Two one-dimensional zinc(II) coordination polymers: catena-poly[[bis­(pentane-2,4-dionato-[kappa]²O,O')zinc]-[mu]-1,4-bis­(x-pyrid­yl)-2,3-diaza­buta-1,3-diene] (x = 3, 4)

The structures of the two title isomeric compounds, [Zn(C₅H₇O₂)₂(C₁₂H₁₀N₄)]_n, are built up around two non-equivalent symmetry centres, one of them at the cation position and the other bisecting the N-N bond in the 1,4-bis­(3/4-pyrid­yl)-2,3-diaza­buta-1,3-diene (3pdb/4pdb) units. Both Zn cations have the Zn atoms an inversion centres and present tetra­gonally distorted octa­hedral environments, but differences in their linkage through the 3pdb and 4pdb ligands give rise to differently shaped weakly inter­acting chains.

S1. Comment

The exo-bidentate bis-pyridyl ligand 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene (4 pd b) has been reported to form coordination polymers with several metal centers (Co^II, Cd^II, Ni^II, Ag^I, Mn^II and Pb^II) containing diverse counter-ions (NO₃⁻, SCN⁻, I⁻ and saccharinate) (Ciurtin et al., 2001; Kallil et al., 2005; Shen, 2003; Shi, Li, Li et al., 2002; Shi, Li, Tong et al., 2002). These polymeric complexes usually present interesting structural topologies, but recently it has been reported that the reaction of zinc perclorate hexahydrate with the bis-pyridyl ligand 4 pd b, under mild conditions, results in the formation of a non-polymeric compound, viz. [Zn(4 pd b)₂(MeOH)₂(H₂O)₂](ClO₄)₂(4 pd b). 1.72MeOH·1.28H₂O (Shoshnik et al., 2005), hereafter (III), with a [2 + 2+2]-octahedral coordination environment around the zinc ion and a trans configuration of the related coordinated species 4 pd b, MeOH and H₂O. Thus, the pyridyl N atoms of two molecules of 4 pd b are bonded axially to the solvated cationic fragment [Zn(MeOH)₂(H₂O)₂]²⁺, giving rise to a linear N—Zn^II—N oligomer. The pyridyl rings of adjacent oligomers are ordered in a such a way as to promote π–π stacking interactions.

In the present work we report on the structural differences found when the neutral ligands providing the O-donor atoms to the Zn(MeOH)₂(H₂O)₂]²⁺ oligomer core in (III) (viz. water and methanol) are replaced by a different O-donor ligand, the β-diketonate acetylacetonate (acac), through the Zn(acac)₂ complex. By contrast with the above Zn(MeOH)₂(H₂O)₂]²⁺ dication, the reaction product of Zn(acac)₂ with the divergent 4 pd b ligand is a polymeric species, [Zn(acac)₂(4 pd b)]_n, (I). As a comparison with the 4 pd b case, the 3-pyridyl isomer 1,4-bis(3-pyridyl)-2,3-diaza-1,3-butadiene (3 pd b) was also included in this study. The resulting coordination polymer, [Zn(acac)₂(3 pd b)]_n, (II), shows that the 3 pd b ligand likewise acts as a spacer, with the Zn(acac)₂ complex as a node.

Figs. 1 and 2 show ellipsoid plots for (I) and (II); Tables 1 and 2, in turn, give selected coordination bond lengths and angles. The structures are built up around two non-equivalent symmetry centers, one at the cation position and the other bisecting the N—N bond in the acac unit. Both compounds present tetragonally distorted octahedral environments around Zn, with the O atoms of two chelating acac groups in the equatorial positions and the pyridyl N atoms as apices. Structure (I) shows a slightly larger departure from ideal C_4v geometry, both in the Zn—O lengths and in the O—Zn—N angles (see Table 1), with a slightly larger apical deviation from the normal to the mean equatorial plane [178.5 (1) versus 179.9 (1)°]. While the Zn—N bond distances in both compounds [2.2689 (17) Å in (I) and 2.271 (3) Å in (II)] are very similar, they are significantly longer than the corresponding bond in the only known related Zn^II complex, (III), where the Zn—N bond length is 2.120 (2) Å. This enlargement could be attributed to a less attractive effect towards the metal centre, due to an increase on its negative charge when the neutral ligands (water and methanol) are replaced by the anionic acac. On the other hand, a shortening of the Zn—O distances should be expected in the polymeric complexes considering the charge effect of the acac anion, which implies a stronger interaction of the acetylacetonate O atoms than those of the water and methanol molecules. In fact, this is actually observed; the Zn—O lengths for (I) and (II) lie in the range 2.0328 (13)–2.0617 (13) Å as compared with 2.0977 (18)–2.1642 (19) Å in (III). In both cases, the structures organize as chains {running along [211] and [201] for (I) and (II), respectively}, where the bridging links are the 4 pd b/3 pd b ligands. These are, in turn, responsible for the different geometries observed in the one-dimensional structures, through the diverse disposition of their N atoms and the associated differences in binding modes. In fact, while in (II) the lateral N3 bite of the 3 pd b ligand generates zigzag chains, the more linear 4 pd b gives rise to very straight one-dimensional chains in (I). This can be quantitatively assessed by considering the angle between the apical axis in each coordination polyhedron and the direction of maximum span of the corresponding 4 pd b/3 pd b connecting ligands, viz. almost linear in (I) [172.1 (1)°] and quite broken in (II) [128.2 (1)°] (see Figs. 3 and 4).

The two structures are similar in favouring the aggregation of chains related by a [100] shift, suggesting some kind of a two-dimensional structure parallel to (011) in the case of (I) and to (010) in (II). However, only in the second case does there seem to be a clear C—H···O hydrogen-bonding interaction (see Fig. 4) [C7—H7···O15(1 + x, y, z), with H···O = 2.41 Å, C···O = 3.33 (s.u.?) Å and a very favourable C—H···O angle of 176° (Desiraju, 1996)]. In (I), instead, only feeble C—H···O contacts link neighbouring chains, with a lower bound for the H···O distances of 2.65 Å and C—H···O angles not larger than 130°. The different chain geometries can, in principle, provide plausible arguments for explaining this behaviour; while in both compounds the 3 pd b and 4 pd b ligands present a near planar structure, with the pyridyl rings perpendicular to the O15—Zn1—O15ⁱ axis [symmetry code: (i) −x + 1, −y + 1, −z + 1], only in (II) does this disposition allow the acidic non-aromatic C7/H7 donor group in the the zigzag chain to be close to the acetylacetonate atom O15. In the most linear structure, (I), a distinct situation occurs; the aromatic groups C2/H2 and C3/H3 are closer to atom O15, thereby shielding it from an eventual interaction with the C7/H7 moiety. Consequently, the particular chain disposition in (II) would more likely correlate with a denser packing than (I), which is confirmed when the calculated densities for the two isomers are compared [1.390 g cm⁻³ for (I) and 1.437 g cm⁻³ for (II)].

S2. Experimental

All solvents were purchased from commercial sources and used without further purification. Zn(acac)₂ was obtained from Merck. The 3 pd b (Dong et al., 2000) and 4 pd b (Ciurtin et al., 2001) ligands were prepared following literature procedures. The coordination polymers [Zn(acac)₂(3 pd b)]_n and [Zn(acac)₂(4 pd b)]_n were prepared in a similar manner from the reaction of an excess of Zn(acac)₂ with the appropiate bidentate Schiff base. The procedure, exemplified in what follows for the 3 pd b compound, consisted in dissolving the ligand (8.3 mg, 0.040 mmol) in MeOH (3.0 ml). A methanol solution (3.0 ml) of Zn(acac)₂ (20.8 mg, 0.080 mmol) was then added and the mixture was stirred for 1 min. After 30 h in a closed container, yellow crystals suitable for X-ray diffraction were filtered, washed firstly with MeOH (3 × 3.0 ml) and then with diethyl ether (3 × 3.0 ml), and finally dried in air.

S3. Refinement

H atoms attached to C atoms were included at their expected positions and allowed to ride [C—H = 0.93 Å except C_methyl—H = 0.96 Å; U_iso(H) = 1.2U_eq(H) except U_iso(H) = 1.5U_eq(C_methyl)]. Methyl groups were allowed to rotate around their local threefold axis.

Computing details

For both compounds, data collection: SMART-NT (Bruker, 2001); cell refinement: SAINT-NT (Bruker, 2000); data reduction: SAINT-NT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL-PC (Sheldrick, 2000 or 1994?); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. : A molecular diagram of (I), showing the way in which the chains are formed. Atom numbering is shown only in the independent part of the coordination polyhedron, which is drawn in full displacement ellipsoids (40% probability level). [Symmetry codes: (i) −x + 1, −y + 1, −z + 1; (ii) −x − 1, y, −z + 2.]
	Fig. 2. : A molecular diagram of (II), showing the way in which the chains are formed. Atom numbering is shown only in the independent part of the coordination polyhedron, which is drawn in full displcement ellipsoids (40% probability level). [Symmetry codes: (i) −x + 1, −y + 1, −z + 1; (ii) −x − 1, y, −z + 2.]
	Fig. 3. Fig.: The packing of (I), viewed down [011], showing the organization of chains into planes parallel to (010) through a [100] shift. H atoms have been omitted.
	Fig. 4. : The packing of (II), viewed down the [010] axis, showing the organization of chains into planes parallel to (010) through a [100] shift. Interchain C—H···O bonds are drawn with broken lines. H atoms not involved in hydrogen bonding have been omitted.

(I) catena-poly[[bis(pentane-2,4-dionato-κ²O,O')zinc]-µ- 1,4-bis(4-pyridyl)-2,3-diazabuta-1,3-diene]

Crystal data

[Zn(C5H7O2)2(C12H10N4)]	Z = 1
Mr = 473.82	F(000) = 246
Triclinic, P1	Dx = 1.390 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.3525 (8) Å	Cell parameters from 1870 reflections
b = 9.0459 (11) Å	θ = 3.3–26.0°
c = 10.3907 (12) Å	µ = 1.12 mm^−1
α = 84.282 (2)°	T = 273 K
β = 72.332 (2)°	Block, yellow
γ = 89.558 (2)°	0.20 × 0.20 × 0.16 mm
V = 565.94 (12) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	2409 independent reflections
Radiation source: fine-focus sealed tube	2293 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.044
ϕ and ω scans	θmax = 28.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→7
Tmin = 0.81, Tmax = 0.84	k = −11→11
4727 measured reflections	l = −13→13

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.097	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0606P)^2] where P = (Fo^2 + 2Fc^2)/3
2409 reflections	(Δ/σ)max = 0.002
144 parameters	Δρmax = 0.40 e Å^−3
0 restraints	Δρmin = −0.43 e Å^−3

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

	x	y	z	Uiso*/Ueq
Zn1	0.5000	0.5000	0.5000	0.03504 (14)
C1	−0.1060 (3)	0.1952 (2)	0.8561 (2)	0.0407 (4)
C2	−0.1242 (3)	0.2353 (2)	0.7280 (2)	0.0398 (4)
H2	−0.2467	0.2042	0.7056	0.048*
C3	0.0393 (3)	0.3210 (2)	0.6346 (2)	0.0386 (4)
H3	0.0235	0.3474	0.5492	0.046*
N4	0.2212 (3)	0.36882 (18)	0.65938 (17)	0.0387 (4)
C5	0.2371 (4)	0.3299 (3)	0.7834 (2)	0.0535 (6)
H5	0.3619	0.3616	0.8030	0.064*
C6	0.0812 (4)	0.2465 (3)	0.8826 (2)	0.0558 (6)
H6	0.0996	0.2239	0.9677	0.067*
C7	−0.2679 (4)	0.1010 (2)	0.9614 (2)	0.0466 (5)
H7	−0.2476	0.0824	1.0464	0.056*
N8	−0.4348 (3)	0.0437 (2)	0.94153 (17)	0.0470 (4)
C9	0.2218 (5)	0.9280 (3)	0.6075 (3)	0.0703 (8)
H9A	0.2524	0.9743	0.5163	0.106*
H9B	0.2607	0.9956	0.6626	0.106*
H9C	0.0673	0.9021	0.6438	0.106*
C10	0.3558 (4)	0.7890 (2)	0.6072 (2)	0.0454 (5)
C11	0.4947 (4)	0.7751 (2)	0.6895 (2)	0.0524 (5)
H11	0.5043	0.8559	0.7364	0.063*
C12	0.6197 (3)	0.6526 (2)	0.7082 (2)	0.0418 (4)
C13	0.7438 (5)	0.6523 (3)	0.8102 (3)	0.0672 (7)
H13A	0.6896	0.5717	0.8800	0.101*
H13B	0.7228	0.7447	0.8500	0.101*
H13C	0.8983	0.6402	0.7660	0.101*
O14	0.6379 (2)	0.53697 (15)	0.64704 (14)	0.0391 (3)
O15	0.3299 (2)	0.69470 (15)	0.53251 (15)	0.0437 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0363 (2)	0.03266 (19)	0.0397 (2)	0.00054 (12)	−0.01659 (14)	−0.00451 (13)
C1	0.0394 (11)	0.0405 (10)	0.0403 (10)	−0.0059 (8)	−0.0102 (8)	−0.0007 (8)
C2	0.0328 (10)	0.0432 (10)	0.0450 (11)	−0.0021 (8)	−0.0146 (8)	−0.0024 (8)
C3	0.0343 (10)	0.0419 (10)	0.0400 (10)	0.0005 (8)	−0.0137 (8)	0.0015 (8)
N4	0.0364 (9)	0.0398 (8)	0.0408 (9)	−0.0044 (7)	−0.0140 (7)	0.0002 (7)
C5	0.0512 (13)	0.0625 (14)	0.0499 (12)	−0.0218 (11)	−0.0238 (10)	0.0078 (11)
C6	0.0578 (14)	0.0729 (16)	0.0399 (11)	−0.0206 (12)	−0.0237 (10)	0.0091 (11)
C7	0.0490 (12)	0.0512 (12)	0.0367 (10)	−0.0086 (10)	−0.0106 (9)	0.0021 (9)
N8	0.0454 (10)	0.0503 (10)	0.0402 (9)	−0.0142 (8)	−0.0080 (8)	0.0049 (8)
C9	0.0771 (19)	0.0475 (13)	0.090 (2)	0.0209 (13)	−0.0280 (15)	−0.0169 (13)
C10	0.0458 (12)	0.0386 (10)	0.0478 (12)	0.0039 (9)	−0.0086 (9)	−0.0039 (9)
C11	0.0645 (14)	0.0454 (12)	0.0536 (13)	0.0061 (10)	−0.0224 (11)	−0.0204 (10)
C12	0.0414 (11)	0.0477 (11)	0.0365 (10)	−0.0057 (9)	−0.0119 (8)	−0.0059 (8)
C13	0.0767 (18)	0.0750 (17)	0.0669 (17)	0.0055 (14)	−0.0426 (15)	−0.0228 (14)
O14	0.0406 (7)	0.0385 (7)	0.0429 (7)	−0.0008 (6)	−0.0193 (6)	−0.0049 (6)
O15	0.0456 (8)	0.0397 (7)	0.0511 (8)	0.0076 (6)	−0.0218 (7)	−0.0069 (6)

Geometric parameters (Å, º)

Zn1—O14^i	2.0328 (13)	C7—N8	1.264 (3)
Zn1—O14	2.0328 (13)	C7—H7	0.9300
Zn1—O15	2.0617 (13)	N8—N8^ii	1.413 (3)
Zn1—O15^i	2.0617 (13)	C9—C10	1.512 (3)
Zn1—N4	2.2689 (17)	C9—H9A	0.9600
Zn1—N4^i	2.2689 (17)	C9—H9B	0.9600
C1—C2	1.383 (3)	C9—H9C	0.9600
C1—C6	1.392 (3)	C10—O15	1.252 (2)
C1—C7	1.458 (3)	C10—C11	1.400 (3)
C2—C3	1.369 (3)	C11—C12	1.390 (3)
C2—H2	0.9300	C11—H11	0.9300
C3—N4	1.341 (2)	C12—O14	1.264 (2)
C3—H3	0.9300	C12—C13	1.501 (3)
N4—C5	1.335 (3)	C13—H13A	0.9600
C5—C6	1.360 (3)	C13—H13B	0.9600
C5—H5	0.9300	C13—H13C	0.9600
C6—H6	0.9300
O14^i—Zn1—O14	180.0	C5—C6—C1	119.7 (2)
O14^i—Zn1—O15	90.49 (5)	C5—C6—H6	120.1
O14—Zn1—O15	89.51 (5)	C1—C6—H6	120.1
O14^i—Zn1—O15^i	89.51 (5)	N8—C7—C1	122.54 (19)
O14—Zn1—O15^i	90.49 (5)	N8—C7—H7	118.7
O15—Zn1—O15^i	180.0	C1—C7—H7	118.7
O14^i—Zn1—N4	90.78 (6)	C7—N8—N8^ii	111.8 (2)
O14—Zn1—N4	89.22 (6)	C10—C9—H9A	109.5
O15—Zn1—N4	91.29 (6)	C10—C9—H9B	109.5
O15^i—Zn1—N4	88.71 (6)	H9A—C9—H9B	109.5
O14^i—Zn1—N4^i	89.22 (6)	C10—C9—H9C	109.5
O14—Zn1—N4^i	90.78 (6)	H9A—C9—H9C	109.5
O15—Zn1—N4^i	88.71 (6)	H9B—C9—H9C	109.5
O15^i—Zn1—N4^i	91.29 (6)	O15—C10—C11	125.56 (19)
N4—Zn1—N4^i	180.00 (7)	O15—C10—C9	115.9 (2)
C2—C1—C6	116.99 (19)	C11—C10—C9	118.5 (2)
C2—C1—C7	123.68 (18)	C12—C11—C10	126.54 (19)
C6—C1—C7	119.32 (19)	C12—C11—H11	116.7
C3—C2—C1	119.51 (18)	C10—C11—H11	116.7
C3—C2—H2	120.2	O14—C12—C11	125.66 (19)
C1—C2—H2	120.2	O14—C12—C13	115.30 (19)
N4—C3—C2	123.53 (18)	C11—C12—C13	119.04 (19)
N4—C3—H3	118.2	C12—C13—H13A	109.5
C2—C3—H3	118.2	C12—C13—H13B	109.5
C5—N4—C3	116.54 (18)	H13A—C13—H13B	109.5
C5—N4—Zn1	120.20 (13)	C12—C13—H13C	109.5
C3—N4—Zn1	123.20 (13)	H13A—C13—H13C	109.5
N4—C5—C6	123.7 (2)	H13B—C13—H13C	109.5
N4—C5—H5	118.2	C12—O14—Zn1	126.31 (13)
C6—C5—H5	118.2	C10—O15—Zn1	125.78 (13)

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

(II) catena-poly[[bis(pentane-2,4-dionato-κ²O,O')zinc]-µ- 1,4-bis(3-pyridyl)-2,3-diazabuta-1,3-diene]

Crystal data

[Zn(C5H7O2)2(C12H10N4)]	Z = 1
Mr = 473.82	F(000) = 246
Triclinic, P1	Dx = 1.437 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.8637 (11) Å	Cell parameters from 1134 reflections
b = 8.6257 (14) Å	θ = 3.5–25.7°
c = 9.9497 (16) Å	µ = 1.16 mm^−1
α = 80.536 (3)°	T = 298 K
β = 73.444 (3)°	Block, yellow
γ = 77.310 (3)°	0.28 × 0.18 × 0.12 mm
V = 547.57 (15) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	2379 independent reflections
Radiation source: fine-focus sealed tube	1898 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
ϕ and ω scans	θmax = 28.1°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→8
Tmin = 0.74, Tmax = 0.88	k = −10→10
4661 measured reflections	l = −12→12

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.125	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0584P)^2] where P = (Fo^2 + 2Fc^2)/3
2379 reflections	(Δ/σ)max < 0.001
144 parameters	Δρmax = 0.54 e Å^−3
0 restraints	Δρmin = −0.31 e Å^−3

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

	x	y	z	Uiso*/Ueq
Zn1	0.5000	0.5000	0.5000	0.0371 (2)
C1	1.1023 (5)	0.4043 (4)	0.1656 (3)	0.0376 (7)
C2	0.9477 (5)	0.4470 (4)	0.2834 (3)	0.0395 (8)
H2	0.9710	0.5151	0.3383	0.047*
N3	0.7661 (4)	0.3971 (3)	0.3243 (3)	0.0384 (6)
C4	0.7409 (5)	0.2940 (4)	0.2471 (4)	0.0433 (8)
H4	0.6169	0.2563	0.2737	0.052*
C5	0.8884 (5)	0.2404 (4)	0.1305 (4)	0.0502 (9)
H5	0.8651	0.1660	0.0817	0.060*
C6	1.0703 (5)	0.2975 (4)	0.0866 (4)	0.0454 (8)
H6	1.1699	0.2656	0.0060	0.054*
C7	1.2880 (5)	0.4750 (4)	0.1268 (3)	0.0415 (8)
H7	1.3105	0.5334	0.1898	0.050*
N8	1.4192 (4)	0.4582 (3)	0.0087 (3)	0.0466 (7)
C9	0.3745 (6)	0.8894 (5)	0.1823 (4)	0.0612 (11)
H9A	0.4270	0.8348	0.0991	0.092*
H9B	0.4138	0.9926	0.1627	0.092*
H9C	0.2265	0.9022	0.2108	0.092*
C10	0.4627 (5)	0.7930 (4)	0.2992 (3)	0.0435 (8)
C11	0.6128 (5)	0.8480 (4)	0.3381 (4)	0.0500 (9)
H11	0.6565	0.9393	0.2853	0.060*
C12	0.7044 (5)	0.7812 (4)	0.4475 (4)	0.0416 (8)
C13	0.8543 (6)	0.8638 (5)	0.4792 (5)	0.0592 (11)
H13A	0.8156	0.8759	0.5781	0.089*
H13B	0.8523	0.9672	0.4258	0.089*
H13C	0.9909	0.8012	0.4542	0.089*
O14	0.6730 (3)	0.6523 (3)	0.5243 (2)	0.0412 (6)
O15	0.3908 (3)	0.6683 (3)	0.3550 (2)	0.0423 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0329 (3)	0.0415 (4)	0.0368 (3)	−0.0158 (2)	−0.0049 (2)	0.0013 (2)
C1	0.0291 (16)	0.0432 (19)	0.0354 (17)	−0.0074 (14)	−0.0018 (14)	−0.0003 (14)
C2	0.0324 (17)	0.045 (2)	0.0395 (18)	−0.0129 (15)	−0.0024 (14)	−0.0053 (15)
N3	0.0301 (14)	0.0448 (16)	0.0356 (15)	−0.0101 (12)	−0.0010 (12)	−0.0006 (12)
C4	0.0332 (17)	0.043 (2)	0.050 (2)	−0.0084 (15)	−0.0046 (16)	−0.0022 (16)
C5	0.044 (2)	0.057 (2)	0.052 (2)	−0.0143 (18)	−0.0060 (17)	−0.0177 (18)
C6	0.0370 (18)	0.052 (2)	0.0401 (19)	−0.0047 (16)	0.0017 (15)	−0.0112 (16)
C7	0.0327 (17)	0.048 (2)	0.0422 (19)	−0.0116 (15)	−0.0035 (15)	−0.0055 (16)
N8	0.0346 (16)	0.062 (2)	0.0423 (17)	−0.0177 (14)	0.0002 (13)	−0.0096 (15)
C9	0.073 (3)	0.054 (2)	0.052 (2)	−0.010 (2)	−0.017 (2)	0.0074 (19)
C10	0.046 (2)	0.039 (2)	0.0370 (19)	−0.0041 (16)	−0.0010 (16)	−0.0041 (15)
C11	0.052 (2)	0.037 (2)	0.057 (2)	−0.0182 (17)	−0.0088 (18)	0.0089 (17)
C12	0.0277 (16)	0.041 (2)	0.052 (2)	−0.0094 (14)	0.0026 (15)	−0.0107 (16)
C13	0.047 (2)	0.052 (2)	0.082 (3)	−0.0239 (18)	−0.012 (2)	−0.005 (2)
O14	0.0370 (12)	0.0461 (14)	0.0411 (13)	−0.0197 (11)	−0.0049 (10)	−0.0001 (11)
O15	0.0410 (13)	0.0448 (14)	0.0416 (13)	−0.0136 (11)	−0.0095 (11)	−0.0001 (11)

Geometric parameters (Å, º)

Zn1—O14^i	2.037 (2)	C7—N8	1.268 (4)
Zn1—O14	2.037 (2)	C7—H7	0.9300
Zn1—O15^i	2.049 (2)	N8—N8^ii	1.408 (5)
Zn1—O15	2.049 (2)	C9—C10	1.508 (5)
Zn1—N3^i	2.271 (3)	C9—H9A	0.9600
Zn1—N3	2.271 (3)	C9—H9B	0.9600
C1—C2	1.378 (4)	C9—H9C	0.9600
C1—C6	1.393 (4)	C10—O15	1.261 (4)
C1—C7	1.459 (4)	C10—C11	1.393 (5)
C2—N3	1.339 (4)	C11—C12	1.391 (5)
C2—H2	0.9300	C11—H11	0.9300
N3—C4	1.334 (4)	C12—O14	1.264 (4)
C4—C5	1.373 (5)	C12—C13	1.499 (4)
C4—H4	0.9300	C13—H13A	0.9600
C5—C6	1.371 (4)	C13—H13B	0.9600
C5—H5	0.9300	C13—H13C	0.9600
C6—H6	0.9300
O14—Zn1—O14^i	180.0	C5—C6—H6	120.7
O14—Zn1—O15	89.49 (9)	C1—C6—H6	120.7
O14—Zn1—O15^i	90.51 (9)	N8—C7—C1	121.2 (3)
O15—Zn1—O15^i	180.00 (9)	N8—C7—H7	119.4
O14—Zn1—N3	90.04 (9)	C1—C7—H7	119.4
O14—Zn1—N3^i	89.96 (9)	C7—N8—N8^ii	111.5 (3)
O15—Zn1—N3	89.88 (9)	C10—C9—H9A	109.5
O15—Zn1—N3^i	90.12 (9)	C10—C9—H9B	109.5
O14—Zn1—N3^i	89.96 (9)	H9A—C9—H9B	109.5
O14—Zn1—N3	90.04 (9)	C10—C9—H9C	109.5
O15—Zn1—N3^i	90.12 (9)	H9A—C9—H9C	109.5
O15—Zn1—N3	89.88 (9)	H9B—C9—H9C	109.5
N3—Zn1—N3^i	180.0	O15—C10—C11	125.4 (3)
C2—C1—C6	117.7 (3)	O15—C10—C9	116.2 (3)
C2—C1—C7	119.3 (3)	C11—C10—C9	118.5 (3)
C6—C1—C7	123.0 (3)	C12—C11—C10	127.1 (3)
N3—C2—C1	124.4 (3)	C12—C11—H11	116.5
N3—C2—H2	117.8	C10—C11—H11	116.5
C1—C2—H2	117.8	O14—C12—C11	125.0 (3)
C4—N3—C2	116.4 (3)	O14—C12—C13	115.7 (3)
C4—N3—Zn1	120.7 (2)	C11—C12—C13	119.3 (3)
C2—N3—Zn1	122.6 (2)	C12—C13—H13A	109.5
N3—C4—C5	123.5 (3)	C12—C13—H13B	109.5
N3—C4—H4	118.2	H13A—C13—H13B	109.5
C5—C4—H4	118.2	C12—C13—H13C	109.5
C6—C5—C4	119.4 (3)	H13A—C13—H13C	109.5
C6—C5—H5	120.3	H13B—C13—H13C	109.5
C4—C5—H5	120.3	C12—O14—Zn1	126.2 (2)
C5—C6—C1	118.5 (3)	C10—O15—Zn1	125.5 (2)

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