Diaqua­bis[2′-(4,5-diaza­fluoren-9-yl­idene)picolinohydrazidato-κ²N,O]zinc(II) tetra­hydrate: a metal–water chain complex containing cyclic water hexa­mers

In the title compound, [Zn(C₁₇H₁₀N₅O)₂(H₂O)₂]·4H₂O, cyclic water hexa­mers forming one-dimensional metal–water chains are observed. The water clusters are trapped by the co-operative association of coordination inter­actions and hydrogen bonds. The Zn^II ion resides on a centre of symmetry and is in an octa­hedral coordination environment comprising two O atoms and two N atoms from two 2′-(4,5-diaza­fluoren-9-yl­idene)picolinohydrazidate ligands and two water mol­ecules.

S1. Comment

Over recent decades, considerable attention has been paid to theoretical (Xantheas, 1994; Kim et al., 1999) and experimental (Neogi et al., 2004) studies of small water clusters, because of their importance in understanding the structures and characteristics of liquid water and ice (Ma et al., 2004). So far, small water clusters, (H₂O)_n (n = 2–8, 10, 12, 14, 16, 18, 45), have been obtained in organic or metal–organic crystal hosts (Li et al., 2006). Of all water clusters, the water hexamer is particularly interesting as it is the building block of ice I_h and appears to be relevant to liquid water as well (Speedy et al., 1987). Theoretical calculations have found that several different isomers for the water hexamer, such as ring, block, bag, cage and prism topologies, are almost isoenergetic (Kim & Kim, 1998). To date, chair (Zhao et al., 2004), boat (Park et al., 1993) and planar (Moorthy et al., 2002) cyclic hexamers trapped by hydrogen bonding in host lattices have been reported. Here, we report the title metal–water chain complex, [Zn(L)₂(H₂O)₂]·4H₂O (L = 4,5-diazafluoren-9-ylidene)picolinohydrazonato), (I), containing the cyclic water hexamer, in which the water cluster is trapped not only by hydrogen bonds but also by coordination interactions.

As shown in Fig. 1, the structure of complex (I) consists of one [Zn(L)₂(H₂O)₂] complex molecule and four solvent water molecules. The Zn^II ion resides on a centre of symmetry and is coordinated by two O atoms and two N atoms from two L ligands arranged trans to each other in the equatorial plane, and two aqua ligands occupying the apical coordination sites to furnish an octahedral geometry. The ligand L coordinates to the Zn^II ion as a mono-deprotonated bidentate ligand via the enolic O atom of the amide group and the N atom of the pyridyl group. Within the hydrazine component, both N atoms (N2 and N3) have effectively planar coordination and the N—N bond distance (Table 1) is typical of the value in hydrazine for both N atoms having planar coordination [mean value 1.401 (3) Å; Allen et al., 1987]. The dihedral angle between the diazafluorene plane and the pyridyl plane is small [22.1 (2) °]. This is due to the small N3—N2—C6—O1 torsion angle [1.5 (5) °] and the sp² hybridization of the C6 (amide) and C7 (diazafluorene) atoms.

The [Zn(L)₂(H₂O)₂] complex molecules are linked into one-dimensional chains along the [101] direction via O2—H2B···N5ⁱ hydrogen-bond interactions [symmetry code: (i) 1 + x, y, z − 1]. Within these chains, the separation between two diazafluorene rings is 3.351 (5) Å, indicating significant π–π stacking interactions. Along the [100] direction, the one-dimensional chains are stacked via π–π interactions between two diazafluorene rings of adjacent chains to generate two-dimensional layers parallel to the ac plane [mean interplanar distance = 3.428 (5) Å] (Fig. 2). The layers are stabilized by five independent hydrogen bonds, of O—H···N and O—H···O types (Table 2).

Interestingly, a cyclic centrosymmetric water hexamer [R₆⁶(12); Bernstein et al., 1995] that adopts a chair conformation (Fig. 3) is observed in the solid state. The hydrogen-bonding parameters are reported in Table 2. The average O···O distance is 2.864 (4) Å, which is nearly identical to the value of 2.854 (6) Å observed in liquid water (Speedy et al., 1987). However, it is longer than the corresponding values in ice I_h [2.759 (3) Å; Benson & Siebert, 1992], and in water trapped in the organic compound DMNY·2.5H₂O [2.783 (3) Å; DMNY is 2,4-dimethyl-5-aminobenzo[b]-1,8-naphthyridine; Custelcean et al., 2000] and the metal–organic framework of [Pr(pbc)(Hpbc)(H₂O)₂]·4H₂O [2.783 (3) Å; H₂pbc is pyridine-2,6-dicarboxylic acid; Ghosh & Bharadwaj, 2003], as well as the calculated value of 2.718 (9) Å for the cyclic water hexamer (Stephens & Vagg, 1982). The average of the widely different O···O···O angles is 102 (12) °, which is smaller than that observed in DMNY·2.5H₂O [116.5 (2)°] and larger than that in [Pr(pbc)(Hpbc)(H₂O)₂]·4H₂O [98.36 (5)°]. The coordinated water molecule (O2) has a tetrahedral geometry, with two O—H···O hydrogen bonds, one O—H···N hydrogen bond and one water–metal coordination bond. Meanwhile, each of the other water molecules (O3 and O4) involves three hydrogen bonds, with two water–water hydrogen bonds and one water–hydrazine hydrogen bond. Therefore, each water molecule acts as both hydrogen donor and acceptor to form a cyclic water hexamer. Two water molecules in the cyclic hexamers bind to the Zn^II ions, resulting in an infinite metal–water chain along the a axis (Fig. 4). To the best of our knowledge, such cyclic water clusters containing metal–water chains are very rare (Ghosh & Bharadwaj, 2003; Turner et al., 2004).

S2. Experimental

An ethanol–dimethylformamide (2:1 v/v) solution (40 ml) of the ligand HL (0.5 mmol, 0.15 g) and an aqueous solution (10 ml) of Zn(NO₃)₂·4H₂O (0.25 mmol, 0.26 g) were mixed together, and then five drops of pyridine were added. Red single crystals of (I) suitable for X-ray structure analysis were obtained after two months by slow evaporation of the solvents at room temperature.

S3. Refinement

H atoms attached to C atoms were included in calculated positions and treated as riding atoms, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C). Water H atoms were found in a difference map, relocated in idealized positions with O—H = 0.85 Å, and refined as riding atoms with U_iso(H) = 1.2U_eq(O).

Computing details

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2004); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The structure of compound (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. [Symmetry code: (v) 1 − x, 1 − y, 1 − z.]
	Fig. 2. The two-dimensional structure of (I). Dashed lines indicate hydrogen bonds. H atoms attached to C atoms have been omitted for clarity. [Symmetry codes: (i) 1 + x, y, z − 1; (ii) −x, 1 − y, 1 − z; (iii) −1 − x, 1 − y, 2 − z; (iv) x − 1, y, z.]
	Fig. 3. A molecular drawing showing the cyclic water hexamer and its coordination environment. [Symmetry codes: (i) 1 + x, y, z − 1; (ii) −x, 1 − y, 1 − z; (iii) −1 − x, 1 − y, 2 − z; (iv) x − 1, y, z.]
	Fig. 4. A view of a metal–water chain along the a axis, containing cyclic water hexamers.

Diaquabis[2'-(4,5-diazafluoren-9-ylidene)picolinohydrazidato-κ²N,O)zinc(II) tetrahydrate

Crystal data

[Zn(C17H10N5O)2(H2O)2]·4H2O	Z = 1
Mr = 774.09	F(000) = 400
Triclinic, P1	Dx = 1.513 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.9310 (16) Å	Cell parameters from 96 reflections
b = 10.340 (2) Å	θ = 1.8–26.1°
c = 11.734 (2) Å	µ = 0.79 mm^−1
α = 74.87 (3)°	T = 291 K
β = 75.64 (3)°	Block, red
γ = 68.06 (3)°	0.30 × 0.20 × 0.20 mm
V = 849.4 (3) Å^3

Data collection

Bruker SMART APEXII CCD area-detector diffractometer	3915 independent reflections
Radiation source: fine-focus sealed tube	2724 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.002
ϕ and ω scans	θmax = 27.5°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −10→9
Tmin = 0.797, Tmax = 0.858	k = −13→0
5042 measured reflections	l = −15→14

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.058	H-atom parameters constrained
wR(F^2) = 0.118	w = 1/[σ^2(Fo^2) + (0.1019P)^2 + 0.1755P] where P = (Fo^2 + 2Fc^2)/3
S = 1.11	(Δ/σ)max < 0.001
3915 reflections	Δρmax = 0.41 e Å^−3
242 parameters	Δρmin = −0.60 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0010 (2)

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
Zn	0.5000	0.5000	0.5000	0.0372 (2)
O1	0.2707 (3)	0.4975 (2)	0.6304 (2)	0.0387 (6)
O2	0.3429 (3)	0.5050 (3)	0.3673 (2)	0.0455 (6)
H2A	0.2976	0.4389	0.3803	0.055*
H2B	0.3982	0.5254	0.2966	0.055*
O3	0.0394 (4)	0.7629 (4)	0.3528 (3)	0.0693 (9)
H3A	−0.0553	0.7616	0.3321	0.083*
H3B	0.1059	0.6760	0.3590	0.083*
O4	0.1380 (4)	0.3246 (3)	0.4015 (3)	0.0641 (8)
H4A	0.0702	0.3900	0.3553	0.077*
H4B	0.0670	0.3113	0.4676	0.077*
N1	0.5550 (4)	0.2816 (3)	0.5565 (3)	0.0378 (6)
N2	0.1483 (4)	0.3428 (3)	0.7768 (2)	0.0396 (7)
N3	0.0075 (4)	0.4630 (3)	0.8093 (2)	0.0399 (7)
N4	−0.2687 (5)	0.2649 (4)	1.2041 (3)	0.0548 (9)
N5	−0.4829 (4)	0.5811 (4)	1.1370 (3)	0.0485 (8)
C1	0.6964 (5)	0.1768 (4)	0.5121 (3)	0.0458 (9)
H1	0.7876	0.2003	0.4524	0.055*
C2	0.7117 (6)	0.0360 (4)	0.5514 (4)	0.0523 (10)
H2	0.8110	−0.0346	0.5189	0.063*
C3	0.5751 (6)	0.0019 (4)	0.6407 (4)	0.0546 (10)
H3	0.5802	−0.0922	0.6680	0.066*
C4	0.4313 (6)	0.1092 (4)	0.6889 (3)	0.0479 (9)
H4	0.3412	0.0877	0.7508	0.057*
C5	0.4227 (5)	0.2490 (4)	0.6439 (3)	0.0379 (7)
C6	0.2696 (5)	0.3756 (4)	0.6852 (3)	0.0352 (7)
C7	−0.0952 (5)	0.4421 (4)	0.9124 (3)	0.0383 (8)
C8	−0.0860 (5)	0.3147 (4)	1.0069 (3)	0.0408 (8)
C9	0.0310 (6)	0.1759 (4)	1.0179 (4)	0.0510 (9)
H9	0.1288	0.1455	0.9574	0.061*
C10	−0.0040 (7)	0.0838 (5)	1.1234 (4)	0.0620 (12)
H10	0.0714	−0.0107	1.1348	0.074*
C11	−0.1505 (7)	0.1321 (5)	1.2115 (4)	0.0620 (12)
H11	−0.1684	0.0673	1.2812	0.074*
C12	−0.2328 (5)	0.3534 (4)	1.1016 (3)	0.0412 (8)
C13	−0.3357 (5)	0.5038 (4)	1.0705 (3)	0.0414 (8)
C14	−0.5497 (6)	0.7197 (5)	1.0893 (4)	0.0558 (10)
H14	−0.6512	0.7771	1.1334	0.067*
C15	−0.4761 (6)	0.7814 (5)	0.9786 (4)	0.0563 (10)
H15	−0.5283	0.8781	0.9505	0.068*
C16	−0.3254 (5)	0.7009 (4)	0.9092 (4)	0.0504 (9)
H16	−0.2751	0.7406	0.8340	0.060*
C17	−0.2531 (5)	0.5582 (4)	0.9572 (3)	0.0402 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn	0.0359 (3)	0.0319 (3)	0.0383 (3)	−0.0123 (2)	0.0049 (2)	−0.0062 (2)
O1	0.0395 (12)	0.0332 (12)	0.0348 (12)	−0.0131 (10)	0.0084 (10)	−0.0046 (10)
O2	0.0461 (14)	0.0568 (16)	0.0353 (13)	−0.0235 (13)	0.0015 (10)	−0.0097 (11)
O3	0.0572 (18)	0.062 (2)	0.095 (2)	−0.0136 (16)	−0.0209 (17)	−0.0265 (18)
O4	0.0625 (19)	0.0493 (17)	0.074 (2)	−0.0125 (15)	−0.0166 (16)	−0.0039 (15)
N1	0.0396 (15)	0.0345 (14)	0.0365 (14)	−0.0131 (12)	0.0028 (12)	−0.0096 (12)
N2	0.0398 (15)	0.0399 (15)	0.0344 (14)	−0.0166 (13)	0.0058 (12)	−0.0054 (12)
N3	0.0372 (15)	0.0453 (16)	0.0360 (15)	−0.0150 (13)	0.0017 (12)	−0.0108 (13)
N4	0.073 (2)	0.059 (2)	0.0395 (17)	−0.035 (2)	0.0041 (16)	−0.0123 (15)
N5	0.0402 (16)	0.067 (2)	0.0393 (16)	−0.0172 (16)	0.0011 (13)	−0.0192 (15)
C1	0.045 (2)	0.0396 (19)	0.045 (2)	−0.0092 (16)	0.0029 (16)	−0.0129 (16)
C2	0.053 (2)	0.0384 (19)	0.053 (2)	−0.0029 (17)	−0.0034 (18)	−0.0107 (17)
C3	0.071 (3)	0.0317 (18)	0.054 (2)	−0.0129 (19)	−0.009 (2)	−0.0026 (16)
C4	0.056 (2)	0.0378 (19)	0.043 (2)	−0.0161 (18)	−0.0007 (17)	−0.0015 (16)
C5	0.0407 (18)	0.0357 (17)	0.0379 (18)	−0.0149 (15)	−0.0041 (14)	−0.0067 (14)
C6	0.0391 (17)	0.0359 (17)	0.0290 (15)	−0.0137 (15)	−0.0035 (13)	−0.0038 (13)
C7	0.0355 (17)	0.050 (2)	0.0326 (17)	−0.0199 (16)	0.0006 (13)	−0.0106 (15)
C8	0.0437 (19)	0.047 (2)	0.0361 (18)	−0.0225 (17)	0.0011 (14)	−0.0119 (15)
C9	0.058 (2)	0.045 (2)	0.048 (2)	−0.0180 (19)	0.0021 (18)	−0.0138 (17)
C10	0.090 (3)	0.043 (2)	0.051 (2)	−0.027 (2)	−0.004 (2)	−0.0048 (18)
C11	0.090 (3)	0.056 (3)	0.045 (2)	−0.040 (3)	0.002 (2)	−0.0081 (19)
C12	0.050 (2)	0.048 (2)	0.0316 (17)	−0.0260 (18)	0.0000 (15)	−0.0098 (14)
C13	0.0371 (18)	0.060 (2)	0.0333 (17)	−0.0221 (17)	0.0011 (14)	−0.0168 (16)
C14	0.046 (2)	0.069 (3)	0.049 (2)	−0.008 (2)	−0.0055 (18)	−0.024 (2)
C15	0.051 (2)	0.060 (3)	0.050 (2)	−0.009 (2)	−0.0084 (18)	−0.0117 (19)
C16	0.046 (2)	0.056 (2)	0.044 (2)	−0.0127 (19)	−0.0074 (17)	−0.0070 (18)
C17	0.0370 (18)	0.053 (2)	0.0333 (17)	−0.0172 (16)	−0.0012 (14)	−0.0144 (16)

Geometric parameters (Å, º)

Zn—O1	2.069 (2)	C3—C4	1.383 (5)
Zn—N1	2.087 (3)	C3—H3	0.9300
Zn—O2	2.202 (3)	C4—C5	1.385 (5)
O1—C6	1.259 (4)	C4—H4	0.9300
O2—H2A	0.8500	C5—C6	1.508 (5)
O2—H2B	0.8500	C7—C17	1.472 (5)
O3—H3A	0.8500	C7—C8	1.475 (5)
O3—H3B	0.8500	C8—C9	1.380 (5)
O4—H4A	0.8500	C8—C12	1.412 (5)
O4—H4B	0.8500	C9—C10	1.389 (6)
N1—C1	1.341 (5)	C9—H9	0.9300
N1—C5	1.348 (4)	C10—C11	1.381 (6)
N2—C6	1.318 (4)	C10—H10	0.9300
N2—N3	1.391 (4)	C11—H11	0.9300
N3—C7	1.296 (4)	C12—C13	1.456 (5)
N4—C11	1.337 (6)	C13—C17	1.401 (5)
N4—C12	1.347 (5)	C14—C15	1.380 (6)
N5—C13	1.337 (5)	C14—H14	0.9300
N5—C14	1.345 (6)	C15—C16	1.384 (6)
C1—C2	1.376 (5)	C15—H15	0.9300
C1—H1	0.9300	C16—C17	1.385 (5)
C2—C3	1.388 (6)	C16—H16	0.9300
C2—H2	0.9300
O1—Zn—O1^i	180.0	O1—C6—C5	118.1 (3)
O1—Zn—N1^i	100.25 (11)	N2—C6—C5	114.2 (3)
O1—Zn—N1	79.75 (11)	N3—C7—C17	121.6 (3)
N1^i—Zn—N1	180.00 (17)	N3—C7—C8	132.1 (3)
N1—Zn—O2^i	89.01 (11)	C17—C7—C8	106.3 (3)
O1—Zn—O2	88.51 (10)	C9—C8—C12	118.6 (3)
O1^i—Zn—O2	91.49 (10)	C9—C8—C7	133.6 (3)
N1—Zn—O2	90.99 (11)	C12—C8—C7	107.8 (3)
O2^i—Zn—O2	180.0	C8—C9—C10	116.9 (4)
C6—O1—Zn	114.7 (2)	C8—C9—H9	121.5
H2A—O2—H2B	116.4	C10—C9—H9	121.5
H3A—O3—H3B	101.2	C11—C10—C9	120.2 (4)
H4A—O4—H4B	105.8	C11—C10—H10	119.9
C1—N1—C5	119.3 (3)	C9—C10—H10	119.9
C1—N1—Zn	127.8 (2)	N4—C11—C10	124.9 (4)
C5—N1—Zn	112.8 (2)	N4—C11—H11	117.5
C6—N2—N3	111.9 (3)	C10—C11—H11	117.5
C7—N3—N2	115.4 (3)	N4—C12—C8	125.0 (4)
C11—N4—C12	114.3 (4)	N4—C12—C13	126.2 (3)
C13—N5—C14	115.7 (3)	C8—C12—C13	108.8 (3)
N1—C1—C2	122.6 (4)	N5—C13—C17	124.2 (4)
N1—C1—H1	118.7	N5—C13—C12	127.2 (3)
C2—C1—H1	118.7	C17—C13—C12	108.6 (3)
C1—C2—C3	118.3 (4)	N5—C14—C15	123.7 (4)
C1—C2—H2	120.9	N5—C14—H14	118.2
C3—C2—H2	120.9	C15—C14—H14	118.2
C4—C3—C2	119.4 (4)	C14—C15—C16	120.6 (4)
C4—C3—H3	120.3	C14—C15—H15	119.7
C2—C3—H3	120.3	C16—C15—H15	119.7
C3—C4—C5	119.3 (3)	C15—C16—C17	116.6 (4)
C3—C4—H4	120.3	C15—C16—H16	121.7
C5—C4—H4	120.3	C17—C16—H16	121.7
N1—C5—C4	121.0 (3)	C16—C17—C13	119.2 (3)
N1—C5—C6	114.5 (3)	C16—C17—C7	132.3 (3)
C4—C5—C6	124.5 (3)	C13—C17—C7	108.5 (3)
O1—C6—N2	127.7 (3)
N1^i—Zn—O1—C6	−177.3 (2)	N3—C7—C8—C9	−1.0 (7)
N1—Zn—O1—C6	2.7 (2)	C17—C7—C8—C9	−179.3 (4)
O2^i—Zn—O1—C6	−86.0 (2)	N3—C7—C8—C12	179.2 (4)
O2—Zn—O1—C6	94.0 (2)	C17—C7—C8—C12	0.9 (4)
O1—Zn—N1—C1	176.4 (3)	C12—C8—C9—C10	−0.7 (6)
O1^i—Zn—N1—C1	−3.6 (3)	C7—C8—C9—C10	179.6 (4)
O2^i—Zn—N1—C1	−91.9 (3)	C8—C9—C10—C11	0.2 (7)
O2—Zn—N1—C1	88.1 (3)	C12—N4—C11—C10	−1.0 (7)
O1—Zn—N1—C5	0.1 (2)	C9—C10—C11—N4	0.8 (8)
O1^i—Zn—N1—C5	−179.9 (2)	C11—N4—C12—C8	0.5 (6)
O2^i—Zn—N1—C5	91.8 (2)	C11—N4—C12—C13	−178.7 (4)
O2—Zn—N1—C5	−88.2 (2)	C9—C8—C12—N4	0.4 (6)
C6—N2—N3—C7	−166.4 (3)	C7—C8—C12—N4	−179.8 (3)
C5—N1—C1—C2	0.7 (6)	C9—C8—C12—C13	179.6 (3)
Zn—N1—C1—C2	−175.4 (3)	C7—C8—C12—C13	−0.5 (4)
N1—C1—C2—C3	−0.2 (6)	C14—N5—C13—C17	−1.0 (5)
C1—C2—C3—C4	−1.4 (6)	C14—N5—C13—C12	178.0 (4)
C2—C3—C4—C5	2.4 (6)	N4—C12—C13—N5	0.1 (6)
C1—N1—C5—C4	0.4 (5)	C8—C12—C13—N5	−179.2 (3)
Zn—N1—C5—C4	177.0 (3)	N4—C12—C13—C17	179.2 (4)
C1—N1—C5—C6	−179.1 (3)	C8—C12—C13—C17	−0.1 (4)
Zn—N1—C5—C6	−2.5 (4)	C13—N5—C14—C15	0.8 (6)
C3—C4—C5—N1	−1.9 (6)	N5—C14—C15—C16	0.1 (7)
C3—C4—C5—C6	177.5 (4)	C14—C15—C16—C17	−0.9 (6)
Zn—O1—C6—N2	175.2 (3)	C15—C16—C17—C13	0.6 (6)
Zn—O1—C6—C5	−4.9 (4)	C15—C16—C17—C7	−178.7 (4)
N3—N2—C6—O1	1.5 (5)	N5—C13—C17—C16	0.3 (6)
N3—N2—C6—C5	−178.4 (3)	C12—C13—C17—C16	−178.8 (3)
N1—C5—C6—O1	5.1 (5)	N5—C13—C17—C7	179.8 (3)
C4—C5—C6—O1	−174.4 (3)	C12—C13—C17—C7	0.7 (4)
N1—C5—C6—N2	−175.0 (3)	N3—C7—C17—C16	0.0 (6)
C4—C5—C6—N2	5.5 (5)	C8—C7—C17—C16	178.4 (4)
N2—N3—C7—C17	−178.1 (3)	N3—C7—C17—C13	−179.4 (3)
N2—N3—C7—C8	3.9 (6)	C8—C7—C17—C13	−1.0 (4)

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
O2—H2A···O4	0.85	1.97	2.799 (4)	166
O2—H2B···N5^ii	0.85	1.92	2.771 (4)	177
O3—H3A···N2^iii	0.85	2.26	2.988 (5)	143
O3—H3B···O2	0.85	2.05	2.847 (5)	157
O4—H4A···N3^iii	0.85	2.19	2.993 (4)	159
O4—H4B···O3^iii	0.85	2.12	2.947 (5)	164

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