A three-dimensional Zn^II coordination framework: poly[[μ₂-(E)-1,2-bis(pyri­din-4-yl)ethene][μ₄-(E)-2,2′-(diazene-1,2-diyl)dibenzoato][μ₂-(E)-2,2′-(di­azene-1,2-di­yl)dibenzoato]dizinc(II)]

In the title coordination polymer, [Zn₂(C₁₄H₈N₂O₄)₂(C₁₂H₁₀N₂)]_n, the asymmetric unit contains one Zn^II cation, two halves of 2,2′-(diazene-1,2-diyl)dibenzoate anions (denoted L²⁻) and half of a 1,2-bis­(pyridin-4-yl)ethene ligand (denoted bpe). The three ligands lie across crystallographic inversion centres. Each Zn^II centre is four-coordinated by three O atoms of bridging carboxyl­ate groups from three L²⁻ ligands and by one N atom from a bpe ligand, forming a tetra­hedral coordination geometry. Two Zn^II atoms are bridged by two carboxyl­ate groups of L²⁻ ligands, generating a [Zn₂(CO₂)₂] ring. Each loop serves as a fourfold node, which links its four equivalent nodes via the sharing of four L²⁻ ligands to form a two-dimensional [Zn₂L₄]_n net. These nets are separated by bpe ligands acting as spacers, producing a three-dimensional framework with a 4⁶6⁴ topology. Powder X-ray diffraction and solid-state photoluminescence were also measured.

S1. Introduction

The design and synthesis of coordination polymers with novel structures have attracted much inter­est in recent years because of their intriguing coordination architectures and potential applications in various fields, including catalysis and photochemistry, and their fluorescence and biological properties (Song et al., 2010; Liu et al., 2011; Cui et al., 2012; Allendorf et al., 2009; Lee et al., 2009). Previously, coordination polymers were usually constructed by metal ions and one type of O- or N-containing ligands. However, the number of such coordination polymers is limited since the types of ligand are limited. So, to construct novel coordination polymers, many chemists usually choose carboxyl­ate-containing ligands with varied coordination modes as the main connectors, and mixed ligands with N-donor groups as ancillary bridges (Batten & Robson, 1998). The use of the 1,2-bis­(pyridin-4-yl)ethene (Bpe) ligand is an effective method of forming meaningful coordination frameworks because it can satisfy and even mediate the coordination needs of the metal centres [Reference needed?].

The flexible di­carboxyl­ate ligand 2,2'-(diazene-1,2-diyl)di­benzoic acid (H₂L) has recently been synthesized and reacted with metal salts (Zn^II, Cd^II and Pb^II), which results in the formation of three-dimensional coordination polymers (Liu, Yu, Sun et al., 2014; Liu, Yu, Zhou et al., 2014 or Liu, Zhou et al., 2014 ?). The H₂L ligand shows a variety of coordination modes and conformations due to the increased flexibility and length of the diazenediyl groups, thus making it easier to form various inter­esting coordination polymers. Moreover, in our previous work, we have synthesized three extended Cd^II coordination frameworks based on H₂L and auxiliary 4,4'-bi­pyridine (bpy), 1,2-bis­(pyridin-4-yl)ethene (bpe) and 1,3-bis­(pyridin-4-yl)propane (bpp) N-donor ligands (Liu, Yu, Sun et al., 2014; Liu, Yu, Zhou et al., 2014 or Liu, Zhou et al., 2014 ?). To further understand the coordination chemistry of flexible di­carboxyl­ate and di­pyridyl ligands, we employed H₂L and bpe as organic ligands in a reaction with Zn^II ions under solvothermal conditions and obtained the title three-dimensional framework, [Zn₂(µ₄-L)(µ₂-L)(bpe)]_n, (I). The photoluminescence properties of (I) in the solid state were also investigated.

S2. Experimental

S2.1. Synthesis and crystallization

H₂L was prepared according to the literature method of Reid & Pritchett (1953). All other chemicals and reagents were obtained from commercial sources (Alfa Aesar) and used as received. A 10 ml Pyrex glass tube was loaded with Zn(OAc)₂.2H₂O (11 mg, 0.05 mmol), H₂L (7 mg, 0.025 mmol), bpe (5 mg, 0.025 mmol), 0.020 M NaOH (0.1 ml) and MeOH–H₂O (1:1 v/v, 4 ml), forming a red solution. The tube was then sealed and heated in an oven to 393 K for 4 d, and then cooled to ambient temperature at a rate of 5 K h^-1. Pink blocks of (I) were collected and washed thoroughly with H₂O and dried in air (yield 5 mg, 57% based on H₂L). Spectroscopic analysis: IR (KBr disc, ν, cm^-1): 3446 (m), 2989 (w), 1604 (s), 1597 (s), 1404 (s), 1221 (w), 1152 (w), 1098 (m), 1032 (w), 962 (m), 864 (m), 782 (m), 772 (m), 735 (m), 664 (m), 526 (w), 460 (w).

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were placed in geometrically idealized positions, with C—H = 0.93 Å for phenyl and pyridine groups, and constrained to ride on their parent atoms, with U_iso(H) = 1.2U_eq(C).

S3. Results and discussion

Polymer (I) crystallizes in the triclinic space group P1, and its asymmetric unit contains half of a [Zn₂(µ₄-L)(µ₂-L)(bpe)] unit. As shown in Fig. 1, each Zn^II centre is tetra­hedrally coordinated by three carboxyl­ate O atoms from three L^2- ligands and one N atom from one bpe ligand. A weak inter­action [2.5002 (4) Å] exists between atoms Zn1 and O3 (Fig. 1). Selected bond lengths and angles for (I) are listed in Table 2.

In the structure of (I), atom Zn1 and its symmetry-related Zn1^v counterpart [symmetry code: (v) -x + 1, -y + 1, -z + 1] are bridged by two carboxyl­ate groups (µ₂-η¹:η¹) from two L^2- ligands to generate a macrocyclic [Zn₂(CO₂)₂] loop with a Zn···Zn distance of 4.122 (2) Å (Fig. 2). Each macrocyclic loop serves as a fourfold node, which links its four equivalent nodes via the sharing of four L^2- ligands to form a two-dimensional (4,4) network extending in the ac plane (Fig. 3). The carboxyl­ate groups ligate the Zn^II centres in two different fashions, in µ₁-η¹:η⁰ and µ₂-η¹:η¹ coordination modes. Furthermore, the bpe ligands are employed as pillars to hold the two-dimensional network, thus affording a three-dimensional framework looking down the [100] direction (Fig. 4). The structure is also stabilized by hydrogen-bonding inter­actions (Table 3). Topologically (Wells, 1997), if the Zn^II centres are considered as nodes and the L^2- and bpe ligands are considered as linkers, the overall structure of (I) can be specified by the Schläfli symbol 4⁶6⁴ (Fig. 5).

As reported previously (Liu, Yu, Sun et al., 2014; Liu, Yu, Zhou et al., 2014 or Liu, Zhou et al., 2014 ?), a Cd^II coordination polymer assembled from H₂L and bpe has been investigated, viz. [Cd(L)(bpe)]_n, (II), and it shows a two-dimensional layer. In (I), each Zn^II centre is four-coordinated by three O atoms and one N atom, forming a tetra­hedron, while in (II) each Cd^II centre is six-coordinated by four O atoms and two N atoms, generating a distorted o­cta­hedron. This difference is possibly due to the fact that the ionic radius of Cd^II is larger than that of Zn^II [Values and reference?]. Moreover, the carboxyl­ate groups of the L^2- ligands in (I) only adopt a bridging coordination mode and link two Zn^II centres, producing a dinuclear Zn₂ unit, and these are further bridged by L^2- ligands, resulting in the two-dimensional [Zn₂L₄]_n network. In (II), the mononuclear Cd^II centres are bridged by L^2- ligands through carboxyl­ate groups (in bridging and chelating coordination modes), generating a one-dimensional [CdL]_n chain. Furthermore, the bpe ligands in (I) are employed as pillars to hold the two-dimensional networks, thus affording a three-dimensional framework with one-dimensional channels. The bpe ligands in (II) are utilized as linkers to bridge the one-dimensional chains, producing a two-dimensional layer. From these comparisons, it is noted that the different species of metal centre greatly affects the coordination modes of the carboxyl­ate groups, the formation of metal-containing units and the whole structures of these compounds.

Compound (I) was also characterized by powder X-ray diffraction (PXRD) at room temperature. The PXRD pattern of (I) is coincident with the simulated pattern derived from the single-crystal X-ray data (Fig. 6), which implies that the structure of the bulk sample is the same as that of the single crystal.

Finally, the photoluminescence properties of (I) in the solid state at room temperature were studied (Fig. 7). H₂L did not show any photoluminescence properties, while excitation of (I) at 349 nm resulted in a strong emission band at 467 nm. This may be ascribed to ligand chelation to the Zn^II centre, which effectively increases the rigidity of the molecule and reduces the loss of energy by radiationless decay.

Related literature

For related literature, see: Allendorf et al. (2009); Batten & Robson (1998); Cui et al. (2012); Lee et al. (2009); Liu et al. (2011); Liu, Yu, Sun, Meng, Ma, Du & Ma (2014); Liu, Yu, Zhou, Sun, Meng, Liu & Sa (2014); Liu, Zhou, Li & Tian (2014); Reid & Pritchett (1953); Song et al. (2010); Wells (1997).

Computing details

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: XP (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL2013 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures

	Fig. 1. The coordination environment of the Zn atom in (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. The dashed line represents the weak interaction between atoms Zn1 and O3. [Symmetry codes: (i) -x, -y + 1, -z + 1; (ii) -x + 1, -y + 1, -z; (iii) -x - 1, -y, -z; (iv) -x + 1, -y + 1, -z + 1.]
	Fig. 2. A view of the macrocyclic [Zn2(CO2)2] loop linked via bridging carboxylate groups. [Symmetry code: (v) -x + 1, -y + 1, -z + 1.]
	Fig. 3. A view of the two-dimensional (4,4) network of (I), extending in the ac plane. All H atoms have been omitted for clarity. [Key says Zn are turquoise spheres, but tetrahedra are used in plot. Consistency is preferable]
	Fig. 4. A view of the three-dimensional framework of (I). All H atoms have been omitted for clarity. [Key says Zn are turquoise spheres, but tetrahedra are used in plot. Consistency is preferable]
	Fig. 5. A view of the topological structure of (I). Turquoise balls represent 5-connected nodes and purple lines represent L^2- and bpe linkers.
	Fig. 6. Experimental and simulated powder X-ray diffraction patterns for (I).
	Fig. 7. The emission spectrum of (I) in the solid state at ambient temperature.

Poly[[µ₂-(E)-1,2-bis(pyridin-4-yl)ethene][µ₄-(E)-2,2'-(diazene-1,2-diyl)dibenzoato][µ₂-(E)-2,2'-(diazene-1,2-diyl)dibenzoato]dizinc(II)]

Crystal data

[Zn(C14H8N2O4)2(C12H10N2)]	Z = 2
Mr = 424.70	F(000) = 432
Triclinic, P1	Dx = 1.609 Mg m^−3
a = 8.1153 (16) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.3797 (19) Å	Cell parameters from 1231 reflections
c = 13.350 (3) Å	θ = 2.4–23.8°
α = 93.81 (3)°	µ = 1.43 mm^−1
β = 105.48 (3)°	T = 296 K
γ = 114.03 (3)°	Block, pink
V = 876.6 (4) Å^3	0.30 × 0.15 × 0.15 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	2925 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.047
φ and ω scans	θmax = 28.4°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −7→10
Tmin = 0.773, Tmax = 0.806	k = −12→12
7799 measured reflections	l = −17→17
4330 independent reflections

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.111	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0443P)^2] where P = (Fo^2 + 2Fc^2)/3
4330 reflections	(Δ/σ)max < 0.001
253 parameters	Δρmax = 0.42 e Å^−3
0 restraints	Δρmin = −0.50 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Zn1	0.38309 (5)	0.45236 (5)	0.33718 (3)	0.03066 (13)
C1	0.3888 (4)	0.6644 (3)	0.5065 (3)	0.0272 (7)
C2	0.3073 (4)	0.7622 (4)	0.5506 (2)	0.0275 (7)
C3	0.4283 (5)	0.9177 (4)	0.6029 (3)	0.0410 (9)
H3	0.5590	0.9539	0.6179	0.049*
C4	0.3601 (6)	1.0208 (4)	0.6334 (3)	0.0487 (10)
H4	0.4444	1.1242	0.6699	0.058*
C5	0.1661 (5)	0.9692 (4)	0.6093 (3)	0.0424 (9)
H5	0.1191	1.0387	0.6279	0.051*
C6	0.0421 (5)	0.8145 (4)	0.5576 (3)	0.0375 (8)
H6	−0.0886	0.7803	0.5408	0.045*
C7	0.1110 (4)	0.7100 (4)	0.5306 (2)	0.0266 (7)
C8	0.6038 (5)	0.5271 (4)	0.2250 (3)	0.0319 (7)
C9	0.7638 (4)	0.6074 (4)	0.1808 (3)	0.0295 (7)
C10	0.9440 (5)	0.7020 (4)	0.2511 (3)	0.0378 (8)
H10	0.9597	0.7287	0.3225	0.045*
C11	1.1019 (5)	0.7576 (4)	0.2169 (3)	0.0454 (9)
H11	1.2224	0.8207	0.2654	0.054*
C12	1.0812 (5)	0.7200 (5)	0.1120 (3)	0.0482 (10)
H12	1.1878	0.7565	0.0896	0.058*
C13	0.9028 (5)	0.6281 (4)	0.0392 (3)	0.0403 (9)
H13	0.8886	0.6020	−0.0320	0.048*
C14	0.7439 (4)	0.5748 (4)	0.0737 (3)	0.0301 (7)
C15	−0.0319 (4)	0.3288 (4)	0.2245 (3)	0.0312 (7)
H15	−0.0138	0.4227	0.2638	0.037*
C16	−0.2094 (4)	0.2310 (4)	0.1563 (3)	0.0335 (8)
H16	−0.3077	0.2606	0.1488	0.040*
C17	−0.2445 (4)	0.0881 (4)	0.0979 (3)	0.0315 (7)
C18	−0.0903 (5)	0.0506 (4)	0.1155 (3)	0.0362 (8)
H18	−0.1071	−0.0460	0.0809	0.043*
C19	0.0861 (5)	0.1564 (4)	0.1839 (3)	0.0339 (8)
H19	0.1871	0.1300	0.1930	0.041*
C20	−0.4296 (4)	−0.0189 (4)	0.0195 (3)	0.0361 (8)
H20	−0.4493	−0.1217	−0.0047	0.043*
N1	−0.0272 (3)	0.5499 (3)	0.4831 (2)	0.0293 (6)
N2	0.5638 (4)	0.4837 (3)	−0.0072 (2)	0.0339 (7)
N3	0.1184 (3)	0.2957 (3)	0.2378 (2)	0.0290 (6)
O1	0.3036 (3)	0.5906 (3)	0.41223 (18)	0.0339 (5)
O2	0.5448 (3)	0.6719 (3)	0.56363 (19)	0.0360 (6)
O3	0.5075 (3)	0.3813 (3)	0.1989 (2)	0.0435 (6)
O4	0.5838 (3)	0.6125 (3)	0.2938 (2)	0.0452 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0231 (2)	0.0353 (2)	0.0287 (2)	0.01081 (16)	0.00582 (16)	−0.00039 (16)
C1	0.0198 (16)	0.0238 (16)	0.0347 (19)	0.0056 (13)	0.0102 (14)	0.0071 (14)
C2	0.0238 (16)	0.0305 (16)	0.0263 (17)	0.0120 (13)	0.0060 (13)	0.0027 (13)
C3	0.0309 (19)	0.0350 (19)	0.049 (2)	0.0111 (16)	0.0084 (17)	−0.0028 (17)
C4	0.050 (2)	0.0276 (19)	0.055 (3)	0.0116 (17)	0.009 (2)	−0.0084 (17)
C5	0.049 (2)	0.0351 (19)	0.048 (2)	0.0233 (18)	0.0162 (19)	0.0024 (17)
C6	0.0322 (19)	0.041 (2)	0.044 (2)	0.0196 (16)	0.0143 (17)	0.0102 (17)
C7	0.0256 (16)	0.0281 (16)	0.0242 (17)	0.0107 (13)	0.0075 (13)	0.0039 (13)
C8	0.0281 (18)	0.0392 (19)	0.034 (2)	0.0178 (15)	0.0138 (15)	0.0101 (16)
C9	0.0282 (17)	0.0314 (17)	0.0316 (19)	0.0143 (14)	0.0116 (15)	0.0062 (14)
C10	0.0330 (19)	0.0393 (19)	0.033 (2)	0.0126 (16)	0.0055 (16)	0.0012 (16)
C11	0.027 (2)	0.043 (2)	0.053 (3)	0.0070 (16)	0.0065 (18)	0.0094 (19)
C12	0.028 (2)	0.059 (2)	0.058 (3)	0.0144 (18)	0.0218 (19)	0.017 (2)
C13	0.035 (2)	0.053 (2)	0.037 (2)	0.0182 (18)	0.0202 (17)	0.0100 (18)
C14	0.0239 (17)	0.0334 (17)	0.0285 (18)	0.0114 (14)	0.0046 (14)	0.0023 (14)
C15	0.0286 (18)	0.0275 (17)	0.0332 (19)	0.0131 (14)	0.0041 (15)	−0.0020 (14)
C16	0.0231 (17)	0.0355 (18)	0.039 (2)	0.0144 (14)	0.0057 (15)	−0.0007 (15)
C17	0.0240 (17)	0.0301 (17)	0.0335 (19)	0.0075 (14)	0.0069 (15)	0.0019 (14)
C18	0.0288 (18)	0.0305 (18)	0.043 (2)	0.0131 (15)	0.0046 (16)	−0.0058 (15)
C19	0.0281 (18)	0.0358 (18)	0.037 (2)	0.0181 (15)	0.0058 (15)	−0.0016 (15)
C20	0.0275 (18)	0.0322 (18)	0.037 (2)	0.0085 (14)	0.0022 (15)	−0.0025 (15)
N1	0.0242 (14)	0.0287 (15)	0.0310 (16)	0.0094 (12)	0.0070 (12)	0.0037 (12)
N2	0.0281 (16)	0.0417 (16)	0.0299 (16)	0.0157 (13)	0.0069 (13)	0.0023 (13)
N3	0.0212 (14)	0.0336 (15)	0.0273 (15)	0.0108 (12)	0.0045 (11)	−0.0012 (12)
O1	0.0244 (12)	0.0419 (13)	0.0301 (13)	0.0134 (10)	0.0054 (10)	−0.0043 (10)
O2	0.0235 (12)	0.0390 (13)	0.0412 (14)	0.0129 (10)	0.0054 (11)	0.0064 (11)
O3	0.0361 (14)	0.0383 (14)	0.0584 (18)	0.0134 (12)	0.0238 (13)	0.0101 (12)
O4	0.0462 (15)	0.0487 (15)	0.0477 (16)	0.0200 (13)	0.0283 (13)	0.0053 (12)

Geometric parameters (Å, º)

Zn1—O2^i	1.950 (2)	C10—H10	0.9300
Zn1—O4	1.968 (3)	C11—C12	1.370 (5)
Zn1—O1	1.988 (2)	C11—H11	0.9300
Zn1—N3	2.046 (3)	C12—C13	1.380 (5)
Zn1—C8	2.548 (3)	C12—H12	0.9300
C1—O1	1.254 (4)	C13—C14	1.396 (4)
C1—O2	1.263 (4)	C13—H13	0.9300
C1—C2	1.502 (4)	C14—N2	1.432 (4)
C2—C3	1.382 (4)	C15—N3	1.347 (4)
C2—C7	1.403 (4)	C15—C16	1.363 (4)
C3—C4	1.383 (5)	C15—H15	0.9300
C3—H3	0.9300	C16—C17	1.385 (4)
C4—C5	1.380 (5)	C16—H16	0.9300
C4—H4	0.9300	C17—C18	1.398 (4)
C5—C6	1.379 (5)	C17—C20	1.468 (4)
C5—H5	0.9300	C18—C19	1.375 (4)
C6—C7	1.382 (4)	C18—H18	0.9300
C6—H6	0.9300	C19—N3	1.338 (4)
C7—N1	1.428 (4)	C19—H19	0.9300
C8—O3	1.234 (4)	C20—C20^ii	1.318 (6)
C8—O4	1.265 (4)	C20—H20	0.9300
C8—C9	1.508 (4)	N1—N1^iii	1.250 (5)
C9—C10	1.381 (4)	N2—N2^iv	1.249 (5)
C9—C14	1.392 (4)	O2—Zn1^i	1.950 (2)
C10—C11	1.387 (5)
O2^i—Zn1—O4	118.20 (10)	C9—C10—H10	119.5
O2^i—Zn1—O1	107.12 (10)	C11—C10—H10	119.5
O4—Zn1—O1	100.81 (10)	C12—C11—C10	120.2 (3)
O2^i—Zn1—N3	104.20 (11)	C12—C11—H11	119.9
O4—Zn1—N3	125.34 (11)	C10—C11—H11	119.9
O1—Zn1—N3	97.67 (10)	C11—C12—C13	120.3 (3)
O2^i—Zn1—C8	109.36 (10)	C11—C12—H12	119.9
O4—Zn1—C8	29.08 (10)	C13—C12—H12	119.9
O1—Zn1—C8	128.64 (10)	C12—C13—C14	119.3 (3)
N3—Zn1—C8	106.88 (11)	C12—C13—H13	120.4
O1—C1—O2	124.6 (3)	C14—C13—H13	120.4
O1—C1—C2	117.1 (3)	C9—C14—C13	121.0 (3)
O2—C1—C2	118.1 (3)	C9—C14—N2	123.3 (3)
C3—C2—C7	117.9 (3)	C13—C14—N2	115.7 (3)
C3—C2—C1	118.6 (3)	N3—C15—C16	123.1 (3)
C7—C2—C1	123.1 (3)	N3—C15—H15	118.4
C2—C3—C4	121.7 (3)	C16—C15—H15	118.4
C2—C3—H3	119.1	C15—C16—C17	120.6 (3)
C4—C3—H3	119.1	C15—C16—H16	119.7
C5—C4—C3	119.5 (3)	C17—C16—H16	119.7
C5—C4—H4	120.2	C16—C17—C18	116.2 (3)
C3—C4—H4	120.2	C16—C17—C20	123.3 (3)
C4—C5—C6	120.0 (3)	C18—C17—C20	120.5 (3)
C4—C5—H5	120.0	C19—C18—C17	120.2 (3)
C6—C5—H5	120.0	C19—C18—H18	119.9
C5—C6—C7	120.4 (3)	C17—C18—H18	119.9
C5—C6—H6	119.8	N3—C19—C18	122.8 (3)
C7—C6—H6	119.8	N3—C19—H19	118.6
C6—C7—C2	120.4 (3)	C18—C19—H19	118.6
C6—C7—N1	116.4 (3)	C20^ii—C20—C17	125.3 (4)
C2—C7—N1	123.2 (3)	C20^ii—C20—H20	117.4
O3—C8—O4	122.8 (3)	C17—C20—H20	117.4
O3—C8—C9	119.5 (3)	N1^iii—N1—C7	112.5 (3)
O4—C8—C9	117.5 (3)	N2^iv—N2—C14	112.2 (3)
O3—C8—Zn1	73.71 (19)	C19—N3—C15	117.1 (3)
O4—C8—Zn1	49.10 (16)	C19—N3—Zn1	121.9 (2)
C9—C8—Zn1	165.6 (2)	C15—N3—Zn1	121.0 (2)
C10—C9—C14	118.2 (3)	C1—O1—Zn1	124.4 (2)
C10—C9—C8	118.3 (3)	C1—O2—Zn1^i	134.9 (2)
C14—C9—C8	123.0 (3)	C8—O4—Zn1	101.8 (2)
C9—C10—C11	121.0 (3)
O1—C1—C2—C3	−131.0 (3)	C8—C9—C14—C13	−167.7 (3)
O2—C1—C2—C3	43.6 (4)	C10—C9—C14—N2	−177.5 (3)
O1—C1—C2—C7	41.2 (4)	C8—C9—C14—N2	11.0 (5)
O2—C1—C2—C7	−144.1 (3)	C12—C13—C14—C9	−2.7 (5)
C7—C2—C3—C4	−1.1 (5)	C12—C13—C14—N2	178.5 (3)
C1—C2—C3—C4	171.5 (3)	N3—C15—C16—C17	1.5 (5)
C2—C3—C4—C5	−1.4 (6)	C15—C16—C17—C18	1.4 (5)
C3—C4—C5—C6	1.7 (6)	C15—C16—C17—C20	−177.0 (3)
C4—C5—C6—C7	0.7 (6)	C16—C17—C18—C19	−2.9 (5)
C5—C6—C7—C2	−3.3 (5)	C20—C17—C18—C19	175.6 (3)
C5—C6—C7—N1	176.4 (3)	C17—C18—C19—N3	1.5 (5)
C3—C2—C7—C6	3.5 (5)	C16—C17—C20—C20^ii	13.6 (7)
C1—C2—C7—C6	−168.8 (3)	C18—C17—C20—C20^ii	−164.8 (5)
C3—C2—C7—N1	−176.2 (3)	C6—C7—N1—N1^iii	−139.0 (4)
C1—C2—C7—N1	11.5 (5)	C2—C7—N1—N1^iii	40.6 (5)
O3—C8—C9—C10	−125.1 (4)	C9—C14—N2—N2^iv	40.5 (5)
O4—C8—C9—C10	49.9 (4)	C13—C14—N2—N2^iv	−140.7 (4)
Zn1—C8—C9—C10	29.9 (11)	C18—C19—N3—C15	1.4 (5)
O3—C8—C9—C14	46.4 (5)	C18—C19—N3—Zn1	−179.0 (3)
O4—C8—C9—C14	−138.6 (3)	C16—C15—N3—C19	−3.0 (5)
Zn1—C8—C9—C14	−158.6 (8)	C16—C15—N3—Zn1	177.5 (3)
C14—C9—C10—C11	−2.6 (5)	O2—C1—O1—Zn1	6.2 (4)
C8—C9—C10—C11	169.3 (3)	C2—C1—O1—Zn1	−179.46 (19)
C9—C10—C11—C12	0.3 (6)	O1—C1—O2—Zn1^i	−91.7 (4)
C10—C11—C12—C13	0.8 (6)	C2—C1—O2—Zn1^i	94.1 (3)
C11—C12—C13—C14	0.4 (6)	O3—C8—O4—Zn1	1.2 (4)
C10—C9—C14—C13	3.8 (5)	C9—C8—O4—Zn1	−173.6 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C16—H16···O3^v	0.93	2.41	3.289 (4)	158
C4—H4···O4^vi	0.93	2.60	3.320 (4)	135
C15—H15···O1	0.93	2.57	3.134 (4)	120

Symmetry codes: (v) x−1, y, z; (vi) −x+1, −y+2, −z+1.