catena-Poly[[aqua­(1,10-phenanthroline-κ²N,N′)zinc(II)]-μ-5-[4-(hydroxy­meth­yl)benz­yloxy]isophthalato-κ³O¹,O^1′:O³-[aqua­(1,10-phenanthroline-κ²N,N′)zinc(II)]-μ-5-[4-(hydroxy­meth­yl)benz­yloxy]isophthalato-κ²O¹:O³]

The title compound, [Zn₂(C₁₆H₁₂O₆)₂(C₁₂H₈N₂)₂(H₂O)₂]_n, consists of linear chains formed through 5-[4-(hydroxy­methyl)­benzyl­oxy]isophthalate (mabobdc) ligands linking five- and six-coordinated Zn^II ions. The linear chains are linked into a bilayer network via O—H...O hydrogen bonds. Adjacent bilayer structures are further linked with each other via C—H...O hydrogen bonds and π–π and C—H...π inter­actions to give a three-dimensional supra­molecular framework. The results demonstrate the coordination and supra­molecular chemistry of the mabobdc ligand.

S1. Comment

Considerable progress has recently been made on the crystal engineering of supramolecular architectures organized and sustained by means of coordinate covalent supramolecular contacts (such as hydrogen bonds and π–π interactions), aurophilicity interactions, and so on (Colacio et al., 2002; Roesky & Andruh, 2003; Guilera & Steed, 1999). As an excellent building block in the design and construction of supramolecular polymers, 1,10-phenanthroline (1,10-phen) is relatively well known. Multicarboxylate ligands are good candidates for the construction of hydrogen-bonding networks. 5-[4-Methanol(benzyloxy)]isophthalic acid (H₂mabobdc) not only has two rigid carboxyl groups but also one flexible hydroxyl group. Thus, the mabobdc ligand may be a suitable ligand not only in the construction of coordination compounds but also in the construction of supramolecular networks. Here, we report the title novel Zn supramolecular complex, [Zn₂(mabobdc)₂(1,10-phen)₂(H₂O)₂]_n, (I), which is the first example of the coordination and supramolecular chemistry of the mabobdc ligand (Cambridge Structural Database, Version?; Allen, 2002).

There are two crystallographically independent mabobdc ligands in complex (I) (Fig. 1). One of these acts as a bidentate bridging ligand linking atoms Zn1 and Zn2 in a monodentate mode, while the other bridges atoms Zn1 and Zn2 in monodentate and chelate fashions, respectively. The mabobdc ligands thus connect the Zn^II centres to form a novel metal–organic chain in which 1,10-phen molecules act as terminal chelating ligands to coordinate to Zn^II centres. Atom Zn1 has a distorted trigonal–bipyramidal coordination, with the equatorial plane defined by atom N4 from a 1,10-phen ligand and two O atoms [O10 and O4 at (x, 1 − y, z)] from two monodentate carboxyl groups of two mabobdc ligands. Atom N3 from the 1,10-phen ligand and water atom O2W are at the apical positions (Table 1). Atom Zn2 has distorted octahedral coordination, with the basal plane consisting of the two 1,10-phen atoms N1 and N2, atom O11 from one chelating carboxyl group of a mabobdc ligand and water atom O1W. The apical sites are occupied by atoms O8 and O12 of two mabobdc ligands (Table 1).

In (I), the Zn—O bond distances lie in the range 2.012 (5)–2.315 (5) Å, which is greater than that in {[Zn₃(5-oxyacetate isophthalic anion)₂(phen)₃]·2H₂O}_n [Zn—O = 2.083 (3)–2.268 (7) Å; Cao et al., 2004]. The Zn—N bond lengths are in the range 2.119 (5)–2.215 (5) Å, which is longer than those reported in {[Zn₃(5-oxyacetate isophthalic anion)₂(phen)₃]·2H₂O}_n [Zn—N = 2.098 (4)–2.112 (6) Å; Cao et al., 2004).

The chains of (I) are linked by O—H···O hydrogen bonds consisting of two different hydroxy and two different carboxylate O atoms (O1—H1···O12ⁱⁱ and O2—H2A···O9ⁱⁱ; symmetry code in Table 2), resulting in monolayer sheets (Fig. 2 and Table 2). These sheets are further linked into bilayer structures via three O—H···O hydrogen bonds (O1W—H1D···O1ⁱⁱⁱ, O2W—H2C···O2^iv and O2W—H2D···O7^v; symmetry codes in Table 2), as shown in Fig. 2; details are given in Table 2.

The hydrogen-bonded bilayer structures are further linked by C—H···O hydrogen bonds and π–π and C—H···π interactions. Three C—H···O hydrogen bonds (Table 2) are formed by C—H groups of 1,10-phen ligands. The principal centroid-to-centroid interactions include Cg1···Cg2 = 3.477 (4) Å [Cg1 is the centroid of the ring N1/C17–C20/C28 and Cg2 is the centroid of the ring C51–C54/N4/C55 at (2 − x, 3 − y, 1 − z)] and Cg3···Cg3* = 3.711 (4) Å [Cg3 is the centroid of the ring C9–C14 and Cg3* is the centroid at (1 − x,1 − y,-z)]. The principal C—H···π interactions are as detailed in Table 2 (Cg4 is the centroid of the aromatic ring C29–C34). These interactions serve to generate a three-dimensional supramolecular framework.

S2. Experimental

The H₂mabobdc ligand was isolated as a byproduct from the reaction of p-xylylene dibromide with dimethyl 5-hydroxyisophthalate. A mixture of Zn(CH₃CO₂)₂·2H₂O (0.3 mmol), H₂mabobdc (0.3 mmol), 1,10-phen (0.3 mmol), K₂CO₃ (0.45 mmol) and water (10 ml) was sealed in a 25 ml Teflon-lined stainless-steel reactor and heated at 433 K for 3 d. [Original text was jumbled up. Please check rephrasing] On completion of the reaction, the reactor was cooled slowly to room temperature and the mixture was filtered, giving yellow single crystals of (I) suitable for X-ray analysis.

S3. Refinement

H atoms bonded to C atoms were positioned geometrically and treated as riding [aromatic C—H = 0.93 Å and aliphatic C—H = 0.97 Å; U_iso(H) = 1.2U_eq(C)]. H atoms bonded to O atoms were positioned geometrically and treated as riding [O—H = 0.82 Å and U_iso(H) = 1.2U_eq(O)], except for the two H atoms on the water molecules, which were located in a difference Fourier map and refined freely.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens,1996); data reduction: SAINT (Siemens,1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Version 2.1c; Bergerhoff et al., 1996); software used to prepare material for publication: SHELXTL (Siemens, 1996).

Figures

	Fig. 1. Part of the structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are plotted at the 30% probability level. Most H atoms have been omitted for clarity. [Symmetry code: (a) x, 1 + y, 1 + z.].
	Fig. 2. A view of (I), showing how the O—H···O hydrogen bonds contribute to the construction of the [Zn2(mabobdc)2(1,10-phen)2(H2O)2]n two-dimensional bilayer network, with hydrogen bonds shown as dashed lines. 1,10-Phen ligands have been omitted for clarity.

catena-Poly[[aqua(1,10-phenanthroline-κ²N,N')zinc(II)]- µ-5-[4-(hydroxymethyl)benzyloxy]isophthalato-κ³O¹,O^1':O³– [aqua(1,10-phenanthroline-κ²N,N')zinc(II)]- µ-5-[4-(hydroxymethyl)benzyloxy]isophthalato-κ²O¹:O³]

Crystal data

[Zn2(C16H12O6)2(C12H8N2)2(H2O)2]	Z = 2
Mr = 1127.73	F(000) = 1156
Triclinic, P1	Dx = 1.566 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.6016 (2) Å	Cell parameters from 5392 reflections
b = 12.2791 (3) Å	θ = 1.1–25.0°
c = 19.6827 (5) Å	µ = 1.08 mm^−1
α = 105.222 (1)°	T = 263 K
β = 92.632 (1)°	Prism, yellow
γ = 103.886 (1)°	0.30 × 0.20 × 0.10 mm
V = 2383.82 (10) Å^3

Data collection

Siemens SMART 1K CCD area-detector diffractometer	8350 independent reflections
Radiation source: fine-focus sealed tube	6518 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
ϕ and ω scans	θmax = 25.0°, θmin = 1.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→8
Tmin = 0.773, Tmax = 0.899	k = −14→14
12481 measured reflections	l = −23→23

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)] = 0.080	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.200	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0526P)^2 + 16.9982P] where P = (Fo^2 + 2Fc^2)/3
8350 reflections	(Δ/σ)max < 0.001
693 parameters	Δρmax = 0.60 e Å^−3
0 restraints	Δρmin = −0.69 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Zn1	0.63125 (7)	1.48016 (7)	0.70015 (4)	0.0282 (2)
Zn2	0.63680 (8)	0.97569 (7)	0.18555 (4)	0.0293 (2)
N1	0.8383 (5)	1.0610 (5)	0.1896 (3)	0.0339 (13)
N2	0.7366 (5)	0.8842 (5)	0.2441 (3)	0.0370 (13)
N3	0.7507 (6)	1.3952 (5)	0.7539 (3)	0.0394 (14)
N4	0.8258 (5)	1.5617 (5)	0.6882 (3)	0.0330 (13)
O1W	0.5801 (5)	1.1057 (4)	0.1475 (3)	0.0437 (12)
H1c	0.5648	1.1551	0.1808	0.065*
H1d	0.503 (9)	1.082 (8)	0.109 (5)	0.08 (3)*
O1	−0.3751 (5)	−0.0002 (5)	−0.0376 (3)	0.0512 (14)
H1	−0.3814	−0.0319	−0.0056	0.077*
O2W	0.5530 (5)	1.5972 (5)	0.6575 (3)	0.0479 (13)
H2C	0.4968	1.5593	0.6242	0.072*
H2D	0.526 (10)	1.653 (9)	0.684 (5)	0.09 (4)*
O2	−0.3546 (5)	0.5365 (5)	0.4586 (3)	0.0543 (14)
H2A	−0.3686	0.5032	0.4896	0.082*
O3	0.6673 (6)	0.6400 (5)	−0.1768 (3)	0.0647 (18)
O4	0.5108 (5)	0.4806 (5)	−0.2237 (2)	0.0457 (13)
O5	0.2704 (5)	0.9374 (4)	0.4612 (3)	0.0454 (13)
O6	0.2302 (4)	0.4257 (4)	−0.0370 (2)	0.0399 (12)
O7	0.5578 (6)	1.2102 (5)	0.2881 (3)	0.0543 (15)
O8	0.5509 (6)	1.0224 (4)	0.2742 (3)	0.0494 (14)
O9	0.6426 (5)	1.4194 (4)	0.5551 (2)	0.0464 (13)
O10	0.5319 (5)	1.3324 (4)	0.6270 (2)	0.0394 (12)
O11	0.4969 (5)	0.8197 (4)	0.1316 (2)	0.0449 (13)
O12	0.6428 (5)	0.8862 (4)	0.0670 (2)	0.0418 (12)
C1	−0.1462 (7)	0.1111 (6)	−0.0345 (4)	0.0361 (16)
C2	−0.0211 (7)	0.1088 (6)	−0.0467 (4)	0.0428 (18)
H2B	−0.0040	0.0380	−0.0692	0.051*
C3	0.0809 (7)	0.2095 (6)	−0.0264 (4)	0.0388 (16)
H3	0.1654	0.2059	−0.0355	0.047*
C4	0.0573 (7)	0.3169 (6)	0.0076 (3)	0.0337 (15)
C5	−0.0693 (7)	0.3173 (6)	0.0213 (4)	0.0384 (16)
H5	−0.0872	0.3872	0.0448	0.046*
C6	−0.1708 (7)	0.2149 (6)	0.0006 (4)	0.0413 (17)
H6	−0.2552	0.2169	0.0106	0.050*
C7	−0.2556 (8)	−0.0019 (7)	−0.0646 (5)	0.057 (2)
H7A	−0.2695	−0.0173	−0.1157	0.068*
H7B	−0.2268	−0.0661	−0.0550	0.068*
C8	0.1685 (7)	0.4254 (6)	0.0262 (3)	0.0353 (16)
H8A	0.1362	0.4945	0.0418	0.042*
H8B	0.2299	0.4244	0.0640	0.042*
C9	0.5012 (6)	0.5871 (6)	−0.1053 (3)	0.0290 (14)
C10	0.5482 (6)	0.6885 (6)	−0.0496 (3)	0.0319 (15)
H10	0.6175	0.7478	−0.0544	0.038*
C11	0.4912 (6)	0.7010 (5)	0.0131 (3)	0.0276 (14)
C12	0.3854 (6)	0.6142 (5)	0.0204 (3)	0.0292 (14)
H12	0.3474	0.6229	0.0625	0.035*
C13	0.3370 (6)	0.5134 (6)	−0.0364 (3)	0.0288 (14)
C14	0.3975 (6)	0.4996 (6)	−0.0977 (3)	0.0292 (14)
H14	0.3682	0.4307	−0.1343	0.035*
C15	0.5653 (7)	0.5709 (6)	−0.1724 (3)	0.0371 (16)
C16	0.5470 (6)	0.8082 (6)	0.0738 (4)	0.0327 (15)
C17	0.8880 (8)	1.1430 (6)	0.1590 (4)	0.0411 (17)
H17	0.8309	1.1685	0.1334	0.049*
C18	1.0226 (8)	1.1933 (6)	0.1633 (4)	0.046 (2)
H18	1.0534	1.2496	0.1401	0.056*
C19	1.1086 (8)	1.1587 (7)	0.2019 (4)	0.0459 (19)
H19	1.1981	1.1927	0.2062	0.055*
C20	1.0590 (7)	1.0705 (6)	0.2351 (4)	0.0402 (17)
C21	1.1385 (8)	1.0292 (8)	0.2765 (4)	0.053 (2)
H21	1.2285	1.0616	0.2829	0.063*
C22	1.0880 (8)	0.9433 (7)	0.3074 (4)	0.050 (2)
H22	1.1430	0.9184	0.3347	0.059*
C23	0.9485 (7)	0.8914 (6)	0.2973 (4)	0.0393 (17)
C24	0.8906 (8)	0.8004 (7)	0.3259 (4)	0.050 (2)
H24	0.9414	0.7713	0.3529	0.060*
C25	0.7585 (8)	0.7558 (7)	0.3135 (4)	0.050 (2)
H25	0.7175	0.6966	0.3326	0.060*
C26	0.6857 (8)	0.7995 (7)	0.2721 (4)	0.0477 (19)
H26	0.5957	0.7673	0.2637	0.057*
C27	0.8685 (6)	0.9308 (5)	0.2571 (3)	0.0310 (15)
C28	0.9221 (6)	1.0230 (6)	0.2260 (3)	0.0313 (15)
C29	−0.1206 (7)	0.6371 (6)	0.4644 (4)	0.0413 (17)
C30	0.0053 (7)	0.6274 (6)	0.4551 (4)	0.0397 (17)
H30	0.0187	0.5543	0.4345	0.048*
C31	0.1103 (7)	0.7231 (6)	0.4755 (4)	0.0440 (18)
H31	0.1939	0.7142	0.4687	0.053*
C32	0.0937 (7)	0.8343 (6)	0.5066 (4)	0.0369 (16)
C33	−0.0307 (7)	0.8437 (6)	0.5174 (4)	0.0425 (17)
H33	−0.0439	0.9165	0.5389	0.051*
C34	−0.1376 (7)	0.7458 (7)	0.4967 (4)	0.0440 (18)
H34	−0.2211	0.7539	0.5048	0.053*
C35	−0.2342 (8)	0.5275 (7)	0.4347 (5)	0.053 (2)
H35A	−0.2442	0.5091	0.3834	0.063*
H35B	−0.2116	0.4626	0.4471	0.063*
C36	0.2112 (8)	0.9385 (6)	0.5255 (4)	0.0425 (18)
H36A	0.1847	1.0102	0.5429	0.051*
H36B	0.2720	0.9324	0.5618	0.051*
C37	0.4962 (6)	1.1249 (6)	0.3819 (3)	0.0309 (14)
C38	0.5412 (6)	1.2263 (6)	0.4379 (3)	0.0323 (15)
H38	0.5953	1.2928	0.4303	0.039*
C39	0.5053 (6)	1.2282 (5)	0.5048 (3)	0.0297 (14)
C40	0.4156 (6)	1.1330 (6)	0.5158 (3)	0.0322 (15)
H40	0.3898	1.1353	0.5606	0.039*
C41	0.3647 (6)	1.0339 (6)	0.4586 (3)	0.0329 (15)
C42	0.4105 (6)	1.0285 (6)	0.3932 (3)	0.0309 (15)
H42	0.3834	0.9594	0.3565	0.037*
C43	0.5382 (6)	1.1205 (6)	0.3088 (3)	0.0331 (15)
C44	0.5642 (7)	1.3356 (6)	0.5661 (3)	0.0338 (15)
C45	0.7122 (10)	1.3107 (8)	0.7861 (4)	0.060 (2)
H45	0.6231	1.2770	0.7837	0.072*
C46	0.7972 (11)	1.2714 (9)	0.8224 (5)	0.067 (3)
H46	0.7659	1.2115	0.8429	0.080*
C47	0.9258 (11)	1.3206 (9)	0.8279 (4)	0.068 (3)
H47	0.9837	1.2961	0.8536	0.082*
C48	0.9745 (9)	1.4084 (8)	0.7955 (4)	0.053 (2)
C49	1.1082 (10)	1.4668 (10)	0.7971 (5)	0.073 (3)
H49	1.1708	1.4475	0.8230	0.088*
C50	1.1486 (8)	1.5482 (9)	0.7633 (5)	0.066 (3)
H50	1.2377	1.5822	0.7655	0.079*
C51	1.0560 (7)	1.5836 (7)	0.7236 (4)	0.0444 (19)
C52	1.0886 (8)	1.6664 (7)	0.6858 (4)	0.054 (2)
H52	1.1761	1.7030	0.6852	0.064*
C53	0.9937 (9)	1.6935 (7)	0.6500 (4)	0.056 (2)
H53	1.0153	1.7476	0.6243	0.067*
C54	0.8629 (8)	1.6388 (6)	0.6525 (4)	0.0433 (18)
H54	0.7985	1.6577	0.6277	0.052*
C55	0.9218 (7)	1.5318 (6)	0.7225 (3)	0.0381 (17)
C56	0.8807 (7)	1.4431 (7)	0.7584 (4)	0.0411 (17)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0282 (4)	0.0305 (4)	0.0204 (4)	0.0017 (3)	0.0038 (3)	0.0032 (3)
Zn2	0.0312 (4)	0.0271 (4)	0.0220 (4)	0.0028 (3)	−0.0002 (3)	−0.0015 (3)
N1	0.040 (3)	0.033 (3)	0.023 (3)	0.003 (3)	0.003 (2)	0.004 (2)
N2	0.032 (3)	0.034 (3)	0.043 (3)	0.002 (3)	0.003 (3)	0.012 (3)
N3	0.045 (4)	0.044 (4)	0.031 (3)	0.011 (3)	0.008 (3)	0.012 (3)
N4	0.034 (3)	0.030 (3)	0.029 (3)	0.000 (2)	0.003 (2)	0.006 (2)
O1W	0.056 (3)	0.045 (3)	0.031 (3)	0.019 (3)	0.003 (2)	0.007 (2)
O1	0.039 (3)	0.059 (4)	0.054 (3)	0.003 (3)	0.006 (2)	0.021 (3)
O2W	0.057 (3)	0.045 (3)	0.042 (3)	0.024 (3)	0.000 (3)	0.004 (2)
O2	0.039 (3)	0.059 (4)	0.065 (4)	0.007 (3)	0.005 (3)	0.024 (3)
O3	0.057 (4)	0.069 (4)	0.045 (3)	−0.019 (3)	0.022 (3)	0.008 (3)
O4	0.048 (3)	0.056 (3)	0.024 (2)	0.009 (3)	0.007 (2)	−0.002 (2)
O5	0.048 (3)	0.036 (3)	0.038 (3)	−0.010 (2)	0.014 (2)	0.003 (2)
O6	0.036 (3)	0.038 (3)	0.033 (3)	−0.008 (2)	0.010 (2)	0.004 (2)
O7	0.083 (4)	0.040 (3)	0.043 (3)	0.019 (3)	0.024 (3)	0.012 (2)
O8	0.080 (4)	0.036 (3)	0.040 (3)	0.027 (3)	0.026 (3)	0.009 (2)
O9	0.044 (3)	0.044 (3)	0.034 (3)	−0.008 (2)	0.009 (2)	0.000 (2)
O10	0.050 (3)	0.040 (3)	0.022 (2)	0.007 (2)	0.001 (2)	0.002 (2)
O11	0.056 (3)	0.038 (3)	0.027 (2)	−0.002 (2)	0.003 (2)	−0.001 (2)
O12	0.041 (3)	0.032 (3)	0.038 (3)	−0.002 (2)	0.002 (2)	−0.003 (2)
C1	0.034 (4)	0.040 (4)	0.035 (4)	0.000 (3)	0.003 (3)	0.019 (3)
C2	0.037 (4)	0.037 (4)	0.050 (4)	0.003 (3)	0.008 (3)	0.010 (3)
C3	0.032 (4)	0.046 (4)	0.039 (4)	0.010 (3)	0.009 (3)	0.012 (3)
C4	0.038 (4)	0.037 (4)	0.026 (3)	0.004 (3)	0.003 (3)	0.015 (3)
C5	0.039 (4)	0.034 (4)	0.046 (4)	0.013 (3)	0.010 (3)	0.014 (3)
C6	0.027 (4)	0.046 (4)	0.054 (5)	0.008 (3)	0.009 (3)	0.019 (4)
C7	0.055 (5)	0.049 (5)	0.057 (5)	−0.001 (4)	0.012 (4)	0.012 (4)
C8	0.039 (4)	0.032 (4)	0.029 (3)	−0.001 (3)	0.006 (3)	0.007 (3)
C9	0.030 (3)	0.036 (4)	0.018 (3)	0.008 (3)	0.003 (2)	0.005 (3)
C10	0.029 (3)	0.035 (4)	0.027 (3)	0.001 (3)	0.004 (3)	0.006 (3)
C11	0.030 (3)	0.026 (3)	0.022 (3)	0.006 (3)	−0.002 (3)	0.002 (2)
C12	0.037 (4)	0.030 (3)	0.021 (3)	0.009 (3)	0.006 (3)	0.007 (3)
C13	0.026 (3)	0.034 (4)	0.024 (3)	0.005 (3)	0.005 (3)	0.006 (3)
C14	0.024 (3)	0.032 (3)	0.026 (3)	0.002 (3)	−0.001 (2)	0.002 (3)
C15	0.033 (4)	0.049 (4)	0.027 (3)	0.007 (3)	0.006 (3)	0.009 (3)
C16	0.033 (4)	0.028 (3)	0.036 (4)	0.009 (3)	−0.001 (3)	0.007 (3)
C17	0.053 (5)	0.040 (4)	0.030 (4)	0.009 (4)	0.005 (3)	0.013 (3)
C18	0.062 (5)	0.029 (4)	0.043 (4)	0.003 (4)	0.024 (4)	0.007 (3)
C19	0.042 (4)	0.042 (4)	0.047 (4)	0.002 (3)	0.014 (4)	0.008 (4)
C20	0.037 (4)	0.042 (4)	0.033 (4)	0.001 (3)	0.007 (3)	0.003 (3)
C21	0.031 (4)	0.072 (6)	0.056 (5)	0.013 (4)	0.004 (4)	0.018 (4)
C22	0.041 (4)	0.062 (5)	0.045 (4)	0.015 (4)	−0.004 (3)	0.015 (4)
C23	0.037 (4)	0.048 (4)	0.034 (4)	0.011 (3)	0.007 (3)	0.013 (3)
C24	0.055 (5)	0.057 (5)	0.049 (5)	0.019 (4)	0.008 (4)	0.027 (4)
C25	0.055 (5)	0.039 (4)	0.060 (5)	0.007 (4)	0.020 (4)	0.024 (4)
C26	0.037 (4)	0.041 (4)	0.062 (5)	−0.001 (3)	0.008 (4)	0.020 (4)
C27	0.034 (4)	0.030 (3)	0.024 (3)	0.006 (3)	0.005 (3)	0.001 (3)
C28	0.033 (4)	0.036 (4)	0.021 (3)	0.005 (3)	0.003 (3)	0.005 (3)
C29	0.050 (5)	0.040 (4)	0.037 (4)	0.003 (3)	0.006 (3)	0.024 (3)
C30	0.037 (4)	0.035 (4)	0.044 (4)	0.008 (3)	0.010 (3)	0.006 (3)
C31	0.039 (4)	0.038 (4)	0.053 (5)	0.007 (3)	0.011 (3)	0.011 (3)
C32	0.036 (4)	0.039 (4)	0.040 (4)	0.011 (3)	0.006 (3)	0.018 (3)
C33	0.048 (5)	0.038 (4)	0.048 (4)	0.016 (3)	0.013 (4)	0.019 (3)
C34	0.039 (4)	0.048 (5)	0.054 (5)	0.016 (4)	0.013 (3)	0.024 (4)
C35	0.046 (5)	0.047 (5)	0.061 (5)	0.001 (4)	0.011 (4)	0.016 (4)
C36	0.053 (5)	0.037 (4)	0.035 (4)	0.006 (3)	0.009 (3)	0.009 (3)
C37	0.029 (3)	0.040 (4)	0.021 (3)	0.010 (3)	0.003 (3)	0.003 (3)
C38	0.027 (3)	0.037 (4)	0.026 (3)	0.002 (3)	0.002 (3)	0.003 (3)
C39	0.033 (3)	0.030 (3)	0.026 (3)	0.013 (3)	0.006 (3)	0.002 (3)
C40	0.035 (4)	0.040 (4)	0.027 (3)	0.017 (3)	0.012 (3)	0.010 (3)
C41	0.031 (4)	0.035 (4)	0.028 (3)	0.003 (3)	0.006 (3)	0.005 (3)
C42	0.034 (4)	0.029 (3)	0.023 (3)	0.009 (3)	0.000 (3)	−0.004 (3)
C43	0.033 (4)	0.031 (4)	0.027 (3)	0.006 (3)	0.001 (3)	−0.001 (3)
C44	0.034 (4)	0.035 (4)	0.027 (3)	0.007 (3)	0.004 (3)	0.002 (3)
C45	0.077 (6)	0.060 (5)	0.047 (5)	0.017 (5)	0.014 (4)	0.023 (4)
C46	0.097 (8)	0.068 (6)	0.052 (5)	0.037 (6)	0.017 (5)	0.030 (5)
C47	0.095 (8)	0.090 (7)	0.038 (5)	0.056 (6)	0.001 (5)	0.023 (5)
C48	0.059 (5)	0.067 (6)	0.029 (4)	0.026 (4)	0.002 (4)	−0.001 (4)
C49	0.063 (6)	0.100 (8)	0.057 (6)	0.039 (6)	−0.011 (5)	0.010 (6)
C50	0.034 (4)	0.096 (8)	0.051 (5)	0.015 (5)	−0.008 (4)	−0.005 (5)
C51	0.033 (4)	0.052 (5)	0.035 (4)	0.005 (3)	0.003 (3)	−0.005 (3)
C52	0.041 (5)	0.054 (5)	0.050 (5)	−0.004 (4)	0.017 (4)	−0.001 (4)
C53	0.061 (6)	0.052 (5)	0.042 (4)	−0.005 (4)	0.017 (4)	0.009 (4)
C54	0.054 (5)	0.039 (4)	0.032 (4)	0.006 (4)	0.005 (3)	0.008 (3)
C55	0.036 (4)	0.046 (4)	0.024 (3)	0.006 (3)	0.005 (3)	0.000 (3)
C56	0.044 (4)	0.052 (5)	0.027 (3)	0.019 (4)	0.004 (3)	0.004 (3)

Geometric parameters (Å, º)

Zn1—O10	2.012 (5)	C14—H14	0.9300
Zn1—O4^i	2.013 (5)	C15—Zn1^ii	2.662 (6)
Zn1—N4	2.119 (5)	C17—C18	1.401 (11)
Zn1—O2W	2.145 (5)	C17—H17	0.9300
Zn1—N3	2.215 (6)	C18—C19	1.371 (11)
Zn1—O3^i	2.631 (6)	C18—H18	0.9300
Zn1—C15^i	2.662 (6)	C19—C20	1.418 (10)
Zn2—O8	2.018 (5)	C19—H19	0.9300
Zn2—O11	2.102 (5)	C20—C21	1.410 (11)
Zn2—O1W	2.126 (5)	C20—C28	1.412 (9)
Zn2—N1	2.129 (6)	C21—C22	1.366 (11)
Zn2—N2	2.201 (6)	C21—H21	0.9300
Zn2—O12	2.315 (5)	C22—C23	1.445 (10)
Zn2—C16	2.543 (7)	C22—H22	0.9300
N1—C17	1.323 (9)	C23—C27	1.386 (10)
N1—C28	1.355 (9)	C23—C24	1.406 (10)
N2—C26	1.318 (9)	C24—C25	1.361 (11)
N2—C27	1.362 (8)	C24—H24	0.9300
N3—C45	1.346 (10)	C25—C26	1.384 (11)
N3—C56	1.351 (9)	C25—H25	0.9300
N4—C54	1.319 (9)	C26—H26	0.9300
N4—C55	1.368 (9)	C27—C28	1.437 (9)
O1W—H1C	0.8200	C29—C34	1.378 (10)
O1W—H1D	1.02 (10)	C29—C30	1.385 (10)
O1—C7	1.399 (9)	C29—C35	1.532 (10)
O1—H1	0.8200	C30—C31	1.365 (10)
O2W—H2C	0.8200	C30—H30	0.9300
O2W—H2D	0.86 (10)	C31—C32	1.398 (10)
O2—C35	1.399 (9)	C31—H31	0.9300
O2—H2A	0.8200	C32—C33	1.373 (10)
O3—C15	1.227 (8)	C32—C36	1.506 (10)
O3—Zn1^ii	2.631 (6)	C33—C34	1.393 (10)
O4—C15	1.277 (8)	C33—H33	0.9300
O4—Zn1^ii	2.013 (5)	C34—H34	0.9300
O5—C41	1.369 (8)	C35—H35A	0.9700
O5—C36	1.436 (8)	C35—H35B	0.9700
O6—C13	1.360 (7)	C36—H36A	0.9700
O6—C8	1.432 (7)	C36—H36B	0.9700
O7—C43	1.247 (8)	C37—C42	1.384 (9)
O8—C43	1.260 (8)	C37—C38	1.392 (9)
O9—C44	1.233 (8)	C37—C43	1.517 (9)
O10—C44	1.269 (8)	C38—C39	1.385 (9)
O11—C16	1.267 (8)	C38—H38	0.9300
O12—C16	1.257 (8)	C39—C40	1.391 (9)
C1—C2	1.364 (10)	C39—C44	1.511 (9)
C1—C6	1.372 (10)	C40—C41	1.397 (9)
C1—C7	1.535 (10)	C40—H40	0.9300
C2—C3	1.385 (10)	C41—C42	1.388 (9)
C2—H2B	0.9300	C42—H42	0.9300
C3—C4	1.400 (10)	C45—C46	1.373 (13)
C3—H3	0.9300	C45—H45	0.9300
C4—C5	1.382 (10)	C46—C47	1.339 (14)
C4—C8	1.500 (9)	C46—H46	0.9300
C5—C6	1.395 (10)	C47—C48	1.400 (13)
C5—H5	0.9300	C47—H47	0.9300
C6—H6	0.9300	C48—C56	1.415 (11)
C7—H7A	0.9700	C48—C49	1.421 (13)
C7—H7B	0.9700	C49—C50	1.340 (14)
C8—H8A	0.9700	C49—H49	0.9300
C8—H8B	0.9700	C50—C51	1.441 (12)
C9—C14	1.384 (9)	C50—H50	0.9300
C9—C10	1.392 (9)	C51—C52	1.400 (12)
C9—C15	1.502 (8)	C51—C55	1.408 (10)
C10—C11	1.388 (9)	C52—C53	1.356 (12)
C10—H10	0.9300	C52—H52	0.9300
C11—C12	1.392 (9)	C53—C54	1.398 (11)
C11—C16	1.498 (8)	C53—H53	0.9300
C12—C13	1.401 (8)	C54—H54	0.9300
C12—H12	0.9300	C55—C56	1.443 (10)
C13—C14	1.383 (8)
O10—Zn1—O4^i	99.6 (2)	O11—C16—Zn2	55.5 (3)
O10—Zn1—N4	119.6 (2)	C11—C16—Zn2	173.8 (5)
O4^i—Zn1—N4	139.1 (2)	N1—C17—C18	123.1 (7)
O10—Zn1—O2W	96.3 (2)	N1—C17—H17	118.4
O4^i—Zn1—O2W	94.1 (2)	C18—C17—H17	118.4
N4—Zn1—O2W	92.6 (2)	C19—C18—C17	119.5 (7)
O10—Zn1—N3	95.6 (2)	C19—C18—H18	120.2
O4^i—Zn1—N3	89.7 (2)	C17—C18—H18	120.2
N4—Zn1—N3	76.4 (2)	C18—C19—C20	118.9 (7)
O2W—Zn1—N3	166.8 (2)	C18—C19—H19	120.5
O10—Zn1—O3^i	153.87 (18)	C20—C19—H19	120.5
O4^i—Zn1—O3^i	54.26 (18)	C21—C20—C28	119.2 (7)
N4—Zn1—O3^i	86.08 (18)	C21—C20—C19	123.6 (7)
O2W—Zn1—O3^i	86.4 (2)	C28—C20—C19	117.2 (7)
N3—Zn1—O3^i	85.5 (2)	C22—C21—C20	122.3 (7)
O10—Zn1—C15^i	127.1 (2)	C22—C21—H21	118.8
O4^i—Zn1—C15^i	27.5 (2)	C20—C21—H21	118.8
N4—Zn1—C15^i	112.2 (2)	C21—C22—C23	119.4 (7)
O2W—Zn1—C15^i	91.0 (2)	C21—C22—H22	120.3
N3—Zn1—C15^i	86.5 (2)	C23—C22—H22	120.3
O3^i—Zn1—C15^i	26.79 (18)	C27—C23—C24	118.4 (7)
O8—Zn2—O11	99.5 (2)	C27—C23—C22	119.2 (7)
O8—Zn2—O1W	90.2 (2)	C24—C23—C22	122.4 (7)
O11—Zn2—O1W	104.1 (2)	C25—C24—C23	118.6 (7)
O8—Zn2—N1	116.7 (2)	C25—C24—H24	120.7
O11—Zn2—N1	140.7 (2)	C23—C24—H24	120.7
O1W—Zn2—N1	91.1 (2)	C24—C25—C26	119.3 (7)
O8—Zn2—N2	85.9 (2)	C24—C25—H25	120.4
O11—Zn2—N2	92.0 (2)	C26—C25—H25	120.4
O1W—Zn2—N2	163.9 (2)	N2—C26—C25	123.8 (7)
N1—Zn2—N2	76.7 (2)	N2—C26—H26	118.1
O8—Zn2—O12	155.7 (2)	C25—C26—H26	118.1
O11—Zn2—O12	59.23 (17)	N2—C27—C23	122.4 (6)
O1W—Zn2—O12	84.47 (19)	N2—C27—C28	116.7 (6)
N1—Zn2—O12	87.23 (18)	C23—C27—C28	121.0 (6)
N2—Zn2—O12	105.2 (2)	N1—C28—C20	123.0 (6)
O8—Zn2—C16	128.7 (2)	N1—C28—C27	118.2 (6)
O11—Zn2—C16	29.8 (2)	C20—C28—C27	118.8 (6)
O1W—Zn2—C16	96.1 (2)	C34—C29—C30	118.3 (7)
N1—Zn2—C16	114.0 (2)	C34—C29—C35	123.5 (7)
N2—Zn2—C16	98.5 (2)	C30—C29—C35	118.1 (7)
O12—Zn2—C16	29.52 (19)	C31—C30—C29	121.2 (7)
C17—N1—C28	118.1 (6)	C31—C30—H30	119.4
C17—N1—Zn2	126.8 (5)	C29—C30—H30	119.4
C28—N1—Zn2	115.1 (4)	C30—C31—C32	120.9 (7)
C26—N2—C27	117.5 (6)	C30—C31—H31	119.6
C26—N2—Zn2	129.1 (5)	C32—C31—H31	119.6
C27—N2—Zn2	113.1 (4)	C33—C32—C31	118.0 (7)
C45—N3—C56	117.1 (7)	C33—C32—C36	122.7 (7)
C45—N3—Zn1	129.5 (6)	C31—C32—C36	119.3 (6)
C56—N3—Zn1	113.2 (5)	C32—C33—C34	121.0 (7)
C54—N4—C55	117.5 (6)	C32—C33—H33	119.5
C54—N4—Zn1	126.8 (5)	C34—C33—H33	119.5
C55—N4—Zn1	115.7 (4)	C29—C34—C33	120.5 (7)
Zn2—O1W—H1c	109.5	C29—C34—H34	119.7
Zn2—O1W—H1d	120 (5)	C33—C34—H34	119.7
H1c—O1W—H1d	107.1	O2—C35—C29	115.0 (7)
C7—O1—H1	109.5	O2—C35—H35A	108.5
Zn1—O2W—H2c	109.5	C29—C35—H35A	108.5
Zn1—O2W—H2d	123 (7)	O2—C35—H35B	108.5
H2c—O2W—H2d	109.6	C29—C35—H35B	108.5
C35—O2—H2A	109.5	H35A—C35—H35B	107.5
C15—O3—Zn1^ii	78.0 (4)	O5—C36—C32	105.9 (6)
C15—O4—Zn1^ii	105.8 (4)	O5—C36—H36A	110.5
C41—O5—C36	119.1 (5)	C32—C36—H36A	110.5
C13—O6—C8	120.1 (5)	O5—C36—H36B	110.5
C43—O8—Zn2	131.0 (5)	C32—C36—H36B	110.5
C44—O10—Zn1	109.7 (4)	H36A—C36—H36B	108.7
C16—O11—Zn2	94.8 (4)	C42—C37—C38	119.4 (6)
C16—O12—Zn2	85.3 (4)	C42—C37—C43	120.1 (5)
C2—C1—C6	119.3 (7)	C38—C37—C43	120.5 (6)
C2—C1—C7	118.2 (7)	C39—C38—C37	120.0 (6)
C6—C1—C7	122.3 (7)	C39—C38—H38	120.0
C1—C2—C3	121.4 (7)	C37—C38—H38	120.0
C1—C2—H2B	119.3	C38—C39—C40	120.7 (6)
C3—C2—H2B	119.3	C38—C39—C44	119.1 (6)
C2—C3—C4	120.2 (7)	C40—C39—C44	120.2 (6)
C2—C3—H3	119.9	C39—C40—C41	119.0 (6)
C4—C3—H3	119.9	C39—C40—H40	120.5
C5—C4—C3	117.7 (6)	C41—C40—H40	120.5
C5—C4—C8	123.2 (6)	O5—C41—C42	115.3 (6)
C3—C4—C8	119.1 (6)	O5—C41—C40	124.9 (6)
C4—C5—C6	121.3 (7)	C42—C41—C40	119.9 (6)
C4—C5—H5	119.4	C37—C42—C41	120.6 (6)
C6—C5—H5	119.4	C37—C42—H42	119.7
C1—C6—C5	120.1 (7)	C41—C42—H42	119.7
C1—C6—H6	120.0	O7—C43—O8	125.8 (6)
C5—C6—H6	120.0	O7—C43—C37	119.6 (6)
O1—C7—C1	114.8 (7)	O8—C43—C37	114.5 (6)
O1—C7—H7A	108.6	O9—C44—O10	123.6 (6)
C1—C7—H7A	108.6	O9—C44—C39	119.2 (6)
O1—C7—H7B	108.6	O10—C44—C39	117.2 (6)
C1—C7—H7B	108.6	N3—C45—C46	123.7 (9)
H7A—C7—H7B	107.5	N3—C45—H45	118.1
O6—C8—C4	106.2 (5)	C46—C45—H45	118.1
O6—C8—H8A	110.5	C47—C46—C45	119.0 (9)
C4—C8—H8A	110.5	C47—C46—H46	120.5
O6—C8—H8B	110.5	C45—C46—H46	120.5
C4—C8—H8B	110.5	C46—C47—C48	121.1 (9)
H8A—C8—H8B	108.7	C46—C47—H47	119.4
C14—C9—C10	119.6 (6)	C48—C47—H47	119.4
C14—C9—C15	120.2 (6)	C47—C48—C56	116.4 (8)
C10—C9—C15	120.2 (6)	C47—C48—C49	126.4 (9)
C11—C10—C9	119.8 (6)	C56—C48—C49	117.2 (9)
C11—C10—H10	120.1	C50—C49—C48	123.4 (9)
C9—C10—H10	120.1	C50—C49—H49	118.3
C10—C11—C12	120.6 (5)	C48—C49—H49	118.3
C10—C11—C16	119.2 (6)	C49—C50—C51	120.8 (9)
C12—C11—C16	120.2 (6)	C49—C50—H50	119.6
C11—C12—C13	119.2 (6)	C51—C50—H50	119.6
C11—C12—H12	120.4	C52—C51—C55	116.8 (7)
C13—C12—H12	120.4	C52—C51—C50	125.1 (8)
O6—C13—C14	115.7 (5)	C55—C51—C50	118.1 (8)
O6—C13—C12	124.5 (5)	C53—C52—C51	120.4 (7)
C14—C13—C12	119.8 (6)	C53—C52—H52	119.8
C13—C14—C9	120.9 (6)	C51—C52—H52	119.8
C13—C14—H14	119.6	C52—C53—C54	118.9 (8)
C9—C14—H14	119.6	C52—C53—H53	120.6
O3—C15—O4	121.8 (6)	C54—C53—H53	120.6
O3—C15—C9	121.1 (6)	N4—C54—C53	123.5 (8)
O4—C15—C9	117.0 (6)	N4—C54—H54	118.2
O3—C15—Zn1^ii	75.2 (4)	C53—C54—H54	118.2
O4—C15—Zn1^ii	46.7 (3)	N4—C55—C51	122.8 (7)
C9—C15—Zn1^ii	163.2 (5)	N4—C55—C56	117.2 (6)
O12—C16—O11	120.5 (6)	C51—C55—C56	120.0 (7)
O12—C16—C11	119.9 (6)	N3—C56—C48	122.7 (7)
O11—C16—C11	119.7 (6)	N3—C56—C55	117.0 (6)
O12—C16—Zn2	65.2 (3)	C48—C56—C55	120.4 (7)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O12^iii	0.82	1.99	2.796 (7)	167
O2—H2A···O9^iii	0.82	1.87	2.665 (8)	165
O1W—H1C···O7	0.82	2.05	2.776 (7)	147
O1W—H1D···O1^iv	1.02 (10)	1.80 (10)	2.797 (7)	164 (8)
O2W—H2C···O2^v	0.82	2.06	2.876 (8)	179
O2W—H2D···O7^vi	0.86 (10)	2.05 (10)	2.870 (8)	160 (10)
C3—H3···O12^vii	0.93	2.58	3.460 (9)	158
C19—H19···O3^viii	0.93	2.42	3.150 (9)	135
C45—H45···O11^ix	0.93	2.51	3.176 (10)	128
C2—H2B···Cg1^vii	0.93	2.75	3.558 (8)	146
C30—H30···Cg2^ix	0.93	2.78	3.604 (8)	149
C24—H24···Cg4^x	0.93	2.81	3.609 (8)	145
C53—H53···Cg4^xi	0.93	2.69	3.400 (8)	134

Symmetry codes: (iii) x−1, y−1, z; (iv) −x, −y+1, −z; (v) −x, −y+2, −z+1; (vi) −x+1, −y+3, −z+1; (vii) −x+1, −y+1, −z; (viii) −x+2, −y+2, −z; (ix) −x+1, −y+2, −z+1; (x) x+1, y, z; (xi) x+1, y+1, z.