Download citation
Download citation
link to html
Two different zinc sulfite compounds have been prepared through the decomposition of pyrosulfite-­di­thionite ions in aqueous solution, viz. a dimeric complex, di-[mu]-sulfito-[kappa]3O,O':O'';[kappa]3O:O',O''-bis­[(4,4'-di­methyl-2,2'-bi­pyridine-[kappa]2N,N')­zinc(II)] dihydrate, [Zn2(SO3)2(C12H12N2)2]·2H2O, (I), which was solved and refined from a twinned sample, and an extended polymer, poly­[[aqua(1,10-phenanthroline-[kappa]2N,N')­zinc(II)]-[mu]3-sulfito-[kappa]2O:O':O''-zinc(II)-[mu]3-sulfito-[kappa]3O:O:O'], [Zn2(SO3)2(C12H10N2)(H2O)]n, (II). In (I), the dinuclear ZnII 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

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104029865/ob1207sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270104029865/ob1207Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270104029865/ob1207IIsup3.hkl
Contains datablock II

CCDC references: 263025; 263026

Comment top

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 ππ 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 ππ 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.

Experimental top

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.

Refinement top

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].

Computing details top

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.

Figures top
[Figure 1] Fig. 1. An XP diagram (Sheldrick, 1994) of the dimeric unit in (I). The independent moiety is drawn with full (50% probability) displacement ellipsoids. Internal hydrogen bonds are shown as broken lines. [Symmetry code: (') 1 − x, 1 − y, 1 − z.]
[Figure 2] Fig. 2. A packing diagram of (I), parallel to (1 1 0), showing non-bonding interactions. Heavy broken lines indicate intradimeric interactions involving the water H atoms; lighter broken lines indicate C—H···O connecting dimers. Superposing 4,4'-dimethyl-2,2'-bipyridine groups provide out-of-plane ππ interactions
[Figure 3] Fig. 3. An XP diagram (Sheldrick, 1994) of the polymeric chain in (II). The independent part is represented by full (50% probability) displacement ellipsoids. Intrachain hydrogen bonds are shown as broken lines. [Symmetry codes: (') −x, 2 − y, −z; (") 1 − x, 2 − y, −z.]
[Figure 4] Fig. 4. A packing diagram of (II), along the chain direction, showing the way in which planes are built up and the hydrogen-bonding interactions; the superposed phenanthroline groups providing the ππ contacts between chain groups are shown at the center of the figure. One of these chains has been highlighted for clarity.
(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)]·2H2OZ = 1
Mr = 695.36F(000) = 356
Triclinic, P1Dx = 1.700 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71070 Å
a = 7.534 (4) ÅCell parameters from 273 reflections
b = 9.621 (5) Åθ = 4.0–25.5°
c = 11.051 (5) ŵ = 1.98 mm1
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 tube1623 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.079
ϕ and ω scansθmax = 27.6°, θmin = 2.1°
Absorption correction: multi-scan
[SADABS (Sheldrick, 1996) in SAINT-NT (Bruker, 2000)]
h = 99
Tmin = 0.66, Tmax = 0.82k = 1111
2037 measured reflectionsl = 014
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.064Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.182H 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 parametersΔρmax = 0.95 e Å3
3 restraintsΔρmin = 1.30 e Å3
Crystal data top
[Zn2(SO3)2(C12H12N2)]·2H2Oγ = 106.746 (9)°
Mr = 695.36V = 679.4 (6) Å3
Triclinic, P1Z = 1
a = 7.534 (4) ÅMo Kα radiation
b = 9.621 (5) ŵ = 1.98 mm1
c = 11.051 (5) ÅT = 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 = 0.82Rint = 0.079
2037 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0643 restraints
wR(F2) = 0.182H atoms treated by a mixture of independent and constrained refinement
S = 1.01Δρmax = 0.95 e Å3
2037 reflectionsΔρmin = 1.30 e Å3
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
xyzUiso*/Ueq
Zn10.57473 (9)0.72053 (8)0.51318 (8)0.0329 (3)
S10.2636 (2)0.5645 (2)0.5775 (2)0.0426 (5)
O10.2433 (6)0.3882 (5)0.5324 (6)0.0444 (13)
O20.2877 (6)0.5956 (6)0.4537 (5)0.0465 (13)
O30.4638 (7)0.6687 (6)0.6720 (6)0.0530 (14)
N10.5933 (7)0.8282 (6)0.3794 (6)0.0326 (12)
N20.7506 (7)0.9559 (6)0.6438 (6)0.0340 (12)
C10.5070 (9)0.7535 (8)0.2435 (7)0.0411 (17)
H10.41340.64950.20490.049*
C20.5531 (9)0.8261 (8)0.1609 (7)0.0395 (16)
H20.49170.77170.06790.047*
C30.6921 (8)0.9812 (8)0.2173 (7)0.0356 (15)
C40.7788 (8)1.0570 (7)0.3549 (6)0.0289 (13)
H40.87341.16070.39500.035*
C50.7249 (8)0.9785 (7)0.4350 (7)0.0276 (13)
C60.8084 (7)1.0543 (7)0.5838 (7)0.0294 (14)
C70.9384 (8)1.2139 (7)0.6608 (7)0.0324 (14)
H70.97611.27940.61810.039*
C81.0115 (8)1.2754 (7)0.7989 (7)0.0358 (15)
C90.9502 (9)1.1742 (8)0.8575 (7)0.0386 (16)
H90.99741.21190.95090.046*
C100.8212 (9)1.0196 (8)0.7802 (7)0.0403 (17)
H100.77990.95500.82320.048*
C110.7470 (11)1.0632 (10)0.1271 (8)0.0514 (19)
H11A0.64121.08760.09500.077*
H11B0.77730.99150.05050.077*
H11C0.85701.16210.17900.077*
C121.1555 (10)1.4472 (8)0.8816 (8)0.0473 (18)
H12A1.08911.51920.91850.071*
H12B1.22521.47950.82400.071*
H12C1.24361.45220.95500.071*
O1W0.2283 (12)0.3627 (9)0.1817 (8)0.081 (2)
H1WB0.315 (9)0.332 (9)0.200 (6)0.06 (3)*
H1WA0.215 (10)0.428 (7)0.251 (4)0.04 (2)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0290 (4)0.0199 (5)0.0529 (6)0.0033 (3)0.0134 (3)0.0226 (4)
S10.0339 (8)0.0317 (10)0.0776 (13)0.0141 (7)0.0285 (8)0.0344 (10)
O10.043 (2)0.018 (2)0.085 (4)0.0108 (19)0.032 (2)0.032 (3)
O20.039 (2)0.044 (3)0.073 (4)0.011 (2)0.013 (2)0.045 (3)
O30.048 (3)0.035 (3)0.075 (4)0.002 (2)0.023 (2)0.030 (3)
N10.030 (2)0.018 (3)0.052 (3)0.0030 (19)0.012 (2)0.022 (3)
N20.031 (2)0.026 (3)0.048 (3)0.004 (2)0.011 (2)0.024 (3)
C10.035 (3)0.033 (4)0.050 (4)0.000 (3)0.001 (3)0.026 (4)
C20.051 (4)0.022 (4)0.040 (4)0.008 (3)0.008 (3)0.012 (3)
C30.037 (3)0.032 (4)0.049 (4)0.015 (3)0.018 (3)0.025 (3)
C40.029 (3)0.021 (3)0.042 (4)0.007 (2)0.008 (2)0.022 (3)
C50.035 (3)0.013 (3)0.048 (4)0.014 (2)0.019 (3)0.021 (3)
C60.023 (2)0.020 (3)0.048 (4)0.007 (2)0.015 (2)0.018 (3)
C70.033 (3)0.019 (3)0.044 (4)0.006 (2)0.012 (3)0.015 (3)
C80.036 (3)0.019 (3)0.051 (4)0.009 (2)0.015 (3)0.014 (3)
C90.050 (3)0.034 (4)0.028 (4)0.016 (3)0.014 (3)0.010 (3)
C100.043 (3)0.030 (4)0.054 (5)0.005 (3)0.014 (3)0.031 (4)
C110.058 (4)0.051 (5)0.056 (5)0.018 (4)0.017 (4)0.036 (4)
C120.052 (4)0.027 (4)0.046 (4)0.001 (3)0.011 (3)0.011 (4)
O1W0.102 (6)0.052 (5)0.063 (5)0.008 (4)0.017 (4)0.027 (4)
Geometric parameters (Å, º) top
Zn1—O1i1.951 (4)C4—H40.9300
Zn1—O22.022 (4)C5—C61.474 (9)
Zn1—N22.049 (5)C6—C71.394 (8)
Zn1—N12.110 (5)C7—C81.371 (9)
Zn1—O32.198 (5)C7—H70.9300
S1—O31.514 (5)C8—C91.375 (9)
S1—O11.522 (5)C8—C121.510 (9)
S1—O21.532 (5)C9—C101.361 (9)
N1—C51.333 (7)C9—H90.9300
N1—C11.356 (9)C10—H100.9300
N2—C101.349 (9)C11—H11A0.9600
N2—C61.361 (8)C11—H11B0.9600
C1—C21.371 (9)C11—H11C0.9600
C1—H10.9300C12—H12A0.9600
C2—C31.385 (8)C12—H12B0.9600
C2—H20.9300C12—H12C0.9600
C3—C41.371 (9)O1W—H1WB0.83 (8)
C3—C111.523 (9)O1W—H1WA0.82 (5)
C4—C51.399 (8)
O1i—Zn1—O2121.9 (2)C3—C4—C5120.0 (5)
O1i—Zn1—N2102.8 (2)C3—C4—H4120.0
O2—Zn1—N2134.7 (2)C5—C4—H4120.0
O1i—Zn1—N199.3 (2)N1—C5—C4121.1 (6)
O2—Zn1—N199.28 (19)N1—C5—C6116.0 (5)
N2—Zn1—N178.6 (2)C4—C5—C6122.9 (5)
O1i—Zn1—O3107.4 (2)N2—C6—C7120.9 (6)
O2—Zn1—O366.9 (2)N2—C6—C5115.0 (5)
N2—Zn1—O394.9 (2)C7—C6—C5124.1 (6)
N1—Zn1—O3153.3 (2)C8—C7—C6120.7 (6)
O3—S1—O1106.8 (3)C8—C7—H7119.6
O3—S1—O299.8 (3)C6—C7—H7119.6
O1—S1—O2105.5 (3)C7—C8—C9117.4 (6)
O3—S1—Zn153.4 (2)C7—C8—C12120.6 (6)
O1—S1—Zn1109.56 (18)C9—C8—C12122.0 (6)
O2—S1—Zn146.85 (17)C10—C9—C8120.6 (6)
S1—O1—Zn1i131.6 (3)C10—C9—H9119.7
S1—O2—Zn199.6 (2)C8—C9—H9119.7
S1—O3—Zn193.0 (3)N2—C10—C9122.8 (6)
C5—N1—C1118.8 (5)N2—C10—H10118.6
C5—N1—Zn1113.7 (4)C9—C10—H10118.6
C1—N1—Zn1126.8 (4)C3—C11—H11A109.5
C10—N2—C6117.5 (5)C3—C11—H11B109.5
C10—N2—Zn1126.8 (4)H11A—C11—H11B109.5
C6—N2—Zn1115.5 (4)C3—C11—H11C109.5
N1—C1—C2122.3 (6)H11A—C11—H11C109.5
N1—C1—H1118.9H11B—C11—H11C109.5
C2—C1—H1118.9C8—C12—H12A109.5
C1—C2—C3119.3 (6)C8—C12—H12B109.5
C1—C2—H2120.3H12A—C12—H12B109.5
C3—C2—H2120.3C8—C12—H12C109.5
C4—C3—C2118.4 (6)H12A—C12—H12C109.5
C4—C3—C11121.4 (6)H12B—C12—H12C109.5
C2—C3—C11120.2 (6)H1WB—O1W—H1WA111 (3)
Symmetry code: (i) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WB···O3i0.83 (8)2.06 (7)2.823 (10)155 (6)
O1W—H1WA···O20.82 (5)2.07 (6)2.835 (10)157 (6)
C7—H7···O1ii0.932.463.247 (7)142
C9—H9···O1Wiii0.932.493.374 (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)]-µ3-sulfito-κ2O:O':O''- zinc(II)-µ3-sulfito-κ3O:O:O'] top
Crystal data top
[Zn2(SO3)2(C12H10N2)(H2O)]Z = 2
Mr = 489.08F(000) = 488
Triclinic, P1Dx = 2.189 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.0271 (16) ÅCell parameters from 25 reflections
b = 9.4817 (19) Åθ = 10.2–16.0°
c = 10.286 (2) ŵ = 3.56 mm1
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 tubeRint = 0.034
Graphite monochromatorθmax = 26.0°, θmin = 2.0°
ω/2θ scansh = 99
Absorption correction: ψ scan
(North et al., 1968)
k = 112
Tmin = 0.37, Tmax = 0.60l = 1212
3847 measured reflections3 standard reflections every 150 reflections
2926 independent reflections intensity decay: 1.2%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.030Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.079H 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 parametersΔρmax = 0.42 e Å3
3 restraintsΔρmin = 0.52 e Å3
Crystal data top
[Zn2(SO3)2(C12H10N2)(H2O)]γ = 75.55 (3)°
Mr = 489.08V = 742.0 (3) Å3
Triclinic, P1Z = 2
a = 8.0271 (16) ÅMo Kα radiation
b = 9.4817 (19) ŵ = 3.56 mm1
c = 10.286 (2) ÅT = 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 = 0.603 standard reflections every 150 reflections
3847 measured reflections intensity decay: 1.2%
2926 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0303 restraints
wR(F2) = 0.079H atoms treated by a mixture of independent and constrained refinement
S = 0.97Δρmax = 0.42 e Å3
2926 reflectionsΔρmin = 0.52 e Å3
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
xyzUiso*/Ueq
Zn10.32018 (6)0.67862 (5)0.16652 (4)0.02456 (13)
Zn20.24315 (6)1.00687 (5)0.05093 (5)0.02562 (14)
S1A0.06614 (13)0.74326 (11)0.04183 (10)0.0248 (2)
O1A0.1620 (4)0.8546 (3)0.1232 (3)0.0325 (7)
O2A0.0487 (4)0.8238 (3)0.0703 (3)0.0316 (7)
O3A0.2031 (4)0.6289 (3)0.0322 (3)0.0285 (7)
S1B0.37973 (12)0.99622 (11)0.20246 (9)0.0218 (2)
O1B0.3261 (4)0.8940 (3)0.1167 (3)0.0262 (6)
O2B0.5763 (3)0.9471 (3)0.1924 (3)0.0295 (7)
O3B0.3328 (4)1.1404 (3)0.1200 (3)0.0352 (7)
N10.3915 (4)0.4869 (4)0.2991 (3)0.0239 (7)
N20.1460 (4)0.7310 (4)0.3443 (3)0.0268 (8)
C10.5108 (6)0.3656 (5)0.2744 (4)0.0324 (10)
H1A0.57070.35990.18910.039*
C20.5492 (6)0.2472 (5)0.3706 (4)0.0337 (10)
H2A0.63300.16380.34960.040*
C30.4638 (6)0.2538 (5)0.4963 (4)0.0358 (11)
H3A0.48990.17510.56170.043*
C40.3369 (5)0.3787 (5)0.5267 (4)0.0271 (9)
C50.2341 (6)0.3936 (5)0.6555 (4)0.0330 (10)
H5A0.25550.31830.72460.040*
C60.1093 (6)0.5135 (5)0.6771 (4)0.0331 (10)
H6A0.04430.51920.76070.040*
C70.0729 (5)0.6341 (5)0.5740 (4)0.0279 (9)
C80.0588 (5)0.7616 (5)0.5910 (4)0.0332 (10)
H8A0.12650.77360.67290.040*
C90.0859 (6)0.8674 (5)0.4852 (4)0.0326 (10)
H9A0.17440.95130.49410.039*
C100.0199 (6)0.8494 (5)0.3633 (4)0.0308 (10)
H10A0.00090.92350.29290.037*
C110.1718 (5)0.6235 (4)0.4479 (4)0.0231 (8)
C120.3048 (5)0.4943 (4)0.4243 (4)0.0228 (8)
O1W0.5756 (4)0.6350 (3)0.0588 (3)0.0349 (7)
H1WB0.612 (5)0.698 (3)0.005 (4)0.042*
H1WA0.636 (5)0.554 (2)0.044 (4)0.042*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0282 (3)0.0208 (3)0.0223 (2)0.0042 (2)0.00138 (19)0.00018 (19)
Zn20.0220 (2)0.0250 (3)0.0242 (2)0.0005 (2)0.00022 (19)0.0028 (2)
S1A0.0223 (5)0.0224 (5)0.0288 (5)0.0011 (4)0.0054 (4)0.0048 (4)
O1A0.0383 (17)0.0293 (16)0.0284 (15)0.0115 (14)0.0011 (13)0.0016 (13)
O2A0.0256 (15)0.0330 (17)0.0275 (15)0.0067 (13)0.0023 (12)0.0007 (13)
O3A0.0283 (15)0.0199 (14)0.0343 (16)0.0043 (12)0.0088 (13)0.0050 (13)
S1B0.0214 (5)0.0217 (5)0.0197 (5)0.0037 (4)0.0013 (4)0.0013 (4)
O1B0.0301 (15)0.0224 (15)0.0270 (15)0.0088 (12)0.0040 (12)0.0007 (12)
O2B0.0234 (15)0.0380 (17)0.0245 (15)0.0076 (13)0.0010 (12)0.0024 (13)
O3B0.0367 (17)0.0184 (15)0.0431 (18)0.0008 (13)0.0002 (14)0.0038 (13)
N10.0225 (17)0.0252 (18)0.0217 (17)0.0041 (15)0.0014 (13)0.0000 (14)
N20.0277 (18)0.0255 (19)0.0273 (19)0.0083 (16)0.0011 (15)0.0048 (15)
C10.032 (2)0.031 (2)0.030 (2)0.005 (2)0.0006 (19)0.0005 (19)
C20.030 (2)0.027 (2)0.039 (3)0.002 (2)0.007 (2)0.001 (2)
C30.040 (3)0.032 (2)0.031 (2)0.004 (2)0.011 (2)0.009 (2)
C40.029 (2)0.030 (2)0.025 (2)0.0104 (19)0.0046 (17)0.0006 (18)
C50.042 (3)0.035 (3)0.023 (2)0.013 (2)0.0066 (19)0.0000 (19)
C60.041 (3)0.038 (3)0.022 (2)0.015 (2)0.0024 (19)0.0048 (19)
C70.028 (2)0.033 (2)0.024 (2)0.0101 (19)0.0016 (18)0.0064 (18)
C80.030 (2)0.037 (3)0.032 (2)0.011 (2)0.0076 (19)0.013 (2)
C90.035 (2)0.023 (2)0.039 (3)0.0037 (19)0.001 (2)0.011 (2)
C100.033 (2)0.028 (2)0.032 (2)0.0079 (19)0.0028 (19)0.0038 (19)
C110.025 (2)0.027 (2)0.0206 (19)0.0137 (18)0.0011 (16)0.0043 (17)
C120.0218 (19)0.025 (2)0.0232 (19)0.0086 (17)0.0045 (15)0.0006 (16)
O1W0.0342 (18)0.0199 (16)0.0418 (19)0.0021 (14)0.0060 (14)0.0042 (14)
Geometric parameters (Å, º) top
Zn1—O3A1.968 (3)C1—H1A0.9300
Zn1—O1B2.037 (3)C2—C31.361 (6)
Zn1—N12.110 (3)C2—H2A0.9300
Zn1—O1W2.136 (3)C3—C41.395 (6)
Zn1—N22.152 (3)C3—H3A0.9300
Zn2—O2Ai1.951 (3)C4—C121.402 (5)
Zn2—O2Bii1.955 (3)C4—C51.447 (6)
Zn2—O1B2.002 (3)C5—C61.335 (6)
Zn2—O1A2.007 (3)C5—H5A0.9300
S1A—O1A1.523 (3)C6—C71.441 (6)
S1A—O2A1.528 (3)C6—H6A0.9300
S1A—O3A1.546 (3)C7—C111.408 (5)
O2A—Zn2i1.951 (3)C7—C81.406 (6)
S1B—O3B1.489 (3)C8—C91.366 (6)
S1B—O2B1.520 (3)C8—H8A0.9300
S1B—O1B1.583 (3)C9—C101.400 (6)
O2B—Zn2ii1.955 (3)C9—H9A0.9300
N1—C11.329 (6)C10—H10A0.9300
N1—C121.362 (5)C11—C121.433 (6)
N2—C101.327 (5)O1W—H1WB0.82 (4)
N2—C111.358 (5)O1W—H1WA0.82 (4)
C1—C21.384 (6)
O3A—Zn1—O1B106.21 (11)C2—C1—H1A118.7
O3A—Zn1—N1107.63 (13)C3—C2—C1119.6 (4)
O1B—Zn1—N1146.14 (13)C3—C2—H2A120.2
O3A—Zn1—O1W96.47 (13)C1—C2—H2A120.2
O1B—Zn1—O1W85.31 (12)C2—C3—C4119.9 (4)
N1—Zn1—O1W89.82 (12)C2—C3—H3A120.1
O3A—Zn1—N2112.27 (13)C4—C3—H3A120.1
O1B—Zn1—N290.22 (12)C3—C4—C12117.4 (4)
N1—Zn1—N278.10 (13)C3—C4—C5124.0 (4)
O1W—Zn1—N2150.99 (14)C12—C4—C5118.6 (4)
O2Ai—Zn2—O2Bii103.79 (12)C6—C5—C4121.3 (4)
O2Ai—Zn2—O1B128.31 (12)C6—C5—H5A119.4
O2Bii—Zn2—O1B115.87 (12)C4—C5—H5A119.4
O2Ai—Zn2—O1A101.47 (13)C5—C6—C7121.5 (4)
O2Bii—Zn2—O1A102.19 (12)C5—C6—H6A119.2
O1B—Zn2—O1A101.07 (12)C7—C6—H6A119.2
O1A—S1A—O2A104.87 (17)C11—C7—C8117.6 (4)
O1A—S1A—O3A105.83 (17)C11—C7—C6118.6 (4)
O2A—S1A—O3A102.59 (16)C8—C7—C6123.8 (4)
S1A—O1A—Zn2125.85 (17)C9—C8—C7118.9 (4)
S1A—O2A—Zn2i126.31 (16)C9—C8—H8A120.5
S1A—O3A—Zn1122.68 (17)C7—C8—H8A120.5
O3B—S1B—O2B109.05 (16)C8—C9—C10119.9 (4)
O3B—S1B—O1B100.10 (17)C8—C9—H9A120.0
O2B—S1B—O1B104.76 (17)C10—C9—H9A120.0
S1B—O1B—Zn2111.33 (15)N2—C10—C9122.6 (4)
S1B—O1B—Zn1127.27 (15)N2—C10—H10A118.7
Zn2—O1B—Zn1121.27 (14)C9—C10—H10A118.7
S1B—O2B—Zn2ii130.44 (17)N2—C11—C7122.8 (4)
C1—N1—C12118.3 (3)N2—C11—C12117.3 (3)
C1—N1—Zn1127.7 (3)C7—C11—C12119.9 (4)
C12—N1—Zn1114.0 (3)N1—C12—C4122.3 (4)
C10—N2—C11118.0 (3)N1—C12—C11117.5 (3)
C10—N2—Zn1129.0 (3)C4—C12—C11120.2 (4)
C11—N2—Zn1112.9 (3)Zn1—O1W—H1WB122 (3)
N1—C1—C2122.6 (4)Zn1—O1W—H1WA126 (3)
N1—C1—H1A118.7H1WB—O1W—H1WA109 (2)
Symmetry codes: (i) x, y+2, z; (ii) x+1, y+2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WA···O3Aiii0.82 (4)2.06 (4)2.873 (4)168 (4)
O1W—H1WB···O3Bii0.82 (4)1.93 (4)2.750 (4)173 (4)
C3—H3A···S1Biv0.932.903.783 (4)160
C8—H8A···S1Bv0.932.893.630 (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)]
Mr695.36489.08
Crystal system, space groupTriclinic, P1Triclinic, P1
Temperature (K)296293
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)
V3)679.4 (6)742.0 (3)
Z12
Radiation typeMo KαMo Kα
µ (mm1)1.983.56
Crystal size (mm)0.22 × 0.20 × 0.100.32 × 0.24 × 0.14
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Rigaku AFC6
diffractometer
Absorption correctionMulti-scan
[SADABS (Sheldrick, 1996) in SAINT-NT (Bruker, 2000)]
ψ scan
(North et al., 1968)
Tmin, Tmax0.66, 0.820.37, 0.60
No. of measured, independent and
observed [I > 2σ(I)] reflections
2037, 2037, 1623 3847, 2926, 1976
Rint0.0790.034
(sin θ/λ)max1)0.6520.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.064, 0.182, 1.01 0.030, 0.079, 0.97
No. of reflections20372926
No. of parameters191232
No. of restraints33
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.95, 1.300.42, 0.52

Computer programs: SMART-NT (Bruker, 2001), MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988), SAINT-NT (Bruker, 2000), MSC/AFC Diffractometer Control Software, SAINT-NT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP in SHELXTL-PC (Sheldrick, 1994), SHELXL97.

Selected geometric parameters (Å, º) for (I) top
Zn1—O1i1.951 (4)Zn1—O32.198 (5)
Zn1—O22.022 (4)S1—O31.514 (5)
Zn1—N22.049 (5)S1—O11.522 (5)
Zn1—N12.110 (5)S1—O21.532 (5)
O1i—Zn1—O2121.9 (2)N2—Zn1—N178.6 (2)
O1i—Zn1—N2102.8 (2)O1i—Zn1—O3107.4 (2)
O2—Zn1—N2134.7 (2)O2—Zn1—O366.9 (2)
O1i—Zn1—N199.3 (2)N2—Zn1—O394.9 (2)
O2—Zn1—N199.28 (19)N1—Zn1—O3153.3 (2)
Symmetry code: (i) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WB···O3i0.83 (8)2.06 (7)2.823 (10)155 (6)
O1W—H1WA···O20.82 (5)2.07 (6)2.835 (10)157 (6)
C7—H7···O1ii0.932.463.247 (7)142
C9—H9···O1Wiii0.932.493.374 (9)159
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1, y+1, z; (iii) x+1, y+1, z+1.
ππ contacts (Å, °) for (I) top
Group 1/Group 2ipd (Å)ccd (Å)sa (°)
Ring B'/Ring A3.46 (1)3.69 (1)20.4 (2)
Ring B''/Ring A3.49 (1)3.86 (1)25.3 (2)
Ring A'/Ring B3.55 (1)3.69 (1)15.9 (2)
Ring A''/Ring B3.60 (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) top
Zn1—O3A1.968 (3)Zn2—O1A2.007 (3)
Zn1—O1B2.037 (3)S1A—O1A1.523 (3)
Zn1—N12.110 (3)S1A—O2A1.528 (3)
Zn1—O1W2.136 (3)S1A—O3A1.546 (3)
Zn1—N22.152 (3)S1B—O3B1.489 (3)
Zn2—O2Ai1.951 (3)S1B—O2B1.520 (3)
Zn2—O2Bii1.955 (3)S1B—O1B1.583 (3)
Zn2—O1B2.002 (3)
O3A—Zn1—O1B106.21 (11)O1W—Zn1—N2150.99 (14)
O3A—Zn1—N1107.63 (13)O2Ai—Zn2—O2Bii103.79 (12)
O1B—Zn1—N1146.14 (13)O2Ai—Zn2—O1B128.31 (12)
O3A—Zn1—O1W96.47 (13)O2Bii—Zn2—O1B115.87 (12)
O1B—Zn1—O1W85.31 (12)O2Ai—Zn2—O1A101.47 (13)
N1—Zn1—O1W89.82 (12)O2Bii—Zn2—O1A102.19 (12)
O3A—Zn1—N2112.27 (13)O1B—Zn2—O1A101.07 (12)
O1B—Zn1—N290.22 (12)Zn2—O1B—Zn1121.27 (14)
N1—Zn1—N278.10 (13)
Symmetry codes: (i) x, y+2, z; (ii) x+1, y+2, z.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WA···O3Aiii0.82 (4)2.06 (4)2.873 (4)168 (4)
O1W—H1WB···O3Bii0.82 (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) top
Group 1/Group 2ipd (Å)ccd (Å)sa (°)
Rings A'B'/Rings AB3.50 (1)3.52 (1)10.0 (2)
Rings B''C''/Rings BC3.34 (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).
 

Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds