Synthesis and structural characterization of the dichloride complex formed by carb­oxy-functionalized Cu(di­aza­cyclam)2+ cation and its heterometallic coordination polymer with CdCl2

Tsymbal, L.V.; Andriichuk, I.L.; Stoica, A.-C.; Lampeka, Y.D.

doi:10.1107/S2056989025003792

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Volume 81| Part 6| June 2025|

https://doi.org/10.1107/S2056989025003792

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Synthesis and structural characterization of the dichloride complex formed by carboxy-functionalized Cu(diazacyclam)²⁺ cation and its heterometallic coordination polymer with CdCl₂

Liudmyla V. Tsymbal,^a Irina L. Andriichuk,^a Alexandru-Constantin Stoica ^b and Yaroslaw D. Lampeka ^a ^*

^aL. V. Pisarzhevskii Institute of Physical Chemistry of the National Academy of Sciences of Ukraine, Prospekt Nauki 31, 03028, Kyiv, Ukraine, and ^b"Petru Poni" Institute of Macromolecular Chemistry, Aleea Gr. Ghica Voda 41A, RO 700487, Iasi, Romania
^*Correspondence e-mail: lampeka@adamant.net

Edited by W. T. A. Harrison, University of Aberdeen, United Kingdom (Received 24 April 2025; accepted 27 April 2025; online 2 May 2025)

The asymmetric unit of the complex [3,10-bis(3-carboxypropyl)-1,3,5,8,10,12-hexaazacyclotetradecane-κ⁴N¹,N⁵,N⁸,N¹²]dichloridocopper(II), [CuCl₂(C₁₆H₃₄N₆O₄)] or [Cu(H₂L)Cl₂] (I), consists of a centrosymmetric macrocyclic Cu^II dication and a chloride anion. The components of the heterometallic compound poly[[aqua[μ₃-3,10-bis(3-carboxypropyl)-1,3,5,8,10,12-hexaazacyclotetradecane-κ⁴N¹,N⁵,N⁸,N¹²:κ²O,O′:κ²O′′,O′′′]-μ-chlorido-copper(II)cadmium(II] 1.25-hydrate], {[CuCd(C₁₆H₃₂N₆O₄)Cl₂(H₂O)]·1.25H₂O}_n or {[CuCd(L)(H₂O)Cl₂]·1.25H₂O}_n (II) are [Cu(L)(H₂O)] moieties coordinated to CdCl₂ units via the deprotonated carboxylic groups of the macrocycle, and four water molecules of crystallization with partial occupancies. In each compound, the Cu^II ion coordinates in the equatorial plane by the four secondary N atoms of the macrocyclic ligand, which adopts the most energetically stable trans-III conformation, and two mutually trans axial ligands in tetragonally elongated trans-CuN₄Cl₂ and trans-CuN₄(H₂O)Cl octahedral geometries in I and II, respectively. The coordination environment of the Cd^II ion in II is a CdO₄Cl₂ distorted octahedron formed by two bidentately coordinated deprotonated carboxylic groups of different macrocycles and two chloride anions, one of which displays a μ₂-bridging function between the Cu^II and Cd^II ions. The extended structures of both complexes are distinctly lamellar. In particular, due to hydrogen–bonding interactions with participation of carboxylic groups, chloride atoms and secondary amino groups of the macrocycle, the electro-neutral molecules in crystal of I are arranged in chains running in the [101] direction; hydrogen bonding between the chains leads to layers parallel to the (101) plane. In crystal of II, polymeric chains running along the [101] direction are joined into layers parallel to the (101) plane via formation of Cu—Cl bonds and interchain hydrogen bonds. There are no hydrogen-bonding interactions between the layers and the three-dimensional structure of II is based on the weak C—H⋯O and C—H⋯Cl contacts.

Keywords: crystal structure; diazacyclam; 3-carboxypropyl substituent; copper; cadmium; coordination polymer; hydrogen bonds..

CCDC references: 2420902; 2420903

1. Chemical context

Owing to exceptionally high thermodynamic stability and kinetic inertness (Yatsimirskii & Lampeka, 1985 ), first row transition-metal complexes of the tetradentate 14-membered azamacrocyclic ligand 1,4,8,11-tetraazacyclotetradecane (cyclam) and its N³,N¹⁰-disubstituted structural analogue 1,3,5,8,10,12-hexaazacyclotetradecane (diazacyclam) are common metal-containing nodes for the design of metal–organic frameworks (MOFs), demonstrating many promising applications (Lampeka & Tsymbal, 2004 ; Suh & Moon, 2007 ; Stackhouse & Ma, 2018 ). The Ni^II and Cu^II complexes of diazacyclam are readily obtainable via template Mannich condensation of bis(ethylenediamine) complexes of these cations with formaldehyde and primary amines (Costisor & Linert, 2000 ). The use of primary amines bearing an additional coordinating groups as locking fragments in these template reactions allows for the preparation of complexes of functionalized diazacyclams. As a result of the interaction of the donor group of the substituents in these species with other metal-containing nodes they can form coordination polymers, without using additional bridging ligands. Indeed, several examples of polymeric compounds formed by the Ni^II or Cu^II complexes of propionitrile-substituted diazacyclam have been described (Suh et al., 1994 ; Liu et al., 2002 ). They are the homometallic products of self-polymerization reactions occurring via coordination of the nitrile groups of the substituents of macrocyclic cation in the axial positions of the metal ions of other macrocyclic units. Similar self-polymerization of building blocks is also characteristic of 3-carboxypropyl-substituted diazacyclam (Lu et al., 2005 ; Ou et al., 2005 see Database survey). Because carboxylates are known as the most popular bridging units in preparation of MOFs (Rao et al., 2004 ; Yoshinari & Konno, 2023 ), the complexes of this ligand are of particular interest because their reactions with other metal ions can lead to formation of new types of heterometallic coordination polymers.

The present work describes the preparation and structural characterization of the molecular Cu^II dichloride complex of the azacyclam ligand 3,10-bis(3-carboxypropyl)-1,3,5,8,10,12-hexaazacyclotetradecane (H₂L), namely, [3,10-bis(3-carboxypropyl)-1,3,5,8,10,12-hexaazacyclotetradecane-κ⁴N¹,N⁵,N⁸,N¹²]dichloridocopper(II), [CuCl₂(C₁₆H₃₄N₆O₄)] or [Cu(H₂L)Cl₂] (I), and the product of its interaction with Cd^II ion, namely, poly{[aqua[μ₃-3,10-bis(3-carboxypropyl)-1,3,5,8,10,12-hexaazacyclotetradecane-κ⁴N¹,N⁵,N⁸,N¹²;κ²O,O′:κ²O′′,O′′′]-μ-chloridocopper(II)cadmium(II] 1.25-hydrate], {[CuCd(C₁₆H₃₂N₆O₄)Cl₂(H₂O)]·1.25H₂O}_n or {[CuCd(L)(H₂O)Cl₂]·1.25H₂O}_n (II), which is the first representative of heterometallic polymeric complexes with carboxyl-substituted Cu-diazacyclam moiety as bridging ligand.

2. Structural commentary

The molecular structures of I and II are shown in Figs. 1 and 2, respectively, while selected geometric parameters characterizing the coordination environment of the Cu^II and Cd^II ions are collected in Tables 1 and 2. The asymmetric unit of I (Fig. 1) represents a half of the neutral centrosymmetric [Cu(H₂L)Cl₂] complex formed by a diazacyclam ligand with protonated carboxylic groups. The asymmetric unit of II contains a [Cu(L)(H₂O)] moiety coordinated to CdCl₂ via deprotonated carboxylic groups of the macrocycle (Fig. 2). Additionally, it includes four water molecules of crystallization with site occupancies 0.5 (O2W) and 0.25 (O3W–O5W) (total 1.25 water molecules).

Table 1
Selected geometric parameters (Å, °) for I

Cu1—Cl1	2.8889 (7)	Cu1—N1	2.000 (2)
Cu1—N3	2.003 (2)

N1—Cu1—N3ⁱ	85.92 (9)	N1—Cu1—N3	94.08 (9)
Symmetry code: (i) .

Table 2
Selected geometric parameters (Å, °) for II

Cd1—Cl1	2.5125 (18)	Cu1—N4	1.993 (5)
Cd1—Cl2	2.515 (2)	Cu1—N1	2.023 (5)
Cd1—O3ⁱ	2.266 (4)	Cu1—N6	2.006 (5)
Cd1—O1	2.275 (5)	Cu1—N3	2.020 (5)
Cd1—O4ⁱ	2.637 (6)	Cu1—O1W	2.446 (5)
Cd1—O2	2.494 (6)	Cu1—Cl1ⁱⁱ	3.048 (2)

Cl1—Cd1—Cl2	104.67 (7)	N4—Cu1—N3	86.5 (2)
O3ⁱ—Cd1—O4ⁱ	52.44 (17)	N6—Cu1—N1	86.6 (2)
O1—Cd1—O2	53.54 (19)	N3—Cu1—N1	93.0 (2)
N4—Cu1—N6	93.9 (2)
Symmetry codes: (i) ; (ii) .

Figure 1
The asymmetric unit in I showing displacement ellipsoids drawn at the 30% probability level. C-bound H atoms are omitted for clarity. Symmetry code: (i) −x + 2, −y + 1, −z + 1.

Figure 2
The extended asymmetric unit in II with displacement ellipsoids drawn at the 30% probability level. The semicoordinative Cu—Cl1 bond is shown as dark green capped stick line. C-bound H atoms are omitted for clarity. Water molecules of crystallization are not shown. Symmetry codes: (i) x + 1, y, z + 1; (ii) x - 1, y, z − 1; (iii) −x + 1, −y, −z + 1.

In both compounds the Cu^II ion coordinates the four secondary N atoms of the macrocycles, which adopt the most energetically stable trans–III (R,R,S,S) conformation (Barefield et al., 1986 ) with the five-membered (N—Ni—N bite angles ca 86°) and six-membered (N—Ni—N bite angles ca 94°) chelate rings adopting gauche and chair conformations, respectively (Tables 1 and 2). The macrocyclic ligands are in stretched forms with remote carboxylic groups. At the same time, the noticeable difference in the distances between their C atoms [C8—C8(–x + 2, –y + 1, –z + 1) of 14.241 (6) Å and C12—C16 of 15.29 (1) Å in I and II, respectively] is caused by different conformations of the trimethylene fragments of the substituents. The methylene groups bound to the distal nitrogen atoms in the six-membered chelate rings are axially oriented. Therewith, the sum of the C—N—C angles around these atoms [345.0° for N2 in I and 347.8 and 351.2° for N2 and N5 in II, respectively] indicates their partial sp² character (Tsymbal et al., 2019 ). The C—O bond lengths in the protonated carboxylic group in I differs significantly [1.319 (4) and 1.204 (3) Å for the C—OH and C=O bond, respectively], while in II they are nearly identical (ca 1.24 Å), thus indicating the lack of electron delocalization in the former and its occurrence in the latter case.

The azamacrocyclic ligands in the complexes under consideration are coordinated to the Cu^II ions by four secondary amine N atoms in a planar fashion forming the equatorial planes in the coordination spheres of the metal ions. The axial positions are occupied by the two chloride anions (in I) or by the O atom from the water molecule and chloride anion belonging to another molecule (in II). Because of a large Jahn–Teller distortion inherent in the 3d⁹ electronic configuration of Cu^II, the equatorial Cu—N bonds are significantly shorter than the axial Cu—Cl and Cu—O ones (Tables 1 and 2), therefore the coordination polyhedra can be described as tetragonally elongated trans-CuN₄(Cl)₂ or trans-CuN₄(O)(Cl) octahedrons in I and II, respectively. The length of the Cu—Cl bond in I is close to those observed in other Cu^II–chloride complexes of diazacyclam ligands (see Database survey). At the same time, the distance Cu1—Cl1(−x + 1, −y, −z + 1) [3.048 (2) Å] in II is significantly longer. Nevertheless, it is shorter than the sum of van der Waals radii of these atoms (3.15 Å) thus allowing to consider this Cu—Cl contact as a week coordinative [or semicoordinative (Valach, 1999 )] bond.

The CuN₄ moiety in I is strictly planar because of the location of the metal ion on crystallographic inversion center, while in II the Cu^II ion is displaced by 0.03 Å from the nearly planar (deviations of ±0.015 Å) mean plane of the N₄ donor atoms towards the O1W atom of water molecule. The axial Cu—D bonds (D = donor atom) in both compounds are nearly orthogonal to the CuN₄ plane with the deviations of the angles N—Cu—D from the normal not exceeding 5°.

The coordination polyhedron of the six-coordinated Cd^II ion in II is formed by the two bidentately coordinated carboxylic groups and two chloride ions. The metal ion possesses a deformed octahedral environment with cis-situated chloride anions. The values of chelate bite angles of the four-membered chelate rings are determined by the geometrical parameters of the coordinated carboxylate groups and analogously to other Cd^II carboxylate complexes (see, for example, Popovych et al., 2024 ) are close to 53° (Table 2). The angle between the mean planes of these chelate rings is 87.8 (2)°. The Cd—Cl bond lengths in II are very similar and are longer than the Cd—O bonds which, in turn, are significantly non-equivalent within each carboxylate group (Table 2).

The macrocyclic dicarboxylate complex anion in II displays a bridging function between two Cd^II cations. Each metal ion coordinates the carboxylate groups of two different macrocyclic ligands, thus resulting in the formation of a linear (the angle Cd⋯Cd⋯Cd = 180°) coordination polymeric chain, running along the [101] direction, with the shortest intrachain Cd^II⋯Cd^II (and Cu^II⋯Cu^II) distances of 19.2082 (8) Å. The distances between hetero metal ions equal 9.296 (1) and 10.414 (1) Å for Cu1⋯Cd1 and Cu1⋯Cd1(x − 1, y, z − 1), respectively (Fig. 2).

3. Supramolecular features

The complex I is characterized by a distinct lamellar structure, which is due to hydrogen-bonding interactions (Table 3). In particular, each carboxylate group of the electro-neutral complex molecule forms a pair of hydrogen bonds to a neighboring one acting as the proton donor for the chloride ion [O1C O1—H1C⋯Cl1(x − 1, y, z − 1)] and as the proton acceptor for the secondary amino group [N1—H1⋯O2(−x + 1, −y + 1, −z)]. This results in the formation of chains running in the [101] direction, with the distance between the metal atoms in a chain equal to 11.1582 (5) Å. These chains interact with each other via the formation of a hydrogen bond between another secondary amino group of the macrocycle and a chloride anion [N3—H3⋯Cl1(x, y, z − 1)], thus leading to layers oriented parallel to the (101) plane (Fig. 3). The shortest interchain Cu⋯Cu distance is 6.9325 (3) Å. There are no hydrogen-bonding contacts between the layers and the three-dimensional coherence of the crystal is provided by van der Waals interactions.

Table 3
Hydrogen-bond geometry (Å, °) for I

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2ⁱ	1.00	2.03	2.877 (3)	141
O1—H1C⋯Cl1ⁱⁱ	0.93 (3)	2.12 (3)	3.030 (2)	168 (3)
N3—H3⋯Cl1ⁱⁱⁱ	1.00	2.52	3.381 (2)	144
Symmetry codes: (i) ; (ii) ; (iii) .

Figure 3
The hydrogen-bonded layer in I oriented parallel to the (010) plane. C-bound H atoms have been omitted. The hydrogen bonds resulting in the formation of one-dimensional chains and those joining them into a layer are shown as magenta and orange dashed lines, respectively.

The parallel polymeric chains in the crystal of II interact with each other via the formation of semicoordinative Cu—Cl1(−x + 1, −y, −z + 1) bonds between atoms belonging to neighboring chains thus joining them into layers oriented parallel to the (10 $[\overline{1}]$ ) plane (Fig. 4). Thus, atom Cl1 in this compound displays a μ₂-bridging function with a Cu⋯Cd distance and Cu—Cl—Cd angle of 4.807 (1) Å and 119.33 (6)°, respectively. The layers are further consolidated by interchain hydrogen bonds formed between coordinated water molecule O1W—H and secondary amino group N4—H as the proton donors and both O atoms of the C16/O3/O4 carboxylic group as the proton acceptors (Fig. 4), as well as by weaker (D⋯A distances ca 3.4 Å) hydrogen bonds with participation of both chloride atoms as proton acceptors (Table 4). The intralayer hydrogen-bonding network also includes the water molecule of crystallization O2W (because of the lower site occupancy factors of O3W–O5W molecules their participation in the hydrogen-bonding interactions is not considered). There are no significant hydrogen-bonding interactions between the layers and the three-dimensional structure of crystal II is based on the weak C—H⋯O and C—H⋯Cl contacts.

Table 4
Hydrogen-bond geometry (Å, °) for II

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WB⋯O3ⁱⁱ	0.85	2.06	2.787 (7)	143
N4—H4⋯O4ⁱⁱⁱ	0.98	2.08	2.961 (8)	148
N1—H1⋯Cl2^iv	0.98	2.54	3.377 (5)	143
N6—H6⋯Cl1ⁱ	0.98	2.77	3.379 (5)	121
N3—H3⋯O2W	0.98	2.04	3.006 (13)	167
O1W—H1WA⋯O2W	0.85	2.28	3.037 (14)	149
O2W—H2WA⋯O2^iv	0.85	1.93	2.721 (14)	154
Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .

Figure 4
The packing in II, showing [101] polymeric chains cross-linked by Cu—Cl semicoordinative bonds (dark-green capped stick lines) to form layers oriented parallel to the (10 $[\overline{1}]$ ) plane. C-bound H atoms are omitted for clarity. Intralayer hydrogen bonds are shown as dashed lines. Hydrogen bonds with participation of chloride anion are not shown.

4. Database survey

The Cambridge Structural Database (CSD, version 5.46, September 2024; Groom et al., 2016 ) contains four structures formed by diazacyclam ligand H₂L with Ni^II [CSD refcodes NARBAK and NARBEO (Lu et al., 2005)] and Cu^II [WAMWEN and WAMWIR (Ou et al., 2005)] ions. Besides, the structure of the Cu^II complex of parent monosubstituted azacyclam ligand 3-(3-carboxypropyl)-1,3,5,8,12-pentaazacyclotetradecane [NUBFOI (Tsymbal et al., 2019)] has been also described. Among these compounds, NARBAK and WAMWEN represent trans-diaqua molecular complexes with the macrocycle L^2– bearing deprotonated but uncoordinated carboxylic groups. NUBFOI and WAMWIR are one- and two-dimensional coordination polymers, respectively, which are the result of self-polymerization due to the coordination of the carboxylic groups to the metal ion of another molecules. Interestingly, in both cases the Cu^II ion is bound with the carbonyl O atom of a protonated carboxylate group. In NARBEO the ligand H₂L is also present in protonated form and the charge of the cation is compensated by deprotonated but-2-enedioate which acts as bridge between the Ni^II centres thus resulting in the formation of a one-dimensional coordination polymer without involving in polymerization the carboxylic groups of the azacyclam ligand. Despite differences in the nature of the metal ions and protonation peculiarities, the macrocycles in all compounds possess very similar stretched trans-III (R,R,S,S) conformations with the distances between carboxylic groups varying between 13.6–15.0 Å, so this distance in II is the longest among all complexes studied.

There are only two examples in the CSD concerning the structure of trans-dichloride complexes of Cu(diazacyclam)²⁺ cations with 2-hydroxyehyl [MANKOB (Lampeka et al., 1998 )] and ethyl [MEDRAP (Jiang et al., 2006 )] substituents at distal nitrogen atoms of the macrocycle. In both cases the Cu—Cl coordination bond lengths are close to that observed in I (ca 2.83 Å), regardless of whether the chloride ion demonstrates monodentate (MEDRAP) or bridging (MANKOB) function. Similar distances are also observed in Cu^II chloride complexes of cyclam [see, for example, FODWAZ (Samoľová et al., 2019 ) and QASKUU (Heinemann et al., 2022 )], though a much shorter Cu—Cl coordination bond was also found [2.446 (4) Å in YEGMEF (Chang et al., 2017 )].

The CSD contains also six hits related to the six-coordinated Cd^II complexes containing two bidentately coordinated carboxylate ligands and two chloride anions. Four of them represent molecular compounds formed by substituted propionic [NASWUZ (Li & Mak, 1997 ); VOGKUZ (Galkina et al., 2014 ); UBILOK (Yang et al., 2021 )] or benzoic [VIQLIR (Deng et al., 2007 )] acids, while two other are one-dimensional coordination polymers based on dicarboxylates [KESGEX (Liu et al., 2017 ); KIRFAW (Jin et al., 2023 )]. Regardless of the structure, the geometrical parameters of the coordination polyhedra of the Cd^II ion in these compounds are very similar and resemble those observed in II.

5. Synthesis and crystallization

All commercially available chemicals and solvents were used in this work as purchased without further purification. The complex [Cu(H₂L)]Cl₂·2H₂O was synthesized according to a procedure described previously (Ou et al., 2005).

The complex [Cu(H₂L)Cl₂] (I) in form of light-violet prisms was obtained by recrystallization of hydrated compounds (55 mg) from a methanol (10 ml) solution. Yield: 40 mg (60%). Analysis calculated for C₁₆H₃₄Cl₂CuN₆O₄: C 37.76, H 6.73, N 16.51%. Found: C 37.65, H 6.82, N 16.35%.

For the preparation of the complex [CuCd(L)(H₂O)Cl₂]_n·1.25H₂O (II), a solution of 47 mg (0.2 mmol) Cd(NO₃)₂ in 5 ml of ethanol was mixed with 10 ml of aqueous solution containing 109 mg (0.2 mml) of Cu(H₂L)Cl₂·2H₂O and refluxed for 2 h. After filtration, the mixture was kept in a refrigerator. A light violet precipitate formed over several days was filtered off, washed with small amounts of methanol and diethyl ether, and dried in air. Yield: 74 mg (56%). Analysis calculated for C₁₆H_36.5 CdCl₂CuN₆O_6.25: C 29.12, H 5.58, N 12.74%. Found: C 29.01, H 5.71, N 12.65%. Single crystals of I and II suitable for X-ray diffraction analysis were selected from the samples resulting from the syntheses.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 5. The methylene H, secondary amine H atoms in I and II and water H atoms in II were placed in geometrically idealized positions and constrained to ride on their parent atoms with U_iso(H) values of 1.2U_eq(C), 1.2U_eq(N) and 1.5U_eq(O), respectively. The carboxylate H atoms in I were positioned geometrically and refined as riding with U_iso(H) = 1.5U_eq(O). Because of low site occupancies the water molecules of crystallization O2W–O5W in II were refined in an isotropic approximation.

Table 5
Experimental details

	I	II
Crystal data
Chemical formula	[CuCl₂(C₁₆H₃₄N₆O₄)]	[CuCd(C₁₆H₃₂N₆O₄)Cl₂(H₂O)]·1.25H₂O
M_r	508.93	659.85
Crystal system, space group	Monoclinic, P2₁/c	Triclinic, P $[\overline{1}]$
Temperature (K)	100	273
a, b, c (Å)	10.0036 (5), 15.8231 (7), 6.9325 (3)	10.1565 (4), 10.4249 (5), 14.6531 (7)
α, β, γ (°)	90, 99.808 (2), 90	80.305 (3), 80.117 (3), 64.149 (3)
V (Å³)	1081.29 (9)	1367.82 (11)
Z	2	2
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	1.29	1.79
Crystal size (mm)	0.12 × 0.07 × 0.06	0.15 × 0.05 × 0.05

Data collection
Diffractometer	Bruker APEXII CCD	Bruker APEXII CCD
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2022 $[Rigaku OD (2022). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )	Multi-scan (CrysAlis PRO; Rigaku OD, 2022 $[Rigaku OD (2022). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.892, 0.920	0.895, 0.910
No. of measured, independent and observed [I > 2σ(I)] reflections	5849, 1844, 1509	12964, 4762, 3446
R_int	0.089	0.040
(sin θ/λ)_max (Å⁻¹)	0.590	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.067, 1.05	0.050, 0.149, 1.04
No. of reflections	1844	4762
No. of parameters	136	297
No. of restraints	0	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.33	1.31, −0.69
Computer programs: CrysAlis PRO (Rigaku OD, 2022 $[Rigaku OD (2022). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT2018/2 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ), Mercury (Macrae et al., 2020 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC references: 2420902; 2420903

Crystal structure: contains datablocks I, II. DOI: https://doi.org/10.1107/S2056989025003792/hb8137sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989025003792/hb8137Isup2.hkl

Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989025003792/hb8137IIsup3.hkl

checkCIF report

Computing details top

[3,10-Bis(3-carboxypropyl)-1,3,5,8,10,12-hexaazacyclotetradecane-κ⁴N¹,N⁵,N⁸,N¹²]dichloridocopper(II) (I) top

Crystal data top

[CuCl₂(C₁₆H₃₄N₆O₄)]	F(000) = 534
M_r = 508.93	D_x = 1.563 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.0036 (5) Å	Cell parameters from 1452 reflections
b = 15.8231 (7) Å	θ = 2.0–24.9°
c = 6.9325 (3) Å	µ = 1.29 mm⁻¹
β = 99.808 (2)°	T = 100 K
V = 1081.29 (9) Å³	Prism, clear light violet
Z = 2	0.12 × 0.07 × 0.06 mm

Data collection top

Bruker APEXII CCD diffractometer	1509 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.089
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2022)	θ_max = 24.8°, θ_min = 2.1°
T_min = 0.892, T_max = 0.920	h = −11→11
5849 measured reflections	k = −18→18
1844 independent reflections	l = 0→8

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.029	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.067	w = 1/[σ²(F_o²) + (0.0246P)² + 0.8397P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
1844 reflections	Δρ_max = 0.30 e Å⁻³
136 parameters	Δρ_min = −0.33 e Å⁻³
0 restraints

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.

Refinement. Refined as a 2-component twin.

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

	x	y	z	U_iso*/U_eq
Cu1	1.000000	0.500000	0.500000	0.01515 (14)
Cl1	1.01968 (7)	0.39266 (4)	0.84077 (10)	0.01969 (18)
N3	0.9904 (2)	0.40064 (14)	0.3191 (3)	0.0158 (5)
H3	0.975658	0.422479	0.181720	0.019*
O1	0.2900 (2)	0.30989 (14)	−0.0055 (3)	0.0279 (5)
H1C	0.213 (3)	0.338 (2)	−0.068 (4)	0.042*
O2	0.3928 (2)	0.39295 (14)	−0.1942 (3)	0.0307 (6)
N1	0.7985 (2)	0.51266 (14)	0.4688 (3)	0.0155 (5)
H1	0.768622	0.542496	0.341645	0.019*
N2	0.7465 (2)	0.37665 (15)	0.3054 (3)	0.0176 (5)
C1	0.7212 (3)	0.43239 (18)	0.4585 (4)	0.0194 (7)
H1A	0.744468	0.402711	0.585529	0.023*
H1B	0.623066	0.445666	0.438437	0.023*
C8	0.3969 (3)	0.33740 (19)	−0.0747 (4)	0.0194 (7)
C5	0.6976 (3)	0.40643 (19)	0.1045 (4)	0.0195 (7)
H5A	0.771170	0.437569	0.056237	0.023*
H5B	0.620731	0.445800	0.104723	0.023*
C4	0.7700 (3)	0.57019 (18)	0.6243 (4)	0.0183 (6)
H4A	0.776660	0.539459	0.749953	0.022*
H4B	0.677474	0.593952	0.589865	0.022*
C7	0.5245 (3)	0.29165 (19)	0.0142 (4)	0.0211 (7)
H7A	0.519929	0.232826	−0.035123	0.025*
H7B	0.529656	0.289377	0.157987	0.025*
C3	1.1253 (3)	0.35995 (18)	0.3585 (4)	0.0175 (6)
H3A	1.136479	0.321178	0.250265	0.021*
H3B	1.135718	0.327019	0.481560	0.021*
C6	0.6522 (3)	0.3330 (2)	−0.0314 (4)	0.0227 (7)
H6A	0.635330	0.353432	−0.168322	0.027*
H6B	0.725710	0.290396	−0.019189	0.027*
C2	0.8799 (3)	0.33948 (18)	0.3360 (4)	0.0176 (6)
H2A	0.881701	0.293733	0.239062	0.021*
H2B	0.897761	0.313604	0.467921	0.021*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0137 (2)	0.0147 (2)	0.0171 (3)	−0.0005 (2)	0.0027 (2)	−0.0023 (2)
Cl1	0.0213 (4)	0.0218 (4)	0.0161 (4)	−0.0002 (3)	0.0034 (3)	0.0017 (3)
N3	0.0140 (12)	0.0170 (12)	0.0155 (12)	−0.0008 (10)	−0.0002 (10)	0.0024 (9)
O1	0.0209 (12)	0.0300 (13)	0.0332 (12)	−0.0003 (10)	0.0056 (10)	0.0070 (10)
O2	0.0233 (12)	0.0330 (13)	0.0343 (13)	0.0010 (10)	0.0007 (10)	0.0156 (11)
N1	0.0180 (12)	0.0166 (14)	0.0122 (12)	0.0004 (10)	0.0034 (10)	0.0009 (10)
N2	0.0176 (13)	0.0188 (13)	0.0152 (13)	−0.0019 (11)	−0.0010 (10)	0.0005 (10)
C1	0.0178 (16)	0.0219 (16)	0.0188 (16)	−0.0027 (13)	0.0039 (12)	0.0016 (13)
C8	0.0234 (17)	0.0184 (16)	0.0164 (15)	−0.0037 (13)	0.0032 (13)	−0.0041 (13)
C5	0.0157 (15)	0.0231 (17)	0.0185 (15)	−0.0031 (13)	−0.0005 (12)	0.0040 (12)
C4	0.0146 (15)	0.0230 (16)	0.0177 (16)	0.0051 (13)	0.0036 (12)	−0.0021 (13)
C7	0.0222 (18)	0.0207 (16)	0.0191 (15)	−0.0012 (13)	−0.0006 (13)	0.0000 (13)
C3	0.0205 (16)	0.0183 (16)	0.0133 (14)	0.0069 (12)	0.0021 (12)	−0.0018 (12)
C6	0.0213 (17)	0.0298 (18)	0.0165 (16)	0.0032 (14)	0.0019 (13)	−0.0019 (13)
C2	0.0202 (16)	0.0154 (15)	0.0162 (15)	−0.0023 (13)	0.0004 (12)	0.0015 (12)

Geometric parameters (Å, º) top

Cu1—Cl1	2.8889 (7)	C1—H1B	0.9900
Cu1—N3	2.003 (2)	C8—C7	1.505 (4)
Cu1—N3ⁱ	2.003 (2)	C5—H5A	0.9900
Cu1—N1ⁱ	2.000 (2)	C5—H5B	0.9900
Cu1—N1	2.000 (2)	C5—C6	1.516 (4)
N3—H3	1.0000	C4—H4A	0.9900
N3—C3	1.478 (4)	C4—H4B	0.9900
N3—C2	1.489 (4)	C4—C3ⁱ	1.513 (4)
O1—H1C	0.93 (4)	C7—H7A	0.9900
O1—C8	1.319 (4)	C7—H7B	0.9900
O2—C8	1.204 (3)	C7—C6	1.515 (4)
N1—H1	1.0000	C3—H3A	0.9900
N1—C1	1.482 (4)	C3—H3B	0.9900
N1—C4	1.475 (4)	C6—H6A	0.9900
N2—C1	1.436 (4)	C6—H6B	0.9900
N2—C5	1.472 (4)	C2—H2A	0.9900
N2—C2	1.441 (4)	C2—H2B	0.9900
C1—H1A	0.9900

N3ⁱ—Cu1—Cl1	87.71 (7)	N2—C5—H5B	109.4
N3—Cu1—Cl1	92.29 (6)	N2—C5—C6	111.0 (2)
N3ⁱ—Cu1—N3	180.0	H5A—C5—H5B	108.0
N1ⁱ—Cu1—Cl1	85.74 (7)	C6—C5—H5A	109.4
N1—Cu1—Cl1	94.26 (7)	C6—C5—H5B	109.4
N1ⁱ—Cu1—N3ⁱ	94.08 (9)	N1—C4—H4A	110.3
N1—Cu1—N3ⁱ	85.92 (9)	N1—C4—H4B	110.3
N1ⁱ—Cu1—N3	85.92 (9)	N1—C4—C3ⁱ	106.9 (2)
N1—Cu1—N3	94.08 (9)	H4A—C4—H4B	108.6
N1—Cu1—N1ⁱ	180.0	C3ⁱ—C4—H4A	110.3
Cu1—N3—H3	108.0	C3ⁱ—C4—H4B	110.3
C3—N3—Cu1	106.34 (16)	C8—C7—H7A	108.9
C3—N3—H3	108.0	C8—C7—H7B	108.9
C3—N3—C2	111.7 (2)	C8—C7—C6	113.2 (2)
C2—N3—Cu1	114.69 (17)	H7A—C7—H7B	107.8
C2—N3—H3	108.0	C6—C7—H7A	108.9
C8—O1—H1C	109.5	C6—C7—H7B	108.9
Cu1—N1—H1	106.7	N3—C3—C4ⁱ	107.1 (2)
C1—N1—Cu1	115.30 (18)	N3—C3—H3A	110.3
C1—N1—H1	106.7	N3—C3—H3B	110.3
C4—N1—Cu1	107.42 (17)	C4ⁱ—C3—H3A	110.3
C4—N1—H1	106.7	C4ⁱ—C3—H3B	110.3
C4—N1—C1	113.6 (2)	H3A—C3—H3B	108.6
C1—N2—C5	115.5 (2)	C5—C6—H6A	109.2
C1—N2—C2	114.7 (2)	C5—C6—H6B	109.2
C2—N2—C5	114.8 (2)	C7—C6—C5	112.0 (2)
N1—C1—H1A	108.8	C7—C6—H6A	109.2
N1—C1—H1B	108.8	C7—C6—H6B	109.2
N2—C1—N1	113.9 (2)	H6A—C6—H6B	107.9
N2—C1—H1A	108.8	N3—C2—H2A	108.8
N2—C1—H1B	108.8	N3—C2—H2B	108.8
H1A—C1—H1B	107.7	N2—C2—N3	113.9 (2)
O1—C8—C7	112.1 (3)	N2—C2—H2A	108.8
O2—C8—O1	123.8 (3)	N2—C2—H2B	108.8
O2—C8—C7	124.1 (3)	H2A—C2—H2B	107.7
N2—C5—H5A	109.4

Cu1—N3—C3—C4ⁱ	−43.6 (2)	C1—N2—C2—N3	−70.1 (3)
Cu1—N3—C2—N2	57.0 (3)	C8—C7—C6—C5	82.0 (3)
Cu1—N1—C1—N2	−56.5 (3)	C5—N2—C1—N1	−67.4 (3)
Cu1—N1—C4—C3ⁱ	40.6 (2)	C5—N2—C2—N3	67.2 (3)
O1—C8—C7—C6	−168.6 (2)	C4—N1—C1—N2	179.0 (2)
O2—C8—C7—C6	11.0 (4)	C3—N3—C2—N2	178.0 (2)
N2—C5—C6—C7	68.7 (3)	C2—N3—C3—C4ⁱ	−169.4 (2)
C1—N1—C4—C3ⁱ	169.3 (2)	C2—N2—C1—N1	69.6 (3)
C1—N2—C5—C6	−146.7 (3)	C2—N2—C5—C6	76.4 (3)

Symmetry code: (i) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ⁱⁱ	1.00	2.03	2.877 (3)	141
O1—H1C···Cl1ⁱⁱⁱ	0.93 (3)	2.12 (3)	3.030 (2)	168 (3)
N3—H3···Cl1^iv	1.00	2.52	3.381 (2)	144

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

Poly[[aqua[µ₃-3,10-bis(3-carboxypropyl)-1,3,5,8,10,12-hexaazacyclotetradecane-κ⁴N¹,N⁵,N⁸,N¹²:κ²O,O':κ²O'',O''']-µ-chloridocopper(II)cadmium(II]] 1.25-hydrate] (II) top

Crystal data top

[CuCd(C₁₆H₃₂N₆O₄)Cl₂(H₂O)]·1.25H₂O	Z = 2
M_r = 659.85	F(000) = 671
Triclinic, P1	D_x = 1.602 Mg m⁻³
a = 10.1565 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.4249 (5) Å	Cell parameters from 2340 reflections
c = 14.6531 (7) Å	θ = 2.5–25.1°
α = 80.305 (3)°	µ = 1.79 mm⁻¹
β = 80.117 (3)°	T = 273 K
γ = 64.149 (3)°	Prism, clear light violet
V = 1367.82 (11) Å³	0.15 × 0.05 × 0.05 mm

Data collection top

Bruker APEXII CCD diffractometer	3446 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.040
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2022)	θ_max = 25.0°, θ_min = 2.5°
T_min = 0.895, T_max = 0.910	h = −11→12
12964 measured reflections	k = −12→12
4762 independent reflections	l = −15→17

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.050	H-atom parameters constrained
wR(F²) = 0.149	w = 1/[σ²(F_o²) + (0.0757P)² + 2.6254P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
4762 reflections	Δρ_max = 1.31 e Å⁻³
297 parameters	Δρ_min = −0.69 e Å⁻³
3 restraints

Special details top

Refinement. Refined as a 2-component twin.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cd1	0.59670 (6)	0.26853 (5)	0.76221 (3)	0.04306 (19)
Cu1	0.33040 (8)	0.22435 (8)	0.19607 (5)	0.0368 (2)
Cl1	0.51803 (19)	0.08287 (18)	0.85462 (13)	0.0485 (4)
Cl2	0.3795 (2)	0.5038 (2)	0.78750 (15)	0.0630 (5)
O3	−0.2427 (5)	0.2757 (5)	−0.1510 (4)	0.0526 (13)
N4	0.1402 (5)	0.2125 (6)	0.1942 (4)	0.0387 (13)
H4	0.163812	0.116420	0.178712	0.046*
O1	0.6079 (6)	0.2308 (6)	0.6120 (3)	0.0617 (14)
N1	0.5280 (6)	0.2264 (6)	0.1986 (4)	0.0391 (13)
H1	0.509753	0.317288	0.220179	0.047*
O4	−0.1352 (6)	0.0727 (6)	−0.2134 (4)	0.0642 (15)
N6	0.3616 (5)	0.2651 (5)	0.0573 (4)	0.0365 (12)
H6	0.402797	0.173055	0.031144	0.044*
N3	0.3019 (6)	0.1802 (6)	0.3358 (4)	0.0389 (12)
H3	0.268598	0.269992	0.363502	0.047*
O1W	0.2008 (7)	0.4777 (6)	0.2217 (4)	0.0706 (16)
H1WA	0.209328	0.487228	0.276563	0.106*
H1WB	0.244848	0.523768	0.186423	0.106*
N2	0.5593 (6)	0.1102 (6)	0.3580 (4)	0.0433 (14)
N5	0.1150 (6)	0.3123 (6)	0.0317 (4)	0.0455 (14)
O2	0.7049 (7)	0.3750 (7)	0.6212 (4)	0.0745 (17)
C16	−0.1341 (8)	0.1573 (8)	−0.1647 (5)	0.0432 (16)
C12	0.6701 (8)	0.3075 (8)	0.5748 (5)	0.0492 (18)
C8	0.5961 (7)	0.2262 (8)	0.1016 (5)	0.0489 (18)
H8A	0.642826	0.129227	0.084057	0.059*
H8B	0.670876	0.262438	0.095161	0.059*
C9	0.5517 (7)	0.2254 (8)	0.4074 (5)	0.0446 (16)
H9A	0.496317	0.223751	0.468128	0.053*
H9B	0.499763	0.317219	0.372695	0.053*
C6	0.2278 (7)	0.3611 (7)	0.0110 (5)	0.0445 (16)
H6A	0.190725	0.456242	0.030616	0.053*
H6B	0.254370	0.368360	−0.055885	0.053*
C2	0.4356 (8)	0.0744 (8)	0.3782 (5)	0.0491 (18)
H2A	0.411541	0.064332	0.445198	0.059*
H2B	0.463691	−0.017891	0.356448	0.059*
C1	0.6218 (7)	0.1091 (8)	0.2624 (5)	0.0473 (18)
H1A	0.641518	0.018262	0.241569	0.057*
H1B	0.715277	0.115140	0.258505	0.057*
C7	0.4782 (8)	0.3202 (8)	0.0389 (5)	0.0483 (17)
H7A	0.437003	0.419018	0.052579	0.058*
H7B	0.519349	0.315835	−0.025881	0.058*
C5	0.0440 (7)	0.3178 (8)	0.1249 (5)	0.0469 (17)
H5A	−0.042463	0.299751	0.126945	0.056*
H5B	0.011290	0.413532	0.142412	0.056*
C4	0.0662 (7)	0.2235 (9)	0.2911 (5)	0.0499 (18)
H4A	−0.009896	0.188734	0.299020	0.060*
H4B	0.020861	0.322564	0.304598	0.060*
C13	0.1324 (8)	0.1938 (8)	−0.0182 (5)	0.0501 (18)
H13A	0.156987	0.106670	0.024350	0.060*
H13B	0.212635	0.178056	−0.067872	0.060*
C3	0.1813 (8)	0.1339 (8)	0.3557 (5)	0.0499 (18)
H3A	0.138471	0.145448	0.419911	0.060*
H3B	0.218770	0.033436	0.346619	0.060*
C14	−0.0074 (8)	0.2270 (8)	−0.0587 (6)	0.056 (2)
H14A	−0.083924	0.232508	−0.007732	0.067*
H14B	−0.037838	0.320795	−0.094049	0.067*
C15	0.0027 (8)	0.1229 (8)	−0.1198 (6)	0.0536 (19)
H15A	0.028909	0.030147	−0.083454	0.064*
H15B	0.082553	0.114088	−0.168889	0.064*
C10	0.7015 (8)	0.2104 (10)	0.4194 (5)	0.059 (2)
H10A	0.756318	0.210913	0.358318	0.070*
H10B	0.752778	0.117877	0.453587	0.070*
C11	0.7026 (10)	0.3245 (11)	0.4692 (5)	0.068 (2)
H11A	0.630509	0.416470	0.445325	0.081*
H11B	0.798489	0.326495	0.453979	0.081*
O5W	−0.129 (3)	0.756 (3)	0.3727 (17)	0.075 (7)*	0.25
H5WA	−0.133178	0.717443	0.327227	0.113*	0.25
H5WB	−0.043408	0.754503	0.363557	0.113*	0.25
O4W	−0.215 (3)	0.686 (3)	0.3405 (19)	0.085 (7)*	0.25
H4WA	−0.178747	0.593968	0.349859	0.127*	0.25
H4WB	−0.210637	0.725748	0.386049	0.127*	0.25
O2W	0.1567 (12)	0.4480 (13)	0.4332 (8)	0.074 (3)*	0.5
H2WA	0.212914	0.489423	0.431887	0.111*	0.5
H2WB	0.144304	0.419643	0.491597	0.111*	0.5
O3W	−0.142 (3)	0.610 (3)	0.2733 (19)	0.088 (8)*	0.25
H3WA	−0.167073	0.670086	0.312565	0.132*	0.25
H3WB	−0.167283	0.544546	0.302075	0.132*	0.25

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.0545 (3)	0.0486 (3)	0.0367 (3)	−0.0289 (3)	−0.0119 (2)	−0.0047 (2)
Cu1	0.0379 (4)	0.0442 (5)	0.0340 (5)	−0.0223 (4)	−0.0087 (3)	0.0006 (4)
Cl1	0.0588 (10)	0.0398 (9)	0.0498 (11)	−0.0251 (8)	−0.0014 (8)	−0.0045 (8)
Cl2	0.0705 (13)	0.0480 (11)	0.0641 (13)	−0.0222 (10)	−0.0027 (10)	−0.0014 (10)
O3	0.053 (3)	0.054 (3)	0.060 (3)	−0.027 (3)	−0.022 (2)	−0.003 (3)
N4	0.034 (3)	0.040 (3)	0.045 (3)	−0.016 (2)	−0.003 (2)	−0.011 (3)
O1	0.093 (4)	0.072 (4)	0.040 (3)	−0.054 (3)	−0.009 (3)	−0.004 (3)
N1	0.042 (3)	0.049 (3)	0.038 (3)	−0.029 (3)	−0.004 (2)	−0.006 (3)
O4	0.076 (4)	0.062 (3)	0.075 (4)	−0.040 (3)	−0.017 (3)	−0.017 (3)
N6	0.044 (3)	0.033 (3)	0.038 (3)	−0.019 (2)	−0.011 (2)	−0.003 (2)
N3	0.046 (3)	0.046 (3)	0.032 (3)	−0.025 (3)	−0.008 (2)	−0.002 (2)
O1W	0.100 (4)	0.047 (3)	0.067 (4)	−0.032 (3)	−0.015 (3)	−0.004 (3)
N2	0.046 (3)	0.052 (3)	0.038 (3)	−0.024 (3)	−0.014 (3)	−0.003 (3)
N5	0.047 (3)	0.044 (3)	0.047 (4)	−0.015 (3)	−0.015 (3)	−0.008 (3)
O2	0.098 (4)	0.096 (5)	0.056 (4)	−0.061 (4)	−0.003 (3)	−0.025 (3)
C16	0.050 (4)	0.042 (4)	0.042 (4)	−0.023 (4)	−0.011 (3)	−0.001 (3)
C12	0.057 (4)	0.050 (4)	0.047 (4)	−0.025 (4)	−0.010 (4)	−0.012 (4)
C8	0.044 (4)	0.064 (5)	0.049 (4)	−0.031 (4)	−0.001 (3)	−0.013 (4)
C9	0.052 (4)	0.052 (4)	0.038 (4)	−0.026 (3)	−0.008 (3)	−0.008 (3)
C6	0.053 (4)	0.038 (4)	0.045 (4)	−0.019 (3)	−0.016 (3)	−0.001 (3)
C2	0.063 (5)	0.051 (4)	0.047 (4)	−0.034 (4)	−0.023 (4)	0.003 (3)
C1	0.043 (4)	0.054 (4)	0.049 (4)	−0.018 (3)	−0.016 (3)	−0.013 (4)
C7	0.062 (4)	0.059 (5)	0.040 (4)	−0.040 (4)	0.003 (3)	−0.010 (3)
C5	0.043 (4)	0.050 (4)	0.049 (4)	−0.015 (3)	−0.012 (3)	−0.012 (3)
C4	0.044 (4)	0.065 (5)	0.045 (4)	−0.026 (4)	0.002 (3)	−0.016 (4)
C13	0.045 (4)	0.050 (4)	0.050 (4)	−0.011 (3)	−0.017 (3)	−0.007 (4)
C3	0.058 (4)	0.065 (5)	0.038 (4)	−0.039 (4)	0.003 (3)	−0.005 (4)
C14	0.050 (4)	0.054 (5)	0.070 (5)	−0.018 (4)	−0.022 (4)	−0.017 (4)
C15	0.053 (4)	0.051 (4)	0.060 (5)	−0.021 (4)	−0.015 (4)	−0.009 (4)
C10	0.063 (5)	0.089 (6)	0.043 (4)	−0.048 (5)	−0.001 (4)	−0.021 (4)
C11	0.093 (6)	0.106 (7)	0.038 (4)	−0.073 (6)	−0.002 (4)	−0.014 (4)

Geometric parameters (Å, º) top

Cd1—Cl1	2.5125 (18)	C8—C7	1.513 (10)
Cd1—Cl2	2.515 (2)	C9—H9A	0.9700
Cd1—O3ⁱ	2.266 (4)	C9—H9B	0.9700
Cd1—O1	2.275 (5)	C9—C10	1.498 (9)
Cd1—O4ⁱ	2.637 (6)	C6—H6A	0.9700
Cd1—O2	2.494 (6)	C6—H6B	0.9700
Cu1—N4	1.993 (5)	C2—H2A	0.9700
Cu1—N1	2.023 (5)	C2—H2B	0.9700
Cu1—N6	2.006 (5)	C1—H1A	0.9700
Cu1—N3	2.020 (5)	C1—H1B	0.9700
Cu1—O1W	2.446 (5)	C7—H7A	0.9700
Cu1—Cl1ⁱⁱ	3.048 (2)	C7—H7B	0.9700
O3—C16	1.265 (8)	C5—H5A	0.9700
N4—H4	0.9800	C5—H5B	0.9700
N4—C5	1.491 (8)	C4—H4A	0.9700
N4—C4	1.486 (8)	C4—H4B	0.9700
O1—C12	1.229 (9)	C4—C3	1.505 (10)
N1—H1	0.9800	C13—H13A	0.9700
N1—C8	1.470 (8)	C13—H13B	0.9700
N1—C1	1.478 (8)	C13—C14	1.510 (9)
O4—C16	1.230 (8)	C3—H3A	0.9700
N6—H6	0.9800	C3—H3B	0.9700
N6—C6	1.487 (8)	C14—H14A	0.9700
N6—C7	1.495 (8)	C14—H14B	0.9700
N3—H3	0.9800	C14—C15	1.479 (10)
N3—C2	1.483 (8)	C15—H15A	0.9700
N3—C3	1.471 (8)	C15—H15B	0.9700
O1W—H1WA	0.8500	C10—H10A	0.9700
O1W—H1WB	0.8500	C10—H10B	0.9700
N2—C9	1.471 (8)	C10—C11	1.501 (10)
N2—C2	1.432 (8)	C11—H11A	0.9700
N2—C1	1.435 (9)	C11—H11B	0.9700
N5—C6	1.416 (9)	O5W—H5WA	0.8500
N5—C5	1.428 (9)	O5W—H5WB	0.8500
N5—C13	1.470 (9)	O4W—H4WA	0.8604
O2—C12	1.242 (8)	O4W—H4WB	0.8605
C16—C15	1.513 (9)	O2W—H2WA	0.8498
C12—C11	1.522 (10)	O2W—H2WB	0.8632
C8—H8A	0.9700	O3W—H3WA	0.8501
C8—H8B	0.9700	O3W—H3WB	0.8501

Cl1—Cd1—Cl2	104.67 (7)	C10—C9—H9A	109.2
Cl1—Cd1—O4ⁱ	84.16 (13)	C10—C9—H9B	109.2
Cl2—Cd1—O4ⁱ	153.76 (12)	N6—C6—H6A	109.0
O3ⁱ—Cd1—Cl1	103.44 (14)	N6—C6—H6B	109.0
O3ⁱ—Cd1—Cl2	101.32 (14)	N5—C6—N6	112.8 (5)
O3ⁱ—Cd1—O1	134.6 (2)	N5—C6—H6A	109.0
O3ⁱ—Cd1—O4ⁱ	52.44 (17)	N5—C6—H6B	109.0
O3ⁱ—Cd1—O2	90.52 (19)	H6A—C6—H6B	107.8
O1—Cd1—Cl1	103.28 (14)	N3—C2—H2A	108.6
O1—Cd1—Cl2	106.49 (16)	N3—C2—H2B	108.6
O1—Cd1—O4ⁱ	95.06 (19)	N2—C2—N3	114.7 (6)
O1—Cd1—O2	53.54 (19)	N2—C2—H2A	108.6
O2—Cd1—Cl1	154.86 (14)	N2—C2—H2B	108.6
O2—Cd1—Cl2	92.68 (16)	H2A—C2—H2B	107.6
O2—Cd1—O4ⁱ	88.2 (2)	N1—C1—H1A	108.7
N4—Cu1—N1	177.4 (2)	N1—C1—H1B	108.7
N4—Cu1—N6	93.9 (2)	N2—C1—N1	114.4 (5)
N4—Cu1—N3	86.5 (2)	N2—C1—H1A	108.7
N4—Cu1—O1W	91.0 (2)	N2—C1—H1B	108.7
N1—Cu1—O1W	91.6 (2)	H1A—C1—H1B	107.6
N6—Cu1—N1	86.6 (2)	N6—C7—C8	107.2 (6)
N6—Cu1—N3	179.1 (2)	N6—C7—H7A	110.3
N6—Cu1—O1W	93.9 (2)	N6—C7—H7B	110.3
N3—Cu1—N1	93.0 (2)	C8—C7—H7A	110.3
N3—Cu1—O1W	86.9 (2)	C8—C7—H7B	110.3
C16—O3—Cd1ⁱⁱⁱ	100.6 (4)	H7A—C7—H7B	108.5
Cu1—N4—H4	107.3	N4—C5—H5A	108.9
C5—N4—Cu1	115.2 (4)	N4—C5—H5B	108.9
C5—N4—H4	107.3	N5—C5—N4	113.5 (5)
C4—N4—Cu1	106.6 (4)	N5—C5—H5A	108.9
C4—N4—H4	107.3	N5—C5—H5B	108.9
C4—N4—C5	112.7 (5)	H5A—C5—H5B	107.7
C12—O1—Cd1	97.8 (4)	N4—C4—H4A	110.2
Cu1—N1—H1	107.7	N4—C4—H4B	110.2
C8—N1—Cu1	106.7 (4)	N4—C4—C3	107.7 (5)
C8—N1—H1	107.7	H4A—C4—H4B	108.5
C8—N1—C1	113.5 (5)	C3—C4—H4A	110.2
C1—N1—Cu1	113.3 (4)	C3—C4—H4B	110.2
C1—N1—H1	107.7	N5—C13—H13A	109.5
C16—O4—Cd1ⁱⁱⁱ	84.1 (4)	N5—C13—H13B	109.5
Cu1—N6—H6	107.3	N5—C13—C14	110.8 (6)
C6—N6—Cu1	116.0 (4)	H13A—C13—H13B	108.1
C6—N6—H6	107.3	C14—C13—H13A	109.5
C6—N6—C7	112.8 (5)	C14—C13—H13B	109.5
C7—N6—Cu1	105.9 (4)	N3—C3—C4	108.8 (6)
C7—N6—H6	107.3	N3—C3—H3A	109.9
Cu1—N3—H3	107.7	N3—C3—H3B	109.9
C2—N3—Cu1	115.1 (4)	C4—C3—H3A	109.9
C2—N3—H3	107.7	C4—C3—H3B	109.9
C3—N3—Cu1	106.6 (4)	H3A—C3—H3B	108.3
C3—N3—H3	107.7	C13—C14—H14A	108.4
C3—N3—C2	111.9 (5)	C13—C14—H14B	108.4
Cu1—O1W—H1WA	109.1	H14A—C14—H14B	107.5
Cu1—O1W—H1WB	108.8	C15—C14—C13	115.5 (6)
H1WA—O1W—H1WB	104.5	C15—C14—H14A	108.4
C2—N2—C9	116.2 (6)	C15—C14—H14B	108.4
C2—N2—C1	115.4 (5)	C16—C15—H15A	108.2
C1—N2—C9	116.2 (6)	C16—C15—H15B	108.2
C6—N5—C5	117.2 (5)	C14—C15—C16	116.5 (6)
C6—N5—C13	116.7 (6)	C14—C15—H15A	108.2
C5—N5—C13	117.3 (6)	C14—C15—H15B	108.2
C12—O2—Cd1	87.1 (5)	H15A—C15—H15B	107.3
O3—C16—C15	117.2 (6)	C9—C10—H10A	108.5
O4—C16—O3	122.9 (6)	C9—C10—H10B	108.5
O4—C16—C15	119.9 (7)	C9—C10—C11	115.1 (7)
O1—C12—O2	121.5 (7)	H10A—C10—H10B	107.5
O1—C12—C11	119.9 (6)	C11—C10—H10A	108.5
O2—C12—C11	118.5 (7)	C11—C10—H10B	108.5
N1—C8—H8A	109.9	C12—C11—H11A	108.3
N1—C8—H8B	109.9	C12—C11—H11B	108.3
N1—C8—C7	108.9 (6)	C10—C11—C12	115.8 (7)
H8A—C8—H8B	108.3	C10—C11—H11A	108.3
C7—C8—H8A	109.9	C10—C11—H11B	108.3
C7—C8—H8B	109.9	H11A—C11—H11B	107.4
N2—C9—H9A	109.2	H5WA—O5W—H5WB	104.5
N2—C9—H9B	109.2	H4WA—O4W—H4WB	113.5
N2—C9—C10	112.0 (6)	H2WA—O2W—H2WB	103.1
H9A—C9—H9B	107.9	H3WA—O3W—H3WB	104.5

Cd1ⁱⁱⁱ—O3—C16—O4	−0.8 (8)	O2—C12—C11—C10	162.1 (7)
Cd1ⁱⁱⁱ—O3—C16—C15	177.9 (5)	C8—N1—C1—N2	178.0 (5)
Cd1—O1—C12—O2	0.0 (8)	C9—N2—C2—N3	74.3 (7)
Cd1—O1—C12—C11	−178.5 (6)	C9—N2—C1—N1	−71.1 (7)
Cd1ⁱⁱⁱ—O4—C16—O3	0.7 (7)	C9—C10—C11—C12	78.6 (10)
Cd1ⁱⁱⁱ—O4—C16—C15	−177.9 (7)	C6—N6—C7—C8	171.2 (5)
Cd1—O2—C12—O1	0.0 (8)	C6—N5—C5—N4	−69.7 (8)
Cd1—O2—C12—C11	178.5 (7)	C6—N5—C13—C14	−131.6 (7)
Cu1—N4—C5—N5	55.3 (7)	C2—N3—C3—C4	−165.0 (6)
Cu1—N4—C4—C3	−41.9 (6)	C2—N2—C9—C10	152.8 (6)
Cu1—N1—C8—C7	38.4 (6)	C2—N2—C1—N1	69.9 (8)
Cu1—N1—C1—N2	−60.1 (6)	C1—N1—C8—C7	163.9 (5)
Cu1—N6—C6—N5	−55.0 (6)	C1—N2—C9—C10	−66.4 (8)
Cu1—N6—C7—C8	43.3 (6)	C1—N2—C2—N3	−66.8 (8)
Cu1—N3—C2—N2	55.6 (7)	C7—N6—C6—N5	−177.3 (5)
Cu1—N3—C3—C4	−38.4 (6)	C5—N4—C4—C3	−169.2 (6)
O3—C16—C15—C14	4.1 (11)	C5—N5—C6—N6	69.0 (8)
N4—C4—C3—N3	54.4 (7)	C5—N5—C13—C14	81.8 (8)
O1—C12—C11—C10	−19.3 (12)	C4—N4—C5—N5	177.9 (6)
N1—C8—C7—N6	−55.6 (7)	C13—N5—C6—N6	−77.7 (7)
O4—C16—C15—C14	−177.2 (7)	C13—N5—C5—N4	76.8 (7)
N2—C9—C10—C11	179.9 (6)	C13—C14—C15—C16	−177.4 (7)
N5—C13—C14—C15	173.1 (7)	C3—N3—C2—N2	177.4 (6)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WB···O3^iv	0.85	2.06	2.787 (7)	143
N4—H4···O4^v	0.98	2.08	2.961 (8)	148
N1—H1···Cl2^vi	0.98	2.54	3.377 (5)	143
N6—H6···Cl1ⁱⁱ	0.98	2.77	3.379 (5)	121
N3—H3···O2W	0.98	2.04	3.006 (13)	167
O1W—H1WA···O2W	0.85	2.28	3.037 (14)	149
O2W—H2WA···O2^vi	0.85	1.93	2.721 (14)	154

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

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