A one-dimensional Zn^II coordination polymer: poly[di­chlorido­([mu]₂-1,4-phenyl­ene­di­acetato-[kappa]²O:O')bis­{[mu]₂-1,3-bis­[(1H-1,2,4-triazol-1-yl)methyl]benzene-[kappa]²N³:N^3'}di­zinc(II)]

In the title one-dimensional Zn^II coordination polymer, [Zn(C₁₀H₈O₄)_0.5Cl(C₁₂H₁₂N₆)]_n, the asymmetric unit consists of a Zn^II cation, a 1,3-bis­[(1H-1,2,4-triazol-1-yl)methyl]benzene ligand and half of a fully deprotonated centrosymmetric 1,4-phenyl­ene­di­acetic acid ligand. The crystal structure shows a one-dimensional rotaxane-like structure. This coordination polymer is reinforced by C-H...O and C-H...Cl hydrogen bonds and [pi]-[pi] inter­actions.

S1. Introduction

The rational design and synthesis of coordination polymers is of great inter­est in modern inorganic chemistry not only because of their diverse topologies and intriguing structures but also due to their potential applications in luminescence, gas storage, molecular adsorption, molecular recognition and catalysis (Cao et al., 1992; Dinca et al., 2006; Plabst et al., 2009). The structure adopted by a coordination polymer is largely affected by a combination of a small number of factors, including the solvent system, temperature, organic ligands and metal atoms (Kan et al., 2012; Liu et al., 2012). Among these factors, the organic ligands play a key role in determining the final architecture. The versatile multi­carboxyl­ate ligands have been extensively used as multifunctional organic linkers to construct coordination polymers because of their excellent coordination capability and flexible coordination patterns. As an important multidentate O-donor ligand, 1,4-phenyl­enedi­acetic acid (1,4-H₂phda) has been used extensively in the construction of a variety of coordination polymers (Farnum et al., 2013; Jia et al., 2013; Liu et al., 2013; Wu et al., 2013). 1,3-Bis[(1H-1,2,4-triazol-1-yl)methyl]­benzene (mbtz), a flexible bis­(triazole) ligand, has been widely used in the construction of coordination polymers, because it can adopt different conformations with varying relative orientations of its –CH₂– groups (Ge et al., 2012; Peng et al., 2006). We have selected 1,4-H₂phda and mbtz as organic linkers, generating the title Zn^II coordination polymer, [Zn(1,4-phda)_0.5Cl(mbtz)]_n, (I), the crystal structure of which we now report.

S2. Experimental

1,3-Bis[(1H-1,2,4-triazol-1-yl)methyl]­benzene (mbtz) was synthesized according to the literature procedure of Peng et al. (2006). All other reagents and solvents used in the experiment were purchased from commercial sources and used without further purification. The IR spectra were recorded from KBr pellets in the range 4000–400 cm^-1 on a VECTOR 22 spectrometer. Elemental analysis was carried out using a Perkin–Elmer 240C elemental analyser.

S2.1. Synthesis and crystallization

A mixture of ZnCl₂·4H₂O (0.0208 g, 0.100 mmol), 1,4-H₂phda (0.0388 g, 0.200 mmol), mbtz (0.0240 g, 0.100 mmol) and KOH (0.00800 g, 0.200 mmol) in H₂O (10 ml) was sealed in a 16 ml Teflon-lined stainless steel container and heated at 423 K for 72 h. After cooling to room temperature, colourless block-shaped crystals of (I) were collected by filtration and washed several times in water and ethanol (yield 12.4%, based on mbtz). Elemental analysis for C₁₇H₁₆ClN₆O₂Zn: C 46.70, H 3.69, N 19.22%; found: C 46.80, H 3.70, N 19.28%. IR (KBr, cm^-1): 3401 (w), 3112 (m), 2342 (w), 2312 (w), 1628 (m), 1387 (s), 745 (w), 663 (w), 565 (w).

S2.2. Refinement

C-bound H atoms were placed in calculated positions and treated using a riding-model approximation, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C) for aromatic H atoms, and C—H = 0.97 Å and U_iso(H) = 1.2U_eq(C) for methyl­ene H atoms.

S3. Results and discussion

[Zn(1,4-phda)_0.5Cl(mbtz)]_n, (I) (Fig. 1), crystallizes in the triclinic space group P1, with an asymmetric unit consisting of a Zn^II cation, an mbtz ligand, an anionic chloride ligand and half of a fully deprotonated 1,4-H₂phda ligand, viz. 1,4-phenyl­enedi­acetate (1,4-phda^2-). The Zn^II cation is coordinated by one chloride ligand [Zn1—Cl1 = 2.2563 (16) Å], one O atom from a monodentate carboxyl­ate group of a 1,4-phda^2- ligand [Zn1—O1 = 1.980 (3) Å] and two N atoms from two different mbtz ligands [Zn1—N1 = 2.020 (4) Å and Zn1—N6^vi = 2.010 (4) Å; symmetry code: (vi) -x + 1, -y + 1, -z + 1] to give a distorted ZnN₂ClO tetra­hedral coordination environment having a ι₄ parameter of 0.91 (ι₄ is 0 for an idealized square-planar geometry or 1 for an idealized tetra­hedral geometry; Yang et al., 2007).

In (I), each 1,4-phda^2- ligand links two Zn^II cations through its two carboxyl­ate groups in a µ₂-κ²O:O'-coordination mode. The dihedral angle between the plane of the carboxyl­ate group at C1 and that of the adjacent benzene ring is 70.5 (2)°. The mbtz ligand adopts a gauche conformation. The dihedral angles between the planes of triazole rings N1–N3/C6/C7 and N4–N6/C16/C17 and that of the benzene ring are 42.9 (2), 196.8 (1)and 73.1 (2)°, respectively. Two crystallographically equivalent Zn^II cations are bridged by two mbtz ligands to form a [Zn₂(mbtz)₂] rhomboid subunit (24-membered macrocycle). The Zn···Zn through-space distance across the dinuclear unit is 9.398 (2) Å. The rhomboid [Zn₂(mbtz)₂] subunits are further bridged by 1,4-phda^2- ligands to form an infinite ladder (Fig. 2) arranged parallel to the a axis. The Zn···Zn contact distance through the 1,4-phda^2- ligand is 12.662 (1) Å. Strikingly, two of these one-dimensional chains inter­penetrate each other, with each ring section of one chain ([Zn₂(mbtz)₂]) penetrated by a `bond' of the other chain (1,4-phda^2- ligand), giving a one-dimensional rotaxane-like structure (Fig. 3).

The structure of (I) is further stabilized by weak but extensive inter- and intra­molecular C—H···O and C—H···Cl hydrogen bonds connecting the one-dimensional chains into an extensive three-dimensional hydrogen-bond network (Table 3). This coordination polymer is reinforced by π–π inter­actions between the benzene and triazole rings, with a Cg1···Cg2^vii separation of 3.760 (3) Å [Cg1 and Cg2 are the centroids of the N4–N6/C16/C17 and C3–C5/C3^viii–C5^viii rings, respectively; symmetry code: (vii) x - 1, y, z; (viii) -x - 1, -y + 1, -z + 1], π–π inter­actions between the triazole rings, with a Cg3···Cg3^iv separation of 3.648 (4) Å [Cg3 is the centroid of the N1–N3/C6/C7 ring; symmetry code: (iv) -x, -y + 2, -z + 1] and π–π inter­actions between the benzene rings, with a Cg4···Cg4^ix separation of 3.709 (3) Å [Cg4 is the centroid of the C9–C14 ring; symmetry code: (ix) -x + 1, -y + 2, -z + 2].

In conclusion, we have successfully synthesized a new zinc^II coordination polymer based on 1,4-phenyl­enedi­acetic acid and 1,3-bis­[(1H-1,2,4-triazol-1-yl)methyl]­benzene, which has been characterized by IR spectroscopy, elemental analysis and single-crystal X-ray diffraction analysis. The crystal structure of (I) shows a novel one-dimensional rotaxane-like structure. This coordination polymer is reinforced by C—H···O and C—H···Cl hydrogen bonds and π–π inter­actions.

Related literature

For related literature, see: Cao et al. (1992); Dinca et al. (2006); Farnum et al. (2013); Ge et al. (2012); Jia et al. (2013); Kan et al. (2012); Liu et al. (2012, 2013); Peng et al. (2006); Plabst et al. (2009); Wu et al. (2013); Yang et al. (2007).

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. A view of the local coordination of the Zn^II cations in (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry code: (vi) -x + 1, -y + 1, -z + 1.]
	Fig. 2. A view of the one-dimensional chain of (I), arranged parallel to the a axis.
	Fig. 3. A view of the one-dimensional rotaxane-like structure of (I).

Poly[dichlorido(µ₂-1,4-phenylenediacetato-κ²O:O')bis{µ₂-1,3-bis[(1H-1,2,4-triazol-1-yl)methyl]benzene-κ²N³:N^3'}dizinc(II)]

Crystal data

[Zn(C10H8O4)0.5Cl(C12H12N6)]	V = 891.1 (4) Å^3
Mr = 437.20	Z = 2
Triclinic, P1	F(000) = 446
Hall symbol: -P 1	Dx = 1.629 Mg m^−3
a = 8.929 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.982 (2) Å	µ = 1.55 mm^−1
c = 11.777 (3) Å	T = 296 K
α = 99.926 (3)°	Block, colourless
β = 106.081 (3)°	0.21 × 0.19 × 0.17 mm
γ = 91.596 (3)°

Data collection

Bruker SMART CCD area-detector diffractometer	3317 independent reflections
Radiation source: fine-focus sealed tube	2100 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.060
ϕ and ω scans	θmax = 25.5°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −10→10
Tmin = 0.736, Tmax = 0.778	k = −10→10
6555 measured reflections	l = −13→14

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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.146	H-atom parameters constrained
S = 0.98	w = 1/[σ^2(Fo^2) + (0.0607P)^2] where P = (Fo^2 + 2Fc^2)/3
3267 reflections	(Δ/σ)max < 0.001
244 parameters	Δρmax = 0.39 e Å^−3
0 restraints	Δρmin = −0.39 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
C1	−0.2374 (6)	0.5944 (6)	0.3110 (4)	0.0323 (12)
C2	−0.4102 (6)	0.5860 (7)	0.2984 (5)	0.0462 (15)
H2A	−0.4626	0.5137	0.2258	0.055*
H2B	−0.4476	0.6843	0.2874	0.055*
C3	−0.4589 (5)	0.5414 (6)	0.4015 (4)	0.0343 (13)
C4	−0.4537 (6)	0.3945 (7)	0.4219 (5)	0.0416 (14)
H4	−0.4211	0.3211	0.3699	0.050*
C5	−0.5047 (6)	0.6465 (7)	0.4831 (5)	0.0441 (14)
H5	−0.5074	0.7471	0.4737	0.053*
C6	0.1268 (6)	0.8000 (7)	0.5381 (5)	0.0408 (14)
H6	0.0848	0.7160	0.5586	0.049*
C7	0.2013 (7)	0.9472 (7)	0.4441 (5)	0.0487 (16)
H7	0.2197	0.9866	0.3808	0.058*
C8	0.2018 (6)	0.9695 (7)	0.7426 (4)	0.0447 (15)
H8A	0.1005	0.9496	0.7545	0.054*
H8B	0.2304	1.0776	0.7678	0.054*
C9	0.3211 (6)	0.8857 (6)	0.8210 (4)	0.0306 (12)
C10	0.2761 (6)	0.7881 (6)	0.8851 (5)	0.0406 (14)
H10	0.1704	0.7698	0.8774	0.049*
C11	0.3840 (7)	0.7167 (7)	0.9604 (5)	0.0469 (15)
H11	0.3513	0.6494	1.0022	0.056*
C12	0.5412 (7)	0.7452 (6)	0.9740 (5)	0.0421 (14)
H12	0.6145	0.7000	1.0275	0.050*
C13	0.5910 (6)	0.8407 (6)	0.9085 (4)	0.0346 (13)
C14	0.4808 (6)	0.9127 (6)	0.8343 (4)	0.0328 (12)
H14	0.5131	0.9801	0.7924	0.039*
C15	0.7609 (6)	0.8649 (6)	0.9190 (5)	0.0402 (14)
H15A	0.7816	0.9645	0.9027	0.048*
H15B	0.8216	0.8624	1.0008	0.048*
C16	0.8511 (6)	0.6126 (6)	0.8487 (5)	0.0373 (13)
H16	0.8590	0.5712	0.9170	0.045*
C17	0.8508 (6)	0.6439 (6)	0.6754 (5)	0.0414 (14)
H17	0.8592	0.6254	0.5973	0.050*
Cl1	0.10373 (18)	0.76885 (18)	0.13296 (13)	0.0545 (4)
N1	0.1318 (5)	0.8090 (5)	0.4287 (4)	0.0352 (11)
N2	0.2422 (6)	1.0240 (6)	0.5551 (4)	0.0576 (14)
N3	0.1894 (5)	0.9260 (5)	0.6146 (4)	0.0362 (11)
N4	0.8117 (5)	0.7506 (5)	0.8362 (4)	0.0336 (10)
N5	0.8109 (5)	0.7728 (5)	0.7253 (4)	0.0464 (12)
N6	0.8781 (5)	0.5413 (5)	0.7471 (4)	0.0367 (11)
O1	−0.1968 (4)	0.6496 (4)	0.2292 (3)	0.0392 (9)
O2	−0.1405 (4)	0.5509 (4)	0.3936 (3)	0.0418 (9)
Zn1	0.03445 (7)	0.66230 (7)	0.27292 (5)	0.0373 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.037 (3)	0.030 (3)	0.030 (3)	−0.003 (2)	0.013 (2)	0.000 (2)
C2	0.036 (3)	0.060 (4)	0.043 (3)	0.005 (3)	0.012 (3)	0.009 (3)
C3	0.026 (3)	0.041 (4)	0.032 (3)	−0.001 (2)	0.010 (2)	−0.004 (3)
C4	0.043 (3)	0.039 (4)	0.041 (3)	−0.002 (3)	0.022 (3)	−0.013 (3)
C5	0.044 (3)	0.036 (3)	0.054 (4)	0.000 (3)	0.019 (3)	0.005 (3)
C6	0.045 (3)	0.043 (4)	0.035 (3)	0.003 (3)	0.012 (3)	0.009 (3)
C7	0.080 (4)	0.038 (4)	0.033 (3)	0.000 (3)	0.021 (3)	0.010 (3)
C8	0.049 (3)	0.055 (4)	0.028 (3)	0.014 (3)	0.008 (2)	0.004 (3)
C9	0.038 (3)	0.029 (3)	0.023 (3)	0.003 (2)	0.012 (2)	−0.004 (2)
C10	0.042 (3)	0.042 (4)	0.037 (3)	0.000 (3)	0.015 (3)	0.001 (3)
C11	0.057 (4)	0.048 (4)	0.043 (3)	−0.002 (3)	0.022 (3)	0.016 (3)
C12	0.051 (4)	0.035 (3)	0.035 (3)	0.010 (3)	0.005 (3)	0.002 (3)
C13	0.040 (3)	0.032 (3)	0.031 (3)	0.003 (2)	0.010 (2)	0.002 (2)
C14	0.049 (3)	0.024 (3)	0.028 (3)	0.002 (2)	0.020 (2)	−0.002 (2)
C15	0.039 (3)	0.035 (3)	0.041 (3)	0.004 (3)	0.009 (3)	−0.004 (3)
C16	0.039 (3)	0.039 (4)	0.037 (3)	0.006 (3)	0.011 (2)	0.015 (3)
C17	0.054 (4)	0.039 (4)	0.034 (3)	0.003 (3)	0.018 (3)	0.005 (3)
Cl1	0.0677 (10)	0.0580 (11)	0.0445 (9)	−0.0004 (8)	0.0244 (8)	0.0145 (8)
N1	0.038 (2)	0.039 (3)	0.029 (2)	0.003 (2)	0.0087 (19)	0.006 (2)
N2	0.078 (4)	0.047 (3)	0.046 (3)	−0.005 (3)	0.014 (3)	0.011 (3)
N3	0.039 (2)	0.036 (3)	0.032 (2)	0.009 (2)	0.008 (2)	0.004 (2)
N4	0.033 (2)	0.036 (3)	0.029 (2)	0.007 (2)	0.0072 (19)	0.004 (2)
N5	0.050 (3)	0.043 (3)	0.048 (3)	0.004 (2)	0.014 (2)	0.014 (3)
N6	0.041 (3)	0.035 (3)	0.033 (2)	0.006 (2)	0.012 (2)	0.000 (2)
O1	0.040 (2)	0.045 (2)	0.036 (2)	−0.0003 (18)	0.0140 (17)	0.0104 (18)
O2	0.036 (2)	0.055 (3)	0.038 (2)	0.0056 (18)	0.0135 (17)	0.0122 (19)
Zn1	0.0385 (4)	0.0400 (4)	0.0336 (4)	0.0060 (3)	0.0126 (3)	0.0036 (3)

Geometric parameters (Å, º)

C1—O2	1.237 (6)	C10—H10	0.9300
C1—O1	1.286 (6)	C11—C12	1.379 (8)
C1—C2	1.507 (7)	C11—H11	0.9300
C2—C3	1.508 (7)	C12—C13	1.387 (7)
C2—H2A	0.9700	C12—H12	0.9300
C2—H2B	0.9700	C13—C14	1.380 (7)
C3—C4	1.382 (7)	C13—C15	1.494 (7)
C3—C5	1.382 (7)	C14—H14	0.9300
C4—C5^i	1.374 (7)	C15—N4	1.462 (6)
C4—H4	0.9300	C15—H15A	0.9700
C5—C4^i	1.374 (7)	C15—H15B	0.9700
C5—H5	0.9300	C16—N4	1.319 (6)
C6—N1	1.317 (6)	C16—N6	1.343 (6)
C6—N3	1.319 (6)	C16—H16	0.9300
C6—H6	0.9300	C17—N5	1.311 (7)
C7—N2	1.315 (7)	C17—N6	1.337 (6)
C7—N1	1.333 (7)	C17—H17	0.9300
C7—H7	0.9300	Cl1—Zn1	2.2563 (16)
C8—N3	1.463 (6)	N1—Zn1	2.020 (4)
C8—C9	1.514 (7)	N2—N3	1.364 (6)
C8—H8A	0.9700	N4—N5	1.352 (6)
C8—H8B	0.9700	N6—Zn1^ii	2.010 (4)
C9—C10	1.370 (7)	O1—Zn1	1.980 (3)
C9—C14	1.400 (7)	Zn1—N6^ii	2.010 (4)
C10—C11	1.372 (8)
O2—C1—O1	121.9 (5)	C13—C12—H12	119.7
O2—C1—C2	122.8 (5)	C14—C13—C12	118.7 (5)
O1—C1—C2	115.3 (4)	C14—C13—C15	121.0 (5)
C1—C2—C3	116.4 (4)	C12—C13—C15	120.3 (5)
C1—C2—H2A	108.2	C13—C14—C9	121.0 (5)
C3—C2—H2A	108.2	C13—C14—H14	119.5
C1—C2—H2B	108.2	C9—C14—H14	119.5
C3—C2—H2B	108.2	N4—C15—C13	112.6 (4)
H2A—C2—H2B	107.3	N4—C15—H15A	109.1
C4—C3—C5	116.6 (5)	C13—C15—H15A	109.1
C4—C3—C2	121.6 (5)	N4—C15—H15B	109.1
C5—C3—C2	121.8 (5)	C13—C15—H15B	109.1
C5^i—C4—C3	122.0 (5)	H15A—C15—H15B	107.8
C5^i—C4—H4	119.0	N4—C16—N6	109.3 (5)
C3—C4—H4	119.0	N4—C16—H16	125.4
C4^i—C5—C3	121.4 (5)	N6—C16—H16	125.4
C4^i—C5—H5	119.3	N5—C17—N6	113.8 (5)
C3—C5—H5	119.3	N5—C17—H17	123.1
N1—C6—N3	110.9 (5)	N6—C17—H17	123.1
N1—C6—H6	124.6	C6—N1—C7	102.7 (5)
N3—C6—H6	124.6	C6—N1—Zn1	128.8 (4)
N2—C7—N1	115.4 (5)	C7—N1—Zn1	128.2 (4)
N2—C7—H7	122.3	C7—N2—N3	101.9 (5)
N1—C7—H7	122.3	C6—N3—N2	109.2 (5)
N3—C8—C9	113.0 (4)	C6—N3—C8	129.9 (5)
N3—C8—H8A	109.0	N2—N3—C8	120.9 (5)
C9—C8—H8A	109.0	C16—N4—N5	109.7 (4)
N3—C8—H8B	109.0	C16—N4—C15	128.8 (5)
C9—C8—H8B	109.0	N5—N4—C15	121.3 (4)
H8A—C8—H8B	107.8	C17—N5—N4	103.7 (4)
C10—C9—C14	118.6 (5)	C17—N6—C16	103.6 (4)
C10—C9—C8	120.8 (5)	C17—N6—Zn1^ii	131.2 (4)
C14—C9—C8	120.5 (5)	C16—N6—Zn1^ii	124.7 (4)
C9—C10—C11	121.3 (5)	C1—O1—Zn1	107.2 (3)
C9—C10—H10	119.4	O1—Zn1—N6^ii	113.31 (16)
C11—C10—H10	119.4	O1—Zn1—N1	111.81 (16)
C10—C11—C12	119.7 (5)	N6^ii—Zn1—N1	117.20 (17)
C10—C11—H11	120.1	O1—Zn1—Cl1	106.69 (11)
C12—C11—H11	120.1	N6^ii—Zn1—Cl1	102.11 (13)
C11—C12—C13	120.6 (5)	N1—Zn1—Cl1	104.19 (14)
C11—C12—H12	119.7
O2—C1—C2—C3	8.2 (8)	N1—C6—N3—C8	176.5 (5)
O1—C1—C2—C3	−172.2 (4)	C7—N2—N3—C6	1.8 (6)
C1—C2—C3—C4	−72.6 (7)	C7—N2—N3—C8	−176.2 (5)
C1—C2—C3—C5	104.6 (6)	C9—C8—N3—C6	72.7 (7)
C5—C3—C4—C5^i	1.5 (8)	C9—C8—N3—N2	−109.8 (6)
C2—C3—C4—C5^i	178.8 (5)	N6—C16—N4—N5	0.4 (6)
C4—C3—C5—C4^i	−1.5 (8)	N6—C16—N4—C15	175.0 (4)
C2—C3—C5—C4^i	−178.8 (4)	C13—C15—N4—C16	−82.1 (6)
N3—C8—C9—C10	−115.3 (6)	C13—C15—N4—N5	91.9 (6)
N3—C8—C9—C14	68.0 (6)	N6—C17—N5—N4	−0.5 (6)
C14—C9—C10—C11	−0.4 (8)	C16—N4—N5—C17	0.0 (6)
C8—C9—C10—C11	−177.1 (5)	C15—N4—N5—C17	−175.0 (5)
C9—C10—C11—C12	1.1 (8)	N5—C17—N6—C16	0.7 (6)
C10—C11—C12—C13	−2.6 (8)	N5—C17—N6—Zn1^ii	−171.9 (4)
C11—C12—C13—C14	3.3 (8)	N4—C16—N6—C17	−0.7 (6)
C11—C12—C13—C15	−176.9 (5)	N4—C16—N6—Zn1^ii	172.5 (3)
C12—C13—C14—C9	−2.6 (7)	O2—C1—O1—Zn1	−4.5 (6)
C15—C13—C14—C9	177.6 (4)	C2—C1—O1—Zn1	175.9 (4)
C10—C9—C14—C13	1.2 (7)	C1—O1—Zn1—N6^ii	70.9 (3)
C8—C9—C14—C13	177.9 (5)	C1—O1—Zn1—N1	−64.2 (3)
C14—C13—C15—N4	−93.5 (6)	C1—O1—Zn1—Cl1	−177.5 (3)
C12—C13—C15—N4	86.7 (6)	C6—N1—Zn1—O1	65.3 (5)
N3—C6—N1—C7	0.2 (6)	C7—N1—Zn1—O1	−106.0 (5)
N3—C6—N1—Zn1	−172.8 (3)	C6—N1—Zn1—N6^ii	−67.9 (5)
N2—C7—N1—C6	1.0 (7)	C7—N1—Zn1—N6^ii	120.7 (5)
N2—C7—N1—Zn1	174.1 (4)	C6—N1—Zn1—Cl1	−179.9 (4)
N1—C7—N2—N3	−1.7 (7)	C7—N1—Zn1—Cl1	8.8 (5)
N1—C6—N3—N2	−1.3 (6)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17···O2^iii	0.93	2.38	3.303 (7)	173
C15—H15B···Cl1^iv	0.97	2.81	3.617 (5)	142
C15—H15A···Cl1^v	0.97	2.72	3.680 (6)	169
C8—H8B···O1^vi	0.97	2.47	3.383 (7)	156
C6—H6···O2^vii	0.93	2.59	3.381 (7)	144
C6—H6···O2	0.93	2.59	3.120 (7)	117

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