During a polymorphism screening of hydroxybenzophenone derivatives, a monohydrate pseudopolymorph of (3,4-dihydroxyphenyl)(phenyl)methanone, C
13H
10O
3·H
2O, (I), was obtained. Structural relationships and the role of water in crystal assembly were established on the basis of the known anhydrous form [Cox, Kechagias & Kelly (2008).
Acta Cryst. B
64, 206–216]. The crystal packing of (I) is stabilized by classical intermolecular O—H
O hydrogen bonds, generating a three-dimensional network.
Supporting information
CCDC reference: 796078
Commercial 3,4-dihydroxybenzophenone (Sigma–Aldrich) was used. Colourless
prismatic crystals of (I) were obtained from a solution in a mixture of water,
ethanol and methanol (1:1:1 v/v) by slow evaporation at room
temperature.
All H atoms were located in a difference Fourier synthesis. Those bound to C
atoms and the 3- and 4-hydroxy groups were subsequently allowed for as riding
on their parent atoms, with C—H = 0.93 and O—H = 0.82 Å [Please check
added text], and with Uiso(H) = 1.2Ueq for phenyl H
atoms. Water H atoms were located by difference Fourier synthesis and their
coordinates restrained using a restraint of O—H = 0.97 (2) Å. For all H
atoms bonded to O, Uiso(H) = 1.5Ueq(O).
Data collection: COLLECT (Nonius, 2000); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997) and SCALEPACK (Otwinowski & Minor,
1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al.,
2006); software used to prepare material for publication: WinGX (Farrugia, 1999).
(3,4-dihydroxyphenyl)(phenyl)methanone monohydrate
top
Crystal data top
C13H10O3·H2O | F(000) = 488 |
Mr = 232.23 | Dx = 1.358 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2483 reflections |
a = 4.2920 (1) Å | θ = 0.4–27.5° |
b = 23.2084 (7) Å | µ = 0.10 mm−1 |
c = 11.4552 (3) Å | T = 298 K |
β = 95.393 (2)° | Prism, colourless |
V = 1136.01 (5) Å3 | 0.60 × 0.15 × 0.09 mm |
Z = 4 | |
Data collection top
Nonius KappaCCD area-detector diffractometer | Rint = 0.032 |
Graphite monochromator | θmax = 27.1°, θmin = 2.5° |
CCD rotation images, thick slices scans | h = −5→5 |
4756 measured reflections | k = −29→29 |
2444 independent reflections | l = −14→14 |
1692 reflections with I > 2σ(I) | |
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)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.158 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0986P)2] where P = (Fo2 + 2Fc2)/3 |
2444 reflections | (Δ/σ)max < 0.001 |
159 parameters | Δρmax = 0.20 e Å−3 |
2 restraints | Δρmin = −0.16 e Å−3 |
Crystal data top
C13H10O3·H2O | V = 1136.01 (5) Å3 |
Mr = 232.23 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 4.2920 (1) Å | µ = 0.10 mm−1 |
b = 23.2084 (7) Å | T = 298 K |
c = 11.4552 (3) Å | 0.60 × 0.15 × 0.09 mm |
β = 95.393 (2)° | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 1692 reflections with I > 2σ(I) |
4756 measured reflections | Rint = 0.032 |
2444 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.050 | 2 restraints |
wR(F2) = 0.158 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.20 e Å−3 |
2444 reflections | Δρmin = −0.16 e Å−3 |
159 parameters | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
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 > 2sigma(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 | 0.6007 (3) | 0.28115 (6) | 0.68593 (13) | 0.0494 (4) | |
C2 | 0.7382 (3) | 0.29750 (6) | 0.58467 (13) | 0.0491 (4) | |
H2 | 0.8394 | 0.27 | 0.5427 | 0.059* | |
C3 | 0.7248 (3) | 0.35352 (6) | 0.54704 (12) | 0.0465 (4) | |
C4 | 0.5614 (3) | 0.39440 (6) | 0.60748 (13) | 0.0493 (4) | |
C5 | 0.4238 (4) | 0.37831 (7) | 0.70710 (13) | 0.0547 (4) | |
H5 | 0.3159 | 0.4054 | 0.7475 | 0.066* | |
C6 | 0.4467 (4) | 0.32225 (7) | 0.74635 (13) | 0.0549 (4) | |
H6 | 0.3576 | 0.3119 | 0.8143 | 0.066* | |
C7 | 0.6235 (4) | 0.22207 (6) | 0.73364 (13) | 0.0535 (4) | |
C8 | 0.6543 (3) | 0.17132 (6) | 0.65680 (12) | 0.0508 (4) | |
C9 | 0.5074 (3) | 0.16865 (7) | 0.54319 (13) | 0.0553 (4) | |
H9 | 0.3957 | 0.2002 | 0.5117 | 0.066* | |
C10 | 0.5274 (4) | 0.11913 (7) | 0.47726 (15) | 0.0642 (5) | |
H10 | 0.4234 | 0.1171 | 0.4024 | 0.077* | |
C11 | 0.6998 (4) | 0.07285 (7) | 0.52163 (16) | 0.0702 (5) | |
H11 | 0.7168 | 0.0401 | 0.4759 | 0.084* | |
C12 | 0.8472 (5) | 0.07488 (7) | 0.63341 (17) | 0.0737 (5) | |
H12 | 0.9635 | 0.0435 | 0.6631 | 0.088* | |
C13 | 0.8233 (4) | 0.12357 (7) | 0.70198 (15) | 0.0621 (5) | |
H13 | 0.9198 | 0.1245 | 0.7781 | 0.075* | |
O1 | 0.6130 (3) | 0.21489 (5) | 0.84058 (10) | 0.0723 (4) | |
O2 | 0.5506 (3) | 0.44891 (5) | 0.56491 (10) | 0.0612 (4) | |
H21 | 0.4124 | 0.4669 | 0.5937 | 0.092* | |
O3 | 0.8637 (2) | 0.37325 (4) | 0.45200 (9) | 0.0571 (4) | |
H3 | 0.942 | 0.3461 | 0.4194 | 0.086* | |
O4 | 0.1104 (3) | 0.51183 (5) | 0.64695 (10) | 0.0643 (4) | |
H41 | 0.126 | 0.5468 | 0.6075 | 0.096* | |
H42 | −0.0909 | 0.4982 | 0.6296 | 0.096* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0575 (9) | 0.0462 (8) | 0.0447 (8) | −0.0037 (6) | 0.0059 (6) | 0.0015 (6) |
C2 | 0.0586 (9) | 0.0430 (8) | 0.0458 (8) | −0.0006 (6) | 0.0063 (6) | 0.0003 (6) |
C3 | 0.0539 (8) | 0.0427 (8) | 0.0435 (8) | −0.0046 (6) | 0.0073 (6) | 0.0014 (6) |
C4 | 0.0560 (8) | 0.0402 (8) | 0.0518 (8) | −0.0013 (6) | 0.0047 (6) | 0.0022 (6) |
C5 | 0.0636 (9) | 0.0483 (9) | 0.0536 (9) | 0.0031 (7) | 0.0129 (7) | −0.0013 (6) |
C6 | 0.0649 (9) | 0.0545 (9) | 0.0465 (8) | −0.0051 (7) | 0.0120 (7) | 0.0019 (7) |
C7 | 0.0626 (9) | 0.0507 (9) | 0.0480 (9) | −0.0055 (6) | 0.0083 (7) | 0.0048 (6) |
C8 | 0.0582 (9) | 0.0435 (8) | 0.0516 (9) | −0.0042 (6) | 0.0100 (7) | 0.0060 (6) |
C9 | 0.0613 (9) | 0.0501 (9) | 0.0551 (9) | −0.0030 (7) | 0.0074 (7) | 0.0048 (7) |
C10 | 0.0751 (11) | 0.0619 (11) | 0.0558 (10) | −0.0130 (8) | 0.0075 (8) | −0.0024 (8) |
C11 | 0.0892 (13) | 0.0510 (10) | 0.0737 (13) | −0.0052 (8) | 0.0256 (10) | −0.0064 (8) |
C12 | 0.0918 (13) | 0.0549 (11) | 0.0764 (12) | 0.0131 (9) | 0.0186 (10) | 0.0098 (9) |
C13 | 0.0725 (11) | 0.0558 (10) | 0.0584 (10) | 0.0028 (8) | 0.0077 (8) | 0.0094 (7) |
O1 | 0.1144 (10) | 0.0567 (8) | 0.0474 (7) | −0.0051 (6) | 0.0153 (6) | 0.0082 (5) |
O2 | 0.0732 (7) | 0.0424 (6) | 0.0709 (8) | 0.0044 (5) | 0.0216 (6) | 0.0058 (5) |
O3 | 0.0774 (8) | 0.0423 (6) | 0.0545 (7) | 0.0022 (5) | 0.0217 (5) | 0.0051 (4) |
O4 | 0.0714 (8) | 0.0524 (7) | 0.0705 (8) | 0.0024 (5) | 0.0142 (6) | 0.0024 (5) |
Geometric parameters (Å, º) top
C1—C6 | 1.383 (2) | C8—C13 | 1.397 (2) |
C1—C2 | 1.4023 (19) | C9—C10 | 1.382 (2) |
C1—C7 | 1.476 (2) | C9—H9 | 0.93 |
C2—C3 | 1.3694 (19) | C10—C11 | 1.374 (2) |
C2—H2 | 0.93 | C10—H10 | 0.93 |
C3—O3 | 1.3682 (16) | C11—C12 | 1.375 (2) |
C3—C4 | 1.401 (2) | C11—H11 | 0.93 |
C4—O2 | 1.3550 (17) | C12—C13 | 1.385 (2) |
C4—C5 | 1.385 (2) | C12—H12 | 0.93 |
C5—C6 | 1.377 (2) | C13—H13 | 0.93 |
C5—H5 | 0.93 | O2—H21 | 0.82 |
C6—H6 | 0.93 | O3—H3 | 0.82 |
C7—O1 | 1.2413 (17) | O4—H41 | 0.9336 |
C7—C8 | 1.484 (2) | O4—H42 | 0.9239 |
C8—C9 | 1.3932 (19) | | |
| | | |
C6—C1—C2 | 119.05 (13) | C9—C8—C13 | 118.99 (14) |
C6—C1—C7 | 118.29 (13) | C9—C8—C7 | 122.12 (13) |
C2—C1—C7 | 122.63 (13) | C13—C8—C7 | 118.82 (14) |
C3—C2—C1 | 120.59 (14) | C10—C9—C8 | 120.09 (15) |
C3—C2—H2 | 119.7 | C10—C9—H9 | 120 |
C1—C2—H2 | 119.7 | C8—C9—H9 | 120 |
O3—C3—C2 | 124.03 (13) | C11—C10—C9 | 120.43 (17) |
O3—C3—C4 | 116.26 (13) | C11—C10—H10 | 119.8 |
C2—C3—C4 | 119.71 (13) | C9—C10—H10 | 119.8 |
O2—C4—C5 | 123.06 (14) | C10—C11—C12 | 120.16 (17) |
O2—C4—C3 | 117.15 (13) | C10—C11—H11 | 119.9 |
C5—C4—C3 | 119.79 (14) | C12—C11—H11 | 119.9 |
C6—C5—C4 | 120.07 (14) | C11—C12—C13 | 120.26 (17) |
C6—C5—H5 | 120 | C11—C12—H12 | 119.9 |
C4—C5—H5 | 120 | C13—C12—H12 | 119.9 |
C5—C6—C1 | 120.75 (14) | C12—C13—C8 | 120.03 (17) |
C5—C6—H6 | 119.6 | C12—C13—H13 | 120 |
C1—C6—H6 | 119.6 | C8—C13—H13 | 120 |
O1—C7—C1 | 118.86 (13) | C4—O2—H21 | 109.5 |
O1—C7—C8 | 119.51 (13) | C3—O3—H3 | 109.5 |
C1—C7—C8 | 121.62 (13) | H41—O4—H42 | 107.5 |
| | | |
C6—C1—C2—C3 | 1.0 (2) | C6—C1—C7—C8 | 153.25 (14) |
C7—C1—C2—C3 | −176.58 (14) | C2—C1—C7—C8 | −29.1 (2) |
C1—C2—C3—O3 | 177.29 (13) | O1—C7—C8—C9 | 144.32 (16) |
C1—C2—C3—C4 | −2.6 (2) | C1—C7—C8—C9 | −34.8 (2) |
O3—C3—C4—O2 | 1.4 (2) | O1—C7—C8—C13 | −32.4 (2) |
C2—C3—C4—O2 | −178.68 (13) | C1—C7—C8—C13 | 148.41 (15) |
O3—C3—C4—C5 | −177.70 (13) | C13—C8—C9—C10 | 0.6 (2) |
C2—C3—C4—C5 | 2.2 (2) | C7—C8—C9—C10 | −176.13 (14) |
O2—C4—C5—C6 | −179.27 (13) | C8—C9—C10—C11 | −2.0 (2) |
C3—C4—C5—C6 | −0.2 (2) | C9—C10—C11—C12 | 1.8 (3) |
C4—C5—C6—C1 | −1.4 (2) | C10—C11—C12—C13 | −0.1 (3) |
C2—C1—C6—C5 | 1.0 (2) | C11—C12—C13—C8 | −1.3 (3) |
C7—C1—C6—C5 | 178.70 (14) | C9—C8—C13—C12 | 1.1 (2) |
C6—C1—C7—O1 | −25.9 (2) | C7—C8—C13—C12 | 177.90 (14) |
C2—C1—C7—O1 | 151.72 (16) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H21···O4 | 0.82 | 1.81 | 2.6302 (15) | 175 |
O3—H3···O1i | 0.82 | 1.87 | 2.6861 (14) | 178 |
O4—H41···O3ii | 0.93 | 1.98 | 2.9043 (14) | 170 |
O4—H42···O2iii | 0.92 | 2 | 2.8922 (16) | 161 |
Symmetry codes: (i) x+1/2, −y+1/2, z−1/2; (ii) −x+1, −y+1, −z+1; (iii) x−1, y, z. |
Experimental details
Crystal data |
Chemical formula | C13H10O3·H2O |
Mr | 232.23 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 298 |
a, b, c (Å) | 4.2920 (1), 23.2084 (7), 11.4552 (3) |
β (°) | 95.393 (2) |
V (Å3) | 1136.01 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.60 × 0.15 × 0.09 |
|
Data collection |
Diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4756, 2444, 1692 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.641 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.158, 1.07 |
No. of reflections | 2444 |
No. of parameters | 159 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.20, −0.16 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H21···O4 | 0.82 | 1.81 | 2.6302 (15) | 174.7 |
O3—H3···O1i | 0.82 | 1.87 | 2.6861 (14) | 178.1 |
O4—H41···O3ii | 0.93 | 1.98 | 2.9043 (14) | 170.4 |
O4—H42···O2iii | 0.92 | 2 | 2.8922 (16) | 161 |
Symmetry codes: (i) x+1/2, −y+1/2, z−1/2; (ii) −x+1, −y+1, −z+1; (iii) x−1, y, z. |
As part of our ongoing studies of polymorphism in molecular compounds and pharmaceutics (Martins, Doriguetto & Ellena, 2010; Martins, Legendre et al., 2010; Martins, Bocelli et al., 2009; Martins, Paparidis et al. 2009; Corrêa et al., 2006; Doriguetto et al., 2004), we have studied 3,4-dihydroxybenzophenone, a synthetic hydroxybenzophenone. Hydroxybenzophenones have absorption bands in the near-UV and they are found in sun-protecting compounds in a variety of plastics and synthetic fabrics (Furukawa et al., 1995; Ito et al., 1994; Onishi et al., 1987). Anti-inflammatory and antioxidant activities have also been reported for hydroxybenzophenone derivatives (Doriguetto et al., 2007).
The structure of 3,4-dihydroxybenzophenone has been determined in its anhydrous form, (II), by X-ray diffraction analysis (Cox et al., 2008). It crystallizes in the space group C2/c, with cell parameters a = 24.4619 (9), b = 7.3737 (2) and c = 12.3961 (4) Å, and β = 115.019 (2)°. In this study, a new P21/n monoclinic pseudopolymorph was found, the title monohydrate, (I) (Fig. 1). An overlay of the molecular backbones in both anhydrous and hydrated forms of 3,4-dihydroxybenzophenone clearly shows the conformational similarity between these structures. The root mean-square deviation between analogous non-H atoms is 0.0891 Å (Fig. 2). Thus, the two compounds do not show conformational differences but only packing changes as a consequence of water inclusion.
In terms of intramolecular geometry, the main difference between the anhydrous and hydrated forms is in the position of the hydroxy H atoms. In the monohydrate form, (I), there is no intramolecular hydrogen bonding between atoms O2 and O3 (Fig. 1). On the other hand, in the anhydrous form, (II), the H atom of atom O2 is localized between atoms O2 and O1 (Fig. 2), resulting in an intramolecular O2—H2···O1 hydrogen bond with O···O = 2.6391 (17) Å and O—H···O = 172 (2)°.
In the monohydrate, (I), the least-squares planes through phenyl rings A and B form an angle of 56.3 (4)°, compared with 49.84 (5)° in the anhydrous form, (II). The similar torsion angles between rings A and B suggest that this feature is related to hindrance effects involving these two rings. In the course of the intramolecular analysis, the geometric parameters of monohydrate (I) were analysed using the Mogul software (Bruno et al., 2004). All geometric values agree with those of other reported hydroxybenzophenone structures (e.g. Cox et al., 2008; Doriguetto et al., 2007; Okabe & Kyoyama, 2002; Ferguson & Glidewell, 1996).
The supramolecular analysis of monohydrate (I) shows that there are four classical hydrogen bonds involving the hydroxyl and carbonyl groups and the water molecule, contributing to stabilize the crystal packing (Figs. 3 and 4, and Table 1). n-Glide-related molecules are linked by O—H···O hydrogen bonds in which the hydroxyl and carbonyl groups are involved as hydrogen-bonding donors and acceptors, respectively. Thus, the hydroxyl group O3—H3 in the meta position is a hydrogen-bond donor to carbonyl atom O1, giving rise to chains along the [101] direction. These chains are connected by two other intermolecular hydrogen bonds along the [010] direction involving the water molecule, O2—H21···O4 and O4—H41···O3ii [symmetry code: (ii) Please complete], giving rise to an inversion-related dimer at (1/2, 1/2, 1/2) and generating an infinite two-dimensional network parallel to the (101) plane, as shown in Fig. 3. The relatively short a axis [a = 4.2920 (1) Å] leads to these two-dimensional networks being stacked along the a direction, in which they are linked by an O4—H42···O2 hydrogen bond to generate a strongly hydrogen-bonded three-dimensional network. This arrangement gives rise to no significant π–π interactions; the shortest centroid-to-centroid separation is 5.53Å between the centroid of the C1–C6 ring and that of the glide-related C8–C13 ring at (1/2 + x, 1/2 - y, 1/2 + z).