Two different zinc sulfite compounds have been prepared through the decomposition of pyrosulfite-dithionite ions in aqueous solution,
viz. a dimeric complex, di-
-sulfito-
3O,
O':
O'';
3O:
O',
O''-bis[(4,4'-dimethyl-2,2'-bipyridine-
2N,
N')zinc(II)] dihydrate, [Zn
2(SO
3)
2(C
12H
12N
2)
2]·2H
2O, (I), which was solved and refined from a twinned sample, and an extended polymer, poly[[aqua(1,10-phenanthroline-
2N,
N')zinc(II)]-
3-sulfito-
2O:
O':
O''-zinc(II)-
3-sulfito-
3O:
O:
O'], [Zn
2(SO
3)
2(C
12H
10N
2)(H
2O)]
n, (II). In (I), the dinuclear Zn
II complex has a center of symmetry. The cation is five-coordinate in a square-pyramidal arrangement, the anion fulfilling a bridging chelating role. Compound (II) comprises two different zinc units, one being five-coordinate (square pyramidal) and the other four-coordinate (trigonal pyramidal), and two independent sulfite groups with different binding modes to the cationic centers.
Supporting information
CCDC references: 263025; 263026
Both compounds were obtained by dissolving the corresponding aromatic amine [4,4'-dimethyl-2,2'-dipyridine for (I) and phenantroline monohydrate for (II)] in ethanol (96%) and allowing this solution to diffuse slowly into an aqueous solution of zinc acetate dihydrate, Na2S2O4·2H2O and K2S2O5 (molar ratios 1:1:1:2). After two months, crystals of a suitable size for X-ray analysis had developed.
Crystals of (I) grow as non-merohedral twins, a fact that was clearly visible with the CCD at the data collection stage. Even though the (two) most important orientations could be separated and non-overlapped reflections integrated, heavily overlapped reflections were impossible to deal with. Since their inclusion impaired the refinement, it was decided to omit them from the data set, considering that in spite of this drawback a very reasonable data-to-parameters ratio of 10:1 could still be obtained, with an even distribution of data in reciprocal space. The only suspicious outcome attributable to poor data quality was the abnormally prolate displacement ellipsoids for atoms C5 and O1. The twin ratio in the crystal measured was about 70:30.
H atoms attached to C atoms and unambiguously defined by the stereochemistry were placed at calculated positions (C—H = 0.93 Å) and allowed to ride. Terminal methyl groups (C—H = 0.96 Å) were allowed to rotate as well. Uiso(H) values were set at 1.2Ueq(parent atom) or 1.5Ueq(Cmethyl). H atoms of water molecules were located from difference Fourier syntheses and refined with restrained parameters [O—H = 0.82 (1) Å and H···H = 1.35 (2) Å].
Data collection: SMART-NT (Bruker, 2001) for (I); MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988) for (II). Cell refinement: SAINT-NT (Bruker, 2000) for (I); MSC/AFC Diffractometer Control Software for (II). Data reduction: SAINT-NT for (I); MSC/AFC Diffractometer Control Software for (II). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL-PC (Sheldrick, 1994); software used to prepare material for publication: SHELXL97.
(I) di-µ-sulfito-
κ3O,
O':
O'';
κ3O:
O',
O''-bis[(4,4'-dimethyl-2,2'-bipyridine-
κ2N,
N')zinc(II)] dihydrate
top
Crystal data top
[Zn2(SO3)2(C12H12N2)]·2H2O | Z = 1 |
Mr = 695.36 | F(000) = 356 |
Triclinic, P1 | Dx = 1.700 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71070 Å |
a = 7.534 (4) Å | Cell parameters from 273 reflections |
b = 9.621 (5) Å | θ = 4.0–25.5° |
c = 11.051 (5) Å | µ = 1.98 mm−1 |
α = 113.233 (8)° | T = 296 K |
β = 96.932 (9)° | Blocks, colorless |
γ = 106.746 (9)° | 0.22 × 0.20 × 0.10 mm |
V = 679.4 (6) Å3 | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 2037 independent reflections |
Radiation source: fine-focus sealed tube | 1623 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.079 |
ϕ and ω scans | θmax = 27.6°, θmin = 2.1° |
Absorption correction: multi-scan [SADABS (Sheldrick, 1996) in SAINT-NT (Bruker, 2000)] | h = −9→9 |
Tmin = 0.66, Tmax = 0.82 | k = −11→11 |
2037 measured reflections | l = 0→14 |
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)] = 0.064 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.182 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | w = 1/[σ2(Fo2) + (0.1397P)2] where P = (Fo2 + 2Fc2)/3 |
2037 reflections | (Δ/σ)max = 0.011 |
191 parameters | Δρmax = 0.95 e Å−3 |
3 restraints | Δρmin = −1.30 e Å−3 |
Crystal data top
[Zn2(SO3)2(C12H12N2)]·2H2O | γ = 106.746 (9)° |
Mr = 695.36 | V = 679.4 (6) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.534 (4) Å | Mo Kα radiation |
b = 9.621 (5) Å | µ = 1.98 mm−1 |
c = 11.051 (5) Å | T = 296 K |
α = 113.233 (8)° | 0.22 × 0.20 × 0.10 mm |
β = 96.932 (9)° | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 2037 independent reflections |
Absorption correction: multi-scan [SADABS (Sheldrick, 1996) in SAINT-NT (Bruker, 2000)] | 1623 reflections with I > 2σ(I) |
Tmin = 0.66, Tmax = 0.82 | Rint = 0.079 |
2037 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.064 | 3 restraints |
wR(F2) = 0.182 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.95 e Å−3 |
2037 reflections | Δρmin = −1.30 e Å−3 |
191 parameters | |
Special details top
Experimental. The crystals grow as non-merohedral twins, a fact which was clearly visible with the CCD at the data collection stage. Even though the (two) most important orientations could be separated and non overlapped reflections integrated, heavyly overlapped ones were impossible to deal with. Since their inclussion impaired the refinement, it was decided to withdraw them from the data set, considering that in spite of this drawback a very reasonable data-to-parameters ratio of 10:1 could anyway be obtained, with an even distribution of data in reciprocal space. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Zn1 | 0.57473 (9) | 0.72053 (8) | 0.51318 (8) | 0.0329 (3) | |
S1 | 0.2636 (2) | 0.5645 (2) | 0.5775 (2) | 0.0426 (5) | |
O1 | 0.2433 (6) | 0.3882 (5) | 0.5324 (6) | 0.0444 (13) | |
O2 | 0.2877 (6) | 0.5956 (6) | 0.4537 (5) | 0.0465 (13) | |
O3 | 0.4638 (7) | 0.6687 (6) | 0.6720 (6) | 0.0530 (14) | |
N1 | 0.5933 (7) | 0.8282 (6) | 0.3794 (6) | 0.0326 (12) | |
N2 | 0.7506 (7) | 0.9559 (6) | 0.6438 (6) | 0.0340 (12) | |
C1 | 0.5070 (9) | 0.7535 (8) | 0.2435 (7) | 0.0411 (17) | |
H1 | 0.4134 | 0.6495 | 0.2049 | 0.049* | |
C2 | 0.5531 (9) | 0.8261 (8) | 0.1609 (7) | 0.0395 (16) | |
H2 | 0.4917 | 0.7717 | 0.0679 | 0.047* | |
C3 | 0.6921 (8) | 0.9812 (8) | 0.2173 (7) | 0.0356 (15) | |
C4 | 0.7788 (8) | 1.0570 (7) | 0.3549 (6) | 0.0289 (13) | |
H4 | 0.8734 | 1.1607 | 0.3950 | 0.035* | |
C5 | 0.7249 (8) | 0.9785 (7) | 0.4350 (7) | 0.0276 (13) | |
C6 | 0.8084 (7) | 1.0543 (7) | 0.5838 (7) | 0.0294 (14) | |
C7 | 0.9384 (8) | 1.2139 (7) | 0.6608 (7) | 0.0324 (14) | |
H7 | 0.9761 | 1.2794 | 0.6181 | 0.039* | |
C8 | 1.0115 (8) | 1.2754 (7) | 0.7989 (7) | 0.0358 (15) | |
C9 | 0.9502 (9) | 1.1742 (8) | 0.8575 (7) | 0.0386 (16) | |
H9 | 0.9974 | 1.2119 | 0.9509 | 0.046* | |
C10 | 0.8212 (9) | 1.0196 (8) | 0.7802 (7) | 0.0403 (17) | |
H10 | 0.7799 | 0.9550 | 0.8232 | 0.048* | |
C11 | 0.7470 (11) | 1.0632 (10) | 0.1271 (8) | 0.0514 (19) | |
H11A | 0.6412 | 1.0876 | 0.0950 | 0.077* | |
H11B | 0.7773 | 0.9915 | 0.0505 | 0.077* | |
H11C | 0.8570 | 1.1621 | 0.1790 | 0.077* | |
C12 | 1.1555 (10) | 1.4472 (8) | 0.8816 (8) | 0.0473 (18) | |
H12A | 1.0891 | 1.5192 | 0.9185 | 0.071* | |
H12B | 1.2252 | 1.4795 | 0.8240 | 0.071* | |
H12C | 1.2436 | 1.4522 | 0.9550 | 0.071* | |
O1W | 0.2283 (12) | 0.3627 (9) | 0.1817 (8) | 0.081 (2) | |
H1WB | 0.315 (9) | 0.332 (9) | 0.200 (6) | 0.06 (3)* | |
H1WA | 0.215 (10) | 0.428 (7) | 0.251 (4) | 0.04 (2)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Zn1 | 0.0290 (4) | 0.0199 (5) | 0.0529 (6) | 0.0033 (3) | 0.0134 (3) | 0.0226 (4) |
S1 | 0.0339 (8) | 0.0317 (10) | 0.0776 (13) | 0.0141 (7) | 0.0285 (8) | 0.0344 (10) |
O1 | 0.043 (2) | 0.018 (2) | 0.085 (4) | 0.0108 (19) | 0.032 (2) | 0.032 (3) |
O2 | 0.039 (2) | 0.044 (3) | 0.073 (4) | 0.011 (2) | 0.013 (2) | 0.045 (3) |
O3 | 0.048 (3) | 0.035 (3) | 0.075 (4) | 0.002 (2) | 0.023 (2) | 0.030 (3) |
N1 | 0.030 (2) | 0.018 (3) | 0.052 (3) | 0.0030 (19) | 0.012 (2) | 0.022 (3) |
N2 | 0.031 (2) | 0.026 (3) | 0.048 (3) | 0.004 (2) | 0.011 (2) | 0.024 (3) |
C1 | 0.035 (3) | 0.033 (4) | 0.050 (4) | 0.000 (3) | −0.001 (3) | 0.026 (4) |
C2 | 0.051 (4) | 0.022 (4) | 0.040 (4) | 0.008 (3) | 0.008 (3) | 0.012 (3) |
C3 | 0.037 (3) | 0.032 (4) | 0.049 (4) | 0.015 (3) | 0.018 (3) | 0.025 (3) |
C4 | 0.029 (3) | 0.021 (3) | 0.042 (4) | 0.007 (2) | 0.008 (2) | 0.022 (3) |
C5 | 0.035 (3) | 0.013 (3) | 0.048 (4) | 0.014 (2) | 0.019 (3) | 0.021 (3) |
C6 | 0.023 (2) | 0.020 (3) | 0.048 (4) | 0.007 (2) | 0.015 (2) | 0.018 (3) |
C7 | 0.033 (3) | 0.019 (3) | 0.044 (4) | 0.006 (2) | 0.012 (3) | 0.015 (3) |
C8 | 0.036 (3) | 0.019 (3) | 0.051 (4) | 0.009 (2) | 0.015 (3) | 0.014 (3) |
C9 | 0.050 (3) | 0.034 (4) | 0.028 (4) | 0.016 (3) | 0.014 (3) | 0.010 (3) |
C10 | 0.043 (3) | 0.030 (4) | 0.054 (5) | 0.005 (3) | 0.014 (3) | 0.031 (4) |
C11 | 0.058 (4) | 0.051 (5) | 0.056 (5) | 0.018 (4) | 0.017 (4) | 0.036 (4) |
C12 | 0.052 (4) | 0.027 (4) | 0.046 (4) | −0.001 (3) | 0.011 (3) | 0.011 (4) |
O1W | 0.102 (6) | 0.052 (5) | 0.063 (5) | 0.008 (4) | −0.017 (4) | 0.027 (4) |
Geometric parameters (Å, º) top
Zn1—O1i | 1.951 (4) | C4—H4 | 0.9300 |
Zn1—O2 | 2.022 (4) | C5—C6 | 1.474 (9) |
Zn1—N2 | 2.049 (5) | C6—C7 | 1.394 (8) |
Zn1—N1 | 2.110 (5) | C7—C8 | 1.371 (9) |
Zn1—O3 | 2.198 (5) | C7—H7 | 0.9300 |
S1—O3 | 1.514 (5) | C8—C9 | 1.375 (9) |
S1—O1 | 1.522 (5) | C8—C12 | 1.510 (9) |
S1—O2 | 1.532 (5) | C9—C10 | 1.361 (9) |
N1—C5 | 1.333 (7) | C9—H9 | 0.9300 |
N1—C1 | 1.356 (9) | C10—H10 | 0.9300 |
N2—C10 | 1.349 (9) | C11—H11A | 0.9600 |
N2—C6 | 1.361 (8) | C11—H11B | 0.9600 |
C1—C2 | 1.371 (9) | C11—H11C | 0.9600 |
C1—H1 | 0.9300 | C12—H12A | 0.9600 |
C2—C3 | 1.385 (8) | C12—H12B | 0.9600 |
C2—H2 | 0.9300 | C12—H12C | 0.9600 |
C3—C4 | 1.371 (9) | O1W—H1WB | 0.83 (8) |
C3—C11 | 1.523 (9) | O1W—H1WA | 0.82 (5) |
C4—C5 | 1.399 (8) | | |
| | | |
O1i—Zn1—O2 | 121.9 (2) | C3—C4—C5 | 120.0 (5) |
O1i—Zn1—N2 | 102.8 (2) | C3—C4—H4 | 120.0 |
O2—Zn1—N2 | 134.7 (2) | C5—C4—H4 | 120.0 |
O1i—Zn1—N1 | 99.3 (2) | N1—C5—C4 | 121.1 (6) |
O2—Zn1—N1 | 99.28 (19) | N1—C5—C6 | 116.0 (5) |
N2—Zn1—N1 | 78.6 (2) | C4—C5—C6 | 122.9 (5) |
O1i—Zn1—O3 | 107.4 (2) | N2—C6—C7 | 120.9 (6) |
O2—Zn1—O3 | 66.9 (2) | N2—C6—C5 | 115.0 (5) |
N2—Zn1—O3 | 94.9 (2) | C7—C6—C5 | 124.1 (6) |
N1—Zn1—O3 | 153.3 (2) | C8—C7—C6 | 120.7 (6) |
O3—S1—O1 | 106.8 (3) | C8—C7—H7 | 119.6 |
O3—S1—O2 | 99.8 (3) | C6—C7—H7 | 119.6 |
O1—S1—O2 | 105.5 (3) | C7—C8—C9 | 117.4 (6) |
O3—S1—Zn1 | 53.4 (2) | C7—C8—C12 | 120.6 (6) |
O1—S1—Zn1 | 109.56 (18) | C9—C8—C12 | 122.0 (6) |
O2—S1—Zn1 | 46.85 (17) | C10—C9—C8 | 120.6 (6) |
S1—O1—Zn1i | 131.6 (3) | C10—C9—H9 | 119.7 |
S1—O2—Zn1 | 99.6 (2) | C8—C9—H9 | 119.7 |
S1—O3—Zn1 | 93.0 (3) | N2—C10—C9 | 122.8 (6) |
C5—N1—C1 | 118.8 (5) | N2—C10—H10 | 118.6 |
C5—N1—Zn1 | 113.7 (4) | C9—C10—H10 | 118.6 |
C1—N1—Zn1 | 126.8 (4) | C3—C11—H11A | 109.5 |
C10—N2—C6 | 117.5 (5) | C3—C11—H11B | 109.5 |
C10—N2—Zn1 | 126.8 (4) | H11A—C11—H11B | 109.5 |
C6—N2—Zn1 | 115.5 (4) | C3—C11—H11C | 109.5 |
N1—C1—C2 | 122.3 (6) | H11A—C11—H11C | 109.5 |
N1—C1—H1 | 118.9 | H11B—C11—H11C | 109.5 |
C2—C1—H1 | 118.9 | C8—C12—H12A | 109.5 |
C1—C2—C3 | 119.3 (6) | C8—C12—H12B | 109.5 |
C1—C2—H2 | 120.3 | H12A—C12—H12B | 109.5 |
C3—C2—H2 | 120.3 | C8—C12—H12C | 109.5 |
C4—C3—C2 | 118.4 (6) | H12A—C12—H12C | 109.5 |
C4—C3—C11 | 121.4 (6) | H12B—C12—H12C | 109.5 |
C2—C3—C11 | 120.2 (6) | H1WB—O1W—H1WA | 111 (3) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WB···O3i | 0.83 (8) | 2.06 (7) | 2.823 (10) | 155 (6) |
O1W—H1WA···O2 | 0.82 (5) | 2.07 (6) | 2.835 (10) | 157 (6) |
C7—H7···O1ii | 0.93 | 2.46 | 3.247 (7) | 142 |
C9—H9···O1Wiii | 0.93 | 2.49 | 3.374 (9) | 159 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1, y+1, z; (iii) x+1, y+1, z+1. |
(II) poly[[aqua(1,10-phenanthroline-
κ2N,
N')zinc(II)]-µ
3-sulfito-
κ2O:
O':
O''- zinc(II)-µ
3-sulfito-
κ3O:
O:
O']
top
Crystal data top
[Zn2(SO3)2(C12H10N2)(H2O)] | Z = 2 |
Mr = 489.08 | F(000) = 488 |
Triclinic, P1 | Dx = 2.189 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.0271 (16) Å | Cell parameters from 25 reflections |
b = 9.4817 (19) Å | θ = 10.2–16.0° |
c = 10.286 (2) Å | µ = 3.56 mm−1 |
α = 80.98 (3)° | T = 293 K |
β = 80.39 (3)° | Plates, colorless |
γ = 75.55 (3)° | 0.32 × 0.24 × 0.14 mm |
V = 742.0 (3) Å3 | |
Data collection top
Rigaku AFC6 diffractometer | 1976 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.034 |
Graphite monochromator | θmax = 26.0°, θmin = 2.0° |
ω/2θ scans | h = −9→9 |
Absorption correction: ψ scan (North et al., 1968) | k = −11→2 |
Tmin = 0.37, Tmax = 0.60 | l = −12→12 |
3847 measured reflections | 3 standard reflections every 150 reflections |
2926 independent reflections | intensity decay: 1.2% |
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)] = 0.030 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.079 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.97 | w = 1/[σ2(Fo2) + (0.039P)2] where P = (Fo2 + 2Fc2)/3 |
2926 reflections | (Δ/σ)max = 0.029 |
232 parameters | Δρmax = 0.42 e Å−3 |
3 restraints | Δρmin = −0.52 e Å−3 |
Crystal data top
[Zn2(SO3)2(C12H10N2)(H2O)] | γ = 75.55 (3)° |
Mr = 489.08 | V = 742.0 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.0271 (16) Å | Mo Kα radiation |
b = 9.4817 (19) Å | µ = 3.56 mm−1 |
c = 10.286 (2) Å | T = 293 K |
α = 80.98 (3)° | 0.32 × 0.24 × 0.14 mm |
β = 80.39 (3)° | |
Data collection top
Rigaku AFC6 diffractometer | 1976 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.034 |
Tmin = 0.37, Tmax = 0.60 | 3 standard reflections every 150 reflections |
3847 measured reflections | intensity decay: 1.2% |
2926 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.030 | 3 restraints |
wR(F2) = 0.079 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.97 | Δρmax = 0.42 e Å−3 |
2926 reflections | Δρmin = −0.52 e Å−3 |
232 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Zn1 | 0.32018 (6) | 0.67862 (5) | 0.16652 (4) | 0.02456 (13) | |
Zn2 | 0.24315 (6) | 1.00687 (5) | −0.05093 (5) | 0.02562 (14) | |
S1A | 0.06614 (13) | 0.74326 (11) | −0.04183 (10) | 0.0248 (2) | |
O1A | 0.1620 (4) | 0.8546 (3) | −0.1232 (3) | 0.0325 (7) | |
O2A | −0.0487 (4) | 0.8238 (3) | 0.0703 (3) | 0.0316 (7) | |
O3A | 0.2031 (4) | 0.6289 (3) | 0.0322 (3) | 0.0285 (7) | |
S1B | 0.37973 (12) | 0.99622 (11) | 0.20246 (9) | 0.0218 (2) | |
O1B | 0.3261 (4) | 0.8940 (3) | 0.1167 (3) | 0.0262 (6) | |
O2B | 0.5763 (3) | 0.9471 (3) | 0.1924 (3) | 0.0295 (7) | |
O3B | 0.3328 (4) | 1.1404 (3) | 0.1200 (3) | 0.0352 (7) | |
N1 | 0.3915 (4) | 0.4869 (4) | 0.2991 (3) | 0.0239 (7) | |
N2 | 0.1460 (4) | 0.7310 (4) | 0.3443 (3) | 0.0268 (8) | |
C1 | 0.5108 (6) | 0.3656 (5) | 0.2744 (4) | 0.0324 (10) | |
H1A | 0.5707 | 0.3599 | 0.1891 | 0.039* | |
C2 | 0.5492 (6) | 0.2472 (5) | 0.3706 (4) | 0.0337 (10) | |
H2A | 0.6330 | 0.1638 | 0.3496 | 0.040* | |
C3 | 0.4638 (6) | 0.2538 (5) | 0.4963 (4) | 0.0358 (11) | |
H3A | 0.4899 | 0.1751 | 0.5617 | 0.043* | |
C4 | 0.3369 (5) | 0.3787 (5) | 0.5267 (4) | 0.0271 (9) | |
C5 | 0.2341 (6) | 0.3936 (5) | 0.6555 (4) | 0.0330 (10) | |
H5A | 0.2555 | 0.3183 | 0.7246 | 0.040* | |
C6 | 0.1093 (6) | 0.5135 (5) | 0.6771 (4) | 0.0331 (10) | |
H6A | 0.0443 | 0.5192 | 0.7607 | 0.040* | |
C7 | 0.0729 (5) | 0.6341 (5) | 0.5740 (4) | 0.0279 (9) | |
C8 | −0.0588 (5) | 0.7616 (5) | 0.5910 (4) | 0.0332 (10) | |
H8A | −0.1265 | 0.7736 | 0.6729 | 0.040* | |
C9 | −0.0859 (6) | 0.8674 (5) | 0.4852 (4) | 0.0326 (10) | |
H9A | −0.1744 | 0.9513 | 0.4941 | 0.039* | |
C10 | 0.0199 (6) | 0.8494 (5) | 0.3633 (4) | 0.0308 (10) | |
H10A | 0.0009 | 0.9235 | 0.2929 | 0.037* | |
C11 | 0.1718 (5) | 0.6235 (4) | 0.4479 (4) | 0.0231 (8) | |
C12 | 0.3048 (5) | 0.4943 (4) | 0.4243 (4) | 0.0228 (8) | |
O1W | 0.5756 (4) | 0.6350 (3) | 0.0588 (3) | 0.0349 (7) | |
H1WB | 0.612 (5) | 0.698 (3) | 0.005 (4) | 0.042* | |
H1WA | 0.636 (5) | 0.554 (2) | 0.044 (4) | 0.042* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Zn1 | 0.0282 (3) | 0.0208 (3) | 0.0223 (2) | −0.0042 (2) | −0.00138 (19) | −0.00018 (19) |
Zn2 | 0.0220 (2) | 0.0250 (3) | 0.0242 (2) | −0.0005 (2) | −0.00022 (19) | 0.0028 (2) |
S1A | 0.0223 (5) | 0.0224 (5) | 0.0288 (5) | −0.0011 (4) | −0.0054 (4) | −0.0048 (4) |
O1A | 0.0383 (17) | 0.0293 (16) | 0.0284 (15) | −0.0115 (14) | 0.0011 (13) | 0.0016 (13) |
O2A | 0.0256 (15) | 0.0330 (17) | 0.0275 (15) | 0.0067 (13) | −0.0023 (12) | −0.0007 (13) |
O3A | 0.0283 (15) | 0.0199 (14) | 0.0343 (16) | 0.0043 (12) | −0.0088 (13) | −0.0050 (13) |
S1B | 0.0214 (5) | 0.0217 (5) | 0.0197 (5) | −0.0037 (4) | 0.0013 (4) | −0.0013 (4) |
O1B | 0.0301 (15) | 0.0224 (15) | 0.0270 (15) | −0.0088 (12) | −0.0040 (12) | −0.0007 (12) |
O2B | 0.0234 (15) | 0.0380 (17) | 0.0245 (15) | −0.0076 (13) | −0.0010 (12) | 0.0024 (13) |
O3B | 0.0367 (17) | 0.0184 (15) | 0.0431 (18) | −0.0008 (13) | −0.0002 (14) | 0.0038 (13) |
N1 | 0.0225 (17) | 0.0252 (18) | 0.0217 (17) | −0.0041 (15) | −0.0014 (13) | 0.0000 (14) |
N2 | 0.0277 (18) | 0.0255 (19) | 0.0273 (19) | −0.0083 (16) | 0.0011 (15) | −0.0048 (15) |
C1 | 0.032 (2) | 0.031 (2) | 0.030 (2) | −0.005 (2) | −0.0006 (19) | −0.0005 (19) |
C2 | 0.030 (2) | 0.027 (2) | 0.039 (3) | 0.002 (2) | −0.007 (2) | −0.001 (2) |
C3 | 0.040 (3) | 0.032 (2) | 0.031 (2) | −0.004 (2) | −0.011 (2) | 0.009 (2) |
C4 | 0.029 (2) | 0.030 (2) | 0.025 (2) | −0.0104 (19) | −0.0046 (17) | −0.0006 (18) |
C5 | 0.042 (3) | 0.035 (3) | 0.023 (2) | −0.013 (2) | −0.0066 (19) | 0.0000 (19) |
C6 | 0.041 (3) | 0.038 (3) | 0.022 (2) | −0.015 (2) | 0.0024 (19) | −0.0048 (19) |
C7 | 0.028 (2) | 0.033 (2) | 0.024 (2) | −0.0101 (19) | 0.0016 (18) | −0.0064 (18) |
C8 | 0.030 (2) | 0.037 (3) | 0.032 (2) | −0.011 (2) | 0.0076 (19) | −0.013 (2) |
C9 | 0.035 (2) | 0.023 (2) | 0.039 (3) | −0.0037 (19) | −0.001 (2) | −0.011 (2) |
C10 | 0.033 (2) | 0.028 (2) | 0.032 (2) | −0.0079 (19) | −0.0028 (19) | −0.0038 (19) |
C11 | 0.025 (2) | 0.027 (2) | 0.0206 (19) | −0.0137 (18) | −0.0011 (16) | −0.0043 (17) |
C12 | 0.0218 (19) | 0.025 (2) | 0.0232 (19) | −0.0086 (17) | −0.0045 (15) | −0.0006 (16) |
O1W | 0.0342 (18) | 0.0199 (16) | 0.0418 (19) | −0.0021 (14) | 0.0060 (14) | 0.0042 (14) |
Geometric parameters (Å, º) top
Zn1—O3A | 1.968 (3) | C1—H1A | 0.9300 |
Zn1—O1B | 2.037 (3) | C2—C3 | 1.361 (6) |
Zn1—N1 | 2.110 (3) | C2—H2A | 0.9300 |
Zn1—O1W | 2.136 (3) | C3—C4 | 1.395 (6) |
Zn1—N2 | 2.152 (3) | C3—H3A | 0.9300 |
Zn2—O2Ai | 1.951 (3) | C4—C12 | 1.402 (5) |
Zn2—O2Bii | 1.955 (3) | C4—C5 | 1.447 (6) |
Zn2—O1B | 2.002 (3) | C5—C6 | 1.335 (6) |
Zn2—O1A | 2.007 (3) | C5—H5A | 0.9300 |
S1A—O1A | 1.523 (3) | C6—C7 | 1.441 (6) |
S1A—O2A | 1.528 (3) | C6—H6A | 0.9300 |
S1A—O3A | 1.546 (3) | C7—C11 | 1.408 (5) |
O2A—Zn2i | 1.951 (3) | C7—C8 | 1.406 (6) |
S1B—O3B | 1.489 (3) | C8—C9 | 1.366 (6) |
S1B—O2B | 1.520 (3) | C8—H8A | 0.9300 |
S1B—O1B | 1.583 (3) | C9—C10 | 1.400 (6) |
O2B—Zn2ii | 1.955 (3) | C9—H9A | 0.9300 |
N1—C1 | 1.329 (6) | C10—H10A | 0.9300 |
N1—C12 | 1.362 (5) | C11—C12 | 1.433 (6) |
N2—C10 | 1.327 (5) | O1W—H1WB | 0.82 (4) |
N2—C11 | 1.358 (5) | O1W—H1WA | 0.82 (4) |
C1—C2 | 1.384 (6) | | |
| | | |
O3A—Zn1—O1B | 106.21 (11) | C2—C1—H1A | 118.7 |
O3A—Zn1—N1 | 107.63 (13) | C3—C2—C1 | 119.6 (4) |
O1B—Zn1—N1 | 146.14 (13) | C3—C2—H2A | 120.2 |
O3A—Zn1—O1W | 96.47 (13) | C1—C2—H2A | 120.2 |
O1B—Zn1—O1W | 85.31 (12) | C2—C3—C4 | 119.9 (4) |
N1—Zn1—O1W | 89.82 (12) | C2—C3—H3A | 120.1 |
O3A—Zn1—N2 | 112.27 (13) | C4—C3—H3A | 120.1 |
O1B—Zn1—N2 | 90.22 (12) | C3—C4—C12 | 117.4 (4) |
N1—Zn1—N2 | 78.10 (13) | C3—C4—C5 | 124.0 (4) |
O1W—Zn1—N2 | 150.99 (14) | C12—C4—C5 | 118.6 (4) |
O2Ai—Zn2—O2Bii | 103.79 (12) | C6—C5—C4 | 121.3 (4) |
O2Ai—Zn2—O1B | 128.31 (12) | C6—C5—H5A | 119.4 |
O2Bii—Zn2—O1B | 115.87 (12) | C4—C5—H5A | 119.4 |
O2Ai—Zn2—O1A | 101.47 (13) | C5—C6—C7 | 121.5 (4) |
O2Bii—Zn2—O1A | 102.19 (12) | C5—C6—H6A | 119.2 |
O1B—Zn2—O1A | 101.07 (12) | C7—C6—H6A | 119.2 |
O1A—S1A—O2A | 104.87 (17) | C11—C7—C8 | 117.6 (4) |
O1A—S1A—O3A | 105.83 (17) | C11—C7—C6 | 118.6 (4) |
O2A—S1A—O3A | 102.59 (16) | C8—C7—C6 | 123.8 (4) |
S1A—O1A—Zn2 | 125.85 (17) | C9—C8—C7 | 118.9 (4) |
S1A—O2A—Zn2i | 126.31 (16) | C9—C8—H8A | 120.5 |
S1A—O3A—Zn1 | 122.68 (17) | C7—C8—H8A | 120.5 |
O3B—S1B—O2B | 109.05 (16) | C8—C9—C10 | 119.9 (4) |
O3B—S1B—O1B | 100.10 (17) | C8—C9—H9A | 120.0 |
O2B—S1B—O1B | 104.76 (17) | C10—C9—H9A | 120.0 |
S1B—O1B—Zn2 | 111.33 (15) | N2—C10—C9 | 122.6 (4) |
S1B—O1B—Zn1 | 127.27 (15) | N2—C10—H10A | 118.7 |
Zn2—O1B—Zn1 | 121.27 (14) | C9—C10—H10A | 118.7 |
S1B—O2B—Zn2ii | 130.44 (17) | N2—C11—C7 | 122.8 (4) |
C1—N1—C12 | 118.3 (3) | N2—C11—C12 | 117.3 (3) |
C1—N1—Zn1 | 127.7 (3) | C7—C11—C12 | 119.9 (4) |
C12—N1—Zn1 | 114.0 (3) | N1—C12—C4 | 122.3 (4) |
C10—N2—C11 | 118.0 (3) | N1—C12—C11 | 117.5 (3) |
C10—N2—Zn1 | 129.0 (3) | C4—C12—C11 | 120.2 (4) |
C11—N2—Zn1 | 112.9 (3) | Zn1—O1W—H1WB | 122 (3) |
N1—C1—C2 | 122.6 (4) | Zn1—O1W—H1WA | 126 (3) |
N1—C1—H1A | 118.7 | H1WB—O1W—H1WA | 109 (2) |
Symmetry codes: (i) −x, −y+2, −z; (ii) −x+1, −y+2, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O3Aiii | 0.82 (4) | 2.06 (4) | 2.873 (4) | 168 (4) |
O1W—H1WB···O3Bii | 0.82 (4) | 1.93 (4) | 2.750 (4) | 173 (4) |
C3—H3A···S1Biv | 0.93 | 2.90 | 3.783 (4) | 160 |
C8—H8A···S1Bv | 0.93 | 2.89 | 3.630 (5) | 138 |
Symmetry codes: (ii) −x+1, −y+2, −z; (iii) −x+1, −y+1, −z; (iv) −x+1, −y+1, −z+1; (v) −x, −y+2, −z+1. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | [Zn2(SO3)2(C12H12N2)]·2H2O | [Zn2(SO3)2(C12H10N2)(H2O)] |
Mr | 695.36 | 489.08 |
Crystal system, space group | Triclinic, P1 | Triclinic, P1 |
Temperature (K) | 296 | 293 |
a, b, c (Å) | 7.534 (4), 9.621 (5), 11.051 (5) | 8.0271 (16), 9.4817 (19), 10.286 (2) |
α, β, γ (°) | 113.233 (8), 96.932 (9), 106.746 (9) | 80.98 (3), 80.39 (3), 75.55 (3) |
V (Å3) | 679.4 (6) | 742.0 (3) |
Z | 1 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.98 | 3.56 |
Crystal size (mm) | 0.22 × 0.20 × 0.10 | 0.32 × 0.24 × 0.14 |
|
Data collection |
Diffractometer | Bruker SMART CCD area-detector diffractometer | Rigaku AFC6 diffractometer |
Absorption correction | Multi-scan [SADABS (Sheldrick, 1996) in SAINT-NT (Bruker, 2000)] | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.66, 0.82 | 0.37, 0.60 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2037, 2037, 1623 | 3847, 2926, 1976 |
Rint | 0.079 | 0.034 |
(sin θ/λ)max (Å−1) | 0.652 | 0.617 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.064, 0.182, 1.01 | 0.030, 0.079, 0.97 |
No. of reflections | 2037 | 2926 |
No. of parameters | 191 | 232 |
No. of restraints | 3 | 3 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.95, −1.30 | 0.42, −0.52 |
Selected geometric parameters (Å, º) for (I) topZn1—O1i | 1.951 (4) | Zn1—O3 | 2.198 (5) |
Zn1—O2 | 2.022 (4) | S1—O3 | 1.514 (5) |
Zn1—N2 | 2.049 (5) | S1—O1 | 1.522 (5) |
Zn1—N1 | 2.110 (5) | S1—O2 | 1.532 (5) |
| | | |
O1i—Zn1—O2 | 121.9 (2) | N2—Zn1—N1 | 78.6 (2) |
O1i—Zn1—N2 | 102.8 (2) | O1i—Zn1—O3 | 107.4 (2) |
O2—Zn1—N2 | 134.7 (2) | O2—Zn1—O3 | 66.9 (2) |
O1i—Zn1—N1 | 99.3 (2) | N2—Zn1—O3 | 94.9 (2) |
O2—Zn1—N1 | 99.28 (19) | N1—Zn1—O3 | 153.3 (2) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WB···O3i | 0.83 (8) | 2.06 (7) | 2.823 (10) | 155 (6) |
O1W—H1WA···O2 | 0.82 (5) | 2.07 (6) | 2.835 (10) | 157 (6) |
C7—H7···O1ii | 0.93 | 2.46 | 3.247 (7) | 142 |
C9—H9···O1Wiii | 0.93 | 2.49 | 3.374 (9) | 159 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1, y+1, z; (iii) x+1, y+1, z+1. |
π–π contacts (Å, °) for (I) topGroup 1/Group 2 | | ipd (Å) | ccd (Å) | sa (°) |
Ring B'/Ring A | | 3.46 (1) | 3.69 (1) | 20.4 (2) |
Ring B''/Ring A | | 3.49 (1) | 3.86 (1) | 25.3 (2) |
Ring A'/Ring B | | 3.55 (1) | 3.69 (1) | 15.9 (2) |
Ring A''/Ring B | | 3.60 (1) | 3.86 (1) | 20.9 (2) |
Ring A: atoms N1 and C1-C5; Ring B: atoms N2 and C6-C10. Symmetry codes: (') 2 − x, 2 − y, 1 − z; (") 1 − x, 2 − y, 1 − z.
ipd: interplanar distance (Distance from one plane to the neighbouring centroid); ccd: center-to-center distance (Distance between ring centroids); sa: slippage angle (Angle subtended by the intercentroid vector to the plane normal). For details, see Janiak (2000). |
Selected geometric parameters (Å, º) for (II) topZn1—O3A | 1.968 (3) | Zn2—O1A | 2.007 (3) |
Zn1—O1B | 2.037 (3) | S1A—O1A | 1.523 (3) |
Zn1—N1 | 2.110 (3) | S1A—O2A | 1.528 (3) |
Zn1—O1W | 2.136 (3) | S1A—O3A | 1.546 (3) |
Zn1—N2 | 2.152 (3) | S1B—O3B | 1.489 (3) |
Zn2—O2Ai | 1.951 (3) | S1B—O2B | 1.520 (3) |
Zn2—O2Bii | 1.955 (3) | S1B—O1B | 1.583 (3) |
Zn2—O1B | 2.002 (3) | | |
| | | |
O3A—Zn1—O1B | 106.21 (11) | O1W—Zn1—N2 | 150.99 (14) |
O3A—Zn1—N1 | 107.63 (13) | O2Ai—Zn2—O2Bii | 103.79 (12) |
O1B—Zn1—N1 | 146.14 (13) | O2Ai—Zn2—O1B | 128.31 (12) |
O3A—Zn1—O1W | 96.47 (13) | O2Bii—Zn2—O1B | 115.87 (12) |
O1B—Zn1—O1W | 85.31 (12) | O2Ai—Zn2—O1A | 101.47 (13) |
N1—Zn1—O1W | 89.82 (12) | O2Bii—Zn2—O1A | 102.19 (12) |
O3A—Zn1—N2 | 112.27 (13) | O1B—Zn2—O1A | 101.07 (12) |
O1B—Zn1—N2 | 90.22 (12) | Zn2—O1B—Zn1 | 121.27 (14) |
N1—Zn1—N2 | 78.10 (13) | | |
Symmetry codes: (i) −x, −y+2, −z; (ii) −x+1, −y+2, −z. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O3Aiii | 0.82 (4) | 2.06 (4) | 2.873 (4) | 168 (4) |
O1W—H1WB···O3Bii | 0.82 (4) | 1.93 (4) | 2.750 (4) | 173 (4) |
Symmetry codes: (ii) −x+1, −y+2, −z; (iii) −x+1, −y+1, −z. |
π-π contacts (Å, °) for (II) topGroup 1/Group 2 | | ipd (Å) | ccd (Å) | sa (°) |
Rings A'B'/Rings AB | | 3.50 (1) | 3.52 (1) | 10.0 (2) |
Rings B''C''/Rings BC | | 3.34 (1) | 3.55 (1) | 18.5 (2) |
Rings AB: atoms N1, C1-C7, C11 and C12; Rings BC: atoms N2 and C4-C12. Symmetry codes: (') 1 − x, 1 − y, 1 − z; (") −x, 1 − y, 1 − z.
ipd: interplanar distance (Distance from one plane to the neighbouring centroid); ccd: center-to-center distance (Distance between group centroids); sa: slippage angle (Angle subtended by the intercentroid vector to the plane normal). For details, see Janiak (2000). |
We have recently commented (Diaz de Vivar et al., 2004) on the feasibility of producing novel thiosulfate complexes of group XII metals, which are otherwise difficult to obtain by conventional methods, through the decomposition of less common sulfur oxoanions, such as dithionite and pyrosulfite. The argument lay in the instability of these anions in aqueous solutions (Remy, 1956), which, when interacting with transition metal ions and organic ligands, can produce a variety of interesting transformation products. Sodium dithionite, for example, which is fairly stable in the solid state, decomposes in solution, yielding pyrosulfite and thiosulfate. On the other hand, the chemistry in solution of the former is similar to those of SO32− and HSO3−, even though in the solid state SIII and SV are the states to be expected for sulfur.
This high anionic instability (which makes their own chemistry so difficult) makes these complexes attractive as precursors. Some previously unintentional outcomes suggested (Harvey et al., 2004) and further intentional synthesis confirmed (Diaz de Vivar et al., 2004) that the method could be an alternative route for the obtention of thiosulfate complexes where direct synthesis had previously proven unsuccessful. The present work deals with an extension of this method, as applied to sulfite complexes, another of the anions present in the complex equilibrium system dithionite–pyrosulfite. We present the pioneering results of these trials, viz. the syntheses and crystal structures of the title compounds, (I) and (II).
Fig. 1 shows an ellipsoid plot of the dimeric unit in (I); the five-coordinated Zn2+ cation appears to be bound to a 4,4'-dimethyl-2,2'-bipyridine unit through its two N atoms and to two symmetry-related sulfite units; one of these provides two bonds in a chelating mode (atoms O2 and O3) and its centrosymmetric counterpart provides a single bond [O1i; symmetry code (i) 1 − x, 1 − y, 1 − z]. The coordination environment is thus square pyramidal, with the two chelate bites [four chelating atoms] defining the base [maximum deviation 0.15 (1) Å for O {which O atom?}] and the cation lying 0.63 (1) Å ?out of the basal plane?, towards the apex. This is occupied by atom O1i, with a Zn—O vector shifted ca 10° from the normal to the plane. The two Zn2+ cations are then connected by two bridges (simple on one side, double on the other), the Zn···Zni distance being 3.943 (1) Å. There is also an intradimeric hydrogen-bonding interaction linking atoms O2 and O3i via atom O1W (Table 2 and Fig. 1). The remaining (and weaker) non-bonding contacts stabilize the structure in three orthogonal directions; the two C—H···O interactions, at right angles to one another, connect dimers in the (1 1 0) plane, into two-dimensional structures (Table 2 and Fig. 2). These broad `planes', in turn, are connected by π—π contacts between centrosymmetrycally related (and therefore strictly parallel) aromatic groups. Table 3 provides some relevant features of these interactions.
Structure (II) comprises instead two independent zinc centers, connected by two non-equivalent sulfite units to form polymeric chains running along the a axis (Fig. 3). One of the cationic centers (Zn12+) is five-coordinated in the form of a square pyramid; the basal plane is defined by atoms N1 and N2 of a chelating phenanthroline group, an O atom from one of the sulfite units (O1B) and one aqua O atom (O1W). The least-squares basal plane has a mean deviation of 0.034 Å, and the cation lies 0.60 (1) Å towards the apex. This is occupied by an O atom from the second sulfite group [O3A—Zn1 = 1.968 (3) Å, the shortest bond in the polyhedron] at 8° from the normal to the plane. The second cation (Zn22+) is four-coordinate in a trigonal pyramidal geometry formed by two O atoms from each of the sulfite groups, viz. atoms O2A', O1B and O2B'' defining the base and atom O1A the apex [symmetry codes: (') −x, 2 − y, −z; ("): 1 − x, 2 − y, −z]. It is the very small deviation of the three apical angles [range 101.1 (1)–101.5 (1)°; Table 4] that favours a trigonal pyramidal instead of, say, a tetrahedral description. The apical vector deviates just 0.6° from the normal to the plane. The two independent sulfite anions coordinate in a diverse way, and this is reflected in their internal geometry. Thus unit A, which binds to each O atom attached to one and only one cationic center, exhibits a rather even distribution of S—O distances (Table 4). Unit B, on the other hand, exhibits the largest span, with a clear inverse correspondence between coordination involvement and S—O bond lengths. Thus, atom O1B, which binds to two metal ions, is involved in the longest S—O bond; atom O2B, with its single bond to a Zn atom, has an intermediate bond length and atom O3B, which does not coordinate at all, is the closest to the S atom.
The unit so far described is the elemental link of a column evolving along <100> in the form of a double chain or strip, into which the symmetry centers along the a axis appear embedded. These chains fit into one another in a gear-like fashion, to form planes parallel to (0 1 1) (Fig. 4), in which the internal cohesion is provided by the π–π contact between phen groups (Table 6) as well as by one hydrogen bond (Table 5), through H1WA from the aqua molecule. The remaining H contact (through H1WB) helps in linking neighbouring planes together.