Tetra­aqua­bis­[5-(3-pyrid­yl-[kappa]N)pyrimi­dine]zinc(II) bis­(trifluoro­methane­sulfonate): a novel cationic complex and three-dimensional hydrogen-bonded network

The title compound, [Zn(C₉H₇N₃)₂(H₂O)₄](CF₃O₃S)₂, con­tains an octa­hedral [ZnL₂(H₂O)₄]²⁺ cationic complex with trans geometry (Zn site symmetry ), and each 5-(3-pyridyl)pyrimidine (L) ligand is coordinated in a monodentate fashion through the pyridine N atom. In the extended structure, these complexes, with both hydrogen-bond acceptor (pyrimidine) and donor (H₂O) functions, are linked to each other by inter­molecular water-pyrimidine O-H...N hydrogen-bonding inter­actions, resulting in a double chain along the crystallographic a axis. The trifluoro­methane­sulfonate anions are integrated into the chains via O-H...O hydrogen bonds between the coordinated water and sulfonate O atoms. These double chains are associated into a novel three-dimensional network through inter­chain water-pyrimidine O-H...N hydrogen bonds. The asymmetric ligand plays an important role in constructing this unusual supra­molecular structure.

S1. Comment

Asymmetric organic ligands with various topologies and coordination natures are widely used by chemists in the construction of coordination polymers and supramolecular complexes. Some of the resulting materials exhibit encouraging potential for applications in magnetism (He et al., 2006), luminescence (Allendorf et al., 2009; Hou et al., 2010) and nonlinear optics (Evans & Lin, 2002; Ye et al., 2005). The geometry of the organic ligands is one of the most important factors in determining the structure of the framework. It is well known that the inclusion of different functional groups, such as pyrimidine and pyridine, can lead to different coordination modes and may play a crucial role in the construction of supramolecular complexes driven by coordinate interactions and hydrogen bonds. Previously, pyrimidine derivatives have occasionally been used in supramolecular chemistry and coordination polymers with versatile structures, and potential properties have been reported. For example, Champness and co-workers have reported a highly unusual three-dimensional polymer, [Cu₃I₃(5-(4-pyridyl)pyrimidine)]_n, in which the 5-(4-pyridyl)pyrimidine ligand bridges two-dimensional brick-wall (CuI)_n sheets (Thébault et al., 2006). Fujita et al. (2005) reported two M₈L₄ cages controlled by the guest molecules, based on the tridentate ligand 3,5-bis(3-pyridyl)-1-(3,5-pyrimidyl)benzene. In addition, some pyrimidine derivatives employed as nucleophilic linkers have received much attention in self-assembly with various hydrogen-bond donors (Georgiev et al. 2004). In this contribution, a new asymmetric organic ligand, 5-(3-pyridyl)pyrimidine (L), has been synthesized and used to create a novel Zn^II complex salt [ZnL₂(H₂O)₄](CF₃SO₃)₂, (I), the structure of which is reported.

The compound crystallizes in the monoclinic space group P2₁/n with one half of a [ZnL₂(H₂O)₄]²⁺ complex cation (Zn is on a centre of inversion) and one CF₃SO₃^- counteranion in the asymmetric unit. The Zn^II centre lies in a highly regular octahedral {ZnN₂O₄} coordination environment, which is composed of two pyridine N-donors from two L ligands in the axial positions and four O-donors from four coordinated water molecules in the equatorial positions (Fig. 1). The fact that L acts as a monodentate ligand in this fashion proves that the pyridine group has a stronger coordination ability than the pyrimidine group in this case. The pyrimidine and pyridine rings in the ligand are significantly twisted. The dihedral angle between the two rings, 42.36 (15)°, is distinctly larger than the value of 34.0 (1)° in [Cu₃I₃(5-(4-pyridyl)pyrimidine)]_n (Thébault et al., 2006). For [ML₂(H₂O)₄] complexes with this type of asymmetric ligand, the two terminal groups of the ligand can be located on either the same or opposite sides of the central pyridine–M–pyridine unit, resulting in cis or trans conformations (Dong et al., 2007; Zheng et al., 2009), which is distinctly different from some [ML₂(H₂O)₄] complexes with non-asymmetric ligands (Khanpour & Morsali, 2009; Peedikakkal & Vittal, 2008; Chen et al., 2008). In (I), the two terminal pyrimidine groups of the [ZnL₂(H₂O)₄]²⁺ complex cation give rise to a trans conformation with respect to the central pyridine–Zn–pyridine unit, as required by the inversion symmetry. Though some similar trans-conformation complexes have been reported (Chen et al., 2004; Cakir et al., 2003; Zhu et al., 2009), the specific combination of interacting groups in (I) leads to a novel three-dimensional network of interactions.

Given the strong hydrogen-bond capability of the uncoordinated pyrimidine groups (Horikoshi et al., 2004; Georgiev et al., 2004), it is not surprising that the [ZnL₂(H₂O)₄]²⁺ complex cation displays a robust hydrogen-bonding framework. The uncoordinated pyrimidine groups act as hydrogen-bond acceptors to link the complexes into double chains along the crystallographic a direction via O5—H5A···N2ⁱ hydrogen bonds between coordinated water molecules and pyrimidine N atoms (Fig. 2) [symmetry code: (i) x - 1, y, z]. In the double chain, the Zn^II···Zn^II separation is 9.360 (2) Å and this space is large enough to accommodate two uncoordinated CF₃SO₃^- anions, which are locked in the chain through O5—H5B···O1 and O4—H4A···O3ⁱⁱⁱ hydrogen bonds between the coordinated water molecules and the CF₃SO₃^- anions [symmetry code: (iii) x + 1, y, z]. The CF₃SO₃^- anions thus play an important role in constructing the hydrogen-bonded supramolecular chain. Notably, the hydrogen-bond driven chain here is distinctly different from that observed in the related compound {[Zn(L1)₂(CH₃CH₂OH)₂(H₂O)₂] (p-CH₃C₆H₄SO₃)₂}_n, (L1 is 1,2-bis{1-[1-(pyridine-3-ylmethyl)benzimidazol-2-yl]ethylidene}hydrazine; Zheng et al., 2009) in which a (Zn complex)···p-CH₃C₆H₄SO₃^-···(Zn complex) chain is constructed only by (O—H)_water···O_sulfonate hydrogen bonds, without the participation of ligand L1. In (I), the chain is generated from a combination of (O—H)_water···N_pyrimidine and (O—H)_water···O_sulfonate hydrogen bonds. Viewed along the crystallographic a direction, all the hydrogen-bond driven chains are parallel and further extend into a three-dimensional framework via O5—H5B···N3ⁱⁱ hydrogen bonds between double chains (Fig. 3) [symmetry code: (ii) x - 1/2, -y + 3/2, z + 1/2].

In summary, the introduction of both pyrimidyl and pyridyl donor groups in the 5-(3-pyridyl)pyrimidine ligand leads to a [ZnL₂(H₂O)₄]²⁺ complex cation with multiple hydrogen-bonding capabilities which combines with the CF₃SO₃^- counteranions to generate a novel three-dimensional network. This study demonstrates that such an asymmetric ligand plays an important role in constructing unusual supramolecular compounds, which may provide a new method for constructing novel functional materials in the future.

Related literature

For related literature, see: Allendorf et al. (2009); Cakir et al. (2003); Chen et al. (2004, 2008); Dong et al. (2007); Evans & Lin (2002); Fujita et al. (2005); Georgiev et al. (2004); He et al. (2006); Horikoshi et al. (2004); Hou et al. (2010); Khanpour & Morsali (2009); Peedikakkal & Vittal (2008); Thébault et al. (2006); Ye et al. (2005); Zheng et al. (2009); Zhu et al. (2009).

S2. Experimental

5-Bromopyrimidine (0.32 g, 2.0 mmol), 3-pyridineboronic acid (0.27 g, 2.2 mmol), [Pd(PPh₃)₄] (0.076 g, 0.066 mmol) and K₂CO₃ (0.83 g, 6.0 mmol) in EtOH–H₂O (3:1 v/v, 20 ml) were heated to reflux for 48 h. After removal of the solvents under vacuum, the residue was purified on silica gel using column chromatography with CH₂Cl₂–THF (10:1 v/v) as the eluent to give L as a colourless crystalline solid (yield 85%). Spectroscopic analysis: IR (KBr pellet, ν, cm^-1): 3026 (m), 1638 (m), 1592 (s), 1574 (s), 1443 (s), 1418 (s), 1400 (m), 1354 (m), 1233 (m), 1026 (m), 994 (m), 805 (m), 729 (s), 708 (s), 634 (s); ¹H NMR (300 MHz, DMSO-d₆, TMS, δ, p.p.m.): 9.27 (s, 1H, C₄H₄N₂), 8.97 (s, 2H, C₄H₄N₂), 8.87 (s, 1H, C₅H₄N), 8.74–8.72 (d, 1H, C₅H₄N), 7.95–7.92 (d, 1H, C₅H₄N), 7.52–7.48 (t, 1H, C₅H₄N). Elemental analysis, calculated for C₉H₇N₃: C 68.77, H 4.49, N 26.74%; found: C 68.54, H 4.57, N 26.83%.

A solution of Zn(OTf)₂ (9.0 mg, 0.025 mmol) in CH₃CN (2 ml) was layered onto a solution of L (7.8 mg, 0.050 mmol) in CH₂Cl₂ (2 ml). The system was left for about three weeks at room temperature and colourless crystals of (I) were obtained (yield 80%).

S3. Refinement

Water H atoms were located in a difference Fourier map and included as riding atoms, with O—H = 0.82 Å and U_iso(H) = 1.5U_eq(O). Other H atoms were placed in idealized positions and treated as riding, with C—H = 0.93 Å (CH) and U_iso(H) = 1.2U_eq(C).

The elongated displacement ellipsoids of the F atoms in the trifluoromethanesulfonate anion indicate possible disorder. However, attempts to refine the anion with split F positions were unsuccessful, resulting in very poor geometry about the C atom. In order to keep the OTf^- anion stable in the refinement, a series of C—F [1.40 (1) Å], C—S [1.65 (2) Å] and F···F [2.20 (2) Å] distance restraints were used.

Computing details

Data collection: SMART (Bruker, 2003); cell refinement: SMART (Bruker, 2003); data reduction: SAINT (Bruker, 2003); 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 Zn^II coordination environment of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 20% probability level. Hydrogen bonds are shown as dashed lines. [Symmetry code: (iv) -x + 1, -y + 1, -z + 1.]
	Fig. 2. The hydrogen-bond driven double chain formed along the crystallographic a direction of (I). Hydrogen bonds are shown as dashed lines. [Symmetry codes: (i) x - 1, y, z; (iii) x + 1, y, z.]
	Fig. 3. The three-dimensional framework of (I) formed via O4—H4B···N3^ii interactions (dashed lines) between double chains. [Symmetry code: (ii) x - 1/2, -y + 3/2, z + 1/2.]

Tetraaquabis[5-(3-pyridyl-κN)pyrimidine]zinc(II) bis(trifluoromethanesulfonate)

Crystal data

[Zn(C9H7N3)2(H2O)4](CF3SO3)2	F(000) = 760
Mr = 749.93	Dx = 1.623 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P2yn	Cell parameters from 3342 reflections
a = 9.3597 (15) Å	θ = 2.4–26.3°
b = 17.198 (3) Å	µ = 1.03 mm^−1
c = 9.6857 (16) Å	T = 298 K
β = 100.187 (2)°	Block, colourless
V = 1534.5 (4) Å^3	0.30 × 0.25 × 0.22 mm
Z = 2

Data collection

Bruker SMART APEX area-detector diffractometer	2854 independent reflections
Radiation source: fine-focus sealed tube	2428 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
ϕ and ω scans	θmax = 25.5°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −11→9
Tmin = 0.747, Tmax = 0.805	k = −20→17
7904 measured reflections	l = −11→11

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)] = 0.066	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.199	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.1235P)^2 + 2.782P] where P = (Fo^2 + 2Fc^2)/3
2854 reflections	(Δ/σ)max = 0.002
207 parameters	Δρmax = 1.24 e Å^−3
7 restraints	Δρmin = −0.93 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	0.6858 (5)	0.5987 (3)	0.3335 (5)	0.0393 (9)
H1	0.7515	0.5929	0.4169	0.047*
C2	0.7296 (5)	0.6407 (3)	0.2268 (5)	0.0458 (11)
C3	0.6292 (6)	0.6495 (4)	0.1046 (7)	0.077 (2)
H3	0.6529	0.6781	0.0304	0.092*
C4	0.4951 (7)	0.6161 (5)	0.0933 (7)	0.084 (2)
H4	0.4273	0.6213	0.0112	0.101*
C5	0.4615 (6)	0.5743 (4)	0.2057 (6)	0.0614 (15)
H5	0.3702	0.5516	0.1973	0.074*
C6	0.8781 (5)	0.6738 (3)	0.2441 (5)	0.0418 (10)
C7	0.9971 (5)	0.6315 (3)	0.3047 (5)	0.0449 (11)
H7	0.9833	0.5820	0.3388	0.054*
C8	1.1466 (6)	0.7289 (3)	0.2655 (6)	0.0515 (12)
H8	1.2407	0.7475	0.2709	0.062*
C9	0.9054 (6)	0.7473 (3)	0.1968 (6)	0.0543 (13)
H9	0.8276	0.7782	0.1564	0.065*
C10	0.0546 (10)	0.6359 (8)	0.8859 (9)	0.252 (13)
F1	−0.0687 (9)	0.6597 (10)	0.9256 (8)	0.372 (12)
F2	0.1027 (9)	0.5808 (9)	0.9805 (8)	0.270 (7)
F3	0.1620 (11)	0.6898 (8)	0.9172 (12)	0.334 (10)
N1	0.5545 (4)	0.5655 (2)	0.3247 (4)	0.0424 (9)
N2	1.1324 (4)	0.6591 (2)	0.3162 (5)	0.0510 (10)
N3	1.0398 (5)	0.7752 (2)	0.2075 (5)	0.0576 (11)
O1	0.1679 (7)	0.5810 (7)	0.7119 (7)	0.162 (4)
O2	−0.0105 (14)	0.6749 (6)	0.6474 (12)	0.220 (6)
O3	−0.0791 (6)	0.5567 (4)	0.6927 (10)	0.150 (3)
O4	0.6236 (3)	0.57343 (19)	0.6463 (4)	0.0477 (8)
H4A	0.7099	0.5679	0.6427	0.072*
H4B	0.5847	0.6160	0.6483	0.072*
O5	0.3230 (3)	0.5719 (2)	0.5052 (4)	0.0491 (8)
H5A	0.2966	0.5913	0.4276	0.074*
H5B	0.2634	0.5681	0.5569	0.074*
S1	0.02853 (16)	0.61022 (10)	0.72069 (16)	0.0635 (4)
Zn1	0.5000	0.5000	0.5000	0.0339 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.035 (2)	0.040 (2)	0.044 (2)	−0.0001 (17)	0.0080 (17)	0.0065 (18)
C2	0.040 (2)	0.045 (2)	0.054 (3)	0.0066 (19)	0.011 (2)	0.014 (2)
C3	0.054 (3)	0.104 (5)	0.070 (4)	−0.006 (3)	0.003 (3)	0.049 (4)
C4	0.054 (3)	0.124 (6)	0.067 (4)	−0.007 (4)	−0.010 (3)	0.044 (4)
C5	0.037 (3)	0.075 (4)	0.069 (3)	−0.007 (2)	0.001 (2)	0.018 (3)
C6	0.042 (2)	0.040 (2)	0.046 (2)	0.0014 (19)	0.0143 (19)	0.0099 (19)
C7	0.044 (2)	0.041 (2)	0.052 (3)	0.0033 (19)	0.013 (2)	0.014 (2)
C8	0.046 (3)	0.050 (3)	0.060 (3)	−0.006 (2)	0.013 (2)	0.008 (2)
C9	0.051 (3)	0.046 (3)	0.068 (3)	0.004 (2)	0.017 (2)	0.019 (2)
C10	0.095 (8)	0.58 (4)	0.067 (6)	0.108 (15)	−0.023 (5)	−0.066 (14)
F1	0.174 (8)	0.81 (3)	0.131 (6)	0.183 (13)	0.019 (6)	−0.167 (12)
F2	0.152 (7)	0.54 (2)	0.126 (6)	0.050 (10)	0.030 (5)	0.167 (10)
F3	0.238 (11)	0.47 (2)	0.237 (12)	0.116 (13)	−0.114 (9)	−0.240 (14)
N1	0.0357 (19)	0.042 (2)	0.050 (2)	0.0016 (15)	0.0084 (16)	0.0089 (17)
N2	0.042 (2)	0.052 (2)	0.060 (2)	0.0009 (18)	0.0096 (18)	0.014 (2)
N3	0.056 (3)	0.043 (2)	0.075 (3)	−0.0034 (19)	0.015 (2)	0.016 (2)
O1	0.077 (4)	0.310 (11)	0.112 (5)	0.029 (5)	0.050 (3)	−0.031 (6)
O2	0.312 (15)	0.128 (7)	0.180 (9)	−0.004 (8)	−0.062 (9)	0.059 (7)
O3	0.067 (3)	0.101 (4)	0.258 (9)	0.003 (3)	−0.036 (4)	−0.047 (5)
O4	0.0365 (16)	0.0396 (17)	0.065 (2)	−0.0010 (13)	0.0041 (15)	−0.0129 (15)
O5	0.0389 (17)	0.058 (2)	0.0533 (19)	0.0189 (15)	0.0148 (14)	0.0090 (16)
S1	0.0558 (8)	0.0761 (10)	0.0595 (8)	0.0026 (7)	0.0131 (6)	−0.0077 (7)
Zn1	0.0266 (4)	0.0318 (4)	0.0438 (4)	0.0003 (2)	0.0082 (3)	−0.0005 (3)

Geometric parameters (Å, º)

C1—N1	1.344 (6)	C9—H9	0.9300
C1—C2	1.382 (6)	C10—F2	1.340 (9)
C1—H1	0.9300	C10—F1	1.343 (8)
C2—C3	1.383 (7)	C10—F3	1.362 (9)
C2—C6	1.483 (6)	C10—S1	1.637 (9)
C3—C4	1.367 (9)	N1—Zn1	2.173 (4)
C3—H3	0.9300	O1—S1	1.415 (6)
C4—C5	1.387 (8)	O2—S1	1.335 (9)
C4—H4	0.9300	O3—S1	1.356 (6)
C5—N1	1.324 (6)	O4—Zn1	2.088 (3)
C5—H5	0.9300	O4—H4A	0.8200
C6—C7	1.372 (6)	O4—H4B	0.8192
C6—C9	1.385 (7)	O5—Zn1	2.075 (3)
C7—N2	1.338 (6)	O5—H5A	0.8200
C7—H7	0.9300	O5—H5B	0.8149
C8—N2	1.312 (6)	Zn1—O5^i	2.075 (3)
C8—N3	1.323 (7)	Zn1—O4^i	2.088 (3)
C8—H8	0.9300	Zn1—N1^i	2.173 (4)
C9—N3	1.334 (7)
N1—C1—C2	124.3 (4)	C5—N1—C1	117.4 (4)
N1—C1—H1	117.9	C5—N1—Zn1	122.0 (3)
C2—C1—H1	117.9	C1—N1—Zn1	120.6 (3)
C1—C2—C3	116.8 (5)	C8—N2—C7	116.8 (4)
C1—C2—C6	120.8 (4)	C8—N3—C9	116.6 (4)
C3—C2—C6	122.4 (4)	Zn1—O4—H4A	109.5
C4—C3—C2	119.9 (5)	Zn1—O4—H4B	111.2
C4—C3—H3	120.1	H4A—O4—H4B	123.3
C2—C3—H3	120.1	Zn1—O5—H5A	109.5
C3—C4—C5	119.2 (5)	Zn1—O5—H5B	127.2
C3—C4—H4	120.4	H5A—O5—H5B	117.8
C5—C4—H4	120.4	O2—S1—O3	109.6 (6)
N1—C5—C4	122.5 (5)	O2—S1—O1	115.6 (8)
N1—C5—H5	118.8	O3—S1—O1	114.0 (5)
C4—C5—H5	118.8	O2—S1—C10	105.9 (7)
C7—C6—C9	116.3 (4)	O3—S1—C10	110.9 (6)
C7—C6—C2	121.2 (4)	O1—S1—C10	100.1 (4)
C9—C6—C2	122.5 (4)	O5—Zn1—O5^i	180.00 (19)
N2—C7—C6	122.1 (4)	O5—Zn1—O4^i	91.62 (13)
N2—C7—H7	118.9	O5^i—Zn1—O4^i	88.38 (13)
C6—C7—H7	118.9	O5—Zn1—O4	88.38 (13)
N2—C8—N3	126.2 (5)	O5^i—Zn1—O4	91.62 (13)
N2—C8—H8	116.9	O4^i—Zn1—O4	180.00 (14)
N3—C8—H8	116.9	O5—Zn1—N1	90.51 (14)
N3—C9—C6	122.0 (5)	O5^i—Zn1—N1	89.49 (14)
N3—C9—H9	119.0	O4^i—Zn1—N1	87.81 (14)
C6—C9—H9	119.0	O4—Zn1—N1	92.19 (14)
F2—C10—F1	102.8 (9)	O5—Zn1—N1^i	89.49 (14)
F2—C10—F3	100.6 (8)	O5^i—Zn1—N1^i	90.51 (14)
F1—C10—F3	111.6 (11)	O4^i—Zn1—N1^i	92.19 (14)
F2—C10—S1	116.8 (9)	O4—Zn1—N1^i	87.81 (14)
F1—C10—S1	112.0 (6)	N1—Zn1—N1^i	180.00 (17)
F3—C10—S1	112.2 (7)
N1—C1—C2—C3	1.0 (8)	C6—C9—N3—C8	0.1 (8)
N1—C1—C2—C6	−178.5 (4)	F2—C10—S1—O2	−176.5 (9)
C1—C2—C3—C4	−1.1 (10)	F1—C10—S1—O2	65.3 (13)
C6—C2—C3—C4	178.4 (7)	F3—C10—S1—O2	−61.1 (10)
C2—C3—C4—C5	0.6 (12)	F2—C10—S1—O3	64.7 (9)
C3—C4—C5—N1	0.2 (12)	F1—C10—S1—O3	−53.5 (12)
C1—C2—C6—C7	43.0 (7)	F3—C10—S1—O3	−179.9 (7)
C3—C2—C6—C7	−136.5 (6)	F2—C10—S1—O1	−56.0 (9)
C1—C2—C6—C9	−139.0 (5)	F1—C10—S1—O1	−174.2 (11)
C3—C2—C6—C9	41.5 (8)	F3—C10—S1—O1	59.4 (9)
C9—C6—C7—N2	−0.8 (8)	C5—N1—Zn1—O5	−57.5 (4)
C2—C6—C7—N2	177.3 (5)	C1—N1—Zn1—O5	122.8 (3)
C7—C6—C9—N3	1.0 (8)	C5—N1—Zn1—O5^i	122.5 (4)
C2—C6—C9—N3	−177.0 (5)	C1—N1—Zn1—O5^i	−57.2 (3)
C4—C5—N1—C1	−0.4 (9)	C5—N1—Zn1—O4^i	34.1 (4)
C4—C5—N1—Zn1	179.9 (6)	C1—N1—Zn1—O4^i	−145.6 (3)
C2—C1—N1—C5	−0.3 (7)	C5—N1—Zn1—O4	−145.9 (4)
C2—C1—N1—Zn1	179.5 (4)	C1—N1—Zn1—O4	34.4 (3)
N3—C8—N2—C7	1.9 (8)	C5—N1—Zn1—N1^i	177 (100)
C6—C7—N2—C8	−0.5 (8)	C1—N1—Zn1—N1^i	−2 (100)
N2—C8—N3—C9	−1.7 (9)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5B···O1	0.81	1.89	2.677 (7)	162
O5—H5A···N2^ii	0.82	2.07	2.762 (5)	142
O4—H4B···N3^iii	0.82	2.02	2.812 (5)	162
O4—H4A···O3^iv	0.82	1.96	2.755 (7)	164

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