Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100018485/bj1012sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100018485/bj1012Isup2.hkl |
CCDC reference: 160009
Compound (I) was made by Houben-Hoesch reaction of phloroglucinol with methoxyacetonitrile in the presence of anhydrous HCl and ZnCl2 (Deng et al., 1997). Crystals were obtained by recrystallization from water.
Program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997).
Fig. 1. A view of (I) with atom-numbering scheme. Displacement ellipsoids enclose 50% probability surfaces. The symmetry element relating the two molecules is (x, -y, z + 1/2). |
C9H10O5·H2O | Dx = 1.518 Mg m−3 |
Mr = 216.19 | Melting point = 197–198 K |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 17.3138 (5) Å | Cell parameters from 24172 reflections |
b = 7.3330 (1) Å | θ = 2.7–27.6° |
c = 16.8507 (5) Å | µ = 0.13 mm−1 |
β = 117.838 (1)° | T = 150 K |
V = 1891.81 (8) Å3 | Block, colourless |
Z = 8 | 0.35 × 0.10 × 0.10 mm |
F(000) = 912 |
Nonius kappa-ccd diffractometer | 2180 independent reflections |
Radiation source: fine-focus sealed tube | 1594 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.076 |
ω–ϕ scans | θmax = 27.6°, θmin = 2.7° |
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997) | h = −22→22 |
Tmin = 0.811, Tmax = 1.000 | k = −9→9 |
24172 measured reflections | l = −21→21 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.041 | All H-atom parameters refined |
wR(F2) = 0.109 | w = 1/[σ2(Fo2) + (0.0647P)2 + 0.0798P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.003 |
2180 reflections | Δρmax = 0.25 e Å−3 |
185 parameters | Δρmin = −0.30 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0031 (7) |
C9H10O5·H2O | V = 1891.81 (8) Å3 |
Mr = 216.19 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 17.3138 (5) Å | µ = 0.13 mm−1 |
b = 7.3330 (1) Å | T = 150 K |
c = 16.8507 (5) Å | 0.35 × 0.10 × 0.10 mm |
β = 117.838 (1)° |
Nonius kappa-ccd diffractometer | 2180 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997) | 1594 reflections with I > 2σ(I) |
Tmin = 0.811, Tmax = 1.000 | Rint = 0.076 |
24172 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.109 | All H-atom parameters refined |
S = 1.05 | Δρmax = 0.25 e Å−3 |
2180 reflections | Δρmin = −0.30 e Å−3 |
185 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.23569 (8) | 0.00284 (15) | 0.00971 (8) | 0.0180 (3) | |
C11 | 0.25519 (8) | 0.06309 (16) | 0.09908 (8) | 0.0195 (3) | |
O11 | 0.19824 (6) | 0.05665 (13) | 0.12456 (6) | 0.0261 (3) | |
C12 | 0.34383 (9) | 0.13446 (18) | 0.16560 (9) | 0.0208 (3) | |
H121 | 0.3602 (9) | 0.239 (2) | 0.1421 (9) | 0.024 (4)* | |
H122 | 0.3880 (9) | 0.0317 (19) | 0.1771 (9) | 0.026 (4)* | |
O13 | 0.34140 (6) | 0.18287 (13) | 0.24528 (6) | 0.0258 (3) | |
C14 | 0.42330 (10) | 0.2538 (2) | 0.31023 (10) | 0.0285 (4) | |
H141 | 0.4389 (11) | 0.363 (2) | 0.2867 (11) | 0.039 (4)* | |
H142 | 0.4170 (11) | 0.280 (2) | 0.3634 (12) | 0.043 (5)* | |
H143 | 0.4686 (11) | 0.162 (2) | 0.3287 (10) | 0.037 (4)* | |
C2 | 0.29487 (8) | 0.01225 (16) | −0.02657 (8) | 0.0187 (3) | |
O2 | 0.37443 (6) | 0.08560 (13) | 0.02463 (6) | 0.0243 (3) | |
H2 | 0.4013 (13) | 0.096 (3) | −0.0067 (12) | 0.052 (6)* | |
C3 | 0.27236 (9) | −0.05141 (17) | −0.11188 (9) | 0.0203 (3) | |
H3 | 0.3131 (9) | −0.0447 (18) | −0.1343 (9) | 0.019 (3)* | |
C4 | 0.19037 (9) | −0.12680 (16) | −0.16349 (9) | 0.0212 (3) | |
O4 | 0.16706 (7) | −0.19456 (14) | −0.24634 (6) | 0.0301 (3) | |
H4 | 0.2034 (14) | −0.161 (3) | −0.2648 (13) | 0.064 (6)* | |
C5 | 0.12936 (9) | −0.13642 (17) | −0.13223 (9) | 0.0215 (3) | |
H5 | 0.0720 (10) | −0.1879 (18) | −0.1684 (9) | 0.021 (4)* | |
C6 | 0.15172 (8) | −0.07230 (17) | −0.04718 (9) | 0.0196 (3) | |
O6 | 0.08997 (6) | −0.08119 (13) | −0.01953 (7) | 0.0260 (3) | |
H6 | 0.1135 (12) | −0.035 (2) | 0.0366 (14) | 0.057 (6)* | |
O1W | 0.04638 (7) | 0.34550 (14) | 0.07748 (7) | 0.0282 (3) | |
H1W | 0.0019 (13) | 0.275 (3) | 0.0575 (13) | 0.058 (6)* | |
H2W | 0.0810 (14) | 0.297 (3) | 0.1330 (16) | 0.064 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0200 (7) | 0.0173 (7) | 0.0184 (7) | 0.0011 (5) | 0.0104 (6) | 0.0022 (5) |
C11 | 0.0220 (7) | 0.0173 (6) | 0.0217 (7) | 0.0015 (5) | 0.0125 (6) | 0.0032 (5) |
O11 | 0.0248 (6) | 0.0348 (6) | 0.0246 (5) | −0.0039 (4) | 0.0165 (5) | −0.0045 (4) |
C12 | 0.0245 (8) | 0.0220 (7) | 0.0188 (7) | −0.0005 (5) | 0.0124 (6) | −0.0008 (5) |
O13 | 0.0254 (6) | 0.0367 (6) | 0.0178 (5) | −0.0048 (4) | 0.0121 (4) | −0.0063 (4) |
C14 | 0.0280 (9) | 0.0347 (9) | 0.0206 (8) | −0.0039 (6) | 0.0095 (7) | −0.0041 (6) |
C2 | 0.0183 (7) | 0.0170 (6) | 0.0205 (7) | 0.0013 (5) | 0.0088 (6) | 0.0022 (5) |
O2 | 0.0188 (5) | 0.0349 (6) | 0.0221 (5) | −0.0048 (4) | 0.0118 (4) | −0.0045 (4) |
C3 | 0.0225 (7) | 0.0212 (7) | 0.0219 (7) | 0.0001 (5) | 0.0143 (6) | 0.0012 (5) |
C4 | 0.0294 (8) | 0.0182 (7) | 0.0178 (7) | −0.0005 (5) | 0.0125 (6) | 0.0010 (5) |
O4 | 0.0367 (7) | 0.0376 (6) | 0.0216 (6) | −0.0122 (5) | 0.0183 (5) | −0.0084 (4) |
C5 | 0.0220 (8) | 0.0218 (7) | 0.0199 (7) | −0.0032 (5) | 0.0092 (6) | 0.0012 (5) |
C6 | 0.0207 (7) | 0.0184 (7) | 0.0229 (7) | 0.0000 (5) | 0.0128 (6) | 0.0022 (5) |
O6 | 0.0225 (6) | 0.0362 (6) | 0.0250 (6) | −0.0074 (4) | 0.0157 (5) | −0.0054 (4) |
O1W | 0.0218 (6) | 0.0355 (6) | 0.0272 (6) | −0.0030 (4) | 0.0115 (5) | 0.0039 (5) |
C1—C2 | 1.4190 (18) | C2—C3 | 1.3831 (18) |
C1—C6 | 1.4265 (18) | O2—H2 | 0.86 (2) |
C1—C11 | 1.4499 (17) | C3—C4 | 1.3872 (19) |
C11—O11 | 1.2466 (15) | C3—H3 | 0.945 (15) |
C11—C12 | 1.5096 (18) | C4—O4 | 1.3537 (16) |
C12—O13 | 1.4084 (16) | C4—C5 | 1.3849 (19) |
C12—H121 | 0.964 (15) | O4—H4 | 0.86 (2) |
C12—H122 | 1.025 (14) | C5—C6 | 1.3808 (18) |
O13—C14 | 1.4246 (17) | C5—H5 | 0.967 (14) |
C14—H141 | 0.986 (16) | C6—O6 | 1.3527 (16) |
C14—H142 | 0.972 (19) | O6—H6 | 0.90 (2) |
C14—H143 | 0.967 (16) | O1W—H1W | 0.86 (2) |
C2—O2 | 1.3495 (15) | O1W—H2W | 0.92 (2) |
C2—C1—C6 | 116.34 (11) | O2—C2—C3 | 120.47 (12) |
C2—C1—C11 | 124.61 (11) | O2—C2—C1 | 118.08 (11) |
C6—C1—C11 | 119.06 (11) | C3—C2—C1 | 121.45 (12) |
O11—C11—C1 | 120.54 (12) | C2—O2—H2 | 109.2 (12) |
O11—C11—C12 | 116.80 (11) | C2—C3—C4 | 119.69 (12) |
C1—C11—C12 | 122.66 (11) | C2—C3—H3 | 119.9 (8) |
O13—C12—C11 | 108.82 (10) | C4—C3—H3 | 120.4 (8) |
O13—C12—H121 | 109.7 (8) | O4—C4—C5 | 117.42 (12) |
C11—C12—H121 | 111.2 (8) | O4—C4—C3 | 121.18 (12) |
O13—C12—H122 | 110.9 (8) | C5—C4—C3 | 121.39 (12) |
C11—C12—H122 | 107.2 (8) | C4—O4—H4 | 110.8 (14) |
H121—C12—H122 | 109.0 (12) | C6—C5—C4 | 118.91 (12) |
C12—O13—C14 | 111.25 (10) | C6—C5—H5 | 119.6 (9) |
O13—C14—H141 | 110.4 (9) | C4—C5—H5 | 121.4 (9) |
O13—C14—H142 | 106.3 (10) | O6—C6—C5 | 117.23 (12) |
H141—C14—H142 | 112.2 (14) | O6—C6—C1 | 120.57 (11) |
O13—C14—H143 | 111.1 (9) | C5—C6—C1 | 122.20 (12) |
H141—C14—H143 | 111.1 (13) | C6—O6—H6 | 107.5 (12) |
H142—C14—H143 | 105.4 (14) | H1W—O1W—H2W | 101.7 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1Wi | 0.85 (2) | 1.85 (2) | 2.7017 (16) | 171 (2) |
O4—H4···O11ii | 0.86 (3) | 1.98 (2) | 2.6727 (15) | 137 (2) |
O4—H4···O13ii | 0.86 (3) | 2.32 (3) | 3.0881 (17) | 149.1 (19) |
O6—H6···O11 | 0.90 (2) | 1.66 (2) | 2.4860 (14) | 150 (2) |
O1W—H1W···O6iii | 0.86 (2) | 2.00 (2) | 2.8514 (16) | 172 (2) |
O1W—H2W···O4iv | 0.92 (2) | 2.02 (2) | 2.9345 (14) | 175 (2) |
Symmetry codes: (i) −x+1/2, −y+1/2, −z; (ii) x, −y, z−1/2; (iii) −x, −y, −z; (iv) x, −y, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C9H10O5·H2O |
Mr | 216.19 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 150 |
a, b, c (Å) | 17.3138 (5), 7.3330 (1), 16.8507 (5) |
β (°) | 117.838 (1) |
V (Å3) | 1891.81 (8) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.13 |
Crystal size (mm) | 0.35 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Nonius kappa-ccd diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995, 1997) |
Tmin, Tmax | 0.811, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 24172, 2180, 1594 |
Rint | 0.076 |
(sin θ/λ)max (Å−1) | 0.651 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.109, 1.05 |
No. of reflections | 2180 |
No. of parameters | 185 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.25, −0.30 |
Computer programs: SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997).
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1Wi | 0.85 (2) | 1.85 (2) | 2.7017 (16) | 171 (2) |
O4—H4···O11ii | 0.86 (3) | 1.98 (2) | 2.6727 (15) | 137 (2) |
O4—H4···O13ii | 0.86 (3) | 2.32 (3) | 3.0881 (17) | 149.1 (19) |
O6—H6···O11 | 0.90 (2) | 1.66 (2) | 2.4860 (14) | 150 (2) |
O1W—H1W···O6iii | 0.86 (2) | 2.00 (2) | 2.8514 (16) | 172 (2) |
O1W—H2W···O4iv | 0.92 (2) | 2.02 (2) | 2.9345 (14) | 175 (2) |
Symmetry codes: (i) −x+1/2, −y+1/2, −z; (ii) x, −y, z−1/2; (iii) −x, −y, −z; (iv) x, −y, z+1/2. |
The molecular geometry in the title compound, (I), was determined in order to study the geometric distortions in a tetra- substituted benzene derivative and to investigate the possibilities for inter- and intra-molecular hydrogen bonding in the solid state. Only a few closely analogous structures have been reported. For example cudranone, (II), and the chalcone (III) are both ketones which contain the 2,6-dihydroxybenzene sub-structure, the former being a benzophenone derivative, the latter having an saturated side-chain (Ottersen et al., 1977; Ulrich et al., 1990). Both have methoxy groups in the 4-position of the hydroxylated ring, whereas (I) is a 2,4,6-trihydroxybenzene derivative. \sch
The intramolecular geometry of (I) is dominated by a cyclic hydrogen bond involving the O6—H6 and the oxygen, O11, of the carbonyl group [O6···O11 2.4860 (14) Å and H6···O11 1.66 (2) Å]. The molecular structure, labelling scheme and partial hydrogen bonding is depicted in Figure 1. The O.·O distances in (II) and (III) are 2.501 (3) and 2.406 (3) Å, respectively. Intramolecular hydrogen bonding has little effect on the length of the C—O bond of the participating phenol group of (I), e.g. C6—O6 is 1.3527 (16) and C4—O4 is 1.3537 (16) Å. The bond lengths of the benzene ring of (I) are distorted: those flanking the carbonyl group, C1—C2 and C1—C6, are 1.4190 (18) and 1.4265 (18) Å, respectively, whereas the others lie between 1.380 and 1.390 Å. The longest ring bond is that which is involved in the cyclic hydrogen bond. Similar features are present in the structures of (II) and (III).
The internal bond angles in the benzene ring of (I) range from 116.34 (11) to 122.20 (12)°, the former being at the point of substitution of the acyl group, and the latter at that of the intramolecularly hydrogen-bonded hydroxy group. The bond angles generally agree well with those calculated using the angular substituent parameters described in Domenicano (1992). The largest deviation (1.3°) is found at C1. Once again similar features are apparent in (II) and (III). The geometry about the C═O group is very similar in (I) and (II). In (I), the aryl-carbon distance, C1—C11 [1.4499 (17) Å] is substantially shorter than that of the alkyl-carbon distance C11—C12 [1.5096 (18) Å], as expected. In (II), the similarity of the magnitude of these two features is more surprising; however, the longer bond length is that to the mono-hydroxylated ring, which is twisted substantially out of plane, and therefore unable to participate in conjugation.
The entire molecule of (I), including the methoxy group, is planar [mean deviation 0.006 Å from the plane of the ring; maximum deviation 0.201 Å for C14]. This is ascribable to the formation of a bifurcated intermolecular hydrogen bond from H4 of a neighbouring molecule to O11 and O13 (Fig. 1). The interaction shown in Fig 1 extends to form corrugated sheets of molecules which are hydrogen bonded together by molecules of water of crystallization (see Table 3).