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A new one-dimensional coordination polymer, catena-poly[[acetatohexa­aqua­{μ4-2,6-bis­[bis­(carboxyl­ato­meth­yl)am­ino­meth­yl]-4-methyl­phenolato}­trizinc(II)] octa­hydrate], [Zn3(C17H17N2O9)(C2H3O2)(H2O)6]·8H2O, is a trinuclear complex consisting of three zinc centers joined by a phenolate bridge and Zn(H2O)4 units. In each complex polymer unit, the three Zn atoms have different coordination modes. Of the two phenolate-bridged Zn ions, one adopts a distorted octa­hedral coordination composed of two carboxyl­ate ligands, one tertiary N atom, two water mol­ecules and the bridging phenolate ligand, while the other adopts a pyramidal geometry composed of two carboxyl­ate ligands, one tertiary N atom from another coordination arm, one acetate anion as the counter-anion and the bridging phenolate ligand. The third type of Zn centre is represented by two independent Zn atoms lying on inversion centres. They both have an octa­hedral coordination consisting of four O atoms from four water mol­ecules and two acetate carbonyl O atoms from the ligand. The latter Zn atoms join the above-mentioned binuclear complex units through O atoms of the carboxyl­ate groups into an infinite chain. Neighboring aromatic rings are distributed above and below the chain in an alternating manner. Between the coordination chains, the Zn...Zn separations are 5.750 (4) and 6.806 (4) Å. The whole structure is stabilized by hydrogen bonds formed mainly by solvent water mol­ecules.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107047282/av3103sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107047282/av3103Isup2.hkl
Contains datablock I

CCDC reference: 677206

Comment top

Zinc enzymes often use coordinated water molecules or internal alcoholic hydroxy residues as nucleophiles to react with electrophilic substrates (Kim & Wyckoff, 1991). The role of zinc centers in these enzymes is to orientate and activate the substrates (Hegg & Burstyn, 1998; Krämer, 1999; Lipscomb & Sträer, 1996). The preparation and development of new metallic model compounds to mimic the activity of nucleases in hydrolytic cleavage of DNA is is an important and prosperous field in bioinorganic chemistry. Previously, we reported a few binuclear metal complexes including Ni2(Meng et al., 2004) and Mg2(Gao, Meng & Wei, 2004) complexes of Cl-HXTA (5-chloro-2-hydroxy-1,3-xylene-α,α-diamine -N,N,N',N'-tetraacetic acid), which are able to scissior DNA hydrolytically. Cl-HXTA is an acyclic dinucleating ligand with a phenolate bridge (Murch et al., 1987). As a pentavalent anionic ligand, it has four methoxycarbonyl chelating arms with two sets of donor atoms, i.e. one N and three O atoms, as the coordination sites. One of the advantages of Cl-HXTA is that most of its dinuclear metal complexes are highly soluble in water.

As a continuation of aforementioned study, we report here a newly synthesized binuclear zinc complex with CH3—HXTA (5-methyl-2-hydroxy-1,3-xylene-α,α-diamine-N,N,N',N'- tetraacetic acid), (I). CH3—HXTA is very similar to Cl-HXTA in structure, with the Cl atom in the later replaced by a methyl group in the former.

Selected geometric parameters of the title compound are listed in Table 1, while the molecular configuration and crystal packing are illustrated in Figs.1 and 2, respectively. Fig.1 shows that the coordination environments of the two oxo-bridged Zn ions are different in geometry and donor atoms, and differ from those in a related Zn complex (Gao, Meng & Zhu, 2004), where the two Zn atoms have similar coordination environments with distorted octahedral geometry. More specifically, The ion Zn1 adopts a distorted octahedral coordination composed of two carboxylate groups, one tertiary N atom, two water molecules, and the bridging phenolate ligand (O1); atom Zn2 adopts a five-coordinate pyramidal geometry, composed of two carboxylate groups, one tertiary N atom from another coordination arm, one acetate anion as the counter-anion, and the bridging phenolate (O1). The Zn1···Zn2 separation of 3.630 (4) Å, which is shorter than the value of 3.745 (3) Å reported by Gao, Meng & Zhu (2004), suggests no obvious metal-metal bond formation. The Zn1—O1 distance is 2.036 (4) Å, while Zn2—O1 distance is 1.990 (4) Å, indicating that the oxo-bridging atom is similar but not equivalent for both Zn1 and Zn2. The Zn1—O1—Zn2 angle is 128.74 (19)° which is less than that found by Gao, Meng & Zhu (2004) [131.7 (3)°]. In spite of this slight difference, the only oxo-bridge is similar to those in the structures reported previously [Zn—O—Zn (Gao, Mneg & Zhu et al., 2004), Ni—O—Ni(Meng et al., 2004) and Mg—O—Mg (Gao, Meng & Wei,2004). The average Zn—O bond length in the phenolate-bridge is 2.014 (4) Å, in accordance with that of the metal-phenolate bonds in other reported dinulear cocomplexes, such as [Fe2(sal)3trien(OMe)]Cl2 (sal=salicylic aldehyde and trien=trethylene tetraamine) (Chiari et al., 1982) and [Fe2(sal)3trien(OH)]Cl2 (Chiari et al., 1983). The complex anion as a whole has a pseudo-C2 axis passing through atoms C7, C3, C6 and O1, as has been reported previously (Sakiyama et al., 1999). The least-square plane of the phenyl ring of CH3—HXTA and the Zn1/O1/Zn2 plane are twisted with a dihedral angle of 52.75 (4)°. Zn3 and Zn4 atoms lie on inversion centers and join binuclear complex units containing Zn1 and Zn2 through O atoms of the carboxylate groups of the CH3—HXTA ligand into an infinire chain (Fig. 2). Zn3 and Zn4 atoms have equal octahedral environment consisting of four O atoms from four water molecules and two acetate carbonyl O atoms from CH3—HXTA ligand. Thus, an infinite one-dimensional coordination poylmer is constructed (Fig. 2). In this chain, the Zn1···Zn3 separation is 5.345 (4) Å and the Zn2···Zn4 separation is 5.775 (4) Å. Along the chain, the neighboring aromatic rings are distributed alternately above and below the chain. This chain extends infinitely with a repeating unit [e.g: Zn3A···Zn3B] of 28.955 (4) Å (Fig. 2). Between the coordination chains, the shortest Zn···Zn separations are 5.750 (4) and 6.806 (4) Å. The whole structure is stabilized by a hydrogen- bond net, which is formed maily by solvent water molecules, as shown in Fig.2. Their geometric parameters are also listed in Table 2.

In summary, we have described a novel coordination polymer structure constructed by Zn—O—Zn bridges and Zn-4H2O units. Its bioactivity, for example as DNA cleavage agent, is under investigation in our laboratory.

Related literature top

For related literature, see: Branum et al. (2001); Chiari et al. (1982, 1983); Gao, Meng & Wei (2004); Gao, Meng & Zhu (2004); Hegg & Burstyn (1998); Kim & Wyckoff (1991); Krämer (1999); Lipscomb & Sträer (1996); Meng et al. (2004); Murch et al. (1987); Sakiyama et al. (1999).

Experimental top

All chemicals were of reagent grade and commercially available from the Beijing Chemical Reagents Company of China, and were used without further purification. The ligand CH3—HXTA was synthesized according to the published procedure (Branum et al., 2001). Zn(CH3COO)2·2H2O (0.4390 g, 2 mmol) and Na4(CH3—HXTA) (0.486 g, 1 mmol) were dissolved in water (5 ml) and mixed with stirring at 323 K for 3 h. The resulting colorless solution was filtered and the filtrate was left to stand at room temperature. Colorless crystals of (I) appeared after half a month as a result of slow evaporation of the aqueous solvent.

Refinement top

H atoms attached to C atoms were placed in geometrically idealized positions, with Csp3—H=0.980 (methyl) with Uiso(H)=1.5Ueq, Csp3—H=0.970 Å (methylene), Csp2=0.940 Å, and constrained to ride on their parentatoms, with Uiso(H)=1.2Ueq. H atoms attached to O atoms (in waters) were located in difference Fourier maps and constrained to ride on their parent atoms, with Uiso(H)=1.5Ueq.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1999); software used to prepare material for publication: SHELXTL/PC (Sheldrick, 1999).

Figures top
[Figure 1] Fig. 1. ORTEP plot of the asymmetric unit of the title compound (I). Displacement ellipsoids are drawn at the 30% probability level. All hydrogen atoms and crystallization water molecules have been omitted for clarity.
[Figure 2] Fig. 2. The part of the coordination polymer chains, viewed along favorable direction close to c axis. Selected atoms were labled (A, B, C only indicate different molecular units in the polymer chain). Free water molecules and all hydrogen atoms that did not involved in H-bonds have been omitted for clarity.
catena-poly[[acetatohexaaqua(µ4-2,6-bis[bis(carboxylatomethyl)aminomethyl]- 4-methylphenolato)trizinc(II)] octahydrate] top
Crystal data top
[Zn3(C2H3O2)(C17H17N2O9)(H2O)6]·8H2OV = 1718.7 (5) Å3
Mr = 900.70Z = 2
Triclinic, P1F(000) = 932
Hall symbol: -P 1Dx = 1.740 Mg m3
a = 10.0095 (18) ÅMo Kα radiation, λ = 0.71073 Å
b = 13.293 (2) ŵ = 2.17 mm1
c = 14.052 (3) ÅT = 213 K
α = 93.573 (3)°Block, colorless
β = 99.225 (3)°0.40 × 0.30 × 0.30 mm
γ = 110.134 (2)°
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer
5932 independent reflections
Radiation source: fine-focus sealed tube4769 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.035
ϕ and ω scansθmax = 25.0°, θmin = 1.6°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2000)
h = 1110
Tmin = 0.477, Tmax = 0.562k = 1515
8459 measured reflectionsl = 1116
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)] = 0.069Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.131H-atom parameters constrained
S = 1.18 w = 1/[σ2(Fo2) + (0.0415P)2]
where P = (Fo2 + 2Fc2)/3
5932 reflections(Δ/σ)max < 0.001
446 parametersΔρmax = 0.92 e Å3
0 restraintsΔρmin = 0.88 e Å3
Crystal data top
[Zn3(C2H3O2)(C17H17N2O9)(H2O)6]·8H2Oγ = 110.134 (2)°
Mr = 900.70V = 1718.7 (5) Å3
Triclinic, P1Z = 2
a = 10.0095 (18) ÅMo Kα radiation
b = 13.293 (2) ŵ = 2.17 mm1
c = 14.052 (3) ÅT = 213 K
α = 93.573 (3)°0.40 × 0.30 × 0.30 mm
β = 99.225 (3)°
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer
5932 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2000)
4769 reflections with I > 2σ(I)
Tmin = 0.477, Tmax = 0.562Rint = 0.035
8459 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0690 restraints
wR(F2) = 0.131H-atom parameters constrained
S = 1.18Δρmax = 0.92 e Å3
5932 reflectionsΔρmin = 0.88 e Å3
446 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.

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
xyzUiso*/Ueq
Zn10.62423 (8)0.19713 (5)0.36362 (5)0.0189 (2)
Zn20.73994 (8)0.24244 (5)0.62603 (5)0.0190 (2)
Zn30.50000.00000.00000.0223 (3)
Zn41.00000.50001.00000.0221 (3)
N10.7606 (5)0.3152 (4)0.2906 (4)0.0188 (12)
N20.6389 (5)0.3399 (4)0.6913 (4)0.0185 (12)
C10.8216 (6)0.4544 (5)0.4318 (4)0.0192 (14)
C20.8481 (6)0.5632 (5)0.4319 (5)0.0223 (15)
H2A0.90650.60140.39030.027*
C30.7909 (7)0.6180 (5)0.4915 (5)0.0232 (16)
C40.7048 (6)0.5593 (5)0.5511 (5)0.0225 (15)
H4A0.66560.59540.59210.027*
C50.6735 (6)0.4498 (5)0.5533 (5)0.0199 (14)
C60.7353 (6)0.3969 (4)0.4945 (4)0.0171 (14)
C70.8255 (7)0.7379 (5)0.4927 (6)0.0364 (19)
H7B0.77570.76210.53780.055*
H7C0.79380.75310.42800.055*
H7D0.92930.77570.51290.055*
C80.8809 (6)0.3942 (5)0.3642 (5)0.0241 (15)
H8A0.94810.44590.33130.029*
H8B0.93460.35600.40220.029*
C90.6725 (6)0.3681 (5)0.2353 (5)0.0216 (15)
H9A0.65730.34310.16590.026*
H9B0.72630.44620.24510.026*
C100.5239 (7)0.3464 (5)0.2638 (5)0.0221 (15)
C110.8099 (6)0.2517 (5)0.2242 (5)0.0214 (15)
H11A0.88770.23210.26020.026*
H11B0.84800.29460.17370.026*
C120.6824 (7)0.1499 (5)0.1775 (5)0.0238 (16)
C130.5701 (6)0.3857 (5)0.6123 (5)0.0209 (15)
H13A0.52550.43220.64090.025*
H13B0.49260.32640.56900.025*
C140.5279 (6)0.2644 (4)0.7353 (5)0.0204 (15)
H14B0.45230.29410.74180.025*
H14A0.57200.25670.80060.025*
C150.4589 (7)0.1535 (5)0.6750 (5)0.0200 (15)
C160.7506 (6)0.4252 (4)0.7643 (5)0.0226 (15)
H16B0.71470.42640.82510.027*
H16A0.76550.49550.74100.027*
C170.8941 (7)0.4095 (5)0.7846 (5)0.0211 (15)
C180.8567 (7)0.0811 (5)0.6591 (5)0.0248 (16)
C190.9284 (8)0.0038 (6)0.6305 (6)0.045 (2)
H19A0.92540.04600.67840.068*
H19B1.02860.04420.62740.068*
H19C0.87740.03630.56740.068*
O10.7090 (4)0.2895 (3)0.4952 (3)0.0186 (10)
O20.4772 (4)0.2722 (3)0.3127 (3)0.0244 (11)
O30.4547 (5)0.4039 (3)0.2296 (4)0.0377 (13)
O40.5844 (4)0.1098 (3)0.2248 (3)0.0227 (10)
O50.6818 (4)0.1117 (3)0.0934 (3)0.0270 (11)
O60.5335 (4)0.1268 (3)0.6202 (3)0.0230 (10)
O70.3362 (5)0.0945 (3)0.6848 (3)0.0289 (11)
O80.9127 (4)0.3372 (3)0.7291 (3)0.0248 (11)
O90.9909 (4)0.4693 (3)0.8511 (3)0.0265 (11)
O100.7732 (4)0.1169 (3)0.3978 (3)0.0258 (11)
H10A0.74970.04940.38260.039*
H10B0.81000.13300.45810.039*
O110.4597 (4)0.0807 (3)0.4124 (3)0.0254 (11)
H11C0.45260.08440.47190.038*
H11D0.45890.01830.39390.038*
O120.8322 (5)0.1379 (3)0.5932 (3)0.0264 (11)
O130.8246 (5)0.0865 (3)0.7394 (3)0.0330 (12)
O140.3864 (4)0.1102 (3)0.0164 (3)0.0278 (11)
H14C0.34110.10210.06330.042*
H14D0.32610.09960.03660.042*
O150.4248 (4)0.0777 (3)0.1138 (3)0.0273 (11)
H15A0.45770.04440.17110.041*
H15B0.33720.11900.10990.041*
O161.1492 (4)0.4212 (3)1.0153 (3)0.0325 (12)
H16C1.15340.38581.06340.049*
H16D1.13000.37880.96300.049*
O171.1671 (5)0.6451 (3)1.0067 (4)0.0352 (13)
H17A1.16400.70801.01610.053*
H17B1.25340.65021.00390.053*
O180.9875 (5)0.0957 (4)0.0994 (4)0.0593 (17)
H18A0.92920.04790.12560.089*
H18B1.04640.07020.07930.089*
O190.5820 (5)0.5477 (3)0.1154 (4)0.0398 (13)
H19D0.55060.51040.15950.060*
H19E0.59810.50790.07230.060*
O200.2607 (4)0.0981 (3)0.1778 (3)0.0306 (11)
H20A0.23350.04390.20860.046*
H20B0.32290.15130.21640.046*
O210.4477 (5)0.6693 (4)0.0101 (3)0.0372 (12)
H21A0.48760.73050.00820.056*
H21B0.50720.65890.05520.056*
O220.1555 (5)0.3179 (3)0.1718 (4)0.0417 (13)
H22A0.24560.32880.18490.063*
H22B0.12710.32780.22430.063*
O230.8712 (5)0.1678 (3)0.9368 (4)0.0385 (13)
H23A0.91550.14530.98250.058*
H23B0.89830.15620.88420.058*
O240.2052 (5)0.1005 (3)0.8460 (3)0.0346 (12)
H24A0.17870.15470.84310.052*
H24B0.25040.09750.80020.052*
O250.1444 (5)0.2896 (4)0.8356 (4)0.0464 (14)
H25A0.07000.29860.80470.070*
H25B0.21870.34560.83620.070*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0191 (4)0.0171 (4)0.0187 (4)0.0049 (3)0.0038 (3)0.0009 (3)
Zn20.0205 (4)0.0177 (4)0.0190 (4)0.0078 (3)0.0034 (3)0.0002 (3)
Zn30.0230 (6)0.0235 (6)0.0191 (6)0.0084 (5)0.0024 (5)0.0026 (5)
Zn40.0197 (6)0.0198 (6)0.0238 (7)0.0064 (5)0.0005 (5)0.0026 (5)
N10.013 (3)0.023 (3)0.020 (3)0.007 (2)0.000 (2)0.000 (2)
N20.023 (3)0.012 (3)0.020 (3)0.006 (2)0.007 (2)0.001 (2)
C10.015 (3)0.023 (3)0.014 (4)0.004 (3)0.005 (3)0.002 (3)
C20.009 (3)0.018 (3)0.029 (4)0.004 (3)0.004 (3)0.002 (3)
C30.020 (4)0.012 (3)0.032 (4)0.005 (3)0.005 (3)0.002 (3)
C40.020 (4)0.024 (4)0.021 (4)0.009 (3)0.004 (3)0.007 (3)
C50.015 (3)0.019 (3)0.020 (4)0.002 (3)0.002 (3)0.001 (3)
C60.015 (3)0.014 (3)0.017 (4)0.004 (3)0.007 (3)0.002 (3)
C70.030 (4)0.023 (4)0.053 (5)0.008 (3)0.009 (4)0.002 (4)
C80.015 (3)0.027 (4)0.025 (4)0.003 (3)0.002 (3)0.003 (3)
C90.021 (4)0.017 (3)0.020 (4)0.003 (3)0.005 (3)0.001 (3)
C100.026 (4)0.016 (3)0.023 (4)0.009 (3)0.001 (3)0.001 (3)
C110.018 (4)0.024 (3)0.020 (4)0.004 (3)0.005 (3)0.001 (3)
C120.029 (4)0.025 (4)0.021 (4)0.017 (3)0.001 (3)0.001 (3)
C130.012 (3)0.023 (3)0.026 (4)0.006 (3)0.001 (3)0.002 (3)
C140.019 (3)0.023 (3)0.021 (4)0.008 (3)0.007 (3)0.000 (3)
C150.018 (4)0.020 (3)0.020 (4)0.007 (3)0.001 (3)0.002 (3)
C160.029 (4)0.014 (3)0.020 (4)0.006 (3)0.001 (3)0.008 (3)
C170.022 (4)0.018 (3)0.024 (4)0.006 (3)0.006 (3)0.009 (3)
C180.021 (4)0.025 (4)0.026 (4)0.009 (3)0.001 (3)0.004 (3)
C190.065 (6)0.042 (5)0.044 (5)0.034 (4)0.017 (4)0.013 (4)
O10.026 (2)0.013 (2)0.016 (2)0.0043 (18)0.0065 (19)0.0034 (18)
O20.019 (2)0.024 (2)0.032 (3)0.009 (2)0.006 (2)0.003 (2)
O30.031 (3)0.037 (3)0.055 (4)0.020 (2)0.012 (3)0.017 (3)
O40.017 (2)0.027 (2)0.020 (3)0.0025 (19)0.006 (2)0.003 (2)
O50.022 (3)0.030 (3)0.023 (3)0.004 (2)0.005 (2)0.004 (2)
O60.023 (2)0.020 (2)0.026 (3)0.0073 (19)0.007 (2)0.002 (2)
O70.025 (3)0.024 (2)0.038 (3)0.006 (2)0.013 (2)0.001 (2)
O80.022 (2)0.022 (2)0.031 (3)0.011 (2)0.002 (2)0.005 (2)
O90.018 (2)0.027 (2)0.027 (3)0.003 (2)0.000 (2)0.009 (2)
O100.030 (3)0.022 (2)0.022 (3)0.010 (2)0.003 (2)0.005 (2)
O110.028 (3)0.021 (2)0.027 (3)0.006 (2)0.009 (2)0.001 (2)
O120.032 (3)0.025 (2)0.026 (3)0.015 (2)0.005 (2)0.000 (2)
O130.045 (3)0.031 (3)0.023 (3)0.013 (2)0.010 (2)0.001 (2)
O140.029 (3)0.034 (3)0.024 (3)0.015 (2)0.008 (2)0.003 (2)
O150.026 (3)0.031 (3)0.017 (3)0.003 (2)0.000 (2)0.002 (2)
O160.031 (3)0.035 (3)0.033 (3)0.019 (2)0.003 (2)0.004 (2)
O170.026 (3)0.019 (2)0.057 (4)0.006 (2)0.009 (2)0.004 (2)
O180.029 (3)0.060 (3)0.094 (5)0.017 (3)0.017 (3)0.030 (4)
O190.045 (3)0.034 (3)0.042 (3)0.015 (2)0.008 (3)0.009 (3)
O200.024 (3)0.033 (3)0.031 (3)0.006 (2)0.003 (2)0.005 (2)
O210.025 (3)0.044 (3)0.037 (3)0.008 (2)0.001 (2)0.010 (3)
O220.031 (3)0.045 (3)0.049 (4)0.015 (2)0.004 (3)0.003 (3)
O230.038 (3)0.038 (3)0.040 (3)0.012 (2)0.015 (2)0.003 (3)
O240.038 (3)0.040 (3)0.035 (3)0.022 (2)0.015 (2)0.009 (2)
O250.035 (3)0.045 (3)0.065 (4)0.021 (3)0.007 (3)0.012 (3)
Geometric parameters (Å, º) top
Zn1—O12.036 (4)C11—C121.523 (8)
Zn1—O112.078 (4)C11—H11A0.9800
Zn1—O22.106 (4)C11—H11B0.9800
Zn1—O42.113 (4)C12—O51.256 (7)
Zn1—O102.126 (4)C12—O41.257 (8)
Zn1—N12.134 (5)C13—H13A0.9800
Zn2—O121.984 (4)C13—H13B0.9800
Zn2—O11.990 (4)C14—C151.525 (8)
Zn2—O82.036 (4)C14—H14B0.9800
Zn2—O62.094 (4)C14—H14A0.9800
Zn2—N22.143 (5)C15—O71.244 (7)
Zn3—O15i2.061 (4)C15—O61.269 (7)
Zn3—O152.061 (4)C16—C171.507 (8)
Zn3—O52.091 (4)C16—H16B0.9800
Zn3—O5i2.091 (4)C16—H16A0.9800
Zn3—O142.164 (4)C17—O91.237 (7)
Zn3—O14i2.164 (4)C17—O81.282 (7)
Zn4—O172.057 (4)C18—O131.227 (8)
Zn4—O17ii2.057 (4)C18—O121.276 (8)
Zn4—O9ii2.088 (4)C18—C191.510 (8)
Zn4—O92.088 (4)C19—H19A0.9700
Zn4—O16ii2.092 (4)C19—H19B0.9700
Zn4—O162.092 (4)C19—H19C0.9700
N1—C91.468 (7)O10—H10A0.8500
N1—C111.471 (7)O10—H10B0.8501
N1—C81.489 (7)O11—H11C0.8500
N2—C141.468 (7)O11—H11D0.8500
N2—C161.483 (7)O14—H14C0.8500
N2—C131.486 (7)O14—H14D0.8500
C1—C21.378 (8)O15—H15A0.8500
C1—C61.407 (8)O15—H15B0.8500
C1—C81.518 (8)O16—H16C0.8500
C2—C31.387 (8)O16—H16D0.8500
C2—H2A0.9400O17—H17A0.8500
C3—C41.380 (9)O17—H17B0.8499
C3—C71.508 (8)O18—H18A0.8500
C4—C51.383 (8)O18—H18B0.8500
C4—H4A0.9400O19—H19D0.8500
C5—C61.398 (8)O19—H19E0.8500
C5—C131.496 (8)O20—H20A0.8500
C6—O11.360 (6)O20—H20B0.8500
C7—H7B0.9700O21—H21A0.8500
C7—H7C0.9700O21—H21B0.8500
C7—H7D0.9700O22—H22A0.8500
C8—H8A0.9800O22—H22B0.8506
C8—H8B0.9800O23—H23A0.8498
C9—C101.538 (8)O23—H23B0.8499
C9—H9A0.9800O24—H24A0.8500
C9—H9B0.9800O24—H24B0.8499
C10—O21.238 (7)O25—H25A0.8500
C10—O31.264 (7)O25—H25B0.8500
O1—Zn1—O1194.90 (16)N1—C8—H8A109.5
O1—Zn1—O297.25 (16)C1—C8—H8A109.5
O11—Zn1—O289.60 (16)N1—C8—H8B109.5
O1—Zn1—O4167.44 (16)C1—C8—H8B109.5
O11—Zn1—O494.77 (16)H8A—C8—H8B108.1
O2—Zn1—O490.82 (17)N1—C9—C10113.7 (5)
O1—Zn1—O1088.64 (16)N1—C9—H9A108.8
O11—Zn1—O1092.99 (16)C10—C9—H9A108.8
O2—Zn1—O10173.35 (17)N1—C9—H9B108.8
O4—Zn1—O1082.86 (16)C10—C9—H9B108.8
O1—Zn1—N192.85 (17)H9A—C9—H9B107.7
O11—Zn1—N1168.87 (18)O2—C10—O3124.8 (6)
O2—Zn1—N181.49 (17)O2—C10—C9119.4 (5)
O4—Zn1—N178.80 (17)O3—C10—C9115.6 (6)
O10—Zn1—N195.18 (17)N1—C11—C12109.0 (5)
O12—Zn2—O197.96 (17)N1—C11—H11A109.9
O12—Zn2—O894.54 (17)C12—C11—H11A109.9
O1—Zn2—O8119.23 (17)N1—C11—H11B109.9
O12—Zn2—O695.87 (16)C12—C11—H11B109.9
O1—Zn2—O699.32 (17)H11A—C11—H11B108.3
O8—Zn2—O6138.07 (18)O5—C12—O4124.1 (6)
O12—Zn2—N2167.19 (19)O5—C12—C11117.4 (6)
O1—Zn2—N294.66 (18)O4—C12—C11118.5 (6)
O8—Zn2—N281.15 (17)N2—C13—C5113.7 (5)
O6—Zn2—N279.83 (17)N2—C13—H13A108.8
O15i—Zn3—O15180.00 (12)C5—C13—H13A108.8
O15i—Zn3—O588.07 (16)N2—C13—H13B108.8
O15—Zn3—O591.93 (16)C5—C13—H13B108.8
O15i—Zn3—O5i91.93 (16)H13A—C13—H13B107.7
O15—Zn3—O5i88.07 (16)N2—C14—C15112.1 (5)
O5—Zn3—O5i180.0 (3)N2—C14—H14B109.2
O15i—Zn3—O1488.38 (16)C15—C14—H14B109.2
O15—Zn3—O1491.63 (16)N2—C14—H14A109.2
O5—Zn3—O1488.70 (16)C15—C14—H14A109.2
O5i—Zn3—O1491.30 (16)H14B—C14—H14A107.9
O15i—Zn3—O14i91.62 (16)O7—C15—O6124.6 (5)
O15—Zn3—O14i88.37 (16)O7—C15—C14118.2 (5)
O5—Zn3—O14i91.30 (16)O6—C15—C14117.1 (5)
O5i—Zn3—O14i88.70 (16)N2—C16—C17113.4 (5)
O14—Zn3—O14i180.0 (3)N2—C16—H16B108.9
O17—Zn4—O17ii180.000 (1)C17—C16—H16B108.9
O17—Zn4—O9ii89.67 (18)N2—C16—H16A108.9
O17ii—Zn4—O9ii90.33 (17)C17—C16—H16A108.9
O17—Zn4—O990.33 (17)H16B—C16—H16A107.7
O17ii—Zn4—O989.67 (18)O9—C17—O8122.6 (6)
O9ii—Zn4—O9180.000 (1)O9—C17—C16119.2 (6)
O17—Zn4—O16ii90.14 (17)O8—C17—C16118.2 (5)
O17ii—Zn4—O16ii89.86 (17)O13—C18—O12123.9 (6)
O9ii—Zn4—O16ii84.85 (17)O13—C18—C19121.4 (7)
O9—Zn4—O16ii95.15 (17)O12—C18—C19114.6 (6)
O17—Zn4—O1689.86 (17)C18—C19—H19A109.5
O17ii—Zn4—O1690.14 (17)C18—C19—H19B109.5
O9ii—Zn4—O1695.15 (17)H19A—C19—H19B109.5
O9—Zn4—O1684.85 (17)C18—C19—H19C109.5
O16ii—Zn4—O16180.000 (2)H19A—C19—H19C109.5
C9—N1—C11110.3 (5)H19B—C19—H19C109.5
C9—N1—C8111.4 (4)C6—O1—Zn2115.5 (4)
C11—N1—C8113.5 (5)C6—O1—Zn1115.4 (4)
C9—N1—Zn1108.4 (4)Zn2—O1—Zn1128.74 (19)
C11—N1—Zn1104.0 (3)C10—O2—Zn1115.1 (4)
C8—N1—Zn1108.8 (4)C12—O4—Zn1112.9 (4)
C14—N2—C16112.5 (5)C12—O5—Zn3124.8 (4)
C14—N2—C13110.4 (5)C15—O6—Zn2114.7 (4)
C16—N2—C13112.2 (4)C17—O8—Zn2117.5 (4)
C14—N2—Zn2104.9 (3)C17—O9—Zn4132.3 (4)
C16—N2—Zn2108.9 (4)Zn1—O10—H10A122.2
C13—N2—Zn2107.6 (4)Zn1—O10—H10B108.5
C2—C1—C6119.3 (6)H10A—O10—H10B108.8
C2—C1—C8121.7 (6)Zn1—O11—H11C121.0
C6—C1—C8119.0 (5)Zn1—O11—H11D109.4
C1—C2—C3121.9 (6)H11C—O11—H11D109.0
C1—C2—H2A119.0C18—O12—Zn2116.9 (4)
C3—C2—H2A119.0Zn3—O14—H14C114.9
C4—C3—C2117.5 (5)Zn3—O14—H14D106.2
C4—C3—C7121.6 (6)H14C—O14—H14D109.1
C2—C3—C7120.9 (6)Zn3—O15—H15A118.4
C3—C4—C5123.1 (6)Zn3—O15—H15B123.0
C3—C4—H4A118.5H15A—O15—H15B109.0
C5—C4—H4A118.5Zn4—O16—H16C118.3
C4—C5—C6118.4 (6)Zn4—O16—H16D106.6
C4—C5—C13122.3 (6)H16C—O16—H16D108.9
C6—C5—C13119.2 (5)Zn4—O17—H17A127.2
O1—C6—C5120.5 (5)Zn4—O17—H17B123.4
O1—C6—C1119.8 (5)H17A—O17—H17B109.3
C5—C6—C1119.7 (5)H18A—O18—H18B109.1
C3—C7—H7B109.5H19D—O19—H19E109.2
C3—C7—H7C109.5H20A—O20—H20B109.2
H7B—C7—H7C109.5H21A—O21—H21B109.1
C3—C7—H7D109.5H22A—O22—H22B108.9
H7B—C7—H7D109.5H23A—O23—H23B109.4
H7C—C7—H7D109.5H24A—O24—H24B108.8
N1—C8—C1110.5 (5)H25A—O25—H25B108.9
O1—Zn1—N1—C9105.6 (4)N2—C16—C17—O9172.8 (6)
O11—Zn1—N1—C928.4 (11)N2—C16—C17—O810.2 (8)
O2—Zn1—N1—C98.7 (3)C5—C6—O1—Zn250.4 (6)
O4—Zn1—N1—C983.8 (4)C1—C6—O1—Zn2131.7 (5)
O10—Zn1—N1—C9165.5 (4)C5—C6—O1—Zn1123.8 (5)
O1—Zn1—N1—C11137.0 (3)C1—C6—O1—Zn154.1 (6)
O11—Zn1—N1—C1189.0 (9)O12—Zn2—O1—C6139.7 (4)
O2—Zn1—N1—C11126.1 (4)O8—Zn2—O1—C639.9 (4)
O4—Zn1—N1—C1133.6 (3)O6—Zn2—O1—C6122.9 (4)
O10—Zn1—N1—C1148.1 (4)N2—Zn2—O1—C642.5 (4)
O1—Zn1—N1—C815.7 (4)O12—Zn2—O1—Zn147.0 (3)
O11—Zn1—N1—C8149.8 (8)O8—Zn2—O1—Zn1146.8 (2)
O2—Zn1—N1—C8112.6 (4)O6—Zn2—O1—Zn150.3 (3)
O4—Zn1—N1—C8154.8 (4)N2—Zn2—O1—Zn1130.7 (3)
O10—Zn1—N1—C873.2 (4)O11—Zn1—O1—C6131.7 (4)
O12—Zn2—N2—C1443.8 (10)O2—Zn1—O1—C641.5 (4)
O1—Zn2—N2—C14126.2 (4)O4—Zn1—O1—C688.1 (8)
O8—Zn2—N2—C14114.9 (4)O10—Zn1—O1—C6135.4 (4)
O6—Zn2—N2—C1427.5 (4)N1—Zn1—O1—C640.3 (4)
O12—Zn2—N2—C1676.9 (9)O11—Zn1—O1—Zn241.6 (3)
O1—Zn2—N2—C16113.1 (4)O2—Zn1—O1—Zn2131.8 (3)
O8—Zn2—N2—C165.8 (4)O4—Zn1—O1—Zn298.6 (7)
O6—Zn2—N2—C16148.2 (4)O10—Zn1—O1—Zn251.3 (3)
O12—Zn2—N2—C13161.3 (7)N1—Zn1—O1—Zn2146.4 (3)
O1—Zn2—N2—C138.7 (3)O3—C10—O2—Zn1177.4 (5)
O8—Zn2—N2—C13127.6 (4)C9—C10—O2—Zn16.8 (7)
O6—Zn2—N2—C1390.0 (3)O1—Zn1—O2—C1093.0 (4)
C6—C1—C2—C30.6 (9)O11—Zn1—O2—C10172.1 (4)
C8—C1—C2—C3178.2 (6)O4—Zn1—O2—C1077.3 (4)
C1—C2—C3—C40.4 (9)O10—Zn1—O2—C1059.1 (15)
C1—C2—C3—C7177.9 (6)N1—Zn1—O2—C101.2 (4)
C2—C3—C4—C50.3 (9)O5—C12—O4—Zn1180.0 (5)
C7—C3—C4—C5178.6 (6)C11—C12—O4—Zn10.5 (7)
C3—C4—C5—C61.9 (9)O1—Zn1—O4—C1229.1 (10)
C3—C4—C5—C13174.8 (6)O11—Zn1—O4—C12169.2 (4)
C4—C5—C6—O1179.2 (5)O2—Zn1—O4—C12101.1 (4)
C13—C5—C6—O14.0 (8)O10—Zn1—O4—C1276.8 (4)
C4—C5—C6—C12.9 (9)N1—Zn1—O4—C1219.9 (4)
C13—C5—C6—C1173.9 (5)O4—C12—O5—Zn316.2 (9)
C2—C1—C6—O1179.8 (5)C11—C12—O5—Zn3163.3 (4)
C8—C1—C6—O11.4 (8)O15i—Zn3—O5—C12143.7 (5)
C2—C1—C6—C52.3 (9)O15—Zn3—O5—C1236.3 (5)
C8—C1—C6—C5176.6 (5)O5i—Zn3—O5—C1297 (68)
C9—N1—C8—C156.3 (7)O14—Zn3—O5—C1255.3 (5)
C11—N1—C8—C1178.4 (5)O14i—Zn3—O5—C12124.7 (5)
Zn1—N1—C8—C163.2 (5)O7—C15—O6—Zn2177.0 (5)
C2—C1—C8—N1112.6 (6)C14—C15—O6—Zn20.7 (7)
C6—C1—C8—N166.2 (7)O12—Zn2—O6—C15151.2 (4)
C11—N1—C9—C10127.4 (5)O1—Zn2—O6—C15109.7 (4)
C8—N1—C9—C10105.5 (6)O8—Zn2—O6—C1547.7 (5)
Zn1—N1—C9—C1014.2 (6)N2—Zn2—O6—C1516.6 (4)
N1—C9—C10—O214.9 (8)O9—C17—O8—Zn2178.1 (5)
N1—C9—C10—O3169.0 (5)C16—C17—O8—Zn25.0 (7)
C9—N1—C11—C1274.0 (6)O12—Zn2—O8—C17168.4 (4)
C8—N1—C11—C12160.1 (5)O1—Zn2—O8—C1789.8 (4)
Zn1—N1—C11—C1242.1 (5)O6—Zn2—O8—C1764.4 (5)
N1—C11—C12—O5149.6 (5)N2—Zn2—O8—C170.6 (4)
N1—C11—C12—O429.9 (8)O8—C17—O9—Zn4124.3 (6)
C14—N2—C13—C5170.9 (5)C16—C17—O9—Zn458.8 (8)
C16—N2—C13—C562.7 (6)O17—Zn4—O9—C17158.4 (6)
Zn2—N2—C13—C557.0 (5)O17ii—Zn4—O9—C1721.6 (6)
C4—C5—C13—N2116.0 (6)O9ii—Zn4—O9—C1772 (100)
C6—C5—C13—N267.3 (7)O16ii—Zn4—O9—C1768.2 (6)
C16—N2—C14—C15153.4 (5)O16—Zn4—O9—C17111.8 (6)
C13—N2—C14—C1580.5 (6)O13—C18—O12—Zn21.3 (8)
Zn2—N2—C14—C1535.1 (5)C19—C18—O12—Zn2179.4 (4)
N2—C14—C15—O7157.2 (5)O1—Zn2—O12—C18173.4 (4)
N2—C14—C15—O624.9 (8)O8—Zn2—O12—C1866.2 (4)
C14—N2—C16—C17106.2 (6)O6—Zn2—O12—C1873.1 (4)
C13—N2—C16—C17128.6 (5)N2—Zn2—O12—C183.5 (10)
Zn2—N2—C16—C179.6 (6)
Symmetry codes: (i) x+1, y, z; (ii) x+2, y+1, z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O25—H25B···O19iii0.851.992.789 (6)157
O25—H25A···O8iv0.851.992.835 (6)173
O24—H24B···O70.851.962.803 (6)173
O24—H24A···O250.851.942.790 (6)172
O23—H23B···O130.852.092.818 (7)144
O23—H23A···O18v0.851.932.772 (7)169
O22—H22A···O30.851.962.772 (6)160
O21—H21B···O190.852.042.786 (6)146
O21—H21A···O14vi0.852.082.910 (6)165
O20—H20B···O20.852.042.887 (6)177
O20—H20A···O13vii0.851.872.710 (6)172
O19—H19E···O21vi0.852.423.182 (6)150
O19—H19D···O30.851.852.687 (7)166
O18—H18B···O20viii0.852.262.768 (6)119
O18—H18A···O24vii0.852.072.893 (7)162
O17—H17B···O21ix0.851.862.707 (6)174
O17—H17A···O23ii0.851.912.734 (6)165
O16—H16D···O25viii0.852.142.964 (6)164
O16—H16C···O22ix0.851.822.667 (7)175
O15—H15B···O23vii0.851.942.737 (6)155
O15—H15A···O40.852.022.678 (5)133
O14—H14D···O24x0.851.892.728 (6)171
O14—H14C···O200.851.912.752 (6)173
O11—H11D···O6vii0.851.952.793 (5)168
O11—H11C···O60.852.082.867 (6)154
O10—H10B···O120.851.872.691 (6)162
O10—H10A···O7vii0.851.922.741 (5)163
Symmetry codes: (ii) x+2, y+1, z+2; (iii) x+1, y+1, z+1; (iv) x1, y, z; (v) x, y, z+1; (vi) x+1, y+1, z; (vii) x+1, y, z+1; (viii) x+1, y, z; (ix) x+1, y, z+1; (x) x, y, z1.

Experimental details

Crystal data
Chemical formula[Zn3(C2H3O2)(C17H17N2O9)(H2O)6]·8H2O
Mr900.70
Crystal system, space groupTriclinic, P1
Temperature (K)213
a, b, c (Å)10.0095 (18), 13.293 (2), 14.052 (3)
α, β, γ (°)93.573 (3), 99.225 (3), 110.134 (2)
V3)1718.7 (5)
Z2
Radiation typeMo Kα
µ (mm1)2.17
Crystal size (mm)0.40 × 0.30 × 0.30
Data collection
DiffractometerBruker SMART 1K CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2000)
Tmin, Tmax0.477, 0.562
No. of measured, independent and
observed [I > 2σ(I)] reflections
8459, 5932, 4769
Rint0.035
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.069, 0.131, 1.18
No. of reflections5932
No. of parameters446
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.92, 0.88

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL/PC (Sheldrick, 1999).

Selected geometric parameters (Å, º) top
Zn1—O12.036 (4)Zn2—N22.143 (5)
Zn1—O112.078 (4)Zn3—O15i2.061 (4)
Zn1—O22.106 (4)Zn3—O152.061 (4)
Zn1—O42.113 (4)Zn3—O142.164 (4)
Zn1—O102.126 (4)Zn4—O172.057 (4)
Zn1—N12.134 (5)Zn4—O92.088 (4)
Zn2—O121.984 (4)Zn4—O162.092 (4)
Zn2—O11.990 (4)C1—C61.407 (8)
Zn2—O82.036 (4)C1—C81.518 (8)
Zn2—O62.094 (4)
O1—Zn1—O1194.90 (16)O12—Zn2—O894.54 (17)
O1—Zn1—O297.25 (16)O1—Zn2—O8119.23 (17)
O11—Zn1—O289.60 (16)O12—Zn2—O695.87 (16)
O1—Zn1—O4167.44 (16)O1—Zn2—O699.32 (17)
O11—Zn1—O494.77 (16)O8—Zn2—O6138.07 (18)
O2—Zn1—O490.82 (17)O12—Zn2—N2167.19 (19)
O1—Zn1—O1088.64 (16)O1—Zn2—N294.66 (18)
O11—Zn1—O1092.99 (16)O8—Zn2—N281.15 (17)
O2—Zn1—O10173.35 (17)O6—Zn2—N279.83 (17)
O4—Zn1—O1082.86 (16)O15—Zn3—O591.93 (16)
O1—Zn1—N192.85 (17)O15—Zn3—O1491.63 (16)
O11—Zn1—N1168.87 (18)O5—Zn3—O1488.70 (16)
O2—Zn1—N181.49 (17)O17—Zn4—O990.33 (17)
O4—Zn1—N178.80 (17)O17—Zn4—O1689.86 (17)
O10—Zn1—N195.18 (17)O9—Zn4—O1684.85 (17)
O12—Zn2—O197.96 (17)
Symmetry code: (i) x+1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O25—H25B···O19ii0.851.992.789 (6)156.8
O25—H25A···O8iii0.851.992.835 (6)172.9
O24—H24B···O70.851.962.803 (6)173.3
O24—H24A···O250.851.942.790 (6)172.4
O23—H23B···O130.852.092.818 (7)143.9
O23—H23A···O18iv0.851.932.772 (7)169.0
O22—H22A···O30.851.962.772 (6)160.1
O21—H21B···O190.852.042.786 (6)145.7
O21—H21A···O14v0.852.082.910 (6)165.4
O20—H20B···O20.852.042.887 (6)176.5
O20—H20A···O13vi0.851.872.710 (6)171.8
O19—H19E···O21v0.852.423.182 (6)150.0
O19—H19D···O30.851.852.687 (7)165.8
O18—H18A···O24vi0.852.072.893 (7)161.6
O17—H17B···O21vii0.851.862.707 (6)174.3
O17—H17A···O23viii0.851.912.734 (6)164.5
O16—H16D···O25ix0.852.142.964 (6)164.4
O16—H16C···O22vii0.851.822.667 (7)174.9
O15—H15B···O23vi0.851.942.737 (6)154.9
O15—H15A···O40.852.022.678 (5)133.3
O14—H14D···O24x0.851.892.728 (6)170.7
O14—H14C···O200.851.912.752 (6)172.7
O11—H11D···O6vi0.851.952.793 (5)168.3
O11—H11C···O60.852.082.867 (6)154.3
O10—H10B···O120.851.872.691 (6)161.6
O10—H10A···O7vi0.851.922.741 (5)163.0
Symmetry codes: (ii) x+1, y+1, z+1; (iii) x1, y, z; (iv) x, y, z+1; (v) x+1, y+1, z; (vi) x+1, y, z+1; (vii) x+1, y, z+1; (viii) x+2, y+1, z+2; (ix) x+1, y, z; (x) x, y, z1.
 

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