A two-dimensional zinc(II) coordination polymer created via in situ ligand synthesis involving C-N bond formation

The novel Zn^II coordination polymer poly[{[mu]₄-2-[3-(pyridin-2-yl)-1H-pyrazol-3-yl]butane­dioato}zinc(II)], [Zn(C₁₂H₉N₃O₄)]_n, has been synthesized hydro­thermally and structurally characterized. The results demonstrate that the complex shows two-dimensional neutral wave-like layers. The complex was prepared by the conjugate addition reaction of 2-(1H-pyrazol-3-yl)pyridine to cis-fumaric acid in the presence of Zn(OAc)₂·2H₂O (OAc is acetate) at 413 K.

S1. Introduction

The rational design and construction of metal–organic coordination polymers has attracted increasing inter­est, not only for their intriguing variety of architectures and topologies (Al-Rasbi et al., 2008; Ronson et al., 2007; Tranchemontagne et al., 2008), but also for the scope they present for developing new hybrid materials with potential applications in the fields of gas absorption, magnetism, nonlinear optics and catalysis (Kitagawa et al., 2004; Fujita et al., 1994; Evans & Lin, 2002). In this regard, it has been realized that the assembly processes are strongly dependent on the nature of the building units, such as metal ions and organic ligands, as well as the reaction routes (Du et al., 2006; Barnett & Champness, 2003; Lu, 2003). The solvothermal technique has been confirmed to be a powerful and effective approach for the preparation of inorganic (Chen & Tong, 2007) and inorganic–organic hybrid materials (Lu, 2003). Of further inter­est are a variety of possible in situ metal/ligand reactions, such as the conjugate addition reaction of C═C. In this way, unexpected coordination compounds that are inaccessibe or not easily obtainable by conventional methods may be achieved, which can provide a new avenue for the development of crystalline materials with unusual structures and properties. We have reported the synthesis of a coordination polymer of cadmium (Cai et al., 2013) which comprises a ligand molecule not included in the original reaction mixture but instead formed in situ during hydro­thermal treatment. In this context, we describe herein the same in situ solvothermal generation of a Zn^II complex, namely poly[{µ₄-2-[3-(pyridin-2-yl)-1H-pyrazol-3-yl]butane­dioato}zinc(II)], [Zn(L1)]_n, (I).

The title complex, (I) (Scheme 1 and Fig. 1), was synthesized from zinc acetate, 2-(1H-pyrazol-3-yl)pyridine and cis-fumaric acid. The ligand is formed by the conjugate addition of 2-(1H-pyrazol-3-yl)pyridine to cis-fumaric acid, as shown in Scheme 2.

S2. Experimental

S2.1. Synthesis and crystallization

A mixture containing Zn(OAc)₂.2H₂O (OAc is acetate; 21.9 mg, 0.10 mmol), 2-(1H-pyrazol-3-yl)pyridine (14.5 mg, 0.10 mmol), cis-fumaric acid (11.6 mg, 0.10 mmol) and H₂O (10 ml) was sealed in a Teflon-lined stainless steel vessel (20 ml), which was heated at 413 K for 3 d and then cooled to room temperature at a rate of 5 K h^-1. Colourless block-shaped crystals suitable for X-ray analysis were obtained in 34% yield. Analysis, calculated for C₁₂H₉N₃O₄Zn: C 40.40, H 2.79, N 12.95%; found: C 40.51, H 2.71, N 12.89%.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. [Please give here details of H-atom treatment and handling of disorder]

S3. Results and discussion

Single-crystal X-ray analysis of (I) shows that the asymmetric unit contains one Zn^II cation and one 2-[3-(pyridin-2-yl)-1H-pyrazol-3-yl]butane­dioate (L1)^2- dianion. As shown in Fig. 1, each Zn^II cation is five-coordinated by two N atoms of one (L1)^2- ligand [Zn1—N = 2.081 (3)–2.160 (4) Å] and by three carboxyl­ate O atoms from three different (L1)^2- ligands [Zn1—O = 1.973 (3)–2.157 (4) Å] to form a ideal square-pyramidal geometry (Table 2) with a τ parameter of 0.00008 (τ = 0 for an ideal square-pyramidal geometry and τ = 1 for an ideal trigonal–bipyramidal geometry; Addison et al., 1984). Three carboxyl­ate O atoms from the (L1)^2- ligand adopt bidentate–bridging and monodentate coordinating modes and each (L1)^2- ligand acts as a µ₄-bridge linking four Zn^II cations, resulting in a two-dimensional layered network extending along the bc plane. In addition, atoms C9 and C11 of (I) are disordered and the site-occupancy factors were handled by changing the value of the SOF instruction from 11.0000 to 21.0000 and -21.0000 for these atoms. The C9 and C9' disordered model, which contains ligands in the R and S forms, was refined with better S (68.8%) and R (31.2%) values. [Not very clear, please reword with no software-specific terms. Please also beware confusing the reliability index R with the enanti­omeric R notation]

Within the two-dimensional layer, weak C8—H8···O2 and C11—H11A···O1 hydrogen-bond inter­actions are observed that further stabilize the crystal structure (Fig. 2). Additionally, adjacent two-dimensional motifs are aligned in a parallel manner and are extended into a three-dimensional supra­molecular network by weak C3—H3···O1 and C4—H4···O2 hydrogen-bond inter­actions (Fig. 3). The geometry of the C3—H3···O1, C4—H4···O2 and C8—H8···O2 hydrogen bonds (Table 3) falls within the range for weak hydrogen bonds (Desiraju, 2002). This indicates that, beyond metal coordination, the (L1)^2- ligand also has potential sites for hydrogen bonding for the formation of supra­molecular networks.

Structural transformation and diversification are observed in the reaction system of [Zn(L1)]_n and [Cd(L1)]_n (Cai et al., 2013). In [Zn(L1)]_n and [Cd(L1)]_n, the deprotonated (L1)^2- ligands play almost the same role. However, the different coordination modes adopted by the ligands lead to a variation in the structural motifs. The structure of [Zn(L1)]_n displays two-dimensional layers in which the (L1)^2- ligand acts in a µ₄-bridging mode. In contrast, the structure of [Cd(L1)]_n displays one-dimensional double-strand chains, with the (L1)^2- ligand acting in a µ₄-bridging mode. The different geometric conformation in the (L1)^2- ligand results in the formation of two-dimensional layers in [Zn(L1)]_n and one-dimensional double-strand chains in [Cd(L1)]_n {torsion angles C10—C9—C11—C12 and N3—C9—C11—C12 = -175.2 and -34.5°, respectively, for [Zn(L1)]_n, and -60.4 and 69.2°, respectively, for [Cd(L1)]_n} [Can this repetition be removed? Are the torsion angles relevant?].

In summary, a novel two-dimensional coordination polymer is formed from 2-(1H-pyrazol-3-yl)pyridine, fumaric acid and Zn(OAc)₂.2H₂O, and diplays a three-dimensional supra­molecular framework. Notably, the results may bring some new insights with regard to inter­esting polymeric complexes formed from in situ metal/ligand reactions, and further efforts in this direction are ongoing.

Computing details

Data collection: APEX2 (Bruker, 2003); cell refinement: APEX2 (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) and DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. A view of the local coordination of the Zn^II cations in (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (i) -x, -y, -z + 1; (ii) x, -y + 1/2, z + 1/2; (iii) x, y, z + 1.]
	Fig. 2. A perspective view of the two-dimensional layer in (I), along the bc plane. [Dashed lines indicate hydrogen bonds?]
	Fig. 3. The three-dimensional supramolecular framework of (I) formed through weak hydrogen-bonding interactions [Dashed lines?].

Poly[{µ₄-2-[3-(pyridin-2-yl)-1H-pyrazol-3-yl]butanedioato}zinc(II)]

Crystal data

[Zn(C12H9N3O4)]	F(000) = 656
Mr = 324.59	Dx = 1.835 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1449 reflections
a = 9.002 (2) Å	θ = 2.6–25.1°
b = 16.553 (4) Å	µ = 2.11 mm^−1
c = 7.8865 (18) Å	T = 296 K
β = 90.212 (4)°	Block, colourless
V = 1175.1 (5) Å^3	0.20 × 0.16 × 0.14 mm
Z = 4

Data collection

Bruker APEXII CCD area-detector diffractometer	2184 independent reflections
Radiation source: fine-focus sealed tube	1587 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.037
ϕ and ω scans	θmax = 25.5°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −10→10
Tmin = 0.678, Tmax = 0.757	k = −20→17
6144 measured reflections	l = −9→9

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.092	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0315P)^2 + 1.3191P] where P = (Fo^2 + 2Fc^2)/3
2184 reflections	(Δ/σ)max = 0.001
200 parameters	Δρmax = 0.48 e Å^−3
8 restraints	Δρmin = −0.43 e Å^−3

Special details

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

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

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Zn1	0.15056 (5)	0.14483 (3)	0.65703 (7)	0.03963 (18)
O1	−0.0019 (3)	−0.05493 (18)	0.3212 (4)	0.0464 (8)
O2	−0.2081 (4)	0.00812 (19)	0.2480 (4)	0.0541 (9)
O3	0.0223 (4)	0.2623 (2)	0.1003 (5)	0.0690 (11)
O4	0.1375 (4)	0.1891 (2)	−0.0862 (5)	0.0697 (10)
N1	0.3801 (4)	0.1565 (2)	0.6771 (4)	0.0379 (8)
N2	0.2283 (4)	0.1055 (2)	0.4117 (4)	0.0384 (9)
N3	0.1732 (4)	0.0782 (2)	0.2638 (5)	0.0470 (10)
C1	0.4530 (5)	0.1854 (3)	0.8125 (6)	0.0497 (12)
H1	0.3981	0.2061	0.9022	0.060*
C2	0.6049 (5)	0.1857 (3)	0.8247 (7)	0.0631 (15)
H2	0.6519	0.2070	0.9200	0.076*
C3	0.6862 (5)	0.1541 (3)	0.6945 (7)	0.0599 (14)
H3	0.7894	0.1536	0.7004	0.072*
C4	0.6141 (5)	0.1230 (3)	0.5540 (6)	0.0471 (12)
H4	0.6676	0.1006	0.4648	0.057*
C5	0.4613 (4)	0.1259 (2)	0.5491 (6)	0.0365 (10)
C6	0.3750 (4)	0.0976 (2)	0.4024 (5)	0.0350 (10)
C7	0.4157 (5)	0.0648 (3)	0.2475 (6)	0.0506 (12)
H7	0.5108	0.0530	0.2089	0.061*
C8	0.2837 (6)	0.0536 (3)	0.1650 (6)	0.0558 (13)
H8	0.2728	0.0321	0.0567	0.067*
C10	−0.0713 (5)	0.0063 (3)	0.2711 (5)	0.0390 (10)
C9	0.0070 (6)	0.0888 (4)	0.2450 (9)	0.0296 (19)	0.688 (10)
H9A	−0.0283	0.1270	0.3308	0.035*	0.688 (10)
C11	−0.0353 (7)	0.1200 (4)	0.0688 (9)	0.039 (2)	0.688 (10)
H11A	−0.0109	0.0796	−0.0158	0.047*	0.688 (10)
H11B	−0.1414	0.1298	0.0636	0.047*	0.688 (10)
C9'	0.0323 (11)	0.0636 (7)	0.1771 (16)	0.035 (5)	0.312 (10)
H9'A	0.0498	0.0442	0.0615	0.043*	0.312 (10)
C11'	−0.0256 (14)	0.1498 (7)	0.1739 (17)	0.038 (4)	0.312 (10)
H11C	−0.0055	0.1755	0.2821	0.046*	0.312 (10)
H11D	−0.1323	0.1493	0.1564	0.046*	0.312 (10)
C12	0.0487 (5)	0.1982 (3)	0.0315 (6)	0.0368 (10)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0316 (3)	0.0379 (3)	0.0495 (3)	−0.0020 (2)	0.0063 (2)	0.0057 (3)
O1	0.0463 (18)	0.0390 (18)	0.054 (2)	−0.0031 (15)	0.0108 (15)	0.0038 (15)
O2	0.048 (2)	0.057 (2)	0.057 (2)	−0.0129 (17)	−0.0018 (16)	0.0068 (17)
O3	0.050 (2)	0.061 (2)	0.096 (3)	−0.0088 (18)	0.0113 (19)	−0.038 (2)
O4	0.059 (2)	0.082 (3)	0.069 (3)	0.007 (2)	0.010 (2)	−0.022 (2)
N1	0.0346 (19)	0.037 (2)	0.042 (2)	−0.0041 (16)	0.0021 (16)	−0.0025 (17)
N2	0.0322 (19)	0.042 (2)	0.041 (2)	−0.0056 (16)	−0.0019 (16)	0.0082 (17)
N3	0.045 (2)	0.056 (3)	0.040 (2)	−0.0166 (19)	−0.0056 (19)	0.0126 (19)
C1	0.047 (3)	0.050 (3)	0.053 (3)	−0.003 (2)	−0.001 (2)	−0.011 (2)
C2	0.047 (3)	0.069 (4)	0.073 (4)	−0.003 (3)	−0.023 (3)	−0.012 (3)
C3	0.030 (2)	0.062 (3)	0.088 (4)	0.000 (2)	−0.012 (3)	0.002 (3)
C4	0.033 (2)	0.049 (3)	0.060 (3)	−0.001 (2)	0.002 (2)	−0.002 (2)
C5	0.032 (2)	0.029 (2)	0.049 (3)	0.0002 (18)	0.002 (2)	0.0076 (19)
C6	0.034 (2)	0.032 (2)	0.039 (3)	−0.0049 (19)	0.0003 (19)	0.0057 (19)
C7	0.054 (3)	0.050 (3)	0.047 (3)	−0.006 (2)	0.012 (2)	−0.001 (2)
C8	0.076 (4)	0.054 (3)	0.037 (3)	−0.018 (3)	−0.005 (3)	0.000 (2)
C10	0.048 (3)	0.043 (3)	0.026 (2)	−0.011 (2)	0.003 (2)	0.000 (2)
C9	0.034 (3)	0.033 (5)	0.022 (4)	−0.007 (3)	−0.006 (3)	−0.005 (3)
C11	0.044 (4)	0.035 (4)	0.038 (4)	−0.010 (3)	−0.011 (3)	−0.001 (3)
C9'	0.050 (10)	0.039 (10)	0.018 (9)	−0.008 (7)	−0.006 (7)	−0.016 (7)
C11'	0.025 (7)	0.036 (9)	0.053 (11)	−0.001 (7)	−0.007 (7)	−0.006 (8)
C12	0.034 (2)	0.037 (3)	0.040 (3)	−0.005 (2)	−0.004 (2)	0.008 (2)

Geometric parameters (Å, º)

Zn1—O3^i	1.973 (3)	C2—H2	0.9300
Zn1—O1^ii	2.009 (3)	C3—C4	1.382 (7)
Zn1—N1	2.081 (3)	C3—H3	0.9300
Zn1—O4^iii	2.157 (4)	C4—C5	1.377 (6)
Zn1—N2	2.160 (4)	C4—H4	0.9300
O1—C10	1.253 (5)	C5—C6	1.467 (6)
O1—Zn1^ii	2.009 (3)	C6—C7	1.388 (6)
O2—C10	1.244 (5)	C7—C8	1.366 (6)
O3—C12	1.215 (5)	C7—H7	0.9300
O3—Zn1^iv	1.973 (3)	C8—H8	0.9300
O4—C12	1.236 (5)	C10—C9'	1.525 (9)
O4—Zn1^v	2.157 (4)	C10—C9	1.551 (6)
N1—C1	1.340 (5)	C9—C11	1.529 (7)
N1—C5	1.347 (5)	C9—H9A	0.9800
N2—C6	1.330 (5)	C11—C12	1.529 (6)
N2—N3	1.344 (5)	C11—H11A	0.9700
N3—C8	1.330 (6)	C11—H11B	0.9700
N3—C9'	1.459 (9)	C9'—C11'	1.519 (10)
N3—C9	1.514 (6)	C9'—H9'A	0.9800
C1—C2	1.371 (6)	C11'—C12	1.536 (9)
C1—H1	0.9300	C11'—H11C	0.9700
C2—C3	1.367 (7)	C11'—H11D	0.9700
O3^i—Zn1—O1^ii	101.94 (14)	C7—C6—C5	132.7 (4)
O3^i—Zn1—N1	121.69 (14)	C8—C7—C6	103.9 (4)
O1^ii—Zn1—N1	136.37 (13)	C8—C7—H7	128.0
O3^i—Zn1—O4^iii	85.09 (16)	C6—C7—H7	128.0
O1^ii—Zn1—O4^iii	97.63 (13)	N3—C8—C7	109.3 (4)
N1—Zn1—O4^iii	87.41 (14)	N3—C8—H8	125.4
O3^i—Zn1—N2	102.88 (15)	C7—C8—H8	125.4
O1^ii—Zn1—N2	94.09 (12)	O2—C10—O1	123.9 (4)
N1—Zn1—N2	76.77 (13)	O2—C10—C9'	121.3 (5)
O4^iii—Zn1—N2	164.17 (13)	O1—C10—C9'	110.6 (6)
C10—O1—Zn1^ii	107.1 (3)	O2—C10—C9	114.1 (4)
C12—O3—Zn1^iv	131.7 (3)	O1—C10—C9	121.8 (4)
C12—O4—Zn1^v	141.6 (3)	N3—C9—C11	111.7 (5)
C1—N1—C5	117.8 (4)	N3—C9—C10	109.6 (4)
C1—N1—Zn1	125.2 (3)	C11—C9—C10	107.9 (5)
C5—N1—Zn1	116.7 (3)	N3—C9—H9A	109.2
C6—N2—N3	106.4 (4)	C11—C9—H9A	109.2
C6—N2—Zn1	113.8 (3)	C10—C9—H9A	109.2
N3—N2—Zn1	139.4 (3)	C12—C11—C9	109.9 (5)
C8—N3—N2	109.7 (4)	C12—C11—H11A	109.7
C8—N3—C9'	109.0 (6)	C9—C11—H11A	109.7
N2—N3—C9'	141.2 (7)	C12—C11—H11B	109.7
C8—N3—C9	136.0 (4)	C9—C11—H11B	109.7
N2—N3—C9	114.1 (4)	H11A—C11—H11B	108.2
N1—C1—C2	122.9 (5)	N3—C9'—C11'	98.6 (9)
N1—C1—H1	118.6	N3—C9'—C10	114.1 (7)
C2—C1—H1	118.6	C11'—C9'—C10	112.4 (9)
C3—C2—C1	118.9 (5)	N3—C9'—H9'A	110.4
C3—C2—H2	120.6	C11'—C9'—H9'A	110.4
C1—C2—H2	120.6	C10—C9'—H9'A	110.4
C2—C3—C4	119.6 (4)	C9'—C11'—C12	110.6 (8)
C2—C3—H3	120.2	C9'—C11'—H11C	109.5
C4—C3—H3	120.2	C12—C11'—H11C	109.5
C5—C4—C3	118.4 (5)	C9'—C11'—H11D	109.5
C5—C4—H4	120.8	C12—C11'—H11D	109.5
C3—C4—H4	120.8	H11C—C11'—H11D	108.1
N1—C5—C4	122.4 (4)	O3—C12—O4	124.8 (4)
N1—C5—C6	115.1 (4)	O3—C12—C11	123.7 (5)
C4—C5—C6	122.5 (4)	O4—C12—C11	111.3 (5)
N2—C6—C7	110.6 (4)	O3—C12—C11'	92.4 (6)
N2—C6—C5	116.6 (4)	O4—C12—C11'	140.3 (6)
O3^i—Zn1—N1—C1	80.4 (4)	C9—N3—C8—C7	173.9 (5)
O1^ii—Zn1—N1—C1	−100.6 (4)	C6—C7—C8—N3	0.1 (5)
O4^iii—Zn1—N1—C1	−2.2 (4)	Zn1^ii—O1—C10—O2	2.6 (5)
N2—Zn1—N1—C1	177.5 (4)	Zn1^ii—O1—C10—C9'	−154.5 (6)
O3^i—Zn1—N1—C5	−105.7 (3)	Zn1^ii—O1—C10—C9	178.1 (4)
O1^ii—Zn1—N1—C5	73.3 (3)	C8—N3—C9—C11	−37.6 (8)
O4^iii—Zn1—N1—C5	171.7 (3)	N2—N3—C9—C11	136.4 (5)
N2—Zn1—N1—C5	−8.6 (3)	C9'—N3—C9—C11	−54.0 (10)
O3^i—Zn1—N2—C6	128.5 (3)	C8—N3—C9—C10	81.9 (7)
O1^ii—Zn1—N2—C6	−128.3 (3)	N2—N3—C9—C10	−104.1 (5)
N1—Zn1—N2—C6	8.5 (3)	C9'—N3—C9—C10	65.5 (10)
O4^iii—Zn1—N2—C6	9.5 (7)	O2—C10—C9—N3	−176.0 (4)
O3^i—Zn1—N2—N3	−59.9 (4)	O1—C10—C9—N3	8.2 (7)
O1^ii—Zn1—N2—N3	43.3 (4)	C9'—C10—C9—N3	−63.8 (10)
N1—Zn1—N2—N3	−179.9 (4)	O2—C10—C9—C11	−54.1 (7)
O4^iii—Zn1—N2—N3	−178.9 (5)	O1—C10—C9—C11	130.0 (5)
C6—N2—N3—C8	0.3 (5)	C9'—C10—C9—C11	58.0 (10)
Zn1—N2—N3—C8	−171.7 (3)	N3—C9—C11—C12	−55.2 (7)
C6—N2—N3—C9'	177.0 (8)	C10—C9—C11—C12	−175.7 (5)
Zn1—N2—N3—C9'	5.0 (10)	C8—N3—C9'—C11'	−121.4 (7)
C6—N2—N3—C9	−175.3 (4)	N2—N3—C9'—C11'	61.8 (11)
Zn1—N2—N3—C9	12.7 (6)	C9—N3—C9'—C11'	46.7 (9)
C5—N1—C1—C2	0.7 (7)	C8—N3—C9'—C10	119.2 (8)
Zn1—N1—C1—C2	174.5 (4)	N2—N3—C9'—C10	−57.6 (13)
N1—C1—C2—C3	−1.0 (8)	C9—N3—C9'—C10	−72.7 (12)
C1—C2—C3—C4	0.2 (8)	O2—C10—C9'—N3	155.6 (7)
C2—C3—C4—C5	0.9 (7)	O1—C10—C9'—N3	−46.5 (11)
C1—N1—C5—C4	0.4 (6)	C9—C10—C9'—N3	73.9 (11)
Zn1—N1—C5—C4	−173.9 (3)	O2—C10—C9'—C11'	44.4 (12)
C1—N1—C5—C6	−178.1 (4)	O1—C10—C9'—C11'	−157.7 (9)
Zn1—N1—C5—C6	7.5 (4)	C9—C10—C9'—C11'	−37.4 (10)
C3—C4—C5—N1	−1.2 (6)	N3—C9'—C11'—C12	79.0 (12)
C3—C4—C5—C6	177.3 (4)	C10—C9'—C11'—C12	−160.4 (8)
N3—N2—C6—C7	−0.2 (5)	Zn1^iv—O3—C12—O4	−36.4 (7)
Zn1—N2—C6—C7	174.1 (3)	Zn1^iv—O3—C12—C11	149.8 (4)
N3—N2—C6—C5	178.4 (3)	Zn1^iv—O3—C12—C11'	129.0 (7)
Zn1—N2—C6—C5	−7.3 (4)	Zn1^v—O4—C12—O3	−123.3 (5)
N1—C5—C6—N2	0.2 (5)	Zn1^v—O4—C12—C11	51.2 (7)
C4—C5—C6—N2	−178.4 (4)	Zn1^v—O4—C12—C11'	80.0 (12)
N1—C5—C6—C7	178.3 (4)	C9—C11—C12—O3	−71.3 (7)
C4—C5—C6—C7	−0.2 (7)	C9—C11—C12—O4	114.1 (6)
N2—C6—C7—C8	0.0 (5)	C9—C11—C12—C11'	−35.0 (8)
C5—C6—C7—C8	−178.2 (4)	C9'—C11'—C12—O3	−157.7 (10)
N2—N3—C8—C7	−0.2 (5)	C9'—C11'—C12—O4	3.4 (17)
C9'—N3—C8—C7	−178.1 (5)	C9'—C11'—C12—C11	51.8 (8)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11A···O1^vi	0.97	2.45	3.278 (8)	144
C8—H8···O2^vi	0.93	2.56	3.478 (6)	170
C4—H4···O2^vii	0.93	2.56	3.468 (6)	167
C3—H3···O1^viii	0.93	2.52	3.285 (6)	140

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