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The X-ray structure of 1,2,4,5-tetra­hydroxy­benzene (benzene-1,2,4,5-tetrol) monohydrate, C6H6O4·H2O, (I), reveals columns of 1,2,4,5-tetra­hydroxy­benzene parallel to the b axis that are separated by 3.364 (12) and 3.453 (11) Å. Molecules in adjacent columns are tilted relative to each other by 27.78 (8)°. Water mol­ecules fill the channels between the columns and are involved in hydrogen-bonding interactions with the 1,2,4,5-tetra­hydroxy­benzene mol­ecules. The crystal structure of the adduct 1,2,4,5-tetra­hydroxy­benzene-2,5-di­hydroxy-1,4-benzo­quinone (1/1), C6H6O4·C6H4O4, (II), reveals alternating mol­ecules of 1,2,4,5-tetra­hydroxy­benzene and 2,5-di­hydroxy-1,4-benzo­quinone (both lying on inversion centers), and a zigzag hydrogen-bonded network connecting mol­ecules in three dimensions. For compound (II), the conventional X-ray determination, (IIa), is in very good agreement with the synchrotron X-ray determination, (IIb). When differences in data collection temperatures are taken into account, even the displacement parameters are in very good agreement.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101003353/da1173sup1.cif
Contains datablocks global, I, IIa, IIb

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101003353/da1173Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101003353/da1173IIasup3.hkl
Contains datablock IIa

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101003353/da1173IIbsup4.hkl
Contains datablock IIb

CCDC references: 166984; 166985; 166986

Comment top

Derivatized porphyrins have found extensive use as models for the heme active sites of myoglobin and hemoglobin (Momenteau & Reed, 1994). Compound (I), 1,2,4,5-tetrahydroxybenzene monohydrate, was prepared as a precursor in the synthesis of elaborated porphyrins containing a benzene `cap' linked to the porphyrin by ethoxy linkages (Ma et al., 1993; Johnson et al., 1996; Slebodnick et al., 1996; Jene et al., 1999; Jene & Ibers, 2000). Compound (I) forms pale-pink crystals. The synthesis of (I) is sensitive to the initial reaction conditions and yields products that vary from these crystals to a gray-black amorphous material. All products work in the capped porphyrin synthesis. To understand these products better, we determined the structures of (I) and of the adduct 1,2,4,5-tetrahydroxybenzene-2,5-dihydroxy-1,4-benzoquinone (1/1), (II). Crystals of (II) are stable and of excellent quality. Consequently, a short wavelength (0.354 Å) data set was collected from a crystal of (II) on the Rigaku R-axis image-plate diffractometer at the Advanced Photon Source (APS). Refinement of this data set provides a check on the APS system and an interesting comparison with the results from a conventional structure determination. \sch

The asymmetric unit of compound (I) contains two half-molecules of 1,2,4,5-tetrahydroxybenzene that sit on inversion centers and two half-water molecules that sit on twofold axes (Fig. 1). Selected bond lengths and angles are listed in Table 1. The benzene rings are planar by symmetry. CC bond lengths in (I) reflect the fully delocalized nature of the benzene ring. The crystal structure is composed of columnar stacking and two-dimensional networks of hydrogen bonding (Fig. 2). Both unique molecules form separate columns parallel to the b axis. The first column is formed from atoms C1, C2, C3, O1, and O2 and their symmetry-generated counterparts; these are separated by 3.453 (11) Å. The second column is formed from atoms C4, C5, C6, O3, and O4 and their symmetry-generated counterparts; these are separated by 3.364 (12) Å. Molecules in different columns are tilted relative to each other by 27.78 (8)°. A ruffled two-dimensional network of hydrogen bonding exists perpendicular to the columns. Intermolecular and intramolecular hydrogen-bonding interactions are listed in Table 2. The two unique half-water molecules, containing atoms O5 and O6, fill neighboring channels of the column structure but are oriented in opposite directions. The O atoms O5 and O6 of the half-water molecules are involved in four hydrogen bonds to four molecules of 1,2,4,5-tetrahydroxybenzene in neighboring columns.

The synthesis (Jones & Shonle, 1945) and crystal structure (Semmingsen, 1977) of 2,5-dihydroxy-1,4-benzoquinone have been known for some time. In addition, dihydroxyquinones substituted at the 3,6-positions have been prepared with fluoro (Krogh Andersen & Krogh Andersen, 1975), chloro (Krogh Andersen, 1967a,b), bromo (Robl, 1987), iodo (Robl & Sheldrick, 1988), and additional hydroxy (Klug, 1965) substituents.

Molecules of 1,2,4,5-tetrahydroxybenzene and 2,5-dihydroxy-1,4-benzoquinone in compound (II) (Fig. 3) are both located on inversion centers, and the benzene and quinone portions of these molecules are planar by symmetry. These two molecules are related by pseudo symmetry if the positions of the H atoms are ignored. However, the positions of these H atoms refine well when constraints are released. The molecules are tilted relative to each other by 64.00 (5)°, as measured by their mean planes. The two kinds of molecules alternate to form two unique stacks parallel to the a axis and two unique stacks parallel to the b axis (Fig. 4). Metrical details are listed in Tables 3–6, and values for discussion are taken from Tables 5 and 6. The interplanar distances between molecules in the stacks are 2.895 (1) and 3.301 (1) Å along the a axis and 3.115 (1) and 3.304 (1) Å along the b axis. There is a three-dimensional zigzag hydrogen-bonded network in the structure.

The 2,5-dihydroxy-1,4-benzoquinone component of (II) shows pronounced quinoid character, with both short and long C—O bonds and three varied CC bond lengths (Tables 3 and 5). These values are similar to those reported earlier by Semmingsen (1977). The difference is an ~180° rotation of a hydroxyl group between the structures. The geometry of the 1,2,4,5-tetrahydroxybenzene component of (II) is very similar to that in (I). The exception is one hydroxyl group that is flipped by ~180° (Tables 3 and 5). This orientation precludes the possibility of intramolecular hydrogen-bonding interactions and underscores the importance of crystal-packing forces on the orientation of hydroxyl groups in compounds of this type.

For compound (II), the conventional X-ray determination, (IIa) (Tables 3 and 4), is in very good agreement with the synchrotron X-ray determination, (IIb) (Table 5 and 6). There are a few possibly significant differences, e.g. C2—C3 [1.389 (2) Å in (IIa) and 1.3953 (4) Å in (IIb)], but since (IIa) is a determination at 163 K and (IIb) at 110 K it is possible that these arise from differences in vibrational foreshortening of the bonds. In this regard, if a linear correction is applied for the differences in temperature (Debye, 1913; Dunitz et al., 1988), then generally the Uij values from the two determinations agree within about 10%. Since, in X-ray structure determinations, it is the Uij values that are most sensitive to a variety of systematic errors, we find this agreement very encouraging. The estimated standard deviations associated with derived quantities for (IIb) are roughly 20% of those for (IIa), in part because there are 5678 independent reflections in (IIb) and 842 in (IIa).

Crystals of (II) are dark and shiny, in sharp contrast to crystals of compound (I). The dark color probably arises from a charge-transfer interaction between molecules of 1,2,4,5-tetrahydroxybenzene acting as donors and molecules of 2,5-dihydroxy-1,4-benzoquinone acting as acceptors. Chowdhury (1961) has shown that charge-transfer interactions occur between quinones and aromatic hydrocarbons. Sakurai (1965) has proposed that the color of quinhydrone results from hydroquinone acting as the donor and quinone as the acceptor molecule. One feature of this interaction is abnormally short C···O interactions. Compound (IIb) has short C···O interactions that range from 3.097 (1)–3.241 (1) Å. The shortest of these is shorter than the 3.2 Å value reported by Sakurai (1965). It is also likely that the gray-black material often present in the synthesis of (I) is a mixture of (I) and (II), with (II) forming by partial air oxidation in solution.

Related literature top

For related literature, see: Anslow & Raistrick (1939); Chowdhury (1961); Debye (1913); Dunitz et al. (1988); Jene & Ibers (2000); Jene et al. (1999); Johnson et al. (1996); Jones & Shonle (1945); Klug (1965); Krogh (1967a, 1967b); Krogh & Krogh Andersen (1975); Ma et al. (1993); Momenteau & Reed (1994); Robl (1987); Robl & Sheldrick (1988); Sakurai (1965); Semmingsen (1977); Slebodnick et al. (1996); Zaleski et al. (1998).

Experimental top

Crystals of compound (I) were prepared by the literature method of Anslow & Raistrick (1939) (m.p. 490–491 K). Compound (II) was prepared by allowing a small quantity of (I) to stand in D2O. After 1 month, shiny dark crystals of (II) formed (m.p. >673 K). Melting points were measured on a Mel-Temp melting point apparatus (Laboratory Instruments, Holliston, Massachusetts).

Refinement top

For compound (IIb), an R-axis IV image plate detector was used in the BMB-5 beamline hutch of the DuPont-Northwestern-Dow Collaborative Access Team (DND-CAT) at the APS. The crystal-to-detector distance was 165.0 (1) mm, and the beam size was 2 mm by 2 mm. Each frame covered 6° in ϕ for 2 min. Data were collected in one group of 20 frames starting at a ϕ setting of 0°. Raw data were corrected for angular variation of the phosphor response of the image plate with a local program, following the method of Zaleski et al. (1998). For all compounds, H atoms were treated as riding, with O—H 0.83–0.84 Å and C—H 0.94–0.95 Å Query. The crystals were attached to glass fibers with a minimum of silicone cement.

Computing details top

Data collection: SMART (Bruker, 1998) for (I); CAD-4 Software (Enraf-Nonius, 1993) for (IIa); HKL (Otwinowski & Minor, 1997) for (IIb). Cell refinement: SMART (Bruker, 1998) for (I); DIRAX (Duisenberg, 1992) for (IIa); HKL for (IIb). Data reduction: SAINT-Plus (Bruker, 1998) for (I); local programs for (IIa); HKL for (IIb). For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL/PC (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL/PC.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atom-numbering scheme and with 50% displacement ellipsoids. H atoms are drawn as small spheres of arbitrary radii.
[Figure 2] Fig. 2. The stereoview of (I), showing columnar stacking, hydrogen-bonding interactions (dashed lines), and the water molecule orientation.
[Figure 3] Fig. 3. The molecular structure of (II) from the R-axis data set, i.e. (IIb), showing the atom-numbering scheme and with 50% displacement ellipsoids. H atoms are drawn as small spheres of arbitrary radii. Only unique atoms are labeled.
[Figure 4] Fig. 4. The stereoview for (IIb) showing columnar stacking and hydrogen-bonding interactions (dashed lines) for compound (IIB).
(I) 1,2,4,5-Tetrahydroxybenzene monohydrate top
Crystal data top
C6H6O4·H2ODx = 1.639 Mg m3
Mr = 160.12Melting point = 490–491 K
Monoclinic, P2/nMo Kα radiation, λ = 0.71073 Å
a = 13.487 (3) ÅCell parameters from 623 reflections
b = 3.647 (1) Åθ = 1.9–28.3°
c = 13.506 (3) ŵ = 0.15 mm1
β = 102.33 (3)°T = 203 K
V = 649.1 (2) Å3Rectangular prism, pale pink
Z = 40.5 × 0.2 × 0.2 mm
F(000) = 336
Data collection top
Bruker Smart1000 CCD
diffractometer
1270 reflections with I > 2σ(I)
Radiation source: standard-focus sealed tubeRint = 0.022
Graphite monochromatorθmax = 28.3°, θmin = 1.9°
ω scansh = 1713
3708 measured reflectionsk = 44
1578 independent reflectionsl = 1118
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.149H-atom parameters constrained
S = 1.22 w = 1/[σ2(Fo2) + (0.036P)2 + 1.0778P]
where P = (Fo2 + 2Fc2)/3
1578 reflections(Δ/σ)max < 0.001
116 parametersΔρmax = 0.39 e Å3
0 restraintsΔρmin = 0.26 e Å3
Crystal data top
C6H6O4·H2OV = 649.1 (2) Å3
Mr = 160.12Z = 4
Monoclinic, P2/nMo Kα radiation
a = 13.487 (3) ŵ = 0.15 mm1
b = 3.647 (1) ÅT = 203 K
c = 13.506 (3) Å0.5 × 0.2 × 0.2 mm
β = 102.33 (3)°
Data collection top
Bruker Smart1000 CCD
diffractometer
1270 reflections with I > 2σ(I)
3708 measured reflectionsRint = 0.022
1578 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0450 restraints
wR(F2) = 0.149H-atom parameters constrained
S = 1.22Δρmax = 0.39 e Å3
1578 reflectionsΔρmin = 0.26 e Å3
116 parameters
Special details top

Experimental. For compound (I) the crystal-to-detector distance was 5.023 cm. Each frame covered -0.3° in ω for 20 s. Data were collected in groups of 606, 435, and 230 frames at ϕ settings of 0°, 90°, and 180°, respectively. For compound (IIa) data were collected at a scan rate of 4° to 8°/minute.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.20737 (11)0.4354 (5)0.57575 (12)0.0246 (4)
H10.23900.46550.53000.033 (8)*
O20.07215 (12)0.2709 (5)0.69800 (12)0.0258 (4)
H20.12710.16210.70360.069 (13)*
O30.07741 (11)1.1076 (5)0.79534 (11)0.0230 (4)
H3A0.03081.12730.76430.042 (9)*
O40.19309 (11)0.7111 (5)1.06635 (12)0.0225 (4)
H40.19860.61911.12350.044 (10)*
O51/40.3507 (7)1/40.0243 (5)
H5A0.298 (2)0.221 (11)0.250 (3)0.051 (11)*
O61/40.8880 (8)3/40.0261 (5)
H6A0.251 (4)0.738 (16)0.692 (3)0.102 (18)*
C10.10420 (16)0.4680 (6)0.53592 (16)0.0190 (5)
C20.03826 (16)0.3815 (6)0.59895 (16)0.0188 (5)
C30.06586 (16)0.4139 (6)0.56214 (16)0.0199 (5)
H3B0.11070.35490.60430.019 (6)*
C40.03683 (16)1.0535 (6)0.89710 (16)0.0176 (4)
C50.05936 (16)0.9069 (6)0.93179 (16)0.0186 (5)
H5B0.09930.84310.88530.019 (6)*
C60.09686 (15)0.8541 (6)1.03462 (16)0.0180 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0151 (7)0.0399 (10)0.0192 (8)0.0018 (7)0.0047 (6)0.0044 (7)
O20.0193 (8)0.0400 (10)0.0187 (8)0.0036 (7)0.0055 (6)0.0094 (7)
O30.0171 (7)0.0380 (10)0.0144 (8)0.0021 (7)0.0048 (6)0.0043 (7)
O40.0162 (7)0.0336 (9)0.0185 (8)0.0060 (7)0.0056 (6)0.0038 (7)
O50.0187 (11)0.0305 (13)0.0232 (12)00.0031 (9)0
O60.0215 (11)0.0355 (14)0.0210 (12)00.0037 (9)0
C10.0150 (9)0.0230 (11)0.0194 (10)0.0008 (8)0.0045 (8)0.0008 (9)
C20.0189 (10)0.0216 (11)0.0158 (10)0.0011 (8)0.0036 (8)0.0016 (8)
C30.0179 (10)0.0255 (12)0.0178 (11)0.0017 (9)0.0074 (8)0.0030 (9)
C40.0170 (10)0.0218 (11)0.0144 (9)0.0012 (8)0.0045 (8)0.0012 (8)
C50.0166 (10)0.0229 (11)0.0182 (10)0.0007 (8)0.0082 (8)0.0004 (8)
C60.0144 (9)0.0195 (10)0.0202 (11)0.0002 (8)0.0042 (8)0.0012 (8)
Geometric parameters (Å, º) top
O1—C11.386 (2)O6—H6Aii0.95 (5)
O1—H10.8300C1—C3iii1.384 (3)
O2—C21.378 (3)C1—C21.392 (3)
O2—H20.8300C2—C31.391 (3)
O3—C41.381 (3)C3—C1iii1.384 (3)
O3—H3A0.8300C3—H3B0.9400
O4—C61.379 (3)C4—C51.389 (3)
O4—H40.8300C4—C6iv1.392 (3)
O5—H5Ai0.80 (4)C5—C61.386 (3)
O5—H5A0.80 (4)C5—H5B0.9400
O6—H6A0.95 (5)C6—C4iv1.392 (3)
C1—O1—H1109.5C1iii—C3—C2120.7 (2)
C2—O2—H2109.5C1iii—C3—H3B119.6
C4—O3—H3A109.5C2—C3—H3B119.6
C6—O4—H4109.5O3—C4—C5122.27 (19)
H5Ai—O5—H5A107 (6)O3—C4—C6iv117.50 (19)
H6A—O6—H6Aii110 (7)C5—C4—C6iv120.2 (2)
C3iii—C1—O1122.50 (19)C6—C5—C4120.41 (19)
C3iii—C1—C2119.9 (2)C6—C5—H5B119.8
O1—C1—C2117.57 (19)C4—C5—H5B119.8
O2—C2—C3118.15 (19)O4—C6—C5118.79 (19)
O2—C2—C1122.5 (2)O4—C6—C4iv121.84 (19)
C3—C2—C1119.4 (2)C5—C6—C4iv119.4 (2)
Symmetry codes: (i) x+1/2, y, z+1/2; (ii) x+1/2, y, z+3/2; (iii) x, y+1, z+1; (iv) x, y+2, z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O4ii0.831.962.756 (2)160
O2—H2···O6v0.831.922.735 (2)166
O3—H3A···O2vi0.831.882.699 (2)169
O4—H4···O5vii0.831.962.767 (2)163
O5—H5A···O3viii0.77 (3)2.07 (3)2.826 (2)165 (3)
O6—H6A···O10.95 (5)1.91 (5)2.832 (2)162 (3)
Symmetry codes: (ii) x+1/2, y, z+3/2; (v) x, y1, z; (vi) x, y+1, z; (vii) x, y, z+1; (viii) x+1/2, y+1, z1/2.
(IIa) 1,2,4,5-Tetrahydroxybenzene-2,5-Dihydroxy-1,4-benzoquinone (1/1) top
Crystal data top
C6H6O4·C6H4O4Dx = 1.784 Mg m3
Mr = 282.20Melting point > 673 K
Monoclinic, P21/nCu Kα radiation, λ = 1.54178 Å
a = 7.387 (3) ÅCell parameters from 25 reflections
b = 6.060 (1) Åθ = 30.8–38.9°
c = 12.198 (2) ŵ = 1.34 mm1
β = 105.78 (2)°T = 163 K
V = 525.4 (3) Å3Rectangular prism, black
Z = 20.43 × 0.15 × 0.05 mm
F(000) = 292
Data collection top
Enraf-Nonius CAD-4
diffractometer
753 reflections with I > 2σ(I)
Radiation source: standard-focus sealed tubeRint = 0.021
Graphite monochromatorθmax = 63.0°, θmin = 6.3°
ω/2θ scansh = 88
Absorption correction: analytical
face-indexed (de Meulenaer & Tompa, 1965)
k = 66
Tmin = 0.877, Tmax = 0.938l = 1414
3379 measured reflections6 standard reflections every 100 reflections
842 independent reflections intensity decay: <2%
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)] = 0.035Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.114H-atom parameters constrained
S = 1.14 w = 1/[σ2(Fo2) + (0.0694P)2 + 0.1389P]
where P = (Fo2 + 2Fc2)/3
842 reflections(Δ/σ)max < 0.001
94 parametersΔρmax = 0.19 e Å3
0 restraintsΔρmin = 0.25 e Å3
Crystal data top
C6H6O4·C6H4O4V = 525.4 (3) Å3
Mr = 282.20Z = 2
Monoclinic, P21/nCu Kα radiation
a = 7.387 (3) ŵ = 1.34 mm1
b = 6.060 (1) ÅT = 163 K
c = 12.198 (2) Å0.43 × 0.15 × 0.05 mm
β = 105.78 (2)°
Data collection top
Enraf-Nonius CAD-4
diffractometer
753 reflections with I > 2σ(I)
Absorption correction: analytical
face-indexed (de Meulenaer & Tompa, 1965)
Rint = 0.021
Tmin = 0.877, Tmax = 0.9386 standard reflections every 100 reflections
3379 measured reflections intensity decay: <2%
842 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0350 restraints
wR(F2) = 0.114H-atom parameters constrained
S = 1.14Δρmax = 0.19 e Å3
842 reflectionsΔρmin = 0.25 e Å3
94 parameters
Special details top

Experimental. For compound (I) the crystal-to-detector distance was 5.023 cm. Each frame covered -0.3° in ω for 20 s. Data were collected in groups of 606, 435, and 230 frames at ϕ settings of 0°, 90°, and 180°, respectively. For compound (IIa) data were collected at a scan rate of 4° to 8°/minute.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.98007 (14)0.55646 (16)0.22730 (7)0.0146 (4)
H10.93840.44340.26570.017*
O20.82695 (13)0.15885 (16)0.08177 (7)0.0131 (4)
H30.78120.06630.03050.016*
O30.99530 (13)0.06305 (16)0.27657 (7)0.0140 (4)
H50.94710.04120.23290.017*
O41.16048 (13)0.34700 (15)0.43160 (7)0.0133 (4)
C10.98734 (18)0.5200 (2)0.11557 (11)0.0106 (4)
C20.90043 (19)0.3446 (2)0.07742 (11)0.0114 (4)
H20.83240.23840.12990.014*
C30.91311 (18)0.3248 (2)0.03786 (11)0.0112 (4)
C40.90720 (19)0.1594 (2)0.41533 (11)0.0116 (4)
H40.84540.26560.36060.014*
C50.98966 (18)0.0161 (2)0.38227 (11)0.0111 (4)
C61.08814 (18)0.1877 (2)0.46676 (11)0.0114 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0228 (6)0.0131 (6)0.0076 (6)0.0044 (4)0.0037 (4)0.0018 (4)
O20.0179 (6)0.0105 (6)0.0107 (5)0.0049 (4)0.0038 (4)0.0010 (4)
O30.0209 (6)0.0131 (6)0.0078 (6)0.0041 (4)0.0036 (4)0.0013 (4)
O40.0161 (6)0.0111 (6)0.0127 (6)0.0029 (4)0.0040 (4)0.0010 (4)
C10.0116 (7)0.0107 (7)0.0095 (7)0.0026 (5)0.0030 (5)0.0004 (5)
C20.0105 (7)0.0116 (8)0.0112 (7)0.0002 (5)0.0013 (5)0.0026 (5)
C30.0099 (7)0.0093 (8)0.0146 (7)0.0013 (5)0.0035 (6)0.0013 (5)
C40.0109 (7)0.0114 (8)0.0115 (7)0.0001 (5)0.0011 (5)0.0027 (5)
C50.0113 (7)0.0116 (7)0.0100 (7)0.0028 (5)0.0024 (5)0.0001 (5)
C60.0088 (7)0.0104 (8)0.0148 (8)0.0027 (5)0.0029 (6)0.0008 (5)
Geometric parameters (Å, º) top
O1—C11.3671 (16)C2—C31.3887 (19)
O1—H10.8400C2—H20.9500
O2—C31.3742 (17)C3—C1i1.394 (2)
O2—H30.8400C4—C51.341 (2)
O3—C51.3320 (16)C4—C6ii1.4395 (19)
O3—H50.8400C4—H40.9500
O4—C61.2355 (17)C5—C61.505 (2)
C1—C21.386 (2)C6—C4ii1.4395 (19)
C1—C3i1.394 (2)
C1—O1—H1109.5C2—C3—C1i120.52 (12)
C3—O2—H3109.5C5—C4—C6ii120.36 (12)
C5—O3—H5109.5C5—C4—H4119.8
O1—C1—C2124.22 (12)C6ii—C4—H4119.8
O1—C1—C3i116.06 (12)O3—C5—C4126.65 (13)
C2—C1—C3i119.71 (13)O3—C5—C6112.26 (12)
C1—C2—C3119.77 (12)C4—C5—C6121.10 (13)
C1—C2—H2120.1O4—C6—C4ii123.02 (12)
C3—C2—H2120.1O4—C6—C5118.44 (12)
O2—C3—C2123.18 (12)C4ii—C6—C5118.54 (12)
O2—C3—C1i116.29 (12)
Symmetry codes: (i) x+2, y+1, z; (ii) x+2, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O4iii0.842.042.737 (1)140
O2—H3···O4iv0.841.852.686 (2)172
O3—H5···O20.841.952.719 (1)152
Symmetry codes: (iii) x+2, y, z; (iv) x1/2, y1/2, z1/2.
(IIb) 1,2,4,5-Tetrahydroxybenzene-2,5-Dihydroxy-1,4-benzoquinone (1/1) top
Crystal data top
C6H6O4·C6H4O4Dx = 1.783 Mg m3
Mr = 282.20Melting point > 673 K
Monoclinic, P21/nSynchrotron radiation, λ = 0.35400 Å
a = 7.382 (1) ÅCell parameters from 4909 reflections
b = 6.065 (1) Åθ = 2.6–25.9°
c = 12.197 (1) ŵ = 0.09 mm1
β = 105.778 (1)°T = 110 K
V = 525.51 (12) Å3Rectangular prism, black
Z = 21.12 × 0.33 × 0.20 mm
F(000) = 292
Data collection top
R-axis IV image plate
diffractometer
4908 reflections with I > 2σ(I)
Radiation source: white-beamRint = 0.032
Silicon crystal monochromatorθmax = 25.9°, θmin = 2.6°
ϕ scansh = 1416
13465 measured reflectionsk = 1212
5678 independent reflectionsl = 2523
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)] = 0.031Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.113H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0738P)2 + 0.021P]
where P = (Fo2 + 2Fc2)/3
5678 reflections(Δ/σ)max = 0.001
94 parametersΔρmax = 0.58 e Å3
0 restraintsΔρmin = 0.48 e Å3
Crystal data top
C6H6O4·C6H4O4V = 525.51 (12) Å3
Mr = 282.20Z = 2
Monoclinic, P21/nSynchrotron radiation, λ = 0.35400 Å
a = 7.382 (1) ŵ = 0.09 mm1
b = 6.065 (1) ÅT = 110 K
c = 12.197 (1) Å1.12 × 0.33 × 0.20 mm
β = 105.778 (1)°
Data collection top
R-axis IV image plate
diffractometer
4908 reflections with I > 2σ(I)
13465 measured reflectionsRint = 0.032
5678 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0310 restraints
wR(F2) = 0.113H-atom parameters constrained
S = 1.04Δρmax = 0.58 e Å3
5678 reflectionsΔρmin = 0.48 e Å3
94 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.98001 (3)0.55561 (4)0.227606 (18)0.01002 (4)
H10.93640.44330.26600.012*
O20.82605 (3)0.15883 (3)0.081429 (18)0.00871 (4)
H30.78030.06680.02990.010*
O30.99517 (3)0.06236 (4)0.276231 (17)0.00943 (4)
H50.94320.04000.23250.011*
O41.16100 (3)0.34706 (3)0.431529 (19)0.00904 (4)
C10.98744 (3)0.51993 (4)0.11610 (2)0.00659 (4)
C20.89983 (3)0.34416 (4)0.07772 (2)0.00687 (4)
H20.83170.23800.13020.008*
C30.91252 (3)0.32451 (4)0.03811 (2)0.00647 (4)
C40.90645 (3)0.16006 (4)0.41520 (2)0.00727 (4)
H40.84430.26630.36060.009*
C50.98999 (3)0.01676 (4)0.38190 (2)0.00670 (4)
C61.08821 (3)0.18730 (4)0.46649 (2)0.00667 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.01595 (8)0.00875 (7)0.00538 (7)0.00306 (5)0.00295 (5)0.00055 (5)
O20.01211 (7)0.00630 (7)0.00769 (7)0.00365 (4)0.00263 (5)0.00007 (5)
O30.01430 (8)0.00847 (7)0.00566 (7)0.00250 (5)0.00292 (5)0.00026 (5)
O40.01214 (7)0.00651 (7)0.00835 (7)0.00341 (4)0.00257 (5)0.00059 (5)
C10.00846 (8)0.00568 (7)0.00551 (7)0.00122 (5)0.00172 (5)0.00042 (5)
C20.00855 (8)0.00569 (8)0.00614 (8)0.00173 (5)0.00160 (5)0.00084 (5)
C30.00780 (8)0.00514 (7)0.00639 (7)0.00132 (4)0.00179 (5)0.00024 (5)
C40.00935 (8)0.00606 (8)0.00627 (7)0.00220 (5)0.00192 (5)0.00090 (5)
C50.00854 (8)0.00576 (7)0.00570 (7)0.00117 (5)0.00176 (5)0.00032 (5)
C60.00803 (8)0.00531 (7)0.00655 (8)0.00132 (5)0.00178 (5)0.00012 (5)
Geometric parameters (Å, º) top
O1—C11.3635 (3)C2—C31.3953 (4)
O1—H10.8400C2—H20.9500
O2—C31.3710 (3)C3—C1i1.3994 (4)
O2—H30.8400C4—C51.3533 (4)
O3—C51.3289 (3)C4—C6ii1.4423 (4)
O3—H50.8400C4—H40.9500
O4—C61.2386 (3)C5—C61.5011 (4)
C1—C21.3923 (4)C6—C4ii1.4423 (4)
C1—C3i1.3994 (4)
C1—O1—H1109.5C2—C3—C1i120.55 (2)
C3—O2—H3109.5C5—C4—C6ii120.02 (2)
C5—O3—H5109.5C5—C4—H4120.0
O1—C1—C2124.09 (2)C6ii—C4—H4120.0
O1—C1—C3i116.21 (2)O3—C5—C4126.27 (2)
C2—C1—C3i119.69 (2)O3—C5—C6112.78 (2)
C1—C2—C3119.76 (2)C4—C5—C6120.94 (2)
C1—C2—H2120.1O4—C6—C4ii122.52 (2)
C3—C2—H2120.1O4—C6—C5118.44 (2)
O2—C3—C2122.87 (2)C4ii—C6—C5119.04 (2)
O2—C3—C1i116.56 (2)
Symmetry codes: (i) x+2, y+1, z; (ii) x+2, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O4iii0.842.042.7316 (4)140
O2—H3···O4iv0.841.852.6816 (4)171
O3—H5···O20.841.952.7186 (3)152
Symmetry codes: (iii) x+2, y, z; (iv) x1/2, y1/2, z1/2.

Experimental details

(I)(IIa)(IIb)
Crystal data
Chemical formulaC6H6O4·H2OC6H6O4·C6H4O4C6H6O4·C6H4O4
Mr160.12282.20282.20
Crystal system, space groupMonoclinic, P2/nMonoclinic, P21/nMonoclinic, P21/n
Temperature (K)203163110
a, b, c (Å)13.487 (3), 3.647 (1), 13.506 (3)7.387 (3), 6.060 (1), 12.198 (2)7.382 (1), 6.065 (1), 12.197 (1)
β (°) 102.33 (3) 105.78 (2) 105.778 (1)
V3)649.1 (2)525.4 (3)525.51 (12)
Z422
Radiation typeMo KαCu KαSynchrotron, λ = 0.35400 Å
µ (mm1)0.151.340.09
Crystal size (mm)0.5 × 0.2 × 0.20.43 × 0.15 × 0.051.12 × 0.33 × 0.20
Data collection
DiffractometerBruker Smart1000 CCD
diffractometer
Enraf-Nonius CAD-4
diffractometer
R-axis IV image plate
diffractometer
Absorption correctionAnalytical
face-indexed (de Meulenaer & Tompa, 1965)
Tmin, Tmax0.877, 0.938
No. of measured, independent and
observed [I > 2σ(I)] reflections
3708, 1578, 1270 3379, 842, 753 13465, 5678, 4908
Rint0.0220.0210.032
(sin θ/λ)max1)0.6670.5781.233
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.045, 0.149, 1.22 0.035, 0.114, 1.14 0.031, 0.113, 1.04
No. of reflections15788425678
No. of parameters1169494
H-atom treatmentH-atom parameters constrainedH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.39, 0.260.19, 0.250.58, 0.48

Computer programs: SMART (Bruker, 1998), CAD-4 Software (Enraf-Nonius, 1993), HKL (Otwinowski & Minor, 1997), DIRAX (Duisenberg, 1992), HKL, SAINT-Plus (Bruker, 1998), local programs, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997a), SHELXTL/PC (Sheldrick, 1997b), SHELXTL/PC.

Selected geometric parameters (Å, º) for (I) top
O1—C11.386 (2)C1—C3iii1.384 (3)
O2—C21.378 (3)C1—C21.392 (3)
O3—C41.381 (3)C2—C31.391 (3)
O4—C61.379 (3)C3—C1iii1.384 (3)
O5—H5Ai0.80 (4)C4—C51.389 (3)
O5—H5A0.80 (4)C4—C6iv1.392 (3)
O6—H6A0.95 (5)C5—C61.386 (3)
O6—H6Aii0.95 (5)C6—C4iv1.392 (3)
C3iii—C1—O1122.50 (19)O3—C4—C5122.27 (19)
C3iii—C1—C2119.9 (2)O3—C4—C6iv117.50 (19)
O1—C1—C2117.57 (19)C5—C4—C6iv120.2 (2)
O2—C2—C3118.15 (19)C6—C5—C4120.41 (19)
O2—C2—C1122.5 (2)O4—C6—C5118.79 (19)
C3—C2—C1119.4 (2)O4—C6—C4iv121.84 (19)
C1iii—C3—C2120.7 (2)C5—C6—C4iv119.4 (2)
Symmetry codes: (i) x+1/2, y, z+1/2; (ii) x+1/2, y, z+3/2; (iii) x, y+1, z+1; (iv) x, y+2, z+2.
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O4ii0.831.962.756 (2)160.4
O2—H2···O6v0.831.922.735 (2)165.8
O3—H3A···O2vi0.831.882.699 (2)168.8
O4—H4···O5vii0.831.962.767 (2)162.9
O5—H5A···O3viii0.77 (3)2.07 (3)2.826 (2)165 (3)
O6—H6A···O10.95 (5)1.91 (5)2.832 (2)162 (3)
Symmetry codes: (ii) x+1/2, y, z+3/2; (v) x, y1, z; (vi) x, y+1, z; (vii) x, y, z+1; (viii) x+1/2, y+1, z1/2.
Selected geometric parameters (Å, º) for (IIa) top
O1—C11.3671 (16)C2—C31.3887 (19)
O2—C31.3742 (17)C3—C1i1.394 (2)
O3—C51.3320 (16)C4—C51.341 (2)
O4—C61.2355 (17)C4—C6ii1.4395 (19)
C1—C21.386 (2)C5—C61.505 (2)
C1—C3i1.394 (2)C6—C4ii1.4395 (19)
O1—C1—C2124.22 (12)C5—C4—C6ii120.36 (12)
O1—C1—C3i116.06 (12)O3—C5—C4126.65 (13)
C2—C1—C3i119.71 (13)O3—C5—C6112.26 (12)
C1—C2—C3119.77 (12)C4—C5—C6121.10 (13)
O2—C3—C2123.18 (12)O4—C6—C4ii123.02 (12)
O2—C3—C1i116.29 (12)O4—C6—C5118.44 (12)
C2—C3—C1i120.52 (12)C4ii—C6—C5118.54 (12)
Symmetry codes: (i) x+2, y+1, z; (ii) x+2, y, z+1.
Hydrogen-bond geometry (Å, º) for (IIa) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O4iii0.842.042.737 (1)139.9
O2—H3···O4iv0.841.852.686 (2)171.6
O3—H5···O20.841.952.719 (1)151.5
Symmetry codes: (iii) x+2, y, z; (iv) x1/2, y1/2, z1/2.
Selected geometric parameters (Å, º) for (IIb) top
O1—C11.3635 (3)C2—C31.3953 (4)
O2—C31.3710 (3)C3—C1i1.3994 (4)
O3—C51.3289 (3)C4—C51.3533 (4)
O4—C61.2386 (3)C4—C6ii1.4423 (4)
C1—C21.3923 (4)C5—C61.5011 (4)
C1—C3i1.3994 (4)C6—C4ii1.4423 (4)
O1—C1—C2124.09 (2)C5—C4—C6ii120.02 (2)
O1—C1—C3i116.21 (2)O3—C5—C4126.27 (2)
C2—C1—C3i119.69 (2)O3—C5—C6112.78 (2)
C1—C2—C3119.76 (2)C4—C5—C6120.94 (2)
O2—C3—C2122.87 (2)O4—C6—C4ii122.52 (2)
O2—C3—C1i116.56 (2)O4—C6—C5118.44 (2)
C2—C3—C1i120.55 (2)C4ii—C6—C5119.04 (2)
Symmetry codes: (i) x+2, y+1, z; (ii) x+2, y, z+1.
Hydrogen-bond geometry (Å, º) for (IIb) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O4iii0.842.042.7316 (4)139.9
O2—H3···O4iv0.841.852.6816 (4)171.4
O3—H5···O20.841.952.7186 (3)151.9
Symmetry codes: (iii) x+2, y, z; (iv) x1/2, y1/2, z1/2.
 

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