Crystal structure of poly[tetra-μ-chlorido-tetra­chlorido­bis­(μ3-4,4′-bi-1,2,4-triazole-κ3N1:N2:N1′)(μ-4,4′-bi-1,2,4-triazole-κ3N1:N1′)tetra­copper(II)]

Domasevitch, K.V.; Lysenko, A.B.

doi:10.1107/S2056989019005516

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Volume 75| Part 6| June 2019| Pages 800-803

https://doi.org/10.1107/S2056989019005516

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Crystal structure of poly[tetra-μ-chlorido-tetrachloridobis(μ₃-4,4′-bi-1,2,4-triazole-κ³N¹:N²:N^1′)(μ-4,4′-bi-1,2,4-triazole-κ³N¹:N^1′)tetracopper(II)]

Kostiantyn V. Domasevitch ^a and Andrey B. Lysenko ^a ^*

^aInorganic Chemistry Department, Taras Shevchenko National University of Kyiv, Volodimirska Street 64, Kyiv 01033, Ukraine
^*Correspondence e-mail: ab_lysenko@univ.kiev.ua

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 18 April 2019; accepted 23 April 2019; online 14 May 2019)

The title Cu²⁺–chloride coordination polymer with the 4,4′-bi-1,2,4-triazole ligand (btr), [Cu₄Cl₈(C₄H₆N₆)₃]_n, crystallizes in the non-centrosymmetric orthorhombic space group Fdd2. The two independent Cu²⁺ cations adopt distorted square-pyramidal geometries with {Cl₂N₂+Cl} coordination polyhedra. The metal atoms are bridged by μ-Cl anions forming left- and right-handed helical chains of sequence [–(μ-Cl)CuCl–]_n along the c-axis direction. In the perpendicular directions, the btr ligands act in μ- and μ₃– coordination modes in a 2:3 ratio. The μ-btr bridges connect neighboring helices of the same handedness, whereas the μ₃-btr ligands link the helices of opposite handedness, leading to a racemic three-dimensional framework. The structure is consolidated by weak C—H⋯Cl and C—H⋯N interactions.

Keywords: crystal structure; 4,4′-bi-1,2,4-triazole; metal–organic frameworks; copper(II) complexes.

CCDC reference: 1911618

1. Chemical context

4,4′-Bi-1,2,4-triazole, C₄H₄N₆, btr, represents a unique example of a bitopic ligand used for the design of coordination solids. Four nitrogen donor sites in the btr molecule provide the possibility of different bridging modes [e.g. bi-N1,N1′ (Liu et al., 2007 ), bi-N1,N2 (Zhang et al., 2008 ) tri-N1,N2,N1′ (Huang, Zhao et al., 2008 ) and tetradentate N1,N2,N1′,N2′ (Lysenko et al., 2006 )], generating extended coordination networks. In this context, small nucleophilic anions play a very important role in the formation of the [M–X–M]_n coordination units (X = OH,⁻ Cl⁻ and Br⁻) that often function as secondary building blocks. In this case, the tri- and tetradentate behavior of btr can be preferably realized (Lysenko et al., 2006, 2007 ). Indeed, the CuCl₂–btr system is very sensitive to the reaction conditions. For example, a one-dimensional coordination polymer of [Cu₃(μ₂-Cl)₂Cl₂(btr)₄]Cl₂ was isolated from an aqueous solution (Lysenko et al., 2006). Another one-dimensional coordination polymer of [Cu(μ₂-Cl)₂(btr)]·H₂O was isolated in the presence of aqueous HCl (Zhang et al., 2008). In this paper, we report the crystal structure of the title three-dimensional coordination polymer, (I), which was also prepared from aqueous solution by mixing CuCl₂, btr and NH₄Cl.

2. Structural commentary

The title compound crystallizes from aqueous solution in the orthorhombic system, non-centrosymmetric space group Fdd2. The asymmetric unit consists of two copper(II) atoms, four chloride anions and one and a half crystallographically independent btr molecules. One btr ligand occupies a general position, while a half of btr sits on a special position (2-twofold axis running along the c axis, perpendicular to the N—N single bond).

The first copper ion, Cu1, adopts a distorted square-pyramidal {Cl₂N₂+Cl} coordination with two triazole N atoms and two chloride anions in the plane [Cu1—N1 = 1.985 (3) Å, Cu1—N4ⁱ = 1.957 (3) Å, N4ⁱ—Cu1—N1 = 168.82 (15)° symmetry code: (i) x − $[{1\over 4}]$ , −y + $[{1\over 4}]$ , z + $[{3\over 4}]$ , and Cu1—Cl2 = 2.2780 (12) Å, Cu1—Cl1 = 2.5146 (11) Å] and one chloride co-ligand at the apical position [Cu1—Cl3 = 2.4155 (10) Å, Fig. 1, Table 1]. Addison et al. (1984 ) introduced the geometric parameter τ to distinguish whether the geometry of five-coordinate systems is square-pyramidal or trigonal–bipyramidal. According to this scheme, trigonal–bipyramidal geometries are associated with a τ value close to 1.00, whereas for square-pyramidal geometries this value is around 0. Here, the value of τ for Cu1 is 0.35, suggesting the coordination is closer to square-pyramidal. The second independent copper cation, Cu2, has a similar square-pyramidal coordination geometry {Cl₂N₂+Cl} with τ = 0.32. Two triazole nitrogen atoms (N2, N7) and two chloride anions (Cl1, Cl4) comprise the basal plane whereas the fifth chloride donor [Cl3ⁱⁱ, symmetry code: (ii) x, y, z − 1] occupies an apical site. The copper polyhedra are linked together through the μ₂-bridging Cl1 and Cl3 anions to form left- and right-handed [Cu1–Cl1–Cu2–Cl3]_n helices running along the c-axis direction (Fig. 2). The helices have a straight line helical axis (2₁ axis), with the pitch being equal to the lattice parameter c. The btr ligands adopt μ- and μ₃- coordination modes in a 2:3 ratio. It is interesting to note that the μ-bridge btr molecules connect two neighboring helices of the same handedness (ΔΔ or ΛΛ). Then, each helix is connected to the other two of opposite handedness through μ₃-bridging btr molecules, thus forming a three-dimensional framework structure (Fig. 3). The btr ligand conformation is characterized by a torsion angle between its triazole planes. The μ- and μ₃-btr ligands are twisted around the N—N single bond adopting a non-coplanar orientation of the triazolyl groups. The dihedral angles between two triazolyl rings are 74.4 (2) and 78.1 (2)° for μ-and μ₃-btr, respectively.

Table 1
Selected bond lengths (Å)

Cu1—N4ⁱ	1.957 (3)	Cu2—N7	2.031 (3)
Cu1—N1	1.985 (3)	Cu2—N2	2.032 (3)
Cu1—Cl2	2.2780 (12)	Cu2—Cl4	2.2769 (9)
Cu1—Cl3	2.4155 (10)	Cu2—Cl1	2.3185 (10)
Cu1—Cl1	2.5146 (11)	Cu2—Cl3ⁱⁱ	2.6238 (13)
Symmetry codes: (i) $[x-{\script{1\over 4}}, -y+{\script{1\over 4}}, z+{\script{3\over 4}}]$ ; (ii) x, y, z-1.

Figure 1
A portion of the structure of (I)

, showing the atom-labeling scheme and the copper coordination environments. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) x − $[{1\over 4}]$ , −y + $[{1\over 4}]$ , z + $[{3\over 4}]$ ; (ii) x, y, z − 1].

Figure 2
A portion of the helical structure of (I)

(view in the ac plane). The μ-btr molecules link two neighboring helices of the same handedness, whereas the μ₃-btr molecules link two neighboring helices of the opposite handedness. Hydrogen atoms are omitted for clarity.

Figure 3
The three-dimensional helical framework structure of (I)

(top view).

3. Supramolecular features

In the crystal, compound (I) exhibits non-classical C—H⋯Cl and C—H⋯N hydrogen bonds (Fig. 4, Table 2). The C5 carbon atom of the triazole ring, as a weak hydrogen-bond donor (Desiraju & Steiner, 1999 ), is involved in a hydrogen bond with the acceptor N5^v atom of the neighboring triazole fragment. There is a bifurcated contact between one C1—H1 fragment and Cl2 (major component) and Cl1ⁱⁱⁱ (minor component). Two other hydrogen-bonding interactions are found between the C4—H4 and C6—H6 fragments and atoms Cl3^iv and Cl2^vi, respectively.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯Cl1ⁱⁱⁱ	0.94	2.74	3.528 (4)	142
C1—H1⋯Cl2	0.94	2.53	3.052 (4)	115
C4—H4⋯Cl3^iv	0.94	2.61	3.390 (4)	141
C5—H5⋯N5^v	0.94	2.47	3.365 (6)	160
C6—H6⋯Cl2^vi	0.94	2.70	3.315 (5)	124
Symmetry codes: (iii) $[x+{\script{1\over 4}}, -y+{\script{1\over 4}}, z+{\script{1\over 4}}]$ ; (iv) $[-x+{\script{1\over 2}}, -y, z-{\script{1\over 2}}]$ ; (v) $[-x+{\script{1\over 2}}, -y, z+{\script{1\over 2}}]$ ; (vi) $[x-{\script{1\over 4}}, -y+{\script{1\over 4}}, z-{\script{5\over 4}}]$ .

Figure 4
The packing of (I)

(view along the [ $[\overline{1}]$ 51] direction), showing the non-classical C—H⋯Cl and C—H⋯N hydrogen-bonded interactions that support the three-dimensional coordination framework. Hydrogen bonds are shown as dashed lines. [Symmetry codes: (iii) $[{1\over 4}]$ + x, $[{1\over 4}]$ − y, $[{1\over 4}]$ + z, (iv) $[{1\over 2}]$ − x, −y, − $[{1\over 2}]$ + z, (v), $[{1\over 2}]$ − x, −y, $[{1\over 2}]$ + z, (vi) − $[{1\over 4}]$ + x, $[{1\over 4}]$ − y, − $[{5\over 4}]$ + z].

In conclusion, the study demonstrates that a combination of a neutral btr molecule and a chloride anion, as complementary donor units, has promising potential in the development and design of metal–organic frameworks.

4. Database survey

According to our CSD search (version 5.39, update May 2018; Groom et al., 2016 ), the ligand geometries in (I) are in agreement with a general tendency for the coordinating btr ligand to adopt a twisted conformation. The only exception was observed for the Mn^II–oxalate complex [Mn₂(btr)(C₂O₄)₂(H₂O)₂]·2H₂O (Huang & Cheng, 2008 ), in which the torsion angle is close to 0°. In the pure ligand, the dihedral angle is equal to ca 88° (Domiano, 1977 ).

5. Synthesis and crystallization

4,4′-Bi-1,2,4-triazole (btr) was prepared in a yield of 60% by the literature transamination reaction between 4-amino-1,2,4-triazole and N,N-dimethylformamide azine (Bartlett & Humphrey, 1967 ).

A solution of CuCl₂·2H₂O (34.0 mg, 0.20 mmol) and NH₄Cl (10.6 mg, 0.20 mmol) in 2 ml of water was added to a solution of btr (27.2 mg, 0.20 mmol) in water (0.5 ml). A drop of 0.10 M HCl aqueous solution was then added. The resulting green solution was left standing for several days to form green prismatic crystals. The product was filtered, washed with water and dried in air (yield 47%). Analysis calculated for C₁₂H₁₂Cl₈Cu₄N₁₈ (I): C, 15.23; H, 1.28; N, 26.65%. Found: C, 15.20; H, 1.32; N, 26.55. IR (KBr disks, selected bands, cm⁻¹): 608s, 668w, 856m, 896w, 950w, 1022s, 1044s, 1076m, 1102m, 1212w, 1308m, 1338w, 1354w, 1400w, 1498m, 1536m, 3088s, 3112s, 3120s.

The thermal stability of (I) was investigated by measurements of temperature-dependent PXRD (Fig. 5). In the temperature-dependent X-ray diffractograms, the initial positions of the main diffraction peaks remain unchanged upon heating to 523 K. Above this temperature, the compound undergoes irreversible thermal decomposition, resulting in an amorphous solid.

Figure 5
(a) PXRD data [calculated (red line) and experimental (dark line)] and (b) two-dimensional thermo-PXRD patterns for (I)

(Cu K_α1 radiation).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. All C-bound H atoms were placed at calculated positions [C—H = 0.94 Å (aromatic)] and refined using a riding model with U_iso(H) = 1.2U_eq(CH).

Table 3
Experimental details

Crystal data
Chemical formula	[Cu₄Cl₈(C₄H₄N₆)₃]
M_r	946.16
Crystal system, space group	Orthorhombic, Fdd2
Temperature (K)	213
a, b, c (Å)	28.869 (2), 31.584 (2), 6.2953 (4)
V (Å³)	5740.1 (7)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	3.71
Crystal size (mm)	0.18 × 0.15 × 0.14

Data collection
Diffractometer	Stoe Image plate diffraction system
Absorption correction	Numerical [X-RED (Stoe & Cie, 2001 ) and X-SHAPE (Stoe & Cie, 1999 )]
T_min, T_max	0.548, 0.608
No. of measured, independent and observed [I > 2σ(I)] reflections	10421, 3323, 3116
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.055, 1.02
No. of reflections	3323
No. of parameters	190
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.88, −0.50
Absolute structure	Flack x determined using 1309 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	−0.010 (9)
Computer programs: IPDS Software (Stoe & Cie, 2000 ), SHELXS97 (Sheldrick, 2008 ), SHELXL2018/1 (Sheldrick, 2015 ), DIAMOND (Brandenburg, 1999 ), WinGX (Farrugia, 2012 ) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1911618

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989019005516/hb7819sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019005516/hb7819Isup2.hkl

checkCIF report

Computing details top

Data collection: IPDS Software (Stoe & Cie, 2000); cell refinement: IPDS Software (Stoe & Cie, 2000); data reduction: IPDS Software (Stoe & Cie, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018/1 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009).

Poly[tetra-µ-chlorido-tetrachloridobis(µ₃-4,4'-bi-1,2,4-triazole-\ κ³N¹:N²:N^{1')(µ-4,4'-bi-1,2,4-triazole-\}^κ3^N1^:^N1')tetracopper(II)] top

Crystal data top

[Cu₄Cl₈(C₄H₄N₆)₃]	D_x = 2.190 Mg m⁻³
M_r = 946.16	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Fdd2	Cell parameters from 8000 reflections
a = 28.869 (2) Å	θ = 1.9–28.0°
b = 31.584 (2) Å	µ = 3.71 mm⁻¹
c = 6.2953 (4) Å	T = 213 K
V = 5740.1 (7) Å³	Prism, green
Z = 8	0.18 × 0.15 × 0.14 mm
F(000) = 3696

Data collection top

Stoe Image plate diffraction system diffractometer	3116 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.027
φ oscillation scans	θ_max = 28.0°, θ_min = 1.9°
Absorption correction: numerical [X-RED (Stoe & Cie, 2001) and X-SHAPE (Stoe & Cie, 1999)]	h = −38→35
T_min = 0.548, T_max = 0.608	k = −41→41
10421 measured reflections	l = −7→7
3323 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.023	H-atom parameters constrained
wR(F²) = 0.055	w = 1/[σ²(F_o²) + (0.0381P)²] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
3323 reflections	Δρ_max = 0.88 e Å⁻³
190 parameters	Δρ_min = −0.50 e Å⁻³
1 restraint	Absolute structure: Flack x determined using 1309 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.010 (9)

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
Cu1	0.19850 (2)	0.11917 (2)	0.94479 (8)	0.01706 (11)
Cu2	0.15568 (2)	0.05097 (2)	0.52000 (9)	0.01686 (11)
Cl1	0.14339 (3)	0.11976 (3)	0.63547 (17)	0.0209 (2)
Cl2	0.26125 (4)	0.14870 (5)	1.1066 (3)	0.0475 (4)
Cl3	0.17082 (4)	0.05490 (3)	1.10950 (19)	0.0239 (2)
Cl4	0.16908 (3)	−0.01996 (3)	0.54022 (18)	0.0218 (2)
N1	0.23912 (10)	0.08783 (9)	0.7448 (6)	0.0167 (7)
N2	0.22374 (10)	0.06244 (9)	0.5786 (6)	0.0179 (7)
N3	0.29808 (10)	0.06871 (9)	0.5595 (6)	0.0170 (7)
N4	0.40573 (10)	0.09304 (9)	0.3439 (6)	0.0177 (7)
N5	0.41628 (11)	0.05456 (10)	0.4425 (7)	0.0226 (8)
N6	0.34333 (10)	0.06931 (9)	0.4869 (6)	0.0155 (7)
N7	0.08703 (10)	0.04075 (10)	0.4717 (6)	0.0204 (7)
N8	0.06179 (12)	0.06766 (11)	0.3404 (7)	0.0279 (8)
N9	0.01831 (10)	0.01434 (9)	0.4350 (6)	0.0200 (7)
C1	0.28398 (12)	0.09087 (11)	0.7326 (7)	0.0158 (8)
H1	0.303232	0.105780	0.826934	0.019*
C2	0.25984 (13)	0.05162 (11)	0.4654 (8)	0.0207 (8)
H2	0.259496	0.035051	0.341342	0.025*
C3	0.36206 (12)	0.10152 (11)	0.3721 (7)	0.0171 (7)
H3	0.346291	0.125570	0.322048	0.021*
C4	0.37822 (13)	0.04129 (11)	0.5283 (8)	0.0219 (8)
H4	0.375067	0.016178	0.607163	0.026*
C5	0.06065 (13)	0.00912 (12)	0.5272 (8)	0.0226 (8)
H5	0.069354	−0.013471	0.615824	0.027*
C6	0.02098 (15)	0.05083 (13)	0.3162 (9)	0.0289 (10)
H6	−0.002904	0.061861	0.231151	0.035*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0133 (2)	0.01689 (19)	0.0210 (3)	0.00071 (16)	0.00427 (17)	−0.00465 (18)
Cu2	0.01083 (18)	0.01540 (19)	0.0244 (3)	−0.00198 (15)	−0.00067 (18)	−0.00141 (17)
Cl1	0.0206 (4)	0.0200 (4)	0.0222 (6)	0.0052 (3)	−0.0041 (3)	−0.0035 (3)
Cl2	0.0170 (5)	0.0704 (8)	0.0550 (9)	0.0052 (5)	−0.0044 (5)	−0.0457 (7)
Cl3	0.0316 (5)	0.0194 (4)	0.0206 (6)	−0.0048 (3)	0.0037 (4)	0.0015 (3)
Cl4	0.0232 (4)	0.0163 (4)	0.0258 (6)	−0.0001 (3)	−0.0024 (4)	0.0027 (4)
N1	0.0151 (14)	0.0192 (13)	0.016 (2)	−0.0012 (11)	0.0024 (12)	−0.0045 (12)
N2	0.0117 (13)	0.0181 (14)	0.024 (2)	−0.0031 (11)	0.0009 (12)	−0.0045 (12)
N3	0.0120 (14)	0.0175 (14)	0.021 (2)	−0.0010 (10)	0.0038 (12)	−0.0031 (12)
N4	0.0160 (15)	0.0163 (13)	0.021 (2)	−0.0008 (11)	0.0028 (13)	0.0034 (12)
N5	0.0180 (15)	0.0172 (14)	0.033 (2)	0.0018 (11)	0.0052 (14)	0.0047 (14)
N6	0.0107 (12)	0.0178 (13)	0.018 (2)	−0.0019 (10)	0.0038 (11)	−0.0024 (12)
N7	0.0153 (14)	0.0188 (14)	0.027 (2)	−0.0019 (11)	−0.0017 (13)	0.0014 (13)
N8	0.0225 (17)	0.0229 (16)	0.038 (3)	−0.0033 (13)	−0.0041 (15)	0.0103 (15)
N9	0.0127 (14)	0.0174 (14)	0.030 (2)	−0.0037 (11)	−0.0007 (13)	0.0017 (13)
C1	0.0134 (15)	0.0155 (14)	0.018 (2)	−0.0008 (12)	0.0018 (14)	−0.0032 (13)
C2	0.0158 (16)	0.0222 (17)	0.024 (3)	−0.0045 (13)	0.0026 (15)	−0.0087 (16)
C3	0.0139 (16)	0.0178 (15)	0.020 (2)	−0.0007 (12)	0.0026 (14)	−0.0009 (14)
C4	0.0186 (17)	0.0174 (16)	0.030 (2)	0.0007 (13)	0.0035 (16)	0.0010 (16)
C5	0.0184 (17)	0.0202 (16)	0.029 (3)	−0.0025 (13)	−0.0035 (17)	0.0044 (16)
C6	0.022 (2)	0.0262 (19)	0.039 (3)	−0.0040 (15)	−0.0051 (18)	0.0107 (18)

Geometric parameters (Å, º) top

Cu1—N4ⁱ	1.957 (3)	N4—N5	1.398 (4)
Cu1—N1	1.985 (3)	N5—C4	1.294 (5)
Cu1—Cl2	2.2780 (12)	N6—C3	1.360 (5)
Cu1—Cl3	2.4155 (10)	N6—C4	1.366 (5)
Cu1—Cl1	2.5146 (11)	N7—C5	1.304 (5)
Cu2—N7	2.031 (3)	N7—N8	1.392 (5)
Cu2—N2	2.032 (3)	N8—C6	1.302 (5)
Cu2—Cl4	2.2769 (9)	N9—C5	1.363 (5)
Cu2—Cl1	2.3185 (10)	N9—C6	1.376 (5)
Cu2—Cl3ⁱⁱ	2.6238 (13)	N9—N9ⁱⁱⁱ	1.392 (6)
N1—C1	1.301 (5)	C1—H1	0.9400
N1—N2	1.391 (5)	C2—H2	0.9400
N2—C2	1.308 (5)	C3—H3	0.9400
N3—C1	1.357 (5)	C4—H4	0.9400
N3—C2	1.364 (5)	C5—H5	0.9400
N3—N6	1.384 (4)	C6—H6	0.9400
N4—C3	1.301 (5)

N4ⁱ—Cu1—N1	168.82 (15)	C3—N4—Cu1^v	123.5 (3)
N4ⁱ—Cu1—Cl2	92.14 (10)	N5—N4—Cu1^v	127.3 (2)
N1—Cu1—Cl2	91.04 (9)	C4—N5—N4	106.4 (3)
N4ⁱ—Cu1—Cl3	95.62 (10)	C3—N6—C4	107.0 (3)
N1—Cu1—Cl3	92.79 (10)	C3—N6—N3	124.1 (3)
Cl2—Cu1—Cl3	114.53 (6)	C4—N6—N3	128.6 (3)
N4ⁱ—Cu1—Cl1	88.14 (11)	C5—N7—N8	108.7 (3)
N1—Cu1—Cl1	83.47 (10)	C5—N7—Cu2	130.7 (3)
Cl2—Cu1—Cl1	147.82 (6)	N8—N7—Cu2	120.2 (2)
Cl3—Cu1—Cl1	97.43 (4)	C6—N8—N7	107.1 (3)
N7—Cu2—N2	177.81 (15)	C5—N9—C6	106.4 (3)
N7—Cu2—Cl4	91.02 (9)	C5—N9—N9ⁱⁱⁱ	127.0 (3)
N2—Cu2—Cl4	90.06 (9)	C6—N9—N9ⁱⁱⁱ	126.0 (3)
N7—Cu2—Cl1	92.67 (10)	N1—C1—N3	107.9 (3)
N2—Cu2—Cl1	85.63 (9)	N1—C1—H1	126.0
Cl4—Cu2—Cl1	158.52 (5)	N3—C1—H1	126.0
N7—Cu2—Cl3ⁱⁱ	91.29 (12)	N2—C2—N3	107.7 (4)
N2—Cu2—Cl3ⁱⁱ	90.54 (11)	N2—C2—H2	126.1
Cl4—Cu2—Cl3ⁱⁱ	94.20 (4)	N3—C2—H2	126.1
Cl1—Cu2—Cl3ⁱⁱ	106.86 (4)	N4—C3—N6	107.7 (3)
Cu2—Cl1—Cu1	97.99 (4)	N4—C3—H3	126.2
Cu1—Cl3—Cu2^iv	121.17 (4)	N6—C3—H3	126.2
C1—N1—N2	108.4 (3)	N5—C4—N6	109.7 (3)
C1—N1—Cu1	126.1 (3)	N5—C4—H4	125.2
N2—N1—Cu1	125.2 (2)	N6—C4—H4	125.2
C2—N2—N1	107.8 (3)	N7—C5—N9	108.5 (4)
C2—N2—Cu2	128.7 (3)	N7—C5—H5	125.8
N1—N2—Cu2	123.2 (2)	N9—C5—H5	125.8
C1—N3—C2	108.1 (3)	N8—C6—N9	109.2 (4)
C1—N3—N6	122.8 (3)	N8—C6—H6	125.4
C2—N3—N6	128.7 (3)	N9—C6—H6	125.4
C3—N4—N5	109.2 (3)

C1—N1—N2—C2	−1.8 (4)	Cu2—N2—C2—N3	175.9 (3)
Cu1—N1—N2—C2	171.8 (3)	C1—N3—C2—N2	−0.9 (5)
C1—N1—N2—Cu2	−176.4 (3)	N6—N3—C2—N2	−173.2 (3)
Cu1—N1—N2—Cu2	−2.8 (4)	N5—N4—C3—N6	−0.2 (5)
C3—N4—N5—C4	−0.4 (5)	Cu1^v—N4—C3—N6	−178.0 (3)
Cu1^v—N4—N5—C4	177.3 (3)	C4—N6—C3—N4	0.7 (5)
C1—N3—N6—C3	−78.1 (5)	N3—N6—C3—N4	175.6 (4)
C2—N3—N6—C3	93.2 (5)	N4—N5—C4—N6	0.8 (5)
C1—N3—N6—C4	95.6 (5)	C3—N6—C4—N5	−1.0 (5)
C2—N3—N6—C4	−93.1 (6)	N3—N6—C4—N5	−175.5 (4)
C5—N7—N8—C6	−1.5 (5)	N8—N7—C5—N9	0.2 (5)
Cu2—N7—N8—C6	172.0 (3)	Cu2—N7—C5—N9	−172.4 (3)
N2—N1—C1—N3	1.2 (4)	C6—N9—C5—N7	1.2 (5)
Cu1—N1—C1—N3	−172.3 (3)	N9ⁱⁱⁱ—N9—C5—N7	172.8 (3)
C2—N3—C1—N1	−0.2 (4)	N7—N8—C6—N9	2.2 (6)
N6—N3—C1—N1	172.6 (3)	C5—N9—C6—N8	−2.1 (6)
N1—N2—C2—N3	1.6 (4)	N9ⁱⁱⁱ—N9—C6—N8	−173.9 (4)

Symmetry codes: (i) x−1/4, −y+1/4, z+3/4; (ii) x, y, z−1; (iii) −x, −y, z; (iv) x, y, z+1; (v) x+1/4, −y+1/4, z−3/4.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···Cl1^vi	0.94	2.74	3.528 (4)	142
C1—H1···Cl2	0.94	2.53	3.052 (4)	115
C2—H2···Cl4^vii	0.94	2.84	3.518 (4)	130
C3—H3···Cl2ⁱⁱ	0.94	2.90	3.672 (4)	140
C3—H3···N8^vi	0.94	2.66	3.242 (5)	121
C4—H4···Cl3^vii	0.94	2.61	3.390 (4)	141
C5—H5···N5^viii	0.94	2.47	3.365 (6)	160
C6—H6···Cl2^ix	0.94	2.70	3.315 (5)	124

Symmetry codes: (ii) x, y, z−1; (vi) x+1/4, −y+1/4, z+1/4; (vii) −x+1/2, −y, z−1/2; (viii) −x+1/2, −y, z+1/2; (ix) x−1/4, −y+1/4, z−5/4.

Funding information

This work was supported by the Ministry of Education and Science of Ukraine (project No. 19BF037-05).

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
Bartlett, R. K. & Humphrey, I. R. (1967). J. Chem. Soc. C, pp. 1664–1666. Google Scholar
Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Desiraju, R. G. & Steiner, T. (1999). The Weak Hydrogen Bond in Structural Chemistry and Biology. New York: Oxford University Press Inc. Google Scholar
Domiano, P. (1977). Cryst. Struct. Commun. 6, 503–506. 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
Huang, Y.-Q. & Cheng, P. (2008). Inorg. Chem. Commun. 11, 66–68. Web of Science CSD CrossRef CAS Google Scholar
Huang, Y.-Q., Zhao, X.-Q., Shi, W., Liu, W.-Y., Chen, Z.-L., Cheng, P., Liao, D.-Z. & Yan, S.-P. (2008). Cryst. Growth Des. 8, 3652–3660. Web of Science CSD CrossRef CAS Google Scholar
Liu, Y.-Y., Huang, Y.-Q., Shi, W., Cheng, P., Liao, D.-Z. & Yan, S.-P. (2007). Cryst. Growth Des. 7, 1483–1489. Web of Science CSD CrossRef CAS Google Scholar
Lysenko, A. B., Govor, E. V. & Domasevitch, K. V. (2007). Inorg. Chim. Acta, 360, 55–60. Web of Science CSD CrossRef CAS Google Scholar
Lysenko, A. B., Govor, E. V., Krautscheid, H. & Domasevitch, K. V. (2006). Dalton Trans. pp. 3772–3776. Web of Science CSD CrossRef Google Scholar
Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249–259. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stoe & Cie (1999). X-SHAPE. Stoe & Cie, Darmstadt, Germany. Google Scholar
Stoe & Cie (2000). IPDS Software. Stoe & Cie, Darmstadt, Germany. Google Scholar
Stoe & Cie (2001). X-RED. Stoe & Cie, Darmstadt, Germany. Google Scholar
Zhang, X.-C., Chen, Y.-H. & Liu, B. (2008). Inorg. Chem. Commun. 11, 446–449. Web of Science CSD CrossRef CAS Google Scholar

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