Nickel and zinc complexes with a monodentate heterocycle and tridentate Schiff base ligands: self-assembly to one- and two-dimensional supra­molecular networks via hydrogen bonding

In the complex (morpholine)[2-hydroxy-N′-(5-nitro-2-oxidobenzyl­id­ene)­benzohydrazidato]nickel(II), [Ni(C₁₄H₉N₃O₅)(C₄H₉NO)], (I), the Ni^II center is in a square-planar N₂O₂ coordination geometry. The complex bis­[μ-2-hydroxy-N′-(2-oxidobenzyl­idene)benzohydrazidato]bis­[(morpholine)zinc(II)], [Zn₂(C₁₄H₁₀N₂O₃)₂(C₄H₉NO)₂], (II), consists of a neutral centrosymmetric dimer with a coplanar Zn₂(μ₂-O)₂ core. The two Zn^II centers are bridged by phenolate O atoms. Each Zn^II center exhibits a distorted square-pyramidal stereochemistry, in which the four in-plane donors come from the O,N,O′-tridentate 2-hydroxy-N′-(2-oxidobenzyl­idene)benzo­hydrazidate(2−) ligand and a symmetry-related phenol­ate O atom, and the axial position is coordinated to the N atom from the morpholine mol­ecule. There are intra­molecular phenol–hydrazide O—H...N hydrogen bonds present in both (I) and (II). In (I), square-planar nickel complexes are linked by inter­molecular morpholine–morpholine N—H...O hydrogen bonds, leading to a one-dimensional chain, while in (II) an infinite two-dimensional network is formed via inter­molecular hydrogen bonds between the coordinated morpholine NH groups and the uncoordinated phenolate O atoms.

S1. Comment

In recent years, self-assemblies of coordination compounds to one-, two- and three-dimensional supramolecules have been of much interest (Bai et al., 2006; Batten & Robson, 1998; Padhi et al., 2008; Rayati et al., 2008). The general strategies used for self-assemblies into such extended supramolecular network structures are the metal ion's preference for different coordination geometry, use of suitable bridging bidentate ligands such as pyrazine (Warda, 1998b) and dioxane (Warda, 1998a), and weak intermolecular interactions such as hydrogen bonding and π–π interactions (Bauer & Weber, 2008; Mukhopadhyay et al., 2003; Padhi et al., 2008). Aroylhydrazones have been extensively investigated by chemists in the synthesis of coordination polymers owing to their inherent coordination and hydrogen-bonding donor/acceptor functionalities, as well as their biological activities (Rayati et al., 2008; Dutta et al., 1995; Lian et al., 2008). In the following account, we report two mixed-ligand bivalent nickel/zinc complexes, [Ni(L₁)(C₄H₉NO)], (I) and [Zn(L₂)(C₄H₉NO)]₂, (II). The common ligand in both complexes is the tridentate aroylhydrazone ligand, N-5-nitrosalicylaldehyde-N'-salicyloylhydrazone (H₂L₁) or N-salicylaldehyde-N'-salicyloylhydrazone (H₂L₂). Neutral N-donor morpholine has been used as the ancillary ligand. The self-assembly of both complex molecules via intermolecular hydrogen bonds involving the heterocyclic morpholine NH group has been demonstrated. As far as we know, complex (II) is the first example of a dinuclear zinc hydrazone complex with morpholine as the ancillary ligand; (II) exhibits an infinite two-dimensional supramolecular network structure.

As shown in Fig. 1, in (I), the tridentate L₁^2- ligand coordinates the Ni^II ion via the phenolate O1, carbonyl O4 and hydrazone N2 atoms, forming one five- and one six-membered chelating ring. The fourth site is occupied by atom N4 of the heterocycle to complete a square-planar N₂O₂ geometry around the metal center. There is nearly no deviation of the metal center from the N₂O₂ square plane; atom Ni1 deviates from the basal plane by 0.0092 (8) Å. The N—N, N═C, and C—O bond distances in the ═ N—N═C(O^-)- fragment of L₁^2- are consistent with the enolate form of the hydrazone functionalities (Chen, 2008; Lin et al., 2007; Lian et al., 2008). The Ni1—N2, Ni1—O1 and Ni1—O4 bond distances (Table 1) are normal, as observed in some similar square-planar Ni^II complexes with aroylhydrazone ligands (Chen, 2008; Lin et al., 2007; Lian et al., 2008). The Ni1—N4 bond length is comparable to the distance observed in the lone example of a tetracoordinated Ni^II complex (Lian et al., 2008) containing a monodentate neutral morpholine moiety.

Both the six-membered chelating ring [r.m.s deviation = 0.0332 (1) Å] and the five-membered chelating ring [r.m.s deviation = 0.0338 (8) Å] are close to planar, and the dihedral angle between them is 3.6 (1)°. The dihedral angle between the phenyl ring and the substituent –NO₂ group is 4.1 (4)°. However, the dihedral angle between the two phenyl rings of the hydrazone ligand in complex (I) is 12.6 (1)°, indicating a slight twist of the whole ligand.

There exists a weak O5—H5B···N3 intramolecular contact (Table 2). In the crystal structure, the asymmetric units are linked by intermolecular N4—H4B···O6ⁱ interactions (symmetry code as in Table 2), forming a one-dimensional zigzag supramolecular network (Fig. 2). The Ni···Ni distance in this uniform arrangement is 8.935 (3) Å.

As shown in Fig. 3, the structure of (II) consists of a centrosymmetric binuclear entity with a coplanar Zn₂(µ₂-O)₂ fragment. Phenolate O atoms bridge the Zn^II ions, with Zn1—O1ⁱ and Zn1ⁱ—O1 bonds of 2.007 (2) Å [symmetry code: (i) -x, y + 1, -z + 1]. Each Zn^II ion is well described as having a distorted square-pyramidal configuration, as evidenced by the structural index parameter τ of 12.7% (Addison et al., 1984). The basal plane is occupied by one N atom from the hydrazone group and three O atoms (two bridging phenolate O atoms and one from the carbonyl group), with an r.m.s deviation from the mean plane of 0.0735 (2) Å. The apical position at each Zn^II ion is occupied by the N atom from the heterocyclic morpholine ligand. Atom Zn1 deviates from the basal plane by a distance of 0.449 (1) Å towards the apical atom N3.

The distances in the coordination plane (Table 3) are comparable to those found in the similar compounds [Zn(C₁₅H₁₂N₂O₂)(C₂H₆OS)]₂ (Ali et al., 2003) and [Zn(C₁₅H₁₂N₂O₃)(py)]₂.2DMF (Huang et al., 2005). The Zn1···Zn1ⁱ separation within the binuclear unit is 3.144 (1) Å. The Zn—O(ph)—Zn bridging angle is 100.6 (1)°, which is in the range observed for five-coordinated Zn^II complexes of related ligands with a coplanar Zn₂(µ₂-O)₂ fragment. For the purpose of comparison, the dimensions of the Zn₂(µ₂-O)₂ fragment in some binuclear zinc complexes of similar O,N,O-ligands are shown in Table 5. Structurally characterized mononuclear Zn^II complexes containing neutral morpholine as a ligand are rare (Ivanov et al., 2001), and complex (II) is the first example of a binuclear Zn^II complex with a coordinated heterocyclic morpholine ligand. In (II), the apical Zn—N(morpholine) bond distance is 2.072 (3) Å, similar to those found in the above mononuclear Zn^II complexes ranging from 2.061 (6) to 2.106 (5) Å. The C8—O2 and C8═ N2 bond distances suggest that the L₂^2- ligands also take the enolate form of the hydrazone functionality, similar to that of (I).

All the non-H atoms of each ligand are nearly coplanar, with a mean deviation of 0.0726 (3) Å from the mean plane. There exists one intramolecular O—H(phenol)···N(hydrazone) hydrogen bond in each ligand, forming a six-membered ring (H3C—O3—C10—C9—C8—N2) (Table 4). On the other hand, in contrast to the one-dimensional assemblies of the complexes [Zn(C₁₅H₁₂N₂O₂)(C₂H₆OS)]₂ (Ali et al., 2003), [Zn(C₁₅H₁₂N₂O₃)(py)]₂.2DMF (Huang et al., 2005) and [Zn(SHSH)(2-Me-py)]₂ (Hu et al., 2007), and the discrete entity of the complex [Zn(SHSH)(py)]₂.2DMF (Huang & Li, 2007), each complex molecule (II) is linked to four adjacent molecules by two pairs of intermolecular N—H(morpholine)···Oⁱⁱ(phenol) hydrogen bonds [symmetry code: (ii) x - 1/2, -y + 1/2 , -z + 1] to form an infinite two-dimensional supramolecular network (see Table 4 and Fig. 4). It is interesting that the packing in the unit cell is also stabilized by weak π–π interactions. The centroid Cg1 (C9–C14) is involved in a weak π–π interaction with Cg2ⁱⁱⁱ [C8/N1/N2/Zn1/O2; symmetry code: (iii) -x + 1/2 , y - 1/2, z] between the interleaved ligands at a distance of 3.993 (1) Å (see Fig. 4).

The IR spectra of the free ligand H₂L₂ displays three bands attributed to C═O, C═N and N—H at 1637, 1619 and 3260 cm^-1, respectively, indicative of its ketonic nature. In (II), these bands are absent, but a new C—O^- stretch appears at 1420 cm^-1 (Rao et al., 1999). In addition, a strong band found at 1600 cm^-1 is attributed to the >C═N—N═C< group (Kuriakose et al., 2007). Such behavior is considered diagnostic for the enolization of the hydrazone residue. Out of the two ν(C—OH) bands observed at 1158 and 1231 cm^-1 in the free ligand, the latter shows shift to 1259 cm^-1, while the former remains unchanged in complex (II). This indicates that one of the phenolate O atoms has undergone deprotonation and coordinated to the metal center (Rao et al., 1999). Thus the Schiff ligand acts as a dianionic tridentate ligand in complex (II), corresponding to the X-ray structure determination. A band also appears at 3500 cm^-1, which may be attributed to the hydrogen-bond interaction. Additionally, in complex (II), coordination of the N and O atoms to the Zn atom is observed by the presence of bands at 460–535 cm^-1, assignable to ν(Zn—N) and ν(Zn—O) (Hu et al., 2007).

Related literature

For related literature, see: Addison et al., (1984); Ali et al., (2003); Bai et al., (2006); Batten & Robson, (1998); Bauer & Weber, (2008); Chen, (2008); Dutta et al., (1995); Hu et al., (2007); Huang & Li, (2007); Huang et al., (2005); Ivanov et al., (2001); Kuriakose et al., (2007); Lian et al., (2008); Lin et al., (2007); Mukhopadhyay et al., (2003); Padhi et al., (2008); Rayati et al., (2008); Rao et al., (1999); Warda, (1998a); Warda, (1998b).

S2. Experimental

The Schiff base ligands H₂L₁ and H₂L₂ were prepared by following a procedure previously reported by Chen (2008).

H₂L₁ (0.2 mmol) and [Ni(OAc)₂].4H₂O (0.2 mmol) were dissolved in C₂H₅OH (15 ml). After stirring for 15 min, morpholine (1 ml) was added to the solution, which was then stirred for another 1 h and filtered. Red single crystals of complex (I) were obtained after 2 d. Analysis calculated for C₁₈H₁₈N₄NiO₆: C 48.58, H 4.08, N 12.59%; found: C 48.69, H 4.03, N 12.52%.

H₂L₂ (0.2 mmol) and [Zn(OAc)₂].H₂O (0.2 mmol) were dissolved in a mixture of DMF (5 ml) and C₂H₅OH (5 ml). After stirring for 15 min, morpholine (1 ml) was added to the mixed solution, which was then stirred for another 1 h and filtered. Yellow single crystals of complex (II) were obtained after one week. Analysis calculated for C₃₆H₃₈N₆O₈Zn₂: C 53.16, H 4.71, N 10.33%; found: C 53.29, H 4.67, N 10.25%.

The molar conductance values of the two complexes measured in DMF solutions are 6.32 and 5.21 S cm² mol^-1, respectively, indicating that both are non-conducting in DMF solutions.

S3. Refinement

H atoms bonded to C atoms in (I) and (II) were positioned geometrically and refined using a riding model [C—H = 0.93—0.97 Å and U_iso(H) = 1.2U_eq(C)]. H atoms bonded to phenolate O and morpholine N atoms were located in a difference Fourier map and were refined with O—H and N—H distance restraints of 0.82 and 0.90 Å, respectively [please provide s.u. values], and with U_iso(H) = 1.5U_eq(O) and 1.2U_eq(N) [from data in CIF these appear to have been refined; please check].

Computing details

For both compounds, data collection: TEXRAY (Molecular Structure Corporation, 1999); cell refinement: TEXRAY (Molecular Structure Corporation, 1999); data reduction: TEXSAN (Molecular Structure Corporation, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEX (McArdle, 1995); software used to prepare material for publication: SHELXL97/2 (Sheldrick, 2008).

Figures

	Fig. 1. A view of (I), showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Dashed lines indicate hydrogen bonding. Only H atoms involved in hydrogen bonds have been included.
	Fig. 2. A packing diagram for (I), with hydrogen bonds shown as dashed lines. Only H atoms involved in hydrogen bonds have been included.
	Fig. 3. A view of (II), showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Dashed lines indicate hydrogen bonding. Only H atoms involved in hydrogen bonds have been included. [Symmetry code: (i) -x, -y + 1, -z +1.]
	Fig. 4. A packing diagram for (II), with hydrogen bonds and π–π stacking interactions, with Cg···Cg distances of 3.991 (3) Å, shown as dashed lines. Only H atoms involved in hydrogen bonds have been included.

(I) (morpholine)[N'-(5-nitro-2-oxidobenzylidene)benzohydrazidato]nickel(II)

Crystal data

[Ni(C14H9N3O5)(C4H9NO)]	F(000) = 1840
Mr = 445.07	Dx = 1.624 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 3196 reflections
a = 11.548 (4) Å	θ = 3.0–27.5°
b = 8.479 (2) Å	µ = 1.11 mm^−1
c = 37.184 (10) Å	T = 293 K
V = 3640.8 (19) Å^3	Block, red
Z = 8	0.45 × 0.28 × 0.15 mm

Data collection

Rigaku R-AXIS RAPID imaging-plate diffractometer	4139 independent reflections
Radiation source: fine-focus sealed tube	3196 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.061
ω scans	θmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan (TEXRAY; Molecular Structure Corporation, 1999)	h = −14→14
Tmin = 0.635, Tmax = 0.851	k = −10→10
32687 measured reflections	l = −48→48

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.088	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0378P)^2 + 2.0267P] where P = (Fo^2 + 2Fc^2)/3
4139 reflections	(Δ/σ)max = 0.001
270 parameters	Δρmax = 0.40 e Å^−3
2 restraints	Δρmin = −0.37 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
Ni1	0.40946 (2)	0.20813 (3)	0.375534 (7)	0.02781 (10)
O1	0.45421 (13)	0.35169 (18)	0.40947 (4)	0.0361 (4)
O2	0.2384 (2)	0.7523 (3)	0.53215 (5)	0.0725 (6)
O3	0.0854 (2)	0.6383 (3)	0.51299 (7)	0.0840 (8)
O4	0.36297 (13)	0.06861 (17)	0.34033 (4)	0.0325 (3)
O5	0.00510 (16)	0.0741 (3)	0.32098 (6)	0.0628 (6)
H5B	0.040 (3)	0.111 (4)	0.3384 (7)	0.089 (13)*
O6	0.76874 (15)	−0.0470 (2)	0.36348 (5)	0.0470 (4)
N1	0.1889 (2)	0.6649 (3)	0.51118 (6)	0.0501 (6)
N2	0.25364 (15)	0.2368 (2)	0.38219 (5)	0.0285 (4)
N3	0.18373 (15)	0.1513 (2)	0.35867 (5)	0.0322 (4)
N4	0.57251 (15)	0.1616 (2)	0.36836 (5)	0.0300 (4)
H4B	0.607 (2)	0.2566 (17)	0.3671 (7)	0.038 (7)*
C1	0.38672 (19)	0.4294 (3)	0.43130 (6)	0.0325 (5)
C2	0.26355 (19)	0.4145 (2)	0.43204 (6)	0.0311 (5)
C3	0.2000 (2)	0.4945 (3)	0.45845 (6)	0.0358 (5)
H3A	0.1199	0.4838	0.4594	0.043*
C4	0.2555 (2)	0.5881 (3)	0.48288 (6)	0.0374 (5)
C5	0.3747 (2)	0.6118 (3)	0.48147 (6)	0.0406 (6)
H5A	0.4105	0.6795	0.4977	0.049*
C6	0.4387 (2)	0.5346 (3)	0.45599 (6)	0.0393 (5)
H6A	0.5182	0.5518	0.4549	0.047*
C7	0.20267 (18)	0.3205 (2)	0.40646 (6)	0.0317 (5)
H7A	0.1222	0.3194	0.4073	0.038*
C8	0.25099 (18)	0.0682 (2)	0.33735 (6)	0.0298 (5)
C9	0.19681 (19)	−0.0251 (3)	0.30838 (6)	0.0326 (5)
C10	0.0785 (2)	−0.0151 (3)	0.30131 (7)	0.0420 (6)
C11	0.0325 (2)	−0.0976 (4)	0.27229 (7)	0.0546 (7)
H11A	−0.0462	−0.0901	0.2673	0.066*
C12	0.1019 (3)	−0.1896 (3)	0.25107 (8)	0.0559 (8)
H12A	0.0700	−0.2433	0.2316	0.067*
C13	0.2191 (3)	−0.2035 (3)	0.25829 (7)	0.0488 (6)
H13A	0.2657	−0.2683	0.2442	0.059*
C14	0.2658 (2)	−0.1201 (3)	0.28656 (6)	0.0387 (5)
H14A	0.3447	−0.1273	0.2912	0.046*
C15	0.6041 (2)	0.0758 (3)	0.33509 (6)	0.0426 (6)
H15A	0.5811	0.1379	0.3144	0.051*
H15B	0.5621	−0.0233	0.3343	0.051*
C16	0.7324 (2)	0.0430 (3)	0.33309 (7)	0.0459 (6)
H16A	0.7496	−0.0147	0.3112	0.055*
H16B	0.7746	0.1418	0.3324	0.055*
C17	0.7479 (2)	0.0409 (3)	0.39552 (7)	0.0470 (6)
H17B	0.7906	0.1393	0.3946	0.056*
H17C	0.7751	−0.0186	0.4161	0.056*
C18	0.6201 (2)	0.0753 (3)	0.39979 (6)	0.0408 (6)
H18B	0.5784	−0.0232	0.4027	0.049*
H18C	0.6082	0.1377	0.4213	0.049*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.01951 (14)	0.02964 (15)	0.03427 (16)	0.00021 (10)	−0.00105 (11)	0.00023 (12)
O1	0.0247 (8)	0.0391 (8)	0.0444 (9)	0.0014 (7)	−0.0007 (7)	−0.0085 (8)
O2	0.0823 (16)	0.0827 (15)	0.0526 (12)	0.0030 (13)	0.0024 (12)	−0.0307 (12)
O3	0.0569 (15)	0.0984 (18)	0.0968 (18)	0.0021 (13)	0.0255 (13)	−0.0436 (16)
O4	0.0226 (7)	0.0359 (8)	0.0391 (8)	−0.0008 (6)	−0.0006 (6)	−0.0021 (7)
O5	0.0268 (10)	0.1034 (17)	0.0583 (12)	0.0033 (10)	−0.0089 (9)	−0.0137 (13)
O6	0.0389 (10)	0.0472 (10)	0.0550 (10)	0.0160 (8)	−0.0024 (8)	−0.0055 (9)
N1	0.0560 (15)	0.0475 (13)	0.0468 (13)	0.0104 (11)	0.0071 (11)	−0.0031 (11)
N2	0.0218 (9)	0.0301 (9)	0.0335 (9)	0.0000 (7)	−0.0020 (7)	0.0058 (8)
N3	0.0241 (9)	0.0386 (10)	0.0339 (10)	−0.0026 (8)	−0.0037 (7)	0.0019 (9)
N4	0.0223 (9)	0.0301 (9)	0.0377 (10)	−0.0002 (7)	−0.0006 (7)	−0.0014 (8)
C1	0.0318 (12)	0.0305 (11)	0.0352 (12)	0.0030 (9)	−0.0022 (9)	0.0029 (10)
C2	0.0303 (11)	0.0295 (10)	0.0335 (11)	0.0020 (9)	0.0002 (9)	0.0066 (10)
C3	0.0325 (12)	0.0325 (11)	0.0424 (13)	0.0056 (9)	0.0029 (10)	0.0058 (11)
C4	0.0468 (14)	0.0319 (11)	0.0334 (11)	0.0095 (10)	0.0030 (10)	0.0024 (10)
C5	0.0460 (14)	0.0353 (12)	0.0404 (13)	0.0039 (10)	−0.0096 (11)	−0.0021 (11)
C6	0.0309 (12)	0.0424 (13)	0.0445 (13)	0.0028 (10)	−0.0046 (10)	−0.0009 (12)
C7	0.0239 (11)	0.0328 (11)	0.0384 (12)	0.0030 (8)	0.0010 (9)	0.0080 (10)
C8	0.0251 (11)	0.0307 (11)	0.0338 (11)	−0.0034 (8)	−0.0017 (9)	0.0086 (10)
C9	0.0314 (12)	0.0343 (12)	0.0320 (11)	−0.0087 (9)	−0.0037 (9)	0.0078 (10)
C10	0.0321 (13)	0.0546 (15)	0.0393 (12)	−0.0071 (11)	−0.0053 (10)	0.0084 (12)
C11	0.0419 (16)	0.0708 (19)	0.0512 (15)	−0.0153 (14)	−0.0167 (12)	0.0031 (15)
C12	0.070 (2)	0.0556 (17)	0.0426 (14)	−0.0194 (15)	−0.0164 (13)	0.0015 (14)
C13	0.0613 (18)	0.0448 (14)	0.0404 (14)	−0.0057 (13)	−0.0030 (12)	−0.0002 (13)
C14	0.0404 (13)	0.0376 (13)	0.0383 (12)	−0.0044 (10)	−0.0025 (10)	0.0053 (11)
C15	0.0330 (13)	0.0590 (16)	0.0358 (12)	0.0082 (11)	0.0014 (10)	−0.0044 (12)
C16	0.0340 (13)	0.0595 (16)	0.0440 (13)	0.0111 (12)	0.0031 (11)	−0.0042 (13)
C17	0.0357 (13)	0.0585 (16)	0.0468 (14)	0.0169 (11)	−0.0076 (11)	−0.0017 (13)
C18	0.0347 (13)	0.0506 (14)	0.0371 (12)	0.0081 (11)	−0.0023 (10)	0.0009 (12)

Geometric parameters (Å, º)

Ni1—O1	1.8280 (16)	C5—C6	1.368 (3)
Ni1—N2	1.8325 (19)	C5—H5A	0.9300
Ni1—O4	1.8442 (15)	C6—H6A	0.9300
Ni1—N4	1.9422 (19)	C7—H7A	0.9300
O1—C1	1.304 (3)	C8—C9	1.475 (3)
O2—N1	1.219 (3)	C9—C14	1.393 (3)
O3—N1	1.218 (3)	C9—C10	1.394 (3)
O4—C8	1.298 (3)	C10—C11	1.391 (4)
O5—C10	1.351 (3)	C11—C12	1.369 (4)
O5—H5B	0.822 (18)	C11—H11A	0.9300
O6—C17	1.426 (3)	C12—C13	1.385 (4)
O6—C16	1.427 (3)	C12—H12A	0.9300
N1—C4	1.457 (3)	C13—C14	1.377 (3)
N2—C7	1.290 (3)	C13—H13A	0.9300
N2—N3	1.394 (2)	C14—H14A	0.9300
N3—C8	1.315 (3)	C15—C16	1.510 (3)
N4—C15	1.481 (3)	C15—H15A	0.9700
N4—C18	1.484 (3)	C15—H15B	0.9700
N4—H4B	0.900 (10)	C16—H16A	0.9700
C1—C6	1.414 (3)	C16—H16B	0.9700
C1—C2	1.428 (3)	C17—C18	1.513 (3)
C2—C3	1.401 (3)	C17—H17B	0.9700
C2—C7	1.427 (3)	C17—H17C	0.9700
C3—C4	1.366 (3)	C18—H18B	0.9700
C3—H3A	0.9300	C18—H18C	0.9700
C4—C5	1.392 (4)
O1—Ni1—N2	95.50 (7)	O4—C8—C9	119.10 (19)
O1—Ni1—O4	178.15 (7)	N3—C8—C9	118.49 (19)
N2—Ni1—O4	83.99 (7)	C14—C9—C10	119.0 (2)
O1—Ni1—N4	87.47 (7)	C14—C9—C8	119.5 (2)
N2—Ni1—N4	175.92 (8)	C10—C9—C8	121.4 (2)
O4—Ni1—N4	93.13 (7)	O5—C10—C11	117.5 (2)
C1—O1—Ni1	126.66 (14)	O5—C10—C9	123.1 (2)
C8—O4—Ni1	110.64 (13)	C11—C10—C9	119.3 (3)
C10—O5—H5B	110 (3)	C12—C11—C10	120.7 (3)
C17—O6—C16	109.43 (18)	C12—C11—H11A	119.7
O3—N1—O2	122.5 (2)	C10—C11—H11A	119.7
O3—N1—C4	118.4 (2)	C11—C12—C13	120.6 (3)
O2—N1—C4	119.1 (2)	C11—C12—H12A	119.7
C7—N2—N3	117.43 (18)	C13—C12—H12A	119.7
C7—N2—Ni1	128.00 (15)	C14—C13—C12	119.1 (3)
N3—N2—Ni1	114.51 (13)	C14—C13—H13A	120.4
C8—N3—N2	108.36 (17)	C12—C13—H13A	120.4
C15—N4—C18	108.92 (18)	C13—C14—C9	121.2 (2)
C15—N4—Ni1	116.94 (14)	C13—C14—H14A	119.4
C18—N4—Ni1	110.54 (14)	C9—C14—H14A	119.4
C15—N4—H4B	106.8 (16)	N4—C15—C16	111.93 (19)
C18—N4—H4B	108.5 (16)	N4—C15—H15A	109.2
Ni1—N4—H4B	104.7 (16)	C16—C15—H15A	109.2
O1—C1—C6	118.0 (2)	N4—C15—H15B	109.2
O1—C1—C2	124.3 (2)	C16—C15—H15B	109.2
C6—C1—C2	117.8 (2)	H15A—C15—H15B	107.9
C3—C2—C7	118.7 (2)	O6—C16—C15	110.4 (2)
C3—C2—C1	119.5 (2)	O6—C16—H16A	109.6
C7—C2—C1	121.8 (2)	C15—C16—H16A	109.6
C4—C3—C2	120.1 (2)	O6—C16—H16B	109.6
C4—C3—H3A	119.9	C15—C16—H16B	109.6
C2—C3—H3A	119.9	H16A—C16—H16B	108.1
C3—C4—C5	121.5 (2)	O6—C17—C18	110.7 (2)
C3—C4—N1	119.5 (2)	O6—C17—H17B	109.5
C5—C4—N1	119.0 (2)	C18—C17—H17B	109.5
C6—C5—C4	119.4 (2)	O6—C17—H17C	109.5
C6—C5—H5A	120.3	C18—C17—H17C	109.5
C4—C5—H5A	120.3	H17B—C17—H17C	108.1
C5—C6—C1	121.5 (2)	N4—C18—C17	111.9 (2)
C5—C6—H6A	119.3	N4—C18—H18B	109.2
C1—C6—H6A	119.3	C17—C18—H18B	109.2
N2—C7—C2	123.3 (2)	N4—C18—H18C	109.2
N2—C7—H7A	118.4	C17—C18—H18C	109.2
C2—C7—H7A	118.4	H18B—C18—H18C	107.9
O4—C8—N3	122.39 (19)
N2—Ni1—O1—C1	5.01 (18)	N1—C4—C5—C6	177.1 (2)
O4—Ni1—O1—C1	79 (2)	C4—C5—C6—C1	−0.9 (4)
N4—Ni1—O1—C1	−172.18 (18)	O1—C1—C6—C5	−175.2 (2)
O1—Ni1—O4—C8	−71 (2)	C2—C1—C6—C5	4.5 (3)
N2—Ni1—O4—C8	2.93 (14)	N3—N2—C7—C2	−179.49 (18)
N4—Ni1—O4—C8	−179.97 (14)	Ni1—N2—C7—C2	3.4 (3)
O1—Ni1—N2—C7	−6.66 (19)	C3—C2—C7—N2	−176.7 (2)
O4—Ni1—N2—C7	175.13 (19)	C1—C2—C7—N2	3.4 (3)
N4—Ni1—N2—C7	129.9 (10)	Ni1—O4—C8—N3	−3.7 (2)
O1—Ni1—N2—N3	176.19 (13)	Ni1—O4—C8—C9	174.54 (14)
O4—Ni1—N2—N3	−2.02 (13)	N2—N3—C8—O4	2.0 (3)
N4—Ni1—N2—N3	−47.2 (11)	N2—N3—C8—C9	−176.18 (17)
C7—N2—N3—C8	−176.82 (18)	O4—C8—C9—C14	4.8 (3)
Ni1—N2—N3—C8	0.6 (2)	N3—C8—C9—C14	−176.88 (19)
O1—Ni1—N4—C15	−163.62 (17)	O4—C8—C9—C10	−172.4 (2)
N2—Ni1—N4—C15	59.6 (11)	N3—C8—C9—C10	5.9 (3)
O4—Ni1—N4—C15	14.62 (17)	C14—C9—C10—O5	−179.9 (2)
O1—Ni1—N4—C18	71.01 (15)	C8—C9—C10—O5	−2.7 (4)
N2—Ni1—N4—C18	−65.8 (11)	C14—C9—C10—C11	−1.3 (3)
O4—Ni1—N4—C18	−110.74 (15)	C8—C9—C10—C11	175.9 (2)
Ni1—O1—C1—C6	179.38 (15)	O5—C10—C11—C12	179.6 (2)
Ni1—O1—C1—C2	−0.3 (3)	C9—C10—C11—C12	0.9 (4)
O1—C1—C2—C3	175.1 (2)	C10—C11—C12—C13	0.6 (4)
C6—C1—C2—C3	−4.6 (3)	C11—C12—C13—C14	−1.7 (4)
O1—C1—C2—C7	−5.1 (3)	C12—C13—C14—C9	1.4 (4)
C6—C1—C2—C7	175.26 (19)	C10—C9—C14—C13	0.1 (3)
C7—C2—C3—C4	−178.7 (2)	C8—C9—C14—C13	−177.1 (2)
C1—C2—C3—C4	1.2 (3)	C18—N4—C15—C16	−52.3 (3)
C2—C3—C4—C5	2.6 (3)	Ni1—N4—C15—C16	−178.49 (17)
C2—C3—C4—N1	−177.3 (2)	C17—O6—C16—C15	−61.7 (3)
O3—N1—C4—C3	2.7 (4)	N4—C15—C16—O6	58.3 (3)
O2—N1—C4—C3	−177.6 (2)	C16—O6—C17—C18	61.2 (3)
O3—N1—C4—C5	−177.2 (3)	C15—N4—C18—C17	51.7 (3)
O2—N1—C4—C5	2.5 (3)	Ni1—N4—C18—C17	−178.51 (17)
C3—C4—C5—C6	−2.8 (4)	O6—C17—C18—N4	−57.2 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5B···N3	0.82 (2)	1.86 (3)	2.578 (3)	145 (4)
N4—H4B···O6^i	0.90 (1)	2.20 (1)	3.081 (3)	166 (2)

Symmetry code: (i) −x+3/2, y+1/2, z.

(II) bis[µ-N'-(5-nitro-2- oxidobenzylidene)benzohydrazidato]bis[(morpholine)zinc(II)

Crystal data

[Zn2(C14H10N2O3)2(C4H9NO)2]	F(000) = 1680
Mr = 813.46	Dx = 1.536 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2484 reflections
a = 17.004 (5) Å	θ = 3.0–27.5°
b = 11.130 (4) Å	µ = 1.43 mm^−1
c = 18.590 (5) Å	T = 293 K
V = 3518.3 (19) Å^3	Block, yellow
Z = 4	0.38 × 0.26 × 0.08 mm

Data collection

Rigaku R-AXIS RAPID imaging-plate diffractometer	3994 independent reflections
Radiation source: fine-focus sealed tube	2484 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.087
ω scans	θmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan (TEXRAY; Molecular Structure Corporation, 1999)	h = −21→22
Tmin = 0.614, Tmax = 0.895	k = −14→14
28663 measured reflections	l = −23→23

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.138	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0706P)^2 + 0.1235P] where P = (Fo^2 + 2Fc^2)/3
3994 reflections	(Δ/σ)max = 0.001
243 parameters	Δρmax = 1.38 e Å^−3
2 restraints	Δρmin = −0.73 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
Zn1	0.05686 (2)	0.38931 (4)	0.50721 (2)	0.03643 (16)
O1	0.04565 (12)	0.5514 (2)	0.45266 (13)	0.0383 (6)
O2	0.10013 (13)	0.2732 (2)	0.58282 (14)	0.0468 (6)
O3	0.34424 (15)	0.2231 (3)	0.57922 (16)	0.0567 (8)
H3C	0.316 (3)	0.271 (5)	0.557 (3)	0.14 (3)*
O4	0.0506 (2)	0.0904 (3)	0.32068 (19)	0.0833 (11)
N1	0.17589 (17)	0.4112 (2)	0.49636 (14)	0.0366 (7)
N2	0.21994 (16)	0.3268 (3)	0.53453 (16)	0.0392 (7)
N3	0.02004 (17)	0.2728 (3)	0.42704 (17)	0.0429 (7)
H3B	−0.0318 (8)	0.288 (3)	0.4256 (19)	0.050 (11)*
C1	0.0996 (2)	0.6148 (3)	0.41558 (18)	0.0352 (8)
C2	0.18056 (19)	0.5814 (3)	0.41560 (18)	0.0349 (8)
C3	0.2330 (2)	0.6500 (3)	0.3750 (2)	0.0434 (9)
H3A	0.2857	0.6279	0.3743	0.052*
C4	0.2098 (2)	0.7494 (4)	0.3360 (2)	0.0495 (10)
H4A	0.2458	0.7933	0.3091	0.059*
C5	0.1313 (2)	0.7816 (3)	0.3380 (2)	0.0484 (10)
H5A	0.1143	0.8489	0.3127	0.058*
C6	0.0783 (2)	0.7159 (3)	0.3767 (2)	0.0453 (9)
H6A	0.0259	0.7399	0.3770	0.054*
C7	0.21415 (19)	0.4839 (3)	0.45664 (19)	0.0399 (8)
H7A	0.2683	0.4732	0.4538	0.048*
C8	0.1742 (2)	0.2627 (3)	0.57800 (19)	0.0370 (8)
C9	0.21523 (19)	0.1711 (3)	0.62187 (19)	0.0389 (8)
C10	0.2968 (2)	0.1542 (3)	0.6201 (2)	0.0419 (9)
C11	0.3311 (2)	0.0635 (4)	0.6608 (2)	0.0518 (10)
H11A	0.3853	0.0524	0.6593	0.062*
C12	0.2861 (3)	−0.0092 (4)	0.7029 (2)	0.0593 (11)
H12A	0.3099	−0.0696	0.7298	0.071*
C13	0.2048 (3)	0.0058 (4)	0.7062 (2)	0.0631 (12)
H13A	0.1741	−0.0439	0.7350	0.076*
C14	0.1708 (2)	0.0953 (3)	0.6660 (2)	0.0510 (10)
H14A	0.1166	0.1058	0.6682	0.061*
C15	0.0351 (3)	0.1447 (4)	0.4451 (2)	0.0626 (12)
H15A	0.0065	0.1240	0.4885	0.075*
H15B	0.0908	0.1340	0.4547	0.075*
C16	0.0108 (4)	0.0614 (4)	0.3855 (3)	0.0871 (16)
H16A	0.0228	−0.0208	0.3990	0.104*
H16B	−0.0455	0.0674	0.3781	0.104*
C17	0.0310 (3)	0.2096 (5)	0.2995 (3)	0.0777 (14)
H17A	−0.0253	0.2151	0.2915	0.093*
H17B	0.0572	0.2284	0.2545	0.093*
C18	0.0549 (2)	0.2996 (4)	0.3557 (2)	0.0556 (11)
H18A	0.1118	0.2999	0.3599	0.067*
H18B	0.0385	0.3791	0.3405	0.067*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0238 (2)	0.0349 (3)	0.0506 (3)	0.00320 (16)	−0.00026 (16)	0.00426 (18)
O1	0.0264 (12)	0.0325 (13)	0.0559 (15)	0.0034 (10)	0.0071 (10)	0.0082 (11)
O2	0.0255 (13)	0.0489 (16)	0.0660 (17)	0.0055 (11)	−0.0009 (11)	0.0175 (13)
O3	0.0300 (15)	0.069 (2)	0.0707 (19)	0.0120 (13)	0.0021 (13)	0.0165 (17)
O4	0.109 (3)	0.062 (2)	0.079 (2)	0.0156 (19)	0.011 (2)	−0.0190 (18)
N1	0.0278 (15)	0.0367 (17)	0.0452 (17)	0.0044 (12)	−0.0034 (12)	0.0048 (13)
N2	0.0269 (15)	0.0401 (17)	0.0506 (17)	0.0031 (13)	−0.0046 (13)	0.0087 (15)
N3	0.0312 (17)	0.0371 (18)	0.060 (2)	0.0050 (13)	0.0028 (14)	0.0013 (15)
C1	0.0317 (19)	0.0340 (19)	0.0399 (19)	0.0012 (15)	0.0040 (14)	−0.0021 (16)
C2	0.0269 (18)	0.034 (2)	0.0436 (19)	−0.0005 (14)	0.0028 (14)	−0.0012 (15)
C3	0.0241 (18)	0.053 (2)	0.053 (2)	−0.0016 (16)	0.0024 (15)	0.0053 (19)
C4	0.043 (2)	0.050 (2)	0.056 (2)	−0.0086 (19)	0.0065 (18)	0.002 (2)
C5	0.053 (2)	0.038 (2)	0.055 (2)	0.0031 (17)	0.0061 (18)	0.0119 (18)
C6	0.035 (2)	0.043 (2)	0.057 (2)	0.0058 (16)	0.0084 (16)	0.0089 (19)
C7	0.0250 (18)	0.045 (2)	0.050 (2)	0.0007 (15)	0.0009 (15)	0.0032 (18)
C8	0.0311 (19)	0.034 (2)	0.046 (2)	0.0018 (15)	−0.0052 (15)	−0.0029 (16)
C9	0.0329 (19)	0.037 (2)	0.047 (2)	0.0058 (15)	−0.0093 (15)	−0.0024 (17)
C10	0.034 (2)	0.042 (2)	0.050 (2)	0.0049 (16)	−0.0054 (16)	−0.0046 (18)
C11	0.043 (2)	0.052 (2)	0.061 (2)	0.0131 (19)	−0.0139 (19)	0.002 (2)
C12	0.063 (3)	0.047 (3)	0.069 (3)	0.011 (2)	−0.017 (2)	0.011 (2)
C13	0.059 (3)	0.054 (3)	0.077 (3)	−0.003 (2)	−0.013 (2)	0.019 (2)
C14	0.041 (2)	0.051 (3)	0.061 (2)	0.0001 (18)	−0.0069 (18)	0.009 (2)
C15	0.087 (3)	0.035 (2)	0.066 (3)	0.001 (2)	0.009 (2)	0.000 (2)
C16	0.117 (5)	0.046 (3)	0.098 (4)	−0.009 (3)	0.016 (4)	−0.013 (3)
C17	0.096 (4)	0.075 (4)	0.062 (3)	0.011 (3)	−0.006 (3)	−0.010 (3)
C18	0.056 (3)	0.054 (3)	0.058 (3)	0.006 (2)	0.002 (2)	0.006 (2)

Geometric parameters (Å, º)

Zn1—O1^i	2.007 (2)	C4—H4A	0.9300
Zn1—O2	2.046 (2)	C5—C6	1.365 (5)
Zn1—N1	2.048 (3)	C5—H5A	0.9300
Zn1—N3	2.072 (3)	C6—H6A	0.9300
Zn1—O1	2.079 (2)	C7—H7A	0.9300
Zn1—Zn1^i	3.1437 (11)	C8—C9	1.480 (5)
O1—C1	1.348 (4)	C9—C14	1.399 (5)
O1—Zn1^i	2.007 (2)	C9—C10	1.400 (5)
O2—C8	1.269 (4)	C10—C11	1.391 (5)
O3—C10	1.348 (5)	C11—C12	1.360 (6)
O3—H3C	0.82 (3)	C11—H11A	0.9300
O4—C16	1.419 (6)	C12—C13	1.395 (6)
O4—C17	1.424 (6)	C12—H12A	0.9300
N1—C7	1.274 (4)	C13—C14	1.372 (5)
N1—N2	1.396 (4)	C13—H13A	0.9300
N2—C8	1.329 (4)	C14—H14A	0.9300
N3—C18	1.483 (5)	C15—C16	1.503 (6)
N3—C15	1.487 (5)	C15—H15A	0.9700
N3—H3B	0.899 (10)	C15—H15B	0.9700
C1—C6	1.385 (5)	C16—H16A	0.9700
C1—C2	1.425 (5)	C16—H16B	0.9700
C2—C3	1.395 (5)	C17—C18	1.503 (6)
C2—C7	1.445 (5)	C17—H17A	0.9700
C3—C4	1.380 (5)	C17—H17B	0.9700
C3—H3A	0.9300	C18—H18A	0.9700
C4—C5	1.383 (5)	C18—H18B	0.9700
O1^i—Zn1—O2	105.34 (10)	N1—C7—C2	125.5 (3)
O1^i—Zn1—N1	148.80 (11)	N1—C7—H7A	117.2
O2—Zn1—N1	77.73 (10)	C2—C7—H7A	117.2
O1^i—Zn1—N3	102.15 (11)	O2—C8—N2	125.1 (3)
O2—Zn1—N3	101.97 (12)	O2—C8—C9	119.5 (3)
N1—Zn1—N3	107.59 (11)	N2—C8—C9	115.4 (3)
O1^i—Zn1—O1	79.42 (10)	C14—C9—C10	117.9 (3)
O2—Zn1—O1	156.40 (10)	C14—C9—C8	119.0 (3)
N1—Zn1—O1	86.52 (10)	C10—C9—C8	123.1 (3)
N3—Zn1—O1	99.47 (11)	O3—C10—C11	118.0 (3)
O1^i—Zn1—Zn1^i	40.54 (7)	O3—C10—C9	122.0 (3)
O2—Zn1—Zn1^i	140.78 (8)	C11—C10—C9	120.0 (4)
N1—Zn1—Zn1^i	120.41 (8)	C12—C11—C10	120.6 (4)
N3—Zn1—Zn1^i	104.08 (9)	C12—C11—H11A	119.7
O1—Zn1—Zn1^i	38.88 (6)	C10—C11—H11A	119.7
C1—O1—Zn1^i	127.6 (2)	C11—C12—C13	120.7 (4)
C1—O1—Zn1	129.9 (2)	C11—C12—H12A	119.6
Zn1^i—O1—Zn1	100.58 (10)	C13—C12—H12A	119.6
C8—O2—Zn1	111.5 (2)	C14—C13—C12	118.7 (4)
C10—O3—H3C	108 (5)	C14—C13—H13A	120.6
C16—O4—C17	109.6 (4)	C12—C13—H13A	120.6
C7—N1—N2	116.6 (3)	C13—C14—C9	122.0 (4)
C7—N1—Zn1	129.6 (2)	C13—C14—H14A	119.0
N2—N1—Zn1	113.6 (2)	C9—C14—H14A	119.0
C8—N2—N1	110.9 (3)	N3—C15—C16	112.2 (4)
C18—N3—C15	109.0 (3)	N3—C15—H15A	109.2
C18—N3—Zn1	113.4 (2)	C16—C15—H15A	109.2
C15—N3—Zn1	112.7 (2)	N3—C15—H15B	109.2
C18—N3—H3B	109 (2)	C16—C15—H15B	109.2
C15—N3—H3B	111 (2)	H15A—C15—H15B	107.9
Zn1—N3—H3B	101 (2)	O4—C16—C15	110.7 (4)
O1—C1—C6	120.9 (3)	O4—C16—H16A	109.5
O1—C1—C2	121.4 (3)	C15—C16—H16A	109.5
C6—C1—C2	117.7 (3)	O4—C16—H16B	109.5
C3—C2—C1	118.3 (3)	C15—C16—H16B	109.5
C3—C2—C7	116.4 (3)	H16A—C16—H16B	108.1
C1—C2—C7	125.3 (3)	O4—C17—C18	111.4 (4)
C4—C3—C2	122.7 (3)	O4—C17—H17A	109.3
C4—C3—H3A	118.7	C18—C17—H17A	109.3
C2—C3—H3A	118.7	O4—C17—H17B	109.3
C3—C4—C5	118.0 (4)	C18—C17—H17B	109.3
C3—C4—H4A	121.0	H17A—C17—H17B	108.0
C5—C4—H4A	121.0	N3—C18—C17	112.3 (4)
C6—C5—C4	120.8 (4)	N3—C18—H18A	109.1
C6—C5—H5A	119.6	C17—C18—H18A	109.1
C4—C5—H5A	119.6	N3—C18—H18B	109.1
C5—C6—C1	122.5 (3)	C17—C18—H18B	109.1
C5—C6—H6A	118.8	H18A—C18—H18B	107.9
C1—C6—H6A	118.8
O1^i—Zn1—O1—C1	164.7 (3)	C6—C1—C2—C3	−1.8 (5)
O2—Zn1—O1—C1	60.6 (4)	O1—C1—C2—C7	−3.5 (5)
N1—Zn1—O1—C1	12.7 (3)	C6—C1—C2—C7	175.8 (3)
N3—Zn1—O1—C1	−94.6 (3)	C1—C2—C3—C4	1.0 (5)
Zn1^i—Zn1—O1—C1	164.7 (3)	C7—C2—C3—C4	−176.8 (3)
O1^i—Zn1—O1—Zn1^i	0.0	C2—C3—C4—C5	0.4 (6)
O2—Zn1—O1—Zn1^i	−104.2 (2)	C3—C4—C5—C6	−0.9 (6)
N1—Zn1—O1—Zn1^i	−152.02 (12)	C4—C5—C6—C1	0.0 (6)
N3—Zn1—O1—Zn1^i	100.72 (12)	O1—C1—C6—C5	−179.4 (3)
O1^i—Zn1—O2—C8	−156.4 (2)	C2—C1—C6—C5	1.4 (5)
N1—Zn1—O2—C8	−8.4 (2)	N2—N1—C7—C2	−176.8 (3)
N3—Zn1—O2—C8	97.3 (2)	Zn1—N1—C7—C2	8.8 (5)
O1—Zn1—O2—C8	−57.6 (4)	C3—C2—C7—N1	−179.5 (3)
Zn1^i—Zn1—O2—C8	−131.9 (2)	C1—C2—C7—N1	2.8 (6)
O1^i—Zn1—N1—C7	−76.3 (4)	Zn1—O2—C8—N2	6.1 (4)
O2—Zn1—N1—C7	−175.7 (3)	Zn1—O2—C8—C9	−172.3 (2)
N3—Zn1—N1—C7	85.5 (3)	N1—N2—C8—O2	2.3 (5)
O1—Zn1—N1—C7	−13.4 (3)	N1—N2—C8—C9	−179.3 (3)
Zn1^i—Zn1—N1—C7	−33.3 (3)	O2—C8—C9—C14	2.1 (5)
O1^i—Zn1—N1—N2	109.2 (3)	N2—C8—C9—C14	−176.4 (3)
O2—Zn1—N1—N2	9.8 (2)	O2—C8—C9—C10	−179.6 (3)
N3—Zn1—N1—N2	−89.1 (2)	N2—C8—C9—C10	1.9 (5)
O1—Zn1—N1—N2	172.1 (2)	C14—C9—C10—O3	−179.9 (3)
Zn1^i—Zn1—N1—N2	152.14 (18)	C8—C9—C10—O3	1.8 (6)
C7—N1—N2—C8	175.1 (3)	C14—C9—C10—C11	0.6 (5)
Zn1—N1—N2—C8	−9.6 (3)	C8—C9—C10—C11	−177.7 (3)
O1^i—Zn1—N3—C18	126.2 (2)	O3—C10—C11—C12	−179.7 (4)
O2—Zn1—N3—C18	−125.0 (2)	C9—C10—C11—C12	−0.3 (6)
N1—Zn1—N3—C18	−44.2 (3)	C10—C11—C12—C13	−0.1 (6)
O1—Zn1—N3—C18	45.1 (3)	C11—C12—C13—C14	0.1 (7)
Zn1^i—Zn1—N3—C18	84.6 (2)	C12—C13—C14—C9	0.3 (6)
O1^i—Zn1—N3—C15	−109.4 (3)	C10—C9—C14—C13	−0.7 (6)
O2—Zn1—N3—C15	−0.6 (3)	C8—C9—C14—C13	177.7 (4)
N1—Zn1—N3—C15	80.1 (3)	C18—N3—C15—C16	−51.3 (5)
O1—Zn1—N3—C15	169.5 (3)	Zn1—N3—C15—C16	−178.0 (3)
Zn1^i—Zn1—N3—C15	−151.1 (2)	C17—O4—C16—C15	−61.1 (6)
Zn1^i—O1—C1—C6	−25.6 (5)	N3—C15—C16—O4	57.8 (6)
Zn1—O1—C1—C6	173.5 (2)	C16—O4—C17—C18	60.5 (6)
Zn1^i—O1—C1—C2	153.6 (2)	C15—N3—C18—C17	50.4 (5)
Zn1—O1—C1—C2	−7.3 (5)	Zn1—N3—C18—C17	176.7 (3)
O1—C1—C2—C3	179.0 (3)	O4—C17—C18—N3	−56.2 (5)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···O3^ii	0.90 (1)	2.11 (1)	2.992 (4)	165 (3)
O3—H3C···N2	0.82 (3)	1.80 (4)	2.547 (4)	149 (6)

Symmetry code: (ii) x−1/2, −y+1/2, −z+1.