A novel O–Zn bridging polymer complex of 2,6-bis­[bis­(carboxylato­meth­yl)amino­meth­yl]-4-methyl­phenolate

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.

S1. Comment

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

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).

S2. Experimental

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.

S3. Refinement

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

Computing details

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

	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.
	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]

Crystal data

[Zn3(C2H3O2)(C17H17N2O9)(H2O)6]·8H2O	V = 1718.7 (5) Å^3
Mr = 900.70	Z = 2
Triclinic, P1	F(000) = 932
Hall symbol: -P 1	Dx = 1.740 Mg m^−3
a = 10.0095 (18) Å	Mo Kα radiation, λ = 0.71073 Å
b = 13.293 (2) Å	µ = 2.17 mm^−1
c = 14.052 (3) Å	T = 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

Bruker SMART 1K CCD area-detector diffractometer	5932 independent reflections
Radiation source: fine-focus sealed tube	4769 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
ϕ and ω scans	θmax = 25.0°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	h = −11→10
Tmin = 0.477, Tmax = 0.562	k = −15→15
8459 measured reflections	l = −11→16

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.069	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.131	H-atom parameters constrained
S = 1.18	w = 1/[σ^2(Fo^2) + (0.0415P)^2] where P = (Fo^2 + 2Fc^2)/3
5932 reflections	(Δ/σ)max < 0.001
446 parameters	Δρmax = 0.92 e Å^−3
0 restraints	Δρmin = −0.88 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Zn1	0.62423 (8)	0.19713 (5)	0.36362 (5)	0.0189 (2)
Zn2	0.73994 (8)	0.24244 (5)	0.62603 (5)	0.0190 (2)
Zn3	0.5000	0.0000	0.0000	0.0223 (3)
Zn4	1.0000	0.5000	1.0000	0.0221 (3)
N1	0.7606 (5)	0.3152 (4)	0.2906 (4)	0.0188 (12)
N2	0.6389 (5)	0.3399 (4)	0.6913 (4)	0.0185 (12)
C1	0.8216 (6)	0.4544 (5)	0.4318 (4)	0.0192 (14)
C2	0.8481 (6)	0.5632 (5)	0.4319 (5)	0.0223 (15)
H2A	0.9065	0.6014	0.3903	0.027*
C3	0.7909 (7)	0.6180 (5)	0.4915 (5)	0.0232 (16)
C4	0.7048 (6)	0.5593 (5)	0.5511 (5)	0.0225 (15)
H4A	0.6656	0.5954	0.5921	0.027*
C5	0.6735 (6)	0.4498 (5)	0.5533 (5)	0.0199 (14)
C6	0.7353 (6)	0.3969 (4)	0.4945 (4)	0.0171 (14)
C7	0.8255 (7)	0.7379 (5)	0.4927 (6)	0.0364 (19)
H7B	0.7757	0.7621	0.5378	0.055*
H7C	0.7938	0.7531	0.4280	0.055*
H7D	0.9293	0.7757	0.5129	0.055*
C8	0.8809 (6)	0.3942 (5)	0.3642 (5)	0.0241 (15)
H8A	0.9481	0.4459	0.3313	0.029*
H8B	0.9346	0.3560	0.4022	0.029*
C9	0.6725 (6)	0.3681 (5)	0.2353 (5)	0.0216 (15)
H9A	0.6573	0.3431	0.1659	0.026*
H9B	0.7263	0.4462	0.2451	0.026*
C10	0.5239 (7)	0.3464 (5)	0.2638 (5)	0.0221 (15)
C11	0.8099 (6)	0.2517 (5)	0.2242 (5)	0.0214 (15)
H11A	0.8877	0.2321	0.2602	0.026*
H11B	0.8480	0.2946	0.1737	0.026*
C12	0.6824 (7)	0.1499 (5)	0.1775 (5)	0.0238 (16)
C13	0.5701 (6)	0.3857 (5)	0.6123 (5)	0.0209 (15)
H13A	0.5255	0.4322	0.6409	0.025*
H13B	0.4926	0.3264	0.5690	0.025*
C14	0.5279 (6)	0.2644 (4)	0.7353 (5)	0.0204 (15)
H14B	0.4523	0.2941	0.7418	0.025*
H14A	0.5720	0.2567	0.8006	0.025*
C15	0.4589 (7)	0.1535 (5)	0.6750 (5)	0.0200 (15)
C16	0.7506 (6)	0.4252 (4)	0.7643 (5)	0.0226 (15)
H16B	0.7147	0.4264	0.8251	0.027*
H16A	0.7655	0.4955	0.7410	0.027*
C17	0.8941 (7)	0.4095 (5)	0.7846 (5)	0.0211 (15)
C18	0.8567 (7)	0.0811 (5)	0.6591 (5)	0.0248 (16)
C19	0.9284 (8)	0.0038 (6)	0.6305 (6)	0.045 (2)
H19A	0.9254	−0.0460	0.6784	0.068*
H19B	1.0286	0.0442	0.6274	0.068*
H19C	0.8774	−0.0363	0.5674	0.068*
O1	0.7090 (4)	0.2895 (3)	0.4952 (3)	0.0186 (10)
O2	0.4772 (4)	0.2722 (3)	0.3127 (3)	0.0244 (11)
O3	0.4547 (5)	0.4039 (3)	0.2296 (4)	0.0377 (13)
O4	0.5844 (4)	0.1098 (3)	0.2248 (3)	0.0227 (10)
O5	0.6818 (4)	0.1117 (3)	0.0934 (3)	0.0270 (11)
O6	0.5335 (4)	0.1268 (3)	0.6202 (3)	0.0230 (10)
O7	0.3362 (5)	0.0945 (3)	0.6848 (3)	0.0289 (11)
O8	0.9127 (4)	0.3372 (3)	0.7291 (3)	0.0248 (11)
O9	0.9909 (4)	0.4693 (3)	0.8511 (3)	0.0265 (11)
O10	0.7732 (4)	0.1169 (3)	0.3978 (3)	0.0258 (11)
H10A	0.7497	0.0494	0.3826	0.039*
H10B	0.8100	0.1330	0.4581	0.039*
O11	0.4597 (4)	0.0807 (3)	0.4124 (3)	0.0254 (11)
H11C	0.4526	0.0844	0.4719	0.038*
H11D	0.4589	0.0183	0.3939	0.038*
O12	0.8322 (5)	0.1379 (3)	0.5932 (3)	0.0264 (11)
O13	0.8246 (5)	0.0865 (3)	0.7394 (3)	0.0330 (12)
O14	0.3864 (4)	0.1102 (3)	0.0164 (3)	0.0278 (11)
H14C	0.3411	0.1021	0.0633	0.042*
H14D	0.3261	0.0996	−0.0366	0.042*
O15	0.4248 (4)	−0.0777 (3)	0.1138 (3)	0.0273 (11)
H15A	0.4577	−0.0444	0.1711	0.041*
H15B	0.3372	−0.1190	0.1099	0.041*
O16	1.1492 (4)	0.4212 (3)	1.0153 (3)	0.0325 (12)
H16C	1.1534	0.3858	1.0634	0.049*
H16D	1.1300	0.3788	0.9630	0.049*
O17	1.1671 (5)	0.6451 (3)	1.0067 (4)	0.0352 (13)
H17A	1.1640	0.7080	1.0161	0.053*
H17B	1.2534	0.6502	1.0039	0.053*
O18	0.9875 (5)	0.0957 (4)	0.0994 (4)	0.0593 (17)
H18A	0.9292	0.0479	0.1256	0.089*
H18B	1.0464	0.0702	0.0793	0.089*
O19	0.5820 (5)	0.5477 (3)	0.1154 (4)	0.0398 (13)
H19D	0.5506	0.5104	0.1595	0.060*
H19E	0.5981	0.5079	0.0723	0.060*
O20	0.2607 (4)	0.0981 (3)	0.1778 (3)	0.0306 (11)
H20A	0.2335	0.0439	0.2086	0.046*
H20B	0.3229	0.1513	0.2164	0.046*
O21	0.4477 (5)	0.6693 (4)	0.0101 (3)	0.0372 (12)
H21A	0.4876	0.7305	−0.0082	0.056*
H21B	0.5072	0.6589	0.0552	0.056*
O22	0.1555 (5)	0.3179 (3)	0.1718 (4)	0.0417 (13)
H22A	0.2456	0.3288	0.1849	0.063*
H22B	0.1271	0.3278	0.2243	0.063*
O23	0.8712 (5)	0.1678 (3)	0.9368 (4)	0.0385 (13)
H23A	0.9155	0.1453	0.9825	0.058*
H23B	0.8983	0.1562	0.8842	0.058*
O24	0.2052 (5)	0.1005 (3)	0.8460 (3)	0.0346 (12)
H24A	0.1787	0.1547	0.8431	0.052*
H24B	0.2504	0.0975	0.8002	0.052*
O25	0.1444 (5)	0.2896 (4)	0.8356 (4)	0.0464 (14)
H25A	0.0700	0.2986	0.8047	0.070*
H25B	0.2187	0.3456	0.8362	0.070*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0191 (4)	0.0171 (4)	0.0187 (4)	0.0049 (3)	0.0038 (3)	−0.0009 (3)
Zn2	0.0205 (4)	0.0177 (4)	0.0190 (4)	0.0078 (3)	0.0034 (3)	0.0002 (3)
Zn3	0.0230 (6)	0.0235 (6)	0.0191 (6)	0.0084 (5)	0.0024 (5)	−0.0026 (5)
Zn4	0.0197 (6)	0.0198 (6)	0.0238 (7)	0.0064 (5)	−0.0005 (5)	−0.0026 (5)
N1	0.013 (3)	0.023 (3)	0.020 (3)	0.007 (2)	0.000 (2)	0.000 (2)
N2	0.023 (3)	0.012 (3)	0.020 (3)	0.006 (2)	0.007 (2)	−0.001 (2)
C1	0.015 (3)	0.023 (3)	0.014 (4)	0.004 (3)	−0.005 (3)	−0.002 (3)
C2	0.009 (3)	0.018 (3)	0.029 (4)	−0.004 (3)	−0.004 (3)	−0.002 (3)
C3	0.020 (4)	0.012 (3)	0.032 (4)	0.005 (3)	−0.005 (3)	−0.002 (3)
C4	0.020 (4)	0.024 (4)	0.021 (4)	0.009 (3)	−0.004 (3)	−0.007 (3)
C5	0.015 (3)	0.019 (3)	0.020 (4)	0.002 (3)	−0.002 (3)	−0.001 (3)
C6	0.015 (3)	0.014 (3)	0.017 (4)	0.004 (3)	−0.007 (3)	−0.002 (3)
C7	0.030 (4)	0.023 (4)	0.053 (5)	0.008 (3)	0.009 (4)	0.002 (4)
C8	0.015 (3)	0.027 (4)	0.025 (4)	0.003 (3)	−0.002 (3)	0.003 (3)
C9	0.021 (4)	0.017 (3)	0.020 (4)	0.003 (3)	−0.005 (3)	−0.001 (3)
C10	0.026 (4)	0.016 (3)	0.023 (4)	0.009 (3)	0.001 (3)	−0.001 (3)
C11	0.018 (4)	0.024 (3)	0.020 (4)	0.004 (3)	0.005 (3)	0.001 (3)
C12	0.029 (4)	0.025 (4)	0.021 (4)	0.017 (3)	−0.001 (3)	0.001 (3)
C13	0.012 (3)	0.023 (3)	0.026 (4)	0.006 (3)	0.001 (3)	−0.002 (3)
C14	0.019 (3)	0.023 (3)	0.021 (4)	0.008 (3)	0.007 (3)	0.000 (3)
C15	0.018 (4)	0.020 (3)	0.020 (4)	0.007 (3)	−0.001 (3)	0.002 (3)
C16	0.029 (4)	0.014 (3)	0.020 (4)	0.006 (3)	0.001 (3)	−0.008 (3)
C17	0.022 (4)	0.018 (3)	0.024 (4)	0.006 (3)	0.006 (3)	0.009 (3)
C18	0.021 (4)	0.025 (4)	0.026 (4)	0.009 (3)	−0.001 (3)	−0.004 (3)
C19	0.065 (6)	0.042 (5)	0.044 (5)	0.034 (4)	0.017 (4)	0.013 (4)
O1	0.026 (2)	0.013 (2)	0.016 (2)	0.0043 (18)	0.0065 (19)	0.0034 (18)
O2	0.019 (2)	0.024 (2)	0.032 (3)	0.009 (2)	0.006 (2)	0.003 (2)
O3	0.031 (3)	0.037 (3)	0.055 (4)	0.020 (2)	0.012 (3)	0.017 (3)
O4	0.017 (2)	0.027 (2)	0.020 (3)	0.0025 (19)	0.006 (2)	−0.003 (2)
O5	0.022 (3)	0.030 (3)	0.023 (3)	0.004 (2)	0.005 (2)	−0.004 (2)
O6	0.023 (2)	0.020 (2)	0.026 (3)	0.0073 (19)	0.007 (2)	−0.002 (2)
O7	0.025 (3)	0.024 (2)	0.038 (3)	0.006 (2)	0.013 (2)	0.001 (2)
O8	0.022 (2)	0.022 (2)	0.031 (3)	0.011 (2)	0.002 (2)	−0.005 (2)
O9	0.018 (2)	0.027 (2)	0.027 (3)	0.003 (2)	0.000 (2)	−0.009 (2)
O10	0.030 (3)	0.022 (2)	0.022 (3)	0.010 (2)	−0.003 (2)	−0.005 (2)
O11	0.028 (3)	0.021 (2)	0.027 (3)	0.006 (2)	0.009 (2)	0.001 (2)
O12	0.032 (3)	0.025 (2)	0.026 (3)	0.015 (2)	0.005 (2)	0.000 (2)
O13	0.045 (3)	0.031 (3)	0.023 (3)	0.013 (2)	0.010 (2)	0.001 (2)
O14	0.029 (3)	0.034 (3)	0.024 (3)	0.015 (2)	0.008 (2)	0.003 (2)
O15	0.026 (3)	0.031 (3)	0.017 (3)	0.003 (2)	0.000 (2)	−0.002 (2)
O16	0.031 (3)	0.035 (3)	0.033 (3)	0.019 (2)	−0.003 (2)	−0.004 (2)
O17	0.026 (3)	0.019 (2)	0.057 (4)	0.006 (2)	0.009 (2)	−0.004 (2)
O18	0.029 (3)	0.060 (3)	0.094 (5)	0.017 (3)	0.017 (3)	0.030 (4)
O19	0.045 (3)	0.034 (3)	0.042 (3)	0.015 (2)	0.008 (3)	0.009 (3)
O20	0.024 (3)	0.033 (3)	0.031 (3)	0.006 (2)	0.003 (2)	0.005 (2)
O21	0.025 (3)	0.044 (3)	0.037 (3)	0.008 (2)	−0.001 (2)	0.010 (3)
O22	0.031 (3)	0.045 (3)	0.049 (4)	0.015 (2)	0.004 (3)	0.003 (3)
O23	0.038 (3)	0.038 (3)	0.040 (3)	0.012 (2)	0.015 (2)	−0.003 (3)
O24	0.038 (3)	0.040 (3)	0.035 (3)	0.022 (2)	0.015 (2)	0.009 (2)
O25	0.035 (3)	0.045 (3)	0.065 (4)	0.021 (3)	0.007 (3)	0.012 (3)

Geometric parameters (Å, º)

Zn1—O1	2.036 (4)	C11—C12	1.523 (8)
Zn1—O11	2.078 (4)	C11—H11A	0.9800
Zn1—O2	2.106 (4)	C11—H11B	0.9800
Zn1—O4	2.113 (4)	C12—O5	1.256 (7)
Zn1—O10	2.126 (4)	C12—O4	1.257 (8)
Zn1—N1	2.134 (5)	C13—H13A	0.9800
Zn2—O12	1.984 (4)	C13—H13B	0.9800
Zn2—O1	1.990 (4)	C14—C15	1.525 (8)
Zn2—O8	2.036 (4)	C14—H14B	0.9800
Zn2—O6	2.094 (4)	C14—H14A	0.9800
Zn2—N2	2.143 (5)	C15—O7	1.244 (7)
Zn3—O15^i	2.061 (4)	C15—O6	1.269 (7)
Zn3—O15	2.061 (4)	C16—C17	1.507 (8)
Zn3—O5	2.091 (4)	C16—H16B	0.9800
Zn3—O5^i	2.091 (4)	C16—H16A	0.9800
Zn3—O14	2.164 (4)	C17—O9	1.237 (7)
Zn3—O14^i	2.164 (4)	C17—O8	1.282 (7)
Zn4—O17	2.057 (4)	C18—O13	1.227 (8)
Zn4—O17^ii	2.057 (4)	C18—O12	1.276 (8)
Zn4—O9^ii	2.088 (4)	C18—C19	1.510 (8)
Zn4—O9	2.088 (4)	C19—H19A	0.9700
Zn4—O16^ii	2.092 (4)	C19—H19B	0.9700
Zn4—O16	2.092 (4)	C19—H19C	0.9700
N1—C9	1.468 (7)	O10—H10A	0.8500
N1—C11	1.471 (7)	O10—H10B	0.8501
N1—C8	1.489 (7)	O11—H11C	0.8500
N2—C14	1.468 (7)	O11—H11D	0.8500
N2—C16	1.483 (7)	O14—H14C	0.8500
N2—C13	1.486 (7)	O14—H14D	0.8500
C1—C2	1.378 (8)	O15—H15A	0.8500
C1—C6	1.407 (8)	O15—H15B	0.8500
C1—C8	1.518 (8)	O16—H16C	0.8500
C2—C3	1.387 (8)	O16—H16D	0.8500
C2—H2A	0.9400	O17—H17A	0.8500
C3—C4	1.380 (9)	O17—H17B	0.8499
C3—C7	1.508 (8)	O18—H18A	0.8500
C4—C5	1.383 (8)	O18—H18B	0.8500
C4—H4A	0.9400	O19—H19D	0.8500
C5—C6	1.398 (8)	O19—H19E	0.8500
C5—C13	1.496 (8)	O20—H20A	0.8500
C6—O1	1.360 (6)	O20—H20B	0.8500
C7—H7B	0.9700	O21—H21A	0.8500
C7—H7C	0.9700	O21—H21B	0.8500
C7—H7D	0.9700	O22—H22A	0.8500
C8—H8A	0.9800	O22—H22B	0.8506
C8—H8B	0.9800	O23—H23A	0.8498
C9—C10	1.538 (8)	O23—H23B	0.8499
C9—H9A	0.9800	O24—H24A	0.8500
C9—H9B	0.9800	O24—H24B	0.8499
C10—O2	1.238 (7)	O25—H25A	0.8500
C10—O3	1.264 (7)	O25—H25B	0.8500
O1—Zn1—O11	94.90 (16)	N1—C8—H8A	109.5
O1—Zn1—O2	97.25 (16)	C1—C8—H8A	109.5
O11—Zn1—O2	89.60 (16)	N1—C8—H8B	109.5
O1—Zn1—O4	167.44 (16)	C1—C8—H8B	109.5
O11—Zn1—O4	94.77 (16)	H8A—C8—H8B	108.1
O2—Zn1—O4	90.82 (17)	N1—C9—C10	113.7 (5)
O1—Zn1—O10	88.64 (16)	N1—C9—H9A	108.8
O11—Zn1—O10	92.99 (16)	C10—C9—H9A	108.8
O2—Zn1—O10	173.35 (17)	N1—C9—H9B	108.8
O4—Zn1—O10	82.86 (16)	C10—C9—H9B	108.8
O1—Zn1—N1	92.85 (17)	H9A—C9—H9B	107.7
O11—Zn1—N1	168.87 (18)	O2—C10—O3	124.8 (6)
O2—Zn1—N1	81.49 (17)	O2—C10—C9	119.4 (5)
O4—Zn1—N1	78.80 (17)	O3—C10—C9	115.6 (6)
O10—Zn1—N1	95.18 (17)	N1—C11—C12	109.0 (5)
O12—Zn2—O1	97.96 (17)	N1—C11—H11A	109.9
O12—Zn2—O8	94.54 (17)	C12—C11—H11A	109.9
O1—Zn2—O8	119.23 (17)	N1—C11—H11B	109.9
O12—Zn2—O6	95.87 (16)	C12—C11—H11B	109.9
O1—Zn2—O6	99.32 (17)	H11A—C11—H11B	108.3
O8—Zn2—O6	138.07 (18)	O5—C12—O4	124.1 (6)
O12—Zn2—N2	167.19 (19)	O5—C12—C11	117.4 (6)
O1—Zn2—N2	94.66 (18)	O4—C12—C11	118.5 (6)
O8—Zn2—N2	81.15 (17)	N2—C13—C5	113.7 (5)
O6—Zn2—N2	79.83 (17)	N2—C13—H13A	108.8
O15^i—Zn3—O15	180.00 (12)	C5—C13—H13A	108.8
O15^i—Zn3—O5	88.07 (16)	N2—C13—H13B	108.8
O15—Zn3—O5	91.93 (16)	C5—C13—H13B	108.8
O15^i—Zn3—O5^i	91.93 (16)	H13A—C13—H13B	107.7
O15—Zn3—O5^i	88.07 (16)	N2—C14—C15	112.1 (5)
O5—Zn3—O5^i	180.0 (3)	N2—C14—H14B	109.2
O15^i—Zn3—O14	88.38 (16)	C15—C14—H14B	109.2
O15—Zn3—O14	91.63 (16)	N2—C14—H14A	109.2
O5—Zn3—O14	88.70 (16)	C15—C14—H14A	109.2
O5^i—Zn3—O14	91.30 (16)	H14B—C14—H14A	107.9
O15^i—Zn3—O14^i	91.62 (16)	O7—C15—O6	124.6 (5)
O15—Zn3—O14^i	88.37 (16)	O7—C15—C14	118.2 (5)
O5—Zn3—O14^i	91.30 (16)	O6—C15—C14	117.1 (5)
O5^i—Zn3—O14^i	88.70 (16)	N2—C16—C17	113.4 (5)
O14—Zn3—O14^i	180.0 (3)	N2—C16—H16B	108.9
O17—Zn4—O17^ii	180.000 (1)	C17—C16—H16B	108.9
O17—Zn4—O9^ii	89.67 (18)	N2—C16—H16A	108.9
O17^ii—Zn4—O9^ii	90.33 (17)	C17—C16—H16A	108.9
O17—Zn4—O9	90.33 (17)	H16B—C16—H16A	107.7
O17^ii—Zn4—O9	89.67 (18)	O9—C17—O8	122.6 (6)
O9^ii—Zn4—O9	180.000 (1)	O9—C17—C16	119.2 (6)
O17—Zn4—O16^ii	90.14 (17)	O8—C17—C16	118.2 (5)
O17^ii—Zn4—O16^ii	89.86 (17)	O13—C18—O12	123.9 (6)
O9^ii—Zn4—O16^ii	84.85 (17)	O13—C18—C19	121.4 (7)
O9—Zn4—O16^ii	95.15 (17)	O12—C18—C19	114.6 (6)
O17—Zn4—O16	89.86 (17)	C18—C19—H19A	109.5
O17^ii—Zn4—O16	90.14 (17)	C18—C19—H19B	109.5
O9^ii—Zn4—O16	95.15 (17)	H19A—C19—H19B	109.5
O9—Zn4—O16	84.85 (17)	C18—C19—H19C	109.5
O16^ii—Zn4—O16	180.000 (2)	H19A—C19—H19C	109.5
C9—N1—C11	110.3 (5)	H19B—C19—H19C	109.5
C9—N1—C8	111.4 (4)	C6—O1—Zn2	115.5 (4)
C11—N1—C8	113.5 (5)	C6—O1—Zn1	115.4 (4)
C9—N1—Zn1	108.4 (4)	Zn2—O1—Zn1	128.74 (19)
C11—N1—Zn1	104.0 (3)	C10—O2—Zn1	115.1 (4)
C8—N1—Zn1	108.8 (4)	C12—O4—Zn1	112.9 (4)
C14—N2—C16	112.5 (5)	C12—O5—Zn3	124.8 (4)
C14—N2—C13	110.4 (5)	C15—O6—Zn2	114.7 (4)
C16—N2—C13	112.2 (4)	C17—O8—Zn2	117.5 (4)
C14—N2—Zn2	104.9 (3)	C17—O9—Zn4	132.3 (4)
C16—N2—Zn2	108.9 (4)	Zn1—O10—H10A	122.2
C13—N2—Zn2	107.6 (4)	Zn1—O10—H10B	108.5
C2—C1—C6	119.3 (6)	H10A—O10—H10B	108.8
C2—C1—C8	121.7 (6)	Zn1—O11—H11C	121.0
C6—C1—C8	119.0 (5)	Zn1—O11—H11D	109.4
C1—C2—C3	121.9 (6)	H11C—O11—H11D	109.0
C1—C2—H2A	119.0	C18—O12—Zn2	116.9 (4)
C3—C2—H2A	119.0	Zn3—O14—H14C	114.9
C4—C3—C2	117.5 (5)	Zn3—O14—H14D	106.2
C4—C3—C7	121.6 (6)	H14C—O14—H14D	109.1
C2—C3—C7	120.9 (6)	Zn3—O15—H15A	118.4
C3—C4—C5	123.1 (6)	Zn3—O15—H15B	123.0
C3—C4—H4A	118.5	H15A—O15—H15B	109.0
C5—C4—H4A	118.5	Zn4—O16—H16C	118.3
C4—C5—C6	118.4 (6)	Zn4—O16—H16D	106.6
C4—C5—C13	122.3 (6)	H16C—O16—H16D	108.9
C6—C5—C13	119.2 (5)	Zn4—O17—H17A	127.2
O1—C6—C5	120.5 (5)	Zn4—O17—H17B	123.4
O1—C6—C1	119.8 (5)	H17A—O17—H17B	109.3
C5—C6—C1	119.7 (5)	H18A—O18—H18B	109.1
C3—C7—H7B	109.5	H19D—O19—H19E	109.2
C3—C7—H7C	109.5	H20A—O20—H20B	109.2
H7B—C7—H7C	109.5	H21A—O21—H21B	109.1
C3—C7—H7D	109.5	H22A—O22—H22B	108.9
H7B—C7—H7D	109.5	H23A—O23—H23B	109.4
H7C—C7—H7D	109.5	H24A—O24—H24B	108.8
N1—C8—C1	110.5 (5)	H25A—O25—H25B	108.9
O1—Zn1—N1—C9	−105.6 (4)	N2—C16—C17—O9	−172.8 (6)
O11—Zn1—N1—C9	28.4 (11)	N2—C16—C17—O8	10.2 (8)
O2—Zn1—N1—C9	−8.7 (3)	C5—C6—O1—Zn2	−50.4 (6)
O4—Zn1—N1—C9	83.8 (4)	C1—C6—O1—Zn2	131.7 (5)
O10—Zn1—N1—C9	165.5 (4)	C5—C6—O1—Zn1	123.8 (5)
O1—Zn1—N1—C11	137.0 (3)	C1—C6—O1—Zn1	−54.1 (6)
O11—Zn1—N1—C11	−89.0 (9)	O12—Zn2—O1—C6	−139.7 (4)
O2—Zn1—N1—C11	−126.1 (4)	O8—Zn2—O1—C6	−39.9 (4)
O4—Zn1—N1—C11	−33.6 (3)	O6—Zn2—O1—C6	122.9 (4)
O10—Zn1—N1—C11	48.1 (4)	N2—Zn2—O1—C6	42.5 (4)
O1—Zn1—N1—C8	15.7 (4)	O12—Zn2—O1—Zn1	47.0 (3)
O11—Zn1—N1—C8	149.8 (8)	O8—Zn2—O1—Zn1	146.8 (2)
O2—Zn1—N1—C8	112.6 (4)	O6—Zn2—O1—Zn1	−50.3 (3)
O4—Zn1—N1—C8	−154.8 (4)	N2—Zn2—O1—Zn1	−130.7 (3)
O10—Zn1—N1—C8	−73.2 (4)	O11—Zn1—O1—C6	−131.7 (4)
O12—Zn2—N2—C14	−43.8 (10)	O2—Zn1—O1—C6	−41.5 (4)
O1—Zn2—N2—C14	126.2 (4)	O4—Zn1—O1—C6	88.1 (8)
O8—Zn2—N2—C14	−114.9 (4)	O10—Zn1—O1—C6	135.4 (4)
O6—Zn2—N2—C14	27.5 (4)	N1—Zn1—O1—C6	40.3 (4)
O12—Zn2—N2—C16	76.9 (9)	O11—Zn1—O1—Zn2	41.6 (3)
O1—Zn2—N2—C16	−113.1 (4)	O2—Zn1—O1—Zn2	131.8 (3)
O8—Zn2—N2—C16	5.8 (4)	O4—Zn1—O1—Zn2	−98.6 (7)
O6—Zn2—N2—C16	148.2 (4)	O10—Zn1—O1—Zn2	−51.3 (3)
O12—Zn2—N2—C13	−161.3 (7)	N1—Zn1—O1—Zn2	−146.4 (3)
O1—Zn2—N2—C13	8.7 (3)	O3—C10—O2—Zn1	−177.4 (5)
O8—Zn2—N2—C13	127.6 (4)	C9—C10—O2—Zn1	6.8 (7)
O6—Zn2—N2—C13	−90.0 (3)	O1—Zn1—O2—C10	93.0 (4)
C6—C1—C2—C3	−0.6 (9)	O11—Zn1—O2—C10	−172.1 (4)
C8—C1—C2—C3	178.2 (6)	O4—Zn1—O2—C10	−77.3 (4)
C1—C2—C3—C4	−0.4 (9)	O10—Zn1—O2—C10	−59.1 (15)
C1—C2—C3—C7	177.9 (6)	N1—Zn1—O2—C10	1.2 (4)
C2—C3—C4—C5	−0.3 (9)	O5—C12—O4—Zn1	180.0 (5)
C7—C3—C4—C5	−178.6 (6)	C11—C12—O4—Zn1	−0.5 (7)
C3—C4—C5—C6	1.9 (9)	O1—Zn1—O4—C12	−29.1 (10)
C3—C4—C5—C13	−174.8 (6)	O11—Zn1—O4—C12	−169.2 (4)
C4—C5—C6—O1	179.2 (5)	O2—Zn1—O4—C12	101.1 (4)
C13—C5—C6—O1	−4.0 (8)	O10—Zn1—O4—C12	−76.8 (4)
C4—C5—C6—C1	−2.9 (9)	N1—Zn1—O4—C12	19.9 (4)
C13—C5—C6—C1	173.9 (5)	O4—C12—O5—Zn3	16.2 (9)
C2—C1—C6—O1	−179.8 (5)	C11—C12—O5—Zn3	−163.3 (4)
C8—C1—C6—O1	1.4 (8)	O15^i—Zn3—O5—C12	143.7 (5)
C2—C1—C6—C5	2.3 (9)	O15—Zn3—O5—C12	−36.3 (5)
C8—C1—C6—C5	−176.6 (5)	O5^i—Zn3—O5—C12	−97 (68)
C9—N1—C8—C1	56.3 (7)	O14—Zn3—O5—C12	55.3 (5)
C11—N1—C8—C1	−178.4 (5)	O14^i—Zn3—O5—C12	−124.7 (5)
Zn1—N1—C8—C1	−63.2 (5)	O7—C15—O6—Zn2	−177.0 (5)
C2—C1—C8—N1	−112.6 (6)	C14—C15—O6—Zn2	0.7 (7)
C6—C1—C8—N1	66.2 (7)	O12—Zn2—O6—C15	151.2 (4)
C11—N1—C9—C10	127.4 (5)	O1—Zn2—O6—C15	−109.7 (4)
C8—N1—C9—C10	−105.5 (6)	O8—Zn2—O6—C15	47.7 (5)
Zn1—N1—C9—C10	14.2 (6)	N2—Zn2—O6—C15	−16.6 (4)
N1—C9—C10—O2	−14.9 (8)	O9—C17—O8—Zn2	178.1 (5)
N1—C9—C10—O3	169.0 (5)	C16—C17—O8—Zn2	−5.0 (7)
C9—N1—C11—C12	−74.0 (6)	O12—Zn2—O8—C17	−168.4 (4)
C8—N1—C11—C12	160.1 (5)	O1—Zn2—O8—C17	89.8 (4)
Zn1—N1—C11—C12	42.1 (5)	O6—Zn2—O8—C17	−64.4 (5)
N1—C11—C12—O5	149.6 (5)	N2—Zn2—O8—C17	−0.6 (4)
N1—C11—C12—O4	−29.9 (8)	O8—C17—O9—Zn4	−124.3 (6)
C14—N2—C13—C5	−170.9 (5)	C16—C17—O9—Zn4	58.8 (8)
C16—N2—C13—C5	62.7 (6)	O17—Zn4—O9—C17	−158.4 (6)
Zn2—N2—C13—C5	−57.0 (5)	O17^ii—Zn4—O9—C17	21.6 (6)
C4—C5—C13—N2	−116.0 (6)	O9^ii—Zn4—O9—C17	72 (100)
C6—C5—C13—N2	67.3 (7)	O16^ii—Zn4—O9—C17	−68.2 (6)
C16—N2—C14—C15	−153.4 (5)	O16—Zn4—O9—C17	111.8 (6)
C13—N2—C14—C15	80.5 (6)	O13—C18—O12—Zn2	1.3 (8)
Zn2—N2—C14—C15	−35.1 (5)	C19—C18—O12—Zn2	−179.4 (4)
N2—C14—C15—O7	−157.2 (5)	O1—Zn2—O12—C18	−173.4 (4)
N2—C14—C15—O6	24.9 (8)	O8—Zn2—O12—C18	66.2 (4)
C14—N2—C16—C17	106.2 (6)	O6—Zn2—O12—C18	−73.1 (4)
C13—N2—C16—C17	−128.6 (5)	N2—Zn2—O12—C18	−3.5 (10)
Zn2—N2—C16—C17	−9.6 (6)

Symmetry codes: (i) −x+1, −y, −z; (ii) −x+2, −y+1, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O25—H25B···O19^iii	0.85	1.99	2.789 (6)	157
O25—H25A···O8^iv	0.85	1.99	2.835 (6)	173
O24—H24B···O7	0.85	1.96	2.803 (6)	173
O24—H24A···O25	0.85	1.94	2.790 (6)	172
O23—H23B···O13	0.85	2.09	2.818 (7)	144
O23—H23A···O18^v	0.85	1.93	2.772 (7)	169
O22—H22A···O3	0.85	1.96	2.772 (6)	160
O21—H21B···O19	0.85	2.04	2.786 (6)	146
O21—H21A···O14^vi	0.85	2.08	2.910 (6)	165
O20—H20B···O2	0.85	2.04	2.887 (6)	177
O20—H20A···O13^vii	0.85	1.87	2.710 (6)	172
O19—H19E···O21^vi	0.85	2.42	3.182 (6)	150
O19—H19D···O3	0.85	1.85	2.687 (7)	166
O18—H18B···O20^viii	0.85	2.26	2.768 (6)	119
O18—H18A···O24^vii	0.85	2.07	2.893 (7)	162
O17—H17B···O21^ix	0.85	1.86	2.707 (6)	174
O17—H17A···O23^ii	0.85	1.91	2.734 (6)	165
O16—H16D···O25^viii	0.85	2.14	2.964 (6)	164
O16—H16C···O22^ix	0.85	1.82	2.667 (7)	175
O15—H15B···O23^vii	0.85	1.94	2.737 (6)	155
O15—H15A···O4	0.85	2.02	2.678 (5)	133
O14—H14D···O24^x	0.85	1.89	2.728 (6)	171
O14—H14C···O20	0.85	1.91	2.752 (6)	173
O11—H11D···O6^vii	0.85	1.95	2.793 (5)	168
O11—H11C···O6	0.85	2.08	2.867 (6)	154
O10—H10B···O12	0.85	1.87	2.691 (6)	162
O10—H10A···O7^vii	0.85	1.92	2.741 (5)	163

Symmetry codes: (ii) −x+2, −y+1, −z+2; (iii) −x+1, −y+1, −z+1; (iv) x−1, 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, z−1.