Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803013096/cf6255sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803013096/cf6255Isup2.hkl |
CCDC reference: 217379
A mixture of 3-carboxy-4-hydroxybenzenesulfonic acid (0.44 g, 2 mmol) and ZnO (0.081 g, 1 mmol) in water (10 ml) was stirred at room temperature for 30 min. Colorless crystals of compound (I) were obtained after leaving the solution to stand at room temperature for several days. Analysis calculated for C14H30CoO22S2: C 24.73, H 4.45%; found: C 24.59, H 4.39%.
All H atoms on C atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C). The H atoms of the carboxyl group and hydroxyl group were also positioned geometrically and refined as riding atoms, with O—H = 0.82 Å and Uiso(H) = 1.5Ueq(O). The water H atoms were located in a difference Fourier map and refined with Uiso(H) = 1.5Ueq(O).
Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1990); software used to prepare material for publication: SHELXL97.
[Zn(H2O)6](C7H5O6S)2·4H2O | Z = 1 |
Mr = 679.87 | F(000) = 352 |
Triclinic, P1 | Dx = 1.685 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.5367 (14) Å | Cell parameters from 22 reflections |
b = 7.2555 (18) Å | θ = 4.8–8.7° |
c = 14.616 (4) Å | µ = 1.17 mm−1 |
α = 92.83 (2)° | T = 293 K |
β = 96.321 (19)° | Block, colorless |
γ = 102.839 (17)° | 0.52 × 0.36 × 0.32 mm |
V = 669.8 (3) Å3 |
Siemens P4 diffractometer | 2101 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.020 |
Graphite monochromator | θmax = 26.0°, θmin = 2.8° |
ω scans | h = −1→8 |
Absorption correction: ψ scan (North et al., 1968) | k = −8→8 |
Tmin = 0.517, Tmax = 0.688 | l = −17→17 |
3445 measured reflections | 3 standard reflections every 97 reflections |
2615 independent reflections | intensity decay: none |
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)] = 0.033 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.088 | w = 1/[σ2(Fo2) + (0.0454P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
2615 reflections | Δρmax = 0.51 e Å−3 |
209 parameters | Δρmin = −0.29 e Å−3 |
10 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.083 (4) |
[Zn(H2O)6](C7H5O6S)2·4H2O | γ = 102.839 (17)° |
Mr = 679.87 | V = 669.8 (3) Å3 |
Triclinic, P1 | Z = 1 |
a = 6.5367 (14) Å | Mo Kα radiation |
b = 7.2555 (18) Å | µ = 1.17 mm−1 |
c = 14.616 (4) Å | T = 293 K |
α = 92.83 (2)° | 0.52 × 0.36 × 0.32 mm |
β = 96.321 (19)° |
Siemens P4 diffractometer | 2101 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.020 |
Tmin = 0.517, Tmax = 0.688 | 3 standard reflections every 97 reflections |
3445 measured reflections | intensity decay: none |
2615 independent reflections |
R[F2 > 2σ(F2)] = 0.033 | 10 restraints |
wR(F2) = 0.088 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.51 e Å−3 |
2615 reflections | Δρmin = −0.29 e Å−3 |
209 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 | 0.4006 (4) | 0.1612 (3) | 0.35540 (16) | 0.0273 (5) | |
C2 | 0.3128 (4) | 0.1613 (3) | 0.43725 (16) | 0.0283 (5) | |
H2 | 0.1692 | 0.1104 | 0.4375 | 0.034* | |
C3 | 0.4389 (4) | 0.2375 (3) | 0.51942 (16) | 0.0277 (5) | |
C4 | 0.6548 (4) | 0.3158 (3) | 0.51830 (17) | 0.0304 (5) | |
C5 | 0.7415 (4) | 0.3125 (4) | 0.43528 (18) | 0.0370 (6) | |
H5 | 0.8853 | 0.3620 | 0.4346 | 0.044* | |
C6 | 0.6161 (4) | 0.2367 (4) | 0.35449 (17) | 0.0352 (6) | |
H6A | 0.6748 | 0.2357 | 0.2994 | 0.042* | |
C7 | 0.3455 (4) | 0.2393 (4) | 0.60727 (17) | 0.0324 (6) | |
O1 | 0.0984 (4) | 0.2068 (3) | 0.23376 (15) | 0.0558 (6) | |
O2 | 0.3650 (3) | 0.0564 (3) | 0.18078 (13) | 0.0519 (6) | |
O3 | 0.1035 (3) | −0.1103 (2) | 0.26922 (12) | 0.0398 (5) | |
O4 | 0.1419 (3) | 0.1632 (3) | 0.59701 (13) | 0.0488 (5) | |
H4 | 0.0974 | 0.1665 | 0.6472 | 0.073* | |
O5 | 0.4479 (3) | 0.3045 (3) | 0.68175 (12) | 0.0455 (5) | |
O6 | 0.7842 (3) | 0.3981 (3) | 0.59463 (13) | 0.0443 (5) | |
H6 | 0.7171 | 0.3917 | 0.6390 | 0.066* | |
OW1 | 0.7107 (4) | 0.3358 (3) | 0.97543 (15) | 0.0553 (6) | |
OW2 | 0.7260 (4) | 0.7416 (3) | 0.97855 (13) | 0.0440 (5) | |
OW3 | 0.6201 (3) | 0.5266 (3) | 1.14047 (13) | 0.0448 (5) | |
OW4 | 0.7399 (3) | 0.0528 (3) | 0.09920 (14) | 0.0465 (5) | |
OW5 | 0.9507 (4) | 0.4486 (3) | 0.83240 (14) | 0.0469 (5) | |
S1 | 0.23299 (10) | 0.07286 (9) | 0.25194 (4) | 0.03017 (18) | |
Zn1 | 0.5000 | 0.5000 | 1.0000 | 0.03347 (17) | |
H1A | 0.744 (5) | 0.245 (4) | 1.0092 (19) | 0.050* | |
H1B | 0.803 (4) | 0.363 (4) | 0.9370 (19) | 0.050* | |
H2A | 0.740 (5) | 0.839 (3) | 1.0199 (18) | 0.050* | |
H2B | 0.712 (5) | 0.793 (4) | 0.9263 (15) | 0.050* | |
H3A | 0.758 (3) | 0.536 (4) | 1.150 (2) | 0.050* | |
H3B | 0.597 (5) | 0.604 (4) | 1.1840 (18) | 0.050* | |
H4A | 0.615 (4) | 0.028 (4) | 0.122 (2) | 0.050* | |
H4B | 0.844 (4) | 0.098 (4) | 0.1448 (17) | 0.050* | |
H5A | 0.896 (5) | 0.347 (3) | 0.7974 (19) | 0.050* | |
H5B | 0.915 (5) | 0.546 (3) | 0.812 (2) | 0.050* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0306 (13) | 0.0270 (12) | 0.0240 (11) | 0.0057 (10) | 0.0038 (10) | 0.0030 (9) |
C2 | 0.0257 (12) | 0.0303 (12) | 0.0285 (12) | 0.0046 (10) | 0.0047 (10) | 0.0025 (10) |
C3 | 0.0309 (12) | 0.0272 (12) | 0.0260 (12) | 0.0078 (10) | 0.0061 (10) | 0.0015 (9) |
C4 | 0.0288 (13) | 0.0314 (13) | 0.0297 (12) | 0.0053 (10) | 0.0012 (10) | 0.0022 (10) |
C5 | 0.0259 (13) | 0.0424 (15) | 0.0383 (14) | −0.0017 (11) | 0.0051 (11) | 0.0004 (11) |
C6 | 0.0343 (14) | 0.0414 (15) | 0.0302 (13) | 0.0045 (12) | 0.0120 (11) | 0.0062 (11) |
C7 | 0.0364 (14) | 0.0337 (13) | 0.0284 (12) | 0.0103 (11) | 0.0073 (11) | −0.0012 (10) |
O1 | 0.0630 (14) | 0.0474 (12) | 0.0551 (13) | 0.0224 (11) | −0.0184 (11) | −0.0001 (10) |
O2 | 0.0455 (12) | 0.0791 (15) | 0.0271 (9) | 0.0014 (11) | 0.0149 (9) | −0.0001 (9) |
O3 | 0.0465 (11) | 0.0385 (10) | 0.0286 (9) | −0.0049 (9) | 0.0117 (8) | −0.0028 (8) |
O4 | 0.0367 (11) | 0.0724 (15) | 0.0316 (10) | −0.0018 (10) | 0.0142 (8) | −0.0088 (9) |
O5 | 0.0445 (12) | 0.0647 (13) | 0.0251 (9) | 0.0102 (10) | 0.0025 (8) | −0.0041 (9) |
O6 | 0.0352 (10) | 0.0575 (13) | 0.0333 (10) | 0.0007 (9) | −0.0026 (8) | −0.0030 (9) |
OW1 | 0.0723 (16) | 0.0613 (14) | 0.0501 (13) | 0.0399 (13) | 0.0284 (12) | 0.0175 (11) |
OW2 | 0.0590 (13) | 0.0421 (11) | 0.0285 (10) | 0.0040 (10) | 0.0090 (10) | 0.0053 (8) |
OW3 | 0.0459 (11) | 0.0653 (14) | 0.0245 (9) | 0.0167 (11) | 0.0052 (9) | −0.0033 (9) |
OW4 | 0.0376 (11) | 0.0581 (13) | 0.0429 (11) | 0.0118 (10) | 0.0030 (9) | −0.0023 (10) |
OW5 | 0.0583 (13) | 0.0375 (11) | 0.0440 (12) | 0.0134 (10) | 0.0012 (10) | −0.0042 (9) |
S1 | 0.0337 (3) | 0.0344 (4) | 0.0214 (3) | 0.0048 (3) | 0.0042 (2) | 0.0040 (2) |
Zn1 | 0.0410 (3) | 0.0373 (3) | 0.0245 (2) | 0.0119 (2) | 0.00789 (18) | 0.00306 (17) |
C1—C2 | 1.383 (3) | O6—H6 | 0.820 |
C1—C6 | 1.395 (4) | OW1—Zn1 | 2.059 (2) |
C1—S1 | 1.768 (2) | OW1—H1A | 0.891 (18) |
C2—C3 | 1.393 (3) | OW1—H1B | 0.868 (18) |
C2—H2 | 0.930 | OW2—Zn1 | 2.088 (2) |
C3—C4 | 1.401 (3) | OW2—H2A | 0.889 (18) |
C3—C7 | 1.482 (3) | OW2—H2B | 0.870 (18) |
C4—O6 | 1.349 (3) | OW3—Zn1 | 2.099 (2) |
C4—C5 | 1.396 (4) | OW3—H3A | 0.887 (18) |
C5—C6 | 1.375 (3) | OW3—H3B | 0.878 (18) |
C5—H5 | 0.930 | OW4—H4A | 0.901 (18) |
C6—H6A | 0.930 | OW4—H4B | 0.890 (18) |
C7—O5 | 1.227 (3) | OW5—H5A | 0.859 (18) |
C7—O4 | 1.311 (3) | OW5—H5B | 0.846 (18) |
O1—S1 | 1.463 (2) | Zn1—OW1i | 2.059 (2) |
O2—S1 | 1.440 (2) | Zn1—OW2i | 2.088 (2) |
O3—S1 | 1.4582 (18) | Zn1—OW3i | 2.099 (2) |
O4—H4 | 0.820 | ||
C2—C1—C6 | 120.3 (2) | H2A—OW2—H2B | 103 (3) |
C2—C1—S1 | 118.77 (18) | Zn1—OW3—H3A | 114 (2) |
C6—C1—S1 | 120.91 (19) | Zn1—OW3—H3B | 127 (2) |
C1—C2—C3 | 120.2 (2) | H3A—OW3—H3B | 104 (3) |
C1—C2—H2 | 119.9 | H4A—OW4—H4B | 109 (3) |
C3—C2—H2 | 119.9 | H5A—OW5—H5B | 113 (3) |
C2—C3—C4 | 119.5 (2) | O2—S1—O3 | 112.10 (12) |
C2—C3—C7 | 120.5 (2) | O2—S1—O1 | 113.37 (14) |
C4—C3—C7 | 120.0 (2) | O3—S1—O1 | 109.74 (13) |
O6—C4—C5 | 117.8 (2) | O2—S1—C1 | 107.70 (12) |
O6—C4—C3 | 122.6 (2) | O3—S1—C1 | 106.94 (11) |
C5—C4—C3 | 119.6 (2) | O1—S1—C1 | 106.62 (12) |
C6—C5—C4 | 120.5 (2) | OW1—Zn1—OW1i | 180.0 |
C6—C5—H5 | 119.7 | OW1—Zn1—OW2 | 89.56 (10) |
C4—C5—H5 | 119.7 | OW1i—Zn1—OW2 | 90.44 (10) |
C5—C6—C1 | 119.9 (2) | OW1—Zn1—OW2i | 90.44 (10) |
C5—C6—H6A | 120.1 | OW1i—Zn1—OW2i | 89.56 (10) |
C1—C6—H6A | 120.1 | OW2—Zn1—OW2i | 180.0 |
O5—C7—O4 | 123.6 (2) | OW1—Zn1—OW3i | 91.40 (9) |
O5—C7—C3 | 123.6 (2) | OW1i—Zn1—OW3i | 88.60 (9) |
O4—C7—C3 | 112.9 (2) | OW2—Zn1—OW3i | 90.05 (8) |
C7—O4—H4 | 109.5 | OW2i—Zn1—OW3i | 89.95 (9) |
C4—O6—H6 | 109.5 | OW1—Zn1—OW3 | 88.60 (9) |
Zn1—OW1—H1A | 128 (2) | OW1i—Zn1—OW3 | 91.40 (9) |
Zn1—OW1—H1B | 123 (2) | OW2—Zn1—OW3 | 89.95 (9) |
H1A—OW1—H1B | 108 (3) | OW2i—Zn1—OW3 | 90.05 (8) |
Zn1—OW2—H2A | 115 (2) | OW3i—Zn1—OW3 | 180.0 |
Zn1—OW2—H2B | 118 (2) | ||
C6—C1—C2—C3 | 0.2 (4) | S1—C1—C6—C5 | 177.0 (2) |
S1—C1—C2—C3 | −177.19 (18) | C2—C3—C7—O5 | −179.9 (2) |
C1—C2—C3—C4 | 0.7 (4) | C4—C3—C7—O5 | −1.0 (4) |
C1—C2—C3—C7 | 179.6 (2) | C2—C3—C7—O4 | 0.3 (3) |
C2—C3—C4—O6 | 177.5 (2) | C4—C3—C7—O4 | 179.2 (2) |
C7—C3—C4—O6 | −1.4 (4) | C2—C1—S1—O2 | −169.8 (2) |
C2—C3—C4—C5 | −1.5 (4) | C6—C1—S1—O2 | 12.8 (2) |
C7—C3—C4—C5 | 179.6 (2) | C2—C1—S1—O3 | −49.2 (2) |
O6—C4—C5—C6 | −177.7 (2) | C6—C1—S1—O3 | 133.4 (2) |
C3—C4—C5—C6 | 1.3 (4) | C2—C1—S1—O1 | 68.2 (2) |
C4—C5—C6—C1 | −0.4 (4) | C6—C1—S1—O1 | −109.2 (2) |
C2—C1—C6—C5 | −0.4 (4) |
Symmetry code: (i) −x+1, −y+1, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
OW1—H1A···OW4ii | 0.89 (2) | 1.96 (2) | 2.827 (3) | 162 (3) |
OW1—H1B···OW5 | 0.87 (2) | 1.95 (2) | 2.797 (3) | 165 (3) |
OW2—H2A···OW4iii | 0.89 (2) | 1.89 (2) | 2.775 (3) | 173 (3) |
OW2—H2B···O2iv | 0.87 (2) | 2.04 (2) | 2.889 (3) | 167 (3) |
OW3—H3A···OW5v | 0.89 (2) | 1.87 (2) | 2.754 (3) | 178 (3) |
OW3—H3B···O5i | 0.88 (2) | 2.11 (2) | 2.938 (3) | 157 (3) |
OW4—H4A···O2 | 0.90 (2) | 1.97 (2) | 2.845 (3) | 163 (3) |
OW4—H4B···O1vi | 0.89 (2) | 1.98 (2) | 2.866 (3) | 173 (3) |
OW5—H5A···O3vii | 0.86 (2) | 1.93 (2) | 2.738 (3) | 155 (3) |
OW5—H5B···O1iv | 0.85 (2) | 1.96 (2) | 2.796 (3) | 167 (3) |
O4—H4···O3viii | 0.82 | 1.88 | 2.653 (3) | 156 |
O6—H6···O5 | 0.82 | 1.92 | 2.637 (3) | 146 |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) x, y, z+1; (iii) x, y+1, z+1; (iv) −x+1, −y+1, −z+1; (v) −x+2, −y+1, −z+2; (vi) x+1, y, z; (vii) −x+1, −y, −z+1; (viii) −x, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Zn(H2O)6](C7H5O6S)2·4H2O |
Mr | 679.87 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 6.5367 (14), 7.2555 (18), 14.616 (4) |
α, β, γ (°) | 92.83 (2), 96.321 (19), 102.839 (17) |
V (Å3) | 669.8 (3) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.17 |
Crystal size (mm) | 0.52 × 0.36 × 0.32 |
Data collection | |
Diffractometer | Siemens P4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.517, 0.688 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3445, 2615, 2101 |
Rint | 0.020 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.088, 1.03 |
No. of reflections | 2615 |
No. of parameters | 209 |
No. of restraints | 10 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.51, −0.29 |
Computer programs: XSCANS (Siemens, 1994), XSCANS, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL-Plus (Sheldrick, 1990), SHELXL97.
C4—O6 | 1.349 (3) | O3—S1 | 1.4582 (18) |
C7—O5 | 1.227 (3) | OW1—Zn1 | 2.059 (2) |
C7—O4 | 1.311 (3) | OW2—Zn1 | 2.088 (2) |
O1—S1 | 1.463 (2) | OW3—Zn1 | 2.099 (2) |
O2—S1 | 1.440 (2) | ||
O5—C7—O4 | 123.6 (2) | OW1—Zn1—OW2 | 89.56 (10) |
O2—S1—O3 | 112.10 (12) | OW1—Zn1—OW3 | 88.60 (9) |
O2—S1—O1 | 113.37 (14) | OW2—Zn1—OW3 | 89.95 (9) |
O3—S1—O1 | 109.74 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
OW1—H1A···OW4i | 0.891 (18) | 1.964 (19) | 2.827 (3) | 162 (3) |
OW1—H1B···OW5 | 0.868 (18) | 1.950 (19) | 2.797 (3) | 165 (3) |
OW2—H2A···OW4ii | 0.889 (18) | 1.891 (18) | 2.775 (3) | 173 (3) |
OW2—H2B···O2iii | 0.870 (18) | 2.035 (19) | 2.889 (3) | 167 (3) |
OW3—H3A···OW5iv | 0.887 (18) | 1.868 (19) | 2.754 (3) | 178 (3) |
OW3—H3B···O5v | 0.878 (18) | 2.111 (19) | 2.938 (3) | 157 (3) |
OW4—H4A···O2 | 0.901 (18) | 1.971 (19) | 2.845 (3) | 163 (3) |
OW4—H4B···O1vi | 0.890 (18) | 1.981 (19) | 2.866 (3) | 173 (3) |
OW5—H5A···O3vii | 0.859 (18) | 1.934 (19) | 2.738 (3) | 155 (3) |
OW5—H5B···O1iii | 0.846 (18) | 1.964 (19) | 2.796 (3) | 167 (3) |
O4—H4···O3viii | 0.82 | 1.88 | 2.653 (3) | 156 |
O6—H6···O5 | 0.82 | 1.92 | 2.637 (3) | 146 |
Symmetry codes: (i) x, y, z+1; (ii) x, y+1, z+1; (iii) −x+1, −y+1, −z+1; (iv) −x+2, −y+1, −z+2; (v) −x+1, −y+1, −z+2; (vi) x+1, y, z; (vii) −x+1, −y, −z+1; (viii) −x, −y, −z+1. |
The crystal structures of five transition metal (Mn, Co, Ni, Cu and Zn) 3-carboxy-4-hydroxybenzenesulfonates have been determined. The structures of the manganese (Ma et al., 2003a), cobalt (Ma et al., 2003b), nickel (Ma et al., 2003c) and copper compound (Ma et al., 2003 d) have been reported in the preceding papers. The crystal structure of the zinc compound, (I), is presented here.
The ZnII atom is located on an inversion center, and all other atoms are in general positions. Selected bond lengths and angles are given in Table 1. Fig. 1 shows the asymmetric unit, together with the complete coordination environment of the ZnII cation. Compound (I) is isostructural with the cobalt compound (Ma et al., 2003b) and nickel compound (Ma et al., 2003c). The Zn—O distances range from 2.059 (2) to 2.099 (2) Å. The average Zn—O distance of 2.082 Å is slightly shorter than the values in other zinc compounds (Li et al., 2002).
The alternating layers of [Zn(H2O)6]2+ cations and sulfonate anions in (I) are shown in Fig.2. Selected hydrogen-bond parameters are listed in Table 2.