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In methylaminium 4′,7-dihydroxyisoflavone-3′-sulfonate dihydrate, CH6N+·C15H9O7S−·2H2O, 11 hydrogen bonds exist between the methylaminium cations, the isoflavone-3′-sulfonate anions and the solvent water molecules. In hexaaquairon(II) bis(4′,7-diethoxyisoflavone-3′-sulfonate) tetrahydrate, [Fe(H2O)6](C19H17O7S)2·4H2O, 12 hydrogen bonds exist between the centrosymmetric [Fe(H2O)6]2+ cation, the isoflavone-3′-sulfonate anions and the solvent water molecules. Additional π–π stacking interactions generate three-dimensional supramolecular structures in both compounds.
Supporting information
CCDC references: 625705; 625706
Sodium 4',7-dihydroxyisoflavone-3'-sulfonate and sodium 4',7-diethoxyisoflavone-3'-sulfonate were prepared as described by Liu et al. (2003) and Zhang & Wang (2005a), respectively. They were dissolved (1 g) in water (10 ml) and then separately mixed with a saturated CH3NH3+Cl− solution (5 ml) or FeSO4·7H2O solution (5 ml) in water. Crystals of (I) and (II) were obtained after 2 and 3 d, respectively. On recrystallization from water, single crystals suitable for X-ray diffraction were obtained by slow evaporation (m.p. 585 and 611 K, respectively; decomposition).
All H atoms were placed in calculated positions and treated as riding, with N—H 0.89 Å, O—H 0.82 Å and C—H in the range 0.93- 0.96 Å and with Uiso(H) = 1.2Ueq(C,N,O) for compound (I), and with O—H in the range 0.84–0.85 Å and C—H in the range 0.93–0.97 Å and with Uiso(H) = 1.2Ueq(C,O) for compound (II).
For both compounds, data collection: SMART (Bruker, 1999); cell refinement: SMART; data reduction: SAINT-Plus (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.
(I) methylaminium 4',7-dihydroxyisoflavone-3'-sulfonate dihydrate
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Crystal data top
CH6N+·C15H9O7S−·2H2O | F(000) = 840 |
Mr = 401.38 | Dx = 1.504 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2270 reflections |
a = 17.852 (13) Å | θ = 2.3–25.2° |
b = 7.365 (5) Å | µ = 0.24 mm−1 |
c = 13.558 (10) Å | T = 298 K |
β = 96.194 (11)° | Rhomboid, colourless |
V = 1772 (2) Å3 | 0.53 × 0.45 × 0.21 mm |
Z = 4 | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 3123 independent reflections |
Radiation source: fine-focus sealed tube | 2147 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.048 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | h = −21→10 |
Tmin = 0.886, Tmax = 0.952 | k = −8→8 |
8930 measured reflections | l = −15→16 |
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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.123 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0606P)2 + 0.3658P] where P = (Fo2 + 2Fc2)/3 |
3123 reflections | (Δ/σ)max < 0.001 |
246 parameters | Δρmax = 0.35 e Å−3 |
0 restraints | Δρmin = −0.27 e Å−3 |
Crystal data top
CH6N+·C15H9O7S−·2H2O | V = 1772 (2) Å3 |
Mr = 401.38 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 17.852 (13) Å | µ = 0.24 mm−1 |
b = 7.365 (5) Å | T = 298 K |
c = 13.558 (10) Å | 0.53 × 0.45 × 0.21 mm |
β = 96.194 (11)° | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 3123 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | 2147 reflections with I > 2σ(I) |
Tmin = 0.886, Tmax = 0.952 | Rint = 0.048 |
8930 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.123 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.35 e Å−3 |
3123 reflections | Δρmin = −0.27 e Å−3 |
246 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | 0.07471 (13) | 0.8347 (3) | 0.73074 (19) | 0.0448 (6) | |
H1A | 0.0435 | 0.8639 | 0.7752 | 0.067* | |
H1B | 0.0597 | 0.7310 | 0.7011 | 0.067* | |
H1C | 0.0744 | 0.9224 | 0.6856 | 0.067* | |
O1 | 0.50035 (10) | 0.5072 (3) | 0.73346 (14) | 0.0417 (5) | |
O2 | 0.35356 (10) | 0.1822 (3) | 0.56181 (14) | 0.0397 (5) | |
O3 | 0.70137 (11) | 0.3641 (3) | 0.55071 (18) | 0.0582 (6) | |
H3 | 0.7111 | 0.3067 | 0.5019 | 0.087* | |
O4 | 0.08814 (10) | 0.2597 (3) | 0.82469 (14) | 0.0430 (5) | |
H4 | 0.0919 | 0.2413 | 0.8847 | 0.065* | |
O5 | 0.10915 (10) | 0.3877 (3) | 0.51389 (13) | 0.0417 (5) | |
O6 | 0.04810 (11) | 0.1607 (3) | 0.60596 (16) | 0.0496 (6) | |
O7 | 0.03388 (10) | 0.4770 (3) | 0.64280 (14) | 0.0407 (5) | |
S1 | 0.08258 (4) | 0.33863 (9) | 0.60804 (5) | 0.0287 (2) | |
C1 | 0.42731 (15) | 0.4882 (4) | 0.7506 (2) | 0.0370 (7) | |
H1 | 0.4118 | 0.5522 | 0.8039 | 0.044* | |
C2 | 0.37561 (14) | 0.3865 (3) | 0.69826 (18) | 0.0271 (6) | |
C3 | 0.39663 (14) | 0.2856 (3) | 0.61197 (19) | 0.0275 (6) | |
C4 | 0.47498 (14) | 0.3128 (3) | 0.59102 (19) | 0.0273 (6) | |
C5 | 0.50372 (15) | 0.2275 (4) | 0.5111 (2) | 0.0321 (6) | |
H5 | 0.4717 | 0.1586 | 0.4672 | 0.038* | |
C6 | 0.57858 (15) | 0.2435 (4) | 0.4960 (2) | 0.0367 (7) | |
H6 | 0.5967 | 0.1861 | 0.4423 | 0.044* | |
C7 | 0.62692 (15) | 0.3462 (4) | 0.5616 (2) | 0.0378 (7) | |
C8 | 0.60027 (15) | 0.4337 (4) | 0.6409 (2) | 0.0377 (7) | |
H8 | 0.6325 | 0.5022 | 0.6847 | 0.045* | |
C9 | 0.52411 (14) | 0.4174 (4) | 0.6540 (2) | 0.0311 (6) | |
C10 | 0.29904 (14) | 0.3641 (3) | 0.73129 (18) | 0.0273 (6) | |
C11 | 0.23411 (14) | 0.3643 (3) | 0.66400 (18) | 0.0264 (6) | |
H11 | 0.2380 | 0.3860 | 0.5972 | 0.032* | |
C12 | 0.16367 (13) | 0.3324 (3) | 0.69543 (18) | 0.0248 (6) | |
C13 | 0.15725 (14) | 0.2993 (4) | 0.79646 (19) | 0.0294 (6) | |
C14 | 0.22148 (15) | 0.3035 (4) | 0.8637 (2) | 0.0345 (7) | |
H14 | 0.2176 | 0.2847 | 0.9308 | 0.041* | |
C15 | 0.29119 (15) | 0.3356 (4) | 0.83161 (19) | 0.0321 (6) | |
H15 | 0.3337 | 0.3382 | 0.8777 | 0.039* | |
C16 | 0.15183 (18) | 0.8126 (5) | 0.7811 (3) | 0.0563 (9) | |
H16A | 0.1664 | 0.9211 | 0.8175 | 0.084* | |
H16B | 0.1862 | 0.7909 | 0.7326 | 0.084* | |
H16C | 0.1530 | 0.7115 | 0.8259 | 0.084* | |
O8 | 0.10240 (13) | 0.8005 (3) | 0.51358 (19) | 0.0688 (7) | |
H81 | 0.0974 | 0.6887 | 0.5029 | 0.083* | |
H82 | 0.0711 | 0.8567 | 0.4774 | 0.083* | |
O9 | 0.25290 (12) | 0.8792 (3) | 0.57526 (18) | 0.0647 (7) | |
H91 | 0.2069 | 0.8842 | 0.5533 | 0.078* | |
H92 | 0.2717 | 0.9792 | 0.5628 | 0.078* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0384 (15) | 0.0467 (15) | 0.0516 (16) | 0.0003 (12) | 0.0159 (12) | −0.0019 (12) |
O1 | 0.0267 (11) | 0.0492 (13) | 0.0505 (12) | −0.0091 (9) | 0.0105 (9) | −0.0186 (10) |
O2 | 0.0258 (10) | 0.0530 (13) | 0.0407 (11) | −0.0066 (9) | 0.0059 (9) | −0.0151 (10) |
O3 | 0.0283 (11) | 0.0664 (16) | 0.0832 (17) | −0.0104 (11) | 0.0203 (11) | −0.0105 (12) |
O4 | 0.0261 (11) | 0.0735 (15) | 0.0307 (11) | −0.0043 (10) | 0.0091 (8) | 0.0116 (10) |
O5 | 0.0320 (11) | 0.0670 (14) | 0.0265 (10) | 0.0064 (10) | 0.0050 (8) | 0.0024 (9) |
O6 | 0.0438 (13) | 0.0425 (12) | 0.0585 (14) | −0.0127 (10) | −0.0125 (10) | 0.0028 (10) |
O7 | 0.0275 (10) | 0.0526 (13) | 0.0430 (12) | 0.0145 (9) | 0.0080 (8) | −0.0005 (10) |
S1 | 0.0225 (4) | 0.0376 (4) | 0.0261 (4) | 0.0028 (3) | 0.0029 (3) | 0.0008 (3) |
C1 | 0.0285 (16) | 0.0444 (18) | 0.0396 (16) | −0.0023 (13) | 0.0107 (13) | −0.0105 (14) |
C2 | 0.0232 (14) | 0.0296 (15) | 0.0288 (14) | 0.0011 (12) | 0.0041 (11) | −0.0001 (11) |
C3 | 0.0224 (14) | 0.0300 (15) | 0.0298 (15) | 0.0004 (12) | 0.0018 (11) | 0.0019 (12) |
C4 | 0.0259 (14) | 0.0267 (14) | 0.0292 (14) | −0.0004 (12) | 0.0029 (11) | 0.0026 (11) |
C5 | 0.0274 (15) | 0.0352 (16) | 0.0342 (15) | −0.0017 (12) | 0.0060 (12) | 0.0003 (12) |
C6 | 0.0321 (16) | 0.0384 (17) | 0.0417 (17) | 0.0036 (13) | 0.0138 (13) | 0.0010 (13) |
C7 | 0.0242 (15) | 0.0348 (16) | 0.0564 (19) | −0.0012 (13) | 0.0139 (13) | 0.0084 (15) |
C8 | 0.0258 (15) | 0.0358 (16) | 0.0515 (18) | −0.0062 (13) | 0.0045 (13) | −0.0027 (14) |
C9 | 0.0274 (14) | 0.0294 (15) | 0.0369 (16) | −0.0016 (12) | 0.0057 (12) | −0.0005 (12) |
C10 | 0.0238 (14) | 0.0296 (15) | 0.0291 (14) | 0.0017 (11) | 0.0049 (11) | −0.0007 (11) |
C11 | 0.0254 (14) | 0.0305 (15) | 0.0241 (13) | 0.0032 (11) | 0.0056 (11) | 0.0011 (11) |
C12 | 0.0218 (13) | 0.0283 (14) | 0.0247 (13) | 0.0014 (11) | 0.0038 (10) | 0.0004 (11) |
C13 | 0.0254 (14) | 0.0353 (16) | 0.0284 (14) | 0.0007 (12) | 0.0065 (11) | 0.0038 (12) |
C14 | 0.0329 (16) | 0.0476 (18) | 0.0236 (14) | −0.0010 (13) | 0.0060 (12) | 0.0037 (12) |
C15 | 0.0262 (15) | 0.0411 (16) | 0.0281 (15) | 0.0013 (13) | −0.0010 (11) | −0.0015 (12) |
C16 | 0.045 (2) | 0.059 (2) | 0.065 (2) | 0.0066 (17) | 0.0042 (17) | 0.0042 (17) |
O8 | 0.0564 (16) | 0.0693 (17) | 0.0791 (18) | 0.0021 (13) | 0.0010 (13) | 0.0038 (13) |
O9 | 0.0479 (14) | 0.0664 (17) | 0.0833 (18) | −0.0065 (12) | 0.0231 (12) | 0.0031 (13) |
Geometric parameters (Å, º) top
N1—C16 | 1.478 (4) | C5—H5 | 0.9300 |
N1—H1A | 0.8900 | C6—C7 | 1.394 (4) |
N1—H1B | 0.8900 | C6—H6 | 0.9300 |
N1—H1C | 0.8900 | C7—C8 | 1.380 (4) |
O1—C1 | 1.356 (3) | C8—C9 | 1.395 (4) |
O1—C9 | 1.370 (3) | C8—H8 | 0.9300 |
O2—C3 | 1.233 (3) | C10—C11 | 1.396 (4) |
O3—C7 | 1.359 (3) | C10—C15 | 1.398 (4) |
O3—H3 | 0.8200 | C11—C12 | 1.390 (3) |
O4—C13 | 1.362 (3) | C11—H11 | 0.9300 |
O4—H4 | 0.8200 | C12—C13 | 1.408 (4) |
O5—S1 | 1.455 (2) | C13—C14 | 1.386 (4) |
O6—S1 | 1.447 (2) | C14—C15 | 1.382 (4) |
O7—S1 | 1.451 (2) | C14—H14 | 0.9300 |
S1—C12 | 1.770 (3) | C15—H15 | 0.9300 |
C1—C2 | 1.332 (4) | C16—H16A | 0.9600 |
C1—H1 | 0.9300 | C16—H16B | 0.9600 |
C2—C3 | 1.469 (4) | C16—H16C | 0.9600 |
C2—C10 | 1.493 (3) | O8—H81 | 0.8393 |
C3—C4 | 1.471 (4) | O8—H82 | 0.8158 |
C4—C9 | 1.389 (4) | O9—H91 | 0.8435 |
C4—C5 | 1.397 (4) | O9—H92 | 0.8340 |
C5—C6 | 1.379 (4) | | |
| | | |
C16—N1—H1A | 109.5 | O3—C7—C6 | 121.9 (3) |
C16—N1—H1B | 109.5 | C8—C7—C6 | 120.5 (3) |
H1A—N1—H1B | 109.5 | C7—C8—C9 | 118.8 (3) |
C16—N1—H1C | 109.5 | C7—C8—H8 | 120.6 |
H1A—N1—H1C | 109.5 | C9—C8—H8 | 120.6 |
H1B—N1—H1C | 109.5 | O1—C9—C4 | 121.5 (2) |
C1—O1—C9 | 118.0 (2) | O1—C9—C8 | 116.6 (2) |
C7—O3—H3 | 109.5 | C4—C9—C8 | 121.9 (3) |
C13—O4—H4 | 109.5 | C11—C10—C15 | 118.2 (2) |
O6—S1—O7 | 111.98 (13) | C11—C10—C2 | 121.8 (2) |
O6—S1—O5 | 112.73 (13) | C15—C10—C2 | 120.0 (2) |
O7—S1—O5 | 111.95 (12) | C12—C11—C10 | 120.9 (2) |
O6—S1—C12 | 107.78 (12) | C12—C11—H11 | 119.5 |
O7—S1—C12 | 106.03 (12) | C10—C11—H11 | 119.5 |
O5—S1—C12 | 105.85 (12) | C11—C12—C13 | 119.9 (2) |
C2—C1—O1 | 126.2 (3) | C11—C12—S1 | 119.47 (19) |
C2—C1—H1 | 116.9 | C13—C12—S1 | 120.60 (19) |
O1—C1—H1 | 116.9 | O4—C13—C14 | 122.0 (2) |
C1—C2—C3 | 119.1 (2) | O4—C13—C12 | 118.8 (2) |
C1—C2—C10 | 120.4 (2) | C14—C13—C12 | 119.2 (2) |
C3—C2—C10 | 120.3 (2) | C15—C14—C13 | 120.3 (2) |
O2—C3—C2 | 123.6 (2) | C15—C14—H14 | 119.8 |
O2—C3—C4 | 121.8 (2) | C13—C14—H14 | 119.8 |
C2—C3—C4 | 114.5 (2) | C14—C15—C10 | 121.3 (2) |
C9—C4—C5 | 117.8 (2) | C14—C15—H15 | 119.3 |
C9—C4—C3 | 120.5 (2) | C10—C15—H15 | 119.3 |
C5—C4—C3 | 121.7 (2) | N1—C16—H16A | 109.5 |
C6—C5—C4 | 121.3 (3) | N1—C16—H16B | 109.5 |
C6—C5—H5 | 119.4 | H16A—C16—H16B | 109.5 |
C4—C5—H5 | 119.4 | N1—C16—H16C | 109.5 |
C5—C6—C7 | 119.7 (3) | H16A—C16—H16C | 109.5 |
C5—C6—H6 | 120.2 | H16B—C16—H16C | 109.5 |
C7—C6—H6 | 120.2 | H81—O8—H82 | 109.9 |
O3—C7—C8 | 117.6 (3) | H91—O9—H92 | 106.8 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O9i | 0.82 | 1.88 | 2.664 (3) | 160 |
O4—H4···O5ii | 0.82 | 1.99 | 2.774 (3) | 160 |
N1—H1B···O7 | 0.89 | 2.06 | 2.950 (4) | 174 |
N1—H1C···O6iii | 0.89 | 2.09 | 2.946 (4) | 162 |
N1—H1A···O7iv | 0.89 | 2.04 | 2.918 (3) | 168 |
O8—H81···O5 | 0.84 | 2.23 | 3.043 (4) | 163 |
O8—H82···O6v | 0.82 | 2.30 | 2.998 (3) | 144 |
O9—H92···O2iii | 0.83 | 2.09 | 2.883 (3) | 158 |
O9—H91···O8 | 0.84 | 1.98 | 2.787 (4) | 159 |
C15—H15···O2ii | 0.93 | 2.49 | 3.201 (4) | 134 |
C1—H1···Cgvi | 0.93 | 2.66 | 3.440 (4) | 143 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, −y+1/2, z+1/2; (iii) x, y+1, z; (iv) −x, y+1/2, −z+3/2; (v) −x, −y+1, −z+1; (vi) −x+1, y−1/2, −z+1/2. |
(II) hexaaquairon(II) bis(4',7-diethoxyisoflavone-3'-sulfonate) tetrahydrate
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Crystal data top
[Fe(H2O)6](C19H17O7S)2·4H2O | Z = 1 |
Mr = 1014.78 | F(000) = 532 |
Triclinic, P1 | Dx = 1.492 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.827 (3) Å | Cell parameters from 1771 reflections |
b = 10.422 (3) Å | θ = 2.6–24.3° |
c = 12.803 (4) Å | µ = 0.51 mm−1 |
α = 88.888 (4)° | T = 298 K |
β = 84.952 (4)° | Needle, colourless |
γ = 74.255 (4)° | 0.47 × 0.21 × 0.18 mm |
V = 1129.2 (6) Å3 | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 3935 independent reflections |
Radiation source: fine-focus sealed tube | 2698 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | h = −9→10 |
Tmin = 0.794, Tmax = 0.913 | k = −12→11 |
5966 measured reflections | l = −15→15 |
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)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.125 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.058P)2 + 0.3331P] where P = (Fo2 + 2Fc2)/3 |
3935 reflections | (Δ/σ)max < 0.001 |
295 parameters | Δρmax = 0.40 e Å−3 |
36 restraints | Δρmin = −0.45 e Å−3 |
Crystal data top
[Fe(H2O)6](C19H17O7S)2·4H2O | γ = 74.255 (4)° |
Mr = 1014.78 | V = 1129.2 (6) Å3 |
Triclinic, P1 | Z = 1 |
a = 8.827 (3) Å | Mo Kα radiation |
b = 10.422 (3) Å | µ = 0.51 mm−1 |
c = 12.803 (4) Å | T = 298 K |
α = 88.888 (4)° | 0.47 × 0.21 × 0.18 mm |
β = 84.952 (4)° | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 3935 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | 2698 reflections with I > 2σ(I) |
Tmin = 0.794, Tmax = 0.913 | Rint = 0.022 |
5966 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.047 | 36 restraints |
wR(F2) = 0.125 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.40 e Å−3 |
3935 reflections | Δρmin = −0.45 e Å−3 |
295 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.2380 (3) | 1.0442 (2) | 1.12947 (16) | 0.0454 (6) | |
O2 | 0.3276 (3) | 1.0277 (3) | 0.81218 (18) | 0.0627 (8) | |
O3 | 0.4298 (3) | 1.4264 (2) | 1.14663 (17) | 0.0508 (7) | |
O4 | 0.0653 (3) | 0.5335 (2) | 0.74718 (18) | 0.0506 (7) | |
O5 | 0.0620 (3) | 0.9117 (2) | 0.59954 (17) | 0.0442 (6) | |
O6 | 0.2101 (3) | 0.6868 (2) | 0.55978 (18) | 0.0489 (6) | |
O7 | −0.0723 (3) | 0.7397 (2) | 0.60177 (18) | 0.0472 (6) | |
S1 | 0.07334 (10) | 0.77116 (8) | 0.61871 (6) | 0.0345 (2) | |
C1 | 0.1992 (4) | 0.9540 (4) | 1.0704 (3) | 0.0444 (9) | |
H1 | 0.1509 | 0.8949 | 1.1059 | 0.053* | |
C2 | 0.2233 (4) | 0.9406 (3) | 0.9654 (2) | 0.0341 (8) | |
C3 | 0.2972 (4) | 1.0325 (4) | 0.9080 (2) | 0.0379 (8) | |
C4 | 0.3325 (4) | 1.1341 (3) | 0.9710 (2) | 0.0346 (8) | |
C5 | 0.3987 (4) | 1.2326 (3) | 0.9258 (2) | 0.0406 (9) | |
H5 | 0.4222 | 1.2331 | 0.8536 | 0.049* | |
C6 | 0.4287 (4) | 1.3268 (4) | 0.9858 (3) | 0.0437 (9) | |
H6 | 0.4719 | 1.3916 | 0.9544 | 0.052* | |
C7 | 0.3951 (4) | 1.3276 (3) | 1.0952 (2) | 0.0380 (8) | |
C8 | 0.3321 (4) | 1.2318 (3) | 1.1429 (3) | 0.0408 (9) | |
H8 | 0.3108 | 1.2306 | 1.2153 | 0.049* | |
C9 | 0.3013 (4) | 1.1370 (3) | 1.0793 (2) | 0.0348 (8) | |
C10 | 0.1788 (4) | 0.8330 (3) | 0.9110 (2) | 0.0343 (8) | |
C11 | 0.1439 (4) | 0.8460 (3) | 0.8065 (2) | 0.0340 (8) | |
H11 | 0.1469 | 0.9243 | 0.7712 | 0.041* | |
C12 | 0.1053 (4) | 0.7471 (3) | 0.7538 (2) | 0.0313 (7) | |
C13 | 0.0979 (4) | 0.6291 (3) | 0.8046 (3) | 0.0383 (8) | |
C14 | 0.1286 (5) | 0.6160 (4) | 0.9101 (3) | 0.0466 (9) | |
H14 | 0.1213 | 0.5395 | 0.9464 | 0.056* | |
C15 | 0.1697 (4) | 0.7155 (4) | 0.9607 (3) | 0.0461 (9) | |
H15 | 0.1920 | 0.7035 | 1.0304 | 0.055* | |
C16 | 0.4203 (5) | 1.4235 (4) | 1.2591 (3) | 0.0531 (10) | |
H16A | 0.4881 | 1.3404 | 1.2828 | 0.064* | |
H16B | 0.3127 | 1.4301 | 1.2870 | 0.064* | |
C17 | 0.4718 (5) | 1.5383 (4) | 1.2965 (3) | 0.0647 (12) | |
H17A | 0.4642 | 1.5389 | 1.3718 | 0.097* | |
H17B | 0.4051 | 1.6200 | 1.2719 | 0.097* | |
H17C | 0.5793 | 1.5298 | 1.2700 | 0.097* | |
C18 | 0.0390 (6) | 0.4190 (4) | 0.7992 (3) | 0.0613 (12) | |
H18A | −0.0543 | 0.4447 | 0.8483 | 0.074* | |
H18B | 0.1286 | 0.3764 | 0.8382 | 0.074* | |
C19 | 0.0173 (6) | 0.3250 (4) | 0.7202 (3) | 0.0777 (14) | |
H19A | −0.0015 | 0.2475 | 0.7549 | 0.117* | |
H19B | 0.1106 | 0.2989 | 0.6726 | 0.117* | |
H19C | −0.0715 | 0.3677 | 0.6820 | 0.117* | |
Fe1 | 0.5000 | 1.0000 | 0.5000 | 0.0352 (2) | |
O8 | 0.2538 (3) | 1.0755 (2) | 0.53780 (17) | 0.0418 (6) | |
H21 | 0.2005 | 1.1335 | 0.4980 | 0.050* | |
H22 | 0.1964 | 1.0239 | 0.5559 | 0.050* | |
O9 | 0.5495 (3) | 1.0104 (3) | 0.65387 (17) | 0.0603 (8) | |
H23 | 0.4796 | 1.0312 | 0.7052 | 0.072* | |
H24 | 0.6194 | 1.0505 | 0.6630 | 0.072* | |
O10 | 0.4824 (3) | 0.7988 (2) | 0.5229 (2) | 0.0596 (7) | |
H25 | 0.5591 | 0.7318 | 0.5048 | 0.071* | |
H26 | 0.4056 | 0.7677 | 0.5444 | 0.071* | |
O12 | 0.7480 (3) | 0.5910 (3) | 0.5019 (2) | 0.0679 (8) | |
H29 | 0.8309 | 0.6074 | 0.5205 | 0.081* | |
H30 | 0.7797 | 0.5123 | 0.4770 | 0.081* | |
O11 | −0.2071 (3) | 1.1273 (3) | 0.6601 (2) | 0.0602 (8) | |
H27 | −0.1232 | 1.0663 | 0.6429 | 0.072* | |
H28 | −0.2029 | 1.1223 | 0.7262 | 0.072* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0665 (17) | 0.0485 (15) | 0.0300 (12) | −0.0327 (13) | 0.0019 (11) | −0.0016 (11) |
O2 | 0.084 (2) | 0.093 (2) | 0.0296 (13) | −0.0583 (18) | 0.0096 (13) | −0.0111 (13) |
O3 | 0.0755 (19) | 0.0448 (15) | 0.0408 (14) | −0.0303 (14) | −0.0069 (13) | −0.0035 (12) |
O4 | 0.0793 (19) | 0.0382 (14) | 0.0441 (14) | −0.0315 (14) | −0.0099 (13) | 0.0029 (11) |
O5 | 0.0549 (16) | 0.0392 (14) | 0.0442 (13) | −0.0206 (12) | −0.0122 (12) | 0.0105 (11) |
O6 | 0.0498 (16) | 0.0547 (16) | 0.0410 (13) | −0.0141 (13) | 0.0052 (12) | −0.0084 (12) |
O7 | 0.0483 (16) | 0.0530 (16) | 0.0506 (14) | −0.0271 (13) | −0.0193 (12) | 0.0096 (12) |
S1 | 0.0385 (5) | 0.0369 (5) | 0.0320 (4) | −0.0159 (4) | −0.0066 (4) | 0.0031 (4) |
C1 | 0.057 (2) | 0.046 (2) | 0.0377 (19) | −0.0277 (19) | −0.0011 (17) | 0.0006 (16) |
C2 | 0.036 (2) | 0.0381 (19) | 0.0295 (17) | −0.0131 (16) | −0.0025 (14) | 0.0009 (14) |
C3 | 0.031 (2) | 0.050 (2) | 0.0347 (19) | −0.0152 (17) | −0.0019 (15) | −0.0019 (16) |
C4 | 0.0312 (19) | 0.041 (2) | 0.0326 (18) | −0.0109 (16) | −0.0026 (14) | 0.0009 (15) |
C5 | 0.047 (2) | 0.050 (2) | 0.0299 (17) | −0.0220 (18) | −0.0011 (16) | 0.0021 (16) |
C6 | 0.055 (2) | 0.043 (2) | 0.0383 (19) | −0.0225 (19) | −0.0034 (17) | 0.0068 (16) |
C7 | 0.045 (2) | 0.0338 (19) | 0.0366 (18) | −0.0131 (17) | −0.0063 (16) | 0.0002 (15) |
C8 | 0.051 (2) | 0.042 (2) | 0.0308 (17) | −0.0155 (18) | −0.0014 (16) | −0.0046 (15) |
C9 | 0.035 (2) | 0.036 (2) | 0.0340 (18) | −0.0102 (16) | −0.0012 (15) | 0.0028 (15) |
C10 | 0.035 (2) | 0.036 (2) | 0.0319 (17) | −0.0102 (16) | −0.0019 (14) | −0.0027 (15) |
C11 | 0.035 (2) | 0.0305 (18) | 0.0372 (18) | −0.0097 (15) | −0.0018 (15) | 0.0016 (14) |
C12 | 0.0297 (18) | 0.0329 (18) | 0.0315 (17) | −0.0091 (15) | −0.0017 (14) | 0.0004 (14) |
C13 | 0.041 (2) | 0.036 (2) | 0.0406 (19) | −0.0162 (17) | −0.0027 (16) | −0.0003 (16) |
C14 | 0.064 (3) | 0.042 (2) | 0.039 (2) | −0.023 (2) | −0.0069 (18) | 0.0113 (17) |
C15 | 0.061 (3) | 0.050 (2) | 0.0342 (19) | −0.025 (2) | −0.0074 (17) | 0.0044 (17) |
C16 | 0.077 (3) | 0.053 (2) | 0.035 (2) | −0.027 (2) | −0.0057 (19) | −0.0062 (18) |
C17 | 0.079 (3) | 0.067 (3) | 0.056 (2) | −0.033 (2) | −0.002 (2) | −0.012 (2) |
C18 | 0.087 (3) | 0.047 (2) | 0.061 (3) | −0.035 (2) | −0.017 (2) | 0.010 (2) |
C19 | 0.120 (4) | 0.055 (3) | 0.074 (3) | −0.049 (3) | −0.015 (3) | −0.004 (2) |
Fe1 | 0.0322 (4) | 0.0426 (4) | 0.0322 (4) | −0.0128 (3) | −0.0017 (3) | 0.0015 (3) |
O8 | 0.0330 (14) | 0.0437 (14) | 0.0486 (14) | −0.0111 (11) | −0.0018 (11) | 0.0064 (11) |
O9 | 0.0514 (17) | 0.104 (2) | 0.0340 (13) | −0.0373 (16) | 0.0017 (12) | −0.0048 (14) |
O10 | 0.0433 (16) | 0.0416 (15) | 0.093 (2) | −0.0141 (13) | 0.0031 (14) | 0.0075 (14) |
O12 | 0.0547 (18) | 0.0548 (18) | 0.093 (2) | −0.0131 (15) | −0.0008 (16) | −0.0254 (16) |
O11 | 0.0598 (18) | 0.0628 (18) | 0.0616 (17) | −0.0221 (15) | −0.0019 (14) | −0.0181 (14) |
Geometric parameters (Å, º) top
O1—C1 | 1.349 (4) | C14—C15 | 1.377 (5) |
O1—C9 | 1.367 (4) | C14—H14 | 0.9300 |
O2—C3 | 1.232 (4) | C15—H15 | 0.9300 |
O3—C7 | 1.350 (4) | C16—C17 | 1.491 (5) |
O3—C16 | 1.435 (4) | C16—H16A | 0.9700 |
O4—C13 | 1.355 (4) | C16—H16B | 0.9700 |
O4—C18 | 1.419 (4) | C17—H17A | 0.9600 |
O5—S1 | 1.458 (2) | C17—H17B | 0.9600 |
O6—S1 | 1.445 (3) | C17—H17C | 0.9600 |
O7—S1 | 1.445 (2) | C18—C19 | 1.481 (5) |
S1—C12 | 1.779 (3) | C18—H18A | 0.9700 |
C1—C2 | 1.346 (4) | C18—H18B | 0.9700 |
C1—H1 | 0.9300 | C19—H19A | 0.9600 |
C2—C3 | 1.453 (4) | C19—H19B | 0.9600 |
C2—C10 | 1.488 (4) | C19—H19C | 0.9600 |
C3—C4 | 1.458 (4) | Fe1—O9i | 2.066 (2) |
C4—C9 | 1.389 (4) | Fe1—O9 | 2.066 (2) |
C4—C5 | 1.405 (4) | Fe1—O8 | 2.116 (2) |
C5—C6 | 1.353 (4) | Fe1—O8i | 2.116 (2) |
C5—H5 | 0.9300 | Fe1—O10 | 2.157 (2) |
C6—C7 | 1.405 (4) | Fe1—O10i | 2.157 (2) |
C6—H6 | 0.9300 | O8—H21 | 0.8501 |
C7—C8 | 1.377 (5) | O8—H22 | 0.8500 |
C8—C9 | 1.388 (4) | O9—H23 | 0.8499 |
C8—H8 | 0.9300 | O9—H24 | 0.8499 |
C10—C15 | 1.388 (5) | O10—H25 | 0.8500 |
C10—C11 | 1.395 (4) | O10—H26 | 0.8501 |
C11—C12 | 1.376 (4) | O12—H29 | 0.8500 |
C11—H11 | 0.9300 | O12—H30 | 0.8500 |
C12—C13 | 1.394 (4) | O11—H27 | 0.8500 |
C13—C14 | 1.398 (5) | O11—H28 | 0.8503 |
| | | |
C1—O1—C9 | 118.1 (3) | C14—C15—H15 | 118.9 |
C7—O3—C16 | 118.6 (3) | C10—C15—H15 | 118.9 |
C13—O4—C18 | 118.8 (3) | O3—C16—C17 | 108.3 (3) |
O7—S1—O6 | 113.41 (15) | O3—C16—H16A | 110.0 |
O7—S1—O5 | 111.59 (14) | C17—C16—H16A | 110.0 |
O6—S1—O5 | 111.04 (15) | O3—C16—H16B | 110.0 |
O7—S1—C12 | 108.22 (14) | C17—C16—H16B | 110.0 |
O6—S1—C12 | 107.06 (15) | H16A—C16—H16B | 108.4 |
O5—S1—C12 | 105.03 (14) | C16—C17—H17A | 109.5 |
C2—C1—O1 | 126.8 (3) | C16—C17—H17B | 109.5 |
C2—C1—H1 | 116.6 | H17A—C17—H17B | 109.5 |
O1—C1—H1 | 116.6 | C16—C17—H17C | 109.5 |
C1—C2—C3 | 117.7 (3) | H17A—C17—H17C | 109.5 |
C1—C2—C10 | 120.8 (3) | H17B—C17—H17C | 109.5 |
C3—C2—C10 | 121.5 (3) | O4—C18—C19 | 109.0 (3) |
O2—C3—C2 | 123.2 (3) | O4—C18—H18A | 109.9 |
O2—C3—C4 | 121.1 (3) | C19—C18—H18A | 109.9 |
C2—C3—C4 | 115.7 (3) | O4—C18—H18B | 109.9 |
C9—C4—C5 | 117.2 (3) | C19—C18—H18B | 109.9 |
C9—C4—C3 | 120.8 (3) | H18A—C18—H18B | 108.3 |
C5—C4—C3 | 122.0 (3) | C18—C19—H19A | 109.5 |
C6—C5—C4 | 121.0 (3) | C18—C19—H19B | 109.5 |
C6—C5—H5 | 119.5 | H19A—C19—H19B | 109.5 |
C4—C5—H5 | 119.5 | C18—C19—H19C | 109.5 |
C5—C6—C7 | 120.5 (3) | H19A—C19—H19C | 109.5 |
C5—C6—H6 | 119.7 | H19B—C19—H19C | 109.5 |
C7—C6—H6 | 119.7 | O9i—Fe1—O9 | 180.000 (1) |
O3—C7—C8 | 124.4 (3) | O9i—Fe1—O8 | 87.26 (9) |
O3—C7—C6 | 115.1 (3) | O9—Fe1—O8 | 92.74 (9) |
C8—C7—C6 | 120.4 (3) | O9i—Fe1—O8i | 92.74 (9) |
C7—C8—C9 | 117.8 (3) | O9—Fe1—O8i | 87.26 (9) |
C7—C8—H8 | 121.1 | O8—Fe1—O8i | 180.000 (1) |
C9—C8—H8 | 121.1 | O9i—Fe1—O10 | 89.12 (11) |
O1—C9—C8 | 116.1 (3) | O9—Fe1—O10 | 90.88 (11) |
O1—C9—C4 | 120.8 (3) | O8—Fe1—O10 | 90.56 (9) |
C8—C9—C4 | 123.1 (3) | O8i—Fe1—O10 | 89.44 (9) |
C15—C10—C11 | 116.6 (3) | O9i—Fe1—O10i | 90.88 (11) |
C15—C10—C2 | 122.3 (3) | O9—Fe1—O10i | 89.12 (11) |
C11—C10—C2 | 121.1 (3) | O8—Fe1—O10i | 89.44 (9) |
C12—C11—C10 | 122.3 (3) | O8i—Fe1—O10i | 90.56 (9) |
C12—C11—H11 | 118.9 | O10—Fe1—O10i | 180.000 (1) |
C10—C11—H11 | 118.9 | Fe1—O8—H21 | 118.9 |
C11—C12—C13 | 120.4 (3) | Fe1—O8—H22 | 121.2 |
C11—C12—S1 | 118.3 (2) | H21—O8—H22 | 105.9 |
C13—C12—S1 | 121.3 (2) | Fe1—O9—H23 | 124.1 |
O4—C13—C12 | 117.5 (3) | Fe1—O9—H24 | 114.9 |
O4—C13—C14 | 124.5 (3) | H23—O9—H24 | 107.1 |
C12—C13—C14 | 118.0 (3) | Fe1—O10—H25 | 121.7 |
C15—C14—C13 | 120.5 (3) | Fe1—O10—H26 | 132.2 |
C15—C14—H14 | 119.7 | H25—O10—H26 | 106.0 |
C13—C14—H14 | 119.7 | H29—O12—H30 | 104.5 |
C14—C15—C10 | 122.2 (3) | H27—O11—H28 | 97.9 |
Symmetry code: (i) −x+1, −y+2, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O11—H27···O5 | 0.85 | 2.01 | 2.853 (4) | 175 |
O11—H28···O1ii | 0.85 | 2.57 | 3.237 (3) | 137 |
O8—H21···O7iii | 0.85 | 2.01 | 2.858 (3) | 176 |
O8—H22···O5 | 0.85 | 1.92 | 2.773 (3) | 178 |
O9—H23···O2 | 0.85 | 1.84 | 2.665 (3) | 164 |
O9—H24···O11iv | 0.85 | 1.91 | 2.749 (3) | 170 |
O12—H29···O7iv | 0.85 | 2.14 | 2.885 (3) | 147 |
O12—H30···O6v | 0.85 | 2.11 | 2.933 (4) | 162 |
O10—H25···O12 | 0.85 | 1.90 | 2.723 (4) | 164 |
O10—H26···O6 | 0.85 | 2.11 | 2.943 (3) | 166 |
C11—H11···O2 | 0.93 | 2.25 | 2.813 (4) | 118 |
C6—H6···O3vi | 0.93 | 2.57 | 3.500 (4) | 174 |
Symmetry codes: (ii) −x, −y+2, −z+2; (iii) −x, −y+2, −z+1; (iv) x+1, y, z; (v) −x+1, −y+1, −z+1; (vi) −x+1, −y+3, −z+2. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | CH6N+·C15H9O7S−·2H2O | [Fe(H2O)6](C19H17O7S)2·4H2O |
Mr | 401.38 | 1014.78 |
Crystal system, space group | Monoclinic, P21/c | Triclinic, P1 |
Temperature (K) | 298 | 298 |
a, b, c (Å) | 17.852 (13), 7.365 (5), 13.558 (10) | 8.827 (3), 10.422 (3), 12.803 (4) |
α, β, γ (°) | 90, 96.194 (11), 90 | 88.888 (4), 84.952 (4), 74.255 (4) |
V (Å3) | 1772 (2) | 1129.2 (6) |
Z | 4 | 1 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.24 | 0.51 |
Crystal size (mm) | 0.53 × 0.45 × 0.21 | 0.47 × 0.21 × 0.18 |
|
Data collection |
Diffractometer | Bruker SMART CCD area-detector diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1999) | Multi-scan (SADABS; Bruker, 1999) |
Tmin, Tmax | 0.886, 0.952 | 0.794, 0.913 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8930, 3123, 2147 | 5966, 3935, 2698 |
Rint | 0.048 | 0.022 |
(sin θ/λ)max (Å−1) | 0.595 | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.123, 1.01 | 0.047, 0.125, 1.03 |
No. of reflections | 3123 | 3935 |
No. of parameters | 246 | 295 |
No. of restraints | 0 | 36 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.35, −0.27 | 0.40, −0.45 |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O9i | 0.82 | 1.88 | 2.664 (3) | 160 |
O4—H4···O5ii | 0.82 | 1.99 | 2.774 (3) | 160 |
N1—H1B···O7 | 0.89 | 2.06 | 2.950 (4) | 174 |
N1—H1C···O6iii | 0.89 | 2.09 | 2.946 (4) | 162 |
N1—H1A···O7iv | 0.89 | 2.04 | 2.918 (3) | 168 |
O8—H81···O5 | 0.84 | 2.23 | 3.043 (4) | 163 |
O8—H82···O6v | 0.82 | 2.30 | 2.998 (3) | 144 |
O9—H92···O2iii | 0.83 | 2.09 | 2.883 (3) | 158 |
O9—H91···O8 | 0.84 | 1.98 | 2.787 (4) | 159 |
C15—H15···O2ii | 0.93 | 2.49 | 3.201 (4) | 134 |
C1—H1···Cgvi | 0.93 | 2.66 | 3.440 (4) | 143 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, −y+1/2, z+1/2; (iii) x, y+1, z; (iv) −x, y+1/2, −z+3/2; (v) −x, −y+1, −z+1; (vi) −x+1, y−1/2, −z+1/2. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O11—H27···O5 | 0.85 | 2.01 | 2.853 (4) | 174.8 |
O11—H28···O1i | 0.85 | 2.57 | 3.237 (3) | 136.5 |
O8—H21···O7ii | 0.85 | 2.01 | 2.858 (3) | 176.1 |
O8—H22···O5 | 0.85 | 1.92 | 2.773 (3) | 178.2 |
O9—H23···O2 | 0.85 | 1.84 | 2.665 (3) | 164.1 |
O9—H24···O11iii | 0.85 | 1.91 | 2.749 (3) | 169.9 |
O12—H29···O7iii | 0.85 | 2.14 | 2.885 (3) | 146.7 |
O12—H30···O6iv | 0.85 | 2.11 | 2.933 (4) | 161.8 |
O10—H25···O12 | 0.85 | 1.90 | 2.723 (4) | 163.9 |
O10—H26···O6 | 0.85 | 2.11 | 2.943 (3) | 166.4 |
C11—H11···O2 | 0.93 | 2.25 | 2.813 (4) | 117.9 |
C6—H6···O3v | 0.93 | 2.57 | 3.500 (4) | 174.0 |
Symmetry codes: (i) −x, −y+2, −z+2; (ii) −x, −y+2, −z+1; (iii) x+1, y, z; (iv) −x+1, −y+1, −z+1; (v) −x+1, −y+3, −z+2. |
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Daidzein (4',7-dihydroxyisoflavone), a natural soy isoflavone, is biologically active, with resistance to hypoxia and anoxemia (Meng et al., 1999). However, because the solubility of this isoflavone is poor, its biological utilization rate is low so the dose required is high (Tang et al., 1989). In order to increase the solubility of the isoflavone, some sulfonated derivatives have been prepared. Sodium 4',7-dihydroxyisoflavonesulfonate (Liu et al., 2003) and sodium 7-methoxy-4'-hydroxyisoflavone-3'-sulfonate (Zhang et al., 2002) have been synthesized and their crystal structures and biological activities have been studied. The results show that these compounds possess better biological activity than the parent compound, daidzein. The water-soluble derivatives Co(H2O)6.X2·8H2O (Zhang & Wang, 2005a), and Mg(H2O)6.X2·8H2O and Zn(H2O)6.X2·8H2O (Zhang & Wang, 2005b) (X is 4',7-diethoxyisoflavone-3'-sulfonate) have been reported. Protonated methylaminium 4',7-dihydroxyisoflavone-3'-sulfonate dihydrate, (I), and hexaaquairon(II) bis(4',7-diethoxyisoflavone-3'-sulfonate) tetrahydrate, (II), are both water-soluble derivatives of daidzein.
Compound (I) is composed of one CH3NH3+ cation, one 4',7-dihydroxyisoflavone-3'-sulfonate anion and two solvent water molecules (Fig. 1). In the anion, the bond lengths and angles of the isoflavone units are similar to those of the sodium salt (Liu et al., 2003). The atoms of the benzopyranone moiety constitute planar rings A (C4–C9) and C (C1–C4/C9/O1) [mean out-of plane deviations are 0.006 (3) and 0.013 (3) Å, respectively], with an interplanar angle of 2.8 (1)°. To avoid intramolecular steric conflicts, the two rigid ring systems, viz. benzene ring B (C10–C15) and the benzopyranone moiety, are rotated by 43.2 (1)° with respect to each other.
In compound (II), the FeII atom lies on an inversion centre and is coordinated by six water molecules, which form a slightly distorted octahedron (Fig. 2). The Fe—O bond lengths fall in the range 2.066 (2)–2.157 (2) Å, and are close to those in the compound Fe(H2O)6·(C17H13O7S)2·8H2O [2.043 (3)–2.155 (3) Å; Zhang & Cheng, 2005]. The atoms of the benzopyranone moiety constitute rings A (C4–C9) and C (C1–C4/C9/O1) [mean out-of-plane deviations are 0.003 (1) and 0.013 (2) Å, respectively], with an interplanar angle of 0.7 (1)°. The two rigid ring systems, viz. benzene ring B (C10–C15) and the benzopyranone moiety, are rotated by 24.8 (1)° with respect to each other. One independent C11—H11···O2 intramolecular hydrogen bond forms a characteristic intramolecular S(6) motif.
Fig. 1 shows how a cyclic dimer is formed in (I) by O—H···O hydrogen bonding and π–π stacking interactions. One hydrogen-bond chain exists between hydroxyl atom H3i of one molecule and sulfonate atom O5 of another molecule, bridged by O3i—H3i···O9i [symmetry code: (i) 1 − x, 1 − y, 1 − z], O9—H91···O8 and O8—H81···O5 hydrogen bonds, pairs of which build a dimeric unit described by the R66(34) synthon (Etter, 1990). Details of other hydrogen bonds are given in Table 1. In the dimer, the isoflavone skeletons are in an anti-parallel mode, with π–π stacking interactions between their A rings with an offset distance of 1.127 Å and Cg···Cgi of 3.610 (5) Å, where Cg and Cgi are the centroids of rings A at (x, y, z) and (1 − x, 1 − y, 1 − z), respectively. A normal range for such interactions is 3.3–3.8 Å (Janiak, 2000). The C—H···π(arene), O—H···O and C—H···O hydrogen bonds, which exist between the dimers, assemble the isoflavone units into an approximately two-dimensional (011) sheet linked by paired O8—H82···O6v hydrogen bonds [symmetry code: (v) −x, 1 − y, 1 − z] (Fig. 3). Atom C1 in the molecule at (1 − x, −1/2 + y, 1/2 − z) acts as hydrogen-bond donor, via axial atom H1, to ring A in the molecule at (x, y, z), with an H···centroid distance of 2.650 Å. Crosslinks between the sheets are provided by strong N—H···O hydrogen bonds, leading to a three-dimensional supramolecular structure.
In compound (II), each H atom of the six water molecules coordinated to the FeII atom and of the two solvent water molecules acts as a donor, leading to the formation of hydrogen bonds (Fig. 2). Atoms O2, O5, O6 and O7 are all trifurcated by hydrogen bonds. Details of the hydrogen bonds are given in Table 2. Similarly, the isoflavone skeletons of compound (II) are in an almost anti-parallel mode and π–π stacking interactions, forming dimers, exist between rings A and C of one molecule and rings C and A of another, with a centroid–centroid distance of 3.720 (2) Å (Fig. 4). The dimers are further linked by paired O11—H27···O5i and O11—H28···O1ii [symmetry codes: (i) −x, 2 − y, 1 − z; (ii) x, y, −1 + z] hydrogen bonds and a column is built along the (001) direction. These columns are also crosslinked by paired C6—H6···O3vi [symmetry code: (vi) 1 − x, 3 − y, 2 − z] hydrogen bonds, which form an R22(8) synthon, and a three-dimensional supramolecular structure of (II) is generated.