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A new polymeric phase of zinc(II) oxydiacetate, catena-poly­[[[di­aqua­zinc(II)]-μ-oxy­diacetato] hydrate], {[Zn(C4H4­O5)­(H2O)2]·H2O}n, isomorphous with the Co homologue [Hatfield, Helms, Rohrs, Singh, Wasson & Weller (1987). Proc. Indian Acad. Sci. Chem. Sci. 98, 23–31], is reported. It presents a chain-like structure, generated by ZnO6 cores which are bridged by carboxyl­ate groups in an antianti conformation along the unique crystallographic b axis. The chains are held together through hydrogen-bonding interactions with the three water mol­ecules.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102021959/ga1002sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102021959/ga1002Isup2.hkl
Contains datablock I

CCDC reference: 204033

Comment top

The interaction of the ZnII ion with carboxylic acids is the subject of extensive research, due to the role of Zn-carboxylate bonds in the active sites of a variety of metalloenzymes and in precursor systems for Zn-containing ceramic materials. Because of the lack of ligand field stabilization energy, the ZnII cation exhibits no preferential coordination numbers, and the actual coordination polyhedra is mainly determined by electrostatic forces and the steric effects of the ligands (Prince, 1987). Oxydiacetate (oda, OOC-CH2—O—CH2—COO) is a versatile complexing agent, having five potential O-donor atoms in different orientations, thus allowing the construction of networks of different dimensionalities. A thorough review of related structures has been reported in a recent study, in which the density functional theory method was applied to investigate the flexibility of this ligand (Grirrane et al., 2002). The only binary zinc oxydiacetate complex known to date is the two-dimensional compound {[Zn(oda)]·0.3H2O}n, hereinafter (II), which consists of sheets perpendicular to the z axis, composed of ZnO5 units bridged by carboxylate groups in an anti-syn conformation (Baggio et al., 1996). For the related CdII compounds, however, three different phases of binary cadmium oxydiacetates have been identified (Boman, 1974, 1977a,b,c), with discrete units, chains and layers containing CdO7 cores. We report here another polymeric phase of ZnII oxydiacetate, formulated as {[Zn(oda)(H2O)2]·H2O}n, (I), and compare it with (II). \sch

The structure of (I) is isomorphous with the homologous cobalt compound, {[Co(oda)(H2O)2]·H2O}n (Hatfield et al., 1987). Comparison of the two structures shows them to be almost identical. A least-squares fit of both coordination polyhedra (XP in SHELXTL-NT; Bruker, 2000) showed them to fit into one another, with deviations ranging from a minimum of 0.007 Å (for atom O1W) to a maximum of 0.027 Å (for atomO5), and with an overall mean of 0.017 Å.

The environment of the Zn in (I) consists of a distorted octahedron, with the basal plane defined by atoms O1, O3 and O5 of the tridentate oda ligand, and atom O2 from an outer carboxylate of a neighbouring oda ligand. The latter serves as the link in the resulting one-dimensional polymer formed along the unique crystallographic b axis (Fig. 1). The apical sites are occupied by two water molecules, and an additional hydrated water molecule completes the unit-cell contents. The resulting polyhedron shows basal angles of ~74 and 166°, instead of the regular values of 90 and 180°, respectively, and the apical Zn—O semi-axes subtend angles of ~5° to the vertical. This is a likely result of the hydrogen-bonding interactions linking atom O1W to atoms O4 and O5, and atom O2W to atoms O4 and O3W (Table 2, Fig. 2).

We note that the large Zn—Oether bonds in structures (I) and (II) are identical, at 2.114 (1) and 2.115 (1) Å, respectively. However, the mean length of the Zn—Ocarboxy bond is slightly larger in (I), at 2.095 (1) versus 2.057 (1) Å, due to the higher coordination number in the former. This corresponds to a smaller out-of-plane deformation of the ligand, the dihedral angle formed by the lateral planar wings (Zn—O3—C2—C1—O1 and Zn—O3—C3—C4—O5) around the Zn—O3 bond being 6.5 (1)° in (I) and 10.1 (1)° in (II).

The major difference between the two polymeric forms of zinc oxydiacetate is in their crystal packing. In form (I), adjacent ZnO6 coordination polyhedra bridged by carboxylate groups in an anti-anti conformation define linear arrays along b, with Zn···Zn nearest-neighbour distances of 5.009 (1) Å within the chains [5.041 (1) Å in the homologous Co compound]. In compound (II), the adjacent ZnO5 polyhedra are bridged by the carboxylate groups in an anti-syn conformation along two mutually orthogonal directions, leading to a two-dimensional structure with closer Zn···Zn contacts within the planes [4.867 (1) Å].

In spite of the differences in the Zn···Zn nearest-neighbour distances in the polymeric arrays, the overall densities in both structures are almost identical [2.034 (1) and 2.032 (1) Mg m−3 for (I) and (II), respectively], suggesting that the `less dense' chains in (I) pack more closely than the `more condensed' planes in (II). The reason for this is to be found in the marked differences of the hydrogen-bonding interactions. In structure (II), hydrogen-bond contacts are few and weak, one of them mediated by a disordered hydration water molecule and the other being of the C—H···O type. In form (I), by contrast, they involve all six water H atoms, which tightly connects the chains to each other.

Experimental top

Analytical grade zinc acetate dihydrate (Fluka) and oxydiacetic acid (Fluka) were used without further purification. Zinc acetate dihydrate (0.20 g, 1 mmol) was dissolved in an aqueous solution (25 ml) of oxydiacetic acid (0.20 g, 1.5 mmol) and stirred at room temperature for 4 h. After four weeks, colourless crystals of (I) suitable for X-ray diffraction were filtered and dried in air. Recrystallization was from water-ethanol (1:1). Analysis calculated for C4H10O8Zn: C 19.10, H 4.00, Zn 26%; found: C 19.00, H 4.05, Zn 25.5%.

Refinement top

H atoms attached to C atoms were added at their expected positions (C—H = 0.97 Å) and not refined, but were allowed to ride. H atoms pertaining to the water molecules were found in the final difference Fourier map and were refined with isotropic displacement factors.

Computing details top

Data collection: SMART-NT (Bruker, 2001); cell refinement: SMART-NT; data reduction: SAINT-NT (Bruker, 2000); program(s) used to solve structure: SHELXTL-NT (Bruker, 2000); program(s) used to refine structure: SHELXTL-NT; molecular graphics: SHELXTL-NT; software used to prepare material for publication: SHELXTL-NT.

Figures top
[Figure 1] Fig. 1. A view of the asymmetric unit of (I), with displacement ellipsoids drawn at the 40% probability level. H atoms are shown as small spheres of arbitrary radii and chain formation is indicated.
[Figure 2] Fig. 2. A schematic packing view of (I) along a, showing the way in which chains (running along b) interact to form a three-dimensional network. Hydrogen bonds are shown as broken lines. H atoms attached to C atoms have been omitted for clarity.
catena-poly[[[diaquazinc(II)]-µ-oxydiacetato]hydrate] top
Crystal data top
[Zn(C4H4O5)(H2O)2]·H2OF(000) = 512
Mr = 251.49Dx = 2.034 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 97 reflections
a = 7.132 (1) Åθ = 7.2–19.3°
b = 10.375 (1) ŵ = 3.01 mm1
c = 11.100 (1) ÅT = 296 K
β = 91.35 (1)°Needle, colourless
V = 821.1 (1) Å30.32 × 0.14 × 0.10 mm
Z = 4
Data collection top
Make Model CCD area-detector
diffractometer
1826 independent reflections
Radiation source: sealed tube1654 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.020
ϕ and ω scansθmax = 27.5°, θmin = 2.7°
Absorption correction: part of the refinement model (ΔF)
(SADABS in SAINT-NT; Bruker, 2000)
h = 98
Tmin = 0.53, Tmax = 0.74k = 1313
6664 measured reflectionsl = 1414
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)] = 0.025Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.064H atoms treated by a mixture of independent and constrained refinement
S = 1.09 w = 1/[σ2(Fo2) + (0.0357P)2 + 0.1545P]
where P = (Fo2 + 2Fc2)/3
1826 reflections(Δ/σ)max = 0.002
142 parametersΔρmax = 0.48 e Å3
0 restraintsΔρmin = 0.31 e Å3
Crystal data top
[Zn(C4H4O5)(H2O)2]·H2OV = 821.1 (1) Å3
Mr = 251.49Z = 4
Monoclinic, P21/nMo Kα radiation
a = 7.132 (1) ŵ = 3.01 mm1
b = 10.375 (1) ÅT = 296 K
c = 11.100 (1) Å0.32 × 0.14 × 0.10 mm
β = 91.35 (1)°
Data collection top
Make Model CCD area-detector
diffractometer
1826 independent reflections
Absorption correction: part of the refinement model (ΔF)
(SADABS in SAINT-NT; Bruker, 2000)
1654 reflections with I > 2σ(I)
Tmin = 0.53, Tmax = 0.74Rint = 0.020
6664 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0250 restraints
wR(F2) = 0.064H atoms treated by a mixture of independent and constrained refinement
S = 1.09Δρmax = 0.48 e Å3
1826 reflectionsΔρmin = 0.31 e Å3
142 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
Zn10.07282 (3)0.10474 (2)0.80326 (2)0.02219 (10)
O10.29383 (19)0.21703 (13)0.73715 (13)0.0255 (3)
O20.4020 (2)0.41137 (13)0.69579 (13)0.0272 (3)
O30.0164 (2)0.29841 (14)0.81713 (17)0.0427 (5)
O40.4139 (2)0.20623 (14)0.97437 (14)0.0328 (4)
O50.1852 (2)0.09755 (12)0.88741 (14)0.0265 (3)
O1W0.2287 (2)0.11133 (15)0.96890 (15)0.0284 (3)
H1WA0.331 (4)0.133 (2)0.968 (2)0.033 (7)*
H1WB0.223 (4)0.052 (3)1.005 (2)0.031 (7)*
O2W0.0305 (3)0.09360 (16)0.62702 (16)0.0345 (4)
H2WA0.143 (4)0.103 (2)0.616 (2)0.033 (8)*
H2WB0.005 (4)0.143 (3)0.588 (2)0.040 (9)*
O3W0.6081 (3)0.16318 (19)0.59656 (18)0.0417 (4)
H3WA0.514 (6)0.173 (4)0.651 (4)0.104 (14)*
H3WB0.616 (4)0.224 (3)0.568 (2)0.034 (8)*
C10.2782 (3)0.33781 (19)0.73514 (16)0.0219 (4)
C20.1013 (3)0.39856 (17)0.7822 (2)0.0288 (5)
H2A0.13120.45390.85040.035*
H2B0.04040.45010.71980.035*
C30.1900 (3)0.32654 (19)0.8696 (2)0.0278 (4)
H3A0.27500.36530.81050.033*
H3B0.17220.38640.93610.033*
C40.2699 (3)0.20088 (19)0.91443 (17)0.0232 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.02146 (15)0.01476 (14)0.03072 (16)0.00053 (8)0.00870 (10)0.00052 (8)
O10.0246 (7)0.0159 (7)0.0365 (8)0.0003 (5)0.0095 (6)0.0024 (6)
O20.0259 (7)0.0175 (7)0.0387 (9)0.0046 (5)0.0096 (6)0.0019 (6)
O30.0350 (9)0.0151 (7)0.0795 (12)0.0003 (6)0.0343 (8)0.0037 (7)
O40.0211 (7)0.0364 (9)0.0413 (9)0.0013 (6)0.0123 (6)0.0056 (7)
O50.0256 (7)0.0196 (7)0.0348 (8)0.0007 (5)0.0115 (6)0.0026 (6)
O1W0.0262 (9)0.0247 (8)0.0343 (9)0.0063 (7)0.0028 (6)0.0067 (7)
O2W0.0348 (10)0.0352 (9)0.0336 (9)0.0040 (7)0.0036 (7)0.0074 (7)
O3W0.0365 (10)0.0377 (11)0.0515 (11)0.0039 (8)0.0131 (8)0.0110 (9)
C10.0239 (9)0.0201 (10)0.0216 (9)0.0010 (8)0.0013 (7)0.0005 (7)
C20.0296 (11)0.0142 (10)0.0430 (13)0.0016 (8)0.0124 (9)0.0021 (8)
C30.0229 (10)0.0211 (10)0.0397 (12)0.0061 (8)0.0089 (8)0.0009 (9)
C40.0186 (9)0.0258 (10)0.0250 (10)0.0009 (8)0.0007 (7)0.0011 (8)
Geometric parameters (Å, º) top
Zn1—O2i2.0143 (14)O1W—H1WA0.77 (3)
Zn1—O2W2.0775 (18)O1W—H1WB0.74 (3)
Zn1—O52.0848 (14)O2W—H2WA0.82 (3)
Zn1—O12.1058 (13)O2W—H2WB0.73 (3)
Zn1—O32.1143 (15)O3W—H3WA0.92 (5)
Zn1—O1W2.1272 (17)O3W—H3WB0.71 (3)
O1—C11.258 (2)C1—C21.514 (3)
O2—C11.254 (2)C2—H2A0.9700
O3—C21.396 (2)C2—H2B0.9700
O3—C31.412 (2)C3—C41.511 (3)
O4—C41.238 (2)C3—H3A0.9700
O5—C41.270 (2)C3—H3B0.9700
O2i—Zn1—O2W88.80 (6)H1WA—O1W—H1WB109 (3)
O2i—Zn1—O592.38 (5)Zn1—O2W—H2WA117.4 (19)
O2W—Zn1—O597.04 (7)Zn1—O2W—H2WB114 (2)
O2i—Zn1—O1119.04 (6)H2WA—O2W—H2WB100 (3)
O2W—Zn1—O187.39 (7)H3WA—O3W—H3WB105 (3)
O5—Zn1—O1148.41 (5)O2—C1—O1123.33 (18)
O2i—Zn1—O3166.69 (6)O2—C1—C2117.79 (17)
O2W—Zn1—O391.19 (7)O1—C1—C2118.88 (17)
O5—Zn1—O374.40 (5)O3—C2—C1107.29 (16)
O1—Zn1—O374.25 (5)O3—C2—H2A110.3
O2i—Zn1—O1W89.01 (6)C1—C2—H2A110.3
O2W—Zn1—O1W169.21 (7)O3—C2—H2B110.3
O5—Zn1—O1W93.61 (6)C1—C2—H2B110.3
O1—Zn1—O1W84.44 (6)H2A—C2—H2B108.5
O3—Zn1—O1W93.36 (7)O3—C3—C4107.37 (16)
C1—O1—Zn1119.35 (12)O3—C3—H3A110.2
C1—O2—Zn1ii131.92 (13)C4—C3—H3A110.2
C2—O3—C3120.00 (16)O3—C3—H3B110.2
C2—O3—Zn1120.19 (13)C4—C3—H3B110.2
C3—O3—Zn1119.66 (12)H3A—C3—H3B108.5
C4—O5—Zn1120.35 (12)O4—C4—O5124.74 (17)
Zn1—O1W—H1WA118.3 (19)O4—C4—C3117.50 (17)
Zn1—O1W—H1WB114 (2)O5—C4—C3117.76 (17)
Symmetry codes: (i) x+1/2, y1/2, z+3/2; (ii) x+1/2, y+1/2, z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3W—H3WB···O1Wiii0.71 (3)2.20 (3)2.877 (3)162 (3)
O3W—H3WA···O10.92 (5)1.91 (5)2.817 (2)167 (4)
O2W—H2WB···O4iii0.73 (3)2.09 (3)2.818 (2)176 (3)
O2W—H2WA···O3Wiv0.82 (3)1.89 (3)2.690 (3)167 (2)
O1W—H1WB···O5v0.74 (3)1.98 (3)2.713 (2)173 (3)
O1W—H1WA···O4vi0.77 (3)1.97 (3)2.732 (2)173 (3)
Symmetry codes: (iii) x+1/2, y+1/2, z1/2; (iv) x1, y, z; (v) x, y, z+2; (vi) x+1, y, z.

Experimental details

Crystal data
Chemical formula[Zn(C4H4O5)(H2O)2]·H2O
Mr251.49
Crystal system, space groupMonoclinic, P21/n
Temperature (K)296
a, b, c (Å)7.132 (1), 10.375 (1), 11.100 (1)
β (°) 91.35 (1)
V3)821.1 (1)
Z4
Radiation typeMo Kα
µ (mm1)3.01
Crystal size (mm)0.32 × 0.14 × 0.10
Data collection
DiffractometerMake Model CCD area-detector
diffractometer
Absorption correctionPart of the refinement model (ΔF)
(SADABS in SAINT-NT; Bruker, 2000)
Tmin, Tmax0.53, 0.74
No. of measured, independent and
observed [I > 2σ(I)] reflections
6664, 1826, 1654
Rint0.020
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.025, 0.064, 1.09
No. of reflections1826
No. of parameters142
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.48, 0.31

Computer programs: SMART-NT (Bruker, 2001), SMART-NT, SAINT-NT (Bruker, 2000), SHELXTL-NT (Bruker, 2000), SHELXTL-NT.

Selected bond lengths (Å) top
Zn1—O2i2.0143 (14)O1—C11.258 (2)
Zn1—O2W2.0775 (18)O2—C11.254 (2)
Zn1—O52.0848 (14)O3—C21.396 (2)
Zn1—O12.1058 (13)O3—C31.412 (2)
Zn1—O32.1143 (15)O4—C41.238 (2)
Zn1—O1W2.1272 (17)O5—C41.270 (2)
Symmetry code: (i) x+1/2, y1/2, z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3W—H3WB···O1Wii0.71 (3)2.20 (3)2.877 (3)162 (3)
O3W—H3WA···O10.92 (5)1.91 (5)2.817 (2)167 (4)
O2W—H2WB···O4ii0.73 (3)2.09 (3)2.818 (2)176 (3)
O2W—H2WA···O3Wiii0.82 (3)1.89 (3)2.690 (3)167 (2)
O1W—H1WB···O5iv0.74 (3)1.98 (3)2.713 (2)173 (3)
O1W—H1WA···O4v0.77 (3)1.97 (3)2.732 (2)173 (3)
Symmetry codes: (ii) x+1/2, y+1/2, z1/2; (iii) x1, y, z; (iv) x, y, z+2; (v) x+1, y, z.
 

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