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During a polymorphism screening of hy­droxy­benzophenone derivatives, a monohydrate pseudopolymorph of (3,4-dihy­droxy­phen­yl)(phen­yl)methanone, C13H10O3·H2O, (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. B64, 206–216]. The crystal packing of (I) is stabilized by classical inter­molecular O—H...O hydrogen bonds, generating a three-dimensional network.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110028544/fg3171sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270110028544/fg3171Isup2.hkl
Contains datablock I

CCDC reference: 796078

Comment top

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 ππ 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).

Related literature top

For related literature, see: Bruno et al. (2004); Corrêa et al. (2006); Cox et al. (2008); Doriguetto et al. (2004, 2007); Ferguson & Glidewell (1996); Furukawa et al. (1995); Ito et al. (1994); Martins, Bocelli, Bonfilio, Araújo, Lima, Neves, Veloso, Doriguetto & Ellena (2009); Martins, Doriguetto & Ellena (2010); Martins, Legendre, Honorato, Ayala, Doriguetto & Ellena (2010); Martins, Paparidis, Doriguetto & Ellena (2009); Okabe & Kyoyama (2002); Onishi et al. (1987).

Experimental top

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.

Refinement top

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).

Computing details top

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).

Figures top
[Figure 1] Fig. 1. The molecular structure of monohydrate (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. A superimposition of the monohydrated (black) and anhydrous (grey) forms of 3,4-dihydroxybenzophenone.
[Figure 3] Fig. 3. The crystal packing of (I), projected onto (101). Hydrogen bonds are shown as dashed lines. [Symmetry codes: (i) x + 1/2, -y + 1/2, z - 1/2; (ii) -x + 1, -y + 1, -z + 1; (iv) x - 1/2, -y + 1/2, z + 1/2.]
[Figure 4] Fig. 4. The crystal packing of (I), showing the role of water in the stabilization of the packing. Hydrogen bonds are shown as dashed lines. [Symmetry codes: (ii) -x + 1, -y + 1, -z + 1; (iii) x - 1, y, z; (v) -x, -y + 1, -z + 1.]
(3,4-dihydroxyphenyl)(phenyl)methanone monohydrate top
Crystal data top
C13H10O3·H2OF(000) = 488
Mr = 232.23Dx = 1.358 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2483 reflections
a = 4.2920 (1) Åθ = 0.4–27.5°
b = 23.2084 (7) ŵ = 0.10 mm1
c = 11.4552 (3) ÅT = 298 K
β = 95.393 (2)°Prism, colourless
V = 1136.01 (5) Å30.60 × 0.15 × 0.09 mm
Z = 4
Data collection top
Nonius KappaCCD area-detector
diffractometer
Rint = 0.032
Graphite monochromatorθmax = 27.1°, θmin = 2.5°
CCD rotation images, thick slices scansh = 55
4756 measured reflectionsk = 2929
2444 independent reflectionsl = 1414
1692 reflections with I > 2σ(I)
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.050Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.158H 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 parametersΔρmax = 0.20 e Å3
2 restraintsΔρmin = 0.16 e Å3
Crystal data top
C13H10O3·H2OV = 1136.01 (5) Å3
Mr = 232.23Z = 4
Monoclinic, P21/nMo Kα radiation
a = 4.2920 (1) ŵ = 0.10 mm1
b = 23.2084 (7) ÅT = 298 K
c = 11.4552 (3) Å0.60 × 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 reflectionsRint = 0.032
2444 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0502 restraints
wR(F2) = 0.158H atoms treated by a mixture of independent and constrained refinement
S = 1.07Δρmax = 0.20 e Å3
2444 reflectionsΔρmin = 0.16 e Å3
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
xyzUiso*/Ueq
C10.6007 (3)0.28115 (6)0.68593 (13)0.0494 (4)
C20.7382 (3)0.29750 (6)0.58467 (13)0.0491 (4)
H20.83940.270.54270.059*
C30.7248 (3)0.35352 (6)0.54704 (12)0.0465 (4)
C40.5614 (3)0.39440 (6)0.60748 (13)0.0493 (4)
C50.4238 (4)0.37831 (7)0.70710 (13)0.0547 (4)
H50.31590.40540.74750.066*
C60.4467 (4)0.32225 (7)0.74635 (13)0.0549 (4)
H60.35760.31190.81430.066*
C70.6235 (4)0.22207 (6)0.73364 (13)0.0535 (4)
C80.6543 (3)0.17132 (6)0.65680 (12)0.0508 (4)
C90.5074 (3)0.16865 (7)0.54319 (13)0.0553 (4)
H90.39570.20020.51170.066*
C100.5274 (4)0.11913 (7)0.47726 (15)0.0642 (5)
H100.42340.11710.40240.077*
C110.6998 (4)0.07285 (7)0.52163 (16)0.0702 (5)
H110.71680.04010.47590.084*
C120.8472 (5)0.07488 (7)0.63341 (17)0.0737 (5)
H120.96350.04350.66310.088*
C130.8233 (4)0.12357 (7)0.70198 (15)0.0621 (5)
H130.91980.12450.77810.075*
O10.6130 (3)0.21489 (5)0.84058 (10)0.0723 (4)
O20.5506 (3)0.44891 (5)0.56491 (10)0.0612 (4)
H210.41240.46690.59370.092*
O30.8637 (2)0.37325 (4)0.45200 (9)0.0571 (4)
H30.9420.34610.41940.086*
O40.1104 (3)0.51183 (5)0.64695 (10)0.0643 (4)
H410.1260.54680.60750.096*
H420.09090.49820.62960.096*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0575 (9)0.0462 (8)0.0447 (8)0.0037 (6)0.0059 (6)0.0015 (6)
C20.0586 (9)0.0430 (8)0.0458 (8)0.0006 (6)0.0063 (6)0.0003 (6)
C30.0539 (8)0.0427 (8)0.0435 (8)0.0046 (6)0.0073 (6)0.0014 (6)
C40.0560 (8)0.0402 (8)0.0518 (8)0.0013 (6)0.0047 (6)0.0022 (6)
C50.0636 (9)0.0483 (9)0.0536 (9)0.0031 (7)0.0129 (7)0.0013 (6)
C60.0649 (9)0.0545 (9)0.0465 (8)0.0051 (7)0.0120 (7)0.0019 (7)
C70.0626 (9)0.0507 (9)0.0480 (9)0.0055 (6)0.0083 (7)0.0048 (6)
C80.0582 (9)0.0435 (8)0.0516 (9)0.0042 (6)0.0100 (7)0.0060 (6)
C90.0613 (9)0.0501 (9)0.0551 (9)0.0030 (7)0.0074 (7)0.0048 (7)
C100.0751 (11)0.0619 (11)0.0558 (10)0.0130 (8)0.0075 (8)0.0024 (8)
C110.0892 (13)0.0510 (10)0.0737 (13)0.0052 (8)0.0256 (10)0.0064 (8)
C120.0918 (13)0.0549 (11)0.0764 (12)0.0131 (9)0.0186 (10)0.0098 (9)
C130.0725 (11)0.0558 (10)0.0584 (10)0.0028 (8)0.0077 (8)0.0094 (7)
O10.1144 (10)0.0567 (8)0.0474 (7)0.0051 (6)0.0153 (6)0.0082 (5)
O20.0732 (7)0.0424 (6)0.0709 (8)0.0044 (5)0.0216 (6)0.0058 (5)
O30.0774 (8)0.0423 (6)0.0545 (7)0.0022 (5)0.0217 (5)0.0051 (4)
O40.0714 (8)0.0524 (7)0.0705 (8)0.0024 (5)0.0142 (6)0.0024 (5)
Geometric parameters (Å, º) top
C1—C61.383 (2)C8—C131.397 (2)
C1—C21.4023 (19)C9—C101.382 (2)
C1—C71.476 (2)C9—H90.93
C2—C31.3694 (19)C10—C111.374 (2)
C2—H20.93C10—H100.93
C3—O31.3682 (16)C11—C121.375 (2)
C3—C41.401 (2)C11—H110.93
C4—O21.3550 (17)C12—C131.385 (2)
C4—C51.385 (2)C12—H120.93
C5—C61.377 (2)C13—H130.93
C5—H50.93O2—H210.82
C6—H60.93O3—H30.82
C7—O11.2413 (17)O4—H410.9336
C7—C81.484 (2)O4—H420.9239
C8—C91.3932 (19)
C6—C1—C2119.05 (13)C9—C8—C13118.99 (14)
C6—C1—C7118.29 (13)C9—C8—C7122.12 (13)
C2—C1—C7122.63 (13)C13—C8—C7118.82 (14)
C3—C2—C1120.59 (14)C10—C9—C8120.09 (15)
C3—C2—H2119.7C10—C9—H9120
C1—C2—H2119.7C8—C9—H9120
O3—C3—C2124.03 (13)C11—C10—C9120.43 (17)
O3—C3—C4116.26 (13)C11—C10—H10119.8
C2—C3—C4119.71 (13)C9—C10—H10119.8
O2—C4—C5123.06 (14)C10—C11—C12120.16 (17)
O2—C4—C3117.15 (13)C10—C11—H11119.9
C5—C4—C3119.79 (14)C12—C11—H11119.9
C6—C5—C4120.07 (14)C11—C12—C13120.26 (17)
C6—C5—H5120C11—C12—H12119.9
C4—C5—H5120C13—C12—H12119.9
C5—C6—C1120.75 (14)C12—C13—C8120.03 (17)
C5—C6—H6119.6C12—C13—H13120
C1—C6—H6119.6C8—C13—H13120
O1—C7—C1118.86 (13)C4—O2—H21109.5
O1—C7—C8119.51 (13)C3—O3—H3109.5
C1—C7—C8121.62 (13)H41—O4—H42107.5
C6—C1—C2—C31.0 (2)C6—C1—C7—C8153.25 (14)
C7—C1—C2—C3176.58 (14)C2—C1—C7—C829.1 (2)
C1—C2—C3—O3177.29 (13)O1—C7—C8—C9144.32 (16)
C1—C2—C3—C42.6 (2)C1—C7—C8—C934.8 (2)
O3—C3—C4—O21.4 (2)O1—C7—C8—C1332.4 (2)
C2—C3—C4—O2178.68 (13)C1—C7—C8—C13148.41 (15)
O3—C3—C4—C5177.70 (13)C13—C8—C9—C100.6 (2)
C2—C3—C4—C52.2 (2)C7—C8—C9—C10176.13 (14)
O2—C4—C5—C6179.27 (13)C8—C9—C10—C112.0 (2)
C3—C4—C5—C60.2 (2)C9—C10—C11—C121.8 (3)
C4—C5—C6—C11.4 (2)C10—C11—C12—C130.1 (3)
C2—C1—C6—C51.0 (2)C11—C12—C13—C81.3 (3)
C7—C1—C6—C5178.70 (14)C9—C8—C13—C121.1 (2)
C6—C1—C7—O125.9 (2)C7—C8—C13—C12177.90 (14)
C2—C1—C7—O1151.72 (16)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H21···O40.821.812.6302 (15)175
O3—H3···O1i0.821.872.6861 (14)178
O4—H41···O3ii0.931.982.9043 (14)170
O4—H42···O2iii0.9222.8922 (16)161
Symmetry codes: (i) x+1/2, y+1/2, z1/2; (ii) x+1, y+1, z+1; (iii) x1, y, z.

Experimental details

Crystal data
Chemical formulaC13H10O3·H2O
Mr232.23
Crystal system, space groupMonoclinic, P21/n
Temperature (K)298
a, b, c (Å)4.2920 (1), 23.2084 (7), 11.4552 (3)
β (°) 95.393 (2)
V3)1136.01 (5)
Z4
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.60 × 0.15 × 0.09
Data collection
DiffractometerNonius KappaCCD area-detector
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
4756, 2444, 1692
Rint0.032
(sin θ/λ)max1)0.641
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.050, 0.158, 1.07
No. of reflections2444
No. of parameters159
No. of restraints2
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.20, 0.16

Computer programs: COLLECT (Nonius, 2000), SCALEPACK (Otwinowski & Minor, 1997), DENZO (Otwinowski & Minor, 1997) and SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H21···O40.821.812.6302 (15)174.7
O3—H3···O1i0.821.872.6861 (14)178.1
O4—H41···O3ii0.931.982.9043 (14)170.4
O4—H42···O2iii0.9222.8922 (16)161
Symmetry codes: (i) x+1/2, y+1/2, z1/2; (ii) x+1, y+1, z+1; (iii) x1, y, z.
 

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