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Zinc(II) formaldehyde sulfoxylate, [Zn(CH3O3S)2], a widely marketed additive in the polymer and textile industry (under the registered trademarks Decroline, Decolin and Safolin, CAS 24887-06-7), possesses, in the solid state, a polymeric framework, with the Zn atoms octahedrally coordinated by six O atoms of four different hydroxymethanesulfinate groups. The latter are found to coordinate through all their O atoms, including the hydroxy ones, and possess a chelating nature. By contrast, in the structure of the only other commercially available salt of this ligand (dihydrated sodium formaldehyde sulfoxylate), the organic residue, being involved in an extensive network of hydrogen-bond contacts, is fully stretched and bridges two NaI ions through a single O atom.
Supporting information
CCDC reference: 293853
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (O-C) = 0.010 Å
- R factor = 0.028
- wR factor = 0.074
- Data-to-parameter ratio = 6.0
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT089_ALERT_3_C Poor Data / Parameter Ratio (Zmax .LT. 18) ..... 6.05
PLAT731_ALERT_1_C Bond Calc 0.82(4), Rep 0.820(10) ...... 4.00 su-Rat
O6 -H6 1.555 1.555
PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) . 1.21 Ratio
Alert level G
REFLT03_ALERT_4_G WARNING: Large fraction of Friedel related reflns may
be needed to determine absolute structure
From the CIF: _diffrn_reflns_theta_max 25.27
From the CIF: _reflns_number_total 653
Count of symmetry unique reflns 653
Completeness (_total/calc) 100.00%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 0
Fraction of Friedel pairs measured 0.000
Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
3 ALERT level C = Check and explain
1 ALERT level G = General alerts; check
1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
0 ALERT type 2 Indicator that the structure model may be wrong or deficient
1 ALERT type 3 Indicator that the structure quality may be low
2 ALERT type 4 Improvement, methodology, query or suggestion
checkCIF publication errors
Alert level A
PUBL023_ALERT_1_A There is a mismatched ^ on line 189
'Masciocchi^, Norberto'
If you require a ^ then it should be escaped
with a \, i.e. \^
Otherwise there must be a matching closing ~, e.g. ^12^C
1 ALERT level A = Data missing that is essential or data in wrong format
0 ALERT level G = General alerts. Data that may be required is missing
Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software; data reduction: local programs; program(s) used to solve structure: SHELXS86 (Sheldrick, 1986); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 in WinGX (Farrugia, 1999); software used to prepare material for publication: SHELXL97.
Poly[di-µ
3-hydroxymethanesulfinato-zinc(II)]
top
Crystal data top
[Zn(CH3O3S)2] | F(000) = 512 |
Mr = 255.56 | Dx = 2.360 Mg m−3 |
Monoclinic, Cc | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: C -2yc | Cell parameters from 25 reflections |
a = 8.332 (5) Å | θ = 9–12° |
b = 10.797 (10) Å | µ = 3.97 mm−1 |
c = 8.939 (2) Å | T = 295 K |
β = 116.56 (3)° | Prism, colourless |
V = 719.3 (8) Å3 | 0.12 × 0.10 × 0.10 mm |
Z = 4 | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.000 |
Radiation source: fine-focus sealed tube, Enraf-Nonius X-ray Generator | θmax = 25.3°, θmin = 3.3° |
Graphite monochromator | h = −10→8 |
ω scan | k = 0→12 |
653 measured reflections | l = 0→10 |
653 independent reflections | 3 standard reflections every 10800 min |
652 reflections with I > 2σ(I) | intensity decay: 5.0% |
Refinement top
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)] = 0.028 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.074 | w = 1/[σ2(Fo2) + (0.0173P)2 + 8.9338P] where P = (Fo2 + 2Fc2)/3 |
S = 1.15 | (Δ/σ)max = 0.013 |
653 reflections | Δρmax = 0.67 e Å−3 |
108 parameters | Δρmin = −0.79 e Å−3 |
4 restraints | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.02 (3) |
Special details top
Experimental. Several crystals have been tested, all showing extreme mosaicity and heavily
broadened, multiple peaks in the ω axis. Eventually, a (nearly)
single-crystal specimen was found, which allowed a satisfactory unit cell
determination, although with far from ideal e.s.d.'s. Of the several data
collections performed with increasing ω scan width, the best results,
reported hereafter, were obtained by the omega scan method with a rather
unconventional scan angle of Δω=6.0 + 0.35tanθ°, 150 s per reflection (see
the caption of Figure 3 for a further comment). Data collection performed with
an Enraf–Nonius CAD-4 four-circle diffractometer equipped with a
scintillation counter, sealed X-ray tube with Mo Kα radiation, graphite
monochromator. Lattice parameters obtained by the indexing and least-squares
refinement procedures of the setting angles of 25 strong reflections randomly
distributed in the 9<θ<12° range. No absorption correction was applied.
Powder diffraction data (Cu Kα radiation) were collected on the bulk
sample, in order to test sample purity, crystal mosaicity and to confirm the
unit cell proposed above. The relevant comments are reported in the caption to
Fig.3. |
Geometry. All e.s.d.'s 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. |
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 | |
Zn | 0.00150 (9) | 0.14440 (7) | 0.55754 (9) | 0.02306 (17) | |
S1 | 0.0926 (2) | 0.34050 (17) | 0.8285 (2) | 0.0264 (4) | |
S2 | 0.2006 (2) | 0.02396 (17) | 0.3735 (2) | 0.0259 (4) | |
O1 | 0.1286 (7) | 0.3027 (5) | 0.6808 (6) | 0.0276 (12) | |
O2 | 0.2496 (6) | 0.2991 (5) | 0.9910 (6) | 0.0284 (12) | |
O3 | 0.3197 (6) | 0.5296 (5) | 0.9125 (6) | 0.0323 (14) | |
C1 | 0.1364 (9) | 0.5070 (8) | 0.8371 (11) | 0.034 (2) | |
H1A | 0.0827 | 0.5408 | 0.7246 | 0.040* | |
H1B | 0.0821 | 0.5479 | 0.8999 | 0.040* | |
O4 | 0.2039 (6) | 0.0495 (5) | 0.5419 (6) | 0.0307 (13) | |
O5 | 0.0352 (7) | −0.0570 (5) | 0.2720 (6) | 0.0281 (12) | |
O6 | −0.0117 (6) | 0.2178 (5) | 0.3204 (6) | 0.0302 (13) | |
C2 | 0.1220 (11) | 0.1736 (7) | 0.2768 (10) | 0.0343 (18) | |
H2A | 0.2213 | 0.2316 | 0.3147 | 0.041* | |
H2B | 0.0727 | 0.1662 | 0.1562 | 0.041* | |
H3 | 0.336 (3) | 0.518 (9) | 0.829 (2) | 0.07 (4)* | |
H6 | −0.113 (3) | 0.207 (7) | 0.244 (5) | 0.04 (3)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Zn | 0.0225 (3) | 0.0221 (3) | 0.0231 (3) | 0.0007 (4) | 0.0089 (2) | 0.0005 (4) |
S1 | 0.0196 (7) | 0.0254 (9) | 0.0325 (9) | −0.0014 (7) | 0.0101 (6) | −0.0049 (7) |
S2 | 0.0218 (7) | 0.0280 (9) | 0.0272 (8) | −0.0009 (7) | 0.0105 (6) | −0.0051 (7) |
O1 | 0.029 (2) | 0.025 (2) | 0.026 (2) | −0.005 (2) | 0.0094 (19) | −0.008 (2) |
O2 | 0.028 (2) | 0.029 (3) | 0.026 (2) | −0.004 (2) | 0.0103 (19) | −0.001 (2) |
O3 | 0.029 (3) | 0.031 (3) | 0.036 (3) | −0.003 (2) | 0.013 (2) | −0.003 (2) |
C1 | 0.024 (4) | 0.022 (3) | 0.047 (4) | 0.005 (3) | 0.009 (3) | −0.001 (3) |
O4 | 0.026 (2) | 0.036 (3) | 0.028 (2) | 0.001 (2) | 0.010 (2) | −0.007 (2) |
O5 | 0.027 (2) | 0.031 (3) | 0.025 (2) | −0.008 (2) | 0.0104 (19) | −0.006 (2) |
O6 | 0.028 (2) | 0.025 (3) | 0.037 (3) | 0.000 (2) | 0.015 (2) | 0.004 (2) |
C2 | 0.039 (4) | 0.028 (4) | 0.043 (4) | −0.003 (3) | 0.025 (3) | −0.001 (3) |
Geometric parameters (Å, º) top
Zn—O2i | 2.004 (5) | O2—Zniii | 2.004 (5) |
Zn—O4 | 2.031 (5) | O3—C1 | 1.388 (9) |
Zn—O5ii | 2.040 (5) | O3—Zniii | 2.398 (6) |
Zn—O1 | 2.053 (5) | O3—H3 | 0.821 (11) |
Zn—O6 | 2.219 (5) | C1—H1A | 0.9700 |
Zn—O3i | 2.398 (6) | C1—H1B | 0.9700 |
S1—O2 | 1.524 (5) | O5—Zniv | 2.040 (5) |
S1—O1 | 1.535 (6) | O6—C2 | 1.418 (10) |
S1—C1 | 1.829 (9) | O6—H6 | 0.820 (10) |
S2—O4 | 1.518 (5) | C2—H2A | 0.9700 |
S2—O5 | 1.539 (5) | C2—H2B | 0.9700 |
S2—C2 | 1.812 (8) | | |
| | | |
O2i—Zn—O4 | 157.7 (2) | S1—O2—Zniii | 122.2 (3) |
O2i—Zn—O5ii | 96.0 (2) | C1—O3—Zniii | 114.6 (5) |
O4—Zn—O5ii | 93.5 (2) | C1—O3—H3 | 97 (2) |
O2i—Zn—O1 | 97.3 (2) | Zniii—O3—H3 | 93 (5) |
O4—Zn—O1 | 102.3 (2) | O3—C1—S1 | 110.4 (5) |
O5ii—Zn—O1 | 93.4 (2) | O3—C1—H1A | 109.6 |
O2i—Zn—O6 | 90.6 (2) | S1—C1—H1A | 109.6 |
O4—Zn—O6 | 78.6 (2) | O3—C1—H1B | 109.6 |
O5ii—Zn—O6 | 171.8 (2) | S1—C1—H1B | 109.6 |
O1—Zn—O6 | 90.5 (2) | H1A—C1—H1B | 108.1 |
O2i—Zn—O3i | 75.7 (2) | S2—O4—Zn | 120.8 (3) |
O4—Zn—O3i | 84.9 (2) | S2—O5—Zniv | 121.9 (3) |
O5ii—Zn—O3i | 86.2 (2) | C2—O6—Zn | 115.7 (4) |
O1—Zn—O3i | 172.9 (2) | C2—O6—H6 | 111 (4) |
O6—Zn—O3i | 90.79 (19) | Zn—O6—H6 | 110 (5) |
O2—S1—O1 | 109.1 (3) | O6—C2—S2 | 109.2 (5) |
O2—S1—C1 | 100.3 (3) | O6—C2—H2A | 109.8 |
O1—S1—C1 | 100.6 (4) | S2—C2—H2A | 109.8 |
O4—S2—O5 | 107.6 (3) | O6—C2—H2B | 109.8 |
O4—S2—C2 | 98.9 (4) | S2—C2—H2B | 109.8 |
O5—S2—C2 | 100.8 (3) | H2A—C2—H2B | 108.3 |
S1—O1—Zn | 115.5 (3) | | |
Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) x, −y, z+1/2; (iii) x+1/2, −y+1/2, z+1/2; (iv) x, −y, z−1/2. |
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