Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109010658/eg3011sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109010658/eg3011Isup2.hkl |
CCDC reference: 742181
A mixture of Pb(NO3)2 (108.7 mg, 0.33 mmol), 4,4'-bipyridine (18.8 mg, 0.12 mmol) and 4,4'-(hexafluoroisopropylidene)bis(phthalic anhydride) (69.6 mg, 0.16 mmol) in H2O (8 ml) was sealed in a 25 ml Teflon-lined stainless steel reactor and heated at 443 K for 72 h. A crop of colorless single crystals of the title compound was obtained after cooling the solution to room temperature. Platelet-shaped crystals were collected and washed with distilled water. The yield is ca 55% based on 4,4'-(hexafluoroisopropylidene)bis(phthalic anhydride). IR (KBr, ν/cm-1): 3540 (vs), 3400 (vs), 2930 (w), 2827 (w), 2653 (w), 2549 (w), 1973 (m), 1713 (vs), 1312 (w), 1254 (w), 1234 (w), 1072 (s), 982 (s), 840 (s), 795 (m), 750 (w), 703 (w), 658 (w), 600 (w).
All water H atoms were positioned from Fourier difference maps and refined subject to the constraint O—H = 0.82Å. The remaining H atoms were positioned geometrically and allowed to ride on their respective parent atoms at distances of C—H = 0.93Å and O—H = 0.82Å (for the carboxyl group), and with Uiso(H) = 1.2Ueq(C) or Uiso(H) = 1.5Ueq(O).
Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL'(Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
C19H10F6O8·6H2O | F(000) = 1208 |
Mr = 588.37 | Dx = 1.558 Mg m−3 |
Orthorhombic, Pbcn | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2n 2ab | Cell parameters from 22570 reflections |
a = 6.9425 (14) Å | θ = 3.3–27.5° |
b = 12.366 (3) Å | µ = 0.16 mm−1 |
c = 29.220 (6) Å | T = 298 K |
V = 2508.5 (9) Å3 | Platelet, colorless |
Z = 4 | 0.46 × 0.39 × 0.09 mm |
Rigaku R-AXIS RAPID diffractometer | 2852 independent reflections |
Radiation source: sealed tube | 2030 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.067 |
ω scans | θmax = 27.5°, θmin = 3.3° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −9→7 |
Tmin = 0.929, Tmax = 0.986 | k = −16→16 |
22570 measured reflections | l = −37→37 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.051 | H-atom parameters constrained |
wR(F2) = 0.109 | w = 1/[σ2(Fo2) + (0.0394P)2 + 1.3747P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max < 0.001 |
2852 reflections | Δρmax = 0.20 e Å−3 |
178 parameters | Δρmin = −0.16 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0063 (8) |
C19H10F6O8·6H2O | V = 2508.5 (9) Å3 |
Mr = 588.37 | Z = 4 |
Orthorhombic, Pbcn | Mo Kα radiation |
a = 6.9425 (14) Å | µ = 0.16 mm−1 |
b = 12.366 (3) Å | T = 298 K |
c = 29.220 (6) Å | 0.46 × 0.39 × 0.09 mm |
Rigaku R-AXIS RAPID diffractometer | 2852 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 2030 reflections with I > 2σ(I) |
Tmin = 0.929, Tmax = 0.986 | Rint = 0.067 |
22570 measured reflections |
R[F2 > 2σ(F2)] = 0.051 | 0 restraints |
wR(F2) = 0.109 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.20 e Å−3 |
2852 reflections | Δρmin = −0.16 e Å−3 |
178 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
F1 | 0.2076 (2) | 0.52973 (11) | 0.23850 (5) | 0.0637 (5) | |
F2 | 0.32395 (18) | 0.39289 (13) | 0.27426 (4) | 0.0575 (4) | |
F3 | 0.1190 (2) | 0.49568 (12) | 0.30730 (4) | 0.0633 (5) | |
O1 | 0.3582 (2) | 0.02704 (14) | 0.10885 (5) | 0.0548 (5) | |
O2 | 0.1164 (2) | 0.08433 (12) | 0.06539 (5) | 0.0462 (4) | |
H2B | 0.1557 | 0.0374 | 0.0479 | 0.069* | |
O3 | 0.4520 (3) | 0.25157 (15) | 0.07696 (5) | 0.0632 (5) | |
O4 | 0.5445 (2) | 0.36972 (13) | 0.12927 (5) | 0.0533 (5) | |
H4B | 0.6269 | 0.3838 | 0.1101 | 0.080* | |
O5 | 1.0118 (2) | 0.28172 (13) | 0.01698 (5) | 0.0504 (4) | |
H1 | 0.9807 | 0.2689 | −0.0096 | 0.076* | |
H2 | 1.0313 | 0.2246 | 0.0305 | 0.076* | |
O6 | 0.8192 (2) | 0.42691 (13) | 0.07227 (5) | 0.0505 (4) | |
H3 | 0.9150 | 0.4553 | 0.0836 | 0.076* | |
H4 | 0.8693 | 0.3771 | 0.0580 | 0.076* | |
O7 | 1.2915 (3) | 0.44327 (13) | 0.00541 (5) | 0.0540 (5) | |
H5 | 1.2081 | 0.3974 | 0.0099 | 0.081* | |
H6 | 1.2514 | 0.4791 | −0.0162 | 0.081* | |
C1 | 0.2269 (3) | 0.08807 (16) | 0.10163 (6) | 0.0336 (5) | |
C2 | 0.1645 (3) | 0.17074 (15) | 0.13612 (6) | 0.0304 (4) | |
C3 | 0.0027 (3) | 0.14948 (16) | 0.16214 (7) | 0.0381 (5) | |
H3A | −0.0733 | 0.0897 | 0.1553 | 0.046* | |
C4 | −0.0475 (3) | 0.21627 (16) | 0.19823 (7) | 0.0354 (5) | |
H4A | −0.1569 | 0.2008 | 0.2154 | 0.043* | |
C5 | 0.0633 (3) | 0.30591 (15) | 0.20908 (6) | 0.0267 (4) | |
C6 | 0.2207 (3) | 0.33007 (15) | 0.18159 (6) | 0.0289 (4) | |
H6A | 0.2932 | 0.3917 | 0.1876 | 0.035* | |
C7 | 0.2716 (3) | 0.26332 (15) | 0.14520 (6) | 0.0291 (4) | |
C8 | 0.4323 (3) | 0.29321 (17) | 0.11384 (6) | 0.0349 (5) | |
C9 | 0.0000 | 0.3763 (2) | 0.2500 | 0.0276 (6) | |
C10 | 0.1639 (3) | 0.44915 (18) | 0.26746 (7) | 0.0431 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
F1 | 0.0853 (11) | 0.0453 (8) | 0.0605 (9) | −0.0314 (8) | 0.0293 (8) | −0.0090 (7) |
F2 | 0.0335 (7) | 0.0948 (11) | 0.0443 (7) | −0.0123 (7) | 0.0000 (6) | −0.0126 (7) |
F3 | 0.0714 (10) | 0.0733 (10) | 0.0452 (8) | −0.0304 (8) | 0.0230 (7) | −0.0328 (7) |
O1 | 0.0591 (11) | 0.0620 (11) | 0.0432 (9) | 0.0254 (9) | −0.0043 (8) | −0.0092 (8) |
O2 | 0.0580 (10) | 0.0459 (9) | 0.0348 (8) | 0.0108 (8) | −0.0097 (7) | −0.0139 (7) |
O3 | 0.0741 (12) | 0.0795 (12) | 0.0359 (8) | −0.0297 (10) | 0.0256 (9) | −0.0207 (9) |
O4 | 0.0482 (9) | 0.0673 (11) | 0.0446 (9) | −0.0255 (8) | 0.0206 (8) | −0.0167 (8) |
O5 | 0.0684 (11) | 0.0458 (9) | 0.0370 (8) | −0.0036 (8) | −0.0073 (8) | −0.0028 (7) |
O6 | 0.0381 (9) | 0.0590 (10) | 0.0544 (10) | −0.0132 (7) | 0.0103 (7) | −0.0102 (8) |
O7 | 0.0696 (12) | 0.0512 (10) | 0.0412 (8) | −0.0138 (9) | 0.0040 (8) | −0.0091 (7) |
C1 | 0.0402 (11) | 0.0328 (10) | 0.0277 (9) | 0.0006 (9) | 0.0021 (9) | 0.0005 (8) |
C2 | 0.0355 (11) | 0.0329 (10) | 0.0229 (9) | 0.0012 (8) | 0.0011 (8) | −0.0002 (8) |
C3 | 0.0421 (12) | 0.0360 (11) | 0.0362 (11) | −0.0111 (9) | 0.0056 (9) | −0.0066 (9) |
C4 | 0.0345 (11) | 0.0397 (11) | 0.0321 (10) | −0.0083 (9) | 0.0094 (9) | −0.0023 (9) |
C5 | 0.0295 (10) | 0.0288 (9) | 0.0218 (8) | 0.0006 (8) | 0.0025 (7) | 0.0003 (7) |
C6 | 0.0306 (10) | 0.0313 (10) | 0.0249 (9) | −0.0033 (8) | 0.0019 (8) | −0.0021 (8) |
C7 | 0.0291 (10) | 0.0348 (10) | 0.0234 (9) | −0.0005 (8) | 0.0022 (8) | 0.0004 (8) |
C8 | 0.0373 (11) | 0.0395 (11) | 0.0280 (10) | −0.0023 (9) | 0.0055 (9) | −0.0032 (8) |
C9 | 0.0291 (14) | 0.0280 (13) | 0.0257 (13) | 0.000 | 0.0051 (11) | 0.000 |
C10 | 0.0509 (14) | 0.0456 (13) | 0.0329 (11) | −0.0144 (11) | 0.0133 (10) | −0.0106 (9) |
F1—C10 | 1.342 (3) | C1—C2 | 1.500 (3) |
F2—C10 | 1.326 (3) | C2—C3 | 1.381 (3) |
F3—C10 | 1.335 (2) | C2—C7 | 1.391 (3) |
O1—C1 | 1.202 (2) | C3—C4 | 1.384 (3) |
O2—C1 | 1.309 (2) | C3—H3A | 0.9300 |
O2—H2B | 0.8200 | C4—C5 | 1.386 (3) |
O3—C8 | 1.202 (2) | C4—H4A | 0.9300 |
O4—C8 | 1.306 (2) | C5—C6 | 1.388 (3) |
O4—H4B | 0.8200 | C5—C9 | 1.543 (2) |
O5—H1 | 0.8210 | C6—C7 | 1.392 (3) |
O5—H2 | 0.8211 | C6—H6A | 0.9300 |
O6—H3 | 0.8211 | C7—C8 | 1.490 (3) |
O6—H4 | 0.8211 | C9—C10 | 1.538 (3) |
O7—H5 | 0.8210 | C9—C10i | 1.538 (3) |
O7—H6 | 0.8209 | C9—C5i | 1.543 (2) |
C1—O2—H2B | 109.5 | C5—C6—H6A | 119.5 |
C8—O4—H4B | 109.5 | C7—C6—H6A | 119.5 |
H1—O5—H2 | 109.5 | C2—C7—C6 | 119.88 (17) |
H3—O6—H4 | 100.5 | C2—C7—C8 | 119.15 (16) |
H5—O7—H6 | 104.8 | C6—C7—C8 | 120.85 (17) |
O1—C1—O2 | 124.38 (19) | O3—C8—O4 | 123.50 (19) |
O1—C1—C2 | 121.95 (18) | O3—C8—C7 | 122.02 (19) |
O2—C1—C2 | 113.47 (17) | O4—C8—C7 | 114.45 (16) |
C3—C2—C7 | 119.11 (17) | C10—C9—C10i | 108.3 (2) |
C3—C2—C1 | 118.38 (18) | C10—C9—C5 | 112.12 (11) |
C7—C2—C1 | 122.32 (17) | C10i—C9—C5 | 106.50 (11) |
C2—C3—C4 | 120.70 (18) | C10—C9—C5i | 106.50 (11) |
C2—C3—H3A | 119.7 | C10i—C9—C5i | 112.12 (11) |
C4—C3—H3A | 119.7 | C5—C9—C5i | 111.3 (2) |
C3—C4—C5 | 120.77 (18) | F2—C10—F3 | 106.93 (19) |
C3—C4—H4A | 119.6 | F2—C10—F1 | 107.12 (18) |
C5—C4—H4A | 119.6 | F3—C10—F1 | 106.41 (18) |
C4—C5—C6 | 118.48 (17) | F2—C10—C9 | 111.25 (18) |
C4—C5—C9 | 118.04 (16) | F3—C10—C9 | 111.63 (16) |
C6—C5—C9 | 123.43 (16) | F1—C10—C9 | 113.13 (18) |
C5—C6—C7 | 120.93 (17) |
Symmetry code: (i) −x, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2B···O7ii | 0.82 | 1.74 | 2.554 (2) | 171 |
O4—H4B···O6 | 0.82 | 1.81 | 2.629 (2) | 173 |
O5—H1···O3iii | 0.82 | 1.99 | 2.806 (2) | 170 |
O5—H2···O2iv | 0.82 | 2.10 | 2.913 (2) | 173 |
O6—H3···O1v | 0.82 | 1.95 | 2.773 (2) | 178 |
O6—H4···O5 | 0.82 | 1.95 | 2.760 (2) | 169 |
O7—H5···O5 | 0.82 | 1.99 | 2.806 (2) | 176 |
O7—H6···O6vi | 0.82 | 2.07 | 2.884 (2) | 174 |
Symmetry codes: (ii) −x+3/2, y−1/2, z; (iii) x+1/2, −y+1/2, −z; (iv) x+1, y, z; (v) −x+3/2, y+1/2, z; (vi) −x+2, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | C19H10F6O8·6H2O |
Mr | 588.37 |
Crystal system, space group | Orthorhombic, Pbcn |
Temperature (K) | 298 |
a, b, c (Å) | 6.9425 (14), 12.366 (3), 29.220 (6) |
V (Å3) | 2508.5 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.16 |
Crystal size (mm) | 0.46 × 0.39 × 0.09 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID diffractometer |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.929, 0.986 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 22570, 2852, 2030 |
Rint | 0.067 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.109, 1.02 |
No. of reflections | 2852 |
No. of parameters | 178 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.20, −0.16 |
Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL'(Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2B···O7i | 0.82 | 1.74 | 2.554 (2) | 171.0 |
O4—H4B···O6 | 0.82 | 1.81 | 2.629 (2) | 173.2 |
O5—H1···O3ii | 0.82 | 1.99 | 2.806 (2) | 169.6 |
O5—H2···O2iii | 0.82 | 2.10 | 2.913 (2) | 173.0 |
O6—H3···O1iv | 0.82 | 1.95 | 2.773 (2) | 177.9 |
O6—H4···O5 | 0.82 | 1.95 | 2.760 (2) | 168.7 |
O7—H5···O5 | 0.82 | 1.99 | 2.806 (2) | 176.3 |
O7—H6···O6v | 0.82 | 2.07 | 2.884 (2) | 173.9 |
Symmetry codes: (i) −x+3/2, y−1/2, z; (ii) x+1/2, −y+1/2, −z; (iii) x+1, y, z; (iv) −x+3/2, y+1/2, z; (v) −x+2, −y+1, −z. |
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Great attention have been paid to small water clusters both in theoretical and experimental studies not only with the aim to understand hydrogen-bonding interactions and the behavior of bulk water, but also due to their fascinating topology when associated with organic molecules or metal-organic frameworks (Ludwig, 2001; Ugalde et al., 2000; Maheshwary et al., 2001; Chesnut, 2002; Sadlej et al., 1999; Custelcean et al., 2000; López et al., 2008). Many discrete water clusters, including tetramers, hexamers, octamers, decamers and higher clusters, have been identified. Among the water clusters, cyclic hexamers are of special interest because they are the building blocks of ice Ih (reference?) and expected to be relevant for the structure of liquid water. Theoretical calculations suggest that several different isomers for the water hexamer, such as ring, book, cage, cyclic and prism, represent nearly isoenergetic clusters (Ludwig, 2001; Chesnut, 2002). However, understanding how the water clusters link into higher dimensional networks is still challenging. Recently, water clusters associated with organic, inorganic, or metal–organic frameworks have been studied. One-dimensional aggregates such as water chains and tapes and a few examples of two- or three-dimensional polymers (Wang et al., 2006; Michaelides et al., 2003; Hu et al., 2007; Mukhopadhyay et al., 2005; Ye et al., 2004; Neogi et al., 2005; Zheng et al., 2005; Ghosh et al., 2004; Ghosh et al., 2005; Ghosh et al., 2003) have been described. In this contribution, we report the synthesis of the title compound under hydrothermal conditions, which contains an unexpected cyclic water hexamer in a chair conformation. Interestingly, an unique three-dimensional supramolecular network is formed by strong intermolecular O—H···O hydrogen bonds between these hexamers and the large organic residue. To our knowledge, this compound is the first example for a (3,4,4,10)-connected 4-nodal supramolecular topology associated with the Schläfli symbol (43.5.6.7)2(43.52.7)2(43)2(46.56.62.78.814.99).
The asymmetric unit of (I) consists of one half the 4,4'-(hexafluoroisopropylidene)bis(phthalic acid) (H4hfipdpt) molecule and three water molecules (Fig. 1). The benzene rings of the bent H4hfipdpt molecule subtend a dihedral angle of 65.8(?)°. As shown in Fig. 2, the carboxylate groups of H4hfipdpt adopt syn–syn 1,3-µ2-carboxylate and 1,1,3-µ3-carboxylate coordination modes, which are crosslinked by different cyclic hexameric water clusters via strong O—H···O intermolecular hydrogen bonds. In each cyclic hexamer unit, the average O···O distance is 2.817(?)Å, which is in the range of the corresponding values in ice Ih (2.759(?)Å; Ludwig, 2001) at 183 K and in liquid water (2.85(?)Å; Ludwig, 2001). The O···O···O angles range from 86.71(?) to 107.85(?)° and are smaller than the value of 109.3° in hexagonal ice (Ludwig, 2001; Michaelides et al., 2003). The water molecules (O5, O6 and O7) of the hexamers adopt 4-, 4- and 3-connected modes, respectively. The hexamers in the subunits are crosslinked with different organic H4hfipdpt molecules via strong intermolecular O—H···O hydrogen bonds [O···O = 2.554 (2)–2.913 (2)Å], which give rise to a unique three-dimensional hydrogen-bonded supramolecular network (Fig. 3). The geometric parameters of the hydrogen bonds are listed in Table 1. The resulting three-dimensional supramolecular framework exhibits an interesting (3,4,4,10)-connected topology. A calculation of the vertex symbol with the help of the program TOPOS (Blatov et al., 2000) shows that the title compound exhibits a unique (3,4,4,10)-connected 4-nodal supramolecular topology with the Schläfli symbol (43.5.6.7)2(43.52.7)2(43)2(46.56.62.78.814.99) (Fig. 4).
The FT–IR spectrum was interpreted in the light of the structural results. The stretching frequency of the O—H bonds was observed at ca 3540 and 3400 cm-1, which is both due to the hexameric water cluster and the carboxyl group. The first peak is close to the value of 3490 cm-1 reported for liquid water, while the second peak is slightly greater than the value of the reported cyclic water hexamer (3335 cm-1) formed in liquid helium and the measured band at 3359 cm-1 for the hexamer in an organic molecular crystal host because of the co-operative effects between the clusters and organic molecules (Custelcean et al., 2000; Michaelides et al., 2003; Buck & Huisken, 2000).