Novel one- and two-dimensional Zn^II coordination polymers based on a versatile 3,6-bis­(pyridin-4-yl)phenanthrene-9,10-dione ligand

Two new Zn^II coordination polymers, namely, catena-poly[[dibromidozinc(II)]-[mu]-[3,6-bis­(pyridin-4-yl)phenanthrene-9,10-dione-[kappa]²N:N']], [ZnBr₂(C₂₄H₁₄N₂O₂)]_n, (1), and poly[[bromido­[[mu]₃-10-hy­droxy-3,6-bis­(pyridin-4-yl)phenanthren-9-olato-[kappa]³N:N':O⁹]zinc(II)] hemihydrate], {[ZnBr(C₂₄H₁₅N₂O₂)]·0.5H₂O}_n, (2), have been synthesized through hydro­thermal reaction of ZnBr₂ and a 60° angular phenanthrene­dione-based linker, i.e. 3,6-bis­(pyridin-4-yl)phenanthrene-9,10-di­one, in dif­ferent solvent systems. Single-crystal analysis reveals that polymer (1) features one-dimensional zigzag chains connected by weak C-H...[pi] and [pi]-[pi] inter­actions to form a two-dimensional network. The two-dimensional networks are further stacked in an ABAB fashion along the a axis through C-H...O hydrogen bonds. Layers A and B comprise left- and right-handed helical chains, respectively. Coordination polymer (2) displays a wave-like two-dimensional layered structure with helical chains. In this compound, there are two opposite helical -Zn-HL- chains [HL is 10-hy­droxy-3,6-bis­(pyridin-4-yl)phenanthren-9-olate] in adjacent layers. The layers are packed in an ABAB sequence and are further connected through O-H...Br and O-H...O hydrogen-bond inter­actions to form a three-dimensional framework. In (1) and (2), the mutidentate L and HL ligands exhibits different coordination modes.

S1. Introduction

\ The design and construction of metal–organic frameworks (MOFs) is still a highly active research area because of the intriguing architectures and topologies of these compounds, as well as their potential applications in molecular magnetism (Clérac et al., 2002; Lloret et al., 1998; Humphrey & Wood, 2004; Galet et al., 2006), catalysis (Fujita et al.,1994; Lee et al., 2002; Merlau et al., 2001), gas sorption (Lin et al., 2007; Mueller et al., 2006; Koh et al., 2008), optical devices (Evans et al., 2002; Binnemans et al., 2009; Allendorf et al., 2009; Henry et al., 2011), and so on (Harbuzaru et al., 2008). In order to synthesize new MOFs with inter­esting compositions and topologies, judicious selection of suitable organic ligands has been one of the key factors (Stang & Olenyuk, 2007; Kim et al., 2007; Ono et al., 2009). Among various organic ligands, bi­pyridine and its bridging derivatives have been the most useful and efficient linkers to generate discrete supra­molecules or coordination polymers (Barnett & Champness, 2003; Kitagawa et al., 2004). Compared with previously reported linear and bent bi­pyridyl ligands, phenanthrene-9,10-dione (PQ) bridged bi­pyridine has its distinguishing features because it contains two neighbouring carbonyl units in an keto–enol tautomeric equilibrium. Thus, this ligand incorporates both pyridyl and hy­droxy as donor groups [see (a) in Scheme 1]. Additionally, this new type of organic ligand contains a rigid conjugated bridging linker phenanthrene, which provides two nitro­gen donors disposed at a 60° angle [see (b) in Scheme 1]. As we know, 60° angular organic ligand provides necessary components for construction of triangular assemblies with linear metal centres. A limited number of such species have been reported (Romero et al., 1996; Kryschenko et al., 2003). To the best of our knowledge, the coordination chemistry of phenanthrene­dione-bridged bi­pyridine has been almost unexplored to date.

We report here the synthesis of such a rigid mutidentate ligand. We have initially explored the coordination chemistry of this new ligand by examining its reactions with ZnBr₂ and synthesized two Zn^II coordination polymers based on 3,6-bis­(pyridin-4-yl)phenanthrene-9,10-dione (L) in different solvent systems. These compounds are catena-poly[zinc(II)-µ-[3,6-bis­(pyridin-4-yl)phenanthrene-9,10-dione]\ -κ²N:N'], [ZnBr₂(L)]_n, (1), and poly[[bromido[µ₃-10-hy­droxy-3,6-bis­(pyridin-4-yl)phenanthren-9-olato-\ κ³N:N':O⁹]zinc(II)] hemihydrate], {[ZnBr(HL)].0.5H₂O}_n, (2). The coordination polymers show a one-dimensional helical chain in (1) and a two-dimensional wave-like net structure in (2), in which the ligand adopts bi- and tridentate coordination modes, respectively (see Scheme 2). Furthermore, weak C—H···π inter­actions and X—H···O (X = C, Br or O) hydrogen bonds play an important role in the construction of polymers (1) and (2).

S2. Experimental

IR samples were prepared as KBr pellets and the spectra were obtained in the 400–4000 cm^-1 range using a PerkinElmer 1600 FT–IR spectrometer. Elemental analyses were performed on a PerkinElmer model 2400 analyzer. ¹H NMR data were collected using an AV-300 spectrometer. Chemical shifts are reported in δ relative to tetra­methyl­silane (TMS). Thermogravimetric analyses were carried out using a PerkinElmer TA Instrument under flowing nitro­gen at a heating rate of 10 K min^-1.

S2.1. Synthesis and crystallization

S2.1.1. Preparation of 3,6-bis­(pyridin-4-yl)phenanthrene-9,10-dione (L)

The precursor 3,6-di­bromo-9,10-di­meth­oxy­phenanthrene was synthesized according to the literature procedure of Boden et al. (2006). The key inter­mediate compound 3,6-bis­(pyridin-4-yl)-9,10-di­meth­oxy­phenanthrene (S) was synthesized by the classic Suzuki coupling reaction from the precursor. IR (KBr pellet, cm^-1): 3031 (w), 2933 (w), 2838 (w), 1594 (s), 1447 (m), 1318 (s), 1241 (m), 1121 (m), 1075 (s), 1044 (m), 988 (m), 812 (s). ¹H NMR (300 MHz, DMSO-d₆, 298 K, TMS): δ 9.38 (s, 2H, Ar—H), 8.74 (d, 4H, Py—H_α), 8.33 (d, 2H, Ar—H), 8.14 (d, 2H, Ar—H), 8.04 (d, 4H, Py—H_β), 4.08 (s, 6H, CH₃).

Upon oxidation with cerium (IV) ammonium nitrate (CAN), the meth­oxy groups in (S) were cleaved and 3,6-bis­(pyridin-4-yl)phenanthrene-9,10-quinone (L) were obtained. IR (KBr pellet, cm^-1): 3023 (w), 1667 (s), 1594 (s), 1385 (m), 1311 (m), 819 (s). ¹H NMR (300 MHz, DMSO-d₆, 298 K, TMS): δ 8.84 (s, 2H, Ar—H), 8.77 (d, 4H, Py—H_α), 8.19 (d, 2H, Ar—H), 7.98 (n, 6H, Ar—H + Py—H_β).

S2.1.2. Preparation of (1)

A mixture of ZnBr₂ (8 mg, 0.035 mmol), L (2 mg, 0.005 mmol) and water/MeOH (3 ml, 20:1 v/v) was sealed in a 1 cm diameter glass tube. The mixture was heated at 423 K for 3 d and then cooled to room temperature at a rate of 5 K h^-1. Yellow block-shaped crystals were obtained in 55% yield (based on L). IR (KBr pellet, cm^-1): 3023 (w), 1678 (s), 1602 (vs), 1384 (m), 832 (s). Analysis calculated for C₂₄H₁₄Br₂N₂O₂Zn: C 49.06, H 2.40 N 4.77%; found: C 49.22, H 2.01, N 4.64%.

S2.1.3. Preparation of (2)

A mixture of ZnBr₂ (8 mg, 0.035 mmol), L (2 mg, 0.005 mmol) and water/EtOH (3 ml, 20:1 v/v) was sealed in a 1 cm diameter glass tube. The mixture was heated at 423 K for 3 d and then cooled to room temperature at a rate of 5 K h^-1. A very small amount of deep-red crystals of (2) were observed. IR (KBr pellet, cm^-1): 3023 (w), 1062 (s), 1579 (s), 1411 (vs), 1384 (vs), 1126 (m), 1031 (s), 814 (s). No other characterization was made for (2) due to the low yield.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. Suitable single crystals of (1) and (3) were selected and mounted in air onto thin glass fibers. [Please provide details of H-atom refinement for the title compounds.]

S2.3. IR analysis

The IR spectra of L, (1) and (2) are similar (see Figs. S1a–c in the Supporting information). The absorption bands in the region 3600–3200 cm^-1 indicate the presence of –OH groups and/or lattice water molecules. The bands at around 3050 and 3020 cm^-1 can be ascribed to C—H stretching vibrations of the pyridine and benzene ring. The feature at around 1600 and 1580 cm^-1 is associated with the presence of pyridine ring and benzene ring. For L and (1), the bands at 1667 and 1678 cm^-1 indicate the presence of carbonyl groups. For (2), the characteristic peaks for carbonyl stretch disappeared, and the new peaks at 1031 cm^-1 can be ascribed to C—O stretching vibrations, which further indicate the presence of –OH. These findings are consistent with the crystal structures. The bands at around 810 cm^-1 can be ascribed to the stretching vibrations of para-substituted benzene.

S3. Results and discussion

S3.1. Structure analysis of (1)

The X-ray single-crystal analysis revealed that compound (1) crystallizes in the monoclinic P2/n space group. As illustrated in Fig. 1, the Zn1 atom is just on the twofold axis of rotation. The Zn^II centres in (1) adopt tetra­hedral coordination geometry. Each Zn^II centre coordinates to two Br atoms and two pyridyl N atoms from two ligands (Table 2). Here, the original o-quinone unit is remained as evidenced by the crystallographic data. The C12—C12ⁱⁱ bond length (Table 2) indicates a C—C single bond (1.54 Å; reference?), and the C12—O2 bond length indicates a classic C═O double bond (1.215 Å; reference?). The two benzene rings of the phenanthrene­dione units are not coplanar, with a dihedral angle between their planes of 20.55 (2)°. The dihedral angle between the planes of the N1-containing pyridyl ring and the adjacent C6-containing benzene ring is 45.09 (2)°.

In (1), L acts as a V-shaped bidentate ligand to bind Zn^II ions into a neutral one-dimensional zigzag chain and these chains are arranged in parallel along the b axis (Fig. 2). There are a series of weak C—H ···π [C8—H8···Cg3 = 3.738 (1) Å; Table 2] inter­actions between adjacent chains. C—H ···π inter­actions, together with weak π–π inter­actions between N1-containing pyridyl rings [the angle between the ring planes is 69° and the distance between the ring centroids is 4.734 (3) Å] link the parallel chains to form two-dimensional network. All Zn^II atoms are located on a linear line. The shortest distance between Zn^II atoms on the same chain is 13.81 (8) Å. Two adjacent two-dimensional networks are further connected by two sets of C2—H2···O2 and C11—H11···O2 hydrogen bonds to form a three-dimensional framework (Fig. 3 and Table 3).

As a further insight into the structure, two adjacent layers comprise two opposite types of helical chains, left-handed chains in layer A and right-handed chains in layer B, respectively (Fig. 4). The whole structure of coordination polymer (1) displays an ABAB stacking motif along the a axis (Fig. 5).

S3.2. Structure analysis of (2)

Coordination polymer (2) crystallizes in the monoclinic P2₁/c space group. The Zn^II centres adopt tetra­hedral coordination geometries. Each Zn^II centre coordinates to one Br atom, two pyridyl N atoms from two 10-hy­droxy-3,6-bis­(pyridin-4-yl)phenanthren-9-olate (HL) ligands and one O atom from a third HL ligand (Fig. 6). The Zn—O and Zn—N bond lengths (Table 4) are consistent with those in reported four-coordinated Zn^II complexes with O- and N-atom donors (Chen et al. 2010). In (2), HL acts as a tridentate ligand. Here, the original o-quinone unit is transformed to o-di­hydroxy which is clearly evidenced by the crystallographic data. For example, the C12—C13 and C36—C37 bond lengths fall into the range of C═C double bonds (1.33 Å; reference?), whereas the C12—O2/C13—O4 and C36—O1/C37—O3 bond lengths are significantly longer than the classic C═O bond length (1.215 Å; reference?). Furthermore, the phenanthrene unit is nearly coplanar: the dihedral angle between adjacent rings are 4.53 (19) (for C6–C11 and C9–C15) and 8.08 (18)° (for C12–C15 and C14–C19) for one unit, and 2.99 (18) (for C30–C35 and C36–C39) and 6.86 (18)° (for C33–C39 and C38–C43) for the other, compared with the phenanthrene­dione unit in polymer (1). The N4-containing pyridyl ring is not coplanar with the phenanthrene unit, exhibiting a dihedral angle of 29.49 (9)°, while the N3-containing pyridyl ring is nearly coplanar with the phenanthrene unit, with a dihedral angle of 4.9 (2)°.

As a further insight into the structure of (2), two 60° angular ligands are connected by Zn^II to form a one-dimensional helical –Zn–HL– chain running along the b axis (Figs. 7a and 7b). Adjacent helical chains are further connected by Zn—O bonds to form two-dimensional networks along the crystallographic ab plane (Figs. 7c and 7d). In this compound, there are two opposite helical chains in adjacent layers. Layer A is composed of right-handed helical –Zn–HL– chains and the adjacent layer B is composed of left-handed helical –Zn–HL– chains. The undulating layers are packed along the [001] direction in the sequence ABAB. All the Zn^II atoms are located at the wave crest and trough. It is noteworthy that there are guest water molecules in the lattice and the wave-like nets are further connected through numerous inter­layer hydrogen-bonding inter­actions between lattice H₂O and coordinated Br atoms, forming a three-dimensional structure (Fig. 7e and Table 5). Besides the O—H···Br hydrogen bonds, there are also O—H···O hydrogen bonds in the structure of (2) (Fig. 8 and Table 5).

S3.3. Powder X-ray diffraction and TG analysis

Simulated and experimental powder X-ray diffraction (PXRD) patterns of (1) are shown in Fig. S2 of the Supporting information. All the peaks in the recorded curves match approximately those in the simulated curves generated from single-crystal diffraction data, which confirms the phase purity of the as-prepared products. All of the coordination polymers are stable under ambient conditions. Thermogravimetric (TG) analyses were performed to assess the thermal stability of complex (1). Polymer (1) was stable up to 483 K, at which temperature it started to decompose. (Fig. S3 in the Supporting information).

S4. Conclusions

In summary, we have successfully synthesized and characterized two Zn^II coordination polymers based on 3,6-bis­(pyridin-4-yl)phenanthrene-9,10-dione. They show one-dimensional zigzag chain and two-dimensional wave-like net structures. A variety of weak inter­actions, including C—H···O C—H···π hydrogen bonds and π–π stacking inter­actions, occur in the structure of (1), while numerous weak O—H···Br, O—H···O and C—H···O hydrogen bonds are observed in the structure of (2). We conclude that the weak inter­actions play a remarkable role in establishing the packing of these two polymers. Both (1) and (2) are packed in an ABAB fashion, and layers A and B are composed of left- and right-handed helical chains, respectively. The angular phenanthrene ligand displays diverse coordination modes, exhibiting N:N'-bidentate and N:N':O-tridentate ligands in complexes (1) and (2), respectively. Moreover, the thermal stabilities of (1) was also discussed.

Computing details

For both compounds, data collection: SMART (Bruker, 1998); cell refinement: SMART (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of (1), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the ??% probability level and H atoms have been omitted for clarity. [Please provide probability level]
	Fig. 2. C—H ···π interactions between the chains to form the two-dimensional network in (1).
	Fig. 3. A presentation of the C—H···O hydrogen bonds between layers in (1).
	Fig. 4. A view of the left- (red) and right-handed (blue) helical chains in (1).
	Fig. 5. The ABAB stacking pattern along the a axis of (1).
	Fig. 6. The molecular structure of (2), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the ??% probability level and H atoms have been omitted for clarity. [Please provide probability level]
	Fig. 7. (a)/(b) The right- and left-hand helical chains in the adjacent layers; (c)/(d) the different two-dimensional networks of (2) including two types of helical chains; (e) the packing of the undulating layers along the [001] direction in the sequence ABAB and a presentation of the hydrogen-bond interactions between two adjacent wave-like nets A and B.
	Fig. 8. The presentation of O···H—O (violet) and Br···H—O (pink) hydrogen bonds in (2).

(130609dm) catena-Poly[[dibromidozinc(II)]-µ-[3,6-bis(pyridin-4-yl)phenanthrene-9,10-dione-κ²N:N']]

Crystal data

[ZnBr2(C24H14N2O2)]	F(000) = 576
Mr = 587.56	Dx = 1.836 Mg m^−3
Monoclinic, P2/n	Mo Kα radiation, λ = 0.71073 Å
a = 10.169 (3) Å	Cell parameters from 1427 reflections
b = 7.858 (2) Å	θ = 2.6–23.3°
c = 13.818 (4) Å	µ = 4.94 mm^−1
β = 105.757 (4)°	T = 298 K
V = 1062.7 (6) Å^3	Block, yellow
Z = 2	0.24 × 0.15 × 0.13 mm

Data collection

Bruker SMART CCD area-detector diffractometer	1982 independent reflections
Radiation source: fine-focus sealed tube	1450 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.037
phi and ω scans	θmax = 25.5°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→10
Tmin = 0.384, Tmax = 0.566	k = −7→9
5333 measured reflections	l = −15→16

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.055	H-atom parameters constrained
S = 0.85	w = 1/[σ^2(Fo^2) + (0.0198P)^2] where P = (Fo^2 + 2Fc^2)/3
1982 reflections	(Δ/σ)max < 0.001
141 parameters	Δρmax = 0.42 e Å^−3
0 restraints	Δρmin = −0.39 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
Br1	0.54664 (4)	0.59811 (5)	0.68437 (3)	0.05252 (15)
C1	0.6232 (3)	0.1654 (5)	0.8316 (2)	0.0396 (9)
H1	0.5528	0.1886	0.7743	0.048*
C2	0.6109 (3)	0.0270 (5)	0.8883 (2)	0.0399 (9)
H2	0.5337	−0.0416	0.8690	0.048*
C3	0.7135 (3)	−0.0115 (4)	0.9750 (2)	0.0312 (8)
C4	0.8236 (3)	0.0994 (4)	1.0000 (2)	0.0358 (9)
H4	0.8933	0.0822	1.0586	0.043*
C5	0.8299 (3)	0.2350 (4)	0.9383 (2)	0.0345 (8)
H5	0.9059	0.3059	0.9560	0.041*
C6	0.7054 (3)	−0.1640 (4)	1.0346 (2)	0.0313 (8)
C7	0.6639 (3)	−0.3170 (4)	0.9839 (2)	0.0389 (9)
H7	0.6376	−0.3194	0.9140	0.047*
C8	0.6621 (3)	−0.4637 (4)	1.0375 (2)	0.0377 (9)
H8	0.6355	−0.5655	1.0034	0.045*
C9	0.6996 (3)	−0.4618 (4)	1.1421 (2)	0.0286 (8)
C10	0.7342 (3)	−0.3087 (4)	1.1942 (2)	0.0264 (7)
C11	0.7383 (3)	−0.1629 (4)	1.1392 (2)	0.0296 (8)
H11	0.7639	−0.0608	1.1731	0.035*
C12	0.7112 (3)	−0.6268 (4)	1.1947 (2)	0.0354 (8)
N1	0.7321 (3)	0.2695 (3)	0.85439 (18)	0.0309 (6)
O2	0.6677 (2)	−0.7608 (3)	1.15359 (18)	0.0494 (7)
Zn1	0.7500	0.44861 (7)	0.7500	0.03071 (16)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0436 (2)	0.0656 (3)	0.0454 (2)	0.0191 (2)	0.00695 (18)	0.0041 (2)
C1	0.034 (2)	0.054 (3)	0.0279 (19)	−0.0034 (18)	0.0020 (16)	0.0076 (17)
C2	0.035 (2)	0.045 (2)	0.037 (2)	−0.0121 (18)	0.0056 (18)	0.0031 (18)
C3	0.034 (2)	0.035 (2)	0.0272 (19)	0.0030 (16)	0.0116 (16)	−0.0006 (15)
C4	0.036 (2)	0.042 (2)	0.0265 (19)	0.0030 (17)	0.0039 (16)	0.0014 (16)
C5	0.0356 (19)	0.035 (2)	0.0317 (19)	−0.0077 (16)	0.0077 (16)	0.0013 (16)
C6	0.036 (2)	0.027 (2)	0.0326 (19)	0.0015 (16)	0.0113 (16)	−0.0017 (15)
C7	0.049 (2)	0.038 (2)	0.0291 (19)	−0.0018 (18)	0.0104 (17)	−0.0044 (17)
C8	0.043 (2)	0.029 (2)	0.043 (2)	−0.0035 (17)	0.0146 (18)	−0.0146 (17)
C9	0.0278 (19)	0.0245 (19)	0.0353 (19)	0.0006 (15)	0.0115 (15)	−0.0003 (15)
C10	0.0303 (18)	0.0223 (19)	0.0284 (17)	0.0019 (15)	0.0111 (15)	−0.0016 (14)
C11	0.0354 (19)	0.0225 (19)	0.0308 (19)	0.0016 (15)	0.0091 (15)	−0.0030 (15)
C12	0.035 (2)	0.030 (2)	0.047 (2)	0.0014 (16)	0.0199 (17)	−0.0073 (17)
N1	0.0324 (16)	0.0348 (17)	0.0256 (15)	−0.0026 (13)	0.0082 (13)	0.0027 (12)
O2	0.0603 (17)	0.0255 (15)	0.0649 (17)	−0.0057 (13)	0.0213 (14)	−0.0096 (13)
Zn1	0.0333 (3)	0.0322 (3)	0.0264 (3)	0.000	0.0077 (2)	0.000

Geometric parameters (Å, º)

Br1—Zn1	2.3367 (7)	C7—C8	1.373 (4)
C1—N1	1.344 (4)	C7—H7	0.9300
C1—C2	1.366 (4)	C8—C9	1.391 (4)
C1—H1	0.9300	C8—H8	0.9300
C2—C3	1.391 (4)	C9—C10	1.398 (4)
C2—H2	0.9300	C9—C12	1.475 (4)
C3—C4	1.387 (4)	C10—C11	1.382 (4)
C3—C6	1.468 (4)	C10—C10^i	1.487 (6)
C4—C5	1.377 (4)	C11—H11	0.9300
C4—H4	0.9300	C12—O2	1.221 (4)
C5—N1	1.334 (4)	C12—C12^i	1.517 (6)
C5—H5	0.9300	N1—Zn1	2.058 (3)
C6—C11	1.392 (4)	Zn1—N1^ii	2.058 (3)
C6—C7	1.398 (4)	Zn1—Br1^ii	2.3367 (7)
N1—C1—C2	123.2 (3)	C9—C8—H8	119.6
N1—C1—H1	118.4	C8—C9—C10	120.3 (3)
C2—C1—H1	118.4	C8—C9—C12	117.8 (3)
C1—C2—C3	120.2 (3)	C10—C9—C12	121.8 (3)
C1—C2—H2	119.9	C11—C10—C9	118.1 (3)
C3—C2—H2	119.9	C11—C10—C10^i	122.71 (18)
C4—C3—C2	116.3 (3)	C9—C10—C10^i	119.18 (18)
C4—C3—C6	122.5 (3)	C10—C11—C6	122.1 (3)
C2—C3—C6	121.1 (3)	C10—C11—H11	118.9
C5—C4—C3	120.1 (3)	C6—C11—H11	118.9
C5—C4—H4	119.9	O2—C12—C9	123.9 (3)
C3—C4—H4	119.9	O2—C12—C12^i	119.5 (2)
N1—C5—C4	123.1 (3)	C9—C12—C12^i	116.52 (19)
N1—C5—H5	118.4	C5—N1—C1	116.9 (3)
C4—C5—H5	118.4	C5—N1—Zn1	124.1 (2)
C11—C6—C7	118.7 (3)	C1—N1—Zn1	118.4 (2)
C11—C6—C3	122.9 (3)	N1^ii—Zn1—N1	93.73 (15)
C7—C6—C3	118.4 (3)	N1^ii—Zn1—Br1^ii	112.23 (7)
C8—C7—C6	119.9 (3)	N1—Zn1—Br1^ii	108.01 (7)
C8—C7—H7	120.0	N1^ii—Zn1—Br1	108.01 (7)
C6—C7—H7	120.0	N1—Zn1—Br1	112.23 (7)
C7—C8—C9	120.8 (3)	Br1^ii—Zn1—Br1	119.64 (4)
C7—C8—H8	119.6
N1—C1—C2—C3	0.5 (6)	C9—C10—C11—C6	2.0 (5)
C1—C2—C3—C4	1.5 (5)	C10^i—C10—C11—C6	−178.4 (3)
C1—C2—C3—C6	−177.1 (3)	C7—C6—C11—C10	1.5 (5)
C2—C3—C4—C5	−2.5 (5)	C3—C6—C11—C10	−178.0 (3)
C6—C3—C4—C5	176.1 (3)	C8—C9—C12—O2	−13.3 (5)
C3—C4—C5—N1	1.5 (5)	C10—C9—C12—O2	171.3 (3)
C4—C3—C6—C11	44.6 (5)	C8—C9—C12—C12^i	163.5 (3)
C2—C3—C6—C11	−136.9 (3)	C10—C9—C12—C12^i	−12.0 (5)
C4—C3—C6—C7	−134.8 (3)	C4—C5—N1—C1	0.6 (5)
C2—C3—C6—C7	43.7 (5)	C4—C5—N1—Zn1	−170.7 (2)
C11—C6—C7—C8	−2.8 (5)	C2—C1—N1—C5	−1.6 (5)
C3—C6—C7—C8	176.6 (3)	C2—C1—N1—Zn1	170.2 (3)
C6—C7—C8—C9	0.8 (5)	C5—N1—Zn1—N1^ii	107.4 (3)
C7—C8—C9—C10	2.7 (5)	C1—N1—Zn1—N1^ii	−63.8 (2)
C7—C8—C9—C12	−172.8 (3)	C5—N1—Zn1—Br1^ii	−7.4 (3)
C8—C9—C10—C11	−4.0 (5)	C1—N1—Zn1—Br1^ii	−178.6 (2)
C12—C9—C10—C11	171.3 (3)	C5—N1—Zn1—Br1	−141.4 (2)
C8—C9—C10—C10^i	176.3 (3)	C1—N1—Zn1—Br1	47.4 (3)
C12—C9—C10—C10^i	−8.3 (5)

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

Hydrogen-bond geometry (Å, º)

Cg3 is the centroid of the N1/C1–C5 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O2^iii	0.93	2.52	3.442 (2)	171
C11—H11···O2^iv	0.93	2.54	3.258 (2)	134
C8—H8···Cg3^v	0.93	2.93	3.738 (1)	147

Symmetry codes: (iii) −x, −y+1, −z+1; (iv) x, y−1, z; (v) x, y+1, z.

(121217f) Poly[[bromido[µ₃-10-hydroxy-3,6-bis(pyridin-4-yl)phenanthren-9-olato-κ³N:N':O⁹]zinc(II)] hemihydrate]

Crystal data

[ZnBr(C24H15N2O2)]·0.5H2O	F(000) = 2072
Mr = 517.67	Dx = 1.745 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 23.138 (9) Å	Cell parameters from 1786 reflections
b = 10.921 (4) Å	θ = 2.3–20.9°
c = 16.490 (7) Å	µ = 3.30 mm^−1
β = 108.931 (7)°	T = 298 K
V = 3941 (3) Å^3	Plan, red
Z = 8	0.14 × 0.12 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer	7314 independent reflections
Radiation source: fine-focus sealed tube	3188 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.095
phi and ω scans	θmax = 25.5°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −28→17
Tmin = 0.655, Tmax = 0.734	k = −13→12
20300 measured reflections	l = −14→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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.071	H-atom parameters constrained
S = 0.82	w = 1/[σ^2(Fo^2) + (0.001P)^2] where P = (Fo^2 + 2Fc^2)/3
7314 reflections	(Δ/σ)max = 0.002
552 parameters	Δρmax = 0.79 e Å^−3
0 restraints	Δρmin = −0.61 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
Br1	0.78429 (3)	0.85690 (7)	0.56283 (5)	0.0626 (2)
Br2	1.27093 (3)	0.75694 (8)	1.03289 (5)	0.0701 (3)
C1	0.8874 (2)	0.7625 (5)	0.7701 (4)	0.0342 (16)
H1	0.8890	0.7797	0.7156	0.041*
C2	0.9409 (2)	0.7337 (5)	0.8337 (4)	0.0273 (15)
H2	0.9772	0.7288	0.8211	0.033*
C3	0.9410 (2)	0.7117 (5)	0.9162 (4)	0.0239 (14)
C4	0.8846 (2)	0.7200 (5)	0.9280 (4)	0.0391 (17)
H4	0.8823	0.7078	0.9827	0.047*
C5	0.8328 (3)	0.7452 (5)	0.8631 (4)	0.0413 (18)
H5	0.7958	0.7475	0.8740	0.050*
C6	0.9970 (2)	0.6737 (5)	0.9872 (4)	0.0246 (15)
C7	1.0546 (2)	0.6706 (5)	0.9751 (4)	0.0297 (16)
H7	1.0581	0.6935	0.9226	0.036*
C8	1.1056 (2)	0.6338 (5)	1.0406 (4)	0.0303 (16)
H8	1.1430	0.6298	1.0308	0.036*
C9	1.1028 (2)	0.6023 (5)	1.1216 (4)	0.0236 (15)
C10	1.0450 (2)	0.5998 (5)	1.1328 (4)	0.0256 (15)
C11	0.9937 (2)	0.6372 (5)	1.0651 (4)	0.0270 (15)
H11	0.9558	0.6372	1.0734	0.032*
C12	1.1575 (3)	0.5752 (5)	1.1920 (4)	0.0277 (16)
C13	1.1516 (3)	0.5439 (5)	1.2686 (4)	0.0311 (17)
C14	1.0938 (2)	0.5303 (5)	1.2816 (4)	0.0261 (16)
C15	1.0397 (3)	0.5552 (5)	1.2123 (4)	0.0246 (15)
C16	0.9842 (2)	0.5260 (5)	1.2247 (4)	0.0312 (17)
H16	0.9485	0.5412	1.1795	0.037*
C17	0.9785 (2)	0.4771 (5)	1.2976 (4)	0.0265 (16)
C18	1.0328 (2)	0.4587 (5)	1.3671 (4)	0.0377 (18)
H18	1.0309	0.4286	1.4189	0.045*
C19	1.0884 (3)	0.4850 (5)	1.3581 (4)	0.0352 (17)
H19	1.1237	0.4724	1.4045	0.042*
C20	0.9191 (3)	0.4410 (5)	1.3039 (4)	0.0270 (16)
C21	0.9062 (3)	0.4431 (5)	1.3803 (4)	0.0336 (17)
H21	0.9354	0.4725	1.4296	0.040*
C22	0.8510 (3)	0.4026 (5)	1.3846 (4)	0.0357 (17)
H22	0.8436	0.4077	1.4367	0.043*
C23	0.8193 (3)	0.3565 (6)	1.2427 (4)	0.0425 (18)
H23	0.7893	0.3271	1.1942	0.051*
C24	0.8731 (3)	0.3979 (5)	1.2337 (4)	0.0400 (18)
H24	0.8783	0.3967	1.1802	0.048*
C25	0.3852 (2)	0.7366 (5)	0.2506 (4)	0.0342 (16)
H25	0.3863	0.7549	0.1960	0.041*
C26	0.4400 (2)	0.7221 (5)	0.3160 (4)	0.0303 (16)
H26	0.4766	0.7285	0.3043	0.036*
C27	0.4407 (2)	0.6983 (5)	0.3979 (4)	0.0301 (16)
C28	0.3835 (2)	0.6893 (5)	0.4101 (4)	0.046 (2)
H28	0.3812	0.6748	0.4646	0.055*
C29	0.3309 (3)	0.7020 (5)	0.3411 (4)	0.0431 (19)
H29	0.2935	0.6935	0.3503	0.052*
C30	0.4985 (2)	0.6796 (5)	0.4720 (4)	0.0311 (17)
C31	0.5561 (2)	0.6922 (5)	0.4623 (4)	0.0359 (17)
H31	0.5591	0.7165	0.4098	0.043*
C32	0.6078 (2)	0.6692 (5)	0.5293 (4)	0.0379 (18)
H32	0.6456	0.6757	0.5210	0.046*
C33	0.6056 (2)	0.6358 (5)	0.6106 (4)	0.0278 (15)
C34	0.5477 (3)	0.6222 (5)	0.6208 (4)	0.0278 (16)
C35	0.4957 (2)	0.6461 (5)	0.5510 (4)	0.0322 (16)
H35	0.4576	0.6390	0.5581	0.039*
C36	0.6610 (3)	0.6176 (5)	0.6828 (4)	0.0313 (17)
C37	0.6556 (3)	0.5888 (5)	0.7603 (4)	0.0293 (16)
C38	0.5988 (3)	0.5661 (5)	0.7726 (4)	0.0287 (16)
C39	0.5436 (2)	0.5809 (5)	0.7020 (4)	0.0258 (15)
C40	0.4890 (2)	0.5463 (5)	0.7146 (4)	0.0310 (16)
H40	0.4530	0.5546	0.6687	0.037*
C41	0.4849 (3)	0.5014 (5)	0.7890 (4)	0.0311 (16)
C42	0.5398 (3)	0.4901 (5)	0.8593 (4)	0.0387 (18)
H42	0.5387	0.4609	0.9118	0.046*
C43	0.5945 (3)	0.5223 (5)	0.8494 (4)	0.0366 (18)
H43	0.6301	0.5145	0.8960	0.044*
C44	0.4247 (3)	0.4670 (5)	0.7960 (4)	0.0324 (17)
C45	0.4106 (3)	0.4726 (5)	0.8707 (4)	0.0373 (18)
H45	0.4400	0.4997	0.9206	0.045*
C46	0.3539 (3)	0.4390 (5)	0.8728 (4)	0.0398 (18)
H46	0.3460	0.4456	0.9245	0.048*
C47	0.3224 (3)	0.3940 (5)	0.7323 (4)	0.0406 (18)
H47	0.2920	0.3678	0.6832	0.049*
C48	0.3777 (3)	0.4264 (5)	0.7247 (4)	0.0431 (19)
H48	0.3838	0.4212	0.6717	0.052*
N1	0.83355 (19)	0.7672 (4)	0.7827 (3)	0.0306 (13)
N2	0.8076 (2)	0.3560 (4)	1.3167 (3)	0.0363 (14)
N3	0.33095 (19)	0.7259 (4)	0.2616 (3)	0.0326 (13)
N4	0.3094 (2)	0.3972 (4)	0.8045 (3)	0.0359 (14)
O1	0.71546 (15)	0.6319 (3)	0.6718 (2)	0.0386 (11)
O2	1.21235 (15)	0.5794 (3)	1.1819 (2)	0.0338 (11)
O3	0.70554 (16)	0.5765 (4)	0.8315 (3)	0.0476 (13)
H3	0.7323	0.5391	0.8193	0.071*
O4	1.20136 (15)	0.5214 (4)	1.3402 (2)	0.0435 (12)
H4A	1.2292	0.4930	1.3256	0.065*
O5	0.7500 (2)	0.5737 (5)	0.4679 (3)	0.130 (2)
H5A	0.7674	0.6266	0.5058	0.195*
H5B	0.7421	0.5039	0.4845	0.195*
Zn1	0.75681 (3)	0.78857 (6)	0.67976 (4)	0.0360 (2)
Zn2	1.25180 (3)	0.72904 (7)	1.16239 (5)	0.0365 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0628 (5)	0.0859 (7)	0.0460 (5)	0.0056 (4)	0.0270 (4)	0.0164 (5)
Br2	0.0673 (5)	0.1042 (7)	0.0486 (5)	0.0136 (5)	0.0323 (4)	0.0210 (5)
C1	0.036 (4)	0.038 (4)	0.030 (4)	0.002 (3)	0.012 (3)	0.004 (3)
C2	0.019 (3)	0.035 (4)	0.027 (4)	0.002 (3)	0.005 (3)	0.003 (3)
C3	0.020 (3)	0.018 (4)	0.029 (4)	−0.003 (3)	0.003 (3)	0.000 (3)
C4	0.023 (4)	0.062 (5)	0.032 (4)	0.008 (3)	0.007 (3)	0.004 (4)
C5	0.033 (4)	0.050 (5)	0.042 (5)	0.011 (3)	0.014 (3)	0.014 (4)
C6	0.020 (3)	0.016 (4)	0.036 (4)	−0.003 (3)	0.007 (3)	0.000 (3)
C7	0.025 (4)	0.039 (4)	0.023 (4)	−0.003 (3)	0.005 (3)	0.002 (3)
C8	0.015 (3)	0.044 (4)	0.033 (4)	−0.001 (3)	0.010 (3)	−0.002 (4)
C9	0.022 (4)	0.018 (4)	0.027 (4)	0.005 (3)	0.002 (3)	−0.001 (3)
C10	0.021 (4)	0.021 (4)	0.030 (4)	−0.001 (3)	0.002 (3)	0.002 (3)
C11	0.019 (3)	0.028 (4)	0.037 (4)	−0.001 (3)	0.013 (3)	0.005 (3)
C12	0.018 (4)	0.027 (4)	0.038 (5)	0.005 (3)	0.009 (3)	−0.001 (3)
C13	0.013 (4)	0.035 (4)	0.039 (5)	0.007 (3)	−0.002 (3)	−0.004 (4)
C14	0.022 (4)	0.025 (4)	0.031 (4)	0.004 (3)	0.008 (3)	−0.001 (3)
C15	0.023 (4)	0.020 (4)	0.031 (4)	0.000 (3)	0.009 (3)	−0.001 (3)
C16	0.023 (4)	0.034 (4)	0.032 (5)	0.005 (3)	0.003 (3)	0.005 (3)
C17	0.023 (4)	0.027 (4)	0.032 (4)	0.001 (3)	0.011 (3)	0.001 (3)
C18	0.033 (4)	0.046 (5)	0.036 (5)	−0.002 (3)	0.014 (4)	0.002 (4)
C19	0.021 (4)	0.049 (5)	0.029 (4)	0.003 (3)	−0.001 (3)	−0.004 (4)
C20	0.022 (4)	0.026 (4)	0.033 (4)	0.000 (3)	0.008 (3)	0.004 (3)
C21	0.029 (4)	0.040 (4)	0.030 (5)	−0.014 (3)	0.007 (3)	−0.010 (3)
C22	0.038 (4)	0.035 (4)	0.040 (5)	−0.007 (3)	0.021 (4)	−0.004 (4)
C23	0.031 (4)	0.054 (5)	0.037 (5)	−0.009 (3)	0.004 (4)	−0.004 (4)
C24	0.038 (4)	0.051 (5)	0.038 (5)	−0.012 (3)	0.021 (4)	0.004 (4)
C25	0.025 (4)	0.039 (4)	0.039 (4)	0.003 (3)	0.011 (3)	0.011 (3)
C26	0.019 (3)	0.035 (4)	0.041 (4)	0.001 (3)	0.016 (3)	0.003 (4)
C27	0.021 (3)	0.031 (4)	0.035 (4)	−0.002 (3)	0.005 (3)	0.000 (3)
C28	0.026 (4)	0.076 (6)	0.031 (4)	0.008 (3)	0.002 (3)	0.005 (4)
C29	0.023 (4)	0.055 (5)	0.055 (5)	0.003 (3)	0.016 (4)	0.013 (4)
C30	0.023 (4)	0.030 (4)	0.034 (4)	−0.003 (3)	0.001 (3)	0.005 (3)
C31	0.027 (4)	0.046 (5)	0.035 (4)	−0.007 (3)	0.010 (3)	0.002 (3)
C32	0.013 (3)	0.053 (5)	0.050 (5)	0.001 (3)	0.013 (3)	0.003 (4)
C33	0.021 (4)	0.025 (4)	0.037 (5)	0.000 (3)	0.010 (3)	−0.005 (3)
C34	0.026 (4)	0.024 (4)	0.031 (4)	0.002 (3)	0.006 (3)	−0.001 (3)
C35	0.016 (3)	0.036 (4)	0.047 (5)	0.001 (3)	0.014 (3)	0.010 (4)
C36	0.019 (4)	0.032 (4)	0.044 (5)	0.003 (3)	0.012 (3)	−0.003 (4)
C37	0.013 (3)	0.033 (4)	0.038 (5)	0.002 (3)	0.003 (3)	−0.003 (3)
C38	0.026 (4)	0.020 (4)	0.037 (5)	0.009 (3)	0.004 (3)	0.002 (3)
C39	0.016 (3)	0.026 (4)	0.035 (4)	0.000 (3)	0.008 (3)	0.000 (3)
C40	0.022 (4)	0.030 (4)	0.035 (4)	−0.001 (3)	0.002 (3)	0.005 (3)
C41	0.033 (4)	0.022 (4)	0.039 (5)	−0.004 (3)	0.013 (4)	0.002 (3)
C42	0.051 (5)	0.040 (5)	0.026 (4)	0.004 (4)	0.013 (4)	−0.001 (3)
C43	0.029 (4)	0.041 (5)	0.037 (5)	0.007 (3)	0.006 (3)	0.003 (4)
C44	0.040 (4)	0.022 (4)	0.037 (5)	0.001 (3)	0.015 (4)	−0.003 (3)
C45	0.036 (4)	0.047 (5)	0.025 (4)	−0.013 (3)	0.005 (3)	−0.008 (4)
C46	0.046 (5)	0.044 (5)	0.034 (5)	−0.009 (4)	0.020 (4)	−0.009 (4)
C47	0.030 (4)	0.050 (5)	0.039 (5)	−0.011 (3)	0.007 (4)	−0.007 (4)
C48	0.044 (4)	0.051 (5)	0.037 (5)	−0.024 (4)	0.017 (4)	−0.002 (4)
N1	0.021 (3)	0.034 (3)	0.033 (3)	−0.003 (2)	0.004 (2)	−0.001 (3)
N2	0.032 (3)	0.037 (4)	0.038 (4)	−0.003 (3)	0.007 (3)	0.004 (3)
N3	0.023 (3)	0.041 (4)	0.032 (3)	0.005 (3)	0.007 (3)	0.006 (3)
N4	0.032 (3)	0.047 (4)	0.030 (4)	−0.004 (3)	0.012 (3)	−0.002 (3)
O1	0.015 (2)	0.044 (3)	0.054 (3)	0.001 (2)	0.007 (2)	0.000 (2)
O2	0.017 (2)	0.045 (3)	0.039 (3)	0.004 (2)	0.009 (2)	0.008 (2)
O3	0.026 (3)	0.073 (4)	0.037 (3)	0.011 (2)	0.000 (2)	−0.011 (3)
O4	0.020 (2)	0.067 (4)	0.040 (3)	0.009 (2)	0.006 (2)	0.001 (3)
O5	0.200 (6)	0.112 (5)	0.073 (5)	0.020 (4)	0.037 (4)	0.021 (4)
Zn1	0.0245 (4)	0.0489 (6)	0.0336 (5)	0.0045 (4)	0.0080 (3)	0.0029 (4)
Zn2	0.0227 (4)	0.0512 (5)	0.0354 (5)	0.0038 (4)	0.0092 (3)	0.0048 (4)

Geometric parameters (Å, º)

Br1—Zn1	2.3398 (13)	C27—C30	1.503 (7)
Br2—Zn2	2.3371 (13)	C28—C29	1.378 (7)
C1—N1	1.331 (6)	C28—H28	0.9300
C1—C2	1.374 (6)	C29—N3	1.337 (7)
C1—H1	0.9300	C29—H29	0.9300
C2—C3	1.381 (7)	C30—C35	1.375 (7)
C2—H2	0.9300	C30—C31	1.399 (7)
C3—C4	1.382 (6)	C31—C32	1.363 (6)
C3—C6	1.495 (6)	C31—H31	0.9300
C4—C5	1.352 (6)	C32—C33	1.406 (7)
C4—H4	0.9300	C32—H32	0.9300
C5—N1	1.353 (7)	C33—C34	1.413 (7)
C5—H5	0.9300	C33—C36	1.451 (7)
C6—C11	1.372 (7)	C34—C35	1.393 (7)
C6—C7	1.411 (6)	C34—C39	1.444 (7)
C7—C8	1.377 (6)	C35—H35	0.9300
C7—H7	0.9300	C36—O1	1.339 (6)
C8—C9	1.401 (7)	C36—C37	1.361 (8)
C8—H8	0.9300	C37—O3	1.361 (6)
C9—C10	1.408 (7)	C37—C38	1.416 (7)
C9—C12	1.444 (7)	C38—C43	1.387 (7)
C10—C11	1.401 (6)	C38—C39	1.431 (7)
C10—C15	1.441 (7)	C39—C40	1.398 (7)
C11—H11	0.9300	C40—C41	1.353 (7)
C12—O2	1.334 (6)	C40—H40	0.9300
C12—C13	1.357 (8)	C41—C42	1.420 (7)
C13—O4	1.379 (6)	C41—C44	1.485 (7)
C13—C14	1.428 (7)	C42—C43	1.374 (7)
C14—C19	1.398 (7)	C42—H42	0.9300
C14—C15	1.422 (7)	C43—H43	0.9300
C15—C16	1.401 (7)	C44—C45	1.372 (8)
C16—C17	1.360 (7)	C44—C48	1.390 (7)
C16—H16	0.9300	C45—C46	1.376 (7)
C17—C18	1.414 (7)	C45—H45	0.9300
C17—C20	1.467 (7)	C46—N4	1.336 (6)
C18—C19	1.372 (7)	C46—H46	0.9300
C18—H18	0.9300	C47—N4	1.319 (7)
C19—H19	0.9300	C47—C48	1.372 (7)
C20—C24	1.376 (7)	C47—H47	0.9300
C20—C21	1.386 (7)	C48—H48	0.9300
C21—C22	1.374 (7)	N2—Zn2^i	2.058 (5)
C21—H21	0.9300	N3—Zn2^ii	2.022 (4)
C22—N2	1.339 (6)	N4—Zn1^iii	2.020 (5)
C22—H22	0.9300	Zn1—O1	1.943 (4)
C23—N2	1.333 (7)	Zn2—O2	1.948 (4)
C23—C24	1.377 (7)	O3—H3	0.8200
C23—H23	0.9300	O4—H4A	0.8200
C24—H24	0.9300	O5—H5A	0.8501
C25—N3	1.331 (6)	O5—H5B	0.8501
C25—C26	1.381 (6)	Zn1—N1	2.033 (4)
C25—H25	0.9300	Zn1—N4^iv	2.020 (5)
C26—C27	1.371 (7)	Zn2—N3^v	2.022 (4)
C26—H26	0.9300	Zn2—N2^vi	2.058 (5)
C27—C28	1.405 (7)
N1—C1—C2	123.1 (5)	C35—C30—C31	118.2 (5)
N1—C1—H1	118.4	C35—C30—C27	120.2 (6)
C2—C1—H1	118.4	C31—C30—C27	121.5 (6)
C1—C2—C3	120.4 (5)	C32—C31—C30	120.5 (6)
C1—C2—H2	119.8	C32—C31—H31	119.7
C3—C2—H2	119.8	C30—C31—H31	119.7
C2—C3—C4	115.3 (5)	C31—C32—C33	121.8 (6)
C2—C3—C6	122.9 (5)	C31—C32—H32	119.1
C4—C3—C6	121.7 (5)	C33—C32—H32	119.1
C5—C4—C3	122.5 (6)	C32—C33—C34	118.0 (5)
C5—C4—H4	118.8	C32—C33—C36	121.5 (6)
C3—C4—H4	118.8	C34—C33—C36	120.5 (6)
C4—C5—N1	121.5 (6)	C35—C34—C33	118.6 (6)
C4—C5—H5	119.3	C35—C34—C39	121.8 (6)
N1—C5—H5	119.3	C33—C34—C39	119.5 (5)
C11—C6—C7	117.9 (5)	C30—C35—C34	122.7 (6)
C11—C6—C3	121.1 (5)	C30—C35—H35	118.6
C7—C6—C3	121.0 (5)	C34—C35—H35	118.6
C8—C7—C6	120.4 (6)	O1—C36—C37	122.0 (6)
C8—C7—H7	119.8	O1—C36—C33	119.5 (6)
C6—C7—H7	119.8	C37—C36—C33	118.4 (6)
C7—C8—C9	121.7 (5)	O3—C37—C36	121.6 (6)
C7—C8—H8	119.1	O3—C37—C38	115.2 (6)
C9—C8—H8	119.1	C36—C37—C38	123.2 (6)
C8—C9—C10	118.1 (5)	C43—C38—C37	122.4 (6)
C8—C9—C12	121.1 (6)	C43—C38—C39	118.2 (6)
C10—C9—C12	120.8 (6)	C37—C38—C39	119.3 (6)
C11—C10—C9	119.0 (6)	C40—C39—C38	117.4 (6)
C11—C10—C15	121.5 (5)	C40—C39—C34	123.8 (5)
C9—C10—C15	119.5 (5)	C38—C39—C34	118.7 (6)
C6—C11—C10	122.7 (5)	C41—C40—C39	124.4 (6)
C6—C11—H11	118.6	C41—C40—H40	117.8
C10—C11—H11	118.6	C39—C40—H40	117.8
O2—C12—C13	120.8 (5)	C40—C41—C42	117.8 (6)
O2—C12—C9	120.9 (6)	C40—C41—C44	120.4 (6)
C13—C12—C9	118.2 (6)	C42—C41—C44	121.8 (6)
C12—C13—O4	122.2 (6)	C43—C42—C41	119.6 (6)
C12—C13—C14	123.2 (6)	C43—C42—H42	120.2
O4—C13—C14	114.5 (6)	C41—C42—H42	120.2
C19—C14—C15	118.6 (6)	C42—C43—C38	122.6 (6)
C19—C14—C13	122.3 (5)	C42—C43—H43	118.7
C15—C14—C13	118.9 (6)	C38—C43—H43	118.7
C16—C15—C14	116.8 (6)	C45—C44—C48	115.2 (6)
C16—C15—C10	124.2 (5)	C45—C44—C41	124.1 (6)
C14—C15—C10	118.8 (6)	C48—C44—C41	120.7 (6)
C17—C16—C15	125.0 (5)	C44—C45—C46	121.1 (6)
C17—C16—H16	117.5	C44—C45—H45	119.4
C15—C16—H16	117.5	C46—C45—H45	119.4
C16—C17—C18	117.2 (6)	N4—C46—C45	123.3 (6)
C16—C17—C20	122.0 (5)	N4—C46—H46	118.3
C18—C17—C20	120.8 (6)	C45—C46—H46	118.3
C19—C18—C17	120.0 (6)	N4—C47—C48	124.7 (6)
C19—C18—H18	120.0	N4—C47—H47	117.7
C17—C18—H18	120.0	C48—C47—H47	117.7
C18—C19—C14	122.2 (5)	C47—C48—C44	120.0 (6)
C18—C19—H19	118.9	C47—C48—H48	120.0
C14—C19—H19	118.9	C44—C48—H48	120.0
C24—C20—C21	115.8 (6)	C1—N1—C5	117.2 (5)
C24—C20—C17	121.3 (6)	C1—N1—Zn1	118.8 (4)
C21—C20—C17	122.9 (6)	C5—N1—Zn1	123.6 (4)
C22—C21—C20	121.3 (6)	C23—N2—C22	116.4 (6)
C22—C21—H21	119.4	C23—N2—Zn2^i	120.0 (4)
C20—C21—H21	119.4	C22—N2—Zn2^i	118.5 (4)
N2—C22—C21	122.5 (6)	C25—N3—C29	116.9 (5)
N2—C22—H22	118.8	C25—N3—Zn2^ii	122.3 (4)
C21—C22—H22	118.8	C29—N3—Zn2^ii	120.5 (4)
N2—C23—C24	124.0 (6)	C47—N4—C46	115.6 (6)
N2—C23—H23	118.0	C47—N4—Zn1^iii	120.3 (4)
C24—C23—H23	118.0	C46—N4—Zn1^iii	120.0 (4)
C20—C24—C23	120.1 (6)	C36—O1—Zn1	124.0 (3)
C20—C24—H24	120.0	C12—O2—Zn2	124.4 (3)
C23—C24—H24	120.0	C37—O3—H3	109.5
N3—C25—C26	123.4 (6)	C13—O4—H4A	109.5
N3—C25—H25	118.3	H5A—O5—H5B	118.2
C26—C25—H25	118.3	O1—Zn1—N4^iv	98.53 (18)
C27—C26—C25	120.4 (6)	O1—Zn1—N1	103.45 (16)
C27—C26—H26	119.8	N4^iv—Zn1—N1	116.9 (2)
C25—C26—H26	119.8	O1—Zn1—Br1	119.01 (12)
C26—C27—C28	116.3 (5)	N4^iv—Zn1—Br1	109.82 (15)
C26—C27—C30	123.4 (6)	N1—Zn1—Br1	109.13 (15)
C28—C27—C30	120.3 (6)	O2—Zn2—N3^v	101.65 (17)
C29—C28—C27	119.8 (6)	O2—Zn2—N2^vi	99.39 (18)
C29—C28—H28	120.1	N3^v—Zn2—N2^vi	110.8 (2)
C27—C28—H28	120.1	O2—Zn2—Br2	119.87 (11)
N3—C29—C28	123.1 (6)	N3^v—Zn2—Br2	110.58 (15)
N3—C29—H29	118.4	N2^vi—Zn2—Br2	113.55 (16)
C28—C29—H29	118.4
N1—C1—C2—C3	−2.2 (9)	C36—C33—C34—C35	177.1 (5)
C1—C2—C3—C4	0.6 (8)	C32—C33—C34—C39	176.3 (5)
C1—C2—C3—C6	176.8 (5)	C36—C33—C34—C39	−4.6 (8)
C2—C3—C4—C5	1.4 (9)	C31—C30—C35—C34	−1.2 (9)
C6—C3—C4—C5	−174.9 (5)	C27—C30—C35—C34	177.1 (5)
C3—C4—C5—N1	−1.9 (10)	C33—C34—C35—C30	1.5 (9)
C2—C3—C6—C11	−171.3 (6)	C39—C34—C35—C30	−176.7 (5)
C4—C3—C6—C11	4.7 (8)	C32—C33—C36—O1	−0.4 (8)
C2—C3—C6—C7	6.7 (8)	C34—C33—C36—O1	−179.4 (5)
C4—C3—C6—C7	−177.4 (5)	C32—C33—C36—C37	178.1 (6)
C11—C6—C7—C8	−1.1 (8)	C34—C33—C36—C37	−0.9 (8)
C3—C6—C7—C8	−179.1 (5)	O1—C36—C37—O3	1.9 (9)
C6—C7—C8—C9	−2.1 (8)	C33—C36—C37—O3	−176.6 (5)
C7—C8—C9—C10	4.9 (8)	O1—C36—C37—C38	−176.2 (5)
C7—C8—C9—C12	−174.0 (5)	C33—C36—C37—C38	5.3 (9)
C8—C9—C10—C11	−4.6 (8)	O3—C37—C38—C43	−6.4 (8)
C12—C9—C10—C11	174.4 (5)	C36—C37—C38—C43	171.8 (6)
C8—C9—C10—C15	173.4 (5)	O3—C37—C38—C39	177.8 (5)
C12—C9—C10—C15	−7.7 (8)	C36—C37—C38—C39	−3.9 (9)
C7—C6—C11—C10	1.4 (8)	C43—C38—C39—C40	−2.0 (8)
C3—C6—C11—C10	179.4 (5)	C37—C38—C39—C40	173.9 (5)
C9—C10—C11—C6	1.5 (8)	C43—C38—C39—C34	−177.8 (5)
C15—C10—C11—C6	−176.4 (5)	C37—C38—C39—C34	−1.8 (8)
C8—C9—C12—O2	0.0 (8)	C35—C34—C39—C40	8.6 (9)
C10—C9—C12—O2	−178.9 (5)	C33—C34—C39—C40	−169.5 (5)
C8—C9—C12—C13	−179.2 (6)	C35—C34—C39—C38	−175.9 (5)
C10—C9—C12—C13	1.9 (8)	C33—C34—C39—C38	5.9 (8)
O2—C12—C13—O4	3.5 (9)	C38—C39—C40—C41	0.9 (9)
C9—C12—C13—O4	−177.3 (5)	C34—C39—C40—C41	176.4 (6)
O2—C12—C13—C14	−175.9 (5)	C39—C40—C41—C42	0.7 (9)
C9—C12—C13—C14	3.3 (9)	C39—C40—C41—C44	−180.0 (5)
C12—C13—C14—C19	172.8 (6)	C40—C41—C42—C43	−1.2 (9)
O4—C13—C14—C19	−6.7 (8)	C44—C41—C42—C43	179.5 (5)
C12—C13—C14—C15	−2.5 (8)	C41—C42—C43—C38	0.0 (9)
O4—C13—C14—C15	178.0 (5)	C37—C38—C43—C42	−174.1 (5)
C19—C14—C15—C16	−3.3 (8)	C39—C38—C43—C42	1.7 (9)
C13—C14—C15—C16	172.2 (5)	C40—C41—C44—C45	−150.2 (6)
C19—C14—C15—C10	−178.9 (5)	C42—C41—C44—C45	29.0 (9)
C13—C14—C15—C10	−3.4 (8)	C40—C41—C44—C48	29.5 (8)
C11—C10—C15—C16	11.0 (9)	C42—C41—C44—C48	−151.2 (6)
C9—C10—C15—C16	−166.9 (5)	C48—C44—C45—C46	0.5 (9)
C11—C10—C15—C14	−173.7 (5)	C41—C44—C45—C46	−179.8 (5)
C9—C10—C15—C14	8.3 (8)	C44—C45—C46—N4	1.2 (9)
C14—C15—C16—C17	0.6 (8)	N4—C47—C48—C44	−0.5 (10)
C10—C15—C16—C17	175.9 (6)	C45—C44—C48—C47	−0.8 (9)
C15—C16—C17—C18	2.4 (9)	C41—C44—C48—C47	179.5 (5)
C15—C16—C17—C20	−175.7 (5)	C2—C1—N1—C5	1.8 (8)
C16—C17—C18—C19	−2.6 (8)	C2—C1—N1—Zn1	−171.9 (4)
C20—C17—C18—C19	175.5 (5)	C4—C5—N1—C1	0.3 (9)
C17—C18—C19—C14	0.0 (9)	C4—C5—N1—Zn1	173.6 (4)
C15—C14—C19—C18	3.1 (9)	C24—C23—N2—C22	2.1 (9)
C13—C14—C19—C18	−172.2 (5)	C24—C23—N2—Zn2^i	−152.3 (5)
C16—C17—C20—C24	32.0 (9)	C21—C22—N2—C23	−3.3 (9)
C18—C17—C20—C24	−146.0 (6)	C21—C22—N2—Zn2^i	151.4 (4)
C16—C17—C20—C21	−150.6 (6)	C26—C25—N3—C29	1.2 (8)
C18—C17—C20—C21	31.4 (8)	C26—C25—N3—Zn2^ii	−173.0 (4)
C24—C20—C21—C22	1.0 (9)	C28—C29—N3—C25	0.5 (9)
C17—C20—C21—C22	−176.6 (5)	C28—C29—N3—Zn2^ii	174.8 (4)
C20—C21—C22—N2	1.9 (9)	C48—C47—N4—C46	2.0 (10)
C21—C20—C24—C23	−2.2 (9)	C48—C47—N4—Zn1^iii	−155.3 (5)
C17—C20—C24—C23	175.4 (5)	C45—C46—N4—C47	−2.3 (9)
N2—C23—C24—C20	0.7 (10)	C45—C46—N4—Zn1^iii	155.0 (5)
N3—C25—C26—C27	−1.7 (9)	C37—C36—O1—Zn1	−93.0 (6)
C25—C26—C27—C28	0.4 (9)	C33—C36—O1—Zn1	85.5 (6)
C25—C26—C27—C30	179.1 (5)	C13—C12—O2—Zn2	−112.4 (5)
C26—C27—C28—C29	1.2 (8)	C9—C12—O2—Zn2	68.4 (6)
C30—C27—C28—C29	−177.6 (5)	C36—O1—Zn1—N4^iv	−4.8 (5)
C27—C28—C29—N3	−1.7 (9)	C36—O1—Zn1—N1	115.7 (4)
C26—C27—C30—C35	−174.6 (6)	C36—O1—Zn1—Br1	−123.2 (4)
C28—C27—C30—C35	4.1 (8)	C1—N1—Zn1—O1	111.3 (4)
C26—C27—C30—C31	3.6 (8)	C5—N1—Zn1—O1	−61.9 (5)
C28—C27—C30—C31	−177.7 (6)	C1—N1—Zn1—N4^iv	−141.7 (4)
C35—C30—C31—C32	1.3 (8)	C5—N1—Zn1—N4^iv	45.1 (5)
C27—C30—C31—C32	−176.9 (5)	C1—N1—Zn1—Br1	−16.3 (4)
C30—C31—C32—C33	−1.9 (9)	C5—N1—Zn1—Br1	170.5 (4)
C31—C32—C33—C34	2.2 (9)	C12—O2—Zn2—N3^v	122.4 (4)
C31—C32—C33—C36	−176.8 (5)	C12—O2—Zn2—N2^vi	8.8 (4)
C32—C33—C34—C35	−1.9 (8)	C12—O2—Zn2—Br2	−115.4 (4)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2^vii	0.82	1.83	2.614 (3)	161
O4—H4A···O1^vii	0.82	1.86	2.606 (5)	151
O5—H5A···Br1^viii	0.85	2.67	3.441 (2)	152
O5—H5B···Br2^ix	0.85	2.72	3.492 (2)	152
C47—H47···O5^x	0.93	2.45	3.201 (3)	138

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