Crystal structure of poly[[aqua­(μ2-pyrazine-κ2N:N′)(μ2-2,3,5,6-tetra­chloro­benzene-1,4-di­car­boxyl­ato-κ2O1:O4)copper(II)] hemihydrate]

Kumagai, H.; Kawata, S.; Ogihara, N.

doi:10.1107/S2056989025003457

research communications

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 81| Part 5| May 2025| Pages 429-432

https://doi.org/10.1107/S2056989025003457

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Crystal structure of poly[[aqua(μ₂-pyrazine-κ²N:N′)(μ₂-2,3,5,6-tetrachlorobenzene-1,4-dicarboxylato-κ²O¹:O⁴)copper(II)] hemihydrate]

Hitoshi Kumagai,^a ^* Satoshi Kawata ^b and Nobuhiro Ogihara ^a

^aToyota Central R&D Labs., Inc., 41-1 Yokomichi, Nagakute, Aichi 480-1192, Japan, and ^bDepartment of Chemistry, Fukuoka University, 8-19-1 Nanakuma Jonan-ku, Fukuoka, 814-0180, Japan
^*Correspondence e-mail: [email protected]

Edited by T. Akitsu, Tokyo University of Science, Japan (Received 26 March 2025; accepted 17 April 2025; online 24 April 2025)

The asymmetric unit of the title compound, {[Cu₂(C₈Cl₄O₄)₂(C₄H₄N₂)₂(H₂O)₂]·H₂O}_n or {[Cu₂(Cl₄bdc)₂(pyz)₂(H₂O)₂]·H₂O}_n comprises of a Cu^II ion, one tetrachlorobenzenedicarboxylate ion (Cl₄bdc²⁻), one pyrazine ligand (pyz), and one and a half water molecules. The Cu^II ion exhibits a five-coordinated square-pyramidal geometry with a CuN₂O₃ coordination environment comprising two oxygen atoms of the Cl₄bdc²⁻ ligands, one oxygen atom of a water molecule, and two nitrogen atoms of the pyz ligands. The carboxylate group is almost perpendicular to the benzene ring and shows monodentate coordination to the Cu^II ion. The Cu^II ions of these units are bridged by both the Cl₄bdc²⁻ and pyz ligands to form two-dimensional (2D) layers, which are linked by alternating hydrogen-bonding and C—Cl⋯π interactions to yield a three-dimensional network.

Keywords: crystal structure; hydrogen bonding; C—Cl⋯π interaction; tetrachloroterephthalate; pyrazine; copper.

CCDC reference: 2444566

1. Chemical context

Metal–organic frameworks (MOFs) or coordination polymers (CPs) consist of infinite assemblies of metal ions bridged by organic linkers such as benzendicarboxylate dianions and are attracting much interest due to their applications, for example in gas adsorption, and their optical and magnetic properties (Eddaoudi et al., 2002 ; Cheetham et al., 1999 ; Lacroix & Nakatani, 1997 ; Kitagawa et al., 2004 ; Kurmoo, 2009 ). We have prepared electrode materials using a benzendicarboxylate dianion and its analogues (Ogihara et al., 2014 , 2023 ; Yasuda & Ogihara, 2014 ; Ozawa et al., 2018 ; Mikita et al., 2020 ), and also magnetic materials that involve polycarboxylates in which the number of carboxylate groups and the distances between them are systematically varied (Kumagai et al., 2001 , 2002 , Kurmoo et al., 2001 , 2003 , 2005 ). The selection of metal ions and appropriate bridging ligands is fundamental for the development of a rational synthetic method to prepare these functional materials. We have reported the fine tuning of crystal structures and the properties of these materials, where not only are the metal ions systematically changed, but also the halogen atoms attached to the benzene ring of benzenedicarboxylate dianions (R₄bdc²⁻; R = H, F, Cl, Br) with pyrazine (pyz) or 4,4′-bipyridine (bpy) as co-bridging ligands (Kumagai et al., 2012 , 2021 ). Among the M/Br₄bdc²⁻/pyz (M = Co^II, Cu^II, Zn^II) systems, the Cu^II compound showed a different structure and water adsorption/desorption properties due to the different coordination geometry around the Cu^II ion (Kumagai et al., 2021). In this contribution, we focus on the use of the Cl₄bdc²⁻ dianion and pyz as a co-bridging ligand in the synthesis of a Cu^II–Cl₄bdc²⁻ dianion system to observe the structural change that results from the substitution of Br₄bdc²⁻ for Cl₄bdc²⁻. Here, we report on the single-crystal structure of [Cu₂(Cl₄bdc)₂(pyz)₂(H₂O)₂](H₂O).

2. Structural commentary

The asymmetric unit of the title compound, [Cu₂(Cl₄bdc)₂(pyz)₂(H₂O)₂](H₂O), consists of one Cu^II ion, one Cl₄bdc²⁻ dianion, one pyz ligand, one water molecule coordinated by the metal and ahalf water molecule of crystallization. The key feature of the structure is a two-dimensional (2D) coordination polymer in which CuN₂O₃ square pyramids bridged by Cl₄bdc²⁻ and pyz ligands are arranged in a lyaer, as shown in Fig. 1. The Cu^II ion is penta-coordinated with a square-pyramidal geometry. Pairs of Cl₄bdc²⁻ and pyz ligands are coordinated trans to each other to give the basal plane of the pyramid, while the coordinated water molecule occupies the apical position. The carboxylate group exhibits monodentate coordination, and the dihedral angle between the benzene ring and the carboxylate group is roughly orthogonal [C6—C1—C7—O1 105.5 (3)°]. We have recently reported a series of 2D layer compounds involving M^II cations (M = Co, Cu, Zn), the tetrabromobenzenedicarboxylate ligand (Br₄bdc²⁻) and pyz as co-bridging ligands (Kumagai et al., 2021). While the metal ions exhibit octahedral coordination environments in these complexes, the Cu^II ion of the title compound has a square-pyramidal geometry. The 2D layers of [M(Br₄bdc)(pyz)(H₂O)] (M = Co, Zn) include pyz molecules between the layers to give [M(Br₄bdc)(pyz)(H₂O)₂](pyz) by hydrogen-bonding and π–π stacking interactions. On the other hand, the [Cu(Br₄bdc)(pyz)(H₂O)₂] layers contain water molecules due to elongation of the Cu—O(H₂O) bond, which prevents the π–π stacking interactions of the pyz molecules. The Cu—O(H₂O) bond length of 2.301 (2) Å in the title compound is longer than that of [M(Br₄bdc)(pyz)(H₂O)₂] [M = Co 2.096 (4) Å, Zn 2.090 (3) Å], but shorter than that in [Cu(Br₄bdc)(pyz)(H₂O)₂] [2.487 (4) Å]. The Cu—N bond lengths of 2.015 (2) and 2.019 (2) Å are similar to that in [Cu(Br₄bdc)(pyz)(H₂O)₂] [2.012 (3) Å]. The Cu⋯Cu separations defined by Cu–Cl₄bdc²⁻–Cu connectivity and Cu–pyz–Cu connectivity within the chain are 10.98 and 6.78 Å, respectively. While the Cu⋯Cu distance in Cu–pyz–Cu is similar to that in [Cu(Br₄bdc)(pyz)(H₂O)₂] (6.79 Å), the separation for Cu–Cl₄bdc²⁻–Cu is slightly shorter than that in [Cu(Br₄bdc)(pyz)(H₂O)₂] (11.14 Å). It has been reported that the synthesis of metal complexes using Cl₄bdc²⁻ gives different structures depending on the synthetic conditions employed (Chen et al., 2011 , 2014 ). The title compound was synthesized by the same procedure as that used for the synthesis of the M/Br₄bdc²⁻/pyz (M = Co^II, Cu^II, Zn^II) systems; therefore, it is considered that the structural differences are attributable to the halogen atoms attached to the benzene ring. A similar coordination network, [Cu(Cl₄bdc)(dioxane)(H₂O)₂]·(dioxane), with dioxane as co-bridging ligand instead of pyz, has previously been synthesized using different synthetic conditions (He et al., 2009 ). The Cu^II ion exhibits an octahedral coordination environment and an almost rectangular 2D framework with dimensions of ca. 11.1 × 7.9 Å defined by the Cu⋯Cu separation. Although the Cu⋯Cu distance for Cu–Cl₄bdc²⁻–Cu in [Cu(Cl₄bdc)(dioxane)(H₂O)₂] is similar to that for the title compound, the Cu⋯Cu distance for Cu–dioxane–Cu is longer than that for Cu–pyz–Cu due to the large Cu—O(dioxane) bond length of 2.575 (2) Å.

Figure 1
The two-dimensional layered structure of the title compound with the atom-labelling scheme and 50% probability displacement ellipsoids. Hydrogen atoms and the water molecules of crystallization are omitted for clarity.

3. Supramolecular features

There are two types of interactions between the 2D networks in the crystal structure, namely hydrogen-bonding and other C—Cl⋯π interactions. The hydrogen-bonding interactions involve water molecules and carboxylate groups. The coordinated water molecules act as hydrogen-bonding donors and the non-coordinated oxygen atoms of the carboxylate groups of the Cl₄bdc²⁻ ligands in the adjacent 2D layer act as hydrogen-bonding acceptors (Fig. 2, Table 1). The coordinated water molecules also act as hydrogen-bonding donors for the water molecules of crystallization. These molecules, in turn, form hydrogen-bonding interactions with the coordinated oxygen atoms of the Cl₄bdc²⁻ ligands in the adjacent 2D layers. The other characteristic feature of the structure is C—Cl⋯π interactions between the 2D layers. The distances Cl3⋯C6ⁱⁱ [3.370 (3) Å, symmetry code: (ii) −x − $[{1\over 2}]$ , y − $[{1\over 2}]$ , z − $[{3\over 2}]$ ] and Cl3⋯centroid of the phenyl ring [3.745 (9) Å] are indicative of C—Cl⋯π interactions (Gilday et al., 2015 ). The layers are thus alternately stacked by hydrogen-bonding and C—Cl⋯π interactions to form a 3D network. The 2D layers in [Cu(Br₄bdc)(pyz)(H₂O)₂] form a 3D network solely by hydrogen-bonding interactions via water molecules between the 2D layers in which Cu^II ions exhibit an octahedral coordination geometry. Chemical modification by replacement of the halogen atoms results not only in different coordination geometries of the Cu^II ions, but also in different inter-layer interactions.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H1⋯O6	0.79 (2)	2.11 (3)	2.781 (7)	143 (4)
O5—H2⋯O3ⁱ	0.82 (2)	2.03 (3)	2.827 (3)	163 (5)
O6—H3⋯O1	0.82 (2)	2.04 (5)	2.763 (6)	147 (8)
O6—H4⋯O1ⁱ	0.82 (2)	2.07 (4)	2.843 (6)	156 (10)
Symmetry code: (i) .

Figure 2
View of inter-molecular hydrogen-bonding and C—Cl⋯π interactions along the b axis, represented by red and blue dashed lines, respectively.

4. Database survey

A search of the SciFinder database for structures with Cl₄bdc²⁻, pyz ligands, and Cu^II ions resulted in no complete matches. A search of the Web of Science database for the keywords 2,4,5,6-tetrachloro-1,3-benzenedicarboxylic acid and copper led to two publications that include dimethylformamide (FUDPUQ), pyridine (XUWRAJ, FUDPIE) and dioxane (FUDPOK) as co-ligands (He et al., 2009; Zheng et al., 2009 ).

5. Synthesis and crystallization

An aqueous solution (5 mL) of copper(II) nitrate trihydrate (0.24 g, 1.0 mmol) was transferred to a glass tube, and an ethanol–water (1:1) mixture (5 mL) of 2,3,5,6-tetrachlorobenzenedicarboxylic acid (0.30 g, 1.0 mmol), NaOH (0.16 g, 2.0 mmol), and pyrazine (0.08 g, 1.0 mmol) was poured into the glass tube without the two solutions being mixed. Blue crystals began to form at ambient temperature in 1 week. One of these crystals was used for X-ray diffraction analysis.

6. Refinement

The crystal data, data collection, and structure refinement details are summarized in Table 2. The hydrogen atoms attached to water molecules were extracted from difference-Fourier maps and refined isotropically. Other hydrogen atoms were located at ideal positions and were refined using a riding model.

Table 2
Experimental details

Crystal data
Chemical formula	[Cu₂(C₈Cl₄O₄)₂(C₄H₄N₂)₂(H₂O)₂]·H₂O
M_r	945.07
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	10.975 (3), 6.7837 (15), 21.803 (4)
β (°)	90.222 (14)
V (Å³)	1623.3 (6)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	2.03
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Rigaku Mercury70
Absorption correction	Multi-scan (REQAB; Rigaku, 2008 )
T_min, T_max	0.429, 0.666
No. of measured, independent and observed [I > 2σ(I)] reflections	15268, 3684, 3391
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.109, 1.18
No. of reflections	3684
No. of parameters	242
No. of restraints	5
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.67
Computer programs: CrystalClear (Rigaku, 2008), SIR92 (Altomare et al., 1994 ), SHELXL2018/3 (Sheldrick, 2015 ) and Yadokari-XG 2009 (Wakita, 2009 ).

Supporting information

CCDC reference: 2444566

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989025003457/jp2018sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989025003457/jp2018Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989025003457/jp2018Isup3.cdx

checkCIF report

Computing details top

Poly[[aqua(µ₂-pyrazine-κ²N:N')(µ₂-2,3,5,6-tetrachlorobenzene-1,4-dicarboxylato-κ²O¹:O⁴)copper(II)] hemihydrate] top

Crystal data top

[Cu₂(C₈Cl₄O₄)₂(C₄H₄N₂)₂(H₂O)₂]·H₂O	F(000) = 936
M_r = 945.07	D_x = 1.934 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.7107 Å
a = 10.975 (3) Å	Cell parameters from 4544 reflections
b = 6.7837 (15) Å	θ = 1.9–30.1°
c = 21.803 (4) Å	µ = 2.03 mm⁻¹
β = 90.222 (14)°	T = 293 K
V = 1623.3 (6) Å³	Prism, colorless
Z = 2	0.20 × 0.20 × 0.20 mm

Data collection top

Rigaku Mercury70 diffractometer	3391 reflections with I > 2σ(I)
Detector resolution: 7.314 pixels mm^-1	R_int = 0.030
ω scans	θ_max = 27.5°, θ_min = 1.9°
Absorption correction: multi-scan (REQAB; Rigaku, 2008)	h = −14→13
T_min = 0.429, T_max = 0.666	k = −8→8
15268 measured reflections	l = −28→28
3684 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.034	Hydrogen site location: mixed
wR(F²) = 0.109	H atoms treated by a mixture of independent and constrained refinement
S = 1.18	w = 1/[σ²(F_o²) + (0.0575P)² + 1.5531P] where P = (F_o² + 2F_c²)/3
3684 reflections	(Δ/σ)_max = 0.002
242 parameters	Δρ_max = 0.49 e Å⁻³
5 restraints	Δρ_min = −0.66 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	Occ. (<1)
Cu1	0.27764 (2)	0.62427 (4)	0.61712 (2)	0.01913 (11)
Cl1	−0.09180 (7)	0.98567 (12)	0.58342 (4)	0.0420 (2)
Cl2	−0.37150 (7)	0.92147 (13)	0.56485 (4)	0.0442 (2)
Cl3	−0.34867 (7)	0.25931 (14)	0.69731 (4)	0.0493 (2)
Cl4	−0.07035 (7)	0.31868 (14)	0.71717 (4)	0.0443 (2)
O1	0.10094 (16)	0.6243 (3)	0.60367 (9)	0.0232 (4)
O2	0.0908 (2)	0.7070 (5)	0.70164 (10)	0.0573 (8)
O3	−0.49156 (19)	0.4414 (4)	0.56869 (10)	0.0404 (5)
O4	−0.55433 (17)	0.6298 (3)	0.64610 (9)	0.0256 (4)
O5	0.2948 (2)	0.6265 (4)	0.51195 (10)	0.0379 (5)
O6	0.0506 (6)	0.5848 (12)	0.4800 (3)	0.0692 (19)	0.5
N1	0.27784 (19)	0.9216 (3)	0.62098 (10)	0.0217 (4)
N2	0.27117 (19)	1.3279 (3)	0.62254 (10)	0.0222 (4)
C1	−0.0938 (2)	0.6454 (4)	0.64777 (11)	0.0247 (5)
C2	−0.1622 (2)	0.7822 (4)	0.61483 (12)	0.0259 (5)
C3	−0.2862 (2)	0.7553 (4)	0.60668 (12)	0.0265 (5)
C4	−0.3430 (2)	0.5911 (4)	0.63065 (12)	0.0231 (5)
C5	−0.2765 (2)	0.4576 (4)	0.66547 (12)	0.0259 (5)
C6	−0.1519 (2)	0.4851 (4)	0.67378 (11)	0.0252 (5)
C7	0.0433 (2)	0.6632 (4)	0.65330 (12)	0.0258 (5)
C8	−0.4746 (2)	0.5481 (4)	0.61336 (12)	0.0239 (5)
C9	0.3304 (3)	1.0246 (4)	0.66616 (13)	0.0296 (6)
H9	0.370398	0.957881	0.697589	0.036*
C10	0.3264 (3)	1.2270 (4)	0.66709 (12)	0.0278 (6)
H10	0.362814	1.294764	0.699390	0.033*
C11	0.2177 (3)	1.2256 (4)	0.57790 (13)	0.0298 (6)
H11	0.177402	1.292424	0.546606	0.036*
C12	0.2209 (3)	1.0233 (4)	0.57707 (13)	0.0289 (6)
H12	0.182535	0.955829	0.545269	0.035*
H1	0.239 (3)	0.641 (6)	0.4894 (16)	0.044 (11)*
H2	0.361 (3)	0.605 (8)	0.495 (2)	0.082 (18)*
H3	0.035 (8)	0.592 (14)	0.5168 (12)	0.06 (3)*	0.5
H4	−0.003 (7)	0.515 (16)	0.465 (4)	0.09 (4)*	0.5

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.01352 (17)	0.01482 (18)	0.02901 (18)	−0.00014 (10)	−0.00327 (11)	0.00023 (10)
Cl1	0.0272 (4)	0.0395 (4)	0.0592 (5)	−0.0092 (3)	−0.0032 (3)	0.0149 (3)
Cl2	0.0246 (4)	0.0445 (5)	0.0635 (5)	0.0030 (3)	−0.0061 (3)	0.0237 (4)
Cl3	0.0308 (4)	0.0530 (5)	0.0641 (5)	−0.0112 (3)	−0.0074 (4)	0.0311 (4)
Cl4	0.0297 (4)	0.0493 (5)	0.0539 (5)	0.0032 (3)	−0.0152 (3)	0.0175 (4)
O1	0.0121 (8)	0.0272 (10)	0.0302 (9)	0.0003 (6)	−0.0014 (7)	−0.0035 (7)
O2	0.0293 (12)	0.115 (2)	0.0270 (10)	−0.0183 (14)	−0.0058 (9)	−0.0104 (13)
O3	0.0232 (10)	0.0596 (15)	0.0383 (11)	−0.0023 (10)	−0.0007 (8)	−0.0149 (11)
O4	0.0152 (8)	0.0243 (10)	0.0371 (10)	0.0004 (7)	−0.0032 (7)	−0.0024 (7)
O5	0.0334 (12)	0.0501 (14)	0.0302 (11)	0.0059 (10)	0.0029 (9)	0.0006 (9)
O6	0.052 (3)	0.119 (6)	0.036 (3)	−0.019 (4)	−0.012 (2)	−0.021 (3)
N1	0.0211 (11)	0.0159 (10)	0.0282 (11)	−0.0002 (8)	−0.0051 (8)	0.0002 (8)
N2	0.0203 (10)	0.0165 (10)	0.0299 (11)	−0.0012 (8)	−0.0042 (8)	0.0014 (8)
C1	0.0153 (11)	0.0380 (15)	0.0209 (11)	−0.0011 (10)	−0.0011 (9)	−0.0031 (10)
C2	0.0171 (12)	0.0313 (14)	0.0293 (12)	−0.0034 (10)	0.0022 (9)	0.0011 (10)
C3	0.0195 (12)	0.0288 (14)	0.0312 (13)	0.0022 (10)	−0.0034 (10)	0.0021 (10)
C4	0.0117 (11)	0.0312 (14)	0.0264 (12)	0.0004 (9)	0.0008 (9)	−0.0009 (10)
C5	0.0170 (12)	0.0333 (14)	0.0274 (12)	−0.0018 (10)	0.0010 (9)	0.0037 (11)
C6	0.0148 (11)	0.0358 (15)	0.0249 (12)	0.0018 (10)	−0.0015 (9)	0.0018 (10)
C7	0.0143 (11)	0.0370 (15)	0.0261 (12)	−0.0030 (10)	−0.0017 (9)	0.0007 (11)
C8	0.0154 (11)	0.0272 (13)	0.0290 (12)	−0.0005 (10)	−0.0032 (9)	0.0032 (10)
C9	0.0359 (15)	0.0220 (13)	0.0308 (13)	−0.0010 (11)	−0.0131 (11)	0.0036 (10)
C10	0.0334 (14)	0.0216 (13)	0.0284 (12)	−0.0032 (11)	−0.0099 (11)	0.0005 (10)
C11	0.0350 (15)	0.0206 (13)	0.0335 (13)	−0.0004 (11)	−0.0173 (11)	0.0023 (10)
C12	0.0317 (14)	0.0201 (13)	0.0348 (14)	−0.0006 (11)	−0.0143 (11)	0.0010 (10)

Geometric parameters (Å, º) top

Cu1—O4ⁱ	1.9475 (19)	N1—C9	1.336 (3)
Cu1—O1	1.9603 (18)	N2—C11	1.330 (3)
Cu1—N2ⁱⁱ	2.015 (2)	N2—C10	1.332 (3)
Cu1—N1	2.019 (2)	C1—C6	1.383 (4)
Cu1—O5	2.301 (2)	C1—C2	1.392 (4)
Cl1—C2	1.725 (3)	C1—C7	1.514 (3)
Cl2—C3	1.724 (3)	C2—C3	1.384 (4)
Cl3—C5	1.710 (3)	C3—C4	1.381 (4)
Cl4—C6	1.722 (3)	C4—C5	1.387 (4)
O1—C7	1.283 (3)	C4—C8	1.520 (3)
O2—C7	1.211 (3)	C5—C6	1.392 (3)
O3—C8	1.227 (3)	C9—C10	1.374 (4)
O4—C8	1.260 (3)	C9—H9	0.9300
O5—H1	0.791 (19)	C10—H10	0.9300
O5—H2	0.82 (2)	C11—C12	1.373 (4)
O6—H3	0.82 (2)	C11—H11	0.9300
O6—H4	0.82 (2)	C12—H12	0.9300
N1—C12	1.334 (3)

O4ⁱ—Cu1—O1	169.61 (8)	C4—C3—Cl2	118.9 (2)
O4ⁱ—Cu1—N2ⁱⁱ	91.93 (8)	C2—C3—Cl2	120.9 (2)
O1—Cu1—N2ⁱⁱ	88.49 (8)	C3—C4—C5	119.8 (2)
O4ⁱ—Cu1—N1	88.08 (8)	C3—C4—C8	119.4 (2)
O1—Cu1—N1	90.41 (8)	C5—C4—C8	120.5 (2)
N2ⁱⁱ—Cu1—N1	173.91 (9)	C4—C5—C6	119.9 (2)
O4ⁱ—Cu1—O5	104.00 (9)	C4—C5—Cl3	119.49 (19)
O1—Cu1—O5	86.33 (8)	C6—C5—Cl3	120.6 (2)
N2ⁱⁱ—Cu1—O5	93.91 (9)	C1—C6—C5	120.4 (2)
N1—Cu1—O5	91.99 (9)	C1—C6—Cl4	120.08 (19)
C7—O1—Cu1	111.38 (16)	C5—C6—Cl4	119.5 (2)
C8—O4—Cu1ⁱⁱⁱ	117.82 (17)	O2—C7—O1	124.9 (2)
Cu1—O5—H1	124 (3)	O2—C7—C1	120.9 (2)
Cu1—O5—H2	121 (4)	O1—C7—C1	114.2 (2)
H1—O5—H2	115 (5)	O3—C8—O4	127.3 (2)
H3—O6—H4	105 (5)	O3—C8—C4	116.8 (2)
C12—N1—C9	117.3 (2)	O4—C8—C4	115.9 (2)
C12—N1—Cu1	119.10 (18)	N1—C9—C10	121.3 (2)
C9—N1—Cu1	123.59 (18)	N1—C9—H9	119.4
C11—N2—C10	117.6 (2)	C10—C9—H9	119.4
C11—N2—Cu1^iv	119.57 (18)	N2—C10—C9	121.2 (2)
C10—N2—Cu1^iv	122.65 (18)	N2—C10—H10	119.4
C6—C1—C2	119.2 (2)	C9—C10—H10	119.4
C6—C1—C7	119.3 (2)	N2—C11—C12	121.4 (2)
C2—C1—C7	121.5 (2)	N2—C11—H11	119.3
C3—C2—C1	120.4 (2)	C12—C11—H11	119.3
C3—C2—Cl1	119.8 (2)	N1—C12—C11	121.3 (2)
C1—C2—Cl1	119.8 (2)	N1—C12—H12	119.4
C4—C3—C2	120.2 (2)	C11—C12—H12	119.4

C6—C1—C2—C3	−1.9 (4)	Cl3—C5—C6—Cl4	−0.6 (3)
C7—C1—C2—C3	175.3 (2)	Cu1—O1—C7—O2	4.4 (4)
C6—C1—C2—Cl1	178.7 (2)	Cu1—O1—C7—C1	−174.14 (18)
C7—C1—C2—Cl1	−4.1 (4)	C6—C1—C7—O2	−73.1 (4)
C1—C2—C3—C4	−0.7 (4)	C2—C1—C7—O2	109.7 (4)
Cl1—C2—C3—C4	178.8 (2)	C6—C1—C7—O1	105.5 (3)
C1—C2—C3—Cl2	−178.9 (2)	C2—C1—C7—O1	−71.6 (4)
Cl1—C2—C3—Cl2	0.6 (3)	Cu1ⁱⁱⁱ—O4—C8—O3	−10.5 (4)
C2—C3—C4—C5	3.1 (4)	Cu1ⁱⁱⁱ—O4—C8—C4	168.05 (17)
Cl2—C3—C4—C5	−178.7 (2)	C3—C4—C8—O3	91.6 (3)
C2—C3—C4—C8	−170.9 (2)	C5—C4—C8—O3	−82.4 (3)
Cl2—C3—C4—C8	7.3 (4)	C3—C4—C8—O4	−87.1 (3)
C3—C4—C5—C6	−2.9 (4)	C5—C4—C8—O4	98.9 (3)
C8—C4—C5—C6	171.0 (2)	C12—N1—C9—C10	−0.4 (4)
C3—C4—C5—Cl3	177.6 (2)	Cu1—N1—C9—C10	−179.0 (2)
C8—C4—C5—Cl3	−8.4 (4)	C11—N2—C10—C9	1.5 (4)
C2—C1—C6—C5	2.0 (4)	Cu1^iv—N2—C10—C9	−173.5 (2)
C7—C1—C6—C5	−175.2 (2)	N1—C9—C10—N2	−0.8 (5)
C2—C1—C6—Cl4	−177.6 (2)	C10—N2—C11—C12	−1.1 (4)
C7—C1—C6—Cl4	5.2 (3)	Cu1^iv—N2—C11—C12	174.1 (2)
C4—C5—C6—C1	0.3 (4)	C9—N1—C12—C11	0.8 (4)
Cl3—C5—C6—C1	179.8 (2)	Cu1—N1—C12—C11	179.5 (2)
C4—C5—C6—Cl4	179.9 (2)	N2—C11—C12—N1	−0.1 (5)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H1···O6	0.79 (2)	2.11 (3)	2.781 (7)	143 (4)
O5—H2···O3^v	0.82 (2)	2.03 (3)	2.827 (3)	163 (5)
O6—H3···O1	0.82 (2)	2.04 (5)	2.763 (6)	147 (8)
O6—H4···O1^v	0.82 (2)	2.07 (4)	2.843 (6)	156 (10)

Symmetry code: (v) −x, −y+1, −z+1.

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