Crystal structure of poly[di-chlorido-(μ-2,5-di-carb-oxy-benzene-1,4-di-carboxyl-ato-κ2O1:O4)bis-[μ-4'-(pyridin-3-yl)-4,2':6',4''-terpyridine-κ2N1:N4']dizinc].

In the title polymeric ZnII complex, [Zn2(C10H4O8)Cl2(C20H14N4)2] n , the ZnII cations are bridged by both 2,5-di-carb-oxy-benzene-1,4-di-carboxyl-ate dianions and 4'-(pyridin-3-yl)-4,2':6',4''-terpyridine ligands, forming ladder-like polymeric chains propagating along [1-10]. The Cl- anion further coordinates the ZnII cation to complete a distorted tetra-hedral environment. In the 4'-(pyridin-3-yl)-4,2':6',4''-terpyridine ligand, the three sideward pyridine rings are twisted with respect to the central pyridine ring by 39.27 (12), 14.89 (13) and 3.36 (13)°, respectively. In the crystal, classical O-H⋯N hydrogen bonds and weak C-H⋯O and C-H⋯Cl hydrogen bonds link the chains into a three-dimensional supra-molecular architecture. π-π stacking is observed between the pyridine and benzene rings of neighbouring polymeric chains, with a centroid-to-centroid distance of 3.7280 (14) Å.

Chemical context

Coordination polymers (CPs) represent a class of crystalline materials which consist of different ligands inter­connected by metallic nodes (Yaghi & Li; 1995 ▸; Hinter­holzinger et al., 2012 ▸). Compared to traditional inorganic materials, CPs have fascinating structures with regular pore shape and size obtained by rational design (Kepert, 2006 ▸; Brammer, 2004 ▸). In addition, studies over several decades have revealed that CPs have multi-functional applications such as gas storage and separation (Rosi et al., 2003 ▸; Jiang et al., 2013 ▸), chemical purification (Li et al., 2012 ▸), catalysis (Seo et al., 2000 ▸), and sensors (Kreno et al., 2012 ▸), etc.

Pyridine-containing compounds, such as 4,2′:6′,4′′-terpyridine derivatives, are of great importance in the design of organic ligands, because conjugated polypyridyl ligands can form a better rigid plane and improve the stability of the network (Hancock, 2013 ▸; Li et al., 2011 ▸; Bhaumik et al., 2011 ▸). As a rigid planar and triangular ligand, 4′-(3-pyrid­yl)-4,2′:6′,4′′-terpyridine (344-pytpy; Housecroft, 2014 ▸) is different from commonly employed polypyridyl ligands such as 1,3,5-tri(4-pyrid­yl)-2,4,6-triazine (Ma & Coppens, 2003 ▸; Kumazawa et al., 2003 ▸), which have been widely studied in the field of coordination chemistry. Its rigidity and trigonal geometry may lead to the formation of nanosized cages and porous frameworks enclosing cavities and channels (Li et al., 2008 ▸; Yoshizawa et al., 2004 ▸; Dai et al., 2008 ▸). 1,2,4,5-Benzene­tetracarbonic acid (H4bta) is frequently employed due to the rich coordination binding sites of the carboxyl­ate groups (Hou et al., 2011 ▸). We selected 344-pytpy and 1,2,4,5-benzene­tetra­carbonic acid as the organic linkers which, when assembled with Zn cations, resulted in the title coordination polymer [Zn2(344-pytpy)2(H2bta)Cl2].

Structural commentary

As shown in Fig. 1 ▸, the asymmetric unit of the title compound contains one ZnII cation, one 344-pytpy ligand, a half of an H2bta2− anion and one coordinating Cl− anion. The ZnII atom is four-coordinated by two nitro­gen atoms (N1, N3) from two different 344-pytpy ligands [Zn1—N1 = 2.070 (2) and Zn1—N3 = 2.0217 (18) Å], one oxygen atom (O2) from an H2bta2− anion [Zn1—O2 = 1.9171 (16) Å] and one Cl atom [Zn1—Cl1 = 2.2278 (7) Å] in a distorted tetra­hedral coordination geometry. The bond lengths around Zn1 are similar to those reported by Wang et al. (2009 ▸). The X—Zn—X (X = N, O or Cl atom) angles range from 97.21 (8) to 115.73 (8)° and the tetra­hedron edge lengths range from 2.992 (3) to 3.591 (2) Å. Each 344-pytpy ligand act as 2-connecting node, linking two Zn atoms by the outer N-terminal atoms (N1, N3), the central and another outer pyridine N atom (N2, N4) are free. The H2bta2− anion is located on an inversion center, and bridges two ZnII atoms through the two carboxyl­ate groups. In this way, chains propagating along [10] are formed (Fig. 2 ▸).

Figure 1

Part of the polymeric structure of the title complex [symmetry codes: (i) −x, −y + 1, −z + 2; (ii) x + 1, y − 1, z]. Displacement ellipsoids are drawn at the 50% probability level.

Figure 2

Part of the polymeric chain.

Supra­molecular features

In the crystal, classical O—H⋯N hydrogen bonds, weak C—H⋯O and C—H⋯Cl hydrogen bonds (Table 1 ▸) link the chains into a three-dimensional supra­molecular architecture. π–π stacking is observed between the N3-pyridine ring and benzene ring of the neighboring chain, with a centroid-to-centroid distance of 3.7280 (14) Å.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3A⋯N4ii	0.82	1.83	2.633 (3)	167
C15—H15⋯O1iii	0.93	2.46	3.383 (3)	172
C17—H17⋯Cl1iv	0.93	2.75	3.678 (3)	173
C22—H22⋯O4v	0.93	2.59	3.305 (4)	134
C25—H25⋯O1iii	0.93	2.34	3.267 (3)	175

Symmetry codes: (ii) ; (iii) ; (iv) ; (v) .

Synthesis and crystallization

4′-(3-Pyrid­yl)-4,2′:6′,4′′-terpyridine was synthesized accord­ing to a literature method (Yang et al., 2014 ▸). 344-pytpy (0.0310 g, 0.1 mmol), ZnCl2 (0.0136 g, 0.1 mmol) and 1,2,4,5-benzene­tetra­carbonic acid (0.0254 g, 0.1 mmol) were adequately dispersed in 10 mL of distilled water, and then the mixture was sealed and heated to 453 K for three days under hydro­thermal conditions. The vial was then allowed to cool to room temperature. Colorless block-shaped crystals were collected (0.010 g, yield 38.9%, based on Zn).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. All H atoms were placed in geometrically idealized positions and treated as riding, with C—H = 0.93 and O—H = 0.82 Å, and with U iso(H) = 1.2U eq(C) and 1.5U eq(O).

Table 2

Experimental details

Crystal data
Chemical formula	[Zn2(C10H4O8)Cl2(C20H14N4)2]
M r	537.24
Crystal system, space group	Triclinic, P
Temperature (K)	296
a, b, c (Å)	8.6557 (6), 12.1432 (8), 12.5842 (9)
α, β, γ (°)	61.396 (1), 74.216 (1), 75.411 (1)
V (Å3)	1105.83 (13)
Z	2
Radiation type	Mo Kα
μ (mm−1)	1.27
Crystal size (mm)	0.23 × 0.22 × 0.17
Data collection
Diffractometer	Bruker SMART APEX CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2000 ▸)
T min, T max	0.758, 0.813
No. of measured, independent and observed [I > 2σ(I)] reflections	7896, 3840, 3435
R int	0.018
(sin θ/λ)max (Å−1)	0.595
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.029, 0.080, 1.07
No. of reflections	3840
No. of parameters	317
H-atom treatment	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	0.32, −0.27

Computer programs: SMART and SAINT (Bruker, 2000 ▸), SHELXS97 and SHELXTL (Sheldrick, 2008 ▸) and SHELXL2013 (Sheldrick, 2015 ▸).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989016016285/xu5893sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989016016285/xu5893Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989016016285/xu5893Isup3.cdx

CCDC reference: 1509671

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Zn2(C10H4O8)Cl2(C20H14N4)2]	Z = 2
Mr = 537.24	F(000) = 546
Triclinic, P1	Dx = 1.613 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.6557 (6) Å	Cell parameters from 4113 reflections
b = 12.1432 (8) Å	θ = 2.5–26.8°
c = 12.5842 (9) Å	µ = 1.27 mm−1
α = 61.396 (1)°	T = 296 K
β = 74.216 (1)°	Block, colorless
γ = 75.411 (1)°	0.23 × 0.22 × 0.17 mm
V = 1105.83 (13) Å3

Bruker SMART APEX CCD diffractometer	3840 independent reflections
Radiation source: fine-focus sealed tube	3435 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
phi and ω scans	θmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −10→10
Tmin = 0.758, Tmax = 0.813	k = −14→12
7896 measured reflections	l = −14→14

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.080	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.043P)2 + 0.4805P] where P = (Fo2 + 2Fc2)/3
3840 reflections	(Δ/σ)max = 0.001
317 parameters	Δρmax = 0.32 e Å−3
0 restraints	Δρmin = −0.27 e Å−3

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 > 2sigma(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.

	x	y	z	Uiso*/Ueq
C1	0.3397 (3)	0.4695 (2)	0.8900 (2)	0.0279 (5)
C2	0.1613 (3)	0.4839 (2)	0.9422 (2)	0.0218 (5)
C3	0.1062 (3)	0.3951 (2)	1.0600 (2)	0.0239 (5)
H3	0.1774	0.3240	1.1002	0.029*
C4	−0.0533 (3)	0.4105 (2)	1.11919 (19)	0.0219 (5)
C5	−0.0971 (3)	0.3173 (2)	1.2513 (2)	0.0306 (6)
C6	0.6841 (3)	0.8624 (2)	0.5920 (2)	0.0297 (5)
H6	0.7535	0.8319	0.5380	0.036*
C7	0.6660 (3)	0.9894 (2)	0.5599 (2)	0.0317 (6)
H7	0.7220	1.0438	0.4860	0.038*
C8	0.5628 (3)	1.0346 (2)	0.6398 (2)	0.0280 (5)
H8	0.5457	1.1208	0.6186	0.034*
C9	0.4845 (3)	0.9514 (2)	0.7519 (2)	0.0228 (5)
C10	0.5101 (3)	0.8245 (2)	0.7761 (2)	0.0269 (5)
H10	0.4580	0.7676	0.8505	0.032*
C11	0.3721 (3)	0.9962 (2)	0.8406 (2)	0.0234 (5)
C12	0.2691 (3)	1.1105 (2)	0.7983 (2)	0.0259 (5)
H12	0.2725	1.1608	0.7143	0.031*
C13	0.1608 (3)	1.1490 (2)	0.8828 (2)	0.0236 (5)
C14	0.2517 (3)	0.9694 (2)	1.0459 (2)	0.0230 (5)
C15	0.3640 (3)	0.9256 (2)	0.9672 (2)	0.0254 (5)
H15	0.4331	0.8497	0.9987	0.030*
C16	0.0390 (3)	1.2655 (2)	0.8443 (2)	0.0237 (5)
C17	0.0453 (3)	1.3573 (2)	0.7232 (2)	0.0303 (6)
H17	0.1331	1.3513	0.6632	0.036*
C18	−0.0777 (3)	1.4565 (2)	0.6922 (2)	0.0299 (6)
H18	−0.0715	1.5165	0.6104	0.036*
C19	−0.2098 (3)	1.3857 (2)	0.8926 (2)	0.0251 (5)
H19	−0.2965	1.3958	0.9514	0.030*
C20	−0.0910 (3)	1.2841 (2)	0.9303 (2)	0.0254 (5)
H20	−0.0971	1.2276	1.0133	0.030*
C21	0.2301 (3)	0.8971 (2)	1.1827 (2)	0.0239 (5)
C22	0.1156 (3)	0.9462 (3)	1.2565 (2)	0.0334 (6)
H22	0.0533	1.0248	1.2213	0.040*
C23	0.0956 (3)	0.8769 (3)	1.3826 (2)	0.0374 (6)
H23	0.0199	0.9115	1.4309	0.045*
C24	0.2886 (3)	0.7152 (2)	1.3680 (2)	0.0331 (6)
H24	0.3473	0.6355	1.4060	0.040*
C25	0.3188 (3)	0.7786 (2)	1.2413 (2)	0.0283 (5)
H25	0.3975	0.7426	1.1955	0.034*
Cl1	0.60963 (8)	0.63418 (6)	0.52615 (5)	0.03639 (17)
N1	0.6063 (2)	0.78037 (18)	0.69741 (18)	0.0272 (4)
N2	0.1514 (2)	1.07932 (18)	1.00421 (17)	0.0252 (4)
N3	−0.2072 (2)	1.47156 (17)	0.77436 (17)	0.0234 (4)
N4	0.1792 (3)	0.7629 (2)	1.43877 (18)	0.0352 (5)
O1	0.4167 (2)	0.36497 (18)	0.9094 (2)	0.0572 (6)
O2	0.3980 (2)	0.57395 (16)	0.83257 (16)	0.0351 (4)
O3	−0.1565 (3)	0.37407 (17)	1.32170 (15)	0.0459 (5)
H3A	−0.1605	0.3216	1.3939	0.069*
O4	−0.0721 (4)	0.20509 (19)	1.2873 (2)	0.0792 (9)
Zn1	0.59827 (3)	0.60234 (2)	0.71763 (2)	0.02356 (10)

	U11	U22	U33	U12	U13	U23
C1	0.0224 (12)	0.0315 (14)	0.0246 (12)	−0.0014 (11)	0.0023 (10)	−0.0128 (11)
C2	0.0208 (11)	0.0233 (12)	0.0210 (11)	−0.0041 (9)	0.0016 (9)	−0.0117 (10)
C3	0.0225 (12)	0.0239 (12)	0.0212 (11)	−0.0017 (9)	−0.0032 (9)	−0.0078 (10)
C4	0.0236 (12)	0.0216 (12)	0.0177 (11)	−0.0052 (9)	0.0018 (9)	−0.0085 (9)
C5	0.0269 (13)	0.0289 (14)	0.0248 (12)	−0.0014 (10)	0.0015 (10)	−0.0074 (11)
C6	0.0296 (13)	0.0293 (13)	0.0285 (12)	−0.0070 (10)	0.0075 (10)	−0.0167 (11)
C7	0.0355 (14)	0.0297 (14)	0.0254 (12)	−0.0126 (11)	0.0064 (10)	−0.0110 (11)
C8	0.0319 (13)	0.0198 (12)	0.0285 (12)	−0.0032 (10)	−0.0028 (10)	−0.0094 (10)
C9	0.0232 (12)	0.0207 (12)	0.0222 (11)	0.0001 (9)	−0.0041 (9)	−0.0092 (10)
C10	0.0277 (13)	0.0223 (12)	0.0221 (11)	−0.0024 (10)	0.0034 (10)	−0.0077 (10)
C11	0.0247 (12)	0.0220 (12)	0.0228 (11)	−0.0017 (9)	−0.0027 (9)	−0.0109 (10)
C12	0.0284 (13)	0.0235 (12)	0.0185 (11)	0.0001 (10)	−0.0017 (9)	−0.0065 (10)
C13	0.0244 (12)	0.0206 (12)	0.0217 (11)	0.0007 (9)	−0.0044 (9)	−0.0078 (9)
C14	0.0242 (12)	0.0199 (12)	0.0228 (11)	0.0002 (9)	−0.0046 (9)	−0.0093 (10)
C15	0.0259 (12)	0.0197 (12)	0.0243 (12)	0.0030 (9)	−0.0051 (10)	−0.0075 (10)
C16	0.0240 (12)	0.0212 (12)	0.0244 (11)	−0.0009 (9)	−0.0039 (9)	−0.0102 (10)
C17	0.0240 (12)	0.0294 (13)	0.0234 (12)	0.0045 (10)	0.0034 (10)	−0.0085 (10)
C18	0.0290 (13)	0.0254 (13)	0.0229 (12)	0.0027 (10)	−0.0004 (10)	−0.0063 (10)
C19	0.0228 (12)	0.0279 (13)	0.0235 (11)	−0.0026 (10)	0.0026 (9)	−0.0145 (10)
C20	0.0301 (13)	0.0227 (12)	0.0207 (11)	−0.0015 (10)	−0.0042 (10)	−0.0088 (10)
C21	0.0255 (12)	0.0231 (12)	0.0216 (11)	−0.0030 (9)	−0.0043 (9)	−0.0089 (10)
C22	0.0314 (14)	0.0353 (15)	0.0274 (13)	0.0053 (11)	−0.0047 (11)	−0.0142 (11)
C23	0.0309 (14)	0.0513 (17)	0.0277 (13)	−0.0027 (12)	0.0020 (11)	−0.0207 (13)
C24	0.0459 (16)	0.0254 (13)	0.0254 (12)	−0.0056 (11)	−0.0115 (11)	−0.0062 (11)
C25	0.0338 (13)	0.0264 (13)	0.0236 (12)	0.0003 (10)	−0.0055 (10)	−0.0122 (10)
Cl1	0.0431 (4)	0.0347 (4)	0.0254 (3)	0.0005 (3)	−0.0060 (3)	−0.0116 (3)
N1	0.0283 (11)	0.0197 (10)	0.0263 (10)	−0.0008 (8)	0.0023 (8)	−0.0094 (8)
N2	0.0246 (10)	0.0228 (10)	0.0229 (10)	0.0026 (8)	−0.0027 (8)	−0.0096 (8)
N3	0.0216 (10)	0.0211 (10)	0.0236 (10)	0.0011 (8)	−0.0020 (8)	−0.0098 (8)
N4	0.0430 (13)	0.0395 (13)	0.0204 (10)	−0.0138 (11)	−0.0020 (9)	−0.0092 (10)
O1	0.0329 (11)	0.0332 (11)	0.0777 (15)	0.0026 (9)	0.0135 (10)	−0.0184 (11)
O2	0.0243 (9)	0.0326 (10)	0.0384 (10)	−0.0087 (8)	0.0103 (8)	−0.0140 (8)
O3	0.0776 (15)	0.0351 (11)	0.0173 (8)	−0.0151 (10)	0.0021 (9)	−0.0076 (8)
O4	0.125 (2)	0.0231 (12)	0.0391 (12)	0.0033 (12)	0.0276 (13)	−0.0023 (9)
Zn1	0.02041 (16)	0.01912 (16)	0.02327 (15)	0.00026 (10)	0.00197 (11)	−0.00766 (11)

C1—O1	1.217 (3)	C14—C15	1.389 (3)
C1—O2	1.277 (3)	C14—C21	1.493 (3)
C1—C2	1.507 (3)	C15—H15	0.9300
C2—C3	1.389 (3)	C16—C20	1.390 (3)
C2—C4i	1.399 (3)	C16—C17	1.389 (3)
C3—C4	1.393 (3)	C17—C18	1.366 (3)
C3—H3	0.9300	C17—H17	0.9300
C4—C2i	1.399 (3)	C18—N3	1.344 (3)
C4—C5	1.503 (3)	C18—H18	0.9300
C5—O4	1.192 (3)	C19—N3	1.345 (3)
C5—O3	1.298 (3)	C19—C20	1.368 (3)
C6—N1	1.339 (3)	C19—H19	0.9300
C6—C7	1.372 (3)	C20—H20	0.9300
C6—H6	0.9300	C21—C22	1.390 (3)
C7—C8	1.379 (3)	C21—C25	1.392 (3)
C7—H7	0.9300	C22—C23	1.379 (3)
C8—C9	1.390 (3)	C22—H22	0.9300
C8—H8	0.9300	C23—N4	1.333 (3)
C9—C10	1.389 (3)	C23—H23	0.9300
C9—C11	1.488 (3)	C24—N4	1.336 (3)
C10—N1	1.341 (3)	C24—C25	1.379 (3)
C10—H10	0.9300	C24—H24	0.9300
C11—C12	1.390 (3)	C25—H25	0.9300
C11—C15	1.392 (3)	Zn1—Cl1	2.2278 (7)
C12—C13	1.393 (3)	Zn1—N1	2.070 (2)
C12—H12	0.9300	Zn1—O2	1.9171 (16)
C13—N2	1.336 (3)	Zn1—N3ii	2.0217 (18)
C13—C16	1.490 (3)	O3—H3A	0.8200
C14—N2	1.343 (3)
O1—C1—O2	125.8 (2)	C20—C16—C13	120.1 (2)
O1—C1—C2	120.4 (2)	C17—C16—C13	122.8 (2)
O2—C1—C2	113.6 (2)	C18—C17—C16	119.9 (2)
C3—C2—C4i	119.3 (2)	C18—C17—H17	120.1
C3—C2—C1	118.5 (2)	C16—C17—H17	120.1
C4i—C2—C1	122.0 (2)	N3—C18—C17	123.1 (2)
C2—C3—C4	121.4 (2)	N3—C18—H18	118.4
C2—C3—H3	119.3	C17—C18—H18	118.4
C4—C3—H3	119.3	N3—C19—C20	123.1 (2)
C3—C4—C2i	119.3 (2)	N3—C19—H19	118.5
C3—C4—C5	117.6 (2)	C20—C19—H19	118.5
C2i—C4—C5	122.9 (2)	C19—C20—C16	119.8 (2)
O4—C5—O3	124.4 (2)	C19—C20—H20	120.1
O4—C5—C4	124.0 (2)	C16—C20—H20	120.1
O3—C5—C4	111.4 (2)	C22—C21—C25	117.5 (2)
N1—C6—C7	122.9 (2)	C22—C21—C14	120.1 (2)
N1—C6—H6	118.5	C25—C21—C14	122.4 (2)
C7—C6—H6	118.5	C23—C22—C21	119.2 (2)
C6—C7—C8	118.5 (2)	C23—C22—H22	120.4
C6—C7—H7	120.7	C21—C22—H22	120.4
C8—C7—H7	120.7	N4—C23—C22	123.4 (2)
C7—C8—C9	120.0 (2)	N4—C23—H23	118.3
C7—C8—H8	120.0	C22—C23—H23	118.3
C9—C8—H8	120.0	N4—C24—C25	123.1 (2)
C8—C9—C10	117.3 (2)	N4—C24—H24	118.4
C8—C9—C11	121.7 (2)	C25—C24—H24	118.4
C10—C9—C11	121.0 (2)	C24—C25—C21	119.3 (2)
N1—C10—C9	123.1 (2)	C24—C25—H25	120.4
N1—C10—H10	118.5	C21—C25—H25	120.4
C9—C10—H10	118.5	C6—N1—C10	118.1 (2)
C12—C11—C15	118.0 (2)	C6—N1—Zn1	119.29 (16)
C12—C11—C9	120.2 (2)	C10—N1—Zn1	121.30 (16)
C15—C11—C9	121.8 (2)	C13—N2—C14	118.72 (19)
C11—C12—C13	119.4 (2)	C18—N3—C19	116.97 (19)
C11—C12—H12	120.3	C18—N3—Zn1iii	120.55 (15)
C13—C12—H12	120.3	C19—N3—Zn1iii	121.90 (15)
N2—C13—C12	122.3 (2)	C23—N4—C24	117.5 (2)
N2—C13—C16	115.34 (19)	C1—O2—Zn1	125.37 (16)
C12—C13—C16	122.25 (19)	C5—O3—H3A	109.5
N2—C14—C15	122.2 (2)	O2—Zn1—N3ii	115.73 (8)
N2—C14—C21	114.85 (19)	O2—Zn1—N1	97.21 (8)
C15—C14—C21	122.9 (2)	N3ii—Zn1—N1	115.16 (8)
C11—C15—C14	119.4 (2)	O2—Zn1—Cl1	119.86 (6)
C11—C15—H15	120.3	N3ii—Zn1—Cl1	104.98 (6)
C14—C15—H15	120.3	N1—Zn1—Cl1	103.51 (6)
C20—C16—C17	117.0 (2)
O1—C1—C2—C3	38.5 (3)	C17—C16—C20—C19	3.6 (3)
O2—C1—C2—C3	−137.7 (2)	C13—C16—C20—C19	−174.3 (2)
O1—C1—C2—C4i	−147.7 (3)	N2—C14—C21—C22	−1.5 (3)
O2—C1—C2—C4i	36.1 (3)	C15—C14—C21—C22	180.0 (2)
C4i—C2—C3—C4	−1.3 (4)	N2—C14—C21—C25	177.0 (2)
C1—C2—C3—C4	172.7 (2)	C15—C14—C21—C25	−1.6 (4)
C2—C3—C4—C2i	1.3 (4)	C25—C21—C22—C23	0.3 (4)
C2—C3—C4—C5	−173.6 (2)	C14—C21—C22—C23	178.9 (2)
C3—C4—C5—O4	−53.0 (4)	C21—C22—C23—N4	−1.1 (4)
C2i—C4—C5—O4	132.3 (3)	N4—C24—C25—C21	−1.2 (4)
C3—C4—C5—O3	123.2 (2)	C22—C21—C25—C24	0.7 (4)
C2i—C4—C5—O3	−51.5 (3)	C14—C21—C25—C24	−177.8 (2)
N1—C6—C7—C8	−0.1 (4)	C7—C6—N1—C10	−1.8 (4)
C6—C7—C8—C9	2.3 (4)	C7—C6—N1—Zn1	165.3 (2)
C7—C8—C9—C10	−2.5 (3)	C9—C10—N1—C6	1.6 (4)
C7—C8—C9—C11	−179.9 (2)	C9—C10—N1—Zn1	−165.17 (18)
C8—C9—C10—N1	0.5 (4)	C12—C13—N2—C14	1.0 (4)
C11—C9—C10—N1	177.9 (2)	C16—C13—N2—C14	176.5 (2)
C8—C9—C11—C12	38.0 (3)	C15—C14—N2—C13	−0.4 (3)
C10—C9—C11—C12	−139.3 (2)	C21—C14—N2—C13	−178.9 (2)
C8—C9—C11—C15	−143.1 (2)	C17—C18—N3—C19	2.2 (4)
C10—C9—C11—C15	39.5 (3)	C17—C18—N3—Zn1iii	−169.2 (2)
C15—C11—C12—C13	−1.1 (3)	C20—C19—N3—C18	−2.1 (3)
C9—C11—C12—C13	177.8 (2)	C20—C19—N3—Zn1iii	169.18 (18)
C11—C12—C13—N2	−0.3 (4)	C22—C23—N4—C24	0.7 (4)
C11—C12—C13—C16	−175.5 (2)	C25—C24—N4—C23	0.4 (4)
C12—C11—C15—C14	1.7 (3)	O1—C1—O2—Zn1	22.1 (4)
C9—C11—C15—C14	−177.2 (2)	C2—C1—O2—Zn1	−161.85 (15)
N2—C14—C15—C11	−1.0 (4)	C1—O2—Zn1—N3ii	−49.0 (2)
C21—C14—C15—C11	177.4 (2)	C1—O2—Zn1—N1	−171.5 (2)
N2—C13—C16—C20	−11.3 (3)	C1—O2—Zn1—Cl1	78.4 (2)
C12—C13—C16—C20	164.2 (2)	C6—N1—Zn1—O2	−152.28 (19)
N2—C13—C16—C17	170.8 (2)	C10—N1—Zn1—O2	14.38 (19)
C12—C13—C16—C17	−13.7 (4)	C6—N1—Zn1—N3ii	84.84 (19)
C20—C16—C17—C18	−3.6 (4)	C10—N1—Zn1—N3ii	−108.50 (18)
C13—C16—C17—C18	174.4 (2)	C6—N1—Zn1—Cl1	−29.16 (19)
C16—C17—C18—N3	0.7 (4)	C10—N1—Zn1—Cl1	137.50 (17)
N3—C19—C20—C16	−0.8 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···N4iv	0.82	1.83	2.633 (3)	167
C15—H15···O1v	0.93	2.46	3.383 (3)	172
C17—H17···Cl1vi	0.93	2.75	3.678 (3)	173
C22—H22···O4vii	0.93	2.59	3.305 (4)	134
C25—H25···O1v	0.93	2.34	3.267 (3)	175