A helical zinc(II) coordination polymer assembled from 1,3-bis[(pyridin-3-yl)meth­oxy]benzene and benzene-1,4-di­carb­oxy­lic acid

In catena-poly[[aqua­[1,3-bis­(pyridine-3-ylmeth­oxy)benzene-κN]zinc(II)]-μ₂-benzene-1,4-di­carboxyl­ato-κ²O¹:O⁴], [Zn(C₈H₄O₄)(C₁₈H₁₆N₂O₂)(H₂O)]_n, each Zn^II centre is tetra­hedrally coordinated by two O atoms of bridging carboxyl­ate groups from two benzene-1,4-di­carboxyl­ate anions (denoted L²⁻), one O atom from a water mol­ecule and one N atom from a 1,3-bis­[(pyridin-3-yl)meth­oxy]benzene ligand (denoted bpmb). (Aqua)O—H...N hydrogen-bonding inter­actions induce the formation of one-dimensional helical [Zn(L)(bpmb)(H₂O)]_n chains which are inter­linked through (aqua)O—H...O hydrogen-bonding inter­actions, producing two-dimensional corrugated sheets.

S1. Introduction

Recently, helical coordination polymers (CPs) have received much attention because of their molecular self-assembly and potential applications in asymmetric catalysis, nonlinear optics and biomimetic chemistry (Zhang et al., 2005; Zhao et al., 2008; Piguet et al., 1997). Significant effort has been devoted to producing CPs with helical structures using various approaches. One of the most successful approaches is the rational selection of flexible N-containing bridging ligands and metal cations to construct target CPs with the desired properties (Chen et al., 2009; Liu, Yu et al., 2014).

Flexible N-containing bridging linkers, such as 1,4-bis­[(pyridin-4-yl)meth­oxy]­benzene, 1,4-bis­[(pyridin-3-yl)meth­oxy]­benzene and 1,3-bis­[(pyridin-4-yl)meth­oxy]­benzene, have been employed as linkers to construct versatile functional CPs (Li, Qin et al., 2012; Li, Zhao et al. 2012; Liu et al., 2010; Oh et al., 2005; Steel & Fitchett, 2013). Liu and co-workers have investigated the coordination chemistry of 1,3-bis­[(pyridin-4-yl)meth­oxy]­benzene with Zn^II, Ag^I and Hg^II salts to form several helical complexes and cage-like structures (Liu et al., 2010). Li and co-workers have prepared and structurally characterized some two- or three-dimensional entangled structures through the assembly of 1,4-bis­[(pyridin-4-yl)meth­oxy]­benzene with Zn^II salts (Li, Qin et al., 2012). However, to the best of our knowledge, the coordination chemistry of 1,3-bis­[(pyridin-3-yl)meth­oxy]­benzene (bpmb) has attracted little attention. A mixed-ligand system consisting of two types of ligand provides more variability in the construction of different topologies (Liu, Yu et al., 2014). Thus, we reacted Zn(OAc)₂·2H₂O (OAc is acetate) with bpmb and benzene-1,4-di­carb­oxy­lic acid (H₂L) to produce the title compound, [Zn(L)(bpmb)(H₂O)]_n, (I).

S2. Experimental

S2.1. Synthesis and crystallization

1,3-Bis[(pyridin-3-yl)meth­oxy]­benzene (bpmb) was prepared according to the literature method of Xiao et al. (2011). All other chemicals and reagents were obtained from commercial sources (Sigma–Aldrich) and used as received. A mixture of Zn(OAc)₂·2H₂O (9 mg, 0.04 mmol), benzene-1,4-di­carb­oxy­lic acid (3 mg, 0.02 mmol), bpmb (6 mg, 0.02 mmol) and H₂O (4 ml) was sealed in a 10 ml Pyrex glass tube and heated at 423 K for 4 d, then cooled to room temperature at a rate of 5 K h^-1. Colourless blocks of (I) were collected and dried in air (yield 4 mg, 37%, based on bpmb). IR (KBr disc, ν, cm^-1): 3396 (w), 3030 (w), 2980 (w), 1659 (m), 1602 (s), 1575 (s), 1535 (m), 1458 (m), 1389 (m), 1326 (w), 1244 (w), 1158 (m), 1041 (m), 990 (w), 889 (w), 862 (w), 837 (w), 786 (m), 646 (m).

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 aromatic H atoms, C—H = 0.97 Å for methyl­ene H atoms and O—H = 0.85 Å for coordinated water H atoms, and refined as riding, with U_iso(H) = 1.2U_eq(C,O).

S3. Results and discussion

Compound (I) crystallizes in the monoclinic space group P2₁/c and its asymmetric unit contains one [Zn(L)(bpmb)(H₂O)] unit. Each Zn^II centre is tetra­hedrally coordinated by two carboxyl­ate O atoms [O3 and O6ⁱ; symmetry code: (i) -x + 1, y + 1/2, -z + 1/2] from two L^2- ligands, one O atom from a water ligand (O1W) and one N atom from one bpmb ligand (Table 2). A weak inter­action [2.5190 (15) Å] exists between atoms Zn1 and O4 (Fig. 1).

In (I), the L^2- ligands adopt a µ₂-η¹:η¹ coordination mode to link two Zn^II cations. The L^2- anions bridge these metal centres in a head-to-tail fashion via the monodentate aromatic carboxyl­ate atoms O3 and O6, to form a one-dimensional [Zn(L)]_n chain extending along the b axis (Fig. 2; purple represents the L^2- ligands), with a Zn···Zn separation of 10.955 (5) Å. Notably, only one N atom (N1) of the bpmb ligand is bound to a Zn^II centre. The other N atom (N2) is employed as an acceptor and inter­acts with the H atom of the water ligand (O1W), forming an intra­molecular hydrogen bond (O1W—H1WB···N2ⁱ). These hydrogen-bonding inter­actions induce the formation of a one-dimensional helical [Zn(L)(bpmb)(H₂O)]_n chain (Fig. 2). Adjacent one-dimensional arrays are inter­connected via O1W—H1WA···O4ⁱⁱ hydrogen bonds [symmetry code: (ii) x - 1, y, z] between the aqua ligands O1W and the uncoordinated carboxyl­ate O4 atoms of L^2-, resulting in two-dimensional corrugated sheets extending in the ab plane.

A previously reported Zn^II coordination polymer, viz. [Zn(L)(3-bpmb)(H₂O)]_n, (II), assembled from 1,4-bis­[(pyridin-3-yl)meth­oxy]­benzene (3-bpmb) and H₂L, shows a three-dimensional coordination framework (Li, Zhao et al., 2012). In (II), each Zn^II cation is five-coordinated and displays a distorted square-pyramidal coordination geometry. The 3-bpmb ligands in (II) adopt a bridging mode to connect two adjacent Zn^II cations, resulting in a meso-helical [Zn(3-bpmb)]_n chain, while in (I) only one N atom of the bpmb ligand coordinates to the Zn^II centre, resulting in helical chains, which are rare in the literature.

In conclusion, a new zinc coordination polymer, (I), containing infinite helical chains has been prepared under solvothermal conditions using flexible bpmb and L^2- ligands. The structural differences between (I) and (II) suggest that the substituted positions of the N atoms in bpmb and 3-bpmb ligands significantly affect the helicity of the resulting CPs.

Related literature

For related literature, see: Chen et al. (2009); Li, Qin, Wang, Wang, Zhao, Yang, Wang, Yuan, Shao & Su (2012); Li, Zhao, Zhang, Zhang, Tan, Lu, Feng & Yang (2012); Liu et al. (2010, 2014); Oh et al. (2005); Piguet et al. (1997); Steel & Fitchett (2013); Xiao et al. (2011); Zhang et al. (2005); Zhao et al. (2008).

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 in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (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 indicates the weak interaction between atoms Zn1 and O4. [Symmetry code: (i) -x + 1, y + 1/2, -z + 1/2.]
	Fig. 2. A view of the one-dimensional helical [Zn(L)(bpmb)(H2O)]n chain of (I), linked via bridging L^2- ligands. All H atoms, except those involved in hydrogen-bonding interactions, have been omitted for clarity.

catena-Poly[[aqua[1,3-bis(pyridine-3-ylmethoxy)benzene-κN]zinc(II)]-µ₂-benzene-1,4-dicarboxylato-κ²O¹:O⁴]

Crystal data

[Zn(C8H4O4)(C18H16N2O2)(H2O)]	F(000) = 1112
Mr = 539.82	Dx = 1.519 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 6.0706 (12) Å	Cell parameters from 5574 reflections
b = 17.914 (4) Å	θ = 2.2–27.1°
c = 21.750 (4) Å	µ = 1.09 mm^−1
β = 93.54 (3)°	T = 296 K
V = 2360.9 (8) Å^3	Block, colourless
Z = 4	0.25 × 0.25 × 0.25 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	3617 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.029
ϕ and ω scans	θmax = 25.3°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −7→7
Tmin = 0.759, Tmax = 0.761	k = −21→21
16703 measured reflections	l = −26→26
4279 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)] = 0.027	Hydrogen site location: mixed
wR(F^2) = 0.069	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0325P)^2 + 0.7485P] where P = (Fo^2 + 2Fc^2)/3
4279 reflections	(Δ/σ)max = 0.003
325 parameters	Δρmax = 0.22 e Å^−3
0 restraints	Δρmin = −0.26 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	0.05847 (4)	0.92079 (2)	0.31918 (2)	0.03109 (8)
C1	−0.1698 (3)	0.93378 (11)	0.43514 (10)	0.0383 (5)
H1	−0.2775	0.9577	0.4101	0.046*
C2	−0.2010 (4)	0.92626 (12)	0.49689 (10)	0.0426 (5)
H2	−0.3260	0.9459	0.5135	0.051*
C3	−0.0443 (4)	0.88922 (12)	0.53366 (10)	0.0416 (5)
H3	−0.0637	0.8830	0.5754	0.050*
C4	0.1426 (3)	0.86114 (11)	0.50832 (9)	0.0359 (4)
C5	0.1642 (3)	0.87254 (11)	0.44631 (9)	0.0354 (4)
H5	0.2905	0.8551	0.4289	0.042*
C6	0.3145 (4)	0.82046 (12)	0.54820 (9)	0.0430 (5)
H6A	0.4008	0.8559	0.5734	0.052*
H6B	0.2437	0.7862	0.5753	0.052*
C7	0.6189 (4)	0.73840 (11)	0.53915 (9)	0.0409 (5)
C8	0.6466 (4)	0.72967 (12)	0.60222 (10)	0.0475 (5)
H8	0.5529	0.7535	0.6282	0.057*
C9	0.8166 (4)	0.68480 (13)	0.62595 (11)	0.0548 (6)
H9	0.8374	0.6788	0.6684	0.066*
C10	0.9550 (4)	0.64899 (14)	0.58831 (11)	0.0576 (6)
H10	1.0678	0.6187	0.6050	0.069*
C11	0.9252 (4)	0.65839 (13)	0.52491 (10)	0.0506 (6)
C12	0.7594 (4)	0.70389 (12)	0.50010 (10)	0.0451 (5)
H12	0.7420	0.7113	0.4578	0.054*
C13	1.0801 (4)	0.63360 (14)	0.42775 (11)	0.0582 (6)
H13A	1.1290	0.6845	0.4220	0.070*
H13B	0.9366	0.6274	0.4062	0.070*
C14	1.2434 (4)	0.57941 (12)	0.40348 (10)	0.0459 (5)
C15	1.2035 (4)	0.54481 (13)	0.34751 (10)	0.0479 (5)
H15	1.0704	0.5548	0.3255	0.057*
C16	1.5836 (4)	0.51371 (16)	0.41171 (12)	0.0632 (7)
H16	1.7157	0.5014	0.4333	0.076*
C17	1.5304 (4)	0.48343 (14)	0.35481 (11)	0.0548 (6)
H17	1.6307	0.4512	0.3380	0.066*
C18	1.4388 (4)	0.56246 (14)	0.43619 (12)	0.0561 (6)
H18	1.4720	0.5840	0.4746	0.067*
C19	0.2979 (4)	0.80707 (11)	0.29104 (9)	0.0388 (5)
C20	0.3903 (3)	0.73703 (10)	0.26583 (9)	0.0336 (4)
C21	0.6058 (3)	0.71618 (11)	0.28222 (10)	0.0406 (5)
H21	0.6920	0.7454	0.3096	0.049*
C22	0.6929 (3)	0.65231 (11)	0.25806 (10)	0.0393 (5)
H22	0.8365	0.6381	0.2701	0.047*
C23	0.5687 (3)	0.60890 (10)	0.21598 (9)	0.0319 (4)
C24	0.3524 (3)	0.62906 (10)	0.20045 (9)	0.0338 (4)
H24	0.2662	0.5996	0.1732	0.041*
C25	0.2634 (3)	0.69257 (10)	0.22507 (9)	0.0350 (4)
H25	0.1178	0.7056	0.2143	0.042*
C26	0.6699 (3)	0.54289 (10)	0.18561 (10)	0.0345 (4)
N1	0.0108 (3)	0.90773 (8)	0.40990 (7)	0.0330 (4)
N2	1.3434 (3)	0.49782 (10)	0.32272 (8)	0.0485 (5)
O1	0.4546 (3)	0.78031 (9)	0.50984 (6)	0.0497 (4)
O2	1.0674 (3)	0.61795 (11)	0.49119 (8)	0.0708 (5)
O3	0.0969 (3)	0.82184 (8)	0.27830 (8)	0.0543 (4)
O4	0.4168 (3)	0.84955 (8)	0.32416 (7)	0.0488 (4)
O5	0.6113 (3)	0.52729 (8)	0.13198 (7)	0.0472 (4)
O6	0.8176 (2)	0.50765 (8)	0.21884 (7)	0.0447 (4)
O1W	−0.2544 (2)	0.93862 (8)	0.28920 (7)	0.0443 (4)
H1WA	−0.3516	0.9066	0.2976	0.053*
H1WB	−0.2929	0.9557	0.2537	0.053*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.03370 (14)	0.02834 (12)	0.03153 (13)	0.00066 (9)	0.00432 (9)	0.00196 (9)
C1	0.0347 (11)	0.0388 (11)	0.0415 (12)	0.0031 (9)	0.0043 (9)	0.0015 (9)
C2	0.0379 (12)	0.0488 (12)	0.0424 (12)	0.0044 (10)	0.0125 (10)	−0.0015 (10)
C3	0.0485 (13)	0.0462 (12)	0.0310 (11)	−0.0024 (10)	0.0087 (10)	0.0016 (9)
C4	0.0405 (11)	0.0342 (10)	0.0331 (11)	−0.0025 (9)	0.0032 (9)	0.0008 (8)
C5	0.0346 (11)	0.0375 (11)	0.0345 (11)	0.0023 (9)	0.0061 (9)	0.0011 (8)
C6	0.0491 (13)	0.0482 (12)	0.0321 (11)	0.0078 (10)	0.0055 (10)	0.0025 (9)
C7	0.0502 (13)	0.0362 (11)	0.0355 (11)	0.0050 (10)	−0.0034 (10)	−0.0003 (9)
C8	0.0593 (14)	0.0482 (13)	0.0351 (12)	0.0115 (11)	0.0033 (11)	−0.0007 (10)
C9	0.0709 (16)	0.0570 (14)	0.0358 (12)	0.0134 (13)	−0.0039 (12)	0.0038 (11)
C10	0.0656 (16)	0.0613 (15)	0.0450 (14)	0.0234 (13)	−0.0037 (12)	0.0033 (11)
C11	0.0590 (15)	0.0493 (13)	0.0433 (13)	0.0135 (11)	0.0006 (11)	−0.0047 (10)
C12	0.0585 (14)	0.0450 (12)	0.0312 (11)	0.0058 (11)	−0.0011 (10)	−0.0019 (9)
C13	0.0712 (17)	0.0566 (14)	0.0470 (14)	0.0173 (13)	0.0067 (12)	−0.0033 (11)
C14	0.0522 (14)	0.0456 (12)	0.0399 (12)	0.0041 (10)	0.0045 (10)	−0.0012 (10)
C15	0.0482 (13)	0.0549 (13)	0.0396 (12)	0.0072 (11)	−0.0054 (10)	0.0016 (11)
C16	0.0463 (14)	0.090 (2)	0.0519 (15)	0.0137 (14)	−0.0070 (12)	−0.0079 (14)
C17	0.0520 (14)	0.0661 (16)	0.0464 (14)	0.0136 (12)	0.0046 (11)	−0.0022 (12)
C18	0.0521 (14)	0.0688 (16)	0.0466 (14)	−0.0002 (12)	−0.0038 (12)	−0.0126 (12)
C19	0.0486 (13)	0.0312 (10)	0.0381 (11)	−0.0005 (9)	0.0156 (10)	0.0013 (9)
C20	0.0373 (11)	0.0297 (10)	0.0345 (11)	−0.0005 (8)	0.0077 (9)	0.0001 (8)
C21	0.0399 (12)	0.0377 (11)	0.0437 (12)	−0.0032 (9)	−0.0012 (10)	−0.0090 (9)
C22	0.0313 (11)	0.0378 (11)	0.0484 (12)	0.0031 (9)	0.0001 (9)	−0.0035 (9)
C23	0.0354 (11)	0.0279 (9)	0.0331 (10)	−0.0012 (8)	0.0073 (8)	0.0021 (8)
C24	0.0372 (11)	0.0316 (10)	0.0326 (10)	−0.0043 (8)	0.0019 (9)	−0.0013 (8)
C25	0.0295 (10)	0.0356 (10)	0.0401 (11)	0.0012 (8)	0.0028 (9)	0.0016 (9)
C26	0.0330 (11)	0.0293 (10)	0.0427 (12)	−0.0041 (8)	0.0127 (9)	−0.0006 (9)
N1	0.0340 (9)	0.0323 (8)	0.0329 (9)	0.0000 (7)	0.0034 (7)	0.0021 (7)
N2	0.0539 (12)	0.0545 (11)	0.0370 (10)	0.0086 (9)	0.0011 (9)	−0.0030 (8)
O1	0.0603 (10)	0.0575 (9)	0.0309 (8)	0.0209 (8)	−0.0008 (7)	0.0001 (7)
O2	0.0859 (13)	0.0836 (13)	0.0438 (10)	0.0432 (11)	0.0097 (9)	0.0014 (9)
O3	0.0472 (9)	0.0453 (9)	0.0703 (11)	0.0126 (7)	0.0030 (8)	−0.0155 (8)
O4	0.0565 (10)	0.0384 (8)	0.0531 (9)	−0.0094 (7)	0.0165 (8)	−0.0120 (7)
O5	0.0594 (10)	0.0456 (8)	0.0374 (8)	0.0049 (7)	0.0094 (7)	−0.0056 (7)
O6	0.0418 (8)	0.0389 (8)	0.0527 (9)	0.0107 (7)	−0.0014 (7)	−0.0099 (7)
O1W	0.0334 (8)	0.0524 (9)	0.0469 (9)	−0.0017 (6)	0.0007 (7)	0.0162 (7)

Geometric parameters (Å, º)

Zn1—O6^i	1.9360 (14)	C13—C14	1.506 (3)
Zn1—O1W	1.9954 (14)	C13—H13A	0.9700
Zn1—O3	2.0032 (15)	C13—H13B	0.9700
Zn1—N1	2.0256 (17)	C14—C15	1.374 (3)
Zn1—C19	2.598 (2)	C14—C18	1.379 (3)
C1—N1	1.340 (3)	C15—N2	1.333 (3)
C1—C2	1.375 (3)	C15—H15	0.9300
C1—H1	0.9300	C16—C18	1.370 (3)
C2—C3	1.375 (3)	C16—C17	1.372 (3)
C2—H2	0.9300	C16—H16	0.9300
C3—C4	1.386 (3)	C17—N2	1.321 (3)
C3—H3	0.9300	C17—H17	0.9300
C4—C5	1.378 (3)	C18—H18	0.9300
C4—C6	1.504 (3)	C19—O4	1.247 (2)
C5—N1	1.342 (2)	C19—O3	1.263 (3)
C5—H5	0.9300	C19—C20	1.492 (3)
C6—O1	1.423 (2)	C20—C21	1.386 (3)
C6—H6A	0.9700	C20—C25	1.389 (3)
C6—H6B	0.9700	C21—C22	1.378 (3)
C7—O1	1.373 (2)	C21—H21	0.9300
C7—C8	1.381 (3)	C22—C23	1.388 (3)
C7—C12	1.386 (3)	C22—H22	0.9300
C8—C9	1.383 (3)	C23—C24	1.383 (3)
C8—H8	0.9300	C23—C26	1.504 (3)
C9—C10	1.368 (3)	C24—C25	1.382 (3)
C9—H9	0.9300	C24—H24	0.9300
C10—C11	1.390 (3)	C25—H25	0.9300
C10—H10	0.9300	C26—O5	1.230 (2)
C11—O2	1.374 (3)	C26—O6	1.282 (2)
C11—C12	1.379 (3)	O6—Zn1^ii	1.9359 (14)
C12—H12	0.9300	O1W—H1WA	0.8500
C13—O2	1.415 (3)	O1W—H1WB	0.8501
O6^i—Zn1—O1W	96.83 (6)	H13A—C13—H13B	108.6
O6^i—Zn1—O3	117.57 (7)	C15—C14—C18	117.2 (2)
O1W—Zn1—O3	97.54 (7)	C15—C14—C13	121.1 (2)
O6^i—Zn1—N1	126.27 (6)	C18—C14—C13	121.7 (2)
O1W—Zn1—N1	98.42 (7)	N2—C15—C14	124.1 (2)
O3—Zn1—N1	110.96 (7)	N2—C15—H15	117.9
O6^i—Zn1—C19	106.97 (7)	C14—C15—H15	117.9
O1W—Zn1—C19	125.71 (7)	C18—C16—C17	118.8 (2)
O3—Zn1—C19	28.27 (6)	C18—C16—H16	120.6
N1—Zn1—C19	104.76 (6)	C17—C16—H16	120.6
N1—C1—C2	122.12 (19)	N2—C17—C16	123.2 (2)
N1—C1—H1	118.9	N2—C17—H17	118.4
C2—C1—H1	118.9	C16—C17—H17	118.4
C1—C2—C3	118.9 (2)	C16—C18—C14	119.5 (2)
C1—C2—H2	120.5	C16—C18—H18	120.3
C3—C2—H2	120.5	C14—C18—H18	120.3
C2—C3—C4	119.85 (19)	O4—C19—O3	121.07 (19)
C2—C3—H3	120.1	O4—C19—C20	120.53 (19)
C4—C3—H3	120.1	O3—C19—C20	118.39 (18)
C5—C4—C3	117.69 (19)	O4—C19—Zn1	72.40 (11)
C5—C4—C6	122.14 (18)	O3—C19—Zn1	48.70 (10)
C3—C4—C6	120.16 (18)	C20—C19—Zn1	166.99 (15)
N1—C5—C4	122.87 (18)	C21—C20—C25	119.15 (18)
N1—C5—H5	118.6	C21—C20—C19	120.15 (18)
C4—C5—H5	118.6	C25—C20—C19	120.69 (18)
O1—C6—C4	108.98 (16)	C22—C21—C20	120.27 (18)
O1—C6—H6A	109.9	C22—C21—H21	119.9
C4—C6—H6A	109.9	C20—C21—H21	119.9
O1—C6—H6B	109.9	C21—C22—C23	120.73 (19)
C4—C6—H6B	109.9	C21—C22—H22	119.6
H6A—C6—H6B	108.3	C23—C22—H22	119.6
O1—C7—C8	124.31 (19)	C24—C23—C22	118.92 (18)
O1—C7—C12	114.58 (18)	C24—C23—C26	120.35 (17)
C8—C7—C12	121.1 (2)	C22—C23—C26	120.67 (17)
C7—C8—C9	118.6 (2)	C25—C24—C23	120.56 (18)
C7—C8—H8	120.7	C25—C24—H24	119.7
C9—C8—H8	120.7	C23—C24—H24	119.7
C10—C9—C8	121.4 (2)	C24—C25—C20	120.32 (18)
C10—C9—H9	119.3	C24—C25—H25	119.8
C8—C9—H9	119.3	C20—C25—H25	119.8
C9—C10—C11	119.3 (2)	O5—C26—O6	125.01 (18)
C9—C10—H10	120.3	O5—C26—C23	119.53 (18)
C11—C10—H10	120.3	O6—C26—C23	115.45 (17)
O2—C11—C12	124.8 (2)	C1—N1—C5	118.51 (17)
O2—C11—C10	114.7 (2)	C1—N1—Zn1	121.92 (13)
C12—C11—C10	120.5 (2)	C5—N1—Zn1	119.57 (13)
C11—C12—C7	119.1 (2)	C17—N2—C15	117.25 (19)
C11—C12—H12	120.5	C7—O1—C6	116.57 (15)
C7—C12—H12	120.5	C11—O2—C13	119.34 (18)
O2—C13—C14	106.90 (19)	C19—O3—Zn1	103.03 (13)
O2—C13—H13A	110.3	C26—O6—Zn1^ii	115.57 (13)
C14—C13—H13A	110.3	Zn1—O1W—H1WA	118.8
O2—C13—H13B	110.3	Zn1—O1W—H1WB	123.9
C14—C13—H13B	110.3	H1WA—O1W—H1WB	106.3
N1—C1—C2—C3	−1.6 (3)	Zn1—C19—C20—C25	−1.4 (7)
C1—C2—C3—C4	0.9 (3)	C25—C20—C21—C22	0.3 (3)
C2—C3—C4—C5	0.6 (3)	C19—C20—C21—C22	−178.71 (18)
C2—C3—C4—C6	−179.89 (19)	C20—C21—C22—C23	1.5 (3)
C3—C4—C5—N1	−1.6 (3)	C21—C22—C23—C24	−2.6 (3)
C6—C4—C5—N1	178.97 (18)	C21—C22—C23—C26	174.80 (19)
C5—C4—C6—O1	−16.3 (3)	C22—C23—C24—C25	1.8 (3)
C3—C4—C6—O1	164.21 (18)	C26—C23—C24—C25	−175.56 (17)
O1—C7—C8—C9	178.8 (2)	C23—C24—C25—C20	0.0 (3)
C12—C7—C8—C9	−0.8 (3)	C21—C20—C25—C24	−1.0 (3)
C7—C8—C9—C10	−0.4 (4)	C19—C20—C25—C24	177.96 (17)
C8—C9—C10—C11	0.5 (4)	C24—C23—C26—O5	32.1 (3)
C9—C10—C11—O2	−177.7 (2)	C22—C23—C26—O5	−145.2 (2)
C9—C10—C11—C12	0.6 (4)	C24—C23—C26—O6	−149.15 (18)
O2—C11—C12—C7	176.3 (2)	C22—C23—C26—O6	33.5 (3)
C10—C11—C12—C7	−1.8 (4)	C2—C1—N1—C5	0.7 (3)
O1—C7—C12—C11	−177.8 (2)	C2—C1—N1—Zn1	−178.78 (15)
C8—C7—C12—C11	1.9 (3)	C4—C5—N1—C1	0.9 (3)
O2—C13—C14—C15	137.8 (2)	C4—C5—N1—Zn1	−179.58 (15)
O2—C13—C14—C18	−42.3 (3)	C16—C17—N2—C15	0.7 (4)
C18—C14—C15—N2	−1.7 (4)	C14—C15—N2—C17	0.9 (4)
C13—C14—C15—N2	178.2 (2)	C8—C7—O1—C6	4.0 (3)
C18—C16—C17—N2	−1.4 (4)	C12—C7—O1—C6	−176.30 (19)
C17—C16—C18—C14	0.5 (4)	C4—C6—O1—C7	−178.57 (17)
C15—C14—C18—C16	0.9 (4)	C12—C11—O2—C13	13.5 (4)
C13—C14—C18—C16	−179.0 (2)	C10—C11—O2—C13	−168.2 (2)
O4—C19—C20—C21	4.1 (3)	C14—C13—O2—C11	−178.5 (2)
O3—C19—C20—C21	−175.50 (19)	O4—C19—O3—Zn1	2.5 (2)
Zn1—C19—C20—C21	177.6 (5)	C20—C19—O3—Zn1	−177.93 (14)
O4—C19—C20—C25	−174.92 (18)	O5—C26—O6—Zn1^ii	−3.2 (3)
O3—C19—C20—C25	5.5 (3)	C23—C26—O6—Zn1^ii	178.12 (12)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O1	0.93	2.38	2.729 (2)	102
C5—H5···O4	0.93	2.45	3.176 (3)	135
O1W—H1WA···O4^iii	0.85	1.86	2.701 (2)	170
O1W—H1WB···N2^i	0.85	1.83	2.679 (2)	173
C1—H1···O5^iv	0.93	2.50	3.412 (3)	165

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