One-dimensional zinc-based coord­in­ation polymers incorporating cyanate anions

Two one-dimensional zinc-based coordination polymers containing cyanate anions are reported. catena-Poly[sodium [[tricyanato­zinc(II)]-μ-1,4-diaza­bicyclo­[2.2.2]octane-κ²N:N′]], {Na[Zn(NCO)₃(C₆H₁₂N₂)]}_n, consists of linear [tricyanato­zinc(II)]-μ-1,4-diaza­bicyclo­[2.2.2]octane strands in which the Zn²⁺ cations adopt trigonal–bipyramidal coordination on sites of m2 point symmetry. Na⁺ cations lie between the strands on sites of m point symmetry, coordinated in a distorted octa­hedral geometry by six O atoms of the cyanate anions. catena-Poly[[dicyanato­zinc(II)]-μ-4,4′-bipyridine-κ²N:N′], [Zn(NCO)₂(C₁₀H₈N₂)]_n, crystallizes in the space group P2₁/n with Z′ = 5. The structure consists of zigzag strands formed by Zn²⁺ cations linked via 4,4′-bipyridine. Each Zn²⁺ cation adopts a tetra­hedral coordination, with two sites occupied by 4,4′-bipyridine and two cyanate anions completing the coordination sphere. The structure is closely comparable with the thio­cyanate and halide analogues [ZnX₂(C₁₀H₈N₂)] (X = NCS, Cl or Br).

S1. Comment

1,4-Diazobicyclo[2.2.2]octane (DABCO) and 4,4'-bipyridine (bipy) are commonly employed as `spacer' ligands for the construction of metal–organic frameworks (MOFs). With Zn^II, the latter ligand in particular has been included in MOFs with three-dimensional (for example, Wang et al., 2004; Tao et al., 2000) and two-dimensional (Gable et al., 1990; Ng, 2003) architectures, and also in numerous one-dimensional coordination polymers (Kondo et al., 1999; Pan et al., 1999; Sampanthar & Vittal, 1999; Ma et al., 2000). MOFs incorporating DABCO are less prevalent, but two-dimensional (He et al., 2002) and three-dimensional (Dybtsev et al., 2004) frameworks have been reported in which DABCO is present in combination with terephthalic acid. Zn–DABCO complexes that incorporate monodentate or chelating ligands have been observed as discrete units (for example, Fronczek et al., 1990; Petrusenko et al., 1997) and as one-dimensional coordination polymers, with both linear (Petrusenko et al., 1997) and zigzag (Huang et al. 1996; Ng, 1999; Braga et al., 2004) geometries. Structures incorporating cyanate anions bonded to Zn^II are rather more rare: only three examples (Choi et al., 1999; Secondo et al., 2000; Soldatov et al., 1999) exist in the Cambridge Structural Database (CSD, Version?; Allen, 2002), and there are no examples in the Inorganic Crystal Structure Database (ICSD, 2005).

In the title complex, Na[Zn(NCO)₃(C₆H₁₂N₂)], (I) (Fig. 1), one-dimensional linear strands are formed from Zn²⁺ cations linked via DABCO moieties. The coordination geometry of the Zn²⁺ cation is trigonal–bipyramidal, with three cyanate anions, coordinated through N, lying in the equatorial plane. The anionic [Zn(NCO)₃(DABCO)]⁻ strands adopt a trigonal arrangement, with the cyanate anions lying in mirror planes at z = 1/4 and 3/4. Na⁺ cations (at z = 0 and 1/2) lie between the mirror planes (Fig. 2), coordinated by the O atoms of the cyanate anions. The single symmetry-independent cyanate anion in the structure is modelled as disordered, with one orientation (atoms C1 and O1) lying along the twofold rotation axis that passes through atoms Zn1 and N1, and a second orientation (atoms C1A and O1A) displaced slightly from the twofold axis. The disordered description was deemed to be more satisfactory than an ordered description incorporating displacement ellipsoids that are grossly distorted in the direction perpendicular to the twofold axis. On the basis of the O-atom sites lying on the twofold axes, the coordination geometry around Na⁺ may be described as distorted octahedral, the distortion being parallel to the threefold axis of the octahedron (the crystallographic c axis). Incorporation of Na⁺ at this coordination site must be consistent with the Zn···Zn separation imposed by the DABCO moiety. That is, the perpendicular separation of 3.54 Å between the mirror planes containing the Zn²⁺ cations and cyanate anions is consistent with an Na—O1 distance of 2.377 (6) Å. Inclusion of a larger spacer ligand such as bipy in a similar structure would provide a coordination site between the cyanate anions that is too large to accommodate Na⁺ efficiently.

The second compound, [Zn(NCO)₂(C₁₀H₈N₂)], (II) (Fig. 3), crystallizes in space group P2₁/n with Z' = 5. This is relatively unusual; only 32 examples exist at present in the CSD of structures in space group P2₁/c (or equivalent) with Z' ≥ 5. The structure of (II) comprises neutral one-dimensional strands in which the coordination geometry around Zn²⁺ is tetrahedral. The environment of atom Zn1 closely resembles that in the comparable mononuclear complex [Zn(NCO)₂(4-N,N'-dimethylaminopyridine)₂] (Secondo et al., 2000). The strands in (II) adopt a zigzag geometry and can be envisaged as lying in layers parallel to the bc plane at x = 1/4 and 3/4. Similar layered arrangements are observed in the thiocyanate and halide analogues [ZnX₂(C₁₀H₈N₂)], where X = NCS (Kondo et al., 1999; Pan et al., 1999), Cl or Br (Hu & Englert, 2001), the Cl derivative having been observed to be dimorphic (Fu et al., 2001). In each of these structures, the layers display regular planar geometry, having mirror or twofold rotation symmetry. In (II), the layers are rather more distorted, and the Zn²⁺ cations in adjacent strands are not strictly co-planar. This distortion appears to be driven to some extent by differing coordination arrangements of the cyanate ligands: on each of the five symmetry-independent Zn²⁺ cations, one cyanate ligand adopts an Zn—NCO geometry that is closer to linear [Zn—N—C angle in the range 158.4 (14)–177.3 (17)°], while the other is more bent at the N atom [Zn—N—C angle in the range 140.2 (14)–146.3 (11)°; Table 1 No values have been flagged in the CIF for inclusion in a table. Do you wish to add one?]. Within the layers, the Zn²⁺ cations in adjacent strands along the c direction lie alternately above and below the mean plane through all Zn²⁺ cations, apparently to optimize the packing arrangement of the cyanate moieties. The layers are stacked one upon the other with an offset that enables the cyanate moieties to project between the phenyl rings of the bipy units in adjacent layers (Fig. 4).

S2. Experimental

Compound (I) was prepared as follows. Sodium cyanate (0.26 g, 4 mmol) in water (4 ml) and 1,4-diazobicyclo[2.2.2]octane (0.234 g, 2 mmol) in methanol (1 ml) were added to a mixture of Zn(NO₃)₂·6H₂O (0.15 g, 0.5 mmol) and concentrated nitric acid (14M, 0.07 ml, 1 mmol) in methanol (3 ml). Crystals of (I) were deposited from the colourless solution over several hours (yield 62 mg, 37%). IR ν(NCO): 2239, 2170 cm⁻¹. Compound (II) was prepared as follows. Sodium cyanate (0.26 g, 4 mmol) in water (4 ml) and 4,4'-bipyridine (0.082 g, 0.53 mmol) in methanol (8 ml) were added to a mixture of Zn(NO₃)₂·6H₂O (154 mg, 0.52 mmol) and concentrated nitric acid (14M, 0.07 ml, 1 mmol) in methanol (3 ml). Crystals of (II) were deposited from the colourless solution over several hours (yield 71 mg, 45%). IR ν(NCO): 2227 cm⁻¹.

S3. Refinement

The disorder of the cyanate ligand in (I) was modelled with two pairs of C and O atoms. One pair (C1 and O1) lie exactly on the twofold axis that passes through atoms Zn1 and N1, and one pair (C1A and O1A) are displaced from it. Both pairs lie in the mirror plane at z = 1/4. The N—C, C—O and N···O distances within each component were restrained to equivalent refined values, with standard uncertainties of 0.01 Å. Initially, the atomic displacement parameters were fixed to 0.04 Ų and the site occupancy factors (s.o.f) were refined with s.o.f·(C1/O1) + s.o.f·(C1A/O1A) = 0.25 (to account for the multiplicity of the atomic sites). The site occupancy factors were subsequently constrained to the refined values (C1 = O1 = 0.05, C1A = O1A =)/5 [Please correct], and two isotropic displacement parameters were refined, one common to both atoms in each component. The crystal of (II) is monoclinic with β ca 90°, and was twinned to appear orthorhombic: twin law (1 0 0, 0 − 1 0, 0 0 − 1), refined BASF 0.497 (3). Diffraction was relatively weak, with less than 50% of the data observed at the 2σ(I) level. The resulting structure is of relatively low precision. The anisotropic displacement parameters of the C, N and O atoms were restrained to be approximately isotropic with a standard uncertainty of 0.01 Ų. The largest peak and deepest hole in the residual electron density are associated with atoms Zn2 and Zn3, respectively. For both structures, H atoms bound to C were positioned geometrically and allowed to ride during subsequent refinement, with C—H = 0.99 Å for the methylene group in the DABCO moiety in (I) and 0.95 Å for the bipy moieties in (II). In both cases, U_iso(H) = 1.2 U_eq(C).

Computing details

For both compounds, data collection: APEX2 (Bruker Nonius, 2004); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The coordination environment of Zn1 in (I), showing displacement ellipsoids at the 50% probability levels. The disorder of the cyanate moiety is shown for only one ligand. [Symmetry codes: (i) x, x-y, z; (ii) 1 − y, x-y, z; (iii) 1 − x + y, 1 − x, z; (iv) x, y, 1/2 − z.]
	Fig. 2. A view of (I), (a) along the c direction and (b) along the a direction. For the cyanate anions, only the disordered components lying on the twofold axes are shown.
	Fig. 3. The asymmetric unit in (II), showing displacement ellipsoids at the 50% probability level. For clarity, C atoms are not labelled. The tetrahedral geometry around Zn is shown most clearly for atom Zn4, and the differing coordination modes of the cyanate anions are illustrated most clearly by N8 (linear) and N7 (bent).
	Fig. 4. A view of a single layer in (II), (a) along the a direction (perpendicular to the layer plane) and (b) along the b direction, showing Zn^2+ cations lying above and below the mean plane of the layer.

(I) catena-Poly[sodium [[tricyanatozinc(II)]-µ-1,4-diazobicyclo[2.2.2]octane-κ²N:N']]

Crystal data

Na[Zn(NCO)3(C6H12N2)]	Dx = 1.689 Mg m^−3
Mr = 326.60	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P63/mmc	Cell parameters from 3837 reflections
Hall symbol: -P 6c 2c	θ = 2.3–30.1°
a = 10.2345 (2) Å	µ = 1.96 mm^−1
c = 7.0799 (3) Å	T = 180 K
V = 642.23 (3) Å^3	Block, colourless
Z = 2	0.35 × 0.25 × 0.20 mm
F(000) = 332

Data collection

Bruker Nonius X8 APEXII CCD area-detector diffractometer	407 independent reflections
Radiation source: fine-focus sealed tube	388 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
thin–slice ω and ϕ scans	θmax = 30.6°, θmin = 3.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −10→14
Tmin = 0.580, Tmax = 0.675	k = −12→10
6400 measured reflections	l = −9→10

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.031	H-atom parameters constrained
wR(F^2) = 0.076	w = 1/[σ^2(Fo^2) + (0.0374P)^2 + 0.743P] where P = (Fo^2 + 2Fc^2)/3
S = 1.11	(Δ/σ)max < 0.001
407 reflections	Δρmax = 0.63 e Å^−3
30 parameters	Δρmin = −0.64 e Å^−3
6 restraints	Extinction correction: SHELXTL (Sheldrick, 2000), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.014 (3)

Special details

Experimental. Apparent disorder in positions of NCO ligands.

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	Occ. (<1)
Zn1	0.6667	0.3333	0.2500	0.0159 (2)
Na1	0.0000	0.0000	0.0000	0.0251 (5)
N2	0.6667	0.3333	0.5668 (4)	0.0156 (6)
C2	0.58907 (13)	0.41093 (13)	0.6419 (3)	0.0262 (5)
H2A	0.4837	0.3596	0.5955	0.031*
N1	0.4425 (4)	0.22125 (18)	0.2500	0.0371 (8)
O1	0.1790 (11)	0.0895 (5)	0.2500	0.037 (3)*	0.20
C1	0.3163 (12)	0.1581 (6)	0.2500	0.037 (3)*	0.20
O1A	0.1827 (5)	0.1518 (5)	0.2500	0.0280 (7)*	0.40
C1A	0.3175 (6)	0.1905 (7)	0.2500	0.0280 (7)*	0.40

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0178 (2)	0.0178 (2)	0.0122 (3)	0.00892 (12)	0.000	0.000
Na1	0.0217 (6)	0.0217 (6)	0.0318 (12)	0.0109 (3)	0.000	0.000
N2	0.0168 (8)	0.0168 (8)	0.0131 (12)	0.0084 (4)	0.000	0.000
C2	0.0400 (10)	0.0400 (10)	0.0143 (8)	0.0318 (12)	−0.0004 (4)	0.0004 (4)
N1	0.0219 (15)	0.0608 (19)	0.0157 (12)	0.0110 (7)	0.000	0.000

Geometric parameters (Å, º)

Zn1—N1	1.987 (3)	Na1—O1A^xi	2.477 (3)
Zn1—N1^i	1.987 (3)	Na1—O1A^vi	2.477 (3)
Zn1—N1^ii	1.987 (3)	Na1—O1A^vii	2.477 (3)
Zn1—N2	2.243 (3)	Na1—O1A^viii	2.477 (3)
Zn1—N2^iii	2.243 (3)	Na1—O1A^xii	2.477 (3)
Na1—O1	2.377 (6)	Na1—O1A^xiii	2.477 (3)
Na1—O1^iv	2.377 (6)	Na1—O1A^xiv	2.477 (3)
Na1—O1^v	2.377 (6)	N2—C2	1.475 (2)
Na1—O1^vi	2.377 (6)	N2—C2^i	1.475 (3)
Na1—O1^vii	2.377 (6)	N2—C2^ii	1.475 (3)
Na1—O1^viii	2.377 (6)	C2—C2^xv	1.531 (4)
Na1—O1A	2.477 (3)	C2—H2A	0.990
Na1—O1A^iv	2.477 (3)	N1—C1	1.119 (11)
Na1—O1A^v	2.477 (3)	N1—C1A	1.154 (6)
Na1—O1A^ix	2.477 (3)	O1—C1	1.217 (11)
Na1—O1A^x	2.477 (3)	O1A—C1A	1.230 (7)
N1—Zn1—N1^i	120.0	O1^vii—Na1—O1A^v	99.76 (17)
N1—Zn1—N1^ii	120.0	O1^iv—Na1—O1A^v	80.24 (17)
N1^i—Zn1—N1^ii	120.0	O1^viii—Na1—O1A^v	165.54 (10)
N2—Zn1—N1	90.0	O1^v—Na1—O1A^v	14.46 (10)
N2—Zn1—N1^i	90.0	O1—Na1—O1A^v	62.74 (14)
N2—Zn1—N1^ii	90.0	O1A^xiv—Na1—O1A^v	52.38 (19)
N2—Zn1—N2^iii	180.0	O1A^xi—Na1—O1A^v	127.62 (19)
N1^i—Zn1—N2^iii	90.0	O1A^viii—Na1—O1A^v	180.00 (17)
N1—Zn1—N2^iii	90.0	O1^vi—Na1—O1A^vi	14.46 (10)
N1^ii—Zn1—N2^iii	90.0	O1^vii—Na1—O1A^vi	62.74 (14)
O1—Na1—O1^vi	180.0	O1^iv—Na1—O1A^vi	117.26 (14)
O1—Na1—O1^vii	109.4 (3)	O1^viii—Na1—O1A^vi	80.24 (17)
O1—Na1—O1^iv	70.6 (3)	O1^v—Na1—O1A^vi	99.76 (17)
O1—Na1—O1^viii	109.4 (3)	O1—Na1—O1A^vi	165.54 (10)
O1—Na1—O1^v	70.6 (3)	O1A^xiv—Na1—O1A^vi	151.1 (2)
O1^vi—Na1—O1^vii	70.6 (3)	O1A^xi—Na1—O1A^vi	28.9 (2)
O1^vi—Na1—O1^iv	109.4 (3)	O1A^viii—Na1—O1A^vi	74.59 (11)
O1^vii—Na1—O1^iv	180.0 (4)	O1A^v—Na1—O1A^vi	105.41 (11)
O1^vi—Na1—O1^viii	70.6 (3)	O1^vi—Na1—O1A^xii	99.76 (17)
O1^vii—Na1—O1^viii	70.6 (3)	O1^vii—Na1—O1A^xii	117.26 (14)
O1^iv—Na1—O1^viii	109.4 (3)	O1^iv—Na1—O1A^xii	62.74 (14)
O1^vi—Na1—O1^v	109.4 (3)	O1^viii—Na1—O1A^xii	165.54 (10)
O1^vii—Na1—O1^v	109.4 (3)	O1^v—Na1—O1A^xii	14.46 (10)
O1^iv—Na1—O1^v	70.6 (3)	O1—Na1—O1A^xii	80.24 (17)
O1^viii—Na1—O1^v	180.0 (4)	O1A^xiv—Na1—O1A^xii	74.59 (11)
O1^vi—Na1—O1A^xiv	165.54 (10)	O1A^xi—Na1—O1A^xii	105.41 (11)
O1^vii—Na1—O1A^xiv	99.76 (17)	O1A^viii—Na1—O1A^xii	151.1 (2)
O1^iv—Na1—O1A^xiv	80.24 (17)	O1A^v—Na1—O1A^xii	28.9 (2)
O1^viii—Na1—O1A^xiv	117.26 (14)	O1A^vi—Na1—O1A^xii	92.60 (15)
O1^v—Na1—O1A^xiv	62.74 (14)	C2—N2—C2^ii	107.75 (14)
O1—Na1—O1A^xiv	14.46 (10)	C2—N2—C2^i	107.75 (14)
O1^vi—Na1—O1A^xi	14.46 (10)	C2^ii—N2—C2^i	107.75 (14)
O1^vii—Na1—O1A^xi	80.24 (17)	C2—N2—Zn1	111.14 (13)
O1^iv—Na1—O1A^xi	99.76 (17)	C2^ii—N2—Zn1	111.14 (14)
O1^viii—Na1—O1A^xi	62.74 (14)	C2^i—N2—Zn1	111.14 (13)
O1^v—Na1—O1A^xi	117.26 (14)	N2—C2—C2^xv	111.14 (13)
O1—Na1—O1A^xi	165.54 (10)	N2—C2—H2A	109.4
O1A^xiv—Na1—O1A^xi	180.00 (16)	C2^xv—C2—H2A	109.4
O1^vi—Na1—O1A^viii	62.74 (14)	C1—N1—Zn1	180.0 (6)
O1^vii—Na1—O1A^viii	80.24 (17)	C1A—N1—Zn1	163.7 (3)
O1^iv—Na1—O1A^viii	99.76 (17)	C1A^xiv—N1—Zn1	163.7 (3)
O1^viii—Na1—O1A^viii	14.46 (10)	C1—O1—Na1	131.87 (17)
O1^v—Na1—O1A^viii	165.54 (10)	C1—O1—Na1^xvi	131.87 (17)
O1—Na1—O1A^viii	117.26 (14)	Na1—O1—Na1^xvi	96.3 (3)
O1A^xiv—Na1—O1A^viii	127.62 (19)	N1—C1—O1	180.0 (12)
O1A^xi—Na1—O1A^viii	52.38 (19)	N1—C1A—O1A	177.4 (6)
O1^vi—Na1—O1A^v	117.26 (14)
N1^i—Zn1—N2—C2	180.0	O1—Na1—O1A—C1A	63.5 (8)
N1—Zn1—N2—C2	−60.0	O1A^xiv—Na1—O1A—C1A	61.2 (4)
N1^ii—Zn1—N2—C2	60.0	O1A^xi—Na1—O1A—C1A	−118.8 (4)
N1^i—Zn1—N2—C2^ii	60.0	O1A^viii—Na1—O1A—C1A	−83.0 (5)
N1—Zn1—N2—C2^ii	180.0	O1A^v—Na1—O1A—C1A	97.0 (5)
N1^ii—Zn1—N2—C2^ii	−60.0	O1A^xii—Na1—O1A—C1A	123.3 (4)
N1^i—Zn1—N2—C2^i	−60.0	O1^vi—Na1—O1A—O1A^xiv	−177.7 (7)
N1—Zn1—N2—C2^i	60.0	O1^vii—Na1—O1A—O1A^xiv	−57.40 (16)
N1^ii—Zn1—N2—C2^i	180.0	O1^iv—Na1—O1A—O1A^xiv	122.60 (16)
C2^ii—N2—C2—C2^xv	−58.01 (16)	O1^viii—Na1—O1A—O1A^xiv	−130.55 (8)
C2^i—N2—C2—C2^xv	58.01 (16)	O1^v—Na1—O1A—O1A^xiv	49.45 (8)
Zn1—N2—C2—C2^xv	180.0	O1—Na1—O1A—O1A^xiv	2.3 (7)
N1^i—Zn1—N1—C1A	180.0	O1A^xi—Na1—O1A—O1A^xiv	180.0
N1^ii—Zn1—N1—C1A	0.0	O1A^viii—Na1—O1A—O1A^xiv	−144.20 (11)
N2^iii—Zn1—N1—C1A	−90.0	O1A^v—Na1—O1A—O1A^xiv	35.80 (11)
N2—Zn1—N1—C1A	90.0	O1A^xii—Na1—O1A—O1A^xiv	62.10 (9)
N1^i—Zn1—N1—C1A^xiv	0.0	O1^vi—Na1—O1A—C1A^xiv	−139.3 (7)
N1^ii—Zn1—N1—C1A^xiv	180.0	O1^vii—Na1—O1A—C1A^xiv	−19.1 (3)
N2^iii—Zn1—N1—C1A^xiv	90.0	O1^iv—Na1—O1A—C1A^xiv	160.9 (3)
N2—Zn1—N1—C1A^xiv	−90.0	O1^viii—Na1—O1A—C1A^xiv	−92.2 (3)
O1^vii—Na1—O1—C1	37.79 (7)	O1^v—Na1—O1A—C1A^xiv	87.8 (3)
O1^iv—Na1—O1—C1	−142.21 (7)	O1—Na1—O1A—C1A^xiv	40.7 (7)
O1^viii—Na1—O1—C1	−37.79 (7)	O1A^xiv—Na1—O1A—C1A^xiv	38.3 (3)
O1^v—Na1—O1—C1	142.21 (7)	O1A^xi—Na1—O1A—C1A^xiv	−141.7 (3)
O1A^xiv—Na1—O1—C1	87.7 (7)	O1A^viii—Na1—O1A—C1A^xiv	−105.9 (3)
O1A^xi—Na1—O1—C1	−92.3 (7)	O1A^v—Na1—O1A—C1A^xiv	74.1 (3)
O1A^viii—Na1—O1—C1	−51.00 (12)	O1A^xii—Na1—O1A—C1A^xiv	100.4 (2)
O1A^v—Na1—O1—C1	129.00 (12)	O1^vi—Na1—O1A—Na1^xvi	107.6 (7)
O1A^vi—Na1—O1—C1	92.3 (7)	O1^vii—Na1—O1A—Na1^xvi	−132.15 (16)
O1A^xii—Na1—O1—C1	153.40 (10)	O1^iv—Na1—O1A—Na1^xvi	47.85 (16)
O1^vii—Na1—O1—Na1^xvi	−142.21 (7)	O1^viii—Na1—O1A—Na1^xvi	154.71 (12)
O1^iv—Na1—O1—Na1^xvi	37.79 (7)	O1^v—Na1—O1A—Na1^xvi	−25.29 (12)
O1^viii—Na1—O1—Na1^xvi	142.21 (7)	O1—Na1—O1A—Na1^xvi	−72.4 (7)
O1^v—Na1—O1—Na1^xvi	−37.79 (7)	O1A^xiv—Na1—O1A—Na1^xvi	−74.74 (11)
O1A^xiv—Na1—O1—Na1^xvi	−92.3 (7)	O1A^xi—Na1—O1A—Na1^xvi	105.26 (11)
O1A^xi—Na1—O1—Na1^xvi	87.7 (7)	O1A^viii—Na1—O1A—Na1^xvi	141.06 (3)
O1A^viii—Na1—O1—Na1^xvi	129.00 (12)	O1A^v—Na1—O1A—Na1^xvi	−38.94 (3)
O1A^v—Na1—O1—Na1^xvi	−51.00 (12)	O1A^xii—Na1—O1A—Na1^xvi	−12.6 (2)
O1A^vi—Na1—O1—Na1^xvi	−87.7 (7)	C1—N1—C1A—O1A^xiv	0.0
O1A^xii—Na1—O1—Na1^xvi	−26.60 (10)	C1A^xiv—N1—C1A—O1A^xiv	0.0
O1^vi—Na1—O1A—C1A	−116.5 (8)	Zn1—N1—C1A—O1A^xiv	180.0
O1^vii—Na1—O1A—C1A	3.8 (4)	O1A^xiv—O1A—C1A—C1A^xiv	0.0
O1^iv—Na1—O1A—C1A	−176.2 (4)	Na1—O1A—C1A—C1A^xiv	−60.9 (3)
O1^viii—Na1—O1A—C1A	−69.4 (4)	Na1^xvi—O1A—C1A—C1A^xiv	60.9 (3)
O1^v—Na1—O1A—C1A	110.6 (4)	C1A^xiv—O1A—C1A—O1A^xiv	0.0

Symmetry codes: (i) −y+1, x−y, z; (ii) −x+y+1, −x+1, z; (iii) x, y, −z+1/2; (iv) −y, x−y, z; (v) −x+y, −x, z; (vi) −x, −y, −z; (vii) y, −x+y, −z; (viii) x−y, x, −z; (ix) y, x, −z; (x) x−y, −y, −z; (xi) −x, −x+y, −z; (xii) −y, −x, z; (xiii) −x+y, y, z; (xiv) x, x−y, z; (xv) x, y, −z+3/2; (xvi) −x, −y, z+1/2.

(II) catena-Poly[[dicyanatozinc(II)]-µ-4,4'-bipyridine-κ²N:N']

Crystal data

[Zn(NCO)2(C10H8N2)]	F(000) = 3080
Mr = 305.59	Dx = 1.619 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1757 reflections
a = 14.388 (1) Å	θ = 3.2–22.8°
b = 16.483 (2) Å	µ = 1.96 mm^−1
c = 26.438 (3) Å	T = 180 K
β = 90.024 (6)°	Block, colourless
V = 6270.0 (11) Å^3	0.25 × 0.10 × 0.10 mm
Z = 20

Data collection

Bruker Nonius X8 APEXII CCD area-detector diffractometer	12763 independent reflections
Radiation source: fine-focus sealed tube	5045 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.130
thin–slice ω and ϕ scans	θmax = 26.4°, θmin = 3.6°
Absorption correction: multi-scan (SADABS: Sheldrick, 2003)	h = −17→17
Tmin = 0.423, Tmax = 0.828	k = −20→13
34766 measured reflections	l = −33→33

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)] = 0.071	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.221	H-atom parameters constrained
S = 0.89	w = 1/[σ^2(Fo^2)] where P = (Fo^2 + 2Fc^2)/3
12763 reflections	(Δ/σ)max < 0.001
857 parameters	Δρmax = 1.31 e Å^−3
540 restraints	Δρmin = −0.90 e Å^−3

Special details

Experimental. Crystal twinned to appear orthorhombic. Twin law: 1 0 0, 0 − 1 0, 0 0 − 1 Refined BASF 0.497 (3).

ISOR restraints applied to all O, N and C atoms.

Highest residual peak/hole in vicinity of Zn2/Zn3, respectively.

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
Zn1	0.22589 (18)	0.13886 (16)	0.49361 (7)	0.0374 (6)
Zn2	0.27908 (18)	0.63796 (15)	0.21052 (7)	0.0374 (6)
Zn3	0.28944 (14)	0.13509 (13)	0.69211 (7)	0.0254 (5)
Zn4	0.20899 (13)	0.63438 (12)	0.41173 (6)	0.0249 (5)
Zn5	0.29291 (11)	0.63440 (10)	0.60965 (8)	0.0230 (4)
O1	0.4893 (9)	0.1308 (8)	0.5599 (5)	0.084 (4)
O2	0.0155 (7)	0.1531 (8)	0.5972 (5)	0.066 (4)
O3	0.5122 (7)	0.6446 (7)	0.1196 (5)	0.071 (4)
O4	0.0367 (9)	0.6415 (9)	0.1198 (6)	0.100 (5)
O5	0.0173 (9)	0.1184 (8)	0.7488 (5)	0.075 (4)
O6	0.4877 (8)	0.1453 (8)	0.7995 (5)	0.062 (3)
O7	−0.0045 (7)	0.6489 (8)	0.3126 (4)	0.058 (4)
O8	0.4701 (8)	0.6261 (7)	0.3403 (5)	0.068 (4)
O9	0.0239 (9)	0.6255 (9)	0.5438 (6)	0.081 (5)
O10	0.4971 (7)	0.6466 (8)	0.5038 (5)	0.058 (3)
N1	0.3369 (8)	0.1326 (7)	0.5293 (4)	0.034 (3)
N2	0.1039 (8)	0.1434 (8)	0.5213 (5)	0.040 (3)
N3	0.4054 (9)	0.6394 (9)	0.1854 (5)	0.048 (4)
N4	0.1663 (8)	0.6389 (9)	0.1710 (5)	0.049 (4)
N5	0.1779 (11)	0.1295 (10)	0.7264 (6)	0.059 (5)
N6	0.4136 (8)	0.1358 (8)	0.7220 (5)	0.036 (3)
N7	0.0821 (7)	0.6326 (8)	0.3867 (6)	0.035 (3)
N8	0.3169 (8)	0.6335 (9)	0.3732 (5)	0.038 (4)
N9	0.1793 (8)	0.6328 (8)	0.5699 (4)	0.024 (3)
N10	0.4128 (8)	0.6341 (9)	0.5819 (5)	0.032 (3)
C1	0.4071 (15)	0.1276 (12)	0.5398 (8)	0.062 (6)
C2	0.0577 (10)	0.1470 (10)	0.5591 (5)	0.040 (4)
C3	0.4528 (11)	0.6407 (12)	0.1531 (6)	0.049 (5)
C4	0.1026 (11)	0.6374 (11)	0.1503 (6)	0.043 (4)
C5	0.0960 (12)	0.1259 (11)	0.7403 (7)	0.041 (5)
C6	0.4470 (11)	0.1376 (12)	0.7589 (7)	0.043 (5)
C7	0.0400 (10)	0.6388 (11)	0.3497 (6)	0.033 (4)
C8	0.3918 (10)	0.6335 (12)	0.3544 (7)	0.041 (4)
C9	0.1032 (11)	0.6255 (10)	0.5612 (7)	0.035 (4)
C10	0.4543 (9)	0.6439 (10)	0.5421 (6)	0.027 (4)
N11	0.2340 (9)	0.2368 (9)	0.4469 (5)	0.032 (4)
N12	0.2679 (9)	0.5381 (9)	0.2574 (5)	0.030 (3)
C11	0.1605 (11)	0.2613 (9)	0.4211 (5)	0.030 (4)
H11A	0.1022	0.2366	0.4278	0.036*
C12	0.1648 (11)	0.3208 (10)	0.3850 (7)	0.037 (5)
H12A	0.1093	0.3364	0.3681	0.045*
C13	0.2478 (7)	0.3592 (12)	0.3722 (7)	0.023 (4)
C14	0.3231 (11)	0.3335 (9)	0.3981 (7)	0.034 (4)
H14A	0.3820	0.3574	0.3917	0.040*
C15	0.3147 (11)	0.2706 (10)	0.4352 (6)	0.037 (5)
H15A	0.3692	0.2523	0.4521	0.045*
C16	0.1873 (10)	0.5231 (9)	0.2803 (6)	0.028 (4)
H16A	0.1344	0.5539	0.2706	0.033*
C17	0.1768 (12)	0.4651 (10)	0.3173 (6)	0.029 (4)
H17A	0.1185	0.4570	0.3334	0.034*
C18	0.2528 (7)	0.4192 (12)	0.3303 (6)	0.020 (4)
C19	0.3364 (11)	0.4340 (10)	0.3060 (6)	0.031 (4)
H19A	0.3903	0.4036	0.3145	0.037*
C110	0.3403 (10)	0.4920 (9)	0.2702 (6)	0.032 (4)
H11B	0.3977	0.5006	0.2532	0.038*
N21	0.2654 (8)	0.7364 (8)	0.2588 (5)	0.029 (4)
N22	0.2309 (9)	1.0406 (8)	0.4452 (5)	0.030 (3)
C21	0.1837 (12)	0.7565 (10)	0.2773 (6)	0.038 (5)
H21A	0.1304	0.7300	0.2641	0.046*
C22	0.1706 (13)	0.8141 (10)	0.3151 (7)	0.036 (5)
H22A	0.1111	0.8257	0.3289	0.043*
C23	0.2526 (7)	0.8544 (12)	0.3316 (8)	0.024 (4)
C24	0.3395 (13)	0.8341 (11)	0.3085 (7)	0.042 (5)
H24A	0.3949	0.8619	0.3176	0.050*
C25	0.3412 (9)	0.7752 (9)	0.2737 (5)	0.028 (4)
H25A	0.3991	0.7605	0.2592	0.034*
C26	0.1587 (13)	1.0187 (11)	0.4198 (7)	0.058 (6)
H26A	0.1009	1.0438	0.4272	0.070*
C27	0.1617 (11)	0.9587 (10)	0.3814 (6)	0.043 (5)
H27A	0.1064	0.9447	0.3637	0.052*
C28	0.2466 (9)	0.9197 (15)	0.3691 (8)	0.042 (6)
C29	0.3220 (11)	0.9487 (10)	0.3987 (6)	0.042 (5)
H29A	0.3821	0.9263	0.3937	0.050*
C210	0.3103 (11)	1.0074 (10)	0.4338 (6)	0.042 (5)
H21B	0.3638	1.0257	0.4515	0.051*
N31	0.2781 (9)	0.2355 (8)	0.6463 (5)	0.026 (3)
N32	0.2225 (10)	0.5381 (8)	0.4595 (4)	0.027 (3)
C31	0.1927 (12)	0.2644 (10)	0.6358 (6)	0.040 (5)
H31A	0.1405	0.2439	0.6538	0.047*
C32	0.1801 (11)	0.3213 (9)	0.6006 (7)	0.029 (4)
H32A	0.1194	0.3416	0.5942	0.034*
C33	0.2564 (8)	0.3515 (12)	0.5726 (6)	0.021 (4)
C34	0.3436 (11)	0.3244 (10)	0.5838 (6)	0.026 (4)
H34A	0.3965	0.3448	0.5666	0.032*
C35	0.3522 (10)	0.2655 (9)	0.6215 (6)	0.029 (4)
H35A	0.4124	0.2460	0.6299	0.035*
C36	0.1512 (11)	0.4907 (10)	0.4728 (6)	0.032 (4)
H36A	0.0927	0.4989	0.4569	0.038*
C37	0.1593 (10)	0.4289 (10)	0.5094 (6)	0.029 (4)
H37A	0.1079	0.3951	0.5173	0.034*
C38	0.2437 (8)	0.4185 (12)	0.5336 (7)	0.027 (5)
C39	0.3181 (12)	0.4682 (10)	0.5196 (6)	0.032 (4)
H39A	0.3767	0.4634	0.5358	0.038*
C310	0.3045 (12)	0.5239 (10)	0.4820 (6)	0.034 (4)
H31B	0.3566	0.5546	0.4711	0.041*
N41	0.2211 (10)	0.7341 (7)	0.4589 (4)	0.024 (3)
N42	0.2802 (9)	1.0404 (8)	0.6433 (4)	0.023 (3)
C41	0.1478 (10)	0.7684 (9)	0.4827 (5)	0.024 (4)
H41A	0.0867	0.7513	0.4742	0.029*
C42	0.1593 (12)	0.8274 (10)	0.5188 (6)	0.031 (4)
H42A	0.1061	0.8490	0.5353	0.037*
C43	0.2439 (8)	0.8552 (12)	0.5315 (7)	0.028 (5)
C44	0.3184 (12)	0.8190 (11)	0.5060 (6)	0.036 (5)
H44A	0.3797	0.8368	0.5133	0.043*
C45	0.3063 (12)	0.7599 (10)	0.4716 (6)	0.038 (5)
H45A	0.3591	0.7360	0.4561	0.046*
C46	0.1980 (13)	1.0253 (10)	0.6230 (7)	0.047 (5)
H46A	0.1463	1.0557	0.6347	0.057*
C47	0.1825 (11)	0.9671 (10)	0.5853 (5)	0.033 (4)
H47A	0.1231	0.9604	0.5701	0.040*
C48	0.2580 (8)	0.9196 (11)	0.5711 (6)	0.020 (4)
C49	0.3418 (11)	0.9323 (9)	0.5929 (6)	0.031 (4)
H49A	0.3939	0.9002	0.5836	0.037*
C410	0.3505 (10)	0.9929 (9)	0.6293 (5)	0.028 (4)
H41B	0.4094	1.0008	0.6449	0.034*
N51	0.2813 (9)	0.5368 (7)	0.6580 (4)	0.021 (3)
N52	0.2194 (9)	0.2320 (7)	0.8448 (4)	0.021 (3)
C51	0.3495 (10)	0.4903 (10)	0.6725 (6)	0.027 (4)
H51A	0.4087	0.4976	0.6573	0.032*
C52	0.3398 (10)	0.4313 (9)	0.7088 (6)	0.029 (4)
H52A	0.3928	0.4011	0.7189	0.035*
C53	0.2551 (7)	0.4149 (12)	0.7308 (6)	0.018 (4)
C54	0.1838 (11)	0.4638 (9)	0.7137 (6)	0.024 (4)
H54A	0.1235	0.4568	0.7276	0.029*
C55	0.1970 (11)	0.5219 (9)	0.6776 (6)	0.026 (4)
H55A	0.1453	0.5525	0.6661	0.031*
C56	0.3010 (11)	0.2645 (10)	0.8332 (6)	0.031 (4)
H56A	0.3535	0.2450	0.8513	0.037*
C57	0.3171 (12)	0.3240 (11)	0.7974 (6)	0.033 (5)
H57A	0.3781	0.3440	0.7916	0.039*
C58	0.2422 (8)	0.3538 (13)	0.7699 (7)	0.025 (5)
C59	0.1544 (12)	0.3226 (11)	0.7838 (7)	0.031 (5)
H59A	0.0994	0.3421	0.7680	0.038*
C510	0.1499 (10)	0.2628 (10)	0.8210 (6)	0.030 (4)
H51B	0.0899	0.2430	0.8296	0.035*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0708 (13)	0.0214 (13)	0.0200 (10)	0.0033 (13)	−0.0043 (9)	0.0003 (9)
Zn2	0.0683 (13)	0.0227 (12)	0.0211 (10)	−0.0028 (14)	0.0074 (9)	−0.0003 (8)
Zn3	0.0299 (11)	0.0213 (12)	0.0250 (10)	−0.0010 (11)	−0.0010 (10)	0.0013 (10)
Zn4	0.0320 (12)	0.0236 (12)	0.0191 (9)	0.0041 (11)	0.0007 (9)	−0.0001 (9)
Zn5	0.0337 (9)	0.0186 (9)	0.0166 (8)	−0.0004 (9)	0.0014 (13)	−0.0001 (10)
O1	0.076 (5)	0.090 (6)	0.087 (6)	0.004 (4)	−0.002 (4)	0.010 (4)
O2	0.064 (5)	0.071 (5)	0.064 (5)	0.003 (4)	−0.001 (4)	−0.003 (4)
O3	0.062 (5)	0.079 (5)	0.071 (5)	0.008 (4)	0.002 (4)	0.005 (4)
O4	0.091 (6)	0.103 (6)	0.106 (7)	0.002 (4)	−0.003 (5)	−0.003 (5)
O5	0.062 (5)	0.082 (6)	0.082 (6)	−0.001 (4)	0.006 (4)	0.015 (4)
O6	0.058 (5)	0.076 (5)	0.052 (5)	−0.008 (4)	−0.017 (4)	0.004 (4)
O7	0.052 (5)	0.071 (5)	0.050 (5)	−0.005 (4)	−0.011 (4)	0.005 (4)
O8	0.048 (5)	0.074 (5)	0.080 (5)	0.003 (4)	0.021 (4)	−0.015 (4)
O9	0.064 (5)	0.085 (6)	0.094 (6)	−0.004 (4)	−0.011 (4)	−0.012 (4)
O10	0.055 (4)	0.071 (5)	0.048 (5)	−0.002 (4)	0.014 (4)	0.008 (4)
N1	0.029 (5)	0.041 (6)	0.032 (5)	0.006 (6)	0.003 (5)	0.001 (5)
N2	0.042 (6)	0.041 (7)	0.037 (6)	0.007 (6)	0.010 (5)	0.012 (6)
N3	0.066 (7)	0.043 (7)	0.035 (6)	0.003 (6)	0.021 (5)	0.000 (6)
N4	0.047 (6)	0.053 (7)	0.048 (6)	0.004 (6)	−0.019 (6)	0.003 (6)
N5	0.074 (8)	0.051 (8)	0.053 (8)	−0.001 (7)	−0.002 (6)	−0.003 (6)
N6	0.024 (5)	0.034 (7)	0.050 (7)	−0.002 (5)	−0.012 (5)	0.002 (6)
N7	0.031 (5)	0.030 (6)	0.044 (7)	−0.005 (5)	−0.005 (6)	0.007 (6)
N8	0.041 (6)	0.048 (7)	0.024 (6)	0.005 (6)	0.007 (5)	−0.001 (5)
N9	0.037 (6)	0.018 (6)	0.016 (5)	0.005 (5)	−0.003 (4)	−0.005 (5)
N10	0.029 (5)	0.039 (7)	0.027 (6)	−0.010 (6)	−0.006 (4)	−0.001 (6)
C1	0.071 (9)	0.057 (9)	0.059 (9)	−0.002 (8)	0.010 (7)	0.019 (7)
C2	0.051 (7)	0.046 (8)	0.023 (6)	0.024 (7)	0.012 (6)	0.004 (6)
C3	0.055 (7)	0.050 (8)	0.044 (8)	−0.002 (7)	0.014 (6)	0.002 (7)
C4	0.049 (7)	0.038 (7)	0.044 (7)	−0.002 (7)	−0.014 (6)	−0.010 (7)
C5	0.043 (7)	0.044 (9)	0.035 (7)	0.002 (7)	−0.001 (6)	0.006 (6)
C6	0.046 (7)	0.038 (8)	0.046 (8)	−0.006 (7)	−0.004 (6)	0.007 (7)
C7	0.033 (6)	0.035 (7)	0.030 (7)	0.005 (6)	0.006 (5)	−0.002 (7)
C8	0.032 (6)	0.045 (8)	0.047 (8)	−0.002 (7)	−0.004 (6)	−0.002 (7)
C9	0.031 (7)	0.036 (8)	0.037 (7)	−0.006 (6)	−0.015 (6)	−0.007 (6)
C10	0.020 (6)	0.030 (7)	0.031 (7)	0.002 (6)	0.005 (5)	−0.002 (6)
N11	0.046 (7)	0.029 (7)	0.021 (6)	−0.004 (5)	0.003 (5)	−0.008 (5)
N12	0.046 (6)	0.022 (6)	0.020 (6)	0.002 (5)	0.004 (5)	−0.001 (5)
C11	0.038 (7)	0.023 (7)	0.028 (7)	0.000 (6)	−0.009 (6)	0.004 (6)
C12	0.044 (7)	0.031 (8)	0.037 (8)	0.010 (6)	−0.010 (7)	−0.001 (6)
C13	0.037 (7)	0.012 (7)	0.021 (6)	−0.005 (6)	0.001 (5)	−0.002 (6)
C14	0.036 (7)	0.022 (7)	0.043 (8)	−0.003 (5)	−0.006 (6)	0.000 (6)
C15	0.039 (7)	0.040 (8)	0.034 (7)	0.020 (6)	−0.004 (6)	0.003 (6)
C16	0.028 (7)	0.025 (7)	0.030 (7)	0.012 (5)	0.008 (5)	0.006 (6)
C17	0.032 (7)	0.023 (8)	0.031 (7)	−0.002 (6)	−0.002 (6)	0.009 (6)
C18	0.028 (7)	0.021 (8)	0.011 (6)	0.008 (5)	0.004 (5)	−0.001 (6)
C19	0.032 (7)	0.031 (7)	0.030 (7)	0.004 (6)	0.004 (5)	0.012 (6)
C110	0.038 (7)	0.026 (7)	0.032 (7)	−0.003 (6)	0.000 (6)	−0.005 (6)
N21	0.037 (6)	0.018 (6)	0.032 (6)	−0.001 (5)	0.002 (5)	−0.001 (5)
N22	0.046 (6)	0.024 (7)	0.019 (6)	0.015 (6)	0.003 (5)	0.004 (5)
C21	0.040 (8)	0.044 (8)	0.031 (7)	0.004 (6)	0.002 (6)	−0.008 (6)
C22	0.042 (8)	0.022 (8)	0.043 (8)	0.001 (6)	−0.001 (6)	−0.001 (6)
C23	0.026 (7)	0.016 (8)	0.029 (7)	0.007 (6)	0.000 (5)	0.008 (6)
C24	0.044 (8)	0.040 (8)	0.042 (8)	−0.010 (6)	0.008 (6)	−0.001 (6)
C25	0.025 (7)	0.026 (7)	0.033 (7)	−0.007 (5)	0.011 (5)	−0.010 (6)
C26	0.052 (8)	0.063 (9)	0.059 (9)	0.009 (7)	−0.010 (7)	−0.008 (7)
C27	0.041 (7)	0.043 (8)	0.044 (8)	0.008 (6)	−0.001 (6)	−0.009 (6)
C28	0.051 (9)	0.039 (10)	0.037 (9)	−0.003 (6)	−0.007 (6)	0.009 (7)
C29	0.040 (7)	0.046 (8)	0.040 (8)	−0.005 (6)	0.004 (6)	−0.001 (7)
C210	0.038 (8)	0.044 (8)	0.046 (7)	−0.010 (6)	0.002 (6)	−0.009 (6)
N31	0.037 (6)	0.020 (6)	0.020 (5)	0.004 (6)	0.002 (5)	0.003 (5)
N32	0.044 (6)	0.020 (6)	0.016 (6)	0.005 (6)	0.006 (5)	−0.004 (5)
C31	0.043 (8)	0.034 (8)	0.041 (8)	−0.003 (7)	0.001 (6)	0.011 (6)
C32	0.027 (7)	0.029 (7)	0.030 (7)	0.001 (5)	0.006 (6)	0.009 (6)
C33	0.025 (7)	0.017 (8)	0.020 (7)	−0.004 (5)	−0.003 (5)	0.009 (6)
C34	0.033 (7)	0.027 (8)	0.019 (7)	0.005 (6)	−0.001 (5)	0.006 (6)
C35	0.034 (6)	0.016 (7)	0.037 (8)	−0.002 (5)	0.010 (6)	0.007 (6)
C36	0.035 (7)	0.033 (8)	0.027 (7)	−0.002 (6)	−0.008 (6)	−0.003 (6)
C37	0.032 (7)	0.030 (7)	0.024 (7)	−0.003 (6)	−0.001 (6)	−0.004 (6)
C38	0.034 (8)	0.028 (8)	0.018 (7)	0.003 (6)	0.001 (5)	0.002 (6)
C39	0.042 (8)	0.031 (8)	0.022 (7)	0.001 (6)	−0.004 (6)	0.001 (6)
C310	0.043 (7)	0.033 (8)	0.026 (7)	0.000 (6)	−0.003 (6)	−0.012 (6)
N41	0.039 (6)	0.013 (6)	0.019 (5)	−0.003 (6)	−0.005 (5)	0.003 (5)
N42	0.031 (5)	0.020 (6)	0.019 (5)	−0.003 (6)	0.003 (5)	0.008 (5)
C41	0.029 (6)	0.019 (7)	0.024 (6)	0.004 (5)	0.007 (5)	−0.006 (5)
C42	0.039 (7)	0.031 (8)	0.022 (7)	0.006 (6)	0.003 (6)	−0.008 (6)
C43	0.040 (8)	0.020 (8)	0.025 (7)	0.007 (6)	0.003 (5)	0.001 (7)
C44	0.030 (8)	0.031 (8)	0.046 (8)	−0.006 (6)	−0.009 (6)	−0.003 (6)
C45	0.043 (8)	0.040 (8)	0.032 (7)	−0.001 (7)	0.005 (6)	−0.007 (6)
C46	0.051 (8)	0.042 (8)	0.048 (8)	0.008 (7)	0.004 (7)	0.001 (7)
C47	0.035 (7)	0.038 (8)	0.028 (7)	−0.006 (6)	−0.010 (6)	−0.006 (6)
C48	0.030 (7)	0.007 (7)	0.024 (7)	−0.003 (5)	−0.003 (5)	−0.002 (6)
C49	0.031 (7)	0.031 (7)	0.031 (7)	−0.004 (6)	−0.001 (5)	0.007 (6)
C410	0.031 (6)	0.025 (7)	0.029 (7)	−0.002 (6)	−0.010 (5)	0.000 (6)
N51	0.025 (5)	0.018 (6)	0.020 (6)	0.003 (5)	−0.004 (5)	−0.001 (5)
N52	0.029 (5)	0.014 (6)	0.021 (5)	0.005 (5)	−0.001 (5)	−0.002 (5)
C51	0.033 (7)	0.028 (8)	0.020 (7)	0.006 (6)	0.010 (6)	0.000 (6)
C52	0.032 (7)	0.027 (7)	0.028 (7)	0.007 (6)	0.000 (6)	−0.001 (6)
C53	0.022 (7)	0.017 (8)	0.014 (6)	−0.002 (5)	−0.002 (5)	0.000 (6)
C54	0.025 (7)	0.023 (7)	0.024 (7)	0.001 (6)	−0.002 (5)	0.006 (6)
C55	0.025 (7)	0.029 (7)	0.022 (6)	−0.006 (6)	0.002 (5)	0.005 (6)
C56	0.029 (7)	0.034 (8)	0.030 (7)	−0.006 (6)	−0.011 (6)	0.006 (6)
C57	0.022 (7)	0.042 (8)	0.033 (8)	−0.004 (6)	−0.008 (6)	0.015 (6)
C58	0.030 (7)	0.022 (8)	0.025 (7)	0.005 (6)	−0.002 (5)	−0.006 (7)
C59	0.026 (7)	0.031 (8)	0.037 (8)	0.006 (6)	−0.001 (6)	0.001 (6)
C510	0.027 (7)	0.024 (8)	0.038 (7)	0.002 (6)	0.011 (6)	−0.008 (6)

Geometric parameters (Å, º)

Zn1—N1	1.859 (11)	C25—H25A	0.950
Zn1—N2	1.904 (11)	C26—C27	1.42 (2)
Zn1—N11	2.037 (15)	C26—H26A	0.950
Zn1—N22^i	2.067 (14)	C27—C28	1.42 (2)
Zn2—N4	1.930 (12)	C27—H27A	0.950
Zn2—N3	1.935 (13)	C28—C29	1.42 (2)
Zn2—N12	2.066 (14)	C29—C210	1.35 (2)
Zn2—N21	2.074 (14)	C29—H29A	0.950
Zn3—N5	1.846 (16)	C210—H21B	0.950
Zn3—N6	1.953 (12)	N31—C35	1.346 (17)
Zn3—N42^i	2.030 (13)	N31—C31	1.35 (2)
Zn3—N31	2.057 (13)	N32—C36	1.337 (19)
Zn4—N8	1.858 (12)	N32—C310	1.34 (2)
Zn4—N7	1.941 (11)	C31—C32	1.33 (2)
Zn4—N32	2.037 (13)	C31—H31A	0.950
Zn4—N41	2.070 (12)	C32—C33	1.414 (19)
Zn5—N10	1.875 (12)	C32—H32A	0.950
Zn5—N9	1.943 (12)	C33—C34	1.364 (19)
Zn5—N52^ii	2.017 (12)	C33—C38	1.52 (3)
Zn5—N51	2.062 (12)	C34—C35	1.396 (18)
O1—C1	1.30 (2)	C34—H34A	0.950
O2—C2	1.182 (17)	C35—H35A	0.950
O3—C3	1.233 (17)	C36—C37	1.41 (2)
O4—C4	1.247 (18)	C36—H36A	0.950
O5—C5	1.161 (18)	C37—C38	1.383 (18)
O6—C6	1.23 (2)	C37—H37A	0.950
O7—C7	1.182 (18)	C38—C39	1.40 (2)
O8—C8	1.192 (17)	C39—C310	1.37 (2)
O9—C9	1.230 (18)	C39—H39A	0.950
O10—C10	1.186 (17)	C310—H31B	0.950
N1—C1	1.05 (2)	N41—C45	1.34 (2)
N2—C2	1.201 (17)	N41—C41	1.352 (17)
N3—C3	1.093 (19)	N42—C46	1.32 (2)
N4—C4	1.066 (17)	N42—C410	1.332 (17)
N5—C5	1.24 (2)	N42—Zn3^iii	2.030 (13)
N6—C6	1.09 (2)	C41—C42	1.37 (2)
N7—C7	1.156 (19)	C41—H41A	0.950
N8—C8	1.187 (18)	C42—C43	1.34 (2)
N9—C9	1.126 (17)	C42—H42A	0.950
N10—C10	1.219 (18)	C43—C44	1.40 (2)
N11—C11	1.322 (18)	C43—C48	1.50 (3)
N11—C15	1.324 (19)	C44—C45	1.34 (2)
N12—C16	1.332 (18)	C44—H44A	0.950
N12—C110	1.333 (17)	C45—H45A	0.950
C11—C12	1.37 (2)	C46—C47	1.40 (2)
C11—H11A	0.950	C46—H46A	0.950
C12—C13	1.39 (2)	C47—C48	1.39 (2)
C12—H12A	0.950	C47—H47A	0.950
C13—C14	1.35 (2)	C48—C49	1.352 (19)
C13—C18	1.49 (2)	C49—C410	1.39 (2)
C14—C15	1.43 (2)	C49—H49A	0.950
C14—H14A	0.950	C410—H41B	0.950
C15—H15A	0.950	N51—C51	1.302 (18)
C16—C17	1.38 (2)	N51—C55	1.34 (2)
C16—H16A	0.950	N52—C510	1.285 (18)
C17—C18	1.37 (2)	N52—C56	1.33 (2)
C17—H17A	0.950	N52—Zn5^iv	2.017 (12)
C18—C19	1.385 (18)	C51—C52	1.37 (2)
C19—C110	1.35 (2)	C51—H51A	0.950
C19—H19A	0.950	C52—C53	1.377 (18)
C110—H11B	0.950	C52—H52A	0.950
N21—C21	1.315 (18)	C53—C54	1.38 (2)
N21—C25	1.324 (17)	C53—C58	1.46 (3)
N22—C26	1.29 (2)	C54—C55	1.37 (2)
N22—C210	1.300 (19)	C54—H54A	0.950
N22—Zn1^iii	2.067 (14)	C55—H55A	0.950
C21—C22	1.39 (2)	C56—C57	1.38 (2)
C21—H21A	0.950	C56—H56A	0.950
C22—C23	1.42 (2)	C57—C58	1.39 (2)
C22—H22A	0.950	C57—H57A	0.950
C23—C24	1.43 (2)	C58—C59	1.41 (2)
C23—C28	1.46 (3)	C59—C510	1.40 (2)
C24—C25	1.34 (2)	C59—H59A	0.950
C24—H24A	0.950	C510—H51B	0.950
N1—Zn1—N2	126.8 (5)	C29—C28—C23	125.1 (14)
N1—Zn1—N11	107.6 (5)	C210—C29—C28	121.6 (15)
N2—Zn1—N11	104.8 (5)	C210—C29—H29A	119.2
N1—Zn1—N22^i	103.9 (5)	C28—C29—H29A	119.2
N2—Zn1—N22^i	107.5 (6)	N22—C210—C29	124.7 (15)
N11—Zn1—N22^i	104.1 (5)	N22—C210—H21B	117.7
N4—Zn2—N3	127.1 (6)	C29—C210—H21B	117.7
N4—Zn2—N12	105.4 (5)	C35—N31—C31	119.5 (13)
N3—Zn2—N12	106.8 (6)	C35—N31—Zn3	121.3 (10)
N4—Zn2—N21	104.3 (5)	C31—N31—Zn3	118.6 (11)
N3—Zn2—N21	106.9 (6)	C36—N32—C310	117.1 (13)
N12—Zn2—N21	104.3 (5)	C36—N32—Zn4	123.1 (11)
N5—Zn3—N6	126.6 (6)	C310—N32—Zn4	119.7 (12)
N5—Zn3—N42^i	102.6 (6)	C32—C31—N31	121.1 (16)
N6—Zn3—N42^i	108.8 (6)	C32—C31—H31A	119.5
N5—Zn3—N31	105.1 (6)	N31—C31—H31A	119.5
N6—Zn3—N31	107.8 (6)	C31—C32—C33	120.5 (15)
N42^i—Zn3—N31	103.9 (4)	C31—C32—H32A	119.8
N8—Zn4—N7	126.8 (6)	C33—C32—H32A	119.8
N8—Zn4—N32	104.7 (6)	C34—C33—C32	119.0 (15)
N7—Zn4—N32	106.8 (6)	C34—C33—C38	119.6 (12)
N8—Zn4—N41	105.4 (6)	C32—C33—C38	121.1 (12)
N7—Zn4—N41	107.2 (6)	C33—C34—C35	117.7 (16)
N32—Zn4—N41	103.7 (5)	C33—C34—H34A	121.2
N10—Zn5—N9	124.2 (5)	C35—C34—H34A	121.2
N10—Zn5—N52^ii	108.5 (6)	N31—C35—C34	122.2 (14)
N9—Zn5—N52^ii	105.0 (5)	N31—C35—H35A	118.9
N10—Zn5—N51	108.4 (6)	C34—C35—H35A	118.9
N9—Zn5—N51	104.9 (5)	N32—C36—C37	122.7 (15)
N52^ii—Zn5—N51	104.2 (4)	N32—C36—H36A	118.7
C1—N1—Zn1	164.7 (16)	C37—C36—H36A	118.7
C2—N2—Zn1	146.3 (11)	C38—C37—C36	118.6 (15)
C3—N3—Zn2	148.7 (15)	C38—C37—H37A	120.7
C4—N4—Zn2	177.3 (17)	C36—C37—H37A	120.7
C5—N5—Zn3	167.8 (15)	C37—C38—C39	118.5 (16)
C6—N6—Zn3	140.2 (14)	C37—C38—C33	120.5 (14)
C7—N7—Zn4	141.3 (12)	C39—C38—C33	120.9 (12)
C8—N8—Zn4	171.5 (13)	C310—C39—C38	118.5 (16)
C9—N9—Zn5	158.4 (14)	C310—C39—H39A	120.8
C10—N10—Zn5	142.0 (11)	C38—C39—H39A	120.8
N1—C1—O1	169 (2)	N32—C310—C39	124.4 (16)
O2—C2—N2	177 (2)	N32—C310—H31B	117.8
N3—C3—O3	174 (2)	C39—C310—H31B	117.8
N4—C4—O4	169 (2)	C45—N41—C41	117.6 (13)
O5—C5—N5	173 (2)	C45—N41—Zn4	118.7 (12)
N6—C6—O6	175 (2)	C41—N41—Zn4	123.1 (10)
N7—C7—O7	177 (2)	C46—N42—C410	117.2 (13)
N8—C8—O8	171 (2)	C46—N42—Zn3^iii	117.5 (12)
N9—C9—O9	168 (2)	C410—N42—Zn3^iii	125.3 (10)
O10—C10—N10	174 (2)	N41—C41—C42	121.8 (15)
C11—N11—C15	117.0 (14)	N41—C41—H41A	119.1
C11—N11—Zn1	120.6 (10)	C42—C41—H41A	119.1
C15—N11—Zn1	121.7 (11)	C43—C42—C41	121.6 (16)
C16—N12—C110	117.3 (13)	C43—C42—H42A	119.2
C16—N12—Zn2	119.3 (11)	C41—C42—H42A	119.2
C110—N12—Zn2	123.1 (10)	C42—C43—C44	115.3 (17)
N11—C11—C12	122.8 (15)	C42—C43—C48	122.5 (13)
N11—C11—H11A	118.6	C44—C43—C48	122.2 (13)
C12—C11—H11A	118.6	C45—C44—C43	122.4 (16)
C11—C12—C13	122.2 (16)	C45—C44—H44A	118.8
C11—C12—H12A	118.9	C43—C44—H44A	118.8
C13—C12—H12A	118.9	N41—C45—C44	121.2 (16)
C14—C13—C12	115.0 (16)	N41—C45—H45A	119.4
C14—C13—C18	123.2 (12)	C44—C45—H45A	119.4
C12—C13—C18	121.6 (13)	N42—C46—C47	124.1 (16)
C13—C14—C15	120.5 (15)	N42—C46—H46A	118.0
C13—C14—H14A	119.8	C47—C46—H46A	118.0
C15—C14—H14A	119.8	C48—C47—C46	116.9 (15)
N11—C15—C14	122.5 (14)	C48—C47—H47A	121.6
N11—C15—H15A	118.8	C46—C47—H47A	121.5
C14—C15—H15A	118.7	C49—C48—C47	119.6 (15)
N12—C16—C17	123.3 (14)	C49—C48—C43	121.7 (14)
N12—C16—H16A	118.4	C47—C48—C43	118.6 (12)
C17—C16—H16A	118.4	C48—C49—C410	119.1 (15)
C18—C17—C16	118.2 (15)	C48—C49—H49A	120.5
C18—C17—H17A	120.9	C410—C49—H49A	120.5
C16—C17—H17A	120.9	N42—C410—C49	123.0 (13)
C17—C18—C19	118.6 (16)	N42—C410—H41B	118.5
C17—C18—C13	120.9 (12)	C49—C410—H41B	118.5
C19—C18—C13	120.3 (12)	C51—N51—C55	117.3 (13)
C110—C19—C18	119.1 (15)	C51—N51—Zn5	125.5 (11)
C110—C19—H19A	120.4	C55—N51—Zn5	117.1 (11)
C18—C19—H19A	120.4	C510—N52—C56	114.6 (13)
N12—C110—C19	123.4 (15)	C510—N52—Zn5^iv	122.5 (11)
N12—C110—H11B	118.3	C56—N52—Zn5^iv	122.5 (11)
C19—C110—H11B	118.3	N51—C51—C52	123.1 (14)
C21—N21—C25	120.2 (14)	N51—C51—H51A	118.5
C21—N21—Zn2	120.8 (11)	C52—C51—H51A	118.5
C25—N21—Zn2	118.9 (9)	C51—C52—C53	121.7 (15)
C26—N22—C210	118.1 (15)	C51—C52—H52A	119.2
C26—N22—Zn1^iii	120.9 (11)	C53—C52—H52A	119.2
C210—N22—Zn1^iii	120.2 (12)	C52—C53—C54	113.8 (15)
N21—C21—C22	124.2 (16)	C52—C53—C58	123.4 (13)
N21—C21—H21A	117.9	C54—C53—C58	122.7 (12)
C22—C21—H21A	117.9	C55—C54—C53	122.3 (15)
C21—C22—C23	115.2 (17)	C55—C54—H54A	118.9
C21—C22—H22A	122.4	C53—C54—H54A	118.9
C23—C22—H22A	122.4	N51—C55—C54	121.6 (15)
C22—C23—C24	118.9 (18)	N51—C55—H55A	119.2
C22—C23—C28	120.1 (13)	C54—C55—H55A	119.2
C24—C23—C28	120.8 (14)	N52—C56—C57	126.4 (15)
C25—C24—C23	118.6 (17)	N52—C56—H56A	116.8
C25—C24—H24A	120.7	C57—C56—H56A	116.8
C23—C24—H24A	120.7	C56—C57—C58	118.5 (16)
N21—C25—C24	122.8 (15)	C56—C57—H57A	120.7
N21—C25—H25A	118.6	C58—C57—H57A	120.7
C24—C25—H25A	118.6	C57—C58—C59	115.5 (17)
N22—C26—C27	122.9 (17)	C57—C58—C53	121.1 (12)
N22—C26—H26A	118.5	C59—C58—C53	123.4 (13)
C27—C26—H26A	118.5	C510—C59—C58	118.8 (16)
C26—C27—C28	120.4 (17)	C510—C59—H59A	120.6
C26—C27—H27A	119.8	C58—C59—H59A	120.6
C28—C27—H27A	119.8	N52—C510—C59	126.0 (15)
C27—C28—C29	112.2 (18)	N52—C510—H51B	117.0
C27—C28—C23	122.6 (14)	C59—C510—H51B	117.0
N2—Zn1—N1—C1	175 (6)	N5—Zn3—N31—C31	−19.6 (13)
N11—Zn1—N1—C1	−60 (7)	N6—Zn3—N31—C31	−156.9 (12)
N22^i—Zn1—N1—C1	50 (7)	N42^i—Zn3—N31—C31	87.8 (12)
N1—Zn1—N2—C2	4 (3)	N8—Zn4—N32—C36	−142.4 (13)
N11—Zn1—N2—C2	−122 (2)	N7—Zn4—N32—C36	−5.8 (14)
N22^i—Zn1—N2—C2	128 (2)	N41—Zn4—N32—C36	107.3 (13)
N4—Zn2—N3—C3	0 (3)	N8—Zn4—N32—C310	42.6 (12)
N12—Zn2—N3—C3	125 (3)	N7—Zn4—N32—C310	179.2 (11)
N21—Zn2—N3—C3	−124 (3)	N41—Zn4—N32—C310	−67.8 (12)
N6—Zn3—N5—C5	−178 (8)	C35—N31—C31—C32	1 (2)
N42^i—Zn3—N5—C5	−53 (8)	Zn3—N31—C31—C32	−169.8 (13)
N31—Zn3—N5—C5	55 (8)	N31—C31—C32—C33	1 (3)
N5—Zn3—N6—C6	−5 (3)	C31—C32—C33—C34	−3 (3)
N42^i—Zn3—N6—C6	−128 (3)	C31—C32—C33—C38	−177.8 (17)
N31—Zn3—N6—C6	120 (3)	C32—C33—C34—C35	2 (3)
N8—Zn4—N7—C7	−10 (2)	C38—C33—C34—C35	177.1 (15)
N32—Zn4—N7—C7	−134 (2)	C31—N31—C35—C34	−2 (2)
N41—Zn4—N7—C7	115 (2)	Zn3—N31—C35—C34	168.8 (11)
N10—Zn5—N9—C9	164 (4)	C33—C34—C35—N31	0 (2)
N52^ii—Zn5—N9—C9	−70 (4)	C310—N32—C36—C37	1 (2)
N51—Zn5—N9—C9	39 (4)	Zn4—N32—C36—C37	−173.9 (12)
N9—Zn5—N10—C10	14 (2)	N32—C36—C37—C38	2 (3)
N52^ii—Zn5—N10—C10	−110 (2)	C36—C37—C38—C39	−2 (3)
N51—Zn5—N10—C10	137 (2)	C36—C37—C38—C33	−178.7 (16)
N1—Zn1—N11—C11	−172.3 (12)	C34—C33—C38—C37	158.6 (18)
N2—Zn1—N11—C11	−35.0 (14)	C32—C33—C38—C37	−27 (3)
N22^i—Zn1—N11—C11	77.8 (13)	C34—C33—C38—C39	−18 (3)
N1—Zn1—N11—C15	18.1 (14)	C32—C33—C38—C39	156.6 (18)
N2—Zn1—N11—C15	155.4 (13)	C37—C38—C39—C310	−1 (3)
N22^i—Zn1—N11—C15	−91.8 (13)	C33—C38—C39—C310	175.8 (16)
N4—Zn2—N12—C16	−43.1 (13)	C36—N32—C310—C39	−4 (2)
N3—Zn2—N12—C16	179.4 (12)	Zn4—N32—C310—C39	170.8 (13)
N21—Zn2—N12—C16	66.4 (12)	C38—C39—C310—N32	4 (3)
N4—Zn2—N12—C110	144.1 (13)	N8—Zn4—N41—C45	−27.2 (13)
N3—Zn2—N12—C110	6.6 (14)	N7—Zn4—N41—C45	−164.7 (11)
N21—Zn2—N12—C110	−106.4 (13)	N32—Zn4—N41—C45	82.6 (12)
C15—N11—C11—C12	−2 (2)	N8—Zn4—N41—C41	161.5 (11)
Zn1—N11—C11—C12	−172.4 (12)	N7—Zn4—N41—C41	24.1 (13)
N11—C11—C12—C13	1 (3)	N32—Zn4—N41—C41	−88.7 (12)
C11—C12—C13—C14	0 (3)	C45—N41—C41—C42	0 (2)
C11—C12—C13—C18	175.3 (16)	Zn4—N41—C41—C42	171.1 (11)
C12—C13—C14—C15	1 (3)	N41—C41—C42—C43	2 (3)
C18—C13—C14—C15	−174.7 (16)	C41—C42—C43—C44	−1 (3)
C11—N11—C15—C14	3 (2)	C41—C42—C43—C48	−179.9 (16)
Zn1—N11—C15—C14	172.8 (12)	C42—C43—C44—C45	−1 (3)
C13—C14—C15—N11	−2 (3)	C48—C43—C44—C45	178.2 (17)
C110—N12—C16—C17	2 (2)	C41—N41—C45—C44	−1 (2)
Zn2—N12—C16—C17	−170.7 (13)	Zn4—N41—C45—C44	−173.2 (13)
N12—C16—C17—C18	−2 (3)	C43—C44—C45—N41	2 (3)
C16—C17—C18—C19	1 (3)	C410—N42—C46—C47	−5 (2)
C16—C17—C18—C13	176.1 (16)	Zn3^iii—N42—C46—C47	173.8 (13)
C14—C13—C18—C17	−156.3 (18)	N42—C46—C47—C48	4 (2)
C12—C13—C18—C17	29 (3)	C46—C47—C48—C49	−1 (3)
C14—C13—C18—C19	19 (3)	C46—C47—C48—C43	178.7 (16)
C12—C13—C18—C19	−156.1 (18)	C42—C43—C48—C49	162.5 (18)
C17—C18—C19—C110	−1 (3)	C44—C43—C48—C49	−16 (3)
C13—C18—C19—C110	−176.1 (16)	C42—C43—C48—C47	−18 (3)
C16—N12—C110—C19	−2 (2)	C44—C43—C48—C47	163.7 (17)
Zn2—N12—C110—C19	170.5 (12)	C47—C48—C49—C410	0 (3)
C18—C19—C110—N12	2 (3)	C43—C48—C49—C410	179.9 (15)
N4—Zn2—N21—C21	35.6 (14)	C46—N42—C410—C49	4 (2)
N3—Zn2—N21—C21	172.4 (13)	Zn3^iii—N42—C410—C49	−175.3 (10)
N12—Zn2—N21—C21	−74.8 (14)	C48—C49—C410—N42	−1 (2)
N4—Zn2—N21—C25	−149.5 (12)	N10—Zn5—N51—C51	9.4 (14)
N3—Zn2—N21—C25	−12.7 (14)	N9—Zn5—N51—C51	143.9 (13)
N12—Zn2—N21—C25	100.2 (13)	N52^ii—Zn5—N51—C51	−106.0 (14)
C25—N21—C21—C22	−4 (3)	N10—Zn5—N51—C55	−173.2 (11)
Zn2—N21—C21—C22	170.7 (13)	N9—Zn5—N51—C55	−38.8 (11)
N21—C21—C22—C23	3 (3)	N52^ii—Zn5—N51—C55	71.4 (11)
C21—C22—C23—C24	1 (3)	C55—N51—C51—C52	−4 (2)
C21—C22—C23—C28	176.4 (17)	Zn5—N51—C51—C52	173.1 (12)
C22—C23—C24—C25	−3 (3)	N51—C51—C52—C53	3 (3)
C28—C23—C24—C25	−178.7 (17)	C51—C52—C53—C54	−1 (3)
C21—N21—C25—C24	2 (3)	C51—C52—C53—C58	−178.9 (17)
Zn2—N21—C25—C24	−173.4 (13)	C52—C53—C54—C55	1 (3)
C23—C24—C25—N21	2 (3)	C58—C53—C54—C55	178.8 (16)
C210—N22—C26—C27	2 (3)	C51—N51—C55—C54	4 (2)
Zn1^iii—N22—C26—C27	171.5 (13)	Zn5—N51—C55—C54	−173.5 (13)
N22—C26—C27—C28	0 (3)	C53—C54—C55—N51	−3 (3)
C26—C27—C28—C29	−1 (3)	C510—N52—C56—C57	−3 (2)
C26—C27—C28—C23	176.7 (18)	Zn5^iv—N52—C56—C57	170.8 (14)
C22—C23—C28—C27	−16 (3)	N52—C56—C57—C58	0 (3)
C24—C23—C28—C27	160.1 (19)	C56—C57—C58—C59	3 (3)
C22—C23—C28—C29	161.5 (19)	C56—C57—C58—C53	−178.3 (17)
C24—C23—C28—C29	−23 (3)	C52—C53—C58—C57	18 (3)
C27—C28—C29—C210	0 (3)	C54—C53—C58—C57	−159.5 (18)
C23—C28—C29—C210	−177.7 (18)	C52—C53—C58—C59	−163.9 (18)
C26—N22—C210—C29	−3 (3)	C54—C53—C58—C59	19 (3)
Zn1^iii—N22—C210—C29	−172.8 (13)	C57—C58—C59—C510	−3 (3)
C28—C29—C210—N22	2 (3)	C53—C58—C59—C510	178.5 (16)
N5—Zn3—N31—C35	169.5 (12)	C56—N52—C510—C59	3 (2)
N6—Zn3—N31—C35	32.2 (14)	Zn5^iv—N52—C510—C59	−170.7 (13)
N42^i—Zn3—N31—C35	−83.1 (13)	C58—C59—C510—N52	0 (3)

Symmetry codes: (i) x, y−1, z; (ii) −x+1/2, y+1/2, −z+3/2; (iii) x, y+1, z; (iv) −x+1/2, y−1/2, −z+3/2.