Two polymorphs of the title compound [systematic name: 1-(2,4-dihydroxyphenyl)ethanone], C
8H
8O
3, were investigated. The known structure [designated (I-M);
P2
1/
c,
Z = 4; previously investigated at room temperature by Robert, Moore, Eichhorn & Rillema (2007).
Acta Cryst. E
63, o4252] was redetermined at low temperature, and a new form [(I-O);
P2
12
12
1,
Z = 12] was discovered in the same sample. In both forms, the molecules are planar (apart from the methyl H atoms) and they contain intramolecular O—H
O=C hydrogen bonds. In polymorph (I-M), molecules are linked into chains by a single intermolecular O—H
O hydrogen bond, and the chains are linked into sheets by two C—H
O hydrogen bonds. Three O—H
O hydrogen bonds link the molecules of polymorph (I-O) into chains and neighbouring chains are connected by one C—H
O interaction to form an offset layer structure. Two weak methyl C—H
O interactions link the layers.
Supporting information
CCDC references: 742186; 742187
From an unsuccessful reaction intended to produce a coronand, flash
chromatography using as eluant a dichloromethane–methanol mixture (99:1,
v/v) gave a series of fractions which were combined and then
allowed to evaporate at ambient temperature, giving after 48 h crystals of
4-acetylresorcinol (one of the starting materials) which were suitable for
single-crystal X-ray diffraction.
Hydroxyl H atoms were located in difference maps and refined freely. Methyl H
toms were located in difference maps, idealized to C—H = 0.98 Å and
H—C—H = 109.5°, and refined as rigid groups which were allowed to rotate
but not to tilt, with Uiso(H) = 1.5Ueq(C). Other H atoms
were treated as riding atoms in calculated positions with C—H = 0.95 Å and
Uiso(H) = 1.2Ueq(C). For the orthorhombic form, which
crystallizes in a Sohncke space group, the Flack x parameter (Flack,
1983) was 0.48 (10), indicating either insignificant anomalous
dispersion or an
inversion twin with approximately equal components. Friedel opposite
reflections were therefore merged, so that the Flack parameter was
indeterminate. To counteract the necessarily rather poor data/parameter ratio
(although the data are 99.3% complete to 2θ = 135°), the displacement
parameters were restrained using the SHELXL (Sheldrick, 2008)
commands
SIMU and DELU [Please rephrase this using non-software-specific
terms].
Data collection: CrysAlis CCD (Version 1.171.32.24; Oxford Diffraction, 2008) for (IM); CrysAlis CCD (Version 1.171.32.15; Oxford Diffraction, 2008) for (IO). Cell refinement: CrysAlis RED (Version 1.171.32.24; Oxford Diffraction, 2008) for (IM); CrysAlis RED (Version 1.171.32.15; Oxford Diffraction, 2008) for (IO). Data reduction: CrysAlis RED (Version 1.171.32.24; Oxford Diffraction, (2008) for (IM); CrysAlis RED (Version 1.171.32.15; Oxford Diffraction, (2008) for (IO). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
(IM) 1-(2,4-dihydroxyphenyl)ethanone
top
Crystal data top
C8H8O3 | F(000) = 320 |
Mr = 152.14 | Dx = 1.430 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4165 reflections |
a = 7.1194 (3) Å | θ = 2.8–32.5° |
b = 13.6690 (6) Å | µ = 0.11 mm−1 |
c = 7.2695 (4) Å | T = 100 K |
β = 92.859 (6)° | Tablet, colourless |
V = 706.55 (6) Å3 | 0.40 × 0.40 × 0.25 mm |
Z = 4 | |
Data collection top
Oxford Diffraction Xcalibur S diffractometer | 1508 reflections with I > 2σ(I) |
Radiation source: Enhance (Mo) X-ray Source | Rint = 0.042 |
Graphite monochromator | θmax = 30.5°, θmin = 2.9° |
Detector resolution: 16.1057 pixels mm-1 | h = −10→10 |
ω scans | k = −19→19 |
12428 measured reflections | l = −10→10 |
2149 independent reflections | |
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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.105 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.95 | w = 1/[σ2(Fo2) + (0.0639P)2] where P = (Fo2 + 2Fc2)/3 |
2149 reflections | (Δ/σ)max < 0.001 |
109 parameters | Δρmax = 0.43 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
Crystal data top
C8H8O3 | V = 706.55 (6) Å3 |
Mr = 152.14 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.1194 (3) Å | µ = 0.11 mm−1 |
b = 13.6690 (6) Å | T = 100 K |
c = 7.2695 (4) Å | 0.40 × 0.40 × 0.25 mm |
β = 92.859 (6)° | |
Data collection top
Oxford Diffraction Xcalibur S diffractometer | 1508 reflections with I > 2σ(I) |
12428 measured reflections | Rint = 0.042 |
2149 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.105 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.95 | Δρmax = 0.43 e Å−3 |
2149 reflections | Δρmin = −0.25 e Å−3 |
109 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.81081 (13) | 0.14406 (7) | 0.06216 (15) | 0.0125 (2) | |
C2 | 0.72889 (14) | 0.23477 (8) | 0.08849 (14) | 0.0124 (2) | |
H2 | 0.7900 | 0.2928 | 0.0513 | 0.015* | |
C3 | 0.55653 (14) | 0.23995 (7) | 0.16981 (14) | 0.0108 (2) | |
C4 | 0.46483 (14) | 0.15387 (7) | 0.22750 (14) | 0.0110 (2) | |
C5 | 0.55579 (14) | 0.06396 (7) | 0.20224 (14) | 0.0124 (2) | |
H5 | 0.4979 | 0.0055 | 0.2418 | 0.015* | |
C6 | 0.72581 (14) | 0.05823 (7) | 0.12202 (15) | 0.0137 (2) | |
H6 | 0.7852 | −0.0033 | 0.1073 | 0.016* | |
C7 | 0.28447 (15) | 0.15935 (8) | 0.31220 (15) | 0.0129 (2) | |
C8 | 0.18931 (15) | 0.06830 (8) | 0.37512 (16) | 0.0175 (2) | |
H8A | 0.0727 | 0.0859 | 0.4333 | 0.026* | |
H8B | 0.2730 | 0.0337 | 0.4642 | 0.026* | |
H8C | 0.1600 | 0.0258 | 0.2689 | 0.026* | |
O1 | 0.97457 (10) | 0.13328 (6) | −0.02234 (12) | 0.0176 (2) | |
H11 | 1.027 (2) | 0.1902 (14) | −0.059 (3) | 0.059 (6)* | |
O2 | 0.47987 (11) | 0.32938 (5) | 0.19053 (11) | 0.01532 (19) | |
H12 | 0.374 (2) | 0.3192 (12) | 0.249 (3) | 0.051 (5)* | |
O3 | 0.20646 (10) | 0.23996 (5) | 0.33314 (11) | 0.0177 (2) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0102 (5) | 0.0150 (5) | 0.0123 (5) | −0.0001 (4) | 0.0020 (4) | −0.0002 (4) |
C2 | 0.0129 (5) | 0.0107 (5) | 0.0136 (5) | −0.0019 (4) | 0.0021 (4) | 0.0013 (4) |
C3 | 0.0131 (5) | 0.0084 (4) | 0.0108 (5) | 0.0015 (3) | 0.0001 (4) | −0.0007 (4) |
C4 | 0.0109 (5) | 0.0104 (4) | 0.0118 (5) | 0.0002 (4) | 0.0017 (4) | −0.0004 (4) |
C5 | 0.0129 (5) | 0.0097 (5) | 0.0146 (5) | −0.0005 (4) | 0.0009 (4) | 0.0007 (4) |
C6 | 0.0134 (5) | 0.0093 (5) | 0.0186 (6) | 0.0021 (4) | 0.0023 (4) | −0.0002 (4) |
C7 | 0.0115 (5) | 0.0162 (5) | 0.0111 (5) | 0.0000 (4) | 0.0003 (4) | −0.0003 (4) |
C8 | 0.0135 (5) | 0.0187 (5) | 0.0208 (6) | −0.0030 (4) | 0.0052 (4) | 0.0024 (4) |
O1 | 0.0136 (4) | 0.0149 (4) | 0.0252 (5) | 0.0008 (3) | 0.0101 (3) | 0.0010 (3) |
O2 | 0.0169 (4) | 0.0088 (4) | 0.0208 (4) | 0.0029 (3) | 0.0057 (3) | −0.0007 (3) |
O3 | 0.0153 (4) | 0.0160 (4) | 0.0223 (5) | 0.0031 (3) | 0.0062 (3) | −0.0013 (3) |
Geometric parameters (Å, º) top
C1—O1 | 1.3527 (12) | C7—C8 | 1.4994 (14) |
C1—C2 | 1.3875 (14) | C2—H2 | 0.9500 |
C1—C6 | 1.3994 (13) | C5—H5 | 0.9500 |
C2—C3 | 1.3902 (13) | C6—H6 | 0.9500 |
C3—O2 | 1.3501 (12) | C8—H8A | 0.9800 |
C3—C4 | 1.4191 (14) | C8—H8B | 0.9800 |
C4—C5 | 1.4055 (14) | C8—H8C | 0.9800 |
C4—C7 | 1.4534 (14) | O1—H11 | 0.908 (19) |
C5—C6 | 1.3717 (14) | O2—H12 | 0.896 (18) |
C7—O3 | 1.2467 (12) | | |
| | | |
O1—C1—C2 | 122.53 (9) | C1—C2—H2 | 120.3 |
O1—C1—C6 | 116.47 (9) | C3—C2—H2 | 120.3 |
C2—C1—C6 | 121.00 (9) | C6—C5—H5 | 119.1 |
C1—C2—C3 | 119.36 (9) | C4—C5—H5 | 119.1 |
O2—C3—C2 | 117.64 (9) | C5—C6—H6 | 120.4 |
O2—C3—C4 | 121.54 (9) | C1—C6—H6 | 120.4 |
C2—C3—C4 | 120.81 (9) | C7—C8—H8A | 109.5 |
C5—C4—C3 | 117.69 (9) | C7—C8—H8B | 109.5 |
C5—C4—C7 | 121.53 (9) | H8A—C8—H8B | 109.5 |
C3—C4—C7 | 120.78 (9) | C7—C8—H8C | 109.5 |
C6—C5—C4 | 121.84 (9) | H8A—C8—H8C | 109.5 |
C5—C6—C1 | 119.26 (9) | H8B—C8—H8C | 109.5 |
O3—C7—C4 | 120.37 (9) | C1—O1—H11 | 114.4 (11) |
O3—C7—C8 | 119.06 (9) | C3—O2—H12 | 105.5 (11) |
C4—C7—C8 | 120.57 (9) | | |
| | | |
O1—C1—C2—C3 | 177.41 (9) | C7—C4—C5—C6 | 179.85 (10) |
C6—C1—C2—C3 | −2.27 (16) | C4—C5—C6—C1 | −0.51 (16) |
C1—C2—C3—O2 | −178.99 (9) | O1—C1—C6—C5 | −177.47 (10) |
C1—C2—C3—C4 | 0.61 (15) | C2—C1—C6—C5 | 2.23 (16) |
O2—C3—C4—C5 | −179.39 (9) | C5—C4—C7—O3 | −179.99 (10) |
C2—C3—C4—C5 | 1.03 (15) | C3—C4—C7—O3 | 0.96 (16) |
O2—C3—C4—C7 | −0.30 (15) | C5—C4—C7—C8 | −0.17 (15) |
C2—C3—C4—C7 | −179.89 (9) | C3—C4—C7—C8 | −179.21 (9) |
C3—C4—C5—C6 | −1.08 (15) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H11···O3i | 0.908 (19) | 1.807 (18) | 2.6466 (10) | 152.7 (17) |
O2—H12···O3 | 0.896 (18) | 1.743 (18) | 2.5610 (11) | 150.5 (16) |
C6—H6···O1ii | 0.95 | 2.56 | 3.4759 (13) | 161 |
C5—H5···O2iii | 0.95 | 2.46 | 3.3127 (13) | 149 |
Symmetry codes: (i) x+1, −y+1/2, z−1/2; (ii) −x+2, −y, −z; (iii) −x+1, y−1/2, −z+1/2. |
(IO) 1-(2,4-dihydroxyphenyl)ethanone
top
Crystal data top
C8H8O3 | F(000) = 960 |
Mr = 152.14 | Dx = 1.424 Mg m−3 |
Orthorhombic, P212121 | Cu Kα radiation, λ = 1.54184 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 13155 reflections |
a = 6.7640 (3) Å | θ = 3.4–71.0° |
b = 13.1193 (6) Å | µ = 0.92 mm−1 |
c = 23.9936 (9) Å | T = 103 K |
V = 2129.17 (16) Å3 | Needle, colourless |
Z = 12 | 0.25 × 0.08 × 0.04 mm |
Data collection top
Oxford Diffraction Xcalibur Nova O diffractometer | 2327 independent reflections |
Radiation source: Nova (Cu) X-ray Source | 2185 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.027 |
Detector resolution: 8.3648 pixels mm-1 | θmax = 71.1°, θmin = 3.8° |
ω scans | h = −6→8 |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008) | k = −15→16 |
Tmin = 0.780, Tmax = 0.964 | l = −28→28 |
20232 measured reflections | |
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)] = 0.030 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.083 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.066P)2 + 0.1332P] where P = (Fo2 + 2Fc2)/3 |
2327 reflections | (Δ/σ)max = 0.001 |
325 parameters | Δρmax = 0.21 e Å−3 |
276 restraints | Δρmin = −0.21 e Å−3 |
Crystal data top
C8H8O3 | V = 2129.17 (16) Å3 |
Mr = 152.14 | Z = 12 |
Orthorhombic, P212121 | Cu Kα radiation |
a = 6.7640 (3) Å | µ = 0.92 mm−1 |
b = 13.1193 (6) Å | T = 103 K |
c = 23.9936 (9) Å | 0.25 × 0.08 × 0.04 mm |
Data collection top
Oxford Diffraction Xcalibur Nova O diffractometer | 2327 independent reflections |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008) | 2185 reflections with I > 2σ(I) |
Tmin = 0.780, Tmax = 0.964 | Rint = 0.027 |
20232 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.030 | 276 restraints |
wR(F2) = 0.083 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.21 e Å−3 |
2327 reflections | Δρmin = −0.21 e Å−3 |
325 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C11 | 0.3400 (3) | 0.40128 (12) | 0.20314 (6) | 0.0208 (3) | |
C12 | 0.3354 (3) | 0.46415 (11) | 0.24983 (7) | 0.0216 (3) | |
H12 | 0.3159 | 0.5355 | 0.2457 | 0.026* | |
C13 | 0.3594 (2) | 0.42244 (12) | 0.30239 (6) | 0.0203 (3) | |
C14 | 0.3906 (2) | 0.31620 (12) | 0.30962 (6) | 0.0200 (3) | |
C15 | 0.3956 (3) | 0.25564 (12) | 0.26135 (7) | 0.0217 (3) | |
H15 | 0.4164 | 0.1843 | 0.2651 | 0.026* | |
C16 | 0.3715 (3) | 0.29584 (11) | 0.20895 (6) | 0.0222 (4) | |
H16 | 0.3761 | 0.2530 | 0.1770 | 0.027* | |
C17 | 0.4108 (2) | 0.27223 (12) | 0.36493 (6) | 0.0207 (3) | |
C18 | 0.4389 (3) | 0.15947 (12) | 0.37181 (7) | 0.0259 (4) | |
H18A | 0.4588 | 0.1436 | 0.4113 | 0.039* | |
H18B | 0.5549 | 0.1375 | 0.3505 | 0.039* | |
H18C | 0.3214 | 0.1236 | 0.3581 | 0.039* | |
O11 | 0.31297 (19) | 0.44485 (9) | 0.15300 (5) | 0.0258 (3) | |
H111 | 0.313 (3) | 0.3981 (17) | 0.1284 (10) | 0.035 (6)* | |
O12 | 0.3520 (2) | 0.48663 (8) | 0.34677 (5) | 0.0262 (3) | |
H112 | 0.368 (4) | 0.4509 (19) | 0.3773 (12) | 0.051 (7)* | |
O13 | 0.40316 (19) | 0.32726 (9) | 0.40723 (5) | 0.0260 (3) | |
C21 | 0.4359 (3) | 0.28363 (12) | 0.55851 (7) | 0.0205 (3) | |
C22 | 0.4373 (3) | 0.32412 (12) | 0.61192 (7) | 0.0214 (3) | |
H22 | 0.4549 | 0.3953 | 0.6172 | 0.026* | |
C23 | 0.4131 (2) | 0.26072 (11) | 0.65741 (6) | 0.0198 (3) | |
C24 | 0.3873 (2) | 0.15368 (11) | 0.65035 (6) | 0.0188 (3) | |
C25 | 0.3838 (3) | 0.11589 (12) | 0.59548 (6) | 0.0213 (3) | |
H25 | 0.3646 | 0.0449 | 0.5897 | 0.026* | |
C26 | 0.4074 (3) | 0.17867 (12) | 0.54997 (6) | 0.0221 (3) | |
H26 | 0.4044 | 0.1514 | 0.5133 | 0.027* | |
C27 | 0.3664 (2) | 0.08772 (12) | 0.69875 (7) | 0.0209 (3) | |
C28 | 0.3508 (3) | −0.02619 (12) | 0.69194 (7) | 0.0273 (4) | |
H28A | 0.3558 | −0.0588 | 0.7287 | 0.041* | |
H28B | 0.4609 | −0.0507 | 0.6691 | 0.041* | |
H28C | 0.2254 | −0.0431 | 0.6737 | 0.041* | |
O21 | 0.4635 (2) | 0.34990 (8) | 0.51629 (5) | 0.0273 (3) | |
H121 | 0.452 (4) | 0.317 (2) | 0.4864 (11) | 0.044 (6)* | |
O22 | 0.4129 (2) | 0.30461 (9) | 0.70836 (5) | 0.0256 (3) | |
H122 | 0.392 (4) | 0.255 (2) | 0.7314 (11) | 0.051 (7)* | |
O23 | 0.36192 (19) | 0.12502 (9) | 0.74660 (4) | 0.0249 (3) | |
C31 | 0.3192 (3) | 0.11514 (12) | 0.88848 (6) | 0.0198 (3) | |
C32 | 0.3163 (3) | 0.08269 (11) | 0.94379 (6) | 0.0207 (3) | |
H32 | 0.3178 | 0.0119 | 0.9522 | 0.025* | |
C33 | 0.3112 (2) | 0.15340 (12) | 0.98649 (6) | 0.0194 (3) | |
C34 | 0.3090 (3) | 0.25978 (12) | 0.97507 (6) | 0.0187 (3) | |
C35 | 0.3095 (3) | 0.28943 (12) | 0.91848 (6) | 0.0211 (3) | |
H35 | 0.3064 | 0.3600 | 0.9097 | 0.025* | |
C36 | 0.3144 (3) | 0.22004 (12) | 0.87595 (6) | 0.0217 (3) | |
H36 | 0.3146 | 0.2424 | 0.8383 | 0.026* | |
C37 | 0.3087 (2) | 0.33376 (12) | 1.02014 (7) | 0.0202 (3) | |
C38 | 0.3085 (3) | 0.44614 (11) | 1.00702 (7) | 0.0245 (4) | |
H38A | 0.3048 | 0.4852 | 1.0418 | 0.037* | |
H38B | 0.1919 | 0.4628 | 0.9845 | 0.037* | |
H38C | 0.4284 | 0.4635 | 0.9862 | 0.037* | |
O31 | 0.32632 (19) | 0.04311 (8) | 0.84877 (5) | 0.0242 (3) | |
H131 | 0.328 (4) | 0.0703 (18) | 0.8167 (11) | 0.041 (6)* | |
O32 | 0.3096 (2) | 0.11749 (9) | 1.03946 (4) | 0.0249 (3) | |
H132 | 0.313 (4) | 0.171 (2) | 1.0595 (11) | 0.048 (7)* | |
O33 | 0.3097 (2) | 0.30534 (8) | 1.06971 (4) | 0.0235 (3) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C11 | 0.0190 (8) | 0.0227 (7) | 0.0207 (7) | −0.0030 (6) | 0.0011 (7) | 0.0017 (6) |
C12 | 0.0224 (8) | 0.0170 (6) | 0.0253 (8) | −0.0015 (7) | 0.0014 (7) | −0.0008 (6) |
C13 | 0.0188 (8) | 0.0204 (7) | 0.0217 (7) | −0.0014 (6) | 0.0010 (7) | −0.0023 (6) |
C14 | 0.0171 (8) | 0.0212 (7) | 0.0218 (7) | −0.0012 (6) | 0.0003 (6) | 0.0009 (6) |
C15 | 0.0221 (8) | 0.0183 (7) | 0.0247 (7) | −0.0016 (7) | 0.0014 (7) | −0.0011 (6) |
C16 | 0.0245 (9) | 0.0192 (7) | 0.0227 (7) | 0.0002 (7) | 0.0010 (7) | −0.0051 (6) |
C17 | 0.0150 (8) | 0.0250 (7) | 0.0221 (7) | −0.0013 (7) | 0.0007 (6) | 0.0014 (6) |
C18 | 0.0270 (9) | 0.0236 (8) | 0.0270 (8) | 0.0007 (7) | 0.0008 (7) | 0.0042 (6) |
O11 | 0.0359 (7) | 0.0224 (5) | 0.0190 (5) | −0.0009 (5) | −0.0018 (5) | −0.0005 (5) |
O12 | 0.0380 (7) | 0.0205 (5) | 0.0201 (5) | 0.0007 (5) | 0.0004 (5) | −0.0034 (4) |
O13 | 0.0302 (7) | 0.0269 (6) | 0.0209 (5) | −0.0019 (5) | 0.0003 (5) | −0.0005 (4) |
C21 | 0.0195 (8) | 0.0205 (7) | 0.0214 (7) | 0.0015 (7) | 0.0013 (7) | 0.0005 (6) |
C22 | 0.0199 (8) | 0.0182 (7) | 0.0262 (8) | 0.0003 (6) | −0.0011 (7) | −0.0012 (6) |
C23 | 0.0166 (8) | 0.0212 (7) | 0.0214 (7) | 0.0020 (6) | −0.0008 (6) | −0.0040 (6) |
C24 | 0.0185 (8) | 0.0177 (7) | 0.0202 (7) | 0.0015 (6) | 0.0001 (6) | −0.0005 (6) |
C25 | 0.0224 (9) | 0.0185 (7) | 0.0230 (7) | −0.0007 (7) | 0.0018 (7) | −0.0028 (6) |
C26 | 0.0252 (9) | 0.0222 (7) | 0.0188 (7) | 0.0012 (7) | −0.0006 (7) | −0.0025 (6) |
C27 | 0.0174 (8) | 0.0228 (7) | 0.0223 (7) | 0.0018 (7) | −0.0002 (7) | 0.0000 (6) |
C28 | 0.0325 (10) | 0.0209 (7) | 0.0283 (8) | −0.0006 (7) | 0.0030 (8) | 0.0043 (6) |
O21 | 0.0428 (8) | 0.0209 (5) | 0.0182 (5) | −0.0004 (6) | 0.0026 (5) | 0.0019 (4) |
O22 | 0.0371 (7) | 0.0214 (5) | 0.0184 (5) | 0.0009 (5) | −0.0012 (5) | −0.0038 (4) |
O23 | 0.0294 (7) | 0.0253 (5) | 0.0199 (5) | 0.0029 (5) | 0.0002 (5) | 0.0012 (4) |
C31 | 0.0174 (8) | 0.0203 (7) | 0.0217 (7) | 0.0004 (7) | −0.0002 (6) | 0.0000 (6) |
C32 | 0.0224 (8) | 0.0167 (6) | 0.0230 (7) | −0.0004 (7) | 0.0005 (7) | 0.0020 (6) |
C33 | 0.0182 (8) | 0.0195 (7) | 0.0206 (7) | −0.0011 (7) | −0.0001 (7) | 0.0034 (6) |
C34 | 0.0177 (8) | 0.0188 (7) | 0.0196 (7) | 0.0002 (7) | 0.0000 (6) | 0.0016 (6) |
C35 | 0.0224 (8) | 0.0179 (7) | 0.0231 (7) | 0.0002 (7) | 0.0006 (7) | 0.0036 (6) |
C36 | 0.0250 (8) | 0.0219 (7) | 0.0183 (7) | 0.0003 (7) | 0.0006 (7) | 0.0031 (6) |
C37 | 0.0162 (8) | 0.0221 (7) | 0.0222 (7) | 0.0006 (7) | 0.0005 (7) | 0.0011 (6) |
C38 | 0.0314 (9) | 0.0181 (7) | 0.0241 (7) | −0.0014 (7) | 0.0022 (7) | −0.0018 (6) |
O31 | 0.0345 (7) | 0.0199 (5) | 0.0184 (5) | 0.0002 (5) | 0.0009 (5) | −0.0004 (4) |
O32 | 0.0376 (7) | 0.0189 (5) | 0.0183 (5) | −0.0005 (6) | 0.0006 (5) | 0.0031 (4) |
O33 | 0.0270 (6) | 0.0227 (5) | 0.0208 (5) | 0.0001 (5) | 0.0007 (5) | −0.0005 (4) |
Geometric parameters (Å, º) top
C11—O11 | 1.3445 (19) | C34—C37 | 1.453 (2) |
C11—C12 | 1.392 (2) | C35—C36 | 1.368 (2) |
C11—C16 | 1.407 (2) | C37—O33 | 1.246 (2) |
C12—C13 | 1.384 (2) | C37—C38 | 1.508 (2) |
C13—O12 | 1.3584 (19) | C12—H12 | 0.9500 |
C13—C14 | 1.420 (2) | C15—H15 | 0.9500 |
C14—C15 | 1.405 (2) | C16—H16 | 0.9500 |
C14—C17 | 1.454 (2) | C18—H18A | 0.9800 |
C15—C16 | 1.373 (2) | C18—H18B | 0.9800 |
C17—O13 | 1.247 (2) | C18—H18C | 0.9800 |
C17—C18 | 1.501 (2) | O11—H111 | 0.85 (2) |
C21—O21 | 1.3480 (19) | O12—H112 | 0.88 (3) |
C21—C22 | 1.387 (2) | C22—H22 | 0.9500 |
C21—C26 | 1.405 (2) | C25—H25 | 0.9500 |
C22—C23 | 1.382 (2) | C26—H26 | 0.9500 |
C23—O22 | 1.3513 (18) | C28—H28A | 0.9800 |
C23—C24 | 1.425 (2) | C28—H28B | 0.9800 |
C24—C25 | 1.407 (2) | C28—H28C | 0.9800 |
C24—C27 | 1.455 (2) | O21—H121 | 0.84 (3) |
C25—C26 | 1.377 (2) | O22—H122 | 0.86 (3) |
C27—O23 | 1.2484 (19) | C32—H32 | 0.9500 |
C27—C28 | 1.507 (2) | C35—H35 | 0.9500 |
C31—O31 | 1.3427 (19) | C36—H36 | 0.9500 |
C31—C32 | 1.394 (2) | C38—H38A | 0.9800 |
C31—C36 | 1.409 (2) | C38—H38B | 0.9800 |
C32—C33 | 1.382 (2) | C38—H38C | 0.9800 |
C33—O32 | 1.3555 (18) | O31—H131 | 0.85 (3) |
C33—C34 | 1.422 (2) | O32—H132 | 0.85 (3) |
C34—C35 | 1.412 (2) | | |
| | | |
O11—C11—C12 | 117.74 (13) | C34—C37—C38 | 119.87 (14) |
O11—C11—C16 | 121.83 (13) | C13—C12—H12 | 120.1 |
C12—C11—C16 | 120.44 (14) | C11—C12—H12 | 120.1 |
C13—C12—C11 | 119.77 (14) | C16—C15—H15 | 118.8 |
O12—C13—C12 | 117.68 (13) | C14—C15—H15 | 118.8 |
O12—C13—C14 | 121.22 (14) | C15—C16—H16 | 120.4 |
C12—C13—C14 | 121.10 (14) | C11—C16—H16 | 120.4 |
C15—C14—C13 | 117.26 (14) | C17—C18—H18A | 109.5 |
C15—C14—C17 | 121.73 (13) | C17—C18—H18B | 109.5 |
C13—C14—C17 | 120.99 (14) | H18A—C18—H18B | 109.5 |
C16—C15—C14 | 122.33 (14) | C17—C18—H18C | 109.5 |
C15—C16—C11 | 119.10 (14) | H18A—C18—H18C | 109.5 |
O13—C17—C14 | 120.63 (14) | H18B—C18—H18C | 109.5 |
O13—C17—C18 | 119.13 (14) | C11—O11—H111 | 108.3 (15) |
C14—C17—C18 | 120.23 (14) | C13—O12—H112 | 108.6 (17) |
O21—C21—C22 | 116.51 (14) | C23—C22—H22 | 120.1 |
O21—C21—C26 | 122.77 (15) | C21—C22—H22 | 120.1 |
C22—C21—C26 | 120.72 (15) | C26—C25—H25 | 119.0 |
C23—C22—C21 | 119.89 (14) | C24—C25—H25 | 119.0 |
O22—C23—C22 | 117.27 (13) | C25—C26—H26 | 120.5 |
O22—C23—C24 | 121.82 (14) | C21—C26—H26 | 120.5 |
C22—C23—C24 | 120.91 (14) | C27—C28—H28A | 109.5 |
C25—C24—C23 | 117.41 (14) | C27—C28—H28B | 109.5 |
C25—C24—C27 | 122.39 (13) | H28A—C28—H28B | 109.5 |
C23—C24—C27 | 120.20 (14) | C27—C28—H28C | 109.5 |
C26—C25—C24 | 121.96 (14) | H28A—C28—H28C | 109.5 |
C25—C26—C21 | 119.09 (14) | H28B—C28—H28C | 109.5 |
O23—C27—C24 | 120.21 (14) | C21—O21—H121 | 107.3 (17) |
O23—C27—C28 | 119.13 (14) | C23—O22—H122 | 105.1 (17) |
C24—C27—C28 | 120.66 (14) | C33—C32—H32 | 120.0 |
O31—C31—C32 | 117.45 (13) | C31—C32—H32 | 120.0 |
O31—C31—C36 | 122.47 (14) | C36—C35—H35 | 118.9 |
C32—C31—C36 | 120.08 (14) | C34—C35—H35 | 118.9 |
C33—C32—C31 | 120.06 (14) | C35—C36—H36 | 120.3 |
O32—C33—C32 | 117.50 (13) | C31—C36—H36 | 120.3 |
O32—C33—C34 | 121.43 (14) | C37—C38—H38A | 109.5 |
C32—C33—C34 | 121.06 (14) | C37—C38—H38B | 109.5 |
C35—C34—C33 | 117.09 (14) | H38A—C38—H38B | 109.5 |
C35—C34—C37 | 122.10 (14) | C37—C38—H38C | 109.5 |
C33—C34—C37 | 120.81 (14) | H38A—C38—H38C | 109.5 |
C36—C35—C34 | 122.27 (14) | H38B—C38—H38C | 109.5 |
C35—C36—C31 | 119.43 (14) | C31—O31—H131 | 110.4 (16) |
O33—C37—C34 | 120.68 (14) | C33—O32—H132 | 104.3 (17) |
O33—C37—C38 | 119.46 (14) | | |
| | | |
O11—C11—C12—C13 | 178.99 (16) | C27—C24—C25—C26 | −178.77 (16) |
C16—C11—C12—C13 | −0.9 (3) | C24—C25—C26—C21 | 0.0 (3) |
C11—C12—C13—O12 | −179.40 (15) | O21—C21—C26—C25 | 178.83 (15) |
C11—C12—C13—C14 | 0.6 (3) | C22—C21—C26—C25 | −1.0 (3) |
O12—C13—C14—C15 | 179.87 (15) | C25—C24—C27—O23 | −176.94 (16) |
C12—C13—C14—C15 | −0.1 (3) | C23—C24—C27—O23 | 3.3 (2) |
O12—C13—C14—C17 | 1.5 (3) | C25—C24—C27—C28 | 3.3 (3) |
C12—C13—C14—C17 | −178.46 (15) | C23—C24—C27—C28 | −176.47 (16) |
C13—C14—C15—C16 | −0.1 (3) | O31—C31—C32—C33 | 179.27 (15) |
C17—C14—C15—C16 | 178.28 (16) | C36—C31—C32—C33 | −0.8 (3) |
C14—C15—C16—C11 | −0.2 (3) | C31—C32—C33—O32 | −179.65 (16) |
O11—C11—C16—C15 | −179.15 (15) | C31—C32—C33—C34 | −0.1 (3) |
C12—C11—C16—C15 | 0.7 (3) | O32—C33—C34—C35 | −179.58 (15) |
C15—C14—C17—O13 | −178.99 (16) | C32—C33—C34—C35 | 0.8 (3) |
C13—C14—C17—O13 | −0.7 (3) | O32—C33—C34—C37 | 1.1 (3) |
C15—C14—C17—C18 | 0.3 (2) | C32—C33—C34—C37 | −178.44 (15) |
C13—C14—C17—C18 | 178.56 (16) | C33—C34—C35—C36 | −0.8 (3) |
O21—C21—C22—C23 | −178.99 (15) | C37—C34—C35—C36 | 178.47 (16) |
C26—C21—C22—C23 | 0.8 (3) | C34—C35—C36—C31 | 0.0 (3) |
C21—C22—C23—O22 | −179.05 (15) | O31—C31—C36—C35 | −179.24 (15) |
C21—C22—C23—C24 | 0.2 (3) | C32—C31—C36—C35 | 0.8 (3) |
O22—C23—C24—C25 | 178.11 (15) | C35—C34—C37—O33 | −179.47 (15) |
C22—C23—C24—C25 | −1.2 (2) | C33—C34—C37—O33 | −0.2 (3) |
O22—C23—C24—C27 | −2.1 (3) | C35—C34—C37—C38 | 0.1 (3) |
C22—C23—C24—C27 | 178.63 (15) | C33—C34—C37—C38 | 179.39 (16) |
C23—C24—C25—C26 | 1.0 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O11—H111···O33i | 0.85 (2) | 1.86 (2) | 2.7101 (16) | 175 (2) |
O12—H112···O13 | 0.88 (3) | 1.79 (3) | 2.5682 (16) | 147 (2) |
O21—H121···O13 | 0.84 (3) | 1.93 (3) | 2.6650 (16) | 145 (2) |
O22—H122···O23 | 0.86 (3) | 1.76 (3) | 2.5519 (16) | 152 (2) |
O31—H131···O23 | 0.85 (3) | 1.84 (3) | 2.6875 (15) | 174 (2) |
O32—H132···O33 | 0.85 (3) | 1.79 (3) | 2.5691 (15) | 153 (2) |
C28—H28C···O12ii | 0.98 | 2.68 | 3.537 (2) | 147 |
C18—H18C···O31iii | 0.98 | 2.42 | 3.254 (2) | 143 |
C22—H22···O31iv | 0.95 | 2.57 | 3.421 (2) | 149 |
Symmetry codes: (i) x, y, z−1; (ii) x−1/2, −y+1/2, −z+1; (iii) −x+1/2, −y, z−1/2; (iv) −x+1, y+1/2, −z+3/2. |
Experimental details
| (IM) | (IO) |
Crystal data |
Chemical formula | C8H8O3 | C8H8O3 |
Mr | 152.14 | 152.14 |
Crystal system, space group | Monoclinic, P21/c | Orthorhombic, P212121 |
Temperature (K) | 100 | 103 |
a, b, c (Å) | 7.1194 (3), 13.6690 (6), 7.2695 (4) | 6.7640 (3), 13.1193 (6), 23.9936 (9) |
α, β, γ (°) | 90, 92.859 (6), 90 | 90, 90, 90 |
V (Å3) | 706.55 (6) | 2129.17 (16) |
Z | 4 | 12 |
Radiation type | Mo Kα | Cu Kα |
µ (mm−1) | 0.11 | 0.92 |
Crystal size (mm) | 0.40 × 0.40 × 0.25 | 0.25 × 0.08 × 0.04 |
|
Data collection |
Diffractometer | Oxford Diffraction Xcalibur S diffractometer | Oxford Diffraction Xcalibur Nova O diffractometer |
Absorption correction | – | Multi-scan (CrysAlis RED; Oxford Diffraction, 2008) |
Tmin, Tmax | – | 0.780, 0.964 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12428, 2149, 1508 | 20232, 2327, 2185 |
Rint | 0.042 | 0.027 |
(sin θ/λ)max (Å−1) | 0.714 | 0.614 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.105, 0.95 | 0.030, 0.083, 1.04 |
No. of reflections | 2149 | 2327 |
No. of parameters | 109 | 325 |
No. of restraints | 0 | 276 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.43, −0.25 | 0.21, −0.21 |
Hydrogen-bond geometry (Å, º) for (IM) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H11···O3i | 0.908 (19) | 1.807 (18) | 2.6466 (10) | 152.7 (17) |
O2—H12···O3 | 0.896 (18) | 1.743 (18) | 2.5610 (11) | 150.5 (16) |
C6—H6···O1ii | 0.95 | 2.56 | 3.4759 (13) | 161.3 |
C5—H5···O2iii | 0.95 | 2.46 | 3.3127 (13) | 149.2 |
Symmetry codes: (i) x+1, −y+1/2, z−1/2; (ii) −x+2, −y, −z; (iii) −x+1, y−1/2, −z+1/2. |
Hydrogen-bond geometry (Å, º) for (IO) top
D—H···A | D—H | H···A | D···A | D—H···A |
O11—H111···O33i | 0.85 (2) | 1.86 (2) | 2.7101 (16) | 175 (2) |
O12—H112···O13 | 0.88 (3) | 1.79 (3) | 2.5682 (16) | 147 (2) |
O21—H121···O13 | 0.84 (3) | 1.93 (3) | 2.6650 (16) | 145 (2) |
O22—H122···O23 | 0.86 (3) | 1.76 (3) | 2.5519 (16) | 152 (2) |
O31—H131···O23 | 0.85 (3) | 1.84 (3) | 2.6875 (15) | 174 (2) |
O32—H132···O33 | 0.85 (3) | 1.79 (3) | 2.5691 (15) | 153 (2) |
C28—H28C···O12ii | 0.98 | 2.68 | 3.537 (2) | 146.7 |
C18—H18C···O31iii | 0.98 | 2.42 | 3.254 (2) | 143.2 |
C22—H22···O31iv | 0.95 | 2.57 | 3.421 (2) | 148.8 |
Symmetry codes: (i) x, y, z−1; (ii) x−1/2, −y+1/2, −z+1; (iii) −x+1/2, −y, z−1/2; (iv) −x+1, y+1/2, −z+3/2. |
In the course of synthetic approaches to coronand systems, the title compound was obtained in crystalline form as an unexpected product. The sample consisted of two types of crystal, large blocks and a smaller quantity of fine needles. Data were measured for a block and corresponded to the known structure of 4-acetylresorcinol, (I) (monoclinic, space group P21/c, Z = 4; Robert et al., 2007). The needles were also measured and it was clear that the asymmetric unit was much larger, but it proved to contain three independent molecules of the same compound (P212121, Z = 12). This is a new polymorph of (I). In view of our interest in the structures of polymorphs (see e.g. Jones & Lozano, 2003a,b; Ossowski et al., 2006; Kuś et al., 2009), and because the structure of Robert et al. (2007) was based on room-temperature data, we retained the low-temperature data of the known polymorph and present here a comparison of the two forms.
The molecule of the monoclinic form, henceforth form (IM), is shown in Fig. 1. Except for the methyl H atoms, it is planar (r.m.s. deviation 0.03 Å). Bond lengths and angles may be regarded as normal. There is an intramolecular O2—H12···O3 hydrogen bond.
The three molecules of the orthorhombic polymorph, henceforth form (IO), connected within the asymmetric unit by hydrogen bonds, are shown in Fig. 2. The molecules are again planar (r.m.s. deviations excluding methyl H atoms 0.03, 0.03, 0.02 Å) and approximately parallel [interplanar angles between molecules 1 and 2 16.27 (4)°, and between molecules 2 and 3 8.27 (3)°]. They are closely similar to each other and to the molecule of the monoclinic form, but there is one important conformational difference: the OH groups are oriented in the same sense in form (IM) (anticlockwise in the plane of Fig. 1), but in the opposite sense in all three molecules of form (IO). Furthermore, the third molecule of form (IO) has the opposite rotational sense in the common plane to the other two (see e.g. the ring atoms, which are clockwise 1–6 for the third molecule but anticlockwise for molecules 1 and 2).
The packing of form (IM) was described briefly by Robert et al. (2007) and the intermolecular O2—H12···O3 hydrogen bond was recognized. The extended packing (Fig. 3) consists of layers parallel to (102), in which the classical hydrogen bonds link the molecules into zigzag chains parallel to [201]. Two C—H···O interactions from ring H atoms to the hydroxyl groups (Table 1) provide the crosslinking.
The crystal structure of form (IO) contains chains of molecules parallel to the c axis, generated by O—H···O hydrogen bonds (Fig. 4, Table 2). The C22—H22···O31 interaction crosslinks the chains to form a layer structure. In contrast with form (IM), however, neighbouring chains are displaced in the third dimension. Chains are weakly linked to those above and below by C—H···O contacts (not shown in Fig. 4) involving the methyl H atoms H18C and H28C.
It is tempting to regard the almost exactly planar layer structure of form (IM) as the energy minimum for the packing of (I), whereas the offset layer structure of form (IO) could be regarded as a kinetic stopping-off point on the way to form (IM). This is consistent with the slightly higher density of form (IM), 1.430 Mg m-3, versus 1.424 Mg m-3 for form (IO). However, more detailed theoretical and physical studies would be necessary to prove this supposition.