Poly[[{[mu]₄-3-[(1H-1,2,4-triazol-1-yl)­meth­yl]benzoato}zinc(II)] hemi­hydrate]: a novel two-dimensional framework formed by self-association of zinc(II) sulfate with 3-[(1H-1,2,4-triazol-1-yl)meth­yl]benzoic acid

The title novel two-dimensional coordination polymer, {[Zn₂(C₁₀H₈N₃O₂)₄]·H₂O}_n, features a {Zn₂L₂} bimetallic ring repeat unit {L is the 3-[(1H-1,2,4-triazol-1-yl)methyl]benzoate ligand}. Each Zn^II cation of the bimetallic ring is further bonded to two other L ligands, resulting in a novel infinite two-dimensional network structure with two channels of different sizes. The crystallographically unique Zn^II atom is thus six-coordinated in a distorted octa­hedral environment of four carboxyl­ate O atoms and two triazole N atoms. Two of these networks inter­penetrate in an orthogonal arrangement to form the full three-dimensional framework, with disordered water mol­ecules located in the channels.

S1. Comment

The construction of supramolecular complexes with novel structures and topologies has received considerable attention over the past decade for their potential applications in many fields, such as gas storage (Chen et al., 2006), catalysis (Pan et al., 2003), anion/guest exchange (Jung et al., 2002), separation (Li et al., 2008), magnetism (Halder et al., 2002) and luminescent materials (Dong et al., 2007). In the reported literature, 1,2,4-triazole, pyrazole, imidazole and their derivatives have been recognized as one of the most useful classes of organic building blocks to construct metal–organic frameworks (MOFs) (Zhang et al., 2008), due to their ability to link metal ions together to afford diverse supramolecular complexes. Triazoles with an alkyl, aryl or amino substituent on the 4-position acting as bridging ligands have been particularly well studied (Bradford et al., 2004; Klingele & Brooker, 2003; Shakir et al., 2003; Wang et al., 2007; Huang et al., 2006). A number of one-, two- and three-dimensional architectures have been obtained by self-assembly of 1,2,4-triazole, pyrazole, imidazole and their derivatives with transition metal salts. The specific structures obtained demonstrate that the nature of the MOF depends strongly on the properties of the organic ligands used in constructing the supramolecular complexes. Supramolecular complexes based on bent unsymmetric ligands containing 1,2,4-triazole and carboxylic acid groups have been less extensively studied (Ding et al., 2008), so these bent unsymmetric ligands offer great potential for creating novel frameworks. Previously, we have reported the M^II (M = Co, Cd and Zn) coordination chemistry of the carboxylate-substituted 1,2,4-triazole 4-[(1H-1,2,4-triazol-1-yl)methyl]benzoic acid (Zhao et al., 2007; Qin et al., 2009). In the present work, the new isomeric bent organic ligand 3-[(1H-1,2,4-triazol-1-yl)methyl]benzoic acid (HL) was employed in a self-assembly reaction with zinc sulfate under hydrothermal conditions to create the title novel supramolecular complex, {[Zn₂L₄].(H₂O)}_n, (I).

Compound (I) crystallizes with one unique six-coordinated Zn^II centre in a distorted octahedral {ZnN₂O₄} environment (Table 1) involving O atoms (O1, O2, O3 and O4) from the carboxylate groups of two L^- ligands and N atoms [N4ⁱ and N3ⁱⁱ; symmetry codes: (i) -x, -y, -z; (ii) -x + 1, y - 1/2, -z + 1/2] from two other L^- ligands (Fig. 1). The coordinated carboxyl group involving atoms O3 and O4 was found to be disordered over two positions, with refined site-occupancy factors of 0.734 (7) (primed) and 0.266 (7) (unprimed). Neighbouring Zn^II ions are bound together by the carboxylate groups and terminal triazole N donors of two L^- ligands to form a {Zn₂L₂} bimetallic ring in which the diagonal Zn···Zn separation is 8.793 (1) Å. Each Zn^II centre of the bimetallic ring is further bonded with two other bridging ligands, resulting in a novel infinite two-dimensional network structure in the ab plane (Fig. 2). The shortest Zn···Zn distance between adjacent bimetallic rings is 11.188 (2) Å.

When viewed down the crystallographic b axis, chains consisting of alternating symmetric ellipse-like cavities of different sizes are found (Fig. 3). The larger cavities are approximately 11.1 × 7.8 Å, and the smaller ones are about 8.8 × 6.8 Å. The chains repeat in an interpenetrating orthogonal arrangement. The water molecules occupy the smaller cavities, where they are statistically disordered between two symmetry-related positions. The water molecules do not appear to interact strongly with the framework. The cavities in this structure are smaller than similar ones composed of two Cd^II centres and two similar bent 4-[(1H-1,2,4-triazol-1-yl)methyl]benzoate ligands, in which the Cd···Cd separation is 12.40 (4) Å (Qin et al., 2009). The smaller cavity size in (I) may be caused by the 3-substituted ligand being shorter than the 4-substituted ligand in terms of the distance from the carboxylate O atoms to the triazole N atom. Specifically, the longest N···O separations in the 3- and 4-substituted ligands are 7.816 (4) and 8.653 (31) Å, respectively. It is worth noting that the Cd compound of the 4-substituted ligand is a 1:1 salt with an additional chloride counterion, while (I) is a 1:2 salt with no other counterions. In addition, the Cd^II coordination polymer structure is also different in that no guest molecules are located in the channels. The structure of (I) further demonstrates the important role the bridging ligand plays in determining the specific nature of the resulting framework, and emphasizes the practically limitless potential for structural diversity in these systems.

Related literature

For related literature, see: Bradford et al. (2004); Chen et al. (2006); Ding et al. (2008); Dong et al. (2007); Halder et al. (2002); Huang et al. (2006); Jung et al. (2002); Klingele & Brooker (2003); Li et al. (2008); Pan et al. (2003); Qin et al. (2009); Shakir et al. (2003); Wang et al. (2007); Zhang et al. (2008); Zhao et al. (2007).

S2. Experimental

A mixture of 3-methylbenzoic acid (1.36 g, 10.0 mmol), succinbromimide (1.78 g, 10.0 mmol), benzoyl peroxide (0.025 g, 0.103 mmol) and tetrachloromethane (40 ml) was refluxed for 5 h. After cooling to room temperature, a pink precipitate was obtained by filtration and subsequently washed with tetrachloromethane and water. Recrystallization from dichloromethane provided 3-bromomethylbenzoic acid as a white solid in 80.3% yield.

KOH (2.8 g, 50.0 mmol) was added with stirring to a solution of 3-bromomethylbenzoic acid (2.15 g, 10.0 mmol) and 1H-1,2,4-triazole (0.69 g, 10.0 mmol) in water (60 ml). The mixture was stirred for 12 h, then acidified with hydrochloric acid to adjust the pH to 2. The white precipitate which formed was filtered off and recrystallized from methanol to give the product, HL (yield 81.3%). ¹H NMR (300 MHz, DMSO-d₆, δ, p.p.m): 12.99 (s, 1H, COOH), 8.71 (s, 1H, CH), 8.01 (s, 1H, CH), 7.89-7.50 (m, 4H, m-C₆H₄), 5.50 (s, 2H, CH₂); IR (KBr, cm^-1): 3450, 3108, 2767, 2516, 1925, 1694, 1611, 1518, 1454, 1276, 1201, 1136, 1019, 980, 891, 783, 742, 679, 656, 590.

A mixture of HL (20.3 mg, 0.10 mmol), ZnSO₄.7H₂O (28.7 mg, 0.10 mmol) and deionized water (2 ml) was sealed in a 5 ml test tube, heated at 453 K for 40 h and cooled slowly to room temperature over a period of 50 h. Colourless crystals of the title compound, (I), were isolated in 80% yield (based on HL). IR (KBr, cm^-1): 3450, 3132, 1694, 1518, 1348, 1276, 1203, 1131, 982, 931, 742, 678, 653; elemental analysis, calculated for C₄₀H₃₄N₁₂O₉Zn₂: C 50.17, H 3.55, N 17.56%; found: C 50.14, H 3.57, N 17.58%.

S3. Refinement

H atoms attached to C atoms were placed in geometrically idealized positions and included as riding atoms, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C) (aromatic) or C—H = 0.97 Å and U_iso(H) = 1.5U_eq(C) (methylene). The O atoms of one coordinated carboxyl group were disordered over two positions; the site-occupancy factors are 0.734 (7) (atoms O3' and O4') and 0.266 (7) (atoms O3 and O4). The anisotropic displacement parameters of atoms O3 and O4 were restrained to be similar to those of O3' and O4' within a standard deviation of 0.005 Ų. The disordered water molecule was modelled as half-occupied. H atoms of the water molecule were located in a difference map and refined as riding, with O—H = 0.85 (1) and U_iso(H) = 1.2U_eq(O).

Computing details

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

Figures

	Fig. 1. The molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity. Both positions of the disordered carboxylate atoms O3 and O4 are shown. [Symmetry codes: (i) -x, -y, -z; (ii) -x + 1, y - 1/2, -z + 1/2.]
	Fig. 2. A schematic representation of the two-dimensional supramolecular framework of (I), viewed down the c axis.
	Fig. 3. A schematic representation of the crystal packing of (I), viewed down the crystallographic b axis. The two interpenetrating orthogonal networks are shown in green (light) and blue (dark). Water molecules are located in the channels. Two disordered positions for the water O atoms, each at 0.50 occupancy, are shown as dark spheres.

Poly[[{µ₄-3-[(1H-1,2,4-triazol-1-yl)methyl]benzoato}zinc(II)] hemihydrate]

Crystal data

[Zn2(C10H8N3O2)4]·H2O	F(000) = 1960
Mr = 957.53	Dx = 1.574 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P2ac2ab	Cell parameters from 3341 reflections
a = 13.875 (3) Å	θ = 2.3–23.1°
b = 13.142 (3) Å	µ = 1.26 mm^−1
c = 22.166 (4) Å	T = 298 K
V = 4041.9 (13) Å^3	Bar, colourless
Z = 4	0.52 × 0.16 × 0.08 mm

Data collection

Bruker SMART CCD area-detector diffractometer	3572 independent reflections
Radiation source: fine-focus sealed tube	2598 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.048
ϕ and ω scans	θmax = 25.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −16→13
Tmin = 0.560, Tmax = 0.906	k = −15→15
19051 measured reflections	l = −26→25

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.118	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0591P)^2 + 2.1694P] where P = (Fo^2 + 2Fc^2)/3
3572 reflections	(Δ/σ)max = 0.001
296 parameters	Δρmax = 0.66 e Å^−3
13 restraints	Δρmin = −0.30 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	Occ. (<1)
C1	0.2564 (3)	0.1632 (3)	0.21933 (16)	0.0466 (9)
C2	0.2874 (2)	0.2329 (3)	0.26849 (14)	0.0410 (8)
C3	0.2332 (2)	0.3176 (3)	0.28192 (17)	0.0506 (10)
H3	0.1779	0.3313	0.2597	0.061*
C4	0.2597 (3)	0.3819 (3)	0.32778 (19)	0.0576 (11)
H4	0.2233	0.4398	0.3358	0.069*
C5	0.3398 (3)	0.3607 (3)	0.36172 (16)	0.0520 (9)
H5	0.3566	0.4037	0.3934	0.062*
C6	0.3960 (2)	0.2761 (3)	0.34945 (15)	0.0414 (8)
C7	0.3698 (2)	0.2132 (2)	0.30197 (15)	0.0423 (8)
H7	0.4079	0.1573	0.2925	0.051*
C8	0.4808 (3)	0.2487 (3)	0.38879 (17)	0.0486 (9)
H8A	0.4571	0.2186	0.4259	0.058*
H8B	0.5195	0.1979	0.3682	0.058*
C9	0.6206 (2)	0.3664 (3)	0.37702 (15)	0.0422 (8)
H9	0.6499	0.3335	0.3447	0.051*
C10	0.5880 (2)	0.4675 (3)	0.44666 (16)	0.0460 (9)
H10	0.5919	0.5226	0.4729	0.055*
C11	−0.0617 (3)	0.0388 (3)	−0.18965 (19)	0.0595 (11)
H11	−0.0540	−0.0206	−0.2119	0.071*
C12	−0.1193 (3)	0.1463 (3)	−0.13059 (16)	0.0497 (9)
H12	−0.1587	0.1803	−0.1033	0.060*
C13	0.0039 (3)	0.2834 (3)	−0.1447 (2)	0.0726 (13)
H13A	−0.0452	0.3291	−0.1293	0.087*
H13B	0.0242	0.3092	−0.1836	0.087*
C14	0.0887 (2)	0.2865 (3)	−0.10262 (16)	0.0437 (8)
C15	0.1521 (3)	0.3656 (3)	−0.10983 (16)	0.0479 (9)
H15	0.1423	0.4121	−0.1408	0.057*
C16	0.2295 (3)	0.3771 (3)	−0.07212 (18)	0.0548 (10)
H16	0.2714	0.4315	−0.0775	0.066*
C17	0.2454 (3)	0.3090 (3)	−0.02672 (17)	0.0517 (10)
H17	0.2983	0.3172	−0.0014	0.062*
C18	0.1832 (2)	0.2278 (3)	−0.01812 (15)	0.0433 (8)
C19	0.1042 (2)	0.2178 (3)	−0.05627 (17)	0.0487 (9)
H19	0.0613	0.1644	−0.0506	0.058*
C20	0.2013 (3)	0.1528 (4)	0.03187 (18)	0.0613 (11)
N1	0.54153 (19)	0.3354 (2)	0.40362 (12)	0.0404 (7)
N2	0.5193 (2)	0.4002 (2)	0.44957 (13)	0.0511 (8)
N3	0.65327 (19)	0.4509 (2)	0.40242 (12)	0.0396 (7)
N4	−0.13604 (19)	0.0539 (2)	−0.15193 (13)	0.0412 (7)
N5	−0.0393 (2)	0.1833 (2)	−0.15342 (15)	0.0514 (8)
N6	−0.0008 (2)	0.1149 (3)	−0.19247 (17)	0.0711 (11)
O1	0.1742 (2)	0.1720 (2)	0.19707 (12)	0.0622 (7)
O2	0.31508 (19)	0.0975 (2)	0.20055 (11)	0.0579 (7)
O5	0.9496 (2)	0.04194 (19)	0.03131 (11)	0.138 (4)	0.50
H5A	1.0100	0.0312	0.0311	0.206*	0.50
H5B	0.9286	0.0821	0.0045	0.206*	0.50
O4	0.2970 (2)	0.18139 (19)	0.06048 (11)	0.060 (2)	0.266 (7)
O3	0.1560 (2)	0.09609 (19)	0.05456 (11)	0.079 (3)	0.266 (7)
O3'	0.2635 (2)	0.16422 (19)	0.06695 (11)	0.0611 (12)	0.734 (7)
O4'	0.1458 (2)	0.07437 (19)	0.03531 (11)	0.0946 (16)	0.734 (7)
Zn1	0.24005 (3)	0.04624 (3)	0.126520 (17)	0.04052 (17)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.055 (2)	0.044 (2)	0.041 (2)	−0.0124 (18)	0.0010 (17)	0.0018 (18)
C2	0.0405 (18)	0.046 (2)	0.0367 (18)	−0.0065 (17)	0.0050 (15)	−0.0010 (16)
C3	0.044 (2)	0.056 (3)	0.052 (2)	0.0031 (18)	−0.0074 (16)	−0.0033 (19)
C4	0.054 (2)	0.053 (3)	0.065 (3)	0.0155 (18)	−0.0086 (19)	−0.014 (2)
C5	0.058 (2)	0.046 (2)	0.052 (2)	0.0043 (19)	−0.0072 (18)	−0.0150 (18)
C6	0.0385 (18)	0.041 (2)	0.045 (2)	−0.0044 (16)	−0.0014 (15)	0.0016 (17)
C7	0.0436 (19)	0.037 (2)	0.046 (2)	−0.0009 (15)	0.0059 (16)	−0.0031 (16)
C8	0.047 (2)	0.038 (2)	0.061 (2)	−0.0023 (17)	−0.0089 (17)	0.0023 (18)
C9	0.046 (2)	0.045 (2)	0.0357 (19)	0.0042 (17)	0.0064 (15)	−0.0031 (16)
C10	0.047 (2)	0.049 (2)	0.042 (2)	−0.0015 (17)	0.0029 (16)	−0.0098 (17)
C11	0.047 (2)	0.055 (3)	0.076 (3)	−0.0044 (19)	0.008 (2)	−0.015 (2)
C12	0.047 (2)	0.053 (2)	0.049 (2)	0.0043 (18)	−0.0028 (17)	−0.0052 (18)
C13	0.068 (3)	0.042 (2)	0.108 (4)	−0.012 (2)	−0.036 (3)	0.011 (2)
C14	0.046 (2)	0.034 (2)	0.052 (2)	0.0024 (16)	−0.0064 (16)	0.0011 (17)
C15	0.058 (2)	0.040 (2)	0.046 (2)	−0.0039 (18)	−0.0034 (17)	0.0051 (16)
C16	0.057 (2)	0.050 (3)	0.056 (2)	−0.0161 (19)	−0.0028 (18)	0.0037 (19)
C17	0.052 (2)	0.058 (3)	0.046 (2)	−0.0052 (18)	−0.0068 (17)	−0.0058 (19)
C18	0.047 (2)	0.047 (2)	0.0355 (19)	0.0076 (17)	0.0032 (15)	0.0010 (16)
C19	0.043 (2)	0.041 (2)	0.062 (2)	−0.0022 (17)	0.0003 (17)	0.0090 (18)
C20	0.069 (3)	0.067 (3)	0.048 (2)	0.031 (2)	0.009 (2)	0.006 (2)
N1	0.0400 (16)	0.0399 (17)	0.0414 (16)	0.0006 (13)	−0.0030 (13)	−0.0040 (13)
N2	0.0472 (17)	0.062 (2)	0.0438 (18)	−0.0052 (16)	0.0071 (14)	−0.0127 (16)
N3	0.0427 (16)	0.0375 (17)	0.0386 (16)	0.0006 (13)	0.0052 (13)	0.0012 (13)
N4	0.0385 (15)	0.0412 (17)	0.0440 (16)	−0.0013 (13)	0.0020 (13)	−0.0023 (14)
N5	0.0445 (18)	0.0425 (18)	0.067 (2)	−0.0050 (15)	−0.0130 (15)	0.0026 (16)
N6	0.049 (2)	0.073 (3)	0.091 (3)	−0.0101 (18)	0.0145 (18)	−0.012 (2)
O1	0.0740 (19)	0.0461 (16)	0.0666 (17)	0.0052 (13)	−0.0220 (14)	−0.0170 (12)
O2	0.0623 (16)	0.0600 (17)	0.0514 (15)	−0.0032 (14)	0.0026 (13)	−0.0164 (14)
O5	0.068 (5)	0.079 (5)	0.266 (12)	−0.008 (4)	0.029 (6)	−0.056 (6)
O4	0.070 (5)	0.049 (4)	0.059 (4)	0.002 (4)	−0.016 (4)	0.002 (4)
O3	0.068 (4)	0.086 (5)	0.083 (5)	−0.020 (4)	−0.011 (4)	0.046 (5)
O3'	0.084 (3)	0.049 (2)	0.051 (2)	0.009 (2)	−0.018 (2)	0.0032 (18)
O4'	0.076 (3)	0.103 (3)	0.105 (4)	−0.016 (2)	−0.014 (2)	0.068 (3)
Zn1	0.0406 (3)	0.0381 (3)	0.0429 (3)	−0.00136 (17)	0.00149 (17)	−0.00094 (18)

Geometric parameters (Å, º)

C1—O1	1.248 (4)	C13—H13A	0.9700
C1—O2	1.257 (4)	C13—H13B	0.9700
C1—C2	1.487 (5)	C14—C15	1.370 (5)
C2—C3	1.375 (5)	C14—C19	1.384 (5)
C2—C7	1.387 (5)	C15—C16	1.369 (5)
C3—C4	1.372 (5)	C15—H15	0.9300
C3—H3	0.9300	C16—C17	1.364 (5)
C4—C5	1.371 (5)	C16—H16	0.9300
C4—H4	0.9300	C17—C18	1.386 (5)
C5—C6	1.386 (5)	C17—H17	0.9300
C5—H5	0.9300	C18—C19	1.391 (5)
C6—C7	1.387 (4)	C18—C20	1.504 (5)
C6—C8	1.507 (5)	C19—H19	0.9300
C7—H7	0.9300	C20—O3	1.096 (5)
C8—N1	1.455 (4)	C20—O3'	1.171 (5)
C8—H8A	0.9700	C20—O4'	1.289 (5)
C8—H8B	0.9700	C20—O4	1.520 (5)
C9—N1	1.311 (4)	N1—N2	1.363 (4)
C9—N3	1.325 (4)	N3—Zn1^i	2.043 (3)
C9—H9	0.9300	N4—Zn1^ii	2.033 (3)
C10—N2	1.302 (4)	N5—N6	1.358 (4)
C10—N3	1.353 (4)	O1—Zn1	2.452 (3)
C10—H10	0.9300	O2—Zn1	2.057 (2)
C11—N6	1.310 (5)	O5—H5A	0.8503
C11—N4	1.343 (4)	O5—H5B	0.8464
C11—H11	0.9300	Zn1—O4	2.434 (2)
C12—N5	1.313 (5)	Zn1—O3	2.081 (3)
C12—N4	1.324 (4)	Zn1—O3'	2.062 (2)
C12—H12	0.9300	Zn1—O4'	2.436 (3)
C13—N5	1.459 (4)	Zn1—N4^ii	2.033 (3)
C13—C14	1.501 (5)	Zn1—N3^iii	2.043 (3)
O1—C1—O2	121.6 (3)	C14—C19—H19	119.6
O1—C1—C2	119.8 (4)	C18—C19—H19	119.6
O2—C1—C2	118.6 (3)	O3—C20—O3'	101.8 (3)
C3—C2—C7	119.1 (3)	O3—C20—O4'	24.14 (12)
C3—C2—C1	119.9 (3)	O3'—C20—O4'	120.2 (4)
C7—C2—C1	121.0 (3)	O3—C20—C18	133.5 (4)
C4—C3—C2	120.8 (3)	O3'—C20—C18	121.8 (4)
C4—C3—H3	119.6	O4'—C20—C18	117.9 (4)
C2—C3—H3	119.6	O3—C20—O4	118.5 (3)
C5—C4—C3	119.9 (4)	O3'—C20—O4	17.64 (9)
C5—C4—H4	120.0	O4'—C20—O4	134.1 (3)
C3—C4—H4	120.0	C18—C20—O4	106.9 (3)
C4—C5—C6	120.8 (3)	C9—N1—N2	109.3 (3)
C4—C5—H5	119.6	C9—N1—C8	128.8 (3)
C6—C5—H5	119.6	N2—N1—C8	121.8 (3)
C5—C6—C7	118.6 (3)	C10—N2—N1	102.8 (3)
C5—C6—C8	121.2 (3)	C9—N3—C10	102.4 (3)
C7—C6—C8	120.1 (3)	C9—N3—Zn1^i	128.9 (2)
C6—C7—C2	120.7 (3)	C10—N3—Zn1^i	127.9 (2)
C6—C7—H7	119.6	C12—N4—C11	102.9 (3)
C2—C7—H7	119.6	C12—N4—Zn1^ii	128.3 (2)
N1—C8—C6	113.3 (3)	C11—N4—Zn1^ii	128.5 (2)
N1—C8—H8A	108.9	C12—N5—N6	109.5 (3)
C6—C8—H8A	108.9	C12—N5—C13	129.1 (4)
N1—C8—H8B	108.9	N6—N5—C13	121.3 (3)
C6—C8—H8B	108.9	C11—N6—N5	102.8 (3)
H8A—C8—H8B	107.7	C1—O1—Zn1	81.3 (2)
N1—C9—N3	110.8 (3)	C1—O2—Zn1	99.3 (2)
N1—C9—H9	124.6	H5A—O5—H5B	116.0
N3—C9—H9	124.6	C20—O4—Zn1	77.66 (18)
N2—C10—N3	114.6 (3)	C20—O3—Zn1	104.2 (3)
N2—C10—H10	122.7	C20—O3'—Zn1	102.3 (3)
N3—C10—H10	122.7	C20—O4'—Zn1	81.3 (2)
N6—C11—N4	114.4 (3)	N4^ii—Zn1—N3^iii	101.80 (11)
N6—C11—H11	122.8	N4^ii—Zn1—O2	110.52 (11)
N4—C11—H11	122.8	N3^iii—Zn1—O2	94.87 (11)
N5—C12—N4	110.5 (3)	N4^ii—Zn1—O3'	140.88 (12)
N5—C12—H12	124.7	N3^iii—Zn1—O3'	98.39 (10)
N4—C12—H12	124.7	O2—Zn1—O3'	100.64 (12)
N5—C13—C14	115.4 (3)	N4^ii—Zn1—O3	91.06 (11)
N5—C13—H13A	108.4	N3^iii—Zn1—O3	110.99 (11)
C14—C13—H13A	108.4	O2—Zn1—O3	142.34 (11)
N5—C13—H13B	108.4	O3'—Zn1—O3	50.27 (5)
C14—C13—H13B	108.4	N4^ii—Zn1—O4	150.44 (11)
H13A—C13—H13B	107.5	N3^iii—Zn1—O4	91.33 (10)
C15—C14—C19	118.8 (3)	O2—Zn1—O4	94.37 (11)
C15—C14—C13	116.8 (3)	O3'—Zn1—O4	9.9
C19—C14—C13	124.4 (3)	O3—Zn1—O4	59.42 (6)
C16—C15—C14	121.1 (3)	N4^ii—Zn1—O4'	86.95 (10)
C16—C15—H15	119.5	N3^iii—Zn1—O4'	102.80 (10)
C14—C15—H15	119.5	O2—Zn1—O4'	152.13 (10)
C17—C16—C15	120.3 (3)	O3'—Zn1—O4'	55.88 (6)
C17—C16—H16	119.8	O3—Zn1—O4'	10.1
C15—C16—H16	119.8	O4—Zn1—O4'	64.19 (6)
C16—C17—C18	120.4 (3)	N4^ii—Zn1—O1	89.73 (10)
C16—C17—H17	119.8	N3^iii—Zn1—O1	152.10 (10)
C18—C17—H17	119.8	O2—Zn1—O1	57.23 (10)
C17—C18—C19	118.7 (3)	O3'—Zn1—O1	87.71 (10)
C17—C18—C20	120.2 (4)	O3—Zn1—O1	93.90 (10)
C19—C18—C20	121.2 (4)	O4—Zn1—O1	90.72 (10)
C14—C19—C18	120.8 (3)	O4'—Zn1—O1	103.12 (9)
O1—C1—C2—C3	−11.6 (5)	O1—C1—O2—Zn1	8.0 (4)
O2—C1—C2—C3	167.3 (3)	C2—C1—O2—Zn1	−170.8 (3)
O1—C1—C2—C7	167.4 (3)	O3—C20—O4—Zn1	4.4 (4)
O2—C1—C2—C7	−13.8 (5)	O3'—C20—O4—Zn1	24.2 (2)
C7—C2—C3—C4	−0.1 (6)	O4'—C20—O4—Zn1	−18.7 (5)
C1—C2—C3—C4	178.9 (3)	C18—C20—O4—Zn1	174.0 (3)
C2—C3—C4—C5	−1.6 (6)	O3'—C20—O3—Zn1	−11.2 (4)
C3—C4—C5—C6	1.5 (6)	O4'—C20—O3—Zn1	131.24 (14)
C4—C5—C6—C7	0.2 (5)	C18—C20—O3—Zn1	−171.4 (4)
C4—C5—C6—C8	−176.3 (4)	O4—C20—O3—Zn1	−5.2 (5)
C5—C6—C7—C2	−1.8 (5)	O3—C20—O3'—Zn1	11.2 (4)
C8—C6—C7—C2	174.7 (3)	O4'—C20—O3'—Zn1	−5.6 (5)
C3—C2—C7—C6	1.8 (5)	C18—C20—O3'—Zn1	174.4 (3)
C1—C2—C7—C6	−177.2 (3)	O4—C20—O3'—Zn1	−151.1 (2)
C5—C6—C8—N1	−45.5 (5)	O3—C20—O4'—Zn1	−39.05 (14)
C7—C6—C8—N1	138.1 (3)	O3'—C20—O4'—Zn1	4.6 (4)
N5—C13—C14—C15	156.4 (4)	C18—C20—O4'—Zn1	−175.3 (3)
N5—C13—C14—C19	−26.4 (6)	O4—C20—O4'—Zn1	18.5 (5)
C19—C14—C15—C16	0.0 (5)	C1—O2—Zn1—N4^ii	−79.8 (2)
C13—C14—C15—C16	177.4 (4)	C1—O2—Zn1—N3^iii	175.6 (2)
C14—C15—C16—C17	0.6 (6)	C1—O2—Zn1—O3'	76.1 (2)
C15—C16—C17—C18	−0.3 (6)	C1—O2—Zn1—O3	41.3 (3)
C16—C17—C18—C19	−0.5 (5)	C1—O2—Zn1—O4	83.9 (2)
C16—C17—C18—C20	179.8 (3)	C1—O2—Zn1—O4'	46.1 (3)
C15—C14—C19—C18	−0.8 (5)	C1—O2—Zn1—O1	−4.1 (2)
C13—C14—C19—C18	−178.0 (4)	C20—O3'—Zn1—N4^ii	−17.7 (3)
C17—C18—C19—C14	1.1 (5)	C20—O3'—Zn1—N3^iii	102.9 (3)
C20—C18—C19—C14	−179.2 (3)	C20—O3'—Zn1—O2	−160.5 (2)
C17—C18—C20—O3	162.2 (5)	C20—O3'—Zn1—O3	−7.5 (3)
C19—C18—C20—O3	−17.5 (7)	C20—O3'—Zn1—O4	148.0 (3)
C17—C18—C20—O3'	5.2 (6)	C20—O3'—Zn1—O4'	3.1 (3)
C19—C18—C20—O3'	−174.5 (4)	C20—O3'—Zn1—O1	−104.5 (3)
C17—C18—C20—O4'	−174.9 (3)	C20—O3—Zn1—N4^ii	−178.4 (3)
C19—C18—C20—O4'	5.5 (5)	C20—O3—Zn1—N3^iii	−75.3 (3)
C17—C18—C20—O4	−5.1 (4)	C20—O3—Zn1—O2	54.9 (3)
C19—C18—C20—O4	175.2 (3)	C20—O3—Zn1—O3'	8.1 (3)
N3—C9—N1—N2	−0.7 (4)	C20—O3—Zn1—O4	3.3 (3)
N3—C9—N1—C8	177.6 (3)	C20—O3—Zn1—O4'	−112.3 (3)
C6—C8—N1—C9	−95.7 (4)	C20—O3—Zn1—O1	91.8 (3)
C6—C8—N1—N2	82.5 (4)	C20—O4—Zn1—N4^ii	−5.7 (3)
N3—C10—N2—N1	−0.3 (4)	C20—O4—Zn1—N3^iii	111.37 (19)
C9—N1—N2—C10	0.6 (4)	C20—O4—Zn1—O2	−153.64 (19)
C8—N1—N2—C10	−177.9 (3)	C20—O4—Zn1—O3'	−24.1 (2)
N1—C9—N3—C10	0.5 (4)	C20—O4—Zn1—O3	−2.4 (2)
N1—C9—N3—Zn1^i	−169.6 (2)	C20—O4—Zn1—O4'	7.8 (2)
N2—C10—N3—C9	−0.1 (4)	C20—O4—Zn1—O1	−96.46 (19)
N2—C10—N3—Zn1^i	170.2 (2)	C20—O4'—Zn1—N4^ii	164.3 (2)
N5—C12—N4—C11	−0.9 (4)	C20—O4'—Zn1—N3^iii	−94.3 (2)
N5—C12—N4—Zn1^ii	172.9 (2)	C20—O4'—Zn1—O2	33.7 (3)
N6—C11—N4—C12	0.4 (5)	C20—O4'—Zn1—O3'	−2.8 (2)
N6—C11—N4—Zn1^ii	−173.4 (3)	C20—O4'—Zn1—O3	50.5 (2)
N4—C12—N5—N6	1.1 (4)	C20—O4'—Zn1—O4	−9.1 (2)
N4—C12—N5—C13	177.0 (3)	C20—O4'—Zn1—O1	75.3 (2)
C14—C13—N5—C12	103.4 (5)	C1—O1—Zn1—N4^ii	119.0 (2)
C14—C13—N5—N6	−81.2 (5)	C1—O1—Zn1—N3^iii	3.6 (3)
N4—C11—N6—N5	0.2 (5)	C1—O1—Zn1—O2	4.1 (2)
C12—N5—N6—C11	−0.8 (4)	C1—O1—Zn1—O3'	−100.1 (2)
C13—N5—N6—C11	−177.0 (3)	C1—O1—Zn1—O3	−150.0 (2)
O2—C1—O1—Zn1	−6.7 (3)	C1—O1—Zn1—O4	−90.6 (2)
C2—C1—O1—Zn1	172.1 (3)	C1—O1—Zn1—O4'	−154.2 (2)

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