Hydro­thermal synthesis and extended structure of poly[aqua­(μ₅-ethyl­ene­diamine­tetra­acetato)dizinc(II)]

In the extended structure of the title compound, [Zn₂(C₁₀H₁₂N₂O₈)(H₂O)], prepared under hydro­thermal conditions, there are two distinct Zn^II sites. The first, with octa­hedral geometry, bonds to two N and three O atoms from one ethyl­ene­diamine­tetra­acetate tetraanion (EDTA) and one water mol­ecule. The second, with tetra­hedral geometry, coordinates to O atoms from four different EDTA ligands. The EDTA ligand almost encapsulates the octa­hedral Zn^II ion and binds to four symmetry-related tetra­hedral Zn^II ions, hence generating the extended structure. One noncoordinated O-atom site on the EDTA ligand connects to the water mol­ecule by hydrogen bonding. Structural comparisons are made with other compounds containing zinc, EDTA and water.

S1. Comment

For the hydrothermal synthesis of sparingly soluble materials, it is essential to utilize a mineralizer or coordinating agent to aid in maintaining optimum concentrations of metal ions for more controlled crystal growth (Rabenau, 1985). In this study, the ethylenediaminetetraacetate tetraanion, EDTA, has been successfully used in our efforts to improve the synthetic reproducibility and increase the size of ZnO crystals grown in subcritical hydrothermal conditions of approximately 473 K and 15 atm (1 atm = 101325 Pa) (DiLeo et al., 2004). Crystals of [Zn₂(EDTA)(H₂O)]_n, (I), were grown in acidic conditions, unusual in this research and corresponding to a thermodynamic phase space where ZnO is less likely to precipitate. Thus, the water-insoluble title compound was discovered.

The asymmetric unit of (I), along with coordination around the distorted Zn^II tetrahedron, is shown in Fig. 1, and selected bond distances and angles are included in Table 1. There are two distinct Zn^II sites in this structure. Atom Zn1 connects to the EDTA tetraanion and the water molecule in a distorted octahedral environment. Atom N2, and the two acetate groups bonded to it via atoms O5 and O7, bonds to Zn1. The other N atom, N1, and one of its acetate groups connect to atom Zn1 via atom O3. The sixth bond to atom Zn1 involves atom O9 of the water molecule. The Zn—O bond distances at the octahedral atom Zn1 are in the range 2.00–2.13 Å, and the lower value corresponds to water coordination. Four of the remaining five EDTA O atoms (O1, O4ⁱⁱ, O6ⁱⁱⁱ and O8ⁱ; see Table 1 for symmetry operations) bond in a distorted tetrahedral coordination to atom Zn2. The Zn—O bond distances at the tetrahedral atom Zn2 are in the range 1.95–2.00 Å. At the octahedral atom Zn1, the trans and cis angles are in the ranges 160.85 (6)–165.78 (6) and 77.50 (7)–110.60 (7)°, respectively, while at the tetrahedral atom Zn2, the range is 95.82 (7)–120.87 (7)°.

Fig. 2 illustrates the hydrogen bonding. Atom O2 is the only EDTA O atom that is uncoordinated to Zn^II and within hydrogen-bonding distance of water atom H9C. Atom O6, which bonds to Zn2, is also within hydrogen-bonding distance of H9D, the second water H atom. Upon inspection of the displacement parameters, it is clear that U₁₁ for O2 is roughly twice that of other atoms in the structure. Because it is the only uncoordinated EDTA O atom, it is reasonable to expect that it would have a higher range of motion.

The polyhedral arrangement along b is illustrated in Fig. 3. Both polyhedra form zigzag chains along b and c, and the tetrahedra form AB-like layers along b and c. Within the structure, there are open channels of 2–3 Å along b, approximated using ATOMS (Dowty, 2006).

Two other related compounds are [Zn₃(HEDTA)₂(H₂O)₆] (Sadikov et al., 2004) and [Zn₂(EDTA)(H₂O)₄].2H₂O (Pozhidaev et al., 1973; Escrivá et al., 1984). Both contain only octahedrally coordinated zinc. In [Zn₃(HEDTA)₂(H₂O)₆], two of the zinc sites coordinate to five O-atom sites on single HEDTA ions and one H₂O molecule. The remaining O-atom site on each of these HEDTA ions coordinates to the third Zn atom, sandwiched in between the other two Zn atoms and coordinating additionally to four H₂O molecules. For [Zn₂(EDTA)(H₂O)₄].2H₂O, one Zn atom is coordinated entirely by a single HEDTA ligand, and the other Zn atom by two H₂O molecules and two O atoms from two distinct HEDTA ions; two solvent water molecules connect to the structure by hydrogen bonding. Similarly to the title compound, both of these related structures are extended such that some of the EDTA carboxylate groups serve to bridge Zn^II ions throughout the structure.

With fewer water molecules per Zn atom (H₂O:Zn ratio of 1:2, compared with 1:1 and 2:1 for the related structures), the title compound represents a denser version of other extended compounds containing zinc, EDTA and water. The previously reported trinuclear and dinuclear compounds have densities of 1.897 and 1.91 Mg m^-3, respectively, whereas Zn₂EDTA(H₂O) has a calculated density of 2.15 Mg m^-3.

S2. Experimental

Several samples were prepared to ensure reproducibility. Zinc chloride, ZnCl₂ (approximately 0.116 g; Aldrich, 98+%), was dissolved in distilled water (10.0 g). To this mixture, disodium dihydrogen ethylenediaminetetraacetate dihydrate, Na₂H₂EDTA.2H₂O (0.27 g; Aldrich, 99+%), was added with stirring. Finally, 1.000 M potassium hydroxide, KOH (1.2 g; Riedel-deHaën Fixanal solution), was added and the entire mixture was allowed to dissolve while stirring. After measuring a pH 3.0–3.4, the colorless solution was placed in a Parr acid-digestion vessel, with a Teflon liner capacity of 25 ml. The autoclave was closed and placed in a 473 K mechanical convection oven for 7 d. The syntheses produced between one and several crystals, ranging in size from approximately 1 to 5 mm along the longest edge. The density of the crystals was measured at ambient temperature using the technique of neutral buoyancy. The sample was placed in a known mass of bromoform (Aldrich, 99+%) and to that chloroform (Aldrich, 99.8%) was added until the crystals were suspended in the liquid mixture. The density of the bromoform–chloroform mixture was found to be 2.07 (3) Mg m^-3, reasonably close to the calculated value from the X-ray structure but differing from that value by an amount that equates to approximately one water molecule. The bulk of the crystals were cloudy except near the edges, which may indicate that water disassociates from the crystal center, producing a lower bulk density compared with the transparent edges. The sample of (I) used for X-ray diffraction was taken from the transparent portion of one of the larger crystals.

S3. Refinement

Reflection data for two twin components were processed in SAINT-Plus (Bruker, 2003) and the lesser component was eventually omitted because of weak intensities. Flack parameter (Flack, 1983) refinement to 0.498 (9) indicated racemic twinning, as expected from the use of non-chiral reagents. In the space group assignment, centrosymmetric Pnam and noncentrosymmetric Pna2₁ were investigated, but Pnam did not result in an ordered structure. This result is consistent with the estimated |E*E-1| = 0.766 within XPREP (SHELXTL; Sheldrick, 2008), which suggested a noncentrosymmetric space group. The two H atoms (H9C and H9D) bonded to atom O9 were then identified. Bond distances O9—H9C and O9—H9D were restrained to 0.84 (1) Å, and the H9C···H9D separation restrained to 1.38 (1) Å. The CH₂ H atoms were constrained to idealized geometry, with C—H = 0.99 Å. For all H atoms, U_iso(H) = 1.2U_eq(C) or 1.5U_eq(O).

Computing details

Data collection: SMART (Bruker, 2003); cell refinement: SMART (Bruker, 2003); data reduction: SAINT-Plus (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and ATOMS (Dowty, 2006); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The asymmetric unit and connectivity for (I), highlighting the Zn-centered tetrahedron and four associated Zn–EDTA species. Only H atoms of the water molecule are shown. Displacement ellipsoids are drawn at the 50% probability level. Primed, double-primed and triple-primed atoms are generated by the symmetry operators ?, ?, ? [Please provide symmetry codes]
	Fig. 2. The partial structure of (I), viewed along [100], with hydrogen bonds shown as thin lines. The Zn-centered octahedron is in the center and connection to other polyhedra is illustrated via EDTA and hydrogen bonding. Atoms H9C and H9D of the water molecule are closest to atoms O2 and O6, respectively. [Symmetry codes: (i) ?; (ii) ?; (iii) ?; (iv) ?; (v) ? Please provide symmetry codes]
	Fig. 3. The unit cell and polyhedral arrangements in (I), viewed along [010], illustrating the zig-zag chains of octahedra and tetrahedra, and the open channels between tetrahedra. Hydrogen bonding is indicated by dashed lines.

poly[aqua(µ₅-ethylenediaminetetraacetato)dizinc(II)]

Crystal data

[Zn2(C10H12N2O8)(H2O)]	F(000) = 880
Mr = 436.97	Dx = 2.149 Mg m^−3 Dm = 2.07 Mg m^−3 Dm measured by neutral buoyancy
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 5304 reflections
a = 12.7099 (8) Å	θ = 2.4–31.5°
b = 11.2854 (7) Å	µ = 3.61 mm^−1
c = 9.4153 (6) Å	T = 100 K
V = 1350.50 (15) Å^3	Block, colourless
Z = 4	0.13 × 0.10 × 0.03 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer	4275 independent reflections
Radiation source: fine-focus sealed tube	4049 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
ϕ and ω scans	θmax = 31.6°, θmin = 2.4°
Absorption correction: multi-scan (SADABS in SAINT-Plus; Bruker, 2003)	h = −18→18
Tmin = 0.336, Tmax = 0.434	k = −16→16
17189 measured reflections	l = −13→13

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.025	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.056	w = 1/[σ^2(Fo^2) + (0.0289P)^2 + 0.3P] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max = 0.001
4275 reflections	Δρmax = 0.83 e Å^−3
215 parameters	Δρmin = −0.40 e Å^−3
4 restraints	Absolute structure: Flack (1983), with 1897 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.498 (9)

Special details

Experimental. Reflection data for two components were processed in SAINT (Bruker), with the lessor component omitted because of weak intensities. Flack parameter refinement to about 0.50 indicated racemic twinning as expected from non-chiral reagents, and this twinning was modeled with the SHELXL commands: twin 1 0 0 0 1 0 0 0 -1 -2 BASF 0.49780

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	0.576933 (16)	0.679170 (17)	0.60875 (3)	0.00880 (5)
Zn2	0.243763 (16)	0.903194 (17)	0.09567 (3)	0.00850 (5)
O1	0.36367 (13)	0.84202 (14)	0.20532 (18)	0.0136 (3)
O2	0.33246 (14)	0.65788 (14)	0.13424 (19)	0.0198 (4)
O3	0.67170 (12)	0.82903 (13)	0.57773 (16)	0.0122 (3)
O4	0.68401 (13)	0.99873 (13)	0.45480 (17)	0.0122 (3)
O5	0.45217 (11)	0.55623 (12)	0.62026 (19)	0.0120 (3)
O6	0.31393 (13)	0.50443 (14)	0.75089 (16)	0.0121 (3)
O7	0.63842 (13)	0.64397 (14)	0.81519 (17)	0.0133 (3)
O8	0.63749 (12)	0.71150 (14)	1.03816 (17)	0.0122 (3)
N1	0.49141 (15)	0.76664 (17)	0.43347 (19)	0.0081 (4)
N2	0.46998 (16)	0.77732 (17)	0.7457 (2)	0.0090 (3)
C1	0.40180 (17)	0.82545 (19)	0.5083 (2)	0.0109 (4)
H1A	0.3435	0.7679	0.5183	0.013*
H1B	0.3761	0.8920	0.4492	0.013*
C2	0.43051 (16)	0.87227 (19)	0.6538 (2)	0.0102 (4)
H2A	0.4851	0.9343	0.6441	0.012*
H2B	0.3677	0.9088	0.6981	0.012*
C3	0.45282 (17)	0.68202 (18)	0.3250 (2)	0.0098 (4)
H3A	0.4174	0.6159	0.3750	0.012*
H3B	0.5147	0.6484	0.2755	0.012*
C4	0.37735 (17)	0.72952 (19)	0.2128 (2)	0.0109 (4)
C5	0.56361 (17)	0.85515 (19)	0.3711 (2)	0.0102 (4)
H5A	0.5224	0.9242	0.3377	0.012*
H5B	0.5996	0.8200	0.2879	0.012*
C6	0.64552 (16)	0.89652 (18)	0.4779 (2)	0.0095 (4)
C7	0.38511 (17)	0.69437 (19)	0.7923 (2)	0.0117 (4)
H7A	0.3160	0.7329	0.7774	0.014*
H7B	0.3930	0.6792	0.8953	0.014*
C8	0.38620 (17)	0.57741 (18)	0.7144 (2)	0.0099 (4)
C9	0.53422 (18)	0.8147 (2)	0.8675 (2)	0.0110 (4)
H9A	0.4881	0.8348	0.9487	0.013*
H9B	0.5753	0.8862	0.8421	0.013*
C10	0.60868 (16)	0.71431 (19)	0.9090 (2)	0.0108 (4)
O9	0.67690 (13)	0.55795 (14)	0.53292 (17)	0.0116 (3)
H9C	0.674 (2)	0.4951 (15)	0.581 (2)	0.017*
H9D	0.686 (2)	0.540 (2)	0.4473 (12)	0.017*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.00918 (9)	0.00890 (9)	0.00833 (10)	0.00068 (7)	−0.00011 (11)	0.00017 (11)
Zn2	0.00852 (9)	0.00950 (9)	0.00749 (9)	−0.00038 (7)	−0.00055 (11)	−0.00007 (11)
O1	0.0141 (7)	0.0115 (7)	0.0153 (8)	0.0011 (6)	−0.0039 (6)	−0.0001 (6)
O2	0.0256 (8)	0.0137 (7)	0.0202 (10)	0.0039 (6)	−0.0128 (7)	−0.0043 (6)
O3	0.0110 (6)	0.0124 (6)	0.0131 (8)	−0.0006 (5)	−0.0023 (6)	0.0018 (6)
O4	0.0145 (7)	0.0115 (7)	0.0106 (7)	−0.0043 (6)	−0.0003 (6)	0.0000 (6)
O5	0.0137 (6)	0.0111 (6)	0.0112 (7)	−0.0011 (5)	0.0011 (7)	0.0009 (6)
O6	0.0125 (7)	0.0150 (7)	0.0090 (7)	−0.0034 (6)	−0.0015 (6)	−0.0002 (6)
O7	0.0148 (7)	0.0146 (7)	0.0104 (7)	0.0050 (6)	−0.0003 (6)	0.0000 (6)
O8	0.0118 (7)	0.0142 (7)	0.0106 (7)	0.0020 (6)	−0.0024 (6)	−0.0009 (6)
N1	0.0086 (8)	0.0078 (8)	0.0078 (8)	0.0004 (6)	0.0001 (6)	−0.0024 (6)
N2	0.0094 (8)	0.0087 (8)	0.0089 (8)	0.0000 (7)	−0.0024 (7)	0.0007 (6)
C1	0.0090 (9)	0.0124 (9)	0.0113 (10)	0.0014 (8)	0.0013 (8)	−0.0015 (8)
C2	0.0094 (9)	0.0119 (9)	0.0092 (8)	0.0011 (7)	−0.0016 (7)	0.0016 (7)
C3	0.0127 (9)	0.0068 (8)	0.0097 (9)	−0.0001 (7)	−0.0023 (8)	−0.0010 (7)
C4	0.0108 (9)	0.0132 (9)	0.0086 (9)	0.0010 (8)	0.0005 (7)	0.0005 (7)
C5	0.0100 (9)	0.0119 (9)	0.0087 (9)	−0.0014 (8)	−0.0012 (7)	0.0020 (7)
C6	0.0088 (8)	0.0103 (9)	0.0094 (9)	0.0012 (7)	0.0021 (7)	−0.0013 (7)
C7	0.0109 (9)	0.0128 (10)	0.0115 (9)	−0.0021 (8)	0.0003 (8)	−0.0001 (8)
C8	0.0108 (9)	0.0112 (9)	0.0078 (9)	0.0003 (7)	−0.0036 (7)	0.0010 (7)
C9	0.0120 (10)	0.0107 (9)	0.0103 (9)	0.0010 (8)	−0.0023 (8)	−0.0019 (8)
C10	0.0088 (9)	0.0124 (9)	0.0112 (9)	−0.0013 (7)	−0.0003 (7)	0.0022 (8)
O9	0.0148 (7)	0.0112 (7)	0.0089 (7)	0.0003 (6)	0.0014 (6)	0.0008 (6)

Geometric parameters (Å, º)

Zn1—O9	1.9989 (16)	N2—C9	1.469 (3)
Zn1—O3	2.0967 (15)	N2—C7	1.494 (3)
Zn1—O5	2.1098 (15)	C1—C2	1.514 (3)
Zn1—O7	2.1322 (17)	C1—H1A	0.9900
Zn1—N2	2.177 (2)	C1—H1B	0.9900
Zn1—N1	2.209 (2)	C2—H2A	0.9900
Zn2—O8^i	1.9476 (16)	C2—H2B	0.9900
Zn2—O4^ii	1.9563 (16)	C3—C4	1.524 (3)
Zn2—O1	1.9660 (16)	C3—H3A	0.9900
Zn2—O6^iii	1.9947 (15)	C3—H3B	0.9900
O1—C4	1.283 (3)	C5—C6	1.521 (3)
O2—C4	1.235 (3)	C5—H5A	0.9900
O3—C6	1.254 (3)	C5—H5B	0.9900
O4—C6	1.272 (2)	C7—C8	1.510 (3)
O5—C8	1.243 (3)	C7—H7A	0.9900
O6—C8	1.281 (3)	C7—H7B	0.9900
O7—C10	1.246 (3)	C9—C10	1.528 (3)
O8—C10	1.270 (3)	C9—H9A	0.9900
N1—C3	1.482 (3)	C9—H9B	0.9900
N1—C5	1.478 (3)	O9—H9C	0.844 (9)
N1—C1	1.494 (3)	O9—H9D	0.839 (9)
N2—C2	1.466 (3)
O9—Zn1—O3	97.88 (6)	N2—C2—C1	111.21 (17)
O9—Zn1—O5	92.64 (6)	N2—C2—H2A	109.4
O3—Zn1—O5	165.78 (6)	C1—C2—H2A	109.4
O9—Zn1—O7	88.00 (6)	N2—C2—H2B	109.4
O3—Zn1—O7	93.83 (6)	C1—C2—H2B	109.4
O5—Zn1—O7	96.09 (7)	H2A—C2—H2B	108.0
O9—Zn1—N2	163.10 (7)	N1—C3—C4	117.35 (17)
O3—Zn1—N2	91.77 (7)	N1—C3—H3A	108.0
O5—Zn1—N2	80.49 (7)	C4—C3—H3A	108.0
O7—Zn1—N2	77.50 (7)	N1—C3—H3B	108.0
O9—Zn1—N1	110.60 (7)	C4—C3—H3B	108.0
O3—Zn1—N1	79.52 (6)	H3A—C3—H3B	107.2
O5—Zn1—N1	87.85 (7)	O2—C4—O1	123.5 (2)
O7—Zn1—N1	160.85 (6)	O2—C4—C3	118.38 (19)
N2—Zn1—N1	84.72 (7)	O1—C4—C3	118.10 (19)
O8^i—Zn2—O4^ii	120.87 (7)	N1—C5—C6	111.69 (17)
O8^i—Zn2—O1	116.76 (6)	N1—C5—H5A	109.3
O4^ii—Zn2—O1	101.01 (7)	C6—C5—H5A	109.3
O8^i—Zn2—O6^iii	109.23 (7)	N1—C5—H5B	109.3
O4^ii—Zn2—O6^iii	110.19 (7)	C6—C5—H5B	109.3
O1—Zn2—O6^iii	95.82 (7)	H5A—C5—H5B	107.9
C4—O1—Zn2	118.76 (14)	O3—C6—O4	125.2 (2)
C6—O3—Zn1	116.21 (13)	O3—C6—C5	119.38 (18)
C6—O4—Zn2^iv	125.28 (14)	O4—C6—C5	115.36 (19)
C8—O5—Zn1	114.65 (14)	N2—C7—C8	113.48 (18)
C8—O6—Zn2^v	115.81 (14)	N2—C7—H7A	108.9
C10—O7—Zn1	114.60 (14)	C8—C7—H7A	108.9
C10—O8—Zn2^vi	118.86 (15)	N2—C7—H7B	108.9
C3—N1—C5	111.54 (17)	C8—C7—H7B	108.9
C3—N1—C1	111.02 (17)	H7A—C7—H7B	107.7
C5—N1—C1	111.12 (18)	O5—C8—O6	123.46 (19)
C3—N1—Zn1	112.94 (14)	O5—C8—C7	121.37 (19)
C5—N1—Zn1	107.06 (13)	O6—C8—C7	115.17 (18)
C1—N1—Zn1	102.79 (13)	N2—C9—C10	109.32 (17)
C2—N2—C9	116.14 (17)	N2—C9—H9A	109.8
C2—N2—C7	112.59 (17)	C10—C9—H9A	109.8
C9—N2—C7	110.64 (18)	N2—C9—H9B	109.8
C2—N2—Zn1	103.65 (13)	C10—C9—H9B	109.8
C9—N2—Zn1	105.16 (13)	H9A—C9—H9B	108.3
C7—N2—Zn1	107.81 (13)	O7—C10—O8	125.1 (2)
N1—C1—C2	113.46 (18)	O7—C10—C9	118.6 (2)
N1—C1—H1A	108.9	O8—C10—C9	116.3 (2)
C2—C1—H1A	108.9	Zn1—O9—H9C	110.9 (17)
N1—C1—H1B	108.9	Zn1—O9—H9D	127 (2)
C2—C1—H1B	108.9	H9C—O9—H9D	108.7 (15)
H1A—C1—H1B	107.7
O8^i—Zn2—O1—C4	12.25 (19)	O5—Zn1—N2—C7	11.77 (13)
O4^ii—Zn2—O1—C4	−120.86 (16)	O7—Zn1—N2—C7	−86.71 (14)
O6^iii—Zn2—O1—C4	127.23 (16)	N1—Zn1—N2—C7	100.46 (14)
O9—Zn1—O3—C6	106.74 (15)	C3—N1—C1—C2	156.65 (18)
O5—Zn1—O3—C6	−30.6 (3)	C5—N1—C1—C2	−78.6 (2)
O7—Zn1—O3—C6	−164.75 (15)	Zn1—N1—C1—C2	35.62 (19)
N2—Zn1—O3—C6	−87.17 (16)	C9—N2—C2—C1	159.00 (18)
N1—Zn1—O3—C6	−2.86 (15)	C7—N2—C2—C1	−72.0 (2)
O9—Zn1—O5—C8	151.21 (15)	Zn1—N2—C2—C1	44.24 (19)
O3—Zn1—O5—C8	−71.0 (3)	N1—C1—C2—N2	−58.2 (2)
O7—Zn1—O5—C8	62.94 (15)	C5—N1—C3—C4	−69.4 (2)
N2—Zn1—O5—C8	−13.25 (15)	C1—N1—C3—C4	55.1 (2)
N1—Zn1—O5—C8	−98.26 (15)	Zn1—N1—C3—C4	169.99 (14)
O9—Zn1—O7—C10	170.55 (16)	Zn2—O1—C4—O2	14.3 (3)
O3—Zn1—O7—C10	72.78 (16)	Zn2—O1—C4—C3	−165.48 (15)
O5—Zn1—O7—C10	−97.00 (15)	N1—C3—C4—O2	−169.7 (2)
N2—Zn1—O7—C10	−18.18 (15)	N1—C3—C4—O1	10.1 (3)
N1—Zn1—O7—C10	4.1 (3)	C3—N1—C5—C6	−149.47 (18)
O9—Zn1—N1—C3	44.58 (16)	C1—N1—C5—C6	86.1 (2)
O3—Zn1—N1—C3	139.14 (15)	Zn1—N1—C5—C6	−25.4 (2)
O5—Zn1—N1—C3	−47.43 (14)	Zn1—O3—C6—O4	169.97 (17)
O7—Zn1—N1—C3	−149.87 (18)	Zn1—O3—C6—C5	−11.8 (2)
N2—Zn1—N1—C3	−128.08 (15)	Zn2^iv—O4—C6—O3	−21.1 (3)
O9—Zn1—N1—C5	−78.58 (14)	Zn2^iv—O4—C6—C5	160.61 (15)
O3—Zn1—N1—C5	15.98 (13)	N1—C5—C6—O3	26.5 (3)
O5—Zn1—N1—C5	−170.59 (14)	N1—C5—C6—O4	−155.08 (19)
O7—Zn1—N1—C5	87.0 (2)	C2—N2—C7—C8	103.8 (2)
N2—Zn1—N1—C5	108.77 (15)	C9—N2—C7—C8	−124.4 (2)
O9—Zn1—N1—C1	164.28 (12)	Zn1—N2—C7—C8	−9.9 (2)
O3—Zn1—N1—C1	−101.16 (13)	Zn1—O5—C8—O6	−169.61 (16)
O5—Zn1—N1—C1	72.27 (13)	Zn1—O5—C8—C7	11.7 (3)
O7—Zn1—N1—C1	−30.2 (3)	Zn2^v—O6—C8—O5	−33.7 (3)
N2—Zn1—N1—C1	−8.37 (12)	Zn2^v—O6—C8—C7	145.07 (15)
O9—Zn1—N2—C2	−174.8 (2)	N2—C7—C8—O5	−0.6 (3)
O3—Zn1—N2—C2	60.21 (13)	N2—C7—C8—O6	−179.48 (18)
O5—Zn1—N2—C2	−107.79 (14)	C2—N2—C9—C10	−153.77 (19)
O7—Zn1—N2—C2	153.74 (14)	C7—N2—C9—C10	76.3 (2)
N1—Zn1—N2—C2	−19.09 (13)	Zn1—N2—C9—C10	−39.9 (2)
O9—Zn1—N2—C9	62.8 (3)	Zn1—O7—C10—O8	−178.25 (17)
O3—Zn1—N2—C9	−62.16 (14)	Zn1—O7—C10—C9	−0.1 (2)
O5—Zn1—N2—C9	129.84 (14)	Zn2^vi—O8—C10—O7	4.6 (3)
O7—Zn1—N2—C9	31.37 (13)	Zn2^vi—O8—C10—C9	−173.57 (14)
N1—Zn1—N2—C9	−141.47 (15)	N2—C9—C10—O7	28.8 (3)
O9—Zn1—N2—C7	−55.2 (3)	N2—C9—C10—O8	−152.90 (19)
O3—Zn1—N2—C7	179.76 (14)

Symmetry codes: (i) x−1/2, −y+3/2, z−1; (ii) −x+1, −y+2, z−1/2; (iii) −x+1/2, y+1/2, z−1/2; (iv) −x+1, −y+2, z+1/2; (v) −x+1/2, y−1/2, z+1/2; (vi) x+1/2, −y+3/2, z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O9—H9C···O2^vii	0.84 (1)	1.80 (1)	2.619 (2)	163 (2)
O9—H9D···O6^viii	0.84 (1)	1.92 (1)	2.750 (2)	172 (3)

Symmetry codes: (vii) −x+1, −y+1, z+1/2; (viii) −x+1, −y+1, z−1/2.