Bis{μ-(E)-2-[(2-pyridyl­amino)(2-pyridyl­imino)meth­yl]benzato}bis­[acetatozinc(II)] tetra­hydrate

In the C₂-symmetric dinuclear title complex, [Zn₂(C₁₈H₁₃N₄O₂)₂(C₂H₃O₂)₂]·4H₂O, each Zn^II ion is five-coordinated in a distorted trigonal bipyramidal fashion by one carboxyl­ate O atom from one benzoate ligand, one imine N atom and two pyridyl N atoms from a second benzoate ligand, and one O atom from an acetate anion. The two Zn atoms are bridged by the two benzoate ligands, forming a dinuclear structure with a 14-membered macrocycle. Adjacent dinuclear units are further connected by extensive hydrogen bonds involving the solvent water mol­ecules, giving a three-dimensional hydrogen-bonded framework. The framework can be regarded as an example of the four-connected node network of the PtS topology.

S1. Comment

The rapidly growing area of coordination polymers based on the interactions of metal cations with organic ligands has given rise to a wide range of fascinating one-, two- and three-dimensional structures (Erxleben, 2003). In designing these polymers, the choice of appropriate organic ligands is a dominant factor in determining the structural and functional outcome of the target polymers. Organic ligands containing N,O-donors are of interest because of their capacity for intriguing structural features and their potential applications (Li et al., 2003; Gao et al., 2004; Fei et al., 2005). Many studies have centred on the use of pyridine(bi)carboxylate ligands, especially 3- or 4-pyridinecarboxylate ligands and 2,5-pyridinedicarboxylate (Xing et al., 1998; Qin et al., 2002; Garcia-Zarracino & Hopfl, 2005). However, there are few reports on the bis(pyridine)carboxylate ligands (Hemmert et al., 1996; Kirin et al., 2005). In order to further explore the self-assembly of coordination networks based on bis(pyridine)carboxylate ligands, we synthesized a new dinuclear zinc complex, [Zn₂(C₁₈H₁₃N₄O₂)₂(CH₃COO)₂].4H₂O, (I), obtained by the reaction of zinc(II) acetate dihydrate and a new ligand, viz. (E)-2-[N,N'-di(pyridin-2-yl)carbamimidoyl]benzoic acid, in methanol solution. To the best of our knowledge, this is the first report of a crystal structure of a metal complex containing this ligand.

The title complex has a dinuclear structure, in which the molecule is situated about a crystallographic twofold axis, as shown in Fig. 1. The unique Zn^II ion lies in a distorted trigonal–bipyramidal coordination environment, which is completed by one carboxylate O atom from one benzoate ligand, one imine N atom and two pyridyl N atoms from a second benzoate ligand, and one O atom from an acetate anion. The equatorial plane of the trigonal bipyramid is defined by atoms N1, O3 and O1ⁱ [symmetry code: (i) -x, y, 1/2 - z], and the displacement of the Zn^II ion from the equatorial plane is 0.13 (3) Å. The axial positions are occupied by pyridyl atoms N2 and N4, and the N2—Zn1—N4 angle deviates significantly from linearity (Table 1). The distortion of the coordination polyhedron is primarily influenced by the very small bite angle imposed by the four-membered ring generated by the coordination of the imine and immediately adjacent pyridyl N atoms to the Zn^II ion.

It is noteworthy that each ligand behaves in a quadridentate coordination fashion involving one monodentate carboxylate O atom, the imine N atom and the two pyridyl N atoms, while the amine N atom is free of coordination with the Zn atoms. Within each benzoate ligand, the two pyridyl rings are nearly parallel to one another, with a dihedral angle of 9.2 (2)°; however, the benzene ring is nearly perpendicular to these two pyridyl rings, with dihedral angles of 89.8 (2) and 89.7 (2)°. The two Zn atoms in the molecule are bridged by the two benzoate ligands to give a 14-membered macrometallacyclic ring with a Zn···Zn separation of 5.0983 (12) Å. Within the dinuclear units, π–π interactions are present between each of the pyridyl rings and their symmetry-related counterparts in the second benzoate ligand. The centroid–centroid distances are 3.573 (2) and 3.817 (2) Å for the pyridyl rings containing atoms N2 and N4, respectively.

The asymmetric unit of the crystal structure includes two solvent water molecules. It can be seen from Fig. 2 that the crystal structure is built through extensive hydrogen bonds. The free water molecules of adjacent asymmetric units form hydrogen bonds amongst themselves (Table 2), which result in eight-membered centrosymmetric rhombic hydrogen-bonded rings. These rings have a graph-set motif of R²₄(8) (Bernstein et al., 1995), where atom O1W acts solely as a hydrogen-bond donor through both of its H atoms and atom O2W acts solely as a hydrogen-bond acceptor. At the same time, the free water molecules also form intermolecular hydrogen bonds with adjacent Zn complex molecules. Atom O1W accepts a hydrogen bond from the uncoordinated amine N atom (N3), while atom O2W donates hydrogen bonds through its two H atoms to acetate atom O3 and carboxylate atom O2 of two different adjacent Zn complex molecules (Table 2). Taken together, the hydrogen-bonding interactions give rise to a regular three-dimensional hydrogen-bonding framework. It is noteworthy that the complex molecules do not interact with one another via direct hydrogen bonds but only via water molecules. A better insight into the nature of this intricate framework can be achieved by the application of a topological approach, reducing multi-dimensional structures to simple node and connection nets. As discussed above, each dinuclear unit and each eight-membered rhombic hydrogen-bonded ring of water molecules can be considered as four-connected nodes. Therefore, the whole structure can be regarded as a PtS net (Wang et al., 2008), as displayed in Fig. 3.

Related literature

For related literature, see: Bernstein et al. (1995); Erxleben (2003); Fei et al. (2005); Gao et al. (2004); Garcia-Zarracino & Hopfl (2005); Hemmert et al. (1996); Kirin et al. (2005); Li et al. (2003); Qin et al. (2002); Wang et al. (2008); Xing et al. (1998).

S2. Experimental

An aqueous solution of zinc(II) acetate dihydrate (0.110 g, 0.5 mmol) was added to an methanol solution of (E)-2-[N,N'-di(pyridin-2-yl)carbamimidoyl]benzoic acid (1.59 g, 5 mmol). The solution was stirred for half an hour and allowed to evaporate at room temperature. Colorless crystals were isolated from the filtered solution after four weeks. Analysis calculated for C₄₀H₄₀N₈O₁₂Zn₂: C 50.28, H 4.22, N 11.73%; found: C 50.24, H 4.25, N 11.77%.

S3. Refinement

H atoms in the Zn complex molecule were placed in calculated positions and included in the refinement by using the riding-model approximation, with phenyl C—H distances of 0.93 Å, methyl C—H distances of 0.96 Å and amine N—H distances of 0.86 Å, and with U_iso(H) values of 1.2U_eq(phenyl C, N) or 1.5U_eq(methyl C). The H atoms of the water molecules were located in a difference map and refined with with O—H distance restraints of 0.85 (1) Å and with U_iso(H) values of 1.5U_eq(O).

Computing details

Data collection: RAPID-AUTO (Rigaku Corporation, 1998); cell refinement: RAPID-AUTO (Rigaku Corporation, 1998); data reduction: RAPID-AUTO (Rigaku Corporation, 1998) and CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of complex (I), showing displacement ellipsoids at the 50% probability level. Hydrogen bonds are shown as dashed lines. [Symmetry code: (i) -x, y, 1/2 - z.]
	Fig. 2. The three-dimensional hydrogen-bonding network structure of complex (I), with uninvolved H atoms omitted.
	Fig. 3. The PtS topology exhibited by the structure of complex (I).

Bis{µ-(E)-2-[(2-pyridylamino)(2- pyridylimino)methyl]benzato}bis[acetatozinc(II)] tetrahydrate

Crystal data

[Zn2(C18H13N4O2)2(C2H3O2)2]·4H2O	F(000) = 1968
Mr = 955.58	Dx = 1.543 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 16786 reflections
a = 13.718 (3) Å	θ = 3.1–27.5°
b = 15.433 (3) Å	µ = 1.24 mm^−1
c = 20.526 (4) Å	T = 295 K
β = 108.83 (3)°	Prism, colorless
V = 4113.0 (16) Å^3	0.36 × 0.35 × 0.23 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID diffractometer	4715 independent reflections
Radiation source: fine-focus sealed tube	4200 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
Detector resolution: 10.00 pixels mm^-1	θmax = 27.5°, θmin = 3.1°
ω scans	h = −17→17
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −20→19
Tmin = 0.654, Tmax = 0.744	l = −26→25
19669 measured 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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.075	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0402P)^2 + 2.5563P] where P = (Fo^2 + 2Fc^2)/3
4715 reflections	(Δ/σ)max = 0.001
293 parameters	Δρmax = 0.30 e Å^−3
6 restraints	Δρmin = −0.34 e Å^−3

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

	x	y	z	Uiso*/Ueq
Zn1	0.109493 (13)	0.556597 (11)	0.170539 (8)	0.03110 (7)
O1	0.03458 (9)	0.55145 (7)	0.38822 (6)	0.0400 (3)
O2	0.05633 (11)	0.64525 (12)	0.47430 (8)	0.0702 (5)
O3	0.21542 (10)	0.55981 (9)	0.12489 (7)	0.0498 (3)
O4	0.33033 (12)	0.54528 (10)	0.22844 (8)	0.0593 (4)
N1	0.13623 (10)	0.58427 (8)	0.27422 (6)	0.0316 (3)
N2	0.11601 (10)	0.69499 (9)	0.20214 (7)	0.0343 (3)
N3	0.17612 (11)	0.44789 (8)	0.32053 (7)	0.0330 (3)
H14	0.2033	0.4204	0.3585	0.040*
N4	0.10710 (11)	0.42690 (8)	0.19911 (7)	0.0346 (3)
C1	0.08803 (12)	0.59836 (11)	0.43713 (8)	0.0366 (3)
C2	0.20219 (12)	0.59636 (10)	0.44797 (8)	0.0344 (3)
C3	0.26978 (14)	0.62865 (13)	0.50908 (9)	0.0475 (4)
H3	0.2440	0.6494	0.5428	0.057*
C4	0.37445 (15)	0.63051 (14)	0.52054 (10)	0.0554 (5)
H4	0.4186	0.6523	0.5618	0.067*
C5	0.41404 (14)	0.60000 (14)	0.47081 (10)	0.0510 (5)
H5	0.4847	0.6003	0.4788	0.061*
C6	0.34778 (13)	0.56901 (12)	0.40904 (9)	0.0416 (4)
H6	0.3742	0.5494	0.3753	0.050*
C7	0.24222 (12)	0.56699 (9)	0.39712 (8)	0.0310 (3)
C8	0.17779 (11)	0.53565 (10)	0.32717 (8)	0.0305 (3)
C9	0.13703 (12)	0.67506 (10)	0.26921 (8)	0.0317 (3)
C10	0.15131 (14)	0.73910 (11)	0.31864 (9)	0.0420 (4)
H10	0.1653	0.7250	0.3648	0.050*
C11	0.14415 (15)	0.82451 (11)	0.29738 (10)	0.0450 (4)
H11	0.1539	0.8687	0.3297	0.054*
C12	0.12275 (14)	0.84500 (11)	0.22880 (10)	0.0432 (4)
H12	0.1174	0.9023	0.2141	0.052*
C13	0.10959 (13)	0.77777 (12)	0.18287 (9)	0.0409 (4)
H13	0.0956	0.7906	0.1365	0.049*
C14	0.13792 (11)	0.39426 (10)	0.26269 (8)	0.0316 (3)
C15	0.13807 (13)	0.30501 (11)	0.27437 (9)	0.0405 (4)
H15	0.1590	0.2833	0.3190	0.049*
C16	0.10699 (15)	0.25009 (11)	0.21917 (11)	0.0496 (4)
H16	0.1077	0.1905	0.2260	0.060*
C17	0.07466 (16)	0.28357 (12)	0.15344 (11)	0.0527 (5)
H17	0.0528	0.2473	0.1153	0.063*
C18	0.07548 (15)	0.37115 (12)	0.14569 (10)	0.0456 (4)
H18	0.0531	0.3937	0.1013	0.055*
C19	0.30836 (15)	0.55728 (11)	0.16660 (11)	0.0454 (4)
C20	0.39118 (19)	0.57135 (18)	0.13360 (16)	0.0741 (7)
H201	0.3913	0.6310	0.1204	0.111*
H202	0.3776	0.5352	0.0936	0.111*
H203	0.4571	0.5567	0.1659	0.111*
O1W	0.25784 (17)	0.34431 (12)	0.44071 (9)	0.0780 (5)
H1W1	0.296 (2)	0.2997 (14)	0.4494 (17)	0.117*
H1W2	0.213 (2)	0.341 (2)	0.4614 (17)	0.117*
O2W	0.36212 (13)	0.18362 (12)	0.47327 (8)	0.0649 (4)
H2W1	0.4260 (8)	0.1812 (18)	0.4780 (14)	0.097*
H2W2	0.3308 (17)	0.1441 (15)	0.4449 (13)	0.097*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.03200 (11)	0.03393 (11)	0.02783 (11)	−0.00038 (7)	0.01027 (7)	0.00074 (7)
O1	0.0317 (6)	0.0468 (7)	0.0385 (6)	0.0003 (5)	0.0074 (5)	−0.0069 (5)
O2	0.0467 (8)	0.1020 (12)	0.0646 (9)	0.0017 (8)	0.0217 (7)	−0.0393 (9)
O3	0.0432 (7)	0.0606 (8)	0.0530 (8)	−0.0040 (6)	0.0257 (6)	−0.0006 (6)
O4	0.0547 (9)	0.0585 (9)	0.0641 (10)	−0.0013 (6)	0.0182 (7)	−0.0009 (7)
N1	0.0373 (7)	0.0293 (6)	0.0282 (6)	0.0012 (5)	0.0103 (5)	−0.0005 (5)
N2	0.0341 (7)	0.0352 (7)	0.0330 (6)	0.0009 (5)	0.0100 (5)	0.0021 (6)
N3	0.0392 (7)	0.0301 (6)	0.0291 (6)	0.0037 (5)	0.0102 (5)	0.0028 (5)
N4	0.0383 (7)	0.0318 (6)	0.0329 (7)	0.0009 (5)	0.0105 (5)	−0.0010 (6)
C1	0.0359 (8)	0.0429 (9)	0.0307 (7)	0.0027 (7)	0.0103 (6)	0.0005 (7)
C2	0.0349 (8)	0.0375 (8)	0.0286 (7)	0.0007 (6)	0.0072 (6)	0.0003 (6)
C3	0.0451 (10)	0.0614 (11)	0.0329 (8)	−0.0026 (8)	0.0083 (7)	−0.0081 (8)
C4	0.0448 (10)	0.0713 (13)	0.0397 (9)	−0.0110 (9)	−0.0010 (8)	−0.0079 (9)
C5	0.0313 (9)	0.0654 (12)	0.0509 (10)	−0.0061 (8)	0.0057 (7)	0.0018 (10)
C6	0.0346 (8)	0.0492 (10)	0.0413 (9)	0.0007 (7)	0.0128 (7)	0.0007 (8)
C7	0.0324 (8)	0.0297 (7)	0.0289 (7)	0.0020 (6)	0.0071 (6)	0.0026 (6)
C8	0.0299 (7)	0.0326 (7)	0.0310 (7)	0.0018 (6)	0.0127 (6)	−0.0001 (6)
C9	0.0300 (7)	0.0317 (7)	0.0335 (7)	0.0009 (6)	0.0105 (6)	0.0004 (6)
C10	0.0564 (11)	0.0348 (8)	0.0359 (8)	0.0026 (7)	0.0164 (8)	0.0006 (7)
C11	0.0550 (11)	0.0310 (8)	0.0521 (10)	0.0009 (7)	0.0215 (8)	−0.0045 (8)
C12	0.0434 (9)	0.0326 (8)	0.0558 (10)	0.0026 (7)	0.0191 (8)	0.0093 (8)
C13	0.0407 (9)	0.0410 (9)	0.0410 (9)	0.0028 (7)	0.0132 (7)	0.0109 (7)
C14	0.0276 (7)	0.0310 (7)	0.0375 (8)	0.0009 (6)	0.0125 (6)	−0.0009 (6)
C15	0.0398 (9)	0.0329 (8)	0.0478 (9)	0.0001 (7)	0.0129 (7)	0.0042 (7)
C16	0.0508 (11)	0.0294 (8)	0.0651 (12)	−0.0011 (7)	0.0137 (9)	−0.0026 (8)
C17	0.0586 (12)	0.0395 (9)	0.0544 (11)	−0.0008 (8)	0.0105 (9)	−0.0148 (9)
C18	0.0525 (10)	0.0415 (9)	0.0395 (9)	0.0002 (8)	0.0102 (8)	−0.0078 (8)
C19	0.0428 (10)	0.0331 (8)	0.0674 (13)	−0.0047 (7)	0.0279 (9)	−0.0100 (8)
C20	0.0544 (13)	0.0849 (17)	0.100 (2)	−0.0152 (12)	0.0484 (14)	−0.0176 (15)
O1W	0.1101 (15)	0.0768 (11)	0.0604 (9)	0.0342 (10)	0.0458 (10)	0.0285 (9)
O2W	0.0613 (9)	0.0789 (11)	0.0592 (9)	0.0187 (8)	0.0259 (8)	−0.0086 (8)

Geometric parameters (Å, º)

Zn1—O1^i	1.9566 (14)	C6—C7	1.389 (2)
Zn1—O3	1.9675 (13)	C6—H6	0.9300
Zn1—N1	2.0838 (13)	C7—C8	1.502 (2)
Zn1—N4	2.0890 (14)	C9—C10	1.384 (2)
Zn1—N2	2.2256 (14)	C10—C11	1.382 (2)
O1—C1	1.263 (2)	C10—H10	0.9300
O1—Zn1^i	1.9566 (14)	C11—C12	1.379 (3)
O2—C1	1.228 (2)	C11—H11	0.9300
O3—C19	1.287 (3)	C12—C13	1.374 (3)
O4—C19	1.220 (3)	C12—H12	0.9300
N1—C8	1.292 (2)	C13—H13	0.9300
N1—C9	1.405 (2)	C14—C15	1.398 (2)
N2—C13	1.332 (2)	C15—C16	1.368 (3)
N2—C9	1.348 (2)	C15—H15	0.9300
N3—C8	1.3607 (19)	C16—C17	1.377 (3)
N3—C14	1.403 (2)	C16—H16	0.9300
N3—H14	0.8600	C17—C18	1.361 (3)
N4—C14	1.334 (2)	C17—H17	0.9300
N4—C18	1.351 (2)	C18—H18	0.9300
C1—C2	1.509 (2)	C19—C20	1.514 (3)
C2—C3	1.389 (2)	C20—H201	0.9600
C2—C7	1.402 (2)	C20—H202	0.9600
C3—C4	1.378 (3)	C20—H203	0.9600
C3—H3	0.9300	O1W—H1W1	0.85 (3)
C4—C5	1.384 (3)	O1W—H1W2	0.85 (3)
C4—H4	0.9300	O2W—H2W1	0.852 (9)
C5—C6	1.385 (3)	O2W—H2W2	0.86 (2)
C5—H5	0.9300
O1^i—Zn1—O3	117.51 (6)	N1—C8—N3	120.35 (14)
O1^i—Zn1—N1	116.59 (6)	N1—C8—C7	125.50 (14)
O3—Zn1—N1	124.59 (6)	N3—C8—C7	113.69 (13)
O1^i—Zn1—N4	91.71 (5)	N2—C9—C10	121.24 (14)
O3—Zn1—N4	103.81 (6)	N2—C9—N1	107.35 (13)
N1—Zn1—N4	85.59 (5)	C10—C9—N1	131.36 (14)
O1^i—Zn1—N2	98.98 (5)	C11—C10—C9	118.08 (16)
O3—Zn1—N2	98.52 (5)	C11—C10—H10	121.0
N1—Zn1—N2	61.86 (5)	C9—C10—H10	121.0
N4—Zn1—N2	147.20 (5)	C12—C11—C10	120.74 (16)
C1—O1—Zn1^i	132.73 (11)	C12—C11—H11	119.6
C19—O3—Zn1	114.08 (12)	C10—C11—H11	119.6
C8—N1—C9	128.97 (14)	C13—C12—C11	117.70 (16)
C8—N1—Zn1	128.64 (11)	C13—C12—H12	121.2
C9—N1—Zn1	97.62 (9)	C11—C12—H12	121.2
C13—N2—C9	119.61 (14)	N2—C13—C12	122.62 (16)
C13—N2—Zn1	147.29 (12)	N2—C13—H13	118.7
C9—N2—Zn1	93.09 (9)	C12—C13—H13	118.7
C8—N3—C14	131.43 (13)	N4—C14—C15	121.48 (15)
C8—N3—H14	114.3	N4—C14—N3	121.27 (14)
C14—N3—H14	114.3	C15—C14—N3	117.18 (14)
C14—N4—C18	118.10 (14)	C16—C15—C14	119.05 (17)
C14—N4—Zn1	127.43 (11)	C16—C15—H15	120.5
C18—N4—Zn1	114.37 (12)	C14—C15—H15	120.5
O2—C1—O1	126.90 (16)	C15—C16—C17	119.63 (17)
O2—C1—C2	118.62 (15)	C15—C16—H16	120.2
O1—C1—C2	114.46 (14)	C17—C16—H16	120.2
C3—C2—C7	118.71 (16)	C18—C17—C16	118.34 (18)
C3—C2—C1	118.95 (15)	C18—C17—H17	120.8
C7—C2—C1	122.26 (14)	C16—C17—H17	120.8
C4—C3—C2	121.09 (18)	N4—C18—C17	123.39 (18)
C4—C3—H3	119.5	N4—C18—H18	118.3
C2—C3—H3	119.5	C17—C18—H18	118.3
C3—C4—C5	120.14 (17)	O4—C19—O3	123.76 (18)
C3—C4—H4	119.9	O4—C19—C20	121.2 (2)
C5—C4—H4	119.9	O3—C19—C20	115.0 (2)
C4—C5—C6	119.65 (17)	C19—C20—H201	109.5
C4—C5—H5	120.2	C19—C20—H202	109.5
C6—C5—H5	120.2	H201—C20—H202	109.5
C5—C6—C7	120.52 (17)	C19—C20—H203	109.5
C5—C6—H6	119.7	H201—C20—H203	109.5
C7—C6—H6	119.7	H202—C20—H203	109.5
C6—C7—C2	119.87 (15)	H1W1—O1W—H1W2	109.9 (16)
C6—C7—C8	115.71 (14)	H2W1—O2W—H2W2	108.5 (15)
C2—C7—C8	124.37 (14)
O1^i—Zn1—O3—C19	−175.58 (11)	C3—C2—C7—C8	−176.10 (16)
N1—Zn1—O3—C19	18.00 (14)	C1—C2—C7—C8	0.7 (2)
N4—Zn1—O3—C19	−76.21 (12)	C9—N1—C8—N3	−174.35 (15)
N2—Zn1—O3—C19	79.59 (12)	Zn1—N1—C8—N3	−24.5 (2)
O1^i—Zn1—N1—C8	115.36 (14)	C9—N1—C8—C7	−2.7 (3)
O3—Zn1—N1—C8	−78.11 (15)	Zn1—N1—C8—C7	147.23 (12)
N4—Zn1—N1—C8	25.65 (14)	C14—N3—C8—N1	2.3 (3)
N2—Zn1—N1—C8	−158.64 (15)	C14—N3—C8—C7	−170.28 (15)
O1^i—Zn1—N1—C9	−87.82 (10)	C6—C7—C8—N1	−92.75 (19)
O3—Zn1—N1—C9	78.72 (10)	C2—C7—C8—N1	84.7 (2)
N4—Zn1—N1—C9	−177.53 (10)	C6—C7—C8—N3	79.42 (18)
N2—Zn1—N1—C9	−1.81 (8)	C2—C7—C8—N3	−103.11 (17)
O1^i—Zn1—N2—C13	−64.2 (2)	C13—N2—C9—C10	0.5 (2)
O3—Zn1—N2—C13	55.6 (2)	Zn1—N2—C9—C10	179.61 (14)
N1—Zn1—N2—C13	−179.6 (2)	C13—N2—C9—N1	178.36 (14)
N4—Zn1—N2—C13	−171.72 (18)	Zn1—N2—C9—N1	−2.57 (12)
O1^i—Zn1—N2—C9	117.30 (10)	C8—N1—C9—N2	159.48 (15)
O3—Zn1—N2—C9	−122.93 (10)	Zn1—N1—C9—N2	2.76 (13)
N1—Zn1—N2—C9	1.88 (9)	C8—N1—C9—C10	−23.0 (3)
N4—Zn1—N2—C9	9.78 (15)	Zn1—N1—C9—C10	−179.72 (17)
O1^i—Zn1—N4—C14	−129.75 (14)	N2—C9—C10—C11	−0.5 (3)
O3—Zn1—N4—C14	111.35 (14)	N1—C9—C10—C11	−177.69 (16)
N1—Zn1—N4—C14	−13.21 (13)	C9—C10—C11—C12	0.4 (3)
N2—Zn1—N4—C14	−20.2 (2)	C10—C11—C12—C13	−0.4 (3)
O1^i—Zn1—N4—C18	54.05 (13)	C9—N2—C13—C12	−0.6 (2)
O3—Zn1—N4—C18	−64.84 (13)	Zn1—N2—C13—C12	−178.84 (14)
N1—Zn1—N4—C18	170.59 (13)	C11—C12—C13—N2	0.5 (3)
N2—Zn1—N4—C18	163.61 (11)	C18—N4—C14—C15	0.2 (2)
Zn1^i—O1—C1—O2	23.6 (3)	Zn1—N4—C14—C15	−175.92 (12)
Zn1^i—O1—C1—C2	−154.67 (11)	C18—N4—C14—N3	177.10 (15)
O2—C1—C2—C3	16.4 (3)	Zn1—N4—C14—N3	1.0 (2)
O1—C1—C2—C3	−165.18 (16)	C8—N3—C14—N4	9.7 (3)
O2—C1—C2—C7	−160.37 (17)	C8—N3—C14—C15	−173.18 (16)
O1—C1—C2—C7	18.1 (2)	N4—C14—C15—C16	0.8 (3)
C7—C2—C3—C4	−1.2 (3)	N3—C14—C15—C16	−176.30 (16)
C1—C2—C3—C4	−178.13 (18)	C14—C15—C16—C17	−1.1 (3)
C2—C3—C4—C5	0.1 (3)	C15—C16—C17—C18	0.4 (3)
C3—C4—C5—C6	1.1 (3)	C14—N4—C18—C17	−0.8 (3)
C4—C5—C6—C7	−1.1 (3)	Zn1—N4—C18—C17	175.76 (16)
C5—C6—C7—C2	−0.1 (3)	C16—C17—C18—N4	0.5 (3)
C5—C6—C7—C8	177.47 (16)	Zn1—O3—C19—O4	7.0 (2)
C3—C2—C7—C6	1.3 (2)	Zn1—O3—C19—C20	−172.42 (14)
C1—C2—C7—C6	178.04 (15)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H14···O1W	0.86	1.99	2.848 (2)	173
O1W—H1W1···O2W	0.85 (3)	2.00 (1)	2.833 (2)	169 (3)
O1W—H1W2···O2W^ii	0.85 (3)	1.97 (3)	2.808 (2)	165 (3)
O2W—H2W1···O2^iii	0.85 (1)	1.90 (1)	2.723 (2)	163 (3)
O2W—H2W2···O3^iv	0.86 (2)	1.89 (1)	2.731 (2)	168 (3)

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