1—C6—C5 | 121.81 (16) | H9B—C9—H9C | 109.5 |
C1—C6—H6 | 119.1 | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2i | 0.84 | 1.98 | 2.8010 (17) | 166 |
O2—H2···O3ii | 0.95 | 1.78 | 2.6728 (17) | 155 |
O3—H3···O1iii | 0.98 | 1.82 | 2.7824 (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
C9H12O4 | F(000) = 392 |
Mr = 184.19 | Dx = 1.455 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4917 reflections |
a = 4.6556 (5) Å | θ = 2.8–25.7° |
b = 14.5930 (15) Å | µ = 0.12 mm−1 |
c = 12.4616 (9) Å | T = 100 K |
β = 96.658 (4)° | Irregular, colourless |
V = 840.92 (14) Å3 | 0.30 × 0.20 × 0.08 mm |
Z = 4 | |
Data collection top
Nonius KappaCCD diffractometer | 1185 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.053 |
Graphite monochromator | θmax = 25.7°, θmin = 2.8° |
ϕ scans | h = −5→5 |
4917 measured reflections | k = −17→17 |
1528 independent reflections | l = −15→15 |
Refinement top
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) = 0.109 | H-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 parameters | Δρmax = 0.17 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
Crystal data top
C9H12O4 | V = 840.92 (14) Å3 |
Mr = 184.19 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 4.6556 (5) Å | µ = 0.12 mm−1 |
b = 14.5930 (15) Å | T = 100 K |
c = 12.4616 (9) Å | 0.30 × 0.20 × 0.08 mm |
β = 96.658 (4)° | |
Data collection top
Nonius KappaCCD diffractometer | 1185 reflections with I > 2σ(I) |
4917 measured reflections | Rint = 0.053 |
1528 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.109 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.17 e Å−3 |
1528 reflections | Δρmin = −0.24 e Å−3 |
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 | x | y | z | Uiso*/Ueq | |
O1 | 0.9721 (3) | 0.46012 (9) | 0.60068 (10) | 0.0254 (3) | |
H1 | 1.0360 | 0.4419 | 0.6681 | 0.030* | |
O2 | 1.0713 (3) | 0.35196 (9) | 0.40032 (10) | 0.0240 (3) | |
H2 | 1.0394 | 0.4156 | 0.4251 | 0.029* | |
O3 | 1.1581 (3) | 0.08398 (9) | 0.30709 (11) | 0.0276 (4) | |
H3 | 1.2766 | 0.0534 | 0.3613 | 0.033* | |
O4 | 0.5570 (3) | 0.07497 (9) | 0.61347 (10) | 0.0243 (3) | |
C1 | 0.7737 (4) | 0.30994 (13) | 0.54130 (15) | 0.0212 (4) | |
C2 | 0.9414 (4) | 0.28799 (13) | 0.45892 (15) | 0.0208 (4) | |
C3 | 0.9789 (4) | 0.19647 (13) | 0.42988 (14) | 0.0198 (4) | |
C4 | 0.8456 (4) | 0.12738 (13) | 0.48285 (15) | 0.0208 (4) | |
H4 | 0.8663 | 0.0666 | 0.4627 | 0.025* | |
C5 | 0.6809 (4) | 0.14876 (13) | 0.56609 (15) | 0.0210 (4) | |
C6 | 0.6460 (4) | 0.23931 (13) | 0.59494 (15) | 0.0217 (4) | |
H6 | 0.5364 | 0.2533 | 0.6506 | 0.026* | |
C7 | 0.7160 (4) | 0.40828 (13) | 0.56661 (17) | 0.0253 (4) | |
H7A | 0.6151 | 0.4370 | 0.5029 | 0.030* | |
H7B | 0.5895 | 0.4104 | 0.6231 | 0.030* | |
C8 | 1.1611 (4) | 0.17773 (13) | 0.33988 (15) | 0.0221 (4) | |
H8A | 1.0916 | 0.2153 | 0.2781 | 0.026* | |
H8B | 1.3590 | 0.1957 | 0.3634 | 0.026* | |
C9 | 0.4065 (4) | 0.09498 (14) | 0.70529 (16) | 0.0275 (5) | |
H9A | 0.5369 | 0.1237 | 0.7606 | 0.041* | |
H9B | 0.3344 | 0.0391 | 0.7327 | 0.041* | |
H9C | 0.2478 | 0.1355 | 0.6838 | 0.041* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0342 (8) | 0.0186 (7) | 0.0234 (7) | −0.0036 (6) | 0.0038 (6) | 0.0008 (5) |
O2 | 0.0302 (7) | 0.0169 (7) | 0.0261 (7) | −0.0015 (5) | 0.0082 (6) | 0.0007 (5) |
O3 | 0.0390 (8) | 0.0214 (7) | 0.0223 (7) | 0.0073 (6) | 0.0024 (6) | −0.0019 (6) |
O4 | 0.0292 (7) | 0.0194 (7) | 0.0258 (7) | 0.0005 (5) | 0.0095 (6) | 0.0012 (5) |
C1 | 0.0209 (9) | 0.0200 (10) | 0.0222 (9) | 0.0014 (7) | 0.0004 (8) | −0.0014 (8) |
C2 | 0.0192 (9) | 0.0209 (10) | 0.0216 (9) | −0.0014 (7) | 0.0002 (8) | 0.0000 (8) |
C3 | 0.0187 (9) | 0.0201 (10) | 0.0201 (9) | 0.0023 (7) | −0.0005 (8) | −0.0005 (7) |
C4 | 0.0227 (10) | 0.0172 (9) | 0.0219 (9) | 0.0021 (7) | 0.0000 (8) | −0.0014 (7) |
C5 | 0.0203 (9) | 0.0204 (10) | 0.0218 (9) | −0.0005 (7) | 0.0009 (8) | 0.0029 (7) |
C6 | 0.0223 (9) | 0.0225 (10) | 0.0204 (9) | 0.0024 (8) | 0.0030 (8) | −0.0005 (8) |
C7 | 0.0243 (10) | 0.0218 (10) | 0.0299 (10) | 0.0012 (8) | 0.0039 (9) | −0.0013 (8) |
C8 | 0.0249 (10) | 0.0206 (10) | 0.0210 (9) | 0.0026 (8) | 0.0037 (8) | −0.0005 (7) |
C9 | 0.0304 (11) | 0.0277 (11) | 0.0260 (10) | −0.0007 (8) | 0.0102 (9) | 0.0024 (8) |
Geometric parameters (Å, º) top
O1—C7 | 1.434 (2) | C3—C8 | 1.508 (2) |
O1—H1 | 0.8983 | C4—C5 | 1.395 (3) |
O2—C2 | 1.369 (2) | C4—H4 | 0.9300 |
O2—H2 | 0.9946 | C5—C6 | 1.384 (3) |
O3—C8 | 1.427 (2) | C6—H6 | 0.9300 |
O3—H3 | 0.9341 | C7—H7A | 0.9700 |
O4—C5 | 1.386 (2) | C7—H7B | 0.9700 |
O4—C9 | 1.439 (2) | C8—H8A | 0.9700 |
C1—C2 | 1.397 (3) | C8—H8B | 0.9700 |
C1—C6 | 1.398 (3) | C9—H9A | 0.9600 |
C1—C7 | 1.500 (3) | C9—H9B | 0.9600 |
C2—C3 | 1.400 (3) | C9—H9C | 0.9600 |
C3—C4 | 1.390 (3) | | |
| | | |
C7—O1—H1 | 107.1 | C5—C6—H6 | 119.7 |
C2—O2—H2 | 112.3 | C1—C6—H6 | 119.7 |
C8—O3—H3 | 105.4 | O1—C7—C1 | 113.83 (15) |
C5—O4—C9 | 116.50 (15) | O1—C7—H7A | 108.8 |
C2—C1—C6 | 119.15 (17) | C1—C7—H7A | 108.8 |
C2—C1—C7 | 120.17 (17) | O1—C7—H7B | 108.8 |
C6—C1—C7 | 120.55 (16) | C1—C7—H7B | 108.8 |
O2—C2—C1 | 123.70 (17) | H7A—C7—H7B | 107.7 |
O2—C2—C3 | 115.89 (16) | O3—C8—C3 | 113.52 (15) |
C1—C2—C3 | 120.39 (17) | O3—C8—H8A | 108.9 |
C4—C3—C2 | 119.55 (17) | C3—C8—H8A | 108.9 |
C4—C3—C8 | 122.85 (17) | O3—C8—H8B | 108.9 |
C2—C3—C8 | 117.60 (16) | C3—C8—H8B | 108.9 |
C3—C4—C5 | 120.34 (17) | H8A—C8—H8B | 107.7 |
C3—C4—H4 | 119.8 | O4—C9—H9A | 109.5 |
C5—C4—H4 | 119.8 | O4—C9—H9B | 109.5 |
C6—C5—O4 | 124.34 (17) | H9A—C9—H9B | 109.5 |
C6—C5—C4 | 119.87 (17) | O4—C9—H9C | 109.5 |
O4—C5—C4 | 115.78 (16) | H9A—C9—H9C | 109.5 |
C5—C6—C1 | 120.69 (17) | H9B—C9—H9C | 109.5 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O3i | 0.90 | 1.80 | 2.6951 (19) | 175 |
O2—H2···O1ii | 0.99 | 1.84 | 2.7496 (18) | 150 |
O3—H3···O4iii | 0.93 | 2.04 | 2.7956 (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
C14H14O4 | F(000) = 520 |
Mr = 246.25 | Dx = 1.333 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 9055 reflections |
a = 11.1451 (11) Å | θ = 3.0–25.7° |
b = 13.5515 (12) Å | µ = 0.10 mm−1 |
c = 8.1935 (9) Å | T = 100 K |
β = 97.486 (6)° | Platelet, colourless |
V = 1226.9 (2) Å3 | 0.25 × 0.20 × 0.08 mm |
Z = 4 | |
Data collection top
Nonius KappaCCD diffractometer | 1350 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.083 |
Graphite monochromator | θmax = 25.7°, θmin = 3.0° |
ϕ scans | h = −13→13 |
9055 measured reflections | k = −16→0 |
2314 independent reflections | l = 0→9 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.069 | H-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 reflections | Δρmax = 0.27 e Å−3 |
164 parameters | Δρmin = −0.26 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.016 (3) |
Crystal data top
C14H14O4 | V = 1226.9 (2) Å3 |
Mr = 246.25 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.1451 (11) Å | µ = 0.10 mm−1 |
b = 13.5515 (12) Å | T = 100 K |
c = 8.1935 (9) Å | 0.25 × 0.20 × 0.08 mm |
β = 97.486 (6)° | |
Data collection top
Nonius KappaCCD diffractometer | 1350 reflections with I > 2σ(I) |
9055 measured reflections | Rint = 0.083 |
2314 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.069 | 0 restraints |
wR(F2) = 0.171 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.27 e Å−3 |
2314 reflections | Δρmin = −0.26 e Å−3 |
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 | x | y | z | Uiso*/Ueq | |
O1 | −0.0185 (2) | 0.91081 (18) | 0.0823 (3) | 0.0296 (6) | |
H1 | −0.0518 | 0.8833 | 0.1586 | 0.035* | |
O2 | 0.0828 (2) | 1.10527 (16) | 0.2397 (3) | 0.0286 (6) | |
H2 | 0.0605 | 1.0834 | 0.1347 | 0.034* | |
O3 | 0.1490 (2) | 1.19638 (17) | 0.7209 (3) | 0.0290 (6) | |
H3 | 0.1081 | 1.2576 | 0.7364 | 0.035* | |
O4 | 0.2683 (2) | 0.84138 (17) | 0.7230 (3) | 0.0298 (6) | |
C1 | 0.1386 (3) | 0.9358 (3) | 0.3159 (4) | 0.0257 (8) | |
C2 | 0.1236 (3) | 1.0346 (2) | 0.3543 (4) | 0.0233 (8) | |
C3 | 0.1542 (3) | 1.0699 (3) | 0.5157 (4) | 0.0249 (8) | |
C4 | 0.2024 (3) | 1.0048 (3) | 0.6364 (4) | 0.0257 (8) | |
H4 | 0.2240 | 1.0270 | 0.7436 | 0.031* | |
C5 | 0.2188 (3) | 0.9064 (3) | 0.5987 (4) | 0.0266 (8) | |
C6 | 0.1865 (3) | 0.8715 (3) | 0.4418 (4) | 0.0268 (8) | |
H6 | 0.1964 | 0.8050 | 0.4190 | 0.032* | |
C7 | 0.1076 (3) | 0.8986 (3) | 0.1424 (4) | 0.0292 (9) | |
H7A | 0.1556 | 0.9339 | 0.0709 | 0.035* | |
H7B | 0.1284 | 0.8292 | 0.1387 | 0.035* | |
C8 | 0.1385 (3) | 1.1774 (3) | 0.5484 (4) | 0.0286 (9) | |
H8A | 0.1995 | 1.2148 | 0.5007 | 0.034* | |
H8B | 0.0596 | 1.1988 | 0.4965 | 0.034* | |
C9 | 0.3891 (3) | 0.8594 (3) | 0.7865 (4) | 0.0266 (9) | |
C10 | 0.4704 (3) | 0.9005 (3) | 0.6931 (5) | 0.0339 (9) | |
H10 | 0.4459 | 0.9185 | 0.5844 | 0.041* | |
C11 | 0.5888 (4) | 0.9146 (3) | 0.7625 (5) | 0.0417 (11) | |
H11 | 0.6434 | 0.9439 | 0.7008 | 0.050* | |
C12 | 0.6273 (4) | 0.8857 (3) | 0.9235 (5) | 0.0401 (11) | |
H12 | 0.7076 | 0.8941 | 0.9685 | 0.048* | |
C13 | 0.5459 (4) | 0.8446 (3) | 1.0152 (5) | 0.0426 (11) | |
H13 | 0.5712 | 0.8253 | 1.1231 | 0.051* | |
C14 | 0.4249 (3) | 0.8313 (3) | 0.9479 (5) | 0.0359 (10) | |
H14 | 0.3695 | 0.8040 | 1.0106 | 0.043* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0282 (15) | 0.0342 (14) | 0.0251 (13) | −0.0040 (11) | −0.0012 (11) | 0.0045 (11) |
O2 | 0.0371 (16) | 0.0270 (14) | 0.0194 (12) | −0.0013 (11) | −0.0045 (11) | 0.0028 (11) |
O3 | 0.0412 (16) | 0.0254 (13) | 0.0200 (13) | 0.0020 (11) | 0.0025 (11) | −0.0026 (11) |
O4 | 0.0242 (14) | 0.0293 (14) | 0.0330 (14) | 0.0001 (11) | −0.0069 (11) | 0.0077 (11) |
C1 | 0.023 (2) | 0.031 (2) | 0.0234 (18) | −0.0039 (15) | 0.0016 (15) | −0.0021 (16) |
C2 | 0.021 (2) | 0.0243 (18) | 0.0236 (19) | 0.0023 (14) | 0.0004 (15) | 0.0038 (16) |
C3 | 0.025 (2) | 0.0260 (19) | 0.0240 (19) | −0.0033 (15) | 0.0032 (15) | −0.0024 (15) |
C4 | 0.027 (2) | 0.0273 (19) | 0.0218 (19) | −0.0029 (15) | −0.0001 (15) | −0.0020 (16) |
C5 | 0.0221 (19) | 0.0279 (19) | 0.0276 (19) | 0.0034 (15) | −0.0052 (15) | 0.0040 (17) |
C6 | 0.024 (2) | 0.0250 (19) | 0.030 (2) | −0.0012 (15) | −0.0009 (16) | −0.0022 (16) |
C7 | 0.030 (2) | 0.029 (2) | 0.028 (2) | 0.0019 (16) | 0.0029 (17) | −0.0025 (17) |
C8 | 0.037 (2) | 0.029 (2) | 0.0189 (18) | −0.0011 (16) | 0.0003 (16) | 0.0008 (16) |
C9 | 0.021 (2) | 0.0264 (19) | 0.031 (2) | 0.0021 (15) | −0.0019 (16) | 0.0002 (16) |
C10 | 0.026 (2) | 0.038 (2) | 0.035 (2) | −0.0012 (17) | −0.0009 (17) | 0.0007 (18) |
C11 | 0.028 (2) | 0.051 (3) | 0.047 (3) | −0.0023 (19) | 0.007 (2) | 0.003 (2) |
C12 | 0.026 (2) | 0.041 (2) | 0.050 (3) | 0.0033 (18) | −0.0068 (19) | −0.007 (2) |
C13 | 0.041 (3) | 0.043 (2) | 0.040 (2) | −0.002 (2) | −0.010 (2) | 0.004 (2) |
C14 | 0.031 (2) | 0.037 (2) | 0.037 (2) | −0.0056 (17) | −0.0068 (18) | 0.0064 (19) |
Geometric parameters (Å, º) top
O1—C7 | 1.437 (4) | C6—H6 | 0.9300 |
O1—H1 | 0.8528 | C7—H7A | 0.9700 |
O2—C2 | 1.375 (4) | C7—H7B | 0.9700 |
O2—H2 | 0.9139 | C8—H8A | 0.9700 |
O3—C8 | 1.427 (4) | C8—H8B | 0.9700 |
O3—H3 | 0.9632 | C9—C10 | 1.378 (5) |
O4—C9 | 1.400 (4) | C9—C14 | 1.384 (5) |
O4—C5 | 1.404 (4) | C10—C11 | 1.380 (5) |
C1—C2 | 1.391 (5) | C10—H10 | 0.9300 |
C1—C6 | 1.402 (5) | C11—C12 | 1.389 (5) |
C1—C7 | 1.506 (5) | C11—H11 | 0.9300 |
C2—C3 | 1.405 (5) | C12—C13 | 1.370 (6) |
C3—C4 | 1.381 (5) | C12—H12 | 0.9300 |
C3—C8 | 1.496 (5) | C13—C14 | 1.401 (5) |
C4—C5 | 1.385 (5) | C13—H13 | 0.9300 |
C4—H4 | 0.9300 | C14—H14 | 0.9300 |
C5—C6 | 1.373 (5) | | |
| | | |
C7—O1—H1 | 101.4 | C1—C7—H7B | 109.1 |
C2—O2—H2 | 116.2 | H7A—C7—H7B | 107.9 |
C8—O3—H3 | 107.9 | O3—C8—C3 | 110.9 (3) |
C9—O4—C5 | 115.3 (3) | O3—C8—H8A | 109.5 |
C2—C1—C6 | 118.6 (3) | C3—C8—H8A | 109.5 |
C2—C1—C7 | 121.1 (3) | O3—C8—H8B | 109.5 |
C6—C1—C7 | 120.3 (3) | C3—C8—H8B | 109.5 |
O2—C2—C1 | 123.7 (3) | H8A—C8—H8B | 108.0 |
O2—C2—C3 | 115.1 (3) | C10—C9—C14 | 120.9 (3) |
C1—C2—C3 | 121.2 (3) | C10—C9—O4 | 122.3 (3) |
C4—C3—C2 | 118.8 (3) | C14—C9—O4 | 116.8 (3) |
C4—C3—C8 | 122.5 (3) | C9—C10—C11 | 119.4 (4) |
C2—C3—C8 | 118.6 (3) | C9—C10—H10 | 120.3 |
C3—C4—C5 | 120.3 (3) | C11—C10—H10 | 120.3 |
C3—C4—H4 | 119.8 | C10—C11—C12 | 120.8 (4) |
C5—C4—H4 | 119.8 | C10—C11—H11 | 119.6 |
C6—C5—C4 | 121.0 (3) | C12—C11—H11 | 119.6 |
C6—C5—O4 | 119.5 (3) | C13—C12—C11 | 119.4 (4) |
C4—C5—O4 | 119.5 (3) | C13—C12—H12 | 120.3 |
C5—C6—C1 | 120.2 (3) | C11—C12—H12 | 120.3 |
C5—C6—H6 | 119.9 | C12—C13—C14 | 120.6 (4) |
C1—C6—H6 | 119.9 | C12—C13—H13 | 119.7 |
O1—C7—C1 | 112.3 (3) | C14—C13—H13 | 119.7 |
O1—C7—H7A | 109.1 | C9—C14—C13 | 118.9 (4) |
C1—C7—H7A | 109.1 | C9—C14—H14 | 120.5 |
O1—C7—H7B | 109.2 | C13—C14—H14 | 120.5 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O3i | 0.85 | 1.90 | 2.727 (3) | 164 |
O2—H2···O1ii | 0.91 | 1.78 | 2.651 (3) | 158 |
O3—H3···O2iii | 0.96 | 1.88 | 2.797 (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
C18H22O4 | F(000) = 1296 |
Mr = 302.36 | Dx = 1.343 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 16226 reflections |
a = 7.0604 (4) Å | θ = 2.6–25.7° |
b = 16.4995 (11) Å | µ = 0.09 mm−1 |
c = 25.6678 (17) Å | T = 100 K |
V = 2990.1 (3) Å3 | Irregular, colourless |
Z = 8 | 0.35 × 0.20 × 0.08 mm |
Data collection top
Nonius KappaCCD diffractometer | 2188 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.064 |
Graphite monochromator | θmax = 25.7°, θmin = 2.6° |
ϕ scans | h = −8→8 |
16226 measured reflections | k = −20→20 |
2824 independent reflections | l = −31→31 |
Refinement top
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.119 | H-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 parameters | Δρmax = 0.25 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
Crystal data top
C18H22O4 | V = 2990.1 (3) Å3 |
Mr = 302.36 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 7.0604 (4) Å | µ = 0.09 mm−1 |
b = 16.4995 (11) Å | T = 100 K |
c = 25.6678 (17) Å | 0.35 × 0.20 × 0.08 mm |
Data collection top
Nonius KappaCCD diffractometer | 2188 reflections with I > 2σ(I) |
16226 measured reflections | Rint = 0.064 |
2824 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.119 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.25 e Å−3 |
2824 reflections | Δρmin = −0.25 e Å−3 |
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 | x | y | z | Uiso*/Ueq | |
O1 | 0.74357 (17) | 0.14395 (7) | 0.46826 (5) | 0.0220 (3) | |
H1 | 0.6278 | 0.1615 | 0.4826 | 0.026* | |
O2 | 0.77232 (17) | −0.10769 (7) | 0.46688 (5) | 0.0234 (3) | |
H2 | 0.8181 | −0.1592 | 0.4714 | 0.028* | |
O3 | 0.93433 (18) | −0.23197 (7) | 0.52217 (5) | 0.0245 (3) | |
H3 | 1.0579 | −0.2040 | 0.5295 | 0.029* | |
O4 | 1.12084 (17) | 0.34651 (7) | 0.68990 (5) | 0.0256 (3) | |
C1 | 0.7401 (2) | 0.01371 (10) | 0.51532 (6) | 0.0191 (4) | |
C2 | 0.7632 (2) | −0.07076 (10) | 0.51498 (6) | 0.0193 (4) | |
C3 | 0.7756 (2) | −0.11425 (10) | 0.56131 (7) | 0.0188 (4) | |
C4 | 0.7599 (2) | −0.07237 (10) | 0.60860 (6) | 0.0197 (4) | |
H4 | 0.7698 | −0.1011 | 0.6396 | 0.024* | |
C5 | 0.7300 (2) | 0.01072 (10) | 0.61056 (6) | 0.0195 (4) | |
C6 | 0.7220 (2) | 0.05245 (10) | 0.56288 (7) | 0.0198 (4) | |
H6 | 0.7038 | 0.1083 | 0.5633 | 0.024* | |
C7 | 0.7341 (2) | 0.05734 (10) | 0.46371 (7) | 0.0204 (4) | |
H7A | 0.8393 | 0.0389 | 0.4425 | 0.024* | |
H7B | 0.6179 | 0.0429 | 0.4458 | 0.024* | |
C8 | 0.8006 (3) | −0.20532 (10) | 0.56110 (7) | 0.0220 (4) | |
H8A | 0.8439 | −0.2227 | 0.5952 | 0.026* | |
H8B | 0.6790 | −0.2308 | 0.5546 | 0.026* | |
C9 | 0.6871 (2) | 0.05623 (10) | 0.66146 (6) | 0.0209 (4) | |
C10 | 0.4733 (2) | 0.07601 (11) | 0.65992 (7) | 0.0258 (4) | |
H10A | 0.4365 | 0.1009 | 0.6922 | 0.039* | |
H10B | 0.4026 | 0.0269 | 0.6550 | 0.039* | |
H10C | 0.4481 | 0.1125 | 0.6316 | 0.039* | |
C11 | 0.7253 (3) | 0.00394 (11) | 0.71011 (7) | 0.0241 (4) | |
H11A | 0.8557 | −0.0125 | 0.7104 | 0.036* | |
H11B | 0.6456 | −0.0432 | 0.7093 | 0.036* | |
H11C | 0.6984 | 0.0350 | 0.7409 | 0.036* | |
C12 | 0.8054 (2) | 0.13376 (10) | 0.66671 (7) | 0.0209 (4) | |
C13 | 0.9807 (3) | 0.14340 (10) | 0.64250 (7) | 0.0228 (4) | |
H13 | 1.0265 | 0.1018 | 0.6215 | 0.027* | |
C14 | 1.0898 (3) | 0.21319 (10) | 0.64861 (7) | 0.0236 (4) | |
H14 | 1.2051 | 0.2182 | 0.6314 | 0.028* | |
C15 | 1.0253 (3) | 0.27532 (10) | 0.68061 (7) | 0.0219 (4) | |
C16 | 0.8525 (3) | 0.26638 (10) | 0.70612 (7) | 0.0238 (4) | |
H16 | 0.8088 | 0.3074 | 0.7279 | 0.029* | |
C17 | 0.7454 (3) | 0.19701 (10) | 0.69939 (7) | 0.0221 (4) | |
H17 | 0.6308 | 0.1921 | 0.7170 | 0.027* | |
C18 | 1.3019 (3) | 0.35616 (11) | 0.66596 (8) | 0.0288 (4) | |
H18A | 1.3865 | 0.3150 | 0.6786 | 0.043* | |
H18B | 1.3519 | 0.4087 | 0.6744 | 0.043* | |
H18C | 1.2891 | 0.3513 | 0.6289 | 0.043* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0243 (6) | 0.0182 (6) | 0.0234 (7) | 0.0003 (5) | 0.0028 (5) | 0.0008 (5) |
O2 | 0.0315 (7) | 0.0202 (6) | 0.0186 (6) | 0.0010 (5) | 0.0004 (5) | −0.0035 (5) |
O3 | 0.0243 (7) | 0.0212 (6) | 0.0280 (7) | 0.0000 (5) | 0.0030 (5) | −0.0056 (5) |
O4 | 0.0256 (7) | 0.0211 (6) | 0.0301 (7) | −0.0020 (5) | −0.0013 (5) | −0.0033 (5) |
C1 | 0.0164 (8) | 0.0218 (8) | 0.0190 (9) | −0.0017 (7) | −0.0001 (6) | 0.0002 (7) |
C2 | 0.0172 (8) | 0.0223 (9) | 0.0183 (9) | −0.0016 (7) | 0.0006 (6) | −0.0030 (7) |
C3 | 0.0164 (8) | 0.0194 (8) | 0.0206 (9) | −0.0005 (7) | 0.0000 (7) | −0.0002 (7) |
C4 | 0.0184 (8) | 0.0226 (9) | 0.0179 (9) | −0.0006 (7) | −0.0002 (7) | 0.0008 (7) |
C5 | 0.0175 (8) | 0.0218 (9) | 0.0194 (9) | 0.0002 (7) | 0.0000 (6) | −0.0013 (7) |
C6 | 0.0204 (9) | 0.0175 (8) | 0.0215 (9) | 0.0000 (7) | 0.0005 (7) | −0.0004 (7) |
C7 | 0.0214 (9) | 0.0188 (8) | 0.0210 (9) | −0.0005 (7) | −0.0001 (7) | −0.0014 (7) |
C8 | 0.0245 (9) | 0.0196 (9) | 0.0218 (9) | −0.0014 (7) | 0.0019 (7) | −0.0012 (7) |
C9 | 0.0231 (9) | 0.0212 (9) | 0.0182 (9) | 0.0021 (7) | 0.0016 (7) | −0.0006 (7) |
C10 | 0.0235 (9) | 0.0291 (10) | 0.0249 (10) | 0.0012 (8) | 0.0016 (7) | −0.0042 (7) |
C11 | 0.0304 (10) | 0.0226 (9) | 0.0193 (9) | −0.0021 (8) | 0.0005 (7) | −0.0011 (7) |
C12 | 0.0246 (9) | 0.0218 (9) | 0.0163 (8) | 0.0013 (7) | −0.0027 (7) | 0.0000 (7) |
C13 | 0.0248 (9) | 0.0213 (9) | 0.0223 (9) | 0.0034 (8) | 0.0001 (7) | −0.0033 (7) |
C14 | 0.0219 (9) | 0.0254 (9) | 0.0235 (9) | 0.0016 (8) | 0.0011 (7) | −0.0004 (7) |
C15 | 0.0268 (9) | 0.0188 (8) | 0.0200 (9) | 0.0010 (7) | −0.0052 (7) | 0.0001 (7) |
C16 | 0.0300 (10) | 0.0215 (9) | 0.0199 (9) | 0.0039 (8) | −0.0010 (7) | −0.0014 (7) |
C17 | 0.0251 (9) | 0.0213 (9) | 0.0199 (9) | 0.0024 (7) | 0.0030 (7) | −0.0002 (7) |
C18 | 0.0300 (10) | 0.0286 (10) | 0.0278 (10) | −0.0065 (8) | 0.0016 (8) | −0.0009 (8) |
Geometric parameters (Å, º) top
O1—C7 | 1.4353 (19) | C9—C12 | 1.534 (2) |
O1—H1 | 0.9420 | C9—C11 | 1.541 (2) |
O2—C2 | 1.378 (2) | C9—C10 | 1.545 (2) |
O2—H2 | 0.9166 | C10—H10A | 0.9600 |
O3—C8 | 1.444 (2) | C10—H10B | 0.9600 |
O3—H3 | 1.0049 | C10—H10C | 0.9600 |
O4—C15 | 1.375 (2) | C11—H11A | 0.9600 |
O4—C18 | 1.427 (2) | C11—H11B | 0.9600 |
C1—C6 | 1.384 (2) | C11—H11C | 0.9600 |
C1—C2 | 1.403 (2) | C12—C13 | 1.394 (3) |
C1—C7 | 1.508 (2) | C12—C17 | 1.404 (2) |
C2—C3 | 1.392 (2) | C13—C14 | 1.394 (2) |
C3—C4 | 1.401 (2) | C13—H13 | 0.9300 |
C3—C8 | 1.513 (2) | C14—C15 | 1.390 (2) |
C4—C5 | 1.388 (2) | C14—H14 | 0.9300 |
C4—H4 | 0.9300 | C15—C16 | 1.393 (3) |
C5—C6 | 1.405 (2) | C16—C17 | 1.383 (2) |
C5—C9 | 1.537 (2) | C16—H16 | 0.9300 |
C6—H6 | 0.9300 | C17—H17 | 0.9300 |
C7—H7A | 0.9700 | C18—H18A | 0.9600 |
C7—H7B | 0.9700 | C18—H18B | 0.9600 |
C8—H8A | 0.9700 | C18—H18C | 0.9600 |
C8—H8B | 0.9700 | | |
| | | |
C7—O1—H1 | 107.3 | C5—C9—C10 | 105.91 (14) |
C2—O2—H2 | 108.3 | C11—C9—C10 | 108.07 (14) |
C8—O3—H3 | 107.4 | C9—C10—H10A | 109.5 |
C15—O4—C18 | 117.38 (14) | C9—C10—H10B | 109.5 |
C6—C1—C2 | 118.36 (15) | H10A—C10—H10B | 109.5 |
C6—C1—C7 | 123.48 (15) | C9—C10—H10C | 109.5 |
C2—C1—C7 | 118.16 (14) | H10A—C10—H10C | 109.5 |
O2—C2—C3 | 122.32 (15) | H10B—C10—H10C | 109.5 |
O2—C2—C1 | 116.74 (14) | C9—C11—H11A | 109.5 |
C3—C2—C1 | 120.94 (15) | C9—C11—H11B | 109.5 |
C2—C3—C4 | 118.76 (15) | H11A—C11—H11B | 109.5 |
C2—C3—C8 | 121.09 (15) | C9—C11—H11C | 109.5 |
C4—C3—C8 | 120.13 (15) | H11A—C11—H11C | 109.5 |
C5—C4—C3 | 122.04 (16) | H11B—C11—H11C | 109.5 |
C5—C4—H4 | 119.0 | C13—C12—C17 | 116.69 (16) |
C3—C4—H4 | 119.0 | C13—C12—C9 | 122.66 (15) |
C4—C5—C6 | 117.28 (15) | C17—C12—C9 | 120.53 (16) |
C4—C5—C9 | 122.91 (15) | C12—C13—C14 | 122.31 (16) |
C6—C5—C9 | 119.54 (15) | C12—C13—H13 | 118.8 |
C1—C6—C5 | 122.56 (16) | C14—C13—H13 | 118.8 |
C1—C6—H6 | 118.7 | C15—C14—C13 | 119.64 (17) |
C5—C6—H6 | 118.7 | C15—C14—H14 | 120.2 |
O1—C7—C1 | 113.73 (14) | C13—C14—H14 | 120.2 |
O1—C7—H7A | 108.8 | O4—C15—C14 | 124.87 (16) |
C1—C7—H7A | 108.8 | O4—C15—C16 | 116.01 (15) |
O1—C7—H7B | 108.8 | C14—C15—C16 | 119.12 (16) |
C1—C7—H7B | 108.8 | C17—C16—C15 | 120.53 (16) |
H7A—C7—H7B | 107.7 | C17—C16—H16 | 119.7 |
O3—C8—C3 | 112.40 (14) | C15—C16—H16 | 119.7 |
O3—C8—H8A | 109.1 | C16—C17—C12 | 121.67 (17) |
C3—C8—H8A | 109.1 | C16—C17—H17 | 119.2 |
O3—C8—H8B | 109.1 | C12—C17—H17 | 119.2 |
C3—C8—H8B | 109.1 | O4—C18—H18A | 109.5 |
H8A—C8—H8B | 107.9 | O4—C18—H18B | 109.5 |
C12—C9—C5 | 112.01 (14) | H18A—C18—H18B | 109.5 |
C12—C9—C11 | 107.47 (14) | O4—C18—H18C | 109.5 |
C5—C9—C11 | 112.37 (14) | H18A—C18—H18C | 109.5 |
C12—C9—C10 | 110.99 (14) | H18B—C18—H18C | 109.5 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O3i | 0.94 | 2.08 | 2.7720 (16) | 129 |
O2—H2···O3 | 0.92 | 1.95 | 2.7436 (17) | 143 |
O3—H3···O1ii | 1.00 | 1.72 | 2.7095 (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 formula | C9H12O3 | C9H12O4 | C14H14O4 | C18H22O4 |
Mr | 168.19 | 184.19 | 246.25 | 302.36 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/c | Monoclinic, P21/c | Orthorhombic, Pbca |
Temperature (K) | 100 | 100 | 100 | 100 |
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), 90 | 90, 96.658 (4), 90 | 90, 97.486 (6), 90 | 90, 90, 90 |
V (Å3) | 808.36 (9) | 840.92 (14) | 1226.9 (2) | 2990.1 (3) |
Z | 4 | 4 | 4 | 8 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.10 | 0.12 | 0.10 | 0.09 |
Crystal size (mm) | 0.20 × 0.20 × 0.05 | 0.30 × 0.20 × 0.08 | 0.25 × 0.20 × 0.08 | 0.35 × 0.20 × 0.08 |
|
Data collection |
Diffractometer | Nonius 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 |
Rint | 0.047 | 0.053 | 0.083 | 0.064 |
(sin θ/λ)max (Å−1) | 0.610 | 0.609 | 0.610 | 0.609 |
|
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 reflections | 1524 | 1528 | 2314 | 2824 |
No. of parameters | 110 | 119 | 164 | 202 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.14, −0.25 | 0.17, −0.24 | 0.27, −0.26 | 0.25, −0.25 |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2i | 0.84 | 1.98 | 2.8010 (17) | 165.6 |
O2—H2···O3ii | 0.95 | 1.78 | 2.6728 (17) | 155.3 |
O3—H3···O1iii | 0.98 | 1.82 | 2.7824 (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···A | D—H | H···A | D···A | D—H···A |
O1—H1···O3i | 0.90 | 1.80 | 2.6951 (19) | 174.7 |
O2—H2···O1ii | 0.99 | 1.84 | 2.7496 (18) | 150.1 |
O3—H3···O4iii | 0.93 | 2.04 | 2.7956 (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···A | D—H | H···A | D···A | D—H···A |
O1—H1···O3i | 0.85 | 1.90 | 2.727 (3) | 164.4 |
O2—H2···O1ii | 0.91 | 1.78 | 2.651 (3) | 158.4 |
O3—H3···O2iii | 0.96 | 1.88 | 2.797 (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···A | D—H | H···A | D···A | D—H···A |
O1—H1···O3i | 0.94 | 2.08 | 2.7720 (16) | 129 |
O2—H2···O3 | 0.92 | 1.95 | 2.7436 (17) | 143 |
O3—H3···O1ii | 1.00 | 1.72 | 2.7095 (17) | 169 |
Symmetry codes: (i) −x+3/2, y+1/2, z; (ii) −x+2, −y, −z+1. |
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 π–π 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 π–π 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 π–π 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 π–π 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 π–π 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.