A [mu]₄-oxide-containing a dimeric variant of a sodium dialk­yl(amido)­zincate reagent

Post-metallation derivatives of the sodium dialk­yl(amido)­zincate reagent (TMEDA)Na([mu]-TMP)Zn(^tBu)₂ (TMEDA is N,N,N',N'-tetra­methyl­ethylenediamine and TMP is 2,2,6,6-tetra­methyl­piperidide) have been of structural inter­est due to the insight they give into aromatic metallation mechanisms. Here, the aromatic substrate is formally replaced with [ZnO]₂ to give tetra-tert-butyldi-[mu]₄-oxido-bis­(tetra­methyl­ethylene­di­amine-[kappa]²N,N')bis­([mu]₂-2,2,6,6-tetra­methyl­piperidin-1-ido-[kappa]²N:N)disodiumtetra­zinc hexane 0.59-solvate, [Na₂Zn₄(C₄H₉)₄(C₉H₁₈N)₂O₂(C₆H₁₆N₂)₂]·0.59C₆H₁₄. The crystallographically centrosymmetric complex retains many of the structural features of its parent monomer but has an unusual dimeric structure, with a central planar Zn-O-Zn-O ring joined to two orthogonal near-planar Zn-O-Na-N rings through the dis­torted tetra­hedral geometries of the oxide ions.

S1. Comment

Deprotozincation (transformation of a C—H bond to a C—Zn bond) is currently receiving widespread attention from synthetic chemists (Armstrong et al., 2010; Dayaker et al., 2010; Mosrin et al., 2009; Mulvey, 2009) as an improved alternative to lithiation (Snieckus, 1990) for labilizing aromatic substrates towards subsequent regioselective functionalization. A key factor in the development of this new type of metallation has been a series of X-ray crystallographic studies (Mulvey, 2006) that have elucidated the structures of both the zincate reagents and the zincated aromatic intermediates they generate on reaction with aromatic substrates. Germane to the present study, the most studied zincate reagent to date has been the sodium dialkyl-amidozincate (TMEDA)Na(µ-TMP)Zn(t-Bu)₂, (I), (TMEDA is N,N,N',N'-tetramethylethylenediamine and TMP is 2,2,6,6-tetramethylpiperidide), which adopts a dinuclear contact ion-pair structure (Andrikopoulos et al., 2005) where a trigonal planar Zn centre is connected to a TMEDA-chelated Na centre through a bridging TMP ligand (see scheme). Generally, this monomeric dinuclear motif is retained on reaction of this zincate base with aromatic substrates, with the deprotonated fragment replacing one of the alkyl units attached to Zn in a bridging position between the two metal centres (Armstrong et al., 2009). Emphasizing the experimental care that must be taken when performing these acutely air- and moisture-sensitive zincation reactions, in the course of investigating the deprotonating action of (I) towards N,N-dimethylbenzylamine we have fortuitously prepared the oxide-containing disodium tetrazinc monoalkyl monoamide complex, [(TMEDA)Na(µ-TMP)Zn₂(µ₄-O)(t-Bu)]₂, (II). Whether the oxide derives from moisture or oxygen contamination is not known. Such mixed s-block metal–zinc complexes have recently been shown to be important in the production of mixed metal oxide semiconducting nanoparticles (Heitz et al., 2011). By elucidating the crystal structure of the partial hexane solvate of (II), we show that what can be described formally as incorporating a molecule of zinc oxide (ZnO) into the structure of the starting zincate base leads to a dimerized variant of the structure common to both (I) and its aromatic-containing derivatives.

The molecular structure of (II) (Fig. 1) has a crystallographically imposed centre of symmetry and a highly unusual framework involving three linked four-membered rings. A search of the Cambridge Structural Database (Version?; Allen, 2002) found only one similar heterometallic structural motif with O and N donors - that of a lithium–indium species (Nöth & Seifert, 2002). Literature examples of heterometallic alkali metal–zinc compounds do not show the same coordination framework. Indeed, they are not normally isolated as 2:4 M:Zn species as seen here. Instead, 1:1, 1:2 and 2:2 M:Zn species are common [for examples, see (I) and Zho et al., 2006; Clegg et al., 2009; Baggio et al., 1997; Purdy & George, 1994]. The large organic substituents ensure that the discrete units of (II) interact with each other only via hydrophobic interactions. The packing could formally be described as stacking of the central ZnOZnO rings along the c direction, but as the distance between the rings corresponds to the c cell dimension this is far from a real intermolecular interaction. The hexane solvent molecules lie in channels that also run parallel to the c axis (Fig. 2).

Within the context of previous work on similar metal–alkyl organometallics, the oxide ions of (II) are also unusual. This is partly because aerobic contamination of such systems typically results in the creation of alkoxide ligands and hence alkoxide complexes (Conway et al., 2005), and this only where complete decomposition of all organometallic species is avoided. Where oxide has been incorporated into similar main group metal amides, it is normally observed to lie at the centre of inverse-crown ether complexes in a square-planar geometry (for example, Kennedy et al., 1999). However, in (II) the oxide ion is four-coordinate but is much nearer to tetrahedral than to square-planar geometry [angular range 88.36 (6)–125.94 (7) °]. This geometry about O ensures that the central, strictly planar, ZnOZnO ring plane is perpendicular to the two ZnONaN ring planes. [The dihedral angle between the ring planes is 89.57 (3)°. The ZnONaN ring deviates slightly from planarity, with the metal atoms displaced `down' and the ligand atoms `up'. The maximum deviation from the plane is -0.0414 (7) Å for atom Zn1].

The outer ZnONaN rings and their substituents retain many of the structural features seen in the ZnCNaN-based rings of aromatic derivatives of (I). Thus, Table 1 shows that each of the crystallographically independent Zn atoms has a three-coordinate geometry, with distortions away from trigonal-planar geometry due to the constraints of being part of the ZnOZnO and ZnONaN four-membered rings. Note that both the Zn—O and Zn—C distances for atom Zn2 with its OOC coordination are slightly shorter than the comparable bond distances involving atom Zn1 with its ONC coordination mode. The Na atoms are four-coordinate and have an ONNN coordination shell. The three unique Na—N bonds display considerable variation in length, with the bond to the anionic TMP ligand understandably shorter than the two bonds involving neutral TMEDA, despite the bridging nature of the TMP ligand.

Related literature

For related literature, see: Allen (2002); Andrikopoulos et al. (2005); Armstrong et al. (2009, 2010); Baggio et al. (1997); Clegg et al. (2009); Conway et al. (2005); Dayaker et al. (2010); Heitz et al. (2011); Kennedy (1999); Mosrin et al. (2009); Mulvey (2006, 2009); Nöth & Seifert (2002); Purdy & George (1994); Snieckus (1990); Spek (2009); Zho et al. (2006).

S2. Experimental

Under what were assumed to be stringently air- and moisture-free conditions and in a Schlenk tube under argon, n-BuNa (2 mmol, 0.16 g) was suspended in hexane (10 ml) and sonicated for 10 min to form a fine dispersion. TMP(H) (2 mmol, 0.34 ml) was introduced and the subsequent yellow suspension was stirred for 1 h. In a separate Schlenk tube, t-Bu₂Zn (2 mmol, 0.36 g) was dissolved in hexane (10 ml) and transferred to the already prepared NaTMP via a cannula. TMEDA was then added (2 mmol, 0.3 ml) and the resulting suspension was gently heated to produce a homogeneous yellow solution, an in situ mixture of (I). N,N-dimethylbenzylamine (2 mmol, 0.3 ml) was added and the reaction mixture was stirred overnight. The resulting orange solution was concentrated by the removal of solvent in vacuo and transferred to a refrigerator (at 278 K). A small number of colourless crystals of (II) were deposited overnight. The synthesis has not been reproduced.

S3. Refinement

H atoms were positioned geometrically and refined in riding modes, with C—H = 0.98 or 0.99 Å for CH₃ and CH₂ groups, respectively, and with U_iso(H) = 1.5U_eq(C) for methyl groups or 1.2U_eq(C) for CH₂ groups. The model of the partially present hexane solvent molecule was restrained, with respect to both C—C distances and U_aniso parameters. Its occupancy was estimated using the SQUEEZE procedure implemented within PLATON (Spek, 2009). The largest remaining residual electron-density peaks all lie close to the solvent molecule.

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis CCD (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of (II), showing 50% probability displacement ellipsoids. H atoms and the partial hexane solvent molecule have been omitted for clarity.
	Fig. 2. A packing diagram for (II), viewed along the c direction.

tetra-tert-butyldi-µ₄-oxido-bis(tetramethylethylenediamine- κ²N,N')bis(µ₂-2,2,6,6-tetramethylpiperidin-1-ido- κ²N:N)disodiumtetrazinc hexane 0.59-solvate

Crystal data

[Na2Zn4(C4H9)4(C9H18N)2O2(C6H16N2)2]·0.59C6H14	F(000) = 2438
Mr = 1131.65	Dx = 1.160 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 13556 reflections
a = 27.3191 (12) Å	θ = 2.7–29.1°
b = 18.7841 (7) Å	µ = 1.51 mm^−1
c = 12.7375 (6) Å	T = 123 K
β = 97.565 (4)°	Plate, colourless
V = 6479.5 (5) Å^3	0.18 × 0.18 × 0.04 mm
Z = 4

Data collection

Oxford Gemini S diffractometer	7387 independent reflections
Radiation source: fine-focus sealed tube	5153 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
ω scans	θmax = 27.5°, θmin = 3.6°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	h = −35→35
Tmin = 0.738, Tmax = 1.000	k = −24→23
42490 measured reflections	l = −16→16

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) = 0.086	H-atom parameters constrained
S = 0.97	w = 1/[σ^2(Fo^2) + (0.0496P)^2] where P = (Fo^2 + 2Fc^2)/3
7387 reflections	(Δ/σ)max = 0.001
313 parameters	Δρmax = 0.85 e Å^−3
35 restraints	Δρmin = −0.25 e Å^−3

Special details

Experimental. CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.33.55 Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

4 low angle reflections with F_o much graeter than Fc were omitted from the final calculations. A small satellite crystal was believed to be present on the sample.

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	0.852809 (9)	0.187293 (12)	0.072448 (19)	0.01863 (8)
Zn2	0.769600 (9)	0.316824 (12)	0.01632 (2)	0.01904 (8)
Na1	0.84231 (3)	0.21327 (4)	−0.16252 (7)	0.0220 (2)
O1	0.79586 (5)	0.22550 (7)	−0.02363 (11)	0.0178 (3)
N1	0.90624 (6)	0.17551 (9)	−0.01791 (15)	0.0212 (4)
N2	0.85961 (8)	0.30121 (10)	−0.31418 (16)	0.0306 (5)
N3	0.81803 (7)	0.15000 (10)	−0.33990 (15)	0.0280 (5)
C1	0.92261 (9)	0.10139 (13)	−0.0290 (2)	0.0311 (6)
C2	0.95890 (10)	0.09755 (15)	−0.1123 (2)	0.0447 (7)
H2A	0.9723	0.0486	−0.1137	0.054*
H2B	0.9407	0.1078	−0.1831	0.054*
C3	1.00163 (10)	0.14989 (18)	−0.0896 (3)	0.0538 (8)
H3A	1.0223	0.1368	−0.0226	0.065*
H3B	1.0226	0.1479	−0.1473	0.065*
C4	0.98162 (10)	0.22460 (15)	−0.0810 (2)	0.0407 (7)
H4A	0.9644	0.2393	−0.1509	0.049*
H4B	1.0095	0.2577	−0.0617	0.049*
C5	0.94567 (8)	0.23037 (13)	0.00175 (19)	0.0291 (6)
C6	0.87696 (10)	0.05811 (12)	−0.0682 (2)	0.0373 (6)
H6A	0.8611	0.0780	−0.1354	0.056*
H6B	0.8538	0.0598	−0.0157	0.056*
H6C	0.8865	0.0086	−0.0790	0.056*
C7	0.94573 (11)	0.06455 (15)	0.0751 (2)	0.0477 (8)
H7A	0.9782	0.0854	0.0987	0.072*
H7B	0.9495	0.0135	0.0623	0.072*
H7C	0.9241	0.0714	0.1299	0.072*
C8	0.92011 (10)	0.30251 (13)	−0.0122 (2)	0.0381 (6)
H8A	0.9018	0.3057	−0.0836	0.057*
H8B	0.9449	0.3405	−0.0024	0.057*
H8C	0.8972	0.3077	0.0403	0.057*
C9	0.97473 (10)	0.23049 (16)	0.1147 (2)	0.0432 (7)
H9A	0.9936	0.1862	0.1262	0.065*
H9B	0.9516	0.2342	0.1670	0.065*
H9C	0.9974	0.2712	0.1223	0.065*
C10	0.84053 (8)	0.17141 (12)	0.22420 (17)	0.0229 (5)
C11	0.88694 (10)	0.16722 (17)	0.3062 (2)	0.0463 (7)
H11A	0.8774	0.1576	0.3763	0.069*
H11B	0.9048	0.2125	0.3077	0.069*
H11C	0.9083	0.1288	0.2868	0.069*
C12	0.80936 (10)	0.23338 (14)	0.2578 (2)	0.0382 (6)
H12A	0.8010	0.2244	0.3291	0.057*
H12B	0.7790	0.2375	0.2079	0.057*
H12C	0.8282	0.2777	0.2577	0.057*
C13	0.81084 (11)	0.10338 (13)	0.2301 (2)	0.0399 (7)
H13A	0.8034	0.0967	0.3026	0.060*
H13B	0.8301	0.0628	0.2098	0.060*
H13C	0.7799	0.1069	0.1816	0.060*
C14	0.79513 (8)	0.41665 (12)	0.04513 (19)	0.0258 (5)
C15	0.82133 (10)	0.44732 (13)	−0.0442 (2)	0.0378 (6)
H15A	0.8315	0.4964	−0.0269	0.057*
H15B	0.7987	0.4467	−0.1106	0.057*
H15C	0.8505	0.4184	−0.0521	0.057*
C16	0.83120 (10)	0.42031 (13)	0.1468 (2)	0.0363 (6)
H16A	0.8424	0.4695	0.1592	0.054*
H16B	0.8597	0.3896	0.1403	0.054*
H16C	0.8147	0.4041	0.2064	0.054*
C17	0.75151 (10)	0.46530 (13)	0.0577 (2)	0.0368 (6)
H17A	0.7346	0.4480	0.1160	0.055*
H17B	0.7284	0.4653	−0.0081	0.055*
H17C	0.7635	0.5138	0.0733	0.055*
C18	0.81955 (12)	0.35247 (15)	−0.3095 (3)	0.0595 (9)
H18A	0.8267	0.3817	−0.2456	0.089*
H18B	0.7884	0.3268	−0.3075	0.089*
H18C	0.8167	0.3832	−0.3722	0.089*
C19	0.90596 (12)	0.34018 (15)	−0.3117 (2)	0.0497 (8)
H19A	0.9048	0.3699	−0.3752	0.075*
H19B	0.9334	0.3064	−0.3097	0.075*
H19C	0.9109	0.3705	−0.2485	0.075*
C20	0.85121 (11)	0.26000 (13)	−0.4128 (2)	0.0398 (7)
H20A	0.8818	0.2337	−0.4218	0.048*
H20B	0.8443	0.2934	−0.4731	0.048*
C21	0.80922 (10)	0.20778 (14)	−0.4166 (2)	0.0355 (6)
H21A	0.7790	0.2337	−0.4037	0.043*
H21B	0.8030	0.1871	−0.4886	0.043*
C22	0.77156 (10)	0.11118 (15)	−0.3365 (2)	0.0431 (7)
H22A	0.7473	0.1429	−0.3106	0.065*
H22B	0.7775	0.0702	−0.2889	0.065*
H22C	0.7588	0.0946	−0.4079	0.065*
C23	0.85420 (10)	0.10021 (14)	−0.3737 (2)	0.0393 (7)
H23A	0.8422	0.0823	−0.4447	0.059*
H23B	0.8589	0.0603	−0.3239	0.059*
H23C	0.8857	0.1248	−0.3752	0.059*
C24	0.9791 (2)	0.4748 (3)	0.4921 (4)	0.0557 (14)	0.59
H24A	0.9498	0.4991	0.5137	0.067*	0.59
H24B	0.9869	0.4343	0.5410	0.067*	0.59
C25	0.9648 (2)	0.4454 (3)	0.3839 (4)	0.0646 (16)	0.59
H25A	0.9535	0.4849	0.3352	0.077*	0.59
H25B	0.9943	0.4239	0.3590	0.077*	0.59
C26	0.92599 (19)	0.3921 (3)	0.3787 (4)	0.0564 (14)	0.59
H26A	0.9356	0.3547	0.4310	0.085*	0.59
H26B	0.9209	0.3711	0.3076	0.085*	0.59
H26C	0.8953	0.4144	0.3939	0.085*	0.59

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.01586 (14)	0.02331 (14)	0.01700 (14)	0.00261 (11)	0.00323 (10)	0.00188 (10)
Zn2	0.01866 (14)	0.01584 (13)	0.02253 (15)	−0.00005 (11)	0.00242 (11)	−0.00062 (10)
Na1	0.0229 (5)	0.0257 (5)	0.0178 (5)	0.0033 (4)	0.0039 (4)	0.0010 (4)
O1	0.0150 (8)	0.0182 (8)	0.0202 (8)	0.0035 (6)	0.0026 (6)	−0.0003 (6)
N1	0.0144 (9)	0.0253 (10)	0.0240 (10)	0.0052 (8)	0.0036 (8)	0.0007 (8)
N2	0.0371 (13)	0.0264 (11)	0.0297 (12)	0.0024 (9)	0.0099 (10)	0.0022 (9)
N3	0.0338 (12)	0.0276 (11)	0.0236 (11)	0.0009 (9)	0.0075 (9)	−0.0019 (9)
C1	0.0268 (14)	0.0343 (14)	0.0329 (14)	0.0141 (11)	0.0065 (11)	0.0023 (11)
C2	0.0378 (17)	0.0536 (17)	0.0449 (18)	0.0227 (14)	0.0136 (14)	−0.0021 (14)
C3	0.0251 (15)	0.091 (2)	0.0478 (19)	0.0104 (16)	0.0148 (14)	−0.0075 (17)
C4	0.0243 (14)	0.0615 (19)	0.0383 (16)	−0.0066 (13)	0.0112 (12)	0.0001 (14)
C5	0.0175 (12)	0.0424 (15)	0.0277 (14)	−0.0045 (11)	0.0047 (10)	0.0000 (11)
C6	0.0459 (17)	0.0219 (12)	0.0446 (17)	0.0069 (12)	0.0079 (13)	−0.0013 (11)
C7	0.0482 (18)	0.0447 (16)	0.0495 (19)	0.0248 (14)	0.0041 (15)	0.0148 (14)
C8	0.0386 (16)	0.0354 (15)	0.0413 (16)	−0.0130 (12)	0.0095 (13)	−0.0026 (12)
C9	0.0260 (14)	0.0646 (19)	0.0379 (16)	−0.0086 (13)	0.0002 (13)	−0.0028 (14)
C10	0.0219 (12)	0.0289 (13)	0.0179 (11)	0.0047 (10)	0.0030 (10)	0.0039 (9)
C11	0.0329 (16)	0.081 (2)	0.0249 (14)	0.0029 (15)	0.0028 (12)	0.0087 (14)
C12	0.0529 (18)	0.0417 (15)	0.0219 (13)	0.0124 (13)	0.0121 (12)	0.0032 (11)
C13	0.0549 (19)	0.0345 (14)	0.0325 (15)	−0.0043 (13)	0.0136 (14)	0.0053 (12)
C14	0.0261 (13)	0.0185 (11)	0.0330 (14)	−0.0027 (10)	0.0048 (11)	−0.0028 (9)
C15	0.0373 (16)	0.0315 (14)	0.0457 (17)	−0.0067 (12)	0.0100 (13)	0.0026 (12)
C16	0.0357 (15)	0.0301 (14)	0.0415 (16)	−0.0037 (12)	−0.0010 (13)	−0.0058 (11)
C17	0.0396 (16)	0.0265 (13)	0.0442 (17)	0.0055 (12)	0.0055 (13)	−0.0029 (11)
C18	0.066 (2)	0.0394 (17)	0.073 (2)	0.0149 (16)	0.0096 (19)	−0.0122 (16)
C19	0.057 (2)	0.0473 (16)	0.0469 (19)	−0.0093 (16)	0.0155 (15)	0.0103 (14)
C20	0.065 (2)	0.0328 (14)	0.0246 (14)	0.0053 (14)	0.0170 (14)	0.0062 (11)
C21	0.0492 (17)	0.0359 (14)	0.0207 (13)	0.0041 (13)	0.0021 (12)	−0.0019 (11)
C22	0.0425 (17)	0.0451 (16)	0.0434 (17)	−0.0036 (13)	0.0120 (14)	−0.0082 (13)
C23	0.0410 (17)	0.0382 (15)	0.0405 (17)	0.0018 (12)	0.0121 (13)	−0.0048 (12)
C24	0.060 (4)	0.055 (3)	0.055 (3)	0.015 (3)	0.018 (3)	0.007 (3)
C25	0.073 (4)	0.066 (4)	0.051 (3)	0.011 (3)	−0.004 (3)	−0.019 (3)
C26	0.046 (3)	0.076 (4)	0.045 (3)	0.028 (3)	−0.002 (3)	0.011 (3)

Geometric parameters (Å, º)

Zn1—O1	1.9829 (14)	C10—C12	1.536 (3)
Zn1—N1	1.9866 (18)	C11—H11A	0.9800
Zn1—C10	2.027 (2)	C11—H11B	0.9800
Zn1—Na1	3.0086 (9)	C11—H11C	0.9800
Zn2—O1	1.9526 (14)	C12—H12A	0.9800
Zn2—O1^i	1.9706 (14)	C12—H12B	0.9800
Zn2—C14	2.017 (2)	C12—H12C	0.9800
Zn2—Zn2^i	2.7395 (5)	C13—H13A	0.9800
Na1—O1	2.3202 (17)	C13—H13B	0.9800
Na1—N1	2.470 (2)	C13—H13C	0.9800
Na1—N2	2.632 (2)	C14—C16	1.522 (3)
Na1—N3	2.562 (2)	C14—C17	1.527 (3)
O1—Zn2^i	1.9706 (14)	C14—C15	1.534 (3)
N1—C1	1.475 (3)	C15—H15A	0.9800
N1—C5	1.488 (3)	C15—H15B	0.9800
N2—C19	1.459 (3)	C15—H15C	0.9800
N2—C18	1.465 (3)	C16—H16A	0.9800
N2—C20	1.468 (3)	C16—H16B	0.9800
N3—C21	1.459 (3)	C16—H16C	0.9800
N3—C23	1.466 (3)	C17—H17A	0.9800
N3—C22	1.470 (3)	C17—H17B	0.9800
C1—C6	1.517 (4)	C17—H17C	0.9800
C1—C2	1.546 (3)	C18—H18A	0.9800
C1—C7	1.554 (3)	C18—H18B	0.9800
C2—C3	1.525 (4)	C18—H18C	0.9800
C2—H2A	0.9900	C19—H19A	0.9800
C2—H2B	0.9900	C19—H19B	0.9800
C3—C4	1.515 (4)	C19—H19C	0.9800
C3—H3A	0.9900	C20—C21	1.505 (4)
C3—H3B	0.9900	C20—H20A	0.9900
C4—C5	1.536 (3)	C20—H20B	0.9900
C4—H4A	0.9900	C21—H21A	0.9900
C4—H4B	0.9900	C21—H21B	0.9900
C5—C8	1.524 (3)	C22—H22A	0.9800
C5—C9	1.549 (3)	C22—H22B	0.9800
C6—H6A	0.9800	C22—H22C	0.9800
C6—H6B	0.9800	C23—H23A	0.9800
C6—H6C	0.9800	C23—H23B	0.9800
C7—H7A	0.9800	C23—H23C	0.9800
C7—H7B	0.9800	C24—C24^ii	1.478 (10)
C7—H7C	0.9800	C24—C25	1.488 (6)
C8—H8A	0.9800	C24—H24A	0.9900
C8—H8B	0.9800	C24—H24B	0.9900
C8—H8C	0.9800	C25—C26	1.454 (6)
C9—H9A	0.9800	C25—H25A	0.9900
C9—H9B	0.9800	C25—H25B	0.9900
C9—H9C	0.9800	C26—H26A	0.9800
C10—C13	1.521 (3)	C26—H26B	0.9800
C10—C11	1.535 (3)	C26—H26C	0.9800
O1—Zn1—N1	105.03 (7)	H9A—C9—H9C	109.5
O1—Zn1—C10	115.28 (8)	H9B—C9—H9C	109.5
N1—Zn1—C10	139.69 (8)	C13—C10—C11	108.8 (2)
O1—Zn1—Na1	50.43 (4)	C13—C10—C12	107.7 (2)
N1—Zn1—Na1	54.75 (5)	C11—C10—C12	106.8 (2)
C10—Zn1—Na1	165.12 (7)	C13—C10—Zn1	109.09 (16)
O1—Zn2—O1^i	91.42 (6)	C11—C10—Zn1	115.51 (17)
O1—Zn2—C14	137.21 (8)	C12—C10—Zn1	108.74 (15)
O1^i—Zn2—C14	131.35 (8)	C10—C11—H11A	109.5
O1—Zn2—Zn2^i	45.98 (4)	C10—C11—H11B	109.5
O1^i—Zn2—Zn2^i	45.44 (4)	H11A—C11—H11B	109.5
C14—Zn2—Zn2^i	176.62 (7)	C10—C11—H11C	109.5
O1—Na1—N1	82.17 (6)	H11A—C11—H11C	109.5
O1—Na1—N3	127.90 (7)	H11B—C11—H11C	109.5
N1—Na1—N3	126.88 (7)	C10—C12—H12A	109.5
O1—Na1—N2	131.81 (6)	C10—C12—H12B	109.5
N1—Na1—N2	123.38 (7)	H12A—C12—H12B	109.5
N3—Na1—N2	72.21 (6)	C10—C12—H12C	109.5
O1—Na1—Zn1	41.21 (4)	H12A—C12—H12C	109.5
N1—Na1—Zn1	41.07 (4)	H12B—C12—H12C	109.5
N3—Na1—Zn1	141.43 (5)	C10—C13—H13A	109.5
N2—Na1—Zn1	146.02 (6)	C10—C13—H13B	109.5
Zn1—O1—Na1	88.36 (6)	H13A—C13—H13B	109.5
Zn2—O1—Zn1	116.26 (7)	C10—C13—H13C	109.5
Zn2^i—O1—Zn1	117.90 (7)	H13A—C13—H13C	109.5
Zn2—O1—Zn2^i	88.58 (6)	H13B—C13—H13C	109.5
Zn2—O1—Na1	122.85 (7)	C16—C14—C17	108.1 (2)
Zn2^i—O1—Na1	125.94 (7)	C16—C14—C15	107.5 (2)
C1—N1—C5	116.62 (18)	C17—C14—C15	107.4 (2)
C1—N1—Zn1	114.56 (14)	C16—C14—Zn2	111.49 (16)
C5—N1—Zn1	113.33 (14)	C17—C14—Zn2	108.63 (16)
C1—N1—Na1	113.17 (14)	C15—C14—Zn2	113.45 (16)
C5—N1—Na1	110.60 (13)	C14—C15—H15A	109.5
Zn1—N1—Na1	84.19 (6)	C14—C15—H15B	109.5
C19—N2—C18	108.7 (2)	H15A—C15—H15B	109.5
C19—N2—C20	108.7 (2)	C14—C15—H15C	109.5
C18—N2—C20	110.4 (2)	H15A—C15—H15C	109.5
C19—N2—Na1	122.56 (17)	H15B—C15—H15C	109.5
C18—N2—Na1	100.10 (17)	C14—C16—H16A	109.5
C20—N2—Na1	105.93 (14)	C14—C16—H16B	109.5
C21—N3—C23	109.6 (2)	H16A—C16—H16B	109.5
C21—N3—C22	108.8 (2)	C14—C16—H16C	109.5
C23—N3—C22	108.07 (19)	H16A—C16—H16C	109.5
C21—N3—Na1	104.27 (14)	H16B—C16—H16C	109.5
C23—N3—Na1	116.67 (15)	C14—C17—H17A	109.5
C22—N3—Na1	109.20 (15)	C14—C17—H17B	109.5
N1—C1—C6	106.92 (18)	H17A—C17—H17B	109.5
N1—C1—C2	109.8 (2)	C14—C17—H17C	109.5
C6—C1—C2	108.8 (2)	H17A—C17—H17C	109.5
N1—C1—C7	115.7 (2)	H17B—C17—H17C	109.5
C6—C1—C7	105.5 (2)	N2—C18—H18A	109.5
C2—C1—C7	109.8 (2)	N2—C18—H18B	109.5
C3—C2—C1	112.6 (2)	H18A—C18—H18B	109.5
C3—C2—H2A	109.1	N2—C18—H18C	109.5
C1—C2—H2A	109.1	H18A—C18—H18C	109.5
C3—C2—H2B	109.1	H18B—C18—H18C	109.5
C1—C2—H2B	109.1	N2—C19—H19A	109.5
H2A—C2—H2B	107.8	N2—C19—H19B	109.5
C4—C3—C2	109.7 (2)	H19A—C19—H19B	109.5
C4—C3—H3A	109.7	N2—C19—H19C	109.5
C2—C3—H3A	109.7	H19A—C19—H19C	109.5
C4—C3—H3B	109.7	H19B—C19—H19C	109.5
C2—C3—H3B	109.7	N2—C20—C21	113.8 (2)
H3A—C3—H3B	108.2	N2—C20—H20A	108.8
C3—C4—C5	112.6 (2)	C21—C20—H20A	108.8
C3—C4—H4A	109.1	N2—C20—H20B	108.8
C5—C4—H4A	109.1	C21—C20—H20B	108.8
C3—C4—H4B	109.1	H20A—C20—H20B	107.7
C5—C4—H4B	109.1	N3—C21—C20	113.9 (2)
H4A—C4—H4B	107.8	N3—C21—H21A	108.8
N1—C5—C8	106.60 (18)	C20—C21—H21A	108.8
N1—C5—C4	110.5 (2)	N3—C21—H21B	108.8
C8—C5—C4	107.9 (2)	C20—C21—H21B	108.8
N1—C5—C9	115.4 (2)	H21A—C21—H21B	107.7
C8—C5—C9	106.2 (2)	N3—C22—H22A	109.5
C4—C5—C9	110.0 (2)	N3—C22—H22B	109.5
C1—C6—H6A	109.5	H22A—C22—H22B	109.5
C1—C6—H6B	109.5	N3—C22—H22C	109.5
H6A—C6—H6B	109.5	H22A—C22—H22C	109.5
C1—C6—H6C	109.5	H22B—C22—H22C	109.5
H6A—C6—H6C	109.5	N3—C23—H23A	109.5
H6B—C6—H6C	109.5	N3—C23—H23B	109.5
C1—C7—H7A	109.5	H23A—C23—H23B	109.5
C1—C7—H7B	109.5	N3—C23—H23C	109.5
H7A—C7—H7B	109.5	H23A—C23—H23C	109.5
C1—C7—H7C	109.5	H23B—C23—H23C	109.5
H7A—C7—H7C	109.5	C24^ii—C24—C25	117.9 (6)
H7B—C7—H7C	109.5	C24^ii—C24—H24A	107.8
C5—C8—H8A	109.5	C25—C24—H24A	107.8
C5—C8—H8B	109.5	C24^ii—C24—H24B	107.8
H8A—C8—H8B	109.5	C25—C24—H24B	107.8
C5—C8—H8C	109.5	H24A—C24—H24B	107.2
H8A—C8—H8C	109.5	C26—C25—C24	113.5 (5)
H8B—C8—H8C	109.5	C26—C25—H25A	108.9
C5—C9—H9A	109.5	C24—C25—H25A	108.9
C5—C9—H9B	109.5	C26—C25—H25B	108.9
H9A—C9—H9B	109.5	C24—C25—H25B	108.9
C5—C9—H9C	109.5	H25A—C25—H25B	107.7
N1—Zn1—Na1—O1	−174.86 (8)	N3—Na1—N2—C20	−6.95 (16)
C10—Zn1—Na1—O1	17.7 (3)	Zn1—Na1—N2—C20	166.32 (13)
O1—Zn1—Na1—N1	174.86 (8)	O1—Na1—N3—C21	107.27 (16)
C10—Zn1—Na1—N1	−167.4 (3)	N1—Na1—N3—C21	−141.11 (15)
O1—Zn1—Na1—N3	−93.65 (10)	N2—Na1—N3—C21	−22.33 (15)
N1—Zn1—Na1—N3	91.49 (11)	Zn1—Na1—N3—C21	163.70 (13)
C10—Zn1—Na1—N3	−75.9 (3)	O1—Na1—N3—C23	−131.68 (16)
O1—Zn1—Na1—N2	96.67 (11)	N1—Na1—N3—C23	−20.1 (2)
N1—Zn1—Na1—N2	−78.19 (12)	N2—Na1—N3—C23	98.72 (17)
C10—Zn1—Na1—N2	114.4 (3)	Zn1—Na1—N3—C23	−75.25 (19)
O1^i—Zn2—O1—Zn2^i	0.0	O1—Na1—N3—C22	−8.83 (19)
C14—Zn2—O1—Zn2^i	178.41 (10)	N1—Na1—N3—C22	102.79 (17)
O1^i—Zn2—O1—Zn1	−120.65 (10)	N2—Na1—N3—C22	−138.43 (17)
C14—Zn2—O1—Zn1	57.76 (14)	Zn1—Na1—N3—C22	47.60 (19)
Zn2^i—Zn2—O1—Zn1	−120.65 (10)	C5—N1—C1—C6	−169.7 (2)
O1^i—Zn2—O1—Na1	133.06 (10)	Zn1—N1—C1—C6	54.5 (2)
C14—Zn2—O1—Na1	−48.53 (14)	Na1—N1—C1—C6	−39.7 (2)
Zn2^i—Zn2—O1—Na1	133.06 (10)	C5—N1—C1—C2	−51.8 (3)
N1—Zn1—O1—Zn2	−121.88 (8)	Zn1—N1—C1—C2	172.41 (16)
C10—Zn1—O1—Zn2	58.74 (10)	Na1—N1—C1—C2	78.1 (2)
Na1—Zn1—O1—Zn2	−126.22 (9)	C5—N1—C1—C7	73.2 (3)
N1—Zn1—O1—Zn2^i	134.82 (8)	Zn1—N1—C1—C7	−62.6 (2)
C10—Zn1—O1—Zn2^i	−44.56 (11)	Na1—N1—C1—C7	−156.85 (18)
Na1—Zn1—O1—Zn2^i	130.48 (9)	N1—C1—C2—C3	53.0 (3)
N1—Zn1—O1—Na1	4.34 (7)	C6—C1—C2—C3	169.7 (2)
C10—Zn1—O1—Na1	−175.04 (7)	C7—C1—C2—C3	−75.3 (3)
N1—Na1—O1—Zn2	117.15 (9)	C1—C2—C3—C4	−55.5 (3)
N3—Na1—O1—Zn2	−111.49 (9)	C2—C3—C4—C5	55.2 (3)
N2—Na1—O1—Zn2	−11.31 (13)	C1—N1—C5—C8	168.7 (2)
Zn1—Na1—O1—Zn2	120.56 (10)	Zn1—N1—C5—C8	−55.0 (2)
N1—Na1—O1—Zn2^i	−127.28 (9)	Na1—N1—C5—C8	37.5 (2)
N3—Na1—O1—Zn2^i	4.08 (12)	C1—N1—C5—C4	51.8 (3)
N2—Na1—O1—Zn2^i	104.25 (10)	Zn1—N1—C5—C4	−171.94 (16)
Zn1—Na1—O1—Zn2^i	−123.88 (10)	Na1—N1—C5—C4	−79.4 (2)
N1—Na1—O1—Zn1	−3.41 (5)	C1—N1—C5—C9	−73.7 (3)
N3—Na1—O1—Zn1	127.95 (7)	Zn1—N1—C5—C9	62.6 (2)
N2—Na1—O1—Zn1	−131.87 (8)	Na1—N1—C5—C9	155.12 (17)
O1—Zn1—N1—C1	−116.95 (15)	C3—C4—C5—N1	−52.4 (3)
C10—Zn1—N1—C1	62.2 (2)	C3—C4—C5—C8	−168.5 (2)
Na1—Zn1—N1—C1	−112.85 (16)	C3—C4—C5—C9	76.1 (3)
O1—Zn1—N1—C5	105.85 (15)	O1—Zn1—C10—C13	77.48 (17)
C10—Zn1—N1—C5	−75.01 (19)	N1—Zn1—C10—C13	−101.60 (19)
Na1—Zn1—N1—C5	109.95 (15)	Na1—Zn1—C10—C13	62.4 (3)
O1—Zn1—N1—Na1	−4.10 (7)	O1—Zn1—C10—C11	−159.69 (17)
C10—Zn1—N1—Na1	175.04 (10)	N1—Zn1—C10—C11	21.2 (2)
O1—Na1—N1—C1	117.68 (15)	Na1—Zn1—C10—C11	−174.73 (19)
N3—Na1—N1—C1	−14.55 (18)	O1—Zn1—C10—C12	−39.74 (18)
N2—Na1—N1—C1	−106.66 (15)	N1—Zn1—C10—C12	141.18 (16)
Zn1—Na1—N1—C1	114.26 (16)	Na1—Zn1—C10—C12	−54.8 (3)
O1—Na1—N1—C5	−109.36 (14)	O1—Zn2—C14—C16	−69.0 (2)
N3—Na1—N1—C5	118.41 (14)	O1^i—Zn2—C14—C16	108.87 (17)
N2—Na1—N1—C5	26.30 (16)	Zn2^i—Zn2—C14—C16	91.2 (12)
Zn1—Na1—N1—C5	−112.77 (15)	O1—Zn2—C14—C17	171.97 (14)
O1—Na1—N1—Zn1	3.42 (5)	O1^i—Zn2—C14—C17	−10.1 (2)
N3—Na1—N1—Zn1	−128.82 (8)	Zn2^i—Zn2—C14—C17	−27.8 (13)
N2—Na1—N1—Zn1	139.08 (7)	O1—Zn2—C14—C15	52.6 (2)
O1—Na1—N2—C19	102.4 (2)	O1^i—Zn2—C14—C15	−129.56 (16)
N1—Na1—N2—C19	−9.3 (2)	Zn2^i—Zn2—C14—C15	−147.2 (11)
N3—Na1—N2—C19	−132.2 (2)	C19—N2—C20—C21	170.0 (2)
Zn1—Na1—N2—C19	41.0 (2)	C18—N2—C20—C21	−70.9 (3)
O1—Na1—N2—C18	−17.6 (2)	Na1—N2—C20—C21	36.6 (2)
N1—Na1—N2—C18	−129.30 (16)	C23—N3—C21—C20	−73.0 (3)
N3—Na1—N2—C18	107.79 (17)	C22—N3—C21—C20	169.0 (2)
Zn1—Na1—N2—C18	−78.94 (19)	Na1—N3—C21—C20	52.6 (2)
O1—Na1—N2—C20	−132.30 (15)	N2—C20—C21—N3	−66.2 (3)
N1—Na1—N2—C20	115.96 (16)	C24^ii—C24—C25—C26	175.1 (6)

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