Influence of nitrogen-containing chelating ligands on the structures of zinc(II) 4,4'-ethyl­enedibenzo­ates

The Zn^II compounds, [mu]-4,4'-ethyl­enedibenzo­ato-bis­[acetato­aqua­(dipyrido[3,2-a:2',3'-c]phenazine)zinc(II)] dihydrate, [Zn₂(C₂H₃O₂)₂(C₁₆H₁₀O₄)(C₁₈H₁₀N₄)₂(H₂O)₂]·2H₂O, (I), and catena-poly[[[aqua­(pyrazino[2,3-f][1,10]phenanthroline)zinc(II)]-[mu]-4,4'-ethyl­enedibenzo­ato] N,N-dimethyl­formamide hemisolvate], {[Zn(C₁₆H₁₀O₄)(C₁₄H₈N₄)(H₂O)]·0.5C₃H₇NO}_n, (II), display very different structures because of the influence of the N-donor chelating ligands. In (I), the coordination geometry of each Zn^II centre is distorted octa­hedral, involving two N atoms from one dipyrido[3,2-a:2',3'-c]phenazine (L1) ligand, and four O atoms from one bis-chelating acetate anion, one bridging 4,4'-ethyl­enedibenzo­ate (bpea) ligand and one water mol­ecule. Adjacent Zn^II atoms are bridged by one bpea ligand to form a dinuclear complex, and the dinuclear species is centrosymmetric. Two types of [pi]-[pi] inter­actions between neighbouring dinuclear species have been found: one is between the L1 ligands, and the second is between the L1 and bpea ligands. In this way, an inter­esting two-dimensional supra­molecular layer is formed. The layers are further linked by O-H...O and O-H...N hydrogen bonds, generating a three-dimensional supra­molecular network. In (II), each Zn^II atom is square-pyramidally coordinated by two N atoms from one pyrazino[2,3-f][1,10]phenanthroline ligand, three O atoms from two different bpea ligands and one water mol­ecule. The two bpea dianions are situated across inversion centres. The bpea dianions bridge neighbouring Zn^II centres, giving a one-dimensional chain structure in the ab plane. As in (I), two types of [pi]-[pi] inter­actions between neighbouring chains complete a three-dimensional supra­molecular structure. The results indicate that the structures of the N-donor chelating ligands are the dominant factors determining the final supra­molecular structures of the two compounds.

S1. Comment

The rational design and synthesis of novel discrete and polymeric metal–organic compounds have attracted increasing interest due to their fascinating structural topologies and their potential applications as functional materials in catalysis, separation and nonlinear optics (Batten & Robson, 1998; Carlucci et al., 2003; Eddaoudi et al., 2001; Ockwig et al., 2005). Considerable progress has been made in controlling the synthesis of networks with interesting topologies (Yang et al., 2008; Batten, 2001) by varying the factors that affect framework formation; however, it is not possible to predict with complete accuracy the exact structure of the resulting framework. It is therefore important to gain a full understanding of the roles of the factors that influence the formation of metal–organic coordination frameworks (Hagrman et al., 1999).

In general, there are several factors that can influence the network structures of their compounds, such as the coordination environments of metal nodes, and the structural characteristics of the ligands, solvents, templates and counterions (Hu et al., 2006). Among these, the selection of an N-containing ligand is extremely important because, by changing the structures of the N-containing ligands, it is possible to adjust the topologies of coordination frameworks, even for structures containing the same spacer ligand and metal cation (Wang et al., 2005). So far, although the effect of an N-containing ligand on the structures of complexes has been studied, few systematic investigations on the influence of N-containing ligands on their complex structures have been carried out (Tong et al., 2000; Zheng et al., 2001). In particular, the influence of N-containing chelating ligands on network construction through π–π interactions has rarely been documented (Yang, Ma et al., 2007). To the best of our knowlege, the influence of different 1,10-phenanthroline derivatives on the structures of metal–dicarboxylates has not been studied to date (Yang, Li et al., 2007). In this work, we chose biphenylethene-4,4'-dicarboxylic acid (H₂bpea) as the bridging ligand, dipyrido[3,2-a:2',3'-c]-phenazine (L1) and pyrazino[2,3-f][1,10]phenanthroline (L2) as the different N-donor chelating ligands, yielding a centrosymmetric dinuclear complex [Zn₂(L1)₂(bpea)(H₂O)₂]^.2H₂O, (I), and a chain [Zn(L2)(bpea)(H₂O)]^.0.5DMF, (II) (DMF = dimethylformamide).

Selected bond lengths and angles for (I) are given in Table 1. In compound (I), the coordination geometry of each Zn^II centre is distorted octahedral, with two N atoms from one L1, and four O atoms from one bis-chelating acetate anion, one bridging bpea and one water molecule (Fig. 1). The adjacent Zn^II atoms are bridged by one bpea ligand to form a dinuclear complex with a long Zn···Zn distance of 17.405 (3) Å (Fig. 1). The dinuclear species is centrosymmetric, with a crystallographic inversion centre midway between the two Zn^II atoms. Notably, the L1 ligands are arranged in a parallel fashion at both sides of a dinuclear species, leading to a structure suitable for aromatic intercalation. Two types of π–π interactions between neighbouring dinuclear species have been found: one is between the L1 ligands [centroid-to-centroid distance of 3.555 (2) Å, vertical face-to-face distance of 3.483 (1) Å, and dihedral angle of 2.212 (1)°], and the second is between the L1 and bpea anion [centroid-to-centroid distance of 4.027 (2) Å, vertical face-to-face distance of 3.505 (1) Å, and dihedral angle of 2.720 (2)°] (Fig. 2). In these modes, a two-dimensional supramolecular layer is formed (Fig. 2). The layers are further linked by O—H···O and O—H···N hydrogen bonds, generating a three-dimensional supramolecular network (Table 2).

It is noteworthy that the structure of (I) is different from that of the related dinuclear structure [Pb(L1)(adip)]₂ (adip is adipate; Yang, Ma et al., 2007), in which the two adip ligands link the two Pb^II centres to give a dinuclear species. A two-dimensional supramolecular layer is formed through only one type of π–π interaction between L1 ligands of neighbouring dinuclear species. The structure of (I) is also entirely different from that of the related polymer [Mn₂(L1)(dpdc)₂]_n (dpdc is the 2,2'-diphenyldicarboxylate dianion; Che et al., 2008). In that structure, four Mn^II atoms are bridged by the carboxylate groups of the dpdc ligands to form an unusual tetranuclear Mn^II cluster; the clusters are further connected together by the aromatic backbone of the dicarboxylate ligands, forming a one-dimensional chain structure along the b axis.

To investigate the influence of N-donor chelating ligands on the complex frameworks, a relatively small ligand L2 was used under the same reaction conditions as for (I), and a structurally different coordination polymer [Zn(L2)(bpea)(H₂O)]^.0.5DMF, (II), was obtained from the reaction system. As shown in Fig. 3, each Zn^II atom is square-pyramidally coordinated by two N atoms from one L2 ligand, three O atoms from two different bpea ligands and one water molecule. The average Zn—O and Zn—N distances in (II) are comparable with those observed for (I) (Table 3). The two bpea dianions are situated across inversion centres. As depicted in Fig. 4, the bpea dianions bridge two neighbouring Zn^II centres, giving a one-dimensional chain structure in the ab plane. Clearly, the N-containing chelating ligand L2 plays an important role in the formation of the chain structure. Two N atoms from the secondary L2 ligand occupy two coordination positions of the Zn^II atom, while the remaining coordination positions are available for bpea ligands, allowing the formation of the chain structure. As in (I), two types of π–π interactions between neighbouring chains have been found: one is between the L2 ligands [centroid-to-centroid distance of 3.705 (1) Å, vertical face-to-face distance of 3.430 (3) Å, and dihedral angle of 0.000 (1)°], and the second is between L2 and bpea anions [centroid-to-centroid distance of 3.632 (1) Å, vertical face-to-face distance of 3.424 (1) Å, and dihedral angle of 5.150 (7)°] (Fig. 5). In these modes, a three-dimensional supramolecular structure is formed (Fig. 5). The O—H···O hydrogen bonds further consolidated the structure of (II) (Table 4).

It is noteworthy that the structure of (II) is entirely different from that of the related structure [Cd₂(L2)₂(1,4-ndc)₂] (1,4-ndc is 1,4-naphthalenedicarboxylate; Qiao et al., 2008), where the tetranuclear cadmium carboxylate clusters are connected together by the aromatic backbone of the dicarboxylate ligands, forming a three-dimensional α-polonium net.

In summary, by varying the N-containing chelating ligand under the same synthesis conditions, two structurally different Zn^II complexes are obtained. In contrast to L2, the bulky phenyl groups in the backbone significantly increase the steric hindrance of the L1 ligand, leading to the formation of (I) and (II) with quite different structures. Therefore, the structures of the N-containing chelating ligands are the dominant factor determining the final supramolecular structures of the two compounds.

Related literature

For related literature, see: Batten (2001); Batten & Robson (1998); Carlucci et al. (2003); Che et al. (2008); Eddaoudi et al. (2001); Hagrman et al. (1999); Hu et al. (2006); Ockwig et al. (2005); Qiao et al. (2008); Tong et al. (2000); Wang et al. (2005); Yang et al. (2008); Yang, Li, Cao, Yue, Li & Chen (2007); Yang, Ma, Liu, Ma & Batten (2007); Zheng et al. (2001).

S2. Experimental

Zn(CH₃COO)₂.2H₂O (0.110 g, 0.5 mmol), H₂bpea (0.133 g, 0.5 mmol) and L1 (0.118 g, 0.5 mmol) were dissolved in a mixed solution of DMF (9 ml) and distilled water (5 ml). The resulting mixture was stirred for about 1 h at room temperature, sealed in a 23 ml Teflon-lined stainless steel autoclave, and heated at 398 K for 8 d under autogenous pressure. The reaction system was gradually cooled to room temperature at a rate of 5 K h^-1. Pale yellow crystals of (I) suitable for single-crystal X-ray diffraction analysis were collected from the final reaction system by filtration, washed several times with DMF, and dried in air at ambient temperature (yield 55% based on Zn^II).

Compound (II) was prepared in the same way as (I), using L2 as an N-donor chelating ligand. Pale yellow crystals were obtained (yield 47% based on Zn^II).

S3. Refinement

For (I) and (II), all H atoms were positioned geometrically (C—H = 0.93 Å) and refined as riding, with U_iso(H)=1.2U_eq(carrier). The water H atoms were located in a difference Fourier, and were refined with distance restraints of O—H 0.85±0.01 and H···H 1.39±0.01 Å. Their temperature factors were freely refined.

The DMF molecule of (II) is disordered about a centre of inversion. The C—O length was restrained to 1.25±0.01 Å, the N–C(carbonyl) length was restrained to 1.35±0.01 Å and the other two N—C lengths to 1.45±0.01 Å. The atoms were restrained to lie on a plane. The anisotropic temperature factors were restrained to be nearly isotropic.

Computing details

For both compounds, data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. A view of the local coordination of the Zn^II cation in (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level [symmetry operation (i): 1 - x, 1 - y, 2 - z].
	Fig. 2. A view of the two-dimensional supramolecular structure of (I).
	Fig. 3. A view of the local coordination of the Zn^II cation in (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level [symmetry operations (i): 3 - x, -y, 1 - z; (ii): 3 - x, 2 - y, -z].
	Fig. 4. A view of the one-dimensional chain of (II).
	Fig. 5. A iew of the three-dimensional supramolecular structure of (II).

(I) µ-4,4'-ethylenedicarboxylato-bis[acetatoaqua(dipyrido[3,2-a:2',3'- c]phenazine)zinc(II)] dihydrate

Crystal data

[Zn2(C2H3O2)2(C16H10O4)(C18H10N4)2(H2O)2]·2H2O	F(000) = 1184
Mr = 1151.73	Dx = 1.546 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4853 reflections
a = 13.1521 (12) Å	θ = 1.1–26.0°
b = 11.9082 (11) Å	µ = 1.05 mm^−1
c = 15.9668 (15) Å	T = 293 K
β = 98.391 (2)°	Block, pale yellow
V = 2473.9 (4) Å^3	0.33 × 0.30 × 0.27 mm
Z = 2

Data collection

Bruker APEX diffractometer	4853 independent reflections
Radiation source: fine-focus sealed tube	3145 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.056
ϕ and ω scans	θmax = 26.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −16→15
Tmin = 0.701, Tmax = 0.755	k = −14→14
13276 measured reflections	l = −11→19

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.116	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0509P)^2 + 0.3893P] where P = (Fo^2 + 2Fc^2)/3
4853 reflections	(Δ/σ)max = 0.001
368 parameters	Δρmax = 0.97 e Å^−3
6 restraints	Δρmin = −0.32 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
C1	1.1960 (3)	0.2598 (3)	0.7662 (2)	0.0391 (10)
H1	1.2227	0.2363	0.8205	0.047*
C2	1.2583 (3)	0.3210 (3)	0.7205 (2)	0.0387 (10)
H2	1.3248	0.3400	0.7445	0.046*
C3	1.2210 (3)	0.3536 (3)	0.6392 (2)	0.0362 (9)
H3	1.2620	0.3947	0.6075	0.043*
C4	1.1203 (3)	0.3242 (3)	0.6047 (2)	0.0288 (8)
C5	1.0621 (2)	0.2653 (3)	0.6559 (2)	0.0260 (8)
C6	0.9543 (2)	0.2354 (3)	0.6260 (2)	0.0248 (8)
C7	0.9085 (2)	0.2682 (3)	0.5453 (2)	0.0265 (8)
C8	0.8049 (3)	0.2408 (3)	0.5223 (2)	0.0332 (9)
H8	0.7708	0.2618	0.4695	0.040*
C9	0.7534 (3)	0.1831 (3)	0.5775 (2)	0.0352 (9)
H9	0.6846	0.1640	0.5626	0.042*
C10	0.8065 (3)	0.1539 (3)	0.6560 (2)	0.0306 (8)
H10	0.7718	0.1143	0.6933	0.037*
C11	0.9694 (3)	0.3267 (3)	0.4896 (2)	0.0280 (8)
C12	1.0743 (3)	0.3544 (3)	0.5183 (2)	0.0273 (8)
C13	1.0871 (3)	0.4338 (3)	0.3895 (2)	0.0312 (8)
C14	0.9822 (3)	0.4082 (3)	0.3616 (2)	0.0300 (8)
C15	0.9365 (3)	0.4426 (3)	0.2792 (2)	0.0382 (9)
H15	0.8676	0.4275	0.2602	0.046*
C16	0.9949 (3)	0.4979 (3)	0.2287 (2)	0.0436 (11)
H16	0.9651	0.5210	0.1750	0.052*
C17	1.0998 (3)	0.5209 (3)	0.2562 (2)	0.0400 (10)
H17	1.1381	0.5582	0.2203	0.048*
C18	1.1449 (3)	0.4894 (3)	0.3337 (2)	0.0403 (10)
H18	1.2143	0.5042	0.3508	0.048*
C19	0.9122 (3)	0.2949 (3)	0.9302 (2)	0.0367 (9)
C20	0.8166 (3)	0.3448 (3)	0.9548 (2)	0.0335 (9)
C21	0.8161 (3)	0.3905 (3)	1.0340 (2)	0.0429 (10)
H21	0.8761	0.3897	1.0729	0.052*
C22	0.7276 (3)	0.4378 (3)	1.0566 (3)	0.0449 (10)
H22	0.7293	0.4691	1.1101	0.054*
C23	0.6363 (3)	0.4390 (3)	1.0000 (2)	0.0366 (9)
C24	0.6372 (3)	0.3898 (3)	0.9203 (2)	0.0372 (9)
H24	0.5770	0.3882	0.8817	0.045*
C25	0.7248 (3)	0.3443 (3)	0.8986 (2)	0.0347 (9)
H25	0.7233	0.3122	0.8453	0.042*
C26	0.5445 (3)	0.4913 (3)	1.0252 (2)	0.0397 (10)
H26	0.5486	0.5143	1.0813	0.048*
C27	0.9690 (3)	−0.0637 (3)	0.8031 (2)	0.0339 (9)
C28	0.9534 (3)	−0.1872 (3)	0.8150 (3)	0.0522 (11)
H28A	0.8965	−0.1985	0.8456	0.078*
H28B	1.0144	−0.2190	0.8464	0.078*
H28C	0.9391	−0.2230	0.7607	0.078*
N1	1.0988 (2)	0.2329 (2)	0.73566 (17)	0.0287 (7)
N2	0.9046 (2)	0.1798 (2)	0.68043 (18)	0.0275 (7)
N3	0.9244 (2)	0.3537 (2)	0.41198 (17)	0.0318 (7)
N4	1.1320 (2)	0.4061 (2)	0.46899 (18)	0.0316 (7)
O1	0.90388 (18)	0.2547 (2)	0.85523 (15)	0.0367 (6)
O2	0.9939 (2)	0.2967 (2)	0.98203 (17)	0.0499 (7)
O1W	1.1021 (2)	0.1477 (3)	0.91089 (15)	0.0368 (6)
HW11	1.072 (3)	0.196 (2)	0.939 (2)	0.052 (15)*
HW12	1.115 (3)	0.091 (2)	0.943 (2)	0.055 (14)*
O3	0.91071 (19)	0.0049 (2)	0.83334 (16)	0.0390 (6)
O2W	1.1392 (3)	−0.0398 (3)	1.00433 (18)	0.0506 (8)
HW21	1.116 (4)	−0.022 (4)	1.049 (2)	0.10 (2)*
HW22	1.201 (2)	−0.059 (6)	1.019 (4)	0.19 (4)*
O4	1.03961 (19)	−0.0296 (2)	0.76466 (16)	0.0413 (7)
Zn1	0.99354 (3)	0.14710 (4)	0.80232 (3)	0.03063 (15)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.032 (2)	0.054 (3)	0.028 (2)	−0.0035 (19)	−0.0059 (17)	0.004 (2)
C2	0.027 (2)	0.055 (3)	0.031 (2)	−0.0093 (18)	−0.0020 (17)	0.0034 (19)
C3	0.030 (2)	0.048 (2)	0.030 (2)	−0.0052 (19)	0.0058 (16)	0.006 (2)
C4	0.0301 (19)	0.032 (2)	0.0241 (18)	0.0005 (16)	0.0026 (16)	0.0017 (16)
C5	0.0268 (19)	0.0278 (19)	0.0229 (18)	0.0041 (15)	0.0022 (15)	−0.0010 (16)
C6	0.0256 (18)	0.0278 (19)	0.0198 (18)	0.0027 (15)	−0.0004 (15)	−0.0008 (15)
C7	0.0270 (19)	0.0289 (19)	0.0229 (18)	0.0080 (15)	0.0017 (15)	−0.0010 (16)
C8	0.031 (2)	0.046 (2)	0.0201 (18)	0.0032 (18)	−0.0037 (16)	0.0019 (18)
C9	0.0219 (19)	0.051 (2)	0.032 (2)	−0.0004 (17)	−0.0005 (16)	0.0000 (19)
C10	0.0275 (19)	0.036 (2)	0.0276 (19)	0.0010 (17)	0.0018 (15)	0.0015 (18)
C11	0.035 (2)	0.029 (2)	0.0201 (17)	0.0075 (16)	0.0021 (16)	0.0016 (15)
C12	0.0342 (19)	0.0279 (19)	0.0203 (17)	0.0039 (17)	0.0058 (15)	0.0004 (17)
C13	0.045 (2)	0.0244 (19)	0.0251 (19)	0.0040 (17)	0.0090 (17)	−0.0005 (17)
C14	0.045 (2)	0.0239 (19)	0.0213 (18)	0.0053 (17)	0.0052 (17)	0.0007 (16)
C15	0.047 (2)	0.041 (2)	0.025 (2)	0.0030 (19)	−0.0005 (18)	0.0008 (19)
C16	0.074 (3)	0.037 (2)	0.0198 (19)	0.005 (2)	0.006 (2)	0.0012 (18)
C17	0.055 (3)	0.039 (2)	0.028 (2)	0.002 (2)	0.014 (2)	0.0042 (19)
C18	0.049 (2)	0.039 (2)	0.034 (2)	0.0016 (19)	0.009 (2)	0.0059 (19)
C19	0.046 (2)	0.034 (2)	0.029 (2)	0.0006 (19)	0.002 (2)	0.0022 (18)
C20	0.040 (2)	0.033 (2)	0.0265 (19)	−0.0006 (18)	0.0021 (17)	0.0002 (18)
C21	0.049 (2)	0.045 (2)	0.032 (2)	0.009 (2)	−0.002 (2)	−0.0030 (19)
C22	0.055 (3)	0.048 (3)	0.030 (2)	0.007 (2)	0.000 (2)	−0.005 (2)
C23	0.047 (2)	0.028 (2)	0.037 (2)	0.0026 (18)	0.0113 (19)	0.0059 (18)
C24	0.040 (2)	0.041 (2)	0.030 (2)	−0.0034 (18)	0.0028 (18)	0.0035 (18)
C25	0.043 (2)	0.036 (2)	0.0250 (19)	−0.0031 (18)	0.0053 (17)	−0.0003 (18)
C26	0.056 (3)	0.033 (2)	0.032 (2)	0.003 (2)	0.0098 (19)	0.0039 (19)
C27	0.033 (2)	0.042 (2)	0.025 (2)	0.0034 (18)	−0.0039 (18)	−0.0020 (18)
C28	0.063 (3)	0.045 (3)	0.049 (3)	0.001 (2)	0.008 (2)	0.008 (2)
N1	0.0266 (16)	0.0391 (18)	0.0190 (15)	−0.0011 (13)	−0.0012 (13)	0.0073 (14)
N2	0.0248 (15)	0.0329 (17)	0.0247 (16)	0.0005 (13)	0.0029 (13)	−0.0007 (14)
N3	0.0376 (17)	0.0348 (17)	0.0214 (15)	0.0029 (15)	−0.0014 (13)	−0.0008 (15)
N4	0.0363 (17)	0.0340 (17)	0.0250 (16)	0.0034 (14)	0.0067 (14)	0.0011 (14)
O1	0.0383 (15)	0.0471 (17)	0.0229 (13)	0.0061 (12)	−0.0015 (12)	0.0020 (13)
O2	0.0473 (17)	0.0581 (18)	0.0397 (16)	0.0056 (15)	−0.0088 (14)	−0.0124 (15)
O1W	0.0317 (15)	0.0511 (18)	0.0264 (14)	0.0015 (14)	0.0004 (12)	0.0065 (16)
O3	0.0395 (15)	0.0458 (16)	0.0317 (14)	0.0116 (13)	0.0058 (12)	0.0029 (13)
O2W	0.056 (2)	0.066 (2)	0.0315 (16)	0.0160 (16)	0.0087 (15)	0.0060 (16)
O4	0.0359 (15)	0.0478 (17)	0.0406 (16)	0.0044 (13)	0.0069 (13)	0.0066 (14)
Zn1	0.0280 (2)	0.0409 (3)	0.0218 (2)	−0.0013 (2)	−0.00023 (17)	0.0054 (2)

Geometric parameters (Å, º)

C1—N1	1.339 (4)	C17—H17	0.9300
C1—C2	1.382 (5)	C18—H18	0.9300
C1—H1	0.9300	C19—O2	1.257 (4)
C2—C3	1.374 (5)	C19—O1	1.278 (4)
C2—H2	0.9300	C19—C20	1.495 (5)
C3—C4	1.403 (5)	C20—C21	1.377 (5)
C3—H3	0.9300	C20—C25	1.395 (5)
C4—C5	1.389 (4)	C21—C22	1.387 (5)
C4—C12	1.468 (4)	C21—H21	0.9300
C5—N1	1.350 (4)	C22—C23	1.394 (5)
C5—C6	1.472 (4)	C22—H22	0.9300
C6—N2	1.337 (4)	C23—C24	1.402 (5)
C6—C7	1.396 (4)	C23—C26	1.466 (5)
C7—C8	1.397 (5)	C24—C25	1.363 (5)
C7—C11	1.458 (5)	C24—H24	0.9300
C8—C9	1.371 (5)	C25—H25	0.9300
C8—H8	0.9300	C26—C26^i	1.337 (7)
C9—C10	1.388 (5)	C26—H26	0.9300
C9—H9	0.9300	C27—O4	1.253 (4)
C10—N2	1.328 (4)	C27—O3	1.264 (4)
C10—H10	0.9300	C27—C28	1.501 (5)
C11—N3	1.332 (4)	C28—H28A	0.9600
C11—C12	1.429 (5)	C28—H28B	0.9600
C12—N4	1.323 (4)	C28—H28C	0.9600
C13—N4	1.361 (4)	O1W—HW11	0.854 (18)
C13—C18	1.416 (5)	O1W—HW12	0.856 (18)
C13—C14	1.421 (5)	O2W—HW21	0.84 (4)
C14—N3	1.350 (4)	O2W—HW22	0.84 (2)
C14—C15	1.424 (5)	Zn1—N1	2.127 (3)
C15—C16	1.363 (5)	Zn1—N2	2.155 (3)
C15—H15	0.9300	Zn1—O1	2.009 (2)
C16—C17	1.412 (5)	Zn1—O3	2.111 (3)
C16—H16	0.9300	Zn1—O4	2.294 (3)
C17—C18	1.347 (5)	Zn1—O1W	2.079 (2)
N1—C1—C2	122.9 (3)	C20—C21—C22	121.0 (4)
N1—C1—H1	118.6	C20—C21—H21	119.5
C2—C1—H1	118.6	C22—C21—H21	119.5
C3—C2—C1	119.3 (3)	C21—C22—C23	120.8 (4)
C3—C2—H2	120.3	C21—C22—H22	119.6
C1—C2—H2	120.3	C23—C22—H22	119.6
C2—C3—C4	119.1 (3)	C22—C23—C24	117.6 (4)
C2—C3—H3	120.5	C22—C23—C26	119.5 (3)
C4—C3—H3	120.5	C24—C23—C26	122.9 (4)
C5—C4—C3	117.7 (3)	C25—C24—C23	121.1 (4)
C5—C4—C12	119.4 (3)	C25—C24—H24	119.5
C3—C4—C12	122.9 (3)	C23—C24—H24	119.5
N1—C5—C4	123.2 (3)	C24—C25—C20	121.2 (3)
N1—C5—C6	115.5 (3)	C24—C25—H25	119.4
C4—C5—C6	121.2 (3)	C20—C25—H25	119.4
N2—C6—C7	123.5 (3)	C26^i—C26—C23	125.8 (5)
N2—C6—C5	116.6 (3)	C26^i—C26—H26	117.1
C7—C6—C5	119.8 (3)	C23—C26—H26	117.1
C6—C7—C8	116.8 (3)	O4—C27—O3	120.8 (4)
C6—C7—C11	119.7 (3)	O4—C27—C28	120.3 (4)
C8—C7—C11	123.5 (3)	O3—C27—C28	118.8 (3)
C9—C8—C7	120.2 (3)	O4—C27—Zn1	64.7 (2)
C9—C8—H8	119.9	O3—C27—Zn1	56.33 (19)
C7—C8—H8	119.9	C28—C27—Zn1	172.9 (3)
C8—C9—C10	118.4 (3)	C27—C28—H28A	109.5
C8—C9—H9	120.8	C27—C28—H28B	109.5
C10—C9—H9	120.8	H28A—C28—H28B	109.5
N2—C10—C9	123.1 (3)	C27—C28—H28C	109.5
N2—C10—H10	118.5	H28A—C28—H28C	109.5
C9—C10—H10	118.5	H28B—C28—H28C	109.5
N3—C11—C12	121.3 (3)	C1—N1—C5	117.7 (3)
N3—C11—C7	118.3 (3)	C1—N1—Zn1	126.1 (2)
C12—C11—C7	120.3 (3)	C5—N1—Zn1	116.1 (2)
N4—C12—C11	121.8 (3)	C10—N2—C6	118.1 (3)
N4—C12—C4	118.7 (3)	C10—N2—Zn1	126.8 (2)
C11—C12—C4	119.5 (3)	C6—N2—Zn1	115.1 (2)
N4—C13—C18	120.0 (3)	C11—N3—C14	117.3 (3)
N4—C13—C14	120.6 (3)	C12—N4—C13	117.4 (3)
C18—C13—C14	119.3 (3)	C19—O1—Zn1	131.1 (2)
N3—C14—C13	121.5 (3)	Zn1—O1W—HW11	97 (3)
N3—C14—C15	119.3 (3)	Zn1—O1W—HW12	124 (3)
C13—C14—C15	119.2 (3)	HW11—O1W—HW12	106 (2)
C16—C15—C14	119.2 (4)	C27—O3—Zn1	93.8 (2)
C16—C15—H15	120.4	HW21—O2W—HW22	106 (3)
C14—C15—H15	120.4	C27—O4—Zn1	85.7 (2)
C15—C16—C17	121.3 (4)	O1—Zn1—O1W	91.20 (11)
C15—C16—H16	119.4	O1—Zn1—O3	93.34 (10)
C17—C16—H16	119.4	O1W—Zn1—O3	97.04 (10)
C18—C17—C16	120.8 (4)	O1—Zn1—N1	111.64 (11)
C18—C17—H17	119.6	O1W—Zn1—N1	89.85 (10)
C16—C17—H17	119.6	O3—Zn1—N1	153.98 (11)
C17—C18—C13	120.2 (4)	O1—Zn1—N2	89.42 (10)
C17—C18—H18	119.9	O1W—Zn1—N2	165.64 (11)
C13—C18—H18	119.9	O3—Zn1—N2	97.25 (10)
O2—C19—O1	124.8 (4)	N1—Zn1—N2	76.61 (10)
O2—C19—C20	119.4 (3)	O1—Zn1—O4	152.73 (10)
O1—C19—C20	115.8 (3)	O1W—Zn1—O4	92.66 (11)
C21—C20—C25	118.2 (4)	O3—Zn1—O4	59.40 (10)
C21—C20—C19	121.0 (3)	N1—Zn1—O4	95.36 (10)
C25—C20—C19	120.7 (3)	N2—Zn1—O4	93.35 (10)
N1—C1—C2—C3	−1.9 (6)	C5—C6—N2—C10	178.5 (3)
C1—C2—C3—C4	0.2 (6)	C7—C6—N2—Zn1	−177.4 (3)
C2—C3—C4—C5	1.6 (5)	C5—C6—N2—Zn1	0.6 (4)
C2—C3—C4—C12	−179.4 (3)	C12—C11—N3—C14	0.2 (5)
C3—C4—C5—N1	−1.8 (5)	C7—C11—N3—C14	179.8 (3)
C12—C4—C5—N1	179.1 (3)	C13—C14—N3—C11	1.1 (5)
C3—C4—C5—C6	177.3 (3)	C15—C14—N3—C11	−177.7 (3)
C12—C4—C5—C6	−1.7 (5)	C11—C12—N4—C13	1.0 (5)
N1—C5—C6—N2	0.0 (4)	C4—C12—N4—C13	−179.5 (3)
C4—C5—C6—N2	−179.2 (3)	C18—C13—N4—C12	179.9 (3)
N1—C5—C6—C7	178.0 (3)	C14—C13—N4—C12	0.3 (5)
C4—C5—C6—C7	−1.1 (5)	O2—C19—O1—Zn1	19.1 (6)
N2—C6—C7—C8	0.4 (5)	C20—C19—O1—Zn1	−162.2 (2)
C5—C6—C7—C8	−177.6 (3)	O4—C27—O3—Zn1	−5.3 (3)
N2—C6—C7—C11	−178.8 (3)	C28—C27—O3—Zn1	173.8 (3)
C5—C6—C7—C11	3.3 (5)	O3—C27—O4—Zn1	4.9 (3)
C6—C7—C8—C9	−0.9 (5)	C28—C27—O4—Zn1	−174.3 (3)
C11—C7—C8—C9	178.3 (3)	C19—O1—Zn1—O1W	−5.7 (3)
C7—C8—C9—C10	0.5 (5)	C19—O1—Zn1—O3	91.5 (3)
C8—C9—C10—N2	0.4 (5)	C19—O1—Zn1—N1	−96.0 (3)
C6—C7—C11—N3	177.9 (3)	C19—O1—Zn1—N2	−171.3 (3)
C8—C7—C11—N3	−1.3 (5)	C19—O1—Zn1—O4	92.5 (4)
C6—C7—C11—C12	−2.5 (5)	C19—O1—Zn1—C27	90.1 (3)
C8—C7—C11—C12	178.4 (3)	C27—O3—Zn1—O1	−177.7 (2)
N3—C11—C12—N4	−1.3 (5)	C27—O3—Zn1—O1W	−86.0 (2)
C7—C11—C12—N4	179.1 (3)	C27—O3—Zn1—N1	18.3 (3)
N3—C11—C12—C4	179.2 (3)	C27—O3—Zn1—N2	92.5 (2)
C7—C11—C12—C4	−0.4 (5)	C27—O3—Zn1—O4	2.89 (18)
C5—C4—C12—N4	−177.0 (3)	C1—N1—Zn1—O1	95.0 (3)
C3—C4—C12—N4	4.0 (5)	C5—N1—Zn1—O1	−83.2 (3)
C5—C4—C12—C11	2.5 (5)	C1—N1—Zn1—O1W	3.7 (3)
C3—C4—C12—C11	−176.5 (3)	C5—N1—Zn1—O1W	−174.5 (3)
N4—C13—C14—N3	−1.4 (5)	C1—N1—Zn1—O3	−102.2 (3)
C18—C13—C14—N3	179.0 (3)	C5—N1—Zn1—O3	79.6 (3)
N4—C13—C14—C15	177.4 (3)	C1—N1—Zn1—N2	178.9 (3)
C18—C13—C14—C15	−2.2 (5)	C5—N1—Zn1—N2	0.7 (2)
N3—C14—C15—C16	179.7 (3)	C1—N1—Zn1—O4	−88.9 (3)
C13—C14—C15—C16	0.9 (5)	C5—N1—Zn1—O4	92.9 (2)
C14—C15—C16—C17	0.5 (6)	C1—N1—Zn1—C27	−91.2 (3)
C15—C16—C17—C18	−0.6 (6)	C5—N1—Zn1—C27	90.6 (3)
C16—C17—C18—C13	−0.8 (6)	C10—N2—Zn1—O1	−65.9 (3)
N4—C13—C18—C17	−177.4 (3)	C6—N2—Zn1—O1	111.7 (2)
C14—C13—C18—C17	2.2 (5)	C10—N2—Zn1—O1W	−158.5 (4)
O2—C19—C20—C21	−1.3 (6)	C6—N2—Zn1—O1W	19.1 (6)
O1—C19—C20—C21	179.9 (3)	C10—N2—Zn1—O3	27.4 (3)
O2—C19—C20—C25	179.9 (3)	C6—N2—Zn1—O3	−155.0 (2)
O1—C19—C20—C25	1.1 (5)	C10—N2—Zn1—N1	−178.4 (3)
C25—C20—C21—C22	−1.8 (6)	C6—N2—Zn1—N1	−0.7 (2)
C19—C20—C21—C22	179.3 (4)	C10—N2—Zn1—O4	86.9 (3)
C20—C21—C22—C23	0.8 (6)	C6—N2—Zn1—O4	−95.4 (2)
C21—C22—C23—C24	0.7 (6)	C10—N2—Zn1—C27	57.5 (3)
C21—C22—C23—C26	−179.0 (4)	C6—N2—Zn1—C27	−124.9 (2)
C22—C23—C24—C25	−1.2 (6)	C27—O4—Zn1—O1	−4.1 (3)
C26—C23—C24—C25	178.5 (3)	C27—O4—Zn1—O1W	93.7 (2)
C23—C24—C25—C20	0.1 (6)	C27—O4—Zn1—O3	−2.92 (18)
C21—C20—C25—C24	1.4 (6)	C27—O4—Zn1—N1	−176.2 (2)
C19—C20—C25—C24	−179.8 (3)	C27—O4—Zn1—N2	−99.4 (2)
C22—C23—C26—C26^i	172.6 (5)	O4—C27—Zn1—O1	177.74 (17)
C24—C23—C26—C26^i	−7.1 (7)	O3—C27—Zn1—O1	2.8 (2)
C2—C1—N1—C5	1.7 (5)	O4—C27—Zn1—O1W	−88.1 (2)
C2—C1—N1—Zn1	−176.5 (3)	O3—C27—Zn1—O1W	96.9 (2)
C4—C5—N1—C1	0.2 (5)	O4—C27—Zn1—O3	175.0 (3)
C6—C5—N1—C1	−179.0 (3)	O4—C27—Zn1—N1	4.6 (2)
C4—C5—N1—Zn1	178.6 (3)	O3—C27—Zn1—N1	−170.35 (18)
C6—C5—N1—Zn1	−0.6 (4)	O4—C27—Zn1—N2	83.5 (2)
C9—C10—N2—C6	−0.9 (5)	O3—C27—Zn1—N2	−91.5 (2)
C9—C10—N2—Zn1	176.7 (3)	O3—C27—Zn1—O4	−175.0 (3)
C7—C6—N2—C10	0.5 (5)

Symmetry code: (i) −x+1, −y+1, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—HW12···O2W	0.86 (2)	1.84 (2)	2.690 (4)	175 (4)
O1W—HW11···O2	0.85 (2)	1.79 (2)	2.634 (4)	170 (4)
O2W—HW21···O3^ii	0.84 (4)	1.97 (2)	2.796 (4)	166 (5)
O2W—HW22···N4^iii	0.84 (2)	2.22 (2)	3.045 (4)	168 (6)

Symmetry codes: (ii) −x+2, −y, −z+2; (iii) −x+5/2, y−1/2, −z+3/2.

(II) catena-poly[[[aqua(pyrazino[2,3-f][1,10]phenanthroline)zinc(II)]-µ- 4,4'-ethylenedicarboxylato] N,N-dimethylformamide hemisolvate]

Crystal data

[Zn(C16H10O4)(C14H8N4)(H2O)]·0.5C3H7NO	Z = 2
Mr = 618.42	F(000) = 636
Triclinic, P1	Dx = 1.462 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 11.2278 (11) Å	Cell parameters from 5517 reflections
b = 11.3944 (11) Å	θ = 1.1–26.1°
c = 11.8165 (11) Å	µ = 0.93 mm^−1
α = 84.345 (2)°	T = 293 K
β = 69.421 (2)°	Block, pale yellow
γ = 83.982 (1)°	0.25 × 0.21 × 0.19 mm
V = 1404.4 (2) Å^3

Data collection

Bruker APEX diffractometer	5517 independent reflections
Radiation source: fine-focus sealed tube	4209 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
ϕ and ω scans	θmax = 26.1°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→11
Tmin = 0.788, Tmax = 0.837	k = −14→14
7901 measured reflections	l = −14→7

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.119	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0622P)^2 + 0.0289P] where P = (Fo^2 + 2Fc^2)/3
5517 reflections	(Δ/σ)max < 0.001
416 parameters	Δρmax = 0.70 e Å^−3
39 restraints	Δρmin = −0.33 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	0.92306 (3)	0.48063 (3)	0.28067 (3)	0.03635 (13)
O1	1.0196 (2)	0.35468 (19)	0.36014 (19)	0.0460 (5)
O2	1.1400 (3)	0.2748 (3)	0.1898 (2)	0.0933 (11)
O3	1.0386 (2)	0.61041 (19)	0.25607 (18)	0.0453 (5)
O4	1.0663 (2)	0.5834 (2)	0.0661 (2)	0.0517 (6)
O5	0.9305 (2)	0.3588 (2)	0.1621 (2)	0.0452 (5)
H5A	1.0011 (16)	0.327 (3)	0.164 (2)	0.046 (10)*
H5B	0.931 (3)	0.381 (3)	0.0923 (14)	0.067 (13)*
N1	0.7821 (2)	0.5086 (2)	0.4535 (2)	0.0355 (6)
N2	0.3724 (3)	0.7116 (2)	0.6486 (2)	0.0494 (7)
N3	0.3540 (2)	0.7773 (2)	0.4194 (3)	0.0483 (7)
N4	0.7685 (2)	0.5784 (2)	0.2355 (2)	0.0395 (6)
C1	1.1102 (3)	0.2869 (3)	0.3005 (3)	0.0483 (8)
C2	1.1913 (3)	0.2168 (3)	0.3640 (3)	0.0400 (7)
C3	1.1615 (3)	0.2119 (3)	0.4881 (3)	0.0436 (8)
H3	1.0869	0.2516	0.5362	0.052*
C4	1.2421 (3)	0.1485 (3)	0.5409 (3)	0.0457 (8)
H4	1.2201	0.1452	0.6247	0.055*
C5	1.3556 (3)	0.0895 (3)	0.4721 (3)	0.0389 (7)
C6	1.3826 (3)	0.0930 (3)	0.3488 (3)	0.0521 (9)
H6	1.4565	0.0523	0.3007	0.063*
C7	1.3031 (3)	0.1552 (3)	0.2955 (3)	0.0520 (9)
H7	1.3242	0.1564	0.2120	0.062*
C8	1.4441 (3)	0.0271 (3)	0.5285 (3)	0.0433 (8)
H8	1.4188	0.0258	0.6125	0.052*
C9	1.0905 (3)	0.6338 (3)	0.1432 (3)	0.0377 (7)
C10	1.1883 (3)	0.7234 (3)	0.1024 (3)	0.0374 (7)
C11	1.2051 (3)	0.7942 (3)	0.1821 (3)	0.0484 (8)
H11	1.1555	0.7866	0.2637	0.058*
C12	1.2964 (3)	0.8778 (3)	0.1413 (3)	0.0537 (9)
H12	1.3065	0.9253	0.1964	0.064*
C13	1.3720 (3)	0.8910 (3)	0.0202 (3)	0.0478 (8)
C14	1.3547 (4)	0.8185 (3)	−0.0578 (3)	0.0634 (11)
H14	1.4047	0.8252	−0.1394	0.076*
C15	1.2650 (3)	0.7357 (3)	−0.0183 (3)	0.0570 (9)
H15	1.2560	0.6875	−0.0735	0.068*
C16	1.4709 (4)	0.9774 (3)	−0.0281 (4)	0.0604 (10)
H16	1.4923	1.0009	−0.1099	0.073*
C17	0.7930 (3)	0.4742 (3)	0.5600 (3)	0.0404 (7)
H17	0.8662	0.4289	0.5621	0.049*
C18	0.6993 (3)	0.5033 (3)	0.6687 (3)	0.0473 (8)
H18	0.7100	0.4779	0.7420	0.057*
C19	0.5917 (3)	0.5692 (3)	0.6671 (3)	0.0437 (8)
H19	0.5280	0.5888	0.7393	0.052*
C20	0.5773 (3)	0.6071 (2)	0.5565 (3)	0.0360 (7)
C21	0.6757 (3)	0.5747 (2)	0.4516 (3)	0.0325 (6)
C22	0.4665 (3)	0.6785 (3)	0.5461 (3)	0.0387 (7)
C23	0.2746 (3)	0.7765 (3)	0.6331 (3)	0.0576 (10)
H23	0.2092	0.8030	0.7012	0.069*
C24	0.2640 (3)	0.8075 (3)	0.5200 (4)	0.0544 (9)
H24	0.1907	0.8510	0.5157	0.065*
C25	0.4572 (3)	0.7132 (3)	0.4318 (3)	0.0393 (7)
C26	0.5605 (3)	0.6796 (3)	0.3231 (3)	0.0388 (7)
C27	0.6672 (3)	0.6121 (2)	0.3333 (3)	0.0345 (7)
C28	0.5582 (3)	0.7118 (3)	0.2066 (3)	0.0531 (9)
H28	0.4884	0.7569	0.1960	0.064*
C29	0.6594 (3)	0.6766 (3)	0.1086 (3)	0.0599 (10)
H29	0.6587	0.6965	0.0306	0.072*
C30	0.7632 (3)	0.6110 (3)	0.1263 (3)	0.0511 (9)
H30	0.8322	0.5888	0.0587	0.061*
O6	1.2083 (13)	0.0650 (11)	0.8305 (11)	0.225 (6)	0.50
N5	1.0380 (9)	0.0152 (9)	0.9902 (10)	0.105 (4)	0.50
C31	1.1435 (11)	0.0708 (9)	0.9406 (12)	0.140 (5)	0.50
H31	1.1701	0.1150	0.9882	0.168*	0.50
C32	0.9893 (17)	−0.0557 (15)	0.9220 (17)	0.144 (7)	0.50
H32A	1.0253	−0.0330	0.8371	0.215*	0.50
H32B	0.8981	−0.0427	0.9480	0.215*	0.50
H32C	1.0126	−0.1379	0.9361	0.215*	0.50
C33	0.9620 (16)	0.0206 (15)	1.1188 (11)	0.148 (8)	0.50
H33A	1.0146	0.0405	1.1619	0.222*	0.50
H33B	0.9293	−0.0549	1.1504	0.222*	0.50
H33C	0.8923	0.0798	1.1286	0.222*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0304 (2)	0.0369 (2)	0.0422 (2)	−0.00262 (14)	−0.01328 (15)	−0.00171 (15)
O1	0.0421 (12)	0.0468 (13)	0.0498 (13)	0.0107 (10)	−0.0194 (10)	−0.0074 (11)
O2	0.090 (2)	0.129 (3)	0.0573 (18)	0.062 (2)	−0.0351 (15)	−0.0260 (17)
O3	0.0452 (12)	0.0542 (13)	0.0383 (13)	−0.0182 (10)	−0.0153 (10)	0.0071 (10)
O4	0.0554 (14)	0.0545 (14)	0.0498 (14)	−0.0222 (12)	−0.0185 (11)	−0.0049 (11)
O5	0.0483 (14)	0.0433 (13)	0.0480 (15)	−0.0042 (11)	−0.0220 (11)	−0.0007 (11)
N1	0.0349 (13)	0.0334 (13)	0.0408 (14)	−0.0048 (11)	−0.0162 (11)	−0.0002 (11)
N2	0.0440 (16)	0.0435 (16)	0.0489 (17)	−0.0035 (13)	−0.0008 (13)	−0.0044 (13)
N3	0.0387 (15)	0.0456 (16)	0.0618 (19)	0.0032 (12)	−0.0203 (14)	−0.0053 (14)
N4	0.0336 (13)	0.0492 (15)	0.0354 (14)	−0.0019 (11)	−0.0120 (11)	−0.0025 (12)
C1	0.0444 (19)	0.053 (2)	0.046 (2)	0.0062 (16)	−0.0170 (15)	−0.0018 (16)
C2	0.0397 (17)	0.0380 (17)	0.0438 (19)	−0.0003 (14)	−0.0171 (14)	−0.0019 (14)
C3	0.0379 (17)	0.0415 (18)	0.048 (2)	0.0032 (14)	−0.0115 (14)	−0.0030 (15)
C4	0.051 (2)	0.0453 (19)	0.0410 (18)	−0.0021 (15)	−0.0165 (15)	−0.0006 (15)
C5	0.0419 (17)	0.0305 (15)	0.0473 (19)	−0.0024 (13)	−0.0196 (14)	−0.0011 (14)
C6	0.052 (2)	0.054 (2)	0.048 (2)	0.0166 (17)	−0.0183 (16)	−0.0081 (17)
C7	0.053 (2)	0.058 (2)	0.0415 (19)	0.0174 (17)	−0.0181 (16)	−0.0068 (16)
C8	0.0470 (18)	0.0367 (17)	0.049 (2)	−0.0011 (14)	−0.0221 (15)	0.0012 (14)
C9	0.0297 (15)	0.0363 (16)	0.0481 (19)	−0.0033 (13)	−0.0161 (14)	0.0037 (14)
C10	0.0356 (16)	0.0372 (16)	0.0423 (18)	−0.0080 (13)	−0.0170 (14)	0.0032 (14)
C11	0.049 (2)	0.051 (2)	0.047 (2)	−0.0141 (16)	−0.0170 (16)	0.0031 (16)
C12	0.061 (2)	0.045 (2)	0.070 (3)	−0.0098 (17)	−0.038 (2)	−0.0074 (18)
C13	0.0378 (18)	0.051 (2)	0.052 (2)	−0.0125 (15)	−0.0118 (15)	0.0073 (16)
C14	0.059 (2)	0.073 (3)	0.053 (2)	−0.029 (2)	−0.0047 (18)	−0.0028 (19)
C15	0.057 (2)	0.063 (2)	0.051 (2)	−0.0244 (19)	−0.0118 (17)	−0.0049 (18)
C16	0.064 (2)	0.059 (2)	0.062 (2)	−0.0140 (19)	−0.0240 (18)	−0.0046 (19)
C17	0.0416 (17)	0.0393 (17)	0.0431 (18)	−0.0026 (14)	−0.0183 (14)	−0.0016 (14)
C18	0.056 (2)	0.0487 (19)	0.0388 (18)	−0.0059 (16)	−0.0198 (16)	0.0031 (15)
C19	0.0451 (19)	0.0448 (18)	0.0368 (18)	−0.0077 (15)	−0.0073 (14)	−0.0039 (14)
C20	0.0344 (16)	0.0338 (16)	0.0386 (17)	−0.0089 (13)	−0.0094 (13)	−0.0022 (13)
C21	0.0315 (15)	0.0274 (14)	0.0390 (16)	−0.0054 (12)	−0.0124 (12)	−0.0006 (12)
C22	0.0341 (16)	0.0311 (15)	0.0468 (19)	−0.0081 (13)	−0.0074 (14)	−0.0025 (14)
C23	0.0406 (19)	0.047 (2)	0.068 (3)	−0.0009 (16)	0.0037 (17)	−0.0080 (18)
C24	0.0342 (18)	0.048 (2)	0.075 (3)	0.0018 (15)	−0.0118 (18)	−0.0040 (19)
C25	0.0343 (16)	0.0326 (16)	0.0508 (19)	−0.0032 (13)	−0.0137 (14)	−0.0050 (14)
C26	0.0351 (16)	0.0389 (17)	0.0441 (18)	−0.0026 (13)	−0.0165 (14)	−0.0010 (14)
C27	0.0314 (15)	0.0326 (15)	0.0402 (17)	−0.0043 (12)	−0.0128 (13)	−0.0021 (13)
C28	0.045 (2)	0.064 (2)	0.051 (2)	0.0117 (17)	−0.0232 (16)	0.0021 (17)
C29	0.057 (2)	0.084 (3)	0.040 (2)	0.011 (2)	−0.0225 (17)	0.0017 (18)
C30	0.0429 (19)	0.070 (2)	0.0372 (19)	0.0023 (17)	−0.0116 (15)	−0.0042 (17)
O6	0.255 (10)	0.238 (9)	0.172 (8)	0.007 (8)	−0.077 (7)	0.023 (7)
N5	0.103 (8)	0.110 (7)	0.110 (6)	0.031 (6)	−0.053 (7)	−0.027 (5)
C31	0.167 (9)	0.146 (9)	0.111 (8)	0.002 (7)	−0.061 (7)	0.003 (7)
C32	0.141 (10)	0.138 (10)	0.160 (10)	0.013 (8)	−0.059 (8)	−0.045 (8)
C33	0.151 (11)	0.130 (10)	0.148 (10)	0.012 (8)	−0.039 (8)	−0.011 (8)

Geometric parameters (Å, º)

Zn1—O3	2.002 (2)	C13—C14	1.371 (5)
Zn1—O5	2.043 (2)	C13—C16	1.483 (5)
Zn1—O1	2.059 (2)	C14—C15	1.379 (5)
Zn1—N1	2.128 (2)	C14—H14	0.9300
Zn1—N4	2.160 (2)	C15—H15	0.9300
O1—C1	1.252 (4)	C16—C16^ii	1.255 (7)
O2—C1	1.249 (4)	C16—H16	0.9300
O3—C9	1.267 (3)	C17—C18	1.388 (4)
O4—C9	1.243 (4)	C17—H17	0.9300
O5—H5A	0.842 (10)	C18—C19	1.359 (4)
O5—H5B	0.835 (10)	C18—H18	0.9300
N1—C17	1.325 (4)	C19—C20	1.394 (4)
N1—C21	1.348 (4)	C19—H19	0.9300
N2—C23	1.317 (4)	C20—C21	1.391 (4)
N2—C22	1.354 (4)	C20—C22	1.450 (4)
N3—C24	1.310 (4)	C21—C27	1.455 (4)
N3—C25	1.348 (4)	C22—C25	1.406 (4)
N4—C30	1.327 (4)	C23—C24	1.391 (5)
N4—C27	1.359 (4)	C23—H23	0.9300
C1—C2	1.497 (4)	C24—H24	0.9300
C2—C3	1.382 (4)	C25—C26	1.449 (4)
C2—C7	1.392 (4)	C26—C27	1.389 (4)
C3—C4	1.379 (4)	C26—C28	1.397 (4)
C3—H3	0.9300	C28—C29	1.366 (5)
C4—C5	1.392 (4)	C28—H28	0.9300
C4—H4	0.9300	C29—C30	1.385 (5)
C5—C6	1.378 (4)	C29—H29	0.9300
C5—C8	1.470 (4)	C30—H30	0.9300
C6—C7	1.367 (4)	O6—C31	1.251 (9)
C6—H6	0.9300	N5—C31	1.321 (9)
C7—H7	0.9300	N5—C32	1.460 (9)
C8—C8^i	1.317 (6)	N5—C33	1.462 (9)
C8—H8	0.9300	C31—H31	0.9300
C9—C10	1.498 (4)	C32—H32A	0.9600
C10—C11	1.371 (4)	C32—H32B	0.9600
C10—C15	1.385 (4)	C32—H32C	0.9600
C11—C12	1.399 (4)	C33—H33A	0.9600
C11—H11	0.9300	C33—H33B	0.9600
C12—C13	1.386 (5)	C33—H33C	0.9600
C12—H12	0.9300
O3—Zn1—O5	128.13 (9)	C14—C13—C16	118.9 (3)
O3—Zn1—O1	97.25 (9)	C12—C13—C16	123.5 (3)
O5—Zn1—O1	87.82 (9)	C13—C14—C15	121.7 (3)
O3—Zn1—N1	103.52 (9)	C13—C14—H14	119.1
O5—Zn1—N1	128.18 (9)	C15—C14—H14	119.1
O1—Zn1—N1	89.82 (9)	C14—C15—C10	120.8 (3)
O3—Zn1—N4	99.89 (9)	C14—C15—H15	119.6
O5—Zn1—N4	89.00 (10)	C10—C15—H15	119.6
O1—Zn1—N4	160.43 (9)	C16^ii—C16—C13	128.0 (5)
N1—Zn1—N4	77.07 (9)	C16^ii—C16—H16	116.0
C1—O1—Zn1	123.0 (2)	C13—C16—H16	116.0
C9—O3—Zn1	108.28 (18)	N1—C17—C18	122.4 (3)
Zn1—O5—H5A	93 (2)	N1—C17—H17	118.8
Zn1—O5—H5B	120 (3)	C18—C17—H17	118.8
H5A—O5—H5B	113.2 (17)	C19—C18—C17	119.4 (3)
C17—N1—C21	118.3 (3)	C19—C18—H18	120.3
C17—N1—Zn1	126.3 (2)	C17—C18—H18	120.3
C21—N1—Zn1	115.29 (19)	C18—C19—C20	119.6 (3)
C23—N2—C22	115.7 (3)	C18—C19—H19	120.2
C24—N3—C25	116.1 (3)	C20—C19—H19	120.2
C30—N4—C27	117.8 (3)	C21—C20—C19	117.5 (3)
C30—N4—Zn1	128.1 (2)	C21—C20—C22	119.1 (3)
C27—N4—Zn1	114.09 (19)	C19—C20—C22	123.4 (3)
O2—C1—O1	124.5 (3)	N1—C21—C20	122.8 (3)
O2—C1—C2	116.9 (3)	N1—C21—C27	116.9 (2)
O1—C1—C2	118.6 (3)	C20—C21—C27	120.3 (3)
C3—C2—C7	118.1 (3)	N2—C22—C25	120.7 (3)
C3—C2—C1	123.0 (3)	N2—C22—C20	118.6 (3)
C7—C2—C1	118.9 (3)	C25—C22—C20	120.7 (3)
C4—C3—C2	120.2 (3)	N2—C23—C24	123.4 (3)
C4—C3—H3	119.9	N2—C23—H23	118.3
C2—C3—H3	119.9	C24—C23—H23	118.3
C3—C4—C5	121.7 (3)	N3—C24—C23	122.1 (3)
C3—C4—H4	119.2	N3—C24—H24	119.0
C5—C4—H4	119.2	C23—C24—H24	119.0
C6—C5—C4	117.4 (3)	N3—C25—C22	122.0 (3)
C6—C5—C8	121.2 (3)	N3—C25—C26	118.2 (3)
C4—C5—C8	121.4 (3)	C22—C25—C26	119.8 (3)
C7—C6—C5	121.3 (3)	C27—C26—C28	117.7 (3)
C7—C6—H6	119.3	C27—C26—C25	119.4 (3)
C5—C6—H6	119.3	C28—C26—C25	122.9 (3)
C6—C7—C2	121.2 (3)	N4—C27—C26	122.8 (3)
C6—C7—H7	119.4	N4—C27—C21	116.5 (3)
C2—C7—H7	119.4	C26—C27—C21	120.7 (3)
C8^i—C8—C5	126.2 (4)	C29—C28—C26	119.3 (3)
C8^i—C8—H8	116.9	C29—C28—H28	120.3
C5—C8—H8	116.9	C26—C28—H28	120.3
O4—C9—O3	122.8 (3)	C28—C29—C30	119.5 (3)
O4—C9—C10	119.3 (3)	C28—C29—H29	120.3
O3—C9—C10	117.9 (3)	C30—C29—H29	120.3
C11—C10—C15	118.3 (3)	N4—C30—C29	122.8 (3)
C11—C10—C9	121.6 (3)	N4—C30—H30	118.6
C15—C10—C9	120.0 (3)	C29—C30—H30	118.6
C10—C11—C12	120.4 (3)	C31—N5—C32	123.0 (13)
C10—C11—H11	119.8	C31—N5—C33	121.6 (12)
C12—C11—H11	119.8	C32—N5—C33	115.4 (11)
C13—C12—C11	121.2 (3)	O6—C31—N5	121.1 (15)
C13—C12—H12	119.4	O6—C31—H31	119.5
C11—C12—H12	119.4	N5—C31—H31	119.5
C14—C13—C12	117.5 (3)
O3—Zn1—O1—C1	−87.2 (3)	C9—C10—C15—C14	179.4 (3)
O5—Zn1—O1—C1	40.9 (3)	C14—C13—C16—C16^ii	−155.0 (6)
N1—Zn1—O1—C1	169.2 (3)	C12—C13—C16—C16^ii	23.9 (8)
N4—Zn1—O1—C1	121.8 (3)	C21—N1—C17—C18	0.2 (4)
O5—Zn1—O3—C9	22.6 (2)	Zn1—N1—C17—C18	175.5 (2)
O1—Zn1—O3—C9	115.55 (19)	N1—C17—C18—C19	0.2 (5)
N1—Zn1—O3—C9	−152.89 (19)	C17—C18—C19—C20	−0.4 (5)
N4—Zn1—O3—C9	−74.0 (2)	C18—C19—C20—C21	0.1 (4)
O3—Zn1—N1—C17	−81.6 (2)	C18—C19—C20—C22	−179.4 (3)
O5—Zn1—N1—C17	102.8 (2)	C17—N1—C21—C20	−0.5 (4)
O1—Zn1—N1—C17	15.8 (2)	Zn1—N1—C21—C20	−176.3 (2)
N4—Zn1—N1—C17	−178.9 (3)	C17—N1—C21—C27	179.4 (2)
O3—Zn1—N1—C21	93.76 (19)	Zn1—N1—C21—C27	3.6 (3)
O5—Zn1—N1—C21	−81.7 (2)	C19—C20—C21—N1	0.3 (4)
O1—Zn1—N1—C21	−168.83 (19)	C22—C20—C21—N1	179.9 (2)
N4—Zn1—N1—C21	−3.48 (19)	C19—C20—C21—C27	−179.6 (3)
O3—Zn1—N4—C30	79.1 (3)	C22—C20—C21—C27	0.0 (4)
O5—Zn1—N4—C30	−49.5 (3)	C23—N2—C22—C25	0.2 (4)
O1—Zn1—N4—C30	−130.1 (3)	C23—N2—C22—C20	179.8 (3)
N1—Zn1—N4—C30	−179.1 (3)	C21—C20—C22—N2	−178.7 (3)
O3—Zn1—N4—C27	−98.9 (2)	C19—C20—C22—N2	0.9 (4)
O5—Zn1—N4—C27	132.5 (2)	C21—C20—C22—C25	1.0 (4)
O1—Zn1—N4—C27	51.9 (4)	C19—C20—C22—C25	−179.5 (3)
N1—Zn1—N4—C27	2.87 (19)	C22—N2—C23—C24	1.9 (5)
Zn1—O1—C1—O2	−11.3 (5)	C25—N3—C24—C23	0.8 (5)
Zn1—O1—C1—C2	167.3 (2)	N2—C23—C24—N3	−2.5 (6)
O2—C1—C2—C3	−173.0 (3)	C24—N3—C25—C22	1.3 (4)
O1—C1—C2—C3	8.3 (5)	C24—N3—C25—C26	−178.8 (3)
O2—C1—C2—C7	8.4 (5)	N2—C22—C25—N3	−1.9 (5)
O1—C1—C2—C7	−170.3 (3)	C20—C22—C25—N3	178.5 (3)
C7—C2—C3—C4	0.6 (5)	N2—C22—C25—C26	178.3 (3)
C1—C2—C3—C4	−178.0 (3)	C20—C22—C25—C26	−1.4 (4)
C2—C3—C4—C5	1.0 (5)	N3—C25—C26—C27	−179.1 (3)
C3—C4—C5—C6	−2.3 (5)	C22—C25—C26—C27	0.8 (4)
C3—C4—C5—C8	176.9 (3)	N3—C25—C26—C28	0.7 (5)
C4—C5—C6—C7	2.0 (5)	C22—C25—C26—C28	−179.4 (3)
C8—C5—C6—C7	−177.1 (3)	C30—N4—C27—C26	−0.8 (4)
C5—C6—C7—C2	−0.4 (6)	Zn1—N4—C27—C26	177.4 (2)
C3—C2—C7—C6	−0.9 (5)	C30—N4—C27—C21	179.8 (3)
C1—C2—C7—C6	177.8 (3)	Zn1—N4—C27—C21	−2.0 (3)
C6—C5—C8—C8^i	2.1 (6)	C28—C26—C27—N4	1.0 (5)
C4—C5—C8—C8^i	−177.0 (4)	C25—C26—C27—N4	−179.2 (3)
Zn1—O3—C9—O4	1.9 (4)	C28—C26—C27—C21	−179.6 (3)
Zn1—O3—C9—C10	−176.0 (2)	C25—C26—C27—C21	0.2 (4)
O4—C9—C10—C11	170.0 (3)	N1—C21—C27—N4	−1.1 (4)
O3—C9—C10—C11	−12.0 (4)	C20—C21—C27—N4	178.8 (2)
O4—C9—C10—C15	−10.4 (5)	N1—C21—C27—C26	179.5 (2)
O3—C9—C10—C15	167.6 (3)	C20—C21—C27—C26	−0.6 (4)
C15—C10—C11—C12	1.0 (5)	C27—C26—C28—C29	−0.1 (5)
C9—C10—C11—C12	−179.5 (3)	C25—C26—C28—C29	−180.0 (3)
C10—C11—C12—C13	−0.2 (5)	C26—C28—C29—C30	−0.9 (6)
C11—C12—C13—C14	−0.6 (5)	C27—N4—C30—C29	−0.4 (5)
C11—C12—C13—C16	−179.5 (3)	Zn1—N4—C30—C29	−178.3 (3)
C12—C13—C14—C15	0.4 (6)	C28—C29—C30—N4	1.2 (6)
C16—C13—C14—C15	179.4 (4)	C32—N5—C31—O6	−0.2 (3)
C13—C14—C15—C10	0.4 (6)	C33—N5—C31—O6	179.5 (3)
C11—C10—C15—C14	−1.1 (5)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O2	0.84 (1)	1.73 (1)	2.562 (3)	170 (3)
O5—H5B···O4^iii	0.84 (1)	1.87 (1)	2.700 (3)	175 (4)

Symmetry code: (iii) −x+2, −y+1, −z.