A novel three-dimensional Zn^II coordination polymer with 1,3,5-tris(imidazol-1-ylmeth­yl)benzene and cyclo­hexane-1,3,5-tri­carboxyl­ate ligands

In the Zn^II compound poly[[bis­([mu]₃-cyclo­hexane-1,3,5-tri­carbox­yl­ato)bis­[[mu]₃-1,3,5-tris­(imidazol-1-yl­methyl)benzene]tri­zinc(II)] hexa­hydrate], {[Zn₃(C₁₈H₁₈N₆)₂(C₉H₉O₆)₂]·6H₂O}_n, based on mixed 1,3,5-tris­(imidazol-1-yl­methyl)benzene and cyclo­hexane-1,3,5-tri­carboxyl­ate ligands, there are two types of crystallographically independent Zn^II centres, one in a general position and one on a crystallographic twofold axis. They have similar fourfold distorted tetra­hedral coordination geometries, ligated by two monodentate carboxyl­ate groups from two cyclo­hexane-1,3,5-tri­carboxyl­ate ligands and by two N atoms from two 1,3,5-tris­(imidazol-1-yl­methyl)benzene lig­ands. The cyclo­hexane-1,3,5-tri­carboxyl­ate anions link the Zn^II cations to generate a two-dimensional layered metal-organic structure running parallel to the (01) plane. Adjacent layers are further connected by tripodal 1,3,5-tris­(imidazol-1-yl­methyl)benzene ligands, resulting in a three-dimensional network. The solvent water mol­ecules are linked to the cyclo­hexane-1,3,5-tri­carboxyl­ate ligands via water-carboxyl­ate O-H...O hydrogen bonds.

S1. Introduction

Supra­molecular assembly of metal–organic coordination frameworks has attracted increasing attention due to the fascinating structures of these frameworks, as well as their potential applications in materials science (Batten & Robson, 1998; Pan et al., 2004; Zhang et al., 2010; Zhong et al., 2011). The polycarboxyl­ate ligands, such as benzene-1,2,4,5-tetra­carboxyl­ate acid (Fabelo et al., 2008), benzene-1,2,3,4-tetra­carboxyl­ate acid (Zhang et al., 2010), benzene-1,2,4-tri­carboxyl­ate acid (Wang et al., 2006), benzene-1,3,5-tri­carboxyl­ate acid (Hao et al., 2012) and cyclo­hexane-1,3,5-tri­carboxyl­ate acid (Lill & Cahill, 2006), have been widely applied in constructing inter­esting coordination polymers, owing to the fact that the carboxyl­ate group may bind to metal ions in various coordination modes and different directions. The crystal engineering of coordination frameworks based on imidazole-containing multidentate ligands has recently received much attention, for example, 1,3,5-tris­(imidazol-1-yl)benzene (Su et al., 2010), 1,3,5-tris­(imidazol-1-yl­methyl)-2,4,6-tri­methyl­benzene (Zhao et al., 2004), 1,2,4,5-tetra­kis(imidazol-1-yl­methyl)­benzene (Hua et al., 2010), 1,3,5-tris­(imidazol-1-yl­methyl)­benzene (Xu et al., 2009), 1,3-bis­(imidazol-1-yl)-5-(imidazol-1-yl­methyl)­benzene (Fan et al., 2003) and 2,4,6-tris­[4-(imidazol-1-yl­methyl)­phenyl]-1,3,5-triazine (Wan et al., 2004) complexes with suitable metal salts have been synthesized and characterized. We have focused our attention on the synthesis of transition metal coordination polymers with mixed polycarboxyl­ate and imidazole-containing multidentate ligands. We report here the crystal structure of the title three-dimensional Zn^II polymeric compound with mixed 1,3,5-tris­(imidazol-1-yl­methyl)­benzene (timb) and cyclo­hexane-1,3,5-tri­carboxyl­ate (chtca) ligands, {[Zn₃(chtca)₂(timb)₂].6H₂O}_n, (I).

S2. Experimental

S2.1. Synthesis and crystallization

ZnSO₄.7H₂O (0.1 mmol), 1,3,5-tris­(imidazol-1-yl­methyl)­benzene (0.1 mmol), cyclo­hexane-1,3,5-tri­carb­oxy­lic acid (0.1 mmol) and water (4.0 ml) were mixed and placed in a thick Pyrex tube, which was sealed and heated to 398 K for 72 h. The tube was then left to cool to ambient temperature [Rephrasing OK?], whereupon colourless block-shaped crystals of (I) were obtained. Analysis, found: C 47.31, H 5.01, N 12.17%; calculated for C₅₄H₆₆N₁₂O₁₈Zn₃: C 47.40, H 4.83, N 12.29%.

S2.2. Refinement

C-bound H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.93–0.98 Å and U_iso(H) = 1.2U_eq(C). Water H atoms were either located in difference density Fourier maps or placed in calculated positions so as to form a reasonable hydrogen-bond network, as far as possible. Initially, their positions were refined with tight restraints on the O—H and H···H distances [0.82 (1) and 1.35 (1) Å, respectively] in order to ensure a reasonable geometry. They were then constrained to ride on their parent O atoms, with U_iso(H) = 1.5U_eq(O). One carboxyl­ate group of a cyclo­hexane-1,3,5-carboxyl­ate ligand is disordered over two positions and was refined as two COO^- groups with site occupancies of 0.800 (6) and 0.200 (6).

S3. Results and discussion

The asymmetric unit of (I) (Fig. 1) contains two crystallographically independent Zn^II centres, one in a general position and one on a twofold crystallographic axis, both with a distorted tetra­hedral ZnN₂O₂ environment. Each Zn^II cation is coordinated by two N atoms from two different tripodal timb ligands and two O atoms from two individual chtca ligands. Atom Zn1 is coordinated by atoms N2, N4ⁱⁱ, O1 and O4ⁱ, and Zn2 is surrounded by atoms N6ⁱ, N6^iv, O6 and O6ⁱⁱⁱ (see Fig. 1 and Table 2 for symmetry codes). The Zn1—N and Zn1—O bond lengths may be compared with the Zn2—N and Zn1—O bond lengths. The N—Zn1—N and O—Zn1—O angles are different from those observed around Zn2 [Values removed to avoid duplication - OK?] (Fig. 1 and Table 2). The slight difference in the Zn—O coordination distances around the two Zn atoms may be attributed to the different degree of distortion around them.

The two monodetentate carboxyl­ate groups of the chtca ligand link two Zn1 atoms to generate a one-dimensional ···Zn–chtca–Zn··· zigzag chain running parallel to the b axis. The remaining carboxyl­ate group of the chtca ligand connects with the Zn2 centre, leading to a two-dimensional layered structure extending parallel to the (201) plane, with approximate Zn···Zn separations of 10.01 (Zn1···Zn1ⁱ), 8.70 (Zn1···Zn2), 18.30 (Zn2···Zn2^viii) and 16.35 Å (Zn2···Zn2^ix). Within the sheets there are 48-membered macrocyclic rings composed of six chtca ligands and six Zn atoms through Zn—O coordination bonds (Fig. 2). The dihedral angles between each pair of the three coordinating COO^- groups of the chtca ligand are 68.6 (3) (O1/C25/O2 and O3/C26/O4), 27.9 (3) (O1/C25/O2 and O5/C27/O6) and 70.3 (5)° (O3/C26/O4 and O5/C27/O6). One carboxyl­ate group of the chtca ligand (O3/C26/O4) is disordered over two positions and was refined with occupancies of 0.800 (6) and 0.200 (6).

The timb ligand, with cis, trans and trans substituent conformations, coordinates to three Zn^II centres (two Zn1 and one Zn2), with approximate metal–metal distances (Zn···Zn) of 12.79 (Zn1···Zn1ⁱⁱ), 11.41 (Zn2^x···Zn1ⁱⁱ) and 7.25 Å (Zn2^x···Zn1), which are evidently different from that observed in the methyl-substituted timb–zinc compound (Zhao et al., 2004). The dihedral angles between the least-squares plane of the timb ligand and those of the coordinated terminal imidazole groups are 77.8 (1) (N1/C12/N2/C11/C10), 68.0 (1) (N3/C15/N4/C14/C13) and 78.0 (1)° (N5/C18/N6/C17/C16). The three planes of the terminal imidazole ring of the timb ligand are oriented with respect to each other at 86.7 (1) (N1/C12/N2/C11/C10 and N3/C15/N4/C14/C13), 75.9 (1) (N1/C12/N2/C11/C10 and N5/C18/N6/C17/C16) and 34.2 (2)° (N3/C15/N4/C14/C13 and N5/C18/N6/C17/C16), which are different from the values found in a previously reported zinc compound (Zhao et al., 2004).

The two timb ligands adopt a face-to-face orientation and are joined together by five Zn^II centres (four Zn1 and one Zn2), giving rise to a one-dimensional screw double chain along the [101] direction (Fig. 3). It is noteworthy that these double chains and the above-mentioned two-dimensional sheets inter­sect each other, resulting in a three-dimensional porous structure (Fig. 4).

Analysis of the crystal packing of (I) shows that the solvent water molecules reside in the porous metal–organic framework via classical inter­molecular O—H···O hydrogen-bonding inter­actions involving the carboxyl­ate groups of the chtca ligands (Table 3 and Fig. 4).

Related literature

For related literature, see: Batten & Robson (1998); Fabelo et al. (2008); Fan et al. (2003); Hao et al. (2012); Hua et al. (2010); Lill & Cahill (2006); Pan et al. (2004); Su et al. (2010); Wan et al. (2004); Wang et al. (2006); Xu et al. (2009); Zhang et al. (2010); Zhao et al. (2004); Zhong et al. (2011).

Computing details

Data collection: CrystalClear (Rigaku, 2007); cell refinement: CrystalClear (Rigaku, 2007); data reduction: CrystalClear (Rigaku, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

Fig. 1. The asymmetric unit of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Dashed lines represent intermolecular O—H···O interactions. All C-bound H atoms have been omitted for clarity. [Symmetry codes: (i) -x + 1/2, y + 1/2, -z + 1/2; (ii) x + 1/2, -y + 1/2, z + 1/2; (iii) -x + 1, y, -z + 3/2; (iv) x + 1/2, y + 1/2, z + 1.]

Fig. 2. The two-dimensional polymeric layer in (I), viewed down the a axis. The 48-membered macrocyclic ring is illustrated. The timb ligand, water molecules and H atoms of the chtca ligand have been omitted for clarity. [Symmetry codes: (i) -x + 1/2, y + 1/2, -z + 1/2; (iii) -x + 1, y, -z + 3/2; (vii) -x + 1/2, y - 1/2, -z + 1/2; (viii) x, y + 1, z; (ix) x - 1/2, y + 1/2, z - 1.]

Fig. 3. The one-dimensional double-chain structure of (I), along the [101] direction. The chtca ligand and water molecules have been omitted for clarity. [Symmetry codes: (ii) x + 1/2, -y + 1/2, z + 1/2; (x) -x + 1, -y + 1, -z + 1.]

Fig. 4. The three-dimensional structure of (I), involving two-dimensional layers (blue, green and purple) and one-dimensional double chains (red), viewed down the b axis, showing interactions between adjacent chains and complex cations. Hydrogen bonds are represented by dashed lines. All C-bound H atoms have been omitted for clarity.

Poly[[bis(µ₃-cyclohexane-1,3,5-tricarboxylato)bis[µ₃-1,3,5-tris(imidazol-1-ylmethyl)benzene]trizinc(II)] hexahydrate]

Crystal data

[Zn3(C18H18N6)2(C9H9O6)2]·6H2O	F(000) = 2832
Mr = 1367.30	Dx = 1.538 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 6396 reflections
a = 25.3826 (8) Å	θ = 2.5–27.4°
b = 18.3013 (5) Å	µ = 1.29 mm^−1
c = 15.0344 (5) Å	T = 223 K
β = 122.244 (1)°	Block, colourless
V = 5906.9 (3) Å^3	0.30 × 0.20 × 0.15 mm
Z = 4

Data collection

Rigaku Mercury CCD area-detector diffractometer	7340 independent reflections
Radiation source: fine-focus sealed tube	5783 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
Detector resolution: 28.5714 pixels mm^-1	θmax = 28.3°, θmin = 1.5°
ω scans	h = −33→32
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	k = −23→24
Tmin = 0.782, Tmax = 1.000	l = −9→20
21212 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.098	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0492P)^2 + 2.9442P] where P = (Fo^2 + 2Fc^2)/3
7340 reflections	(Δ/σ)max = 0.001
421 parameters	Δρmax = 0.62 e Å^−3
36 restraints	Δρmin = −0.43 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	Occ. (<1)
Zn1	0.209200 (11)	0.438330 (12)	0.09148 (2)	0.03888 (8)
Zn2	0.5000	0.379001 (17)	0.7500	0.03712 (9)
O1	0.25408 (7)	0.39896 (8)	0.23844 (13)	0.0502 (4)
O1W	0.10266 (8)	0.20522 (11)	0.11883 (14)	0.0665 (5)
H1WA	0.1319	0.2325	0.1336	0.100*
H1WB	0.0956	0.2070	0.1661	0.100*
O2	0.19061 (8)	0.30946 (10)	0.14750 (13)	0.0608 (5)
O2W	0.45616 (18)	0.14046 (15)	0.7925 (2)	0.1439 (13)
H2WA	0.4918	0.1546	0.8153	0.216*
H2WB	0.4318	0.1750	0.7684	0.216*
O3W	0.35098 (17)	−0.0338 (2)	0.2209 (3)	0.1549 (14)
H3WA	0.3275	−0.0235	0.2410	0.232*
H3WB	0.3559	−0.0782	0.2205	0.232*
O3	0.31544 (13)	0.06600 (12)	0.3318 (2)	0.0615 (8)	0.800 (6)
O3'	0.2919 (5)	0.0530 (5)	0.5084 (10)	0.066 (4)	0.200 (6)
O4	0.27076 (13)	0.03843 (14)	0.4191 (4)	0.0630 (11)	0.800 (6)
O4'	0.2747 (7)	0.0503 (7)	0.3505 (9)	0.064 (5)	0.200 (6)
O5	0.41330 (10)	0.28182 (11)	0.70841 (14)	0.0711 (5)
O6	0.43413 (8)	0.34540 (10)	0.60920 (12)	0.0559 (4)
N1	0.01644 (8)	0.42389 (9)	−0.06275 (14)	0.0387 (4)
N2	0.11558 (8)	0.43952 (9)	−0.00249 (14)	0.0399 (4)
N3	−0.17058 (8)	0.18462 (10)	−0.45415 (14)	0.0424 (4)
N4	−0.24325 (9)	0.11298 (10)	−0.46554 (16)	0.0494 (5)
N5	−0.04348 (8)	0.05094 (9)	−0.11977 (14)	0.0377 (4)
N6	−0.04119 (8)	−0.04597 (9)	−0.20339 (14)	0.0404 (4)
C1	−0.05257 (9)	0.31760 (10)	−0.13575 (17)	0.0394 (5)
C2	−0.08144 (9)	0.31404 (11)	−0.24506 (18)	0.0421 (5)
H2A	−0.0950	0.3567	−0.2846	0.063*
C3	−0.09000 (9)	0.24764 (11)	−0.29475 (16)	0.0384 (4)
C4	−0.06947 (9)	0.18399 (11)	−0.23431 (16)	0.0378 (4)
H4A	−0.0739	0.1393	−0.2671	0.045*
C5	−0.04270 (9)	0.18622 (10)	−0.12683 (16)	0.0355 (4)
C6	−0.03433 (9)	0.25378 (11)	−0.07837 (16)	0.0379 (4)
H6A	−0.0161	0.2558	−0.0059	0.045*
C7	−0.04076 (10)	0.39016 (11)	−0.0800 (2)	0.0485 (6)
H7A	−0.0758	0.4226	−0.1220	0.058*
H7B	−0.0370	0.3828	−0.0130	0.058*
C8	−0.12300 (11)	0.24252 (13)	−0.41316 (17)	0.0485 (5)
H8A	−0.1426	0.2890	−0.4444	0.058*
H8B	−0.0929	0.2321	−0.4324	0.058*
C9	−0.02313 (11)	0.11857 (11)	−0.05905 (17)	0.0436 (5)
H9A	0.0219	0.1181	−0.0134	0.052*
H9B	−0.0402	0.1207	−0.0148	0.052*
C10	0.02043 (11)	0.47979 (13)	−0.11864 (19)	0.0528 (6)
H10A	−0.0125	0.5062	−0.1724	0.063*
C11	0.08133 (11)	0.48925 (13)	−0.08077 (19)	0.0512 (6)
H11A	0.0978	0.5243	−0.1042	0.061*
C12	0.07455 (10)	0.40118 (11)	0.00575 (18)	0.0424 (5)
H12A	0.0847	0.3631	0.0532	0.051*
C13	−0.17828 (15)	0.12976 (16)	−0.5202 (2)	0.0716 (8)
H13A	−0.1570	0.1236	−0.5544	0.086*
C14	−0.22282 (17)	0.08571 (18)	−0.5270 (3)	0.0838 (11)
H14A	−0.2375	0.0433	−0.5672	0.101*
C15	−0.21013 (10)	0.17239 (12)	−0.42341 (19)	0.0459 (5)
H15A	−0.2139	0.2025	−0.3773	0.055*
C16	−0.10301 (11)	0.02342 (12)	−0.1757 (2)	0.0506 (6)
H16A	−0.1378	0.0422	−0.1782	0.061*
C17	−0.10086 (10)	−0.03610 (12)	−0.2263 (2)	0.0510 (6)
H17A	−0.1346	−0.0660	−0.2700	0.061*
C18	−0.00843 (9)	0.00763 (11)	−0.13935 (16)	0.0372 (4)
H18A	0.0339	0.0146	−0.1111	0.045*
C19	0.25828 (9)	0.29043 (10)	0.33223 (17)	0.0400 (5)
H19A	0.2271	0.2916	0.3516	0.048*
C20	0.26628 (11)	0.21048 (11)	0.31258 (19)	0.0521 (6)
H20A	0.2271	0.1921	0.2542	0.063*
H20B	0.2971	0.2071	0.2932	0.063*
C21	0.28638 (10)	0.16433 (11)	0.4071 (2)	0.0506 (6)
H21A	0.2538	0.1669	0.4234	0.061*
C22	0.34694 (10)	0.19285 (11)	0.50283 (18)	0.0457 (5)
H22A	0.3571	0.1641	0.5642	0.055*
H22B	0.3807	0.1874	0.4908	0.055*
C23	0.34084 (10)	0.27337 (11)	0.52354 (17)	0.0395 (4)
H23A	0.3082	0.2758	0.5396	0.047*
C24	0.31853 (10)	0.32010 (10)	0.42588 (16)	0.0383 (4)
H24A	0.3119	0.3698	0.4402	0.046*
H24B	0.3504	0.3212	0.4089	0.046*
C25	0.23249 (9)	0.33541 (11)	0.23277 (17)	0.0409 (5)
C26	0.29175 (16)	0.0835 (2)	0.3814 (5)	0.0426 (8)	0.800 (6)
C26'	0.2853 (6)	0.0848 (8)	0.4302 (15)	0.042 (3)	0.200 (6)
C27	0.39983 (10)	0.30130 (11)	0.61991 (17)	0.0413 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.03507 (13)	0.03259 (13)	0.04489 (15)	0.00156 (9)	0.01859 (11)	0.00365 (10)
Zn2	0.04412 (19)	0.03156 (17)	0.03036 (17)	0.000	0.01630 (14)	0.000
O1	0.0551 (9)	0.0350 (8)	0.0465 (9)	−0.0012 (7)	0.0177 (8)	0.0060 (7)
O1W	0.0547 (10)	0.0871 (13)	0.0557 (11)	−0.0159 (9)	0.0281 (9)	−0.0084 (10)
O2	0.0528 (10)	0.0612 (10)	0.0437 (9)	−0.0127 (8)	0.0092 (8)	0.0056 (8)
O2W	0.209 (4)	0.0795 (17)	0.120 (2)	0.048 (2)	0.073 (3)	0.0434 (17)
O3W	0.165 (3)	0.174 (3)	0.184 (4)	0.027 (3)	0.132 (3)	0.033 (3)
O3	0.0736 (18)	0.0421 (12)	0.0721 (17)	0.0068 (11)	0.0412 (14)	−0.0035 (11)
O3'	0.070 (6)	0.045 (5)	0.077 (8)	−0.015 (4)	0.035 (6)	0.009 (5)
O4	0.0571 (15)	0.0282 (14)	0.117 (4)	−0.0022 (11)	0.056 (2)	−0.0008 (15)
O4'	0.065 (8)	0.035 (6)	0.047 (7)	0.001 (5)	−0.001 (6)	−0.008 (5)
O5	0.1017 (15)	0.0645 (11)	0.0406 (10)	−0.0027 (11)	0.0335 (10)	0.0030 (9)
O6	0.0533 (9)	0.0702 (11)	0.0385 (9)	−0.0208 (8)	0.0207 (8)	−0.0098 (8)
N1	0.0365 (9)	0.0280 (8)	0.0444 (10)	−0.0018 (6)	0.0167 (8)	−0.0039 (7)
N2	0.0385 (9)	0.0327 (8)	0.0417 (10)	−0.0027 (7)	0.0167 (8)	0.0017 (7)
N3	0.0428 (9)	0.0442 (10)	0.0338 (9)	−0.0096 (8)	0.0162 (8)	0.0022 (8)
N4	0.0498 (11)	0.0461 (10)	0.0517 (12)	−0.0132 (8)	0.0267 (9)	−0.0067 (9)
N5	0.0433 (9)	0.0325 (8)	0.0369 (9)	0.0068 (7)	0.0211 (8)	0.0047 (7)
N6	0.0404 (9)	0.0335 (8)	0.0440 (10)	0.0038 (7)	0.0203 (8)	0.0012 (7)
C1	0.0305 (9)	0.0332 (10)	0.0498 (12)	−0.0038 (8)	0.0183 (9)	−0.0065 (9)
C2	0.0362 (10)	0.0331 (10)	0.0484 (12)	−0.0054 (8)	0.0168 (9)	0.0040 (9)
C3	0.0349 (10)	0.0387 (10)	0.0365 (11)	−0.0078 (8)	0.0156 (9)	0.0023 (9)
C4	0.0421 (11)	0.0324 (9)	0.0356 (10)	−0.0036 (8)	0.0185 (9)	−0.0029 (8)
C5	0.0337 (9)	0.0344 (10)	0.0363 (10)	0.0019 (8)	0.0174 (8)	0.0003 (8)
C6	0.0334 (9)	0.0404 (10)	0.0359 (11)	−0.0006 (8)	0.0158 (8)	−0.0056 (9)
C7	0.0390 (11)	0.0378 (11)	0.0671 (16)	−0.0042 (9)	0.0274 (11)	−0.0137 (11)
C8	0.0482 (12)	0.0510 (13)	0.0381 (11)	−0.0172 (10)	0.0174 (10)	0.0054 (10)
C9	0.0536 (12)	0.0397 (11)	0.0333 (11)	0.0077 (9)	0.0203 (10)	0.0000 (9)
C10	0.0459 (12)	0.0446 (12)	0.0467 (13)	0.0023 (10)	0.0105 (10)	0.0108 (10)
C11	0.0494 (13)	0.0454 (12)	0.0476 (13)	−0.0049 (10)	0.0184 (11)	0.0124 (10)
C12	0.0398 (11)	0.0328 (10)	0.0473 (13)	0.0007 (8)	0.0183 (10)	0.0054 (9)
C13	0.092 (2)	0.0764 (19)	0.0719 (19)	−0.0347 (16)	0.0611 (18)	−0.0289 (16)
C14	0.112 (3)	0.082 (2)	0.088 (2)	−0.0521 (19)	0.074 (2)	−0.0472 (18)
C15	0.0457 (12)	0.0425 (11)	0.0490 (13)	−0.0082 (9)	0.0249 (10)	−0.0063 (10)
C16	0.0417 (12)	0.0435 (12)	0.0702 (16)	0.0051 (9)	0.0322 (12)	0.0052 (11)
C17	0.0408 (12)	0.0399 (11)	0.0670 (16)	−0.0023 (9)	0.0253 (11)	−0.0001 (11)
C18	0.0354 (10)	0.0388 (10)	0.0352 (10)	0.0046 (8)	0.0173 (9)	0.0021 (8)
C19	0.0381 (10)	0.0299 (9)	0.0441 (12)	0.0005 (8)	0.0166 (9)	0.0032 (9)
C20	0.0415 (11)	0.0335 (10)	0.0513 (14)	0.0020 (9)	0.0047 (10)	−0.0078 (10)
C21	0.0386 (11)	0.0275 (10)	0.0721 (16)	−0.0012 (8)	0.0203 (11)	0.0035 (10)
C22	0.0431 (11)	0.0298 (10)	0.0498 (13)	0.0003 (8)	0.0151 (10)	0.0053 (9)
C23	0.0415 (11)	0.0350 (10)	0.0409 (11)	−0.0014 (8)	0.0212 (9)	0.0017 (9)
C24	0.0421 (11)	0.0287 (9)	0.0395 (11)	−0.0039 (8)	0.0187 (9)	0.0005 (8)
C25	0.0365 (10)	0.0387 (10)	0.0436 (12)	0.0032 (8)	0.0187 (9)	0.0034 (9)
C26	0.0269 (15)	0.0316 (18)	0.051 (3)	0.0011 (12)	0.0088 (17)	−0.0012 (18)
C26'	0.030 (6)	0.026 (7)	0.048 (9)	0.000 (4)	0.005 (6)	−0.002 (6)
C27	0.0508 (12)	0.0351 (10)	0.0365 (11)	0.0044 (9)	0.0223 (10)	−0.0029 (9)

Geometric parameters (Å, º)

Zn1—O4^i	1.930 (3)	C2—H2A	0.9300
Zn1—O1	2.0032 (16)	C3—C4	1.396 (3)
Zn1—N2	2.0152 (17)	C3—C8	1.513 (3)
Zn1—N4^ii	2.0439 (19)	C4—C5	1.379 (3)
Zn1—O4'^i	2.178 (13)	C4—H4A	0.9300
Zn2—O6	1.9692 (15)	C5—C6	1.393 (3)
Zn2—O6^iii	1.9692 (15)	C5—C9	1.509 (3)
Zn2—N6^iv	2.0619 (17)	C6—H6A	0.9300
Zn2—N6^i	2.0619 (17)	C7—H7A	0.9700
O1—C25	1.269 (2)	C7—H7B	0.9700
O1W—H1WA	0.8203	C8—H8A	0.9700
O1W—H1WB	0.8206	C8—H8B	0.9700
O2—C25	1.243 (3)	C9—H9A	0.9700
O2W—H2WA	0.8202	C9—H9B	0.9700
O2W—H2WB	0.8200	C10—C11	1.343 (3)
O3W—H3WA	0.8201	C10—H10A	0.9300
O3W—H3WB	0.8231	C11—H11A	0.9300
O3—C26	1.225 (6)	C12—H12A	0.9300
O3'—C26'	1.24 (2)	C13—C14	1.347 (4)
O4—C26	1.267 (6)	C13—H13A	0.9300
O4—Zn1^v	1.930 (3)	C14—H14A	0.9300
O4'—C26'	1.25 (2)	C15—H15A	0.9300
O4'—Zn1^v	2.178 (13)	C16—C17	1.346 (3)
O5—C27	1.237 (3)	C16—H16A	0.9300
O6—C27	1.259 (3)	C17—H17A	0.9300
N1—C12	1.337 (3)	C18—H18A	0.9300
N1—C10	1.362 (3)	C19—C25	1.516 (3)
N1—C7	1.468 (3)	C19—C24	1.523 (3)
N2—C12	1.315 (3)	C19—C20	1.528 (3)
N2—C11	1.370 (3)	C19—H19A	0.9800
N3—C15	1.329 (3)	C20—C21	1.490 (3)
N3—C13	1.351 (3)	C20—H20A	0.9700
N3—C8	1.472 (3)	C20—H20B	0.9700
N4—C15	1.312 (3)	C21—C26'	1.500 (17)
N4—C14	1.373 (3)	C21—C22	1.532 (3)
N4—Zn1^vi	2.0439 (19)	C21—C26	1.553 (5)
N5—C18	1.336 (3)	C21—H21A	0.9800
N5—C16	1.374 (3)	C22—C23	1.531 (3)
N5—C9	1.459 (3)	C22—H22A	0.9700
N6—C18	1.314 (3)	C22—H22B	0.9700
N6—C17	1.374 (3)	C23—C27	1.513 (3)
N6—Zn2^vii	2.0619 (17)	C23—C24	1.523 (3)
C1—C6	1.377 (3)	C23—H23A	0.9800
C1—C2	1.399 (3)	C24—H24A	0.9700
C1—C7	1.512 (3)	C24—H24B	0.9700
C2—C3	1.382 (3)
O4^i—Zn1—O1	114.34 (14)	C11—C10—H10A	126.8
O4^i—Zn1—N2	101.30 (11)	N1—C10—H10A	126.8
O1—Zn1—N2	122.76 (7)	C10—C11—N2	109.7 (2)
O4^i—Zn1—N4^ii	99.28 (10)	C10—C11—H11A	125.1
O1—Zn1—N4^ii	100.47 (7)	N2—C11—H11A	125.1
N2—Zn1—N4^ii	116.76 (8)	N2—C12—N1	111.42 (19)
O1—Zn1—O4'^i	91.3 (3)	N2—C12—H12A	124.3
N2—Zn1—O4'^i	99.8 (4)	N1—C12—H12A	124.3
N4^ii—Zn1—O4'^i	125.0 (5)	C14—C13—N3	106.7 (2)
O6—Zn2—O6^iii	143.60 (11)	C14—C13—H13A	126.7
O6—Zn2—N6^iv	106.24 (7)	N3—C13—H13A	126.7
O6^iii—Zn2—N6^iv	97.83 (7)	C13—C14—N4	109.5 (2)
O6—Zn2—N6^i	97.83 (7)	C13—C14—H14A	125.2
O6^iii—Zn2—N6^i	106.24 (7)	N4—C14—H14A	125.2
N6^iv—Zn2—N6^i	96.49 (10)	N4—C15—N3	112.3 (2)
C25—O1—Zn1	106.53 (14)	N4—C15—H15A	123.8
H1WA—O1W—H1WB	109.0	N3—C15—H15A	123.8
H2WA—O2W—H2WB	110.1	C17—C16—N5	106.26 (19)
H3WA—O3W—H3WB	111.9	C17—C16—H16A	126.9
C26—O4—Zn1^v	112.9 (4)	N5—C16—H16A	126.9
C26'—O4'—Zn1^v	101.1 (13)	C16—C17—N6	109.6 (2)
C27—O6—Zn2	108.13 (14)	C16—C17—H17A	125.2
C12—N1—C10	107.11 (18)	N6—C17—H17A	125.2
C12—N1—C7	125.89 (19)	N6—C18—N5	111.64 (18)
C10—N1—C7	126.80 (19)	N6—C18—H18A	124.2
C12—N2—C11	105.29 (18)	N5—C18—H18A	124.2
C12—N2—Zn1	128.68 (15)	C25—C19—C24	114.24 (16)
C11—N2—Zn1	125.44 (14)	C25—C19—C20	111.19 (19)
C15—N3—C13	106.90 (19)	C24—C19—C20	110.42 (17)
C15—N3—C8	125.36 (19)	C25—C19—H19A	106.9
C13—N3—C8	127.4 (2)	C24—C19—H19A	106.9
C15—N4—C14	104.6 (2)	C20—C19—H19A	106.9
C15—N4—Zn1^vi	123.22 (17)	C21—C20—C19	111.8 (2)
C14—N4—Zn1^vi	129.44 (17)	C21—C20—H20A	109.3
C18—N5—C16	106.95 (18)	C19—C20—H20A	109.3
C18—N5—C9	125.87 (18)	C21—C20—H20B	109.3
C16—N5—C9	126.92 (18)	C19—C20—H20B	109.3
C18—N6—C17	105.51 (18)	H20A—C20—H20B	107.9
C18—N6—Zn2^vii	120.58 (14)	C20—C21—C26'	137.0 (8)
C17—N6—Zn2^vii	133.90 (16)	C20—C21—C22	111.36 (18)
C6—C1—C2	119.12 (18)	C26'—C21—C22	104.2 (5)
C6—C1—C7	119.8 (2)	C20—C21—C26	109.5 (3)
C2—C1—C7	121.1 (2)	C22—C21—C26	112.4 (2)
C3—C2—C1	120.59 (19)	C20—C21—H21A	107.8
C3—C2—H2A	119.7	C26'—C21—H21A	82.4
C1—C2—H2A	119.7	C22—C21—H21A	107.8
C2—C3—C4	119.05 (19)	C26—C21—H21A	107.8
C2—C3—C8	121.29 (19)	C23—C22—C21	111.06 (17)
C4—C3—C8	119.63 (19)	C23—C22—H22A	109.4
C5—C4—C3	121.15 (19)	C21—C22—H22A	109.4
C5—C4—H4A	119.4	C23—C22—H22B	109.4
C3—C4—H4A	119.4	C21—C22—H22B	109.4
C4—C5—C6	118.77 (18)	H22A—C22—H22B	108.0
C4—C5—C9	123.07 (18)	C27—C23—C24	113.73 (17)
C6—C5—C9	118.14 (18)	C27—C23—C22	111.36 (17)
C1—C6—C5	121.25 (19)	C24—C23—C22	111.74 (18)
C1—C6—H6A	119.4	C27—C23—H23A	106.5
C5—C6—H6A	119.4	C24—C23—H23A	106.5
N1—C7—C1	110.64 (17)	C22—C23—H23A	106.5
N1—C7—H7A	109.5	C19—C24—C23	111.37 (16)
C1—C7—H7A	109.5	C19—C24—H24A	109.4
N1—C7—H7B	109.5	C23—C24—H24A	109.4
C1—C7—H7B	109.5	C19—C24—H24B	109.4
H7A—C7—H7B	108.1	C23—C24—H24B	109.4
N3—C8—C3	110.65 (17)	H24A—C24—H24B	108.0
N3—C8—H8A	109.5	O2—C25—O1	121.4 (2)
C3—C8—H8A	109.5	O2—C25—C19	119.44 (19)
N3—C8—H8B	109.5	O1—C25—C19	119.20 (19)
C3—C8—H8B	109.5	O3—C26—O4	124.2 (5)
H8A—C8—H8B	108.1	O3—C26—C21	122.5 (4)
N5—C9—C5	113.22 (17)	O4—C26—C21	113.3 (5)
N5—C9—H9A	108.9	O3'—C26'—O4'	121.5 (17)
C5—C9—H9A	108.9	O3'—C26'—C21	131.6 (14)
N5—C9—H9B	108.9	O4'—C26'—C21	107 (2)
C5—C9—H9B	108.9	O5—C27—O6	120.6 (2)
H9A—C9—H9B	107.7	O5—C27—C23	119.8 (2)
C11—C10—N1	106.4 (2)	O6—C27—C23	119.53 (19)
O4^i—Zn1—O1—C25	175.14 (15)	Zn1^vi—N4—C15—N3	162.91 (15)
N2—Zn1—O1—C25	51.98 (16)	C13—N3—C15—N4	−0.1 (3)
N4^ii—Zn1—O1—C25	−79.58 (15)	C8—N3—C15—N4	−173.7 (2)
O4'^i—Zn1—O1—C25	154.5 (5)	C18—N5—C16—C17	0.4 (3)
O6^iii—Zn2—O6—C27	52.96 (14)	C9—N5—C16—C17	174.7 (2)
N6^iv—Zn2—O6—C27	−76.42 (16)	N5—C16—C17—N6	−0.4 (3)
N6^i—Zn2—O6—C27	−175.56 (15)	C18—N6—C17—C16	0.1 (3)
O4^i—Zn1—N2—C12	−147.8 (2)	Zn2^vii—N6—C17—C16	−178.52 (17)
O1—Zn1—N2—C12	−18.9 (2)	C17—N6—C18—N5	0.2 (2)
N4^ii—Zn1—N2—C12	105.60 (19)	Zn2^vii—N6—C18—N5	179.04 (13)
O4'^i—Zn1—N2—C12	−116.8 (4)	C16—N5—C18—N6	−0.4 (2)
O4^i—Zn1—N2—C11	22.1 (2)	C9—N5—C18—N6	−174.73 (18)
O1—Zn1—N2—C11	151.01 (18)	C25—C19—C20—C21	−175.07 (18)
N4^ii—Zn1—N2—C11	−84.5 (2)	C24—C19—C20—C21	57.0 (3)
O4'^i—Zn1—N2—C11	53.1 (4)	C19—C20—C21—C26'	159.3 (11)
C6—C1—C2—C3	−1.8 (3)	C19—C20—C21—C22	−56.8 (3)
C7—C1—C2—C3	177.69 (19)	C19—C20—C21—C26	178.3 (2)
C1—C2—C3—C4	0.1 (3)	C20—C21—C22—C23	54.7 (3)
C1—C2—C3—C8	177.98 (19)	C26'—C21—C22—C23	−149.9 (9)
C2—C3—C4—C5	2.0 (3)	C26—C21—C22—C23	177.9 (3)
C8—C3—C4—C5	−175.93 (19)	C21—C22—C23—C27	178.29 (19)
C3—C4—C5—C6	−2.3 (3)	C21—C22—C23—C24	−53.3 (3)
C3—C4—C5—C9	176.43 (19)	C25—C19—C24—C23	178.59 (17)
C2—C1—C6—C5	1.6 (3)	C20—C19—C24—C23	−55.2 (2)
C7—C1—C6—C5	−177.92 (18)	C27—C23—C24—C19	−178.64 (18)
C4—C5—C6—C1	0.4 (3)	C22—C23—C24—C19	54.2 (2)
C9—C5—C6—C1	−178.35 (19)	Zn1—O1—C25—O2	−1.2 (3)
C12—N1—C7—C1	−71.4 (3)	Zn1—O1—C25—C19	178.98 (15)
C10—N1—C7—C1	102.7 (3)	C24—C19—C25—O2	166.6 (2)
C6—C1—C7—N1	97.1 (2)	C20—C19—C25—O2	40.8 (3)
C2—C1—C7—N1	−82.4 (2)	C24—C19—C25—O1	−13.5 (3)
C15—N3—C8—C3	43.2 (3)	C20—C19—C25—O1	−139.3 (2)
C13—N3—C8—C3	−129.1 (3)	Zn1^v—O4—C26—O3	8.6 (7)
C2—C3—C8—N3	−131.9 (2)	Zn1^v—O4—C26—C21	−169.7 (2)
C4—C3—C8—N3	46.1 (3)	C20—C21—C26—O3	42.9 (4)
C18—N5—C9—C5	99.6 (2)	C26'—C21—C26—O3	−162.1 (13)
C16—N5—C9—C5	−73.6 (3)	C22—C21—C26—O3	−81.4 (5)
C4—C5—C9—N5	−8.4 (3)	C20—C21—C26—O4	−138.8 (4)
C6—C5—C9—N5	170.28 (18)	C26'—C21—C26—O4	16.2 (9)
C12—N1—C10—C11	−0.6 (3)	C22—C21—C26—O4	96.9 (4)
C7—N1—C10—C11	−175.6 (2)	Zn1^v—O4'—C26'—O3'	−10 (2)
N1—C10—C11—N2	0.6 (3)	Zn1^v—O4'—C26'—C21	170.7 (7)
C12—N2—C11—C10	−0.4 (3)	C20—C21—C26'—O3'	−163.3 (10)
Zn1—N2—C11—C10	−172.21 (17)	C22—C21—C26'—O3'	51.2 (18)
C11—N2—C12—N1	0.0 (3)	C26—C21—C26'—O3'	161 (2)
Zn1—N2—C12—N1	171.48 (14)	C20—C21—C26'—O4'	15 (2)
C10—N1—C12—N2	0.4 (3)	C22—C21—C26'—O4'	−130.1 (11)
C7—N1—C12—N2	175.47 (19)	C26—C21—C26'—O4'	−20.3 (10)
C15—N3—C13—C14	0.0 (3)	Zn2—O6—C27—O5	−5.6 (3)
C8—N3—C13—C14	173.4 (3)	Zn2—O6—C27—C23	172.99 (15)
N3—C13—C14—N4	0.2 (4)	C24—C23—C27—O5	159.9 (2)
C15—N4—C14—C13	−0.3 (4)	C22—C23—C27—O5	−72.7 (3)
Zn1^vi—N4—C14—C13	−161.4 (2)	C24—C23—C27—O6	−18.6 (3)
C14—N4—C15—N3	0.2 (3)	C22—C23—C27—O6	108.7 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O2	0.82	1.98	2.790 (2)	169
O1W—H1WB···O5^viii	0.82	2.03	2.844 (3)	174
O2W—H2WB···O5	0.82	2.10	2.830 (3)	148
O2W—H2WA···O2W^iii	0.82	2.59	3.102 (8)	122
O3W—H3WA···O3	0.82	2.26	2.921 (4)	139
O3W—H3WB···O2W^ix	0.82	2.45	3.005 (5)	126

Symmetry codes: (iii) −x+1, y, −z+3/2; (viii) −x+1/2, −y+1/2, −z+1; (ix) x, −y, z−1/2.