Di­aqua­bis­{μ-1,5-bis­[(pyridin-2-yl)methyl­idene]carbonohydrazide(1–)}di-μ-chlorido-tetra­chlorido­tetra­zinc(II)

Seck, T.M.; Gaye, P.A.; Ndoye, C.; Thiam, I.E.; Diouf, O.; Retailleau, P.; Gaye, M.

doi:10.1107/S2056989020009834

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 76| Part 8| August 2020| Pages 1349-1352

https://doi.org/10.1107/S2056989020009834

Open

access

Diaquabis{μ-1,5-bis[(pyridin-2-yl)methylidene]carbonohydrazide(1–)}di-μ-chlorido-tetrachloridotetrazinc(II)

Thierno Moussa Seck,^a Papa Aly Gaye,^b ^* Cheikh Ndoye,^a Ibrahima Elhadji Thiam,^a Ousmane Diouf,^a Pascal Retailleau ^c and Mohamed Gaye ^a

^aDépartement de Chimie, Faculté des Sciences et Techniques, Université Cheikh Anta Diop, Dakar, Senegal, ^bDépartement de Chimie, UFR Sciences et Techniques, Université Assane Seck, Ziguinchor, Senegal, and ^cSubstances Naturelles, CNRS UPR 2301, Université Paris-Sud, Université, Paris-Saclay, 1 av. de la Terrasse, 91198 Gif-sur-Yvette, France
^*Correspondence e-mail: mlgayeastou@yahoo.fr

Edited by J. Ellena, Universidade de Sâo Paulo, Brazil (Received 4 July 2020; accepted 17 July 2020; online 24 July 2020)

A tetranuclear Zn^II complex, [Zn₄(C₁₃H₁₁N₆O)₂Cl₆(H₂O)₂] or {[Zn₂(HL)(H₂O)(Cl₂)](μCl)₂[Zn₂(HL)(H₂O)(Cl)]}₂, was synthesized by mixing an equimolar amount of a methanol solution containing ZnCl₂ and a methanol solution containing the ligand H₂L [1,5-bis(pyridin-2-ylmethylene)carbonohydrazide]. In the tetranuclear complex, each of the two ligand molecules forms a dinuclear unit that is connected to another dinuclear unit by two bridging chloride anions. In each dinuclear unit, one Zn^II cation is pentacoordinated in a N₂OCl₂ in a distorted square-pyramidal geometry, while the other Zn^II cation is hexacoordinated in a N₃OCl₂ environment with a distorted octahedral geometry. The basal plane around the pentacoordinated Zn^II cation is formed by one chloride anion, one oxygen atom, one imino nitrogen atom and one pyridine nitrogen atom with the apical position occupied by a chloride anion. The basal plane of the hexacoordinated Zn^II cation is formed by one chloride anion, one hydrazinyl nitrogen atom, one imino nitrogen atom and one pyridine nitrogen atom with the apical positions occupied by a water oxygen atom and a bridged chloro anion from another dinuclear unit, leading to a tetranuclear complex. A series of intramolecular C—H⋯Cl hydrogen bonds is observed in each tetranuclear unit. In the crystal, the tetranuclear units are connected by intermolecular C—H⋯Cl, C—H⋯O and N—H⋯O hydrogen bonds, forming a planar two-dimensional structure in the ac plane.

Keywords: zinc; complex; crystal structure; tetranuclear; square-pyramidal coordination.

CCDC reference: 2011426

1. Chemical context

Symmetrical dicarbonohydrazide Schiff bases possess two cavitiess, which make them versatile. During complexation, either one or both of the cages can be occupied by a metal ion depending on the reaction conditions. The presence of an amidic bond in these molecules leads to the keto-enol tautomer, which can act in neutral or deprotonated forms. These compounds can adopt two different configurations, e.g. S-cis or S-trans, yielding different structures with the same metal cation. These ligands can coordinate to transition metals in a pentadentate or hexadentate manner (El-Gammal et al., 2012 ; Sow et al., 2013 ), as well as in the ketonic or enolic form (Zhang et al., 2014 ). When the configuration of this kind of ligand is S-trans, it acts in a hexadentate fashion. In this case, the formation of a dinuclear complex with a μ-N,N bridge is generally observed, for example in a dinuclear copper(II) complex (Dragancea et al., 2014 ). The S-cis–enol configuration leads to the formation of square-grid complexes by directed self-assembly (Bikas et al., 2015 ; Sow et al., 2013; Li et al., 2014 ). In these complexes, μ-O and μ-N,N atoms bridge the metal ions, which display N₄O₂ or N₅O octahedral environments (Shuvaev et al., 2010 ).

The behavior of these molecules has attracted the interest of chemists working in coordination chemistry. The free dicarbonohydrazide exhibits biological activities (Bacchi et al., 1999 ; Kothari & Sharma, 2010 ), which are increased upon complexation with certain transition metals (Wu et al., 2009 ; Bikas et al., 2015). The synthesis of high nuclearity complexes of transition metals derived from these types of ligands are highly targeted because of their magnetic (Sow et al., 2013; Zhang et al., 2014a; Dragancea et al., 2014), catalytic (Bikas et al., 2015), biological (Zhang et al., 2014) and optical (Easwaran potti et al., 2007 ) properties. Recently, our research group synthesized a new tetranuclear grid complex [Zn₄(HL¹)₄](NO₃)₄·2H₂O where H₂L¹ is 1,5-bis[1-(pyridin-2-yl)ethylidene)carbonohydrazide]. The study of the fluorescence properties of the ligand H₂L¹ and its complex revealed that complexation increased the fluorescent properties of the ligand (Seck et al., 2018 ). In a continuation of our work on symmetrical dicarbonohydrazide ligands, we have synthesized and characterized a new tetranuclear zinc(II) complex formulated as {[Zn₂(HL)(H₂O)(Cl₂)](μCl)₂[Zn₂(HL)(H₂O)(Cl)]}₂ where H₂L is 1,5-bis(pyridin-2-ylmethylene)carbonohydrazide.

2. Structural commentary

The title compound is a centrosymmetric tetranuclear Zn^II complex composed by two dinuclear entities. Each dinuclear entity contains one ligand molecule acting in monodeprotonated form, three bonded chloride anions, one bonded water molecule, and two Zn^II cations. The two units are linked by two choride anions acting as bridges (Fig. 1). Each monodeprotonated organic molecule acts through two azomethine nitrogen atoms, two pyridine nitrogen atoms, one hydrazinyl nitrogen atom and one carbonyl oxygen atom, resulting in a hexadentate ligand. The Zn1 and Zn2 cations are situated, respectively in N₂OCl₂ and N₃OCl₂ coordination sites (Fig. 1). In the structure of the complex, the two ligand molecules are arranged in the Z–E form.

Figure 1
A view of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are plotted at the 30% probability level. Unlabelled atoms are generated by the symmetry operation 1 − x, 1 − y, −z.

The Zn1 atom is pentacoordinated by one pyridine nitrogen atom, one azomethine nitrogen atom, one oxygen atom, and two terminal chloride anions. According to the Addison (1984 ) index, the coordination geometry around a pentacoordinated metal center can be discussed in terms of the τ parameter [defined as τ = (β - α)/60 where β and α are the largest values of the bond angles around the central atom]; τ = 0 for a perfect square pyramidal geometry while τ = 1 for a perfect trigonal–bipyramidal geometry. In the case of the title complex, the τ value of 0.1085 is indicative of a distorted square-pyramidal geometry around the Zn1 center. The equatorial plane is occupied by atoms N5, N6, Cl3, O2 while the apical position is occupied by Cl2. The angles N5—Zn1—O2 [72.76 (9)°], O2—Zn1—Cl3 [96.00 (6)°], Cl3—Zn1—N6 [97.10 (8)°] and N6—Zn1—N5 [75.82 (10)°] deviate from those for a regular square pyramid. The transoid angles in the basal plane O2—Zn1—N6 and N5—Zn1—Cl3 deviate severely from linearity with values of 144.87 (10) and 138.36 (8)°, respectively (Table 1). The angles involving the atoms in the axial position deviate severely from the ideal value of 90°, being in the range 97.45 (7)–110.85 (8)°.

Table 1
Selected geometric parameters (Å, °)

Zn1—N5	2.069 (2)	Zn2—O1	2.132 (3)
Zn1—N6	2.191 (3)	Zn2—N4	2.139 (3)
Zn1—O2	2.237 (2)	Zn2—N1	2.184 (3)
Zn1—Cl3	2.2477 (9)	Zn2—Cl1	2.2873 (8)
Zn1—Cl2	2.2573 (10)	Zn2—Cl1ⁱ	2.7489 (10)
Zn2—N2	2.117 (2)

N5—Zn1—N6	75.82 (10)	N2—Zn2—N1	74.29 (9)
N5—Zn1—O2	72.76 (9)	O1—Zn2—N1	87.40 (10)
N6—Zn1—O2	144.87 (10)	N4—Zn2—N1	148.24 (10)
N5—Zn1—Cl3	138.36 (8)	N2—Zn2—Cl1	171.67 (8)
N6—Zn1—Cl3	97.10 (8)	O1—Zn2—Cl1	95.98 (8)
O2—Zn1—Cl3	96.00 (6)	N4—Zn2—Cl1	111.20 (7)
N5—Zn1—Cl2	110.85 (8)	N1—Zn2—Cl1	100.33 (7)
N6—Zn1—Cl2	108.19 (9)	N2—Zn2—Cl1ⁱ	85.59 (8)
O2—Zn1—Cl2	97.45 (7)	O1—Zn2—Cl1ⁱ	172.20 (7)
Cl3—Zn1—Cl2	110.31 (4)	N4—Zn2—Cl1ⁱ	92.27 (8)
N2—Zn2—O1	90.19 (11)	N1—Zn2—Cl1ⁱ	85.15 (8)
N2—Zn2—N4	73.95 (9)	Cl1—Zn2—Cl1ⁱ	87.63 (3)
O1—Zn2—N4	92.86 (10)	Zn2—Cl1—Zn2ⁱ	92.37 (3)
Symmetry code: (i) -x+1, -y+1, -z.

The geometry around the hexacoordinated Zn2 atom is best described as distorted octahedral. The basal plane is occupied by atoms N2, N4, N1 and Cl1 with cissoid bond angles in the range 73.95 (9)–111.20 (7)° and transoid angles of 171.67 (8)° [N2—Zn2—Cl1] and 148.24 (10)° [N4—Zn2—N1]. The sum of the angles subtended by the atoms in the plane is 359.77°. The apical positions are occupied by O1 and Cl1ⁱ with O 1—Zn2—Cl1ⁱ = 172.20 (7)° (Table 1). The deviation of the angles around the Zn2 cation with respect to the valence angles for a regular octahedron (180 and 90°) indicates that the geometry around the Zn2 ion is a distorted octahedron (Fig. 1). The five-membered rings (NCNNZn and NCCNZn) formed by the ligand with Zn2 impose large distortions on the ideal angles of a regular octahedron with bite angles in the range 73.95 (9)–74.29 (9)°.

The Zn2—Cl1—Zn2ⁱ angle of 92.37 (3)° is in accordance with the value reported for the complex di-μ-chlorido-bis{[2-({[2-(2-pyridyl)ethyl](2-pyridylmethyl)amino}methyl)-phenol]zinc(II)} bis(perchlorate) dihydrate (Coelho et al., 2010 ). The zinc–halogen distances Zn2—Cl1 and Zn2ⁱ—Cl1 of 2.2873 (8) and 2.7489 (10) Å, respectively, agree with those for a chloride anion in a bridging position (Coelho et al., 2010; Yu et al., 2009 ). The distances Zn1—Cl2 and Zn1—Cl3 of 2.2573 (10) and 2.2477 (9) Å, respectively, are indicative of a unidentate terminal chloride anion (Sanyal et al., 2014 ).

Only one weak intramolecular C—H⋯O hydrogen bond (Table 2) occurs.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯Cl3ⁱⁱ	0.82 (2)	2.27 (2)	3.052 (3)	161 (5)
O1—H1B⋯Cl2ⁱⁱⁱ	0.82 (2)	2.32 (2)	3.129 (3)	169 (5)
C8—H8⋯Cl1	0.93	2.82	3.649 (3)	149
C2—H2⋯O1^iv	0.93	2.50	3.342 (4)	151
C6—H6⋯Cl3^v	0.93	2.55	3.425 (3)	158
N3—H3N⋯O2^v	0.85 (4)	2.00 (4)	2.837 (3)	170 (4)
Symmetry codes: (ii) -x+2, -y+1, -z+1; (iii) x, y+1, z; (iv) -x+1, -y+2, -z; (v) -x+1, -y+1, -z+1.

3. Supramolecular features

In the crystal, numerous intermolecular O—H⋯Cl, C—H⋯O, C—H⋯Cl and N—H⋯O hydrogen bonds are observed (Fig. 2, Table 2). An N—H⋯O type occurs between the oxygen atom O2 of the ligand, which acts as a proton acceptor, and the nitrogen atom of the hydrazinyl group, which acts as the proton donor. An O—H⋯Cl link is established between a water molecule in the apical position of the Zn2 ion, acting as proton donor, and a terminal chloride ions linked to Zn1 as proton acceptor. These intermolecular hydrogen bonds ensure the cohesion of the crystal, developing a planar two-dimensional structure in the ac plane.

Figure 2
View of the chains formed by hydrogen bonds in the ac plane.

4. Database survey

A survey of the Cambridge Structural Database (CSD, Version 5.40, October 2019; Groom et al., 2016 ) reveals five examples of crystal structures containing H₂L derivatives where the molecule is monoprotonated (H₃L⁺) or diprotonated (H₄L²⁺) and additionally one Dy complex molecule in which HL⁻ and L²⁻ are present as ligands. Among the diprotonated molecules, three different counter-ions are present: I⁻ in AVOSOV (Hoque et al., 2016 ), ClO₄⁻ in LOFDUH (Hoque et al., 2014 ), and SO₄²⁻ in LOFFAP (Hoque et al., 2014) and LOFFAP01 (Hoque et al., 2016). In the structure incorporating monoprotonated H₃L⁺, H₂PO₄⁻ is the counter-ion (LOFFIX; Hoque et al., 2014). The tetranuclear Dy³⁺ complex has a [2 x 2] grid structure (DIGQER; Randell et al., 2013 ).

5. Synthesis and crystallization

Synthesis of the H₂L ligand

Carbonohydrazide (2 g, 22.2 mmol) was introduced into a 100 mL flask containing 20 mL of methanol. To the resulting suspension was added a methanolic solution containing 2-pyridinecarbaldehyde (4.757 g 44.4 mmol) and two drops of glacial acetic acid. The mixture was stirred under reflux for 2 h. After being kept for two days at 277 K, the resulting orange solution yielded a precipitate, which was recovered by filtration. The solid was washed successively with cold methanol (2 × 10 mL) and diethyl ether (2 × 10 mL) before being dried under P₂O₅; m.p. 489 K, yield 82%. Analysis calculated for [C₁₃H₁₂N₆O] C, 58.20; H, 4.51; N, 31.33. Found: C, 58.17; H, 4.49; N, 31.30. IR (cm⁻¹): 3439, 3204, 3198, 3055, 2936, 1684, 1582, 1610, 1582, 1532, 1467, 1360, 1274, 1131. ¹H NMR (DMSO-d₆, δ in ppm): 7.6–8.72 (m, 8H, H_Py); 10.82 (s, 2H, H—N); 8.03 (s, 2H, H—C=N). ¹³C NMR (DMSO-d₆, δ in ppm): 157.9 (C=O); 154.70 (C_Py); 148.07 (C_Py); 146.67 (C=N) imine; 137.60 (CPy); 123.00 (C_Py); 119.09 (C_Py).

Synthesis of the title complex

The title complex was prepared by mixing a solution of H₂L (134.15 mg, 0.5 mmol) in 10 mL of methanol and a methanolic solution of ZnCl₂ (68.15 mg, 0.5 mmol). A yellow solution was obtained after stirring for 1 h at room temperature. The solution was filtered, and the filtrate left for slow evaporation. After two weeks, yellow crystals suitable for X-ray diffraction were collected, yield 87.9%. Analysis calculated for [C₂₆H₂₆Cl₆Zn₄N₁₂O₄] C, 29.89; H, 2.51; N, 16.09. Found: C, 29.88; H, 2.49; N, 16.05. Λ_M (S cm² mol⁻): 11. IR (cm⁻¹): 3428, 3116, 3043, 1585, 1553, 1497, 1461, 1377, 1313, 1226, 1143, 820.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. N- and C-bound H atoms were refined with U_iso(H) = 1.2U_eq(N) or 1.5U_eq(O). C atoms were placed in calculated positions and refined as riding with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C).

Table 3
Experimental details

Crystal data
Chemical formula	[Zn₄(C₁₃H₁₁N₆O)₂Cl₆(H₂O)₂]
M_r	1044.77
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	293
a, b, c (Å)	9.2002 (4), 9.4306 (4), 11.7651 (4)
α, β, γ (°)	94.639 (3), 110.091 (4), 97.599 (3)
V (Å³)	941.47 (7)
Z	1
Radiation type	Mo Kα
μ (mm⁻¹)	2.99
Crystal size (mm)	0.21 × 0.10 × 0.05

Data collection
Diffractometer	XtaLAB AFC12 (RINC): Kappa single
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2018 $[Rigaku OD (2018). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.375, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	15934, 4132, 3343
R_int	0.049
(sin θ/λ)_max (Å⁻¹)	0.641

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.103, 1.05
No. of reflections	4127
No. of parameters	244
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.80, −0.94
Computer programs: CrysAlis PRO (Rigaku OD, 2018 $[Rigaku OD (2018). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ) and ORTEP-3 for Windows (Farrugia, 2012 ).

Supporting information

CCDC reference: 2011426

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989020009834/ex2035sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989020009834/ex2035Isup2.hkl

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2018); cell refinement: CrysAlis PRO (Rigaku OD, 2018); data reduction: CrysAlis PRO (Rigaku OD, 2018); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012).

Diaquabis{µ-1,5-bis[(pyridin-2-yl)methylidene]carbonohydrazide(1-)}di-µ-chlorido-tetrachloridotetrazinc(II) top

Crystal data top

[Zn₄(C₁₃H₁₁N₆O)₂Cl₆(H₂O)₂]	Z = 1
M_r = 1044.77	F(000) = 520
Triclinic, P1	D_x = 1.843 Mg m⁻³
a = 9.2002 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.4306 (4) Å	Cell parameters from 6440 reflections
c = 11.7651 (4) Å	θ = 4.3–30.7°
α = 94.639 (3)°	µ = 2.99 mm⁻¹
β = 110.091 (4)°	T = 293 K
γ = 97.599 (3)°	Tab, pale yellow
V = 941.47 (7) Å³	0.21 × 0.10 × 0.05 mm

Data collection top

XtaLAB AFC12 (RINC): Kappa single diffractometer	4132 independent reflections
Radiation source: micro-focus sealed X-ray tube, Rigaku (Mo) X-ray Source	3343 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.049
ω scans	θ_max = 27.1°, θ_min = 4.4°
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2018)	h = −11→11
T_min = 0.375, T_max = 1.000	k = −12→12
15934 measured reflections	l = −15→15

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.039	Hydrogen site location: mixed
wR(F²) = 0.103	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0583P)² + 0.5038P] where P = (F_o² + 2F_c²)/3
4127 reflections	(Δ/σ)_max < 0.001
244 parameters	Δρ_max = 0.80 e Å⁻³
2 restraints	Δρ_min = −0.94 e Å⁻³

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Zn1	0.80255 (4)	0.26414 (4)	0.42860 (3)	0.03096 (12)
Zn2	0.57362 (4)	0.62337 (4)	0.14274 (3)	0.03302 (12)
Cl1	0.66995 (10)	0.59565 (10)	−0.01140 (7)	0.0390 (2)
Cl2	0.61634 (11)	0.06523 (11)	0.34885 (11)	0.0537 (3)
Cl3	0.93484 (10)	0.25785 (12)	0.62765 (8)	0.0500 (3)
O1	0.7387 (3)	0.8113 (3)	0.2417 (2)	0.0427 (6)
H1A	0.823 (3)	0.802 (5)	0.291 (4)	0.064*
H1B	0.718 (6)	0.878 (4)	0.278 (4)	0.064*
N1	0.4062 (3)	0.7669 (3)	0.0700 (2)	0.0312 (6)
N4	0.6695 (3)	0.4927 (3)	0.2813 (2)	0.0316 (6)
N5	0.7847 (3)	0.4085 (3)	0.3030 (2)	0.0290 (5)
O2	0.6460 (3)	0.4146 (3)	0.4577 (2)	0.0366 (5)
N2	0.4518 (3)	0.6419 (3)	0.2652 (2)	0.0297 (5)
C5	0.3207 (4)	0.7960 (4)	0.1389 (3)	0.0345 (7)
C7	0.6080 (4)	0.4865 (3)	0.3697 (3)	0.0291 (6)
N3	0.4932 (3)	0.5689 (3)	0.3617 (3)	0.0362 (7)
H3N	0.442 (5)	0.567 (4)	0.409 (4)	0.043*
C1	0.3864 (4)	0.8307 (4)	−0.0303 (3)	0.0397 (8)
H1	0.444294	0.809996	−0.078687	0.048*
C10	1.1160 (4)	0.3293 (4)	0.2278 (4)	0.0423 (8)
H10	1.115666	0.386847	0.167216	0.051*
N6	0.9966 (3)	0.2407 (3)	0.3647 (3)	0.0359 (6)
C9	1.0000 (4)	0.3243 (4)	0.2777 (3)	0.0325 (7)
C4	0.2147 (5)	0.8905 (4)	0.1096 (4)	0.0481 (9)
H4	0.156102	0.908579	0.158053	0.058*
C8	0.8767 (4)	0.4134 (4)	0.2430 (3)	0.0327 (7)
H8	0.866238	0.470241	0.180546	0.039*
C2	0.2826 (5)	0.9266 (4)	−0.0646 (3)	0.0480 (9)
H2	0.270608	0.969450	−0.135049	0.058*
C11	1.2334 (5)	0.2466 (5)	0.2698 (4)	0.0510 (10)
H11	1.312414	0.247754	0.237298	0.061*
C6	0.3499 (4)	0.7248 (4)	0.2481 (3)	0.0385 (8)
H6	0.297366	0.738940	0.301839	0.046*
C3	0.1979 (5)	0.9572 (5)	0.0069 (4)	0.0544 (10)
H3	0.129191	1.022847	−0.013639	0.065*
C13	1.1100 (4)	0.1625 (4)	0.4044 (4)	0.0459 (9)
H13	1.107789	0.104825	0.464524	0.055*
C12	1.2309 (5)	0.1637 (5)	0.3596 (4)	0.0522 (10)
H12	1.309318	0.108995	0.390059	0.063*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0313 (2)	0.0364 (2)	0.0331 (2)	0.01189 (15)	0.01808 (15)	0.00942 (15)
Zn2	0.0394 (2)	0.0418 (2)	0.0306 (2)	0.01887 (17)	0.02281 (16)	0.01138 (16)
Cl1	0.0456 (5)	0.0475 (5)	0.0364 (4)	0.0111 (4)	0.0291 (4)	0.0070 (3)
Cl2	0.0430 (5)	0.0450 (5)	0.0757 (7)	0.0007 (4)	0.0311 (5)	−0.0103 (5)
Cl3	0.0343 (4)	0.0852 (7)	0.0373 (4)	0.0232 (5)	0.0152 (4)	0.0142 (4)
O1	0.0397 (14)	0.0429 (15)	0.0450 (15)	0.0176 (12)	0.0110 (11)	0.0047 (11)
N1	0.0327 (13)	0.0373 (15)	0.0285 (13)	0.0097 (11)	0.0152 (11)	0.0078 (11)
N4	0.0349 (14)	0.0408 (15)	0.0309 (13)	0.0187 (12)	0.0209 (11)	0.0106 (11)
N5	0.0287 (13)	0.0330 (14)	0.0329 (13)	0.0123 (11)	0.0173 (11)	0.0077 (11)
O2	0.0470 (13)	0.0480 (14)	0.0323 (12)	0.0270 (11)	0.0263 (10)	0.0183 (10)
N2	0.0337 (13)	0.0371 (14)	0.0275 (12)	0.0163 (11)	0.0175 (11)	0.0101 (11)
C5	0.0331 (16)	0.0419 (18)	0.0329 (16)	0.0152 (14)	0.0136 (13)	0.0077 (14)
C7	0.0296 (15)	0.0359 (17)	0.0279 (15)	0.0123 (13)	0.0155 (12)	0.0047 (12)
N3	0.0420 (16)	0.0511 (18)	0.0326 (14)	0.0273 (14)	0.0251 (12)	0.0166 (13)
C1	0.0441 (19)	0.043 (2)	0.0340 (17)	0.0059 (16)	0.0165 (15)	0.0098 (15)
C10	0.0406 (19)	0.047 (2)	0.052 (2)	0.0100 (16)	0.0311 (17)	0.0059 (16)
N6	0.0330 (14)	0.0446 (16)	0.0402 (15)	0.0168 (12)	0.0212 (12)	0.0092 (12)
C9	0.0285 (15)	0.0394 (17)	0.0359 (16)	0.0083 (13)	0.0188 (13)	0.0046 (13)
C4	0.046 (2)	0.056 (2)	0.052 (2)	0.0282 (19)	0.0211 (18)	0.0166 (18)
C8	0.0348 (16)	0.0367 (17)	0.0377 (17)	0.0136 (14)	0.0230 (14)	0.0102 (13)
C2	0.049 (2)	0.052 (2)	0.043 (2)	0.0120 (18)	0.0111 (17)	0.0210 (17)
C11	0.0386 (19)	0.057 (2)	0.070 (3)	0.0108 (18)	0.0369 (19)	0.001 (2)
C6	0.0401 (18)	0.053 (2)	0.0368 (17)	0.0227 (16)	0.0247 (15)	0.0124 (15)
C3	0.049 (2)	0.057 (3)	0.062 (3)	0.029 (2)	0.0153 (19)	0.023 (2)
C13	0.046 (2)	0.054 (2)	0.051 (2)	0.0236 (18)	0.0266 (17)	0.0155 (18)
C12	0.040 (2)	0.065 (3)	0.065 (3)	0.0294 (19)	0.0281 (19)	0.011 (2)

Geometric parameters (Å, º) top

Zn1—N5	2.069 (2)	C7—N3	1.374 (4)
Zn1—N6	2.191 (3)	N3—H3N	0.85 (4)
Zn1—O2	2.237 (2)	C1—C2	1.384 (5)
Zn1—Cl3	2.2477 (9)	C1—H1	0.9300
Zn1—Cl2	2.2573 (10)	C10—C9	1.381 (4)
Zn2—N2	2.117 (2)	C10—C11	1.391 (5)
Zn2—O1	2.132 (3)	C10—H10	0.9300
Zn2—N4	2.139 (3)	N6—C13	1.333 (4)
Zn2—N1	2.184 (3)	N6—C9	1.348 (4)
Zn2—Cl1	2.2873 (8)	C9—C8	1.465 (4)
Zn2—Cl1ⁱ	2.7489 (10)	C4—C3	1.378 (5)
O1—H1A	0.816 (19)	C4—H4	0.9300
O1—H1B	0.819 (19)	C8—H8	0.9300
N1—C1	1.335 (4)	C2—C3	1.367 (6)
N1—C5	1.346 (4)	C2—H2	0.9300
N4—C7	1.345 (4)	C11—C12	1.369 (6)
N4—N5	1.374 (3)	C11—H11	0.9300
N5—C8	1.274 (4)	C6—H6	0.9300
O2—C7	1.258 (4)	C3—H3	0.9300
N2—C6	1.273 (4)	C13—C12	1.385 (5)
N2—N3	1.344 (3)	C13—H13	0.9300
C5—C4	1.382 (5)	C12—H12	0.9300
C5—C6	1.457 (4)

N5—Zn1—N6	75.82 (10)	C4—C5—C6	122.1 (3)
N5—Zn1—O2	72.76 (9)	O2—C7—N4	126.6 (3)
N6—Zn1—O2	144.87 (10)	O2—C7—N3	117.8 (3)
N5—Zn1—Cl3	138.36 (8)	N4—C7—N3	115.6 (3)
N6—Zn1—Cl3	97.10 (8)	N2—N3—C7	116.7 (3)
O2—Zn1—Cl3	96.00 (6)	N2—N3—H3N	120 (3)
N5—Zn1—Cl2	110.85 (8)	C7—N3—H3N	123 (3)
N6—Zn1—Cl2	108.19 (9)	N1—C1—C2	122.3 (3)
O2—Zn1—Cl2	97.45 (7)	N1—C1—H1	118.9
Cl3—Zn1—Cl2	110.31 (4)	C2—C1—H1	118.9
N2—Zn2—O1	90.19 (11)	C9—C10—C11	118.9 (3)
N2—Zn2—N4	73.95 (9)	C9—C10—H10	120.6
O1—Zn2—N4	92.86 (10)	C11—C10—H10	120.6
N2—Zn2—N1	74.29 (9)	C13—N6—C9	118.7 (3)
O1—Zn2—N1	87.40 (10)	C13—N6—Zn1	128.7 (2)
N4—Zn2—N1	148.24 (10)	C9—N6—Zn1	112.5 (2)
N2—Zn2—Cl1	171.67 (8)	N6—C9—C10	121.8 (3)
O1—Zn2—Cl1	95.98 (8)	N6—C9—C8	115.8 (3)
N4—Zn2—Cl1	111.20 (7)	C10—C9—C8	122.3 (3)
N1—Zn2—Cl1	100.33 (7)	C3—C4—C5	118.5 (4)
N2—Zn2—Cl1ⁱ	85.59 (8)	C3—C4—H4	120.8
O1—Zn2—Cl1ⁱ	172.20 (7)	C5—C4—H4	120.8
N4—Zn2—Cl1ⁱ	92.27 (8)	N5—C8—C9	116.3 (3)
N1—Zn2—Cl1ⁱ	85.15 (8)	N5—C8—H8	121.9
Cl1—Zn2—Cl1ⁱ	87.63 (3)	C9—C8—H8	121.9
Zn2—Cl1—Zn2ⁱ	92.37 (3)	C3—C2—C1	118.7 (3)
Zn2—O1—H1A	119 (3)	C3—C2—H2	120.6
Zn2—O1—H1B	124 (4)	C1—C2—H2	120.6
H1A—O1—H1B	101 (5)	C12—C11—C10	119.1 (3)
C1—N1—C5	118.6 (3)	C12—C11—H11	120.4
C1—N1—Zn2	127.0 (2)	C10—C11—H11	120.4
C5—N1—Zn2	114.4 (2)	N2—C6—C5	115.8 (3)
C7—N4—N5	108.9 (2)	N2—C6—H6	122.1
C7—N4—Zn2	116.75 (19)	C5—C6—H6	122.1
N5—N4—Zn2	134.33 (19)	C2—C3—C4	119.9 (3)
C8—N5—N4	120.9 (3)	C2—C3—H3	120.1
C8—N5—Zn1	119.3 (2)	C4—C3—H3	120.1
N4—N5—Zn1	119.75 (19)	N6—C13—C12	122.5 (4)
C7—O2—Zn1	109.38 (18)	N6—C13—H13	118.7
C6—N2—N3	123.3 (3)	C12—C13—H13	118.7
C6—N2—Zn2	119.7 (2)	C11—C12—C13	119.0 (3)
N3—N2—Zn2	116.96 (18)	C11—C12—H12	120.5
N1—C5—C4	122.1 (3)	C13—C12—H12	120.5
N1—C5—C6	115.8 (3)

C7—N4—N5—C8	−169.4 (3)	C13—N6—C9—C8	−176.8 (3)
Zn2—N4—N5—C8	10.8 (5)	Zn1—N6—C9—C8	0.1 (4)
C7—N4—N5—Zn1	13.8 (3)	C11—C10—C9—N6	−0.7 (6)
Zn2—N4—N5—Zn1	−166.03 (17)	C11—C10—C9—C8	176.9 (4)
C1—N1—C5—C4	−0.6 (5)	N1—C5—C4—C3	−0.5 (6)
Zn2—N1—C5—C4	176.8 (3)	C6—C5—C4—C3	177.8 (4)
C1—N1—C5—C6	−179.0 (3)	N4—N5—C8—C9	177.2 (3)
Zn2—N1—C5—C6	−1.6 (4)	Zn1—N5—C8—C9	−6.0 (4)
Zn1—O2—C7—N4	−10.3 (4)	N6—C9—C8—N5	3.7 (5)
Zn1—O2—C7—N3	170.3 (2)	C10—C9—C8—N5	−174.0 (3)
N5—N4—C7—O2	−1.0 (5)	N1—C1—C2—C3	0.2 (6)
Zn2—N4—C7—O2	178.8 (3)	C9—C10—C11—C12	−0.4 (6)
N5—N4—C7—N3	178.4 (3)	N3—N2—C6—C5	179.5 (3)
Zn2—N4—C7—N3	−1.7 (4)	Zn2—N2—C6—C5	2.9 (4)
C6—N2—N3—C7	−178.3 (3)	N1—C5—C6—N2	−0.7 (5)
Zn2—N2—N3—C7	−1.6 (4)	C4—C5—C6—N2	−179.1 (4)
O2—C7—N3—N2	−178.4 (3)	C1—C2—C3—C4	−1.3 (7)
N4—C7—N3—N2	2.2 (5)	C5—C4—C3—C2	1.5 (7)
C5—N1—C1—C2	0.8 (5)	C9—N6—C13—C12	−0.1 (6)
Zn2—N1—C1—C2	−176.2 (3)	Zn1—N6—C13—C12	−176.5 (3)
C13—N6—C9—C10	0.9 (5)	C10—C11—C12—C13	1.2 (7)
Zn1—N6—C9—C10	177.9 (3)	N6—C13—C12—C11	−1.0 (7)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···Cl3ⁱⁱ	0.82 (2)	2.27 (2)	3.052 (3)	161 (5)
O1—H1B···Cl2ⁱⁱⁱ	0.82 (2)	2.32 (2)	3.129 (3)	169 (5)
C8—H8···Cl1	0.93	2.82	3.649 (3)	149
C2—H2···O1^iv	0.93	2.50	3.342 (4)	151
C6—H6···Cl3^v	0.93	2.55	3.425 (3)	158
N3—H3N···O2^v	0.85 (4)	2.00 (4)	2.837 (3)	170 (4)

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

References

Addison, A. W., Rao, T. N., Reedijk, J., van Rijn, J. & Verschoor, G. C. (1984). J. Chem. Soc. Dalton Trans. pp. 1349–1356. CSD CrossRef Web of Science Google Scholar
Bacchi, A., Carcelli, M., Pelagatti, P., Pelizzi, C., Pelizzi, G. & Zani, F. (1999). J. Inorg. Biochem. 75, 123–133. Web of Science CrossRef PubMed CAS Google Scholar
Bikas, R., Hosseini-Monfared, H., Aleshkevych, P., Szymczak, R., Siczek, M. & Lis, T. (2015). Polyhedron, 88, 48–56. CSD CrossRef CAS Google Scholar
Coelho, S. E., Terra, G. G. & Bortoluzzi, A. J. (2010). Acta Cryst. E66, m229–m230. CSD CrossRef IUCr Journals Google Scholar
Dragancea, D., Shova, S., Enyedy, A., Breza, M., Rapta, P., Carrella, L. M., Rentschler, E., Dobrov, A. & Arion, V. B. (2014). Polyhedron, 80, 180–192. CSD CrossRef CAS Google Scholar
Easwaran potti, M., Kurup, M. R. P. P. & Fun, H.-K. (2007). Inorg. Chem. Commun. 10, 324–328. CSD CrossRef Google Scholar
El-Gammal, O. A., Abu El-Reash, G. M., Ghazy, S. E. & Radwan, A. H. (2012). J. Mol. Struct. 1020, 6–15. CAS Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Hoque, Md. N., Basu, A. & Das, G. (2014). Cryst. Growth Des. 14, 6–10. CSD CrossRef CAS Google Scholar
Hoque, M. N., Manna, U. & Das, G. (2016). Polyhedron, 119, 307–316. CSD CrossRef CAS Google Scholar
Kothari, R. & Sharma, B. (2010). Orient. J. Chem. 26, 1577–1579. CAS Google Scholar
Li, J., Zhang, L., Xu, G.-C., Yu, W.-X. & Jia, D.-Z. (2014). Inorg. Chem. Commun. 45, 40–43. CSD CrossRef Google Scholar
Randell, N. M., Anwar, M. U., Drover, M. W., Dawe, L. N. & Thompson, L. K. (2013). Inorg. Chem. 52, 6731–6742. CSD CrossRef CAS PubMed Google Scholar
Rigaku OD (2018). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England. Google Scholar
Sanyal, R., Guha, A., Ghosh, T., Mondal, T. K., Zangrando, E. & Das, D. (2014). Inorg. Chem. 53, 85–96. Web of Science CSD CrossRef CAS PubMed Google Scholar
Seck, T. M., Diop, M., Diouf, D., Diouf, O., Barry, A. H. & Gaye, M. (2018). IOSR J. Appl. Chem. 11, 6–14. CAS Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Shuvaev, K. V., Dawe, L. N. & Thompson, L. K. (2010). Dalton Trans. 39, 4768–4776. CSD CrossRef CAS PubMed Google Scholar
Sow, M. M., Diouf, O., Gaye, M., Sall, A. S., Pérez-Lourido, P., Valencia-Matarranz, L., Castro, G., Caneschi, A. & Sorace, L. (2013). Inorg. Chim. Acta, 406, 171–175. CSD CrossRef CAS Google Scholar
Wu, D.-Y., Sato, O., Einaga, Y. & Duan, C.-Y. (2009). Angew. Chem. Int. Ed. 48, 1475–1478. Web of Science CSD CrossRef CAS Google Scholar
Yu, M.-M., Shi, Q.-Z., Zhang, Y.-N. & Li, Z.-X. (2009). Acta Cryst. E65, m744–m745. Web of Science CSD CrossRef IUCr Journals Google Scholar
Zhang, L., Wang, J.-J. & Xu, G.-C. (2014). Inorg. Chem. Commun. 39, 66–69. CrossRef CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.